Polymerizable liquid crystal formulation

Abstract

This invention relates to polymerizable liquid crystal (LC) formulations (as a subclass of liquid crystal materials), and more particularly to polymerizable LC ink formulations for inkjet printing, preferably free of PFAS (which enables the reduction of perfluorocarbons and provides an environmentally friendly material), and comprising one or more polymerizable mesocrystalline compounds (also known as reactive mesocrystalline (RM)) and three or more organic solvents. It also relates to polymers and polymer films obtained from such formulations, and the use of said formulations, polymers, and polymer films in optical or electro-optical components or devices, particularly for digital optics or augmented reality or virtual reality (AR / VR) applications, such as polarizers, optical compensators, reflective films, diffraction or surface gratings, Bragg polarization gratings (Bragg PG), polarization volume gratings (PVG), polarization volume holograms (PVH), Panchara Thamnam-Berry (PB) gratings, non-mechanical beam steering elements, optical waveguides, optical couplers, optical combiners, optical deflectors, polarization beam splitters, partial mirrors, or lenses.

Description

Technical Field

[0001] This invention relates to polymerizable liquid crystal (LC) formulations (as a subclass of liquid crystal materials), and more particularly to polymerizable LC ink formulations for inkjet printing, preferably free of PFAS (which enables the reduction of perfluorinated carbon and provides an environmentally friendly material), and comprising one or more polymerizable mesocrystalline compounds (also known as reactive mesocrystalline (RM)) and three or more organic solvents. It also relates to polymers and polymer films obtained from such formulations, and the use of said formulations, polymers, and polymer films in optical or electro-optical components or devices, particularly for digital optics or augmented reality or virtual reality (AR / VR) applications, such as polarizers, optical compensators, reflective films, diffraction or surface gratings, Bragg polarization gratings (Bragg PG), polarization volume gratings (PVG), polarization volume holograms (PVH), Panchara Thamnam-Berry (PB) gratings, non-mechanical beam steering elements, optical waveguides, optical couplers, optical combiners, optical deflectors, polarization beam splitters, partial mirrors, or lenses. Background Technology

[0002] Reactive mesocrystalline (RM), or polymerizable liquid crystal (LC), combines the properties of liquid crystals and polymers. RM can be used to fabricate functional films or coatings with tunable refractive indices, polarization, and surface alignment. These materials can be applied to waveguides or optics in AR or VR devices to enhance performance, image quality, field of view, and overall user experience. Furthermore, polymerizable RM can form thin films with high birefringence, which can be integrated into flexible, lightweight devices. The quality of the RM layer is crucial for visual quality and device performance.

[0003] Inkjet printing (IJP) is one of the most promising methods for solution-deposited RM materials because it enables selective material deposition in regions of interest. Several requirements must be met for RM formulations to be used in inkjet printing, such as jettability, stability (shelf life), and process compatibility. Additionally, substrate-solution interactions limit the quality of the resulting device. Solvent selection has a specific impact on formulation parameters and often determines whether a formulation is suitable for inkjet printing. In the case of RM formulations, additional requirements related to good LC alignment are also crucial.

[0004] In the prior art, typical solvents recommended for RM formulations are selected from short-chain, low-boiling-point ketones, alcohols, glycols, or their esters. Toluene and xylene are also frequently mentioned among aromatic compounds. However, the impact of solvent selection on the quality of printed films in terms of wetting and shape retention is generally not addressed.

[0005] However, solvent selection has a specific impact on formulation parameters and often determines its suitability for inkjet printing onto a particular substrate. In many cases, solvents suitable for inkjet printing have poor solute solubility or are unsuitable for further processing conditions, and vice versa. In addition to substrate-liquid interactions, the formulation should also be suitable in terms of solubility and jet stability.

[0006] Furthermore, when manufacturing multilayer optical elements in which multiple RM layers are directly deposited onto each other, it is important to ensure good and uniform alignment quality to prevent damage to the lower RM layer when the next RM layer is deposited on top of it, and to achieve strong intermolecular interactions between the RM layers to impart an alignment direction from one RM layer to the next. Simultaneously, solvents used in the formulation for depositing the second RM layer onto the first RM layer should be avoided to prevent damage to the first layer or to allow individual components of the second RM formulation to migrate into the first layer.

[0007] Therefore, it is desirable to provide inks that are particularly suitable for use as printing inks and can achieve good solubility of RM, while exhibiting other advantageous properties such as good wetting, good jetting properties, high jetting stability, long shelf life, and good process compatibility with standard printing processes, especially inkjet printing, which avoids damage to the cured RM layer used as a substrate, and can also be used in RM formulations for large-scale production.

[0008] One object of the present invention is to provide an RM formulation exhibiting one or more of the advantages described above. Other objects of the present invention will be apparent to those skilled in the art from the following detailed description.

[0009] Surprisingly, the inventors of this invention have discovered that these objectives can be achieved by providing the RM formulation according to the invention as described and claimed below.

[0010] Therefore, the inventors of this invention have surprisingly discovered that by using solvents and solvent blends in combination with the RMs according to the invention as described below, formulations exhibiting one or more of the following characteristics—optimal solubility, good wetting, good jetting properties, high stability, suitable processing window, and good process compatibility—and allowing for the adjustment of parameters required for inkjet printing. While these RM formulations are particularly suitable for inkjet printing, they can also be used in other printing or coating methods as described below. Summary of the Invention

[0011] This invention relates to a formulation (hereinafter also referred to as a "RM formulation") comprising a polymerizable mesocrystalline compound (hereinafter also referred to as a "reactive mesocrystalline compound" or "RM") or a mixture of two or more polymerizable mesocrystalline compounds (hereinafter also referred to as a "RM mixture"), and further comprising a solvent blend consisting of three or more, preferably three, organic solvents.

[0012] The solvent blend comprises a first solvent, a second solvent, and a third solvent. The first solvent is a cycloalkanone having 5, 6, 7, or 8 carbon atoms, preferably cyclohexanone or cycloheptanone. The second solvent is an aromatic ketone or aromatic ester, preferably selected from formulas S1A and S1B. The third solvent is an aliphatic ketone, aliphatic or aromatic alcohol, or diol, preferably selected from formulas S2A, S2B, S2C, and S2D.

[0013] Ar S1 -(CH2) a -CO-R S1 S1A

[0014] Ar S2 -(CH2) b -Z S -R S2 S1B

[0015] R S3 -CO-R S4 S2A

[0016] R S3 -C(OH)R S4 R S5 S2B

[0017] R S6 -OH S2C

[0018] R S7 -O-(CHR S8 -CHR S9 -O) c -R S10 S2D

[0019] Each of these groups, independently of each other and in the same or different manner each time it appears, has the following meaning:

[0020] Ar S1 Ar S2 It is an aryl or heteroaryl group having 5 or 6 ring atoms, optionally containing one or two heteroatoms selected from N, O and S, preferably phenyl, and optionally surrounded by one or more L groups. S replace,

[0021] L S It is an alkyl, alkoxy, alkyl carbonyl, alkoxy carbonyl, alkyl carbonyloxy, or alkoxy carbonyloxy group having 1 to 5 carbon atoms, preferably an alkyl group having 1 to 5 carbon atoms, which is F, Cl, or optionally halogenated.

[0022] R S1The alkyl group has 1 to 8, preferably 1 to 6, carbon atoms, with methyl, ethyl, n-propyl, sec-propyl, isopropyl, n-butyl, sec-butyl, isobutyl, or tert-butyl being very preferred, and ethyl or isobutyl being most preferred.

[0023] Z S It is -CO-O- or -O-CO-.

[0024] R S2 It is an alkyl group having 1 to 8, preferably 1 to 6, carbon atoms, very preferably methyl, ethyl, propyl or butyl, and most preferably methyl or ethyl.

[0025] R S3 It is an alkyl group having 1 to 7, preferably 1 to 5, carbon atoms, very preferably methyl, ethyl, propyl or butyl, and most preferably methyl or ethyl.

[0026] R S4 It is an alkyl group having 1 to 15, preferably 5 to 11, carbon atoms.

[0027] and R S3 and R S4 It can also form cycloalkyl groups with 5 to 8, preferably 5 or 6, ring atoms, with optional substitution together with the hydroxyl C atom.

[0028] R S5 It is H or an alkyl group having 1 to 6 carbon atoms, preferably H.

[0029] The total number of C atoms in formulas S2A and S2B is 5 to 16, with 5 to 12 being highly preferred.

[0030] R S6 It is an alkyl group having 1 to 12, preferably 4 to 11 carbon atoms, or a phenylalkyl group having 1 to 4 alkyl carbon atoms, preferably phenylmethyl, 2-phenylethyl, or 3-phenylpropyl.

[0031] R S7 It is H, methyl, acetyl, or phenyl, with H, acetyl, or phenyl being very preferred.

[0032] R S8 R S9 It is H, methyl or ethyl, with H or methyl being very preferred.

[0033] R S10 It is H, methyl or ethyl.

[0034] a is 0 or 1.

[0035] b is 0 or 1.

[0036] c is 1, 2, or 3.

[0037] The present invention further relates to RM formulations as described above and below, which further comprise one or more additives, preferably selected from polymerization initiators, surfactants, stabilizers, catalysts, sensitizers, inhibitors, chain transfer agents, co-reactive monomers, reactive thickeners, surfactants, lubricants, wetting agents, dispersants, hydrophobic agents, adhesives, flow improvers, degassing or defoaming agents, degassing agents, diluents, reactive diluents, auxiliaries, colorants, dyes, pigments, and nanoparticles.

[0038] The present invention further relates to polymers or polymer films that are available or obtainable from RM formulations as described above and below.

[0039] The present invention further relates to a method for preparing a polymer or polymer film from an RM formulation containing RM or an RM mixture and a solvent or solvent blend as described above and below, comprising the steps of: depositing a layer of the RM formulation onto a substrate, preferably removing the solvent, optionally annealing the layer, and polymerizing the RM or RM mixture, preferably at a temperature at which it exhibits a liquid crystal phase, wherein the RM formulation is preferably deposited onto the substrate by printing, very preferably by inkjet printing.

[0040] The present invention further relates to the use of RM formulations, polymers or polymer films as described above and below in optical, electro-optical or electronic components or devices.

[0041] The present invention further relates to an optical, electro-optical or electronic device or component comprising an RM formulation, polymer or polymer film as described above and below.

[0042] The components include, but are not limited to, optical delay films such as quarter-wave plates (QWP) or half-wave plates (HWP), polarizers, optical compensators, reflective films, diffraction or surface gratings such as Bragg polarization gratings (Bragg PG), polarization volume gratings (PVG), polarization volume holograms (PVH), Panchara Tunnam-Berry (PB) gratings, and non-mechanical beam steering elements, optical waveguides, optical couplers, deflectors or combiners, polarization beam splitters, partial mirrors, reflective films, alignment layers, color filters, anti-static protective sheets, electromagnetic interference protective sheets, lenses for light guiding, focusing and optical effects, polarization control lenses, PB deflectors, PB lenses and infrared reflective films; for example, for use in LC displays (LCD), organic light-emitting diodes (OLED), autostereoscopic 3D displays, near-eye displays, augmented reality (AR) or virtual reality (VR) systems, switchable windows, spatial light modulators, optical data storage, remote optical sensing, holography, spectroscopy, optical communication, polarization or front / back illumination.

[0043] The devices include, but are not limited to, optoelectronic displays, especially LCDs, OLEDs, nonlinear optical (NLO) devices, autostereoscopic 3D displays, perspective near-eye displays, head-up displays, AR / VR systems, glasses for AR / VR applications (goggle), switchable windows, spatial light modulators, optical data storage devices, optical sensors, holographic devices, spectrometers, optical communication systems, polarizers, or headlights / backlights. Attached Figure Description

[0044] Figure 1 Nine square test patterns with different amounts of deposited material are shown to test the shape quality of the printed film as described in the examples below.

[0045] Figure 2a -d (x2 magnification) shows a stitched micrograph of a polymer film prepared by inkjet-printed RM reference formulation (ac) and the RM formulation according to the invention (d) as described in Example 1, between cross polarizers.

[0046] Figure 3a &b (x2 magnification) shows a stitched micrograph of a polymer film prepared according to the present invention using an inkjet-printed RM formulation as described in Example 2, between cross polarizers.

[0047] Figure 4a &b (x2 magnification) shows a stitched micrograph of a polymer film prepared by inkjet printing according to the RM formulation described in Example 3, between cross polarizers.

[0048] Figure 5a -c (x2 magnification) shows a stitched micrograph of a polymer film prepared by inkjet-printed RM reference formulation (a) and the RM formulation according to the invention (b & c) as described in Example 4, spliced ​​between cross polarizers.

[0049] Definition of terminology

[0050] Throughout the embodiments described herein and the appended claims, the words “comprise” and “containing”, and variations thereof, such as “comprising” and “comprises”, mean “including but not limited to”, and do not intend to exclude other components.

[0051] Unless otherwise expressly indicated in the text, as used herein, the plural form of a term should be considered to include the singular form and vice versa.

[0052] As used herein, the term "membrane" includes rigid or flexible, self-supporting or independent membranes with mechanical stability, and coatings or layers on or between two substrates.

[0053] As used herein, the terms “reactive mesocrystalline” and “RM” should be understood to mean a compound containing a mesocrystalline or liquid crystal framework and, optionally, one or more functional groups connected thereto via spacer groups, suitable for polymerization and also referred to as “polymerizable groups” or “P”.

[0054] Unless otherwise stated, the term “polymerizable compound” as used herein should be understood to mean a polymerizable monomeric compound.

[0055] A polymerizable compound or RM with one polymerizable group is also called a "single-reactive" compound; a polymerizable compound or RM with two polymerizable groups is called a "two-reactive" compound; and a polymerizable compound or RM with more than two polymerizable groups is called a "multi-reactive" compound. A compound without any polymerizable groups is also called a "non-reactive" compound.

[0056] The terms “liquid crystal,” “mesocrystalline,” and “mesocrystalline compound” as used in this article refer to compounds that can exist as an intermediate phase or, more specifically, as an LC phase under suitable temperature, pressure, and concentration conditions.

[0057] The term "clearing point" refers to the temperature at which the transition between the mesophase and the isotropic phase, which has the highest temperature range, occurs.

[0058] As used herein, the term "mesocrystalline group" is known to those skilled in the art and described in the literature, and means a group that substantially contributes to the formation of a liquid crystal (LC) phase in low molecular weight or polymeric substances due to the anisotropy of its attractive and repulsive interactions. A compound containing a mesocrystalline group (mesocrystalline compound) does not necessarily possess an LC phase itself. Mesocrystalline compounds may also exhibit LC phase characteristics only after being mixed with other compounds and / or after polymerization. Typical mesocrystalline groups are, for example, rigid rod-shaped or disk-shaped units. An overview of the terms and definitions used in conjunction with mesocrystalline or LC compounds is provided in [the relevant section]. Pure Appl. Chem. 2001, 73(5), 888 and C. Tschierske, G. Pelzl, S. Diele, Angew.Chem. As given in 2004, 116, 6340-6368.

[0059] As used herein, the term "spacer group" (also referred to below as "Sp") is known to those skilled in the art and described in the literature, see, for example... Pure Appl. Chem. 2001, 73(5), 888 and C.Tschierske, G. Pelzl, S. Diele, Angew. Chem.2004, 116, 6340-6368. As used herein, the term "spacer group" or "spacer base" means a flexible group, such as an alkylene group, that connects the mesocrystalline group and the polymerizable group in a polymerizable mesocrystalline compound.

[0060] As used herein, the term "RM formulation" refers to a formulation comprising at least one RM or a mixture of RMs as described above and below, and further comprising one or more solvents (preferably selected from organic solvents).

[0061] As used herein, the term "RM mixture" means a mixture comprising one or more, preferably two or more, more preferably two to ten, and most preferably two to six RMs. The RM mixture optionally further comprises one or more solid additives, including, but not limited to, polymerization initiators, inhibitors, surfactants, and adhesion promoters as described in more detail below.

[0062] Unless otherwise stated, the percentages of compounds in RM mixtures given above and below refer to the weight of all solids in the RM mixture.

[0063] Unless otherwise stated, the percentages of compounds in RM formulations given above and below refer to the weight of all solids in the RM formulation (including liquid additives as described below, but excluding solvents).

[0064] As used herein, the term "perfluoroalkyl and polyfluoroalkyl substances (PFAS)" (as defined by the OECD) refers to a substance or compound containing at least one perfluoromethyl or methylene C atom (without any H / Cl / Br / I atoms attached to it), i.e., a compound having at least one CF3 or CF2 group.

[0065] As used herein, “polyfluorinated alkyl or aryl” refers to an alkyl or aryl group that is substituted with two or more F atoms (where the F atoms may be attached to the same or different C atoms), and therefore includes perfluorinated carbon groups.

[0066] As used herein, the term "polymer" should be understood to mean a molecule encompassing a backbone of one or more different types of repeating units (the smallest constituent units of a molecule) and includes commonly known terms such as "oligomer," "copolymer," "homogene," and the like. Furthermore, 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 these residues should be understood not to be covalently incorporated into the polymer. Moreover, although these residues and other elements are typically removed during post-polymerization purification processes, they are generally mixed or blended with the polymer, and thus usually remain with the polymer when it is transferred between vessels or between solvents or dispersion media.

[0067] The term "polymerization" refers to the chemical process of forming a polymer by joining together multiple polymerizable groups or polymer precursors (polymerizable compounds) containing these polymerizable groups.

[0068] The term "chirality" is generally used to describe objects that cannot be superimposed on their mirror images.

[0069] A "non-chiral" object is an object that is identical to its mirror image.

[0070] Unless otherwise expressly stated, the terms “chiral nematic” and “cholesterol” are used synonymously in this application.

[0071] The term "isomerizable / photoisomerizable compound" refers to a compound that includes one or more isomerizable or photoisomerizable groups, respectively.

[0072] The term "isomerizable group" refers to a molecular functional group that undergoes a change in molecular geometry (i.e., isomerization) through bond rotation, skeletal rearrangement, or atom- or group transfer, or through dimerization (which can be induced, for example, by thermal or photochemical means or by the addition of a catalyst).

[0073] The term "photoisomerizable group" refers to a molecular functional group that undergoes a change in molecular geometry (i.e., isomerization (photoisomerization)) when irradiated with light of a suitable wavelength that the molecule can absorb, through bond rotation, skeletal rearrangement, atom- or group transfer, or dimerization.

[0074] Examples of photoisomerizable groups are -C=C- double bonds and azo groups (-N=N-). Examples of molecular structures and substructures including such photoisomerizable groups include stilbene, (1,2-difluoro-2-phenyl-vinyl)benzene, cinnamate, α-cyanocinate, 4-phenylbut-3-en-2-one, and Schiff bases (i.e., groups R). i R ii C=NR iii , where R iii Unlike H and being, for example, alkyl or aryl), 2-benzylidene-1-indanone, chalcone, coumarin, chromone, dicyclopentadienone, and azobenzene.

[0075] The chiral RM formulations of the present invention can be prepared, for example, by doping a master mixture comprising one or more RMs with a chiral compound having high torsional strength.

[0076] Then, the concentration c of the chiral compound (expressed as a percentage) and the helical torsion force HTP (expressed in nm) are used to determine the concentration of the chiral compound. -1The pitch p (also referred to below as "chiral pitch" or "spiral pitch") of the induced cholesteric spiral is given by the following equation (denoted in nm):

[0077] p = (HTP c) -1

[0078] The lower pitch value is referred to as "short pitch" below, and the higher pitch value is referred to as "long pitch" below. In addition, short pitch corresponds to a highly twisted structure (i.e., a higher twist angle), and long pitch corresponds to a slowly twisted structure (i.e., a lower twist angle) around the helical axis over a given distance.

[0079] When using more than one chiral compound, the total HTP (HTP) of chiral compounds with the same configuration or tortuosity type. 总 Then it approximately satisfies the following equation:

[0080] HTP 总 = ∑ i c i HTP i

[0081] Where c i It is the concentration of each individual chiral compound and HTP i It is the helical twisting force of each individual chiral compound.

[0082] HTP (IHTP) of all chiral compounds in mixtures with different configurations or different twist directions Δ I) then approximately satisfy the following equation:

[0083] IHTP Δ I = (∑ s c s HTP s ) - ((∑ r c r HTP r )

[0084] Where c s It is the concentration of each individual chiral compound with the S configuration, HTP s It is the helical torsion force of each individual chiral compound having the S configuration, and where c r It is the concentration of each individual chiral compound with the R configuration, and HTP R It is the helical twisting force of each individual chiral compound with the R configuration.

[0085] The birefringence Δn is defined as follows:

[0086] Δn=n e -n o

[0087] Where n e It is an unusual refractive index and n o It is the ordinary refractive index, and the effective average refractive index n av. It is given by the following equation:

[0088] n av. =((2n o 2 +n e 2 ) / 3) ½

[0089] The average refractive index n can be measured using an Abbe refractometer. av. and ordinary refractive index n o Then, Δn can be calculated using the above equation.

[0090] The term "visible light" refers to electromagnetic radiation with wavelengths ranging from about 400 nm to about 740 nm. "Ultraviolet (UV) light" refers to electromagnetic radiation with wavelengths ranging from about 200 nm to about 450 nm.

[0091] According to the present invention, the term "linearly polarized light" means light that is at least partially linearly polarized. Preferably, the aligned light is linearly polarized with a brightness polarization ratio greater than 5:1. The wavelength, intensity, and energy of the linearly polarized light are selected based on the photosensitivity of the photoalignable material. 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 includes light with a wavelength less than 450 nm, more preferably less than 420 nm, and preferably includes light with a wavelength greater than 280 nm, preferably greater than 320 nm, and more preferably greater than 350 nm.

[0092] At the molecular level, the birefringence of liquid crystals depends on the anisotropy of polarization index. The term "polarization rate" refers to the ease with which the electron distribution in an atom or molecule can be distorted. The polarization rate increases with the number of electrons and the diffusion of the electron cloud. The polarization rate can be calculated using methods described, for example, in Jap. J. Appl. Phys. 42, (2003) p. 3463.

[0093] The term "director" is known in the art and refers to the preferred orientation direction of the long molecular axis (in the case of rod-shaped compounds) or short molecular axis (in the case of disc-shaped compounds) of a liquid crystal or RM molecule. In the case of such anisotropic molecular uniaxial ordering, the director is the anisotropic axis.

[0094] The terms "alignment" or "orientation" refer to the alignment (orientation ordering) of anisotropic units (e.g., fragments of small or large molecules) of a material along a consistent direction (referred to as the "alignment direction"). In the alignment layer of a liquid crystal material or RM material, the liquid crystal director is aligned with the alignment direction such that the alignment direction corresponds to the direction of the material's anisotropic axis.

[0095] The term "uniform orientation" or "uniform alignment" in liquid crystal or RM materials, for example within a layer of the material, refers to the long molecular axes (in the case of rod-shaped compounds) or short molecular axes (in the case of disc-shaped compounds) of the liquid crystal or RM molecules being oriented substantially in the same direction. In other words, the lines pointing to the liquid crystal are parallel.

[0096] The term "vertical structure / alignment / orientation" refers to a membrane in which the optical axis is substantially perpendicular to the membrane plane.

[0097] The term "planar structure / alignment / orientation" refers to a membrane in which the optical axis is substantially parallel to the membrane plane.

[0098] All temperatures (e.g., the melting point of liquid crystals T(C,N) or T(C,S), the transition point from smectic (S) phase to nematic (N) phase T(S,N), and the clearing point T(N,I)) are expressed in degrees Celsius. All temperature differences are expressed as variations.

[0099] In cases of doubt, the definition given in C. Tschierske, G. Pelzl and S. Diele, Angew. Chem. 2004, 116, 6340-6368 shall prevail.

[0100] In the formula shown in the context, group R, including any variations thereof, such as R 1 R 0 R 00 R 0 R 11 R R R C R 3 R 4 If "etc." or "L" indicates an alkyl and / or alkoxy group, then it can be straight-chain or branched. It is preferably straight-chain, having 2, 3, 4, 5, 6 or 7 C atoms and therefore preferably represents ethyl, propyl, butyl, pentyl, hexyl, heptyl, ethoxy, propoxy, butoxy, pentoxy, hexoxy or heptoxy, and also methyl, octyl, nonyl, decyl, undecyl, dodecyl, tridecyl, tetradecyl, pentadecyl, methoxy, octyloxy, nonoxy, decyloxy, undecyloxy, dodecyloxy, tridecyloxy or tetradecyloxy.

[0101] In the formula shown in the context, group R, including any variations thereof, such as R 1 R 0 R 00 , 0 R 11 R 22 R C R 3 R 4 "Equal to" or "L" indicates alkyl and / or alkoxy, which can be straight-chain or branched. It is preferably straight-chain, having 2, 3, 4, 5, 6 or 7 C atoms and therefore preferably represents ethyl, propyl, butyl, pentyl, hexyl, heptyl, ethoxy, propoxy, butoxy, pentoxy, hexoxy or heptoxy, and also methyl, octyl, nonyl, decyl, undecyl, dodecyl, tridecyl, tetradecyl, pentadecyl, methoxy, octyloxy, nonoxy, decyloxy, undecyloxy, dodecyloxy, tridecyloxy or tetradecyloxy.

[0102] In the formula shown in the context, group R, including any variations thereof, such as R 1 R 0 R 00 R 0 R 11 R 22 R C R 3 R 4 "Equal to" or "L" indicates that one or more of the CH2 groups are S-substituted alkyl groups, which can be straight-chain or branched. It is preferably straight-chain, having 1, 2, 3, 4, 5, 6 or 7 C atoms and therefore preferably represents thiomethyl, thioethyl, thiopropyl, thiobutyl, thiopentyl, thiohexyl or thioheptyl.

[0103] The oxane preferably represents straight-chain 2-oxapropyl (=methoxymethyl), 2-oxabutyl (=ethoxymethyl) or 3-oxabutyl (=2-methoxyethyl), 2-, 3- or 4-oxapentyl, 2-, 3-, 4- or 5-oxahexyl, 2-, 3-, 4-, 5- or 6-oxaheptyl, 2-, 3-, 4-, 5-, 6- or 7-oxaoctyl, 2-, 3-, 4-, 5-, 6-, 7- or 8-oxanonyl, 2-, 3-, 4-, 5-, 6-, 7-, 8- or 9-oxadecyl.

[0104] If the group R in the formula shown above and below (including any variant thereof, such as R) 1 R 0 R 00 , 0 R 11 R22 R C R 3 R 4 (etc.) or L represents alkoxy or oxaalkyl, and may also contain one or more additional oxygen atoms, with the restriction that the oxygen atoms are not directly connected to each other.

[0105] In another preferred embodiment, one or more of R include any variations thereof, such as R 1 R 0 R 00 , 0 R 11 R 22 R C R 3 R 4 Choose from the following groups:

[0106]

[0107] -S 1 -F, -OS 1 -F, -O-S1-O-S2, where S 1 It is C 1-12 Alkylene or C 2-12 alkenyl group, and S 2 It is H, C 1-12 Alkyl or C 2-12 Alkenyl, and very preferably selected from the group consisting of:

[0108]

[0109] -OCH2OCH3, -O(CH2)2OCH3, -O(CH2)3OCH3, -O(CH2)4OCH3, -O(CH2)2F, -O(CH2)3F and -O(CH2)4F.

[0110] In the formula shown in the context, group R, including any variations thereof, such as R 1 R 0 R 00 , 0 R 11 R 22 R C R 3 R 4"Equal" or "L" indicates that one of the CH2 groups has been substituted with -CH=CH-, which can be straight-chain or branched. It is preferably straight-chain and has 2 to 10 carbon atoms. Therefore, in particular, it represents vinyl, prop-1- or -2-enyl, but-1-, -2- or -3-enyl, pent-1-, -2-, -3- or -4-enyl, hex-1-, -2-, -3-, -4- or -5-enyl, hep-1-, -2-, -3-, -4-, -5- or -6-enyl, oct-1-, -2-, -3-, -4-, -5-, -6- or -7-enyl, non-1-, -2-, -3-, -4-, -5-, -6-, -7- or -8-enyl, dec-1-, -2-, -3-, -4-, -5-, -6-, -7-, -8- or -9-enyl.

[0111] In the formula shown in the context, group R, including any variations thereof, such as R 1 R 0 R 00 , 0 R 11 R 22 R C R 3 R 4 "Equal to" or "L" indicates an alkyl or alkenyl group that is at least monosubstituted with a halogen. This group is preferably straight-chain, and the halogen is preferably F or Cl. In the case of multiple substitution, the halogen is preferably F. The resulting group also includes perfluorinated groups. In the case of monosubstituted substitution, the fluorine or chlorine substituent can be at any desired position, but is preferably at the ω-position.

[0112] In the context, or This indicates the trans-1,4-cyclohexyl ring, and It represents a 1,4-phenylene ring.

[0113] The halogen is preferably F or Cl, with F being the most preferred.

[0114] Group -CR 0 =CR 00 - Preferably -CH=CH-.

[0115] -OC-, -CO-, -C(=O)-, and -C(O)- represent carbonyl groups, i.e. .

[0116] Preferred substituents L are, for example, F, Cl, Br, I, -CN, -NO2, -NCO, -NCS, -OCN, -SCN, -C(=O)N(R) x )2、-C(=O)Y 1 -C(=O)R x -N(R)x 2. One or more H atoms may be optionally replaced by F or Cl from straight-chain or branched alkyl, alkoxy, alkyl carbonyl, alkoxy carbonyl, alkyl carbonyloxy, or alkoxy carbonyloxy groups, optionally substituted silyl groups having 1 to 20 Si atoms, or optionally substituted aryl groups having 6 to 25, preferably 6 to 15, C atoms.

[0117] Where R x The symbol represents H, F, Cl, CN, or a straight-chain, branched, or cyclic alkyl group having 1 to 25 carbon atoms, wherein one or more non-adjacent CH2- groups are optionally substituted by -O-, -S-, -CO-, -CO-O-, -O-CO-, -O-CO-O- with O- and / or S- atoms not directly connected to each other, and wherein one or more H atoms are optionally substituted by F, Cl, P-, or P-Sp-, and Y 1 It represents halogens.

[0118] Particularly preferred substituents L are, for example, F, Cl, CN, NO2, CH3, C2H5, OCH3, SCH3, OC2H5, SC2H5, COCH3, COC2H5, COOCH3, COOC2H5, CF3, OCF3, OCHF2, OC2F5, and phenyl.

[0119] Preferred , , or ,

[0120] L has one of the meanings indicated above.

[0121]

[0122] Throughout this application, the term "aryl and heteroaryl" encompasses groups that can be monocyclic or polycyclic, meaning they may have one ring (e.g., phenyl) or two or more rings that may be fused (e.g., naphthyl) or covalently linked (e.g., biphenyl), or contain a combination of fused and linking rings. Heteroaryl groups contain one or more heteroatoms preferably selected from O, N, S, and Se. Particularly preferred are monocyclic, bicyclic, or tricyclic aryl groups having 6 to 25 carbon atoms and monocyclic, bicyclic, or tricyclic heteroaryl groups having 2 to 25 carbon atoms, optionally containing a fused ring and optionally being substituted. Other preferred are 5-membered, 6-membered, or 7-membered aryl and heteroaryl groups, wherein one or more CH groups may be substituted with N, S, or O in a manner where the O and / or S atoms are not directly linked to each other. Preferred aryl groups are, for example, phenyl, biphenyl, triphenyl, [1,1':3',1”]triphenyl-2'-yl, naphthyl, anthraceneyl, binatyl, phenanthryl, pyrene, dihydropyrene, etc. The compounds are benzo[a], peryl, tetraphenyl, pentaphenyl, benzo[a]pyrene, fluorenyl, indene, indo[a]fluorenyl, spirodifluorenyl, and more preferably 1,4-phenylene, 4,4'-biphenylene, and 1,4-bitriphenylene.

[0123] Preferred heteroaryl groups are, for example, 5-membered rings, such as pyrrole, pyrazole, imidazole, 1,2,3-triazole, 1,2,4-triazole, tetrazolium, furan, thiophene, selenophene, oxazole, isoxazole, 1,2-thiazole, 1,3-thiazole, 1,2,3-oxadiazole, 1,2,4-oxadiazole, 1,2,5-oxadiazole, 1,3,4-oxadiazole, 1,2,3-thiadiazole, 1,2,4-thiadiazole, 1,2,5-thiadiazole, 1,3,4-thiadiazole, 6-membered rings, such as pyridine, pyridazine, pyrimidine, pyrazine, 1,3,5-triazine, 1,2,4-triazine, 1,2,3-triazine, 1,2,4,5-tetraazine, 1,2,3,4-tetraazine, 1,2,3,5-tetraazine, or fused groups, such as indole, isoindole. Indazine, Indazole, Benzimidazole, Benzitriazole, Purine, Naphthemidazole, Phenylenazole, Pyridinazole, Pyrazinazole, Quinoxaline, Benzooxazole, Naphthemidazole, Anthrazooxazole, Phenylenazole, Isoxazole, Benzothiazol, Benzofuran, Isobenzofuran, Dibenzofuran, Quinoline, Isoquinoline, Pteridine, Benzo-5,6-quinoline, Benzo-6,7-quinoline Benzo-7,8-quinoline, benzoisoquinoline, acridine, phenothiazine, phenoxazine, benzopyridinium, quinoxaline, phenothiazine, naphthidine, azacarbazole, benzocarbine, phenanthridine, phenanthroxaline, thieno[2,3b]thiophene, thieno[3,2b]thiophene, dithieno[2,3b]thiophene, isobenzothiophene, dibenzothiophene, benzothiadiazolethiophene, or combinations of these groups. Heteroaryl groups may also be substituted with alkyl, alkoxy, thioalkyl, fluorine, fluoroalkyl, or other aryl or heteroaryl groups.

[0124] At group In the diagram, the single bond between two ring atoms can attach to any empty position on the benzene ring.

[0125] -OC-, -CO-, -C(=O)-, and -C(O)- represent carbonyl groups, i.e. .

[0126] Polymerizable group P, including any variation thereof, such as P 0 P 1 P 2 , 0It is a group suitable for polymerization reactions, such as, for example, free radical or ionic chain polymerization, addition polymerization or condensation polymerization, or suitable for polymer-like reactions, such as addition or condensation on the main polymer chain. It is particularly preferred to be a group for chain polymerization, especially those containing C=C double bonds or -C≡C- triple bonds, and a group suitable for ring-opening polymerization, such as, for example, oxobutane or epoxy groups.

[0127] Preferred group P, including any variation thereof, such as P 0 P 1 P 2 , 0 Choose from the following groups:

[0128] CH2=CW 1 -CO-O-、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-, HO-CW 2 W 3 -、HS-CW 2 W 3 -、HW 2 N-, HO-CW 2 W 3 -NH-, CH2=CW 1 -CO-NH-, CH2=CH-(COO) k1 -Phe-(O) k2 - CH2=CH-(CO) k1 -Phe-(O) k2 -, Phe-CH=CH-, HOOC-, OCN- and W 4 W 5 W 6 Si-, where W 1This indicates H, F, Cl, CN, CF3, phenyl, or alkyl groups having 1 to 5 carbon atoms, particularly H, F, Cl, or CH3, W 2 and W 3 Each independently represents H or an alkyl group having 1 to 5 carbon atoms, particularly H, methyl, ethyl, or n-propyl, W 4 W 5 and W 6 Each independently represents Cl, an oxaalkyl or oxacarbonylalkyl group having 1 to 5 carbon atoms, and W. 7 and W 8 Each of them independently represents H, Cl or an alkyl group having 1 to 5 C atoms, Phe represents 1,4-phenylene, which is optionally substituted with one or more L groups other than P-Sp- as defined above, k1, k2 and k3 each independently represent 0 or 1, k3 preferably represents 1, and k4 represents an integer from 1 to 10.

[0129] The highly preferred group P, including any variation thereof, such as P 0 P 1 P 2 , 0 Choose from the following groups:

[0130] CH2=CW 1 -CO-O-、CH2=CW 1 -CO-、 , , , , CH2=CW 2 -O-、CH2=CW 2 -、CW 1 =CH-CO-(O) k3 -、CW 1 =CH-CO-NH-、CH2=CW 1 -CO-NH-, (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- and W 4 W 5 W 6Si-, where W 1 This indicates H, F, Cl, CN, CF3, phenyl, or alkyl groups having 1 to 5 carbon atoms, particularly H, F, Cl, or CH3, W 2 and W 3 Each independently represents H or an alkyl group having 1 to 5 carbon atoms, particularly H, methyl, ethyl, or n-propyl, W 4 W 5 and W 6 Each independently represents Cl, an oxaalkyl or oxacarbonylalkyl group having 1 to 5 carbon atoms, and W. 7 and W 8 Each of them independently represents H, Cl or an alkyl group having 1 to 5 C atoms, Phe represents 1,4-phenylene, k1, k2 and k3 each independently represent 0 or 1, k3 preferably represents 1, and k4 represents an integer from 1 to 10.

[0131] The very particularly preferred group P, including any variation thereof, such as P 0 P 1 P 2 , 0 Choose from the following groups: CH2=CW 1 -CO-O-, especially CH2=CH-CO-O-, CH2=C(CH3)-CO-O- and CH2=CF-CO-O-, and also CH2=CH-O-, (CH2=CH)2CH-O-CO-, (CH2=CH)2CH-O- and .

[0132] Other preferred polymerizable groups P, including any variations thereof, such as P 0 P 1 P 2 , 0 The group is selected from the following: ethylene oxy, acrylate, methacrylate, fluoroacrylate, chloroacrylate, oxetane and epoxy, with the most preferred group being acrylate and methacrylate.

[0133] In another preferred embodiment of the invention, the polymerizable compounds disclosed above and below include those of the formulas D, M, T, A, and I. In the compounds of the formula and its derivatives, all polymerizable groups have the same meaning and preferably represent acrylates or methacrylates, with acrylates being very preferred.

[0134] Spacer groups, including any variations thereof, such as Sp 0 Sp1 Sp 2 S 0 When it differs from a single bond, it is preferable to have the formula Sp"-X, such that the corresponding group P-Sp-, etc., conforms to the formula P-Sp"-X"-, wherein

[0135] "Sp" represents a straight-chain or branched alkylene group having 1 to 20, preferably 1 to 12, carbon atoms, optionally monosubstituted or polysubstituted with F, Cl, Br, I, or CN, wherein, in addition, one or more non-adjacent CH2 groups may be independently substituted with -O-, -S-, -NH-, or -N(R) atoms. 0 )-、-Si(R 0 R 00 )-, -CO-, -CO-O-, -O-CO-, -O-CO-O-, -S-CO-, -CO-S-, -N(R 00 -CO-O-、-O-CO-N(R) 0 )-、-N(R 0 )-CO-N(R 00 -, -CH=CH-, or -C≡C- are replaced by O and / or S atoms that are not directly connected to each other.

[0136] X" means -O-, -S-, -CO-, -CO-O-, -O-CO-, -O-CO-O-, -CO-N(R 0 )-、-N(R 0 )-CO-、-N(R 0 )-CO-N(R 00 )-, -OCH2-, -CH2O-, -SCH2-, -CH2S-, -CF2O-, -OCF2-, -CF2S-, -SCF2-, -CF2CH2-, -CH2CF2-, -CF2CF2-, -CH=N-, -N=CH-, -N=N-, -CH=CR 0 -、-CY 2 =CY 3 -, -C≡C-, -CH=CH-CO-O-, -O-CO-CH=CH- or single bonds

[0137] R 0 and R 00 Each independently represents H or an alkyl group having 1 to 20 carbon atoms, and

[0138] Y 2 and Y 3 Each can be represented independently as H, F, Cl, or CN.

[0139] X" is preferably -O-, -S-, -CO-, -COO-, -OCO-, -O-COO-, or -CO-NR. 0 -、-NR 0 -CO-、-NR 0 -CO-NR 00 - or a single key.

[0140] Typical spacer group Sp, including any variations thereof, such as Sp 0 Sp 1 Sp 2 S 0 And -Sp"-X"- is, for example, -(CH2). p1 -、-(CH2) p1 -O-、-(CH2) p1 -O-CO-、-(CH2) p1 -CO-O-、-(CH2) p1 -O-CO-O-、-(CH2CH2O) q1 -CH2CH2-, -CH2CH2-S-CH2CH2-, -CH2CH2-NH-CH2CH2- or -(SiR) 0 R 00 -O) p1 - where p1 is an integer from 1 to 12, q1 is an integer from 1 to 3, and R 0 and R 00 It has the meaning indicated above.

[0141] The particularly preferred group Sp, including any variation thereof, such as Sp 0 Sp 1 Sp 2 S 0 And -Sp"-X"- is -(CH2) p1 -、-(CH2) p1 -O-、-(CH2) p1 -O-CO-、-(CH2) p1 -CO-O-、-(CH2) p1 -O-CO-O-, where p1 and q1 have the meanings indicated above.

[0142] The particularly preferred group Sp" is, in each case, a straight chain, ethylene, propyleneene, butylene, pentylene, hexylene, heptylene, octylene, nonylene, decylene, undecylene, dodecylene, octadecylene, ethyleneoxyethylene, methyleneoxybutylene, ethylenethioethylene, ethylene-N-methyliminoethylene, 1-methylalkylene, vinylene, propenylene, and butenylene.

[0143] In another preferred embodiment of the invention, polymerizable compounds such as those disclosed above and below include those of the formulas D, M, T, A, and I. Compounds thereof and their derivatives containing a spacer group Sp substituted with one or more polymerizable groups P, including any variants thereof such as Sp 0 Sp 1 Sp 2 Sp 0 This is to make the groups Sp-P, etc., correspond to Sp(P). s , where s is ≥2 (branched polymerizable groups).

[0144] The preferred polymerizable compounds according to this preferred embodiment are those in which s is 2, i.e., compounds containing the Sp(P)2 group. A very preferred polymerizable compound according to this preferred embodiment contains groups selected from the following formula:

[0145] -X-alkyl-CHPP Sp1

[0146] -X-alkyl-CH((CH2) aa P)((CH2) bb P) Sp2

[0147] -XN((CH2) aa P)((CH2) bb P) Sp3

[0148] -X-alkyl-CHP-CH2-CH2P Sp4

[0149] -X-alkyl-C(CH2P)(CH2P)-C aa H 2aa+1 SP5

[0150] -X-alkyl-CHP-CH2P Sp6

[0151] -X-alkyl-CPP-C aa H 2aa+1 SP7

[0152] -X-alkyl-CHPCHP-C aa H 2aa+1 Sp8

[0153] Where P is defined above,

[0154] Alkyl refers to a straight-chain or branched alkylene group with a single bond or 1 to 12 carbon atoms, which is unsubstituted or monosubstituted or polysubstituted with F, Cl, or CN, and wherein one or more non-adjacent CH2 groups may be independently bonded to each other by -C(R) atoms in a manner in which O and / or S atoms are not directly connected to each other. 0 )=C(R 0 )-、-C C-、-N(R 0 )-, -O-, -S-, -CO-, -CO-O-, -O-CO-, -O-CO-O- substitution, where R 0 It has the meaning indicated above.

[0155] aa and bb each independently represent 0, 1, 2, 3, 4, 5, or 6.

[0156] X has one of the meanings indicated by X", and is preferably O, CO, SO2, O-CO-, CO-O or a single bond.

[0157] The preferred group Sp(P)2 is selected from formulas Sp1, Sp2 and Sp3.

[0158] The highly preferred group Sp(P)2 is selected from the following formulas:

[0159] -CHPP Sp1a

[0160] -O-CHPP Sp1b

[0161] -CH2-CHPP Sp1c

[0162] -OCH2-CHPP Sp1d

[0163] -CH(CH2-P)(CH2-P) Sp2a

[0164] -OCH(CH2-P)(CH2-P) Sp2b

[0165] -CH2-CH(CH2-P)(CH2-P) Sp2c

[0166] -OCH2-CH(CH2-P)(CH2-P) Sp2d

[0167] -CO-NH((CH2)2P)((CH2)2P) Sp3a Detailed Implementation

[0168] The RM formulations according to the present invention contain solvent blends as described above and below, which, when combined with RMs as described above and below, can provide RM formulations exhibiting advantageous properties such as good solubility, good wetting, good jetting properties, high stability, suitable processing window, and good process compatibility, and allow for the adjustment of parameters required for printing, especially inkjet printing.

[0169] In particular, the inventors of this invention have been able to determine solvent blends suitable for both printing applications and deposition onto selected substrates of RM inks. Therefore, high-quality RM films deposited via inkjet printing can be obtained by optimizing key parameters such as solubility, jetting, process compatibility, and wetting.

[0170] By carefully optimizing the solvent blends, the inventors of this invention were able to develop RM formulations with optimal spraying, processing windows, and wetting. Importantly and surprisingly, the solvent blends according to the invention exhibit synergistic effects of the components during the processing steps, which could not be expected from the prior art and common sense.

[0171] Therefore, as demonstrated in the comparative examples below, when using a single solvent with very good wetting properties, this may result in strong spreading of the printed RM formulation on the substrate, but it may also lead to overflow and thus poor shape retention of the printed pattern. On the other hand, when using a single solvent with less significant wetting properties, this may result in poor spreading of the printed RM formulation on the substrate or even partial dewetting. By using solvent blends as described above and below, preferably containing one or more solvents exhibiting good wetting and one or more solvents exhibiting less significant wetting, the inventors of the present invention can formulate a solvent blend that achieves sufficient wetting to ensure strong spreading and high layer uniformity of the printed RM formulation, while avoiding overflow and thus ensuring high shape retention of the printed pattern.

[0172] RM formulations using solvent blends according to the invention have been found to be particularly suitable for inkjet printing on cinnamic acid ester photoalignment layers, where they exhibit better film quality than when using solvents known to date and used for this purpose from the prior art.

[0173] Furthermore, the RM formulations according to the present invention are also suitable for other printing or coating methods further specified below.

[0174] In particular, the RM formulations according to the present invention exhibit one or more of the following preferred properties, which are associated with good inkjet printing processes:

[0175] - This RM is soluble at a solid content of 15-30% by weight, and soluble at a maximum temperature of 70°C.

[0176] - This RM formulation is stable for several days at room temperature (RT).

[0177] - This RM formulation can be jetted at a viscosity of at least 3.5 cP (at 20°C), thus ensuring compatibility with inkjet printing.

[0178] - The solvent or solvent blend has a boiling point temperature Tb ≥ 180°C to allow for easy evaporation after the printing process.

[0179] - The solvent or solvent blend can be removed under processing conditions, preferably at a maximum temperature of 100°C for a maximum of 5 minutes, to achieve RM alignment.

[0180] - The solvent or solvent blend does not damage the underlying photoalignment layer or another layer, such as another RM layer, on which the RM formulation is deposited.

[0181] - The solvent selection allows individual droplets to coalesce at the target film thickness and exhibits a size difference of preferably less than 15% from the intended design (e.g., the width of a square).

[0182] The RM formulation according to the invention preferably consists of a solvent component and an RM component, wherein the solvent component contains a solvent as described above and below or a solvent blend of three or more solvents, and the RM component comprises RM or a mixture of RM and optionally one or more additives.

[0183] Preferably, all solvents in the RM formulation and solvent blend according to the present invention are selected from organic solvents.

[0184] The first solvent is a cycloalkanone having 5, 6, 7 or 8 C atoms, preferably cyclohexanone or cycloheptanone, with cyclohexanone being very preferred.

[0185] The second solvent is selected from formula S1A and S1B, preferably from formula S1A.

[0186] In equation S1A, Ar S1 Preferably selected from phenyl, pyrrole, furan, thiophene, pyridine, pyran or 2,2-, 2,4- or 2,6-thiaran, very preferably selected from phenyl, all of which are optionally decorated with one or more L groups. S replace.

[0187] In equation S1A, R S1 The preferred selection is from methyl, ethyl, n-propyl, isopropyl, n-butyl, sec-butyl, isobutyl, and tert-butyl, with a very preferred selection from ethyl and isopropyl.

[0188] In equation S1B, Ar S2Preferably selected from phenyl, pyrrole, furan, thiophene, pyridine, pyran or 2,2-, 2,4- or 2,6-thiaran, very preferably selected from phenyl, all of which are optionally decorated with one or more L groups. S replace.

[0189] In equation S1B, R S2 The preferred selection is from methyl, ethyl, propyl, and butyl, with a very high preference for methyl and ethyl.

[0190] In equation S1A, L S Preferably selected from alkyl, alkoxy, or alkyl carbonyl groups having 1 to 5 carbon atoms.

[0191] The preferred solvent for formula S1A is selected from the following sub-formulas:

[0192]

[0193] Where R S1 It has one of the meanings given in Formula S1A or the preferred meanings given above and below, and is preferably selected from methyl, ethyl, n-propyl, isopropyl, n-butyl, sec-butyl, isobutyl and tert-butyl, and very preferably selected from ethyl and isopropyl.

[0194] Very preferably, the solvent of formula S1A is selected from acetophenone, phenylacetone, phenylbutanone and isobutyrophenone, and most preferably from acetophenone, phenylbutanone and isobutyrophenone.

[0195] In equation S1B, Ar S2 Preferably selected from phenyl, pyrrole, furan, thiophene, pyridine, pyran or 2,2-, 2,4- or 2,6-thiaran, very preferably selected from phenyl, all of which are optionally decorated with one or more L groups. S replace.

[0196] In equation S1B, R S2 The preferred selection is from methyl, ethyl, propyl, and butyl, with a very high preference for methyl and ethyl.

[0197] In equation S1B, L S Preferably selected from alkyl, alkoxy, or alkyl carbonyl groups having 1 to 5 carbon atoms.

[0198] The solvent of the highly preferred formula S1B is selected from the following sub-formulas:

[0199]

[0200] Where R S2 It has one of the meanings given in Formula S1B or the preferred meanings given above and below, and is preferably methyl or ethyl.

[0201] Preferably, the solvent of formula S1B is selected from methyl benzoate, ethyl benzoate, methyl phenylacetate, butyl benzoate, benzyl propionate, and phenyl propionate, and is very preferably selected from methyl benzoate, methyl phenylacetate, and ethyl benzoate.

[0202] The third solvent is an aliphatic ketone, aliphatic or aromatic alcohol, or diol, preferably selected from formulas S2A, S2B, S2C, and S2D. The aliphatic or aromatic alcohol can be a primary, secondary, or tertiary alcohol, and can be a linear or cyclic aliphatic or aromatic alcohol, i.e., containing a hydroxyl group preferably indirectly bonded to an aromatic hydrocarbon group via an alkyl group.

[0203] The solvent of the preferred formula S2A is selected from 2-nonanone, 2-decanone and 2-undecanone, and is very preferably selected from 2-decanone and 2-undecanone.

[0204] The solvent for the preferred formula S2B is selected from 2-heptanol, 2-octanol, 2-nonanol, cyclopentanol and cyclohexanol, with cyclopentanol and cyclohexanol being very preferred.

[0205] The preferred solvent for formula S2C is selected from 1-hexanol, 1-heptanol, 1-octanol, 1-nonanol, phenylmethanol, 2-phenylethanol and 3-phenyl-1-propanol, with 2-phenylethanol being very preferred.

[0206] In formula S2D, preferably, R S8 and R S9 One of them is methyl or H, and the other is H.

[0207] The preferred solvent for the S2D formula is selected from propylene glycol monomethyl ether (PGME, 1-methoxy-2-propanol), dipropylene glycol monomethyl ether (DPM, usually a mixture of isomers), tripropylene glycol monomethyl ether (TPM, usually a mixture of isomers), propylene glycol monomethyl ether acetate (PGEMA, 1-methoxy-2-propanol acetate), di(propylene glycol) methyl ether acetate (DPMA, usually a mixture of isomers), diethylene glycol monoethyl ether acetate (DEGMEA), triethylene glycol monomethyl ether (TEGME), and phenoxyethanol, with PGME, PGMEA, DEGMEA, TEGME, and phenoxyethanol being particularly preferred.

[0208] Preferably, the solvent blend used in the RM formulation according to the invention has a boiling point of ≥180°C, very preferably 190°C to 300°C, and most preferably 195°C to 260°C.

[0209] The (by weight) ratio of the first solvent to the sum of the second and third solvents in the solvent blend of the RM formulation is preferably 5:1 to 1:2, and very preferably 4:1 to 1:1.

[0210] The (weight) ratio of the second solvent to the third solvent in the solvent blend of the RM formulation is preferably 1:1 to 8:1, and very preferably 2:1 to 7:1.

[0211] Preferably, the solvent blend in the RM formulation according to the present invention is a ternary solvent blend.

[0212] In a preferred embodiment, the solvent blend comprises cyclohexanone or cycloheptanone, preferably cycloheptanone, a solvent of formula S1A or a subformula thereof, preferably phenylbutanone or isobutyrophenone, and a solvent of formula S2A, preferably 2-undecanetone.

[0213] In another preferred embodiment, the solvent blend consists of cyclohexanone or cycloheptanone, preferably cyclohexanone, a solvent of formula S1A or a subformula thereof, preferably phenylbutanone or isobutyrophenone, and a solvent of formula S2B, preferably 2-nonanol or cyclopentanol.

[0214] In another preferred embodiment, the solvent blend consists of cyclohexanone or cycloheptanone, preferably cyclohexanone, a solvent of formula S1A or a subformula thereof, preferably phenylbutanone or isobutyrophenone, and a solvent of formula S2C, preferably 1-hexanol, 1-octanol or 2-phenylethanol.

[0215] In another preferred embodiment, the solvent blend comprises cyclohexanone or cycloheptanone, preferably cyclohexanone, a solvent of formula S1A or a subformula thereof, preferably phenylbutanone or isobutyrophenone, and a solvent of formula S2D (preferably selected from PGME, DPM, TPM, PGMEA, DPMA and DEGMEA).

[0216] More preferably, the RM formulation and solvent blend does not contain any solvent other than the first solvent, second solvent and third solvent as defined above and below.

[0217] Unless otherwise stated, the concentrations of RM and additives given above and below refer to the RM components or RM mixtures of the RM formulation and may also be expressed as "total solids by weight %" or "all solids by weight %".

[0218] In the RM formulation according to the present invention, the proportion of all solvents is preferably 50 to 95% by weight, very preferably 60 to 95% by weight, and most preferably 65 to 90% by weight.

[0219] The total concentration of all solids (including RM) in the RM formulation is preferably 5 to 50% by weight, more preferably 5 to 40% by weight, and most preferably 10 to 35% by weight.

[0220] Preferably, the RM formulation comprises one or more RMs having a polymerizable functional group (single reactive RM) and / or one or more RMs having two or more polymerizable functional groups (two reactive or multi reactive RM).

[0221] In a preferred embodiment, the RM formulation comprises one or more bireactive or multireactive RMs. These bireactive or multireactive RMs are preferably selected from formula D.

[0222] P 1 -Sp 1 -MG-Sp 2 -P 2 D

[0223] Each of these groups, independently of each other and in the same or different manner each time it appears, has the following meaning:

[0224] P 1 P 2 It is a polymerizable group.

[0225] Sp 1 Sp 2 For spacer groups or single bonds, and

[0226] MG is a rod-shaped mesocrystalline group, preferably selected from the formula MG.

[0227] -(A 1 -Z 1 ) n -A 2 - MG

[0228] A 1 and A 2 It is an aromatic or alicyclic group, optionally containing one or more heteroatoms selected from N, O, and S, and optionally mono- or poly-substituted with L.

[0229] L is P-Sp-, F, Cl, Br, I, -CN, -NO2, -NCO, -NCS, -OCN, -SCN, -C(=O)NR x R y -C(=O)OR x -C(=O)R x -NR x R y -OH, -SF5, optionally substituted silyl groups, aryl or heteroaryl groups having 1 to 12, preferably 1 to 6, carbon atoms, and straight-chain or branched alkyl, alkoxy, alkyl carbonyl, alkoxy carbonyl, alkyl carbonyloxy, or alkoxy carbonyloxy groups having 1 to 12, preferably 1 to 6, carbon atoms, wherein one or more H atoms are optionally replaced by F or Cl.

[0230] R x and R y It is H or an alkyl group having 1 to 12 carbon atoms.

[0231] Z 1 for -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, preferably -COO-, -OCO- or a single bond.

[0232] R 00 and R 000 It is H or an alkyl group having 1 to 12 carbon atoms.

[0233] Y 1 and Y 2 It can be H, F, Cl or CN.

[0234] n can be 1, 2, 3, or 4, preferably 1 or 2, and most preferably 2.

[0235] n1 is an integer from 1 to 10, preferably 1, 2, 3 or 4.

[0236] Preferred group A 1 and A 2 Including but not limited to furan, pyrrole, thiophene, oxazole, thiazole, thiadiazole, imidazole, phenylene, cyclohexylene, bicyclohexylene, cyclohexenylene, pyridine, pyrimidine, pyrazine, azulene, indane, fluorene, naphthalene, tetrahydronaphthalene, anthracene, phenanthrene, and dithienothiophene, all of which are unsubstituted or substituted with 1, 2, 3, or 4 L groups as defined above.

[0237] Particularly preferred group A 1 and A 2The group is selected from 1,4-phenylene, pyridin-2,5-diyl, pyrimidin-2,5-diyl, thiophene-2,5-diyl, naphthyl-2,6-diyl, 1,2,3,4-tetrahydronaphthalene-2,6-diyl, indane-2,5-diyl, bicyclopentylene, or 1,4-cyclohexylene, wherein one or two non-adjacent CH2 groups are optionally substituted with O and / or S, wherein these groups are unsubstituted or substituted with 1, 2, 3, or 4 groups L as defined above.

[0238] The preferred formula D's RM is selected from formula Da.

[0239]

[0240] Each of these groups, independently of each other and in the same or different manner each time it appears, has the following meaning:

[0241] P 0 The polymerizable group is preferably acryloyl, methacryl, oxetane, epoxy, vinyl, heptaene, ethyleneoxy, propylene ether, or styrene.

[0242] Z 0 -COO-, -OCO-, -CH2CH2-, -CF2O-, -OCF2-, -C C-, -CH=CH-, -OCO-CH=CH-, -CH=CH-COO- or single bonds

[0243] L has one of the meanings given in formula D, and is preferably selected from F, Cl, CN, or optionally halogenated alkyl, alkoxy, alkyl carbonyl, alkoxy carbonyl, alkyl carbonyloxy, or alkoxy carbonyloxy groups having 1 to 5 carbon atoms.

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

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

[0246] z is 0 or 1, where z is 0 if the adjacent x or y is 0.

[0247] The preferred RM of formula D is selected from the following formula:

[0248]

[0249]

[0250] Where P 0 L, r, x, y and z are defined as in equation Da, s is 0, 1, 2 or 3, and t is 0, 1 or 2.

[0251] Compounds of formulas Da1, Da2 and Da3 are particularly preferred, especially those of formula Da1.

[0252] In another preferred embodiment, the RM formulation contains one or more direactive RMs of formula D, wherein at least one Z group 1 Indicates -C C is preferably selected from formulas Df, Dg, Dh, Di, Dk, and Dm.

[0253] In another preferred embodiment, the RM formulation comprises one or more monoreactive RMs. These monoreactive RMs are preferably selected from formula M:

[0254] P 1 -Sp 1 -MG-R 22 M

[0255] Where P 1 Sp 1 MG has the meaning given in equation D, but L in equation MG is different from P-Sp-.

[0256] R 22 This represents P-Sp-, F, Cl, Br, I, -CN, -NO2, -NCO, -NCS, -OCN, -SCN, and -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 groups, straight-chain or branched alkyl groups having 1 to 12, preferably 1 to 6, carbon atoms, alkoxy, alkyl carbonyl, alkoxy carbonyl, alkyl carbonyloxy, or alkoxy carbonyloxy, wherein one or more H atoms are optionally replaced by F or Cl.

[0257] X is a halogen, preferably F or Cl, and

[0258] R x and R y Each is independently H or an alkyl group having 1 to 12 C atoms.

[0259] Preferably, the RM of formula M is selected from the following formula.

[0260]

[0261]

[0262]

[0263] Where P0 L, r, x, y, z, s, and t are defined as in equations Da and Dk, but L differs from P-Sp-.

[0264] R 0 It is an alkyl, alkoxy, thioalkyl, alkylcarbonyl, alkoxycarbonyl, alkylcarbonyl or alkoxycarbonyl group having one or more, preferably 1 to 15 C atoms, or representing Y. 0 Or P-(CH2) y -(O) z -,

[0265] X 0 Is -O-, -S-, -CO-, -COO-, -OCO-, -O-COO-, -CO-NR 01 -、-NR 01 -CO-、-NR 01 -CO-NR 01 -, -OCH2-, -CH2O-, -SCH2-, -CH2S-, -CF2O-, -OCF2-, -CF2S-, -SCF2-, -CF2CH2-, -CH2CF2-, -CF2CF2-, -CH=N-, -N=CH-, -N=N-, -CH=CR 01 -、-CF=CF-、-C C-, -CH=CH-COO-, OCO-CH=CH-, or single bonds.

[0266] Y 0 It is F, Cl, CN, NO2, OCH3, OCN, SCN, SF5, or monofluorinated, low-fluorinated, or polyfluorinated alkyl or alkoxy groups having 1 to 4 carbon atoms.

[0267] Z 0 It can be -COO-, -OCO-, -CH2CH2-, -CF2O-, -OCF2-, -CH=CH-, -OCO-CH=CH-, -CH=CH-COO-, or a single bond.

[0268] A 0 In cases where they appear multiple times, they are independently unsubstituted or substituted with 1, 2, 3, or 4 L groups, representing 1,4-phenylene or trans-1,4-cyclohexylene.

[0269] R 01,02 H and R are independent of each other. 0 Or Y 0 ,

[0270] u and v are independent of each other and can be 0, 1, or 2.

[0271] w is 0 or 1.

[0272] Furthermore, the benzene and naphthalene rings can be substituted by one or more identical or different groups L.

[0273] Compounds of formulas M1, M4, M7, M8, M9, M10, and M11 are particularly preferred, especially those of formulas M1, M4, and M7, and even more so those of formulas M8, M9, and M10.

[0274] In another preferred embodiment, the RM formulation contains one or more monoreactive RMs of formula M, wherein the MG group 1 Contains at least one Z group 1 It represents -C C is preferably selected from formulas M8 to M10.

[0275] In formulas D, M and their preferred sub-formulas, L is preferably selected from F, Cl, CN, NO2 or straight-chain or branched alkyl, alkoxy, alkyl carbonyl, alkoxy carbonyl, alkyl carbonyloxy or alkoxy carbonyloxy having 1 to 12 C atoms, wherein the alkyl group is optionally perfluorinated or P-Sp-.

[0276] Very preferably, L is selected from F, Cl, CN, NO2, CH3, C2H5, C(CH3)3, CH(CH3)2, CH2CH(CH3)C2H5, OCH3, OC2H5, COCH3, COC2H5, COOCH3, COOC2H5, CF3, OCF3, OCHF2, OC2F5 or P-Sp-, especially F, Cl, CN, CH3, C2H5, C(CH3)3, CH(CH3)2, OCH3, COCH3 or OCF3, most preferably F, Cl, CH3, C(CH3)3, OCH3 or COCH3 or P-Sp-.

[0277] In another preferred embodiment of the invention, the RM formulation contains one or more RMs of formula T.

[0278]

[0279] Each of these groups, independently of each other and in the same or different manner each time it appears, has the following meaning:

[0280] P is a polymerizable group.

[0281] Sp can be a spacer group or a single bond.

[0282] R 11 H, F, Cl, CN, or optionally fluorinated alkyl, alkoxy, thioalkyl, alkylcarbonyl, alkoxycarbonyl, alkylcarbonyl or alkoxycarbonyloxy, or P-Sp, having 1 to 15, preferably 1 to 5, carbon atoms.

[0283] A, B, D, and E are selected from 1,4-phenylene, naphthio-1,4-diyl, naphthio-2,6-diyl, phenanthrene-2,7-diyl, anthracene-9,10-diyl, fluorene-2,7-diyl, dibenzothiophene-2,7-diyl, dibenzofuran-2,7-diyl, benzo[1,2-b:4,5-b']dithiophene-2,5-diyl, indole-4,7-diyl, benzothiophene-4,7-diyl, 9,10-dihydro-phenanthrene-2,7-diyl, 1,2,3,4-tetrahydronaphthalene-5,8-diyl, or indane-2,5-diyl, wherein, in addition, one or more CH groups in these groups may be replaced by N, and all of them may optionally be replaced by one or more L or P-Sp- groups.

[0284] C is selected from phenyl-1,4-diyl, naphthyl-1,4-diyl, anthracene-9,10-diyl, fluorene-2,7-diyl, dibenzofuran-2,7-diyl, dibenzothiophene-2,7-diyl, benzo[1,2-b:4,5-b']dithiophene-2,5-diyl, indole-4,7-diyl, and benzothiophene-4,7-diyl, all of which may optionally be substituted with one or more L or P-Sp groups.

[0285] Furthermore, either ring C or ring D can represent a single bond.

[0286] L is F, Cl, -CN, -SCN, P-Sp-, or a straight-chain, branched, or cyclic alkyl group having 1 to 25 C atoms, wherein one or more non-adjacent CH2- groups are optionally replaced by the following groups in such a way that the O atoms and / or S atoms are not directly connected to each other: -O-, -S-, -CO-, -CO-O-, -O-CO-, -O-CO-O-, CR 0 =CR 00 -、-C C-、

[0287]

[0288] Furthermore, one or more H atoms may be optionally replaced by P-Sp-, F, or Cl, or two substituents L connected to directly adjacent C atoms may form cycloalkyl or cycloalkenyl groups with 5, 6, 7, or 8 C atoms.

[0289] Z 11 Z 12 for -O-, -S-, -CO-, -COO-, -OCO-, -S-CO-, -CO-S-, -O-COO-, -CO-NR 0 -、-NR 0 -CO-、-NR 0 -CO-NR 00 -NR0 -CO-O-、-O-CO-NR 0 -, -OCH2-, -CH2O-, -SCH2-, -CH2S-, -CF2O-, -OCF2-, -CF2S-, -SCF2-, -CH2CH2-, -(CH2) n1 , -CF2CH2-, -CH2CF2-, -CF2CF2-, -CH=N-, -N=CH-, -N=N-, -CH=CR 0 -、-CY 1 =CY 2 -、-C C-, -CH=CH-COO-, -OCO-CH=CH- or single bonds, preferably -COO-, -OCO-, or -C. C- or a single bond, with a single bond being the optimal choice.

[0290] R 0 R 00 It is H or an alkyl group having 1 to 12 carbon atoms.

[0291] Y 1 Y 2 For H, F, Cl, NCS or CN,

[0292] m1 and m2 can be 0, 1, 2, 3, or 4, preferably 0, 1, or 2, very preferably 0 or 1, and most preferably 0.

[0293] n1 can be 1, 2, 3 or 4.

[0294] The RM of formula T exhibits an unusually high refractive index n e And high birefringence.

[0295] Preferably, A, B, D, and E in formula T are selected from...

[0296]

[0297] Each of these groups, independently of each other and in the same or different manner each time it appears, has the following meaning:

[0298] L is P-Sp-, -CN, F, Cl, or optionally fluorinated and has 1 to 6, preferably 1 to 3, more preferably 1 or 2 C atoms, of an alkyl, alkoxy, or thioalkyl group, preferably P-Sp-, -CN, F, Cl, OCH3, SCH3, C2H5, OC2H5, or SC2H5.

[0299] r can be 0, 1, 2, 3 or 4, preferably 0, 1 or 2.

[0300] s can be 0, 1, 2, or 3, preferably 0 or 1.

[0301] t can be 0, 1, or 2, preferably 0 or 1.

[0302] More preferably, rings A, B, D and / or E in formula T are selected from phenyl-1,4-diyl, naphthyl-1,4-diyl, naphthyl-2,6-diyl, phenanthrene-2,7-diyl, anthracene-9,10-diyl, fluorene-2,7-diyl, dibenzofuran-2,7-diyl, dibenzothiophene-2,7-diyl, benzo[1,2-b:4,5-b']dithiophene-2,5-diyl, indole-4,7-diyl, benzothiophene-4,7-diyl, all of which are optionally substituted by one or more groups L and / or P-Sp-.

[0303] Very preferably, one, two, three, four or more rings A, B, D and / or E in formula T are selected from...

[0304]

[0305] Wherein L, in each occurrence, represents P-Sp-, -CN, F, Cl, or optionally fluorinated and has 1 to 6, preferably 1 to 3, more preferably 1 or 2 C atoms, of an alkyl, alkoxy, or thioalkyl group, preferably P-Sp-, -CN, F, Cl, OCH3, SCH3, C2H5, OC2H5, or SC2H5.

[0306] Particularly preferred are compounds of formula T, especially those in which n=m=0, wherein rings B and D are selected from phenyl-1,4-diyl, naphthol-1,4-diyl, naphthol-2,6-diyl or anthracene-9,10-diyl, all of which are optionally mono- or di-substituted by L and / or P-Sp-.

[0307] Preferably, the ring C in formula T is selected from...

[0308]

[0309] Each of these groups, independently of each other and in the same or different manner each time it appears, has the following meaning:

[0310] L is P-Sp-, -CN, F, Cl, or optionally fluorinated and has 1 to 6, preferably 1 to 3, more preferably 1 or 2 C atoms, of an alkyl, alkoxy, or thioalkyl group, preferably P-Sp-, -CN, F, Cl, OCH3, SCH3, C2H5, OC2H5, or SC2H5.

[0311] r can be 0, 1, 2, 3 or 4, preferably 0, 1 or 2.

[0312] s can be 0, 1, 2, or 3, preferably 0 or 1.

[0313] t can be 0, 1, or 2, preferably 0 or 1.

[0314] More preferably, C in formula T is selected from

[0315]

[0316] Wherein L, in each occurrence, represents P-Sp-, -CN, F, Cl, or optionally fluorinated and has 1 to 6, preferably 1 to 3, more preferably 1 or 2 C atoms, of an alkyl, alkoxy, or thioalkyl group, preferably P-Sp-, -CN, F, Cl, OCH3, SCH3, C2H5, OC2H5, or SC2H5.

[0317] Very preferably, the ring C in formula T is selected from phenyl-1,4-diyl, naphthalene-1,4-diyl, or anthracene-9,10-diyl, all of which are optionally mono- or di-substituted by L and / or P-Sp-.

[0318] Further preferred are compounds of formula T, especially those in which n=m=0, wherein rings B, C, and D form mesocrystalline groups selected from the following formulas or their mirror images:

[0319]

[0320]

[0321]

[0322] The naphthalene and phenanthrene groups are optionally replaced by one or two groups L, and L and r are as defined in formula T.

[0323] In formulas TM1 to TM28, preferably, L, in each occurrence, represents P-Sp-, -CN, F, Cl, or optionally fluorinated and has 1 to 6, preferably 1 to 3, more preferably 1 or 2 C atoms of an alkyl, alkoxy, or thioalkyl group, very preferably P-Sp-, methyl, ethyl, methoxy, ethoxy, thiomethyl, or thioethyl, most preferably methyl or ethyl, and r is preferably 0, 1, 2, or 3, very preferably 0, 1, or 2.

[0324] Groups of formulas TM01 to TM10 are highly preferred, especially groups of formulas TM01 to TM07.

[0325] The most preferred compounds of formula T are selected from the following sub-formulas:

[0326]

[0327]

[0328]

[0329]

[0330]

[0331]

[0332]

[0333]

[0334] The naphthalene and phenanthrene groups are optionally substituted by one or two groups L, and P, Sp, L, and r independently and, each time they appear, have the same or different meanings given in Formula T or one of the preferred meanings given above and below, and R has the meaning of R in Formula T. 11 One of the given meanings is preferably OCH3 or SCH3, with OCH3 being very preferred. L is preferably selected from alkyl, alkoxy, or thioalkyl groups having 1 to 6, more preferably 1, 2, or 3 C atoms, and is very preferably selected from methyl or ethyl groups. P is preferably an acrylate.

[0335] Compounds of formulas T-1 to T-20 are highly preferred, especially compounds of formulas T-1 to T-16.

[0336] In another preferred embodiment of the invention, the RM formulation comprises one or more RMs of formula T, which contain -C in the spacer group. The C-group (acetylene group), preferably a -C group directly attached to the benzene or naphthalene group of the mesocrystalline nucleus. C-groups. These RMs are preferably selected from formula A:

[0337]

[0338] Each of these groups, independently of each other and in the same or different manner each time it appears, has the following meaning:

[0339] P is a polymerizable group.

[0340] Sp can be a spacer group or a single bond.

[0341] Sp 1 It is a spacer group or a single bond, preferably an alkylene group having 1 to 12, more preferably 3 to 6 carbon atoms.

[0342] R 33 H, F, Cl, CN, CH=CH2, optionally fluorinated or chlorinated alkyl, alkoxy, thioalkyl, alkylcarbonyl, alkoxycarbonyl, alkylcarbonyl or alkoxycarbonyloxy, or P-Sp, having 1 to 6, preferably 1 to 3, carbon atoms.

[0343] A A B AThe groups are phenylene-1,4-diyl, naphthio-1,4-diyl, naphthio-2,6-diyl, fluorene-2,7-diyl, dibenzothiophene-2,7-diyl, dibenzofuran-2,7-diyl, benzo[1,2-b:4,5-b']dithiophene-2,5-diyl, indole-4,7-diyl, benzothiophene-4,7-diyl, 9,10-dihydro-phenanthroline-2,7-diyl, or 1,2,3,4-tetrahydronaphthalene-5,8-diyl, wherein one or more CH groups in these groups may be replaced by N, and all of them may optionally be replaced by one or more L or P-Sp- groups.

[0344] C A The group is phenylene-1,4-diyl, naphthol-1,4-diyl, or naphthol-2,6-diyl, preferably phenylene-1,4-diyl or naphthol-2,6-diyl, wherein one or more CH groups in these groups may be replaced by N, and optionally by one or more L or P-Sp- groups.

[0345] Preferably, A A B A and C A No more than one of them represents naphthalene-1,4-diyl.

[0346] L is F, Cl, -CN, -SCN, P-Sp-, or a straight-chain, branched, or cyclic alkyl group having 1 to 25 C atoms, wherein one or more non-adjacent CH2- groups are optionally replaced by the following groups in such a way that the O atoms and / or S atoms are not directly connected to each other: -O-, -S-, -CO-, -CO-O-, -O-CO-, -O-CO-O-, CR 0 =CR 00 -、-C C-、

[0347]

[0348] Furthermore, one or more H atoms may be optionally replaced by P-Sp-, F, or Cl, or two substituents L connected to directly adjacent C atoms may form cycloalkyl or cycloalkenyl groups with 5, 6, 7, or 8 C atoms.

[0349] Z 11 for -O-, -S-, -CO-, -COO-, -OCO-, -S-CO-, -CO-S-, -O-COO-, -CO-NR 0 -、-NR 0 -CO-、-NR 0 -CO-NR 00 -NR 0 -CO-O-、-O-CO-NR 0-, -OCH2-, -CH2O-, -SCH2-, -CH2S-, -CF2O-, -OCF2-, -CF2S-, -SCF2- 、 -CH2CH2-、-(CH2) n1 , -CF2CH2-, -CH2CF2-, -CF2CF2-, -CH=N-, -N=CH-, -N=N-, -CH=CR 0 -、-CY 1 =CY 2 -、-C C-, -CH=CH-COO-, -OCO-CH=CH- or single bonds, preferably -COO-, -OCO-, or -C. C- or a single bond, with a single bond being the optimal choice.

[0350] R 0 R 00 It is H or an alkyl group having 1 to 12 carbon atoms.

[0351] Y 1 Y 2 For H, F, Cl, NCS or CN,

[0352] m2 can be 0, 1, 2, 3 or 4, preferably 0, 1 or 2, more preferably 0 or 1, and most preferably 0.

[0353] m3 is 0 or 1.

[0354] n1 is 1, 2, 3, or 4.

[0355] s can be 0, 1, 2 or 3, preferably 0, 1 or 2.

[0356] The RM of formula A exhibits a very high unusual refractive index n e They also exhibit very high birefringence. Furthermore, their maximum absorption peaks shift to lower wavelengths, resulting in a steeper pitch in the UV absorbance curve, which leads to lower coloration of the RM and polymer films made from it.

[0357] In the compound of formula A, preferably, A A and B A Selected from

[0358]

[0359] Where A A and B A At least one of the groups is selected from phenylene-1,4-diyl and naphthalene-2,6-diyl, and wherein each group, independently of each other and in each occurrence, has the following meaning, either identically or differently.

[0360] L is P-Sp-, -CN, F, Cl, or optionally fluorinated and has 1 to 6, preferably 1 to 3, more preferably 1 or 2 C atoms, of an alkyl, alkoxy, or thioalkyl group, preferably P-Sp-, -CN, F, Cl, OCH3, SCH3, C2H5, OC2H5, SC2H5, CHO, COCH3, COOCH3, or COOH.

[0361] r can be 0, 1, 2, 3 or 4, preferably 0, 1 or 2.

[0362] s can be 0, 1, 2, or 3, preferably 0 or 1.

[0363] t can be 0, 1, or 2, preferably 0 or 1.

[0364] More preferably, the ring A in formula A A and B A Selected from phenylene-1,4-diyl, naphthalene-1,4-diyl and naphthalene-2,6-diyl, all of which are optionally substituted by one or more groups L and / or P-Sp-, wherein not more than one of A and B may represent naphthalene-1,4-diyl.

[0365] Very preferably, ring A in formula A A and B A One, two, three, four or more selected from

[0366]

[0367] Where A A and B A No more than one of them may represent naphthalene-1,4-diyl, and wherein L, in each occurrence, may represent P-Sp-, -CN, F, Cl or optionally fluorinated and having 1 to 6, preferably 1 to 3, more preferably 1 or 2 C atoms of an alkyl, alkoxy or thioalkyl group, preferably P-Sp-, F, Cl, CN, CH3, OCH3, SCH3, C2H5, OC2H5 or SC2H5.

[0368] Compounds of formula A are particularly preferred, especially those in which n=m=0, and ring B A It is selected from phenylene-1,4-diyl, naphthalene-1,4-diyl and naphthalene-2,6-diyl, preferably phenylene-1,4-diyl, naphthalene-1,4-diyl and naphthalene-2,6-diyl, all of which are optionally monosubstituted or disubstituted by L and / or P-Sp-.

[0369] Preferably, the ring C in formula A A Selected from

[0370]

[0371] Wherein L, in each occurrence, represents P-Sp-, -CN, F, Cl, or optionally fluorinated and has 1 to 6, preferably 1 to 3, more preferably 1 or 2 C atoms, of an alkyl, alkoxy, or thioalkyl group, preferably P-Sp-, F, Cl, CN, CH3, OCH3, SCH3, C2H5, OC2H5, or SC2H5.

[0372] Further preferred are compounds of formula A, wherein m=1 and / or ring B. A and C A At least one of them represents naphthalene-2,6-dimethyl.

[0373] Further preferred are compounds of formula A in which m=0, and more preferably those in which n=0, wherein ring B A and C A Together with phenylene-1,4-diyl, it forms a group selected from the following formula or its mirror image, wherein Indicates the connection with the acetylene group in formula A:

[0374]

[0375] The naphthalene group is optionally replaced by one or two groups L, r is 0, 1, 2, 3 or 4, preferably 0, 1 or 2, and L is as defined in Formula A.

[0376] Further preferred are compounds of formula A in which m=1, and more preferably those in which n=0, wherein ring B A and C A Together with naphthalene-2,6-diyl, it forms a group selected from the following formula or its mirror image, wherein Indicates the connection with the acetylene group in formula A:

[0377]

[0378] The naphthalene group is optionally replaced by one or two groups L, r is 0, 1, 2, 3 or 4, preferably 0, 1 or 2, and L is as defined in Formula A.

[0379] In formulas AM01 to AM08 and AM1 to AM9, L preferably represents P-Sp-, -CN, F, Cl or optionally fluorinated P-Sp-, -CN, F, Cl or either C-sp- or -CN, and has 1 to 6, preferably 1 to 3, more preferably 1 or 2 C atoms of alkyl, alkoxy or thioalkyl, very preferably P-Sp-, F, Cl, CN, CH3, OCH3, SCH3, C2H5, OC2H5 or SC2H5, most preferably CH3 or C2H5, and r is preferably 0, 1, 2 or 3, very preferably 0, 1 or 2.

[0380] Especially preferred are groups of formulas AM01, AM02, AM03, AM04, AM1, AM2 and AM3.

[0381] The most preferred compounds of formula A are selected from the following sub-formulas:

[0382]

[0383]

[0384]

[0385]

[0386]

[0387] The naphthalene group is optionally substituted by one or two groups L, and P, Sp, L, and r independently and, each time they appear, have the same or different meanings given above, and R has the meaning of R in formula A. 11 One of the given meanings is preferably OCH3 or SCH3, with OCH3 being very preferred. L is preferably selected from F, Cl, CN, CH3, OCH3, SCH3, C2H5, OC2H5, or SC2H5. P is preferably an acrylate.

[0388] Further preferred are two reactive compounds of formulas A and A-1 to A-64, wherein one of the two Sp groups is a single bond and the other Sp group is different from a single bond.

[0389] In compounds of formulas D, M, T, A and their sub-formulas as described above and below, P is preferably selected from ethylene oxides, acrylates, methacrylates, fluoroacrylates, chloroacrylates, oxetanes and epoxides, very preferably selected from acrylates and methacrylates, and most preferably acrylates.

[0390] Further preferred are compounds of formulas D, M, T, A and their sub-formulas as described above and below, wherein all polymerizable groups P present in the compound have the same meaning and very preferably represent acrylates or methacrylates, most preferably acrylates.

[0391] Further preferred are compounds of formulas D, M, T, A and their sub-formulas as described above and below, which contain one, two, three or four P-Sp groups, with two or three P-Sp groups being very preferred.

[0392] Further preferred are compounds of formulas T, A, and their derivatives as described above and below, wherein R 11 It is P-Sp-.

[0393] Further preferred are compounds of formulas M, T, A and their derivatives as described above and below, wherein R 22 Or R 11 The atom is selected from F, Cl, CN, CF3, CCl3, CH=CH2 or optionally fluorinated alkoxy, thioalkyl, alkylcarbonyl, alkoxycarbonyl, alkylcarbonyloxy or alkoxycarbonyloxy having 1 to 3 C atoms, more preferably from F, Cl, CN, OCH3, SCH3, OCF3, CF3, CH=CH2, CHO, COCH3, COOCH3, COOC2H5 and CCl3, very preferably from OCH3, OCF3 or CHO, and most preferably from OCH3 or OCF3.

[0394] Further preferred are compounds of formulas D, M, T, A and their derivatives as described above and below, wherein Sp 1 and / or Sp 2 If it exists, it represents -(CH2). s1 - where s1 is an integer from 1 to 12, more preferably 3, 4, 5 or 6.

[0395] Further preferred are compounds of formulas D, M, T, A and their derivatives as described above and below, wherein Sp 1 and / or Sp 2 If present, it indicates a single bond or -(CH2). p1 -、-O-(CH2) p1 -、-O-CO-(CH2) p1 Or -CO-O-(CH2) p1 , where p1 is 2, 3, 4, 5, or 6, and if Sp is -O-(CH2). p1 -、-O-CO-(CH2) p1 Or -CO-O-(CH2) p1 The O atom or CO group is attached to the benzene ring.

[0396] Further preferred are compounds of formulas D, M, T, A and their derivatives as described above and below, wherein Sp 1 and / or Sp 2 If it exists, it is a single bond.

[0397] Further preferred are compounds of formulas D, M, T, A and their derivatives as described above and below, wherein Sp 1 and / or Sp 2 If it exists, it is different from a single bond.

[0398] Further preferred are compounds of formulas D, M, T, A and their sub-formulas as described above and below, where m is 1.

[0399] Further preferred are compounds of formulas T, A and their sub-formulas as described above and below, wherein at least one of B and C represents naphthalene-2,6-diyl or naphthalene-1,4-diyl, very preferably naphthalene-2,6-diyl, which is optionally substituted with one or more groups L or P-Sp-.

[0400] Further preferred are compounds of formulas T, A, and their derivatives as described above and below, wherein L is a p-Sp-, F, Cl, -CN, or a straight-chain, branched, or cyclic alkyl group having 1 to 25 C atoms, wherein one or more non-adjacent CH2- groups are optionally replaced by the following groups in such a manner that the O atoms and / or S atoms are not directly connected to each other: -O-, -S-, -CO-, -CO-O-, -O-CO-, -O-CO-O-, CR 0 =CR 00 -、-C C-、

[0401]

[0402] Furthermore, one or more H atoms may be optionally replaced by P-Sp-, F, or Cl, or two substituents L connected to directly adjacent C atoms may form cycloalkyl or cycloalkenyl groups having 5, 6, 7, or 8 C atoms, and R may be used to form cycloalkyl or cycloalkenyl groups. 0 and R 00 Each can be independently represented by H or an alkyl group having 1 to 12 carbon atoms.

[0403] Highly preferred are compounds of formulas T, A and their sub-formulas as described above and below, wherein L is F, Cl, CN or a straight-chain alkyl, alkoxy or thioalkyl having 1 to 6 C atoms or a branched or cyclic alkyl, alkoxy or thioalkyl having 3 to 8 C atoms, most preferably F, Cl, CN, CH3, OCH3, SCH3, C2H5, OC2H5 or SC2H5.

[0404] Further preferred are compounds of formulas T, A, and their derivatives as described above and below, wherein Z 11 and Z 12 This indicates -COO-, -OCO-, and -C. C- or a single bond, more preferably -C C- or single bond, with single bond being the preferred choice.

[0405] Further preferred compounds of formulas T and A and their sub-formulas are selected from the following preferred embodiments, including any combination thereof:

[0406] - n = 0, and / or

[0407] - Ring C or C AEach of the above represents phenylene-1,4-diyl, which is substituted with an alkyl, alkoxy, or thioalkyl group having 1 to 3, preferably 1 or 2, carbon atoms, more preferably methyl or ethyl, and most preferably ethyl.

[0408] - Ring C or C A Each represents naphthalene-2,6-dimethyl, which is optionally substituted with one or more L or P-Sp- groups, and / or

[0409] - Ring B or B A Each represents naphthalene-2,6-dimethyl, which is optionally substituted with one or more L or P-Sp- groups, and / or

[0410] - m=1 and / or at least one of B and C, or B A and C A At least one of them, representing naphthalene-2,6-diyl, which is optionally substituted with one or more L or P-Sp- groups.

[0411] - m=0, and at least one of B and C, or B A and C A At least one of them, representing naphthalene-2,6-diyl, which is optionally substituted with one or more L or P-Sp- groups.

[0412] - P indicates acrylate or methacrylate, and / or

[0413] - Sp 1 It represents -(CH2) s1 - where s1 is an integer from 1 to 12, preferably 3, 4, 5 or 6, and / or

[0414] - Sp represents Sp"-X", preferably, -Sp"-X"- represents -(CH2) p1 -、-(CH2) p1 -O-、-(CH2) p1 -O-CO-、-(CH2) p1 -CO-O-、-(CH2) p1 -O-CO-O-、-(CH2CH2O) q1 -CH2CH2-, -CH2CH2-S-CH2CH2-, or -CH2CH2-NH-CH2CH2-, where p1 is an integer from 1 to 12, q1 is an integer from 1 to 3, and / or

[0415] - L is selected from P-Sp-, F, Cl, CN, CH3, OCH3, SCH3, C2H5, OC2H5 or SC2H5, with CH3 or C2H5 being highly preferred, and r represents 1, and / or

[0416] - The ring C is replaced by an L, where L represents P-Sp-, preferably acrylate, and / or

[0417] - R 11 It is P-Sp-, or

[0418] - R 11 It is F, Cl, CN, OCH3 or SCH3, preferably OCH3 or SCH3, and very preferably OCH3.

[0419] The following are highly preferred compounds of formula T:

[0420]

[0421]

[0422]

[0423]

[0424]

[0425]

[0426]

[0427]

[0428] Especially preferred are compounds of formulas T-3, T-19, T-21, T-24, T-25, T-30, T-47, T-50, T-53, T-59, T-60, T-68, T-70, T-71, T-73 and T-75.

[0429] The following are highly preferred compounds of formula A:

[0430]

[0431]

[0432]

[0433] Compounds of formulas D, M, T, A and their sub-formulas, alone or in combination with other RMs in RM formulations, particularly and preferably simultaneously exhibit high birefringence, good solubility in well-known organic solvents used in mass production, improved orientation, favorable transition temperature and high tolerance to yellowing upon exposure to ultraviolet light.

[0434] Preferably, the RM formulation contains one or more compounds selected from the formulas D, M, T, A and their derivatives.

[0435] Most preferably, the RM formulation contains 1 to 6, most preferably 1 to 4 RMs, preferably selected from D, M, T, A and their subforms.

[0436] If the RM formulation contains one or more di-reactive or multi-reactive RMs of formula D or its sub-formulas, their concentration is preferably 1 to 50% of the total solids, very preferably 5 to 30%.

[0437] If the RM formulation contains one or more monoreactive RMs of formula M or its derivatives, their concentration is preferably 1 to 70% of the total solids, very preferably 10 to 50%.

[0438] If the RM formulation contains one or more RMs of formula T or its derivatives, their concentration is preferably 1 to 70% of the total solids, very preferably 10 to 50%.

[0439] If the RM formulation contains one or more RMs of formula A or its derivatives, their concentration is preferably 1 to 70% of the total solids, very preferably 10 to 50%.

[0440] In another preferred embodiment, the RM formulation further comprises one or more optional polymerizable and / or isomerizable chiral compounds.

[0441] In another preferred embodiment, the RM formulation contains one or more, preferably exactly one, chiral compound, preferably selected from polymerizable chiral compounds, and very preferably selected from monoreactive or direactive chiral polymerizable compounds.

[0442] Suitable polymerizable chiral compounds preferably comprise one or more ring elements linked together by direct bonds or via linking groups, wherein two of these ring elements may optionally be linked to each other directly or via linking groups, which may be the same as or different from the linking groups mentioned. The ring elements are preferably selected from quaternary, pentagonal, hexaternary, or septagonal rings, with pentagonal or hexaternary rings being preferred.

[0443] Preferred polymerizable chiral compounds are selected from formulas C1, C2, and C3:

[0444]

[0445] Each of these groups, independently of each other and in the same or different manner each time it appears, has the following meaning:

[0446] P 0 It is a polymerizable group.

[0447] Sp 0 Spacer groups or single bonds

[0448] R 0 F, Cl, CN, alkyl, alkoxy, thioalkyl, alkylcarbonyl, alkoxycarbonyl, alkylcarbonyl or alkoxycarbonyloxy, having 1 to 15, preferably 1 to 6, carbon atoms, P 0 -or P 0 -Sp -,

[0449] A 0 B 0 E 0 F 0 It is an unsubstituted or L-substituted 1,4-phenylene, or trans-1,4-cyclohexylene.

[0450] L is F, Cl, CN, P-Sp- or optionally fluorinated alkyl, alkoxy, thioalkyl, alkylcarbonyl, alkoxycarbonyl, alkylcarbonyl or alkoxycarbonyl groups having 1 to 5 carbon atoms.

[0451] X 1 X 2 It can be -O-, -COO-, -OCO-, -O-CO-O-, or a single bond.

[0452] Z 0 is -COO-, -OCO-, -O-CO-O-, -OCH2-, -CH2O-, -CF2O-, -OCF2-, -CH2CH2-, -(CH2)4-, -CF2CH2-, -CH2CF2-, -CF2CF2-, -C C-, -CH=CH-, -CH=CH-COO-, -OCO-CH=CH- or a single bond, preferably -COO-, -OCO- or a single bond.

[0453] a0 can be 0, 1, or 2, preferably 0 or 1.

[0454] b0 is 0 or an integer from 1 to 12, preferably an integer from 1 to 6.

[0455] t0 is 0, 1, 2, or 3.

[0456] z0 can be 0 or 1, preferably 1.

[0457] Furthermore, the naphthalene ring can be substituted by one or more identical or different groups L.

[0458] Further preferred are the stereoisomers of formula C2, wherein the central isosorbide unit is replaced by isomannitol or isoidide units.

[0459] Compounds of formula C1 are preferably selected from the following formulas:

[0460]

[0461] Where A 0 B 0 Z 0 X 2 P 0 a and b have one of the meanings given in formula Ca or the preferred meanings given above and below, and (OCO) represents -O-CO- or a single bond.

[0462] Further preferred compounds of formula C are selected from the following sub-formulas:

[0463]

[0464]

[0465] Where R It is as defined in equation C1-1 -X 2 -(CH2) t -P 0 Furthermore, the benzene and naphthalene rings are either unsubstituted or substituted with 1, 2, 3, or 4 L groups as defined above and below.

[0466] In the presence of one or more polymerizable chiral compounds, their concentration in the RM formulation is preferably 0.1 to 10% by weight of the total solids, more preferably 0.5 to 8% by weight.

[0467] Preferably, the polymerizable chiral compounds, individually or in combination, have a diameter of 20 µm. -1 Or larger, preferably 40 µm -1 Or larger, preferably 60 µm -1 Or larger, preferably at 80 µm -1 Or even larger than 260 µm -1 Helical torsional force (IHTP) within the range 总 The absolute value of I).

[0468] In another preferred embodiment, as a supplement to or alternative to the chiral compounds described above and below, the RM formulation contains one or more isomerizable, preferably photoisomerizable, and most preferably photoisomerizable and polymerizable chiral compounds. Most preferably, these compounds can be photoisomerized by ultraviolet light irradiation.

[0469] More preferably, the RM formulation contains only polymerizable chiral isomerizable compounds, preferably selected from monoreactive or direactive chiral isomerizable compounds.

[0470] In another preferred embodiment, the RM formulation comprises at least two, more preferably exactly two, chiral compounds with opposite chirality, one containing an isomerizable group and the other not containing an isomerizable group, and wherein one or both, preferably both, of the chiral compounds are polymerizable. Irradiation of the isomerizable chiral compound alters its torsional force, while the torsional force of the non-isomerizable chiral compound remains unchanged. This allows for the control and adjustment of the torsional distribution in the final RM layer accordingly.

[0471] Suitable polymerizable chiral isomerizable compounds preferably comprise one or more ring elements linked together by direct bonds or via linking groups, wherein two of these ring elements may optionally be linked to each other directly or via linking groups, which may be the same as or different from the mentioned linking groups. The ring elements are preferably selected from quaternary, pentagonal, hexaternary, or septagonal rings, with pentagonal or hexaternary rings being preferred.

[0472] Preferred chiral isomerizable compounds are selected from formula I :

[0473] R 3 -(A 3 -Z 3 ) m -G(-(Z 4 -A 4 ) l -R 4 ) k I

[0474] Each of these groups, independently of each other and in the same or different manner each time it appears, has the following meaning:

[0475] R 3 R 4It is H, F, Cl, CN, P-Sp-, or an alkyl group having up to 25 C atoms, which may be unsubstituted, monosubstituted or polysubstituted with halogen or CN, and may also include one or more non-adjacent CH2 groups, each independently of each other in such a way that the oxygen atoms are not directly connected to each other, and are represented by -O-, -S-, -NH-, -N(CH3)-, -CO-, -COO-, -OCO-, -OCO-O-, -S-CO-, -CO-S-, or -C. C-substitution,

[0476] P is a polymerizable group.

[0477] Sp can be a spacer group or a single bond.

[0478] Z 3 Z 4 is -CO-O-, -O-CO-, -CH2CH2-, -OCH2-, -CH2O-, -CH=CH-, -CH=CH-CO-O-, -O-CO-CH=CH-, -CH=C(CN)-CO-O-, -O-CO-C(CN)=CH-, -N=N-, -CH=N-, -N=CH-, -C C- or single bond,

[0479] A 3 A 4 It is an alicyclic, heterocyclic, aromatic, or heteroaromatic group having 4 to 20 ring atoms, which is monocyclic or polycyclic and optionally substituted by one or more L or P-Sp groups.

[0480] G is a chiral group.

[0481] L is F, Cl, -CN, -SCN, P-Sp-, or a straight-chain, branched, or cyclic alkyl group having 1 to 25 C atoms, wherein one or more non-adjacent CH2- groups are optionally replaced by the following groups in such a way that the O atoms and / or S atoms are not directly connected to each other: -O-, -S-, -CO-, -CO-O-, -O-CO-, -O-CO-O-, CR 0 =CR 00 -、-C C-

[0482]

[0483] Furthermore, one or more H atoms may be optionally replaced by P-Sp-, F, or Cl, or two substituents L connected to directly adjacent C atoms may form cycloalkyl or cycloalkenyl groups with 5, 6, 7, or 8 C atoms.

[0484] m and l are independently 0, 1, 2 or 3.

[0485] k is 0, 1, or 2.

[0486] The compound contains at least one isomerizable group, preferably a photoisomerizable group, and more preferably, R 3 and R 4 At least one of them represents P-Sp-.

[0487] Preferred Formula I Compounds of the formula R and its derivatives are those in which R 3 and R 4 At least one of them, preferably R 3 and R 4 Both refer to those of P-Sp-.

[0488] Further preferred formula I Compounds of the formula R and its derivatives are those in which R 3 and R 4 At least one of them, preferably R 3 and R 4 Both differ from P-Sp-, and preferably represent alkyl or alkoxy groups having 1 to 12, more preferably 1 to 6 C atoms, and R 3 and R 4 One can also refer to those of F, Cl, or CN.

[0489] Preferred Formula I The compounds with the following formulas and sub-formulas are: where A 3 and A 4 The group is selected from 1,4-phenylene, naphthalene-1,4-diyl, naphthalene-2,6-diyl, 1,4-cyclohexylene (wherein one or two non-adjacent CH2 groups may be replaced by O and / or S), 1,4-cyclohexenylene, 1,4-bicyclo(2,2,2)octylene, piperidine-1,4-diyl, naphthalene-2,6-diyl, decahydronaphthalene-2,6-diyl, or 1,2,3,4-tetrahydronaphthalene-2,6-diyl, with 1,4-phenylene or 1,4-cyclohexylene being most preferred, all of which may optionally be substituted with one or more L or P-Sp groups.

[0490] Further preferred formula I The compounds of the Z formula are among them. 3 and Z 4 Those that independently represent -CO-O-, -O-CO-, or single bonds.

[0491] Further preferred formula I The compounds thereof and their derivatives are those in which L is selected from F, Cl, CN, CH3, C2H5, OCH3, OC2H5, COCH3, COC2H5, CF3, OCF3, P-Sp-, especially F, Cl, CN, CH3, C2H5, OCH3, COCH3 or OCF3, with the most preferred being those of F, CH3, OCH3 or COCH3.

[0492] Further preferred formula I The compounds thereof and their derivatives are wherein P is selected from ethylene oxide, acrylate, methacrylate, fluoroacrylate, chloroacrylate, oxetane and epoxide, very preferably selected from acrylate and methacrylate, and most preferably those of acrylate.

[0493] Further preferred formula I Compounds with the following formulas are those in which Sp represents a single bond or -(CH2). p1 -、-O-(CH2) p1 -、-O-CO-(CH2) p1 Or -CO-O-(CH2) p1 Where p1 is an integer from 2 to 10, preferably 2, 3, 4, 5 or 6, and if Sp is -O-(CH2) p1 -、-O-CO-(CH2) p1 Or -CO-O-(CH2) p1 Then the O atoms or CO groups are respectively attached to those of the benzene ring.

[0494] Further preferred formula I Compounds of the same or different formulas are those in which all polymerizable groups P present in the compound have the same meaning, and are very preferably acrylates or methacrylates, most preferably those acrylates.

[0495] Further preferred formula I Compounds of the same or their derivatives contain one, two, three or four P-Sp groups, with those containing two or three P-Sp groups being particularly preferred.

[0496] Further preferred formula I Compounds of which at least one Sp group is a single bond are those.

[0497] Further preferred formula I Compounds of the following formulas are those in which at least one Sp group is a single bond and at least one Sp group is different from a single bond.

[0498] Further preferred formula I Compounds of which at least one Sp group is different from a single bond and is selected from -(CH2) are...p1 -、-O-(CH2) p1 -、-O-CO-(CH2) p1 Or -CO-O-(CH2) p1 Where p1 is an integer from 2 to 10, preferably 2, 3, 4, 5 or 6, and if Sp is -O-(CH2) p1 -、-O-CO-(CH2) p1 Or -CO-O-(CH2) p1 Then the O atoms or CO groups are respectively attached to those of the benzene ring.

[0499] In R 3 Or R 4 In the case of a group of the formula P-Sp-, the spacer groups on each side of the mesocrystalline nucleus can be the same or different.

[0500] In Equation I In the compound, m and l are preferably 0 or 1.

[0501] Preferred Formula I Compounds of the formula G and its derivatives are those in which G represents or contains a photoisomerizable group.

[0502] Further preferred formula I The compounds of the Z formula are among them. 3 and / or Z 4 Those that independently represent -CH=CH-CO-O-, -O-CO-CH=CH-, -CH=C(CN)-CO-O-, -O-CO-C(CN)=CH-, -CH=N-, -N=CH-, or -N=N-.

[0503] Further preferred formula I Its derivatives are those containing isomerizable groups selected from the following: stilbene, (1,2-difluoro-2-phenyl-vinyl)benzene, cinnamate, α-cyanocinate, 4-phenylbut-3-en-2-one, Schiff base, 2-benzylidene-1-indanone, chalcone, coumarin, chromone, dicyclopentadienone, or azobenzene.

[0504] Further preferred formula I Compounds thereof are those in which the chiral group G is selected from or derived from the following: disohydrohexitol, preferably isosorbide, isomannitol or iso-idyl alcohol, 1,1'-bis-2-naphthol (binaphthol), 1,2-diphenyl-1,2-ethylenediol (hydrogenated benzoin), 2-benzyl-p-menthane-3-one and menthyl cinnamate ((2 E )-3-phenyl-2-acrylic acid (1 R ,2 S 5R 5-methyl-2-(1-methylethyl)cyclohexyl ester.

[0505] Highly Preferred Formula I The compounds in which the chiral group G is selected from those of formula A are:

[0506]

[0507] Where X is -CO-O-, -CH=CH-CO-O-, or -CH=C(CN)-CO-O-, with the O- atom of the ester attached to the furan ring, or -N=N-, q is 0, 1, 2, 3, or 4, and L has formula I. The meaning of, or one of its preferred meanings as given above and below.

[0508] Formula A includes the following stereoisomers based on the corresponding disohydrated hexitol:

[0509]

[0510] Where X, L, and q have the meanings given in formula A, and where Ai is based on isosorbide, Aii is based on isomannitol, and Aiii is based on isoidolitol. Ai is particularly preferred.

[0511] Further preferred formula I The compounds of the Z formula are among them. 3 and Z 4 One or both of them independently represent -CH=CH-CO-O-, -O-CO-CH=CH-, -CH=C(CN)-CO-O-, -O-CO-C(CN)=CH-, -CH=N-, -N=CH- or -N=N-, and / or where G is formula A, preferably Ai, and X represents those of -CH=CH-CO-O-, -CH=C(CN)-CO-O- or -N=N-.

[0512] Further preferred formula I The compounds thereof are those in which G is of formula A, preferably formula Ai, and X represents -CH=CH-CO-O-, -CH=C(CN)-CO-O-, or -N=N-, with -CH=CH-CO-O- being the most preferred.

[0513] Further preferred formula I Compounds thereof and their derivatives are those in which the chiral group G is selected from those of the following formulas.

[0514]

[0515] in

[0516] X, L, and q have the meanings given in Equation A or one of the preferred meanings given above and below.

[0517] R 11 and R 12 Represented independently as in Equation I -(Z) is defined in 4 -A 4 ) l -R 4 ,

[0518] Or R 11 and R 12 Together with the O atom, they form cyclic or spirocyclic groups, which are optionally composed of a compound as shown in Formula I. The group defined in the middle -(Z) 4 -A 4 ) l -R 4 replace,

[0519] R 13 and R 14 Represented independently as in Equation I R as defined in 3 -(A 3 -Z 3 ) m -,

[0520] a1 and a2 are independently 0, 1, or 2.

[0521] And the dashed line represents equation I. The connection of adjacent groups in the [structure / structure].

[0522] Preferred Formula I The compounds are selected from the following formula:

[0523]

[0524] Where R 3 R 4 Z 4 A 4 L and q are independent of each other and, in each occurrence, have the same or different characteristics in Equation I. The meaning given in the text, or one of the preferred meanings given above and below, is l1 0, 1, or 2, R 13 R 14 a1 and a2 have the meanings given in equation G or one of the preferred meanings given above and below, R 15 Represented as in Equation I -(Z) is defined in 4 -A 4 ) l -R 4 And X11 and X 12 It represents -O-CO-CH=CH-.

[0525] Highly Preferred Formula I Compounds of A are selected from the following formulas:

[0526]

[0527]

[0528] Where P, Sp, L, and q have in equation I R is given the meaning or one of the preferred meanings given above and below. Having Equation I The R that is different from P-Sp- 3 One of the meanings of R, and R Having Equation I The R that is different from P-Sp- 4 One of the meanings of .

[0529] Formula I is particularly preferred. A3 compounds.

[0530] Further preferred is formula I A, I B, I A1、I A2 and I A stereoisomer of A3, wherein the central isosorbide unit is replaced by isomannitol or isoidutol unit.

[0531] In Equation I A, I B, I A1、I A2 and I In compounds of A3, P is preferably an acrylate or a methacrylate, very preferably an acrylate, and Sp is preferably -O-(CH2). p1 -、-O-CO-(CH2) p1 -or -CO-O-(CH2) p1 -, Highly Preferred -O-(CH2) p1 - where the O atom or CO group is attached to the benzene ring, p1 is an integer from 1 to 6, more preferably 2, 3, 4, 5 or 6, and R 4 P-Sp- is preferred.

[0532] Further preferred formula I Compounds of the following formula and their derivatives are selected from the following:

[0533]

[0534]

[0535]

[0536]

[0537]

[0538] Among them, P, Sp, R R L and q have in Equation I and I The meaning given in A1, or one of the preferred meanings given above and below, R 16 and R 17 Each of the above can be independently represented as an alkyl group having 1 to 12, preferably 1 to 6, carbon atoms, with methyl, ethyl, or propyl being most preferred, and R 18 It represents P-Sp-, H or an alkyl group having 1 to 12, preferably 1 to 6, carbon atoms, with H being very preferred.

[0539] In Equation I C1 to I In the compound G1, P is preferably an acrylate or a methacrylate, very preferably an acrylate, and Sp is preferably -O-(CH2). p1 -、-O-CO-(CH2) p1 -or -CO-O-(CH2) p1 -, Highly Preferred -O-(CH2) p1 - where the O atom or CO group is attached to the benzene ring, p1 is an integer from 1 to 6, more preferably 2, 3, 4, 5 or 6, R and R Preferably, they are alkyl or alkoxy groups having 1 to 12, very preferably 1 to 6 C atoms, and are independent of each other.

[0540] Formula IA The compounds can be prepared, for example, according to or similar to the methods described in GB 2314839 A. Formula I E1 to I The compounds of E15 can be prepared, for example, according to or similar to the methods described in WO 02 / 40614 A1.

[0541] Preferably, the chiral isomerizable compounds used, individually or in combination, have a molecular weight of 20 µm. -1 Or larger, preferably 40 µm -1 Or larger, preferably 60 µm -1 Or larger, preferably at 80 µm -1Or even larger than 260 µm -1 Helical torsional force (IHTP) within the range 总 The absolute value of I).

[0542] Preferably, the chiral isomerizable compound, especially those selected from formula I Those of the following, or their sub-formulas, are present in a proportion of 0.1 to 4% by weight in the total RM mixture according to the invention, very preferably in a proportion of 0.2 to 3% by weight, and most preferably in a proportion of 0.3 to 2% by weight.

[0543] In another preferred embodiment, the RM formulation contains one or more, preferably exactly one, non-polymerizable chiral dopant.

[0544] Preferred chiral dopants are selected from compounds of formulas C1 to C-III.

[0545]

[0546] Formulas C-II and C-III comprise their respective (S,S) enantiomers, and E and F are each independently 1,4-phenylene or trans-1,4-cyclohexylene, v is 0 or 1, and Z is 1,4-phenylene or trans-cyclohexylene. 0 It is -COO-, -OCO-, -CH2CH2- or a single bond, and R c It is an alkyl, alkoxy, or alkanoyl group having 1 to 12 carbon atoms.

[0547] Further preferred are stereoisomers of formula C-II, wherein the central isosorbide unit is replaced by isomannitol or isoidutol units.

[0548] Compounds of formula C1 and their synthesis are described in EP1389199 A1. Compounds of formula C-II and their synthesis are described in WO98 / 00428 A1. Compounds of formula C-III and their synthesis are described in GB2328207 A.

[0549] Further preferred chiral dopants are, for example, commercially available R / S-6011, R / S-5011, R / S-4011, R / S-3011, R / S-2011, R / S-1011, R / S-811 and CB-15 (from Merck KGaA, Darmstadt, Germany).

[0550] The amount of the non-polymerizable chiral dopant in the RM formulation is preferably 0.1 to 10% by weight of all solids, more preferably 0.5 to 8% by weight.

[0551] In another preferred embodiment, the RM formulation according to the invention does not contain any chiral compounds.

[0552] The RM mixture contained in the RM formulation preferably exhibits a nematic phase at room temperature, or, in the presence of a chiral compound, a chiral nematic (also known as "cholesterol") LC phase, or a chiral smectic LC phase and a chiral nematic LC phase, most preferably a nematic or chiral nematic LC phase.

[0553] The RM mixture contained in the RM formulation preferably has a birefringence in the range of 0.18 to 0.8, more preferably in the range of 0.20 to 0.7, and even more preferably in the range of 0.25 to 0.6. n).

[0554] The proportion of the RM mixture in the RM formulation is preferably 85 to 100% of the total solid and liquid additives (i.e., excluding solvents), more preferably 85 to 99%, and very preferably 90 to 99%.

[0555] Selected from equations D, M, T, A and their sub-equations, and arbitrarily selected from equations C1, C2, C3, D, M, I The total proportion of the compounds of the same and their derivatives in the RM formulation according to the invention is preferably 85 to 100% of the total solids (i.e., excluding solvents), more preferably 85 to 99%, and very preferably 90 to 99%.

[0556] The RM formulation preferably exhibits a chiral nematic LC phase, or a chiral smectic LC phase and a chiral nematic LC phase at room temperature, with a chiral nematic LC phase being highly preferred.

[0557] The RM formulation preferably has a birefringence in the range of 0.10 to 0.8, more preferably in the range of 0.12 to 0.7, and even more preferably in the range of 0.12 to 0.6. n).

[0558] Preferably, the RM formulation comprises a non-chiral host mixture and a chiral component. The non-chiral host mixture preferably comprises, and very preferably comprises, one or more mono-reactive and / or di-reactive non-chiral RMs (preferably selected from formulas D, M, T, and A and their derivatives), but does not contain chiral compounds. The chiral component preferably comprises, and very preferably comprises, one or more chiral compounds (preferably selected from formulas C1, C2, and C3 and their derivatives).

[0559] The proportion of the non-chiral main component mixture in the RM formulation is preferably 90 to 99.7%, very preferably 94 to 99.5%. The proportion of the chiral component in the chiral RM mixture is preferably 0.3 to 10%, very preferably 0.5 to 6%.

[0560] In another preferred embodiment, the RM formulation is prepared by blending an achiral host mixture with another RM formulation containing a higher amount of chiral compound than the final RM formulation after blending. The achiral host mixture comprises, very preferably, one or more mono- and / or di-reactive achiral RMs (preferably selected from formulas D, M, T, and A and their sub-formulas), but does not contain chiral compounds.

[0561] In another preferred embodiment, the RM formulation optionally includes one or more additives selected from polymerization initiators, surfactants, stabilizers, catalysts, sensitizers, inhibitors, chain transfer agents, co-reactive monomers, reactive thinners, surfactants, lubricants, wetting agents, dispersants, hydrophobic agents, adhesives, flow improvers, degassing or defoaming agents, degassing agents, diluents, reactive diluents, auxiliaries, colorants, dyes, pigments, and nanoparticles.

[0562] In another preferred embodiment of the invention, the RM formulation is free of compounds having at least one CF3 or CF2 group (PFAS). Most preferably, the RM formulation is free of compounds having perfluorinated alkyl or aryl or perfluorinated carbon groups. More preferably, the RM formulation is free of compounds having fluorinated aliphatic C atoms. Most preferably, the RM mixture and / or the RM formulation is free of compounds having fluorinated C atoms. The RM formulation according to this preferred embodiment is therefore indeed capable of reducing perfluorinated carbon.

[0563] Another object of the present invention is the RM formulation described above and below that is free of PFAS, more preferably free of perfluorinated carbon compounds, very preferably free of compounds having polyfluorinated C atoms, and most preferably free of compounds having fluorinated C atoms.

[0564] In another preferred embodiment, the RM formulation comprises one or more specific antioxidant additives, preferably selected from the Irganox® series, such as the commercially available antioxidants Irganox® 1076 and Irganox® 1010 from Ciba, Switzerland.

[0565] In another preferred embodiment, the RM formulation comprises a photoinitiator, or one or more, more preferably a combination of two or more photoinitiators, such as those selected from the commercially available Omnirad® or Darocur® series (from IGM Resins), particularly Omnirad 127, Omnirad 184, Omnirad 369, Omnirad 651, Omnirad 817, Omnirad 907, Omnirad 1300, Omnirad, Omnirad 2022, Omnirad 2100, Omnirad 2959 or Darocur TPO, and also selected from commercially available OXE02 (Ciba AG), NCI 930, N1919T (Adeka), SPI-03 or SPI-04 (Samyang), TR-PBG304 or TR-PBG 345 (Tronly).

[0566] The concentration of polymerization initiator (one or more) in the RM formulation is preferably 0.1 to 6% of the total solids, very preferably 0.3 to 4%, and more preferably 0.7 to 2%.

[0567] In another preferred embodiment, the ratio between the concentration of the photoinitiator and the overall concentration of the chiral compound is in the range of 2:1 to 1:5, more preferably in the range of 2:1 to 1:4, and even more preferably in the range of 2:1 to 1:3.

[0568] In another preferred embodiment, the RM formulation optionally includes one or more additives selected from polymerizable non-mesomorphic compounds (reactive thickeners). The amount of these additives in the RM formulation is preferably 0 to 30% of the total solids, very preferably 0 to 25%.

[0569] The reactive tack reducer used is not only a substance that is practically called a reactive tack reducer, but also the auxiliary compound mentioned above, which contains one or more complementary reactive units (e.g., hydroxyl, thiol- or amino) that can react with the polymerizable units of the liquid crystal compound.

[0570] Substances typically capable of photopolymerization include, for example, mono-, di-, or polyfunctional compounds containing at least one olefinic double bond. Examples include vinyl esters of carboxylic acids, such as vinyl esters of lauric acid, myristic acid, palmitic acid, and stearic acid; vinyl esters of dicarboxylic acids, such as vinyl esters of succinic acid and adipic acid; allyl and vinyl ethers of monofunctional alcohols and methacrylates and acrylates, such as allyl and vinyl ethers of lauryl alcohol, myristic alcohol, palmitol, and stearyl alcohol and methacrylates and acrylates; and diallyl and divinyl ethers of difunctional alcohols, such as diallyl and divinyl ethers of ethylene glycol and 1,4-butanediol.

[0571] Also suitable are, for example, methacrylates and acrylates of polyfunctional alcohols, especially those that contain no functional groups other than hydroxyl groups, or at most contain ether groups. Examples of such alcohols are difunctional alcohols, such as ethylene glycol, propylene glycol and their higher condensation representatives, such as diethylene glycol, triethylene glycol, dipropylene glycol, tripropylene glycol, etc., butanediol, pentanediol, hexanediol, neopentanediol, alkoxylated phenolic compounds, such as ethoxylated and propoxylated bisphenols, cyclohexanediol, trifunctional and polyfunctional alcohols, such as glycerol, trimethylolpropane, glycerol, trimethylolethane, pentaerythritol, ditrimethylolpropane, dipentaerythritol, sorbitol, mannitol, and the corresponding alkoxylated, especially ethoxylated and propoxylated alcohols.

[0572] Other suitable reactive tack reducers are polyester (meth)acrylates, which are (meth)acrylates of polyesterol.

[0573] Examples of suitable polyester alcohols are those that can be prepared by esterifying a polycarboxylic acid, preferably a dicarboxylic acid, using a polyol, preferably a diol. Starting materials for such hydroxyl-containing polyesters are known to those skilled in the art. Suitable dicarboxylic acids are succinic acid, glutaric acid, adipic acid, sebacic acid, phthalic acid and its isomers and hydrogenated products, and esterifiable or ester-transferable derivatives of said acids, such as anhydrides and dialkyl esters. Suitable polyols are the alcohols mentioned above, preferably ethylene glycol, 1,2- and 1,3-propanediol, 1,4-butanediol, 1,6-hexanediol, neopentyl glycol, cyclohexanediol, and polyols of the ethylene glycol and propylene glycol classes.

[0574] In addition, suitable reactive tack reducers are 1,4-divinylbenzene, triallyl cyanurate, and acrylates of tricyclodecenyl alcohol of the following formula.

[0575]

[0576] It is also known as dihydrodicyclopentadienyl acrylate, as well as allyl esters of acrylic acid, methacrylic acid and cyanoacrylate.

[0577] In the reactive viscosity reducers mentioned by way of example, and in particular, in consideration of the preferred compositions mentioned above, those containing photopolymerizable groups are used.

[0578] This group includes, for example, diols and polyols, such as ethylene glycol, propylene glycol and their higher condensation representatives, such as diethylene glycol, triethylene glycol, dipropylene glycol, tripropylene glycol, etc., butanediol, pentanediol, hexanediol, neopentanediol, cyclohexanediol, glycerol, trimethylolpropane, glycerol, trimethylolethane, pentaerythritol, ditrimethylolpropane, dipentaerythritol, sorbitol, mannitol and the corresponding alkoxylation, especially ethoxylated and propoxylated alcohols.

[0579] In addition, the groups also include, for example, alkoxylated phenolic compounds, such as ethoxylated and propoxylated bisphenols.

[0580] In addition, these reactive tack reducers can be, for example, epoxy or urethane (meth)acrylate.

[0581] For example, epoxy (meth)acrylates are those that can be obtained by reacting epoxidized olefins or poly- or diglycidyl ethers such as bisphenol A diglycidyl ether with (meth)acrylate, as is known to those skilled in the art.

[0582] In particular, urethane (meth)acrylates are products of the reaction of hydroxyalkyl (meth)acrylates with poly- or diisocyanates, as is also known to those skilled in the art.

[0583] Such epoxy and urethane (meth)acrylate esters are included as "mixed forms" in the compounds listed above.

[0584] If reactive viscosity reducers are used, their quantity and properties must be matched to the corresponding conditions to achieve satisfactory desired effects, such as the desired color of the composition according to the invention, on the one hand, without unduly impairing the phase behavior of the liquid crystal composition on the other hand. For example, low-crosslinked (high-crosslinked) liquid crystal compositions can be prepared using corresponding reactive viscosity reducers having a relatively low (high) number of reactive units per molecule.

[0585] For example, the group of diluents includes:

[0586] C1-C4-alcohols, such as methanol, ethanol, n-propanol, isopropanol, butanol, isobutanol, sec-butanol, and particularly C5-C12-alcohols, n-pentanol, n-hexanol, n-heptanol, n-octanol, n-nonanol, n-decanol, n-undecanol and n-dodecanol and their isomers; diols, such as 1,2-ethylene glycol, 1,2- and 1,3-propanediol, 1,2-, 2,3- and 1,4-butanediol, di- and triethylene glycol and di- and tripropylene glycol; ethers, such as methyl tert-butyl ether, 1,2-ethylene glycol 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 pentyl acetate, aliphatic and aromatic hydrocarbons such as pentane, hexane, heptane, octane, isooctane, petroleum ether, toluene, xylene, ethylbenzene, tetrahydronaphthalene, decahydronaphthalene, dimethylnaphthalene, white solvent oils, Shellsol® and Solvesso® mineral oils such as gasoline, kerosene, diesel and fuel oil, and natural oils such as olive oil, soybean oil, rapeseed oil, linseed oil and sunflower oil.

[0587] Of course, mixtures of these diluents can also be used in the compositions according to the invention.

[0588] These diluents can also be mixed with water as long as at least partial miscibility exists. Examples of suitable diluents are C1-C4 alcohols, such as methanol, ethanol, n-propanol, isopropanol, butanol, isobutanol, and sec-butanol; diols, such as 1,2-ethylene glycol, 1,2- and 1,3-propanediol, 1,2-, 2,3- and 1,4-butanediol, di- and tri-ethylene glycol, and di- and tri-propanediol; 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.

[0589] The diluent may be used at a rate of about 0 to 10.0% by weight, preferably about 0 to 5.0% by weight, based on the total weight of the RM formulation.

[0590] Defoamers and degassing agents (c1), lubricants and flow aids (c2), thermosetting or radiation curing aids (c3), substrate wetting aids (c4), wetting and dispersing aids (c5), hydrophobic agents (c6), adhesion promoters (c7), and scratch resistance promoters (c8) cannot be strictly separated from each other in their function.

[0591] For example, lubricants and flow aids are often also used as defoamers and / or degassing agents and / or scratch-resistant agents. Radiation curing aids can also be used as lubricants and flow aids and / or degassing agents and / or substrate wetting agents. In various cases, some of these aids can also function as adhesion promoters (C8).

[0592] Accordingly, certain additives can therefore be classified into several groups c1) to c8) as described below.

[0593] In group c1), defoamers include silicone-free and silicone-containing polymers. Silicone-containing polymers are, for example, unmodified or modified polydialkylsiloxanes or branched copolymers, comb-shaped or block copolymers comprising polydialkylsiloxane and polyether units, the latter of which may be obtained from ethylene oxide or propylene oxide.

[0594] In group C1), degassing agents include, for example, organic polymers such as polyethers and polyacrylates, dialkyl polysiloxanes, particularly dimethyl polysiloxanes, organically modified polysiloxanes such as arylalkyl modified polysiloxanes, and fluorosiloxanes.

[0595] The function of defoamers is essentially based on preventing foam formation or destroying existing foam. In the medium to be degassed, such as in the compositions according to the invention, defoamers work essentially by promoting the coalescence of fine gas or air bubbles to obtain larger bubbles, thereby accelerating the escape of gas (or air). Since defoamers can often also be used as degassing agents and vice versa, these additives have been included in group c1).

[0596] TEGO® Foamex 800、TEGO® Foamex 805、TEGO® Foamex 810、TEGO® Foamex 815、TEGO® Foamex 825、TEGO® Foamex 835、TEGO® Foamex 840、TEGO® Foamex 842、TEGO® Foamex 1435、TEGO® Foamex 1488、TEGO® Foamex 1495、TEGO® Foamex 3062、TEGO® Foamex 7447、TEGO® Foamex 8020、TEGO® Foamex N、TEGO® Foamex K 3、TEGO® Antifoam 2-18、TEGO® Antifoam 2-18、TEGO®Antifoam 2-57、TEGO® Antifoam 2-80、TEGO® Antifoam 2-82、TEGO® Antifoam 2-89、TEGO® Antifoam 2-92、TEGO® Antifoam 14、TEGO® Antifoam 28、TEGO® Antifoam81、TEGO® Antifoam D 90、TEGO® Antifoam 93、TEGO® Antifoam 200、TEGO®Antifoam 201、TEGO® Antifoam 202、TEGO® Antifoam 793、TEGO® Antifoam 1488、TEGO® Antifoam 3062、TEGOPREN® 5803、TEGOPREN® 5852、TEGOPREN® 5863、TEGOPREN® 7008、TEGO® Antifoam 1-60、TEGO® Antifoam 1-62、TEGO® Antifoam 1-85、TEGO®Antifoam 2-67、TEGO® Antifoam WM 20、TEGO® Antifoam 50、TEGO® Antifoam 105、TEGO® Antifoam 730、TEGO® Antifoam MR 1015、TEGO® Antifoam MR 1016、TEGO®Antifoam 1435、TEGO® Antifoam N、TEGO® Antifoam KS 6、TEGO® Antifoam KS 10、TEGO® Antifoam KS 53、TEGO®Antifoam KS 95, TEGO® Antifoam KS 100, TEGO® Antifoam KE 600, TEGO® Antifoam KS 911, TEGO® Antifoam MR 1000, TEGO® Antifoam KS 1100, TEGO® Twin 4000, Tego® Airex 900, Tego® Airex 910, Tego®Airex 931, Tego® Airex 935, Tego® Airex 936, Tego® Airex 960, Tego® Airex970, Tego® Airex 980 and Tego® Airex 985 is commercially available and available from BYK as BYK®-011, BYK®-019, BYK®-020, BYK®-021, BYK®-022, BYK®-023, BYK®-024, BYK®-025, BYK®-027, BYK®-031, BYK®-032, BYK®-033, BYK®-034, BYK®- 035, BYK®-036, BYK®-037, BYK®-045, BYK®-051, BYK®-052, BYK®-053, BYK®-055, B YK®-057, BYK®-065, BYK®-066, BYK®-070, BYK®-080, BYK®-088, BYK®-141 and BYK®-A Available commercially for 530.

[0597] The adjuvants in group c1) may be used at a rate of about 0 to 3.0% by weight, preferably about 0 to 2.0% by weight, based on the total weight of the RM formulation.

[0598] In group C2), lubricants and flow aids typically include silicone-free and silicone-containing polymers, such as polyacrylates or modifiers, low molecular weight polydialkylsiloxanes. The modification involves replacing some of the alkyl groups with a wide variety of organic groups. These organic groups are, for example, polyethers, polyesters, or even long-chain alkyl groups, with the former being the most commonly used.

[0599] In correspondingly modified polysiloxanes, the polyether groups are typically composed of ethylene oxide and / or propylene oxide units. Generally, the higher the proportion of these alkylene oxide units in the modified polysiloxane, the higher the hydrophilicity of the resulting product.

[0600] For example, such adjuvants are commercially available from Tego as TEGO® Glide 100, TEGO® Glide ZG 400, TEGO® Glide 406, TEGO® Glide 410, TEGO® Glide 411, TEGO® Glide 415, TEGO® Glide 420, TEGO® Glide 435, TEGO® Glide 440, TEGO® Glide 450, TEGO® Glide A 115, TEGO® Glide B 1484 (which can also be used as an antifoaming and degassing agent), TEGO® Flow ATF, TEGO® Flow 300, TEGO® Flow 460, TEGO® Flow 425 and TEGO® Flow ZFS 460. Suitable radiation-curable lubricants and flow aids, which can also be used to improve scratch resistance, are products TEGO® Rad 2100, TEGO® Rad 2200, TEGO® Rad 2500, TEGO® Rad 2600 and TEGO® Rad 2700, which are also available from TEGO.

[0601] For example, such adjuvants can be obtained from BYK as BYK®-300, BYK®-306, BYK®-307, BYK®-310, BYK®-320, BYK®-333, BYK®-341, BYK® 354, BYK® 361, BYK® 361N, and BYK® 388.

[0602] The adjuvants in group c2) may be used in an amount of about 0 to 3.0% by weight, preferably about 0 to 2.0% by weight, based on the total weight of the RM formulation.

[0603] In group C3), radiation curing aids include, in particular, polysiloxanes having terminal double bonds, such as those with acrylate groups. Such aids can be crosslinked by photochemical or, for example, electron radiation. These aids typically combine several properties. In their uncrosslinked state, they can function as defoamers, degassing agents, lubricants, flow aids, and / or substrate wetting aids; while in their crosslinked state, they particularly improve the scratch resistance of coatings or films, for example, that can be prepared using the compositions according to the invention. Specifically, improvements in the gloss properties of such coatings or films are essentially considered a result of the action of these aids as defoamers, degassing agents, and / or lubricants and flow aids (in the uncrosslinked state).

[0604] Examples of suitable radiation curing aids are TEGO® Rad 2100, TEGO® Rad 2200, TEGO® Rad 2500, TEGO® Rad 2600 and TEGO® Rad 2700, which are available from TEGO, and BYK®-371, which is available from BYK.

[0605] In group c3), thermosetting aids contain, for example, primary OH groups that can react with, for example, isocyanate groups of adhesives.

[0606] Examples of available thermosetting aids are BYK®-370, BYK®-373 and BYK®-375, which are products available from BYK.

[0607] The adjuvants in group c3) may be used at a rate of about 0 to 5.0% by weight, preferably about 0 to 3.0% by weight, based on the total weight of the RM formulation.

[0608] Substrate wetting aids in group c4) are specifically used to improve the wettability of substrates to be printed or coated, for example, by printing ink or coating compositions (e.g., compositions according to the invention). Such improvements in the lubrication and flow behavior of the printing ink or coating compositions typically have an impact on the appearance of the resulting (e.g., crosslinked) prints or coatings.

[0609] A wide variety of such adjuvants are available, for example, from Tego as TEGO® Wet KL 245, TEGO® Wet 250, TEGO® Wet 260 and TEGO® Wet ZFS 453 and from BYK as BYK®-306, BYK®-307, BYK®-310, BYK®-333, BYK®-344, BYK®-345, BYK®-346, BYK®-348 and BYK®-3550.

[0610] The additives in group C4) may be used at a ratio 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.

[0611] The wetting and dispersing aids in group C5) are particularly useful for preventing pigment floating, blooming, and deposition, and are therefore particularly suitable (if necessary) for coloring compositions according to the invention.

[0612] These additives essentially stabilize pigment dispersions through electrostatic repulsion and / or steric hindrance of the pigment particles containing these additives, in which case the interaction between the additives and the surrounding medium (e.g., binders) plays a significant role.

[0613] Since the use of such wetting and dispersing agents is common practice, for example in the fields of printing inks and paints, the selection of suitable agents of this type usually does not present any difficulty to those skilled in the art (if they are used).

[0614] Such wetting and dispersing additives are available, for example, from Tego as TEGO® Dispers 610, TEGO® Dispers 610 S, TEGO® Dispers 630, TEGO® Dispers 700, TEGO® Dispers 705, TEGO® Dispers 710, TEGO® Dispers 720 W, TEGO® Dispers 725 W, TEGO® Dispers 730 W, TEGO® Dispers 735 W and TEGO® Dispers 740 W and from BYK with Disperbyk®, Disperbyk®-107, Disperbyk®-108, Disperbyk®-110, Disperbyk®-111, Disperbyk®-115, Disp erbyk®-130, Disperbyk®-160, Disperbyk®-161, Disperbyk®-162, Disperbyk®-163, Disperbyk®-164, Disperbyk®-1 65. Disperbyk®-166, Disperbyk®-167, Disperbyk®-170, Disperbyk®-174, Disperbyk®-180, Disperbyk®-181, Disp erbyk®-182, Disperbyk®-183, Disperbyk®-184, Disperbyk®-185, Disperbyk®-190, Anti-Terra®-U, Anti-Terra®-U 80. Anti-Terra®-P, Anti-Terra®-203, Anti-Terra®-204, Anti-Terra®-206, BYK®-151, BYK®-154, BYK®-155, BYK®-P 104 S, BYK®-P 105, Lactimon®, Lactimon®-WS and Bykumen® are commercially available.

[0615] In group C5), the amount of adjuvants is used based on the average molecular weight of the adjuvant. Therefore, preliminary experiments are desirable in any case, but this can be easily performed by those skilled in the art.

[0616] Another preferred group of additives that can be assigned to groups c2), c4), or c5) includes wetting agents, flow agents, and leveling agents, particularly based on nonionic fluorosurfactants, which can be obtained from Synthomer via Polyfox. TM Series, such as Polyfox TM Purchased from PF-656.

[0617] The hydrophobic agents in group C6) can be used to impart hydrophobic properties to prints or coatings manufactured using, for example, the compositions according to the invention. This prevents or at least significantly inhibits swelling due to water absorption and thus, for example, changes in the optical properties of the prints or coatings. Furthermore, when the compositions are used as printing inks, for example, in offset printing, water absorption can thereby be prevented or at least significantly reduced.

[0618] Such hydrophobic agents are available, for example, from Tego as Tego® Phobe WF, Tego® Phobe 1000, Tego® Phobe 1000 S, Tego® Phobe 1010, Tego® Phobe 1030, Tego® Phobe 1010, Tego® Phobe 1010, Tego® Phobe 1030, Tego® Phobe 1040, Tego® Phobe 1050, Tego® Phobe 1200, Tego® Phobe 1300, Tego® Phobe 1310 and Tego® Phobe 1400 are commercially available.

[0619] The adjuvants in group C6) may be used at a rate of about 0 to 5.0% by weight, preferably about 0 to 3.0% by weight, based on the total weight of the RM formulation.

[0620] Adhesion accelerators from group C7) are used to improve the adhesion of two interfaces in contact. It is directly apparent that, essentially, the only effective portion of an adhesion accelerator is the portion located at one or the other interface, or both interfaces. If, for example, it is desired to apply liquid or paste-like printing inks, coating compositions, or varnishes to a solid substrate, this usually means that the adhesion accelerator must be added directly to the latter, or the substrate must be pretreated with the adhesion accelerator (also known as applying a primer), i.e., to impart altered chemical and / or physical surface properties to the substrate.

[0621] If a primer has been applied to the substrate beforehand, this means that the contact interface is one side of the primer interface and the other side of the printing ink or coating composition or paint interface. In this case, not only the adhesion between the substrate and the primer, but also the adhesion between the substrate and the printing ink or coating composition or paint, plays a role in the adhesion of the entire multilayer structure on the substrate.

[0622] In a broader sense, adhesion promoters can also be mentioned, as are the substrate wetting aids already listed in group C4), but these generally do not have the same adhesion promoting ability.

[0623] Given the wide range of physical and chemical properties of the substrates and the printing inks, coating compositions, and varnishes intended for use, such as printing or coating them, the diversity of adhesive accelerator systems is not surprising.

[0624] Silane-based adhesion promoters include, for example, 3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, 3-aminopropylmethyldiethoxysilane, N-aminoethyl-3-aminopropyltrimethoxysilane, N-aminoethyl-3-aminopropylmethyldiethoxysilane, N-methyl-3-aminopropyltrimethoxysilane, 3-ureopropyltriethoxysilane, 3-methacryloyloxypropyltrimethoxysilane, 3-glycidyloxypropyltrimethoxysilane, 3-mercaptopropyltrimethoxysilane, 3-chloropropyltrimethoxysilane, and vinyltrimethoxysilane. These and other silanes are commercially available from Hüls, for example, under the trade name DYNASILAN®.

[0625] The relevant technical information should generally be obtained from the manufacturer of such additives, or information that can be obtained by those skilled in the art through appropriate preliminary experiments in a simple manner.

[0626] However, if these additives are to be added as adjuvants from group C7) to the RM formulation according to the invention, their proportions may optionally correspond to about 0 to 5.0% by weight, based on the total weight of the RM formulation. These concentration data are for guidance only, as the amount and identity of the additives are determined in each individual case by the properties of the substrate and the printing / coating composition. In this case, the relevant technical information is generally available from the manufacturer of such additives, or can be determined by those skilled in the art in a simple manner through corresponding preliminary experiments.

[0627] Additives for improving scratch resistance in group C8) include, for example, the Tego products mentioned above, TEGO® Rad 2100, TEGO® Rad 2200, TEGO® Rad 2500, TEGO® Rad 2600 and TEGO® Rad 2700.

[0628] The data on the amounts given for group c3) also apply to these additives, i.e., these additives are optionally used in proportions 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.

[0629] Examples of light, heat, and / or oxidation stabilizers that may be mentioned are the following substances:

[0630] 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, and nonylphenol having straight-chain or branched side chains, for example... Examples include 2,6-dinonyl-4-methylphenol, 2,4-dimethyl-6-(1′-methylundecane-1′-yl)phenol, 2,4-dimethyl-6-(1′-methylheptadecane-1′-yl)phenol, 2,4-dimethyl-6-(1′-methyltetrazane-1′-yl)phenol, and mixtures thereof; 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.

[0631] Hydroquinone 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-hydroxyanisole, 3,5-di-tert-butyl-4-hydroxyanisole stearate, and bis(3,5-di-tert-butyl-4-hydroxyphenyl) adipate.

[0632] Tocopherols, such as α-tocopherol, β-tocopherol, γ-tocopherol, δ-tocopherol, and mixtures of these compounds, as well as tocopherol derivatives, such as tocopherol acetate, tocopherol succinate, tocopherol nicotinate, and tocopherol polyoxyethylene succinate (“tocofersolate”).

[0633] 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-pentylphenol), and 4,4′-bis(2,6-dimethyl-4-hydroxyphenyl) disulfide.

[0634] Alkylbisphenols, such as 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-ethylbis( 4,6-di-tert-butylphenol), 2,2′-ethylidene bis(6-tert-butyl-4-isobutylphenol), 2,2′-methylene bis[6-(α-methylbenzyl)-4-nonylphenol], 2,2′-methylene bis[6-(α,α-dimethylbenzyl)-4-nonylphenol], 4,4′-methylene bis(2,6-di-tert-butylphenol), 4,4′-methylene bis(6-tert-butyl-2-methylphenol), 1,1-bis(5-tert-butyl-4-hydroxy-2- 2,6-bis(3-tert-butyl-5-methyl-2-hydroxybenzyl)-4-methylphenol, 1,1,3-tris(5-tert-butyl-4-hydroxy-2-methylphenyl)butane, 1,1-bis(5-tert-butyl-4-hydroxy-2-methylphenyl)-3-dodecyl-mercaptobutane, ethylene glycol bis[3,3-bis(3′-tert-butyl-4′-hydroxyphenyl)butyrate], bis(3-tert-butyl-4-hydroxy-5-methylphenyl)dicyclopentadiene, bis [2-(3′-tert-butyl-2′-hydroxy-5′-methylbenzyl)-6-tert-butyl-4-methylphenyl] terephthalate, 1,1-bis(3,5-dimethyl-2-hydroxyphenyl)butane, 2,2-bis(3,5-di-tert-butyl-4-hydroxyphenyl)propane, 2,2-bis(5-tert-butyl-4-hydroxy-2-methylphenyl)-4-dodecyl-mercaptobutane and 1,1,5,5-tetra(5-tert-butyl-4-hydroxy-2-methylphenyl)pentane.

[0635] O-, N-, and S-benzyl compounds, such as 3,5,3′,5′-tetra-tert-butyl-4,4′-dihydroxydibenzyl ether, octadecyl 4-hydroxy-3,5-dimethylbenzyl mercaptoacetate, tridecyl 4-hydroxy-3,5-di-tert-butylbenzyl mercaptoacetate, tris(3,5-di-tert-butyl-4-hydroxybenzyl)amine, bis(4-tert-butyl-3-hydroxy-2,6-dimethylbenzyl)dithioterephthalate, bis(3,5-di-tert-butyl-4-hydroxybenzyl) sulfide, and isooctyl-3,5-di-tert-butyl-4-hydroxybenzyl mercaptoacetate.

[0636] Aromatic hydroxybenzyl compounds, such as 1,3,5-tris(3,5-di-tert-butyl-4-hydroxybenzyl)-2,4,6-trimethylbenzene, 1,4-bis(3,5-di-tert-butyl-4-hydroxybenzyl)-2,3,5,6-tetramethylbenzene, and 2,4,6-tris(3,5-di-tert-butyl-4-hydroxybenzyl)phenol,

[0637] Triazine compounds, such as 2,4-bis(octylmercapto)-6-(3,5-di-tert-butyl-4-hydroxyaniline)-1,3,5-triazine, 2-octylmercapto-4,6-bis(3,5-di-tert-butyl-4-hydroxyaniline)-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, etc. -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,

[0638] Benzylphosphonates, such as dimethyl 2,5-di-tert-butyl-4-hydroxybenzylphosphonate, diethyl 3,5-di-tert-butyl-4-hydroxybenzylphosphonate, di(octadecane) 3,5-di-tert-butyl-4-hydroxybenzylphosphonate, and di(octadecane) 5-tert-butyl-4-hydroxy-3-methylbenzylphosphonate.

[0639] Acylaminophenols, such as 4-hydroxylauroyl aniline, 4-hydroxystearoyl aniline, and octyl N-(3,5-di-tert-butyl-4-hydroxyphenyl)carbamate,

[0640] For example, propionates and acetates of monohydroxy or polyhydroxy alcohols, such as methanol, ethanol, n-octanol, isooctanol, octadecyl alcohol, 1,6-hexanediol, 1,9-nonanediol, ethylene glycol, 1,2-propanediol, neopentyl glycol, thiodiethylene glycol, diethylene glycol, triethylene glycol, pentaerythritol, tris(hydroxyethyl)isocyanurate, N,N′-bis(hydroxyethyl)oxalamide, 3-thiadecanoyl alcohol, 3-thiapentadecanol, trimethylhexanediol, trimethylolpropane, and propionates and acetates of 4-hydroxymethyl-1-phospha-2,6,7-trioxabicyclo[2.2.2]octane.

[0641] 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.

[0642] Ascorbic acid (vitamin C) and ascorbic acid derivatives, such as ascorbate palmitate, ascorbate laurate, and ascorbate stearate, as well as ascorbate sulfate and ascorbate phosphate.

[0643] 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-toluenesulfonyl)diphenylamine, N,N′-dimethyl-N,N′-di-sec-butyl-p-phenylenediamine, diphenylamine, N-allyl diphenylamine, 4-isopropoxydiphenylamine, N-phenyl-1-naphthylamine, N-(4-tert-octylphenyl)-1-naphthylamine, N-phenyl-2-naphthylamine, octyl-substituted diphenylamines such as p,p′-di-tert-octyldiphenylamine, 4-n-butylaminophenol, 4-butyrylaminophenol, 4-nonanoylaminophenol, 4-dodecanoylaminophenol, 4-octadecanoylaminophenol, bis(4-methoxyphenyl)amine, 2,6-di-tert-butyl-4-dimethylaminoamine 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)biguanidine, bis[4-(1′,3′-dimethylbutyl)phenyl]amine, tert-octyl-substituted N-phenyl-1-naphthylamine, mixtures of mono- and di-alkylated tert-butyl / tert-octyl diphenylamine, mixtures of mono- and di-alkylated nonyl diphenylamine, mixtures of mono- and di-alkylated dodecyl diphenylamine, and mono- and di-alkylated isopropyl / isohexyl diphenylamine. Mixtures, mixtures of mono- and di-alkylated tert-butyl diphenylamine, 2,3-dihydro-3,3-dimethyl-4H-1,4-benzothiazine, phenothiazine, mixtures of mono- and di-alkylated tert-butyl / tert-octylphenothiazine, mixtures of mono- and di-alkylated tert-octylphenothiazine, N-allylphenothiazine, N,N,N′,N′-tetraphenyl-1,4-diaminobut-2-ene, N,N-bis(2,2,6,6-tetramethylpiperidin-4-yl)hexamethylenediamine, bis(2,2,6,6-tetramethylpiperidin-4-yl) sebacate, 2,2,6,6-tetramethylpiperidin-4-one and 2,2,6,6-tetramethylpiperidin-4-ol,

[0644] Phosphites, phosphites, and phosphonates, such as triphenylphosphine, triphenyl phosphite, diphenylalkyl phosphite, phenyl dialkyl phosphite, tris(nonylphenyl) phosphite, trilauryl phosphite, tri(octadecyl) phosphite, distearate pentaerythritol diphosphite, tris(2,4-di-tert-butylphenyl) phosphite, diisodecyl pentaerythritol diphosphite, bis(2,4-di-tert-butylphenyl) pentaerythritol diphosphite, bis(2,6-di-tert-butyl-4-methylphenyl) pentaerythritol diphosphite, diisodecoxy pentaerythritol diphosphite, bis(2,4-di-tert-butyl-6-methylphenyl) pentaerythritol diphosphite, bis(2,4,6-tris(tert-butylphenyl)) Pentaerythritol diphosphite, tripearyl sorbitol triphosphite, tetrakis(2,4-di-tert-butylphenyl)4,4′-diphenylphosphite, 6-isooctyloxy-2,4,8,10-tetra-tert-butyl-12H-dibenzo[d,g]-1,3,2-dioxaphosphacene, 6-fluoro-2,4,8,10-tetra-tert-butyl-12-methyl-dibenzo[d,g]-1,3,2-dioxaphosphacene, bis(2,4-di-tert-butyl-6-methylphenyl)methyl phosphite, and bis(2,4-di-tert-butyl-6-methylphenyl)ethyl phosphite.

[0645] 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 2-Chlorobenzotriazole, 2-(3′-sec-butyl-5′-tert-butyl-2′-hydroxyphenyl)benzotriazole, 2-(2′-hydroxy-4′-octoxyphenyl)benzotriazole, 2-(3′,5′-di-tert-pentyl-2′-hydroxyphenyl)benzotriazole, 2-(3,5′-bis-(α,α-dimethylbenzyl)-2′-hydroxyphenyl)benzotriazole, and mixtures thereof: 2-(3′-tert-butyl-2′-hydroxy-5′-(2-octoxycarbonylethyl)phenyl)-5-chlorobenzotriazole, 2-(3′-tert-butyl-5′-hydroxyphenyl ... -[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]-5′-hydroxyphenyl)benzotriazole, 2-(3′-tert-butyl-5′-[2-(2-ethylhexyloxy)carbonylethyl)benzotriazole The product of complete esterification of 2-[3′-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-benzotriazole-2-ylphenol]; and 2-[3′-tert-butyl-5′-(2-methoxycarbonylethyl)-2′-hydroxyphenyl]-2H-benzotriazole with polyethylene glycol 300;

[0646] Sulfur-containing peroxide scavengers and sulfur-containing antioxidants, such as esters of 3,3′-thiodipropionic acid, e.g., lauryl, stearyl, myristyl, and tridecyl esters; zinc salts of mercaptobenzimidazole and 2-mercaptobenzimidazole; dibutylzinc dithiocarbamate; di(octadecyl)disulfide; and pentaerythritol tetra(β-dodecylmercapto)propionate.

[0647] 2-Hydroxybenzophenone, such as 4-hydroxy, 4-methoxy, 4-octoxy, 4-decoxy, 4-dodecoxy, 4-benzyloxy, 4,2′,4′-trihydroxy, and 2′-hydroxy-4,4′-dimethoxy derivatives,

[0648] Unsubstituted and substituted benzoic acid esters, 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-hydroxybenzoic acid, 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.

[0649] 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, and bis(1-octoxy-2,2,6,6-tetramethylpiperidin-4-yl) sebacate. Sebacic acid ester, bis(1,2,2,6,6-pentamethylpiperidin-4-yl)-n-butyl-3,5-di-tert-butyl-4-hydroxybenzylmalonic acid ester, 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)hydantoin triacetate, tetra(2,2,6,6-tetramethylpiperidin-4-yl)1,2,3,4-butanetetracarboxylate, 1,1′-(1,2-ethylidene) ) 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-octoxy-2,2,6,6-tetramethylpiperidin-4-yl)sepiacetate, bis(1-octoxy-2,2,6,6-tetramethylpiperidin-4-yl)succinate, N,N′-bis(2 The condensation product of 2,6,6-tetramethylpiperidin-4-yl)hexamethylenediamine and 4-morpholino-2,6-dichloro-1,3,5-triazine, the condensation product of 2-chloro-4,6-bis(4-n-butylamino-2,2,6,6-tetramethylpiperidin-4-yl)-1,3,5-triazine and 1,2-bis(3-aminopropylamino)ethane, the condensation product of 2-chloro-4,6-bis(4-n-butylamino-1,2,2,6,6-pentamethylpiperidin-4-yl)-1,3,5-triazine and 1,2-bis(3-aminopropylamino)ethane, and 8-acetyl-3-dodecyl-7,7,9,9-tetramethyl-1,3,8-triazaspiro[4].5]-Decane-2,4-dione, 3-dodecyl-1-(2,2,6,6-tetramethylpiperidin-4-yl)pyrrolidine-2,5-dione, 3-dodecyl-1-(1,2,2,6,6-pentamethylpiperidin-4-yl)pyrrolidine-2,5-dione, a mixture of 4-hexadecyloxy- and 4-stearyloxy-2,2,6,6-tetramethylpiperidine, a condensation product of N,N′-bis(2,2,6,6-tetramethylpiperidin-4-yl)hexamethylenediamine and 4-cyclohexylamino-2,6-dichloro-1,3,5-triazine, a condensation product of 1,2-bis(3-aminopropylamino)ethane and 2,4,6-trichloro-1,3,5-triazine, 4-butylamino-2,2,6,6-tetramethyl The condensation products of piperidine, N-(2,2,6,6-tetramethylpiperidin-4-yl)-dodecylsuccinimide, N-(1,2,2,6,6-pentamethylpiperidin-4-yl)-dodecylsuccinimide, 2-undecyl-7,7,9,9-tetramethyl-1-oxa-3,8-diaza-4-oxo-spiro[4.5]decane, 7,7,9,9-tetramethyl-2-cycloundecyl-1-oxa-3,8-diaza-4-oxospiro[4.5]decane and epichlorohydrin, and the condensation products of 4-amino-2,2,6,6-tetramethylpiperidine with tetrahydroxymethylethynyl diurea and poly(methoxypropyl-3-oxy)-[4(2,2,6,6-tetramethyl)piperidinyl]-siloxane.

[0650] Oxalides, such as 4,4′-dioctyloxyoxalaniline, 2,2′-diethoxyoxalaniline, 2,2′-dioctyloxy-5,5′-di-tert-butoxalaniline (butoxanilide), 2,2′-di(dodecyloxy)-5,5′-di-tert-butoxalaniline, 2-ethoxy-2′-ethyloxalaniline, N,N′-bis(3-dimethylaminopropyl)oxalamide, 2-ethoxy-5-tert-butyl-2′-ethoxalaniline (ethoxanilide) and mixtures thereof with 2-ethoxy-2′-ethyl-5,4′-di-tert-butoxalaniline, and mixtures thereof of o-, p-methoxy-disubstituted oxalanilines and mixtures thereof of o- and p-ethoxy-disubstituted oxalanilines, and

[0651] 2-(2-hydroxyphenyl)-1,3,5-triazine, such as 2,4,6-tri-(2-hydroxy-4-octoxyphenyl)-1,3,5-triazine, 2-(2-hydroxy-4-octoxyphenyl)-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-octoxyphenyl)-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-tetrazoloxyphenyl)-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 / tetrazyloxy-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.

[0652] In another preferred embodiment, the RM formulation contains an additive selected from formula IA:

[0653]

[0654] Where R 1A The term indicates an alkyl group having 12 to 25, preferably 14 to 22 carbon atoms, which is preferably straight-chain, very preferably n-octadecyl, and R 2 The term indicates an alkyl group having 1 to 6 carbon atoms, preferably methyl or ethyl, with methyl being the most preferred.

[0655] The most preferred compounds of formula IA are those of formula IA1:

[0656]

[0657] Compounds of formulas IA and IA1 improve the orientation of RM layers, especially CLC RM layers, without excessively reducing surface tension. This allows for the deposition of multiple RM or chiral RM layers without coating defects.

[0658] The concentration of compounds of formula IA and IA1 in the RM formulation is preferably 0.05 to 2% of the total solids, very preferably 0.1 to 1%, and most preferably 0.2 to 0.7%.

[0659] Preferably, the RM formulation comprises one or more components selected from the following components or any combination thereof:

[0660] a) One or more polymerizable mesocrystalline compounds that are multi-reactive or di-reactive, preferably selected from compounds of formula D and its derivatives, and / or

[0661] b) One or more monoreactive polymerizable mesocrystalline compounds, preferably selected from compounds of formula M and its subforms, and / or

[0662] c) One or more polymerizable mesocrystalline compounds selected from compounds of formulas T and A and their subforms, and / or

[0663] d) One or more polymerizable chiral compounds, preferably selected from formula C or its sub-formulas, and / or

[0664] e) One or more chiral isomerizable compounds, which may be polymerizable or nonpolymerizable, preferably selected from formula I. ,

[0665] f) One or more non-polymerizable and non-isomerizable chiral compounds, preferably selected from formulas C1, C-II, and C-III, and / or

[0666] g) One or more photoinitiators, and / or

[0667] h) One or more antioxidant additives, and / or

[0668] i) One or more adhesion promoters, and / or

[0669] j) One or more surfactants, and / or

[0670] k) One or more polymerizable non-mesomorphic compounds that are monoreactive, direactive, or multireactive, and / or

[0671] l) One or more dyes that exhibit a maximum absorption at the wavelength used to initiate photopolymerization, and / or

[0672] m) One or more chain transfer agents, and / or

[0673] n) One or more (UV) stabilizers, and / or

[0674] o) One or more lubricants and flow aids, and

[0675] p) One or more diluents, and / or

[0676] q) Non-polymerizable nematic components, and

[0677] r) Three or more organic solvents as described above and below.

[0678] More preferably, the RM formulation comprises:

[0679] 1) One or more, preferably two or more, two-reactive polymerizable mesocrystalline compounds, preferably selected from formula Da-1, and / or

[0680] 2) One or more, preferably two or more, monoreactive polymerizable mesocrystalline compounds, preferably selected from formulas M-1, M-4, M-6 and M-8 to M10, and / or

[0681] 3) One or more compounds of formula T or A or their preferred formula,

[0682] 4) Optionally one or more polymerizable chiral compounds, preferably selected from formula C or its sub-formulas.

[0683] 5) Optionally one or more chiral isomerizable compounds, preferably selected from formula I More preferably selected from Formula I A, or its corresponding preferred form.

[0684] 6) Optionally, one or more non-polymerizable and non-isomerizable chiral compounds, preferably selected from formulas C1, C-II, and C-III.

[0685] 7) Optionally, one or more antioxidant additives,

[0686] 8) One or more photoinitiators,

[0687] 9) Three or more organic solvents as described above and below,

[0688] Or any combination of the above components 1) to 9), provided that at least one of component 9) and components 1) to 3) is present.

[0689] RM mixtures and RM formulations can be prepared in their usual manner, for example by mixing one or more of the RMs defined above, and optionally with other additives, and dissolving these RMs and additives in a solvent or solvent blend.

[0690] The present invention further relates to a method for preparing a polymer or polymer film from an RM formulation as described above and below, comprising the steps of: depositing a layer of the RM formulation onto a substrate, optionally removing a solvent, optionally annealing the RM-containing layer, optionally aligning the RM to a uniform orientation, and polymerizing the RM, preferably at a temperature that causes the RM to exhibit a liquid crystal phase, wherein the RM formulation is deposited onto the substrate by a printing method, most preferably by inkjet printing.

[0691] Preferably, the RMs are aligned to a uniform orientation. More preferably, the alignment and polymerization of the RMs are carried out at a temperature that causes the RMs or RM mixtures to exhibit a liquid crystal phase, preferably a nematic phase or a cholesteric (chiral nematic) phase.

[0692] A preferred embodiment of the present invention relates to a method for preparing a polymer film, comprising the following steps, preferably consisting of the following steps:

[0693] - The RM formulation as described above and below is deposited onto a substrate by a printing method, most preferably by inkjet printing, the substrate optionally having an alignment layer and / or surface gratings or patterns.

[0694] - Remove solvent,

[0695] - Optionally, the RM layer may be annealed (i.e., solvent-free), preferably at a temperature that causes the RM mixture to exhibit a nematic or cholesteric phase.

[0696] - The RM layer is irradiated with photochemical radiation, preferably ultraviolet radiation, to induce the polymerization of RM and the formation of a polymer film.

[0697] - Optionally, the polymer film may be removed from the substrate.

[0698] In another preferred embodiment of the invention, particularly if the RM formulation contains a photoisomerizable chiral compound (which is preferably also polymerizable) as described above and below, the method for preparing the polymer film comprises two UV irradiation steps, and more specifically, the following steps, preferably consisting of the following steps:

[0699] - The RM formulation as described above and below is deposited onto a substrate by a printing method, most preferably by inkjet printing, the substrate optionally having an alignment layer and / or surface gratings or patterns.

[0700] - Remove solvent,

[0701] - Optionally, the RM layer may be annealed (i.e., solvent-free), preferably at a temperature that makes the RM mixture a cholesteric phase.

[0702] - The first step (first UV step) involves irradiating the RM layer in the air with photochemical radiation, preferably with ultraviolet radiation.

[0703] - Optionally, the RM layer may be annealed, preferably at a temperature that makes the RM mixture a cholesteric phase, and

[0704] - A second step (second UV step) involves irradiating the RM layer with photochemical radiation, preferably ultraviolet radiation, in an inert gas atmosphere.

[0705] - Optionally remove the formed polymer film from the substrate.

[0706] The present invention further relates to polymers or polymer films that can be obtained by one of the methods described above and below.

[0707] Preferably, in the method according to the invention, all printing, irradiation, or ultraviolet exposure steps are performed at room temperature.

[0708] In the two-step irradiation method according to the second preferred embodiment, the first irradiation or first UV step induces photoisomerization of the chiral compound containing photoisomerizable groups, providing a chiral structure with a biased pitch. The second irradiation or second UV step induces photopolymerization of the polymerizable mesocrystalline compound, thereby fixing the chiral structure. This method can be advantageously used to obtain a chiral pitch gradient along the film thickness direction, wherein the chiral rotation angle gradually increases or decreases with respect to film thickness.

[0709] After the RM formulation is deposited onto the substrate, the solvent is evaporated before polymerization. In most cases, heating the mixture to promote solvent evaporation is appropriate.

[0710] RM formulations can be deposited onto substrates using conventional coating or printing techniques known to those skilled in the art, including but not limited to spin coating, bar coating, slot die coating, inkjet printing, nozzle printing, screen printing, flexographic printing, offset printing, roll-to-roll printing, letterpress printing, gravure printing, rotary gravure printing, intaglio printing, pad printing, heat sealing printing, or printing using molds or printing plates. Printing methods, especially inkjet printing, are highly preferred.

[0711] Suitable substrate media and substrates are known to those skilled in the art and described in the literature, such as conventional substrates used in the optical film industry, like glass or plastic. 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), cyclic olefin polymers (COP), or commonly known color filter materials, preferably triacetyl cellulose (TAC), cyclic olefin polymers (COP), or commonly known color filter materials.

[0712] In another preferred embodiment, the substrate has a surface grating or surface pattern, preferably a periodic diffraction grating, and very preferably a PB deflection grating or a PB lens grating. In another preferred embodiment, the substrate is prepared from a photoalignment layer (PAL) that can be patterned by laser interferometry to form a grating pattern with a defined pitch.

[0713] In another preferred embodiment, the substrate comprises an alignment layer containing a cinnamate ester material, preferably PAL, onto which the RM formulation is printed. Suitable and preferred cinnamate ester (P)AL materials are commercially available, for example, from Nissan Chemical.

[0714] If the RM does not spontaneously align to the desired orientation on the selected substrate, an additional alignment layer capable of inducing the desired alignment can be used adjacent to the RM layer. For example, planar alignment can be promoted by coating the substrate with a polyimide layer and then rubbing the alignment layer with a velvet cloth.

[0715] Other suitable planar alignment layers are known in the art, such as rubbed polyimide or alignment layers prepared by photoalignment as described in US 5,602,661, US 5,389,698 or US 6,717,644.

[0716] Typically, reviews of alignment techniques are given, for example, by I. Sage in "Thermotropic Liquid Crystals," edited by GW Gray, John Wiley & Sons, 1987, pp. 75–77; and by T. Uchida and H. Seki in "Liquid Crystals – Applications and Uses, Vol. 3," edited by B. Bahadur, World Scientific Publishing, Singapore 1992, pp. 1–63. Further reviews of alignment materials and techniques are given by J. Cognard, Mol. Cryst. Liq. Cryst. 78, Supplement 1 (1981), pp. 1–77.

[0717] In a preferred embodiment, the method according to the invention comprises the method step of allowing the RM mixture or RM formulation to stand for a period of time to allow the polymerizable LC medium to be uniformly redistributed on the substrate (referred to herein as "annealing").

[0718] In a preferred embodiment, after the RM formulation is provided onto the substrate, the RM layer is annealed at a given temperature for a given time.

[0719] The annealing time is preferably between 10 seconds and 1 hour, more preferably between 20 seconds and 10 minutes, and most preferably between 30 seconds and 5 minutes.

[0720] Annealing is preferably carried out at a temperature between room temperature and 100°C, and very preferably between room temperature and 80°C.

[0721] The RM mixture preferably consists of compounds that spontaneously align when deposited as a mixture onto a substrate. Therefore, preferably, the RM mixture is not subjected to heat treatment to orient the mesocrystalline or liquid crystal compounds before UV exposure.

[0722] If necessary, the layer can be annealed at an elevated temperature and then cooled to room temperature. This cooling can be carried out actively with the aid of cooling aids or passively simply by allowing the stack of layers to stand for a given time.

[0723] Photopolymerization (hereinafter also referred to as "curing") of the RM layer is preferably achieved by exposing it to photochemical radiation. Photochemical radiation refers to irradiation with light, such as ultraviolet, infrared, or visible light, with X-rays or gamma rays, or with high-energy particles, such as ions or electrons. Preferably, polymerization is carried out by light irradiation, particularly with ultraviolet light. As a source of photochemical radiation, for example, a single ultraviolet lamp or a group of ultraviolet lamps can be used. When using high lamp power, the curing time can be reduced. Another possible source of light radiation is a laser, such as a UV laser, an IR laser, or a visible laser.

[0724] The curing time depends in particular on the reactivity of the RM and other polymerizable components, the thickness of the RM layer, and the power and wavelength of the UV lamp.

[0725] The orientation quality of polymer films can also be improved by optimizing the curing time and curing temperature.

[0726] Preferred curing time 5 minutes, highly recommended 3 minutes, more preferably ≤ 90 seconds, most preferably 30 to 90 seconds. For mass production, ≤ 60 seconds or even longer. A curing time of 30 seconds is preferred.

[0727] The curing temperature is preferably room temperature to 50°C, and very preferably 35 to 45°C. For curing at 35°C or higher, the curing time is preferably at least 50 seconds, and more preferably 50 to 90 seconds.

[0728] The appropriate UV radiation power in the first UV step is preferably between 5 and 300 mW / cm². -2 More preferably, it is within the range of 50 to 250 mW / cm². -2 Within the range of 100 to 180 mW / cm², the optimal value is preferred. -2 Within the range.

[0729] Regarding the applied UV radiation and its variation over time, a suitable UV dose is preferably between 20 and 1000 mJ / cm². -2 More preferably, it is within the range of 30 to 800 mJ / cm. -2 Within the range of 40 to 500 mJ / cm, it is highly preferred. -2 Within the range, the optimal value is between 40 and 200 mJ / cm. -2 Within the range.

[0730] In the two-step irradiation method according to the second preferred embodiment, the first irradiation step or the first UV step for isomerizing the chiral compound is preferably carried out in air. Preferably, the first irradiation step or the first UV step is carried out at room temperature.

[0731] The optimal UV radiation power for photopolymerization is preferably between 100 and 1000 mW / cm². -2 More preferably, it is within the range of 200 to 800 mW / cm². -2 Within the range, the optimal value is between 300 and 600 mW / cm². -2 Within the range.

[0732] Regarding the applied UV radiation and its variation over time, a suitable UV dose is preferably between 25 and 16500 mJ / cm². -2 More preferably, it is within the range of 50 to 7200 mJ / cm. -2 Within the range of 100 to 3500 mJ / cm, it is highly preferred. -2 Within the range of 200 to 2000 mJ / cm, the optimal value is between 200 and 2000 mJ / cm. -2 Within the range.

[0733] Photopolymerization (or the second irradiation step or the second UV step in a two-step process) is preferably carried out in an inert gas atmosphere, preferably in a nitrogen atmosphere. More preferably, photopolymerization (or the second irradiation step or the second UV step in a two-step process) is preferably carried out at room temperature.

[0734] The preferred thickness and delay of the polymer film according to the invention are determined by the optical properties required in the film or the final product.

[0735] For optical applications of polymer films, a thickness of 0.1 to 10 μm is preferred, 0.1 to 2 μm is very preferred, and particularly 0.1 to 1 μm is preferred.

[0736] In a preferred embodiment, the polymer film according to the invention exhibits planar orientation, i.e., the LC molecules are oriented parallel to the film plane and the helical axis is substantially perpendicular to the film plane.

[0737] In another preferred embodiment, the polymer film according to the invention exhibits a tilted orientation, i.e., the LC molecules are oriented at an angle to the film plane, and the helical axis is oriented at an angle to the film plane, also referred to as the tilt angle. In the tilted film, the tilt angle between the helical axis and the axis perpendicular to the film plane is 5° to 45°, very preferably 15° to 45°. In another preferred embodiment, the tilt angle between the helical axis and the axis perpendicular to the film plane is 0° to 15°, very preferably 0° to 5°.

[0738] Planar alignment can be induced, for example, by providing an alignment layer on the substrate, such as a polyimide alignment layer as described above. Tilted alignment can be achieved, for example, by adding an alignment additive to the RM mixture, or by using a substrate with a surface grating or pattern, such as a PB grating.

[0739] The birefringence of the polymer film according to the present invention ( n) is preferably in the range of 0.1 to 0.8, more preferably 0.2 to 0.7.

[0740] After photopolymerization, the resulting polymer film can be removed from the substrate and combined with other substrates or optical films using lamination methods known to those skilled in the art. Suitable substrates and optical films are given above, and in particular include polarizers, especially linear polarizers, photoalignment layers, or diffraction gratings, such as PB gratings.

[0741] The polymer film according to the invention exhibits good adhesion to plastic substrates, particularly TAC, COP, and color filters. Therefore, it can be used as an adhesive or primer for subsequent polymeric RM or LC layers that would otherwise not adhere well to the substrate.

[0742] In a preferred embodiment, the substrate contains a cinnamic acid ester photoalignment layer on which the RM formulation is printed.

[0743] The polymer film of the present invention can also be used as an alignment film or substrate for other liquid crystal or RM materials. The inventors have discovered that polymer films obtainable from RM formulations as described above and below are particularly suitable for multilayer applications due to their improved desiccation properties. In this way, stacks of optical films or, preferably, polymeric LC films can be prepared.

[0744] A preferred embodiment of the present invention relates to a method for fabricating an optical element, comprising the following steps:

[0745] A1) The first layer of the RM formulation according to the invention is provided on a substrate, preferably by inkjet printing, by means of a printing method, wherein the substrate optionally has an alignment layer and / or surface gratings or patterns.

[0746] A2) Remove any solvent present.

[0747] A3) Optionally, the first RM layer is annealed (i.e., solvent-free), preferably at a temperature that makes it a nematic or chiral nematic phase.

[0748] A4) Preferably, the RM layer is polymerized by exposure to ultraviolet light in an inert atmosphere.

[0749] B1) The second layer of the RM formulation according to the invention is provided on the first RM layer by means of printing, most preferably by inkjet printing.

[0750] B2) Remove any solvent present.

[0751] B3) Optionally, the second RM layer is annealed (i.e., solvent-free), preferably at a temperature that makes it a nematic or chiral nematic phase.

[0752] B4) Preferably, the RM layer is polymerized by exposure to ultraviolet light in an inert atmosphere.

[0753] The third, fourth, or further RM layers can be prepared by repeating steps B1) to B4) using the same or different RM formulations.

[0754] The RM formulations for the first and second layers are preferably different from each other. In a preferred embodiment, the RM formulations used to prepare the first and second layers contain different amounts of chiral compounds (one or more), and / or contain chiral compounds with different HTP. Therefore, the pitches of the first and second layers are different from each other. Alternatively, an RM mixture or RM formulation containing chiral dopants (chiral mixture) is blended with an RM mixture or RM formulation without chiral compounds (chiral mixture), which allows for easy variation of the amount of chiral dopants in the blend of chiral and chiral mixtures, thereby easily adjusting the pitch of the final layer and polymer film. The first and second layers can then be prepared from such RM mixtures or blends of RM mixtures. Very preferably, the RM mixture or formulation for the second layer contains a higher amount of the same chiral compound than the RM mixture or formulation for the first layer, and / or the RM mixture or formulation for the second layer contains a chiral compound with a higher HTP than the RM mixture or formulation for the first layer. Preferably, the pitch in the first layer is longer than the pitch in the second layer.

[0755] Therefore, by using a chiral RM host mixture comprising one or more compounds selected from formulas D, M, A, and T, or a chiral RM host mixture comprising one or more compounds selected from formulas D, M, A, and T, the RM formulations and methods of the present invention enable the simple preparation of multilayers of two or more chiral LC polymer films. This chiral RM host mixture can be used to prepare individual layers. Chiral RM mixtures for the first, second, or further layers are prepared by adding different amounts of the same chiral compound to the RM host mixture or by adding chiral compounds with different HTP to the RM host mixture.

[0756] The polymer film according to the invention exhibits good adhesion to plastic substrates, particularly TAC, COP, and color filters. Therefore, it can be used as an adhesive or primer for subsequent LC layers that would otherwise not adhere well to the substrate.

[0757] The polymer film of the present invention can also be used as an alignment film or substrate for other liquid crystal or RM materials. The inventors have discovered that polymer films obtainable from RM formulations as described above and below are particularly suitable for multilayer applications due to their improved desiccant properties. In this way, optical films or stacks of preferably polymer films can be prepared.

[0758] The present invention further relates to an optical, electro-optical, or electronic device or component comprising an RM mixture, RM formulation, or polymer film as described above and below.

[0759] The components include, but are not limited to, optical delay films such as quarter-wave plates (QWP) or half-wave plates (HWP), polarizers, optical compensators, reflective films, diffraction or surface gratings such as Bragg polarization gratings (Bragg PG), polarization volume gratings (PVG), polarization volume holograms (PVH), Panchara Tunnam-Berry (PB) gratings, and non-mechanical beam steering elements, optical waveguides, optical couplers, deflectors or combiners, polarization beam splitters, partial mirrors, reflective films, alignment layers, color filters, anti-static protective sheets, electromagnetic interference protective sheets, lenses for light guiding, focusing and optical effects, polarization control lenses, PB deflectors, PB lenses and infrared reflective films; for example, for use in LC displays (LCD), organic light-emitting diodes (OLED), autostereoscopic 3D displays, near-eye displays, augmented reality (AR) or virtual reality (VR) systems, switchable windows, spatial light modulators, optical data storage, remote optical sensing, holography, spectroscopy, optical communication, polarization or front / back illumination.

[0760] The devices include, but are not limited to, optoelectronic displays, especially LCDs, OLEDs, nonlinear optical (NLO) devices, autostereoscopic 3D displays, near-eye displays, head-up displays, AR / VR systems, glasses for AR / VR applications, switchable windows, spatial light modulators, optical data storage devices, optical sensors, holographic devices, spectrometers, optical communication systems, polarizers, or headlights / backlights.

[0761] Preferably, the component is a diffraction grating, most preferably PBG, PBL, or Bragg PG, which comprises one or more waveplates according to the invention as described above and below, optionally together with other waveplates, polarizers, and / or other components.

[0762] The waveplates according to the invention are particularly suitable for use in OLED displays or LC displays, head-up displays (e.g., for automotive applications), NLO devices, autostereoscopic 3D displays, perspective near-eye displays, AR / VR systems, or glasses for AR / VR applications.

[0763] The invention has been described above and below by special reference to preferred embodiments. It should be understood that various changes and modifications may be made therein without departing from the spirit and scope of the invention.

[0764] Many of the compounds or mixtures thereof mentioned above and below are commercially available. As described in the literature (e.g., in standard works such as Houben-Weyl, Methoden der Organischen Chemie [Methods of Organic Chemistry], Georg-Thieme-Verlag, and Stuttgart), all these compounds are known or can be prepared by methods known per se, specifically under known and suitable reaction conditions. Variations known per se but not mentioned herein may also be used.

[0765] It should be understood that variations may be made to the foregoing embodiments of the present invention, but these variations shall still remain within the scope of the present invention. Unless otherwise stated, alternative features for the same, equivalent, or similar purposes may replace the features disclosed herein. Therefore, unless otherwise stated, the disclosed features are merely one example of a series of general equivalent or similar features.

[0766] Except for at least some mutually exclusive combinations of such features and / or steps, all features disclosed in this specification can be combined in any combination. In particular, preferred features of the invention apply to all aspects of the invention and can be used in any combination. Similarly, features described in non-essential combinations can be used individually (not in combination).

[0767] It should be understood that many features of the particularly preferred embodiments described above are inventive in themselves and are not merely part of the embodiments of this invention. Independent protection may be sought for these features in addition to or in lieu of any currently claimed invention.

[0768] Unless otherwise expressly stated, all temperature values ​​indicated in this application, such as melting point T(K,N), transition from smectic (S) to nematic (N) phase T(S,N), and clearing point T(N,I), are referred to in degrees Celsius (°C). Furthermore, K denotes the crystalline state, N denotes the nematic phase, and I denotes the isotropic phase. The data between these symbols represent transformation temperatures.

[0769] Unless otherwise expressly stated, all physical properties have been determined according to "Merck Liquid Crystals, Physical Properties of Liquid Crystals", Status Nov. 1997, Merck KGaA, Germany, and are given at a temperature of 20°C.

[0770] In this context, unless otherwise stated, percentages are by weight. All temperatures are given in degrees Celsius. All boiling points are given at atmospheric pressure.

[0771] In the preceding and following text, mp represents the melting point, and T... NI And cl.p. denotes the nematic-isotropic phase transition temperature (or clearing point), T g This indicates the glass transition temperature. Additionally, C represents the crystalline state, N represents the nematic phase, and S represents the crystallinity. A S B Equals represent smectic A phase, smectic B phase, etc., S X X represents an unidentified smectic phase, X represents an unidentified mesophase, and I represents an isotropic phase. The values ​​between these symbols represent the transformation temperature (in °C). Unless otherwise specified, T is given. NI The initial temperature. Δn represents the optical anisotropy or birefringence at 589 nm and room temperature (Δn = n). e - n o , where n o The refractive index is perpendicular to the longitudinal molecular axis and n e (Represents the refractive index parallel to the longitudinal molecular axis). Unless otherwise explicitly stated, optical and electro-optical data are measured at 20°C.

[0772] "Clearing point" and "clearing point temperature" refer to the transition temperature from the LC phase to the isotropic phase.

[0773] Unless otherwise stated, the percentage of individual solid compounds in an RM mixture as described above and below refers to the total amount of solids (i.e., without any solvent) in the mixture.

[0774] Unless otherwise stated, all optical, electro-optical properties and physical parameters, such as birefringence, dielectric constant, conductivity, resistivity and sheet resistance, refer to a temperature of 20°C.

[0775] The present invention will now be described in more detail with reference to the following working examples, which are illustrative only and do not limit the scope of the invention.

[0776] Example 1

[0777] 1.1 RM formulation

[0778] To test wetting properties and inkjet printing performance, RM mixture R1 was prepared as follows:

[0779]

[0780]

[0781] The RM formulation F1 according to the present invention is prepared by dissolving the mixture R1 in 15% by weight solids in a ternary solvent blend of cyclohexanone (first solvent): isobutyrylbenzene (second solvent): 2-undecaneone (third solvent) in a ratio of 60:30:10.

[0782] For comparison, reference RM formulations C1 and C2 were prepared by dissolving mixture R1 in 15% by weight solids in binary solvent blends cyclohexanone:isobutyrophenone 30:70 (C1) and cyclohexanone:2-undecanetone 60:40 (C2), respectively.

[0783] 1.2 Contact Angle Measurement

[0784] Typically, the wetting properties of a liquid on a given substrate can be estimated by measuring the contact angle of the corresponding liquid on that substrate. The contact angle formed at the liquid-solid interface when a droplet is placed on a substrate surface provides insight into the liquid / solid affinity. A low contact angle (typically less than 90 degrees, but often less than 60 degrees) indicates good wetting, meaning the liquid spreads easily on the surface. A high contact angle (greater than 90 degrees) indicates poor wetting, where the liquid tends to form beads. When applied to inkjet printing, a contact angle greater than 60 degrees can cause the liquid to fail to form a continuous film.

[0785] The cinnamic acid ester photoalignment layer (PAL) was prepared as follows: a layer of cinnamic acid ester precursor material (from Nissan Chemical) was spin-coated onto a glass substrate at 2000 rm for 25 seconds, annealed on a hot plate at 70°C for 2 minutes, irradiated with linearly polarized UV light using a UV LED lamp (365 nm) via a wire grid polarizer, and then annealed again on a hot plate at 140°C for 3 minutes.

[0786] For each of formulations C1, C2, and F1, the contact angle on cinnamic acid ester PAL was measured as follows: Formulation droplets were dispensed onto the substrate, and the contact angle between the solid, liquid, and air interfaces was measured using a droplet shape analyzer. Measurements were repeated for four different droplets, and the average values ​​are reported in Table 1.

[0787] Table 1: Contact angles (CA) of RM formulations C1, C2, and F1 on cinnamic acid ester PAL

[0788]

[0789] All RM formulations C1, C2, and F1 exhibited low contact angles, indicating excellent wetting on the cinnamic acid ester PAL substrate.

[0790] 1.3 Inkjet printing and wetting

[0791] The reference RM formulation C3 was prepared by dissolving mixture R1 in pure cyclohexanone as 15% by weight solids.

[0792] Using an LP50 inkjet printer and Dimatix Samba ink cartridges, reference formulations C1, C2, and C3, and formulation F1 according to the invention, were respectively deposited on cinnamic acid ester PAL by inkjet printing at room temperature. The printed RM layers were then annealed at 80°C for 3 minutes and subjected to high-pressure mercury vapor lamp (100 mW·cm⁻¹). -2 It is cured by UV irradiation at 40°C for 60 seconds to form a polymer film.

[0793] Then, the wetting quality and film formation of RM formulations C1, C2, C3, and F1 on cinnamic acid ester PAL were studied by microscopy. Different amounts of deposition materials were selected, such as... Figure 1 The nine square test patterns shown are used to test the quality of the printed film in terms of shape.

[0794] Figure 2a -d shows a stitched micrograph (x2 magnification) of polymer patterns prepared by inkjet-printed RM formulations C1 (a), C2 (b), C3 (c) and F1 (d) between cross polarizers.

[0795] from Figure 2a As can be seen, the polymerization pattern prepared by formulation C1 exhibits good layer uniformity, but the formulation has strong spreading and overflow characteristics. From... Figure 2b As can be seen, the polymer pattern prepared by formulation C2 exhibits partial dehydration. From... Figure 2c As can be seen, the polymer pattern prepared from the reference formulation C3 in pure cyclohexanone exhibits a very significant striping effect due to rapid solvent evaporation.

[0796] Therefore, although pure solvent cyclohexanone and its binary blends with a second or third solvent as defined above exhibited low contact angle values ​​(<10 degrees, see Table 1) on the tested photoalignment layers, indicating good wetting properties, inkjet-printed films deposited from a blend of cyclohexanone and 2-undecanene (C2) showed poor wetting and film formation, while samples prepared by inkjet printing from a mixture of cyclohexanone and isobutyrylbenzene (C1) showed good wetting but poor shape retention. As used herein, "shape retention" refers to... Figure 1 The correlation between the shape of the expected printed pattern shown and the obtained pattern shown in Figure 2, etc.

[0797] In comparison, from Figure 2dAs can be seen, the polymeric pattern prepared by formulation F1 according to the present invention exhibits good wetting and good shape retention. Formulation F1 according to the present invention contains a ternary solvent blend, a blend of cyclohexanone as the first solvent and isobutyrylbenzene as the second solvent with better wetting and 2-undecane ketone as the third solvent with lower wetting (as determined by the above inkjet printing).

[0798] As shown below, the solvent blend can be further optimized by further changing the ratio between the second solvent (which has good wetting) and the third solvent (which has low wetting).

[0799] Example 2

[0800] The RM formulations F2 and F3 according to the present invention are prepared by dissolving the polymerizable mixture R1 of Example 1 in 15% by weight solids in a ternary solvent blend, which consists of a blend of 60% cyclohexanone and 40% isobutyrylbenzene and 2-undecaneone in different ratios as shown in Table 2.

[0801] Table 2: Ratio of the second and third solvents in RM formulations F2 and F3

[0802]

[0803] As described in Example 1, formulations F2 and F3 were inkjet printed onto cinnamate PAL to prepare a polymeric pattern.

[0804] Figure 3a &b shows stitched micrographs (x2 magnification) of polymeric patterns prepared by inkjet printing of RM formulations F2(a) and F3(b) according to the invention, respectively, between cross polarizers. It can be seen that the polymeric patterns prepared by the printed formulation exhibit improved shape retention at different ratios of the second and third solvents.

[0805] Example 3

[0806] Alternatively, other preferred ternary solvent blends containing aromatic ketones as the second solvent and aliphatic ketones as the third solvent can be used to optimize wetting behavior.

[0807] The RM formulations F4 and F5 according to the present invention are prepared by dissolving the polymerizable mixture R1 of Example 1 in 15% by weight solids in a ternary solvent blend, which consists of a blend of 60% cyclohexanone and 40% phenylbutanone and 2-decanone in different ratios as shown in Table 3.

[0808] Table 3: Ratio of second and third solvents in RM formulations F4 and F5

[0809]

[0810] As described in Example 1, formulations F4 and F5 were inkjet printed onto cinnamate PAL to prepare a polymeric pattern.

[0811] Figure 4a &b shows stitched micrographs (x2 magnification) of polymeric patterns prepared by inkjet-printed RM formulations F4 (a) and F5 (b), respectively, between cross-polarizers. It can be seen that the polymeric patterns prepared by the printed formulations exhibit very good wetting and shape retention at different ratios of the second and third solvents.

[0812] Example 4

[0813] Similar wetting behavior can be achieved when using solvent blends containing one of the solvents of the S2D formula, such as diethylene glycol monoethyl ether acetate (DEGMEA).

[0814] The reference RM formulation C4 was prepared by dissolving the polymerizable mixture R1 of Example 1 in 15% by weight solids in a binary solvent blend consisting of 70% cyclohexanone and 30% DEGMEA.

[0815] The RM formulations F6 and F7 according to the present invention are prepared by dissolving the polymerizable mixture R1 of Example 1 in 15% by weight solids in a ternary solvent blend, which consists of a blend of 60% cyclohexanone and 40% isobutyrylbenzene and DEGMEA in different ratios as shown in Table 4.

[0816] Table 4: Ratio of second and third solvents in RM formulations F6 and F7

[0817]

[0818] As described in Example 1, formulations C4, F6, and F7 were inkjet printed onto cinnamate PAL to prepare a polymer pattern.

[0819] Figure 5a -c shows stitched micrographs (x2 magnification) of polymeric patterns prepared from inkjet-printed RM formulations C4 (a), F6 (b), and F7 (c) between cross-polarizers. From Figure 5a As can be seen, reference formulation C4, using a binary solvent blend of cyclohexanone and DEGMEA, exhibits strong dehumidification. From... Figure 5b As can be seen from &c, formulations F6 and F7 according to the present invention, which use a ternary solvent blend comprising cyclohexanone (first solvent), isobutyrobenzoylbenzene (second solvent), and DEGMEA (third solvent), can optimize wetting behavior and shape retention.

Claims

1. A formulation comprising reactive mesomorphs (RM) or a mixture of two or more RMs, and further comprising a solvent blend consisting of three or more, preferably three, organic solvents. The solvent blend comprises a first solvent, a second solvent, and a third solvent, wherein the first solvent is a cycloalkanone having 5, 6, 7, or 8 C atoms, the second solvent is an aromatic ketone or aromatic ester, and the third solvent is an aliphatic ketone, aliphatic or aromatic alcohol, or diol.

2. The formulation according to claim 1, characterized in that... The first solvent is a cycloalkanone having 5, 6, 7, or 8 carbon atoms, preferably cyclohexanone or cycloheptanone; the second solvent is selected from formulas S1A and S1B; and the third solvent is selected from formulas S2A, S2B, S2C, and S2D. Ar S1 -(CH2) a -CO-R S1 S1A Ar S2 -(CH2) b -Z S -R S2 S1B R S3 -CO-R S4 S2A R S3 -C(OH)R S4 R S5 S2B R S6 -OHS2C R S7 -O-(CHR S8 -CHR S9 -O) c -R S10 S2D Each of these groups, independently of each other and in the same or different manner each time it appears, has the following meaning: Ar S1 Ar S2 It is an aryl or heteroaryl group having 5 or 6 ring atoms, optionally containing one or two heteroatoms selected from N, O and S, preferably phenyl, and optionally surrounded by one or more L groups. S replace, L S It is an alkyl, alkoxy, alkyl carbonyl, alkoxy carbonyl, alkyl carbonyloxy, or alkoxy carbonyloxy group having 1 to 5 carbon atoms, preferably an alkyl group having 1 to 5 carbon atoms, which is F, Cl, or optionally halogenated. R S1 The alkyl group has 1 to 8, preferably 1 to 6, carbon atoms, with methyl, ethyl, n-propyl, sec-propyl, isopropyl, n-butyl, sec-butyl, isobutyl, or tert-butyl being very preferred, and ethyl or isobutyl being most preferred. Z S is -CO-O- or -O-CO- R S2 It is an alkyl group having 1 to 8, preferably 1 to 6, carbon atoms, very preferably methyl, ethyl, propyl or butyl, and most preferably methyl or ethyl. R S3 It is an alkyl group having 1 to 7, preferably 1 to 5, carbon atoms, very preferably methyl, ethyl, propyl or butyl, and most preferably methyl or ethyl. R S4 It is an alkyl group having 1 to 15, preferably 8 to 12, carbon atoms. and R S3 and R S4 It can also form cycloalkyl groups with 5 to 8, preferably 5 or 6, ring atoms, with optional substitution together with the hydroxyl C atom. R S5 It is H or an alkyl group having 1 to 6 carbon atoms, preferably H. The total number of C atoms in formulas S2A and S2B is 5 to 16, with 5 to 12 being highly preferred. R S6 It is an alkyl group having 1 to 12, preferably 4 to 11 carbon atoms, or a phenylalkyl group having 1 to 4 alkyl carbon atoms, preferably phenylmethyl, 2-phenylethyl, or 3-phenylpropyl. R S7 It is H, methyl, acetyl, or phenyl, with H, acetyl, or phenyl being very preferred. R S8 R S9 It is methyl or ethyl, with methyl being the most preferred. R S10 It is H, methyl or ethyl. a is 0 or 1. b is 0 or 1. c can be 1, 2, or 3.

3. The formulation according to claim 1 or 2, characterized in that... The second solvent is selected from the following formula: Where R S1 Having the meaning given in claim 2 and preferably selected from methyl, ethyl, n-propyl, isopropyl, n-butyl, sec-butyl, isobutyl, and tert-butyl, very preferably selected from ethyl and isopropyl, and R S2 It has the meaning given in claim 2 and is preferably methyl or ethyl.

4. The formulation according to one or more of claims 1 to 3, characterized in that... The second solvent is selected from acetophenone, phenylacetone, phenylbutanone, isobutyrophenone, methyl benzoate, ethyl benzoate, methyl phenylacetate, butyl benzoate, benzyl propionate and phenyl propionate, preferably selected from acetophenone, phenylbutanone, isobutyrophenone, methyl phenylacetate and ethyl benzoate.

5. The formulation according to one or more of claims 1 to 4, characterized in that... The third solvent is selected from 2-nonanone, 2-decanone, 2-undecanone, 2-heptanol, 2-octanol, 2-nonanol, cyclopentanol, cyclohexanol, 1-hexanol, 1-heptanol, 1-octanol, 1-nonanol, 2-phenylethanol, phenylmethanol, 3-phenyl-1-propanol, PGME, DPM, TPM, PGMEA, DPMA, DEGMEA, TEGME, and phenoxyethanol, preferably selected from 2-decanone, 2-undecanone, cyclopentanol, cyclohexanol, 2-phenylethanol, PGME, PGMEA, DEGMEA, TEGME, and phenoxyethanol.

6. The formulation according to one or more of claims 1 to 5, characterized in that... The weight ratio of the first solvent to the sum of the second and third solvents in the solvent blend is 5:1 to 1:2, preferably 4:1 to 1:

1.

7. The formulation according to one or more of claims 1 to 6, characterized in that... The (weight) ratio of the second solvent to the third solvent in the solvent blend is preferably 1:1 to 8:1, more preferably 1.5:1 to 7:

1.

8. The formulation according to one or more of claims 1 to 7, characterized in that... It contains one or more RMs selected from formulas D and M. P 1 -Sp 1 -MG-Sp 2 -P 2 D P 1 -Sp 1 -MG-R 22 M Each of these groups, independently of each other and in the same or different manner each time it appears, has the following meaning: P 1 P 2 It is a polymerizable group. Sp 1 Sp 2 It is a spacer group or a single bond. MG is a rod-shaped mesocrystalline group, preferably selected from the formula MG. -(A 1 -Z 1 ) n -A 2 -MG A 1 and A 2 It is an aromatic or alicyclic group, optionally containing one or more heteroatoms selected from N, O, and S, and optionally mono- or poly-substituted with L. L is P-Sp-, F, Cl, Br, I, -CN, -NO2, -NCO, -NCS, -OCN, -SCN, -C(=O)NR x R y -C(=O)OR x -C(=O)R x -NR x R y -OH, -SF5, optionally substituted silyl groups, aryl or heteroaryl groups having 1 to 12, preferably 1 to 6, carbon atoms, and straight-chain or branched alkyl, alkoxy, alkylcarbonyl, alkoxycarbonyl, alkylcarbonyloxy, or alkoxycarbonyloxy groups having 1 to 12, preferably 1 to 6, carbon atoms, wherein one or more H atoms are optionally replaced by F or Cl, and L in formula M is different from P-Sp-. R x and R y It is H or an alkyl group having 1 to 12 carbon atoms. Z 1 for -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, preferably -COO-, -OCO- or a single bond. R 00 R 000 It is H or an alkyl group having 1 to 12 carbon atoms. Y 1 and Y 2 It can be H, F, Cl or CN. R 22 For P-Sp-, F, Cl, Br, I, -CN, -NO2, -NCO, -NCS, -OCN, -SCN, -C(=O)NR x R y -C(=O)X, -C(=O)OR x -C(=O)R y -NR x R y -OH, -SF5, optionally substituted silyl groups, straight-chain or branched alkyl groups having 1 to 12, preferably 1 to 6, carbon atoms, alkoxy, alkyl carbonyl, alkoxy carbonyl, alkyl carbonyloxy, or alkoxy carbonyloxy, wherein one or more H atoms are optionally replaced by F or Cl. X is a halogen, preferably F or Cl. n can be 1, 2, 3, or 4, preferably 1 or 2, with 2 being the most preferred. n is an integer from 11 to 10, preferably 1, 2, 3 or 4.

9. The formulation according to one or more of claims 1 to 8, characterized in that... It contains one or more RMs selected from formulas T and A. Each of these groups, independently of each other and in the same or different manner each time it appears, has the following meaning: P is a polymerizable group. Sp can be a spacer group or a single bond. Sp 1 It is a spacer group or a single bond, preferably an alkylene group having 1 to 12, more preferably 3 to 6 carbon atoms. R 11 H, F, Cl, CN, or optionally fluorinated alkyl, alkoxy, thioalkyl, alkylcarbonyl, alkoxycarbonyl, alkylcarbonyl or alkoxycarbonyloxy, or P-Sp, having 1 to 15, preferably 1 to 5, carbon atoms. R 33 H, F, Cl, CN, CH=CH2, optionally fluorinated or chlorinated alkyl, alkoxy, thioalkyl, alkylcarbonyl, alkoxycarbonyl, alkylcarbonyl or alkoxycarbonyloxy, or P-Sp, having 1 to 6, preferably 1 to 3, carbon atoms. A, B, D, and E are selected from 1,4-phenylene, 1,4-naphthyl-1,4-diyl, 2,6-diyl-naphthyl, 2,7-diyl-phenanthroline, 9,10-diyl-anthracene, 2,7-diyl-fluorene, 2,7-diyl-dibenzothiophene-2,7-diyl-dibenzofuran, 2,5-diyl-benzo[1,2-b:4,5-b']dithiophene-2,5-diyl, indole-4,7-diyl, 4,7-diyl-benzothiophene-4,7-diyl, 9,10-dihydro-phenanthroline-2,7-diyl, 1,2,3,4-tetrahydronaphthyl-5,8-diyl, or indane-2,5-diyl. Furthermore, one or more CH groups in these groups may be replaced by N, and all of them may optionally be replaced by one or more L or P-Sp- groups. C is selected from phenyl-1,4-diyl, naphthyl-1,4-diyl, anthracene-9,10-diyl, fluorene-2,7-diyl, dibenzofuran-2,7-diyl, dibenzothiophene-2,7-diyl, benzo[1,2-b:4,5-b']dithiophene-2,5-diyl, indole-4,7-diyl, and benzothiophene-4,7-diyl, all of which may optionally be substituted with one or more L or P-Sp groups. Furthermore, either ring C or ring D can represent a single bond. A A B A The groups are phenylene-1,4-diyl, naphthio-1,4-diyl, naphthio-2,6-diyl, fluorene-2,7-diyl, dibenzothiophene-2,7-diyl, dibenzofuran-2,7-diyl, benzo[1,2-b:4,5-b']dithiophene-2,5-diyl, indole-4,7-diyl, benzothiophene-4,7-diyl, 9,10-dihydro-phenanthroline-2,7-diyl, or 1,2,3,4-tetrahydronaphthalene-5,8-diyl, wherein one or more CH groups in these groups may be replaced by N, and all of them may optionally be replaced by one or more L or P-Sp- groups. C A The group is phenylene-1,4-diyl, naphthol-1,4-diyl, or naphthol-2,6-diyl, preferably phenylene-1,4-diyl or naphthol-2,6-diyl, wherein one or more CH groups in these groups may be replaced by N, and optionally by one or more L or P-Sp- groups. Preferably, A A B A and C A No more than one of them represents naphthalene-1,4-diyl. L is F, Cl, -CN, -SCN, P-Sp- or a straight-chain, branched, or cyclic alkyl group having 1 to 25 C atoms, wherein one or more non-adjacent CH2- groups are optionally replaced by the following groups in such a way that the O atoms and / or S atoms are not directly connected to each other: -O-, -S-, -CO-, -CO-O-, -O-CO-, -O-CO-O-, CR 0 =CR 00 -、-C C-、 Furthermore, one or more H atoms may be optionally replaced by P-Sp-, F, or Cl, or two substituents L connected to directly adjacent C atoms may form cycloalkyl or cycloalkenyl groups with 5, 6, 7, or 8 C atoms. Z 11 Z 12 for -O-, -S-, -CO-, -COO-, -OCO-, -S-CO-, -CO-S-, -O-COO-, -CO-NR 0 -、-NR 0 -CO-、-NR 0 -CO-NR 00 -NR 0 -CO-O-、-O-CO-NR 0 -, -OCH2-, -CH2O-, -SCH2-, -CH2S-, -CF2O-, -OCF2-, -CF2S-, -SCF2-, -CH2CH2-, -(CH2) n1 , -CF2CH2-, -CH2CF2-, -CF2CF2-, -CH=N-, -N=CH-, -N=N-, -CH=CR 0 -、-CY 1 =CY 2 -、-C C-, -CH=CH-COO-, -OCO-CH=CH- or single bonds, preferably -COO-, -OCO-, or -C. C- or a single bond, with a single bond being the optimal choice. R 0 R 00 It is H or an alkyl group having 1 to 12 carbon atoms. Y 1 Y 2 For H, F, Cl, NCS or CN, m1 and m2 can be 0, 1, 2, 3, or 4, preferably 0, 1, or 2, very preferably 0 or 1, and most preferably 0. m3 is 0 or 1. n1 is 1, 2, 3, or 4. s can be 0, 1, 2 or 3, preferably 0, 1 or 2.

10. The formulation according to one or more of claims 1 to 9, characterized in that... It further comprises one or more optional polymerizable and / or isomerizable chiral compounds.

11. The formulation according to one or more of claims 1 to 10, characterized in that... It further comprises one or more additives, preferably selected from polymerization initiators, surfactants, stabilizers, catalysts, sensitizers, inhibitors, chain transfer agents, co-reactive monomers, reactive thickeners, surface-active compounds, lubricants, wetting agents, dispersants, hydrophobic agents, adhesives, flow improvers, degassing or defoaming agents, degassing agents, diluents, reactive diluents, auxiliaries, colorants, dyes, pigments, and nanoparticles.

12. A polymer or polymer film that is available or obtained from an agent according to one or more of claims 1 to 11.

13. A method for preparing the polymer or polymer film according to claim 12, comprising the following steps: The preparation of one or more of claims 1 to 11 is deposited onto a substrate, preferably with solvent removed, optionally with the layer annealed, and the RM or RM mixture polymerized, preferably at a temperature at which it exhibits a liquid crystal phase, and wherein the preparation is preferably deposited onto the substrate by printing, very preferably by inkjet printing.

14. The method according to claim 13, characterized in that... The substrate comprises a cinnamate alignment layer, onto which the RM formulation is printed.

15. Use of the formulation, polymer or polymer film according to one or more of claims 1 to 14 in optical, electro-optical or electronic components or devices.

16. An optical, electro-optical, or electronic device or a component thereof comprising a formulation, polymer, or polymer film according to one or more of claims 1 to 12.

17. The component of claim 16, selected from optical delay films such as quarter-wave plates (QWP) or half-wave plates (HWP), polarizers, optical compensators, reflective films, diffraction or surface gratings such as Bragg polarization gratings (Bragg PG), polarization volume gratings (PVG), polarization volume holograms (PVH), Panchara Thamnamm-Berry (PB) gratings, and non-mechanical beam steering elements, optical waveguides, optical couplers, deflectors or combiners, polarization beam splitters, partial mirrors, reflective films, alignment layers, color filters, anti-static protective sheets, electromagnetic interference protective sheets, lenses for light guiding, focusing and optical effects, polarization control lenses, PB deflectors, PB lenses and infrared reflective films.

18. The device of claim 16, selected from liquid crystal displays, organic light-emitting diodes, nonlinear optical (NLO) devices, autostereoscopic 3D displays, head-up displays, near-eye displays, AR / VR systems, glasses for AR / VR applications, switchable windows, spatial light modulators, optical data storage devices, optical sensors, holographic devices, spectrometers, optical communication systems, polarizers, or headlights / backlights.

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