EP1279517A2 - Colour writing or marking of plastics and lacquers - Google Patents
Colour writing or marking of plastics and lacquers Download PDFInfo
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- EP1279517A2 EP1279517A2 EP02016489A EP02016489A EP1279517A2 EP 1279517 A2 EP1279517 A2 EP 1279517A2 EP 02016489 A EP02016489 A EP 02016489A EP 02016489 A EP02016489 A EP 02016489A EP 1279517 A2 EP1279517 A2 EP 1279517A2
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- Prior art keywords
- plastics
- pigments
- plastic
- marked
- colored
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
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- 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
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- 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 inscription or marking of plastics, lacquers, including powder lacquers, a colorant being transferred into the plastics or lacquer by laser radiation with the aid of a laser light-absorbing substance.
- 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 an opacifying agent and a chromogenic substance.
- plastics and paints can be labeled in color if the surface of a laser-markable plastic or varnish is coated with a mixture of colorant and absorber substance and is partially or fully entered into the surface.
- the colorant in combination with the laser-absorbing substance, is introduced into the plastic or lacquer surface melted by laser radiation. Through the entry in the surface of the plastic or varnish, colored inscriptions with very high abrasion resistance can be achieved.
- the invention relates to plastics and lacquers which can be labeled or marked in color, characterized in that a mixture consisting of one or more colorants and one or more laser-absorbing substances is applied to the plastic or lacquer surface.
- the ratio of colorant / laser light-absorbing substance is 10: 1 to 1:10, preferably 95: 5 to 70:30, in particular 90:10 to 80:20.
- the concentration of the colorant and the laser light-absorbing substance on the surface of the plastic or lacquer depends on the plastic system or lacquer composition used and the area of the lettering.
- Suitable organic colorants are preferably those selected from the group of the organic pigments mentioned below: Copper phthalocyanines, dioxazines, anthraquinones, monoazo and Diazo pigments, diketopyrolopyrrole, polycyclic pigments, anthrapyrimidines, quinacridones, quinaphtalones, perinones, perylenes.
- Suitable dyes are e.g. B. acridines, azo dyes, phthalocyanines, xanthenes and phenazines.
- the dyes can be cationic, anionic and nonionic dyes.
- Suitable inorganic colorants are e.g. B. 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 can also be a mixture of two or more substances.
- the laser-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 made of, for example, layered silicates, such as synthetic or natural mica, talc, kaolin, glass platelet SiO 2 platelets or synthetic carrier-free platelets. Furthermore, platelet-shaped metal oxides such. B. platelet-shaped iron oxide, aluminum oxide, titanium dioxide, silicon dioxide, LCP's (Liquid Crystal Polymers), holographic pigments, conductive pigments or coated graphite platelets.
- metal platelets can also be used, which are uncoated or with one or more metal oxide layers can be covered; z.
- Particularly preferred substrates are mica flakes coated with one or more metal oxides.
- Colorless, highly refractive metal oxides such as, in particular, titanium dioxide, antimony (III) oxide, zinc oxide, tin oxide and / or zirconium dioxide, and colored metal oxides such as, for example, chromium oxide, nickel oxide, copper oxide, cobalt oxide and in particular iron oxide (Fe 2 O 3 , Fe 3 O 4 ).
- Antimony (III) oxide is particularly preferably used alone or in combination with tin oxide as the absorber material.
- Coated SiO 2 platelets are e.g. B. known from WO 93/08237 (wet chemical coating) and DE-OS 196 14 637 (CVD process).
- Multilayer pigments based on phyllosilicates are known, for example, from German published documents DE 196 18 569, DE 196 38 708, DE 197 07 806 and DE 198 03 550.
- Multi-layer pigments which have the following structure are particularly suitable: 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 -Plate + 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 can also be a mixture of two or more components.
- thermoplastics as well as Duraplast, e.g. in Ullmann, vol. 15, pp. 457 ff., publisher VCH, can be permanently and abrasion-resistant inscribed using a laser using the method according to the invention.
- Suitable plastics are in particular polyethylene, polypropylene, polyamides, polyesters, polyester esters, polyether esters, polyphenylene ethers, polyacetal, polybutylene terephthalate, polymethyl methacrylate, polyvinyl acetal, polystyrene, acrylonitrile-butadiene-styrene (ABS), acrylonitrile-styrene-acrylic esters (ASA), polycarbonate, polyethersulfone and polyether ketones and their copolymers and / or mixture.
- Lacquers are understood to be all lacquers known to the person skilled in the art, such as, for B. car paints, industrial paints, refinish paints, powder coatings.
- Particularly suitable powder coatings are based on polyester, epoxy resins, polyester epoxy resins (mixed powder), polyurethanes, acrylates, fluidized bed powders (polyamide base).
- So-called carrier substances of the colorant / absorber component can be added to improve the color input into the matrix of the plastic or the powder coating. These significantly improve the entry into the surface of the plastic or powder coating, but are not retained as a component in the marking.
- Suitable carriers are e.g. B. mineral oils, waxes, paraffins and nitrocellulose varnishes.
- the proportion of carrier substance based on 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 becomes even more high-contrast if the plastic or coating system to be labeled is additionally doped with one or more laser light-absorbing substances. The entry of the colorant into the surface of the system to be marked is then significantly improved.
- the dopant in the plastic or in the lacquer can be the same or different with the laser light-absorbing substance of the colorant / absorber component.
- Suitable laser-absorbing substances in plastic or lacquer are in particular platelet-shaped transparent or semi-transparent substrates which are coated with one or more colored or colorless metal oxides. Dopants based on mica substrates are particularly preferred. These platelet-shaped pigments are known and are commercially available under the brand Iriodin® LS from Merck KGaA.
- the marking of plastics and powder coatings is simple and easy to use.
- the colored marking takes place predominantly in the plastic or powder coating matrix, ie not by melting another plastic or coating component.
- the colorant / absorber component can be applied directly to the plastic or lacquer to be labeled.
- the colorant / absorber component is applied to the surface of the system to be marked by customary techniques, such as brushing, brushing, printing, spraying, knife coating.
- the layer thickness is generally 0.1 to 10000 nm, preferably 10 to 5000 nm, in particular 50 to 3000 nm.
- the entry into the plastic surface is made directly by the laser beam focused on the plastic or lacquer surface.
- lasers with different wavelengths can be used, but preferably CO 2 lasers at a wavelength of 10.6 ⁇ m, and Nd: YAG lasers at 1064 nm by simply wiping the surface of the marked system from the unused colorant / absorber component.
- the laser inscription is such that the sample body is brought into the beam path of a pulsed laser, preferably a CO 2 or Nd: YAG laser. Labeling with an excimer laser, for example using a mask technique, is also possible. However, the desired results can also be achieved with other conventional laser types which have a wavelength in a high absorption range of the laser light-absorbing substance used.
- the marking obtained is determined by the irradiation time (or the number of pulses in the case of pulse lasers) and the irradiation power of the laser and the plastic system or coating system used. The power of the lasers used depends on the respective application and can be easily determined by a specialist in individual cases.
- the laser used generally has a wavelength in the range from 157 nm to 10.6 ⁇ m, preferably in the range from 532 nm to 10.6 ⁇ m.
- CO 2 lasers (10.6 ⁇ m) and Nd: YAG lasers (1064 or 532 nm) or pulsed UV lasers may be mentioned here.
- the excimer lasers have the following wavelengths: F 2 excimer laser (157 nm), ArF excimer laser (193 nm), KrCI excimer laser (222 nm), KrF excimer laser (248 nm), XeCl excimer laser (308 nm), XeF excimer laser (351 nm), frequency multiplied
- Nd YAG laser with wavelengths of 355 nm (frequency tripled) or 265 nm (frequency quadrupled).
- Nd YAG lasers (1064 or 532 nm) and CO 2 lasers 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 0.3 mJ / cm 2 to 10 J / cm 2 .
- the pulse frequency is generally in the range from 1 to 30 kHz.
- Corresponding lasers that can be used in the method according to the invention are commercially available.
- the plastic or varnish according to the invention can be used in all fields where previously customary printing processes have been used for labeling plastics.
- moldings made from the plastic according to the invention can be used in the electrical, electronics and motor vehicle 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, which consist of the plastic according to the invention, can be marked with the aid of laser light even in hard-to-reach places.
- the plastic system 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 by the fact that they are smudge-proof and scratch-resistant, stable during subsequent sterilization processes, and can be applied hygienically during the marking process.
- Complete label images can be permanently applied to the packaging for a reusable system.
- Another important area of application for laser marking is plastic tags for the individual identification of animals, so-called cattle tags or ear tags.
- the information that is specific to the animal is stored via a barcode system. If necessary, these can be called up again using a scanner.
- the lettering has to be very durable, because the mark remains on the animals for several years.
- the paints and powder coatings of the invention 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 plates, packaging, plugs, grids, developer parts.
- Injection molded bodies are made from a thermoplastic polypropylene (type: PPH 10 from DSM, Geelen), which is 1% titanium dioxide (Kronos, from Kronos) and 0.2% Iriodin® LS 825 (coated with (Sn, Sb) O 2 ) Mica from Merck KGaA, Darmstadt) included.
- a thermoplastic polypropylene type: PPH 10 from DSM, Geelen
- Ti dioxide Kronos, from 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 spraying process.
- the injection molded bodies show a white body color under daylight.
- a mixture of a blue color pigment (PV real blue, from Clariant) and a tin-antimony mixed oxide (Zelec ECP-3010-XC, from Dupont Chemicals) is applied to the surface of the injection molded body at a mixing ratio of 2: 8 applied.
- the mixture is mixed in a ratio of 1: 1 with a mineral oil (Energol WM6 from BP Lubricant GmbH).
- the uniform color layer of colorant and laser absorber obtained after spraying is applied to the surface with a commercially available Nd: YAG laser (type Starkmark, from Baasel Lasertechnik). Then the surface is removed by simply wiping off the color layer that has not been entered. What remains are blue, high-contrast lettering, which is characterized by a high surface quality and very good abrasion resistance.
- Example 7 Analogous to Example 1, but with a red color pigment (PV Echtrot, from Clariant) and a tin-antimony mixed oxide (Zelec ECP-3010-XC, from Dupont Chemicals), the mixing ratio being 3: 7. It shows red, high-contrast lettering, which are characterized by a high surface quality and very good abrasion resistance.
- Example 2 Analogous to Example 2, but with a yellow color pigment (PV real yellow, from Clariant) and a tin-antimony mixed oxide (Zelec ECP-3010-XC, from Dupont Chemicals), the mixing ratio being 1: 9. It shows yellow, high-contrast lettering, which are characterized by a high surface quality and very good abrasion resistance.
- a yellow color pigment PV real yellow, from Clariant
- Zelec ECP-3010-XC tin-antimony mixed oxide
- Injection moldings are produced from a thermoplastic polyamide (type Schulamid, from 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 spraying process.
- the injection molded bodies show a black body color under daylight.
- the laser marking is carried out analogously to Example 1. You get blue, high-contrast lettering, which is characterized by a high surface quality and 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. You get blue, high-contrast lettering, which is characterized by a high surface quality and very good abrasion resistance.
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- Physics & Mathematics (AREA)
- Optics & Photonics (AREA)
- Thermal Transfer Or Thermal Recording In General (AREA)
- Paints Or Removers (AREA)
- Application Of Or Painting With Fluid Materials (AREA)
- Compositions Of Macromolecular Compounds (AREA)
- Laser Beam Printer (AREA)
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Abstract
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 inscription or marking of plastics, lacquers, including powder lacquers, a colorant being transferred into the plastics or lacquer by laser radiation with the aid of a laser light-absorbing substance.
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 production goods is becoming increasingly important in almost all branches of industry. So often z. B. Production dates, expiry dates, barcodes, company logos, serial numbers, etc. can be applied to products. Currently, these markings are mainly carried out using conventional techniques such as printing, embossing, stamping and labeling. With the help of a laser beam, inscriptions can be applied to glass, metal and ceramic, especially in the infrared range. The materials from which the subsequent inscription is made are melted onto the surface. However, this method is not suitable for labeling plastics. The dark marking with lasers is becoming increasingly important for plastics. With this technique it is possible to use graphic labels such as Barcodes can be applied to a non-flat surface at high speed. Since the label is 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 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. Colored laser marking of a dark plastic is disclosed in EP 0 522 370 A1. For example, 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 an opacifying 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 methods known from the prior art for the colored labeling of plastics have the disadvantage that they do not enable colored marking on plastics with bright colors or that several lasers with different wavelengths are required for the colored labeling 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.It was therefore an object of the present invention to find a method which, under the action of laser light, enables colored marking with high contrast on each plastic color 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 was found that plastics and paints can be labeled in color if the surface of a laser-markable plastic or varnish is coated with a mixture of colorant and absorber substance and is partially or fully entered into the surface. The colorant, in combination with the laser-absorbing substance, is introduced into the plastic or lacquer surface melted by laser radiation. Through the entry in the surface of the plastic or varnish, colored inscriptions with very high abrasion resistance can be achieved.
Gegenstand der Erfindung sind farbig beschriftbare oder markierbare Kunststoffe und Lacke, dadurch gekennzeichnet, dass auf die Kunststoffoder Lackoberfläche ein Gemisch bestehend aus einem oder mehreren Farbmitteln und einer oder mehreren laserlichtabsorbierenden Substanzen appliziert wird.The invention relates to plastics and lacquers which can be labeled or marked in color, characterized in that a mixture consisting of one or more colorants and one or more laser-absorbing substances is applied to the plastic or lacquer surface.
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 if the ratio of colorant / laser light-absorbing substance is 10: 1 to 1:10, preferably 95: 5 to 70:30, in particular 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 lacquer, however, depends on the plastic system or lacquer composition used and the area of the lettering.
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.Both organic and inorganic colorants can be used for labeling. All colorants known to the person skilled in the art which do not decompose during laser irradiation are suitable.
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 organic pigments mentioned below:
Copper phthalocyanines, dioxazines, anthraquinones, monoazo and
Diazo pigments, diketopyrolopyrrole, polycyclic pigments, anthrapyrimidines, quinacridones, quinaphtalones, 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 e.g. B. acridines, azo dyes, phthalocyanines, xanthenes and phenazines. The dyes can 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 e.g. B. 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 can 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-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 made of, for example, layered silicates, such as synthetic or natural mica, talc, kaolin, glass platelet SiO 2 platelets or synthetic carrier-free platelets. Furthermore, platelet-shaped metal oxides such. B. platelet-shaped iron oxide, aluminum oxide, titanium dioxide, silicon dioxide, LCP's (Liquid Crystal Polymers), holographic pigments, conductive pigments or coated graphite platelets.
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-, Agund 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, metal platelets can also be used, which are uncoated or with one or more metal oxide layers can be covered; z. B. Al, Cr, Fe, Au, Ag and steel plates. Should corrosion-prone metal plates 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. Colorless, highly refractive metal oxides, such as, in particular, titanium dioxide, antimony (III) oxide, zinc oxide, tin oxide and / or zirconium dioxide, and colored metal oxides such as, for example, chromium oxide, nickel oxide, copper oxide, cobalt oxide and in particular iron oxide (Fe 2 O 3 , Fe 3 O 4 ). Antimony (III) oxide is particularly preferably used alone or in combination with tin oxide as the absorber material.
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 for the most part commercially available, e.g. B. under the brand Iriodin® LS from Merck KGaA, and / or can be prepared by standard methods known to those skilled in the art. Pigments based on transparent or semi-transparent platelet-shaped substrates are used, for. B. described in the
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, 31 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 e.g. B. known from WO 93/08237 (wet chemical coating) and DE-OS 196 14 637 (CVD process).
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:
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 can 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, Polymethyl methacrylat, 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, e.g. in Ullmann, vol. 15, pp. 457 ff., publisher VCH, can be permanently and abrasion-resistant inscribed using a laser using the method according to the invention. Suitable plastics are in particular polyethylene, polypropylene, polyamides, polyesters, polyester esters, polyether esters, polyphenylene ethers, polyacetal, polybutylene terephthalate, polymethyl methacrylate, polyvinyl acetal, polystyrene, acrylonitrile-butadiene-styrene (ABS), acrylonitrile-styrene-acrylic esters (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.Lacquers are understood to be all lacquers known to the person skilled in the art, such as, for B. car paints, industrial paints, refinish paints, powder coatings.
Besonders geeignete Pulverlacke sind auf Basis von Polyester, Epoxidharzen, Polyesterepoxidharzen (Mischpulver), Polyurethanen, Acrylaten, Wirbelsinterpulvern (Polyamidbasis).Particularly suitable powder coatings are based on polyester, epoxy resins, polyester epoxy resins (mixed powder), polyurethanes, acrylates, fluidized bed powders (polyamide base).
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.So-called carrier substances of the colorant / absorber component can be added to improve the color input into the matrix of the plastic or the powder coating. These significantly improve the entry into the surface of the plastic or powder coating, but are not retained as a component in the marking.
Geeignete Träger sind z. B. mineralische Öle, Wachse, Paraffine und Nitrocelluloselacke.Suitable carriers are e.g. B. mineral oils, waxes, paraffins and nitrocellulose varnishes.
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 based on 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 special embodiment, the colored marking of the plastics and powder coatings becomes even more high-contrast if the plastic or coating system to be labeled is additionally doped with one or more laser light-absorbing substances. The entry of the colorant into 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 lacquer can be the same or different with the laser light-absorbing substance of the colorant / absorber component. Suitable laser-absorbing substances in plastic or lacquer are in particular platelet-shaped transparent or semi-transparent substrates which are coated with one or more colored or colorless metal oxides. Dopants based on mica substrates are particularly preferred. These platelet-shaped pigments are known and are commercially available under the brand 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 plastics and powder coatings is simple and easy to use. The colored marking takes place predominantly in the plastic or powder coating matrix, ie not by melting another plastic or coating component. For application, the colorant / absorber component can be applied directly to the plastic or lacquer to be labeled. The colorant / absorber component is applied to the surface of the system to be marked by customary techniques, such as brushing, brushing, printing, spraying, knife coating. The layer thickness is generally 0.1 to 10000 nm, preferably 10 to 5000 nm, in particular 50 to 3000 nm. The entry into the plastic surface is made directly by the laser beam focused on the plastic or lacquer surface. Depending on the colorant / absorber combinations used, lasers with different wavelengths can be used, but preferably CO 2 lasers at a wavelength of 10.6 μm, and Nd: YAG lasers at 1064 nm by simply wiping 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 laser inscription is such that the sample body is brought into the beam path of a pulsed laser, preferably a CO 2 or Nd: YAG laser. Labeling with an excimer laser, for example using a mask technique, is also possible. However, the desired results can also be achieved with other conventional laser types which have a wavelength in a high absorption range of the laser light-absorbing substance used. The marking obtained is determined by the irradiation time (or the number of pulses in the case of pulse lasers) and the irradiation power of the laser and the plastic system or coating system used. The power of the lasers used depends on the respective application and can be easily determined by a specialist in individual cases.
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), KrCI-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 from 157 nm to 10.6 μm, preferably in the range from 532 nm to 10.6 μm. For example, CO 2 lasers (10.6 µm) and Nd: YAG lasers (1064 or 532 nm) or pulsed UV lasers may be mentioned here. The excimer lasers have the following wavelengths: F 2 excimer laser (157 nm), ArF excimer laser (193 nm), KrCI excimer laser (222 nm), KrF excimer laser (248 nm), XeCl excimer laser (308 nm), XeF excimer laser (351 nm), frequency multiplied Nd: YAG laser with wavelengths of 355 nm (frequency tripled) or 265 nm (frequency quadrupled). Nd: YAG lasers (1064 or 532 nm) and CO 2 lasers 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 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 from 1 to 30 kHz. Corresponding lasers that can be used in the method according to the invention are commercially available.
Die Verwendung des erfindungsgemäßen Kunststoffes bzw. Lacks 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-, 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, die aus dem erfindungsgemäßen Kunststoff bestehen, können selbst an schwer zugänglichen Stellen mit Hilfe von Laserlicht markiert werden. Weiterhin kann das erfindungsgemäße Kunststoffsystem 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 plastic or varnish according to the invention can be used in all fields where previously customary printing processes have been used for labeling plastics. For example, moldings made from the plastic according to the invention can be used in the electrical, electronics and motor vehicle 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, which consist of the plastic according to the invention, can be marked with the aid of laser light even in hard-to-reach places. Furthermore, the plastic system 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 by the fact that they are smudge-proof and scratch-resistant, stable during subsequent sterilization processes, and can be applied hygienically during the marking process. Complete label images can be permanently applied to the packaging for a reusable system. Another important area of application for laser marking is plastic tags for the individual identification of animals, so-called cattle tags or ear tags. The information that is specific to the animal is stored via a barcode system. If necessary, these can be called up again using a scanner. The lettering has to be very durable, because the mark remains on the animals for several years.
Die erfindungsgemäßen 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 of the invention 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 plates, packaging, plugs, grids, developer 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 percentages by weight.
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 made from a thermoplastic polypropylene (type: PPH 10 from DSM, Geelen), which is 1% titanium dioxide (Kronos, from Kronos) and 0.2% Iriodin® LS 825 (coated with (Sn, Sb) O 2 ) Mica from Merck KGaA, Darmstadt) included.
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 spraying process. The injection molded bodies show a white body color under daylight. Using a commercially available airbrush gun, a mixture of a blue color pigment (PV real blue, from Clariant) and a tin-antimony mixed oxide (Zelec ECP-3010-XC, from Dupont Chemicals) is applied to the surface of the injection molded body at a mixing ratio of 2: 8 applied. For use in the airbrush gun, the mixture is mixed in a ratio of 1: 1 with a mineral oil (Energol WM6 from BP Lubricant GmbH). The uniform color layer of colorant and laser absorber obtained after spraying is applied to the surface with a commercially available Nd: YAG laser (type Starkmark, from Baasel Lasertechnik). Then the surface is removed by simply wiping off the color layer that has not been entered. What remains are blue, high-contrast lettering, which is characterized by a high surface quality and very good abrasion resistance.
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.Analogous to Example 1, but with a red color pigment (PV Echtrot, from Clariant) and a tin-antimony mixed oxide (Zelec ECP-3010-XC, from Dupont Chemicals), the mixing ratio being 3: 7. It shows red, high-contrast lettering, which are characterized by a high surface quality and very good abrasion resistance.
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.Analogous to Example 2, but with a yellow color pigment (PV real yellow, from Clariant) and a tin-antimony mixed oxide (Zelec ECP-3010-XC, from Dupont Chemicals), the mixing ratio being 1: 9. It shows yellow, high-contrast lettering, which are characterized by a high surface quality and very good abrasion resistance.
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 moldings are produced from a thermoplastic polyamide (type Schulamid, from 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 spraying process. The injection molded bodies show a black body color under daylight. The laser marking is carried out analogously to Example 1. You get blue, high-contrast lettering, which is characterized by a high surface quality and very good abrasion resistance.
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. You get blue, high-contrast lettering, which is characterized by a high surface quality and very good abrasion resistance.
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DE10136479A DE10136479A1 (en) | 2001-07-27 | 2001-07-27 | Colored labeling and marking of plastics and paints |
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Cited By (9)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
WO2005097514A1 (en) * | 2004-03-30 | 2005-10-20 | Merck Patent Gmbh | Sealing of plastic inscriptions |
EP1918096A2 (en) * | 2006-11-02 | 2008-05-07 | Mitsubishi Polyester Film GmbH | White multi-layer, laser-cuttable polyester film |
EP2065165A1 (en) * | 2007-11-30 | 2009-06-03 | Eckart GmbH | Utilisation of a mixture of spherical metal particles and metal flakes as laser markability or laser weldability means and laser markable and/or laser weldable plastic |
CN100496993C (en) * | 2004-03-30 | 2009-06-10 | 默克专利股份有限公司 | Method for the permanent abrasion-resistant colored inscription and/or marking of plastics and plastic obtained therefrom |
CN102171104A (en) * | 2008-10-09 | 2011-08-31 | 利乐拉瓦尔集团及财务有限公司 | Method and device for traceability marking and packaging line provider with traceability marking device |
US8278243B2 (en) * | 2004-01-14 | 2012-10-02 | Datalase Ltd. | Laser imaging |
US8435205B2 (en) | 2010-01-29 | 2013-05-07 | The Procter & Gamble Company | Applicator having a color gradient |
WO2013135416A1 (en) * | 2012-03-15 | 2013-09-19 | Robert Bosch Gmbh | Powder-coating apparatus and powder-coating method |
CN105082812A (en) * | 2014-05-23 | 2015-11-25 | 默克专利股份有限公司 | Method for the laser treatment of coatings |
Families Citing this family (23)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
FR2833518B1 (en) * | 2001-12-14 | 2004-06-25 | Gemplus Card Int | LASER MARKED INFORMATION MEDIUM |
DE10252007A1 (en) * | 2002-11-06 | 2004-05-27 | Merck Patent Gmbh | Laser-markable pigments |
EP1664919A2 (en) * | 2003-09-08 | 2006-06-07 | Laser Projection Technologies, Inc. | 3d projection with image recording |
PL1664172T3 (en) * | 2003-09-17 | 2007-05-31 | Ciba Specialty Chemicals Holding Inc | Laser markable polymeric compositions |
NZ528993A (en) * | 2003-10-17 | 2006-04-28 | Leyhatton Innovations Ltd | Indelible marking of labels |
US20070080146A1 (en) * | 2003-11-10 | 2007-04-12 | Werner Stockum | Coloured laser marking |
US20050255406A1 (en) * | 2004-05-11 | 2005-11-17 | Shlomo Assa | Marking on a thin film |
GB2421221B (en) * | 2004-12-20 | 2007-11-28 | Uponor Innovation Ab | Marking of pipes |
DE102005057474A1 (en) | 2005-11-30 | 2007-05-31 | Merck Patent Gmbh | Method for flexible and individual marking of products, documents of value and security documents, involves introduction of security features into layer system |
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WO2012092104A1 (en) | 2010-12-30 | 2012-07-05 | Ticona Llc | Powder containing a polyoxymethylene polymer for coating metallic substrates |
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US20130168133A1 (en) * | 2011-03-18 | 2013-07-04 | Mitsubishi Chemical Europe Gmbh | Process for producing a circuit carrier |
US9776210B2 (en) | 2012-03-01 | 2017-10-03 | Ferro Corporation | Laser absorbing compounds |
JP6345602B2 (en) * | 2012-03-01 | 2018-06-20 | フエロ コーポレーション | Laser absorbing compound |
BR112018016589A2 (en) | 2016-02-19 | 2018-12-18 | Gen Cable Technologies Corp | laser marked cables and system to do the same |
EP3281974A1 (en) * | 2016-08-11 | 2018-02-14 | Innocabs B.V. | Laser marking additive |
Citations (8)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
DE1467468A1 (en) | 1961-06-28 | 1968-12-12 | Du Pont | Mica flake pigment |
DE1959998A1 (en) | 1969-11-29 | 1971-07-08 | Merck Patent Gmbh | Pearlescent pigments and processes for their manufacture |
DE2009566B1 (en) | 1970-02-28 | 1971-11-11 | Merck Patent Gmbh | Process for the production of titanium dioxide or titanium dioxide aquate coatings |
DE2215191A1 (en) | 1971-03-30 | 1972-10-12 | E I du Pont de Nemours and Co , Wilmington, Del (V St A) | Improved Pigments |
DE2214454A1 (en) | 1971-03-24 | 1972-11-02 | Kabushiki Kaisha Suwa Seikosha, Tokio | Method of controlling a printer |
DE2244298A1 (en) | 1972-09-09 | 1974-03-28 | Merck Patent Gmbh | PEARL PIGMENTS AND THE PROCESS FOR THEIR MANUFACTURING |
EP0522370A1 (en) | 1991-06-29 | 1993-01-13 | Hoechst Aktiengesellschaft | Polymeric moulding composition containing pigment |
EP0684144B1 (en) | 1994-05-25 | 1998-08-26 | Sodirep Sarl | Compositions for coloured marking of plastic materials by laser irradiation |
Family Cites Families (15)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
GB341388A (en) * | 1928-11-01 | 1931-01-15 | British Celanese | Improvements in the manufacture of hollow artificial filaments, straws and the like |
DE59008746D1 (en) * | 1989-08-18 | 1995-04-27 | Ciba Geigy Ag | Laser marking of plastic objects in any shape with special effects. |
FR2654982B1 (en) * | 1989-11-29 | 1992-03-06 | Merlin Gerin | LASER MARKING PROCESS AND PAINT. |
US6521688B1 (en) * | 1994-05-05 | 2003-02-18 | Merck Patent Gesellschaft Mit Beschrankter Haftung | Laser-markable plastics |
DE4415802A1 (en) * | 1994-05-05 | 1995-11-09 | Merck Patent Gmbh | Laser-markable plastics |
US5489639A (en) * | 1994-08-18 | 1996-02-06 | General Electric Company | Copper salts for laser marking of thermoplastic compositions |
US5584922A (en) * | 1994-09-14 | 1996-12-17 | Ciba-Geigy Corporation | Stir-in organic pigments |
DE19522397A1 (en) * | 1995-06-23 | 1997-01-02 | Merck Patent Gmbh | Laser-markable plastics |
US6075223A (en) * | 1997-09-08 | 2000-06-13 | Thermark, Llc | High contrast surface marking |
DE19836885A1 (en) * | 1998-08-14 | 2000-02-17 | Clariant Gmbh | Laser marking of effect coatings |
US6133342A (en) * | 1999-01-21 | 2000-10-17 | Marconi Data Systems Inc. | Coating composition |
US6261348B1 (en) * | 1999-06-25 | 2001-07-17 | Marconi Data Systems Inc. | Laser markable coating |
DE19961304A1 (en) * | 1999-12-18 | 2001-06-21 | Merck Patent Gmbh | Laser-markable plastics |
US6503316B1 (en) * | 2000-09-22 | 2003-01-07 | Dmc2 Degussa Metals Catalysts Cerdec Ag | Bismuth-containing laser markable compositions and methods of making and using same |
US6693657B2 (en) * | 2001-04-12 | 2004-02-17 | Engelhard Corporation | Additive for YAG laser marking |
-
2001
- 2001-07-27 DE DE10136479A patent/DE10136479A1/en not_active Withdrawn
-
2002
- 2002-07-23 DE DE50205815T patent/DE50205815D1/en not_active Expired - Fee Related
- 2002-07-23 EP EP02016489A patent/EP1279517B1/en not_active Expired - Lifetime
- 2002-07-23 AT AT02016489T patent/ATE317767T1/en not_active IP Right Cessation
- 2002-07-26 US US10/202,838 patent/US6924077B2/en not_active Expired - Fee Related
- 2002-07-29 JP JP2002219132A patent/JP2003175571A/en active Pending
Patent Citations (8)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
DE1467468A1 (en) | 1961-06-28 | 1968-12-12 | Du Pont | Mica flake pigment |
DE1959998A1 (en) | 1969-11-29 | 1971-07-08 | Merck Patent Gmbh | Pearlescent pigments and processes for their manufacture |
DE2009566B1 (en) | 1970-02-28 | 1971-11-11 | Merck Patent Gmbh | Process for the production of titanium dioxide or titanium dioxide aquate coatings |
DE2214454A1 (en) | 1971-03-24 | 1972-11-02 | Kabushiki Kaisha Suwa Seikosha, Tokio | Method of controlling a printer |
DE2215191A1 (en) | 1971-03-30 | 1972-10-12 | E I du Pont de Nemours and Co , Wilmington, Del (V St A) | Improved Pigments |
DE2244298A1 (en) | 1972-09-09 | 1974-03-28 | Merck Patent Gmbh | PEARL PIGMENTS AND THE PROCESS FOR THEIR MANUFACTURING |
EP0522370A1 (en) | 1991-06-29 | 1993-01-13 | Hoechst Aktiengesellschaft | Polymeric moulding composition containing pigment |
EP0684144B1 (en) | 1994-05-25 | 1998-08-26 | Sodirep Sarl | Compositions for coloured marking of plastic materials by laser irradiation |
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CN100496993C (en) * | 2004-03-30 | 2009-06-10 | 默克专利股份有限公司 | Method for the permanent abrasion-resistant colored inscription and/or marking of plastics and plastic obtained therefrom |
US8343412B2 (en) | 2004-03-30 | 2013-01-01 | Merck Patent Gmbh | Sealing of inscriptions on plastics |
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EP1918096A2 (en) * | 2006-11-02 | 2008-05-07 | Mitsubishi Polyester Film GmbH | White multi-layer, laser-cuttable polyester film |
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CN102171104A (en) * | 2008-10-09 | 2011-08-31 | 利乐拉瓦尔集团及财务有限公司 | Method and device for traceability marking and packaging line provider with traceability marking device |
US8435205B2 (en) | 2010-01-29 | 2013-05-07 | The Procter & Gamble Company | Applicator having a color gradient |
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EP2946938A1 (en) * | 2014-05-23 | 2015-11-25 | Merck Patent GmbH | Method for the laser treatment of coatings |
EP2946938B1 (en) | 2014-05-23 | 2017-04-12 | Merck Patent GmbH | Method for the laser treatment of coatings |
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CN105082812B (en) * | 2014-05-23 | 2020-01-10 | 默克专利股份有限公司 | Method for laser treatment of coatings |
Also Published As
Publication number | Publication date |
---|---|
US6924077B2 (en) | 2005-08-02 |
EP1279517B1 (en) | 2006-02-15 |
DE10136479A1 (en) | 2003-02-06 |
JP2003175571A (en) | 2003-06-24 |
US20040013969A1 (en) | 2004-01-22 |
ATE317767T1 (en) | 2006-03-15 |
EP1279517A3 (en) | 2003-06-25 |
DE50205815D1 (en) | 2006-04-20 |
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