EP0991523B1 - Plastics which can be laser-marked - Google Patents

Plastics which can be laser-marked Download PDF

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Publication number
EP0991523B1
EP0991523B1 EP98929407A EP98929407A EP0991523B1 EP 0991523 B1 EP0991523 B1 EP 0991523B1 EP 98929407 A EP98929407 A EP 98929407A EP 98929407 A EP98929407 A EP 98929407A EP 0991523 B1 EP0991523 B1 EP 0991523B1
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EP
European Patent Office
Prior art keywords
laser
plastic
markable
plastics according
markable plastics
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EP98929407A
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German (de)
French (fr)
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EP0991523A1 (en
Inventor
Reiner Delp
Jürgen Solms
Gerhard Edler
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Merck Patent GmbH
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Merck Patent GmbH
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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
    • B41M5/36—Thermography ; Marking by high energetic means, e.g. laser otherwise than by burning, and characterised by the material used using a polymeric layer, which may be particulate and which is deformed or structurally changed with modification of its' properties, e.g. of its' optical hydrophobic-hydrophilic, solubility or permeability properties
    • B41M5/366—Thermography ; Marking by high energetic means, e.g. laser otherwise than by burning, and characterised by the material used using a polymeric layer, which may be particulate and which is deformed or structurally changed with modification of its' properties, e.g. of its' optical hydrophobic-hydrophilic, solubility or permeability properties using materials comprising a polymeric matrix containing a polymeric particulate material, e.g. hydrophobic heat coalescing particles
    • 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
    • B41M5/36—Thermography ; Marking by high energetic means, e.g. laser otherwise than by burning, and characterised by the material used using a polymeric layer, which may be particulate and which is deformed or structurally changed with modification of its' properties, e.g. of its' optical hydrophobic-hydrophilic, solubility or permeability properties
    • 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 present invention relates to laser-markable plastics characterized in that a difficult to laser plastic as an absorber material one or more intrinsically laser-markable polymers in Form of micro-milled particles with a particle size of 0.1-100 ⁇ m contains.
  • the labeling of production goods is used in almost all branches of industry increasingly important. For example, production data, Expiry dates, barcodes, company logos, serial numbers etc. be applied.
  • these markings are mostly with conventional techniques such as printing, embossing, stamping and labeling executed.
  • the non-contact, very fast and flexible marking with lasers especially with plastics.
  • PET polyethylene
  • PP polypropylene
  • PA polyamide
  • PMMA polymethyl methacrylate
  • POM polyoxymethylene
  • PUR polyurethane
  • PET polyurethane
  • a CO 2 laser which emits light in the infrared range at 10.6 ⁇ m, only produces a weak, barely legible marking on polyolefins, even at very high outputs, since the absorption coefficient of the plastics to be processed at these wavelengths is not high enough to match one To induce color change in the polymeric material.
  • the plastic must not fully reflect or let the laser light through, as there is no interaction. However, strong absorption must also not occur, since in this case the plastic evaporates and only one engraving remains.
  • EP 0 190 997 A describes laser-inscribable molding compositions, i.a. PE or PS, made by the high molecular weight organic Material adds at least one inorganic pigment.
  • EP 0 330 869 PBT and PET are mixed with TiO 2 and carbon black.
  • the lettering is dark on a light background.
  • the use of carbon black and / or graphite as an absorber in the laser marking of polyester is known from EP 0 485 181.
  • the fillers known for laser marking either have the disadvantage that they permanently color the plastic to be labeled and consequently laser marking, which is usually dark Writing on a lighter background is then no longer sufficient high contrast, i.e. is readable, or that, such as. B. with kaolin, the marking is very weak and only with high amounts of the aggregate is clearly visible.
  • polymers that without the addition of additives dark and very high contrast using a Lasers are markable.
  • these include e.g. B. PET, butadiene styrene (ABS), Polystyrene, polyphenyl ether (PPO), liquid crystal polymers (LCP), polyphenylene sulfide, Polyarylates, polyaryl sulfides, polyaryl sulfones, polyaryl ether ketones as well as their blends.
  • the object of the present invention was therefore laser-markable plastics to find a laser mark under the influence of laser light enable with high contrast.
  • the filler or the successful one Absorbent should have a very bright neutral color or the Have properties of the pre-colored plastic to be marked or not or only marginally influence them.
  • the invention therefore relates to laser-markable plastics, characterized in that difficult to leave plastics one or several intrinsically laser-markable polymers in the form of micro-ground particles with a particle size of 0.1 up to 100 ⁇ m included.
  • intrinsically markable polymers By adding micro-milled, intrinsically markable polymers as an absorber in concentrations of 0.1 to 10% by weight, preferably 0.1 to 5% by weight, and in particular 0.1 to 2% by weight, based on the plastic system becomes a high contrast when laser marking achieved.
  • concentration of the intrinsically markable polymers in the plastic depends on the plastic system used and the laser used.
  • Suitable polymers or polymer mixtures are all known laserable plastics such.
  • Micro-ground thermoplastics with a very high melting range of> 300 ° C.
  • the edge sharpness of the Marking is particularly due to the particle size of the micromilled Polymers determined.
  • the polymers preferably have Particle sizes in the range from 0.1 to 50 ⁇ m, in particular from 1 to 20 ⁇ m.
  • the marking result is influenced positively if the intrinsic Markable polymer as a further absorber, a light-sensitive pigment, such as B. a filler, a conductive pigment and / or an effect pigment, contains.
  • a light-sensitive pigment such as B. a filler, a conductive pigment and / or an effect pigment.
  • the Contrast increased depending on the plastic system used.
  • the amount of light-sensitive pigment added should be between 0.1 and 90% be.
  • Particularly suitable light-sensitive pigments are fillers, such as. B. TiO 2 and SiO 2 , and layered silicates.
  • light or white mica can be used as the silicate plate.
  • other natural mica such as phlogopite and biotite, synthetic mica, talc and glass flakes can also be used.
  • Suitable conductive pigments are e.g. B. the pigments sold by Merck KGaA under the trade name Minatec®.
  • CuO ⁇ P 2 O 5 is particularly preferred ⁇ H 2 O or Cu 3 (PO 4) 2 ⁇ Cu (OH) 2 has.
  • Further suitable copper phosphates are 6 CuO ⁇ P 2 O 5 ⁇ 3 H 2 O, Cu 3 (PO 4 ) 2 ⁇ 3 Cu (OH) 2 , 5 CuO ⁇ P 2 O 5 ⁇ 3 H 2 O, Cu 3 (PO 4 ) 2 ⁇ 2 Cu (OH) 2 ⁇ H 2 O, 4 CuO ⁇ P 2 O 5 , 4 CuO ⁇ P 2 O 5 ⁇ 3H 2 O, 4 CuO ⁇ P 2 O 5 ⁇ 1.5 H 2 O, 4 CuO ⁇ P 2 O 5 ⁇ 1.2 H 2 O.
  • an improvement in laser markability is also achieved if in addition to the intrinsically labeling polymer, one or more of the above light-sensitive pigments added to the plastic as a further component becomes.
  • the weight fraction of all absorbers in the plastic should be in Combination with the micro-milled polymers a total of 10% by weight in relation to the plastic system.
  • the plastic contains 0-5% by weight of light-sensitive pigments, in particular 0-1% by weight. The mixing ratio of the light sensitive pigments with the micro-milled polymers, none is subject to this Restriction.
  • Color pigments can also be used in the hard-to-laser plastic be added that allow color variations of any kind and at the same time ensure that the laser marking is retained.
  • the light-sensitive pigments and / or color pigments are added preferably together with the polymers, but in principle is also separate addition possible. It can also be a mixture of different ones light-sensitive pigments can be added to the plastic.
  • High-energy radiation is preferably used for the marking, in general in the wavelength range from 150 nm to 10600 nm, in particular in the range from 150 nm to 1100 nm.
  • CO 2 lasers 10600 nm
  • Nd YAG lasers (1064 nm or 532 nm) or pulsed UV laser (excimer laser) mentioned.
  • Nd YAG lasers (1064 nm or 532 nm) and CO 2 lasers (10600 nm) are particularly preferably used.
  • the energy densities of the lasers used are generally in the range from 0.3 mJ / cm 2 to 50 J / cm 2 , preferably in the range from 0.3 mJ / cm 2 to 10 J / cm 2 .
  • Thermosets polyethylene (PE-HD, PE-LD, PE-LLD), Polypropylene (PP), polyester, polyacetal, polyamide (PA), poly-urethane (PUR), polybutylene terephthalate, polymethyl methacrylate (PMMA), polyvinyl acetal, Polystyrene, butadiene styrene (ABS), acrylonitrile styrene acrylic ester (ASA), and their copolymers and / or mixtures thereof.
  • polyolefins, polyurethanes, polyoxymethylenes and polyamides their mechanical properties, the inexpensive processing methods and their poor laser markability for doping suitable with the polymers according to the invention.
  • micro-ground polymer is incorporated into the plastic according to the processes known for pigments and fillers. Subsequently the pigmented plastic is then deformed under the influence of heat.
  • the intrinsically markable polymer to be ground is too note that the particle structure is retained after incorporation, d. that is, the particles should not be soluble in the melt or melt with them. This is achieved by appropriate coordination of the Melting ranges of the plastic system with that of the micro-ground Polymer.
  • the plastic granulate can be incorporated into the micromilled Polymers optionally adhesives, organic polymer compatible Solvents, stabilizers, optical brighteners, color pigments, dyes, Fillers, reinforcing materials, flame retardants, antistatic agents and / or temperature-stable surfactants added under the working conditions become.
  • adhesives organic polymer compatible Solvents, stabilizers, optical brighteners, color pigments, dyes, Fillers, reinforcing materials, flame retardants, antistatic agents and / or temperature-stable surfactants added under the working conditions become.
  • organic polymer compatible Solvents organic polymer compatible Solvents
  • stabilizers stabilizers
  • optical brighteners color pigments
  • dyes dyes
  • Fillers reinforcing materials
  • temperature-stable surfactants added under the working conditions become.
  • other additives not mentioned here, added to the plastic become.
  • the presence of other additives in existing plastic systems can
  • the production of the plastic granulate / polymer mixture takes place in the As a rule, the plastic granulate is placed in a suitable mixer, is wetted with any additives and then the micro-ground Polymers are added and mixed in. The so obtained Mixing can then be done directly in an extruder or an injection molding machine are processed. The moldings formed during processing usually show a very homogeneous distribution of the polymers or of the polymer mixture. Lastly, the laser marking takes place, preferably with an Nd: YAG laser instead.
  • the labeling with the laser takes place in such a way that the sample body is brought into the beam path of a pulsed laser, preferably an Nd: YAG laser. Labeling with a CO 2 or excimer laser is also possible. However, the desired results can also be achieved with other types of lasers which have a wavelength in a region of high absorption of the intrinsically marking polymer.
  • the hue obtained and the depth of color are determined by the laser parameters, such as the irradiation time and irradiation power.
  • the power of the laser used depends on the respective application and can be determined easily by a specialist in individual cases.
  • the use of the plastic doped according to the invention can be limited to in all areas, where previously customary printing methods for labeling of plastics.
  • molded articles from the plastic according to the invention in electrical, electronics and Motor vehicle industry find application.
  • the labeling and Labeling of e.g. Housings, cables, key caps, trim strips or functional parts in the heating, ventilation and cooling area or Switches, plugs, levers and handles that result from the invention Plastic can help even in hard-to-reach places done by laser light.
  • the plastic system according to the invention due to its low heavy metal content in packaging be used in the food sector or in the toy sector.
  • the Markings on the packaging are characterized by the fact that they smudge-proof and scratch-resistant, stable during subsequent sterilization processes, can be applied hygienically during the marking process.
  • complete Label images can be permanently on the packaging for a reusable system be applied.
  • Another important area of application for the laser inscription are ID cards and plastic brands individual identification of animals, so-called cattle tags or Earmarks. The laser marking of plastic objects or moldings, which consist of the plastic according to the invention is thus possible.
  • the components are mixed physically and using an injection molding machine homogenized and shaped into platelets.
  • the caption with an Nd: YAG laser at 532 and 1064 nm wavelengths shows about a high-contrast black marking with a wide setting range smooth surface.
  • the components are mixed and using an injection molding machine homogenized and shaped into platelets.
  • the label with a Nd: YAG laser shows a black over a wide setting range high-contrast marking with smooth surface.
  • the components are mixed and using an injection molding machine homogenized and shaped into platelets.
  • the label with a Nd: YAG laser shows a deep black over a wide setting range high-contrast marking with smooth surface.
  • the components are mixed and using an injection molding machine homogenized and shaped into platelets.
  • the label with a Nd: YAG laser shows a black over a wide setting range high-contrast marking with smooth surface.
  • the components are mixed and using an injection molding machine homogenized and shaped into platelets.
  • the label with a Nd: YAG laser shows a black over a wide setting range high-contrast marking with smooth surface.
  • the polyphenylene sulfide becomes homogeneous in the liquid polyester casting resin stirred. After adding accelerator (Co-Octoat) and hardener (Cyclohexanone peroxide) the mixture is poured into a mold. To the hardening gives a molded part, which by means of Nd: YAG laser is black and can be marked with high contrast.

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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)

Description

Die vorliegende Erfindung betrifft lasermarkierbare Kunststoffe, die sich dadurch auszeichnen, daß ein schwer belaserbarer Kunststoff als Absorbermaterial ein oder mehrere intrinsisch lasermarkierbare Polymere in Form von mikrovermahlenen Partikeln mit einer Teilchengröße von 0,1-100 µm enthält.The present invention relates to laser-markable plastics characterized in that a difficult to laser plastic as an absorber material one or more intrinsically laser-markable polymers in Form of micro-milled particles with a particle size of 0.1-100 µm contains.

Die Kennzeichnung von Produktionsgütern wird in fast allen Industriezweigen zunehmend wichtiger. So müssen häufig zum Beispiel Produktionsdaten, Verfallsdaten, Barcodes, Firmenlogos, Seriennummern etc. aufgebracht werden. Derzeit werden diese Markierungen überwiegend mit konventionellen Techniken wie Drucken, Prägen, Stempeln und Etikettieren ausgeführt. Wachsende Bedeutung gewinnt aber die berührungslose, sehr schnelle und flexible Markierung mit Lasern, insbesondere bei Kunststoffen. Mit dieser Technik ist es möglich graphische Beschriftungen, wie z.B. Barcodes, mit hoher Geschwindigkeit auch auf eine nicht plane Oberfläche aufzubringen. Da sich die Beschriftung im Kunststoffkörper selbst befindet, ist sie dauerhaft und abriebbeständig.The labeling of production goods is used in almost all branches of industry increasingly important. For example, production data, Expiry dates, barcodes, company logos, serial numbers etc. be applied. Currently, these markings are mostly with conventional techniques such as printing, embossing, stamping and labeling executed. However, the non-contact, very fast and flexible marking with lasers, especially with plastics. With this technique it is possible to write graphics such as e.g. Barcodes, at high speed, even on a non-flat surface applied. Since the labeling in the plastic body itself is permanent and abrasion resistant.

Viele Kunststoffe, wie z.B. Polyethylen (PE), Polypropylen (PP), Polyamid (PA), Polymethylmethacrylat (PMMA), Polyoxymethylen (POM), Polyurethan (PUR), Polyester, lassen sich bisher nur schwierig oder überhaupt nicht mit dem Laser markieren. Ein CO2-Laser, der Licht im Infrarotbereich bei 10,6 µm aussendet, bewirkt bei Polyolefinen selbst bei sehr hohen Leistungen nur eine schwache, kaum lesbare Markierung, da der Absorptionskoeffizient der zu verarbeitenden Kunststoffe bei diesen Wellenlängen nicht hoch genug ist, um einen Farbumschlag im polymeren Material zu induzieren. Der Kunststoff darf das Laserlicht nicht völlig reflektieren oder durchlassen, da es dann zu keiner Wechselwirkung kommt. Es darf aber auch nicht zu einer starken Absorption kommen, da in diesem Fall der Kunststoff verdampft und nur eine Gravur zurückbleibt. Die Absorption der Laserstrahlen und somit die Wechselwirkung mit der Materie ist abhängig von dem chemischen Aufbau des Kunststoffes und der verwendeten Wellenlänge des Lasers. Vielfach ist es notwendig, damit Kunststoffe laserbeschriftbar werden, entsprechende Zusatzstoffe, z. B. Absorber, zuzugeben.Many plastics, such as polyethylene (PE), polypropylene (PP), polyamide (PA), polymethyl methacrylate (PMMA), polyoxymethylene (POM), polyurethane (PUR), polyester, have so far been difficult or impossible to mark with a laser. A CO 2 laser, which emits light in the infrared range at 10.6 µm, only produces a weak, barely legible marking on polyolefins, even at very high outputs, since the absorption coefficient of the plastics to be processed at these wavelengths is not high enough to match one To induce color change in the polymeric material. The plastic must not fully reflect or let the laser light through, as there is no interaction. However, strong absorption must also not occur, since in this case the plastic evaporates and only one engraving remains. The absorption of the laser beams and thus the interaction with the material depends on the chemical structure of the plastic and the wavelength of the laser used. In many cases, it is necessary for plastics to be laser-inscribable, corresponding additives, e.g. B. absorber to admit.

Aus dem Artikel "Pearl Lustre Pigments-Characteristics und Functional Effects" in Speciality Chemicals, Mai 1982, Vol.2, Nr. 2 ist die Verwendung von Perlglanzpigmenten für die Lasermarkierung bekannt. Perlglanzpigmente haben aber den Nachteil, daß sie die koloristische Beschaffenheit des Kunststoffes sehr stark verändern, was oft unerwünscht ist.From the article "Pearl Luster Pigments-Characteristics and Functional Effects "in Specialty Chemicals, May 1982, Vol.2, No. 2 is the use of pearlescent pigments known for laser marking. pearlescent but have the disadvantage that they have a coloristic nature of the plastic change very much, which is often undesirable.

Aus der DE-OS 29 36 926 ist bekannt, die Beschriftung eines polymeren Materials mittels Laserlicht dadurch zu erzielen, daß man dem Kunststoff einen sich bei der Einwirkung von Energiestrahlung verfärbenden Füllstoff wie Ruß oder Graphit beimischt.From DE-OS 29 36 926 it is known to label a polymer To achieve material by means of laser light by looking at the plastic a filler that changes color when exposed to energy radiation like carbon black or graphite.

In der EP 0 190 997 A werden Laser-beschriftbare Formmassen, u.a. PE oder PS, dadurch hergestellt, daß man dem hochmolekularem organischem Material mindestens ein anorganisches Pigment zusetzt.EP 0 190 997 A describes laser-inscribable molding compositions, i.a. PE or PS, made by the high molecular weight organic Material adds at least one inorganic pigment.

In der EP 0 330 869 werden PBT und PET mit TiO2 und Ruß versetzt. Die Beschriftung ist dunkel auf hellem Grund. Die Verwendung von Ruß und/oder Graphit als Absorber bei der Lasermarkierung von Polyester ist aus der EP 0 485 181 bekannt.In EP 0 330 869, PBT and PET are mixed with TiO 2 and carbon black. The lettering is dark on a light background. The use of carbon black and / or graphite as an absorber in the laser marking of polyester is known from EP 0 485 181.

Die für die Lasermarkierung bekannten Füllstoffe besitzen aber entweder den Nachteil, daß sie den zu beschriftenden Kunststoff nachhaltig einfärben und folglich die Laserbeschriftung, die üblicherweise eine dunkle Schrift auf einem helleren Untergrund ist, dann nicht mehr ausreichend kontrastreich, d.h. lesbar, ist oder daß, wie z. B. bei Kaolin, die Markierung sehr schwach ist und erst bei hohen Einsatzmengen des Zuschlagstoffes gut sichtbar wird.The fillers known for laser marking either have the disadvantage that they permanently color the plastic to be labeled and consequently laser marking, which is usually dark Writing on a lighter background is then no longer sufficient high contrast, i.e. is readable, or that, such as. B. with kaolin, the marking is very weak and only with high amounts of the aggregate is clearly visible.

In der DE 195 36 047 wird die Verwendung von Polycarbonat, welches aufgrund seiner amorphen Struktur selber nur schlecht lasermarkierbar ist, in einer Polymermatrix eines Polyalkylenterephthalats beschrieben. Durch Absorption von Laserenergie können in der Polymermatrix eines Polyalkylenterephthalats dunkle Zeichen auf hellem Hintergrund erreicht werden.DE 195 36 047 describes the use of polycarbonate, which Due to its amorphous structure, it is itself difficult to laser mark, described in a polymer matrix of a polyalkylene terephthalate. By Absorption of laser energy can occur in the polymer matrix of a polyalkylene terephthalate Achieved dark characters on a light background become.

Neben den oben genannten Kunststoffen gibt es aber auch Polymere, die ohne Zusatz von Additiven dunkel und sehr kontrastreich mittels eines Lasers markierbar sind. Hierzu zählen z. B. PET, Butadien-Styrol (ABS), Polystyrol, Polyphenylether (PPO), Liquid Crystal Polymers (LCP), Polyphenylensulfid, Polyarylate, Polyarylsulfide, Polyarylsulfone, Polyaryletherketone sowie deren Blends.In addition to the plastics mentioned above, there are also polymers that without the addition of additives dark and very high contrast using a Lasers are markable. These include e.g. B. PET, butadiene styrene (ABS), Polystyrene, polyphenyl ether (PPO), liquid crystal polymers (LCP), polyphenylene sulfide, Polyarylates, polyaryl sulfides, polyaryl sulfones, polyaryl ether ketones as well as their blends.

Aufgabe der vorliegenden Erfindung war es daher lasermarkierbare Kunststoffe zu finden, die unter Einwirkung von Laserlicht eine Lasermarkierung mit hohem Kontrast ermöglichen. Der Füllstoff bzw. das erfolgreiche Absorptionsmittel sollte dabei eine sehr helle neutrale Eigenfarbe bzw. die Eigenschaften des zu markierenden vorgefärbten Kunststoffes besitzen oder diese nicht oder nur unwesentlich beeinflussen.The object of the present invention was therefore laser-markable plastics to find a laser mark under the influence of laser light enable with high contrast. The filler or the successful one Absorbent should have a very bright neutral color or the Have properties of the pre-colored plastic to be marked or not or only marginally influence them.

Überraschenderweise wurde gefunden, daß ein schwer belaserbarer Kunststoff sich sehr gut markierten läßt, wenn man dem Kunststoff z.B. eines der vorgenannten intrinsisch markierbaren Polymere in feiner Verteilung zusetzt. Die intrinsiche Markierbarkeit des Polymers wird somit auf den Kunststoff übertragen, der dieses Verhalten nicht oder nur in geringem Maße aufweist. Ein derart dotierter Kunststoff zeigt nach dem Laserbeschuß kontrastreiche und kantenscharfe Markierungen selbst bei geringen Laserintensitäten.Surprisingly, it was found that a difficult to laser Plastic can be marked very well if you e.g. plastic one of the aforementioned intrinsically markable polymers in fine distribution added. The intrinsic markability of the polymer is thus reduced transfer the plastic that does not or only slightly Has dimensions. Plastic doped in this way shows after laser bombardment high-contrast and sharp-edged markings, even with small ones Laser intensities.

Gegenstand der Erfindung sind daher lasermarkierbare Kunststoffe, dadurch gekennzeichnet, daß schwer belasserbare Kunststoffe ein oder mehrere intrinsisch lasermarkierbare Polymere in Form von mikrovermahlenen Partikeln mit einer Teilchengröße von 0,1 bis 100 µm enthalten.The invention therefore relates to laser-markable plastics, characterized in that difficult to leave plastics one or several intrinsically laser-markable polymers in the form of micro-ground particles with a particle size of 0.1 up to 100 µm included.

Durch den Zusatz von mikrovermahlenen, intrinsisch markierbaren Polymeren als Absorber in Konzentrationen von 0,1 bis 10 Gew.%, vorzugsweise 0,1 bis 5 Gew.%, und insbesondere 0,1 bis 2 Gew.%, bezogen auf das Kunststoffsystem, wird bei der Lasermarkierung ein hoher Kontrast erzielt. Die Konzentration der intrinsisch markierbaren Polymere im Kunststoff ist allerdings abhängig von dem eingesetzten Kunststoffsystem und dem verwendeten Laser.By adding micro-milled, intrinsically markable polymers as an absorber in concentrations of 0.1 to 10% by weight, preferably 0.1 to 5% by weight, and in particular 0.1 to 2% by weight, based on the plastic system becomes a high contrast when laser marking achieved. The concentration of the intrinsically markable polymers in the plastic depends on the plastic system used and the laser used.

Geeignete Polymere bzw. Polymergemische sind alle bekannten gut belaserbaren Kunststoffe wie z. B. PET, ABS, Polystyrol, PPO, Polyphenylensulfid, Polyphenylensulfon, Polyimidsulfon, LCPs.Suitable polymers or polymer mixtures are all known laserable plastics such. B. PET, ABS, polystyrene, PPO, polyphenylene sulfide, Polyphenylene sulfone, polyimide sulfone, LCPs.

Insbesondere geeignet sind mikrovermahlene Thermoplaste mit einem sehr hohen Schmelzbereich von > 300 °C. Die Kantenschärfe der Markierung wird insbesondere durch die Partikelgröße der mikrovermahlenen Polymere bestimmt. Vorzugsweise weisen die Polymere Partikelgrößen im Bereich von 0,1 bis 50 µm, insbesondere von 1 bis 20 µm auf.Micro-ground thermoplastics with a very high melting range of> 300 ° C. The edge sharpness of the Marking is particularly due to the particle size of the micromilled Polymers determined. The polymers preferably have Particle sizes in the range from 0.1 to 50 µm, in particular from 1 to 20 µm.

Das Markierungsergebnis wird positiv beeinflußt, wenn das intrinsich markierbare Polymer als weiteren Absorber ein lichtsensitives Pigment, wie z. B. einen Füllstoff, ein leitfähiges Pigment und/oder ein Effektpigment, enthält. Durch die Zugabe eines weiteren Absorbers wird der Kontrast in Abhängigkeit des verwendeten Kunststoffsystems verstärkt. Die Zusatzmenge an lichtsensitivem Pigment sollte zwischen 0,1 und 90 % betragen.The marking result is influenced positively if the intrinsic Markable polymer as a further absorber, a light-sensitive pigment, such as B. a filler, a conductive pigment and / or an effect pigment, contains. By adding another absorber, the Contrast increased depending on the plastic system used. The amount of light-sensitive pigment added should be between 0.1 and 90% be.

Besonders geeignete lichtsensitive Pigmente sind Füllstoffe, wie z. B. TiO2 und SiO2, und Schichtsilikate. Als silikatische Plättchen kommen dabei insbesondere helle bzw. weiße Glimmer in Betracht. Selbstverständlich können auch andere natürliche Glimmer wie Phlogopit und Biotit, synthetischer Glimmer, Talk- und Glasschuppen verwendet werden. Unter Effektpigment sind alle bekannten Glanz-, Metall- und Perlglanzpigmente zu verstehen, wie sie z. B. von den Firmen Mearl, Eckart-Werken und Merck KGaA vertrieben werden. Geeignete leitfähige Pigmente sind z. B. die unter dem Handelsnamen Minatec® vertriebenen Pigmente der Fa. Merck KGaA. Hierbei handelt es sich um plättchenförmige TiO2/Glimmerpigmente, die als leitfähige Schicht eine äußere Schicht aus Zinn-/Antimonoxid enthalten. Als geeignete lichtsensitive Pigmente sind weiterhin die Oxide, Hydroxide, Sulfide, Sulfate und Phosphate von Metallen, wie z. B. Kupfer, Bismuth, Zinn, Zink, Silber, Antimon, Mangan, Eisen, Nickel und Chrom hier zu nennen. Hierbei ist insbesondere die Verwendung von Antimon, Bismutoxichlorid und basischem Kupfer(II)-hydroxidphosphat zu erwähnen. Besonders bevorzugt ist hierbei ein Produkt, wie es durch Erhitzen von blauem Cu(II)orthophosphat (Cu3(PO4)2·3 H2O) auf 100 bis 200 °C entsteht und die chemische Summenformel 4 CuO·P2O5·H2O oder Cu3(PO4)2·Cu(OH)2 aufweist. Weitere geeignete Kupferphosphate sind 6 CuO·P2O5·3 H2O, Cu3(PO4)2·3 Cu(OH)2, 5 CuO·P2O5·3 H2O, Cu3(PO4)2·2 Cu(OH)2·H2O, 4 CuO·P2O5, 4 CuO·P2O5·3H2O, 4 CuO·P2O5·1,5 H2O, 4 CuO·P2O5· 1,2 H2O.Particularly suitable light-sensitive pigments are fillers, such as. B. TiO 2 and SiO 2 , and layered silicates. In particular, light or white mica can be used as the silicate plate. Of course, other natural mica such as phlogopite and biotite, synthetic mica, talc and glass flakes can also be used. Under effect pigment all known gloss, metal and pearlescent pigments are to be understood, as they z. B. are distributed by the companies Mearl, Eckart-Werke and Merck KGaA. Suitable conductive pigments are e.g. B. the pigments sold by Merck KGaA under the trade name Minatec®. These are platelet-shaped TiO 2 / mica pigments that contain an outer layer of tin / antimony oxide as a conductive layer. Suitable oxides, hydroxides, sulfides, sulfates and phosphates of metals, such as, for example, are suitable as light-sensitive pigments. B. copper, bismuth, tin, zinc, silver, antimony, manganese, iron, nickel and chrome to name here. The use of antimony, bismuth oxychloride and basic copper (II) hydroxide phosphate should be mentioned in particular. A product such as is produced by heating blue Cu (II) orthophosphate (Cu 3 (PO 4 ) 2 · 3 H 2 O) to 100 to 200 ° C. and the chemical formula 4 CuO · P 2 O 5 is particularly preferred · H 2 O or Cu 3 (PO 4) 2 · Cu (OH) 2 has. Further suitable copper phosphates are 6 CuO · P 2 O 5 · 3 H 2 O, Cu 3 (PO 4 ) 2 · 3 Cu (OH) 2 , 5 CuO · P 2 O 5 · 3 H 2 O, Cu 3 (PO 4 ) 2 · 2 Cu (OH) 2 · H 2 O, 4 CuO · P 2 O 5 , 4 CuO · P 2 O 5 · 3H 2 O, 4 CuO · P 2 O 5 · 1.5 H 2 O, 4 CuO · P 2 O 5 · 1.2 H 2 O.

Eine Verbesserung der Lasermarkierbarkeit wird auch erreicht, wenn neben dem intrinsisch markierenden Polymer eine oder mehrere o.g. lichtsensitive Pigmente als weitere Komponente dem Kunststoff beigefügt wird. Dabei sollte der Gewichtsanteil aller Absorber im Kunststoff in Kombination mit den mikrovermahlenen Polymeren insgesamt 10 Gew.% bezogen auf das Kunststoffsystem nicht übersteigen. Vorzugsweise enthält der Kunststoff 0-5 Gew.% an lichtsensitiven Pigmenten, insbesondere 0-1 Gew.%. Das Mischungsverhältnis der lichtsensitiven Pigmente mit den mikrovermahlenen Polymeren unterliegt hierbei keiner Beschränkung.An improvement in laser markability is also achieved if in addition to the intrinsically labeling polymer, one or more of the above light-sensitive pigments added to the plastic as a further component becomes. The weight fraction of all absorbers in the plastic should be in Combination with the micro-milled polymers a total of 10% by weight in relation to the plastic system. Preferably the plastic contains 0-5% by weight of light-sensitive pigments, in particular 0-1% by weight. The mixing ratio of the light sensitive pigments with the micro-milled polymers, none is subject to this Restriction.

Ferner können dem schwer belaserbaren Kunststoff auch Farbpigmente zugesetzt werden, die farbliche Variationen jeder Art zulassen und gleichzeitig eine Beibehaltung der Lasermarkierung gewährleisten.Color pigments can also be used in the hard-to-laser plastic be added that allow color variations of any kind and at the same time ensure that the laser marking is retained.

Die Zugabe der lichtsensitiven Pigmente und/oder Farbpigmente erfolgt vorzugsweise zusammen mit den Polymeren, prinzipiell ist aber auch die separate Zugabe möglich. Es kann auch ein Gemisch verschiedener lichtsensitiver Pigmente dem Kunststoff zugesetzt werden. The light-sensitive pigments and / or color pigments are added preferably together with the polymers, but in principle is also separate addition possible. It can also be a mixture of different ones light-sensitive pigments can be added to the plastic.

Vorzugsweise wird bei der Markierung energiereiche Strahlung eingesetzt, im allgemeinem, im Wellenlängenbereich von 150 nm bis 10600 nm, insbesondere im Bereich 150 nm bis 1100 nm. Beispielsweise seien hier CO2-Laser (10600 nm), Nd:YAG-Laser (1064 nm bzw. 532 nm) oder gepulste UV-Laser (Excimer-Laser) erwähnt. Besonders bevorzugt werden Nd:YAG-Laser (1064 nm bzw. 532 nm) und CO2-Laser (10600 nm) eingesetzt. Die Energiedichten der eingesetzten Laser liegen im allgemeinen im Bereich von 0,3 mJ/cm2 bis 50 J/cm2, vorzugsweise im Bereich von 0,3 mJ/cm2 bis 10 J/cm2.High-energy radiation is preferably used for the marking, in general in the wavelength range from 150 nm to 10600 nm, in particular in the range from 150 nm to 1100 nm. For example, here are CO 2 lasers (10600 nm), Nd: YAG lasers (1064 nm or 532 nm) or pulsed UV laser (excimer laser) mentioned. Nd: YAG lasers (1064 nm or 532 nm) and CO 2 lasers (10600 nm) are particularly preferably used. The energy densities of the lasers used are generally in the range from 0.3 mJ / cm 2 to 50 J / cm 2 , preferably in the range from 0.3 mJ / cm 2 to 10 J / cm 2 .

Alle bekannten nur sehr schlecht lasermarkierbaren Kunststoffe, wie sie z.B. im Ullmann, Bd. 15, S. 457 ff., Verlag VCH oder Saechtling Kunststoff Taschenbuch beschrieben werden, können durch Zusatz der erfindungsgemäßen Polymere für die Lasermarkierung Anwendung finden. Solche Kunststoffe sind z.B. Duroplaste, Polyethylen (PE-HD, PE-LD, PE-LLD), Polypropylen (PP), Polyester, Polyacetal, Polyamide (PA), Poly-urethane (PUR), Polybutylenterephthalat, Polymethylmethacrylat (PMMA), Polyvinylacetal, Polystyrol, Butadien-Styrol (ABS), Acrylnitril-Styrol-Acrylester (ASA), und ihre Copolymere und/oder deren Mischungen. Insbesondere sind Polyolefine, Polyurethane, Polyoxymethylene und Polyamide aufgrund ihrer mechanischen Eigenschaften, den kostengünstigen Verarbeitungsmethoden und ihrer schlechten Lasermarkierbarkeit für die Dotierung mit den erfindungsgemäßen Polymeren geeignet.All known, very poorly laser-markable plastics such as these e.g. in Ullmann, vol. 15, pp. 457 ff., publisher VCH or Saechtling Kunststoff Paperback can be described by adding the invention Find polymers for laser marking. Such Plastics are e.g. Thermosets, polyethylene (PE-HD, PE-LD, PE-LLD), Polypropylene (PP), polyester, polyacetal, polyamide (PA), poly-urethane (PUR), polybutylene terephthalate, polymethyl methacrylate (PMMA), polyvinyl acetal, Polystyrene, butadiene styrene (ABS), acrylonitrile styrene acrylic ester (ASA), and their copolymers and / or mixtures thereof. In particular are due to polyolefins, polyurethanes, polyoxymethylenes and polyamides their mechanical properties, the inexpensive processing methods and their poor laser markability for doping suitable with the polymers according to the invention.

Die Einarbeitung des mikrovermahlenen Polymers in den Kunststoff erfolgt nach den für Pigmente und Füllstoffe bekannten Verfahren. Anschließend wird der pigmentierte Kunststoff dann unter Wärmeeinwirkung verformt. Bei der Wahl des zu vermahlenen intrinsisch markierbaren Polymers ist zu beachten, daß die Partikelstruktur nach der Einarbeitung erhalten bleibt, d. h., die Partikel sollten nicht in der Schmelze löslich sein, bzw. mit aufschmelzen. Dies wird erreicht durch entsprechende Abstimmung der Schmelzbereiche des Kunststoffsystems mit dem des mikrovermahlenen Polymers. The micro-ground polymer is incorporated into the plastic according to the processes known for pigments and fillers. Subsequently the pigmented plastic is then deformed under the influence of heat. When choosing the intrinsically markable polymer to be ground is too note that the particle structure is retained after incorporation, d. that is, the particles should not be soluble in the melt or melt with them. This is achieved by appropriate coordination of the Melting ranges of the plastic system with that of the micro-ground Polymer.

Dem Kunststoffgranulat können bei der Einarbeitung des mikrovermahlenen Polymers gegebenenfalls Haftmittel, organische polymerverträgliche Lösungsmittel, Stabilisatoren, optische Aufheller, Farbpigmente, Farbstoffe, Füllstoffe, Verstärkungsstoffe, Flammschutzadditive, Antistatika und/oder unter den Arbeitsbedingungen temperaturstabile Tenside zugesetzt werden. Neben den üblicherweise eingesetzten Hilfsstoffen können noch weitere, hier nicht erwähnte Additive, dem Kunststoff zugesetzt werden. Das Vorhandensein weiterer Zusätze im bestehenden Kunststoffsystemen kann allerdings einen Einfluß auf das Markierergebnis ausüben.The plastic granulate can be incorporated into the micromilled Polymers optionally adhesives, organic polymer compatible Solvents, stabilizers, optical brighteners, color pigments, dyes, Fillers, reinforcing materials, flame retardants, antistatic agents and / or temperature-stable surfactants added under the working conditions become. In addition to the commonly used auxiliaries other additives, not mentioned here, added to the plastic become. The presence of other additives in existing plastic systems can, however, have an influence on the marking result.

Die Herstellung der Kunststoffgranulat-/ Polymer-Mischung erfolgt in der Regel so, daß in einem geeigneten Mischer das Kunststoffgranulat vorgelegt, mit eventuellen Zusätzen benetzt wird und danach die mikrovermahlenen Polymere zugesetzt und untergemischt werden. Die so erhaltene Mischung kann dann direkt in einem Extruder oder einer Spritzgußmaschine verarbeitet werden. Die bei der Verarbeitung gebildeten Formkörper zeigen meist eine sehr homogene Verteilung der Polymere bzw. des Polymergemisches. Zuletzt findet die Lasermarkierung, vorzugsweise mit einem Nd:YAG-Laser, statt.The production of the plastic granulate / polymer mixture takes place in the As a rule, the plastic granulate is placed in a suitable mixer, is wetted with any additives and then the micro-ground Polymers are added and mixed in. The so obtained Mixing can then be done directly in an extruder or an injection molding machine are processed. The moldings formed during processing usually show a very homogeneous distribution of the polymers or of the polymer mixture. Lastly, the laser marking takes place, preferably with an Nd: YAG laser instead.

Die Beschriftung mit dem Laser erfolgt derart, daß der Probenkörper in den Strahlengang eines gepulsten Lasers, vorzugsweise eines Nd:YAG-Lasers gebracht wird. Ferner ist eine Beschriftung mit einem CO2- oder einem Excimer-Laser möglich. Jedoch sind auch mit anderen Lasertypen, die eine Wellenlänge in einem Bereich hoher Absorption des intrinsisch markierenden Polymers aufweisen, die gewünschten Ergebnisse zu erzielen. Der erhaltene Farbton und die Farbtiefe werden durch die Laserparameter, wie die Bestrahlungszeit und Bestrahlungsleistung bestimmt. Die Leistung der verwendeten Lasers hängt von der jeweiligen Anwendung ab und kann im Einzelfall vom Fachmann ohne weiteres ermittelt werden. The labeling with the laser takes place in such a way that the sample body is brought into the beam path of a pulsed laser, preferably an Nd: YAG laser. Labeling with a CO 2 or excimer laser is also possible. However, the desired results can also be achieved with other types of lasers which have a wavelength in a region of high absorption of the intrinsically marking polymer. The hue obtained and the depth of color are determined by the laser parameters, such as the irradiation time and irradiation power. The power of the laser used depends on the respective application and can be determined easily by a specialist in individual cases.

Die Verwendung des erfindungsgemäß dotierten Kunststoffes kann auf allen Gebieten erfolgen, wo bisher übliche Druckverfahren zur Beschriftung von Kunststoffen eingesetzt werden. Beispielsweise können Formkörper aus dem erfindungsgemäßen Kunststoff in der Elektro-, Elektronikund Kraftfahrzeugindustrie Anwendung finden. Die Kennzeichnung und Beschriftung von z.B. Gehäusen, Leitungen, Tastenkappen, Zierleisten bzw. Funktionsteilen im Heizungs-, Lüftungs- und Kühlbereich oder Schalter, Stecker, Hebel und Griffe, die aus dem erfindungsgemäßen Kunststoff bestehen, kann selbst an schwer zugänglichen Stellen mit Hilfe von Laserlicht erfolgen. Weiterhin kann das erfindungsgemäße Kunststoffsystem aufgrund seines geringen Schwermetallanteils bei Verpackungen im Lebensmittelbereich oder im Spielzeugbereich eingesetzt werden. Die Markierungen auf den Verpackungen zeichnen sich dadurch aus, daß sie wisch- und kratzfest, stabil bei nachträglichen Sterilisationsprozessen, hygienisch rein beim Markierungsprozeß aufbringbar sind. Komplette Etikettenbilder können dauerhaft auf die Verpackung für ein Mehrwegsystem aufgebracht werden. Ein weiteres wichtiges Anwendungsgebiet für die Laserbeschriftung sind Ausweiskarten und Kunststoffmarken zur individuellen Kennzeichnung von Tieren, sogenannte Cattle Tags oder Ohrmarken. Die Lasermarkierung von Kunststoffgegenständen bzw. Formkörpern, die aus dem erfindungsgemäßen Kunststoff bestehen, ist somit möglich.The use of the plastic doped according to the invention can be limited to in all areas, where previously customary printing methods for labeling of plastics. For example, molded articles from the plastic according to the invention in electrical, electronics and Motor vehicle industry find application. The labeling and Labeling of e.g. Housings, cables, key caps, trim strips or functional parts in the heating, ventilation and cooling area or Switches, plugs, levers and handles that result from the invention Plastic, can help even in hard-to-reach places done by laser light. Furthermore, the plastic system according to the invention due to its low heavy metal content in packaging be used in the food sector or in the toy sector. The Markings on the packaging are characterized by the fact that they smudge-proof and scratch-resistant, stable during subsequent sterilization processes, can be applied hygienically during the marking process. complete Label images can be permanently on the packaging for a reusable system be applied. Another important area of application for the laser inscription are ID cards and plastic brands individual identification of animals, so-called cattle tags or Earmarks. The laser marking of plastic objects or moldings, which consist of the plastic according to the invention is thus possible.

Die nachfolgenden Beispiele sollen die Erfindung erläutern ohne sie jedoch zu begrenzen. The following examples are intended to illustrate the invention without it limit however.

BeispieleExamples Beispiel 1example 1

99 Teile99 parts Polypropylen (Stamylan PPH 10 der Fa. DSM)Polypropylene (Stamylan PPH 10 from DSM) 1 Teil1st chapter Polyphenylensulfid vermahlen auf Teilchengröße < 25 µmPolyphenylene sulfide is ground to particle size <25 µm

Die Komponenten werden physikalisch gemischt und mittels einer Spritzgußmaschine homogenisiert und zu Plättchen geformt. Die Beschriftung mit einem Nd:YAG-Laser bei 532 und 1064 nm Wellenlängen zeigt über einen weiten Einstellbereich eine schwarze kontrastreiche Markierung mit glatter Oberfläche.The components are mixed physically and using an injection molding machine homogenized and shaped into platelets. The caption with an Nd: YAG laser at 532 and 1064 nm wavelengths shows about a high-contrast black marking with a wide setting range smooth surface.

Beispiel 2Example 2

99,5 Teile99.5 parts Polypropylen (Stamylan PPH 10)Polypropylene (Stamylan PPH 10) 0,5 Teil0.5 part Polyphenylensulfon vermahlen auf Teilchengröße < 10 µmPolyphenylene sulfone is ground to particle size <10 µm

Die Komponenten werden gemischt und mittels einer Spritzgußmaschine homogenisiert und zu Plättchen geformt. Die Beschriftung mit einem Nd:YAG-Laser zeigt über einen weiten Einstellbereich eine schwarze kontrastreiche Markierung mit glatter Oberfläche.The components are mixed and using an injection molding machine homogenized and shaped into platelets. The label with a Nd: YAG laser shows a black over a wide setting range high-contrast marking with smooth surface.

Beispiel 3Example 3

99 Teile99 parts Polyamid 6 (Ultramid B3K der Fa. BASF)Polyamide 6 (Ultramid B3K from BASF) 1 Teil1st chapter Polyimidsulfon vermahlen auf Teilchengröße < 15 µmPolyimide sulfone grind to particle size <15 µm

Die Komponenten werden gemischt und mittels einer Spritzgußmaschine homogenisiert und zu Plättchen geformt. Die Beschriftung mit einem Nd:YAG-Laser zeigt über einen weiten Einstellbereich eine tiefschwarze kontrastreiche Markierung mit glatter Oberfläche. The components are mixed and using an injection molding machine homogenized and shaped into platelets. The label with a Nd: YAG laser shows a deep black over a wide setting range high-contrast marking with smooth surface.

Beispiel 4Example 4

99,6 Teile99.6 parts Polyamid 6 (Ultramid B3K)Polyamide 6 (Ultramid B3K) 0,4 Teile0.4 parts Polyphenylensulfid vermahlen auf Teilchengröße < 10 µmPolyphenylene sulfide is ground to particle size <10 µm

Die Komponenten werden gemischt und mittels einer Spritzgußmaschine homogenisiert und zu Plättchen geformt. Die Beschriftung mit einem Nd:YAG-Laser zeigt über einen weiten Einstellbereich eine schwarze kontrastreiche Markierung mit glatter Oberfläche.The components are mixed and using an injection molding machine homogenized and shaped into platelets. The label with a Nd: YAG laser shows a black over a wide setting range high-contrast marking with smooth surface.

Beispiel 5Example 5

99 Teile99 parts Polyoxymethylen (Delrin der Fa. Du Pont)Polyoxymethylene (Delrin from Du Pont) 1 Teil1st chapter Polyphenylensulfid vermahlen auf Teilchengröße < 5 µmPolyphenylene sulfide is ground to a particle size of <5 µm

Die Komponenten werden gemischt und mittels einer Spritzgußmaschine homogenisiert und zu Plättchen geformt. Die Beschriftung mit einem Nd:YAG-Laser zeigt über einen weiten Einstellbereich eine schwarze kontrastreiche Markierung mit glatter Oberfläche.The components are mixed and using an injection molding machine homogenized and shaped into platelets. The label with a Nd: YAG laser shows a black over a wide setting range high-contrast marking with smooth surface.

Beispiel 6Example 6

99 Teile99 parts ungesättigtes Polyesterharz (Palatal der Fa. BASF)unsaturated polyester resin (Palatal from BASF) 1 Teil1st chapter Polyphenylensulfid vermahlen auf Teilchengröße < 10 µmPolyphenylene sulfide is ground to particle size <10 µm

Das Polyphenylensulfid wird in das flüssige Polyestergießharz homogen eingerührt. Nach Zugabe von Beschleuniger (Co-Octoat) und Härter (Cyclohexanonperoxid) wird die Mischung in eine Form gegossen. Nach der Aushärtung erhält man ein Formteil, welches mittels Nd:YAG-Laser schwarz und kontrastreich markierbar ist. The polyphenylene sulfide becomes homogeneous in the liquid polyester casting resin stirred. After adding accelerator (Co-Octoat) and hardener (Cyclohexanone peroxide) the mixture is poured into a mold. To the hardening gives a molded part, which by means of Nd: YAG laser is black and can be marked with high contrast.

Beispiel 7Example 7

99 Teile Polysulfon (Ultrason der Fa. BASF) werden zusammen mit 1 Teil Glimmer mittels Extruder compoundiert. Das Compound wird mikrovermahlen auf eine Teilchengröße von < 10 µm. Von dem so erhaltenen Pulver werden 0,5 % einem PMMA zugesetzt. Diese Mischung wird auf einem Extruder zu Platten verarbeitet, welche schwarz und kontrastreich mit einem Nd:YAG-Laser bei 532 und 1.064 nm Wellenlänge markierbar sind.99 parts of polysulfone (Ultrason from BASF) together with 1 part Mica compounded using an extruder. The compound is micro-milled to a particle size of <10 µm. From the so obtained Powder is added 0.5% to a PMMA. This mix is going on an extruder into sheets that are black and rich in contrast Markable with an Nd: YAG laser at 532 and 1,064 nm wavelength are.

Beispiel 8Example 8

96 Teile Polyphenylensulfid werden analog Beispiel 7 mit 4 Teilen basischem Kupferphosphat compoundiert. Mit dem mikrovermahlenen Pulver dieser Mischung erhält man mit einem Nd:YAG-Laser bereits bei einer Zugabe von je 0,4 % in üblicherweise nicht lasermarkierbaren Kunststorfen, wie.

  • (a) Polyethylen (PE)
  • (b) Polypropylen (PP)
  • (c) Polyamid (PA)
  • (d) Polymethylmethacrylat (PMMA)
  • (e) Polyurethan (PUR)
  • (f) Polyoxymethylen (POM)
    • tiefschwarze kontrastreiche und kantenscharfe Markierungen.96 parts of polyphenylene sulfide are compounded analogously to Example 7 with 4 parts of basic copper phosphate. With the micro-ground powder of this mixture, an Nd: YAG laser is obtained with an addition of 0.4% in usually non-laser-markable plastics such as.
  • (a) polyethylene (PE)
  • (b) polypropylene (PP)
  • (c) polyamide (PA)
  • (d) polymethyl methacrylate (PMMA)
  • (e) polyurethane (PUR)
  • (f) polyoxymethylene (POM)
    • deep black high-contrast and sharp-edged markings.

    Claims (12)

    1. Laser-markable plastics, characterised in that a plastic which is difficult to laser-mark comprises, as absorber material, an intrinsically laser-markable polymer in the form of microground particles having a particle size of 0.1 -100 µm.
    2. Laser-markable plastics according to Claim 1, characterised in that the absorber material is a plastic which is solid at high temperatures.
    3. Laser-markable plastics according to Claim 1 or 2, characterised in that the absorber material is polyphenylene sulfide, polysulfone, polyarylate, polyimide, liquid-crystalline polymers (LCPs), PET, ABS, polystyrene, PPO, polyphenylene sulfone, polyimide sulfone or a mixture thereof.
    4. Laser-markable plastics according to one of Claims 1 to 3, characterised in that the proportion of the absorber material, based on the plastic system, is 0.1 - 10% by weight.
    5. Laser-markable plastics according to one of Claims 1 to 4, characterised in that the particle structure of the intrinsically markable polymer is retained in the plastic.
    6. Laser-markable plastics according to one of Claims 1 to 5, characterised in that the absorber material additionally comprises, as further absorber, one or more light-sensitive pigments.
    7. Laser-markable plastics according to one of Claims 1 to 6, characterised in that the light-sensitive pigment is a filler, natural or synthetic mica, copper phosphate, an effect pigment, a conductive pigment, a metal nitrate, metal sulfate, metal sulfide, metal oxide, talc and glass flakes, antimony, bismuth oxychloride, or basic copper(II) hydroxide phosphate.
    8. Laser-markable plastics according to one of Claims 1 to 7, characterised in that the proportion of the light-sensitive pigments in the plastic is from 0 to 5% by weight, based on the plastic system.
    9. Laser-markable plastics according to one of Claims 1 to 8, characterised in that the plastic which is difficult to laser-treat is polyethylene, polypropylene, polyamide, polyoxymethylene, polyester, polymethyl methacrylate, polyurethane or a copolymer thereof.
    10. Laser-markable plastics according to one of Claims 1 to 9, characterised in that they additionally comprise coloured pigments.
    11. Use of the laser-markable plastics according to Claim 1 as material for the production of mouldings which are marked with the aid of lasers.
    12. Moulding consisting of the laser-markable plastic according to Claim 1.
    EP98929407A 1997-06-19 1998-05-30 Plastics which can be laser-marked Expired - Lifetime EP0991523B1 (en)

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    DE19726136 1997-06-19
    PCT/EP1998/003250 WO1998058805A1 (en) 1997-06-19 1998-05-30 Plastics which can be laser-marked

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    DE102008034021A1 (en) 2008-07-16 2010-01-21 Merck Patent Gmbh Method for producing a security and / or value product with random pattern and correlated identity string
    DE102008034022A1 (en) 2008-07-16 2010-01-21 Merck Patent Gmbh Method for producing a security and / or value product with subregions with different luminescence emission
    WO2011006634A2 (en) 2009-07-17 2011-01-20 Leonhard Kurz Stiftung & Co. Kg Method for the production of a multilayer element, and multilayer element

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    DE59805984D1 (en) 2002-11-21
    EP0991523A1 (en) 2000-04-12
    KR20010013893A (en) 2001-02-26
    ES2183381T3 (en) 2003-03-16
    BR9810065A (en) 2000-09-19
    DE19880779D2 (en) 2000-09-07
    CN1260752A (en) 2000-07-19
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    WO1998058805A1 (en) 1998-12-30
    JP2002504947A (en) 2002-02-12

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