WO2005016654A1 - Procede d'impression d'integrateur de temps-temperature sur un substrat - Google Patents

Procede d'impression d'integrateur de temps-temperature sur un substrat Download PDF

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Publication number
WO2005016654A1
WO2005016654A1 PCT/EP2004/051733 EP2004051733W WO2005016654A1 WO 2005016654 A1 WO2005016654 A1 WO 2005016654A1 EP 2004051733 W EP2004051733 W EP 2004051733W WO 2005016654 A1 WO2005016654 A1 WO 2005016654A1
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WO
WIPO (PCT)
Prior art keywords
group
radical
atom
indicator
alkyl radical
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Application number
PCT/EP2004/051733
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English (en)
Inventor
Thomas Bolle
Hans Reichert
Peter Simmendinger
Original Assignee
Ciba Specialty Chemicals Holding Inc.
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Publication date
Application filed by Ciba Specialty Chemicals Holding Inc. filed Critical Ciba Specialty Chemicals Holding Inc.
Publication of WO2005016654A1 publication Critical patent/WO2005016654A1/fr

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Classifications

    • 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
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B41—PRINTING; LINING MACHINES; TYPEWRITERS; STAMPS
    • B41M—PRINTING, DUPLICATING, MARKING, OR COPYING PROCESSES; COLOUR PRINTING
    • B41M3/00—Printing processes to produce particular kinds of printed work, e.g. patterns
    • B41M3/14—Security printing
    • B41M3/142—Security printing using chemical colour-formers or chemical reactions, e.g. leuco-dye/acid, photochromes
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B65—CONVEYING; PACKING; STORING; HANDLING THIN OR FILAMENTARY MATERIAL
    • B65D—CONTAINERS FOR STORAGE OR TRANSPORT OF ARTICLES OR MATERIALS, e.g. BAGS, BARRELS, BOTTLES, BOXES, CANS, CARTONS, CRATES, DRUMS, JARS, TANKS, HOPPERS, FORWARDING CONTAINERS; ACCESSORIES, CLOSURES, OR FITTINGS THEREFOR; PACKAGING ELEMENTS; PACKAGES
    • B65D79/00—Kinds or details of packages, not otherwise provided for
    • B65D79/02—Arrangements or devices for indicating incorrect storage or transport
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D11/00—Inks
    • C09D11/50—Sympathetic, colour changing or similar inks
    • G—PHYSICS
    • G01—MEASURING; TESTING
    • G01K—MEASURING TEMPERATURE; MEASURING QUANTITY OF HEAT; THERMALLY-SENSITIVE ELEMENTS NOT OTHERWISE PROVIDED FOR
    • G01K11/00—Measuring temperature based upon physical or chemical changes not covered by groups G01K3/00, G01K5/00, G01K7/00 or G01K9/00
    • G01K11/12—Measuring temperature based upon physical or chemical changes not covered by groups G01K3/00, G01K5/00, G01K7/00 or G01K9/00 using changes in colour, translucency or reflectance
    • G01K11/16—Measuring temperature based upon physical or chemical changes not covered by groups G01K3/00, G01K5/00, G01K7/00 or G01K9/00 using changes in colour, translucency or reflectance of organic materials
    • G—PHYSICS
    • G01—MEASURING; TESTING
    • G01K—MEASURING TEMPERATURE; MEASURING QUANTITY OF HEAT; THERMALLY-SENSITIVE ELEMENTS NOT OTHERWISE PROVIDED FOR
    • G01K3/00—Thermometers giving results other than momentary value of temperature
    • G01K3/02—Thermometers giving results other than momentary value of temperature giving means values; giving integrated values
    • G01K3/04—Thermometers giving results other than momentary value of temperature giving means values; giving integrated values in respect of time
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B41—PRINTING; LINING MACHINES; TYPEWRITERS; STAMPS
    • B41M—PRINTING, DUPLICATING, MARKING, OR COPYING PROCESSES; COLOUR PRINTING
    • B41M7/00—After-treatment of prints, e.g. heating, irradiating, setting of the ink, protection of the printed stock
    • B41M7/0081—After-treatment of prints, e.g. heating, irradiating, setting of the ink, protection of the printed stock using electromagnetic radiation or waves, e.g. ultraviolet radiation, electron beams
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B41—PRINTING; LINING MACHINES; TYPEWRITERS; STAMPS
    • B41M—PRINTING, DUPLICATING, MARKING, OR COPYING PROCESSES; COLOUR PRINTING
    • B41M7/00—After-treatment of prints, e.g. heating, irradiating, setting of the ink, protection of the printed stock
    • B41M7/009—After-treatment of prints, e.g. heating, irradiating, setting of the ink, protection of the printed stock using thermal means, e.g. infrared radiation, heat
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B65—CONVEYING; PACKING; STORING; HANDLING THIN OR FILAMENTARY MATERIAL
    • B65D—CONTAINERS FOR STORAGE OR TRANSPORT OF ARTICLES OR MATERIALS, e.g. BAGS, BARRELS, BOTTLES, BOXES, CANS, CARTONS, CRATES, DRUMS, JARS, TANKS, HOPPERS, FORWARDING CONTAINERS; ACCESSORIES, CLOSURES, OR FITTINGS THEREFOR; PACKAGING ELEMENTS; PACKAGES
    • B65D2203/00—Decoration means, markings, information elements, contents indicators
    • G—PHYSICS
    • G01—MEASURING; TESTING
    • G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
    • G01N31/00—Investigating or analysing non-biological materials by the use of the chemical methods specified in the subgroup; Apparatus specially adapted for such methods
    • G01N31/22—Investigating or analysing non-biological materials by the use of the chemical methods specified in the subgroup; Apparatus specially adapted for such methods using chemical indicators
    • G01N31/229—Investigating or analysing non-biological materials by the use of the chemical methods specified in the subgroup; Apparatus specially adapted for such methods using chemical indicators for investigating time/temperature history

Definitions

  • the present invention relates to a method of printing a substrate, comprising (a) printing onto the substrate a time-temperature integrator (TTI) which comprises at least one indicator having photochromic properties based on transfer reactions.
  • TTI time-temperature integrator
  • perishable materials When perishable materials are used it is often desirable to ascertain the age and the current usable condition of the materials. While the application of an expiry date to the packaging was formerly considered sufficient, for a large number of products such a procedure is nowadays too inaccurate and insufficiently tamper-proof.
  • the condition of perishable products is generally a function not only of time but also of other variables, such as, especially, temperature.
  • US-B-3,999,946 addresses this problem and proposes providing the perishable products with an indicator giving the time/temperature history.
  • the originally colourless acetylene-based indicator exhibits a characteristic, irreversible colour change from which the quality of the stored perishable product can be inferred.
  • EP-A-117 390 describes a time-temperature integrator based on diacetylene materials, wherein the change in the reflectance of the diacetylene materials is measured and the diacetylene materials are applied to the substrate by means of customary printing techniques, such as flexographic printing, intaglio printing, screen printing, ink-jet printing or letterpress printing.
  • US-B-5,057,434 describes a time-temperature integrator which consists of at least two functional layers.
  • One layer can be, for example, a diacetylene material that expires after 21 days at 3.3°C.
  • the second layer consists of a material having a melting point above 6°C and a dye. At temperatures above 6°C, the dye becomes mobile in the second layer, that is to say it diffuses through the layers and makes an additive colour contribution to the indicator.
  • This system makes it possible, on the one hand, to monitor the shelf life of the foodstuff and, on the other hand, to indicate storage at too high a temperature.
  • the layers are preferably applied by means of customary printing techniques.
  • TTI time-temperature integrator
  • WO 99/39197 relates to a substrate for the packaging of, or for application to, ageing- and temperature-sensitive products, the substrate having, arranged in the region of the substrate, a planar time-temperature integrator comprising a matrix and at least one reversible indicator embedded therein, the indicator having photochromic properties based on transfer reactions.
  • the nature and the amount of the TTI used for printing can be matched to the perishable products.
  • the TTI can be used in the form of a solution and/or in the form of an aqueous dispersion.
  • the problem underlying the invention is to provide a method which enables the quality of the products to be determined and which is simple to handle.
  • a method of determining the quality of ageing- and temperature-sensitive products which comprises the following steps: a) printing onto a substrate a time-temperature integrator which comprises at least one indicator having photochromic properties based on transfer reactions, especially a reversible indicator of formula I, II, III, IV, V orVI, as defined below, b) activation, especially photo-induced coloration, of the indicator, c) optionally application of a protector which prevents renewed photo-induced coloration of the indicator, and d) determination of the degree of time- or temperature-induced decoloration and, taking account of the degree of decoloration, the quality of the product; or by a method of printing a substrate, comprising
  • a transfer reaction is generally to be understood as being a reaction which includes a change in the atomic connectivities, the rearrangement of at least one atom being involved.
  • An example thereof is the transfer of a hydrogen atom (or a proton or hydride).
  • the above-mentioned species is transferred from a "donor” group to an "acceptor” group and in so doing forms a tautomeric compound.
  • isomeric or charged species may be formed in the transfer reaction.
  • the indicator can undergo photo-induced coloration by irradiation with photons of a specific energy range, the coloration being followed by a time- and temperature-dependent decoloration.
  • the coloration of the indicator can take place at a defined timepoint, preferably, for example, immediately after printing of the substrate, which is especially the packaging of a perishable material.
  • the time-temperature clock can accordingly be started at a defined desired timepoint and does not begin to run irreversibly at the time of the indicator synthesis.
  • Decoloration is preferred for consideration according to the invention, but the use of an indicator in which the coloration process forms the basis of the time-temperature clock is also conceivable.
  • the time-temperature integrator is, if necessary, provided with a protector which prevents the renewed photo-induced coloration of the reversible indicator.
  • a protector may be a protective coating (overprint varnish) or a laminate that comprises a filter which, by filtering out certain wavelength ranges, is intended to prevent undesirable renewed coloration of the indicator after the time-temperature clock has started.
  • a further, irreversible indicator is arranged e.g. alongside or over the reversible indicator.
  • the further indicator indicates by means of an irreversible colour change that the reversible indicator has undergone renewed coloration after production or packaging of the perishable goods.
  • indicators having more than one characteristic time domain can have, for example, a phase transition, with the different phases exhibiting different decoloration behaviours.
  • the actual determination of the quality of ageing- or temperature-sensitive products is preceded by the photo-induced coloration of the reversible indicator.
  • the coloration is effected prior to the application of a filter or of the irreversible indicator.
  • the degree of time- or temperature-induced decoloration is then measured and the quality of the product is inferred therefrom.
  • the method according to the invention is suitable for marking perishable products such as foodstuffs (e.g. frozen foods), medicaments, drugs, transplant organs and perishable raw materials.
  • foodstuffs e.g. frozen foods
  • medicaments e.g. frozen foods
  • drugs e.g. transplant organs
  • perishable raw materials e.g.
  • the photochromic indicator reactions can be based, for example, on reversible electron transfer or on the reversible transfer of a charged or uncharged hydrogen atom (proton, hydride) or a hydrogen isotope (deuterium, tritium). Preference is given to the transfer of protons, deuterons, halogen radical ions or simple chemical groups, such as methyl groups.
  • B radical v — -"' being a Ce-Csoaryl radical or C 2 -C 30 heteroaryl radical, which can be unsubstituted or substituted,
  • the radical is a C 2 -C 3 oheteroaryl radical, which can be unsubstituted or substituted, and B 5 , R 5 and R 6 are as defined below.
  • examples in which B is not a ring system include:
  • R is a C 1-18 alkyl radical.
  • Preferred as reversible indicators are compounds of general formula
  • a 1 is a nitrogen atom or a group C-R 1 ,
  • a 2 is a nitrogen atom or a group C-R 2 ,
  • a 3 is a nitrogen atom or a group C-R 3 ,
  • a 4 is a nitrogen atom or a group C-R 4 , wherein
  • R 1 , R 2 , R 3 and R 4 are each independently of the others a hydrogen atom, an isotope thereof or a fluorine atom, a chlorine atom, a bromine atom, a C 1- 8 alkyl radical, especially a C ⁇ -4 alkyl radical, or a C 6 -C-
  • R 5 is a hydrogen atom, an isotope thereof (D or T), a nitrile group, an ester group, an aldehyde group, a carboxylic acid group, a keto group, a fluorine atom, a chlorine atom, a bromine atom or a C ⁇ . ⁇ _alkyl radical, especially a C ⁇ -4 alkyl radical, a C 6 -C 14 aryl radical, especially an unsubstituted or substituted phenyl group, or a C 2 -C ⁇ 3 heteroaryI radical, especially an unsubstituted or substituted pyridine group,
  • R 6 is a hydrogen atom (H) or an isotope thereof (D or T),
  • B 1 is a nitrogen atom or a group C-R 7
  • B 2 is a nitrogen atom or a group C-R 8 ,
  • B 3 is a nitrogen atom or a group C-R 9 ,
  • B 4 is a nitrogen atom or a group C-R 10 ,
  • B 5 is a nitrogen atom or a group C-R 11 , wherein
  • R 7 , R 8 , R 9 and R 10 are each independently of the others a hydrogen atom, an isotope thereof or a fluorine atom, a chlorine atom, a bromine atom or a Ci.igalkyl radical, especially a
  • R 11 is a nitro group, a cyano group, a carboxylic acid group or a derivative thereof, such as a carboxylic acid ester group or a carboxylic acid amide group, a ketone group or an aldehyde group; compounds of general formula
  • a 5 is a nitrogen atom or a group C-R 14
  • a 6 is a nitrogen atom or a group C-R 15
  • a 7 is a nitrogen atom or a group C-R 16
  • a 8 is a nitrogen atom or a group C-R 17
  • a 9 is a nitrogen atom or a group C-R 18
  • a 10 is a nitrogen atom or a group C-R 19
  • a 11 is a nitrogen atom or a group C-R 20 , wherein
  • R 4 , R 15 , R 16 , R 17 , R 18 , R 19 and R 20 are each independently of the others a hydrogen atom, an isotope thereof, a fluorine atom, a chlorine atom, a bromine atom, a Ci_i 8 alkyl radical, especially a radical, or a C 6 -C ⁇ 4 aryl radical, especially a phenyl group
  • R 12 is a hydrogen atom, an isotope thereof (D or T), a nitrile group, an ester group, an aldehyde group, a carboxylic acid group, a keto group, a fluorine atom, a chlorine atom, a bromine atom or a C h al y!
  • R 13 is a hydrogen atom (H) or an isotope thereof (D or T)
  • B 6 is a group C-R 21
  • B 7 is a group C-R 22
  • B 8 is a group C-R 23
  • B 9 is a group C-R 24
  • B 10 is a group C-R 25 , wherein
  • R 21 , R 22 , R 23 and R 24 are each independently of the others a hydrogen atom, an isotope thereof or a fluorine atom, a chlorine atom, a bromine atom or a d -18 alkyl radical, especially a C ⁇ -4 alkyl radical, or a C ⁇ -C-uaryl radical, especially a phenyl group
  • R 25 is a nitro group, a cyano group, a carboxylic acid group or a derivative thereof, such as a carboxylic acid ester group or a carboxylic acid amide group, a ketone group or an aldehyde group; compounds of general formula
  • R 26 , R 27 and R 28 are each independently of the others a C 1-8 alkyl radical, especially a methyl or ethyl group; compounds of general formula
  • R 29 , R 30 , R 31 and R 32 are each independently of the others a hydrogen atom, a fluorine atom, a chlorine atom, a bromine atom, a C 1 _ 1 ⁇ al yl radical, especially a C 1-4 alkyl radical, or a
  • R 50 , R 51 , R 52 and R 53 are each independently of the others H, a C C ⁇ 8 alkyl radical or a C 6 -C ⁇ 8 aryl radical, which can be unsubstituted or substituted; compounds of general formula (V), wherein R 33 is a C 1-18 alkyl radical,
  • R 34 , R 35 and R 3 ⁇ are each independently of the others a hydrogen atom or a C ⁇ -18 alkyl radical; or compounds of general formula
  • R 38 , R 39 , R 40 , R 41 , R 42 , R 43 , R 44 , R 45 and R 46 are each independently of the others a hydrogen atom, a Ci.i ⁇ alkyI radical or a C ⁇ - ⁇ 8 a!koxy radical, or two of the radicals R 38 , R 39 , R 40 , R 41 , R 42 , R 43 , R 44 , R 45 and R 46 together form a group of the formula , wherein R 50 , R 51 , R 52 and R 53 are each independently of the others H, a C C ⁇ 8 alkyl radical or a C 6 -C 18 aryl radical, which can be unsubstituted or substituted.
  • R 50 , R 51 , R 52 and R 53 are each independently of the others H, a C C ⁇ 8 alkyl radical or a C 6 -C 18 aryl radical, which can be unsubstituted or substituted.
  • the reversible indicator is more especially a compound of general formula I or II, namely
  • Proton transfer reactions are shown diagrammatically by way of example below.
  • the initially colourless indicator is irradiated with UV light or near-UV light, whereupon a proton transfer and an associated indicator coloration take place.
  • Such a photo- induced proton transfer then proceeds as a function of time and temperature in the other direction again, so that the indicator is successively decolorised.
  • Analogous reactions based on the transfer of methyl groups or halogen radicals, are likewise shown.
  • a compound having two crystalline phases and two different characteristic time domains is described below.
  • a phase transfer takes place from a first crystalline phase having long decoloration times to a second crystalline phase having a decoloration time that is shorter by a factor of 10.
  • halogen atom denotes an iodine atom, a fluorine atom, a bromine atom or a chlorine atom, preferably a fluorine atom, a bromine atom or a chlorine atom.
  • d-C ⁇ lkyl denotes methyl, ethyl, n-propyl, isopropyl, n-butyl, sec-butyl, isobutyl or tert-butyl;
  • C C 8 alkyl denotes, for example, methyl, ethyl, n-propyl, isopropyl, n-butyl, sec-butyl, isobutyl, tert-butyl, n-amyl, tert-amyl or hexyl;
  • C C 18 alkyl denotes, for example, methyl, ethyl, n- propyl, isopropyl, n-butyl, sec-butyl, isobutyl, tert-butyl, n-amyl, tert-amyl, hexyl, heptyl, octyl, 2-ethylhexyl, non
  • C 6 -C 30 aryl radical is typically a C 6 -C 24 aryl radical, such as phenyl, indenyl, azulenyl, naphthyl, biphenyl, as-indacenyl, s-indacenyl, acenaphthylenyl, phenanthryl, fluoranthenyl, triphenylenyl, chrysenyl, naphthacenyl, picenyl, perylenyl, pentaphenyl, hexacenyl, pyrenyl or anthryl, preferably phenyl, 1 -naphthyl, 2-naphthyl, 9-phenanthryl, 2- or 9-fluorenyl, 3- or 4-biphenyl, which can be unsubstituted or substituted.
  • Examples of C 6 -C 1 aryl are phenyl, 1-naphthyl
  • C 2 -C 30 heteroaryl radical is a ring or ring system in which O, S or N are possible hetero atoms and is typically an unsaturated heterocyclic radical having from 5 to 30 atoms, which has at least 6 conjugated ⁇ -electrons, such as thienyl, benzo[b]thienyl, dibenzo[b,d]thienyl, thianthrenyl, furyl, furfuryl.
  • the above-mentioned groups can be substituted, for example, by a C ⁇ -C 8 alkyl radical, a hydroxyl group, a mercapto group, a CrC 8 alkoxy radical, a C C 8 alkylthio radical, a halogen atom, a halo-C C 8 alkyl radical, a cyano group, an aldehyde group, a ketone group, a carboxyl group, an ester group, a carbamoyl radical, an amino group or a nitro group.
  • the "carbamoyl radical” is typically a C ⁇ -18 carbamoyl radical, preferably a C ⁇ -8 carbamoyl radical, which can be unsubstituted or substituted, for example carbamoyl, methylcarbamoyl, ethylcarbamoyl, n-butylcarbamoyl, tert-butylcarbamoyl, dimethylcarbamoyloxy, morpholino- carbamoyl or pyrrolidinocarbamoyl.
  • Examples of a C 7 -C ⁇ 2 aralkyl radical are benzyl, 2-benzyl-2-propyl, ⁇ -phenyl-ethyl, ⁇ ,o dimethylbenzyl, oophenyl-butyl or ⁇ ,o>dimethyl- ⁇ -phenyl-butyl, it being possible for both the alkyl moiety and the aryl moiety to be unsubstituted or substituted.
  • halo-C Caalkyl radical denotes alkyl radicals in which some or all of the hydrogen atoms have been replaced by halogen atoms, such as, for example, a trifluoromethyl group etc.
  • aldehyde group, ketone group and ester group include those groups which can be substituted by a CrC t salkyl radical, a C 6 -C 4 aryl radical or a C 7 -C 2 aralkyl radical, it being possible for the aryl radical and the aralkyl radical to be unsubstituted or substituted.
  • the printing inks according to the invention comprise the indicators, especially the compounds of formulae I, II, III, IV, V and VI, advantageously in a concentration of from 0.01 to 75 % by weight, preferably from 1 to 50 % by weight, especially from 5 to 40 % by weight, more especially from 10 to 25 % by weight, based on the total weight of the printing ink, and can be used, for example, for electrophotography, intaglio printing, flexographic printing, screen printing, offset printing or letterpress printing.
  • the printing ink is, for example, a liquid or paste-form dispersion comprising colorant (indicator), binder and optionally solvent and/or optionally water and additives.
  • the binder and, where applicable, the additives are generally dissolved in a solvent.
  • Customary viscosities in the Brookfield viscometer are, for example, from 20 to 5000 mPa-s, for example from 20 to 1000 mPa-s, for liquid printing inks.
  • the values range, for example, from 1 to 100 Pa ⁇ s, preferably from 5 to 50 Pa-s.
  • the person skilled in the art will be familiar with the ingredients and compositions of printing inks.
  • the printing inks can be used, for example, for electrophotography, intaglio printing, flexographic printing, screen printing, offset printing, lithography or letterpress printing.
  • Suitable printing inks are both solvent-based printing inks and water-based printing inks.
  • Of interest are, for example, printing inks based on aqueous acrylates.
  • Such inks are to be understood as including polymers or copolymers that are obtained by polymerisation of at
  • Suitable organic solvents are water-miscible solvents customarily used by the person skilled in the art, for example alcohols, such as methanol, ethanol and isomers of propanol, butanol and pentanol, ethylene glycol and ethers thereof, such as ethylene glycol methyl ether and ethylene glycol ethyl ether, and ketones, such as acetone, ethyl methyl ketone or cyclohexanone, for example isopropanol. Water and alcohols are preferred.
  • Suitable printing inks comprise, for example, as binder primarily an acrylate polymer or copolymer and the solvent is selected, for example, from the group consisting of water,
  • CrC ⁇ alcohols ethylene glycol, 2-(C 1 -C 5 alkoxy)-ethanol, acetone, ethyl methyl ketone and any mixtures thereof.
  • the printing inks may also comprise customary additives known to the person skilled in the art in customary concentrations.
  • a printing ink is usually prepared by dilution of a printing ink concentrate and can then be used in accordance with methods known perse.
  • the printing inks may, for example, also comprise alkyd systems that dry oxidatively.
  • a suitable aqueous printing ink composition comprises, for example, an indicator, a dispers- ant and a binder.
  • Dispersants that come into consideration include, for example, customary dispersants, such as water-soluble dispersants based on one or more arylsulfonic acid/formaldehyde condensation products or on one or more water-soluble oxalkylated phenols, non-ionic dispersants or polymeric acids.
  • customary dispersants such as water-soluble dispersants based on one or more arylsulfonic acid/formaldehyde condensation products or on one or more water-soluble oxalkylated phenols, non-ionic dispersants or polymeric acids.
  • arylsulfonic acid/formaldehyde condensation products are obtainable, for example, by sulfonation of aromatic compounds, such as naphthalene itself or naphthalene-containing mixtures, and subsequent condensation of the resulting arylsulfonic acids with formaldehyde.
  • aromatic compounds such as naphthalene itself or naphthalene-containing mixtures
  • Suitable oxalkylated phenols are likewise known and are described, for example, in US-A-4,218,218 und DE-A-197 27 767.
  • Suitable non-ionic dispersants are, for example, alkylene oxide adducts, polymerisation products of vinylpyrrolidone, vinyl acetate or vinyl alcohol and co- or ter-polymers of vinyl pyrrolidone with vinyl acetate and/or vinyl alcohol. It is also possible, for example, to use polymeric acids which act both as dispersants and as binders.
  • suitable binder components include acrylate-group- containing, vinyl-group-containing and/or epoxy-group-containing monomers, prepolymers and polymers and mixtures thereof. Further examples are melamine acrylates and silicone acrylates.
  • the acrylate compounds may also be non-ionically modified (e.g. provided with amino groups) or ionically modified (e.g. provided with acid groups or ammonium groups) and used in the form of aqueous dispersions or emulsions (e.g. EP-A-704 469, EP-A- 12 339).
  • the solventless acrylate polymers can be mixed with so-called reactive diluents, for example vinyl-group- containing monomers.
  • Further suitable binder components are epoxy-group-containing compounds.
  • the printing ink compositions may also comprise as additional component, for example, an agent having a water-retaining action (humectant), e.g. polyhydric alcohols, polyalkylene glycols, which renders the compositions especially suitable for ink-jet printing.
  • an agent having a water-retaining action e.g. polyhydric alcohols, polyalkylene glycols, which renders the compositions especially suitable for ink-jet printing.
  • the printing inks may comprise further auxiliaries, such as are customary in the printing and coating industries, for example preservatives (such as glutaric dialdehyde and/or tetramethylolacetyleneurea, anti-oxidants, degassers/defoamers, viscosity regulators, flow improvers, anti-settling agents, gloss improvers, lubricants, adhesion promoters, anti-skin agents, matting agents, emulsifiers, stabilisers, hydrophobic agents, light stabilisers, handle improvers and anti-statics.
  • preservatives such as glutaric dialdehyde and/or tetramethylolacetyleneurea, anti-oxidants, degassers/defoamers, viscosity regulators, flow improvers, anti-settling agents, gloss improvers, lubricants, adhesion promoters, anti-skin agents, matting agents, emulsifiers, stabilisers, hydrophobic
  • the printing inks may also, for example, comprise solubilisers, e.g. ⁇ -caprolactam.
  • the printing inks may, inter alia for the purpose of adjusting the viscosity, comprise thickeners of natural or synthetic origin. Examples of thickeners include commercially available alginate thickeners, starch ethers or locust bean flour ethers.
  • the printing inks comprise such thickeners e.g. in an amount of from 0.01 to 2 % by weight, based on the total weight of the printing ink.
  • the printing inks may comprise buffer substances, for example borax, borate, phosphate, polyphosphate or citrate, in amounts of e.g. from 0.1 to 3 % by weight, in order to establish a pH value of e.g. from 4 to 9, especially from 5 to 8.5.
  • such printing inks may comprise surfactants or humectants.
  • Surfactants that come into consideration include commercially available anionic and non-ionic surfactants.
  • Humectants that come into consideration include, for example, urea or a mixture of sodium lactate (advantageously in the form of a 50 to 60 % aqueous solution) and glycerol and/or propylene glycol in amounts of e.g. from 0.1 to 30 % by weight, especially from 2 to 30 % by weight, in the printing inks.
  • the printing inks may also comprise customary additives, for example foam- reducing agents or especially substances that inhibit the growth of fungi and/or bacteria.
  • additives are usually used in amounts of from 0.01 to 1 % by weight, based on the total weight of the printing ink.
  • the printing inks may also be prepared in customary manner by mixing the individual components together, for example in the desired amount of water.
  • it may be necessary for e.g. the viscosity or other physical properties of the printing ink, especially those properties which influence the affinity of the printing ink for the substrate in question, to be adapted accordingly.
  • Substrate materials that may be mentioned include, for example:
  • - silicate materials such as glass, china and ceramics, which may likewise be coated, - polymeric materials of all kinds, such as polystyrene, polyamides, polyester, polyethylene, polypropylene, melamine resins, polyacrylates, polyacrylonitrile, polyurethanes, polycarbonates, polyvinyl chloride and corresponding copolymers and block copolymers,
  • polyester modified polyester
  • polyester blends cellulosic materials, such as cotton, cotton blends, jute, flax, hemp and ramie, viscose, wool, silk, polyamide, polyamide blends, polyacrylonitrile, triacetate, acetate, polycarbonate, polypropylene, polyvinyl chloride, polyester microfibres and glass fibre fabrics,
  • Especially suitable substrates are e.g. paper, coated paper, cardboard and plastic or metal foils, such as aluminium foils.
  • the printing of the substrate is preferably effected by means of continous or dropwise ink-jet printing.
  • the present invention relates also to non-aqueous or aqueous ink-jet inks which comprise a time-temperature integrator comprising at least one reversible indicator having photochromic properties based on transfer reactions, especially a reversible indicator of formula l, II, 111, IV, V or VI, as defined above.
  • Aqueous ink-jet inks are preferred.
  • the inks may be non-aqueous inks which consist of a solution of the TTI in an organic solvent or a mixture of organic solvents.
  • solvents that can be used for this purpose are alkyl carbitols, alkyl cellosolves, dialkylformamides, dialkylacetamides, alcohols, acetone, methyl ethyl ketone, diethyl ketone, methyl isobutyl ketone, diisopropyl ketone, dibutyl ketone, dioxane, ethyl butyrate, ethyl isovalerate, diethyl malonate, diethyl succinate, butyl acetate, triethyl phosphate, ethyl glycol acetate, toluene, xylene, Tetralin or petroleum ether fractions.
  • solid waxes as solvents that, as ink vehicles, have to be heated first, are stearic or palmi
  • the inks preferably comprise a total content of indicators of from 1 to 35 % by weight, especially from 1 to 30 % by weight and preferably from 1 to 20 % by weight, based on the total weight of the ink.
  • the inks may comprise water-miscible organic solvents, for example CrC 4 alcohols, e.g. methanol, ethanol, n-propanol, isopropanol, n-butanol, sec-butanol, tert-butanol or iso- butanol; amides, e.g. dimethylformamide or dimethylacetamide; ketones or ketone alcohols, e.g. acetone, diacetone alcohol; ethers, e.g. tetrahydrofuran or dioxane; nitrogen-containing heterocyclic compounds, e.g.
  • CrC 4 alcohols e.g. methanol, ethanol, n-propanol, isopropanol, n-butanol, sec-butanol, tert-butanol or iso- butanol
  • amides e.g. dimethylformamide or dimethylacetamide
  • poly- alkylene glycols e.g. polyethylene glycol, or polypropylene glycol
  • C 2 -C 6 alkylene glycols and thioglycols e.g. ethylene glycol, propylene glycol, butylene glycol, triethylene glycol, thio- diglycol, hexylene glycol and diethylene glycol
  • further polyols e.g. glycerol or 1 ,2,6-hexane- triol
  • C ⁇ -C 4 alkyl ethers of polyvalent alcohols e.g.
  • 2-methoxyethan ⁇ l 2-(2-methoxy- ethoxy)ethanol, 2-(2-ethoxyethoxy)ethanol, 2-[2-(2-methoxyethoxy)ethoxy]-ethanol or 2-[2-(2- ethoxyethoxy)ethoxy]ethanol; preferably N-methyl-2-pyrrolidone, diethylene glycol, glycerol or especially 1,2-propylene glycol, usually in an amount of from 2 to 30 % by weight, especially from 5 to 30 % by weight and preferably from 10 to 25 % by weight, based on the total weight of the ink.
  • the inks may also comprise solubilisers, e.g. ⁇ -caprolactam.
  • the printing inks may, inter alia for the purpose of adjusting the viscosity, comprise thickeners of natural or synthetic origin.
  • the pigment preparations according to the invention may comprise a photoinitiator which initiates the polymerisation.
  • Suitable photoinitiators for free radical photopolymerisations are e.g. benzophenone and benzo- phenone derivatives, such as 4-phenylbenzophenone and 4-chlorobenzophenone, aceto- phenone derivatives, such as 1 -benzoylcyclohexan-1-ol, 2-hydroxy-2,2-dimethylaceto- phenone and 2,2-dimethoxy-2-phenylacetophenone, benzoin and benzoin ethers, such as methyl, ethyl and butyl benzoin ethers, benzil ketals, such as benzil dimethyl ketal, 2- methyl-1-[4-(methylthio)phenyl]-2-morpholinopropan-1-one, acylphosphine oxides, such as 2,4,6-trimethylbenzoyldiphenylphosphine oxide and bisacylphosphine oxide
  • Suitable photoinitiators for cationic photopolymerisations are, for example, aryldiazonium salts, such as 4-methoxybenzenediazonium hexafluorophosphate, benzenediazonium tetrafluoroborate and toluenediazonium tetrafluoroarsenate, aryliodonium salts, such as diphenyliodonium hexafluoroarsenate, arylsulfonium salts, such as triphenylsulfonium hexafluorophosphate, benzene- and toluene-sulfonium hexafluorophosphate and bis[4- diphenylsulfonio-phenyljsulfide-bis-hexafluorophosphate, disulfones, such as diphenyl disulfone and phenyl
  • the content thereof is generally from 0.1 to 10 % by weight, preferably from 0.1 to 8 % by weight.
  • thickeners examples include commercially available alginate thickeners, starch ethers or locust bean flour ethers, especially sodium alginate on its own or in admixture with modified cellulose, for example methyl-, ethyl-, carboxymethyl-, hydroxyethyl-, methylhydroxyethyl-, hydroxypropyl- or hydroxypropyl methyl-cellulose, especially having preferably from 20 to 25 % by weight carboxymethylcellulose.
  • Synthetic thickeners that may be mentioned are, for example, those based on poly(meth)acrylic acids or poly(meth)acrylamides.
  • the inks comprise such thickeners e.g. in an amount of from 0.01 to 2 % by weight, especially from 0.01 to 1 % by weight and preferably from 0.01 to 0.5 % by weight, based on the total weight of the ink.
  • the inks may comprise buffer substances, for example borax, borate, phosphate, polyphosphate or citrate.
  • buffer substances for example borax, borate, phosphate, polyphosphate or citrate.
  • the inks may comprise surfactants or humectants.
  • Suitable humectants in the inks according to the invention include, for example, urea or a mixture of sodium lactate (advantageously in the form of a 50 to 60 % aqueous solution) and glycerol and/or propylene glycol in amounts of preferably from 0.1 to 30 % by weight, especially from 2 to 30 % by weight.
  • the inks may also comprise customary additives, for example preservatives (such as glutaric dialdehyde and/or tetramethylolacetyleneurea), anti-oxidants, degassers/defoamers, viscosity regulators, flow improvers, anti-settling agents, gloss improvers, lubricants, adhesion promoters, anti-skin agents, matting agents, emulsifiers, stabilisers, hydrophobic agents, light stabilisers, handle improvers and anti-statics.
  • preservatives such as glutaric dialdehyde and/or tetramethylolacetyleneurea
  • anti-oxidants such as glutaric dialdehyde and/or tetramethylolacetyleneurea
  • degassers/defoamers such as sodium bicarbonate, sodium bicarbonate, sodium bicarbonate, sodium bicarbonate, sodium bicarbonate, sodium bicarbonate, sodium bicarbonate, sodium bicarbonate, sodium
  • the inks can be prepared in customary manner by mixing together the individual constituents in the desired amount of water.
  • the inks according to the invention are especially suitable for use in recording systems of the kind in which an ink is expressed from a small opening in the form of droplets which are directed towards a substrate on which an image is formed.
  • Suitable substrates are, for example, paper, textile fibre materials, metal foils or plastics foils.
  • Suitable recording systems are e.g. commercially available ink-jet printers for use in paper or textile printing.
  • the viscosity or other physical properties of the ink especially those properties which influence the affinity of the ink for the substrate in question, to be adapted accordingly.
  • ink-jet printing individual droplets of ink are sprayed onto a substrate in a controlled manner from a nozzle.
  • the continuous ink-jet method the droplets are produced continuously and any droplets not required for the printing are conveyed to a collecting vessel and recycled.
  • droplets are produced and printed as required; that is to say droplets are produced only when required for the printing.
  • the production of the droplets can be effected, for example, by means of a piezo-inkjet head or by means of thermal energy (bubble jet).
  • the subsequent curing of the binder can be effected in customary manner with the aid of heat or high-energy radiation.
  • the print is irradiated either with electrons under an inert gas atmosphere (e.g. nitrogen) (electron beam curing) or with high-energy electromagnetic radiation, preferably in a wavelength range of from 220 to 450 nm.
  • an inert gas atmosphere e.g. nitrogen
  • high-energy electromagnetic radiation preferably in a wavelength range of from 220 to 450 nm.
  • the chosen light intensities should be matched to the curing speed in order to avoid decomposition of the indicator.
  • a time-temperature integrator comprising at least one reversible indicator having photochromic properties based on transfer reactions, especially a reversible indicator of formula I, II, III, IV, V or VI, as defined above, is applied by means of ink-jet printing to the substrate, especially to the packaging of ageing- and temperature-sensitive products or to labels that are applied to the packaging.
  • Step a) it is possible additionally to apply, by means of ink-jet printing, a reference scale which reproduces the change in the colour of the indicator as a function of time, and it is possible to apply, preferably in black ink, further text (or information), such as an expiry date, product identification, weight, contents etc..
  • Step a) is followed by Step b), activation, especially photo-induced coloration of the reversible indicator.
  • the photo-induced curing of the binder advantageously includes the photo-induced coloration of the reversible indicator.
  • an irreversible photo-sensitive indicator can be applied as tamper-proofing in the form of a covering over the time-temperature integrator.
  • Suitable irreversible indicators include, for example, pyrrole derivatives, such as 2-phenyl-di(2- pyrrole)methane. Such a material turns irreversibly red when it is exposed to UV light.
  • Step c) is followed by the application of a protector, especially a colour filter, which prevents renewed photo-induced coloration of the reversible indicator.
  • a protector especially a colour filter, which prevents renewed photo-induced coloration of the reversible indicator.
  • yellow filters which are permeable only to light having typical wavelengths of more than 430 nm.
  • the protective film that is to say the colour filter, can likewise be applied by means of ink-jet printing.
  • time-temperature integrator and the reference scale are advantageously arranged on a light-coloured substrate in order to facilitate reading.
  • Suitable substrate materials are both inorganic and organic materials, preferably those known from conventional layer and packaging techniques. There may be mentioned by way of example polymers, glass, metals, paper, cardboard etc..
  • the substrate can simultaneously form the packaging material for the perishable products or it can be applied to the packaging material, for example in the form of a label.
  • a printing ink concentrate and/or an ink-jet ink comprising a time-temperature integrator described above can be applied to the packaging of ageing- and temperature-sensitive products in the form of a barcode.
  • the time- and/or temperature-induced decoloration of the indicator is advantageously so adjusted that once the expiry date has been passed, the barcode can no longer be read by a scanner.
  • the time- and/or temperature-dependent decoloration of the indicator can also bring about a change in the barcode such that it can still be read, but, on being read, the information relating to the expiry date is given.
  • a prerequisite for the above-described time- and/or temperature-dependent visualisation of a barcode is, however, that the application of the indicator and its activation by irradiation are followed by the application of a protector, e.g. a colour filter, which prevents renewed photo- induced coloration of the reversible indicator.
  • a protector e.g. a colour filter
  • the method according to the invention allows counterfeit-proof marking of documents as originals in a variety of ways. For example, identification papers, passports, banknotes, cheques and share certificates can be marked as being originals.
  • the method according to the invention can equally be used for creating counterfeit-proof product identification labels.
  • the economic damage caused to the global economy by product piracy and counterfeit goods is immense. It is necessary particularly to prevent counterfeiting in the case of pharmaceutical products.
  • the method according to the invention allows, for example, the counterfeit-proof marking of blister packs, so that it is possible to have a decisive effect in preventing inferior preparations being passed off as the original articles. There is extremely wide scope for use of the marking technology based on the method according to the invention.
  • a strip of a reversible indicator that is not visible under normal circumstances could be applied to a suitable substrate of a product or document to be protected against counterfeiting.
  • Checking the authenticity of the article could then be effected very simply by irradiation (e.g. with a lamp that emits light of a suitable wavelength), so that the indicator strip would be visible to an observer or, in the event of a counterfeit, not visible to the observer.
  • the authenticity of branded products could also be checked in this way. It might be possible for the reproduction of a mark on packaging to be so changed under the action of light of a certain intensity and/or a certain wavelength spectrum that a consumer would be in no doubt as to the origin of the goods. Limits will thus be set on brand and/or product piracy.
  • the above-described principle of counterfeit protection by means of the method according to the invention can also be used for protection against pirate copies, where the original is duplicated by irradiation with light using a copier, scanner etc..
  • a banknote could be provided with an invisible indicator strip which would become visible under the action of light during the copying operation and thus would clearly identify a copy as such. After a certain time period has elapsed, the indicator becomes invisible again so that the original is restored to its original state.
  • the invention accordingly relates also to a method for the counterfeit-proof labelling of products, which comprises the step of printing a time-temperature integrator as product label onto a product or onto the packaging of a product, wherein the time-temperature integrator comprises at least one indicator having photochromic properties based on transfer reactions, especially a reversible indicator of formula I, II, III, IV, V or VI, as defined above, the product label being capable of being rendered visible by activation, especially by photo-induced coloration of the indicator.

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  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Organic Chemistry (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • General Physics & Mathematics (AREA)
  • Materials Engineering (AREA)
  • Wood Science & Technology (AREA)
  • Physics & Mathematics (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • General Chemical & Material Sciences (AREA)
  • Mechanical Engineering (AREA)
  • Inks, Pencil-Leads, Or Crayons (AREA)
  • Printing Methods (AREA)
  • Non-Silver Salt Photosensitive Materials And Non-Silver Salt Photography (AREA)

Abstract

L'invention concerne un procédé d'impression sur un substrat, qui comporte l'étape consistant à : (a) imprimer sur le substrat un intégrateur de temps-température qui comprend au moins un indicateur possédant des propriétés photochromiques dépendant de réactions de transfert.
PCT/EP2004/051733 2003-08-15 2004-08-06 Procede d'impression d'integrateur de temps-temperature sur un substrat WO2005016654A1 (fr)

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Application Number Priority Date Filing Date Title
EP03102553.9 2003-08-15
EP03102553 2003-08-15

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WO2005016654A1 true WO2005016654A1 (fr) 2005-02-24

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Cited By (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2005097925A1 (fr) * 2004-04-01 2005-10-20 Sun Chemical Corporation Photo-initiateurs utilises dans des encres d'impression en creux
WO2007021294A1 (fr) * 2005-08-12 2007-02-22 Vitale Rodney P Appareil et procede d'utilisation d'indicateurs thermochromiques et photochromiques
DE102005051471A1 (de) * 2005-10-21 2007-05-16 Bizerba Gmbh & Co Kg Vorrichtung zur Bereitstellung von aktivierten Indikatoren zur Warenkennzeichnung, Warenkennzeichnung und Verfahren zur Bereitstellung von Indikatoren zur Warenkennzeichnung
EP1882919A2 (fr) 2006-07-27 2008-01-30 Bizerba GmbH & Co. KG Indicateur de temps-température destiné au marquage de marchandises
WO2008049755A3 (fr) * 2006-10-26 2008-06-19 Ciba Holding Inc Couche absorbant la lumière pour des systèmes photochromiques
EP2151323A1 (fr) 2008-08-01 2010-02-10 Alcan Technology & Management Ltd. Matériau d'emballage

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Publication number Priority date Publication date Assignee Title
EP0117390A2 (fr) * 1983-02-25 1984-09-05 Lifelines Technology, Inc. Procédé de surveillance de l'exposé incrémental à l'environnement des produits, subissant des changements de qualité progressifs suite aux stimulations extérieures
GB2272861A (en) * 1992-11-28 1994-06-01 Univ Cardiff Apparatus for reading security documents bearing photochromic or thermochromic prints.
US5593486A (en) * 1995-12-05 1997-01-14 Xerox Corporation Photochromic hot melt ink compositions
WO1999039197A1 (fr) * 1998-01-28 1999-08-05 Dietrich Haarer Substrat pour emballer des produits perissables ou destine a etre applique sur lesdits produits, et procede pour determiner la qualite desdits produits

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0117390A2 (fr) * 1983-02-25 1984-09-05 Lifelines Technology, Inc. Procédé de surveillance de l'exposé incrémental à l'environnement des produits, subissant des changements de qualité progressifs suite aux stimulations extérieures
GB2272861A (en) * 1992-11-28 1994-06-01 Univ Cardiff Apparatus for reading security documents bearing photochromic or thermochromic prints.
US5593486A (en) * 1995-12-05 1997-01-14 Xerox Corporation Photochromic hot melt ink compositions
WO1999039197A1 (fr) * 1998-01-28 1999-08-05 Dietrich Haarer Substrat pour emballer des produits perissables ou destine a etre applique sur lesdits produits, et procede pour determiner la qualite desdits produits

Cited By (12)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2005097925A1 (fr) * 2004-04-01 2005-10-20 Sun Chemical Corporation Photo-initiateurs utilises dans des encres d'impression en creux
US7615110B2 (en) 2004-04-01 2009-11-10 Sun Chemical Corporation Photoinitiators for use in intaglio printing inks
WO2007021294A1 (fr) * 2005-08-12 2007-02-22 Vitale Rodney P Appareil et procede d'utilisation d'indicateurs thermochromiques et photochromiques
DE102005051471A1 (de) * 2005-10-21 2007-05-16 Bizerba Gmbh & Co Kg Vorrichtung zur Bereitstellung von aktivierten Indikatoren zur Warenkennzeichnung, Warenkennzeichnung und Verfahren zur Bereitstellung von Indikatoren zur Warenkennzeichnung
US8323430B2 (en) 2005-10-21 2012-12-04 Bizerba Gmbh & Co. Kg Apparatus and a method for the provision of activated indicators for product marking and a product marking
EP1882919A2 (fr) 2006-07-27 2008-01-30 Bizerba GmbH & Co. KG Indicateur de temps-température destiné au marquage de marchandises
EP1882919A3 (fr) * 2006-07-27 2008-02-13 Bizerba GmbH & Co. KG Indicateur de temps-température destiné au marquage de marchandises
WO2008049755A3 (fr) * 2006-10-26 2008-06-19 Ciba Holding Inc Couche absorbant la lumière pour des systèmes photochromiques
US8007900B2 (en) 2006-10-26 2011-08-30 Basf Se Light absorbing layer for photo-chromic systems
EP2151323A1 (fr) 2008-08-01 2010-02-10 Alcan Technology & Management Ltd. Matériau d'emballage
DE102008035881A1 (de) 2008-08-01 2010-02-25 Alcan Technology & Management Ag Verpackungsmaterial, Verpackung, Verpackungs-Produkt-Einheit und Verfahren zur Kennzeichnung und Prüfung einer Verpackungs-Produkt-Einheit
DE102008035881B4 (de) * 2008-08-01 2013-02-28 Amcor Flexibles Kreuzlingen Ag Verpackungsfolie, Verpackung, Verpackungs-Produkt-Einheit und Verfahren zur Kennzeichnung

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