Patent Application
20250050668
The present invention relates to terrylene diimides which are substituted in the skeleton and their homologous quaterrylene diimides. The present invention also relates to the use of these compounds, especially their use in an ink formulation for security printing applications.
Visible light absorbers and infrared (IR) light absorbers meet a significant technical need in a wide range of applications, such as security printing (bank notes, credit cards, identity cards, passports etc.), invisible and/or IR readable barcodes and specifically fluorescent barcodes (when the visible light absorbers and IR light absorbers show fluorescence), the laser-welding of plastics, the curing of surface-coatings using IR radiators, the drying and curing of prints, the fixing of toners on paper or plastics, optical filters for PDPs (plasma display panels), laser marking e.g. of paper or plastics, the heating of plastics preforms or heat shielding applications.
To prevent counterfeiting, marking is currently extensively used for the recogni-tion, identification and authentication of individual items. The application of markings is frequently carried out by a printing process which uses a printing ink with specific optical properties that are imparted to the ink by one or more substances contained therein such as, e.g., fluorescent dyes or pigments emitting in the IR wavelength range of the electromagnetic spectrum that can be detected upon excitation with an activating light of a suitable excitation wavelength spectrum; and/or colorless or barely colored IR absorbers that can be detected under IR light.
A further important application of IR absorbing dyes and fluorescent dyes is in liquids, especially fuel oils such as mineral oils, as marker. In this way, heating oil, which usually enjoys tax privileges, can be differentiated from the generally more highly taxed diesel oil.
A substance class which is suitable for marking purposes are the higher rylene-tetracarboximides, especially terrylenebis(dicarboximides) (also referred to as terrylene diimides) and quaterrylenebis(dicarboximides) (also referred to as quaterrylene diimides) because of their stability and strong absorption in the long-wavelength red and near-infrared region of the electromagnetic spectrum. The terrylenebis(dicarboximides) absorb electromagnetic radiation mainly in the visible range and generally emit at from 690 to 780 nm, while the higher rylene homolog quaterrylenebis(dicarboximides) principally have an absorption in the near infrared (NIR) and some of them also emit in the NIR. The representatives of this substance class may be substituted on the terrylene and quaterrylene core, respectively, by phenyl, phenoxy or thiophenoxy substituents which in turn may be monosubstituted, for example by tert-alkyl, or disub-stituted, for example by alkyl containing up to 4 carbon atoms.
WO 2007/099059 describes inter alia the use of terrylene and quaterrylene diimides that are substituted in the skeleton by alkyl-substituted phenoxy radicals as marker for liquids, especially oils such as mineral oils.
WO 2007/031446 describes fluorescence solar conversion cells based on aryloxy substituted terrylene dyes.
WO 2020/193309 describes the use of aryloxy-substituted terrylene diimides as wavelength conversion material for agriculture.
None of these documents describes terrylene or quaterrylene diimide compounds having the characteristic substituents attached at the skeleton as claimed in the present invention.
The performance of these terrylene and quaterrylene colorants is not always sat-isfactory. In particular, they often suffer from one or more of the following drawbacks: low solubility or dispersibility in liquid media such as those which are useful in printing inks—this low solubility/dispersibility limits the suitability of terrylene and quaterrylene compounds as colorants for liquids in general, also making the colorants unsuitable for detection —; low fluorescence quantum yield and/or low molar extinction coefficient, resulting in the article appearing more colored; loss of fluorescent properties by agglom-eration of fluorescent sites (quenching).
Further, for use in the field of security printing, it would be advantageous to provide a security image on an item requiring a security image which could be detected at wavelengths in the range from 690 to 1000 nm and in which a strongly coloured image is not created by the compound(s) utilised.
It was an object of the present invention to provide substituted terrylene diimides and quaterrylene diimides which have advantageous application properties and can be incorporated efficiently into the particular application medium. Preferably, the novel terrylene diimides and quaterrylene diimides should fulfil at least one of the following criteria:
It was surprisingly found that these and further objectives are achieved by the compounds of formula (I) as defined herein below.
Thus, in a first aspect, the invention relates to a compound of formula (I)
The compounds of formula (1) are substituted in the ring system either by aryloxy radicals substituted by one alkyl radical containing 6 to 20 carbon atoms and at least one further alkyl radical containing up to 20 carbon atoms, or they are substituted in the ring system by aryl radicals substituted by at least one alkyl radical having 5 to 20 carbon atoms, thereby rendering the compounds of formula (1) dispersible or soluble in a given application medium. The compounds of formula (1) are new, show a very strong absorbance in the wavelength range of from 690 to 1000 nm and fulfil at least one, preferably two, three, four or more than four of the above-mentioned criteria (ii) to (xi).
Thus, a further aspect of the present invention relates to the use of the compound of formula (1) as defined above and in the following in security printing, for coloring coatings, printing inks including printing inks for 3D printing and plastics, for data storage, for optical labels, for security labels in documents and for brand protection, for solar collectors, for optical waveguides, for the laser welding of plastics or as a fluorescent label for biomolecules.
A further aspect of the present invention relates to an article comprising at least one fluorescent film layer, the film layer comprising in a polymeric matrix the compound of formula (1) as defined above and in the following.
A further aspect of the present invention relates to a printing ink for security printing, comprising
A further aspect of the invention relates to a security document, comprising a substrate and the compound of formula (1) as defined above and in the following.
A further aspect of the invention relates to a security document, obtainable, preferably obtained, by a printing process, wherein a printing ink formulation is used that comprises the compound of formula (1) as defined above and in the following.
A further aspect of the invention relates to a method of detecting the authenticity of the security document as defined above and in the following, the method comprising the steps of:
Here and throughout the specification, the term “polymer matrix” refers to a polymer in which the compound of formula (1) is molecularly dissolved.
Here and throughout the specification, the term “fluorescence quantum yield” (QY) is defined as ratio of the number of photons emitted to the number of photons absorbed. Here and throughout the specification, substances which absorb electromagnetic radiation in the wavelength range of IR radiation are also referred to as IR absorbers or more specially as near infrared absorbers. IR absorbers preferably have an absorption in the wavelength range from 750 to 2000 nm, more preferably from 750 to 1000 nm (near-infrared light).
Here and throughout the specification, the term “zero or low absorption in the visible spectral range” is intended to mean that the absorber should ideally have no absorption at all in the visible spectral range. For the purposes of this invention, however, it is usually sufficient if the absorption of the absorber—in the chosen amounts—in the visible spectral range is so low that the color impression of the printing ink is not ad-versely affected. Of course, this also depends on the hue and on the color strength of the respective printing ink. An absorber which is no longer suitable for a printing ink having a very specific hue and a very specific color strength may in certain circum-stances be entirely suitable for another printing ink having another hue and another color strength.
Here and throughout the specification, the term “colorant” includes pigment, dye, mixtures of pigments, mixture of dyes and mixtures of pigments and dyes. The colorant is capable of absorbing light, the wavelength of maximum absorbance is either in the visible or in the infra-red.
Here and throughout the specification, colorants which absorb visible light are also referred to as colored absorber.
Here and throughout the specification, the term “visible light” denotes light that ranges from approximately 380 nm to less than 750 nm.
Here and throughout the specification, the term “near infra-red” (NIR) denotes light that ranges from 750 nm to 1000 nm.
Here and throughout the specification, the term “coating” means a film or layer applied on a substrate and dried and/or cured, i.e., final for use. The coating may comprise one or more layers.
Here and throughout the specification, the singular form “a”, “an” and “the” includes plural references unless the content clearly dictates otherwise. The term “a” (or “an”), in phrases such as “comprising a” means “at least one” and not “one and only one”. When the term “at least one” is specifically used, this should not be construed as having a limitation on the definition of “a”.
Here and throughout the specification, the term “compound of formula #” is also referred to as “formula #” or “compound #”.
Here and throughout the specification, the term “essentially” in the context of the polymeric material encompasses the terms “completely”, “wholly” and “all”. The term encompasses a proportion of 90% or more, such as 95% or more, especially 99% or 100%.
Here and throughout the specification, the term “halogen” denotes fluorine, bromine, chlorine or iodine, particularly chlorine, bromide or iodine Here and throughout the specification, the prefixes Cn-Cm used in connection with compounds or molecular moieties each indicate a range for the number of possible carbon atoms that a molecular moiety or a compound can have.
The term “C1-Cn-alkyl” denotes a group of linear or branched saturated hydrocarbon radicals having from 1 to n carbon atoms. For example, the term C1-C20-alkyl denominates a group of linear or branched saturated hydrocarbon radicals having from 1 to 20 carbon atoms, while the term C1-Ca-alkyl denominates a group of linear or branched saturated hydrocarbon radicals having from 1 to 4 carbon atoms, the term C5-C20 alkyl denominates a group of linear or branched saturated hydrocarbon radicals having from 5 to 20 carbon atoms and the term C6-C20-alkyl denominates a group of linear or branched saturated hydrocarbon radicals having from 6 to 20 carbon atoms. Examples of alkyl include but are not limited to methyl, ethyl, n-propyl, isopropyl, n-butyl, sec-butyl, isobutyl, 1,1-dimethylethyl (tert.-butyl), pentyl, 1-methylbutyl, 2-methylbutyl, 3-methylbutyl, 2,2-dimethylpropyl, 1-ethylpropyl, hexyl, 1,1-dimethylpropyl, 1,2-dimethylpropyl, 1-methylpentyl, 2-methylpentyl, 3-methylpentyl, 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, 1-ethyl-2-methylpropyl, heptyl, octyl, 2-ethylhexyl, 1,1,3,3-tetramethylbutyl (tert-octyl), nonyl, isononyl, decyl, undecyl, dodecyl, tridecyl, isotridecyl, tetradecyl, pentadecyl, hexadecyl, heptadecyl, octadecyl, nonadecyl, eicosyl, heneico-syl docosyl and in case of nonyl, isononyl, decyl, undecyl, dodecyl, tridecyl, isotridecyl, tetradecyl, pentadecyl, hexadecyl, heptadecyl, octadecyl, nonadecyl, eicosyl, heneico-syl, docosyl, their isomers, in particular mixtures of isomers such as “isononyl”, “isodecyl”. Examples of C1-C4-alkyl are for example methyl, ethyl, propyl, 1-methylethyl, butyl, 1-methylpropyl, 2-methylpropyl or 1,1-dimethylethyl.
The term “C1-C24-haloalkyl” as used herein denotes straight-chain or branched C1-C24 alkyl as defined above, where some or all of the hydrogen atoms in these groups are replaced by halogen atoms as mentioned above. Examples for C1-C2-haloalkyl are chloromethyl, bromomethyl, dichloromethyl, trichloromethyl, fluoromethyl, difluoromethyl, trifluoromethyl, chlorofluoromethyl, dichlorofluoromethyl, chlorodifluoro-methyl, 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 and pentafluoroethyl.
The term “C1-C24-fluoroalkyl” as used herein denotes straight-chain or branched C1-C24 alkyl as defined above, where some or all of the hydrogen atoms in these groups are replaced by fluorine. Examples for C1-C2-fluoroalkyl are fluoromethyl, difluoromethyl, trifluoromethyl, 1-fluoroethyl, 2-fluoroethyl, 2,2-difluoroethyl, 2,2,2-trifluoroethyl and pentafluoroethyl.
The term “C1-C24-alkoxy” as used herein denotes straight-chain or branched C1-C24 alkyl as defined above bound to the remainder of the molecule through an oxygen. Examples for C1-C4-alkoxy are methoxy, ethoxy, n-propoxy, 1-methylethoxy, butoxy, 1-methylpropoxy, 2-methylpropoxy and 1,1-dimethylethoxy.
The term “C3-C24-cycloalky” as used herein denotes a mono-, bi- or tricyclic cycloalkyl radical. Examples of C3-C24-cycloalkyl include but are not limited to cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, methylcyclohexyl, dimethylcyclohexyl, cycloheptyl, cyclooctyl, cyclododecyl, cyclohexadecyl and norbornyl (=bicyclo[2.2.1]heptyl).
The term “heterocyclyl” as used herein refers to a mono- or bicyclic saturated or partially unsaturated ring system having 3, 4, 5, 6, 7 or 8 ring members, comprising besides carbon atoms as ring members, one, two, three or four heteroatoms or heteroa-tom-containing groups selected from O, N, S, SO and S(O)2 as ring members.
The term “C6-C10-aryl” as used herein denotes phenyl or naphthyl.
The term “C6-C10-aryloxy” as used herein denotes phenoxy and naphthyloxy.
The term “alkylene” or “alkanediyl” as used herein denotes a straight-chain or branched alkyl radical as defined above, wherein one hydrogen atom at any position of the carbon backbone is replaced by one further binding site, thus forming a bivalent moiety.
The term “C6-C10-aryl-C1-C10-alkylene” (which may also be referred to as aralkyl) as used herein refers to C6-C10-aryl-substituted C1-C10-alkyl radicals having at least one unsubstituted or substituted C6-C10-aryl group, as defined herein. The alkyl group of the aralkyl radical may be interrupted by one or more nonadjacent groups selected from O, S and NRb, wherein Rb is as defined above. C6-C10-aryl-C1-C10-alkylene is preferably phenyl-C1-C10-alkylene, more preferably phenyl-C1-C4-alkylene, for example benzyl, 1-phenylethyl, 2-phenylethyl, 1-phenylprop-1-yl, 2-phenylprop-1-yl, 3-phenylprop-1-yl, 1-phenylbut-1-yl, 2-phenylbut-1-yl, 3-phenylbut-1-yl, 4-phenylbut-1-yl, 1-phenylbut-2-yl, 2-phenylbut-2-yl, 3-phenylbut-2-yl or 4-phenylbut-2-yl; preferably benzyl and 2-phenylethyl.
The term “hetaryl” or “heteroaryl” as used herein refers to heteroaromatic, monocyclic, bicyclic or tricyclic condensed systems with 5, 6, 7, 8, 9, 10, 11, 12, 13 or 14 ring members in which at least one of the rings is aromatic and which contain 1, 2, 3 or 4 heteroatoms selected from N, S or O. Monocyclic hetaryl groups are preferably 5- or 6-membered hetaryl groups comprising 1, 2, 3 or 4 heteroatoms selected from O, S or N such as 2-furyl (furan-2-yl), 3-furyl (furan-3-yl), 2-thienyl (thiophen-2-yl), 3-thienyl (thio-phen-3-yl), 1H-pyrrol-2-yl, 1H-pyrrol-3-yl, pyrrol-1-yl, imidazol-2-yl, imidazol-1-yl, imid-azol-4-yl, pyrazol-1-yl, pyrazol-3-yl, pyrazol-4-yl, pyrazol-5-yl, 3-isoxazolyl, 4-isoxazolyl, 5-isoxazolyl, 3-isothiazolyl, 4-isothiazolyl, 5-isothiazolyl, 2-oxazolyl, 4-oxazolyl, 5-oxazolyl, 2-thiazolyl, 4-thiazolyl, 5-thiazolyl, 1,2,4-oxadiazol-3-yl, 1,2,4-oxadiazol-5-yl, 1,3,4-oxadiazol-2-yl, 1,2,4-thiadiazol-3-yl, 1,2,4-thiadiazol-5-yl, 1,3,4-thiadiazol-2-yl, 4H-[1,2,4]-triazol-3-yl, 1,3,4-triazol-2-yl, 1,2,3-triazol-1-yl, 1,2,4-triazol-1-yl, pyridin-2-yl, pyridin-3-yl, pyridin-4-yl, 3-pyridazinyl, 4-pyridazinyl, 2-pyrimidinyl, 4-pyrimidinyl, 5-pyrimidinyl, 2-pyrazinyl, 1,3,5-triazin-2-yl and 1,2,4-triazin-3-yl. Bicyclic throughout aromatic heteroaryl is 9- or 10-membered and contains 1, 2, 3 or 4 heteroatoms selected from O, S or N. Examples are quinolinyl, isoquinolinyl, indolyl, isoindolyl, indolizinyl, benzofuranyl, isobenzofuranyl, benzothiophenyl, benzoxazolyl, benzisoxazolyl, benzthi-azolyl, benzoxadiazolyl, benzothiadiazolyl, benzoxazinyl, benzopyrazolyl, benzimidaz-olyl, benzotriazolyl, benzotriazinyl.
When # or * appear in a formula showing a substructure of a compound of the present invention, it denotes the attachment bond in the remainder molecule.
With respect to the intended use of the compounds of formula (I), (Ia), (Ib), particular preference is given to the following meanings of the substituents X, R1 to R6 and the variables n and x, in each case on their own or in combination:
More preferably, R1 and R2, independently of each other, are selected from the group consisting of linear C1-C24-alkyl, branched C3-C24-alkyl, C5-C8-cycloalkyl, phenyl and phenyl-C1-C10-alkylene, where the rings of cycloalkyl, phenyl and phenyl-alkylene in the three last-mentioned radicals are unsubstituted or substituted by 1, 2 or 3 identical or different substituents Ra, wherein Ra is as defined above.
Even more preferably, R1 and R2, independently of each other, are selected from the group consisting of C5-C8-cycloalkyl that is unsubstituted or substituted by one, two or three C1-C6-alkyl substituents; linear C4-C20-alkyl; a radical of formula (A.1); a radical of formula (A.2); a radical of formula (A.3); a radical of formula (B.1); and a radical of formula (B.2)
Among the radicals of formulae (A.1), (A.2) and (A.3), the radical of formula (A.3) is preferred. In the context of the radical (A.3), Rh and Ri, independently of each other, are preferably selected from linear C4-C10-alkyl.
Among the radicals of formulae (B.1) and (B.2), those are preferred, in which y is 0, i.e. the variable B is absent. Irrespectively of its occurrence, in the context of the radicals of formulae (B.1) and (B.2), each Ra is preferably C1-C24-alkyl, more preferably linear C1-C10-alkyl or branched C3-C10-alkyl, e.g. linear C1-C6-alkyl or branched C3-C6-alkyl; in particular branched C3-C6-alkyl; and especially isopropyl or tert-butyl. In particular, the radical of formula (B.2) is preferred. Specific examples of radicals of formula (B.2) are 2,6-dimethylphenyl, 2,4-di(tert-butyl)phenyl, 2,6-diisopropylphenyl or 2,6-di(tert-butyl)phenyl.
Most preferably, R1 and R2 have the same meaning and are linear C4-C20-alkyl, a radical of formula (A.1), a radical of formula (A.2), a radical of formula (A.3) or a radical of formula (B.2), in which y is 0, i.e. the variable B is absent.
A specific embodiment of the present invention relates to compounds of formula (I), wherein the radicals R1 and R2 are each a radical of formula (B.2), in which y is 0, i.e. the variable B is absent; Ra is linear C1-C10-alkyl or branched C3-C10-alkyl, in particular linear C1-C6-alkyl or branched C3-C6-alkyl, specially branched C3-C6-alkyl; and z is 1, 2 or 3, especially 1 or 2.
Preferred compounds according to the invention are compounds of formula (I), wherein x is 0.
Preferred compounds according to the invention are also compounds of formula (I), wherein x is 1 or 2. According to a preferred embodiment, each X is independently phenoxy, which is substituted by one substituent R7 and one or two substituents R7a, wherein R7 and R7a have one of the above general, or, in particular, one of the below preferred meanings. In case of two substituents R7a, the substituents R7a may be identical or different, but are preferably the same. Preferably, R7 is attached to phenoxy in para-position, relative to the attachment point of X to the terrylene or quaterrylene scaffold; and at least one of the substituents R7a is attached to phenoxy in the ortho-position. In case of two substituents R7a, preferably both R7a are attached to phenoxy at both ortho-positions. Preferably, R7 is linear or branched C6-C15-alkyl and more preferably linear or branched C6-C12-alkyl. Specifically, R7 is branched C6-C12-alkyl. Preferably, each R7a is independently linear C1-C10-alkyl or branched C3-C10-alkyl. Specifically R7a is branched C3-C10-alkyl.
Likewise preferably, each X is independently phenyl which is substituted by one substituent R8 and zero, one or two substituents R8a, wherein R8 and R8a have one of the above general, or, in particular, one of the below preferred meanings. Preferably, phenyl is substituted by R8 in the para-position, relative to the attachment point of X to the terrylene or quaterrylene scaffold. Preferably, R8 is linear or branched C5-C12-alkyl, in particular linear C5-C12-alkyl. Preferably each R8a, if present, is C1-C12-alkyl. Spe-cially, phenyl is not substituted by R8a.
If x is 2, both X preferably have the same meaning.
Preferred compounds according to the invention are compounds of formula (I) wherein R3, R4, R5 and R6, independently of each other, are selected from phenoxy, which is substituted by one substituent R7, and by one or two substituents R7a, wherein R7 and R7a have one of the above general, or, in particular, one of the below preferred meanings. In case of two substituents R7a, the substituents R7a may be identical or different, but are preferably the same. Preferably, R7 is attached to phenoxy in para-position, relative to the attachment point of R3 to R6 to the terrylene or quaterrylene scaffold; and at least one of the substituents R7a is attached to phenoxy in the ortho-position. In case of two substituents R7a, preferably both R7a are attached to phenoxy at both ortho-positions. Preferably, R7 is linear or branched C6-C15-alkyl and more preferably linear or branched C6-C12-alkyl. Specifically R7 is branched C6-C12-alkyl. Preferably, each R7a is independently linear C1-C10-alkyl or branched C3-C10-alkyl. Specifically R7a is branched C3-C10-alkyl.
Likewise preferred compounds according to the invention are compounds of formula (I) wherein R3, R4, R5 and R6, independently of each other, are phenyl which is substituted by one substituent R8 and zero, one or two substituents R8a, wherein R8 and R8a have one of the above general, or, in particular, one of the below preferred meanings. Preferably, phenyl is substituted by R8 in the para-position. Preferably, R8 is linear or branched C5-C12-alkyl. Preferably each R8a, if present, is C1-C12-alkyl. Spe-cially, phenyl is not substituted by R8a.
Preferably, R7 is C6-C15-alkyl, more preferably linear C6-C12-alkyl or branched C6-C12-alkyl. Examples for linear C6-C12-alkyl are n-hexyl, n-heptyl, n-octyl, n-nonyl, n-decyl, n-undecyl or n-dodecyl. Examples for branched C6-C12-alkyl are 1,1-dimethylbutyl, 2,2-dimethylbutyl, 1-methylpentyl, 2-methylpentyl, 1-methylhexyl, 1-ethylpentyl, 1-methylheptyl, 2-ethylhexyl, 6-methylheptyl (isooctyl), 1,1,3,3-tetramethylbutyl (tert-octyl), isononyl, 1,1-dimethylheptyl, isodecyl and positional isomers thereof. Specifically, R7 is branched C6-C12-alkyl. In particular, R7 is tert-octyl.
Preferably, R7a is linear C1-C10-alkyl or branched C3-C10-alkyl. Examples for linear C1-C10-alkyl are methyl, ethyl, n-propyl, n-butyl, n-pentyl, n-hexyl, n-heptyl, n-octyl, n-nonyl and n-decyl. Examples for branched C3-C10-alkyl are isopropyl, sec-butyl, iso-butyl, tert-butyl, 1-methylbutyl, 2-methylbutyl, 3-methylbutyl, 2,2-dimethylpropyl, 1-ethylpropyl, 1,1-dimethylpropyl, 1,2-dimethylpropyl, 1-methylpentyl, 2-methylpentyl, 3-methylpentyl, 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, 1-ethyl-2-methylpro-pyl, 2-ethylhexyl, 1,1,3,3-tetramethylbutyl (tert-octyl), isononyl, 1,1-dimethylheptyl, isodecyl and positional isomers thereof. More preferably, R7a is branched C3-C10-alkyl.
R8 is preferably linear or branched C5-C12-alkyl. Examples of linear C5-C12-alkyl are n-pentyl, n-hexyl, n-heptyl, n-octyl, n-nonyl, n-decyl, n-undecyl or n-dodecyl. Examples for branched C5-C12-alkyl are isopentyl, neopentyl, tert-pentyl, 1,1-dimethylbutyl, 2,2-dimethylbutyl, 1-methylpentyl, 2-methylpentyl, 1-methylhexyl, 1-ethylpentyl, 1-methylheptyl, 2-ethylhexyl, 6-methylheptyl (isooctyl), 1,1,3,3-tetramethylbutyl (tert-octyl), isononyl, 1,1-dimethylheptyl, isodecyl and the position isomers thereof.
R8a, if present, is preferably C1-C12-alkyl. Specifically, R8a is absent.
Preference is given to compounds of formula (I), wherein n is 1. These com-pounds are also referred to as terrylene compounds of formula (I).
Likewise preference is given to compounds of formula (I), wherein n is 2. These compounds are also referred to as quaterrylene compounds of formula (I).
Even more preferably, in the compounds of formula (I) the substituents and indi-ces are defined as follows:
In a particular embodiment, the compound of formula (1) is a compound of formula (1) as defined above, wherein
More particularly, the compound of formula (1) is a compound of formula (1) as de-fined above, wherein
According to a preferred embodiment of the invention, if n is 1, the radicals R3, R4, R5 and R6 have the same meaning and X is absent.
According to a preferred embodiment of the invention, if n is 2, the radicals R3, R4, R5, R6 and X have the same meaning.
Preferred compounds of the formula (1) are especially those of the formula (Ia)
In a particular embodiment, the compound of formula (1) is a compound of formula (Ia) as defined above, wherein
More particularly, the compound of formula (1) is a compound of formula (Ia) as defined above, wherein
Likewise in a particular embodiment, the compound of formula (1) is a compound of formula (Ia) as defined above, wherein
More particularly, the compound of formula (1) is a compound of formula (Ia) as defined above, wherein
In the compounds of formula (Ia), R1, R2, R3, R4, R5 and R6 have one of the above preferred meanings. Specifically, in the compounds of formula (Ia), R1 and R2 are 2,6-dimethylphenyl, 2,4-di(tert-butyl)phenyl, 2,6-diisopropylphenyl or 2,6-di(tert-bu-tyl)phenyl. Specifically, in the compounds of formula (Ia), R3, R4, R5 and R6 preferably are each 2,6-diisopropyl-4-(1,1,3,3-tetramethylbutyl)-phenoxy, 2,6-di-(tert-butyl)-4-(1,1,3,3-tetramethylbutyl)-phenoxy, 2,4-bis(1,1,3,3-tetramethylbutyl)phenoxy or 2,4,6-tris(1,1,3,3-tetramethylbutyl)phenoxy. Likewise preferably, in the compounds of formula (Ia), R3, R4, R5 and R6 are each 4-n-hexylphenyl or 4-n-octylphenyl.
Preferred compounds of the formula (1) are also those of the formula (Ib)
In a particular embodiment, the compound of formula (1) is a compound of formula (Ib) as defined above, wherein
In the compounds of formula (Ib), R1, R2, R3, R4, R5 and R6 have one of the above preferred meanings.
More particularly, the compound of formula (I) is a compound of formula (Ib) as defined above, wherein
Specifically, in the compounds of formula (Ib), R1 and R2 are 2,6-dimethylphenyl, 2,4-di-(tert-butyl)-phenyl, 2,6-diisopropylphenyl or 2,6-di-(tert-butyl)-phenyl. Specifically, in the compounds of formula (Ib), X, R3, R4, R5 and R6 have the same meaning and preferably are each 2,6-diisopropyl-4-(1,1,3,3-tetramethylbutyl)-phenoxy, 2,6-di-(tert-butyl)-4-(1,1,3,3-tetramethylbutyl)-phenoxy, 2,4-bis(1,1,3,3-tetramethylbutyl)phenoxy or 2,4,6-tris(1,1,3,3-tetramethylbutyl)phenoxy.
Examples of preferred compounds are
The compounds of the present invention can be prepared by using routine techniques familiar to a skilled person. In particular, the compounds of the formula (1) can be prepared according to the following routes or as described in the experimental part of this application. A skilled person will readily understand that if x=0, the radical X is absent in the compound of formula (1).
Compounds of formula (1), wherein R3, R4, R5, R6 and X, if present, are C6-C10-aryloxy which is substituted by one substituent R7 and one or more identical or different substituents R7a can be prepared in analogy to standard methods as described in WO 03/104232 or WO 2007/006717.
For example, they can be prepared by reacting a halogenated compound of formula (XVII)
Ar—OH (XVIII)
The reaction is typically carried out in the presence of a non-nucleophilic solvent such as a polar aprotic solvent or a nonpolar aprotic solvent. Suitable polar aprotic solvents are especially aliphatic carboximides such as N,N-di-C1-C4-alkyl-C1-C4-carboximides and lactams such as dimethylformamide, diethylformamide, dimethylacetamide, dimethylbutyramide and N-methylpyrrolidone (NMP). Suitable nonpolar aprotic solvents include aromatic hydrocarbons. Preferably, the reaction is carried out in the presence of a polar aprotic solvent. It is also possible to use solvent mixtures.
The reaction is typically carried out in the presence of a base. Suitable bases are in particular inorganic and organic alkali metal or alkaline earth metal based, the alkali metal bases being particularly preferred. Examples of inorganic bases are the carbonates and hydrogencarbonates, hydroxides, hydrides and amides of alkali metals and alkaline earth meats; examples of organic bases are alkoxides, (phenyl) alkylamides and triphenylmethylmetallates based on alkali metals and alkaline earth metals. Preferred bases are the carbonates and hydrogencarbonates. Preferred alkali metals are lithium, sodium, potassium and cesium. Very particularly preferred are sodium carbonate, potassium carbonate and cesium carbonate
The reaction may be carried out in the presence of a transfer catalyst such as quaternary ammonium or phosphonium salt.
The reaction temperature is generally within the range from 30 to 150° C.
It may be advantageous to initially charge only a portion of the compound of formula (XVIII) and of the base and to add the rest only at a later stage.
The starting compound of formula (XVII) can be prepared as described in WO 2006/037539 or in analogy to the method described therein.
The starting hydroxy-containing aromatic compounds of formula (XVIII) are either commercially available or can be prepared by alkylating an appropriate substituted hy-droxyl-containing aromatic compound with an olefin in the sense of a Friedel-Crafts-al-kylation.
Compounds of formula (1), wherein R3, R4, R5, R6 and X, if present, are aryl which is substituted by one substituent R8 and zero, one or more identical or different substit-uents R8a can be prepared by a cross-coupling reaction in the presence of a transition metal catalyst starting from a compound of formula (XVII) and an organometallic compound of formula (XIX)
Ar*-Met (XIX)
Preference is given to effecting the reaction in the presence of catalytically active amounts of a transition metal of transition group VIII of the Periodic Table (group 10 according to IUPAC), for example nickel, palladium or platinum, especially in the presence of a palladium catalyst. Suitable catalysts are, for example, palladium-phosphine complexes such as tetrakis(triphenylphosphine)palladium(0), PdCl2(o-tolyl3P)2, bis(tri-phenylphosphine)palladium(II) chloride, the [1,1′-bis(diphenylphosphino)ferrocene]pal-ladium(II) chloride-dichloromethane complex, bis[1,2-bis(diphenylphosphino)ethane]-palladium(0) and [1,4-bis(diphenylphosphino)butane]palladium(II) chloride, palladium on activated carbon in the presence of phosphine compounds, and palladium(II) com-pounds such as palladium(II) chloride or bis(acetonitrile)palladium(II) chloride in the presence of phosphine compounds such as triphenylphosphine, 1,1′-bis(diphenyl-phosphino)ferrocene, 1,2-bis(diphenylphosphino)ethane, 1,3-bis(diphenylphosphino)-propane and 1,4-bis(diphenylphosphino)butane. The amount of catalyst is typically 10 to 150 mol %, based on the compounds of the formula (II).
Especially suitable organometallic compounds (XIX) are an appropriately substi-tuted arylboronic acid and arylboronic esters of formula (XIX), where Met=B(OH)2 or B(OR′)(OR″) where R′, R″═C1-C4-alkyl, or R′ and R″ together are C2-C4-alkylene optionally bearing 1, 2, 3 or 4 substituents selected from C1-C4-alkyl.
The arylboronic acids and esters thereof are known from the literature, commercially available, or can be prepared from the corresponding arylmagnesium compounds by reaction with appropriate boric esters.
The reaction of (XVII) with the organometallic compound (XIX), especially in the case of the Suzuki coupling, is effected under basic conditions. Suitable bases are alkali metal carbonates and alkali metal hydrogencarbonates such as sodium carbonate, potassium carbonate, cesium carbonate, sodium hydrogencarbonate, alkaline earth metal carbonates and alkaline earth metal hydrogencarbonates such as magnesium carbonate or magnesium hydrogencarbonate, or tertiary amines such as triethylamine, trimethylamine, triisopropylamine or N-ethyl-N-diisopropylamine.
Typically, the coupling of the compound of formula (XVII) with the compound of formula (XIX) is effected in a solvent. Suitable solvents are organic solvents such as aromatics, e.g. toluene, mesitylene, acyclic ethers, e.g. 1,2-dimethoxyethane, cyclic ethers such as tetrahydrofuran or 1,4-dioxane, polyalkylene glycols such as diethylene glycol, carbonitriles such as acetonitrile, propionitrile, carboxamides such as dimethylformamide or dimethylacetamide. In the Suzuki coupling, the aforementioned solvents can also be used in a mixture with water; for example, the ratio of organic solvent to water may be in the range from 5:1 to 1:5.
At least one mole of the organometallic compound (XIX) is used per mole of halogen atom to be exchanged. It may be advantageous to use a 5 to 30% molar excess of organometallic compound of formula (XIX) per mole of halogen atom to be exchanged.
Compounds of the formula (XIX) are commercially available or can be prepared according to known methods in the art.
All reactions are typically carried out in the absence of oxygen and moisture.
As a rule, the reaction mixtures are worked up in the customary manner, for example by mixing with water, separating the phases, and, if appropriate purifying the crude product by chromatography. If the end product is obtained as a solid, it may be purified by recrystallization.
The compounds of formula (I) according to the invention are notable for their high solubility or dispersibility in, i.e. their very good compatibility with, not only polar media (e.g. aliphatic alcohols and esters on the one hand and polyacrylates, polycarbonates and polyesters on the other) but also nonpolar media (such as alkanes and polyolefins, for example). Accordingly, the compounds of the formula (I) according to the invention may be incorporated without any problem into organic and inorganic materials and are therefore suitable for a whole series of end uses, some of which will be listed by way of example below.
In general, the terrylene compounds of formula (I) are fluorescent dyes or pigments that absorb light having a wavelength in the range from 450 to 800 nm. They generally have their absorption maximum in the range from 690 to 750 nm. They generally emit light in a range from 700 to 950 nm. The fluorescence light thusly generated is advantageously detected with a semiconductor detector, especially with a silicon photodiode or a germanium photodiode. For these applications, it is important to use the compound of formula (I) in high concentration to convert as much of the absorbed light as possible.
In general, the fluorescent or non-fluorescent quaterrylene compounds of formula (I) are useful as pigments or fluorescent dyes. They absorb in a wavelength range from 700 to 1000 nm and generally have their absorption maximum in the range from 700 to 950 nm. The fluorescence is typically in the near-infrared region.
In sum, the compounds of formula (1) are characterized by intense absorption in the wavelength range from 690 to 1000 nm, namely in the long-wavelength red and near infrared region of the electromagnetic spectrum, high heat stability, high light stability and low manufacture costs. The compounds of formula (1) are also characterized by a high solubility or dispersibility in liquid media such as printing inks or fuel oils. Spe-cially, the compounds of formula (1) are also characterized by high fastness to boiling water and high fastness to acids and alkalines. Specially, the compounds of formula (1) are also characterized by high compatibility with a number of formulations, in particular printing ink formulations used especially in security printing or 3D printing. Compositions such as inks comprising a compound of formula (1) are also characterized by good adhesion to paper and other materials such as plastics. Some of the compounds of formula (1) are also characterized by zero or low absorption in the visible spectral range from 380 to less than 750 nm, e.g. they have a transmittance of at least 75% in the range of from 380 to less than 750 nm. Some of the compounds of formula (1) are also characterized by intense emission in the wavelength range from 690 to 1000 nm, i.e., by high fluorescence quantum yield.
Accordingly, the compounds of formula (1) according to the invention are suitable for a wide variety of applications. Thus, the invention further relates to the use of the compound of formula (1) as defined above in security printing, for coloring coatings, in printing inks including printing inks for 3D printing and plastics, for data storage, for optical labels, for security labels in documents and for brand protection, for solar collectors, for optical waveguides, for the laser welding of plastics or as a fluorescent label for biomolecules.
The compounds of the formula (1) according to the present invention are useful as fluorescent dye or pigment. Among these, preference is given to those of the formula (Ia). Specially, the compounds of formula (Ia) are particularly suitable for optical waveguides. In general, the content of compounds of the general formula (Ia) is a total of between 0.0001 to 2% by weight based on the material used for wavelength conversion.
The compounds of formula (1) are also particularly suitable for laser welding of materials, wherein the materials are first contacted with compounds of the general formula (1). In general, the content of compounds of the general formula (1) is a total of between 0.0001 to 1% by weight based on the material to be welded.
The compounds of formula (1) are also particularly suitable in a fluorescent solar concentrator.
The compounds of formula (1) are also particularly suitable for homogeneously coloring high molecular weight organic and inorganic materials, for example, plastics, in particular thermoplastics, coatings and printing inks including printing inks for security printing and printing inks for 3D printing, and also oxidic layer systems.
The compounds of formula (1) are also particularly suitable as near infrared absorbers for heat management and as NIR laser beam-absorbent materials in the fusion treatment of plastics parts. These applications are described in detail, for example, in DE 10 2004 018 547, WO 02/77081 and WO 04/05427.
The compounds of formula (1) are also particularly suitable for laser marking and laser inscription. In this case, the laser light absorbed by the compound of formula (1) brings about heating of the plastic, which leads to its foaming or the conversion of a dye additionally present, and in this way gives rise to a marking or inscription. In addition, the quaterrylene compounds of formula (1) which absorb in the NIR can function in particular as protective filters for NIR radiation.
The compounds of formula (1) are also particularly suitable as labeling groups in detection methods, especially in diagnostic and analytical methods on biological samples, including living cells.
The compounds of formula (1) are also particularly suitable for use in an ink for machine readability and/or security applications. The essential component of the ink is at least one compound of formula (1) that absorbs radiation in the wavelength range of 690-1000 nm. Specifically, the ink also shows a high transparency for visible light.
The compounds of formula (1), owing to their pronounced high molar extinction coefficient, are also of interest for obtaining markings and inscriptions which are either visible to the human eye, when the compound of formula (1) absorbs visible light, or are invisible to the human eye, when the compound of formula (1) is an IR absorber. Thus, the present invention also relates to the use of the compound of formula (1) as defined above for brand protection or as marker for liquids. Useful liquids which can be marked with the compounds of the formula (1) preferably include oils such as fuel oils of mineral or regenerative origin, vegetable and animal fatty oils, and ethereal oils.
Examples of such oils are natural oils such as olive oil, soybean oil or sunflower oil, or natural or synthetic motor oils, hydraulic oils or transmission oils, for example motor vehicle oil or sewing machine oil, or brake fluids and fuel oils of mineral or regenerative origin, in particular fuel oil of mineral origin such as gasoline, kerosene, diesel oil and also heating oil. Particular preference is given to mineral oils such as gasoline, kerosene, diesel oil or heating oil, in particular gasoline, diesel oil or heating oil. Particularly advantageously, the above-mentioned compounds of the formula (1) are used as markers for fuel oils in which labelling is required, for example for tax reasons. In order to minimize the costs of labelling, but also in order to minimize possible interactions of the marked mineral oils with any other ingredients present, such as polyisobutene-amine (PIBA), efforts are made to minimize the amount of markers. A further reason to minimize the amount of markers may be to prevent their possible harmful influences, for example on the fuel intake and exhaust gas outlet region of internal combustion en-gines.
The compound of formula (1) to be used as markers is added to the liquids in such amounts that reliable detection is ensured. Typically, the (weight-based) total content of markers in the marked liquid is from about 0.1 to 5000 ppb, preferably from 1 to 2000 ppb and more preferably from 1 to 1000 ppb. The detection of the marking can be undertaken, for example, with the aid of an (absorption) spectrometer
The compound of the formula (1) may if appropriate also be used in a mixture with other markers/colorants.
To mark the liquids, the compounds are generally added in the form of solutions (stock solutions). Especially in the case of fuel oils, suitable solvents for providing these stock solutions are preferably aromatic hydrocarbons such as toluene, xylene or rela-tively high-boiling aromatics mixtures.
The present invention further relates to an article comprising at least one film layer, the film layer comprising in a polymeric matrix the compound of formula (1) as de-fined above. The compounds of the general formula (1) can be processed into virtually all plastics with the aid of processes known to those skilled in the art.
Preferably, the polymeric matrix comprises at least one thermoplastic polymer. Preferably, the thermoplastic polymer is selected from the group consisting of
Likewise possible is incorporation into blends which comprise the above-mentioned plastics as components, or into polymers which have been derived from these classes and have been modified by subsequent reactions. These materials are known and commercially available in a wide variety.
Mention may be made by way of example of polyacrylates having identical or different alcohol moieties derived from the group of the C4-C8-alcohols (particularly of bu-tanol, hexanol, octanol, and 2-ethylhexanol), polycarbonate, polymethyl methacrylate (PMMA), methyl methacrylate, butyl acrylate copolymers, acrylonitrile-butadiene-styrene copolymers (ABSs), ethylene-propylene copolymers, ethylene-propylene-diene copolymers (EPDMs), polystyrene (PS), styrene-acrylonitrile copolymers (SANs), acry-lonitrile-styrene-acrylate (ASA), styrene-butadiene-methyl methacrylate copolymers (SBMMAs), styrene-maleic anhydride copolymers, styrene-methacrylic acid copolymers (SMAs), polyoxymethylene (POM), polyvinyl alcohol (PVAL), polyvinyl acetate (PVA), polyvinylbutyral (PVB), polycaprolactone (PCL), polyhydroxybutyric acid (PHB), polyhydroxyvaleric acid (PHV), polylactic acid (PLA), ethylcellulose (EC), cellulose ace-tate (CA), cellulose propionate (CP), and cellulose acetate/butyrate (CAB).
Preferably, the polymeric matrix material comprises, in particular consists of, a polymer selected from the group consisting of polyester, especially polyethylene terephthalate, polycarbonate (PC), polystyrene (PS), polymethyl methacrylate (PMMA), polyvinylchloride, polyamide, polyethylene, polypropylene, styrene/acrylonitrile (SAN), acrylonitrile/butadiene/styrene (ABS) and mixtures of two or more thereof. Particular preference is given to polycarbonate, polyester, especially polyethylene terephthalate, or poly(methyl-methacrylate).
The polymeric matrix material may further comprise suitable stabilizers to stabi-lize the polymer. Such stabilizers are known to the skilled person and include antioxidants, UV absorbers, light stabilizers, hindered amine light stabilizers, antiozonants and the like, in particular hindered amine light stabilizers. The term “hindered amine light stabilizer” refers to sterically hindered amines of the class of compounds typically represented by 2,2,6,6 tetraalkyl piperidines.
In case the polymeric matrix material comprises a stabilizer, the matrix material preferably comprises the stabilizer in an amount of 0.001% by weight to 10% by weight, based on the total weight of the sum of all plastic materials.
According to a further embodiment, the polymeric matrix material comprises at least one scattering agent. Suitable light scattering agents are inorganic white pigments, for example titanium dioxide, barium sulfate, lithopone, zinc oxide, zinc sulfide, calcium carbonate with a mean particle size to DIN 13320 of 0.01 to 10 μm, preferably 0.1 to 1 μm, more preferably 0.15 to 0.4 μm. These light scattering agents are included typically in an amount of 0.01 to 2.0% by weight, preferably 0.05 to 1.0% by weight, more preferably 0.1 to 0.6% by weight, based in each case on the polymer of the layer comprising scattering bodies.
Examples of suitable organic light scattering agents include scattering polymers such as those based on poly(acrylates); poly (alkyl methacrylates), for example poly(methyl methacrylate) (PMMA); poly (tetrafluoroethylene) (PTFE); silicone-based scattering agents, for example hydrolyzed poly(alkyl trialkoxysilanes), and mixtures thereof. The size of these light scattering agents (average diameter-weight average) is usually in the range from 0.5 to 50 μm, preferably 1 to 10 μm. These light scattering agents are typically included in an amount of 1 to 10% by weight, based in each case on the polymer of the layer comprising scattering bodies. Useful light scattering agents are for example a mixture of 3 to 5% by weight of PMMA based scattering agent and 1.5 to 2% by weight of silicone based scattering agent.
Also suitable are light-scattering compositions which contain polymeric particles based on vinyl acrylate with a core/shell morphology in combination with TiO2 as described in EP-A 634 445.
In a preferred embodiment, the article is a color converter. According to this embodiment, the color converter preferably comprises at least one inorganic white pigment as a scattering body. Likewise preferably, the color converter comprises at least one further fluorescent material selected from garnets, silicates, sulfides, nitrides, oxy-nitrides, quantum dots and organic fluorescent colorants. Among these, preference is given to organic fluorescent colorants B from the groups (B1), (B2), (B3), (B4), (B5), (B6), (B7), (B8), (B9), (B10), (B111), (B12), (B13), (B14), (B15) or mixtures thereof. (B1) a cyanated naphthoylbenzimidazole compound of formula (II)
Preferably, the colorants from groups (B1) to (B15) are organic fluorescent dyes. The colorants of groups (B1) to (B15) can absorb light comprising a wavelength in the range from 400 to less than 680 nm and emit the absorbed light at a wavelength of greater than 500 to less than 680 nm. For example, said wavelength range is relevant to plant photophysiology.
Cyanated naphthoylbenzimidazole compound of formula (II) are known from WO 2015/019270. Compounds of formula (II) are usually green fluorescent dyes. With regard to the use in the converter of the present invention, the compound (II) is preferably selected from a compound of formula (II-A)
More preferred are the compounds specified in WO 2015/019270 on page 16, 2nd paragraph to page 20, 3rd paragraph. With regard to the use in the converter of the present invention, especially preferred are compounds of formula (II) selected from com-pounds of formulae (II-1), (II-2), (II-3), (II-4), (II-5), (II-6), (II-7), (II-8), (II-9), (II-10), (II-11), (II-12), (II-13), (II-14), (II-15), (II-16), (II-17), (II-18), (II-19), (II-20), (II-21), (II-22), (II-23), (II-24), (II-25), (II-26), (II-27), (II-28), (II-29), (II-30), (II-31), (II-32), (II-33), (II-34), (II-35), (II-36), (II-37), (II-38), (II-39), (II-40), (II-41), (II-42), (II-43), (II-44), (II-45), (II-46), (II-47), (II-48), (II-49), (II-50) or mixtures thereof
More especially preferred are compounds (II-11), (II-12), (II-13) and (II-14) and mixtures thereof.
Compounds of formula (III) are known from WO 2015/169935. Compounds of formula (III) are usually green fluorescent dyes. With regard to the use in the converter of the present invention, the compound of formula (III) encompasses the following com-pounds of formulae (III-a) and (III-b) as well as compounds of formulae (III-c) and (IIII-d):
individually and mixtures thereof,
In particular, preference is given to the compounds specified in WO 2015/169935 on page 12, line 9 to page 13, line 31. With regard to the use in the converter of the present invention, preferred are compounds of formula (III) selected from compounds of formulae (III-1), (III-2), (III-3), (III-4), (III-5), (III-6), (III-7), (III-8), (III-9), (III-10), (III-11), (III-12), (III-13), (III-14), (III-15), (III-16), (III-17), (III-18), (III-19), (III-20)
and mixtures thereof,
In a special embodiment, Z3* has the same meaning as Z3.
Among these, specific preference is given to perylene compounds of formulae (10.a), (10.b)
and mixtures of compounds of formulae (10.a) and (10.b),
Cyanated compounds of formula (IV) are subject-matter of WO 2016/151068. Compounds of formula (IV) are usually green fluorescent dyes. With regard to the use in the converter of the present invention, the compound of formula (IV) is preferably a compound, wherein X40 is O. Also preferred are compounds of formula (IV), wherein X40 is S. Preference is given to the compounds specified in WO 2016/151068 on page 24, line 10 to page 34, line 4.
Among these, compounds of formula (IV) are especially preferred, wherein A is a radical of formula (A.2). Compounds of formula (IV), where A is a radical of formula (A.2) are also referred to as compounds of formula (IV-A.2),
In the compounds of formula (I-A.2), R46 is preferably selected from hydrogen, linear C1-C24-alkyl, branched C3-C24-alkyl, C6-C10-aryl and C6-C10-aryl-C1-C10-alkylene, where the aryl ring in the two last mentioned moieties is unsubstituted or substituted with 1, 2, 3, 4 or 5 identical or different radicals R46a. Especially, R46 is selected from linear C1-C24-alkyl, a radical of formula (B.1) and a radical of formula (B.2)
Preferred radicals of formula (B.1) are: 1-methylethyl, 1-methylpropyl, 1-methylbutyl, 1-methylpentyl, 1-methylhexyl, 1-methylheptyl, 1-methyloctyl, 1-ethylpropyl, 1-ethylbutyl, 1-ethylpentyl, 1-ethylhexyl, 1-ethylheptyl, 1-ethyloctyl, 1-propylbutyl, 1-propylpentyl, 1-propylhexyl, 1-propylheptyl, 1-propyloctyl, 1-butylpentyl, 1-butylhexyl, 1-butylheptyl, 1-butyloctyl, 1-pentylhexyl, 1-pentylheptyl, 1-pentyloctyl, 1-hexylheptyl, 1-hexyloctyl, 1-heptyloctyl.
A particularly preferred radical of formula (B.2) is tert.-butyl.
Likewise especially, R46 is a radical of formula (C.1), a radical of formula (C.2) or a radical of formula (C.3)
Preferably, y is 0, i.e. the variable B is absent.
Irrespectively of its occurrence, Ri is preferably selected from C1-C24-alkyl, more preferably linear C1-C10-alkyl or branched C3-C10-alkyl, especially isopropyl. Irrespectively of its occurrence, Rk is preferably selected from C1-C24-alkyl, more preferably linear C1-C10-alkyl or branched C3-C10-alkyl. The variable x in formulae C.2 and C.3 is preferably 1, 2 or 3.
A special group of embodiments relates to compounds of formula (IV-A.2), wherein the variables m4, X40, R41, R42, R43, R44, and R45 independently of each other or in particular in combination, have the following meanings:
Even more preferably,
Examples for preferred compounds of formula (IV-A.2) are shown below:
In particular, organic fluorescent colorant (B4) is selected from compounds IV-A.2-1, IV-A.2-6 or IV-A.2-9.
Benzoxanthene compounds of formula (V) are known from WO 2014/131628. They are usually green fluorescent dyes. Benzothioxanthene compounds of formula (V) are known for example from U.S. Pat. No. 3,357,985.
Preferred are benzoxanthene compounds of formula (V), wherein R51 is phenyl which is unsubstituted or carries 1 or 2 substituents selected from C1-C10-alkyl, R53 and R54 are each phenyl and R52, R55, R56, R57, R58 and R59 are each hydrogen. Suitable compounds are depicted in FIG. 2A, FIG. 2B and FIG. 2C of WO 2014/131628. Preferred are also benz(othi)oxanthene compounds of formula (V), wherein X5 is O or S, R51 is C1-C24-alkyl and R52 to R59 are hydrogen. Preferably, R51 is C6-C20-alkyl. Suitable compounds are depicted below
Benzimidazoxanthenisoquinoline compounds of formula (VIA) and (VIB) are known from WO 2015/062916. In general, they are green fluorescent dyes. Suitable compounds are depicted at page 3, line 24 to page 8, line 24, especially FIG. 3A, FIG. 3B, FIG. 3C of WO 2015/062916.
Compounds having a structural unit of formula (VII) are known from WO 2012/168395. In general, they are green fluorescent dyes. With regard to the use in the converter of the present invention, the compound having a structural unit of formula (VII) is preferably a compound as specified in WO 2012/168395, at page 28, line 14 to page 32, line 5.
With regard to the use in the converter of the present invention, the compound having a structural unit of formula (VII) is more preferably selected from compounds of formulae (VII-1), (VII-2), (VII-3), (VII-4), (VII-5), (VII-6), (VII-7), (VII-8), (VII-9), (VII-10), (VII-11), (VII-12), (VII-13), (VII-14), (VII-15), (VII-16), (VII-17), (VII-18), (VII-19), (VII-20), (VII-21), (VII-22), (VII-23), (VII-24), (VII-25), (VII-26), (VII-27), (VII-28), (VII-29), (VII-30), (VII-31), (VII-32), (VII-33), (VII-34), (VII-35), (VII-36), (VII-37), (VII-38), (VII-39), (VII-40), (VII-41), (VII-42), (VII-43), (VII-44), (VII-45), (VII-46), (VII-47), (VII-48), (VII-49), (VII-50), (VII-51), (VII-52), (VII-53), (VII-54), (VII-55), or mixtures thereof
Especially preferred are the compounds of formulae (VII-5), (VII-6), (VII-7) and (VII-8) and mixtures thereof. More especially preferred are the compounds of formulae (VII-5), (VII-7) or a mixture of the compounds of formulae (VII-5) and (VII-7). Especially preferred are also the compounds of formulae (VII-56), (VII-57), (VII-58) and (VII-59) and mixtures thereof.
Perylene imide compounds of formula (VIII) and (IX) are well known in the art, e.g. from WO 2007/006717 or U.S. Pat. No. 6,472,050. 9-Cyano substituted perylene-3,4-dicarboxylic acid monoimides of formula (IX) are also known from WO 2004/029028. They are usually green fluorescent dyes.
Preferably, in compounds of formula (VIII), R81 and R82 are a linear or branched C1-C18 alkyl radical, a C4-C8 cycloalkyl radical which may be mono- or polysubstituted by halogen or by linear or branched C1-C18 alkyl, or phenyl or naphthyl which may be mono- or polysubstituted by halogen or by linear or branched C1-C18 alkyl. Preferably, R81 and R82 have the same meaning.
In one embodiment, R81 and R82 in formula VIII represent compounds with what is called swallowtail substitution, as specified in WO 2009/037283 A1 at page 16, line 19 to page 25, line 8. In a preferred embodiment, R81 and R82, independently of each other, are a 1-alkylalkyl, for example 1-ethylpropyl, 1-propylbutyl, 1-butylpentyl, 1-pentylhexyl or 1-hexylheptyl.
In a preferred embodiment, the organic fluorescent colorant (B7) is selected from compounds of formula (VIII-1)
Preferably, x8 is 2. Preferably, y8 is 2. Preferably, R181 and R182 are selected from isopropyl and tert-butyl.
A preferred compound of formula (VIII) is N,N′-bis(2,6-diisopropylphenyl)-3,4,9,10-perylenetetracarboxylic diimide (CAS-number: 82953-57-9).
Suitable 9-cyano substituted perylene-3,4-dicarboxylic acid monoimides of formula (IX) are preferably those, wherein R92 is a linear or branched C1-C18 alkyl radical, a C4-C8 cycloalkyl radical which may be mono- or polysubstituted by halogen or by linear or branched C1-C18 alkyl, or phenyl or naphthyl which may be mono- or polysubstituted by halogen or by linear or branched C1-C18 alkyl.
In one embodiment, R92 in formula IX represents compounds with what is called swallowtail substitution, as specified in WO 2009/037283 A1 at page 16, line 19 to page 25, line 8. In a preferred embodiment, R92, is a 1-alkylalkyl, for example 1-ethylpropyl, 1-propylbutyl, 1-butylpentyl, 1-pentylhexyl or 1-hexylheptyl. In another preferred embodiment, R92 is 2,4-di(tert-butyl)phenyl 2,6-diisopropylphenyl or 2,6-di(tert-butyl)phenyl. In particular, R92 is 2,6-diisopropylphenyl.
4-Amino-substituted naphthalimide compounds of formula (X) are known in the art. They are usually green fluorescent compounds. Suitable 4-amino substituted naphthalimide compounds of formula (X) are preferably those, wherein R101 is linear or branched C1-C10-alkyl, C2-C10-alkyl which is interrupted by one or more oxygen, or C3-C5-cycloalkyl. R102 is preferably hydrogen. A suitable compound of formula (X) is 4-(butylamino)-N-butyl-1,8-naphthalimide (CAS Number: 19125-99-6). Likewise preferably, R102 is linear or branched C1-C10-alkyl. The compounds of formula (X) can be synthesized in two steps. The first step may be the condensation of 4-chloro-1,8-naph-thalic anhydride with amines in a solvent, such as 1,4-dioxane or 2-methoxyethanol under reflux yielding the corresponding 4-chloro-1,8-naphthalimides. The second step in-volves the substitution of the chlorine atom with aliphatic primary or secondary amines.
7-(Diethylamino)-3-(5-methylbenzo[d]oxazol-2-yl)-2H-chromen-2-one is also known as Disperse Yellow (CAS Registry no. 34564-13-1). It is a green fluorescent compound
Compounds of formulae (XIA) and (XIB) are known from U.S. Pat. No. 5,470,502. They are usually green fluorescent dyes. Preferred are compounds of formulae (XIA) and (XIB), wherein R111 is linear C1-C10-alkyl or branched C3-C10-alkyl. Preferred examples are diisobutyl-3,9-perylenedicarboxylate, diisobutyl-3,10-perylenedicarboxylate and mixtures thereof. Especially preferred is a mixture of diisobutyl-3,9-perylenedicarboxylate and diisobutyl-3,10-perylenedicarboxylate.
Compounds of formulae (XIIA) and (XIIB) are known from U.S. Pat. No. 5,470,502. They are usually green fluorescent dyes. Preferred are compounds of formulae (XIIA) and (XIIB), wherein R121 is linear C1-C10-alkyl or branched C3-C10-alkyl. Preferred examples are diisobutyl-4,10-dicyanoperylene-3,9-dicarboxylate and diisobutyl-4,9-dicyanop-erylene-3,10-dicarboxylate and mixtures thereof. Especially preferred is a mixture of diisobutyl-4,10-dicyanoperylene-3,9-dicarboxylate and diisobutyl-4,9-dicyanoperylene-3,10-dicarboxylate.
Naphthoylbenzimidazole compounds of formula (1) are known from WO 2018/134261. Compounds of formula (XIII) are usually green fluorescent com-pounds.
With regard to the use in converters, compounds of formula (XIII) are preferred which correspond to a compound of formula (XIII-A)
Among the compounds of formula (XIII-A), preference is given to compounds, in which R138 and R1310 have the same meaning. Likewise, preference is given to com-pounds, in which R137 and R139 have the same meaning. In particular, R138 and R1310 have the same meaning and R137 and R139 have the same meaning. In particular, R137 and R139 have the same meaning and are hydrogen.
A particular preferred embodiment of the invention relates to compounds of formula (XIII-A), wherein
In particular, R138 is 4-cyanophenyl. In particular, R1310 is 4-cyanophenyl. Even more preferred are compounds of formula (XIII-A), wherein
In particular, R133 is phenyl which carries 1 cyano group; Likewise even more preferred are compounds of formula (XIII-A), wherein
Examples of preferred compounds of formula (XIII-A) are the compounds of formulae (XIII-A.1), (XIII-A.2) (XIII-A.3) and (XIII-A.4)
Compounds of formula (XIV) are subject matter of WO 2017/121833. Compounds of formula (XIV) are usually red fluorescent colorants. Preference is given to compounds of formula (XIV), where R141 and R142 are, independently of each other, selected from phenyl which is unsubstituted or substituted by 1, 2 or 3 C1-C6-alkyl; and R143, R144, R145, R146, R147, R148, R149, R1410, R1411, R1412, R1413, R1414, R1415, R1416, R1417 and R1418 are each hydrogen. The compound of formula (XIV) as defined above is preferably
Suitable examples of compounds of formula (XV) are for example the perylene derivatives specified in WO 2007/006717, especially at page 1, line 5 to page 22, line 6; in U.S. Pat. No. 4,845,223, especially col. 2, line 54 to col. 6, line 54; in WO 2014/122549, especially at page 3, line 20 to page 9, line 11; in EP 3072887 and WO 2018/065502, especially at page 35, line 34 to page 37, line 29. The compounds of formula (XV) are usually red fluorescent colorants. Preferred are compounds of formula (XV), wherein R151 and R152 are each independently selected from C1-C10-alkyl, 2,6-di(C1-C10-al-kyl) aryl and 2,4-di(C1-C10-alkyl) aryl. More preferably, R151 and R152 are identical. Very particularly, R131 and R132 are each 2,6-diisopropylphenyl or 2,4-di-tert-butylphenyl. R153 is preferably phenoxy, which is unsubstituted or substituted by 1 or 2 identical or different substituents selected from fluorine, chlorine, C1-C10-alkyl and phenyl. Preferably, p13 is 2, 3 or 4, in particular 2 or 4.
The compounds of formula (XV) can be prepared in analogy to the methods described for example in WO 2007/006717, U.S. Pat. No. 4,845,223, EP 3072887 and WO 2014/122549.
Suitable organic fluorescent colorants B14 are, for example, N,N′-bis(2,6-diiso-propylphenyl)-1,6,7,12-tetraphenoxyperylene-3,4:9,10-tetracarboximide, N,N′-bis(2,6-diisopropylphenyl)-1,7-di(2,6-diisopropylphenoxy)perylene-3,4:9,10-tetracarboximide, N,N′-bis(2,6-diisopropylphenyl)-1,6-di(2,6-diisopropylphenoxy)perylene-3,4:9,10-tetracarboximide, N,N′-bis(2,6-diisopropylphenyl)-1,7-di(p-tert-octylphe-noxy)perylene-3,4;9,10-tetracarboximide, N,N′-bis(2,6-diisopropylphenyl)-1,7-diphenox-yperylene-3,4;9,10-tetracarboximide, N,N′-bis(2,6-diisopropylphenyl)-1,7-di(2,6-diphe-nylphenoxy)perylene-3,4;9,10-tetracarboximide, N,N′-bis(2,6-diisopropylphenyl)-1,6-di(2,6-diphenylphenoxy)perylene-3,4;9,10-tetracarboximide, N,N′-bis(2,6-diiso-propylphenyl)-1,6,7,12-tetra(2-phenylphenoxy)perylene-3,4:9,10-tetracarboximide, N,N′-bis(2,6-diisopropylphenyl)-1,7-di(2,3-difluorophenoxy)perylene-3,4:9,10-tetracarboximide, N,N′-bis(2,6-diisopropylphenyl)-1,6,7,12-tetra(2,3-difluorophenoxy)perylene-3,4:9,10-tetracarboximide, N,N′-bis(2,6-diisopropylphenyl)-1,6,7,12-tetra(3-fluorophe-noxy)perylene-3,4:9,10-tetracarboximide, N,N′-bis(2,6-diisopropylphenyl)-1,6,7,12-tetra(2,6-difluorophenoxy)perylene-3,4:9,10-tetracarboximide, N,N′-bis(2,6-diiso-propylphenyl)-1,6,7,12-tetra(2,5-difluorophenoxy)perylene-3,4:9,10-tetracarboximide, N,N′-bis(2,6-diisopropylphenyl)-1,6,7,12-tetra(2,3-dichlorophenoxy)perylene-3,4:9,10-tetracarboximide, N,N′-bis(2,6-diisopropylphenyl)-1,6,7,12-tetra(3-chlorophe-noxy)perylene-3,4:9,10-tetracarboximide, N,N′-bis(2,6-diisopropylphenyl)-1,6,7,12-tetra(2,6-dichlorophenoxy)perylene-3,4:9,10-tetracarboximide, N,N′-bis(2,6-diiso-propylphenyl)-1,6,7,12-tetra(2,5-dichlorophenoxy)perylene-3,4:9,10-tetracarboximide. In particular, the organic fluorescent colorant (B14) is selected from compounds (XV-1), (XV-2), (XV-3) and (XV-4)
Compounds of formula (XVI) are subject matter of WO 2019/121602. The compounds of formula (XVI) are usually green fluorescent compounds. Preferred compounds according to the invention are compounds of formula (XVI), wherein the variable X is oxygen.
Preferred compounds are compounds of formula (XVI), wherein R162, R163, R164 and R165 are selected from the group consisting of the group consisting of hydrogen and C6-C10-aryl, which carries one, two or three cyano groups.
More preferably, R162 and R164 are selected from the group consisting of C6-C10-aryl, which carries one, two or three cyano groups. Particularly preferred R162 and R164 are each phenyl, which carries one, two or three cyano groups, especially one or two cyano group(s). Particularly preferred R163 and R165 are each hydrogen.
Preferably, the variable A in the compounds of formula (XVI) is a diradical of formula (A.162). In the context of the diradical (A.162), R166 is preferably selected from the group consisting of the group consisting of hydrogen, linear C1-C24-alkyl, branched C3-C24-alkyl, C6-C10-aryl and C6-C10-aryl-C1-C10-alkylene, where the aryl ring in the two last mentioned moieties is unsubstituted or substituted with 1, 2, 3, 4 or 5 identical or different radicals R166a. More preferably, R166 is selected from the group consisting of linear C1-C24-alkyl, a radical of formula (B.1), a radical of formula (B.2) and a radical of formula (B.3)
In particular, R166 is linear C6-C24-alkyl. Herein, specific examples of the radical B.1 are 1-methylethyl, 1-methylpropyl, 1-methylbutyl, 1-methylpentyl, 1-methylhexyl, 1-methylheptyl, 1-methyloctyl, 1-ethylpropyl, 1-ethylbutyl, 1-ethylpentyl, 1-ethylhexyl, 1-ethylheptyl, 1-ethyloctyl, 1-propylbutyl, 1-propylpentyl, 1-propylhexyl, 1 propylheptyl, 1-propyloctyl, 1-butylpentyl, 1-butylhexyl, 1-butylheptyl, 1-butyloctyl, 1 pentylhexyl, 1-pentylheptyl, 1-pentyloctyl, 1-hexylheptyl, 1-hexyloctyl, 1-heptyloctyl. Herein, a specific example of the radical B.2 is tert-butyl.
Herein, specific examples of the radical B.3 are isobutyl, 2-methylbutyl, 2-ethylbutyl, 2-ethylpentyl and 2-ethylhexyl.
Likewise more preferably, R166 is selected from the group consisting of a radical of formula (C.1), a radical of formula (C.2) and a radical of formula (C.3).
In the context of R166, y in formulae C.1, C.2 or C.3 is preferably zero, i.e. B is absent. In the context of R166, Rm in formula C.2 is preferably C1-C24-alkyl. In the context of R6, x in formula C.2 is preferably 1 or 2. In the context of R166, Rn in formula C.3 is preferably C1-C24-alkyl. In the context of R6, x in formula C.3 is preferably 1 or 2.
According to another embodiment, the variable A in the compounds of formula (XVI) is a diradical of formula (A.163). In the context of (A.163), n in formula (A.163) is preferably zero, one or two. R167, if present, is preferably selected from the group consisting of cyano, bromine and phenyl which is unsubstituted or carries 1 or 2 radicals selected from the group consisting of C1-C4-alkyl.
According to another embodiment, the variable A in the compounds of formula (XVI) is a diradical of formula (A.164). In the context of (A.164), o and p in formula (A.164) are preferably zero, i.e. R168 and R169 are both absent. Likewise preferably, in the context of A.4, the sum of o and p is 1, 2, 3 or 4. In this context, R168 and R169 are, independently of each other, preferably selected from the group consisting of cyano, bromine, chlorine, C1-C4-alkyl, C1-C4-alkoxy, C1-C4-haloalkyl, phenyl and phenyloxy, wherein phenyl in the two last mentioned radicals is unsubstituted or carries 1, 2 or 3 substituents selected from the group consisting of C1-C10-alkyl.
Preferred compounds are compounds of formula (XVI), wherein m in formula (XVI) is zero, one or two and when m is one or two, each R161 is independently selected from the group consisting of the group consisting of linear C1-C24-alkyl, a radical of formula (D.1), a radical of formula (D.2), a radical of formula (D.3), a radical of formula (D.4) and a radical of formula (D.5),
In the context of R161, m in formula (XVI) is preferably zero, i.e. R161 is absent. Likewise more preferably, in the context of R161, m in formula I is one, two or three. R161, if present, is preferably selected from the group consisting of linear C6-C24-alkyl. Herein, specific examples of R161 are n-hexyl, n-heptyl, n-octyl, n-nonyl, n-decyl, n-undecyl, n-dodecyl, n-tridecyl, n-tetradecyl, n-pentadecyl, n-hexadecyl, n-heptadecyl, n-octadecyl, n-nonadecyl, n-eicosyl, n-uneicosyl, n-docosyl.
In the context of R161, Ro and RP in formula (D.1) preferably are each independently C1-C12-alkyl. In the context of R161, Rq and Rs in formula (D.2) preferably are each independently C1-C6-alkyl and Rr in formula (D.2) preferably is branched C4-C21-alkyl. A specific example of the radical (D.2) is tert-octyl. In the context of R161, x in formula (D.5) preferably is 1 or 2, R161a preferably is cyano or C1-C12-alkyl. More preferably, R161 is absent or is a radical of formula (D.2) or a radical of formula (D.5), where Ra is cyano, y is 0 and x is 1 or 2. Herein, a preferred example of the radical (D.5) is 4-cyanophenyl.
Examples of preferred compounds of formula (XVI) are those depicted below:
Preferably, each compound of groups (B1) to (B15) has a fluorescence quantum yield of at least 80%, measured in a polymer film.
The skilled person will appreciate that the kind and amount of additional color-ant(s) B depend on the intended use of the color converter. When the color converter is intended for use in horticultural lighting, the color converter typically comprises at least one colorant B. Among the colorants (B), those of groups (B6), (B13) and (B14) are preferred.
The concentration of the compound of formula (I) as defined above and, if appropriate, of further colorants in the polymer matrix is set as a function of the thickness of the color converter and the type of polymer. If a thin polymer layer is used, the concentration of the compound of formula (I) and, if appropriate the concentration of further colorants, is generally higher than in the case of a thick polymer layer. Preferably, the concentration of the compound of formula (I) according to the present invention is in the range of from 0.001 to 2% by weight, especially 0.001 to 1% by weight, based on the weight of the polymeric matrix material.
The present invention also relates to a printing ink formulation for security printing. Security printing is the field that deals with the printing of items such as currency, passports, tamper-evident labels, stock certificates, postage stamps, identity cards, etc. The main goal of security printing is to prevent forgery, tampering or counterfeiting.
In the field of automated banknote processing, absorption in the visible wavelength range, IR-absorption and/or fluorescence play an important role. Preference is given to using IR absorbing compounds of formula (I) which are “colourless”, which means that they have a minimal absorption in the VIS range of the electromagnetic spectrum, in particular in the range from 400 to 700 nm. Likewise, preference is given to fluorescent compounds of formula (I). Most of the actually circulating currency carries not only visible coloured printings, but also specific features which are only detect-able in the infrared part of the spectrum and/or by irradiation with UV light. Generally, these features are implemented for use by automatic currency processing equipment, in banking and vending applications (automatic teller machines, automatic vending machines, etc.), in order to recognize a determined currency bill and to verify its authenticity, in particular to discriminate it from replicas made by colour copiers.
All security documents are required to have good stability and durability. In the case of bank notes, these requirements are extreme, as bank notes are subjected to toughest use conditions by the public—they are subjected to material stress by folding, crumpling etc., subjected to abrasion, exposed to weather, exposed to body fluids such as perspiration, laundered, dry-cleaned, ironed etc. —and, after having been subjected to this, are expected to be as legible as when they started. Furthermore, it is essential that the documents nevertheless should have a reasonable life time, ideally of some years, despite suffering the afore-mentioned conditions. During this time, the documents, and thus the inks on them (including invisible security markings), should be resistant to fading or colour change. Hence, any ink used in a security printing process should, when cured, be robust, water-resistant, resistant to various chemicals and flexi-ble. Moreover, as certain states are moving away from the use of paper as the substrate for bank notes, the employed printing ink formulations should be useable on plastics as well as paper. The compound of formula (I), because of its unique application properties, is especially suitable for printing ink formulations that are employed for security printing and in particular for bank notes.
In security printing, the compound of formula (I) is generally added to a printing ink formulation. Suitable printing inks are water-based, oil-based or solvent-based printing inks, based on pigment or dye, for inkjet printing, flexographic printing, screen printing, intaglio printing, offset printing, laser printing or letterpress printing and for use in electrophotography. Printing inks for these printing processes usually comprise solvents, binders, and also various additives, such as plasticizers, antistatic agents or waxes. Printing inks for offset printing and letterpress printing are usually formulated as high-viscosity paste printing inks, whereas printing inks for flexographic printing and intaglio printing are usually formulated as liquid printing inks with comparatively low viscosity.
In the context of the present invention, the expression “printing ink” also encompasses formulations that in addition to the compound of formula (I) comprise a colorant. The expression “printing ink” also encompasses printing lacquers that comprise no colorant.
The printing ink formulation for security printing according to the invention preferably comprises
In a preferred embodiment, the printing ink formulation comprises
Suitable components of printing inks are conventional and are well known to those skilled in the art. Examples of such components are described in “Printing Ink Manual”, fourth edition, Leach R. H. et al. (eds.), Van Nostrand Reinhold, Wokingham, (1988). Details of printing inks and their formulation are also disclosed in “Printing Inks”-Ullmann's Encyclopedia of Industrial Chemistry, Sixth Edition, 1999 Electronic Release. A formulation of an IR-absorbing intaglio ink formulation is described in US20080241492A1. The disclosure of the afore-mentioned documents is incorporated herein by reference.
The printing ink formulation according to the invention contains in general from 0.0001 to 25% by weight, preferably from 0.001 to 5% by weight, in particular from 0.01 to 0.1% by weight, based on the total weight of the printing ink formulation, of at least one compound of formula (I), component a). The good solubility/dispersibility of the compound of formula (1) in the printing ink formulation allows for incorporating high amounts of absorber into the formulation. Thus, it is possible to obtain formulations containing high amounts of the visible light/IR absorbing compound of formula (1) and comparatively low amount of other ingredients which might affect the absorbance of the compound of formula (1) or other properties.
The printing ink formulation according to the invention contains in general from 5 to to 99.9999% by weight, often from 5 to 75% by weight, preferably from 10 to 60% by weight, more preferably from 15 to 40% by weight, based on the total weight of the printing ink formulation, of a binder [component b)].
Suitable polymeric binders b) for the printing ink formulation according to the invention are for example selected from natural resins, phenol resins, phenol-modified resins, alkyd resins, polystyrene homo- and copolymers, terpene resins, silicone resins, polyurethane resins, urea-formaldehyde resins, melamine resins, polyamide resins, polyacrylates, polymethacrylates, chlorinated rubber, vinyl ester resins, acrylic resins, epoxy resins, nitrocellulose, hydrocarbon resins, cellulose acetate, and mixtures thereof.
The printing ink formulation according to the invention can also comprise components that form a polymeric binder by a curing process. Thus, the printing ink formulation according to the invention can also be formulated to be energy-curable, e.g. able to be cured by UV light or EB (electron beam) radiation. In this embodiment, the binder comprises one or more curable monomers and/oligomers. Corresponding formulations are known in the art and can be found in standard textbooks such as the series “Chemistry & Technology of UV & EB Formulation for Coatings, Inks & Paints”, published in 7 volumes in 1997-1998 by John Wiley & Sons in association with SITA Technology Limited.
Suitable monomers and oligomers (also referred to as prepolymers) include epoxy acrylates, acrylated oils, urethane acrylates, polyester acrylates, silicone acrylates, acrylated amines, and acrylic saturated resins. Further details and examples are given in “Chemistry & Technology of UV & EB Formulation for Coatings, Inks & Paints”, Volume 1l: Prepolymers & Reactive Diluents, edited by G Webster.
If a curable polymeric binder is employed, it may contain reactive diluents, i.e. monomers which act as a solvent and which upon curing are incorporated into the polymeric binder. Reactive monomers are typically chosen from acrylates or methacrylates, and can be monofunctional or multifunctional. Examples of multifunctional monomers include polyester acrylates or methacrylates, polyol acrylates or methacrylates, and polyether acrylates or methacrylates.
The printing ink formulation according to the invention contains in general from 0 to 94.9999% by weight, preferably from 5 to 90% by weight, in particular from 10 to 85% by weight, based on the total weight of the printing ink formulation, of a solvent c).
Suitable solvents c) are selected from water, organic solvents and mixtures thereof. For the purpose of the invention, reactive monomers which also act as solvent are regarded as part of the afore-mentioned binder component b).
Examples of solvents c) comprise water; alcohols, e.g. ethanol, 1-propanol, 2-propanol, ethylene glycol, propylene glycol, diethylene glycol and ethoxy propanol; esters, e.g. ethyl acetate, isopropyl acetate, n-propyl acetate and n-butyl acetate; hydrocarbons, e.g. toluene, xylene, mineral oils and vegetable oils, and mixtures thereof.
The printing ink formulation according to the invention may contain one or more additional colorants d) which impart a specific optical property (i.e. colorants or components which are different from the compound of formula (1)). Preferably, the printing ink formulation contains in from 0 to 25% by weight, more preferably from 0.1 to 20% by weight, in particular from 1 to 15% by weight, based on the total weight of the printing ink formulation, of a colorant d).
Suitable colorants d) are selected conventional dyes, and in particular conventional pigments. The term “pigment” is used in the context of this invention comprehen-sively to identify all pigments and fillers, examples being colour pigments, white pigments, and inorganic fillers. These include inorganic white pigments such as titanium dioxide, preferably in the rutile form, barium sulfate, zinc oxide, zinc sulfide, basic lead carbonate, antimony trioxide, lithopones (zinc sulfide+barium sulfate), or colored pigments, examples being iron oxides, carbon black, graphite, zinc yellow, zinc green, ul-tramarine, manganese black, antimony black, manganese violet, Paris blue or Schweinfurt green. Besides the inorganic pigments the printing ink formulation of the invention may also comprise organic colour pigments, examples being sepia, gam-boge, Cassel brown, toluidine red, para red, Hansa yellow, indigo, azo dyes, anthraqui-nonoid and indigoid dyes, and also azo, dioxazine, quinacridone, perylene, quinoph-thalone, diketopyrrolopyrrole, phthalocyanine, isoindoline, isoindolinone, and metal complex pigments. Also suitable are synthetic white pigments with air inclusions to in-crease the light scattering, such as the Rhopaque® dispersions. Suitable fillers are, for example, aluminosilicates, such as feldspars, silicates, such as kaolin, talc, mica, mag-nesite, alkaline earth metal carbonates, such as calcium carbonate, in the form for example of calcite or chalk, magnesium carbonate, dolomite, alkaline earth metal sul-fates, such as calcium sulfate, silicon dioxide, etc.
Although they are invisible to the human eye, in terms of the present invention, further IR absorbers are also considered to belong to colorants d). Preferred further IR absorbers are selected from the group consisting of polymethines, phthalocyanines, quinone-diimmonium salts, aminium salts, inorganic IR absorbers and mixtures thereof.
The printing ink formulation may comprise at least one colorant d) for establishing a desired hue, especially transparent organic pigments and dyes, for example C.I. Pigment Yellow 13, 14, 17, 74, 138, 139, 147, 150, 151, 155, 183, 185 192 and 196, C.I. Pigment Orange 34, 64, 70, C.I. Pigment Red 48:1, 48:2, 57:1, 149, 178 and 179, 181, 263, C.I. Pigment Violet 19, 37 and 29, C.I. Pigment Blue 15, 15:1, 15:3 and 15:4, 15:6, 16, 60, C.I. Pigment Green 7 and 36, C.I. Solvent Yellow 14, 21, 93, 130, 133, 145, 162, 163, C.I. Solvent Red 52, 135, 195, 213, 214 and 225, C.I. Solvent Blue 35, 45, 67, 68, 97, 104, 122, 132, C.I. Solvent Violet 13, 46, 49, C.I. Solvent Green 3, 5 and 28, C.I. Solvent Orange 47, 60, 86, 114, and 163, C.I. Solvent Brown 35, 53, and also C.I. Disperse Yellow 54, 87, 201, C.I. Disperse Orange 30, C.I. Disperse Red 60 and C.I. Disperse Violet 57.
The printing ink formulation according to the invention may contain at least one additive e). Preferably, the printing ink formulation contains from 0 to 25% by weight, more preferably from 0.1 to 20% by weight, in particular from 1 to 15% by weight, based on the total weight of the printing ink formulation, of at least one component e).
Suitable additives (component e) are selected from plasticizers, waxes, siccatives, antistatic agents, chelators, antioxidants, stabilizers, adhesion promoters, surfac-tants, flow control agents, defoamers, biocides, thickeners, etc. and combinations thereof. These additives serve in particular for fine adjustment of the application-related properties of the printing ink, examples being adhesion, abrasion resistance, drying rate, or slip.
A further possible additive group is that of additives which likewise modify the vis-ual appearance, the mechanical properties or else the tactile properties, for example matting agents, such as titanium dioxide, chalk, barium sulfate, zinc sulfide, fillers, such as nanoparticulate silicon dioxide, aluminium hydroxide, clay and other sheet silicates, glass fibers and glass spheres.
In the case of printing ink formulations to be cured by UV radiation, it is usually necessary to include at least one photoinitiator (component f) to initiate the curing reaction of the monomers upon exposure to UV radiation. Photoinitiators are understood to be substances which, when exposed to UV radiation, i.e. light with a wavelength below 420 nm, in particular below 410 nm, decompose with the formation of radicals and thus trigger a polymerization of the ethylenically unsaturated double bonds. Therefore, such photoinitiators are tuned to the wavelength of the light source and typically have at least one absorption band which has a maximum in the range from 220 to 420 nm, in particular in the range from 230 to 410 nm that.
Examples of useful photoinitiators f) can be found in standard textbooks such as “Chemistry & Technology of UV & EB Formulation for Coatings, Inks & Paints”, Volume III, “Photoinitiators for Free Radical Cationic and Anionic Polymerisation”, 2nd edition, by J. V. Crivello & K. Dietliker, edited by G. Bradley and published in 1998 by John Wiley & Sons in association with SITA Technology Limited. It may also be advantageous to include a sensitizer in conjunction with the photoinitiator in order to achieve efficient curing. Preferred photoinitiators are especially alpha-hydroxyalkylphenones, alpha-dialkoxyacetophenones, phenylglyoxalic acid esters, benzophenones, benzoins and acylphosphinoxides.
In another preferred embodiment, the at least one compound of formula (1) is incorporated in a UV curable printing formulation. In this case, the formulation typically comprises
According to a further embodiment, the polymeric binder b) of the printing ink formulation is an oxidative drying resin.
Oxidation is the classical drying mechanism for lithographic inks, involving the ox-ygen-induced free radical polymerisation of unsaturated (drying) polymers, such as vegetable oils, for example, linseed oil and tung oil. The oxidant is atmospheric oxygen. It is a chemical process which can be catalysed (accelerated) by small amounts of appropriate metal, usually transition metal, driers, such as cobalt and/or manganese catalysts (siccatives). Examples of thermally or oxidatively drying binders are alkyd resins, such as in particular long oil alkyd resins, polyamide resins, (meth)acrylic resins, polyurethane resins, phenolic resins, vinyl resins, rosin modified maleic resins and varnishes made by cooking a resin, such as an alkyd, polyurethane or phenolic resin, with an oxidative drying oil, such as tung oil, linseed oil, poppy seed oil or perilla oil, as well as mixtures of these resins and varnishes. The aforementioned resins and varnishes are well known and e.g. described in more detail by R. van Gorkum et al., Coordination Chemistry Reviews 249 (2005) 1709-1728; J. F. Black, J. Am. Chem. Soc., 1978, 100, 527, J. Mallégol et al., Prog. Org. Coatings 39 (2000) 107-113, The Printing ink manual, R. H. Leach and R. J. Pierce, Springer Edition, 5th Edition and commercially available, e.g. from Epple Druckfarben AG.
The printing ink formulations according to the invention are advantageously prepared in a conventional manner, for example by mixing the individual components. As mentioned above, at least one compound of formula (1) according to the invention is present in the printing ink formulation. Additional colorants may be employed in the printing ink formulation of the invention or in a separate ink formulation. When additional colorants are to be employed in a separate formulation, the order of application of the printing ink formulation according to the invention is usually not relevant. The printing ink formulation according to the invention can for example be applied first and then be overprinted with conventional printing inks. But it is also possible to reverse this sequence or, alternatively, to apply the printing ink formulation according to the invention in a mixture with conventional printing inks. In every case the prints are readable with suitable light sources.
Primers can be applied to the substrate prior to the printing ink formulation according to the invention. By way of example, the primers are applied in order to improve adhesion to the substrate. It is also possible to apply additional printing lacquers, e.g. in the form of a covering to protect the printed image. Additional printing lacquers may also be applied to serve aesthetic purposes, or serve to control application-related properties. By way of example, suitably formulated additional printing lacquers can be used to influence the roughness of the surface of the substrate, the electrical properties, or the water-vapour-condensation properties. Printing lacquers are usually applied in-line by means of a lacquering system on the printing machine employed for printing the printing ink formulation according to the invention.
The printing ink formulations according to the invention are also suitable for use in multilayer materials. Multilayer materials are e.g. composed of two or more plastics foils, such as polyolefin foils, metal foils, or metallised plastics foils, which are bonded to one another, by way of example, via lamination or with the aid of suitable laminating adhesives. These composites may also comprise other functional layers, such as odour-barrier layers or water-vapour barriers.
These layers may additionally comprise one or more UV absorbers. UV absorbers are well known in the plastics, coatings and cosmetic industry.
The present invention also relates to a method for producing a security feature or a security document, which comprises applying a printing ink formulation to a substrate by a printing process.
In a further aspect the invention provides a security document, the security document comprising a substrate, a cured ink which ink comprises at least one compound of the formula (I) as defined above.
Yet in a further aspect, the invention provides a security document, obtainable by a printing process, wherein a printing ink formulation is used that comprises at least one compound of formula (I) as defined above. “Obtainable” indicates that the security document can also be obtained by a process different from printing, e.g. by manual application, or by spin coating or slot die coating. This notwithstanding, the resulting security document comprises at least one compound of formula (I) as defined above. Preferably however, the security document is indeed obtained by a printing process, in which process the printing ink formulation of the invention is used that comprises at least one compound of formula (1) as defined above.
The printing ink formulations of the invention may be applied by a printing process preferably selected from the group consisting of offset-printing processes, rotogra-vure printing processes, silkscreen printing processes, copperplate intaglio printing processes, flexographic printing processes, letterpress printing processes; more preferably by offset-printing processes and copperplate intaglio printing processes. The aforementioned printing techniques are well known to a skilled person.
In this context, the term “security feature” is in particular a specific image that is printed on a substrate; and term “substrate” means any object which is intended to be furnished with a security feature, or intended to be converted into a security document by applying the ink formulation in order to produce a security feature.
The term “security document” means any document intended to be protected against forgery or counterfeiting. Such security documents include in particular value documents and value commercial goods. Typical example of value documents include e.g. banknotes, documents, deeds, tickets, checks, vouchers, fiscal stamps and tax labels, agreements and the like, identity documents such as passports, identity cards, vi-sas, driving licenses, bank cards, credit cards, transactions cards, access documents or cards, entrance tickets, public transportation tickets or titles and the like, preferably banknotes, identity documents, right-conferring documents, driving licenses and credit cards. The term “value commercial good” refers e.g. to packaging materials, in particular for cosmetic articles, nutraceutical articles, pharmaceutical articles, alcohols, tobacco articles, beverages or foodstuffs, electrical/electronic articles, fabrics or jewelry, i.e. articles that shall be protected against counterfeiting and/or illegal reproduction in order to warrant the content of the packaging like for instance genuine drugs. Examples of these packaging materials include e.g. labels, such as authentication brand labels, tamper evidence labels and seals. It is pointed out that the disclosed substrates, value documents and value commercial goods are given exclusively for exemplifying purposes, without restricting the scope of the invention.
The present invention also relates to a method of detecting the authenticity of the security document as defined above, comprising the steps of:
The printing formulations of the invention are particularly suitable for this type of security printing, as they enable security images exhibiting remission (radiation reflectance and scattering) of wavelengths in the range of 700 to 1100 nm, especially of 700 to 900 nm, that is reduced by at least 40%, in particular at least 50%, in comparison to the blank substrate.
The invention will be illustrated in detail by the examples.
The starting materials used in the examples are either commercially available or can be synthesized by the average skilled person trained in organic chemistry following routine laboratory practice as outlined, for example, in the examples below.
A mixture of 10.16 g (48 mmol) of 4-tert.-octylphenol, 5.41 g (48 mmol) of 2,4,4-trimethylpent-1-ene and 100 mL of dichloromethane was cooled to −20° C. 5 mL of methanesulfonic acid were slowly added and the mixture was kept between −18° C. and −12° C. for three hours. Water was added, phases separated and the organic phase repeatedly washed with water, dried with MgSO4 and evaporated. The product was purified by column chromatography on silica using cyclohexane and toluene. 10.4 g (68%) of a colorless oil were isolated.
Rf=(toluene:ethyl acetate=10:1)=0.83.
A mixture of 10.00 g (54.4 mmol) of 2,6-diisopropylphenol, 6.18 g (54.4 mmol) of 2,4,4-trimethylpent-1-ene and 100 mL of dichloromethane was cooled to −12° C. Then 7.44 g (77 mmol) of methane sulfonic acid were slowly added within 15 minutes. The reaction mixture was stirred at −18° C. for 2 hours. Then 100 mL of water were added, the phases were separated and dried with MgSO4, organics were evaporated and the residue was subjected to column chromatography using silica gel and cyclohexane toluene 90:10 for purification. 15.07 g (81%) of a yellow oil were obtained.
The title compound was prepared according to EP 1802 622.
The title compound was prepared according to WO 96/22332.
A mixture of 2.80 g (2.4 mmol) of N,N′-bis(2,6-diisopropylphenyl)-1,6,9,14-tetrabro-moterrylen-3,4;11,12-tetracarboxylic acid diimide from a3), 4.89 g (14.6 mmol) of the phenol from a1), 750 mg (5.3 mmole) of K2CO3 and 50 mL of N-methylpyrrolidone were heated to 90° C. for two days. Afterwards the temperature was raised to 130° C. for 2 hours. Further 340 mg of potassium carbonate and 376 mg of the phenol from a1) were added and the reaction mixture kept at this temperature for 20 hours. The mixture was cooled to room temperature, 50 mL of 20% hydrochloric acid were added and the precipitate was filtered, washed with water and dried under reduced pressure. The residue was subjected to column chromatography using cyclohexane/toluene as eluent to obtain 940 mg of the green title product.
Rf (petroleum ether toluene 30:70)=0.5; lambda max absorption (CH2Cl2): 694 nm
A mixture of 6 mL of N-methylpyrrolidone, 502 mg (392 mmol) of N,N′-bis(2,6-diiso-propylphenyl)-1,6,9,14-tetrabromoterrylen-3,4,11,12-tetracarboxylic acid diimide from a3), 537 mg (1.72 mmol) of the phenol from a2) and 190 mg (1.17 mmol) of potassium carbonate was heated to 105° C. for 6 hours. The mixture was cooled to room temperature, and 200 mL of water and 100 mL of tert-butyl methylether were added. The phases were separated and the organic phase was washed three times with water, dried with Na2SO4 evaporated and the residue was subjected to column chromatography using cyclohexane toluene mixtures to yield 260 mg (34%) of the blue title product.
Rf (toluene)=0.76; lambda max absorption (CH2Cl2): 699 nm
A mixture of 200 mg (0.157 mmol) of N,N′-bis(2,6-diisopropylphenyl)-1,6,9,14-tetrabro-moterrylen-3,4;11,12-tetracarboxylic acid diimide from a3), 142.3 mg (0.691 mmol) of 4-n-hexylphenylboronic acid, 65.1 mg (0.471 mmole) of K2CO3, 0.2 mg (0.157 μm) of tetrakistriphenylphopshinepalladium and 5 mL of toluene were heated to 85° C. for a day. The mixture was cooled to room temperature, water and methylene chloride were added and the phases were separated. To the organic phase, brine was added, the phases separated, dried with MgSO4, the precipitate was filtered, and the residue evaporated. The crude product was purified by column chromatography on silica using cyclohexane and toluene to yield 106.7 mg (46%) of the turquoise title product. Rf (toluene)=0.31; lambda max absorption (CH2Cl2): 720 nm
A flask was heated and cooled down under argon. Then a mixture of 500 mg (0.3 mmol -1 eq) of N,N′-bis(2,6-diisopropylphenyl)-1,6,8,11,16,18-hexabromoquaterrylen-3,4,13,14-tetracarboxylic acid diimide from a4), 650 mg (1.9 mmol-6.6 eq) of the phenol from a1), 135 mg (1.0 mmol-3.3 eq) K2CO3 and 10 mL of anhydrous N-methylpyrrolidone were heated to 97° C. for 20 h. The mixture was cooled to room temperature, water and methylene chloride were added and the phases were separated. To the organic phase NaCl solution was added, phases separated, dried with MgSO4 and evaporated. The residue was subjected to column chromatography using cyclohexane/toluene as eluent to yield 200 mg of a green product.
Rf (toluene)=0.81; lambda max absorption (CH2Cl2): 777 nm
A mixture of 1.00 g (0.643 mmol) of N,N′-bis(2,6-diisopropylphenyl)-1,6,8, 11,16,18-hexabromoquaterrylen-3,413,14-tetracarboxylic acid diimide from a4), 1.45 g (4.243 mmol) of the phenol from a2), 296 mg (2.12 mmol) of potassium carbonate and 20 mL of N-methylpyrrolidone was heated 95° C. for 20 hours. The workup and purification were done as described in example 4 to yield 140 mg (8.1%) of a green oil. Rf (toluene)=0.75; lambda max absorption (CH2Cl2): 786 nm
The title compound was prepared as described in example 29 of WO 2003/104232; lambda max absorption (CH2Cl2): 677.09 nm
The title compound was prepared as decribed in example 2 of WO 2007/006717.
Here and in the following, the abbreviations have the following meanings:
Fluorescence quantum yields (QY) of the analysis samples were measured with the C9920-02 quantum yield measuring system from Hamamatsu. This was done by illuminating each of the samples in an integrating sphere (Ulbricht sphere). By comparison with the reference measurement in the Ulbricht sphere without sample, the unabsorbed fraction of the excitation light and the fluorescent light emitted by the sample are determined by means of a CCD spectrometer. Integration of the intensities of the spectrum of the unabsorbed excitation light and of that of the emitted fluorescent light gives the degree of absorption and fluorescence intensity, respectively, and thus the fluorescence quantum yield of each sample can be calculated.
For preparation of the samples, the dye in question, polycarbonate (PC, Makrolon 2808) and TiO2 (Kronos 2233, 0.5% by weight) were mixed together according to the desired concentration (see Table I-V). The concentrations are given relative to the amount of polycarbonate used. Then methylene chloride was added and the mixtures were stirred overnight. The solutions/dispersions were coated onto a glass surface by doctor blading. After the solvent had dried off for 2 hours, the film was detached from the glass and dried in vacuum at 50° C. Samples were cut from the foils and had a thickness of 67 μm.
As can be seen, a bathochrome shift of the emission occurs with increasing concentration of the fluorescent dye.
The quantum yield decreases at higher concentration due to aggregate formation and reabsorption effects.
The results show that the novel terrylene bisimide compounds can be used in higher concentration while still retaining a high quantum yield compared to the compounds of prior art.
0.1 g of the compound of example 1, 100 g of Laromer® PE 46T and 3 g diphe-nyl(2,4,6-trimethylbenzoyl)phosphinoxide (or ethyl(2,4,6-trimethylbenzoyl)phenyl-phosphinate) were mixed in a speedmixer apparatus in a 60 mL jar. A drawdown was prepared with a 12 (or 24) μm spiral wirebar on PET foil. The coated PET foil was cured 3 times at 120 W/cm2 under a UV belt (Technigraf Aktiprint T/e with Hg-lamp (UT 51072-0004)). The achieved film showed an emission in the wavelength range from 700 to 1000 nm.
Example 2 was prepared according to the general procedure of example 1, but using Laromer® EA 9081 instead of Laromer® PE 46T.
Example 3 was prepared according to the general procedure of example 1, but using Laromer® LR 8986 instead of the Laromer® PE 46T.
0.05 g of the compound of example 4 was dissolved in 3.5 g of Laromer® DPGDA. 1.5 g of Omnirad® 184 was dissolved in 3.5 g of Laromer® DPGDA. Both solutions were added to 40 g of Laromer® UA 9048 and mixed either by hand or in a speedmixer equipment. A drawdown with a 24 μm spiral wirebar on a PET film was cured with a Technigraf Aktiprint T/e with Hg-lamp (UT 51072-0004) at 120 W/cm2 with 20 m/min or 2×40 m/min at 120 W/cm2). The obtained films showed an absorption at 780 nm.
Example 5 was prepared according to the general procedure of example 4, but using Omnirad®2959 instead of the Omnirad®184.
0.125 g of the compound of example 3, 100 g Laromer® UA 9072, 25 g of Laromer® DPGDA and 6.25 g of diphenyl(2,4,6-trimethylbenzoyl)phosphinoxide were mixed in a Speedmixer DAC 400.1 FVZ in a 60 mL jar with 5 glass beads with a 4 mm diameter for 2×140 minutes. The draw down with 12 μm spiral wirebar on Lumirror 4001/50 μm showed after UV curing (3*120 W/cm2) a fluorescence in the NIR.
Example 7 was prepared according to the general procedure of example 6, but using Laromer® LR 8887 instead of the Laromer® DPGDA.
Example 8 was prepared according to the general procedure of example 6, but using Laromer® DPHA instead of Laromer® UA 9072.
An offset ink was prepared by mixing the following components by means of an automatic pigment muller: 1000 nm of Offset varnish, 200 mg of trithiocyanuric acid, 40 mg of the compound of example 4, 20 mg of siccative. Immediately afterwards the freshly prepared offset ink was printed onto uncoated paper with a printability tester (IGT Orange Proofer). The print showed an absorption with two maxima at 710 and 790 nm and by excitation at 660 nm an emission at 980 nm.
0.5 g of the compound of example 3 in 39.5 g of VINNOL E 15/48A (10% in ethyl ace-tate/methyl ethyl ketone/methyl isobutyl ketone=20:30:47) was dispersed in a 100 mL glass jar with 50 g of glass beads with a diameter of 2 mm for 30 minutes in the scan-dex. With a 24 μm spiral wirebar a drawdown was prepared on acetate film. The film showed an absorption at 720 nm.
| Number | Date | Country | Kind |
|---|---|---|---|
| 21213300.3 | Dec 2021 | EP | regional |
| Filing Document | Filing Date | Country | Kind |
|---|---|---|---|
| PCT/EP2022/085121 | 12/9/2022 | WO |
