WO2023025694A1 - Nouveaux émetteurs nir à base de pérylène - Google Patents

Nouveaux émetteurs nir à base de pérylène Download PDF

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Publication number
WO2023025694A1
WO2023025694A1 PCT/EP2022/073245 EP2022073245W WO2023025694A1 WO 2023025694 A1 WO2023025694 A1 WO 2023025694A1 EP 2022073245 W EP2022073245 W EP 2022073245W WO 2023025694 A1 WO2023025694 A1 WO 2023025694A1
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group
compound
formula
phenyl
alkyl
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PCT/EP2022/073245
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English (en)
Inventor
Yulian ZAGRANYARSKI
Artem Nikolaevich SKABEEV
Chen Li
Klaus Muellen
Hans Reichert
Helmut Reichelt
Korinna Dormann
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Basf Se
MAX-PLANCK-Gesellschaft zur Förderung der Wissenschaften e.V.
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Publication of WO2023025694A1 publication Critical patent/WO2023025694A1/fr

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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B42—BOOKBINDING; ALBUMS; FILES; SPECIAL PRINTED MATTER
    • B42D—BOOKS; BOOK COVERS; LOOSE LEAVES; PRINTED MATTER CHARACTERISED BY IDENTIFICATION OR SECURITY FEATURES; PRINTED MATTER OF SPECIAL FORMAT OR STYLE NOT OTHERWISE PROVIDED FOR; DEVICES FOR USE THEREWITH AND NOT OTHERWISE PROVIDED FOR; MOVABLE-STRIP WRITING OR READING APPARATUS
    • B42D25/00—Information-bearing cards or sheet-like structures characterised by identification or security features; Manufacture thereof
    • B42D25/30—Identification or security features, e.g. for preventing forgery
    • B42D25/36—Identification or security features, e.g. for preventing forgery comprising special materials
    • B42D25/378—Special inks
    • B42D25/382—Special inks absorbing or reflecting infrared light
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B42—BOOKBINDING; ALBUMS; FILES; SPECIAL PRINTED MATTER
    • B42D—BOOKS; BOOK COVERS; LOOSE LEAVES; PRINTED MATTER CHARACTERISED BY IDENTIFICATION OR SECURITY FEATURES; PRINTED MATTER OF SPECIAL FORMAT OR STYLE NOT OTHERWISE PROVIDED FOR; DEVICES FOR USE THEREWITH AND NOT OTHERWISE PROVIDED FOR; MOVABLE-STRIP WRITING OR READING APPARATUS
    • B42D25/00—Information-bearing cards or sheet-like structures characterised by identification or security features; Manufacture thereof
    • B42D25/30—Identification or security features, e.g. for preventing forgery
    • B42D25/36—Identification or security features, e.g. for preventing forgery comprising special materials
    • B42D25/378—Special inks
    • B42D25/387—Special inks absorbing or reflecting ultraviolet light
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09B—ORGANIC DYES OR CLOSELY-RELATED COMPOUNDS FOR PRODUCING DYES, e.g. PIGMENTS; MORDANTS; LAKES
    • C09B5/00—Dyes with an anthracene nucleus condensed with one or more heterocyclic rings with or without carbocyclic rings
    • C09B5/62—Cyclic imides or amidines of peri-dicarboxylic acids of the anthracene, benzanthrene, or perylene series
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D11/00—Inks
    • C09D11/02—Printing inks
    • C09D11/03—Printing inks characterised by features other than the chemical nature of the binder
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D11/00—Inks
    • C09D11/02—Printing inks
    • C09D11/03—Printing inks characterised by features other than the chemical nature of the binder
    • C09D11/037—Printing inks characterised by features other than the chemical nature of the binder characterised by the pigment
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D11/00—Inks
    • C09D11/50—Sympathetic, colour changing or similar inks
    • G—PHYSICS
    • G07—CHECKING-DEVICES
    • G07D—HANDLING OF COINS OR VALUABLE PAPERS, e.g. TESTING, SORTING BY DENOMINATIONS, COUNTING, DISPENSING, CHANGING OR DEPOSITING
    • G07D7/00—Testing specially adapted to determine the identity or genuineness of valuable papers or for segregating those which are unacceptable, e.g. banknotes that are alien to a currency
    • G07D7/06—Testing specially adapted to determine the identity or genuineness of valuable papers or for segregating those which are unacceptable, e.g. banknotes that are alien to a currency using wave or particle radiation
    • G07D7/12—Visible light, infrared or ultraviolet radiation
    • G—PHYSICS
    • G07—CHECKING-DEVICES
    • G07D—HANDLING OF COINS OR VALUABLE PAPERS, e.g. TESTING, SORTING BY DENOMINATIONS, COUNTING, DISPENSING, CHANGING OR DEPOSITING
    • G07D7/00—Testing specially adapted to determine the identity or genuineness of valuable papers or for segregating those which are unacceptable, e.g. banknotes that are alien to a currency
    • G07D7/06—Testing specially adapted to determine the identity or genuineness of valuable papers or for segregating those which are unacceptable, e.g. banknotes that are alien to a currency using wave or particle radiation
    • G07D7/12—Visible light, infrared or ultraviolet radiation
    • G07D7/1205—Testing spectral properties

Definitions

  • the present invention relates to compounds of the formula (I), a process for its preparation and its use as fluorescent dye that absorbs light emitted from an irradiation source and emits light different from that of the irradiation source and having a wavelength in the range from 680 to 1000 nm; in photovoltaic applications; or as semiconductor in organic electronic applications; as laser dye, in an ink for machine readability and/or security applications or for the laser-welding of plastics; or for brand protection or as marker for liquids.
  • the compounds of formula (I) may have a high fluorescence quantum yield, a high molar extinction coefficient, a high solubility and stability in the application medium, good storage stability and/or good detectability even in very small amounts in the correspondingly marked liquids.
  • WO2014147525 relates to perylenemonoimide and naphthalenemonoimide derivatives and their use in dye-sensitized solar cells.
  • WO2014033620 relates to double donor functionalisation of the peri-positions of perylene and naphthalene monoimide via versatile building blocks.
  • US20070151478A1 relates to black perylene pigments.
  • WO2009/141387A1 relates to quinoid rylene dicarboximides and its use as visible or invisible marking materials, for coloring of materials, in laser welding of materials, for identification of bases, acids or pH changes, as dispersion agents, pigment additives for organic pigments and intermediate products for the manufacture of pigment additives, in thermal management or energy management, in the photovoltaic or optical data storage.
  • Perylene chromophores having been commercialized as the LUMOGEN series, cover the absorption range from UV to red light and often give nearly quantitative fluorescence (I. A. Carbone, K. R. Frawley, M. K. McCann, Int. J. Photoenergy. 2019, 8680931). They are used for coloring plastics, but also as active components of LEDs and solar concentrators (M. Kang, J. Y. Park, H. K. Yang, M. Kwak, Mol. Cryst. Liq. Cryst. 2017, 659, 154-159).
  • the push-pull substituted perylenemonoimides 4 exhibit Stokes shifts larger than 80 nm, but weak absorption in the NIR region (C. Li, J. Schoneboom, Z. H. Liu, N. G. Pschirer, P. Erk, A. Herrmann, K. Mullen, Chem-Eur. J., 2009, 15, 878-884).
  • the highly NIR fluorescent perylenemonoimides 6 are obtained.
  • This structure contains a benzoacridine moiety thanks to the occurrence of C-N/C-C domino reactions (Y.
  • NIR fluorophores a new class of NIR fluorophores is readily obtained by C-N/C-C domino reactions between diphenylamines and 9,10-dibromoperylenemonoimides. These dyes show emission maxima up to 804 nm with fluorescence quantum yields from 47% to 80%. Owing to their rigid, planarized structure and pronounced push-pull substitution, they exhibit large Stokes shifts and ultra-high photostability, making them useful NIR emitters for applications as biomarkers and security inks.
  • the invention relates to compounds of the formula (I), especially a compound of formula wherein R x is hydrogen, a Ci-C24-alkyl group, which may be interrupted by O, or NR 18 ' ; or a group of formula ;
  • R 1 and R 2 are selected from hydrogen, a Ci-C24-alkyl group, a Ci-C24-alkoxy group, a Ci-C24-haloalkyl group, a C3-C24-cycloalkyl group, a Ce-C -aryloxy group and a group NR 19 R 20 ; or
  • R 3 , R 4 , R 5 and R 6 are selected from a Ci-C24-alkoxy group, - NR 18 ", hydrogen and chlorine;
  • R 7 is selected from the group consisting of hydrogen, a Ci-C24-alkyl group, a Ci-C24-haloalkyl group, a C3-C24-cycloalkyl group, a Ce-Cw-aryl group and a Ce-Cw-aryl-Ci-Cw-alkylene group, where the rings of cycloalkyl, aryl, and aryl-alkylene in the three last-mentioned radicals are unsubstituted or substituted with one or more substituents R 17 ', and where the Ci-C24-alkyl group, the Ci-C24-haloalkyl group and the alkylene moiety of Ce-Cw-aryl-Ci-Cw- alkylene may be interrupted by one or more heteroatoms or heteroatomic groups selected from O, S and NR 18 ;
  • R 8 and R 9 are hydrogen, or together form a group -O-, or -S-;
  • R 18 , R 18 ', R 18 ", R 19 and R 20 are selected from hydrogen, a Ci- C2o-alkyl group, a C3-C24-cycloalkyl group, a heterocycloalkyl group, a hetaryl and a Ce-Cw- aryl groups, where the rings of cycloalkyl, heterocycloalkyl, hetaryl and aryl in the four last- mentioned radicals are unsubstituted or substituted with one or more substituents R 17 ; and each R 17 and R 17 ' is selected from a Ci-C24-alkyl group, a Ci-C24-fluoroalkyl group, a C1-C24- alkoxy group, fluorine, chlorine or bromine, or a compound obtainable by reaction of a compound of formula (I), especially a compound of formula (I'), with sulfuric acid, with the proviso that a compound of formula (6a) of formula is excluded
  • a further aspect of the present invention relates to the use of the compound of formula (I), especially the compound of formula (I'), as defined above as fluorescent dye that absorbs light emitted from an irradiation source and emits light different from that of the irradiation source and having a wavelength in the range from 680 to 1000 nm.
  • a further aspect of the present invention relates to the use of the compound of formula (I), especially the compound of formula (I'), as defined above in a near infrared spectrometer apparatus.
  • a further aspect of the present invention relates to the use of the compound of formula (I), especially the compound of formula (I'), as defined above including the compound (6a) in an agricultural film.
  • a further aspect of the present invention relates to the use of the compound of formula (I), especially the compound of formula (I'), as defined above including the compound (6a) as semiconductor in organic electronic applications.
  • a further aspect of the present invention relates to the use of the compound of formula (I), especially the compound of formula (I'), as defined above including the compound (6a) as laser dye, for bio-imaging, in an ink for machine readability and/or security applications or for the laser-welding of plastics.
  • a further aspect of the present invention relates to the use of the compound of formula (I), especially the compound of formula (I'), as defined above including the compound (6a) for brand protection or as marker for liquids, especially oils.
  • the compound of formula (I), especially the compound of formula (I'), as described herein provides several benefits, in particular high solubility and (photo)stability in the application medium. Moreover, certain compounds of formula (I), especially certain compounds of formula (I'), are outstandingly suitable as fluorescent dye so that they can be used as NIR compound emitting light comprising a wavelength of 680 to 1000 nm due to their good solubility in the application medium and the high (NIR) fluorescence quantum yield.
  • the compound of formula (I), especially the compound of formula (I') is outstandingly suitable as marker for liquids, especially oils, such as mineral oils due to its favorable application properties such as good solubility in the liquids, high fluorescence quantum yield, high molar extinction coefficient, good photo and storage stability and good detectability even in very small amounts in the correspondingly marked liquids.
  • Fig. 1 Top: Dye concentration dependent detection in flow cytometry. Bottom: Timedependent decay in flow cytometry.
  • Fig. 2 Confocal fluorescence images of WS-6e (1 ug/mL) in HeLa cells.
  • WS-6e WS-6e treated cells;
  • DAPI cell nucleus stained with DAPI (4',6-diamidino-2-phenylindole);
  • DIC differential interference microscopy image of cells, i.e. bright field;
  • Merge double-color staining images, (scale bars: 25 pm).
  • Fig. 3 Invisible ink based on 6e: a) Image under white light, indicating that the coating is noncolored and transparent, b) Fluorescence image under excitation light at 730 nm, indicating that the coating shows high fluorescence, c) Overlay of the fluorescence and white light images, d) The mixed solution of compound 6e (10 -5 M) and PMMA (0.08 mg/mL) in dichloromethane. DETAILED DESCRIPTION OF THE INVENTION
  • fluorescence quantum yield is defined as ratio of the number of photons emitted to the number of photons absorbed.
  • near-infrared light denotes light that ranges from 680 to 1000 nm.
  • visible light denotes light that ranges from approximately 380 nm to 740 nm.
  • Ci-C n -alkyl denotes a group of linear or branched saturated hydrocarbon radicals having from 1 to n carbon atoms.
  • Ci-C24-alkyl denominates a group of linear or branched saturated hydrocarbon radicals having from 1 to 24 carbon atoms
  • Ci-C4-alkyl denominates a group of linear or branched saturated hydrocarbon radicals having from 1 to 4 carbon atoms
  • C5-C20 alkyl denominates a group of linear or branched saturated hydrocarbon radicals having from 5 to 20 carbon atoms
  • alkyl examples include but are not limited to methyl, ethyl, n-propyl, isopropyl, n-butyl, sec-butyl, isobutyl, tert-butyl, 2-methylpropyl (isopropyl),
  • Ci-C4-alkyl are for example methyl, ethyl, propyl, 1 -methylethyl, butyl, 1 -methylpropyl, 2-methylpropyl or 1 ,1 -dimethylethyl.
  • Ci-C24-haloalkyl denotes straight-chain or branched C1-C24 alkyl as defined above, where some or all of the hydrogen atoms in these groups may be replaced by halogen atoms as mentioned above.
  • Ci-C2-haloalkyl examples are chloromethyl, bromomethyl, dichloromethyl, trichloromethyl, fluoromethyl, difluoromethyl, trifluoromethyl, chlorofluoromethyl, dichlorofluoromethyl, chlorodifluoromethyl, 1 -chloroethyl, 1 -bromoethyl, 1 -fluoroethyl, 2-fluoroethyl, 2,2-difluoroethyl, 2,2,2-trifluoroethyl, 2-chloro-2-fluoroethyl, 2- chloro-2,2-difluoroethyl, 2,2-dichloro-2-fluoroethyl, 2,2,2-trichloroethyl and pentafluoroethyl.
  • Ci-C24-fluoroalkyl denotes straight-chain or branched C1-C24 alkyl as defined above, where some or all of the hydrogen atoms in these groups may be replaced by fluorine above.
  • Examples for Ci-C2-fluoroalkyl are fluoromethyl, difluoromethyl, trifluoromethyl, 1 -fluoroethyl, 2-fluoroethyl, 2,2-difluoroethyl, 2,2,2-trifluoroethyl and pentafluoroethyl.
  • C1-C24-alkoxy 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.
  • C3-C24-cycloalky denotes a mono-, bi- or tricyclic cycloalkyl radical which is unsubstituted or substituted by one or more radicals R 7 , for example 1 , 2, 3 or 4 R 7 radicals.
  • Ce-Cw-aryl denotes phenyl or naphthyl.
  • Cs-Cw-aryloxy denotes phenoxy and naphthyloxy.
  • 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.
  • Cs-Cw-aryl-Ci-Cw-alkylene (which may also be referred to as aralkyl) as used herein refers to Ce-Cw-aryl-substituted alkyl radicals having at least one unsubstituted or substituted 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 NR 18 , wherein R 18 is as defined above.
  • Cs-Cw-aryl-Ci-Cw-alkylene is preferably phenyl-Ci-Cw-alkylene, more preferably phenyl-Ci-C4-alkylene, for example benzyl, 1-phenethyl, 2-phenethyl, 1-phenprop- 1-yl, 2-phenprop-1-yl, 3-phenprop-1-yl, 1-phenbut-1-yl, 2-phenbut-1-yl, 3-phenbut-1-yl, 4- phenbut-1-yl, 1-phenbut-2-yl, 2-phenbut-2-yl, 3-phenbut-2-yl or 4-phenbut-2-yl; preferably benzyl and 2-phenethyl.
  • R 3 , R 4 , R 5 and R 6 have the same meaning and are preferably hydrogen, or chlorine, more preferably chlorine.
  • R 1 and R 2 are selected from hydrogen, a Ci-C24-alkyl group, a Ci-C24-alkoxy group and a group NR 19 R 20 ; wherein R 19 and R 20 are a Ce-Cw-aryl group, especially a phenyl group, which is unsubstituted or substituted by 1 , 2 or 3 identical or different substituents R 17 wherein R 17 is defined above and is preferably Ci-Cw-alkyl.
  • R 19 and R 20 are especially a phenyl group, which is unsubstituted.
  • R 7 is a linear Ci-C24-alkyl group, a branched C3-C24-alkyl group, a Cs-Cs-cycloalkyl group, a phenyl group, or a phenyl-Ci-Cw-alkylene group, 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 R 17 ', wherein R 17 ' is defined above and is preferably C1- Ci2-alkyl,
  • R 7 is preferably selected from a C4-C2o-alkyl group, a Cs-Cs-cycloalkyl group, or a phenyl group, wherein the two last-mentioned substituents are substituted by one, two or three C1- Cs-alkyl substituents.
  • R 7 is selected from the group consisting of Cs-Cs-cycloalkyl, such as, for example, cyclopentyl, cyclohexyl, methylcyclohexyl, dimethylcyclohexyl, cycloheptyl and cyclooctyl, that is unsubstituted or substituted by one, two or three Ci-Ce-alkyl substituents; linear C4-C2o-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); or a radical of formula (B.2) in which
  • # represents the bonding site to the imide nitrogen atom
  • R c , R d and R e , in formula (A.1) are independently selected from Ci-Ci?-alkyl, where the sum of the carbon atoms of the R c , R d and R e radicals is an integer from 3 to 19;
  • R f and R g in formula (A.2) are independently selected from C1-C17-alkyl, where the sum of the carbon atoms of the R f and R g radicals is an integer from 2 to 18;
  • R h and R' in formula (A.3), independently from each other are selected from Ci-Cis-alkyl, where the sum of the carbon atoms of the R h and R' radicals is an integer from 3 to 19;
  • B where present in formulae (B.1) and (B.2), is a Ci-Cw-alkylene group; y is 0 or 1 ;
  • R 7 ' is independently of one another selected from Ci-C24-alkyl, Ci-C24-fluoroalkyl, C1-C24- alkoxy, fluorine, chlorine or bromine; z in formula (B.2) is 1 , 2 or 3.
  • radical of formula (A.3) is preferred.
  • R h and R' independently of each other, are preferably selected from linear C2-Cio-alkyl.
  • R 7 ' is preferably selected from C1-C24- alkyl, more preferably linear Ci-C -alkyl or branched Cs-C -alkyl, especially isopropyl or tert-butyl.
  • the radical of formula (B.2) is preferred.
  • R 7 is a radical of formula (B.2), wherein (B) y is absent.
  • 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.
  • the present invention is directed to compounds of formula
  • R 1 is selected from a Ci-C24-alkyl group, a Ci-C24-alkoxy group and a group NR 19 R 20 and R 2 is hydrogen; or R 1 is hydrogen and R 2 is selected from a Ci-C24-alkyl group, a Ci-C24-alkoxy group and a group NR 19 R 20 ; wherein R 19 and R 20 are a Ce-Cw-aryl group, especially a phenyl group, which is unsubstituted or substituted by 1 , 2 or 3 identical or different substituents R 17 wherein R 17 is Ci-Ci2-alkyl;
  • R 3 , R 4 , R 5 and R 6 have the same meaning and are hydrogen, or chlorine;
  • R 7 is a linear Ci-C24-alkyl group, a branched C3-C24-alkyl group, a Cs-Cs-cycloalkyl group, a phenyl group, or a phenyl-Ci-Cw-alkylene group, 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 R 17 ', wherein R 17 ' is defined above and is preferably Ci- Ci2-alkyl.
  • At least one of the substituents R 1 and R 2 is different from hydrogen.
  • R 1 is selected from a Ci-C24-alkyl group, a Ci-C24-alkoxy group and a group NR 19 R 20 and R 2 is hydrogen; or R 1 is hydrogen and R 2 is selected from a Ci-C24-alkyl group, a C1-C24- alkoxy group and a group NR 19 R 20 , wherein R 19 and R 20 are a Ce-Cw-aryl group, especially a phenyl group, which is unsubstituted or substituted by 1 , 2 or 3 identical or different substituents R 17 wherein R 17 is defined above and is preferably Ci-Cw-alkyl.
  • R 1 is hydrogen and R 2 is selected from a Ci-Cw-alkyl group, a Ci-Cw-alkoxy group and a group NR 19 R 20 , wherein R 19 and R 20 are a a phenyl group, which is unsubstituted or substituted by 1 , 2 or 3 identical or different substituents R 17 wherein R 17 is a Ci-Cw-alkyl group.
  • the compound of formula (la) is more preferably a compound of formula (Ia2), wherein
  • R 1 is selected from a Ci-C24-alkyl group, a Ci-C24-alkoxy group and a group NR 19 R 20 and R 2 is hydrogen; or R 1 is hydrogen and R 2 is selected from a Ci-C24-alkyl group, a Ci-C24-alkoxy group and a group NR 19 R 20 ; wherein R 19 and R 20 are a Ce-C -aryl group, especially a phenyl group, which is unsubstituted or substituted by 1 , 2 or 3 identical or different substituents R 17 wherein R 17 is Ci-Ci2-alkyl;
  • R 7 is a linear Ci-C24-alkyl group, a branched C3-C24-alkyl group, a Cs-Cs-cycloalkyl group, a phenyl group, or a phenyl-Ci-Cw-alkylene group, 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 R 17 ', wherein R 17 ' is defined above and is preferably Ci- Ci2-alkyl.
  • the Ci-Ci2-alkyl group in case of R 17 , R 1 and R 2 is a linear, or branched Ci-Ci2-alkyl group.
  • Examples for a linear Ci-Ci2-alkyl group are methyl, ethyl, n-propyl, n-butyl, n-hexyl, n-heptyl, n-octyl, n-nonyl, n-decyl, n-undecyl or n-dodecyl.
  • Ci-Ci2-alkyl group examples include sec-butyl, isobutyl, tert-butyl, 2-methylpropyl (isopropyl), 1 ,1 -dimethylethyl (tert-butyl), pentyl, 1 -methylbutyl, 2-methylbutyl, 3-methylbutyl, 2,2-dimethylpropyl, 1 -ethylpropyl, 1 ,1- dimethylbutyl, 2,2-dimethyl-butyl, 1 -methylpentyl, 2-methylpentyl, 1 -methylhexyl, 1- ethylpentyl, 1 -methylheptyl, 2-ethylhexyl, 6-methylheptyl (isooctyl), 1 ,1 ,3,3-teramethylbutyl (tert-octyl), isononyl, 1 ,1 -dimethylheptyl, isodec
  • the compounds of formula (I), especially the compounds of formula (I'), very especially the compounds of formula (la) can be sulfonated by treating them with concentrated sulfuric acid at elevated temperature, such as, for example, 50 to 100 °C for 0.5 to 24 h to obtain compounds of formula (I), especially compounds of formula (la) substituted with 1 to 5 SO3H groups.
  • concentrated sulfuric acid such as, for example, 50 to 100 °C for 0.5 to 24 h
  • compound of formula (la) substituted with 1 to 5 SO3H groups for example, compound WS-6e is obtained by treating compound 6e with concentrated sulfuric acid at 100 °C for 12 h.
  • the present invention is directed to compounds of formula
  • R 1 and R 2 are selected from hydrogen, a Ci-C24-alkyl group, a Ci-C24-alkoxy group and a group NR 19 R 20 ; wherein R 19 and R 20 are a Ce-C -aryl group, especially a phenyl group, which is unsubstituted or substituted by 1 , 2 or 3 identical or different substituents R 17 wherein R 17 is a Ci-Ci2-alkyl group;
  • R 3 , R 4 , R 5 and R 6 have the same meaning and are hydrogen, or chlorine;
  • R 7 is a linear Ci-C24-alkyl group, a branched C3-C24-alkyl group, a Cs-Cs-cycloalkyl group, a phenyl group, or a phenyl-Ci-Cw-alkylene group, 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 R 17 ', wherein R 17 ' is defined above and is preferably Ci- Ci2-alkyl; and
  • X is O, or S.
  • R 1 and R 2 are preferably hydrogen.
  • Compounds of formula (Ib2) are more preferred than compounds of formula (Ib1).
  • the present invention is directed to compounds of formula
  • R 3 , R 4 , R 5 and R 6 have the same meaning and are hydrogen, or chlorine;
  • R 7 is a linear Ci-C24-alkyl group, a branched C3-C24-alkyl group, a Cs-Cs-cycloalkyl group, a phenyl group, or a phenyl-Ci-Cw-alkylene group, 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 R 17 ', wherein R 17 ' is defined above and is preferably Ci- Ci2-alkyl;
  • R 1 ' and R 2 ' are a Ci-C24-alkoxy group
  • R x ' is hydrogen, or a Ci-C24-alkyl group.
  • R 3 , R 4 , R 5 and R 6 have the same meaning and are hydrogen, or chlorine, especially chlorine;
  • R 7 is a linear Ci-C24-alkyl group, a branched C3-C24-alkyl group, a Cs-Cs-cycloalkyl group, a phenyl group, or a phenyl-Ci-Cw-alkylene group, 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 R 17 ', wherein R 17 ' is defined above and is preferably Ci- Ci2-alkyl;
  • R 1 ' and R 2 ' are a Ci-C4-alkoxy group
  • R x ' is hydrogen, or a Ci-Cs-alkyl group.
  • R 7 is preferably selected from radicals of formula
  • # represents the bonding site to the imide nitrogen atom
  • R h and R' in formula (A.3), independently from each other are selected from Ci-Cis-alkyl, where the sum of the carbon atoms of the R h and R' radicals is an integer from 3 to 19;
  • B where present in formulae (B.1) and (B.2), is a Ci-Cw-alkylene group; y is 0 or 1 ; R 7 ' is independently of one another selected from Ci-C24-alkyl, Ci-C24-fluoroalkyl, C1-C24- alkoxy, fluorine, chlorine or bromine; z in formula (B.2) is 1 , 2 or 3.
  • R h and R' independently of each other, are preferably selected from linear C2-Cio-alkyl.
  • R 7 ' is preferably selected from C1-C24- alkyl, more preferably linear Ci-C -alkyl or branched Cs-C -alkyl, especially isopropyl or tert-butyl.
  • the radical of formula (B.2) is preferred.
  • R 7 is a radical of formula (B.2), wherein (B) y is absent.
  • 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.
  • Examples of particularly preferred compounds are compounds (6b), (6c), (6d), (6e), WS-6e, (6f), (6g), (6h), (6a'), (6b'), (6c'), (6d'), (6e'), (6f) and (6g') described in claim 8.
  • a further aspect of the present invention is a process for the preparation of a compound of 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 IIIPAC), for example nickel, palladium or platinum, especially in the presence of a palladium catalyst.
  • a transition metal of transition group VIII of the Periodic Table group 10 according to IIIPAC
  • nickel, palladium or platinum especially in the presence of a palladium catalyst.
  • Suitable catalysts are, for example, selected palladium-phosphine complexes, such as, for example, Pd(PPh 3 )2Cl2, Pd(PPh 3 ) 4 , Pd(dba)2, Pd2(dba) 3 , PdCh, Palladium(ll) acetate (Pd(OAc) 2 ), [Pd(allyl)CI] 2 , Pd(dppf)CI 2 , PdBr 2 (PtBu 3 ) 2 , Pd(crotyl)(PtBu 3 )CI, Pd(PtBu 3 ) 2 , Pd(Amphos) 2 CI 2 , Pd(allyl)(Amphos)CI, Pd(Binap)Br 2 , Pd(dcpp)CI 2 , Pd(DiPrPF)CI 2 , Pd- PEPPSI-IPr, Chloro(2-dicyclohexylphosphino-2',4
  • the ligand may be one or more ligands selected from the group of PPh 3 , P(oTol) 3 , P(oTol)Ph 2 , P(pTol) 3 , PtBu 3 , PtBu 3 *HBF 4 , PCy 3 , PCy3*HBF 4 , P(OiPr) 3 , DPE-Phos, dppf, dppe, dppp, dcpp, dppb, P(Furyl) 3 , CPhos, SPhos, RuPhos, XPhos, DavePhos, JohnPhos and Xantphos.
  • the ligand may be present in a range from about 2 mol % to about 50 mol %.
  • 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.
  • Suitable solvents are organic solvents such as aromatics, e.g. toluene, mesitylene, 1 -chloronaphthalene, 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, or mixtures thereof.
  • organic solvents such as aromatics, e.g. toluene, mesitylene, 1 -chloronaphthalene, acyclic ethers, e.g. 1 ,2-dimethoxyethane, cyclic ethers such as tetrahydrofuran or 1 ,4-dioxane
  • polyalkylene glycols such as diethylene glycol
  • the reaction temperature is generally within the range of 30 to 180 °C. At least one mole of the compound (VI) is used per mole of the compound (V). It may be advantageous to use a 5 to 30% molar excess of compound of the formula (VI) per mole of the compound (VI) .
  • Compounds of the formula (V) can be prepared according to known methods in the art.
  • 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 solids, they may be purified by recrystallization.
  • the compounds of the present invention can be prepared by using routine techniques familiar to a skilled person.
  • the compounds of the formula (I) can be prepared according to the following routes or as described in the experimental part of this application.
  • perylenemonoimides 6 were synthesized by using different diphenylamines in yields of 60- 70%.
  • Perylenemonoimides with stronger donor function could be obtained by using substituted aniline (6f), phenoxazine (6g) and phenothiazine (6h). All compounds are well soluble in common organic solvents such as CH2CI2, CHCI3, THF, etc. According to the procedure (Y. Zagranyarski, L. Chen, Y. F. Zhao, H. Wonneberger, C. Li, K. Mullen, Org.
  • the optical properties of the title compounds 6 and 6’ were examined in either dichloromethane or toluene (Table 1). All chromophores 6 and 6’ exhibit strong absorption (molar attenuation coefficient s is in the range of 2-8x10 4 M' 1 cnv 1 ) in the range between 600 and 800 nm and emission from 700 to 900 nm. Additionally, the absorption spectra of 6’ reveal prominent bathochromic shifts of more than 100 nm and around 2X 10 4 M' 1 cnv 1 higher absorption coefficients (E) compared with those of the reported mono-donor-substituted perylenemonoimides (Y. J. Zhao, A. A. Sukhanov, R. M. Duan, A.
  • the absorption spectra of 6’ possess an additional ⁇ 30 nm bathochromic shift compared with those of 6 due to planarization of the molecular skeleton after removal of the halogen groups.
  • the distorted perylene core 6 is proven by X-ray diffraction of 12a crystals as shown in Figure 1.
  • 12a adopts a highly twisted structure in which the dihedral angle between the two naphthalene planes is 31 °.
  • the molecules form dimers and pack in a head-to-tail manner due to the dipole-dipole interactions, while the electron-donating diphenylamine moieties are stacked on top of the neighboring electron-withdrawing anhydride unit. These dimers further stack to form a columnar structure.
  • Bending within a polycyclic aromatic hydrocarbon is known to not only enhance solubility, but also reduce aggregation (Z. Z. Wang, R. J. Li, Y. L. Chen, Y. Z. Tan, Z. Y. Tu, X. J. J. Gao, H. L. Dong, Y. P. Yi, Y. Zhang, W. P. Hu, K. Mullen, L. Chen, J. Mater. Chem. C, 2017, 5, 1308- 1312).
  • This is important since the well soluble chromophores 6 exhibit intensive fluorescence with wavelengths in the NIR region, whereas in case of 6’, only 6b’ with two tert-octyl groups has relatively high rof 33 ⁇ 1% in toluene.
  • 6 and 6’ are solvatochromicwith solvent-dependent absorption and emission maxima.
  • the absorption and emission maxima of 6e are shifted from 699 and 757 nm, respectively, in toluene to 723 and 804 nm, respectively, in dichloromethane.
  • 6e has a fluorescence quantum yield ( ⁇ >/) of about 55 ⁇ 1% (measured in both dichloromethane and toluene using Rhodamine 800 ethanol solution as reference) (R. Tormos, F. Bosca, Rsc. Adv., 2013, 3, 12031-12034).
  • the rof 6e was further determined by Edinburgh Instruments (El) FLS920 using an integrating sphere for the absolute values with 61 ⁇ 1 % in toluene and 59 ⁇ 1 % in dichloromethane, respectively.
  • WS-6e water-soluble derivatives
  • MTT 3-(4,5-dimethylthiazol-2-yl)-2,5- diphenyltetrazolium bromide
  • a security ink was prepared by mixing polymethylmethacrylate (PMMA) with 6e in dichloromethane (Z. Lei, X. Li, X. Luo, H. He, J. Zheng, X. Qian, Y. Yang, Angew. Chem. Int. Ed. 2017, 56, 1-6).
  • PMMA polymethylmethacrylate
  • the transparent and colorless ink was directly drop cast onto a grid coverslip (Ibidi).
  • Thunder Imager from Leica, the coating was not visible under white light, but only with excitation by NIR light at 730 nm (compatible emission bandpass from 770 - 850 nm). It follows that 6e-based inks can be coated on any colored as well as non-colored surface with the resulting coatings only be detectable under NIR light excitation and with a NIR camera.
  • the new NIR fluorophores absorb and emit in the far-red as well as NIR spectral region. Additionally, they reveal high thermal, chemical, and photostability. Among them, 6e with the strongest electron-donating substitution has absorption and emission maxima at 723 and 804 nm, respectively. More importantly, 6e is so far the first NIR emitter with Stokes shift larger than 50 nm ( ⁇ 81 nm) and fluorescence quantum yield higher than 20% (-60%), which render 6e being useful with extremely low concentration. Low doses not only make the 6e colorless, but also low cytotoxicity. Thus 6e is a promising candidate to make accessible the spectral region between 750 and 850 nm for various applications, such as bio-imaging and security inks.
  • the compounds of the formula (I), especially the compounds of 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.
  • the compounds of formula (I) are fluorescent dyes that absorb light having a wavelength in the range from 450 to 950 nm. They generally have their absorption maximum in the range from 600 to 880 nm. They generally emit light in a range from 615 to 950 nm.
  • the fluorescence light thus 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.
  • the compounds of formula (I) are outstandingly suitable for homogeneously coloring high molecular weight organic and inorganic materials, in particular, for example, plastics, in particular thermoplastics, coatings and printing inks, and also oxidic layer systems.
  • NIR spectroscopy is a well-established technique for detecting both chemical and physical properties of various materials.
  • NIR spectroscopy may be used for a nondestructive food analysis or for a non-destructive plant analysis in agriculture.
  • the compounds of formula (I) are also especially useful as fluorescent dye in a near infrared spectrometer apparatus for providing light having a wavelength in the range from 680 to 950 nm.
  • the compounds of formula (I) are also of interest as active components in photovoltaics.
  • the present invention also relates to the use of the compounds of formula (I) in photovoltaic applications, especially in a fluorescent solar concentrator.
  • the solar concentrator is based on solar cells and a polymeric matrix material comprising the compound of formula (I) and the solar cells are located at the outer edges of the polymeric material.
  • the compounds of formula (I) are also of interest as dye for laser applications.
  • the compounds of formula (I) are also of interest as semiconductor in organic electronic applications, especially as semiconductor in an organic field effect transistor or as semiconductor in an organic electroluminescent device.
  • the compounds of formula (I) may also be used as semiconductor in dye-sensitized solar cells.
  • the compounds of formula (I) are 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 102004 018 547, WO 02/77081 and WO 04/05427.
  • the compounds of formula (I) may also be used advantageously for laser marking and laser inscription.
  • the laser light absorbed by the compound of formula (I) brings about heating of the plastic, which leads to it foaming or the conversion of a dye present in addition, and in this way gives rise to a marking or inscription.
  • the compounds of formula (I) are also of interest as labeling groups in detection methods, especially in diagnostic and analytical methods on biological samples, including living cells.
  • the compounds of formula (I) are also of interest for use in an ink for machine readability and/or security applications.
  • the compounds of formula (I) owing to their pronounced absorption in the near infrared region of the electromagnetic spectrum, are also of interest for obtaining markings and inscriptions which absorb near infrared light and are invisible to the human eye.
  • the present invention also relates to the use of the compound of formula (I) as defined above for brand protection or as marker for liquids.
  • Useful liquids which can be marked with the compounds of the formula (I) preferably include oils such as mineral oils, vegetable and animal fatty oils, and ethereal oils.
  • oils examples include 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 mineral oils which, according to the invention, comprise gasoline, kerosene, diesel oil and also heating oil.
  • mineral oils such as gasoline, kerosene, diesel oil or heating oil, in particular gasoline, diesel oil or heating oil.
  • the above-mentioned compounds of the formula (I) are used as markers for mineral oils in which labeling is simultaneously required, for example for tax reasons.
  • the compounds of the formula (I) to be used as markers are added to the liquids in such amounts that reliable detection is ensured.
  • 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 compounds of the formula (I) may if appropriate also be used in a mixture with other markers/dyes.
  • the compounds are generally added in the form of solutions.
  • suitable solvents for providing these stock solutions are preferably aromatic hydrocarbons such as toluene, xylene or relatively high-boiling aromatics mixtures.
  • the compounds of formula (I) can also be used in the form of a mixture, comprising the compound of formula (I) and at least one further IR absorber different from the compound of formula (I).
  • Suitable further IR absorbers are in principle all known classes of IR absorbers that are compatible with the compound of formula (I).
  • Preferred further IR absorbers are selected from polymethines, phthalocyanines, naphthalocyanines, quinone-diimmonium salts, aminium salts, rylenes, inorganic IR absorbers and mixtures thereof.
  • Further polymethine IR absorbers are preferably selected from cyanines, squaraines, croconaines and mixtures thereof.
  • Further inorganic IR absorbers are preferably selected from indium tin oxide, antimony tin oxide, lanthanum hexaboride, tungsten bronzes, copper salts etc.
  • the IR absorbers can be generally used in a concentration of from 10 ppm to 25%, preferably 100 ppm to 10%, depending on the chosen application.
  • the compounds of formula (I) and IR absorber mixtures are especially suitable 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.
  • IR-absorption plays an important role. Most of the actually circulating currency carries not only visibly coloured printings, but also specific features which are only detectable in the infrared part of the spectrum. Generally, these IR- 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.
  • the present invention also relates to a method of detecting the authenticity of a security document as defined above, or below, comprising the steps of: a) measuring an absorbance, reflectance or transmittance spectrum of the security document in the VIS/NIR range of the electromagnetic spectrum; and b) comparing the spectrum measured under a) and/or information derived therefrom with a corresponding spectrum and/or information of an authentic security element.
  • any ink used in a security printing process should, when cured, be robust, water-resistant, resistant to various chemicals and flexible.
  • the employed printing ink formulations should be useable on plastics as well as paper.
  • the compounds of formula (I) because of its unique application properties are especially suitable for printing ink formulations that are employed for security printing and in particular for bank notes, identity cards, passports, tax stamps, stock certificates, credit cards, labels etc.
  • the IR absorber is 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, gravure 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, intaglio printing and letterpress printing are usually formulated as high-viscosity paste printing inks, whereas printing inks for inkjet printing, flexographic printing and gravure printing are usually formulated as liquid printing inks with comparatively low viscosity.
  • the expression “printing ink” also encompasses formulations that in addition to at least one IR absorber of the general formula (I) comprise a colorant.
  • the expression “printing ink” also encompasses printing lacquers that comprise no colorant.
  • the printing ink formulation for security printing preferably comprises a) a compound of formula (I), especially the compounds of formula (I'), as defined above, b) a polymeric binder, c) a solvent, d) optionally at least one colorant, and e) optionally at least one further additive.
  • 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 lnks"-Ullmann's Encyclopedia of Industrial Chemistry, Sixth Edition, 1999 Electronic Release. A formulation of an IR- absorbing intaglio ink formulation is described in US 20080241492 A1. 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 15% by weight, in particular from 0.01 to 5% by weight, based on the total weight of the printing ink formulation, of component a).
  • the compound of formula (I), especially the compounds of formula (I'), is present in the printing ink formulation in dissolved form or in solid form (in a finely divided state).
  • the printing ink formulation according to the invention contains in general from 5 to 74% 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 component b).
  • Suitable polymeric binders b) for the printing ink formulation according to the invention are for example selected from natural resins, phenol resin, 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.
  • 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.
  • 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 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 II: Prepolymers & Reactive Diluents, edited by G Webster.
  • a curable polymeric binder 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 1 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 are selected from water, organic solvents and mixtures thereof.
  • reactive monomers which also act as solvents are regarded as part of the afore-mentioned binder component b).
  • solvents 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.
  • 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
  • the printing ink formulation according to the invention may contain an additional colorant d).
  • 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 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 comprehensively 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, lithopones (zinc sulfide + barium sulfate), or coloured pigments, examples being iron oxides, bismuth vanadates, lead chromates, lead molybdates, iron blue, Cobalt blue, Cobalt green, Ni-rutile yellow, Cr-rutil yellow, zinc yellow, zinc green, ultramarine, manganese black, antimony black, manganese violet, carbon black, graphite,.
  • inorganic white pigments such as titanium dioxide, preferably in the rutile form, barium sulfate, zinc oxide
  • the printing ink formulation of the invention may also comprise organic colour pigments, examples being Monoazo, Disazo, B-Naphthol, Naphthol AS, Azo pigment Lakes, Benzimidazolone, Metal complex pigments, Isoindolinone, Isoindoline, Phthalocyanine, Quinacridone, Perylene, perinone, Diketopyrrolo- Pyrrol, Thioindigo, Anthraquinone, Anthrapyrimidine, Indanthrone, Flavanthrone, Pyranthrone, Dioxazine, Triarylcarbonium, Quinophthalone.
  • organic colour pigments examples being Monoazo, Disazo, B-Naphthol, Naphthol AS, Azo pigment Lakes, Benzimidazolone, Metal complex pigments, Isoindolinone, Isoindoline, Phthalocyanine, Quinacridone, Perylene, perinone, Diketopyrrolo-
  • Suitable fillers are, for example, aluminosilicates, such as feldspars, silicates, such as kaolin, talc, mica, magnesite, alkaline earth metal carbonates, such as calcium carbonate, in the form for example of calcite or chalk, magnesium carbonate, dolomite, alkaline earth metal sulfates, such as calcium sulfate, silicon dioxide, etc.
  • the printing ink formulation according to the invention may contain at least one additive e).
  • 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, surfactants, 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.
  • the printing ink formulation for security printing preferably contains a) 0.0001 to 25% by weight of the compound of formula (I), especially the compounds of formula (I'), b) 5 to 74% by weight of at least one polymeric binder, c) 1 to 94.9999% by weight of at least one a solvent, d) 0 to 25% by weight of at least one colorant, and e) 0 to 25% by weight of at least one further additive, wherein the sum of components a) to e) adds up to 100%.
  • the printing ink formulations according to the invention are advantageously prepared in a conventional manner, for example by mixing the individual components.
  • the compound of formula (I) is present in the printing ink formulations in a dissolved or finely divided solid form.
  • Additional colorants may be employed in the printing ink formulation of the invention or in a separate ink formulation.
  • the time of application of the printing ink formulation according to the invention is usually immaterial.
  • 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 prior to the printing ink formulation according to the invention.
  • the primers are applied in order to improve adhesion to the substrate.
  • 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.
  • 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.
  • 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.
  • 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 watervapour barriers.
  • the compound of formula (I), especially the compounds of formula (I'), and IR absorber mixtures are also especially suitable for laser welding of plastics.
  • the laser welding is preferably carried out using an ND:YAG laser at 1064 nm or using a diode laser at 980 nm or 940 nm.
  • concentration of the new crystal form of compound (1) or an IR absorber mixtures is e.g. from 5 to 500 ppm, preferably from 10 to 200 ppm.
  • plastics components are welded to one another.
  • the plastics components to be fused may have any shape.
  • at least one of the plastics components may be a film.
  • the compound of formula (I), especially the compounds of formula (I'), is suitable for welding transparent at least translucent plastics materials.
  • the employed plastics materials may be colourless or coloured.
  • the plastics components to be fused may be composed of the same polymer or of different polymers.
  • the plastics components employed for laser welding are selected from thermoplastic polymers.
  • it is also possible that neither of the plastics components to be fused is composed of thermoplastic; however, a coating of at least one part with a thermoplastic comprising the compound of formula (I) is required.
  • the plastics components employed for laser welding preferably comprise or consist of at least one polymer selected from polyolefins, polyolefin copolymers, polytetrafluoroethylenes, ethylene-tetrafluoroethylene copolymers, polyvinyl chlorides, polyvinylidene chlorides, polyvinyl alcohols, polyvinyl esters, polyvinyl alkanals, polyvinyl ketals, polyamides, polyimides, polycarbonates, polycarbonate blends, polyesters, polyester blends, poly(meth)acrylates, poly(meth)acrylate-styrene copolymer blends, poly(meth)acrylate- polyvinylidene difluoride blends, polyurethanes, polystyrenes, styrene copolymers, polyethers, polyether ketones and polysulfones and mixtures thereof.
  • matrix polymers from the group of the polyolefins, polyolefin copolymers, polyvinyl alkanals, polyamides, polycarbonates, polycarbonate-polyester blends, polycarbonate-styrene copolymer blends, polyesters, polyester blends, poly(meth)acrylates, poly(meth)acrylate-styrene copolymer blends, poly(meth)acrylate-polyvinylidene difluoride blends, styrene copolymers and polysulfones and mixtures thereof.
  • Particularly preferred polymers are transparent or at least translucent.
  • Examples include: polypropylene, polyvinylbutyral, nylon-[6], nylon-[6,6], polycarbonate, polycarbonatepolyethylene terephthalate blends, polycarbonate-polybutylene terephthalate blends, polycarbonate-acrylonitrile/styrene/acrylonitrile copolymer blends, polycarbonate- acrylonitrile/butadiene/styrene copolymer blends, polymethyl methacrylate- acrylonitrile/butadiene/styrene copolymer blends (MABS), polyethylene terephthalate, polybutylene terephthalate, polymethyl methacrylate, impact-modified polymethyl methacrylate, polybutyl acrylate, polymethyl methacrylate-polyvinylidene difluoride blends, acrylonitrile/butadiene/styrene copolymers (ABS), st
  • Suitable polymer preparations for laser welding comprise
  • thermoplastic matrix polymer suitable for forming the plastics parts
  • Those polymer preparations for laser welding are likewise in accordance with the invention and are suitable for producing fusion-bonded plastics parts with the aid of laser radiation whose wavelength is outside the visible region.
  • Polymer preparations for laser welding may advantageously be produced by a conventional extrusion or kneading process.
  • the components B), and, if present, C) may be mixed from the outset, in the weight ratio corresponding to the desired end concentration, with the matrix polymer A) (direct compounding), or a distinctly higher concentration of B) and, if present, C) may initially be selected and the concentrate formed (masterbatch) subsequently diluted with further matrix polymer A) in the course of the manufacture of the parts to be fused.
  • Suitable additives C) are UV stabilizers, antioxidants, processing plasticizers, etc.
  • the polymer preparations for laser welding may comprise at least one colorant for establishing a desired hue as additive, especially transparent organic pigments and in particular dyes, for example C.l. Pigment Yellow 109, 110, 128, 138, 139, 150, 151, 147, 180, 183, 185 192 and 196, C.l. Pigment Orange 70, C.l. Pigment Red 122, 149, 178 and 179, 181 , 202, 263, C.l. Pigment Violet 19, 23, 37 and 29, C.l. Pigment Blue 15, 15:1, 15:3 and 15:4, 60, C.l. Pigment Green 7 and 36, C.l. Solvent Yellow 14, 21 , 93, 130, 133, 145, 163, C.l.
  • transparent organic pigments and in particular dyes for example C.l. Pigment Yellow 109, 110, 128, 138, 139, 150, 151, 147, 180, 183, 185 192 and 196, C.l. Pigment Orange 70, C.l.
  • Solvent Red 52 135, 195, 213, 214 and 225, C.l. Solvent Blue 35, 45, 67, 68, 97, 104, 122, 132, C.l. Solvent Violet 13, 46, 49, C.l. Solvent Green 3, 5 and 28, C.l. Solvent Orange 47, 60, 86, 114, and 163, C.l. Solvent Brown 35, 53, and also C.l. Disperse Yellow 54, 87, 201 , C.l. Disperse Orange 30, C.l. Disperse Red 60 and C.l. Disperse Violet 57.
  • a further possible additive group is that of additives which likewise modify the visual 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.
  • 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.
  • the present invention further provides a color converter comprising
  • a polymeric matrix material selected from a polystyrene, polycarbonate, polyacrylate, polymethylmethacrylate, polymethacrylate, polyvinylpyrrolidone, polyvinyl acetate, polyvinyl chloride, polybutene, silicone, epoxy resin, polyvinyl alcohol, poly(ethylene vinylalcohol)-copolymer, polyacrylonitrile, polyvinylidene chloride, polystyrene acrylonitrile, polybutylene terephthalate, polyethylene terephthalate, a 2,5- furandicarboxylate polyester, polyvinyl butyrate, polyvinyl chloride, polyamides, polyoxymethylenes, polyimides, polyetherimides or mixtures thereof; and
  • 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.
  • 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 color converter does not comprise a light scattering agent.
  • the color converter comprises a light scattering agent.
  • the polymeric matrix material comprises scattering agents. 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 pm, preferably 0.1 to 1 pm, more preferably 0.15 to 0.4 pm. 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.
  • 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 is usually in the range from 0.5 to 50 pm, prefeably 1 to 10 pm.
  • 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.
  • light-scattering compositions which contain polymeric particles based on vinyl acrylate with a core/shell morphology in combination with TiC>2 as described in EP-A 634 445.
  • the polymeric matrix material can also comprise at least one further additive selected from an UV absorber, a hindered amine light stabilizer, flame retardant, UV stabilizer, thermal stabilizer, anti-oxidant, plasticizer, antifogging agent, nucleating agent, antistatic agent, filler or a reinforcing material, or combinations thereof.
  • Hindered amine light stabilizers, UV stabilizers and thermal stabilizers are known to those skilled in the art.
  • Suitable antioxidants or free-radical scavengers are, for example, phenols, especially sterically hindered phenols, such as butylhydroxyanisole (BHA) or butylhydroxytoluene (BHT), or sterically hindered amines (HALS).
  • Stabilizers of this kind are sold, for example, by BASF under the Irganox® trade name.
  • antioxidants and free-radical scavengers can be supplemented by secondary stabilizers, such as phosphites or phosphonites, as sold, for example, by BASF under the Irgafos® trade name.
  • UV absorbers are, for example, benzotriazoles, such as 2-(2-hydroxyphenyl)-2H- benzotriazole (BTZ), triazines, such as (2-hydroxyphenyl)-s-triazine (HPT), hydroxybenzophenones (BP) or oxalanilides. UV absorbers of this kind are sold, for example, by BASF under the Uvinul® trade name.
  • the color converter comprising the compound of formula (I), especially the compounds of formula (I'), can be part of an agricultural foil, agricultural netting or a greenhouse screen or an illumination device.
  • the color converter may be supported by glass.
  • the agricultural foil, agricultural netting or greenhouse screen consists of the color converter used according to the invention.
  • the color converter according to the present invention can also be part of a near infrared light source.
  • a further object of the present invention relates to a near infrared light source, comprising
  • a light source selected from a blue LED, red LED or white LED
  • the near infrared light source may be part of a NIR-LED or a near infrared spectrometer.
  • UV-Vis (CH 2 CI 2 ): A max 709 (64 800) nm (M’ 1 ).
  • UV-Vis (CH2CI2): Amax 686 (54600) nm ( /Mcnr 1 ).
  • UV-Vis (CH2CI2): A max 722 (60200) nm (M’ 1 ).
  • UV-Vis (CH2CI2): 4 ma x 680 (39 150) nm ( /Mcnr 1 ).
  • UV-Vis (CH2CI2): Amax 664 (42 500) nm (M’ 1 ).

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Abstract

La présente invention concerne des composés de formule (I'), un procédé pour les préparer et leur utilisation en tant que colorants fluorescents absorbant la lumière émise par une source d'irradiation et émettant une lumière différente de celle de la source d'irradiation et possédant une longueur d'onde comprise entre 680 et 1000 nm ; et ce dans des applications photovoltaïques ; ou en tant que semi-conducteurs dans des applications électroniques organiques ; en tant que colorants laser, dans une encre pour des applications de lecture automatique et/ou de sécurité ou pour le soudage au laser de matières plastiques ; ou pour la protection de marques ou en tant que marqueurs pour liquides. Les composés de formule (I) peuvent avoir un rendement quantique de fluorescence élevé, un coefficient d'extinction molaire élevé, une solubilité et une stabilité élevées dans le milieu d'application, une bonne stabilité au stockage et/ou une bonne détectabilité, même en très petites quantités, dans les liquides marqués de manière correspondante.
PCT/EP2022/073245 2021-08-24 2022-08-19 Nouveaux émetteurs nir à base de pérylène WO2023025694A1 (fr)

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