EP0953068A1 - Stratified composite with phosphorescent properties, method for the production and the use thereof - Google Patents

Stratified composite with phosphorescent properties, method for the production and the use thereof

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Publication number
EP0953068A1
EP0953068A1 EP97951999A EP97951999A EP0953068A1 EP 0953068 A1 EP0953068 A1 EP 0953068A1 EP 97951999 A EP97951999 A EP 97951999A EP 97951999 A EP97951999 A EP 97951999A EP 0953068 A1 EP0953068 A1 EP 0953068A1
Authority
EP
European Patent Office
Prior art keywords
enamel
laminated body
body according
layer
substrate
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.)
Granted
Application number
EP97951999A
Other languages
German (de)
French (fr)
Other versions
EP0953068B1 (en
Inventor
Annett Bretschneider
Wolfgang KÜHN
Jürgen WIECZORECK
Andreas Winterfeldt
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 Riedel de Haen AG
Original Assignee
Riedel de Haen AG
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Riedel de Haen AG filed Critical Riedel de Haen AG
Publication of EP0953068A1 publication Critical patent/EP0953068A1/en
Application granted granted Critical
Publication of EP0953068B1 publication Critical patent/EP0953068B1/en
Anticipated expiration legal-status Critical
Expired - Lifetime legal-status Critical Current

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Classifications

    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23D—ENAMELLING OF, OR APPLYING A VITREOUS LAYER TO, METALS
    • C23D5/00—Coating with enamels or vitreous layers
    • C23D5/06—Coating with enamels or vitreous layers producing designs or letters
    • A—HUMAN NECESSITIES
    • A62—LIFE-SAVING; FIRE-FIGHTING
    • A62B—DEVICES, APPARATUS OR METHODS FOR LIFE-SAVING
    • A62B3/00—Devices or single parts for facilitating escape from buildings or the like, e.g. protection shields, protection screens; Portable devices for preventing smoke penetrating into distinct parts of buildings
    • 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
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10S—TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10S428/00—Stock material or miscellaneous articles
    • Y10S428/917—Electroluminescent

Definitions

  • the present invention relates to a laminate which comprises a substrate and, applied to it on one or both sides, at least one layer which contains an enamel, the layer containing at least one phosphor.
  • a laminate has afterglow properties.
  • the present invention relates to a method for producing the laminated body defined above, its use to impart afterglow properties to an object provided with it, and to these objects per se.
  • the laminated body according to the invention can be used wherever a dangerous situation for people can arise due to a sudden failure of the general lighting. This can be done in the form of markings and safety signs as part of a long-luminescent safety guidance system to safely guide people to an exit or a safe area on a predetermined escape route.
  • the present invention was therefore based on the object of producing laminates with good afterglow properties, which are preferably non-combustible and do not release any irritating or toxic gases when exposed to heat. Furthermore, these laminated bodies should be able to be freely designed by screen printing or by other printing processes.
  • the laminate should be inexpensive to manufacture, use and be easily exchangeable.
  • the present invention relates to a laminate comprising a substrate which preferably contains aluminum or an aluminum alloy and, applied thereon on one or both sides, at least one layer which contains an enamel, characterized in that the at least one layer of enamel is a phosphor contains.
  • the laminated body according to the invention can be made free of plastics.
  • All enamelled substrates in particular those based on metal, such as e.g. Iron materials, aluminum or materials containing an aluminum alloy, copper, silver, gold and titanium-containing materials are used.
  • a substrate is preferably used which contains aluminum or an aluminum alloy.
  • foils with a thickness of about 50 to about 500 ⁇ m, more preferably about 100 to about 400 ⁇ m, and especially about 200 to about 300 ⁇ m There is practically no restriction with regard to the free perforated area of the perforated sheets, but preferably perforated sheets with a free perforated area of about 20 to about 45% are used.
  • all known aluminum alloys can be used as substrates in the context of the present invention, copper, magnesium, silicon, manganese and zinc as the most important alloy additives, and mixtures of two or more thereof and, in smaller amounts, nickel, cobalt, chromium, vanadium, titanium , Lead, tin, cadmium, bismuth, zirconium and silver, as well as mixtures of two or more thereof.
  • the laminated body according to the invention comprises a layer which contains an enamel which is applied either on one or on both sides of the substrate defined above.
  • the term "email” as used in the context of the present application corresponds to the definition according to "email and enamelling technology", Petzold / Pöschmann, German publisher for basic material industry, Leipzig / Stuttgart, 2nd revised edition 1992, page 15. According to that Enamel a mass, preferably vitreous solidified, from melting or frits, with an inorganic, mainly oxidic-silicate composition, which is to be melted or melted in one or more layers, partly with aggregates, on metal workpieces.
  • the enamel used according to the invention can be produced from an enamel frit that contains or contains no heavy metals.
  • free of heavy metals means that the enamel frit used is completely or essentially free of metals which have an atomic number which is greater than the atomic number of calcium.
  • the substrate contains aluminum and / or an aluminum alloy
  • it is enamelled with a so-called aluminum enamel.
  • the following should be noted in this regard.
  • the low melting point of aluminum and its alloys requires enamels that can be baked at around 520 ° C to 560 ° C. This corresponds to a softening temperature of around 450 ° C. Accordingly, in this embodiment, enamel frits which take the above-mentioned properties into account are used as the starting material.
  • B. glasses with a high content of Li 2 O, BaO and V 2 O 5 can be used.
  • Eutectics that contain fluoride or phosphate-based enamels also meet the temperature requirement.
  • additional components are preferably added to increase the chemical resistance of the resulting enamel. For example, changing the ratios of Li 2 O and TiO 2 and the levels of alkaline earth metal and ZnO can result in good values for the resistance of the resulting enamels against aggressive media. Details can be found in Migonadziev, AS, Steklo i keramika (1966), ⁇ 2, p. 15.
  • Aluminum enamels can be produced in all colors as well as in black and white.
  • opacifying additives such as B. TiO 2 added, in which case the ratio of Li 2 O to TiO 2 must be correspondingly high, ie approximately 1 to 1.5 to 2 must be selected. Colored aluminum enamels can be produced in many shades.
  • This mixture is in a porcelain mill to a slip with a defined fineness of z. B. 0, 1 to 0.5 nB (according to Bayer) and a specific weight of z. B. 1, 5 to 2.0, preferably 1, 7 to 1, 8 g / cm 3 .
  • This slip is usually applied to the part to be enamelled by a spraying process.
  • the thickness of the at least one layer of enamel is preferably 400 ⁇ m or less, more preferably approximately 300 ⁇ m or less, and in particular approximately 200 ⁇ m or less, the lower limit of the layer thickness of the enamel being approximately 30 ⁇ m.
  • a reflection layer can also be produced directly on the substrate, for example by electrical oxidation and / or by incorporation of inorganic pigments, such as, for example, TiO 2 .
  • the enamel which contains a phosphor, can also be applied directly to the substrate without a reflection layer.
  • Examples include:
  • Phosphors as described, for example, in Ullmanns Encyklopadie der Technischen Chemie, 4th edition, volume 16, pp. 179ff (1975), e.g. those based on sulfides, e.g. CaS: Bi, CaSrS: Bi, ZnS: Cu and ZnCdS: Cu.
  • alkaline earth aluminates e.g. alkaline earth metal aluminates activated with europium or lead, the alkaline earth metal being strontium or a mixture of strontium and calcium, e.g. described in EP-A-0 094 132 and US 3,294,699 (Sr aluminate / Europium), likewise alkaline earth aluminates activated by europium, with barium and strontium as alkaline earth metals, as described in DE-A-1 811 732;
  • Phosphors comprising a matrix of the formula M ⁇ . x Al 2 O 4 . x , where M is at least one metal selected from Ca, Sr and Ba, and X is an integer other than 0, and the matrix Eu as activator and as co-activator at least one from La, Ce, Pr, Nd, Sm, Gd Contains, Tb, Dy, Ho, Er, Tm, Yb, Lu, Mn, Sn and Bi as described in EP-A-0 710 709; Phosphors comprising a composition MO - a (Al 1.
  • MO represents at least one divalent metal oxide selected from MgO, CaO, SrO and ZnO, and R represents Eu and at least one additional rare earth element, as described in DE-A 195 21 119;
  • Rare earth metal doped alkaline earth aluminates as in EP-A-0 710 709 and DE-A 195 21 119;
  • Luminescent materials comprising a matrix of the formula MAl 2 O, where M is calcium, strontium or barium and the matrix europium as activator and as co-activator is at least one of lanthanum, cerium, preseodymium, neodymium, samarium, gadolinium, dysprosium, holmium, erbium, Contains thulium, ytterbium, lutetium, tin and bismuth as described in EP-B-0 622 440; Europium activated ternary metal oxides containing SrO or BaO or mixtures thereof, Al 2 O 3 or a mixture of Al 2 O 3 and Ga 2 O 3 and ZnO or MgO, as described in US Pat. No.
  • Phosphors based on an alkaline earth aluminate are preferably used, in particular the phosphors described in EP-B-0 622 440, EP-A 0 710 709, DE-A 195 21 119 and US 5 376 303.
  • the amount of phosphor used is not particularly limited, but is generally up to approximately 50% by weight, based on the total weight of the laminate, for economic reasons.
  • the lower limit for the amount of phosphor results in particular from the desired afterglow intensity and can therefore be varied over a wide range depending on the application.
  • the present invention also relates to a method for producing the laminate described above, which comprises the following steps: applying at least one or both sides of a layer containing an enamel to a substrate and baking the applied, at least one Layer containing an enamel, characterized in that it contains at least one layer at least one phosphor.
  • the enamel is applied and stoved using conventional methods known from the prior art.
  • a generally degreased and passivated aluminum or aluminum alloy film is applied to the substrate with the aid of an application device, such as a spray gun, the enamel applied in the form of an aqueous suspension (enamel slip) or as a fine powder and then baked at temperatures between about 500 and about 600 ° C.
  • an application device such as a spray gun
  • the enamel applied in the form of an aqueous suspension (enamel slip) or as a fine powder and then baked at temperatures between about 500 and about 600 ° C.
  • these are usually applied one after the other and baked together.
  • the laminated body according to the invention can then at any time on a suitable carrier material, preferably on a non-combustible carrier material, such as e.g. a metal plate, by gluing or welding, or also directly on the object to be marked, also by gluing or mechanical fastening, such as Rivets, clamps or screws.
  • a suitable carrier material preferably on a non-combustible carrier material, such as e.g. a metal plate
  • gluing or welding or also directly on the object to be marked, also by gluing or mechanical fastening, such as Rivets, clamps or screws.
  • the layer which contains an enamel and at least one phosphor can be applied by screen printing or other printing methods, sliding image, stenciling, spraying with stencils or hand lettering.
  • the present invention also relates to the use of a laminated body, as described above, or a laminated body produced as defined above, to impart afterglow properties to an object, and to afterglow objects, characterized in that they are provided with such a laminated body.
  • Objects to be provided with the laminated body according to the invention in the context of the present invention are measuring instruments, dials, safety signs, keys, guardrails, helmets, any type of markings, such as in or on elevators or as traffic control devices, electrical switches, writing instruments, toys or household items - and sports equipment.
  • the present invention relates to the use of a phosphor to provide afterglow properties to a laminate comprising a substrate and, applied thereon on one or both sides, at least one layer containing an enamel.
  • An aluminum foil with a thickness of 80 ⁇ m was unwound from a roll in a continuously operating installation and passed through two degreasing, a rinsing and a passivation bath and was then dried.
  • a white enamel with a thickness of approx. 60 ⁇ m was then applied to both sides by means of spray guns, dried and baked.
  • an aluminum foil with a thickness of 100 ⁇ m, which already had a whitish color due to the incorporation of TiO 2 was anodically pretreated and then freely suspended on the back with a waste aluminum enamel and on the front with an enamel slip, to which a phosphor as in Example 1 was added, coated, dried and baked.
  • the thickness of the enamel layer obtained was 150 ⁇ m.
  • a sheet of AlFeSi aluminum alloy with a sheet thickness of 3 mm was degreased with alkaline, then rinsed with demineralized water and dried.
  • a slip was then produced using the following mixture: 100 parts of aluminum frit 15 parts of adjusting agent 40 parts of water 12 parts of TiO 2
  • This slip was applied to the sheet by spraying, dried and baked at 570 ° C.
  • a body made of a sand casting alloy was degreased alkaline, rinsed several times and passivated with HNO 3 , then dried. This body was coated with a white slip according to Example 3 and baked. A slip was then produced according to the following recipe: 100 parts of aluminum frit and 60 parts of water

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  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Organic Chemistry (AREA)
  • Materials Engineering (AREA)
  • Metallurgy (AREA)
  • Mechanical Engineering (AREA)
  • Emergency Management (AREA)
  • General Engineering & Computer Science (AREA)
  • Electromagnetism (AREA)
  • Business, Economics & Management (AREA)
  • General Health & Medical Sciences (AREA)
  • Health & Medical Sciences (AREA)
  • Physics & Mathematics (AREA)
  • Laminated Bodies (AREA)
  • Luminescent Compositions (AREA)
  • Processing And Handling Of Plastics And Other Materials For Molding In General (AREA)
  • Surface Treatment Of Glass (AREA)
  • Electroluminescent Light Sources (AREA)
  • Glass Compositions (AREA)

Abstract

Laminar body comprising a substrate, and applied thereto on one or both sides, at least one layer containing an enamel, wherein the layer or layers containing an enamel contains at least one phosphor.

Description

Schichtkörper mit Nachleuchteigenschaften, Verfahren zu dessen Herstellung und dessen Verwendung Laminated body with afterglow properties, process for its production and its use
Die vorliegende Erfindung betrifft einen Schichtkörper, der ein Substrat und, darauf ein- oder beidseitig aufgebracht, mindestens eine Schicht, die ein Email enthält, umfaßt, wobei die Schicht mindestens einen Leuchtstoff enthält. Ein derartiger Schichtkörper besitzt Nachleuchteigenschaften. Ferner betrifft die vorliegende Erfindung ein Verfahren zur Herstellung des oben definierten Schichtkörpers, dessen Verwendung, um einem damit versehenen Gegenstand Nachleuchteigenschaften zu verleihen, sowie diese Gegenstände an sich.The present invention relates to a laminate which comprises a substrate and, applied to it on one or both sides, at least one layer which contains an enamel, the layer containing at least one phosphor. Such a laminate has afterglow properties. Furthermore, the present invention relates to a method for producing the laminated body defined above, its use to impart afterglow properties to an object provided with it, and to these objects per se.
Der erfindungsgemäße Schichtkörper kann überall dort verwendet werden, wo durch plötzlichen Ausfall der Allgemeinbeleuchtung eine Gefahrensituation für Menschen eintreten kann. Dies kann vorgenommen werden in Form von Kennzeichnungen und Sicherheitszeichen im Rahmen eines langnachleuchtenden Sicherheitsleitsystems, um Menschen auf vorgegebenem Rettungsweg sicher zu einem Ausgang bzw. zu einem sicheren Bereich zu führen.The laminated body according to the invention can be used wherever a dangerous situation for people can arise due to a sudden failure of the general lighting. This can be done in the form of markings and safety signs as part of a long-luminescent safety guidance system to safely guide people to an exit or a safe area on a predetermined escape route.
Verfahren zur Herstellung von langnachleuchtenden Stahlemails sind bekannt. Die Herstellung von langnachleuchtenden Stahlemails erfolgte bislang unter Verwendung von Leuchtpigmenten auf Basis von Zinksulfiden.Methods for producing long-afterglow steel enamels are known. Long-afterglow steel enamels have so far been produced using luminous pigments based on zinc sulfides.
Um bestimmte Mindestnachleuchtwerte erzielen zu können, mußte ein relativ dicker leuchtstoffhaltiger Emailüberzug gewählt werden. Im Rahmen dieser Verfahren besteht keine technische Möglichkeit, dünne, flexible und damit mehr oder weniger universell einsetzbare Substrate, z.B. Folien auf Basis von Aluminium oder Aluminiumlegierungen, zu emaillieren.In order to be able to achieve certain minimum afterglow values, a relatively thick fluorescent enamel coating had to be selected. Within the scope of these processes, there is no technical possibility of thin, flexible and therefore more or less universally usable substrates, for example foils based of aluminum or aluminum alloys.
Der Versuch, die Schichtdicken von Emails durch den Einsatz von kaschierten Folien zu senken, führte aber zu Schichtkörpern, die partiell brennbar oder thermisch zersetzbar sind. Solche langnachleuchtenden Schichtkörper zeigen gute Nachleuchtwerte, besitzen aber den entscheidenden Nachteil der thermischen Zersetzbarkeit. Diese thermische Zersetzung von Kunststoffen ist immer verbunden mit der Freisetzung von reizenden und giftigen Gasen und macht solche Schichtkörper deshalb für eine Reihe von Anwendungen unbrauchbar.Attempting to reduce the layer thickness of enamels by using laminated foils, however, led to layered bodies that are partially flammable or thermally decomposable. Such long-afterglow laminates show good afterglow values, but have the decisive disadvantage of thermal decomposability. This thermal decomposition of plastics is always associated with the release of irritating and toxic gases and therefore makes such laminates unusable for a number of applications.
Der vorliegenden Erfindung lag somit die Aufgabe zugrunde, Schichtkörper mit guten Nachleuchteigenschaften herzustellen, die vorzugsweise nicht brennbar sind und bei Wärmeeinwirkung keine reizenden oder giftigen Gase freisetzen. Ferner sollen diese Schichtkörper durch Siebdruck oder auch durch andere Druckverfahren frei gestaltbar sein.The present invention was therefore based on the object of producing laminates with good afterglow properties, which are preferably non-combustible and do not release any irritating or toxic gases when exposed to heat. Furthermore, these laminated bodies should be able to be freely designed by screen printing or by other printing processes.
Darüber hinaus sollen die Schichtkörper kostengünstig herstellbar, einsetzbar und problemlos austauschbar sein.In addition, the laminate should be inexpensive to manufacture, use and be easily exchangeable.
Diese und weitere Aufgaben werden durch den erfindungsgemäßen Schichtkörper gelöst.These and other tasks are solved by the laminate according to the invention.
Demgemäß betrifft die vorliegende Erfindung einen Schichtkörper, umfassend ein Substrat, das vorzugsweise Aluminium oder eine Aluminiumlegierung enthält, und, darauf ein- oder beidseitig aufgebracht, mindestens eine Schicht, die ein Email enthält, dadurch gekennzeichnet, daß die mindestens eine Schicht aus Email einen Leuchtstoff enthält.Accordingly, the present invention relates to a laminate comprising a substrate which preferably contains aluminum or an aluminum alloy and, applied thereon on one or both sides, at least one layer which contains an enamel, characterized in that the at least one layer of enamel is a phosphor contains.
Sofern bei der Anwendung vollständige Nichtbrennbarkeit vonnöten ist, kann der erfindungsgemäße Schichtkörper frei von Kunststoffen ausgeführt werden.If complete non-combustibility is required during the application, the laminated body according to the invention can be made free of plastics.
Als Substrat im erfindungsgemäßen Schichtkörper können alle emaillierbaren Substrate, insbesondere solche auf Metall-Basis, wie z.B. Eisenwerkstoffe, Aluminium oder eine Aluminiumlegierung enthaltende Werkstoffe, Kupfer-, Silber-, Gold- und Titan-haltige Werkstoffe eingesetzt werden. Vorzugsweise wird ein Substrat eingesetzt, das Aluminium oder eine Aluminiumlegierung enthält.All enamelled substrates, in particular those based on metal, such as e.g. Iron materials, aluminum or materials containing an aluminum alloy, copper, silver, gold and titanium-containing materials are used. A substrate is preferably used which contains aluminum or an aluminum alloy.
Obwohl bezüglich der Dicke und der Struktur des Substrats keine besonderen Beschränkungen existieren, werden vorzugsweise Lochbleche mit einer Dicke von etwa 0,2 bis etwa 2,5 mm, weiter bevorzugt etwa 0,5 bis etwa 2,0 mm und insbesondere etwa 0,5 bis etwa 1,5 mm, oder Folien mit einer Dicke von etwa 50 bis etwa 500 um, weiter bevorzugt etwa 100 bis etwa 400 um und insbesondere etwa 200 bis etwa 300 um, eingesetzt. Eine Beschränkung bezüglich der freien Lochfläche der Lochbleche existiert praktisch nicht, vorzugsweise werden jedoch Lochbleche mit einer freien Lochfläche von etwa 20 bis etwa 45 % eingesetzt.Although there are no particular restrictions on the thickness and structure of the substrate, perforated sheets with a thickness of about 0.2 to about 2.5 mm, more preferably about 0.5 to about 2.0 mm, and in particular about 0.5 are preferred to about 1.5 mm, or foils with a thickness of about 50 to about 500 µm, more preferably about 100 to about 400 µm, and especially about 200 to about 300 µm. There is practically no restriction with regard to the free perforated area of the perforated sheets, but preferably perforated sheets with a free perforated area of about 20 to about 45% are used.
Prinzipiell können im Rahmen der vorliegenden Erfindung als Substrat alle bekannten Aluminiumlegierungen verwendet werden, wobei als wichtigste Legierungszusätze Kupfer, Magnesium, Silicium, Mangan und Zink sowie Gemische aus zwei oder mehr davon und, in kleineren Mengen, Nickel, Cobalt, Chrom, Vanadium, Titan, Blei, Zinn, Cadmium, Wismut, Zirconium und Silber sowie Gemische aus zwei oder mehr davon zu nennen sind.In principle, all known aluminum alloys can be used as substrates in the context of the present invention, copper, magnesium, silicon, manganese and zinc as the most important alloy additives, and mixtures of two or more thereof and, in smaller amounts, nickel, cobalt, chromium, vanadium, titanium , Lead, tin, cadmium, bismuth, zirconium and silver, as well as mixtures of two or more thereof.
Ferner umfaßt der erfindungsgemäße Schichtkörper eine Schicht, die ein Email enthält, die entweder ein- oder beidseitig auf dem oben definierten Substrat aufgebracht wird. Die Bezeichnung "Email", wie sie im Rahmen der vorliegenden Anmeldung verwendet wird, entspricht der Definition gemäß "Email und Emailliertechnik", Petzold/Pöschmann, Deutscher Verlag für Grundstoffindustrie, Leipzig/Stuttgart, 2. überarbeitete Auflage 1992, Seite 15. Demnach ist Email eine durch Schmelzen oder Fritten entstandene, vorzugsweise glasig erstarrte Masse mit anorganischer, in der Hauptsache oxidisch-silicatischer Zusammensetzung, die in einer oder mehreren Schichten teils mit Zuschlägen auf Werkstücke aus Metall aufgeschmolzen werden soll oder aufgeschmolzen worden ist.Furthermore, the laminated body according to the invention comprises a layer which contains an enamel which is applied either on one or on both sides of the substrate defined above. The term "email" as used in the context of the present application corresponds to the definition according to "email and enamelling technology", Petzold / Pöschmann, German publisher for basic material industry, Leipzig / Stuttgart, 2nd revised edition 1992, page 15. According to that Enamel a mass, preferably vitreous solidified, from melting or frits, with an inorganic, mainly oxidic-silicate composition, which is to be melted or melted in one or more layers, partly with aggregates, on metal workpieces.
Dabei kann das erfindungsgemäß verwendete Email ausgehend von einer schwermetallhaltigen oder schwermetallfreien Emailfritte hergestellt werden.The enamel used according to the invention can be produced from an enamel frit that contains or contains no heavy metals.
Dabei bedeutet der Begriff "schwermetallfrei", daß die verwendete Emailfritte vollständig oder im wesentlichen frei ist von Metallen, die eine Ordnungszahl besitzen, die größer als die Ordnungszahl von Calcium ist.The term "free of heavy metals" means that the enamel frit used is completely or essentially free of metals which have an atomic number which is greater than the atomic number of calcium.
In einer bevorzugten Ausführungsform der vorliegenden Erfindung, in der das Substrat Aluminum und/oder eine Aluminiumlegierung enthält, wird mit einem sogenannten Aluminiumemail emailliert. Diesbezüglich ist folgendes zu beachten. Der niedrige Schmelzpunkt von Aluminium und seinen Legierungen verlangt Emails, die bei etwa 520 °C bis 560 °C eingebrannt werden können. Das entspricht einer Erweichungstemperatur von ungefähr 450 °C. Demgemäß werden in dieser Ausführungsform als Ausgangsmaterial Emailfritten, die den oben genannten Eigenschaften Rechnung tragen, verwendet.In a preferred embodiment of the present invention, in which the substrate contains aluminum and / or an aluminum alloy, it is enamelled with a so-called aluminum enamel. The following should be noted in this regard. The low melting point of aluminum and its alloys requires enamels that can be baked at around 520 ° C to 560 ° C. This corresponds to a softening temperature of around 450 ° C. Accordingly, in this embodiment, enamel frits which take the above-mentioned properties into account are used as the starting material.
Dazu können z. B. Gläser mit einem hohen Gehalt an Li2O, BaO und V2O5 verwendet werden. Auch Eutektika, die Fluorid enthalten oder Emails auf Phosphatbasis erfüllen die Temperaturanforderung. Obwohl mit der Zugabe dieser Bestandteile zwar die o. g. Bedingungen bzgl. des Erweichungspunktes erreicht werden können, werden vorzugsweise weitere Bestandteile zur Erhöhung der chemischen Beständigkeit des resultierenden Emails zugegeben. So lassen sich beispielsweise durch eine Veränderung der Verhältnisse von Li2O und TiO2 und der Gehalte an Erdalkalimetall und ZnO gute Werte für die Resistenz der resultierenden Emails gegen aggressive Medien erreichen. Details hierzu lassen sich Migonadziev, A.S. , Steklo i keramika (1966), \2, S. 15 entnehmen.For this, e.g. B. glasses with a high content of Li 2 O, BaO and V 2 O 5 can be used. Eutectics that contain fluoride or phosphate-based enamels also meet the temperature requirement. Although with the encore of these components, although the above-mentioned conditions regarding the softening point can be achieved, additional components are preferably added to increase the chemical resistance of the resulting enamel. For example, changing the ratios of Li 2 O and TiO 2 and the levels of alkaline earth metal and ZnO can result in good values for the resistance of the resulting enamels against aggressive media. Details can be found in Migonadziev, AS, Steklo i keramika (1966), \ 2, p. 15.
Aluminumemails lassen sich in allen Farben sowie in schwarz und weiß herstellen. Bei den Weißemails werden Trübungszusätze, wie z. B. TiO2 zugegeben, wobei dann das Verhältnis von Li2O zu TiO2 entsprechend hoch, d. h. ungefähr 1 zu 1,5 bis 2 gewählt werden muß. Farbige Aluminiumemails lassen sich in vielen Nuancen herstellen.Aluminum enamels can be produced in all colors as well as in black and white. In the case of white emails, opacifying additives such as B. TiO 2 added, in which case the ratio of Li 2 O to TiO 2 must be correspondingly high, ie approximately 1 to 1.5 to 2 must be selected. Colored aluminum enamels can be produced in many shades.
Beispielhaft sei hier nochmals die Zusammensetzung einer erfindungsgemäß sehr gut verwendbaren Emails beschrieben:The composition of an email that can be used very well according to the invention is again described here by way of example:
100 Teile Fritte 15 Teile Leuchpigment100 parts frit 15 parts fluorescent pigment
4 Teile Borsäure 2 Teile KOH 1 Teil Wasserglas 45 Teile Wasser4 parts boric acid 2 parts KOH 1 part water glass 45 parts water
Diese Mischung wird in einer Porzellanmühle zu einem Schlicker mit definierter Mahlfeinheit von z. B. 0, 1 bis 0,5 n.B. (nach Bayer) und einem spezifischen Gewicht von z. B. 1 ,5 bis 2,0, vorzugsweise 1 ,7 bis 1 ,8 g/cm3 vermählen. Dieser Schlicker wird üblicherweise durch ein Spritzverfahren auf das zu emaillierende Teil aufgebracht.This mixture is in a porcelain mill to a slip with a defined fineness of z. B. 0, 1 to 0.5 nB (according to Bayer) and a specific weight of z. B. 1, 5 to 2.0, preferably 1, 7 to 1, 8 g / cm 3 . This slip is usually applied to the part to be enamelled by a spraying process.
Weitere Details bzgl. derartiger Aluminiumemails, bzw. des Emaillierens von Aluminium oder Aluminiumlegierungen enthaltenden Substraten lassen sich u. a. einem Übersichtsartikel "Mitteilungen des Vereins Deutscher Emailfachleute e. V. Bd. 43, 1995 (Heft 5), S. 56 ff. " entnehmen.Further details regarding such aluminum enamels or the enamelling of substrates containing aluminum or aluminum alloys can be found u. a. see an overview article "Messages from the Association of German Email Specialists eV, Vol. 43, 1995 (No. 5), pp. 56 ff."
Vorzugsweise beträgt die Dicke der mindestens einen Schicht aus Email 400 μm oder weniger, weiter bevorzugt etwa 300 um oder weniger, und insbesondere etwa 200 um oder weniger, wobei die Untergrenze der Schichtdicke des Emails bei etwa 30 um liegt.The thickness of the at least one layer of enamel is preferably 400 μm or less, more preferably approximately 300 μm or less, and in particular approximately 200 μm or less, the lower limit of the layer thickness of the enamel being approximately 30 μm.
In einer weiteren bevorzugten Ausführungsform wird zunächst ein- oder beidseitig eine Reflexionsschicht aus einem weißen oder einem hellen Email mit einem Weißgehalt von mindestens etwa 78% , weiter bevorzugt mindestens etwa 82% , und danach mindestens eine weitere Schicht aus Email aufgebracht.In a further preferred embodiment, a reflection layer made of white or light-colored enamel with a white content of at least about 78%, more preferably at least about 82%, and then at least one further layer of enamel is first applied on one or both sides.
Ferner kann auch direkt auf das Substrat eine Reflexionsschicht, beispielsweise durch elektrische Oxidation und/oder durch Einlagerung anorganischer Pigmente, wie z.B. TiO2, hergestellt werden.Furthermore, a reflection layer can also be produced directly on the substrate, for example by electrical oxidation and / or by incorporation of inorganic pigments, such as, for example, TiO 2 .
Selbstverständlich kann das Email, das einen Leuchtstoff enthält, auch ohne Reflexionsschicht direkt auf das Substrat aufgebracht werden.Of course, the enamel, which contains a phosphor, can also be applied directly to the substrate without a reflection layer.
Sofern mehr als eine Schicht, die ein Email enthält, ein- oder beidseitig aufgebracht wird, ist es insbesondere aus ökonomischen Gründen vorteilhaft, daß lediglich die äußere Schicht, die ein Email enthält, einen Leuchtstoff enthält. Als Leuchtstoffe sind im Rahmen der vorliegenden Erfindung prinzipiell alle bekannten anorganischen Leuchtstoffe einsetzbar.If more than one layer containing an enamel is applied on one or both sides, it is particularly advantageous for economic reasons that only the outer layer containing an enamel contains a phosphor. In principle, all known inorganic phosphors can be used as phosphors in the context of the present invention.
Beispielhaft zu nennen sind:Examples include:
Leuchtstoffe, wie sie beispielsweise in Ullmanns Encyklopädie der Technischen Chemie, 4. Auflage, Band 16, S. 179ff (1975) beschrieben sind, z.B. solche auf Basis von Sulfiden, wie z.B. CaS:Bi, CaSrS:Bi, ZnS:Cu und ZnCdS:Cu.Phosphors as described, for example, in Ullmanns Encyklopadie der Technischen Chemie, 4th edition, volume 16, pp. 179ff (1975), e.g. those based on sulfides, e.g. CaS: Bi, CaSrS: Bi, ZnS: Cu and ZnCdS: Cu.
Leuchtstoffe auf Basis von Erdalkali- Aluminaten, wie z.B. mit Europium oder mit Blei aktivierte Erdalkalimetall-Aluminate, wobei das Erdalkalimetall Strontium oder ein Gemisch aus Strontium und Calcium ist, wie z.B. in der EP-A-0 094 132 und der US 3,294,699 (Sr-Aluminat/Europium) beschrieben, ebenfalls durch Europium aktivierte Erdalkali- Aluminate, mit Barium und Strontium als Erdalkalimetalle, wie in DE-A-1 811 732 beschrieben;Phosphors based on alkaline earth aluminates, e.g. alkaline earth metal aluminates activated with europium or lead, the alkaline earth metal being strontium or a mixture of strontium and calcium, e.g. described in EP-A-0 094 132 and US 3,294,699 (Sr aluminate / Europium), likewise alkaline earth aluminates activated by europium, with barium and strontium as alkaline earth metals, as described in DE-A-1 811 732;
Leuchtstoffe umfassend eine Matrix der Formel Mι.xAl2O4.x, wobei M mindestens ein Metall ausgewählt unter Ca, Sr und Ba ist, und X eine ganze Zahl ungleich 0 ist, und die Matrix Eu als Aktivator und als Co- Aktivator mindestens ein unter La, Ce, Pr, Nd, Sm, Gd, Tb, Dy, Ho, Er, Tm, Yb, Lu, Mn, Sn und Bi enthält, wie in der EP-A-0 710 709 beschrieben; Leuchtstoffe umfassend eine Zusammensetzung MO — a(Al1.bBb)2O3 : cR, worin 0,5 < a ≤ 10,0, 0,0001 < b ≤ 0,5 und 0,0001 < c < 0,2 ist, MO mindestens ein zweiwertiges Metalloxid, ausgewählt aus MgO, CaO, SrO und ZnO, darstellt, und R Eu und mindestens ein zusätzliches Seltenerdelement darstellt, wie in der DE-A 195 21 119 beschrieben;Phosphors comprising a matrix of the formula Mι. x Al 2 O 4 . x , where M is at least one metal selected from Ca, Sr and Ba, and X is an integer other than 0, and the matrix Eu as activator and as co-activator at least one from La, Ce, Pr, Nd, Sm, Gd Contains, Tb, Dy, Ho, Er, Tm, Yb, Lu, Mn, Sn and Bi as described in EP-A-0 710 709; Phosphors comprising a composition MO - a (Al 1. B B b ) 2 O 3 : cR, where 0.5 <a ≤ 10.0, 0.0001 <b ≤ 0.5 and 0.0001 <c <0, 2, MO represents at least one divalent metal oxide selected from MgO, CaO, SrO and ZnO, and R represents Eu and at least one additional rare earth element, as described in DE-A 195 21 119;
Seltenerdmetalidotierte Erdalkalialuminate, wie in der EP-A-0 710 709 und der DE-A 195 21 119 beschrieben;Rare earth metal doped alkaline earth aluminates, as in EP-A-0 710 709 and DE-A 195 21 119;
Leuchtstoffe umfassend eine Matrix der Formel MAl2O , wobei M Calcium, Strontium oder Barium ist und die Matrix Europium als Aktivator und als Co-Aktivator mindestens ein unter Lanthan, Cer, Praeseodym, Neodym, Samarium, Gadolinium, Dysprosium, Holmium, Erbium, Thulium, Ytterbium, Lutetium, Zinn und Wismut enthält, wie in der EP-B-0 622 440 beschrieben; durch Europium aktivierte ternäre Metalloxide enthaltend SrO oder BaO oder Gemische davon, Al2O3 oder ein Gemisch aus Al2O3 und Ga2O3 und ZnO oder MgO, wie in US 4 216 408 beschrieben; und Leuchtstoffe, enthaltend mindestens ein Metalloxid, ausgewählt unter MgO, CaO, SrO und ZnO, sowie als Aktivator Eu2+ und mindestens ein zusätzliches Seltenerdelement, ausgewählt unter Pr, Nd, Dy und Tm, vorzugsweise Dy, wie in US 5,376,303 beschrieben.Luminescent materials comprising a matrix of the formula MAl 2 O, where M is calcium, strontium or barium and the matrix europium as activator and as co-activator is at least one of lanthanum, cerium, preseodymium, neodymium, samarium, gadolinium, dysprosium, holmium, erbium, Contains thulium, ytterbium, lutetium, tin and bismuth as described in EP-B-0 622 440; Europium activated ternary metal oxides containing SrO or BaO or mixtures thereof, Al 2 O 3 or a mixture of Al 2 O 3 and Ga 2 O 3 and ZnO or MgO, as described in US Pat. No. 4,216,408; and phosphors containing at least one metal oxide selected from MgO, CaO, SrO and ZnO, and as activator Eu 2+ and at least one additional rare earth element selected from Pr, Nd, Dy and Tm, preferably Dy, as described in US Pat. No. 5,376,303.
Dabei werden vorzugsweise Leuchtstoffe auf der Basis eines Erdalkali- Aluminats, insbesondere die in der EP-B-0 622 440, der EP-A 0 710 709, der DE-A 195 21 119 und der US 5 376 303 beschriebenen Leuchtstoffe, eingesetzt.Phosphors based on an alkaline earth aluminate are preferably used, in particular the phosphors described in EP-B-0 622 440, EP-A 0 710 709, DE-A 195 21 119 and US 5 376 303.
Die Menge des verwendeten Leuchtstoffs ist nicht in besonderer Weise beschränkt, beträgt jedoch aus ökonomischen Erwägungen im allgemeinen bis zu ungefähr 50 Gew.-%, bezogen auf das Gesamtgewicht des Schichtkörpers. Die Untergrenze für die Menge des Leuchtstoffs ergibt sich insbesondere aus der gewünschten Nachleuchtintensität und kann demnach je nach Anwendung in weiten Bereichen variiert werden.The amount of phosphor used is not particularly limited, but is generally up to approximately 50% by weight, based on the total weight of the laminate, for economic reasons. The lower limit for the amount of phosphor results in particular from the desired afterglow intensity and can therefore be varied over a wide range depending on the application.
Ferner betrifft die vorliegende Erfindung auch ein Verfahren zur Herstellung der oben beschriebenen Schichtkörper, das die folgenden Schritte umfaßt: Ein- oder beidseitiges Aufbringen mindestens einer Schicht, die ein Email enthält, auf ein Substrat und Einbrennen der aufgebrachten, mindestens einen Schicht, die ein Email enthält, dadurch gekennzeichnet, daß diese mindestens eine Schicht mindestens einen Leuchtstoff enthält.Furthermore, the present invention also relates to a method for producing the laminate described above, which comprises the following steps: applying at least one or both sides of a layer containing an enamel to a substrate and baking the applied, at least one Layer containing an enamel, characterized in that it contains at least one layer at least one phosphor.
Das Aufbringen und Einbrennen des Emails erfolgt nach herkömmlichen, aus dem Stand der Technik bekannten Verfahren. So wird auf das Substrat, beispielsweise eine in der Regel entfettete und passivierte Folie aus Aluminium oder Aluminiumlegierung, mit Hilfe einer Aufbringvorrichtung, wie z.B. einer Spritzpistole, das Email in Form einer wäßrigen Suspension (Email-Schlicker) oder als feines Pulver aufgetragen und anschließend bei Temperaturen zwischen etwa 500 und etwa 600 °C eingebrannt. Bei Verwendung mehrerer Schichten aus Email werden diese in der Regel nacheinander aufgebracht und gemeinsam eingebrannt.The enamel is applied and stoved using conventional methods known from the prior art. Thus, for example, a generally degreased and passivated aluminum or aluminum alloy film is applied to the substrate with the aid of an application device, such as a spray gun, the enamel applied in the form of an aqueous suspension (enamel slip) or as a fine powder and then baked at temperatures between about 500 and about 600 ° C. When using several layers of enamel, these are usually applied one after the other and baked together.
Der erfindungsgemäße Schichtkörper kann danach jederzeit auf ein geeignetes Trägermaterial, vorzugsweise auf ein nicht brennbares Trägermaterial, wie z.B. eine Metallplatte, durch Verkleben oder Verschweißen, oder aber auch direkt auf den zu kennzeichnenden Gegenstand, ebenfalls durch Verkleben oder mechanische Befestigung, wie z.B. Nieten, Klemmen oder Schrauben, aufgebracht werden.The laminated body according to the invention can then at any time on a suitable carrier material, preferably on a non-combustible carrier material, such as e.g. a metal plate, by gluing or welding, or also directly on the object to be marked, also by gluing or mechanical fastening, such as Rivets, clamps or screws.
In einer weiteren bevorzugten Ausführungsform kann die Schicht, die ein Email und mindestens einen Leuchtstoff enthält, durch Siebdruck oder andere Druckverfahren, Schiebebild, Schablonieren, Spritzen mit Schablonen oder Handbeschriftung aufgebracht werden.In a further preferred embodiment, the layer which contains an enamel and at least one phosphor can be applied by screen printing or other printing methods, sliding image, stenciling, spraying with stencils or hand lettering.
Darüber hinaus betrifft die vorliegende Erfindung auch die Verwendung eines Schichtkörpers, wie oben beschrieben, oder eines wie oben definiert hergestellten Schichtkörpers, um einem Gegenstand Nachleuchteigenschaften zu verleihen, sowie nachleuchtende Gegenstände, dadurch gekennzeichnet, daß sie mit einem derartigen Schichtkörper versehen sind. Als im Rahmen der vorliegenden Erfindung vorzugsweise mit dem erfindungsgemäßen Schichtkörper zu versehende Gegenstände sind Meßinstrumente, Zifferblätter, Sicherheitszeichen, Schlüssel, Schutzgeländer, Helme, jede Art von Markierungen, wie z.B. in oder an Aufzügen oder als Verkehrsleiteinrichtungen, elektrische Schalter, Schreibinstrumente, Spielzeug oder Haushalts- und Sportgeräte zu nennen.In addition, the present invention also relates to the use of a laminated body, as described above, or a laminated body produced as defined above, to impart afterglow properties to an object, and to afterglow objects, characterized in that they are provided with such a laminated body. Objects to be provided with the laminated body according to the invention in the context of the present invention are measuring instruments, dials, safety signs, keys, guardrails, helmets, any type of markings, such as in or on elevators or as traffic control devices, electrical switches, writing instruments, toys or household items - and sports equipment.
Darüber hinaus betrifft die vorliegende Erfindung in ihrer allgemeinsten Ausgestaltung die Verwendung eines Leuchtstoffs, um einen Schichtkörper, umfassend ein Substrat und, darauf ein- oder beidseitig aufgebracht, mindestens eine Schicht, die ein Email enthält mit Nachleuchteigenschaften zu versehen.In addition, in its most general embodiment, the present invention relates to the use of a phosphor to provide afterglow properties to a laminate comprising a substrate and, applied thereon on one or both sides, at least one layer containing an enamel.
Im folgenden soll die vorliegende Erfindung nunmehr anhand von einigen Ausführungsbeispielen näher erläutert werden.The present invention will now be explained in more detail below with the aid of a few exemplary embodiments.
Beispiel 1example 1
Eine Aluminiumfolie mit einer Dicke von 80 um wurde in einer kontinuierlich arbeitenden Anlage von einer Rolle abgewickelt und durchlief zwei Entfettungs-, ein Spül- und ein Passivierungsbad und wurde anschließend getrocknet.An aluminum foil with a thickness of 80 µm was unwound from a roll in a continuously operating installation and passed through two degreasing, a rinsing and a passivation bath and was then dried.
Danach wurde mittels Spritzpistolen beidseitig ein Weißemail mit einer Dicke von ca. 60 um aufgebracht, getrocknet und eingebrannt.A white enamel with a thickness of approx. 60 μm was then applied to both sides by means of spray guns, dried and baked.
Anschließend wurde ein Aluminiumemail-Schlicker, dem ein Europium- Dysprosium-dotiertes Strontiumaluminat (Lumilux Grün SN der Firma Riedeide Haen) als Leuchtstoff in einer Menge von 40 Gew.-% , bezogen auf das Email, zugesetzt worden war, aufgebracht und dieser Emailauftrag getrocknet und kontinuierlich eingebrannt. Danach wurde die Folie wiederum auf eine Rolle aufgewickelt.An aluminum enamel slip to which a europium dysprosium-doped strontium aluminate (Lumilux Grün SN from Riedeide Haen) had been added as a phosphor in an amount of 40% by weight, based on the enamel, was applied and this enamel application was dried and burned in continuously. The film was then wound up again on a roll.
Bei der anschließenden Verwendung wurden entsprechende Längen von dieser Rolle abgewickelt und direkt verwendet.In the subsequent use, appropriate lengths were unwound from this roll and used directly.
Beispiel 2Example 2
Zunächst wurde eine Aluminiumfolie mit einer Dicke von 100 μm, die durch Einlagerung von TiO2 bereits eine weißliche Färbung aufwies, anodisch vorbehandelt und anschließend freihängend auf der Rückseite mit einem Abfallaluminiumemail und auf der Vorderseite mit einem Email-Schlicker, dem ein Leuchtstoff wie in Beispiel 1 zugesetzt wurde, beschichtet, getrocknet und eingebrannt. Die Dicke der erhaltenen Email-Schicht betrug 150 μm.First, an aluminum foil with a thickness of 100 μm, which already had a whitish color due to the incorporation of TiO 2 , was anodically pretreated and then freely suspended on the back with a waste aluminum enamel and on the front with an enamel slip, to which a phosphor as in Example 1 was added, coated, dried and baked. The thickness of the enamel layer obtained was 150 μm.
Beispiel 3Example 3
Ein Blech der Aluminiumlegierung AlFeSi mit einer Blechdicke von 3 mm wurde alkalisch entfettet, danach mit demineralisiertem Wasser gespült und getrocknet. Danach wurde ein Schlicker nach folgendem Versatz hergestellt: 100 Teile Aluminiumfritte 15 Teile Stellmittel 40 Teile Wasser 12 Teile TiO2 A sheet of AlFeSi aluminum alloy with a sheet thickness of 3 mm was degreased with alkaline, then rinsed with demineralized water and dried. A slip was then produced using the following mixture: 100 parts of aluminum frit 15 parts of adjusting agent 40 parts of water 12 parts of TiO 2
Dieser Schlicker wurde durch Spritzen auf das Blech aufgebracht, getrocknet und bei 570 °C eingebrannt.This slip was applied to the sheet by spraying, dried and baked at 570 ° C.
Anschließend wurde ein weiterer Schlicker nach folgendem Versatz hergestellt: 100 Teile Aluminiumfritte 30 Teile Stellmittel 60 Teile Wasser 200 Teile Leuchtpigment Dieser Schlicker wurde auf die gleiche Weise wie oben beschrieben verarbeitet.Another slip was then produced after the following offset: 100 parts aluminum frit 30 parts adjusting agent 60 parts water 200 parts luminous pigment This slip was processed in the same way as described above.
Beispiel 4Example 4
Ein Körper aus einer Sandgußlegierung wurde alkalisch entfettet, mehrfach gespült und mit HNO3 passiviert, danach getrocknet. Dieser Körper wurde mit einem Weißschlicker nach Beispiel 3 überzogen und eingebrannt. Danach wurde ein Schlicker nach folgender Rezeptur hergestellt: 100 Teile Aluminiumfritte 60 Teile WasserA body made of a sand casting alloy was degreased alkaline, rinsed several times and passivated with HNO 3 , then dried. This body was coated with a white slip according to Example 3 and baked. A slip was then produced according to the following recipe: 100 parts of aluminum frit and 60 parts of water
25 Teile Stellmittel 250 Teile Leuchtstoff Dieser Schlicker wurde getrocknet, zu einem Pulver verrieben, auf das Gußteil gepudert und eingebrannt. 25 parts of setting agent 250 parts of phosphor This slurry was dried, ground into a powder, powdered onto the casting and baked.

Claims

Patentansprüche claims
1. Schichtkörper, umfassend ein Substrat und, darauf ein- oder beidseitig aufgebracht, mindestens eine Schicht, die ein Email enthält, dadurch gekennzeichnet, daß die mindestens eine Schicht, die ein Email enthält, mindestens einen Leuchtstoff enthält.1. Laminated body comprising a substrate and, applied thereon on one or both sides, at least one layer which contains an enamel, characterized in that the at least one layer which contains an enamel contains at least one phosphor.
2. Schichtkörper nach Anspruch 1, dadurch gekennzeichnet, daß das Substrat Aluminium oder eine Aluminiumlegierung enthält.2. Laminated body according to claim 1, characterized in that the substrate contains aluminum or an aluminum alloy.
3. Schichtkörper nach Anspruch 1 oder 2, dadurch gekennzeichnet, daß das Email ausgehend von einer schwermetallhaltigen Emailfritte hergestellt wird.3. Laminated body according to claim 1 or 2, characterized in that the enamel is produced starting from an enamel frit containing heavy metals.
4. Schichtkörper nach einem der vorstehenden Ansprüche, dadurch gekennzeichnet, daß das Substrat ein Lochblech mit einer Dicke von 0,2 bis 2,5 mm oder eine Folie mit einer Dicke von 50 bis 500 μm aufweist.4. Laminated body according to one of the preceding claims, characterized in that the substrate has a perforated plate with a thickness of 0.2 to 2.5 mm or a film with a thickness of 50 to 500 microns.
5. Schichtkörper nach einem der vorstehenden Ansprüche, dadurch gekennzeichnet, daß die mindestens eine Schicht, die ein Email enthält, eine Dicke von 400 μm oder weniger aufweist.5. Laminated body according to one of the preceding claims, characterized in that the at least one layer containing an enamel has a thickness of 400 microns or less.
6. Schichtkörper nach einem der vorstehenden Ansprüche, dadurch gekennzeichnet, daß er als mindestens einen Leuchtstoff ein Seltenerdelement dotiertes Erdalkalialuminat enthält.6. Laminated body according to one of the preceding claims, characterized in that it contains a rare earth element doped alkaline earth aluminate as at least one phosphor.
7. Schichtkörper nach einem der vorstehenden Ansprüche, dadurch gekennzeichnet, daß er zusätzlich ein- oder beidseitig eine Reflexionsschicht aus einem weißen oder hellen Email mit einem Weißgehalt von mindestens 78 % enthält.7. Laminated body according to one of the preceding claims, characterized characterized in that it additionally contains on one or both sides a reflective layer made of white or light enamel with a white content of at least 78%.
8. Verfahren zur Herstellung eines Schichtköφers, das die folgenden Schritte umfaßt: ein- oder beidseitiges Aufbringen mindestens einer Schicht, die ein Email enthält, auf ein Substrat,8. A method for producing a layered body, which comprises the following steps: one-sided or two-sided application of at least one layer containing an enamel to a substrate,
Einbrennen der aufgebrachten mindestens einen Schicht, die ein Email enthält, dadurch gekennzeichnet, daß die mindestens eine Schicht, die ein Email enthält, mindestens einen Leuchtstoff enthält.Burning in the applied at least one layer containing an enamel, characterized in that the at least one layer containing an enamel contains at least one phosphor.
9. Verwendung eines Schichtköφers gemäß einem der Ansprüche 1 bis 7 oder eines Schichtköφers, hergestellt wie in Anspruch 8 definiert, um einem Gegenstand Nachleuchteigenschaften zu verleihen.9. Use of a layered body according to one of claims 1 to 7 or a layered body produced as defined in claim 8 in order to impart afterglow properties to an object.
10. Nachleuchtender Gegenstand, dadurch gekennzeichnet, daß er mit einem Schichtköφer gemäß einem der Ansprüche 1 bis 7 oder einem Schichtköφer, hergestellt wie in Anspruch 8 definiert, versehen ist.10. Afterglow object, characterized in that it is provided with a layered body according to one of claims 1 to 7 or a layered body, as defined in claim 8.
11. Verwendung eines Leuchtstoffs, um einen Schichtköφer, umfassend ein Substrat und, darauf ein- oder beidseitig aufgebracht, mindestens eine Schicht, die ein Email enthält, mit Nachleuchteigenschaften zu versehen. 11. Use of a phosphor in order to provide a layer body comprising a substrate and, applied to it on one or both sides, at least one layer containing an enamel with afterglow properties.
EP97951999A 1996-11-29 1997-11-28 Stratified composite with phosphorescent properties, method for the production and the use thereof Expired - Lifetime EP0953068B1 (en)

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PCT/EP1997/006638 WO1998023791A1 (en) 1996-11-29 1997-11-28 Stratified composite with phosphorescent properties, method for the production and the use thereof

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PT953068E (en) 2002-03-28
JP2001504552A (en) 2001-04-03
JP3792731B2 (en) 2006-07-05
EP0953068B1 (en) 2001-10-10
DE19649662A1 (en) 1998-06-04
AU5557398A (en) 1998-06-22
CN1238811A (en) 1999-12-15
CA2273165A1 (en) 1998-06-04
DK0953068T3 (en) 2002-01-28
ATE206773T1 (en) 2001-10-15
WO1998023791A1 (en) 1998-06-04
KR20000057302A (en) 2000-09-15
US20020119333A1 (en) 2002-08-29
US6528186B1 (en) 2003-03-04
US6699598B2 (en) 2004-03-02
ES2165100T3 (en) 2002-03-01
CN1189594C (en) 2005-02-16
DE59704902D1 (en) 2001-11-15

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