WO2008004015A2 - Compositions anti-stokes de fluorescence blanche et procédés - Google Patents

Compositions anti-stokes de fluorescence blanche et procédés Download PDF

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Publication number
WO2008004015A2
WO2008004015A2 PCT/IB2006/001640 IB2006001640W WO2008004015A2 WO 2008004015 A2 WO2008004015 A2 WO 2008004015A2 IB 2006001640 W IB2006001640 W IB 2006001640W WO 2008004015 A2 WO2008004015 A2 WO 2008004015A2
Authority
WO
WIPO (PCT)
Prior art keywords
fluorescence
safety mark
article
stokes
substantially white
Prior art date
Application number
PCT/IB2006/001640
Other languages
English (en)
Inventor
Petrik Viktor Ivanovich
Original Assignee
Petrik Viktor Ivanovich
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Petrik Viktor Ivanovich filed Critical Petrik Viktor Ivanovich
Priority to PCT/IB2006/001640 priority Critical patent/WO2008004015A2/fr
Publication of WO2008004015A2 publication Critical patent/WO2008004015A2/fr

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Classifications

    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B42—BOOKBINDING; ALBUMS; FILES; SPECIAL PRINTED MATTER
    • B42D—BOOKS; BOOK COVERS; LOOSE LEAVES; PRINTED MATTER CHARACTERISED BY IDENTIFICATION OR SECURITY FEATURES; PRINTED MATTER OF SPECIAL FORMAT OR STYLE NOT OTHERWISE PROVIDED FOR; DEVICES FOR USE THEREWITH AND NOT OTHERWISE PROVIDED FOR; MOVABLE-STRIP WRITING OR READING APPARATUS
    • B42D25/00—Information-bearing cards or sheet-like structures characterised by identification or security features; Manufacture thereof
    • B42D25/20—Information-bearing cards or sheet-like structures characterised by identification or security features; Manufacture thereof characterised by a particular use or purpose
    • B42D25/29—Securities; Bank notes
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B42—BOOKBINDING; ALBUMS; FILES; SPECIAL PRINTED MATTER
    • B42D—BOOKS; BOOK COVERS; LOOSE LEAVES; PRINTED MATTER CHARACTERISED BY IDENTIFICATION OR SECURITY FEATURES; PRINTED MATTER OF SPECIAL FORMAT OR STYLE NOT OTHERWISE PROVIDED FOR; DEVICES FOR USE THEREWITH AND NOT OTHERWISE PROVIDED FOR; MOVABLE-STRIP WRITING OR READING APPARATUS
    • B42D25/00—Information-bearing cards or sheet-like structures characterised by identification or security features; Manufacture thereof
    • B42D25/30—Identification or security features, e.g. for preventing forgery
    • B42D25/36—Identification or security features, e.g. for preventing forgery comprising special materials
    • B42D25/378—Special inks
    • B42D25/387—Special inks absorbing or reflecting ultraviolet light

Definitions

  • the field of the invention is compositions and methods for anti-stokes (up-converting) fluorescent materials, and especially as they relate to authentication of documents and labels marked with such materials.
  • Anti-stokes fluorescence is a well known effect of certain materials in which incident light of a lower wavelength is absorbed by a material and then emitted after up-conversion as fluorescence light of a shorter wavelength.
  • especially useful anti-stokes materials include those in which an inorganic matrix (e.g., oxides, fluorides, oxysulfides, oxychlorides, etc.) include Yttrium as a matrix component to thereby form a rare earth metal-containing inorganic matrix (e.g., Y 2 O 3 -YOF, YF 3 , Y 2 O 2 S, YOCl, etc.), which in almost all cases further includes a sensitizer and an activator.
  • an inorganic matrix e.g., oxides, fluorides, oxysulfides, oxychlorides, etc.
  • Yttrium e.g., Y 2 O 3 -YOF, YF 3 , Y 2 O 2 S
  • the rare earth metal in the matrix i.e., the rare earth metal matrix component
  • the sensitizer is most typically a single type of rare earth metal (e.g., ytterbium or erbium)
  • the activator is another single type of rare earth metal (e.g., erbium or thulium).
  • the color of the anti- stokes fluorescence will depend on the particular choice of the activator.
  • Y 2 O 2 SiYb, Er Y as rare earth metal matrix component, Yb as sensitizer, and Er as activator, both present in the crystal lattice at low concentration
  • Y 2 O 2 S: Yb, Tm Y as rare earth metal matrix component, Yb as sensitizer, and Tm as activator, both present in the crystal lattice at low concentration
  • the presently known anti-stoked materials have the general formula A n O 2 S:X m Y q with A, X, and Y being rare earth metals, n being 1 or 2, and m and q being independently between O and 1.
  • fluorescence emission is limited to a single color (e.g., blue or red).
  • the spectral footprint can be relatively easily repeated once the chemical composition is known (e.g., using energy dispersive electron microscopy), thus severely limiting the usefulness for security related applications.
  • compositions and methods for anti-stokes materials are known in the art, all or almost all of them suffer from one or more problems. Thus, there is still a need for new compositions and methods for such materials, and especially for those having substantially white fluorescence.
  • the present invention is directed to compositions and methods related to materials having substantially white anti-stokes fluorescence. Such materials are most preferably employed in safety marks to authenticate an article (e.g., security document, identification card, bank note, excise label, etc.), but other uses are also contemplated.
  • materials having substantially white anti-stokes fluorescence are most preferably employed in safety marks to authenticate an article (e.g., security document, identification card, bank note, excise label, etc.), but other uses are also contemplated.
  • a safety mark comprises a material having substantially white anti-stokes fluorescence.
  • contemplated materials will have a formula OfE n O 2 S : G ml , J m2 , L 1113 , Q m4 , X m5 , Y m6 , wherein E is Y, La, or Yb, and G is Er or Yb, J, L, Q, X, and Y are independently cerium, erbium, europium, dysprosium, gadolinium, lutetium, lanthanum, praseodymium, promethium, terbium, or thulium, n is 1 or 2, ml is between 1 and 25 mass %, and m2, m3, m4, m5, and m6 are independently between 0 and 1 mass %.
  • suitable materials include those in which E is Y, and G is Yb, and/or those in which J, L, Q, X, and Y are independently erbium, europium, dysprosium, gadolinium, and thulium.
  • the material is disposed in a paper, a fabric, a dye, a natural or synthetic polymer, a metal, a metal alloy, and/or cellular structure. It is especially pointed out that a spectral footprint of the substantially white anti-stokes fluorescence from a first batch is irreproducible in a second batch of the same material.
  • contemplated that the substantially white anti-stokes fluorescence has within a spectral range of between 450 ran and 700 nm a maximum emission peak with an emission intensity of E maX5 and that at least 30% (more typically 45%, and most typically at least 55%) of the spectral range is covered by a plurality of additional peaks having a fluorescence intensity of at least 0.5 times E m3x .
  • contemplated safety marks may further include (at the same or a different site, separate or in admixture) a second material having a colored anti-stokes fluorescence.
  • second materials may have blue, red, and/or green fluorescence.
  • a method of protecting authenticity of an article will comprise a step of labeling the article with contemplated safety marks.
  • the safety mark may be applied by printing the safety mark on the article (e.g., in an lithographic process, or hand-written ink), incorporating the safety mark into at least part of the article (e.g., admixing the material into a carrier), and/or direct application of the material onto at least part of the article.
  • the article is associated with a spectral footprint of the substantially white anti-stokes fluorescence of the safety mark, and where desirable, a second material having a colored anti-stokes fluorescence may be applied or included into the article.
  • a method of verifying authenticity of an article comprises a step of irradiating the article with infrared light and registering substantially white anti-stokes fluorescence.
  • the step of registering may be performed with a hand-held infrared laser, and that the step of registering will then typically include visual detection of the substantially white anti-stokes fluorescence.
  • the step of registering may also comprise spectral analysis of the substantially white anti-stokes fluorescence to thereby obtain a spectral footprint, wherein the footprint may then be correlated with a spectral footprint in a database (which may or may not include information about the article).
  • Figure IA is a fluorescence emission spectrum of one known anti-stokes material with apparent red color.
  • Figure IB is a fluorescence emission spectrum of another known anti-stokes material with apparent blue color.
  • Figure 1C is a fluorescence emission spectrum of one known anti-stokes material with apparent green color.
  • Figure 2 is a fluorescence emission spectrum of the anti-stokes material according to the inventive subject matter with substantially white fluorescence.
  • each particle is comprised of a material that emits substantially white light.
  • material having substantially white anti-stokes fluorescence refers to any chemically uniform material (as opposed to a mixture or combination of different materials) having a single structural formula that exhibits upon irradiation with infrared light ⁇ i.e., light with a wavelength of between 800 nm and 2000 nm) substantially white anti-stokes fluorescence. Therefore, a chemically uniform and isolated material according to the inventive subject matter (which may or may not be part of a composition) will fall within the scope of this definition so long as such material will exhibit substantially white anti-stokes fluorescence. In contrast, a mixture of multiple and chemically distinct materials (e.g., a mixture of three distinct anti-stokes materials having red, green, and blue anti-stokes fluorescence, respectively) is specifically excluded from the scope of this definition.
  • substantially white anti-stokes fluorescence refers to emitted light of a material in response to irradiation of the compound with infrared light, wherein the emitted light can be characterized as having within a continuous spectral range of between 450 nm and 700 nm a maximum emission peak with an emission intensity OfE 102x , and wherein at least 30% (more typically at least 45%, and most typically at least 55%) of that spectral range is occupied by a plurality of additional emission peaks having a fluorescence intensity of at least 0.5 times E m3x .
  • all or almost all of the shades of the substantially white fluorescence will appear on a color display using an RGB color representation of 256 bits per red (R), green (G), and blue (B) channel as a color represented in a space in which each of R, G, and B have independently a value of between 245 and 255 (e.g., R-249, G-252, B-250), inclusive.
  • an ink composition was formed using commercially available fountain pen ink (e.g., Pelikan ink, Royal Blue Art Brown, 2 West 46th Street, New York, NY 10036) and substantially white fluorescent anti-stokes material having the formula OfY 2 O 2 S : Yb 10 , Er 0003 , Eu 0 . 03 , Dy 0.15 , Gd o. i 3 , Tm o. ] 2 (e.g., commercially available from SupraCarbonic, 348 N. Eckhoff Street - Orange, CA 92868, USA; numerals for sensitizer and activator are mass%).
  • fountain pen ink e.g., Pelikan ink, Royal Blue Art Brown, 2 West 46th Street, New York, NY 10036
  • substantially white fluorescent anti-stokes material having the formula OfY 2 O 2 S : Yb 10 , Er 0003 , Eu 0 . 03 , Dy 0.15 , Gd o. i 3 , Tm o. ] 2
  • the concentration of the substantially white fluorescent anti-stokes material was about 5 mg per ml of ink, which was applied to various materials (e.g., personal check paper, letter paper, baseball, wood, etc.) using a regular fountain pen.
  • a composition was formed using a 10 wt% glycerol/water mixture to which was added the substantially white fluorescent anti-stokes material described above.
  • the concentration of the substantially white fluorescent anti-stokes material was about 5 mg per ml of fluid, which was transferred onto a stamp pad.
  • a rubber stamp was then used to apply the solution to various materials (e.g., personal check paper, letter paper, baseball, wood, etc.) to thereby leave after drying a mark that was invisible to the unaided eye without IR irradiation.
  • substantially white fluorescence was visually observed upon irradiation of the anti-stokes material using a hand-held diode laser having a wavelength of 980 nm and an output of 10 mW (e.g., using Lasermate Group LTG98012AH).
  • the substantially white fluorescence was bright, and visible to the unaided eye, and could be generated from an amount of as little as 50 micrograms.
  • Further analysis of the spectral footprint of the substantially white fluorescent material e.g., using Jasco FP-6500 surprisingly showed that different batches of the fluorescent material had individual spectral footprints, which could not be reproduced.
  • suitable materials need not be limited to the exemplary composition above, but that alternative materials are also deemed suitable.
  • the material will include an inorganic matrix, which contains a rare earth matrix component, and at least five, and more typically six to eight rare earth metals that together act as sensitizer(s) and activators.
  • Suitable matrices particularly include oxysulfides, but oxides, fluorides, and/or oxychlorides are also contemplated herein.
  • suitable rare earth matrix components may vary considerably. However, it is most typically preferred that the rare earth matrix component is yttrium, ytterbium, and/or lanthanum.
  • Preferred sensitizers) and activators will be selected from rare earth metals, and especially include cerium, erbium, europium, dysprosium, gadolinium, thulium, lanthanum, praseodymium, promethium, terbium, and lutetium.
  • the substantially white fluorescing compositions will have yttrium or ytterbium as rare earth metal matrix component, ytterbium as sensitizer, and at least three, and more typically at least four or five (or even more) distinct rare earth metals as activators, wherein the activators, sensitizers, and rare earth matrix component(s) are selected such that incident infrared light is up-converted to substantially white light.
  • substantially white fluorescing compositions will have a chemical composition of formula E n O 2 S : G m] J ⁇ i2, L m 3, Q m4 , X m5 , Y m6 with E being Y or Yb, G being Er or Yb, and J, L, Q, X, and Y being independently selected from the group consisting of erbium, europium, dysprosium, gadolinium, lanthanum, lutetium, praseodymium, promethium, terbium, and thulium, n being 1 or 2, and ml is between 1 and 25 mass %, more preferably between 5 and 15 mass%, and even more preferably between 8 and 12 mass%.
  • m2, m3, m4, m5, and m ⁇ are independently between 0 and 1 mass %, more typically between 0.0005 and 0.5 mass%, and most typically between 0.001 and 0.3 mass%.
  • E is Y
  • G is Yb
  • J, L, Q, X, and Y are independently selected from the group consisting of erbium, europium, dysprosium, gadolinium, and thulium, typically at the amounts as indicated above.
  • such materials can also be characterized as having a substantially white anti-stokes fluorescence that has, within a continuous spectral range of between 450 nm and 700 nm, a maximum emission peak with an emission intensity OfE n13x , wherein at least 30% (more typically at least 45%, and most typically at least 55%) of the spectral range is covered by a plurality of additional peaks having a fluorescence intensity of at least 0.5 times E n13x .
  • FIGS 1A-1C depict exemplary emission spectra of known anti-stokes compounds having red, blue, and green fluorescence, respectively.
  • each of the spectra has within the continuous spectrum of between 450 nm and 700 nm emission maxima that correspond to the respective colors of the fluorescence.
  • the vertical dotted lines depict the end points of the continuous spectral range, while the dotted horizontal line depicts an emission intensity of 50% E max , wherein E max is characterized as the maximum fluorescence emission within the continuous spectral range.
  • E n ax is found in the red area of the spectrum at about 660 run, while in the blue fluorescent material of Figure IB, E max is found in the blue area of the spectrum at about 485 nm. E max at those peaks is then set to 100%, and 50% E ⁇ x is determined accordingly.
  • the exemplary emission spectrum of one substantially white fluorescing composition covers substantially the entire spectral range with more than 62% of the continuous spectrum covered by a plurality of peaks having at least 50% of E 1H3x .
  • emitted light had an intensity of at least 50% OfE m3x .
  • emission was perceived as substantially white light.
  • varying degrees of colored hues may be imparted.
  • the exact spectral characteristics were found to be irreproducible (all spectra were obtained at an excitation wavelength of about 980 nm).
  • the substantially white fluorescing compounds may also be based at least in part on an organic carrier, which bind (e.g., in complex, ionic interaction, or other manner) one or more rare earth metals in predetermined positions relative to each other.
  • an organic carrier which bind (e.g., in complex, ionic interaction, or other manner) one or more rare earth metals in predetermined positions relative to each other.
  • suitable organic carriers and/or chelators are described in U.S. Pat. App. No. 2004/0227694 or 2004/0232826, which are incorporated by reference herein.
  • it is typically preferred that a plurality of chemically distinct rare earth metals are in proximity to each other.
  • one molecule may provide more than one (e.g., two, three, or more) binding or coordination sites for rare earth metals.
  • excitation is in the infrared range of the spectrum, and most typically between 900 nm and 1000 nm.
  • irradiation may also include visible light or even ultraviolet light (i.e., less than 380 nm). It is further preferred that the irradiation light provides the light in a relatively narrow band, and most preferably as laser light.
  • polychromatic IR (ad other) light is also expressly contemplated.
  • irradiation may be performed with a hand-held IR laser using energies of less than 10 mW at a wavelength of 908 ran, 930 ran, or 980 nm.
  • a f ⁇ uorometer may be used at a fixed, and/or variable wavelength excitation. Consequently, emission spectra expressly include 2- dimensional footprints (Le., emission spectrum obtained by excitation at a fixed wavelength) and 3-dimensional footprints (i.e., emission spectrum obtained by excitation at variable wavelengths).
  • substantially white fluorescent materials can be combined with any material in nay manner.
  • contemplated articles to be labeled include bank and security notes, excise labels, magnetic and optical data storage media, documents for personal identification, drugs, biological structures, fashion merchandise, textiles, etc. Therefore, and among numerous other materials, suitable materials include paper, fabric, dye, natural and/or synthetic polymers, metals, metal alloys, cellular structure, etc.
  • the substantially white fluorescent material can be applied in various manners, including liquid preparations (i.e., substantially white fluorescent material in a liquid carrier), dry preparations, (e.g., direct application of powder or in a solid carrier [e.g., in transparent polymer or glass]), and all reasonable combinations thereof. Consequently, the manner of application will depend on the formulation and article. For example, where an autograph is to be authenticated, ink comprising the fluorescent materials may be written from a fountain pen. On the other hand, where the applied safety mark should be invisible to the unaided eye, the mark may be stamped, soaked in, or otherwise applied (with or without carrier).
  • the mark may also be embedded in a transparent plastic that is then employed as a laminated cover over a document.
  • the safety mark may further include anti-stokes materials with colored (e.g., red, green, and/or blue) fluorescence emission to further enhance resistance to forgery, wherein the second colored anti- stokes materials may be present in the same or different location.
  • contemplated substantially white fluorescing materials are most preferably used as a safety mark to label, authenticate, and/or verify a particular article.
  • information about that article may be associated to provide verification.
  • such information may be available to selected personnel (e.g., customs or law enforcement), or only available to a single recipient.
  • a spectral footprint is associated with a mark (and with that with an article)
  • it is contemplated that at least part of such information is located in a remote database.
  • methods of protecting authenticity of an article, wherein that article is labeled with the substantially white fluorescing material are also contemplated.
  • substantially white fluorescence is registered (e.g., visually using a hand-held IR laser, or with a detector, and most typically with fluorometer) upon irradiation with infrared radiation.

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  • Business, Economics & Management (AREA)
  • Accounting & Taxation (AREA)
  • Finance (AREA)
  • Investigating, Analyzing Materials By Fluorescence Or Luminescence (AREA)

Abstract

L'invention présente des compositions et de procédés pour des matériaux présentant une fluorescence anti-stokes sensiblement blanche. Dans des aspects clairement préférables, de tels matériaux sont employés dans des marques de sécurité pour aider à protéger et/ou à valider une authenticité. Il faut remarquer que, alors que les matériaux envisagés présentent une fluorescence blanche, apparente de lot à lot, les empreintes spectrales de tels matériaux ne sont pas reproductibles parmi les lots. Par conséquent, les matériaux envisagés constituent des outils d'identification inestimables étant donné que, dans des lots de fabrication distincts, les matériaux eux-mêmes sont uniquement distincts.
PCT/IB2006/001640 2006-06-07 2006-06-07 Compositions anti-stokes de fluorescence blanche et procédés WO2008004015A2 (fr)

Priority Applications (1)

Application Number Priority Date Filing Date Title
PCT/IB2006/001640 WO2008004015A2 (fr) 2006-06-07 2006-06-07 Compositions anti-stokes de fluorescence blanche et procédés

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
PCT/IB2006/001640 WO2008004015A2 (fr) 2006-06-07 2006-06-07 Compositions anti-stokes de fluorescence blanche et procédés

Publications (1)

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WO2008004015A2 true WO2008004015A2 (fr) 2008-01-10

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Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2017190831A1 (fr) * 2016-05-03 2017-11-09 Giesecke+Devrient Currency Technology Gmbh Élément de sécurité doté d'une impression luminescente

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2017190831A1 (fr) * 2016-05-03 2017-11-09 Giesecke+Devrient Currency Technology Gmbh Élément de sécurité doté d'une impression luminescente

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