Chiral reactive mesogen mixture

Abstract

A mixture of chiral reactive mesogens is provided. [Solution] The present invention relates to chiral reactive mesogen (RM) mixtures and formulations containing them (as a subcategory of liquid crystal materials), preferably PFAS-free (to enable the reduction of perfluorocarbons and provide environmentally friendly materials), polymers and polymer films obtained from such chiral RM mixtures, as well as the use of chiral RM mixtures, formulations, polymers and polymer films in optical components or electro-optical components or devices, particularly in digital optical systems or augmented reality or virtual reality (AR / VR) applications (such as polarizers, optical compensators, reflective films, diffraction gratings or surface gratings, Bragg polarizing gratings (Bragg PG), polarizing volume gratings (PVG), polarizing volume holograms (PVH), Pancharatnam Berry (PB) gratings, non-mechanical beam steering elements, optical waveguides, optical couplers, optical combiners, polarizing beam splitters, partial mirrors or lenses).

Description

[Technical Field]

[0001] The present invention relates to chiral reactive mesogen (RM) mixtures and formulations containing them (as a subcategory of liquid crystal materials), preferably PFAS-free (to enable the reduction of perfluorocarbons and provide environmentally friendly materials), polymers and polymer films obtained from such chiral RM mixtures, as well as the use of chiral RM mixtures, formulations, polymers and polymer films in optical components or electro-optical components or devices, particularly in digital optical systems or augmented reality or virtual reality (AR / VR) applications (such as polarizers, optical compensators, reflective films, diffraction gratings or surface gratings, Bragg polarizing gratings (Bragg PG), polarizing volume gratings (PVG), polarizing volume holograms (PVH), Pancharatnam Berry (PB) gratings, non-mechanical beam steering elements, optical waveguides, optical couplers, optical combiners, polarizing beam splitters, partial mirrors or lenses). [Background technology]

[0002] Reactive mesogens (RMs), mixtures or formulations containing them, and liquid crystal polymer (LCP) films obtained therefrom can be used in the manufacture of optical components such as compensating films, phase difference films, polarizing films, and lenses. These optical components can be used in optical devices or electro-optical devices such as liquid crystal displays. Typically, RMs or RM mixtures are polymerized by an in-situ polymerization process.

[0003] The availability of high birefringence RM materials and LCP films is crucial in the manufacture of optical components for modern display devices such as LCDs, and is also important in emerging fields such as augmented reality or virtual reality (AR / VR) applications, where LCP films can be used, for example, as optical waveguides. In these applications, a high average refractive index (Δn) is required while maintaining high birefringence (Δn). <n>Materials exhibiting the following characteristics are required. RM materials and LCP films have been proposed for the manufacture of lenses, such as diffraction gratings like Pancharatnam-Berry gratings (PBGs), Bragg polarizing gratings (Bragg PGs), or polarizing volume gratings (PVGs). The optimal orientation of RM in PVGs is usually achieved in chiral nematic (hereinafter also referred to as "cholesteric") systems, where the chiral structure promotes the self-assembly of bulk liquid crystals.

[0004] To maximize the performance of optical elements, several properties of the cholesteric RM material and LCP film, such as cholesteric pitch and refractive index (anomalous refractive index (n), are important. e ), normal refractive index (n o ), average refractive index ( <n>), birefringence Δn, film thickness (d), etc., must be designed and carefully controlled. In addition, it may be necessary to vary these properties within a single optical element, such as when using multiple LCP layers with different pitches, thicknesses, refractive indices, and / or tilt angles.

[0005] Furthermore, when manufacturing multilayer optical elements by directly layering and coating multiple RM layers, it is important to ensure good and uniform orientation quality, prevent damage when coating the lower RM layer on top of it, and impart an orientation direction from one RM layer to the next through strong intermolecular interactions between the RM layers.

[0006] Some optical components in LCD and AR / VR devices require the manufacture of cholesteric LCP films with a wide reflection bandwidth and high birefringence.

[0007] For certain applications, such as diffractive optical elements used as optical waveguides, it is considered even more desirable to provide LCP films made from chiral RM materials having an asymmetric helical structure. This can be achieved by providing cholesteric LCP with a pitch gradient. In other words, the helical pitch gradually increases or decreases from a low pitch on one side to a high pitch on the opposite side.

[0008] Therefore, it is desirable to provide a chiral RM material for use in the manufacture of cholesteric LC polymer films that exhibits high birefringence and / or a wide reflection bandwidth, allows for easy and accurate control of optical properties such as birefringence, average refractive index, and chiral pitch, achieves good orientation quality even in multilayer systems, and enables the fabrication of films with a pitch gradient. [Disclosure of the Invention] [Problems that the invention aims to solve]

[0009] The object of the present invention is to provide chiral RM mixtures and LCP films exhibiting one or more of the above advantages. Other objects of the present invention will be immediately apparent to those skilled in the art from the following detailed description.

[0010] Surprisingly, the inventors of the present invention have found that these objectives can be achieved by providing a chiral reactive mesogen mixture, also hereinafter referred to as the “RM mixture,” in accordance with the present invention described and claimed below. [Means for solving the problem]

[0011] The present invention relates to a mixture (hereinafter referred to as "RM mixture") comprising at least one, preferably exactly one, chiral isomerizable, preferably chiral photoisomerizable (preferably polymerizable) compound and at least one compound of formula I.

[0012] [ka]

[0013] In the formula, each base, independently of the others, and identical or different in each instance, has the following meanings: P is a polymerizable group, Sp is a spacer group or a single bond. R 11 This is an alkyl, alkoxy, thioalkyl, alkylcarbonyl, alkoxycarbonyl, alkylcarbonyloxy or alkoxycarbonyloxy (which may be fluorinated) having H, F, Cl, CN, 1 to 15, preferably 1 to 5 C atoms, or P-Sp. 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-dihydrophenanthrene-2,7-diyl, 1,2,3,4-tetrahydronaphthalene-5,8-diyl, or indan-2,5-diyl, provided that one or more CH groups in these groups may be replaced with N, and all of them may be replaced with one or more L or P-Sp- groups. C is selected from the group consisting of benzene-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, and benzothiophene-4,7-diyl, all of which may be substituted with one or more groups L or P-Sp-. Furthermore, one of rings C and D may represent a single bond. L is a linear, branched, or cyclic alkyl group having 1 to 25 carbon atoms, wherein one or more non-adjacent CH2- groups are arranged such that the oxygen and / or sulfur atoms are not directly linked to each other, resulting in -O-, -S-, -CO-, -CO-O-, -O-CO-, -O-CO-O-, -CR 0 =CR 00 -, -C≡C-, [ka] It may be replaced by, however, one or more H atoms may be replaced by P-Sp-, F or Cl, or two substituents L directly attached to adjacent C atoms may also form a cycloalkyl or cycloalkenyl group having 5, 6, 7 or 8 C atoms. Z 11 、Z 12 is -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 0 、R 00 is H or alkyl having 1 to 12 C atoms, Y 1 、Y 2 is H, F, Cl, NCS, or CN, n is 0, 1, 2, 3 or 4, preferably 0, 1 or 2, more preferably 0 or 1, most preferably 0, m is 0, 1, 2, 3 or 4, preferably 0, 1 or 2, more preferably 0 or 1, most preferably 0.

[0014] The present invention further relates to a formulation, hereinafter referred to as "RM formulation", which contains one or more chiral isomerizable compounds and one or more compounds of formula I as described above and below, or a RM mixture, and further contains one or more solvents and / or additives.

[0015] The present invention further relates to polymer films obtained by polymerizing the RM mixtures or RM formulations described above and below, and to methods for producing the same, wherein the RM is oriented, and preferably the polymerization is carried out at a temperature in which the RM or RM mixture exhibits a liquid crystal phase.

[0016] The present invention further relates to the use of the RM mixtures or polymer films described above and below in optical components, electro-optical components, or electronic components or devices.

[0017] The present invention further relates to optical components, electro-optical components, or electronic devices or components comprising the RM mixture or polymer film described above and below.

[0018] The aforementioned components include, but are not limited to, optical delay films, polarizers, optical compensators, reflective films, Bragg polarizing gratings (Bragg PG), polarizing volume gratings (PVG), Pancharatnam Berry (PB) gratings, diffraction gratings or surface gratings, as well as non-mechanical beam steering elements, optical waveguides, optical couplers or combiners, polarizing beam splitters, partial mirrors, reflective films, alignment layers, color filters, antistatic sheets, electromagnetic interference prevention sheets, optical guide lenses, focusing and optical effects, polarization control lenses, and IR reflective films. For example, they are used in LCD displays (LCDs), organic light-emitting diodes (OLEDs), naked-eye stereoscopic 3D displays, see-through myopia displays, augmented reality (AR) or virtual reality (VR) systems, switchable windows, spatial light modulators, optical data storage, remote optical sensing, holography, spectroscopy, optical communications, polarization measurement methods, front / back illumination, and the like.

[0019] The aforementioned devices include, but are not limited to, electro-optical displays, particularly LCDs, OLEDs, automated stereoscopic 3D displays, see-through near-eye displays, AR / VR systems, goggles for AR / VR applications, switchable windows, spatial light modulators, optical data storage devices, optical sensors, holographic devices, spectrometers, optical communication systems, polarimeters, or front / backlights. [Brief explanation of the drawing]

[0020] [Figure 1] Figure 1 shows the CLC pitch as a function of the concentration of the chiral isomerizing compound used in polymer films prepared using Example 1 with different UV power levels during the isomerization process. [Figure 2] Figure 2 shows the CLC pitch as a function of UV output during the isomerization process of polymer films prepared according to Example 1 at different concentrations of the chiral isomerizing compound. [Modes for carrying out the invention]

[0021] <Definition of Terms> Throughout this description and the claims, the words “comprise” and “contain,” and variations thereof, such as “comprising” and “comprises,” mean “not limited to these,” and are not intended to exclude, nor do they exclude, other components.

[0022] Unless otherwise clearly indicated by the context, the plural form of a term used herein shall be interpreted as including the singular form, and vice versa.

[0023] As used herein, the term "film" includes rigid or flexible, self-supporting or independent films having mechanical stability, as well as coatings or layers on or between a supporting substrate.

[0024] As used herein, the terms “reactive mesogen” and “RM” are understood to mean a compound comprising a mesogen or liquid crystal skeleton and one or more functional groups bonded thereto, which are suitable for polymerization and also called “polymerizable groups” or “P”, optionally bonded via spacer groups.

[0025] Unless otherwise specified, the term "polymerizable compound" as used herein shall be understood to mean a polymerizable monomer compound.

[0026] Polymerizable compounds or polymeric compounds (RMs) with one polymerizable group are also called "monoreactive" compounds, polymerizable compounds or RMs with two polymerizable groups are also called "direactive" compounds, and polymerizable compounds or RMs with three or more polymerizable groups are also called "polyreactive" compounds. Compounds without polymerizable groups are also called "nonreactive" compounds.

[0027] As used herein, the terms “liquid crystal,” “mesogen,” and “mesogenous compound” refer to compounds that can exist as an intermediate phase, or in particular as an LC phase, under appropriate conditions of temperature, pressure, and concentration.

[0028] The "transparency point" refers to the temperature at which a transition occurs between the intermediate phase, which has the highest temperature range, and the isotropic phase.

[0029] As used herein, the term “mesogenic group” refers to a group known to those skilled in the art, documented in the literature, that, due to the anisotropy of its attractive and repulsive interactions, essentially contributes to the formation of a liquid crystal (LC) phase in low molecular weight or polymeric materials. Compounds containing mesogenic groups (mesogenic compounds) do not necessarily have an LC phase themselves. Mesogenic compounds may also exhibit LC phase behavior only after being mixed with other compounds and / or polymerized. Typical mesogenic groups are, for example, rigid rod-shaped or disc-shaped units. A summary of terms and definitions used in relation to mesogenic compounds or LC compounds is given in Pure Appl. Chem. 2001, Vol. 73 (No. 5), p. 888 and in C. Tschierske, G. Pelzl, S. Diele, Angew. Chem. 2004, Vol. 116, pp. 6340–6368.

[0030] As used herein, the term "spacer group" (hereinafter also referred to as "Sp") is known to those skilled in the art and is described in the literature, for example, Pure Appl. Chem. 2001, Vol. 73 (No. 5), p. 888 and C. Tschierske, G. Pelzl, S. Diele, Angew. Chem. 2004, Vol. 116, pp. 6340-6368. As used herein, the term "spacer group" or "spacer" means a flexible group that links a mesogenic group to a polymerizable group in a polymerizable mesogenic compound, such as an alkylene group.

[0031] As used herein, the term "RM mixture" means a mixture containing one or more types of RM, preferably two or more types, more preferably two to ten types, and very preferably two to six types.

[0032] As used herein, the term “RM formulation” means at least one type of RM or RM mixture, and one or more other materials added to at least one type of RM or RM mixture to give or modify specific properties of the RM formulation and / or at least one type of RM. It will be understood that the RM formulation is also a medium that allows the RM to be carried onto a substrate and formed on it in layers or structures. Illustrative materials include, but are not limited to, solvents, polymerization initiators, surfactants, and adhesion promoters, as will be described in more detail below.

[0033] Unless otherwise stated, the percentages of compounds in the RM mixture given above and below mean weight percent of the total RM mixture, excluding the solvents and liquid additives used in the RM formulation as described above and below.

[0034] Unless otherwise stated, the percentages of compounds in the RM formulations given above and below refer to the weight percentage of the total solids in the RM formulation, excluding the solvent and including the liquid additives listed below.

[0035] As used herein, the term “per and / or polyfluoroalkyl compound (PFAS)” means (as defined by the OECD) a substance or compound containing at least one fully fluorinated methyl or methylene C atom (without any H / Cl / Br / I atoms bonded to it), i.e., a compound having at least one CF3 or CF2 group.

[0036] As used herein, the expression "polyfluoroalkyl or aryl group" means an alkyl or aryl group substituted with two or more F atoms (the F atoms may be linked to the same or different C atoms), and therefore includes a perfluorocarbon group.

[0037] As used herein, the term “polymer” means a molecule that contains a backbone of one or more different types of repeating units (the smallest constituent units of a molecule), and is understood to include commonly known terms such as “oligomer,” “copolymer,” and “homopolymer.” Furthermore, the term polymer is understood to include not only the polymer itself, but also residues from initiators, catalysts, and other elements accompanying the synthesis of such polymers, and such residues are not covalently incorporated. Moreover, such residues and other elements are usually removed during the post-polymerization purification process, but typically remain with the polymer when it is moved between containers or between solvents or dispersion media, typically mixed or blended with the polymer.

[0038] The term "polymerization" refers to the chemical process of forming a polymer by combining multiple polymerizable groups or polymer precursors (polymerizable compounds) that contain such polymerizable groups.

[0039] A "polymer network" is a network in which all polymer chains are interconnected by numerous crosslinks, forming a single macroscopic entity.

[0040] Polymer networks include the following types: Graft polymer molecules are branched polymer molecules in which one or more side chains are structurally or constitutively different from the main chain. A star polymer molecule is a branched polymer molecule from which multiple linear chains or arms arise from a single branching point. If the arms are identical, the star polymer molecule is said to be regular. If adjacent arms are composed of different repeating subunits, the star polymer molecule is said to be diverse. • Comb-shaped polymer molecules consist of a main chain with two or more triplicate branching points and linear side chains. If the arm portions are identical, the comb-shaped polymer molecule can be said to be regular. • Brush-type polymer molecules consist of a main chain with linear, unbranched side chains, and have functionality in four or more directions at one or more branching points.

[0041] The term "chiral" is generally used to describe objects that cannot be superimposed onto a mirror image.

[0042] An "achiral" (non-chiral) object is an object that is identical to its mirror image.

[0043] In this application, unless otherwise explicitly stated, the terms "chiral nematic" and "cholesteric" are used synonymously.

[0044] The term "isomerizing / photoisomerizing compound" refers to a compound that contains one or more isomerizing or photoisomerizing groups.

[0045] The term "isomerizing group" refers to a molecular functional group that causes a change in the shape of a molecule, i.e., isomerization, through bond rotation, skeletal rearrangement, movement of atoms or groups, or dimerization induced, for example, thermally or photochemically, or by the addition of a catalyst.

[0046] The term "photoisomerizing group" refers to a molecular functional group that, when irradiated with light of an appropriate wavelength that the molecule can absorb, causes a change in the shape of the molecule, i.e., isomerization, through bond rotation, skeletal rearrangement, movement of atoms or groups, or dimerization (photoisomerization).

[0047] Examples of photoisomerizable groups include the -C=C- double bond and the azo group (-N=N-). Examples of molecular structures and substructures containing such photoisomerizable groups include stilbene, (1,2-difluoro-2-phenyl-vinyl)benzene, cinnamate, α-cyanocinnamate, 4-phenylbuta-3-en-2-one, and Schiff bases (i.e., the group R). i R ii C=NR iii , here, R iii Unlike H, it is, for example, alkyl or aryl. Examples include 2-benzylidene-1-indanone, chalcone, coumarin, chromone, pentarenone, and azobenzene.

[0048] The chiral RM mixture according to the present invention can be prepared, for example, by doping a host mixture containing one or more types of RM with a chiral compound having high torsional strength.

[0049] The pitch p (nm) of the induced cholesteric helix (hereinafter also called "chiral pitch" or "helical pitch") is determined by the concentration c (%) of the chiral compound and the helical torsional force HTP (nm). -1 It is given by the following formula:

[0050]

number

[0051] A small pitch value is also referred to as a "short pitch," and a large pitch value is also referred to as a "long pitch." Furthermore, a short pitch corresponds to a highly twisted structure, i.e., a higher twist angle, while a long pitch corresponds to a structure that twists slowly around the helical axis within a given distance, i.e., a lower twist angle.

[0052] The twist angle θ across the thickness d is defined by the following equation.

[0053]

number

[0054] In the formula, p is the pitch as defined above.

[0055] When multiple chiral compounds are used, the total HTP (HTP) of chiral compounds with the same configuration or torsional orientation is calculated. total The following equation holds true for approximately the following:

[0056]

number

[0057] In the formula, c i This represents the concentration of each individual chiral compound, HTP i This represents the helical torsional force of each individual chiral compound.

[0058] HTP(|HTP) all chiral compounds in a mixture of different compositions or different torsional directions Δ |) can be expressed in approximately the following formula.

[0059]

number

[0060] In the formula, c s This refers to the concentration of each chiral compound in the S conformation, HTP s is the helical torsional force of each chiral compound in the S configuration, where c r The concentration of each chiral compound in the R configuration, HTP R is the helical torsional force of each chiral compound in the R conformation.

[0061] The birefringence Δn is defined as follows:

[0062]

number

[0063] where n e is the abnormal refractive index, and n o is the normal refractive index. The effective average refractive index n av. is given by the following formula.

[0064]

Equation

[0065] The average refractive index n av. and the normal refractive index n o can be measured using an Abbe refractometer. Δn can be calculated from the above formula.

[0066] The central wavelength λ and bandwidth Δλ of the reflection band of a cholesteric RM or LC material or a cholesteric polymer film are given by the following formula in terms of the pitch p of the cholesteric helix, the average refractive index n av. , and the birefringence Δn of the cholesteric liquid crystal.

[0067]

Equation

[0068] The term "visible light" means electromagnetic radiation having wavelengths in the range of approximately 400 nm to approximately 740 nm. "Ultraviolet (UV) light" means electromagnetic radiation having wavelengths in the range of approximately 200 nm to approximately 450 nm.

[0069] According to the present application, the term "linearly polarized light" means light that is at least partially linearly polarized. Preferably, the oriented light is linearly polarized with a degree of polarization exceeding 5:1. The wavelength, intensity, and energy of the linearly polarized light are selected according to the photosensitivity of the photoalignment material. Usually, the wavelength is in the range of UV-A, UV-B, UV-C or the visible range. Preferably, the linearly polarized light includes light having a wavelength less than 450 nm, more preferably less than 420 nm, and at the same time the linearly polarized light preferably includes light having a wavelength longer than 280 nm, preferably longer than 320 nm, more preferably exceeding 350 nm.

[0070] Irradiance (E e ) or radiant power is defined as the electromagnetic radiant power (dθ) per unit area (dA) incident on a surface.

[0071]

number

[0072] Radiation exposure or radiation dose (H e ) is the irradiance or radiant power (E) per unit time (t). e ) is defined as.

[0073]

number

[0074] At the molecular level, the birefringence of liquid crystals is due to the anisotropy of polarizability (Δα=α ∥ -α ⊥ It depends on the number of electrons. "Polarizability" refers to the ease with which the electron distribution within an atom or molecule can be distorted. Polarizability increases with increasing electron number and diffusion of the electron cloud. Polarizability can be calculated, for example, using the method described in Jap.J.Appl.Phys. Vol. 42 (2003), p. 3463.

[0075] The "optical delay" of a liquid crystal or birefringent material layer at a specific wavelength R(λ) (in nm) is defined as the product of the birefringence at that wavelength Δn(λ) and the layer thickness d (in nm) by the following formula:

[0076]

number

[0077] Optical delay R represents the difference in optical path length (in nanometers) that S-polarized and P-polarized light travel when passing through a birefringent material. "On-axis" delay refers to the delay when the light is incident perpendicularly to the sample surface.

[0078] The retardation of the material (R(λ)) can be measured using a spectroscopic ellipsometer, for example, the M2000 spectroscopic ellipsometer manufactured by J.A. Woollam. This instrument can typically measure the optical retardation of birefringent samples such as quartz in nanometers over a wavelength range from 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.

[0079] The method for performing these measurements was published by N. Singh under the title "Spectroscopic Ellipsometry, Part1 - Theory and Fundamentals, Part2 - Practical Examples and Part3 - measurements" at the National Physical Laboratory (London) in October 2006. It follows the measurement procedures described in the "Retardation Measurement (RetMeas) Manual (2002) and Guide to WVASE (2002) (Woollam Variable Angle Spectroscopic Ellipsometer)" published by J.A. Woollam (Lincoln, Nebraska, USA). Unless otherwise specified, this method is used to determine the retardation of the materials, films, and devices described in the present invention.

[0080] The term "director" is known in the prior art and refers to the preferential orientation direction of the long molecular axis (in the case of calamitic compounds) or the short molecular axis (in the case of discotic compounds) of liquid crystal molecules or RM molecules. In the case of uniaxial orientation of such anisotropic molecules, the director becomes the anisotropic axis.

[0081] The terms "alignment" or "orientation" are related to the alignment (orientation order) of anisotropic units of a material, such as small molecules or fragments of large molecules, in a common direction called the "orientation direction". In the alignment layer of a liquid crystal or RM material, the liquid crystal director coincides with the orientation direction, and the orientation direction corresponds to the direction of the anisotropic axis of the material.

[0082] The terms "uniform orientation" or "uniform alignment" in liquid crystal or RM materials mean, for example, that within a layer of the material, the long molecular axes (in the case of calamic compounds) or short molecular axes (in the case of discotic compounds) of the liquid crystal or RM molecules are oriented in substantially the same direction. In other words, the lines of the liquid crystal directors are parallel.

[0083] The term "homeotropic structure / alignment / orientation" refers to a film in which the optical axis is substantially perpendicular to the film plane.

[0084] The term "planar structure / alignment / orientation" refers to a film in which the optical axis is substantially parallel to the film plane.

[0085] For example, all temperatures, such as the melting point T(C,N) or T(C,S), the transition from the smectic (S) phase to the nematic (N) phase T(S,N), and the transparency point T(N,I) of liquid crystals, are expressed in Celsius. All temperature differences are expressed in degrees.

[0086] If there is any doubt, the definition provided in C. Tschierske, G. Pelzl, and S. Diele, Angew. Chem. 2004, Vol. 116, pp. 6340–6368, applies.

[0087] In the equations shown above and below, R 1 , R 0 , R 00 , R 0* , R 11 , R * , R ** , R C , R 3 , R 4 If the group R or L, including all its variations, represents an alkyl and / or alkoxy group, it may be linear or branched. It is preferably linear and has 2, 3, 4, 5, 6 or 7 C atoms, and therefore preferably represents ethyl, propyl, butyl, pentyl, hexyl, heptyl, ethoxy, propoxy, butoxy, pentoxy, hexyloxy or heptyloxy, and furthermore methyl, octyl, nonyl, decyl, undecyl, dodecyl, tridecyl, tetradecyl, pentadecyl, methoxy, octyloxy, nonyloxy, decyloxy, undecyloxy, dodecyloxy, tridecyloxy or tetradecyloxy.

[0088] In the equations shown above and below, R 1 , R 0 , R 00 , R 0* , R 11 , R * , R ** , R C , R 3 , R 4 If the group R or L, including all its variations, represents an alkyl and / or alkoxy group, it may be linear or branched. It is preferably linear and has 2, 3, 4, 5, 6 or 7 C atoms, and therefore preferably represents ethyl, propyl, butyl, pentyl, hexyl, heptyl, ethoxy, propoxy, butoxy, pentoxy, hexyloxy or heptyloxy, and furthermore methyl, octyl, nonyl, decyl, undecyl, dodecyl, tridecyl, tetradecyl, pentadecyl, methoxy, octyloxy, nonyloxy, decyloxy, undecyloxy, dodecyloxy, tridecyloxy or tetradecyloxy.

[0089] In the equations shown above and below, R 1 , R 0 , R 00 , R 0* , R 11 , R * , R ** , R C , R 3 , R 4 A group R, or L, which includes any variations thereof such as those mentioned above, when representing an alkyl group in which one or more CH2 groups are replaced by S, may be linear or branched. It is preferably linear and has 1, 2, 3, 4, 5, 6 or 7 C atoms, and thus preferably represents thiomethyl, thioethyl, thiopropyl, thiobutyl, thiopentyl, thiohexyl or thioheptyl.

[0090] The oxaalkyl is preferably linear 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.

[0091] In the formulas shown above and below, R 1 、R 0 、R 00 、R 0* 、R 11 、R * 、R ** 、R C 、R 3 、R 4 A group R, or L, which includes any variations thereof such as those mentioned above, when representing an alkoxy group or an oxaalkyl group, may contain one or more additional oxygen atoms, provided that the oxygen atoms are not directly bonded to each other.

[0092] In another preferred embodiment, R 1 、R 0 、R 00 、R 0* 、R 11 、R * 、R ** 、R C 、R 3 、R 4 A group R, or L, which includes any variations thereof such as those mentioned above, [Chemistry] -S 1 -F, -O-S 1 selected from the group consisting of -F, -O-S1-O-S2, wherein S 1 is C 1~12 -alkylene or C 2~12 -alkenylene, and S 2 is H, C 1~12 -alkyl or C 2~12 -alkenyl, and very preferably [Chemistry] selected from the group consisting of -OCH2OCH3, -O(CH2)2OCH3, -O(CH2)3OCH3, -O(CH2)4OCH3, -O(CH2)2F, -O(CH2)3F, and O(CH2)4F.

[0093] In the formulas shown above and below, R 1 , R 0 , R 00 , R 0* , R 11 , R * , R ** , R C , R 3 , R 4 etc., including all variations of the group R, or when L represents an alkyl group in which one CH2 group is replaced by -CH=CH-, this may be linear or branched. Preferably linear and having 2 to 10 C atoms. Thus, it particularly 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, hept-1-, -2-, -3-, -4-, -5- or -6-enyl, oct-1-, -2-, -3-, -4-, -5-, -6- or -7-enyl, non-1-, -2-, -3-, -4-, -5-, -6-, -7- or -8-enyl, dec-1-, -2-, -3-, -4-, -5-, -6-, -7-, -8- or -9-enyl.

[0094] In the equations shown above and below, R 1 , R 0 , R 00 , R 0* , R 11 , R * , R ** , R C , R 3 , R 4 If the group R or L, including all its variations, represents an alkyl or alkenyl radical that is at least monosubstituted with a halogen, the group is preferably linear, and the halogen is preferably F or Cl. In the case of polysubstituted groups, the halogen is preferably F. The resulting radicals also include perfluoro radicals. In the case of monosubstituted groups, the fluorine or chlorine substituent may be at any position, but is preferably at the ω-position.

[0095] Above and below, [ka] represents a trans-1,4-cyclohexylene ring, and [ka] This represents a 1,4-phenylene ring.

[0096] The halogen is preferably F or Cl, and very preferably F.

[0097] Group-CR 0 =CR 00 - is preferably -CH=CH-.

[0098] -OC-, -CO-, -C(=O)-, and -C(O)- are carbonyl groups, i.e., [ka] It represents.

[0099] Preferred substituents L include, 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, each having 1 to 25 C atoms, a linear or branched alkyl, alkoxy, alkylcarbonyl, alkoxycarbonyl, alkylcarbonyloxy or alkoxycarbonyloxy (wherein one or more H atoms may be substituted with F or Cl), a substituted silyl having 1 to 20 Si atoms, or a substituted aryl having 6 to 25, preferably 6 to 15 C atoms,

[0100] In the formula, R x is a linear, branched, or cyclic alkyl having H, F, Cl, CN, or 1 to 25 C atoms, wherein one or more non-adjacent CH2 groups may be substituted with -O-, -S-, -CO-, -CO-O-, -O-CO-, -O-CO-O-, such that the O and / or S atoms are not directly linked to each other, and one or more H atoms may be substituted with F, Cl, P- or P-Sp-, and Y 1 This represents halogen.

[0101] Particularly preferred substituents L include, for example, F, Cl, CN, NO2, CH3, C2H5, and OCH3. 3、 SCH3, OC2H5, SC2H5, COCH3, COC2H5, COOCH3, COOC2H5, CF3, OCF3, OCHF2, OC2F5, and also phenyl.

[0102] [ka] And, In the formula, L has one of the meanings described above.

[0103] Throughout this application, the terms “aryl groups and heteroaryl groups” encompass groups that can be monocyclic or polycyclic. That is, they may have one ring (e.g., phenyl) or two or more rings, and they may also be condensed (e.g., naphthyl) or covalently bonded (e.g., biphenyl), or include a combination of fused and bonded rings. Heteroaryl groups preferably contain one or more heteroatoms 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, which optionally include fused rings and are optionally substituted. Furthermore, 5, 6, or 7-membered aryl and heteroaryl groups are preferred, in which case one or more CH groups may be replaced with N, S, or O such that the O and / or S atoms are not directly bonded to each other. Preferred aryl groups include, for example, phenyl, biphenyl, terphenyl, [1,1':3',1”]terphenyl-2'-yl, naphthyl, anthracene, binaphthyl, phenanthrene, pyrene, dihydropyrene, chrysene, perylene, tetracene, pentacene, benzopyrene, fluorene, indene, indenofluorene, spirobifluorene, and more preferably 1,4-phenylene, 4,4'-biphenylene, and 1,4-tephenylene.

[0104] Preferred heteroaryl groups include, for example, five-membered rings such as pyrrole, pyrazole, imidazole, 1,2,3-triazole, 1,2,4-triazole, tetrazole, furan, thiophene, selenophene, oxazole, isoxazole, 1,2-thiazole, 1,3-thiazole, 1,2,3-oxadiazole, 1,2,4-oxadiazole, 1,2,5-oxadiazole, 1,3,4-oxadiazole, 1,2,3-thiadiazole, 1,2,4-thiadiazole, 1,2,5-thiadiazole, and 1,3,4-thiadiazole, as well as six-membered rings such as pyridine, pyridazine, pyrimidine, pyrazine, and 1,3,5-triazine. 1,2,4-triazine, 1,2,3-triazine, 1,2,4,5-tetrazine, 1,2,3,4-tetrazine, 1,2,3,5-tetrazine, or condensation groups, e.g., indole, iso-indole, indidine, indazole, benzimidazole, benzotriazole, purine, naphthoimidazole, phenanthrimidazole, pyridimidazole, pyrazinimidazole, quinoxalinimidazole, benzoxazole, naphthoxazole, anthroxazole, fenantroxazole, isoxazole, benzothiazole, benzofuran, isobenzofuran, diben These include zofuran, quinoline, isoquinoline, pteridine, benzo-5,6-quinoline, benzo-6,7-quinoline, benzo-7,8-quinoline, benzoisoquinoline, acridine, phenothiazine, phenoxazine, benzopyridazine, benzopyrimidine, quinoxaline, phenazine, naphthyridine, azacarbazole, benzocarbolin, phenantholidine, phenanthroline, thieno[2,3b]thiophene, thieno[3,2b]-thiophene, dithienothiophene, isobenzothiophene, dibenzothiophene, benzothiadiazothiophene, or combinations of these. The heteroaryl group may be substituted with alkyl, alkoxy, thioalkyl, fluorine, fluoroalkyl, or further aryl or heteroaryl groups.

[0105] base [ka] In this example, the single bond shown between the two ring atoms can be bonded to any free position on the benzene ring.

[0106] -OC-, -CO-, -C(=O)-, and -C(O)- are carbonyl groups, i.e., [ka] It represents.

[0107] Polymerizable group P is P 0 , P 1 , P 2 , P *0 These groups are suitable for polymerization reactions such as free radical or ionic chain polymerization, polyaddition or polycondensation, or polymer-like reactions such as addition or condensation onto a main polymer chain, including all variations thereof. Particularly preferred are groups for chain polymerization, especially those containing a C=C double bond or a -C≡C- triple bond, and groups suitable for ring-opening polymerization, such as oxetane or epoxide groups.

[0108] The preferred group P is P 0 , P 1 , P 2 , P *0 Including all of its variations, CH2=CW 1 -CO-O-, CH2=CW 1 -CO-, [ka] 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 Selected from the group consisting of Si-, in the formula, W 1 This represents H, F, Cl, CN, CF3, phenyl, or alkyl having 1 to 5 C atoms, especially H, F, Cl or CH3, and W 2 and W 3 Each of these independently represents an alkyl group having H or 1 to 5 C atoms, particularly H, methyl, ethyl, or n-propyl, and W 4 , W 5 and W 6 Each of these independently represents a chlorine, oxaalkyl, or oxacarbonylalkyl group having 1 to 5 C atoms, and W 7 and W 8 k1, k2, and k3 each independently represent H, chlorine, or an alkyl group having 1 to 5 C atoms; Phe represents 1,4-phenylene which may be substituted with one or more groups L 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.

[0109] A very preferred group P is P 0 , P 1 , P 2 , P *0 Including all of its variations, CH2=CW 1 -CO-O-, CH2=CW 1 -CO-, [ka] 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 6 Selected from the group consisting of Si-, in the formula, W 1 This represents H, F, Cl, CN, CF3, phenyl, or alkyl having 1 to 5 C atoms, especially H, F, Cl or CH3, and W 2 and W 3 Each of these independently represents an alkyl group having H or 1 to 5 C atoms, particularly H, methyl, ethyl, or n-propyl, and W 4 , W 5 and W 6 Each of these independently represents a chlorine, oxaalkyl, or oxacarbonylalkyl group having 1 to 5 C atoms, and W 7 and W 8 k1, k2, and k3 each independently represent H, chlorine, 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.

[0110] A particularly preferred group P is P 0 , P 1 , P 2 , P *0 Including all of its variations, CH2=CW 1 -CO-O-, especially CH2=CH-CO-O-, CH2=C(CH3)-CO-O- and CH2=CF-CO-O-, and furthermore CH2=CH-O-, (CH2=CH)2CH-O-CO-, [ka] (CH2=CH)2CH-O-, [ka] Selected from the group consisting of

[0111] A more preferred polymerizable group P is P 0 , P 1 , P 2 , P *0 From the group consisting of vinyloxy, acrylate, methacrylate, fluoroacrylate, chloroacrylate, oxetane, and epoxide, including all variations thereof, acrylate and methacrylate are most preferably selected.

[0112] In another preferred embodiment of the present invention, in polymerizable compounds disclosed above and below, including compounds of formula I and its subformulas, all polymerizable groups have the same meaning and preferably represent acrylate or methacrylate, very preferably acrylate.

[0113] A spacer group different from a single bond is Sp 0 , Sp 1 , Sp 2 , Sp *0 Including all its variations, each base P-Sp- etc. is a formula Sp"-X" such that it matches formula P-Sp"-X", and in the formula, Sp'' represents a linear or branched alkylene having 1 to 20, preferably 1 to 12, carbon atoms, which may be monosubstituted or polysubstituted with F, Cl, Br, I, or CN, and in addition, one or more non-adjacent CH2 groups are independently of each other such that the O and / or S atoms are not directly linked to each other, such as -O-, -S-, -NH-, -N(R) 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- can be used as substitutes, “X” is -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 bond are represented. R 0 and R 00 Each of these independently represents an alkyl group having either H or 1 to 20 C atoms, and Y 2 and Y 3 Each of these independently represents H, F, Cl, or CN.

[0114] X'' is preferably -O-, -S-, -CO-, -COO-, -OCO-, -O-COO-, -CO-NR 0 -, -NR 0 -CO-, -NR 0 -CO-NR 00 -or it is a single bond.

[0115] A typical spacer base Sp is Sp 0 , Sp 1 , Sp 2 , Sp *0 , and all its variations such as -Sp”-X”-, 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 - and in the formula, p1 is an integer from 1 to 12, q1 is an integer from 1 to 3, R 0 and R 00 The above has the meanings shown.

[0116] A particularly preferred group Sp is Sp 0 , Sp 1 , Sp 2 , Sp *0 , and all its variations such as -Sp”-X”-, -(CH2) p1 -,-(CH2) p1 -O-, -(CH2) p1 -O-CO-, -(CH2) p1 -CO-O-, -(CH2) p1 The equation is -O-CO-O-, where p1 and q1 have the meanings described above.

[0117] Particularly preferred groups Sp'' are, in each case, linear ethylene, propylene, butylene, pentylene, hexylene, heptylene, octylene, nonylene, decylene, undecylene, dodecylene, octadecylene, ethyleneoxyethylene, methyleneoxybutylene, ethylenethioethylene, ethylene-N-methyliminoethylene, 1-methylalkylene, etenylene, propenylene, and butenylene.

[0118] In another preferred embodiment of the present invention, polymerizable compounds as disclosed above and below include compounds of formula I and its subformulas, such as Sp-P and Sp(P). s Sp is substituted with one or more polymerizable groups P to correspond to (where s is 2 or greater). 0 , Sp 1 , Sp 2 , Sp *0 This includes all variations of such groups, including spacer groups (branched polymerizable groups) Sp.

[0119] A preferred polymerizable compound according to this preferred embodiment is a compound in which s is 2, i.e., a compound containing the group Sp(P)2. A very preferred polymerizable compound according to this preferred embodiment contains a group selected from the following formulas.

[0120] [ka]

[0121] In the formula, P is defined as in formula I, Alkyl represents a linear or branched alkylene having single bonds or 1 to 12 carbon atoms, which is either unsubstituted or mono- or polysubstituted with F, Cl, or CN, wherein one or more non-adjacent CH2 groups are independently linked to each other, and the oxygen and / or sulfur atoms are not directly linked to each other, such that -C(R 0 )=C(R 0 )-, -C≡C-, -N(R 0 )-, -O-, -S-, -CO-, -CO-O-, -O-CO-, -O-CO-O- can be substituted, and in the formula, R 0 It has the above meaning, aa and bb each independently represent 0, 1, 2, 3, 4, 5, or 6. X has one of the meanings indicated by X'', and is preferably O, CO, SO2, O-CO-, CO-O, or a single bond.

[0122] A preferred spacer base Sp(P)2 is selected from formulas S1, S2, and S3.

[0123] A highly preferred spacer base Sp(P)2 is selected from the following sub-formulas.

[0124] [ka]

[0125] <Detailed explanation> In the compounds of formula I and its subformulas described above, P is preferably selected from the group consisting of vinyloxy, acrylate, methacrylate, fluoroacrylate, chloroacrylate, oxetane, and epoxide, very preferably selected from acrylate and methacrylate, and most preferably acrylate.

[0126] Even more preferred are compounds of the above and the following formula I and its subformulas, where all polymerizable groups P present in the compound have the same meaning, very preferably representing acrylate or methacrylate, and most preferably acrylate.

[0127] More preferably are compounds of the above and the following formula I and its subformulas, which contain 1, 2, 3, or 4 P-Sp groups, very preferably 2 or 3 P-Sp groups.

[0128] Even more preferable is R 11 The compound is P-Sp-, and is a compound of the above and the following formula I and its subformulas.

[0129] Even more preferable is R 11 Unlike P-Sp-, it preferably has CN, -SCN, preferably 1 to 12, preferably 1 to 6 C atoms, and is a compound selected from alkyl, alkoxy, thioalkyl, alkylcarbonyl, alkoxycarbonyl, alkylcarbonyloxy or alkoxycarbonyloxy which may be fluorinated, and is the above and the following formula I and its subformulas.

[0130] Even more preferable is that Sp is a single bond or -(CH2) p1 -, -O-(CH2) p1 -, -O-CO-(CH2) p1 , or -CO-O-(CH2) p1 (In the formula, p1 is 2, 3, 4, 5, or 6.) where Sp is -O-(CH2) p1 -, -O-CO-(CH2) p1 , or -CO-O-(CH2) p1 In this case, the compounds are those of the above and the following formula I and its subformulas, in which an O atom or a CO group is linked to the benzene ring, respectively.

[0131] Even more preferable are compounds of the above formula I and its subformulas, wherein at least one Sp group is a single bond.

[0132] More preferably are compounds of the above formula I and its subformulas, wherein at least one group Sp is a single bond and at least one group Sp is different from a single bond.

[0133] Even more preferable is that at least one group Sp, unlike a single bond, is -(CH2) p1 -, -O-(CH2) p1 -, -O-CO-(CH2) p1 , or -CO-O-(CH2) p1 (wherein p1 is an integer from 2 to 10, preferably 2, 3, 4, 5, or 6.) Sp is selected from -O-(CH2) p1 -, -O-CO-(CH2) p1 , or -CO-O-(CH2) p1 In this case, the compounds are those of the above and the following formula I and its subformulas, in which an O atom or a CO group is linked to the benzene ring, respectively.

[0134] More preferably are compounds of formula I and its subformulas as described above and below, where L is a P-Sp-, -CN, or a linear, branched, or cyclic alkyl having 1 to 25 C atoms, wherein one or more non-adjacent CH2- groups are O-, -S-, -CO-, -CO-O-, -O-CO-, -O-CO-O-, CR such that the O- and / or S- atoms are not directly bonded to each other. 0 =CR 00 -, -C≡C-, [ka] It may be replaced by, however, one or more H atoms may each be replaced by a substituent L which may form a cycloalkyl or cycloalkenyl group having 5, 6, 7, or 8 C atoms, with two of them directly bonded to an adjacent C atom.

[0135] Of particular preference are compounds of formula I and its subformulas as described above and below, where L is a linear 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.

[0136] Even more preferred are compounds of formula I and its subformulas as described above and below, where Z 11 and Z 12 -COO-, -OCO-, -C≡C-, or a single bond, more preferably -C≡C- or a single bond, most preferably a single bond.

[0137] Preferably, A, B, D and E in formula I are

[0138] [ka] Selected from the group consisting of,

[0139] In the formula, each base is independent of the others and, in each instance, identical or different in meaning as follows: L is an alkyl, alkoxy, or thioalkyl group that may be P-Sp-, -CN, F, C, or fluorinated, having 1 to 6, preferably 1 to 3, more preferably 1 or 2 C atoms, preferably P-Sp-, -CN, F, Cl, OCH3, SCH3, C2H5, OC2H5, SC2H5. r is 0, 1, 2, 3 or 4, preferably 0, 1 or 2. s is 0, 1, 2, or 3, preferably 0 or 1. t is 0, 1, or 2, preferably 0 or 1.

[0140] More preferably, rings A, B, D and / or E in formula I are selected from the group consisting of benzene-1,4-diyl, naphthalene-1,4-diyl, naphthalene-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, and benzothiophene-4,7-diyl, all of which may be substituted with one or more groups L and / or P-Sp-.

[0141] Very preferably, one, two, three, four or more rings A, B, D and / or E in formula I are

[0142] [ka] Selected from the group consisting of,

[0143] In the formula, L represents an alkyl, alkoxy, or thioalkyl group having 1 to 6, preferably 1 to 3, more preferably 1 or 2 C atoms, which may be P-Sp-, -CN, F, Cl, or fluorinated, and is the same or different in each occurrence, and is preferably P-Sp-, -CN, F, Cl, OCH3, SCH3, C2H5, OC2H5, or SC2H5.

[0144] Particularly preferred are compounds of formula I, in particular n=m=0, where rings B and D are selected from the group consisting of benzene-1,4-diyl, naphthalene-1,4-diyl, naphthalene-2,6-diyl, or anthracene-9,10-diyl, all of which may be monosubstituted or disubstituted with L and / or P-Sp-.

[0145] Preferably, the ring C in formula I is

[0146] [ka] Selected from the group consisting of,

[0147] In the formula, each base is independent of the others and, in each instance, identical or different in meaning as follows: L is an alkyl, alkoxy, or thioalkyl group that may be P-Sp-, -CN, F, C, or fluorinated, having 1 to 6, preferably 1 to 3, more preferably 1 or 2 C atoms, preferably P-Sp-, -CN, F, Cl, OCH3, SCH3, C2H5, OC2H5, SC2H5. r is 0, 1, 2, 3 or 4, preferably 0, 1 or 2. s is 0, 1, 2, or 3, preferably 0 or 1. t is 0, 1, or 2, preferably 0 or 1.

[0148] More preferably, C in formulas I, I1 and I2 is

[0149] [ka] Selected from the group consisting of,

[0150] In the formula, L represents an alkyl, alkoxy, or thioalkyl group having 1 to 6, preferably 1 to 3, more preferably 1 or 2 C atoms, which may be P-Sp-, -CN, F, Cl, or fluorinated, and is the same or different in each occurrence, preferably P-Sp-, -CN, F, Cl, OCH3, SCH3, C2H5, OC2H5, or SC2H5.

[0151] The ring C in formula I is very preferably selected from the group consisting of benzene-1,4-diyl, naphthalene-1,4-diyl, or anthracene-9,10-diyl, all of which may be monosubstituted or disubstituted with L and / or P-Sp-.

[0152] Preferably, the compound is of formula I, where n=m=0, and rings B, C, and D form groups selected from the following formulas or their mirror images.

[0153] [ka]

[0154] [ka]

[0155] [ka]

[0156] In the formula, the naphthalene group and the phenanthrene group may be substituted with one or two groups L, 1 and L 2 Each of these independently represents H or has one of the meanings given to L in formula I, where r is 0, 1, 2, 3, or 4, preferably 0, 1, or 2, and L is as defined in formula I.

[0157] In formulas T1 to T30, L preferably represents an alkyl, alkoxy or thioalkyl having 1 to 6 C atoms, preferably 1 to 3, more preferably 1 or 2, and may be P-Sp-, -CN, F, Cl, or fluorinated, and is the same or different in each occurrence, and is very preferably P-Sp-, methyl, ethyl, methoxy, ethoxy, thiomethyl or thioethyl, most preferably methyl or ethyl, and r preferably 0, 1, 2 or 3, very preferably 0, 1 or 2.

[0158] Of particular preference are the bases of formulas T1 to T7.

[0159] A highly preferred compound of formula I is selected from the following sub-formulas.

[0160]

change

[0161]

change

[0162]

change

[0163]

change

[0164]

change

[0165]

change

[0166]

change

[0167]

change

[0168]

change

[0169]

change

[0170]

change

[0171] In the formula, the naphthalene group and the phenanthrene group may be substituted with one or two groups L, and P, Sp, L, and r each independently, identical or different in each occurrence, have the meaning shown in formula I or one of the preferred meanings shown above and below, and R is the R in formula I 11 It has one of the meanings indicated by and preferably represents 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 from methyl or ethyl groups. P is preferably an acrylate.

[0172] Even more preferable are compounds of formulas I and I-1 to I-103, in which one of the two Sp groups is a single bond and the other Sp group is not a single bond.

[0173] Further preferred compounds of formulas I and I-1 to I-103 are selected from the following preferred embodiments, including any combination thereof: n=m=0, or n=1 and m=0, or n=m=1 and / or • One of rings B and D is a single bond, and / or • Ring C represents naphthalene-1,4-diyl or anthracene-9,10-diyl, or The ring C represents a benzene-1,4-diyl substituted with an alkyl, alkoxy or thioalkyl, more preferably methyl or ethyl, most preferably ethyl, having 1 to 3, preferably 1 or 2 C atoms, and / or At least one of rings B and D represents naphthalene-1,4-diyl, naphthalene-2,6-diyl, or anthracene-9,10-diyl, and may be substituted with one or more L or P-Sp- groups, and / or At least one of rings B, C, and D represents naphthalene-1,4-diyl, naphthalene-2,6-diyl, or anthracene-9,10-diyl, which may be substituted with one or more L or P-Sp- groups, and / or at least one of rings B, C, and D is benzene-1,4-diyl substituted with an ethyl group. • P represents acrylate or methacrylate, and / or Sp is Sp"-X", preferably -Sp"-X"- is -(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 ·R 11 Or, if R is P-Sp-, then both P-Sp- bases are identical, or ·R 11 Or, if R is P-Sp-, one Sp group is a single bond, the other Sp group is not a single bond, and / or ·L is selected from methyl, ethyl, methoxy, ethoxy, thiomethyl or thiomethyl, more preferably from methyl or ethyl, very preferably from ethyl, r represents 1, and / or ·L is selected from methyl, ethyl, methoxy, ethoxy, thiomethyl or thiomethyl, more preferably from methyl or ethyl, very preferably from ethyl, r represents 2, and / or • Ring C is substituted with one L representing P-Sp-, preferably an acrylate, and / or ·R 11 is P-Sp-, or ·R 11 The component is F, Cl, CN, OCH3 or SCH3, preferably OCH3 or SCH3, and very preferably OCH3.

[0174] The following are highly preferred compounds of formula I.

[0175] [ka]

[0176] [ka]

[0177] [ka]

[0178] [ka]

[0179] [ka]

[0180] [ka]

[0181] [ka]

[0182] [ka]

[0183] [ka]

[0184] [ka]

[0185] Of particular preference are the compounds of 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-71, I-72, and I-73.

[0186] The synthesis of compounds of formula I and its subformulas can be carried out by methods known to those skilled in the art from the literature, or by similar methods, as described, for example, in International Publication No. 2022 / 33908.

[0187] Compounds of formula I, either alone or in combination with other RMs in an RM mixture, particularly preferably simultaneously, exhibit high birefringence, good solubility in commonly known organic solvents used in mass production, improved orientation in RM mixtures, a favorable transition temperature, and high resistance to yellowing after exposure to ultraviolet light.

[0188] Preferably, the RM mixture contains one or more compounds selected from formula I, preferably 1 to 5, very preferably 1, 2, or 3, preferably selected from formula I-1 to I-97, and very preferably selected from formula I1 to I76.

[0189] The concentration of compound of formula I or its sub-formula in the RM mixture is preferably 35-99%, and very preferably 40-98%.

[0190] The RM mixture according to the present invention further comprises, in addition to a polymerizable compound of formula I or a subformula of formula I, one or more chiral isomerizing compounds preferably selected from chiral photoisomerizing compounds.

[0191] Chiral isomerized compounds may or may not be polymerizable. They may be non-mesogenic or mesogenic compounds. If chiral isomerized compounds are polymerizable, they may be monoreactive or polyreactive.

[0192] In preferred embodiments, the RM mixture according to the present invention comprises one or more polymerizable chiral isomerized compounds.

[0193] In another preferred embodiment, the RM mixture according to the present invention comprises exactly one chiral isomerized compound.

[0194] More preferably, the RM mixture comprises only polymerizable and chiral isomerized compounds, and is preferably selected from mono- or di-reactive chiral isomerized compounds.

[0195] More preferably, the RM mixture does not contain isomerizing groups, and in particular, does not contain chiral compounds that do not contain photoisomerizing groups.

[0196] In another preferred embodiment, the RM mixture according to the present invention does not contain other chiral compounds in addition to the chiral isomerizing compound (one or more).

[0197] A suitable polymerizable chiral isomerized compound preferably comprises one or more ring elements linked directly or via a linking group, two of which may optionally be linked to each other directly or via a linking group, the linking group being the same as or different from the aforementioned linking group. The ring elements are preferably selected from the group of 4-membered rings, 5-membered rings, 6-membered rings, or 7-membered rings, preferably 5-membered rings or 6-membered rings.

[0198] Preferred chiral isomerized compounds are those of formula I * Selected from.

[0199] [ka]

[0200] In the formula, each base is independent of the others and, in each instance, identical or different in meaning as follows: R 3 , R 4 These are H, F, Cl, CN, P-Sp-, or alkyl groups containing up to 25 C atoms, which may be unsubstituted, monosubstituted or polysubstituted with halogens or CN, and one or more non-adjacent CH2 groups may be independently replaced in each case with -O-, -S-, -NH-, -N(CH3)-, -CO-, -COO-, -OCO-, -OCO-O-, -S-CO-, -CO-S-, or -C≡C-, such that the oxygen atoms are not directly bonded to each other. P is a polymerizable group, Sp is a spacer group or a single bond. Z 3 , Z 4 These are -CO-O-, -O-CO-, -CH2CH2-, -OCH2-, -CH2O-, -CH=CH-, -CH=CH-CO-O-, -O-CO-CH=CH-, -CH=C(CN)-CO-O-, -O-CO-C(CN)=CH-, -N=N-, -CH=N-, -N=CH-, -C≡C- or single bonds. A 3 , A 4 This refers to an alicyclic, heterocyclic, aromatic, or heteroaromatic group having 4 to 20 ring atoms, which may be monocyclic or polycyclic, and may be substituted with one or more L or P-Sp- groups. G is a chiral group, L is a linear, branched, or cyclic alkyl group having F, Cl, -CN, -SCN, P-Sp-, or 1 to 25 C atoms, and one or more non-adjacent CH2 groups such that the O- and / or S atoms are not directly linked to each other, such as -O-, -S-, -CO-, -CO-O-, -O-CO-, -O-CO-O-, -CR 0 =CR 00 -, -C≡C-, [ka] It may be replaced by, however one or more H atoms may each be replaced with P-Sp-, F or Cl, or two substituents L directly bonded to adjacent C atoms may form a cycloalkyl or cycloalkenyl group containing 5, 6, 7 or 8 C atoms. m and l are 0, 1, 2, or 3, independently of each other. k is 0, 1, or 2. However, the compound contains at least one isomerizing group, which is preferably a photoisomerizing group.

[0201] Formula I described above and below * In the compounds of the same subformula, R 3 or R 4 If the group is an alkyl or alkoxy group, i.e., if the terminal CH2 group is replaced by -O-, it may be linear or branched. It is preferably linear and has 2, 3, 4, 5, 6, 7 or 8 carbon atoms, and therefore preferably ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, ethoxy, propoxy, butoxy, pentoxy, hexoxy, heptoxy or octoxy, and furthermore methyl, nonyl, decyl, undecyl, dodecyl, tridecyl, tetradecyl, pentadecyl, methoxy, nonoxy, decoxy, undecoxy, dodecoxy, tridecoxy or tetradecoxy.

[0202] In the case of oxaalkyl, i.e., where one CH2 group is replaced by -O-, it is preferably linear 2-oxapropyl (=methoxymethyl), 2-(=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.

[0203] Equation I * and preferred compounds of the subformula are R 3 and R 4 At least one of, preferably R 3 and R 4 Both are compounds that represent P-Sp-.

[0204] Equation I * And a more preferred compound of the subformula is R 3 and R 4 At least one of, preferably R 3 and R 4 Both are different from P-Sp- and represent an alkyl or alkoxy having preferably 1 to 12, more preferably 1 to 12 C atoms, and R 3 and R 4 One of these compounds may represent F, Cl, or CN.

[0205] Equation I * A more preferred compound of the subformula is A 3 and A 4 However, 1,4-phenylene, 1,3-phenylene, naphthalene-1,4-diyl, naphthalene-2,6-diyl, phenanthrene-2,7-diyl, 9,10-dihydrophenanthrene-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, flavones (however, one or more CH groups in these groups may be replaced with N), cyclohexane-1,4-diyl (however, these Compounds selected from the group consisting of 1,4-cyclohexenylene, 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, indan-2,5-diyl, octahydro-4,7-methanoindan-2,5-diyl, 2-benzylidene-1-indanone, chalcone, chromone, and pentarenone, all of which may be substituted with one or more L or P-Sp- groups.

[0206] Equation I * A very preferred compound of the subformula is A 3 and A 4 However, the compounds are selected from the group consisting of 1,4-phenylene, naphthalene-1,4-diyl, naphthalene-2,6-diyl, 1,4-cyclohexylene (wherein one or more non-adjacent CH2 groups in these groups may be replaced 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-tetrahydronaphthalene-2,6-diyl, very preferably 1,4-phenylene or 1,4-cyclohexylene, all of which may be substituted with one or more L or P-Sp- groups.

[0207] Equation I * And a more preferred compound of the subformula is Z 3 and Z 4 These represent -CO-O-, -O-CO-, or a single bond, independently of each other.

[0208] Equation I * More preferred compounds of the subformula are compounds in which L is selected from F, Cl, CN, CH3, C2H5, OCH3, OC2H5, COCH3, COC2H5, CF3, OCF3, P-Sp-, particularly F, Cl, CN, CH3, C2H5, OCH3, COCH3 or OCF3, most preferably F, CH3, OCH3 or COCH3.

[0209] Equation I * A more preferred compound of the subformula is one in which P is selected from the group consisting of vinyloxy, acrylate, methacrylate, fluoroacrylate, chloroacrylate, oxetane, and epoxide, very preferably from acrylate and methacrylate, and most preferably from acrylate.

[0210] Equation I * And a more preferred compound of the subformula is one in which Sp is a single bond or -(CH2) p1 -, -O-(CH2) p1 -, -O-CO-(CH2) p1 , or -CO-O-(CH2) p1 This represents a function where p1 is an integer from 2 to 10, preferably 2, 3, 4, 5, or 6, and Sp is -O-(CH2) p1 -, -O-CO-(CH2) p1 or -CO-O-(CH2) p1 In this case, an O atom or a CO group is linked to the benzene ring.

[0211] Equation I * In the more preferred compounds of the same subformula, all polymerizable groups P present in the compound have the same meaning, and very preferably represent acrylate or methacrylate, most preferably acrylate.

[0212] Equation I * More preferred compounds of the same subformula contain one, two, three, or four P-Sp groups, particularly two or three P-Sp groups.

[0213] Equation I * A more preferred compound of the subformula is one in which at least one Sp group is a single bond.

[0214] Equation I * A more preferred compound of the subformula is one in which at least one group Sp is a single bond and at least one group Sp is not a single bond.

[0215] Equation I * A more preferred compound of the subformula is one in which at least one group Sp differs from a single bond, -(CH2) p1 -, -O-(CH2) p1 -, -O-CO-(CH2) p1 , or -CO-O-(CH2) p1 Selected from, p1 is an integer from 2 to 10, preferably 2, 3, 4, 5 or 6, and Sp is -O-(CH2) p1 -, -O-CO-(CH2) p1 , or -CO-O-(CH2) p1 In this case, an O atom or a CO group is linked to the benzene ring.

[0216] R a or R b If the base is of formula P-Sp-, the spacer groups on both sides of the mesogenic core may be the same or different.

[0217] The above and the following formula I * In the compounds of the same subformula, m and l are preferably 0 or 1.

[0218] The above and the following formula I * In the compounds of the same subformula, q is preferably 0 or 1, and very preferably 0.

[0219] Equation I * Of the compounds, the following are particularly preferred:

[0220] [ka]

[0221] In the formula, P, Sp, A 3 , A 4 , Z 3 , Z 4 And G is, Equation I * The meaning given by, or having one of the preferred meanings described above, R * This is different from P-Sp- and R 3 It has one of the meanings of, and R ** This is different from P-Sp- and R 4 It has one of the meanings.

[0222] Of these preferred compounds, Formula I * 8~I * 10 compounds are particularly preferred, and formula I * Compound 8 is particularly preferred.

[0223] Equation I * 1~I * A smaller group of the 10 particularly preferred compounds is shown below. For simplicity, Phe is 1,4-phenylene which may be substituted with L at the 2 and / or 3 positions, and Cyc is 1,4-cyclohexylene.

[0224] Equation I * 2, I3, I * 5. I * 6. I * 7, I * 9 and I * The 10 particularly preferred compounds are those with the following formula:

[0225] [ka]

[0226] [ka]

[0227] In the formula, P, Sp, Z 3 , Z 4 And G is given by Equation I * Having the meaning given in or one of the preferred meanings described above and below, R * This is different from P-Sp- and formula I * R 3 It has one of the meanings, R ** This is different from P-Sp- and formula I * R 4 It has one of the meanings.

[0228] Preferably, Formula I * 2-1~I * In compound 7-4, R * and R ** Each of them is independently an alkyl or alkoxy having 1 to 12 carbon atoms, or an alkyl or alkoxy having 1 to 12 carbon atoms, and the other is F, Cl or CN. Furthermore, -Sp- is preferably an alkylene or alkylene oxy having 1 to 12 carbon atoms, P is preferably an acrylate or methacrylate, and Z 3 and Z 4 Each of these independently represents -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 a single bond, more preferably -CO-O-, -O-CO- or a single bond.

[0229] Equation I * The preferred compounds of the subformula are those in which G represents or contains a photoisomerizing group.

[0230] Equation I * And a more preferred compound of the subformula is Z 3 and / or Z 4 However, each of these independently represents -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-.

[0231] Equation I * More preferred compounds of the same subformula contain an isomerizing group selected from stilbene, (1,2-difluoro-2-phenylvinyl)benzene, cinnamate, α-cyanocinnamate, 4-phenylbuta-3-en-2-one, Schiff base, 2-benzylidene-1-indanone, chalcone, coumarin, chromone, pentarenone, or azobenzene.

[0232] Equation I * More preferred compounds of the subformula thereof are those in which the chiral group G is selected from or derived from dianhydrohexitol, preferably isosorbide, isomannide or isoidide, 1,1'-bi-2-naphthol (binol), 1,2-diphenyl-1,2-ethanediol (hydrobenzoin), 2-benzylidene-p-menthan-3-one and menthyl cinnamate ((1R,2S,5R)-5-methyl-2-(1-methylethyl)cyclohexyl(2E)-3-phenyl-2-propenoate).

[0233] Equation I * A very preferred compound of the subformula is one in which the chiral group G is selected from formula A:

[0234] [ka]

[0235] In the formula, X is -CO-O-, -CH=CH-CO-O-, or -CH=C(CN)-CO-O-, where the ester O atom is linked to the furan ring, or -N=N-, q is 0, 1, 2, 3, or 4, and L is formula I * It has the meaning of, or one of the preferred meanings shown above and below.

[0236] Formula A includes the following stereoisomers based on the corresponding dianhydrohexitol:

[0237] [ka]

[0238] In the formula, X, L, and q have the meanings given in formula A, Ai is based on isosorbide, Aii is based on isomannide, and Aiii is based on isoidide. Ai is particularly preferred.

[0239] Equation I * And a more preferred compound of the subformula is Z 3 and Z 4 One or both of them independently represent -CH=CH-CO-O-, -O-CO-CH=CH-, -CH=C(CN)-CO-O-, -O-CO-C(CN)=CH-, -CH=N-, -N=CH-, or -N=N-, and / or G in equation A is preferably Ai, and X represents -CH=CH-CO-O-, -CH=C(CN)-CO-O-, or -N=N-.

[0240] Equation I * A more preferred compound of the subformula is one in which G in formula A is preferably Ai, and X represents -CH=CH-CO-O-, -CH=C(CN)-CO-O- or -N=N-, very preferably -CH=CH-CO-O-.

[0241] Equation I * A more preferred compound of the subformula is one in which the chiral group G is selected from the following formulas.

[0242] [ka]

[0243] During the ceremony, X, L, and q have the meanings given in formula A or one of the preferred meanings given above and below. R 11 and R 12 These are, independently of each other, equation I * -(Z 4 -A 4 ) l -R 4 Does it represent, or R 11 and R 12 It combines with the O atom, and formula I * -(Z 4 -A 4 ) l -R 4 A cyclic or spirocyclic group may be substituted with, R 13 and R 14 These are, independently of each other, equation I * R as defined by 3 -(A 3 -Z 3 ) m - represents, a1 and a2 are each independently 0, 1, or 2. And the dashed line is Equation I * This represents a connection to an adjacent base within the structure.

[0244] Equation I * The preferred compound is selected from the following formulas.

[0245] [ka]

[0246] [ka]

[0247] In the formula, R 3 , R 4 , Z 4 , A 4 , L and q are given by formula I * It has the meaning given by or one of the preferred meanings given above and below, where l1 is 0, 1 or 2, and R 13 , R 14 a1 and a2 have the meanings given by formula G or one of the preferred meanings given by above and below, R 15 is equation I * -(Z 4 -A 4 ) l -R 4 This represents X 11 and X 12 -O-CO-CH=CH represents -O-CO-CH=CH.

[0248] Equation I * A highly preferred compound of A is selected from the following sub-formulas:

[0249] [ka]

[0250] [ka]

[0251] In the formula, P, Sp, L, and q are given in formula I * Having the meaning given by or one of the preferred meanings given above and below, R * P-Sp- is different from formula I * R 3 It has one of the meanings, R ** P-Sp- is different from formula I * R 4 It has one of the meanings.

[0252] Equation I is particularly preferred. * It is a compound of A3.

[0253] Even more preferable is formula I in which the central isosorbide unit is replaced with an isomannide or isoidide unit. * A, I * B, I * A1, I * A2 and I * It is a stereoisomer of A3.

[0254] 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 -, very preferably -O-(CH2) p1 - and in the formula, an O atom or a CO group is linked to a benzene ring, p1 is an integer from 1 to 6, more preferably 2, 3, 4, 5 or 6, and R 4 It is preferably P-Sp-.

[0255] Equation I * And more preferred compounds of the subformula are selected from the following formulas:

[0256] [ka]

[0257] [ka]

[0258] [ka]

[0259] [ka]

[0260] [ka]

[0261] In the formula, P, Sp, R * , R ** , L and q are given by formula I * and I * Having the meaning given in A1 or one of the preferred meanings as given above and below, R 16 and R 17 Each of these independently represents an alkyl group having 1 to 12, preferably 1 to 6, carbon atoms, very preferably methyl, ethyl, or propyl, and R 18 represents P-Sp-, H, or an alkyl group having 1 to 12, preferably 1 to 6, carbon atoms, and very preferably H.

[0262] Equation I * C1~I * In the compound G1, 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 -, very preferably -O-(CH2) p1 - and in the formula, an O atom or a CO group is linked to a benzene ring, p1 is an integer from 1 to 6, more preferably 2, 3, 4, 5 or 6, R * and R ** Preferably, each is an alkyl or alkoxy having 1 to 12, very preferably 1 to 6, carbon atoms, independently of each other.

[0263] Formula IA * The compound can be produced, for example, by the method described in British Patent Application Publication No. 2314839, or by a similar method. Formula I * E1~I * Compound E15 can be prepared, for example, by the method described in International Publication No. 02 / 40614, or by a similar method.

[0264] Preferably, the chiral isomerizing compounds used, individually or in combination, exhibit helical torsional forces (|HTP). total |) The absolute value is 20 μm -1 Preferably 40 μm -1 More preferably 60 μm -1 Within the above range, most preferably 80 μm -1 More than ~260μm -1 It is within the range.

[0265] If the RM mixture contains two or more chiral isomerized compounds, these compounds may have the same or opposite twist directions.

[0266] In preferred embodiments, the RM mixture is preferably polymerizable, i.e., contains at least one group P-Sp-, and very preferably formula I * It contains only one chiral isomerized compound selected from its sub-formulas.

[0267] In another preferred embodiment, the RM mixture is Formula I * No chiral compounds other than the compound mentioned are included.

[0268] Preferably, the chiral isomerized compound, particularly of formula I, is present in the entire RM mixture according to the present invention. * The proportion of the chiral isomerized compound selected from the subformula is in the range of 0.1 to 10% by weight, very preferably in the range of 0.2 to 8.5% by weight, and most preferably in the range of 0.5 to 4% by weight.

[0269] In another preferred embodiment, the RM mixture includes one or more non-isomerizable chiral compounds in addition to the chiral isomerizable compound.

[0270] The central wavelength of the reflection band of the RM mixture can be adjusted by adding one or more non-isomerizing chiral compounds. The additional non-isomerizing chiral compounds may have the same or opposite twist direction as the chiral isomerizing compound. Thus, the reflection wavelength band of the RM mixture will be shifted to a shorter or longer wavelength, respectively.

[0271] In another preferred embodiment, the RM mixture is particularly of formula I * The material comprises one or more, preferably exactly one, chiral isomerizable and polymerizable compounds selected from or its subformulas, and further comprises one or more, preferably exactly one polymerizable chiral compound that is not isomerizable and very preferably has a twist direction opposite to that of the chiral isomerizable and polymerizable compounds, preferably selected from formula CRM or its subformulas.

[0272] Preferably, additional polymerizable chiral compounds, either individually or in combination, exert helical twist forces (|HTP). total |) The absolute value is 20 μm -1 Preferably 40 μm -1 More preferably 60 μm -1 Within the above range, most preferably 80 μm -1 More than ~260μm -1 It is within the range.

[0273] The additional polymerizable chiral compound is preferably selected from monoreactive or direactive compounds.

[0274] A suitable polymerizable chiral compound preferably comprises one or more ring elements linked directly or via linking groups, two of which may optionally be linked to each other directly or via linking groups, the linking groups of which may be the same as or different from the aforementioned linking groups. The ring elements are preferably selected from the group of 4-membered rings, 5-membered rings, 6-membered rings, or 7-membered rings, preferably 5-membered rings or 6-membered rings.

[0275] Preferred polymerizable chiral compounds are selected from formulas CRM1, CRM2, and CRM3.

[0276] [ka]

[0277] In the formula, each base is independent of the others and, in each instance, identical or different in meaning as follows: P 0* It is a polymerizable group, Sp 0* These are spacer groups or single bonds, R 0* F, Cl, CN, alkyl, alkoxy, thioalkyl, alkylcarbonyl, alkoxycarbonyl, alkylcarbonyloxy or alkoxycarbonyloxy having 1 to 15, preferably 1 to 6 C atoms, P 0* or P 0* -Sp * -and, A 0 B 0 , E 0 F 0 This is 1,4-phenylene or trans-1,4-cyclohexylene, which is either unsubstituted or substituted with 1, 2, 3, or 4 L groups. L is an alkyl, alkoxy, thioalkyl, alkylcarbonyl, alkoxycarbonyl, alkylcarbonyloxy or alkoxycarbonyloxy which may be fluorinated and have F, Cl, CN, P-Sp-, or 1 to 5 C atoms. X 1 , X 2 These are -O-, -COO-, -OCO-, -O-CO-O-, or single bonds. Z 0* These are -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 is 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 is 0 or 1, preferably 1. However, the naphthalene ring may be further substituted with one or more identical or different groups L.

[0278] Even more preferable are the stereoisomers of formula CRM2 in which the central isosorbide unit is replaced with an isomannide or isoidide unit.

[0279] The compound of formula CRM1 is preferably selected from the following formulas.

[0280] [ka]

[0281] In the formula, A 0 B 0 , Z 0* , X 2 , P 0* a and b have the meanings given in formula CRMa or one of the preferred meanings given above and below, and (OCO) represents -O-CO- or a single bond.

[0282] Particularly preferred compounds of formula CRM are selected from the group consisting of the following sub-formulas.

[0283] [ka]

[0284] [ka]

[0285] In the formula, R * -X as defined in CRM1-1 2 -(CH2) t -P 0* The benzene ring and naphthalene ring are either unsubstituted or substituted with 1, 2, 3, or 4 groups L as defined above and below.

[0286] If one or more polymerizable chiral compounds are present, their concentrations in the RM mixture are preferably 0.1 to 10% by weight, more preferably 0.5 to 8% by weight, of the total RM mixture.

[0287] In another preferred embodiment, the RM mixture preferably comprises one or more additional RMs selected from achiral RMs different from formula I, CRM1 to CRM3 and their sub-formulas. Preferably, the RM mixture comprises one or more additional RMs selected from RMs having only one polymerizable functional group (monoreactive RMs) and / or RMs having two or more polymerizable functional groups (direactive or polyreactive RMs).

[0288] The additional bireactive or polyreactive RM is preferably selected from formula DRM.

[0289] [ka]

[0290] During the ceremony, P 1 , P 2 These represent polymerizable groups independently of each other, Sp 1 , Sp 2 These are spacer groups or single bonds, independently of each other. MG is a rod-shaped mesogenic group, which is preferably selected from formula MG.

[0291] [ka]

[0292] During the ceremony, A 1 and A 2 If multiple groups exist, they independently represent aromatic or alicyclic groups, and these groups may contain one or more heteroatoms selected from N, O, and S, and may be monosubstituted or polysubstituted with L. L is P-Sp-, F, Cl, Br, I, -CN, -NO2, -NCO, -NCS, -OCN, -SCN, -C(=O)NR x R y , -C(=O)OR x -C(=O)R x , -NR x R y -OH, -SF5, substituted silyl, aryl or heteroaryl having 1 to 12, preferably 1 to 6 C atoms, and linear or branched alkyl, alkoxy, thioalkyl, alkylcarbonyl, alkoxycarbonyl, alkylcarbonyloxy or alkoxycarbonyloxy having 1 to 12, preferably 1 to 6 C atoms, wherein one or more H atoms may be replaced with F or Cl. R x and R y Each of these represents an alkyl group having either H or 1 to 12 C atoms independently of each other. Z 1 If multiple instances exist, they are treated independently of each other 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 single bond, preferably -COO-, -OCO- or single bond, Y 1 and Y 2 Each of these independently represents H, F, Cl, or CN. n is 1, 2, 3 or 4, preferably 1 or 2, most preferably 2. n1 is an integer between 1 and 10, preferably 1, 2, 3, or 4.

[0293] Preferred base A 1 and A 2 Examples include, but are not limited to, furan, pyrrole, thiophene, oxazole, thiazole, thiadiazole, imidazole, phenylene, cyclohexylene, bicyclooctylene, cyclohexenylene, pyridine, pyrimidine, pyrazine, azulene, indan, fluorene, naphthalene, tetrahydronaphthalene, anthracene, phenanthrene, and dithienothiophene, all of which are either unsubstituted or substituted with one, two, three, or four groups L as defined above.

[0294] Particularly preferred base A 1 and A 2 is selected from 1,4-phenylene, pyridine-2,5-diyl, pyrimidine-2,5-diyl, thiophene-2,5-diyl, naphthalene-2,6-diyl, 1,2,3,4-tetrahydronaphthalene-2,6-diyl, indan-2,5-diyl, bicyclooctylene, or 1,4-cyclohexylene, where one or two non-adjacent CH2 groups are optionally replaced by O and / or S, where these groups are either unsubstituted or substituted by one, two, three, or four L groups as defined above.

[0295] The preferred RM in formula DRM is selected from formula RDMA.

[0296] [ka]

[0297] During the ceremony, P 0 If multiple groups appear, they are independently polymerizable groups, preferably acrylic, methacrylic, oxetane, epoxy, vinyl, heptadiene, vinyloxy, propenyl ether, or styrene groups. Z 0 These are -COO-, -OCO-, -CH2CH2-, -CF2O-, -OCF2-, -C≡C-, -CH=CH-, -OCO-CH=CH-, -CH=CH-COO-, or single bonds. L is the same or different in each occurrence in equation I. 1 It has one of the meanings given to it, and if it appears multiple times, it is independently selected from alkyl, alkoxy, alkylcarbonyl, alkoxycarbonyl, alkylcarbonyloxy or alkoxycarbonyloxy which may be halogenated and have F, Cl, CN or 1 to 5 C atoms. r is 0, 1, 2, 3, or 4. x and y are each independent of each other, either 0, or identical or different integers between 1 and 12. z is either 0 or 1, except when adjacent x or y is 0.

[0298] The most preferred RM of the DRM formula is selected from the following formulas.

[0299] [ka]

[0300] [ka]

[0301] In the formula, P 0 L, r, x, y, and z are defined in formula DRMa.

[0302] Compounds of formulas DRMa1, DRMa2, and DRMa3 are preferred, with the compound of formula DRMa1 being particularly preferred.

[0303] In another preferred embodiment, the RM mixture comprises one or more monoreactive RMs in addition to the compound of formula I. These additional monoreactive RMs are preferably selected from formula MRM.

[0304] [ka]

[0305] In the formula, P 1 , Sp 1 And MG has the meaning given in formula DRM, R 22 P-Sp-, F, Cl, Br, I, -CN, -NO2, -NCO, -NCS, -OCN, -SCN, -C(=O)NR x R y -C(=O)X, -C(=O)OR x -C(=O)R y , -NR x R y Represents a linear or branched alkyl, alkoxy, alkylcarbonyl, alkoxycarbonyl, alkylcarbonyloxy or alkoxycarbonyloxy having 1 to 12, preferably 1 to 6 C atoms, wherein one or more H atoms may be replaced with F or Cl. X is a halogen, preferably F or Cl. R x and R y Each of these is an alkyl group that independently has either H or 1 to 12 C atoms.

[0306] Preferably, RM in formula MRM is selected from the following formulas.

[0307] [ka]

[0308] [ka]

[0309] [ka]

[0310] [ka]

[0311] In the formula, P 0 L, r, x, y, and z are as defined in formulas DRMa and DRMk, R 0 , R 01 and R 02 is an alkyl, alkoxy, thioalkyl, alkylcarbonyl, alkoxycarbonyl, alkylcarbonyloxy or alkoxycarbonyloxy having one or more, preferably 1 to 15 carbon atoms, or Y 0 Or P-(CH2) y -(O) z - represents, X 0 -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 bond, Y 0 These are F, Cl, CN, NO2, OCH3, OCN, SCN, SF5, or monofluorinated, oligofluorinated, or polyfluorinated alkyl or alkoxy compounds having 1 to 4 carbon atoms. Z 0 These are -COO-, -OCO-, -CH2CH2-, -CF2O-, -OCF2-, -CH=CH-, -OCO-CH=CH-, -CH=CH-COO- or single bonds. A 0 If multiple groups exist, they are 1,4-phenylene or trans-1,4-cyclohexylene, which are either unsubstituted or substituted with one, two, three, or four L groups independently of each other. R 01、02 H and R are independent of each other. 0 or Y 0 And, u and v are each independently 0, 1, or 2. w is either 0 or 1. However, the benzene ring and the naphthalene ring may be further substituted with one or more identical or different groups L.

[0312] Of particular preference are compounds of formulas MRM1, MRM2, MRM3, MRM4, MRM5, MRM6, MRM7, MRM9, and MRM10, with compounds of formulas MRM1, MRM4, MRM6, and MRM7 being especially preferred.

[0313] In formulas DRM, MRM, and their preferred subformulas, L is preferably selected from F, Cl, CN, NO2, or linear or branched alkyl, alkoxy, alkylcarbonyl, alkoxycarbonyl, alkylcarbonyloxy or alkoxycarbonyloxy having 1 to 12 C atoms, wherein the alkyl group may be perfluorinated or P-Sp-.

[0314] 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-, particularly F, Cl, CN, CH3, C2H5, C(CH3)3, CH(CH3)2, OCH3, COCH3, or OCF3, most preferably F, Cl, CH3, C(CH3)3, OCH3, or COCH3, or P-Sp-.

[0315] The concentration of additional bireactive or polyreactive RM in the RM mixture, preferably of formula DRM and its sub-formulas, is preferably 1-50%, and very preferably 2-30%.

[0316] The concentration of additional one-reactive RM, preferably of formula MRM, in the RM mixture is preferably 1-40%, and very preferably 2-20%.

[0317] In another preferred embodiment, the RM mixture contains only a small amount of the compound of formula I. Therefore, it preferably consists mainly of monoreactive, direactive, and / or polyreactive RMs selected from formulas DRM and MRM and their sub-formulas, and contains a small amount, preferably 5-30%, of the compound of formula I, and more preferably formula I * It is possible to provide an RM mixture containing one or more chiral isomerizing compounds selected from the following.

[0318] In the RM mixture according to this preferred embodiment, the concentration of the direactive or polyreactive RM represented by formula DRM and its sub-formulas is preferably 15-75%, and very preferably 25-65%. In the RM mixture according to this preferred embodiment, the concentration of the monoreactive RM, preferably of formula MRM, is preferably 1-50%, and very preferably 5-30%.

[0319] The RM mixture preferably exhibits a chiral nematic LC phase, or a chiral smectic LC phase and a chiral nematic LC phase, and very preferably exhibits a chiral nematic LC phase at room temperature.

[0320] The RM mixture preferably has a birefringence (Δn) 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.

[0321] Another object of the present invention is an RM formulation comprising the above and below RM mixtures, and further comprising one or more solvents and / or additives.

[0322] In RM formulations, Formulas I and I * The RM mixture preferably comprises compounds selected from their sub-formulas, and optionally compounds selected from formulas CRM1, CRM2, CRM3, DRM, and MRM, and their sub-formulas, with the proportion of the RM mixture being 85-100%, more preferably 85-99%, and very preferably 90-99%, of the total solids and liquid additives (i.e., excluding the solvent).

[0323] In another preferred embodiment of the present invention, the chiral RM mixture does not contain compounds of formula DRM or MRM. In another preferred embodiment, the chiral RM mixture contains compounds of formulas I and I * It consists of compounds selected from the following.

[0324] In another preferred embodiment, the RM mixture of the present invention further comprises one or more chiral compounds that are not polymerizable or isomerizable. These chiral compounds may be non-mesogenic or mesogenic compounds.

[0325] Further chiral compounds may have the same or opposite twist direction as the chiral isomerizable compound. This makes it possible to shift the reflection wavelength band of the RM mixture to the shorter or longer wavelength side, as described above.

[0326] Preferred non-polymerizable chiral compounds are selected from the group consisting of compounds of formulas CI to C-III.

[0327] [ka]

[0328] In the formulas, formulas C-II and C-III contain their respective (S,S) enantiomers, E and F are independently 1,4-phenylene or trans-1,4-cyclohexylene, v is 0 or 1, and Z 0 R is -COO-, -OCO-, -CH2CH2- or a single bond, c These are alkyl, alkoxy, or alkanoyl compounds having 1 to 12 carbon atoms.

[0329] Even more preferable are the stereoisomers of formula C-II in which the central isosorbide unit is replaced by an isomannide or isoidide unit.

[0330] The compound of formula Cl and its synthesis are described in European Patent Application Publication No. 1389199. The compound of formula C-II and its synthesis are described in International Publication No. 98 / 00428. The compound of formula C-III and its synthesis are described in UK Patent Application Publication No. 2328207.

[0331] Further preferred additional chiral dopants include, for example, the 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 (Merck, Darmstadt, Germany).

[0332] The amount of nonpolymerizable chiral dopant in the RM formulation is preferably 0.1 to 10%, more preferably 0.5 to 8%, relative to the weight of the total solids.

[0333] In another preferred embodiment, the RM mixture or RM formulation may contain one or more additives selected from the group consisting of polymerization initiators, surfactants, stabilizers, catalysts, sensitizers, inhibitors, chain transfer agents, co-reaction monomers, reactive diluents, surfactants, lubricants, wetting agents, dispersants, hydrophobic agents, adhesives, flow improvers, degassing or defoaming agents, degassing agents, diluents, reactive diluents, auxiliary agents, colorants, dyes, pigments, and nanoparticles.

[0334] In another preferred embodiment of the present invention, the RM mixture and / or RM formulation does not contain any compounds having at least one CF3 or CF2 group (PFAS), and very preferably, the RM mixture and / or RM formulation does not contain any compounds having a polyfluoroalkyl or aryl group or a perfluorocarbon group. More preferably, the RM mixture and / or RM formulation does not contain any compounds having a fluorinated aliphatic C atom, and most preferably, the RM mixture and / or RM formulation does not contain any compounds having a fluorinated C atom. Thus, the RM mixture and RM formulation according to this preferred embodiment allows for a reduction in perfluorocarbons.

[0335] The above and below RM mixtures and / or RM formulations are free of PFAS, more preferably free of perfluorocarbon compounds, very preferably free of compounds having polyfluorocarbon atoms, and most preferably free of compounds having fluorinated carbon atoms, which is another objective of the present invention.

[0336] In another preferred embodiment, the RM formulation preferably comprises one or more specific antioxidant additives selected from the Irganox® series, for example, the antioxidants Irganox® 1076 and Irganox® 1010, which are commercially available from Ciba of Switzerland.

[0337] In another preferred embodiment, the RM formulation includes, for example, a combination of one or more, more preferably two or more, photoinitiators selected from the commercially available Irgacure® or Darocure® (Ciba) series, particularly Irgacure 127, Irgacure 184, Irgacure 369, Irgacure 651, Irgacure 817, Irgacure 907, Irgacure 1300, Irgacure, Irgacure 2022, Irgacure 2100, Irgacure 2959, or Darcure TPO, and further comprising one or more, more preferably two or more, photoinitiators selected from the commercially available OXE02 (Ciba), NCI 930, N1919T (Adeka), SPI-03 or SPI-04 (Samyang), TR-PBG 304 or TR-PGB 345 (Tronly).

[0338] The photoinitiator is preferably selected to have an absorption maximum different from the absorption maximum of the chiral photoisomer compound, and very preferably to have an absorption maximum at least 15 nm higher or lower than the absorption maximum of the chiral photoisomer compound.

[0339] The overall concentration of polymerization initiators (one or more) in the RM formulation is preferably 0.1-6%, very preferably 0.3-5%, and more preferably 0.7-4%.

[0340] In another preferred embodiment, in the chiral RM mixture, the ratio of the concentration of the photoinitiator to the total concentration of the chiral compound is in the range of 2:1 to 1:5, more preferably in the range of 2:1 to 1:4, and even more preferably in the range of 2:1 to 1:3.

[0341] In another preferred embodiment, the RM formulation may contain one or more additives selected from polymerizable non-mesogenic compounds (reactive thinners). The amount of these additives in the RM formulation is preferably 0 to 30%, and very preferably 0 to 25%.

[0342] The reactive thinner used is not only a substance called a reactive thinner in the literal sense, but also one of the auxiliary compounds already mentioned above, which contain one or more complementary reactive units, such as a hydroxyl group, a thiol group, or an amino group, through which a reaction with the polymerization units of the liquid crystalline compound can occur.

[0343] Typically, photopolymerizable substances include, for example, monofunctional, difunctional, and polyfunctional compounds containing at least one olefinic double bond. Examples include vinyl esters of carboxylic acids, such as lauric acid, myristic acid, palmitic acid, and stearic acid; vinyl esters of dicarboxylic acids, such as succinic acid, adipic acid, allyl, and vinyl ethers; methacrylic and acrylic esters of monofunctional alcohols, such as methacrylic and acrylic esters of lauryl, myristyl, palmityl, and stearyl alcohols; and difunctional alcohols, such as diallyl and divinyl ethers of ethylene glycol and 1,4-butanediol.

[0344] Also suitable are, for example, methacrylic acid and acrylic acid esters of polyfunctional alcohols, particularly those that do not contain any additional functional groups other than the hydroxyl group, or that contain at most an ether group. Examples of such alcohols include difunctional alcohols, e.g., ethylene glycol, propylene glycol and representative of their more highly condensed forms, e.g., diethylene glycol, triethylene glycol, dipropylene glycol, tripropylene glycol, etc., butanediol, pentanediol, hexanediol, neopentyl glycol, alkoxylated phenol compounds, e.g., ethoxylated and propoxylated bisphenol, cyclohexanedimethanol, trifunctional and polyfunctional alcohols, e.g., glycerol, trimethylolpropane, butanetriol, trimethylolethane, pentaerythritol, ditrimethylolpropane, dipentaerythritol, sorbitol, mannitol, and the corresponding alkoxylated, particularly ethoxylated and propoxylated alcohols.

[0345] Another suitable reactive thinner is polyester (meth)acrylate, which is a (meth)acrylic acid ester of polyesterol.

[0346] Suitable polyesterols can be prepared by esterifying polycarboxylic acids, preferably dicarboxylic acids, with polyols, preferably diols. Starting materials for such hydroxyl-containing polyesters are known to those skilled in the art. Dicarboxylic acids that can be used include succinic acid, glutaric acid, adipic acid, sebacic acid, o-phthalic acid and their isomers and hydrogenation products, as well as esterifiable and transesterifiable derivatives of the acids, such as anhydrides and dialkyl esters. Suitable polyols are the alcohols mentioned above, preferably ethylene glycol, 1,2- and 1,3-propylene glycol, 1,4-butanediol, 1,6-hexanediol, neopentyl glycol, cyclohexanedimethanol, and polyglycols of the ethylene glycol and propylene glycol type.

[0347] Suitable reactive thinners are also acrylic esters of tricyclodecenyl alcohols, known by the names 1,4-divinylbenzene, triallyl cyanurate, dihydrodicyclopentadienyl acrylate, and the following formulas, as well as allyl esters of acrylic acid, methacrylic acid, and cyanoacrylic acid.

[0348] [ka]

[0349] Among the reactive thinners listed as examples, those having photopolymerizable groups are used in particular, and from the viewpoint of the preferred compositions described above.

[0350] Examples of this group include dihydric and polyhydric alcohols, such as ethylene glycol, propylene glycol, and representative of their more highly condensed forms, such as diethylene glycol, triethylene glycol, dipropylene glycol, and tripropylene glycol, as well as butanediol, pentanediol, hexanediol, neopentyl glycol, cyclohexanedimethanol, glycerol, trimethylolpropane, butanetriol, trimethylolethane, pentaerythritol, ditrimethylolpropane, dipentaerythritol, sorbitol, mannitol, and corresponding alkoxylated, particularly ethoxylated and propoxylated alcohols.

[0351] Further examples of this group include alkoxylated phenol compounds, such as ethoxylated and propoxylated bisphenols.

[0352] These reactive thinners may further be, for example, epoxides or urethane (meth)acrylates.

[0353] Epoxy (meth)acrylates are obtained, for example, by the reaction of epoxidized olefins or poly or diglycidyl ethers, such as bisphenol A diglycidyl ether, which are known to those skilled in the art, with (meth)acrylic acid.

[0354] Urethane (meth)acrylates are, in particular, products of the reaction of hydroxyalkyl (meth)acrylates with poly or diisocyanates, which are also known to those skilled in the art.

[0355] Such epoxides and urethane (meth)acrylates are included in the compounds listed above as “mixed forms.”

[0356] When reactive thinners are used, their quantities and properties must be adapted to the respective conditions so that, on the one hand, a satisfactory desired effect, such as the desired color of the composition according to the present invention, is obtained, and on the other hand, the phase behavior of the liquid crystal composition is not excessively impaired. Low-crosslinked (high-crosslinked) liquid crystal compositions can be prepared, for example, using the corresponding reactive thinner having a relatively small (large) number of reactive units per molecule.

[0357] Examples of diluents include: C1-C4 alcohols, e.g. methanol, ethanol, n-propanol, isopropanol, butanol, isobutanol, sec-butanol, especially C5-C12 alcohols, n-pentanol, n-hexanol, n-heptanol, n-octanol, n-nonanol, n-decanol, n-undecanol and n-dodecanol, and their isomers, glycols, e.g., 1,2-ethylene glycol, 1,2- and 1,3-propylene glycol, 1,2-, 2,3- and 1,4-butylene glycol, di- and triethylene glycol, and di- and tripropylene glycol, ethers, e.g., methyl tert-butyl ether, 1,2-ethylene glycol mono- and dimethyl ether, 1,2-ethylene glycol mono- and diethyl ether, 3-methyl Examples include cypropanol, 3-isopropoxypropanol, tetrahydrofuran and dioxane, ketones such as acetone, methyl ethyl ketone, methyl isobutyl ketone and diacetone alcohol (4-hydroxy-4-methyl-2-pentanone), C1-C5 alkyl esters such as methyl acetate, ethyl acetate, propyl acetate, butyl acetate and amyl acetate, aliphatic and aromatic hydrocarbons such as pentane, hexane, heptane, octane, isooctane, petroleum ether, toluene, xylene, ethylbenzene, tetralin, decalin, dimethylnaphthalene, white spirit, Shellsol® and Solvesso® mineral oils such as gasoline, kerosene, diesel fuel and heating oil, and natural oils such as olive oil, soybean oil, rapeseed oil, linseed oil and sunflower oil.

[0358] Naturally, mixtures of these diluents can also be used in the composition according to the present invention.

[0359] These diluents can also be mixed with water, provided they are at least partially miscible. Suitable examples of diluents herein are C1-C4 alcohols, e.g., methanol, ethanol, n-propanol, isopropanol, butanol, isobutanol and sec-butanol; glycols, e.g., 1,2-ethylene glycol, 1,2- and 1,3-propylene glycol, 1,2-, 2,3- and 1,4-butylene glycol, di- and triethylene glycol and di- and tripropylene glycol; ethers, e.g., tetrahydrofuran and dioxane; ketones, e.g., acetone, methyl ethyl ketone and diacetone alcohol (4-hydroxy-4-methyl-2-pentanone); and C1-C4 alkyl esters, e.g., methyl, ethyl, propyl and butyl acetate.

[0360] The diluent is used as desired in a proportion 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.

[0361] Antifoaming and degassing agents (c1), lubricants and flow aids (c2), thermosetting or radiation-curing aids (c3), substrate wetting aids (c4), wetting and dispersion aids (c5), hydrophobic agents (c6), adhesion promoters (c7), and scratch-resistant aids (c8) do not need to be strictly distinguished from one another in their function.

[0362] For example, lubricants and flow aids often act as defoamers and / or defoamers, and / or as additives to improve scratch resistance. Radiation curing aids may also act as lubricants, flow aids, and / or defoamers, and / or substrate wetting aids. In some cases, some of these aids may also function as adhesion promoters (c8).

[0363] Accordingly, certain additives can therefore be classified into the following numerous groups c1) to c8).

[0364] The defoaming agents of group c1) include silicone-free and silicone-containing polymers. Silicone-containing polymers are, for example, unmodified or modified polydialkylsiloxanes or branched copolymers, comb or block copolymers containing polydialkylsiloxanes and polyether units, the latter of which are obtained from ethylene oxide or propylene oxide.

[0365] Examples of degassing agents in group c1) include organic polymers, such as polyethers and polyacrylates, dialkylpolysiloxanes, particularly dimethylpolysiloxanes, organically modified polysiloxanes, such as arylalkyl-modified polysiloxanes, and fluorosilicones.

[0366] The action of an antifoaming agent is essentially based on preventing foam formation or destroying foam that has already formed. Antifoaming agents essentially work by promoting the aggregation of finely divided gas or bubbles, thereby generating larger bubbles in the medium to be defoamed, for example, in the composition according to the present invention, and thus promoting the escape of gas (air). Antifoaming agents can also be frequently used as defoaming agents, and vice versa, and these additives are collectively included in group c1).

[0367] Such auxiliary agents include, for example, TEGO® Foamex800, TEGO® Foamex805, TEGO® Foamex810, TEGO® Foamex815, TEGO® Foamex825, TEGO® Foamex835, TEGO® Foamex840, TEGO® Foamex842, TEGO® Foamex1435, TEGO® Foamex1488, TEGO® Foamex1495, TEGO® Fo amex3062, TEGO(registered trademark) Foamex7447, TEGO(registered trademark) Foamex8020, Tego(registered trademark) FoamexN, TEGO(registered trademark) FoamexK3, TEGO(registered trademark) Antifoam2-18, TEGO(registered trademark) Antifoam2-18, TEGO(registered trademark) Antifoam2-57, TEGO(registered trademark) Antifoam2-80, TEGO(registered trademark) Antifoam2-82, TEGO(registered trademark) Antifoam2-89, TEGO(registered trademark) Antifoam2-92 TEGO® Antifoam14, TEGO® Antifoam28, TEGO® Antifoam81, TEGO® AntifoamD90, TEGO® Antifoam93, TEGO® Antifoam200, TEGO® Antifoam201, TEGO® Antifoam202, TEGO® Antifoam793, TEGO® Antifoam1488, TEGO® Antifoam3062, TEGOPRE N(registered trademark) 5803, TEGOPREN(registered trademark) 5852, TEGOPREN(registered trademark) 5863, TEGOPREN(registered trademark) 7008, TEGO(registered trademark) Antifoam1-60, TEGO(registered trademark) Antifoam1-62, TEGO(registered trademark) Antifoam1-85, TEGO(registered trademark) Antifoam2-67, TEGO(registered trademark) AntifoamWM20, TEGO(registered trademark) Antifoam50, TEGO(registered trademark) Antifoam105, TEGO(registered trademark) Antifoam730,TEGO® Antifoam MR1015, TEGO® Antifoam MR1016, TEGO® Antifoam 1435, TEGO® Antifoam N, TEGO® Antifoam KS6, TEGO® Antifoam KS10, TEGO® Antifoam KS53, TEGO® Antifoam KS95, TEGO® Antifoam KS100, TEGO® Antifoam KE6 00, TEGO(registered trademark) AntifoamKS911, TEGO(registered trademark) AntifoamMR1000, TEGO(registered trademark) AntifoamKS1100, Tego(registered trademark) Airex900, Tego(registered trademark) Airex910, Tego(registered trademark) Airex931, Tego(registered trademark) Airex935, Tego(registered trademark) Airex936, Tego(registered trademark) Airex960, Tego(registered trademark) Airex970, Tego(registered trademark) Airex980 and It is also sold by Tego as Tego(registered trademark) Airex985, and is available in the following versions: BYK(registered trademark)-011, BYK(registered trademark)-019, BYK(registered trademark)-020, BYK(registered trademark)-021, BYK(registered trademark)-022, BYK(registered trademark)-023, BYK(registered trademark)-024, BYK(registered trademark)-025, BYK(registered trademark)-027, BYK(registered trademark)-031, BYK(registered trademark)-032, BYK(registered trademark)-033, BYK(registered trademark)-034, BYK(registered trademark)-03 5. These are commercially available from BYK as BYK(registered trademark)-036, BYK(registered trademark)-037, BYK(registered trademark)-045, BYK(registered trademark)-051, BYK(registered trademark)-052, BYK(registered trademark)-053, BYK(registered trademark)-055, BYK(registered trademark)-057, BYK(registered trademark)-065, BYK(registered trademark)-066, BYK(registered trademark)-070, BYK(registered trademark)-080, BYK(registered trademark)-088, BYK(registered trademark)-141, and BYK(registered trademark)-A530.

[0368] The auxiliary agents of group c1) are used as desired in a proportion of approximately 0 to 3.0% by weight, preferably approximately 0 to 2.0% by weight, based on the total weight of the RM formulation.

[0369] In group c2), lubricants and fluidizing agents typically include not only silicon-free polymers but also silicon-containing polymers, such as polyacrylates or modifiers, and low molecular weight polydialkylsiloxanes. Modifications lie in several alkyl groups replaced by a wide variety of organic groups. These organic groups are, for example, polyethers, polyesters, or even longer-chain alkyl groups, with the former being the most frequently used.

[0370] The polyether groups in the corresponding modified polysiloxanes 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 more hydrophilic the resulting product becomes.

[0371] Such additives are commercially available from Tego as, for example, TEGO® Glide100, TEGO® GlideZG400, TEGO® Glide406, TEGO® Glide410, TEGO® Glide411, TEGO® Glide415, TEGO® Glide420, TEGO® Glide435, TEGO® Glide440, TEGO® Glide450, TEGO® GlideA115, TEGO® GlideB1484 (which can also be used as an antifoaming and defoaming agent), TEGO® FlowATF, TEGO® Flow300, TEGO® Flow460, TEGO® Flow425, and TEGO® FlowZFS460. Suitable radiation-curable lubricants and flow aids, which can also be used to improve scratch resistance, are products of TEGO® Rad2100, TEGO® Rad2200, TEGO® Rad2500, TEGO® Rad2600, and TEGO® Rad2700, which are also available from TEGO.

[0372] Such additives are available from BYK as, for example, BYK(registered trademark)-300, BYK(registered trademark)-306, BYK(registered trademark)-307, BYK(registered trademark)-310, BYK(registered trademark)-320, BYK(registered trademark)-333, BYK(registered trademark)-341, Byk(registered trademark)354, Byk(registered trademark)361, Byk(registered trademark)361N, and BYK(registered trademark)388.

[0373] The auxiliary agents of group c2) are used as desired in a proportion of approximately 0 to 3.0% by weight, preferably approximately 0 to 2.0% by weight, based on the total weight of the RM formulation.

[0374] In group c3), radiation curing aids include, in particular, polysiloxanes having terminal double bonds, for example, acrylate groups. Such aids can be crosslinked by chemical beams or, for example, electron beams. These aids generally possess a combination of many properties. In their uncrosslinked state, they can act as defoamers, defoamers, lubricants, flow aids, and / or substrate wetting aids, but in their crosslinked state, they particularly improve the scratch resistance of, for example, coatings or films that can be manufactured using compositions according to the present invention. For example, precisely, the improvement in the gloss properties of these coatings or films is considered to be essentially a result of the actions of these aids as defoamers, defoamers, and / or lubricants, and flow aids (in their uncrosslinked state).

[0375] Examples of suitable radioscaling aids include TEGO®Rad2100, TEGO®Rad2200, TEGO®Rad2500, TEGO®Rad2600, and TEGO®Rad2700, available from TEGO, and BYK®-371, available from BYK.

[0376] The thermosetting aids of group c3) include, for example, primary OH groups that can react with the isocyanate group of the binder.

[0377] Examples of thermosetting aids that may be used are BYK®-370, BYK®-373, and BYK®-375, which are available from BYK.

[0378] The auxiliary agents of group c3) are used as desired in a proportion of approximately 0 to 5.0% by weight, preferably approximately 0 to 3.0% by weight, based on the total weight of the RM formulation.

[0379] The substrate wetting aids of group c4) are particularly useful in improving the wettability of substrates to be printed or coated with, for example, printing inks or coating compositions, such as the compositions according to the present invention. Often, this improvement in the lubrication and flow behavior of such printing inks or coating compositions also affects the appearance of the finished (e.g., crosslinked) print or coating.

[0380] Such a wide variety of excipients are commercially available from Tego as TEGO(registered trademark)WetKL245, TEGO(registered trademark)Wet250, TEGO(registered trademark)Wet260 and TEGO(registered trademark)WetZF453, and from BYK as BYK(registered trademark)-306, BYK(registered trademark)-307, BYK(registered trademark)-310, BYK(registered trademark)-333, BYK(registered trademark)-344, BYK(registered trademark)-345, BYK(registered trademark)-346 and BYK(registered trademark)-348.

[0381] The additives of group c4) are used optionally in a proportion of about 0 to 3.0% by weight, preferably about 0 to 1.5% by weight, based on the total weight of the liquid crystal composition.

[0382] The wetting and dispersing agents of group c5) play a role in preventing the pigment from immersing, floating, or settling, and are therefore particularly suitable for the pigment composition according to the present invention, as needed.

[0383] These additives essentially stabilize the pigment dispersion through electrostatic repulsion and / or steric hindrance of the pigment particles containing these additives, although in the latter case, the interaction between the additive and the surrounding medium (e.g., binder) plays a major role.

[0384] The use of such wetting and dispersing aids is common in fields such as printing inks and coatings, so there is generally no problem for those skilled in the art when using appropriate aids of this type.

[0385] Such wetting and dispersing aids include, for example, TEGO® Dispers610, TEGO® Dispers610S, TEGO® Dispers630, TEGO® Dispers700, TEGO® Dispers705, TEGO® Dispers710, TEGO® Dispers720W, TEGO® Dispers725W, TEGO® Dispers730W, TEGO® Dispers735W, and TEG It is commercially available as O(registered trademark)Dispers740W, and also by BYK as Disperbyk(registered trademark), Disperbyk(registered trademark)-107, Disperbyk(registered trademark)-108, Disperbyk(registered trademark)-110, Disperbyk(registered trademark)-111, Disperbyk(registered trademark)-115, Disperbyk(registered trademark)-130, Disperbyk(registered trademark)-160, Disperbyk(registered trademark)-161, Disperbyk(registered trademark)-162, Disperbyk(registered trademark) )-163, Disperbyk(registered trademark)-164, Disperbyk(registered trademark)-165, Disperbyk(registered trademark)-166, Disperbyk(registered trademark)-167, Disperbyk(registered trademark)-170, Disperbyk(registered trademark)-174, Disperbyk(registered trademark)-180, Disperbyk(registered trademark)-181, Disperbyk(registered trademark)-182, Disperbyk(registered trademark)-183, Disperbyk(registered trademark)-184, Disperbyk(registered trademark)-185, D isperbyk(registered trademark)-190, Anti-Terra(registered trademark)-U, Anti-Terra(registered trademark)-U80, Anti-Terra(registered trademark)-P, Anti-Terra(registered trademark)-203, Anti-Terra(registered trademark)-204, Anti-Terra(registered trademark)-206, BYK(registered trademark)-151, BYK(registered trademark)-154, BYK(registered trademark)-155, BYK(registered trademark)-P104S, BYK(registered trademark)-P105, Lactimon(registered trademark), Lactimon(registered trademark)-WS,It is also sold as Bykumen (registered trademark).

[0386] The amount of additive used in group c5) is based on the average molecular weight of the additive. Therefore, in all cases, preliminary experiments are desirable, but this can be easily done by those skilled in the art.

[0387] Another preferred group of auxiliary agents that can be assigned to group c2), c4), or c5) includes wetting agents, fluidizers, and smoothing agents based on nonionic fluorinated surfactants, particularly those marketed by Synthomer as the Polyfox® series (e.g., Polyfox® PF-656).

[0388] The hydrophobic agents of group c6) can be used, for example, to impart water repellency to prints or coatings produced using the compositions according to the present invention. This prevents, or at least significantly suppresses, swelling due to water absorption, and consequently, changes in the optical properties of such prints or coatings. Furthermore, when the compositions are used, for example, as printing inks in offset printing, water absorption can be prevented, or at least significantly reduced.

[0389] Such hydrophobic agents are commercially available from Tego, for example, as Tego®PhobeWF, Tego®Phobe1000, Tego®Phobe1000S, Tego®Phobe1010, Tego®Phobe1030, Tego®Phobe1010, Tego®Phobe1010, Tego®Phobe1030, Tego®Phobe1040, Tego®Phobe1050, Tego®Phobe1200, Tego®Phobe1300, Tego®Phobe1310, and Tego®Phobe1400.

[0390] The auxiliary agents of group c6) are used as desired in a proportion of approximately 0 to 5.0% by weight, preferably approximately 0 to 3.0% by weight, based on the total weight of the RM formulation.

[0391] Adhesion promoters from group c7) help improve adhesion between two contacting interfaces. From this, it is immediately apparent that the only effective part of an adhesion promoter is located at either one or both interfaces. For example, when it is desirable to apply a liquid or paste-like printing ink, coating composition, or paint to a solid substrate, this generally means that the adhesion promoter must be added directly to the latter, or the substrate must be pre-treated with an adhesion promoter (also known as a priming), i.e., the substrate is given modified chemical and / or physical surface properties.

[0392] If the substrate is pre-coated with a primer, this means that the interface in contact is, on the one hand, that of the primer, and on the other hand, that of the printing ink or coating composition or paint. 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 contributes to the adhesion of the entire multilayer structure on the substrate.

[0393] Adhesion promoters, which can be described in a broader sense, are also substrate wetting aids already listed in group c4), but these generally do not have the same adhesion promoting ability.

[0394] Given the wide variety of physical and chemical properties of substrates, and of, for example, printing inks, coating compositions, and paints intended for printing or coating them, the diversity of adhesion promoter systems is not surprising.

[0395] Silane-based adhesion promoters include, for example, 3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, 3-aminopropylmethyldiethoxysilane, N-aminoethyl-3-aminopropyltrimethoxysilane, N-aminoethyl-3-aminopropylmethyldimethoxysilane, N-methyl-3-aminopropyltrimethoxysilane, 3-ureidopropyltriethoxysilane, 3-methacryloyloxypropyltrimethoxysilane, 3-glycidyloxypropyltrimethoxysilane, 3-mercaptopropyltrimethoxysilane, 3-chloropropyltrimethoxysilane, and vinyltrimethoxysilane. These and other silanes are commercially available from Huels, for example, under the trade name DYNASILAN®.

[0396] Corresponding technical information from the manufacturers of such additives should be made publicly available, or those skilled in the art can obtain this information in a simple manner through corresponding preliminary experiments.

[0397] However, when these additives are added to the RM formulation according to the present invention as auxiliary agents from group c7), their proportions are, arbitrarily, equivalent to about 0 to 5.0% by weight, based on the total weight of the RM formulation. These concentration data are merely guidelines, as the amount and type of additives are determined in each case by the properties of the substrate and the properties of the printing / coating composition. Corresponding technical information is usually available in this case from the manufacturer of such additives or can be obtained by those skilled in the art through corresponding preliminary experiments in a simple manner.

[0398] Examples of additives for improving the scratch resistance of group c8) include the above-mentioned products available from Tego: TEGO® Rad2100, TEGO® Rad2200, TEGO® Rad2500, TEGO® Rad2600, and TEGO® Rad2700.

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

[0400] Examples that may be mentioned regarding light, heat, and / or oxidative stabilizers are as follows: Alkylated monophenols, e.g., 2,6-di-tert-butyl-4-methylphenol, 2-tert-butyl-4,6-dimethylphenol, 2,6-di-tert-butyl-4-ethylphenol, 2,6-di-tert-butyl-4-n-butylphenol, 2,6-di-tert-butyl-4-isobutylphenol, 2,6-dicyclopentyl-4-methylphenol, 2-(α-methylcyclohexyl)-4,6-dimethylphenol, 2,6-dioctadecyl-4-methylphenol, 2,4,6-tricyclohexylphenol, 2,6-di-tert-butyl-4-methoxymethylphenol, linear or branched chains. Nonylphenols having a side chain, for example, 2,6-dinonyl-4-methylphenol, 2,4-dimethyl-6-(1'-methylundeca-1'-yl)phenol, 2,4-dimethyl-6-(1'-methylheptadeca-1'-yl)phenol, 2,4-dimethyl-6-(1'-methyltrideca-1'-yl)phenol and mixtures of these compounds, alkylthiomethylphenols, for example, 2,4-dioctylthiomethyl-6-tert-butylphenol, 2,4-dioctylthiomethyl-6-methylphenol, 2,4-dioctylthiomethyl-6-ethylphenol and 2,6-didodecylthiomethyl-4-nonylphenol,

[0401] Hydroquinones and alkylated hydroquinones, for example, 2,6-di-tert-butyl-4-methoxyphenol, 2,5-di-tert-butylhydroquinone, 2,5-di-tert-amylhydrocrinone, 2,6-diphenyl-4-octadecyloxyphenol, 2,6-di-tert-butylhydroquinone, 2,5-di-tert-butyl-4-hydroxyanisole, 3,5-di-tert-butyl-4-hydroxyanisole, 3,5-di-tert-butyl-4-hydroxyphenyl stearate and bis(3,5-di-tert-butyl-4-hydroxyphenyl) adipate.

[0402] Tocopherols, such as α-tocopherol, β-tocopherol, γ-tocopherol, δ-tocopherol and mixtures thereof, as well as tocopherol derivatives, such as tocopheryl acetate, succinate, nicotinate and polyoxyethylene succinate ("tocopherolsolates"),

[0403] Hydroxylated diphenyl thioethers, for example, 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-disec-amylphenol), and 4,4'-bis(2,6-dimethyl-4-hydroxyphenyl) disulfide.

[0404] Alkylidenebisphenols, for example, 2,2'-methylenebis(6-tert-butyl-4-methylphenol), 2,2'-methylenebis(6-tert-butyl-4-ethylphenol), 2,2'-methylenebis[4-methyl-6-(α-methylcyclohexyl)phenol], 2,2'-methylenebis(4-methyl-6-cyclohexylphenol), 2,2'-methylenebis(6-nonyl-4-methylphenol), 2,2'-methylenebis(4,6-di-tert-butylphenol), 2,2-ethylidenebis(4,6- Di-tert-butylphenol), 2,2'-ethylidenebis(6-tert-butyl-4-isobutylphenol), 2,2'-methylenebis[6-(α-methylbenzyl)-4-nonylphenol], 2,2'-methylenebis[6-(α,α-dimethylbenzyl)-4-nonylphenol], 4,4'-methylenebis(2,6-di-tert-butylphenol), 4,4'-methylenebis(6-tert-butyl-2-methylphenol), 1,1-bis(5-tert-butyl-4-hydroxy-2-methylphenyl)butane, 2,6-bis(3-tert-butyl-5-methyl-2-hydroxybenzyl)-4-methylphenol, 1,1,3-tris(5-tert-butyl-4-hydroxy-2-methylphenyl)butane, 1,1-bis(5-tert-butyl-4-hydroxy-2-methylphenyl)-3-n-dodecyl-mercaptobutane, ethylene glycol bis[3,3-bis(3'-tert-butyl-4'-hydroxyphenyl)butyrate], bis(3-tert-butyl-4-hydroxy-5-methylphenyl)dicyclopentadiene, bis [2-(3'-tert-butyl-2'-hydroxy-5'-methylbenzyl)-6-tert-butyl-4-methylphenyl]terephthalate, 1,1-bis(3,5-dimethyl-2-hydroxyphenyl)butane, 2,2-bis(3,5-di-tert-butyl-4-hydroxyphenyl)propane, 2,2-bis(5-tert-butyl-4-hydroxy-2-methylphenyl)-4-n-dodecyl-mercaptobutane and 1,1,5,5-tetrakis(5-tert-butyl-4-hydroxy-2-methylphenyl)pentane,

[0405] O-, N-, and S-benzyl compounds, e.g., 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.

[0406] Aromatic hydroxybenzyl compounds, for example, 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,

[0407] Triazine compounds, for example, 2,4-bis(octylmercapto)-6-(3,5-di-tert-butyl-4-hydroxyanilino)-1,3,5-triazine, 2-octylmercapto-4,6-bis(3,5-di-tert-butyl-4-hydroxyanilino)-1,3,5-triazine, 2-octylmercapto-4,6-bis(3,5-di-tert-butyl-4-hydroxyphenoxy)-1,3,5-triazine, 2,4,6-tris(3,5-di-tert-butyl-4-hydroxyphenoxy)-1,2,3-triazine, 1,3,5-tris(3,5-di-tert-butyl (Tyl-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,

[0408] Benzylphosphonates, for example, dimethyl 2,5-di-tert-butyl-4-hydroxybenzylphosphonate, diethyl 3,5-di-tert-butyl-4-hydroxybenzylphosphonate, dioctadecyl 3,5-di-tert-butyl-4-hydroxybenzylphosphonate, and dioctadecyl 5-tert-butyl-4-hydroxy-3-methylbenzylphosphonate.

[0409] Acylaminophenols, for example, 4-hydroxylauroylanilide, 4-hydroxystearoylanilide, and octyl N-(3,5-di-tert-butyl-4-hydroxyphenyl)carbamate,

[0410] Propionic acid and acetic acid esters of monohydric or polyhydric alcohols, such as methanol, ethanol, n-octanol, i-octanol, octadecanol, 1,6-hexanediol, 1,9-nonanediol, ethylene glycol, 1,2-propanediol, neopentyl glycol, thiodiethylene glycol, diethylene glycol, triethylene glycol, pentaerythritol, tris(hydroxyethyl)isocyanurate, N,N'-bis(hydroxyethyl)oxalamide, 3-thiaundecanol, 3-thiapentadecanol, trimethylhexanediol, trimethylolpropane, and 4-hydroxymethyl-1-phospha-2,6,7-trioxabicyclo[2.2.2]-octan,

[0411] Propionamides based on amine derivatives, for example, 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.

[0412] Ascorbic acid (vitamin C) and ascorbic acid derivatives, such as ascorbyl palmitate, laurate and stealth, as well as ascorbyl sulfate and phosphate,

[0413] Antioxidants based on amine compounds, for example, 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 Nirenediamine, N,N'-bis(2-naphthyl)-p-phenylenediamine, N-isopropyl-N'-phenyl-p-phenylenediamine, N-(1,3-dimethylbutyl)-N'-phenyl-p-phenylenediamine, N-(1-methylheptyl)-N'-phenyl-p-phenylenediamine, N-cyclohexyl-N'-phenyl-p-phenylenediamine, 4-(p-toluenesulfamoyl)diphenylamine, N,N'-dimethyl-N,N'-di-sec-butyl- p-phenylenediamine, diphenylamine, N-allyldiphenylamine, 4-isopropoxydiphenylamine, N-phenyl-1-naphthylamine, N-(4-tert-octylphenyl)-1-naphthylamine, N-phenyl-2-naphthylamine, octyl-substituted diphenylamine, e.g., p,p'-di-tert-octyldiphenylamine, 4-n-butylaminophenol, 4-butyrylaminophenol, 4-nonanoylaminophenol, 4-dodecanoyl Aminophenol, 4-octadecanoylaminophenol, bis[4-methoxyphenyl)amine, 2,6-di-tert-butyl-4-dimethylaminomethylphenol, 2,4-diaminodiphenylmethane, 4,4'-diaminodiphenylmethane, N,N,N',N'-tetramethyl-4,4'-diaminodiphenylmethane, 1,2-bis[(2-methylphenyl)amino]ethane, 1,2-bis(phenylamino)propane, (o-tolyl)biguanide, bis[4-(1',[3'-dimethylbutyl)phenyl]amine, tert-octyl-substituted N-phenyl-1-naphthylamine, mixtures of monoalkylated and dialkylated tert-butyl / tert-octyldiphenylamine, mixtures of monoalkylated and dialkylated nonyldiphenylamine, mixtures of monoalkylated and dialkylated dodecyldiphenylamine, mixtures of monoalkylated and dialkylated isopropyl / isohexyldiphenylamine, mixtures of monoalkylated and dialkylated tert-butyldiphenylamine, 2,3-dihydro-3,3-dimethyl-4H-1,4-benzothiazine , phenothiazine, mixtures of monoalkylated and dialkylated tert-butyl / tert-octylphenothiazine, mixtures of monoalkylated and dialkylated tert-octylphenothiazine, N-allylphenothiazine, N,N,N',N'-tetraphenyl-1,4-diaminobuta-2-ene, N,N-bis(2,2,6,6-tetramethylpiperidine-4-yl)hexamethylenediamine, bis(2,2,6,6-tetramethylpiperidine-4-yl)sevacate, 2,2,6,6-tetramethylpiperidine-4-one and 2,2,6,6-tetramethylpiperidine-4-ol,

[0414] Phosphines, phosphites and phosphonits, for example, triphenylphosphine, triphenylphosphine, diphenylalkylphosphine, phenyldialkylphosphine, tris(nonylphenyl)phosphine, trilaurylphosphine, trioctadecylphosphine, distearyl pentaerythritol diphosphine, tris(2,4-di-tert-butylphenyl)phosphine, diisodecyl pentaerythritol diphosphine, bis(2,4-di-tert-butylphenyl) pentaerythritol diphosphine, bis(2,6-di-tert-butyl-4-methylphenyl) pentaerythritol diphosphine, diisodecyloxypentaerythritol diphosphine, bis(2,4-di-tert-butyl-6- Methylphenyl) pentaerythritol diphosphine, bis(2,4,6-tris(tert-butylphenyl)) pentaerythritol diphosphine, tristearyl sorbitol triphosphine, tetrakis(2,4-di-tert-butylphenyl)4,4'-biphenylenediphosphonit, 6-isooctyloxy-2,4,8,10-tetra-tert-butyl-12H-dibenzo[d,g]-1,3,2-dioxaphosphosine, 6-fluoro-2,4,8,10-tetra-tert-butyl-12-methyl-dibenzo[d,g]-1,3,2-dioxaphosphosine, bis(2,4-di-tert-butyl-6-methylphenyl) methylphosphine and bis(2,4-di-tert-butyl-6-methylphenyl) ethylphosphine,

[0415] 2-(2'-hydroxyphenyl)benzotriazole, e.g., 2-(2'-hydroxy-5'-methylphenyl)benzotriazole, 2-(3',5'-di-tert-butyl-2'-hydroxyphenyl)benzotriazole, 2-(5'-tert-butyl-2'-hydroxyphenyl)benzotriazole, 2-(2'-hydroxy-5'-(1,1,3,3-tetramethylbutyl)phenyl)benzotriazole, 2-(3',5'-di-tert-butyl-2'-hydroxyphenyl)-5-chlorobenzotriazole, 2-(3'- tert-butyl-2'-hydroxy-5'-methylphenyl)-5-chlorobenzotriazole, 2-(3'-sec-butyl-5'-tert-butyl-2'-hydroxyphenyl)benzotriazole, 2-(2'-hydroxy-4'-octyloxyphenyl)benzotriazole, 2-(3',5'-ditert-amyl-2'-hydroxyphenyl)benzotriazole, 2-(3,5'-bis-(α,α-dimethylbenzyl)-2'-hydroxyphenyl)benzotriazole, 2-(3'-tert-butyl-2'-hydroxy-5' A mixture of -(2-octyloxycarbonylethyl)phenyl)-5-chlorobenzotriazole, 2-(3'-tert-butyl-5'-[2-(2-ethylhexyloxy)carbonylethyl]-2'-hydroxyphenyl)-5-chlorobenzotriazole, 2-(3'-tert-butyl-2'-hydroxy-5'-(2-methoxycarbonylethyl)phenyl)-5-chlorobenzotriazole, 2-(3'-tert-butyl-2'-hydroxy-5'-(2-methoxycarbonylethyl)phenyl)benzotriazole, 2-(3'-t ert-butyl-2'-hydroxy-5'-(2-octyloxycarbonylethyl)phenyl)benzotriazole, 2-(3'-tert-butyl-5'-[2-(2-ethylhexyloxy)carbonylethyl]-2'-hydroxyphenyl)benzotriazole, 2-(3'-dodecyl-2'-hydroxy-5'-methylphenyl)benzotriazole and 2-(3'-tert-butyl-2'-hydroxy-5'-(2-isooctyloxycarbonylethyl)phenylbenzotriazole, 2,2'-methylenebis[4-(1,1,3,[3-tetramethylbutyl)-6-benzotriazole-2-ylphenol]; the product of complete esterification of 2-[3'-tert-butyl-5'-(2-methoxycarbonylethyl)-2'-hydroxyphenyl]-2H-benzotriazole with polyethylene glycol 300,

[0416] Sulfur-containing peroxide scavengers and sulfur-containing antioxidants, for example, esters of 3,3'-thiodipropionic acid, for example, lauryl, stearyl, myristyl and tridecyl esters, mercaptobenzimidazole, and 2-mercaptobenzimidazole, dibutylzinc dithiocarbamate, dioctadecyl disulfide and zinc salts of pentaerythritol tetrakis(β-dodecylmercapto)propionate.

[0417] 2-Hydroxybenzophenones, for example, 4-hydroxy, 4-methoxy, 4-octyloxy, 4-decyclooxy, 4-dodecyloxy, 4-benzyloxy, 4,2',4'-trihydroxy, 2'-hydroxy-4,4'-dimethoxy derivatives,

[0418] Unsubstituted and substituted benzoic acid esters, e.g., 4-tert-butylphenyl salicylate, phenyl salicylate, octylphenyl salicylate, dibenzoyl resorcinol, bis(4-tert-butylbenzoyl)resorcinol, benzoyl resorcinol, 2,4-di-tert-butylphenyl 3,5-di-tert-butyl-4-hydroxybenzoate, hexadecyl-3,5-di-tert-butyl-4-hydroxybenzoate, octadecyl-3,5-di-tert-butyl-4-hydroxybenzoate, and 2-methyl-4,6-di-tert-butylphenyl-3,5-di-tert-butyl-4-hydroxybenzoate.

[0419] Acrylates, for example, ethyl α-cyano-β,β-diphenyl acrylate, isooctyl α-cyano-β,β-diphenyl acrylate, methyl α-methoxycarbonyl cinnamate, methyl α-cyano-β-methyl-p-methoxycinnamate, butyl-α- Cyano-β-methyl-p-methoxycinnamate and methyl-α-methoxycarbonyl-p-methoxycinnamate, sterically hindered amines, e.g., bis(2,2,6,6-tetramethylpiperidine-4-yl)sevacate, bis(2,2,6,6-tetramethylpiperidine-4-yl)succinate, bis(1,2,2,6,6-pentamethylpiperidine-4-yl)sevacate, bis(1-octyloxy -2,2,6,6-tetramethylpiperidine-4-yl) sevacate, bis(1,2,2,6,6-pentamethylpiperidine-4-yl)-n-butyl-3,5-di-tert-butyl-4-hydroxybenzylmalonate, condensation product of 1-(2-hydroxyethyl)-2,2,6,6-tetramethyl-4-hydroxypiperidine and succinic acid, N,N'-bis(2,2,6,6-tetramethylpiperidine- Condensation product of 4-yl)hexamethylenediamine and 4-tert-octylamino-2,6-dichloro-1,3,5-triazine, tris(2,2,6,6-tetramethylpiperidine-4-yl)nitrilotriacetate, tetrakis(2,2,6,6-tetramethylpiperidine-4-yl)1,2,3,4-butanetetracarboxylate, 1,1'-(1,2-ethylene)bis(3,3,5,5-tetra Methylpiperazinone), 4-benzoyl-2,2,6,6-tetramethylpiperidine, 4-stearyloxy-2,2,6,6-tetramethylpiperidine, bis(1,2,2,6,6-pentamethylpiperidine-4-yl)2-n-butyl-2-(2-hydroxy-3,5-di-tert-butylbenzyl)malonate, 3-n-octyl-7,7,9,9-tetramethyl-1,3,8-triazaspiro[4.5] Decane-2,4-dione, bis(1-octyloxy-2,2,6,6-tetramethylpiperidine-4-yl)sebacate, bis(1-octyloxy-2,2,6,6-tetramethylpiperidine-4-yl)succinate, condensation product of N,N'-bis(2,2,6,6-tetramethylpiperidine-4-yl)hexamethylenediamine and 4-morpholino-2,6-dichloro-1,3,5-triazine, 2-chloro-4,6-bis(4-n-butylamino-2,2,6,6-tetramethylpiperidine-4-yl)-1,3 Condensation product of 5-triazine and 1,2-bis(3-aminopropylamino)ethane, condensation product of 2-chloro-4,6-di(4-n-butylamino-1,2,2,6,6-pentamethylpiperidine-4-yl)-1,3,5-triazine and 1,2-bis(3-aminopropylamino)ethane, 8-acetyl-3-dodecyl-7,7,9,9-tetramethyl-1,3,8-triazaspiro[4.5]-decane-2,4-dione, 3-dodecyl-1-(2,2,6,6-tetramethylpiperidine-4-yl)pyrrolidine-2, A mixture of 5-dione, 3-dodecyl-1-(1,2,2,6,6-pentamethylpiperidine-4-yl)pyrrolidine-2,5-dione, 4-hexadecyloxy- and 4-stearyloxy-2,2,6,6-tetramethylpiperidine, a condensation product of N,N'-bis(2,2,6,6-tetramethylpiperidine-4-yl)hexamethylenediamine and 4-cyclohexylamino-2,6-dichloro-1,3,5-triazine, 1,2-bis(3-aminopropylamino)ethane and 2,4,6-trichloro-1,3,5 - Condensation product of triazine, 4-butylamino-2,2,6,6-tetramethylpiperidine, N-(2,2,6,6-tetramethylpiperidine-4-yl)-n-dodecylsuccinimide, N-(1,2,2,6,6-pentamethylpiperidine-4-yl)-n-dodecylsuccinimide, 2-undecyl-7,7,9,9-tetramethyl-1-oxa-3,8-diaza-4-oxospiro[4.5]-decane, 7,7,9,9-tetramethyl-2-cycloundecyl-1-oxa-3,8-diaza-4-oxospiro-[4.5] Condensation product of decane and epichlorohydrin, condensation product of 4-amino-2,2,6,6-tetramethylpiperidine and tetramethylolacetylenediurea and poly(methoxypropyl-3-oxy)-[4(2,2,6,6-tetramethyl)piperidinyl]-siloxane.

[0420] Oxalamides, for example, 4,4'-dioctyloxyoxanilide, 2,2'-diethoxyoxanilide, 2,2'-dioctyloxy-5,5'-di-tert-butoxanilide, 2,2'-didodecyloxy-5,5'-di-tert-butoxanilide, 2-ethoxy-2'-ethyloxanilide, N,N'-bis(3-dimethylaminopropyl)oxalamide, mixtures thereof with 2-ethoxy-5-tert-butyl-2'-ethoxanilide and 2-ethoxy-2'-ethyl-5,4'-di-tert-butoxanilide, and mixtures thereof with ortho-, para-methoxy-disubstituted oxanilides, and mixtures thereof with ortho- and para-ethoxy-disubstituted oxanilides, and

[0421] 2-(2-hydroxyphenyl)-1,3,5-triazine, for example, 2,4,6-tris-(2-hydroxy-4-octyloxyphenyl)-1,3,5-triazine, 2-(2-hydroxy-4-octyloxyphenyl)-4,6-bis(2,4-dimethylphenyl)-1,3,5-triazine, 2-(2,4-dihydroxyphenyl)-4,6-bis(2,4-dimethylphenyl)-1,3,5-triazine, 2,4-bis(2-hydroxy-4-propyloxyphenyl)-6-(2,4-dimethylphenyl) Nyl)-1,3,5-triazine, 2-(2-hydroxy-4-octyloxyphenyl)-4,6-bis(4-methylphenyl)-1,3,5-triazine, 2-(2-hydroxy-4-dodecyloxyphenyl)-4,6-bis(2,4-dimethylphenyl)-1,3,5-triazine, 2-(2-hydroxy-4-tridecyloxyphenyl)-4,6-bis(2,4-dimethylphenyl)-1,3,5-triazine, 2-[2-hydroxy-4-(2-hydroxy-3-butyloxypropoxy)phenyl]- 4,6-bis(2,4-dimethyl)-1,3,5-triazine, 2-[2-hydroxy-4-(2-hydroxy-3-octyloxypropoxy)phenyl]-4,6-bis(2,4-dimethyl)-1,3,5-triazine, 2-[4-(dodecyloxy / tridecyloxy-2-hydroxypropoxy)-2-hydroxyphenyl]-4,6-bis(2,4-dimethylphenyl)-1,3,5-triazine, 2-[2-hydroxy-4-(2-hydroxy-3-dodecyloxypropoxy)phenyl]-4,6-bis Su-(2,4-dimethylphenyl)-1,3,5-triazine, 2-(2-hydroxy-4-hexyloxyphenyl)-4,6-diphenyl-1,3,5-triazine, 2-(2-hydroxy-4-methoxyphenyl)-4,6-diphenyl-1,3,5-triazine, 2,4,6-tris[2-hydroxy-4-(3-butoxy-2-hydroxypropoxy)phenyl]-1,3,5-triazine, and 2-(2-hydroxyphenyl)-4-(4-methoxyphenyl)-6-phenyl-1,3,5-triazine.

[0422] In a preferred embodiment, the RM formulation is dissolved in a suitable solvent preferably selected from organic solvents.

[0423] The solvent is preferably selected from ketones, such as acetone, methyl ethyl ketone, methyl propyl ketone, methyl isobutyl ketone, or cyclohexanone; acetates, such as methyl, ethyl, or butyl acetate, or methyl acetacetate; alcohols, such as methanol, ethanol, or isopropyl alcohol; aromatic solvents, such as toluene or xylene; alicyclic hydrocarbons, such as cyclopentane or cyclohexane; halogenated hydrocarbons, such as dichloromethane or trichloromethane; glycols or their esters, such as PGMEA (propyl glycol monomethyl ether acetate) or γ-butyrolactone. It is also possible to use binary, ternary, or more mixtures of the above solvents. Methyl isobutyl ketone is a preferred solvent, especially in multilayer applications.

[0424] If the RM formulation contains one or more solvents, the total concentration of all solids containing RM in the solvent is preferably 5-60%, more preferably 10-50%, and particularly 10-35%.

[0425] Preferably, the RM formulation includes one or more compounds or formula I and chiral isomerized compounds, in addition to the following: a) Optionally, one or more polyreactive or bireactive polymerizable mesogenic compounds (preferably selected from compounds of formula DRM and corresponding sub-formulas), and / or b) Optionally, one or more additional polymerizable chiral compounds preferably selected from formula CRM or its sub-formulas, and / or c) Optionally, one or more additional nonpolymerizable chiral compounds preferably selected from formulas CI, C-II, and C-III, and / or d) Optionally, one or more monoreactive mesogenic compounds (preferably selected from compounds of formula MRM and corresponding sub-formulas), and / or e) Optionally, one or more photoinitiators, and / or f) Optionally, one or more antioxidants, and / or g) Optionally, one or more adhesion promoters, and / or h) Optionally, one or more surfactants, and / or i) Optionally, one or more monoreactive, direactive, or polyreactive polymerizable nonmesogenic compounds, and / or j) Optionally, one or more dyes that exhibit an absorption maximum at the wavelength used to initiate photopolymerization, and / or k) Optionally, one or more chain transfer agents, and / or l) Optionally, one or more (UV) stabilizers, and / or m) Optionally, one or more types of lubricants and fluidity enhancers, and n) Optionally, one or more diluents, and / or o) Optionally, non-polymerizable nematic components, and / or p) Optionally, one or more organic solvents.

[0426] More preferably, the RM formulation includes: a) Compounds of formula I or its corresponding preferred sub-formula, b) Preferably formula I * More preferably, formula I * One or more chiral isomerized compounds selected from A or its corresponding preferred sub-formulas, c) Optionally, one or more, preferably two or more, bireactive polymerizable mesogenic compounds selected from the compounds of formula DRM-1, d) Optionally, one or more, preferably two or more, monoreactive polymerizable mesogenic compounds selected from the compounds represented by formula MRM-1 and / or MRM-4 and / or MRM-6 and / or MRM-7, e) Optionally, one or more additional polymerizable chiral compounds preferably selected from formula CRM or its sub-formulas, f) Optionally, one or more additional nonpolymerizable chiral compounds preferably selected from formulas CI, C-II, and C-III, g) Optionally, one or more antioxidants, h) Optionally, one or more photoinitiators, i) Optionally, one or more organic solvents.

[0427] RM mixtures and RM formulations can themselves be prepared by conventional methods, for example, by mixing one or more of the above-mentioned chiral isomerizing compounds with one or more of the RMs defined above, and adding further additives as necessary.

[0428] The present invention further relates to a method for producing polymer fill, and preferably comprises the following steps: • A step of providing a layer of the RM mixture or RM formulation described above and below on a substrate. The substrate may optionally be provided with an orientation layer that can induce planar orientation relative to adjacent layers of the RM mixture. If a solvent is present, remove it as needed. Optionally, a step of annealing the RM mixture layer (i.e., without solvent), preferably at a temperature at which a chiral nematic phase is formed. • The RM layer is irradiated with ultraviolet light, preferably in air (first ultraviolet step). Optionally, anneal the RM mixture layer. Preferably, anneal at a temperature that results in a chiral nematic phase, and • A second step (second ultraviolet step) involves irradiating the RM layer with ultraviolet light, preferably in an inert gas atmosphere.

[0429] The present invention further relates to polymer fills obtained by this method.

[0430] More preferably, the method for producing polymer fill according to the present invention includes the following steps: Preferably, a layer of the above and below RM mixture or RM formulation, or a solution thereof, is provided on a substrate having an orientation layer that induces a planar orientation layer, such as a rubbing-treated polyimide layer or a photo-orientation layer, for example, by spin coating or printing, and the present solvent is removed as necessary. If necessary, anneal the RM mixture layer (i.e., without solvent) at a temperature that preferably results in a chiral nematic phase. The layer of RM mixture (i.e., without solvent) is exposed to ultraviolet light, preferably unpolarized UV light, very preferably unpolarized UVA light, for example, 40-500 mJ / cm², to induce photoisomerization of the chiral compound containing the photoisomerizable group and impart a chiral structure with a polarized helical pitch. 2 The exposure is performed at a dose of this magnitude, preferably in an atmospheric environment at room temperature ("first UV step"). If necessary, the RM mixture layer is annealed at a temperature that preferably results in a chiral nematic phase. The RM mixture layer is exposed to unpolarized UV light, very preferably unpolarized UVA light, for example, 200-2000 mJ / cm². 2 A step of irradiating at room temperature, preferably in an inert gas atmosphere (e.g., nitrogen), with the specified irradiation dose ("second UV step").

[0431] Preferably, in the method according to the present invention, all irradiation or UV exposure steps are performed at room temperature, and the RM mixture or formulation layer is not subjected to heat treatment during or between the irradiation or UV exposure steps.

[0432] The first irradiation or first UV step induces photoisomerization of the chiral compound containing the photoisomerizable group, conferring a chiral structure with an uneven helical pitch. The second irradiation, i.e., the second UV irradiation step, induces photopolymerization of the polymerizable mesogenic compound, thereby immobilizing the chiral structure.

[0433] While not bound by any particular theory, the inventors believe that oxygen present in the air during the first UV irradiation step inhibits free radical polymerization. This effect offers several advantages.

[0434] Firstly, this effect allows the use of RMs that have an absorption maximum in the same UV wavelength range as the photoisomerized chiral compound, and therefore polymerize unless inhibited. Since finding a suitable RM with very high birefringence and a suitable chiral photoisomerized compound is often difficult, this effect broadens the selection of suitable mixed components and makes it easier to adjust the chiral RM mixed composition to the specific requirements when the polymer film is ultimately used as an optical element.

[0435] Secondly, this effect can be advantageously utilized to polymerize the film partially by creating a gradient in the thickness direction of the film. Thus, the molecular chains at the top of the film are exposed to oxygen and therefore polymerize more slowly, while the molecular chains at the substrate interface at the bottom of the film are exposed to less oxygen and are more susceptible to oxygen inhibition, thus polymerizing more easily.

[0436] The presence of a photoisomerizable chiral compound causes photoisomerization during the first UV irradiation step, reducing the helical twist force (HTP) of the photoisomerizable chiral compound upon UV irradiation. Changes in the chiral structure are physically suppressed in regions of high polymer density. At the top or surface of the film, where the polymer density is low, the chiral structure can change more freely. However, at the bottom of the film adjacent to the substrate, more photopolymerization occurs, resulting in higher polymer density and thus inhibiting changes in the chiral structure. This creates a chiral pitch gradient within the film. Therefore, after the above method is performed, the polymerized RM mixture exhibits accelerated chiral rotation in the main surface of the polymer film or in the thickness direction of the film. Preferably, the polymerized RM mixture exhibits a biased pitch such that the chiral rotation angle increases or decreases stepwise across the film thickness.

[0437] This RM mixture or formulation can be applied or printed onto a substrate using known techniques such as spin coating or printing, with the solvent evaporated before polymerization. In many cases, heating the coated solution is suitable to accelerate the evaporation of the solvent.

[0438] RM mixtures or formulations can be applied to substrates by conventional coating techniques such as spin coating or blade coating. They can also be applied to substrates by conventional printing techniques known to experts, such as screen printing, offset printing, reel-to-reel printing, letterpress printing, gravure printing, rotogravure printing, flexographic printing, intaglio printing, pad printing, heat seal printing, inkjet printing, and printing with stamps or printing plates.

[0439] Suitable substrate media and substrates are known to experts and described in the literature as conventional substrates used in the optical film industry, such as glass or plastic. Preferred substrates particularly suitable for polymerization are polyesters such as polyethylene terephthalate (PET) or polyethylene naphthalate (PEN), polyvinyl alcohol (PVA), polycarbonate (PC), triacetylcellulose (TAC), cycloolefin polymer (COP), or generally known color filter materials, preferably triacetylcellulose (TAC), cycloolefin polymer (COP), or generally known color filter materials.

[0440] In another preferred embodiment, the substrate has a surface grid or surface pattern. In another preferred embodiment, the substrate is fabricated from a photo-aligned layer (PAL) that is patterned by laser interferometry to form a grid pattern having a specified pitch.

[0441] The Friedel-Creagh-Kmetz rule states that the RM layer (γ RM ) and substrate (γ s By comparing the surface energies of the two components, it can be used to predict whether a mixture will have a planar or homeotropic orientation.

[0442] γ RM >γ s In this case, the reactive mesogenic compound exhibits homeotropic orientation, γ RM <γ s In this case, the reactive mesogenic compound exhibits homogeneous orientation.

[0443] While we do not wish to be bound by any particular theory, it is thought that when the surface energy of the substrate is relatively low, the intermolecular forces between reactive mesogens become stronger than the forces across the interface between the reactive mesogens and the substrate. As a result, the reactive mesogens are likely to orient perpendicular to the substrate to maximize the intermolecular forces (homeotropic orientation). Therefore, an additional orientation layer is needed that can induce planar orientation relative to adjacent layers of RM mixtures or formulations.

[0444] When the surface tension of the substrate is greater than that of the standard material, forces across the interface become dominant. If the reactive mesogens are aligned parallel to the substrate, the interfacial energy is minimized, and the long axis of the standard material can interact with the substrate. One method to promote parallel orientation is to coat the substrate with a polyimide layer and rub it with a velvet cloth.

[0445] Other suitable planar oriented layers are known in the art, such as rubbing polyimide or alignment layers prepared by photoalignment, as described in, for example, U.S. Patent No. 5,602,661, U.S. Patent No. 5,389,698, or U.S. Patent No. 6,717,644.

[0446] In general, an overview of orientation techniques can be found, for example, in I. Sage, "Thermotropic Liquid Crystals," edited by G.G. Ray, John Wiley & Sons, 1987, pp. 75-77; and in T. Uchida and H. Seki, "Liquid Crystals - Applications and Uses Vol. 3," edited by B. Bahadur, World Scientific Publishing, Singapore, 1992, pp. 1-63. An overview of orientation materials and techniques can be found in J. Cognard, Mol. Cryst. Liq. Cryst. Vol. 78, Supplement 1 (1981), pp. 1-77.

[0447] In a preferred embodiment, the method of the present invention includes a step of allowing the RM mixture or formulation to stand for a certain period of time in order to uniformly redistribute the RM mixture or formulation onto a substrate (hereinafter referred to as "annealing").

[0448] In a preferred embodiment, after supplying the RM mixture or RM formulation onto the substrate, the laminate is annealed for 10 seconds to 1 hour, preferably 20 seconds to 10 minutes, most preferably 30 seconds to 2 minutes. Annealing is preferably carried out at room temperature.

[0449] The RM mixture preferably consists of compounds that spontaneously orient themselves when deposited on a substrate as a mixture. Therefore, preferably, the RM mixture does not undergo heat treatment to orient the mesogenic or liquid crystalline compounds before UV irradiation.

[0450] If necessary, the laminate can be cooled to room temperature after annealing at high temperatures. Cooling can be performed actively using a cooling aid, or passively by leaving the laminate to stand for a certain period of time.

[0451] In a preferred embodiment, in a first ultraviolet irradiation step, the RM mixture is exposed to chemical irradiation, for example, as described in International Publication 01 / 20394, British Patent No. 2,315,072, or International Publication 98 / 04651.

[0452] Chemical irradiation refers to irradiation with light such as ultraviolet rays, infrared rays, and visible light, or irradiation with X-rays, gamma rays, or high-energy particles such as ions and electrons. Preferably, the first ultraviolet irradiation step is carried out by irradiation with light, particularly ultraviolet rays, especially UVA light.

[0453] For chemical irradiation, a single UV lamp or multiple UV lamps can be used as the light source. Increasing the lamp output can shorten the curing time. Other light sources for light irradiation include lasers such as UV lasers, infrared lasers, and visible lasers.

[0454] The curing time depends, in particular, on the reactivity of the photoreactive compound, the thickness of the coating layer, and the output and selected wavelength of the UV lamp. The curing time is preferably 5 minutes or less, very preferably 3 minutes or less, and most preferably 1 minute or less. For mass production, a short curing time of 30 seconds or less is preferred.

[0455] The appropriate UV irradiation output in the first UV step is preferably 5 to 300 mW / cm². -2 More preferably 50-250 mW / cm² -2 Most preferably 100-180 mW / cm² -2 It is within the range.

[0456] In relation to the ultraviolet radiation irradiated, and as a function of time, the appropriate ultraviolet radiation dose is preferably 20 to 1000 mJcm². -2 The range is, more preferably 30 to 800 mJ cm. -2 The range is very preferably 40-500 mJ / cm². -2 The range is most preferably 40-200 mJ / cm². -2 It is within the range.

[0457] The first irradiation step or the first ultraviolet step is preferably carried out in air.

[0458] The first irradiation step or the first ultraviolet step is preferably carried out at room temperature.

[0459] Photopolymerization of the RM mixture in the second irradiation step is preferably achieved by exposing it to chemical radiation. Chemical radiation refers to irradiation with light such as ultraviolet, infrared, or visible light, X-ray or gamma ray irradiation, or irradiation with high-energy particles such as ions or electrons. Preferably, polymerization is carried out by light irradiation, especially ultraviolet irradiation. As a chemical radiation source, for example, a single UV lamp or a group of UV lamps can be used. If the lamp output is high, the curing time can be shortened. Other usable light irradiation sources include lasers such as UV lasers, IR lasers, and visible lasers.

[0460] The curing time in photopolymerization depends, in particular, on the reactivity of the RM mixture, the thickness of the coating layer, the type of polymerization initiator, and the power of the UV lamp. The curing time is preferably ≤5 minutes, very preferably ≤3 minutes, and most preferably ≤1 minute. For mass production, a short curing time of ≤30 seconds is preferred.

[0461] The appropriate UV irradiation dose for photopolymerization is preferably 100 to 1000 mW / cm². -2 The range is, more preferably, 200 to 800 mW / cm². -2 The range is, most preferably 300-600 mW / cm². -2 It is within the range.

[0462] As a function of the amount and duration of UV irradiation, an appropriate UV irradiation dose is preferably 25 to 16500 mJcm². -2 This range is more preferably 50 to 7200 mJcm -2 The range is, and very preferably, 100 to 3500 mJcm -2 The range is, most preferably 200 to 2000 mJ / cm². -2 It is within the range.

[0463] Photopolymerization (second irradiation step or second ultraviolet step) is preferably carried out under an inert gas atmosphere, preferably under a nitrogen atmosphere.

[0464] Photopolymerization (second irradiation step or second ultraviolet step) is preferably carried out at room temperature.

[0465] The preferred thickness of the polymerized LC film according to the present invention is determined by the optical properties required for the film or the final product.

[0466] When polymer films are used for optical applications, their thickness is preferably 0.1 to 10 μm, very preferably 0.1 to 2 μm, and particularly 0.1 to 1 μm.

[0467] In a preferred embodiment, the polymer film according to the present invention exhibits a planar orientation. That is, the LC molecules are oriented parallel to the film surface, and the helical axes are oriented substantially perpendicular to the film surface.

[0468] In another preferred embodiment, the polymer film according to the present invention exhibits a tilt orientation. That is, the liquid crystal molecules are oriented at a certain angle to the film surface, and the helical axis is oriented at a certain angle to the film surface, and this angle is also called the tilt angle. In the tilt film, the tilt angle between the helical axis and the axis perpendicular to the film surface is 5° to 45°, very preferably 15° to 45°.

[0469] In another preferred embodiment, the inclination angle between the helical axis and the axis perpendicular to the film plane is 0° to 15°, very preferably 0° to 5°.

[0470] Planar orientation can be induced, for example, by providing an orientation layer, such as a polyimide orientation layer, on the substrate, as described above. Gradual orientation can be achieved, for example, by adding an orientation additive to a chiral RM mixture, or by using a substrate with a surface grid or pattern, such as a PB grid.

[0471] The optical delay (δ(λ)) of the polymer film as a function of the wavelength (λ) of the incident beam is given by the following equation (7):

[0472]

number

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

[0474] Birefringence and the resulting optical delay depend on the film thickness and the tilt angle of the optical axis within the film (see Berek compensation). Therefore, those skilled in the art recognize that different optical delays or different birefringences can be induced by adjusting the orientation of liquid crystal molecules within a polymer film.

[0475] The birefringence (Δn) of the polymer film according to the present invention is preferably in the range of 0.25 to 0.80, more preferably 0.30 to 0.70, and very preferably 0.30 to 0.55.

[0476] After photopolymerization, the resulting polymer film can be peeled from the substrate and combined with other substrates or optical films by lamination methods known to those skilled in the art. Suitable substrates and optical films are shown above, and include, in particular, polarizers, especially linear polarizers, photo-alignment layers, or diffraction gratings, such as PB gratings.

[0477] The polymer film according to the present invention has good adhesion to plastic substrates, particularly TAC, COP, and color filters. Therefore, it can be used as an adhesive or base coat for subsequent polymerized RM or LC layers that have low adhesion to the substrate.

[0478] The polymer film of the present invention can also be used as an alignment film or substrate for other liquid crystal materials or RM materials. The inventors have found that polymer films obtained from the above and below RM formulations are particularly useful for multilayer applications due to their improved dewetting properties. In this way, stacks of optical films or preferably polymerized LC films can be prepared.

[0479] The present invention further relates to an optical element, electro-optical element, or electronic element or component comprising the RM mixture or polymer film described above and below.

[0480] Preferably, the component is a diffraction grating, particularly preferably PBG or Bragg PG, and comprises a polymer film obtained from the RM mixture or RM formulation according to the present invention as described above and below.

[0481] In summary, the polymer films and RM mixtures of the present invention are useful as optical elements such as polarizers, compensating plates, alignment layers, circular polarizers, or color filters in liquid crystal displays or projection systems, decorative images for the manufacture of liquid crystals or effect pigments, and in particular as reflective films having spatially varying reflective colors, for example, as multicolor images for decorative, information storage, or security applications (e.g., anti-counterfeiting documents such as identification cards, credit cards, and banknotes).

[0482] 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, particularly LCDs.

[0483] The present invention is described above and below with particular reference to preferred embodiments. It should be understood that various changes and modifications can be made therewith without departing from the spirit and scope of the invention.

[0484] Many of the compounds or mixtures described above and below are commercially available. All of these compounds are either publicly known or can be prepared under known reaction conditions suitable for the reactions described above by methods known in themselves and described in the literature (e.g., Houben-Weyl, Methoden der Organischen Chemie [Methods of Organic Chemistry], Georg-Thieme-Verlag, Stuttgart, etc.). Modifications known in themselves but not mentioned herein can also be used.

[0485] It will be understood that modifications are possible to the above-described embodiments of the present invention within the scope of the invention. Unless otherwise specified, alternative features serving the same, equivalent, or similar purposes may replace each of the features disclosed herein. Therefore, unless otherwise specified, each disclosed feature is merely one example of a general set of equivalent or similar features.

[0486] All features disclosed herein can be combined in any combination, except for any combination in which at least some of such features and / or steps are mutually exclusive. In particular, preferred features of the present invention are applicable to all aspects of the invention and can be used in any combination. Similarly, features described in non-essential combinations may be used separately (without combination).

[0487] Many of the features described above, and especially those of preferred embodiments, will be understood to be inventive not only as part of embodiments of the present invention but also in themselves. These features may be protected separately, either in addition to or in lieu of the claimed invention.

[0488] Unless explicitly stated otherwise, all temperature values ​​expressed in this application, such as the melting point T(K,N), the transition from the smectic (S) phase to the nematic (N) phase T(S,N), and the transparency point T(N,I), are cited in degrees Celsius (°C). Furthermore, K represents the crystalline state, N represents the nematic phase, and I represents the isotropic phase. The data between these symbols represents the transition temperature.

[0489] Unless otherwise explicitly stated, all physical properties are determined based on "Merck Liquid Crystals, Physical Properties of Liquid Crystals," November 1997, Merck AG, Germany. Unless otherwise specified, temperature is measured at 20°C. Optical anisotropy (Δn) is measured at a wavelength of 589.3 nm.

[0490] In the above and below, percentages are weight percentages unless otherwise stated. All temperatures are expressed in Celsius.

[0491] In the above and below, mp represents the melting point, cl.p. represents the transparency point, and T g represents the glass transition temperature. Furthermore, C represents the crystalline state, N represents the nematic phase, and S represents the glass transition temperature. A S B These represent smectic phase A, smectic phase B, etc. x represents an unidentified smectic phase, X represents an unidentified intermediate phase, and I represents an isotropic phase. The values ​​between these symbols represent the transition temperature (°C). Δn is the optical anisotropy or birefringence (Δn=n) measured at a wavelength of 589 nm and 20°C. e -n o , where n o n represents the refractive index perpendicular to the long axis of the molecule, e The ∫ represents the refractive index parallel to the long axis of the molecule. Optical and electro-optical data are measured at 20°C unless otherwise specified. "Transparency point" and "transparency temperature" refer to the temperature of the transition from the LC phase to the isotropic phase.

[0492] Unless otherwise specified, the percentages of solid components in the above and below RM mixtures or RM formulations refer to the total amount of solids in the mixture or formulation, i.e., the total amount excluding the solvent.

[0493] Unless otherwise specified, all optical properties, electro-optical properties, and physical parameters such as birefringence, dielectric constant, electrical conductivity, electrical resistivity, and sheet resistance refer to a temperature of 20°C.

[0494] The present invention will be described in more detail with reference to the following embodiments, which are for illustrative purposes only and do not limit the scope of the invention. [Examples]

[0495] <Example 1> RM mixture M1 is prepared with the following composition.

[0496] [Table 1]

[0497] RM I25 has a high birefringence of 0.292, and RM I49 has a high birefringence of 0.300. Polyfox® PF-656 is a surfactant commercially available from Synthomer. The photoinitiator NCI-930 is commercially available from Adeka. The additive Irganox® 1076 is commercially available from CIBA GmbH in Switzerland.

[0498] RM I49 has an absorption peak at approximately 355 nm, but it is a chiral photoisomerized compound I * A1a has an absorption peak at approximately 350 nm. Although the absorption bands of these compounds overlap, a highly birefringent cholesteric polymer film with controllable pitch can be fabricated using the two-step process described herein, as shown below.

[0499] <Example 2> RM mixture M2 is prepared with the following composition.

[0500] [Table 2]

[0501] <Example 3> RM mixture M3 is prepared with the following composition.

[0502] [Table 3]

[0503] <Example 4> RM mixture M4 is prepared with the following composition.

[0504] [Table 4]

[0505] <Example 5> RM mixture M5 is prepared with the following composition.

[0506] [Table 5]

[0507] <Usage example 1> Multiple samples of chiral polymer films are prepared using the following method.

[0508] Multiple samples of each mixture M1, M2, M3, M4, and M5 were dissolved in a mixed ketone solvent system of butane-2-one, cyclopentanone, 4-methylpentane-2-one, and 2-undecanone (1:2:1:2) at a solid content of 20%. Each solution was spin-coated onto polyimide-coated glass slides at 1000 rpm. The wetted layer was heated on a hot stage to 80°C for 60 seconds to evaporate the solvent and anneal the RM layer.

[0509] In the first irradiation step (isomerization step), each RM layer is irradiated with unpolarized UV-A light from a fusion lamp in a room-temperature air environment. Different irradiation powers are applied to the different samples of the RM layers of each mixture M1, M2, M3, M4, and M5. The ultraviolet wavelength is for chiral compound I * Because it lies within the A1a absorption band, it causes isomerization of the compound, leading to a decrease in helical twist force.

[0510] Next, the RM layer undergoes a second annealing by heating it on a hot stage at 80°C for 60 seconds.

[0511] In the second irradiation step (polymerization step), each RM layer is irradiated with 365nm unpolarized UV light from a UV LED lamp under a nitrogen atmosphere at 40°C to completely polymerize the RM layer and form a polymer film. The wavelength of 365nm is suitable for chiral compounds I * Since it is outside the absorption band of A1a, it does not cause further isomerization of the compound. The thickness of the film after polymerization is approximately 1 μm.

[0512] The reflectance spectrum of the film is measured using an ocean optics spectrometer. Reflectance peak λ c The central bandwidth is measured, and the pitch P (nm) of the cholesteric liquid crystal (CLC) is determined from the following formula.

[0513]

number

[0514] In the formula, under the assumption that the twist pitch is uniform throughout the RM layer, n e and n o is λ c These are the normal refractive index and the extraordinary refractive index in [location].

[0515] Chiral Compound I * A1a helical twist force HTP (μm) -1 ) is determined according to the following formula.

[0516]

number

[0517] In the formula, c is the concentration (%) of the compound.

[0518] Table 1 shows the results for each sample of polymer film prepared from mixtures M1 to M5 using different UV powers applied in the first UV irradiation step (isomerization step), for chiral compound I * The CLC pitch and HTP of A1a are shown. An irradiation dose of 0 means that the first irradiation step (isomerization step) is completely omitted.

[0519]

[0520] [Table 6]

[0521] Figure 1 shows the effects of different UV power levels on chiral isomerized compound I in the isomerization process. * This shows the CLC pitch as a function of A1a concentration.

[0522] Figure 2 shows chiral isomerized compound I * The CLC pitch with respect to UV output is shown for different concentrations of A1a.

[0523] From Table 1, Figure 1, and Figure 2, chiral isomerized compound I * It can be seen that the HTP of A1a decreases with increasing UV output during the first UV irradiation process, and the CLC pitch increases. It can also be seen that the CLC pitch decreases with increasing concentration of chiral isomerizing compounds.

[0524] This demonstrates the concept that the helical pitch of a highly birefringent chiral polymer film can be easily and controlledly altered by changing the concentration and / or UV output of the chiral isomerizing compound in the first UV irradiation step (isomerization step) of the film manufacturing process.

[0525] Furthermore, this demonstrates that both photoisomerization and photopolymerization can be controlled even when using chiral photoisomerizable compounds with UV absorption bands overlapping with highly birefringent RMs. This expands the range of suitable mixed components.< / n> < / n>

Claims

1. A mixture comprising at least one chiral isomerized compound and at least one compound of formula I. 【Chemistry 1】 (In the formula, each base is independent of the others, and in each instance is identical or different, and has the following meanings: P is a polymerizable group, Sp is a spacer group or a single bond. R １１ This is an alkyl, alkoxy, thioalkyl, alkylcarbonyl, alkoxycarbonyl, alkylcarbonyloxy or alkoxycarbonyloxy (which may be fluorinated) having H, F, Cl, CN, 1 to 15, preferably 1 to 5 C atoms, or P-Sp. 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-dihydrophenanthrene-2,7-diyl, 1,2,3,4-tetrahydronaphthalene-5,8-diyl, or indan-2,5-diyl, wherein one or more CH groups in these groups may be replaced with N, and all of them may be replaced with one or more L or P-Sp- groups. C is selected from the group consisting of benzene-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, and benzothiophene-4,7-diyl, all of which may be substituted with one or more groups L or P-Sp-. Furthermore, one of rings C and D may represent a single bond. L is F, Cl, -CN, -SCN, P-Sp-, or a linear, branched, or cyclic alkyl having 1 to 25 C atoms, provided that there is one or more non-adjacent CH ２ - The group is formed such that the O atom and / or S atom are not directly linked to each other, such as -O-, -S-, -CO-, -CO-O-, -O-CO-, -O-CO-O-, -CR ０ =CR ００ -, -C≡C-, 【Chemistry 2】 It may be replaced by, however, one or more H atoms may be replaced by P-Sp-, F or Cl, or two substituents L directly attached to adjacent C atoms may form a cycloalkyl or cycloalkenyl group having 5, 6, 7 or 8 C atoms. Z １１ 、Z １２ is -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 -, -OCH ２ -, -CH ２ O-, -SCH ２ -, -CH ２ S-, -CF ２ O-, -OCF ２ -, -CF ２ S-, -SCF ２ -, -CH ２ CH ２ -, -(CH ２ ) ｎ１ -, -CF ２ CH ２ -, -CH ２ CF ２ -, -CF ２ CF ２ -, -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 ０ , R ００ This is an alkyl having H or 1 to 12 C atoms, Y １ , Y ２ It contains H, F, Cl, NCS, or CN. n is 0, 1, 2, 3 or 4, preferably 0, 1 or 2, more preferably 0 or 1, 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.

2. The mixture according to claim 1, characterized in that, in the compound of formula I, rings A, B, D and / or E of formula I are selected from the group consisting of benzene-1,4-diyl, naphthalene-1,4-diyl, naphthalene-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, and benzothiophene-4,7-diyl, all of which may be substituted with one or more groups L and / or P-Sp-.

3. The mixture according to claim 1 or 2, characterized in that, in the compound of formula I, ring C is selected from the group consisting of benzene-1,4-diyl, naphthalene-1,4-diyl, or anthracene-9,10-diyl, all of which may be monosubstituted or disubstituted with L and / or P-Sp-.

4. The mixture according to any one of claims 1 to 3, characterized in that in the compound of formula I, n = m = 0, and rings B, C, and D form a group selected from the following formulas or their mirror images. 【Transformation 3】 【Chemistry 4】 【Transformation 5】 (In the formula, the naphthalene and phenanthrene groups may be substituted with one or two groups L, L １ and L ２ Each of these terms independently represents H or has one of the meanings given to L in claim 1, where r is 0, 1, 2, 3, or 4, preferably 0, 1, or 2, and L is as defined in claim 1.

5. The mixture according to any one of claims 1 to 4, characterized in that the compound of formula I is selected from the following sub-formulas. 【Transformation 6】 【Transformation 7】 【Transformation 8】 【Chemistry 9】 【Chemistry 10】 【Chemistry 11】 【Chemistry 12】 【Chemistry 13】 【Chemistry 14】 【Chemistry 15】 (In the formula, the naphthalene and phenanthrene groups may be substituted with one or two groups L, and P, Sp, L and r are each independently of each other, identical or different in appearance, having the meanings given in claim 1 or 4, and R is R in claim 1) １１ (It has one of the meanings that can be given to it.)

6. In the compound of formula I, P is an acrylate or methacrylate, preferably an acrylate, and Sp is -(CH ２ ) ｐ１ -, - (CH ２ ) ｐ１ -O-, -(CH ２ ) ｐ１ -O-CO-, -(CH ２ ) ｐ１ -CO-O- or -(CH ２ ) ｐ１ The mixture according to any one of claims 1 to 5, characterized in that it is -O-CO-O-, and in the formula, p1 is an integer from 1 to 6.

7. Isomerizable chiral compounds are of formula I ＊ A mixture according to any one of claims 1 to 6, characterized in that it is selected from among. 【Chemistry 16】 (In the formula, each base is independent of the others and, in each instance, is identical or different in the following sense) R ３ , R ４ is an alkyl group having H, F, Cl, CN, P-Sp-, or up to 25 C atoms, which may be unsubstituted, or monosubstituted or polysubstituted with halogen or CN, and may contain one or more non-adjacent CH ２ The groups, in each case independently of each other, are -O-, -S-, -NH-, -N(CH) such that the oxygen atoms do not directly bond to one another. ３ ) can be replaced with -, -CO-, -COO-, -OCO-, -OCO-O-, -S-CO-, -CO-S- or -C≡C-, P is a polymerizable group, Sp is a spacer group or a single bond. Z ３ 、Z ４ is -CO-O-, -O-CO-, -CH ２ CH ２ -, -OCH ２ -, -CH ２ O-, -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 This is an alicyclic, heterocyclic, aromatic, or heteroaromatic group having 4 to 20 ring atoms, which may be monocyclic or polycyclic, and which may be substituted with one or more L or P-Sp- groups. G is a chiral group, L is F, Cl, -CN, -SCN, P-Sp-, or a linear, branched, or cyclic alkyl having 1 to 25 C atoms, provided that there is one or more non-adjacent CH ２ The groups are such that the O and / or S atoms are not directly linked to each other, -O-, -S-, -CO-, -CO-O-, -O-CO-, -O-CO-O-, -CR ０ =CR ００ -, -C≡C-, 【Chemistry 17】 It may be replaced by, however, one or more H atoms may be replaced by P-Sp-, F or Cl, or two substituents L directly attached to adjacent C atoms may form a cycloalkyl or cycloalkenyl group having 5, 6, 7 or 8 C atoms. m and l are each independently 0, 1, 2, or 3. k is 0, 1, or 2. However, the compound contains at least one isomerizing group, which is preferably a photoisomerizing group.

8. Equation I ＊ The compound contains an isomerizing group selected from stilbene, (1,2-difluoro-2-phenylvinyl)benzene, cinnamate, α-cyanocinnamate, 4-phenylbuta-3-en-2-one, 2-benzylidene-1-indanone, Schiff base, chalcone, coumarin, chromone, pentarenone, or azobenzene group, and / or Z ３ and / or Z ４ The mixture according to claim 7, characterized in that each of them independently represents -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-.

9. Equation I ＊ The mixture according to claim 7 or 8, characterized in that the chiral group G in the compound is selected from or derived from dianhydrohexitol, preferably isosorbide, isomannide or isoidide, 1,1'-bi-2-naphthol or 1,2-diphenyl-1,2-ethanediol group.

10. Equation I ＊ The mixture according to any one of claims 7 to 9, characterized in that G is selected from the following formula in the compound. [Chemistry 18] 【Chemistry 19】 (In the formula, X is -CO-O-, -CH=CH-CO-O-, -CH=C(CN)-CO-O- (in each of these, the ester O atom is linked to the furan ring), or -N=N-. q is 0, 1, 2, 3, or 4. L has the meaning of claim 7, R １１ and R １２ Each of these is R as defined in claim 7, independently of the others. ３ - (A ３ -Z ３ ) ｍ - represents, or R １１ and R １２ Together with the O atom, the group - (Z) as defined in claim 7 ４ -A ４ ) ｌ -R ４ A cyclic or spirocyclic group may be substituted with, R １３ and R １４ Each of these is R as defined in claim 7, independently of the others. ３ - (A ３ -Z ３ ) ｍ - represents, a1 and a2 are each independently 0, 1, or 2. and the dashed lines represent the linkage to adjacent group(s) in Formula I ＊ (s).)

11. Equation I ＊ The mixture according to any one of claims 7 to 10, characterized in that the compound is selected from the following sub-formulas. 【Chemistry 20】 【Chemistry 21】 【Chemistry 22】 【Chemistry 23】 【Chemistry 24】 【Chemistry 25】 【Chemistry 26】 【Chemistry 27】 (Wherein, P, Sp, L and q have the meanings given in claim 7, and R ＊ has one of the meanings of R in claim 7 that is different from P-Sp-, and R ３ has one of the meanings of R in claim 7 that is different from P-Sp-, and R ＊＊ has one of the meanings of R in claim 7 that is different from P-Sp-, and R ４ has one of the meanings of R in claim 7 that is different from P-Sp-, and R １６ and R １７ each independently represent an alkyl having 1 to 12, preferably 1 to 6 carbon atoms, very preferably methyl, ethyl or propyl, and R １８ represents P-Sp-, H or an alkyl having 1 to 12, preferably 1 to 6 carbon atoms, very preferably H.)

12. Equation I ＊ Alternatively, in the subformula, P is acrylate or methacrylate, and Sp is -O-(CH ２ ) ｐ１ -, -O-CO-(CH ２ ) ｐ１ - or - CO - O - (CH ２ ) ｐ１ - where each O atom or CO group is linked to a benzene ring, p1 is an integer from 1 to 6, and R ４ The mixture according to any one of claims 7 to 11, characterized in that it is P-Sp-.

13. The mixture according to any one of claims 1 to 12, characterized by further comprising one or more RMs having only one polymerizable functional group, and one or more RMs having two or more polymerizable functional groups.

14. A compound comprising the mixture described in any one of claims 1 to 13, further comprising one or more solvents and / or additives.

15. A polymer film that can be obtained by polymerizing a mixture or formulation according to any one of claims 1 to 14, wherein the polymerizable compound is preferably oriented, and preferably polymerized at a temperature in which the polymerizable compound or mixture exhibits a liquid crystal phase.

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

17. An optical, electro-optical, or electronic device or component thereof, comprising the mixture or polymer described in any one of claims 1 to 15.

18. The component of claim 17, selected from optical delay films, polarizers, optical compensators, reflective films, diffraction gratings or surface gratings, Bragg polarizing gratings (Bragg PG), polarizing volume gratings (PVG), or Pancharatnam Berry (PB) gratings, as well as non-mechanical beam steering elements, optical waveguides, optical couplers or combiners, polarizing beam splitters, partial mirrors, reflective films, alignment layers, color filters, antistatic protective sheets, electromagnetic interference protective sheets, optical guide lenses, focusing and optical effects, polarization control lenses, and infrared reflective films.

19. The device of claim 17, selected from liquid crystal displays, organic light-emitting diodes, naked-eye stereoscopic 3D displays, see-through myopia displays, AR / VR systems, goggles for AR / VR applications, switchable windows, spatial light modulators, optical data storage devices, optical sensors, holographic devices, spectrometers, optical communication systems, polarimeters, or front / backlights.

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