EP1175469A2 - Substances luminescentes minerales a grain tres fin - Google Patents

Substances luminescentes minerales a grain tres fin

Info

Publication number
EP1175469A2
EP1175469A2 EP00926996A EP00926996A EP1175469A2 EP 1175469 A2 EP1175469 A2 EP 1175469A2 EP 00926996 A EP00926996 A EP 00926996A EP 00926996 A EP00926996 A EP 00926996A EP 1175469 A2 EP1175469 A2 EP 1175469A2
Authority
EP
European Patent Office
Prior art keywords
phosphor
mixture
fiber
luminescent
phosphors
Prior art date
Legal status (The legal status 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 status listed.)
Withdrawn
Application number
EP00926996A
Other languages
German (de)
English (en)
Inventor
Bianca Bley
Uwe Fischbeck
Thomas Potrawa
Alfred Siggel
Jürgen WIECZORECK
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Honeywell Specialty Chemicals Seelze GmbH
Original Assignee
Honeywell Specialty Chemicals Seelze GmbH
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
Priority claimed from DE1999117887 external-priority patent/DE19917887A1/de
Priority claimed from DE1999134436 external-priority patent/DE19934436B4/de
Application filed by Honeywell Specialty Chemicals Seelze GmbH filed Critical Honeywell Specialty Chemicals Seelze GmbH
Publication of EP1175469A2 publication Critical patent/EP1175469A2/fr
Withdrawn legal-status Critical Current

Links

Classifications

    • D—TEXTILES; PAPER
    • D21—PAPER-MAKING; PRODUCTION OF CELLULOSE
    • D21H—PULP COMPOSITIONS; PREPARATION THEREOF NOT COVERED BY SUBCLASSES D21C OR D21D; IMPREGNATING OR COATING OF PAPER; TREATMENT OF FINISHED PAPER NOT COVERED BY CLASS B31 OR SUBCLASS D21G; PAPER NOT OTHERWISE PROVIDED FOR
    • D21H21/00—Non-fibrous material added to the pulp, characterised by its function, form or properties; Paper-impregnating or coating material, characterised by its function, form or properties
    • D21H21/14—Non-fibrous material added to the pulp, characterised by its function, form or properties; Paper-impregnating or coating material, characterised by its function, form or properties characterised by function or properties in or on the paper
    • D21H21/40—Agents facilitating proof of genuineness or preventing fraudulent alteration, e.g. for security paper
    • D21H21/44—Latent security elements, i.e. detectable or becoming apparent only by use of special verification or tampering devices or methods
    • D21H21/48—Elements suited for physical verification, e.g. by irradiation
    • 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
    • C09K11/02—Use of particular materials as binders, particle coatings or suspension media therefor
    • C09K11/025—Use of particular materials as binders, particle coatings or suspension media therefor non-luminescent particle coatings or suspension media
    • 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
    • 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
    • C09K11/57—Luminescent, e.g. electroluminescent, chemiluminescent materials containing inorganic luminescent materials containing manganese or rhenium
    • C09K11/572—Chalcogenides
    • C09K11/574—Chalcogenides with zinc or cadmium
    • 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
    • C09K11/58—Luminescent, e.g. electroluminescent, chemiluminescent materials containing inorganic luminescent materials containing copper, silver or gold
    • C09K11/582—Chalcogenides
    • C09K11/584—Chalcogenides with zinc or cadmium
    • 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
    • C09K11/60—Luminescent, e.g. electroluminescent, chemiluminescent materials containing inorganic luminescent materials containing iron, cobalt or nickel
    • C09K11/602—Chalcogenides
    • C09K11/605—Chalcogenides with zinc or cadmium
    • 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
    • C09K11/64—Luminescent, e.g. electroluminescent, chemiluminescent materials containing inorganic luminescent materials containing aluminium
    • C09K11/641—Chalcogenides
    • C09K11/642—Chalcogenides with zinc or cadmium
    • 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
    • C09K11/67—Luminescent, e.g. electroluminescent, chemiluminescent materials containing inorganic luminescent materials containing refractory metals
    • C09K11/671—Chalcogenides
    • C09K11/672—Chalcogenides with zinc or cadmium
    • D—TEXTILES; PAPER
    • D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
    • D01F—CHEMICAL FEATURES IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS; APPARATUS SPECIALLY ADAPTED FOR THE MANUFACTURE OF CARBON FILAMENTS
    • D01F1/00—General methods for the manufacture of artificial filaments or the like
    • D01F1/02—Addition of substances to the spinning solution or to the melt
    • D01F1/04—Pigments
    • D—TEXTILES; PAPER
    • D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
    • D01F—CHEMICAL FEATURES IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS; APPARATUS SPECIALLY ADAPTED FOR THE MANUFACTURE OF CARBON FILAMENTS
    • D01F2/00—Monocomponent artificial filaments or the like of cellulose or cellulose derivatives; Manufacture thereof
    • D01F2/06—Monocomponent artificial filaments or the like of cellulose or cellulose derivatives; Manufacture thereof from viscose
    • D01F2/08—Composition of the spinning solution or the bath
    • D01F2/12—Addition of delustering agents to the spinning solution
    • D01F2/14—Addition of pigments

Definitions

  • the present invention relates to very fine-grained inorganic phosphors, a process for their preparation and their use, in particular the incorporation of such phosphors in luminescent viscose fibers.
  • UV-stimulable phosphors are known and are used, for example, in security documents or machine-readable documents.
  • the UV-stimulable phosphors are also used in so-called fluorescent lamps or fluorescent advertising tubes and in high-pressure mercury lamps.
  • the phosphors are selected according to the desired emission color.
  • excitation by UV rays there are other excitation options depending on the phosphor.
  • some phosphors can be excited by electron beams, which is mainly used in television and computer screens as well as in oscillograph tubes and image converters.
  • Electro-luminescent phosphors are of particular importance which, after excitation with short-wave visible light, continue to shine for a long time after switching off the exciting light source, that is to say show strong phosphorescence.
  • the afterglow colors have recently become very important because they can be used to mark escape routes that can still be recognized in the event of light failure.
  • electroluminescent phosphors ie phosphors that glow when an electric field is applied.
  • Electro-luminescent compounds are, for example, ZnS, ZnSe, CdS etc., which are combined with various activators such as Cu or Mn, are activated.
  • the electroluminescent phosphors are used, for example, on the dials of measuring instruments.
  • Phosphors can either consist of organic compounds or inorganic compounds.
  • Inorganic phosphors generally have the advantage of very good light fastness compared to the organic phosphors.
  • the hardness and the high density are major disadvantages for special applications of the previously known inorganic phosphors.
  • a large grain size leads to a low resolution of the individual structures, e.g. fine lines, pixels, small letters or picture elements. Small outlet openings in mechanical pressure devices can become blocked by particles that are too large.
  • High hardness can cause mechanical abrasion and wear in the printing press.
  • a high density causes the phosphor to sit on in a liquid medium and thus an inhomogeneous distribution of the phosphor in the color.
  • the phosphor suspension must be homogenized before use.
  • Inorganic phosphors are usually polycrystalline powders. It is well known that the crystals lose considerable brightness when their grain size is reduced, for example by mechanical grinding. It is not possible to grind crystalline inorganic phosphors without loss of brightness. Therefore, the use of inorganic phosphors was previously limited to printing inks for screen, gravure and flat printing, depending on the size of the particles. Small particle sizes are required especially for the production of security documents or machine-readable documents, the printing of which should consist of fine structures.
  • the conventional inorganic phosphors are too coarse for a process such as inkjet printing, in which the ink is applied to the material to be printed through a fine nozzle, since they are the nozzles would clog. This processing technique was previously reserved for organic phosphors.
  • inorganic phosphors are zinc sulfides containing various activators, for example ZnS: Cu, ZnS: Ag and ZnS: Mn.
  • Such phosphors are usually represented by means of solid-state synthesis.
  • the inorganic phosphors produced using the known solid-state syntheses have average grain sizes of significantly more than 1 micrometer.
  • GB 1 454 854 further relates to a method for producing an electro-luminescent powder based on a manganese-activated zinc sulfide, which comprises heating a starting mixture of a zinc sulfide powder and a manganese compound in an atmosphere comprising carbon disulfide at a temperature in the range of 600 up to 900 ° C. and introducing the mixture heated in this way into an aqueous solution containing copper ions, wherein the amount of manganese in the manganese compound based on the zinc sulfide powder is 0.1 to 0.5% by weight.
  • an inorganic phosphor with an average particle size of at most 1000 nm, preferably of at most 800 nm, more preferably of at most 600 nm and particularly preferably of at most 400 nm, is produced by means of solid-state synthesis.
  • the phosphor according to the invention has an average particle size which is at least 10 nm, preferably at least 20 nm.
  • the average grain size of the phosphor particles is in the range from approximately 50 nm to approximately 400 nm, particularly preferably in a range from approximately 100 nm to approximately 200 nm.
  • the inorganic phosphor according to the invention comprises at least one host lattice based on ZnS and / or ZnS / ZnO and / or ZnS / CdS and at least one activator.
  • the activator has at least one of the elements from the group comprising Co, Cu, Al, Ag, Au, Mn, Cr, Ti, Th and the rare earth metals and / or a mixture of two or more elements of this group.
  • the weight fraction of the activators in the total weight of the phosphor particles is less than 5%, particularly preferably less than 1%.
  • the phosphor comprises a host grid based on ZnS and / or ZnS / ZnO and / or ZnS / CdS and activators from the group Cu, Ag, Au, Mn with a weight fraction of at most 5%, in particular less than 1% and additionally about 1 ppm to about 0.1% by weight, preferably about 1 ppm to about 50 ppm, particularly preferably about 2 to about 20 ppm, in each case based on the sum of the metal sulfides, at least one further one as defined above Elementes, preferably of Co and / or Al.
  • the copper and / or silver content as activator is preferably at most 100 ppm each. If manganese is used as an activator, its content is preferably above 0.5 to 5% by weight and in particular 1 to 4% by weight.
  • the invention further relates to a method for producing an inorganic phosphor having an average particle size of at most 1000 nm, the method comprising at least the following step (i):
  • other compounds of at least one of the elements Zn and Cd which can be decomposed under sintering conditions are preferably sulfates, carbonates and / or chlorides of Zn and / or Cd.
  • the starting compounds optionally together with water and / or sulfur and / or others Additives, such as, for example, melting agents, are mixed or ground with one another, preferably fine grinding here. If fine grinding is carried out in the presence of water, the resulting slurry of the compounds is filtered and the mixture obtained is dried and then sieved.
  • Additives such as, for example, melting agents
  • the phosphor particles obtained by the method of the invention can be in the form of needles, platelets, double pyramids, octahedra, tetrahedra, prisms and as spherical particles.
  • the phosphor particles obtained are preferably in the form of spheres.
  • Further additives are preferably used to influence the crystallization of the phosphor.
  • Ammonium and / or alkali and / or alkaline earth halides and / or phosphates and / or borates and / or carbonates and / or compounds which form a corresponding halide, phosphate or borate under the present reaction conditions are preferred and / or Mixtures of two or more of the aforementioned compounds are used.
  • the sintering temperature and the duration of the sintering process also influence the grain size of the phosphor obtained.
  • the individual particles of the phosphor to be sintered become denser, the higher the sintering temperature and the longer the sintering time.
  • the sintering time in the invention is preferably between approximately 0.5 to approximately 15 hours, particularly preferably between approximately 2 and 10 hours.
  • the sintering temperature is generally in a range from 400 to 1500 ° C, preferably in a range from 600 ° C to 1000 ° C.
  • the starting mixture is heated to a temperature of about 500 ° C. in about 20 minutes.
  • the mixture heated in this way is then held at this temperature of about 500 ° C. for about 240 minutes.
  • the reaction mixture is then brought to a temperature in a range from 600 ° C to 700 ° C, preferably to about 650 ° C, at which the mixture is then held for about 150 minutes.
  • the phosphors according to the present invention differ with respect to the known electroluminescent phosphors, as are mentioned, for example, in GB 1 454 854 mentioned at the outset, in that when copper is used as an activator, for example, it is homogeneously distributed over the phosphor, while in the case of known electroluminescent phosphors, copper is always present in the outer region of the phosphor particles as a “conductor strip”.
  • the atmosphere during sintering in the process according to the invention does not contain any critical substances, such as carbon disulfide, but rather can exist in an oxygen-containing atmosphere, such as air, but also in inert gases such as nitrogen.
  • the invention further relates to a printing ink which has a phosphor and / or a phosphor which has been produced by means of the method according to the invention and / or a mixture of two or more thereof.
  • This is preferably a printing ink that can be used in inkjet printing machines or a steel engraving or offset printing ink.
  • the printing ink according to the invention contains conventional components.
  • the printing ink can be produced, for example, by mixing an extender, a wax, a phosphor according to the invention and other additives, such as, for example, a gloss agent, a leveling agent and / or an antioxidant, or mixtures of two or more thereof together with resinous components and a solvent, such as, for example Hydrocarbon or an aqueous medium.
  • additives such as, for example, a gloss agent, a leveling agent and / or an antioxidant, or mixtures of two or more thereof together with resinous components and a solvent, such as, for example Hydrocarbon or an aqueous medium.
  • the phosphor according to the invention is preferably used for applications on substrates. These applications can be done by various application methods, such as electrophoresis, photolithography, application in a binder or primer, but preferably by different printing techniques, such as, for example, by means of plan printing, steel engraving, offset printing or ink jet printing.
  • the invention further relates to an object which has at least one phosphor according to the invention or a mixture of two or more phosphors according to the invention.
  • the object is preferably a security document.
  • Security documents are understood to mean, for example, identity cards, passports, driving licenses or use or import permits, banknotes, shares or other securities, travel, flight or lottery tickets, credit cards or plastic check cards, travel or bank checks.
  • the object according to the invention can be authenticated by appropriate irradiation, ie as a function of the phosphor which the object comprises and the observation or the mechanical detection of the light emitted following the lighting. Phosphors which can be excited by UV light are preferably used. The emitted light to be observed then lies in the visible range.
  • the excitation of the phosphor can be done with known ones Irradiation facilities take place.
  • Phosphors are preferably used which can be excited by UV radiation in the wavelength ranges from approximately 200 nm to approximately 400 nm.
  • afterglow afterglow can also occur after removal of the excitation source.
  • the invention further relates to a luminescent fiber made from at least one fiber-forming material with at least one fine-grained inorganic phosphor pigment according to the invention distributed therein.
  • the incorporated phosphor pigments according to the invention preferably have an average particle size of less than 200 nm.
  • they when excited with UV radiation, they preferably show intense luminescence effects in the visible wavelength range, in particular a blue, green or orange luminescence.
  • the content of the phosphor pigments submitted according to the invention in the luminescent fibers can vary within a wide range and is expediently in an amount of 0.01 to 50% by weight, preferably more than 5% by weight up to 50% by weight. %, based on the anhydrous total fiber mass. Percentages of from 7 to 40, in particular from 10 to 20,% by weight, based on the anhydrous total fiber mass, are further preferred.
  • the fiber-forming material there is no particular restriction according to the invention, provided that the fiber-forming material is miscible with the phosphor pigments of the claimed particle size.
  • the following can be mentioned in particular as fiber-forming materials: viscose; Polyesters such as polyethylene terephthalate homo- and copolymers; Polyamides such as nylon-6 and nylon-6,6; Polyolefins such as polypropylene; Polyarylene ethers and polyarylene sulfides.
  • the fiber-forming material is preferably viscose, since luminescent fibers produced in this way Fibers with the usual paper raw materials based on cellulose are well tolerated and can be printed with various printing processes, such as offset, so that such fibers can be used without problems for the identification of papers, especially documents of value.
  • the methods according to the invention can also be used in the textile sector for the covert or open finishing of high-quality branded products.
  • the achievable intensive luminescence, combined with high light fastness, makes the luminescent fibers according to the invention particularly suitable for the security marking of any fiber-containing objects, especially textiles, papers and especially value documents.
  • the process for producing the luminescent fibers according to the invention is simple and only requires that the fine-grained inorganic phosphor pigment doped with the activator is added to the fiber-forming material or a solution thereof and fibers are spun therefrom.
  • the doped pigment viscose mass is added, from which fibers are spun by the viscose spinning process.
  • the doped pigments can also be added to a cellulose solution and fibers can be spun therefrom, for example using the cupro process, the lyocell process or a process using low-substituted cellulose ethers.
  • As a solvent for example, N-methylmo holinoxid / water can be used.
  • such viscose fibers can be used for the security marking of products, the proof of originality and for the control of automatic recognition processes of textiles, value documents and security papers in the broadest sense.
  • materials and security features that are very difficult to counterfeit and in combination with others Security features can be produced.
  • the corresponding security features depending on the security level, can only be clearly proven analytically with increased effort.
  • Luminescent fibers allow a localized, high signal intensity and thus a better signal-to-noise ratio in comparison to the areal application of corresponding phosphor pigments using conventional security printing technologies.
  • the long-term endeavor in the production of security features is the technical / scientific lead over the counterfeiter and the reduction in motivation for counterfeiting due to the complexity inherent in the security feature.
  • the fibers according to the invention offer great advantages in terms of simple, rapid, contactless and inexpensive control, machine readability, combinability with other effects, targeted excitation with different wavelengths and the different luminescent colors with excitation with different wavelengths.
  • the materials according to the invention are suitable for the production of non-copyable textiles, valuable documents and security papers, are well compatible with the raw materials based on cellulose and can be printed with various printing processes, in particular steel engraving and offset printing, so that the possibility of combining them with security printing inks or with other security features is given is.
  • the luminescent viscose fibers according to the invention with a phosphorescence effect can serve, for example, for the open security marking of products and the proof of their originality.
  • the fibers according to the invention with a phosphorescence effect offer great advantages in the simple, rapid, contactless and inexpensive control by everyone Individuals, since the necessary excitation of the phosphorescence effect is already possible with white daylight or artificial light, and a visual inspection in a darkened environment is sufficient to verify the security feature.
  • machine readability is also provided in a simple manner, the phosphorescence effect also permitting the spatial separation of the excitation location from the verification location.
  • the fibers according to the invention with fluorescence, but without a phosphorescence effect, also allow control by each individual, but the UV excitation required for detection already increases the degree of difficulty for detection and therefore represents a higher security level.
  • inorganic phosphors In addition to the very fine-grained inorganic phosphors according to the present invention, other phosphor pigments, such as. B. those that emit visible light with excitation with visible or ultraviolet radiation in the wavelength range from 200 to 700 nm after the end of the excitation with spectral components in the wavelength range from 380 to 700 nm, alkaline earth aluminates activated with europium and possibly with another rare Earth element as co-activator, in particular dysprosium, are used, alkaline earth aluminates according to EP-A 0 622 440 and US 5,376,303 being particularly preferred. Furthermore, such inorganic phosphor pigments can be used which have a fluorescence effect when excited with ultraviolet radiation.
  • inorganic phosphor pigments can be used which have a fluorescence effect when excited with ultraviolet radiation.
  • infrared-active pigments ie pigments which contain infrared-active phosphors with a luminescence process, on which at least partially long-wave infrared radiation with wavelengths above of 630 nm is used.
  • infrared-active pigments ie pigments which contain infrared-active phosphors with a luminescence process, on which at least partially long-wave infrared radiation with wavelengths above of 630 nm is used.
  • These include, in particular, anti-Stokes phosphors, as described, inter alia, in WO 98/39392.
  • infrared-active phosphors for the identification and counterfeit protection of documents of value represents an even higher security level, since the low signal intensity of infrared-active phosphor pigments increases the analytical effort for excitation and verification very clearly and already only makes the detection of corresponding security equipment more difficult.
  • the invention also relates to a method for identifying an object or a turf 'shaped article comprising at least one phosphor according to the invention and / or a mixture of two or more thereof, said method comprising the steps of at least: (i') irradiating the Object with a light that can be excited by the phosphor,
  • FIG. 1 shows the grain size distribution of the phosphors according to Examples 1 and 6 below.
  • the manufacturing conditions for a phosphor with an average particle size of less than 400 nanometers were examined in the ZnS: Cu system.
  • ZnS CuCl 2
  • melting agent such as NaCl or NH 4 CI
  • Examples 3 and 4 were prepared under the same reaction conditions as Examples 1 and 2, starting from a raw material mixture with different doping. Under UV excitation, orange-yellow fluorescent phosphors resulted, whose average grain sizes are less than 400 nanometers.
  • Example 5 was prepared under reaction conditions similar to Examples 1 to 4, starting from a raw material mixture with the activator Ag.
  • the result was a phosphor fluorescing blue under UV radiation with an average particle size of well below 400 nm.
  • the grain size shown in Table 1 and Fig. 1 was determined by means of laser dispersion analysis.
  • the fluorescence brightness of the phosphors produced by the process according to the invention is almost as high as the fluorescence brightness of the comparison materials from Examples 6 to 8, although the phosphors according to the invention from Examples 1 to 5 have an average grain size of less than 15% of the have average grain size of the comparison materials.
  • the phosphors according to the invention therefore offer the advantage of being able to be processed in applications which were previously not possible for inorganic phosphors and at the same time with good fluorescence brightness.

Landscapes

  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Organic Chemistry (AREA)
  • Inorganic Chemistry (AREA)
  • Textile Engineering (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • General Chemical & Material Sciences (AREA)
  • Manufacturing & Machinery (AREA)
  • Luminescent Compositions (AREA)
  • Artificial Filaments (AREA)
  • Woven Fabrics (AREA)
  • Paper (AREA)
  • Credit Cards Or The Like (AREA)
  • Investigating, Analyzing Materials By Fluorescence Or Luminescence (AREA)
  • Treatment Of Fiber Materials (AREA)
  • Pigments, Carbon Blacks, Or Wood Stains (AREA)

Abstract

La présente invention concerne: une substance minérale obtenue par synthèse en phase solide, ayant une taille de grain moyenne inférieure ou égale à 1000 nm, et un procédé de préparation d'une substance minérale ayant une taille de grain moyenne inférieure ou égale à 1000 nm; une encre d'imprimerie et un objet présentant chacun une substance luminescente de l'invention et/ou une substance luminescente préparée selon le procédé de l'invention et/ou un mélange des deux ou de plusieurs d'entre eux; un procédé d'identification d'un objet de l'invention présentant une substance luminescente de l'invention et/ou une substance luminescente préparée selon le procédé de l'invention et/ou un mélange des deux ou de plusieurs d'entre eux.
EP00926996A 1999-04-20 2000-04-19 Substances luminescentes minerales a grain tres fin Withdrawn EP1175469A2 (fr)

Applications Claiming Priority (5)

Application Number Priority Date Filing Date Title
DE19917887 1999-04-20
DE1999117887 DE19917887A1 (de) 1999-04-20 1999-04-20 Feinstkörnige anorganische Leuchtstoffe
DE19934436 1999-07-22
DE1999134436 DE19934436B4 (de) 1999-07-22 1999-07-22 Verwendung feinstkörniger anorganischer Leuchtstoffe
PCT/EP2000/003543 WO2000063317A2 (fr) 1999-04-20 2000-04-19 Substances luminescentes minerales a grain tres fin

Publications (1)

Publication Number Publication Date
EP1175469A2 true EP1175469A2 (fr) 2002-01-30

Family

ID=26052996

Family Applications (1)

Application Number Title Priority Date Filing Date
EP00926996A Withdrawn EP1175469A2 (fr) 1999-04-20 2000-04-19 Substances luminescentes minerales a grain tres fin

Country Status (4)

Country Link
EP (1) EP1175469A2 (fr)
JP (1) JP2002542373A (fr)
AU (1) AU4553000A (fr)
WO (1) WO2000063317A2 (fr)

Families Citing this family (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US6749773B2 (en) * 2001-04-03 2004-06-15 Hewlett-Packard Development Company, L.P. Phosphorescent ink for use in an ink-jet printer
AU2002366253B2 (en) * 2001-12-18 2007-06-14 Centrum Fur Angewandte Nanotechnologie (Can) Gmbh Security printing liquid and method using nanoparticles
JP4594926B2 (ja) * 2003-02-18 2010-12-08 テクスティルフォーシュンクスイスティチュート ツーリンゲン−フォークトランド エー．ファウ． 複数の導電性繊維又は導電性を有する繊維の配列からなるテキスタイルの表面の構造及びその製造方法
JP2005158551A (ja) * 2003-11-27 2005-06-16 Sumitomo Electric Ind Ltd Ｅｌファイバー及び光触媒反応容器
WO2006119561A1 (fr) * 2005-05-10 2006-11-16 Commonwealth Scientific And Industrial Research Organisation Suivi haute resolution de materiaux utilises dans des processus industriels en incorporant sous forme de traces des marqueurs luminescents
DE102011102428A1 (de) * 2011-05-24 2012-11-29 Glanzstoff Bohemia S.R.O. Lumineszierende cellulosische Regeneratfaser und Verfahren zu deren Herstellung
DE102014018586A1 (de) * 2014-12-17 2016-06-23 Merck Patent Gmbh Lasermarkierbare und laserschweißbare polymere Materialien
KR102081824B1 (ko) * 2018-08-06 2020-02-26 심동훈 침입자의 흔적 확인 또는 야간 피아식별을 위한 형광물질 페이스트의 제조방법 및 이를 이용한 형광물질 스프레이 장치

Family Cites Families (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH0745655B2 (ja) * 1985-11-07 1995-05-17 化成オプトニクス株式会社 蛍光体の製造方法
JPS6366282A (ja) * 1986-09-05 1988-03-24 Res Dev Corp Of Japan 超微粒子蛍光体
DE19539315A1 (de) * 1995-10-23 1997-04-24 Hoechst Ag UV-aktive Regeneratcellulosefasern
US5985173A (en) * 1997-11-18 1999-11-16 Gray; Henry F. Phosphors having a semiconductor host surrounded by a shell
DE19802588A1 (de) * 1998-01-23 1999-07-29 Riedel De Haen Ag Lumineszierende Fasern, Verfahren zu deren Herstellung und deren Verwendung

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
See references of WO0063317A3 *

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