EP1279517B1 - Colour writing or marking of plastics and lacquers - Google Patents

Colour writing or marking of plastics and lacquers Download PDF

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Publication number
EP1279517B1
EP1279517B1 EP02016489A EP02016489A EP1279517B1 EP 1279517 B1 EP1279517 B1 EP 1279517B1 EP 02016489 A EP02016489 A EP 02016489A EP 02016489 A EP02016489 A EP 02016489A EP 1279517 B1 EP1279517 B1 EP 1279517B1
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EP
European Patent Office
Prior art keywords
pigments
plastic
process according
laser
marking
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EP02016489A
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German (de)
French (fr)
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EP1279517A2 (en
EP1279517A3 (en
Inventor
Reiner Delp
Matthias Dr. Kuntz
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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
    • B41M5/267—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
    • Y10S430/165—Thermal imaging composition

Definitions

  • the present invention relates to the colored labeling or marking of plastics, paints, including powder coatings, wherein a colorant is transferred by means of a laser light absorbing substance by laser radiation in the plastic or paint.
  • EP 0 684 144 B1 describes a dopant for the colored marking of plastic materials, which is characterized in that it contains a mixture of a clouding agent and a chromogenic substance.
  • the object of the present invention was therefore to find a method which, under the action of laser light, permits a colored marking with high contrast on each plastic ink using only one laser or laser wavelength.
  • the invention relates to a method for colored labeling and marking of Hunststoffen or paints, according to claim 1 and a shaped article according to claim 9.
  • the ratio colorant / laser light absorbing substance is 10: 1 to 1:10, preferably 95: 5 to 70: 30, especially 90: 10 to 80: 20.
  • the concentration of the colorant and the laser light absorbing substance on the surface of the plastic or the paint depends on the plastic system used or the paint composition and the surface of the label.
  • Suitable organic colorants are preferably those selected from the group of the following organic pigments: copper phthalocyanines, dioxazines, anthraquinones, monoazo and diazo pigments, diketopyrolopyrrole, polycyclic pigments, anthrapyrimidines, quinacridones, quinaphthalenes, perinones, perylenes.
  • Suitable dyes are, for. As acridines, azo dyes, phthalocyanines, xanthenes and phenazines.
  • the dyes may be cationic, anionic and nonionic dyes.
  • Suitable inorganic colorants are, for. Example, colored oxide and oxide hydroxide pigments, oxide mixed phase pigments, sulfide and sulfide selenium pigments, carbonate pigments, chromate, chromate-molybdate mixed phase pigments, complex salt pigments and silicate pigments.
  • the colorant may also be a mixture of two or more substances.
  • the laser light-absorbing substances suitable for the marking are preferably based on anthracene, pentaerythritol, copper hydroxide phosphates, molybdenum disulfide, antimony (III) oxide and bismuth oxychloride, platelet-shaped, in particular transparent or semitransparent substrates of, for example, phyllosilicates, such as synthetic or natural mica, talc, kaolin, glass slides, SiO 2 platelets or synthetic carrier-free platelets.
  • platelet-shaped metal oxides such. For example, platy iron oxide, alumina, titanium dioxide, silicon dioxide, LCP's (liquid crystal polymers), holographic pigments, conductive pigments or coated graphite platelets into consideration.
  • metal platelets which are uncoated or else with one or more metal oxide layers can be covered; preferred are z.
  • B. Al, Fe or steel plates are used uncoated, they are preferably coated with a protective polymer layer.
  • Particularly preferred substrates are mica flakes coated with one or more metal oxides.
  • both colorless high-index metal oxides in particular titanium dioxide, antimony (III) oxide, zinc oxide, tin oxide and / or zirconium dioxide are used as metal oxides, as well as colored metal oxides such as chromium oxide, nickel oxide, copper oxide, cobalt oxide and in particular iron oxide (Fe 2 O 3 , Fe 3 O 4 ).
  • the absorber material used is antimony (III) oxide alone or in combination with tin oxide.
  • Coated SiO 2 platelets are z. B. known from WO 93/08237 (wet-chemical coating) and DE-OS 196 14 637 (CVD method).
  • Multilayered pigments based on phyllosilicates are known, for example, from German published patent applications DE 196 18 569, DE 196 38 708, DE 197 07 806 and DE 198 03 550. Particularly suitable are multilayer pigments which have the following structure: Mica + TiO 2 + SiO 2 + TiO 2 Mica + TiO 2 + SiO 2 + TiO 2 / Fe 2 O 3 Mica + TiO 2 + SiO 2 + (Sn, Sb) O 2 SiO 2 platelets + TiO 2 + SiO 2 + TiO 2
  • laser light absorbing substances are anthracene, pentaerythritol, copper hydroxide phosphates, molybdenum disulfide, antimony (III) oxide and bismuth oxychloride.
  • the laser light absorbing substance may also be a mixture of two or more components.
  • thermoplastics as well as duraplast, as e.g. in Ullmann, Vol. 15, p. 457 et seq., Verlag VCH, can be permanently and abrasion-resistant by means of a laser according to the method of the invention.
  • plastics are polyethylene, polypropylene, polyamides, polyesters, polyester esters, polyether esters, polyphenylene ethers, polyacetal, polybutylene terephthalate, polymethyl methacrylate, polyvinyl acetal, polystyrene, acrylonitrile-butadiene-styrene (ABS), acrylonitrile-styrene-acrylate (ASA), polycarbonate, Polyethersulfone and polyether ketones and their copolymers and / or mixture.
  • Particularly suitable powder coatings are based on polyesters, epoxy resins, polyester epoxy resins (mixed powder), polyurethanes, acrylates, fluidized bed sponges (polyamide-based).
  • carrier substances of the colorant / absorber component can be added. These significantly improve the entry into the surface of the plastic or powder coating, but do not remain as an ingredient in the marking.
  • Suitable carriers are for. As mineral oils, waxes, paraffins and nitrocellulose paints.
  • the proportion of carrier substance relative to the colorant / absorber component is 0.1 to 99.9% by weight, preferably 10 to 90% by weight, in particular 25 to 75% by weight.
  • the colored marking of the plastics and powder coatings is even more contrast when the plastic or paint system to be inscribed is additionally doped with one or more laser light absorbing substances. The entry of the colorant in the surface of the system to be marked is then significantly improved.
  • the dopant in the plastic or in the paint can be the same or different with the laser light absorbing substance of the colorant / absorber component.
  • Suitable laser-absorbing substances in the plastic or lacquer are in particular platelet-shaped transparent or semitransparent substrates which are coated with one or more colored or colorless metal oxides. Particular preference is given to dopants based on mica substrates. These platelet-shaped pigments are known and commercially available under the trade name Iriodin® LS from Merck KGaA.
  • the marking of the plastics and powder coatings is simple and easy to handle.
  • the colored marking is predominantly in the plastic or powder coating matrix, ie not by melting a further plastic or paint component.
  • the colorant / absorber component can be applied directly to the plastic or paint to be inscribed.
  • the colorant / absorber component is applied to the surface of the system to be marked by conventional techniques such as brushing, brushing, printing, spraying, squeegeeing.
  • the layer thickness is usually 0.1 to 10,000 nm, preferably 10 to 5000 nm, in particular 50 to 3000 nm.
  • the entry in the plastic surface is made directly by the focused on the plastic or paint surface laser beam.
  • / absorber combinations can lasers are used at different wavelengths depending on the used coloring agent, but preferably CO 2 laser at a wavelength of 10.6 microns and Nd: YAG laser at 1064 nm Lastly. simply wipe off the surface of the marked system from the unused colorant / absorber component.
  • the inscription with the laser takes place in such a way that the specimen is brought into the beam path of a pulsed laser, preferably a CO 2 or Nd: YAG laser. Furthermore, an inscription with an excimer laser, for example via a mask technique, is possible. However, even with other conventional types of lasers having a wavelength in a high absorption region of the laser light absorbing substance used, the desired results are to be obtained.
  • the mark obtained is determined by the irradiation time (or pulse number in pulse lasers) and the irradiation power of the laser and the plastic system or paint system used. The power of the laser used depends on the particular application and can be determined in individual cases by the skilled person readily.
  • the laser used generally has a wavelength in the range of 157 nm to 10.6 ⁇ m, preferably in the range of 532 nm to 10.6 ⁇ m.
  • a wavelength in the range of 157 nm to 10.6 ⁇ m, preferably in the range of 532 nm to 10.6 ⁇ m.
  • CO 2 lasers (10.6 ⁇ m) and Nd: YAG lasers (1064 or 532 nm) or pulsed UV lasers.
  • the excimer lasers have the following wavelengths: F 2 excimer laser (157 nm), ArF excimer laser (193 nm), KrCl excimer laser (222 nm), KrF excimer laser (248 nm), XeCl excimer laser (308 nm), XeF excimer laser (351 nm), frequency-multiplied Nd: YAG lasers with wavelengths of 355 nm (frequency tripled) or 265 nm (frequency-quadrupled). Particular preference is given to using Nd: YAG lasers (1064 or 532 nm) and CO 2 lasers.
  • the energy densities of the lasers used are generally in the range from 0.3 mJ / cm 2 to 50 J / cm 2 , preferably 0.3 mJ / cm 2 to 10 J / cm 2 .
  • the pulse frequency is generally in the range of 1 to 30 kHz.
  • Corresponding lasers which can be used in the process according to the invention are commercially available.
  • the use of the method according to the invention can be carried out in all fields where hitherto customary printing processes for the inscription of plastics are used.
  • moldings of the invention can be used in the electrical, electronics and automotive industries.
  • the marking and labeling of e.g. Cables, lines, moldings or functional parts in the heating, ventilation and cooling area or switches, plugs, levers and handles can be marked according to the inventive method even in hard to reach places with the help of laser light.
  • the method according to the invention can be used in packaging in the food sector or in the toy sector.
  • the markings on the packaging are characterized in that they are wipe and scratch resistant, stable in subsequent sterilization processes, and hygienically pure in the marking process can be applied.
  • paints and powder coatings mentioned can be used in the identification of functional parts in the automotive and industrial sectors, in the electrical sector and in levers, handles, tools, metal plates, pipes, ceramic tiles, packaging, connectors, grids, building parts.
  • Injection molded bodies are produced from a thermoplastic polypropylene (type: PPH 10 from DSM, Geelen) which comprises 1% titanium dioxide (Kronos, Kronos) and 0.2% Iriodin® LS 825 (coated with (Sn, Sb) O 2 Mica from Merck KGaA, Darmstadt).
  • a thermoplastic polypropylene type: PPH 10 from DSM, Geelen
  • Ti dioxide Kronos, Kronos
  • Iriodin® LS 825 coated with (Sn, Sb) O 2 Mica from Merck KGaA, Darmstadt.
  • the additives are added in the form of polypropylene concentrates before the injection process.
  • the injection molded bodies show a white body color under daylight.
  • a mixture of a blue color pigment (PV Echtblau, Fa. Clariant) and a tin-antimony mixed oxide (Zelec ECP-3010-XC, Dupont Chemicals) at a mixing ratio of 2 is applied to the surface of the injection-molded body. 8 applied.
  • the mixture is mixed in the ratio 1: 1 with a mineral oil (Energol WM6 from BP Schmierstoff GmbH).
  • the uniform color coat of colorant and laser absorber obtained after spraying is introduced into the surface with a commercially available Nd: YAG laser (type Starkmark, Fa. Baasel Lasertechnik). Thereafter, the surface is removed by simply wiping the unregistered color layer. What remains are blue, high-contrast inscriptions, which are characterized by a high surface quality and a very good abrasion resistance.
  • Example 7 Analogously to Example 1, but with a red color pigment (PV Echtrot, Fa. Clariant) and a tin-antimony mixed oxide (Zelec ECP-3010-XC, Dupont Chemicals), wherein the mixing ratio is 3: 7. It shows red, high-contrast labels, which are characterized by a high surface quality and a very good abrasion resistance.
  • Example 2 Analogously to Example 2, but with a yellow color pigment (PV Echtgelb, Fa. Clariant) and a tin-antimony mixed oxide (Zelec ECP-3010-XC, Fa. Dupont Chemicals), wherein the mixing ratio is 1: 9. It shows yellow, high-contrast labels, which are characterized by a high surface quality and a very good abrasion resistance.
  • a yellow color pigment PV Echtgelb, Fa. Clariant
  • Zelec ECP-3010-XC Fa. Dupont Chemicals
  • Injection molded bodies are produced from a thermoplastic polyamide (type Schulamid, Messrs. Schulmann) which contain 0.8% Iriodin® LS 835 (mica coated with Fe 3 O 4 from Merck KGaA, Darmstadt). The additives are added in the form of concentrates in polyamide before the injection process.
  • the injection molded bodies show a black body color under daylight.
  • the laser marking is carried out analogously to Example 1. This gives a blue, high-contrast lettering, which is characterized by a high surface quality and a very good abrasion resistance.
  • Metal bodies are powder-coated with a powder coating based on polyester, the powder coating containing 2% Iriodin® LS 820 (Merck KGaA).
  • the laser marking is carried out analogously to Example 1. This gives blue, high-contrast markings, which are characterized by a high surface quality and a very good abrasion resistance.

Landscapes

  • Physics & Mathematics (AREA)
  • Optics & Photonics (AREA)
  • Thermal Transfer Or Thermal Recording In General (AREA)
  • Paints Or Removers (AREA)
  • Compositions Of Macromolecular Compounds (AREA)
  • Application Of Or Painting With Fluid Materials (AREA)
  • Laminated Bodies (AREA)
  • Dot-Matrix Printers And Others (AREA)
  • Laser Beam Printer (AREA)
  • Laser Beam Processing (AREA)
  • Inks, Pencil-Leads, Or Crayons (AREA)

Abstract

Surprisingly, it has been found that colored recordings or inscriptions can be made on laser markable synthetic plastic and paints when their surfaces are coated with a mixture of colorants and absorbing substances, which are partially drawn into or cover the surface. The colorant in combination with the laser light absorbing substance is drawn into the synthetic plastic or paint surface melted by laser radiation, and the inscriptions have high abrasion resistance. Independent claims are included for: (1) A process for colored inscription and colored marking of synthetic plastics and paints, in which the synthetic plastics or paint surfaces are coated with a mixture of one or more laser light absorbing substances, and this layer is partially or over the whole surface transferred partially or completely into the synthetic plastic or paint; (2) a shaped body in synthetic plastic, paint or powdered paint inscribed or marked by the process.

Description

Die vorliegende Erfindung betrifft die farbige Beschriftung oder Markierung von Kunststoffen, Lacken, inklusive Pulverlacken, wobei ein Farbmittel mit Hilfe einer laserlichtabsorbierenden Substanz durch Laserstrahlung in den Kunststoff oder Lack transferiert wird.The present invention relates to the colored labeling or marking of plastics, paints, including powder coatings, wherein a colorant is transferred by means of a laser light absorbing substance by laser radiation in the plastic or paint.

Die Kennzeichnung von Produktionsgütern wird in fast allen Industriezweigen zunehmend wichtiger. So müssen häufig z. B. Produktionsdaten, Verfallsdaten, Barcodes, Firmenlogos, Seriennummern, etc. auf Produkte aufgebracht werden. Derzeit werden diese Markierungen überwiegend mit konventionellen Techniken wie Drucken, Prägen, Stempeln und Etikettieren ausgeführt. Mit Hilfe eines Laserstrahls können insbesondere im Infrarotbereich Beschriftungen auf Glas, Metall und Keramik aufgebracht werden. Hierbei werden die Materialien aus denen die spätere Beschriftung besteht auf der Oberfläche aufgeschmolzen. Für die Beschriftung von Kunststoffen ist dieses Verfahren hingegen nicht geeignet. Wachsende Bedeutung gewinnt die dunkle Markierung mit Lasern 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 abriebbeständig.The labeling of manufactured goods is becoming increasingly important in almost all industries. So z. As production data, expiration dates, barcodes, company logos, serial numbers, etc. are applied to products. Currently, these markings are predominantly carried out by conventional techniques such as printing, embossing, stamping and labeling. With the help of a laser beam inscriptions on glass, metal and ceramic can be applied especially in the infrared range. Here, the materials from which the later inscription is melted on the surface. For the labeling of plastics, however, this method is not suitable. The dark marking with lasers in plastics is gaining increasing importance. With this technique it is possible to use graphic labels, such as e.g. Barcodes can also be applied to a non-planar surface at high speed. Since the inscription is located in the plastic body itself, it is permanently resistant to abrasion.

Neben der dunklen Markierung von Kunststoffen steigt zunehmend das Interesse nach farbigen Markierungen.In addition to the dark marking of plastics, there is an increasing interest in colored markings.

Absorbermaterialien für die farbige Markierung von Kunststoffen sind bekannt. Eine farbige Lasermarkierung eines dunklen Kunststoffes wird in der EP 0 522 370 A1 offenbart. So beschreibt die EP 0 684 144 B1 einen Dotierstoff für die farbige Markierung von Kunststoffmaterialien, der sich dadurch auszeichnet, dass er eine Mischung eines Trübungsmittels und einer chromogenen Substanz enthält.Absorber materials for the colored marking of plastics are known. A colored laser marking of a dark plastic is disclosed in EP 0 522 370 A1. Thus, EP 0 684 144 B1 describes a dopant for the colored marking of plastic materials, which is characterized in that it contains a mixture of a clouding agent and a chromogenic substance.

Die aus dem Stand der Technik bekannten Verfahren für die farbige Beschriftung von Kunststoffen besitzen aber den Nachteil, dass sie eine farbige Markierung auf Kunststoffen mit hellen Einfärbungen nicht ermöglichen bzw. mehrere Laser mit verschiedenen Wellenlängen zur farbigen Beschriftung des Kunststoffs benötigt werden.However, the known from the prior art process for the colored inscription of plastics have the disadvantage that they do not allow a colored marking on plastics with bright colorations or more lasers are required with different wavelengths for colored inscription of the plastic.

Aufgabe der vorliegenden Erfindung war es daher ein Verfahren zu finden, welches unter Einwirkung von Laserlicht eine farbige Markierung mit hohem Kontrast auf jeder Kunststofffarbe unter Verwendung nur eines Lasers bzw. Laserwellenlänge ermöglicht.The object of the present invention was therefore to find a method which, under the action of laser light, permits a colored marking with high contrast on each plastic ink using only one laser or laser wavelength.

Überraschenderweise wurde gefunden, dass man Kunststoffe und Lacke farbig beschriften kann, wenn man die Oberfläche eines lasermarkierbaren Kunststoff oder Lacks mit einem Gemisch aus Farbmittel und Absorbersubstanz belegt und diese teilweise oder flächendeckend in die Oberfläche einträgt. Das Farbmittel wird in Kombination mit der laserlichtabsorbierenden Substanz in die durch Laserbestrahlung aufgeschmolzene Kunststoff- oder Lackoberfläche eingetragen. Durch den Eintrag in die Oberfläche des Kunststoffs oder Lacks lassen sich farbige Beschriftungen mit sehr hoher Abriebfestigkeit erzielen.Surprisingly, it has been found that it is possible to label plastics and lacquers in color if the surface of a laser-markable plastic or lacquer is coated with a mixture of colorant and absorber substance and these are introduced partially or completely into the surface. The colorant is added in combination with the laser light absorbing substance in the melted by laser irradiation plastic or paint surface. By entering the surface of the plastic or paint, colored inscriptions with very high abrasion resistance can be achieved.

Gegenstand der Erfindung sind ein Verfahren zur farbigen Beschriftung und Markierung von Hunststoffen oder Lacken, gemäß Anspruch 1 und ein Formkörper gemäß Anspruch 9.The invention relates to a method for colored labeling and marking of Hunststoffen or paints, according to claim 1 and a shaped article according to claim 9.

Gute Markierungsergebnisse werden erzielt, wenn das Verhältnis Farbmittel / laserlichtabsorbierende Substanz 10 : 1 bis 1 : 10, vorzugsweise 95 : 5 bis 70 : 30, insbesondere 90 : 10 bis 80 : 20, beträgt.Good marking results are achieved when the ratio colorant / laser light absorbing substance is 10: 1 to 1:10, preferably 95: 5 to 70: 30, especially 90: 10 to 80: 20.

Die Konzentration des Farbmittels und der laserlichtabsorbierenden Substanz auf der Oberfläche des Kunststoffs bzw. des Lacks ist allerdings abhängig von dem eingesetzten Kunststoffsystem bzw. der Lackzusammensetzung und der Fläche der Beschriftung.The concentration of the colorant and the laser light absorbing substance on the surface of the plastic or the paint, however, depends on the plastic system used or the paint composition and the surface of the label.

Für die Beschriftung kommen sowohl organische als auch anorganische Farbmittel in Frage. Geeignet sind alle dem Fachmann bekannten Farbmittel, die sich bei der Laserbestrahlung nicht zersetzen.For the labeling both organic and inorganic colorants come into question. Suitable are all known to the expert colorants that do not decompose in the laser irradiation.

Geeignete organische Farbmittel sind vorzugsweise solche ausgewählt aus der Gruppe der nachfolgend genannten organischen Pigmente: Kupferphthalocyanine, Dioxazine, Anthrachinone, Monoazo- und Diazopigmente, Diketopyrolopyrrol, polycyclische Pigmente, Anthrapyrimidine, Chinacridone, Chinaphtalone, Perinone, Perylene.Suitable organic colorants are preferably those selected from the group of the following organic pigments: copper phthalocyanines, dioxazines, anthraquinones, monoazo and diazo pigments, diketopyrolopyrrole, polycyclic pigments, anthrapyrimidines, quinacridones, quinaphthalenes, perinones, perylenes.

Geeignete Farbstoffe sind z. B. Acridine, Azofarbstoffe, Phthalocyanine, Xanthene und Phenazine. Bei den Farbstoffen kann es sich um kationische, anionische und nichtionische Farbstoffe handeln.Suitable dyes are, for. As acridines, azo dyes, phthalocyanines, xanthenes and phenazines. The dyes may be cationic, anionic and nonionic dyes.

Geeignete anorganische Farbmittel sind z. B. farbige Oxid- und Oxidhydroxidpigmente, Oxid-Mischphasenpigmente, Sulfid- und Sulfid-Selenpigmente, Carbonatpigmente, Chromat-, Chromat-Molybdat-Mischphasenpigmente, Komplexsalzpigmente und Silikatpigmente.Suitable inorganic colorants are, for. Example, colored oxide and oxide hydroxide pigments, oxide mixed phase pigments, sulfide and sulfide selenium pigments, carbonate pigments, chromate, chromate-molybdate mixed phase pigments, complex salt pigments and silicate pigments.

Bei dem Farbmittel kann es sich auch um ein Gemisch aus zwei oder mehr Substanzen handeln.The colorant may also be a mixture of two or more substances.

Die für die Markierung geeigneten laserlichtabsorbierenden Substanzen basieren vorzugsweise auf Antracen, Pentaerythrit, Kupferhydroxidphosphate, Molybdändisulfid, Antimon(III)oxid und Wismuthoxychlorid, plättchenförmigen, insbesondere transparenten oder semitransparenten Substraten aus z.B. Schichtsilikaten, wie etwa synthetischer oder natürlicher Glimmer, Talkum, Kaolin, Glasplättchen, SiO2-Plättchen oder synthetischen trägerfreien Plättchen. Weiterhin kommen auch plättchenförmige Metalloxide wie z. B. plättchenförmiges Eisenoxid, Aluminiumoxid, Titandioxid, Siliziumdioxid, LCP's (Liquid Crystal Polymers), holographische Pigmente, leitfähige Pigmente oder beschichtete Graphitplättchen in Betracht.The laser light-absorbing substances suitable for the marking are preferably based on anthracene, pentaerythritol, copper hydroxide phosphates, molybdenum disulfide, antimony (III) oxide and bismuth oxychloride, platelet-shaped, in particular transparent or semitransparent substrates of, for example, phyllosilicates, such as synthetic or natural mica, talc, kaolin, glass slides, SiO 2 platelets or synthetic carrier-free platelets. Furthermore, platelet-shaped metal oxides such. For example, platy iron oxide, alumina, titanium dioxide, silicon dioxide, LCP's (liquid crystal polymers), holographic pigments, conductive pigments or coated graphite platelets into consideration.

Als plättchenförmige Pigmente können auch Metallplättchen eingesetzt werden, die unbeschichtet oder auch mit einer oder mehreren Metalloxidschichten bedeckt sein können; bevorzugt sind z. B. Al-, Cr-, Fe-, Au-, Ag-und Stahlplättchen. Sollten korrosionsanfällige Metallplättchen wie z. B. Al-, Fe- oder Stahlplättchen unbeschichtet eingesetzt werden, werden sie vorzugsweise mit einer schützenden Polymerschicht überzogen.As platelet-shaped pigments it is also possible to use metal platelets which are uncoated or else with one or more metal oxide layers can be covered; preferred are z. B. Al, Cr, Fe, Au, Ag and steel flakes. Should corrosion-prone metal flakes such. B. Al, Fe or steel plates are used uncoated, they are preferably coated with a protective polymer layer.

Besonders bevorzugte Substrate sind mit ein oder mehreren Metalloxiden beschichtete Glimmerschuppen. Als Metalloxide werden dabei sowohl farblose hochbrechende Metalloxide, wie insbesondere Titandioxid, Antimon(III)oxid, Zinkoxid, Zinnoxid und/oder Zirkoniumdioxid verwendet als auch farbige Metalloxide wie z.B. Chromoxid, Nickeloxid, Kupferoxid, Kobaltoxid und insbesondere Eisenoxid (Fe2O3, Fe3O4). Insbesondere bevorzugt wird als Absorbermaterial Antimon(III)oxid allein oder in Kombination mit Zinnoxid verwendet.Particularly preferred substrates are mica flakes coated with one or more metal oxides. In this case, both colorless high-index metal oxides, in particular titanium dioxide, antimony (III) oxide, zinc oxide, tin oxide and / or zirconium dioxide are used as metal oxides, as well as colored metal oxides such as chromium oxide, nickel oxide, copper oxide, cobalt oxide and in particular iron oxide (Fe 2 O 3 , Fe 3 O 4 ). Particularly preferably, the absorber material used is antimony (III) oxide alone or in combination with tin oxide.

Diese Substrate sind bekannt und größtenteils kommerziell erhältlich, z. B. unter der Marke Iriodin® LS der Fa. Merck KGaA, und/oder können nach dem Fachmann bekannten Standardverfahren hergestellt werden. Pigmente auf der Basis transparenter oder semitransparenter plättchenförmiger Substrate werden z. B. beschrieben in den deutschen Patenten und Patentanmeldungen 14 67 468, 19 59 998, 20 09 566, 22 14 454, 22 15 191, 22 44 298, 23 13 331, 25 22 572, 31 37 808, 31 37 809, 31 51 343, 31 51 354, 31 51 355, 32 11 602, 32 35 017, 38 42 330, 44 41 223.These substrates are known and mostly commercially available, for. B. under the trade name Iriodin® LS Fa. Merck KGaA, and / or can be prepared by standard methods known in the art. Pigments based on transparent or semi-transparent platelet-shaped substrates are e.g. As described in German patents and patent applications 14 67 468, 19 59 998, 20 09 566, 22 14 454, 22 15 191, 22 44 298, 23 13 331, 25 22 572, 31 37 808, 31 37 809, 31st 51 343, 31 51 354, 31 51 355, 32 11 602, 32 35 017, 38 42 330, 44 41 223.

Beschichtete SiO2-Plättchen sind z. B. bekannt aus der WO 93/08237 (nasschemische Beschichtung) und der DE-OS 196 14 637 (CVD-Verfahren).Coated SiO 2 platelets are z. B. known from WO 93/08237 (wet-chemical coating) and DE-OS 196 14 637 (CVD method).

Mehrschichtpigmente basierend auf Schichtsilikaten sind beispielsweise aus den deutschen Offenlegungsschriften DE 196 18 569, DE 196 38 708, DE 197 07 806 und DE 198 03 550 bekannt. Besonders geeignet sind Mehrschichtpigmente, die folgenden Aufbau besitzen:

        Glimmer + TiO2 + SiO2 + TiO2

        Glimmer + TiO2 + SiO2 + TiO2/Fe2O3

        Glimmer + TiO2 + SiO2 + (Sn, Sb)O2

        SiO2-Plättchen + TiO2 + SiO2 + TiO2
Multilayered pigments based on phyllosilicates are known, for example, from German published patent applications DE 196 18 569, DE 196 38 708, DE 197 07 806 and DE 198 03 550. Particularly suitable are multilayer pigments which have the following structure:

Mica + TiO 2 + SiO 2 + TiO 2

Mica + TiO 2 + SiO 2 + TiO 2 / Fe 2 O 3

Mica + TiO 2 + SiO 2 + (Sn, Sb) O 2

SiO 2 platelets + TiO 2 + SiO 2 + TiO 2

Besonders bevorzugte laserlichtabsorbierende Substanzen sind Anthracen, Pentaeerythrit, Kupferhydroxidphosphate, Molybdändisulfid, Antimon(III)oxid und Wismuthoxychlorid.Particularly preferred laser light absorbing substances are anthracene, pentaerythritol, copper hydroxide phosphates, molybdenum disulfide, antimony (III) oxide and bismuth oxychloride.

Die laserlichtabsorbierende Substanz kann auch ein Gemisch aus zwei oder mehr Komponenten sein.The laser light absorbing substance may also be a mixture of two or more components.

Alle bekannten Thermoplaste sowie Duraplast, wie sie z.B. im Ullmann, Bd. 15, S. 457 ff., Verlag VCH beschrieben werden, können nach dem erfindungsgemäßen Verfahren dauerhaft und abriebfest mittels eines Lasers beschriftet werden. Geeignete Kunststoffe sind insbesondere Polyethylen, Polypropylen, Polyamide, Polyester, Polyesterester, Polyetherester, Polyphenylenether, Polyacetal, Polybutylenterephthalat, Poly-methylmethacrylat, Polyvinylacetal, Polystyrol, Acrylnitril-Butadien-Styrol (ABS), Acrylnitril-Styrol-Acrylester (ASA), Polycarbonat, Polyethersulfone und Polyetherketone sowie deren Copolymeren und/oder Mischung.All known thermoplastics as well as duraplast, as e.g. in Ullmann, Vol. 15, p. 457 et seq., Verlag VCH, can be permanently and abrasion-resistant by means of a laser according to the method of the invention. Particularly suitable plastics are polyethylene, polypropylene, polyamides, polyesters, polyester esters, polyether esters, polyphenylene ethers, polyacetal, polybutylene terephthalate, polymethyl methacrylate, polyvinyl acetal, polystyrene, acrylonitrile-butadiene-styrene (ABS), acrylonitrile-styrene-acrylate (ASA), polycarbonate, Polyethersulfone and polyether ketones and their copolymers and / or mixture.

Unter Lacke werden alle dem Fachmann bekannten Lacke verstanden, wie z. B. Autolacke, Industrielacke, Reparaturlacke, Pulverlacke.Under paints are all known in the art paints understood, such. As car paints, industrial coatings, refinish, powder coatings.

Besonders geeignete Pulverlacke sind auf Basis von Polyester, Epoxidharzen, Polyesterepoxidharzen (Mischpulver), Polyurethanen, Acrylaten, Wirbelsinterpulvern (Polyamidbasis).Particularly suitable powder coatings are based on polyesters, epoxy resins, polyester epoxy resins (mixed powder), polyurethanes, acrylates, fluidized bed sponges (polyamide-based).

Zur Verbesserung des Farbeintrages in die Matrix des Kunststoffs oder des Pulverlacks können sogenannte Trägersubstanzen der Farbmittel-/Absorber-Komponente zugegeben werden. Diese verbessern deutlich den Eintrag in die Oberfläche des Kunststoffes bzw. Pulverlacks, bleiben jedoch nicht als Bestandteil in der Markierung erhalten.To improve the color input in the matrix of the plastic or powder coating so-called carrier substances of the colorant / absorber component can be added. These significantly improve the entry into the surface of the plastic or powder coating, but do not remain as an ingredient in the marking.

Geeignete Träger sind z. B. mineralische Öle, Wachse, Paraffine und Nitrocelluloselacke.Suitable carriers are for. As mineral oils, waxes, paraffins and nitrocellulose paints.

Der Anteil an Trägersubstanz bezogen auf die Farbmittel/Absorber-Komponente beträgt 0,1 bis 99,9 Gew. %, vorzugsweise 10 bis 90 Gew. %, insbesondere 25 bis 75 Gew. %.The proportion of carrier substance relative to the colorant / absorber component is 0.1 to 99.9% by weight, preferably 10 to 90% by weight, in particular 25 to 75% by weight.

In einer besonderen Ausführungsform wird die farbige Markierung der Kunststoffe und Pulverlacke noch kontrastreicher, wenn das zu beschriftende Kunststoff- bzw. Lacksystem zusätzlich mit einer oder mehreren laserlichtabsorbierenden Substanzen dotiert ist. Der Eintrag des Farbmittels in die Oberfläche des zu markierenden Systems wird dann deutlich verbessert.In a particular embodiment, the colored marking of the plastics and powder coatings is even more contrast when the plastic or paint system to be inscribed is additionally doped with one or more laser light absorbing substances. The entry of the colorant in the surface of the system to be marked is then significantly improved.

Der Dotierstoff im Kunststoff bzw. im Lack kann mit der laserlichtabsorbierenden Substanz der Farbmittel/Absorber-Komponente gleich oder verschieden sein. Geeignete laserabsorbierende Substanzen im Kunststoff oder Lack sind insbesondere plättchenförmige transparente oder semitransparente Substrate, die mit ein oder mehreren farbigen oder farblosen Metalloxiden belegt sind. Besonders bevorzugt sind Dotierstoffe auf Basis von Glimmersubstraten. Diese plättchenförmigen Pigmente sind bekannt und kommerziell erhältlich unter der Marke Iriodin® LS der Firma Merck KGaA.The dopant in the plastic or in the paint can be the same or different with the laser light absorbing substance of the colorant / absorber component. Suitable laser-absorbing substances in the plastic or lacquer are in particular platelet-shaped transparent or semitransparent substrates which are coated with one or more colored or colorless metal oxides. Particular preference is given to dopants based on mica substrates. These platelet-shaped pigments are known and commercially available under the trade name Iriodin® LS from Merck KGaA.

Die Markierung der Kunststoffe und Pulverlacke ist einfach und leicht zu handhaben. Die farbige Markierung erfolgt überwiegend in der Kunststoff- bzw. Pulverlackmatrix, d. h. nicht durch Aufschmelzen einer weiteren Kunststoff- oder Lackkomponente. Zur Applikation kann die Farbmittel-/Absorber-Komponente direkt auf den zu beschriftenden Kunststoff oder Lack aufgetragen werden. Die Farbmittel/Absorber-Komponente wird auf die Oberfläche des zu markierenden Systems durch übliche Techniken, wie pinseln, bürsten, drucken, sprühen, rakeln, aufgetragen. Die Schichtdicke beträgt in der Regel 0,1 bis 10000 nm, vorzugsweise 10 bis 5000 nm, insbesondere 50 bis 3000 nm. Der Eintrag in die Kunststoffoberfläche erfolgt direkt durch den auf die Kunststoff- bzw. Lackoberfläche fokussierten Laserstrahl. Hierbei können in Abhängigkeit von den eingesetzten Farbmittel/Absorber-Kombinationen Laser mit verschiedenen Wellenlängen eingesetzt werden, bevorzugt jedoch CO2-Laser bei einer Wellenlänge von 10,6 µm, sowie Nd: YAG Laser bei 1064 nm. Zuletzt wird durch einfaches Abwischen die Oberfläche des markierten Systems von der nicht verbrauchten Farbmittel/Absorber-Komponente befreit.The marking of the plastics and powder coatings is simple and easy to handle. The colored marking is predominantly in the plastic or powder coating matrix, ie not by melting a further plastic or paint component. For application, the colorant / absorber component can be applied directly to the plastic or paint to be inscribed. The colorant / absorber component is applied to the surface of the system to be marked by conventional techniques such as brushing, brushing, printing, spraying, squeegeeing. The layer thickness is usually 0.1 to 10,000 nm, preferably 10 to 5000 nm, in particular 50 to 3000 nm. The entry in the plastic surface is made directly by the focused on the plastic or paint surface laser beam. Here, / absorber combinations can lasers are used at different wavelengths depending on the used coloring agent, but preferably CO 2 laser at a wavelength of 10.6 microns and Nd: YAG laser at 1064 nm Lastly. simply wipe off the surface of the marked system from the unused colorant / absorber component.

Die Beschriftung mit dem Laser erfolgt derart, daß der Probenkörper in den Strahlengang eines gepulsten Lasers, vorzugsweise eines CO2- oder Nd:YAG-Lasers gebracht wird. Ferner ist eine Beschriftung mit einem Excimer-Laser, z.B. über eine Maskentechnik, möglich. Jedoch sind auch mit anderen herkömmlichen Lasertypen, die eine Wellenlänge in einem Bereich hoher Absorption der verwendeten laserlichtabsorbierenden Substanz aufweisen, die gewünschten Ergebnisse zu erzielen. Die erhaltene Markierung wird durch die Bestrahlungszeit (bzw. Pulszahl bei Pulslasern) und Bestrahlungsleistung des Lasers sowie des verwendeten Kunststoffsystems bzw. Lacksystems bestimmt. Die Leistung der verwendeten Laser hängt von der jeweiligen Anwendung ab und kann im Einzelfall vom Fachmann ohne weiteres ermittelt werden.The inscription with the laser takes place in such a way that the specimen is brought into the beam path of a pulsed laser, preferably a CO 2 or Nd: YAG laser. Furthermore, an inscription with an excimer laser, for example via a mask technique, is possible. However, even with other conventional types of lasers having a wavelength in a high absorption region of the laser light absorbing substance used, the desired results are to be obtained. The mark obtained is determined by the irradiation time (or pulse number in pulse lasers) and the irradiation power of the laser and the plastic system or paint system used. The power of the laser used depends on the particular application and can be determined in individual cases by the skilled person readily.

Der verwendete Laser hat im allgemeinen eine Wellenlänge im Bereich von 157 nm bis 10,6 µm, vorzugsweise im Bereich von 532 nm bis 10,6 µm. Beispielsweise seien hier CO2-Laser (10,6 µm) und Nd:YAG-Laser (1064 bzw. 532 nm) oder gepulste UV-Laser erwähnt. Die Excimerlaser weisen folgende Wellenlängen auf: F2-Excimerlaser (157 nm), ArF-Excimerlaser (193 nm), KrCl-Excimerlaser (222 nm), KrF-Excimerlaser (248 nm), XeCl-Excimer-laser (308 nm), XeF-Excimerlaser (351 nm), frequenzvervielfachte Nd:YAG-Laser mit Wellenlängen von 355 nm (frequenzverdreifacht) oder 265 nm (frequenzvervierfacht). Besonders bevorzugt werden Nd:YAG-Laser (1064 bzw. 532 nm) und CO2-Laser eingesetzt. Die Energiedichten der eingesetzten Laser liegen im allgemeinen im Bereich von 0,3 mJ/cm2 bis 50 J/cm2, vorzugsweise 0,3 mJ/cm2 bis 10 J/cm2.The laser used generally has a wavelength in the range of 157 nm to 10.6 μm, preferably in the range of 532 nm to 10.6 μm. For example, mention may be made here of CO 2 lasers (10.6 μm) and Nd: YAG lasers (1064 or 532 nm) or pulsed UV lasers. The excimer lasers have the following wavelengths: F 2 excimer laser (157 nm), ArF excimer laser (193 nm), KrCl excimer laser (222 nm), KrF excimer laser (248 nm), XeCl excimer laser (308 nm), XeF excimer laser (351 nm), frequency-multiplied Nd: YAG lasers with wavelengths of 355 nm (frequency tripled) or 265 nm (frequency-quadrupled). Particular preference is given to using Nd: YAG lasers (1064 or 532 nm) and CO 2 lasers. The energy densities of the lasers used are generally in the range from 0.3 mJ / cm 2 to 50 J / cm 2 , preferably 0.3 mJ / cm 2 to 10 J / cm 2 .

Bei der Verwendung von gepulsten Lasern liegt die Pulsfrequenz im allgemeinen im Bereich von 1 bis 30 kHz. Entsprechende Laser, die im erfindungsgemäßen Verfahren eingesetzt werden können, sind kommerziell erhältlich.When using pulsed lasers, the pulse frequency is generally in the range of 1 to 30 kHz. Corresponding lasers which can be used in the process according to the invention are commercially available.

Die Verwendung des erfindungsgemäßen Verfahren kann auf allen Gebieten erfolgen, wo bisher übliche Druckverfahren zur Beschriftung von Kunststoffen eingesetzt werden. Beispielsweise können erfindungsgemäße Formkörper in der Elektro-, Elektronik- und Kraftfahrzeugindustrie Anwendung finden. Die Kennzeichnung und Beschriftung von z.B. Kabeln, Leitungen, Zierleisten bzw. Funktionsteilen im Heizungs-, Lüftungs- und Kühlbereich oder Schalter, Stecker, Hebel und Griffe, können nach dem erfindungsgemäßen verfahren selbst an schwer zugänglichen Stellen mit Hilfe von Laserlicht markiert werden. Weiterhin kann das erfindungsgemäße verfahren 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, und 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 Kunststoffmarken zur individuellen Kennzeichnung von Tieren, sogenannte Cattle Tags oder Ohrmarken. Über ein Barcodesystem werden die Informationen gespeichert, welche spezifisch dem Tier zugehörig sind. Diese können bei Bedarf wieder mit Hilfe eines Scanners abgerufen werden. Die Beschriftung muß sehr dauerhaft werden, da die Marke teilweise über mehrere Jahre an den Tieren verbleiben.The use of the method according to the invention can be carried out in all fields where hitherto customary printing processes for the inscription of plastics are used. For example, moldings of the invention can be used in the electrical, electronics and automotive industries. The marking and labeling of e.g. Cables, lines, moldings or functional parts in the heating, ventilation and cooling area or switches, plugs, levers and handles can be marked according to the inventive method even in hard to reach places with the help of laser light. Furthermore, the method according to the invention can be used in packaging in the food sector or in the toy sector. The markings on the packaging are characterized in that they are wipe and scratch resistant, stable in subsequent sterilization processes, and hygienically pure in the marking process can be applied. Complete label images can be permanently applied to the packaging for a reusable system. Another important field of application for laser marking are plastic brands for the individual marking of animals, so-called cattle tags or ear tags. A barcode system stores the information that is specific to the animal. These can be recalled when needed with the help of a scanner. The label must be very durable, since the mark sometimes remain on the animals for several years.

Die erwähnten Lacke und Pulverlacke können Anwendung finden bei der Kennzeichnung von Funktionsteilen im Automobil- und Industriebereich, im Elektrobereich sowie bei Hebel, Griffen, Werkzeugen, Metallplatten, Rohren, Keramikplatten, Verpackungen, Stecker, Gitter, Bauträgerteilen.The paints and powder coatings mentioned can be used in the identification of functional parts in the automotive and industrial sectors, in the electrical sector and in levers, handles, tools, metal plates, pipes, ceramic tiles, packaging, connectors, grids, building parts.

Die folgenden Beispiele sollen die Erfindung erläutern ohne sie jedoch zu begrenzen. Die angegebenen Prozentangaben sind Gewichtsprozent.The following examples are intended to illustrate the invention without, however, limiting it. The percentages given are percent by weight.

BeispieleExamples Beispiel 1example 1

Es werden Spritzgusskörper aus einem thermoplastischen Polypropylen (Typ: PPH 10 Fa. DSM, Geelen) hergestellt, die 1 % Titandioxid (Kronos, Fa. Kronos) und 0,2 % Iriodin® LS 825 (mit (Sn, Sb)O2 beschichteter Glimmer der Fa. Merck KGaA, Darmstadt) enthalten.Injection molded bodies are produced from a thermoplastic polypropylene (type: PPH 10 from DSM, Geelen) which comprises 1% titanium dioxide (Kronos, Kronos) and 0.2% Iriodin® LS 825 (coated with (Sn, Sb) O 2 Mica from Merck KGaA, Darmstadt).

Die Zusatzstoffe werden in Form von Polypropylenkonzentraten vor dem Abspritzvorgang hinzugegeben. Die Spritzgusskörper zeigen unter Tageslicht eine weiße Körperfarbe. Mit einer handelsüblichen Airbrushpistole wird auf die Oberfläche der Spritzgusskörper eine Mischung aus einem blauen Farbpigment (PV Echtblau, Fa. Clariant) und eines Zinn-Antimon-Mischoxides (Zelec ECP-3010-XC, Fa. Dupont Chemicals) bei einem Mischverhältnis von 2 : 8 aufgebracht. Zur Anwendung in der Airbrushpistole wird die Mischung im Verhältnis 1 : 1 mit einem mineralischen Öl (Energol WM6 der BP Schmierstoff GmbH) versetzt. Die nach dem Aufsprühen erzielte gleichmäßige Farbschicht aus Farbmittel und Laserabsorber wird mit einem handelsüblichen Nd:YAG Laser (Typ Starkmark, Fa. Baasel Lasertechnik) in die Oberfläche eingetragen. Danach wird die Oberfläche durch einfaches Abwischen von der nicht eingetragenen Farbschicht befreit. Zurück bleiben blaue, kontrastreiche Beschriftungen, welche sich durch eine hohe Oberflächengüte sowie eine sehr gute Abriebfestigkeit auszeichnen.The additives are added in the form of polypropylene concentrates before the injection process. The injection molded bodies show a white body color under daylight. With a commercially available airbrush gun, a mixture of a blue color pigment (PV Echtblau, Fa. Clariant) and a tin-antimony mixed oxide (Zelec ECP-3010-XC, Dupont Chemicals) at a mixing ratio of 2 is applied to the surface of the injection-molded body. 8 applied. For application in the airbrush gun, the mixture is mixed in the ratio 1: 1 with a mineral oil (Energol WM6 from BP Schmierstoff GmbH). The uniform color coat of colorant and laser absorber obtained after spraying is introduced into the surface with a commercially available Nd: YAG laser (type Starkmark, Fa. Baasel Lasertechnik). Thereafter, the surface is removed by simply wiping the unregistered color layer. What remains are blue, high-contrast inscriptions, which are characterized by a high surface quality and a very good abrasion resistance.

Beispiel 2Example 2

Analog Beispiel 1, aber mit einem roten Farbpigment (PV Echtrot, Fa. Clariant) und eines Zinn-Antimon Mischoxides (Zelec ECP-3010-XC, Fa. Dupont Chemicals), wobei das Mischverhältnis 3 : 7 ist. Es zeigen sich rote, kontrastreiche Beschriftungen, welche sich durch eine hohe Oberflächengüte sowie eine sehr gute Abriebfestigkeit auszeichnen.Analogously to Example 1, but with a red color pigment (PV Echtrot, Fa. Clariant) and a tin-antimony mixed oxide (Zelec ECP-3010-XC, Dupont Chemicals), wherein the mixing ratio is 3: 7. It shows red, high-contrast labels, which are characterized by a high surface quality and a very good abrasion resistance.

Beispiel 3Example 3

Analog Beispiel 2, aber mit einem gelben Farbpigment (PV Echtgelb, Fa. Clariant) und eines Zinn-Antimon Mischoxides (Zelec ECP-3010-XC, Fa. Dupont Chemicals), wobei das Mischverhältnis 1 : 9 ist. Es zeigen sich gelbe, kontrastreiche Beschriftungen, welche sich durch eine hohe Oberflächengüte sowie eine sehr gute Abriebfestigkeit auszeichnen.Analogously to Example 2, but with a yellow color pigment (PV Echtgelb, Fa. Clariant) and a tin-antimony mixed oxide (Zelec ECP-3010-XC, Fa. Dupont Chemicals), wherein the mixing ratio is 1: 9. It shows yellow, high-contrast labels, which are characterized by a high surface quality and a very good abrasion resistance.

Beispiel 4Example 4

Es werden Spritzgusskörper aus einem thermoplastischen Polyamid (Typ Schulamid, Fa. Schulmann) hergestellt, die 0,8 % Iriodin® LS 835 (mit Fe3O4 beschichteter Glimmer der Fa. Merck KGaA, Darmstadt) enthalten. Die Zusatzstoffe werden in Form von Konzentraten in Polyamid vor dem Abspritzvorgang hinzugegeben. Die Spritzgusskörper zeigen unter Tageslicht eine schwarze Körperfarbe. Die Lasermarkierung wird analog Beispiel 1 durchgeführt. Man erhält eine blaue, kontrastreiche Beschriftung, die sich durch eine hohe Oberflächengüte sowie eine sehr gute Abriebfestigkeit auszeichnet.Injection molded bodies are produced from a thermoplastic polyamide (type Schulamid, Messrs. Schulmann) which contain 0.8% Iriodin® LS 835 (mica coated with Fe 3 O 4 from Merck KGaA, Darmstadt). The additives are added in the form of concentrates in polyamide before the injection process. The injection molded bodies show a black body color under daylight. The laser marking is carried out analogously to Example 1. This gives a blue, high-contrast lettering, which is characterized by a high surface quality and a very good abrasion resistance.

Beispiel 5Example 5

Es werden Metallkörper mit einem Pulverlack auf Basis Polyester pulverlackiert, wobei der Pulverlack 2% Iriodin® LS 820 (Firma Merck KGaA) enthält. Die Lasermarkierung wird analog Beispiel 1 durchgeführt. Man erhält blaue, kontrastreiche Beschriftungen, welche sich durch eine hohe Oberflächengüte sowie eine sehr gute Abriebfestigkeit auszeichnen.Metal bodies are powder-coated with a powder coating based on polyester, the powder coating containing 2% Iriodin® LS 820 (Merck KGaA). The laser marking is carried out analogously to Example 1. This gives blue, high-contrast markings, which are characterized by a high surface quality and a very good abrasion resistance.

Claims (9)

  1. Process for the coloured inscription and coloured marking of plastics or coatings, characterised in that the surface of the plastic or coating is covered with a mixture consisting of one or more colorants and one or more laser light-absorbing substances, and this layer is transferred completely over part or all of the surface into the plastic or coating surface which has been melted by laser irradiation.
  2. Process according to Claim 1, characterised in that the colorant : laser light-absorbing substance ratio is 10 : 1 to 1 : 10.
  3. Process according to Claim 1 or 2, characterised in that the colorant is a dye and/or an organic or inorganic pigment.
  4. Process according to Claim 3, characterised in that the colorant is selected from the group of the copper phthalocyanines, dioxazines, anthraquinones, monoazo and diazo pigments, diketopyrrolopyrrole, polycyclic pigments, anthrapyrimidines, quinacridones, quinaphthalones, perinones, perylenes, acridines, azo dyes, phthalocyanines, xanthenes and phenazines, coloured oxide and oxyhydroxide pigments, oxide mixed-phase pigments, sulfide and sulfide/selenium pigments, carbonate pigments, chromate and chromate/molybdate mixed-phase pigments, complex-salt pigments and silicate pigments.
  5. Process according to one of Claims 1 to 4, characterised in that the plastic is a thermoplastic or a thermoset.
  6. Process according to Claim 5, characterised in that the plastic consists of polyethylene, polypropylene, polyamide, polyester, polyester-ester, polyether-ester, polyphenylene ether, polyacetal, polybutylene terephthalate, polymethyl methacrylate, polyvinyl acetal, polystyrene, acrylonitrile-butadiene-styrene (ABS), acrylonitrile-styrene-acrylate (ASA), polycarbonate, polyether sulfones and polyether ketones, as well as copolymers and/or mixture thereof.
  7. Process according to one of Claims 1 to 6, characterised in that the plastic or coating itself comprises one or more laser light-absorbing substances.
  8. Process according to one of Claims 1 to 7, characterised in that a CO2 or Nd:YAG laser is used.
  9. Plastic mouldings, coatings and powder coatings provided with a coloured inscription or marking by the process according to one of Claims 1 to 8.
EP02016489A 2001-07-27 2002-07-23 Colour writing or marking of plastics and lacquers Expired - Lifetime EP1279517B1 (en)

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US20040013969A1 (en) 2004-01-22
DE50205815D1 (en) 2006-04-20
US6924077B2 (en) 2005-08-02
JP2003175571A (en) 2003-06-24
DE10136479A1 (en) 2003-02-06
EP1279517A2 (en) 2003-01-29
EP1279517A3 (en) 2003-06-25

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