EP1279517B1 - 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
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
Authority
EP
European Patent Office
Prior art keywords
pigments
plastic
process according
laser
marking
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.)
Expired - Lifetime
Application number
EP02016489A
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German (de)
English (en)
Other versions
EP1279517A3 (fr
EP1279517A2 (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
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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 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)
  • Inks, Pencil-Leads, Or Crayons (AREA)
  • Application Of Or Painting With Fluid Materials (AREA)
  • Dot-Matrix Printers And Others (AREA)
  • Laser Beam Printer (AREA)
  • Laser Beam Processing (AREA)
  • Laminated Bodies (AREA)

Claims (9)

  1. Procédé pour l'inscription colorée et le marquage coloré de matières plastiques ou de revêtements, caractérisé en ce que la surface de matière plastique ou de revêtement est recouverte d'un mélange qui est constitué par un ou plusieurs colorants et par une ou plusieurs substances absorbeuses de lumière laser et cette couche est transférée complètement sur une partie ou sur la totalité de la surface dans la surface de matière plastique ou de revêtement qui a été fondue par irradiation laser.
  2. Procédé selon la revendication 1, caractérisé en ce que le rapport colorant : substance absorbeuse de lumière laser est de 10 : 1 à 1 : 10.
  3. Procédé selon la revendication 1 ou 2, caractérisé en ce que le colorant est une teinture et/ou un pigment organique ou inorganique.
  4. Procédé selon la revendication 3, caractérisé en ce que le colorant est choisi parmi le groupe qui comprend les phthalocyanines de cuivre, les dioxazines, les anthraquinones, les pigments monoazo et diazo, le dikétopyrrolopyrrole, les pigments polycycliques, les anthrapyrimidines, les quinacridones, les quinaphthalones, les perynones, les perylènes, les acridines, les teintures azo, les phthalocyanines, les xanthènes et les phénazines, les pigments d'oxyde et d'oxy-hydroxyde colorés, les pigments à phase mixte d'oxyde, les pigments de sulfure et de sulfure/sélénium, les pigments de carbonate, les pigments à phase mixte de chromate et de chromate/molybdate, les pigments de sel complexe et les pigments de silicate.
  5. Procédé selon l'une des revendications 1 à 4, caractérisé en ce que la matière plastique est une matière plastique thermoplastique ou une matière plastique thermodurcissable.
  6. Procédé selon la revendication 5, caractérisé en ce que la matière plastique est constituée par polyéthylène, polypropylène, polyamide, polyester, polyester-ester, polyéther-ester, éther de polyphénylène, polyacétal, téréphthalate de polybutylène, méthacrylate de poly-méthyle, acétal de polyvinyle, polystyrène, acrylonitrile-butadiène-styrène (ABS), acrylonitrile-styrène-acrylate (ASA), polycarbonate, sulfones de polyéther et cétones de polyéther de même que des copolymères et/ou un mélange afférents.
  7. Procédé selon l'une des revendications 1 à 6, caractérisé en ce que la matière plastique ou le revêtement lui-même comprend une ou plusieurs substances absorbeuse(s) de lumière laser.
  8. Procédé selon l'une des revendications 1 à 7, caractérisé en ce qu'un laser CO2 ou Nd:YAG est utilisé.
  9. Moulages en matière plastique, revêtements et revêtements pulvérulents munis d'une inscription colorée ou d'un marquage coloré au moyen du procédé selon l'une des revendications 1 à 8.
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 EP1279517A2 (fr) 2003-01-29
EP1279517A3 EP1279517A3 (fr) 2003-06-25
EP1279517B1 true EP1279517B1 (fr) 2006-02-15

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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)

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Also Published As

Publication number Publication date
DE50205815D1 (de) 2006-04-20
JP2003175571A (ja) 2003-06-24
EP1279517A3 (fr) 2003-06-25
DE10136479A1 (de) 2003-02-06
EP1279517A2 (fr) 2003-01-29
US6924077B2 (en) 2005-08-02
US20040013969A1 (en) 2004-01-22
ATE317767T1 (de) 2006-03-15

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