EP0327508A2 - Process for laser marking of pigmented systems - Google Patents

Process for laser marking of pigmented systems Download PDF

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Publication number
EP0327508A2
EP0327508A2 EP89810091A EP89810091A EP0327508A2 EP 0327508 A2 EP0327508 A2 EP 0327508A2 EP 89810091 A EP89810091 A EP 89810091A EP 89810091 A EP89810091 A EP 89810091A EP 0327508 A2 EP0327508 A2 EP 0327508A2
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EP
European Patent Office
Prior art keywords
pigment
laser
marking
additive
bleachable
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.)
Withdrawn
Application number
EP89810091A
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German (de)
French (fr)
Other versions
EP0327508A3 (en
Inventor
Manfred Dr. Hofmann
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.)
Novartis AG
Original Assignee
Ciba Geigy AG
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Filing date
Publication date
Application filed by Ciba Geigy AG filed Critical Ciba Geigy AG
Publication of EP0327508A2 publication Critical patent/EP0327508A2/en
Publication of EP0327508A3 publication Critical patent/EP0327508A3/en
Withdrawn legal-status Critical Current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
    • B41M5/28—Thermography ; Marking by high energetic means, e.g. laser otherwise than by burning, and characterised by the material used using thermochromic compounds or layers containing liquid crystals, microcapsules, bleachable dyes or heat- decomposable compounds, e.g. gas- liberating
    • B41M5/286—Thermography ; Marking by high energetic means, e.g. laser otherwise than by burning, and characterised by the material used using thermochromic compounds or layers containing liquid crystals, microcapsules, bleachable dyes or heat- decomposable compounds, e.g. gas- liberating using compounds undergoing unimolecular fragmentation to obtain colour shift, e.g. bleachable dyes
    • 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
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B42—BOOKBINDING; ALBUMS; FILES; SPECIAL PRINTED MATTER
    • B42D—BOOKS; BOOK COVERS; LOOSE LEAVES; PRINTED MATTER CHARACTERISED BY IDENTIFICATION OR SECURITY FEATURES; PRINTED MATTER OF SPECIAL FORMAT OR STYLE NOT OTHERWISE PROVIDED FOR; DEVICES FOR USE THEREWITH AND NOT OTHERWISE PROVIDED FOR; MOVABLE-STRIP WRITING OR READING APPARATUS
    • B42D25/00—Information-bearing cards or sheet-like structures characterised by identification or security features; Manufacture thereof
    • B42D25/30—Identification or security features, e.g. for preventing forgery
    • B42D25/36—Identification or security features, e.g. for preventing forgery comprising special materials
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B42—BOOKBINDING; ALBUMS; FILES; SPECIAL PRINTED MATTER
    • B42D—BOOKS; BOOK COVERS; LOOSE LEAVES; PRINTED MATTER CHARACTERISED BY IDENTIFICATION OR SECURITY FEATURES; PRINTED MATTER OF SPECIAL FORMAT OR STYLE NOT OTHERWISE PROVIDED FOR; DEVICES FOR USE THEREWITH AND NOT OTHERWISE PROVIDED FOR; MOVABLE-STRIP WRITING OR READING APPARATUS
    • B42D25/00—Information-bearing cards or sheet-like structures characterised by identification or security features; Manufacture thereof
    • B42D25/30—Identification or security features, e.g. for preventing forgery
    • B42D25/36—Identification or security features, e.g. for preventing forgery comprising special materials
    • B42D25/378—Special inks
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B42—BOOKBINDING; ALBUMS; FILES; SPECIAL PRINTED MATTER
    • B42D—BOOKS; BOOK COVERS; LOOSE LEAVES; PRINTED MATTER CHARACTERISED BY IDENTIFICATION OR SECURITY FEATURES; PRINTED MATTER OF SPECIAL FORMAT OR STYLE NOT OTHERWISE PROVIDED FOR; DEVICES FOR USE THEREWITH AND NOT OTHERWISE PROVIDED FOR; MOVABLE-STRIP WRITING OR READING APPARATUS
    • B42D25/00—Information-bearing cards or sheet-like structures characterised by identification or security features; Manufacture thereof
    • B42D25/40—Manufacture
    • B42D25/405—Marking
    • B42D25/41—Marking using electromagnetic radiation
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03C—PHOTOSENSITIVE MATERIALS FOR PHOTOGRAPHIC PURPOSES; PHOTOGRAPHIC PROCESSES, e.g. CINE, X-RAY, COLOUR, STEREO-PHOTOGRAPHIC PROCESSES; AUXILIARY PROCESSES IN PHOTOGRAPHY
    • G03C7/00—Multicolour photographic processes or agents therefor; Regeneration of such processing agents; Photosensitive materials for multicolour processes
    • G03C7/02—Direct bleach-out processes; Materials therefor; Preparing or processing such materials

Definitions

  • the present invention relates to a method for laser inscription of high molecular organic material with colored contrast marking, and the inscribed material.
  • European Patent Application No. 0036680 it is proposed in European Patent Application No. 0036680 to mark an object, of which at least one surface part consists of a synthetic synthetic resin material, with a laser beam of a certain intensity.
  • the material to be marked contains a dye and a silicon-containing inorganic compound or a silicon-containing dye, the dye being decomposed by laser irradiation, which leads to the formation of a white marking at the irradiated areas with good color contrast with respect to the non-irradiated colored part of the material.
  • plastic parts with a colored contrast marking.
  • an additive that causes discoloration due to laser radiation for example an inorganic and / or organic pigment. This creates a change in color at the irradiated area of the material, usually black or white.
  • Japanese patent application Sho 60-155493 also deals with the laser marking of plastic parts or films with colored contrast markings, with a yellow iron oxide, possibly mixed with a yellow, yellowish green or red pigment, being mixed into the plastic. Laser radiation causes the yellow iron oxide to turn red at the irradiated areas, so that red, orange or brown markings are created.
  • Japanese Patent Application No. 58-210937 proposed plastic compositions for laser marking, the plastic being mixed with two different colorants, one of which evaporates during laser irradiation, discolors or fades and the other remains unchanged, so that a colored contrast marking is produced.
  • Some organic pigments and dyes are listed as examples of changing colorants, while some inorganic pigments are mentioned as stable compounds. This document does not indicate which laser devices, energy, power, wavelength and pulse duration are to be used for this.
  • the present invention accordingly relates to a method for laser marking high-molecular organic material in the form of objects, foils and films, according to which the material containing at least one radiation-sensitive bleachable additive and at least one less radiation-sensitive non-bleaching compound is exposed to a laser beam, the energy of the laser beam is directed towards the surface of the material to be marked in accordance with the shape of the marking to be applied, so that the Irradiated areas are given a visual, colorful contrast marking without the surface of the labeled material being visibly damaged by the eye, characterized in that pulsed laser light, the wavelength of which is in the near UV and / or visible range, is used, and in that it is used as a bleachable additive at least one azo and / or an indanthrone pigment and at least one inorganic and / or organic pigment and / or a polymer-soluble dye used as the non-bleaching compound.
  • the high molecular weight organic material can be of natural or artificial origin.
  • it can be natural resins, drying oils or rubber.
  • they can also be modified natural substances, for example chlorinated rubber, oil-modified alkyd resins or cellulose derivatives, such as cellulose esters or cellulose ethers, and in particular fully synthetic organic polyplastics, i.e. plastics that are produced by polymerization, polycondensation or polyaddition.
  • plastics From the class of these plastics, the following may be mentioned in particular: polyethylene, polypropylene, polyisobutylene, polystyrene, polyvinyl chloride, polyvinylidene chloride, polyvinyl acetals, polyacrylonitrile, polyacrylic acid and polymethacrylic acid esters or polybutadiene, and copolymers thereof, in particular ABS or EVA; Polyesters, especially high molecular esters of aromatic polycarboxylic acids with polyfunctional alcohols; Polyamides, polyimides, polycarbonates, polyurethanes, polyethers such as polyphenylene oxide, polyacetals, the condensation products of formaldehyde with phenols, the so-called phenoplasts, and the condensation products of formaldehyde with urea, thiourea and melamine, the so-called aminoplastics; the polyaddition or polycondensation products of epichlorohydrin with diols or polyphenols known under the name "e
  • High molecular weight organic materials in dissolved form as film formers or binders for paints or printing inks are also possible, e.g. Linseed oil varnish, nitrocellulose, alkyd resins, phenolic resins, melamine resins, acrylic resins and urea-formaldehyde resins, and the films obtained therefrom can be labeled according to the invention.
  • polyvinyl esters such as polyvinyl acetals, furthermore polyacrylic acid and polymethacrylic acid esters, polyesters, polyamides, polyimides, polycarbonates, polyurethanes, polyethers, in particular polyphenylene oxides, furthermore polyacetals such as polyoxymethylene, phenoplasts, aminoplasts or epoxy resins.
  • Very particularly suitable materials are polyacrylic acid and polymethacrylic acid esters, polyesters, polyamides, polycarbonates, polyphenylene oxides or an epoxy resin.
  • Polymethacrylic acid esters in particular methyl polymethacrylic acid esters, and epoxy resins are very particularly preferred.
  • Azo pigments which preferably absorb in the near UV and / or visible range are suitable as a radiation-sensitive bleachable additive.
  • the visible range is the range between 0.38 ⁇ m and 0.78 ⁇ m and the near UV range is the range between 0.25 ⁇ m and 0.38 ⁇ m.
  • Azo pigments which are suitable according to the invention are, for example, mono- and disazo pigments, such as, for example, mono- or disazo compounds of acetoacetarylide, pyrazolone, 2,3-oxynaphthoic acid arylide, barbituric acid, thiobarbituric acid, 2,4,6-triamino-pyrimidine-1, 3- and 3-cyano-4-methylpyridone series, as well as the metal salts of azo compounds.
  • mono- and disazo pigments such as, for example, mono- or disazo compounds of acetoacetarylide, pyrazolone, 2,3-oxynaphthoic acid arylide, barbituric acid, thiobarbituric acid, 2,4,6-triamino-pyrimidine-1, 3- and 3-cyano-4-methylpyridone series, as well as the metal salts of azo compounds.
  • Particularly suitable azo pigments are disazo pigments from the acetoacetarylide, pyrazolone and 2,3-oxynaphthoic acid arylide series.
  • Examples of azo pigments are C.I. Pigment Brown 23, Pigment Orange 31, Pigment Orange 60, Pigment Orange 64, Pigment Scarlet 160, Pigment Red 220 and Pigment Red 221, as well as ®Cyan Blue 2C (Ilford).
  • indanthrone pigment is the commercial product ®Cromophthal Blue A3R (C.I. Pigment Blue 60; Ciba-Geigy AG).
  • Examples of the present invention not ausbleichenden inorganic pigments are metal oxides such as titanium dioxide, nickel-antimony titanate, chromium-antimony titanate, manganese blue, manganese violet, cobalt blue, cobalt chromium blue, cobalt nickel gray, or ultramarine blue, further Berlin blue, lead chromate, lead sulfochromates and zirconium silicates such as Zirkonvanadiumblau and Zirkon rempliseodymgelb .
  • organic pigments as non-bleaching compounds according to the invention are anthraquinone, flavanthrone, phthalocyanine, perinone, perylene, dioxazine, thioindigo, isoindoline, isoindolinone, quinacridone, pyrrolopyrrole or quinophthalone pigments, furthermore metal complexes of e.g. Azo, azomethine or methine dyes, as well as the azo condensation pigment yellow pigment C.I. No. 93 and the azo pigment Pigment Yellow 116.
  • anthraquinone pigments are Pigment Red C.I. No. 177 and Pigment Yellow C.I. No.
  • an example of a flavanthrone pigment is Pigment Yellow C.I. No. 24
  • examples of phthalocyanines are Pigment Blue C.I. No. 15: 3 and Pigment Green C.I. No. 7
  • an example of a perylene pigment is Pigment Red C.I. No. 149.
  • Dispersion dyes such as those of the anthraquinone series, for example hydroxyl, amino, alkylamino, cyclohexylamino, arylamino, hydroxyamino or phenylmercaptoanthraquinones, and metal complexes of azo dyes, in particular 1: 2-chromium, are suitable, for example, as polymer-soluble dyes which do not bleach according to the invention - or cobalt complexes of monoazo dyes, also fluorescent dyes, such as those from the coumarin, naphthalimide, pyrazoline, acridine, xanthene, thioxanthene, oxazine, thiazine or benzothiazole series. Examples of this are Solvent Yellow CI No. 163 (anthraquinone derivative), Solvent Black CI No. 29 (1: 2 chromium complex), and Pigment Yellow CI No. 147 (anthraquinone derivative).
  • the anthraquinone derivatives are preferred polymer-soluble dyes according to the invention.
  • Copper phthalocyanine and chlorinated copper phthalocyanine are preferred as organic pigments and metal oxides, in particular titanium dioxide, Berlin blue, the lead chromates and lead sulfochromates and the zirconium silicates are preferred as inorganic pigments.
  • An inorganic or organic pigment or a polymer-soluble dye is expediently used as the non-bleaching compound, and an azo or indanthrone pigment is used as the bleachable additive.
  • inorganic and organic pigments which are suitable according to the invention and the polymer-soluble dyes can also be used in combination with fillers and / or white pigments, such as titanium dioxide (anatase, rutile), zinc oxide, antimony trioxide, zinc sulfide, basic lead carbonate or basic lead silicate.
  • fillers and / or white pigments such as titanium dioxide (anatase, rutile), zinc oxide, antimony trioxide, zinc sulfide, basic lead carbonate or basic lead silicate.
  • Suitable additives are, for example, fatty acids with at least 12 carbon atoms, such as stearic acid or behenic acid, their amides, salts or esters, such as magnesium stearate, zinc stearate, aluminum stearate or magnesium behenate, and also quaternary ammonium compounds, such as tri (C1-C4) alkylbenzylammonium salts, waxes, such as polyethylene wax, resin acids such as abietic acid, rosin soap, hydrogenated or dimerized rosin, C12-C18 paraffin disulfonic acids or alkylphenols.
  • fatty acids with at least 12 carbon atoms such as stearic acid or behenic acid
  • their amides, salts or esters such as magnesium stearate, zinc stearate, aluminum stearate or magnesium behenate
  • quaternary ammonium compounds such as tri (C1-C4) alkylbenzylammonium salts
  • waxes such as poly
  • the additive which can be bleached according to the invention and the non-bleaching compound can be used in the high-molecular organic material which is suitable according to the invention, e.g. present in amounts of 0.001 to 10% by weight, in particular 0.01 to 3% by weight, based on the high molecular weight organic material.
  • the bleachable additive and the non-bleaching compound are added to the high-molecular organic material to be processed into objects (molded parts), foils or films by methods known per se, for example in such a way that these two components are optionally in the form of masterbatches, the organic material using extruders, rolling mills, mixers or grinders.
  • the material obtained is then brought into the desired final shape by processes known per se, such as calendering, pressing, extrusion, brushing, centrifuging, casting, extruding or by injection molding.
  • plasticizers can be incorporated into the polymers before or after the incorporation of the additive according to the invention or the non-bleaching compound.
  • organic material such as fillers such as kaolin, mica, feldspar, wollastonite, aluminum silicate, barium sulfate, calcium sulfate, chalk, calcite and dolomite, and also light stabilizers, antioxidants, flame retardants, heat stabilizers, reinforcing agents, such as glass fibers, or processing aids which are customary in the processing of plastics and are known to the person skilled in the art.
  • fillers such as kaolin, mica, feldspar, wollastonite, aluminum silicate, barium sulfate, calcium sulfate, chalk, calcite and dolomite
  • light stabilizers antioxidants, flame retardants, heat stabilizers, reinforcing agents, such as glass fibers, or processing aids which are customary in the processing of plastics and are known to the person skilled in the art.
  • the high molecular weight organic materials and the above two color components are optionally used together with other paint and printing ink additives, finely dispersed or dissolved in a common organic solvent or solvent mixture. You can do this by dispersing or dissolving the individual components for yourself or several together, and only then bringing all the components together.
  • the homogenized lacquer or the printing ink is then applied to a substrate by methods known per se and baked or dried, and the lacquer or printing ink film obtained is then labeled according to the invention.
  • each of these color components into a separate lacquer or printing ink film, the lower layer applied to the substrate preferably containing the non-bleaching component.
  • High-energy laser sources are used to label the high-molecular organic materials that are possible according to the invention.
  • the energy radiation is corresponding to the shape of the character to be applied, e.g. almost directed vertically onto the surface of the material to be marked, optionally focused, a discoloration occurring at the irradiated points without the surface of the labeled material being visibly damaged by the eye.
  • laser sources are solid-state pulse lasers, such as ruby lasers or frequency-multiplied Nd: YAG lasers, pulsed lasers with additional devices, such as pulsed dye lasers or Raman shifters, and continuous wave lasers with pulse modifications (Q-Switch, Mode-Locker), for example based on CW Nd: YAG lasers with a frequency multiplier, or CW ion lasers (Ar, Kr), also pulsed metal vapor lasers, such as for example Cu vapor lasers or Au vapor lasers, or possibly powerful pulsed semiconductor lasers that emit visible light by frequency doubling, furthermore pulsed gas lasers such as excimer and nitrogen lasers.
  • solid-state pulse lasers such as ruby lasers or frequency-multiplied Nd: YAG lasers
  • pulsed lasers with additional devices such as pulsed dye lasers or Raman shifters
  • continuous wave lasers with pulse modifications Q-Switch, Mode-Locker
  • CW Nd YAG lasers with a frequency multipli
  • pulse energies up to a few joules, power densities up to terawatts per cm2, pulse widths from femto-seconds to micro-seconds and repetition rates up to gigahertz are possible. Pulse energies of microjoules to joules, power densities of Kilowatts per cm2 to 100 megawatts per cm2, pulse widths from micro-seconds to pico-seconds and repetition rates from Hertz to 250 Megahertz.
  • Pulsed or pulse-modified, frequency-doubled Nd YAG lasers or metal vapor lasers, such as Au or in particular Cu vapor lasers, and excimer lasers are preferably used.
  • a pulsed frequency-doubled Nd: YAG laser between 0.01 and 1 joule per cm2 of pulse energy, about 40 megawatt peak power, 6-8 nano-second pulse width and 20 Hertz repetition rate (model Quanta Ray DCR-2 A from Spectra Physics, Mountain View, California).
  • exposure is, for example, to 250 millijoules per cm2 of pulse energy, approximately 10 kilowatts of peak power, 30 nano-seconds pulse width and 6 kilohertz repetition rate.
  • Lasers with good adjustability of their laser parameters allow optimal adaptation to the needs of the materials to be labeled.
  • the optimal wavelength to be selected for irradiation is the one at which the radiation-sensitive bleachable additive absorbs the least, the non-bleaching compound and the organic material to be labeled on the other hand least absorb.
  • the bleachable additive and the non-bleaching compound With the right choice of the bleachable additive and the non-bleaching compound, a clear color change is also possible if both absorb the irradiated wavelength.
  • the mask method There are generally three different methods for labeling with lasers: the mask method, the linear labeling and the dot-matrix method.
  • the laser is preferably coupled to a laser labeling system, so that the inorganic material can be labeled with any numbers, letters and special characters programmed in a computer, for example.
  • the choice of the laser system with regard to power and repetition rate is basically based on the labeling method used. High power and low repetition rates, as with solid-state pulse lasers and excimer lasers, are preferred for mask exposures. Medium to low performance and fast repetition rates In the case of pulsed metal vapor lasers or continuous wave lasers with pulse modifications, they are preferred for labels that require dynamic beam guidance.
  • the beam deflection can take place, for example, acousto-optically, holographically, with galvo mirrors or polygon scanners.
  • the dynamic beam guidance enables extremely flexible labeling or marking, since the characters can be generated electronically.
  • plastic objects, shapes or foils as well as lacquer and printing ink films can be labeled using the method according to the invention. Examples of this are tapes, boards, tubes and profiles, buttons and plastic-encased electronic components or parts with different colors produced using the two-phase injection molding process.
  • Typical application examples are the labeling of switches, printed circuit boards, printed circuits, active and passive electronic components, encapsulated high-voltage transformers, plugs and sockets, housings, mechanical components from the precision engineering and watch industry, vehicle components, keyboards, electronic components, cables, pipes, paints, Films, films and packaging foils, banknotes, credit cards and securities, as well as display windows and dials.
  • the method according to the invention enables a colorful contrast marking, which cannot be blurred and is therefore resistant to abrasion and scratches.
  • the markings obtained according to the invention are also corrosion-resistant, dimensionally stable, deformation-free, light-, heat- and weatherproof, and legible and have clean margins.
  • the mechanical and physical properties of the material so labeled are practically unaffected, such as mechanical strength and chemical resistance.
  • the depth of penetration of the marking depends on the labeled material. It is usually less than 1 mm.
  • the high-molecular organic material is largely protected. Inscriptions are therefore possible that do not cause any loss of surface gloss that can be seen by the eye and do not impair the strength properties of the workpiece.
  • a color change with a pronounced contrast occurs at the irradiated areas of the material under laser irradiation.
  • ®Araldit GY 250 epoxy resin diglycidyl ether of bisphenol A with an epoxy content between 5.25-5.4 VAL per kg, from Ciba-Geigy AG, Switzerland
  • ®Cromophthal Red G diisazo condensation pigment, CI Pigment Red 220 , Ciba-Geigy AG
  • the viscous lacquer is applied to a cleaned, grease-free glass plate (microscope slide) with a drawing stick for 100 ⁇ m wet film thickness and cured in a drying
  • the finished layer is labeled with a laser beam deflected via two orthogonal movable mirrors in accordance with the shape of the marking to be applied.
  • An Nd: YAG pulse laser (®Quanta Ray DCR 2, Spectra Physics) with frequency doubler (harmonic generator) and frequency filter (harmonic separator) is used as the laser source.
  • the laser is adjusted and attenuated with neutral filters so that the beam, which is focused vertically via a lens (focal length 200 mm) on the slice, reaches a pulse energy of 0.2 mJ with a pulse width of 10 nano-seconds.
  • the deflection unit with the orthogonal, movable mirrors is part of a ®GRETAG 6210 laser marking system (GRETAG AG, Switzerland). The inscription obtained in this way appears green on the dark blue colored paint.
  • Laser marking is carried out analogously to Example 1; a yellow label is created on the orange colored background.
  • a coating solution is prepared by dissolving 75 g of polymethyl methacrylate (PMMA, ®LUCITE from DuPont) in 425 g of methyl ethyl ketone (MEK) with stirring at room temperature for 48 hours on a magnetic stirrer.
  • a first colored lacquer is produced by intensively mixing 50 g of the above lacquer solution with 79 mg ®Cromophthal Red G (disazo condensation pigment, C.I. Pigment Red 220, Ciba-Geigy AG) in an ultrasonic bath; a second color lacquer is produced in the same way from 50 g of the same lacquer solution and 413 mg ®Cromophthal Green GFN (halogenated copper phthalocyanine, C.I.
  • Example 1 Pigment Green 7, Ciba-Geigy AG.
  • the same parts of the first and second color varnish are mixed homogeneously, then drawn onto a slide with a drawing stick for 100 ⁇ m wet film thickness.
  • the film is dried in an oven at 50 ° C. for one hour, then labeled as in Example 1; a green label is created on the purple background.
  • ®Cromophthal Red G can also be used as a bleachable compound in other systems, such as in a PVB or PES film.
  • PVB stands for polyvinyl butyral (e.g. ®Movital B30H, Hoechst AG), PES for a polyester (e.g. ®Dynapol L206, Dynamit Nobel).
  • ®Movital B3OH e.g. in 2-methoxyethanol
  • ®Dynapol L206 e.g. be dissolved in tetrahydrofuran.
  • polyacetal copolymer ®Ultraform N 2320 polyoxymethylene base, BASF
  • polyacetal copolymer ®Ultraform N 2320 polyoxymethylene base, BASF
  • 0.24 g ®Cromophthal Braun 5R diisazo condensation pigment, CI Pigment Braun 23, Ciba-Geigy AG
  • 0.08 g ®Cromophthal Red BRN diisazocondensation pigment, CI Pigment Red 144, Ciba-Geigy AG
  • 0.18 g ®Cromophthal Blue A3R indanthrone pigment, CI Pigment Blue 60, Ciba-Geigy AG
  • 2 g titanium dioxide mixed dry and extruded at 180-190 ° C.
  • the granulated compound thus obtained is injected at 180-190 ° C into molded parts (width: 5 cm; length: 6 cm; thickness; 2 mm).
  • the gray areas to be marked are marked with a labeling system ®Gretag 6411-System 2 (Gretag AG, Switzerland).
  • a continuously pumped, Q-switched Nd: YAG laser serves as the laser source and is frequency-doubled, the energy of the laser beam being directed onto the surface of the material to be marked in accordance with the shape of the marking to be applied.
  • the laser beam with an energy of 0.1-1.0 mJ and a pulse width of 100-400 ns (nano-seconds) is focused on the surface to be marked via a lens with a focal length of 160 mm.
  • the lettering obtained appears in white on a gray background.
  • polyacetal copolymer ®Ultraform N 2320 100 g polyacetal copolymer ®Ultraform N 2320 (BASF) are mixed with 0.08 g ®Cromophthal scarlet RN (disazo condensation pigment, CI Pigment Red 166, Ciba-Geigy AG), 0.09 g ®Cromophthal green GFN (copper phthalocyanine pigment, CI pigment green 7) and 0.5 g of titanium dioxide mixed dry.
  • the granules obtained are extruded as in Example 5, injection molded into shaped articles and marked. The marking appears green on the gray background.
  • 100 g polyacetal copolymer ®Ultraform N 2320 are mixed with 0.1 g ®Cromophthal Braun 5R (disazo condensation pigment, CI Pigment Braun 23, Ciba-Geigy AG), 0.05 g ®Cromophthal Blue 4GNP ( ⁇ -copper phthalocyanine pigment, CI Pigment Blue 15: 3, Ciba-Geigy AG), 0.04 g ®Cromophthal Red BRN (disazo condensation pigment, CI Pigment Red 144, Ciba-Geigy AG) and 1 g of titanium dioxide dry mixed, and the granules obtained are extruded as described in Example 5, injected into molded parts and marked. The marking appears blue on the gray background.
  • ®Cromophthal Braun 5R diazo condensation pigment, CI Pigment Braun 23, Ciba-Geigy AG
  • 0.05 g ®Cromophthal Blue 4GNP ⁇ -copper phthalocyanine pigment, CI Pigment Blue

Abstract

Process for the laser marking of high-molecular-weight organic material in the form of objects, sheets and films in which the material, containing at least one radiation-sensitive bleachable additive and at least one less radiation-sensitive nondiscolourable compound, is exposed to a laser beam, where the energy of the laser beam is directed on to the surface of the material to be given the marking in a manner corresponding to the design of the marking to be applied, so that a visual, coloured contrast marking develops at the irradiated points without there being any damage to the surface of the marked material which is visible to the eye, characterised in that pulsed laser light is used with a wavelength in the near UV and/or visible region and that at least one azo pigment and/or one indanthrone pigment is used as the bleachable additive and at least one inorganic and/or organic pigment and/or a polymer-soluble dye is used as the non-bleaching compound. The laser marking is carried out using masks or by means of a guided beam under computer control, in which case, however, a pulsed or pulse-modified laser is used.

Description

Die vorliegende Erfindung betrifft ein Verfahren zur Laserbeschriftung von hochmolekularem organischem Material mit bunter Kontrastmarkierung, sowie das beschriftete Material.The present invention relates to a method for laser inscription of high molecular organic material with colored contrast marking, and the inscribed material.

Das Lasermarkieren von Kunststoffgegenständen durch Bildung einer Farbkontrastmarkierung an den bestrahlten Stellen ist bekannt.Laser marking of plastic objects by forming a color contrast marking on the irradiated areas is known.

So wird beispielsweise in der europäischen Patentanmeldung Nr. 0036680 vorgeschlagen, einen Gegenstand, von dem wenigstens ein Oberflächenteil aus einem synthetischen Kunstharzmaterial besteht, mit einem Laserstrahl einer bestimmten Intensität zu markieren. Das zu markierende Material enthält einen Farbstoff und eine siliziumhaltige anorganische Verbindung oder einen siliziumhaltigen Farbstoff, wobei sich der Farbstoff durch Laserbestrahlung zersetzt, was an den bestrahlten Stellen zur Bildung einer weissen Markierung mit gutem Farbkontrast gegenüber dem nicht bestrahlten farbigen Teil des Materials führt.For example, it is proposed in European Patent Application No. 0036680 to mark an object, of which at least one surface part consists of a synthetic synthetic resin material, with a laser beam of a certain intensity. The material to be marked contains a dye and a silicon-containing inorganic compound or a silicon-containing dye, the dye being decomposed by laser irradiation, which leads to the formation of a white marking at the irradiated areas with good color contrast with respect to the non-irradiated colored part of the material.

Es ist weiterhin auch bekannt, Kunststoffteile mit einer bunten Kontrast­markierung zu beschriften. So werden gemäss der europäischen Patentan­meldung Nr. 0190997 hochmolekulare, organische Materialien in Form von Teilen, Folien oder Filmen beschriftet, wobei ein eine Verfärbung durch Laserbestrahlung verursachender Zusatzstoff, z.B. ein anorganisches und/oder organisches Pigment, verwendet wird. Dabei entsteht an der bestrahlten Stelle des Materials ein Farbumschlag, meistens nach schwarz oder weiss.It is also known to label plastic parts with a colored contrast marking. For example, according to European Patent Application No. 0190997, high-molecular organic materials in the form of parts, foils or films are labeled, using an additive that causes discoloration due to laser radiation, for example an inorganic and / or organic pigment. This creates a change in color at the irradiated area of the material, usually black or white.

Auch die japanische Patentanmeldung Sho 60-155493 befasst sich mit der Laserbeschriftung von Kunststoffteilen oder -filmen mit bunter Kontrast­markierung, wobei dem Kunststoff ein gelbes Eisenoxid, gegebenenfalls in Abmischumg mit einem gelben, gelbstichig grünen oder rotem Pigment, beigemischt wird. Durch Laserbestrahlung verfärbt sich das gelbe Eisen­oxid an den bestrahlten Stellen rot, so dass rote, orange oder braune Markierungen entstehen.Japanese patent application Sho 60-155493 also deals with the laser marking of plastic parts or films with colored contrast markings, with a yellow iron oxide, possibly mixed with a yellow, yellowish green or red pigment, being mixed into the plastic. Laser radiation causes the yellow iron oxide to turn red at the irradiated areas, so that red, orange or brown markings are created.

Schliesslich werden in der japanischen Patentanmeldung No. 58-210937 Kunststoffzusammensetzungen für die Laserbeschriftung vorgeschlagen, wobei dem Kunststoff zwei verschiedene Farbmittel beigemischt werden, von denen das eine bei der Laserbestrahlung abdampft, sich verfärbt oder ausbleicht und das andere unverändert bleibt, so dass eine farbige Kontrastmarkierung entsteht. Als Beispiele für sich verändernde Farb­mittel sind dort einige organische Pigmente und Farbstoffe aufgeführt, währenddem als stabile Verbindungen einige anorganische Pigmente erwähnt sind. Welche Lasergeräte, -energie, -leistung, -wellenlänge und Pulsdauer hierfür anzuwenden sind, ist diesem Dokument nicht zu entnehmen.Finally, Japanese Patent Application No. 58-210937 proposed plastic compositions for laser marking, the plastic being mixed with two different colorants, one of which evaporates during laser irradiation, discolors or fades and the other remains unchanged, so that a colored contrast marking is produced. Some organic pigments and dyes are listed as examples of changing colorants, while some inorganic pigments are mentioned as stable compounds. This document does not indicate which laser devices, energy, power, wavelength and pulse duration are to be used for this.

Die oben aufgeführten Verfahren bzw. Zusammensetzungen vermögen jedoch den heutigen Anforderungen der Praxis nicht immer zu genügen; meistens wird die Oberfläche des beschrifteten Materials an den bestrahlten Stellen beschädigt, was zu unerwünschten Rillen, Vertiefungen oder Verätzungen führt und darüber hinaus zu Markierungen ungenügender allgemeiner Qualitäten, wie ungenügende Abrieb- und Kratzfestigkeit, schlechte Beständigkeit gegen Chemikalien und Verschmutzung sowie Deformation, und unsaubere Randzonen, führt.However, the methods and compositions listed above are not always able to meet today's practical requirements; mostly the surface of the labeled material is damaged at the irradiated areas, which leads to undesirable grooves, depressions or burns and also to markings of insufficient general qualities, such as insufficient abrasion and scratch resistance, poor resistance to chemicals and dirt as well as deformation, and unclean edge zones , leads.

Gegenstand der vorliegenden Erfindung ist demnach ein Verfahren zur Laserbeschriftung von hochmolekularem organischem Material in Form von Gegenständen, Folien und Filmen, wonach das mindestens einen strahlungs­empfindlichen ausbleichbaren Zusatzstoff und mindestens eine weniger strahlungsempfindliche nicht ausbleichende Verbindung enthaltende Material einem Laserstrahl ausgesetzt ist, wobei die Energie des Laser­strahls entsprechend der Form der aufzubringenden Markierung auf die Oberfläche des zu markierenden Materials gerichtet wird, so dass an den bestrahlten Stellen eine visuelle bunte Kontrastmarkierung entsteht, ohne dass die Oberfläche des beschrifteten Materials von Auge erkennbar beschädigt wird, dadurch gekennzeichnet, dass man gepulstes Laserlicht, dessen Wellenlänge im nahen UV- und/oder sichtbaren Bereich liegt, verwendet, und dass man als ausbleichbaren Zusatzstoff mindestens ein Azo- und/oder ein Indanthronpigment und als nicht ausbleichende Verbin­dung mindestens ein anorganisches und/oder organisches Pigment und/oder einen polymerlöslichen Farbstoff verwendet.The present invention accordingly relates to a method for laser marking high-molecular organic material in the form of objects, foils and films, according to which the material containing at least one radiation-sensitive bleachable additive and at least one less radiation-sensitive non-bleaching compound is exposed to a laser beam, the energy of the laser beam is directed towards the surface of the material to be marked in accordance with the shape of the marking to be applied, so that the Irradiated areas are given a visual, colorful contrast marking without the surface of the labeled material being visibly damaged by the eye, characterized in that pulsed laser light, the wavelength of which is in the near UV and / or visible range, is used, and in that it is used as a bleachable additive at least one azo and / or an indanthrone pigment and at least one inorganic and / or organic pigment and / or a polymer-soluble dye used as the non-bleaching compound.

Das hochmolekulare organische Material kann natürlicher oder künstlicher Herkunft sein. Es kann sich z.B. um Naturharze, trocknende Oele oder Kautschuk handeln. Es kann sich aber auch um abgewandelte Naturstoffe handeln, beispielsweise um Chlorkautschuk, um ölmodifizierte Alkydharze oder um Cellulosederivate, wie Celluloseester oder Celluloseäther, und besonders um vollsynthetische organische Polyplaste, das heisst um Kunststoffe, die durch Polymerisation, Polykondensation oder Polyaddi­tion hergestellt sind. Aus der Klasse dieser Kunststoffe seien besonders folgende genannt: Polyäthylen, Polypropylen, Polyisobutylen, Polystyrol, Polyvinylchlorid, Polyvinylidenchlorid, Polyvinylacetale, Polyacryl­nitril, Polyacrylsäure- und Polymethacrylsäureester oder Polybutadien, sowie Copolymerisate davon, insbesondere ABS oder EVA; Polyester, insbe­sondere hochmolekulare Ester aromatischer Polycarbonsäuren mit poly­funktionellen Alkoholen; Polyamide, Polyimide, Polycarbonate, Poly­urethane, Polyäther wie Polyphenylenoxid, Polyacetale, die Kondensa­tionsprodukte von Formaldehyd mit Phenolen, die sogenannten Phenoplaste, und die Kondensationsprodukte von Formaldehyd mit Harnstoff, Thioharn­stoff und Melamin, die sogenannten Aminoplaste; die unter dem Namen "Epoxyharze" bekannten Polyadditions- bzw. Polykondensationsprodukte von Epichlorhydrin mit Diolen oder Polyphenolen und ferner die als Lackharze verwendeten Polyester, und zwar sowohl gesättigte, wie z.B. Alkydharze als auch ungesättigte, wie beispielsweise Maleinatharze. Es sei betont, dass nicht nur die einheitlichen Verbindungen, sondern auch Gemische von Polyplasten, sowie Mischkondensate und Mischpolymerisate, wie z.B. solche auf Basis von Butadien, erfindungsgemäss verwendet werden können.The high molecular weight organic material can be of natural or artificial origin. For example, it can be natural resins, drying oils or rubber. However, they can also be modified natural substances, for example chlorinated rubber, oil-modified alkyd resins or cellulose derivatives, such as cellulose esters or cellulose ethers, and in particular fully synthetic organic polyplastics, i.e. plastics that are produced by polymerization, polycondensation or polyaddition. From the class of these plastics, the following may be mentioned in particular: polyethylene, polypropylene, polyisobutylene, polystyrene, polyvinyl chloride, polyvinylidene chloride, polyvinyl acetals, polyacrylonitrile, polyacrylic acid and polymethacrylic acid esters or polybutadiene, and copolymers thereof, in particular ABS or EVA; Polyesters, especially high molecular esters of aromatic polycarboxylic acids with polyfunctional alcohols; Polyamides, polyimides, polycarbonates, polyurethanes, polyethers such as polyphenylene oxide, polyacetals, the condensation products of formaldehyde with phenols, the so-called phenoplasts, and the condensation products of formaldehyde with urea, thiourea and melamine, the so-called aminoplastics; the polyaddition or polycondensation products of epichlorohydrin with diols or polyphenols known under the name "epoxy resins" and also the polyesters used as coating resins, both saturated, such as, for example, alkyd resins and unsaturated, such as, for example, maleate resins. It should be emphasized that not only the uniform compounds, but also mixtures of polyplastics, and also mixed condensates and copolymers, such as, for example, those based on butadiene, can be used according to the invention.

Hochmolekulare organische Materialen in gelöster Form als Filmbildner oder Bindemittel für Lacke oder Druckfarben kommen auch in Frage, wie z.B. Leinölfirnis, Nitrocellulose, Alkydharze, Phenolharze, Melamin­harze, Acrylharze und Harnstoff-Formaldehydharze, wobei die daraus erhaltenen Filme erfindungsgemäss beschriftet werden können.High molecular weight organic materials in dissolved form as film formers or binders for paints or printing inks are also possible, e.g. Linseed oil varnish, nitrocellulose, alkyd resins, phenolic resins, melamine resins, acrylic resins and urea-formaldehyde resins, and the films obtained therefrom can be labeled according to the invention.

Für das erfindungsgemässe Verfahren besonders geeignete Materialien sind Polyvinylester, wie Polyvinylacetale, ferner Polyacrylsäure-und Poly­methacrylsäureester, Polyester, Polyamide, Polyimide, Polycarbonate, Polyurethane, Polyäther, insbesondere Polyphenylenoxide, ferner Poly­acetale wie Polyoxymethylen, Phenoplaste, Aminoplaste oder Epoxyharze.Materials particularly suitable for the process according to the invention are polyvinyl esters, such as polyvinyl acetals, furthermore polyacrylic acid and polymethacrylic acid esters, polyesters, polyamides, polyimides, polycarbonates, polyurethanes, polyethers, in particular polyphenylene oxides, furthermore polyacetals such as polyoxymethylene, phenoplasts, aminoplasts or epoxy resins.

Ganz besonders geeignete Materialien sind Polyacrylsäure- und Poly­methacrylsäureester, Polyester, Polyamide, Polycarbonate, Polyphenylen­oxide oder ein Epoxyharz.Very particularly suitable materials are polyacrylic acid and polymethacrylic acid esters, polyesters, polyamides, polycarbonates, polyphenylene oxides or an epoxy resin.

Ganz besonders bevorzugt sind Polymethacrylsäureester, insbesonders Polymethacrylsäuremethylester, und Epoxyharze.Polymethacrylic acid esters, in particular methyl polymethacrylic acid esters, and epoxy resins are very particularly preferred.

Als strahlungsempfindlicher ausbleichbarer Zusatzstoff kommen Azopigmente in Frage, welche vorzugsweise im nahen UV- und/oder sichtbaren Bereich absorbieren.Azo pigments which preferably absorb in the near UV and / or visible range are suitable as a radiation-sensitive bleachable additive.

Unter sichtbarem Bereich versteht man den Bereich zwischen 0,38 µm und 0,78 µm und unter nahem UV-Bereich den Bereich zwischen 0,25 µm und 0,38 µm.The visible range is the range between 0.38 µm and 0.78 µm and the near UV range is the range between 0.25 µm and 0.38 µm.

Erfindungsgemäss in Frage kommende Azopigmente sind z.B. Mono- und Disazopigmente, wie z.B. Mono- oder Disazoverbindungen der Acetoacet­arylid-, Pyrazolon-, 2,3-Oxynaphthoesäurearylid-, Barbitursäure-, Thiobarbitursäure-, 2,4,6-Triamino-pyrimidin-1,3- und 3-Cyano-4-methyl­pyridon-Reihe, sowie die Metallsalze von Azoverbindungen.Azo pigments which are suitable according to the invention are, for example, mono- and disazo pigments, such as, for example, mono- or disazo compounds of acetoacetarylide, pyrazolone, 2,3-oxynaphthoic acid arylide, barbituric acid, thiobarbituric acid, 2,4,6-triamino-pyrimidine-1, 3- and 3-cyano-4-methylpyridone series, as well as the metal salts of azo compounds.

Besonders geeignete Azopigmente sind Disazopigmente der Acetoacet­arylid-, Pyrazolon- und 2,3-Oxynaphthoesäurearylidreihe. Beispiele von Azopigmenten sind C.I. Nr. Pigment Braun 23, Pigment Orange 31, Pigment Orange 60, Pigment Orange 64, Pigment Scharlach 160, Pigment Rot 220 und Pigment Rot 221, sowie ®Cyan Blau 2C (Ilford).Particularly suitable azo pigments are disazo pigments from the acetoacetarylide, pyrazolone and 2,3-oxynaphthoic acid arylide series. Examples of azo pigments are C.I. Pigment Brown 23, Pigment Orange 31, Pigment Orange 60, Pigment Orange 64, Pigment Scarlet 160, Pigment Red 220 and Pigment Red 221, as well as ®Cyan Blue 2C (Ilford).

Ein Beispiel eines Indanthronpigments ist das Handelsprodukt ®Cromophtal Blau A3R (C.I. Pigment Blau 60; Ciba-Geigy AG).An example of an indanthrone pigment is the commercial product ®Cromophthal Blue A3R (C.I. Pigment Blue 60; Ciba-Geigy AG).

Beispiele von erfindungsgemäss nicht ausbleichenden anorganischen Pigmenten sind Metalloxide, wie Titandioxid, Nickel-antimon-titanat, Chrom-antimon-titanat, Manganblau, Manganviolett, Kobaltblau, Kobalt­chromblau, Kobaltnickelgrau oder Ultramarinblau, ferner Berlinerblau, Bleichromate, Bleisulfochromate und Zirkonsilikate, wie Zirkonvanadium­blau und Zirkonpräseodymgelb.Examples of the present invention not ausbleichenden inorganic pigments are metal oxides such as titanium dioxide, nickel-antimony titanate, chromium-antimony titanate, manganese blue, manganese violet, cobalt blue, cobalt chromium blue, cobalt nickel gray, or ultramarine blue, further Berlin blue, lead chromate, lead sulfochromates and zirconium silicates such as Zirkonvanadiumblau and Zirkonpräseodymgelb .

Beispiele von organischen Pigmenten als erfindungsgemäss nichtausblei­chende Verbindungen sind Anthrachinon-, Flavanthron-, Phthalocyanin-, Perinon-, Perylen-, Dioxazin-, Thioindigo-, Isoindolin-, Isoindolinon-, Chinacridon-, Pyrrolopyrrol- oder Chinophthalonpigmente, ferner Metall­komplexe von z.B. Azo-, Azomethin-oder Methinfarbstoffen, sowie das Azokondensationspigment Pigment Gelb C.I. Nr. 93 und das Azopigment Pigment Gelb 116. Beispiele von Anthrachinonpigmenten sind Pigment Rot C.I. Nr. 177 und Pigment Gelb C.I. Nr. 147, ein Beispiel für ein Flavanthronpigment ist Pigment Gelb C.I. Nr. 24, Beispiele für Phthalo­cyanine sind Pigment Blau C.I. Nr. 15:3 und Pigment Grün C.I. Nr. 7, und ein Beispiel für ein Perylenpigment ist Pigment Rot C.I. Nr. 149.Examples of organic pigments as non-bleaching compounds according to the invention are anthraquinone, flavanthrone, phthalocyanine, perinone, perylene, dioxazine, thioindigo, isoindoline, isoindolinone, quinacridone, pyrrolopyrrole or quinophthalone pigments, furthermore metal complexes of e.g. Azo, azomethine or methine dyes, as well as the azo condensation pigment yellow pigment C.I. No. 93 and the azo pigment Pigment Yellow 116. Examples of anthraquinone pigments are Pigment Red C.I. No. 177 and Pigment Yellow C.I. No. 147, an example of a flavanthrone pigment is Pigment Yellow C.I. No. 24, examples of phthalocyanines are Pigment Blue C.I. No. 15: 3 and Pigment Green C.I. No. 7, and an example of a perylene pigment is Pigment Red C.I. No. 149.

Als erfindungsgemäss nicht ausbleichende polymerlösliche Farbstoffe eignen sich beispielsweise Dispersionsfarbstoffe, wie solche der Anthra­chinonreihe, beispielsweise Hydroxy-, Amino-, Alkylamino-, Cyclohexyl­amino-, Arylamino-, Hydroxyamino- oder Phenylmercapto-anthrachinone, sowie Metallkomplexe von Azofarbstoffen, insbesondere 1:2-Chrom- oder Kobaltkomplexe von Monoazofarbstoffen, ferner Fluoreszenzfarbstoffe, wie solche aus der Cumarin-, Naphthalimid-, Pyrazolin-, Acridin-, Xanthen-, Thioxanthen-, Oxazin-, Thiazin- oder Benzthiazolreihe. Beispiele hierfür sind Solvent Gelb C.I. Nr. 163 (Anthrachinonderivat), Solvent Schwarz C.I. Nr. 29 (1:2-Chromkomplex), und Pigment Gelb C.I. Nr. 147 (Anthra­chinonderivat).Dispersion dyes such as those of the anthraquinone series, for example hydroxyl, amino, alkylamino, cyclohexylamino, arylamino, hydroxyamino or phenylmercaptoanthraquinones, and metal complexes of azo dyes, in particular 1: 2-chromium, are suitable, for example, as polymer-soluble dyes which do not bleach according to the invention - or cobalt complexes of monoazo dyes, also fluorescent dyes, such as those from the coumarin, naphthalimide, pyrazoline, acridine, xanthene, thioxanthene, oxazine, thiazine or benzothiazole series. Examples of this are Solvent Yellow CI No. 163 (anthraquinone derivative), Solvent Black CI No. 29 (1: 2 chromium complex), and Pigment Yellow CI No. 147 (anthraquinone derivative).

Erfindungsgemäss bevorzugte polymerlösliche Farbstoffe sind die Anthra­chinonderivate. Als organische Pigmente sind Kupferphthalocyanin und chloriertes Kupferphthalocyanin und als anorganische Pigmente die Metalloxide, insbesonders Titandioxid, Berlinerblau, die Bleichromate und Bleisulfochromate sowie die Zirkonsilikate bevorzugt.The anthraquinone derivatives are preferred polymer-soluble dyes according to the invention. Copper phthalocyanine and chlorinated copper phthalocyanine are preferred as organic pigments and metal oxides, in particular titanium dioxide, Berlin blue, the lead chromates and lead sulfochromates and the zirconium silicates are preferred as inorganic pigments.

Zweckmässig verwendet man als nicht ausbleichende Verbindung ein anor­ganisches oder organisches Pigment oder einen polymerlöslichen Farbstoff, und als ausbleichbaren Zusatzstoff ein Azo- oder Indanthronpigment.An inorganic or organic pigment or a polymer-soluble dye is expediently used as the non-bleaching compound, and an azo or indanthrone pigment is used as the bleachable additive.

Die obigen, erfindungsgemäss in Frage kommenden anorganischen und organischen Pigmente sowie die polymerlöslichen Farbstoffe können auch in Kombination mit Füllern und/oder Weisspigmenten, wie Titandioxide (Anatas, Rutil), Zinkoxid, Antimontrioxid, Zinksulfid, basisches Blei­carbonat oder basisches Bleisilikat, eingesetzt werden.The above-mentioned inorganic and organic pigments which are suitable according to the invention and the polymer-soluble dyes can also be used in combination with fillers and / or white pigments, such as titanium dioxide (anatase, rutile), zinc oxide, antimony trioxide, zinc sulfide, basic lead carbonate or basic lead silicate.

Sie können aber auch mit anderen, dem Fachmann geläufigen Zusätzen verwendet werden. Es muss lediglich darauf geachtet werden, dass diese Zusätze mit dem erfindungsgemäss verwendeten hochmolekularen organischen Material verträglich sind und dessen mechanische oder sonstige Eigen­schaften nicht beeinträchtigen. Geeignete Zusätze sind beispielsweise Fettsäuren mit mindestens 12 C-Atomen, wie Stearinsäure oder Behensäure, deren Amide, Salze oder Ester, wie Magnesiumstearat, Zinkstearat, Aluminiumstearat oder Magnesiumbehenat, ferner quartäre Ammoniumver­bindungen, wie Tri-(C₁-C₄)-alkylbenzylammoniumsalze, Wachse, wie Polyäthylenwachs, Harzsäuren, wie Abietinsäure, Kolophoniumseife, hydriertes oder dimerisiertes Kolophonium, C₁₂-C₁₈-Paraffindisulfonsäuren oder Alkylphenole.However, they can also be used with other additives known to the person skilled in the art. It is only necessary to ensure that these additives are compatible with the high molecular weight organic material used according to the invention and do not impair its mechanical or other properties. Suitable additives are, for example, fatty acids with at least 12 carbon atoms, such as stearic acid or behenic acid, their amides, salts or esters, such as magnesium stearate, zinc stearate, aluminum stearate or magnesium behenate, and also quaternary ammonium compounds, such as tri (C₁-C₄) alkylbenzylammonium salts, waxes, such as polyethylene wax, resin acids such as abietic acid, rosin soap, hydrogenated or dimerized rosin, C₁₂-C₁₈ paraffin disulfonic acids or alkylphenols.

Der erfindungsgemäss ausbleichbare Zusatzstoff und die nicht ausblei­chende Verbindung können im erfindungsgemäss in Frage kommenden hoch­molekularen organischen Material z.B. in Mengen von 0,001 bis 10 Gew.-%, insbesondere von 0,01 bis 3 Gew.-%, bezogen auf das hochmolekulare organische Material, vorliegen.The additive which can be bleached according to the invention and the non-bleaching compound can be used in the high-molecular organic material which is suitable according to the invention, e.g. present in amounts of 0.001 to 10% by weight, in particular 0.01 to 3% by weight, based on the high molecular weight organic material.

Die Zugabe des ausbleichbaren Zusatzstoffes und der nicht ausbleichenden Verbindung zu dem zu Gegenständen (Formteilen), Folien oder Filmen zu verarbeitenden hochmolekularen organischen Material erfolgt nach an sich bekannten Methoden, beispielsweise derart, dass man diese beiden Kompo­nenten gegebenenfalls in Form von Masterbatches, dem organischen Material unter Verwendung von Extrudern, Walzwerken, Misch- oder Mahl­apparaten zumischt. Das erhaltene Material wird hierauf nach an sich bekannten Verfahren wie Kalandrieren, Pressen, Strangpressen, Streichen, Schleudern, Giessen, Extrudieren oder durch Spritzguss in die gewünschte endgültige Form gebracht. Oft ist es erwünscht, zur Herstellung von nicht starren Formlingen oder zur Verringerung ihrer Sprödigkeit, den hoch­molekularen organischen Verbindungen vor der Verformung sogenannte Weichmacher einzuverleiben. Als solche können z.B. Ester der Phosphor­säure, Phthalsäure oder Sebacinsäure dienen. Die Weichmacher können vor oder nach der Einverleibung des erfindungsgemäss in Frage kommenden Zusatzstoffes bzw. der nicht ausbleichenden Verbindung in die Polymeren eingearbeitet werden.The bleachable additive and the non-bleaching compound are added to the high-molecular organic material to be processed into objects (molded parts), foils or films by methods known per se, for example in such a way that these two components are optionally in the form of masterbatches, the organic material using extruders, rolling mills, mixers or grinders. The material obtained is then brought into the desired final shape by processes known per se, such as calendering, pressing, extrusion, brushing, centrifuging, casting, extruding or by injection molding. It is often desirable to incorporate so-called plasticizers into the high-molecular organic compounds before the molding in order to produce non-rigid moldings or to reduce their brittleness. As such, e.g. Serve esters of phosphoric acid, phthalic acid or sebacic acid. The plasticizers can be incorporated into the polymers before or after the incorporation of the additive according to the invention or the non-bleaching compound.

Je nach Verwendungszweck können ferner dem hochmolekularen organischen Material noch weitere Stoffe zugefügt werden, wie beispielsweise Füllstoffe wie Kaolin, Glimmer, Feldspate, Wollastonit, Aluminiumsilikat, Bariumsulfat, Calciumsulfat, Kreide, Calcit und Dolomit, ferner Licht­schutzmittel, Antioxidantien, Flammschutzmittel, Hitzestabilisatoren, Verstärkungsmittel, wie Glasfasern, oder Verarbeitungshilfsmittel, welche bei der Verarbeitung von Kunststoffen üblich und dem Fachmann bekannt sind.Depending on the intended use, other substances can also be added to the high molecular weight organic material, such as fillers such as kaolin, mica, feldspar, wollastonite, aluminum silicate, barium sulfate, calcium sulfate, chalk, calcite and dolomite, and also light stabilizers, antioxidants, flame retardants, heat stabilizers, reinforcing agents, such as glass fibers, or processing aids which are customary in the processing of plastics and are known to the person skilled in the art.

Zur Herstellung von Lacken und Druckfarben werden die hochmolekularen organischen Materialien und die obigen beiden Farbkomponenten [ausbleich­barer Zusatzstoff/nicht ausbleichende Verbindung] gegebenenfalls zusammen mit weiteren Lack- und Druckfarbenzusätzen, in einem gemeinsamen organischen Lösungsmittel oder Lösungsmittelgemisch fein dispergiert bzw. gelöst. Man kann dabei so verfahren, dass man die einzelnen Kompo­nenten für sich oder auch mehrere gemeinsam dispergiert bzw. löst, und erst hierauf alle Komponenten zusammenbringt. Der homogenisierte Lack bzw. die Druckfarbe wird dann auf einem Substrat nach an sich bekannten Verfahren aufgetragen und eingebrannt bzw. getrocknet, und der erhaltene Lack- bzw. Druckfarbenfilm dann erfindungsgemäss beschriftet.For the production of lacquers and printing inks, the high molecular weight organic materials and the above two color components [bleachable additive / non-bleaching compound] are optionally used together with other paint and printing ink additives, finely dispersed or dissolved in a common organic solvent or solvent mixture. You can do this by dispersing or dissolving the individual components for yourself or several together, and only then bringing all the components together. The homogenized lacquer or the printing ink is then applied to a substrate by methods known per se and baked or dried, and the lacquer or printing ink film obtained is then labeled according to the invention.

Es ist auch möglich, jede dieser Farbkomponenten in einen getrennten Lack- oder Druckfarbenfilm einzuarbeiten, wobei vorzugsweise die untere auf dem Substrat aufgebrachte Schicht die nicht ausbleichende Komponente enthält.It is also possible to incorporate each of these color components into a separate lacquer or printing ink film, the lower layer applied to the substrate preferably containing the non-bleaching component.

Zur Beschriftung der erfindungsgemäss in Frage kommenden hochmolekularen organischen Materialien werden energiereiche Laser-Quellen verwendet. Dabei wird die Energiestrahlung entsprechend der Form des aufzubringenden Schriftzeichens z.B. nahezu auf die Oberfläche des zu markierenden Materials senkrecht gerichtet, gegebenenfalls fokussiert, wobei an den bestrahlten Stellen eine Verfärbung entsteht, ohne dass die Oberfläche des beschrifteten Materials von Auge erkennbar beschädigt wird.High-energy laser sources are used to label the high-molecular organic materials that are possible according to the invention. The energy radiation is corresponding to the shape of the character to be applied, e.g. almost directed vertically onto the surface of the material to be marked, optionally focused, a discoloration occurring at the irradiated points without the surface of the labeled material being visibly damaged by the eye.

Beispiele für solche Laser-Quellen sind Festkörper-Pulslaser, wie Rubin­laser oder frequenzvervielfachte Nd:YAG-Laser, gepulste Laser mit Zusatz­einrichtung, wie gepulste Farbstofflaser oder Ramanshifter, weiter Dauerstrichlaser mit Pulsmodifikationen (Q-Switch, Mode-Locker), beis­pielsweise auf Basis von CW Nd:YAG-Lasern mit Frequenzvervielfacher, oder CW Ionen-Laser (Ar, Kr), ferner gepulste Metalldampflaser, wie beispiels­weise Cu-Dampflaser oder Au-Dampflaser, oder allenfalls leistungsstarke gepulste Halbleiter-Laser, die durch Frequenzverdopplung sichtbares Licht emittieren, ferner gepulste Gaslaser, wie Excimer- und Stickstofflaser.Examples of such laser sources are solid-state pulse lasers, such as ruby lasers or frequency-multiplied Nd: YAG lasers, pulsed lasers with additional devices, such as pulsed dye lasers or Raman shifters, and continuous wave lasers with pulse modifications (Q-Switch, Mode-Locker), for example based on CW Nd: YAG lasers with a frequency multiplier, or CW ion lasers (Ar, Kr), also pulsed metal vapor lasers, such as for example Cu vapor lasers or Au vapor lasers, or possibly powerful pulsed semiconductor lasers that emit visible light by frequency doubling, furthermore pulsed gas lasers such as excimer and nitrogen lasers.

Je nach eingesetztem Laser-System sind Pulsenergien bis einige Joule, Leistungsdichten bis Terawatt pro cm², Pulsbreiten von Femto-Sekunden bis Micro-Sekunden und Repetitionsraten bis Gigahertz möglich. Vorteilhafter­weise werden Pulsenergien von Microjoule bis Joule, Leistungsdichten von Kilowatt pro cm² bis 100 Megawatt pro cm², Pulsbreiten von Micro-Sekunden bis Pico-Sekunden und Repetitionsraten von Hertz bis 250 Megahertz eingesetzt.Depending on the laser system used, pulse energies up to a few joules, power densities up to terawatts per cm², pulse widths from femto-seconds to micro-seconds and repetition rates up to gigahertz are possible. Pulse energies of microjoules to joules, power densities of Kilowatts per cm² to 100 megawatts per cm², pulse widths from micro-seconds to pico-seconds and repetition rates from Hertz to 250 Megahertz.

Bevorzugt werden gepulste oder pulsmodifizierte frequenzverdoppelte Nd:YAG-Laser oder Metalldampf-Laser, wie Au- oder insbesonders Cu-Dampf­laser, sowie Excimer-Laser verwendet.Pulsed or pulse-modified, frequency-doubled Nd: YAG lasers or metal vapor lasers, such as Au or in particular Cu vapor lasers, and excimer lasers are preferably used.

In der folgenden Tabelle sind einige handelsübliche Laser aufgeführt, die erfindungsgemäss in Frage kommen können.

Figure imgb0001
The following table lists some commercially available lasers that can be used according to the invention.
Figure imgb0001

Gemäss dem erfindungsgemässen Verfahren wird beispielsweise mit einem gepulsten frequenzverdoppelten Nd:YAG-Laser zwischen 0,01 und 1 Joule pro cm² Pulsenergie, etwa 40 Megawatt Spitzenleistung, 6-8 Nano-Sekunden Pulsbreite und 20 Hertz Repetitionsrate (Modell Quanta Ray DCR-2 A der Firma Spectra Physics, Mountain View, California) gearbeitet.According to the method according to the invention, for example, with a pulsed frequency-doubled Nd: YAG laser between 0.01 and 1 joule per cm² of pulse energy, about 40 megawatt peak power, 6-8 nano-second pulse width and 20 Hertz repetition rate (model Quanta Ray DCR-2 A from Spectra Physics, Mountain View, California).

Verwendet man einen Cu-Dampflaser (Plasma Kinetics Modell 151) mit Fokussieroptik, so wird beispielsweise mit 250 Millijoule pro cm² Pulsenergie, etwa 10 Kilowatt Spitzenleistung, 30 Nano-Sekunden Puls­breite und 6 Kilohertz Repetitionsrate belichtet.If a Cu vapor laser (Plasma Kinetics Model 151) with focusing optics is used, then exposure is, for example, to 250 millijoules per cm² of pulse energy, approximately 10 kilowatts of peak power, 30 nano-seconds pulse width and 6 kilohertz repetition rate.

Laser mit guter Einstellbarkeit ihrer Laserparameter, wie beispielsweise Pulsenergie und Einwirkzeit, erlauben eine optimale Anpassung an die Bedürfnisse der zu beschriftenden Materialien.Lasers with good adjustability of their laser parameters, such as pulse energy and exposure time, allow optimal adaptation to the needs of the materials to be labeled.

Die optimale, zur Bestrahlung auszuwählende Wellenlänge ist diejenige, bei welcher der strahlungsempfindliche ausbleichbare Zusatzstoff am meisten, die nicht ausbleichende Verbindung und das zu beschriftende organische Material dagegen am wenigsten absorbieren. Bei richtiger Wahl des ausbleichbaren Zusatzstoffes und der nicht ausbleichenden Verbindung ist aber auch eine deutliche Farbänderung möglich, wenn beide die eingestrahlte Wellenlänge absorbieren.The optimal wavelength to be selected for irradiation is the one at which the radiation-sensitive bleachable additive absorbs the least, the non-bleaching compound and the organic material to be labeled on the other hand least absorb. With the right choice of the bleachable additive and the non-bleaching compound, a clear color change is also possible if both absorb the irradiated wavelength.

Zur Beschriftung mit Lasern kommen im allgemeinen drei verschiedene Verfahren in Frage: das Maskenverfahren, die linienförmige Beschriftung und das Punkt-Matrix-Verfahren. Bei den zwei letztgenannten Beschrif­tungsarten (dynamische Strahlführung) wird der Laser bevorzugt mit einem Laserbeschriftungssystem gekoppelt, so dass das anorganische Material mit beliebigen, beispielsweise in einem Computer programmierten Ziffern, Buchstaben und Sonderzeichen beschriftet werden kann.There are generally three different methods for labeling with lasers: the mask method, the linear labeling and the dot-matrix method. In the latter two types of labeling (dynamic beam guidance), the laser is preferably coupled to a laser labeling system, so that the inorganic material can be labeled with any numbers, letters and special characters programmed in a computer, for example.

Die Wahl des Lasersystems bezüglich Leistung und Repetitionsrate richtet sich grundsätzlich nach dem zur Anwendung gelangenden Beschriftungsver­fahren. Hohe Leistung und niedere Repetitionsrate, wie beim Festkörper-­Pulslaser und Excimerlaser, werden bevorzugt für Maskenbelichtungen angewandt. Mittlere bis kleine Leistungen und schnelle Repetitionsraten beim gepulsten Metalldampflaser oder beim Dauerstrichlaser mit Pulsmodi­fikationen werden bevorzugt für Beschriftungen angewandt, die eine dynamische Strahlführung erfordern. Die Strahlablenkung kann beispiels­weise akustooptisch, holographisch, mit Galvo-Spiegeln oder Polygon-­Scannern erfolgen. Die dynamische Strahlführung erlaubt eine äusserst flexible Beschriftung oder Markierung, da die Zeichen elektronisch erzeugt werden können.The choice of the laser system with regard to power and repetition rate is basically based on the labeling method used. High power and low repetition rates, as with solid-state pulse lasers and excimer lasers, are preferred for mask exposures. Medium to low performance and fast repetition rates In the case of pulsed metal vapor lasers or continuous wave lasers with pulse modifications, they are preferred for labels that require dynamic beam guidance. The beam deflection can take place, for example, acousto-optically, holographically, with galvo mirrors or polygon scanners. The dynamic beam guidance enables extremely flexible labeling or marking, since the characters can be generated electronically.

Nach dem erfindungsgemässen Verfahren können die verschiedensten Be­schriftungsarten erhalten werden. Beispiele hierfür sind: Variable Textprogrammierung von numerischen Zeichen mittels Texteingabe über ein Bildschirmterminal, Textprogramme von Standardzeichen oder Sonderzeichen, wie Namenszüge, ferner Initialen und Widmungen, Identitätskarten, Signete oder sich oft wiederholende Daten, fortlaufende Stückzahlnumerierung, Eingabe von Messgrössen, Eingabe eines gespeicherten Programms, Linien­beschriftung oder auch Dekorationen.The most varied types of inscription can be obtained by the process according to the invention. Examples of this are: Variable text programming of numerical characters by entering text on a screen terminal, text programs of standard characters or special characters, such as names, initials and dedications, identity cards, signs or frequently repeated data, consecutive numbering of items, input of measurement quantities, input of a saved program, Line lettering or decorations.

Nach dem erfindungsgemässen Verfahren können die verschiedensten Kunst­stoff-Gegenstände, -Formen oder -Folien sowie Lack- und Druckfarben-Filme beschriftet werden. Beispiele hierfür sind Bänder, Tafeln, Rohre und Profile, Tasten und mit Kunststoff umhüllte elektronische Bauteile oder im Zweiphasen-Spritzgussverfahren hergestellte Teile mit unterschied­lichen Einfärbungen.A wide variety of plastic objects, shapes or foils as well as lacquer and printing ink films can be labeled using the method according to the invention. Examples of this are tapes, boards, tubes and profiles, buttons and plastic-encased electronic components or parts with different colors produced using the two-phase injection molding process.

Typische Anwendungsbeispiele sind die Beschriftung von Schaltern, Leiterplatten, gedruckten Schaltungen, aktiven und passiven elektro­nischen Komponenten, enkapsulierten Hochspannungstransformatoren, Stecker und Steckdosen, Gehäusen, mechanischen Bestandteilen aus der Feintechnik und der Uhrenindustrie, Fahrzeugbestandteilen, Tastaturen, elektro­nischen Bauteilen, Kabeln, Rohren, Lacken, Folien, Filmen und Ver­packungsfolien, Banknoten, Kreditkarten und Wertschriften, sowie Anzeigefenster und Zifferblätter.Typical application examples are the labeling of switches, printed circuit boards, printed circuits, active and passive electronic components, encapsulated high-voltage transformers, plugs and sockets, housings, mechanical components from the precision engineering and watch industry, vehicle components, keyboards, electronic components, cables, pipes, paints, Films, films and packaging foils, banknotes, credit cards and securities, as well as display windows and dials.

Das erfindungsgemässe Verfahren ermöglicht eine bunte Kontrast-Mar­kierung, welche nicht verwischt werden kann und daher abrieb- und kratzfest ist. Die erfindungsgemäss erhaltenen Markierungen sind ferner korrosionsbeständig, dimensionsstabil, deformationsfrei, licht-, hitze- und wetterbeständig, und gut lesbar und haben saubere Randzonen. Ferner werden die mechanischen und physikalischen Eigenschaften des so be­schrifteten Materials praktisch nicht beeinträchtigt, wie beispielsweise die mechanische Festigkeit und die chemische Resistenz. Die Eindringtiefe der Markierung hängt vom beschrifteten Material ab. Sie beträgt üblicher­weise weniger als 1 mm. Das hochmolekulare organische Material wird dabei weitgehendst geschont. Es sind somit Beschriftungen möglich, die keinen von Auge erkennbaren Verlust am Oberflächenglanz bewirken und die Festig­keitseigenschaften des Werkstückes nicht beeinträchtigen.The method according to the invention enables a colorful contrast marking, which cannot be blurred and is therefore resistant to abrasion and scratches. The markings obtained according to the invention are also corrosion-resistant, dimensionally stable, deformation-free, light-, heat- and weatherproof, and legible and have clean margins. Furthermore, the mechanical and physical properties of the material so labeled are practically unaffected, such as mechanical strength and chemical resistance. The depth of penetration of the marking depends on the labeled material. It is usually less than 1 mm. The high-molecular organic material is largely protected. Inscriptions are therefore possible that do not cause any loss of surface gloss that can be seen by the eye and do not impair the strength properties of the workpiece.

Gemäss dem vorliegenden Verfahren tritt unter Laserbestrahlung an den bestrahlten Stellen des Materials ein Farbumschlag mit einem ausgeprägten Kontrast ein. Dabei verändert sich die durch das Einfärben des organi­schen Materials mit den zwei verschiedenen, erfindungsgemäss in Betracht gezogenen Farbstoffkomponenten (= ausbleibarer Zusatzstoff und nicht ausbleichende Verbindung) erhaltene Mischfarbe derart, dass eine Farbkomponente (bestehend aus einer einzelnen oder mehreren Farbstoff­komponenten) an den bestrahlten Stellen teilweise oder ganz ausbleicht, so dass für den Beobachter nur noch eine andersfarbige Kontrastmar­kierung entsprechend der Farbe der resistenten zweiten Farbkomponente (bestehend aus einer einzelnen oder mehreren Farbstoffkomponenten) sichtbar wird.According to the present method, a color change with a pronounced contrast occurs at the irradiated areas of the material under laser irradiation. The mixed color obtained by coloring the organic material with the two different dye components (= additive that cannot be bleached and non-bleaching compound) taken into account changes in such a way that a color component (consisting of a single or more dye components) partially at the irradiated areas or completely bleached out, so that the observer only sees a different colored contrast marking corresponding to the color of the resistant second color component (consisting of a single or several dye components).

In den folgenden Beispielen bedeuten Teile, sofern nicht anders ange­geben, Gewichtsteile.In the following examples, parts are by weight unless otherwise specified.

Beispiel 1:Example 1:

45 g Epoxidharz ®Araldit GY 250 (Diglycidylaether von Bisphenol A mit einem Epoxidgehalt zwischen 5,25-5,4 VAL pro kg, Firma Ciba-Geigy AG, Schweiz) werden mit 5 g ®Cromophtal Rot G (Disazokonden­sationspigment, C.I. Pigment Rot 220, Firma Ciba-Geigy AG) vermischt und in einem Scheibenrührer zusammen mit 100 g Glaskugeln während 100 Minuten bei 45°C gut dispergiert (=Farbpaste 1). Ein Lack bestehend aus 9,85 g Epoxidharz ®Araldit GY 250 (Ciba-Geigy AG), 2,4 g Härter ®HY 956 (flüs­siges modifiziertes aliphatisches Polyamin, Ciba-Geigy AG), 0,15 g obiger Farbpaste 1, 0,1 g Farbpaste DWO135 (Epoxidharz-Paste auf Diglycidyl­aether-Bisphenol-A-Basis mit einem Epoxidgehalt zwischen 5,25-5,4 VAL pro kg und enthaltend 15 Gew.% ®Cromophtal Blau A3R, Indanthron, C.I. Pigment Blau 60, Ciba-Geigy AG) und 2 Tropfen eines Netzmittels (®FC 430, fluorierter Alkylester, Firma 3M, Schweiz) wird bei 45°C homogen ver­mischt und von Gasblasen befreit. Der dickflüssige Lack wird mit einem Ziehstab für 100 µm Nassfilmdicke auf eine gereinigte, fettfreie Glasplatte (Mikroskop-Objektträger) aufgetragen und im Trockenschrank während 4 Stunden bei 100°C ausgehärtet.45 g of ®Araldit GY 250 epoxy resin (diglycidyl ether of bisphenol A with an epoxy content between 5.25-5.4 VAL per kg, from Ciba-Geigy AG, Switzerland) are mixed with 5 g of ®Cromophthal Red G (disazo condensation pigment, CI Pigment Red 220 , Ciba-Geigy AG) and mixed well in a disk stirrer together with 100 g glass balls for 100 minutes at 45 ° C. (= color paste 1). A varnish consisting of 9.85 g epoxy resin ®Araldit GY 250 (Ciba-Geigy AG), 2.4 g hardener ®HY 956 (liquid modified aliphatic polyamine, Ciba-Geigy AG), 0.15 g of the above color paste 1, 0, 1 g color paste DWO135 (epoxy resin paste based on diglycidylaether bisphenol A with an epoxy content between 5.25-5.4 VAL per kg and containing 15% by weight ®Cromophthal Blue A3R, indanthrone, CI pigment Blau 60, Ciba-Geigy AG) and 2 drops of a wetting agent (®FC 430, fluorinated alkyl ester, company 3M, Switzerland) are mixed homogeneously at 45 ° C and freed of gas bubbles. The viscous lacquer is applied to a cleaned, grease-free glass plate (microscope slide) with a drawing stick for 100 µm wet film thickness and cured in a drying cabinet at 100 ° C for 4 hours.

Die fertige Schicht wird mit einem über zwei orthogonale bewegliche Spiegel abgelenkten Laserstrahl entsprechend der Form der aufzubringenden Markierung beschriftet. Als Laserquelle wird ein Nd:YAG Pulslaser (®Quanta Ray DCR 2, Spectra Physics) mit Frequenzverdoppler (Harmonic Generator) und Frequenzfilter (Harmonic Separator) verwendet. Der Laser wird so eingestellt und mit Neutralfiltern abgeschwächt, dass der über eine Linse (Brennweite 200 mm) senkrecht fokussierte Strahl auf der Schicht eine Puls-Energie von 0,2 mJ bei einer Pulsbreite von 10 Nano-­Sekunden erreicht. Die Ablenkeinheit mit den orthogonalen, beweglichen Spiegeln ist Bestandteil eines ®GRETAG 6210 Laserbeschriftungssystems (GRETAG AG, Schweiz). Die so erzielte Beschriftung erscheint grün auf dem dunkelblau eingefärbten Lack.The finished layer is labeled with a laser beam deflected via two orthogonal movable mirrors in accordance with the shape of the marking to be applied. An Nd: YAG pulse laser (®Quanta Ray DCR 2, Spectra Physics) with frequency doubler (harmonic generator) and frequency filter (harmonic separator) is used as the laser source. The laser is adjusted and attenuated with neutral filters so that the beam, which is focused vertically via a lens (focal length 200 mm) on the slice, reaches a pulse energy of 0.2 mJ with a pulse width of 10 nano-seconds. The deflection unit with the orthogonal, movable mirrors is part of a ®GRETAG 6210 laser marking system (GRETAG AG, Switzerland). The inscription obtained in this way appears green on the dark blue colored paint.

Beispiel 2:Example 2:

Ein Lack bestehend aus 9,8 g Epoxidharz ®Araldit GY 250 (gemäss Beispiel 1), 2,4 g Härter ®HY 956 (gemäss Beispiel 1), 0,15 g Farbpaste ®DWO132 (Epoxidharz-Paste auf Diglycidylaether-Bisphenol-A-­Basis mit einem Epoxidgehalt zwischen 5,25-5,4 VAL pro kg und enthaltend 15 Gew% ®Cromophtal Gelb 3G, Disazokondensationspigment, C.I. Pigment Gelb 93, Ciba-Geigy AG), 0,1 g Farbpaste ®DWO133 (Epoxidharz-Paste auf Diglycidylaether-Bisphenol-A-Basis mit einem Epoxidgehalt zwischen 5,25-5,4 VAL pro kg und enthaltend 13,5 Gew% ®Cromophtal Rot G, Dis­azokondensationspigment, C.I. Pigment Rot 220, und 1,5 Gew% ®Cromophtal Gelb 30, Disazokondensationspigment, C.I. Pigment Gelb 93, Ciba-Geigy AG) und 2 Tropfen Netzmittel (®FC 430, gemäss Beispiel 1) wird bei 45°C homogen vermischt und von Gasblasen befreit. Der dickflüssige Lack wird mit einem Ziehstab für 100 µm Nassfilmdicke auf eine gereinigte, fettfreie Glasplatte (Mikroskop-Objektträger) aufgetragen und im Trocken­schrank während 4 Stunden bei 100°C ausgehärtet.A varnish consisting of 9.8 g epoxy resin ®Araldit GY 250 (according to example 1), 2.4 g hardener ®HY 956 (according to example 1), 0.15 g color paste ®DWO132 (epoxy resin paste on diglycidyl ether-bisphenol-A -Base with an epoxy content between 5.25-5.4 VAL per kg and containing 15% by weight ®Cromophthal Yellow 3G, disazo condensation pigment, CI Pigment Yellow 93, Ciba-Geigy AG), 0.1 g color paste ®DWO133 (epoxy resin paste based on diglycidyl ether-bisphenol A with an epoxy content between 5.25-5.4 VAL per kg and containing 13.5% by weight ®Cromophthal Red G, disazo condensation pigment, CI Pigment Red 220 and 1.5% by weight ®Cromophthal yellow 30, disazo condensation pigment, CI Pigment Yellow 93, Ciba-Geigy AG) and 2 drops of wetting agent (®FC 430, according to Example 1) are mixed homogeneously at 45 ° C. and gas bubbles are removed. The viscous lacquer is applied to a cleaned, grease-free glass plate (microscope slide) with a drawing stick for 100 µm wet film thickness and cured in a drying cabinet at 100 ° C for 4 hours.

Die Laserbeschriftung erfolgt analog zu Beispiel 1; es entsteht eine gelbe Beschriftung auf dem orange eingefärbten Hintergrund.Laser marking is carried out analogously to Example 1; a yellow label is created on the orange colored background.

Beispiel 3:Example 3:

Eine Lacklösung wird durch Auflösen von 75 g Polymethyl­methacrylat (PMMA, ®LUCITE von DuPont) in 425 g Methyl-Ethyl-Keton (MEK) unter Rühren bei Raumtemperatur während 48 Stunden auf einem Magnetrührer hergestellt. Ein erster Farblack wird durch intensive Mischung von 50 g der obigen Lacklösung mit 79 mg ®Cromophtal Rot G (Disazokondensations­pigment, C.I. Pigment Rot 220, Ciba-Geigy AG) im Ultraschallbad herge­stellt; ein zweiter Farblack wird auf die gleiche Weise aus 50 g der gleichen Lacklösung und 413 mg ®Cromophtal Grün GFN (halogeniertes Kupfer-Phthalocyanin, C.I. Pigment Grün 7, Ciba-Geigy AG) hergestellt. Gleiche Teile des ersten und zweiten Farblackes werden homogen vermischt, dann mit einem Ziehstab für 100 µm Nassfilmdicke auf einen Objektträger aufgezogen. Der Film wird während einer Stunde bei 50°C im Trocken­schrank getrocknet, dann wie im Beispiel 1 beschriftet; es entsteht eine grüne Beschriftung auf dem violetten Hintergrund.A coating solution is prepared by dissolving 75 g of polymethyl methacrylate (PMMA, ®LUCITE from DuPont) in 425 g of methyl ethyl ketone (MEK) with stirring at room temperature for 48 hours on a magnetic stirrer. A first colored lacquer is produced by intensively mixing 50 g of the above lacquer solution with 79 mg ®Cromophthal Red G (disazo condensation pigment, C.I. Pigment Red 220, Ciba-Geigy AG) in an ultrasonic bath; a second color lacquer is produced in the same way from 50 g of the same lacquer solution and 413 mg ®Cromophthal Green GFN (halogenated copper phthalocyanine, C.I. Pigment Green 7, Ciba-Geigy AG). The same parts of the first and second color varnish are mixed homogeneously, then drawn onto a slide with a drawing stick for 100 µm wet film thickness. The film is dried in an oven at 50 ° C. for one hour, then labeled as in Example 1; a green label is created on the purple background.

In Analogie zum obigen Beispiel 3 kann ®Cromophtal Rot G auch in anderen Systemen, wie in einem PVB- oder PES-Film, als ausbleichbare Verbindung eingesetzt werden. PVB steht für Polyvinylbutyral (z.B. ®Movital B30H, Hoechst AG), PES für einen Polyester (z.B. ®Dynapol L206, Dynamit Nobel). Zur Filmbildung können ®Movital B3OH z.B. in 2-Methoxy-ethanol und ®Dynapol L206 z.B. in Tetrahydrofuran gelöst werden.In analogy to Example 3 above, ®Cromophthal Red G can also be used as a bleachable compound in other systems, such as in a PVB or PES film. PVB stands for polyvinyl butyral (e.g. ®Movital B30H, Hoechst AG), PES for a polyester (e.g. ®Dynapol L206, Dynamit Nobel). ®Movital B3OH e.g. in 2-methoxyethanol and ®Dynapol L206 e.g. be dissolved in tetrahydrofuran.

Beispiel 4:Example 4:

100 Teile Polyethylen (®Lupolen, BAYER), 2 Teile Calcium­metasilikat, 0,6 Teile Glycerin-Monostearat (Gleitmittel), 1 Teil ®Cromo­phtal Rot G (Disazokondensationspigment, C.I. Pigment Rot 220, Ciba-Geigy AG) und 3 Teile Titandioxyd werden trocken gemischt und dann mit einem Schneckenextruder bei 180-190°C zu Bändern mit einem Quer­schnitt von 2 x 21 mm geformt. Die Laserbeschriftung erfolgt analog zu Beispiel 1; es entsteht eine hellgraue Beschriftung auf dem roten Hintergrund. Wird die Beschriftung mit einer Wellenlänge von 355 nm anstelle von 532 nm durchgeführt, so entsteht eine grauschwarze Be­schriftung auf dem roten Hintergrund.100 parts of polyethylene (®Lupolen, BAYER), 2 parts of calcium metasilicate, 0.6 part of glycerol monostearate (lubricant), 1 part of ®Cromophthal Red G (disazo condensation pigment, CI Pigment Red 220, Ciba-Geigy AG) and 3 parts of titanium dioxide become dry mixed and then formed with a screw extruder at 180-190 ° C into strips with a cross section of 2 x 21 mm. Laser marking is carried out analogously to Example 1; a light gray label is created on the red background. If the labeling is carried out with a wavelength of 355 nm instead of 532 nm, a gray-black label is created on the red background.

Beispiel 5:Example 5:

100 g Polyacetal-Copolymer ®Ultraform N 2320 (Polyoxy­methylenbasis, BASF) werden mit 0,24 g ®Cromophtal Braun 5R (Disazo­kondensationspigment, C.I. Pigment Braun 23, Ciba-Geigy AG), 0,08 g ®Cromophtal Rot BRN (Disazokondensationspigment, C.I. Pigment Rot 144, Ciba-Geigy AG), 0,18 g ®Cromophtal Blau A3R (Indanthronpigment, C.I. Pigment Blau 60, Ciba-Geigy AG) und 2 g Titandioxid trocken gemischt und bei 180-190°C extrudiert. Das so erhaltene granulierte Compound wird bei 180-190°C zu Formteilen (Breite: 5 cm; Länge: 6 cm; Dicke; 2 mm) verspritzt.100 g polyacetal copolymer ®Ultraform N 2320 (polyoxymethylene base, BASF) are mixed with 0.24 g ®Cromophthal Braun 5R (disazo condensation pigment, CI Pigment Braun 23, Ciba-Geigy AG), 0.08 g ®Cromophthal Red BRN (disazocondensation pigment, CI Pigment Red 144, Ciba-Geigy AG), 0.18 g ®Cromophthal Blue A3R (indanthrone pigment, CI Pigment Blue 60, Ciba-Geigy AG) and 2 g titanium dioxide mixed dry and extruded at 180-190 ° C. The granulated compound thus obtained is injected at 180-190 ° C into molded parts (width: 5 cm; length: 6 cm; thickness; 2 mm).

Die zu markierenden grauen Flächen werden mit einem Beschriftungssystem ®Gretag 6411-System 2 (Gretag AG, Schweiz) markiert. Als Laserquelle dient ein kontinuierlich gepumpter, gütegeschalteter Nd:YAG-Laser, der frequenzverdoppelt wird, wobei die Energie des Laserstrahls entsprechend der Form der aufzubringenden Markierung auf die Oberfläche des zu mar­kierenden Materials gerichtet wird.The gray areas to be marked are marked with a labeling system ®Gretag 6411-System 2 (Gretag AG, Switzerland). A continuously pumped, Q-switched Nd: YAG laser serves as the laser source and is frequency-doubled, the energy of the laser beam being directed onto the surface of the material to be marked in accordance with the shape of the marking to be applied.

Der Laserstrahl mit einer Energie von 0,1-1,0 mJ und einer Pulsbreite von 100-400 ns (Nano-Sekunden) wird über eine Linse mit einer Brennweite von 160 mm auf die zu markierende Fläche fokussiert. Die erzielte Beschriftung erscheint weiss auf grauem Untergrund.The laser beam with an energy of 0.1-1.0 mJ and a pulse width of 100-400 ns (nano-seconds) is focused on the surface to be marked via a lens with a focal length of 160 mm. The lettering obtained appears in white on a gray background.

Beispiel 6:Example 6:

100 g Polyacetal-Copolymer ®Ultraform N 2320 (BASF) werden mit 0,08 g ®Cromophtal Scharlach RN (Disazokondensationspigment, C.I. Pigment Rot 166, Ciba-Geigy AG), 0,09 g ®Cromophtal Grün GFN (Kupferphthalocyaninpigment, C.I. Pigment Grün 7) und 0,5 g Titandioxid trocken gemischt. Das erhaltene Granulat wird wie in Beispiel 5 extru­diert, zu Formteilen verspritzt und markiert. Die Markierung erscheint auf dem grauen Untergrund grün.100 g polyacetal copolymer ®Ultraform N 2320 (BASF) are mixed with 0.08 g ®Cromophthal scarlet RN (disazo condensation pigment, CI Pigment Red 166, Ciba-Geigy AG), 0.09 g ®Cromophthal green GFN (copper phthalocyanine pigment, CI pigment green 7) and 0.5 g of titanium dioxide mixed dry. The granules obtained are extruded as in Example 5, injection molded into shaped articles and marked. The marking appears green on the gray background.

Beispiel 7:Example 7:

100 g Polyacetal-Copolymer ®Ultraform N 2320 (BASF) werden mit 0,1 g ®Cromophtal Braun 5R (Disazokondensationspigment, C.I. Pig­ment Braun 23, Ciba-Geigy AG), 0,05 g ®Cromophtal Blau 4GNP (β-Kupfer­phthalocyaninpigment, C.I. Pigment Blau 15:3, Ciba-Geigy AG), 0,04 g ®Cromophtal Rot BRN (Disazokondensationspigment, CI Pigment Rot 144, Ciba-Geigy AG) und 1 g Titandioxid trocken gemischt, und das erhaltene Granulat wird wie unter Beispiel 5 beschrieben extrudiert, zu Formteilen verspritzt und markiert. Die Markierung erscheint auf dem grauen Untergrund blau.100 g polyacetal copolymer ®Ultraform N 2320 (BASF) are mixed with 0.1 g ®Cromophthal Braun 5R (disazo condensation pigment, CI Pigment Braun 23, Ciba-Geigy AG), 0.05 g ®Cromophthal Blue 4GNP (β-copper phthalocyanine pigment, CI Pigment Blue 15: 3, Ciba-Geigy AG), 0.04 g ®Cromophthal Red BRN (disazo condensation pigment, CI Pigment Red 144, Ciba-Geigy AG) and 1 g of titanium dioxide dry mixed, and the granules obtained are extruded as described in Example 5, injected into molded parts and marked. The marking appears blue on the gray background.

Beispiel 8:Example 8:

100 g Polypropylen glasgefüllt (®PROCOM GC 3OH 251, ICI) werden mit 0,74 g eines Masterbatch aus 75 Gew.% LDPE und 25 Gew.% ®Cromophtal Braun 5R, 0,56 g eines Masterbatch aus 75 Gew.% LDPE und 25 Gew.% ®Cromophtal Blau A3R, und 1,43 g eines 70%igen TiO₂-LDPE-Master­batch gemischt und bei 180-190°C extrudiert, um maximale Dispergierung zu erreichen. Nach dem Granulieren wird das so erhaltene Granulat zu Formteilen verarbeitet und wie unter Beispiel 5 beschrieben markiert. Die Markierung erscheint weiss auf grauem Untergrund.
[LDPE = "low density" Polyethylen].100 g of polypropylene filled with glass (®PROCOM GC 3OH 251, ICI) are mixed with 0.74 g of a masterbatch made of 75% by weight LDPE and 25% by weight ®Cromophthal Brown 5R, 0.56 g of a masterbatch made of 75% by weight LDPE and 25% by weight ®Cromophthal Blue A3R, and 1.43 g of a 70% TiO₂-LDPE masterbatch mixed and extruded at 180-190 ° C to achieve maximum dispersion. After granulation, the granules obtained in this way are processed into moldings and marked as described in Example 5. The marking appears white on a gray background.
[LDPE = "low density" polyethylene].

Claims (14)

1. Verfahren zur Laserbeschriftung von hochmolekularem organischem Material in Form von Gegenständen, Folien und Filmen, wonach das min­destens einen strahlungsempfindlichen ausbleichbaren Zusatzstoff und mindestens eine weniger strahlungsempfindliche nicht ausbleichende Verbindung enthaltende Material einem Laserstrahl ausgesetzt ist, wobei die Energie des Laserstrahls entsprechend der Form der aufzubringenden Markierung auf die Oberfläche des zu markierenden Materials gerichtet wird, so dass an den bestrahlten Stellen eine visuelle bunte Kontrast­markierung entsteht, ohne dass die Oberfläche des beschrifteten Materials von Auge erkennbar beschädigt wird, dadurch gekennzeichnet, dass man gepulstes Laserlicht, dessen Wellenlänge im nahen UV- und/oder sichtbaren Bereich liegt, verwendet, und dass man als ausbleichbaren Zusatzstoff mindestens ein Azo- und/oder ein Indanthronpigment und als nicht aus­bleichende Verbindung mindestens ein anorganisches und/oder organisches Pigment und/oder einen polymerlöslichen Farbstoff verwendet.1. A method for laser marking of high molecular weight organic material in the form of objects, foils and films, according to which the material containing at least one radiation-sensitive bleachable additive and at least one less radiation-sensitive non-bleaching compound is exposed to a laser beam, the energy of the laser beam corresponding to the shape of the material to be applied Marking is directed onto the surface of the material to be marked, so that a colored visual contrast marking is created at the irradiated areas without the surface of the labeled material being visibly damaged by the eye, characterized in that pulsed laser light, the wavelength of which is in the near UV and / or visible range, and that at least one azo and / or indanthrone pigment is used as the bleachable additive and at least one inorganic and / or organic pigment and / or as the non-bleaching compound used a polymer-soluble dye. 2. Verfahren gemäss Anspruch 1, dadurch gekennzeichnet, dass man ge­pulstes Laserlicht mit einem gepulsten oder pulsmodifizierten, fre­quenzverdoppelten Nd:YAG-Laser oder einem Metalldampf-Laser oder einem Excimer-Laser erzeugt.2. The method according to claim 1, characterized in that pulsed laser light is generated with a pulsed or pulse-modified, frequency-doubled Nd: YAG laser or a metal vapor laser or an excimer laser. 3. Verfahren gemäss Anspruch 1, dadurch gekennzeichnet, dass man als hochmolekulares organisches Material Polyvinylester, Polyacrylsäure- und Polymethacrylsäureester, Polyester, Polyamide, Polyimide, Polycarbonate, Polyurethane, Polyäther, Polyacetale, Phenoplaste, Aminoplaste oder Epoxyharze verwendet.3. The method according to claim 1, characterized in that polyvinyl esters, polyacrylic acid and polymethacrylic acid esters, polyesters, polyamides, polyimides, polycarbonates, polyurethanes, polyethers, polyacetals, phenoplasts, aminoplasts or epoxy resins are used as the high molecular weight organic material. 4. Verfahren gemäss Anspruch 3, dadurch gekennzeichnet, dass man Polyacrylsäure- und Polymethacrylsäureester, Polyester, Polyamide, Polycarbonate, Polyphenylenoxide oder ein Epoxyharz verwendet.4. The method according to claim 3, characterized in that one uses polyacrylic acid and polymethacrylic acid esters, polyesters, polyamides, polycarbonates, polyphenylene oxides or an epoxy resin. 5. Verfahren gemäss Anspruch 3, dadurch gekennzeichnet, dass man einen Polymethacrylsäureester oder ein Epoxyharz verwendet.5. The method according to claim 3, characterized in that one uses a polymethacrylic acid ester or an epoxy resin. 6. Verfahren gemäss Anspruch 5, dadurch gekennzeichnet, dass man als Polymethacrylsäureester Polymethacrylsäuremethylester verwendet.6. The method according to claim 5, characterized in that polymethacrylic acid methyl ester is used as the polymethacrylic acid ester. 7. Verfahren gemäss Anspruch 1, dadurch gekennzeichnet, dass man als Azopigmente Mono- oder Disazoverbindungen der Acetoacetarylid-, Pyra­zolon-, 2,3-Oxynaphthoesäurearylid-, Barbitursäure-, Thiobarbitursäure-, 2,4,6-Triamino-pyrimidin-1,3- und 3-Cyan-4-methylpyridon-Reihe, sowie Metallsalze von Azoverbindungen, verwendet.7. The method according to claim 1, characterized in that as azo pigments mono- or disazo compounds of acetoacetarylide, pyrazolone, 2,3-oxynaphthoic acid arylide, barbituric acid, thiobarbituric acid, 2,4,6-triamino-pyrimidine-1, 3- and 3-cyan-4-methylpyridone series, as well as metal salts of azo compounds. 8. Verfahren gemäss Anspruch 7, dadurch gekennzeichnet, dass man ein Disazopigment der Acetoacetarylid-, Pyrazolon- oder 2,3-Oxynaphthoe­säurearylidreihe verwendet.8. The method according to claim 7, characterized in that one uses a disazo pigment of the acetoacetarylide, pyrazolone or 2,3-oxynaphthoic acid arylide series. 9. Verfahren gemäss Anspruch 1, dadurch gekennzeichnet, dass man als nicht ausbleichende Verbindung einen polymerlöslichen Farbstoff ver­wendet.9. The method according to claim 1, characterized in that a polymer-soluble dye is used as the non-bleaching compound. 10. Verfahren gemäss Anspruch 9, dadurch gekennzeichnet, dass man als polymerlöslichen Farbstoff ein Anthrachinonderivat verwendet.10. The method according to claim 9, characterized in that an anthraquinone derivative is used as the polymer-soluble dye. 11. Verfahren gemäss Anspruch 1, dadurch gekennzeichnet, dass man als anorganisches Pigment Metalloxide, Berlinerblau, Bleichromate, Bleisul­fochromate oder Zirkonsilikate verwendet.11. The method according to claim 1, characterized in that metal oxides, Berlin blue, lead chromates, lead sulfochromates or zirconium silicates are used as the inorganic pigment. 12. Verfahren gemäss Anspruch 1, dadurch gekennzeichnet, dass man als organisches Pigment Kupferphthalocyanin oder chloriertes Kupferphthalo­cyanin verwendet.12. The method according to claim 1, characterized in that copper phthalocyanine or chlorinated copper phthalocyanine is used as the organic pigment. 13. Das nach Anspruch 1 beschriftete Material.13. The material labeled according to claim 1. 14. Verfahren zur Laserbeschriftung von hochmolekularem organischem Material in Form von Gegenständen, Folien und Filmen, wonach das min­destens einen strahlungsempfindlichen ausbleichbaren Zusatzstoff und mindestens eine weniger strahlungsempfindliche nicht verfärbbare Ver­bindung enthaltende Material einem Laserstrahl ausgesetzt ist, wobei die Energie des Laserstrahls entsprechend der Form der aufzubringenden Markierung auf die Oberfläche des zu markierenden Materials gerichtet wird, so dass an den bestrahlten Stellen eine visuelle bunte Kontrast­markierung entsteht, ohne dass die Oberfläche des beschrifteten Materials von Auge erkennbar beschädigt wird, dadurch gekennzeichnet, dass man gepulstes Laserlicht, dessen Wellenlänge im nahen UV- und/oder sichtbaren Bereicht liegt, verwendet, und dass man als ausbleichbaren Zusatzstoff mindestens ein Azo- und/oder ein Indanthronpigment und als nicht ver­färbbare Verbindung mindestens ein anorganisches und/oder organisches Pigment und/oder einen polymerlöslichen Farbstoff verwendet.14. A method for laser marking of high molecular weight organic material in the form of objects, foils and films, according to which the material containing at least one radiation-sensitive bleachable additive and at least one less radiation-sensitive non-discolorable compound is exposed to a laser beam, the energy of the laser beam corresponding to the shape of the material to be applied Marking directed at the surface of the material to be marked is characterized in such a way that a colored visual contrast marking is created at the irradiated areas without the surface of the labeled material being visibly damaged by the eye, characterized in that pulsed laser light whose wavelength is in the near UV and / or visible range is used, and that at least one azo and / or indanthrone pigment is used as the bleachable additive and at least one inorganic and / or organic pigment and / or a polymer-soluble dye is used as the non-discolorable compound.
EP19890810091 1988-02-03 1989-02-02 Process for laser marking of pigmented systems Withdrawn EP0327508A3 (en)

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EP0993964A3 (en) * 1998-10-16 2000-11-22 Markem Corporation Coatings for marking by laser
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EP0327508A3 (en) 1991-02-06

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