EP0413664B1 - Marquage par laser d'objets en plastique de toutes sortes utilisant des effets spéciaux - Google Patents

Marquage par laser d'objets en plastique de toutes sortes utilisant des effets spéciaux Download PDF

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Publication number
EP0413664B1
EP0413664B1 EP90810601A EP90810601A EP0413664B1 EP 0413664 B1 EP0413664 B1 EP 0413664B1 EP 90810601 A EP90810601 A EP 90810601A EP 90810601 A EP90810601 A EP 90810601A EP 0413664 B1 EP0413664 B1 EP 0413664B1
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EP
European Patent Office
Prior art keywords
laser
marking
pulse
molybdenum disulfide
marked
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EP90810601A
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German (de)
English (en)
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EP0413664A2 (fr
EP0413664A3 (en
Inventor
Fridolin Bäbler
Manfred Hofmann
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Novartis AG
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Ciba Geigy AG
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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
    • 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
    • Y10S430/00—Radiation imagery chemistry: process, composition, or product thereof
    • Y10S430/146—Laser beam
    • 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
    • Y10S430/00—Radiation imagery chemistry: process, composition, or product thereof
    • Y10S430/165—Thermal imaging composition

Definitions

  • the present invention relates to a method for laser marking plastic objects in any shape per se with special effects, and the material thus marked.
  • Laser marking of plastic objects with a contrast marking at the irradiated areas of the plastic is known.
  • a laser-sensitive additive is often added to the material to be inscribed, the additive discoloring, fading, decomposing or causing discoloration due to absorption of the laser energy, so that a contrast marking is generated at the irradiated areas (see, for example, EP patent applications No. 0036680 and No. 0190997 and U.S. Patent No. 4307047).
  • the additive is e.g. a mixture of different dyes has been proposed, only one component of the mixture discoloring or fading during the irradiation, so that a color contrast is produced at the irradiated areas (see, for example, JP patent applications No. 58-210937 or No. 60-155493) .
  • EP-A-0 327 508 describes a method for laser marking of organic materials which contain a radiation-sensitive, bleachable additive and a non-discolourable compound, for example an inorganic pigment.
  • Soot and graphite have also been proposed as an additive in the laser marking of plastics.
  • U.S. Patent No. 4391764 e.g. mixed with the plastic as filler carbon black or graphite in such a concentration that the absorption of the energy radiation triggers a local decomposition (a melt-gassing process) in the plastic and therefore causes a mostly black and white contrast marking.
  • a laser marking method has now been found which leads to effect markings which, depending on the angle of illumination and observation, appear clearly visible or completely invisible and also have perfect general properties, such as abrasion and scratch resistance, and good resistance to chemicals, light and weather.
  • the new process allows so-called subcutaneous labeling of the material without the surface of the object being visibly damaged.
  • the present subject of the invention accordingly relates to a method for laser marking plastic objects in any desired form, according to which the object to be labeled contains a radiation-sensitive additive which causes a change in light reflection and is exposed to a laser with pulsed light in such a way that the laser beam corresponds to the shape the marking to be applied is shaped by means of a mask or is guided over the surface of the object to be marked, so that a visual effect marking is produced at the irradiated areas of the object without the surface of the labeled object being visibly damaged by the eye, characterized in that as Additive molybdenum disulfide is used and the laser parameters wavelength, pulse energy density and pulse width are selected so that an effect marking is generated, the contrast of which changes visually depending on the angle of illumination and observation.
  • Additive molybdenum disulfide is used and the laser parameters wavelength, pulse energy density and pulse width are selected so that an effect marking is generated, the contrast of which changes visually depending on the angle of illumination and observation.
  • the effect is peculiar in that the marking becomes visible at certain lighting and observation angles, but invisible at other angles.
  • the marking is black at larger observation angles, for example at angles of 60 ° -90 °.
  • the dark marking disappears, ie there is no longer any contrast.
  • the method according to the invention allows a marking with an additional effect, in that the marking appears dark in the top view, but in the view appears light and almost transparent.
  • Plastic can e.g. are modified natural substances, for example cellulose derivatives, such as cellulose esters or cellulose ethers, and in particular fully synthetic organic polyplastics, that is to say plastics which are produced by polymerization, polycondensation or polyaddition.
  • cellulose derivatives such as cellulose esters or cellulose ethers
  • fully synthetic organic polyplastics that is to say plastics which are produced by polymerization, polycondensation or polyaddition.
  • polyolefins such as polyethylene, polypropylene, polybutylene or polyisobutylene, furthermore polystyrene, polyvinyl chloride, polyvinylidene chloride, the fluorine-containing polymers, such as polytetrafluoroethylene, furthermore polyvinyl acetals, polyacrylonitrile, polyacrylic acid and polymethacrylic acid esters or polybutadiene, and also copolymerisate thereof , especially ABS or EVA; Polyesters, especially high molecular esters of aromatic polycarboxylic acids with polyfunctional alcohols; Polyamides, polyimides, polycarbonates, polyurethanes, polyethers, such as polyphenylene oxide, also polyacetals, the condensation products of formaldehyde with phenols, the so-called phenoplasts, and the condensation products of formaldehyde with urea, thiourea or melamine, the so
  • Diols or polyphenols and also the unsaturated polyesters used as coating resins, such as maleate resins.
  • coating resins such as maleate resins.
  • Plastics in dissolved form as film formers or binders for paints or printing inks are also possible, e.g. Linseed oil varnish, nitrocellulose, alkyd resins, phenolic resins, melamine resins, acrylic resins and urea-formaldehyde resins, and the films obtained therefrom can be labeled according to the invention.
  • Plastics which are particularly suitable for the process according to the invention are polyvinyl chloride, polyvinyl esters, such as polyvinyl acetals, furthermore polyacrylic acid and polymethacrylic acid esters, polyesters, polyamides, polyimides, polycarbonates, polyurethanes, polyethers, in particular polyphenylene oxides, furthermore polyacetals, phenoplasts, aminoplasts, epoxy resins and very particularly polyolefins, such as Polyethylene and polypropylene.
  • polyvinyl chloride polyvinyl esters, such as polyvinyl acetals, furthermore polyacrylic acid and polymethacrylic acid esters
  • polyesters polyamides, polyimides, polycarbonates, polyurethanes, polyethers, in particular polyphenylene oxides, furthermore polyacetals, phenoplasts, aminoplasts, epoxy resins and very particularly polyolefins, such as Polyethylene and polypropylene.
  • molybdenum disulfide in flake or platelet form with a particle diameter of less than 100 »m, but very particularly with a particle diameter of 0.1 to 25» m, and a thickness of up to 4 »m.
  • molybdenum disulfide in the preferred particle nature can be obtained in a known manner, for example by grinding in air jet, sand or ball mills.
  • a grinding device which contains metal, glass or porcelain balls, plastic granules or sand grains as grinding media.
  • These grinding media are set in motion, for example, by rotating the vessel or by vibrators or stirrers.
  • the optimal effect markings can be determined by varying the amount of molybdenum disulfide within the range specified below.
  • preference is given to using from 1.0 to 15.0% by weight, in particular from 1.0 to 10% by weight, of molybdenum disulfide, based on the dry layer of paint or printing ink.
  • preference is given to using from 0.01 to 5.0% by weight, in particular from 0.05 to 1% by weight, of molybdenum disulfide, based on the plastic material.
  • flaky or platelet-shaped molybdenum disulfide with 60-95% by weight of the particles which have a median value of 1-12 »m. They expediently have a diameter of 0.1 to 25 »m.
  • the colorant or mixture thereof may only be present in the plastic in such a concentration that the effect marking produced according to the invention is not impaired or covered.
  • the concentration is appropriately 0.01 to 0.5% by weight or 0.5 to 5% by weight.
  • Inorganic or organic pigments and polymer-soluble dyes are suitable as additional colorants, in particular those which absorb in the visible range.
  • inorganic pigments are white pigments, such as titanium dioxide (anatase, rutile), zinc oxide, antimony trioxide, zinc sulfide, lithopone, basic lead carbonate, basic lead sulfate or basic lead silicate, and also colored pigments, such as iron oxides, nickel-antimony-titanate, chromium-antimony-titanate, Manganese blue, manganese violet, cobalt blue, Cobalt chromium blue, cobalt nickel gray, or ultramarine blue, Berlin blue, lead chromate, lead sulfochromates, molybdate orange, molybdate red, cadmium sulfides, cadmium, antimony, zirconium silicates such as Zirkonvanadiumblau and Zirkonpraseodymgelb, as well as carbon black or graphite in a
  • organic pigments examples include azo, azomethine, methine, anthraquinone, indanthrone, pyranthrone, flavanthrone, benzanthrone, phthalocyanine, perinone, perylene, dioxazine, thioindigo, isoindoline, isoindolinone, Quinacridone, pyrrolopyrrole or quinophthalone pigments, furthermore metal complexes of eg Azo, azomethine or methine dyes, or metal salts of azo compounds and also platelet-shaped organic pigments.
  • Suitable polymer-soluble dyes are, for example, disperse dyes, such as those of the anthraquinone series, for example hydroxy, amino, alkylamino, cyclohexylamino, arylamino, hydroxylamino or phenylmercaptoanthraquinones, and metal complexes of azo dyes, in particular 1: 2 chromium or - Cobalt complexes of monoazo dyes, also fluorescent dyes, such as those from the coumarin, naphthalimide, pyrazoline, acridine, xanthene, thioxanthene, oxazine, thiazine or benzothiazole series.
  • disperse dyes such as those of the anthraquinone series, for example hydroxy, amino, alkylamino, cyclohexylamino, arylamino, hydroxylamino or phenylmercaptoanthraquinones
  • the inorganic and organic pigments or polymer-soluble dyes can be used individually or as mixtures, optionally together with pigment additives.
  • Suitable pigment additives are, for example, fatty acids with at least 12 carbon atoms, such as stearic acid or behenic acid, their amides, salts or esters, such as magnesium stearate, zinc stearate, aluminum stearate or magnesium behenate, and also quaternary ammonium compounds, such as tri (C1-C4) alkylbenzylammonium salts, waxes, such as polyolefin waxes, for example polyethylene wax, and also resin acids, such as abietic acid, rosin soap, hydrogenated or dimerized rosin, C12-C18 paraffin disulfonic acid or alkylphenols, Alcohols, such as ® TCD alcohol M, or vicinal aliphatic 1,2-diols.
  • fatty acids with at least 12 carbon atoms such as stearic acid or behenic acid, their amides, salts or esters, such as magnesium stearate, zinc stearate, aluminum stearate
  • the plastic objects are produced by methods known per se, for example in such a way that the required color components (molybdenum disulfide and, if appropriate, an additional colorant) are optionally in the form of masterbatches, the plastic material and the customary additives using extruders, rolling mills, mixing or grinders.
  • the mixture obtained is then brought into the desired final shape by processes known per se, such as calendering, pressing, extrusion, brushing, centrifuging, casting, extruding, blowing or by injection molding.
  • plasticizers can be incorporated into the polymers before or after incorporation of the coloring components that are possible according to the invention.
  • plastic material such as fillers such as kaolin, mica, feldspar, wollastonite, aluminum silicate, quartz or glass powder, barium sulfate, calcium sulfate, chalk, talc, calcite and dolomite, as well as light stabilizers, antioxidants, Flame retardants, heat stabilizers, glass fibers or processing aids, which are common in the processing of plastics and are known to the person skilled in the art.
  • fillers such as kaolin, mica, feldspar, wollastonite, aluminum silicate, quartz or glass powder, barium sulfate, calcium sulfate, chalk, talc, calcite and dolomite, as well as light stabilizers, antioxidants, Flame retardants, heat stabilizers, glass fibers or processing aids, which are common in the processing of plastics and are known to the person skilled in the art.
  • the plastic material, the molybdenum disulfide and, if appropriate, an additional colorant, together with further paint and printing ink additives are finely dispersed or dissolved in water or a common organic solvent or solvent mixture. You can do this by dispersing or dissolving the individual components for yourself or several together, and only then bringing all the components together.
  • the homogenized paint or printing ink is then applied to a substrate according to methods known per se and baked or dried, and the coating or printing ink film obtained is then labeled according to the invention.
  • High-energy pulsed laser sources are used to label the plastic objects that are suitable according to the invention.
  • the energy radiation according to the shape of the marking to be applied expediently at a steep angle, directed onto the surface of the material to be marked, optionally focused, an effect marking being formed at the irradiated points without the surface of the labeled material being visibly damaged.
  • laser sources are solid-state pulse lasers, such as ruby lasers or frequency-multiplied Nd: YAG lasers, pulsed lasers with additional devices, such as pulsed dye lasers or Raman shifters, and continuous wave lasers with pulse modifications (Q-Switch, Mode-Locker), for example based on CW Nd: YAG lasers with a frequency multiplier, or CW ion lasers (Ar, Kr), also pulsed metal vapor lasers, such as Cu vapor lasers or Au vapor lasers, or possibly powerful pulsed semiconductor lasers that emit visible light directly or by frequency doubling , also pulsed gas lasers, such as excimer and nitrogen lasers.
  • solid-state pulse lasers such as ruby lasers or frequency-multiplied Nd: YAG lasers
  • pulsed lasers with additional devices such as pulsed dye lasers or Raman shifters
  • continuous wave lasers with pulse modifications Q-Switch, Mode-Locker
  • CW Nd YAG lasers with a frequency
  • pulse energy densities up to a few joules per cm2 power densities up to terawatts per cm2
  • pulse widths from femto-seconds to micro-seconds and repetition rates up to gigahertz are possible.
  • Pulse energy densities from millijoules to one kilojoule per cm2 and pulse widths from micro seconds to pico seconds are advantageously used. This corresponds to power densities from kilowatts per cm2 to megawatts per cm2 and repetition rates from a few Hertz to 50 Kilohertz.
  • Pulsed or pulse-modified, frequency-doubled Nd YAG lasers or metal vapor lasers, such as Au or in particular Cu vapor lasers, and excimer lasers are preferably used.
  • a pulsed frequency-doubled Nd: YAG laser between 0.05 and 1 joule per cm2 of pulse energy density, about 4 kilowatts of peak power, 6-8 nano-seconds pulse width and 30 Hertz repetition rate (model Quanta Ray DCR-2 A from Spectra Physics, Mountain View, California).
  • exposure is, for example, at 250 millijoules per cm2 of pulse energy density, about 10 kilowatts peak power, 30 nano-seconds pulse width and 6 kilohertz repetition rate.
  • Lasers with good adjustability of their laser parameters allow optimal adaptation to the needs of the materials to be labeled.
  • the optimum wavelength to be selected for irradiation is the one at which the radiation-sensitive MoS2 and possibly the additional colorant absorb the most, whereas the plastic to be labeled absorbs little.
  • Laser light with a wavelength in the near UV and / or visible and / or near IR range is expediently used, but preferably with a wavelength in the visible range.
  • the visible range is the range between 0.38 »m and 0.78» m
  • the near IR range is the range between 0.78 »m and 2» m
  • the near UV range is the range between 0.25 » m and 0.38 »m.
  • the mask method There are generally three different methods for labeling with lasers: the mask method, the linear labeling and the dot-matrix method.
  • the laser is preferably coupled to a laser labeling system, so that the plastic can be labeled with any numbers, letters and special characters programmed in a computer, for example.
  • the choice of laser system in terms of power and repetition rate is based on the labeling method used. High performance and low repetition rate, as with the solid-state pulse laser and excimer laser, are preferred for mask exposures. Medium to low power and fast repetition rates for pulsed metal vapor lasers or for continuous wave lasers with pulse modifications are preferred for labels that require dynamic beam guidance.
  • the beam deflection can take place, for example, acousto-optically, holographically, with galvo mirrors or polygon scanners.
  • the dynamic beam guidance enables extremely flexible labeling or marking, as the characters can be generated electronically.
  • marking and labeling can be obtained by the method according to the invention.
  • Examples of this are: Variable text programming of numeric characters using text input via a keyboard, text program of standard characters or special characters, such as names, initials and dedications, identity cards, signs or frequently repeated data, consecutive numbering of items, input of measurement quantities, input of stored programs, Line lettering or graphics and decorations, as well as security documents such as checks, traveler checks, banknotes, lottery tickets, credit cards, passports with data from computer programs, graphic data records or templates that can be read in with digitizing devices or scanners.
  • plastic objects can be labeled using the method according to the invention, such as molded plastic bodies or foils and also paint and printing ink films.
  • plastic objects can be labeled using the method according to the invention, such as molded plastic bodies or foils and also paint and printing ink films.
  • examples of these are tapes, boards, tubes and profiles, buttons, buttons and plastic-covered electronic components or parts with different colors that are manufactured using the two-phase injection molding process.
  • the markings obtained according to the invention are corrosion-resistant, dimensionally stable, deformation-free, light, heat and weather resistant. They have a clean edge zone and are easily readable by the naked eye in the area described at the beginning, without having to use IR or UV readers, for example. Furthermore, the mechanical and physical properties of the material so labeled are practically unaffected, such as mechanical strength and chemical resistance. The depth of penetration of the marking depends on the labeled plastic. It is usually less than 1 mm. The plastic material is largely protected. Inscriptions are therefore possible that do not cause any loss of surface gloss that can be seen by the eye and do not impair the strength properties of the workpiece.
  • a change in reflection with a variable contrast occurs at the irradiated points of the material under laser irradiation. Most of the time there is a color change to black or dark gray in the top view, bright markings in the view and the markings disappear when the viewing angle is narrow or reduced. Depending on the laser system, it is also possible to generate a contrast marking which, when viewed under a microscope, also has a clearly recognizable fine structure.
  • Example 1 A mixture of 10.0 g of a platelet-shaped molybdenum IV sulfide pigment in which 85% of the particles have a particle size of 6-24 »m with a median value of 9.6» m (measured on a granulometer 715 E 598 from Company CILAS, F-91463 Marcoussis / FR), 1.0 g of antioxidant (®IRGANOX 1010, CIBA-GEIGY AG) and 1000 g of polyethylene-HD granules (®VESTOLEN A 60-16, HUELS) are in a glass bottle for 15 minutes mixed on a rolling bench.
  • the mixture is then extruded in two passages on a single-shaft extruder, the granules obtained in this way are injected into plates on the injection molding machine (Allround Aarburg 200) at 220 ° C., which are then pressed at 180 ° C. for 5 minutes.
  • the press plates have a homogeneous metallic gray shimmering color.
  • the press plates thus obtained are labeled with a laser beam deflected over two orthogonally movable mirrors in accordance with the shape of the marking to be applied (in the present case the inscription "GRETAG"; height and width of the letters 6 mm; font width 0.1 mm).
  • An Nd: YAG pulse laser (®Quanta Ray DCR 2, Spectra Physics) with frequency doubler (harmonic generator) and frequency filter (harmonic separator) is used as the laser.
  • the laser is adjusted and attenuated with neutral filters so that the beam focused on a lens (focal length 200 mm) on the surface of the plate reaches a pulse energy of 0.2 mJ with a pulse width of 10 nano-seconds.
  • the deflection unit with the orthogonally movable mirrors is part of a ®GRETAG 6210 laser marking system (GRETAG AG, Switzerland) and is mounted vertically above the sample plate.
  • the labeling achieved in this way is dark (black on the gray underlay with approximately vertical supervision) and stands out clearly from the unmarked metallic gray shimmering colored article. Depending on the incidence of light and the angle of observation, the marking is clearly recognizable or disappears completely.
  • Examples 2-9 The plastic granules are mixed according to the information in the list below with the molybdenum disulfide pigment described in Example 1 and injected into flakes of size 55 ⁇ 45 ⁇ 1.5 mm.
  • the samples thus produced are labeled according to Example 1 using the device described there; Instead of the 'GRETAG' lettering, two markings are made in the form of a circular arc (3/4 circle) and a rectangle (9x9 mm).
  • the labeled plates all show the effect that the markings are only visible under certain lighting and viewing angles, but practically disappear when the lighting is flat.
  • Test concentration 0.1% molybdenum disulfide pigment; Polymer: ABS [®TERLURAN 877M, BASF, DE]; Approach: 1000 g; Mix polymer + pigment: 3 l glass bottle, 15 min. At 60 rpm, roller frame; Extrude: 2x at 190 ° C - small extruder type 133, [Fa. Collin, DE]; Granulate: Strand pelletizing machine - [Fa. WILCO AG, CH]; Dry: 90 ° C for 4 hours - granular fan dryer [Turb. Etuve TE 25, MAPAG AG, CH]; Spray temperature: 220 ° C; Automatic spray gun Aarburg 200 allrounder; [Fa. Aarburg, DE]; Sample size: 55x45 mm - 1.5 mm thick.
  • Test concentration 0.1% molybdenum disulfide pigment
  • Polymer ®MACROLON 2800 [BASF]; Mix polymer + pigment: 15 min at 60 rpm; Predrying: 120 ° C for 4 hours; Extrude: 2x at 270 ° C; Dry: 120 ° C for 4 hours; Spray temperature: 300 ° C.
  • Test concentration 0.1% molybdenum disulfide pigment
  • Polymer ®ULTRAMID B3K [BASF]
  • Mix polymer + pigment 15 min at 60 rpm
  • Predrying 120 ° C for 4 hours
  • Extrude 2x at 220 ° C
  • Dry 120 ° C for 4 hours
  • Spray temperature 240 ° C.
  • Test concentration 0.1% molybdenum disulfide pigment
  • Polymer ®XENOY CL 100, powder quality [General Electric, NL] ;
  • Test concentration 0.1% molybdenum disulfide pigment
  • Polymer ®MELINOR B 90 [ICI, GB]; Mix polymer + pigment: 15 min at 60 rpm; Predrying: 90 ° C for 4 hours; Extrude: 2x at 270 ° C; Dry: 90 ° C for 4 hours; Spray temperature: 280 ° C.
  • Test concentration 0.1% molybdenum disulfide pigment
  • Polymer ®Plexiglas molding compound N 6 [Röhm GMBH, DE]; Mix polymer + pigment: 15 min at 60 rpm; Predrying: 90 ° C for 8 hours; Extrude: 2x at 220 ° C; Spray temperature: 240 ° C.
  • Test concentration 0.1% molybdenum disulfide pigment
  • Polymer ®VESTOLEN A 6016 [Huls AG, DE]; Mix polymer + pigment: 15 min at 60 rpm; Extrude: 2x at 200 ° C; Spray temperature: 220 ° C.
  • Test concentration 0.1% molybdenum disulfide pigment
  • Polymer ®STAMYLAN P 83 HF 10 [DSM, NL]
  • Mix polymer + pigment 15 min at 60 rpm
  • Extrude 2x at 200 ° C
  • Spray temperature 240 ° C.
  • Example 10 200 mg of a platelet-shaped molybdenum IV disulfide pigment with a particle fraction of 80-90%, a size of 4-25 micrometers and a median value of 9.5 micrometers (measured on granulometer 715E598 from CILAS, F-91460, Marcoussis / FR), 7.3 ml of dioctyl phthalate and 13.3 g of stabilized polyvinyl chloride are mixed well in a beaker with a glass rod and then processed on a roller mill at 160 ° C. for 5 minutes to form a thin film. The film thus obtained is labeled with a laser beam in accordance with Example 1. The inscriptions obtained are dark (black on the gray surface) when viewed from a vertical angle, but they appear bright when viewed through with a pronounced fine structure.

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  • Physics & Mathematics (AREA)
  • Optics & Photonics (AREA)
  • Thermal Transfer Or Thermal Recording In General (AREA)
  • Compositions Of Macromolecular Compounds (AREA)
  • Treatments Of Macromolecular Shaped Articles (AREA)

Claims (11)

  1. Procédé de marquage au laser d'objets en plastique, sous une forme quelconque, procédé selon lequel l'objet à inscrire contient un additif sensible au rayonnement, provoquant une modification de la réflexion lumineuse, et est exposé à un laser à lumière pulsée, de telle sorte que le faisceau laser prenne, à l'aide d'un masque, la forme du marquage à appliquer, ou encore est guidé sur la surface de l'objet à marquer de telle sorte qu'il se crée en les points irradiés de l'objet un marquage à effets visuels, sans qu'il en résulte une détérioration, visible à l'oeil nu, de la surface de l'objet marqué, caractérisé en ce qu'on utilise comme additif du disulfure de molybdène, et que l'on choisit les paramètres du laser tels que la longueur d'onde, la densité d'énergie d'impulsion et la largeur de l'impulsion, de façon à produire un marquage à effets dont le contraste varie visuellement en fonction de l'angle d'éclairement et de l'angle d'observation.
  2. Procédé selon la revendication 1, caractérisé en ce qu'on utilise une lumière laser ayant une longueur d'onde dans l'UV proche et/ou dans le visible et/ou dans l'IR proche.
  3. Procédé selon la revendication 1, caractérisé en ce qu'on utilise une lumière laser dont la longueur d'onde est dans le visible.
  4. Procédé selon la revendication 1, caractérisé en ce qu'on utilise un laser à Nd:YAG à doublement de fréquence, pulsé ou à modification d'impulsion, ou encore un laser à vapeur métallique ou un laser à excimère.
  5. Procédé selon la revendication 1, caractérisé en ce qu'on utilise des densités d'énergie d'impulsion comprises entre 1 millijoule et 1 kilojoule par cm² et des largeurs d'impulsions comprises entre quelques microsecondes et quelques picosecondes.
  6. Procédé selon la revendication 1, caractérisé en ce qu'on utilise un disulfure de molybdène sous forme de lamelles ou d'écailles ayant une granulométrie inférieure à 100 »m et une épaisseur allant jusqu'à 4 »m.
  7. Procédé selon la revendication 1, caractérisé en ce qu'on utilise pour les plastiques colorés dans la masse de 0,01 à 5,0 % en poids de disulfure de molybdène, et, pour les plastiques utilisés sous forme d'une peinture ou d'une encre d'imprimerie, de 1,0 à 15,0 % en poids de disulfure de molybdène, par rapport respectivement au matériau plastique ou encore au feuil de peinture sec ou au film d'encre d'imprimerie sec.
  8. Procédé selon la revendication 1, caractérisé en ce que le plastique est le poly(chlorure de vinyle), un ester polyvinylique, un polyacrylate ou polyméthacrylate, un polyester, un polyamide, un polyimide, un polycarbonate, un polyuréthanne, un polyéther, un polyacétal, un phénoplaste, un aminoplaste, une résine époxyde ou une polyoléfine.
  9. Procédé selon la revendication 1, caractérisé en ce qu'on mélange du matériau plastique un colorant supplémentaire ou un mélange de colorants.
  10. Procédé selon la revendication 9, caractérisé en ce qu'on utilise comme colorant un pigment organique ou minéral ou un colorant soluble dans les polymères.
  11. Le matériau inscrit selon la revendication 1.
EP90810601A 1989-08-18 1990-08-09 Marquage par laser d'objets en plastique de toutes sortes utilisant des effets spéciaux Expired - Lifetime EP0413664B1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
CH3011/89 1989-08-18
CH301189 1989-08-18

Publications (3)

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EP0413664A2 EP0413664A2 (fr) 1991-02-20
EP0413664A3 EP0413664A3 (en) 1991-10-16
EP0413664B1 true EP0413664B1 (fr) 1995-03-22

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EP90810601A Expired - Lifetime EP0413664B1 (fr) 1989-08-18 1990-08-09 Marquage par laser d'objets en plastique de toutes sortes utilisant des effets spéciaux

Country Status (4)

Country Link
US (1) US5075195A (fr)
EP (1) EP0413664B1 (fr)
JP (1) JPH03106944A (fr)
DE (1) DE59008746D1 (fr)

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Also Published As

Publication number Publication date
EP0413664A2 (fr) 1991-02-20
EP0413664A3 (en) 1991-10-16
DE59008746D1 (de) 1995-04-27
JPH03106944A (ja) 1991-05-07
US5075195A (en) 1991-12-24

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