WO2008012292A1 - Mélange de cristaux liquides - Google Patents

Mélange de cristaux liquides Download PDF

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Publication number
WO2008012292A1
WO2008012292A1 PCT/EP2007/057588 EP2007057588W WO2008012292A1 WO 2008012292 A1 WO2008012292 A1 WO 2008012292A1 EP 2007057588 W EP2007057588 W EP 2007057588W WO 2008012292 A1 WO2008012292 A1 WO 2008012292A1
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alkyl
groups
tego
component
methyl
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PCT/EP2007/057588
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German (de)
English (en)
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Oliver Seeger
Arno BÖHM
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Basf Se
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    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K19/00—Liquid crystal materials
    • C09K19/52—Liquid crystal materials characterised by components which are not liquid crystals, e.g. additives with special physical aspect: solvents, solid particles
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K19/00—Liquid crystal materials
    • C09K19/04—Liquid crystal materials characterised by the chemical structure of the liquid crystal components, e.g. by a specific unit
    • C09K19/38—Polymers
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K19/00—Liquid crystal materials
    • C09K19/04—Liquid crystal materials characterised by the chemical structure of the liquid crystal components, e.g. by a specific unit
    • C09K19/42—Mixtures of liquid crystal compounds covered by two or more of the preceding groups C09K19/06 - C09K19/40
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K19/00—Liquid crystal materials
    • C09K19/52—Liquid crystal materials characterised by components which are not liquid crystals, e.g. additives with special physical aspect: solvents, solid particles
    • C09K19/54—Additives having no specific mesophase characterised by their chemical composition
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K19/00—Liquid crystal materials
    • C09K19/04—Liquid crystal materials characterised by the chemical structure of the liquid crystal components, e.g. by a specific unit
    • C09K2019/0444—Liquid crystal materials characterised by the chemical structure of the liquid crystal components, e.g. by a specific unit characterized by a linking chain between rings or ring systems, a bridging chain between extensive mesogenic moieties or an end chain group
    • C09K2019/0448—Liquid crystal materials characterised by the chemical structure of the liquid crystal components, e.g. by a specific unit characterized by a linking chain between rings or ring systems, a bridging chain between extensive mesogenic moieties or an end chain group the end chain group being a polymerizable end group, e.g. -Sp-P or acrylate

Definitions

  • the present invention relates to a liquid-crystalline mixture
  • a liquid-crystalline mixture comprising at least one curable component A which reflects in the UV and / or visible wavelength range and which comprises at least one achiral nematic polymerizable monomer in combination with at least one chiral polymerizable monomer; at least one cholesteric polymerizable monomer; at least one cholesteric crosslinkable monomer; and / or at least one cholesteric polymer in a polymerizable diluent, and as component B at least one radiation-absorbing and optionally fluorescent conjugated polycyclic compound.
  • the invention relates to the use of such mixtures for coating and printing of substrates, in printing inks, in electro-optical components and / or for counterfeit-proof marking of objects.
  • the invention also provides polymers or polymerized films which are obtainable by polymerization of the mixture according to the invention and their use as optical filters, polarizers, decorating agents, counterfeit-proof marking agents or reflection agents in the visible wavelength range; and a process for printing or coating substrates and substrates obtainable by this process, pigments containing the mixture according to the invention in cured form, and coating compositions containing the pigments according to the invention.
  • liquid-crystalline phases When heating formanisotropic substances, liquid-crystalline phases, so-called mesophases, can occur.
  • the individual phases are distinguished by the spatial arrangement of the molecular centers on the one hand and by the molecular arrangement with respect to the longitudinal axes on the other hand (G.W. Gray, P.A Winsor, Liquid Crystals and Plastic Crystals, EINs Horwood Limited, Chichester, 1974).
  • the nematic liquid-crystalline phase is characterized by parallel orientation of the molecular longitudinal axes (one-dimensional order state).
  • a so-called chiral nematic (cholesteric) phase is formed in which the longitudinal axis of the molecules forms a helical superstructure perpendicular to them (H. Baessler, Fest redesigne Xl, 1971).
  • the pitch is the distance between two imaginary layers with the same orientation of the molecular axes.
  • the chiral moiety may be present in the liquid crystalline molecule itself as well as added as a dopant to the nematic phase, thereby inducing the chiral nematic phase. This phenomenon was first observed in cholesterol (see B. Baessler, M., Chem. Phys., 52, 631 (1970)). By changing the concentration of a chiral dopant, the pitch and thus the wavelength range of selectively reflected radiation of a chiral nematic layer can be varied.
  • the chiral nematic phase has special optical properties: a high optical rotation and a pronounced circular dichroism, which results from selective reflection of circularly polarized light within the chiral nematic layer.
  • Such chiral nematic systems offer interesting possibilities for practical use.
  • Chiral nematic polymerisable monomers or chiral nematic polymers in polymerisable diluents which, after curing (polymerization / crosslinking) with optionally preceding orientation, exhibit liquid-crystalline properties and in particular high optical anisotropy, and their use for printing or coating substrates, in particular for decoration purposes, are known and described for example in WO 00/47694, WO 96/02597, WO 95/16007, WO 95/24454, WO 97/00600, DE 19843724 and EP-A-0750029.
  • the prior art liquid crystalline layers or prints often do not exhibit the desired level of brilliance and brightness, and in particular, no satisfactory color flop.
  • Color flop which is also known as a color shift, is the change in the color impression when the viewing angle on the liquid-crystalline layer changes.
  • WO 00/47694 describes the use of certain chiral-nematic polymerizable monomers for the preparation of counterfeit-proof markings. These are prepared by applying the chiral nematic polymerizable monomers to a suitable substrate, polymerizing, applying to this layer a further layer which contains dyes or pigments which absorb in the IR or UV range or have fluorescent dyes or pigments, and then apply a final absorption layer. applied layer.
  • the disadvantage of these tamper-proof markings is that the liquid-crystal compounds which mediate the viewing angle-dependent color impression and the dyes or pigments which absorb the infrared or UV radiation which form the hidden additional safety marking are produced in two different ways Layers must be applied. Also, the color flop is not particularly pronounced. It is an object of the present invention to provide liquid-crystalline mixtures which, on the one hand, lead to a greater color shift (color shift) and, on the other hand, allow a simpler production of counterfeit-proof markings.
  • (A.1) at least one achiral nematic polymerizable monomer and at least one chiral polymerizable monomer; or (A.2) at least one cholesteric polymerizable monomer; or (A.3) at least one cholesteric crosslinkable polymer; or (A.4) at least one cholesteric polymer in a polymerizable diluent
  • component B at least one radiation-absorbing and optionally fluorescent conjugated polycyclic compound.
  • Halogen is preferably fluorine, chlorine or bromine.
  • aliphatic radicals are understood as meaning alkyl groups, eg. C 1 -C 30 alkyl groups, alkenyl groups, C 2 -C 30 alkenyl groups, polyenyl groups such as alkadienyl groups, e.g. As C4-C 30 -Alkadienyl phenomenon and Alkatrie- nyl phenomenon, z. B. C 6 -Cs 0 -Alkatrienyl phenomenon, and alkynyl groups, for example. B. C 2 -C 3 alkynyl groups.
  • the carbon chains may be substituted by one or more groups selected from -O-, -S-, -NR-, -CO- and -SO 2 -, wherein R is H or C 1 -C 6 -alkyl, interrupted where 2 oxygen atoms may be adjacent, and / or one or more substituents selected from halogen, CN, C 3 -C 10 cycloalkyl, aryl, aryloxy, heterocyclyl and heterocyclyloxy.
  • Aromatic radicals which are also referred to as aryl radicals ("aryl") are understood in the context of the present invention carbocyclic aryl groups, for. B.
  • C 6 -Cu aryl groups such as phenyl, naphthyl, anthracenyl or phenanthrenyl, which may be unsubstituted or one or more, for. B.
  • 1, 2, 3, 4 or 5 may bear identical or different substituents which are selected from halogen, CN, C 3 -C 10 -cycloalkyl, C 3 -C 10 -cycloalkoxy, C 3 -C 10 - cycloalkenyl, C 3 -C 10 cycloalkenyloxy, aryl, aryloxy, heterocyclyl, heterocyclyloxy, C 1 -C 10 alkyl, C 2 -C 10 alkenyl, C 4 -C 10 -alkadienyl, C 6 -C 10 - alkatrienyl, C C 1 -C 10 -alkoxy, C 2 -C 10 -alkenyloxy, C 3 -C 10 -alkynyloxy, C 1 -C 10 -alkylthio, C 2 -C 10 -alkenylthio, C 3 -C 10 -alkynylthio, C 1 - C 10 alkylcarbonyl,
  • Aryloxy in the context of the present invention is an oxygen-bonded aryl radical.
  • araliphatic radicals are aryl radicals (as defined above) which are bonded via an aliphatic radical (as defined above), eg. B. via a C 1 -C 4 -alkyl radical.
  • alicyclic radicals are understood as meaning cycloalkyl radicals, eg. C 3 -C 10 cycloalkyl, cycloalkenyl radicals, e.g. B. C 3 -C 10 cycloalkenyl, Bicycloalkyl radicals, z. C 7 -C 10 bicycloalkyl, and bicycloalkenyl radicals, e.g. C 7 -C 10 bicycloalkenyl.
  • the alicyclic radicals may be unsubstituted or one or more, for. B. 1, 2, 3 or 4 substituents. Suitable substituents are those mentioned for aryl.
  • Heterocyclic radicals which are also referred to as heterocyclyl radicals ("heterocyclyl"), are understood in the context of the present invention to mean saturated, tially unsaturated or aromatic 3-g heterocyclyl groups which contain 1, 2, 3 or 4 heteroatoms selected from O, N and S, and optionally 1 or 2 CO groups as ring members.
  • the heterocyclic radicals may be unsubstituted or one or more, for. B. 1, 2, 3 or 4 substituents. Suitable substituents are those mentioned for aryl.
  • Aromatic heterocyclyl radicals are also referred to in the context of the present invention as hetaryl or as heteroaromatic radicals.
  • Heteroaromatic radicals which are also referred to as Het (ero) aryl radicals ("het (ero) aryl") are understood in the context of the present invention to be aromatic 5- or 6-membered heterocyclyl groups, the 1, 2, 3 or 4 heteroatoms, the are selected from O, N and S as ring members.
  • the heteroaromatic radicals may be unsubstituted or one or more, for. B. 1, 2, 3 or 4 substituents gene. Suitable substituents are those mentioned in aryl.
  • carboxylate is understood as meaning both the esters and any desired alcohols, for example As with C 1 -C 10 alcohols, poly (ether poly) ols or phenols, as well as the salts of the underlying carboxylic acid, for. With alkali metals such as sodium or potassium, alkaline earth metals such as calcium or magnesium, transition metals such as iron, or with ammonium ions.
  • C 1 -C 2 alkyl is methyl or ethyl.
  • C 1 -C 4 -alkyl is, for example, propyl, isopropyl, butyl, 1-methylpropyl (sec-butyl), 2-methylpropyl (isobutyl) or 1, 1-dimethylethyl (tert-butyl).
  • C 1 -C 6 -alkyl is, for example, pentyl, 1-methylbutyl, 2-ethylbutyl, 3-methylbutyl, 2,2-dimethylpropyl, 1-ethylpropyl, 1, 1-dimethylpropyl, 1, 2-dimethylpropyl, Hexyl, 1-methylpentyl, 2-methylpentyl, 3-ethylpentyl, 4-methylpentyl, 1, 1-dimethylbutyl, 1, 2-dimethylbutyl, 1, 3-dimethylbutyl, 2,2-dimethylbutyl, 2,3-dimethylbutyl, 3, 3-dimethylbutyl, 1-ethylbutyl, 2-ethylbutyl, 1, 1, 2-trimethylpropyl, 1, 2,2-trimethylpropyl, 1-ethyl-1-methylpropyl, or 1-ethyl-2-methylpropyl.
  • C 1 -C 8 -alkyl is, for example, heptyl, octyl, isooctyl, 2-ethylhexyl and positional isomers thereof.
  • C 1 -C 10 -alkyl is, for example, nonyl, isononyl, decyl, isodecyl and positional isomers thereof.
  • C 1 -C 20 -alkyl is, for example, undecyl, dodecyl, tridecyl, isotridecyl, tetradecyl, pentadecyl, hexadecyl, heptadecyl, octadecyl, nonadecyl and eicosyl, and positional isomers thereof.
  • C 1 -C 30 -alkyl is, for example, henicosyl, docosyl, tricosyl, Tetracosyl, pentacosyl, hexacosyl, hep y, acosyl, nonacosyl, squalyl, and positional isomers thereof.
  • Isooctyl, isononyl, isodecyl and isotridecyl are trivial names derived from the alcohols obtained by the oxo process.
  • Haloalkyl straight-chain or branched alkyl groups having 1 to 2, 1 to 4, 1 to 6, 1 to 8 or 1 to 10 carbon atoms (as mentioned above), wherein in these groups partially or completely the hydrogen atoms may be replaced by halogen atoms as mentioned above ; in particular C 1 -C 3 -haloalkyl such as methylmethyl, bromomethyl, dichloromethyl, trichloromethyl, fluoromethyl, difluoromethyl, trifluoromethyl, chlorofluoromethyl, dichlorofluoromethyl, chlorodifluoromethyl, 1-chloroethyl,
  • 1-bromoethyl 1-fluoroethyl, 2-fluoroethyl, 2,2-difluoroethyl, 2,2,2-trifluoroethyl, 2-chloro-2-fluoroethyl, 2-chloro-2,2-difluoroethyl, 2,2-dichloro 2-fluoroethyl, 2,2,2-trichloroethyl, pentafluoroethyl or 1,1,1-trifluoroprop-2-yl;
  • Hydroxyalkyl straight-chain or branched alkyl groups having 1 to 2, 1 to 4, 2 to 4, 1 to 6, 2 to 6, 1 to 8, 2 to 8, 1 to 10, 2 to 10, 2 to 20 or 2 to 30 Carbon atoms (as mentioned above), wherein at least one of the hydrogen atoms is replaced by a hydroxy group, as in 2-hydroxyethyl or 3-hydroxypropyl.
  • Alkyl e.g. C 2 -C 4 alkyl, C 2 -C 6 alkyl, C 2 -C 8 alkyl, C 2 -C 10 alkyl, C 2 -C 20 alkyl, or C 2 -C 30 alkyl , whose carbon chain can be interrupted by one or more groups -O-, for example, 2-methoxyethyl, 2-ethoxyethyl, 2-propoxyethyl, 2-isopropoxyethyl, 2-butoxyethyl, 2- and 3-methoxypropyl, 2- and 3-ethoxypropyl, 2- and 3-propoxypropyl, 2- and 3-butoxypropyl, 2- and 4-methoxybutyl, 2- and 4-ethoxybutyl, 2- and 4-propoxybutyl, 3,6-dioxaheptyl, 3,6-dioxaoctyl , 4,8-dioxanonyl, 3,7-dioxaoctyl
  • Alkyl e.g. C 2 -C 4 alkyl, C 2 -C 6 alkyl, C 2 -C 8 alkyl, C 2 -C 10 alkyl, C 2 -C 20 alkyl, or C 2 -C 30 alkyl , whose carbon chain can be interrupted by one or more groupings -S-, for example, represents 2-methylthioethyl, 2-ethylthioethyl, 2-propylthioethyl, 2-isopropylthioethyl, 2-butylthioethyl, 2- and 3-methylthiopropyl, 2- and 3-ethylthiopropyl, 2- and 3-propylthiopropyl, 2- and 3-butylthiopropyl, 2- and 4-methylthiobutyl, 2- and 4-ethylthiobutyl, 2- and 4-propylthiobutyl, 3,6-dithiaheptyl, 3,6-dithiaocty
  • Alkyl e.g. C 2 -C 4 -alkyl, C 2 -C 6 -alkyl, C 2 -C 8 -alkyl, C 2 -C 10 -alkyl, C 2 -C 20 -alkyl, or C 2 -C 30 - Alkyl whose carbon chain can be interrupted by one or more -NR- groupings is, for example, 2-monomethyl- and 2-monoethylaminoethyl, 2-dimethylaminoethyl, 2- and 3-dimethylaminopropyl, 3-monoisopropylaminopropyl, 2- and 4- Monopropylaminobutyl, 2- and 4-monomethylaminobutyl, 6-methyl-3,6-diazaphthyl, 3,6-dimethyl-3,6-diazaheptyl, 3,6-diazaoctyl, 3,6-dimethyl-3,6-diazaoctyl , 9
  • Alkyl e.g. C 2 -C 4 -alkyl, C 2 -C 6 -alkyl, C 2 -C 8 -alkyl, C 2 -C 10 -alkyl, C 2 -C 20 -alkyl, or C 2 -C 30 - Alkyl, whose carbon chain can be interrupted by one or more groups -CO-, represents, for example, propan-2-one-1-yl, butan-3-one-1-yl, butan-3-one-2-yl or 2-ethylpentan-3-one-1-yl.
  • Alkyl e.g. C 2 -C 4 -alkyl, C 2 -C 6 -alkyl, C 2 -C 8 -alkyl, C 2 -C 10 -alkyl, C 2 -C 20 -alkyl, or C 2 -C 30 - Alkyl, whose carbon chain can be interrupted by one or more groups -SO 2 - is, for example, 2-methylsulfonylethyl, 2-ethylsulfonylethyl, 2-propylsulfonylethyl, 2-isopropylsulfonylethyl, 2-butylsulfonylethyl, 2- and 3-methylsulfonylpropyl, 2 and 3-ethylsulfonylpropyl, 2- and 3-propylsulfonylpropyl, 2- and 3-butylsulfonylpropyl, 2- and 4-methylsulfonylbutyl, 2- and
  • C 2 -C 6 alkenyl such as ethenyl, 1-propenyl, 2-propenyl, 1-methylethenyl, 1-butenyl, 2-butenyl, 3-butenyl, 1-methyl-1-propenyl, 2-methyl-1-propenyl , 1-methyl-2-propenyl, 2-methyl-2-propenyl, 1-pentenyl, 2-pentenyl, 3-pentenyl, 4-pentenyl, 1-methyl-1-butenyl, 2-methyl-1-butenyl, 3 -Methyl-1-butenyl, 1-methyl-2-butenyl, 2-methyl-2-butenyl, 3-methyl-2-butenyl, 1-methyl-3-butenyl, 2-methyl-3-butenyl, 3-methyl 3-butenyl, 1, 1-dimethyl-2-propenyl, 1, 2-dimethyl-1-propenyl, 1, 2-dimethyl-2-propenyl, 1-ethyl-1-propenyl, 1-eth
  • Alkadienyl diunsaturated, straight-chain or branched hydrocarbon radicals having 4 to 6, 4 to 8 or 4 to 10 carbon atoms and two double bonds in any position, but preferably not cumulated, eg. B. 1, 3-butadienyl, 1-methyl-1,3-butadienyl, 2-methyl-1,3-butadienyl, penta-1,3-dien-1-yl, hexa-1,4-diene-1 yl, hexa-1, 4-dien-3-yl, hexa-1, 4-dien-6-yl, hexa-1, 5-dien-1-yl, hexa-1, 5-dien-3-yl, Hexa-1, 5-dien-4-yl, hepta-1, 4-dien-1-yl, hepta-1, 4-dien-3-yl, hepta-1, 4-dien-6-yl, Hepta-1, 4-dien-7-yl, hepta-1,
  • Alkatrienyl triunsaturated, straight-chain or branched hydrocarbon radicals having 6 to 8, 6 to 10, 6 to 20 or 6 to 30 carbon atoms and three double bonds in any position, but preferably not cumulated, eg. B. 1, 3,5-hexatrienyl, 1, 3,5-heptatrienyl, 1, 3,6-heptatrienyl, 1, 3,5-octatrienyl, 1, 3,6-octatrienyl, 1, 3,7-octatrienyl, 2,4,6-octatrienyl and the like.
  • Higher alkyl and alkenyl groups are for example by polymerization of lower alkanes, such as ethylene, propylene, butenes, pentenes or hexenes available.
  • Higher polyenyl groups alkadienes and trienes
  • monomer streams which are also diunsaturated monomers, such as
  • Butadiene or isoprene Higher alkylene, alkenylene and polyenylene groups are often not uniform due to their origin from polymerization reactions.
  • C 2 -C 6 alkynyl such as ethynyl, 1-propynyl, 2-propynyl, 1-butynyl, 2-butynyl, 3-butynyl, 1-methyl-2-propynyl, 1-pentynyl, 2-pentynyl, 3-pentynyl , 4-pentynyl, 1-methyl-2-butynyl, 1-methyl-3-butynyl, 2-methyl-3-butynyl, 3-methyl-1-butynyl, 1, 1-dimethyl-2-propynyl, 1-ethyl 2-propynyl, 1-hexynyl, 2-hexynyl, 3-hexynyl, 4-hexynyl, 5-hexynyl, 1-methyl-2-pentynyl, 1-methyl-3-pentynyl, 1-methyl-4-pentynyl, 2 -Methyl-3-pentynyl, 2-
  • Cycloalkyl-C 1 -C 4 -alkyl C 1 -C 4 -alkyl (as defined above) wherein a hydrogen atom is replaced by a cycloalkyl group, e.g. Cyclopropylmethyl, cyclopentylmethyl, cyclohexylmethyl and the like.
  • Cycloalkyl-C 3 -C 10 -alkyl C 3 -C 10 -alkyl (as defined above) wherein a hydrogen atom is replaced by a cycloalkyl group, e.g. Cyclopropylpropyl, cyclopropylbutyl, cyclopropylhexyl, cyclopropyloctyl, cyclopentylpropyl, cyclohexylpropyl and the like.
  • Cycloalkenyl monocyclic, monounsaturated hydrocarbon groups having 3 to 10, 3 to 8, 3 to 6, preferably 5 to 6 carbon ring members, such as cyclopenten-1-yl, cyclopenten-3-yl, cyclohexen-1-yl, cyclohexen-3-yl Cyclohexen-4-yl and the like;
  • Bicycloalkyl bicyclic hydrocarbon radical having 7 to 10 carbon atoms, such as bicyclo [2.2.1] hept-1-yl, bicyclo [2.2.1] hept-2-yl, bicyclo [2.2.1] hept-7-yl, bicyclo [2.2.2] oct-1-yl, bicyclo [2.2.2] oct-2-yl, bicyclo [3.3.0] octyl, bicyclo [4.4.0] decyl, decalin and the like;
  • Bicycloalkenyl bicyclic hydrocarbon radical with 5 to 10 C atoms such as bicyclo [2.2.1] hept-2-en-1-yl, bicyclo [2.2.1] hept-2-en-2-yl, bicyclo [2.2.1 ] hept-2-en-7-yl, bicyclo [2.2.2] oct-2-en-1-yl, bicyclo [2.2.2] oct-2-en-2-yl, bicyclo [2.2.2] oct-2-en-7-yl, bicyclo [3.3.0] oct-2-en-1-yl, bicyclo [3.3.0] oct-2-en-2-yl, bicyclo [3.3.0] oct -2-en-3-yl, bicyclo [4.4.0] dec-2-en-1-yl, bicyclo [4.4.0] dec-2-en-2-yl, bicyclo [4.4.0] decyl, 2-en-3-yl, bicyclo- [
  • Alkoxy for an oxygen-bonded alkyl group.
  • C 1 -C 2 alkoxy is methoxy or ethoxy.
  • C 1 -C 4 -alkoxy is, for example, n-propoxy, 1-methylethoxy (isopropoxy), butoxy, 1-methylpropoxy (sec-butoxy), 2-methylpropoxy (isobutoxy) or 1, 1-dimethylethoxy (tert-butoxy).
  • C 1 -C 6 -alkoxy is, for example, pentoxy, 1-methylbutoxy, 2-methylbutoxy, 3-methylbutoxy, 1, 1-dimethylpropoxy, 1, 2-dimethylpropoxy, 2,2-dimethylpropoxy, 1-ethylpropoxy, hexoxy, 1 Methylpentoxy, 2-methylpentoxy, 3-methylpentoxy, 4-methylpentoxy, 1, 1-dimethylbutoxy, 1, 2-dimethylbutoxy, 1, 3-dimethylbutoxy, 2,2-dimethylbutoxy, 2,3-dimethylbutoxy, 3 , 3-dimethylbutoxy, 1-ethylbutoxy, 2-ethylbutoxy, 1, 1, 2-trimethylpropoxy, 1, 2,2-trimethylpropoxy, 1-ethyl-1-methylpropoxy or 1-ethyl-2-methylpropoxy.
  • C 1 -C 8 alkoxy furthermore represents, for example, heptyloxy, octyloxy, 2-ethylhexyloxy and positional isomers thereof.
  • C 1 -C 10 -alkoxy is, for example, nonyloxy, decyloxy and positional isomers thereof.
  • Alkenyloxy Alkenyl as mentioned above, which is bonded via an oxygen atom, for. C 3 -C 6 alkenyloxy such as 1-propenyloxy, 2-propenyloxy, 1-methylethenyloxy, 1-butenyloxy, 2-butenyloxy, 3-butenyloxy, 1-methyl-1-propenyloxy, 2-methyl-1-propenyloxy, 1 Methyl 2-propenyloxy, 2-methyl-2-propenyloxy, 1-pentenyloxy, 2-pentenyloxy, 3-pentenyloxy, 4-pentenyloxy, 1-methyl-1-butenyloxy, 2-methyl-1-butenyloxy, 3-methyl 1-butenyloxy, 1-methyl-2-butenyloxy, 2-methyl-2-butenyloxy, 3-methyl-2-butenyloxy, 1-methyl-3-butenyloxy, 2-methyl-3-butenyloxy, 3-methyl-3 -butenyloxy, 1, 1-dimethyl-2-propenyloxy
  • Alkynyloxy alkynyl as mentioned above, which is bonded via an oxygen atom, for.
  • B. C 3 -C 6 alkynyloxy such as 2-propynyloxy, 2-butynyloxy, 3-butynyloxy, 1-methyl-2-propynyloxy, 2-pentynyloxy, 3-pentynyloxy, 4-pentynyloxy, 1-methyl-2-butynyloxy, 1 -Methyl-3-butynyloxy, 2-methyl-3-butynyloxy, 1-ethyl-2-propynyloxy, 2-hexynyloxy, 3-hexynyloxy, 4-hexynyloxy, 5-hexynyloxy, 1-methyl-2-pentynyloxy, 1-methyl 3-pentynyloxy and the like;
  • Cycloalkoxy Cycloalkyl as mentioned above, which is bonded via an oxygen atom, z. C 3 -C 10 cycloalkoxy or C 3 -C 8 cycloalkoxy such as cyclopropoxy, cyclopentoxy, cyclohexoxy, cycloheptoxy, cyclooctoxy and the like;
  • Cycloalkenyloxy Cycloalkenyl as mentioned above, which is bonded via an oxygen atom, for. C 3 -C 10 cycloalkenyloxy, C 3 -C 8 cycloalkenyloxy or, preferably, C 5 -C 6 cycloalkenyloxy such as cyclopent-1-enoxy, cyclopent-2-enoxy, cyclohex-1-enoxy and cyclohex-2-enoxy;
  • Alkylcarbonyl group of the formula R-CO-, wherein R is an alkyl group as defined above, e.g. Example for C 1 -C 10 alkyl, C 1 -C 8 -alkyl, C 1 -C 6 -alkyl, C 1 -C 4 -alkyl or C 1 -C 2 -alkyl. Examples are acetyl, propionyl and the like.
  • Alkenylcarbonyl group of the formula R-CO-, wherein R is an alkenyl group as defined above, e.g. B. for C 2 -C 10 alkenyl, C 2 -C 8 alkenyl, C 2 -C 6 alkenyl or C 2 -C 4 - alkenyl.
  • Alkynylcarbonyl group of the formula R-CO-, wherein R is an alkynyl group as defined above, e.g. B. for C 2 -C 10 alkynyl, C 2 -C 8 -alkynyl, C 2 -C 6 -alkynyl or C 2 -C 4 - alkynyl.
  • Alkylcarbonyloxy group of the formula R-CO-O-, in which R is an alkyl group as defined above, eg. Example for C 1 -C 10 alkyl, C 1 -C 8 -alkyl, C 1 -C 6 -alkyl, C 1 -C 4 -alkyl or C 1 -C 2 -alkyl. Examples are acetyloxy, propionyloxy and the like.
  • Alkenylcarbonyloxy group of the formula R-CO-O-, in which R stands for an alkenyl group as defined above, eg. B. C 2 -C 10 alkenyl, C 2 -C 8 alkenyl, C 2 -C 6 alkenyl or C 2 -C 4 alkenyl.
  • Alkynylcarbonyloxy group of the form in which R is an alkynyl group as defined above, eg. B. for C 2 -C 10 alkynyl, C 2 -C 8 alkynyl, C 2 -C 6 alkynyl or C 2 -C 4 alkynyl.
  • Alkoxycarbonyl group of the formula R-CO-, wherein R is an alkoxy group as defined above, e.g. B. for C 1 -C 10 alkoxy, C 1 -Cs-alkoxy, C 1 -C 6 alkoxy, C 1 -C 4 -alkoxy or C 1 -C 2 -alkoxy. Examples are methoxycarbonyl, ethoxycarbonyl and the like.
  • Alkenyloxycarbonyl group of the formula R-CO- in which R is an alkenyloxy group as defined above, eg. B. for C 2 -C 10 alkenyloxy, C 2 -C 8 alkenyloxy, C 2 -C 6 alkenyloxy or C 2 -C 4 alkenyloxy.
  • Alkynyloxycarbonyl group of the formula R-CO-, in which R stands for an alkynyloxy group as defined above, eg. B. for C 2 -C 10 alkynyloxy, C 2 -C 8 alkynyloxy, C 2 -C 6 alkynyloxy or C 2 -C 4 alkynyloxy.
  • Alkoxycarbonyloxy group of the formula R-CO-O- in which R is an alkoxy group as defined above, eg. B. for C 1 -C 10 alkoxy, C 1 -Cs alkoxy, C 1 -C 6 alkoxy, C 1 -C 4 - alkoxy or C 1 -C 2 alkoxy. Examples are methoxycarbonyl, ethoxycarbonyl and the like.
  • Alkenyloxycarbonyloxy group of the formula R-CO-O-, wherein R is an alkenyloxy group as defined above, e.g. B. for C 2 -C 10 alkenyloxy, C 2 -C 8 alkenyloxy, C 2 -C 6 alkenyloxy or C 2 -C 4 alkenyloxy.
  • Alkynyloxycarbonyloxy group of the formula R-CO-O-, wherein R is an alkynyloxy group as defined above, e.g. B. for C 2 -C 10 alkynyloxy, C 2 -C 8 alkynyloxy, C 2 -C 6 alkynyloxy or C 2 -C 4 alkynyloxy.
  • Alkylthio C 1 -C 10 -alkyl, as defined above, which is bonded via an S-atom.
  • Examples are methylthio, ethylthio, propylthio, isopropylthio, n-butylthio, sec-butylthio, isobutylthio, tert-butylthio, pentylthio, hexylthio, heptylthio, octylthio, 2-ethylhexylthio, nonylthio, decylthio and their positional isomers.
  • Alkenylthio C 2 -C 10 alkenyl, as defined above, attached via an S atom.
  • Alkynylthio C 3 -C 10 -alkynyl, as defined above, which is bonded via an S-atom.
  • heterocyclyl Five- or six-membered saturated or partially unsaturated heterocycle (hereinafter also heterocyclyl) containing one, two, three or four heteroatoms selected from the group oxygen, nitrogen (as N or NR X ) and sulfur and optionally 1 or 2 carbonyl groups Ring members: z.
  • B monocyclic saturated or partially unsaturated heterocycles containing in addition to carbon ring members one to three nitrogen atoms and / or an oxygen or sulfur atom or one or two oxygen and / or sulfur atoms and optionally 1 or 2 carbonyl groups, eg.
  • B. C-linked 5-membered heteroaryl containing one to three nitrogen atoms or one or two nitrogen atoms and a sulfur or oxygen atom as ring members such as 2-furyl, 3-furyl, 2-thienyl, 3-thienyl, 2-pyrrolyl , 3-Pyrrolyl, 3-isoxazolyl, 4-isoxazolyl, 5-isoxazolyl, 3-isothiazolyl, 4-isothiazolyl, 5-isothiazolyl, 3-pyrazolyl, 4-pyrazolyl, 5-pyrazolyl, 2-oxazolyl, 4 Oxazolyl, 5-oxazolyl, 2-thiazolyl, 4-thiazolyl, 5-thiazolyl, 2-imidazolyl,
  • Alkylene divalent, linear or branched saturated aliphatic groups having 2 to 30, 2 to 12 or 2 to 4 carbon atoms, eg. B. 1, 2-ethylene (CH 2 CH 2 ), 1, 2-propylene (CH (CH 3 ) CH 2 ), 1, 3-propylene (CH 2 CH 2 CH 2 ), 1, 4-butylene (CH 2 CH 2 CH 2 CH 2 ), 1, 5-pentylene (CH 2 CH 2 CH 2 CH 2 CH 2 ), 1, 6-hexylene (CH 2 CH 2 CH 2 CH 2 CH 2 CH 2 ) and the higher homologues ;
  • C 1 -C 10 -alcohol stands for a C 1 -C 10 -alkane, C 3 -C 10 -cycloalkane, C 2 -C 10 -alkene or C 2 -C 1 0 -alkyne, especially for a C 1 - C 10 alkane in which one or more hydrogen atoms, which are preferably not on the same carbon atom, are replaced by hydroxy groups.
  • saturated aliphatic monohydric alcohols ie those derived from C 1 -C 10 -alkanes
  • saturated aliphatic monohydric alcohols are methanol, ethanol, propanol, isopropanol, n-butanol, sec-butanol, isobutanol, tert-butanol, pentanol, amyl alcohol, hexanol , Hepanol, octanol, 2-ethylhexyl alcohol, nonanol, decanol and positional isomers thereof.
  • Examples of unsaturated alcohols ie those derived from C 2 -C 10 -alkenes or C 2 -C 10 -alkynes, are allyl alcohol and propargyl alcohol.
  • Examples of alicyclic alcohols ie those derived from C 3 -C 10 cycloalkanes, are cyclohexanol and cyclopentanol.
  • Examples of polyhydric alcohols in which more than one hydrogen atom is replaced by OH are ethylene glycol, propylene glycol, glycerol, pentaerythritol, sorbitol and the sugars such as glucose and fructose.
  • Polyether polyols are compounds of the formula HO-A- [OA-] n -OR, in which A is C 2 -C 6 -alkylene, preferably C 2 -C 4 -alkylene, particularly preferably C 2 -Cs-alkylene, in particular R is ethylene, R is H or C 1 -C 4 alkyl and n is an integer from 1 to 20.
  • A is C 2 -C 6 -alkylene, preferably C 2 -C 4 -alkylene, particularly preferably C 2 -Cs-alkylene, in particular R is ethylene, R is H or C 1 -C 4 alkyl and n is an integer from 1 to 20.
  • Examples thereof are diethylene glycol, triethylene glycol, tetraethylene glycol, diethylene glycol monomethyl ether, triethylene glycol monomethyl ether, tetraethylene glycol monomethyl ether and the like.
  • Component A is that Besta inventive mixture that gives this the liquid-crystalline properties (which, however, become visible only after curing of the mixture with optionally previous orientation of the applied to a substrate or a carrier mixture). However, these liquid-crystalline properties, especially those based on optical anisotropy, are markedly enhanced by the combination with component B.
  • component A to reflect in the UV and / or in the visible wavelength range is attributable to the fact that after orientation and curing of component A at least a portion of the oriented polymer is polymerized by polymerization (A.1). or (A.2) available cholesteric polymers or at least a portion of the oriented polymers (A.3) or (A.4) have a pitch of the helical superstructure, which corresponds to a wavelength in the UV and / or visible spectral range speaks.
  • Hardening means in the context of the present invention both the polymerization of monomers and the crosslinking of polymers.
  • Radiation-absorbing compounds B should be understood to mean those which are in the spectral range of the infrared (IR radiation), d. H. in the spectral range with a wavelength of> 750 nm (eg 751 nm) to about 1 mm, preferably from 751 nm to about 2000 nm, and / or in the visible spectral range, d. H. in the spectral range with a wavelength of 350 to 750 nm, preferably from 550 to 750 nm, and / or in the spectral range of ultraviolet (UV) radiation, d. H. in the spectral range with a wavelength of 10 nm to ⁇ 350 nm (eg 349 nm), preferably from 100 nm to 349 nm.
  • IR radiation infrared
  • the compounds of component B in the spectral range of the infrared, in particular the near infrared (NIR), d. H. from> 750 (eg 751) to 2000 nm, and / or in the visible spectral range, in particular from 550 to 750 nm.
  • NIR near infrared
  • the compounds B absorb in the spectral range of the infrared, in particular the near infrared (NIR), ie from> 750 (eg 751) to 2000 nm, and optionally also in the visible spectral range, in particular from 550 to 750 nm.
  • NIR near infrared
  • the compounds absorb in both the IR and visible spectral regions, they preferably exhibit the highest absorption maximum in the IR region and a smaller maximum (often in the form of a so-called absorption shoulder) in the visible region.
  • the compounds B absorb in the visible spectral range, ie from 350 to 750 nm, preferably from 400 to 750 nm and in particular from 550 to 700 nm.
  • the compounds B absorb in the spectral range of the infrared, in particular the near infrared (NIR), d. H. from> 750 (eg 751) to 2000 nm, and optionally also in the visible spectral range, in particular from 550 to 750 nm.
  • NIR near infrared
  • Fluorescence is the transition of a system excited by absorption of electromagnetic radiation (usually visible light, UV radiation, X-rays or electron beams) into a state of lower energy by spontaneous emission of radiation of equal (resonance fluorescence) or longer wavelength.
  • electromagnetic radiation usually visible light, UV radiation, X-rays or electron beams
  • Preferred compounds of component B when they fluoresce, exhibit fluorescence in the IR spectral range, preferably in the NIR.
  • the compounds of component B in the spectral range of the infrared in particular the near infrared (NIR), d. H. from> 750 (eg 751) to 2000 nm, and optionally also in the visible spectral range, in particular from 550 to 750 nm, and also show fluorescence in the IR spectral range, preferably in the NIR spectral range.
  • NIR near infrared
  • the radiation-absorbing and optionally fluorescent conjugated polycyclic compound of component B is preferably selected from among naphthalenes, anthracenes, phenanthrenes, tetracenes, perylenes, terrylenes, quaterrylenes, pentarylenes, hexarylenes, anthraquinones, indanthrones, acridines, carbazoles, dibenzofurans, dinaphthofurans, benzimidazoles, Benzothiazoles, phenazines, dioxazines, quinacridones, metallophthalocyanines, metalnaphthalocyanines, metalloporphyrins, coumarins, dibenzofuranones, dinaphthofuranones, benzimidazolones, indigo compounds, thioindigo compounds, quinophthalones, naphthoquinophthalones and diketopyrrolopyrroles.
  • the radiation absorbing and optionally fluorescent conjugated polycyclic compound of component B is selected from naphthalenes, anthracenes, phenanthrenes, tetracenes, perylenes, terrylenes, quaterrylenes, pentaarylenes and hexarylenes, more preferably among perylenes, terrylenes and quaterrylenes, and more particularly among Terry and quaterrylenes. Specifically, it is a quaterrylene.
  • the polycyclic compounds B preferably carry from 1 to 28 substituents, with the maximum number of substituents depending of course on the number of substitutable carbon atoms in the respective polycycle.
  • Suitable substituents are selected from halogen, CN, C 1 -C 20 -alkyl, aryl, hetaryl, O-bound aliphatic, aromatic, araliphatic, alicyclic, heterocyclic and / or heteroaromatic radicals, carboxyl, carboxylate and carboxamide, where two carboxyl groups which are sufficiently close together can also together form a carboxylic acid anhydride group or two carboxamide groups which are sufficiently close together can form a carboximide group.
  • At least one of the other substituents is particularly preferably an oxygen-bonded aliphatic, aromatic, araliphatic, alicyclic or heterocyclic radical and in particular an oxygen-bonded aromatic radical.
  • Preferred substituents on the polycyclic compounds B are selected from halogen, CN, C 1 -C 20 -alkyl, phenyl, naphthyl, 5- or 6-membered hetaryl having 1, 2, 3 or 4 heteroatoms as ring members, which are selected under O, N and S, where phenyl, naphthyl and hetaryl can carry 1, 2, 3 or 4 substituents which are selected from C 1 -C 10 -alkyl, C 1 -C 6 -alkoxy and halogen; COR 1 and OR 13 , wherein
  • each R 1 is independently OR 2 or NR 3 R 4 ; wherein R 2 is H, C 1 -C 30 -alkyl, C 2 -C 30 -hydryl, n is the radical of the formula
  • Heteroatoms selected from O, N and S, and optionally containing 1 or 2 carbonyl groups as ring members;
  • R 3 and R 4 independently of one another are H, C 1 -C 30 -alkyl, C 2 -C 30 -hydroxyalkyl, a radical of the formula -A- [OA] x -OR 5 , a radical of the formula -A- [NR 6 -A-] X -V, C 3 -C 10 -
  • Cycloalkyl C 3 -C 10 -cycloalkyl-C 1 -C 4 -alkyl, aryl, aryl-C 1 -C 4 -alkyl, heterocyclyl or heterocyclyl-C 1 -C 4 -alkyl, where heterocyclyl in both last-mentioned radicals represents a 5 or 6-membered saturated, partially unsaturated or aromatic heterocyclic ring containing 1, 2, 3 or 4 heteroatoms selected from O, N and S, and optionally containing 1 or 2 carbonyl groups as ring members;
  • V is OR 5 or NR 7 R 8 ;
  • each R 5 is independently H or C 1 -C 4 alkyl
  • R 6 , R 7 and R 8 are independently H, C 1 -C 4 alkyl or C 1 -C 4 hydroxyalkyl;
  • each A is independently C 2 -C 4 alkylene
  • each x is independently a number from 1 to 20;
  • two groups COR 1 which are in each case in sufficiently close proximity to one another, can also together form a group -C (O) -OC (O) - or -C (O) -NR 9 -C (O) -, in which
  • each R 9 independently represents H, C 1 -C 30 -alkyl whose carbon chain is represented by one or more groups selected from -O-, -S-, -NR 10 -, -CO- and -SO 2 -, may be interrupted, wherein the carbon chain may be mono- or polysubstituted with the same or different radicals which are selected from C 1 -C 6 alkoxy and a bound via a nitrogen atom, 5, 6 or 7-membered saturated, partially ggn or aromatic heterocyclic radical, in addition to the one nitrogen atom 1, 2 or 3 further heteroatoms, which are selected from O, N and S, and / or 1 or 2 CO groups as ring members may contain; Cs-Cs-cycloalkyl which may be unsubstituted or substituted by 1, 2, 3 or 4 dC 6 -alkyl groups and / or 1 or 2
  • heterocyclyl which contains 1, 2, 3 or 4 heteroatoms or heteroatom-containing groups which are selected from O, S, N, NR 10 and SO 2, and optionally containing 1 or 2 CO groups as ring members, where heterocyclyl may be unsubstituted or may carry 1, 2, 3 or 4 C 1 -C 6 -alkyl substituents;
  • Aryl or hetaryl which is selected from pyrrolyl, pyrazolyl, imidazolyl, oxazolyl, thiazolyl, pyridinyl, pyridazinyl, pyrimidinyl, pyrazinyl, indolyl, quinolinyl, isoquinolinyl and quinaldinyl, wherein aryl and hetaryl each one or more times by C 1 -C 20 alkyl, C 1 -C 6 alkoxy, cyano, -CONH-R 11 and / or -NH-
  • R 10 , R 11 and R 12 are independently H, C 1 -C 10 alkyl, C 2 -C 10 hydroxyalkyl or C 1 -C 10 haloalkyl;
  • R 13 is C 1 -C 2 0 -alkyl, a radical of the formula -A '- [O-A'] y -OR 14 , C 3 -C 10 -cycloalkyl, C 3 -C 10 -cycloalkyl-C 1 - C4-alkyl, aryl, aryl-C 1 -C 4 alkyl, a 5- or 6-membered saturated, partially unsaturated or aromatic heterocyclic ring containing 1, 2, 3 or 4 heteroatoms selected from O, N and S and optionally containing 1 or 2 carbonyl groups as ring members, or such a heterocyclic ring bonded via CrC 4 -alkyl, in which
  • R 14 is H or C 1 -C 4 alkyl
  • a ' is C 2 -C 4 alkylene
  • y is 0 or an integer from 1 to 10;
  • At least one of the substituents is COR 1 and / or at least two substituents COR 1 together form a group -C (O) -OC (O) - or -C (O) -NR 9 -C (O) -.
  • At least one of the other substituents is particularly preferably an OR 13 radical.
  • Particularly preferred polycyclic compounds are selected from naphthalenes, anthracenes, phenanthrenes, tetracenes, perylenes, terrylenes, quaterrylenes, pentaarylenes and hexarylenes, which are preferably substituted as described above, and in particular among perylenes, terrylenes and quaterrenes, preferably as above are described substituted.
  • polycyclic compounds of component B are selected from compounds of the formula I,
  • X 1 and X 2 are halogen, CN or COR 1 , wherein at least one of X 1 and X 2 is COR 1 ;
  • X 3 and X 4 are halogen, CN or COR 1 , wherein at least one of X 3 and X 4 is COR 1 ;
  • each R 1 is independently OR 2 or NR 3 R 4 ;
  • R 2 is H, C 1 -C 30 -alkyl, C 2 -C 30 -hydroxyalkyl, a radical of the formula
  • R 3 and R 4 independently of one another are alkyl, C 2 -C 30 -hydroxyalkyl, a radical of the formula -A- [OA] x -OR 5 , a radical of the formula -A- [NR 6 -A-] X - V, C 3 -C 10 -cycloalkyl, C 3 -C 10 -cycloalkyl-C 1 -C 4 -alkyl, aryl, aryl-C 1 -C 4 -alkyl, heterocyclyl or heterocyclyl-C 1 -C 4 -alkyl, wherein heterocyclyl in both last-named radicals is a 5- or 6-membered saturated, partially unsaturated or aromatic heterocyclic ring having 1, 2, 3 or 4 heteroatoms selected from O, N and S, and optionally 1 or contains 2 carbonyl groups as ring members;
  • V is OR 5 or NR 7 R 8 ;
  • each R 5 is independently H or C 1 -C 4 alkyl
  • R 6 , R 7 and R 8 are independently H, C 1 -C 4 alkyl or C 1 -C 4 hydroxyalkyl;
  • each A is independently C 2 -C 4 alkylene
  • each x is independently a number from 1 to 20;
  • X 1 and X 2 and / or X 3 and X 4 together form a group -C (O) -OC (O) - or -C (O) -NR 9 -C (O) -, in which
  • each R 9 independently represents H, C 1 -C 30 -alkyl whose carbon chain is represented by one or more groups selected from -O-, -S-, -NR 10 -, -CO- and -SO 2 -, may be interrupted, wherein the carbon chain may be mono- or polysubstituted with the same or different radicals which are selected from C 1 -C 6 alkoxy and a bound via a nitrogen atom, 5, 6 or
  • 7-membered saturated, partially unsaturated or aromatic heterocyclic radical in addition to the one nitrogen atom 1, 2 or 3 further heteroatoms, which are selected from O, N and S, and / or 1 or 2 CO groups as ring members may contain; Cs-Cs-cycloalkyl which may be unsubstituted or substituted by 1, 2, 3 or 4 C 1 -C 6 -alkyl groups and / or 1 or 2
  • R 10 , R 11 and R 12 are independently H, C 1 -C 10 alkyl, C 2 -C 10 hydroxyalkyl or C 1 -C 10 haloalkyl;
  • each Y is independently selected from halo, C 1 -C 20 alkyl, phenyl, naphthyl, 5- or 6-membered hetaryl having 1, 2, 3 or 4 heteroatoms as ring members selected from O, N and S, wherein Phenyl, naphthyl and hetaryl may carry 1, 2, 3 or 4 substituents which are selected from C 1 -C 10 alkyl, C 1 -C 6 alkoxy and halogen; and a residue OR 13 , in which
  • R 13 is C 1 -C 2 0 -alkyl, a radical of the formula -A '- [O-A'] y -OR 14 , C 3 -C 10 -cycloalkyl, C 3 -C 10 -cycloalkyl-C 1 - C4-alkyl, aryl, aryl-C 1 -C 4 alkyl, a 5- or 6-membered saturated, partially unsaturated or aromatic heterocyclic ring containing 1, 2, 3 or 4 heteroatoms selected from O, N and S and optionally containing 1 or 2 carbonyl groups as ring members, or such a heterocyclic ring bonded via CrC 4 -alkyl, in which
  • R 14 is H or C 1 -C 4 alkyl
  • a ' is C 2 -C 4 alkylene
  • y is O or an integer from 1 to 10;
  • n O, 1, 2, 3 or 4;
  • n O or an integer from 1 to 24;
  • o O or 1
  • p O or 1.
  • n is preferably 0, 1 or 2
  • compounds I contain neither carboxyl groups nor carboxylic anhydride groups.
  • X 1 together with X 2 and / or X 3 together with X 4 particularly preferably represents a group -C (O) -NR 9 -C (O) -. Especially are both X 1 and X 2 and X 3 and X 4 in each case together are a group -C (O) -NR 9 -C (O) -.
  • R 9 is not H.
  • the compounds of component B and in particular the compounds of formula I contain no attack by bases or nucleophiles groups and in particular no -C (O) -NH-C (O) -, -C (O) -OC (O) - and COOH groups.
  • n in compounds I is O or an integer from 1 to 24. It goes without saying that the maximum possible number of substituents Y depends on the number of substituable carbon atoms in the polycyclic compound I, and ⁇ 8 + nx 4 ) ⁇ ; d. H. the compounds I contain O to ⁇ 8 + (n x 4) ⁇ substituents Y.
  • m is a number from 1 to ⁇ 8 + (n x 4) ⁇ , and more preferably from 4 to ⁇ 8 + (n x 4) ⁇ . More preferably, m is a number from 4 to ⁇ 4 + (n x 2) ⁇ .
  • At least one radical Y is OR 13 . More preferably, at least half of the m substituents Y is a radical OR 13 . If not all radicals Y are OR 13 , the remaining radicals Y are preferably halogen. In particular, all radicals Y are OR 13 . m is preferably a number from 2 to 6.
  • R 13 is preferably selected from aryl and aryl-C 1 -C 4 -alkyl and in particular from aryl.
  • Aryl is preferably phenyl or substituted phenyl.
  • Suitable substituents on the phenyl ring are those mentioned above for aryl.
  • R 13 is substituted phenyl, it is particularly preferably a radical of the formula
  • R 15 is a linear or preferably branched C 1 -C 10 -alkyl radical whose carbon chain may be interrupted by one or more groups selected from -O-, -S-, -NR 16 -, -CO- and -SO 2 - where the carbon chain is optionally mono- or polysubstituted by identical or different radicals selected from C 1 -C 6 -alkoxy or a 5- to 7-membered heterocyclic radical bonded via a nitrogen atom and optionally contains heteroatoms and / or is aromatic, for C 3 -C 10 -cycloalkyl which may be unsubstituted or substituted by 1, 2, 3 or 4 dC 6 alkyl groups and / or contain 1 or 2 CO groups as ring members may be or is 3- to 10-membered saturated or partially unsaturated heterocyclyl having 1, 2, 3 or 4 heteroatoms or heteroatom-containing groups selected from O, S, N, NR 10 and SO 2, and optionally 1 or 2 CO Groups as ring members,
  • R 16 is hydrogen or C 1 -C 6 alkyl.
  • R 15 is linear or preferably branched C 1 -C 10 -alkyl or C 3 -C 10 -cycloalkyl.
  • R 15 is linear or preferably branched C 1 -C 10 -alkyl.
  • R 9 preferably represents aryl, in particular phenyl, which is unsubstituted or carries 1, 2, 3 or 4 substituents which are selected from C 1 -C 6 -alkyl, C 1 -C 6 -
  • Haloalkyl C 1 -C 6 -alkoxy, C 1 -C 6 -haloalkoxy, halogen and CN, more preferably under C 1 -C 6 -alkyl and C 1 -C 6 -alkoxy and in particular under C 1 -C 6 alkyl.
  • R 9 is particularly preferably phenyl which carries 1, 2 or 3 linear or preferably branched C 1 -C 6 -alkyl radicals. Specifically, R 9 is 2,6-diisopropylphenyl.
  • n is 0, 1 or 2; d.
  • Compounds I are more preferably perylene, terrylene or quaterrylene compounds, more preferably 1 or 2, d.
  • Compounds I are more preferably terrylene or quaterrylene compounds, and even more preferably for 2, d. H.
  • Compounds I are even more preferably quaterrylene compounds.
  • perylene monoimides in particular N-substituted perylene-3,4-dicarboxylic acid monoimides
  • perylene diimides in particular N, N'-disubstituted perylene-3,4: 9,10-tetracarboxylic diimides
  • terrylene monoimides in particular N-substituted terrylene-3,4-dicarboxylic de
  • terrylene diimides in particular N, N'-disubstituted terrylene-3,4: 11,12-tetracarboxylic diimides
  • quaterrylene monoimides in particular N-substituted quaterrylene-3,4-dicarboxylic acid monoimides
  • Quaterthylene diimides in particular N, N'-disubstituted quaterrylene-3,4: 13,14-tetracarboxylic diimides.
  • Particularly preferred compounds of component B are those which in the spectral range of the infrared, d. H. in the spectral range with a wavelength of> 750 nm to about 1 mm, preferably in the range of the near infrared (NIR), d. H. in the spectral range with a wavelength of> 750 nm z. 751 nm) to 2000 nm and, if appropriate, also in the visible spectral range, in particular from 550 to 750 nm.
  • particularly preferred compounds of component B preferably also exhibit fluorescence in this wavelength range. When the compounds absorb in both the IR and visible spectral regions, they preferably exhibit the largest absorption maximum in the IR range and a smaller maximum (often in the form of a so-called absorption shoulder) in the visible range.
  • the compounds B absorb in the visible spectral range, ie. H. from 350 to 750 nm, preferably from 400 to 750 nm and in particular from 550 to 700 nm.
  • the compounds B absorb in the spectral range of the infrared, in particular the near infrared (NIR), d. H. from> 750 (eg 751) to 2000 nm, and optionally also in the visible spectral range, in particular from 550 to 750 nm.
  • the compounds also exhibit fluorescence in this wavelength range.
  • Component A describes preferred monomers of group (A.1) in WO 99/19267, WO 03/064559 and WO 2004/005427 and in the references cited therein, to which reference is hereby fully made.
  • At least one achiral nematic polymerizable monomer of group (A.1) is polyfunctional and in particular difunctional polymerizable.
  • Preferred achiral nematic difunctionally polymerizable monomers correspond to the general formula V
  • Y 1 , Y 2 , Y 3 , Y 4 are each independently a chemical bond, -O-, -S-, -CO-O-, -O-CO-, -O-CO-O-, -CO-S -, -S-CO-, -CO-N (R 3 ) -, -N (R 3 ) -CO-, -N (R a ) -CO-O-,
  • R a is hydrogen or C 1 -C 4 alkyl
  • a 1 , A 2 represent identical or different spacers, for example linear C 2 -C 30 -alkylene groups, preferably C 2 -C 12 -alkylene groups, which may be interrupted by oxygen, sulfur, optionally monosubstituted nitrogen, these interrupting groups not may be adjacent;
  • M is a mesogenic group which preferably has the general formula VI:
  • T is identical or different divalent alicyclic, saturated or partially unsaturated heterocyclic, aromatic or heteroaromatic radicals, preferably 1, 4-bonded unsubstituted or 1 to more than once, for. B. 1 to 4-fold, substituted benzene rings,
  • R b is fluorine, chlorine, bromine, C 1 -C 20 -alkyl, C 1 -C 10 -alkoxy, C 1 -d 0 -alkylcarbonyl, C 1 -C 10 -alkylcarbonyloxy, hydroxy, nitro, CHO or CN, preferably chlorine , Bromo or C 1 -C 4 alkyl and especially methyl; and
  • n is an integer from 0 to 4, preferably 0 to 2 and especially 0 or 1;
  • n is an integer from 0 to 3, preferably 0, 1 or 2, in particular 1 or 2 and especially 2.
  • the mesogenic group preferably comprises a substituted 1,4-dioxybenzene building block, in particular a methyl-substituted 1,4-dioxybenzene building block.
  • Particularly preferred mesogenic groups have the following structures VII: 35 (VII) wherein
  • R b is fluorine, chlorine, bromine, C 1 -C 10 alkyl, C 1 -C 10 alkoxy, C 1 -d 0 alkylcarbonyl, C 1 -C 10 alkylcarbonyloxy, hydroxy, nitro, CHO or CN;
  • n is an integer from 0 to 4.
  • R b is chlorine, bromine or C 1 -C 4 -alkyl, and in particular methyl and n is 0 to 2, in particular 0 or 1, especially 1.
  • component (A.1) may also contain a monofunctionally polymerizable achiral nematic monomer.
  • the achiral nematic monofunctionally polymerizable monomer preferably corresponds to the general formula Va or Vb
  • component (A.1) does not contain the monofunctionally polymerizable achiral nematic monomer as the sole achiral nematic polymerizable monomer, but in combination with a polyfunctional, preferably difunctionally polymerizable achiral nematic monomer.
  • the monofunctionally polymerizable monomer is preferably present in an amount of at most 20% by weight, more preferably at most 10% by weight and in particular at most 5% by weight, based on the total weight of polyfunctional and monofunctional polymerizable achiral nematic monomers.
  • Component (A.1) particularly preferably contains no monofunctionally polymerizable achiral nematic monomers, but only poly-, especially difunctionally polymerizable, achiral nematic monomers.
  • the chiral polymerizable monomer of the group (A.1) preferably corresponds to the formula IX
  • Z 1 , Y 1 , Y 2 , Y 3 and M are as defined above,
  • o, p are 0 or 1, where o and p can not simultaneously be 0,
  • a 3 and A 4 are the same or different and
  • n, m are 0, 1 or 2, where the sum n + m is 1 or 2, preferably 2;
  • X stands for a chiral radical.
  • chiral radicals X of the compounds of the general formula IX inter alia, owing to their easier availability, preference is given in particular to those derived from sugars, dinaphthyl or diphenyl derivatives and also optically active glycols, alcohols or amino acids.
  • the sugars include, in particular, pentoses and hexoses and derivatives derived therefrom.
  • radicals X are the following structures, wherein the terminal lines each denote the free valencies.
  • L 1 is C 1 -C 4 alkyl, C 1 -C 4 alkoxy, halogen, COOR c , OCOR c or NHCOR c and R c is C 1 -C 4 alkyl or hydrogen.
  • chiral groups are also suitable which have the following structures:
  • the nematic achiral difunctional polymerizable monomer has the following structural formula X.
  • the chiral polymerizable monomer has the following structural formula XI or XII (XI)
  • the amount ratio of achiral nematic monomer to chiral monomer is selected in the mixture according to the invention so that the polymer resulting from these monomers after orientation has a pitch of the helical superstructure which corresponds to a wavelength in the visible and / or UV spectral range.
  • the quantity ratio depends on the type of nematic and chiral monomers and must be determined on a case-by-case basis.
  • At least one cholesteric polymerizable monomer of group (A.2) can be used as component A.
  • the monomers b) comprise at least one cholesteric polymerizable monomer of the formula XIII
  • At least one cholesteric crosslinkable polymer of group (A.3) can be used as component A.
  • mixed esters in which the hydroxyalkyl radicals of component (1) bonded via ether functions comprise straight-chain or branched C 2 -C 10 -hydroxyalkyl radicals, in particular hydroxypropyl and / or hydroxyethyl radicals.
  • Component (1) of the employable mixed esters preferably has a molecular weight of about 500 to about 1 million.
  • Preferred amounts of the anhydroglucose units of the cellulose are etherified with an average molar degree of substitution of 2 to 4 with hydroxyalkyl radicals.
  • the hydroxyalkyl groups in the cellulose may be the same or different. Up to 50% of these can also be replaced by alkyl groups (in particular C 1 -C 10 -alkyl groups). An example of this is the hydroxypropylmethyl cellulose.
  • component (2) of the miscible esters which can be used straight-chain aliphatic C 1 -C 10 -carboxylic acids, in particular C 2 -C 6 -carboxylic acids, branched aliphatic C 4 -C 10 -carboxylic acids, in particular C 4 -C 6 -carboxylic acids or straight-chain or branched halocarboxylic acids are useful.
  • Component (2) may also be benzoic acid or aromatic substituted aliphatic carboxylic acids, especially phenylacetic acid.
  • Component (2) is particularly preferably selected from acetic acid, propionic acid, n-butyric acid, isobutyric acid or n-valeric acid, in particular under propionic acid, 3-CI-propionic acid, n-butyric acid or isobutyric acid.
  • the component (3) is selected from unsaturated C 3 -C 1 2-mono- or dicarboxylic acids or monoesters of such a dicarboxylic acid, in particular ⁇ , ß-ethylenically unsaturated Cs-C ⁇ -mono- or dicarboxylic acids or monoesters of the dicarboxylic acids.
  • the component (3) of the usable mixed esters is particularly preferably selected from acrylic acid, methacrylic acid, crotonic acid, vinylacetic acid, maleic acid, fumaric acid or undecenoic acid, in particular under acrylic acid or methacrylic acid.
  • the component (1) is having an average molar degree of substitution of from 1, 5 to 3, in particular from 1, 6 to 2.7, particularly preferably from 2.3 to 2,6 with the components (2) and (3) are preferably about 1 to 30%, in particular 1 to 20% or 1 to 10%, particularly preferably about 5 to 7% of the OH groups of the component (1 ) esterified with the component (3).
  • the quantitative ratio of component (2) to component (3) determines the reflection wavelength of the polymer.
  • Highly suitable polymers of the group (A.3) are also the propargyl-terminated, cholesteric polyesters or polycarbonates described in DE-A-197 17 371.
  • polyesters or polycarbonates having at least one propargyl end group of the formula R d C ⁇ C-CH 2 -, in which R d is H, C 1 -C 4 -alkyl, aryl or aryl-C 1 -C 4 -alkyl (For example, benzyl or phenethyl), which is bonded directly or via a link to the polyester or polycarbonates.
  • the link is preferably selected from
  • R e is H, C 1 -C 4 alkyl or phenyl
  • Z is O, S or NR f
  • R f is H, C 1 -C 4 alkyl or phenyl.
  • the propargyl end group is over
  • the polyesters preferably contain (4) at least one aromatic per den Dicarbon Textreread and / or at least one aromatic or araliphatic Hydroxycarbon Textreappel and
  • Preferred dicarboxylic acid units are those of the formula
  • each of the phenyl groups or the naphthyl group can have 1, 2 or 3 substituents independently of one another selected from C 1 -C 4 -alkyl, C 1 -C 4 -alkoxy, halogen or phenyl, where in the above formulas W is NR g , S, O, (CH 2 ) r O (CH 2 ) q, (C) e is single bond, R g is alkyl or hydrogen, s is an integer from 1 to 15, and r and q are independently stand for integers from 0 to 10.
  • Preferred hydroxycarboxylic acid units are those of the formula
  • each phenyl group or naphthyl group may have 1, 2 or 3 substituents independently selected from C 1 -C 4 alkyl, C 1 -C 4 alkoxy, halogen or phenyl.
  • Preferred diol units are those of the formula
  • L represents alkyl, alkoxy, halogen, COOR h , OCOR h , CONHR h or NHCOR h ,
  • X is S, O, N, CH 2 or a single bond
  • A is a single bond, (CH 2 ) n , O (CH 2 ) n , S (CH 2 ) n , NR '(CH 2 ) n,
  • R 1 is alkyl or hydrogen
  • R h is hydrogen, halogen, alkyl or phenyl and n is an integer from 1 to 15.
  • polyesters which contain at least one dicarboxylic acid unit of the formula
  • R j is H, halogen, C 1 -C 4 alkyl, in particular CH 3 or C (CH 3 ) 3 , or phenyl.
  • P is a propargyl end group of the formula defined above
  • each phenyl group or py group can have 1, 2 or 3 substituents which are independently selected from C 1 -C 4 alkyl, C 1 -C 4 alkoxy, halogen or phenyl, and A (together with the adjacent Oxygen atoms) for one of the abovementioned diol units.
  • diesters are those of the above formula in which B is for
  • Preferred polycarbonates are those which contain, as diol units, at least one mesogenic unit of the formula
  • R j has the meanings given above and in particular represents H or CH 3 .
  • Particularly preferred polycarbonates are those with Propargylend phenomenon of the formula HC ⁇ CCH 2 O-R'-CO, wherein R 1 is
  • Suitable polymers of group (A.3) are cholesteric polycarbonates which also contain photoreactive groups at a non-terminal position. Such polycarbonates are described in DE-A-196 31 658. They preferably correspond to the formula XIV
  • the molar ratio w / x / y / z is about 1 to 20 / about 1 to 5 / about 0 to 10 / about 0 to 10. Particularly preferred is a molar ratio w / x / y / z of about 1 to 5 / about 1 to 2 / about 0 to 5 / about 0 to 5.
  • A is a mesogenic group of the formula
  • D is a photoreactive group of the formula
  • L represents alkyl, alkoxy, halogen, COOR 15 , OCOR n , CONHR n or NHCOR n ,
  • X is S, O, N, CH 2 or a single bond
  • R is alkyl or hydrogen
  • A is a single bond, (CH 2 ) n , O (CH 2 ) n , S (CH 2 ) n , NR (CH 2 ) n ,
  • R m is hydrogen, halogen, alkyl or phenyl and n is an integer from 1 to 15.
  • R m is alkyl or halogen and A is a single bond or when R m is H or alkyl and A is
  • Isosorbide, isomannide and / or isoidide is the preferred chiral component.
  • the proportion of the chiral diol structural units is preferably in the range from 1 to 80 mol% of the total content of diol structural units, particularly preferably 2 to 20 mol%, depending on the desired reflection behavior.
  • a cholesteric polymer can be used in a polymerizable diluent (group (A.4)).
  • Preferred polymers of the group (A.4) are, for example, crosslinkable, cholesteric copolyisocyanates, as described in US-A-08 834 745, to which reference is hereby fully made.
  • Such copolyisocyanates have repeating units of the formulas
  • R ° is a chiral aliphatic or aromatic radical
  • R p is a crosslinkable radical
  • R q is an achiral radical
  • alkyl (also in terms such as alkoxy, dialkyl, alkylthio, etc.) is a branched and unbranched C 1 -C 12 -alkyl, preferably C 3 -C 12 , particularly preferably C 4 -C 10, in particular C 6 -C 10 -alkyl.
  • R ° is selected from (chiral) branched or unbranched alkyl, alkoxyalkyl, alkylthioalkyl, cycloalkyl, alkylphenyl or C 3 -C 9 -epoxyalkyl radicals or radicals of esters of C 1 -C 6 -fatty acids with C C 1 -C 6 -alkanols or C 3 -C 9 -dialkyl ketones.
  • the ester radical can be bonded to the N atom both via the fatty acid moiety and via the alkanol moiety.
  • the radical R ° can be 1, 2 or 3 substituents having the same or different g are selected from alkoxy groups, di-C 1 -C 4 alkylamino groups, CN, halogen atoms or C 1 -C 4 alkylthio groups.
  • R ° is selected from alkyl, alkoxyalkyl, residues of esters of C 1 -C 6 fatty acids with C 1 -C 6 -alkanols, C 3 -C 9 dialkyl ketones and epoxidized C 3 -C 9 -epoxyalkyl radicals, wherein R ° may be substituted by 1 or 2 radicals which are identical or different and are selected from alkoxy, halogen, CN or CF3.
  • Preferred substituents for branched or unbranched alkyl or alkoxy radicals are selected from alkoxy groups, halogen atoms or CN; for esters of C 1 -C 6 -fatty acids with C 1 -C 6 -alkanols among alkoxy groups, halogen atoms, CN or CF 3 and for C 3 -C 9 -dialkyl ketones among alkoxy groups, halogen atoms or CN.
  • the main chain of the radical R ° has a length of 3 to 12, in particular 6 to 10, preferably 6 to 8 members (C, O and / or S atoms).
  • component XV of the usable copolyisocyanates is derived from 2,6-dimethylheptyl isocyanate.
  • the radical is selected from methyl acrylate, ethyl acrylate, propyl acrylate, n-butyl acrylate, isobutyl acrylate, 2-ethylhexyl acrylate, methyl methacrylate, ethyl methacrylate, propyl methacrylate, n-butyl methacrylate, isobutyl methacrylate, 2-ethylhexyl methacrylate, in particular ethyl acrylate or ethyl methacrylate.
  • the radical R q preferably has the same meanings as the radical R °. But it is achiral, ie it has no center of chirality or exists as a racemic mixture.
  • the main chain of the radical R q has a length of 4 to 12, in particular 6 to 10, preferably 6 to 8 members (C, O and / or S atoms).
  • component XVII of the copolyisocyanates of the invention is derived from n-hexyl isocyanate, n-heptyl isocyanate or n-octyl isocyanate.
  • the components XV, XVI and XVII are preferably in the molar ratio XV: XVI: XVII of about 1 to 20: 1 to 20: 50 to 98, in particular about 5 to 15: 5 to 15: 65 to 90, particularly preferably about 15:10 : 75 available.
  • the units XV, XVI and XVII may be randomly distributed in the usable copolyisocyanates.
  • component A (A.1) as component A.
  • the component (A.1) contains the nematic polymerizable monomer in an amount of 40 to 99.5% by weight and the chiral polymerizable monomer in an amount of 0.5 to 60% by weight, respectively based on the total weight of component (A.1).
  • the proportion of chiral nematic monomer determines in which spectral region component A reflects.
  • the desired reflection range can be adjusted depending on the individual nematic and chiral components and their respective concentration with the aid of simple preliminary experiments.
  • the component (A.1) contains the nematic polymerizable
  • Monomer in an amount of 80 to 99.5 wt .-%, in particular from 90 to 99.5% by weight and the chiral polymerizable monomer in an amount of 0.5 to 20 wt .-% and in particular of 0.5 to 10 wt .-%, each based on the total weight of component (A.1).
  • the compound or the sum of the compounds B is preferably in an amount of from 0.01 to 20% by weight, particularly preferably from 0.01 to 15% by weight, very particularly preferably from 0.01 to 10 Wt .-%, in particular from 0.01 to 7 wt .-% and especially 0.01 to 5 wt .-%, based on the total weight of component A, before.
  • the composition according to the invention is preferably either an intimate mixture of components A and B or a solution or dispersion of components A and B in a suitable diluent.
  • the proportion of diluent is preferably from 5 to 95% by weight, more preferably from 30 to 80% by weight, in particular from 40 to 70% by weight, based on the total weight of the composition.
  • Suitable diluents are described below as component (C.3).
  • Reactive diluents are described as component (C.2).
  • the mixture according to the invention may contain, in addition to the components A and B, further mixing constituents which are selected from
  • thermosetting and / or radiation-curing aids (C.6) thermosetting and / or radiation-curing aids; (C.7) Substrate Wetting Agents; (C.8) wetting and dispersing aids; (C.9) water repellents; (C.10) bonding agents; and (C.1 1) scratch resistance improvers;
  • (V) at least one component E, which in turn is selected from light, heat and oxidation stabilizers.
  • the mixture according to the invention may contain commercially available photoinitiators.
  • photoinitiators are, for example, isobutyl benzoin ethers, 2,4,6-trimethylbenzoyldiphenylphosphine oxide, 1-hydroxycyclohexyl phenyl ketone, 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) -furan-1-one, mixtures of benzophenone and 1-Hydroxycyclohexyl phenyl ketone, 2,2-dimethoxy-2-phenylacetophenone, perfluorinated diphenyltitanocenes, 2-methyl-1- (4- [methylthio] phenyl) -2- (4-morpholinyl) -1-propanone, 2-hydroxy 2-methyl-1-phenylpropan-1-one, 4- (2-hydroxyethoxy) phenyl-2
  • Suitable commercial photo-initiators are for example those which are commercially available under the trade name Lucirin ®, Irgacure ® and Darocure ®.
  • the initiators Lucirin ® TPO, Irgacure ® 184, Irgacure ® 369, Irgacure ® 907 and Darocure ® be used 1 vorzugt loading 173rd
  • the photoinitiators are usually used in the proportion of about 0.5 to 5.0% by weight, based on the total weight of the liquid-crystalline mixture.
  • Reactive diluents are z. B. used as a polymerizable diluents in component te (A.4); they are then mandatory ingredient of the mixture according to the invention.
  • Reactive diluents are not only those substances which are to be designated as reactive diluents in the actual sense (group C.2.1), but also auxiliary compounds which contain one or more complementary reactive units, eg. As hydroxy or amino groups, via which a reaction with the polymerizable units of the liquid-crystalline compounds can be carried out (group C.2.2).
  • the substances of group (C.2.1), which are usually capable of photopolymerization, include, for example, mono-, bi- or polyfunctional compounds having at least one olefinic double bond.
  • examples of these are vinyl esters of carboxylic acids, such as.
  • methacrylic or acrylic acid esters of polyfunctional alcohols in particular those which in addition to the hydroxyl groups no further functional groups or possibly contain ether groups.
  • examples of such alcohols are, for. B. bifunctional alcohols, such as ethylene glycol, propylene glycol, and their higher-condensed representatives, such as. B.
  • diethylene glycol triethylene glycol, dipropylene glycol, tripropylene glycol, etc., butanediol, pentanediol, hexanediol, neopentyl glycol, alkoxylated phenolic compounds such as ethoxylated or propoxylated bisphenols, cyclohexanedimethanol, trifunctional and higher functional alcohols such as glycerol, trimethylolpropane, butantriol, trimethylolethane , Pentaerythritol, ditrimethylolpropane, dipentaerythritol, sorbitol, mannitol and the corresponding alkoxylated, in particular ethoxy- and propoxylated alcohols.
  • polyester (meth) acrylate these being the (meth) acrylic esters of polyesterols.
  • suitable polyesterols are those which can be prepared by esterification of polycarboxylic acids, preferably dicarboxylic acids, with polyols, preferably diols.
  • the starting materials for such hydroxyl-containing polyesters are known to the person skilled in the art.
  • dicarboxylic acids succinic acid, glutaric acid, adipic acid, sebacic acid, o-phthalic acid and their isomers and hydrogenation products, as well as esterifiable or transesterifiable derivatives of said acids, such as.
  • Suitable polyols are the abovementioned alcohols, preferably ethylene glycol, 1,2- and 1,3-propylene glycol, 1,4-butanediol, 1,6-hexanediol, neopentyl glycol, cyclohexanedimethanol and also polyglycols of the ethylene glycol and propylene glycol type.
  • reactive diluents of group (C.2.1) are 1, 4-divinylbenzene, triallyl cyanurate, acrylic esters of tricyclodecenyl alcohol of the formula below
  • .0-CO-CH CH 0 also known under the name Dihydrodicyclopentadienylacrylat, and the allyl esters of acrylic acid, methacrylic acid and cyanoacrylic acid.
  • the group (C.2.2) include, for example, di- or polyhydric alcohols, such as.
  • ethylene glycol, propylene glycol, and their higher condensed representatives for.
  • diethylene glycol triethylene glycol, dipropylene glycol, tripropylene glycol, etc.
  • group (C.2.2) also includes, for example, alkoxylated phenolic compounds, such as ethoxylated or propoxylated bisphenols.
  • Epoxy (meth) acrylates are, for.
  • such h-known in the art reaction of epoxidized olefins or poly- or diglycidyl ethers, such as bisphenol A diglycidyl ether, with (meth) acrylic acid are available.
  • Urethane (meth) acrylates are, in particular, reaction products of hydroxyalkyl (meth) acrylates with polyisocyanates or diisocyanates which are likewise known to the person skilled in the art.
  • Such epoxide or urethane (meth) acrylates are to be understood as "mixed forms" of the compounds listed under groups (C.2.1) and (C.2.2).
  • reactive diluents are used, their quantity and properties must be adapted to the respective conditions such that, on the one hand, a satisfactory desired effect, eg. B. the desired color of the mixtures according to the invention is achieved, on the other hand, however, the phase behavior of the liquid-crystalline mixture is not impaired too much.
  • a satisfactory desired effect eg. B. the desired color of the mixtures according to the invention is achieved, on the other hand, however, the phase behavior of the liquid-crystalline mixture is not impaired too much.
  • corresponding reactive diluents which have a relatively low (high) number of reactive units per molecule.
  • the reactive diluents are usually used in a proportion of about 0.5 to 20.0% by weight, based on the total weight of the liquid-crystalline mixture.
  • the components (A.1), (A.2) or (A.3) or mixtures according to the invention which contain these components may also contain polymerizable diluents in small amounts.
  • Preferred (A.1), (A.2) or (A.3) addition polymerizable solvents are acrylates, in particular higher-functional acrylates such as bis-, tris- or tetra-acrylates, particularly preferably high-boiling oligoacrylates.
  • the preferred additional amount is about 5 wt .-%, based on the total weight of the mixture.
  • C 1 -C 4 alcohols such as.
  • ethers 1, 2-ethylene glycol, 1, 2 or 1, 3-propylene glycol, 1, 2, 2,3 or 1, 4-butylene glycol, di- or triethylene glycol or di- or tripropylene glycol, ethers, eg. Example, open-chain ethers, such as methyl tert-butyl ether, 1, 2-ethylene glycol mono- or dimethyl ether, 1, 2-ethylene glycol mono- or diethyl, oxypropanol or 3-isopropoxypropanol, or cyclic ethers, such as tetrahydrofuran or dioxane, ketones, such as.
  • open-chain ethers such as methyl tert-butyl ether, 1, 2-ethylene glycol mono- or dimethyl ether, 1, 2-ethylene glycol mono- or diethyl, oxypropanol or 3-isopropoxypropanol, or cyclic ethers, such as tetrahydrofuran or dioxane, ketones, such as.
  • acetone methyl ethyl ketone, methyl isobutyl ketone or diacetone alcohol (4-hydroxy-4-methyl-2-pentanone), d-Cs-alkyl esters, such as.
  • methyl acetate, ethyl acetate, propyl acetate, butyl acetate or acetic acid amyl ester carboxylic acid amides such as dimethylformamide, N-heterocycles such as N-methylpyrrolidone, aliphatic or aromatic hydrocarbons such.
  • Example pentane, hexane, heptane, octane, isooctane, petroleum ether, toluene, xylene, ethylbenzene, tetralin, decalin, dimethylnaphthalene, white spirit, Shellsol® or Solvesso®, mineral oils such.
  • mineral oils such as gasoline, kerosene, diesel oil or fuel oil, but also natural oils, such as.
  • olive oil soybean oil, rapeseed oil, linseed oil or sunflower oil.
  • mixtures of these diluents are also suitable for use in the mixtures according to the invention.
  • these diluents can also be mixed with water.
  • C1-C4 alcohols eg.
  • glycols for.
  • B. 1, 2-ethylene glycol, 1, 2 or 1, 3-propylene glycol, 1, 2, 2,3 or 1, 4-butylene glycol, di- or triethylene glycol or di- or tripropylene glycol
  • ethers eg. For example, tetrahydrofuran or dioxane, ketones, z.
  • acetone, methyl ethyl ketone or diacetone alcohol (4-hydroxy-4-methyl-2-pentanone), or C 1 -C 4 alkyl esters such as.
  • methyl acetate, ethyl, propyl or butyl ester into consideration.
  • Such water-containing mixtures often have a limited miscibility with nonpolar diluents, such as.
  • nonpolar diluents such as.
  • mineral oils but also natural oils which then ternary (or quasi-ternary) diluents of water, with water at least partially miscible and immiscible with water diluents can be prepared and used.
  • Suitable diluents for the compounds of groups (A.1) or (A.2) are linear or branched esters, especially acetic acid esters, cyclic ethers and esters, alcohols, lactones, aliphatic and aromatic hydrocarbons, such as toluene, xylene and cyclohexane, and ketones , Amides, N-alkylpyrrolidones, especially N-methylpyrrolidone, and especially tetrahydrofuran (THF), dioxane and methyl ethyl ketone (MEK).
  • esters especially acetic acid esters, cyclic ethers and esters, alcohols, lactones, aliphatic and aromatic hydrocarbons, such as toluene, xylene and cyclohexane, and ketones .
  • Suitable diluents for the polymers of the group (A.3) are, in particular, ethers and cyclic ethers, such as tetrahydrofuran or dioxane, chlorinated hydrocarbons, such as dichloromethane, trichloromethane, carbon tetrachloride, dichloroethane, 1, 1, 2,2-tetrachloroethane, 1-chloronaph, enzol or 1, 2-dichlorobenzene.
  • chlorinated hydrocarbons such as dichloromethane, trichloromethane, carbon tetrachloride, dichloroethane, 1, 1, 2,2-tetrachloroethane, 1-chloronaph, enzol or 1, 2-dichlorobenzene.
  • Suitable diluents for cellulose derivatives are, for example, ethers, such as dioxane, or ketones, such as acetone.
  • the diluents are usually used in a proportion of about 0.5 to 10.0 wt .-%, preferably from about 1, 0 to 5.0 wt .-%, based on the total weight of the mixture according to the invention.
  • the proportion of diluent is preferably from 5 to 95% by weight, particularly preferably from 30 to 80% by weight and in particular from 40 to 70% by weight, based - conditions on the total weight of the mixture according to the invention.
  • defoamers and deaerators listed under component C, lubricants and flow aids (C.5), thermosetting or radiation-curing aids (C.6), substrate wetting aids (C.7), wetting and dispersing aids (C. .8), water repellents (C.9), primers (C.10) and scratch resistance improvers (C.11) are usually not strictly differentiated in their effect.
  • lubricants and flow control agents often additionally act as defoamers and / or deaerators and / or as aids to improving the scratch resistance.
  • Radiation-curing auxiliaries can in turn act as lubricants and flow aids and / or deaerators and / or as substrate wetting aids. In some cases, some of these aids can also fulfill the function of a primer (C.1.1). According to the above, therefore, a certain additive may be assigned to a plurality of groups (C.4) to (C.1.1) described below.
  • the defoamers of the group (C.4) are silicon-free and silicon-containing polymers.
  • the silicon-containing polymers are, for example, unmodified or modified polydialkylsiloxanes or branched copolymers,
  • the deaerators of group (C.4) include, for example, organic polymers, such as polyethers and polyacrylates, dialkyl, especially dimethylpolysiloxanes, organically modified polysiloxanes, such as arylalkyl-modified polysiloxanes or fluorosilicones.
  • organic polymers such as polyethers and polyacrylates
  • dialkyl especially dimethylpolysiloxanes
  • organically modified polysiloxanes such as arylalkyl-modified polysiloxanes or fluorosilicones.
  • the effect of defoaming agents is essentially based on preventing foaming or destroying already formed foam.
  • Air exhausters essentially act in such a way that they cause the coalescence of finely divided gas or air Blow to larger bubbles in the entlum, for example, the inventive mixtures, promote and thus accelerate the escape of the gas (the air).
  • auxiliaries are, for example, commercially available from Tego as TEGO® Foamex 800, TEGO® Foamex 805, TEGO® Foamex 810, TEGO® Foamex 815, TEGO® Foamex 825, TEGO® Foamex 835, TEGO® Foamex 840, TEGO® Foamex 842, TEGO® Foamex 1435, TEGO® Foamex 1488, TEGO® Foamex 1495, TEGO® Foamex 3062, TEGO® Foamex 7447, TEGO® Foamex 8020, Tego® Foamex N, TEGO® Foamex K 3, TEGO® Antifoam 2 18, TEGO® Antifoam 2-57, TEGO® Antifoam 2-80, TEGO® Antifoam 2-82, TEGO
  • the auxiliaries of the group (C.4) are usually present in a proportion of about 0.05 to 3.0 wt .-%, preferably from about 0.5 to 2.0 wt .-% based on the total weight of the liquid-crystalline Mixed used.
  • the group (C.5) of the lubricants and flow control agents typically include silicon-free but also silicon-containing polymers, such as.
  • silicon-free but also silicon-containing polymers such as.
  • polyacrylates or modified, low molecular weight polydialkylsiloxanes As polyacrylates or modified, low molecular weight polydialkylsiloxanes.
  • the modification is that a part of the alkyl groups is replaced by a variety of organic radicals. These organic radicals are, for example, polyethers, polyesters or else long-chain alkyl radicals, the former being used most frequently.
  • the polyether radicals of the correspondingly modified polysiloxanes are usually built up via ethylene and / or propylene oxide units. The higher the proportion of these alkylene oxide units in the modified polysiloxane, the more hydrophilic the resulting product is in general.
  • auxiliaries are commercially available, for example, from Tego as TEGO® Glide 100, TEGO® Glide ZG 400, TEGO® Glide 406, TEGO® Glide 410, TEGO® GIide 41 1, TEGO® Glide 415, TEGO® Glide 420, TEGO ® Glide 435, TEGO® Glide 440, TEGO® Glide 450, TEGO® Glide A 1 15, TEGO® Glide B 1484 (also usable as defoamer and deaerator), TEGO® Flow ATF, TEGO® Flow 300, TEGO® Flow 460, TEGO® Flow 425 and TEGO® Flow ZFS 460 available.
  • Tego TEGO® Glide 100, TEGO® Glide ZG 400, TEGO® Glide 406, TEGO® Glide 410, TEGO® GIide 41 1, TEGO® G
  • TEGO® Rad 2100, TEGO® Rad 2200, TEGO® Rad 2500, TEGO® Rad 2600 and TEGO® Rad products which are also available from Tego, can be used Insert 2700.
  • Such additives are available from BYK, for example, as BYK®-300 BYK®-306, BYK®-307, BYK®-310, BYK®-320, BYK®-333, BYK®-341, Byk® 354 and Byk® 361 available.
  • the auxiliaries of the group (C.5) are usually present in a proportion of about 0.05 to 3.0 wt .-%, preferably from about 0.5 to 2.0 wt .-% based on the total weight of the liquid-crystalline Mixed used.
  • the group (C.6) belong as radiation-curing aids especially polysiloxanes with terminal double bonds, which z. B. are part of an acrylate group.
  • Such adjuvants may be replaced by actinic or z. B. electron radiation for networking can be brought.
  • These tools usually combine several properties. In the uncrosslinked state, they can act as defoamers, deaerators, lubricants and flow aids and / or substrate wetting aids, in the crosslinked state they increase, above all, the scratch resistance, for example.
  • coatings or films which can be prepared with the mixtures of the invention. The improvement of the gloss behavior, z. B.
  • Radiation-hardening auxiliaries can be, for example, the TEGO® Rad 2100, TEGO® Rad 2200, TEGO® Rad 2500, TEGO® Rad 2600 and TEGO® Rad 2700 products available from Tego and the BYK® product available from BYK. 371.
  • Thermo-curing agents of the group (C.6) contain, for example, primary OH groups which react with isocyanate groups, for example. B. the binder can react.
  • Thermo-curing auxiliaries can be, for example, the BYK®-370, BYK®-373 and BYK®-375 products available from BYK.
  • the auxiliaries of the group (C.6) are usually present in a proportion of about 0.1 to 5.0 wt .-%, preferably from about 0.1 to 3.0 wt .-% based on the total weight of the liquid crystalline Mixed used.
  • auxiliaries of the group (C.7) of the substrate wetting aids serve above all to increase the wettability of the substrate, which is achieved, for example, by printing inks or laminating agents, eg. B. mixtures according to the invention, printed or coated to be the.
  • the generally associated improvement in the sliding and running behavior of such printing inks or coating compositions has an effect on the appearance of the finished (for example, crosslinked) print or the finished (for example, crosslinked) layer .
  • auxiliaries are commercially 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.
  • the auxiliaries of the group (C.7) are usually present in a proportion of about 0.05 to 3.0% by weight, preferably from about 0.1 to 1.5% by weight, based on the total weight of the liquid-crystalline Mixed used.
  • auxiliaries of the group (C.8) of the wetting and dispersing aids serve above all to prevent the floating out and floating as well as the settling of pigments and therefore, if necessary, are especially suitable for pigmented mixtures according to the invention.
  • auxiliaries stabilize pigment dispersions essentially by electrostatic repulsion and / or steric hindrance of the additized pigment particles, in which latter case the interaction of the auxiliary with the surrounding medium (eg binder) plays a greater role. Since the use of such wetting and dispersing aids, for. As is customary in the technical field of printing inks and paints, in the given case, the selection of such a suitable auxiliary agent usually presents no difficulties to the person skilled in the art.
  • Such wetting and dispersing aids are commercially available, for example, from the Tego company 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 as well as from Bbybyk®, Disperbyk®-107, Disperbyk®-108, Disperbyk® "10, Disperbyk® 1 1 1, Disperbyk® 1 15, Disperbyk® 130, Disperbyk ®-160, Disperbyk®-161, Disperbyk®-162, Disperbyk®-163, Disperbyk®-164, Disperbyk®-165, Disperbyk®-166, Disperbyk®-167, Disperbyk®-170, Disperby
  • the dosage of the auxiliaries of the group (C.8) depends mainly on the surface of the pigments to be coated and on the average molecular weight of the auxiliary.
  • inorganic pigments and low molecular weight auxiliaries it is customary to use a proportion of the latter of from about 0.5 to 2.0% by weight, based on the total weight, of pigment and auxiliaries. In the case of high molecular weight auxiliaries, the proportion increases to about 1.0 to 30% by weight.
  • the proportion of the latter is about 1.0 to 5.0% by weight, based on the total weight of pigment and auxiliaries.
  • this proportion can range from about 10.0 to 90 wt .-%.
  • preliminary tests are therefore recommended, which, however, can be accomplished by the skilled person in a simple manner.
  • the water repellents of group (C.9) can be used in view of the fact that, for example, prints or coatings produced with mixtures according to the invention obtain water-repellent properties. As a result, a swelling by water absorption and thus a change z. B. the optical properties of such prints or coatings are no longer possible or at least strongly suppressed. In addition, when using the mixtures z. B. as ink in offset printing prevent their water absorption or at least greatly curb.
  • hydrophobizing agents are, for example, from Tego as Tego® Phobe WF, Tego® Phobe 1000, Tego® Phobe 1000 S, 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.
  • the auxiliaries of the group (C.9) are in a proportion of about 0.05 to 5.0 wt .-%, preferably from about 0.1 to 3.0 wt .-% based on the total weight of the liquid-crystalline Mixed used.
  • Adhesion promoters of the group (C.10) serve to improve the adhesion of two contacting interfaces. From this it is directly apparent that essentially only the portion of the adhesion promoter is effective, which is located in one, the other or in both interfaces. If it is desired, for example, to apply liquid or pasty printing inks, coating materials or paints to a solid substrate, this generally means that either the latter can be added directly to the adhesion promoter or the substrate subjected to pretreatment with the adhesion promoters must (also called primer), d. H. that this substrate is given altered chemical and / or physical surface properties.
  • the substrate has been previously primed with a background color
  • the adhesion properties between the substrate and the underlying color but also between the underlying color and the printing ink or the coating or coating material play a role in the adhesion of the entire composite to the substrate.
  • the substrate wetting agents already listed under group (C.7) can also be mentioned, but these generally do not possess the same ability to mediate liability.
  • Bonding agents based on silanes 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,
  • M is titanium or zirconium and R, R 1 and R 2 are C 1 -C 4 -alkyl, such as. B. isopropyl or n-butyl.
  • R, R 1 and R 2 are C 1 -C 4 -alkyl, such as. B. isopropyl or n-butyl.
  • examples of such compounds are, for example, tetraisopropyl titanate, tetra-n-butyl titanate, titanium bis (acetylacetonate) diisopropoxide, titanium bis (acetylacetonate) dibutoxide, titanium bis (acetylacetonate) monobutanolate monopropanolate or titanium bis (acetylacetonate) -monoethanolat-monoisopropanolat.
  • titanium and zirconium compounds which can be used as adhesion promoters are n-butyl polytitanate, isopropyl triisostearoyl titanate, isopropyltris (N-ethylaminoethylamino) titanate and zirconium bis (diethyl citrate) diisopropoxide.
  • Such and other titanium and zirconium compounds are, for. B. under the brand name TYZOR® (Du Pont), Ken-React® (Kenrich Petrochemicals Inc.) and Tilcom® (Tioxide Chemicals) available.
  • As a primer zirconium aluminates can serve, as z. B. under the brand name Manchem® (Rhone Poulenc) are available.
  • chlorinated polyolefins for example obtainable from the companies Eastman Chemical and Toyo Kasei
  • polyesters for example from Hüls AG, BASF Aktiengesellschaft, Gebr. Borchers AG.
  • sucrose for example sucrose benzoate or sucrose toisobutyrate (the latter available, for example, from Eastman Chemical), phosphoric acid esters (for example from the Companies The Lubrizol Company and Hoechst AG available) and polyethyleneimines (eg available from BASF Aktiengesellschaft) and, for example, as adhesion-promoting additives in printing inks for flexographic, film and packaging printing rosin esters (eg from the company Robert Kraemer GmbH available)).
  • sucrose benzoate or sucrose toisobutyrate the latter available, for example, from Eastman Chemical
  • phosphoric acid esters for example from the Companies The Lubrizol Company and Hoechst AG available
  • polyethyleneimines eg available from BASF Aktiengesellschaft
  • adhesion-promoting additives in printing inks for flexographic, film and packaging printing rosin esters eg from the company Robert Kraemer GmbH available
  • the substrate to be printed or coated will be appropriately pretreated, i. H. use such additives as primers.
  • the manufacturers of such additives are usually required to obtain corresponding technical information or the expert can
  • the group (C.11) of the auxiliaries for improving scratch resistance includes, for example, the TEGO® Rad 2100, TEGO® Rad 2200, TEGO® Rad 2500, TEGO® Rad 2600 and TEGO products available from Tego and already mentioned above ® wheel 2700.
  • the quantities given in group (C.6) are also considered, i. H.
  • These additives are usually used in a proportion of about 0.1 to 5.0 wt .-%, preferably from about 0.1 to 3.0 wt .-% based on the total weight of the liquid-crystalline mixture.
  • dyes (D.1) examples include azo dyes, metal complex dyes, basic dyes such as di- and triarylmethane dyes and their salts, azomethine derivatives, polymethines, anthraquinone dyes and the like.
  • azo dyes include azo dyes, metal complex dyes, basic dyes such as di- and triarylmethane dyes and their salts, azomethine derivatives, polymethines, anthraquinone dyes and the like.
  • photochromic, thermochromic or luminescent dyes and also dyes which have a combination of these properties can also be added to the mixtures according to the invention.
  • Fluorescent dyes include, in addition to the typical fluorescent dyes, optical brighteners.
  • Q 1 are each C 1 -C 4 alkoxycarbonyl or cyano
  • Q 2 benzoxazol-2-yl which may be mono- or disubstituted by C 1 -C 4 alkyl, especially methyl or, Q 3 C 1 -C 4 alkoxycarbonyl, or 3- (C 1 -C 4 alkyl) -1,2,4-oxadiazol-3-yl.
  • optical brighteners from the class of benzoxazoles are, for example, those of the formulas
  • n is an integer value of 0 to 2.
  • Suitable optical brighteners from the class of coumarins have z.
  • Q 5 is C 1 -C 4 -alkyl and Q 6 is phenyl or 3-halopyrazol-1-yl, in particular 3-chloropyrazol-1-yl.
  • Q 7 is in each case C 1 -C 4 -alkoxy, in particular methoxy.
  • the above-mentioned brighteners can be used alone or mixed with one another.
  • optical brighteners are generally known and commercially available products. They are described, for example, in Ullmann's Encyclopedia of Industrial Chemistry, 5th Edition, Volume A18, pages 156 to 161, or can be obtained by the methods mentioned there.
  • the latter can be used as individual compounds, but also as a mixture of isomeric compounds.
  • optical brighteners are commercially available as Ultraphor® SF 004, Ultraphor® SF MO, Ultraphor® SF MP, and Ultraphor® SF PO from BASF.
  • the group (D.2) of the pigments includes both inorganic and organic pigments.
  • An overview of inorganic colored pigments which can be used in the mixtures according to the invention is given in the book by H. Endriß "A Meetinge anorganische Bunt-Pigmente” (publisher U. Zorll, Curt R. Vincentz Verlag Hannover 1997) and the book G. Buxbaum, "Industrial Inorganic Pigments", Wiley-VCH, Weinheim, 3rd edition 2005.
  • Pigment Black 6 and Pigment Black 7 carbon black
  • Pigment Black 1 1 iron oxide black, Fe 3 O 4
  • Pigment White 4 zinc oxide, ZnO
  • Pigment White 5 Lihopone, ZnS / BaSO 4
  • Pigment White 6 titanium oxide, TiO 2
  • Pigment White 7 Zinc sulfide, ZnS
  • pigments with luminescent properties come next to some organic, such as. B. Lumogen® Yellow 0790 (BASF Aktiengesellschaft), also inorganic, doped or undoped compounds in question, which are essentially on alkaline earth metal oxides, alkaline earth metal, alkaline earth metal / aluminum, alkaline earth metal / silicon or alkaline earth metal / phosphorus oxides, alkaline earth metal halides, Zn / silicon oxides, Zn / alkaline earth metal halides, rare earth metal oxides, rare earth metal / transition metal, rare earth metal / aluminum, Rare earth metal / silicon or rare earth metal / phosphorus oxides, rare earth metal oxide sulfides or oxide halides, zinc oxide, sulfide or selenide, cadmium oxide, sulfide or selenide or zinc / cadmium oxide, sulfide or selenide, the cadmium-containing compounds being their toxicological and ecological relevance lose importance.
  • the dopants used in these compounds are usually aluminum, tin, antimony, rare earth metals such as cerium, europium or terbium, transition metals such as manganese, copper, silver or zinc or else combinations of these elements.
  • luminescent pigments are given below, the notation “compound: element (s)” meaning the person skilled in the art that said compound is doped with the corresponding element (s).
  • compound element (s)
  • (P, V) means that corresponding lattice sites in the solid state structure of the pigment are statistically occupied by phosphorus and vanadium.
  • Examples of such compounds capable of luminescence are MgWO 4 , CaWO 4 , Sr 4 Ah 4 O 25 : Eu, BaMg 2 AliOO 27 : Eu, MgAlnO 19 : Ce, Tb, MgSiO 3 : Mn, Caio (PO 4 ) 6 (F , CI): Sb, Mn, (SrMg) 2 P 2 O 7 ) Eu, SrMg 2 P 2 O 7 ) Sn, BaFCl: Eu, Zn 2 Si0 4 : Mn,
  • suitable components E of the light, heat and / or oxidation stabilizers are alkylated monophenols, such as 2,6-di-tert-butyl-4-methylphenol, 2-tert-butyl-4,6-dimethylphenol, 2 , 6-di-tert-butyl-4-ethylphenol, 2,6-di-tert-butyl-4-n-butylphenol, 2,6-di-tert-butyl-4-isobutylphenol, 2,6-dicyclopentyl-4 -methylphenol, 2- ( ⁇ -methylcyclohexyl) -4,6-dimethylphenol, 2,6-dioctadecyl-4-methylphenol, 2,4,6-tricyclohexylphenol, 2,6-di-tert-butyl-4-methoxymethylphenol , Nonylphenols which have a linear or branched side chain, for example 2,6-dinonyl-4-methylphenol, 2,4-dimethyl-6
  • 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-hydroxyphenyl stearate and bis (3,5-di-tert-butyl-4-hydroxyphenyl) adipate, tocopherols such as ⁇ -tocopherol, ⁇ -tocopherol, ⁇ -tocopherol, ⁇ -tocopherol and mixtures of these compounds, as well as tocopherol derivatives such as Toco pheryl a
  • Alkylidene bisphenols such as 2,2'-methylenebis (6-tert-butyl-4-methylphenol), 2,2'-methylenebis (6-tert-butyl-4-ethylphenol), 2,2'-methylenebis [4-methylphenol) 6- ( ⁇ -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- ( ⁇ -methylbenzyl) -4-nonylphenol], 2,2'-methylenebis [6- ( ⁇ , ⁇ -dimethylbenzyl) -4-nonylphenol], 4,4
  • O-, N- and S-benzyl compounds such as 3,5,3 ', 5'-tetra-tert-butyl-4,4'-dihydroxydibenzyl ether, octadecyl-4-hydroxy-3,5-dimethylbenzylmercaptoacetate, tridecyl-4 hydroxy-3,5-di-tert-butylbenzylmercaptoacetate, tris (3,5-di-tert-butyl-4-hydroxybenzyl) -amine, bis (4-tert-butyl-3-hydroxy-2,6- dimethylbenzyl) dithioterephthalate, bis (3,5-di-tert-butyl-4-hydroxybenzyl) sulfide and isooctyl-3,5-di-tert-butyl-4-hydroxybenzyl mercaptoacetate, aromatic hydroxybenzyl compound,, 5-tris (3,5-di-tert-butyl-4-hydroxybenzyl
  • Triazine compounds such as 2,4-bis (octylmercapto) -6- (3,5-di-tert-butyl-4-hydroxyanilino) -1,3,5-triazine, 2-octylmercapto-4,6-bis (3,5 -di-tert-butyl-4-hydroxyanilino) -1, 3,5-triazine, 2-octylmercapto-4,6-bis (3,5-di-tert-butyl-4-hydroxyphenoxy) -1, 3.5 triazine, 2,4,6-tris (3,5-di-tert-butyl-4-hydroxyphenoxy) -1, 2,3-triazine, 1, 3,5-tris (3,5-di-tert-butyl) butyl-4-hydroxybenzyl) isocyanurate, 1,3,5-tris (4-tert-butyl-3-hydroxy-2,6-dimethylbenzyl) isocyanurate, 2,4,6-
  • Acylaminophenols such as 4-Hydroxylauroylanilid, 4-hydroxystearoylanilide and octyl-N- (3,5-di-tert-butyl-4-hydroxyphenyl) carbamate, propionic and acetic acid esters, for example of mono- or polyhydric alcohols such as methanol, ethanol, n-octanol , Isooctanol, 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) oxamide, 3-thiaundecanol, 3-thiapentadecano
  • Propionic acid amides 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,
  • vitamin C Ascorbic acid (vitamin C) and ascorbic acid derivatives such as ascorbyl palmitate, laurate and stearate, and ascorbyl sulfate and phosphate, antioxidants based on amine compounds such as N, N'-di-isopropyl-p-phenylenediamine, N, N'- Di-sec-butyl-p-phenylenediamine, N, N'-bis (1, 4-dimethylpentyl) -p-phenyl-endiamine, 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-pheny
  • Phosphites and phosphonites such as triphenyl phosphite, diphenyl alkyl phosphite, phenyldi- alkyl phosphite, tris (nonylphenyl) phosphite, trilauryl phosphite, trioctadecyl phosphite, distearyl phthaloerythritol diphosphite, tris (2,4-di-tert-butylphenyl) phosphite, diisodecyl pentaerythritol diphosphite, bis (2,4-di-tert-butylphenyl) phosphite tert-butylphenyl) pentaerythritol diphosphite,
  • esters of 3,3'-thiodipropionic acid for example the lauryl, stearyl, myristyl or tridecyl ester, mercaptobenzimidazole or the zinc salt of 2-mercaptobenzimidazole, zinc dibutyl dithiocarbamate, dioctadecyl disulfide and pentaerythritol tetrakis ( ⁇ -dodecylmercapto) propionate, 2-hydroxybenzophenones such as 4-hydroxy, 4-methoxy, 4-octyloxy, 4-decycloxy, 4-dodecyloxy, 4-benzyloxy, 4,2 ', 4'-trihydroxy and 2'-hydroxybenzophenones;Hydroxy-4,4'-dimethoxy derivatives,
  • Esters of unsubstituted and substituted benzoic acid for example 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 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-butylbenzoate.
  • butylphenyl 3,5-di-tert-butyl-4-hydroxybenzoate
  • Acrylates such as, for example, ethyl- ⁇ -cyano- ⁇ , ⁇ -diphenyl acrylate, isooctyl- ⁇ -cyano- ⁇ , ⁇ -diphenyl acrylate, methyl ⁇ -methoxycarbonyl cinnamate, methyl ⁇ -cyano- ⁇ -methyl-p-methoxycinnamate, butyl ⁇ cyano-.beta.-methyl-p-methoxy-cinnamate and methyl-.alpha.-methoxycarbonyl-p-methoxycinnamate, sterically hindered amines such as bis (2,2,6,6-tetramethylpiperidin-4-yl) sebacate, bis (2 , 2,6,6-tetramethylpiperidin-4-yl) succinate, bis (1, 2,2,6,6-pentamethylpiperidin-4-yl) sebacate, bis (1-octyloxy-2,2,6,6 tetramethylpiperidin
  • Coating agents are to be understood as meaning all formulations of the mixture according to the invention which are suitable for applying the mixture to substrates.
  • coating compositions contain, in addition to the components A and B, at least one auxiliary which is preferably selected from the additives described above as components C, D and E, eg. From solution / thinning agents, photoinitiators, leveling agents and the like.
  • the coating agents may contain various auxiliaries which are known to the person skilled in the art as suitable for the respective type of coating agent.
  • auxiliaries are described, for example, in Ullmann's Encyclopedia of Industrial Chemistry, Chapter “Paints and Coatings” and “Printing Inks", 6th edition, Electronic Release, 2000, Wiley-VCH, to which reference is hereby made in its entirety.
  • the coating composition preferably contains at least one diluent and / or at least one photoinitiator and, if appropriate, at least one further additive which is selected from the components C, D and E described above.
  • coating compositions according to the invention are printing inks and coatings.
  • Printing inks and paints usually contain, in addition to the components A and B according to the invention, at least one auxiliary agent.
  • Suitable adjuvants are known to the person skilled in the art and are described, for example, in Ullmann's Encyclopedia of Industrial Chemistry, Chapter “Paints and Coatings” and "Printing Inks", 6th edition, Electronic Release, 2000, Wiley-VCH, to which reference is hereby made in its entirety becomes.
  • the auxiliaries are preferably selected from components C, D and E described above.
  • An object of the present invention relates to printing inks containing the inventive mixture.
  • Printing inks usually contain binders and usual auxiliaries in addition to their own. Suitable binders and auxiliaries are those which are used in customary printing inks and are described in the literature cited above and in part also above in the case of components C, D and E.
  • component A of the mixture according to the invention itself has binder properties, it is not absolutely necessary for the printing ink according to the invention to add further binders.
  • the printing ink according to the invention preferably contains at least one diluent and / or at least one photoinitiator and optionally at least one further additive selected from the above-described components C, D and E, e.g. B. at least one leveling agent.
  • the printing inks according to the invention are preferably used in through, flat or high-pressure processes.
  • Another object of the present invention is the use of the inventive liquid-crystalline mixtures and their preferred embodiments for printing or coating substrates.
  • Textile, leather or jewelry sector the decorative area, the gift article area, the field of writing utensils, the packaging materials sector, the construction and household sector, the field of printed matter, the cosmetic or even the medical field in question.
  • Examples of such substrates / articles are cardboard boxes, packaging, textile and plastic carrier bags, papers, labels, plastic films, vehicles of any kind, such as children's vehicles, bicycles, motorcycles, passenger and cargo vehicles, passenger and goods Lorries and related vehicle / aircraft and vehicle / aircraft accessories, entertainment electronics and data processing equipment and in particular housings of such equipment, roller skates, in-line skaters, skis, (wind) surfboards, kites, medical devices and eyeglass frames.
  • the use of the liquid-crystalline mixtures according to the invention and their preferred embodiments for the production of films or coatings which selectively reflect light in the wavelength range from 250 to 750 nm is claimed.
  • the reflection of ultraviolet light should also be mentioned here. This can serve, for example, for protecting the substrates provided with such films or coatings against UV radiation.
  • liquid-crystalline mixtures according to the invention and their preferred embodiments in electro-optical components is claimed.
  • low-crosslinking or low-crosslinking mixtures according to the invention can be used as liquid-crystalline matrices, for example. B. in liquid crystal displays and screens.
  • the mixtures according to the invention are also suitable as orientation layers in such displays and screens.
  • component A may alternatively or additionally reflect in the IR spectral range.
  • the property of component A, (also) to reflect in the IR wavelength range is due to the fact that after orientation and curing of component A at least a portion of the oriented, by polymerization of the monomers (A.1) or (A. 2) available cholesteric polymers or at least a portion of the oriented polymers
  • (A.3) or (A.4) have a pitch of the helical superstructure which corresponds to a wavelength in the IR spectral range.
  • component A may alternatively or additionally reflect in the IR spectral range.
  • the counterfeit-proof items to be marked include, for example, banknotes, stocks and other securities, check or credit cards, identity cards, admission tickets and coupons, but also packaging of high-priced luxury foods, pharmaceuticals and luxury goods or such luxury goods themselves The latter is aimed at preventing or at least hindering brand piracy.
  • the invention also provides forgery-proof markings (also called securing features or security marking) which are produced from the mixture according to the invention.
  • the securing feature according to the invention contains, via component B, if it is chosen such that it absorbs in the invisible spectral range, ie in the UV or in the IR, hidden detectable features which can be detected spectrometrically (eg by IR, UV and / or IR). or fluorescence spectrometry) can be detected, e.g. B. as a defined absorption in the IR or UV range, preferably in the NIR range, and / or as defined fluorescence in the IR or UV range, preferably in the NIR range.
  • the counterfeit-proof marking according to the invention contains only hidden elements; ie the reflection wavelength of component A is outside the visible spectral range, z. B. in UV or IR.
  • the tamper-resistant markings produced from the liquid-crystalline mixture according to the invention can of course be combined with numerous other security features.
  • a substrate which has been coated with a liquid-crystalline mixture according to the invention can be equipped with further layers which contain safety features.
  • further layers are layers which are provided with fluorescent, IR-transparent and / or IR-absorbing or remitting substances, magnetically and / or electrically active layers, thermochromic layers, fluorescent layers and layers, the markers included, such as As DNA tags, nanotubes or biomarkers.
  • the present invention furthermore relates to polymers or polymerized films which can be obtained by polymerization of the liquid-crystalline mixtures according to the invention and their preferred embodiments.
  • the present invention additionally provides a process for printing or coating substrates, comprising the following steps: (i) applying a composition according to the invention to the substrate and, if appropriate, orienting the mixture on the substrate; and
  • the application of the mixture according to the invention to the substrate can be carried out by customary methods, for example by means of processes selected from air knife coating, knife coating, air knife coating, squeeze coating, impregnation coating, reverse roll coating, transfer roll coating, gravure coating, kissing Coating, casting coating, spray coating, spin coating or printing processes, such as gravure, gravure, intaglio, flexo, offset, inkjet, book, tampon, heat seal or screen printing processes.
  • printing processes within the meaning of the invention are also those in which the coating composition is applied to a substrate, for example by application of a ballpoint pen or a fountain pen.
  • the applied layer Before curing, the applied layer can be oriented. Although the orientation of the cholesteric layer usually takes place spontaneously during the application process, it can also take place in a subsequent step. In this case, the orientation is carried out by known methods, for. As the interaction of the coated layer with orientation layers, the application of electrical or magnetic fields or the mechanical doctoring of the liquid crystal layers. However, the orientation preferably takes place spontaneously under the action of the shear forces which occur during application.
  • the applied layer can be dried by conventional methods, for example with hot air.
  • the layer can preferably be oriented again mechanically, for example by means of a smooth roll or a relief roll, a roll, by compressed air or by plushes, shortly before complete drying.
  • At least one further non-liquid-crystalline print or at least one further non-liquid-crystalline layer may be applied to the substrate before or after the application of the mixture (step (i-1)).
  • at least one absorption layer and / or a protective layer and / or an optionally thermally activatable adhesive layer can be applied (step (i-2))
  • Curing (step (N)) may be carried out either by applying each individual pressure or layer of steps (i) and optionally (i-1) and / or (i-2) or simultaneously.
  • the polymerization of the cholesteric layer can be effected thermally, by electron beam or preferably photochemically.
  • the cholesteric layer can be provided with a transparent protective layer, a so-called topcoat.
  • a transparent protective layer a so-called topcoat.
  • Suitable topcoats are described, for example, in WO 03/064559, to which reference is hereby fully made.
  • the coating can be carried out in certain substrates, in particular leather and plastic, but also in all other of the aforementioned substrates, also in the transfer process. Suitable transfer processes and transfer films used are described, for example, in WO 03/064559, to which reference is hereby fully made.
  • the substrates are suitably treated prior to coating or printing, in particular in order to improve their adhesion properties and / or wetting properties and / or orientation properties.
  • the substrates are pretreated in such a way that the surface is as closed as possible, less absorbent and smooth.
  • Adhesion promoters which have already been listed by way of example among the additives of the group (C.10) (priming of the substrates) are suitable for improving the adhesion properties.
  • substrate wetting aids are suitable with which the substrate can be pretreated accordingly and which have already been listed by way of example under the additives of group (C.7).
  • the adhesion and wetting properties of the substrates can also be improved by any form of physicochemical activation.
  • An improvement in the orientation of the substrates relative to the liquid-crystalline mixtures according to the invention and their preferred embodiments can be achieved, for example, by mechanical or chemical modification of the substrate surface, e.g. B. by stretching, grinding, dissolving, etching or plasma treatment.
  • the present invention relates to a previously mentioned analogous method for printing or coating substrates which are at least partially permeable in the wavelength range from 250 to 1300 nm.
  • Such printed or coated substrates prepared according to the method are referred to below as composites for the sake of simplicity.
  • the method according to the invention is not to be understood as meaning that in all method steps (i) and optionally (i-1) only prints or only layers are applied, but also that prints and layers occur alternately or in any desired sequence and number the substrates can be applied.
  • the former method relates above all to the production of composites, their properties in supervision, the latter method to the production of composites, their properties in plan view or in review (ie the corresponding substrates are in the wavelength range of 250 to 1300 nm at least partially permeable) should come into effect.
  • liquid-crystalline mixtures according to the invention to the substrates and, if appropriate, subsequently to at least one further non-liquid-crystalline print or at least one further non-liquid-crystalline layer or to bring the latter first onto the substrate and then coated or printed with the liquid-crystalline mixture (s).
  • the composite produced according to the invention is to be used as a laminating film, then in the laminated product the (at least partially transparent) substrate of the composite itself forms the outermost layer, the application of a protective layer (process step (i-2)) is not absolutely necessary ,
  • the composite can also be in the g that, for example, between the in the wavelength range of 250 to 1300 nm at least partially transparent substrate and the liquid-crystalline mixture, a release layer is applied, which, after application of the composite with the side facing away from the substrate on a further substrate, a detachment of the (now outer) first substrate allows.
  • This can be z. B. accomplish in the context of a hot stamping process (see above-mentioned transfer method).
  • the application of a release layer may optionally be dispensed with.
  • the (first) substrate can be removed directly after application to the further substrate.
  • the composite contains colored liquid-crystalline mixtures, it is possible to apply an absorption layer to reinforce or vary the hue. If this composite z. B. used as laminating for dark colored articles, so not only the application of a protective layer but also a corresponding absorption layer (step (i-2)) can be omitted.
  • Curing may be carried out immediately following each application according to steps (i) and optionally (i-1) and / or (i-2) or, if appropriate measures such.
  • the substrates to be printed or coated can be monochromatic or multicolored precoated.
  • substrates which are magnetic, electrically conductive, photochromic, thermochromic or luminescent or have a combination of these properties.
  • the substrates may possess the stated properties per se (bulk or bulk properties).
  • these properties can also be achieved by mixing (for example doping) corresponding substances (for example magnetic, electrically conductive, photochromic, thermochromic or luminescent pigments or photochromic, thermochromic or luminescent dyes) or by coating. printing, printing or vapor deposition of medium-term printing inks, coating or vaporization agents.
  • a fluorescent plastic film (eg colored with fluorescent dyes or pigments in bulk) may additionally be printed with a magnetic or electrically conductive printing ink or paste or vapor-coated with a metal layer.
  • the substrates are monochromatically or multicoated precoated, improved by suitable pretreatment in their adhesion properties and / or wetting properties and / or orientation properties or imparted by coating, printing or vapor deposition magnetic, electrically conductive, photochromic, thermochromic and / or luminescent properties if these pretreatments are to be understood as belonging to the substrate and not in the sense of a process step (i-1), provided that this is carried out before process step (i).
  • These inks or coating compositions are based on common binders and solvents and usually still contain (effect) dyes and / or pigments, such as. B. such already mentioned above substances of groups (D.1) and (D.2).
  • absorption and / or protective layers may optionally also be applied.
  • coating compositions are in turn based on customary binders and solvents and generally contain absorbing dyes and / or pigments and usually also additives which give these absorption and / or protective layers, for example, increased scratch resistance (see, for example, those already described above counteract the listed additives of group (C.1.1)) or the degradation of these layers caused by light, heat and / or oxidation (eg the additives of component E already mentioned above).
  • Particularly advantageous composites, z. B. with regard to the provision of tamper-proof markers, can be prepared by applying in step (i) photochemically polymerizable liquid crystalline mixtures of the invention on substrates (such as plastic films of polyethylene terephthalate), polymerized by UV light, optionally in step (i- 1) further prints or layers applied, which z.
  • substrates such as plastic films of polyethylene terephthalate
  • step (i- 1) further prints or layers applied, which z.
  • step (i- 1) further prints or layers applied, which z.
  • IR or UV-absorbing or de dyes or pigments contained optionally (optionally after curing of these prints or layers) applies a final absorption layer.
  • coating methods for the liquid-crystalline mixtures and other non-liquid-crystalline layers can also be full-tone printing processes, such as flexographic, screen or offset printing.
  • the present invention furthermore relates to substrates to which liquid-crystalline mixtures according to the invention and their preferred embodiments or polymers or polymerized films obtained therefrom are applied or which are coated according to the processes of the invention.
  • the invention furthermore relates to pigments which contain the mixture according to the invention in hardened form.
  • pigments are obtainable, for example, by applying the mixture to a support, optionally orienting it, optionally drying it, curing it, detaching the hardened layer from the support and then comminuting it to the desired pigment size.
  • the invention also relates to the use of the pigments according to the invention in optical filters, polarizers, decorating means, electro-optical components, counterfeit-proof markings and / or reflection media for the selective reflection of radiation in the wavelength range from 250 to 750 nm.
  • the invention relates to coating compositions which contain these pigments.
  • the coating compositions as a rule contain further components (auxiliaries). Suitable auxiliaries are known to the person skilled in the art for the respective type of coating composition and are described, for example, in Ullmann's Encyclopedia of Industrial Chemistry, Chapter “Paints and Coatings” and “Printing Inks", 6th edition, Electronic Release, 2000, Wiley-VCH, which is hereby incorporated by reference Full reference is made. With respect to suitable and preferred components of the coating compositions, these in addition to the inventive Pigments is also referenced embodiments, it being understood that z. B. photoinitiators are not included.
  • coating compositions according to the invention are printing inks and coatings.
  • Printing inks and paints usually contain, in addition to the pigments of the invention, at least one auxiliary agent.
  • Suitable auxiliaries are known to the person skilled in the art and are described, for example, in Ullmann's Encyclopedia of Industrial Chemistry, Chapter “Paints and Coatings” and "Printing Inks", 6th edition, Electronic Release, 2000, Wiley-VCH Reference is made.
  • the auxiliaries are preferably selected from components C, D and E described above.
  • the coating compositions according to the invention contain, in addition to the pigments according to the invention, at least one diluent and optionally at least one leveling agent.
  • the combination according to the invention of a liquid-crystalline component (A) with a radiation-absorbing polycyclic compound (B) markedly increases the brilliance of the color shift of the applied, optionally oriented and cured liquid-crystalline mixture in comparison with corresponding compositions which do not contain component B. even if the polycyclic compound B has no absorption band in the visible spectral range.
  • the mixture according to the invention makes it possible to produce counterfeit-proof markings with invisible elements in a simplified manner.
  • the doctoring RV1 to RV3 and R1 to R5 were measured colorimetrically.
  • the squeegees were fixed on a black glass and measured with a goniometric spectrophotometer GKR 311 (Zeiss) depending on the angle.
  • the difference Angle between angle and angle is kept constant at 10 ° while the angle of illumination is changed in 5 ° increments.
  • RV1 and R1 show an angle-dependent color shift from green in a blue to oblique view.
  • the doctoring R1 according to the invention shows a much more brilliant color shift than the comparative doctoring RV1.
  • RV1 and R2 show an angle-dependent color shift from green in blue to blue in oblique view.
  • the doctoring R2 according to the invention shows a much more brilliant color shift than the comparative doctoring RV1.
  • RV2 and R3 show an angle-dependent color shift from red in plan to green in oblique view.
  • the doctoring R3 according to the invention shows a much more brilliant color shift than the comparative doctoring RV2.
  • RV2 and R4 show an angle-dependent color shift from red in plan view to green in oblique view.
  • the doctoring R4 according to the invention shows a much more brilliant color shift than the comparative doctoring RV2.
  • RV3 and R5 show no angle-dependent color shift, as the liquid-crystalline mixture was adjusted so that the "color shift" is completely concealed from top to bottom in the UV spectrum.

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  • Chemical & Material Sciences (AREA)
  • Crystallography & Structural Chemistry (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Organic Chemistry (AREA)
  • Paints Or Removers (AREA)

Abstract

La présente invention concerne un mélange de cristaux liquides, comprenant au moins un composant A durcissable, réfléchissant dans la gamme des longueurs d'onde UV et/ou visibles, qui contient au moins un monomère polymérisable nématique achiral en combinaison avec au moins un monomère polymérisable chiral ; au moins un monomère polymérisable cholestérique ; au moins un monomère réticulable cholestérique et/ou au moins un polymère choléstérique dans un agent de dilution polymérisable, et comme composant B, au moins un composé polycyclique conjugué absorbant un rayonnement et le cas échéant, fluorescent. De plus, l'invention concerne l'utilisation de tels mélanges pour le revêtement et l'impression de substrats, dans des encres d'impression, dans des éléments électrooptiques et/ou pour le marquage anti-fraude d'objets. L'invention a également pour objet des polymères ou des films polymérisables, qui sont obtenus par polymérisation des mélanges suivant l'invention, et leur utilisation comme filtres optiques, polariseurs, agents de décoration, agents de marquage anti-fraude ou agents de réflexion dans la gamme de longueurs d'onde visibles ; ainsi qu'un procédé pour l'impression ou le revêtement de substrats, et les substrats, qui sont accessibles par ce procédé, les pigments, qui contiennent le mélange suivant l'invention sous forme durcie, et les agents de revêtement, qui contiennent les pigments suivant l'invention.
PCT/EP2007/057588 2006-07-24 2007-07-23 Mélange de cristaux liquides WO2008012292A1 (fr)

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EP06117754 2006-07-24

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WO2011132137A1 (fr) 2010-04-20 2011-10-27 Basf Se Films polymérisés avec texture de lignes ou texture en empreintes digitales
US9222024B2 (en) 2010-04-20 2015-12-29 Basf Se Polymerized films with line texture or fingerprint texture
EP2937402A4 (fr) * 2013-06-21 2016-11-16 Huizhou Foryou Optical Technology Co Ltd Composition de cristaux liquides
WO2019206846A1 (fr) 2018-04-25 2019-10-31 Basf Se Procédé de production de films de cristaux liquides à forte adhérence, sur des substrats flexibles
WO2020064522A1 (fr) 2018-09-24 2020-04-02 Basf Se Composition photodurcissable destinée à être utilisée en impression 3d
WO2020064523A1 (fr) 2018-09-24 2020-04-02 Basf Se Composition durcissable par uv destinée à être utilisée dans une impression 3d
EP3680274A1 (fr) 2019-01-14 2020-07-15 Basf Se Prépolymères d'acrylate d'hydroxyuréthane (meth) à utiliser en impression 3d
EP3680263A1 (fr) 2019-01-14 2020-07-15 Basf Se (méth)acrylates à base de limonène pour l'impression 3d
WO2021032518A1 (fr) 2019-08-19 2021-02-25 Basf Se Procédé de production de films de cristaux liquides exempts de texture d'empreinte digitale

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CN102124079A (zh) * 2008-06-17 2011-07-13 巴斯夫欧洲公司 绝热膜和层压材料
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EP2937402A4 (fr) * 2013-06-21 2016-11-16 Huizhou Foryou Optical Technology Co Ltd Composition de cristaux liquides
EP2937402B1 (fr) 2013-06-21 2020-11-18 Huizhou Foryou Optical Technology Co. Ltd. Utilisation d'une composition de cristaux liquides comme encre ou colorant
WO2019206846A1 (fr) 2018-04-25 2019-10-31 Basf Se Procédé de production de films de cristaux liquides à forte adhérence, sur des substrats flexibles
WO2020064523A1 (fr) 2018-09-24 2020-04-02 Basf Se Composition durcissable par uv destinée à être utilisée dans une impression 3d
WO2020064522A1 (fr) 2018-09-24 2020-04-02 Basf Se Composition photodurcissable destinée à être utilisée en impression 3d
US11999865B2 (en) 2018-09-24 2024-06-04 Basf Se UV curable composition for use in 3D printing
EP3680274A1 (fr) 2019-01-14 2020-07-15 Basf Se Prépolymères d'acrylate d'hydroxyuréthane (meth) à utiliser en impression 3d
EP3680263A1 (fr) 2019-01-14 2020-07-15 Basf Se (méth)acrylates à base de limonène pour l'impression 3d
WO2020148189A1 (fr) 2019-01-14 2020-07-23 Basf Se (méth)acrylates à base de limonène destinés à être utilisés dans une impression 3d
WO2020148190A1 (fr) 2019-01-14 2020-07-23 Basf Se Prépolymères de (méth)acrylate d'hydroxyuréthane destinés à être utilisés dans l'impression 3d
WO2021032518A1 (fr) 2019-08-19 2021-02-25 Basf Se Procédé de production de films de cristaux liquides exempts de texture d'empreinte digitale

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