WO2003072682A1 - Anti-stokes fluorescent material composition - Google Patents

Anti-stokes fluorescent material composition Download PDF

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Publication number
WO2003072682A1
WO2003072682A1 PCT/EP2002/014254 EP0214254W WO03072682A1 WO 2003072682 A1 WO2003072682 A1 WO 2003072682A1 EP 0214254 W EP0214254 W EP 0214254W WO 03072682 A1 WO03072682 A1 WO 03072682A1
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Prior art keywords
intensity
composition according
less
radiation
fluorescent material
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PCT/EP2002/014254
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French (fr)
Inventor
Bianca Bley
Uwe Fischbeck
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Honeywell Speciality Chemicals Seelze Gmbh
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Priority to US10/506,018 priority Critical patent/US7648648B2/en
Priority to JP2003571372A priority patent/JP2005518475A/en
Priority to KR1020047004224A priority patent/KR100899858B1/en
Priority to KR1020087006955A priority patent/KR100874728B1/en
Priority to AU2002361414A priority patent/AU2002361414B2/en
Application filed by Honeywell Speciality Chemicals Seelze Gmbh filed Critical Honeywell Speciality Chemicals Seelze Gmbh
Priority to EP02796632A priority patent/EP1478715B8/en
Priority to IL15817902A priority patent/IL158179A0/en
Priority to CA002443847A priority patent/CA2443847A1/en
Priority to AT02796632T priority patent/ATE502096T1/en
Priority to DE60239490T priority patent/DE60239490D1/en
Publication of WO2003072682A1 publication Critical patent/WO2003072682A1/en

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    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K11/00—Luminescent, e.g. electroluminescent, chemiluminescent materials
    • C09K11/08—Luminescent, e.g. electroluminescent, chemiluminescent materials containing inorganic luminescent materials
    • C09K11/77—Luminescent, e.g. electroluminescent, chemiluminescent materials containing inorganic luminescent materials containing rare earth metals
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K11/00—Luminescent, e.g. electroluminescent, chemiluminescent materials
    • C09K11/08—Luminescent, e.g. electroluminescent, chemiluminescent materials containing inorganic luminescent materials
    • C09K11/77—Luminescent, e.g. electroluminescent, chemiluminescent materials containing inorganic luminescent materials containing rare earth metals
    • C09K11/7766—Luminescent, e.g. electroluminescent, chemiluminescent materials containing inorganic luminescent materials containing rare earth metals containing two or more rare earth metals
    • C09K11/7767—Chalcogenides
    • C09K11/7769—Oxides
    • C09K11/7771—Oxysulfides
    • G—PHYSICS
    • G06—COMPUTING; CALCULATING OR COUNTING
    • G06K—GRAPHICAL DATA READING; PRESENTATION OF DATA; RECORD CARRIERS; HANDLING RECORD CARRIERS
    • G06K19/00—Record carriers for use with machines and with at least a part designed to carry digital markings
    • G06K19/06—Record carriers for use with machines and with at least a part designed to carry digital markings characterised by the kind of the digital marking, e.g. shape, nature, code
    • G06K19/08—Record carriers for use with machines and with at least a part designed to carry digital markings characterised by the kind of the digital marking, e.g. shape, nature, code using markings of different kinds or more than one marking of the same kind in the same record carrier, e.g. one marking being sensed by optical and the other by magnetic means
    • G06K19/10—Record carriers for use with machines and with at least a part designed to carry digital markings characterised by the kind of the digital marking, e.g. shape, nature, code using markings of different kinds or more than one marking of the same kind in the same record carrier, e.g. one marking being sensed by optical and the other by magnetic means at least one kind of marking being used for authentication, e.g. of credit or identity cards
    • G06K19/14—Record carriers for use with machines and with at least a part designed to carry digital markings characterised by the kind of the digital marking, e.g. shape, nature, code using markings of different kinds or more than one marking of the same kind in the same record carrier, e.g. one marking being sensed by optical and the other by magnetic means at least one kind of marking being used for authentication, e.g. of credit or identity cards the marking being sensed by radiation
    • G—PHYSICS
    • G06—COMPUTING; CALCULATING OR COUNTING
    • G06K—GRAPHICAL DATA READING; PRESENTATION OF DATA; RECORD CARRIERS; HANDLING RECORD CARRIERS
    • G06K7/00—Methods or arrangements for sensing record carriers, e.g. for reading patterns
    • G06K7/10—Methods or arrangements for sensing record carriers, e.g. for reading patterns by electromagnetic radiation, e.g. optical sensing; by corpuscular radiation
    • G06K7/12—Methods or arrangements for sensing record carriers, e.g. for reading patterns by electromagnetic radiation, e.g. optical sensing; by corpuscular radiation using a selected wavelength, e.g. to sense red marks and ignore blue marks

Definitions

  • the invention relates to an anti-Stokes fluorescent material composition which can be excited by IR radiation to emit IR radiation without visible blue light being emitted at the same time to a major extent.
  • the fluorescent material composition is therefore particularly suitable for the application to articles of marks not visible to the human eye.
  • Anti-Stokes fluorescent materials also sometimes called up- conversion fluorescent materials, are known from the state of the art. They are characterized in that, upon excitation by IR radiation of a high wavelength, they emit light of a lower wavelength and thus higher energy. This phenomenon is due to the fact that, for example, multi-photon processes can take place in the fluorescent material.
  • anti-Stokes fluorescent materials emitting green or red light, thus e.g. in O-A-98/39392, which discloses a non-green anti-Stokes fluorescent material.
  • Anti-Stokes fluorescent materials emitting blue light have also already been described e.g. by ⁇
  • the anti- Stokes fluorescent materials emitting blue light are in general compounds doped with thulium.
  • the blue emission is very weak, in comparison to the green emission in the ant i - Stokes fluorescent materials emitting green light, as three photons of IR-radiation are actually required for one photon of blue light.
  • the fluorescent material (Gd 0 . B7 Yb 0 .i 3 T ⁇ «o.oo ⁇ ) 2 ⁇ 2 S has furthermore been described by P. Yokom in Met. Trans. 2 (1971), pages 763- 767 which, upon excitation by IR radiation, emits blue visible light as well as IR radiation of a smaller wavelength than the exciting radiation. This is therefore also an anti-Stokes process.
  • the IR emission band is however much more intense as, in contrast to the blue emission, only two quanta of infra-red light of higher wavelength are required for one quantum of IR light of a lower wavelength.
  • the fluorescent material also displays, in addition to the said IR band and blue band, an emission of red light.
  • a feature common to the IR light-emitting anti-stokes fluorescent materials available hitherto is therefore that, because of the portion of emitted visible light, in particular blue light, they are still recognizable to the human eye when they are excited by IR radiation. This is particularly disadvantageous when the fluorescent materials are used to mark and authenticate items such as documents, bank notes and credit cards.
  • the object of the invention was therefore to provide an IR light-emitting anti-Stokes fluorescent material in which the portion of emitted blue light is clearly reduced and which can thus be used for a security mark which is completely invisible to the human eye.
  • This object is surprisingly achieved by the anti-Stokes fluorescent material composition of the invention according to any one of claims 1 to 10.
  • the invention likewise relates to the process for the preparation of the composition according to claims 11 to 13, its use according to claims 14 and 15 as well as the marked article according to claim 16.
  • the fluorescent material composition according to the invention is characterized in that it comprises the chemical elements M, ytterbium, thulium, oxygen and sulphur in a molar ratio relative to each other corresponding to the following formula (I) , wherein M is selected from the group consisting of yttrium, gadolinium and lanthanum
  • composition in which y lies in the range from 0.15 to 0.3 is preferred.
  • the fluorescent material composition according to the invention can also contain additional chemical elements in addition to those named in Formula (I), it being advantageous if the latter are present in a quantity of less than or equal to 1000 wppm, preferably less than or equal to 500 wppm and particularly preferably less than or equal to 100 wppm, relative to Yb.
  • additional chemical elements are further rare earth metals.
  • Preferred further rare earth metals are selected from the group dysprosium and samarium.
  • the invention also relates to an anti-Stokes fluorescent material composition which, when subjected to IR radiation of a wavelength of 975 nm,
  • the intensity I 43 o n ⁇ is less than 45 % of the intensity l 79S nm and the reference material is l. 52 4Yt > o. 474 T 0 . 0 . 31 8 ⁇ 2 S .
  • a composition is preferred wherein the intensity l480nm is less than 40%, in particular less than 30% and particularly preferred, less than 20% of the intensity l ⁇ g ⁇ m.
  • the preferred procedure for the preparation of the composition according to the invention is that an oxide of M, an oxide of Yb, an oxide of Tm and sulphur are sintered together with a flux.
  • the sinter temperature can vary within a wide range, the sintering preferably being carried out at a sinter temperature of 800 to 1300°C, in particular 1000 to 1100°C.
  • the starting compounds are mixed with each other or ground, in particular finely ground, optionally together with water and/or sulphur and/or flux. If fine grinding is carried out in the presence of water, then the suspension of the rare earth metal compounds obtained is dried and subsequently sieved.
  • fluxes are e.g. alkali metal, alkaline-earth metal and ammonium compounds, such as borates, carbonates, hydrogen carbonates, phosphates, hydrogen phosphates, halides and thiosulphates, as well as mixtures of these compounds.
  • the fluorescent material composition according to the invention is used to authenticate articles by providing the articles with the composition in order to form a marked article.
  • the marked article is irradiated with IR light and the radiation thereupon emitted by the article is analyzed.
  • the analysis takes place as a rule with usual detectors for IR radiation. It is possible to cover individual bands, only or also the whole IR spectrum.
  • the articles to be marked are above all data carriers or documents, with chip cards, cheque cards or credit cards being used in particular as data carriers and identity cards, bank notes and certificates as documents.
  • the fluorescent materials according to the invention are colourless not only upon irradiation with daylight but also upon irradiation with IR light, they generate a mark not recognizable to the observer, which is important for precisely these article which, like e.g. chip cards, cheque cards or credit cards as well as identity cards, bank notes and certificates, are often exposed to attempts at forgery.
  • the irradiation of these articles with IR light generates a characteristic IR emission spectrum without significant quantities of blue light being emitted at the same time which is visible to the eye, as with known fluorescent materials.
  • the emission spectra produced by special compositions according to the invention in each case are then a sure sign for the checker of a marked article that the latter was marked with the compositions and that an article is therefore genuine. Consequently, the fluorescent material compositions according to the invention serve to prevent attempts at forgery or to detect attempts at forgery.
  • the fluorescent material compositions according to the invention can be incorporated per se in customary manner into the articles to be marked. It is however also conceivable that they are used in the form of mixtures with auxiliaries which comprise the fluorescent materials e.g. together with a binder. In particular acrylic polymers, polyamides, polyurethanes, polyesters and polyethylene terephthalates as well as the corresponding monomers and oligomers can be considered as suitable binder. Furthermore . it is also conceivable that the fluorescent material compositions according to the invention are used together with a liquid carrier, e.g. in the form of dispersions. Such dispersions can then be used for example to impregnate the articles to be marked. Such a procedure is possible e.g. for the preparation of marked safety threads which are then incorporated e.g. into identity cards, bank notes, cheques and certificates.
  • the invention also relates to marked articles -which comprise the fluorescent material composition according to the invention.
  • a total of 16 different fluorescent material compositions according to the invention were prepared. Radiation intensities of ' the emitted light were analysed with a Shimadzu spectro fluoro photometer RF 5000 having an extended wave length range.
  • mixtures of Y 2 0 3 optionally replaced by Gd 2 0 3 or a 2 ⁇ 3/ with Yb 2 0 3 , Tm 2 0 3 , Na 2 C0 3 , K 2 C0 3/ S and Na 3 HP0 4 were produced. These mixtures were introduced into an aluminium oxide crucible and calcined for several hours in an furnace at 1000-1100°C. After cooling to room temperature, the calcined products were removed, stirred in water and, after several washings with water, dis gglomerated by grinding in a ball mill and then washed with hydrochloric acid and ammonia solution.
  • the value for I 48 on m s based on the intensity of the emitted blue light of a wavelength of 480 nm of a reference material whose intensity "was arbitrarily set to be 100%.
  • the value for l 796 ⁇ is based on the intensity of the emitted IR light of a wavelength of 480 nm of a reference material whose intensity was also arbitrarily set to be 100%.
  • the reference material was ⁇ . 524 Y o. 474 l o.ooi 8 2 S which in the table is mentioned as "comparison” and which is a conventional fluorescent material with small quantities of thulium.
  • excitation . took place with a xenon short-arc lamp which emitted IR radiation of a wavelength of 975 nm.
  • table 1 includes values for the percentage of the emitted blue light in form of values for the expression
  • the fluorescent materials according to the invention emit a quantity of blue light that is clearly reduced relative to the emitted IR radiation, which is very desirable. It is very surprising that this could be achieved in particular by increasing the quantity of T .
  • examples 6 to 8 show that, even with the addition of small quantities of other substances such as Dy 2 0 3 and Sm 2 0 3 , fluorescent materials with a low blue-light emission can be prepared.

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  • Engineering & Computer Science (AREA)
  • Chemical & Material Sciences (AREA)
  • Physics & Mathematics (AREA)
  • Theoretical Computer Science (AREA)
  • General Physics & Mathematics (AREA)
  • Organic Chemistry (AREA)
  • Materials Engineering (AREA)
  • Inorganic Chemistry (AREA)
  • Health & Medical Sciences (AREA)
  • Electromagnetism (AREA)
  • General Health & Medical Sciences (AREA)
  • Toxicology (AREA)
  • Artificial Intelligence (AREA)
  • Computer Vision & Pattern Recognition (AREA)
  • Luminescent Compositions (AREA)
  • Vessels And Coating Films For Discharge Lamps (AREA)
  • Analysing Materials By The Use Of Radiation (AREA)

Abstract

The invention relates to anti-Stokes fluorescent material compositions which, upon excitation by IR radiation, for their part emit IR radiation without significant quantities of visible blue light being emitted at the same time, and which are therefore suitable as invisible security marks.

Description

Vnti-Stoke3 Fluorescent Material Composition
The invention relates to an anti-Stokes fluorescent material composition which can be excited by IR radiation to emit IR radiation without visible blue light being emitted at the same time to a major extent. The fluorescent material composition is therefore particularly suitable for the application to articles of marks not visible to the human eye.
Anti-Stokes fluorescent materials, also sometimes called up- conversion fluorescent materials, are known from the state of the art. They are characterized in that, upon excitation by IR radiation of a high wavelength, they emit light of a lower wavelength and thus higher energy. This phenomenon is due to the fact that, for example, multi-photon processes can take place in the fluorescent material.
The literature on anti-Stokes fluorescent materials is extensive. In particular, there have been various reports on fluorescent materials emitting green or red light, thus e.g. in O-A-98/39392, which discloses a non-green anti-Stokes fluorescent material. Anti-Stokes fluorescent materials emitting blue light have also already been described e.g. by Λ
2 E. Bielejec in J. Lumin. 72-74 (1997), pages 62-64. The anti- Stokes fluorescent materials emitting blue light are in general compounds doped with thulium. The blue emission is very weak, in comparison to the green emission in the anti- Stokes fluorescent materials emitting green light, as three photons of IR-radiation are actually required for one photon of blue light.
The fluorescent material (Gd0.B7Yb0.i3Tι«o.ooι)2θ2S has furthermore been described by P. Yokom in Met. Trans. 2 (1971), pages 763- 767 which, upon excitation by IR radiation, emits blue visible light as well as IR radiation of a smaller wavelength than the exciting radiation. This is therefore also an anti-Stokes process. The IR emission band is however much more intense as, in contrast to the blue emission, only two quanta of infra-red light of higher wavelength are required for one quantum of IR light of a lower wavelength. However, the fluorescent material also displays, in addition to the said IR band and blue band, an emission of red light.
A feature common to the IR light-emitting anti-stokes fluorescent materials available hitherto is therefore that, because of the portion of emitted visible light, in particular blue light, they are still recognizable to the human eye when they are excited by IR radiation. This is particularly disadvantageous when the fluorescent materials are used to mark and authenticate items such as documents, bank notes and credit cards.
The object of the invention was therefore to provide an IR light-emitting anti-Stokes fluorescent material in which the portion of emitted blue light is clearly reduced and which can thus be used for a security mark which is completely invisible to the human eye. This object is surprisingly achieved by the anti-Stokes fluorescent material composition of the invention according to any one of claims 1 to 10.
The invention likewise relates to the process for the preparation of the composition according to claims 11 to 13, its use according to claims 14 and 15 as well as the marked article according to claim 16.
The fluorescent material composition according to the invention is characterized in that it comprises the chemical elements M, ytterbium, thulium, oxygen and sulphur in a molar ratio relative to each other corresponding to the following formula (I) , wherein M is selected from the group consisting of yttrium, gadolinium and lanthanum
(Mx, Yby, Tmz)202S (I)
and wherein χ + y + z = 1, x > 0, y > 0 and z ≥ 0.0025.
Surprisingly, it was possible, in particular by changing the quantity of thulium, to prepare a fluorescent material composition which displays a greatly reduced blue emission and in addition emits light even more strongly in the IR range.
Upon examination of a fluorescent material (Y, Yb)z°aS:TmOι0018, taken as comparison, a maximum blue emission was to be recorded. Surprisingly, the intensities of the blue band and of the IR band did not change to the same extent when the thulium concentration changed. With increased thulium concentrations, the IR band surprisingly increases still further in absolute intensity whereas the blue band increasingly loses in intensity. The result is a very low intensity of the blue band and simultaneously a very high intensity of the IR emission in the composition according to the invention as defined above.
Such a composition in which z lies in the range from 0.0025 to 0.03 and preferably in the range from 0.0075 to 0.02 has proved particularly favourable.
Furthermore, a composition in which y lies in the range from 0.15 to 0.3 is preferred.
The fluorescent material composition according to the invention can also contain additional chemical elements in addition to those named in Formula (I), it being advantageous if the latter are present in a quantity of less than or equal to 1000 wppm, preferably less than or equal to 500 wppm and particularly preferably less than or equal to 100 wppm, relative to Yb. Possible additional chemical elements are further rare earth metals. Preferred further rare earth metals are selected from the group dysprosium and samarium.
The invention also relates to an anti-Stokes fluorescent material composition which, when subjected to IR radiation of a wavelength of 975 nm,
(i) emits IR light of a wavelength of 796 nm in an intensity I796nmr based on the intensity of a reference material set to be 100%, and
(ii) emits blue light of a wavelength of 480 nm in an intensity I48onm based on the intensity of a reference material set to be 100%,
wherein the intensity I43onιΛ is less than 45 % of the intensity l79Snm and the reference material is l.524Yt>o.474T 0.0.318θ2S . A composition is preferred wherein the intensity l480nm is less than 40%, in particular less than 30% and particularly preferred, less than 20% of the intensity lηgβπm.
The preferred procedure for the preparation of the composition according to the invention is that an oxide of M, an oxide of Yb, an oxide of Tm and sulphur are sintered together with a flux. The sinter temperature can vary within a wide range, the sintering preferably being carried out at a sinter temperature of 800 to 1300°C, in particular 1000 to 1100°C.
Furthermore, it is likewise possible to use at least one of the oxides in the form of a precursor compound which converts into the corresponding oxide under the sintering conditions.
Before the actual sintering, the starting compounds are mixed with each other or ground, in particular finely ground, optionally together with water and/or sulphur and/or flux. If fine grinding is carried out in the presence of water, then the suspension of the rare earth metal compounds obtained is dried and subsequently sieved.
In general, compounds or mixtures of these which are capable of forming a (poly) sulphide with sulphur or sulphur-containing rare earth metal compounds upon sintering can be used as fluxes. Possible fluxes are e.g. alkali metal, alkaline-earth metal and ammonium compounds, such as borates, carbonates, hydrogen carbonates, phosphates, hydrogen phosphates, halides and thiosulphates, as well as mixtures of these compounds.
Preferably, the fluorescent material composition according to the invention is used to authenticate articles by providing the articles with the composition in order to form a marked article.
It is further preferred that, to detect the presence of the mark, the marked article is irradiated with IR light and the radiation thereupon emitted by the article is analyzed. As the emitted radiation is in the infrared range, the analysis takes place as a rule with usual detectors for IR radiation. It is possible to cover individual bands, only or also the whole IR spectrum.
The articles to be marked are above all data carriers or documents, with chip cards, cheque cards or credit cards being used in particular as data carriers and identity cards, bank notes and certificates as documents.
As the fluorescent materials according to the invention are colourless not only upon irradiation with daylight but also upon irradiation with IR light, they generate a mark not recognizable to the observer, which is important for precisely these article which, like e.g. chip cards, cheque cards or credit cards as well as identity cards, bank notes and certificates, are often exposed to attempts at forgery. On the other hand, the irradiation of these articles with IR light generates a characteristic IR emission spectrum without significant quantities of blue light being emitted at the same time which is visible to the eye, as with known fluorescent materials. The emission spectra produced by special compositions according to the invention in each case are then a sure sign for the checker of a marked article that the latter was marked with the compositions and that an article is therefore genuine. Consequently, the fluorescent material compositions according to the invention serve to prevent attempts at forgery or to detect attempts at forgery.
The fluorescent material compositions according to the invention can be incorporated per se in customary manner into the articles to be marked. It is however also conceivable that they are used in the form of mixtures with auxiliaries which comprise the fluorescent materials e.g. together with a binder. In particular acrylic polymers, polyamides, polyurethanes, polyesters and polyethylene terephthalates as well as the corresponding monomers and oligomers can be considered as suitable binder. Furthermore . it is also conceivable that the fluorescent material compositions according to the invention are used together with a liquid carrier, e.g. in the form of dispersions. Such dispersions can then be used for example to impregnate the articles to be marked. Such a procedure is possible e.g. for the preparation of marked safety threads which are then incorporated e.g. into identity cards, bank notes, cheques and certificates.
Finally, the invention also relates to marked articles -which comprise the fluorescent material composition according to the invention.
The invention is explained in more detail in the following examples .
Examples
Examples 1 to 16
A total of 16 different fluorescent material compositions according to the invention were prepared. Radiation intensities of ' the emitted light were analysed with a Shimadzu spectro fluoro photometer RF 5000 having an extended wave length range.
To this end, firstly, mixtures of Y203, optionally replaced by Gd203 or a2θ3/ with Yb203, Tm203, Na2C03, K2C03/ S and Na3HP04 were produced. These mixtures were introduced into an aluminium oxide crucible and calcined for several hours in an furnace at 1000-1100°C. After cooling to room temperature, the calcined products were removed, stirred in water and, after several washings with water, dis gglomerated by grinding in a ball mill and then washed with hydrochloric acid and ammonia solution. After filtering off and drying in a drying cupboard, solid powders were obtained which were sieved by means of a stainless-steel sieve (mesh size 80 μ ) . In the following Table 1, the quantities of starting materials used in each case, the yields obtained of the fluorescent materials according to the invention and the corresponding formulae are given. In addition, for all fluorescent materials prepared, the intensity of the emitted blue light of a wavelength of 480 nm, referred to as
Figure imgf000009_0001
and the intensity of the emitted IR radiation at 796 n , referred to as l796nm/ are given. The value for I48onm s based on the intensity of the emitted blue light of a wavelength of 480 nm of a reference material whose intensity "was arbitrarily set to be 100%. Likewise, the value for l796π is based on the intensity of the emitted IR light of a wavelength of 480 nm of a reference material whose intensity was also arbitrarily set to be 100%, In both cases the reference material was ι.524Y o.474l o.ooi8 2S which in the table is mentioned as "comparison" and which is a conventional fluorescent material with small quantities of thulium. In all experiments excitation . took place with a xenon short-arc lamp which emitted IR radiation of a wavelength of 975 nm.
Additionally, table 1 includes values for the percentage of the emitted blue light in form of values for the expression
Figure imgf000009_0002
It is apparent that the fluorescent materials according to the invention emit a quantity of blue light that is clearly reduced relative to the emitted IR radiation, which is very desirable. It is very surprising that this could be achieved in particular by increasing the quantity of T .
Furthermore, examples 6 to 8 show that, even with the addition of small quantities of other substances such as Dy203 and Sm203, fluorescent materials with a low blue-light emission can be prepared. rH Φ Λ rα
Figure imgf000010_0001
Figure imgf000011_0001
Figure imgf000012_0002
Figure imgf000012_0001

Claims

Claims
Anti-Stokes fluorescent material composition which comprises the chemical elements M, ytterbium, thulium, oxygen and sulphur in a molar ratio relative to each other corresponding to the following formula (I), wherein M is selected from the group consisting of yttrium, gadolinium and lanthanum
(Mx, Yby, ϊm2)202S (I)
and wherein x + y + z = 1, x > 0, y > 0 and z > 0.0025.
Composition according to claim 1, in which z lies in the range from 0.0025 to 0.03, in particular in the range from 0.0075 to 0.02.
Composition according to claim 1 or 2, in which y lies in the range from 0.15 to 0.3.
Composition according to any one of claims 1 to 3, which comprises additional chemical elements in a quantity less than or equal to 1000 wppm, in particular of less than or equal to 500 wppm, relative to Yb.
Composition according to claim 4, in which the additional elements are further rare earth metals.
Composition according to claim 5, in which the further rare earth metal is selected from the group of dysprosium and samarium. 02 14254
13
Anti-Stokes fluorescent material composition which, when subjected to IR radiation of a wavelength of 975 nm,
(i) emits IR light of a wavelength of 796 nm in an intensity 1786™, based on the intensity of a reference material set to be 100%, and
(ii) emits blue light of a wavelength of 480 nm in an intensity laoι based on the intensity of a reference material set to be 100%,
wherein the intensity I480nπ is less than 45 % of the intensity I796nm and the reference material is
Yj..S24Ybθ .474Tmrj.ooi8θ2S .
Composition according to claim 7, wherein the intensity l80nm is less than 40 % of the intensity l796r_m-
Composition according to claim 7, wherein the intensity l80nm is less than 30 % of the intensity l796nm«
Composition according to claim 7, wherein the intensity lήβorro is less than 20 % of the intensity I796n.1i'
Process for the preparation of the composition according to any one of claims 1 to 10, wherein an oxide of M, an oxide of Yb, an oxide of Tm and sulphur are sintered together with a flux and wherein M is selected from the group consisting of yttrium, gadolinium and lanthanum.
Process according to claim 11, wherein the sintering is carried out at a sinter temperature of 800 to 1300°C.
Process according to claim 11 or 12, wherein at least one of the oxides is used in the form of a precursor compound which converts into the oxide under the sintering conditions. 4254
14 Use of the composition according to any one of claims 1 to 10 for the authentication of an article by providing the article, with the composition in order to form a marked article.
Use according to claim 14, wherein the marked article is irradiated with IR radiation and the radiation emitted by the marked article is analyzed.
Marked article which comprises the composition according to any one of claims 1 to 10.
PCT/EP2002/014254 2002-02-27 2002-12-13 Anti-stokes fluorescent material composition WO2003072682A1 (en)

Priority Applications (10)

Application Number Priority Date Filing Date Title
DE60239490T DE60239490D1 (en) 2002-02-27 2002-12-13 FLUORESCENT MATERIAL CONNECTION OF TYPE ANTI-STOKES
JP2003571372A JP2005518475A (en) 2002-02-27 2002-12-13 Anti-Stokes fluorescent material composition
KR1020047004224A KR100899858B1 (en) 2002-02-27 2002-12-13 Anti-Stokes Fluorescent Material Composition
KR1020087006955A KR100874728B1 (en) 2002-02-27 2002-12-13 Anti-Stokes Fluorescent Material Composition
AU2002361414A AU2002361414B2 (en) 2002-02-27 2002-12-13 Anti-stokes fluorescent material composition
US10/506,018 US7648648B2 (en) 2002-02-27 2002-12-13 Anti-stokes fluorescent material composition
EP02796632A EP1478715B8 (en) 2002-02-27 2002-12-13 Anti-stokes fluorescent material composition
IL15817902A IL158179A0 (en) 2002-02-27 2002-12-13 Anti-stokes fluorescent material composition
CA002443847A CA2443847A1 (en) 2002-02-27 2002-12-13 Anti-stokes fluorescent material composition
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EP1241021A3 (en) * 2001-03-16 2004-03-10 BUNDESDRUCKEREI GmbH Document of value and/or security document
EP1498545B1 (en) 2003-07-14 2017-09-27 Flex Products, Inc. a JDS Uniphase Company Security thread comprising an optically variable structure
EP1760134A1 (en) * 2005-08-30 2007-03-07 Viktor Ivanovich Petrik White-flourescent anti-strokes compositions and methods for identification and protection of excise labels, bank notes, securities, documents and products
US10532071B2 (en) 2007-03-14 2020-01-14 BLüCHER GMBH High-performance adsorbents based on activated carbon having high meso- and macroporosity
WO2008132223A2 (en) * 2007-04-30 2008-11-06 Österreichische Staatsdruckerei Gmbh Use of a luminophore as security feature security printing ink method and device for checking a document and document and security feature
WO2008132223A3 (en) * 2007-04-30 2009-01-15 Oesterreichische Staatsdrucker Use of a luminophore as security feature security printing ink method and device for checking a document and document and security feature
RU2610592C2 (en) * 2015-05-18 2017-02-14 Общество с ограниченной ответственностью научно-производственная фирма "ЛЮМ" LUMINOPHOR OF COMPLEX PRINCIPLE OF ACTION ON BASIS OF YTTRIUM, LANTHANUM AND GADOLINIUM OXYSULFIDES, ACTIVATED WITH IONS OF Yb3+ AND Tm3+
WO2017220079A1 (en) * 2016-06-21 2017-12-28 Polysecure Gmbh Method for identifying materials
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