WO2023241950A1 - Mixtures of compounds having improved solubility for use as markers - Google Patents

Mixtures of compounds having improved solubility for use as markers Download PDF

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Publication number
WO2023241950A1
WO2023241950A1 PCT/EP2023/064835 EP2023064835W WO2023241950A1 WO 2023241950 A1 WO2023241950 A1 WO 2023241950A1 EP 2023064835 W EP2023064835 W EP 2023064835W WO 2023241950 A1 WO2023241950 A1 WO 2023241950A1
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WIPO (PCT)
Prior art keywords
formula
meaning
mixture
different
compounds
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PCT/EP2023/064835
Other languages
French (fr)
Inventor
Hans Reichert
Oliver Seeger
Korinna Dormann
Holger Leybach
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Basf Se
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Publication of WO2023241950A1 publication Critical patent/WO2023241950A1/en

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Classifications

    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D487/00—Heterocyclic compounds containing nitrogen atoms as the only ring hetero atoms in the condensed system, not provided for by groups C07D451/00 - C07D477/00
    • C07D487/22—Heterocyclic compounds containing nitrogen atoms as the only ring hetero atoms in the condensed system, not provided for by groups C07D451/00 - C07D477/00 in which the condensed system contains four or more hetero rings
    • 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
    • C09D11/30—Inkjet printing inks
    • C09D11/32—Inkjet printing inks characterised by colouring agents
    • 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
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10L—FUELS NOT OTHERWISE PROVIDED FOR; NATURAL GAS; SYNTHETIC NATURAL GAS OBTAINED BY PROCESSES NOT COVERED BY SUBCLASSES C10G, C10K; LIQUEFIED PETROLEUM GAS; ADDING MATERIALS TO FUELS OR FIRES TO REDUCE SMOKE OR UNDESIRABLE DEPOSITS OR TO FACILITATE SOOT REMOVAL; FIRELIGHTERS
    • C10L1/00—Liquid carbonaceous fuels
    • C10L1/003—Marking, e.g. coloration by addition of pigments

Definitions

  • the present invention relates to mixtures of compounds of the formula (la), (lb), (Ic) and (Id), a process for its preparation and its use in security applications; for brand protection or as marker for liquids.
  • the compounds of formula (I) have 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.
  • the process of the present invention leads to a complex mixture of compounds of formula (la), (lb), (Ic) and (Id).
  • composition of the mixture of compounds of formula (la), (lb), (Ic) and (Id) can be controlled by varying the reaction conditions and can be analyzed using various methods, such as, for example, HPLC, LC-MS, MALDI-Tof, NMR etc.
  • US5932723A relates to a process for preparing metal-free phthalocyanine by reductive cyclization of phthalonitrile in the presence of an aliphatic alcohol, of a redox catalyst and of an inorganic base comprises effecting the cyclization in the presence of one or more phthalocyanine derivatives selected from the group consisting of phthalocyaninesulfonic acids and -carboxylic acids and their alkali metal, ammonium and alkylammonium salts, the amino-substituted and aminomethylated phthalocyanines and their reaction products with alkylating agents, sulfonic acids, sulfonyl chlorides and carbonyl chlorides, the imidomethylene- and amidomethylene-substituted phthalocyanines, the alkyl-, aryl- and cyano-substituted phthalocyanines, the hydroxyland alkoxy-substituted phthalocyanines and their reaction products with tetraal
  • EP0983274B1 (WO98/52950A1) relates to the use of phthalocyanines of the formula
  • Me is twice hydrogen, twice lithium, magnesium, zinc, copper, nickel, VO, TiO, AICI, AIOH, AIOCOCH3, AIOCOCF3, SiCI 2 or Si(OH) 2
  • at least four of the radicals R 1 to R 16 are each independently of the others pyrrolidin-1 - yl, pyrazolidin-1 -yl, imidazolidin-1-yl, oxazolidin-3-yl, isoxazolidin-2-yl, piperidin-1-yl, piperazin-1-yl, morpholin-4-yl or thiomorpholin-4-yl, which radicals can be monosubstituted or polysubstituted by Ci-C4-alkyl, benzyl, phenylethyl or phenyl, and which are bonded to the phthalocyanine structure via a ring nitrogen atom
  • any remaining radicals R 1 to R 16 are each hydrogen, halogen, hydroxysulfonyl or Ci-C
  • WO98/14520A1 relates to novel phthalocyanines of formula which are substituted by 1-4 formyl, carbonyl, hydroxymethyl or carboxyl groups, to their use in recording layers of optical recording media, as well as to a novel process for the preparation of some of these compounds.
  • US5, 817,804 relates to a mixture of isomeric alkoxy-substituted phthalocyanines and to a process for their preparation by reacting compounds of the formula (V) in the presence of a metal salt, a Lewis acid, urea and selected solvents.
  • W0200640021A2 relates to cobalt (lll)phthalocyanine mixtures containing isomers selected from the group of formulas (Iw), (lx), (ly) and (Iz), wherein the amount of both of the isomers ly and Iz have a maximum of 20 wt. %, in relation to the total of the isomers Iw to Iz and their use as optical data carrier.
  • WO2011/012698A2 describes a phthalocyanine derivative of formula (I) consisting of 4 isomers wherein the relative isomer B content is less than or equal to 1% by weight and its use for the preparation of a pharmaceutical composition.
  • W02007/104685 relates to the use of phthalocyanines of the formula (I) as markers for liquids, especially mineral oils.
  • W02002/50216A2 relates to a method for the marking of hydrocarbons, by addition of at least one first marking agent( subsequently referred to as first marking agent), characterised in that, in addition, at least one further second marking agent is added to the hydrocarbon, which, under conditions for removal of the first marking agent, is not completely removable from the hydrocarbon.
  • W02005/070935 relates to the use of special phthalocyanines carrying substituents bound by methylene groups on the skeletal structure thereof, as marking substances for liquids, especially mineral oils and liquids, and especially mineral oils containing at least one such phthalocyanine as a marking substance.
  • W02005/066179A1 describes a method for preparing metal-free phthalocyanines phthalodinitrile of formula (la) in an inert solvent having a boiling temperature of at least 120 °C (under normal pressure) in the presence of ammonia.
  • the variable n can take the value of 1 , 2, 3 or 4 and the radicals R denote a five- or six-membered saturated, nitrogen-containing heterocyclic ring that is optionally substituted by one or two Ci-Cs alkyl groups, the heterocyclic ring being bonded to the benzene ring by a nitrogen atom in the ring; the heterocyclic ring may further contain one or two additional nitrogen atoms or an additional oxygen or sulphur atom.
  • the method is characterised in that the reaction is performed in the presence of an alkaline metal hydroxide or alkaline metal carbonate.
  • W02007/104685A1 relates to the use of phthalocyanines of the formula (I) as marking substances for liquids, , wherein
  • M is twice hydrogen, twice lithium, magnesium, zinc, copper, nickel, VO, TiO, AICI, AIOCOCH3, AIOCOCF3, SiCI 2 or Si(OH) 2 ;
  • m is 1 , 2, 3, or 4;
  • n is identical or different and is 0, 1 , 2, 3 or 4;
  • r is the same or different and is 0, 1 , 2, 3 or 4;
  • m+r is 1 , 2, 3, or 4;
  • n+r is 0, 1 , 2, 3 or 4;
  • R is the same or different
  • R 1 is the same or different H, halogen, or R 2 ;
  • R 2 is the same or different (C1 -C1 8 )-alkyl, (C4-C8)-Cycloalkyl, (C2-CI2)- alkenyl, (Ce- C10)-aryl, (C7- C2o)aralkyl or (C2- Cl2)alkynyl, where aryl radicals may be unsubstituted or substituted by one or more halogen, cyano, nitro, hydroxy, amino, 20-alkyl which is optionally interrupted by 1 to 4 oxygen atoms in ether function, Ci-C2o-alkoxy, CI-C2O- alkylamino or C1-C2o-dialkylamino;
  • R 3 is the same or different from R 1 or two radicals R 3 or a radical R 1 and R 3 together form a further ring system;
  • R 4 , R 5 , R 6 are identical or different and are H, halogen, CH3 or C2H5, Y 1 , Y 2 , Y 3 , Y 4 , Y 5 , Y 6 are the same or different (Ci.C4)-alkylene, which is unsubstituted or substituted by one or more halogen atoms; s is O, 1 , 2, 3, 4, 5, or 6; and t is 0, 1 , 2, 3.
  • W02016/015208A1 relates to a phthalocyanine compound of formula which is suitable for forming a color filter used for a liquid crystal display device, a method for synthesis the phthalocyanine compound and a color filter formed from the composition, wherein Ri to R4 are selected from a saturated or unsaturated hydrocarbon group having 1 to 50 carbon atoms and an organic group containing amine and 1 to 8 carbon atoms, m to n4 are integer from 1 to 4, M is a divalent ion, provided that (a) at least one of R1 to R4 is a saturated or unsaturated hydrocarbon group having 6 to 20 carbon atoms and (b) at least one of R1 to R4 is an organic group containing amine and 1 to 8 carbon atoms.
  • the invention relates to mixture of compounds of the formula
  • Ra, Rb, Rc and Rd have independently of each other the meaning of R 1 , R 2 and R 3 , R 1 is present in the compounds of formula (la), (lb), (Ic) and (Id) in an average amount x,
  • R 2 is present in the compounds of formula (la), (lb), (Ic) and (Id) in an average amount y, and
  • R 3 is present in the compounds of formula (la), (lb), (Ic) and (Id) in an average amount z, wherein
  • R 1 is a group of formula
  • R 2 has the meaning of R 1 and is different from R 1 ;
  • R 3 has the meaning of R 1 and is different from R 1 and R 2 ;
  • R 2 has the meaning of R 1 and is different from R 1 ;
  • R 3 has the meaning of R 1 and is different from R 1 and R 2 ;
  • R 4 is a Ci-Ci2alkyl group
  • R 5 is a hydrogen atom, or a Ci-Ci2alkyl group
  • R 6 is a hydrogen atom, or a Ci-C ⁇ alkyl group
  • R 7 is a hydrogen atom, a Ci-C ⁇ alkyl group, or a phenyl group
  • R 8 is a hydrogen atom, a Ci-C ⁇ alkyl group, or a phenyl group
  • R 9 is a hydrogen atom, a Ci-Ci2alkyl group, or a phenyl group
  • m is 0, 1 or 2
  • x is 0.05 to 3.95
  • y is 0.05 to 3.95
  • z is 0 to 2.00
  • the sum of x, y and z is 4.
  • x is 0.50 to 3.50 and y is 3.50 to 0.50, especially x is 1 .50 to 2.50 and y is 2.50 to 1.50, with the proviso that the sum of x, y and z is 4.
  • z is 0, x is 2 and y is 2.
  • x is 0.50 to 3.50, y is 0.50 to 3.50, z is 0.10 to 1.50, more preferably x is 1.00 to 2.00, y is 1.00 to 2.00, z is 0.50 to 1.50, with the proviso that the sum of x, y and z is 4.
  • the present invention provides the following advantages: i) The process of the present invention leads to a complex mixture of compounds of formula (la), (lb), (Ic) and (Id).
  • the exact composition of the mixture of compounds of formula (la), (lb), (Ic) and (Id) can be controlled by varying the reaction conditions and can be analyzed using various methods, such as, for example, HPLC, LC-MS, MALDI- Tof, NMR etc.
  • ii) While certain macroscopic properties remain almost the same (absorption, emission etc.), the composition of the mixture of compounds of formula (la), (lb), (Ic) and (Id) can be varied and a batch assignment can be made.
  • the mixture of compounds according to the present invention is preferably obtainable by reaction of
  • R 1 is a group of formula
  • R 2 has the meaning of R 1 and is different from R 1 ; and R 3 has the meaning of R 1 and is different from R 1 and R 2 ; or the mixture of compounds according to the present invention is preferably obtainable by reaction of x/4 mol of a compound of formula y/4 mol of a compound of formula (lib), and z/4 mol of a compound of formula mol NH 3 , wherein
  • R 2 has the meaning of R 1 and is different from R 1 ; and R 3 has the meaning of R 1 and is different from R 1 and R 2 ; and R 4 , R 5 , R 6 , R 7 , R 8 , R 9 , m, x, y and z are defined in claim 1.
  • Groups of formula , which are substituted in ortho and/or para position are preferred against groups of formula (IVa), which are substituted in meta position.
  • R 1 and R 2 R 1 and R 2 represent groups of formula wherein at least one of the substituents R 7 , R 8 and R 9 is different from a hydrogen atom.
  • Mixtures of compounds of the present application having three different substituents R 1 , R 2 and R 3 are preferred against mixtures of compounds of the present application having two different substituents R 1 and R 2 .
  • Ci-Ci2alkyl group denominates a group of linear or branched saturated hydrocarbon radicals having from 1 to 12 carbon atoms.
  • Ci-Ci2alkyl group examples include but are not limited to methyl, ethyl, n-propyl, isopropyl, n-butyl, 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, 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, 2,2-
  • R 1 is selected from
  • R 2 has the meaning of R 1 and is different from R 1 ;
  • R 3 has the meaning of R 1 and is different from R 1 and R 2 ,
  • R 7 is a Ci-Ci2alkyl group
  • R 7 ' and R 7 " are independently of each other a Ci-C ⁇ alkyl group, or a phenyl group; and R 8 and R 9 are independently of each other a Ci-C ⁇ alkyl group, and
  • R 9 ' is a hydrogen atom, or a Ci-C ⁇ alkyl group.
  • R 2 has the meaning of R 1 and is different from R 1 ;
  • R 3 has the meaning of R 1 and is different from R 1 and R 2 .
  • R 1 is selected from the group
  • R 2 has the meaning of R 1 and is different from R 1 ;
  • R 3 has the meaning of R 1 and is different from R 1 and R 2 , R 4 is a hydrogen atom, or a Ci-C ⁇ alkyl group;
  • R 5 is a hydrogen atom, or a Ci-C ⁇ alkyl group
  • R 6 is a hydrogen atom, or a Ci-C ⁇ alkyl group.
  • R 1 is preferably selected from the group of formula
  • R 2 has the meaning of R 1 and is different from R 1 ;
  • R 3 has the meaning of R 1 and is different from R 1 and R 2 .
  • the present invention is related to mixtures of compounds of formula (la), (lb), (Ic) and (Id), wherein
  • Ra, Rb, Rc and Rd have independently of each other the meaning of R 1 , R 2 and R 3 , wherein R 1 , R 2 and R 3 as well as x, y and z have the meaning given in the below table:
  • Mixtures of compounds of the present application having three different substituents R 1 , R 2 and R 3 are preferred against mixtures of compounds of the present application having two different substituents R 1 and R 2 .
  • R 1 , R 2 and R 3 are derived from a group of formula the mixtures B-1 and B-6 are particularly preferred.
  • R 1 , R 2 and R 3 are derived from a group of formula (IVb) the mixture A-1 is particularly preferred.
  • a further aspect of the present invention relates to the use of the mixture of compounds according to the present invention 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 950 nm.
  • a further aspect of the present invention relates to the use of the mixture of compounds according to the present invention in an ink for machine readability and/or security applications.
  • a further aspect of the present invention relates to the use of the mixture of compounds according to the present invention in an ink for machine readability and/or security applications, or for brand protection or as marker for liquids, especially oils.
  • mixture of compounds according to the present invention as described herein provides several benefits, in particular high solubility and stability in the application medium.
  • certain mixtures of compounds according to the present invention are outstandingly suitable as fluorescent dyes so that they can be used as NIR compounds emitting light comprising a wavelength of 680 to 950 nm due to their good solubility in the application medium and the high fluorescence quantum yield.
  • the mixture of compounds according to the present invention 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 molar extinction coefficient, good storage stability and good detectability even in very small amounts in the correspondingly marked liquids.
  • 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 1100 nm.
  • visible light denotes light that ranges from approximately 380 nm to 740 nm.
  • the compounds in the mixture according to the present invention 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 mixture of compounds according to the present invention are also of interest for use in an ink for machine readability and/or security applications.
  • the mixtures of compounds according to the present invention 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 mixtures of compounds according to the present invention for brand protection or as marker for liquids.
  • Useful liquids which can be marked with the mixture of compounds according to the present invention preferably include oils such as mineral oils (fuels), 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 (fuels) in which labeling is simultaneously required, for example for tax reasons.
  • the mixture of compounds according to the present invention to be used as markers are added to the liquids, especially fuels 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 present invention relates to a method of marking liquids, especially fuels, comprising the steps of a) adding the mixture of compounds according to the present application, to the liquid, especially fuel; and b) measuring an absorbance, reflectance or transmittance spectrum of the liquid, especially fuel in the VIS/NIR range of the electromagnetic spectrum; and c) comparing the spectrum measured under b) and/or information derived therefrom with a corresponding spectrum and/or information of an authentic liquid, especially fuel; as well as to the use of the mixture of compounds according to the present invention in marking liquids, especially fuels.
  • the liquid is preferably a fuel.
  • fuel refers to products having a predominantly hydrocarbon composition, although they may contain minor amounts of oxygen, nitrogen, sulfur or phosphorus.
  • fuel includes crude oils, as well as products derived from petroleum refining processes.
  • a “fuel” includes without limitation crude oil, lubricating oil, hydraulic fluid, brake fluid, gasoline, diesel fuel, kerosene, jet fuel, heating oil and heavy fuel oil.
  • the petroleum hydrocarbon is selected from the group consisting of gasoline, diesel fuel, kerosene, and jet fuel, and even more preferably from the group consisting of gasoline and diesel fuel.
  • mixtures of compounds according to the present invention may if appropriate also be used in a mixture with other markers/dyes.
  • the mixtures of compounds according to the present invention are generally added in the form of concentrates.
  • the present invention is directed to a concentrate for marking liquids, especially fuels, comprising a) the mixture of compounds according to the present invention as defined above, c) a solvent, d) optionally at least one colorant, and e) optionally at least one further additive.
  • the mixture of compounds according to the present invention as defined above is preferably provided as a concentrate for addition to the liquid, especially fuel to be marked.
  • a concentrate of between 1% to 10% of the marker in an organic solvent is used.
  • Organic solvents suitable for this purpose are, for example, alkyl benzenes, alkylnaphthalenes or a proprietary blend of such compounds.
  • Polar organic solvents may be included to increase the solubility of the marker compound in the concentrate, such as formamide, N,N-dimethylformamide and N-methylpyrrolidone.
  • the solvents are a mixture of aromatic and aprotic solvents. These solvents may be used singly or in blends but must be miscible with the liquid, in particular the fuel, being marked.
  • the mixtures of compounds according to the present invention 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 mixtures of compounds according to the present invention 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 mixture of compounds according to the present invention 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.
  • printing ink also encompasses formulations that comprise a colorant.
  • the printing ink formulation for security printing preferably comprises a) the mixture of compounds according to the present invention 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 Inks”- 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 mixture of compounds according to the present invention 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, (1- 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, (1- Naphthol, Naphthol AS, Azo pigment Lakes, Benzimidazolone, Metal complex pigments, Isoindolinone, Isoindoline, Phthalocyanine, Quinacridone, Perylene, perinone, Diketopyrrolo-P
  • 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 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 according to the invention preferably contains a) 0.0001 to 25% by weight of the mixture of compounds according to the present invention, 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 mixture of compounds according to the present invention 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 water-vapour barriers.
  • the present invention relates to security documents, comprising a substrate and the mixture of compounds according to the present invention, or security documents, obtainable by a printing process, wherein the printing ink formulation as defined above is employed.
  • the security document is preferably selected from a bank note, a passport, a check, a voucher, an ID- or transaction card, a stamp and a tax label.
  • Ra, Rb, Rc and Rd have independently of each other the meaning of R 1 , R 2 and R 3 , comprises reacting x/4 mol of a compound of formula y/4 mol of a compound of formula (lib), and z/4 mol of a compound of formula mol of a reducing agent, especially a compound of formula wherein
  • R 1 is a group of formula
  • R 2 has the meaning of R 1 and is different from R 1 ;
  • R 3 has the meaning of R 1 and is different from R 1 and R 2 ; or a process for the preparation of the mixture of compounds of formula (la), (lb), (Ic) and (Id), or comprises reacting x/4 mol of a compound of formula y/4 mol of a compound of formula (lib), and z/4 mol of a compound of formula mol NH 3 , wherein
  • R 2 has the meaning of R 1 and is different from R 1 ;
  • R 3 has the meaning of R 1 and is different from R 1 and R 2 ; and R 4 , R 5 , R 6 , R 7 , R 8 , R 9 , m, x, y and z are defined above.
  • mixtures of compounds according to the present invention can be made by reacting a compound of formula (Ila), a compound of formula (lib), and optionally a compound of formula (He) with NH3 in an inert solvent with a boiling point of at least 120° C, such as, for example, ethylene glycol, diethylene glycol, propylene glycol, 1 ,2-butanediol, 1 ,3-butanediol, 1 ,4- butanediol, 2,3-butanediol, the mono- and di(C1-C4-alkyl) ethers of the abovementioned diols, 2-[di(C1-C4-alkyl)amino]ethanol and 3-[di(C1-C4- alkyl)amino]propanol, in the presence of a base, such as, for example, an alkali metal hydroxide or alkali metal carbonate, optionally in the presence of a metall
  • mixtures of compounds according to the present invention can be made by reacting a compound of formula (Ila), a compound of formula (lib), and optionally a compound of formula (He) with a reducing agent in the presence of a base in the melt.
  • Suitable reducing agents are, for example, hydroquinone, resorcinol, pyrocatechol and pyrogallol (1,2,3-trihydroxybenzene) or mixtures thereof, preference being given to hydroquinone.
  • Suitable bases are, for example, alkalimetal hydroxides, oxides and carbonates, preference being given to NaOH.
  • the molar ratio of phthalonitrile (compound of formula (Ila), compound of formula (lib), and optionally compound of formula (He)) to reducing agent is generally from 0.1 to 10:1 , preferably from 0.5 to 2:1. In general, from 0.1 to 1 equivalent, preferably from 0.2 to 0.5 equivalent, of base is used.
  • the reaction is carried out in the melt, preferably at temperatures of from 140 to 250° C., more preferably from 150 to 200° C.
  • the reaction time is generally from 1 to 24 h.
  • the reaction is effected generally under atmospheric pressure, but may also be carried out at elevated or reduced pressure if appropriate.
  • a phenoxy substituted phthalonitrile mixture was prepared in the same way as described in Synthesis Example 1 , except that an equimolar mixture of 2,4-di-tert- pentylphenol, 2-tert-pentylphenol and 4-tert-pentylphenol was used.
  • a phthalocyanine mixture B-2 was prepared in the same way as described in Example 1, except that the mixture obtained in Synthesis Example 2 was used ( m ax (toluene): 728 nm).
  • a phenoxy substituted phthalonitrile mixture was prepared in the same way as described in Synthesis Example 1, except that an equimolar mixture of 2,4,6- trimethylphenol, 2,4-dimethylphenol and 2,6-dimethylphenol is used.
  • a phthalocyanine mixture B-3 was prepared in the same way as described in Example 1, except that the mixture obtained in Synthesis Example 3 was used ( m ax (toluene):
  • a phthalocyanine mixture B-4 was prepared in the same way as described in Example 1, except that the mixture obtained in Synthesis Example 4 was used ( m ax (toluene): 726 nm).
  • the black reaction solution was afterwards cooled to 50° C. and 1000 ml of methanol were added thereto within 2 hours with stirring, in order to completely precipitate the solid produced on cooling.
  • the suspension was stirred for a further hour at 50° C., then cooled to ambient temperature and filtered on a suction filter.
  • the filter cake was washed first with 800 ml of methanol and then with 1000 ml of water and finally pulled dry. After drying under vacuum at 60° C., a black powder was obtained in a yield of 170.4 g (70% of theory, based on the pure substance).

Abstract

The present invention relates to mixtures of compounds of the formula (Ia), (Ib), (Ic) and (Id), a process for its preparation and its use in security applications; for brand protection or as marker for liquids. The compounds of formula (I) have 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. The process of the present invention leads to a complex mixture of compounds of formula (Ia), (Ib), (Ic) and (Id). The exact composition of the mixture of compounds of formula (Ia), (Ib), (Ic) and (Id) can be controlled by varying the reaction conditions and can be analyzed using various methods, such as, for example, HPLC, LC-MS, MALDI-Tof, NMR etc.

Description

Mixtures of compounds having improved solubility for use as markers
DESCRIPTION
The present invention relates to mixtures of compounds of the formula (la), (lb), (Ic) and (Id), a process for its preparation and its use in security applications; for brand protection or as marker for liquids. The compounds of formula (I) have 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. The process of the present invention leads to a complex mixture of compounds of formula (la), (lb), (Ic) and (Id). The exact composition of the mixture of compounds of formula (la), (lb), (Ic) and (Id) can be controlled by varying the reaction conditions and can be analyzed using various methods, such as, for example, HPLC, LC-MS, MALDI-Tof, NMR etc.
TECHNICAL BACKGROUND
US5932723A relates to a process for preparing metal-free phthalocyanine by reductive cyclization of phthalonitrile in the presence of an aliphatic alcohol, of a redox catalyst and of an inorganic base comprises effecting the cyclization in the presence of one or more phthalocyanine derivatives selected from the group consisting of phthalocyaninesulfonic acids and -carboxylic acids and their alkali metal, ammonium and alkylammonium salts, the amino-substituted and aminomethylated phthalocyanines and their reaction products with alkylating agents, sulfonic acids, sulfonyl chlorides and carbonyl chlorides, the imidomethylene- and amidomethylene-substituted phthalocyanines, the alkyl-, aryl- and cyano-substituted phthalocyanines, the hydroxyland alkoxy-substituted phthalocyanines and their reaction products with tetraalkyl- and tetraalkoxy-silanes and the halogenated phthalocyanines.
EP0983274B1 (WO98/52950A1) relates to the use of phthalocyanines of the formula
Figure imgf000003_0001
(I), where
Me is twice hydrogen, twice lithium, magnesium, zinc, copper, nickel, VO, TiO, AICI, AIOH, AIOCOCH3, AIOCOCF3, SiCI2 or Si(OH)2, at least four of the radicals R1 to R16 are each independently of the others pyrrolidin-1 - yl, pyrazolidin-1 -yl, imidazolidin-1-yl, oxazolidin-3-yl, isoxazolidin-2-yl, piperidin-1-yl, piperazin-1-yl, morpholin-4-yl or thiomorpholin-4-yl, which radicals can be monosubstituted or polysubstituted by Ci-C4-alkyl, benzyl, phenylethyl or phenyl, and which are bonded to the phthalocyanine structure via a ring nitrogen atom, and any remaining radicals R1 to R16 are each hydrogen, halogen, hydroxysulfonyl or Ci-C4-dialkylsulfamoyl, as markers for liquids, especially mineral oils.
WO98/14520A1 relates to novel phthalocyanines of formula
Figure imgf000004_0001
which are substituted by 1-4 formyl, carbonyl, hydroxymethyl or carboxyl groups, to their use in recording layers of optical recording media, as well as to a novel process for the preparation of some of these compounds.
US5, 817,804 relates to a mixture of isomeric alkoxy-substituted phthalocyanines and to
Figure imgf000004_0002
a process for their preparation by reacting compounds of the formula (V) in the presence of a metal salt, a Lewis acid, urea and selected solvents.
W0200640021A2 relates to cobalt (lll)phthalocyanine mixtures containing isomers selected from the group of formulas (Iw), (lx), (ly) and (Iz), wherein the amount of both of the isomers ly and Iz have a maximum of 20 wt. %, in relation to the total of the isomers Iw to Iz and their use as optical data carrier.
WO2011/012698A2 describes a phthalocyanine derivative of formula (I) consisting of 4 isomers wherein the relative isomer B content is less than or equal to 1% by weight and its use for the preparation of a pharmaceutical composition.
W02007/104685 relates to the use of phthalocyanines of the formula (I) as markers for liquids, especially mineral oils.
W02002/50216A2 relates to a method for the marking of hydrocarbons, by addition of at least one first marking agent( subsequently referred to as first marking agent), characterised in that, in addition, at least one further second marking agent is added to the hydrocarbon, which, under conditions for removal of the first marking agent, is not completely removable from the hydrocarbon.
W02005/070935 relates to the use of special phthalocyanines carrying substituents bound by methylene groups on the skeletal structure thereof, as marking substances for liquids, especially mineral oils and liquids, and especially mineral oils containing at least one such phthalocyanine as a marking substance.
W02005/066179A1 describes a method for preparing metal-free phthalocyanines
Figure imgf000005_0002
phthalodinitrile of formula (la) in an inert solvent having a boiling temperature of at least 120 °C (under normal pressure) in the presence of ammonia. In formulae I and la, the variable n can take the value of 1 , 2, 3 or 4 and the radicals R denote a five- or six-membered saturated, nitrogen-containing heterocyclic ring that is optionally substituted by one or two Ci-Cs alkyl groups, the heterocyclic ring being bonded to the benzene ring by a nitrogen atom in the ring; the heterocyclic ring may further contain one or two additional nitrogen atoms or an additional oxygen or sulphur atom. The method is characterised in that the reaction is performed in the presence of an alkaline metal hydroxide or alkaline metal carbonate.
W02007/104685A1 relates to the use of phthalocyanines of the formula (I) as marking substances for liquids,
Figure imgf000005_0001
, wherein
M is twice hydrogen, twice lithium, magnesium, zinc, copper, nickel, VO, TiO, AICI, AIOCOCH3, AIOCOCF3, SiCI2 or Si(OH)2; m is 1 , 2, 3, or 4; n is identical or different and is 0, 1 , 2, 3 or 4; r is the same or different and is 0, 1 , 2, 3 or 4; m+r is 1 , 2, 3, or 4; n+r is 0, 1 , 2, 3 or 4;
R is the same or different
Figure imgf000006_0001
R1 is the same or different H, halogen, or R2;
R2 is the same or different (C1 -C18)-alkyl, (C4-C8)-Cycloalkyl, (C2-CI2)- alkenyl, (Ce- C10)-aryl, (C7- C2o)aralkyl or (C2- Cl2)alkynyl, where aryl radicals may be unsubstituted or substituted by one or more halogen, cyano, nitro, hydroxy, amino, 20-alkyl which is optionally interrupted by 1 to 4 oxygen atoms in ether function, Ci-C2o-alkoxy, CI-C2O- alkylamino or C1-C2o-dialkylamino;
R3 is the same or different from R1 or two radicals R3 or a radical R1 and R3 together form a further ring system;
R4, R5, R6 are identical or different and are H, halogen, CH3 or C2H5, Y1, Y2, Y3, Y4, Y5, Y6 are the same or different (Ci.C4)-alkylene, which is unsubstituted or substituted by one or more halogen atoms; s is O, 1 , 2, 3, 4, 5, or 6; and t is 0, 1 , 2, 3.
W02016/015208A1 relates to a phthalocyanine compound of formula
Figure imgf000006_0002
which is suitable for forming a color filter used for a liquid crystal display device, a method for synthesis the phthalocyanine compound and a color filter formed from the composition, wherein Ri to R4 are selected from a saturated or unsaturated hydrocarbon group having 1 to 50 carbon atoms and an organic group containing amine and 1 to 8 carbon atoms, m to n4 are integer from 1 to 4, M is a divalent ion, provided that (a) at least one of R1 to R4 is a saturated or unsaturated hydrocarbon group having 6 to 20 carbon atoms and (b) at least one of R1 to R4 is an organic group containing amine and 1 to 8 carbon atoms.
Ma Chunyu et al., Synthesis (2005) pages 741-748 relates to the synthesis and characterization of several soluble tertraphenoxy-substituted copper and zinc phthalocyanines. Pinal Rodolfo, Organic & Biomolecular Chemistry, 2 (2004), page 2692 reviews the common concept in chemistry, that an asymmetric molecule has in principle an improved solubility over a symmetric one.
None of these documents describes the mixtures of compounds as claimed in the present invention.
Thus, it is an object of the present invention to provide mixtures of compounds which are 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 molar extinction coefficient, good storage stability and good detectability even in very small amounts in the correspondingly marked liquids.
SUMMARY OF THE INVENTION
It was surprisingly found that these and further objectives are achieved by the mixtures of compounds of the formula (la), (lb), (Ic) and (Id) as defined herein below.
Thus, in a first aspect, the invention relates to mixture of compounds of the formula
Figure imgf000007_0001
Figure imgf000008_0001
Ra, Rb, Rc and Rd have independently of each other the meaning of R1, R2 and R3, R1 is present in the compounds of formula (la), (lb), (Ic) and (Id) in an average amount x,
R2 is present in the compounds of formula (la), (lb), (Ic) and (Id) in an average amount y, and
R3 is present in the compounds of formula (la), (lb), (Ic) and (Id) in an average amount z, wherein
R1 is a group of formula
Figure imgf000008_0002
R2 has the meaning of R1 and is different from R1; and
R3 has the meaning of R1 and is different from R1 and R2; or
Figure imgf000008_0003
, or ;
R2 has the meaning of R1 and is different from R1; and
R3 has the meaning of R1 and is different from R1 and R2;
R4 is a Ci-Ci2alkyl group;
R5 is a hydrogen atom, or a Ci-Ci2alkyl group;
R6 is a hydrogen atom, or a Ci-C^alkyl group;
R7 is a hydrogen atom, a Ci-C^alkyl group, or a phenyl group;
R8 is a hydrogen atom, a Ci-C^alkyl group, or a phenyl group; R9 is a hydrogen atom, a Ci-Ci2alkyl group, or a phenyl group; m is 0, 1 or 2; x is 0.05 to 3.95, y is 0.05 to 3.95, z is 0 to 2.00, and the sum of x, y and z is 4.
If z is 0, x is 0.50 to 3.50 and y is 3.50 to 0.50, especially x is 1 .50 to 2.50 and y is 2.50 to 1.50, with the proviso that the sum of x, y and z is 4. Of particular interest are mixtures of compounds, wherein z is 0, x is 2 and y is 2.
If z is not 0, preferably x is 0.50 to 3.50, y is 0.50 to 3.50, z is 0.10 to 1.50, more preferably x is 1.00 to 2.00, y is 1.00 to 2.00, z is 0.50 to 1.50, with the proviso that the sum of x, y and z is 4. Of particular interest are mixtures of compounds, wherein x = y = z = 4/3 (~ 1 .33) and the sum of x, y and z is 4.
For the sake of simplicity, the mixture of compounds of formula (la), (lb), (Ic) and (Id) may be represented by the following formula
Figure imgf000009_0001
The present invention provides the following advantages: i) The process of the present invention leads to a complex mixture of compounds of formula (la), (lb), (Ic) and (Id). The exact composition of the mixture of compounds of formula (la), (lb), (Ic) and (Id) can be controlled by varying the reaction conditions and can be analyzed using various methods, such as, for example, HPLC, LC-MS, MALDI- Tof, NMR etc. ii) While certain macroscopic properties remain almost the same (absorption, emission etc.), the composition of the mixture of compounds of formula (la), (lb), (Ic) and (Id) can be varied and a batch assignment can be made. Thus, it is very difficult for imitators to achieve exactly the same composition (fingerprint) which fact leads to higher protection against counterfeiting. iii) The relative solubility of the mixture of compounds of formula (la), (lb), (Ic) and (Id), wherein Ra, Rb, Rc and Rd have at least two different meanings, R1 and R2, especially three different meanings, R1, R2 and R3, is higher in comparison to mixtures of compounds of formula (la), (lb), (Ic) and (Id), wherein Ra, Rb, Rc and Rd have the same meaning, i.e. R1. roup of
Figure imgf000010_0003
und of formula
Figure imgf000010_0001
, rendering falsification more difficult.
The mixture of compounds according to the present invention is preferably obtainable by reaction of
CN
Jl .CN x/4 mol of a compound of formula Q R' (Ila), y/4 mol of a compound of formula
Figure imgf000010_0002
(lib), and z/4 mol of a compound of formula mol of a reducing agent,
Figure imgf000011_0001
especially a compound of formula , where ■in
R1 is a group of formula
Figure imgf000011_0002
R2 has the meaning of R1 and is different from R1; and R3 has the meaning of R1 and is different from R1 and R2; or the mixture of compounds according to the present invention is preferably obtainable by reaction of x/4 mol of a compound of formula y/4 mol of a compound of formula
Figure imgf000011_0003
(lib), and z/4 mol of a compound of formula
Figure imgf000011_0004
mol NH3, wherein
Figure imgf000011_0005
R2 has the meaning of R1 and is different from R1; and R3 has the meaning of R1 and is different from R1 and R2; and R4, R5, R6, R7, R8, R9, m, x, y and z are defined in claim 1.
Groups of formula
Figure imgf000012_0001
, which are substituted in ortho and/or para position are preferred against groups of formula (IVa), which are substituted in meta position.
In mixtures of compounds of the present application having two different substituents
R1 and R2 R1 and R2 represent groups of formula
Figure imgf000012_0002
wherein at least one of the substituents R7, R8 and R9 is different from a hydrogen atom.
Mixtures of compounds of the present application having three different substituents R1, R2 and R3 are preferred against mixtures of compounds of the present application having two different substituents R1 and R2.
With respect to the groups R4, R5, R6, R7, R8 and R9 the term Ci-Ci2alkyl group denominates a group of linear or branched saturated hydrocarbon radicals having from 1 to 12 carbon atoms. Examples of a Ci-Ci2alkyl group include but are not limited to methyl, ethyl, n-propyl, isopropyl, n-butyl, 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, 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 and dodecyl.
Figure imgf000013_0001
In a preferred embodiment of the present invention R1 is selected from
Figure imgf000013_0002
R2 has the meaning of R1 and is different from R1; and
R3 has the meaning of R1 and is different from R1 and R2,
R7 is a Ci-Ci2alkyl group,
R7' and R7" are independently of each other a Ci-C^alkyl group, or a phenyl group; and R8 and R9 are independently of each other a Ci-C^alkyl group, and
R9' is a hydrogen atom, or a Ci-C^alkyl group.
Figure imgf000013_0003
Figure imgf000014_0001
R2 has the meaning of R1 and is different from R1; and
R3 has the meaning of R1 and is different from R1 and R2.
In another preferred embodiment of the present invention R1 is selected from the group
Figure imgf000014_0002
R2 has the meaning of R1 and is different from R1; and
R3 has the meaning of R1 and is different from R1 and R2, R4 is a hydrogen atom, or a Ci-C^alkyl group;
R5 is a hydrogen atom, or a Ci-C^alkyl group; and R6 is a hydrogen atom, or a Ci-C^alkyl group.
Figure imgf000014_0003
In said embodiment R1 is preferably selected from the group of formula
Figure imgf000014_0004
R2 has the meaning of R1 and is different from R1; and
R3 has the meaning of R1 and is different from R1 and R2.
In a particularly preferred embodiment the present invention is related to mixtures of compounds of formula (la), (lb), (Ic) and (Id), wherein
Ra, Rb, Rc and Rd have independently of each other the meaning of R1, R2 and R3, wherein R1, R2 and R3 as well as x, y and z have the meaning given in the below table:
Figure imgf000015_0001
Figure imgf000016_0002
Mixtures of compounds of the present application having three different substituents R1, R2 and R3 are preferred against mixtures of compounds of the present application having two different substituents R1 and R2. Among the mixtures of compounds of the present application, wherein R1 , R2 and R3 are derived from a group of formula
Figure imgf000016_0001
the mixtures B-1 and B-6 are particularly preferred. Among the mixtures of compounds of the present application, wherein R1, R2 and R3
Figure imgf000017_0001
are derived from a group of formula (IVb) the mixture A-1 is particularly preferred.
A further aspect of the present invention relates to the use of the mixture of compounds according to the present invention 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 950 nm.
A further aspect of the present invention relates to the use of the mixture of compounds according to the present invention in an ink for machine readability and/or security applications.
A further aspect of the present invention relates to the use of the mixture of compounds according to the present invention in an ink for machine readability and/or security applications, or for brand protection or as marker for liquids, especially oils.
The mixture of compounds according to the present invention as described herein provides several benefits, in particular high solubility and stability in the application medium. Moreover, certain mixtures of compounds according to the present invention are outstandingly suitable as fluorescent dyes so that they can be used as NIR compounds emitting light comprising a wavelength of 680 to 950 nm due to their good solubility in the application medium and the high fluorescence quantum yield. In addition, the mixture of compounds according to the present invention 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 molar extinction coefficient, good storage stability and good detectability even in very small amounts in the correspondingly marked liquids.
DETAILED DESCRIPTION OF THE INVENTION
In the context of the present invention, 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, the term "near-infrared light" denotes light that ranges from 680 to 1100 nm.
Here and throughout the specification, the term "visible light" denotes light that ranges from approximately 380 nm to 740 nm. In general, the compounds in the mixture according to the present invention 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 mixture of compounds according to the present invention are also of interest for use in an ink for machine readability and/or security applications.
The mixtures of compounds according to the present invention 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. Thus, the present invention also relates to the use of the mixtures of compounds according to the present invention for brand protection or as marker for liquids. Useful liquids which can be marked with the mixture of compounds according to the present invention preferably include oils such as mineral oils (fuels), 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 mineral oils which, according to the invention, comprise 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 (I) are used as markers for mineral oils (fuels) in which labeling is simultaneously required, for example for tax reasons. In order to minimize the costs of labeling, but also in order to minimize possible interactions of the marked mineral oils with any other ingredients present, such as polyisobuteneamine (PI BA), 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 engines.
The mixture of compounds according to the present invention to be used as markers are added to the liquids, especially fuels 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.
Accordingly, the present invention relates to a method of marking liquids, especially fuels, comprising the steps of a) adding the mixture of compounds according to the present application, to the liquid, especially fuel; and b) measuring an absorbance, reflectance or transmittance spectrum of the liquid, especially fuel in the VIS/NIR range of the electromagnetic spectrum; and c) comparing the spectrum measured under b) and/or information derived therefrom with a corresponding spectrum and/or information of an authentic liquid, especially fuel; as well as to the use of the mixture of compounds according to the present invention in marking liquids, especially fuels.
The liquid is preferably a fuel. The term "fuel" refers to products having a predominantly hydrocarbon composition, although they may contain minor amounts of oxygen, nitrogen, sulfur or phosphorus. As used herein, the term “fuel” includes crude oils, as well as products derived from petroleum refining processes. Preferably, a “fuel” includes without limitation crude oil, lubricating oil, hydraulic fluid, brake fluid, gasoline, diesel fuel, kerosene, jet fuel, heating oil and heavy fuel oil. More preferably, the petroleum hydrocarbon is selected from the group consisting of gasoline, diesel fuel, kerosene, and jet fuel, and even more preferably from the group consisting of gasoline and diesel fuel.
The mixtures of compounds according to the present invention may if appropriate also be used in a mixture with other markers/dyes.
To mark the liquids, especially fuels the mixtures of compounds according to the present invention are generally added in the form of concentrates.
Accordingly, the present invention is directed to a concentrate for marking liquids, especially fuels, comprising a) the mixture of compounds according to the present invention as defined above, c) a solvent, d) optionally at least one colorant, and e) optionally at least one further additive.
The mixture of compounds according to the present invention as defined above is preferably provided as a concentrate for addition to the liquid, especially fuel to be marked. Preferably, a concentrate of between 1% to 10% of the marker in an organic solvent is used. Organic solvents suitable for this purpose are, for example, alkyl benzenes, alkylnaphthalenes or a proprietary blend of such compounds. Polar organic solvents may be included to increase the solubility of the marker compound in the concentrate, such as formamide, N,N-dimethylformamide and N-methylpyrrolidone. Preferably, the solvents are a mixture of aromatic and aprotic solvents. These solvents may be used singly or in blends but must be miscible with the liquid, in particular the fuel, being marked. The mixtures of compounds according to the present invention 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.
In the field of automated banknote processing, 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.
Accordingly, 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.
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 bodily 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 flexible. 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 mixtures of compounds according to the present invention 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. In security printing, the mixture of compounds according to the present invention 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.
In the context of the present invention, the expression "printing ink" also encompasses formulations that comprise a colorant.
The printing ink formulation for security printing according to the invention preferably comprises a) the mixture of compounds according to the present invention 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 Inks"- 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 mixture of compounds according to the present invention 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. 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 II: 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.
In the case of printing ink formulations to be cured by UV radiation, it is usually necessary to include at least one photoinitiator to initiate the curing reaction of the monomers upon exposure to UV radiation. Examples of useful photoinitiators 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. 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. For the purpose of the invention, reactive monomers which also act as solvents are regarded as part of the afore-mentioned binder component b).
Examples of 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.
The printing ink formulation according to the invention may contain an additional colorant d). 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 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,. Besides the inorganic pigments the printing ink formulation of the invention may also comprise organic colour pigments, examples being Monoazo, Disazo, (1- 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. Also suitable are synthetic white pigments with air inclusions to increase the light scattering, such as the Rhopaque® dispersions. 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). 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, 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.
In particular, the printing ink formulation for security printing according to the invention preferably contains a) 0.0001 to 25% by weight of the mixture of compounds according to the present invention, 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. As mentioned earlier, the mixture of compounds according to the present invention 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. When additional colorants are to be employed in a separate 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. 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.
In addition, the present invention relates to security documents, comprising a substrate and the mixture of compounds according to the present invention, or security documents, obtainable by a printing process, wherein the printing ink formulation as defined above is employed.
The security document is preferably selected from a bank note, a passport, a check, a voucher, an ID- or transaction card, a stamp and a tax label.
The process for the preparation of the mixture of compounds of formula
Figure imgf000025_0001
wherein
Ra, Rb, Rc and Rd have independently of each other the meaning of R1, R2 and R3, comprises reacting x/4 mol of a compound of formula y/4 mol of a compound of formula
Figure imgf000026_0001
(lib), and z/4 mol of a compound of formula mol of a reducing agent,
Figure imgf000026_0002
especially a compound of formula wherein
R1 is a group of formula
Figure imgf000026_0003
R2 has the meaning of R1 and is different from R1; and
R3 has the meaning of R1 and is different from R1 and R2; or a process for the preparation of the mixture of compounds of formula (la), (lb), (Ic) and (Id), or comprises reacting x/4 mol of a compound of formula y/4 mol of a compound of formula
Figure imgf000026_0004
(lib), and z/4 mol of a compound of formula
Figure imgf000026_0005
mol NH3, wherein
Figure imgf000027_0001
, or ;
R2 has the meaning of R1 and is different from R1; and
R3 has the meaning of R1 and is different from R1 and R2; and R4, R5, R6, R7, R8, R9, m, x, y and z are defined above.
Mixtures of compounds according to the present invention, wherein R4, R5 and R6 are derived from a group of formula (IVb), are obtainable in a conventional manner, for example as described in J. Gen. Chem. USSR 51 (1981) 1405-1411 , F. H. Moser, A. L. Thomas, The Phthalocyanines, CRC Press, Boca Rota, Fla., 1983, or J. Am. Chem. Soc. 106 (1984) 7404-7410. For instance, mixtures of compounds according to the present invention can be made by reacting a compound of formula (Ila), a compound of formula (lib), and optionally a compound of formula (He) with NH3 in an inert solvent with a boiling point of at least 120° C, such as, for example, ethylene glycol, diethylene glycol, propylene glycol, 1 ,2-butanediol, 1 ,3-butanediol, 1 ,4- butanediol, 2,3-butanediol, the mono- and di(C1-C4-alkyl) ethers of the abovementioned diols, 2-[di(C1-C4-alkyl)amino]ethanol and 3-[di(C1-C4- alkyl)amino]propanol, in the presence of a base, such as, for example, an alkali metal hydroxide or alkali metal carbonate, optionally in the presence of a metallizing reagent. Reference is made to W02005/066179.
Mixtures of compounds according to the present invention, wherein R4, R5 and R6 are derived from a group of formula (IVa), can be prepared by known methods familiar to the person skilled in the art, as described, for example, in F. H. Moser and a. L. Thomas in Phthalocyanine Compounds, ACS Monograph Series, Chapman & Hall, New York, 1963, F. H. Moser and a. L. Thomas in The phthalocyanines, Manufacture and Applications, Vol. 2, CRC Press, Boca Raton, 1983, C. C. Leznoff in phthalocyanines, Properties and Application (Eds.: C. C. Leznoff and a. b. P. Lever), Vol. 1 , VCH, New York, Weinheim, Cambridge, 1989, m. Hanack, H. Heck mann and R. Polley in Houben-Weyl, Methods of Organic Chemistry (Ed.: E. Schaumann), 4th Edition, Vol. E 9 d, p. 727, Thieme, Stuttgart, New York, 1998, US3509146, EP-A- 0373643, EP0658604, EP-A-0703280, EP0848040 and US6348250. For instance, mixtures of compounds according to the present invention can be made by reacting a compound of formula (Ila), a compound of formula (lib), and optionally a compound of formula (He) with a reducing agent in the presence of a base in the melt.
Suitable reducing agents are, for example, hydroquinone, resorcinol, pyrocatechol and pyrogallol (1,2,3-trihydroxybenzene) or mixtures thereof, preference being given to hydroquinone. Suitable bases are, for example, alkalimetal hydroxides, oxides and carbonates, preference being given to NaOH.
The molar ratio of phthalonitrile (compound of formula (Ila), compound of formula (lib), and optionally compound of formula (He)) to reducing agent is generally from 0.1 to 10:1 , preferably from 0.5 to 2:1. In general, from 0.1 to 1 equivalent, preferably from 0.2 to 0.5 equivalent, of base is used. The reaction is carried out in the melt, preferably at temperatures of from 140 to 250° C., more preferably from 150 to 200° C. The reaction time is generally from 1 to 24 h. The reaction is effected generally under atmospheric pressure, but may also be carried out at elevated or reduced pressure if appropriate.
Various aspects and features of the present invention will be further discussed in terms of the examples. The following examples are intended to illustrate various aspects and features of the present invention.
Examples
Synthesis Example 1
Figure imgf000028_0001
26 parts of cesium carbonate are added with stirring to a solution of 13 parts of 3- nitrophthalonitrile in 75 parts of N-methyl-2-pyrrolidinone. 13.5 parts of an equimolar mixture of 2,4-diisopropylphenol and 2,6-diisopropylphenol are added and the reaction mixture is heated to 40° C and stirred for 24 hours. After cooling to room temperature, the reaction mixture is poured into 700 parts of ice-water. The precipitate is filtered off, washed with water and dried at 60° C in an oven under vacuum. The crude product (24 parts) is dissolved in 300 parts of methanol and reprecipitated by addition of 1200 parts of water. The precipitate is filtered off, washed with 200 parts of a water-methanol mixture (10:1) and dried at 60° C in an oven under vacuum giving rise to 16 parts of phenoxy substituted phthalonitriles.
Example 1
Figure imgf000029_0001
A mixture of 16 parts of phenoxy substituted phthalonitriles obtained in Synthesis Example 1, 5.8 parts of hydroquinone and 0.5 parts of sodium hydroxide was heated for four hours at 175° C. During that time the mixture solidified. After cooling to room temperature, the solid was ground into small pieces and suspended in 350 parts of water containing 5% of methanol. The solid was filtered off, washed three times with 100 parts of methanol and dried in a vacuum oven at 60°C (yield: 6 parts of phthalocyanine mixture B-1 , 7,max (toluene): 726 nm).
Synthesis Example 2
Figure imgf000029_0002
A phenoxy substituted phthalonitrile mixture was prepared in the same way as described in Synthesis Example 1 , except that an equimolar mixture of 2,4-di-tert- pentylphenol, 2-tert-pentylphenol and 4-tert-pentylphenol was used.
Example 2
Figure imgf000030_0001
A phthalocyanine mixture B-2 was prepared in the same way as described in Example 1, except that the mixture obtained in Synthesis Example 2 was used ( max (toluene): 728 nm).
Synthesis Example 3
Figure imgf000030_0002
A phenoxy substituted phthalonitrile mixture was prepared in the same way as described in Synthesis Example 1, except that an equimolar mixture of 2,4,6- trimethylphenol, 2,4-dimethylphenol and 2,6-dimethylphenol is used.
Example 3
Figure imgf000030_0003
A phthalocyanine mixture B-3 was prepared in the same way as described in Example 1, except that the mixture obtained in Synthesis Example 3 was used ( max (toluene):
724 nm). Synthesis Example 4
Figure imgf000031_0001
A 1:1 mixture of 2,6-diphenylphenol and 4-tert. butyl-2,6-diphenylphenol was reacted with 3-nitrophthalodinitrile in the same way as described in Synthesis Example 1.
Example 4
Figure imgf000031_0002
A phthalocyanine mixture B-4 was prepared in the same way as described in Example 1, except that the mixture obtained in Synthesis Example 4 was used ( max (toluene): 726 nm).
Comparative Example 1
The preparation of 1(4),8(11),15(18),22(25)-tetra(3-methylpiperidino)phthalocyanine (CC-1) was done as described in the examples of US20070155961A1 :
225.3 g (1.00 mol) of 3-(3-methylpiperidino)phthalodinitrile were introduced into 500 ml of 3-dimethylaminopropanol in a 2 I flange flask at ambient temperature with stirring (150 revolutions/min). 4.85 g (0.035 mol; 3.5 mol %) of potassium carbonate were subsequently added. A total of 34.1 g (2.00 mol) of ammonia were introduced in the gaseous form into the reaction mixture over 9 hours (2 h during the heat-up phase and 7 h during the reaction phase) via a dip pipe with a volumetric flow rate of approximately 83 ml/min, the reaction mixture being heated to a final temperature of 150° C. and being maintained at this temperature for 15 hours. The black reaction solution was afterwards cooled to 50° C. and 1000 ml of methanol were added thereto within 2 hours with stirring, in order to completely precipitate the solid produced on cooling. The suspension was stirred for a further hour at 50° C., then cooled to ambient temperature and filtered on a suction filter. The filter cake was washed first with 800 ml of methanol and then with 1000 ml of water and finally pulled dry. After drying under vacuum at 60° C., a black powder was obtained in a yield of 170.4 g (70% of theory, based on the pure substance).
The compound CC-1 is present as a mixture of different positional isomers with the following structures:
Figure imgf000032_0001
Synthesis Example 5
Figure imgf000033_0001
13.5 parts of potassium carbonate are suspended in 65 parts of DMF at room temperature. Then, 10 parts of 3-nitrophthalodinitrile are added in portions. The mixture is heated up to 35 C and stirred for 30 min. 7.8 parts of an equimolar mixture of piperidine, 3-methylpiperidine and 3,6-dimethylpiperidine is added dropwise within 3 hours. The mixture is stirred over night and poured into ice/water. The formed precipitate is filtered off, washed two times with 450 parts water and dried in an oven under vacuum at 60°C. Yield: 11.5 parts solid (subst. piperidino)phthalodinitrile mixture
Example 5
Figure imgf000033_0002
23 parts of the piperidino substituted phthalonitrile mixture prepared in Synthesis Example 5 were added to 45 parts 3-dimethylaminopropanol at room temperature. Afterwards, 0.5 parts K2CO3 were added and ammonia is fed via an immersion pipe at 5 mL/min. The mixture is heated up to 150°C. The addition of ammonia is stopped after three hours, stirring continues for another 12 hours at 150°C. The mixture is cooled down to 50 °C, 100 parts methanol are added. The precipitate is filtered off, washed with methanol and water and dried in an oven under vacuum at 60 °C (yield: 17 parts of black powder, max (toluene): 772 nm).
For the sake of simplicity, the mixture of compounds according to the present application is represented by the following formula:
Figure imgf000034_0001
Figure imgf000034_0002
Figure imgf000035_0001
Figure imgf000036_0001
1) Comparison of solubility of synthetic mixture of compounds (A-1) having 3 different substituents R1, R2 and R3 with the same averaged molecular weight to solubility of "single" compound (CC-1).
2) Comparison of solubility of synthetic mixture of compounds (B-5) having 3 different substituents R1, R2 and R3with the same averaged molecular weight to solubility of "single" compound (CC-2).
3) Comparison of solubility of synthetic mixture of compounds (B-5) having 3 different substituents R1, R2 and R3with the same averaged molecular weight to solubility of "single" compound (CC-3).
4) Comparison of solubility of synthetic mixture of compounds having 2 different substituents R1 and R2 to solubility of physical mixture of 2 compounds having only one substituent R1 and R2, respectively.
5) Comparison of solubility of synthetic mixture of compounds having 3 different substituents R1, R2 and R3 to solubility of physical mixture of 3 compounds having only one substituent R1, R2 and R3, respectively.

Claims

Claims
1. A mixture of compounds of the formula
Figure imgf000037_0001
wherein
Ra, Rb, Rc and Rd have independently of each other the meaning of R1, R2 and
R3,
R1 is present in the compounds of formula (la), (lb), (Ic) and (Id) in an average amount x,
R2 is present in the compounds of formula (la), (lb), (Ic) and (Id) in an average amount y, and
R3 is present in the compounds of formula (la), (lb), (Ic) and (Id) in an average amount z, wherein R1 is a group of formula
Figure imgf000037_0002
R2 has the meaning of R1 and is different from R1; and
R3 has the meaning of R1 and is different from R1 and R2; or
Figure imgf000038_0005
, or ;
R2 has the meaning of R1 and is different from R1; and
R3 has the meaning of R1 and is different from R1 and R2;
R4 is a Ci-Ci2alkyl group;
R5 is a hydrogen atom, or a Ci-C^alkyl group;
R6 is a hydrogen atom, or a Ci-C^alkyl group;
R7 is a hydrogen atom, a Ci-C^alkyl group, or a phenyl group;
R8 is a hydrogen atom, a Ci-C^alkyl group, or a phenyl group;
R9 is a hydrogen atom, a Ci-C^alkyl group, or a phenyl group; m is 0, 1 or 2; x is 0.05 to 3.95, y is 0.05 to 3.95, z is 0 to
2.00, and the sum of x, y and z is 4. The mixture of compounds according to claim 1 , which is obtainable by reaction of x/4 mol of a compound of formula
Figure imgf000038_0001
y/4 mol of a compound of formula
Figure imgf000038_0002
(lib), and z/4 mol of a compound of formula mol of a reducing
Figure imgf000038_0003
Figure imgf000038_0004
agent, especially a compound of formula , wherein R1 is a group of formula
Figure imgf000039_0001
R2 has the meaning of R1 and is different from R1; and
R3 has the meaning of R1 and is different from R1 and R2; or the mixture of compounds according to claim 1 , which is obtainable by reaction of x/4 mol of a compound of formula
Figure imgf000039_0002
y/4 mol of a compound of formula
Figure imgf000039_0003
(lib), and z/4 mol of a compound of formula
Figure imgf000039_0004
(He) with 1 mol NH3, wherein
Figure imgf000039_0006
, or
R2 has the meaning of R1 and is different from R1; and
R3 has the meaning of R1 and is different from R1 and R2; and R4, R5, R6, R7, R8, R9, m, x, y and z are defined in claim 1.
3. The mixture of compounds according to claim 1 , or 2, wherein
R1 is selected from
Figure imgf000039_0005
Figure imgf000040_0001
R2 has the meaning of R1 and is different from R1; and
R3 has the meaning of R1 and is different from R1 and R2,
R7 is a Ci-Ci2alkyl group, R7' and R7" are independently of each other a Ci-Ci2alkyl group, or a phenyl group; and
R8 and R9 are independently of each other a Ci-Ci2alkyl group, and R9' is a hydrogen atom, or a Ci-Ci2alkyl group.
4. The mixture of compounds according to claim 3, wherein
Figure imgf000040_0002
R2 has the meaning of R1 and is different from R1; and
R3 has the meaning of R1 and is different from R1 and R2.
5. The mixture of compounds according to claim 1 , or 2, wherein
Figure imgf000041_0001
R1 is selected from the group of formula
Figure imgf000041_0002
R2 has the meaning of R1 and is different from R1; and R3 has the meaning of R1 and is different from R1 and R2, R4 is a hydrogen atom, or a Ci-C^alkyl group;
R5 is a hydrogen atom, or a Ci-Ci2alkyl group; and
R6 is a hydrogen atom, or a Ci-C^alkyl group.
6. The mixture of compounds according to claim 5, wherein
Figure imgf000041_0003
R1 is selected from the group of formula
Figure imgf000041_0004
R2 has the meaning of R1 and is different from R1; and
R3 has the meaning of R1 and is different from R1 and R2.
7. The mixture of compounds according to any of claims 1 , and 3 to 6, which is a mixture of compounds of formula (la), (lb), (Ic) and (Id), wherein
Ra, Rb, Rc and Rd have independently of each other the meaning of R1, R2 and R3, wherein R1, R2 and R3 as well as x, y and z have the meaning given in the below table:
Figure imgf000041_0005
Figure imgf000042_0001
Figure imgf000043_0001
Use of the mixture of compounds according to any one of claims 1 to 7 in an ink for machine readability and/or security applications, or for brand protection or as marker for liquids, especially oils. A printing ink formulation for security printing, comprising a) the mixture of compounds according to any one of claims 1 to 7, b) a polymeric binder, c) a solvent, d) optionally at least one colorant, and e) optionally at least one further additive, or a concentrate for marking liquids, especially fuels, comprising a) the mixture of compounds according to any one of claims 1 to 7, c) a solvent, e) optionally at least one colorant, and e) optionally at least one further additive. Security document, comprising a substrate and the mixture of compounds according to any one of claims 1 to 7, or security document, obtainable by a printing process, wherein the printing ink formulation as defined in claim 9 is employed. Security document according to claim 10, selected from a bank note, a passport, a check, a voucher, an ID- or transaction card, a stamp and a tax label. A method of detecting the authenticity of the security document as defined in claims 10, or 11, 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. A method of marking liquids, especially fuels, comprising the steps of a) adding the mixture of compounds according to any one of claims 1 to 7, to the liquid, especially fuel; and b) measuring an absorbance, reflectance or transmittance spectrum of the liquid, especially fuel in the VIS/NIR range of the electromagnetic spectrum; and c) comparing the spectrum measured under b) and/or information derived therefrom with a corresponding spectrum and/or information of an authentic liquid, especially fuel. Use of the mixture of compounds according to any one of claims 1 to 7, or the concentrate according to claim 9 in marking liquids, especially fuels. A process for the preparation of the mixture of compounds of formula
Figure imgf000044_0001
Figure imgf000045_0001
wherein Ra, Rb, Rc and Rd have independently of each other the meaning of R1,
R2 and R3, comprising reacting x/4 mol of a compound of formula y/4 mol of a compound of formula
Figure imgf000045_0002
(lib), and z/4 mol of a compound of formula
Figure imgf000045_0003
(He) with 1 mol of a reducing
O H
Figure imgf000045_0004
Figure imgf000045_0005
agent, especially a compound of formula , wherein
R1 is a group of formula
Figure imgf000045_0006
R2 has the meaning of R1 and is different from R1; and
R3 has the meaning of R1 and is different from R1 and R2; or a process for the preparation of the mixture of compounds of formula (la), (lb), (Ic) and (Id), comprising reacting x/4 mol of a compound of formula
Figure imgf000046_0001
y/4 mol of a compound of formula
Figure imgf000046_0002
(lib), and z/4 mol of a compound of formula
Figure imgf000046_0003
(He) with 1 mol NH3, wherein
Figure imgf000046_0004
R2 has the meaning of R1 and is different from R1; and
R3 has the meaning of R1 and is different from R1 and R2; and R4, R5, R6, R7, R8, R9, m, x, y and z are defined in claim 1.
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