Polymerizable compounds, polymerizable LC materials and polymer films

Abstract

The present invention relates to polymerizable (LC) compounds, corresponding polymerizable LC materials, polymer films with flat, negative or positive optical dispersion obtainable from such materials, and the use of the polymerizable LCs, polymerizable LC materials and / or polymer films in optical, electro-optical, electronic, semiconducting or fluorescent components or devices.

Description

[Technical field]

[0001] FIELD OF THEINVENTION The present invention relates to polymerisable (LC) compounds, corresponding polymerisable LC materials, polymer films with flat, negative or positive optical dispersion obtained from such materials, and the use of the polymerisable LCs, polymerisable LC materials and / or polymer films in optical, electro-optical, electronic, semiconducting or fluorescent components or devices. [Background technology]

[0002] Background and Prior Art Polymerizable liquid crystal materials are known in the prior art for the preparation of anisotropic polymer films. These films are usually prepared by applying a thin layer of a polymerizable liquid crystal mixture onto a substrate, aligning the mixture into a uniform orientation, and finally fixing the orientation of the liquid crystal molecules by polymerizing the polymerizable liquid crystal material. Thereby, the orientation of the liquid crystal molecules in the polymerized film can be planar, i.e. the liquid crystal molecules are oriented substantially parallel to the layer, homeotropic (rectangular or perpendicular to the layer), or tilted. Corresponding optical films are described, for example, in EP 0 940 707 B1, EP 0 888 565 B1 and GB2 329 393 B1.

[0003] As is generally known by experts, optical films based on polymerizable liquid crystal materials typically exhibit wavelength-dependent retardation. In this regard, three main types of optical behavior are known: i) "normal" or "positive" optical dispersion, as described, for example, in EP 0 940 707 B1 ii) "reverse" or "negative" optical dispersion, as described, for example, in WO 2016 / 020035 A1, and iii) "Flat" optical dispersion as described, for example, in WO 2009 / 058396 A1.

[0004] For example, flat dispersion or negative dispersion polymerizable liquid crystal materials can be produced by adding to the formulation at least one component whose ordinary refractive index (no) is higher than its extraordinary refractive index (ne). This requires highly conjugated substituents at positions perpendicular to the long axis of the molecule. The latter materials absorb part of the UV dose during the curing of optical films, resulting in poor cure and poor thermal durability of the cured films. Furthermore, the latter molecular blocks can easily oxidize at high temperatures in the presence of oxygen. The same is true for highly birefringent formulations containing highly conjugated reactive mesogens, which reduce the thermal durability of the cured films and are generally prone to yellowing.

[0005] For example, WO 2008 / 119427 A1 describes a birefringent polymer film with negative optical dispersion obtained from a polymerizable LC material comprising as a negative dispersion component compound having the structure shown below or a derivative thereof: [ka]

[0006] The proportion of negatively dispersed components in the polymerizable LC materials disclosed in WO 2008 / 119427 A1 is, for example, 50-60% of the total amount of solids (ie without solvent).

[0007] However, the bulky nature of prior art negative dispersion compounds typically makes it difficult to formulate or provide a formulation with a narrow process window for annealing temperatures, which is inconvenient for mass production.

[0008] Furthermore, prior art flat or negative dispersion films are undesirably thick (30-100 μm) due to the low birefringence of the utilized LC materials. Since the retardation of an optical retardation film is determined by the product of birefringence and film thickness, and thin films are generally preferred for flat panel display applications, it is desirable to increase the birefringence of the film and reduce the film thickness while achieving the same retardation. In addition, prior art flat dispersion films often require undesirable processing steps due to their undesirable film thickness, making them unsuitable for mass production processes.

[0009] Therefore, there remains a need for new and preferably improved polymerizable liquid crystal materials or resulting polymer films that do not exhibit the disadvantages of the prior art materials, or, if they do, exhibit them to a lesser extent.

[0010] The polymerizable LC media containing them, to be used for film preparation, must exhibit good thermal properties, in particular a moderate melting point, good solubility in LC hosts and organic solvents, and a reasonably extrapolated clearing point, and furthermore must exhibit excellent optical properties.

[0011] Advantageously, said polymerizable LC material should preferably be applicable for the preparation of distinct, uniformly oriented polymer films and at the same time - Must exhibit good adhesion to the substrate, -It must be highly transparent to visible light (VIS-light), - Must exhibit a yellow coloration (yellowing) that diminishes over time; - the need to exhibit high birefringence in order to reduce the film thickness, - must exhibit good high temperature stability or durability, and further - Uniformly oriented polymer films need to be produced by commonly known methods that are compatible for mass production.

[0012] Other objects of the present invention will become readily apparent to those skilled in the art from the following detailed description. Surprisingly, the inventors of the present invention have found that by using a polymerisable LC material as claimed in claim 1 one or more, preferably all of the above mentioned requirements are preferably met simultaneously. Summary of the Invention

[0013] Summary of the Invention The present invention relates to a compound of formula T [ka] During the ceremony R T1 and R T2 each independently of the other represents H or a hydrocarbon group having 1 to 20 carbon atoms, the group may have a substituent, any carbon atom may be replaced by a heteroatom, and R T1 and R T2 At least one of the following is P-Sp-: P represents a polymerizable group; Sp represents a spacer group; AT 1 and A T3 represents, each and independently and at each occurrence, a 1,4-phenylene group, a 1,4-cyclohexylene group, a pyridine-2,5-diyl group, a pyrimidine-2,5-diyl group, a naphthalene-2,6-diyl group, a naphthalene-1,4-diyl group, a tetrahydronaphthalene-2,6-diyl group, a decahydronaphthalene-2,6-diyl group, or a 1,3-dioxane-2,5-diyl group, which may be unsubstituted or substituted with one or more of the substituents L; L, each and independently in each occurrence, represents F, Cl, Br, I, pentafluorosulfuranyl group, nitro group, cyano group, isocyano group, amino group, hydroxyl group, mercapto group, methylamino group, dimethylamino group, diethylamino group, diisopropylamino group, trimethylsilyl group, dimethylsilyl group, thioisocyano group, or a linear or branched alkyl group having 1 to 20 carbon atoms, preferably 1 to 12 carbon atoms, and preferably 1 to 12 carbon atoms, and one of the -CH2 - or two or more non-adjacent -CH2- may each independently be substituted by -O-, -S-, -CO-, -COO-, -OCO-, -CO-S-, -S-CO-, -O-CO-O-, -CO-NH-, -NH-CO-, -CH=CH-COO-, -CH=CH-OCO-, -COO-CH=CH-, -OCO-CH=CH-, -CH=CH-, -CF=CF-, or -C≡C-, any hydrogen atom in the alkyl group may be substituted by F, or L may represent a group represented by P-Sp-, Z T1 ~Z T3 each independently represents -O-, -S-, -OCH2-, -CH2O-, -CH2CH2-, -CO-, -COO-, -OCO-, -CO-S-, -S-CO-, -O-CO-O-, -CO-NH-, -NH-CO-, -OCO-NH-, -NH-COO-, -NH-CO-NH-, -NH-O-, -O-NH-, -SCH2-, -CH2S-, -CF2O-, -OCF2-, -CF2S-, -SCF2-, -CH=CH-COO- , -CH=CH-OCO-, -COO-CH=CH-, -OCO-CH=CH-, -COO-CH2CH2-, -OCO-CH2CH2-, -CH2CH2-COO-, -CH2CH2-OCO-, -COO-CH2-, -OCO-CH2-, -CH2-COO-, -CH2-OCO-, -CH=CH-, -N=N-, -CH=N-, -N=CH-, -CH=NN=CH-, -CF=CF-, -C≡C- or a single bond, G T1 is the base [ka] indicates, Ch each and independently represents a chalcogen such as O, S, Se, or Te, preferably O and / or S, more preferably S; R 0 and R 00 each independently represents a hydrogen atom, F, Cl, Br, I, or a straight-chain or branched alkyl group having 1 to 20, preferably 1 to 12, and more preferably 1 to 5 carbon atoms, in which one -CH2- or two or more non-adjacent -CH2- may each independently be substituted by -O-, -S-, -CO-, -COO-, -OCO-, -CO-S-, -S-CO-, -O-CO-O-, -CO-NH-, -NH-CO-, -CH=CH-COO-, -CH=CH-OCO-, -COO-CH=CH-, -OCO-CH=CH-, -CH=CH-, -CF=CF-, or -C≡C-, and any hydrogen atom in the alkyl group may be substituted by F or Cl, but is preferably H; W1 and W2 independently represent a group selected from groups containing an aromatic group and / or a non-aromatic group having 1 to 40, preferably 1 to 20, carbon atoms, which may be substituted, the aromatic group may be a hydrocarbon ring or a heterocycle, and the non-aromatic group may be a hydrocarbon group, in which any carbon atom in the hydrocarbon group is replaced with a heteroatom (provided that the oxygen atoms are not directly bonded to each other); Preferably, the group -(Z T3 -A T3 -) m3 -A T4 -Y, which means Z T3 is Z T1 or Z T2 has one of the meanings given for A T3 and A T4 A T1 Or A T2 and m3 each and independently represents 0, 1, or 2, and Y represents a hydrogen atom, F, Cl, Br, I, a pentafluorosulfuranyl group, a nitro group, a cyano group, an isocyano group, an amino group, a hydroxyl group, a mercapto group, a methylamino group, a dimethylamino group, a diethylamino group, a diisopropylamino group, a trimethylsilyl group, a dimethylsilyl group, a thioisocyano group, or a linear or branched alkyl group having 1 to 20 carbon atoms, wherein one -CH2- or two or more non-adjacent -CH2- are each independently any hydrogen atom in the alkyl group may be substituted by F; Y may represent a group represented by P-Sp-; More preferably, it is a group selected from the following: [ka] Even more preferably, the group [ka] and Y represents a hydrogen atom, F, Cl, Br, I, a pentafluorosulfuranyl group, a nitro group, a cyano group, an isocyano group, an amino group, a hydroxyl group, a mercapto group, a methylamino group, a dimethylamino group, a diethylamino group, a diisopropylamino group, a trimethylsilyl group, a dimethylsilyl group, a thioisocyano group, or a linear or branched alkyl group having 1 to 20 carbon atoms, wherein the one -CH2- or two or more non-adjacent -CH2- are each independently any hydrogen atom in the alkyl group may be substituted by F; or Y may represent a group represented by P-Sp-; Preferably, each and independently is H, F, -OCH3, or CN; More preferably, it is H or F. each r independently represents 0, 1, 2, 3, or 4, preferably each and independently represents 0, 1, or 2; m1 and m2 each independently represent an integer of 1 to 6, preferably each independently represent an integer of 1 to 4, more preferably each independently represent 1 or 2; Each m3 independently represents 0, 1, or 2.

[0014] The invention relates to a polymerisable liquid crystal (LC) medium comprising one or more compounds of formula T as defined above and below.

[0015] The invention further relates to the use of a polymerizable LC medium or a polymer film as described above and below in optical, electronic and electro-optical components and devices, preferably optical films, retarders or compensators with flat optical dispersion.

[0016] The present invention further relates to a birefringent polymer film which is obtained or which can be obtained by polymerizing a polymerizable LC medium as described above and below in the LC phase in an oriented state, preferably in the form of a thin film.

[0017] The present invention particularly relates to a polymer film as described above and below which is an A-plate or a C-plate, preferably a positive A-plate (+A-plate) or a positive C-plate (+C-plate).

[0018] The invention further relates to an optical, electronic or electro-optical component or device comprising a polymerizable LC medium or a polymer film as described above and below.

[0019] Such devices include, but are not limited to, electro-optic displays, LCDs, non-linear optical (NLO) devices, optical information storage devices, electronic devices, electroluminescent displays, organic photovoltaic (OPV) devices, lighting devices, sensor devices, electrophotographic recording devices, and organic memory devices.

[0020] The components include optical films, retarders, compensators, polarizers, beam splitters, reflective films, alignment layers, color filters, holographic elements, hot stamp foils, color images, decorative or security markings, LC pigments, adhesives, organic semiconductors, organic field effect transistors (OFETs), integrated circuits (ICs), thin film transistors (TFTs), radio frequency identification (RFID) tags, organic light emitting diodes (OLEDs), organic light emitting transistors (OLETs), organic solar cells (O-SCs), organic laser diodes (O-lasers), organic integrated circuits (O-ICs), electrode materials, photoconductors, photodetectors, capacitors, charge injection layers, Schottky diodes, planarization layers, antistatic films, conductive substrates, conductive patterns, photoconductors, electrophotographic applications, electrophotographic recording, biosensors, biochips.

[0021] Terms and Definitions The term "polymer" as used herein is understood to mean a molecule that encompasses a backbone of one or more different types of repeating units (the smallest building blocks of a molecule), and includes the commonly known terms "oligomer," "copolymer," and "homopolymer." Furthermore, the term polymer is understood to include, in addition to the polymer itself, residues from initiators, catalysts, and other elements associated with the synthesis of such polymers, and such residues are understood to be not covalently incorporated into the polymer. Moreover, such residues and other elements are usually removed during post-polymerization purification processes, but are usually mixed or co-mingled with the polymer and generally remain with the polymer when it is transferred between containers or between solvents or dispersion media.

[0022] In the present invention, "(meth)acrylic polymer" includes polymers obtained from acrylic monomers, polymers obtained from methacrylic monomers, and the corresponding copolymers obtained from mixtures of these monomers.

[0023] The term "polymerization" refers to the chemical process of forming a polymer by linking together multiple polymerizable groups or polymer precursors (polymerizable compounds) containing such polymerizable groups.

[0024] The terms "film" and "layer" include rigid or flexible, self-supporting or free-standing films with mechanical stability, and coatings or layers on a supporting substrate or between two substrates.

[0025] The term "liquid crystal or mesogenic compound" refers to a compound containing one or more calamitic (rod-like or plate-like / lath-like) or discotic (disk-like) mesogenic groups. The term "mesogenic group" refers to a group capable of inducing liquid crystal (LC) phase behavior. Compounds containing mesogenic groups do not necessarily exhibit LC phases by themselves. It is also possible that they exhibit LC phase behavior only in mixtures with other compounds or when the mesogenic compound or material, or a mixture thereof, is polymerized. For simplicity, hereafter the term "liquid crystal" is used for both mesogenic and LC materials. For an overview of the definition, see C. Tschierske, G. Pelzl and S. Diele, Angew. Chem. 2004, 116, 6340-6368.

[0026] Calamitic mesogenic groups typically comprise a mesogenic core consisting of one or more aromatic or non-aromatic cyclic groups bonded to each other directly or via a linking group, optionally comprising terminal groups attached to the ends of the mesogenic core, and optionally comprising one or more side groups attached to the long sides of the mesogenic core, the terminal and side groups typically being selected from the group consisting of, for example, carbyl or hydrocarbyl groups, polar groups such as halogen, nitro, hydroxy, or polymerizable groups.

[0027] The term "reactive mesogen" (RM) refers to a polymerizable mesogenic or liquid crystal compound.

[0028] Polymerizable compounds with one polymerizable group are also called "monoreactive" compounds, those with two polymerizable groups are also called "direactive" compounds, and those with three or more polymerizable groups are also called "multireactive" compounds. Compounds with no polymerizable groups are also called "nonreactive" compounds.

[0029] The term "polymerizable LC material" means a material which comprises more than 90% by weight, preferably more than 95% by weight, more preferably more than 98% by weight of polymerizable compounds as defined above and below.

[0030] The term "non-mesogenic compound or material" means a compound or material that does not contain a mesogenic group as defined above.

[0031] 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.

[0032] Irradiance (E e ) or radiation force is defined as the force of electromagnetic radiation (dθ) per unit area (dA) incident on a surface. E e =dθ / dA

[0033] Radiation exposure or radiation dose (H e ) is the irradiance or radiant power (E e ) as H e =E e t

[0034] All temperatures are expressed in degrees Celsius, for example the melting point T(C,N) or T(C,S), the transition from the smectic (S) to the nematic (N) phase of a liquid crystal T(S,N), the clearing point of a liquid crystal T(N,I), etc. All temperature differences are quoted in degrees difference.

[0035] The term "clearing point" refers to the temperature at which the transition between the mesophase and isotropic phases occurs over the maximum temperature range.

[0036] The term "director" is known in the art and refers to the preferred orientation direction of the long molecular axis (for calamitic compounds) or short molecular axis (for 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.

[0037] 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 measured at a wavelength of 589.3 nm.

[0038] In case of doubt, the definitions as given in C. Tschierske, G. Pelzl, S. Diele, Angew Chem 2004, 116, 6340-6368 shall apply. Unless otherwise stated in a given general formula, the following terms have the following meanings.

[0039] "Carbyl group" means a monovalent or polyvalent organic group containing at least one carbon atom, either containing no further atoms (e.g., -C≡C-) or optionally containing one or more additional atoms, such as, for example, N, O, S, P, Si, Se, As, Te, or Ge (e.g., carbonyl). "Hydrocarbyl group" means a carbyl group containing one or more H atoms and, optionally, further containing one or more heteroatoms, such as, for example, N, O, S, P, Si, Se, As, Te, or Ge.

[0040] The carbyl or hydrocarbyl group may be a saturated or unsaturated group. Unsaturated groups are, for example, aryl, alkenyl, or alkynyl groups. Carbyl or hydrocarbyl groups having more than 3 carbon atoms may be linear, branched, and / or cyclic, and may contain spiro-linked or fused rings.

[0041] Preferred carbyl and hydrocarbyl groups are optionally substituted alkyl, alkenyl, alkynyl, alkoxy, alkylcarbonyl, alkoxycarbonyl, alkylcarbonyloxy and alkoxycarbonyloxy having 1 to 40, preferably 1 to 25, particularly preferably 1 to 18 C atoms, optionally substituted aryl or aryloxy having 6 to 40, preferably 6 to 25 C atoms, or optionally substituted alkylaryl, arylalkyl, alkylaryloxy, arylalkyloxy, arylcarbonyl, aryloxycarbonyl, arylcarbonyloxy and aryloxycarbonyloxy having 6 to 40, preferably 6 to 25 C atoms.

[0042] More preferred carbyl and hydrocarbyl groups are C1-C 40 Alkyl, C2-C 40 Alkenyl, C2-C 40 Alkynyl, C3-C 40 Allyl, C4-C 40 Alkyldienyl, C4-C 40 Polyenyl, C6-C 40 Aryl, C6-C 40 Alkylaryl, C6-C 40 Arylalkyl, C6-C 40 Alkylaryloxy, C6-C 40 Arylalkyloxy, C2-C 40 Heteroaryl, C4-C 40 Cycloalkyl, C4-C 40 cycloalkenyl, etc. Preferred are C-C 22 Alkyl, C2-C 22 Alkenyl, C2-C 22 Alkynyl, C3-C 22 Allyl, C4-C 22 Alkyldienyl, C6-C 12 Aryl, C6-C 20 Aryl alkyl, and C2-C 20 Given to heteroaryl.

[0043] Further preferred carbyl and hydrocarbyl groups are linear, branched or cyclic alkyl radicals having 1 to 40, preferably 1 to 25, C atoms, more preferably 1 to 12 C atoms, which are unsubstituted or mono- or polysubstituted by F, Cl, Br, I or CN, in which one or more non-adjacent CH groups are each -C(R x )=C(R x )-, -C≡C-, -N(R x ) -, -O-, -S-, -CO-, -CO-O-, -O-CO-, -O-CO-O- may be independently replaced by O and / or S atoms in a manner that they are not directly bonded to each other.

[0044] In the above, R x represents preferably H, a halogen, or a linear, branched or cyclic alkyl chain having 1 to 25 C atoms, and further, one or more non-adjacent C atoms may be replaced by -O-, -S-, -CO-, -CO-O-, -O-CO-, or -O-CO-O-, and one or more H atoms may be replaced by fluorine, an optionally substituted aryl or aryloxy group having 6 to 40 carbon atoms, or an optionally substituted heteroaryl or heteroaryloxy group having 2 to 40 carbon atoms.

[0045] Preferred alkyl groups are, for example, methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, s-butyl, t-butyl, 2-methylbutyl, n-pentyl, s-pentyl, n-hexyl, 2-ethylhexyl, n-heptyl, n-octyl, n-nonyl, n-decyl, n-undecyl, n-dodecyl, dodecanyl, trifluoromethyl, perfluoro-n-butyl, 2,2,2-trifluoroethyl, perfluorooctyl, perfluorohexyl, and the like.

[0046] Preferred alkenyl groups are, for example, ethenyl, propenyl, butenyl, pentenyl, cyclopentenyl, hexenyl, cyclohexenyl, heptenyl, cycloheptenyl, octenyl, cyclooctenyl, and the like. Preferred alkynyl groups are, for example, ethynyl, propynyl, butynyl, pentynyl, hexynyl, octynyl and the like.

[0047] Preferred alkoxy groups are, for example, methoxy, ethoxy, 2-methoxyethoxy, n-propoxy, i-propoxy, n-butoxy, i-butoxy, s-butoxy, t-butoxy, 2-methylbutoxy, n-pentoxy, n-hexoxy, n-heptyloxy, n-octyloxy, n-nonyloxy, n-decyloxy, n-undecyloxy, n-dodecyloxy, and the like. Preferred amino groups are, for example, dimethylamino, methylamino, methylphenylamino, phenylamino, and the like.

[0048] Aryl and heteroaryl groups can be monocyclic or polycyclic, i.e., have one ring (such as, for example, phenyl) or two or more rings, and can be fused (such as, for example, naphthyl) or covalently linked (such as, for example, biphenyl), or can contain a combination of fused and linked rings. Heteroaryl groups contain one or more heteroatoms, preferably selected from O, N, S and Se.

[0049] 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, which optionally contain fused rings and which may be optionally substituted.Furthermore, 5-, 6- or 7-membered aryl and heteroaryl groups, in which in addition one or more CH groups may be replaced by N, S or O in such a way that the O and / or S atoms are not directly bonded to each other, are preferred.

[0050] 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, and the like.

[0051] 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. 5-membered rings such as 1,3,4-thiadiazole, 1,2,5-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 indole, isoindole, indolizine, indazole, benzimidazole, benzotriazole, proline. phosphorus, naphthimidazole, phenanthrimidazole, pyridoimidazole, pyrazineimidazole, quinoxalineimidazole, benzoxazole, naphthoxazole, anthraxazole, phenanthrioxazole, isoxazole, benzothiazole, benzofuran, isobenzofuran, dibenzofuran, quinoline, isoquinoline, pteridine, benzo-5,6-quinoline, benzo-6,7-quinoline, benzo-7,8-quinoline, The heteroaryl groups may be fused groups such as 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 thereof. The heteroaryl groups may also be substituted with alkyl, alkoxy, thioalkyl, fluorine, fluoroalkyl or further aryl or heteroaryl groups.

[0052] (Non-aromatic) alicyclic and heterocyclic groups cover both saturated rings, i.e. rings containing only single bonds, and partially unsaturated rings, i.e. rings which may also contain multiple bonds. Heterocyclic rings contain one or more heteroatoms, preferably selected from Si, O, N, S and Se.

[0053] (Non-aromatic) alicyclic and heterocyclic groups can be monocyclic, i.e. containing only one ring (e.g. cyclohexane) or polycyclic, i.e. containing several rings (e.g. decahydronaphthalene or bicyclooctane). Saturated groups are preferred. Furthermore, monocyclic, bicyclic or tricyclic groups having 3 to 25 C atoms, optionally containing fused rings and optionally substituted, are preferred. Further preferred are 5-, 6-, 7- or 8-membered carbocyclic groups, in which in addition one or more C atoms may be replaced by Si and / or one or more CH groups may be replaced by N and / or one or more non-adjacent CH2 groups may be replaced by -O- and / or -S-.

[0054] Preferred alicyclic and heterocyclic groups are, for example, 5-membered groups such as cyclopentane, tetrahydrofuran, tetrahydrothiofuran, pyrrolidine, 6-membered groups such as cyclohexane, silinane, cyclohexene, tetrahydropyran, tetrahydrothiopyran, 1,3-dioxane, 1,3-dithiane, piperidine, 7-membered groups such as cycloheptane, and fused groups such as tetrahydronaphthalene, decahydronaphthalene, indane, bicyclo[1.1.1]pentane-1,3-diyl, bicyclo[2.2.2]octane-1,4-diyl, spiro[3.3]heptane-2,6-diyl, octahydro-4,7-methanoindan-2,5-diyl.

[0055] The aryl, heteroaryl, (non-aromatic) alicyclic and heterocyclic groups may optionally carry one or more substituents, preferably silyl, sulfo, sulfonyl, formyl, amine, imine, nitrile, mercapto, nitro, halogen, C1-C 12 Alkyl, C6-C 12 Aryl, C1-C12 The radical is selected from the group comprising alkoxy, hydroxyl, or a combination thereof.

[0056] Preferred substituents are solubility-promoting groups such as, for example, alkyl or alkoxy, electron-withdrawing groups such as fluorine, nitro or nitrile, or substituents for increasing the glass transition temperature (Tg) of the polymer, especially bulky groups such as, for example, t-butyl groups or optionally substituted aryl groups.

[0057] Preferred substituents, hereinafter also referred to as "L", are, for example, F, Cl, Br, I, -OH, -CN, -NO2, -NCO, -NCS, -OCN, -SCN, -C(=O)N(R x )2, -C(=O)Y x , -C(=O)R x , -C(=O)OR x , -N(R x )2, and R x has the above meaning, and Y x is halogen, optionally substituted silyl, optionally substituted aryl or heteroaryl having 4 to 40, preferably 4 to 20, ring atoms, and linear or branched alkyl, alkenyl, alkynyl, alkoxy, alkylcarbonyl, alkoxycarbonyl, alkylcarbonyloxy or alkoxycarbonyloxy having 1 to 25 C atoms, where one or more H atoms may optionally be replaced by F or Cl.

[0058] "Substituted silyl or aryl" is preferably halogen, -CN, R y , -OR y , -CO-R y , -CO-OR y , -O-CO-R y OR-O-CO-OR y means to be replaced by R y denotes H, a linear, branched or cyclic alkyl chain having 1 to 12 C atoms.

[0059] In the formulae shown herein, the substituted phenylene ring is [ka] and wherein L, whether identically or differently in each occurrence, has one of the meanings given herein and is preferably F, Cl, CN, NO2, CH3, C2H5, C(CH3)3, CH(CH3)2, CH2CH(CH3)C2H5, OCH3, OC2H5, COCH3, COC2H5, COOCH3, COOC2H5, CF3, OCF3, OCHF2, OC2F5 or P-Sp-, very preferably F, Cl, CN, CH3, C2H5, OCH3, COCH3, OCF3 or P-Sp-, most preferably F, Cl, CH3, OCH3, COCH3 or OCF3.

[0060] "Halogen" refers to F, Cl, Br or I, preferably F or Cl, more preferably F. The "polymerizable group" (P) is preferably selected from groups containing a C=C double bond or a C≡C triple bond and a group suitable for polymerization involving ring opening, such as an oxetane or epoxide group.

[0061] Preferably, the polymerizable group (P) is CH2=CW 1 -COO-, CH2=CW 1 -CO-, [ka] CH2=CW 2 -(O) k3 -, C.W. 1 =CH-CO-(O) k3 -, C.W. 1 =CH-CO-NH-, CH2=CW 1 -CO-NH-, CH3-CH=CH-O-, (CH2=CH)2CH-OCO-, (CH2=CH-CH2)2CH-OCO-, (CH2=CH)2CH-O-, (CH2=CH-CH2)2N-, (CH2=CH-CH2)2N-CO-, CH2=CW 1-CO-NH-, CH2=CH-(COO) k1 -Phe-(O) k2 -, CH2=CH-(CO) k1 -Phe-(O) k2 -, Phe-CH=CH-, During the ceremony, W 1 denotes H, F, Cl, CN, CF3, phenyl or alkyl having 1 to 5 C atoms, in particular H, F, Cl or CH3, W 2 denotes H or alkyl having 1 to 5 C atoms, in particular H, methyl, ethyl or n-propyl, W 3 and W 4 each independently of the other denotes H, Cl or alkyl having 1 to 5 C atoms, Phe denotes 1,4-phenylene, which may be optionally substituted by one or more radicals L as defined above but different from P-Sp, preferably preferred substituents L are F, Cl, CN, NO2, CH3, C2H5, OCH3, OC2H5, COCH3, COC2H5, COOCH3, COOC2H5, CF3, OCF3, OCHF2, OC2F5, also phenyl, and k1, k2 and k3 each independently represent 0 or 1, k3 preferably represents 1, and k4 represents an integer from 1 to 10.

[0062] Particularly preferred polymerizable groups P are H2=CH-COO-, CH2=C(CH3)-COO-, CH2=CF-COO-, CH2=CH-, CH2=CH-O-, (CH2=CH)2CH-OCO-, (CH2=CH)2CH-O-, [ka] Here, W 2 denotes H or alkyl having 1 to 5 C atoms, in particular H, methyl, ethyl or n-propyl,

[0063] Further preferred polymerizable groups (P) are vinyloxy, acrylate, methacrylate, fluoroacrylate, chloroacrylate, oxetane and epoxide, most preferably acrylate or methacrylate, especially acrylate.

[0064] Preferably, all multireactive polymerizable compounds and subformulas thereof contain, instead of one or more radicals P-Sp-, one or more branched radicals (multireactive polymerizable radicals) containing two or more polymerizable groups P.

[0065] Suitable radicals of this type, and polymerizable compounds containing them, are described, for example, in US 7,060,200 B1 or US 2006 / 0172090 A1.

[0066] Preference is given to multireactive polymerizable radicals selected from the following formulae: [ka] [ka] During the ceremony, Alkyl denotes a single bond or a straight-chain or branched alkylene having 1 to 12 C atoms, where one or more non-adjacent CH groups are each independently -C(R x )=C(R x )-, -C≡C-, -N(R x )-, -O-, -S-, -CO-, -CO-O-, -O-CO-, -O-CO-O- in a manner that the O and / or S atoms are not directly bonded to each other, and in addition, one or more H atoms may be replaced by F, Cl or CN, R x has the meaning given above, aa and bb each independently represents 0, 1, 2, 3, 4, 5, or 6; X is meant to represent X', and P v ~P z each independently of the other has the meaning given above for P.

[0067] Preferred spacer groups Sp and Sp 1-4 is selected from the formula Sp'-X' such that the radical "P-Sp-" fits the formula "P-Sp'-X'-"; Sp' denotes an alkylene having 1 to 20, preferably 1 to 12, C atoms, optionally mono- or polysubstituted by F, Cl, Br, I or CN, and in addition, one or more non-adjacent CH groups are each independently of one another -O-, -S-, -NH-, -NR x -, -SiR x R y -, -CO-, -COO-, -OCO-, -OCO-O-, -S-CO-, -CO-S-, -NR x -CO-O-, -O-CO-NR x -, -NR x -CO-NR y -, -CH=CH- or -C≡C- may replace O and / or S atoms in a manner that they are not directly bonded to each other, X' is -O-, -S-, -CO-, -COO-, -OCO-, -O-COO-, -CO-NR xx -, -NR xx -CO-, -NR xx -CO-NR yy -, -OCH2-, -CH2O-, -SCH2-, -CH2S-, -CF2O-, -OCF2-, -CF2S-, -SCF2-, -CF2CH2-, -CH2CF2-, -CF2CF2-, -CH=N-, -N=CH-, -N=N-, -CH=CR xx -, -CY xx =CY xx -, -CC-, -CH=CH-COO-, -OCO-CH=CH- or a single bond; R x and R y each independently of the other denotes H or alkyl having 1 to 12 C atoms, and Y xxand Y yy each independently represents H, F, Cl or CN.

[0068] X' is preferably -O-, -S--CO-, -COO-, -OCO-, -O-COO-, -CO-NR xx -, -NR xx -CO-, -NR xx -CO-NR yy - or a single bond. A typical spacer group Sp' is, for example, -(CH2) p1 -, -(CH2CH2O) q1 -CH2CH2-, -CH2CH2-S-CH2CH2-, -CH2CH2-NH-CH2CH2- or -(SiR xx R yy -O) p1 where p1 is an integer from 1 to 20, q1 is an integer from 1 to 3, and R xx and R yy has the meaning given above.

[0069] Particularly preferred groups -X'-Sp'- are -(CH2) p1 -, -O-(CH2) p1 -, -OCO-(CH2) p1 -,-OCOO-(CH2) p1 where p1 is an integer from 1 to 12.

[0070] Particularly preferred radicals Sp' are, for example, in each case straight-chain, methylene, ethylene, propylene, butylene, pentylene, hexylene, heptylene, octylene, nonylene, decylene, undecylene, dodecylene, octadecylene, ethyleneoxyethylene, methyleneoxybutylene, ethylenethioethylene, ethylene-N-methyliminoethylene, 1-methylalkylene, ethenylene, propenylene and butenylene.

[0071] For the purposes of the present invention, [ka] represents trans-1,4-cyclohexylene, and [ka] indicates 1,4-phenylene.

[0072] In the present invention, the group -COO--C(=O)O- or -CO2- denotes an ester group of the formula [ka] and the groups -OCO-, -OC(=O)-, -OC- or -OOC- represent an ester group of the formula [ka] The ester group is shown below.

[0073] At the molecular level, the birefringence of liquid crystals is determined by the anisotropy of the polarization rate (α = α ii -α ┴ ) The "polarization ratio" means the tendency of the electron distribution in an atom or molecule to be distorted. The polarization ratio increases as the number of electrons increases and the electron cloud becomes more diffuse. The polarization ratio is described, for example, in Jap. J. Appl. Phys. 42 , (2003) p. 3463.

[0074] The "optical retardation" of a layer of liquid crystalline or birefringent material at a given wavelength R(λ) (nm) is given by the formula R(λ)=Δn(λ) d is defined as the product of the birefringence Δn (λ) at that wavelength and the layer thickness d (nm), according to

[0075] Optical retardation, R, represents the difference in nanometers in the optical path length traveled by S-polarized and P-polarized light while passing through a birefringent material. "On-axis" retardation refers to the retardation at normal incidence to the sample surface.

[0076] The term "negative (optical) dispersion" refers to a birefringent or liquid crystal material or layer that exhibits reverse birefringence dispersion, in which the magnitude of birefringence (Δn) increases with increasing wavelength λ, i.e.

number

number

number

number

[0077] Since optical retardation at a given wavelength is defined as the product of birefringence and layer thickness as discussed above, [R(λ) = Δn(λ) d], optical dispersion can be expressed as "birefringence dispersion" in the ratio Δn(450) / Δn(550), or as "retardation dispersion" in the ratio R(450) / R(550), where R(450) and R(550) are the retardations of the material measured at wavelengths of 450 nm and 550 nm, respectively. Since the layer thickness d does not change with wavelength, R(450) / R(550) is equal to Δn(450) / Δn(550). Thus, a negative or reverse dispersion material or layer has R(450) / R(550)<1 or

number

number

number

number

[0078] In the present invention, unless otherwise specified, "optical dispersion" means retardation dispersion, ie the ratio R(450) / R(550).

[0079] The term "high variance" means that the absolute value of the variance exhibits a large deviation from 1, and the term "low variance" means that the absolute value of the variance exhibits a small deviation from 1. Thus, for example, "high negative variance" means that the variance value is significantly less than 1, and "low negative variance" means that the variance value is only slightly less than 1.

[0080] The retardation (R(λ)) of a material can be measured using a spectroscopic ellipsometer, such as the JA Woollam M2000 Spectroscopic Ellipsometer. This instrument can measure the optical retardation in nanometers of a birefringent sample, such as quartz, typically in the wavelength range of 370 nm to 2000 nm. From this data, the dispersion of the material (R(450) / R(550) or Δn(450) / Δn(550)) can be calculated.

[0081] In October 2006, N. Singh published a paper entitled "Spectroscopic Ellipsometry, Part 1 - Theory and Fundamentals, Part 2 - Practical Examples and Part 3 - Measurements" at the National Physical Laboratory (London, UK) on how to perform these measurements. The Retardation Measurement (RetMeas) Manual (2002) and Guide to WVASE (2002) ( W oollam V Available A ngle S pectroscopic E The retardation was measured by a 300 nm hologram measuring instrument (Woollam Co. Inc., Lincoln, NE, USA) according to the measurement procedure described in the 300 nm hologram measuring instrument (Woollam Co. Inc., Lincoln, NE, USA). Unless otherwise stated, this method is used to determine the retardation of the materials, films and devices described in this invention.

[0082] The term "A-plate" refers to an optical retarder utilizing a layer of uniaxially birefringent material with its extraordinary axis oriented parallel to the plane of the layer.

[0083] The term "C-plate" refers to an optical retarder utilizing a layer of uniaxially birefringent material with its extraordinary axis oriented perpendicular to the plane of the layer. In an A / C-plate with uniformly oriented optically uniaxially birefringent liquid crystal material, the optic axis of the film is given by the direction of the extraordinary axis. An A(or C)-plate that contains an optically uniaxially birefringent material with positive birefringence is also called a "positive A(or C)-plate" or "+A(or +C)-plate". An A(or C)-plate that contains a film of an optically uniaxially birefringent material with negative birefringence, such as a discotic anisotropic material, is also called a "negative A(or C)-plate" or "-A(or C)-plate", 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 negative C-plate optics.

[0084] The birefringence Δn is defined as Δn=n e -n o In the formula, n e is the extraordinary refractive index, n o is the ordinary refractive index, and the effective average refractive index n aV is given by: n av. =((2n o 2 +n e 2 ) / 3) 1 / 2

[0085] Average refractive index n av. Normal refractive index n o can be measured using an Abbe refractometer. Δn can be calculated from the above formula. Unless the context clearly indicates otherwise, plural forms of the terms used herein are to be construed as including the singular and vice versa.

[0086] Throughout the description and claims of this specification, the words "comprise" and "containing," and variations of these words, such as "comprises" and "contains," are intended to mean "including but not limited to" and are not intended to (and do not) exclude other elements. Meanwhile, the term "comprises" also encompasses, but is not limited to, the term "consisting of."

[0087] Throughout the description and claims of this specification, the words "obtainable" and "obtained" and variations of these words mean "including but not limited to" and are not intended to (and do not) exclude other elements, whereas "obtainable" also encompasses "obtained" but is not limited to it.

[0088] All concentrations are given in weight percent and relate to their respective mixture totals, all temperatures are given in degrees Celsius, and all temperature differences are given in degrees differential.

[0089] Detailed Description of the Invention Preferably, the compound of formula T is T1 and R T2 At least one of them shows P-Sp-, and the other R T1 or R T2is preferably a hydrogen atom, F, Cl, Br, I, a pentafluorosulfuranyl group, a cyano group, a nitro group, an isocyano group, a thioisocyano group, or a linear or branched alkyl group having 1 to 20 carbon atoms, in which any hydrogen atom in the group may be substituted by F, and one -CH2- or two or more non-adjacent -CH2- are each independently -O-, -S-, -OCH2-, -CHO-, -CO-, -COO-, -OCO-, -CO-S-, -S-CO-, -O-CO-O-, -CO-NH-, -NH-CO-, -SCH2-, -CH2S-, -CF2O-, -OCF2-, -CF2S-, -SCF2-, -CH=CH-COO-, -CH=CH-OCO-, -COO-CH=CH-, -OCO-CH=CH-, -COO-CH2CH2-, -OCO-CH2CH -CH-, -CHCH-COO-, -CHCH-OCO-, -COO-CH-, -OCO-CH-, -CH-COO-, -CH-OCO-, -CH=CH-, -N=N-, -CH=NN=CH-, -CF=CF-, or -C≡C-, more preferably a hydrogen atom, F, Cl, or a linear or branched alkyl group having 1 to 12 carbon atoms, wherein one -CH- or two or more non-adjacent -CH- groups each independently represent -O-, -COO-, -OCO-, or -O-CO-O-, even more preferably a hydrogen atom, F, Cl, a linear alkyl group or a linear alkoxy group having 1 to 8 carbon atoms, and particularly preferably a linear alkyl group or a linear alkoxy group having 1 to 8 carbon atoms.

[0090] In another preferred embodiment, R T1 and R T2 Both indicate P-Sp-.

[0091] In a further preferred embodiment, A in formula T T1 and A T2each independently in each occurrence preferably represents a 1,4-phenylene group, a 1,4-cyclohexylene group, or a naphthalene-2,6-diyl group, which may be unsubstituted or each and independently in each occurrence may be substituted, the substituents L: [ka] In the formula, r represents an integer between 0 and 4, and p and q each and independently represent an integer between 0 and 3.

[0092] In a further preferred embodiment, A in formula T T1 and A T2 represents, independently and at each occurrence, a group selected from the following formulae A-1 to A-11, [ka] Furthermore, groups selected from formulae (A-1) to (A-8) are preferred, groups selected from formulae (A-1) to (A-4) are particularly preferred, and groups selected from formulae (A-1) and / or (A-2) are further preferred.

[0093] In a preferred embodiment, in formula T, the group G T1 The group Z adjacent to T1 Group A linked to T1 , and the group G T1 The group Z adjacent to T2 A connected to T2 Each of the groups represented by the formula: preferably represents a 1,4-cyclohexylene group, which may be unsubstituted or substituted with one or more of the substituents L (A-III), more preferably a group represented by the formula A-2.

[0094] In another preferred embodiment, a plurality of groups A T1 and A T2 If A exists, T1 and A T2 The group represented by T1 A adjacent toT1 and A T2 are independently selected from G T1 A group that is not adjacent to or adjacent to T1 and A T2 may be different or the same, and preferably each independently represents a 1,4-phenylene group or a naphthalene-2,6-diyl group which may be unsubstituted or substituted with one or more substituent groups L, more preferably a group selected from formulae (A-1) and (A-3) to (A-11), still more preferably a group selected from formulae (A-1) and (A-3) to (A-8), and particularly preferably a group selected from formulae (A-1), (A-3), and (A-4).

[0095] Z T1 When a plurality of Z are present, they may be different from each other or may be the same. T2 When present, they may be different from each other or may be the same.

[0096] Also, Z T1 and Z T2 When a plurality of groups are present, each group independently represents preferably -OCH-, -CHO-, -COO-, -OCO-, -CFO-, -OCF-, -CHCH-, -CFCF-, -CH=CH-COO-, -CH=CH-OCO-, -COO-CH=CH-, -OCO-CH=CH-, -COO-CHCH-, -OCO-CHCH-, -CHCH-COO-, -CHCH-OCO-, -CH=CH-, -CF=CF-, -C≡C- or a single bond, and more preferably -OCH-, -CHO-, -CO It represents O-, -OCO-, -CF2O-, -OCF2-, -CH2CH2-, -COO-CH2CH2-, -OCO-CH2CH2-, -CH2CH2-COO-, -CH2CH2-OCO-, -CH=CH-, -C≡C- or a single bond, further preferably -OCH2-, -CHO-, -COO-, -OCO-, -CF2O-, -OCF2- or a single bond, more preferably -OCH2-, -CHO-, -COO-, -OCO- or a single bond, and particularly preferably -OCH2-, -CHO-, -COO- or -OCO-.

[0097] In formula T, m1 and m2 each independently represent an integer of 1 to 6, and preferably, m1+m2 represents an integer of 1 to 6.

[0098] More preferably, m1 and m2 each independently represent an integer of 1 to 3, and particularly preferably an integer of 1 or 2. Preferably, m1 and m2 are the same as each other, but it is equally preferable that m1 and m2 are different.

[0099] The preferred compounds of formula T are preferably selected from the group of compounds of formulae (Ta) to (Tf): [ka] During the ceremony R T1 , R T2 , and G T1 has the same meaning as in formula T, A T11 ~A T23 is the A of formula T T1 and A T2 has the same meaning as Z T11 ~Z T23 is the formula T ZT1 and ZT2 has the same meaning as

[0100] The group R in formulas (Ta) to (Tf) T1 , R T2 , G T1 , A T11 ~A T22 and Z T11 ~Z T22 Preferred forms of each of the formulas are the same as those for formula T. Further preferred compounds of formula T are preferably selected from the group of compounds of formula (Td):

[0101] Preferred compounds of formula T are preferably selected from the group of compounds of formula (Td-1) or (Td-2): [ka] During the ceremony P, Sp and G T1 has the same meaning as in formula T, A T11 ~A T22 is the A of formula T T1 and A T2 has the same meaning as Z T11 ~Z T22 is Z in formula T T1 and Z T2 has the same meaning as

[0102] Further, the preferred compound represented by formula T is preferably selected from the group of compounds represented by formula (Td-2), and more preferably selected from the group of compounds represented by formulas (Td-2-1) to (Td-2-3): [ka] During the ceremony P, Sp and G T1 has the same meaning as in formula T, A T11 ~A T22 is the A of formula T T1 and A T2 has the same meaning as Z T11 ~Z T22 is Z in formula T T1 and Z T2 has the same meaning as

[0103] Further, preferred compounds of formula T are preferably selected from the group of compounds of formula (Td-2-1) and / or (Td-2-3), and more preferably from the group of compounds of the following formulae: [ka] During the ceremony P, Sp and G T1 has the same meaning as in formula T, A T11 ~A T22 is the A of formula T T1 and A T2 has the same meaning as Z T11 ~Z T22 is the formula T ZT1 and ZT2 has the same meaning as X 11 and X 21 has one of the meanings as given for X' as given above.

[0104] Further preferred compounds of formula T are preferably selected from the group of compounds of formulae (Td-2-1) and / or (Td-2-3) which are selected from the group of compounds of the following formulae: [ka] During the ceremony P, Sp and G T1 has the same meaning as in formula T, and X 11 and X 21 has one of the meanings given for X' as given above, CYC denotes 1,4-cyclohexylene, and PheL denotes 1,4-phenylene, in which one or more H atoms can be replaced by L, which at each occurrence have the same meaning as in formula T.

[0105] Preferably, in the group of compounds of the formulae (Td-2-1a-1) to (Td-2-3b-3) and sub-formulae thereof, -P preferably each and independently represents an acrylate or methacrylate group, and / or -Sp is preferably each and independently -(CH) p1 -, where p1 is an integer from 1 to 12, preferably from 3 to 6; and / or -X 11 and X 21preferably each independently represents -O-, -S-CO-, -COO-, -OCO-, -O-COO-, preferably -O-, and / or -G T1 is preferably [ka] -R 0 and R 00 denotes a branched or linear alkyl group having 1 to 5 C atoms, -W 1 and W 2 are each independently [ka] [ka] in which Y has one of the meanings as given in formula T and preferably denotes F or H, and / or -CYC represents 1,4-cyclohexylene, and / or -PheL represents 1,4-phenylene.

[0106] The compounds of formula (T), (TA-1) to (TA-3) and subformulae thereof can be prepared by analogy with processes known to those skilled in the art and standard works of organic chemistry such as, for example, Houben-Weyl, Methoden der organischen Chemie [Methods of Organic Chemistry], Thieme-Verlag, Stuttgart.

[0107] Compounds of formula T can be advantageously utilized in polymerizable LC media. Preferably, such a polymerisable LC medium comprises one, two or more compounds of formula T, more preferably one compound of formula T.

[0108] In preferred embodiments, compounds of formula T include compounds of formulas 1-5 of, for example, US 2015175564, WO 17079867 A1, WO16104317 A, US 2015277007 A1, or WO 16171041 A1 and US 2015175564 A1, or H-type compounds as disclosed in WO 2008 / 119427 A1.

[0109] The proportion of the compound of formula T in the polymerizable liquid crystal material according to the present invention is preferably in the range of 1 to 99.9% by weight, more preferably in the range of 2 to 80% by weight, and further preferably in the range of 3 to 60% by weight.

[0110] Preferably, the compound of formula T is utilised together with other preferably mesogenic or liquid crystalline compounds. More preferably, the LC material comprises one or more additional compounds selected from reactive mesogens (RM), most preferably selected from monoreactive and direactive RMs.

[0111] Preferably, the polymerizable LC medium comprises one or more di- or multi-reactive mesogenic compounds selected from the group of compounds of formula DRM P 1 -Sp 1 -MG-Sp 2 -P 2 DRM During the ceremony P 1 and P 2 each independently represents a polymerizable group, Sp1 and Sp 2 are, independently of each other, a spacer group (Sp) or a single bond, MG is a rod-shaped mesogenic group, preferably selected from the formula MG -(A 1D -Z 1D ) n -A 2D - M.G. During the ceremony A 1D and A 2Drepresent, independently of one another, an aromatic or alicyclic group, which optionally contains one or more heteroatoms selected from N, O and S, and optionally L 1 may be mono- or polysubstituted by L 1 each independently has one of the meanings given above in formula T, R 00 and R 000 denote, independently of one another, H or alkyl having 1 to 12 C atoms, Z 1 When there are a plurality of groups, each independently represents -O-, -S-, -CO-, -COO-, -OCO-, -S-CO-, -CO-S-, -O-COO-, -CO-NR 00 -, -NR 00 -CO-, -NR 00 -CO-NR 000 , -NR 00 -CO-O-, -O-CO-NR 00 -, -OCH2-, -CH2O-, -SCH2-, -CH2S-, -CF2O-, -OCF2-, -CF2S-, -SCF2-, -CH2CH2-, -(CH2) n1、 -CF2CH2-, -CH2CF2-, -CF2CF2-, -CH=N-, -N=CH-, -N=N-, -CH=CR 00 -, -CY 1 =CY 2 -, -C≡C-, -CH=CH-COO-, -OCO-CH=CH- or a single bond; Y 1 and Y 2 are each independently H, F, Cl or CN, n is 1, 2, 3 or 4, preferably 1 or 2, most preferably 2 n1 is an integer from 1 to 10, preferably 1, 2, 3 or 4; Here, compounds of formula T are excluded.

[0112] Preferred group A 1D and A 2Dincludes, without limitation, 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 may be unsubstituted or mono-, di-, tri- or tetra-substituted by groups L as defined above.

[0113] Preferred group A 1D and A 2D 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 optionally be replaced by O and / or S, in which these groups may be unsubstituted or one-, two-, three- or four-substituted by a group L as defined above.

[0114] Preferred group Z 1D is preferably selected at each occurrence from -COO-, -OCO-, -CHCH-, -CFO-, -OCF-, -C≡C-, -CH=CH-, -OCO-CH=CH-, -CH=CH-COO-, or a single bond;

[0115] Highly preferred multiactive or bireactive mesogenic compounds of formula DRM are selected from the following formulae: [ka] JPEG2024538996000036.jpg101144 During the ceremony P 0are, when present in plurality, mutually independent, a polymerizable group (P), preferably an acrylic, methacrylic, oxetane, epoxy, vinyl, heptadiene, vinyloxy, propenyl ether or styrene group, L has, identically or differently in each occurrence, one of the meanings given in formula DRM and is preferably, in the case of several occurrences, independently of one another, selected from F, Cl, CN or alkyl, alkoxy, alkylcarbonyl, alkoxycarbonyl, alkylcarbonyloxy or alkoxycarbonyloxy having 1 to 5 C atoms, which may be optionally halogenated, r is 0, 1, 2, 3 or 4; x and y are each independently 0 or an integer from 1 to 12, which may be the same or different; Each z is independently 0 or 1, provided that when the adjacent x or y is 0, z is 0.

[0116] Particularly preferred are compounds of the formulae DRMa1, DRMa2, DRMa3, DRMa7 and DRMf, in particular compounds of the formulae DRMa1, DRMa7 and DRMf.

[0117] Preferably, the polymerisable LC material additionally comprises at least one monoreactive mesogenic compound, preferably of formula MRM P 1 -Sp 1 -MG-R MRM In the formula, P 1 , Sp 1 and MG has one of the meanings given above in the formula DRM, R is 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, straight-chain 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, and R x and R y are selected from, independently of one another, H or alkyl having 1 to 12 C atoms.

[0118] Preferably, the monoreactive mesogenic compound of formula MRM is selected from the following formulae: [ka] JPEG2024538996000038.jpg214154 JPEG2024538996000039.jpg224157 JPEG2024538996000040.jpg162153 In the formula, P 0 , L, r, x, y and z are as defined in Formula DRMa-1 to Formula DRMe; R 0 is alkyl, alkoxy, thioalkyl, alkylcarbonyl, alkoxycarbonyl, alkylcarbonyloxy or alkoxycarbonyloxy having one or more, preferably 1 to 15, C atoms, or Y 0 indicates, Y 0 is F, Cl, CN, NO2, OCH3, OCN, SCN, SF5 or 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, A0 are, in the case of a plurality of occurrences, independently of one another, 1,4-phenylene which may be unsubstituted or substituted by 1, 2, 3 or 4 radicals L, or trans-1,4-cyclohexylene, u and v are independently 0, 1 or 2; w is 0 or 1, and wherein the benzene and naphthalene rings may be further substituted with one or more identical or different groups L.

[0119] Further 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, especially compounds of formulae MRM1 and MRM7.

[0120] Compounds of formula DRM, MRM and their subformulae are known to those skilled in the art and can be prepared analogously to processes described in standard works of organic chemistry such as, for example, Houben-Weyl, Methoden der organischen Chemie [Methods of Organic Chemistry], Thieme-Verlag, Stuttgart.

[0121] The proportion of the monoreactive, direactive, or trireactive liquid crystal compound in the polymerizable liquid crystal material according to the present invention is preferably in the range of 30 to 99% by weight, more preferably in the range of 40 to 99% by weight, and even more preferably in the range of 50 to 99% by weight.

[0122] In a preferred embodiment, the proportion of the direactive or multireactive polymerizable mesogenic compound in the polymerizable liquid crystal material according to the present invention is preferably in the range of 5 to 99% by weight, more preferably in the range of 10 to 97% by weight, and even more preferably in the range of 15 to 95% by weight.

[0123] In a preferred embodiment, the proportion of the monoreactive polymerizable mesogenic compound in the polymerizable liquid crystal material according to the present invention, if present, is preferably in the range of 5 to 80% by weight, more preferably in the range of 10 to 75% by weight, and even more preferably in the range of 15 to 75% by weight.

[0124] In another preferred embodiment, the proportion of the multireactive polymerizable mesogenic compound in the polymerizable liquid crystal material according to the present invention, if present, is preferably in the range of 1 to 30% by weight, more preferably in the range of 2 to 20% by weight.

[0125] In another preferred embodiment the polymerisable LC material does not contain any polymerisable mesogenic compounds with more than one polymerisable group. In another preferred embodiment the polymerisable LC material does not contain any polymerisable mesogenic compounds with less than two polymerisable groups.

[0126] In another preferred embodiment the polymerisable LC material is an achiral material, ie it does not contain chiral polymerisable mesogenic compounds or any other chiral compounds.

[0127] In a further preferred embodiment the polymerisable LC material comprises at least one monoreactive mesogenic compound, preferably selected from formula MRM-1, at least one direactive mesogenic compound, preferably selected from formula DRMa-1, and at least one compound of formula T, respectively.

[0128] In a further preferred embodiment the polymerisable LC material comprises at least one monoreactive mesogenic compound, preferably selected from formula MRM-7, at least one direactive mesogenic compound, preferably selected from formula DRMa-7 and / or DRMf, and at least one compound of formula T, respectively.

[0129] In a further preferred embodiment the polymerisable LC material comprises at least two monoreactive mesogenic compounds, preferably selected from compounds of formulae MRM-1 and / or MRM-7, at least one bireactive mesogenic compound, preferably selected from compounds of formulae DRMa-7 and / or DRMf, and at least one compound of formula T, respectively.

[0130] In a further preferred embodiment the polymerisable LC material comprises at least two monoreactive mesogenic compounds, preferably selected from compounds of formula MRM-1 and / or MRM-7, at least two direactive mesogenic compounds, preferably selected from compounds of formula DRMa-7 and / or DRMf, respectively, and at least one compound of formula T.

[0131] In a further preferred embodiment the polymerisable LC material comprises at least two direactive mesogenic compounds, preferably selected from compounds of formula DRMa-7 and / or DRMf, and at least one compound of formula T, respectively.

[0132] In a further preferred embodiment the polymerisable LC material may optionally comprise one or more additives or auxiliaries selected from the group consisting of further polymerisation initiators, antioxidants, surfactants, stabilizers, catalysts, sensitisers, inhibitors, chain transfer agents, co-reactant monomers, reactive thinners, surface active compounds, lubricants, wetting agents, dispersants, hydrophobising agents, adhesives, flow improvers, degassing or antifoaming agents, degassing agents, diluents, reactive diluents, auxiliaries, colourants, dyes, pigments and nanoparticles.

[0133] Such auxiliaries are commercially available from TEGO, for example as TEGO® Glide 100, TEGO® Glide ZG 400, TEGO® Glide 406, TEGO® Glide 410, TEGO® Glide 411, TEGO® Glide 415, TEGO® Glide 420, TEGO® Glide 435, TEGO® Glide 440, TEGO® Glide 450, TEGO® Glide A 115, TEGO® Glide B 1484 (which may also be used as a defoamer and degasser), TEGO® Flow ATF, TEGO® Flow 300, TEGO® Flow 460, TEGO® Flow 425 and TEGO® Flow ZFS 460. Suitable radiation curable lubricants and flow aids that can also be used to improve scratch resistance are TEGO® Rad 2100, TEGO® Rad 2200, TEGO® Rad 2500, TEGO® Rad 2600 and TEGO® Rad 2700, also available from TEGO.

[0134] Such auxiliaries are also available from BYK as, for example, BYK®-300, BYK®-306, BYK®-307, BYK®-310, BYK®-320, BYK®-333, BYK®-341, Byk® 354, BYK® 361, Byk® 361N, BYK® 388. Such an auxiliary is available, for example, from 3M as FC4430®.

[0135] Such agents are available, for example, as FluorN® 561 or FluorN® 562 from Cytonix. Such auxiliaries are available, for example, as Tivida® FL 2300 and Tivida® FL 2500 from Merck KGaA.

[0136] 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. Examples of heat curing coagents that can be used are the products BYK®-370, BYK®-373 and BYK®-375 available from BYK.

[0137] A wide variety of such auxiliaries are available, for example, from Tego as TEGO® Wet KL 245, TEGO® Wet 250, TEGO® Wet 260 and TEGO® Wet ZFS 453, and from BYK as BYK®-306, BYK®-307, BYK®-310, BYK®-333, BYK®-344, BYK®-345, BYK®-346, and BYK®-348.

[0138] Wetting and dispersing aids are available, for example, from Tego as TEGO® Dispers 610, TEGO® Dispers 610 S, TEGO® Dispers 630, TEGO® Dispers 700, TEGO® Dispers 705, TEGO® Dispers 710, TEGO® Dispers 720 W, TEGO® Dispers 725 W, TEGO® Dispers 730 W, TEGO® Dispers 735 W and TEGO® Dispers 740. W and from BYK 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®-168, Disperbyk®-169, Disperbyk®-200, Disperbyk®-201, Disperbyk®-202, Disperbyk®-203, Disperbyk®-204, Disperbyk®-205, Disperbyk®-206, Disperbyk®-207, Disperbyk®-208, Disperbyk®-209, Disperbyk®-300, Disperbyk®-310, Disperbyk®-311, Disperbyk®-312, Disperbyk®-313, Disperbyk®-314, Disperbyk®-315, Disperbyk®-320, Disperbyk®-325, Disperbyk®-326, Disperbyk®-327, Disperbyk®-328, Disperbyk®-329, Disperbyk®-401, Disperbyk®-410, Disperbyk®-421, Disperbyk®-422, Disperbyk®-423, Disperbyk®-424, Disperbyk®-425, Disperbyk®-430, Disperbyk®-440, Disperbyk®-445, Disperbyk®-446 )-165, Disperbyk®-166, Disperbyk®-167, Disperbyk®-170, Disperbyk®-174, Disperbyk®-180, Disperbyk®-181, Disperbyk®-182, Disperbyk®-183, Disperbyk®-184, Disperbyk®-185, Disperbyk®-190, Anti-Terra®-U, Anti-Terra®-U 80, Anti-Terra®-P, Anti-Terra®-203, Anti-Terra®-204, Anti-Terra®-206, BYK®-151, BYK®-154, BYK®-155, BYK®-P 104 S, BYK®-P 105, Lactimon®, Lactimon®-WSand Bykumen®.

[0139] Such hydrophobizing agents are commercially available, for example from Tego, as Tego® Phobe WF, Tego® Phobe 1000, Tego® Phobe 1000 S, Tego® Phobe 1010, Tego® Phobe 1030, Tego® Phobe 1010, Tego® Phobe 1010, Tego® Phobe 1030, Tego® Phobe 1040, Tego® Phobe 1050, Tego® Phobe 1200, Tego® Phobe 1300, Tego® Phobe 1310 and Tego® Phobe 1400.

[0140] Adhesion promoters in the broad sense also include the substrate wetting aids already listed, but these generally do not have the same adhesion promoting capabilities.

[0141] The variety of adhesion promoter systems is not surprising, considering the widely differing physical and chemical properties of substrates, printing inks, coating compositions, and paints intended for printing, coating, etc.

[0142] Silane 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®.

[0143] Although corresponding technical information from the manufacturers of such additives should generally be used, the skilled person can obtain this information in a simple manner through corresponding preliminary experiments.

[0144] Auxiliaries for improving scratch resistance include, for example, the above-mentioned products TEGO® Rad 2100, TEGO® Rad 2200, TEGO® Rad 2500, TEGO® Rad 2600 and TEGO® Rad 2700, available from Tego.

[0145] Examples of light, heat and / or oxidation stabilizers may be described below. 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, nonylphenols with linear or branched side chains alkylated monophenols such as 2,6-dinonyl-4-methylphenol, 2,4-dimethyl-6-(1'-methylundec-1'-yl)phenol, 2,4-dimethyl-6-(1'-heptadec-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;

[0146] hydroquinones 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-hydroxyphenylstearate and bis(3,5-di-tert-butyl-4-hydroxyphenyl)adipate;

[0147] Tocopherols, such as α-tocopherol, β-tocopherol, γ-tocopherol, δ-tocopherol and mixtures of these compounds, and tocopherol derivatives, such as tocopheryl acetate, succinate, nicotinate and 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;

[0148] 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- alkylidene bisphenols such as 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;

[0149] 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

[0150] Hydroxybenzyl compounds such as 1,3,5-tris(3,5-di-tert-butyl-4-hydroxybenzyl)-2,4,6-trimethyl-benzene, 1,4-bis(3,5-di-tert-butyl-4-hydroxybenzyl)-2,3,5,6-tetramethyl-benzene and 2,4,6-tris(3,5-di-tert-butyl-4-hydroxybenzyl)phenol aromatics;

[0151] 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-4-hydroxybenzo triazine compounds such as 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;

[0152] 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;

[0153] Esters of propionate and acetate, mono- or polyhydric alcohols, such as methanol, ethanol, n-octanol, i-octanol, octadecanol, 1,6-hexanediol, 1,9-nonanediol, ethylene glycol, 1,2-propanediol, neopentyl glycol, thiodiethylene glycol, diethylene glycol, triethylene glycol, pentaerythritol, tris(hydroxyethyl)isocyanurate, N,N'-bis(hydroxyethyl)oxalamide, 3-thiaundecanol, 3-thiapentadecanol, trimethylhexanediol, trimethylolpropane and 4-hydroxymethyl-1-phospha-2,6,7-trioxabicyclo[2.2.2]-octane,

[0154] 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, laurate and stearate, and ascorbyl sulfate and phosphate;

[0155] N,N'-Diisopropyl-p-phenylenediamine, N,N'-Di-sec-butyl-p-phenylenediamine, N,N'-Bis(1,4-dimethylpentyl)-p-phenylenediamine, N,N'-Bis(1-ethyl-3-methylpentyl)-p-phenylenediamine, N,N'-Bis(1-methylheptyl)-p-phenylenediamine, N,N'-Dicyclohexyl-p-phenylenediamine, N,N'-Diphenyl-p-phenylenediamine, N,N'-Bis( 2-Naphthyl)-p-phenylenediamine, N-isopropyl-N'-phenyl-p-phenylenediamine, N-(1,3-dimethylbutyl)-N'-phenyl-p-phenylenediamine, N-(1-methylheptyl)-N'-phenyl-p-phenylenediamine, N-cyclohexyl-N'-phenyl-p-phenylenediamine, 4-(p-toluenesulfamoyl)diphenylamine, N,N'-dimethyl-N,N'-di-sec-butyl-p-phenylenediamine , octyl-substituted diphenylamines such as diphenylamine, N-allyldiphenylamine, 4-isopropoxydiphenylamine, N-phenyl-1-naphthylamine, N-(4-tert-octylphenyl)-1-naphthylamine, N-phenyl-2-naphthylamine, p,p′-di-tert-octyldiphenylamine, 4-n-butylaminophenol, 4-butyrylaminophenol, 4-nonanoylaminophenol, 4-dodecanoylaminophenol, , 4-octadecanoylaminophenol, bis[4-methoxyphenyl)amine, 2,6-di-tert-butyl-4-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)phenylamine, 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, mono- and dialkylated tert-butyldiphenylamines, 2,3-dihydro-3,3-dimethyl-4H-1,4-benzothiazine, phenothiazides, Antioxidants based on amine compounds such as mixtures of azines, mixtures of mono- and dialkylated tert-butyl / tert-octyl phenothiazines, mixtures of mono- and dialkylated tert-octyl phenothiazines, N-allyl phenothiazine, 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,

[0156] Triphenylphosphine Triphenyl phosphite, diphenyl alkyl phosphite, phenyl dialkyl phosphite, 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, diisodecyloxy pentaerythritol diphosphite, bis(2,4-di-tert-butyl-6-methylphenyl) pentaerythritol diphosphite, bis(2 Phosphines, phosphites and phosphonites such as 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-dioxaphosphine, 6-fluoro-2,4,8,10-tetra-tert-butyl-12-methyl-dibenz[d,g]-1,3,2-dioxaphosphine, bis(2,4-di-tert-butyl-6-methylphenyl)methyl phosphite and bis(2,4-di-tert-butyl-6-methylphenyl)ethyl phosphite.

[0157] 2-(2′-hydroxy-5′-methylphenyl)benzotriazole, 2-(3′,5′-di-tert-butyl-2′-hydroxyphenyl)benzotriazole, 2-(5′-tert-butyl-2′-hydroxyphenyl)benzotriazole, 2-(2′-hydroxy-5′-(1,1,3,3-tetramethylbutyl)phenyl)benzotriazole, 2-(3′,5′-di-tert-butyl-2′-hydroxyphenyl)-5-chlorobenzotriazole, 2-(3′-tert-butyl-2′-hydroxy-5′-methylphenyl)-5 -Chlorobenzotriazole, 2-(3'-sec-butyl-5'-tert-butyl-2'-hydroxyphenyl)benzotriazole, 2-(2'-hydroxy-4'-octyloxyphenyl)benzotriazole, 2-(3',5'-di-tert-amyl-2'-hydroxyphenyl)benzotriazole, 2-(3,5'-bis-(α,α-dimethylbenzyl)-2'-hydroxyphenyl)benzotriazole, 2-(3'-tert-butyl-2'-hydroxy-5'-(2-octyloxycarbonylethyl)phenyl)-5-chlorobenzazole, Mixture of benzotriazole, 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-octyloxycarbonyl)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-(2'-hydroxyphenyl)benzotriazoles, such as the fully esterified product of 2-[3'-tert-butyl-5'-(2-methoxycarbonylethyl)-2'-hydroxyphenyl]-2H-benzotriazole with polyethylene glycol 300;

[0158] Sulfur-containing peroxide scavengers and sulfur-containing antioxidants (such as esters of 3,3'-thiodipropionic acid), for example, 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;

[0159] 2-hydroxybenzophenones, such as their 4-hydroxy, 4-methoxy, 4-octyloxy, 4-decycloxy, 4-dodecyloxy, 4-benzyloxy, 4,2',4'-trihydroxy and 2'-hydroxy-4,4'-dimethoxy derivatives;

[0160] 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;

[0161] 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, 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-tetramethyl- Condensation products of 4-hydroxypiperidine and succinic acid, N,N'-bis(2,2,6,6-tetramethylpiperidin-4-yl)hexamethylenediamine and 4-tert-octylamino-2,6-dichloro-1,3,5-triazine, tris(2,2,6,6-tetramethylpiperidin-4-yl)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-tetramethylpiperidine, condensation product of N,N'-bis(2,2,6,6-tetramethylpiperidin-4-yl)hexamethylenediamine and 4-cyclohexylamino-2,6-dichloro-1,3,5-triazine, 1,2-bis(3-aminopropylamino)ethane and 2,4,6-trichloro-1,3,5-triazine Condensation products of azines, 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] Sterically bulky amines such as the condensation product of decane and epichlorohydrin, and the condensation product of 4-amino-2,2,6,6-tetramethylpiperidine and poly(methoxypropyl-3-oxy)-[4(2,2,6,6-tetramethyl)piperidinyl]-siloxane with tetramethylolacetylenediurea.

[0162] 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 its mixture with 2-ethoxy-2'-ethyl-5,4'-di-tert-butoxanilide, and mixtures of ortho-, para-methoxy-disubstituted oxanilides, and mixtures of ortho- and para-ethoxy-disubstituted oxanilides, and

[0163] 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(2,4-dimethylphenyl)-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-(2-hydroxyphenyl)-1,3,5-triazines such as (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.

[0164] In another preferred embodiment, the polymerizable LC material comprises one or more specific antioxidant additives, preferably selected from the Irganox® series, such as the antioxidants Irganox® 1076 and Irganox® 1010 commercially available from Ciba, Switzerland.

[0165] In another preferred embodiment, the polymerizable LC material comprises one or more, more preferably two or more photoinitiators. Typically, radical photoinitiators that can be utilized are selected, for example, 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, Darcure TPO. Further suitable photoinitiators are preferably selected from commercially available oxime ester photoinitiators, for example Oxe02 (Ciba), N-1919T (Adeka) or SPI-02 to SPI-04 (Samyang).

[0166] The overall concentration of the polymerization initiator in the polymerizable LC medium is preferably 0.5-10%, very preferably 0.8-8%, more preferably 1-6%.

[0167] Preferably, the polymerisable LC material comprises, besides one or more compounds of formula T, a) one or more di- or multi-reactive polymerizable mesogenic compounds, b) one or more photoinitiators; c) optionally one or more monoreactive polymerizable mesogenic compounds, e) optionally one or more antioxidant additives; f) optionally one or more adhesion promoters; g) optionally one or more surfactants; g) optionally one or more stabilizers; h) optionally one or more mono-, di- or polyreactive polymerizable non-mesogenic compounds, i) optionally, one or more dyes that exhibit an absorption maxima at the wavelengths used to initiate photopolymerization; j) optionally one or more chain transfer agents; k) optionally one or more stabilizers; l) optionally one or more lubricants and flow aids, and m) optionally one or more diluents;

[0168] More preferably, said polymerizable LC material comprises a) one or more compounds of formula T, b) one or more photoinitiators c) one or more, preferably two or more, direactive polymerizable mesogenic compounds, preferably in an amount, if present, of 10 to 90% by weight, very preferably 15 to 75% by weight, preferably selected from the compounds of formula DRMa-1 and / or DRMa-7, and / or DRMf, or LC242 commercially available from BASF, d) optionally one or more, preferably two or more, monoreactive polymerizable mesogenic compounds, preferably in an amount of 10 to 95% by weight, very preferably 25 to 85%, preferably selected from the compounds of formula MRM-1 and / or MRM-7, e) optionally one or more antioxidants, preferably selected from esters of unsubstituted and substituted benzoic acid, in particular Irganox® 1076 and / or Irgacure, 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 lubricants and flow aids, preferably selected from BYK® 388, FC 4430, Fluor N 561 and / or Fluor N 562, if present, preferably in an amount of 0.1-5 wt.-%, very preferably 0.2-0.3 wt.-%.

[0169] The invention further relates to a method for the preparation of a polymerisable LC material as described above and below, comprising the step of providing one or more compounds of formula T to one or more of formula MRM and / or DRM.

[0170] The present invention further comprises: - providing a layer of a polymerizable LC material as described above and below on a substrate; -Polymerization of polymerizable LC materials by photopolymerization - optionally removing the polymerized LC material from the substrate and / or optionally providing it on another substrate, The present invention relates to a method for preparing a polymer film by

[0171] In a preferred embodiment, a layer of polymerizable LC material is provided on a substrate by first dissolving the polymerizable LC material in one or more solvents, preferably selected from organic solvents. The solvents are preferably selected from ketones such as acetone, methyl ethyl ketone, methyl propyl ketone, methyl isobutyl ketone or cyclohexanone; acetates such as methyl, ethyl or butyl acetate or methyl 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 di- or trichloromethane; glycols or their esters such as PGMEA (propyl glycol monomethyl ether acetate), γ-butyrolactone. Binary, ternary or higher mixtures of the above solvents can also be used.

[0172] When the polymerizable LC material is dissolved in one or more solvents, the total concentration of all solids, including the RM, in the solvent is preferably 10-60%.

[0173] This solution can then be coated or printed onto a substrate, for example by spin coating, printing, or other known techniques, and the solvent is allowed to evaporate prior to polymerization. In most cases, it is preferred to heat the mixture to facilitate evaporation of the solvent.

[0174] The polymerizable LC material can be applied onto the substrate by conventional coating techniques such as spin coating, bar coating, blade coating, etc. It can also be applied to the substrate by conventional printing techniques known to those skilled in the art, such as screen printing, offset printing, reel-to-reel printing, letterpress printing, gravure printing, rotogravure printing, flexographic printing, intaglio printing, pad printing, heat seal printing, inkjet printing or printing with a stamp or printing plate.

[0175] Suitable substrate materials and substrates are known to those skilled in the art and described in the literature, for example as conventional substrates used in the optical film industry, such as glass or plastic.Particularly suitable and preferred substrates for polymerization are polyesters, such as polyethylene terephthalate (PET) or polyethylene naphthalate (PEN), polyvinyl alcohol (PVA), polycarbonate (PC), triacetyl cellulose (TAC), cycloolefin polymer (COP), or commonly known color filter materials, in particular triacetyl cellulose (TAC), or cycloolefin polymer (COP), or commonly known color filter materials.

[0176] The polymerisable LC material preferably exhibits uniform alignment throughout the layer.Preferably the polymerisable LC material exhibits uniform planar or homeotropic alignment.

[0177] A preferred method used to support homeotropic alignment is to apply a corona discharge treatment to the plastic substrate, generating 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.

[0178] To produce a polymer film according to the present invention, the polymerizable compounds in the polymerizable LC material are polymerized or crosslinked by in situ photopolymerization (if one compound contains two or more polymerizable groups).

[0179] Photopolymerization can be carried out in one step, or it is possible to photopolymerize or crosslink compounds that did not react in the first step in a second step ("end curing").

[0180] Photopolymerization of the LC material is preferably achieved by exposing it to actinic radiation. Actinic radiation means irradiation with light, such as UV light, IR light, visible light, irradiation with X-rays or gamma rays, or irradiation with high-energy particles, such as ions or electrons. Preferably, polymerization is carried out by photoirradiation, 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. When using high lamp power, the curing time can be reduced. Another possible source of actinic radiation is a laser, such as for example a UV laser, an IR laser, or a visible laser.

[0181] 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.

[0182] The cure time is preferably 5 minutes or less, very preferably 3 minutes or less, and most preferably 1 minute or less. For mass production, short cure times of 30 seconds or less are preferred.

[0183] The suitable UV radiation power is preferably 5 to 200 mW cm -2 More preferably, it is in the range of 50 to 175 mWcm -2 The range is preferably 100 to 150 mWcm -2 The range is.

[0184] 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 500 to 7200 mJcm -2 and most preferably in the range of 3000 to 7200 mJcm -2 The range is.

[0185] The photopolymerization is preferably carried out in an inert gas atmosphere, preferably in a heated nitrogen atmosphere, but polymerization in air is also possible. The photopolymerization is preferably carried out at a temperature of 1 to 70°C, more preferably 5 to 50°C, and even more preferably 15 to 30°C.

[0186] The polymerized LC films according to the invention have good adhesion to plastic substrates, especially TAC, COP, and color filters, and can therefore be used as adhesives or base coatings for subsequent LC layers that would otherwise not adhere well to the substrate.

[0187] The preferred thickness of the polymerized LC film according to the present invention is determined by the optical properties desired in the film or final product. For example, if the polymerized LC film does not act primarily as an optical layer, but for example as an adhesive, alignment layer or protective layer, its thickness is preferably 1 μm or less, in particular 0.5 μm or less, very preferably 0.2 μm or less.

[0188] For example, the uniformly homeotropic or planar aligned polymer films of the present invention can be used as retardation or compensation films, for example in LCDs, to improve contrast and brightness at large viewing angles and reduce chromaticity. They can be used outside the switchable liquid crystal cell in the LCD, or between substrates (usually glass substrates) that form the switchable liquid crystal cell and contain the switchable liquid crystal medium (in cell application).

[0189] For optical applications of the polymer film, the polymer film preferably has a thickness of 0.5 to 10 μm, very preferably 0.5 to 5 μm, in particular 0.5 to 3 μm.

[0190] The optical retardation (δ(λ)) of a polymer film as a function of the wavelength (λ) of the incident beam is given by Equation (7): δ(λ)=(2πΔn d) / λ(7) where (Δn) is the birefringence of the film, (d) is the film thickness, and λ is the wavelength of the incident light.

[0191] According to Snelius' law, birefringence as a function of the direction of the incident beam is defined as: Δn=sinθ / sinΨ (8) where sin θ is the angle of incidence or tilt of the optical axis within the film and sin Ψ is the corresponding angle of reflection.

[0192] Based on these laws, the birefringence and therefore the optical retardation depend on the thickness of the film and the tilt angle of the optical axis within the film (see Berek's compensator). Therefore, 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.

[0193] Depending on the amount of compounds of formula T and I utilized, the polymer film according to the present invention has a R(450) / R(550)<1 or

number

number

number

number

[0194] Preferred optical films of the present invention exhibit a birefringence higher than 0.07, more preferably in the range of 0.08 to 0.150. The polymeric films according to the present invention have an optical retardation as a function of film thickness of less than 200 nm, preferably less than 180 nm, more preferably less than 150 nm.

[0195] Particularly with regard to in-cell applications, the polymer film according to the present invention exhibits high temperature stability, thus the polymer film exhibits temperature stability up to 300°C, preferably up to 250°C, more preferably up to 230°C.

[0196] In summary, the polymerized LC films and polymerizable LC materials according to the present invention are useful in reflective films such as polarizers, compensation plates, alignment layers, circular polarizers or color filters in liquid crystal displays or projection systems, for the preparation of decorative images, liquid crystals or effect pigments, in particular with spatially varying reflected color, multicolor images for decoration, information storage or security applications such as identity cards or credit cards, unforgeable documents such as banknotes etc.

[0197] The polymerized LC film according to the present invention can be used in transmissive or reflective displays.They can be used in conventional OLED displays or LCDs, especially in DAP (altered phase alignment) or VA (vertically aligned) mode LCDs, such as ECB (electrically controlled birefringence), CSH (color super homeotropic), VAN or VAC (vertically aligned nematic or cholesteric) displays, MVA (multi-domain vertical alignment) or PVA (patterned vertical alignment) displays, displays in bend mode or hybrid type displays, such as OCB (optically compensated bend cell or optically compensated birefringence), R-OCB (reflective OCB), HAN (hybrid alignment nematic), pi-cell (pi-cell) displays, and also in TN (twisted nematic), HTN (highly twisted nematic), STN (super twisted nematic) mode, AMD-TN (active matrix driven TN) displays, or in IPS (in-plane switching) mode, also known as "super TFT" displays. Particularly preferred are VA, MVA, PVA, OCB, and π-cell displays.

[0198] The present invention is described above and below 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.

[0199] Many of the compounds mentioned herein or their mixtures are commercially available.All of these compounds are either known or can be prepared by methods known per se, as described in the literature (e.g. in standard works such as Houben-Weyl, Methoden der Organischen Chemie [Methods of Organic Chemistry], Georg-Thieme-Verlag, Stuttgart), or, more precisely, under reaction conditions known and suitable for said reactions.Variants known per se, but not mentioned here, can also be used here.

[0200] It will be understood that modifications can be made to the foregoing aspects 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 generic example of a series of equivalent or similar features.

[0201] 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).

[0202] It will be appreciated that many of the features described above, particularly the preferred aspects, are inventive in their own right and not just as part of aspects of the present invention, and independent protection may be sought for these features in addition to, or as an alternative to, the presently claimed invention.

[0203] The present invention will now be described in more detail with reference to the following examples, which are merely illustrative and are not intended to limit the scope of the invention. The following examples serve to illustrate the invention without limiting it, preferred combinations of parameters being described.

[0204] example Compound example Material M-1 is prepared according to the following reaction scheme: [ka] [ka] [ka]

[0205] N,N-Diethylthiophene-3-carboxamide (2) Thiophene-3-carboxylic acid (1) (125.00 g; 965.67 mmol; 1.00 equiv.) was mixed with thionyl chloride (178.54 ml; 2423.20 mmol; 2.51 equiv.) and the suspension was stirred at room temperature for 3 h until a clear yellow solution was obtained. The solution was heated at 80 °C for 1.5 h until gas evolution ceased. The mixture was then cooled and excess thionyl chloride was removed by distillation under reduced pressure to give a brown crystalline solid. The solid was dissolved in dry diethyl ether (500 ml) and added dropwise to a solution of diethylamine (249.60 ml; 2423.08 mmol; 2.51 equiv.) in diethyl ether (1.5 L) at 0 °C over 30 min to give a thick white suspension. The reaction was allowed to warm to room temperature and proceed for 1 h. The reaction mixture is vacuum filtered and the white filter cake (diethylammonium chloride) is washed thoroughly with diethyl ether. The filtrate is reduced in vacuo to give an orange oil (170.32 g). The oil is heated at 99.5° C. for 1.4×10 min. -1 Distill at reduced pressure at mBar to give a colourless oil (163.75 g).

[0206] 1 H NMR (400 MHz, chloroform-d) δ 7.48 (dd, J = 3.0, 1.2 Hz, 1H), 7.32 (dd, J = 5.0, 2.9 Hz, 1H), 7.19 (dd, J = 5.0, 1.2 Hz, 1H), 3.44 (m, 4H), 1.21 (t, J = 7.8 Hz, 6H).

[0207] Benzo[1,2-b:4,5-b']dithiophene-2,8-dione (3) A solution of N,N-diethylthiophene-3-carboxamide (163.75 g; 893.48 mmol; 1.00 equiv) in THF, dry (1.00 L) is cooled to -78°C. n-BuLi (564.01 ml; 902.42 mmol; 1.01 equiv) is then added slowly via addition funnel over 1 h. Cooling is removed and the reaction is allowed to warm to room temperature and stirred for 20 h. The suspension is then poured into 2.5 L of ice / water and mixed until dissolved. The resulting suspension is filtered and the filter cake is washed again with water, methanol, water, and methanol and then air dried before being placed in a vacuum oven overnight to give a yellow solid (86.39 g).

[0208] 2,8-Dimethoxybenzo[1,2-b:4,5-b']dithiophene (4) To a stirred solution of benzo[1,2-b:4,5-b']dithiophene-2,8-dione (86.39 g; 2157.20 mmol; 1.00 equiv.) in ethanol 99% denatured with methanol (1.25 L; 21435.70 mmol; 54.65 equiv.) and water (1.25 L; 69386.62 mmol; 176.92 equiv.), add sodium borohydride (81.61 g; 2157.10 mmol; 5.50 equiv.) over 60 min and stir for an additional 60 min. Potassium hydroxide solution (10 M, 156.88 ml; 1568.80 mmol; 4.00 equiv.) is then added and the mixture is stirred for 30 min. The mixture is heated to reflux and dimethyl sulfate (350.00 ml; 3690.55 mmol; 9.41 equiv) is added over 2 hours. Reflux is maintained for a further 2 hours and then allowed to cool overnight, GCMS shows good product formation. Water is then added, the solution neutralised with NaHCO3 is filtered and the mixture is filtered to recover the product, washed with water and then with IMS (x3) and the recovered solid is dried overnight at 40°C in a vacuum oven to give a sand coloured solid (94.89 g).

[0209] 1 H NMR (400 MHz, chloroform-d) δ 7.51 (d, J = 5.5 Hz, 2H), 7.40 (d, J = 5.5 Hz, 2H), 4.14 (s, 6H).

[0210] 5,11-Diiodo-2,8-dimethoxy-benzodithiophene (5) To a solution of tetramethylethylenediamine (4.48 ml; 29.96 mmol; 7.50 equiv) in THF anhydrous (20.00 ml; 20.00 V) is added under N2 at -78°C and stirred for 10 minutes. After this, 2,8-dimethoxy-benzodithiophene (1.00 g; 3.99 mmol; 1.00 equiv) is added as a solution in anhydrous THF (10.00 ml; 10.00 V). The temperature is then increased to -40°C to deprotonate and cooled to -78°C. Iodine (2.89 g; 11.38 mmol; 2.85 equiv) is then added and the reaction is left overnight without replenishing the cooling bath, slowly returning to room temperature. Water is then carefully added to the reaction mixture, followed by sodium thiosulfate to remove excess iodine. The resulting suspension is then further diluted with water and then filtered. Wash the filter cake with water (x2), methanol, very dilute HCl, then methanol (x2) and dry the crude in a vacuum oven to give an off-white solid (1.655 g), 97% by GCMS.

[0211] 1 H NMR (400 MHz, chloroform-d) δ 7.67(s, 2H), 4.06(s, 6H).

[0212] 5,11-bis(4-fluoro-2-methylphenyl)-2,8-dimethoxy-benzodithiophene (6) To a flask charged with 5,11-diiodo-2,8-dimethoxy-benzodithiophene (7.50 g; 14.94 mmol; 1.00 equiv), (4-fluoro-2-methylphenyl)boronic acid (4.85 g; 31.52 mmol; 2.11 equiv), XPhosPdG3 (505.71 mg; 0.60 mmol; 0.04 equiv) and cesium carbonate (14.60 g; 44.81 mmol; 3.00 equiv) is added 1,4-dioxane (150.00 ml; 20.00 V) and the reaction mixture is placed under N2 and heated to 100 °C. After 19 hours, additional (4-fluoro-2-methylphenyl)boronic acid (1.15 g; 7.47 mmol; 0.50 equiv) and XPhosPdG3 (100.00 mg; 0.12 mmol; 0.01 equiv) were added and heating was continued for 12 hours before being allowed to cool. After this time, the reaction was cooled, diluted with water, acidified with dilute hydrochloric acid, and the resulting suspension was filtered to give a brown solid which was washed well with water (x3) and MeOH (x4). This solid was then dissolved in ethyl acetate (1 L), heated to ~60 °C, dried over MgSO4, filtered, and reduced pressure to give a yellow solid (6.34 g). The crude product was recrystallized from acetonitrile / dichloromethane by hot filtration. The mother liquor is absorbed onto Celite and columned with 7-60% dichloromethane in petrol, with the cleanest fractions combined with the recrystallized solid to give the final product as an orange solid (3.18 g).

[0213] 1 H NMR (400 MHz, chloroform-d) δ 7.51 (dd, J = 8.5, 5.9 Hz, 2H), 7.41 (s, 2H), 7.05 (dd, J = 9.6, 2.7 Hz, 2H), 7.00 (td, J = 8.3, 2.8 Hz, 2H), 4.17 (s, 6H), 2.53 (s, 6H).

[0214] 5,11-bis(4-fluoro-2-methylphenyl)-benzodithiophene-2,8-diol (7) 5,11-Bis(4-fluoro-2-methylphenyl)-2,8-dimethoxy-benzodithiophene (0.29 g; 0.62 mmol; 1.00 equiv) is dissolved in dichloromethane (10.15 ml; 35.00 V), placed under N2 and cooled to -78 °C using an acetone / dry ice bath in oven-dried glassware. Boron tribromide (1.55 ml; 1.55 mmol; 2.50 equiv) is then slowly added and stirred for 15 minutes. The cooling bath is then replaced with a water / ice bath and the reaction is allowed to slowly warm to room temperature overnight. After this time, the reaction is quenched by the addition of water (10 ml). The flask is then rinsed with dichloromethane and acetone, then reduced in vacuum to remove the organic solvent and precipitate the product. This is then collected by filtration and washed with water and methanol before drying in a vacuum oven to give the crude product (0.27 g).

[0215] 1 H NMR (400 MHz, DMSO-d6) δ 9.96 (br. s, 2H), 7.66 (s, 2H), 7.56 (dd, J = 8.5, 6.0 Hz, 2H), 7.28 (d, J = 10.0 Hz, 2H), 7.17 (t, J = 8.2 Hz, 3H).

[0216] Methyl 4-(4-hydroxyphenyl)cyclohexane-1-carboxylate (9) To a flask charged with 4-(4-chlorophenyl)cyclohexane-1-carboxylic acid (3.00 g; 12.57 mmol; 1.00 equiv), Pd2dba3 (230.17 mg; 0.25 mmol; 0.02 equiv), tBuXPhos (426.94 mg; 1.01 mmol; 0.08 equiv) and potassium hydroxide (2.82 g; 50.27 mmol; 4.00 equiv), add 1,4-dioxane (30.00 ml; 10.00 V) and water (20.00 ml; 6.67 V). The resulting mixture is placed under N2, sonicated for 5 min, then heated to 110 °C for 3.5 h, then cooled. The reaction is diluted with water and extracted with ethyl acetate, the organics washed with KOH (1M solution), the organics discarded and the combined aqueous layers acidified with Dil HCl to induce precipitation of the free acid. HCl to induce precipitation of the free acid. The suspension is extracted with ethyl acetate and the organics dried over MgSO4, filtered and reduced to give a pale yellow solid (3.47 g, wet) which is recrystallized from MeOH to give an off-white solid (1.55 g). The mother liquor is reduced to give a pale yellow solid (1.52 g).

[0217] 1 H NMR (400 MHz, Acetone-d6) δ 10.46 (s, 1H), 8.05 (s, 1H), 7.11 - 7.02 (m, 2H), 6.79 - 6.71 (m, 2H), 2.51 - 2.39 (m, 1H), 2.34 (tt, J = 11.8, 3.7 Hz, 1H), 2.08 (d, J = 9.9 Hz, 2H), 1.92 - 1.84 (m, 2H), 1.62 - 1.41 (m, 6H).

[0218] In a separate flask, the solid is dissolved in MeOH (~35 ml), H2SO4 (conc, 0.1 ml) is added and heated at 70 °C for 4 h, at which time the reaction is cooled, after which NaHCO3 solution is added and the mixture is extracted with ethyl acetate and water to give an off-white solid (1.34 g, 95% GCMS) and a sandy coloured solid (1.51 g, 80% GCMS).

[0219] The impure material is columned with 15% petroleum ether, then 30% isocratic ethyl acetate (40-60) to give an off-white solid (1.07 g). 100% GCMS, combined with other products to give an off-white solid (2.58 g).

[0220] 1 H NMR (400 MHz, chloroform-d) δ 7.09 - 7.01 (m, 2H), 6.81 - 6.72 (m, 2H), 5.41 (s, 1H), 3.70 (s, 3H), 2.45 (tt, J = 12.0, 3.5 Hz, 1H), 2.35 (tt, J = 12.2, 3.6 Hz, 1H), 2.14 - 2.03 (m, 2H), 2.00 - 1.89 (m, 2H), 1.58 (qd, J = 12.9, 3.2 Hz, 2H), 1.42 (qd, J = 13.0, 3.2 Hz, 2H).

[0221] Methyl 4-{4-[(8-hydroxyoctyl)oxy]phenyl}cyclohexane-1-carboxylate (10) Methyl 4-(4-hydroxyphenyl)cyclohexane-1-carboxylate (2.00 g; 8.54 mmol; 1.00 equiv.), potassium iodide (0.14 g; 0.85 mmol; 0.10 equiv.) and potassium carbonate (2.54 g; 18.36 mmol; 2.15 equiv.) are dissolved in N,N-dimethylformamide (20.00 ml; 258.30 mmol; 30.26 equiv.). 8-Bromooctan-1-ol (1.68 ml; 9.82 mmol; 1.15 equiv.) is added and stirred at room temperature until depletion of phenol by TLC. The reaction mixture is diluted with ethyl acetate, acidified with dilute hydrochloric acid, washed with water, the organics are dried over MgSO4, filtered and reduced pressure to give a yellow oil (3.33 g).

[0222] 1H NMR (400 MHz, chloroform-d) δ 7.15 - 7.10 (m, 2H), 6.88 - 6.82 (m, 2H), 3.94 (t, J = 6.5 Hz, 2H), 3.71 (s, 3H), 3.66 (t, J = 6.6 Hz, 3H), 2.48 (tt, J = 11.9, 3.5 Hz, 1H), 2.36 (tt, J = 12.2, 3.6 Hz, 1H), 2.11 (dd, J = 13.7, 3.6 Hz, 2H), 1.97 (dd, J = 13.6, 3.5 Hz, 2H), 1.82 - 1.72 (m, 2H), 1.68 - 1.53 (m, 5H), 1.47 (td, J = 12.6, 3.2 Hz, 5H), 1.42 - 1.31 (m, 8H).

[0223] 4-{4-[(8-hydroxyoctyl)oxy]phenyl}cyclohexane-1-carboxylic acid (11) To a solution of crude methyl 4-{4-[(8-hydroxyoctyl)oxy]phenyl}cyclohexane-1-carboxylate (3.30 g; 9.10 mmol; 1.00 equiv.) in tetrahydrofuran (35.00 ml; 431.52 mmol; 47.40 equiv.), lithium hydroxide (0.65 g; 27.31 mmol; 3.00 equiv.) is added in water (15.00 ml; 832.64 mmol; 91.46 equiv.). The mixture is placed under N2 and heated to 50° C. overnight. After this time a sample is taken to check for loss of ester.

[0224] Once the reaction is complete, it is diluted with water, filtered, and acidified with dilute hydrochloric acid to pH 1-2. The resulting precipitate is collected by filtration, washed with water and a small amount of IPA to give the crude product as a white solid. This solid is dissolved in ethyl acetate / acetone, dried over MgSO4, and reduced in vacuum to give the product as a white solid (2.69 g). This is then recrystallized from acetonitrile by hot filtration to give a white solid (2.133 g).

[0225] 1H NMR (400 MHz, chloroform-d) δ 7.16 - 7.08 (m, 2H), 6.89 - 6.81 (m, 2H), 3.95 (t, J = 6.5 Hz, 2H), 3.67 (t, J = 6.6 Hz, 2H), 2.49 (tt, J = 13.1, 4.1 Hz, 1H), 2.41 (tt, J = 12.1, 3.6 Hz, 1H), 2.22 - 2.12 (m, 2H), 2.05 - 1.94 (m, 2H), 1.84 - 1.72 (m, 2H), 1.70 - 1.25 (m, 15H).

[0226] 4-[4-({8-[(3-chloropropanoyl)oxy]octyl}oxy)phenyl]cyclohexane-1-carboxylic acid (12) 4-{4-[(8-hydroxyoctyl)oxy]phenyl}cyclohexane-1-carboxylic acid (2.13 g; 6.11 mmol; 1.00 equiv.) is dissolved in pyridine (1.48 ml; 18.34 mmol; 3.00 equiv.) and tetrahydrofuran (20.00 ml; 246.58 mmol; 9.39 V). 3-Chloropropionyl chloride (1.17 ml; 12.22 mmol; 2.00 equiv.) is then added dropwise at room temperature, heated to 60° C., and after 2 hours, more pyridine (1.00 ml; 12.41 mmol; 2.03 equiv.) is added. After a further 2 hours, the reaction is cooled. 3-Chloropropionyl chloride (1.00 ml; 10.47 mmol; 1.71 equiv) and pyridine (2.00 ml; 24.83 mmol; 4.06 equiv) were added and the reaction was left at 50° C. overnight before extraction with ethyl acetate to give a pale yellow semi-solid (2.21 g) NMR indicated ∼90% product which was used without further purification.

[0227] 1H NMR (400 MHz, chloroform-d) δ 7.13 (dd, J = 8.7, 1.9 Hz, 2H), 6.89 - 6.82 (m, 2H), 4.15 (t, J = 6.7 Hz, 2H), 3.95 (t, J = 6.5 Hz, 2H), 3.78 (t, J = 6.7 Hz, 2H), 2.81 (t, J = 6.7 Hz, 2H), 2.56 - 2.35 (m, 2H), 2.29 - 2.13 (m, 2H), 2.06 - 1.95 (m, 2H), 1.84 - 1.72 (m, 2H), 1.74 - 1.56 (m, 5H), 1.60 - 1.41 (m, 4H), 1.38 (q, J = 4.3, 3.9 Hz, 6H).

[0228] 8-{4-[4-(carbonochloridoyl)cyclohexyl]phenoxy}octyl 3-chloropropanoate (13) To a solution of 4-[4-({8-[(3-chloropropanoyl)oxy]octyl}-oxy)phenyl]cyclohexane-1-carboxylic acid (0.77 g; 1.75 mmol; 1.00 equiv.) in dichloromethane (11.52 ml; 15.00 V) in N2 cooled in an ice bath, thionyl chloride (0.15 ml; 2.01 mmol; 1.15 equiv.) is then added dropwise. N,N-dimethylformamide (1 drop) is then added and the reaction is allowed to warm to room temperature and left overnight. After this time the solvent is removed in vacuo to give a pale orange oil (0.70 g).

[0229] 5,11-Bis(4-fluoro-2-methylphenyl)-8-[4-(4-{[8-(prop-2-enoyloxy)octyl]oxy}phenyl)cyclohexanecarbonyloxy]-4,10-dithiatricyclo[7.3.0.03,7]dodeca-1,3(7),5,8,11-pentaen-2-yl 4-(4-{[8-(prop-2-enoyloxy)octyl]oxy}phenyl)cyclohexane-1-carboxylate (14) A flask was charged with 5,11-bis(4-fluoro-2-methylphenyl)-4,10-benzodithiophene-2,8-diol (0.29 g; 0.66 mmol; 1.00 equiv), triethylamine (0.74 ml; 5.29 mmol; 8.00 equiv) and N,N-dimethylpyridin-4-amine (10.00 mg; 0.08 mmol; 0.12 equiv) in dichloromethane (10.00 ml; 156.60 mmol; 236.79 equiv) and placed under N2. 8-{4-[4-(carbonochloridoyl)cyclohexyl]phenoxy}octyl 3-chloropropanoate (0.67 g; 1.45 mmol; 2.20 equiv.) dissolved in dichloromethane (5.00 ml; 78.30 mmol; 118.39 equiv.) was added dropwise, and after 2 h additional acid chloride (100 mg) was added and allowed to react overnight. After this time, triethylamine (1 ml) and dichloromethane (7.5 ml) were added, warmed to 30°C, and allowed to stand over the weekend. After this time, both esterification and acrylate formation were complete. The mixture was diluted with ethyl acetate, poured into water and acidified, extracted with ethyl acetate, gravity filtered, and the organics washed with water and brine, dried over MgSO4, filtered, and reduced pressure until an orange solid (0.94 g) was obtained. Purify by column chromatography eluting with 2-20% ethyl acetate in petroleum ether to give the product fraction as two peaks, reduce the cleanest fraction to give a pale orange waxy solid (0.25 g) which is dissolved in ethyl acetate and petroleum ether is added until turbidity is observed, filter through a syringe and reduce pressure to give an orange oil (0.24 g) which crystallizes very slowly at 96.1% by HPLC.

[0230] 1H NMR (400 MHz, クロロホルム-d) δ 7.16 - 7.11 (m, 4H), 7.09 (s, 4H), 6.89 - 6.80 (m, 4H), 6.40 (dd, J = 17.4, 1.5 Hz, 2H), 6.12 (dd, J = 17.3, 10.4 Hz, 2H), 5.81 (dd, J = 10.4, 1.5 Hz, 2H), 4.15 (t, J = 6.7 Hz, 4H), 3.93 (t, J = 6.5 Hz, 4H), 2.56 (dtt, J = 27.6, 12.0, 3.5 Hz, 4H), 2.30 - 2.21 (m, 4H), 2.07 - 1.97 (m, 4H), 1.82 - 1.61 (m, 12H), 1.52 (dd, J = 12.6, 3.2 Hz, 3H), 1.49 - 1.41 (m, 5H), 1.41 - 1.35 (m, 12H). 13 C NMR (101 MHz, クロロホルム-d) δ 174.36, 166.35, 157.48, 148.14, 138.71, 130.46, 130.45, 128.64, 127.54, 122.34, 114.39, 67.93, 64.67, 43.06, 42.65, 33.44, 29.71, 29.31, 29.26, 29.18, 28.60, 26.00, 25.87.

[0231] Similar to the above procedure, the following compounds M-2 to M-60 are synthesized:

change

change

change

change

change

[0232] Examples of mixtures The following examples (including Comparative Example C-1) were prepared according to the following table: [Table 1]

[0233] Irganox 1076 is a stabilizer and is commercially available (Ciba AG, Basel, Switzerland). Darocure TPO is a photoinitiator and is commercially available (Ciba AG, Basel, Switzerland). FluorN 561 is a surfactant that is commercially available (Cytonix, USA). RM-1 is commercially available, for example, as 1,4-bis-[4-(3-acryloyloxypropyloxy)benzoyloxy]-2-methylbenzene from Sigma-Aldrich, Germany.

[0234] Each formulation is oven heated at 70° C. until completely dissolved, filtered through a PTFE filter with a pore size of 0.2 μm, and the clearing point (TNI) is measured in ° C. by POM. Each formulation is spin-coated twice at 4000 rpm for 30 seconds onto a PI-coated glass substrate.

[0235] All samples were NI The film is then annealed at 40° C. lower for 60 seconds. All samples were analyzed using a DELO lamp (80 mW / cm 2 ) for 60 seconds at 20° C. under nitrogen. The retardation of each slide is measured using an ellipsometer, and the thickness of each slide is measured using a profilometer.

[0236] The raw retardation data is fitted to a distribution in the Selmier equation to remove thin film interference from the measurement. This data is then converted to birefringence using the measured thickness data for each film, and the data for each blend film is averaged to give the final data set. The following table summarizes the results. [Table 2]

[0237] From this data, it can be observed that at the extrapolation point of 100% M-1, Δn(450 nm) is lower than Δn(550 nm), indicating a negative wavelength dispersion of birefringence. In contrast, the birefringence dispersion of reference C-1 is positive.

Claims

1. Formula T 【Chemical 1】 During the ceremony R Ｔ１ and R Ｔ２ each independently of the other represents H or a hydrocarbon group having 1 to 20 carbon atoms, the group may have a substituent, and any carbon atom may be replaced with a heteroatom; and R Ｔ１ and R Ｔ２ At least one of the following is P-Sp-; P represents a polymerizable group; Sp represents a spacer group; A Ｔ１ and AT2 each and independently and at each occurrence represent a 1,4-phenylene group, a 1,4-cyclohexylene group, a pyridine-2,5-diyl group, a pyrimidine-2,5-diyl group, a naphthalene-2,6-diyl group, a naphthalene-1,4-diyl group, a tetrahydronaphthalene-2,6-diyl group, a decahydronaphthalene-2,6-diyl group, or a 1,3-dioxane-2,5-diyl group, wherein these groups may be unsubstituted or substituted with one or more of the substituents L; L each independently in each occurrence represents F, Cl, Br, I, pentafluorosulfuranyl group, nitro group, cyano group, isocyano group, amino group, hydroxyl group, mercapto group, methylamino group, dimethylamino group, diethylamino group, diisopropylamino group, trimethylsilyl group, dimethylsilyl group, thioisocyano group, or a linear or branched alkyl group having 1 to 20 carbon atoms, and one of said -CH ２ - or two or more non-adjacent -CH ２ - is optionally substituted by each independently -O-, -S-, -CO-, -COO-, -OCO-, -CO-S-, -S-CO-, -O-CO-O-, -CO-NH-, -NH-CO-, -CH=CH-COO-, -CH=CH-OCO-, -COO-CH=CH-, -OCO-CH=CH-, -CH=CH-, -CF=CF- or -C≡C-, and any hydrogen atom in the alkyl group may be substituted by F, or L may represent a group represented by P-Sp-, : Ｔ１ __________________________________________. ２ _、!| ２ ﯁、!H ２ ヨ ２ The ................... ................. . ２ _、!| ２ 3.、!.. ２ ﯁、!C ２ 、!F ２ 3.、+. ２ �fit The ２ ヨ ２ 、!C﯁CH ２ ヨ ２ _、!| ２ ヨ ２ ____、!H ２ ( ２ _____、________________________________ ２ 、!C﯁CH ２ _、!| ２ ____、!H ２ The __________________________________________________________________. G Ｔ１ is the base 【Chemistry 2】 indicates, Ch each and independently represents a chalcogen; R ０ and R ００ each independently represents a hydrogen atom, F, Cl, Br, I, or a linear or branched alkyl group having 1 to 20 carbon atoms, ２ - or two or more non-adjacent -CH ２ - is optionally substituted at each occurrence by -O-, -S-, -CO-, -COO-, -OCO-, -CO-S-, -S-CO-, -O-CO-O-, -CO-NH-, -NH-CO-, -CH=CH-COO-, -CH=CH-OCO-, -COO-CH=CH-, -OCO-CH=CH-, -CH=CH-, -CF=CF- or -C≡C-, and any hydrogen atom in the alkyl group is optionally substituted by F or Cl, W １ and W ２ are independently selected from groups containing aromatic and / or non-aromatic groups having 1 to 40 carbon atoms, which may be substituted, and the aromatic group may be a hydrocarbon ring or a heterocycle, and the non-aromatic group may be a hydrocarbon group or a group in which any carbon atom in the hydrocarbon group has been replaced with a heteroatom (provided that the oxygen atoms are not directly bonded to each other); m1 and m2 each independently represent an integer of 1 to 6. A compound represented by the formula:

2. The compound according to claim 1, wherein m1 and m2 in formula T each independently represent an integer of 1 or 2.

3. G Ｔ１ W in １ and / or W ２ Based on -(Z Ｔ３ -A Ｔ３ -) ｍ３ -A Ｔ４ -Y where Z Ｔ３ In claim 1, Z Ｔ２ has one of the meanings as given for A Ｔ３ and A Ｔ４ A Ｔ１ and A Ｔ２ has one of the meanings as given in claim 1, m3 each and independently represents 0, 1, or 2; and Y represents a hydrogen atom, F, Cl, Br, I, a pentafluorosulfuranyl group, a nitro group, a cyano group, an isocyano group, an amino group, a hydroxyl group, a mercapto group, a methylamino group, a dimethylamino group, a diethylamino group, a diisopropylamino group, a trimethylsilyl group, a dimethylsilyl group, a thioisocyano group, or a linear or branched alkyl group having 1 to 20 carbon atoms, ２ - or two or more non-adjacent -CH ２ - may be independently substituted by -O-, -S-, -CO-, -COO-, -OCO-, -CO-S-, -S-CO-, -O-CO-O-, -CO-NH-, -NH-CO-, -CH=CH-COO-, -CH=CH-OCO-, -COO-CH=CH-, -OCO-CH=CH-, -CH=CH-, -CF=CF-, or -C≡C-, and any hydrogen atom in the alkyl group may be substituted by F, or Y may represent a group represented by P-Sp- as defined in claim 1, Showing, The compound of claim 1.

4. A T1 to A T4 in formula T each independently and at each occurrence represent a group selected from formulas A-1 to A-11, 【Chemistry 3】 4. Compounds according to claim 3, in which L has one of the meanings given in claim 1.

5. Formula G Ｔ１ The compound according to claim 1, wherein Ch represents S.

6. R Ｔ１ and R Ｔ２ The compound according to claim 1, wherein represents P-Sp-.

7. One or more compounds according to claim 1 and preferably of the following formula: 【Chemistry 4-1】 【Chemistry 4-2】 (In the ceremony P ０ When appearing multiple times, each independently represents a polymerizable group (P), L each and independently at each occurrence has one of the meanings as given for the substituent L in claim 1; 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 each and independently 0 or 1, and when the adjacent x or y is 0, z is 0. A polymerizable LC material comprising one or more multi- or di-reactive mesogenic compounds selected from:

8. The following formula 【Chemistry 5-1】 【Chemistry 5-2】 【Chemistry 5-3】 【Chemistry 5-4】 (In the ceremony P ０ , L, r, x, and z are as defined in formulas DRMa-1 to DRMf in claim 7; R ０ is alkyl, alkoxy, thioalkyl, alkylcarbonyl, alkoxycarbonyl, alkylcarbonyloxy or alkoxycarbonyloxy having one or more, preferably 1 to 15, C atoms, or Y ０ indicates, Y ０ are F, Cl, CN, NO ２ , OCH ３ , OCN, SCN, SF ５ or a mono-, oligo- or polyfluorinated alkyl or alkoxy having 1 to 4 C atoms, Z ０ is -COO-, -OCO-, -CH ２ CH ２ -, -CF ２ O-, -OCF ２ -, -CH=CH-, -OCO-CH=CH-, -CH=CH-COO-, or a single bond; A ０ in the case of multiple occurrences, independently of one another, are 1,4-phenylene or trans-1,4-cyclohexylene, which may be unsubstituted or substituted by 1, 2, 3 or 4 radicals L, u and v are independently 0, 1 or 2; w is 0 or 1, and The benzene and naphthalene rings may be further substituted with one or more identical or different substituents L as defined in claim 1.

8. A polymerisable LC material according to claim 7, comprising one or more monoreactive mesogenic compounds selected from:

9. The polymerizable LC material of claim 7 comprising one or more photoinitiators.

10. 8. The polymerizable LC material of claim 7, comprising one or more additives selected from the group consisting of surfactants, stabilizers, catalysts, sensitizers, inhibitors, chain transfer agents, co-reactant monomers, reactive thinners, surface-active compounds, lubricants, wetting agents, dispersants, hydrophobizing agents, adhesives, flow improvers, degassing or anti-foaming agents, degassing agents, diluents, reactive diluents, auxiliaries, colorants, dyes, pigments and nanoparticles.

11. - providing a layer of a polymerizable LC material according to claim 7 on a substrate, - photopolymerizing the polymerizable LC material; - Optionally removing the polymerized LC material from the substrate and / or optionally providing it on another substrate Preparation process of polymer film by.

12. From the polymerizable LC material according to claim 7 - providing a layer of polymerizable LC material on a substrate, - photopolymerizing the LC material, and - optionally removing the polymerized LC material from the substrate and / or optionally providing it on another substrate; A polymer film obtainable by a process comprising:

13. 13. The polymer film of claim 12, wherein the polymer exhibits positive, negative, or flat dispersion.

14. Use of a polymer film according to claim 12 or 13 or a polymerizable LC material according to any one of claims 7 to 9 in optical, electro-optical, information storage, decorative and security applications.

15. An optical component or device comprising at least one polymer film according to claim 12 or 13 or a polymerizable LC material according to any one of claims 7 to 9.

Images