EP0953068B1 - 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 Download PDF

Info

Publication number
EP0953068B1
EP0953068B1 EP97951999A EP97951999A EP0953068B1 EP 0953068 B1 EP0953068 B1 EP 0953068B1 EP 97951999 A EP97951999 A EP 97951999A EP 97951999 A EP97951999 A EP 97951999A EP 0953068 B1 EP0953068 B1 EP 0953068B1
Authority
EP
European Patent Office
Prior art keywords
enamel
laminar body
layer
body according
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.)
Expired - Lifetime
Application number
EP97951999A
Other languages
German (de)
French (fr)
Other versions
EP0953068A1 (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

Links

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 comprising a substrate and thereon applied on one or both sides, at least one layer containing an enamel, comprises, wherein the layer contains at least one phosphor.
  • Such one Laminate has afterglow properties.
  • the present concerns Invention a method for producing the laminate defined above, its use to an object provided with it To give afterglow properties, as well as these items themselves.
  • the laminated body according to the invention can be used wherever by sudden failure of general lighting a dangerous situation for people can occur. This can be done in the form of labels and Safety signs in the context of a long-luminescent safety control system, in order to safely lead people to an exit or on a given escape route in a safe area.
  • fluorescent enamel coating In order to achieve certain minimum afterglow values, one had to be relatively thick fluorescent enamel coating can be selected. As part of these procedures there is no technical possibility, thin, flexible and therefore more or less universally applicable substrates, e.g. Foils based on aluminum or Aluminum alloys to be enamelled.
  • BE-A 426 424 relates to a method for enamelling objects with non-radioactive luminescent powders, characterized in that the luminescent powder is heated to 1300 ° C before use and the Bake the powder after applying it to the object a temperature between 500 and 900 ° C is carried out.
  • CH-A 166 802 relates to a method for producing a composition for luminescent enamels, which is characterized in that the for education of an email suitable components are mixed and fused, then finely pulverized and finally the powder obtained with a phosphorescent compound is mixed.
  • FR-A 897 807 relates to a further method for producing luminescent Emails as defined in it.
  • the present invention was therefore based on the object of having laminated bodies produce good afterglow properties that are preferably non-flammable and do not release irritating or toxic gases when exposed to heat. Further these laminated bodies should be screen printed or by other printing processes can be freely designed.
  • the laminate should be inexpensive to manufacture, use and be easily interchangeable.
  • the present invention relates to a laminate comprising a Substrate which preferably contains aluminum or an aluminum alloy, and, applied on one or both sides, at least one layer, which is an enamel contains, characterized in that the at least one layer of enamel a Contains phosphor based on an alkaline earth aluminate.
  • Laminates according to the invention can be executed free of plastics.
  • All enamels can be used as the substrate in the laminated body according to the invention
  • Substrates especially those based on metal, e.g. Iron materials, Aluminum or materials containing an aluminum alloy, copper, silver, Gold and titanium containing materials are used.
  • a Used substrate that contains aluminum or an aluminum alloy.
  • 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 up to about 1.5 mm, or foils with a thickness of about 50 to about 500 ⁇ m , more preferably about 100 to about 400 ⁇ m and in particular about 200 to about 300 ⁇ m .
  • foils with a thickness of about 50 to about 500 ⁇ m more preferably about 100 to about 400 ⁇ m and in particular about 200 to about 300 ⁇ m .
  • free perforated area of the perforated sheets but preferably perforated sheets with a free perforated area of about 20 to about 45% are used.
  • the laminate according to the invention comprises a layer which is an enamel contains either one or both sides of the substrate defined above is applied.
  • enamel is one by melting or frits, preferably glassy solidified mass with inorganic, in the main oxidic silicate composition, which in one or more Layers are partially melted onto metal workpieces using aggregates should or has been melted.
  • the email used according to the invention can be based on a heavy metal free or heavy metal free enamel frit.
  • 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.
  • further constituents are preferably added to increase the chemical resistance of the resulting enamel.
  • 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), 12 , 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 made 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 sprayed onto the enamelled part applied.
  • 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 .
  • one or both sides are used first a reflection layer made of a white or a light enamel with a Whiteness of at least about 78%, more preferably at least about 82%, and then at least one additional layer of enamel is applied.
  • 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 that contains a phosphor can also be used without Reflective layer can be applied directly to the substrate.
  • phosphors are used as phosphors Based on alkaline earth aluminates, e.g. activated with Europium or with lead Alkaline earth metal aluminates, the alkaline earth metal strontium or a mixture of strontium and calcium, e.g. in EP-A-0 094 132 and US 3,294,699 (Sr aluminate / Europium), also described by Europium activated alkaline earth aluminates, with barium and strontium as alkaline earth metals, such as described in DE-A-1 811 732;
  • Phosphors based on an alkaline earth aluminate as in EP-B-0 622 440, EP-A 0 710 709, DE-A 195 21 119 and No. 5,376,303 are used.
  • the amount of the phosphor used is not particularly limited, however, is generally up to about 50 for economic considerations % By weight, based on the total weight of the laminate.
  • the lower limit for the amount of the phosphor results in particular from the desired one Afterglow intensity and can therefore vary depending on the application can be varied.
  • the present invention also relates to a method for producing the laminates described above, which comprises the following steps: Applying one or both sides of at least one layer containing an enamel to a substrate and baking the applied at least one layer containing an enamel, characterized in that this at least one layer contains at least one phosphor based on an alkaline earth metal aluminate.
  • the application and firing of the enamel takes place according to conventional, from the Methods known in the prior art.
  • the substrate for example a degreased and passivated foil made of aluminum or Aluminum alloy
  • an application device such as one Spray gun
  • the enamel in the form of an aqueous suspension (enamel slip) or applied as a fine powder and then at temperatures between about 500 and about 600 ° C baked.
  • enamel slip aqueous suspension
  • these are usually applied one after the other and baked together.
  • the laminate according to the invention can then be changed to a suitable one at any time Backing material, preferably on a non-combustible backing material, e.g. a Metal plate, by gluing or welding, or also directly to the characteristic object, also by gluing or mechanical Attachment, such as Rivets, clamps or screws.
  • a suitable one at any time Backing material preferably on a non-combustible backing material, e.g. a Metal plate, by gluing or welding, or also directly to the characteristic object, also by gluing or mechanical Attachment, such as Rivets, clamps or screws.
  • the layer comprising an email and contains at least one phosphor by screen printing or other printing processes, Sliding picture, stenciling, spraying with stencils or hand lettering be applied.
  • the present invention also relates to the use of a Laminate, as described above, or one produced as defined above Laminate to give afterglow properties to an object, as well luminescent objects, characterized in that they have such Laminates are provided.
  • Laminates preferably with the Laminates according to the invention are objects to be provided Measuring instruments, dials, safety signs, keys, guardrails, Helmets, any kind of markings, e.g. in or on lifts or as Traffic control devices, electrical switches, writing instruments, toys or To name household and sports equipment.
  • the present invention relates to its most general Embodiment the use of a phosphor based on a Alkaline earth aluminate, around a laminate comprising a substrate and thereon applied on one or both sides, with at least one layer containing an enamel To provide afterglow properties.
  • An aluminum foil with a thickness of 80 ⁇ m was continuous in one working system unwound from a roll and went through two degreasing, one Rinsing and a passivation bath and was then dried.
  • an aluminum enamel slip was doped with a Europium dysprosium Strontium aluminate (Lumilux® Green SN from Riedel-de Ha ⁇ n) as a phosphor in an amount of 40% by weight, based on the enamel, had been added, applied and this enamel application dried and burned in continuously. Then the film was again on a roll wound up.
  • a Europium dysprosium Strontium aluminate Lilux® Green SN from Riedel-de Ha ⁇ n
  • an aluminum foil with a thickness of 100 ⁇ m which already had a whitish color due to the incorporation of TiO 2 , was 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 .
  • This slip was applied to the sheet by spraying, drying and Baked at 570 ° C.
  • This slip was processed in the same way as described above.
  • This slip was dried, ground into a powder, on the casting powdered and baked.

Landscapes

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

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 comprising a substrate and thereon applied on one or both sides, at least one layer containing an enamel, comprises, wherein the layer contains at least one phosphor. Such one Laminate has afterglow properties. Furthermore, the present concerns Invention a method for producing the laminate defined above, its use to an object provided with it To give afterglow properties, as well as these items themselves.

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 by sudden failure of general lighting a dangerous situation for people can occur. This can be done in the form of labels and Safety signs in the context of a long-luminescent safety control system, in order to safely lead people to an exit or on a given escape route in a safe area.

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. The Long-afterglow steel enamels have so far been produced under Use of luminescent 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 achieve certain minimum afterglow values, one had to be relatively thick fluorescent enamel coating can be selected. As part of these procedures there is no technical possibility, thin, flexible and therefore more or less universally applicable substrates, e.g. Foils based on aluminum or Aluminum alloys to be enamelled.

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 the layer thicknesses of emails by using laminated Lowering foils, however, resulted in laminates that were partially flammable or are thermally decomposable. Such long afterglow laminates show good Afterglow values, but have the decisive disadvantage of thermal Degradability. This thermal decomposition of plastics is always connected with the release of irritant and toxic gases and exposes them Laminates are therefore unusable for a number of applications.

Die BE-A 426 424 betrifft ein Verfahren zum Emailieren von Gegenständen mit nichtradioaktiven lumineszierenden Pulvern, das dadurch gekennzeichnet ist, daß das lumineszierende Pulver vor seiner Verwendung bis auf 1300°C erhitzt und das Verbacken des Pulvers nach dem Aufbringen desselben auf den Gegenstand bei einer Temperatur zwischen 500 und 900°C durchgeführt wird.BE-A 426 424 relates to a method for enamelling objects with non-radioactive luminescent powders, characterized in that the luminescent powder is heated to 1300 ° C before use and the Bake the powder after applying it to the object a temperature between 500 and 900 ° C is carried out.

Die CH-A 166 802 betrifft ein Verfahren zur Herstellung einer Zusammensetzung für lumineszierende Emails, das dadurch gekennzeichnet ist, daß die zur Bildung eines Emails geeigneten Komponenten vermischt und verschmolzen werden, anschließend fein pulverisiert werden und abschließend das erhaltene Pulver mit einer phosphoreszierenden Verbindung vermischt wird.CH-A 166 802 relates to a method for producing a composition for luminescent enamels, which is characterized in that the for education of an email suitable components are mixed and fused, then finely pulverized and finally the powder obtained with a phosphorescent compound is mixed.

Die FR-A 897 807 betrifft ein weiteres Verfahren zur Herstellung lumineszierender Emails, wie darin definiert.FR-A 897 807 relates to a further method for producing luminescent Emails as defined in it.

Ein Verfahren zum Aufbringen einer Leuchtstoffschicht auf einen Leuchtschirmträger unter Verwendung von Leuchtstoffipulver und Glaslotpulver und Anwendung einer das Glaslotpulver erweichenden Temperatur, wobei gemäß dieser Druckschrift die Leuchtstoffleilchen zunächst mit dem Glaslotpulver ummantelt werden, und dann die ummantelten Leuchtstoffteilchen auf den Leuchtstoffträger aufgebracht und aufgeschmolzen wird in der EP-A 0 427 049 offenbart.A method of applying a phosphor layer to a Luminescent screen support using fluorescent powder and glass solder powder and Application of a temperature softening the glass solder powder, whereby according to this The fluorescent lamp is first coated with the glass solder powder and then the coated phosphor particles onto the phosphor support applied and melted is disclosed in EP-A 0 427 049.

Gemäß des Abstracts CA 114, 11018k, Moa Xianghui et al., "Study of [nonradioactive]luminous enamels from II-VI compounds", Seite 268 und Hunan Shifan Daxue Ziran Kexue Xuebao, Bd. 13, Nr. 1, 1990, Seiten 43-46 einer wissenschaftlichen Publikation in chinesischer Sprache wird dort ein lumineszierendes Email beschrieben, das einen nicht-radioaktiven lumineszierenden Leuchtstoff umfaßt.According to abstract CA 114, 11018k, Moa Xianghui et al., "Study of [nonradioactive] luminous enamels from II-VI compounds ", page 268 and Hunan Shifan Daxue Ziran Kexue Xuebao, Vol. 13, No. 1, 1990, pages 43-46 one scientific publication in Chinese language will be there described luminescent enamel, which is a non-radioactive luminescent Fluorescent covers.

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 having laminated bodies produce good afterglow properties that are preferably non-flammable and do not release irritating or toxic gases when exposed to heat. Further these laminated bodies should be screen printed or by other printing processes can be freely designed.

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 interchangeable.

Diese und weitere Aufgaben werden durch den erfindungsgemäßen Schichtkörper gelöst.These and other tasks are achieved by the laminate according to the invention solved.

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 auf Basis eines Erdalkalialuminats enthält.Accordingly, the present invention relates to a laminate comprising a Substrate which preferably contains aluminum or an aluminum alloy, and, applied on one or both sides, at least one layer, which is an enamel contains, characterized in that the at least one layer of enamel a Contains phosphor based on an alkaline earth aluminate.

Sofern bei der Anwendung vollständige Nichtbrennbarkeit vonnöten ist, kann der erfindungsgemäße Schichtkörper frei von Kunststoffen ausgeführt werden. If complete non-combustibility is required during use, the Laminates according to the invention can be executed 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 enamels can be used as the substrate in the laminated body according to the invention Substrates, especially those based on metal, e.g. Iron materials, Aluminum or materials containing an aluminum alloy, copper, silver, Gold and titanium containing materials are used. Preferably a Used substrate that 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 µm, weiter bevorzugt etwa 100 bis etwa 400 µm und insbesondere etwa 200 bis etwa 300 µm, 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 up 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 in particular 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 can be used as substrate in the context of the present invention known aluminum alloys are used, the most important being Alloy additives copper, magnesium, silicon, manganese and zinc as well Mixtures of two or more of them and, in smaller quantities, nickel, cobalt, Chromium, vanadium, titanium, lead, tin, cadmium, bismuth, zirconium and silver as well as mixtures of two or more of them.

Ferner umfaßt der erfindungsgemäße Schichtkörper eine Schicht, die ein Email enthält, die entweder ein- oder beidseitig auf dem oben definierten Substrat aufgebracht wird.Furthermore, the laminate according to the invention comprises a layer which is an enamel contains either one or both sides of the substrate defined above is applied.

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.The designation "email" as used in the context of the present application used corresponds to the definition according to "enamel and enamelling technology", Petzold / Pöschmann, German publishing house for basic materials industry, Leipzig / Stuttgart, 2. revised edition 1992, page 15. According to this, enamel is one by melting or frits, preferably glassy solidified mass with inorganic, in the main oxidic silicate composition, which in one or more Layers are partially melted onto metal workpieces using aggregates should or has been melted.

Dabei kann das erfindungsgemäß verwendete Email ausgehend von einer schwermetallhaltigen oder schwermetallfreien Emailfritte hergestellt werden.The email used according to the invention can be based on a heavy metal free or heavy metal free enamel frit.

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 "heavy metal free" means that the enamel frit used is completely or essentially free of metals which is an atomic number possess that 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), 12, 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 the above-mentioned conditions regarding the softening point can be achieved with the addition of these constituents, further constituents 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), 12 , 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 hersteilen.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 made in many shades.

Beispielhaft sei hier nochmals die Zusammensetzung einer erfindungsgemäß sehr gut verwendbaren Emails beschrieben:

  • 100 Teile Fritte
  • 15 Teile Leuchpigment
  • 4 Teile Borsäure
  • 2 Teile KOH
  • 1 Teil Wasserglas
  • 45 Teile Wasser
    • The composition of an email that can be used very well according to the invention is again described here by way of example:
  • 100 parts of frit
  • 15 parts of fluorescent pigment
  • 4 parts of boric acid
  • 2 parts of KOH
  • 1 part water glass
  • 45 parts of 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 vermahlen.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 .

    Dieser Schlicker wird üblicherweise durch ein Spritzverfahren auf das zu emaillierende Teil aufgebracht.This slip is usually sprayed onto the enamelled part applied.

    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 u. a. an overview article "Messages from the Association of German Email Specialists" 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 µm oder weniger, und insbesondere etwa 200 µm oder weniger, wobei die Untergrenze der Schichtdicke des Emails bei etwa 30 µm 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, one or both sides are used first a reflection layer made of a white or a light enamel with a Whiteness of at least about 78%, more preferably at least about 82%, and then at least one additional layer of enamel is applied.

    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 that contains a phosphor can also be used without Reflective layer can be applied directly to the substrate.

    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.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, which contains an enamel, contains a phosphor.

    Als Leuchtstoffe sind im Rahmen der vorliegenden Erfindung 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; In the context of the present invention, phosphors are used as phosphors Based on alkaline earth aluminates, e.g. activated with Europium or with lead Alkaline earth metal aluminates, the alkaline earth metal strontium or a mixture of strontium and calcium, e.g. in EP-A-0 094 132 and US 3,294,699 (Sr aluminate / Europium), also described by Europium activated alkaline earth aluminates, with barium and strontium as alkaline earth metals, such as described in DE-A-1 811 732;

    Leuchtstoffe umfassend eine Matrix der Formel M1-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;
  • Seltenerdmetalldotierte Erdalkalialuminate, wie in der EP-A-0 710 709 und der DE-A 195 21 119 beschrieben;
  • Leuchtstoffe umfassend eine Matrix der Formel MAl2O4, 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, verwendbar.
    • Phosphors comprising a matrix of the formula M 1-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 contains at least one of La, Ce, Pr, Nd, Sm, Gd, 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;
  • Rare earth metal doped alkaline earth aluminates, as described in EP-A-0 710 709 and DE-A 195 21 119;
  • Luminescent materials comprising a matrix of the formula MAl 2 O 4 , where M is calcium, strontium or barium and the matrix europium as activator and as co-activator 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, wie sie 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 beschrieben sind, eingesetzt.Phosphors based on an alkaline earth aluminate, as in EP-B-0 622 440, EP-A 0 710 709, DE-A 195 21 119 and No. 5,376,303 are used.

    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 the phosphor used is not particularly limited, however, is generally up to about 50 for economic considerations % By weight, based on the total weight of the laminate. The lower limit for the amount of the phosphor results in particular from the desired one Afterglow intensity and can therefore vary depending on the application can be varied.

    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 auf Basis eines Erdalkalialuminats enthält.    Furthermore, the present invention also relates to a method for producing the laminates described above, which comprises the following steps:
    Applying one or both sides of at least one layer containing an enamel to a substrate and baking the applied at least one layer containing an enamel, characterized in that this at least one layer contains at least one phosphor based on an alkaline earth metal aluminate.

    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 application and firing of the enamel takes place according to conventional, from the Methods known in the prior art. So on the substrate, for example a degreased and passivated foil made of aluminum or Aluminum alloy, by means of an application device such as one Spray gun, the enamel in the form of an aqueous suspension (enamel slip) or applied as a fine powder and then at temperatures between about 500 and about 600 ° C baked. When using multiple 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 laminate according to the invention can then be changed to a suitable one at any time Backing material, preferably on a non-combustible backing material, e.g. a Metal plate, by gluing or welding, or also directly to the characteristic object, also by gluing or mechanical Attachment, 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 comprising an email and contains at least one phosphor, by screen printing or other printing processes, Sliding picture, stenciling, spraying with stencils or hand lettering be applied.

    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.In addition, the present invention also relates to the use of a Laminate, as described above, or one produced as defined above Laminate to give afterglow properties to an object, as well luminescent objects, characterized in that they have such Laminates are provided.

    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.As in the context of the present invention preferably with the Laminates according to the invention are objects to be provided Measuring instruments, dials, safety signs, keys, guardrails, Helmets, any kind of markings, e.g. in or on lifts or as Traffic control devices, electrical switches, writing instruments, toys or To name household and sports equipment.

    Darüber hinaus betrifft die vorliegende Erfindung in ihrer allgemeinsten Ausgestaltung die Verwendung eines Leuchtstoffs auf der Basis eines Erdalkalialuminats, um einen Schichtkörper, umfassend ein Substrat und, darauf ein- oder beidseitig aufgebracht, mindestens eine Schicht, die ein Email enthält mit Nachleuchteigenschaften zu versehen.Furthermore, the present invention relates to its most general Embodiment the use of a phosphor based on a Alkaline earth aluminate, around a laminate comprising a substrate and thereon applied on one or both sides, with at least one layer containing an enamel To provide afterglow properties.

    Im folgenden soll die vorliegende Erfindung nunmehr anhand von einigen Ausführungsbeispielen näher erläutert werden.In the following, the present invention will now be described with reference to some Embodiments are explained in more detail.

    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 continuous in one working system unwound from a roll and went through two degreasing, one Rinsing and a passivation bath and was then dried.

    Danach wurde mittels Spritzpistolen beidseitig ein Weißemail mit einer Dicke von ca. 60 µm aufgebracht, getrocknet und eingebrannt.Then a white enamel with a thickness of approx. 60 µm applied, dried and baked.

    Anschließend wurde ein Aluminiumemail-Schlicker, dem ein Europium-Dysprosium-dotiertes Strontiumaluminat (Lumilux® Grün SN der Firma Riedel-de Haën) 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.Then an aluminum enamel slip was doped with a Europium dysprosium Strontium aluminate (Lumilux® Green SN from Riedel-de Haën) as a phosphor in an amount of 40% by weight, based on the enamel, had been added, applied and this enamel application dried and burned in continuously. Then the film was again on a roll wound up.

    Bei der anschließenden Verwendung wurden entsprechende Längen von dieser Rolle abgewickelt und direkt verwendet.In the subsequent use, corresponding lengths were made from this Roll unwound 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 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 the aluminum alloy AlFeSi with a sheet thickness of 3 mm was degreased with alkaline, then rinsed with demineralized water and dried. A slip was then produced after the following offset:
  • 100 parts of aluminum frit
  • 15 parts of adjusting device
  • 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, drying 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
    • Another slip was then produced after the following offset:
  • 100 parts of aluminum frit
  • 30 parts of adjusting means
  • 60 parts of water
  • 200 parts of luminous pigment

    • Dieser Schlicker wurde auf die gleiche Weise wie oben beschrieben verarbeitet.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 Wasser
  • 25 Teile Stellmittel
  • 250 Teile Leuchtstoff
    • 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. Then a slip was produced according to the following recipe:
  • 100 parts of aluminum frit
  • 60 parts of water
  • 25 parts of adjusting device
  • 250 parts of fluorescent

    • Dieser Schlicker wurde getrocknet, zu einem Pulver verrieben, auf das Gußteil gepudert und eingebrannt.This slip was dried, ground into a powder, on the casting powdered and baked.

    Claims (11)

    1. Laminar body comprising a substrate and, applied thereto on one or both sides, at least one layer containing an enamel, characterized in that the layer or layers containing an enamel contains/contain at least one phosphor based on an alkaline earth metal aluminate.
    2. Laminar body according to Claim 1, characterized in that the substrate contains aluminium or an aluminium alloy.
    3. Laminar body according to Claim 1 or 2, characterized in that the enamel is produced from an enamel frit containing heavy metals.
    4. Laminar body according to any of the preceding claims, characterized in that the substrate comprises a perforated metal sheet having a thickness of from 0.2 to 2.5 mm or a foil having a thickness of from 50 to 500 µm.
    5. Laminar body according to any of the preceding claims, characterized in that the layer or layers containing an enamel has/have a thickness of 400 µm or less.
    6. Laminar body according to any of the preceding claims, characterized in that it contains, as at least one phosphor, an alkaline earth metal aluminate doped with rare earth elements.
    7. Laminar body according to any of the preceding claims, characterized in that it additionally contains, on one or both sides, a reflective layer of a white or light-coloured enamel having a reflectance of at least 78%.
    8. Process for producing a laminar body, which comprises the following steps:
      application of at least one layer containing an enamel to one or both sides of a substrate,
      firing the applied layer or layers containing an enamel,
      characterized in that the layer or layers containing an enamel contains/contain at least one phosphor based on an alkaline earth metal aluminate.
    9. Use of a laminar body according to any of Claims 1 to 7 or a laminar body produced as defined in Claim 8 to give an article phosphorescent properties.
    10. Phosphorescent article, characterized in that it is provided with a laminar body according to any of Claims 1 to 7 or a laminar body produced as defined in Claim 8.
    11. Use of a phosphor based on an alkaline earth metal aluminate to provide a laminar body comprising a substrate and, applied thereto on one or both sides, at least one layer containing an enamel with phosphorescent 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)

    Applications Claiming Priority (3)

    Application Number Priority Date Filing Date Title
    DE19649662A DE19649662A1 (en) 1996-11-29 1996-11-29 Laminated body with afterglow properties, process for its production and its use
    DE19649662 1996-11-29
    PCT/EP1997/006638 WO1998023791A1 (en) 1996-11-29 1997-11-28 Stratified composite with phosphorescent properties, method for the production and the use thereof

    Publications (2)

    Publication Number Publication Date
    EP0953068A1 EP0953068A1 (en) 1999-11-03
    EP0953068B1 true EP0953068B1 (en) 2001-10-10

    Family

    ID=7813222

    Family Applications (1)

    Application Number Title Priority Date Filing Date
    EP97951999A Expired - Lifetime EP0953068B1 (en) 1996-11-29 1997-11-28 Stratified composite with phosphorescent properties, method for the production and the use thereof

    Country Status (13)

    Country Link
    US (2) US6528186B1 (en)
    EP (1) EP0953068B1 (en)
    JP (1) JP3792731B2 (en)
    KR (1) KR20000057302A (en)
    CN (1) CN1189594C (en)
    AT (1) ATE206773T1 (en)
    AU (1) AU5557398A (en)
    CA (1) CA2273165A1 (en)
    DE (2) DE19649662A1 (en)
    DK (1) DK0953068T3 (en)
    ES (1) ES2165100T3 (en)
    PT (1) PT953068E (en)
    WO (1) WO1998023791A1 (en)

    Families Citing this family (9)

    * Cited by examiner, † Cited by third party
    Publication number Priority date Publication date Assignee Title
    DE19935179B4 (en) * 1999-07-27 2005-09-08 Fraunhofer-Gesellschaft zur Förderung der angewandten Forschung e.V. Photobiologically active coating composition and its use
    US6815095B2 (en) * 2001-12-03 2004-11-09 Agfa-Gevaert Binderless phosphor screen having a pigmented interlayer
    US20040087698A1 (en) * 2002-10-15 2004-05-06 Schott Corporation Products incorporating luminescent sealants
    US20050262616A1 (en) * 2004-05-27 2005-12-01 Erb Industries Protective helmet
    US8156671B2 (en) * 2004-10-29 2012-04-17 Yale Security Inc. Photoluminescent exit device
    JP4091063B2 (en) * 2005-06-07 2008-05-28 株式会社フジクラ Light emitting element mounting substrate and light emitting element module
    US7977696B2 (en) * 2006-05-31 2011-07-12 Fujikura Ltd. Light-emitting element mounting substrate, light-emitting element package, display device, and illumination device
    FR2903610B1 (en) * 2006-07-13 2009-02-20 Bacou Dalloz Plaintel Soc Par INDIVIDUAL RESPIRATORY MASK VISIBLE IN DARKNESS.
    BE1017595A3 (en) * 2007-05-11 2009-01-13 Polyvision Nv Visual communication panel for road signs, contains light emitting enamel layer comprising pigment and transparent enamel

    Family Cites Families (26)

    * Cited by examiner, † Cited by third party
    Publication number Priority date Publication date Assignee Title
    BE426424A (en)
    US1407534A (en) * 1919-09-15 1922-02-21 Thomas Howard Luminous composition
    US1637963A (en) * 1924-10-04 1927-08-02 Sauvage Fernand Phosphorescent luminous enamel
    CH166802A (en) 1932-10-13 1934-01-31 Andre Alphonse Process for preparing a composition for luminous enamel.
    FR897807A (en) 1939-11-23 1945-04-03 Process for manufacturing luminescent oven-enamelled signs
    US2436182A (en) * 1941-11-26 1948-02-17 Gilbert T Schmidling Phosphorescent resin composition
    DE1154215B (en) * 1962-02-08 1963-09-12 Patra Patent Treuhand Inorganic phosphor and process for its manufacture
    NL6716351A (en) 1967-12-01 1969-06-03
    US3742494A (en) * 1970-05-22 1973-06-26 Smiths Industries Ltd Information display arrangements
    NL160869C (en) 1972-11-03 Philips Nv LUMINESCENT SCREEN, AS WELL AS DISCHARGE LAMP AND KATHODE BEAM TUBE, FITTED WITH SUCH SCREEN.
    US4359536A (en) * 1981-06-24 1982-11-16 General Electric Company Frit glass composition
    JPS58173182A (en) 1982-04-05 1983-10-12 Shigaken Light-storing glaze and light-storing fluorescent pottery product
    NL8201943A (en) 1982-05-12 1983-12-01 Philips Nv LUMINESCENT SCREEN.
    DE3937008A1 (en) 1989-11-07 1991-05-08 Licentia Gmbh METHOD FOR APPLYING A LUMINAIRE LAYER
    US5084309A (en) * 1990-03-14 1992-01-28 Timothy J. Martin Product presenting different artistic images in the presence and absence of ambient light and fabrication method therefor
    US6137217A (en) * 1992-08-28 2000-10-24 Gte Products Corporation Fluorescent lamp with improved phosphor blend
    US5643674A (en) * 1992-12-18 1997-07-01 E. I. Du Pont De Nemours And Company Luminescent materials prepared by coating luminescent compositions onto substrate particles
    CH687989A5 (en) * 1993-02-18 1997-04-15 Alusuisse Lonza Services Ag Aluminiumhaeltiges substrate.
    JP3388796B2 (en) * 1993-02-18 2003-03-24 矢崎総業株式会社 Inorganic dispersed light emitting device and method of manufacturing the same
    JP3259788B2 (en) * 1993-02-24 2002-02-25 矢崎総業株式会社 Inorganic dispersion type light emitting device
    JP2543825B2 (en) * 1993-04-28 1996-10-16 根本特殊化学株式会社 Luminescent phosphor
    TW349984B (en) * 1993-09-13 1999-01-11 Starck H C Gmbh Co Kg Pastes for the coating of substrates, methods for manufacturing them and their use
    US5479069A (en) * 1994-02-18 1995-12-26 Winsor Corporation Planar fluorescent lamp with metal body and serpentine channel
    US5376303A (en) 1994-06-10 1994-12-27 Nichia Chemical Industries, Ltd. Long Decay phoaphors
    JP3456553B2 (en) 1994-11-01 2003-10-14 根本特殊化学株式会社 Phosphorescent phosphor
    JPH08165140A (en) * 1994-12-08 1996-06-25 Nekusuto I:Kk Glaze and glazed product

    Also Published As

    Publication number Publication date
    JP2001504552A (en) 2001-04-03
    CA2273165A1 (en) 1998-06-04
    US6528186B1 (en) 2003-03-04
    JP3792731B2 (en) 2006-07-05
    DK0953068T3 (en) 2002-01-28
    KR20000057302A (en) 2000-09-15
    CN1238811A (en) 1999-12-15
    DE19649662A1 (en) 1998-06-04
    EP0953068A1 (en) 1999-11-03
    US6699598B2 (en) 2004-03-02
    ES2165100T3 (en) 2002-03-01
    ATE206773T1 (en) 2001-10-15
    PT953068E (en) 2002-03-28
    WO1998023791A1 (en) 1998-06-04
    CN1189594C (en) 2005-02-16
    AU5557398A (en) 1998-06-22
    DE59704902D1 (en) 2001-11-15
    US20020119333A1 (en) 2002-08-29

    Similar Documents

    Publication Publication Date Title
    DE102006028763B4 (en) Alkali lead- and cadmium-free glass frit, process for their preparation and their use, process for producing a ceramic paint and ceramic paint obtainable therefrom
    EP1006088B1 (en) Lead and alkali metal free glass compositions
    DE112010001377B4 (en) A glass composition, composition for an electric conductive paste containing the same, electrode wiring member, and electronic component
    EP3169735B1 (en) Ceramic ink jet printing ink for low-expansion glass and/or low-expansion glass-ceramic and use thereof
    DE19506123C2 (en) Lead-free glass frit, process for its manufacture and its use
    EP0953068B1 (en) Stratified composite with phosphorescent properties, method for the production and the use thereof
    EP0558942B1 (en) Zinc containing, lead-free and cadmium-free glass frits, method of their preparation and their utilization
    DE60101912T2 (en) COMPOSITION OF A BLACK Glaze On A Glass Substrate
    EP2144858B1 (en) Laser pigments for ceramics
    DE60223112T2 (en) Lead-free enamel composition, corresponding enamels and glass-ceramic articles and lead-free glass
    EP1452498A1 (en) Ceramic color composition and ceramic color paste
    DE19600340C1 (en) Process for the production of long afterglow signs, stickers, markings and the like
    EP0895969A1 (en) Lead-free glass compositions having a low melting point
    JPH09142882A (en) Ceramic colored composition containing luminous pigment and glass product coated with the same
    DE2336668C3 (en)
    EP0546365B1 (en) Glass body provided with electrically conductive tracks and process for its manufacturing
    EP0377062A1 (en) Enamel for glass panes provided with silver electric paths
    JP2000154038A (en) Ceramic color composition and production of curved glass sheet
    DE102008052339B4 (en) Process for coloring temperature-resistant substrates
    DE19548183C1 (en) Process for applying a fire retardant layer to a magnesium component
    EP1078895A2 (en) Method of preparing black enamels for glass which can be recycled, glass colourant therefor and glass substrates enamelled therewith
    DE10100669A1 (en) Zinc sulfide doped with copper, silver, manganese, aluminum, europium or dysprosium is used as a pigment in ceramic color, useful for screen printing on e.g. sanitary or architectural glass, ceramics or porcelain
    DD209431A1 (en) METHOD FOR PRODUCING MICROGLASS BALLS WITH CRACKED VALUES OVER 2.2
    DE2352395A1 (en) STATIC ELECTRICITY CONDUCTIVE ENAMELS
    DE1289626B (en) Boron-free enamel coatings with high insulating properties and process for their production

    Legal Events

    Date Code Title Description
    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

    17P Request for examination filed

    Effective date: 19990611

    AK Designated contracting states

    Kind code of ref document: A1

    Designated state(s): AT BE CH DE DK ES FI FR GB GR IE IT LI LU MC NL PT SE

    GRAG Despatch of communication of intention to grant

    Free format text: ORIGINAL CODE: EPIDOS AGRA

    17Q First examination report despatched

    Effective date: 20001110

    GRAG Despatch of communication of intention to grant

    Free format text: ORIGINAL CODE: EPIDOS AGRA

    GRAH Despatch of communication of intention to grant a patent

    Free format text: ORIGINAL CODE: EPIDOS IGRA

    GRAH Despatch of communication of intention to grant a patent

    Free format text: ORIGINAL CODE: EPIDOS IGRA

    GRAA (expected) grant

    Free format text: ORIGINAL CODE: 0009210

    AK Designated contracting states

    Kind code of ref document: B1

    Designated state(s): AT BE CH DE DK ES FI FR GB GR IE IT LI LU MC NL PT SE

    REF Corresponds to:

    Ref document number: 206773

    Country of ref document: AT

    Date of ref document: 20011015

    Kind code of ref document: T

    REG Reference to a national code

    Ref country code: CH

    Ref legal event code: EP

    REG Reference to a national code

    Ref country code: IE

    Ref legal event code: FG4D

    Free format text: GERMAN

    REF Corresponds to:

    Ref document number: 59704902

    Country of ref document: DE

    Date of ref document: 20011115

    REG Reference to a national code

    Ref country code: GB

    Ref legal event code: IF02

    REG Reference to a national code

    Ref country code: DK

    Ref legal event code: T3

    GBT Gb: translation of ep patent filed (gb section 77(6)(a)/1977)

    Effective date: 20020114

    PGFP Annual fee paid to national office [announced via postgrant information from national office to epo]

    Ref country code: MC

    Payment date: 20020227

    Year of fee payment: 5

    ET Fr: translation filed
    REG Reference to a national code

    Ref country code: ES

    Ref legal event code: FG2A

    Ref document number: 2165100

    Country of ref document: ES

    Kind code of ref document: T3

    REG Reference to a national code

    Ref country code: PT

    Ref legal event code: SC4A

    Free format text: AVAILABILITY OF NATIONAL TRANSLATION

    Effective date: 20011212

    REG Reference to a national code

    Ref country code: GR

    Ref legal event code: EP

    Ref document number: 20020400056

    Country of ref document: GR

    PLBE No opposition filed within time limit

    Free format text: ORIGINAL CODE: 0009261

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

    Free format text: STATUS: NO OPPOSITION FILED WITHIN TIME LIMIT

    26N No opposition filed
    PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

    Ref country code: MC

    Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

    Effective date: 20030601

    PGFP Annual fee paid to national office [announced via postgrant information from national office to epo]

    Ref country code: AT

    Payment date: 20041004

    Year of fee payment: 8

    Ref country code: DK

    Payment date: 20041004

    Year of fee payment: 8

    PGFP Annual fee paid to national office [announced via postgrant information from national office to epo]

    Ref country code: NL

    Payment date: 20041006

    Year of fee payment: 8

    PGFP Annual fee paid to national office [announced via postgrant information from national office to epo]

    Ref country code: SE

    Payment date: 20041105

    Year of fee payment: 8

    Ref country code: FR

    Payment date: 20041105

    Year of fee payment: 8

    PGFP Annual fee paid to national office [announced via postgrant information from national office to epo]

    Ref country code: ES

    Payment date: 20041123

    Year of fee payment: 8

    PGFP Annual fee paid to national office [announced via postgrant information from national office to epo]

    Ref country code: BE

    Payment date: 20041130

    Year of fee payment: 8

    PGFP Annual fee paid to national office [announced via postgrant information from national office to epo]

    Ref country code: CH

    Payment date: 20050107

    Year of fee payment: 8

    PGFP Annual fee paid to national office [announced via postgrant information from national office to epo]

    Ref country code: LU

    Payment date: 20050927

    Year of fee payment: 9

    PGFP Annual fee paid to national office [announced via postgrant information from national office to epo]

    Ref country code: GR

    Payment date: 20051024

    Year of fee payment: 9

    PGFP Annual fee paid to national office [announced via postgrant information from national office to epo]

    Ref country code: IE

    Payment date: 20051026

    Year of fee payment: 9

    PGFP Annual fee paid to national office [announced via postgrant information from national office to epo]

    Ref country code: FI

    Payment date: 20051114

    Year of fee payment: 9

    PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

    Ref country code: IT

    Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES;WARNING: LAPSES OF ITALIAN PATENTS WITH EFFECTIVE DATE BEFORE 2007 MAY HAVE OCCURRED AT ANY TIME BEFORE 2007. THE CORRECT EFFECTIVE DATE MAY BE DIFFERENT FROM THE ONE RECORDED.

    Effective date: 20051128

    Ref country code: AT

    Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

    Effective date: 20051128

    PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

    Ref country code: SE

    Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

    Effective date: 20051129

    Ref country code: ES

    Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

    Effective date: 20051129

    PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

    Ref country code: LI

    Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

    Effective date: 20051130

    Ref country code: DK

    Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

    Effective date: 20051130

    Ref country code: CH

    Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

    Effective date: 20051130

    Ref country code: BE

    Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

    Effective date: 20051130

    PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

    Ref country code: NL

    Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

    Effective date: 20060601

    REG Reference to a national code

    Ref country code: DK

    Ref legal event code: EBP

    REG Reference to a national code

    Ref country code: CH

    Ref legal event code: PL

    EUG Se: european patent has lapsed
    PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

    Ref country code: FR

    Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

    Effective date: 20060731

    NLV4 Nl: lapsed or anulled due to non-payment of the annual fee

    Effective date: 20060601

    REG Reference to a national code

    Ref country code: FR

    Ref legal event code: ST

    Effective date: 20060731

    PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

    Ref country code: IE

    Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

    Effective date: 20061128

    Ref country code: FI

    Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

    Effective date: 20061128

    REG Reference to a national code

    Ref country code: ES

    Ref legal event code: FD2A

    Effective date: 20051129

    REG Reference to a national code

    Ref country code: IE

    Ref legal event code: MM4A

    BERE Be: lapsed

    Owner name: *RIEDEL-DE HAEN A.G.

    Effective date: 20051130

    PGFP Annual fee paid to national office [announced via postgrant information from national office to epo]

    Ref country code: PT

    Payment date: 20071011

    Year of fee payment: 11

    PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

    Ref country code: LU

    Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

    Effective date: 20061128

    PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

    Ref country code: GR

    Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

    Effective date: 20070604

    PGFP Annual fee paid to national office [announced via postgrant information from national office to epo]

    Ref country code: DE

    Payment date: 20081128

    Year of fee payment: 12

    REG Reference to a national code

    Ref country code: PT

    Ref legal event code: MM4A

    Free format text: LAPSE DUE TO NON-PAYMENT OF FEES

    Effective date: 20090528

    PGFP Annual fee paid to national office [announced via postgrant information from national office to epo]

    Ref country code: GB

    Payment date: 20081008

    Year of fee payment: 12

    PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

    Ref country code: PT

    Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

    Effective date: 20090528

    GBPC Gb: european patent ceased through non-payment of renewal fee

    Effective date: 20091128

    PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

    Ref country code: DE

    Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

    Effective date: 20100601

    PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

    Ref country code: GB

    Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

    Effective date: 20091128