EP3841181A2 - Procédé d'activation et de désactivation de la phosphorescence d'une structure, procédé de fabrication d'une structure phosphorescente et structure phosphorescente, étiquette comprenant une structure phosphorescente, procédé de description, de lecture et de suppression d'une étiquette, ainsi que capteur uv - Google Patents

Procédé d'activation et de désactivation de la phosphorescence d'une structure, procédé de fabrication d'une structure phosphorescente et structure phosphorescente, étiquette comprenant une structure phosphorescente, procédé de description, de lecture et de suppression d'une étiquette, ainsi que capteur uv

Info

Publication number
EP3841181A2
EP3841181A2 EP19759343.7A EP19759343A EP3841181A2 EP 3841181 A2 EP3841181 A2 EP 3841181A2 EP 19759343 A EP19759343 A EP 19759343A EP 3841181 A2 EP3841181 A2 EP 3841181A2
Authority
EP
European Patent Office
Prior art keywords
oxygen
light
phosphor
sensor
characteristic
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.)
Pending
Application number
EP19759343.7A
Other languages
German (de)
English (en)
Inventor
Max GMELCH
Heidi THOMAS
Sebastian Reineke
Felix Simon Fries
Paul-Anton WILL
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.)
Technische Universitaet Dresden
Original Assignee
Technische Universitaet Dresden
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 DE102018214374.9A external-priority patent/DE102018214374A1/de
Priority claimed from DE102018214375.7A external-priority patent/DE102018214375B4/de
Application filed by Technische Universitaet Dresden filed Critical Technische Universitaet Dresden
Publication of EP3841181A2 publication Critical patent/EP3841181A2/fr
Pending legal-status Critical Current

Links

Classifications

    • 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
    • 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
    • C09K11/06—Luminescent, e.g. electroluminescent, chemiluminescent materials containing organic luminescent materials
    • C09K11/07—Luminescent, e.g. electroluminescent, chemiluminescent materials containing organic luminescent materials having chemically interreactive components, e.g. reactive chemiluminescent compositions
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J7/00—Adhesives in the form of films or foils
    • C09J7/20—Adhesives in the form of films or foils characterised by their carriers
    • F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
    • F21—LIGHTING
    • F21K—NON-ELECTRIC LIGHT SOURCES USING LUMINESCENCE; LIGHT SOURCES USING ELECTROCHEMILUMINESCENCE; LIGHT SOURCES USING CHARGES OF COMBUSTIBLE MATERIAL; LIGHT SOURCES USING SEMICONDUCTOR DEVICES AS LIGHT-GENERATING ELEMENTS; LIGHT SOURCES NOT OTHERWISE PROVIDED FOR
    • F21K2/00—Non-electric light sources using luminescence; Light sources using electrochemiluminescence
    • G—PHYSICS
    • G01—MEASURING; TESTING
    • G01J—MEASUREMENT OF INTENSITY, VELOCITY, SPECTRAL CONTENT, POLARISATION, PHASE OR PULSE CHARACTERISTICS OF INFRARED, VISIBLE OR ULTRAVIOLET LIGHT; COLORIMETRY; RADIATION PYROMETRY
    • G01J1/00—Photometry, e.g. photographic exposure meter
    • G01J1/42—Photometry, e.g. photographic exposure meter using electric radiation detectors
    • G01J1/429—Photometry, e.g. photographic exposure meter using electric radiation detectors applied to measurement of ultraviolet light
    • 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
    • G06K19/06009—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 with optically detectable marking
    • G06K19/06046—Constructional details
    • G06K19/0614—Constructional details the marking being selective to wavelength, e.g. color barcode or barcodes only visible under UV or IR
    • 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
    • G06K19/06009—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 with optically detectable marking
    • G06K19/06046—Constructional details
    • G06K19/0615—Constructional details the marking being of the rewritable type, e.g. thermo-chromic barcodes
    • 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
    • C09K2211/00—Chemical nature of organic luminescent or tenebrescent compounds
    • C09K2211/10—Non-macromolecular compounds
    • C09K2211/1018—Heterocyclic compounds
    • C09K2211/1022—Heterocyclic compounds bridged by heteroatoms, e.g. N, P, Si or B

Definitions

  • Method for activating and deactivating the phosphorescence of a structure method for producing a phosphorescent structure and phosphorescent structure, label with a phosphorescent structure, method for writing on, reading out and
  • the invention is based on a method for producing phosphorescence.
  • Phosphorescence has been known for a long time and is the property of a substance that afterglow with light continues to shine for a longer period of time.
  • the long afterglow of the phosphorescence distinguishes it from the fluorescence, which can no longer be perceived very quickly when the radiation is switched off.
  • Phosphorescence and fluorescence result from the fact that a substance is excited by incident light and electrons of the substance from a low energy level
  • transitions between energy levels follow certain selection rules. There are transitions with high transition probabilities that occur quickly and there are transitions with low transition probabilities that occur slowly.
  • inorganic phosphorescent substances such as Europium-doped SrALCL
  • organic phosphorescent substances are powdery substances, difficult to process or require rare earths and are therefore expensive.
  • the organic phosphorescent substances are easier to use and also cheaper.
  • the ground state is usually a singlet state in which all
  • Electrons are paired.
  • a phosphorescent transition in organic substances is, for example, the transition from an excited triplet state to the ground state. This transition is “forbidden” in quantum mechanics and therefore with less
  • Oxygen which is usually in a triplet state, interacts with the electrons in the excited triplet state and thus quickly depopulates it. So there is no long-lasting afterglow.
  • phosphorescent substances are usually produced under vacuum or in an inert gas and provided with an oxygen barrier.
  • these procedures are cumbersome and expensive.
  • Another approach is to deactivate the oxygen in the phosphorescent substance. This is attempted with UV light and solutions or gels containing heavy metals, but is far from being technically feasible and, because of its toxicity, is not a good alternative for applications that are mostly in the area of possible direct contact with people, such as toys.
  • Deactivating the phosphorescence of a structure to provide a method for producing a phosphorescent structure and a phosphorescent structure which are inexpensive, readily available and simple to manufacture.
  • the object is achieved by a method according to claim 1 and by the method of claim 2.
  • the object of the present invention is further achieved by a method for activating and deactivating the phosphorescence of a structure, the structure being illuminated in a first activation step for photochemically deactivating oxygen in the structure with light having a first characteristic and in a second activation step for Initiate the phosphorescence, the structure is illuminated with light of a second characteristic, being used for deactivation in one
  • Deactivation step oxygen is introduced into the structure.
  • the phosphorescence of the structure is deactivated in the deactivation step by introducing oxygen.
  • the terms irradiate light, irradiate light, illuminate with light and illuminate with light and the terms irradiate, irradiate and illuminate synonyms.
  • machine-readable code such as bar code or QR code.
  • the first material has a first organic material and / or the second material has a second organic material.
  • the first material is preferably a first organic material and / or the second material is a second organic material.
  • the first material has a first organic material which can be oxidized by singlet oxygen.
  • the first material is particularly preferably a first organic material.
  • the first organic material is preferably able to form a chemical compound with singlet oxygen.
  • the first material has a polymer, preferably an organic polymer.
  • the first material is particularly preferably a, in particular organic, polymer.
  • the first material is preferably transparent and can be processed by wet processing.
  • the first material has, for example, polymethyl methacrylate (PMMA), polystyrene (PS) and / or cycloolefin copolymers (COC).
  • the second material has a second organic material, preferably an organic polymer.
  • the second material is preferably an organic polymer.
  • the second material preferably has a second organic material that is oxygen impermeable at ambient temperature.
  • the second material is preferably transparent and can be processed, for example, by wet processing.
  • the second material is particularly preferably a second organic material which can be processed in combination with the first material. The second material points
  • the phosphor is admixed with the first, in particular organic, material, for example the phosphor and the first, in particular organic, material form a host-guest complex, the first, in particular organic, material forming the host ( engl host) and the phosphor acts as a guest.
  • Oxygen in particular molecular oxygen, ie O2, is present in the region of the phosphor.
  • the oxygen in particular the molecular oxygen, is preferred in the non-irradiated and / or non-heated state, ie for example in the case of a
  • Ambient temperature not bound to the phosphor and / or to the first, in particular organic, material.
  • the phosphor is an organic phosphor, which can be excited to phosphorescence particularly preferably at an ambient temperature.
  • the phosphor is preferably an organic phosphor, the phosphorescence of which is prevented by oxygen.
  • the phosphor is particularly preferably an organic phosphor that can be processed by wet processing.
  • the ambient temperature denotes the temperature of the medium surrounding the structure during activation and / or deactivation, e.g. Air in which the second, in particular organic, material is impermeable to oxygen.
  • the ambient temperature is room temperature, i.e. 293 K.
  • the second, in particular organic, material advantageously prevents oxygen from penetrating to the first, in particular organic, material and / or the phosphor admixed with it.
  • oxygen in particular molecular oxygen, is introduced into the structure in the deactivation step.
  • the oxygen preferably penetrates to the first, in particular organic, material and / or the phosphor and prevents phosphorescence.
  • the heat, and / or the light having a third characteristic converts the second, in particular organic, material from an oxygen-impermeable state to an oxygen-permeable state, so that oxygen is transferred to the first, in particular organic, material and / or the phosphor penetrates and prevents phosphorescence.
  • Molecular oxygen preferably diffuses through the oxygen-permeable second, in particular organic, material.
  • infrared light IR light
  • light from the third characteristic is preferably introduced into the structure, the heat converting the second, in particular organic, material from an oxygen-impermeable state to an oxygen-permeable state.
  • the second, in particular organic, material is photochemically processed by one
  • Heating the structure produces a much faster introduction of oxygen.
  • Illuminating the structure with light of the third characteristic is an advantageously elegant and simple technical realization of heating the structure.
  • light with a first intensity is used as light of the first characteristic, the light of the first characteristic having a wavelength of less than 700 nm, preferably less than 550 nm, particularly preferably less than 460 nm, preferably using the light of the first characteristic with a second intensity as the light of the second characteristic.
  • the light of the first characteristic thus has a first intensity and the light of the second characteristic has a second intensity, the second intensity preferably being different from the first intensity.
  • the light of the first characteristic and the light of the second characteristic differ only in their intensity.
  • the light of the first characteristic is preferably UV light, for example UV light with a wavelength of approximately 365 nm.
  • the light of the second characteristic is therefore the light of the first characteristic with a second intensity.
  • the light of the first characteristic then has a first intensity.
  • the first intensity is higher than the second intensity. It is conceivable that the first intensity is 10 times to 100 times greater, preferably 20 times to 90 times greater, particularly preferably 50 times to 80 times greater and in particular approximately 70 times greater than the second intensity. It is conceivable that the first intensity between 1 mWcnr 2 and
  • the second intensity is between 0.01 mWcnr 2 and 1 mWcnr 2 , preferably between 0.05 mWcnr 2 and 0.5 mWcnr 2 and in particular approximately 0.1 mWcnr 2 .
  • Intensity that is to say to generate the attenuation of the light intensity, one or more filters and / or two polarizers and / or one or more beam splitters are used.
  • the oxygen is bound in a binding step to a first, in particular organic, material, before
  • Binding step preferably the oxygen in a triplet-triplet interaction with a phosphor mixed with the first, in particular organic, material from a triplet ground state of the oxygen to an excited singlet state of the
  • the oxygen is usually in a triplet ground state of the oxygen.
  • the oxygen is preferably in a triplet-triplet interaction with the phosphor from the triplet ground state of the
  • Oxygen converted into an excited singlet state of oxygen is highly reactive.
  • the oxygen can be bound in the binding step by oxidation of the first, in particular organic, material. It is conceivable that the phosphor is a doping of the first, in particular organic, material.
  • the phosphor prior to the triplet-triplet interaction, changes from the light of the first characteristic from a singlet state of the phosphor to an excited one Is transferred to the singlet state of the phosphor and then by intercombination from the excited singlet state of the phosphor to a triplet state of the phosphor, preferably in the second activation step converting the phosphor from a singlet state of the phosphor to an excited triplet state of the phosphor becomes.
  • the phosphor is preferably organic.
  • the phosphor is usually in an unexcited singlet state, preferably the singlet ground state.
  • the light of the first characteristic converts the phosphor into an excited singlet state of the phosphor, from which the phosphor can transition through an combination into an excited triplet state of the phosphor, which is then available for a triplet-triplet interaction with the oxygen.
  • heat is introduced into the structure by the light of the third characteristic in the deactivation step, preferably a second, in particular organic, material from an oxygen-impermeable state to one by the heat
  • the second, in particular organic, material forms an oxygen barrier which keeps oxygen away from the first, in particular organic, material and thus enables the unbound oxygen to be reduced in the first activation step by oxidation of the first, in particular organic, material .
  • the third light i.e. the light of the third characteristic, preferably IR light
  • the first, in particular organic, material is heated and this heat to the second, in particular
  • the second, in particular organic, material contains ethylene-vinyl alcohol copolymers (EVOH) and / or polyvinyl alcohol (PVA).
  • EVOH ethylene-vinyl alcohol copolymers
  • PVA polyvinyl alcohol
  • the second, in particular organic, material preferably has only EVOH or PVA apart from impurities which may be caused by production technology.
  • the first, in particular organic, material is a long-chain material organic polymer, preferably polymethyl methacrylate (PMMA), polystyrene (PS) and / or cycloolefin copolymers (COC), is used, the first, in particular organic, material preferably having the phosphor as doping and / or as a secondary chain. That is, the first material has an organic material.
  • the first material preferably has a long-chain organic polymer.
  • the first material particularly preferably has PMMA, PS and / or COC.
  • the first material is particularly preferably an organic material and has only a long-chain polymer, in particular PMMA, PS or COC.
  • PMMA, PS or COC preferably forms a guest-host complex with the phosphor.
  • PMMA, PS and COC are cheap, robust and very easy to process.
  • PMMA, PS and COC are optically transparent, essentially non-toxic and advantageously suitable for binding and thus deactivating oxygen in the first activation step.
  • N, N'-di (1-naphthyl) -N, N'-diphenyl- (1, 1'-biphenyl) -4,4'-diamine NB
  • Tetra-N-phenylbensidine TPB
  • PhenDPA Tetra-N-phenylbensidine
  • PhenTPA Tetra-N-phenylbensidine
  • TA Thianthrene
  • BP-TA Benzophenone-Thianthrene
  • Br-BP-TA Brom-Benzophenone-Thianthrene
  • Br-BP-TA Benzophenone-2-Thianthrene
  • DPS-TA diphenylsulfone thianthrene
  • Diphenylsulfone-2-thianthrene (DPS-2TA), bromo-diphenylsulfone-thianthrene (Br-DPS-TA), difluoroborone-9-hydroxyphenalenone (BF2 (HPhN)) and / or difluoroborone-6-hydroxybenz [de] anthracene-7- on (BF2 (HBAN)) can be used.
  • NPB is in the
  • the phosphor preferably has NPB, PhenDPA, PhenTPA, TA, BP-TA, Br-BP-TA, BP-2TA, DPS-TA, DPS-2TA, Br-DPS-TA, BF2 (HPhN) and / or BF2 (HBAN ) on.
  • the phosphor particularly preferably has
  • the phosphor is preferably selected from the group of the following compounds: wherein R 1 , R 2 and R 3 are identical or different from one another. Furthermore:
  • R 1 is a substituted or unsubstituted aryl or a substituted or
  • R 2 is a substituted or unsubstituted aryl or a substituted or
  • R 3 is a substituted or unsubstituted alkyl or a substituted or
  • R 3 is selected from the group H, OR 4 or N0 2 ;
  • R 4 is H or a (Ci - Cs) alkyl;
  • R 5 is either H, a halogen or a thianthrene;
  • X is P or N;
  • Y 1 , Y 2 , Y 3 and Y 4 are each independently selected from C or N, with either two or four of Y 1 , Y 2 , Y 3 and Y 4 being N.
  • Z 1 and Z 2 are preferably chosen independently of one another.
  • Z 1 is either an enol or sulfoxide.
  • Z 2 is absent or a hetero atom or selected from the group consisting of -NR 4 .
  • Z 3 is selected from the group consisting of -NR 4 or -CR 4 R 4 .
  • the structure is partially covered with a mask in the first activation step and / or the structure is only partially illuminated with the first light in the first activation step by a locally meandering or line-wise scanning light beam and / or the structure is only partially illuminated in the first activation step in that the structure is illuminated with a light beam with a steel profile.
  • Intensity of the light beam incident on the surface of the structure varies so much locally that the intensity of the light steel at locations with high intensity above a threshold value for carrying out a reaction and at locations with low intensity below this
  • Threshold is.
  • the reaction can be, for example, the conversion of the phosphor from the singlet state of the phosphor to the excited singlet state of the phosphor or the heating up to the transfer of the second, in particular organic, material from the oxygen-impermeable state to the oxygen-permeable state.
  • This enables the targeted partial activation of the phosphorescence of the structure and thus the creation of geometric phosphorescent patterns.
  • This makes it possible, for example, to store information in the form of fonts, images, logos, codes, pictograms, machine-readable fonts, bar codes, GR codes or the like on the structure. Due to the possibility of repeated activation, deactivation and reactivation of the phosphorescence, the structure can be rewritten several times.
  • the structure in the deactivation step is partially covered with a mask and / or the structure in the deactivation step is only partially illuminated with the light of the third characteristic by a locally meandering or line-wise scanning light beam and / or the structure in the deactivation step is thereby only partially is illuminated that the structure is illuminated with a light beam with a steel profile.
  • Another object of the present invention is a structure for use in a method according to any one of claims 1 to 12, wherein the structure comprises a first and a second material, wherein the first material is mixed with a phosphor and in the non-irradiated and / or not heated State oxygen is present in the area of the phosphor and the second material is at an ambient temperature
  • the first material is oxygen impermeable and, in the oxygen impermeable state, acts as an oxygen barrier between the first material and an environment of the structure.
  • the first material preferably has a first organic material and / or the second material second organic material.
  • the first material is particularly preferably a first organic material and the second material is a second organic material.
  • the first, in particular organic, material is preferably different from the second, in particular organic, material.
  • the first, especially organic, material forms with the
  • Phosphor for example, a guest-host complex, wherein the first, in particular organic, material forms the host and the phosphor forms the guest.
  • the second, in particular organic, material functions at an ambient temperature, for example
  • Room temperature i.e. 293 K, as an oxygen barrier and prevents oxygen from penetrating to the first, in particular organic, material and thus also to the phosphor. This prevents oxygen from preventing phosphorescence.
  • the first material has a first organic material which can be oxidized by singlet oxygen.
  • the first material is particularly preferably a first organic material.
  • the first organic material is preferably able to form a chemical compound with singlet oxygen.
  • the first material has a polymer, preferably an organic polymer.
  • the first material is particularly preferably a, in particular organic, polymer.
  • the first material is preferably transparent and can be processed by wet processing.
  • the first material has, for example, polymethyl methacrylate (PMMA), polystyrene (PS) and / or cycloolefin copolymers (COC).
  • the second material has a second organic material, preferably an organic polymer.
  • the second material is preferably an organic polymer.
  • the second material preferably has a second organic material that is oxygen impermeable at ambient temperature.
  • the second material is preferably transparent and can be processed, for example, by wet processing.
  • the second material is particularly preferably a second organic material which can be processed in combination with the first material. The second material points
  • PVA polyvinyl alcohol
  • EVOH ethylene-vinyl alcohol copolymers
  • the phosphor is an organic phosphor, which can be excited to phosphorescence particularly preferably at an ambient temperature.
  • the phosphor is preferably an organic phosphor, the phosphorescence of which is prevented by oxygen.
  • the phosphor is particularly preferably an organic phosphor that can be processed by wet processing.
  • the phosphor preferably has N PB, PhenDPA, PhenTPA, TA, BP-TA, Br-BP-TA, BP-2TA, DPS-TA, DPS-2TA, Br-DPS-TA, BF2 (HPhN) and / or BF2 (HBAN).
  • the phosphor particularly preferably has exclusively NPB, PhenDPA, PhenTPA, TA, BP-TA, Br-BP-TA, BP-2TA, DPS-TA, DPS-2TA, Br-DPS-TA, BF 2 (HPhN) or BF 2 (HBAN) on.
  • the phosphor particularly preferably has at least one of the following compounds:
  • R 1 , R 2 and R 3 are identical or different from one another. Furthermore:
  • R 1 is a substituted or unsubstituted aryl or a substituted or
  • R 2 is a substituted or unsubstituted aryl or a substituted or
  • R 3 is a substituted or unsubstituted alkyl or a substituted or
  • R 3 is selected from the group H, OR 4 or N0 2 ;
  • R 4 is H or a (Ci - Cs) alkyl;
  • R 5 is either H, a halogen or a thianthrene;
  • X is P or N;
  • Y 1 , Y 2 , Y 3 and Y 4 are each independently selected from C or N, with either two or four of Y 1 , Y 2 , Y 3 and Y 4 being N.
  • Z 1 and Z 2 are preferably chosen independently of one another.
  • Z 1 is either an enol or sulfoxide.
  • Z 2 is absent or a hetero atom or selected from the group consisting of -NR 4 .
  • Z 3 is selected from the group consisting of -NR 4 or -CR 4 R 4 .
  • the second, in particular organic, material can be converted from an oxygen-impermeable to an oxygen-permeable state by supplying heat and / or light.
  • the conversion from the oxygen-impermeable to the oxygen-permeable state is preferably carried out thermally and / or photochemically.
  • the structure has a substrate.
  • the substrate has, for example, the second, in particular organic, material.
  • the substrate is preferably transparent.
  • the substrate has a, in particular transparent, film or a glass plate.
  • the substrate is preferably provided with an adhesive and / or magnetic underside.
  • the substrate has a self-adhesive and / or magnetic film.
  • the structure can thus be attached easily and, in the case of the magnetic film, reversibly.
  • the substrate is a preferably transparent plate.
  • the substrate is a glass or plastic pane.
  • the substrate is flexible.
  • the substrate is a film, a rubberized structure or a rubber.
  • the structure has a first layer with a first layer thickness of the first, in particular organic, material and / or at least a second layer with a second layer thickness of the second, in particular organic, material, the first layer being between the Substrate and the at least second layer is arranged.
  • the structure preferably has exactly one second layer.
  • the structure has a plurality of, for example two, second layers.
  • the quality of the oxygen barrier can be determined by the number of layers. In particular, the oxygen impermeability increases
  • the first layer thickness is, for example, 200 nm to 2000 nm, preferably 900 nm.
  • the at least second layer thickness is, for example, between 800 nm and 30 pm or between 500 nm and 50 pm.
  • the sum of the thicknesses of the second is preferably
  • the first, in particular organic, material and the second, in particular organic, material are applied as a mixture to the substrate.
  • the first, in particular organic, material preferably has PMMA, PS and / or COC, in particular the first material is an organic material and only has PMMA, PS or COC.
  • the second, in particular organic, material preferably has EVOH and / or PVA, in particular the second material is an organic material and exclusively has EVOH or PVA.
  • Another object of the present invention is a method for producing a structure according to one of claims 14 to 27, wherein on a substrate a first,
  • the production method is suitable for producing a structure in which phosphorescence can be activated and deactivated.
  • the phosphorescence can be activated and deactivated.
  • the manufacturing process is very simple to carry out and advantageously does not require the absence of oxygen.
  • the method for manufacturing can thus be carried out outside of vacuum chambers or chambers flooded with inert gas.
  • the second, in particular organic, material is used as the substrate. It is also conceivable that glass, metal or plastic is used as the substrate.
  • the first, in particular organic, material by means of spin coating and / or line application methods and / or pipetting and / or printing methods and / or
  • Spraying method in particular as a first layer, is applied to the substrate and / or the second, in particular organic, material is applied by means of spin coating and / or line application processes and / or pipetting and / or printing processes and / or spray processes, in particular as at least one second layer.
  • the first, in particular organic, material and the second, in particular organic, material preferably each form a layer.
  • the first, in particular organic, material is NPMA doped with NPB.
  • PMMA and NPB form a guest-host complex, with PMMA acting as the host and NPB as the guest.
  • the first, in particular organic, material for application is dissolved in an organic solvent.
  • the first, in particular organic, material is dissolved in anisole, chlorobenzene, water or ethyl lactate.
  • the second, in particular organic, material is also dissolved in an organic solvent for application. It is conceivable that the second, in particular organic, material is dissolved in anisole, chlorobenzene, water or ethyl lactate.
  • the first, in particular organic, material and / or the second, in particular organic, material are preferably dried after the application. This allows the solvent to be evaporated in a controlled manner. It is conceivable that this takes place in an oven or on a hot plate.
  • first, in particular organic, material and the second, in particular organic, material are applied as a mixture. This means that no oxygen-impermeable substrate is necessary.
  • a solid substrate or a film is used as the substrate, preferably a solid substrate with a self-adhesive backing facing away from the first, in particular organic, material or a film with a self-adhesive backing from the first, in particular organic, material-facing back is used.
  • Another object of the invention is a label having a functional layer, the functional layer having a structure according to one of claims 13 to 29.
  • the label according to the invention can be described and erased several times.
  • Descriptions are preferably carried out by irradiation with light of the first characteristic.
  • oxygen present in the region of the first, in particular organic material, in particular in the region of the phosphor is preferably converted into an excited singlet state and is reacted with the second, in particular organic, material.
  • the oxygen can therefore be any suitable oxygen present in the region of the first, in particular organic material, in particular in the region of the phosphor.
  • the label can preferably be read out by irradiation with light having a second characteristic.
  • the light of the second characteristic stimulates the phosphor to phosphorescence.
  • the label can be erased by introducing heat and / or radiation of light with a third characteristic, in particular IR light.
  • the introduction of heat and / or the irradiation of light of the third characteristic converts the second, in particular organic, material from an oxygen-impermeable to an oxygen-permeable state. Oxygen can penetrate from the environment to the first, in particular organic, material and in particular to the phosphor and the phosphorescence
  • the label has a substrate. It is also conceivable that the functional layer is arranged on the substrate. It is also conceivable that the substrate is arranged in one plane. However, it is also conceivable that the substrate is arranged in a non-flat surface. For this purpose, the substrate has a non-constant geometric profile. It is conceivable that the functional structure has the same geometric profile as the substrate. It is also conceivable that the substrate is impermeable to oxygen.
  • the functional layer has a first, in particular organic, material and a second, in particular organic, material, a phosphor for phosphorescence being added to the first, in particular organic, material, and the second, especially organic material at room temperature in an oxygen impermeable state.
  • the first, in particular organic, material is arranged in a lower layer and the second, in particular organic, material in an upper layer is arranged, wherein the lower layer is arranged between a substrate and the upper layer.
  • the lower layer preferably has a layer thickness between 200 nm and 2000 nm, preferably between 500 nm and 1500 nm, in particular of approximately 900 nm, and / or the upper layer has a layer thickness of between 500 nm and 50 pm.
  • the substrate is made from the second, in particular organic, material.
  • first, in particular organic, material and the second, in particular organic, material are a mixture.
  • the functional layer can be converted from the non-phosphorescent state into the phosphorescent state by the incidence of light of a first characteristic and / or by the incidence of light of a second characteristic can be transferred to the functional layer from the phosphorescent state to the non-phosphorescent state and / or can be converted from the phosphorescent state to the non-phosphorescent state by the introduction of heat into the functional layer.
  • the light of the first characteristic is also suitable for exciting phosphorescence.
  • the light of the first characteristic has a wavelength of less than 700 nm, preferably less than 550 nm, particularly preferably less than 460 nm.
  • the light of the second characteristic is preferably IR light.
  • Phosphorescence is the light of the first characteristic with a second intensity.
  • the light of the first characteristic then has a first intensity.
  • the first is intensity higher than the second intensity.
  • the first intensity is 10 times to 100 times greater, preferably 20 times to 90 times greater, particularly preferably 50 times to 80 times greater and in particular approximately 70 times greater than the second intensity.
  • the first intensity is between 1 mWcnr 2 and 20 mWcnr 2 , preferably between 3 mWcnr 2 and 15 mWcnr 2 , particularly preferably between 5 mWcnr 2 and 10 mWcnr 2 and
  • the second intensity between 0.01 mWcnr 2 and 1 mWcnr 2 , preferably between 0.05 mWcnr 2 and
  • the first, in particular organic, material is configured for binding oxygen by the incidence of light of the first characteristic. This enables the removal of oxygen from the functional layer and thus enables the
  • the second, in particular organic, material is provided by the incidence of light of the second characteristic and / or the introduction of heat into one
  • oxygen-permeable state is convertible. It is thus advantageously possible
  • the functional layer is configured such that when light of the second characteristic is incident, the first, in particular organic, material is heated and the heat is transported to the second, in particular organic, material. It is also conceivable that the second, in particular organic, material can be converted into an oxygen-permeable state by this heating.
  • the first, in particular organic, material is PMMA, PS and / or COC and / or the second, in particular organic, material contains EVOH and / or PVA and / or the phosphor NPB, PhenDPA, PhenTPA, TA, BP-TA, Br-BP-TA, BP-2TA, DPS-TA, DPS-2TA, Br-DPS-TA, BF2 (HPhN) and / or BF2 (HBAN).
  • the phosphor particularly preferably has exclusively NPB, PhenDPA, PhenTPA, TA, BP-TA, Br-BP-TA, BP-2TA, DPS-TA, DPS-2TA, Br-DPS-TA, BF2 (HPhN) or BF2 (HBAN ) is. These materials are widely used, easy to process and inexpensive.
  • NPB NPB
  • PhenDPA PhenTPA
  • TA TA
  • BP-TA Br-BP-TA
  • BP-2TA Br-BP-TA
  • BP-2TA Br-BP-TA
  • DPS-TA DPS-2TA
  • Br-DPS-TA Br-DPS-TA
  • BF2 HPhN
  • HBAN BF2
  • the substrate is a film, the side of the substrate facing away from the functional layer preferably being self-adhesive or magnetic. This advantageously enables the label to be easily applied to the label to be labeled
  • a film is flexible. This means that the label can also be applied to uneven objects.
  • the film is transparent. This enables a completely unobtrusive appearance of the label.
  • the label can be attached to window panes or screens, for example, and does not affect their function. This is particularly advantageous in the case of objects to be labeled that offer hardly any surface that is not optically functional.
  • the substrate is a plastic plate, preferably a transparent plastic plate, or a metal plate, the side of the substrate facing away from the functional layer preferably being self-adhesive or magnetic. This advantageously enables mechanical protection of the functional layer.
  • Another object of the present invention is a method for writing on a label according to claim 30, wherein for writing on the label in one
  • Points of the functional layer are selectively transferred from the non-phosphorescent state to the phosphorescent state locally in a contactless manner, the points forming a phosphorescent region, the phosphorescent region being irradiated with light of a first characteristic during the writing process, the Oxygen present in the area of the phosphor is bound to the first, in particular organic, material.
  • point means a locally extended location in the functional layer.
  • the sum of all points is the functional layer.
  • selectively transferable locally means that the points can be transferred individually in a targeted manner. This means that one point can be transferred without another point being transferred.
  • the phosphorescent region denotes a region suitable for phosphorescence.
  • oxygen present in the phosphorescent region only in the excited singlet state. The selective irradiation of partial areas of the label prevents oxygen from suppressing the phosphorescence only in these areas and thus only provides a structure in these areas which can be excited to phosphorescence by irradiation with light.
  • the phosphorescent area is preferably irradiated with light of the first characteristic, the functional layer being partially covered with a mask such that only the phosphorescent area is illuminated and / or the functional layer with light of the first characteristic from a locally meandering area or line-by-line rasterizing light beam is irradiated only in the phosphorescent area and / or the functional layer is illuminated only in the phosphorescent area, in that the functional layer is illuminated with a light beam with a beam profile, the beam profile on the functional layer corresponding to the phosphorescent area.
  • the label can be written quickly and reliably with a code or other characters.
  • the sign with which the label was written is not visible to the naked eye.
  • the label is barely perceptible to the naked eye.
  • the label described is preferably transparent.
  • a label is therefore advantageously provided which is also suitable for use in exposed areas, for example also on transparent objects such as a glass bottle or a window. It is therefore not necessary to affix labels to the inside or to other, non-directly visible locations of a product.
  • the label can be attached to the outside of the goods in an easy-to-read location and yet remains almost invisible to traffic. The look of the product is not compromised by the label. This simplifies, for example, the picking, packaging and logistics of goods.
  • the label is preferably read out by irradiating the label with light having a second characteristic.
  • the light of the second characteristic preferably differs from the light of the first characteristic only in intensity.
  • the phosphor is excited to phosphorescence in the areas previously irradiated with light of the first characteristic.
  • Another object of the present invention is a method for deleting a label according to claim 30, wherein for deleting the label in a deletion process, the functional layer is essentially completely converted into the non-phosphorescent state, heat being introduced into the functional layer during the deletion process is and / or the functional layer is irradiated with light of a second characteristic, the second material being converted from an oxygen-impermeable state to an oxygen-permeable state by the heat and / or by the irradiation with the light of the second characteristic. Oxygen present in the environment can thus penetrate to the phosphor and prevent phosphorescence.
  • the heat is preferred by irradiation with light of the second characteristic
  • Another object of the present invention is a method for writing and erasing a label according to claim 30, wherein the label is described in a writing method according to one of claims 31 to 33 and in a subsequent one
  • Deletion method according to one of claims 34 to 36 is deleted.
  • the label is preferably written in a writing process according to one of claims 31 to 33, erased in a subsequent erasing process according to one of claims 34 to 36 and rewritten in a writing process following the erasing process according to one of claims 31 to 33.
  • points of the functional layer are selectively transferred locally from the non-phosphorescent state to the phosphorescent state in a writing process in order to write the label in a contactless manner, the points forming a phosphorescent area for erasing the label in a deletion process the functional layer is essentially completely converted into the non-phosphorescent state and the writing process is carried out to rewrite the label.
  • the phosphorescent area is illuminated with light of the first characteristic during the writing process, the functional layer preferably being partially so a mask is covered that only the phosphorescent area is illuminated and / or the functional layer is illuminated with light of the first characteristic by a locally meandering or line-by-line rastering light beam only in the phosphorescent area and / or the functional layer is thereby illuminated only in the phosphorescent area that the functional layer with a light beam with a
  • UV light is used as the light of the first characteristic, with oxygen preferably being bound to the first, in particular organic, material in a binding step, the oxygen preferably being in a triplet before the binding step.
  • oxygen preferably being bound to the first, in particular organic, material in a binding step, the oxygen preferably being in a triplet before the binding step.
  • Oxygen is converted into an excited singlet state of oxygen, the phosphor prior to the triplet-triplet interaction from the light of the first characteristic from a singlet state of the phosphor to an excited singlet state of the phosphor and then by intercombination of the excited singlet - The state of the phosphor is converted into an excited triplet state of the phosphor.
  • heat is provided in the functional layer during the deletion process
  • the heat preferably the second, in particular organic, material from an oxygen-impermeable state into one
  • oxygen it is also conceivable for oxygen to be introduced into the functional layer by waiting during the deletion process. Due to imperfections of the functional layer, the oxygen barrier formed by the second, in particular organic, material is not perfect, so that oxygen can diffuse in over a longer period of time.
  • the heat is introduced by irradiation with light of the second characteristic, the light of the second characteristic preferably being IR light.
  • the functional layer is partially covered with a mask in such a way that it closes the area to be deleted is illuminated and / or the functional layer is illuminated with light of the second characteristic by a locally meandering or line-by-line rastering light beam only in the area to be deleted and / or the functional layer is illuminated only in the area to be deleted that the functional layer with a light beam is illuminated with a steel profile, the beam profile on the functional layer corresponding to the area to be deleted.
  • Another object of the present invention is a sensor for determining the dose of ultraviolet light, comprising a structure according to one of claims 13 to 29.
  • the sensor determines the energy absorbed by the sensor per unit area when irradiated with ultraviolet light.
  • the sensor according to the invention thus provides a measuring device for determining the dose of ultraviolet radiation impinging on an object.
  • the sensor according to the invention provides information about the absolute value of the dose of ultraviolet radiation (UV dose).
  • the sensor does not require any electronics and is therefore independent of a power source.
  • the sensor is preferably designed as a film. This enables flexible and easy attachment. An electronics-free, large-area executable and flexible sensor for determining the UV dose is thus provided.
  • the senor has a dose threshold value, wherein when irradiated with ultraviolet light with a dose that the
  • Dose threshold equals or exceeds the phosphorescence onset.
  • the dose threshold can be varied, for example, by the material composition of the structure and by the first and second layer thickness of the structure.
  • the senor has a main extension plane and the dose threshold is homogeneous in the main extension plane. This advantageously provides a sensor for the spatially resolved determination of the UV dose.
  • the main extension plane of the sensor runs in particular parallel to the substrate and / or to the first and second layers of the structure.
  • the main extension plane of the sensor with UV light is triggered in the areas of phosphorescence in which the dose threshold value is reached or exceeded. In the remaining areas, the phosphorescence is due to the molecular structure present
  • the senor can be used to determine when and where a certain UV dose defined by the dose threshold value has been exceeded.
  • the senor has a neutral density filter.
  • the dose threshold can be set and easily changed.
  • the neutral density filter is preferred as a film on the sensor surface
  • the dose threshold can be set via material parameters of the structure.
  • the senor has a main extension plane and the dose threshold value has a gradient or a gradation of transparency in the main extension plane.
  • the sensor has one
  • Neutral density filter wherein the neutral density filter has a gradient or a gradation of transparency.
  • the neutral density filter is designed, for example, as a gray gradient filter or a GND filter (graduated neutral density filter).
  • the material composition of the structure has a gradient or a gradation in the composition.
  • the dose threshold increases along at least one axis in the main extension plane.
  • the UV dose required to trigger the phosphorescence thus changes along at least one axis in the main plane of extent of the sensor.
  • the at least one axis runs parallel to an edge of the sensor.
  • the dose threshold value preferably increases along the at least one axis.
  • the sensor only shines due to the phosphorescence, for example, only in the lower region of the at least one axis, while at higher doses the luminous region along the
  • the senor extends at least one axis.
  • the sensor preferably has a scale along the at least one axis, the scale indicating the respective dose threshold value.
  • the irradiated UV dose can thus be read off directly.
  • the use of reading devices is advantageously avoided. This enables one-dimensional, but absolute UV dose determination.
  • Another object of the present invention is a method for the spatially resolved determination of a dose of ultraviolet radiation, in particular an object hitting it, with a sensor according to one of claims 39 to 42, wherein in one
  • the senor preferably with the object, is irradiated with ultraviolet light of a dose to be determined and in a determination step in the
  • the molecular oxygen present in the region of the first, in particular organic, material and / or in the region of the phosphor prevents the
  • molecular oxygen which is present in the region of the first, in particular organic, material and / or in the region of the phosphor is deactivated photochemically.
  • the oxygen is bound to the first, in particular organic, material.
  • the phosphor is stimulated to phosphorescence by further irradiation with UV light.
  • the inventive method check the homogeneity of irradiation with UV light. If the phosphorescence appears everywhere and at the same time in the main plane of the sensor, the UV dose is homogeneous.
  • Another object of the present invention is a method for
  • the phosphorescence in the areas of the main extension plane of the sensor in which the irradiated dose prevents the
  • the oxygen can therefore no longer prevent the phosphorescence.
  • the phosphor is stimulated to phosphorescence by further irradiation with UV light.
  • the senor is irradiated with light and / or heated in a neutralization step, oxygen penetrating into the sensor due to the irradiation and / or heating and preventing the phosphorescence.
  • the sensor is thus advantageously neutralized and can be reused for further UV dose determinations.
  • the neutralization step is followed in each case by at least one irradiation step and at least one determination step according to one of claims 47 or 48.
  • the UV dose determination is preferably repeated several times for the same or for different objects and / or for the same or for different UV sources.
  • the senor is on a roll
  • UV dose with which objects on the production line are actually irradiated can thus advantageously be determined.
  • information about the spatial resolution of the UV dose and / or the absolute value of the UV dose can be obtained.
  • sensors are preferably arranged on the production line, so that both a two-dimensional UV dose threshold measurement and a one-dimensional, absolute UV dose measurement are made possible. Since the sensor is electronics-free and can be designed as a self-adhesive film, it can be easily and inexpensively integrated into existing production lines.
  • the senor can also be sized, shaped and
  • Sensitivity can easily be tailored to the individual application.
  • the senor is arranged directly on the object whose UV dose is to be determined. It is particularly advantageous here that the sensor is electronics-free and can be operated independently of a power source. For example, the sensor can be applied directly to the object as a self-adhesive film.
  • Figures 1 (a) - (b) show schematic views of the structure and method for
  • Figure 2 shows a schematic of the first activation step according to a
  • FIG. 3 shows a schematic of the second activation step according to an exemplary embodiment of the present invention.
  • Figures 4 (a) - (b) show schematic views of the label and description according to an exemplary embodiment of the present invention.
  • Figure 6 (a) - (b) schematically show the sensor and the method for determining the UV dose according to exemplary embodiments of the present invention.
  • Figure 7 shows schematically the sensor and the method for determining the
  • UV dose according to an exemplary embodiment of the present invention.
  • FIG. 1 (a) shows a schematic view of structure 1 according to an exemplary embodiment of the present invention.
  • the structure 1 has the substrate 2.
  • the substrate 2 is a transparent film.
  • the substrate 2 consists of the second organic material.
  • the first organic material 3 is applied to the substrate 2 in a 900 nm thick layer.
  • the first organic material 3 consists, for example, of polymethyl methacrylate (PMMA), which contains approximately two percent by mass of N, N'-di (1-naphthyl) -N, N'-diphenyl- (1, T-biphenyl) -4,4'-diamine is added.
  • PMMA polymethyl methacrylate
  • the second organic material 4 is applied over the layer of the first organic material 3 and contains ethylene-vinyl alcohol copolymers.
  • the second organic material 4 is oxygen-impermeable in a normal state at room temperature and serves as an oxygen barrier between the first organic material 3 and the surroundings of the structure 1.
  • the first material can, for example, alternatively or additionally contain PS and / or COC.
  • the phosphor also includes, for example, PhenDPA, PhenTPA, TA, BP-TA, Br-BP-TA, BP-2TA, DPS-TA, DPS-2TA, Br-DPS-TA, BF 2 (HPhN) and / or BF 2 (HBAN) suitable.
  • FIG. 1 (b) schematically shows the method for activating the phosphorescence 30 of structure 1, more precisely the first activation step, according to an example
  • the structure 1 is partially illuminated by the light of the first characteristic 8.
  • the structure 1 is partially covered with a mask 7 with respect to the light source of the light of the first characteristic 8.
  • the mask preferably has a resolution of up to 700 dpi.
  • the light of the first characteristic 8 thus irradiates the first area 5 of the structure.
  • the second area 6 of the structure is not illuminated by the light of the first characteristic 8.
  • FIG. 2 shows a schematic of the first activation step according to an exemplary embodiment of the present invention.
  • the light of the first characteristic 8 (not shown) with a wavelength of approximately 365 nm induces a transition of the phosphor mixed with the first organic material 3 in the first region of the structure 8 (see FIG. 1 (b)) from the singlet state of the
  • the layer of the first organic material 3 contains oxygen 9, which is one Phosphorescence 30 prevented.
  • the oxygen 9 is in a triplet ground state of the oxygen T0.
  • the phosphor goes from the excited triplet state of the phosphor T1 to the singlet state of the phosphor SO and the oxygen 9 from the triplet ground state of the
  • the oxygen 9 is highly reactive, oxidizes the first organic material 3 and is bound in the process (not shown).
  • the oxygen 9 present in the layer of the first organic material 3 is thus effectively deactivated.
  • the second organic material 4 prevents additional oxygen from entering the layer of the first organic material 3.
  • the second area 6 is not illuminated by the light of the first characteristic 8 and is consequently not activated. In this area, the oxygen 9 does not reach the first organic one
  • FIG. 3 shows a schematic of the second activation step according to an exemplary embodiment of the present invention.
  • the mask 7 is removed and the light of the first characteristic 8 with significantly reduced intensity is still used for the irradiation (not shown here).
  • a transition of the phosphor from the singlet state of the phosphor SO into the excited singlet state of the phosphor S1 is then further induced in the first region 5. From this excited singlet state of the phosphor S1, the phosphor can change into the excited triplet state of the doping T1 via intercombination 10.
  • the transition from the excited triplet state of the phosphor T1 to the singlet state of the phosphor T0 is “forbidden” in terms of quantum mechanics, and the excited triplet state of the phosphor T1 therefore has a long lifespan.
  • FIG. 4 (a) shows a schematic view of the label 12 according to an exemplary embodiment of the present invention.
  • the label 12 has the substrate 2 on.
  • the substrate 2 is a transparent film.
  • the first organic material 3 is applied to the substrate 2 in a lower layer of 900 nm thickness.
  • the first organic material 3 consists, for example, of polymethyl methacrylate (PMMA), which contains approximately two percent by mass of N, N'-di (1-naphthyl) -N, N'-diphenyl- (1, 1'-biphenyl) -4,4'- dia ine is mixed.
  • PMMA polymethyl methacrylate
  • the first material can, for example, alternatively or additionally contain PS and / or COC.
  • the phosphor also includes, for example, PhenDPA, PhenTPA, TA, BP-TA, Br-BP-TA, BP-2TA, DPS-TA, DPS-2TA, Br-DPS-TA, BF 2 (HPhN) and / or
  • the second organic material 4 is applied in an upper layer above the layer of the first organic material 3 and contains, for example, ethylene-vinyl alcohol copolymers and / or PVA.
  • the second organic material 4 is oxygen impermeable in a normal state at room temperature and serves as
  • the transparent film is preferably adhesive or magnetic. Thus, it can be easily, and in the case of the magnetic film, also reversibly attached to goods, for example.
  • FIG. 4 (b) schematically shows the description of the label 12 according to an exemplary embodiment of the present invention.
  • the label 12 is partially illuminated by the light of the first characteristic 8.
  • the label 12 is compared to the
  • Light source of the light of the first characteristic 8 partially covered with a mask 7.
  • the mask is preferably a negative of the character with which the label 12 is to be written.
  • Possible characters are, for example, one-, two- and three-dimensional codes such as barcodes, QR codes or others. It is also conceivable to put an indication of origin on the label. This can take the form of an image, for example the brand, the manufacturer or the supplier.
  • the light of the first characteristic 8 thus irradiates the phosphorescent area 5 of the label.
  • the non-phosphorescent area 6 of the label 12 is not irradiated by the light of the first characteristic 8.
  • the first phosphorescent region 5 can thus be irradiated with light from the second
  • the label 12 can thus advantageously be written with a resolution of up to 700 dpi.
  • the label 12 is in
  • a label 12 is thus advantageously provided, the content of which cannot be seen with the naked eye.
  • label 12 will be erased by irradiation with IR light with a wavelength of approximately 4 pm for a period of 1 min.
  • the radiation is preferably absorbed by PMMA, PS and / or COC, which heats up as a result.
  • the second organic material 4 which acts as an oxygen barrier at ambient temperature, is thus converted into an oxygen-permeable state.
  • the first organic material 3 is filled with oxygen again, phosphorescence is prevented.
  • Write and erase cycles can be repeated several times. If the write and erase procedures are repeated 40 times, for example, the emission will still reach 40% of its initial value.
  • FIG. 5 (a) schematically shows the structure of the sensor 13 for determining the dose of ultraviolet light 17 according to an exemplary embodiment of the present invention.
  • the sensor 13 has a structure 1.
  • the structure 1 has a first and a second material 3, 4, a phosphor being added to the first material 3 and oxygen 9 being present in the region of the phosphor, and the second material 4 being oxygen-impermeable at an ambient temperature and in
  • oxygen-impermeable state acts as an oxygen barrier between the first material 3 and an environment of the structure 1.
  • the second material 4 is preferred by supplying heat and / or light from the oxygen-impermeable state to the
  • the structure 1 also preferably has a substrate 2.
  • the substrate 2 has, for example, the second material 4.
  • the substrate 2 preferably has a film, particularly preferably a self-adhesive or magnetic film. This gives the sensor 13 great flexibility. Furthermore, the sensor 13 can be attached easily, possibly even reversibly.
  • Structure 1 has, for example, a first layer with a first layer thickness made of first material 3 and / or at least a second layer with a second layer thickness made of second material 4.
  • the first layer is preferably arranged between the substrate 2 and the at least second layer.
  • the first material 3 is preferably an organic material.
  • the second material 4 is also preferably an organic material.
  • the first material 3 and the phosphor preferably form a guest-host complex.
  • the first material 3 has PMMA, PS and / or COC and the second material 4 has, for example, EVOH and / or PVA.
  • the phosphor has, for example, NPB, PhenDPA, PhenTPA, TA, BP-TA, Br-BP-TA, BP-2TA, DPS-TA, DPS-2TA, Br-DPS-TA, BF 2 (HPhN) and / or BF 2 (HBAN) on.
  • the sensor 13 preferably has a dose threshold value, wherein when the sensor 13 is irradiated with ultraviolet light 17 with a dose that corresponds to the dose threshold value corresponds to or exceeds this, uses phosphorescence 30.
  • the dose threshold value depends, among other things, on the material composition of structure 1 and can be varied via this.
  • FIG. 6 (a) shows schematically the sensor 13 and the method for determining the UV dose according to an exemplary embodiment of the present invention.
  • the sensor 13 has those described in the description of FIGS. 5 (a) and 5 (b)
  • the sensor 13 preferably has a main extension plane 14.
  • the main extension plane 14 runs parallel to the substrate 2.
  • the dose threshold value is homogeneous in the main extension plane 14. That means that at every point in the
  • Main extension plane 14 the same UV dose is necessary to excite phosphorescence 30.
  • the sensor 13 is irradiated with UV light 17 of a dose to be determined in an irradiation step.
  • a determination step in regions 5 of the main extension plane 14, in which the irradiated dose reaches or exceeds the dose threshold, molecular oxygen 9 is bound in sensor 13 and phosphorescence 30 is triggered.
  • the molecular oxygen 9 present in particular in the area of the first, in particular organic, material 3 and / or in the area of the phosphor, prevents the
  • Phosphorescence 30 In areas 5 in which the UV dose reaches or exceeds the dose threshold, phosphorescence 30 occurs. In areas 6 in which the UV dose remains below the dose threshold, no phosphorescence 30 occurs. The appearance of the phosphorescence 30 can thus be used to determine when and where the UV dose has reached or exceeded the dose threshold.
  • a method for spatially resolved determination of a UV dose is thus advantageously provided. This can be used, for example, to check the homogeneity of radiation. Homogeneous irradiation, ie irradiation with a spatially homogeneous UV dose, takes place when the phosphorescence 30 occurs simultaneously in the main extension plane 14 everywhere.
  • the dose threshold value can be set via material parameters or a neutral density filter which is preferably arranged on the sensor surface.
  • the neutral density filter is preferably designed as a film.
  • FIG. 6 (b) shows schematically the sensor 13 and the method for determining the UV dose according to an alternative exemplary embodiment of the present invention.
  • the sensor 13 has the in the description of Figures 5 (a) and 5 (b)
  • the sensor 13 preferably has a main extension plane 14.
  • the main extension plane 14 runs parallel to the substrate 2.
  • the dose threshold has a gradient or a gradation along an axis 15.
  • the dose threshold increases, for example linearly, along the axis 15.
  • the sensor 13 has, for example
  • the material composition of structure 1 has a gradient or a gradation in the composition.
  • a lower UV dose is sufficient to excite phosphorescence 30 in the initial region of the axis 15.
  • a higher UV dose is necessary in order to
  • the sensor 13 is irradiated with UV light 17 of a dose to be determined.
  • molecular oxygen 9 is bound in the sensor 13 and phosphorescence 30 is triggered in the areas 5 of the main extension plane 14 of the sensor 13, in which the irradiated dose in each case reaches or exceeds the dose threshold value variable in the main extension plane 14.
  • regions 6 of the main extension plane 14, in which the irradiated dose falls below the variable dose threshold value in the main extension plane 14 the molecular oxygen 9 present in the region 13 of the first, in particular organic, material 3 and / or in the region of the phosphor prevents one Phosphorescence.
  • the sensor 13 When the UV dose is very low, the sensor 13 lights up only in the initial area of the axis 15, and when the UV dose is higher, the illuminated area 5 grows upwards.
  • the sensor 13 preferably has a scale 16 along the at least one axis 15, which indicates the respective dose threshold value. This enables a direct reading of the irradiated UV dose without additional reading devices. One-dimensional absolute values of the UV dose can thus be determined with the sensor 13. The regarding the method described in FIGS. 6 (a) and 6 (b) preferably follows
  • the second, in particular organic, material 4 no longer functions as an oxygen barrier.
  • Oxygen can penetrate structure 1 from the surroundings of sensor 13.
  • the oxygen penetrates into the area of the first, in particular organic, material 3 and / or into the area of the phosphor and prevents the phosphorescence 30 here.
  • the sensor 13 is advantageously neutralized and can be used for a further determination of a UV dose , Irradiation, determination and neutralization steps are preferably repeated several times, for example for different UV sources or different objects.
  • FIG. 7 schematically shows the sensor 13 according to an exemplary embodiment of the present invention.
  • the sensor 13 has the in relation to the
  • the sensor 13 is arranged on a roller 18 of a production line.
  • the sensor 13 is preferably glued to the roll 18.
  • the sensor 13 preferably has a self-adhesive film.
  • the sensor 13 is preferably placed like the objects transported on the roller 18 in normal operation. The measured values determined by means of the sensor 13 thus provide information about the UV dose to which the objects are exposed.
  • the sensor 13 is attached directly to the object.
  • the axis 15 runs along the transport direction of the roller 18.
  • the sensor 13 preferably extends perpendicular to the axis 15 over the width of the roller 18 used.
  • the roller 18 carries out objects, for example for UV curing, under a UV source. With the help of the sensor 13, the absolute value of the UV dose can be determined over the entire width of the roller 18 used. Deviations from the target value can be identified and corrected if necessary.

Landscapes

  • Engineering & Computer Science (AREA)
  • Physics & Mathematics (AREA)
  • Chemical & Material Sciences (AREA)
  • General Physics & Mathematics (AREA)
  • Theoretical Computer Science (AREA)
  • Organic Chemistry (AREA)
  • General Engineering & Computer Science (AREA)
  • Electromagnetism (AREA)
  • Materials Engineering (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • General Chemical & Material Sciences (AREA)
  • Spectroscopy & Molecular Physics (AREA)
  • Luminescent Compositions (AREA)
  • Photometry And Measurement Of Optical Pulse Characteristics (AREA)

Abstract

L'invention concerne un procédé d'activation et de désactivation de la phosphorescence d'une structure. Aux fins de l'activation lors d'une première étape d'activation servant à la désactivation photochimique d'oxygène dans la structure, la structure est éclairée de lumière présentant une première caractéristique et lors d'une deuxième étape d'activation servant à initier la phosphorescence, la structure est éclairée de lumière présentant une deuxième caractéristique. Aux fins de la désactivation lors d'une étape de désactivation, la structure est éclairée aux fins de l'introduction d'oxygène de lumière présentant une troisième caractéristique. L'invention concerne par ailleurs une structure destinée à être utilisée dans le procédé selon l'invention, un procédé de fabrication servant à fabriquer la structure, ainsi qu'une étiquette comportant la structure selon l'invention, ainsi qu'un procédé de description, de lecture et de suppression de l'étiquette, ainsi qu'un capteur UV comportant la structure selon l'invention, ainsi qu'un procédé de définition de dose UV avec le capteur UV.
EP19759343.7A 2018-08-24 2019-08-23 Procédé d'activation et de désactivation de la phosphorescence d'une structure, procédé de fabrication d'une structure phosphorescente et structure phosphorescente, étiquette comprenant une structure phosphorescente, procédé de description, de lecture et de suppression d'une étiquette, ainsi que capteur uv Pending EP3841181A2 (fr)

Applications Claiming Priority (3)

Application Number Priority Date Filing Date Title
DE102018214374.9A DE102018214374A1 (de) 2018-08-24 2018-08-24 Phosphoreszierendes etikett, verfahren zum beschreiben, löschen und wiederbeschreiben des etiketts
DE102018214375.7A DE102018214375B4 (de) 2018-08-24 2018-08-24 Verfahren zur aktivierung und deaktivierung der phosphoreszenz einer struktur, verfahren zur herstellung einer phosphoreszierenden struktur und phosphoreszierende struktur
PCT/EP2019/072636 WO2020039090A2 (fr) 2018-08-24 2019-08-23 Procédé d'activation et de désactivation de la phosphorescence d'une structure, procédé de fabrication d'une structure phosphorescente et structure phosphorescente, étiquette comprenant une structure phosphorescente, procédé de description, de lecture et de suppression d'une étiquette, ainsi que capteur uv

Publications (1)

Publication Number Publication Date
EP3841181A2 true EP3841181A2 (fr) 2021-06-30

Family

ID=67770495

Family Applications (1)

Application Number Title Priority Date Filing Date
EP19759343.7A Pending EP3841181A2 (fr) 2018-08-24 2019-08-23 Procédé d'activation et de désactivation de la phosphorescence d'une structure, procédé de fabrication d'une structure phosphorescente et structure phosphorescente, étiquette comprenant une structure phosphorescente, procédé de description, de lecture et de suppression d'une étiquette, ainsi que capteur uv

Country Status (4)

Country Link
US (1) US11859115B2 (fr)
EP (1) EP3841181A2 (fr)
KR (1) KR20210049846A (fr)
WO (1) WO2020039090A2 (fr)

Families Citing this family (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE102021109797A1 (de) 2021-04-19 2022-10-20 Technische Universität Dresden Sensor und Sensorvorrichtung zum Ermitteln einer Strahlungsdosis, Auslesevorrichtung zum Auslesen eines Sensors und ein Verfahren zum Ermitteln von einer Strahlungsdosis
CN114851657A (zh) * 2022-05-12 2022-08-05 深圳大学 可编辑的动态磷光柔性薄膜及其应用方法
CN118219689B (zh) * 2024-05-24 2024-07-12 广东工业大学 一种隐藏图案信息的防伪标签及其制作方法和图案显现方法

Family Cites Families (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3612866A (en) 1969-07-08 1971-10-12 Brian Stevens Instrument for determining oxygen quantities by measuring oxygen quenching of fluorescent radiation
US6211526B1 (en) 1998-09-30 2001-04-03 The United States Of America As Represented By The Secretary Of The Navy Marking of materials using luminescent and optically stimulable glasses
US7067072B2 (en) 2001-08-17 2006-06-27 Nomadics, Inc. Nanophase luminescence particulate material
EP3764080A1 (fr) * 2010-02-04 2021-01-13 Spectra Systems Corporation Modifications activées par gaz de caractéristiques d'absorption et d'émission de lumière pour des articles de sécurité
WO2012116351A2 (fr) * 2011-02-24 2012-08-30 Myplace, Inc. Système et procédé d'autorisation d'un droit ou d'un avantage

Also Published As

Publication number Publication date
WO2020039090A3 (fr) 2020-04-16
KR20210049846A (ko) 2021-05-06
US20210261859A1 (en) 2021-08-26
WO2020039090A2 (fr) 2020-02-27
US11859115B2 (en) 2024-01-02
WO2020039090A9 (fr) 2020-06-25

Similar Documents

Publication Publication Date Title
WO2020039090A2 (fr) Procédé d'activation et de désactivation de la phosphorescence d'une structure, procédé de fabrication d'une structure phosphorescente et structure phosphorescente, étiquette comprenant une structure phosphorescente, procédé de description, de lecture et de suppression d'une étiquette, ainsi que capteur uv
EP2050046B1 (fr) Document de sécurité et/ou de valeur avec un motif de composants modifiés par rayonnement et procédé de fabrication
DE202018101256U1 (de) Fahrzeugbeleuchtungsbaugruppe
DE102014100767B4 (de) Optisches Element und organisches Licht emittierendes Bauelement mit optischem Element
EP1322478B1 (fr) Procede et dispositif pour personnaliser des caracteristiques d'authenticite luminescentes
DE102014207323A1 (de) Verfahren zur Identifikation eines Gegenstandes
DE102015219400B4 (de) Verfahren zur Prüfung der Identität und/oder Echtheit eines Gegenstandes
DE102014207318A1 (de) Identifikationsmerkmal mit mehreren in einer definiert begrenzten Fläche angeordneten Identifikationselementen zur Identifikation eines Gegenstandes
EP1882519A2 (fr) Microcapsules couche par couche codées en couleur en tant que bibliothèques d'analyse combinatoires et en tant que capteurs optiques spécifiques
WO2011151117A1 (fr) Procédé d'identification d'un substrat
Zanazzi et al. Photoluminescence enhancement of colloidal CdSe/ZnS quantum dots embedded in polyvinyl alcohol after 2 MeV proton irradiation: crucial role of the embedding medium
DE102015219388B4 (de) Verfahren zur Produktionskontrolle von mit einer Druckmaschine auf einen Bedruckstoff oder Gegenstand gedruckten Identifikationsmerkmalen
EP3201005B1 (fr) Caractéristique d'identification servant à identifier un objet
DE102018214374A1 (de) Phosphoreszierendes etikett, verfahren zum beschreiben, löschen und wiederbeschreiben des etiketts
DE102019125646A1 (de) Materialien zur Verstärkung der Aufkonvertierung von nahinfraroter und/oder sichtbarer Strahlung
DE102018214375B4 (de) Verfahren zur aktivierung und deaktivierung der phosphoreszenz einer struktur, verfahren zur herstellung einer phosphoreszierenden struktur und phosphoreszierende struktur
DE10252628A1 (de) Verfahren zur Codierung von Informationen sowie Vorrichtung und Verfahren zur Auswertung der codierten Information
WO2010020238A1 (fr) Pièce plastique, notamment cage pour palier, en plastique pouvant réticuler par irradiation, et procédé de fabrication de cette pièce
DE102015219393B4 (de) Verfahren zur Identifikation eines Gegenstandes
DE102017207921A1 (de) Verfahren zum Aufbringen einer Kennzeichnung auf ein Objekt, Vorrichtung zum Markieren von Objekten und Trägerkörper mit einer Mehrzahl von Kennzeichnungskörpern
DE102018214373B4 (de) Nachleuchtende beleuchtungsvorrichtung für transportmittel, verfahren zum betrieb einer beleuchtungsvorrichtung und transportmittel mit einer beleuchtungsvorrichtung
DE202019100982U1 (de) Beleuchtetes Fahrzeugdisplay
DE10304107A1 (de) Pfandwertgebinde, Verfahren zur Entwertung der Pfandmarkierung bei der Rücknahme an Automaten und Anlage zur Durchführung des Verfahrens
DE102011120845A1 (de) Vorrichtung zur Bestimmung des Gasgehaltes imScheibenzwischenraum bei der Isolierglasproduktion(Inline-Verfahren)
EP2579217A1 (fr) Procédé et dispositif de marquage d'étiquettes de valeur

Legal Events

Date Code Title Description
STAA Information on the status of an ep patent application or granted ep patent

Free format text: STATUS: UNKNOWN

STAA Information on the status of an ep patent application or granted ep patent

Free format text: STATUS: THE INTERNATIONAL PUBLICATION HAS BEEN MADE

STAA Information on the status of an ep patent application or granted ep patent

Free format text: STATUS: THE INTERNATIONAL PUBLICATION HAS BEEN MADE

PUAI Public reference made under article 153(3) epc to a published international application that has entered the european phase

Free format text: ORIGINAL CODE: 0009012

STAA Information on the status of an ep patent application or granted ep patent

Free format text: STATUS: REQUEST FOR EXAMINATION WAS MADE

17P Request for examination filed

Effective date: 20201216

AK Designated contracting states

Kind code of ref document: A2

Designated state(s): AL AT BE BG CH CY CZ DE DK EE ES FI FR GB GR HR HU IE IS IT LI LT LU LV MC MK MT NL NO PL PT RO RS SE SI SK SM TR

DAV Request for validation of the european patent (deleted)
DAX Request for extension of the european patent (deleted)
STAA Information on the status of an ep patent application or granted ep patent

Free format text: STATUS: EXAMINATION IS IN PROGRESS

17Q First examination report despatched

Effective date: 20230522