Diffractive optical elements

Abstract

To provide a diffractive optical element. [Solution] The present invention relates to a diffractive optical element comprising at least one achromatic half-wave plate and at least one chromatic half-wave plate, each half-wave plate comprising at least two layers of polymerized chiral liquid crystal (LC) material on a substrate, and at least one substrate having a periodic surface diffraction grating; a method for manufacturing the same; and optical components or electro-optical components or devices, particularly methods for using the same in digital optics, augmented reality or virtual reality (AR / VR) applications (such as non-mechanical beam steering elements, optical waveguides, optical couplers, optical combiners, optical deflectors, polarizing beam splitters, partial mirrors or lenses).

Description

[Technical Field]

[0001] The present invention relates to a diffractive optical element comprising at least one achromatic half-wave plate and at least one chromatic half-wave plate, wherein each half-wave plate comprises at least two layers of polymerized chiral liquid crystal (LC) material on a substrate, and at least one of the substrates has a periodic surface diffraction grating; a method for manufacturing the same; and optical components or electro-optical components or devices, particularly for use in digital optics, augmented reality or virtual reality (AR / VR) applications (such as non-mechanical beam steering elements, optical waveguides, optical couplers, optical combiners, optical deflectors, polarizing beam splitters, partial mirrors or lenses). [Background technology]

[0002] Waveplates such as half-wave plates (HWP, HWF) and quarter-wave plates (QWP, QWF) are important components in the field of digital optics. They are suitable for use in Pancharatnam Berry (PB) optical elements (PBOE), also known as cycloidal diffraction waveplates, as described, for example, in Yun-Han Lee, Opt. Data Process. Storage; 3, pp. 79-88 (2017) (Non-Patent Literature 1). PBOEs can be designed, for example, as patterned waveplates (HWP), in which case the director profile changes continuously as a function along the XY plane. PBOEs include, for example, PB lenses (PBL), PB gratings (PBG), or PB deflection plates (PBD). In PBLs, the director usually changes continuously parabolic along the radial axis, while in PBGs or PBDs, the director profile usually changes linearly along the longitudinal direction.

[0003] PBOEs such as PBLs and PBGs are suitable for use as optical waveguides in or within augmented reality (AR), virtual reality (VR), and augmented reality (XR) headsets and other AR / VR devices, head-up displays, and other automotive display devices. These may be active devices fabricated from LC materials such as electrically switchable LC mixtures. Alternatively, static devices can be fabricated from polymerizable LC (also called reactive mesogens (RMs)), forming thin-film lenses or diffraction gratings on plastic substrates. These RM films offer advantages such as high versatility, easy manufacturing processes, and generally high mechanical and chemical stability.

[0004] In such applications, controlling the polarization state of light is crucial. For light rays in a specific wavelength range, the polarization conversion to red, green, and blue (RGB) must be perfect as the ray passes through the light stack. Typically, this is achieved using negative-dispersive materials, which perform well only in the green and blue wavelength ranges. At red wavelengths, they generally do not provide good polarization conversion to the required polarization state.

[0005] Furthermore, it is known that waveplates using a single RM film suffer from chromatic aberration problems due to the optical dispersion of RM. Therefore, an RM film of a thickness designed to function as a half-wave plate (HWP) for a specific wavelength will not function as an HWP for all other wavelengths, resulting in light leakage. As mentioned above, one way to improve this light leakage is to use a negative dispersion RM film. The advantage of a negative dispersion RM film is that a single film can compensate for the blue and green regions of the visible spectrum. However, a trade-off always occurs because the dispersion flattens at red wavelengths. Light leakage is minimal in the green and blue regions of the visible spectrum, but undesirable light leakage occurs in the red region. In addition, the individual RM single crystals used in negative dispersion RM films are very expensive and have low birefringence. Therefore, HWPs using negative dispersion RM films are very expensive.

[0006] Conventional techniques have shown that using a multi-twist retarder containing multiple CLC RM films can yield superior achromatic properties compared to negative-dispersion RM films. However, this method typically requires three or more layers to achieve good achromatic properties across the entire visible light spectrum.

[0007] For example, Z. Luo et al., in Light:Science&Applications (2023) 12:230 (Non-Patent Literature 2), reported on an achromatic diffracting LC optical element that corrects chromatic aberration, which causes different diffraction angles for each color of RGB light, thereby reducing lateral color shift. This LC optical element has a structure in which three PBOE films are stacked. The first component is a broadband PBL, which is effective for all RGB wavelengths but provides different optical powers to the input RGB light. As a result, red light receives the highest optical power and blue light receives the lowest optical power, causing chromatic aberration and reversing the polarization state of RGB light from left circular polarization (LCP) to right circular polarization (RCP). The second component is an unpatterned blue HWP (B HWP) placed after the broadband PBL, which is designed to convert the polarization state of blue light from RCP to LCP without affecting red and green light. The third component is a red / blue BL (RB PBL) that is effective only on red and blue light, diverging red light and focusing blue light. It has been reported that an achromatic LC diffractive optical element can be realized by stacking these three components.

[0008] Z. Luo et al. further describe that each component consists of an RM layer provided on the photoalignment layer to induce a desired LC director. The RM layers of the broadband PBL and RB PBL further contain chiral dopants to induce a twisted structure. The broadband PBL has a multi-twist structure induced by the interference pattern of each photoalignment layer. The RM layer of the B HWP exhibits a uniform, untwisted structure. Each individual RM layer is UV photopolymerized to fix its respective orientation.

[0009] Manufacturing such a multilayer PBOE requires multiple RM coating steps. The first RM layer is coated onto an orientation layer or patterned substrate (usually a photoalignment layer (PAL) or an orientation layer or substrate fabricated by lithography, e.g., a PB grid substrate). The RM layer adopts the orientation direction promoted by the orientation layer or substrate, and the RM material is cured to form a polymer film. The next RM layer is coated directly onto the previously polymerized RM layer.

[0010] However, including so many layers complicates the fabrication of multilayer stacks. The coating and curing processes of multiple RM layers can lead to problems such as poor wettability and misalignment, and these problems worsen as more layers are added to the stack.

[0011] To achieve good orientation, strong intermolecular interactions must occur between RM layers, and the orientation direction must be transmitted from one layer to the next. At the same time, each RM layer being coated must not damage the previous RM layer.

[0012] In addition to the reduced wettability of the RM material on the surface of the previous layer, the migration of substances such as chiral dopants added to the RM material between layers is also a serious problem. Such undesirable "chiral migration" can alter the desirable torsion angle of both layers. As a result, it becomes necessary to dopage the underlying layer and / or the currently coated layer with additional chiral material. This makes the entire manufacturing process more complex and less reproducible, making it unsuitable for mass production.

[0013] Another problem is undesirable spontaneous crystallization, which occurs when using RM materials that contain a large amount of direactive RM, or are composed solely of direactive RM. Direactive RM tends to have lower solubility than monoreactive RM. Furthermore, a large amount of direactive RM can also negatively affect the orientation quality of the polymerized film.

[0014] Therefore, there remains a need for improved waveplates and PBOEs made from RM materials that can be used as diffractive optical components, particularly PBGs, PBDs, and PBLs, with reduced chromatic aberration across most of the visible spectrum, as well as for methods of manufacturing them. Furthermore, there is a need for diffractive deflectors and lenses, particularly PBDs and PBLs, that have reduced chromatic aberration and can be used in optical waveguides for AR, VR, and XR devices. These waveplates and PBOEs must not exhibit, or exhibit, the shortcomings of conventional materials, methods, and films, or only to a small degree, and must be manufactured in a simple, time- and cost-effective manner suitable for mass production with highly reproducible quality. In particular, there is a need for improved waveplates and PBOEs made of multiple RM layers that exhibit high-precision alignment and consistent optical properties, and do not exhibit the shortcomings seen in conventional RM multilayer laminates, such as undesirable spontaneous crystallization, reduced wettability, and undesirable changes in torsion angle due to undesirable chiral movement between RM layers. [Prior art documents] [Non-patent literature]

[0015] [Non-Patent Document 1] Yun-Han Lee, Opt.Data Process. Storage; 3, pp. 79-88 (2017) [Non-Patent Document 2] Z. Luo, Light: Science & Applications (2023) 12:230 [Disclosure of the Invention] [Problems that the invention aims to solve]

[0016] One object of the present invention is to provide an improved diffractive optical element, particularly a PBOE, comprising two or more multilayer RM waveplates and a method for manufacturing the same. Another object of the present invention is to provide an improved RM multilayer waveplate with reduced chromaticity and a PBOE comprising the same. Other objects of the present invention will be readily apparent to those skilled in the art from the following detailed description.

[0017] Surprisingly, the inventors of the present invention have found that one or more of these objectives can be achieved by providing a diffractive optical element and a method for manufacturing the same, which combine two or more RM multilayer waveplates as disclosed below and described in the claims. [Means for solving the problem]

[0018] (Summary of the invention) The present invention relates to a diffractive optical element (DOE) that includes the following elements. - At least one achromatic half-wave plate (HWP), -Includes at least one, preferably two or more, chromatic HWPs, However, each HWP includes a substrate, preferably consisting of the substrate, on which two or more cholesteric liquid crystal (CLC) layers are formed, the first CLC layer being deposited directly on the substrate, and the second and subsequent CLC layers being deposited directly on their respective preceding CLC layers. Each CLC layer consists of a polymerized chiral reactive mesogen (RM) mixture, the LC director exhibits a helical twist having a predetermined twist angle along the helical axis in the thickness direction of the CLC layer, and the chiral RM mixture comprises one or more RMs selected from monoreactive, direactive, and polyreactive RMs, preferably one or more direactive RMs and one or more monoreactive RMs, and one or more chiral compounds selected from chiral RMs, and a photoinitiator. In at least one achromatic and chromatic HWP, the substrate includes a periodic surface diffraction grating that induces rotation of the LC director in the in-plane direction of the first CLC layer, preferably a PB deflector or PB lens grating. Preferably, in at least one, and very preferably, in each chromatic and achromatic HWP, at least two, preferably all, CLC layers have different torsion angles (i.e., different torsion angles from the other CLC layers).

[0019] The present invention further relates to a method for producing the DOE described above and below.

[0020] The present invention further relates to a PB optical element (PBOE), preferably a PB lens or PB deflector, comprising the DOE described above and below.

[0021] The present invention further relates to the individual chromatic HWPs or achromatic HWPs or grids described above and below.

[0022] The present invention further relates to optical, electronic, or electro-optical components or devices including the DOE described above and below. The present invention further relates to optical, electro-optical, or electronic devices or components including the DOE described above and below.

[0023] The aforementioned components include, but are not limited to, optical delay films such as quarter-wave plates (QWP) or half-wave plates (HWP) used in LC displays (LCDs), organic light-emitting diodes (OLEDs), autostereoscopic 3D displays, see-through near-eye displays, augmented reality (AR) or virtual reality (VR) systems, switching windows, spatial light modulators, optical data storage, remote optical sensing, holography, spectrometers, optical communications, polarimeters, front / backlights, etc., polarizers, optical compensators, reflective films, diffraction gratings or surface diffraction gratings such as Bragg polarizing gratings (Bragg PG), polarizing volume gratings (PVG), polarizing volume holograms (PVH), Pancharatnam Berry (PB) gratings, as well as non-mechanical beam steering elements, optical waveguides, optical couplers, deflectors or couplers, polarizing beam splitters, partial mirrors, reflective films, alignment layers, color filters, antistatic sheets, electromagnetic interference prevention sheets, optical guides, focusing and optical effect lenses, polarization control lenses, and IR reflective films.

[0024] The aforementioned devices include, but are not limited to, electro-optical displays, particularly LCDs, OLEDs, nonlinear optical (NLO) devices, autostereoscopic 3D displays, see-through near-eye displays, head-up displays, AR / VR systems, goggles for AR / VR applications, switching 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]

[0025] [Figure 1] Figures 1a and 1b illustrate and schematicly show an LC director in a PBOE according to the present invention, where the grating pitch is indicated by a thick black line, (a) where the pitch is constant throughout the region and corresponds to a PB grating or PB deflector, and (b) where the pitch increases radially symmetrically with respect to the center and corresponds to a PB lens.

[0026] [Figure 2] Figure 2 illustrates and schematicly shows a DOE according to the present invention, which functions as an achromatic PBD and comprises an achromatic HWP (201), a blue HWP (202), a red and blue HWP (203), and a red HWP (204), as described above and below, where the achromatic HWP and RB HWP each have a substrate containing a PB deflection grating. The arrows indicate incident circularly polarized red (R, dotted), green (G, dashed), and blue (B, solid) light, respectively. The angles αR, G, and B indicate the deflection angles of the red, green, and blue light with respect to the normal in the direction of incidence, respectively. The polarization state of each color of light is represented as RCP (right circular polarization) or LCP (left circular polarization).

[0027] [Figure 3]Figures 3a-e illustrate and schematicly show a DOE(305) according to the present invention, functioning as an achromatic PBL, comprising an achromatic HWP(301), a blue HWP(302), a red-blue HWP(303), and a red HWP(304), as described above and below, where the achromatic HWP and RB HWP each have a substrate containing a PB lens grating. The arrows indicate the incidence of circularly polarized light of red (R, dotted), green (G, dashed), and blue (B, solid), respectively. The polarization state of light of each color is given as RCP (right circular polarization) or LCP (left circular polarization). [Modes for carrying out the invention]

[0028] <Definition of Terms> As used herein, the term "diffractive" refers to optical components and devices that manipulate light using the principle of diffraction. In diffractive liquid crystal lenses and diffraction gratings, a spatially varying phase profile is generated across the entire lens aperture by modulating the orientation of liquid crystal molecules using an applied electric field. This modulation causes specific phase delays in different parts of the incident light wave. As a result, the light exhibits constructive and destructive interference patterns, and the lens or diffraction grating can focus, shape, or guide the light by diffraction. These components and devices achieve the desired optical effect by controlling the interference of light waves, rather than by the refraction of light rays due to changes in refractive index.

[0029] As used herein with respect to optical elements such as waveplates or lenses, the term "achromatic" means that the optical element has substantially the same effect on all R, G, and B light. On the other hand, with respect to optical elements such as waveplates or lenses, the term "chromatic" means that the optical element has different effects on at least two of the R, G, and B light.

[0030] The term "achromatic waveplate" refers to a waveplate that acts as, for example, a quarter-waveplate, half-waveplate, or full-waveplate for each of the R, G, and B light spectrums. The term "chromatic waveplate" refers to a waveplate that acts as, for example, a quarter-waveplate, half-waveplate, or full-waveplate for only one or more of the R, G, and B light spectrums, and exhibits a different effect on the remaining R, G, and B light spectrum.

[0031] The term "broadband deflector / lens / PBD / PBL, PB-HWP" refers to a deflector, lens, PBD, PBL, or PB-HWP that deflects or converges / diverges all R, G, and B light, but can also deflect or converge / diverge one or more of the R, G, and B light at different angles.

[0032] In the case of a PB-HWP in which an HWP is mounted on a PB deflector or PB lens grating, even if the HWP is an achromatic HWP, i.e., an HWP that functions as an HWP for all R, G, and B light, the resulting PB-HWP may still be chromatic in the sense that it deflects or converges / diverges one or more of the R, G, and B light at different angles. To avoid doubt, such components will be referred to below as "broadband PB-HWP / PBD / PBL".

[0033] The term "achromatic deflector / lens / PBD / PBL / PB-HWP" refers to a deflector, lens, PBD, PBL, or PB-HWP that deflects or converges / diverges all R, G, and B light to approximately the same angle or the same focal point.

[0034] Unless otherwise specified, the optical elements described below and those disclosed in the examples are optimized for "red (R)" light with wavelengths of 630-670 nm, preferably 650 ± 10 nm, "green (G)" light with wavelengths of 500-540 nm, preferably 520 ± 10 nm, and "blue (B)" light with wavelengths of 430-470 nm, preferably 450 ± 10 nm. For other wavelengths, the optical elements can be appropriately adjusted and / or optimized.

[0035] As used herein, "LCP" means left circular polarization, "RCP" means right circular polarization, "LxP" means linearly polarized light with the polarization plane parallel to the x direction, "LyP" means linearly polarized light with the polarization plane parallel to the y direction, and "LzP" means linearly polarized light with the polarization plane parallel to the z direction.

[0036] Throughout the description and claims of this specification, the words "comprise" and "contain" and variations thereof, such as "comprising" and "comprises", mean "including but not limited to" and are not intended to exclude other components nor to be exclusive.

[0037] Unless the context clearly dictates otherwise, the plural forms of the terms used herein are to be construed as including the singular forms, and vice versa.

[0038] As used herein, the term "film" includes rigid or flexible, self - standing or free - standing films having mechanical stability, as well as coatings or layers on a support substrate or between two substrates.

[0039] The term "multilayer" (in contrast to "monolithic") means a retarder or film composed of multiple layers of a specific material, such as the polymerized chiral RM mixtures described above and below.

[0040] As used herein, the terms "reactive mesogen" and "RM" are understood to mean a compound containing a mesogen or liquid - crystal backbone and one or more functional groups bonded thereto, optionally via a spacer group, which are suitable for polymerization and are also referred to as "polymerizable groups" or "P".

[0041] Unless otherwise specified, the term "polymerizable compound" as used herein is understood to mean a polymerizable monomer compound.

[0042] 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.

[0043] 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.

[0044] 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.

[0045] 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.

[0046] 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.

[0047] 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.

[0048] 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.

[0049] As used herein, the term "polymerized (chiral) RM mixture" means, for example, the polymerization product of an RM mixture obtained by the polymerization process described above or below, particularly the photopolymerization process, preferably in its oriented LC phase. On the other hand, unless otherwise specified, the components of the RM mixture, such as monoreactive, direactive, or polyreactive RMs, chiral dopants, photoinitiators, or other additives, and their concentrations refer to the RM mixture before polymerization.

[0050] 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.

[0051] 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.

[0052] 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.

[0053] 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.

[0054] 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.

[0055] The term "polymerization" means a chemical process of forming a polymer by bonding a plurality of polymerizable groups or a polymer precursor (a polymerizable compound) containing such polymerizable groups.

[0056] The term "chiral" is generally used to represent an object that cannot be superimposed with its mirror image.

[0057] An "achiral" (non-chiral) object is an object identical to its mirror image.

[0058] In this application, unless otherwise explicitly stated, the terms "chiral nematic" and "cholesteric" are used as synonyms.

[0059] The term "isomerizable / photoisomerizable compound" means a compound containing one or more isomerizable or photoisomerizable groups, respectively.

[0060] The term "isomerizable group" means a functional group of a molecule that causes a change in the shape of the molecule, i.e., isomerization, by bond rotation, skeletal rearrangement, movement of atoms or groups, or dimerization induced, for example, thermally or photochemically, or by the addition of a catalyst.

[0061] The term "photoisomerizable group" means a functional group of a molecule that causes a change in the shape of the molecule, i.e., isomerization, by bond rotation, skeletal rearrangement, movement of atoms or groups, or dimerization upon irradiation with light of an appropriate wavelength that can be absorbed by the molecule (photoisomerization).

[0062] Examples of photoisomerizable groups are -C=C- double bonds and azo groups (-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-phenylbut-3-en-2-one, Schiff base (i.e., the group R i R ii C=NR iii where R iiiUnlike H, it is, for example, alkyl or aryl. Examples include 2-benzylidene-1-indanone, chalcone, coumarin, chromone, pentarenone, and azobenzene.

[0063] 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.

[0064] 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:

[0065]

number

[0066] 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.

[0067] The twist angle θ across the thickness d is defined by the following equation.

[0068]

number

[0069] In the formula, p is the pitch as defined above.

[0070] 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:

[0071]

Number

[0072] In the formula, c i is the concentration of each individual chiral compound, and HTP i is the helical twisting power of each individual chiral compound.

[0073] The HTP (|HTP Δ |) of all chiral compounds in a mixture of different configurations or different twisting directions is approximately represented by the following formula.

[0074]

Number

[0075] In the formula, c s is the concentration of each chiral compound in the S conformation, HTP s is the helical twisting power of each chiral compound in the S configuration, in the formula, c r is the concentration of each chiral compound in the R configuration, HTP R is the helical twisting power of each chiral compound in the R conformation.

[0076] [[ID=第43]]The birefringence Δn is defined as follows.

[0077]

Number

[0078] In the formula, n e is the abnormal refractive index, n o is the normal refractive index, and the effective average refractive index n av. is given by the following formula.

[0079]

Number

[0080] The average refractive index n av. and the normal refractive index no This can be measured using an Abbe refractometer. Δn can be calculated from the above formula.

[0081] The central wavelength λ and bandwidth Δλ of the reflection band of a cholesteric RM or LC material or cholesteric polymer film are given by the pitch p of the cholesteric helix and the average refractive index n. av. The following equation is given by the birefringence Δn of the cholesteric liquid crystal, and by the birefringence Δn of the cholesteric liquid crystal.

[0082]

number

[0083] The term "visible light" refers to electromagnetic radiation with wavelengths in the range of approximately 400 nm to 740 nm. "Ultraviolet (UV) light" refers to electromagnetic radiation with wavelengths in the range of approximately 200 nm to 450 nm.

[0084] According to this application, the term “linearly polarized” means light that is at least partially linearly polarized. Preferably, the aligning light is linearly polarized with a polarization ratio greater than 5:1. The wavelength, intensity, and energy of the linearly polarized light are selected according to the photosensitivity of the photo-aligning material. Typically, the wavelength is in the UV-A, UV-B, UV-C range or the visible range. Preferably, the linearly polarized light includes light with wavelengths less than 450 nm, more preferably less than 420 nm, and at the same time, the linearly polarized light includes light with wavelengths longer than 280 nm, more preferably longer than 320 nm, and more preferably longer than 350 nm.

[0085] Irradiance (E e ) or radiant power is defined as the electromagnetic radiant power (dθ) per unit area (dA) incident on a surface.

[0086]

number

[0087] Radiation exposure or radiation dose (H e) is the irradiance or radiant power (E) per unit time (t). e ) is defined as.

[0088]

number

[0089] 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.

[0090] 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:

[0091]

number

[0092] 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.

[0093] The optical delay (R(λ)) of a material can be measured using a spectroscopic ellipsometer, such as the M2000 spectroscopic ellipsometer from JAWoollam. This instrument can typically measure the optical delay of birefringent samples, such as quartz, in nanometer units over a wavelength range of 370 nm to 2000 nm. From this data, the dispersion of the material (R(450) / R(550) or Δn(450) / Δn(550)) can be calculated.

[0094] The method for performing these measurements was presented by N. Singh in October 2006 at the National Physical Laboratory (London), UK, in a paper titled "Spectroscopic Ellipsometry, Part 1 - Theory and Fundamentals, Part 2 - Practical Examples and Part 3 - Measurements." The measurement procedures are as described in the "Retardation Measurement (RetMeas) Manual (2002) and Guide to WVASE (2002) (Woollam Variable Angle Spectroscopic Ellipsometer)" published by JAWoollam (Lincoln, Nebraska, USA). Unless otherwise specified, this method is used to determine the delay of the materials, films, and devices described in this invention.

[0095] The term "director" is known in the prior art and refers to the preferred orientation direction of the long molecular axis (in the case of calamistic compounds) or 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.

[0096] The term "alignment" or "orientation" refers to the orientation (orientational order) of anisotropic units of a material, such as small molecules or fragments of large molecules, towards a common direction called the "orientation direction." In the orientation layer of liquid crystal or RM materials, the liquid crystal director coincides with the orientation direction, and the orientation direction corresponds to the direction of the anisotropic axis of the material.

[0097] 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.

[0098] The term "homeotropic structure / alignment / orientation" refers to a film in which the optical axis is substantially perpendicular to the film plane.

[0099] The term "planar structure / alignment / orientation" refers to a film in which the optical axis is substantially parallel to the film plane.

[0100] The term "helical twist" refers to a CLC or chiral RM layer / film in which the optical axis and LC director are twisted helically along the helical axis perpendicular to the layer / film plane (thickness direction). It also includes orientations where the helical axis is tilted by an angle relative to the direction perpendicular to the layer / film plane. Unless otherwise specified, the twist angle values ​​shown above and below refer to helical twist in the thickness direction, or helical twist tilted in the thickness direction.

[0101] 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.

[0102] 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.

[0103] In the equations shown above and below, R 1 , R 0 , R 00 , R 0* , R 11 , R * , R ** , R C , R 3 , R 4If 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.

[0104] In the equations shown above and below, R 1 , R 0 , R 00 , R 0* , R 11 , R 22 , 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.

[0105] In the equations shown above and below, R 1 , R 0 , R 00 , R 0* , R 11 , R 22 , R C , R 3 , R 4If the group R or L, including all its variations, represents an alkyl group in which one or more CH2 groups are replaced by S, it may be linear or branched. Preferably linear and having 1, 2, 3, 4, 5, 6 or 7 C atoms, and therefore preferably representing thiomethyl, thioethyl, thiopropyl, thiobutyl, thiopentyl, thiohexyl or thioheptyl.

[0106] Oxaalkyl preferably represents 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, or 2-, 3-, 4-, 5-, 6-, 7-, 8- or 9-oxadecyl.

[0107] In the equations shown above and below, R 1 , R 0 , R 00 , R 0* , R 11 , R 22 , R C , R 3 , R 4 If the group R or L, including all its variations, represents an alkoxy group or an oxaalkyl group, it may contain one or more additional oxygen atoms, as long as the oxygen atoms are not directly bonded to each other.

[0108] In another preferred embodiment, R 1 , R 0 , R 00 , R 0* , R 11 , R 22 , R C , R 3 , R 4 The base R, or L, which includes all its variations, [ka] -S 1 -F, -OS 1 Selected from the group consisting of -F and -O-S1-O-S2, where S 1 is C 1~12 - Alkylene or C 2~12 -It is an alkenylene, S 2 H, C 1~12 -alkyl or C 2~12 -It is an alkenyl, and very preferably, [ka] 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.

[0109] 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 group in which one CH2 group is replaced with -CH=CH-, it may be linear or branched. Preferably it is linear and has 2 to 10 C atoms. Therefore, it represents vinyl, prop-1- or -2-enyl, but-1-, -2- or -3-enyl, pent-1-, -2-, -3- or -4-enyl, hexa-1-, -2-, -3-, -4- or -5-enyl, hept-1-, -2-, -3-, -4-, -5- or -6-enyl, octo-1-, -2-, -3-, -4-, -5-, -6- or -7-enyl, non-1-, -2-, -3-, -4-, -5-, -6-, -7- or -8-enyl, deca-1-, -2-, -3-, -4-, -5-, -6-, -7-, -8- or -9-enyl.

[0110] In the equations shown above and below, R 1 , R0 , R 00 , R 0* , R 11 , R * , R ** , R C , R 3 , R 4 Group R, including all its variations such as etc., or L represents an alkyl or alkenyl radical that is at least monosubstituted with halogen. In this case, this group is preferably linear, and the halogen is preferably F or Cl. In the case of polysubstitution, the halogen is preferably F. The resulting radicals also include perfluororadicals. In the case of monosubstitution, the fluorine or chlorine substituent may be at any position, but is preferably at the ω-position.

[0111] Above and below,

Chem.

Chem.

[0112] The halogen is preferably F or Cl, very preferably F.

[0113] Group -CR 0 =CR 00 - is preferably -CH=CH-.

[0114] -OC-, -CO-, -C(=O)- and -C(O)- are carbonyl groups, that is,

Chem.

[0115] Preferred substituents L are, for example, F, Cl, Br, I, -CN, -NO2, -NCO, -NCS, -OCN, -SCN, -C(=O)N(R x)2, -C(=O)Y 1 -C(=O)R x , -N(R x )2, 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,

[0116] 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.

[0117] 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.

[0118] [ka] And, In the formula, L has one of the meanings described above.

[0119] 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 atoms 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.

[0120] 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.

[0121] 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.

[0122] -OC-, -CO-, -C(=O)-, and -C(O)- are carbonyl groups, i.e., [ka] It represents.

[0123] 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.

[0124] 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-CW2 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.

[0125] 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=CW2 -, 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.

[0126] 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] It is selected from the group consisting of the following.

[0127] 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.

[0128] 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.

[0129] 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.

[0130] 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.

[0131] 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.

[0132] 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.

[0133] 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.

[0134] In another preferred embodiment of the present invention, polymerizable compounds as disclosed above and below include compounds of formulas D, M, T, A, C1-C3 and their subformulas, such as Sp-P, and Sp(P). sSp 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.

[0135] 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.

[0136] [ka] i

[0137] 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.

[0138] A preferred spacer base Sp(P)2 is selected from formulas S1, S2, and S3.

[0139] A highly preferred spacer base Sp(P)2 is selected from the following sub-formulas.

[0140] [ka]

[0141] <Detailed explanation>

[0142] In the DOE according to the present invention, at least one HWP, preferably at least one achromatic HWP, more preferably the achromatic HWP and the chromatic HWP, includes a substrate having a periodic surface diffraction grating or surface pattern.

[0143] Surface diffraction gratings or surface patterns can be fabricated by known methods, such as forming a photoalignment layer (PAL) on a substrate that has been patterned by laser interferometry to create a grating pattern with a predetermined pitch.

[0144] Preferably, the surface diffraction grating or surface pattern has a predetermined period that rotates the LC director along the in-plane direction of the CLC layer provided thereon, and is preferably a PB deflection plate or PB lens grating. These HWPs will be abbreviated as PB-HWP below.

[0145] Figures 1a and 1b schematically illustrate the LC director in the PB-HWP according to the present invention, where the grating pitch is shown by a thick black line. (a) corresponds to a PB grating or PB deflector where the pitch is constant throughout the region, and (b) corresponds to a PB lens where the pitch increases radially symmetrically with respect to the center.

[0146] The lattice pitch can be varied according to the desired function of the PB-HWP. In a preferred embodiment, the lattice pitch of the patterned orientation layer of the first PB-HWP is 1 to 5 μm, preferably 1 to 3 μm, and the lattice pitch of the patterned orientation layer of the second PB-HWP is 6 to 15 μm, preferably 8 to 12 μm.

[0147] In another preferred embodiment, the DOE comprises one or more HWPs, preferably chromatic HWPs, including a substrate having an unpatterned planar-oriented layer.

[0148] In another preferred embodiment, the DOE according to the present invention further comprises one or more quarter-wave plates (QWPs) positioned in front of the first HWP or PB-HWP and / or behind the last HWP or PB-HWP when viewed from the direction of incident light. The QWPs may be fabricated from a CLC multilayer film containing multiple polymerized chiral RM layers, as described above and below, or selected from commercially available standard QWPs.

[0149] As with the HWP, PB-HWP, QWP, and other optical elements in the DOE according to the present invention, individual waveplates can be laminated by conventional means and methods well known to those skilled in the art. For example, they can be laminated together or bonded with adhesive layers, and can also be optically bonded using, for example, commercially available optically transparent adhesives (OCAs).

[0150] A preferred DOE according to the present invention includes the following components: - An achromatic HWP comprising a substrate having a periodic surface diffraction grating, preferably consisting of the substrate, wherein two or more CLC layers are formed on the substrate, the first CLC layer is deposited directly on the substrate, and the second and subsequent CLC layers are deposited directly on each preceding CLC layer. - A chromatic HWP comprising at least one, preferably two or more, chromatic HWPs, each comprising a substrate preferably having a planar oriented layer, preferably consisting of the substrate, on which two or more CLC layers are formed, the first CLC layer being deposited directly on the substrate, and the second and subsequent CLC layers being deposited directly on their respective preceding CLC layers. -Optionally, a chromatic HWP comprising a substrate having a periodic surface diffraction grating, preferably consisting of the substrate, wherein two or more CLC layers are formed on the substrate, the first CLC layer is deposited directly on the substrate, and the second and subsequent CLC layers are deposited directly on their respective preceding CLC layers. However, each CLC layer consists of a polymerized chiral RM mixture having a helical twist along the helical axis in the thickness direction of the CLC layer, and the chiral RM mixture comprises one or more RMs selected from monoreactive, direactive, and polyreactive RMs, preferably one or more direactive RMs and one or more monoreactive RMs, and further comprises one or more chiral compounds selected from chiral RMs and a photoinitiator. Preferably, at least one of chromatic and achromatic HWP, preferably at least two, preferably all CLC layers, have different torsion angles. The periodic surface diffraction grating induces rotation of the LC director in the in-plane direction of the first CLC layer, and is preferably a PB deflection grating or a PB lens grating.

[0151] Preferably, the chromatic PB-HWP is a half-wave plate for one or more, preferably two, of red, green, and blue light, and particularly preferably for red and blue light.

[0152] A first preferred embodiment of the present invention relates to a DOE comprising the following components in the order shown when viewed from the direction of incident light. - The first achromatic HWP, effective for all red (R), green (G), and blue (B) light. -A second chromatic HWP that is effective for one of the R, G, and B lights, preferably only for the B light, and not for the other RGB lights, preferably the R or G light. - A third chromatic HWP that is effective for R and B light, but not for G light. -A fourth chromatic HWP that is effective only for one of the RGB lights, preferably the R light, and not for the other RGB lights, preferably the G light or the B light. However, the first, second, third, and fourth HWP each contain two or more CLC layers, the first CLC layer is deposited directly onto the substrate, and the second and subsequent CLC layers are deposited directly on their respective preceding CLC layers. Each CLC layer consists of a polymerized chiral RM mixture having a helical twist along the helical axis in the thickness direction of the CLC layer, the chiral RM mixture comprising one or more bireactive RMs, one or more monoreactive RMs, one or more chiral compounds selected from chiral RMs, and a photoinitiator. The substrates of the first and third HWPs include a PB deflection grating, while the substrates of the second and fourth HWPs have a planar orientation layer.

[0153] Figure 2 illustrates and schematicly shows a DOE according to this first preferred embodiment, which functions as an achromatic PBD, comprising a broadband PB-HWP (201), a blue (B) HWP (202), a red-blue (RB) PB-HWP (203), and a red (R) HWP (204), as described above and below, where the broadband PB-HWP and RB PB-HWP have a substrate containing a PB deflection grating. The arrows indicate incident circularly polarized red (R, solid), green (G, dashed), and blue (B, dotted) light, respectively. Angle α R , G , B These indicate the deflection angles of red, green, and blue light relative to the normal direction, respectively. The polarization state of each color is indicated by RCP (right circular polarization) or LCP (left circular polarization).

[0154] The broadband PB-HWP(201) is designed to convert the chirality (handness) of all incident circularly polarized RGB light from right-circularly polarized (RCP) to left-circularly polarized (LCP), or vice versa. As a result, for example, incident RCP light is converted to LCP light. At the same time, the broadband PB-HWP(201) has different deflection angles α for R, G, and B light in the xz plane. R , α G , α B This causes α R >α G >α B The following relationship holds true.

[0155] The B HWP(202) is a chromatic HWP designed to convert the chirality of incident blue light only from RCP to LCP, or vice versa. As a result, for example, incident LCP B light is converted to RCP B light, but the chirality of incident LCP R and G light remains unchanged. The deflection angles αR, αG, and αB of RGB light produced by the broadband PB-HWP(201) are substantially unchanged by the B HWP(202).

[0156] The RB HWP(203) is designed to convert only the chirality of the incident circularly polarized R and B light from LCP to RCP, or vice versa. As a result, for example, incident LCP R light is converted to RCP R light, and incident RCP B light is converted to LCP B light, but the chirality of the incident LCP G light remains unchanged. At the same time, the RB PB-HWP(203) controls the deflection angle α of the R and B light produced by the broadband PB-HWP(201). R and α B It is designed to convert this into the value of the deflection angle αG of the G light. As a result, the R, G, and B light after passing through the second PB-HWP(203) all have almost the same deflection angle.

[0157] The R HWP(204) is a chromatic HWP designed to convert only the chirality of incident red light from RCP to LCP, or vice versa. As a result, for example, the R light of the incident RCP is converted to the B light of the LCP, but the chirality of the B and G light of the incident LCP remains unchanged. The deflection angles αR, αG, and αB of RGB light produced by broadband and RP PB-HWP(201, 203) are also substantially unchanged by the R HWP(204).

[0158] As a result, for example, RGB light incident on a broadband PB-HWP(201) is emitted from the R HWP(204) as inversely polarized light, i.e., LCP RGB light, with the deflection angles αR=αG=αB being nearly identical. A DOE containing a complete stack of broadband PB-HWP(201), RP PB-HWP(203), B HWP(202), and R HWP(204) functions as an achromatic PB lens for circularly polarized light.

[0159] More preferably, the DOE according to this preferred embodiment further comprises a first QWP in front of the broadband HWP(201) and a second QWP behind the R HWP(204) when viewed from the direction of the incident light (not shown in Figure 2). As a result, incident linearly polarized RGB light having a polarization plane parallel to the x-axis direction (LxP) is deflected and emitted from the DOE at the same angle αR=αG=αB, ideally while maintaining its original polarization state.

[0160] Therefore, the DOE according to this first preferred embodiment can function and be used as an achromatic PB deflector that deflects all colors of RGB light, whether linearly polarized (with QWP) or circularly polarized (without QWP), at the same deflection angle.

[0161] A second preferred embodiment of the present invention relates to a DOE having components in the following order when viewed from the direction of incident light. - The first achromatic HWP, effective for all red (R), green (G), and blue (B) light. -A second chromatic HWP that is effective only for one of the R, G, and B lights, preferably B light, and not effective for the other RGB lights, preferably R or G light. -A third chromatic HWP that is effective for R and B light but not for G light. -Optionally, a fourth chromatic HWP that is effective only for one of the RGB lights, preferably the R light, and not for the other RGB lights, preferably the G or B light. However, the first, second, third, and fourth HWP each contain two or more CLC layers, the first CLC layer is deposited directly onto the substrate, and the second and subsequent CLC layers are deposited directly on their respective preceding CLC layers. Each CLC layer consists of a polymerized chiral RM mixture having a helical twist along the helical axis in the thickness direction of the CLC layer, the chiral RM mixture comprising one or more bireactive RMs, one or more monoreactive RMs, one or more chiral compounds selected from chiral RMs, and a photoinitiator. The substrates of the first and third HWPs include a PB lens grating, while the substrates of the second and fourth HWPs have a planar oriented layer.

[0162] Figures 3a-e illustrate and schematicly show the individual components of a preferred DOE(305) according to this second preferred embodiment, functioning as an achromatic PBL, all of which include a broadband PB-HWP(301), a blue HWP(302), a red-blue (RB) PB-HWP(303), and a red HWP(304), as described above and below, with the broadband PB-HWP and RB PB-HWP each having a substrate containing a PB lens grating. The arrows indicate the incident circularly polarized red (R, dotted), green (G, dashed), and blue (B, solid) light, respectively. The polarization state of the light of each color is indicated by RCP (right circular polarization) or LCP (left circular polarization).

[0163] The broadband PB-HWP(301), schematically shown in Figure 3a, is designed to convert the chirality of all incident circularly polarized RGB light from LCP to RCP, or vice versa. As a result, for example, incident LCP light is converted to RCP light. At the same time, the broadband PB-HWP(301) focuses the R, G, and B light at different angles, with the R light focusing the strongest and the B light focusing the weakest.

[0164] The B HWP(302), schematically shown in Figure 3b, is a chromatic HWP designed to convert the chirality of incident blue light only from RCP to LCP, or vice versa. As a result, for example, incident LCP B light is converted to RCP B light, but the chirality of incident LCP R and G light remains unchanged. The angles of RGB light produced by the broadband PB-HWP(301) are substantially unchanged by the B HWP(302).

[0165] The RB HWP(303) schematically shown in Figure 3c is designed to convert only the chirality of the incident circularly polarized R and B light from LCP to RCP, or vice versa. As a result, for example, incident LCP R light is converted to RCP R light, and incident RCP B light is converted to LCP B light, but the chirality of the incident LCP G light remains unchanged. At the same time, the RB PB-HWP(303) is designed to diffuse the R light and focus the B light, so that the angle of the G light remains virtually unchanged.

[0166] The R HWP(304), schematically shown in Figure 3d, is a chromatic HWP designed to convert only the chirality of the incident red light from RCP to LCP, or vice versa. As a result, for example, the R light of the incident LCP is converted to the R light of the RCP, but the chirality of the B and G light of the incident LCP remains unchanged. The angles of the RGB light produced by the RB PB-HWP(303) are substantially unchanged by the R HWP(304).

[0167] As a result, as schematically shown in Figure 3e, the RGB light incident on the DOE (305) maintains almost the same convergence angle even after leaving the DOE. The DOE, which includes a complete stacked structure of broadband PB-HWP (301), B HWP (302), RB PB-HWP (303), and R HWP (304), functions as an achromatic PB lens.

[0168] More preferably, the DOE according to this preferred embodiment further has a first QWP in front of the broadband PB-HWP(301) and a second QWP on the back of the R HWP(304) when viewed from the direction of the incident light (not shown in Figure 3). As a result, the incident linearly polarized RGB light exits the DOE at the same angle and while maintaining its initial polarization state.

[0169] Therefore, the DOE according to this preferred embodiment can function and be used as an achromatic PB lens that focuses all colors of RGB light, whether linearly polarized (with QWP) or circularly polarized (without QWP), to substantially the same focal point.

[0170] Other DOEs having CLC multilayer films containing two or more chromatic and / or achromatic HWPs, stacked in an order different from that described in the preferred embodiments above, can also be readily fabricated using the materials and methods of the present invention.

[0171] The PB-HWP and HWP in the DOE according to the present invention preferably have 2 to 12, more preferably 2 to 10, very preferably 2 to 8, and most preferably 2 to 6 individual CLC layers, as described above and below. Such a component including two or more individual CLC layers is also referred to above and below as a "CLC multilayer film" or "multi-twist phase difference plate / waveplate".

[0172] Each CLC layer is preferably planar oriented, and by adding a small amount of chiral dopant with high torsional force, a helical twist is induced in one direction throughout the film thickness. The dopant concentration can be varied for each individual CLC layer, thereby allowing at least two CLC layers to have different twist angles in at least one, preferably both, of the chromatic and achromatic HWP.

[0173] In the PB-HWP and HWP described above and below, each CLC layer comprises a photoinitiator and at least one chiral compound selected from monoreactive, direactive, and polyreactive RMs, preferably one or more direactive RMs and one or more monoreactive RMs, and preferably a chiral RM.

[0174] The optical properties of the individual components of the DOE, such as HWP and PB-HWP described above and below, including deflection angle, focal point, (a) chromaticity, and phase difference (e.g., half-wavelength phase difference or full-wavelength phase difference), can be controlled and adjusted by selecting the corresponding layer thickness, torsion direction, and torsional force of each CLC layer constituting the multilayer stack, as well as the pitch of the PB grating or PB lens. This makes it possible to fabricate multi-twist phase difference plates from these chiral RM mixtures, where each CLC layer has a different torsion angle, and can function as an achromatic or chromatic waveplate with a desired phase difference, for example, as a half-wave plate or a full-wave plate for linearly polarized or circularly polarized light.

[0175] By using the chiral RM mixture and CLC multilayer film according to the present invention, as well as their manufacturing methods, in the process of multi-twist phase difference plates, it becomes possible to design waveplates and PB-HWPs that vary from completely achromatic across the entire visible wavelength range to highly chromatic at specific wavelengths.

[0176] Individual optical components of the DOE according to the present invention (such as PB-HWP and HWP) are preferably manufactured by depositing a first layer of the chiral RM mixture described above and below onto a substrate, annealing the chiral RM material as necessary, and then curing the RM material by polymerization, preferably UV photopolymerization. Next, a second layer, and optionally more layers of chiral RM material, are deposited individually and sequentially, and annealed as necessary, and cured on the previously cured chiral RM layer.

[0177] According to the present invention, the process for manufacturing individual optical components such as PB-HWP preferably includes the following steps. A1) A step of forming a surface diffraction grating, preferably a PB deflection grating or a PB lens grating, on the substrate surface. A2) A step of depositing a first layer of the chiral RM mixture described above and below, or an RM formulation containing the chiral RM mixture described above and below and a solvent or solvent mixture, onto a surface diffraction grating. A3) Steps to remove the existing solvent, A4) Optionally, the first layer of the chiral RM mixture is annealed at a temperature at which it becomes a cholesteric phase. A5) A step of polymerizing the first layer of chiral RM mixture by irradiating it with chemical rays, preferably ultraviolet rays, at a temperature at which it becomes a cholesteric phase. B1) A step of depositing a chiral RM mixture described above and below, or a second layer of an RM formulation containing the chiral RM mixture described above and below and a solvent or solvent mixture, onto a first chiral RM layer obtained by polymerization. B2) Step to remove the existing solvent, B3) Optionally, the second layer of chiral RM mixture is annealed at a temperature at which it becomes a cholesteric phase. B4) A step of polymerizing the second layer of chiral RM mixture by irradiating it with chemical rays, preferably ultraviolet rays, at a temperature at which it becomes a cholesteric phase. Optionally, steps B1 to B4 are repeated one or more times, and chiral RM mixtures such as the third layer and fourth layer are applied to each polymerized chiral RM layer and polymerized.

[0178] HWPs other than PB-HWPs used in the DOE according to the present invention can be manufactured according to this preferred method, but in step A1), the substrate does not include a surface diffraction grating and instead preferably includes a planar oriented layer.

[0179] As described above, the birefringence, thickness, helical pitch, and twist angle values ​​of the single-layer CLC layer in the waveplate according to the present invention can be varied according to the desired function of the multi-twist waveplate. These values ​​can be easily and reproducibly adjusted by using the chiral RM mixture described above and below, in particular a mixture of the chiral RM mixture and the achiral RM mixture, and by using the multilayer film fabrication method described above and below.

[0180] The thickness of the multilayer waveplate, such as PB-HWP or HWP according to the present invention, is preferably 2 to 20 μm, and very preferably 2 to 15 μm.

[0181] The thickness of each CLC layer in the multilayer waveplate according to the present invention is preferably 1 to 10 μm, and very preferably 1 to 3 μm.

[0182] The torsion angle in each CLC layer of the multilayer waveplate preferably varies in the range of 0.1 to 150°.

[0183] In a preferred embodiment, the CLC layer is planarly oriented with a helical twist, i.e., the LC molecules are oriented substantially parallel to the film plane and the helical axis is oriented substantially perpendicular to the film plane.

[0184] In another preferred embodiment, one or more CLC layers have a helical twisted tilt orientation. That is, the LC molecules are oriented at an angle to the film plane and / or the helical axis is oriented at an angle to a direction perpendicular to the layer plane (this is called the tilt angle). Preferably, the tilt angle between the helical axis and the direction perpendicular to the film plane is 5° to 45°, most preferably 15° to 45°. In another preferred embodiment, the tilt angle between the helical axis and the direction perpendicular to the layer plane is 0° > to 15°, most preferably 0° > to 5°.

[0185] Planar orientation can be induced, for example, by providing an orientation layer, such as a polyimide orientation layer, on the substrate, as will be described later. Gradual orientation can be achieved, for example, by adding an orientation additive to a chiral RM mixture, or by using a substrate containing a surface diffraction grating or pattern, such as a PB grating.

[0186] The birefringence (Δn) of single-layer CLC is preferably in the range of 0.15 to 0.4, more preferably in the range of 0.16 to 0.35, and most preferably in the range of 0.18 to 0.3.

[0187] The optical delay of the half-wave plate according to the present invention is preferably 200 to 400 nm.

[0188] The optical delay of the all-wavelength plate according to the present invention is preferably 400 to 800 nm.

[0189] Individual cholesteric liquid crystal (CLC) layers in a waveplate according to the present invention can be prepared from the same or different chiral RM mixtures. Chiral RM mixtures can be easily and reproducibly prepared from achiral and chiral RM base mixtures, and examples include an achiral RM mixture that does not contain chiral components, a first chiral RM mixture containing a predetermined amount of a chiral compound having a specific chirality (i.e., right-handed or left-handed), and a second RM mixture containing a predetermined amount of a chiral compound having the opposite chirality. By mixing these base mixtures in predetermined ratios, multiple chiral RM mixtures having desired chirality and helical twist can be prepared.

[0190] Furthermore, the chiral RM mixture and CLC layer manufacturing process according to the present invention offers the following advantages. - The chiral RM mixture of the first CLC layer can be easily oriented to a desired orientation, for example, on a planar oriented layer or on a surface diffraction grating such as a PB lattice. -By adding only a small amount of a chiral compound with high HTP, it is possible to induce a helical twist in one direction throughout the entire film thickness. -By depositing the chiral RM mixture of the second and subsequent CLC layers onto the preceding CLC layers, the desired orientation can be induced in the subsequent layers, and the twisted orientation can be fixed by polymerization in situ. -By mixing chiral RM mixtures with achiral RM mixtures, the desired helical pitch and twist angle in each final CLC layer can be easily adjusted. - This can reduce the decrease in wettability and chiral migration between RM materials in adjacent CLC layers. - Undesirable spontaneous crystallization of RM can be suppressed. -The easy adjustment of the twist angle and suppression of chiral migration using the RM mixture blend makes it possible to manufacture multi-twist CLC layer stacks simply and reproducibly, making them suitable for large-scale production.

[0191] In the chiral RM mixture used to prepare the CLC layer, the proportion of the direactive RM mixture is preferably 40-90%, more preferably 45-80%. More preferably, the chiral compound is selected from chiral RMs. Even more preferably, the photoinitiator is selected from oxime esters, and particularly preferably from carbazole oxime esters.

[0192] It was found that using a chiral RM mixture containing a large amount of direactive RM represented by formula D can suppress unwanted chiral migration. On the other hand, the amount of direactive RM should not be too high to prevent unwanted crystallization and poor orientation. Considering these trade-offs, it is necessary to carefully control the ratio of monoreactive RM represented by formula M to direactive RM represented by formula M in the chiral RM mixture to achieve an optimal balance between advantages and disadvantages.

[0193] Furthermore, it was found that undesirable chiral migration between CLC layers can be suppressed by using a polymerizable chiral compound preferably selected from formulas C1 to C3.

[0194] Furthermore, it was found that by using an oxime ester-based photoinitiator preferably selected from formula P, rapid and complete polymerization of the CLC layer can be ensured while simultaneously suppressing chiral migration.

[0195] In a preferred embodiment, the chiral RM mixture comprises one or more direactive or polyreactive RMs. These direactive or polyreactive RMs are preferably selected from those represented by formula D.

[0196] [ka]

[0197] 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.

[0198] [ka]

[0199] 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, 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, R 00 and R 000 This represents an alkyl group having H or 1 to 12 C atoms. Y 1 and Y 2 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.

[0200] 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.

[0201] 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.

[0202] The preferred RM of formula DRM is selected from formula Da.

[0203] [ka]

[0204] In the formula, each base is independent of the others and, in each occurrence, is either identical or different, and has the following meanings: P 0 This is a polymerizable group, preferably an acrylic, methacrylic, oxetane, epoxy, vinyl, heptadiene, vinyloxy, propenyl ether, or styrene group. Z 0These are -COO-, -OCO-, -CH2CH2-, -CF2O-, -OCF2-, -C≡C-, -CH=CH-, -OCO-CH=CH-, -CH=CH-COO-, or single bonds. L has one of the meanings in formula D and is preferably selected from F, Cl, CN, or halogenable alkyl, alkoxy, alkylcarbonyl, alkoxycarbonyl, alkylcarbonyloxy or alkoxycarbonyloxy having 1 to 5 C atoms. r is 0, 1, 2, 3, or 4. x and y are each 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.

[0205] The most preferred RM for formula D is selected from the following formulas.

[0206] [ka]

[0207] [ka]

[0208] In the formula, P 0 L, r, x, y, and z are as defined in equation Da, s is 0, 1, 2, or 3, and t is 0, 1, or 2.

[0209] Compounds of formulas Da1, Da2, and Da3 are preferred, with the compound of formula Da1 being particularly preferred.

[0210] In another preferred embodiment, the chiral RM mixture comprises one or more bireactive RMs represented by formula D, wherein formula D contains at least one group Z 1 represents -C≡C, and is preferably selected from the formulas Df, Dg, Dh, Di, Dk, and Dm.

[0211] In formula D and its preferred subformulas, L is preferably selected from F, Cl, CN, NO2, or a linear or branched alkyl group, alkoxy group, alkylcarbonyl group, alkoxycarbonyl group, alkylcarbonyloxy group, or alkoxycarbonyloxy group having 1 to 12 carbon atoms, and the alkyl group may optionally be perfluorinated or a P-Sp- group.

[0212] 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, and especially selected from F, Cl, CN, CH3, C2H5, C(CH3)CH3, CH(CH3)2, OCH3, COCH3, or OCF3, most preferably selected from F, Cl, CH3, C(CH3)3, OCH3, or COCH3, or selected from P-Sp-.

[0213] In another preferred embodiment, the chiral RM mixture comprises one or more monoreactive RMs. These monoreactive RMs are preferably selected from formula M.

[0214] [ka]

[0215] During the ceremony, Each base, independent of the others, and identical or different in its respective appearance, has the following meanings: P 1 This represents a polymerizable group, Sp 1 , Sp 2 These are spacer groups or single bonds, MG M This is a rod-shaped mesogenic group, which is preferably selected from formula MGM.

[0216] [ka]

[0217] During the ceremony, A 1M and A 2M L represents an aromatic or alicyclic group, which may contain one or more heteroatoms selected from N, O, and S. M This may be performed by one substitution or multiple substitution, L M 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, 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 This represents an alkyl group having H or 1 to 12 C atoms. Z 1 -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, R 00 and R 000 This represents an alkyl group having H or 1 to 12 C atoms. Y 1 and Y 2 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.

[0218] 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.

[0219] Preferred base A 1M and A 2MThis includes, but is not limited to, furan, pyrrole, thiophene, oxazole, thiazole, thiadiazole, imidazole, phenylene, cyclohexylene, bicyclooctylene, cyclohexenylene, pyridine, pyrimidine, pyrazine, azulene, indan, fluorene, naphthalene, tetrahydronaphthalene, anthracene, phenanthrene, dithienothiophene, etc., which are either unsubstituted or substituted with group L as defined above by group 1, 2, 3, or 4.

[0220] Preferred specific base A 1M and A 2M The group 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, in which one or two non-adjacent CH2 groups are optionally substituted with O and / or S, and these groups are either unsubstituted or substituted with group 1, 2, 3, or 4 of the above-defined group L.

[0221] Preferably, RM in formula M is selected from the following formulas.

[0222] [ka]

[0223] [ka]

[0224] [ka]

[0225] [ka]

[0226] In the formula, P 0 r, x, y, z, and t are defined by equations Da and Dk, L is L in the above formula M. M One of the meanings given to it is preferably selected from F, Cl, CN, or optionally halogenated alkyl, alkoxy, alkylcarbonyl, alkoxycarbonyl, alkylcarbonyloxy or alkoxycarbonyloxy groups having 1 to 5 carbon atoms. R 0 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 0If 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 naphthalene ring may have one or more identical or different groups L added to them. M It can be replaced with this.

[0227] Of particular preference are compounds of formulas M1, M2, M3, M4, M5, M6, M7, M9, M10 and M11, with compounds of formulas M1, M4 and M7 being especially preferred, and formulas M8, M9 and M10 being even more preferred.

[0228] In another preferred embodiment, the chiral RM mixture comprises one or more single-reactive RMs represented by formula M, and formula MG M This is at least one group Z that exhibits -C≡C 1 It includes and is very preferably selected from formulas M8 to M10.

[0229] In formula M and its preferred sub-formulas, L M Preferably, the alkyl group is selected from F, Cl, CN, NO2, or a linear or branched alkyl group, alkoxy group, alkylcarbonyl group, alkoxycarbonyl group, alkylcarbonyloxy group, or alkoxycarbonyloxy group having 1 to 12 carbon atoms, and the alkyl group may optionally be perfluorinated.

[0230] L MThe most preferred 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, particularly F, Cl, CN, CH3, C2H5, C(CH3)3, CH(CH3)2, OCH3, COCH3 or OCF3, most preferably selected from F, Cl, CH3, C(CH3)3, OCH3 or COCH3.

[0231] In another preferred embodiment of the present invention, the chiral RM mixture comprises one or more RMs represented by formula T.

[0232] [ka]

[0233] 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 -O-, -S-, -CO-, -COO-, -OCO-, -S-CO-, -CO-S-, -O-COO-, -CO-NR 0 -, -NR 0 -CO-, -NR 0 -CO-NR 00 -, -NR 0 -CO-O-, -O-CO-NR 0 -, -OCH2-, -CH2O-, -SCH2-, -CH2S-, -CF2O-, -OCF2-, -CF2S-, -SCF2-, -CH2CH2-, -(CH2) n1 -, -CF2CH2-, -CH2CF2-, -CF2CF2-, -CH=N-, -N=CH-, -N=N-, -CH=CR 0 -, -CY 1 =CY 2 -, -C≡C-, -CH=CH-COO-, -OCO-CH=CH-, or single bond, preferably -COO-, -OCO-, -C≡C-, or single bond, most preferably a single bond. R 0 , R 00 It is an alkyl having H or 1 to 12 C atoms, Y 1 , Y 2 It contains H, F, Cl, NCS, or CN. m1 and m2 are 0, 1, 2, 3, or 4, preferably 0, 1, or 2, more preferably 0 or 1, and most preferably 0. n1 is 0, 1, 2, 3, or 4. In equation T, RM is a high anomalous refractive index n e It exhibits high birefringence.

[0234] Preferably, A, B, D and E in formula T are

[0235] [ka] Selected from the group consisting of,

[0236] 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.

[0237] More preferably, rings A, B, D and / or E in formula T 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-.

[0238] Very preferably, one, two, three, four or more rings A, B, D and / or E in formula T are

[0239] [ka] Selected from the group consisting of,

[0240] 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.

[0241] Particularly preferred are compounds of formula T, 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-.

[0242] Preferably, the ring C in formula T is

[0243] [ka] Selected from the group consisting of,

[0244] 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.

[0245] More preferably, C in formula T is

[0246] [ka] Selected from the group consisting of,

[0247] 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.

[0248] The ring C in formula T 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-.

[0249] Preferably, the compound has n=m=0, and more preferably, the compound has formula T in which rings B, C, and D form groups selected from the following formulas or their mirror images.

[0250] [ka]

[0251] [ka]

[0252] [ka]

[0253] In the formula, the naphthalene group and the phenanthrene group may be substituted with one or two groups L, where L and r are defined in formula T.

[0254] In formulas TM1 to TM28, 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.

[0255] Particularly preferred are the bases of formulas TM01 to TM10, and especially those of formulas TM01 to TM07.

[0256] A highly preferred compound of formula T is selected from the following sub-formulas.

[0257] [ka] TIFF2026110585000046.tif248157

[0258] [ka]

[0259] [ka]

[0260] [ka]

[0261] [ka]

[0262] [ka]

[0263] [ka]

[0264] [ka]

[0265] [ka]

[0266] 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 T 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.

[0267] Even more preferred are compounds of formulas T-1 to T-20, and in particular, compounds of formulas T-1 to T-16.

[0268] In another preferred embodiment of the present invention, the chiral RM mixture comprises one or more RMs of formula T containing a -C≡C- group (acetylene group) in the spacer, preferably containing a -C≡C- group directly bonded to a benzene or naphthalene group outside the mesogenic core. These RMs are preferably selected from formula A.

[0269] [ka]

[0270] 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. Sp 1 This is an alkylene having spacer groups or single bonds, preferably 1 to 12, more preferably 3 to 6 C atoms. R 33 This is an alkyl, alkoxy, thioalkyl, alkylcarbonyl, alkoxycarbonyl, alkylcarbonyloxy or alkoxycarbonyloxy (which may be fluorinated or chlorinated) having H, F, Cl, CN, CH=CH2, 1 to 6, preferably 1 to 3 C atoms, or P-Sp. A A B A This group is selected from the group consisting of phenylene-1,4-diyl, naphthalene-1,4-diyl, naphthalene-2,6-diyl, fluorene-2,7-diyl, dibenzothiophene-2,7-diyl, dibenzofuran-2,7-diyl, benzo[1,2-b:4,5-b']dithiophene-2,5-diyl, indole-4,7-diyl, benzothiophene-4,7-diyl, 9,10-dihydrophenanthrene-2,7-diyl, or 1,2,3,4-tetrahydronaphthalene-5,8-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 A This is phenylene-1,4-diyl, naphthalene-1,4-diyl, or naphthalene-2,6-diyl, preferably phenylene-1,4-diyl or naphthalene-2,6-diyl, provided that one or more CH groups in these groups may be replaced with N, and these may be replaced with one or more L or P-Sp- groups. And also A A B A and C A One or fewer of these represent naphthalene-1,4-diyl, 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 -O-, -S-, -CO-, -COO-, -OCO-, -S-CO-, -CO-S-, -O-COO-, -CO-NR 0 -, -NR 0 -CO-, -NR 0 -CO-NR 00 -, -NR 0 -CO-O-, -O-CO-NR 0 -, -OCH2-, -CH2O-, -SCH2-, -CH2S-, -CF2O-, -OCF2-, -CF2S-, -SCF2-, -CH2CH2-, -(CH2) n1 -, -CF2CH2-, -CH2CF2-, -CF2CF2-, -CH=N-, -N=CH-, -N=N-, -CH=CR 0 -, -CY 1 =CY 2 -, -C≡C-, -CH=CH-COO-, -OCO-CH=CH-, or single bond, preferably -COO-, -OCO-, -C≡C-, or single bond, most preferably a single bond. R 0 , R 00 It is an alkyl having H or 1 to 12 C atoms, Y 1 , Y 2 It contains H, F, Cl, NCS, or CN. m2 is 0, 1, 2, 3 or 4, preferably 0, 1 or 2, more preferably 0 or 1, most preferably 0. m3 is either 0 or 1. n1 is 0, 1, 2, 3, or 4. s is 0, 1, 2, or 3, preferably 0, 1, or 2.

[0271] In equation A, RM is a very high anomalous refractive index n e It exhibits very high birefringence. Furthermore, the maximum absorption peak shifts to shorter wavelengths, and the slope of the UV absorption curve becomes steeper, resulting in less coloration of RM and polymer films made using it.

[0272] In the compound of formula A, preferably A A and B A teeth,

[0273] [ka] Selected from the group consisting of,

[0274] In the formula, A A and B A At least one of the groups is selected from phenylene-1,4-diyl and naphthalene-2,6-diyl, and each group independently of the others has the following meanings in each occurrence, identical or different: L is P-Sp-, -CN, F, Cl, or fluorinated, and is an alkyl, alkoxy, or thioalkyl 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.

[0275] More preferably, ring A in formula A A and B A A is selected from the group consisting of phenylene-1,4-diyl, naphthalene-1,4-diyl, and naphthalene-2,6-diyl, and all of these rings may be optionally substituted with one or more groups L and / or P-Sp-, and no more than one of A and B represents naphthalene-1,4-diyl.

[0276] More preferably, ring A in formula A A and B A teeth,

[0277] [ka] Selected from the group consisting of A A and B A Only one of these represents naphthalene-1,4-diyl. 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-, F, Cl, -CN, CH3, OCH3, SCH3, C2H5, OC2H5, or SC2H5.

[0278] Particularly preferable is when n=m=0, and ring B A The compound is selected from the group consisting of phenylene-1,4-diyl, naphthalene-1,4-diyl, and naphthalene-2,6-diyl, preferably phenylene-1,4-diyl, naphthalene-1,4-diyl, and naphthalene-2,6-diyl, all of which are compounds of formula A that may be monosubstituted or disubstituted with L and / or P-Sp-.

[0279] Ring C in equation A A teeth,

[0280] [ka] Selected from the group consisting of, 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-, F, Cl, -CN, CH3, OCH3, SCH3, C2H5, OC2H5, or SC2H5.

[0281] Even more preferable is when m=1, and ring B A and C A It is a compound of formula A, which is naphthalene-2,6-diyl.

[0282] Even more preferable is m=0, preferably n=0, and ring B A and C A Together with the phenylene-1,4-diyl group, it forms a group selected from the following formula or its mirror image, and * is a compound represented by formula A, indicating a bond to the acetylene group in formula A.

[0283] [ka]

[0284] In the formula, the naphthalene group is optionally substituted with one or two groups L, where r is 0, 1, 2, 3, or 4, preferably 0, 1, or 2, and L is defined by formula A.

[0285] Even more preferable is m=1, preferably n=0, and ring B A and C A The compound is represented by formula A, where * indicates a bond to the acetylene group in formula A, and * is a compound represented by formula A, where * is a bond to the acetylene group in formula A.

[0286] [ka]

[0287] In the formula, the naphthalene group may be substituted with one or two groups L, where r is 0, 1, 2, 3, or 4, preferably 0, 1, or 2, and L is as defined in formula A.

[0288] In formulas AM01 to AM08 and AM1 to AM9, 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 very preferably P-Sp-, -CN, F, Cl, CH3, OCH3, SCH3, C2H5, OC2H5 or SC2H5, most preferably CH3 or C2H5, and r preferably 0, 1, 2 or 3, very preferably 0, 1 or 2.

[0289] Particularly preferred are the bases of formulas AM01, AM02, AM03, AM04, AM1, AM2, and AM3.

[0290] A highly preferred compound of formula A is selected from the following sub-formulas.

[0291] [ka]

[0292] [ka]

[0293] [ka]

[0294] [ka]

[0295] [ka]

[0296] [ka]

[0297] The naphthalene group is optionally substituted with one or two L groups, and P, Sp, L, and r each independently have the same or different meanings in their respective appearances. R is R in equation A 11 It has one of the meanings shown, and preferably represents OCH3 or SCH3, especially OCH3. L is preferably selected from F, Cl, CN, CH3, OCH3, SCH3, C2H5, OC2H5 or SC2H5. P is preferably an acrylate.

[0298] Furthermore, bireactive compounds represented by formulas A and A-1 to A-64 are preferred, in which one of the two Sp groups is a single bond and the other Sp group is not a single bond.

[0299] P is preferably selected from the group consisting of vinyloxy, acrylate, methacrylate, fluoroacrylate, chloroacrylate, oxetane, and epoxy, and very preferably selected from acrylate and methacrylate, and most preferably acrylate, and more preferably compounds represented by formulas D, M, T, A and their sub-formulas as described above and below.

[0300] Compounds represented by formulas D, M, T, A and their sub-formulas described above and below are more preferred, in which all polymerizable groups P present in the compound have the same meaning, and particularly preferably represent acrylate or methacrylate, most preferably acrylate.

[0301] Compounds represented by formulas D, M, T, A and their sub-formulas, described above and below, containing one, two, three, or four P-Sp groups, and particularly containing two or three P-Sp groups, are more preferred.

[0302] R 11 Compounds represented by formulas T, A, and their subformulas, as described above and below, where P-Sp- is more preferred.

[0303] In the formula, R 22 or R 11 Each of these is selected from F, Cl, CN, CF3, CCl3, CH=CH2, or an alkoxy group having 1 to 3 carbon atoms, a thioalkyl group, an alkylcarbonyl group, an alkoxycarbonyl group, an alkylcarbonyloxy group, or an alkoxycarbonyloxy group, which may optionally be fluorinated, more preferably selected from F, Cl, CN, OCH3, SCH3, OCF3, CF3, CH=CH2, CHO, COCH3, COOCH3, COOC2H5 and CCl3, very preferably selected from OCH3, OCF3 or CHO, and most preferably selected from OCH3 or OCF3, and further preferred are compounds represented by formulas M, T, A and their sub-formulas as described above and below.

[0304] In the formula, Sp 1 and / or Sp 2 (If present) -(CH2) s1 Compounds represented by formulas D, M, T, A and their sub-formulas described above and below are even more preferred, where s1 is an integer from 1 to 12, more preferably 3, 4, 5, or 6.

[0305] In the formula, Sp 1 and / or Sp 2 (If present) a single bond, or -(CH2) p1 -, -O-(CH2) p1 -, -O-CO-(CH2) p1 , or -CO-O-(CH2) p1 This represents a configuration where p1 is 2, 3, 4, 5, or 6, and Sp is -O-(CH2) p1 -, -O-CO-(CH2) p1 or -CO-O-(CH2) p1In that case, compounds represented by formulas D, M, T, A and their sub-formulas described above and below, each having an O atom or a CO group bonded to a benzene ring, are even more preferred.

[0306] In the formula, Sp 1 and / or Sp 2 Compounds represented by formulas D, M, T, A and their sub-formulas, described above and below, which (if present) have a single bond, are even more preferred.

[0307] In the formula, Sp 1 and / or Sp 2 Compounds represented by formulas D, M, T, A and their sub-formulas, described above and below, which are different from single bonds (if present), are even more preferred.

[0308] Compounds represented by formulas D, M, T, A and their subformulas, as described above and below, where m is 1, are even more preferred.

[0309] Compounds represented by formulas T, A and their subformulas as described above and below are even more preferred, wherein at least one of B and C in the formula is naphthalene-2,6-diyl or naphthalene-1,4-diyl, particularly naphthalene-2,6-diyl, in which case at least one of B and C may be optionally substituted with one or more groups L or P-Sp-.

[0310] Formula L is a linear, branched, or cyclic alkyl group having P-Sp-, F, Cl, -CN, or 1 to 25 C atoms, and one or more non-adjacent CH2 groups are optionally -O-, -S-, -CO-, -CO-O-, -O-CO-, -O-CO-O-, CR such that the O atoms and / or S atoms are not directly bonded to each other. 0 =CR 00 -, -C≡C-,

[0311] [ka] Substituting with, where one or more H atoms are optionally substituted with P-Sp-, F, or Cl, or two substituents L directly bonded to adjacent C atoms may form a cyclic alkyl or cyclic alkenyl group having 5, 6, 7, or 8 C atoms, R 0 and R 00 Compounds represented by formulas T, A, and their sub-formulas described above and below are more preferred, where each independently represents an alkyl group having H or 1 to 12 C atoms.

[0312] In the formulas, L is F, Cl, CN, or 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, most preferably F, Cl, CN, CH3, OCH3, SCH3, C2H5, OC2H5, or SC2H5. Compounds represented by formulas T, A and their subformulas as described above and below are highly preferred.

[0313] In the formula, Z 11 and Z 12 Compounds represented by formulas T, A and their sub-formulas described above and below are even more preferred, where -COO-, -OCO-, -C≡C-, or a single bond is more preferably -C≡C- or a single bond, with the most preferred being a single bond.

[0314] Further preferred compounds of formulas T and A and their sub-formulas are selected from the following preferred embodiments, including any combination thereof: n=m=0, and / or • Ring C or C A Each represents an alkyl, alkoxy, or thioalkyl, more preferably methyl or ethyl, most preferably ethyl-substituted phenylene-1,4-diyl having 1 to 3, preferably 1 or 2 C atoms, or • Ring C or C A Each of these represents a naphthalene-2,6-diyl which may be substituted with one or more L or P-Sp- groups, and / or - Ring B or B A Each of these represents a naphthalene-2,6-diyl which may be substituted with one or more L or P-Sp- groups, and / or ·m=1 and / or at least one of B and C, or B A and C A At least one of them represents a naphthalene-2,6-diyl which may be substituted with one or more L or P-Sp- groups. · m=0 and / or at least one of B and C, or B A and C A Each of these represents a naphthalene-2,6-diyl which may be substituted with one or more L or P-Sp- groups, • P represents acrylate or methacrylate, and / or ·Sp 1 ha-(CH2) s1 - represents, where s1 is an integer between 1 and 1, preferably 3, 4, 5 or 6, 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 ·L is P-Sp-, F, Cl, CN, CH3, OCH3, SCH3, C2H5, OC2H5 or SC2H5, very preferably CH3 or C2H5, r represents 1, and / or • Ring C is substituted with one L representing P-Sp-, preferably an acrylate, and / or ·R 11 is P-Sp-, or ·R 11The component is F, Cl, CN, OCH3 or SCH3, preferably OCH3 or SCH3, and very preferably OCH3.

[0315] The following are highly preferred compounds of formula T.

[0316] [ka]

[0317] [ka]

[0318] [ka]

[0319] [ka]

[0320] [ka]

[0321] [ka]

[0322] [ka]

[0323] [ka]

[0324] [ka]

[0325] Of particular preference are compounds of formulas T-3, T-19, T-21, T-24, T-25, T-30, T-47, T-50, T-53, T-59, T-60, T-68, T-70, T-71, T-73, and T-75.

[0326] The following are highly preferred compounds of formula A.

[0327] [ka]

[0328] [ka]

[0329] [ka]

[0330] [ka]

[0331] The synthesis of compounds represented by formulas D, M, T, A and their subformulas can be carried out by methods known to those skilled in the art, either in the literature or similarly, as described in, for example, WO2022 / 33908 A1.

[0332] Compounds represented by formulas D, M, T, A and their subformulas, when used alone or in combination with other RMs in chiral RM mixtures, exhibit, in particular, preferably simultaneously, high birefringence, good solubility in commonly known organic solvents used in mass production, excellent orientation, a favorable phase transition temperature, and high resistance to yellowing after UV irradiation.

[0333] Preferably, the chiral RM mixture comprises one or more compounds selected from formulas D, M, T, A and their sub-formulas.

[0334] More preferably, the chiral RM mixture comprises preferably 1 to 6, and very preferably 1 to 4, RMs selected from D, M, T, A and their sub-formulas.

[0335] The concentration of direactive or polyreactive RM (preferably represented by formula D or its sub-formula) in the chiral RM mixture is preferably 20-75%, and very preferably 25-65%, relative to the total solids.

[0336] The concentration of single-reactive RM (preferably represented by formula M or a sub-formula) in the chiral RM mixture is preferably 10-70%, and very preferably 15-55%, relative to the total solid content.

[0337] The amount of chiral compound in the chiral RM mixture is preferably 0.1 to 10%, more preferably 0.5 to 8%, relative to the total solid content.

[0338] The compounds represented by formulas A and T, and their subformulas, exhibit very high birefringence, good solubility in commonly known organic solvents, excellent orientation in RM mixtures, a favorable phase transition temperature, and high resistance to yellowing after UV irradiation. These compounds can be synthesized by methods known to those skilled in the art, either in the literature or similarly, for example, by the method described in International Publication No. 2022 / 33908A1.

[0339] Preferably, the RM mixture comprises one or more compounds selected from formula D or its sub-formulas, preferably one, two, or three compounds; one or more compounds selected from formula M or its sub-formulas, preferably one to five, very preferably two, three, or four compounds; and optionally, one or more compounds selected from formula A and / or T or its sub-formulas, preferably one to five, very preferably two, three, or four compounds.

[0340] When the chiral RM mixture contains one or more RMs represented by formula T or its sub-formulas, their concentrations are preferably 10-70%, and very preferably 10-50%, relative to the total solids.

[0341] When the chiral RM mixture contains one or more RMs represented by formula A or its sub-formulas, their concentrations are preferably 10-70% of the total solids, and very preferably 10-50%.

[0342] In another preferred embodiment, the chiral RM mixture is selected from one or more, preferably exactly one, polymerizable chiral compounds, and more preferably from monoreactive or direactive chiral polymerizable compounds.

[0343] 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.

[0344] Preferred polymerizable chiral compounds are selected from formulas C1, C2, and C3.

[0345] [ka]

[0346] 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.

[0347] Even more preferable are the stereoisomers of formula C2 in which the central isosorbide unit is replaced with an isomannide or isoidide unit.

[0348] The compound of formula C1 is preferably selected from the following formulas.

[0349] [ka]

[0350] In the formula, A 0 B 0 , Z 0* , X 2 , P 0* a and b have the meanings shown in formula Ca, or the preferred meanings shown above and below, and (OCO) represents -O-CO- or a single bond.

[0351] Particularly preferred compounds of formula C are selected from the group consisting of the following sub-formulas.

[0352] [ka]

[0353] [ka]

[0354] In the formula, R * -X is defined as in C1-1. 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.

[0355] 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.

[0356] Preferably, polymerizable chiral compounds, 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.

[0357] In another preferred embodiment, the chiral RM mixture comprises a photoinitiator selected from oxime esters, preferably selected from carbazole oxime esters and fluorene oxime esters.

[0358] Preferably, the photoinitiator is selected from formulas PI and PII.

[0359] [ka]

[0360] In the formula, each base has the following meanings, independently of the others and identical or different in each occurrence: L 31 is, -(CH2) p2 -A 32 Show, L 32 This includes H, alkyl, alkoxy, thioalkyl, alkylcarbonyl, alkoxycarbonyl, alkylcarbonyloxy, or alkoxycarbonyloxy having 1 to 5 carbon atoms, F, Cl, CN, NO2, OCN, SCN, or mono-, oligo-, or polyfluoroalkyl or alkoxy or -(CH2) having 1 to 4 carbon atoms. p3 -A 33 Preferably exhibiting methyl or benzene, L 33 This is an alkyl group having H or 1 to 12 C atoms, preferably ethyl. L 34,35 This is an alkyl group having H or 1 to 12 C atoms, preferably methyl. A 31 is, A 3 or C(L 36 )=NOC(=O)-L32 Show, A 32 This represents an aryl, heteroaryl, (non-aromatic) alicyclic, or heterocyclic group, and optionally includes silyl, sulfo, sulfonyl, formyl, amine, imine, nitrile, mercapto, nitro, halogen, and C. 1~12 Alkyl, C 6~12 Ariel, C 1~12 It has one or more substituents selected from the group consisting of alkoxy, hydroxyl, or combinations thereof, preferably A 32 This represents a C4-C8 alicyclic or heterocyclic group, very preferably cyclopentane or cyclohexane. A 33 is an aryl, heteroaryl, (non-aromatic) alicyclic or heterocyclic group, optionally silyl, sulfo, sulfonyl, formyl, amine, imine, nitrile, mercapto, nitro, halogen, C 1~12 Alkyl, C 6~12 Ariel, C 1~12 It has one or more substituents selected from the group consisting of alkoxy, hydroxyl, or combinations thereof, and is preferably benzene. A 34 is an aryl, heteroaryl, (non-aromatic) alicyclic or heterocyclic group, optionally silyl, sulfo, sulfonyl, formyl, amine, imine, nitrile, mercapto, nitro, halogen, C 1~12 Alkyl, C 6~12 Ariel, C 1~12 It has one or more substituents selected from the group consisting of alkoxy, hydroxyl, or combinations thereof, preferably C 1~12 The terms represent benzene or thiophene substituted with an alkyl group (preferably at the 2nd position), very preferably 2-methylbenzene or thiophene-2-yl. L 36This represents H, an alkyl, alkoxy, thioalkyl, alkylcarbonyl, alkoxycarbonyl, alkylcarbonyloxy, or alkoxycarbonyloxy having 1 to 5 carbon atoms, F, Cl, CN, NO2, OCN, SCN, or a mono-, oligo-, or polyfluoroalkyl or alkoxy having 1 to 4 carbon atoms, preferably C 1~6 It indicates alkyl, R 31,32 This represents H, alkyl, alkoxy, or mono-, oligo-, or polyfluoroalkyl or alkoxy, preferably H or an alkyl group having 1 to 12 C atoms. R 33 H, alkyl, alkoxy, thioalkyl, alkylcarbonyl, alkoxycarbonyl, alkylcarbonyloxy, or alkoxycarbonyloxy; halogen, CN, NO2, OCN, SCN, or mono-, oligo- or polyfluoroalkyl or alkoxy; or -(Sp 31 -A 31 ), preferably H, halogen, CN, or NO2, R 34,35 is H, alkyl, mono-, oligo- or polyfluoroalkyl, or -(CH2) p5 -A 35 Preferably H, alkyl, or -(CH2) p5 -A 35 Show, A 35 These are aryl, heteroaryl, (non-aromatic) alicyclic, and heterocyclic groups, and optionally silyl, sulfo, sulfonyl, formyl, amine, imine, nitrile, mercapto, nitro, halogen, and C 1~12 Alkyl, C 6~12 Ariel, C 1~12 It has one or more substituents selected from the group consisting of alkoxy, hydroxyl, or combinations thereof, preferably phenyl, cyclohexyl, or cyclopentyl. p1 is either 0 or 1. p2 is 0, 1, 2, 3, 4, 5, or 6, preferably 1 or 2. p3 is 0, 1, or 2, preferably 0. p4 is 0 or 1, preferably 1. p5 is 0, 1, 2, 3, 4, 5, or 6, preferably 1 or 2.

[0361] The preferred compounds represented by formulas PI and PII are selected from the following preferred embodiments, including any combination thereof: -A 31 C(L 34 )=NOC(=O)-L 32 And, -A 31 It is 2-methylbenzene or thiophen-2-yl, -A 32 is cyclopentane or cyclohexane, -A 33 It is benzene, -A 34 It is 2-methylbenzene or thiophen-2-yl, -L 32 It is a C1-C5 alkyl group, preferably methyl. -L 32 It is benzene, -L 33 It is a C1-C4 alkyl group, preferably ethyl. -L 34 and L 35 It is methyl, -L 36 C 1-6 Alkyl, preferably hexyl, -R 31 , R 32 is methyl, ethyl, n-propyl, or n-butyl, preferably methyl or ethyl. -R 33 H is, -R 34 It is methyl, -R 35 is methyl, ethyl, or phenyl, -p1 is 0, -p1 is 1, -p2 is 1 or 2. -p3 is 0, -p4 is 1, -p5 is either 1 or 2.

[0362] The preferred compound represented by formula PI is selected from the following sub-formulas.

[0363] [ka]

[0364] In the formula, L 32 , L 33 , L 34 , L 35 , L 36 , A 32 , A 34 p2 and p2, independently, in each occurrence, have either the same or different meanings as shown in formula PI, or either the preferred meanings shown above and below.

[0365] Further preferred compounds of formula P are selected from the group consisting of the following sub-formulas.

[0366] [ka]

[0367] [ka]

[0368] [ka]

[0369] [ka]

[0370] [ka]

[0371] Compounds represented by formulas P2 and P7 are particularly preferred.

[0372] The preferred compound represented by formula PII is selected from the following sub-formulas.

[0373] [ka]

[0374] In the formula, alkyl is methyl, ethyl, n-propyl, or n-butyl, R 33 is H, Br, CN, or NO2, preferably H, and R 34 and R 35 These terms, independently of each other, in their respective appearances, may be identical or different, and have either the meaning shown in formula PII or either the preferred meaning shown above and below, preferably R 34 and R 35 It is methyl or ethyl.

[0375] Highly preferred compounds of formulas PII and PIIa are selected from the following sub-formulas.

[0376] [ka]

[0377] In the formula, R 35 This has any of the meanings shown in formula PII, or any of the preferred meanings shown above and below, and is preferably methyl or ethyl.

[0378] Further preferred compounds of formulas PII and PIIa are selected from the group consisting of the following sub-formulas.

[0379] [ka]

[0380] Of particular preference are compounds represented by formula P22.

[0381] Particularly preferred compounds represented by formula P are the TR-PBG series photoinitiators commercially available from Changzhou Tronly New Electronic Materials (China), such as TR-PBG-304, TR-PBG-314, and TR-PBG-345. Even more preferred are the SPI series photoinitiators commercially available from Sanyang (South Korea), such as SPI-02, SPI-03, and SPI-04. Even more preferred are the Irgacue OXE series photoinitiators commercially available from BASF (Germany), such as OXE-02, OXE-03, and OXE-05.

[0382] In another preferred embodiment, the chiral RM mixture further comprises one or more, preferably just one, nonpolymerized chiral dopants.

[0383] Preferred chiral dopants are selected from the group consisting of compounds represented by formula CI to C-III.

[0384] [ka]

[0385] 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.

[0386] Even more preferable are the stereoisomers of formula C-II in which the central isosorbide unit is replaced by an isomannide or isoidide unit.

[0387] 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.

[0388] 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).

[0389] 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.

[0390] In another preferred embodiment, the chiral RM mixture includes, in addition to or in lieu thereof, one or more isomerizable, preferably photoisomerizable, and more preferably photoisomerizable and polymerizable chiral compounds, in addition to the chiral compounds described above and below. More preferably, these compounds are photoisomerizable by ultraviolet irradiation.

[0391] Isomerizable groups in chiral compounds undergo photo-driven E / Z isomerization reactions, resulting in a reduction of helical torsional force (HTP). This allows for rapid, photo-driven adjustment of the chiral pitch in the RM layer. By changing the formulation and processing conditions, orientation profiles with variable pitch, nonlinear torsional profiles, and profiles where torsion is accelerated or decreased in the layer thickness direction can be fabricated. When oriented on a lattice orientation layer, it is possible to expand the lattice angle bandwidth.

[0392] In another preferred embodiment, the chiral RM mixture comprises at least two, more preferably exactly two, chiral compounds having opposite chiralities, one compound containing an isomerizable group and the other compound not containing an isomerizable group, and one or both, preferably both, are polymerizable. When the isomerizable chiral compound is irradiated with light, its torsional force changes, while the torsional force of the non-isomerizable chiral compound does not. This makes it possible to control and adjust the torsional profile of the final RM layer.

[0393] Preferred chiral isomerizable compounds are those of formula I * It is represented as follows.

[0394] [ka]

[0395] In the formula, each base has the following meanings, independently of the others and identical or different in each occurrence: R 3 , R 4 This is an alkyl group having up to 25 carbon atoms, which may be H, F, Cl, CN, P-Sp-, or unsubstituted, or monosubstituted or polysubstituted with halogens or CN, and may also have one or more non-adjacent CH2 groups independently of each other, with oxygen atoms not directly bonded to each other, such that -O-, -S-, -NH-, -N(CH3)-, -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 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. A3 , A 4 This is an alicyclic, heterocyclic, aromatic, or heteroaromatic group having 4 to 20 ring atoms, and can be monocyclic or polycyclic, and may be substituted with one or more groups L or P-Sp-. G is a chiral group, L is a linear, branched, or cyclic alkyl group having F, Cl, -SCN, P-Sp-, or 1 to 25 C atoms, and one or more non-adjacent CH2 groups are optionally -O-, -S-, -CO-, -CO-O-, -O-CO-, -O-CO-O-, CR such that the O atoms and / or S atoms are not directly bonded to each other. 0 =CR 00 -, -C≡C-,

[0396] [ka] Substituting with, where one or more H atoms are optionally substituted with P-Sp-, F, or Cl, or two substituents L directly bonded to adjacent C atoms may form a cyclic alkyl or cyclic alkenyl group having 5, 6, 7, or 8 C atoms. m and l are independently 0, 1, 2, or 3. k is 0, 1, or 2. However, the compound contains at least one isomerizable group, preferably a photoisomerizable group, preferably R 3 and R 4 At least one of them is P-Sp-.

[0397] Equation I * and preferred compounds of the subformula are R 3 and R 4 At least one, preferably both, of these is P-Sp-.

[0398] Equation I * And a more preferred compound of the subformula is R 3 and R 4At least one, preferably both, of the P-Sp- is an alkyl or alkoxy having 1 to 12, more preferably 1 to 1C atoms, and R 3 and R 4 One of them may be F, Cl, or CN.

[0399] Equation I * A 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 (which may also have one or more non-adjacent CH2 groups substituted with O and / or S), 1,4-cyclohexenylene, 1,4-bicyclo(2,2,2)octylene, piperidine-1,4-diyl, naphthalene-2,6-diyl, decahydronaphthalene-2,6-diyl, or 1,2,3,4-tetrahydronaphthalene-2,6-diyl, with 1,4-phenylene or 1,4-cyclohexylene being particularly preferred. All of these compounds may optionally be substituted with one or more L groups or P-Sp groups.

[0400] Equation I * And a more preferred compound of the subformula is Z 3 and Z 4 However, each of these compounds independently represents -CO-O-, -O-CO-, or a single bond.

[0401] Equation I * More preferred compounds of the subformula are those in which L is selected from F, Cl, CN, CH3, C2H5, OCH3, OC2H5, COCH3, COC2H5, CF3, OCF3, P-Sp-, and in particular from F, Cl, CN, CH3, C2H5, OCH3, COCH3, or OCF3, with the most preferred being compounds selected from F, CH3, OCH3, or COCH3.

[0402] Equation I *A more preferred compound of the subformula is a compound in which P is selected from the group consisting of vinyloxy, acrylate, methacrylate, fluoroacrylate, chloroacrylate, oxetane, and epoxide, with very preferred being selected from acrylate and methacrylate, and most preferred being acrylate.

[0403] Equation I * And more preferred compounds of the subformula are those in which Sp is a single bond or -(CH2) p1 -, -O-(CH2) p1 -, -O-CO-(CH2) p1 , or -CO-O-(CH2) p1 The compound is represented by -O-(CH2) p1 -, -O-CO-(CH2) p1 , or -CO-O-(CH2) p1 In this case, the O atom or CO group is bonded to the benzene ring, respectively.

[0404] Equation I * More preferred compounds of the subformula are compounds in which all polymerizable groups P present in the compound have the same meaning, and very preferably represent acrylate or methacrylate, most preferably acrylate.

[0405] Equation I * More preferred compounds of the subformula contain one, two, three, or four P-Sp groups, and are particularly preferred to contain two or three P-Sp groups.

[0406] Equation I * A more preferred compound of the subformula is one in which at least one group Sp is a single bond.

[0407] Equation I * A more preferred compound of the subformula is one in which at least one Sp group is a single bond and at least one Sp group is not a single bond.

[0408] 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 A compound selected from the following, 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 bonded to the benzene ring, respectively.

[0409] R 3 or R 4 If the group is represented by the formula P-Sp-, the spacer groups on both sides of the mesogenic core may be the same or different.

[0410] Equation I * In the compound, m and l are preferably 0 or 1.

[0411] Equation I * The preferred compounds of the subformula are those in which G represents or contains a photoisomerizable group.

[0412] Equation I * And a more preferred compound of the subformula is Z 3 and / or Z 4 These terms 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-.

[0413] Equation I *More preferred compounds of the subformula are compounds containing an isomerized group selected from stilbene, (1,2-difluoro-2-phenylvinyl)benzene, cinnamic acid ester, α-cyanocinnamic acid ester, 4-phenylbuto-3-en-2-one, Schiff base, 2-benzylidene-1-indanone, chalcone, coumarin, chromone, pentarenone, or azobenzene.

[0414] Equation I * More preferred compounds of the subformula include 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).

[0415] Equation I * A highly preferred compound is one in which the chiral group G is selected from formula A:

[0416] [ka]

[0417] 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.

[0418] Formula A includes the following stereoisomers based on the corresponding dianhydrohexitol:

[0419] [ka]

[0420] 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.

[0421] 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-.

[0422] 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-.

[0423] Equation I * A more preferred compound of the subformula is one in which the chiral group G is selected from the following formulas.

[0424] [ka]

[0425] 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 -R4 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.

[0426] Equation I * The preferred compound is selected from the following formulas.

[0427] [ka]

[0428] 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.

[0429] Equation I * A highly preferred compound of A is selected from the following sub-formulas:

[0430] [ka]

[0431] [ka]

[0432] 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.

[0433] Equation I is particularly preferred. * It is a compound of A3.

[0434] 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.

[0435] 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-.

[0436] Equation I * And more preferred compounds of the subformula are selected from the following formulas:

[0437] [ka]

[0438] [ka]

[0439] [ka]

[0440] [ka]

[0441] [ka]

[0442] [ka]

[0443] 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 17Each 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.

[0444] 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.

[0445] 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.

[0446] 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.

[0447] The chiral isomerized compound, particularly of formula I, in the entire RM mixture according to the present invention. * The proportion of compounds selected from the or subformulas is preferably in the range of 0.1 to 4% by weight, very preferably 0.2 to 3% by weight, and most preferably 0.3 to 2% by weight.

[0448] The chiral RM mixture preferably exhibits a chiral nematic LC phase at room temperature, or both a chiral smectic LC phase and a chiral nematic LC phase, and very preferably exhibits a chiral nematic LC phase.

[0449] The chiral RM mixture preferably has a birefringence (Δn) in the range of 0.10 to 0.8, more preferably 0.12 to 0.7, and even more preferably 0.12 to 0.6.

[0450] The chiral 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.

[0451] The chiral RM mixture preferably has a birefringence (Δn) in the range of 0.18 to 0.8, more preferably in the range of 0.20 to 0.7, and even more preferably in the range of 0.25 to 0.6.

[0452] Preferably, the chiral RM mixture comprises an achiral host mixture and a chiral component. The achiral host mixture preferably comprises, more preferably, one or more monoreactive and / or direactive achiral RMs selected from formulas D, M, T, A and their sub-formulas, and does not contain a chiral compound. The chiral component preferably comprises, more preferably, one or more chiral compounds selected from formulas C1, C2, C3 and their sub-formulas.

[0453] The proportion of achiral host mixture in the chiral RM mixture is preferably 90-99.7%, and very preferably 94-99.5%. The proportion of chiral components in the chiral RM mixture is preferably 0.3-10%, and very preferably 0.5-6%.

[0454] In another preferred embodiment, the chiral RM mixture is preferably prepared by mixing an achiral host mixture, which preferably consists of one or more monoreactive and / or direactive achiral RMs selected from formulas D, M, T, A and their sub-formulas, but does not contain a chiral compound, with another chiral RM mixture containing a larger amount of chiral compound than the final chiral RM mixture after mixing.

[0455] In another preferred embodiment of the present invention, the achiral host mixture and the chiral RM mixture do not contain compounds of formula T or A. In another preferred embodiment, the chiral RM mixture consists of compounds selected from formulas D, M, C1, C2, C3, P or their subformulas, and optionally one or more additives described later, and the achiral host mixture consists of compounds selected from formulas D and M, and optionally one or more additives described later.

[0456] Another object of the present invention is an RM formulation comprising the chiral or achiral RM mixtures described above and below (hereinafter also simply referred to as "RM mixtures"), and further comprising one or more solvents and / or additives.

[0457] The proportion of the RM mixture in the RM formulation is preferably 85-100%, more preferably 85-99%, and most preferably 90-99%, which is the proportion relative to the total solids and liquid additives (i.e., excluding the solvent).

[0458] In another preferred embodiment, the chiral 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.

[0459] 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.

[0460] 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.

[0461] In another preferred embodiment, the RM mixture or 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.

[0462] In another preferred embodiment, the RM mixture or RM formulation is selected from, for example, 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 comprises a combination of 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).

[0463] The overall concentration of polymerization initiators (one or more) in the RM formulation is preferably 0.1-6%, very preferably 0.3-4%, and more preferably 0.7-2%.

[0464] In another preferred embodiment, in the 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.

[0465] In another preferred embodiment, the RM mixture or 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%.

[0466] 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.

[0467] 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.

[0468] 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.

[0469] Another suitable reactive thinner is polyester (meth)acrylate, which is a (meth)acrylic acid ester of polyesterol.

[0470] 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.

[0471] 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.

[0472] [ka]

[0473] 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.

[0474] 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.

[0475] Further examples of this group include alkoxylated phenol compounds, such as ethoxylated and propoxylated bisphenols.

[0476] These reactive thinners may further be, for example, epoxides or urethane (meth)acrylates.

[0477] 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.

[0478] 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.

[0479] Such epoxides and urethane (meth)acrylates are included in the compounds listed above as “mixed forms.”

[0480] 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.

[0481] 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.

[0482] Naturally, mixtures of these diluents can also be used in the composition according to the present invention.

[0483] 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.

[0484] 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.

[0485] 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.

[0486] 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).

[0487] Accordingly, certain additives can therefore be classified into the following numerous groups c1) to c8).

[0488] 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.

[0489] 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.

[0490] 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).

[0491] 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.

[0492] 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.

[0493] 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.

[0494] 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.

[0495] 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.

[0496] 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.

[0497] 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.

[0498] 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).

[0499] 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.

[0500] The thermosetting aids of group c3) include, for example, primary OH groups that can react with the isocyanate group of the binder.

[0501] Examples of thermosetting aids that may be used are BYK®-370, BYK®-373, and BYK®-375, which are available from BYK.

[0502] 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.

[0503] 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.

[0504] 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.

[0505] 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.

[0506] 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.

[0507] 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.

[0508] 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.

[0509] 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).

[0510] 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.

[0511] 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).

[0512] 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.

[0513] 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.

[0514] 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.

[0515] 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.

[0516] 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.

[0517] 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.

[0518] 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.

[0519] 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®.

[0520] 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.

[0521] 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.

[0522] 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.

[0523] 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.

[0524] 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,

[0525] 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.

[0526] 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"),

[0527] 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.

[0528] 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,

[0529] 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.

[0530] 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,

[0531] 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,

[0532] 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.

[0533] Acylaminophenols, for example, 4-hydroxylauroylanilide, 4-hydroxystearoylanilide, and octyl N-(3,5-di-tert-butyl-4-hydroxyphenyl)carbamate,

[0534] 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,

[0535] 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.

[0536] Ascorbic acid (vitamin C) and ascorbic acid derivatives, such as ascorbyl palmitate, laurate and stealth, as well as ascorbyl sulfate and phosphate,

[0537] 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,

[0538] 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,

[0539] 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,

[0540] 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.

[0541] 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,

[0542] 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.

[0543] 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.

[0544] 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

[0545] 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.

[0546] In another preferred embodiment, the chiral RM mixture or RM formulation includes an additive selected from formula IA.

[0547] [ka]

[0548] In the formula, R 11A This represents an alkyl group having 12 to 25, preferably 14 to 22, carbon atoms, preferably a linear chain, and most preferably an n-octadecyl group, R 12A This represents an alkyl group having 1 to 6 carbon atoms, preferably methyl or ethyl, and most preferably methyl.

[0549] A very preferred compound of formula IA is the compound of formula IA1.

[0550] [ka]

[0551] The compounds represented by formulas IA and IA1 improve the orientation of RM layers, particularly CLC RM layers, without excessively reducing surface tension. This makes it possible to coat multiple RM layers or chiral RM layers in layers without coating defects.

[0552] The concentrations of the compounds represented by formulas IA and IA1 in the chiral RM mixture are preferably 0.05 to 2%, very preferably 0.1 to 1%, and most preferably 0.2 to 0.7% relative to the total solids.

[0553] In a preferred embodiment, the RM formulation is obtained by dissolving it in a suitable solvent preferably selected from organic solvents.

[0554] 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.

[0555] 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%.

[0556] Preferably, the RM mixture or RM formulation contains one or more components selected from the group consisting of the following components, or any combination thereof. a) One or more polyreactive or bireactive polymerizable mesogenic compounds or RM, preferably selected from compounds represented by formula D and its subformulas. b) One or more monoreactive polymerizable mesogenic compounds or RM, preferably selected from compounds represented by formula M and its subformulas. c) One or more polymerizable chiral compounds, preferably selected from formulas C1 to C3 or their sub-formulas. d) One or more photoinitiators, e) Optionally, one or more polymerizable mesogenic compounds or RM selected from compounds represented by formulas T and A and their subformulas, f) Optionally, preferably, a nonpolymerizable chiral compound selected from formulas CI, C-II, and C-III, g) Optionally, preferably, an isomerizable chiral compound selected from polymerizable photoisomerizable chiral compounds, h) Optionally, one or more additives selected from adhesion promoters, surfactants, wetting agents, defoamers, lubricants, fluidizers, diluents, antioxidants, and UV stabilizers. i) One or more organic solvents of any kind.

[0557] More preferably, the RM mixture or RM formulation contains the following components: 1) One or more, preferably two or more, bireactive polymerizable mesogenic compounds selected from formula Da-1, 2) One or more, preferably two or more, single-reactive polymerizable mesogenic compounds selected from formulas M-1, M-4, M-6, M-8 to M10, 3) One or more polymerizable chiral compounds, preferably selected from formulas C1 to C3 or their sub-formulas, 4) One or more photoinitiators, 5) Optionally, one or more compounds of formula T or A, or their preferred sub-formulas, 6) Optionally, one or more nonpolymerizable chiral compounds, preferably selected from formulas CI, C-II, and C-III, 7) Optionally, one or more isomerized chiral compounds selected from polymerizable photoisomerized chiral compounds, 8) Optionally, one or more additives selected from adhesion promoters, surfactants, wetting agents, defoamers, lubricants, fluidizers, diluents, antioxidants, and UV stabilizers. 9) One or more organic solvents of any kind, Alternatively, any combination of components 1) to 7) above (provided that at least components 1) to 4) are present).

[0558] RM mixtures and RM formulations can be prepared by conventional methods, for example, by mixing one or more of the above-defined RMs, optionally adding further additives, and dissolving these RMs and additives in a solvent or solvent mixture.

[0559] The present invention further relates to a method for preparing individual RM layers, and more preferably comprises the following steps. - A step of depositing a layer of the chiral RM mixture or RM formulation described above and below onto a substrate having an orientation layer or a surface diffraction grating, - A step to remove the existing solvent. -Optionally, a step of annealing the chiral RM mixture, preferably at a temperature in which the RM mixture exhibits a cholesteric phase (without using a solvent), - A step of irradiating a chiral RM mixture with chemical rays, preferably ultraviolet light, to polymerize the RM and form a polymer film. - A process of optionally removing the polymer film from the substrate.

[0560] A preferred embodiment of the present invention relates to a method for manufacturing a multilayer RM waveplate, comprising the following steps. A1) A step of depositing a first layer of the chiral RM mixture or RM formulation according to the present invention onto a substrate, preferably a substrate having a surface diffraction grating or pattern, A2) Steps to remove the existing solvent, A3) Optionally, the first layer of the chiral RM mixture is annealed (without using a solvent) at a temperature at which it becomes a cholesteric phase. A4) A step of polymerizing the first layer of chiral RM mixture by ultraviolet irradiation at a temperature at which it becomes a cholesteric phase, preferably in an inert atmosphere. B1) A step of depositing a second layer of the RM compound according to the present invention onto a polymerized first RM layer. B2) Step to remove the existing solvent, B3) Optionally, the second layer of chiral RM mixture is annealed (without solvent) at a temperature at which it becomes a cholesteric phase. B4) A step of polymerizing the second layer of chiral RM mixture by ultraviolet irradiation at a temperature at which it becomes a cholesteric phase, preferably in an inert atmosphere.

[0561] The third, fourth, fifth, or subsequent layers can be prepared by repeating steps B1) to B4) using different chiral RM mixtures or RM formulations.

[0562] If the waveplate is not PBOE, it can be fabricated by the method described above, but in step A1), the substrate does not include a surface diffraction grating and preferably includes a planar orientation layer instead.

[0563] If the chiral RM mixture further contains a photoisomerizable chiral compound, the method for producing an optical element according to the present invention preferably includes an additional UV irradiation step for photoisomerization performed before the (photo)polymerization step. In a preferred embodiment, one or more of steps A4) and B4) in the method for producing an optical element described above and below consists of the following (sub)steps. 4.1) A first irradiation step (first UV step) is performed to induce photoisomerization of the chiral compound that can be photoisomerized in air by chemical irradiation, preferably UV irradiation, of the chiral RM mixture. 4.2) A step of optionally annealing the chiral RM mixture at a temperature that preferably results in a cholesteric phase, and 4.3) A second UV irradiation step (second UV step) in which the chiral RM mixture is subjected to chemical beam, preferably UV irradiation, to induce photopolymerization of the photoisomerizable compound in an inert gas atmosphere.

[0564] The initial irradiation, or first UV irradiation step, induces photoisomerization of the chiral compound containing the photoisomerizable group, forming a chiral structure with a biased helical pitch. The second irradiation, i.e., the second UV irradiation step, induces photopolymerization of the polymerizable mesogenic compound, fixing the chiral structure.

[0565] The chiral RM mixtures used for each individual RM layer are preferably different from one another. In a preferred embodiment, the RM mixtures used for the production of the first, second, and further layers each contain different amounts of chiral compounds and / or chiral compounds having different HTPs and / or chiralities. As a result, the helical pitch and helix angle in the first, second, and further RM layers can be adjusted to be different from one another.

[0566] In a preferred embodiment, an RM mixture containing a chiral dopant (chiral mixture) and an RM mixture without a chiral compound (achiral mixture) are mixed in various ratios, thereby easily varying the amount of chiral dopant in the mixture of the chiral and achiral mixtures. As a result, the desired helical pitch and twist angle in each final RM layer can be easily adjusted. From such RM mixtures or mixed RM mixtures, first, second, and further chiral RM layers having the same or different twist angles can be prepared in a simple and highly reproducible manner, making it suitable for large-scale production.

[0567] The RM mixtures, formulations, and methods of the present invention enable the simple preparation of multilayer films of two or more chiral LC polymer films by using an achiral RM host mixture containing or consisting of one or more compounds selected from formulas D, M, A, and T. This achiral RM host mixture can be used to prepare individual layers. The chiral RM mixtures used for the first, second, or subsequent layers are prepared by adding the same chiral compound in different amounts to the RM host mixture, or by adding chiral compounds with different HTPs to the RM host mixture.

[0568] This RM mixture or RM 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.

[0569] RM mixtures or RM formulations can be applied to substrates by conventional coating techniques such as spin coating, bar coating, and 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.

[0570] 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.

[0571] In another preferred embodiment, the substrate has a surface diffraction grating or surface pattern, preferably a PB diffraction grating as shown in Figure 1a or 1b, for example. The surface diffraction grating is fabricated from a photo-aligned layer (PAL) that is patterned by laser interferometry to form a grating pattern having a specified pitch.

[0572] In another preferred embodiment, the substrate comprises an orientation layer that induces or promotes the planar orientation of RM molecules, and may be, for example, a polyimide orientation layer that can be rubbed with a velvet cloth, a photo-orientation layer, or an orientation-cured RM layer.

[0573] 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.

[0574] 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.

[0575] 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 mixture.

[0576] 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 RM 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.

[0577] 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.

[0578] 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.

[0579] In a preferred embodiment, the method of the present invention includes a step of allowing the RM mixture to stand for a certain period of time in order to uniformly redistribute the RM mixture onto the substrate (hereinafter referred to as "annealing").

[0580] 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.

[0581] The RM mixture preferably consists of compounds that spontaneously orient themselves when deposited on a substrate as a mixture. Therefore, preferably, the LC medium does not undergo heat treatment to orient the mesogenic or liquid crystalline compounds before UV irradiation.

[0582] 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.

[0583] 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.

[0584] 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, more preferably 30 to 800 mJcm -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.

[0585] The first irradiation step or the first ultraviolet step is preferably carried out in air.

[0586] The first irradiation step or the first ultraviolet step is preferably carried out at room temperature.

[0587] Photopolymerization of RM mixtures is preferably achieved by exposing them 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.

[0588] 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.

[0589] 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.

[0590] 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.

[0591] Photopolymerization is preferably carried out under an inert gas atmosphere, preferably under a nitrogen atmosphere.

[0592] Photopolymerization is preferably carried out at room temperature.

[0593] 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.

[0594] 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.

[0595] 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.

[0596] The present invention further relates to optical, electro-optical, or electronic devices or components including the waveplates described above and below.

[0597] The aforementioned components include, but are not limited to, liquid crystal displays (LCDs), organic light-emitting diodes (OLEDs), autostereoscopic 3D displays, see-through near-eye displays, augmented reality (AR) or virtual reality (VR) systems, switchable windows, spatial light modulators, optical data storage, remote light sensing, holography, spectrometers, optical communications, polarimeters, or optical phase difference films such as quarter-wave plates (QWPs) or half-wave plates (HWPs) for use in front / backlighting, polarizers, and optical compensators. This includes reflective films, Bragg polarizing gratings (Bragg PG), polarizing volume gratings (PVG), polarizing volume holograms (PVH), Pancharatnam Berry (PB) gratings, and other diffraction gratings or surface diffraction gratings, as well as non-mechanical beam steering elements, optical waveguides, optical couplers, deflectors or combiners, polarizing beam splitters, partial mirrors, reflective films, alignment layers, color filters, antistatic protective sheets, electromagnetic interference protective sheets, optical waveguides, lenses for focusing and optical effects, polarization control lenses, PB deflectors, PB lenses, and IR reflective films.

[0598] The above devices include, but are not limited to, electro-optical displays, particularly LCDs, OLEDs, nonlinear optical (NLO) devices, autostereoscopic 3D displays, see-through near-eye displays, head-up 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.

[0599] Preferably, this component is a diffraction grating, particularly preferably a PBG, PBL, or Bragg PG, and includes one or more waveplates according to the present invention as described above and below, and can be optionally combined with other waveplates, polarizers, and / or other components.

[0600] The waveplate according to the present invention is particularly suitable for use in OLED displays or LC displays, such as automotive head-up displays, NLO devices, autostereoscopic 3D displays, see-through near-eye displays, AR / VR systems, or goggles for AR / VR applications.

[0601] 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.

[0602] 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.

[0603] 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.

[0604] 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).

[0605] 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.

[0606] 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.

[0607] 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.

[0608] In the above and below, percentages are weight percentages unless otherwise stated. All temperatures are expressed in Celsius.

[0609] 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.

[0610] 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.

[0611] 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.

[0612] 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]

[0613] <Example 1 - Achromatic HWP on PB deflection lattice, 4-layer structure> Prepare the following RM mixture.

[0614] [Table 1]

[0615] Irganox® 1076 is a commercially available stabilizer (Ciba AG, Basel, Switzerland). BYK®-310 is a commercially available surfactant (BYK, Germany). TR-PBG-304 is a commercially available photoinitiator (Tronly, China). Paliocolor® LC242 is a commercially available bireactive achiral RM (BASF, Germany).

[0616] [Table 2]

[0617] [Table 3]

[0618] Achiral RM mixture M1 and chiral RM mixtures M2 and M3 were each dissolved in diethyl carbonate at a solid content concentration of 30%. From these solutions, blends 1 to 6 were prepared to achieve the chiral concentrations required to obtain the CLC pitch for each RM layer, as shown in Table 1.1. By using the chiral RM of formula C1-1-6a in either an S configuration or an R configuration, chiral RM layers with left-handed or right-handed twists can be obtained.

[0619] <Table 1.1 - Chiral RM mixture blends>

[0620] [Table 4]

[0621] Using blends 1-4, a twisted RM multilayer film is fabricated that functions as a broadband half-wave plate (HWP) for circularly polarized light, as shown in Table 1.2.

[0622] <Table 1.2 - Multilayer Film Structure>

[0623] [Table 5]

[0624] The multilayer film is manufactured using the following process: The SD1 photoalignment layer is spin-coated onto an untreated glass substrate at 3000 rpm and annealed at 80°C for 60 seconds.

[0625] [ka]

[0626] The annealed SD1 layer is irradiated with polarized UV light using a laser interferometer with a Coherent Genesis 355nm laser (as described in Shin-Tson Wu, J.Opt.Soc.Am.B, 36(5), D52-D65 (2019)), thereby forming a PB-bending lattice with a lattice pitch length of 2 μm, as shown in Figure 1a.

[0627] On this PB grid, a layer of Blend 1 was applied at 2484 rpm for 30 seconds, annealed at 60°C for 60 seconds, and then cured under a nitrogen atmosphere using a broadband omnicure lamp (100 mW / cm²). 2 Cure for 60 seconds using ). Next, apply, anneal, and cure a layer of Blend 2 on top of the cured layer of Blend 1 under the same conditions, except that annealing is performed at 40°C for 30 seconds. Repeat this process for Blend 3 and Blend 4, applying each on top of the previous cured layer.

[0628] When the resulting multilayer film is observed using a crossed nicol polarizer, a highly transmittance white film is observed. This is consistent with the expected performance of the broadband HWP.

[0629] <Example 2-Blue HWP, 6-layer structure> The RM mixtures M1 to M3 from Example 1 are each dissolved in diethyl carbonate at a 40% solids concentration. Blends 5 to 10 are prepared from these solutions as shown in Table 2.1.

[0630] <Table 2.1 - Chiral RM mixture blends> [Table 6]

[0631] Using blends 5-10, a twisted RM multilayer is fabricated that functions as a blue HWP with the configuration shown in Table 2.2.

[0632] <Table 2.2 - Multilayer Film Configuration> [Table 7]

[0633] A layer of Blend 5 was coated onto a Corning Eagle XG substrate having a planar rubbing polyimide orientation layer at 3188 rpm for 30 seconds, annealed at 60°C for 60 seconds, and then cured under a nitrogen atmosphere using a broadband omnicure lamp (100 mW / cm²). 2 Cure for 60 seconds using ( ). Next, apply a layer of blend 6 onto the cured layer of blend 1 under the same conditions except that the annealing temperature is 40°C for 30 seconds, then anneal and cure. Repeat this process for blends 7 to 10, applying each one onto the previously cured layer.

[0634] When the resulting multilayer film was observed using a crossed nicol polarizer, a vivid blue film was observed. This is consistent with the expected performance of the blue HWP and the red / green full-wavelength plates.

[0635] <Example 3 - Red-blue HWP with PB deflection grid, 6-layer structure> The RM mixtures M1 to M3 from Example 1 are each dissolved in diethyl carbonate at a 35% solids concentration. Blends 11 to 16 are prepared from these solutions as shown in Table 3.1.

[0636] <Table 3.1 - Chiral RM mixture blends> [Table 8]

[0637] Using blends 11-16, a twisted RM multilayer was fabricated that functions as a HWP for red and blue light in the configurations shown in Table 3.2.

[0638] <Table 3.2 - Multilayer Film Structure> [Table 9]

[0639] A multilayer film is fabricated on a PB deflection grid using the same method as described in Example 1, except that the spin speed is 3105 rpm and the grid pitch length is 11 μm.

[0640] When the resulting multilayer film is observed with a crossed nicol polarizer, a vivid purple film is observed. This is consistent with the expected performance of the red and blue HWP and the green all-wave plate.

[0641] <Example 4-Red HWP, 7-layer structure> The RM mixtures M1 to M3 from Example 1 are each dissolved in diethyl carbonate at a 40% solids concentration. Blends 17 to 23 are prepared from these solutions as shown in Table 4.1.

[0642] <Table 4.1 - Chiral RM mixture blends> [Table 10]

[0643] Using blends 17-23, a twisted RM multilayer is fabricated that functions as a HWP for red light with the configuration shown in Table 4.2.

[0644] <Table 4.2 - Multilayer Film Structure> [Table 11]

[0645] A multilayer film is fabricated on a planar photoalignment layer by the process described in Example 2, except that the spin speed is 3696 rpm.

[0646] When the resulting multilayer film is observed with a crossed nicol polarizer, a vivid red film is observed. This is consistent with the expected performance of the red HWP and the green / blue full-wavelength plate.

[0647] <Example 5 - Chromatic HWP for blue light> Prepare the following RM mixture.

[0648] [Table 12]

[0649] OXE-05 is a commercially available photoinitiator (manufactured by BASF).

[0650] [Table 13]

[0651] [Table 14]

[0652] Achiral RM mixture M4 and chiral RM mixtures M5 and M6 are each dissolved in diethyl carbonate at a solid content concentration of 40%. From these solutions, blends 24-29 are prepared to achieve the chiral concentration required to realize the CLC pitch for each RM layer, as shown in Table 5.1. By using the chiral RM of formula C1-1-6a in either the S or R configuration, chiral RM layers with left-handed or right-handed twists are obtained. Furthermore, achiral mixture M4 is used in one of the layers.

[0653] <Table 5.1 - Chiral RM mixture blends> Prepare the following RM mixture.

[0654] [Table 15]

[0655] Using blends 24-29 and mixture M4, a twisted RM multilayer was fabricated to be used as a chromatic waveplate that selectively functions as a HWP for blue circularly polarized light, as shown in Table 5.2.

[0656] <Table 5.2 - Multilayer Film Structure> [Table 16]

[0657] The annealing temperature was 40°C, and the curing light intensity was 60 mW / cm². 2 Except for the above, a multilayer film is prepared on a rubbing-treated polyimide orientation film according to the process described in Example 2.

[0658] When the resulting multilayer film is observed using a crossed nicol polarizer, a blue transmission film is observed. This is consistent with the expected performance of blue HWP.

[0659] <Example 6 - Chromatic PB deflection grating for red and blue light> The RM mixtures M4 to M6 from Example 5 are each dissolved in diethyl carbonate at a solid content concentration of 40%. Blends 30 to 37 are prepared from these solutions as shown in Table 6.1.

[0660] <Table 6.1 - Chiral RM mixture blends> [Table 17]

[0661] Using blends 30-37, a twisted RM multilayer is fabricated to be used as a chromatic diffraction grating that selectively diffracts red and blue light but does not diffract green light, with the configuration shown in Table 6.2.

[0662] <6.2-Multilayer Film Configuration> [Table 18]

[0663] The annealing temperature was 40°C, and the curing light intensity was 60 mW / cm². 2 Except for the above, a multilayer film is fabricated on a PB diffraction grating with a grating pitch of 11 μm according to the process described in Example 1.

[0664] When the resulting multilayer film was observed through transmission, it was confirmed that it selectively diffracted red and blue light but not green light, which is consistent with the expected performance of a chromatic diffraction grating that functions as a PB deflector for red and blue light.

[0665] <Example 7 - Achromatic PB deflection grating> Prepare the following RM mixture.

[0666] [Table 19]

[0667] [Table 20]

[0668] [Table 21]

[0669] RM mixtures M7 to M9 are each dissolved in PGEMA at a solid content concentration of 25%. Mixtures 38 to 41 are prepared from these solutions as shown in Table 7.1.

[0670] <Table 7.1 - Chiral RM mixture blends>

[0671] [Table 22]

[0672] Using blends 37-40, a twisted RM multilayer structure with the configuration shown in Table 7.2 is fabricated to be used as an achromatic diffraction grating.

[0673] <7.2-Multilayer Film Configuration> [Table 23]

[0674] A multilayer film is fabricated on a PB diffraction grating with a grating pitch of 2 μm, following the process described in Example 1, except that the annealing temperature is 20°C, curing is performed in a nitrogen atmosphere, at 60% power output, and using a conveyor belt type melting lamp with a belt speed of 10 m / min.

[0675] When the resulting multilayer film was observed through transmission, it was confirmed that it diffracted red, green, and blue light, indicating that it met the expected performance requirements as an achromatic diffraction grating that functions as an achromatic PB deflector.

[0676] <Example 8 - Achromatic deflection grating> As shown in Figure 2, the multilayer structures of Examples 1, 2, 3, and 4 are stacked with air layers in between to form a laminated structure. The resulting laminated structure functions as an achromatic PB deflector with a deflection angle of 15° for circularly polarized RGB light.

[0677] As described above, QWPs are added to the front and back of the multilayer stack. As a result, the enlarged stack functions as an achromatic PB deflector with a deflection angle of 15° for linearly polarized RGB light.

Claims

1. - At least one achromatic half-wave plate (HWP), - A diffractive optical element (DOE) comprising at least one chromatic HWP, Each HWP includes a substrate on which two or more cholesteric liquid crystal (CLC) layers are formed, the first CLC layer being deposited directly onto the substrate, and subsequent CLC layers being deposited directly on their respective preceding CLC layers. Each CLC layer consists of a polymerized chiral reactive mesogen (RM) mixture, the LC director exhibits a helical twist having a predetermined twist angle along the helical axis in the thickness direction of the CLC layer, the chiral RM mixture comprises one or more RMs selected from monoreactive, direactive, and polyreactive RMs, and further comprises one or more chiral compounds selected from chiral RMs, and a photoinitiator. In at least one achromatic and chromatic HWP, the substrate is a diffractive optical element comprising a periodic surface diffraction grating that induces rotation of the LC director in the in-plane direction of the first CLC layer.

2. The DOE according to claim 1, characterized in that at least one of the chromatic HWP and the achromatic HWP has at least two CLC layers with different torsion angles.

3. The DOE according to claim 1 or 2, characterized by comprising two or more chromatic HWPs.

4. The DOE according to any one of claims 1 to 3, further characterized by comprising one or more quarter-wave plates (QWPs).

5. - An achromatic HWP comprising a substrate having a periodic surface diffraction grating, preferably consisting of the substrate, wherein two or more CLC layers are formed on the substrate, the first CLC layer is deposited directly on the substrate, and the second and subsequent CLC layers are deposited directly on their respective preceding CLC layers. - A chromatic HWP comprising at least one, preferably two or more, chromatic HWPs, each preferably comprising a substrate having optionally a planar oriented layer, preferably comprising the substrate, wherein two or more CLC layers are formed on the substrate, the first CLC layer is deposited directly on the substrate, and the second and subsequent CLC layers are deposited directly on their respective preceding CLC layers, - Optionally, a chromatic HWP comprising a substrate having a periodic surface diffraction grating, preferably consisting of the substrate, wherein two or more CLC layers are formed on the substrate, the first CLC layer is deposited directly on the substrate, and the second and subsequent CLC layers are deposited directly on their respective preceding CLC layers. Each CLC layer is made of a polymerized chiral RM mixture having a helical twist along the helical axis in the thickness direction of the CLC layer, the chiral RM mixture comprising one or more RMs selected from monoreactive, direactive, and polyreactive RMs, and one or more chiral compounds further selected from chiral RMs, and a photoinitiator. In at least one of chromatic and achromatic HWP, preferably in each, at least two CLC layers have different torsion angles. The DOE according to any one of claims 1 to 4, characterized in that the periodic surface diffraction grating induces rotation of the LC director in the in-plane direction of the first CLC layer, and is preferably a PB deflection grating or a PB lens grating.

6. When viewed from the direction of incident light, the DOE includes the following components in the following order: - A first achromatic HWP (201, 301) effective for all red (R), green (G), and blue (B) light. - A second chromatic HWP (202, 302) that is effective only for one of the RGB light, preferably B light, and not for the other RGB light, preferably R or G light. - A third chromatic HWP (203, 303) that is effective for R and B light but not for G light. -Optionally, a fourth chromatic HWP (204, 304) which is effective only for one of the RGB light, preferably the R light, and not for the other RGB light, preferably the G or B light, The first, second, third, and fourth HWP each contain two or more CLC layers, the first CLC layer is deposited directly onto the substrate, and the second and subsequent CLC layers are deposited directly on their respective preceding CLC layers. Each CLC layer consists of a polymerized chiral RM mixture having a helical twist along the helical axis in the thickness direction of the CLC layer, the chiral RM mixture comprising one or more bireactive RMs, one or more monoreactive RMs, one or more chiral compounds selected from chiral RMs, and a photoinitiator. The DOE according to any one of claims 1 to 5, characterized in that the substrates of the first and third HWPs include a PB deflector or a PB lens grating, and the substrates of the second and fourth HWPs have a planar alignment layer.

7. The DOE according to claim 6, characterized in that, when viewed from the direction of incident light, the first QWP is located in front of the first HWP (201, 301) and the second QWP is located on the back of the fourth HWP (204, 304).

8. The DOE according to any one of claims 1 to 7, characterized in that the surface diffraction grating is a PB deflection diffraction grating and the DOE is an achromatic PB deflector.

9. The DOE according to any one of claims 1 to 8, characterized in that the surface diffraction grating is a PB lens diffraction grating and the DOE is an achromatic PB lens.

10. The DOE according to any one of claims 1 to 9, characterized in that the chiral RM mixture comprises one or more compounds selected from formula D and / or one or more compounds selected from formula M. 【Chemistry 1】 (In the formula, 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. 【Chemistry 2】 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, -NO ２ , -NCO, -NCS, -OCN, -SCN, -C(=O)NR ｘ R ｙ , -C(=O)OR ｘ , -C(=O)R ｘ , -NR ｘ R ｙ , -OH, -SF ５ , optionally substituted silyl, aryl or heteroaryl having from 1 to 12, preferably from 1 to 6 C atoms and linear or branched alkyl, alkoxy, alkylcarbonyl, alkoxycarbonyl, alkylcarbonyloxy or alkoxycarbonyloxy having from 1 to 1, preferably from 1 to 6 C atoms, provided that one or more H atoms may be replaced by F or Cl, MG M This is a rod-shaped mesogenic group, which is preferably selected from formula MGM. 【Transformation 3】 A １Ｍ and A ２Ｍ If multiple groups exist, they independently represent aromatic or alicyclic groups, and each group may contain one or more heteroatoms selected from N, O, and S, L Ｍ This may be performed by one substitution or multiple substitution, L Ｍ F, Cl, Br, I, -CN, -NO ２ , -NCO, -NCS, -OCN, -SCN, -C(=O)NR ｘ R ｙ , -C (=O) OR ｘ , -C(=O)R ｘ , -NR ｘ R ｙ -OH, -SF ５ , substituted silyls, aryls or heteroaryls having 1 to 12, preferably 1 to 6 C atoms, and linear or branched alkyls, alkoxys, alkylcarbonyls, alkoxycarbonyls, alkylcarbonyloxys or alkoxycarbonyloxys 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 there are multiple instances, 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 -, -OCH ２ -ien-CH ２ O-, -SCH ２ -ien-CH ２ S-, -CF ２ O-, -OCF ２ -, -CF ２ S-, -SCF ２ -ien-CH ２ CH ２ -, - (CH ２ ) ｎ１ , -CF ２ CH ２ -ien-CH ２ CF ２ -, -CF ２ CF ２ -, -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. R ００ and R ０００ Each of these independently represents an alkyl group having H or 1 to 12 C atoms. R ２２ is P-Sp-, F, Cl, Br, I, -CN, -NO ２ , -NCO, -NCS, -OCN, -SCN, -C(=O)NR ｘ R ｙ , -C(=O)X, -C(=O)OR ｘ , -C(=O)R ｙ , -NR ｘ R ｙ -OH, -SF ５ , 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. 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.

11. The DOE according to any one of claims 1 to 10, characterized in that the chiral RM mixture contains a chiral compound selected from formulas C1, C2, and C3. 【Chemistry 4】 (In the formula, each base is independent of the others and, in each instance, is identical or different in the following sense) 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 groups L. L is an alkyl, alkoxy, thioalkyl, alkylcarbonyl, alkoxycarbonyl, alkylcarbonyloxy or alkoxycarbonyloxy which may be fluorinated and has 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＊ is -COO-, -OCO-, -O-CO-O-, -OCH ２ -, -CH ２ O-, -CF ２ O-, -OCF ２ -, -CH ２ CH ２ -, -(CH ２ ) ４ -, -CF ２ CH ２ -, -CH ２ CF ２ -, -CF ２ CF ２ -, -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.

12. The DOE according to any one of claims 1 to 11, characterized in that the chiral RM mixture contains a photoinitiator selected from oxime esters, preferably carbazole oxime esters.

13. An optical, electro-optical, or electronic device or component thereof, comprising a DOE as described in any one of claims 1 to 12.

14. The components according to claim 13, selected from optical phase difference films such as quarter-wave plates (QWP) or half-wave plates (HWP), polarizers, optical compensators, reflective films, diffraction gratings or surface diffraction gratings such as Bragg polarizing gratings (Bragg PG), polarizing volume gratings (PVG), polarizing volume holograms (PVH), Pancharatnam Berry (PB) gratings, as well as non-mechanical beam steering elements, optical waveguides, optical couplers, deflectors or combiners, polarizing beam splitters, partial mirrors, reflective films, alignment layers, color filters, antistatic protective sheets, electromagnetic interference protective sheets, optical waveguides, lenses for focusing and optical effects, polarization control lenses, PB deflectors, PB lenses, and IR reflective films.

15. The device according to claim 13, selected from liquid crystal displays, organic light-emitting diodes, nonlinear optical (NLO) devices, autostereoscopic 3D displays, head-up displays, see-through near-eye displays, augmented reality / virtual reality (AR / VR) systems, goggles for augmented reality / virtual reality (AR / VR) applications, switching windows, spatial light modulators, optical data storage devices, optical sensors, holographic devices, spectrometers, optical communication systems, polarimeters, or front / backlights. 。

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