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EP0841186A1 - Compositions polymères à mouler, marquables au laser - Google Patents

Compositions polymères à mouler, marquables au laser Download PDF

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Publication number
EP0841186A1
EP0841186A1 EP97118622A EP97118622A EP0841186A1 EP 0841186 A1 EP0841186 A1 EP 0841186A1 EP 97118622 A EP97118622 A EP 97118622A EP 97118622 A EP97118622 A EP 97118622A EP 0841186 A1 EP0841186 A1 EP 0841186A1
Authority
EP
European Patent Office
Prior art keywords
granules
bis
laser
weight
thermoplastic
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Withdrawn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
EP97118622A
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German (de)
English (en)
Inventor
Detlev Dr. Joachimi
Herbert Magerstedt
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.)
Bayer AG
Original Assignee
Bayer AG
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Bayer AG filed Critical Bayer AG
Publication of EP0841186A1 publication Critical patent/EP0841186A1/fr
Withdrawn legal-status Critical Current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
    • B41M5/267—Marking of plastic artifacts, e.g. with laser

Definitions

  • the invention relates to the use of at least two differently pigmented polymeric molding compounds for the production of molded parts that have a dark have marbled or colored marbled surface or covered with one colored lacquer are provided and after laser inscription a two or multi-colored show colored marking with high contrast.
  • the present invention relates to the use of at least two different colored thermoplastic molding compositions, preferably in the form of their Granules, for the production of molded parts, which after laser marking on the laser-marked areas are at least two-colored.
  • the present invention furthermore relates to the one described above Use for the production of the shaped bodies by two- or multi-component injection molding as well as by hot pressing two or more different colored granules to form bodies, the two or multicolored molded parts, if necessary, colored with a suitable muted Paint or foil are provided and by laser inscription on the marked areas of the paint or film is eliminated and thereby different colors of the surface with good contrast to the lacquer layer or film layer (background).
  • the present invention also relates to a method as above described for the production of the molded body by two- or multi-component injection molding or by hot pressing, the different colored components After laser inscription, a light to white, paired with a single or multi-colored or dark to black lettering or possibly a dark to black, paired with a one or multi-colored lettering with good contrast to the colored, if necessary black / white marbled, possibly black / colored marbled, optionally white / finished marbled, possibly monochrome dark or if necessary, monochrome light background.
  • the two- or multi-component injection molding process is known per se.
  • Two or more different colored thermoplastic granules are used for separately in a two- or multi-component injection molding machine at and processed into molded articles for known injection molding parameters. in the processing is generally carried out at temperatures in the range from 100 to 400 ° C, preferably 130 to 380 ° C, especially 150 to 350 ° C, depending on thermoplastic used.
  • temperatures in the range from 100 to 400 ° C, preferably 130 to 380 ° C, especially 150 to 350 ° C, depending on thermoplastic used.
  • the border areas of the processed two or more thermoplastic moldings are obtained in a transition phase, otherwise the components themselves are not mixed here. Consequently you get a juxtaposed two or multi-phase structure in the thermoplastic molded body.
  • thermoplastic molding compounds in an almost molten Bring condition.
  • hot pressing Temperatures from 70 to 350 ° C, preferably 90 to 300 ° C, especially 100 to 260 ° C applied, depending on the thermoplastic used. Under pressure these mixed granules are then pressed into the final shape. By Cooling below the melting temperature range causes the molded body to solidify Condition above and can be taken from the form.
  • the moldings produced in this way are optionally also painted and then marked with a laser beam in the manner described above.
  • the energy source can be used.
  • the wavelength can be between 193 and 10 600 nm, preferably 532 and 1 064 nm.
  • the molding compositions used according to the invention can be used to apply optical information in the form of patterns, graphics, numbers, letters, Characters, pictures (e.g. passport photos, portraits, photos) etc. by means of Laser energy, e.g. can be used by laser beam recorders.
  • Molding compounds are transferred.
  • Polymers or copolymers e.g. B. based on Polyalkylene terephthalates, aromatic polyesters, polyamide, polycarbonate, polyacrylate, Polymethacrylate, ABS graft polymers, polyolefins such as polyethylene or polypropylene, polystyrene, polyvinyl chloride, polyoxymethylene, polyimide, polyether and polyether ketones, individually or as a blend of different polymers can be used.
  • Polyalkylene terephthalates in the sense of the invention are reaction products from aromatic dicarboxylic acid or its reactive derivatives (e.g. dimethyl esters or anhydrides) and aliphatic, cycloaliphatic or araliphatic Diols and mixtures of these reaction products.
  • Preferred polyalkylene terephthalates can be derived from terephthalic acid (or its reactive derivatives) and aliphatic or cycloaliphatic diols with 2 Manufacture up to 10 carbon atoms using known methods (Kunststoff-Handbuch, Vol. VIII, p. 695 FF, Karl-Hanser-Verlag, Kunststoff 1973).
  • Preferred polyethylene terephthalates contain at least 80, preferably 90 mol%, based on the dicarboxylic acid, terephthalic acid residues and at least 80, preferably at least 90 mol%, based on the diol component, Ethylene glycol and / or 1,4-butanediol residues.
  • the preferred polyalkylene terephthalates can, in addition to terephthalic acid residues 20 mol% of residues of other aromatic dicarboxylic acids with 8 to 14 carbon atoms or contain aliphatic dicarboxylic acids with 4 to 12 carbon atoms, such as residues of Phthalic acid, isophthalic acid, naphthalene-2,6-dicarboxylic acid, 4,4'-diphenyldicarboxylic acid, Succinic, adipic, sebacic, azelaic, cyclohexanediacetic acid.
  • the preferred polyalkylene terephthalates can, in addition to ethylene or 1,4-butanediol glycol residues up to 20 mol% of other aliphatic diols with 3 to 12 carbon atoms or cycloaliphatic diols containing 6 to 21 carbon atoms, e.g.
  • the polyalkylene terephthalates can be 3- or by incorporating relatively small amounts 4-valent alcohols or 3- or 4-basic carboxylic acid, such as those e.g. in the DE-OS 19 00 270 and U.S. Patent 3,692,744 are described.
  • preferred branching agents are trimesic acid, trimellitic acid, trimethylolethane and propane and pentaerythritol.
  • Polyalkylene terephthalates which consist solely of terephthalic acid are particularly preferred and their reactive derivatives (e.g. their dialkyl esters) and ethylene glycol and / or 1,4-butanediol have been produced (polyethylene and polybutylene terephthalate), and mixtures of these polyalkylene terephthalates.
  • Preferred polyalkylene terephthalates are also copolyesters which consist of at least two of the above acid components and / or from at least two of the above alcohol components are produced, particularly preferred copolyesters are poly (ethylene glycol / 1,4-butanediol) terephthalates.
  • the polyalkylene terephthalates preferably used as component A have generally an intrisic viscosity of about 0.4 to 1.5 dl / g, preferably 0.5 to 1.3 dl / g, each measured in phenol / o-dichlorobenzene (1: 1 parts by weight) at 25 ° C.
  • the diphenols can be used both individually and in a mixture.
  • Particularly preferred aromatic polycarbonates are based on polycarbonates of 2,2-bis (4-hydroxyphenyl) propane or one of the others as preferred called diphenols.
  • 2,2-bis (4-hydroxyphenyl) propane are very particularly preferred, 2,2-bis (3,5-dimethyl-4-hydroxyphenyl) propane or 1,1-bis (4-hydroxyphenyl) -3,3,5-trimethylcyclohexane or mixtures of 2,2-bis (4-hydroxyphenyl) propane and 1,1-bis (4-hydroxyphenyl) -3,3,5-trimethylcyclohexane.
  • the aromatic polycarbonates can be produced by known processes e.g. by melt transesterification with a corresponding bisphenol Diphenyl carbonate and in solution from bisphenols and phosgene.
  • the solution can be homogeneous (pyridine process) or heterogeneous (two-phase interface process) (see H. Schnell, "Chemistry and Physics of Polycarbonates", Polymer Reviews, Vol. IX, S 33ff, Intersciencs Publ. 1964).
  • the aromatic polycarbonates generally have average molecular weights M w from approx. 10,000 to 200,000, preferably 20,000 to 80,000 (determined by gel chromatography after prior calibration).
  • Copolycarbonates in the sense of the invention are in particular polydiorganosiloxane-polycarbonate block copolymers with medium molecular weight M w from approximately 10,000 to 200,000, preferably 20,000 to 80,000 (determined by gel chromatography after prior calibration) and with a content of aromatic carbonate structural units of about 75 to 97.5% by weight, preferably 85 to 97% by weight and a content on polydiorganosiloxane structural units from about 25 to 2.5% by weight, preferably 15 to 3% by weight, the block copolymers starting from polydiorganosiloxanes containing ⁇ , ⁇ -bishydroxyaryloxy end groups and having a degree of polymerization P n of 5 to 100, preferably 20 to 80 , getting produced.
  • M w medium molecular weight
  • M w medium molecular weight
  • 20,000 to 80,000 determined by gel chromatography after prior calibration
  • a content of aromatic carbonate structural units of about 75 to 97.5% by weight, preferably 85
  • the polydiorganosiloxane-polycarbonate block polymers can also be a Mixture of polydiorganosiloxane-polycarbonate block copolymers with conventional ones be polysiloxane-free, thermoplastic polycarbonates, the total content about 2.5 to 25% by weight of polydiorganosiloxane structural units in this mixture is.
  • Alkyl in the above formula (2) is, for example, C 1 -C 20 -alkyl
  • alkenyl in the above formula (2) is, for example, C 2 -C 6 -alkenyl
  • Aryl in the above formula (2) is C 6 -C 14 aryl.
  • Halogenated in the above formula means partially or completely chlorinated, brominated or fluorinated.
  • alkyls, alkenyls, aryls, halogenated alkyls and halogenated aryls are methyl, ethyl, propyl, n-butyl, tert-butyl, vinyl, phenyl, naphthyl, Chloromethyl, perfluorobutyl, perfluorooctyl and chlorophenyl.
  • Such polydiorganosiloxane-polycarbonate block copolymers are e.g. from US PS 3,189,662, U.S. Patent 3,821,325 and U.S. Patent 3,832,419.
  • Preferred polydiorganosiloxane-polycarbonate block copolymers are produced by using polydiorganosiloxanes containing ⁇ , ⁇ -bishydroxyaryloxy end groups together with other diphenols, optionally with the use of Branching in the usual amounts, e.g. according to the two-phase interface method (see also H. Schnell, Chemistry and Physics of Polycarbonates Polymer Rev. Vol. IX, page 27 ff, Interscience Publishers New York 1964) each selected the ratio of the bifunctional phenolic reactants is that the content of aromatic carbonate structural units according to the invention and diorganosiloxy units results.
  • Such ⁇ , ⁇ -bishydroxyaryloxy end group-containing polydiorganosiloxanes are e.g. known from US 3,419,634.
  • ABS graft polymers in the sense of the invention are graft polymers from
  • the graft monomers in the grafting reaction are not necessarily complete grafted onto the graft base arise from the graft monomers Copolymers.
  • the term ABS graft polymers are also to understand those products which, due to polymerization, are precisely these copolymers contain.
  • the average particle diameter d 50 of the ABS graft polymer is generally 0.5 to 5 nm, preferably 0.1 to 2 nm.
  • the average particle diameter d 50 is the diameter above and below which 50% by weight of the particles lie. It can be determined by means of ultracentrifuge measurements (W. Scholtan, H. Lange, Kolloid, Z. Polymer 250 (1972), 782-796).
  • Polyolefins are polyethylene, polypropylene, poly-1-butene and polymethylpentene, which still contain small amounts of non-conjugated dienes in copolymerized form can. These polymers are known and are in Roempp's chemistry dictionary, 8th edition 1987, vol. 5, page 3307 and in the literature cited therein. Prefers is polypropylene.
  • polyamides or polyamides with a predominantly aliphatic content are used as polyamides in the thermoplastic polyamide molding compositions.
  • diamines preferably C 4 -C 16 -, in particular C 4 -C 8 -alkylenediamines
  • dicarboxylic acids preferably C 4 -C 12 -, in particular C 4 -C 8 - are preferred Alkylenedicarboxylic acids
  • pigments Dyes Both organic and inorganic pigments and / or are suitable as pigments Dyes. If necessary, carbon black or graphite can also be added. Optionally, the pigments / dyes and / or carbon blacks, graphites too be used as a batch.
  • inorganic pigments used as additives for discoloration used are antimony trioxide, antimony pentoxide, basic lead carbonate, basic lead sulfate or lead silicate, lithopone, titanium dioxide (anatase, rutile), Zinc oxide, zinc sulfide, metal oxides such as Berlin blue, lead chromate, lead sulfochromates, Chromium-antimony-titanate, chromium oxides, iron oxides, cobalt blue, cobalt chrome blue, Cobalt nickel gray, manganese blue, manganese violet, molybdenum orange, Molybdate red, nickel antimony titanate, ultramarine blue, and metal sulfides such as Arsenic disulfide, antimony trisulfide, cadmium sulfide, cadmium sulfoselenide, zirconium silicates such as zirconium vanadium blue, zirconium presode yellow.
  • organic pigments used as additives for discoloration are used are anthraquinone, azo, azomethine, benzanthrone, Quinacridone, quinophthalone, dioxazine, flavanthrone, indanthrone, isoindo-lin, Isoindolinone, methine, perinone, perylene, phthalocyanine, pyranthrone, Pyrrolopyrrole, thioindigo pigments and metal complexes of e.g. B. azo, Azomethine, methine dyes or metal salts of azo compounds.
  • Dispersion dyes are suitable as polymer-soluble dyes, such as those of the anthraquinone series, for example alkylamino, amino, arylamino, Cyclohexylamino, hydroxy, hydroxyamino or phenylmercaptoanthraquinones, as well as metal complexes of azo dyes, in particular 1: 2 chromium or cobalt complexes of monoazo dyes, and fluorescent dyes, for example those from the benzthiazole, coumarin, oxarin, or thiazine series.
  • polymer-soluble dyes such as those of the anthraquinone series, for example alkylamino, amino, arylamino, Cyclohexylamino, hydroxy, hydroxyamino or phenylmercaptoanthraquinones, as well as metal complexes of azo dyes, in particular 1: 2 chromium or cobalt complexes of monoazo dyes, and fluorescent dye
  • the polymer-soluble dyes are preferred in combinations with fillers and / or pigments, in particular with inorganic pigments such as titanium dioxide used.
  • pigments or polymer-soluble dyes with or without Pigment additives are used.
  • all you have to do is pay attention that they with the thermoplastic polymers used in the invention are compatible and their mechanical or other properties are not affect.
  • Suitable pigment additives are, for example, fatty acids with at least 12 carbon atoms, such as behenic acid or stearic acid, their amides, salts or esters, such as aluminum stearate, magnesium stearate, zinc stearate, or magnesium behenate, and quaternary ammonium compounds, such as tri (C 1 -C 4 ) alkylbenzylammonium salts Waxes, such as polyethylene wax, resin acids, such as abietic acid, rosin soap, hydrogenated or dimerized rosin, C 12 -C 18 paraffin disulfonic acids or alkylphenols.
  • fatty acids with at least 12 carbon atoms such as behenic acid or stearic acid, their amides, salts or esters, such as aluminum stearate, magnesium stearate, zinc stearate, or magnesium behenate
  • quaternary ammonium compounds such as tri (C 1 -C 4 ) alkylbenzylammonium salt
  • the metal-containing pigments such as the inorganic pigments
  • Pigments especially titanium dioxide and the metal complexes of azo, Azomethine or methine dyes.
  • anthraquinone azo, azomethine, quinacridone, dioxazine, Isoindoline, isoindolinone, methine, perylene, phthalocyanine, pyrrolopyrrole, or thioindigo pigments.
  • the inorganic metal-containing pigments are particularly preferably phthalocyanine-metal complex, Copper phthalocyanine, monoazo 1: 2 chromium complexes, azo metal complex and bismuth vanadate.
  • Pigment blacks and titanium dioxides are also particularly preferred.
  • Preferred reinforcing materials are commercially available Fiberglass.
  • the glass fibers which generally have a fiber diameter between 8 and 14 ⁇ m, can be used as continuous fibers. or as cut or ground glass fibers are used, the fibers with a suitable Sizing system and an adhesion promoter or adhesion promoter system based on silane can be equipped.
  • the mixture is preferably 8 to 45, in particular 10 to 40 parts by weight of fillers and reinforcing materials are added.
  • organic compounds or halogen compounds are flame retardant additives with synergists or commercially available organic nitrogen compounds or organic / inorganic phosphorus compounds.
  • mineral flame retardants such as Mg hydroxide or Ca-Mg carbonate hydrate can be used.
  • the molding compositions according to the invention can contain up to 20, preferably 3 to 18, in particular 6 to 15 parts by weight of halogenated compounds and up to 8, preferably 2 to 6 parts by weight of antimony compounds, especially antimony trioxide or contain antimony pentoxide.
  • Poly (pentabromobenzyl acrylate) generally has average molecular weights M w (weight average) from 10,000 to 200,000, brominated polystyrene generally from 10,000 to 500,000.
  • Epoxidized tetrabromobisphenol-A and tetrabromobisphenol-A oligocarbonate are preferred used.
  • Expoxidized tetrabromobisphenol-A is a known diepoxide resin with a molecular weight of about 350 to about 2,100, preferably 360 to 1,000, particularly preferably 370 to 400, and consists essentially of at least one condensation product of bisphenol A and epihalohydrin and is described by the formula (I ) wherein X represents hydrogen or bromine and n is an average number between zero and less than 2.3 (see, for example, EP-A 180 471).
  • Tetrabromobisphenol A oligocarbonate or tetrachlorobisphenol A oligocarbonate is described by formula (II), the oligomers being terminated either with phenol or with tribromophenol or trichlorophenol: where X represents hydrogen, bromine or chlorine, n is an average number between 4 and 7.
  • Tetrabromo (chloro) bisphenol A oligocarbonate is known and according to known methods producible.
  • the phosphorus compounds are in accordance with EP-A 345 522 (US-PS 061.745) or DE-OS 43 28 656.9 in those described there Suitable amounts, e.g. Triphenyl phosphate, oligomeric phosphates, resorcinol diphosphate or a mixture of them.
  • EP (D) M rubbers graft rubbers come as elastomer modifiers based on butadiene, styrene, acrylonitrile (see e.g. those described above ABS graft polymers), acrylate rubbers, thermoplastic polyurethanes or EVA copolymers with or without functional coupling groups questionable.
  • Antimony trioxide is well known and can e.g. B. from Campine be acquired.
  • the molding compositions according to the invention can be conventional additives, such as lubricants and Mold release agents, nucleating agents, antistatic agents, stabilizers contain.
  • the molding compositions according to the invention from the respective components and optionally other known additives such as stabilizers, lubricants and mold release agents, Reinforcing agents, nucleating agents and antistatic agents can be prepared by the respective components in a known manner, optionally in the form of masterbatches, admixed with the thermoplastic polymer and at temperatures from 180 ° C to 330 ° C in common units such as Internal kneaders, extruders, twin-screw extruders or melt-compounded melt extruded.
  • the material obtained is then known per se Process in two- or multi-component injection molding into the desired final Formed.
  • the material obtained can optionally also be injection molded into shaped articles processed, but it should be noted that the at least 2 different colored thermoplastic molding compositions do not mix homogeneously.
  • the two-colored or multicolored thermoplastic molding thus obtained can according to the invention with a preferably covered lacquer, wherein laser marking on the marked areas eliminates the paint and therefore different colors of the surface with good contrast to Lacquer layer are caused.
  • Saturated resins for example, can be used as coating resins for the process according to the invention and unsaturated polyester can be used.
  • unsaturated polyester come z.
  • unsaturated resins come for example maleate resins in question.
  • High molecular weight organic ones can also be used for the process according to the invention Dissolved materials as film formers or binders for paints or Printing inks are used.
  • acrylic resins for example, acrylic resins, alkyd resins, urea-formaldehyde resins, Melamine resins, linseed oil varnish, nitrocellulose, phenolic resins can be used.
  • thermoplastic molded body with a suitable colored film be provided, the laser marking at the marked points Foil is eliminated and therefore different colors of the surface with good contrast to the film layer (background).
  • High-energy sources are used to label the thermoplastic molded articles like laser used.
  • the energy radiation is according to the shape of the characters to be applied to the surface of the material to be marked directed, possibly focused, with discoloration at the irradiated areas arises.
  • Such sources are solid-state pulse lasers such as ruby lasers or frequency multipliers Nd: YAG laser, pulsed laser with additional device such as pulsed dye laser or Raman shifter, further continuous wave laser with pulse modification (Q switch, mode locker), for example based on CW Nd: YAG laser with frequency multiplier or CW ion laser (Ar, Kr), also pulsed Metal vapor lasers, such as Cu vapor lasers or Au vapor lasers, or at most powerful pulsed semiconductor lasers.
  • Nd YAG laser
  • pulsed laser with additional device such as pulsed dye laser or Raman shifter
  • Q switch, mode locker further continuous wave laser with pulse modification
  • Q switch, mode locker for example based on CW Nd: YAG laser with frequency multiplier or CW ion laser (Ar, Kr)
  • pulsed Metal vapor lasers such as Cu vapor lasers or Au vapor lasers, or at most powerful pulsed semiconductor lasers.
  • pulse energies are up to a few joules, power densities up to terawatts per cm 2 ; Pulse widths up to femto seconds and repetition rates up to gigahertz possible. Pulse energies from microjoules to joules, power densities from kilowatts per cm 2 to 100 megawatts per cm 2 , pulse widths from micro seconds to pico seconds and repetition rates from hertz to 250 megahertz are advantageously used.
  • Lasers with pulsed light are preferably used. Are particularly preferred pulsed or pulse-modified, frequency-doubled Nd-YAG laser or metal vapor laser such as Au or especially Cu steam lasers.
  • Lasers with good adjustability of their laser parameters such as pulse energy with exposure time allow an optimal adaptation to the needs of the labeling materials.
  • the Mask process There are three different methods for marking with lasers: the Mask process, the line-shaped labeling and the dot matrix process.
  • the laser is preferably coupled to a laser marking system, so that the high molecular organic material with any, for example in one Computer programmed digits, letters and special characters on the Impact point of the laser beam can be labeled.
  • the choice of laser system in terms of power and repetition rate is based basically according to the labeling method used. High performance and low repetition rates as with the solid-state pulse laser preferably used for mask exposures. Medium to small performances and fast repetition rates with the pulsed metal vapor laser or as with the Continuous wave lasers with pulse modifications are preferred for labeling applied that require dynamic beam guidance.
  • the beam deflection can be acousto-optic, holographic with galvo mirrors or polygon scanners respectively.
  • the dynamic beam guidance allows an extremely flexible Lettering or marking as the characters are generated electronically can.
  • the most varied types of labeling can be used be preserved.
  • Examples include: variable text programming numerical characters using text input on a screen terminal, Test programs for standard characters or special characters such as names, signets or repetitive data, sequential numbering, Input of measurement parameters, input of a saved program, line labeling or decorations.
  • strips, sheets, Pipes and profiles, buttons and electronic components encased in plastic be marked by a laser beam.
  • Typical application examples are the labeling of circuits, printed circuit boards, printed circuits, active and passive electronic components, encapsulated high-voltage transformers, sockets, housings, mechanical Components from the precision engineering and the watch industry, vehicle components, Keyboards, electronic components, cables, pipes, paints, foils and packaging films, as well as banknotes and securities.
  • the method according to the invention enables marking which does not blur can be and is therefore abrasion and scratch resistant.
  • markings obtained are also corrosion-resistant, dimensionally stable, free of deformation, light, heat and weather resistant, easy to read and with clean Marginal zones.
  • the mechanical and physical properties of the material so labeled is practically unaffected.
  • the depth of penetration of the Marking depends on the labeled material. It is up to approx. 1 mm.
  • the High molecular organic material is largely spared. There are inscriptions are therefore possible that do not show any loss visible to the eye Effect surface gloss.
  • laser irradiation occurs on the irradiated Set the material a color change with a pronounced contrast.
  • Granules 1 and 2 are 2-component injection molded with those described in the text usual manufacturing conditions on a two-component Engel injection molding machine according to known injection molding processes at 260 ° C melt temperature Molded bodies processed.
  • the granules 3 and 4 are in 2-component injection molding according to the instructions at Example 1 processed into moldings.
  • the granules 1 and 4 are 2-component injection molding according to Example 1 Molded bodies processed.
  • Granules 1 and 5 are in 2-component injection molding according to the instructions at Example 1 processed into moldings.
  • Granules 2 and 5 are injection molded in two components according to the instructions processed into moldings in Example 1.
  • the granules 3 and 5 are 2-component injection molded according to the instructions processed into moldings in Example 1.
  • the granules 4 and 5 are 2-component injection molded according to the instructions processed into moldings in Example 1.
  • the moldings are produced on a two-component Engel injection molding machine using known injection molding processes at a melt temperature of 260 ° C.
  • the granules 1 and 2 become molded articles under the action of pressure and temperature pressed at approx. 220 ° C.
  • the granules 3 and 4 become molded articles under the action of pressure and temperature pressed at approx. 220 ° C.
  • Granules 1 and 4 become molded articles under the action of pressure and temperature pressed at approx. 220 ° C.
  • Granules 1 and 5 become molded articles under the action of pressure and temperature pressed at approx. 220 ° C.
  • the granules 2 and 5 become molded articles under the action of pressure and temperature pressed at approx. 220 ° C.
  • the molded articles are produced on a Lauffer press using known pressing processes.
  • the granules 3 and 5 become molded articles under the action of pressure and temperature pressed at approx. 220 ° C.
  • the granules 4 and 5 become molded articles under the action of pressure and temperature pressed at approx. 220 ° C.
  • Granules 1 and 6 become molded articles under the action of pressure and temperature pressed at approx. 220 ° C.
  • the granules 2 and 6 become molded articles under the action of pressure and temperature pressed at approx. 220 ° C.
  • the granules 3 and 6 become molded articles under the action of pressure and temperature pressed at approx. 220 ° C.
  • the molded articles are produced on a Lauffer press using known pressing processes.
  • the granules 4 and 6 become molded articles under the action of pressure and temperature pressed at approx. 220 ° C.
  • the granules 1 and 3 and 6 become molded articles under the action of pressure and temperature pressed at approx. 220 ° C.
  • the granules 1 and 4 and 6 become molded articles under the action of pressure and temperature pressed at approx. 220 ° C.
  • the granules 1 and 2 and 3 and 6 become molded articles under pressure and Temperature impact pressed at approx. 220 ° C.
  • the granules 1 and 2 and 3 and 4 and 6 become molded articles under pressure and temperature influence pressed at approx. 220 ° C.
  • the molded articles are produced on a Lauffer press using known pressing processes.
  • Examples 18th 19th 20th 21 22 Background color very dark to black marbled font several mixed colors Font colors white and orange white, blue and yellow white, blue and orange white, blue, green and yellow white, blue, green, yellow and orange Contrast rating 2+ 2+ 2+ 2+ 2+ Laser parameters: Current [A] 12-16 Frequency [Hz] 1,000 - 8,000 Labeling speed [mm / s] 300 - 1,500

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  • Physics & Mathematics (AREA)
  • Optics & Photonics (AREA)
  • Compositions Of Macromolecular Compounds (AREA)
  • Casting Or Compression Moulding Of Plastics Or The Like (AREA)
  • Injection Moulding Of Plastics Or The Like (AREA)
  • Manufacture Of Macromolecular Shaped Articles (AREA)
EP97118622A 1996-11-07 1997-10-27 Compositions polymères à mouler, marquables au laser Withdrawn EP0841186A1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
DE19645871 1996-11-07
DE1996145871 DE19645871A1 (de) 1996-11-07 1996-11-07 Laserbeschriftbare Polymerformmassen

Publications (1)

Publication Number Publication Date
EP0841186A1 true EP0841186A1 (fr) 1998-05-13

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EP (1) EP0841186A1 (fr)
JP (1) JPH10138293A (fr)
DE (1) DE19645871A1 (fr)

Cited By (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US6383721B1 (en) * 1998-11-17 2002-05-07 Matsushita Electric Industrial Co., Ltd. Marking method and marked resin molded piece
WO2004050767A1 (fr) * 2002-12-04 2004-06-17 Dsm Ip Assets B.V. Composition d'ecriture par laser
WO2006042715A1 (fr) * 2004-10-15 2006-04-27 Ticona Gmbh Matieres moulables ignifuges marquables au laser et produits marquables ou marques au laser obtenus a partir de ces matieres moulables
WO2021250053A1 (fr) * 2020-06-10 2021-12-16 Röhm Gmbh Composition de moulage thermoplastique présentant une résistance aux intempéries améliorée
CN115746532A (zh) * 2022-11-29 2023-03-07 金旸（厦门）新材料科技有限公司 一种继电器用可镭雕无卤阻燃增强聚碳酸酯材料及其制备方法

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DE10053639B4 (de) * 2000-10-28 2007-04-12 Chemische Fabrik Budenheim Kg Verwendung von Eisen-, Cobalt-, Nickel- oder Molybdänsalzen
JP4936601B2 (ja) * 2001-03-08 2012-05-23 出光興産株式会社 レーザーマーキング用樹脂及び樹脂組成物並びに成形品
DE102010021120A1 (de) * 2010-05-19 2011-11-24 Faurecia Innenraum Systeme Gmbh Verfahren zum Herstellen eines Dekors auf einer Sichtseite eines Kunststoffteils sowie Kunststoffteil mit einem Dekor
DE102010030539A1 (de) * 2010-06-25 2011-12-29 Faber-Castell Ag Verfahren zur Herstellung eines Stiftes mit einem aus Kunststoff bestehenden, erhaben aus seiner Oberfläche vorstehende Strukturen aufweisenden Schaft
DE102011115256A1 (de) 2011-09-27 2013-03-28 Bernd Hansen Verfahren zum Einbringen mindestens einer Struktur in ein Kunststoffbehältererzeugnis
DE102013003160A1 (de) * 2013-02-26 2014-08-28 Photon Energy Gmbh Verfahren zur Modifizierung der Oberfläche eines Kunststoffs
EP3792303A1 (fr) * 2019-09-10 2021-03-17 LANXESS Deutschland GmbH Composants haut voltage
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WO2004050767A1 (fr) * 2002-12-04 2004-06-17 Dsm Ip Assets B.V. Composition d'ecriture par laser
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WO2006042715A1 (fr) * 2004-10-15 2006-04-27 Ticona Gmbh Matieres moulables ignifuges marquables au laser et produits marquables ou marques au laser obtenus a partir de ces matieres moulables
WO2021250053A1 (fr) * 2020-06-10 2021-12-16 Röhm Gmbh Composition de moulage thermoplastique présentant une résistance aux intempéries améliorée
CN115715307A (zh) * 2020-06-10 2023-02-24 罗姆化学有限责任公司 具有改进耐候性的热塑性模塑组合物
CN115715307B (zh) * 2020-06-10 2025-09-30 罗姆化学有限责任公司 具有改进耐候性的热塑性模塑组合物
CN115746532A (zh) * 2022-11-29 2023-03-07 金旸（厦门）新材料科技有限公司 一种继电器用可镭雕无卤阻燃增强聚碳酸酯材料及其制备方法

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