EP0953068B1 - Stratifie a proprietes de phosphorescence, son procede de fabrication et son utilisation - Google Patents

Stratifie a proprietes de phosphorescence, son procede de fabrication et son utilisation Download PDF

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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)
English (en)
Other versions
EP0953068A1 (fr
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/fr
Application granted granted Critical
Publication of EP0953068B1 publication Critical patent/EP0953068B1/fr
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.

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

Claims (11)

  1. Corps stratifié comprenant un substrat et au moins une couche, qui contient un émail, appliquée d'un ou des deux côtés sur ledit substrat, caractérisé en ce que ladite au moins une couche, qui contient un émail, contient au moins une substance phosphorescente à base d'un aluminate alcalino-terreux.
  2. Corps stratifié selon la revendication 1, caractérisé en ce que le substrat contient de l'aluminium ou un alliage d'aluminium.
  3. Corps stratifié selon les revendications 1 ou 2, caractérisé en ce que l'émail est fabriqué à partir d'un matériau fritté d'émail contenant un métal lourd.
  4. Corps stratifié selon l'une quelconque des revendications précédentes, caractérisé en ce que le substrat présente une tôle trouée présentant une épaisseur de 0,2 à 2,5 mm ou un film présentant une épaisseur de 50 à 500 µm.
  5. Corps stratifié selon l'une quelconque des revendications précédentes, caractérisé en ce que ladite au moins une couche qui contient un émail présente une épaisseur de 400 µm ou moins.
  6. Corps stratifié selon l'une quelconque des revendications précédentes, caractérisé en ce qu'il contient en tant qu'au moins une substance phosphorescente, un aluminate alcalino-terreux dopé avec un élément de terre rare.
  7. Corps stratifié selon l'une quelconque des revendications précédentes, caractérisé en ce qu'il contient en outre, d'un côté ou des deux côtés, une couche de réflexion en un émail blanc ou clair présentant une teneur en blanc d'au moins 78%.
  8. Procédé de fabrication d'un corps stratifié, qui comprend les étapes suivantes :
    application sur un ou les deux côtés d'un substrat d'au moins une couche, qui contient un émail,
    cuisson de ladite au moins une couche appliquée qui contient un émail,
    caractérisé en ce que ladite au moins une couche, qui contient un émail, contient au moins une substance phosphorescente à base d'un aluminate alcalino-terreux.
  9. Utilisation d'un corps stratifié selon l'une quelconque des revendications 1 à 7 ou d'un corps stratifié fabriqué comme défini dans la revendication 8, afin de donner des propriétés phosphorescentes à un objet.
  10. Objet phosphorescent, caractérisé en ce qu'il est pourvu d'un corps stratifié selon l'une quelconque des revendications 1 à 7 ou d'un corps stratifié fabriqué comme défini dans la revendication 8.
  11. Utilisation d'une substance phosphorescente à base d'un aluminate alcalino-terreux afin de donner des propriétés phosphorescentes à un corps stratifié, comprenant un substrat et au moins une couche, qui contient un émail, appliquée d'un côté ou des deux côtés sur ledit substrat.
EP97951999A 1996-11-29 1997-11-28 Stratifie a proprietes de phosphorescence, son procede de fabrication et son utilisation Expired - Lifetime EP0953068B1 (fr)

Applications Claiming Priority (3)

Application Number Priority Date Filing Date Title
DE19649662A DE19649662A1 (de) 1996-11-29 1996-11-29 Schichtkörper mit Nachleuchteigenschaften, Verfahren zu dessen Herstellung und dessen Verwendung
DE19649662 1996-11-29
PCT/EP1997/006638 WO1998023791A1 (fr) 1996-11-29 1997-11-28 Stratifie a proprietes de phosphorescence, son procede de fabrication et son utilisation

Publications (2)

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

Family

ID=7813222

Family Applications (1)

Application Number Title Priority Date Filing Date
EP97951999A Expired - Lifetime EP0953068B1 (fr) 1996-11-29 1997-11-28 Stratifie a proprietes de phosphorescence, son procede de fabrication et son utilisation

Country Status (13)

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

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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 (ja) * 2005-06-07 2008-05-28 株式会社フジクラ 発光素子実装用基板および発光素子モジュール
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 (fr) * 2006-07-13 2009-02-20 Bacou Dalloz Plaintel Soc Par Masque respiratoire individuel visible dans l'obscurite.
BE1017595A3 (nl) * 2007-05-11 2009-01-13 Polyvision Nv Visueel communicatiepaneel en werkwijze voor het vervaardigen ervan.

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Also Published As

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

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