Half-wave plate

Abstract

The invention relates to a half-wave plate comprising two layers of chiral liquid crystal (LC) polymers (which are subclasses of liquid crystal materials) with pitch gradients; a preparation method thereof; the invention also relates to the use thereof as a diffractive optical element in optical or electro-optical components or devices, in particular for digital optical or augmented reality or virtual reality (AR / VR) applications, such as a polarizer, an optical compensator, a reflective film, a diffraction grating or surface grating, a Bragg polarization grating (Bragg PG), a polarization volume grating (PVG), a polarization volume hologram (PVH), a Pangulam-Bell (PB) grating, a non-mechanical beam steering element, an optical waveguide, an optical coupler, an optical combiner, a polarization beam splitter, a partial mirror or a lens.

Description

Technical Field

[0001] This invention relates to a half-wave plate comprising two layers of chiral liquid crystal (LC) polymers (as a subclass of liquid crystal materials) with pitch gradients; a method for preparing the half-wave plate; and its use as a diffractive optical element 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 gratings or surface gratings, Bragg polarization gratings (Bragg PG), polarization volume gratings (PVG), polarization volume holograms (PVH), Panchara Thamnam-Berry (PB) gratings, non-mechanical beam manipulation elements, optical waveguides, optical couplers, optical combiners, polarized beam splitters, partial mirrors or lenses. Background Technology

[0002] Half-wave plates are extremely important in the field of digital optics. They are used in Panchara Thamnamm-Berry (PB) optical elements, also known as cycloidal diffraction waveplates, such as those used by Yun-Han Lee et al. Opt. Data Processing. Storage As described in ;3, 79-88 (2017). These are patterned half-wave plates in which the profile distribution continuously varies with the XY plane. PB optical elements include PB lenses (PBL) and PB gratings (PBG). In the PBL, as... Figure 1 As shown in a, the pointer vector continuously changes parabolically along the radial axis, while in PBG, as... Figure 1 As shown in b, the distribution of the pointer vector changes linearly in the longitudinal direction, and both cases are shown in the aforementioned references.

[0003] PBL and PBG gratings can be active devices made of liquid crystals that can be electrically switched. Alternatively, they can be static devices made of polymerizable LC (also known as reactive mesocrystalline (RM)) to provide thin lenses and gratings on a plastic substrate.

[0004] It is known in the prior art that half-wave plates using a single film made of refractive index (RM) suffer from chromaticity problems due to the light dispersion of the RM. Optimizing the thickness of the RM film to obtain a half-wave plate for a specific wavelength means that for all other wavelengths, the film will not be a half-wave plate and will therefore exhibit light leakage. A common method to improve this light leakage due to material dispersion is to use a negatively dispersive RM film. This has the advantage that a single film can compensate for the blue and green regions of the visible spectrum. However, as the dispersion in this region tends to flatten, there is always a trade-off in the red wavelength. While the green and blue regions of the visible spectrum will exhibit low light leakage, the red region of the visible spectrum will leak through undesirable means. The individual RM monomers used in negatively dispersive RM films are also extremely expensive and have low birefringence. The compounds used to manufacture half-wave plates using negatively dispersive RM films are excessively expensive.

[0005] It is known in the prior art that multilayer RM films can improve achromaticity, even compared to negative dispersion RM films. However, this method typically requires three or more layers to achieve good achromaticity in the visible spectrum. Including multiple layers introduces complexity during film coating and can also introduce problems such as wetting resistance and alignment difficulties, which may be exacerbated when more layers are added to the stack. Therefore, it is advantageous to reduce the number of layers to two or even a single layer while maintaining achromaticity.

[0006] Therefore, there is still a need for improved polymer films made of RM materials and their production methods, which can be used as half-wave plates to exhibit reduced chromaticity across most of the visible spectrum, without exhibiting the shortcomings of existing materials, methods and films or exhibiting only to a lesser extent when shortcomings are present, and can be mass-produced with reproducible quality and compatibility with mass production through simple, time-efficient and cost-effective methods.

[0007] One object of the present invention is to provide an improved polymer film and a method for producing the same, which can be used as a half-wave plate with reduced chromaticity. Other objects of the invention will become apparent to those skilled in the art from the following embodiments.

[0008] Surprisingly, the inventors of this invention have discovered that one or more of these objectives can be achieved by providing polymer films prepared from chiral RM mixtures and methods thereof, as disclosed and claimed below. Summary of the Invention

[0009] The present invention relates to a half-wave plate comprising two layers, preferably consisting of two layers, each layer comprising a polymeric chiral RM mixture having a helical twisted structure, preferably consisting of the polymeric chiral RM mixture, wherein the helical pitch in each layer increases or decreases in the film thickness direction, and wherein the two layers have opposite twisting directions.

[0010] Preferably, the half-wave plate comprises two quarter-wave plates, each of which comprises a layer of a polymeric chiral RM mixture having a helical twisted structure, preferably composed thereof, wherein the helical pitch increases or decreases in the film thickness direction, and wherein the two quarter-wave plates have opposite twisting directions.

[0011] Preferably, the chiral RM mixture comprises at least one, preferably exactly one, chiral compound having one or more isomerizable groups, preferably one or more photoisomerizable groups, which is preferably polymerizable.

[0012] Very preferably, the chiral RM mixture contains at least two, more preferably exactly two, chiral compounds with opposite optical rotations, one of which contains an isomerizable group and the other does not contain an isomerizable group, and one or both of the chiral compounds are polymerizable.

[0013] The present invention further relates to a method for preparing a half-wave plate as described above and below.

[0014] The present invention further relates to an optical, electronic, or electro-optical component or device that also includes the half-wave plate described above and below. The present invention further relates to an optical, electro-optical, or electronic device or component that includes the half-wave plate described above and below.

[0015] This component includes, but is not limited to, optical retardation films, polarizers, optical compensators, diffraction or surface gratings such as Bragg polarization gratings (Bragg PG), polarization volume gratings (PVG), Panchara-Thamnamm-Berry gratings (PBG), or Panchara-Thamnamm-Berry lenses (PBL), as well as non-mechanical beam manipulation elements, optical waveguides, optical couplers 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, and IR reflective films; for example, 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 sensing optical sensing, holography, spectroscopy, optical communication, polarization measurement, or front / backlighting.

[0016] The device includes, but is not limited to, electro-optic displays, especially LCDs, OLEDs, nonlinear optical (NLO) devices, automated stereoscopic 3D displays, near-eye vision displays, AR / VR systems, AR / VR application goggles, switchable windows, spatial light modulators, optical data storage devices, optical sensors, holographic devices, spectrometers, optical communication systems, polarimeters, or front / backlights. Attached Figure Description

[0017] Figure 1 a and Figure 1 b. Exemplary and schematic illustration of the LC pointing vector orientation in the PB lens (a) and PB grating (b).

[0018] Figure 2 The distortion profile in a half-wave plate according to Embodiment 1 of the present invention is shown.

[0019] Figure 3Transmittance versus wavelength plots are shown for a film stack (a) of Embodiment 1 with a half-wave plate according to the invention between orthogonal polarizers and a film stack (b) of Comparative Embodiment 1 with a standard half-wave plate between orthogonal polarizers. The half-wave plate according to the invention consists of two quarter-wave plates with a pitch gradient.

[0020] Figure 4 Transmittance versus wavelength plots are shown for a film stack (a) of Embodiment 1 with a half-wave plate according to the invention between orthogonal polarizers and a film stack (b) of Comparative Embodiment 2 with a standard half-wave plate between orthogonal polarizers. The half-wave plate according to the invention consists of two quarter-wave plates with a pitch gradient, and the standard half-wave plate consists of two standard quarter-wave plates.

[0021] Terms and Definitions

[0022] In the preceding and following text, the statement "two layers (or quarter-wave plates) have opposite twisting characteristics" means that the twisting direction of the spiral twisting structure in the first of the two layers (or quarter-wave plates) is opposite to the twisting direction of the spiral twisting structure in the second of the two layers (or quarter-wave plates).

[0023] Throughout the embodiments and claims of this specification, the terms “comprise” and “containing”, and variations thereof, such as “comprising” and “comprises”, mean “including but not limited to”, and do not intend to exclude other components.

[0024] 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.

[0025] 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.

[0026] The term "monolayer membrane" refers to a single layer (or monolayer) of a particular material (such as the polymerized chiral RM mixture described above and below).

[0027] 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”.

[0028] Unless otherwise stated, the term “polymerizable compound” as used herein should be understood to mean a polymerizable monomeric compound.

[0029] 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.

[0030] 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.

[0031] 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.

[0032] 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.

[0033] 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.

[0034] 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.

[0035] As used herein, the term "RM formulation" means at least one RM or a mixture of RMs, and one or more other materials added to at least one RM or a mixture of RMs to provide or modify the RM formulation and / or a particular property of the at least one RM. It should be understood that RM formulations are also media for carrying RMs to a substrate to enable the formation of layers or structures thereon. Exemplary materials include, but are not limited to, solvents, polymerization initiators, surfactants, and adhesion promoters, as described in more detail below.

[0036] Unless otherwise stated, the percentages of compounds in RM mixtures given above and below mean by weight of the total RM mixture, excluding solvents or additives used in RM formulations as described above and below.

[0037] Unless otherwise stated, the percentage of compounds in RM formulations given above and below means by weight % of all solids in the RM formulation, including but not limited to liquid additives as described below.

[0038] As used herein, the term "perfluoroalkyl and / or polyfluoroalkyl substances (PFAS)" (in accordance with the OECD definition) means a substance or compound containing at least one fully fluorinated methyl or methylene C atom (without any H / Cl / Br / I atoms attached thereto), i.e., a compound having at least one CF3 or CF2 group.

[0039] As used herein, the term "polyfluorinated alkyl or aryl" means an alkyl or aryl group 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.

[0040] 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.

[0041] 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.

[0042] A "polymer network" is a network in which all polymer chains are interconnected to form a single macroscopic entity through many crosslinks.

[0043] Polymer networks can appear in the following types:

[0044] -A grafted polymer molecule is a branched polymer molecule in which one or more side chains are structurally or configurationally different from the main chain.

[0045] A star polymer molecule is a branched polymer molecule in which a single branch point generates multiple linear chains or arms. If the arms are identical, the star polymer molecule is called regular. If adjacent arms are composed of different repeating subunits, the star polymer molecule is called diverse.

[0046] - Comb-like polymer molecules consist of a main chain with two or more three-way branching points and linear side chains. If the arms are the same, the comb-like polymer molecule is called regular.

[0047] - Brush-like polymer molecules consist of a linear main chain and unbranched side chains, wherein one or more of the branch points have four or more functionalities.

[0048] The term "chirality" is generally used to describe objects that cannot be superimposed on their mirror images.

[0049] A "non-chiral" object is an object that is identical to its mirror image.

[0050] Unless otherwise expressly stated, the terms “chiral nematic” and “cholesterol type” are used synonymously in this application.

[0051] The term "isomerizable / photoisomerizable compound" refers to a compound that includes one or more isomerizable or photoisomerizable groups, respectively.

[0052] 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).

[0053] 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.

[0054] 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.

[0055] The chiral RM mixture 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.

[0056] Then, the concentration c of the chiral compound (expressed as a percentage) and the helical twisting force HTP (expressed in nm) are used to determine the concentration of the chiral compound. -1 The pitch p (also referred to below as "chiral pitch" or "spiral pitch") of the induced cholesterol helix is ​​given by the following equation (denoted in nm):

[0057] p = (HTP c) -1

[0058] The lower pitch value is referred to as "short pitch" below, and the higher pitch value is referred to as "long pitch" below. Short pitch corresponds to a highly twisted structure (i.e., a higher twist angle), while long pitch corresponds to a slowly twisted structure (i.e., a lower twist angle) around the helical axis over a given distance.

[0059] The twist angle θ is defined by the following equation based on the thickness d:

[0060]

[0061] Where p is the pitch as defined above.

[0062] When using more than one chiral compound, the total HTP (HTP) of chiral compounds with the same configuration or tortuosity type is... 总 Then it approximately satisfies the following equation:

[0063] HTP 总 = ∑ i c i HTP i

[0064] 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.

[0065] HTP (IHTP) of all chiral compounds in mixtures with different configurations or different twist directions Δ I) then approximately satisfy the following equation:

[0066] IHTP Δ I =(∑ s c s HTP s ) -((∑ r c r HTP r )

[0067] 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.

[0068] The birefringence Δn is defined as follows:

[0069] Δn=n e -n o

[0070] 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:

[0071] n av. =(2n o 2 +n e 2 ) / 3) ½

[0072] 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.

[0073] The center wavelength λ and bandwidth Δλ of the reflection band of cholesterol RM or LC materials or cholesterol polymer films are determined by the pitch p of the cholesterol helix and the average refractive index n of the cholesterol liquid crystal. av. The birefringence Δn is given by the following equation:

[0074] λ=n av. . p

[0075] Δλ=Δn. p

[0076] 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.

[0077] 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 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.

[0078] Irradiance (E) e Or, radiation power is defined as the electromagnetic radiation power (dθ) incident on a surface per unit area (dA):

[0079] E e = dθ / dA.

[0080] Radiation exposure or radiation dose (H) e ) represents the irradiance or radiant power (E) per time (t). e ):

[0081] H e = E e t.

[0082] At the molecular level, the birefringence of liquid crystals depends on the anisotropy of polarization index (Δα=α). װ -α ┴ The term "polarization rate" refers to the ease with which the distribution of electrons 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.

[0083] The "optical retardation" R(λ) (in nm) of a liquid crystal or birefringent material layer at a given wavelength is defined as the product of the birefringence Δn(λ) at that wavelength and the layer thickness d (in nm) according to the following equation:

[0084] R(λ) = Δn(λ) . d

[0085] Optical retardation R represents the difference (in nanometers) in the optical path length of S-polarized light and P-polarized light as they propagate through a birefringent material. "On-axis" retardation refers to the retardation when light is incident perpendicularly to the sample surface.

[0086] The retardation (R(λ)) of a material can be measured using a spectroelometric ellipsometry (e.g., the M2000 spectroelometric ellipsometry manufactured by JA Woollam Co.). This instrument measures the optical retardation (in nanometers) of birefringent samples (e.g., quartz) typically in the wavelength range of 370 nm to 2000 nm. From this data, the dispersion of the material (R(450) / R(550) or Δn(450) / Δn(550)) can be calculated.

[0087] A method for performing this measurement was presented by N. Singh in October 2006 at the National Physics Laboratory (London, UK) under the title “Spectroscopic Ellipsometry, Part 1 - Theory and Fundamentals, Part 2 - Practical Examples and Part 3 - Measurements”. This method is based on the Retardation Measurement (RetMeas) Manual (2002) and Guide to WVASE (2002) published by JA Woollam Co. Inc (Lincoln, NE, USA) (Woollam Variable Angle Spectroellipsometry). W oollam V ariable A ngle S pectroscopic E The measurement procedure described in the lipsometer is used to determine the delay of the materials, membranes, and devices described in this invention, unless otherwise stated.

[0088] The term "director" is known in the art and refers to the preferred orientation of the long molecular axis (in the case of rod-shaped compounds) or short molecular axis (in the case of disk-shaped compounds) of a liquid crystal or RM molecule. In the case of such anisotropic molecular uniaxial ordering, the director is the anisotropic axis.

[0089] The terms "alignment" or "orientation" refer to the alignment (orientational 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.

[0090] The term "uniform orientation" or "uniform alignment" in liquid crystal or RM materials, for example within layers of the material, refers to the orientation of 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 in essentially the same direction. In other words, the lines pointing to the liquid crystal are parallel.

[0091] The term "vertical structure / alignment / orientation" refers to a membrane in which the optical axis is substantially perpendicular to the membrane plane.

[0092] The term "planar structure / alignment / orientation" refers to a membrane in which the optical axis is substantially parallel to the membrane plane.

[0093] 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.

[0094] In cases of doubt, the definition given in C. Tschierske, G. Pelzl and S. Diele, Angew. Chem. 2004, 116, 6340-6368 shall prevail.

[0095] 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.

[0096] 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.

[0097] 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 "etc." 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.

[0098] 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.

[0099] 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 R 22R 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.

[0100] 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:

[0101] ,

[0102] -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:

[0103]

[0104] -OCH2OCH3, -O(CH2)2OCH3, -O(CH2)3OCH3, -O(CH2)4OCH3, -O(CH2)2F, -O(CH2)3F and -O(CH2)4F.

[0105] 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.

[0106] 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.

[0107] In the context, or This indicates the trans-1,4-cyclohexyl ring, and It represents a 1,4-phenylene ring.

[0108] The halogen is preferably F or Cl, with F being the most preferred.

[0109] Group -CR 0 =CR 00 - Preferably -CH=CH-.

[0110] -OC-, -CO-, -C(=O)-, and -C(O)- represent carbonyl groups, i.e. .

[0111] 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.

[0112] 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.

[0113] 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.

[0114] Preferred , , or ,

[0115] L has one of the meanings indicated above.

[0116] 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.

[0117] 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, benzotriazole, purine, naphzimidazole, phenanthrenemidazole, pyridinium imidazole, pyrazinium imidazole, quinoxaline imidazole, benzoxazole, naphzimidazole, anthraquinoxazole, phenanthrenemidazole, isoxazole, benzothiazole, 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.

[0118] At group In the diagram, the single bond between two ring atoms can attach to any empty position on the benzene ring.

[0119] -OC-, -CO-, -C(=O)-, and -C(O)- represent carbonyl groups, i.e. .

[0120] 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.

[0121] Preferred group P, including any variation thereof, such as P 0 P 1 P 2 , 0 Choose from the following groups:

[0122] 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.

[0123] The highly preferred group P, including any variation thereof, such as P 0 P 1 P 2 , 0 Choose from the following groups:

[0124] 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.

[0125] 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 .

[0126] 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.

[0127] In another preferred embodiment of the invention, in the polymerizable compounds disclosed in the context, including compounds of formula I and its sub-formulas, all polymerizable groups have the same meaning and preferably represent acrylate or methacrylate groups, very preferably acrylate groups.

[0128] Spacer groups, including any variations thereof, such as Sp 0 Sp 1 Sp 2S 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

[0129] "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.

[0130] 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

[0131] R 0 and R 00 Each independently represents H or an alkyl group having 1 to 20 carbon atoms, and

[0132] Y 2 and Y 3 Each can be represented independently as H, F, Cl, or CN.

[0133] 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.

[0134] 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.

[0135] 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.

[0136] 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.

[0137] In another preferred embodiment of the invention, polymerizable compounds as disclosed in the context include those of formula I and its sub-formulas, containing a spacer group Sp, including any variation thereof, such as Sp 0 Sp 1 Sp 2 S 0 It is formed by the substitution of one or more polymerizable groups P, such that groups Sp-P, etc., correspond to Sp(P). s , and s ≥2 (branched polymerizable groups).

[0138] Preferred polymerizable compounds according to this preferred embodiment are those in which s is 2, i.e., compounds containing the Sp(P)2 group. Very preferred polymerizable compounds according to this preferred embodiment contain groups selected from the following formula:

[0139] -X-alkyl-CHPP S1

[0140] -X-alkyl-CH((CH2) aa P)((CH2) bb P) S2

[0141] -XN((CH2) aa P)((CH2) bb P) S3

[0142] -X-alkyl-CHP-CH2-CH2P S4

[0143] -X-alkyl-C(CH2P)(CH2P)-C aa H 2aa+1 S5

[0144] -X-alkyl-CHP-CH2P S6

[0145] -X-alkyl-CPP-C aa H 2aa+1 S7

[0146] -X-alkyl-CHPCHP-C aa H 2aa+1 S8

[0147] Where P is defined as in Equation I.

[0148] 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 in which one or more non-adjacent CH2 groups can be independently substituted with -C(R) 0 )=C(R 0)-、-C≡C-、-N(R 0 -, -O-, -S-, -CO-, -CO-O-, -O-CO-, -O-CO-, -O-CO-O- are replaced by O and / or S atoms that are not directly connected to each other, where R 0 It has the meaning of the instructions above.

[0149] aa and bb each independently represent 0, 1, 2, 3, 4, 5, or 6.

[0150] X has one of the meanings indicated by X", and is preferably O, CO, SO2, O-CO-, CO-O or a single bond.

[0151] The preferred spacer group Sp(P)2 is selected from formulas S1, S2 and S3.

[0152] The highly preferred spacer group Sp(P)2 is selected from the following formulas:

[0153] -CHPP S1a

[0154] -O-CHPP S1b

[0155] -CH2-CHPP S1c

[0156] -OCH2-CHPP S1d

[0157] -CH(CH2-P)(CH2-P) S2a

[0158] -OCH(CH2-P)(CH2-P) S2b

[0159] -CH2-CH(CH2-P)(CH2-P) S2c

[0160] -OCH2-CH(CH2-P)(CH2-P) S2d

[0161] -CO-NH((CH2)2P)((CH2)2P) S3a Detailed Implementation

[0162] The inventors of this invention unexpectedly discovered that a half-wave plate can be provided by combining two quarter-wave plates with high achromaticity, each quarter-wave plate consisting of a polymer film formed from a polymeric chiral RM mixture with a helical twisted structure exhibiting a pitch gradient, i.e., the helical pitch increases or decreases in the film thickness direction, and the helices in the two quarter-wave plates have opposite twisting directions. By combining two such quarter-wave plates with opposite twisting directions, a half-wave plate with excellent achromaticity in the visible spectrum can be achieved.

[0163] Each quarter-wave plate according to the invention comprises a monolayer film of a polymeric chiral RM mixture. The chiral RM mixture is also referred to hereinafter as "RM mixture (according to the invention)". The film of the polymeric chiral RM mixture forming the quarter-wave plate is also simply referred to hereinafter as "polymer film (according to the invention)". The half-wave plate according to the invention therefore comprises, preferably comprises, the two polymer films according to the invention described above and below.

[0164] To achieve a nonlinear twisted profile, the RM mixture used to prepare the polymer film preferably contains at least one RM and at least one chiral compound having one or more isomerizable groups (preferably one or more photoisomerizable groups, such as, for example, cinnamic acid ester groups). The chiral compound having one or more isomerizable groups is preferably polymerizable.

[0165] One or more isomerizable groups in this chiral compound can undergo photo-driven E / Z isomerization, exhibiting a reduction in helical twist force (HTP) during this process. This allows for rapid photo-driven tuning of the chiral pitch in the RM layer, and alignment profiles with variable pitch can be produced by changing the formulation and processing conditions. When aligned on the grating alignment layer, it is possible to increase the grating angular bandwidth.

[0166] Furthermore, this allows bilayer chiral RM films, as described in the prior art, to be replicated as single-layer or monolayer films. This avoids problems associated with multilayer film fabrication, where multiple RM layers with different pitch values ​​must be coated onto each other, such as insufficient alignment transfer between RM layers, the occurrence of alignment defects, damage to lower RM layers caused by subsequent layers, or the control of different pitch values ​​and tilt angles in each RM layer.

[0167] Conversely, the polymer film according to the invention exhibits a nonlinear tortuous profile with accelerated torsion across the film thickness, which can be achieved by using a photoisomerizable chiral compound that undergoes isomerization during partial polymerization.

[0168] In particular, the nonlinear twisted profile can be achieved by the method for preparing polymer films according to the present invention as described above and below. This method comprises two steps of irradiating the chiral RM layer with photochemical radiation (e.g., UV light), which causes photoisomerization of the chiral compound and photopolymerization of the RM.

[0169] The first irradiation step involves UV irradiating the RM layer in air, rather than in an inert atmosphere (such as nitrogen). Without wanting to be bound by a particular theory, the inventors believe that an oxygen-rich environment during photocuring inhibits free radical polymerization. This effect is utilized to allow the RM layer to partially polymerize along a gradient with film depth. The polymerization rate is low at the top of the RM layer exposed to oxygen because polymerization is partially hindered by the oxygen environment, while photoisomerization of chiral compounds still occurs. At the bottom of the film at the substrate interface, which is not directly affected by oxygen, polymerization is much less hindered by oxygen and occurs more readily.

[0170] Simultaneously, due to the presence of at least one photoisomerizable chiral compound, photoisomerization occurs during the first UV irradiation step, and the helical twist force (HTP) of the photoreactive chiral compound decreases upon exposure to UV light. In regions of higher polymer density, changes in the chiral structure are physically resisted. As described above, due to the lower polymer density at the top or surface of the RM layer, the chiral structure and helical pitch can be modified more freely. At the bottom of the film adjacent to the substrate (where more photopolymerization occurs), the polymer density is higher, thus hindering changes in the chiral structure and helical pitch. This results in a pitch gradient within the film, where the chiral rotation angle gradually increases or decreases across the film thickness (depending on the observation direction).

[0171] Therefore, after performing the method described above, the polymerized LC medium exhibits accelerated chiral rotation in a direction perpendicular to the main plane of the polymer film (i.e., in the film thickness direction), thereby generating nonlinear twisting through the film thickness.

[0172] The second irradiation step is carried out in an inert gas atmosphere (e.g., nitrogen), which also completes the polymerization process in the upper region of the RM layer, so that the RM layer is fully polymerized into a polymer film with locked nonlinear twist.

[0173] The polymer film and its preparation method according to the present invention offer several advantages, some of which have been described above and below.

[0174] The polymer film according to the invention has planar orientation and, by adding a small amount of chiral dopant with high torsional force, induces helical twisting in the direction through the film thickness. Therefore, vertical orientation can be provided in a single film using only one RM mixture. This achieves low material cost and increased market competitiveness.

[0175] It has been achieved by applying low-intensity UV light to create a biased helical pitch (or helical pitch gradient) in the polymer film according to the invention, i.e., where the chiral twist angle gradually increases through the film thickness (i.e. in the direction perpendicular to the film plane).

[0176] In addition to the advantageous effects described above and below, the polymer film and its preparation method according to the present invention also provide the following advantages:

[0177] - Chiral RM mixtures can be easily aligned to the desired orientation, for example, on a planar alignment layer or on a PB grating.

[0178] - By adding only a small amount of chiral compounds with high HTP, helical twisting is induced throughout the entire film thickness.

[0179] - Vertical orientation can be provided in a single membrane using only one RM mixture, which achieves low material costs and increases market competitiveness.

[0180] - It has been possible to achieve helical pitch gradients in polymer films by applying low-intensity UV light.

[0181] Compared to conventional methods for preparing single-planar aligned RM films, the method for preparing polymer films requires only one additional process step.

[0182] - This additional method step involves low-intensity UV exposure in air to induce photoisomerization of the chiral compound, without requiring an inert gas atmosphere or additional heating or cooling of the membrane.

[0183] Preferably, each quarter-wave plate according to the invention contains only one polymer film formed from a polymeric chiral RM mixture having a pitch gradient.

[0184] The half-wave plate according to the invention comprises, preferably, two polymer films formed from a mixture of polymeric chiral RM having a pitch gradient.

[0185] The chiral RM mixture used to prepare the polymer film or quarter-wave plate according to the invention comprises one or more chiral isomerizable compounds, preferably selected from chiral photoisomerizable compounds.

[0186] Chiral isomerizable compounds can be polymerizable or non-polymerizable. They can be amorphous or mesomorphic compounds. If a chiral isomerizable compound is polymerizable, it can be monoreactive or polyreactive.

[0187] In a preferred embodiment, the chiral RM mixture comprises one or more polymerizable chiral isomerizable compounds.

[0188] In another preferred embodiment, the chiral RM mixture contains exactly one chiral isomerizable compound.

[0189] More preferably, the chiral RM mixture contains only chiral isomerizable compounds selected from polymerizable, preferably monoreactive or direactive chiral isomerizable compounds.

[0190] In another preferred embodiment, the chiral RM mixture comprises at least two, more preferably exactly two, chiral compounds having opposite optical rotations, one of which contains an isomerizable group and the other does not contain an isomerizable group, and one or two, preferably two, chiral compounds are polymerizable.

[0191] In another preferred embodiment, the chiral RM mixture does not contain any chiral compound with no isomerizable groups (especially no photoisomerizable groups). Most preferably, according to this preferred embodiment, the chiral RM mixture does not contain any other chiral compound besides one or more chiral isomerizable compounds.

[0192] Suitable and preferred polymerizable chiral isomerizable compounds comprise one or more ring elements linked together by direct bonds or via a linking group, wherein either of these ring elements may be linked to each other directly or via a linking group, which may be the same as or different from the mentioned linking group. The ring elements are preferably selected from groups of 4-, 5-, 6-, or 7-, preferably 5- or 6-membered rings.

[0193] Preferred chiral isomerizable compounds are selected from formula I :

[0194] R 3 -(A 3 -Z 3 ) m -G(-(Z 4 -A 4 ) l -R 4 ) k I

[0195] Each group, independently of the others and in the same or different manner each time it appears, has the following meaning:

[0196] R 3 R 4 It is H, F, Cl, CN, P-Sp- or an alkyl group having up to 25 carbon atoms, which may be unsubstituted, monosubstituted or polysubstituted with halogen or CN, and one or more non-adjacent CH2 groups may also (in each case) be independently substituted with -O-, -S-, -NH-, -N(CH3)-, -CO-, -COO-, -OCO-, -OCO-O-, -S-CO-, -CO-S- or -C≡C- in such a way that the oxygen atoms are not directly connected to each other.

[0197] P is a polymerizable group.

[0198] Sp is a spacer group or a single bond.

[0199] 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 a single bond,

[0200] 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.

[0201] G is a chiral group.

[0202] 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 substituted with -O-, -S-, -CO-, -CO-O-, -O-CO-, -O-CO-O-, or CR-. 0 =CR 00 -、-C≡C-、 , , , , or The O and / or S atoms can be substituted in a way that prevents them from being directly connected to each other, and one or more H atoms can be optionally substituted by P-Sp-, F or Cl, or two substituents L connected to directly adjacent C atoms can also form cycloalkyl or cycloalkenyl groups with 5, 6, 7 or 8 C atoms.

[0203] m and l are independently 0, 1, 2 or 3.

[0204] k is 0, 1, or 2.

[0205] 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-.

[0206] In Equation I as described above and below In its daughter compounds, if R 3 or R 4If it is an alkyl or alkoxy group (i.e., the terminal CH2 group is substituted with -O-), it can be straight-chain or branched. It is preferably straight-chain, having 2, 3, 4, 5, 6, 7 or 8 carbon atoms, and is therefore preferably ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, ethoxy, propoxy, butoxy, pentoxy, hexoxy, heptoxy or octoxy, and also, for example, methyl, nonyl, decyl, undecyl, dodecyl, tridecyl, tetradecyl, pentadecyl, methoxy, nonoxy, decoxy, undecyloxy, dodecyloxy, tridecyloxy or tetradecyloxy.

[0207] The oxane group (i.e., one of the CH2 groups is -O-substituted) is preferably, for example, 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 or 2-, 3-, 4-, 5-, 6-, 7-, 8- or 9-oxadecyl.

[0208] Preferred Formula I Its daughter compounds are R 3 and R 4 At least one of them, preferably R 3 and R 4 Both refer to those of P-Sp-.

[0209] Other preferred formulations I Its daughter compounds are R 3 and R 4 At least one of them, preferably R 3 and R 4 Both differ from P-Sp- and preferably represent those having 1 to 12, more preferably 1 to 1 C atoms, of alkyl or alkoxy groups, R 3 and R 4 One of them can also represent F, Cl or CN.

[0210] Other preferred formulations I Its daughter compounds are A 3 and A 4Selected from the group consisting of: 1,4-phenylene, 1,3-phenylene, naphthalene-1,4-diyl, naphthalene-2,6-diyl, phenanthrene-2,7-diyl, 9,10-dihydro-phenanthrene-2,7-diyl, anthracene-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, coumarin, flavonoids, wherein, in addition, one or more CH groups in these groups may be replaced by N, cyclohexane-1,4-diyl In addition, one or more non-adjacent CH2 groups may be substituted with O and / or S, including 1,4-cyclohexenyl, bicyclo[1.1.1]pentane-1,3-diyl, bicyclo[2.2.2]octane-1,4-diyl, spiro[3.3]heptane-2,6-diyl, piperidine-1,4-diyl, decahydronaphthalene-2,6-diyl, 1,2,3,4-tetrahydronaphthalene-2,6-diyl, dihydroindene-2,5-diyl, octahydro-4,7-methylenedihydroindene-2,5-diyl, 2-benzyl-1-indone, chalcone, cronone, and dicyclopentadienone, all of which may optionally be substituted with one or more groups L or P-Sp-.

[0211] Very preferred form I Its daughter compounds are A 3 and A 4 Those selected from the group consisting of: 1,4-phenylene, naphthalene-1,4-diyl, naphthalene-2,6-diyl, 1,4-cyclohexylene, wherein, in addition, one or two non-adjacent CH2 groups may be substituted with 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-tetrahydro-naphthalene-2,6-diyl, very preferably 1,4-phenylene or 1,4-cyclohexylene, all of which may optionally be substituted with one or more groups L or P-Sp-.

[0212] Other preferred formulas I Its daughter compounds are Z. 3 and Z 4 Those that represent -CO-O-, -O-CO-, or single bonds independently of each other.

[0213] Other preferred formulas I The compound and its daughter formulas are those in which L is selected from the following: F, Cl, CN, CH3, C2H5, OCH3, OC2H5, COCH3, COC2H5, CF3, OCF3, P-Sp-, and in particular F, Cl, CN, CH3, C2H5, OCH3, COCH3 or OCF3, most preferably F, CH3, OCH3 or COCH3.

[0214] Other preferred formulations I The compounds thereof are those in which P is selected from the group consisting of: vinyloxy groups, acrylates, methacrylates, fluoroacrylates, chloroacrylates, oxetanes and epoxides, very preferably selected from acrylates and methacrylates, and most preferably acrylates.

[0215] Other preferred formulations I Its daughter compounds are those in which Sp represents a single bond or -(CH2). p1 -、-O-(CH2) p1 -、-O-CO-(CH2) p1 Or -CO-O-(CH2) p1 Those, 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 atom or CO- group is attached to the benzene ring.

[0216] Other preferred formulations I Compounds thereof are those in which all polymerizable groups P present in the compound have the same meaning and very preferably represent acrylate or methacrylate, most preferably acrylate.

[0217] Other preferred formulations I Compounds thereof are those containing one, two, three or four P-Sp groups, very preferably two or three P-Sp groups.

[0218] Other preferred formulations I Compounds thereof and their derivatives are those in which at least one Sp group is a single bond.

[0219] Other preferred formulations I Compounds thereof 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.

[0220] Other preferred formulations I Its derivative compounds are those in which at least one Sp group is different from a single bond and is selected from -(CH2). p1-、-O-(CH2) p1 -、-O-CO-(CH2) p1 Or -CO-O-(CH2) p1 Those, 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 atom or CO- group is attached to the benzene ring.

[0221] In R a or R b In the case of the P-Sp- group, the spacer groups on each side of the mesocrystalline nucleus may be the same or different.

[0222] In Equation I as described above and below In the compound and its derivatives, m and l are preferably 0 or 1.

[0223] In Equation I as described above and below In the compound and its daughter formulas, q is preferably 0 or 1, and very preferably 0.

[0224] The following formula I The following compounds are particularly preferred:

[0225] R -G- I 1

[0226] R -A 3 -Z 3 -GR I 2

[0227] R -A 3 -Z 3 -GZ 4 -A 4 -R I 3

[0228] P-Sp-G- I 4

[0229] P-Sp-A 3 -Z 3 -GR I 5

[0230] P-Sp-GZ 4 -A4 -R I 6

[0231] P-Sp-A 3 -Z 3 -GZ 4 -A 4 -R I 7

[0232] P-Sp-G-Sp-P I 8

[0233] P-Sp-A 3 -Z 3 -G-Sp-P I 9

[0234] P-Sp-A 3 -Z 3 -GZ 4 -A 4 -Sp-P I 10

[0235] P-Sp-A 3 -Z 3 -A 3 -Z 3 -GZ 4 -A 4 -Sp-P I 11

[0236] P-Sp-A 3 -Z 3 -A 3 -Z 3 -GZ 4 -A 4 -Z 4 -A 4 -Sp-P I 12

[0237] Among them, P, Sp, A 3 A 4 Z 3 Z 4 And G has the formula I as described above and below. The given meaning or one of its preferred meanings, R Having R different from P-Sp- 3 One of the meanings, and R Having R different from P-Sp- 4 One of the meanings.

[0238] Among these preferred compounds, Formula I is particularly preferred. 8 to I Of those 10, Formula I is particularly preferred. Those with the number 8.

[0239] Equation I is listed below. 1 to I The more preferred group of compounds of 10. For simplicity, Phe is a 1,4-phenylene optionally L-substituted at the 2- and / or 3-position, and Cyc is a 1,4-cyclohexylene.

[0240] Formula I 2, I3, I 5. I 6. I 7. I 9 and I The particularly preferred compounds of 10 are those with the following formula:

[0241] R -Phe-Z 3 -GR I 2-1

[0242] R -Cyc-Z 3 -GR I 2-2

[0243] R -Phe-Z 3 -GZ 4 -Phe-R I 3-1

[0244] R -Cyc-Z 3 -GZ 4 -Cyc-R I 3-2

[0245] R -Phe-Z 3 -GZ 4 -Cyc-R I 3-3

[0246] P-Sp-Cyc-Z 3 -GR I 5-1

[0247] P-Sp-Phe-Z 3 -GR I 5-2

[0248] P-Sp-G-Z 4 -Phe-R I 6-1

[0249] P-Sp-G-Z 4 -Cyc-R I 6-2

[0250] P-Sp-Phe-Z 3 -G-Z 4 -Phe-R I 7-1

[0251] P-Sp-Cyc-Z 3 -G-Z 4 -Cyc-R I 7-2

[0252] P-Sp-Phe-Z 3 -G-Z 4 -Cyc-R I 7-3

[0253] P-Sp-Cyc-Z 3 -G-Z 4 -Phe-R I 7-4

[0254] P-Sp-Cyc-Z 3 -G-Sp-P I 9-1

[0255] P-Sp-Phe-Z 3 -G-Sp-P I 9-2

[0256] P-Sp-Phe-Z 3 -G-Z 4 -Phe-Sp-P I 10-1

[0257] P-Sp-Cyc-Z 3 -G-Z 4 -Cyc-Sp-P I 10-2

[0258] P-Sp-Phe-Z 3 -G-Z4 -Cyc-Sp-P I 10-3

[0259] P-Sp-Phe-Z 3 -Phe-Z 3 -G-Z 4 -Phe-Sp-P I 11-1

[0260] P-Sp-Phe-Z 3 -Cyc-Z 3 -G-Z 4 -Phe-Sp-P I 11-2

[0261] P-Sp-Cyc-Z 3 -Phe-Z 3 -G-Z 4 -Phe-Sp-P I 11-3

[0262] P-Sp-Phe-Z 3 -Phe-Z 3 -G-Z 4 -Cyc-Sp-P I 11-4

[0263] P-Sp-Phe-Z 3 -Cyc-Z 3 -G-Z 4 -Cyc-Sp-P I 11-5

[0264] P-Sp-Cyc-Z 3 -Phe-Z 3 -G-Z 4 -Cyc-Sp-P I 11-6

[0265] P-Sp-Cyc-Z 3 -Cyc-Z 3 -G-Z 4 -Cyc-Sp-P I 11-7

[0266] P-Sp-Phe-Z 3 -Phe-Z 3 -G-Z 4 -Phe-Z 4 -Phe-Sp-P I 12-1

[0267] P-Sp-Phe-Z3 -Cyc-Z 3 -G-Z 4 -Phe-Z 4 -Phe-Sp-P I 12-2

[0268] P-Sp-Cyc-Z 3 -Phe-Z 3 -G-Z 4 -Phe-Z 4 -Phe-Sp-P I 12-3

[0269] P-Sp-Phe-Z 3 -Cyc-Z 3 -G-Z 4 -Cyc-Z 4 -Phe-Sp-P I 12-4

[0270] P-Sp-Cyc-Z 3 -Phe-Z 3 -G-Z 4 -Phe-Z 4 -Cyc-Sp-P I 12-5

[0271] P-Sp-Phe-Z 3 -Phe-Z 3 -G-Z 4 -Cyc-Z 4 -Cyc-Sp-P I 12-6

[0272] P-Sp-Cyc-Z 3 -Phe-Z 3 -G-Z 4 -Cyc-Z 4 -Cyc-Sp-P I 12-7

[0273] P-Sp-Phe-Z 3 -Cyc-Z 3 -G-Z 4 -Cyc-Z 4 -Cyc-Sp-P I 12-8

[0274] P-Sp-Cyc-Z 3 -Cyc-Z 3 -G-Z 4 -Cyc-Z 4 -Cyc-Sp-P I 12-9

[0275] Among them, P, Sp, Z 3 Z 4 And G has the formula I as described above and below. The given meaning or one of its preferred meanings, R Having Equation I R, which is different from P-Sp- 3 One of the meanings, and R Having Equation I R, which is different from P-Sp- 4 One of the meanings.

[0276] Preferably in formula I 2-1 to I In compound 10⁻⁶, R and R Independently, each is an alkyl or alkoxy group having 1 to 12 carbon atoms, or an alkyl or alkoxy group having 1 to 12 carbon atoms and the other being F, Cl, or CN. Furthermore, -Sp- is preferably an alkylene or alkylene group having 1 to 12 carbon atoms, P is preferably an acrylate or methacrylate, and Z... 3 and Z 4 They can be independently represented as -CO-O-, -O-CO-, -CH=CH-CO-O-, -O-CO-CH=CH-, -CH=C(CN)-CO-O-, -O-CO-C(CN)=CH-, -CH=N-, -N=CH-, -N=N- or single bonds, more preferably -CO-O-, -O-CO- or single bonds.

[0277] Preferred Formula I Its derivatives are those in which G represents or contains a photoisomerizable group.

[0278] Other preferred formulations I Its daughter compounds are Z. 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-.

[0279] Other preferred formulations 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.

[0280] Other preferred formulations I Compounds thereof are those in which the chiral group G is selected from or derived from the following: disohydrohexitol, preferably isosorbide, isomannitol or isotretinoin, 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 5 R 5-methyl-2-(1-methylethyl)cyclohexyl ester.

[0281] Very preferred form I Its derivative compounds are those in which the chiral group G is selected from formula A:

[0282]

[0283] Where X is -CO-O-, -CH=CH-CO-O-, or -CH=C(CN)-CO-O-, wherein the O atom of the ester in each is attached to a 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 given above and below.

[0284] Formula A includes the following stereoisomers based on the corresponding disohydrated hexitol:

[0285]

[0286]

[0287] Where X, L, and q have the meanings given in formula A, and Ai is based on isosorbide, Aii is based on isomannitol, and Aiii is based on isoidolitol. Ai is particularly preferred.

[0288] Other preferred formulations I Its daughter compounds are Z. 3 and Z 4One 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-.

[0289] Other preferred formulations 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-, and most preferably -CH=CH-CO-O-.

[0290] Other preferred formulations I Its derivatives are those in which the chiral group G is selected from the following formulas:

[0291]

[0292]

[0293] in

[0294] X, L, and q have one of the meanings or preferred meanings given in Equation A above and below.

[0295] R 11 and R 12 Represented independently as in Equation I -(Z) as defined in 4 -A 4 ) l -R 4 ,

[0296] or R 11 and R 12 Together with O atoms, they form optional structures as shown in Formula I. The group defined in the document -(Z) 4 -A 4 ) l -R 4 Substituted cyclic or spirocyclic groups,

[0297] R 13 and R 14 Represented independently as in Equation I R as defined in 3 -(A 3 -Z 3 ) m -,

[0298] a1 and a2 are independently 0, 1, or 2.

[0299] And the dashed line represents equation I. The bonding of adjacent groups in the middle.

[0300] Preferred Formula I The compounds are selected from the following formula:

[0301]

[0302] Where R 3 R 4 Z 4 A 4 L and q independently possess the same or different formula I each time they appear. The meaning given in the text or the preferred meaning given above and below, where I1 is 0, 1 or 2, R 13 R 14 a1 and a2 have one of the meanings given in formula G or the preferred meanings given above and below, R 15 Expression I -(Z) as defined in 4 -A 4 ) l -R 4 And X 11 and X 12 It represents -O-CO-CH=CH-.

[0303] Highly Preferred Formula I Compound A is selected from the following formulas:

[0304]

[0305]

[0306] Where P, Sp, L, and q have the equation I given above and below. R is one of the meanings or preferred meanings given in the text. Having a different formula I from P-Sp- Chinese R 3 One of the meanings, and R Having a different formula I from P-Sp- Chinese R 4 One of the meanings.

[0307] Formula I is particularly preferred. Compound A3.

[0308] Other preferred options are formula I. A, I B, I A1、I A2 and I A stereoisomer of A3, wherein the central isosorbide unit is replaced by an isomannitol or isoidutol unit.

[0309] In Equation I A, I B, I A1、I A2 and I In compound A3, P is preferably an acrylate or methacrylate, very preferably an acrylate, and Sp is preferably -O-(CH2). p1 -、-O-CO-(CH2) p1 -or -CO-O-(CH2) p1 - Most preferably -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.

[0310] Other preferred formulations I Its daughter compounds are selected from the following formulas:

[0311]

[0312]

[0313]

[0314]

[0315]

[0316]

[0317] Among them, P, Sp, R R L and q have the formula I given above and below. and I One of the meanings or preferred meanings given in A1, R 16 and R 17 Each of the above independently represents an alkyl group having 1 to 12, preferably 1 to 6, carbon atoms, most preferably methyl, ethyl, or propyl, and R 18 It represents P-Sp-, H or an alkyl group having 1 to 12, preferably 1 to 6, carbon atoms, very preferably H.

[0318] In Equation I C1 to I In 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 -, most preferably -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, independently of each other.

[0319] Formula IA can be prepared, for example, according to or similar methods described in GB 2314839 A. Compound. Formula I can be prepared, for example, according to or similar methods described in WO 02 / 40614 A1. E1 to I E15 compounds.

[0320] Preferably, the chiral isomerizable compounds used possess, individually or in combination, a helical torsion force (IHTP). 总 I) Absolute value is 20 µm -1 or higher, preferably 40 µm -1 Or higher, more preferably at 60 µm -1 Or in a higher range, most preferably at 80 µm -1 or even higher up to 260 µm -1 Within the range.

[0321] Preferably, the chiral isomerizable compound (especially selected from formula I) The proportion of the chiral isomerizable compound (or its derivative) in the RM mixture according to the invention is generally in the range of 0.1 to 4% by weight, very preferably in the range of 0.2 to 3% by weight, and most preferably in the range of 0.3 to 2% by weight.

[0322] In a preferred embodiment, in addition to the chiral isomerizable compound, the RM mixture also contains one or more, preferably exactly one, non-isomerizable chiral compound.

[0323] Preferably, the configuration of the isomerizable chiral compound is selected to be different from that of the non-isomerizable chiral compound. For example, if the isomerizable chiral compound is selected to have an (R) configuration, then a non-isomerizable chiral compound with an (S) configuration is preferred, and vice versa. Therefore, with respect to their respective helical torsion forces, the values ​​of HTP for the chiral compounds with different configurations can compensate for each other to obtain the resulting absolute value of HTP, which is also referred to below as IHTP. D I.

[0324] In a preferred embodiment, the chiral RM mixture comprises one or more chiral compounds having an (S)-configuration and one or more additional chiral compounds having an (R)-configuration, wherein at least one, preferably exactly one, of the chiral compounds having an (S)-configuration or (R)-configuration is selected from isomerizable chiral compounds, and the resulting IHTP D I at 0.1 µm -1 Up to 100 µm -1 Within the range, more preferably within 0.5 µm -1 up to 50 µm -1 Within the range, the optimal selection is at 1 µm. -1 up to 25 µm -1 Within the range.

[0325] The center wavelength of the reflection band of the RM mixture can be tuned by adding one or more non-isomerizable chiral compounds. The additional non-isomerizable chiral compound may have the same or opposite twist direction as the chiral isomerizable compound. Therefore, the reflection band of the RM mixture will shift to shorter or longer wavelengths, respectively. Preferably, the isomerizable and non-isomerizable chiral compounds have opposite optical rotations and therefore opposite twist directions.

[0326] In another preferred embodiment, the RM mixture contains one or more, preferably exactly one, chiral isomerizable compound, which is preferably polymerizable, especially selected from formula I. Or a compound of the formula thereof, and further comprising one or more, preferably exactly one, non-isomerizable chiral compound, optionally polymerizable and very preferably having a twist direction opposite to that of the chiral isomerizable compound.

[0327] Preferably, the additional polymerizable chiral compounds, alone or in combination with each other, have a molecular weight of 20 µm. -1 Or higher, preferably 40 µm -1 Or higher, more preferably at 60 µm -1 Or in a higher range, preferably at 80 µm -1 or even higher up to 260 µm -1 Absolute value of helical torsional force within the range (IHTP) 总 I).

[0328] In a preferred embodiment, the additional non-isomerizable chiral compound is selected from polymerizable compounds, which are preferably monoreactive or direactive.

[0329] Suitable non-isomerizable 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 that may be the same as or different from the mentioned linking groups. The ring elements are preferably selected from four-membered, five-membered, six-membered, or seven-membered rings, preferably the group consisting of five-membered or six-membered rings.

[0330] Preferred non-isomerizable polymerizable chiral compounds are selected from formulas CRM1, CRM2, and CRM3:

[0331]

[0332] Each group is independent of the others and, each time it appears, has the same or different meanings as follows:

[0333] P 0 It is a polymerizable group.

[0334] Sp 0 It is a spacer group or a single bond.

[0335] 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 -S -,

[0336] A 0 B 0 E 0 F 0 It is 1,4-phenylene, either unsubstituted or L-substituted with 1, 2, 3, or 4 groups, or trans-1,4-cyclohexylene.

[0337] 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.

[0338] X 1 X 2 It can be -O-, -COO-, -OCO-, -O-CO-O-, or a single bond.

[0339] Z 0 The bond type can be -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.

[0340] a0 can be 0, 1, or 2, preferably 0 or 1.

[0341] b0 is 0 or an integer from 1 to 12, preferably an integer from 1 to 6.

[0342] t0 is 0, 1, 2, or 3.

[0343] z0 can be 0 or 1, preferably 1.

[0344] Furthermore, the naphthalene ring may be substituted by one or more identical or different groups L.

[0345] Furthermore, the preferred stereoisomer is CRM2, wherein the central isosorbide unit is replaced by an isomannitol or isoidide unit.

[0346] The CRM1 compound is preferably selected from the following formula:

[0347]

[0348] Where A 0 B 0 Z 0 X 2 P 0 a and b have one of the meanings given in formula CRMa or the preferred meanings given in the context, and (OCO) represents -O-CO- or a single bond.

[0349] The preferred CRM compounds are selected from the group consisting of the following formulas:

[0350]

[0351]

[0352]

[0353] Where R -X as defined in formula CRM1-1 2-(CH2) t -P 0 Furthermore, the benzene ring and naphthalene ring are not substituted or are substituted by 1, 2, 3 or 4 groups L as defined above and below.

[0354] In the presence of one or more non-isomerizable polymerizable chiral compounds, the concentration of the chiral compound in the RM mixture is preferably 0.1% to 10%, more preferably 0.5% to 8%, based on the total weight of the RM mixture.

[0355] In another preferred embodiment, the additional non-isomerizable chiral compound is selected from non-polymerizable compounds. These chiral compounds may be amorphous or mesomorphic compounds.

[0356] Preferred non-isomerizable, non-polymerizable chiral compounds are selected from the group consisting of free C1 to C-III compounds.

[0357]

[0358]

[0359] Formulas C-II and C-III include the corresponding (S,S) enantiomers, wherein E and F are each independently 1,4-phenylene or trans-1,4-cyclohexylene, v is 0 or 1, and Z is 1. 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.

[0360] More preferably, it is a stereoisomer of formula C-II, wherein the central isosorbide unit is replaced by an isomannitol or isoidutol unit.

[0361] 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.

[0362] More preferred additional 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).

[0363] The amount of nonpolymerizable and non-isomerizable chiral dopant in the chiral RM mixture is preferably 0.1% to 10%, more preferably 0.5% to 8%, based on the weight of all solids.

[0364] Preferably, in addition to the chiral compound, the chiral RM mixture also contains one or more achiral RMs. Preferably, the RM mixture contains one or more additional achiral RMs having only one polymerizable functional group (single-reactive RM), and / or one or more additional achiral RMs having two or more polymerizable functional groups (two-reactive or multi-reactive RM).

[0365] Additional achiral bireactive or multireactive RMs are preferably selected from formula DRMs:

[0366] P 1 -Sp 1 -MG-Sp 2 -P 2 DRM

[0367] in

[0368] P 1 P 2 Each can independently represent a polymerizable group.

[0369] Sp 1 Sp 2 Each is an independent spacer group or a single bond, and

[0370] MG is a rod-shaped mesocrystalline group, preferably selected from the formula MG.

[0371] -(A 1 -Z 1 ) n -A 2 - MG

[0372] in

[0373] A 1 and A 2 In cases where they appear multiple times, they independently represent aromatic or alicyclic groups, which optionally contain one or more heteroatoms selected from N, O, and S, and are optionally mono- or poly-substituted with L.

[0374] L represents P-Sp-, F, Cl, Br, I, -CN, -NO2, -NCO, -NCS, -OCN, -SCN, and -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 substituted with F or Cl.

[0375] R x and R y Each can be independently represented by H or an alkyl group having 1 to 12 carbon atoms.

[0376] Z 1 When they appear multiple times, they can be represented independently as -O-, -S-, -CO-, -COO-, -OCO-, -S-CO-, -CO-S-, -O-COO-, -CO-NR. 00 -、-NR 00 -CO-、-NR 00 -CO-NR 000 -NR 00 -CO-O-、-O-CO-NR 00 -, -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.

[0377] Y 1 and Y 2 Each can be represented independently of H, F, Cl, or CN.

[0378] n can be 1, 2, 3, or 4, preferably 1 or 2, and most preferably 2.

[0379] n1 is an integer from 1 to 10, preferably 1, 2, 3 or 4.

[0380] Preferred group A 1 and A 2Including but not limited to furan, pyrrole, thiophene, oxazole, thiazole, thiadiazole, imidazole, phenylene, cyclohexylene, dicyclohexylene, cyclohexenylene, pyridine, pyrimidine, pyrazine, chamomile, indane, fluorene, naphthalene, tetrahydronaphthalene, anthracene, phenanthrene, and dithienothiophene, all of which are unsubstituted or substituted with 1, 2, 3, or 4 of the groups L as described above.

[0381] Especially preferred group A 1 and A 2 The 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-tetrahydro-naphthyl-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.

[0382] The preferred DRM is selected from the formula DRMa.

[0383]

[0384] in

[0385] P 0 When appearing multiple times, these groups are polymerizable independently, preferably acryloyl, methacryl, oxetane, epoxy, vinyl, heptaene, vinyloxy, propylene ether, or styrene.

[0386] Z 0 It can be -COO-, -OCO-, -CH2CH2-, -CF2O-, -OCF2-, -C≡C-, -CH=CH-, -OCO-CH=CH-, -CH=CH-COO-, or a single bond.

[0387] L, each time it appears, has the same or different meanings for the L in formula I. 1 One of the given meanings, and preferably, when appearing multiple times, is independently 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.

[0388] r is 0, 1, 2, 3, or 4.

[0389] x and y are independently 0 or the same or different integers selected from 1 to 12.

[0390] z is 0 or 1, and if the adjacent x or y is 0, then z is 0.

[0391] The preferred RM for the DRM formula is selected from the following formula:

[0392]

[0393]

[0394] Where P 0 L, r, x, y, and z are defined as in the formula DRMa.

[0395] Compounds of formula DRMa1, DRMa2 and DRMa3 are particularly preferred, especially compounds of formula DRMa1.

[0396] Additional non-chiral monoreactive RM is preferably selected from formula MRM:

[0397] P 1 -Sp 1 -MG-R 22 MRM

[0398] Where P 1 Sp 1 And MG has the meaning given in the DRM formula,

[0399] 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 substituted with F or Cl.

[0400] X is a halogen, preferably F or Cl, and

[0401] R x and R y They are H or alkyl groups having 1 to 12 carbon atoms, independent of each other.

[0402] The preferred MRM is selected from the following formula:

[0403]

[0404]

[0405]

[0406] Where P 0 L, r, x, y, and z are defined as in equation DRMa.

[0407] R 0 R 01 and R 02 Each is independently an alkyl, alkoxy, thioalkyl, alkylcarbonyl, alkoxycarbonyl, alkylcarbonyl or alkoxycarbonyloxy or representing Y having one or more, preferably one to 15 C atoms. 0 Or P-(CH2) y -(O) z -,

[0408] 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

[0409] Y 0 It is F, Cl, CN, NO2, OCH3, OCN, SCN, SF5, or a monofluorinated, oligofluorinated, or polyfluorinated alkyl or alkoxy group having 1 to 4 carbon atoms.

[0410] Z 0 It can be -COO-, -OCO-, -CH2CH2-, -CF2O-, -OCF2-, -CH=CH-, -OCO-CH=CH-, -CH=CH-COO-, or a single bond.

[0411] A 0 In multiple occurrences, 1,4-phenylene or trans-1,4-cyclohexylene is independently unsubstituted or L-substituted with 1, 2, 3, or 4 groups.

[0412] R 01、02 H and R are independent of each other. 0 Or Y 0 ,

[0413] u and v are 0, 1, or 2 independently of each other.

[0414] w is 0 or 1.

[0415] Furthermore, the benzene and naphthalene rings can be substituted by one or more identical or different groups L.

[0416] Compounds of formulas MRM1, MRM2, MRM3, MRM4, MRM5, MRM6, MRM7, MRM9 and MRM10 are particularly preferred, especially those of formulas MRM1, MRM4, MRM6 and MRM7.

[0417] In the formulas DRM, MRM, 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-.

[0418] 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 selected from F, Cl, CN, CH3, C2H5, C(CH3)3, CH(CH3)2, OCH3, COCH3 or OCF3, and most preferably selected from F, Cl, CH3, C(CH3)3, OCH3 or COCH3 or P-Sp-.

[0419] Preferably, the RM mixture comprises one or more RMs selected from DRM and MRM.

[0420] In the RM mixture according to this preferred embodiment, the concentration of the di-reactive or multi-reactive RM of the formula DRM and its sub-formulas is preferably 15% to 75%, and very preferably 25% to 65%. In the RM mixture according to this preferred embodiment, the concentration of the mono-reactive RM, preferably the mono-reactive RM of the formula MRM, is preferably 1% to 50%, and very preferably 5% to 30%.

[0421] In another preferred embodiment of the invention, in addition to or as an alternative to compounds of formula DRM and MRM, the chiral RM mixture also comprises one or more achiral RMs selected from formula I:

[0422]

[0423] Each group, independently of the others and in the same or different manner each time it appears, has the following meaning:

[0424] P is a polymerizable group.

[0425] Sp can be a spacer group or a single bond.

[0426] R 11 H, F, Cl, CN, or an optionally fluorinated alkyl, alkoxy, thioalkyl, alkylcarbonyl, alkoxycarbonyl, alkylcarbonyloxy, or alkoxycarbonyloxy group having 1 to 15 carbon atoms, preferably 1 to 5 carbon atoms, or P-Sp.

[0427] A, B, D, and E are selected from the group consisting of: 1,4-phenylene, naphthalene-1,4-diyl, naphthalene-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 one or more CH groups in these groups may be substituted with N, and all of the above may be optionally substituted with one or more L or P-Sp- groups.

[0428] C is selected from the group consisting of: phenyl-1,4-diyl, naphthalene-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, benzothiophene-4,7-diyl, all of which may be optionally substituted with one or more L or P-Sp groups.

[0429] Furthermore, either ring C or ring D can represent a single bond.

[0430] 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 substituted with -O-, -S-, -CO-, -CO-O-, -O-CO-, -O-CO-O-, or CR-. 0 =CR 00 -、-C≡C-、 Replacement

[0431] The alternative is that the O-atom and / or S-atom are not directly connected to each other, and one or more H atoms are each optionally replaced by P-Sp-, F or Cl, or the two substituents L connected to the directly adjacent C atom can also form a cycloalkyl or cycloalkenyl group with 5, 6, 7 or 8 C atoms.

[0432] Z 11 Z 12for -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 a single bond, preferably -COO-, -OCO-, -C≡C- or a single bond, most preferably a single bond.

[0433] n1 is 1, 2, 3, or 4.

[0434] r can be 0, 1, 2, 3 or 4, preferably 0, 1 or 2.

[0435] s can be 0, 1, 2, or 3, preferably 0, 1, or 2.

[0436] t can be 0, 1, or 2, preferably 0 or 1.

[0437] R 0 R 00 It is H or an alkyl group having 1 to 12 carbon atoms.

[0438] Y 1 Y 2 For H, F, Cl, NCS or CN,

[0439] n is 0, 1, 2, 3 or 4, preferably 0, 1 or 2, more preferably 0 or 1, and most preferably 0.

[0440] m is 0, 1, 2, 3 or 4, preferably 0, 1 or 2, more preferably 0 or 1, and most preferably 0.

[0441] In the compounds of formula I and its sub-formulas as described above and below, P is preferably selected from the group consisting of: ethylene oxy, acrylate, methacrylate, fluoroacrylate, chloroacrylate, oxetane and epoxide, very preferably selected from acrylate and methacrylate, and most preferably acrylate.

[0442] More preferably, compounds of formula I and its 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, and most preferably acrylates.

[0443] More preferably, compounds of formula I and its sub-formulas as described above and below, which contain one, two, three or four P-Sp groups, and very preferably contain two or three P-Sp groups.

[0444] More preferably, compounds of formula I and its derivatives as described above and below, wherein R 11 It is P-Sp-.

[0445] More preferably, compounds of formula I and its derivatives as described above and below, wherein R 11 Unlike P-Sp-, and preferably selected from CN, -SCN, preferably having 1 to 12, more preferably 1 to 6 C atoms, of optionally fluorinated alkyl, alkoxy, thioalkyl, alkylcarbonyl, alkoxycarbonyl, alkylcarbonyloxy or alkoxycarbonyloxy.

[0446] More preferably, compounds of formula I and its sub-formulas as described above and below, wherein Sp represents 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 Then the O-atom or CO-group is bonded to the benzene ring.

[0447] More preferably, compounds of formula I and its sub-formulas as described above and below, wherein at least one Sp group is a single bond.

[0448] More preferably, compounds of formula I and its sub-formulas as described above and below, wherein at least one group Sp is a single bond and at least one group Sp is different from the single bond.

[0449] More preferably, compounds of formula I and its sub-formulas as described above and below, wherein at least one Sp group differs from the single bond and is selected from -(CH2). p1 -、-O-(CH2) p1 -、-O-CO-(CH2) p1 Or -CO-O-(CH2) p1Where 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-atom or CO-group is bonded to the benzene ring.

[0450] More preferably, compounds of formula I and its derivatives as described above and below, wherein L is a p-Sp-, -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 substituted with -O-, -S-, -CO-, -CO-O-, -O-CO-, -O-CO-O-, or CR-. 0 =CR 00 -、-C≡C-、 Replacement

[0451] The alternative is that the O-atom and / or S-atom are not directly connected to each other, and one or more H atoms are each optionally replaced by P-Sp-, F or Cl, or the two substituents L connected to the directly adjacent C atom can also form a cycloalkyl or cycloalkenyl group with 5, 6, 7 or 8 C atoms.

[0452] Highly preferred are compounds of formula I and its sub-formulas as described above and below, wherein L is a straight-chain alkyl, alkoxy, or thioalkyl having 1 to 6 carbon atoms, or a branched or cyclic alkyl, alkoxy, or thioalkyl having 3 to 8 carbon atoms.

[0453] More preferably, compounds of formula I and its sub-formulas as described above and below, wherein Z 11 and Z 12 It can be represented as -COO-, -OCO-, -C≡C- or a single bond, more preferably -C≡C- or a single bond, and most preferably a single bond.

[0454] Preferably, A, B, D, and E in Formula I are selected from the group consisting of the following:

[0455]

[0456] Each group, independently of the others and in the same or different manner each time it appears, has the following meaning:

[0457] L is P-Sp-, -CN, F, Cl, or optionally fluorinated and has 1 to 6, preferably 1 to 3, more preferably alkyl, alkoxy, or thioalkyl with 1 or 2 C atoms, preferably P-Sp-, -CN, F, Cl, OCH3, SCH3, C2H5, OC2H5, or SC2H5.

[0458] r can be 0, 1, 2, 3 or 4, preferably 0, 1 or 2.

[0459] s can be 0, 1, 2, or 3, preferably 0 or 1.

[0460] t can be 0, 1, or 2, preferably 0 or 1.

[0461] More preferably, rings A, B, D and / or E in Formula I are selected from the group consisting of: 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 may optionally be substituted with one or more groups L and / or P-Sp-.

[0462] Very preferably, one, two, three, four or more of rings A, B, D and / or E in Formula I are selected from the group consisting of:

[0463]

[0464] ,

[0465] 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 alkyl, alkoxy, or thioalkyl, preferably P-Sp-, -CN, F, Cl, OCH3, SCH3, C2H5, OC2H5, or SC2H5.

[0466] Especially preferred are compounds of formula I, particularly where n=m=0, wherein rings B and D are selected from the group consisting of: phenyl-1,4-diyl, naphthalene-1,4-diyl, naphthalene-2,6-diyl or anthracene-9,10-diyl, all of which may be optionally monosubstituted or disubstituted by L and / or P-Sp-.

[0467] Preferably, the ring C in formula I is selected from the group consisting of the following:

[0468] , , and

[0469] Each group, independently of the others and in the same or different manner each time it appears, has the following meaning:

[0470] L is P-Sp-, -CN, F, Cl, or optionally fluorinated and has 1 to 6, preferably 1 to 3, more preferably alkyl, alkoxy, or thioalkyl with 1 or 2 C atoms, preferably P-Sp-, -CN, F, Cl, OCH3, SCH3, C2H5, OC2H5, or SC2H5.

[0471] r can be 0, 1, 2, 3 or 4, preferably 0, 1 or 2.

[0472] s can be 0, 1, 2, or 3, preferably 0 or 1.

[0473] t can be 0, 1, or 2, preferably 0 or 1.

[0474] More preferably, C in formulas I, I1, and I2 is selected from the group consisting of the following:

[0475] 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 alkyl, alkoxy, or thioalkyl, preferably P-Sp-, -CN, F, Cl, OCH3, SCH3, C2H5, OC2H5, or SC2H5.

[0476] Very preferably, the ring C in Formula I is selected from the group consisting of: phenyl-1,4-diyl, naphthalene-1,4-diyl, or anthracene-9,10-diyl, all of which may be optionally monosubstituted or disubstituted with L and / or P-Sp-.

[0477] More preferably, compounds of formula I, especially those in which n=m=0, wherein rings B, C, and D form groups selected from the following formulas or their mirror images:

[0478]

[0479]

[0480]

[0481]

[0482] The naphthalene and phenanthrene groups are optionally substituted with one or two L groups, and L 1 and L 2 H can be represented independently of each other or have one of the meanings given for L in Equation I, and L and r are as defined in Equation I.

[0483] In formulas T1 to T28, preferably, L represents P-Sp-, -CN, F, Cl or optional fluorination in each occurrence 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-, 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.

[0484] Especially preferred are groups of formulas T1 to T7.

[0485] The most preferred compounds of formula I are selected from the following sub-formulas:

[0486]

[0487]

[0488]

[0489]

[0490]

[0491]

[0492]

[0493]

[0494]

[0495]

[0496] 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 I or one of the preferred meanings given above and below, and R has the meaning of R in Formula I1. 11 One of the given meanings is given, and it is preferably OCH3 or SCH3, very preferably OCH3. L is preferably selected from alkyl, alkoxy, or thioalkyl groups having 1 to 6, more preferably 1, 2, or 3 C atoms, and very preferably selected from methyl or ethyl groups. P is preferably an acrylate.

[0497] More preferably, compounds of formula I1 and I1-1 to I1-103, wherein one of the two Sp groups is a single bond and the other Sp group is different from the single bond.

[0498] More preferably, the compounds of formula I and I-1 to I1-103 are selected from the following preferred embodiments (including any combination thereof):

[0499] - n=m=0, or

[0500] - n=1 and m=0, or

[0501] - n=m=1, and / or

[0502] - One of ring B and ring D is a single bond, and / or

[0503] - The ring C represents naphthalene-1,4-diyl or anthracene-9,10-diyl, or

[0504] - The ring C represents phenyl-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, and / or

[0505] - At least one of rings B and D represents naphthalene-1,4-diyl, naphthalene-2,6-diyl, or anthracene-9,10-diyl, optionally substituted with one or more L or P-Sp groups, and / or

[0506] - At least one of rings B, C, and D represents naphthalene-1,4-diyl, naphthalene-2,6-diyl, or anthracene-9,10-diyl, optionally substituted with one or more L- or P-Sp- groups, and / or at least one of rings B, C, and D is an ethyl-substituted phenyl-1,4-diyl.

[0507] - P indicates acrylate or methacrylate, and / or

[0508] - 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

[0509] - If R 11 If R is P-Sp-, then the two groups are the same (P-Sp-).

[0510] - If R 11 Or R is P-Sp-, then one of the Sp groups is a single bond and the other Sp group is different from the single bond, and / or

[0511] - L is selected from methyl, ethyl, methoxy, ethoxy, or thiomethyl, more preferably methyl or ethyl, very preferably ethyl, and r represents 1, and / or

[0512] - L is selected from methyl, ethyl, methoxy, ethoxy, or thiomethyl, more preferably methyl or ethyl, very preferably ethyl, and r represents 2, and / or

[0513] - The ring C is substituted with an L, where L represents P-Sp-, preferably an acrylate, and / or

[0514] - R 11 For P-Sp-, or

[0515] - R 11 The component is F, Cl, CN, OCH3 or SCH3, preferably OCH3 or SCH3. ， OCH3 is the most preferred.

[0516] The most preferred compounds of formula I are listed below:

[0517]

[0518]

[0519]

[0520]

[0521]

[0522]

[0523]

[0524]

[0525]

[0526]

[0527] Particularly preferred are compounds of the formulas I-3, I-19, I-21, I-24, I-25, I-30, I-47, I-50, I-53, I-59, I-67, I-69, I-70, I-72 and I-73.

[0528] Compounds of Formula I are characterized by very high birefringence. The synthesis of compounds of Formula I and its sub-formulas can be carried out by methods known to those skilled in the art from the literature itself or in a similar manner, such as those described in WO 2022 / 33908A1.

[0529] Compounds of Formula I, obtained alone or in combination with other RMs in RM mixtures, particularly and preferably simultaneously exhibit high birefringence, good solubility in commonly known organic solvents used in mass production, modified orientation in RM mixtures, favorable transition temperatures, and high resistance to yellowing after exposure to UV light.

[0530] Preferably, the RM mixture contains one or more, preferably 1 to 5, very preferably 1, 2 or 3 compounds selected from Formula I, preferably selected from Formula I-1 to I-97, and very preferably selected from Formula I1 to I76.

[0531] The concentration of the compound of formula I or its derivatives in the RM mixture is preferably 65 to 99%, and very preferably 25 to 98%.

[0532] In another preferred embodiment, the RM mixture contains only a small amount of a compound of formula I. Therefore, it is possible to provide an RM mixture primarily composed of monoreactive, direactive, and / or multireactive RMs, preferably selected from formulas DRM and MRM, and their derivatives, doped with a small amount, preferably 5% to 30%, of a compound of formula I, and additionally containing one or more compounds preferably selected from formula I. Chiral isomerizable compounds.

[0533] Preferably, the chiral RM mixture comprises at least one RM with a birefringence ≥ 0.25, most preferably ≥ 0.28. Suitable RMs with high birefringence are, for example, those selected from Formula I and its sub-formulas as defined above and below.

[0534] The RM mixture preferably exhibits a chiral nematic LC phase, or a chiral smectic LC phase and a chiral nematic LC phase, most preferably a chiral nematic LC phase at room temperature.

[0535] The birefringence (Δn) of the RM mixture is preferably in the range of 0.2 to 0.8, more preferably in the range of 0.25 to 0.7, and even more preferably in the range of 0.35 to 0.6.

[0536] Preferably, the chiral RM mixture comprises an achiral host mixture and a chiral component. The achiral host mixture preferably comprises one or more monoreactive and / or direactive achiral RMs, most preferably selected from formulas DRM, MRM, and I and their derivatives, and is very preferably composed thereof. The chiral component preferably comprises one or more chiral compounds, most preferably composed thereof, at least one of which is isomerizable and preferably selected from formula I. CRM1, CRM2 and CRM3 and their sub-forms.

[0537] The proportion of the non-chiral host mixture in the chiral RM mixture 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%.

[0538] In a preferred embodiment, a chiral RM mixture of two quarter-wave plates with opposite twist directions is prepared by adding a chiral component that induces opposite twist directions to a non-chiral bulk mixture. For example, two chiral isomerizable compounds with opposite twist directions can be used. Alternatively, two chiral components can be used, each comprising a first isomerizable chiral compound and a second non-isomerizable chiral compound with opposite twist directions, wherein the concentrations and HTP values ​​of the first and second chiral compounds can be selected such that the two chiral components have opposite twist directions after the isomerization process.

[0539] In another preferred embodiment, the chiral RM mixture used to prepare the first quarter-wave plate and the chiral RM mixture used to prepare the second quarter-wave plate are based on the same achiral host mixture, to which (R)-stereoisomers or (S)-stereoisomers of the same chiral isomerizable compound are added respectively to prepare two chiral RM mixtures with opposite twists for the first and second quarter-wave plates.

[0540] Therefore, for example, the chiral RM mixture for the first quarter-wave plate is prepared by adding the (R)-stereoisomer of the chiral isomerizable compound to the achiral RM main mixture, and the chiral RM mixture for the second quarter-wave plate is prepared by adding the corresponding (S)-stereoisomer of the chiral isomerizable compound to the achiral RM main mixture, or vice versa.

[0541] Another object of the present invention is an RM formulation comprising the RM mixture described above and below, and further comprising one or more solvents and / or additives.

[0542] Includes selections from formulas I and I The proportion of the RM mixture consisting of the following compounds, 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%, in the RM formulation.

[0543] In another preferred embodiment of the invention, the chiral RM mixture does not contain compounds of formula I or MRM. In another preferred embodiment, the chiral RM mixture is composed of compounds selected from formulas I and II. It is composed of compounds selected from CRM1, CRM2, CRM3, CI, C-II and C-III.

[0544] In another preferred embodiment, the RM formulation optionally includes one or more additives selected from the group consisting of: polymerization initiators, surfactants, stabilizers, catalysts, photosensitizers, inhibitors, chain transfer agents, co-reactive monomers, reactive thickeners, surfactants, lubricants, wetting agents, dispersants, hydrophobic agents, adhesives, flow improvers, degassing agents or defoamers, degassing agents, diluents, reactive diluents, auxiliaries, colorants, dyes, pigments, and nanoparticles.

[0545] In another preferred embodiment of the invention, the RM mixture and / or RM formulation does not contain compounds having at least one CF3 or CF2 group (PFAS), and very preferably, the RM mixture and / or RM formulation does not contain compounds having polyfluorinated alkyl, aryl, or perfluorocarbon groups. More preferably, the RM mixture and / or RM formulation does not contain compounds having fluorinated aliphatic C atoms, and most preferably, the RM mixture and / or RM formulation does not contain compounds having fluorinated C atoms. Therefore, the RM mixture and RM formulation of this preferred embodiment can indeed reduce perfluorocarbon compounds.

[0546] Another objective of this invention is the RM mixtures and / or RM formulations (which are free of PFAS, more preferably free of perfluorocarbons, very preferably free of compounds with polyfluorinated C atoms, and most preferably free of compounds with fluorinated C atoms) as described above and below.

[0547] In another preferred embodiment, the RM formulation includes one or more specific antioxidant additives preferably selected from the Irganox® series, such as antioxidants Irganox® 1076 and Irganox® 1010 purchased from Ciba, Switzerland.

[0548] In another preferred embodiment, the RM formulation comprises a combination of one or more, more preferably 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, further selected from commercially available OXE02 (Ciba AG), NCI 930, N1919T (Adeka), SPI-03 or SPI-04 (Samyang), TR-PBG 304 or TR-PGB 345 (Tronly).

[0549] The concentration of one or more polymerization initiators in the RM formulation is generally preferred to be 0.1 to 6%, very preferred to be 0.3 to 4%, and more preferably 0.7 to 2%.

[0550] In another preferred embodiment, the ratio between the concentration of the photoinitiator and the concentration of the chiral compound in the chiral RM mixture is generally 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.

[0551] In another embodiment, the RM formulation optionally includes one or more additives (reactive thickeners) selected from polymerizable non-mesomorphic compounds. The amount of these additives in the RM formulation is preferably 0 to 30%, and very preferably 0 to 25%.

[0552] 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.

[0553] 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.

[0554] 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.

[0555] Other suitable reactive tack reducers are polyester (meth)acrylates, which are (meth)acrylates of polyesterol.

[0556] 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.

[0557] In addition, suitable reactive tack reducers are 1,4-divinylbenzene, triallyl cyanurate, and acrylates of tricyclodecenyl alcohol of the following formula.

[0558]

[0559] It is also known as dihydrodicyclopentadienyl acrylate, as well as allyl esters of acrylic acid, methacrylic acid and cyanoacrylate.

[0560] 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.

[0561] 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.

[0562] In addition, the groups also include, for example, alkoxylated phenolic compounds, such as ethoxylated and propoxylated bisphenols.

[0563] In addition, these reactive tack reducers can be, for example, epoxy or urethane (meth)acrylate.

[0564] 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.

[0565] 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.

[0566] Such epoxy and urethane (meth)acrylate esters are included as "mixed forms" in the compounds listed above.

[0567] 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.

[0568] For example, the group of diluents includes:

[0569] 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, tetrahydropropanol, etc. Furans and dioxanes, 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 heating oil, and natural oils such as olive oil, soybean oil, rapeseed oil, linseed oil and sunflower oil.

[0570] Of course, mixtures of these diluents can also be used in the compositions according to the invention.

[0571] 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.

[0572] The diluent may be used at a ratio of approximately 0 to 10.0% by weight, preferably approximately 0 to 5.0% by weight, based on the total weight of the RM formulation.

[0573] 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-resistant aids (c8) cannot be strictly separated from each other by their functions.

[0574] 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 aids. In various cases, some of these aids can also function as adhesion promoters (c8).

[0575] Accordingly, certain additives can therefore be classified into several groups c1) to c8) as described below.

[0576] 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.

[0577] 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.

[0578] 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).

[0579] 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® Airex 900, Tego® Airex 910, Tego® Airex 931, Tego®Airex 935, Tego® Airex 936, Tego® Airex 960, Tego® Airex 970, Tego® Airex 980 and Tego® Airex 985 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.

[0580] 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.

[0581] 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.

[0582] 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.

[0583] 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.

[0584] 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.

[0585] 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.

[0586] 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 act 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).

[0587] 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.

[0588] In group c3), thermosetting aids contain, for example, primary OH groups that can react with, for example, isocyanate groups of adhesives.

[0589] Examples of available thermosetting aids are BYK®-370, BYK®-373 and BYK®-375, which are products available from BYK.

[0590] 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.

[0591] 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.

[0592] 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 and BYK®-348.

[0593] 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.

[0594] 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.

[0595] 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.

[0596] 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).

[0597] Such wetting and dispersing aids 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.

[0598] 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.

[0599] 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.

[0600] 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.

[0601] 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.

[0602] 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.

[0603] Adhesion promoters from group C7) are used to improve the adhesion between two interfaces of a contact. It is directly apparent that, essentially, the only effective portion of an adhesion promoter is 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 promoter must be added directly to the latter, or the substrate must be pretreated with the adhesion promoter (also known as applying a primer), i.e., to impart altered chemical and / or physical surface properties to the substrate.

[0604] 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.

[0605] In a broader sense, adhesion promoters can also be mentioned, as are substrate wetting aids already listed in group C4), but these generally do not have the same adhesion promoting ability.

[0606] Given the wide range of physical and chemical properties of 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.

[0607] 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®.

[0608] 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.

[0609] 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.

[0610] 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.

[0611] 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.

[0612] Examples of light, heat, and / or oxidation stabilizers that may be mentioned are the following substances:

[0613] 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.

[0614] 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.

[0615] 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”).

[0616] 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.

[0617] 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.

[0618] 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.

[0619] 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,

[0620] 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,

[0621] 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.

[0622] Acylaminophenols, such as 4-hydroxylauroyl aniline, 4-hydroxystearoyl aniline, and octyl N-(3,5-di-tert-butyl-4-hydroxyphenyl)carbamate,

[0623] 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.

[0624] 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.

[0625] 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.

[0626] 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,

[0627] 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.

[0628] 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;

[0629] 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.

[0630] 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,

[0631] 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.

[0632] 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.

[0633] 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

[0634] 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.

[0635] In a preferred embodiment, the RM formulation is dissolved in a suitable solvent, preferably an organic solvent.

[0636] Solvents are preferably selected from ketones, such as acetone, methyl ethyl ketone, methyl propyl ketone, methyl isobutyl ketone, or cyclohexanone; acetate esters, such as methyl acetate, ethyl acetate, butyl acetate, or methyl acetoacetate; alcohols, such as methanol, ethanol, or isopropanol; aromatic solvents, such as toluene or xylene; alicyclic hydrocarbons, such as cyclopentane or cyclohexane; halogenated hydrocarbons, such as dichloromethane or chloroform; glycols or their esters, such as PGMEA (propylene glycol monomethyl ether acetate) or γ-butyrolactone. Binary, ternary, or higher mixtures of the above solvents may also be used. In particular, methyl isobutyl ketone is a preferred solvent for multilayer applications.

[0637] When the RM formulation contains one or more solvents, the total concentration of all solids (including RM) in the solvent is preferably 5 to 60%, more preferably 10 to 50%, and particularly 10 to 35%.

[0638] Preferably, in addition to one or more compounds of Formula I and chiral isomerizable compounds, the RM formulation also comprises:

[0639] a) One or more of the following multi-reactive or two-reactive polymerizable mesocrystalline compounds, preferably selected from compounds of the formula DRM and its corresponding formula, and / or

[0640] b) Optional one or more additional polymerizable chiral compounds, preferably selected from formula CRM or its subformulas, and / or

[0641] c) Optional one or more additional non-polymerizable chiral compounds, preferably selected from formulas C1, C-II, and C-III, and / or

[0642] d) Optional one or more monoreactive mesomorphs, preferably selected from compounds of formula MRM and its counterpart, and / or

[0643] e) One or more photoinitiators, and / or

[0644] f) Optional one or more antioxidant additives, and / or

[0645] g) Optional one or more adhesion promoters, and / or

[0646] h) One or more surfactants, and / or

[0647] i) Any one or more monoreactive, direactive, or multireactive polymerizable non-mesomorphic compounds, and / or

[0648] j) One or more dyes, optionally, that exhibit maximum absorption at the wavelength used to initiate photopolymerization, and / or

[0649] k) Optional one or more chain transfer agents, and / or

[0650] l) Optional one or more (UV) stabilizers, and / or

[0651] m) One or more optional lubricants and flow aids, and

[0652] n) One or more optional diluents, and / or

[0653] o) Optional non-polymerizable nematic components, and / or

[0654] p) One or more organic solvents may be used.

[0655] More preferably, the RM formulation comprises:

[0656] a) One or more compounds of formula I or their corresponding preferred formulas.

[0657] b) One or more chiral isomerizable compounds, preferably selected from formula I. More preferably selected from Formula I A or its corresponding preferred sub-formula

[0658] c) Optionally one or more, preferably two or more, two-reactive polymerizable mesocrystalline compounds, preferably selected from compounds of formula DRMa-1.

[0659] d) Optionally one or more, preferably two or more, monoreactive polymerizable mesocrystalline compounds, preferably selected from compounds of formula MRM-1 and / or MRM-4 and / or MRM-6 and / or MRM-7.

[0660] e) Optional one or more additional polymerizable chiral compounds, preferably selected from formula CRM or its subforms.

[0661] f) Optionally one or more additional non-polymerizable chiral compounds, preferably selected from formulas C1, C-II, and C-III.

[0662] g) Optional one or more antioxidant additives,

[0663] h) One or more photoinitiators may be selected.

[0664] i) One or more organic solvents, optionally.

[0665] RM mixtures and RM formulations can be prepared in conventional ways, such as by mixing one or more of the chiral isomerizable compounds mentioned above with one or more RMs as defined above, and optionally with other additives.

[0666] The present invention further relates to a method for preparing various polymer films, comprising the following steps, preferably consisting of the following steps:

[0667] p1) A first layer of the RM mixture or RM formulation described above and below is provided on a substrate, the substrate optionally having an alignment layer capable of inducing planar alignment with adjacent layers of the RM mixture.

[0668] p2) If any solvent is present, it may be removed optionally.

[0669] p3) Optionally, the RM mixture (i.e., without solvent) is preferably annealed at the temperature at which it is a chiral nematic phase.

[0670] p4) First irradiation step (first UV step): Irradiate the RM mixture in air with photochemical radiation, preferably with UV radiation.

[0671] p5) Optionally, the RM mixture is preferably annealed at a temperature at which it is a chiral nematic phase, and

[0672] p6) Second irradiation step (second UV step): Irradiate the RM mixture with photochemical radiation, preferably with UV radiation, in an inert gas atmosphere.

[0673] More preferably, the method for preparing the various polymer films according to the present invention includes the following steps:

[0674] p11) A layer or solution of the RM mixture or RM formulation described above and below is provided onto a substrate, preferably equipped with an alignment layer (e.g., a rubbed polyimide layer or a photo-alignment layer) induced by spin coating or printing, and optionally any present solvent is removed.

[0675] p22) If any solvent is present, it may be removed optionally.

[0676] p33) Optionally, the RM mixture layer (i.e., without solvent) is preferably annealed at the temperature at which it is a chiral nematic phase.

[0677] (p44) Preferably, the RM mixture layer (i.e., without solvent) is exposed to UV light in an air environment at ambient temperature, which causes photoisomerization of the chiral compound containing photoisomerizable groups and provides a chiral structure with a biased helical pitch. Exposure to unpolarized UV light is preferred, and exposure to unpolarized UVA light is very preferred, for example at 40 to 500 mJ / cm². 2 The dosage (“first UV step”),

[0678] (p55) Optionally, the RM mixture is preferably annealed at a temperature at which it is a chiral nematic phase.

[0679] P66) Preferably, the RM mixture layer is exposed to UV light in an inert gas atmosphere (e.g., nitrogen) at ambient temperature, which causes photopolymerization of the RM. Exposure to unpolarized UV light is preferred, and exposure to unpolarized UVA light is very preferred, for example, at 200 to 2000 mJ / cm². 2 cm 2 The dose (“second UV step”).

[0680] The present invention further relates to a method for preparing a half-wave plate, which includes the following steps, preferably consisting of the following steps:

[0681] p1) The first quarter-wave plate is formed by a method comprising the following steps, preferably the following steps:

[0682] p11) A layer of the chiral RM mixture described above and below is provided on a substrate, which optionally has an alignment layer capable of inducing planar alignment with adjacent layers of the chiral reactive mesocrystalline mixture.

[0683] p12) If any solvent is present, it may be removed optionally.

[0684] p13) Optionally, the chiral reactive mesocrystalline mixture layer is preferably annealed at the temperature at which it is a chiral nematic phase.

[0685] p14) The first step (first UV step) involves irradiating the chiral reactive mesocrystalline mixture in air with photochemical radiation, preferably UV radiation.

[0686] p15) Optionally, the chiral reactive mesocrystalline mixture layer is preferably annealed at the temperature at which it is a chiral nematic phase, and

[0687] p16) The second step (second UV step) involves irradiating the chiral reactive mesocrystalline mixture with photochemical radiation, preferably UV radiation, in an inert gas atmosphere.

[0688] p2) A second quarter-wave plate is formed by a method comprising steps p11) to p16) as described above, preferably consisting of these steps, wherein the chiral RM mixture of the first and second quarter-wave plates has opposite twists.

[0689] p3) Combine the first quarter-wave plate and the second quarter-wave plate to form a half-wave plate.

[0690] The first and second quarter-wave plates can be combined with each other, for example, by laminating films onto each other. Alternatively, the second quarter-wave plate can be prepared directly on top of the first quarter-wave plate, which serves as a substrate. Film lamination or coating can also be performed in a roll-to-roll process.

[0691] Preferably, in the method according to the invention, all irradiation or UV exposure steps are performed at room temperature, and the layer of the RM mixture or RM formulation is not subjected to heat treatment during or between irradiation or UV exposure steps.

[0692] The first irradiation step or the first UV step induces photoisomerization of the chiral compound containing photoisomerizable groups and provides a chiral structure with a biased helical pitch. The second irradiation step or the second UV step induces photopolymerization of the polymerizable mesocrystalline compound and thereby fixes the chiral structure.

[0693] Without being bound by a specific theory, the inventors believe that the presence of oxygen in the air during the first UV step inhibits free radical polymerization. This effect offers several advantages.

[0694] First, this effect also allows for the use of RMs with maximum absorption in the same UV wavelength range as the photoisomerizable chiral compounds, and therefore, unless hindered, they will polymerize. Because suitable RMs with extremely high birefringence and suitable chiral photoisomerizable compounds are typically difficult to find, this allows for a wider selection of suitable mixture components, making the chiral RM mixture composition more readily adaptable to the specific requirements of the polymer film's end use as a half-wave plate.

[0695] Second, this effect can be advantageously applied to partially polymerized membranes with a gradient in the membrane thickness direction. Thus, the RM at the top of the membrane exposed to oxygen has a lower polymerization rate, while the RM at the bottom of the membrane (at the substrate interface) is much less hindered by oxygen and therefore can polymerize more easily.

[0696] Due to the presence of photoisomerizable chiral compounds, photoisomerization occurs during the first UV step, and the helical twist force (HTP) of the photoisomerizable chiral compounds decreases upon exposure to UV light. In regions of higher polymer density, changes in the chiral structure are physically resisted. At the top or surface of the film, the polymer density is low, allowing for greater freedom in modifying the chiral structure. However, at the bottom of the film adjacent to the substrate (where more photopolymerization occurs), the polymer density is higher, thus hindering changes in the chiral structure. This results in a chiral pitch gradient within the film. Therefore, after the method described above, the polymerized RM mixture exhibits accelerated chiral rotation in the direction of the principal plane of the polymer film or the film thickness. Preferably, the polymerized RM mixture exhibits an offset pitch such that the chiral rotation angle gradually increases or decreases across the film thickness.

[0697] RM mixtures or RM formulations can be coated or printed onto a substrate, for example by spin coating, printing, or other known techniques, with the solvent evaporated before polymerization. In most cases, heating the mixture to promote solvent evaporation is suitable.

[0698] RM mixtures or RM formulations can be coated onto the substrate using conventional coating techniques such as spin coating, bar coating, or blade coating. They can also be applied to the substrate using conventional printing techniques known to the expert, such as screen printing, offset printing, roll-to-roll printing, letterpress printing, gravure printing, rotary gravure printing, flexographic printing, engraving gravure printing, pad printing, heat-sealing printing, inkjet printing, or printing via stamps or printing plates.

[0699] Suitable substrate media and substrates are known to experts and described in the literature, such as conventional substrates used in the optical film industry, such as glass or plastic. 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.

[0700] In another preferred embodiment, the substrate has a surface grating or surface pattern. In another preferred embodiment, the substrate is prepared from a photoalignment layer (PAL), and the photoalignment layer is patterned by laser interferometry to produce a grating pattern with a defined pitch.

[0701] The Friedel-Creagh-Kmetz law can be used to compare the surface energy (γ) of the RM layer. RM ) and the surface energy (γ) of the substrate s To predict whether a mixture will adopt planar or perpendicular alignment:

[0702] If γ RM > γ s Then the reactive mesocrystalline compound will exhibit perpendicular alignment, if γ RM <γ s In this case, the reactive mesocrystalline compound will exhibit face-oriented alignment.

[0703] In situations where it is undesirable to be bound by a specific theory, when the surface energy of the substrate is relatively low, the intermolecular forces between reactive mestic crystals are stronger than the forces pervading the RM-substrate interface. Consequently, the reactive mestic crystals are aligned perpendicular to the substrate (perpendicular alignment) to maximize the intermolecular forces. Therefore, an additional alignment layer is needed that can induce planar alignment with the adjacent RM mixture.

[0704] When the surface tension of the substrate is greater than that of the RM, the forces throughout the interface dominate. If the reactive mesomorph is aligned parallel to the substrate, the interfacial energy is minimized, and thus the long axis of the RM can interact with the substrate. Unidirectional planar alignment can be promoted by coating the substrate with a polyimide layer and then rubbing the alignment layer with a velvet cloth.

[0705] Other suitable planar alignment layers are known in the art, such as rubbed polyimides or alignment layers prepared by photoalignment, as described in US 5,602,661, US 5,389,698 or US 6,717,644.

[0706] Generally, a review of alignment techniques is given, for example, by I. Sage in "Thermotropic Liquid Crystals" (GW Gray, ed., John Wiley & Sons, 1987, pp. 75-77); and by T. Uchida and H. Seki in "Liquid Crystals - Applications and Uses Vol. 3" (B. Bahadur, ed., World Scientific Publishing, Singapore 1992, pp. 1-63). Another review of alignment materials and techniques is given by J. Cognard, Mol.Cryst. Liq. Cryst. 78, Supplement 1 (1981), pp. 1-77.

[0707] In a preferred embodiment, the process of the present invention includes a process step (referred to herein as "annealing") that allows the RM mixture to stand for a period of time to allow the RM mixture to be uniformly redistributed onto the substrate.

[0708] In a preferred embodiment, after the RM mixture or RM formulation is provided onto the substrate, the laminate is annealed for between 10 seconds and 1 hour, preferably between 20 seconds and 10 minutes, and most preferably between 30 seconds and 2 minutes. Annealing is preferably performed at room temperature.

[0709] The RM mixture preferably consists of compounds that spontaneously align when deposited as a mixture onto a substrate. Therefore, the LC dielectric is preferably not heat-treated to align with the mesocrystalline or liquid crystal compound before UV exposure.

[0710] If necessary, the laminate can be cooled to room temperature after annealing at an elevated temperature. Cooling can be carried out actively with the aid of a cooling agent or passively simply by allowing the laminate to stand still for a given time.

[0711] In a preferred embodiment, the RM mixture is exposed to photochemical radiation as described, for example, in WO 01 / 20394, GB 2,315,072 or WO 98 / 04651, during the first UV step.

[0712] Photochemical radiation means irradiation with light (such as UV light, IR light, or visible light), irradiation with X-rays or gamma rays, or irradiation with high-energy particles (such as ions or electrons). Preferably, the first UV step is carried out by light irradiation, specifically with UV light, and in particular with UVA light.

[0713] As a source of photochemical radiation, a single UV lamp or a group of UV lamps can be used. Using higher lamp power can reduce curing time. Another possible source of photochemical radiation is laser, such as a UV laser, an IR laser, or a visible laser.

[0714] The curing time depends particularly on the reactivity of the photoreactive compound, the thickness of the coated layer, and the power and wavelength of the UV lamp. The curing time is preferably ≤ 5 minutes, very preferably ≤ 3 minutes, and most preferably ≤ 1 minute. For mass production, a short curing time of ≤ 30 seconds is preferred.

[0715] The suitable UV radiation power in the first UV step is preferably between 5 and 300 mW / cm². -2 Within the range, more preferably within 50 to 250 mW / cm² -2 Within the range and most preferably in the range of 100 to 180 mW / cm -2 Within the range.

[0716] Regarding the applied UV radiation and its variation over time, the suitable UV dose is preferably between 20 and 1000 mJ / cm². -2 Within the range, more preferably from 30 to 800 mJ / cm -2 Within the range, and most preferably within the range of 40 to 500 mJ / cm -2 Within the range, and most preferably in the range of 40 to 200 mJ / cm -2 Within the range.

[0717] The first irradiation step or the first UV step is preferably carried out in air.

[0718] The first irradiation step or the first UV step is preferably performed at room temperature.

[0719] Photopolymerization in the second irradiation step of the RM mixture is preferably achieved by exposing it to photochemical radiation. Photochemical radiation means irradiation with light (such as UV light, IR light, or visible light), irradiation with X-rays or gamma rays, or irradiation with high-energy particles (such as ions or electrons). Preferably, polymerization is carried out by light irradiation (specifically UV light). As a source of photochemical radiation, for example, a single UV lamp or a group of UV lamps can be used. When using higher lamp power, the curing time can be reduced. Another possible source of light radiation is a laser, such as a UV laser, IR laser, or visible laser.

[0720] The curing time of photopolymerization depends particularly on the reactivity of the RM mixture, the thickness of the coating, the type of polymerization initiator, and the power of the UV lamp. The curing time is preferably ≤ 5 minutes, very preferably ≤ 3 minutes, and most preferably ≤ 1 minute. For large-scale production, a short curing time of ≤ 30 seconds is preferred.

[0721] The suitable UV radiation power for photopolymerization is preferably between 100 and 1000 mW / cm². -2 Within the range, more preferably 200 to 800 mW / cm -2 Within the range and most preferably in the range of 300 to 600 mW / cm -2 Within the range.

[0722] Regarding the applied UV radiation and its variation over time, the suitable UV dose is preferably between 25 and 16500 mJ / cm². -2 Within the range, more preferably from 50 to 7200 mJ / cm -2 Within the range, and most preferably within the range of 100 to 3500 mJ / cm -2 Within the range, and most preferably in the range of 200 to 2000 mJ / cm -2 Within the range.

[0723] Photopolymerization (second irradiation step or second UV step) is preferably carried out in an inert gas atmosphere, preferably in a nitrogen atmosphere.

[0724] Photopolymerization (second irradiation step or second UV step) is preferably carried out at room temperature.

[0725] The preferred thickness of the polymer film according to the invention is determined by the desired optical properties of the film or the final product.

[0726] For optical applications of polymer films, the thickness is preferably 0.1 to 10 μm, very preferably 0.2 to 5 μm, and especially 0.3 to 3 μm.

[0727] As mentioned above, due to the photoisomerization of the chiral compound during the first UV step, its HTP decreases and the helical pitch lengthens to a larger value, where this effect is stronger at the top or surface of the film than at the bottom of the polymer film adjacent to the substrate, resulting in a pitch gradient in the film, where the helical pitch gradually increases or decreases through the film thickness, depending on the observation direction.

[0728] Preferably, in the polymer film according to the invention, the minimum helical pitch is ≤1200 nm, and very preferably 200 to 1200 nm. More preferably, the helical pitch increases throughout the thickness direction from the side of the polymer film near the substrate on which the polymer film is prepared.

[0729] In a preferred embodiment, the polymer film of the present invention exhibits planar orientation, i.e., the LC molecules are oriented parallel to the film plane and the helical axis is oriented substantially perpendicular to the film plane.

[0730] In another preferred embodiment, the polymer film of the present invention exhibits a tilted orientation, i.e., the LC molecules are oriented at an angle (also called a tilt angle) to the film plane and the helical axis is oriented at an angle to the film plane. 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°.

[0731] In another preferred embodiment, the inclination angle between the helical shaft and the shaft perpendicular to the membrane plane is 0 to 15°, very preferably 0 to 5°.

[0732] Planar alignment can be induced, for example, by providing an alignment layer (e.g., a polyimide alignment layer) to the substrate as described above. Tilt alignment can be achieved, for example, by adding an alignment additive to a chiral RM mixture or by using a substrate having a surface grating or pattern (e.g., a PB grating).

[0733] The birefringence (Δn) of the polymer film according to the invention is preferably in the range of 0.20 to 0.60, more preferably 0.25 to 0.55, and very preferably 0.30 to 0.50.

[0734] The optical retardation (δ(λ)) of the polymer film, which varies with the wavelength (λ) of the incident beam, is given by the following equation (7):

[0735] δ(λ) =(2πΔn d) / λ (7)

[0736] Where (Δn) is the birefringence of the film, (d) is the thickness of the film, and λ is the wavelength of the incident beam.

[0737] The birefringence and corresponding optical retardation depend on the film thickness and the tilt angle of the optical axis in the film (see Berek compensator). Therefore, those skilled in the art will recognize that different optical retardations or different birefringences can be induced by adjusting the orientation of liquid crystal molecules in the polymer film.

[0738] The optical retardation, which varies with the thickness of the polymer film according to the invention, is less than 200 nm, preferably less than 180 nm, and even more preferably less than 150 nm.

[0739] In another preferred embodiment, the optical retardation varies with the thickness of the polymer film according to the invention in the range of 110 nm to 170 nm, very preferably 130 nm to 150 nm.

[0740] In the polymer film according to the invention, preferably, the minimum twist angle is 0°. More preferably, the maximum twist angle is in the range of 70° to 150°, very preferably 80° to 120°, and most preferably 90° to 110°. Preferably, the twist angle varies in the film thickness direction in the range of 0° to 150°, very preferably 0° to 120°, and most preferably 0° to 110°.

[0741] Preferably, the lower twist value is located on the side of the polymer film adjacent to the substrate on which the polymer film is formed. The average twist angle in the polymer film is preferably in the range of 10° to 40°, very preferably 15° to 35°, and most preferably 20° to 30°.

[0742] After photopolymerization, the resulting polymer film can be removed from the substrate and combined with other substrates or optical films via lamination processes known to those skilled in the art. Suitable substrates and optical films are given above, and in particular polarizers (linear polarizers in particular), photoalignment layers, or diffraction gratings (e.g., PB gratings).

[0743] The polymer film of this invention exhibits good adhesion to plastic substrates, and specifically TAC, COP, and color filters. Therefore, it can be used as an adhesive or base coating for subsequent LC layers that would otherwise not adhere sufficiently to the substrate.

[0744] To prepare the half-wave plate according to the invention, two polymer films, each representing a quarter-wave plate, are combined into a bilayer.

[0745] Two quarter-wave plates can be combined by directly laminating one quarter-wave plate onto the other. In another preferred embodiment, the second quarter-wave plate is fabricated directly on the first quarter-wave plate, which serves as the substrate.

[0746] Therefore, the present invention further relates to a method for preparing a half-wave plate, wherein two quarter-wave plates having a pitch gradient are formed by the method described above and below, the method comprising method steps p1) to p6), preferably p11) to p66), preferably consisting of these steps, and wherein the first quarter-wave plate is laminated onto the second quarter-wave plate, or vice versa.

[0747] The present invention further relates to a method for preparing a half-wave plate, wherein a first quarter-wave plate having a pitch gradient is formed by the method described above and below, the method comprising method steps p1) to p6), preferably p11) to p66), preferably consisting of the steps, and a second quarter-wave plate is formed by the method described above and below, wherein the first quarter-wave plate is used as a substrate.

[0748] Preferably, two quarter-wave plates are combined such that their surfaces with higher twist face each other (inner surfaces), and their surfaces with lower twist represent the outer surfaces of the resulting double layer. Since low twist corresponds to a long pitch (i.e., a high pitch value) and high twist corresponds to a short pitch (i.e., a low pitch value), this means that in this preferred embodiment, the two quarter-wave plates in the half-wave plate are combined such that their surfaces with shorter pitch face each other.

[0749] This is Figure 2 The figure exemplarily and schematically illustrates a twisted profile in a half-wave plate according to the invention, composed of two quarter-wave plates L1 and L2, each of which is formed from a layer of a polymeric chiral RM mixture having a helical twisted structure and a pitch gradient. The black line indicates the boundary between the inner surfaces of the two layers L1 and L2.

[0750] The polymer film of this 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 the RM formulations described above and below are particularly suitable for multilayer applications due to their improved anti-wetting properties. In this way, optical films or stacks of preferably polymer films can be prepared.

[0751] The present invention further relates to optical, electro-optical or electronic devices or components comprising the half-wave plate described above and below.

[0752] Preferably, the component is a diffraction grating, most preferably PBG, PBL, or Bragg PG, which comprises a half-wave plate obtained from the RM mixture or RM formulation according to the invention described above and below.

[0753] In summary, the polymer film and RM mixture according to the present invention can be used in optical elements such as polarizers, compensators, alignment layers, circular polarizers or color filters in liquid crystal displays or projection systems, decorative images to prepare liquid crystals or effect pigments, and especially in reflective films having reflective colors that vary with space, for example as multicolor images for decorative, information storage or security purposes (such as unforgeable documents, such as ID cards or credit cards, banknotes, etc.).

[0754] The polymer film according to the present invention can be used in transmissive or reflective displays. It can be used in conventional OLED displays or LCDs, especially LCDs.

[0755] 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.

[0756] 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.

[0757] 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.

[0758] 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).

[0759] 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.

[0760] 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.

[0761] 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.

[0762] Unless otherwise stated, percentages are by weight throughout the text. All temperatures are given in degrees Celsius.

[0763] In this context, mp represents the melting point, cl.p. represents the clearing point, and T... g This indicates the glass transition temperature. Furthermore, C represents the crystalline state, N represents the nematic phase, and S represents the... A S B Equals represent smectic A phase, smectic B phase, etc., S X X represents an unidentified smectic phase, X represents an unidentified intermediate phase, and I represents an isotropic phase. The values ​​between these symbols represent transition temperatures in °C. Δn represents optical anisotropy or birefringence (Δn = n). e - n o , where n o Represents the refractive index perpendicular to the longitudinal molecular axis and n e (Refractive index parallel to it), at 589 nm and 20°C. Unless otherwise explicitly stated, optical and electro-optical data are measured at 20°C. "Clearing point" and "clearing temperature" refer to the temperature at which the LC phase transforms into the isotropic phase.

[0764] Unless otherwise stated, the percentage of solid components in an RM mixture or RM formulation as described in the context refers to the total amount of solids in the mixture or formulation, i.e., without any solvent.

[0765] 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.

[0766] 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.

[0767] Example 1

[0768] Prepare the following RM mixture:

[0769]

[0770] Omnirad® 907 is a commercially available photoinitiator (IGM Resins). BYK®-388 is a commercially available surfactant (BYK, Germany).

[0771] The achromaticity of the half-wave plate according to the present invention when placed between two orthogonal polarizers is compared with that of the prior art half-wave plate.

[0772] The half-wave plate between the orthogonal polarizers will allow up to 50% of the light to pass through the top polarizer. Any reduction in light intensity across the wavelength range will degrade performance and make the polarizer less suitable for this application. Therefore, in this embodiment, any reduction in light intensity less than 49% is considered a failure.

[0773] The achromaticity of the film stack S1, which includes a half-wave plate according to the invention between two orthogonal polarizers, as shown in Table 1 below, was determined using DIMOS 1D software. The half-wave plate in Table 1 consists of two layers, L1 and L2, of a polymeric mixture M2, each layer having a different twist with a calculated asymmetric twist profile as shown in Table 2 below and a quarter-wave delay.

[0774] Figure 2 The diagram illustrates the twisted profile of a half-wave plate according to the invention, which consists of two layers L1 and L2 having an asymmetric twisted profile. The black lines indicate the boundary between the inner surfaces of the two layers L1 and L2.

[0775] Table 1 - Membrane stack S1 of Example 1

[0776]

[0777] Table 2 - Twist profiles of membranes 1 and 2

[0778]

[0779] For comparative purposes, the achromaticity of the film stack CS1, which includes a half-wave plate according to the prior art between two orthogonal polarizers, as shown in Table 3 below, was determined using DIMOS1D software. The half-wave plates in Table 3 consist of a non-twisted layer C1 of a polymeric mixture M2 with a half-wave delay.

[0780] Table 3 - Comparative Example 1 membrane stack CS1

[0781]

[0782] Achromaticity was measured for unpolarized light input (400-700 nm, step size 1 nm), where light was detected after leaving the complete stack including the polarizer.

[0783] Figure 3 (a) and Table 4 show the transmittance versus wavelength of a film stack S1 of Embodiment 1 with a half-wave plate according to the invention between orthogonal polarizers, the half-wave plate being composed of two quarter-wave plates L1 and L2 having an asymmetric twisted profile (b).

[0784] Table 4 - Achromaticity of the film stack S1 in Example 1

[0785]

[0786] Figure 3 (b) and Table 5 show the transmittance of the film stack CS1 of Comparative Example 1 with standard half-wave plates between orthogonal polarizers as a function of wavelength.

[0787] Table 5 - Achromaticity of the film stack CS1 in Comparative Example 1

[0788]

[0789] As can be seen from the data, the achromaticity of the film stack S1 according to the present invention, which has a half-wave plate consisting of two layers with an asymmetrical twisted profile, is much higher than that of the film stack CS1 with a standard half-wave plate according to the prior art.

[0790] Due to the dispersion of the RM mixture, the standard half-wave plate film stack CS1 of the prior art only achieves 49% transmittance at a wavelength of 550 nm. In contrast, the film stack S1 with the variable twisted half-wave plate of the present invention has a spectral bandwidth greater than 200 nm, thus exhibiting significantly improved performance across the entire visible spectrum.

[0791] Example 2

[0792] In this embodiment, a half-wave plate according to Embodiment 1 of the present invention is compared with a prior art half-wave plate made by controlling the stack of two untwisted RM films at a precise angle on top of each other.

[0793] The achromaticity of the film stack of Example 1 with the half-wave plate according to the present invention was determined using DIMOS 1D software.

[0794] Figure 4 (a) and Table 7 show the transmittance versus wavelength of a film stack S1 of Embodiment 1 with a half-wave plate according to the invention between orthogonal polarizers, the half-wave plate consisting of two quarter-wave plates having an asymmetric twisted profile.

[0795] Table 7 - Achromaticity of the film stack S1 in Example 1

[0796]

[0797] For comparative purposes, the achromaticity of the film stack CS2 shown in Table 6 was determined using DIMOS 1D software. The half-wave plate in the stack CS2 consists of two partial wave plates, each consisting of a non-distorted layer C2 or C3 of a polymeric mixture M2 with a quarter-wave delay.

[0798] Table 6 - Comparative Example 2 membrane stacks CS2

[0799]

[0800] Achromaticity was measured for unpolarized light input (400-700 nm, step size 1 nm), where light was detected after leaving the complete stack including the polarizer.

[0801] Figure 4 (a) and Table 7 show the transmittance versus wavelength of a film stack S1 of Embodiment 1 with a half-wave plate according to the invention between orthogonal polarizers, the half-wave plate consisting of two quarter-wave plates L1 and L2 having an asymmetric twisted profile.

[0802] Table 7 - Achromaticity of the film stack S1 in Example 1

[0803]

[0804] Figure 4 (b) and Table 8 show the transmittance of the film stack CS2 of Comparative Example 2 with a standard half-wave plate between orthogonal polarizers as a function of wavelength, the half-wave plate consisting of two untwisted quarter-wave plates C2 and C3.

[0805] Table 8 - Achromaticity of the film stack CS2 in Comparative Example 2

[0806]

[0807] As can be seen from the data, compared with the prior art film stack CS2 having a half-wave plate composed of two untwisted and partially quarter-wave plates, the film stack S1 of the present invention having a much higher achromaticity and a spectral bandwidth greater than 200 nm and good performance across the entire visible spectrum.

[0808] The half-wave plate of the present invention also has the advantage of simpler manufacturing. Therefore, the first RM layer L1 can act as the alignment layer of the second RM layer L2, and vice versa. Using this method, it is extremely easy to construct an RM film stack by coating an additional layer on top of the cured RM film.

[0809] Example 3 - Preparation of a quarter-wave plate with an asymmetric twisted profile

[0810] Prepare the following chiral RM mixture:

[0811]

[0812] Irganox® 1076 is a commercially available stabilizer (Ciba AG, Basel, Switzerland). NCI®-930 is a commercially available photoinitiator (Adeka Coorporation, Japan). BYK®-310 is a commercially available surfactant (BYK, Germany).

[0813] RM formulation F1 was prepared by dissolving a 36% solid mixture M1 in a solvent blend of toluene:cyclohexanone (7:3).

[0814] Polymer films were prepared by self-preparing formulation F1 using the following method:

[0815] An alignment layer was prepared on a 60µm thick TAC substrate by rod coating with Nissan PAL HSPA-152 using an MB#3 rod, baking the coated substrate at 110°C for 60 seconds, and exposing it to polarized UV light using a wire grid polarizer and a high-pressure mercury lamp (LH6 melting) at 67mW / cm² and 12mJ / cm².

[0816] Using MB#6 rods and annealing at 60°C for 60 seconds, the first exposure step is performed in air atmosphere using a high-pressure mercury lamp (LH6 melt) with 180mW / cm² and 40mJ / cm² UVA, and the formulation F1 rod is applied to the alignment layer.

[0817] After the first UV exposure step, the sample was purged with nitrogen for 60 seconds and then exposed to UV light for a second step using a high-pressure mercury lamp (LH6 fusion) at 520 mW / cm² and 220 mJ / cm² UVA.

[0818] The polymer film P1 was measured using Axometrics Axostep once. membrane upward (Light source, substrate, polymer film, detector) and once Membrane downward (Light source, polymer film, substrate, detector). Plot the spectral polarization state on a Poincaré sphere. The polarization ellipse varies with each wavelength, but all exhibit left-handed rotation. Due to the asymmetry of the twist in the z-direction, the film effect is irreversible.

Claims

1. A half-wave plate comprising two layers of a polymeric chiral RM mixture having a helical twisted structure, wherein the helical pitch in each layer increases or decreases in the film thickness direction, and wherein the two layers have opposite twisting directions.

2. The half-wave plate according to claim 1, characterized in that... The two layers of the polymeric chiral RM mixture are arranged such that their surfaces with shorter pitch face each other.

3. The half-wave plate according to claim 1 or 2, characterized in that... The chiral RM mixture contains at least one, preferably exactly one, chiral compound having one or more isomerizable groups, preferably one or more photoisomerizable groups, which is preferably polymerizable.

4. A half-wave plate according to one or more of claims 1 to 3, characterized in that... The chiral RM mixture further comprises at least one, preferably exactly one, chiral compound that does not contain isomerizable groups.

5. The half-wave plate according to claim 4, characterized in that... The chiral compound having one or more isomerizable groups and the chiral compound not containing isomerizable groups have opposite twisting directions.

6. A half-wave plate according to one or more of claims 1 to 5, characterized in that... The chiral RM mixture contains ingredients selected from formula I. Isomerizable chiral compounds: R 3 -(A 3 -Z 3 ) m -G(-(Z 4 -A 4 ) l -R 4 ) k I Each group, independently of the others and in the same or different manner each time it appears, has the following meaning: R 3 R 4 It can be H, F, Cl, CN, P-Sp-, or an alkyl group having up to 25 carbon atoms, either unsubstituted, halogenated, or mono- or poly-substituted with CN. One or more non-adjacent CH2 groups can also be independently substituted with -O-, -S-, -NH-, -N(CH3)-, -CO-, -COO-, -OCO-, -OCO-O-, -S-CO-, -CO-S-, or -C≡C-, in such cases as to prevent the oxygen atoms from being directly bonded to each other. P is a polymerizable group. Sp can be a spacer group or a single bond. 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 a single bond, 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. G is a chiral group. 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 may optionally be substituted with the following groups: -O-, -S-, -CO-, -CO-O-, -O-CO-, -O-CO-O-, CR 0 =CR 00 -、-C≡C-、 ， The alternative is that the O- and / or S- atoms are not directly connected to each other, and one or more H atoms are each optionally replaced by P-Sp-, F or Cl, or the two substituents L connected to the directly adjacent C atom can also form a cycloalkyl or cycloalkenyl group with 5, 6, 7 or 8 C atoms. m and l are independently 0, 1, 2 or 3. k is 0, 1, or 2. The compound contains at least one isomerizable group, preferably a photoisomerizable group.

7. The half-wave plate according to claim 6, characterized in that... Equation I The compound contains an isomerizable group selected from the following: stilbene, (1,2-difluoro-2-phenyl-vinyl)benzene, cinnamate, α-cyanocinate, 4-phenylbut-3-en-2-one, 2-benzyl-1-indanone, Schiff base, chalcone, coumarin, chromone, dicyclopentadienone or azophenyl group, and / or Z 3 and / or Z 4 They can be represented independently as -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-.

8. The half-wave plate according to claim 6 or 7, characterized in that... In Equation I In the compound, the chiral group G is selected from or derived from: disohydrohexitol, preferably isosorbide, isomannitol or isotretinoin, 1,1'-bis-2-naphthol or 1,2-diphenyl-1,2-ethylene glycol group.

9. A half-wave plate according to one or more of claims 1 to 8, characterized in that... This chiral RM mixture contains non-isomerizable chiral compounds selected from formulas CRM1, CRM2, and CRM3: Each group, independently of the others and in the same or different manner each time it appears, has the following meaning: P 0 It is a polymerizable group. Sp 0 It is a spacer group or a single bond. R 0 F, Cl, CN, having 1 to 15, preferably 1 to 6, carbon atoms, of the following compounds: alkyl, alkoxy, thioalkyl, alkylcarbonyl, alkoxycarbonyl, alkylcarbonyloxy, or alkoxycarbonyloxy; P 0 -, or P 0 -Sp -, A 0 B 0 E 0 F 0 It is 1,4-phenylene, either unsubstituted or L-substituted with 1, 2, 3, or 4 groups, or trans-1,4-cyclohexylene. 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. X 1 X 2 It can be -O-, -COO-, -OCO-, -O-CO-O-, or a single bond. Z 0 The bond type can be -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. a0 can be 0, 1, or 2, preferably 0 or 1. b0 is 0 or an integer from 1 to 12, preferably from 1 to 6. t0 is 0, 1, 2, or 3. z0 can be 0 or 1, preferably 1. Furthermore, the naphthalene ring may be substituted by one or more identical or different groups L.

10. A half-wave plate according to one or more of claims 1 to 9, characterized in that... This chiral RM mixture contains one or more RMs selected from DRM and MRM: P 1 -Sp 1 -MG-Sp 2 -P 2 DRM P 1 -Sp 1 -MG-R 22 MRM in P 1 P 2 Each can independently represent a polymerizable group. Sp 1 Sp 2 Each is an independent spacer group or single bond, and MG is a rod-shaped mesocrystalline group, preferably selected from the formula MG. -(A 1 -Z 1 ) n -A 2 - MG in A 1 and A 2 When appearing multiple times, they independently represent aromatic or alicyclic groups, which optionally contain one or more heteroatoms selected from N, O, and S and optionally undergo L mono- or poly-substituted substitution. 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 substituted with F or Cl. R x and R y Each can be independently represented by H or an alkyl group having 1 to 12 carbon atoms. Z 1 When they appear multiple times, they can be represented independently as -O-, -S-, -CO-, -COO-, -OCO-, -S-CO-, -CO-S-, -O-COO-, -CO-NR. 00 -、-NR 00 -CO-、-NR 00 -CO-NR 000 -NR 00 -CO-O-、-O-CO-NR 00 -, -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. Y 1 and Y 2 Each can be represented independently of H, F, Cl, or CN. 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 substituted with F or Cl. X is a halogen, preferably F or Cl. n can be 1, 2, 3, or 4, preferably 1 or 2, and most preferably 2. n1 is an integer from 1 to 10, preferably 1, 2, 3 or 4.

11. A half-wave plate according to one or more of claims 1 to 10, characterized in that... This chiral RM mixture contains one or more compounds of formula I: Each group, independently of the others 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. R 11 H, F, Cl, CN, or an optionally fluorinated alkyl, alkoxy, thioalkyl, alkylcarbonyl, alkoxycarbonyl, alkylcarbonyloxy, or alkoxycarbonyloxy group having 1 to 15 carbon atoms, preferably 1 to 5 carbon atoms, or P-Sp. A, B, D, and E are selected from the group consisting of: 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-tetrahydronaphthyl-5,8-diyl, or indane-2,5-diyl. Additionally, one or more CH groups in these groups may be substituted with N, and all of the above may be optionally substituted with one or more L or P-Sp- groups. C is selected from the group consisting of: 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, benzothiophene-4,7-diyl, all of which may be optionally substituted with one or more L or P-Sp groups. Furthermore, either ring C or ring D can represent a single bond. 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 substituted with -O-, -S-, -CO-, -CO-O-, -O-CO-, -O-CO-O-, or CR-. 0 =CR 00 -、-C≡C-、 The substitution is performed such that the O-atom and / or S-atom are not directly connected to each other, and one or more H atoms are each optionally substituted by P-Sp-, F or Cl, or the two substituents L connected to the directly adjacent C atom can also form a cycloalkyl or cycloalkenyl group 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 a single bond, preferably -COO-, -OCO-, -C≡C- or a single bond, most preferably a single bond. n1 is 1, 2, 3, or 4. r can be 0, 1, 2, 3, or 4, preferably 0, 1, or 2. s can be 0, 1, 2, or 3, preferably 0, 1, or 2. t can be 0, 1, or 2, preferably 0 or 1. 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, n is 0, 1, 2, 3 or 4, preferably 0, 1 or 2, more preferably 0 or 1, and most preferably 0. m is 0, 1, 2, 3 or 4, preferably 0, 1 or 2, more preferably 0 or 1, and most preferably 0.

12. A half-wave plate according to one or more of claims 6 to 11, characterized in that... In Equation I In the compounds CRM1, CRM2, CRM3, DRM, MRM, and I, the polymerizable group is selected from acrylates and methacrylates, preferably acrylates, and the spacer group is selected from -(CH2). p1 -、-(CH2) p1 -O-、-(CH2) p1 -O-CO-、-(CH2) p1 -CO-O- and -(CH2) p1 -O-CO-O-, where p1 is an integer from 1 to 6.

13. A method for preparing a half-wave plate according to one or more of claims 1 to 12, comprising the following steps, preferably consisting of the following steps: p1) The first quarter-wave plate is formed by a method comprising the following steps, preferably the following steps: p11) A layer of a chiral RM mixture as defined in one or more of claims 1 to 15 is provided on a substrate, the substrate optionally having an alignment layer capable of inducing planar alignment with adjacent layers of the chiral reactive mesocrystalline mixture. p12) Optional removal of any solvent present. p13) Optionally, the layer of the chiral reactive mesocrystalline mixture is preferably annealed at the temperature at which it is a chiral nematic phase. p14) The first step (first UV step) involves irradiating the chiral reactive mesocrystalline mixture in air with photochemical radiation, preferably UV radiation. p15) Optionally, the layer of the chiral reactive mesocrystalline mixture is preferably annealed at the temperature at which the chiral nematic phase is located, and p16) The second step (second UV step) involves irradiating the chiral reactive mesocrystalline mixture with photochemical radiation, preferably UV radiation, in an inert gas atmosphere. p2) A second quarter-wave plate is formed by a method comprising steps p11) to p16) as described above, preferably consisting thereof, wherein the chiral RM mixture of the first and second quarter-wave plates has opposite twists. p3) Combine the first quarter-wave plate and the second quarter-wave plate to form a half-wave plate.

14. The method according to claim 13, characterized in that... The substrate has a surface grating or pattern.

15. The method according to claim 13 or 14, characterized in that... The first quarter-wave plate is laminated onto the second quarter-wave plate, or vice versa.

16. The method according to claim 15, characterized in that... The first quarter-wave plate is used as a substrate for fabricating the second quarter-wave plate.

17. An optical, electro-optical, or electronic device or a component thereof comprising a half-wave plate according to one or more of claims 1 to 12.

18. The component of claim 17, selected from optical retardation films, polarizers, optical compensators, diffraction or surface gratings, Bragg polarization gratings (Bragg PG), polarization volume gratings (PVG), Panchara-Tnamberg gratings (PBG) or Panchara-Tnamberg lenses (PBL), and also non-mechanical beam manipulation elements, optical waveguides, optical couplers 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 and IR reflective films.

19. The apparatus of claim 17, wherein the device is selected from liquid crystal displays, organic light-emitting diodes, autostereoscopic 3D displays, perspective near-eye displays, AR / VR systems, AR / VR application goggles, switchable windows, spatial light modulators, optical data storage devices, optical sensors, holographic devices, spectrometers, optical communication systems, polarimeters, or front / backlights.

Images