EP0914257A1 - Process for writing on foils by means of a laser - Google Patents

Process for writing on foils by means of a laser

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Publication number
EP0914257A1
EP0914257A1 EP97934462A EP97934462A EP0914257A1 EP 0914257 A1 EP0914257 A1 EP 0914257A1 EP 97934462 A EP97934462 A EP 97934462A EP 97934462 A EP97934462 A EP 97934462A EP 0914257 A1 EP0914257 A1 EP 0914257A1
Authority
EP
European Patent Office
Prior art keywords
laser
film
additive
layer
cover layer
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Granted
Application number
EP97934462A
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German (de)
French (fr)
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EP0914257B1 (en
Inventor
Norbert Fenten
Dieter Carl
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Quarzwerke GmbH
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Quarzwerke GmbH
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Publication of EP0914257A1 publication Critical patent/EP0914257A1/en
Application granted granted Critical
Publication of EP0914257B1 publication Critical patent/EP0914257B1/en
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Classifications

    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B41—PRINTING; LINING MACHINES; TYPEWRITERS; STAMPS
    • B41M—PRINTING, DUPLICATING, MARKING, OR COPYING PROCESSES; COLOUR PRINTING
    • B41M5/00—Duplicating or marking methods; Sheet materials for use therein
    • B41M5/26—Thermography ; Marking by high energetic means, e.g. laser otherwise than by burning, and characterised by the material used
    • B41M5/267—Marking of plastic artifacts, e.g. with laser

Definitions

  • the invention relates to a method for laser marking of colored or uncolored films with at least one top layer and one base layer.
  • the labeling of production and consumer goods is becoming increasingly important. Compared to conventional labeling techniques such as printing, embossing and labeling, the non-contact marking of packaging foils or moldings with the help of lasers is becoming more and more important because it can easily be used in ongoing production processes.
  • thermoplastics especially the polyolefins, polystyrene and polyamides
  • lasers with low energies there is either no labeling or only labeling with poor contrast.
  • lasers with correspondingly higher energies the polymeric material generally decomposes, which leads to blackening.
  • the labeling of foils in particular, is very difficult since, when using laser radiation with high energies, undesired carbonization of the foil occurs, which can lead to the destruction of the foil in the irradiated areas.
  • polyolefins cannot be inscribed with the usual laser inscription systems for plastics, or only insufficiently, because on the one hand they do not absorb the wavelength of the laser light in certain areas and on the other hand the necessary sharpness of the marking is not achieved by light scattering.
  • This disadvantage means that polyolefins, which, due to their appearance and properties, are ideal for packaging purposes, can only be insufficiently labeled with laser technology. The reason for this is that the polyolefin matrix does not absorb laser beams in the typical wavelengths of standard lasers used, such as 284, 351, 532, 1064 nm, or only little. For other polymers that absorb more, thermal damage to the polymer is generated at these wavelengths, causing the material to be engraved and blackened. The following labeling processes are essentially based on this effect.
  • DE AI 39 17 294.5 describes laser-inscribable polyolefins. These materials contain 0.2 to 4.5% by weight of copper (II) hydroxide phosphate or 0.2 to 2.5% by weight of molybdenum (VI) oxide as an additive.
  • a neodymium-YAG laser at a wavelength of 1064 nm or an excimer laser at wavelengths of 308 or 351 nm is preferably used as the laser. With this process, black inscriptions with good contrast are achieved on polymer injection molded parts.
  • thermoplastic molding compositions with laser-sensitive pigmentation which contain 0.001 to 0.199% by weight of copper (II) hydroxide phosphate as an additive.
  • polyolefins are used as thermoplastics.
  • the laser marking is carried out with the aid of a neodymium-YAG solid-state laser with a wavelength of 1060 nm. A black marking was obtained on molded articles made of polypropylene.
  • EP-Bl 0 190 997 describes a method for laser marking pigmented colored polyolefins.
  • plastics such as polyethylene and polypropylene are first colored with inorganic or organic pigments or polymer-soluble dyes, these colorants preferably absorbing in the near UV and / or visible or near IR range.
  • these thermoplastic molding must be labeled with laser radiation, the laser light having a wavelength in the UV range (0.25 and 0.38 ⁇ m) and / or in the visible range and / or in the IR range (0.78 and 2 ⁇ m).
  • the process creates black labels for polyolefins.
  • EP-AI 0 111 357 describes a method for laser marking molded articles made of polyolefins by irradiation with a TEA-CO 2 laser.
  • the intensity of the laser pulse is 333 kW / cm 2 .
  • the polyolefin contains calcium metasilicate, aluminum silicate or kaolin. The procedure produces black lettering.
  • the polyolefins is added as an additive from about 0.1% by weight of a mica pigment, sold under the name Iriodin ®: is commercially available (manufactured by Merck, Darmstadt).
  • Iriodin ® is commercially available (manufactured by Merck, Darmstadt).
  • the flat mica flakes are coated with a thin layer of a metal oxide with a high refractive index.
  • the pigment flakes are oriented parallel to the surface. If a laser beam hits the pigment platelets, part of the light is reflected on the pigments, the rest is transmitted. Due to the geometry of the platelets, the incident and the reflecting light beam are close together, so that in the area of the laser light beam the available energy density is increased and a surface layer of the plastic is carbonized. This results in a high-contrast black marking.
  • the smooth surface of the film is adversely changed in laser marking, and these changes result in numerous disadvantages for the use of the films.
  • the foaming or the engraving mechanically weaken the film. It becomes more brittle and loses its mechanical properties. Since the foaming or engraving of the surface of the film also causes roughening, there is a tendency for the surface of the film to become dirty at these points, which means that the labels become illegible over time and lose their contrast.
  • the packaging area there is also the great disadvantage that bacteria can also nest in this rough surface layer, which are undesirable particularly in the packaging of foodstuffs.
  • Multi-layer films are known from the prior art. They can be equipped in various ways depending on the intended use and can be produced by coextrusion.
  • the cover layer consists of polymers or copolymers of polyethylene, polypropylene, polybutene-1, polyisobutylene, poly-4-methylpentene-1, polyacetylene or polyamide.
  • the carrier layer preferably consists of a polyolefin and contains 0.05 to 10% by weight of an additive selected from the group consisting of silicates and silicon dioxide with a particle size of 0.01 to 100 ⁇ .
  • the additive for the base layer is selected from the group consisting of silicon dioxide in crystalline or amorphous form, mica, feldspar, calcined kaolin, kaolin, nepheline syenite, talc, calcium silicate hydrate, silica, pyrogenic or precipitated silica, cristobalite, diatomaceous earth , Diatomaceous earth, micro-glass balls or mixtures thereof.
  • Excimer lasers have wavelengths in the UV range from 193 to 351 nm, for example 196, 248, 308 and 351 nm.
  • Neodymium YAG lasers are used in the visible and in the near IR range, for example at wavelengths of 532 and 1064 nm.
  • the use of pulsed lasers with pulse durations of 1 to 1000 ns is particularly preferred.
  • the energy densities used are preferably between 1 and 20 J / cm.
  • Inorganic or organic pigments or polymer-soluble dyes are preferably used for coloring the film.
  • the additive for the base layer can also be used in a mixture with polyolefin as a masterbatch.
  • a CO 2 laser at wavelengths of 10,600 or 9,300 nm is preferably used for laser marking.
  • the foils can have an energy density of 1 to 10 J / cm 2 ,
  • FIG. 1 shows an SEM image of the cross section of a brittle fracture of a multilayer film which was produced by the method according to the invention.
  • FIG. 2 shows a SEM image of a brittle fracture of a laser-inscribed film of the prior art in supervision.
  • FIG. 3 shows an SEM image of the cross section of a brittle fracture of a laser-inscribed film of the prior art.
  • the polyolefins used for the support layer are preferably those derived from alkenes having 2 to 10 carbon atoms.
  • Homopolymers or copolymers of ethylene, propylene or butylene are preferably used.
  • Polyethylenes can be manufactured using the high, medium or low pressure process. Ren. Copolymers of ethylene with phenyl esters, acrylic esters or with propylene can also be used. In a particularly preferred manner, high-density polyethylene or linear low-density polyethylene are used.
  • Polyethylenes which contain conventional fillers, stabilizers and antiblocking agents can also be used.
  • polypropylene Another polyolefin that can be used in a preferred manner is polypropylene, which is used, for example, according to the gas phase process using Ziegler-Natta
  • Catalysts can be made. Also to be mentioned are copolymers of propylene which consist, for example, of propylene homopolymer and polypropylene copolymer with copolymerized C2 to CIO-alk-1-enes. Ethylene, butene-1, pentene-1, hexene-1 or octene-1 or mixtures thereof are used, for example, as polymerized C2 to cin-alkenes. Ethylene and butene-1 are preferred.
  • propylene copolymers are prepared by polymerization using Ziegler-Natta catalysts, preferably in the gas phase using the polymerization reactors customary in the art. Processes for the production of polyolefins are generally known and are described in "Ullmann's Encyclopedia of Industrial Chemistry", 4th edition, volume 19, pages 167 to 226.
  • the polyolefin suitable for laser marking can also contain conventional additives or pigments.
  • inorganic pigments that cause discoloration are white pigments, such as titanium oxide, zinc oxide, antimony trioxide, zinc sulfide, lithopone, basic lead carbonate, basic lead sulfate or basic lead silicate, and also metal oxide, such as iron oxides, chromium oxides, nickel antimony titanate, chromium antimony titanate, manganese blue, manganese violet , Cobalt blue, cobalt chrome blue, cobalt nickel gray or ultramarine blue, Berlin blue, lead chromates, lead sulfochromates, molybdate orange, molybdate red, metal sulfides such as cadmium sulfide, arsenic disulfide, antimony tri sulfide or Cadmiu sulfoselenide, zirconium silicates such as zirconium vanadium blue and zirconium praseodymium
  • organic pigments examples include azo, azomethine, methine, anthraquinone, indanthrone, pyranthrone, flavonthrone, benzanthrone, phthalocyanine, perylene, dioxazine, thioindigo, isoindoline, isoindolinone, quinacridone, Pyrrolopyrrole or quinophthalone pigments and metal complexes of azo, azomethine, methine, anthraquinone, indanthrone, pyranthrone, flavonthrone, benzanthrone, phthalocyanine, perylene, dioxazine, thioindigo, isoindoline, isoindolinone, quinacridone, Pyrrolopyrrole or quinophthalone pigments and metal complexes of azo, azomethine, methine, anthraquinone, indanthrone, pyranthro
  • the polyolefins can also contain fillers, such as kaolin, mica, feldspar, wollastonite, aluminum sili
  • the polyolefin for the carrier layer can also be produced as a concentrate (masterbatch). It then has correspondingly higher additions of the additive according to the invention, in the range from 20 to customary for masterbatch
  • This masterbatch is then mixed with a polyolefin before the production of films, so that the necessary concentrations of the additive of 0.05 to 10% by weight in the total amount are achieved.
  • the energy radiation of the laser used is preferably in the range of a wavelength in the far IR. In preferred
  • the energy radiation of the laser used is at a wavelength of 9,300 or 10,600 nm.
  • a laser with pulsed light is particularly preferably used, with
  • Polymer material is preferably carried out via an optical system consisting of a mirror, mask and lens.
  • the polyolefins can also be colored with various customary pigments or dyes.
  • the dye is generally brightened, the degree of brightening of which can be influenced by the energy density of the laser radiation used.
  • the process according to the invention has the advantage that there is no change in the surface of the laser-marked film when irradiated through the cover layer of the multilayer film, and thus the disadvantages of the prior art processes mentioned at the outset are completely avoided become.
  • the inscriptions produced using the method according to the invention are considerably more wear-resistant and can also be used without problems for packaging in the food sector, since this does not roughen the surface of the films.
  • the markings achieved are also high-contrast, sharp, abrasion-resistant and solvent-resistant.
  • the use for the labeling method according to the invention is intended for film packaging made of polyolefins, in particular for food packaging, for example films which are used for meat packaging.
  • the laser marking method according to the invention can also print, for example, packaging data, expiry dates, bar codes and other data on running filling lines in the filling cycle. Since the additives according to the invention have no color-imparting influence in visible light, foils equipped with them can be over-colored with colorants as desired, whereby the color intensity can easily be graded by adding the colorant.
  • FIG. 1 shows an SEM image of the cross section of a brittle fracture of a multilayer film which was produced by the method according to the invention. It can be seen on the picture that the surfaces of the film are unchanged and only in the middle part, where the laser-inscribable base layer is located, can foaming be seen.
  • FIG. 2 shows an SEM image of a brittle fracture of a laser-inscribed film of the prior art in a top view.
  • FIG. 3 shows a SEM image of a brittle fracture of the same film of the prior art in cross section. It can be clearly seen here that foaming and roughening occur on the surface of the layer, so that dirt particles or bacteria can penetrate into the film surface.
  • a single-layer film made of polyethylene (Escorene "LD-100 BW was produced on a film casting machine from Leistritz, Nuremberg. Cristobalite flour in the form of a masterbatch (50% filler degrees) distributed homogeneously in the film.
  • the labeling was carried out using a C02 laser, type Almark AL 861K from Alltech GmbH & Co KG, Luebeck, at a wavelength of 9300 nm. Energy densities of 3.5 J / cm " 4 resulted in clear white labeling.
  • REM 2 and 3 show recordings on a film cross section, the writing being recognizable as an open-pore foam structure on the film surface. The surface is foamed and rough.
  • a film with at least three layers was produced from polyethylene (Escorene ® LD-100 BW) as a test specimen on a multi-layer film casting system from Leistritz, Nuremberg.
  • the film was constructed as follows: top and bottom cover layers each 20 ⁇ m thick without additive; in the middle layer, also 20 ⁇ m thick, 2% cristobalite flour in the form of a masterbatch (50% filling degree) was homogeneously distributed as an additive.
  • the labeling was carried out using the CO 2 laser according to Comparative Example 1. The energy density of 3.5 J / cm gave clear labeling.
  • the SEM image of the film cross section is shown in FIG. 1. The position of the lettering as a foam structure in the middle layer can be seen. The other two layers, especially the surface of the foils, were not foamed and not rough.
  • a film was produced as in Example 1.
  • a surface-treated mica was (Iriodin 100 ® from Merck, Darmstadt) incorporated as a laser-sensitive additive. Labeling was carried out as in Comparative Example 1. The typeface was created in the middle layer without foaming the surface.

Landscapes

  • Physics & Mathematics (AREA)
  • Optics & Photonics (AREA)
  • Thermal Transfer Or Thermal Recording In General (AREA)
  • Laminated Bodies (AREA)
  • Treatments Of Macromolecular Shaped Articles (AREA)
  • Compositions Of Macromolecular Compounds (AREA)
  • Laser Beam Processing (AREA)
  • Electronic Switches (AREA)
  • Paper (AREA)

Abstract

A process is disclosed for writing by means of a laser on coloured or uncoloured foils having at least one covering layer and a base layer. The process is characterised in that the foil is irradiated by the laser radiation through the covering layer. The covering layer is selected so as to not absorb the used laser radiation and the supporting layer is finished so as to become able to receive an inscription made by a laser.

Description

Verfahren zur Laserbeschriftung von Folien Process for laser marking foils
Gegenstand der Erfindung ist ein Verfahren zur Laserbeschriftung von gefärbten oder ungefärbten Folien mit mindestens einer Deckschicht und einer Basisschicht.The invention relates to a method for laser marking of colored or uncolored films with at least one top layer and one base layer.
Gegenwärtig gewinnt die Kennzeichnung von Produktions- und Konsumgütern wachsende Bedeutung. Gegenüber den konventionellen Techniken der Beschriftung wie Bedrucken, Prägen und Etikettieren wird das berührungslose Markieren von Verpackungsfolien oder Formkörpern mit Hilfe von Lasern immer bedeutsamer, weil es auf einfache Weise auch in laufenden Produkti- onsprozessen angewandt werden kann.The labeling of production and consumer goods is becoming increasingly important. Compared to conventional labeling techniques such as printing, embossing and labeling, the non-contact marking of packaging foils or moldings with the help of lasers is becoming more and more important because it can easily be used in ongoing production processes.
Bei einigen thermoplastischen Kunststoffen, insbesondere den Polyolefinen, Polystyrol und Polyamiden, war es jedoch bisher schwierig, eine Lasermarkierung in ausreichender Schärfe, Lesbarkeit und mit gutem Kontrast zu erzielen. Werden Laser mit geringen Energien verwendet, kommt es entweder zu keiner Beschriftung oder nur zu einer Beschriftung mit schlechtem Kontrast. Werden Laser mit entsprechend höheren Energien verwendet, erfolgt im allgemeinen eine Zersetzung des polymeren Materials, was zu einer Schwarzfärbung fuhrt. Insbesondere die Beschriftung von Folien bereitet große Schwierigkeiten, da hier bei Anwendung von Laserstrahlung mit hohen Energien eine unerwünschte Verkohlung der Folie eintritt, die bis zur Zerstörung der Folie in den bestrahlten Bereichen führen kann.With some thermoplastics, especially the polyolefins, polystyrene and polyamides, however, it has so far been difficult to achieve laser marking with sufficient sharpness, legibility and good contrast. If lasers with low energies are used, there is either no labeling or only labeling with poor contrast. If lasers with correspondingly higher energies are used, the polymeric material generally decomposes, which leads to blackening. The labeling of foils, in particular, is very difficult since, when using laser radiation with high energies, undesired carbonization of the foil occurs, which can lead to the destruction of the foil in the irradiated areas.
Somit sind Polyolefine mit den üblichen Laserbeschrif ungssystemen für Kunststoffe nicht oder nur unzureichend beschriftbar, da sie einerseits die Wellenlänge des Laserlichts in be- stimmten Bereichen nicht absorbieren und andererseits die notwendige Schärfe der Markierung durch Lichtstreuung nicht erreicht wird. Dieser Nachteil führt dazu, daß Polyolefine, die aufgrund ihres Aussehens und ihrer Eigenschaften hervorragend für Verpackungszwecke geeignet sind, nur unzureichend mit Lasertechniken beschriftet werden können. Der Grund hierfür ist, daß die Polyolefinmatrix Laserstrahlen in den typi- sehen Wellenlängen von verwendeten Standardlasern wie 284, 351, 532, 1064 nm nicht oder nur wenig absorbiert. Bei anderen Polymeren, die stärker absorbieren, wird bei diesen Wellenlängen eine thermische Schädigung des Polymers erzeugt, wodurch es zu einer Gravur und zu einer Schwarzfärbung des Materials kommt. Die nachfolgenden Beschriftungsverfahren basieren im wesentlichen auf diesem Effekt.This means that polyolefins cannot be inscribed with the usual laser inscription systems for plastics, or only insufficiently, because on the one hand they do not absorb the wavelength of the laser light in certain areas and on the other hand the necessary sharpness of the marking is not achieved by light scattering. This disadvantage means that polyolefins, which, due to their appearance and properties, are ideal for packaging purposes, can only be insufficiently labeled with laser technology. The reason for this is that the polyolefin matrix does not absorb laser beams in the typical wavelengths of standard lasers used, such as 284, 351, 532, 1064 nm, or only little. For other polymers that absorb more, thermal damage to the polymer is generated at these wavelengths, causing the material to be engraved and blackened. The following labeling processes are essentially based on this effect.
Die DE AI 39 17 294.5 beschreibt mit Laserlicht beschriftbare Polyolefine. Diese Materialien enthalten als Zuschlagstoff 0,2 bis 4,5 Gew% Kupfer( II )-hydroxidphosphat oder 0,2 bis 2,5 Gew% Molybdän(VI)-oxid. Als Laser wird bevorzugt ein Neodym- YAG-Laser bei einer Wellenlänge von 1064 nm oder ein Excimer- Laser bei Wellenlängen von 308 oder 351 nm verwendet. Mit diesem Verfahren werden auf polymeren Spritzgußteilen schwär- ze Beschriftungen mit gutem Kontrast erzielt.DE AI 39 17 294.5 describes laser-inscribable polyolefins. These materials contain 0.2 to 4.5% by weight of copper (II) hydroxide phosphate or 0.2 to 2.5% by weight of molybdenum (VI) oxide as an additive. A neodymium-YAG laser at a wavelength of 1064 nm or an excimer laser at wavelengths of 308 or 351 nm is preferably used as the laser. With this process, black inscriptions with good contrast are achieved on polymer injection molded parts.
Die DE AI 41 36 994 beschreibt thermoplastische Formmassen mit lasersensitiver Pigmentierung, die als Zusatzstoff 0,001 bis 0,199 Gew% Kupfer( II )-hydroxidphosphat enthalten. Dabei werden als Thermoplasten unter anderem auch Polyolefine eingesetzt. Die Laserbeschriftung erfolgt mit Hilfe eines Neo- dym-YAG-Festkörperlasers mit einer Wellenlänge von 1060 nm. Man erhielt auf Formkörpern aus Polypropylen eine schwarze Beschriftung.DE AI 41 36 994 describes thermoplastic molding compositions with laser-sensitive pigmentation which contain 0.001 to 0.199% by weight of copper (II) hydroxide phosphate as an additive. Among other things, polyolefins are used as thermoplastics. The laser marking is carried out with the aid of a neodymium-YAG solid-state laser with a wavelength of 1060 nm. A black marking was obtained on molded articles made of polypropylene.
Die EP-Bl 0 190 997 beschreibt ein Verfahren zur Laserbeschriftung pigmentierter farbiger Polyolefine. Hierbei werden Kunststoffe wie Polyethylen und Polypropylen zunächst mit anorganischen oder organischen Pigmenten oder polymer-lösliehen Farbstoffen eingefärbt, wobei diese Farbmittel bevorzugt im nahen UV- und/oder sichtbaren oder nahen IR- Bereich absorbieren. Anschließend werden diese thermoplastischen Formma- ssen mit Laserstrahlung beschriftet, wobei das Laserlicht eine Wellenlänge im UV-Bereich (0,25 und 0,38 um) und/oder im sichtbaren Bereich und/oder im IR-Bereich (0,78 und 2 μm) besitzt. Mit dem Verfahren werden bei Polyolefinen schwarze Be- schriftungen erzeugt.EP-Bl 0 190 997 describes a method for laser marking pigmented colored polyolefins. Here, plastics such as polyethylene and polypropylene are first colored with inorganic or organic pigments or polymer-soluble dyes, these colorants preferably absorbing in the near UV and / or visible or near IR range. Then these thermoplastic molding must be labeled with laser radiation, the laser light having a wavelength in the UV range (0.25 and 0.38 μm) and / or in the visible range and / or in the IR range (0.78 and 2 μm). The process creates black labels for polyolefins.
EP-AI 0 111 357 beschreibt ein Verfahren zur Laserbeschriftung von Formkörpern aus Polyolefinen durch Bestrahlung mit einem TEA-Cθ2~Laser . Die Intensität des Laserpulses beträgt 333 kW/cm2. Das Polyolefin enthält als Zusatzstoff Calciumme- tasilikate, Aluminiumsilikat oder Kaolin. Mit dem Verfahren wird eine schwarze Beschriftung erzielt.EP-AI 0 111 357 describes a method for laser marking molded articles made of polyolefins by irradiation with a TEA-CO 2 laser. The intensity of the laser pulse is 333 kW / cm 2 . As an additive, the polyolefin contains calcium metasilicate, aluminum silicate or kaolin. The procedure produces black lettering.
Aus "Kunststoffe 79 (1989) ,11" ist ein Verfahren zur Laserbe- schriftung von Polyolefinfolien bekannt, das eine schwarze Markierung ergibt. Dabei wird den Polyolefinen als Zusatzstoff etwa 0,1 Gew% eines Glimmerpigmentes zugegeben, das unter der Bezeichnung Iriodin® ( Hersteller: Merck, Darmstadt) im Handel erhältlich ist. Die flachen Glimmerplättchen werden mit einer dünnen Schicht eines Metalloxids mit hoher Brechzahl beschichtet. Im Kunststoff sind die Pigmentplättchen parallel zur Oberfläche orientiert. Trifft ein Laserstrahl auf die Pigmentplättchen, so wird ein Teil des Lichts an den Pigmenten reflektiert, der übrige Teil transmittiert . Durch die Geometrie der Plättchen liegen der einfallende und der reflektierende Lichtstrahl dicht beieinander, so daß im Bereich des Laserlichtstrahls die zur Verfügung stehende Energiedichte erhöht und eine Oberflächenschicht des Kunststoffs carbonisiert wird. Dies ergibt eine kontrastreiche schwarze Markierung.From "Kunststoffe 79 (1989), 11" a method for laser inscription of polyolefin films is known which results in a black marking. In this case, the polyolefins is added as an additive from about 0.1% by weight of a mica pigment, sold under the name Iriodin ®: is commercially available (manufactured by Merck, Darmstadt). The flat mica flakes are coated with a thin layer of a metal oxide with a high refractive index. In the plastic, the pigment flakes are oriented parallel to the surface. If a laser beam hits the pigment platelets, part of the light is reflected on the pigments, the rest is transmitted. Due to the geometry of the platelets, the incident and the reflecting light beam are close together, so that in the area of the laser light beam the available energy density is increased and a surface layer of the plastic is carbonized. This results in a high-contrast black marking.
Verfahren zur Laserbeschriftung von Polyolefinen mit denen eine gute weiße oder graue Beschriftung erzeugt wird sind bisher nur in geringem Maße bekannt. So wird beispielsweise in der DE 195 25 958.0 ein Verfahren zur Herstellung laserbeschrifteter Folien vorgeschlagen, wobei die Folien aus einem Polyolefin bestehen und 0,2 bis 10 Gew% eines Zusatzstoffes enthalten. Als Zusatzstoff wird ein Silikat oder Siliciumdi- oxid mit einer Teilchengröße von 0,01 bis 100 μ verwendet. Die so hergestellten Folien werden dann mit Laserstrahlung mit einer Energiedichte von 1 bis 10 J/cπr* bestrahlt. Mit diesem Verfahren werden kontrastreiche weiße oder hellgraue Beschriftungen erzielt.Processes for laser marking polyolefins with which good white or gray marking is produced have hitherto been known only to a limited extent. For example, DE 195 25 958.0 proposes a process for producing laser-labeled films, the films consisting of a polyolefin and 0.2 to 10% by weight of an additive contain. A silicate or silicon dioxide with a particle size of 0.01 to 100 μ is used as additive. The films thus produced are then irradiated with laser radiation with an energy density of 1 to 10 J / cπr * . With this process, high-contrast white or light gray lettering is achieved.
Die bisherigen Laserbeschriftungsverfahren aus dem Stand der Technik besitzen den Nachteil, daß sie die Oberflächen der mit Laser beschrifteten Folien verändern. Hierbei werden verschiedene Effekte beobachtet. Es kann durch die Laserbestrahlung zu einem Aufschäumen des Materials kommen. Bei dem Einsatz von Laserstrahlen höherer Energien wird das Material an der Oberfläche abgetragen oder carbonisiert . Es entsteht eine Gravur an der Oberfläche der Folie.The previous laser marking methods from the prior art have the disadvantage that they change the surfaces of the films marked with laser. Various effects are observed here. Laser radiation can cause the material to foam. When using higher energy laser beams, the material is removed or carbonized on the surface. An engraving is created on the surface of the film.
In jedem Fall wird bei der Laserbeschriftung die glatte Oberfläche der Folie nachteilig verändert, und aus diesen Veränderungen ergeben sich zahlreiche Nachteile für die Verwendung der Folien. Zunächst kommt es durch die Aufschäumung oder durch die Gravur zu einer mechanischen Schwächung der Folie. Sie wird spröder und verliert ihre mechanischen Eigenschaften. Da es bei der Aufschäumung oder der Gravur der Oberfläche der Folie auch zu einer Aufrauhung kommt, entsteht an diesen Stellen eine Verschmutzungsneigung an der Folienoberfläche, was dazu führt, daß die Beschriftungen mit der Zeit unleserlich werden und ihren Kontrast verlieren. Im Verpak- kungsbereich besteht weiterhin der große Nachteil, daß sich in diese rauhe Oberflächenschicht auch Bakterien einnisten können, die insbesondere bei Verpackungen von Lebensmitteln unerwünscht sind.In any case, the smooth surface of the film is adversely changed in laser marking, and these changes result in numerous disadvantages for the use of the films. First, the foaming or the engraving mechanically weaken the film. It becomes more brittle and loses its mechanical properties. Since the foaming or engraving of the surface of the film also causes roughening, there is a tendency for the surface of the film to become dirty at these points, which means that the labels become illegible over time and lose their contrast. In the packaging area, there is also the great disadvantage that bacteria can also nest in this rough surface layer, which are undesirable particularly in the packaging of foodstuffs.
Hinzu kommt, daß eine Beschriftung auf einer offenen rauhen Oberfläche keineswegs verschleißfest ist, sondern mit der Zeit abgetragen werden kann. Das technische Problem der Erfindung war es daher, ein Verfahren zur Laserbeschriftung von Folien zu entwickeln, bei dem die oben beschriebenen Nachteile nicht auftreten und insbesondere die Oberflächenschicht der Folie nicht verändert oder aufgerauht wird.In addition, lettering on an open, rough surface is by no means wear-resistant, but can be removed over time. The technical problem of the invention was therefore to develop a method for laser marking foils in which the disadvantages described above do not occur and in particular the surface layer of the foil is not changed or roughened.
Dieses technische Problem wird gelöst durch ein Verfahren zur Laserbeschriftung von gefärbten oder ungefärbten Folien mit mindestens einer Deckschicht und einer Basisschicht, wobei die Folie durch die Deckschicht hindurch mit Laserstrahlung bestrahlt wird und die Deckschicht so gewählt wird, daß sie die verwendete Laserstrahlung nicht absorbiert und die Trägerschicht laserbeschriftbar ausgerüstet ist. Mehrschichtige Folien sind aus dem Stand der Technik bekannt. Sie können verschiedenartig je nach Verwendungszweck ausgerüstet und durch Koextrusion hergestellt werden.This technical problem is solved by a method for laser marking of colored or uncolored films with at least one cover layer and a base layer, the film being irradiated with laser radiation through the cover layer and the cover layer being chosen such that it does not absorb the laser radiation used and the Carrier layer is equipped with laser marking. Multi-layer films are known from the prior art. They can be equipped in various ways depending on the intended use and can be produced by coextrusion.
In bevorzugter Ausführungsform besteht die Deckschicht aus Polymerisaten oder Copolymerisaten des Polyethylens, Polypro- pylens, Polybuten-1, Polyisobutylens, Poly-4-methylpenten-l, Polyacetylen oder Polyamid. Die Trägerschicht besteht in bevorzugter Weise aus einem Polyolefin und enthält 0,05 bis 10 Gew% eines Zusatzstoffes ausgewählt aus der Gruppe Silikate und Siliciumdioxid mit einer Teilchengröße von 0,01 bis 100 μ .In a preferred embodiment, the cover layer consists of polymers or copolymers of polyethylene, polypropylene, polybutene-1, polyisobutylene, poly-4-methylpentene-1, polyacetylene or polyamide. The carrier layer preferably consists of a polyolefin and contains 0.05 to 10% by weight of an additive selected from the group consisting of silicates and silicon dioxide with a particle size of 0.01 to 100 μ.
In besonders bevorzugter Ausführungsform wird der Zusatzstoff für die Basisschicht ausgewählt aus der Gruppe Siliciumdioxid in kristalliner oder amorpher Form, Glimmer, Feldspat, calci- nierter Kaolin, Kaolin, Nephelinsyenit, Talkum, Calciumsili- cathydrat, Kieselsäure, pyrogene oder gefällte Kieselsäure, Cristobalit, Diatomeenerde, Kieselgur, Mikro-Glaskugeln oder Gemische derselben.In a particularly preferred embodiment, the additive for the base layer is selected from the group consisting of silicon dioxide in crystalline or amorphous form, mica, feldspar, calcined kaolin, kaolin, nepheline syenite, talc, calcium silicate hydrate, silica, pyrogenic or precipitated silica, cristobalite, diatomaceous earth , Diatomaceous earth, micro-glass balls or mixtures thereof.
Zur Laserbestrahlung wird in bevorzugter Weise ein Excimer- Laser, ein Neodym-YAG-Laser oder ein C02-Laser eingesetzt. Excimer-Laser besitzen Wellenlängen im UV-Bereich von 193 bis 351 nm, beispielsweise 196, 248, 308 und 351 nm. Neodym-YAG- Laser finden im sichtbaren und im nahen IR-Bereich Anwendung, beispielsweise bei Wellenlängen von 532 und 1064 nm. Als weiterer Laser, der im Infrarot-Bereich emittiert, ist der C02- Laser zu nennen. Dieser Laser emittiert beispielsweise im fernen IR-Bereich bei Wellenlängen von 10.600 nm bzw. 9.300 nm. Besonders bevorzugt ist der Einsatz von gepulsten Lasern mit Pulsdauern von 1 bis 1000 ns. Die verwendeten Energiedichten liegen bevorzugt zwischen 1 und 20 J/cm .An excimer laser, a neodymium-YAG laser or a CO 2 laser is preferably used for laser irradiation. Excimer lasers have wavelengths in the UV range from 193 to 351 nm, for example 196, 248, 308 and 351 nm. Neodymium YAG lasers are used in the visible and in the near IR range, for example at wavelengths of 532 and 1064 nm. As a further laser that emits in the infrared range to name the C02 laser. This laser emits, for example, in the far IR range at wavelengths of 10,600 nm or 9,300 nm. The use of pulsed lasers with pulse durations of 1 to 1000 ns is particularly preferred. The energy densities used are preferably between 1 and 20 J / cm.
Zur Färbung der Folie werden in bevorzugter Weise anorganische oder organische Pigmente oder polymerlösliche Farbstoffe eingesetzt. Der Zusatzstoff für die Basisschicht kann weiterhin im Gemisch mit Polyolefin als Masterbatch eingesetzt wer- den.Inorganic or organic pigments or polymer-soluble dyes are preferably used for coloring the film. The additive for the base layer can also be used in a mixture with polyolefin as a masterbatch.
In bevorzugter Weise wird zur Laserbeschriftung ein Cθ2-Laser bei Wellenlängen von 10.600 oder 9.300 nm eingesetzt. Die Folien können mit einer Energiedichte von 1 bis 10 J/cm2, be-A CO 2 laser at wavelengths of 10,600 or 9,300 nm is preferably used for laser marking. The foils can have an energy density of 1 to 10 J / cm 2 ,
- vorzugt 1 bis 7 J/cra' bestrahlt werden.- preferably 1 to 7 J / cra 'are irradiated.
Figur 1 zeigt eine REM-Aufnahme des Querschnitts eines Spröd- bruchs einer mehrschichtigen Folie, die nach dem erfindungsgemäßen Verfahren hergestellt wurde.FIG. 1 shows an SEM image of the cross section of a brittle fracture of a multilayer film which was produced by the method according to the invention.
Die Figur 2 zeigt eine REM-Aufnahme eines Sprödbruchs einer laserbeschrifteten Folie des Standes der Technik in Aufsicht.FIG. 2 shows a SEM image of a brittle fracture of a laser-inscribed film of the prior art in supervision.
Die Figur 3 zeigt eine REM-Aufnahme des Querschnitts eines Sprödbruchs einer laserbeschrifteten Folie des Standes der Technik.FIG. 3 shows an SEM image of the cross section of a brittle fracture of a laser-inscribed film of the prior art.
Als Polyolefine für die Trägerschicht werden bevorzugt solche verwendet, die sich von Alkenen mit 2 bis 10 C-Atomen ablei- ten. Bevorzugt werden Homo- oder Copolymerisate des Ethylens, Propylens oder Butylens verwendet. Polyethylene können hergestellt werden nach dem Hoch-, Mittel- oder Niederdruckverfah- ren. Weiterhin können Copolymerisate von Ethylen mit Phenyl- estern, Acrylestern oder mit Propylen eingesetzt werden. In besonders bevorzugter Weise werden Polyethylen hoher Dichte oder lineares Polyethylen niedriger Dichte eingesetzt. Es können weiterhin auch Polyethylene eingesetzt werden, die übliche Füllstoffe, Stabilisatoren, Antiblockmittel enthalten.The polyolefins used for the support layer are preferably those derived from alkenes having 2 to 10 carbon atoms. Homopolymers or copolymers of ethylene, propylene or butylene are preferably used. Polyethylenes can be manufactured using the high, medium or low pressure process. Ren. Copolymers of ethylene with phenyl esters, acrylic esters or with propylene can also be used. In a particularly preferred manner, high-density polyethylene or linear low-density polyethylene are used. Polyethylenes which contain conventional fillers, stabilizers and antiblocking agents can also be used.
Ein weiteres Polyolefin das in bevorzugter Weise verwendet werden kann, ist Polypropylen, das beispielsweise nach dem Gasphasen-Verfahren unter Verwendung von Ziegler-Natta-Another polyolefin that can be used in a preferred manner is polypropylene, which is used, for example, according to the gas phase process using Ziegler-Natta
Katalysatoren hergestellt werden kann. Weiterhin sind Copolymerisate des Propylens zu nennen, die beispielsweise aus Pro- pylenhomopolymerisat und Polypropylencopolymerisat mit einpo- lymerisiertem C2 bis Cιo-Alk-1-enen bestehen. Als einpolyme- risierte C2 bis Cin-Alkene werden beispielsweise Ethylen, Bu- ten-1, Penten-1, Hexen-1 oder Octen-1 oder Gemische dieser verwendet. Bevorzugt sind Ethylen und Buten-1.Catalysts can be made. Also to be mentioned are copolymers of propylene which consist, for example, of propylene homopolymer and polypropylene copolymer with copolymerized C2 to CIO-alk-1-enes. Ethylene, butene-1, pentene-1, hexene-1 or octene-1 or mixtures thereof are used, for example, as polymerized C2 to cin-alkenes. Ethylene and butene-1 are preferred.
Die Herstellung dieser Propylencopolymerisate erfolgt durch Polymerisation mit Hilfe von Ziegler-Natta-Katalysatoren, vorzugsweise in der Gasphase mit den in der Technik gebräuchlichen Polymerisationsreaktoren. Allgemein sind Verfahren zur Herstellung von Polyolefinen bekannt und werden in "Ullmanns Enzyklopädie der technischen Chemie", 4. Auflage, Band 19, Seiten 167 bis 226, beschrieben.These propylene copolymers are prepared by polymerization using Ziegler-Natta catalysts, preferably in the gas phase using the polymerization reactors customary in the art. Processes for the production of polyolefins are generally known and are described in "Ullmann's Encyclopedia of Industrial Chemistry", 4th edition, volume 19, pages 167 to 226.
Das zur Laserbeschriftung geeignete Polyolefin kann weiterhin übliche Zusatzstoffe oder Pigmente enthalten. Beispiele von anorganischen Pigmenten, die eine Verfärbung verursachen, sind Weißpigmente, wie Titanoxid, Zinkoxid, Antimontrioxid, Zinksulfid, Lithopone, basisches Bleikarbonat, basisches Bleisulfat oder basisches Bleisilicat, ferner Metalloxid, wie Eisenoxide, Chromoxide, Nickelantimontitanat, Chromantimonti- tanat, Manganblau, Manganviolett, Kobaltblau, Kobaltchrom- blau, Kobaltnickelgrau oder Ultramarinblau, Berlinerblau, Bleichromate, Bleisulfochromate, Molybdatorange, Molybdatrot, Metallsulfide, wie Cadmiumsulfid, Arsendisulfid, Antimontri- sulfid oder Cadmiu sulfoselenide, Zirkoniumsilicate wie Zirkoniumvanadiumblau und Zirkoniumpraseodymgelb, ferner Ruß oder Graphit in kleinen Konzentrationen.The polyolefin suitable for laser marking can also contain conventional additives or pigments. Examples of inorganic pigments that cause discoloration are white pigments, such as titanium oxide, zinc oxide, antimony trioxide, zinc sulfide, lithopone, basic lead carbonate, basic lead sulfate or basic lead silicate, and also metal oxide, such as iron oxides, chromium oxides, nickel antimony titanate, chromium antimony titanate, manganese blue, manganese violet , Cobalt blue, cobalt chrome blue, cobalt nickel gray or ultramarine blue, Berlin blue, lead chromates, lead sulfochromates, molybdate orange, molybdate red, metal sulfides such as cadmium sulfide, arsenic disulfide, antimony tri sulfide or Cadmiu sulfoselenide, zirconium silicates such as zirconium vanadium blue and zirconium praseodymium yellow, also carbon black or graphite in small concentrations.
5 Beispiele organischer Pigmente sind Azo-, Azomethin-, Methin- , Anthrachinon-, Indanthron-, Pyranthron-, Flavonthron-, Benzanthron- , Phtalocyanin-, Perylen-, Dioxazin-, Thioindigo- , Isoindolin-, Isoindolinon-, Chinacridon-, Pyrrolopyrrol- oder Chinophtalonpigmente sowie Metallkomplexe von Azo-, Azo-5 Examples of organic pigments are azo, azomethine, methine, anthraquinone, indanthrone, pyranthrone, flavonthrone, benzanthrone, phthalocyanine, perylene, dioxazine, thioindigo, isoindoline, isoindolinone, quinacridone, Pyrrolopyrrole or quinophthalone pigments and metal complexes of azo, azo
10 methin- oder Methinfarbstoffen oder Metallsalzen von Azover- bindungen.10 methine or methine dyes or metal salts of azo compounds.
Die Polyolefine können weiterhin auch Füllstoffe enthalten, wie Kaolin, Glimmer, Feldspate, Wollastonit, Aluminiumsili-The polyolefins can also contain fillers, such as kaolin, mica, feldspar, wollastonite, aluminum sili
15 cat, Bariumsulfat, Calciumsulfat, Kreide, Calcit und Dolomit. Weiterhin können Lichtschutzmittel, Antioxidantien, Flammschutzmittel, Hitzestabilisatoren, Glasfasern oder Verarbeitungsmittel, welche bei der Verarbeitung von Kunststoffen üblich sind, eingesetzt werden.15 cat, barium sulfate, calcium sulfate, chalk, calcite and dolomite. Furthermore, light stabilizers, antioxidants, flame retardants, heat stabilizers, glass fibers or processing agents which are customary in the processing of plastics can be used.
2020th
Das Polyolefin für die Trägerschicht kann weiterhin auch als Konzentrat (Masterbatch) hergestellt werden. Es besitzt dann entsprechend höhere Zusätze des erfindungsgemäßen Zuschlagstoffes, die in für Masterbatch üblichen Bereichen von 20 bisThe polyolefin for the carrier layer can also be produced as a concentrate (masterbatch). It then has correspondingly higher additions of the additive according to the invention, in the range from 20 to customary for masterbatch
25 80 Gew% liegen. Dieses Masterbatch wird dann vor der Erzeugung von Folien mit einem Polyolefin gemischt, so daß die notwendigen Konzentrationen des Zuschlagstoffes von 0,05 bis 10 Gew% in der Gesamtmenge erreicht werden.25 80% by weight. This masterbatch is then mixed with a polyolefin before the production of films, so that the necessary concentrations of the additive of 0.05 to 10% by weight in the total amount are achieved.
30 Die Energiestrahlung des verwendeten Lasers liegt bevorzugt im Bereich einer Wellenlänge im fernen IR. In bevorzugter30 The energy radiation of the laser used is preferably in the range of a wavelength in the far IR. In preferred
Weise liegt die Energiestrahlung des verwendeten Lasers bei einer Wellenlänge von 9.300 oder 10.600 nm. Es wird besonders bevorzugt ein Laser mit gepulstem Licht verwendet, wobei mitThe energy radiation of the laser used is at a wavelength of 9,300 or 10,600 nm. A laser with pulsed light is particularly preferably used, with
35 einer Energiedichte von 1 bis 10 J/cm' , bevorzugt 2,5 bis 8 ~ J/cm , bestrahlt wird. Die Bestrahlung des erfindungsgemäßen Polymermaterials erfolgt in bevorzugter Weise über ein optisches System aus Spiegel, Maske und Linse.35 an energy density of 1 to 10 J / cm ', preferably 2.5 to 8 ~ J / cm, is irradiated. Irradiation of the invention Polymer material is preferably carried out via an optical system consisting of a mirror, mask and lens.
Mit dem erfindungsgemäßen Verfahren lassen sich hervorragende Beschriftungen insbesondere auf naturfarbenen Polyolefinmehr- schichtfolien in weiß oder grau erzielen. Die Polyolefine können jedoch auch eingefärbt sein mit verschiedenen üblichen Pigmenten oder Farbstoffen. Bei der Laserbeschriftung wird dann im allgemeinen eine Aufhellung des Farbstoffes erzielt, deren Aufhellungsgrad durch die Energiedichte der verwendeten Laserstrahlung beeinflußt werden kann.With the method according to the invention, excellent inscriptions, in particular on natural-colored polyolefin multilayer films in white or gray, can be achieved. However, the polyolefins can also be colored with various customary pigments or dyes. In the case of laser marking, the dye is generally brightened, the degree of brightening of which can be influenced by the energy density of the laser radiation used.
Gegenüber bisherigen bekannten Laserbeschriftungsverfahren für Folien besitzt das erfindungsgemäße Verfahren den Vor- teil, daß es bei der Bestrahlung durch die Deckschicht der mehrschichtigen Folie hindurch zu keiner Veränderung der Oberfläche der laserbeschrifteten Folie kommt und damit die eingangs erwähnten Nachteile der Verfahren des Standes der Technik vollständig vermieden werden. Die mit dem erfindungs- gemäßen Verfahren hergestellten Beschriftungen sind erheblich verschleißfester und können ohne weiteres auch für Verpackungen im Lebensmittelbereich eingesetzt werden, da es hierbei nicht zu einer Aufrauhung der Oberfläche der Folien kommt. Die erzielten Beschriftungen sind ferner kontrastreich, kan- tenscharf, abriebfest und lösungsmittelfest.Compared to previously known laser marking processes for films, the process according to the invention has the advantage that there is no change in the surface of the laser-marked film when irradiated through the cover layer of the multilayer film, and thus the disadvantages of the prior art processes mentioned at the outset are completely avoided become. The inscriptions produced using the method according to the invention are considerably more wear-resistant and can also be used without problems for packaging in the food sector, since this does not roughen the surface of the films. The markings achieved are also high-contrast, sharp, abrasion-resistant and solvent-resistant.
Der Einsatz für das erfindungsgemäße Beschriftungsverfahren ist vorgesehen für Folienverpackungen aus Polyolefinen, insbesondere für LebensmittelVerpackungen, beispielsweise Foli- en, die zur Fleischverpackung verwendet werden. Das erfindungsgemäße Laserbeschriftungsverfahren kann beispielsweise auch an laufenden Abfüllstraßen im Abfülltakt z.B. Abpackdaten, Verfallsdaten, Barcodes und andere Daten aufdrucken. Da die erfindungsgemäßen Zuschlagsstoffe im sichtbaren Licht keinen farbgebenden Einfluß besitzen, können damit ausgerüstete Folien mit Farbmitteln beliebig überfärbt werden, wobei die Farbintensität über die Zugabe des Farbmittels leicht abstufbar ist.The use for the labeling method according to the invention is intended for film packaging made of polyolefins, in particular for food packaging, for example films which are used for meat packaging. The laser marking method according to the invention can also print, for example, packaging data, expiry dates, bar codes and other data on running filling lines in the filling cycle. Since the additives according to the invention have no color-imparting influence in visible light, foils equipped with them can be over-colored with colorants as desired, whereby the color intensity can easily be graded by adding the colorant.
Die nachfolgenden Figuren zeigen laserbestrahlte Folien, die mit dem herkömmlichen Verfahren gemäß DE 195 25 958.0 bestrahlt wurden und Folien, die mit dem erfindungsgemäßen Verfahren bestrahlt wurden.The following figures show laser-irradiated foils which have been irradiated with the conventional method according to DE 195 25 958.0 and foils which have been irradiated with the method according to the invention.
Figur 1 zeigt eine REM-Aufnahme des Querschnitts eines Spröd- bruchs einer mehrschichtigen Folie, die nach dem erfindungsgemäßen Verfahren hergestellt wurde. Auf der Aufnahme ist zu erkennen, daß die Oberflächen der Folie unverändert sind und lediglich im mittleren Teil, wo sich die laserbeschriftbare Basisschicht befindet, eine Aufschäumung zu erkennen ist.FIG. 1 shows an SEM image of the cross section of a brittle fracture of a multilayer film which was produced by the method according to the invention. It can be seen on the picture that the surfaces of the film are unchanged and only in the middle part, where the laser-inscribable base layer is located, can foaming be seen.
Die Figur 2 zeigt eine REM-Aufnahme eines Sprödbruchs einer laserbeschrifteten Folie des Standes der Technik in der Aufsicht. Die Figur 3 zeigt eine REM-Aufnahme eines Sprödbruchs derselben Folie des Standes der Technik im Querschnitt. Hier ist deutlich zu erkennen, daß es an der Oberfläche der Schicht zu einer Aufschäumung und Aufrauhung kommt, so daß Schmutzpartikel oder Bakterien in die Folienoberfläche eindringen können.FIG. 2 shows an SEM image of a brittle fracture of a laser-inscribed film of the prior art in a top view. FIG. 3 shows a SEM image of a brittle fracture of the same film of the prior art in cross section. It can be clearly seen here that foaming and roughening occur on the surface of the layer, so that dirt particles or bacteria can penetrate into the film surface.
Die nachfolgenden Beispiele sollen die Erfindung näher erläutern.The following examples are intended to explain the invention in more detail.
BEISPIELEEXAMPLES
Verqleichsbeispiel 1Comparative Example 1
Es wurde eine einschichtige Folie aus Polyethylen(Escorene " LD-100 BW auf einer Folien-Gießanlage der Firma Leistritz, Nürnberg hergestellt. Bei der Herstellung wurde als Zusatzstoff Cristobalitmehl in Form eines Masterbatches (50% Füll- grad) homogen in der Folie verteilt. Die Beschriftung erfolgte mit einem C02- Laser, Typ Almark AL 861K der Firma Alltech GmbH & Co KG, Lübeck bei einer Wellenlänge von 9300 nm. Ener- giedichten von 3,5 J/cm"4, ergaben weiße deutliche Beschriftun- gen. REM-Aufnahmen an einem Folienquerschnitt zeigen die Figuren 2 und 3 , wobei die Schrift als offenporige Schaumstruktur auf der Folienoberfläche zu erkennen ist. Die Oberfläche ist aufgeschäumt und rauh.A single-layer film made of polyethylene (Escorene "LD-100 BW was produced on a film casting machine from Leistritz, Nuremberg. Cristobalite flour in the form of a masterbatch (50% filler degrees) distributed homogeneously in the film. The labeling was carried out using a C02 laser, type Almark AL 861K from Alltech GmbH & Co KG, Luebeck, at a wavelength of 9300 nm. Energy densities of 3.5 J / cm " 4 resulted in clear white labeling. REM 2 and 3 show recordings on a film cross section, the writing being recognizable as an open-pore foam structure on the film surface. The surface is foamed and rough.
Beispiel 1example 1
Als Probekörper wurde aus Polyethylen (Escorene® LD-100 BW) eine Folie mit mindestens drei Schichten auf einer Mehr- schichtfolien-Gießanlage der Firma Leistritz, Nürnberg hergestellt. Die Folie war wie folgt aufgebaut: obere und untere Deckschicht je 20 um stark ohne Zusatzstoff; in der mittleren Schicht, ebenfalls 20 um stark, wurde als Zusatzstoff 2% Cri- stobalitmehl in Form eines Masterbatches (50% Füllgrad) homo- gen verteilt. Die Beschriftung erfolgte mit dem Cθ2-Laser gemäß Vergleichsbeispiel 1. Die Energiedichte von 3,5 J/cm ergab deutliche Beschriftungen. Die REM-Aufnahme des Folienquerschnittes zeigt Figur 1. Die Lage der Beschriftung als Schaumstruktur in der mittleren Schicht ist zu erkennen. Die beiden anderen Schichten, insbesondere die Oberfläche der Folien, waren nicht aufgeschäumt und nicht rauh.A film with at least three layers was produced from polyethylene (Escorene ® LD-100 BW) as a test specimen on a multi-layer film casting system from Leistritz, Nuremberg. The film was constructed as follows: top and bottom cover layers each 20 μm thick without additive; in the middle layer, also 20 µm thick, 2% cristobalite flour in the form of a masterbatch (50% filling degree) was homogeneously distributed as an additive. The labeling was carried out using the CO 2 laser according to Comparative Example 1. The energy density of 3.5 J / cm gave clear labeling. The SEM image of the film cross section is shown in FIG. 1. The position of the lettering as a foam structure in the middle layer can be seen. The other two layers, especially the surface of the foils, were not foamed and not rough.
Beispiel 2Example 2
Es wurde eine Folie wie in Beispiel 1 hergestellt. In die mittlere Schicht wurde als lasersensitives Additiv 0,5% eines oberflächenbehandelten Glimmers ( Iriodin 100® der Firma Merck, Darmstadt) eingearbeitet. Beschriftet wurde wie in Vergleichsbeispiel 1. Das Schriftbild ist in der mittleren Schicht ohne Aufschäumen der Oberfläche entstanden. A film was produced as in Example 1. In the middle layer 0.5% of a surface-treated mica was (Iriodin 100 ® from Merck, Darmstadt) incorporated as a laser-sensitive additive. Labeling was carried out as in Comparative Example 1. The typeface was created in the middle layer without foaming the surface.

Claims

PATENTANSPRÜCHE PATENT CLAIMS
1. Verfahren zur Laserbeschriftung von gefärbten oder unge- färbten Folien mit mindestens einer Deckschicht und einer Basisschicht, dadurch gekennzeichnet, daß die Folie durch die Deckschicht mit Laserstrahlung bestrahlt wird, wobei die Deckschicht so gewählt wird, daß sie die verwendete LaserStrahlung nicht absorbiert und die Träger- schicht laserbeschriftbar ausgerüstet ist.1. A method for laser inscription of colored or non-colored films with at least one cover layer and a base layer, characterized in that the film is irradiated with laser radiation through the cover layer, the cover layer being selected such that it does not absorb the laser radiation used and the Carrier layer is equipped with laser inscription.
2. Verfahren nach Anspruch 1 , dadurch gekennzeichnet, daß die Deckschicht aus Polymerisaten oder Copolymerisaten des Polyethylens, Polypropylens, Polybuten-1, Polyiso- butylen, Poly-4-Methylpenten-l, Polyacetylen oder Polyamid besteht.2. The method according to claim 1, characterized in that the cover layer consists of polymers or copolymers of polyethylene, polypropylene, polybutene-1, polyisobutylene, poly-4-methylpentene-1, polyacetylene or polyamide.
3. Verfahren nach Anspruch 1 oder Anspruch 2, dadurch gekennzeichnet, daß die Trägerschicht aus einem Polyolefin und 0.05 bis 10 Gew% eines Zusatzstoffes ausgewählt aus der Gruppe Silikate und Siliciumdioxid mit einer Teilchengröße von 0,01 bis 100 um besteht.3. The method according to claim 1 or claim 2, characterized in that the carrier layer consists of a polyolefin and 0.05 to 10% by weight of an additive selected from the group consisting of silicates and silicon dioxide with a particle size of 0.01 to 100 µm.
4. Verfahren nach den Ansprüchen 1 bis 3, dadurch gekenn- zeichnet, daß der Zusatzstoff ausgewählt ist aus der4. The method according to claims 1 to 3, characterized in that the additive is selected from the
Gruppe Siliciumdioxid in kristalliner oder amorpher Form, Glimmer, Feldspat, calcinierter Kaolin, Kaolin, Nephelinsyenit, Talkum, Calciumsilicathydrat, Kieselsäure, pyrogene oder gefällte Kieselsäure, Cristobalit, Diatomeenerde, Kieselgur, Mikro-Glaskugeln oder Gemische derselben.Group of silicon dioxide in crystalline or amorphous form, mica, feldspar, calcined kaolin, kaolin, nepheline syenite, talc, calcium silicate hydrate, silicic acid, pyrogenic or precipitated silicic acid, cristobalite, diatomaceous earth, diatomaceous earth, micro-glass balls or mixtures thereof.
5. Verfahren nach den Ansprüchen 1 bis 4, dadurch gekennzeichnet, daß zur Laserbestrahlung ein Excimer-Laser, Neodym-YAG-Laser oder Cθ2-Laser eingesetzt wird. 5. The method according to claims 1 to 4, characterized in that an excimer laser, neodymium-YAG laser or CO 2 laser is used for laser irradiation.
6. Verfahren nach den Ansprüchen 1 bis 5, dadurch gekennzeichnet, daß zur Färbung der Folie anorganische oder organische Pigmente oder polymerlösliche Farbstoffe eingesetzt werden.6. Process according to claims 1 to 5, characterized in that inorganic or organic pigments or polymer-soluble dyes are used for coloring the film.
7. Verfahren nach den Ansprüchen 1 bis 6, dadurch gekennzeichnet, daß der Zusatzstoff für die Trägerschicht im Gemisch mit Polyolefin als Masterbatch eingesetzt wird.7. The method according to claims 1 to 6, characterized in that the additive for the carrier layer in a mixture with polyolefin is used as a master batch.
8. Verfahren nach den Ansprüchen 1 bis 7, dadurch gekennzeichnet, daß die Folien mit einer Energiedichte von 18. The method according to claims 1 to 7, characterized in that the films with an energy density of 1
2 bis 10 J/cm bestrahlt werden. 2 to 10 J / cm are irradiated.
9. Verfahren nach den Ansprüchen 1 bis 8, dadurch gekenn- zeichnet, daß die Energiestrahlung des Lasers eine Wellenlänge von 10.600 nm oder 9.300 nm besitzt. 9. The method according to claims 1 to 8, characterized in that the energy radiation of the laser has a wavelength of 10,600 nm or 9,300 nm.
EP97934462A 1996-07-27 1997-07-14 Process for writing on foils by means of a laser Expired - Lifetime EP0914257B1 (en)

Applications Claiming Priority (3)

Application Number Priority Date Filing Date Title
DE19630478 1996-07-27
DE19630478A DE19630478A1 (en) 1996-07-27 1996-07-27 Process for laser marking foils
PCT/EP1997/003757 WO1998004417A1 (en) 1996-07-27 1997-07-14 Process for writing on foils by means of a laser

Publications (2)

Publication Number Publication Date
EP0914257A1 true EP0914257A1 (en) 1999-05-12
EP0914257B1 EP0914257B1 (en) 2001-11-07

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EP97934462A Expired - Lifetime EP0914257B1 (en) 1996-07-27 1997-07-14 Process for writing on foils by means of a laser

Country Status (6)

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EP (1) EP0914257B1 (en)
JP (1) JP2000501670A (en)
AT (1) ATE208280T1 (en)
DE (2) DE19630478A1 (en)
ES (1) ES2167763T3 (en)
WO (1) WO1998004417A1 (en)

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Also Published As

Publication number Publication date
EP0914257B1 (en) 2001-11-07
JP2000501670A (en) 2000-02-15
DE59705289D1 (en) 2001-12-13
ATE208280T1 (en) 2001-11-15
DE19630478A1 (en) 1998-01-29
WO1998004417A1 (en) 1998-02-05
ES2167763T3 (en) 2002-05-16

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