EP2488368B1 - Use of marking agents having narrow bands - Google Patents

Use of marking agents having narrow bands Download PDF

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Publication number
EP2488368B1
EP2488368B1 EP10768457.3A EP10768457A EP2488368B1 EP 2488368 B1 EP2488368 B1 EP 2488368B1 EP 10768457 A EP10768457 A EP 10768457A EP 2488368 B1 EP2488368 B1 EP 2488368B1
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EP
European Patent Office
Prior art keywords
article
process according
methyl
absorption
marker
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Revoked
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EP10768457.3A
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German (de)
French (fr)
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EP2488368A1 (en
Inventor
Rüdiger Sens
Thomas Gessner
Erwin Thiel
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BASF SE
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BASF SE
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Classifications

    • 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
    • G—PHYSICS
    • G07—CHECKING-DEVICES
    • G07D—HANDLING OF COINS OR VALUABLE PAPERS, e.g. TESTING, SORTING BY DENOMINATIONS, COUNTING, DISPENSING, CHANGING OR DEPOSITING
    • G07D7/00—Testing specially adapted to determine the identity or genuineness of valuable papers or for segregating those which are unacceptable, e.g. banknotes that are alien to a currency
    • G07D7/06—Testing specially adapted to determine the identity or genuineness of valuable papers or for segregating those which are unacceptable, e.g. banknotes that are alien to a currency using wave or particle radiation
    • G07D7/12—Visible light, infrared or ultraviolet radiation
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B41—PRINTING; LINING MACHINES; TYPEWRITERS; STAMPS
    • B41M—PRINTING, DUPLICATING, MARKING, OR COPYING PROCESSES; COLOUR PRINTING
    • B41M1/00—Inking and printing with a printer's forme
    • B41M1/26—Printing on other surfaces than ordinary paper
    • 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
    • B41M3/144—Security printing using fluorescent, luminescent or iridescent effects
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B41—PRINTING; LINING MACHINES; TYPEWRITERS; STAMPS
    • B41M—PRINTING, DUPLICATING, MARKING, OR COPYING PROCESSES; COLOUR PRINTING
    • B41M5/00—Duplicating or marking methods; Sheet materials for use therein
    • B41M5/0041—Digital printing on surfaces other than ordinary paper

Definitions

  • the present invention relates to methods for detecting marks on articles.
  • Another object of the invention are methods for authenticating objects.
  • US 6,303,213 B1 describes substrates protected by the application of visible information against unauthorized copying.
  • the visible information is applied with the aid of dyes or pigments which have a half-width of less than 150 nm, preferably less than 100 nm, in the reflectance spectrum for the longest wavelength band.
  • dyes or pigments which have a half-width of less than 150 nm, preferably less than 100 nm, in the reflectance spectrum for the longest wavelength band.
  • the value of the absorption in solution can be used for the half-width.
  • US 5,238,903 describes azomethine dyes for thermal printing with a half-width at the absorption maximum of 60 to 80 nm in ethyl acetate solution (Example 1).
  • the absorption maxima of the dyes are between 430 and 620 nm.
  • the security tag is achieved by means of an identification tag containing colorless or faintly colored, IR absorbing dyes.
  • IR absorbing dyes include nitroso, cyanine, iminium, diiminium, dithiolene compounds, phthalocyanines or azo compounds.
  • the printing inks described above contain at least one dye or pigment having at least one absorption maximum in the visible region of the electromagnetic spectrum, which is clearly different from the absorption maxima of the primary colors of the CIEXYZ system and / or an absorption band in the visible region of the electromagnetic spectrum having a half-width of, more preferably less than 1500 cm -1 .
  • Dyes and pigments are selected from the classes of cyanines, quinones, porphyrins, phthalocyanines or the hetero-substituted polycyclic hydrocarbons.
  • An object of the present invention was thus to provide such methods which are easy to apply with higher security against counterfeiting.
  • Expressions of the form C a -C b designate in the context of this invention chemical compounds or substituents with a certain number of carbon atoms.
  • the number of carbon atoms can be selected from the entire range from a to b, including a and b, a is at least 1 and b is always greater than a.
  • Further specification of the chemical compounds or substituents is made by terms of the form C a -C b -V.
  • V here stands for a chemical compound class or substituent class, for example for alkyl compounds or alkyl substituents.
  • Halogen is fluorine, chlorine, bromine or iodine, preferably fluorine, chlorine or bromine, particularly preferably fluorine or chlorine.
  • UV wavelength range of the electromagnetic spectrum is from 180 to 380 nm. Accordingly, the visible and IR wavelength ranges of the electromagnetic spectrum of 380 to 780 nm and 780 to 1800 nm.
  • the narrow bands have a half width of ⁇ (less than) 1500 cm -1 .
  • the half width of a narrow band is ⁇ (less than) 1200 cm -1 , more preferably ⁇ (less than) 1000 cm -1 , most preferably from 20 to 1000 cm -1 , especially from 20 to 800 cm -1 .
  • the marker remains permanently attached to the article after being brought into contact with the article to be marked.
  • the marker may be attached to or bonded to the article to be marked by chemical bonding or physical forces such as adsorption.
  • a permanent connection is achieved by the marker is connected by an intense interaction with the object to be marked. This intense interaction causes the label to be permanently, i. at least for a period of a few minutes to a few years, preferably from a few days to 25 years, more preferably from one year to 20 years, in particular from one year to 10 years remains associated with the object.
  • An advantage of the method according to the invention is therefore that the marking agents have not only isolated, for example in solution, narrow bands, but also after bringing into contact with the object to be marked, for example after a printing operation.
  • the marker is in contact with an article, e.g. a label, this item itself serving to mark another item by temporarily or permanently attaching it to the other item, e.g. via an adhesive.
  • At least one of the markers has at least two narrow bands with a half-value width of ⁇ 1500 cm -1 and these narrow bands are in the UV and / or visible and / or IR wavelength range of the electromagnetic spectrum.
  • the absorption maximum of at least one narrow band is preferably in the wavelength range from 180 to 1100 nm, particularly preferably in the wavelength range from 350 to 900 nm, very particularly preferably from 350 to 750 nm, in particular from 400 to 750 nm.
  • markers selected from organic dyes or pigments are used, these being ironic bands in contact with the article to be marked.
  • inorganic chromophores are also suitable as markers, for example rare earth or transition metal compounds.
  • the ions of the rare earths are to be mentioned here with often very narrow-band emission lines, which are used for example in fluorescent lamps and in cathode ray tubes. Examples are Y 2 O 3 : Eu complexes, Mg 4 GeO 5 .5F or (Ce, Tb) MgAl 11 O 19 (see Industrial Inorganic Pigments: edited by Gunter Buxbaum and Gerhard Pfaff, WILEY-VCH, pp. 274-275 , third, completely revised and extended edition).
  • the narrow band absorption lines of the holmium oxides used for the spectral calibration are Ho 2 O 3 , furthermore Ho (3+) in LiYF 4 or Nd: YAG compounds.
  • the markers are preferably selected from metal-containing or metal-free phthalocyanines, preferably copper phthalocyanines, silicon phthalocyanines, aluminum phthalocyanines, zinc phthalocyanines, particularly preferably silicon phthalocyanines which are provided with sterically demanding substituents on the silicon atom or the Phthalocyaninchromophors; Cyanine dyes, preferably charged cyanine dyes, more preferably rhodamine, oxazine or pseudoisocyanine dyes; Merocyanines, preferably electroneutral merocyanines, more preferably merocyanines in Cyanlimit; perylene; Violanthrones, Isoviolanthrones; Squaric acid dyes; Quinones, coumarins, rhodamines, or porphyrins.
  • metal-containing or metal-free phthalocyanines preferably copper phthalocyanines, silicon phthalocyanines, aluminum phthalocyanines, zinc phthalocyanines, particularly preferably silicon
  • aryl radicals in the general form in the para position may also contain sulfonic acid radicals or alkali metal salts of these substituents (eg -SO 3 H, -SO 3 Na, -SO 3 K).
  • merocyanine dyes are also suitable EP 08168116.5 (Formula IIa p.34 and Formula L2-03 p.37).
  • the merocyanine dye with suitably narrow absorption band.
  • an amount of the marking substance is used which can still be detected with the aid of the respective method for a later detection of the presence of the marking substance.
  • This amount of label may vary over a wide range, for example, depending on the nature of the label or detection method. As a rule, from 50% by weight up to a few ppb, based on the total amount of marker and article to be marked, of the marker is brought into contact with the article to be marked, preferably from 0.01 to 10% by weight.
  • the article to be marked is preferably brought into contact with at least one marker at at least one point on its surface.
  • the location to be marked on the surface is often relatively small in relation to the total surface of the article.
  • the area of the site to be marked is from one square millimeter to one square centimeter.
  • the article to be marked preferably contains paper, for example cardboard or cardboard, metal, glass, ceramic or plastic. Particularly preferably, the article to be marked contains from 1 to 99 wt .-% paper, metal, glass, ceramic or plastic, most preferably from 10 to 99 wt .-%.
  • the object to be marked consists essentially of paper, metal, glass, ceramic and / or plastic.
  • the article to be marked is based on a composite material containing, for example, paper or cardboard and plastic.
  • the object to be marked is based on multilayer plastic films (laminate).
  • the object to be marked contains paper and is a banknote, a security, an admission ticket, a document, a packaging, a label or a document.
  • the object to be marked contains plastic and is a check card, a foil or a packaging.
  • the object to be marked represents a packaging for consumer goods, in particular pharmaceuticals, cosmetics, cleaning agents, foodstuffs or industrial goods, in particular automobile parts.
  • the contacting of the marker with the article to be marked is accomplished by printing the marker or a mixture containing the marker on the article.
  • Inkjet printing inkjet
  • screen printing offset printing
  • flexographic printing thermal printing
  • thermal printing or (electro) photography are preferably used as printing processes.
  • printing inks or inks are used as mixtures containing the marking substance.
  • the formulation of the mixture and / or the application of the marker or the mixture can be done with either aqueous or oil based inks or inks.
  • step b a change in the position of the at least one narrow band made by a solvatochromic, electrochromic, or thermochromic influence.
  • the change in the position of the narrow band by the action of electric and Thermochromism made.
  • a solvatochromic influence on the spectral position of the narrow band can be brought about, for example, by a change in the solvent.
  • Electrochromic influence results from the application and the change of an electric field and a thermochromic influence results from the change of the temperature.
  • a photochromic influence results from the irradiation of electromagnetic radiation.
  • the change of the spectral position is preferably recurring and is modulated with a certain frequency.
  • the modulation frequency is in this case preferably from 0.1 to 10 Hz, in particular from 0.1 to 5 Hz.
  • the irradiation of the object with electromagnetic radiation is preferably carried out with the aid of a narrow-band radiation source.
  • narrow-band radiation sources lasers such as dye lasers, solid-state lasers or laser diodes are used.
  • the narrow-band radiation source preferably has a half-width of 0.01 to 10 nm for the radiation emitted by it, particularly preferably from 0.1 to 5 nm, particularly preferably from 0.1 to 2 nm.
  • the irradiation is carried out with the help of at least two narrow-band radiation sources.
  • At least one of the markers (step a.) Has at least two narrow bands with a half width of 20 cm -1 to 800 cm -1 and these narrow bands are in the UV - and / or visible and / or IR wavelength range of the electromagnetic spectrum and the irradiation (step b.) Is performed by means of at least two narrow-band radiation sources.
  • the determination of the absorption (step d.) Is carried out visually.
  • At least one of the markers (step a.) Has at least two narrow bands with a half-width of 0.5 nm to 10 nm, and these narrow bands are in the UV and / or visible and / or IR wavelength range of the electromagnetic spectrum and the irradiation (step b.) Is performed by means of at least two narrow-band light sources and the determination of the absorption (step d.) Is carried out visually.
  • two light sources are preferably modulated in antiphase (visual lock-in method).
  • the Intensities of the two light beams adjusted so that unlabeled (areas of) objects offer the visual system very similar or substantially the same brightness.
  • the modulation frequency is in this case preferably from 0.1 to 10 Hz, in particular from 0.1 to 5 Hz.
  • the determination of the absorption Is carried out by measuring an absorption spectrum with the aid of a spectrometer.
  • At least one of the markers (step a.) Has at least two narrow bands with a half-value width of 20 cm -1 to 800 cm -1 and these narrow bands are in the UV and / or visible and / or IR wavelength range of the electromagnetic spectrum and the irradiation (step b.) Is performed by means of at least two narrow-band light sources and the determination of the absorption (step d.) Is by measuring an absorption spectrum using a Spectrometer performed.
  • two light sources are preferably modulated in antiphase (electronic lock-in method).
  • the intensities of the two light beams are adjusted so that unmarked (areas of) objects offer the spectrometer very similar or substantially the same intensities.
  • the spectrometer as detection or detection apparatus in marked areas determines an oscillation with the modulation frequency of the light sources.
  • the modulation frequency is in this case preferably from 0.1 to 10 Hz, in particular from 0.1 to 5 Hz.
  • quantities derived from the absorption or the absorption spectrum are used to compare the absorption or the absorption spectrum (step b.).
  • these quantities are intensities or positions of absorption maxima.
  • the comparison Is performed by means of a computer having access to stored data for absorption, absorption spectrum or derived quantities of the authentic object.
  • the method according to the invention can also be carried out using fluorescence measurements, using appropriately markers with narrow fluorescence signals. These markers are preferably selected from the group of the above-mentioned markers.
  • the authentication is carried out with the aid of a ticket, ticket or cash machine.
  • the authentication is performed by means of a portable device.
  • the inventive method for authenticating an article is used in the authentication of consumer goods or industrial goods, in particular securities, documents, packaging.
  • the methods according to the invention for marking for detection and authentication can be carried out with the aid of devices which are known to the person skilled in the art from the prior art and thus can be easily implemented.
  • the combination of narrow band absorption bands, narrow band radiation sources, and the modulation of the radiation source or banding provide an increased safety standard of the tag over known tagging of articles.
  • the basis for the production of the marking ink was the clear lacquer (matt) from Horstmann-Steinberg (ACRYLAC® Matt 57 0080/40, water-based dispersion lacquer).
  • this paint 0.01 wt .-% of the marker at room temperature (21 ° C) were stirred until a homogeneous distribution of the marker was reached.
  • the marker used was a mixture of silicon phthalocaninines:
  • the compounds were used in a 1: 2: 1 (A: B: C) mixture.
  • This marker shows in the marking ink before and after printing a sharp absorption at 666 nm.
  • the solution ethyl acetate shows the mixture at 666 nm a half-width of 265 cm -1 and after printing a half-width of 610 cm -1 .
  • the printing process was carried out with a printing machine from Heidelberger Druckmaschinen type GOT 52 two-color (offset printing).
  • a mark by printing was applied on white SM paper.
  • the concentration The above-mentioned marking substance in the printing ink was reduced to such an extent that, when illuminated with daylight or white artificial light, the marking was located just below the limit of visibility, ie could not be seen with the naked eye.
  • the marked white paper was overprinted with a color image (demo object). This happened with a commercial inkjet printer.
  • This illumination device contains two light sources with different wavelengths. Two laser diodes with wavelengths of 666 nm (absorption maximum of the marker) and 650 nm were used (only weakly absorbed by the marker because of the narrow absorption band).
  • This lighting device has been implemented as a light source in the form of a light pen, with which the mark for the perception can be continuously illuminated with the human eye.
  • Example 1 can be carried out analogously for the case that the detection of the marker pattern is not carried out with the human eye, but with a spectrometer that is used to detect the modulation of an absorption or fluorescence signal.

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  • Health & Medical Sciences (AREA)
  • General Health & Medical Sciences (AREA)
  • Toxicology (AREA)
  • Physics & Mathematics (AREA)
  • General Physics & Mathematics (AREA)
  • Credit Cards Or The Like (AREA)
  • Inks, Pencil-Leads, Or Crayons (AREA)
  • Ink Jet Recording Methods And Recording Media Thereof (AREA)
  • Inspection Of Paper Currency And Valuable Securities (AREA)
  • Printing Methods (AREA)

Description

Die vorliegende Erfindung betrifft Verfahren zum Nachweis von Markierungen auf Gegenständen. Ein weiterer Gegenstand der Erfindung sind Verfahren zur Authentifizierung von Gegenständen.The present invention relates to methods for detecting marks on articles. Another object of the invention are methods for authenticating objects.

Weitere Ausführungsformen der vorliegenden Erfindung sind den Ansprüchen, der Beschreibung und den Beispielen zu entnehmen. Es versteht sich, dass die vorstehend genannten und die nachstehend noch zu erläuternden Merkmale des erfindungsgemäßen Gegenstandes nicht nur in der jeweils konkret angegebenen Kombination, sondern auch in anderen Kombinationen verwendbar sind, ohne den Rahmen der Erfindung zu verlassen. Bevorzugt bzw. ganz bevorzugt sind die Ausführungsformen der vorliegenden Erfindung in denen alle Merkmale die bevorzugten bzw. ganz bevorzugten Bedeutungen haben.Further embodiments of the present invention can be taken from the claims, the description and the examples. It is understood that the features mentioned above and those yet to be explained of the subject matter according to the invention can be used not only in the particular concretely specified combination but also in other combinations without departing from the scope of the invention. Preferred or very preferred are the embodiments of the present invention in which all features have the preferred or very preferred meanings.

US 6,303,213 B1 beschreibt Substrate, die durch das Auftragen von sichtbaren Informationen gegen unbefugtes Kopieren geschützt sind. Die sichtbare Information wird mit Hilfe von Farbstoffen oder Pigmenten aufgetragen, die im Remissionsspektrum für die längstwellige Bande eine Halbwertsbreite von kleiner 150 nm, bevorzugt kleiner 100 nm aufweisen. Für lösliche fluoreszierende Farbstoffe kann für die Halbwertsbreite der Wert der Absorption in Lösung verwendet werden. US 6,303,213 B1 describes substrates protected by the application of visible information against unauthorized copying. The visible information is applied with the aid of dyes or pigments which have a half-width of less than 150 nm, preferably less than 100 nm, in the reflectance spectrum for the longest wavelength band. For soluble fluorescent dyes, the value of the absorption in solution can be used for the half-width.

US 5,238,903 beschreibt Azomethinfarbstoffe für den Thermodruck mit einer Halbwertsbreite des Absorptionsmaximums von 60 bis 80 nm in Ethylacetatlösung (Beispiel 1). Die Absorptionsmaxima der Farbstoffe liegen zwischen 430 und 620 nm. US 5,238,903 describes azomethine dyes for thermal printing with a half-width at the absorption maximum of 60 to 80 nm in ethyl acetate solution (Example 1). The absorption maxima of the dyes are between 430 and 620 nm.

In der EP 0 340 898 A2 wird ein Verfahren zur Markierung eines Gegenstandes beschrieben. Die Sicherheitsmarkierung wird mit Hilfe einer Identifizierungsmarkierung erreicht, enthaltend farblose oder schwach gefärbte, im IR absorbierenden Farbstoffe. Als IR-Farbstoffe sind unter anderem Nitroso-, Cyanin-, Iminium-, Diiminium-, Dithiolenverbindungen, Phthalocyanine oder Azoverbindungen genannt.In the EP 0 340 898 A2 a method for marking an article is described. The security tag is achieved by means of an identification tag containing colorless or faintly colored, IR absorbing dyes. Among others, nitroso, cyanine, iminium, diiminium, dithiolene compounds, phthalocyanines or azo compounds are mentioned as IR dyes.

In der WO 2004/029163 A1 werden Druckfarben zur Markierung und Authentifizierung von Gegenständen beschrieben. Hierbei werden die Farbstoffe oder Pigmente der WO 2004/029163 A1 so ausgewählt, dass die Wahrnehmung des Farbraums der ausgewählten Farbstoffe mit Hilfe des menschlichen Auges nicht vollständig ist. Die in der WO 2004/029163 A1 beschriebenen Druckfarben enthalten wenigstens einen Farbstoff oder ein Pigment mit wenigstens einem Absorptionsmaximum im sichtbaren Bereich des elektromagnetischen Spektrums, das deutlich verschieden von den Absorptionsmaxima der Grundfarben des CIEXYZ Systems ist und/oder eine Absorptionsbande im sichtbaren Bereich des elektromagnetischen Spektrums mit einer Halbwertsbreite von besonders bevorzugt weniger als 1500 cm-1 aufweist. Farbstoffe und Pigmente werden gewählt aus den Verbindungsklassen der Cyanine, Chinone, Porphyrine, Phthalocyanine oder der heterosubstituierten polycyclischen Kohlenwasserstoffe.In the WO 2004/029163 A1 Printing inks are described for marking and authenticating objects. Here, the dyes or pigments of the WO 2004/029163 A1 chosen so that the perception of the color space of the selected dyes with the help of the human eye is not complete. The in the WO 2004/029163 A1 The printing inks described above contain at least one dye or pigment having at least one absorption maximum in the visible region of the electromagnetic spectrum, which is clearly different from the absorption maxima of the primary colors of the CIEXYZ system and / or an absorption band in the visible region of the electromagnetic spectrum having a half-width of, more preferably less than 1500 cm -1 . Dyes and pigments are selected from the classes of cyanines, quinones, porphyrins, phthalocyanines or the hetero-substituted polycyclic hydrocarbons.

Trotz der bereits beschriebenen Ansätze zur Markierung und Authentifizierung von Gegenständen besteht ein Bedarf an weiteren Verfahren, insbesondere solche Verfahren, die einfach anzuwenden sind und einen höheren Grad an Sicherheit gegenüber Fälschungen bieten.Despite the approaches to mark and authenticate items already described, there is a need for further methods, particularly those methods that are easy to use and offer a higher level of security against counterfeiting.

Eine Aufgabe der vorliegenden Erfindung war somit die Bereitstellung solcher Verfahren, die bei höherer Fälschungssicherheit einfach anzuwenden sind.An object of the present invention was thus to provide such methods which are easy to apply with higher security against counterfeiting.

Diese Aufgabe wurde gelöst durch ein Verfahren gemäß Anspruch 1.This object has been achieved by a method according to claim 1.

Ausdrücke der Form Ca-Cb bezeichnen im Rahmen dieser Erfindung chemische Verbindungen oder Substituenten mit einer bestimmten Anzahl von Kohlenstoffatomen. Die Anzahl an Kohlenstoffatomen kann aus dem gesamten Bereich von a bis b, einschließlich a und b gewählt werden, a ist mindestens 1 und b immer größer als a. Eine weitere Spezifizierung der chemischen Verbindungen oder der Substituenten erfolgt durch Ausdrücke der Form Ca-Cb-V. V steht hierbei für eine chemische Verbindungsklasse oder Substituentenklasse, beispielsweise für Alkylverbindungen oder Alkylsubstituenten.Expressions of the form C a -C b designate in the context of this invention chemical compounds or substituents with a certain number of carbon atoms. The number of carbon atoms can be selected from the entire range from a to b, including a and b, a is at least 1 and b is always greater than a. Further specification of the chemical compounds or substituents is made by terms of the form C a -C b -V. V here stands for a chemical compound class or substituent class, for example for alkyl compounds or alkyl substituents.

Halogen steht für Fluor, Chlor, Brom, oder lod, vorzugsweise für Fluor, Chlor oder Brom, besonders bevorzugt für Fluor oder Chlor.Halogen is fluorine, chlorine, bromine or iodine, preferably fluorine, chlorine or bromine, particularly preferably fluorine or chlorine.

Im Einzelnen haben die für die verschiedenen Substituenten angegebenen Sammelbegriffe folgende Bedeutung:

  • C1-C20-Alkyl: geradkettige oder verzweigte Kohlenwasserstoffreste mit bis zu 20 Kohlenstoffatomen, beispielsweise C1-C10-Alkyl oder C11-C20-Alkyl, bevorzugt C1-C10-Alkyl beispielsweise C1-C3-Alkyl, wie Methyl, Ethyl, Propyl, Isopropyl, oder C4-C6-Alkyl, n-Butyl, sec-Butyl, tert.-Butyl, 1,1-Dimethylethyl, Pentyl, 2-Methylbutyl, 1,1-Dimethylpropyl, 1,2-Dimethylpropyl, 2,2-Dimethylpropyl, 1-Ethylpropyl, Hexyl, 2-Methylpentyl, 3-Methyl-pentyl, 1,1-Dimethylbutyl, 1,2-Dimethylbutyl, 1,3-Dimethylbutyl, 2,2-Dimethylbutyl, 2,3-Dimethylbutyl, 3,3-Dimethylbutyl, 2-Ethylbutyl, 1,1,2-Trimethylpropyl, 1,2,2-Trimethylpropyl, 1-Ethyl-1-methylpropyl, 1-Ethyl-2-methylpropyl, oder C7-C10-Alkyl, wie Heptyl, Octyl, 2-Ethyl-hexyl, 2,4,4-Trimethylpentyl, 1,1,3,3-Tetramethylbutyl, Nonyl oder Decyl sowie deren Isomere.
  • C2-C20-Alkenyl: ungesättigte, geradkettige oder verzweigte Kohlenwasserstoffreste mit 2 bis 20 Kohlenstoffatomen und einer Doppelbindung in einer beliebigen Position, beispielsweise C2-C10-Alkenyl oder C11-C20-Alkenyl, bevorzugt C2-C10-Alkenyl wie C2-C4-Alkenyl, wie Ethenyl, 1-Propenyl, 2-Propenyl, 1-Methylethenyl, 1-Butenyl, 2-Butenyl, 3-Butenyl, 1-Methyl-1-propenyl, 2-Methyl-1-propenyl, 1-Methyl-2-propenyl, 2-Methyl-2-propenyl, oder C5-C6-Alkenyl, wie 1-Pentenyl, 2-Pentenyl, 3-Pentenyl, 4-Pentenyl, 1-Methyl-1-butenyl, 2-Methyl-1-butenyl, 3-Methyl-1-butenyl, 1-Methyl-2-butenyl, 2-Methyl-2-butenyl, 3-Methyl-2-butenyl, 1-Methyl-3-butenyl, 2-Methyl-3-butenyl, 3-Methyl-3-butenyl, 1,1-Dimethyl-2-propenyl, 1,2-Dimethyl-1-propenyl, 1,2-Dimethyl-2-propenyl, 1-Ethyl-1-propenyl, 1-Ethyl-2-propenyl, 1-Hexenyl, 2-Hexenyl, 3-Hexenyl, 4-Hexenyl, 5-Hexenyl, 1-Methyl-1-pentenyl, 2-Methyl-1-pentenyl, 3-Methyl-1-pentenyl, 4-Methyl-1-pentenyl, 1-Methyl-2-pentenyl, 2-Methyl-2-pentenyl, 3-Methyl-2-pentenyl, 4-Methyl-2-pentenyl, 1-Methyl-3-pentenyl, 2-Methyl-3-pentenyl, 3-Methyl-3-pentenyl, 4-Methyl-3-pentenyl, 1-Methyl-4-pentenyl, 2-Methyl-4-pentenyl, 3-Methyl-4-pentenyl, 4-Methyl-4-pentenyl, 1,1-Dimethyl-2-butenyl, 1,1-Dimethyl-3-butenyl, 1,2-Dimethyl-1-butenyl, 1,2-Dimethyl-2-butenyl, 1,2-Dimethyl-3-butenyl, 1,3-Dimethyl-1-butenyl, 1,3-Dimethyl-2-butenyl, 1,3-Dimethyl-3-butenyl, 2,2-Dimethyl-3-butenyl, 2,3-Dimethyl-1-butenyl, 2,3-Dimethyl-2-butenyl, 2,3-Dimethyl-3-butenyl, 3,3-Dimethyl-1-butenyl, 3,3-Dimethyl-2-butenyl, 1-Ethyl-1-butenyl, 1-Ethyl-2-butenyl, 1-Ethyl-3-butenyl, 2-Ethyl-1-butenyl, 2-Ethyl-2-butenyl, 2-Ethyl-3-butenyl, 1,1,2-Trimethyl-2-propenyl, 1-Ethyl-1-methyl-2-propenyl, 1-Ethyl-2-methyl-1-propenyl oder 1-Ethyl-2-methyl-2-propenyl, sowie C7-C10-Alkenyl, wie die Isomere von Heptenyl, Octenyl, Nonenyl oder Decenyl.
  • C2-C20-Alkinyl: geradkettige oder verzweigte Kohlenwasserstoffgruppen mit 2 bis 20 Kohlenstoffatomen und einer Dreifachbindung in einer beliebigen Position, beispielsweise C2-C10-Alkinyl oder C11-C20-Alkinyl, bevorzugt C2-C10-Alkinyl wie C2-C4-Alkinyl, wie Ethinyl, 1-Propinyl, 2-Propinyl, 1-Butinyl, 2-Butinyl, 3-Butinyl, 1-Me-thyl-2-propinyl, oder C5-C7-Alkinyl, wie 1-Pentinyl, 2-Pentinyl, 3-Pentinyl, 4-Pentinyl, 1-Methyl-2-butinyl, 1-Me-thyl-3-butinyl, 2-Methyl-3-butinyl, 3-Methyl-1-butinyl, 1,1-Dimethyl-2-propinyl, 1-Ethyl-2-propinyl, 1-Hexinyl, 2-Hexinyl, 3-Hexinyl, 4-Hexinyl, 5-Hexinyl, 1-Methyl-2-pentinyl, 1-Methyl-3-pentinyl, 1-Methyl-4-pentinyl, 2-Methyl-3-pentinyl, 2-Methyl-4-pentinyl, 3-Methyl-1-pentinyl, 3-Methyl-4-pentinyl, 4-Methyl-1-pentinyl, 4-Methyl-2-pentinyl, 1,1-Dimethyl-2-butinyl, 1,1-Dimethyl-3-butinyl, 1,2-Dimethyl-3-butinyl, 2,2-Dimethyl-3-butinyl, 3,3-Dimethyl-1-butinyl, 1-Ethyl-2-butinyl, 1-Ethyl-3-butinyl, 2-Ethyl-3-butinyl oder 1-Ethyl-1-methyl-2-propinyl sowie C7-C10-Alkinyl, wie die Isomere von Heptinyl, Octinyl, Noninyl, Decinyl.
  • C3-C15-Cycloalkyl: monocyclische, gesättigte Kohlenwasserstoffgruppen mit 3 bis zu 15 Kohlenstoffringgliedern, bevorzugt C3-C8-Cycloalkyl wie Cyclopropyl, Cyclobutyl, Cyclopentyl, Cyclohexyl, Cycloheptyl oder Cyclooctyl sowie ein gesättigtes oder ungesättigtes cyclisches System wie z. B. Norbornyl oder Norbenyl.
  • Aryl: ein ein- bis dreikerniges aromatisches Ringsystem enthaltend 6 bis 14 Kohlenstoffringglieder, z. B. Phenyl, Naphthyl oder Anthracenyl, bevorzugt ein ein- bis zweikerniges, besonders bevorzugt ein einkerniges aromatisches Ringsystem.
  • C1-C20-Alkoxy bedeutet eine geradkettige oder verzweigte Alkylgruppe mit 1 bis 20 Kohlenstoffatomen (wie vorstehend genannt), welche über ein Sauerstoffatom (-O-) an gebunden sind, beispielsweise C1-C10-Alkoxy oder C11-C20-Alkoxy, bevorzugt C1-C10-Alkyloxy, insbesondere bevorzugt C1-C3-Alkoxy, wie beispielweise Methoxy, Ethoxy, Propoxy.
  • Aryloxy ist ein ein- bis dreikerniges aromatisches Ringsystem (wie vorstehend genannt), welches über ein Sauerstoffatom (-O-) angebunden ist, bevorzugt ein ein- bis zweikerniges, besonders bevorzugt ein einkerniges aromatisches Ringsystem.
  • Arylalkyl ist ein ein- bis dreikerniges aromatisches Ringsystem (wie vorstehend genannt), welches über eine C1-C20-Alkylengruppe angebunden ist, bevorzugt ein ein- bis zweikerniges, besonders bevorzugt ein einkerniges aromatisches Ringsystem.
  • Hetaryl: Heterocyclische Substituenten, die sich formal von Aryl-Gruppen ableiten indem eine oder mehrere Methin- (-C=) und/oder Vinylengruppe (-CH=CH-) durch Tri-oder divalente Heteroatome ersetzt werden. Bevorzugt sind als Heteroatome Sauerstoff, Stickstoff und/oder Schwefel. Besonders bevorzugt Stickstoff und/oder Sauerstoff.
  • Heteroatome sind Phosphor, Sauerstoff, Stickstoff oder Schwefel bevorzugt Sauerstoff, Stickstoff oder Schwefel, deren freie Valenzen gegebenenfalls durch H-Atome abgesättigt sind.
In detail, the collective terms given for the various substituents have the following meaning:
  • C 1 -C 20 alkyl: straight-chain or branched hydrocarbon radicals having up to 20 carbon atoms, for example C 1 -C 10 alkyl or C 11 -C 20 alkyl, preferably C 1 -C 10 alkyl, for example C 1 -C 3 - Alkyl, such as methyl, ethyl, propyl, isopropyl, or C 4 -C 6 alkyl, n-butyl, sec-butyl, tert-butyl, 1,1-dimethylethyl, pentyl, 2-methylbutyl, 1,1-dimethylpropyl , 1,2-dimethylpropyl, 2,2-dimethylpropyl, 1-ethylpropyl, hexyl, 2-methylpentyl, 3-methyl-pentyl, 1,1-dimethylbutyl, 1,2-dimethylbutyl, 1,3-dimethylbutyl, 2,2 Dimethylbutyl, 2,3-dimethylbutyl, 3,3-dimethylbutyl, 2-ethylbutyl, 1,1,2-trimethylpropyl, 1,2,2-trimethylpropyl, 1-ethyl-1-methylpropyl, 1-ethyl-2-methylpropyl , or C7-C10-alkyl, such as heptyl, octyl, 2-ethyl-hexyl, 2,4,4-trimethylpentyl, 1,1,3,3-tetramethylbutyl, nonyl or decyl and their isomers.
  • C 2 -C 20 -alkenyl: unsaturated, straight-chain or branched hydrocarbon radicals having 2 to 20 carbon atoms and a double bond in any position, for example C 2 -C 10 -alkenyl or C 11 -C 20 -alkenyl, preferably C 2 -C 10 Alkenyl, such as C 2 -C 4 alkenyl, such as ethenyl, 1-propenyl, 2-propenyl, 1-methylethenyl, 1-butenyl, 2-butenyl, 3-butenyl, 1-methyl-1-propenyl, 2-methyl- 1-propenyl, 1-methyl-2-propenyl, 2-methyl-2-propenyl, or C 5 -C 6 -alkenyl, such as 1-pentenyl, 2-pentenyl, 3-pentenyl, 4-pentenyl, 1-methyl- 1-butenyl, 2-methyl-1-butenyl, 3-methyl-1-butenyl, 1-methyl-2-butenyl, 2-methyl-2-butenyl, 3-methyl-2-butenyl, 1-methyl-3- butenyl, 2-methyl-3-butenyl, 3-methyl-3-butenyl, 1,1-dimethyl-2-propenyl, 1,2-dimethyl-1-propenyl, 1,2-dimethyl-2-propenyl, 1- Ethyl 1-propenyl, 1-ethyl-2-propenyl, 1-hexenyl, 2-hexenyl, 3-hexenyl, 4-hexenyl, 5-hexenyl, 1-methyl-1-pentenyl, 2-methyl-1-pentenyl, 3-methyl-1-pentenyl, 4-methyl-1-pentenyl, 1-methyl-2-pentenyl, 2-methyl-2-pen tenyl, 3-methyl-2-pentenyl, 4-methyl-2-pentenyl, 1-methyl-3-pentenyl, 2-methyl-3-pentenyl, 3-methyl-3-pentenyl, 4-methyl-3-pentenyl, 1-methyl-4-pentenyl, 2-methyl-4-pentenyl, 3-methyl-4-pentenyl, 4-methyl-4-pentenyl, 1,1-dimethyl-2-butenyl, 1,1-dimethyl-3 butenyl, 1,2-dimethyl-1-butenyl, 1,2-dimethyl-2-butenyl, 1,2-dimethyl-3-butenyl, 1,3-dimethyl-1-butenyl, 1,3-dimethyl-2- butenyl, 1,3-dimethyl-3-butenyl, 2,2-dimethyl-3-butenyl, 2,3-dimethyl-1-butenyl, 2,3-dimethyl-2-butenyl, 2,3-dimethyl-3- butenyl, 3,3-dimethyl-1-butenyl, 3,3-dimethyl-2-butenyl, 1-ethyl-1-butenyl, 1-ethyl-2-butenyl, 1-ethyl-3-butenyl, 2-ethyl 1-butenyl, 2-ethyl-2-butenyl, 2-ethyl-3-butenyl, 1,1,2-trimethyl-2-propenyl, 1-ethyl-1-methyl-2-propenyl, 1-ethyl-2- methyl-1-propenyl or 1-ethyl-2-methyl-2-propenyl; and C 7 -C 10 alkenyl, such as the isomers of heptenyl, octenyl, nonenyl or decenyl.
  • C 2 -C 20 alkynyl: straight-chain or branched hydrocarbon groups having 2 to 20 carbon atoms and a triple bond in any position, for example C 2 -C 10 -alkynyl or C 11 -C 20 -alkynyl, preferably C 2 -C 10 -alkynyl, such as C 2 -C 4 -alkynyl, such as ethynyl, 1-propynyl, 2-propynyl, 1-butynyl, 2 Butinyl, 3-butynyl, 1-methyl-2-propynyl, or C 5 -C 7 -alkynyl, such as 1-pentynyl, 2-pentynyl, 3-pentynyl, 4-pentynyl, 1-methyl-2-butynyl, 1-methyl-3-butynyl, 2-methyl-3-butynyl, 3-methyl-1-butynyl, 1,1-dimethyl-2-propynyl, 1-ethyl-2-propynyl, 1-hexynyl, 2- Hexynyl, 3-hexynyl, 4-hexynyl, 5-hexynyl, 1-methyl-2-pentynyl, 1-methyl-3-pentynyl, 1-methyl-4-pentynyl, 2-methyl-3-pentynyl, 2-methyl 4-pentynyl, 3-methyl-1-pentynyl, 3-methyl-4-pentynyl, 4-methyl-1-pentynyl, 4-methyl-2-pentynyl, 1,1-dimethyl-2-butynyl, 1,1- Dimethyl-3-butynyl, 1,2-dimethyl-3-butynyl, 2,2-dimethyl-3-butynyl, 3,3-dimethyl-1-butynyl, 1-ethyl-2-butynyl, 1-ethyl-3-yl butinyl, 2-ethyl-3-butynyl or 1-ethyl-1-methyl-2-propynyl and C7-C10 alkynyl such as the isomers of heptynyl, octynyl, nonynyl, decynyl.
  • C 3 -C 15 cycloalkyl: monocyclic, saturated hydrocarbon groups having 3 to 15 carbon ring members, preferably C 3 -C 8 cycloalkyl such as cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl or cyclooctyl and a saturated or unsaturated cyclic system such as. B. norbornyl or norbenyl.
  • Aryl: a mono- to trinuclear aromatic ring system containing 6 to 14 carbon ring members, e.g. As phenyl, naphthyl or anthracenyl, preferably a mono- to binuclear, more preferably a mononuclear aromatic ring system.
  • C 1 -C 20 -alkoxy represents a straight-chain or branched alkyl group having 1 to 20 carbon atoms (as mentioned above) which are bonded via an oxygen atom (-O-), for example C 1 -C 10 -alkoxy or C 11 -C 20 -alkoxy, preferably C 1 -C 10 -alkyloxy, particularly preferably C 1 -C 3 -alkoxy, such as methoxy, ethoxy, propoxy.
  • Aryloxy is a mono- to trinuclear aromatic ring system (as mentioned above) which is attached via an oxygen atom (-O-), preferably a mono- to binuclear, particularly preferably a mononuclear aromatic ring system.
  • Arylalkyl is a mono- to trinuclear aromatic ring system (as mentioned above) which is attached via a C 1 -C 20 -alkylene group, preferably a mononuclear to dinuclear, more preferably a mononuclear aromatic ring system.
  • Hetaryl: heterocyclic substituents which formally derive from aryl groups by replacing one or more methine (-C) and / or vinylene (-CH = CH-) groups with trivalent or divalent heteroatoms. Preferred heteroatoms are oxygen, nitrogen and / or sulfur. Particularly preferably nitrogen and / or oxygen.
  • Heteroatoms are phosphorus, oxygen, nitrogen or sulfur, preferably oxygen, nitrogen or sulfur whose free valencies are optionally saturated by H atoms.

Der für die Erfindung relevante UV-Wellenlängenbereich des elektromagnetischen Spektrums ist von 180 bis 380 nm. Entsprechend sind die sichtbaren und IR-Wellenlängenbereiche des elektromagnetischen Spektrums von 380 bis 780 nm und 780 bis 1800 nm.The relevant for the invention UV wavelength range of the electromagnetic spectrum is from 180 to 380 nm. Accordingly, the visible and IR wavelength ranges of the electromagnetic spectrum of 380 to 780 nm and 780 to 1800 nm.

Erfindugsgemäß weisen die schmalen Banden eine Halbwertsbreite von < (weniger als) 1500 cm-1 auf. Bevorzugt beträgt die Halbwertsbreite einer schmalen Bande < (weniger als) 1200 cm-1, besonders bevorzugt < (weniger als) 1000 cm-1, ganz besonders bevorzugt von 20 bis 1000 cm-1, insbesondere von 20 bis 800 cm-1.In accordance with the invention, the narrow bands have a half width of <(less than) 1500 cm -1 . Preferably, the half width of a narrow band is <(less than) 1200 cm -1 , more preferably <(less than) 1000 cm -1 , most preferably from 20 to 1000 cm -1 , especially from 20 to 800 cm -1 .

Bevorzugt bleibt der Markierstoff nachdem er mit dem zu markierenden Gegenstand in Kontakt gebracht wurde dauerhaft mit dem Gegenstand verbunden. Beispielsweise kann der Markierstoff durch chemische Bindung oder physikalische Kräfte wie beispielsweise durch Adsorption an dem zu markierenden Gegenstand anhaften bzw. mit ihm verbunden sein. Eine dauerhafte Verbindung wird erreicht, indem der Markierstoff durch eine intensive Wechselwirkung mit dem zu markierenden Gegenstand verbunden ist. Diese intensive Wechselwirkung sorgt dafür, dass das Markierungsmittel dauerhaft, d.h. wenigstens für den Zeitraum von einigen Minuten bis einigen Jahren, bevorzugt von einigen Tagen bis 25 Jahren, besonders bevorzugt von einem Jahr bis zu 20 Jahren, insbesondere von einem Jahr bis zu 10 Jahren mit dem Gegenstand verbunden bleibt.Preferably, the marker remains permanently attached to the article after being brought into contact with the article to be marked. For example, the marker may be attached to or bonded to the article to be marked by chemical bonding or physical forces such as adsorption. A permanent connection is achieved by the marker is connected by an intense interaction with the object to be marked. This intense interaction causes the label to be permanently, i. at least for a period of a few minutes to a few years, preferably from a few days to 25 years, more preferably from one year to 20 years, in particular from one year to 10 years remains associated with the object.

Ein Vorteil des erfindungsgemäßen Verfahrens ist es daher, dass die Markierungsmittel nicht nur isoliert, beispielsweise in Lösung, schmale Banden aufweisen, sondern auch nach dem in Kontakt bringen mit dem zu markierenden Gegenstand, beispielsweise nach einem Druckvorgang.An advantage of the method according to the invention is therefore that the marking agents have not only isolated, for example in solution, narrow bands, but also after bringing into contact with the object to be marked, for example after a printing operation.

In einer bevorzugten Ausführungsform des erfindungsgemäßen Verfahrens ist der Markierstoff in Kontakt mit einem Gegenstand, z.B. einem Etikett, wobei dieser Gegenstand selbst dazu dient, einen weiteren Gegenstand zu markieren indem er temporär oder permanent mit dem weiteren Gegenstand, z.B. über einen Klebstoff, verbunden wird.In a preferred embodiment of the method according to the invention, the marker is in contact with an article, e.g. a label, this item itself serving to mark another item by temporarily or permanently attaching it to the other item, e.g. via an adhesive.

In einer weiteren bevorzugten Ausführungsform des erfindungsgemäßen Verfahrens weist mindestens einer der Markierstoffe mindestens zwei schmale Banden mit einer Halbwertbreite von < 1500 cm-1 und diese schmalen Banden befinden sich im UV-und/oder sichtbaren und/oder IR-Wellenlängenbereich des elektromagnetischen Spektrums.In a further preferred embodiment of the method according to the invention, at least one of the markers has at least two narrow bands with a half-value width of <1500 cm -1 and these narrow bands are in the UV and / or visible and / or IR wavelength range of the electromagnetic spectrum.

Bevorzugt befindet sich im Rahmen des erfindungsgemäßen Verfahrens das Absorptionsmaximum mindestens einer schmalen Bande im Wellenlängenbereich von 180 bis 1100 nm befindet, besonders bevorzugt im Wellenlängenbereich von 350 bis 900 nm, ganz besonders bevorzugt von 350 bis 750 nm, insbesondere von 400 bis 750 nm.Within the scope of the process according to the invention, the absorption maximum of at least one narrow band is preferably in the wavelength range from 180 to 1100 nm, particularly preferably in the wavelength range from 350 to 900 nm, very particularly preferably from 350 to 750 nm, in particular from 400 to 750 nm.

In der Regel finden im Rahmen des erfindungsgemäßen Verfahrens Markierstoffe gewählt werden aus organischen Farbstoffen oder Pigmenten Anwendung, wobei diese in Kontakt mit dem zu markierenden Gegenstand schmale Banden aufeisen.As a rule, within the scope of the process according to the invention, markers selected from organic dyes or pigments are used, these being ironic bands in contact with the article to be marked.

Weiterhin kommen aber auch anorganische Chromophore als Markierstoffe in Betracht, beispielsweise Seltenerd- oder Übergangsmetallverbindungen. Hier sind insbesondere die Ionen der seltenen Erden zu nennen mit häufig sehr schmalbandigen Emissionslinien, welche beispielsweise in fluoreszierenden Lampen und in Kathodenstrahlröhren verwendet werden. Beispielhaft seien Y2O3:Eu Komplexe, Mg4GeO5.5F oder (Ce,Tb)MgAl11O19 (siehe Industrial Inorganic Pigments: edited by Gunter Buxbaum and Gerhard Pfaff, WILEY-VCH, S. 274-275 , third, completely revised and extended edition) genannt. Ausserdem sind die schmalbandigen Absorptionslinien der für die spektrale Eichung verwendeten Holmiumoxide Ho2O3 zu nennen, ferner Ho(3+) in LiYF4 oder Nd:YAG Verbindungen.In addition, however, inorganic chromophores are also suitable as markers, for example rare earth or transition metal compounds. In particular, the ions of the rare earths are to be mentioned here with often very narrow-band emission lines, which are used for example in fluorescent lamps and in cathode ray tubes. Examples are Y 2 O 3 : Eu complexes, Mg 4 GeO 5 .5F or (Ce, Tb) MgAl 11 O 19 (see Industrial Inorganic Pigments: edited by Gunter Buxbaum and Gerhard Pfaff, WILEY-VCH, pp. 274-275 , third, completely revised and extended edition). In addition, the narrow band absorption lines of the holmium oxides used for the spectral calibration are Ho 2 O 3 , furthermore Ho (3+) in LiYF 4 or Nd: YAG compounds.

Bevorzugt werden die Markierstoffe gewählt aus metallhaltigen oder metallfreien Phthalocyaninen, bevorzugt Kupfer- Phthalocyaninen, Silizium-Phthalocyaninen, Aluminium-Phthalocyaninen, Zink-Phthalocyaninen, besonders bevorzugt Silizium-Phthalocyaninen, welche mit sterisch anspruchsvollen Substituenten am Siliciumatom oder des Phthalocyaninchromophors versehen sind; Cyaninfarbstoffen, bevorzugt geladenen Cyaninfarbstoffen, besonders bevorzugt Rhodamin-, Oxazin- oder Pseudoisocyaninfarbstoffe; Merocyaninen, bevorzugt elektroneutralen Merocyaninen, besonders bevorzugt Merocyaninen im Cyanlimit; Perylenfarbstoffen; Violanthronen, Isoviolanthronen; Quadratsäurefarbstoffen; Chinonen, Coumarinen, Rhodaminen, oder Porphyrinen.The markers are preferably selected from metal-containing or metal-free phthalocyanines, preferably copper phthalocyanines, silicon phthalocyanines, aluminum phthalocyanines, zinc phthalocyanines, particularly preferably silicon phthalocyanines which are provided with sterically demanding substituents on the silicon atom or the Phthalocyaninchromophors; Cyanine dyes, preferably charged cyanine dyes, more preferably rhodamine, oxazine or pseudoisocyanine dyes; Merocyanines, preferably electroneutral merocyanines, more preferably merocyanines in Cyanlimit; perylene; Violanthrones, Isoviolanthrones; Squaric acid dyes; Quinones, coumarins, rhodamines, or porphyrins.

In bevorzugten Ausführungsformen des erfindungsgemäßen Verfahrens werden als Markierstoffe die folgenden Verbindungen eingesetzt:

Figure imgb0001
mit

R
Aryl, Hetaryl, C1-C20-Alkyl, C2-C20-Alkenyl, C2-C20-Alkinyl, C3-C15-Cycloalkyl, C1-C20-Alkoxy, Aryloxy, Arylalkyl,
R1, R2, R3, R4, R5, R6
unabhängig voneinander, gleich oder verschieden, Aryl, Hetaryl, C1-C20-Alkyl, C2-C20-Alkenyl, C2-C20-Alkinyl, C3-C15-Cycloalkyl, C1-C20-Alkoxy, Aryloxy, Arylalkyl,
oder
Figure imgb0002
 In preferred embodiments of the method according to the invention, the following compounds are used as markers:
Figure imgb0001
 With
R
Aryl, hetaryl, C 1 -C 20 -alkyl, C 2 -C 20 -alkenyl, C 2 -C 20 -alkynyl, C 3 -C 15 -cycloalkyl, C 1 -C 20 -alkoxy, aryloxy, arylalkyl,
R 1 , R 2 , R 3 , R 4 , R 5 , R 6
independently of one another, identical or different, aryl, hetaryl, C 1 -C 20 -alkyl, C 2 -C 20 -alkenyl, C 2 -C 20 -alkynyl, C 3 -C 15 -cycloalkyl, C 1 -C 20 -alkoxy , Aryloxy, arylalkyl,
or
Figure imgb0002

Die Arylreste können in der allgemeinen Form in der para-Position auch Sulfonsäurereste oder Alkalisalze dieser Substituenten (z.B. -SO3H, -SO3Na, -SO3K) enthalten.The aryl radicals in the general form in the para position may also contain sulfonic acid radicals or alkali metal salts of these substituents (eg -SO 3 H, -SO 3 Na, -SO 3 K).

Weitere solche Verbindungen sind:

Figure imgb0003
Figure imgb0004
Figure imgb0005
Figure imgb0006
 mit

M
2 H, Zn, AIR7
R7
C1-C20-Alkyl, C3-C15-Cycloalkyl, Aryl, Hetaryl, N-Heterocyclus,
Figure imgb0007
 Bu: unabhängig voneinander, gleich oder verschieden, n-butyl, isobutyl, bevorzugt gleich,
Figure imgb0008
R8, R9
unabhängig voneinander, gleich oder verschieden, H, Cl, Br, CN, Aryloxy, C1-C20-Alkoxy, N-Heterocyclus
N-Heterocyclus hier bevorzugt Pyrrolidin oder Piperidin. Aryloxy-Reste können in der para-Position Sulfonsäurereste oder Alkalisalze dieser Substituenten (-SO3H, -SO3Na, -SO3K) enthalten.
Figure imgb0009
Figure imgb0010
M1
2 H, Cu, Zn,
R11, R12, R13, R14
H, SO3H, SO3Na, SO3K, SO2NH(CH2)3N(CH3)2
R21, R22, R23
H, C1-C20-Alkyl, C2H5OH,
n
1,2,3,4
X
Cl, Br, BF4, PF6,
Figure imgb0011
Figure imgb0012
R24
C1-C20-Alkyl, Aryl,
Figure imgb0013
 Other such compounds are:
Figure imgb0003
Figure imgb0004
Figure imgb0005
Figure imgb0006
 With
M
2H, Zn, AIR 7
R 7
C 1 -C 20 -alkyl, C 3 -C 15 -cycloalkyl, aryl, hetaryl, N-heterocycle,
Figure imgb0007
 Bu: independently of one another, identical or different, n-butyl, isobutyl, preferably the same,
Figure imgb0008
R 8 , R 9
independently, the same or different, H, Cl, Br, CN, aryloxy, C 1 -C 20 alkoxy, N-heterocycle
N-heterocycle here preferably pyrrolidine or piperidine. Aryloxy radicals may contain in the para position sulfonic acid residues or alkali metal salts of these substituents (-SO 3 H, -SO 3 Na, -SO 3 K).
Figure imgb0009
Figure imgb0010
M 1
2H, Cu, Zn,
R 11 , R 12 , R 13 , R 14
H, SO 3 H, SO 3 Na, SO 3 K, SO 2 NH (CH 2 ) 3 N (CH 3 ) 2
R 21 , R 22 , R 23
H, C 1 -C 20 -alkyl, C 2 H 5 OH,
n
1,2,3,4
X
Cl, Br, BF 4 , PF 6 ,
Figure imgb0011
Figure imgb0012
R 24
C 1 -C 20 -alkyl, aryl,
Figure imgb0013

Beispielhaft seien weiterhin Merocyaninfarbstoffe entspreechend der EP 08168116.5 genannt (Formel IIa S.34 und Formel L2-03 S.37). Insbesondere der Merocyaninfarbstoff:

Figure imgb0014
mit geeignet schmaler Absorptionsbande.By way of example, merocyanine dyes are also suitable EP 08168116.5 (Formula IIa p.34 and Formula L2-03 p.37). In particular, the merocyanine dye:
Figure imgb0014
 with suitably narrow absorption band.

In der Regel kommt im Rahmen des erfindungsgemäßen Verfahrens eine Menge des Markierstoffs zur Anwendung, die mit Hilfe des jeweiligen Verfahrens für einen späteren Nachweis des Vorhandenseins des Markierstoffs noch nachweisbar ist. Diese Menge an Markierstoff kann, beispielsweise abhängig von der Natur des Markierstoffs oder des Nachweisverfahrens über einen weiten Bereich variieren. In der Regel werden von 50 Gew.-% bis zu wenigen ppb, bezogen auf die Gesamtmenge an Markierstoff und zu markierendem Gegenstand, des Markierstoffs mit dem zu markierenden Gegenstand in Kontakt gebracht, bevorzugt von 0,01 bis 10 Gew.-%.As a rule, in the context of the process according to the invention, an amount of the marking substance is used which can still be detected with the aid of the respective method for a later detection of the presence of the marking substance. This amount of label may vary over a wide range, for example, depending on the nature of the label or detection method. As a rule, from 50% by weight up to a few ppb, based on the total amount of marker and article to be marked, of the marker is brought into contact with the article to be marked, preferably from 0.01 to 10% by weight.

Bevorzugt wird im Rahmen des erfindungsgemäßen Verfahrens der zu markierende Gegenstand an mindestens einer Stelle seiner Oberfläche mit mindestens einem Markierstoff in Kontakt gebracht. Die zu markierende Stelle an der Oberfläche ist dabei häufig relativ gering im Verhältnis zur Gesamtoberfläche des Gegenstandes. Bevorzugt beträgt die Fläche der zu markierenden Stelle von einem Quadratmillimeter bis zu einem Quadratzentimeter.In the context of the method according to the invention, the article to be marked is preferably brought into contact with at least one marker at at least one point on its surface. The location to be marked on the surface is often relatively small in relation to the total surface of the article. Preferably, the area of the site to be marked is from one square millimeter to one square centimeter.

Der zu markierende Gegenstand enthält im Rahmen des erfindungsgemäßen Verfahrens bevorzugt Papier, beispielsweise Pappe oder Karton, Metall, Glas, Keramik oder Kunststoff. Besonders bevorzugt enthält der zu markierende Gegenstand dabei von 1 bis 99 Gew.-% Papier, Metall, Glas, Keramik oder Kunststoff, ganz besonders bevorzugt von 10 bis 99 Gew.-%. In einer bevorzugten Ausführungsform besteht der zu markierende Gegenstand im Wesentlichen aus Papier, Metall, Glas, Keramik und/oder Kunststoff. In einer weiteren bevorzugten Ausführungsform basiert der zu markierende Gegenstand auf einem Verbundmaterial, enthaltend beispielsweise Papier oder Karton und Kunststoff. In einer weiteren bevorzugten Ausführungsform basiert der zu markierende Gegenstand auf mehrlagigen Kunststofffolien (Laminat).In the context of the method according to the invention, the article to be marked preferably contains paper, for example cardboard or cardboard, metal, glass, ceramic or plastic. Particularly preferably, the article to be marked contains from 1 to 99 wt .-% paper, metal, glass, ceramic or plastic, most preferably from 10 to 99 wt .-%. In a preferred embodiment, the object to be marked consists essentially of paper, metal, glass, ceramic and / or plastic. In a further preferred embodiment, the article to be marked is based on a composite material containing, for example, paper or cardboard and plastic. In a further preferred embodiment, the object to be marked is based on multilayer plastic films (laminate).

In einer bevorzugten Ausführungsform des erfindungsgemäßen Verfahrens enthält der zu markierende Gegenstand Papier und ist eine Banknote, ein Wertpapier, eine Eintrittskarte, eine Urkunde, eine Verpackung, ein Etikett oder ein Dokument.In a preferred embodiment of the method according to the invention, the object to be marked contains paper and is a banknote, a security, an admission ticket, a document, a packaging, a label or a document.

In einer anderen bevorzugten Ausführungsform des erfindungsgemäßen Verfahrens enthält der zu markierende Gegenstand Kunststoff und ist eine Scheckkarte, eine Folie oder eine Verpackung.In another preferred embodiment of the method according to the invention, the object to be marked contains plastic and is a check card, a foil or a packaging.

In einer weiteren bevorzugten Ausführungsform stellt der zu markierende Gegenstand eine Verpackung für Konsumgüter, insbesondere Arzneimittel, Kosmetika, Reinigungsmittel, Lebensmittel oder Industriegüter, insbesondere Automobilteile dar.In a further preferred embodiment, the object to be marked represents a packaging for consumer goods, in particular pharmaceuticals, cosmetics, cleaning agents, foodstuffs or industrial goods, in particular automobile parts.

Häufig erfolgt das in Kontakt bringen des Markierstoffes mit dem zu markierenden Gegenstand durch ein Aufdrucken des Markierstoffes, oder eines Gemisches, enthaltend den Markierstoff auf den Gegenstand. Bevorzugt werden als Druckverfahren Tintenstrahldruck (Ink-Jet), Siebdruck, Offset-Druck, Flexodruck, Thermodruck, oder (Elektro)photographie eingesetzt. Als Gemische enthaltend den Markierstoff werden beispielsweise Druckfarben oder Tinten eingesetzt. Die Formulierung des Gemisches und/oder das Aufbringen des Markierstoffes oder des Gemisches kann sowohl mit wässrig- oder öl-basierten Druckfarben oder Tinten erfolgen.Frequently, the contacting of the marker with the article to be marked is accomplished by printing the marker or a mixture containing the marker on the article. Inkjet printing (inkjet), screen printing, offset printing, flexographic printing, thermal printing, or (electro) photography are preferably used as printing processes. For example, printing inks or inks are used as mixtures containing the marking substance. The formulation of the mixture and / or the application of the marker or the mixture can be done with either aqueous or oil based inks or inks.

Ein Gegenstand der vorliegenden Erfindung ist ein Verfahren zum Nachweis von Markierungen auf Gegenständen, die, wie oben beschrieben, markiert wurden, welches die folgenden Schritte umfasst:

  1. a. Markierung des Gegenstandes gemäß dem oben beschriebenen Verfahren,
  2. b. Bestrahlung des Gegenstandes mit elektromagnetischer Strahlung umfassend einen Wellenlängenbereich, der mit der mindestens einen schmalen Bande des mindestens einen Markierstoffs zumindest teilweise überlappt,
  3. c. optional, während des Schrittes b. die Durchführung einer Änderung der Lage der mindestens einen schmalen Bande durch einen solvatochromen, elektrochromen, photochromen oder thermochromen Einfluss, und
  4. d. Bestimmung der Absorption des Gegenstandes, umfassend einen Wellenlängenbereich, der mit der mindestens einen schmalen Bande des mindestens einen Markierstoffs zumindest teilweise überlappt.
An object of the present invention is a method for detecting markings on articles which have been marked as described above, comprising the following steps:
  1. a. Marking the article according to the method described above,
  2. b. Irradiating the article with electromagnetic radiation comprising a wavelength range that at least partially overlaps with the at least one narrow band of the at least one marker,
  3. c. optionally, during step b. carrying out a change in the position of the at least one narrow band by a solvatochromic, electrochromic, photochromic or thermochromic influence, and
  4. d. Determining the absorption of the article, comprising a wavelength range that at least partially overlaps with the at least one narrow band of the at least one marker.

In einer bevorzugten Ausführungsform des erfindungsgemäßen Verfahrens zum Nachweis von Markierungen auf Gegenständen wird (Schritt c.) während des Schrittes b. eine Änderung der Lage der mindestens einen schmalen Bande durch einen solvatochromen, elektrochromen, oder thermochromen Einfluss vorgenommen. Bevorzugt wird die Änderung der Lage der schmalen Bande durch das Einwirken von Elektro- und Thermochromie vorgenommen. Ein solvatochromer Einfluss auf die spektrale Lage der schmalen Bande lässt sich beispielsweise durch eine Änderung des Lösungsmittels bewirken. Ein elektrochromer Einfluss ergibt sich durch das Anlegen und die Änderung eines elektrischen Feldes und ein thermochromer Einfluss resultiert aus der Änderung der Temperatur. Ein photochromer Einfluss ergibt sich durch das Einstrahlen von elektromagnetischer Strahlung.In a preferred embodiment of the method according to the invention for detecting markings on objects (step c.) During step b. a change in the position of the at least one narrow band made by a solvatochromic, electrochromic, or thermochromic influence. Preferably, the change in the position of the narrow band by the action of electric and Thermochromism made. A solvatochromic influence on the spectral position of the narrow band can be brought about, for example, by a change in the solvent. Electrochromic influence results from the application and the change of an electric field and a thermochromic influence results from the change of the temperature. A photochromic influence results from the irradiation of electromagnetic radiation.

Die Änderung der spektralen Lage ist bevorzugt wiederkehrend und wird mit einer bestimmten Frequenz moduliert. Die Modulationsfrequenz beträgt hierbei bevorzugt von 0,1 bis 10 Hz, insbesondere von 0,1 bis 5 Hz.The change of the spectral position is preferably recurring and is modulated with a certain frequency. The modulation frequency is in this case preferably from 0.1 to 10 Hz, in particular from 0.1 to 5 Hz.

Bevorzugt wird die Bestrahlung des Gegenstandes mit elektromagnetischer Strahlung (Schritt b.) mit Hilfe einer schmalbandingen Strahlungsquelle durchgeführt. Als schmalbandige Strahlungsquellen werden Laser wie Farbstofflaser, Festkörperlaser oder Laserdioden eingesetzt. Die schmalbandige Strahlungsquelle weist für die von ihr ausgehende Strahlung bevorzugt eine Halbwertsbreite von 0,01 bis 10 nm auf, besonders bevorzugt von 0,1 bis 5 nm, insbesondere bevorzugt von 0,1 bis 2 nm.The irradiation of the object with electromagnetic radiation (step b.) Is preferably carried out with the aid of a narrow-band radiation source. As narrow-band radiation sources, lasers such as dye lasers, solid-state lasers or laser diodes are used. The narrow-band radiation source preferably has a half-width of 0.01 to 10 nm for the radiation emitted by it, particularly preferably from 0.1 to 5 nm, particularly preferably from 0.1 to 2 nm.

Die Bestrahlung wird mit Hilfe von mindestens zwei schmalbandigen Strahlungsquellen durchgeführt.The irradiation is carried out with the help of at least two narrow-band radiation sources.

In einer besonders bevorzugten Ausführungsform des erfindungsgemäßen Verfahrens zum Nachweis von Markierungen auf Gegenständen weist mindestens einer der Markierstoffe (Schritt a.) mindestens zwei schmale Banden mit einer Halbwertsbreite von 20 cm-1 bis 800 cm-1 auf und diese schmalen Banden befinden sich im UV- und/oder sichtbaren und/oder IR-Wellenlängenbereich des elektromagnetischen Spektrums und die Bestrahlung (Schritt b.) wird mit Hilfe von mindestens zwei schmalbandigen Strahlungsquellen durchgeführt.In a particularly preferred embodiment of the method according to the invention for the detection of marks on articles, at least one of the markers (step a.) Has at least two narrow bands with a half width of 20 cm -1 to 800 cm -1 and these narrow bands are in the UV - and / or visible and / or IR wavelength range of the electromagnetic spectrum and the irradiation (step b.) Is performed by means of at least two narrow-band radiation sources.

In einer weiteren bevorzugten Ausführungsform des erfindungsgemäßen Verfahrens zum Nachweis von Markierungen auf Gegenständen wird die Bestimmung der Absorption (Schritt d.) visuell durchgeführt.In a further preferred embodiment of the method according to the invention for detecting markings on objects, the determination of the absorption (step d.) Is carried out visually.

In einer besonders bevorzugten Ausführungsform des erfindungsgemäßen Verfahrens zum Nachweis von Markierungen auf Gegenständen weist mindestens einer der Markierstoffe (Schritt a.) mindestens zwei schmale Banden mit einer Halbwertbreite von 0,5 nm bis 10 nm auf und diese schmalen Banden befinden sich im UV- und/oder sichtbaren und/oder IR-Wellenlängenbereich des elektromagnetischen Spektrums und die Bestrahlung (Schritt b.) wird mit Hilfe von mindestens zwei schmalbandigen Lichtquellen durchgeführt und die Bestimmung der Absorption (Schritt d.) wird visuell durchgeführt. Bevorzugt werden zur Verbesserung der visuellen Wahrnehmung zwei Lichtquellen gegenphasig moduliert (visuelles Lock-In Verfahren). Hierbei werden die Intensitäten der beiden Lichtstrahlen so abgeglichen, dass unmarkierte (Bereiche der) Gegenstände dem visuellen System sehr ähnliche oder im Wesentlichen die gleichen Helligkeiten anbieten. Demgegenüber beobachtet der Betrachter visuell in markierten Bereichen ein Oszillieren mit der Modulationsfrequenz der Lichtquellen, die Modulationsfrequenz beträgt hierbei bevorzugt von 0,1 bis 10 Hz, insbesondere von 0,1 bis 5 Hz.In a particularly preferred embodiment of the method according to the invention for detecting markings on articles, at least one of the markers (step a.) Has at least two narrow bands with a half-width of 0.5 nm to 10 nm, and these narrow bands are in the UV and / or visible and / or IR wavelength range of the electromagnetic spectrum and the irradiation (step b.) Is performed by means of at least two narrow-band light sources and the determination of the absorption (step d.) Is carried out visually. To improve the visual perception, two light sources are preferably modulated in antiphase (visual lock-in method). Here are the Intensities of the two light beams adjusted so that unlabeled (areas of) objects offer the visual system very similar or substantially the same brightness. In contrast, the viewer observes visually in marked areas an oscillation with the modulation frequency of the light sources, the modulation frequency is in this case preferably from 0.1 to 10 Hz, in particular from 0.1 to 5 Hz.

Ein Vorteil dieses Verfahrens ist es, dass das visuelle System des Menschen in diesem Frequenzbereich der Modulation sehr empfindlich reagiert. Damit werden durch das visuelle Lock-In-Verfahren mögliche Störungen effizient unterdrückt und der Markierungseffekt tritt deutliche hervor.An advantage of this method is that the human visual system is very sensitive to modulation in this frequency range. Thus, the visual lock-in method effectively suppresses possible disturbances and the marking effect is evident.

In einer weiteren bevorzugten Ausführungsform des erfindungsgemäßen Verfahrens zum Nachweis von Markierungen auf Gegenständen wird die Bestimmung der Absorption (Schritt d.) durch die Messung eines Absorptionsspektrums mit Hilfe eines Spektrometers durchgeführt.In a further preferred embodiment of the method according to the invention for detecting markings on objects, the determination of the absorption (step d.) Is carried out by measuring an absorption spectrum with the aid of a spectrometer.

Nach einer besonders bevorzugten Ausführungsform des erfindungsgemäßen Verfahrens zum Nachweis von Markierungen auf Gegenständen weist mindestens einer der Markierstoffe (Schritt a.) mindestens zwei schmale Banden mit einer Halbwertbreite von 20 cm-1 bis 800 cm-1 auf und diese schmalen Banden befinden sich im UV-und/oder sichtbaren und/oder IR-Wellenlängenbereich des elektromagnetischen Spektrums und die Bestrahlung (Schritt b.) wird mit Hilfe von mindestens zwei schmalbandigen Lichtquellen durchgeführt und die Bestimmung der Absorption (Schritt d.) wird durch die Messung eines Absorptionsspektrums mit Hilfe eines Spektrometers durchgeführt. Bevorzugt werden zur Verbesserung des Nachweises zwei Lichtquellen gegenphasig moduliert (elektronisches Lock-In Verfahren). Hierbei werden die Intensitäten der beiden Lichtstrahlen so abgeglichen, dass unmarkierte (Bereiche der) Gegenstände dem Spektrometer sehr ähnliche oder im Wesentlichen die gleichen Intensitäten anbieten. Demgegenüber stellt das Spektrometer als Nachweis- oder Detektionsapparatur in markierten Bereichen ein Oszillieren mit der Modulationsfrequenz der Lichtquellen fest. Die Modulationsfrequenz beträgt hierbei bevorzugt von 0,1 bis 10 Hz, insbesondere von 0,1 bis 5 Hz.According to a particularly preferred embodiment of the method according to the invention for detecting markings on articles, at least one of the markers (step a.) Has at least two narrow bands with a half-value width of 20 cm -1 to 800 cm -1 and these narrow bands are in the UV and / or visible and / or IR wavelength range of the electromagnetic spectrum and the irradiation (step b.) Is performed by means of at least two narrow-band light sources and the determination of the absorption (step d.) Is by measuring an absorption spectrum using a Spectrometer performed. To improve the detection, two light sources are preferably modulated in antiphase (electronic lock-in method). In this case, the intensities of the two light beams are adjusted so that unmarked (areas of) objects offer the spectrometer very similar or substantially the same intensities. In contrast, the spectrometer as detection or detection apparatus in marked areas determines an oscillation with the modulation frequency of the light sources. The modulation frequency is in this case preferably from 0.1 to 10 Hz, in particular from 0.1 to 5 Hz.

Ein weiterer Gegenstand der vorliegenden Erfindung ist ein Verfahren zur Authentifizierung eines Gegenstandes, umfassend die folgenden Schritte:

  1. a. Nachweis der Markierung gemäß dem erfindungsgemäßen Verfahren,
  2. b. Vergleich der Absorption oder des Absorptionsspektrums mit einer entsprechenden Absorption oder eines Absorptionsspektrums eines authentischen Gegenstandes.
A further subject of the present invention is a method for authenticating an article, comprising the following steps:
  1. a. Detection of the marking according to the method of the invention,
  2. b. Comparison of the absorption or absorption spectrum with a corresponding absorption or absorption spectrum of an authentic article.

Bevorzugt werden zum Vergleich der Absorption oder des Absorptionsspektrums (Schritt b.) von der Absorption oder dem Absorptionsspektrum abgeleitete Größen verwendet. Beispielsweise handelt es sich bei diesen Größen um Intensitäten oder Lage von Absorptionsmaxima.Preferably, quantities derived from the absorption or the absorption spectrum are used to compare the absorption or the absorption spectrum (step b.). For example, these quantities are intensities or positions of absorption maxima.

Bevorzugt wird der Vergleich (Schritt b.) mit Hilfe eines Computers durchgeführt, der Zugriff auf gespeicherte Daten zur Absorption, zum Absorptionsspektrum oder davon abgeleiteten Größen des authentischen Gegenstandes hat.Preferably, the comparison (step b.) Is performed by means of a computer having access to stored data for absorption, absorption spectrum or derived quantities of the authentic object.

Das erfindungsgemäße Verfahren kann auch unter Verwendung von Fluoreszenzmessungen durchgeführt werden, wobei entsprechend Markierstoffe mit schmalen Fluoreszenzsignalen verwendet werden. Diese Markierstoffe werden bevorzugt aus der Gruppe der oben bereits genannten Markierstoffe gewählt.The method according to the invention can also be carried out using fluorescence measurements, using appropriately markers with narrow fluorescence signals. These markers are preferably selected from the group of the above-mentioned markers.

In einer bevorzugten Ausführungsform des Verfahrens zur Authentifizierung eines Gegenstandes wird die Authentifizierung mit Hilfe eines Fahrkarten-, Eintrittskarten-, oder Bankautomaten durchgeführt. Besonders bevorzugt wird die Authentifizierung mit Hilfe eines tragbaren Gerätes durchgeführt.In a preferred embodiment of the method for authenticating an object, the authentication is carried out with the aid of a ticket, ticket or cash machine. Particularly preferably, the authentication is performed by means of a portable device.

Das erfindungsgemäße Verfahren zur Authentifizierung eines Gegenstandes findet Verwendung bei der Authentifizierung von Konsumgütern oder Industriegütern, insbesondere Wertpapieren, Dokumenten, Verpackungen.The inventive method for authenticating an article is used in the authentication of consumer goods or industrial goods, in particular securities, documents, packaging.

Gegenstände, werden mit Hilfe des erfindungsgemäßen Verfahrens markiert.Articles are marked using the method according to the invention.

Häufig lassen sich die erfindungsgemäßen Verfahren zur Markierung zum Nachweis und zur Authentifizierung mit Hilfe von Geräten durchführen, die dem Fachmann aus dem Stand der Technik bekannt und somit einfach umsetzbar sind. Die Verbindung von schmalbandigen Absorptionsbanden, schmalbandigen Strahlungsquellen sowie der Modulation der Strahlungsquelle oder der Bandenlage bieten einen erhöhten Sicherheitsstandard der Markierung gegenüber bekannten Markierungen von Gegenständen.Frequently, the methods according to the invention for marking for detection and authentication can be carried out with the aid of devices which are known to the person skilled in the art from the prior art and thus can be easily implemented. The combination of narrow band absorption bands, narrow band radiation sources, and the modulation of the radiation source or banding provide an increased safety standard of the tag over known tagging of articles.

Die Erfindung wird durch die Beispiele näher erläutert ohne dass die Beispiele den Gegenstand der Erfindung einschränken.The invention is explained in more detail by the examples without the examples restricting the subject matter of the invention.

Beispiele:Examples: Herstellung Druckfarbe enthaltend Markierstoff:Preparation of Printing Ink Containing Marker:

Als Basis für die Herstellung der Markierdruckfarbe diente der Klar-Lack (matt) der Fa. Horstmann-Steinberg (ACRYLAC® Matt 57 0080/40; Dispersionslack auf wässriger Basis). In diesen Lack wurden 0,01 Gew.-% des Markierstoffes bei Raumtemperatur (21 °C) eingerührt bis eine homogene Verteilung des Markierstoffes erreicht war.The basis for the production of the marking ink was the clear lacquer (matt) from Horstmann-Steinberg (ACRYLAC® Matt 57 0080/40, water-based dispersion lacquer). In this paint 0.01 wt .-% of the marker at room temperature (21 ° C) were stirred until a homogeneous distribution of the marker was reached.

Als Markierstoff wurde eine Mischung von Siliciumphthalocanininen verwendet:

Figure imgb0015
The marker used was a mixture of silicon phthalocaninines:
Figure imgb0015

Die Verbindungen wurden in einer 1:2:1 (A:B:C) Mischung eingesetzt. Dieser Markierstoff zeigt in der Markierdruckfarbe vor und nach dem Druckvorgang eine scharfe Absorption bei 666 nm. In der Lösung (Essigsäureethylester) zeigt die Mischung bei 666 nm eine Halbwertsbreite von 265 cm-1 und nach dem Druckvorgang eine Halbwertsbreite von 610 cm-1.The compounds were used in a 1: 2: 1 (A: B: C) mixture. This marker shows in the marking ink before and after printing a sharp absorption at 666 nm. In the solution (ethyl acetate) shows the mixture at 666 nm a half-width of 265 cm -1 and after printing a half-width of 610 cm -1 .

Aufbringen der Markierung: DruckvorgangApplication of the marking: Printing process

Der Druckvorgang wurde mit einer Druckmaschine der Fa. Heidelberger-Druckmaschinen vom Typ GOT 52 Zweifarben durchgeführt (Offsetdruck).The printing process was carried out with a printing machine from Heidelberger Druckmaschinen type GOT 52 two-color (offset printing).

Bedruckt wurde sowohl einfaches Schreibmaschinenpapier (SM-Papier, DIN 6730), als auch gestrichenes SM-Papier.Both plain typewriter paper (SM paper, DIN 6730) and coated SM paper were printed on.

Beispiel 1:Example 1:

Entsprechend einer gewählten Druckvorlage (Markierungsmuster) wurde eine Markierung (durch den Druckvorgang) auf weißem SM-Papier aufgebracht. Die Konzentration des oben genannten Markierstoffes in der Druckfarbe wurde dabei soweit reduziert, dass die Markierung bei Beleuchtung mit Tages- oder weißem Kunstlicht dicht unter der Sichtbarkeitsgrenze lag, also mit bloßem Auge nicht zu erkennen war.According to a selected artwork (mark pattern), a mark (by printing) was applied on white SM paper. The concentration The above-mentioned marking substance in the printing ink was reduced to such an extent that, when illuminated with daylight or white artificial light, the marking was located just below the limit of visibility, ie could not be seen with the naked eye.

Zur weiteren Maskierung des Markierungsmusters wurde das markierte weiße Papier mit einem Farbbild überdruckt (Demonstartionsobjekt). Dies geschah mit einem kommerziellen Inkjet-Drucker.To further mask the marking pattern, the marked white paper was overprinted with a color image (demo object). This happened with a commercial inkjet printer.

Wurde dieses Demonstrationsobjekt mit rotem Licht beleuchtet konnte das Markierungsmuster mit bloßem Auge wahrgenommen werden.If this demonstration object was illuminated with red light, the marking pattern could be perceived with the naked eye.

Die Wahrnehmung des Markierungsmusters war, insbesondere bei heller Hintergrundbeleuchtung möglich aber nur schwach ausgeprägt.The perception of the marking pattern was possible, but only weakly, especially with bright backlighting.

Um den visuellen Effekt der Wahrnehmung des Markierungsmusters zu verstärken wurde eine spezielle Beleuchtungseinrichtung verwendet.In order to enhance the visual effect of the perception of the marking pattern, a special lighting device was used.

Diese Beleuchtungseinrichtung enthält zwei Lichtquellen mit unterschiedlicher Wellenlänge. Verwendet wurden zwei Laserdioden mit Wellenlängen von 666 nm (Absorptionsmaximum des Markierstoffes) bzw. 650 nm (wird vom Markierstoff wegen der schmalen Absorptionsbande nur schwach absorbiert). Diese Beleuchtungseinrichtung wurde als Lichtquelle in Form eines Lichtstiftes umgesetzt, mit dem die Markierung für die Wahrnehmung mit dem menschlichen Auge kontinuierlich beleuchtet werden kann.This illumination device contains two light sources with different wavelengths. Two laser diodes with wavelengths of 666 nm (absorption maximum of the marker) and 650 nm were used (only weakly absorbed by the marker because of the narrow absorption band). This lighting device has been implemented as a light source in the form of a light pen, with which the mark for the perception can be continuously illuminated with the human eye.

Beide obengenannten Wellenlängen wurden abwechselnd im Ein-Hz-Rhythmus moduliert. Für das menschliche Auge erschienen beide Wellenlängen in der gleichen Farbe.Both of the above-mentioned wavelengths were alternately modulated in one-Hz rhythm. For the human eye both wavelengths appeared in the same color.

Die Intensität beider Laserstrahlen war hierbei so abgeglichen worden, dass sie auf weißem Hintergrund für das menschliche Auge gleich hell waren. Daher nahm das Auge die Modulation auf weißem Hintergrund nicht war.The intensity of both laser beams was adjusted so that they were equally bright on a white background to the human eye. Therefore, the eye took the modulation on a white background was not.

Beleuchtete man mit dieser Lichtquelle jedoch das aufgedruckte Markierungsmuster, so blinkte dieses im Ein-Hz-Rhythmus auf. Dieser Effekt ist wahrscheinlich darauf zurückzuführen, dass zwischen einer Wellenlänge bei der der Markierstoff absorbiert und einer Wellenlänge bei der keine Absorption vorliegt hin und her geschaltet wird. Dieses Verfahren kann daher als visuelles Lock-In Verfahren bezeichnet werden. Es führt zu einer drastischen verbesserten Widererkennung des Markierungsmusters. Es hat darüber hinaus den Vorteil, dass es die Aufmerksamkeit des Beobachters auf das Markierungsmuster lenkt.If, however, the printed marking pattern was illuminated with this light source, this flashed in a one-Hz rhythm. This effect is probably due to switching between a wavelength at which the marker absorbs and a wavelength at which there is no absorption. This method can therefore be called a visual lock-in method. It leads to a drastic improved recognition of the marking pattern. It also has the advantage of drawing the observer's attention to the marking pattern.

Beispiel 2:Example 2:

Beispiel 1 lässt sich analog für den Fall durchführen, dass die Detektion des Markirungsmusters nicht mit dem menschlichen Auge, sondern mit einem Spektrometer erfolgt, dass zur Erfassung der Modulation eines Absorptions- oder Fluoreszenzsignals eingesetzt wird.Example 1 can be carried out analogously for the case that the detection of the marker pattern is not carried out with the human eye, but with a spectrometer that is used to detect the modulation of an absorption or fluorescence signal.

Claims (15)

  1. A process for detecting markings on articles, comprising the following steps:
    a. marking the article, by contacting the article to be marked with at least one marker, the absorption spectrum of the at least one marker in contact with the article having at least one narrow band with a halfheight width of < 1500 cm-1 and the at least one narrow band being in the UV and/or visible and/or IR wavelength region of the electromagnetic spectrum,
    b. irradiating the article with electromagnetic radiation comprising a wavelength range which at least partly overlaps with the at least one narrow band of the at least one marker,
    c. optionally, during step b., conducting a change in the position of the at least one narrow band by a solvatochromic, electrochromic, photochromic or thermochromic effect, and
    d. determining the absorption of the article comprising a wavelength range which at least partly overlaps with the at least one narrow band of the at least one marker,
    wherein
    the irradiation of the article with electromagnetic radiation is performed with the aid of at least two narrow-band radiation sources, switching back and forth between a wavelength at which the marker absorbs and a wavelength at which there is no absorption.
  2. The process according to claim 1, wherein step c. is performed.
  3. The process according to claims 1 and 2, wherein the determination of the absorption is performed visually.
  4. The process according to claims 1 and 2, wherein the determination of the absorption is performed by measuring the absorption spectrum with the aid of a spectrometer.
  5. The process according to claims 1 to 4, wherein the markers are selected from organic dyes, inorganic chromophores and pigments.
  6. The process according to claims 1 to 5, wherein the markers are selected from metal-containing or metal-free phthalocyanines; cyanine dyes; merocyanines; perylene dyes; violanthrones, isoviolanthrones; squaric acid dyes; quinones, coumarins, rhodamines, porphyrins and rare earth or transition metal compounds.
  7. The process according to claims 1 to 6, wherein the article to be marked is contacted with at least one marker at at least one site on its surface.
  8. The process according to claims 1 to 7, wherein the article to be marked comprises paper, metal, glass, ceramic or plastic.
  9. The process according to claim 8, wherein the article to be marked comprises paper and is a bank note, security, entrance ticket, certificate, wrapper, label or document.
  10. The process according to claim 8, wherein the article to be marked comprises plastic and is a check card, film or wrapper.
  11. The process according to claim 9 or 10, wherein the article to be marked is a wrapper for consumer goods or industrial goods.
  12. The process according to claims 1 to 11, wherein the contacting is effected by print application of the marker or of a mixture comprising the marker to the article.
  13. A process for authenticating an article, comprising the following steps:
    a. detecting the marking according to claims 1 to 12,
    b. comparing the absorption or the absorption spectrum with a corresponding absorption or absorption spectrum of an authentic article.
  14. The process according to claim 13, wherein the authentication is performed with the aid of a travel ticket machine, entrance ticket machine or ATM.
  15. The use of the process according to claims 13 and 14 for authentication of consumer goods or industrial goods.
EP10768457.3A 2009-10-16 2010-10-12 Use of marking agents having narrow bands Revoked EP2488368B1 (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
EP10768457.3A EP2488368B1 (en) 2009-10-16 2010-10-12 Use of marking agents having narrow bands

Applications Claiming Priority (3)

Application Number Priority Date Filing Date Title
EP09173310 2009-10-16
PCT/EP2010/065234 WO2011045294A1 (en) 2009-10-16 2010-10-12 Marking agents having narrow bands
EP10768457.3A EP2488368B1 (en) 2009-10-16 2010-10-12 Use of marking agents having narrow bands

Publications (2)

Publication Number Publication Date
EP2488368A1 EP2488368A1 (en) 2012-08-22
EP2488368B1 true EP2488368B1 (en) 2014-05-14

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EP10768457.3A Revoked EP2488368B1 (en) 2009-10-16 2010-10-12 Use of marking agents having narrow bands

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US (1) US8610893B2 (en)
EP (1) EP2488368B1 (en)
JP (1) JP2013507276A (en)
CN (1) CN102574405B (en)
WO (1) WO2011045294A1 (en)

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US9087991B2 (en) 2011-02-01 2015-07-21 Basf Se Photovoltaic element
CN103874742B (en) 2011-08-12 2016-08-17 巴斯夫欧洲公司 Carbazole carbazole-two (two carbimides) and they are as the purposes of semiconductor
AT16766U1 (en) * 2018-12-06 2020-08-15 Engel Austria Gmbh Marking and detection processes for thermoplastic semi-finished products

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EP0340898B1 (en) 1988-04-05 1996-09-04 Zeneca Limited Security coding
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TW280893B (en) * 1994-05-06 1996-07-11 Kansai Paint Co Ltd
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EP1041436A1 (en) 1999-04-01 2000-10-04 Bayer Ag Substrates protected against unauthorised copying and method for their manufacture
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Publication number Publication date
CN102574405A (en) 2012-07-11
US20120194801A1 (en) 2012-08-02
WO2011045294A1 (en) 2011-04-21
US8610893B2 (en) 2013-12-17
JP2013507276A (en) 2013-03-04
CN102574405B (en) 2014-11-05
EP2488368A1 (en) 2012-08-22

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