Polymerizable liquid crystal materials and polymerized liquid crystal films

Abstract

A polymerizable liquid crystal material and a polymerized liquid crystal film are provided. The present invention relates to a polymerizable LC material comprising at least one di- or multi-reactive mesogenic compound and at least one compound of formula I. Furthermore, the present invention relates to a method for the preparation of the polymerizable LC material, a polymer film obtainable from the corresponding polymerizable LC material, a method for the preparation of such a polymer film, and the use of the polymer film and said polymerizable LC material for optical, electro-optical, decorative or security devices. TIFF2023535130000096.tif66165 (where parameter R 1 , A 1 , Z 1 , Z 2 ,n,Sp,P,p1,p2,L 1 , L 2 , r1, r2, m and R 2 has one of the meanings as given in claim 1.

Description

[Technical Field]

[0001] The present invention relates to a polymerizable LC material comprising at least one bireactive or polyreactive mesogenic compound and at least one compound of formula I.

[0002] [ka]

[0003] During the ceremony, R 1 represents an alkyl or alkoxy group having H and 1 to 15 C atoms, provided that in addition, one or more CH2 groups in these groups are arranged such that the O atoms are not directly bonded to each other, such as -CH=CH-, -C≡C-, -CF2O-, -CH=CH-, [ka] -O-, -CO-O-, -O-CO- may be substituted, and in the group, one or more H atoms may be substituted with halogens. R 2 This represents an alkyl group having H or 1 to 8 C atoms, particularly H, CH3, C2H5, C3H7, and C4H9. [ka] This represents, L 1 and L 2 In each case, each represents independently of the others F, Cl, Br, I, -CN, -NO2, -NCO, -NCS, -OCN, -SCN, an alkyl, alkoxy, alkylcarbonyl, alkoxycarbonyl, alkylcarbonyloxy or alkoxycarbonyloxy having 1 to 5 C atoms in a linear or branched chain, and one or more H atoms in the group may be replaced with F or Cl. L 3In each case, each represents independently of the others H, F, Cl, Br, I, -CN, -NO2, -NCO, -NCS, -OCN, -SCN, an alkyl, alkoxy, alkylcarbonyl, alkoxycarbonyl, alkylcarbonyloxy or alkoxycarbonyloxy having 1 to 5 C atoms in a linear or branched chain, and one or more H atoms in the group may be replaced with F or Cl. m represents 0, 1, or 2. n represents 2, P represents a polymerizable group, Sp represents a spacer group (also called a spacer) or a single bond. Z 1 and Z 2 In each case, these represent a single bond, -O-, -S-, -CO-, -CO-O-, -OCO-, -O-CO-O-, -OCH2-, -CH2-, -CH2O-, -CF2O-, -OCF2-, -CH2CH2-, -(CH2)4-, -CF2CH2-, -CH2CF2-, -CF2CF2-, -CH=CH-, -CF=CF-, -C≡C-, -CH=CH-COO-, or -OCO-CH=CH-, p1 represents 1, 2, or 3, preferably 2 or 3. r1 is 0, 1, 2, or 3, where p1+r1 is less than or equal to 4. p2 represents 0, 1, 2, or 3. r² represents 0, 1, 2, or 3, where p² + r² is less than or equal to 4.

[0004] The present invention also relates to methods for preparing the same, polymer films that can be obtained from the corresponding polymerizable LC material, methods for preparing such polymer films, and the use of the polymer films and the polymerizable LC material for optical, electro-optical, decorative or security devices. The present invention also relates to the compound of formula I. [Background technology]

[0005] Polymerizable liquid crystal materials are known in the prior art for preparing anisotropic polymer films having uniform orientation. These films are typically prepared by coating a thin layer of polymerizable liquid crystal mixture onto a substrate, oriented the mixture to a uniform orientation, and polymerizing the mixture. The orientation of the film can be planar, i.e., the liquid crystal molecules are oriented substantially parallel to the layer, or homeotropic (orthogonal or perpendicular to the layer) or tilted.

[0006] Such optical films are described, for example, in European Patent No. 0940707 (Patent Document 1), European Patent No. 0888565 (Patent Document 2), and British Patent No. 2329393 (Patent Document 3).

[0007] Conventional homeotropically oriented films require a polyimide (PI) layer to induce the desired homeotropic orientation of the RM. Besides the significant cost of manufacturing this layer, undesirable interactions between PI and RM often lead to undesirable dark-state transmission. Therefore, it is desirable to remove the PI while providing the required uniform homeotropic orientation.

[0008] Furthermore, as described in International Publication No. 18050608 (Patent Document 4), additives that prevent the presence of a PI layer require pretreatment of the substrate prior to RM coating. This can take the form of corona discharge (CD) treatment or UV-ozone treatment, but is not limited to these examples. Providing a solution that enables +C orientation without requiring prior surface treatment is advantageous compared to what is currently possible with the prior art.

[0009] Therefore, there remains a need for novel, preferably improved, polymerizable liquid crystal materials or mixtures that do not exhibit, or exhibit to a small degree, the drawbacks of prior art materials. [Prior art documents] [Patent Documents]

[0010] [Patent Document 1] European Patent No. 0940707 [Patent Document 2] European Patent No. 0888565 [Patent Document 3] British Patent No. 2329393 [Patent Document 4] International Publication No. 18050608 [Disclosure of the Invention] [Problems that the invention aims to solve]

[0011] Advantageously, such polymerizable LC materials should preferably be applicable to the preparation of polymer films with different uniform orientations, and especially simultaneously, • Exhibits good adhesion to the substrate, • Highly transparent to VIS light, • Shows reduced transmission in dark conditions. • Exhibits desirable high-temperature stability or durability, and in addition, • Uniformly oriented polymer films must be manufactured using compatible and commonly known methods for mass production.

[0012] Other objects of the present invention will be immediately apparent to those skilled in the art from the following detailed description.

[0013] Surprisingly, the inventors of the present invention have found that by using the polymerizable LC material described in claim 1, one or more, preferably all, of the above-required objectives can be achieved, preferably simultaneously. [Means for solving the problem]

[0014] Therefore, the present invention relates to a polymerizable LC material comprising at least one bireactive or polyreactive mesogenic compound and at least one compound of formula I.

[0015] Furthermore, the present invention also relates to a corresponding method for producing polymerizable LC materials.

[0016] The present invention further relates to polymer films that can be obtained, or preferably obtained, from polymerizable LC materials as described above and below, and to methods for producing polymer films as described above and below.

[0017] The present invention further relates to the use of polymer films or polymerizable LC materials as described above and below in optical, electro-optical, information storage, decorative, and security applications such as liquid crystal displays, projection systems, polarizers, compensators, alignment layers, circular polarizers, color filters, decorative images, liquid crystal pigments, reflective films having spatially varying reflective colors, multicolor images, and non-articulated documents such as IDs, credit cards, or banknotes.

[0018] The present invention further relates to optical components or devices, polarizers, patterned retarders, compensators, alignment layers, circular polarizers, color filters, decorative images, liquid crystal lenses, liquid crystal pigments, reflective films whose reflected color changes spatially, and multicolor images for decoration or information storage, comprising at least one polymer film or polymerizable LC material as described above and below.

[0019] The present invention further relates to a liquid crystal display comprising at least one polymer film or polymerizable LC material or optical component as described above and below.

[0020] The present invention further relates to authentication, verification, or security marking, color or multicolor images for security applications, IDs, or non-counterfeit objects or valuable documents such as credit cards or banknotes, comprising at least one polymer film or polymerizable LC material or optical component as described above and below. [Modes for carrying out the invention]

[0021] <Terms and Definitions>

[0022] As used herein, the term “polymer” is understood to mean a molecule that contains a backbone of one or more different types of repeating units (the smallest constituent units of a molecule), and includes well-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 associated with the synthesis of such polymer, where such residues are understood not to be covalently incorporated therein. Moreover, such residues and other elements are usually removed in post-polymerization purification processes, but are typically mixed or contaminated with the polymer and generally remain with the polymer when they move between containers or between solvents or dispersion media.

[0023] As used in this invention, the term "(meth)acrylic polymer" includes polymers obtained from acrylic monomers, polymers obtained from methacrylic monomers, and corresponding copolymers obtained from mixtures of such monomers.

[0024] The term "polymerization" refers to the chemical process of forming a polymer by bonding together multiple polymerizable groups or polymer precursors (polymerizable compounds) that contain such polymerizable groups.

[0025] The terms “film” and “layer” include rigid or flexible self-supporting or freestanding films with mechanical stability, as well as coatings or layers on or between a support substrate.

[0026] The term "liquid crystal" or "LC (liquid crystal)" refers to materials that have a liquid crystalline intermediate phase within a certain temperature range (thermotropic LC) or a certain concentration range in solution (lyotropic LC). These materials always contain a mesogenic compound.

[0027] The terms "mesogenic compound" and "liquid crystal compound" refer to compounds containing one or more calamistic (rod or board / lath-shaped) or discotic (disc-shaped) mesogenic groups. The term "mesogenic group" refers to a group that has the ability to induce the behavior of a liquid crystal (LC) phase. Compounds containing mesogenic groups do not necessarily have to exhibit a liquid crystal intermediate phase themselves. They may exhibit a liquid crystal intermediate phase only in mixtures with other compounds, or when the mesogenic compound or material, or mixtures thereof, polymerize. This includes low-molecular-weight, non-reactive liquid crystal compounds, reactive or polymerizable liquid crystal compounds, and liquid crystal polymers.

[0028] A calamistic mesogenic group typically comprises a mesogenic core consisting of one or more aromatic or non-aromatic cyclic groups bonded to each other directly or via linking groups, optionally including terminal groups bonded to the ends of the mesogenic core, and optionally including one or more side groups bonded to the long chain of the mesogenic core, where these terminal and side groups are typically selected from, for example, carbyl groups, hydrocarbyl groups, polar groups such as halogen groups, nitro groups, hydroxyl groups, etc., or polymerizable groups.

[0029] The term "reactive mesogen (RM)" refers to a polymerizable mesogen or liquid crystal compound, preferably a monomer compound. These compounds can be used as pure compounds or as mixtures of a reactive mesogen with other compounds that function as photoinitiators, inhibitors, surfactants, stabilizers, chain transfer agents, nonpolymerizable compounds, etc.

[0030] Furthermore, polymerizable compounds with one polymerizable group are also called "monoreactive" compounds, compounds with two polymerizable groups are called "direactive" compounds, and compounds with three or more polymerizable groups are called "polyreactive" compounds. Compounds that do not have polymerizable groups are also called "nonreactive" compounds.

[0031] The term "polymerizable LC material" means a material containing more than 90% by weight, preferably more than 95% by weight, more preferably more than 98% by weight of the polymerizable compounds as described above.

[0032] The term "non-mesogenic compound or material" means a compound or material that does not contain a mesogenic group as defined above.

[0033] Visible light is electromagnetic radiation having wavelengths in the range of about 400 nm to about 740 nm. Ultraviolet (UV) light is electromagnetic radiation having wavelengths in the range of about 200 nm to about 450 nm.

[0034] Irradiance (E e ) or radiation output is defined as the output of electromagnetic waves (dθ) per unit area (dA) incident on a surface: E e = dθ / dA.

[0035] Radiation exposure or radiation dose (H e ) is defined as the irradiance or radiation output (E e ) per unit time (t): H e = E e ·t.

[0036] All temperatures, such as the melting point T(C,N) or T(C,S) of a liquid crystal, the transition T(S,N) from the smectic (S) phase to the nematic (N) phase, and its clearing point T(N,I), are expressed in degrees Celsius. All temperature differences are expressed as differences in degrees Celsius.

[0037] The term "clearing point" means the temperature at which the transition between the mesophase and the isotropic phase occurs within the highest temperature range.

[0038] The term "director" is known in the prior art and refers to the favorable 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 or RM molecules. When such anisotropic molecules are arranged uniaxially, the director is the anisotropic axis.

[0039] The term "alignment" or "orientation" refers to the orientation (orientational order) of anisotropic units of a material, such as fragments of small and macromolecules, in a common direction called the "orientation direction." In the orientation layer of a liquid crystal or RM material, the liquid crystal director coincides with the orientation direction so that the orientation direction corresponds to the direction of the anisotropy axis of the material.

[0040] For example, the terms "uniform orientation" or "uniform alignment" of liquid crystal or RM materials in a material layer mean that 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 liquid crystal director lines are parallel.

[0041] The terms "homeotropic structure" or "homeotropic orientation" refer to a film in which the optical axis is substantially perpendicular to the film plane.

[0042] The terms "planar structure" or "planar orientation" refer to a film in which the optical axis is substantially parallel to the film plane.

[0043] The term "negative (optical) dispersion" refers to the inverse birefringence dispersion exhibited in birefringent or liquid crystalline materials or layers, where the magnitude of birefringence (Δn) increases with increasing wavelength (λ). That is, |Δn(450)| < |Δn(550)|, or Δn(450) / Δn(550) < 1, where Δn(450) and Δn(550) are the birefringences of the material measured at wavelengths of 450 nm and 550 nm, respectively. In contrast, "positive (optical) dispersion" refers to a material or layer where |Δn(450)| > |Δn(550)| or Δn(450) / Δn(550) > 1. For example, see A. Uchiyama and T. Yatabe, "Control of Wavelength Dispersion of Birefringence for Oriented Copolycarbonate Films Containing Positive and Negative Birefringent Units," J. Appl. Phys., Vol. 42, pp. 6941-6945 (2003).

[0044] As described above, the optical phase difference at a given wavelength is defined as the product of birefringence and layer thickness [R(λ)=Δn(λ)·d]. Therefore, the optical dispersion can be expressed as "birefringence dispersion" with ratio Δn(450) / Δn(550) or as "phase difference dispersion" with ratio R(450) / R(550), where R(450) and R(550) are the phase differences of the material measured at wavelengths of 450 nm and 550 nm, respectively. Since the layer thickness d does not change with wavelength, R(450) / R(550) is equal to Δn(450) / Δn(550). Therefore, a material or layer with negative or inverse dispersion has R(450) / R(550)<1 or |R(450)|<|R(550)|, and a material or layer with positive or normal dispersion has R(450) / R(550)>1 or |R(450)|>|R(550)|.

[0045] In this invention, unless otherwise specified, "optical dispersion" means phase difference dispersion, i.e., ratio R(450) / R(550).

[0046] The term "high variance" means that the absolute value of the variance deviates significantly from 1, while the term "low variance" means that the absolute value of the variance deviates slightly from 1. Therefore, "high negative variance" means that the variance is considerably less than 1, and "low negative variance" means that the variance is only slightly less than 1.

[0047] The phase difference (R(λ)) of a material can be measured using a spectroscopic ellipsometer, such as the M2000 spectroscopic ellipsometer manufactured by JAWoollam. This instrument can measure the optical phase difference in nanometer units of a birefringent sample, for example, the optical phase difference over a typical wavelength range of 370 nm to 2000 nm for quartz. From this data, it is possible to calculate the dispersion of the material (R(450) / R(550) or Δn(450) / Δn(550)).

[0048] The method for performing these measurements was published in October 2006 by N. Singh at the National Physics Laboratory (London, UK) under the title "Spectroscopic Ellipsometry, Part 1 - Theory and Fundamentals, Part 2 - Practical Examples and Part 3 - Measurements." Following this measurement, the procedure is described in the Retardation Measurement (RetMeas) Manual (2002) and the Guide to WVASE (2002) (Woollam Variable Angle Spectroscopic Ellipsometer) published by JAWoollam Ltd. (Lincoln, Nebraska, USA). Unless otherwise specified, this method is used to determine the phase difference of the materials, films, and devices described in this invention.

[0049] The term "A-plate" refers to an optical phase difference plate that utilizes a layer of uniaxial birefringent material in which its anomalous axis is oriented parallel to the plane of the layer.

[0050] The term "C-plate" refers to an optical phase difference plate that utilizes a layer of uniaxial birefringent material in which its anomalous axis is oriented perpendicular to the plane of the layer.

[0051] In an A / C plate containing a uniformly oriented optically uniaxial birefringent liquid crystal material, the optical axis of the film is given by the direction of the anomalous axis. An A (or C) plate containing a positively birefringent optically uniaxial birefringent material is also called a "positive A (or C) plate" or "+A (or +C) plate".

[0052] A (or C) plates containing films of optically uniaxial birefringent materials with negative birefringence, such as discotic anisotropic materials, are also called "negative A (or C) plates" or "-A (or C) plates" depending on the orientation of the discotic material. Films made of cholesteric calamistic materials that have a reflection band in the UV portion of the spectrum also have the optics of a negative C plate.

[0053] The birefringence Δn is defined as follows: Δn = n e -n o , In the formula, ne is the anomalous refractive index, no is the ordinary refractive index, and n is the effective average refractive index. av. It is given by the following equation: n av. =((2n o 2 +n e 2 ) / 3) 1 / 2 .

[0054] Average refractive index n av. and the normal refractive index n o This can be measured using an Abbe refractometer. Δn can be calculated from the above formula.

[0055] Unless otherwise clearly indicated by the context, the plural form of a term used herein should be interpreted as including the singular form, and vice versa, as used herein.

[0056] All physical properties were determined according to "Merck Liquid Crystals, Physical Properties of Liquid Crystals," published November 1997, Merck, Germany, and are given at a temperature of 20°C unless otherwise explicitly stated. Optical anisotropy (Δn) is determined at a wavelength of 589.3 nm.

[0057] In case of doubt, the definition set forth in C. Tschierske, G. Pelzl, and S. Diele, Angew. Chem. 2004, Vol. 116, pp. 6340–6368 shall be followed.

[0058] Unless otherwise specified in the given general formula, the following terms have the following meanings:

[0059] A "carbyl group" refers to a monovalent or polyvalent organic group having at least one carbon atom, which may contain no further atoms (e.g., -C≡C-) or optionally contain one or more further atoms, such as N, O, S, P, Si, Se, As, Te, or Ge (e.g., carbonyl). A "hydrocarbyl group" means a carbyl group further containing one or more H atoms and optionally one or more heteroatoms, such as N, O, S, P, Si, Se, As, Te, or Ge.

[0060] Calville or hydrocarbyl groups can be saturated or unsaturated. Unsaturated groups include, for example, aryl, alkenyl, or alkynyl groups. Calville or hydrocarbyl groups having more than three carbon atoms may be linear, branched, and / or cyclic, and may contain spirobonds or fused rings.

[0061] Preferred carbyl and hydrocarbyl groups are optionally substituted alkyl, alkenyl, alkynyl, alkoxy, alkylcarbonyl, alkoxycarbonyl, alkylcarbonyloxy and alkoxycarbonyloxy groups having 1 to 40, preferably 1 to 25, and particularly preferably 1 to 18 carbon atoms; optionally substituted aryl or aryloxy groups having 6 to 40, preferably 6 to 25 carbon atoms; or optionally substituted alkylaryl, arylalkyl, alkylaryloxy, arylalkyloxy, arylcarbonyl, aryloxycarbonyl, arylcarbonyloxy and aryloxycarbonyloxy groups having 6 to 40, preferably 6 to 25 carbon atoms. Even more preferred carbyl and hydrocarbyl groups are C1-C 40 Alkyl, C2~C 40 Alkenyl, C2~C 40 Alkinyl, C3~C 40 Allyl, C4~C 40 Alkyldienyl, C4~C 40 Polyenyl, C6~C 40 Aryl, C6~C 40 Alkylaryl, C6~C 40 Arylalkyl, C6~C 40 Alkylaryloxy, C6~C 40 Arylalkyloxy, C2~C 40 Heteroaryl, C4~C 40 Cycloalkyl, C4~C 40 These include cycloalkenyls, in particular C1-C 22 Alkyl, C2~C 22 Alkenyl, C2~C 22 Alkinyl, C3~C 22 Allyl, C4~C 22 Alkyldienyl, C6~C 12 Aryl, C6~C 20 Arylalkyl and C2-C 20 Heteroaryls are preferred.

[0062] A more preferred carbyl and hydrocarbyl group is a linear, branched, or cyclic alkyl group having 1 to 40, preferably 1 to 25, more preferably 1 to 12 carbon atoms, wherein the group is unsubstituted or monosubstituted or polysubstituted with F, Cl, Br, I, or CN, and one or more non-adjacent CH2 groups are independently bonded to each other such that the O and / or S atoms are not directly bonded to each other, such as -C(R x )=C(R x )-, -C≡C-, -N(R x )-, -O-, -S-, -CO-, -CO-O-, -O-CO-, -O-CO-O- may be used as substitutes.

[0063] In the above, R x Preferably, represents H, a halogen, and a linear, branched, or cyclic alkyl chain having 1 to 25 carbon atoms, where one or more non-adjacent carbon atoms may be replaced by -O-, -S-, -CO-, -CO-O-, -O-CO-, or -O-CO-O-, and one or more H atoms may be replaced by fluorine, an optionally substituted aryl or aryloxy group having 6 to 40 carbon atoms, or an optionally substituted heteroaryl or heteroaryloxy group having 2 to 40 carbon atoms.

[0064] Preferred alkyl groups include, for example, methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, s-butyl, t-butyl, 2-methylbutyl, n-pentyl, s-pentyl, cyclopentyl, n-hexyl, cyclohexyl, 2-ethylhexyl, n-heptyl, cycloheptyl, n-octyl, cyclooctyl, n-nonyl, n-decyl, n-undecyl, n-dodecyl, dodecanyl, trifluoromethyl, perfluoron-butyl, 2,2,2-trifluoroethyl, perfluorooctyl, and perfluorohexyl.

[0065] Preferred alkenyl groups include, for example, ethenyl, propenyl, butenyl, pentenyl, cyclopentenyl, hexenyl, cyclohexenyl, heptenyl, cycloheptenyl, octenyl, and cyclooctenyl.

[0066] Preferred alkynyl groups include, for example, ethynyl, propynyl, butynyl, pentynyl, hexynyl, and octinyl.

[0067] Preferred alkoxy groups include, for example, methoxy, ethoxy, 2-methoxyethoxy, n-propoxy, i-propoxy, n-butoxy, i-butoxy, s-butoxy, t-butoxy, 2-methylbutoxy, n-pentoxy, n-hexoxy, n-heptyloxy, n-octyloxy, n-nonyloxy, n-decyloxy, n-undecyloxy, and n-dodecyloxy.

[0068] Preferred amino groups include, for example, dimethylamino, methylamino, methylphenylamino, and phenylamino.

[0069] The aryl and heteroaryl groups may be monocyclic or polycyclic, meaning they may have one ring (e.g., phenyl) or two or more rings, which may be condensed (e.g., naphthyl) or covalently bonded (e.g., biphenyl), or may include a combination of a condensed ring and a linking ring. The heteroaryl group preferably contains one or more heteroatoms selected from O, N, S, and Se.

[0070] In particular, 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 are preferred, and these groups optionally include fused rings and are optionally substituted. Furthermore, 5-membered, 6-membered, or 7-membered aryl groups and heteroaryl groups are preferred, where one or more CH groups may be replaced by N, S, or O such that the O atoms and / or S atoms are not directly bonded to each other.

[0071] 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 the like.

[0072] 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, selenofen, oxazole, isoxazole, 1,2-thiazole, 1,3-thiazole, 1,2,3-oxadiazole, and 1,2,4-oxadiazole. , 1,2,5-oxadiazole, 1,3,4-oxadiazole, 1,2,3-thiadiazole, 1,2,4-thiadiazole, 1,2,5-thiadiazole, 1,3,4-thiadiazole, 6-membered rings, e.g., pyridine, pyridazine, pyrimidine, pyrazine, 1,3,5-triazine, 1,2,4-triazine, 1,2,3-triazine, 1,2,4,5-tetrazine, 1,2,3,4-tetrazine, 1,2,3,5-tetrazine, or condensation groups, e.g., indole, isoindole, indidine, indazole, benzimidazole, benzotriazole, purine, naphthoimidazole, phenantrimidazole, pyridoimidazole, pyrazineimidazole, quinoxalineimidazole, benzoxazole, naphth These are oxazoles, anthroxazoles, phenantroxazoles, isoxazoles, benzothiazoles, benzofurans, isobenzofurans, dibenzofurans, quinolines, isoquinolines, pteridines, benzo-5,6-quinolines, benzo-6,7-quinolines, benzo-7,8-quinolines, benzoisoquinolines, acridines, phenothiazines, phenoxazines, benzopyridazines, benzopyrimidines, quinoxalines, phenazines, naphthyridines, azacarbazoles, benzocarbolins, phenanthridines, phenanthrolines, thieno[2,3b]thiophenes, thieno[3,2b]thiophenes, dithienothiophenes, isobenzothiophenes, dibenzothiophenes, benzothiadiazothiophenes, or combinations thereof. The heteroaryl group may be substituted with alkyl, alkoxy, thioalkyl, fluorine, fluoroalkyl, or further aryl or heteroaryl groups.

[0073] (Non-aromatic) alicyclic and heterocyclic groups include both saturated rings, i.e., those containing only single bonds, and partially unsaturated rings, i.e., those that may contain multiple bonds. Heterocyclic rings preferably contain one or more heteroatoms selected from Si, O, N, S, and Se.

[0074] (Non-aromatic) alicyclic and heterocyclic groups may be monocyclic, i.e., containing only one ring (e.g., cyclohexane), or polycyclic, i.e., containing multiple rings (e.g., decahydronaphthalene or bicyclooctane). Saturated groups are particularly preferred. Furthermore, monocyclic, bicyclic, or tricyclic groups having 3 to 25 carbon atoms are preferred, which may optionally contain fused rings and may optionally be substituted. Furthermore, 5-membered, 6-membered, 7-membered, or 8-membered carbocyclic groups are preferred, where one or more carbon atoms may be replaced by Si, and / or one or more CH groups may be replaced by N, and / or one or more non-adjacent CH2 groups may be replaced by -O- and / or -S-.

[0075] Preferred alicyclic and heterocyclic groups include, for example, five-membered ring groups such as cyclopentane, tetrahydrofuran, tetrahydrothiofuran, and pyrrolidine; six-membered ring groups such as cyclohexane, silinane, cyclohexene, tetrahydropyran, tetrahydrothiopyran, 1,3-dioxane, 1,3-dithiane, and piperidine; seven-membered ring groups such as cycloheptane; and condensation groups such as tetrahydronaphthalene, decahydronaphthalene, indane, bicyclo[1.1.1]-pentane-1,3-diyl, bicyclo[2.2.2]octane-1,4-diyl, spiro[3.3]heptane-2,6-diyl, and octahydro-4,7-methanoindan-2,5-diyl.

[0076] The aryl, heteroaryl, (non-aromatic)alicyclic, and heterocyclic groups optionally have one or more substituents, which are preferably silyl, sulfo, sulfonyl, formyl, amine, imine, nitrile, mercapto, nitro, halogen, or C1-C 12 Alkyl, C6~C 12 Aryl, C1~C 12 The group is selected from those comprising alkoxy, hydroxyl, or combinations thereof.

[0077] Preferred substituents include, for example, dissolution-promoting groups such as alkyl or alkoxy groups, electron-withdrawing groups such as fluorine, nitro or nitrile groups, or substituents that increase the glass transition temperature (Tg) of the polymer, particularly bulky groups such as t-butyl or optionally substituted aryl groups.

[0078] The preferred substituents, also referred to as "L" below, include, for example, F, Cl, Br, I, -OH, -CN, -NO2, -NCO, -NCS, -OCN, -SCN, -C(=O)N(R) x )2, -C(=O)Y x -C(=O)R x , -C(=O)OR x , -N(R x )2, where Rx has the meaning described above, and Yx represents a halogen, an optionally substituted silyl, an optionally substituted aryl or heteroaryl having 4 to 40, preferably 4 to 20 ring atoms, and a linear or branched alkyl, alkenyl, alkynyl, alkoxy, alkylcarbonyl, alkoxycarbonyl, alkylcarbonyloxy or alkoxycarbonyloxy having 1 to 25 carbon atoms, where one or more H atoms may optionally be replaced by F or Cl.

[0079] "Substituting silyl or aryl" is preferably halogen, -CN, R y , -OR y ,-CO-R y , -CO-OR y ,-O-CO-R y or -O-CO-OR y (In the formula, R y This means that it is substituted with H (which represents a linear, branched, or cyclic alkyl chain having 1 to 12 carbon atoms).

[0080] In the equations shown above and below, the substituted phenylene ring [ka] In the formula, L is the same or different and has one of the meanings shown above and below, and is preferably F, Cl, CN, NO2, CH3, C2H5, C(CH3)3, CH(CH3)2, CH2CH(CH3)C2H5, OCH3, OC2H5, COCH3, COC2H5, COOCH3, COOC2H5, CF3, OCF3, OCHF2, OC2F5 or P-Sp-, very preferably F, Cl, CN, CH3, C2H5, OCH3, COCH3, OCF3 or P-Sp-, and most preferably F, Cl, CH3, OCH3, COCH3 or OCF3.

[0081] "Halogen" represents F, Cl, Br, or I, preferably F or Cl, more preferably F.

[0082] The "polymerizable group" (P) is preferably selected from groups containing a CC double bond (-C=C-) or a CC triple bond (-C≡C-), and groups suitable for polymerization involving ring opening, such as oxetane or epoxide groups.

[0083] Preferably, the polymerizable group (P) is CH2=CW 1 -COO-, 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-, CH2=CW 1 -CO-NH-, CH2=CH-(COO) k1 -Phe-(O) k2 -, CH2=CH-(CO) k1 -Phe-(O) k2- Selected from the group consisting of Phe-CH=CH-, During the ceremony, W 1 This represents H, F, Cl, CN, CF3, a phenyl or alkyl group having 1 to 5 carbon atoms, especially H, F, Cl or CH3. W 2 This represents H or an alkyl group having 1 to 5 carbon atoms, particularly H, methyl, ethyl, or n-propyl. W 3 and W 4 Each of these independently represents H, Cl, or an alkyl group having 1 to 5 carbon atoms, and Phe represents 1,4-phenylene, which is optionally substituted with one or more groups L as defined above, but is different from P-Sp, and preferably, preferred substituents L are F, Cl, CN, NO2, CH3, C2H5, OCH3, OC2H5, COCH3, COC2H5, COOCH3, COOC2H5, CF3, OCF3, OCHF2, OC2F5, and also phenyl. k1, k2, and k3 each independently represent either 0 or 1, k3 preferably represents 1, and k4 is an integer between 1 and 10.

[0084] Particularly preferred groups P are CH2=CH-COO-, CH2=C(CH3)-COO-, CH2=CF-COO-, CH2=CH-, CH2=CH-O-, (CH2=CH)2CH-OCO-, (CH2=CH)2CH-O-, [ka] And in the formula W 2 This represents an alkyl group having H or 1 to 5 carbon atoms, particularly H, methyl, ethyl, or n-propyl.

[0085] Further preferred groups (P) are vinyloxy, acrylate, methacrylate, fluoroacrylate, chloroacrylate, oxetane, and epoxide, with acrylate or methacrylate being most preferred, and acrylate being particularly preferred.

[0086] Preferably, all polyreactive polymerizable compounds and their subformulas contain one or more PS groups. Instead of p-, it contains one or more branched groups containing two or more polymerizable groups P (polyreactive polymerizable groups).

[0087] Suitable groups of this type, and polymerizable compounds containing them, are described, for example, in U.S. Patent No. 7,060,200 or U.S. Patent Application Publication No. 2006 / 0172090.

[0088] In particular, the following formula: [ka] A highly reactive polymerizable group selected from the following is preferred. During the ceremony, Alkyl represents a single-bonded, linear, or branched alkylene having 1 to 12 carbon atoms, where one or more non-adjacent CH2 groups are independently bonded to each other such that the O and / or S atoms are not directly bonded to each other, and -C(R x )=C(R x )-, -C≡C-, -N(R x ) may be replaced by -, -O-, -S-, -CO-, -CO-O-, -O-CO-, -O-CO-O-, where one or more H atoms may be replaced by F, Cl or CN, where R x It has one of the above meanings, aa and bb each independently represent 0, 1, 2, 3, 4, 5, or 6. X has one of the meanings shown for X', and P v ~P z Each of these terms, independently of the others, has one of the meanings for P as described above.

[0089] The spacer group Sp is selected from the following group: Sp is an alkylene having 1 to 20, preferably 1 to 12 carbon atoms, which may be mono- or polysubstituted by F, Cl, Br, I or CN, and in addition, in this group, one or more non-adjacent CH2 groups are each independently of the other, so that O and / or S atoms do not bond directly to each other, -O-, -S-, -NH-, -NR xx -, -SiR xx R yy -, -CO-, -COO-, -OCO-, -OCO-O-, -S-CO-, -CO-S-, -NR xx -CO-O-, -O-CO-NR 0xx -, -NR xx -CO-NR yy -, may be replaced by -CH=CH- or -C≡C-, R xx and R yy are each independently of the other H or an alkyl having 1 to 12 carbon atoms, or is selected from Sp'-X' such that the group "P-Sp-" corresponds to the formula "P-Sp'-X'-", where in the formula, Sp' represents an alkylene having 1 to 20, preferably 1 to 12 carbon atoms, which is optionally mono- or polysubstituted by F, Cl, Br, I or CN, and here, furthermore, one or more non-adjacent CH2 groups are each, independently of the other, such that O and / or S atoms do not bond directly to each other, -O-, -S-, -NH-, -NR xx -, -SiR xx R<^ yy -, -CO-, -COO-, -OCO-, -OCO-O-, -S-CO-, -CO-S-, -NR xx -CO-O-, -O-CO-NR 0xx -, -NR xx -CO-NR yy -, may be replaced by -CH=CH- or -C≡C-, X' is -O-, -S-, -CO-, -COO-, -OCO-, -O-COO-, -CO-NR xx -, -NR xx -CO-, -NR xx -CO-NR yy-, -OCH2-, -CH2O-, -SCH2-, -CH2S-, -CF2O-, -OCF2-, -CF2S-, -SCF2-, -CF2CH2-, -CH2CF2-, -CF2CF2-, -CH=N-, -N=CH-, -N=N-, -CH=CR xx -, -CY xx =CY xx - represents -C≡C-, -CH=CH-COO-, -OCO-CH=CH-, or a single bond. R xx and R yy Each of these independently represents either H or an alkyl group having 1 to 12 carbon atoms, and Y xx and Y yy Each of these elements independently represents either H, F, Cl, or CN.

[0090] X' is typically -O-, -S-, -CO-, -COO-, -OCO-, -O-COO-, -CO-NR xx -, -NR xx -CO-, -NR xx -CO-NR yy -or it is a single bond.

[0091] Typical spacer bases Sp or Sp' are, for example, -(CH2) p1 -,-(CH2CH2O) q1 -, -CH2CH2-, -CH2CH2-S-CH2CH2-, -CH2CH2-NH-CH2CH2- or -(SiR xx R yy -O) p1 -where p1 is an integer from 1 to 12, q1 is an integer from 1 to 3, and R xx and R yy The above terms are used.

[0092] A particularly preferred group is the -X'-Sp'- group, which is -(CH2) p1 -, -O-(CH2) p1 -, -OCO-(CH2) p1 -, -OCOO-(CH2) p1 -In the formula, p1 is an integer between 1 and 12.

[0093] Particularly preferred groups Sp' are, for example, 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.

[0094] In the case of the present invention, [ka] This represents trans-1,4-cyclohexylene, [ka] This represents 1,4-phenylene.

[0095] In the present invention, the group -COO-, -C(=O)O-, or -CO2- is the formula [ka] The ester group is represented by -OCO-, -OC(=O)-, -O2C-, or -OOC- in formula [ka] It represents the ester group.

[0096] A "polymer network" is a network in which all polymer chains are interconnected by numerous crosslinks, forming a single macroscopic entity.

[0097] Polymer networks occur in the following types:

[0098] Graft polymer molecules are polymer molecules in which one or more side chains are branched and structurally or spatially different from the main chain.

[0099] • Star polymer molecules are branched polymer molecules from which multiple linear chains or arms arise from a single branching point. If the arms are identical, the star polymer molecule is said to be regular. If adjacent arms consist of different repeating subunits, the star polymer molecule is said to be diverse.

[0100] • Comb-shaped polymer molecules consist of a main chain with two or more triplicate branching points and linear side chains. Comb-shaped polymer molecules are said to be regular when the main chains are identical.

[0101] • Brush polymer molecules consist of a main chain and linear, unbranched side chains, with one or more branching points having functional groups in four or more directions.

[0102] Throughout this description and the claims, the terms “including” and “containing” and their variations, such as “comprising” and “comprises,” mean “including, but not limited to,” and are not intended to exclude other elements. On the other hand, the term “comprise” also includes, but is not limited to, the term “consisting of.”

[0103] Throughout this description and the claims, the terms “possible to obtain” and “obtainable” and their variations thereof mean “including, but not limited to, these” and are not intended to exclude (or not exclude) other elements. On the other hand, the term “possible to obtain” also includes, but is not limited to, the term “obtainable.”

[0104] All concentrations are expressed in weight percentage, and for each whole mixture, all temperatures are expressed in degrees Celsius (°C), and all temperature differences are expressed in degrees Celsius.

[0105] <Detailed explanation>

[0106] In the preferred compound of formula I, R1 Preferably linear or branched alkyl groups, particularly CH3, C2H5, n-C3H7, n-C4H9, n-C5H 11 n-C6H 13 Or CH2C(C2H5)C4H9, and also alkenyl oxy, especially OCH2CH=CH2, OCH2CH=CHCH3, OCH2CH=CHC2H5, alkoxy, especially OC2H5, OC3H7, OC4H9, OC5H 11 and OC6H 13 This represents R. 1 is a linear alkyl group, preferably C5H 11 It represents.

[0107] In the preferred compound of formula I, Z 1 and Z 2 preferably represents a single bond, -C2H4-, -CF2O-, or -CH2O-. In a particularly preferred embodiment, Z 1 and Z 2 Each of these independently represents a single bond.

[0108] In the preferred compound of formula I, L 1 and L 2 Each of these elements independently preferably represents F or an alkyl group, preferably CH3, C2H5, or C3H7. In a preferred embodiment, r2 represents 1 or r1 represents 0.

[0109] Preferred compounds of formula I are exemplified by the following sub-formulas IA to ID.

[0110] [ka]

[0111] [ka]

[0112] [ka]

[0113] In the formula, R 1 , Z 1 , Z 2 Sp, P, r1, and r2 have the meanings defined in Equation I. L 2 , L 3 L is defined independently by equation I. 1 or L 2 It has one of the meanings given to it, R a teeth, [ka] This represents, In the formula, m represents 0, 1, or 2.

[0114] especially, [ka] It represents.

[0115] Preferred compounds of formula I are those of the following subformulas.

[0116] [ka]

[0117] [ka]

[0118] [ka]

[0119] [ka]

[0120] [ka]

[0121] [ka]

[0122] [ka]

[0123] [ka]

[0124] [ka]

[0125] During the ceremony, R a teeth, [ka] This represents, In the formula, m represents 0, 1, or 2.

[0126] Preferably, [ka]

[0127] especially, [ka] This represents,

[0128] R 1 has the meaning given in claim 1, and is preferably a linear alkyl group having 1 to 8 carbon atoms, preferably C2H5, n-C3H7, n-C4H9, n-C5H 11 n-C6H 13 Or n-C7H 15 Most preferably n-C5H 11 It represents.

[0129] The mixture according to the present invention more particularly includes at least one self-orienting additive selected from the following group of compounds.

[0130] [ka]

[0131] [ka]

[0132] [ka]

[0133] [ka]

[0134] [ka]

[0135] [ka]

[0136] [ka]

[0137] [ka]

[0138] [ka]

[0139] [ka]

[0140]

change

[0141]

change

[0142]

change

[0143]

change

[0144]

change

[0145]

change

[0146]

change

[0147]

change

[0148]

change

[0149]

change

[0150]

change

[0151]

Chem.

[0152] In the compounds of formula I and the sub-formulas of the compounds of formula I, R a is preferably

Chem.

[0153] The compounds of formula I can be prepared by methods known per se, for example, as described in standard books of organic chemistry such as Houben-Weyl, Methoden der organischen Chemie, Thieme-Verlag, Stuttgart.

[0154] Preferably, the compounds of formula I can be prepared as given in WO 2017 / 041893.

[0155] The medium according to the invention preferably contains one, two, three, four or more, preferably one self-aligning additive selected from the compounds of formula I, preferably from the compounds of formulae I-1 to I-17.

[0156] The self-aligning additive of formula I is preferably employed in the liquid crystal medium in an amount of 0.1 to 10% by weight, based on the total mixture. Particularly preferred are liquid crystal media containing one or more self-aligning additives, in particular additives selected from the group of compounds of formulae I-1 to I-60, in an amount of 0.5 to 8% by weight, preferably 1 to 5% by weight, based on the total mixture.

[0157] Preferably, using 1.0 to 8% by weight of one or more compounds of formula I results in complete homeotropic orientation of the LC layer for substrate materials with conventional LC thicknesses (3 to 4 μm) and those used in the display industry. Special surface treatments can significantly reduce the amount of one or more compounds of formula I, meaning less than 1.0% by weight.

[0158] Preferably, at least one bireactive or polyreactive mesogenic compound is selected from formula DRM.

[0159] [ka]

[0160] During the ceremony, P 1 and P 2 These represent polymerizable groups independently of each other, Sp 1 and 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. [ka] During the ceremony, A 11 and A 12 When multiple units exist independently of each other, they represent aromatic or alicyclic groups, which optionally contain one or more heteroatoms selected from N, O, and S, and L 11 This can be arbitrarily performed as one or multiple substitutions, L 11 P-Sp-, F, Cl, Br, I, -CN, -NO2, -NCO, -NCS, -OCN, -SCN, -C(=O)NR x R y , -C(=O)OR x -C(=O)R x , -NR x R y-OH, -SF5, optionally substituted silyl, aryl or heteroaryl having 1 to 12, preferably 1 to 6 carbon atoms, and linear or branched alkyl, alkoxy, alkylcarbonyl, alkoxycarbonyl, alkylcarbonyloxy or alkoxycarbonyloxy having 1 to 12, preferably 1 to 6 carbon atoms, where one or more H atoms are optionally replaced by F or Cl. R 00 and R 000 These represent, independently of each other, an alkyl group having H or 1 to 12 carbon atoms. Z 11 When multiple instances exist independently of each other, they are -O-, -S-, -CO-, -COO-, -OCO-, -S-CO-, -CO-S-, -O-COO-, -CO-NR 00 -, -NR 00 -CO-, -NR 00 -CO-NR 000 , -NR 00 -CO-O-, -O-CO-NR 00 -, -OCH2-, -CH2O-, -SCH2-, -CH2S-, -CF2O-, -OCF2-, -CF2S-, -SCF2-, -CH2CH2-, -(CH2) n1 , -CF2CH2-, -CH2CF2-, -CF2CF2-, -CH=N-, -N=CH-, -N=N-, -CH=CR 00 -, -CY 1 =CY 2 -, -C≡C-, -CH=CH-COO-, -OCO-CH=CH- or single bond, preferably -COO-, -OCO- or single bond, Y 1 and Y 2 These represent H, F, Cl, or CN independently of each other. 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.

[0161] Preferred base A 11 and A 12Examples 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.

[0162] Preferred base A 11 and A 12 is selected from 1,4-phenylene, pyridine-2,5-diyl, pyrimidine-2,5-diyl, thiophene-2,5-diyl, naphthalene-2,6-diyl, 1,2,3,4-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.

[0163] Particularly preferred group Z 11 Each of these is preferably selected independently from each other from -COO-, -OCO-, -CH2CH2-, -CF2O-, -OCF2-, -C≡C-, -CH=CH-, -OCO-CH=CH-, -CH=CH-COO-, or a single bond.

[0164] A highly preferred bireactive mesogenic compound for formula DRM is selected from the following formulas.

[0165] [ka]

[0166] [ka]

[0167] During the ceremony, P 0 If multiple groups are present, they are polymerizable groups independently of each other, preferably acrylic, methacrylic, oxetane, epoxy, vinyl, heptadiene, vinyloxy, propenyl ether, or styrene groups. L is the L of formula DRM at each occurrence. 11 Having the same or different meanings as given for, preferably, if multiple occurrences occur independently of each other, they are selected from F, Cl, CN, or alkyl, alkoxy, alkylcarbonyl, alkoxycarbonyl, alkylcarbonyloxy or alkoxycarbonyloxy having 1 to 5 optionally halogenated C atoms. r is 0, 1, 2, 3, or 4. x and y are independent integers, either 0 or identical or distinct integers between 1 and 12. z is either 0 or 1, and z is 0 if an adjacent x or y is 0.

[0168] Compounds of formulas DRMa1, DRMa2, and DRMa3 are preferred, with the compound of formula DRMa1 being particularly preferred.

[0169] Preferably, the polymerizable LC material contains one or more reactive RMs selected from formula MRM.

[0170] [ka]

[0171] In the formula, P 1 , Sp 1 And MG has the meaning given in formula DRM, R is 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 Ry 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.

[0172] Preferably, the reactive mesogen compound of formula MRM is selected from the following formulas.

[0173] [ka]

[0174] [ka]

[0175] [ka]

[0176] [ka]

[0177] In the formula, P 0 L, r, x, y, and z are defined as in equations DRMa-1 to DRMe, 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 This represents, Y 0These are F, Cl, CN, NO2, OCH3, OCN, SCN, SF5, or monofluorinated, oligofluorinated, or polyfluorinated alkyl or alkoxy compounds having 1 to 4 carbon atoms. Z 0 These are -COO-, -OCO-, -CH2CH2-, -CF2O-, -OCF2-, -CH=CH-, -OCO-CH=CH-, -CH=CH-COO-, or single bonds. A 0 If multiple molecules exist independently of each other, they are either unsubstituted or trans-1,4-cyclohexylene, which is substituted with one, two, three, or four L groups. u and v are each independently 0, 1, or 2. w is either 0 or 1. However, the benzene ring and the naphthalene ring may be further substituted with one or more identical or different groups L.

[0178] Compounds of formulas MRM1, MRM2, MRM3, MRM4, MRM5, MRM6, MRM7, MRM9, and MRM10 are preferred, with those of formulas MRM1, MRM4, MRM6, and MRM7 being particularly preferred, and those of MRM1 and MRM7 being even more preferred.

[0179] Compounds of formulas DRM, MRM, and their subformulas are known to those skilled in the art and can be prepared by processes similar to those described in standard organic chemistry textbooks such as Houben-Weyl, Methoden der organischen Chemie [Methods of Organic Chemistry], Thieme-Verlag, and Stuttgart.

[0180] The proportion of the monoreactive, direactive, or polyreactive liquid crystal compound in the entire polymerizable liquid crystal material according to the present invention is preferably in the range of 30 to 99.9% by weight, more preferably in the range of 40 to 99.9% by weight, and even more preferably in the range of 50 to 99.9% by weight.

[0181] In preferred embodiments, the proportion of the bireactive or polyreactive polymerizable mesogenic compound in the polymerizable liquid crystal material according to the present invention is preferably in the range of 5 to 99% by weight, more preferably in the range of 10 to 97% by weight, and even more preferably in the range of 15 to 95% by weight.

[0182] In another preferred embodiment, the proportion of the monoreactive polymerizable mesogenic compound in the polymerizable liquid crystal material according to the present invention, if present, is preferably in the range of 5 to 80% by weight, more preferably in the range of 10 to 75% by weight, and even more preferably in the range of 15 to 70% by weight.

[0183] In another preferred embodiment, the proportion of the polyreactive polymerizable mesogenic compound in the polymerizable liquid crystal material according to the present invention, if present, is preferably in the range of 1 to 30% by weight, more preferably in the range of 2 to 20% by weight, and even more preferably in the range of 3 to 10% by weight.

[0184] In another preferred embodiment, the polymerizable LC material does not contain polymerizable mesogenic compounds having more than two polymerizable groups.

[0185] In another preferred embodiment, the polymerizable LC material does not contain polymerizable mesogenic compounds having fewer than two polymerizable groups.

[0186] In another preferred embodiment, the polymerizable LC material is an achiral material, i.e., it does not contain a chiral polymerizable mesogenic compound or other chiral compound.

[0187] In a further preferred embodiment, the polymerizable LC material preferably comprises at least one monoreactive mesogenic compound selected from formula MRM-1, preferably at least one direactive mesogenic compound selected from formula DRMa-1, and at least one compound of formula I.

[0188] In a further preferred embodiment, the polymerizable LC material preferably comprises at least one monoreactive mesogenic compound selected from formula MRM-7, preferably at least one direactive mesogenic compound selected from formula DRMa-1, and at least one compound of formula I.

[0189] In a further preferred embodiment, the polymerizable LC material preferably comprises at least one monoreactive mesogen compound selected from formula MRM-1 and / or MRM-7, preferably at least one direactive mesogen compound selected from formula DRMa-1, and at least one compound of formula I.

[0190] In a further preferred embodiment, the polymerizable LC material preferably comprises at least two monoreactive mesogenic compounds selected from formula MRM-1 and / or MRM-7, at least one direactive mesogenic compound selected from formula DRMa-1, and at least one compound of formula I.

[0191] In a further preferred embodiment, the polymerizable LC material preferably comprises at least two bireactive mesogenic compounds selected from formula DRMa-1 and at least one compound of formula I.

[0192] In preferred embodiments, the RM formulation optionally includes one or more additives selected from the group consisting of polymerization initiators, surfactants, further stabilizers, catalysts, sensitizers, inhibitors, chain transfer agents, co-reaction monomers, reactive thinners, surfactant compounds, lubricants, wetting agents, dispersants, hydrophobic agents, adhesives, flow improvers, degassing or defoaming agents, defoaming agents, diluents, reactive diluents, auxiliary agents, colorants, dyes, pigments, and nanoparticles.

[0193] In another preferred embodiment, the RM formulation optionally includes one or more additives selected from polymerizable non-mesogenic compounds (reactive thinners). The amount of these additives in the RM formulation is preferably 0-30%, and very preferably 0-25%.

[0194] The reactive thinner used is not only a substance called a reactive thinner in the actual sense, but also one of the auxiliary compounds already mentioned above, which contains one or more complementary reactive units or reactive groups P, 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.

[0195] 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.

[0196] 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.

[0197] Another suitable reactive thinner is polyester (meth)acrylate, which is a (meth)acrylic acid ester of polyesterol.

[0198] 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.

[0199] A suitable reactive thinner is also known by the following formula: 1,4-divinylbenzene, triallyl cyanurate, and dihydrodicyclopentadienyl acrylate. [ka] These are acrylic acid esters of tricyclodecenyl alcohol, as well as allyl esters of acrylic acid, methacrylic acid, and cyanoacrylic acid.

[0200] 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.

[0201] 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.

[0202] Further examples of this group include alkoxylated phenol compounds, such as ethoxylated and propoxylated bisphenols.

[0203] These reactive thinners may further be, for example, epoxides or urethane (meth)acrylates.

[0204] 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.

[0205] 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.

[0206] Such epoxides and urethane (meth)acrylates are included in the compounds listed above as “mixed forms.”

[0207] 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.

[0208] 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.

[0209] Naturally, mixtures of these diluents can also be used in the composition according to the present invention.

[0210] 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.

[0211] 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 polymerizable LC material.

[0212] Antifoaming and defoaming 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 agents for promoting scratch resistance (c8) cannot be strictly distinguished from one another in their respective functions.

[0213] 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).

[0214] Accordingly, certain additives can therefore be classified into the following numerous groups c1) to c8).

[0215] 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.

[0216] 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.

[0217] 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).

[0218] 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.

[0219] 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.

[0220] 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.

[0221] 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.

[0222] 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.

[0223] Such additives are also 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.

[0224] For example, such an additive is also available from 3M as FC4430 (registered trademark).

[0225] For example, such additives are also available from Cytonix as FluorN® 561 or FluorN® 562.

[0226] For example, such fertilizers are also available from Merck as Tivida® FL2300 and Tivida® FL2500.

[0227] 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.

[0228] 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).

[0229] 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.

[0230] The thermosetting aids of group c3) include, for example, primary OH groups that can react with the isocyanate group of the binder.

[0231] Examples of thermosetting aids that may be used are BYK®-370, BYK®-373, and BYK®-375, which are available from BYK.

[0232] The additives of group c3) are used as desired 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 polymerizable LC material.

[0233] 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.

[0234] 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.

[0235] 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.

[0236] 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.

[0237] 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.

[0238] 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.

[0239] 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).

[0240] 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.

[0241] 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.

[0242] 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.

[0243] The additives of group c6) are used as desired 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 polymerizable LC material.

[0244] Further 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.

[0245] 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.

[0246] 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.

[0247] 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.

[0248] 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®.

[0249] 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.

[0250] However, when these additives are added to the polymerizable LC material 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 polymerizable LC material. Since 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, these concentration data are merely guidelines. 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.

[0251] 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.

[0252] 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.

[0253] 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,

[0254] 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.

[0255] 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"),

[0256] 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.

[0257] 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,

[0258] 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.

[0259] 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,

[0260] 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,

[0261] 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.

[0262] Acylaminophenols, for example, 4-hydroxylauroylanilide, 4-hydroxystearoylanilide, and octyl N-(3,5-di-tert-butyl-4-hydroxyphenyl)carbamate,

[0263] 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,

[0264] 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.

[0265] Ascorbic acid (vitamin C) and ascorbic acid derivatives, such as ascorbyl palmitate, laurate and stealth, as well as ascorbyl sulfate and phosphate,

[0266] 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,

[0267] 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,

[0268] 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,

[0269] 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.

[0270] 2-hydroxybenzophenones such as derivatives of 4-hydroxy, 4-methoxy, 4-octyloxy, 4-decyclooxy, 4-dodecyloxy, 4-benzyloxy, 4,2',4'-trihydroxy and 2'-hydroxy-4,4'-dimethoxy,

[0271] 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.

[0272] 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.

[0273] 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

[0274] 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.

[0275] In another preferred embodiment, the polymerizable LC material preferably comprises one or more specific antioxidants selected from the Irganox® series, for example, Irganox® 1076 and Irganox® 1010, which are commercially available from Ciba and Switzerland.

[0276] In another preferred embodiment, the polymerizable LC material comprises one or more, more preferably two or more, photopolymerization initiators. Typically available radical photoinitiators are 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, and Darcure TPO. Further suitable photoinitiators are preferably selected from commercially available oxime ester photoinitiators such as Oxe02 (Ciba) or N-1919 T (ADEKA).

[0277] The overall concentration of polymerization initiators (one or more types) in the polymerizable LC material is preferably 0.1 to 10%, very preferably 0.5 to 8%, and more preferably 2 to 6%.

[0278] Preferably, the polymerizable LC material includes one or more compounds of formula I, a) One or more bireactive or polyreactive polymerizable mesogenic compounds, b) One or more photoinitiators of any kind, c) Optionally one or more monoreactive polymerizable mesogenic compounds, d) One or more antioxidants as optional, e) One or more types of adhesion promoters, f) One or more surfactants of any kind, g) One or more stabilizers of any kind, h) Optionally, one or more monoreactive, direactive, or polyreactive polymerizable nonmesogenic compounds, i) One or more dyes that exhibit an absorption maximum at a wavelength used to initiate photopolymerization, j) One or more chain transfer agents of any choice, k) One or more stabilizers of any kind, l) One or more types of lubricants and flow aids, and m) One or more diluents of your choice Includes.

[0279] More preferably, polymerizable LC materials are a) One or more compounds of formula I, preferably selected from compounds of formula I-1 to I-60, preferably in an amount of 0.1 to 10% by weight, b) One or more monoreactive polymerizable mesogenic compounds, preferably two or more monoreactive polymerizable mesogenic compounds, and preferably in an amount of 10 to 95% by weight, very preferably 25 to 85% by weight, preferably selected from compounds of formula MRM-1 and / or MRM-7. c) One or more photoinitiators, preferably in an amount of 0.1 to 10% by weight, d) Optionally one or more, preferably two or more, bireactive polymerizable mesogenic compounds, and, if present, in a total amount preferably 10 to 90% by weight, very preferably 15 to 75% by weight, preferably selected from compounds of formula DRM-1. e) Optionally, one or more antioxidants, esters of unsubstituted and substituted benzoic acid, and particularly preferably selected from Irganox® 1076, if present, preferably in an amount of 0.01 to 2% by weight, and very preferably 0.05 to 1% by weight. f) Optionally, one or more lubricants and flow aids preferably selected from BYK® 388, FC4430 and / or FluorN562, and if present, preferably in an amount of 0.1 to 5% by weight, very preferably 0.2 to 3% by weight, and g) Optionally, one or more diluents, preferably selected from n-dodecanol, in an amount of preferably 0.1 to 5% by weight, and very preferably 0.2 to 3% by weight. Includes.

[0280] The present invention further relates to a method for preparing polymerizable LC materials as described above and below, comprising the step of mixing one or more compounds of formula I with at least one bireactive or polyreactive mesogenic compound.

[0281] The present invention further, • Provide layers of polymerizable LC material described above and below on a substrate, • Polymerizable LC material is polymerized by photopolymerization. Optionally, remove the polymerized LC material from the substrate and / or optionally, transfer it to another substrate. This relates to a method for preparing polymer films.

[0282] Furthermore, polymerizable LC materials can be dissolved in a suitable solvent.

[0283] In another preferred embodiment, the polymerizable LC material comprises one or more solvents preferably selected from organic solvents. The solvents are preferably selected from ketones, e.g., acetone, methyl ethyl ketone, methyl propyl ketone, methyl isobutyl ketone, or cyclohexanone; acetates, e.g., methyl, ethyl, or butyl acetate, or methyl acetate; alcohols, e.g., methanol, ethanol, or isopropyl alcohol; aromatic solvents, e.g., toluene or xylene; alicyclic hydrocarbons, e.g., cyclopentane or cyclohexane; halogenated hydrocarbons, e.g., dichloromethane or trichloromethane; glycols or esters thereof, e.g., PGMEA (propyl glycol monomethyl ether acetate), γ-butyrolactone. It is also possible to use binary, ternary, or more mixtures of the above solvents.

[0284] When the polymerizable LC material contains one or more solvents, the total concentration of all solids containing RM in the solvent (one or more) is preferably 10 to 60%.

[0285] This solution is then applied or printed onto a substrate using known techniques such as spin coating or printing, and the solvent is evaporated before polymerization. In many cases, heating the coated solution is suitable to accelerate the evaporation of the solvent.

[0286] Polymerizable LC materials can be applied to substrates using conventional coating techniques such as spin coating and blade coating. They can also be applied to substrates using 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 using stamps or printing plates.

[0287] Suitable substrate materials and substrates are known to experts and documented in the literature, for example, as conventional substrates used in the optical film industry, such as glass or plastic. Preferred substrates particularly suitable for polymerization include polyesters such as polyethylene terephthalate (PET) or polyethylene naphthalate (PEN), polyvinyl alcohol (PVA), polycarbonate (PC), triacetylcellulose (TAC), or cycloolefin polymer (COP), or commonly known color filter materials.

[0288] Preferably, optical films obtained or that can be obtained from other polymerizable LC materials, and even more preferably, O-plates, A-plates, and other materials with different orientations, can function as substrates.

[0289] The polymerizable LC material preferably exhibits a uniform orientation throughout the entire layer. Preferably, the polymerizable LC material exhibits a uniform homeotropic orientation.

[0290] Another method used to support homeotropic orientation involves corona discharge treatment of a plastic substrate to generate functional groups such as alcohols or ketones on the substrate surface. These polar groups can interact with polar groups present in RM or surfactants, thereby promoting homeotropic orientation.

[0291] To produce the polymer film according to the present invention, the polymerizable compound in the polymerizable LC material is polymerized or crosslinked in situ by photopolymerization (when one type of compound contains two or more polymerizable groups).

[0292] Photopolymerization can be carried out in a single step. Furthermore, compounds that did not react in the first step can be photopolymerized or crosslinked in a second step ("final curing").

[0293] In a preferred preparation method, the polymerizable LC material is coated onto a substrate and then photopolymerized, for example by exposure to light irradiation, as described in International Publication 01 / 20394, British Patent No. 2,315,072, or International Publication 98 / 04651.

[0294] Photopolymerization of LC materials is preferably achieved by exposure to chemical radiation. Chemical radiation refers to irradiation with light such as ultraviolet, infrared, and visible light, irradiation with X-rays and gamma rays, or irradiation with high-energy particles such as ions and electrons. Preferably, polymerization is carried out by light irradiation, particularly with UV light. As a light source for chemical radiation, for example, a single UV lamp or a set of UV lamps can be used. When high lamp power is used, the curing time can be shortened. Another possible light source for light radiation is a laser, for example, a UV laser, IR laser, or visible laser.

[0295] The curing time depends particularly on the reactivity of the polymerizable LC material, the thickness of the coating layer, the type of polymerization initiator, and the output of the UV lamp. The curing time is preferably 5 minutes or less, very preferably 3 minutes or less, and most preferably 1 minute or less. For mass production, a short curing time of 30 seconds or less is preferred.

[0296] A suitable UV radiation power is preferably 5 to 200 mW / cm². -2 Within the range of 50 to 175 mW / cm², more preferably 50 to 175 mW / -2 Within this range, most preferably 100-150 mW / cm² -2 It is within the range.

[0297] As a function of time in relation to the applied UV radiation, a suitable UV dose is preferably 25 to 7200 mJcm². -2 Within the range of 500 to 7200 mJcm -2 Within this range, most preferably 3000 to 7200 mJcm -2 It is within the range.

[0298] Photopolymerization is preferably carried out under an inert gas atmosphere, preferably under a heated nitrogen atmosphere, but polymerization in air is also possible.

[0299] Photopolymerization is preferably carried out at a temperature of 1 to 70°C, more preferably 5 to 50°C, and even more preferably 15 to 30°C.

[0300] The polymerized LC film according to the present invention exhibits good adhesion to plastic substrates, particularly TAC, COP, and color filters. Therefore, it can be used as an adhesive or base coating for subsequent LC layers that would otherwise not adhere well to the substrate.

[0301] The preferred thickness of the polymerized LC film according to the present invention is determined by the desired optical properties of the film or the final product. For example, if the polymerized LC film does not primarily act as an optical layer, but rather as, for example, an adhesive layer, alignment layer, or protective layer, its thickness is preferably 1 μm or less, particularly 0.5 μm or less, and very preferably 0.2 μm or less.

[0302] For example, the uniform homeotropic or planar-aligned polymer films of the present invention can be used, for example, as phase difference films or compensation films in liquid crystal displays to improve contrast and brightness at wide viewing angles and reduce chromaticity. These can be used outside of switchable liquid crystal cells in LCDs, or between substrates that form switchable liquid crystal cells and contain switchable liquid crystal media, usually glass substrates (in cell applications).

[0303] For optical applications of polymer films, the thickness is preferably 0.5 to 10 μm, very preferably 0.5 to 5 μm, and especially 0.5 to 3 μm.

[0304] The optical retardation (δ(λ)) of a polymer film is given by equation (7) below as a function of the wavelength of the incident light: δ(λ)=(2πΔn·d) / λ (7) In the equation, (Δn) is the birefringence of the film, (d) is the thickness of the film, and λ is the wavelength of the incident beam.

[0305] According to Snellius's law, birefringence as a function of the direction of the incident beam is defined as follows: Δn = sinΘ / sinΨ (8) In the formula, sinΘ is the angle of incidence to the film or the tilt angle of the optical axis, and sinΨ is This is the corresponding angle of reflection.

[0306] Based on these laws, birefringence, and consequently optical delay, depends on the film thickness and the tilt angle of the optical axis within the film (see Berek compensator). Therefore, those skilled in the art recognize that different optical retardations or different birefringences can be induced by adjusting the orientation of liquid crystalline molecules in a polymer film.

[0307] The birefringence (Δn) of the polymer film according to the present invention is preferably in the range of 0.01 to 0.30, more preferably in the range of 0.01 to 0.25, and even more preferably in the range of 0.01 to 0.16.

[0308] The optical retardation as a function of the thickness of the polymer film according to the present invention is less than 200 nm, preferably less than 180 nm, and more preferably less than 150 nm.

[0309] In particular, the polymer film according to the present invention exhibits high temperature stability for intracellular applications. Therefore, the polymer film exhibits temperature stability up to 300°C, preferably up to 250°C, and more preferably up to 230°C.

[0310] Furthermore, the polymer film of the present invention can also be used as an alignment film for other liquid crystal or RM materials. For example, in an LCD, it can be used to induce or improve the alignment of a switchable liquid crystal medium, or to align a subsequent layer of polymerizable LC material coated thereon. In this way, a stack of polymerized LC films can be fabricated.

[0311] In short, the polymerized LC film and polymerizable LC material according to the present invention are useful in optical elements such as liquid crystal displays or projection systems, decorative images, polarizers, compensators, alignment layers, circular polarizers or color filters for the preparation of liquid crystals or effect pigments, and in reflective films having spatially changing reflective colors, such as multicolor images for decorative, information storage or security applications, such as IDs or credit cards and banknotes.

[0312] The polymerized LC film according to the present invention can be used in transmissive or reflective displays. These include conventional OLED displays or LCDs, particularly LCDs in DAP (deformation of aligned phase) or VA (vertically aligned) mode, such as ECB (electrically controlled birefringence), CSH (colour super homeotropic), VAN or VAC (vertically aligned nematic or cholesteric) displays, MVA (multi-domain vertically aligned) or PVA (patterned vertically aligned) displays, as well as bend-mode displays or hybrid-type displays, such as OCB (optically compensated bend cell or optically compensated birefringence), R-OCB (reflective OCB), HAN (hybrid aligned nematic), or π-cell displays, and furthermore, TN (twisted It can be used in displays in nematic (twisted nematic), HTN (highly twisted nematic), or STN (super twisted nematic) modes, in AMD-TN (active matrix driven TN), or in IPS (in-plane switching) mode displays, also known as "super TFT" displays. VA, MVA, PVA, OCB, and pycell displays are particularly preferred.

[0313] The polymerizable LC materials and polymer films according to the present invention are particularly useful for 3D displays, as described in European Patent Publication No. 0829744, European Patent Publication No. 0887666, European Patent Publication No. 0887692, U.S. Patent No. 6,046,849, U.S. Patent No. 6,437,915 and page 280 of the "Proceedings of the SID 20th International Display Research Conference, 2000". A 3D display of this type, including the polymer film according to the present invention, is another object of the present invention.

[0314] 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.

[0315] Many of the compounds or mixtures of the compounds 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.). Varieties known in themselves but not mentioned herein can also be used.

[0316] 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.

[0317] 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).

[0318] 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.

[0319] Next, the present invention will be described in more detail with reference to the following examples, but these examples are illustrative and do not limit the scope of the present invention.

[0320] The example below is intended to illustrate the present invention without limiting it. [Examples]

[0321] <RM used> For the following mixtures, the following RMs are used.

[0322] [ka]

[0323] <Surface-active additives used>

[0324] [ka]

[0325] <Additives used>

[0326] [ka]

[0327] <Mixtures used> The following comparative mixture CM-1 is prepared.

[0328] [Table 1]

[0329] The following comparative mixture CM-2 is prepared.

[0330] [Table 2]

[0331] The following mixture M-1 is prepared.

[0332] [Table 3]

[0333] The following mixture M-2 is prepared.

[0334] [Table 4]

[0335] The following mixture M-3 is prepared.

[0336] [Table 5]

[0337] The following mixture M-4 is prepared.

[0338] [Table 6]

[0339] The following mixture M-5 is prepared.

[0340] [Table 7]

[0341] The following mixture M-6 is prepared.

[0342] [Table 8]

[0343] The following mixture M-7 is prepared.

[0344] [Table 9]

[0345] The following mixture M-8 is prepared.

[0346] [Table 10]

[0347] The following mixture M-9 is prepared.

[0348] [Table 11]

[0349] The following mixture M-10 is prepared.

[0350] [Table 12]

[0351] The following mixture M-11 is prepared.

[0352] [Table 13]

[0353] The following mixture M-12 is prepared.

[0354] [Table 14]

[0355] In each case, the mixture was dissolved in toluene:cyclohexanone (7:3) in the 30% solids component.

[0356] <Experiment 1> Polymer films are produced from mixtures CM-1 and M-1 using the following methods, respectively. • The dissolved mixture is bar-coated onto the substrate using a Meyer bar 4. Either the substrate is subjected to corona treatment prior to coating, or corona discharge treatment is not performed. Annealing for 60 seconds at room temperature, followed by 60 seconds at 50°C. • Using a belt conveyor type fusion lamp Light Hammer 6, curing under N2 (74% output, 3.6 m·min) -1 )

[0357] Each film was visually inspected for +C orientation between cross polarizers after each annealing process and after curing, and this data is shown below.

[0358] [Table 15]

[0359] When using CSA-1, +C orientation is not observed unless corona treatment is performed.

[0360] <Experiment 2> Polymer films are produced from mixtures M-2 to M-5 using the following methods. • The dissolved mixture is bar-coated onto the substrate using a Meyer bar 4. • The substrate is not subjected to corona discharge treatment prior to coating. Annealing for 60 seconds at room temperature, followed by 60 seconds at 50°C. • Using a belt conveyor type fusion lamp Light Hammer 6, curing under N2 (74% output, 3.6 m·min) -1 )

[0361] Each film was visually inspected for +C orientation between cross polarizers after each annealing process and after curing, and this data is shown below.

[0362] [Table 16]

[0363] <Experiment 3> Polymer films are produced from mixtures CM-2 and M-6 to M-10 using the following methods, respectively. • The dissolved mixture is bar-coated onto the substrate using a Meyer bar 4. • The substrate is not subjected to corona discharge treatment prior to coating. Annealing for 60 seconds at room temperature, followed by 60 seconds at 50°C. • Using a belt conveyor type fusion lamp Light Hammer 6, curing under N2 (74% output, 3.6 m·min) -1 )

[0364] Each film was visually inspected for +C orientation between cross polarizers after each annealing process and after curing, and this data is shown below.

[0365] [Table 17]

[0366] <Experiment 4> Polymer films are produced from mixtures M11 and M12 using the following methods, respectively. • M11 is spin-coated onto PI glass at 1500 rpm for 30 seconds. The film is annealed at 60°C for 60 seconds. The film was cured under N2 using a belt-conveyor type fusion lamp Light Hammer 6 (74% output, 3.6 m·min). -1 ) • M12 is spin-coated onto the cured M11 film at 1500 rpm for 30 seconds. The film is annealed at room temperature for 60 seconds. The film was cured under N2 using a belt-conveyor type fusion lamp Light Hammer 6 (74% output, 3.6 m·min). -1 )

[0367] Each film was visually inspected for orientation between cross polarizers after each annealing process and after curing, and this data is shown below.

[0368] [Table 18]

[0369] This example shows that coating the top of a cured M-11 film with M-12 results in good off-axis performance.

[0370] Even when the double-layer film is tilted off-axis, there is no visible change in color. However, if the M-12 film is not on top, there is a visible change in color when viewed between the cross polarizers.

Claims

1. A polymerizable LC material comprising at least one bireactive or polyreactive mesogenic compound in a total proportion ranging from 5 to 99% by weight, and at least one compound of formula I in a total proportion ranging from 1 to 5% by weight. 【Chemistry 1】 (In the formula, R １ represents an alkyl or alkoxy group having H, 1 to 15 C atoms, and in addition, one or more CH groups. ２ The groups are -CH=CH-, -C≡C-, and -CF, where the oxygen atoms are not directly bonded to each other, independently of each other. ２ O-, -CH=CH-, 【Chemistry 2】 -O-, -CO-O-, -O-CO- may be substituted, and in the group, one or more H atoms may be substituted with halogens. R ２ This represents an alkyl group having H or 1 to 8 C atoms. 【Transformation 3】 This represents, L １ and L ２ In each case, F, Cl, Br, I, -CN, and -NO are independent of each other. ２ -NCO, -NCS, -OCN, -SCN, represents an alkyl, alkoxy, alkylcarbonyl, alkoxycarbonyl, alkylcarbonyloxy or alkoxycarbonyloxy having 1 to 5 C atoms in a linear or branched structure, and one or more H atoms in the group may be replaced with F or Cl. L ３ is, in each case independently of one another, H, F, Cl, Br, I, -CN, -NO ２ , -NCO, -NCS, -OCN, -SCN, alkyl, alkoxy, alkylcarbonyl, alkoxycarbonyl, alkylcarbonyloxy or alkoxycarbonyloxy having 1 to 5 C atoms in linear or branched form, and in addition one or more H atoms in the group may be replaced by F or Cl, m represents 0, 1, or 2. n represents 2, P represents a polymerizable group, Sp represents a spacer group (also called a spacer) or a single bond. Z １ and Z ２ In each case, they are independent single bonds: -O-, -S-, -CO-, -CO-O-, -OCO-, -O-CO-O-, -OCH ２ -ien-CH ２ -ien-CH ２ O-, -CF ２ O-, -OCF ２ -ien-CH ２ CH ２ -, - (CH ２ ) ４ -, -CF ２ CH ２ -ien-CH ２ CF ２ -, -CF ２ CF ２ -, -CH=CH-, -CF=CF-, -C≡C-, -CH=CH-COO- or -OCO-CH=CH-, p1 represents 1, 2, or 3. r1 is 0, 1, 2, or 3, where p1 + r1 is 4 or less. p2 represents 0, 1, 2, or 3. r² represents 0, 1, 2, or 3, where p² + r² is less than or equal to 4.

2. The polymerizable LC material according to claim 1, comprising two or more monoreactive mesogenic compounds and two or more direactive mesogenic compounds.

3. The polymerizable LC material according to claim 1 or 2, wherein R2 represents H, CH3, C2H5, C3H7, or C4H9.

4. The polymerizable LC material according to any one of claims 1 to 3, wherein p1 represents 2 or 3.

5. The polymerizable LC material according to claim 1 or 2, wherein at least one compound of formula I is selected from the following sub-formulas. 【Chemistry 4】 【Transformation 5】 【Transformation 6】 【Transformation 7】 【Transformation 8】 【Chemistry 9】 【Chemistry 10】 【Chemistry 11】 【Chemistry 12】 (In the formula, Ra is, 【Chemistry 13】 This represents, In the formula, m represents 0, 1, or 2. R1 represents C2H5, n-C3H7, n-C4H9, n-C5H11, n-C6H13, or n-C7H15. R2 represents H, CH3, C2H5, C3H7, or C4H9.

6. The polymerizable LC material according to claim 1 or 2, wherein at least one compound of formula I is selected from the following sub-formulas. 【Chemistry 14】 【Chemistry 15】 【Chemistry 16】 【Chemistry 17】 [Chemistry 18] 【Chemistry 19】 【Chemistry 20】 【Chemistry 21】 【Chemistry 22】 【Chemistry 23】 【Chemistry 24】 【Chemistry 25】 【Chemistry 26】 【Chemistry 27】 【Chemistry 28】 【Chemistry 29】 【Transformation 30】 【Chemistry 31】 【Chemistry 32】 【Transformation 33】 【Transformation 34】 【Chemistry 35】

7. The polymerizable LC material according to any one of claims 1 to 6, wherein at least one bireactive or polyreactive mesogen compound is selected from formula DRM. 【Transformation 36】 (In the formula, P １ and P ２ Each of these independently represents a polymerizable group, Sp １ and Sp ２ These are each independently of each other, either a spacer group or a single bond. MG is a rod-shaped mesogenic group, and this group is selected from formula MG. 【Chemistry 37】 During the ceremony, A １１ and A １２ If multiple instances of L appear, they independently represent aromatic or alicyclic groups, and each group may contain one or more heteroatoms selected from N, O, and S. １１ It may be replaced by one or multiple substitutions. L １１ is P-Sp-, F, Cl, Br, I, -CN, -NO ２ , -NCO, -NCS, -OCN, -SCN, -C(=O)NR ００ R ０００ , -C (=O) OR ００ , -C(=O)R ００ , -NR ００ R ０００ -OH, -SF ５ , which may be substituted, silyl, aryl or heteroaryl having 1 to 12 C atoms, linear or branched alkyl, alkoxy, alkylcarbonyl, alkoxycarbonyl, alkylcarbonyloxy or alkoxycarbonyloxy having 1 to 12 C atoms, wherein one or more H atoms may be replaced with F or Cl. R ００ and R ０００ Each of these represents an alkyl group having either H or 1 to 12 C atoms independently of each other. Z １１ If multiple occurrences occur, 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 are represented. Y １ and Y ２ Each of these independently represents H, F, Cl, or CN. n is 1, 2, 3 or 4, and n1 is an integer between 1 and 10.

8. The polymerizable LC material according to any one of claims 1 to 7, wherein at least one bireactive mesogenic compound is selected from the following formulas. 【Transformation 38】 【Chemistry 39】 (In the formula, P ０ If multiple groups appear, they are independently acrylic, methacrylic, oxetane, epoxy, vinyl, heptadiene, vinyloxy, propenyl ether, or styrene groups. L is the same or different in each occurrence in formula DRM １１ It has one of the meanings that can be given to it, r is 0, 1, 2, 3, or 4. x and y are either 0 or identical or distinct integers between 1 and 12, respectively. z is either 0 or 1 independently, and if an adjacent x or y is 0, then z is 0.

9. A polymerizable LC material according to any one of claims 1 to 8, comprising at least one reactive mesogenic compound selected from formula MRM. 【Chemistry 40】 (In the formula, P １ , Sp １ And MG has the meaning as given in formula DRM, R is 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 C atoms which may be substituted, where one or more H atoms may be replaced with F or Cl. X is a halogen, and R ｘ and R ｙ Each of these is an alkyl group that independently has either H or 1 to 12 C atoms.

10. The polymerizable LC material according to any one of claims 1 to 9, wherein at least one type of reactive mesogenic compound is selected from the following formulas. 【Chemistry 41】 【Chemistry 42】 【Chemistry 43】 【Chemistry 44】 (In the formula, P ０ L, r, x, y, and z are defined as given in claim 8, R ０ is alkyl, alkoxy, thioalkyl, alkylcarbonyl, alkoxycarbonyl, alkylcarbonyloxy or alkoxycarbonyloxy having 1 to 15 C atoms, or Y ０ represents, Y ０ These are F, Cl, CN, NO ２ , OCH ３ , OCN, SCN, SF ５ or a monofluorinated, oligofluorinated, or polyfluorinated alkyl or alkoxy having 1 to 4 C atoms, Z ０ is -COO-, -OCO-, -CH ２ CH ２ -, -CF ２ O-, -OCF ２ -, -CH=CH-, -OCO-CH=CH-, -CH=CH-COO- or a single bond, A ０ If multiple instances occur, they are 1,4-phenylene or trans-1,4-cyclohexylene, either unsubstituted or substituted with one, two, three, or four L groups, independently of each other. u and v are each independently 0, 1, or 2. w is 0 or 1, and However, the benzene and naphthalene rings may be substituted with one or more identical or different groups L.

11. The polymerizable LC material according to any one of claims 2 to 10, wherein the proportion of a reactive polymerizable mesogenic compound is in the range of 5 to 80% by weight.

12. A polymerizable LC material according to any one of claims 1 to 11, comprising one or more photoinitiators.

13. A polymerizable LC material according to any one of claims 1 to 8, comprising one or more additives selected from the group consisting of surfactants, further stabilizers, catalysts, sensitizers, inhibitors, chain transfer agents, co-reaction monomers, reactive thinners, surfactant compounds, lubricants, wetting agents, dispersants, hydrophobic agents, adhesives, flow improvers, degassing or defoaming agents, defoaming agents, diluents, reactive diluents, auxiliary agents, colorants, dyes, pigments, and nanoparticles.

14. A method for preparing a polymerizable LC material according to any one of claims 1 to 13, A method comprising the step of mixing one or more compounds of formula I with at least one bireactive or polyreactive mesogenic compound.

15. A method for preparing a polymer film, - Provide a layer of polymerizable LC material according to any one of claims 1 to 13 on a substrate, - Photopolymerize polymerizable LC material, and A method for optionally removing polymerized LC material from a substrate and / or optionally providing it on another substrate.

16. A polymer film which is a polymer of the polymerizable LC material according to any one of claims 1 to 13.

17. The polymer film according to claim 16, wherein the LC material is homeotopically oriented.

18. Use of the polymer film according to claim 16 or 17 or the polymerizable LC material according to any one of claims 1 to 13 in optical applications, electro-optical applications, information storage applications, decorative applications and security applications.

19. An optical component or device comprising at least one polymer film according to claim 16 or 17 or a polymerizable LC material according to any one of claims 1 to 13.

20. A polymer film according to at least one type of claim 16 or 17, and One or more optical films which are polymers of polymerizable LC materials different from the polymerizable LC material described in any one of claims 1 to 13, and An optical component or device according to claim 19, including the following:

Images