Reactive Mesogens

Abstract

The present invention relates to reactive mesogens (RMs), mixtures and formulations containing same, polymers obtained from such RMs and RM mixtures, and the use of RMs, RM mixtures and polymers in optical or electro-optical components or devices.

Description

[Technical field]

[0001] The present invention relates to reactive mesogens (RMs), mixtures and formulations containing same, polymers obtained from such RMs and RM mixtures, and the use of RMs, RM mixtures and polymers in optical or electro-optical components or devices.

[0002] Background and Prior Art Reactive mesogens (RMs), mixtures or formulations containing them and the polymers obtained therefrom can be used to produce optical components such as compensation films, retardation films, polarizing films or lenses. These optical components can be used in optical or electro-optical devices such as LC displays. Usually, the RMs or RM mixtures are polymerized by an in-situ polymerization process.

[0003] The production of RM film products with high birefringence is crucial in producing the optical components of modern display devices such as LCD and virtual reality (AR / VR) applications. For example, brightness enhancement films such as 3M DBEF™ are often integrated into displays to increase brightness or reduce the number of light sources in the backlight unit. Broadband cholesteric films can also be used for this purpose, with their optical properties dependent on the broadening that can be achieved during processing. A film with good broadening ability can be processed faster on the production line and also have better optical properties.

[0004] In this regard, it is possible to polymerize cholesteric reactive mesogen films to obtain a gradient of helical pitch, thereby broadening the reflection band of the film. Thin films with good optical properties depend on the inclusion of at least one suitable highly birefringent RM.

[0005] The broadening of the cholesteric film is determined by the structure of the highly birefringent material in the reactive mesogen mixture. The compound must be highly birefringent, allowing for band broadening, while also having good solubility and a wide nematic range, preferably without too high a melting point. Highly birefringent reactive mesogens produced to date with these properties can only broaden the band of a cholesteric film by a certain amount before the film becomes hazy.

[0006] It is possible to increase the birefringence of the RM while maintaining its polymerizability and good physical properties, but this requires the incorporation of certain chemical groups into the compound, such as tolane groups.

[0007] Mesogenic tolane derivatives are known, for example, from US Pat. No. 6,514,578, GB Pat. No. 2 388 599, US Pat. No. 7,597,942, US Pat. No. 2003-072893, US Pat. No. 2006-0119783 or JP 2015-205843 A1.

[0008] In general, the tolane group is relatively reactive and in most cases unsuitable for exposure to light, making it difficult to use in many optical applications due to yellowing and other degradation effects. Furthermore, mesogenic tolane derivatives often have limited solubility in RM mixtures and organic solvents, limiting their use.

[0009] It is therefore an object of the present invention to provide improved RMs, RM mixtures and RM formulations that do not have the disadvantages of the materials known from the prior art. In particular, it is an object to provide RMs, RM mixtures and RM formulations that are suitable for the preparation of polymers by in situ polymerization and at the same time exhibit high birefringence, good solubility, improved broadbanding ability, favorable transition temperatures and high resistance to yellowing after exposure to UV light. Other objects of the present invention will be immediately apparent to the expert from the following description.

[0010] Surprisingly, the inventors of the present invention have found that the polymerizable tolane derivatives according to claim 1 meet one or more of the objectives set out above.

[0011] Summary of the Invention Thus, the present invention relates to a compound of formula I [ka] [In the formula, P is a polymerizable group, Sp is a spacer group or a single bond; R 11 is F, Cl, CN, NCS, alkyl, alkoxy, thioalkyl, alkylcarbonyl, alkoxycarbonyl, alkylcarbonyloxy or alkoxycarbonyloxy, preferably having 1 to 15 C atoms and more preferably optionally fluorinated, or is P-Sp, A, B, D and E, if present in plurality, independently of one another, represent an alicyclic, heterocyclic, aromatic or heteroaromatic group having 4 to 20 ring atoms, which is monocyclic or polycyclic, optionally substituted by one or more groups L or P-Sp-, and one of the rings C and D may also represent a single bond, L is F, Cl, -CN, P-Sp- or a linear, branched or cyclic alkyl having 1 to 25 C atoms, and one or more non-adjacent CH2- groups are optionally -O-, -S-, -CO-, -CO-O-, -O-CO-, -O-CO-O-, CR-, -CO-O ... 0 =CR 00 -, [ka] wherein one or more H atoms are optionally replaced by P-Sp-, F or Cl, respectively, or two substituents L bonded to directly adjacent C atoms may form a cycloalkyl or cycloalkenyl group having 5, 6, 7 or 8 C atoms, C is [ka] [ka] represents M represents CH2, C(CH3)2, CHF, CF2, NH, S or O; Z 11 , Z 12 When there are more than one, each independently represents -O-, -S-, -CO-, -COO-, -OCO-, -S-CO-, -CO-S-, -O-COO-, -CO-NR 0 -, -NR 0 -CO-, -NR 0 -CO-NR 00 , -NR 0 -CO-O-, -O-CO-NR 0 -, -OCH2-, -CH2O-, -SCH2-, -CH2S-, -CF2O-, -OCF2-, -CF2S-, -SCF2-, -CH2CH2-, -(CH2) n1 , -CF2CH2-, -CH2CF2-, -CF2CF2-, -CH=N-, -N=CH-, -N=N-, -CH=CR 0 -, -CY 1 =CY 2 -, [ka] , -CH=CH-COO-, -OCO-CH=CH- or a single bond, preferably -COO-, -OCO-, [ka] or a single bond, n1 is 1, 2, 3 or 4; r represents 0, 1, 2, 3 or 4, preferably 0, 1 or 2; s represents 0, 1, 2 or 3, preferably 0, 1 or 2, very preferably 0 or 1, t represents 0, 1 or 2, preferably 0 or 1, very preferably 0, R 0 , R 00represents H or alkyl having 1 to 12 C atoms, Y 1 , Y 2 represent, independently of one another, H, F, Cl, NCS or CN, n is 0, 1, 2, 3 or 4, preferably 0, 1 or 2, more preferably 0 or 1, most preferably 0; m is 0, 1, 2, 3 or 4, preferably 0, 1 or 2, more preferably 0 or 1, and most preferably 0. The present invention relates to a compound of the formula:

[0012] The present invention further relates to mixtures comprising two or more RMs, at least one of which is a compound of formula I (hereinafter "RM mixtures").

[0013] The present invention further relates to formulations (hereinafter "RM formulations") comprising one or more compounds of formula I or RM mixtures as described above and below, and further comprising one or more solvents and / or additives.

[0014] The present invention further relates to a polymer which is obtainable or has been obtained by polymerizing a compound of formula I or a mixture of RMs as described above and below, preferably with the RMs aligned, preferably at a temperature at which the RMs or the mixture of RMs exhibit a liquid crystalline phase.

[0015] The present invention further relates to the use of compounds of formula I or RM mixtures or polymers as described above and below in optical, electro-optical or electrical components or devices.

[0016] The present invention further relates to optical, electro-optical or electronic devices or components comprising the RM, RM blends or polymers described above and below.

[0017] The components include, but are not limited to, optical retardation films, polarizers, compensators, beam splitters, reflective films, alignment layers, color filters, antistatic protection sheets, electromagnetic interference protection sheets, polarization control lenses, e.g. for naked-eye stereoscopic 3D displays, IR reflective films, e.g. for window applications, spatial light modulators, and lenses for light guiding, focusing and optical effects, e.g. for 3D, holography, communication.

[0018] Such devices include, but are not limited to, electro-optical displays, particularly LC displays, autostereoscopic 3D displays, organic light emitting diodes (OLEDs), optical data storage devices, Google and Windows for AR / VR applications.

[0019] Definition of Terms As used herein, the term "RM mixture" refers to a mixture containing 2, 3, 4, 5, 6, 7, 8, 9 or more RMs.

[0020] The term "RM formulation" as used herein means at least one RM or RM mixture and one or more other materials added to the at least one RM or RM mixture to impart or modify certain properties of the RM formulation and / or at least one RM therein. It will be understood that the RM formulation is also a vehicle for carrying the RM to a substrate so that it can form a layer or structure thereon. Exemplary materials include, but are not limited to, solvents, polymerization initiators, surfactants, and adhesion promoters, etc., as described in more detail below.

[0021] The terms "reactive mesogen" and "RM" as used herein will be understood to mean a compound that comprises a mesogenic or liquid crystal backbone and one or more functional groups, also called "polymerizable groups" or "P", attached thereto that are suitable for polymerization.

[0022] Unless otherwise stated, the term "polymerizable compound" as used herein will be understood to mean a polymerizable monomeric compound.

[0023] The terms "liquid crystal", "mesogen" and "mesogenic compound" as used herein mean compounds that can exist as a mesophase, or especially an LC phase, under suitable conditions of temperature, pressure and concentration.

[0024] The term "mesogenic group" as used herein is known to those skilled in the art and described in the literature and means a group that essentially contributes to the formation of a liquid crystal (LC) phase of low-molecular or high-molecular substances due to the anisotropy of attractive and repulsive interactions. Compounds containing mesogenic groups (mesogenic compounds) do not necessarily have an LC phase by themselves. It is also possible that mesogenic compounds only show LC phase behavior after mixing with other compounds and / or after polymerization. Typical mesogenic groups are, for example, rigid or discotic units. An overview of terms and definitions used in connection with mesogenic or LC compounds is given in Pure Appl. Chem. 2001, 73(5), 888 and C. Tschierske, G. Pelzl, S. Diele, Angew. Chem. 2004, 116, 6340-6368.

[0025] The term "spacer group" (hereinafter also referred to as "Sp") used herein is known to those skilled in the art and described in the literature. See, for example, Pure Appl. Chem. 2001, 73(5), 888 and C. Tschierske, G. Pelzl, S. Diele, Angew. Chem. 2004, 116, 6340-6368. The term "spacer group" or "spacer" used herein means a flexible group, such as an alkylene group, that connects a mesogenic group and a polymerizable group in a polymerizable mesogenic compound.

[0026] In the formulas shown above and below, R 1 , R 0 , R11 If the group R or L, including any variants such as, represents an alkyl radical and / or an alkoxy radical, this may be linear or branched. It is preferably linear and has 2, 3, 4, 5, 6 or 7 C atoms and therefore preferably represents ethyl, propyl, butyl, pentyl, hexyl, heptyl, ethoxy, propoxy, butoxy, pentoxy, hexyloxy or heptyloxy, but also methyl, octyl, nonyl, decyl, undecyl, dodecyl, tridecyl, tetradecyl, pentadecyl, methoxy, octyloxy, nonyloxy, decyloxy, undecyloxy, dodecyloxy, tridecyloxy or tetradecyloxy.

[0027] In the formulas shown above and below, R 1 , R 0 , R 11 If the group R or L, including any variants such as, represents an alkyl radical and / or an alkoxy radical, this may be linear or branched. It is preferably linear and has 2, 3, 4, 5, 6 or 7 C atoms and therefore preferably represents ethyl, propyl, butyl, pentyl, hexyl, heptyl, ethoxy, propoxy, butoxy, pentoxy, hexyloxy or heptyloxy, but also methyl, octyl, nonyl, decyl, undecyl, dodecyl, tridecyl, tetradecyl, pentadecyl, methoxy, octyloxy, nonyloxy, decyloxy, undecyloxy, dodecyloxy, tridecyloxy or tetradecyloxy.

[0028] In the formulas shown above and below, R 1 , R 0 , R 11 When the group R or L, including any of the variants such as, represents an alkyl radical in which one or more CH2 groups are replaced by S, this may be linear or branched. It is preferably linear and has 1, 2, 3, 4, 5, 6 or 7 C atoms and therefore preferably represents thiomethyl, thioethyl, thiopropyl, thiobutyl, thiopentyl, thiohexyl or thioheptyl.

[0029] Oxaalkyl preferably denotes straight-chain 2-oxapropyl (=methoxymethyl), 2-(=ethoxymethyl) or 3-oxabutyl (=2-methoxyethyl), 2-, 3- or 4-oxapentyl, 2-, 3-, 4- or 5-oxahexyl, 2-, 3-, 4-, 5- or 6-oxaheptyl, 2-, 3-, 4-, 5-, 6- or 7-oxaoctyl, 2-, 3-, 4-, 5-, 6-, 7- or 8-oxanonyl, 2-, 3-, 4-, 5-, 6-, 7-, 8- or 9-oxa-decyl.

[0030] In the formulas shown above and below, R 1 , R 0 , R 11 When the group R or L, including any of the variations such as, represents an alkoxy group or an oxaalkyl group, it may also contain one or more additional oxygen atoms, provided that the oxygen atoms are not directly bonded to each other.

[0031] In another preferred embodiment, R 1 , R 0 , R 11 One or more of R or L, including any variations such as [ka] -S 1 -F, -OS 1 -F, -O-S1-O-S2 [wherein, S 1 is C 1~12 Alkylene or C 2~12 Alkenylene, S 2 is H, C 1~12 Alkyl or C 2~12 alkenyl, very preferably [ka] is selected from the group consisting of:

[0032] In the formulas shown above and below, R 1 , R 0 , R 11If the group R or L, including any of the variants such as , represents an alkyl radical in which one CH2 group is replaced by -CH=CH-, this may be linear or branched. It is preferably linear and has 2 to 10 C atoms. It therefore stands in particular for vinyl, prop-1- or -2-enyl, but-1-, -2- or -3-enyl, pent-1-, -2-, -3- or -4-enyl, hex-1-, -2-, -3-, -4- or -5-enyl, hept-1-, -2-, -3-, -4-, -5- or -6-enyl, oct-1-, -2-, -3-, -4-, -5-, -6- or -7-enyl, non-1-, -2-, -3-, -4-, -5-, -6-, -7- or -8-enyl, dec-1-, -2-, -3-, -4-, -5-, -6-, -7-, -8- or -9-enyl.

[0033] In the formulas shown above and below, R 1 , R 0 , R 11 When the group R or L, including any of the optional variations such as, represents an alkyl or alkenyl radical which is at least monosubstituted by a halogen, this radical is preferably linear and the halogen is preferably F or Cl. In the case of polysubstitution, the halogen is preferably F. The resulting radicals also include fully fluorinated radicals. In the case of monosubstitution, the fluorine or chlorine substituent can be in any desired position, but is preferably in the ω-position.

[0034] Halogen is preferably F or Cl, very preferably F.

[0035] Group-CR 0 =CR 00 - is preferably -CH=CH-.

[0036] -OC-, -CO-, -C(=O)- and -C(O)- are carbonyl groups, i.e. [ka] Represents.

[0037] Preferred substituents L are, for example, F, Cl, Br, I, -CN, -NO2, -NCO, -NCS, -OCN, -SCN, -C(=O)N(R x )2, -C(=O)Y 1 , -C(=O)R x , -N(R x 2) linear or branched alkyl, alkoxy, alkylcarbonyl, alkoxycarbonyl, alkylcarbonyloxy or alkoxycarbonyloxy, each having 1 to 25 C atoms, in which one or more H atoms may be optionally substituted by F or Cl, an optionally substituted silyl having 1 to 20 Si atoms or an optionally substituted aryl having 6 to 25, preferably 6 to 15, C atoms, R in the formula 1 , R 0 , R 11 R, including any of the optional variations thereof, represents H, F, Cl, CN or linear, branched or cyclic alkyl having 1 to 25 C atoms; in which one or more non-adjacent CH2- groups are optionally replaced by -O-, -S-, -CO-, -CO-O-, -O-CO-, -O-CO-O-, and one or more H atoms are optionally replaced by F, Cl, P- or P-Sp-, respectively, such that the O and / or S atoms are not directly bonded to each other; Y 1 represents a halogen.

[0038] Particularly preferred substituents L are, for example, F, Cl, CN, NO2, CH3, C2H5, OCH3, OC2H5, COCH3, COC2H5, COOCH3, COOC2H5, CF3, OCF3, OCHF2, OC2F5, and also phenyl. [ka] is preferably [ka] and In the formula, L has one of the meanings given above.

[0039] The polymerizable group P is a group suitable for polymerization reactions, such as free-radical or ionic chain polymerization, polyaddition or polycondensation, or polymer-analogous reactions, such as addition or condensation onto a polymer backbone. Particularly preferred are groups for chain polymerization, especially C=C double bonds or [ka] Groups containing a triple bond and groups suitable for polymerization involving ring-opening, such as oxetane and epoxide groups.

[0040] Preferred groups P are [ka] and W 4 W 5 W 6 Si-, wherein W 1 stands for H, F, Cl, CN, CF3, phenyl or alkyl having 1 to 5 C atoms, in particular H, F, Cl or CH3, W 2 and W 3 each independently of the other denotes H or alkyl having 1 to 5 C atoms, in particular H, methyl, ethyl or n-propyl, W 4 , W 5 and W 6 each independently represents Cl or an oxaalkyl or oxacarbonylalkyl having 1 to 5 C atoms, W 7 and W 8 each independently of one another represents H, Cl or alkyl having 1 to 5 C atoms, Phe represents 1,4-phenylene, which is optionally substituted by one or more radicals L as defined above other than P-Sp-, and k1, k2 and k3 each independently of one another represent 0 or 1, k3 preferably represents 1 and k4 represents an integer from 1 to 10.

[0041] Highly preferred groups P are [ka] and W 4 W 5 W 6 Si-, wherein W 1 stands for H, F, Cl, CN, CF3, phenyl or alkyl having 1 to 5 C atoms, in particular H, F, Cl or CH3, W 2 and W 3 each independently of one another denotes H or alkyl having 1 to 5 C atoms, in particular H, methyl, ethyl or n-propyl, W 4 , W 5 and W 6 each independently represents Cl or an oxaalkyl or oxacarbonylalkyl having 1 to 5 C atoms, W 7 and W 8 each independently represents H, Cl or an alkyl having 1 to 5 C atoms; Phe represents 1,4-phenylene; k1, k2 and k3 each independently represent 0 or 1, k3 preferably represents 1, and k4 represents an integer from 1 to 10.

[0042] Very particularly preferred groups P are CH2=CW 1 -CO-O-, in particular CH2=CH-CO-O-, CH2=C(CH3)-CO-O- and CH2=CF-CO-O-, further CH2=CH-O-, (CH2=CH)2CH-O-CO-, [ka] is selected from the group consisting of:

[0043] More preferably, the polymerizable group P is selected from the group consisting of vinyloxy, acrylate, methacrylate, fluoroacrylate, chloroacrylate, oxetane and epoxide, most preferably from acrylate and methacrylate.

[0044] Very preferably, all polymerizable groups in the polymerizable compound have the same meaning.

[0045] If the spacer group Sp is different from a single bond, it is preferably of the formula Sp"-X", such that each radical P-Sp- corresponds to the formula P-Sp"-X"-, in which Sp" represents a straight-chain or branched alkylene having 1 to 20, preferably 1 to 12, C atoms, which is optionally mono- or polysubstituted by F, Cl, Br, I or CN, and furthermore, one or more non-adjacent CH groups may be, independently of one another, -O-, -S-, -NH-, -N(R 0 )-, -Si(R 0 R 00 )-, -CO-, -CO-O-, -O-CO-, -O-CO-O-, -S-CO-, -CO-S-, -N(R 00 )-CO-O-, -O-CO-N(R 0 )-, -N(R 0 )-CO-N(R 00 )-, CH=CH- or [ka] may be replaced by, respectively, “X” is -O-, -S-, -CO-, -CO-O-, -O-CO-, -O-CO-O-, -CO-N(R 0 )-, -N(R 0 )-CO-, -N(R 0 )-CO-N(R 00 )-, -OCH2-, -CH2O-, -SCH2-, -CH2S-, CF2O-, -OCF2-, -CF2S-, -SCF2-, -CF2CH2-, -CH2CF2-, -CF2CF2-, CH=N-, -N=CH-, -N=N-, -CH=CR 0 -, -CY 2 =CY 3 -, [ka] , -CH=CH-CO-O-, -O-CO-CH=CH- or a single bond; R 0 and R 00 each independently of the others denotes H or alkyl having 1 to 20 C atoms, Y 2 and Y 3 each independently represents H, F, Cl or CN.

[0046] X″ is preferably —O—, —S—, —CO—, —COO—, —OCO—, —O—COO—, —CO—NR 0 -, -NR 0 -CO-, -NR 0 -CO-NR 00 - or a single bond.

[0047] Exemplary spacer groups Sp and -Sp"-X"- include, for example, -(CH2) p1 -, -(CH2) p1 -O-, -(CH2) p1 -O-CO-, -(CH2) p1 -CO-O-, -(CH2) p1 -O-CO-O-, -(CH2CH2O) q1 -CH2CH2-, -CH2CH2-S-CH2CH2-, -CH2CH2-NH-CH2CH2- or -(SiR 0 R 00 -O) p1 In the formula, p1 is an integer from 1 to 12, q1 is an integer from 1 to 3, and R 0 and R 00 has the meaning given above.

[0048] Particularly preferred groups Sp and -Sp"-X"- are -(CH2) p1 -, -(CH2) p1 -O-, -(CH2) p1 -O-CO-, -(CH2) p1 -CO-O-, -(CH2) p1 -O-CO-O-, in which p1 and q1 have the meanings given above.

[0049] Particularly preferred radicals Sp" are in each case straight-chain ethylene, propylene, butylene, pentylene, hexylene, heptylene, octylene, nonylene, decylene, undecylene, dodecylene, octadecylene, ethyleneoxyethylene, methyleneoxybutylene, ethylenethioethylene, ethylene-N-methyliminoethylene, 1-methylalkylene, ethenylene, propenylene and butenylene.

[0050] In a preferred embodiment of the invention, the compounds of formula I and subformulae thereof comprise a spacer group Sp substituted with one or more polymerizable groups P, such that the group Sp-P is Sp(P) s and s is ≧2 (branched polymerizable groups).

[0051] Preferred compounds of formula I according to this preferred embodiment are those in which s is 2, i.e. those which contain the group Sp(P)2. Highly preferred compounds of formula I according to this preferred embodiment have the following formula: -X-Alkyl-CHPP S1 -X-Alkyl-CH((CH2) aa P)((CH2) bb P) S2 -XN((CH2) aa P)((CH2) bb P) S3 -X-Alkyl-CHP-CH2-CH2P S4 -X-alkyl-C(CH2P)(CH2P)-C aa H 2aa+1 S5 -X-Alkyl-CHP-CH2P S6 -X-Alkyl-CPP-C aa H 2aa+1 S7 -X-Alkyl-CHPCHP-C aa H 2aa+1 S8 [In the formula, P is as defined in formula 1; Alkyl denotes a single bond or a straight-chain or branched alkylene having 1 to 12 C atoms which is unsubstituted or mono- or polysubstituted by F, Cl or CN, in which one or more non-adjacent CH groups are each independently of one another denoted by -C(R 0 )=C(R 0 )-, [ka] , -N(R 0 )-, -O-, -S-, -CO-, -CO-O-, -O-CO-, -O-CO-O-, R 0 has the meaning given above, aa and bb each independently represent 0, 1, 2, 3, 4, 5 or 6; X has one of the meanings given for X″ and is preferably O, CO, SO2, O—CO—, CO—O or a single bond. The present invention includes a group selected from the group consisting of

[0052] Preferred spacer groups Sp(P)2 are selected from formulae S1, S2 and S3.

[0053] Highly preferred spacer groups Sp(P)2 have the following sub-formula: -CHPP S1a -O-CHPP S1b -CH2-CHPP S1c -OCH2-CHPP S1d -CH(CH2-P)(CH2-P) S2a -OCH(CH2-P)(CH2-P) S2b -CH2-CH(CH2-P)(CH2-P) S2c -OCH2-CH(CH2-P)(CH2-P) S2d -CO-NH((CH2)2P)((CH2)2P) S3a is selected from.

[0054] P is preferably selected from the group consisting of vinyloxy, acrylate, methacrylate, fluoroacrylate, chloroacrylate, oxetane and epoxide, very preferably selected from acrylates and methacrylates, most preferably selected from methacrylates.

[0055] More preferably, all polymerizable groups P present in the same compound have the same meaning and very preferably represent acrylate or methacrylate, most preferably acrylate.

[0056] The term "film" as used herein includes not only rigid or flexible self-supporting or free-standing films with mechanical stability, but also coatings or layers on a supporting substrate or between two substrates. "Thin film" means a film having a thickness in the nanometer or micrometer range, preferably at least 10 nm, very preferably at least 100 nm, preferably 100 μm or less, very preferably 10 μm or less.

[0057] Throughout the application, the term "aryl and heteroaryl groups" encompasses groups which may be monocyclic or polycyclic, i.e. they may have one ring (such as phenyl) or two or more rings, which may be fused (such as naphthyl) or covalently linked (such as biphenyl) or may contain a combination of fused and linked rings. Heteroaryl groups contain one or more heteroatoms, preferably one or more heteroatoms selected from O, N, S and Se. Particularly preferred are monocyclic, bicyclic or tricyclic aryl groups having 6 to 25 C atoms and monocyclic, bicyclic or tricyclic heteroaryl groups having 2 to 25 C atoms, optionally containing fused rings and optionally substituted. Five-, six- or seven-membered aryl and heteroaryl groups are further preferred, in which one or more CH groups may be replaced by N, S or O, so that the O and / or S atoms are not directly bonded to each other. Preferred aryl groups are, 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, more preferably 1,4-phenylene, 4,4'-biphenylene, 1,4-terphenylene.

[0058] Preferred heteroaryl groups are, for example, pyrrole, pyrazole, imidazole, 1,2,3-triazole, 1,2,4-triazole, tetrazole, furan, thiophene, selenophene, oxazole, isoxazole, 1,2 thiazole, 1,3-thiazole, 1,2,3-oxadiazole, 1,2,4 oxadiazole, 1,2,5-oxadiazole, 1,3,4-oxadiazole, 1,2,3-thiadiazole, 1,2,4 -thiadiazole, 1,2,5-thiadiazole, 1,3,4-thiadiazole, 6-membered rings such as pyridine, pyridazine, pyrimidine, pyrazine, 1,3,5-triazine, 1,2,4-triazine, 1,2,3-triazine, 1,2,4,5-tetrazine, 1,2,3,4-tetrazine, 1,2,3,5-tetrazine or condensed groups such as indole, isoindole, indolizine, indazole, benzimidazole, benzotriazolidine, , purine, naphthimidazole, phenanthrimidazole, pyrimidazole, pyrazinimidazole, quinoxalimidazole, benzoxazole, naphthoxazole, anthroxazole, phenanthroxazole, isoxazole, benzothiazole, benzofuran, isobenzofuran, dibenzofuran, quinoline, isoquinoline, pteridine, benzo-5,6-quinoline, benzo-6,7-quinoline, benzo-7,8-quinoline, Benzoisoquinoline, acridine, phenothiazine, phenoxazine, benzopyridazine, benzopyrimidine, quinoxaline, phenazine, naphthyridine, azacarbazole, benzocarboline, phenanthridine, phenanthroline, thieno[2,3b]thiophene, thieno[3,2b]-thiophene, dithienothiophene, isobenzothiophene, dibenzothiophene, benzothiadiazothiophene or combinations of these groups. The heteroaryl group may be substituted by alkyl, alkoxy, thioalkyl, fluorine, fluoroalkyl or further aryl or heteroaryl groups.

[0059] The term "chiral" is commonly used to describe an object that is not superimposable on its mirror image.

[0060] An "achiral" (non-chiral) object is one that is identical to its mirror image.

[0061] The terms "chiral nematic" and "cholesteric" are used interchangeably in this application unless otherwise specified.

[0062] The reflected wavelength λ is determined by the pitch p of the cholesteric helix and the average birefringence n of the cholesteric liquid crystal, as follows: λ=n p is given according to

[0063] CLC media can be prepared, for example, by doping a nematic LC medium with a chiral dopant having a high twisting power. The pitch p of the induced cholesteric helix then depends on the concentration c and the helical twisting power HTP of the chiral dopant according to the following formula: p=(HTPc) -1 is given according to

[0064] It is also possible to use two or more dopants, for example to compensate for the temperature dependence of the HTP of the individual dopants and thus achieve a low temperature dependence of the helical pitch and reflection wavelength of the CLC medium. In that case, the total HTP (HTP total) For, the formula is roughly: HTP total =Σ i c i HTP i [In the formula, c i is the concentration of each dopant, and HTP i is the helical twisting power of each dopant] holds true.

[0065] As described above and below [ka] represents a trans-1,4-cyclohexylene ring, [ka] represents a 1,4-phenylene ring.

[0066] Visible light is electromagnetic radiation having wavelengths ranging from about 400 nm to about 740 nm. Ultraviolet (UV) light is electromagnetic radiation having wavelengths ranging from about 200 nm to about 450 nm.

[0067] Irradiance (E e ) or radiant power is the power of electromagnetic radiation (dθ) per unit area (dA) incident on a surface: E e =dθ / dA It is defined as:

[0068] Radiation exposure or radiation dose (H e ) is the irradiance or radiant power (E e ): H e =E e ·t It is expressed as:

[0069] All temperatures, such as the melting point T(C,N) or T(C,S), the transition from the smectic (S) to the nematic (N) phase T(S,N) and the clearing point T(N,I) of liquid crystals, are given in degrees Celsius. All temperature differences are given in degrees.

[0070] The term "clearing point" means the temperature at which the transition between the mesophase and the isotropic phase occurs in the highest temperature range.

[0071] The term "director" is known in the prior art and refers to the preferred orientation direction of the long molecular axis (in the case of calamitic compounds) or the short molecular axis (in the case of discotic compounds) of the liquid crystal or RM molecules. In the case of uniaxial ordering of such anisotropic molecules, the director is the axis of anisotropy.

[0072] The term "alignment" or "orientation" refers to the alignment (orientational ordering) of anisotropic units of a material, such as fragments of small or large molecules, in a common direction termed the "alignment direction". In an aligned layer of liquid crystal or RM material, the liquid crystal director coincides with the alignment direction, so that the alignment direction corresponds to the direction of the anisotropic axis of the material.

[0073] The term "uniform orientation" or "uniform alignment" of liquid crystal or RM materials, for example in a layer of material, means that the long molecular axes (for calamitic compounds) or short molecular axes (for discotic compounds) of the liquid crystal or RM molecules are aligned in substantially the same direction. In other words, the lines of the liquid crystal directors are parallel.

[0074] The terms "homeotropic structure" or "homeotropic orientation" refer to a film in which the optic axis is substantially perpendicular to the film plane.

[0075] The terms "planar structure" or "planar orientation" refer to a film in which the optical axis is substantially parallel to the film plane.

[0076] The term "A-plate" refers to an optical retarder that utilizes a layer of uniaxially birefringent material with its extraordinary axis oriented parallel to the plane of the layer.

[0077] The term "C-plate" refers to an optical retarder that utilizes a layer of uniaxially birefringent material with its extraordinary axis oriented perpendicular to the plane of the layer.

[0078] In an A / C plate containing optically uniaxial birefringent liquid crystal material with uniform orientation, the optic axis of the film is given by the direction of the extraordinary axis. An A (or C) plate containing optically uniaxial birefringent material with positive birefringence is also called a "positive A (or C) plate" or "+A (or +C) plate".

[0079] A (or C) plates comprising 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 from cholesteric calamitic materials with reflection bands in the UV part of the spectrum also have the optical functionality of a negative C plate.

[0080] The birefringence Δn is: Δn=n e -n o [where n e is the extraordinary refractive index, and n o is the ordinary refractive index, and the average effective refractive index n av. is the following formula: n av. =((2n o 2 +n e 2 ) / 3) 1 / 2 is given by] is defined as follows.

[0081] Mean effective refractive index n av. and the ordinary refractive index n o can be measured using an Abbe refractometer, where Δn can be calculated from the above formula.

[0082] Unless the context clearly indicates otherwise, plural forms of the terms used herein are to be construed as including the singular and vice versa.

[0083] All physical properties are determined according to "Merck Liquid Crystals, Physical Properties of Liquid Crystals", Status Nov. 1997, Merck KGaA, Germany and are given at a temperature of 20° C. unless otherwise stated. The optical anisotropy (Δn) is determined at a wavelength of 589.3 nm.

[0084] base [ka] In the formula (I), the single bond shown between the two ring atoms can be attached to any free position of the benzene ring.

[0085] -OC-, -CO-, -C(=O)- and -C(O)- are carbonyl groups, i.e. [ka] Represents.

[0086] Above and below, percentages are by weight unless otherwise stated. All temperatures are given in degrees Celsius. mp stands for melting point, cl.p. stands for clearing point, T g represents the glass transition temperature. Furthermore, C=crystalline state, N=nematic phase, S=smectic phase, and I=isotropic phase. The data between these symbols represent the transition temperatures. Δn represents the optical anisotropy or birefringence measured at 550 nm and 20° C. (Δn=n e -n o , n o represents the refractive index perpendicular to the longitudinal axis of the molecule, and n e denotes the refractive index parallel thereto). Optical and electro-optical data are measured at 20° C. unless otherwise stated. "Clearing point" and "clearing temperature" refer to the transition temperature from the LC phase to the isotropic phase.

[0087] Unless otherwise stated, the percentages of solid components in a RM mixture or formulation above and below refer to the total amount of solids in the mixture or formulation, ie, without solvent.

[0088] Unless otherwise stated, all optical properties, electro-optical properties and physical parameters, such as birefringence, dielectric constant, electrical conductivity, electrical resistivity and sheet resistance, refer to a temperature of 20°C.

[0089] Unless the context clearly indicates otherwise, plural forms of the terms used herein are to be construed as including the singular and vice versa.

[0090] Throughout the description and claims of this specification, the words "comprise" and "contain" and variations of this word, such as "comprising" and "comprises," mean "including but not limited to" and are not intended to (and do not) exclude other elements.

[0091] It will be understood that modifications to the embodiments of the invention may be made while remaining within the scope of the invention. Each feature disclosed herein, unless otherwise stated, may be replaced with alternative features serving the same, equivalent or similar purpose. Thus, unless otherwise stated, each feature disclosed is only one example of a whole series of equivalent or similar features.

[0092] All features disclosed herein may be combined in any combination, except combinations in which at least some of such features and / or steps are mutually exclusive. In particular, preferred features of the invention are applicable to all aspects of the invention and may be used in any combination. Similarly, features described in non-essential combinations may be used individually (not in combination).

[0093] A "polymer network" is a network in which all polymer chains are interconnected to form a single macroscopic entity through multiple cross-links.

[0094] The polymer networks can occur in the following types: · Graft polymer molecules are branched polymer molecules in which one or more side chains are structurally or configurationally different from the main chain. A star polymer molecule is a branched polymer molecule with multiple chains or arms arising from a single branch point. If the arms are identical, the star polymer molecule is said to be regular. If adjacent arms are composed of different repeating subunits, the star polymer molecule is said to be mixed chain. Comb polymer molecules consist of a main chain with two or more three-way branch points and linear side chains. If the arms are identical, the comb polymer molecule is said to be regular. Brush polymer molecules consist of a main chain with linear, unbranched side chains, with one or more branch points carrying functional groups in four or more directions.

[0095] Detailed Description In the compounds of formula I and subformulas thereof above and below, P is preferably selected from the group consisting of vinyloxy, acrylate, methacrylate, fluoroacrylate, chloroacrylate, oxetane and epoxide, very preferably selected from acrylate and methacrylate, most preferably acrylate.

[0096] Further preferred are compounds of formula I and sub-formulae thereof above and below, in which all polymerizable groups P present in the compound have the same meaning, very preferably representing acrylate or methacrylate, most preferably acrylate.

[0097] Further preferred are compounds of formula I and sub-formulae thereof above and below, which contain 1, 2, 3 or 4 groups P-Sp, very preferably 2 or 3 groups P-Sp.

[0098] More preferably, R 11 is a compound of formula I and subformulae thereof, above and below, wherein

[0099] More preferably, Sp is a single bond or -(CH2) p1 -, -O-(CH2) p1 -, -O-CO-(CH2) p1or -CO-O-(CH2) p1 [Wherein, p1 is 2, 3, 4, 5 or 6, and Sp is -O-(CH2) p1 -, -O-CO-(CH2) p1 or -CO-O-(CH2) p1 where, respectively, an O atom or a CO group is attached to the benzene ring.

[0100] Further preferred are compounds of formula I and subformulae thereof above and below, in which at least one group Sp is a single bond.

[0101] Further preferred are compounds of formula I and subformulae thereof above and below, in which at least one group Sp is a single bond and at least one group Sp is different from a single bond.

[0102] Further preferred are those in which at least one group Sp is different from a single bond and is -(CH2) p1 -, -O-(CH2) p1 -, -O-CO-(CH2) p1 or -CO-O-(CH2) p1 [Wherein, p1 is 2, 3, 4, 5 or 6, and Sp is -O-(CH2) p1 -, -O-CO-(CH2) p1 or -CO-O-(CH2) p1 where, respectively, an O atom or a CO group is attached to the benzene ring.

[0103] Highly preferred are compounds of formula I and subformulae thereof above and below, in which at least one group Sp is different from a single bond and is selected from -(CH2)2-, -(CH2)3-, -(CH2)4-, -O-(CH2)2-, -O-(CH2)3-, -O-CO-(CH2)2 and -CO-O-(CH)2-, in which the O atom or CO group is attached to the benzene ring.

[0104] Preferably, one or more of rings A, B, D and / or E in formula I are 1,4-phenylene, 1,3-phenylene, naphthalene-1,4-diyl, naphthalene-2,6-diyl, phenanthrene-2,7-diyl, 9,10-dihydro-phenanthrene-2,7-diyl, anthracene-2,7-diyl, anthracene-9,10-diyl, fluorene-2,7-diyl, dibenzothiophene-2,7-diyl, dibenzofuran-2,7-diyl, benzo[1,2-b:4,5-b']dithiophene-2,5-diyl, indole-4,7-diyl, benzothiophene-4,7-diyl, coumarin, flavone [furthermore, one or more CH groups of these groups may be N,N-cyclohexane- 1,4-diyl, and further one or more non-adjacent CH groups may be replaced by O and / or S], 1,4-cyclohexenylene, bicyclo-[1.1.1]-pentane-1,3-diyl, bicyclo[2.2.2]octane-1,4-diyl, spiro[3.3]-heptane-2,6-diyl, piperidine-1,4-diyl, decahydronaphthalene-2,6-diyl, 1,2,3,4-tetrahydronaphthalene-2,6-diyl, indan-2,5-diyl or octahydro-4,7-methanoindan-2,5-diyl, all of which may be optionally substituted by one or more groups L or P-Sp-.

[0105] Very preferably, one or more of the rings A, B, D and / or E in formula I are selected from the group consisting of benzene-1,4-diyl, naphthalene-1,4-diyl, naphthalene-2,6-diyl, phenanthrene-2,7-diyl, anthracene-9,10-diyl, fluorene-2,7-diyl, dibenzofuran-2,7-diyl, dibenzothiophene-2,7-diyl, benzo[1,2-b:4,5-b']dithiophene-2,5-diyl, indole-4,7-diyl, benzothiophene-4,7-diyl, all of which may be optionally substituted by one or more groups L or P-Sp-. In these rings A, B, D and E, naphthalene is preferably naphthalene-2,6-diyl or naphthalene-1,4-diyl, and anthracene is preferably anthracene-9,10-diyl.

[0106] Ring C in formula I is preferably selected from the group consisting of benzene-1,4-diyl, naphthalene-1,4-diyl, anthracene-9,10-diyl, fluorene-2,7-diyl, dibenzofuran-2,7-diyl, dibenzothiophene-2,7-diyl, benzo[1,2-b:4,5-b']dithiophene-2,5-diyl, indole-4,7-diyl, benzothiophene-4,7-diyl, very preferably benzene-1,4-diyl, naphthalene-1,4-diyl or anthracene-9,10-diyl, all of which may be optionally substituted by one or more groups L or P-Sp-.

[0107] When ring C is a benzene ring, it is preferably mono- or di-substituted with L.

[0108] More preferably, one, two, three, four or more of rings A, B, D and / or E in formula I are: [ka] [In the formula, L are each independently of one another alkyl, alkoxy or thioalkyl having 1 to 6 C atoms, P-Sp-, -CN, F, Cl, OCF3, CF3, CH2F, CHF2 or two substituents L bonded to directly adjacent C atoms may form a cyclic group containing 5, 6, 7 or 8 C atoms, r represents 0, 1, 2 or 3; s represents 0, 1 or 2; t represents 0, 1 or 2; M represents CH2, C(CH3)2, CHF, CF2, NH, S or O. is selected from the group consisting of:

[0109] More preferably, one or both of rings B and / or D in formula I are: [ka] [In the formula, L are each independently of one another alkyl, alkoxy or thioalkyl having 1 to 6 C atoms, P-Sp-, -CN, F, Cl, OCF3, CF3, CH2F, CHF2 or two substituents L bonded to directly adjacent C atoms may form a cyclic group containing 5, 6, 7 or 8 C atoms, r represents 0, 1, 2 or 3; s represents 0, 1 or 2; t represents 0, 1 or 2; M represents CH2, C(CH3)2, CHF, CF2, NH, S or O. is selected from the group consisting of:

[0110] Particularly preferred are compounds of formula I in which one or both of rings B and / or D represent a 2,6-naphthalene radical or a 1,4-naphthalene radical.

[0111] Preferably, ring C in formula I is: [ka] [In the formula, L are each independently P-Sp-, F, -CN or alkyl, alkoxy or thioalkyl having 1 to 6, preferably 1 to 3 and more preferably 1 or 2 C atoms, r represents 0, 1, 2 or 3; s represents 0, 1, 2 or 3; t represents 0, 1 or 2; M represents CH2, C(CH3)2, CHF, CF2, NH, S or O; M 1 represents S, O or NH. is selected from the group consisting of:

[0112] Highly preferably, ring C in formula I is: [ka] [wherein L's independently represent P-Sp-, F, -CN or alkyl, alkoxy or thioalkyl having 1 to 6, preferably 1 to 3 and more preferably 1 or 2 C atoms] is selected from the group consisting of:

[0113] More preferred are those in which n=m=0 and rings B, C and D are each a group [ka] [In the formula, L each independently represents P-Sp-, F, -CN or alkyl, alkoxy or thioalkyl having 1 to 6, preferably 1 to 3 and more preferably 1 or 2 C atoms, r represents 0, 1, 2 or 3, preferably 1 or 2. The compound of formula I is formed as follows:

[0114] More preferred are those in which n=m=0 and rings B, C and D are each a group [ka] wherein L is methyl, ethyl, methoxy, ethoxy, thiomethyl or thioethyl, preferably ethyl. The compound of formula I is formed as follows:

[0115] Preferred compounds of formula I have the following subformula: [ka] [In the formula, R 11 rings B and D, P and Sp have one of the meanings in formula I or one of the preferred meanings given above, L each independently represents P-Sp-, F, -CN or alkyl, alkoxy or thioalkyl having 1 to 6, preferably 1 to 3 and more preferably 1 or 2 C atoms, L 1 and L 2 each independently represents H or L, M is S, O, NH, CH2 or C(CH3)2; M 1 is NH or S] is selected from.

[0116] Highly preferred compounds of formula I have the following subformula: [ka] [ka] [ka] [ka] [ka] [ka] [ka] [In the formula, P is a polymerizable group, Sp is a spacer group or a single bond; R is alkyl, alkoxy, thioalkyl, alkylcarbonyl, alkoxycarbonyl, alkylcarbonyloxy or alkoxycarbonyloxy, preferably having 1 to 15 C atoms and more preferably optionally fluorinated, L is preferably an acrylate, P-Sp-, F, Cl, -CN or a linear, branched or cyclic alkyl having 1 to 25 C atoms, in which one or more non-adjacent CH2- groups are optionally separated such that O and / or S atoms are not directly bonded to each other; [ka] wherein one or more H atoms are optionally replaced by P-Sp-, F or Cl, respectively, and two substituents L bonded to directly adjacent C atoms may form a cyclic group having 5, 6, 7 or 8 C atoms, r represents 0, 1, 2, 3 or 4, preferably 0, 1 or 2. is selected from.

[0117] Further preferred are compounds of the formulae I-1-2, I-2-2, I-3-2, I-4-2, I-5-2, I-6-2, I-1-5, I-2-5, I-3-5, I-4-5, I-5-5, I-6-5, I-1-7, I-2-7, I-3-7, I-4-7, I-5-7, I-6-7, I-1-9, I-2-9, I-3-9, I-4-9, I-5-9, I-6-9, I-1-11, I-2-11, I-3-11, I-4-11, I-5-11 and I-6-11, in which one of the two groups Sp is a single bond and the other group Sp is different from a single bond.

[0118] Preferred compounds of formulae I, I-1 to I-9 and I-1-1 to I-6-11 are n=m=0, or n=1 and m=1, or n=m=1 and / or n=m=0 and one of ring B and ring D is a single bond, and / or Ring C represents naphthalene-1,4-diyl or anthracene-9,10-diyl, or Ring C represents benzene-1,4-diyl substituted by ethyl, and / or P represents an acrylate or methacrylate, and / or Sp represents Sp"-X", preferably -Sp"-X"- is -(CH2) p1 -, -(CH2) p1 -O-, -(CH2) p1 -O-CO-, -(CH2) p1 -CO-O-, -(CH2) p1 -O-CO-O-, -(CH2CH2O) q1 -CH2CH2-, -CH2CH2-S-CH2CH2- or -CH2CH2-NH-CH2CH2-, where p1 is an integer from 1 to 12 and q1 is an integer from 1 to 3; and / or ·R 11 or when R is P-Sp-, then both groups P-Sp- are identical, or ·R 11 or when R is P-Sp-, one of the groups Sp is a single bond and the other of the groups Sp is different from a single bond; and / or L represents methyl or ethyl, preferably ethyl, and r represents 1, and / or L represents methyl or ethyl and r represents 2, and / or r denotes 2 and two substituents L are bonded to directly adjacent C atoms and together with the C atoms to which they are bonded form a cyclic group having 5 or 6 C atoms, preferably a cyclohexenyl group, and / or Ring C is substituted by one L representing P-Sp-, preferably acrylate, R or R 11is alkyl, alkoxy, thioalkyl, alkylcarbonyl, alkoxycarbonyl, alkylcarbonyloxy or alkoxycarbonyloxy, preferably having 1 to 15 C atoms, more preferably optionally fluorinated, very preferably methyl, methoxy, ethyl, ethoxy, propyl, isopropyl, propyloxy, isopropyloxy or linear or branched butyl or butyloxy, The compound is selected from the group consisting of:

[0119] Further preferred compounds of formula I are outlined in the Examples section below.

[0120] The synthesis of the compounds of formula I and its subformulas can be carried out analogously to the exemplary reactions given below or in the Examples. The preparation of further compounds according to the invention can also be carried out by other methods known per se to those skilled in the art from the literature.

[0121] For example, compounds of formula I can be synthesized according to or analogously to the methods shown in the Examples.

[0122] The compounds of formula I, alone or in combination with other RMs in RM mixtures, in particular and preferably simultaneously exhibit high birefringence, good solubility in commonly known organic solvents used in mass production, improved band broadening capabilities in chiral RM mixtures, favorable transition temperatures, and high resistance to yellowing after exposure to UV light.

[0123] The concentration of the compound of formula I in the RM mixture is preferably 35-99%, very preferably 50-99%.

[0124] Preferably, the RM mixture comprises one or more RMs with only one polymerizable functional group (monoreactive RMs) and one or more RMs with two or more polymerizable functional groups (direactive or multireactive RMs).

[0125] The bireactive or multireactive RM is preferably of the formula DRM P 1 -Sp 1 -MG-Sp 2 -P 2 DRM wherein: P 1 and P 2 represent, independently of one another, a polymerizable group, Sp 1 and Sp 2 are, independently of each other, a spacer group or a single bond, MG is a rod-shaped mesogenic group, preferably of the formula MG -(A 1 -Z 1 ) n -A 2 - M.G. is selected from the group consisting of A 1 and A 2 represents, when present in plurality, independently of one another, an aromatic or alicyclic group optionally containing one or more heteroatoms selected from N, O and S and optionally mono- or polysubstituted by L, L is P-Sp-, F, Cl, Br, I, -CN, -NO2, -NCO, -NCS, -OCN, -SCN, -C(=O)NR x R y , -C(=O)OR x , -C(=O)R x , -NR x R y , -OH, -SF5, optionally substituted silyl, aryl or heteroaryl having 1 to 12, preferably 1 to 6, C atoms and linear or branched alkyl, alkoxy, alkylcarbonyl, alkoxycarbonyl, alkylcarbonyloxy or alkoxycarbonyloxy having 1 to 12, preferably 1 to 6, C atoms, in which one or more H atoms may optionally be replaced by F or Cl, R x and R y represent, independently of one another, H or alkyl having 1 to 12 C atoms, Z 1 If there are multiple, they are independent of each other. [ka] or a single bond, preferably -COO-, -OCO- or a single bond; Y 1 and Y 2 represent, independently of one another, H, F, Cl or CN, n is 1, 2, 3 or 4, preferably 1 or 2, most preferably 2; n1 is an integer of 1 to 10, and is preferably 1, 2, 3 or 4.

[0126] Preferred group A 1 and A 2 include, but are not limited to, furan, pyrrole, thiophene, oxazole, thiazole, thiadiazole, imidazole, phenylene, cyclohexylene, bicyclooctylene, cyclohexenylene, pyridine, pyrimidine, pyrazine, azulene, indane, fluorene, naphthalene, tetrahydronaphthalene, anthracene, phenanthrene, and dithienothiophene, all of which are unsubstituted or substituted by 1, 2, 3 or 4 groups L as defined above.

[0127] Particularly preferred groups A 1 and A 2 is selected from 1,4-phenylene, pyridine-2,5-diyl, pyrimidine-2,5-diyl, thiophene-2,5-diyl, naphthalene-2,6-diyl, 1,2,3,4-tetrahydro-naphthalene-2,6-diyl, indan-2,5-diyl, bicyclooctylene or 1,4-cyclohexylene, in which one or two non-adjacent CH groups may be optionally replaced by O and / or S, which groups are unsubstituted or substituted by 1, 2, 3 or 4 groups L as defined above.

[0128] A preferred RM of the formula DRM is [ka] [In the formula, P 0 are, when present in plurality, independently of one another, a polymerizable group, preferably an acrylic, methacrylic, oxetane, epoxy, vinyl, heptadiene, vinyloxy, propenyl ether or styrene group, Z 0 teeth, [ka] or a single bond, and L, at each occurrence, is L of formula I 1 and preferably, if several are present, independently of one another, are selected from F, Cl, CN or optionally halogenated alkyl, alkoxy, alkylcarbonyl, alkoxycarbonyl, alkylcarbonyloxy or alkoxycarbonyloxy having 1 to 5 C atoms, r is 0, 1, 2, 3 or 4; x and y are each independently 0 or the same or different integers from 1 to 12; z is 0 or 1, and z is 0 if the adjacent x or y is 0. The following are selected from:

[0129] A highly preferred RM of formula DRM is of the formula: [ka] [ka] [In the formula, P 0 , L, r, x, y and z are as defined in formula DRMa] is selected from.

[0130] Particularly preferred are compounds of formula DRMa1, DRMa2 and DRMa3, especially the compound of formula DRMa1.

[0131] The concentration of the di- or polyreactive RMs in the RM mixture, preferably the concentration of the formula DRM and its subformulas, is preferably 1% to 60%, very preferably 2 to 40%.

[0132] In another preferred embodiment, the RM mixture comprises one or more monoreactive RMs in addition to the compound of formula I. These additional monoreactive RMs preferably have the formula MRM: P 1 -Sp 1 -MG-R MRM [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 R y , -OH, -SF5, optionally substituted silyl, linear or branched alkyl, alkoxy, alkylcarbonyl, alkoxycarbonyl, alkylcarbonyloxy or alkoxycarbonyloxy having 1 to 12, preferably 1 to 6, C atoms, in which one or more H atoms may optionally be replaced by F or Cl, X is a halogen, preferably F or Cl; R x and R y are, independently of one another, H or alkyl having 1 to 12 C atoms. is selected from.

[0133] A highly preferred RM of formula DRM is of the formula: [ka] [ka] [ka] [ka] [In the formula, P 0 , L, r, x, y and z are as defined in formula DRMa; R 0 , R 01 and R 02 are each independently an alkyl, alkoxy, thioalkyl, alkylcarbonyl, alkoxycarbonyl, alkylcarbonyloxy or alkoxycarbonyloxy having one or more, preferably 1 to 15, C atoms, or Y 0 or P-(CH2) y -(O) z - represents X 0 teeth, [ka] or a single bond, Y 0 is F, Cl, CN, NO2, OCH3, OCN, SCN, SF5 or a mono-, oligo- or polyfluorinated alkyl or alkoxy having 1 to 4 C atoms, Z 0 is -COO-, -OCO-, -CH2CH2-, -CF2O-, -OCF2-, -CH=CH-, -OCO-CH=CH-, -CH=CH-COO- or a single bond, A 0 are, when present in plurality, each independently 1,4-phenylene or trans-1,4-cyclohexylene which is unsubstituted or substituted by 1, 2, 3 or 4 L groups; R 01、02 are, independently of each other, H, R 0 or Y 0 and u and v are, independently of each other, 0, 1 or 2; w is 0 or 1; The benzene and naphthalene rings can be further substituted with one or more of the same or different groups L. is selected from.

[0134] Particularly preferred are compounds of formulae MRM1, MRM2, MRM3, MRM4, MRM5, MRM6, MRM7, MRM9 and MRM10, in particular compounds of formulae MRM1, MRM4, MRM6 and MRM7.

[0135] The concentration of the monoreactive RM, preferably of formula MRM, in the RM mixture is preferably 1-80%, very preferably 5-20%.

[0136] The RM mixture preferably exhibits a nematic LC phase or a smectic LC phase and a nematic LC phase at room temperature, very preferably a nematic LC phase.

[0137] In the formulae DRM, MRM and preferred sub-formulae thereof, L is preferably selected from F, Cl, CN, NO2 or linear or branched alkyl, alkoxy, alkylcarbonyl, alkoxycarbonyl, alkylcarbonyloxy or alkoxycarbonyloxy having 1 to 12 C atoms, the alkyl groups of which may optionally be fully fluorinated, or P-Sp-.

[0138] Very preferably, L is selected from F, Cl, CN, NO2, CH3, C2H5, C(CH3)3, CH(CH3)2, CH2CH(CH3)C2H5, OCH3, OC2H5, COCH3, COC2H5, COOCH3, COOC2H5, CF3, OCF3, OCHF2, OC2F5 or P-Sp-, in particular F, Cl, CN, CH3, C2H5, C(CH3)3, CH(CH3)2, OCH3, COCH3 or OCF3, most preferably F, Cl, CH3, C(CH3)3, OCH3 or COCH3 or P-Sp-.

[0139] Preferably, the RM mixture according to the present invention optionally comprises one or more chiral compounds. These chiral compounds may be non-mesogenic or mesogenic compounds. Furthermore, these chiral compounds, whether mesogenic or non-mesogenic, may be non-reactive, monoreactive or polyreactive.

[0140] Preferably, the chiral compounds utilized, either alone or in combination with one another, are less than 20 μm -1 More than 40 μm, preferably -1 More preferably, 60 μm -1 The above range, most preferably 80 μm -1 Above 260μm -1 in particular the absolute value of the helical twisting force (IHTP total I).

[0141] Preferably, the non-polymerizable chiral compound is represented by the formulae CI to C-III [ka] [In the formula, E and F are each independently 1,4-phenylene or trans-1,4-cyclohexylene; v is 0 or 1, Z 0 is -COO-, -OCO-, -CH2CH2- or a single bond, R is alkyl, alkoxy or alkanoyl having 1 to 12 C atoms. wherein the latter includes its respective (S,S) enantiomer.

[0142] Particularly preferred liquid crystal media contain one or more chiral compounds, which do not necessarily exhibit a liquid crystal phase.

[0143] The compounds of formula C-II and their synthesis are described in WO 98 / 00428. Particularly preferred is compound CD-1, shown in Table D below. The compounds of formula C-III and their synthesis are described in German Patent No. 2328207.

[0144] Further typically used chiral compounds are for example commercially available R / S-5011, CD-1, R / S-811 and CB-15 (from Merck KGaA, Darmstadt, Germany).

[0145] The above mentioned chiral compounds R / S-5011 and CD-1 as well as the (other) compounds of formulae CI, C-II and C-III are particularly useful for the purposes of the present invention since they exhibit very high helical twisting power (HTP).

[0146] The RM mixture preferably comprises 1 to 5, in particular 1 to 3, very preferably 1 or 2 chiral compounds selected from above formula C-II, in particular CD-1 and / or formula C-III and / or R-5011 or S-5011, very preferably the chiral compound is R-5011, S-5011 or CD-1.

[0147] Preferably, the RM mixture optionally comprises one or more non-reactive chiral compounds and / or one or more reactive chiral compounds, preferably selected from monoreactive and / or polyreactive chiral compounds.

[0148] Suitable mesogenic reactive chiral compounds preferably comprise one or more ring elements linked together by a direct bond or via a linking group, two of which may be optionally linked to each other directly or via a linking group, which may be the same or different from the linking groups mentioned above. The ring elements are preferably selected from 4-, 5-, 6- or 7-membered rings, preferably 5- or 6-membered ring groups.

[0149] Suitable polymerizable chiral compounds and their synthesis are described in US Pat. No. 7,223,450.

[0150] Preferred monoreactive chiral compounds have the formula CRM [ka] [In the formula, P 0* is a polymerizable group, P; A 0 and B. 0 are, when present in plurality, independently of one another, 1,4-phenylene or trans-1,4-cyclohexylene which are unsubstituted or substituted by 1, 2, 3 or 4 radicals L as defined above, X 1 and X 2 are, independently of one another, -O-, -COO-, -OCO-, -O-CO-O- or a single bond, Z 0* when there are a plurality of them, they are each independently -COO-, -OCO-, -O-CO-O-, -OCH2-, -CHO-, -CF2O-, -OCF2-, -CH2CH2-, -(CH2)4-, -CF2CH2-, -CH2CF2-, -CF2CF2-, -C≡C-, -CH=CH-, -CH=CH-COO-, -OCO-CH=CH- or a single bond; t's are, independently of one another, 0, 1, 2 or 3; a is 0, 1 or 2; b is 0 or an integer from 1 to 12 z is 0 or 1; The naphthalene ring can be further substituted with one or more of the same or different groups L, L are, independently of one another, F, Cl, CN, a halogenated alkyl having 1 to 5 C atoms, an alkoxy, an alkylcarbonyl, an alkoxycarbonyl, an alkylcarbonyloxy or an alkoxycarbonyloxy. The compound is selected from the group consisting of

[0151] The compound of formula CRM is preferably of formula CRM-a [ka] [In the formula, A 0 , B 0 , Z 0* , P 0* , a and b have the meanings given in formula CRM or one of the preferred meanings given above and below, (OCO) represents -O-CO- or a single bond. The compound is selected from the group consisting of:

[0152] Particularly preferred compounds of formula CRM have the following subformula: [ka] [ka] [ka] [In the formula, R is defined by the formula CRM-a -X 2 -(CH2) x -P 0* and The benzene and naphthalene rings are unsubstituted or substituted with 1, 2, 3 or 4 groups L as defined above and hereinafter. is selected from the group consisting of:

[0153] The amount of the chiral compound in the liquid crystal medium is preferably 1 to 20% by weight, more preferably 1 to 15% by weight, further preferably 1 to 10% by weight, and most preferably 2 to 6% by weight of the entire mixture.

[0154] Another object of the present invention is a RM formulation comprising one or more compounds or RM mixtures of formula I above and below and further comprising one or more solvents and / or additives.

[0155] In a preferred embodiment, the RM formulation optionally comprises one or more additives selected from the group consisting of polymerization initiators, surfactants, stabilizers, catalysts, sensitizers, inhibitors, chain transfer agents, co-reacting monomers, reactive diluents (thinners), surface active compounds, lubricants, wetting agents, dispersants, hydrophobizing agents, adhesives, flow improvers, degassing or antifoaming agents, degassing agents, diluents, reactive diluents, auxiliaries, colorants, dyes, pigments and nanoparticles.

[0156] In another preferred embodiment, the RM formulation optionally comprises one or more additives selected from polymerizable non-mesogenic compounds (reactive diluents). The amount of these additives in the RM formulation is preferably 0-30%, very preferably 0-25%.

[0157] The reactive diluents used include not only substances which are called reactive diluents in the actual sense, but also the auxiliary compounds already mentioned above which contain one or more complementary reactive units, such as hydroxyl, thiol or amino groups, capable of reacting with the polymerizable units of the liquid crystal compound.

[0158] Photopolymerizable substances usually include, for example, mono-, di- and polyfunctional compounds containing at least one olefinic double bond. Examples of these are the vinyl esters and allyl and vinyl ethers of carboxylic acids, such as lauric acid, myristic acid, palmitic acid, stearic acid, and dicarboxylic acids, such as succinic acid, adipic acid, and monofunctional alcohols, such as lauryl, myristyl, palmityl, stearyl alcohol, methacrylic acid and acrylic acid esters, and difunctional alcohols, such as ethylene glycol and 1,4-butanediol, diallyl and divinyl ethers.

[0159] Also suitable are, for example, the methacrylic and acrylic esters of polyfunctional alcohols, especially those which do not contain any other functional groups other than hydroxyl groups or, at most, only ether groups.Examples of such alcohols are difunctional alcohols, such as ethylene glycol, propylene glycol and their more highly condensed representatives, such as diethylene glycol, triethylene glycol, dipropylene glycol, tripropylene glycol, butanediol, pentanediol, hexanediol, neopentyl glycol, alkoxylated phenolic compounds, such as ethoxylated and propoxylated bisphenols, cyclohexanedimethanol, trifunctional and polyfunctional alcohols, such as glycerol, trimethylolpropane, butanetriol, trimethylolethane, pentaerythritol, ditrimethylolpropane, dipentaerythritol, sorbitol, mannitol and the corresponding alkoxylated, especially ethoxylated and propoxylated alcohols.

[0160] Other suitable reactive diluents are polyester(meth)acrylates, which are (meth)acrylic acid esters of polyesterols.

[0161] Examples of suitable polyesterols are those which can be prepared by esterifying polycarboxylic acids, preferably dicarboxylic acids, with polyols, preferably diols. The starting materials for such hydroxyl-containing polyesters are known to those skilled in the art. Usable dicarboxylic acids are 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 said 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.

[0162] Suitable reactive diluents are further represented by the formula: [ka] and the allyl esters of acrylic acid, methacrylic acid and cyanoacrylic acid.

[0163] Among the reactive diluents given as examples, in particular and in view of the preferred compositions mentioned above, those containing photopolymerizable groups are used.

[0164] This group includes, for example, di- and polyhydric alcohols, such as ethylene glycol, propylene glycol and their more highly condensed representatives, such as diethylene glycol, triethylene glycol, dipropylene glycol, tripropylene glycol, butanediol, pentanediol, hexanediol, neopentyl glycol, cyclohexanedimethanol, glycerol, trimethylolpropane, butanetriol, trimethylolethane, pentaerythritol, ditrimethylolpropane, dipentaerythritol, sorbitol, mannitol and the corresponding alkoxylated, especially ethoxylated and propoxylated, alcohols.

[0165] This group also includes, for example, alkoxylated phenolic compounds, such as ethoxylated and propoxylated bisphenols.

[0166] These reactive diluents may furthermore be, for example, epoxides or urethane (meth)acrylates.

[0167] Epoxide (meth)acrylates are obtainable, for example, by reaction of epoxidized olefins or poly- or diglycidyl ethers, such as bisphenol A diglycidyl ether, with (meth)acrylic acid, as known to those skilled in the art.

[0168] The urethane (meth)acrylates are in particular the products of reactions of hydroxylalkyl (meth)acrylates with polyisocyanates or diisocyanates, which are likewise known to the person skilled in the art.

[0169] Such epoxides and urethane (meth)acrylates are included in the compounds listed above as "mixed forms."

[0170] When reactive diluents are used, their amount 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 invention, is achieved, but, on the other hand, the phase behavior of the liquid crystal composition is not excessively impaired. A low crosslinking (high crosslinking) liquid crystal composition can be prepared, for example, using a corresponding reactive diluent having a relatively low (high) number of reactive units per molecule.

[0171] Groups of diluents include, for example: C1-C4 alcohols, such as methanol, ethanol, n-propanol, isopropanol, butanol, isobutanol, sec-butanol, in particular C5-C12 alcohols, n-pentanol, n-hexanol, n-heptanol, n-octanol, n-nonanol, n-decanol, n-undecanol and n-dodecanol and their isomers, glycols, such as 1,2-ethylene glycol, 1,2- and 1,3-propylene glycol, 1,2-, 2,3- and 1,4-butylene glycol, di- and triethylene glycol, di- and tripropylene glycol, ethers, such as methyl tert-butyl ether, 1,2-ethylene glycol mono- and dimethyl ether, 1,2-ethylene glycol mono- and diethyl ether, 3-methyl-, 4-methyl-, 5-methyl-, 6-methyl-, 7-methyl-, 8-methyl-, 9-methyl-, 10-methyl-, 11-methyl-, 12-methyl-, 13-methyl-, 14-methyl-, 15-methyl-, 16-methyl-, 17-methyl-, 18-methyl-, 19-methyl-, 20-methyl-, 21-methyl-, 22-methyl-, 23-methyl-, 24-methyl-, 25-methyl-, 26-methyl-, 27-methyl-, 28-methyl-, 29-methyl-, 30-methyl-, 31-methyl-, 32-methyl-, 33-methyl-, 34-methyl-, 35-methyl-, 36-methyl-, 37-methyl-, 38-methyl-, 39-methyl-, 40-methyl-, 41-methyl-, 42-methyl-, 43-methyl-, 44-methyl-, 45-methyl xypropanol, 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 oil and heating oil and natural oils such as olive oil, soybean oil, rapeseed oil, linseed oil and sunflower oil. Examples include:

[0172] It is of course also possible to use mixtures of these diluents in the compositions according to the invention.

[0173] These diluents can also be mixed with water, as long as they are at least somewhat miscible. Examples of suitable diluents here are C1-C4 alcohols, such as methanol, ethanol, n-propanol, isopropanol, butanol, isobutanol and sec-butanol, glycols, such as 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, such as tetrahydrofuran and dioxane, ketones, such as acetone, methyl ethyl ketone and diacetone alcohol (4-hydroxy-4-methyl-2-pentanone), and C1-C4 alkyl esters, such as methyl acetate, ethyl acetate, propyl acetate and butyl acetate.

[0174] A diluent is optionally used in a proportion of about 0 to 10.0% by weight, preferably about 0 to 5.0% by weight, based on the total weight of the RM formulation.

[0175] The defoamers and degassing agents (c1)), lubricants and flow aids (c2)), heat- and radiation-curing aids (c3)), substrate-wetting aids (c4)), wetting and dispersing aids (c5)), hydrophobizing agents (c6)), adhesion promoters (c7)) and aids which promote scratch resistance (c8)) cannot be strictly separated from one another in their functions.

[0176] For example, lubricants and flow aids often also function as defoamers and / or degassing agents and / or aids for improving scratch resistance. Radiation curing aids can also function as lubricants and flow aids and / or degassing agents and / or substrate wetting aids. In individual cases, some of these aids can also perform the function of adhesion promoters (c8)).

[0177] Therefore, in accordance with the above, certain additives can be classified into a number of groups c1) to c8) as described below.

[0178] The antifoaming agents of group c1) include silicon-free polymers and silicon-containing polymers, for example unmodified or modified polydialkylsiloxanes or branched, comb or block copolymers containing polydialkylsiloxanes and polyether units, the latter being derived from ethylene oxide or propylene oxide.

[0179] Degassing agents of group c1) include, for example, organic polymers such as polyethers and polyacrylates, dialkylpolysiloxanes, in particular dimethylpolysiloxanes, organically modified polysiloxanes, such as arylalkyl-modified polysiloxanes and fluorosilicones.

[0180] The action of antifoaming agents is essentially based on preventing the formation of foam or on destroying foam that has already formed. Antifoaming agents essentially work by promoting the coalescence of finely divided gases or bubbles to give larger bubbles in the medium to be deaerated, e.g. the composition according to the invention, and thus promoting the escape of gas (air). Antifoaming agents can often also be used as deaerating agents and vice versa, so these additives are included together in group c1).

[0181] Such auxiliaries are, for example, from TEGO: TEGO® Foamex 800, TEGO® Foamex 805, TEGO® Foamex 810, TEGO® Foamex 815, TEGO® Foamex 825, TEGO® Foamex 835, TEGO® Foamex 840, TEGO® Foamex 842, TEGO® Foamex 1435, TEGO® Foamex 1488, TEGO® Foamex 1495, TEGO® Foamex 3062, TEGO® Foamex 7447, TEGO® Foamex 8020, Tego® Foamex N, TEGO® Foamex K3, TEGO® Antifoam 2-18, TEGO® Antifoam 2-18, TEGO® Antifoam 2-57, TEGO® Antifoam 2-80, TEGO® Antifoam 2-82, TEGO® Antifoam 2-89, TEGO® Antifoam 2-92, TEGO® Antifoam 14, TEGO® Antifoam 28, TEGO® Antifoam 81, TEGO® Antifoam D90, TEGO® Antifoam 93, TEGO® Antifoam 200, TEGO® Antifoam 201, TEGO® Antifoam 202, TEGO® Antifoam 793, TEGO® Antifoam 1488, TEGO® Antifoam 3062, TEGOPREN® 5803, TEGOPREN® 5852, TEGOPREN® 5863, TEGOPREN® 7008, TEGO® Antifoam 1-60, TEGO® Antifoam 1-62, TEGO® Antifoam 1-85, TEGO® Antifoam 2-67, TEGO® Antifoam WM20, TEGO® Antifoam50, TEGO® Antifoam 105, TEGO® Antifoam 730, 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 KE600, TEGO® Antifoam KS911, TEGO® Antifoam MR1000, TEGO® Antifoam KS1100, Tego® Airex 900, Tego® Airex 910, Tego® Airex 931, Tego® Airex 935, Tego® Airex 936, Tego® Airex 960, Tego® Airex 970, Tego® Airex 980 and Tego® Airex 985 as well as from BYK as BYK®-011, BYK®-019, BYK®-020, BYK®-021, BYK®-022, BYK®-023, BYK®-024, BYK®-025, BYK®-027, BYK®-031, BYK®-032, BYK®-033, BYK®-034, BYK®-035, BYK®

[0033] BYK®-036, BYK®-037, BYK®-045, BYK®-051, BYK®-052, BYK®-053, BYK®-055, BYK®-057, BYK®-065, BYK®-066, BYK®-070, BYK®-080, BYK®-088, BYK®-141, and BYK®-A530.

[0182] The auxiliaries of group c1) are optionally used in a proportion of about 0 to 3.0% by weight, preferably about 0 to 2.0% by weight, based on the total weight of the RM formulation.

[0183] In group c2), the lubricants and flow aids typically do not contain silicon, but also include silicon-containing polymers, such as polyacrylates or modifiers, such as low molecular weight polydialkylsiloxanes. The modification consists in replacing part of the alkyl groups with various organic radicals, such as polyethers, polyesters, or even long-chain alkyl radicals, the former being most frequently used.

[0184] The polyether radicals in the corresponding modified polysiloxanes are usually composed of ethylene oxide and / or propylene oxide units. In general, the higher the proportion of these alkylene oxide units in the modified polysiloxane, the more hydrophilic the resulting product will be.

[0185] Such auxiliaries are commercially available, for example, from TEGO as TEGO® Glide 100, TEGO® Glide ZG400, TEGO® Glide 406, TEGO® Glide 410, TEGO® Glide 411, TEGO® Glide 415, TEGO® Glide 420, TEGO® Glide 435, TEGO® Glide 440, TEGO® Glide 450, TEGO® Glide A115, TEGO® Glide B1484 (which can also be used as a defoamer and degasser), TEGO® Flow ATF, TEGO® Flow 300, TEGO® Flow 460, TEGO® Flow 425 and TEGO® Flow ZFS460. Suitable radiation curable lubricants and flow aids that can also be used to improve scratch resistance are the products TEGO® Rad 2100, TEGO® Rad 2200, TEGO® Rad 2500, TEGO® Rad 2600 and TEGO® Rad 2700, also available from TEGO.

[0186] Such auxiliaries are available, for example, from BYK as BYK®-300, BYK®-306, BYK®-307, BYK®-310, BYK®-320, BYK®-333, BYK®-341, Byk® 354, Byk® 361, Byk® 361N, BYK® 388.

[0187] The auxiliaries of group c2) are optionally used in a proportion of about 0 to 3.0% by weight, preferably about 0 to 2.0% by weight, based on the total weight of the RM formulation.

[0188] In group c3), radiation curing auxiliaries include, in particular, polysiloxanes with terminal double bonds, which are, for example, constituents of acrylate groups. Such auxiliaries can be crosslinked by actinic radiation or, for example, electron beams. These auxiliaries usually combine many properties. In the uncrosslinked state, they can function as defoamers, degassing agents, lubricants, flow auxiliaries and / or substrate wetting auxiliaries, whereas in the crosslinked state, they improve, in particular, the scratch resistance of coatings or films that can be produced, for example, using the compositions according to the invention. The improvement of the gloss properties, for example, precisely of those coatings or films, is essentially considered to be the result of the action of these auxiliaries as defoamers, degassing agents and / or lubricants and of flow auxiliaries (in the uncrosslinked state).

[0189] Examples of suitable radiation curing coagents are the products TEGO® Rad 2100, TEGO® Rad 2200, TEGO® Rad 2500, TEGO® Rad 2600 and TEGO® Rad 2700 available from TEGO and the product BYK®-371 available from BYK.

[0190] The heat curing coagents of group c3) contain, for example, primary OH groups which can react with, for example, isocyanate groups of the binder.

[0191] Examples of heat curing coagents that can be used are the products BYK®-370, BYK®-373 and BYK®-375 available from BYK.

[0192] The auxiliaries of group c3) 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 RM formulation.

[0193] Substrate wetting aids of group c4) have in particular the function of increasing the wetting of the substrate to be printed or coated with, for example, a printing ink or coating composition, for example a composition according to the invention. The generally accompanying improvement in the lubrication and flow behavior of such printing inks or coating compositions influences the appearance of the finished (e.g. crosslinked) print or coating.

[0194] A variety of such auxiliaries are commercially available, for example from Tego as TEGO® Wet KL245, TEGO® Wet 250, TEGO® Wet 260 and TEGO® Wet ZFS453, and from BYK as BYK®-306, BYK®-307, BYK®-310, BYK®-333, BYK®-344, BYK®-345, BYK®-346 and Byk®-348.

[0195] The auxiliary of group c4) is optionally used 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.

[0196] The wetting and dispersing auxiliaries of group c5) have the function in particular of preventing pigment floating and unevenness and settling and are therefore particularly suitable for pigmented compositions according to the invention, if required.

[0197] These auxiliaries essentially stabilize the pigment dispersions by electrostatic repulsion and / or steric hindrance of the pigment particles containing these additives. In the latter case, the interaction of the auxiliaries with the surrounding medium (e.g. binder) plays the main role.

[0198] The use of such wetting and dispersing aids is common practice, for example in the art of printing inks and paints, so that the selection of suitable auxiliaries of this type, when they are used, generally presents no difficulty to the skilled artisan.

[0199] Such wetting and dispersing aids are available, for example, from Tego as TEGO® Dispers 610, TEGO® Dispers 610S, TEGO® Dispers 630, TEGO® Dispers 700, TEGO® Dispers 705, TEGO® Dispers 710, TEGO® Dispers 720W, TEGO® Dispers 725W, TEGO® Dispers 730W, TEGO® Dispers 735W and TEGO® Dispers740W as well as from BYK Disperbyk®, Disperbyk®-107, Disperbyk®-108, Disperbyk®-110, Disperbyk®-111, Disperbyk®-115, Disperbyk®-130, Disperbyk®-160, Disperbyk®-161, Disperbyk®-162, Disperbyk®-163, Disperbyk®-164, Disperbyk®-165, Disperbyk®-166, Disperbyk®-167, Disperbyk®-170, Disperbyk®-174, Disperbyk®-180, D Commercially available as isperbyk®-181, Disperbyk®-182, Disperbyk®-183, Disperbyk®-184, Disperbyk®-185, Disperbyk®-190, Anti-Terra®-U, Anti-Terra®-U80, Anti-Terra®-P, Anti-Terra®-203, Anti-Terra®-204, Anti-Terra®-206, BYK®-151, BYK®-154, BYK®-155, BYK®-P104S, BYK®-P105, Lactimon®, Lactimon®-WS and Bykumen®.

[0200] The amount of auxiliary in group c5) used is determined based on the average molecular weight of the auxiliary, therefore it is advisable in each case to carry out preliminary experiments, which can easily be carried out by a person skilled in the art.

[0201] Hydrophobizing agents of group c6) can be used, for example, to impart water-repellent properties to prints or coatings produced with the compositions according to the invention, thereby preventing or at least greatly reducing swelling due to water absorption, which in turn changes, for example, the optical properties of such prints or coatings. Furthermore, this can prevent or at least greatly reduce water absorption, for example when the compositions are used as printing inks in offset printing.

[0202] Such hydrophobizing agents are commercially available, for example, from Tego as Tego® Phobe WF, Tego® Phobe 1000, Tego® Phobe 1000S, Tego® Phobe 1010, Tego® Phobe 1030, Tego® Phobe 1010, Tego® Phobe 1010, Tego® Phobe 1030, Tego® Phobe 1040, Tego® Phobe 1050, Tego® Phobe 1200, Tego® Phobe 1300, Tego® Phobe 1310 and Tego® Phobe 1400.

[0203] The auxiliaries of group c6) 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 RM formulation.

[0204] Adhesion promoters of group c7) have the function of improving the adhesion of two interfaces in contact. From this it follows directly that essentially the only part of the adhesion promoter that is effective is that part that is located at one or the other or both interfaces. For example, if it is desired to apply a liquid or pasty 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 pretreated (also called priming) with the adhesion promoter, i.e. the substrate is endowed with modified chemical and / or physical surface properties.

[0205] If the substrate has been primed beforehand, this means that the contacting interfaces are, 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 adhesive properties between the substrate and the primer but also those between the substrate and the printing ink or coating composition or paint are involved in the adhesion of the entire multilayer structure on the substrate.

[0206] Adhesion promoters in the broad sense may also include the substrate wetting aids already listed in group c4), but these do not generally have the same adhesion promoting capabilities.

[0207] Considering the wide variation in the physical and chemical properties of the substrates and of e.g. printing inks, coating compositions and paints intended for printing and coating, the diversity of adhesion promoter systems is not surprising.

[0208] Silane-based adhesion promoters are, 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, for example, from Huels under the trade name DYNASILAN®.

[0209] Corresponding technical information from the manufacturers of such additives should generally be used, or a person skilled in the art can obtain this information in a simple manner through corresponding preliminary experiments.

[0210] However, if these additives are added to the RM formulation according to the invention as auxiliaries of group c7), their proportion optionally corresponds to about 0-5.0% by weight, based on the total weight of the RM formulation. These concentration data serve only as a guideline, since the amount and what the additive is is determined in each individual case by the nature of the substrate and the printing / coating composition. The corresponding technical information in this case is usually available from the manufacturers of such additives or can be determined in a simple manner by the skilled person through corresponding preliminary experiments.

[0211] Examples of auxiliaries for improving the scratch resistance of group c8) include the abovementioned products TEGO® Rad 2100, TEGO® Rad 2200, TEGO® Rad 2500, TEGO® Rad 2600 and TEGO® Rad 2700, which are available from Tego.

[0212] For these auxiliaries, the amount data given in group c3) are likewise relevant, i.e. 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.

[0213] Examples of light, heat and / or oxidation stabilizers include: Alkylated monophenols, such as 2,6-di-tert-butyl-4-methylphenol, 2-tert-butyl-4,6-dimethylphenol, 2,6-di-tert-butyl-4-ethylphenol, 2,6-di-tert-butyl-4-n-butylphenol, 2,6-di-tert-butyl-4-isobutylphenol, 2,6-dicyclopentyl-4-methylphenol, 2-(α-methylcyclohexyl)-4,6-dimethylphenol, 2,6-dioctadecyl-4-methylphenol, 2,4,6-tricyclohexylphenol, 2,6-di-tert-butyl-4-methoxymethylphenol, linear or branched nonylphenols having side chains, such as 2,6-dinonyl-4-methylphenol, 2,4-dimethyl-6-(1'-methylundec-1'-yl)phenol, 2,4-dimethyl-6-(1'-methylheptadec-1'-yl)phenol, 2,4-dimethyl-6-(1'-methyltridec-1'-yl)phenol and mixtures of these compounds, alkylthiomethylphenols, such as 2,4-dioctylthiomethyl-6-tert-butylphenol, 2,4-dioctylthiomethyl-6-methylphenol, 2,4-dioctylthiomethyl-6-ethylphenol and 2,6-didodecylthiomethyl-4-nonylphenol, Hydroquinone and alkylated hydroquinones, such as 2,6-di-tert-butyl-4-methoxyphenol, 2,5-di-tert-butylhydroquinone, 2,5-di-tert-amylhydroquinone, 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; Tocopherols, such as α-tocopherol, β-tocopherol, γ-tocopherol, δ-tocopherol and mixtures of these compounds, as well as tocopherol derivatives, such as tocopheryl acetate, tocopheryl succinate, tocopheryl nicotinate and tocopheryl polyoxyethylene succinate ("tocofersolate"); Hydroxylated diphenyl thioethers, such as 2,2'-thiobis(6-tert-butyl-4-methylphenol), 2,2'-thiobis(4-octylphenol), 4,4'-thiobis(6-tert-butyl-3-methylphenol), 4,4'-thiobis(6-tert-butyl-2-methylphenol), 4,4'-thiobis(3,6-di-sec-amylphenol) and 4,4'-bis(2,6-dimethyl-4-hydroxyphenyl) disulfide; Alkylidene bisphenols, such as 2,2'-methylenebis(6-tert-butyl-4-methylphenol), 2,2'-methylenebis(6-tert-butyl-4-ethylphenol), 2,2'-methylenebis[4-methyl-6-(α-methylcyclohexyl)phenol], 2,2'-methylenebis(4-methyl-6-cyclohexylphenol), 2,2'-methylenebis(6-nonyl-4-methylphenol), 2,2'-methylenebis(4,6-di-tert-butylphenol), 2,2-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, O-, N- and S-benzyl compounds, such as 3,5,3',5'-tetra-tert-butyl-4,4'-dihydroxydibenzyl ether, octadecyl 4-hydroxy-3,5-dimethylbenzyl mercaptoacetate, tridecyl 4-hydroxy-3,5-di-tert-butylbenzyl mercaptoacetate, tris(3,5-di-tert-butyl-4-hydroxybenzyl)amine, bis(4-tert-butyl-3-hydroxy-2,6-dimethylbenzyl)dithioterephthalate, bis(3,5-di-tert-butyl-4-hydroxybenzyl)sulfide and isooctyl-3,5-di-tert-butyl-4-hydroxybenzyl mercaptoacetate, Aromatic hydroxybenzyl compounds, such as 1,3,5-tris(3,5-di-tert-butyl-4-hydroxybenzyl)-2,4,6-trimethylbenzene, 1,4-bis(3,5-di-tert-butyl-4-hydroxybenzyl)-2,3,5,6-tetramethylbenzene and 2,4,6-tris(3,5-di-tert-butyl-4-hydroxybenzyl)phenol; Triazine compounds, such as 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 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. Benzyl phosphonates, such as 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; Acylaminophenols, such as 4-hydroxylauroylanilide, 4-hydroxystearoylanilide and octyl N-(3,5-di-tert-butyl-4-hydroxyphenyl)carbamate; Propionate and acetate esters, for example esters of mono- or polyhydric alcohols, for example esters of 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]-octane, Propionamides based on amine derivatives, such as N,N'-bis(3,5-di-tert-butyl-4-hydroxyphenylpropionyl)hexamethylenediamine, N,N'-bis(3,5-di-tert-butyl-4-hydroxyphenylpropionyl)trimethylenediamine and N,N'-bis(3,5-di-tert-butyl-4-hydroxyphenylpropionyl)hydrazine, Ascorbic acid (vitamin C) and ascorbic acid derivatives, such as ascorbyl palmitate, ascorbyl laurate, ascorbyl stearate, ascorbyl sulfate and ascorbyl phosphate, Antioxidants based on amine compounds, such as N,N'-diisopropyl-p-phenylenediamine, N,N'-di-sec-butyl-p-phenylenediamine, N,N'-bis(1,4-dimethylpentyl)-p-phenylenediamine, N,N'-bis(1-ethyl-3-methylpentyl)-p-phenylenediamine, N,N'-bis(1-methylheptyl)-p-phenylenediamine, N,N'-dicyclohexyl-p-phenylenediamine, N,N'-diphenyl-p-phenylenediamine, Diamine, 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 diphenylamines such as p,p'-di-tert-octyldiphenylamine, 4-n-butylaminophenol, 4-butyrylaminophenol, 4-nonanoylaminophenol, 4-dodecanoylaminophenol, 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-naphthylamines, mixtures of mono- and dialkylated tert-butyl / tert-octyldiphenylamines, mixtures of mono- and dialkylated nonyldiphenylamines, mixtures of mono- and dialkylated dodecyldiphenylamines, mixtures of mono- and dialkylated isopropyl / isohexyldiphenylamines, mixtures of mono- and dialkylated tert-butyldiphenylamines, 2,3-dihydro-3,3-dimethyl-4H-1,4-benzothiazine, phenothiazine phenothiazine, mixture of mono- and dialkylated tert-butyl / tert-octylphenothiazines, mixture of mono- and dialkylated tert-octylphenothiazines, N-allylphenothiazine, N,N,N',N'-tetraphenyl-1,4-diaminobut-2-ene, N,N-bis(2,2,6,6-tetramethylpiperidin-4-yl)hexamethylenediamine, bis(2,2,6,6-tetramethylpiperidin-4-yl)sebacate, 2,2,6,6-tetramethylpiperidin-4-one and 2,2,6,6-tetramethylpiperidin-4-ol, Phosphines, phosphites and phosphonites, such as triphenylphosphine, triphenylphosphite, diphenyl alkyl phosphites, phenyl dialkyl phosphites, tris(nonylphenyl)phosphite, trilauryl phosphite, trioctadecyl phosphite, distearyl pentaerythritol diphosphite, tris(2,4-di-tert-butylphenyl)phosphite, diisodecyl pentaerythritol diphosphite, bis(2,4-di-tert-butylphenyl)pentaerythritol diphosphite, bis(2,6-di-tert-butyl-4-methylphenyl)pentaerythritol diphosphite, diisodecyloxypentaerythritol diphosphite, bis(2,4-di-tert-butyl-6-methylphenyl)pentaerythritol diphosphite, methylphenyl)pentaerythritol diphosphite, bis(2,4,6-tris(tert-butylphenyl))pentaerythritol diphosphite, tristearyl sorbitol triphosphite, tetrakis(2,4-di-tert-butylphenyl)4,4'-biphenylene diphosphonite, 6-isooctyloxy-2,4,8,10-tetra-tert-butyl-12H-dibenz[d,g]-1,3,2-dioxaphosphocin, 6-fluoro-2,4,8,10-tetra-tert-butyl-12-methyl-dibenz[d,g]-1,3,2-dioxaphosphocin, bis(2,4-di-tert-butyl-6-methylphenyl)methyl phosphite and bis(2,4-di-tert-butyl-6-methylphenyl)ethyl phosphite, 2-(2'-hydroxyphenyl)benzotriazoles, such as 2-(2'-hydroxy-5'-methylphenyl)benzotriazole, 2-(3',5'-di-tert-butyl-2'-hydroxyphenyl)benzotriazole, 2-(5'-tert-butyl-2'-hydroxyphenyl)benzotriazole, 2-(2'-hydroxy-5'-(1,1,3,3-tetramethylbutyl)phenyl)benzotriazole, 2-(3',5'-di-tert-butyl-2'-hydroxyphenyl)-5-chlorobenzotriazole, 2-(3'-tert t-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'-di-tert-amyl-2'-hydroxyphenyl)benzotriazole, 2-(3,5'-bis-(α,α-dimethylbenzyl)-2'-hydroxyphenyl)benzotriazole, mixtures containing the following: 2-(3'-tert-butyl-2'- Hydroxy-5'-(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' -tert-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-benzotriazol-2-ylphenol]; 2-[3'-tert-butyl-5'-(2-methoxycarbonylethyl)-2'-hydroxyphenyl]-2H-benzotriazole completely esterified with polyethylene glycol 300, Sulfur-containing peroxide scavengers and sulfur-containing antioxidants, such as esters of 3,3'-thiodipropionic acid, such as the lauryl, stearyl, myristyl and tridecyl esters, zinc salts of mercaptobenzimidazole and 2-mercaptobenzimidazole, dibutyl zinc dithiocarbamate, dioctadecyl disulfide and pentaerythritol tetrakis(β-dodecylmercapto)propionate; 2-hydroxybenzophenones, such as the 4-hydroxy, 4-methoxy, 4-octyloxy, 4-decyloxy, 4-dodecyloxy, 4-benzyloxy, 4,2',4'-trihydroxy and 2'-hydroxy-4,4'-dimethoxy derivatives; Esters of unsubstituted and substituted benzoic acids, such as 4-tert-butylphenyl salicylate, phenyl salicylate, octylphenyl salicylate, dibenzoylresorcinol, bis(4-tert-butylbenzoyl)resorcinol, benzoylresorcinol, 2,4-di-tert-butylphenyl 3,5-di-tert-butyl-4-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, Acrylates, such as ethyl α-cyano-β,β-diphenylacrylate, isooctyl α-cyano-β,β-diphenylacrylate, methyl α-methoxycarbonylcinnamate, methyl α-cyano-β-methyl-p-methoxycinnamate, butyl-α-cyano-β-methyl-p-methoxycinnamate and methyl-α-methoxycarbonyl-p-methoxycinnamate, sterically hindered amines, such as bis(2,2,6,6-tetramethylpiperidin-4-yl) ) sebacate, bis(2,2,6,6-tetramethylpiperidin-4-yl) succinate, bis(1,2,2,6,6-pentamethylpiperidin-4-yl) sebacate, bis(1-octyloxy-2,2,6,6-tetramethylpiperidin-4-yl) sebacate, bis(1,2,2,6,6-pentamethylpiperidin-4-yl)-n-butyl-3,5-di-tert-butyl-4-hydroxybenzyl malonate, 1-(2-hydroxyethyl)-2,2,6,6- Condensation products of tetramethyl-4-hydroxypiperidine with succinic acid, Condensation products of N,N'-bis(2,2,6,6-tetramethylpiperidin-4-yl)hexamethylenediamine with 4-tert-octylamino-2,6-dichloro-1,3,5-triazine, Tris(2,2,6,6-tetramethylpiperidin-4-yl)nitrilotriacetate, Tetrakis(2,2,6,6-tetramethylpiperidin-4-yl)1,2,3,4-butanetetracarboxylate , 1,1'-(1,2-ethylene)bis(3,3,5,5-tetramethylpiperazinone), 4-benzoyl-2,2,6,6-tetramethylpiperidine, 4-stearyloxy-2,2,6,6-tetramethylpiperidine, bis(1,2,2,6,6-pentamethylpiperidin-4-yl)2-n-butyl-2-(2-hydroxy-3,5-di-tert-butylbenzyl)malonate, 3-n-octyl-7,7,9,9-tetramethyl-1,3,8-triazaspiro[4.5]Decane-2,4-dione, bis(1-octyloxy-2,2,6,6-tetramethylpiperidin-4-yl)sebacate, bis(1-octyloxy-2,2,6,6-tetramethylpiperidin-4-yl)succinate, N,N'-bis(2,2,6,6-tetramethylpiperidin-4-yl)hexamethylenediamine and condensation product of 4-morpholino-2,6-dichloro-1,3,5-triazine, 2-chloro-4,6-bis(4-n-butylamino-2,2,6,6-tetramethylpiperidin-4-yl)-1, Condensation products of 3,5-triazine and 1,2-bis(3-aminopropylamino)ethane, 2-chloro-4,6-di(4-n-butylamino-1,2,2,6,6-pentamethylpiperidin-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-tetramethylpiperidin-4-yl)pyrrolidine-2 ,5-dione, 3-dodecyl-1-(1,2,2,6,6-pentamethylpiperidin-4-yl)pyrrolidine-2,5-dione, mixture of 4-hexadecyloxy- and 4-stearyloxy-2,2,6,6-tetramethylpiperidines, condensation products of N,N'-bis(2,2,6,6-tetramethylpiperidin-4-yl)hexamethylenediamine with 4-cyclohexylamino-2,6-dichloro-1,3,5-triazine, 1,2-bis(3-aminopropylamino)ethane with 2,4,6-trichloro-1,3,5-triazine, Condensation products with riazine, 4-butylamino-2,2,6,6-tetramethylpiperidine, N-(2,2,6,6-tetramethylpiperidin-4-yl)-n-dodecylsuccinimide, N-(1,2,2,6,6-pentamethylpiperidin-4-yl)-n-dodecylsuccinimide, 2-undecyl-7,7,9,9-tetramethyl-1-oxa-3,8-diaza-4-oxo-spiro[4.5]-decane, 7,7,9,9-tetramethyl-2-cycloundecyl-1-oxa-3,8-diaza-4-oxospiro-[4.5] Condensation products of decane with epichlorohydrin, condensation products of 4-amino-2,2,6,6-tetramethylpiperidine with tetramethylolacetylenediurea and poly(methoxypropyl-3-oxy)-[4(2,2,6,6-tetramethyl)piperidinyl]-siloxane. Oxalamides, such as 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, 2-ethoxy-5-tert-butyl-2'-ethoxanilide and mixtures thereof with 2-ethoxy-2'-ethyl-5,4'-di-tert-butoxanilide and mixtures of ortho-, para-methoxy-disubstituted oxanilides and mixtures of ortho-, para-ethoxy-disubstituted oxanilides, 2-(2-hydroxyphenyl)-1,3,5-triazines, such as 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)-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-(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 Examples include:

[0214] In another preferred embodiment, the RM formulation contains one or more specific antioxidant additives, preferably antioxidant additives selected from the Irganox® series, such as the antioxidants Irganox® 1076 and Irganox® 1010 available from Ciba, Switzerland.

[0215] In another preferred embodiment, the RM formulation contains a combination of one or more, more preferably two or more, photoinitiators, for example selected from the commercially available Irgacure® or Darocure® (Ciba AG) series, in particular Irgacure 127, Irgacure 184, Irgacure 369, Irgacure 651, Irgacure 817, Irgacure 907, Irgacure 1300, Irgacure, Irgacure 2022, Irgacure 2100, Irgacure 2959 or Darcure TPO, further selected from the commercially available OXE02 (Ciba AG), NCI930, N1919T (Adeka), SPI-03 or SPI-04 (Samyang).

[0216] The overall concentration of polymerization initiator in the RM formulation is preferably 0.5-10%, highly preferably 0.8-8%, more preferably 1-6%.

[0217] In a preferred embodiment, the RM formulation is dissolved in a suitable solvent, preferably selected from organic solvents.

[0218] The solvent is preferably selected from ketones such as acetone, methyl ethyl ketone, methyl propyl ketone, methyl isobutyl ketone or cyclohexanone; acetates such as methyl acetate, ethyl acetate, butyl acetate or methyl acetoacetate; alcohols such as methanol, ethanol or isopropyl alcohol; aromatic solvents such as toluene or xylene; alicyclic hydrocarbons such as cyclopentane or cyclohexane; halogenated hydrocarbons such as dichloromethane or trichloromethane; glycols or their esters such as PGMEA (propyl glycol monomethyl ether acetate) or γ-butyrolactone. It is also possible to use binary, ternary or higher mixtures of the above solvents. In particular, for multilayer applications, methyl isobutyl ketone is the solvent preferably utilized.

[0219] When the RM formulation includes one or more solvents, the total concentration of all solids, including the RM, in the solvent is preferably 10-60%, more preferably 20-50%, especially 30-45%.

[0220] Preferably, the RM formulation comprises, in addition to one or more compounds of formula I, a) optionally one or more multireactive or direactive polymerizable mesogenic compounds, preferably selected from compounds of formula DRM and corresponding subformulas, and / or b) optionally one or more chiral mesogenic compounds, preferably selected from the compounds of formula CRM and its subformulae, and / or c) optionally one or more monoreactive mesogens, preferably selected from compounds of formula MRM and corresponding subformulas, and / or d) optionally one or more photoinitiators, and / or e) optionally one or more antioxidant additives, and / or f) optionally one or more adhesion promoters, and / or g) optionally one or more surfactants, and / or h) optionally one or more mono-, di- or multireactive polymerizable non-mesogenic compounds, and / or i) optionally, one or more dyes that exhibit an absorption maxima at the wavelengths used to initiate photopolymerization; and / or j) optionally one or more chain transfer agents, and / or k) optionally one or more (UV) stabilizers, and / or l) optionally one or more lubricants and flow aids, and m) optionally one or more diluents, and / or n) an optional non-polymerizable nematic component, and / or o) optionally one or more organic solvents; Contains:

[0221] More preferably, the RM formulation comprises: a) one or more compounds of formula I or corresponding preferred subformulas thereof, b) optionally one or more, preferably two or more, direactive polymerizable mesogenic compounds, preferably selected from compounds of formula DRMa-1, c) optionally one or more, preferably two or more, monoreactive polymerizable mesogenic compounds, preferably selected from the compounds of formula MRm-1 and / or MRM-4 and / or MRM-6 and / or MRM-7, d) optionally one or more chiral mesogenic compounds of formula CRM; e) optionally one or more antioxidant additives, preferably selected from unsubstituted and substituted esters of benzoic acid, in particular Irganox® 1076, if present, preferably in an amount of 0.01 to 2% by weight, very preferably 0.05 to 1% by weight; f) optionally, one or more photoinitiators, preferably Irgacure® 907 and / or SPI-3 g) optionally one or more organic solvents, preferably methyl isobutyl ketone Contains:

[0222] The present invention further comprises: providing a layer of the above and below mentioned RM formulation on a substrate, Polymerizing the polymerizable components of the RM formulation by photopolymerization, and Optionally peeling the polymerized film from the substrate and / or optionally providing it onto another substrate. The present invention relates to a method for producing a polymer film.

[0223] The RM formulation can be coated or printed onto a substrate, for example by spin coating, printing or other known techniques, and the solvent allowed to evaporate prior to polymerization. In most cases, it will be appropriate to heat the mixture to facilitate evaporation of the solvent.

[0224] The RM formulations can be applied to the substrate by conventional coating techniques such as spin coating, bar coating or blade coating, or by conventional printing techniques known to the expert, such as screen printing, offset printing, reel-to-reel printing, letterpress printing, gravure printing, rotogravure printing, flexography, intaglio printing, pad printing, heat seal printing, inkjet printing or printing by stamp or printing plate.

[0225] Suitable substrate materials and substrates are known to the expert and described in the literature, for example as conventional substrates used in the optical film industry, such as glass and plastics. Preferred substrates that are particularly suitable for polymerization are polyesters, such as polyethylene terephthalate (PET) or polyethylene naphthalate (PEN), polyvinyl alcohol (PVA), polycarbonate (PC), triacetyl cellulose (TAC) or cycloolefin polymer (COP) or commonly known color filter materials, in particular triacetyl cellulose (TAC), cycloolefin polymer (COP) or commonly known color filter materials. Also optical films obtained from different or the same RM materials can serve as substrates. This is particularly preferred when it is necessary to design a multilayer system containing one, two, three, four, five or more optical films in the optical component.

[0226] The RM formulation preferably exhibits uniform alignment throughout the layer. Preferably, the RM formulation exhibits uniform planar, uniform homeotropic, uniform cholesteric or patterned alignment.

[0227] RM layer (γ RM ) and the substrate (γ s The Friedel-Creagh-Kmetz rule can be used to predict whether a mixture will adopt a planar or homeotropic alignment by comparing the surface energies of the two molecules.

[0228] Gamma RM >γ s In the case of γ, the reactive mesogenic compound exhibits homeotropic alignment, RM <γ s In this case, the reactive mesogenic compound exhibits homogeneous alignment.

[0229] Without being bound by theory, when the surface energy of the substrate is relatively low, the intermolecular forces between the reactive mesogens are stronger than the forces across the RM-substrate interface, resulting in the reactive mesogens aligning perpendicular to the substrate (homeotropic alignment) to maximize the intermolecular forces.

[0230] Homeotropic alignment can also be achieved by using amphiphilic materials. They can be added directly to the polymerizable LC material or the substrate can be treated with these materials in the form of a homeotropic alignment layer. The polar heads of the amphiphilic materials are chemically bonded to the substrate and the hydrocarbon tails point perpendicular to the substrate. Intermolecular interactions between the amphiphilic materials and the RMs promote homeotropic alignment. Commonly used amphiphilic surfactants are listed above.

[0231] Another method used to promote homeotropic alignment is to subject plastic substrates to corona discharge treatment, which creates alcohol or ketone functional groups on the substrate surface. These polar groups can interact with polar groups present in the RM or surfactant to promote homeotropic alignment.

[0232] When the surface tension of the substrate is greater than that of the RM, the forces across the interface will dominate. The interfacial energy is minimized when the reactive mesogens align parallel to the substrate so that the long axis of the RM can interact with the substrate. One way that planar alignment can be promoted is to coat the substrate with a polyimide layer and then rub the alignment layer with a velvet cloth.

[0233] Other suitable planar alignment layers are known in the art, such as alignment layers made by rubbed polyimide or photoalignment as described in U.S. Pat. Nos. 5,602,661, 5,389,698 or 6,717,644.

[0234] In general, reviews of alignment techniques are given, for example, in "Thermotropic Liquid Crystals" by I. Sage, edited by GW Gray, John Wiley & Sons, 1987, pages 75-77; and "Liquid Crystals - Applications and Uses Vol. 3" by T. Uchida and H. Seki, edited by B. Bahadur, World Scientific Publishing, Singapore 1992, pages 1-63. Further reviews of alignment materials and alignment techniques are given in J. Cognard, Mol. Cryst. Liq. Cryst. 78, Supplement 1 (1981), pages 1-77.

[0235] However, it is also preferred that the orientation of the RM molecules varies with the layer thickness, such as types of splay, tilt or twist orientation, as are commonly known to the expert.

[0236] For the preparation of polymeric films according to the present invention, the polymerizable compounds in the RM formulation are polymerized or crosslinked (if one compound contains two or more polymerizable groups) by in-situ photopolymerization.

[0237] Photopolymerization can be carried out in one step. Compounds that did not react in the first step can also be photopolymerized or crosslinked in a second step ("final cure").

[0238] In a preferred method of preparation, the RM formulation is coated onto a substrate and subsequently photopolymerized by exposure to actinic radiation as described, for example, in WO 01 / 20394, DE 2,315,072 or WO 98 / 04651.

[0239] The photopolymerization of the LC material is preferably carried out by exposure to actinic radiation. Actinic radiation means irradiation with light, such as UV light, IR light or visible light, irradiation with X-rays or gamma rays or irradiation with high energy particles, such as ions or electrons. Preferably, the polymerization is carried out by light irradiation, in particular UV light. As a source of actinic radiation, for example a single UV lamp or a set of UV lamps can be used. Using high lamp power allows shortening the curing time. Another possible source of light radiation is a laser, such as for example a UV laser, an IR laser or a visible laser. Another possible source of light radiation is an LED lamp.

[0240] The curing time depends, inter alia, on the reactivity of the polymerizable LC material, the thickness of the coating layer, the type of polymerization initiator and the power of the UV lamp. The curing time is preferably less than 5 minutes, very preferably less than 3 minutes, most preferably less than 1 minute. For mass production, short curing times of less than 30 seconds are preferred.

[0241] Suitable UV radiation power is preferably between 5 and 200 mWcm -2 in the range of 50 to 175 mWcm -2 in the range of 100-150 mWcm -2 The range is.

[0242] In relation to the applied UV radiation and as a function of time, a suitable UV dose is preferably between 25 and 7200 mJcm -2 More preferably, it is in the range of 100 to 7200 mJcm -2 The range is preferably 200 to 7200 mJcm -2 The range is.

[0243] The photopolymerization is preferably carried out in an inert gas atmosphere, preferably in a heated nitrogen atmosphere, but polymerization in air is also possible.

[0244] The photopolymerization is carried out at a temperature of preferably 1 to 70°C, more preferably 5 to 50°C, and further preferably 15 to 30°C.

[0245] The polymerized LC film according to the invention has good adhesion to plastic substrates, especially TAC, COP and color filters, and can therefore be used as an adhesive or base coating for subsequent LC layers that would not otherwise adhere well to the substrate.

[0246] For optical applications of the polymer film, this preferably has a thickness of 0.5 to 10 μm, very preferably 0.5 to 5 μm, in particular 0.5 to 3 μm.

[0247] The optical retardation (δ(λ)) of a polymer film as a function of the wavelength (λ) of the incident beam is given by the following equation (7): δ(λ)=(2πΔn d) / λ (7) where (Δn) is the birefringence of the film, (d) is the thickness of the film, and λ is the wavelength of the incident beam. is given by:

[0248] According to Snelius' law, the birefringence as a function of the direction of the incident beam is given by Δn=sinΘ / sinΨ where sin Θ is the angle of incidence or tilt of the optical axis at the film, and sin Ψ is the corresponding angle of reflection. It is defined as follows:

[0249] Based on these laws, the birefringence and therefore the optical retardation depends on the thickness of the film and the tilt angle of the optical axis in the film (see Berek's compensator). Thus, those skilled in the art recognize that by adjusting the orientation of the liquid crystal molecules in a polymer film, different optical retardations or different birefringences can be induced.

[0250] The birefringence (Δn) of the polymer film of the present invention is preferably in the range of 0.1 to 0.8, more preferably in the range of 0.2 to 0.7, and further preferably in the range of 0.2 to 0.6.

[0251] The optical retardation as a function of thickness of the polymeric films according to the invention is less than 200 nm, more preferably less than 180 nm, and even more preferably less than 150 nm.

[0252] The polymer films of the present invention can also be used as alignment layers or substrates for other liquid crystal or RM materials. The inventors have found that the polymer films obtained from the above and below mentioned RM formulations are particularly useful for multilayer applications due to their improved dewetting properties. This allows the manufacture of optical films or preferably stacks of polymerized LC films.

[0253] In summary, the polymerised LC films and polymerisable LC materials according to the present invention are useful in optical elements such as polarisers, compensators, alignment layers, circular polarisers or colour filters in liquid crystal displays or projection systems and decorative images, for the preparation of liquid crystals or effect pigments and in particular in reflective films with spatially varying reflected colour, as multicolour images for decorative, information storage or security applications, e.g. unforgeable documents such as identity cards, credit cards, bank notes etc.

[0254] The polymerized LC films according to the invention can be used in transmissive or reflective displays. They can be used in conventional OLED displays or LCDs, especially LCDs.

[0255] The present invention is described above and hereinafter with particular reference to preferred embodiments, it being understood that various changes and modifications can be made without departing from the spirit and scope of the invention.

[0256] Many of the compounds mentioned above and below or their mixtures are commercially available.All of these compounds are known or can be prepared by methods known per se, as described in the literature (e.g. standard works such as Houben-Weyl, Methoden der Organischen Chemie [Methods of Organic Chemistry], Georg-Thieme-Verlag, Stuttgart), precisely under known reaction conditions suitable for said reactions.Herein, it is also possible to use variants known per se but not mentioned here.

[0257] It will be understood that modifications can be made to the above-described embodiments of the invention while remaining within the scope of the invention. Unless otherwise stated, alternative features serving the same, equivalent or similar purpose may replace each feature disclosed herein. Thus, unless otherwise stated, each feature disclosed is only one example of a generic series of equivalent or similar features.

[0258] All features disclosed herein may be combined in any combination, except combinations in which at least some of such features and / or steps are mutually exclusive. In particular, preferred features of the invention are applicable to all aspects of the invention and may be used in any combination. Similarly, features described in non-essential combinations may be used individually (not in combination).

[0259] It will be appreciated that many of the features described above, particularly many of the preferred embodiments, are inventive in their own right and are not merely part of an embodiment of the present invention, and independent protection may be sought for these features in addition to or in place of the invention claimed in this application.

[0260] The present invention will now be described in more detail with reference to the following examples, which are illustrative only and are not intended to limit the scope of the invention.

[0261] Unless otherwise stated, all temperature values ​​given in this application, such as for example the melting point T(K,N), the smectic (S) to nematic (N) phase transition T(S,N) and the clearing point T(N,I), are expressed in degrees Celsius (°C). Furthermore, K denotes the crystalline state, N denotes a nematic phase, SmX denotes an unidentified smectic phase, X denotes an unidentified mesophase and I denotes an isotropic phase. The data between these symbols represent the transition temperatures in °C.

[0262] Working Example Compound (RM-1) can be synthesized according to the following scheme: [ka] It was prepared according to

[0263] Preparation of Stage 1 [ka]

[0264] 2-Bromo-6-hydroxynaphthalene (44.6 g, 200 mmol), potassium carbonate (33.2 g, 240 mmol), sodium iodide (6 g, 40 mmol) and butanone (125 ml) are heated to 80° C. 6-Bromohexanol (40 g, 220 mmol) is added dropwise over 1.25 hours. After 24 hours, the mixture is cooled, filtered, washed with acetone and the solvent from the filtrate is removed in vacuo to give product G (70 g). Product G (70 g) is dissolved in DCM (100 ml) and purified by vacuum flash chromatography on silica (220 g) eluting with:- DCM:ethyl acetate 200:0, 198:2, 196:4, 194:6, 192:8, 190:10, 188:12, 186:14, 184:16, 182:18, 180:20, 178:22, 176:24, 174:26 ml. Fractions 4-14 are combined and the solvent removed in vacuo to give product H (44 g). Product H (44 g) and product E (10.9 g) are combined and recrystallized with toluene (100 ml) and heptane (100 ml). Cool in the fridge for 1 hour, filter, and wash with fridge-cooled toluene / petrol 1:1, then petrol to give product I (36 g). The solvent from the filtrate is removed in vacuo to give product J (18 g). Product C (22.4 g) and product I (36 g) are combined and purified by vacuum flash chromatography on silica (220 g) eluting with:- DCM:Ethyl acetate 200:0, 200:0, 200.0, 200:0, 200:0, 198:2, 196:4, 194:6, 192:8, 190:10, 188:12, 186:14, 184:16, 182:18, 180:20 ml. Fractions 5-14 are combined and the solvent removed in vacuo to give pure product K (55.1 g). The overall yield was product F (14.5 g) and product K (55.1 g), totalling 69.6 g (54% yield).

[0265] Preparation of Stage 2 [ka]

[0266] The reaction is carried out in two identical batches. The product of stage 1 (22 g, 68 mmol), trimethylsilylacetylene (11.5 ml, 83 mmol) and diisopropylamine (150 ml, 1.05 mmol) are sonicated for 30 min. Palladium II acetate (570 mg, 2.5 mmol), tri-tert-butylphosphonium tetrafluoroborate (644 mg, 2.2 mmol) and copper I iodide (284 mg, 1.5 mmol) are added. The mixture is slowly heated to 40° C. The reaction is exothermic and a thick precipitate forms. After reaching 65° C., it is cooled to 40° C. The mixture is kept at 40° C. for another hour and then cooled to room temperature. DCM (300 ml) is added followed by hydrochloric acid (550 ml, 2 M, 1.1 mol). The two layers are separated and the aqueous layer is extracted with DCM (2 x 50 ml). The organic layer is dried over anhydrous sodium sulfate, filtered and the solvent from the filtrate is removed in vacuo. Both batches are combined. The residue is dissolved in DCM and silica (150 g) is added. The mixture is purified by vacuum flash chromatography on silica (300 g) eluting with:- DCM:ethyl acetate 200:0, 198:2, 196:4, 194:6, 192:8, 190:10, 188:12, 186:14, 184:16, 182:18, 180:20, 178:22, 176:24, 174:26, 172:28, 170:30, 168:32, 166:34, 164:36, 162:38, 160:40, 158:42, 156:44, 154:46, 152:48, 150:50, 148:52, 146:54 ml. Fractions 13-23 are combined and the solvent removed in vacuo. The solid (approximately 41 g) is recrystallized from acetonitrile (80 ml), chilled in the freezer for 1 hour, filtered off, and washed with freezer-chilled acetonitrile to give the desired product as a white solid (35.5 g, 77%).

[0267] Preparation of Stage 3 [ka]

[0268] The product of stage 2 (17 g, 50 mmol) is dissolved in methanol (100 ml). Potassium carbonate (0.74 g, 5.4 mmol) is added and the mixture is stirred overnight. The solvent is removed in vacuo. The residue is dissolved in DCM (100 ml) and purified by vacuum flash chromatography on silica (120 g) eluting with:- DCM:Ethyl acetate 100:0, 95:5, 90:10, 90:10, 90:10 ml. Fractions 2-5 are combined and the solvent is removed in vacuo. The solid is recrystallised from DCM (10 ml) and petrol (90 ml), chilled in the fridge for 1 hour, filtered off and washed with chilled petrol to give the desired product as a white solid (13.04 g, 97% yield).

[0269] Preparation of Stage 4 [ka]

[0270] Sodium hydride (4.8 g, 120 mmol) is suspended in DMF (90 ml). 6-Bromo-2-naphthol (24 g, 108 mmol) is added portionwise over 20 min at 10°C-15°C. The mixture is stirred for a further 30 min. Isopropyl iodide (11.4 ml, 114 mmol) is added and the mixture is stirred over the weekend. Water (300 ml) is added carefully. Ethyl acetate (150 ml) and petrol (150 ml) are added and the two layers are separated. The organic layer is washed with water (2 x 50 ml). The organic layer is dried over anhydrous sodium sulfate, filtered and the solvent from the filtrate is removed in vacuo. The residue is dissolved in toluene (100 ml) and purified by vacuum flash chromatography on silica (120 g) eluting with toluene (100 ml fractions). Fractions 2-4 are combined and the solvent is removed in vacuo. Triturate the residue with freezer-chilled petrol (100 ml) and filter to give the desired product as a white solid (22 g, 77% yield).

[0271] Preparation of Stage 5 [ka]

[0272] The product of stage 4 (22 g, 83 mmol), trimethylsilylacetylene (14.8 ml, 105 mmol) and diisopropylamine (225 ml, 1.6 mol) are sonicated for 30 min. Palladium II acetate (210 mg, 0.94 mmol), tri-tert-butylphosphonium tetrafluoroborate (240 mg, 0.82 mmol) and copper I iodide (100 mg, 0.52 mmol) are added. The mixture is slowly heated to 45°C. The reaction is exothermic and a thick precipitate forms. After reaching 55°C, it is cooled to 50°C. The mixture is held at 50°C for a further hour and then cooled to room temperature. DCM (300 ml) is added followed by hydrochloric acid (850 ml, 2M, 1.7 mol). The two layers are separated and the aqueous layer is extracted with DCM (2 x 100 ml). The organic layer is dried over anhydrous sodium sulfate, filtered and the solvent from the filtrate is removed in vacuo. The residue is dissolved in petrol (100 ml) and silica (60 g) is added. The mixture is purified by vacuum flash chromatography on silica (60 g) eluting with:- petrol:ethyl acetate 100:0, 99:1, 98:2, 97:3, 96:4, 95:5, 94:6, 93:7, 92:8, 91:9, 90:10 ml. Fractions 1-9 are combined and the solvent removed in vacuo. The solid is dissolved in methanol (200 ml). Potassium carbonate (1.16 g, 8.4 mmol) is added and the mixture is stirred overnight. The solvent is removed in vacuo and the residue is dissolved in petrol (100 ml). Silica (60 g) is added and the mixture is purified by vacuum flash chromatography on silica (60 g) eluting with:- petrol:ethyl acetate 200:0, 196:4, 192:8, 188:12, 184:16, 180:20, 176:24, 172:28 ml. Fractions 6-7 are combined and the solvent removed in vacuo to give the desired product as a white solid (16 g, 92% yield).

[0273] Preparation of Stage 6 [ka]

[0274] The product of stage 3 (17.7 g, 66 mmol), 4-bromo-2-ethyliodobenzene (20.54 g, 66 mmol), toluene (130 ml) and triethylamine (22 ml, 158 mmol) are sonicated for 30 minutes. Bis(triphenylphosphine)palladium II chloride (480 mg, 0.67 mmol) and copper I iodide (200 mg, 1.05 mmol) are added. The mixture is slowly heated to 40°C and held at 40°C for 2 hours, after which it is cooled to room temperature. DCM (500 ml) is added, followed by hydrochloric acid (200 ml, 1 M, 200 mmol). The two layers are separated and the aqueous layer is extracted with DCM (2 x 50 ml). The organic layer is dried over anhydrous sodium sulfate, filtered and the solvent from the filtrate is removed in vacuo. The residue is dissolved in DCM (200 ml) and purified by vacuum flash chromatography on silica (200 g) eluting with:- DCM:ethyl acetate 200:0, 198:2, 196:4, 194:6, 192:8, 190:10, 188:12, 186:14, 184:16, 182:18, 180:20, 178:22, 176:24, 174:26, 172:28, 170:30, 168:32, 166:34, 164:36, 162:38, 160:40 ml. Fractions 7-19 are combined and the solvent reduced in vacuo to approximately 150 ml. Add petrol (150ml), chill in the fridge for 1 hour, filter off and wash with chilled petrol to give the desired product as a white solid (20g, 67% yield).

[0275] Preparation of Stage 7 [ka]

[0276] The products of stage 6 (20.1 g, 44.6 mmol) and stage 5 (9.77 g, 46.5 mmol) and diisopropylamine (140 ml, 1.0 mol) are sonicated for 30 min. Palladium II acetate (320 mg, 1.4 mmol), tri-tert-butylphosphonium tetrafluoroborate (360 mg, 1.2 mmol) and copper I iodide (160 mg, 0.8 mmol) are added. The mixture is slowly heated to 45°C. The reaction is exothermic and a thick precipitate forms. After reaching 55°C, it is cooled to 45°C. The mixture is held at 45°C for 1.5 h and then cooled to room temperature. DCM (500 ml) is added followed by hydrochloric acid (500 ml, 2 M, 1 mol). The two layers are separated and the aqueous layer is extracted with DCM (2 x 50 ml). The organic layer is dried over anhydrous sodium sulfate, filtered and the solvent from the filtrate is removed in vacuum. The residue is dissolved in DCM (200 ml) and silica (100 g) is added. The mixture is purified by vacuum flash chromatography on silica (100 g) eluting with:- DCM:Ethyl acetate 200:0, 198:2, 196:4, 194:6, 192:8, 190:10, 188:12, 186:14, 184:16, 182:18, 180:20, 178:22, 176:24, 174:26, 172:28, 170:30, 168:32, 166:34, 164:36, 162:38, 160:40 ml. Fractions 3-21 are combined and the solvent is removed in vacuum. The solid is recrystallised from DCM (40ml) and petrol (160ml), chilled in the fridge for 1 hour, filtered off and washed with chilled petrol to give the desired product as a white solid (24.73g, 96% yield).

[0277] Stage 8 Preparation [ka]

[0278] Alcohol (APN2187, 24.1 g, 41.6 mmol), triethylamine (25 ml, 178 mmol) and DCM (250 ml) are stirred in an ice bath. 3-Chloropropionyl chloride (4.7 ml, 49.2 mmol) in DCM (10 ml) is added dropwise over 20 minutes. The mixture is stirred for a further 30 minutes. Additional triethylamine (75 ml, 539 mmol) is added and heated to 35° C. for 18 hours, then cooled to room temperature. DCM (1000 ml) is added to the reaction mixture, followed by hydrochloric acid (360 ml, 2M, 720 mmol). The two layers are separated and the aqueous layer is extracted with DCM (2×250 ml). The organic layer is dried over anhydrous sodium sulfate, filtered and the solvent from the filtrate is removed in vacuo. The residue is dissolved in DCM (100 ml) and purified by vacuum flash chromatography on silica (220 g) eluting with DCM (200 ml fractions). Fractions 2-6 are combined and the solvent removed in vacuo. The solid is recrystallised three times from DCM (60 ml) and petrol (240 ml), chilled in the fridge for 1 hour, filtered off and washed with chilled petrol to give the desired product as a white solid (23.07 g, 88% yield).

[0279] This compound exhibits the phase transition K79N163I.

[0280] Compound (RM-46) was synthesized according to the following scheme: [ka] It is prepared according to

[0281] Preparation of Stage 1 [ka]

[0282] 4-Iodophenol (66 g, 300 mmol), potassium carbonate (52.2 g, 378 mmol), 3-bromopropanol (45 g, 323 mmol), sodium iodide (0.3 g, 2 mmol) and butanone (100 ml) are heated to 80°C overnight. The mixture is cooled, filtered, washed with acetone and the solvent from the filtrate is removed in vacuo. The oil is crystallised from petrol (250 ml), chilled in the refrigerator for 1 hour, filtered off and washed with chilled petrol to give the product as a solid (77.9 g, 93% yield).

[0283] Preparation of Stage 2 [ka]

[0284] The product of stage 1 (75 g, 270 mmol), trimethylsilylacetylene (45 ml, 326 mmol), triethylamine (60 ml, 431 mmol) and toluene (360 ml) are sonicated for 15 minutes. Copper(I) iodide (0.54 g, 2.8 mmol), bis(triphenylphosphine)palladium II chloride (1.08 g, 1.5 mmol) are added and the mixture is stirred at room temperature. The reaction is exothermic and reaches 35°C. After the temperature has stabilized, the mixture is heated to 40°C and held for 2 hours, then cooled to room temperature. Hydrochloric acid (250 ml, 2 M, 0.5 mol) is added. The two layers are separated and the aqueous layer is extracted with toluene (50 ml). Silica (200 g) is added to the combined filtrate. The mixture is purified by vacuum flash chromatography on silica (200 g) eluting with: DCM:ethyl acetate 500:0, 1000:0, 980:20, 960:40, 940:60, 920:80 ml. Fractions 3-6 are combined and the solvent removed in vacuo to give the product as an orange oil (55 g, 82%).

[0285] Preparation of Stage 3 [ka]

[0286] The product of stage 2 (54.6 g, 220 mmol) is dissolved in methanol (300 ml). Potassium carbonate (3.03 g, 22 mmol) is added and the mixture is stirred at 40° C. for 1 h. The solvent is removed in vacuo. DCM (200 ml) and silica (150 g) are added to the residue. The mixture is purified by vacuum flash chromatography on silica (200 g) eluting with:- DCM:Ethyl acetate 1000:0, 980:20, 960:40, 940:60, 920:80, 900:100, 880:120 ml. Fractions 2-7 are combined and the solvent is removed in vacuo. The oil is triturated with petrol (100 ml), cooled in the refrigerator for 1 h, filtered off and washed with chilled petrol to give the product as a solid (36.7 g, 95% yield).

[0287] Preparation of Stage 4 [ka]

[0288] 2-tert-Butylanthracene (2.3 g, 9.8 mmol) and DCM (50 ml) are cooled in an ice bath. Bromine (3.2 g, 20 mmol) dissolved in DCM (50 ml) is added dropwise at 5° C. over 1.5 h. The mixture is allowed to warm to room temperature for 16 h. Water (50 ml) is added. The two layers are separated and the organic layer is washed with saturated sodium bicarbonate. The organic layer is dried over anhydrous sodium sulfate, filtered and the solvent from the filtrate is removed in vacuo. The solid is dissolved in DCM (50 ml). IMS (75 ml) is added and the mixture is boiled to remove the DCM. The mixture is placed in the refrigerator for 1 h. The solid is filtered off and washed with refrigerator-cooled IMS to give the desired product (3.4 g, 88% yield).

[0289] Preparation of Stage 5 [ka]

[0290] The products of stage 4 (1.7 g, 4.3 mmol) and stage 3 (1.7 g, 9.7 mmol), THF (5 ml) and diisopropylamine (25 ml, 178 mmol) are sonicated for 30 min. Palladium II acetate (90 mg, 0.40 mmol), tri-tert-butylphosphonium tetrafluoroborate (102 mg, 0.35 mmol) and copper I iodide (45 mg, 0.24 mmol) are added. The mixture is heated very slowly to 60° C. and then held for a further 1.5 h, forming a thick precipitate. The mixture is cooled, diluted with water (35 ml) and acidified with concentrated hydrochloric acid (15 ml, 11.6 M, 174 mmol). The mixture is extracted with DCM (500 ml and 2×50 ml). The solvent from the combined organic extracts is removed in vacuo. The residue is dissolved in DCM (100 ml). Silica (40 g) is added and the mixture is purified by vacuum flash chromatography on silica (40 g) eluting with:- DCM:ethyl acetate:IPA 200:0:0, 198:2:0, 196:4:0, 194:6:0, 192:8:0, 190:10:0, 188:10:2, 186:10:4, 184:10:6, 182:10:8, 180:10:10, 178:10:12 ml. Fractions 11-12 are combined and the solvent reduced to give the product. (1.71 g, 68% yield).

[0291] Preparation of Stage 6 [ka]

[0292] The product of stage 5 (1.71 g, 2.9 mmol), DCM (30 ml) and 3-chloropropionyl chloride (0.8 ml, 8.4 mmol) are stirred on an ice bath. Triethylamine (3 ml, 22 mmol) in DCM (10 ml) is added dropwise over 20 minutes. Additional triethylamine (17 ml, 122 mmol) is added over 10 minutes. The mixture is allowed to warm to room temperature and held at room temperature for 30 minutes. The mixture is heated at 35° C. for 18 hours and then cooled to room temperature. DCM (150 ml) and hydrochloric acid (80 ml, 2M, 160 mmol) are added. The two layers are separated and the aqueous layer is extracted with DCM (2×50 ml). The solvent from the combined extracts is removed in vacuo. The residue is dissolved in DCM (100 ml) and silica (40 g) is added. The mixture is purified by vacuum flash chromatography on silica (80 g) eluting with DCM (150 ml fractions). Fractions 5-8 are combined and the solvent reduced to 20 ml. Petrol (100 ml) is added and cooled in the refrigerator for 1 hour. The solid is filtered off and washed with chilled petrol to give the product (1.16 g, 57% yield, HPLC assay 99.7%).

[0293] This compound exhibits a phase transition K155I.

[0294] Compound (RM-59) was synthesized according to the following scheme: [ka] It is prepared according to

[0295] All reactions were carried out under nitrogen unless otherwise stated. Petroleum ether = 40-60℃ fraction

[0296] Preparation of Stage 1 [ka]

[0297] A mixture of 6-bromo-1-(tert-butyldimethylsilyloxy)hexane (7.2 g; 0.024 mol), 4-bromo-3-ethylphenol (4.9 g; 0.024 mol) and potassium carbonate (7.4 g; 0.054 mol) is stirred in anhydrous DMF (80 ml) at 80° C. for 16 h. After cooling, the mixture is partitioned between ethyl acetate / petroleum ether and water. The separated organic layer is washed with water, brine, dried over sodium sulfate and evaporated in vacuo. The residue is dissolved in petroleum ether, layered on silica (125 g) and eluted with 5% ethyl acetate in petroleum ether to give the product as a colorless oil (7.7 g; 76%).

[0298] Preparation of Stage 2 [ka]

[0299] To a solution of the product of stage 1 (7.7 g; 0.019 mol) in THF (150 ml) is added 2 M HCl (50 ml). The resulting solution is stirred for 75 min, then excess organic solvent is removed in vacuo, and the mixture is partitioned between ethyl acetate and brine, dried over sodium sulfate, and evaporated in vacuo to give the product as a mixture with tert-butyldimethylsilanol (overall yield 8 g; assuming quantitative yield of about 5.3 g), which is used directly in the next step.

[0300] Preparation of Stage 3 [ka]

[0301] To a degassed solution of the product of stage 2 (8.0 g crude; assumed pure 5.3 g; 0.0186 mol) and TMS acetylene (2.36 g; 0.024 mol) in diisopropylamine (50 ml) was added copper I iodide (44 mg), tri-(tert-butylphosphonium) tetrafluoroborate (109 mg), followed by palladium II acetate (89 mg). The mixture was heated at 45° C. for 2 hours, cooled, evaporated in vacuo, slurried in ethyl acetate, then filtered, and the filtrate evaporated in vacuo before azeotroping with petroleum ether. The residue was chromatographed on silica (125 g) eluting with 33% petroleum ether in DCM followed by 5% ethyl acetate in DCM to give the product as a brown oil (5.4 g).

[0302] This product was not analyzed by NMR but was carried forward to the next reaction, where NMR comparison revealed the presence of a 40% impurity, which was likely also present in the precursor product.

[0303] Preparation of Stage 4 [ka]

[0304] To a solution of the product of Stage 3 (5.4 g; 0.018 mol) in methanol (150 ml) is added potassium carbonate (0.25 g; 0.0018 mol). The mixture is stirred at ambient temperature overnight then evaporated in vacuo and azeotroped with DCM and petrol, then layered onto silica (90 g) in DCM and eluted with DCM then ethyl acetate to give the product as an orange oil (4.2 g).

[0305] NMR analysis shows this to be about a 40% impurity that cannot be separated, which will be removed in the next reaction. The material is assumed to be 50% pure to ensure an excess in the next step.

[0306] Preparation of Stage 5 [ka]

[0307] To a degassed solution of the product of stage 4 (4.2 g crude; assumed pure 2.1 g; 0.008 mol) and 3,7-dibromodibenzothiophene (1.37 g; 0.004 mol) in diisopropylamine (25 ml) is added copper I iodide (47 mg), tri-(tert-butylphosphonium) tetrafluoroborate (121 mg), followed by palladium II acetate (96 mg). The mixture is heated to 45° C. for 2 hours, cooled, evaporated in vacuum, then stirred in a mixture of ethyl acetate and 2M hydrochloric acid, filtered, then washed with ethyl acetate and water to give the product as an off-white solid after drying in vacuum at 50° C. (1.9 g; 71%).

[0308] Preparation of Stage 6 [ka]

[0309] To an ice / water bath cooled slurry of the product of stage 5 (1.9 g; 0.0028 mol) in anhydrous DCM (600 ml) and triethylamine (1.25 ml; 0.009 mol) is added 3-chloropropionyl chloride (0.94 g; 0.0074 mol) dropwise over 15 minutes. After 30 minutes, a further amount of triethylamine (2.5 ml) is added dropwise over 10 minutes. After 15 minutes, additional trimethylamine (3 ml) is added over 5 minutes, followed by 3-chloropropionyl chloride (0.35 ml; 0.0037 mol) over 5 minutes. The reaction mixture is allowed to warm to room temperature for 20 minutes. TLC analysis of the opaque mixture still showed traces of starting material so further trimethylamine (3 ml) followed by 3-chloropropionyl chloride (0.35 ml) are added successively at room temperature which immediately gave a solution. After 20 minutes, trimethylamine (30 ml) and a small amount of Irganox are added and the solution is heated to 38° C. overnight, cooled and evaporated in vacuo. The residue is dissolved in DCM (100 ml) and petroleum ether (50 ml) is added and the mixture is filtered and washed with 2:1 DCM:petroleum ether. The filtrate is evaporated in vacuo, then redissolved in DCM, washed with 2M hydrochloric acid, dried over sodium sulfate and evaporated in vacuo.

[0310] The residue is dissolved in DCM (30ml) and petroleum ether is added (10ml) then layered onto silica (60g) and eluted with 50-100% DCM in petroleum ether to give the crude product as a cream / white solid. This is dissolved in DCM (25ml) and petroleum ether (100ml) is added and placed in the freezer for 30 minutes before filtering and washing with 4:1 petroleum ether:DCM then petroleum ether to give the product as a white solid after drying in vacuo at 30°C (1.3g; 59%).

[0311] This compound exhibits the phase transition K130N160I.

[0312] Compound (RM-57) was synthesized according to the following scheme: [ka] It is prepared according to

[0313] Preparation of Stage 1 [ka]

[0314] 4-Bromo-3-methylphenol (18.7 g, 100 mmol), 3-bromopropanol (15.3 g, 110 mmol), potassium carbonate (16.5 g, 120 mmol) and butanone (50 ml) are heated at 80° C. for 2.5 hours. Additional 3-bromopropanol (1.8 g, 12.9 mmol), potassium carbonate (1.8 g, 13 mmol) are added and heated at 80° C. for an additional 3.5 hours. The mixture is cooled, filtered, washed with acetone and the solvent from the filtrate is removed in vacuo (24.5 g, 100% yield).

[0315] Preparation of Stage 2 [ka]

[0316] The product of stage 1 (24.5 g, 100 mmol), trimethylsilylacetylene (18 ml, 128 mmol) and diisopropylamine (270 ml, 1.94 mmol) are sonicated for 30 min. Palladium II acetate (240 mg, 1.07 mmol), tri-tert-butylphosphonium tetrafluoroborate (280 mg, 0.97 mmol) and copper I iodide (120 mg, 0.63 mmol) are added. The mixture is slowly heated to 55 °C (no exotherm, slow reaction). The mixture is cooled to 30 °C. Additional palladium II acetate (240 mg, 1.07 mmol), tri-tert-butylphosphonium tetrafluoroborate (280 mg, 0.97 mmol) and copper I iodide (120 mg, 0.63 mmol) are added. The mixture is slowly heated to 45 °C and held at 45 °C for 6 h. Further trimethylsilylacetylene (18 ml, 128 mmol), palladium II acetate (480 mg, 2.14 mmol), tri-tert-butylphosphonium tetrafluoroborate (560 mg, 1.93 mmol) and copper I iodide (240 mg, 1.26 mmol) are added and then heated to 55° C. for a further 6 h. The mixture is cooled to room temperature. Hydrochloric acid (1000 ml, 2 M, 2 mol) is added. DCM (250 ml) is added, the two layers are separated and the aqueous layer is extracted with DCM (2×100 ml). The combined organic layers are dried over anhydrous sodium sulfate, filtered and the solvent from the filtrate is removed in vacuo. The residue is dissolved in DCM (100 ml) and silica (60 g) is added. The mixture is purified by vacuum flash chromatography on silica (140 g) eluting with:- DCM:Ethyl acetate 200:0, 196:4, 192:8, 188:12, 184:16, 180:20, 176:24, 172:28, 168:32, 164:36, 160:40 ml. Fractions 3-9 are combined and the solvent removed in vacuo (24 g). The oil (24 g) is dissolved in petrol (80 ml) and purified by vacuum flash chromatography on silica (80 g) eluting with:- petrol:Ethyl acetate 100:0, 95:5, 90:10, 85:15, 80:20, 75:25, 70:30, 65:35, 60:40, 55:45, 50:50 ml.Fractions 6-10 are combined and the solvent removed in vacuo (16.5 g). The oil (16.5 g) is dissolved in methanol (120 ml). Potassium carbonate (0.87 g, 6.3 mmol) is added and the mixture is stirred at room temperature overnight. The solvent is removed in vacuo. The residue is suspended in a mixture of ethyl acetate (20 ml) and petrol (80 ml). The mixture is purified by vacuum flash chromatography on silica (80 g) eluting with:- petrol:ethyl acetate 100:0, 95:5, 90:10, 85:15, 80:20, 75:25, 70:30, 65:35, 60:40, 55:45, 50:50 ml. Fractions 5-9 are combined and the solvent removed in vacuo to give the desired product (6 g, 32% yield).

[0317] Preparation of Stage 3 [ka]

[0318] The product of Stage 2 (6 g, 31.6 mmol), triethylamine (15 ml, 108 mmol) and DCM (100 ml) are stirred in an ice bath. 3-Chloropropionyl chloride (3.4 ml, 35.4 mmol) in DCM (10 ml) is added dropwise over 15 minutes. The mixture is stirred for a further 30 minutes. Additional triethylamine (30 ml, 216 mmol) is added and heated to 35° C. for 18 hours, then cooled to room temperature. The mixture is acidified with hydrochloric acid (150 ml, 2M, 300 mmol). The two layers are separated and the aqueous layer is extracted with DCM (2×25 ml). The combined organic layers are dried over anhydrous sodium sulfate, filtered and the solvent from the filtrate is removed in vacuo. The residue is dissolved in DCM (100 ml) and purified by vacuum flash chromatography on silica (120 g) eluting with DCM (100 ml) fractions. Fractions 2-5 were combined to give the desired product (7 g, 91% yield).

[0319] Preparation of Stage 4 [ka]

[0320] The product of stage 3 (5.3 g, 21.7 mmol), 2,6-dibromo[1,2-b:4,5-b]dithiophene (3.48 g, 10 mmol), THF (80 ml) and diisopropylamine (40 ml, 0.35 mol) are sonicated for 15 min. Palladium II acetate (240 mg, 0.89 mmol), tri-tert-butylphosphonium tetrafluoroborate (270 mg, 0.78 mmol) and copper I iodide (120 mg, 0.52 mmol) are added. The mixture is slowly heated to 55 °C and held at 55 °C for 1 h before being cooled to room temperature. DCM (300 ml) is added and the mixture is purified by vacuum flash chromatography on silica (100 g) eluting with DCM (500 ml). The volume of the solvent is reduced to 40 ml. Add petrol (40ml), chill in the fridge for 1 hour, filter off and wash with chilled petrol to give the desired product (5.94g, 85% yield). Further purify the product (4g) by dissolving in boiling DCM (200ml). Add silica (40g) and purify the mixture by vacuum flash chromatography on silica (80g) eluting with DCM (200ml) fractions. Combine fractions 3-6. Reduce the solvent volume to 50ml. Add petrol (50ml), chill in the fridge for 1 hour, filter off and wash with chilled petrol to give the desired product as a lemon yellow solid (3.2g, 80% recovery).

[0321] This compound exhibits the phase transition K174N229I.

[0322] Compound Examples The following compounds are prepared by the synthetic methods described above or by methods analogous thereto. [Table 1-1] [Table 1-2] [Table 1-3] [Table 1-4] [Table 1-5] [Table 1-6] [Table 1-7] [Table 1-8] [Table 1-9] [Table 1-10] [Table 1-11] [Table 1-12] [Table 1-13]

[0323] Examples of Blends and Polymer Films Mixture M1 is prepared with the following composition: mixture M1 [Table 2]

[0324] The additives BYK361, Irgacure® 651 and Irganox® 1076 are commercially available from Byk Gulden, Germany and CIBA, Switzerland.

[0325] Polymer Film Manufacturing The mixture was dissolved in 1:2:1 MEK:cyclopentanone:MIBK to obtain a 20% solids solution, then subjected to the following process: Spin coat the substrate at 3000 rpm for 30 seconds Anneal at 90℃ for 60 seconds UV exposure, high pressure mercury lamp 250-450 nm (Dr. Hoenle), 80 mW / cm in nitrogen atmosphere 2 for 60 seconds applies.

[0326] The retardance of the resulting polymer film is measured by ellipsometry, and then the thickness is measured by profilometry. The data obtained is then used to calculate the birefringence, which is determined to be 0.547 at 550 nm and 20°C.

[0327] Further mixtures M2-M25 are prepared by replacing compound RM-1 in example mixture M1 with an equal amount of a compound shown in Table 1 selected from the compound examples above.

[0328] Polymer films are prepared and the birefringence is measured as described above, and the results are shown in Table 1. [Table 3]

[0329] Example mixture M26 [Table 4]

[0330] POLYFOX™ PF-656 is commercially available from Synthomer plc, TR-PBG-304 is commercially available from Changzou Tronly, and NCI-803 is commercially available from Adeka.

[0331] The mixture was dissolved in 1:2:1:2 MIBK:cyclopentanone:MEK:3-undecane-one to give a 20% solids solution, and then polymer films were prepared as follows: Spin coat the substrate at 3000 rpm for 30 seconds Anneal at 66°C for 60 seconds UV exposure, high pressure mercury lamp 250-450 nm (Dr. Hoenle), 80 mW / cm in nitrogen atmosphere 2 for 60 seconds Manufactured in.

[0332] The birefringence of the polymer film is determined as described above to be 0.375 at 550 nm and 20°C.

[0333] Example mixture M27 [Table 5]

[0334] Example mixture M28 [Table 6]

[0335] Preparation of polymer film 1 Mixtures M27 and M28 are each dissolved to obtain mixtures in 1:2:1 MIBK:cyclopentanone:MEK at 20% solids. Films of each mixture are then produced by spin-coating onto KBr discs and annealing at 80 °C for 30 s. The uncured films are then placed in an FTIR analysis chamber purged with N2. The IR spectrum of the film is recorded for 2 min at 2 s intervals. After the 30 s measurements, the film is illuminated with broadband UV light (250-450 nm, 60 mW cm at 365 nm). -2 ) for 1 minute to form a hardened polymer film.

[0336] The spectrum obtained shows the carbonyl peak (1800-1735 cm -1 λ max =1735cm-1 ) and acrylic C=C bonds (1646-1613cm -1 λ max =1629cm -1 The intensity is analyzed by measuring the area of ​​the peak (ρ) over time. To compare the relative peak intensities over time, the intensity value is calculated as the product of the areas of the two peaks on the spectrum (ρ). This value is then converted to the degree of cure by Equation 1. The data obtained are shown in Table 1. Curing%=1-ρ t / ρ i Formula 1: Formula for calculating degree of cure (%), ρ t - intensity product at time t, ρ i -Initial intensity product

[0337] In this case, due to the overlap of aromatic C=C stretching and acrylic C=C stretching, this peak cannot be completely removed and the measured value does not reach 100% cure, even though a fully cured hard film is obtained. Therefore, for comparison, the calculated values ​​were normalized to the highest level of cure obtained, which was taken as 100%. [Table 7]

[0338] As can be seen from Table 1, mixture 28 containing compound RM-47 with only one spacer group reaches a normalized cure degree that is 10-15% higher compared to mixture 27 with the same composition except that compound RM-47 is replaced with a corresponding amount of compound RM-12 with a similar structure but with spacer groups on both sides of the mesogenic core. This suggests that compound RM-47 with only one spacer group contributes positively to achieving a higher cure degree.

[0339] Polymer film production 2 Mixtures M27 and M28 were each dissolved to give mixtures in 1:2:1 MIBK:cyclopentanone:MEK at 20% solids. A film of each mixture was then spin-coated onto rubbed polyimide-coated glass, and the resulting film was illuminated with UV light (400 nm, 80 mW cm). -2 The film is polymerized by exposure to 1000 dl / s (60 s in N2). The retardance of the resulting polymer film is measured by ellipsometry and then the thickness is measured by profilometry. The resulting data is then used to calculate the birefringence data shown in Table 2. [Table 8]

[0340] From Table 2, it can be seen that the polymer films made from blends M27 and M28 give nearly identical optical performance, which is attributed to the common host blend and the similar structures of RM-12 and RM-47.

[0341] The above results indicate that compounds of formula I having only one spacer group are particularly suitable for producing polymer films with both high birefringence and high degree of cure.

Claims

1. Formula I 【Chemistry 1】 [In the formula, P is a polymerizable group, Sp is a spacer group or a single bond; R １１ is F, Cl, CN, NCS, alkyl, alkoxy, thioalkyl, alkylcarbonyl, alkoxycarbonyl, alkylcarbonyloxy or alkoxycarbonyloxy, preferably having 1 to 15 C atoms and more preferably optionally fluorinated, or is P-Sp, A, B, D and E, if present in plurality, independently of one another, represent an alicyclic, heterocyclic, aromatic or heteroaromatic group having 4 to 20 ring atoms, which is monocyclic or polycyclic and optionally substituted by one or more groups L or P-Sp-, and one of the rings C and D may also represent a single bond, L is F, Cl, -CN, P-Sp- or linear, branched or cyclic alkyl having 1 to 25 C atoms and is ２ The - group is optionally such that the O and / or S atoms are not directly bonded to each other. 【Chemistry 2】 wherein one or more H atoms are optionally replaced by P-Sp-, F or Cl, respectively, or two substituents L bonded to directly adjacent C atoms may form a cycloalkyl or cycloalkenyl group having 5, 6, 7 or 8 C atoms, C is, 【Chemistry 3】 【Chemistry 4】 represents M is CH ２ , C(CH ３ ) ２ , C.H.F., C.F. ２ , NH, S or O, Z １１ , Z １２ When a plurality of groups are present, they each independently represent -O-, -S-, -CO-, -COO-, -OCO-, -S-CO-, -CO-S-, -O-COO-, -CO-NR ０ --, --NR ０ —CO—, —NR ０ -CO-NR ００ , -NR ０ -CO-O-, -O-CO-NR ０ --, --OCH ２ --, --CH ２ O-, -SCH ２ --, --CH ２ S-, -CF ２ O-, -OCF ２ -, -CF ２ S-, -SCF ２ --, --CH ２ CH ２ -, -(CH ２ ) ｎ１ , -CF ２ CH ２ --, --CH ２ CF ２ -, -CF ２ CF ２ -, -CH=N-, -N=CH-, -N=N-, -CH=CR ０ -, -CY １ = C.Y. ２ --, 【Chemistry 5】 , —CH═CH—COO—, —OCO—CH═CH— or a single bond, preferably —COO— or —OCO—, 【Chemistry 6】 or a single bond, n1 is 1, 2, 3 or 4; r represents 0, 1, 2, 3 or 4, preferably 0, 1 or 2; s represents 0, 1, 2 or 3, preferably 0, 1 or 2; t represents 0, 1 or 2, preferably 0 or 1; R ０ , R ００ represents H or alkyl having 1 to 12 C atoms, Y １ , Y ２ represent, independently of one another, H, F, Cl, NCS or CN, n is 0, 1, 2, 3 or 4, preferably 0, 1 or 2, more preferably 0 or 1, and most preferably 0; m is 0, 1, 2, 3 or 4, preferably 0, 1 or 2, more preferably 0 or 1, and most preferably 0. Compound.

2. One, two, three, four or more of rings A, B, D and / or E in formula I are 【Chemistry 7】 [In the formula, L is each independently an alkyl, alkoxy or thioalkyl having 1 to 6 C atoms, P-Sp-, -CN, F, Cl, OCF ３ , C.F. ３ , C.H. ２ F, C.H.F. ２ or two substituents L bonded to directly adjacent C atoms may form a cyclic group containing 5, 6, 7 or 8 C atoms, r represents 0, 1, 2 or 3; s represents 0, 1 or 2; t represents 0, 1 or 2; M is CH ２ , C(CH ３ ) ２ , C.H.F., C.F. ２ , NH, S or O.

2. The compound of claim 1 selected from the group consisting of:

3. In formula I, one or both of rings B and D are 【Chemistry 8】 [In the formula, L is each independently an alkyl, alkoxy or thioalkyl having 1 to 6 C atoms, P-Sp-, -CN, F, Cl, OCF ３ , C.F. ３ , C.H. ２ F, C.H.F. ２ or two substituents L bonded to directly adjacent C atoms may form a cyclic group containing 5, 6, 7 or 8 C atoms, r represents 0, 1, 2 or 3; s represents 0, 1 or 2; t represents 0, 1 or 2; M is CH ２ , C(CH ３ ) ２ , C.H.F., C.F. ２ , NH, S or O.

2. The compound of claim 1 selected from the group consisting of:

4. Ring C in formula I is 【Chemistry 9】 [In the formula, L each independently represent P-Sp-, F, -CN or alkyl, alkoxy or thioalkyl having 1 to 6, preferably 1 to 3 and more preferably 1 or 2 C atoms, r represents 0, 1, 2 or 3; s represents 0, 1, 2 or 3; t represents 0, 1 or 2; M is CH ２ , C(CH ３ ) ２ , C.H.F., C.F. ２ , NH, S or O, M １ represents S, O or NH. The compound according to claim 1, characterized in that it is selected from the group consisting of:

5. The subexpression 【Chemistry 10】 [In the formula, R １１ rings B and C, P and Sp have one of the meanings according to claim 1, L each independently represent P-Sp-, F, CN or alkyl, alkoxy or thioalkyl having 1 to 6, preferably 1 to 3 and more preferably 1 or 2 C atoms, L １ and L ２ each independently represents H or L, M is S, O, NH, CH ２ or C(CH ３ ) ２ and M １ is NH or S.

2. The compound according to claim 1, characterized in that it is selected from:

6. The subexpression 【Chemistry 11-1】 【Chemistry 11-2】 【Chemistry 11-3】 【Chemistry 11-4】 【Chemistry 11-5】 【Chemistry 11-6】 【Chemistry 11-7】 [In the formula, P is a polymerizable group, Sp is a spacer group or a single bond; R is alkyl, alkoxy, thioalkyl, alkylcarbonyl, alkoxycarbonyl, alkylcarbonyloxy or alkoxycarbonyloxy, preferably having 1 to 15 C atoms and more preferably optionally fluorinated, L is preferably an acrylate, P-Sp-, F, Cl, -CN or a linear, branched or cyclic alkyl having 1 to 25 C atoms and having one or more non-adjacent CH ２ The - group is optionally such that the O and / or S atoms are not directly bonded to each other. 【Chemistry 12】 wherein one or more H atoms are optionally replaced by P-Sp-, F or Cl, respectively, and two substituents L bonded to directly adjacent C atoms may form a cyclic group having 5, 6, 7 or 8 C atoms, r represents 0, 1, 2, 3 or 4, preferably 0, 1 or 2.

2. The compound according to claim 1, characterized in that it is selected from:

7. The compound of claim 1 , wherein P represents an acrylate or methacrylate group.

8. A mixture comprising two or more reactive mesogens (RM), at least one of which is a compound of formula I according to claim 1.

9. 9. The mixture of claim 8, comprising one or more RMs having only one polymerizable functional group and one or more RMs having two or more polymerizable functional groups.

10. 8. A formulation comprising one or more compounds of formula I according to any one of claims 1 to 7 and further comprising one or more solvents and / or additives.

11. A polymer obtainable by polymerizing a compound of formula I according to any one of claims 1 to 7.

12. 8. Use of a compound of formula I as defined in any one of claims 1 to 7 in an optical, electro-optical or electronic component or device.

13. 8. An optical, electro-optical or electronic device or part thereof comprising a RM according to any one of claims 1 to 7.

14. 14. The component of claim 13, selected from optical retardation films, polarizers, compensators, beam splitters, reflective films, alignment layers, color filters, antistatic protective sheets, electromagnetic interference protective sheets, polarization control lenses, IR reflective films, and lenses for light guiding, focusing, and optical effects.

15. 14. The device of claim 13, selected from LC displays, autostereoscopic 3D displays, organic light emitting diodes (OLEDs), optical data storage devices, Google and Windows for AR / VR applications.

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