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

Description

The present invention relates to methods for detecting marks on articles. Another object of the invention are methods for authenticating objects.

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 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 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 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 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.

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.

An object of the present invention was thus to provide such methods which are easy to apply with higher security against counterfeiting.

This object has been achieved by a method according to claim 1.

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.

• 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.

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.

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 .

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.

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 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 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.

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.

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.

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.

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.

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

In preferred embodiments of the method according to the invention, the following compounds are used as markers:

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

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).

mit

M

2 H, Zn, AIR⁷

R⁷

C₁-C₂₀-Alkyl, C₃-C₁₅-Cycloalkyl, Aryl, Hetaryl, N-Heterocyclus,

Bu: unabhängig voneinander, gleich oder verschieden, n-butyl, isobutyl, bevorzugt gleich,

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.

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,

R²⁴

C₁-C₂₀-Alkyl, Aryl,

Other such compounds are:

With

M

2H, Zn, AIR ⁷

R ⁷

C ₁ -C ₂₀ -alkyl, C ₃ -C ₁₅ -cycloalkyl, aryl, hetaryl, N-heterocycle,

Bu: independently of one another, identical or different, n-butyl, isobutyl, preferably the same,

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).

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 ,

R ²⁴

C ₁ -C ₂₀ -alkyl, aryl,

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:

with suitably narrow absorption band.

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.

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.

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 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 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 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.

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.

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 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.

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 (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.

The irradiation is carried out with the help of at least two narrow-band radiation sources.

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 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 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.

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 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.

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.

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.

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.

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.

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 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.

The inventive method for authenticating an article is used in the authentication of consumer goods or industrial goods, in particular securities, documents, packaging.

Articles are marked using the method according to the invention.

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.

The invention is explained in more detail by the examples without the examples restricting the subject matter of the invention.

Examples: Preparation of Printing Ink Containing Marker:

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.

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. 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 .

Application of the marking: Printing process

The printing process was carried out with a printing machine from Heidelberger Druckmaschinen type GOT 52 two-color (offset printing).

Both plain typewriter paper (SM paper, DIN 6730) and coated SM paper were printed on.

Example 1:

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.

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.

If this demonstration object was illuminated with red light, the marking pattern could be perceived with the naked eye.

The perception of the marking pattern was possible, but only weakly, especially with bright backlighting.

In order to enhance the visual effect of the perception of the marking pattern, a special lighting device was used.

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.

Both of the above-mentioned wavelengths were alternately modulated in one-Hz rhythm. For the human eye both wavelengths appeared in the same color.

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.

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.

Example 2:

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.