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 PDFInfo
- 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
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- Prior art keywords
- enamel
- laminar body
- layer
- body according
- substrate
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- 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.)
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Classifications
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- 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
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- 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
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- 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
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- 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.
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- Organic Chemistry (AREA)
- Mechanical Engineering (AREA)
- Metallurgy (AREA)
- Materials Engineering (AREA)
- Business, Economics & Management (AREA)
- Electromagnetism (AREA)
- Physics & Mathematics (AREA)
- Health & Medical Sciences (AREA)
- General Health & Medical Sciences (AREA)
- General Engineering & Computer Science (AREA)
- Emergency Management (AREA)
- Laminated Bodies (AREA)
- Luminescent Compositions (AREA)
- Electroluminescent Light Sources (AREA)
- Processing And Handling Of Plastics And Other Materials For Molding In General (AREA)
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- Surface Treatment Of Glass (AREA)
Abstract
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:
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;
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.
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.
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 .
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:
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:
Dieser Schlicker wurde auf die gleiche Weise wie oben beschrieben verarbeitet.This slip was processed in the same way as described above.
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:
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)
- 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.
- Laminar body according to Claim 1, characterized in that the substrate contains aluminium or an aluminium alloy.
- Laminar body according to Claim 1 or 2, characterized in that the enamel is produced from an enamel frit containing heavy metals.
- 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.
- 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.
- 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.
- 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%.
- 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,
- 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.
- 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.
- 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.
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DE19649662 | 1996-11-29 | ||
DE19649662A DE19649662A1 (en) | 1996-11-29 | 1996-11-29 | Laminated body with afterglow properties, process for its production and its use |
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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EP0953068A1 EP0953068A1 (en) | 1999-11-03 |
EP0953068B1 true EP0953068B1 (en) | 2001-10-10 |
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US (2) | US6528186B1 (en) |
EP (1) | EP0953068B1 (en) |
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PT (1) | PT953068E (en) |
WO (1) | WO1998023791A1 (en) |
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- 1996-11-29 DE DE19649662A patent/DE19649662A1/en not_active Ceased
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1997
- 1997-11-20 US US09/308,782 patent/US6528186B1/en not_active Expired - Fee Related
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- 1997-11-28 AT AT97951999T patent/ATE206773T1/en not_active IP Right Cessation
- 1997-11-28 WO PCT/EP1997/006638 patent/WO1998023791A1/en not_active Application Discontinuation
- 1997-11-28 JP JP52429298A patent/JP3792731B2/en not_active Expired - Fee Related
- 1997-11-28 ES ES97951999T patent/ES2165100T3/en not_active Expired - Lifetime
- 1997-11-28 PT PT97951999T patent/PT953068E/en unknown
-
2002
- 2002-04-15 US US10/122,533 patent/US6699598B2/en not_active Expired - Fee Related
Also Published As
Publication number | Publication date |
---|---|
EP0953068A1 (en) | 1999-11-03 |
JP3792731B2 (en) | 2006-07-05 |
PT953068E (en) | 2002-03-28 |
US20020119333A1 (en) | 2002-08-29 |
WO1998023791A1 (en) | 1998-06-04 |
CN1189594C (en) | 2005-02-16 |
KR20000057302A (en) | 2000-09-15 |
CA2273165A1 (en) | 1998-06-04 |
DK0953068T3 (en) | 2002-01-28 |
CN1238811A (en) | 1999-12-15 |
ES2165100T3 (en) | 2002-03-01 |
AU5557398A (en) | 1998-06-22 |
DE59704902D1 (en) | 2001-11-15 |
JP2001504552A (en) | 2001-04-03 |
US6699598B2 (en) | 2004-03-02 |
ATE206773T1 (en) | 2001-10-15 |
US6528186B1 (en) | 2003-03-04 |
DE19649662A1 (en) | 1998-06-04 |
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