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

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• 1989
  • 1989-02-02 EP EP19890810091 patent/EP0327508A3/fr not_active Withdrawn
  • 1989-02-03 JP JP1025626A patent/JPH024584A/ja active Pending

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