EP1279517A2 - Ecriture et marquage en couleur sur une matière synthétique ou sur une surface laquée - Google Patents

Ecriture et marquage en couleur sur une matière synthétique ou sur une surface laquée Download PDF

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Publication number
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
Authority
EP
European Patent Office
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.)
Granted
Application number
EP02016489A
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German (de)
English (en)
Other versions
EP1279517B1 (fr
EP1279517A3 (fr
Inventor
Reiner Delp
Matthias Dr. Kuntz
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Merck Patent GmbH
Original Assignee
Merck Patent GmbH
Priority date (The priority date 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 date listed.)
Filing date
Publication date
Application filed by Merck Patent GmbH filed Critical Merck Patent GmbH
Publication of EP1279517A2 publication Critical patent/EP1279517A2/fr
Publication of EP1279517A3 publication Critical patent/EP1279517A3/fr
Application granted granted Critical
Publication of EP1279517B1 publication Critical patent/EP1279517B1/fr
Anticipated expiration legal-status Critical
Expired - Lifetime legal-status Critical Current

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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 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)
  • Laser Beam Processing (AREA)
  • Laminated Bodies (AREA)
  • Dot-Matrix Printers And Others (AREA)
  • Laser Beam Printer (AREA)
  • Compositions Of Macromolecular Compounds (AREA)
  • Application Of Or Painting With Fluid Materials (AREA)
  • Inks, Pencil-Leads, Or Crayons (AREA)
EP02016489A 2001-07-27 2002-07-23 Ecriture et marquage en couleur sur une matière synthétique ou sur une surface laquée Expired - Lifetime EP1279517B1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
DE10136479A DE10136479A1 (de) 2001-07-27 2001-07-27 Farbige Beschriftung und Markierung von Kunststoffen und Lacken
DE10136479 2001-07-27

Publications (3)

Publication Number Publication Date
EP1279517A2 true EP1279517A2 (fr) 2003-01-29
EP1279517A3 EP1279517A3 (fr) 2003-06-25
EP1279517B1 EP1279517B1 (fr) 2006-02-15

Family

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Family Applications (1)

Application Number Title Priority Date Filing Date
EP02016489A Expired - Lifetime EP1279517B1 (fr) 2001-07-27 2002-07-23 Ecriture et marquage en couleur sur une matière synthétique ou sur une surface laquée

Country Status (5)

Country Link
US (1) US6924077B2 (fr)
EP (1) EP1279517B1 (fr)
JP (1) JP2003175571A (fr)
AT (1) ATE317767T1 (fr)
DE (2) DE10136479A1 (fr)

Cited By (9)

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Publication number Priority date Publication date Assignee Title
WO2005097514A1 (fr) * 2004-03-30 2005-10-20 Merck Patent Gmbh Scellement d'inscriptions plastiques
EP1918096A3 (fr) * 2006-11-02 2009-03-11 Mitsubishi Polyester Film GmbH Feuille de polyester multicouches, blanche pouvant être découpée par laser
EP2065165A1 (fr) * 2007-11-30 2009-06-03 Eckart GmbH Utilisation d'un mélange de particules métalliques sphériques et de flocons métalliques jouant le rôle d'agent de marquage laser ou d'agent apte au soudage laser, et matériau plastique apte au marquage laser et/ou au soudage laser
CN100496993C (zh) * 2004-03-30 2009-06-10 默克专利股份有限公司 将塑料永久和耐磨性地有色刻记和/或标记的方法以及由其获得的塑料
CN102171104A (zh) * 2008-10-09 2011-08-31 利乐拉瓦尔集团及财务有限公司 用于可追溯性标记的方法和装置以及设有可追溯性标记装置的包装线
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 (fr) * 2012-03-15 2013-09-19 Robert Bosch Gmbh Dispositif de revêtement par pulvérisation et procédé de revêtement par pulvérisation
EP2946938A1 (fr) * 2014-05-23 2015-11-25 Merck Patent GmbH Procédé de traitement laser de revêtements

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DE10252007A1 (de) * 2002-11-06 2004-05-27 Merck Patent Gmbh Lasermarkierbare Pigmente
CA2537873A1 (fr) * 2003-09-08 2005-03-24 Laser Projection Technologies, Inc. Projection 3d avec enregistrement d'image
PL1664172T3 (pl) * 2003-09-17 2007-05-31 Ciba Specialty Chemicals Holding Inc Kompozycje polimerowe do znakowania laserowego
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 (de) 2005-11-30 2007-05-31 Merck Patent Gmbh Lasertransfer von Sicherheitsmerkmalen
JP3889431B1 (ja) * 2006-02-08 2007-03-07 日本カラリング株式会社 レーザーマーキング用多層シート及びレーザーマーキング方法
DE102007021820A1 (de) * 2007-05-07 2008-11-13 Chemische Fabrik Budenheim Kg Laserpigmente für Keramiken
US7829258B2 (en) * 2008-01-22 2010-11-09 Appleton Papers Inc. Laser coloration of coated substrates
WO2010087327A1 (fr) * 2009-01-27 2010-08-05 静岡県 Procédé de marquage au laser
EP2547723A4 (fr) * 2010-03-16 2017-08-02 Basf Se Procédé destiné à marquer des compositions polymères contenant des nanolamelles de graphite
WO2012056385A1 (fr) 2010-10-25 2012-05-03 Sabic Innovative Plastics Ip B.V. Amélioration des performances de dépôt autocatalytique de matériaux utilisés en structuration directe par laser
EP3046401A1 (fr) * 2010-10-26 2016-07-20 SABIC Global Technologies B.V. Matériaux de structuration directe au laser avec prise en compte de toutes les couleurs
WO2012092104A1 (fr) 2010-12-30 2012-07-05 Ticona Llc Poudre contenant un polymère de polyoxyméthylène pour revêtir des substrats métalliques
WO2012128219A1 (fr) 2011-03-18 2012-09-27 ミツビシ ケミカル ヨーロッパ ゲーエムベーハー Composition de résine thermoplastique, moulage de résine et procédé de fabrication d'un moulage de résine ayant une couche de placage fixée à celui-ci
CN103154135B (zh) * 2011-03-18 2014-10-15 三菱化学欧洲合资公司 生产电路载体的方法
US9776210B2 (en) 2012-03-01 2017-10-03 Ferro Corporation Laser absorbing compounds
ES2655965T3 (es) * 2012-03-01 2018-02-22 Ferro Corporation Compuestos absorbentes de láser
US10290398B2 (en) 2016-02-19 2019-05-14 General Cable Technologies Corporation Laser-markable cables and systems for making the same
EP3281974A1 (fr) * 2016-08-11 2018-02-14 Innocabs B.V. Additif de marquage au laser
US12378409B1 (en) 2020-04-09 2025-08-05 Southwire Company, Llc High contrast laser markable cables and marking methods

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DE1467468A1 (de) 1961-06-28 1968-12-12 Du Pont Glimmerschuppenpigment
DE1959998A1 (de) 1969-11-29 1971-07-08 Merck Patent Gmbh Perlglanzpigmente und Verfahren zu ihrer Herstellung
DE2009566B1 (de) 1970-02-28 1971-11-11 Merck Patent Gmbh Verfahren zur Herstellung von Titandioxid- bzw. Titandioxidaquatüberzügen
DE2214454A1 (de) 1971-03-24 1972-11-02 Kabushiki Kaisha Suwa Seikosha, Tokio Verfahren zum Steuern eines Druckers
DE2215191A1 (de) 1971-03-30 1972-10-12 E I du Pont de Nemours and Co , Wilmington, Del (V St A) Verbesserte Pigmente
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EP0684144B1 (fr) 1994-05-25 1998-08-26 Sodirep Sarl Compositions destinées au marquage coloré des matériaux plastiques par irradiation laser

Cited By (20)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US8278243B2 (en) * 2004-01-14 2012-10-02 Datalase Ltd. Laser imaging
CN100496993C (zh) * 2004-03-30 2009-06-10 默克专利股份有限公司 将塑料永久和耐磨性地有色刻记和/或标记的方法以及由其获得的塑料
RU2405678C2 (ru) * 2004-03-30 2010-12-10 Мерк Патент Гмбх Герметизация надписей на пластиках
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DE10136479A1 (de) 2003-02-06
DE50205815D1 (de) 2006-04-20
JP2003175571A (ja) 2003-06-24
US6924077B2 (en) 2005-08-02
EP1279517B1 (fr) 2006-02-15
US20040013969A1 (en) 2004-01-22
ATE317767T1 (de) 2006-03-15
EP1279517A3 (fr) 2003-06-25

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