WO2006029677A1 - Materiaux polymeres pouvant etre marques et soudes au laser - Google Patents

Materiaux polymeres pouvant etre marques et soudes au laser Download PDF

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Publication number
WO2006029677A1
WO2006029677A1 PCT/EP2005/008677 EP2005008677W WO2006029677A1 WO 2006029677 A1 WO2006029677 A1 WO 2006029677A1 EP 2005008677 W EP2005008677 W EP 2005008677W WO 2006029677 A1 WO2006029677 A1 WO 2006029677A1
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Prior art keywords
laser
markable
boride
polymers according
weldable
Prior art date
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PCT/EP2005/008677
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German (de)
English (en)
Inventor
Silvia Rosenberger
Manfred Kieser
Reinhold Rueger
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Merck Patent Gmbh
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Publication of WO2006029677A1 publication Critical patent/WO2006029677A1/fr

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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/38—Boron-containing compounds
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C65/00—Joining or sealing of preformed parts, e.g. welding of plastics materials; Apparatus therefor
    • B29C65/02—Joining or sealing of preformed parts, e.g. welding of plastics materials; Apparatus therefor by heating, with or without pressure
    • B29C65/14—Joining or sealing of preformed parts, e.g. welding of plastics materials; Apparatus therefor by heating, with or without pressure using wave energy, i.e. electromagnetic radiation, or particle radiation
    • B29C65/16—Laser beams
    • B29C65/1677—Laser beams making use of an absorber or impact modifier
    • 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
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C65/00—Joining or sealing of preformed parts, e.g. welding of plastics materials; Apparatus therefor
    • B29C65/02—Joining or sealing of preformed parts, e.g. welding of plastics materials; Apparatus therefor by heating, with or without pressure
    • B29C65/14—Joining or sealing of preformed parts, e.g. welding of plastics materials; Apparatus therefor by heating, with or without pressure using wave energy, i.e. electromagnetic radiation, or particle radiation
    • B29C65/16—Laser beams
    • B29C65/1603—Laser beams characterised by the type of electromagnetic radiation
    • B29C65/1606—Ultraviolet [UV] radiation, e.g. by ultraviolet excimer lasers
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C65/00—Joining or sealing of preformed parts, e.g. welding of plastics materials; Apparatus therefor
    • B29C65/02—Joining or sealing of preformed parts, e.g. welding of plastics materials; Apparatus therefor by heating, with or without pressure
    • B29C65/14—Joining or sealing of preformed parts, e.g. welding of plastics materials; Apparatus therefor by heating, with or without pressure using wave energy, i.e. electromagnetic radiation, or particle radiation
    • B29C65/16—Laser beams
    • B29C65/1603—Laser beams characterised by the type of electromagnetic radiation
    • B29C65/1612—Infrared [IR] radiation, e.g. by infrared lasers
    • B29C65/1616—Near infrared radiation [NIR], e.g. by YAG lasers
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C65/00—Joining or sealing of preformed parts, e.g. welding of plastics materials; Apparatus therefor
    • B29C65/02—Joining or sealing of preformed parts, e.g. welding of plastics materials; Apparatus therefor by heating, with or without pressure
    • B29C65/14—Joining or sealing of preformed parts, e.g. welding of plastics materials; Apparatus therefor by heating, with or without pressure using wave energy, i.e. electromagnetic radiation, or particle radiation
    • B29C65/16—Laser beams
    • B29C65/1603—Laser beams characterised by the type of electromagnetic radiation
    • B29C65/1612—Infrared [IR] radiation, e.g. by infrared lasers
    • B29C65/1619—Mid infrared radiation [MIR], e.g. by CO or CO2 lasers
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C65/00—Joining or sealing of preformed parts, e.g. welding of plastics materials; Apparatus therefor
    • B29C65/02—Joining or sealing of preformed parts, e.g. welding of plastics materials; Apparatus therefor by heating, with or without pressure
    • B29C65/14—Joining or sealing of preformed parts, e.g. welding of plastics materials; Apparatus therefor by heating, with or without pressure using wave energy, i.e. electromagnetic radiation, or particle radiation
    • B29C65/16—Laser beams
    • B29C65/1629—Laser beams characterised by the way of heating the interface
    • B29C65/1654—Laser beams characterised by the way of heating the interface scanning at least one of the parts to be joined
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C65/00—Joining or sealing of preformed parts, e.g. welding of plastics materials; Apparatus therefor
    • B29C65/02—Joining or sealing of preformed parts, e.g. welding of plastics materials; Apparatus therefor by heating, with or without pressure
    • B29C65/14—Joining or sealing of preformed parts, e.g. welding of plastics materials; Apparatus therefor by heating, with or without pressure using wave energy, i.e. electromagnetic radiation, or particle radiation
    • B29C65/16—Laser beams
    • B29C65/1629—Laser beams characterised by the way of heating the interface
    • B29C65/1674—Laser beams characterised by the way of heating the interface making use of laser diodes
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C65/00—Joining or sealing of preformed parts, e.g. welding of plastics materials; Apparatus therefor
    • B29C65/02—Joining or sealing of preformed parts, e.g. welding of plastics materials; Apparatus therefor by heating, with or without pressure
    • B29C65/14—Joining or sealing of preformed parts, e.g. welding of plastics materials; Apparatus therefor by heating, with or without pressure using wave energy, i.e. electromagnetic radiation, or particle radiation
    • B29C65/16—Laser beams
    • B29C65/1696—Laser beams making use of masks
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C66/00—General aspects of processes or apparatus for joining preformed parts
    • B29C66/70—General aspects of processes or apparatus for joining preformed parts characterised by the composition, physical properties or the structure of the material of the parts to be joined; Joining with non-plastics material
    • B29C66/71—General aspects of processes or apparatus for joining preformed parts characterised by the composition, physical properties or the structure of the material of the parts to be joined; Joining with non-plastics material characterised by the composition of the plastics material of the parts to be joined
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C66/00—General aspects of processes or apparatus for joining preformed parts
    • B29C66/70—General aspects of processes or apparatus for joining preformed parts characterised by the composition, physical properties or the structure of the material of the parts to be joined; Joining with non-plastics material
    • B29C66/73—General aspects of processes or apparatus for joining preformed parts characterised by the composition, physical properties or the structure of the material of the parts to be joined; Joining with non-plastics material characterised by the intensive physical properties of the material of the parts to be joined, by the optical properties of the material of the parts to be joined, by the extensive physical properties of the parts to be joined, by the state of the material of the parts to be joined or by the material of the parts to be joined being a thermoplastic or a thermoset
    • B29C66/739—General aspects of processes or apparatus for joining preformed parts characterised by the composition, physical properties or the structure of the material of the parts to be joined; Joining with non-plastics material characterised by the intensive physical properties of the material of the parts to be joined, by the optical properties of the material of the parts to be joined, by the extensive physical properties of the parts to be joined, by the state of the material of the parts to be joined or by the material of the parts to be joined being a thermoplastic or a thermoset characterised by the material of the parts to be joined being a thermoplastic or a thermoset
    • B29C66/7392—General aspects of processes or apparatus for joining preformed parts characterised by the composition, physical properties or the structure of the material of the parts to be joined; Joining with non-plastics material characterised by the intensive physical properties of the material of the parts to be joined, by the optical properties of the material of the parts to be joined, by the extensive physical properties of the parts to be joined, by the state of the material of the parts to be joined or by the material of the parts to be joined being a thermoplastic or a thermoset characterised by the material of the parts to be joined being a thermoplastic or a thermoset characterised by the material of at least one of the parts being a thermoplastic
    • B29C66/73921—General aspects of processes or apparatus for joining preformed parts characterised by the composition, physical properties or the structure of the material of the parts to be joined; Joining with non-plastics material characterised by the intensive physical properties of the material of the parts to be joined, by the optical properties of the material of the parts to be joined, by the extensive physical properties of the parts to be joined, by the state of the material of the parts to be joined or by the material of the parts to be joined being a thermoplastic or a thermoset characterised by the material of the parts to be joined being a thermoplastic or a thermoset characterised by the material of at least one of the parts being a thermoplastic characterised by the materials of both parts being thermoplastics
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C66/00—General aspects of processes or apparatus for joining preformed parts
    • B29C66/70—General aspects of processes or apparatus for joining preformed parts characterised by the composition, physical properties or the structure of the material of the parts to be joined; Joining with non-plastics material
    • B29C66/73—General aspects of processes or apparatus for joining preformed parts characterised by the composition, physical properties or the structure of the material of the parts to be joined; Joining with non-plastics material characterised by the intensive physical properties of the material of the parts to be joined, by the optical properties of the material of the parts to be joined, by the extensive physical properties of the parts to be joined, by the state of the material of the parts to be joined or by the material of the parts to be joined being a thermoplastic or a thermoset
    • B29C66/739—General aspects of processes or apparatus for joining preformed parts characterised by the composition, physical properties or the structure of the material of the parts to be joined; Joining with non-plastics material characterised by the intensive physical properties of the material of the parts to be joined, by the optical properties of the material of the parts to be joined, by the extensive physical properties of the parts to be joined, by the state of the material of the parts to be joined or by the material of the parts to be joined being a thermoplastic or a thermoset characterised by the material of the parts to be joined being a thermoplastic or a thermoset
    • B29C66/7394—General aspects of processes or apparatus for joining preformed parts characterised by the composition, physical properties or the structure of the material of the parts to be joined; Joining with non-plastics material characterised by the intensive physical properties of the material of the parts to be joined, by the optical properties of the material of the parts to be joined, by the extensive physical properties of the parts to be joined, by the state of the material of the parts to be joined or by the material of the parts to be joined being a thermoplastic or a thermoset characterised by the material of the parts to be joined being a thermoplastic or a thermoset characterised by the material of at least one of the parts being a thermoset
    • B29C66/73941—General aspects of processes or apparatus for joining preformed parts characterised by the composition, physical properties or the structure of the material of the parts to be joined; Joining with non-plastics material characterised by the intensive physical properties of the material of the parts to be joined, by the optical properties of the material of the parts to be joined, by the extensive physical properties of the parts to be joined, by the state of the material of the parts to be joined or by the material of the parts to be joined being a thermoplastic or a thermoset characterised by the material of the parts to be joined being a thermoplastic or a thermoset characterised by the material of at least one of the parts being a thermoset characterised by the materials of both parts being thermosets
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29K—INDEXING SCHEME ASSOCIATED WITH SUBCLASSES B29B, B29C OR B29D, RELATING TO MOULDING MATERIALS OR TO MATERIALS FOR MOULDS, REINFORCEMENTS, FILLERS OR PREFORMED PARTS, e.g. INSERTS
    • B29K2023/00—Use of polyalkenes or derivatives thereof as moulding material
    • B29K2023/10—Polymers of propylene
    • B29K2023/12—PP, i.e. polypropylene

Definitions

  • the present invention relates to laser-markable and laser-weldable polymeric materials, which are characterized in that they contain at least one boride compound as an absorber.
  • Barcodes can also be applied to a non-planar surface at high speed. Since the inscription is located in the plastic body itself, it is permanently resistant to abrasion.
  • the marking of plastics by laser marking as well as the welding of plastic parts by means of laser energy is known per se. Both are effected by absorption of the laser energy in the plastic material either directly by interaction with the polymer or indirectly by means of a plastic material added laser-sensitive agent.
  • the laser-sensitive agent may be an organic dye or a pigment which causes absorption of the laser energy.
  • laser marking this causes a local visible discoloration of the plastic or the compound is converted when irradiated with laser light from an invisible, colorless in a visible form.
  • the plastic material is so strongly heated by absorption of the laser energy in the joining area that the plastic melts and weld both parts together.
  • Nd YAG lasers are increasingly being used for the laser marking of plastics.
  • the commonly used YAG lasers emit a pulsed energy beam with a characteristic wavelength of 1064 nm or 532 nm.
  • the absorber material must show a pronounced absorption in this special NIR range in order to show a sufficient response in the fast labeling processes.
  • the object of the present invention was therefore to find laser-markable or laser-weldable polymeric materials which, when exposed to laser light, produce a mark with high contrast or a good contrast
  • the absorber or the successful one Absorbent should therefore hardly change the polymer properties and at the same time only have to be used in very small amounts.
  • the laser marking of polymeric materials, in particular the contrast of the label, as well as the laser welding can be improved if one uses a boride compound in low concentrations as an absorber.
  • the boride compound shows such low intrinsic coloration in the visible spectral range (light wavelength 400-750 nm) in low concentrations that it is particularly suitable for crystal-clear polymers.
  • the doped polymer shows a mark with high contrast and pronounced edge sharpness.
  • CW Nd: YAG lasers even transparent plastics can be welded very well.
  • a boride compound in particular in concentrations of from 0.001 to 10% by weight, preferably from 0.001 to 7% by weight, and in particular from 0.0015 to 3% by weight, based on the polymer, is used in the laser marking of polymers significantly higher contrast achieved than with the commercially available absorbers at comparable concentrations Konzen ⁇ .
  • the boride compound is preferably used in concentrations of from 0.001 to 10% by weight, in particular from 0.001 to 7% by weight and very particularly preferably from 0.01 to 3% by weight.
  • the invention thus relates to a laser-markable or laser-weldable polymeric material, characterized in that the polymer contains at least one boride compound as absorber.
  • the concentration of the absorber in the polymer preferably thermoplastics, thermosets, elastomers, however, depends on the polymer material used.
  • the low proportion of absorber changes the polymer system insignificantly and does not affect its processability.
  • Boride compounds are, in particular, aluminum boride, magnesium boride, molybdenum boride, chromium boride, niobium boride, silicon hexaboride, - A -
  • the boride compounds have particle sizes in the range of 50 nm -
  • 100 ⁇ m preferably from 0.05 to 50 ⁇ m and in particular from 0.05 to 10 ⁇ m. Very particular preference is given to particle sizes of 0.1-5 ⁇ m.
  • the commercially available boride compounds usually have particle sizes significantly> 50 microns, so they are before use as
  • Absorber with a suitable grinding device e.g. a bead mill or ball mill, must be milled to the appropriate particle sizes.
  • the fine grinding is preferably carried out in suspension in water, organic solvents or solvent mixtures, if appropriate in the presence of dispersants.
  • Preferred dispersing aids are those which simultaneously facilitate the incorporation of the finely divided inorganic borides into the plastics compositions, e.g. by hydrophobization of the particle surfaces.
  • the borides are preferably stretched with an inert substance that has no intrinsic color and is compatible with the plastics.
  • Suitable diluents are e.g. precipitated silicas or pyrogens
  • Silicic acids or inorganic fillers e.g. Kaolin or mica.
  • the fabrics can be added before or after fine grinding.
  • the laser light absorbing substances suitable for the marking are preferably based on anthracene, pentaerythritol, copper phosphates, copper hydroxide phosphates, eg libethenite, molybdenum disulfide, molybdenum oxide, antimony (III) oxide and bismuth oxychloride, platelet-shaped, in particular transparent or semitransparent, substrates of e.g. B. Schicht ⁇ silicates, such as synthetic or natural mica, talc, kaolin, glass flakes, SiO 2 platelets or synthetic carrier-free platelets.
  • platelet-shaped metal oxides such as Example, platelet-shaped iron oxide, alumina, titanium dioxide, silicon dioxide, LCP's (liquid crystal polymers), holographic pigments, conductive pigments or coated or uncoated graphite platelets into consideration.
  • metal flakes which may be uncoated or else covered with one or more metal oxide layers; preferred are z.
  • AI, Fe or steel plates are used uncoated, they are preferably coated with a protective polymer layer.
  • Particularly preferred substances are uncoated or coated with one or more metal oxides mica flakes.
  • metal oxides mica flakes are used as metal oxides, as well as colored metal oxides, such.
  • Particularly preferred is as a laser light absorbing substance
  • Antimony (III) oxide, antimony tin oxide or combinations of tin oxide with antimony (III) oxide used.
  • Pigments based on transparent or semitransparent platelet-shaped substrates are e.g. As described in German patents and patent applications 14 67 468, 19 59 998, 20 09 566, 22 14 454, 22 15 191, 22 44 298, 23 13 331, 25 22 572, 31 37 808, 31 37 809, 31 51 343, 31 51 354, 31 51 355, 32 11 602, 32 35 017, 38 42 330, 44 41 223, 196 18 569, 196 38 708, 197 07 806 and 198 03 550.
  • Coated SiO 2 platelets are z. B. known from WO 93/08237 (wet-chemical coating) and DE-OS 196 14 637 (CVD method).
  • Multilayered pigments based on phyllosilicates are known, for example, from German published patent applications DE 196 18 569, DE 196 38 708, DE 197 07 806 and DE 198 03 550. Particularly suitable are multilayer pigments which have the following structure:
  • laser light absorbing substances are natural or synthetic mica, coated with TiO 2 mica platelets, conductive pigments, such as with (Sn, Sb) O 2 coated platelet-shaped substrates, antimony and antimony (III) oxide, anthracene, pentaerythritol, copper (hydroxide) phosphates , Molybdenum disulfide, molybdenum oxide, undoped or antimony-doped tin oxide and bismuth oxychloride, and mixtures of said substances.
  • the mixing ratio boride compound with a further laser-light-sensitive substance is preferably 1:10 to 10: 1, in particular 1:10.
  • Preferred absorber mixtures are
  • Particularly preferred mixtures contain lathanhexaboride.
  • the total concentration of the mixture absorber / light-sensitive substance should not exceed 10% by weight, based on the polymer, in the case of laser marking.
  • the concentration should be ⁇ 10% by weight in the joining area.
  • compositions of the absorber the addition of small amounts of a metal halide, preferably calcium chloride, ⁇ 5% by weight is advantageous for the laser marking contrast of the polymer.
  • colorants can be added to the polymers which allow color variations of any kind and at the same time ensure retention of the laser marking or of the laser welding.
  • Suitable colorants are in particular colored metal oxide pigments and organic pigments and dyes.
  • thermoplastics in particular thermoplastics, furthermore thermosetting plastics and elastomers, are suitable, as described, for example, in Ulimann, Vol. 15, p. 457 ff., Verlag VCH.
  • Suitable polymers are, for example, polyethylene, polypropylene, polyamides, polyesters, polyester esters, polyether esters, polyphenylene ethers, polyacetal, polyurethane, polybutylene terephthalate (PBT), polymethyl methacrylate, polyvinyl acetal, polystyrene, acrylonitrile-butadiene-styrene (ABS), acrylonitrile-styrene Acrylic ester (ASA), polycarbonate, polyether sulfones and polyether ketones and their copolymers, mixtures, and / or polymer blends, such as PC / ABS, MABS.
  • drilling compound (s) and optionally another laser-sensitive substance, e.g. an effect pigment, molybdenum oxide,
  • Kupferphoshats, an antimony compound and / or phyllosilicate, in the polymer, preferably a thermoplastic takes place by the polymer granules are mixed with the absorber and then deformed under hills ⁇ effect.
  • the addition of the absorber or absorber mixture to the polymer can take place simultaneously or successively.
  • adhesives, organic polymer-compatible solvents, stabilizers and / or surfactants which are stable under the working conditions may be added to the polymer, preferably a plastic granulate.
  • the preparation of the doped plastic granules is usually carried out so that presented in a suitable mixer, the plastic granules, wetted with any additives and then the absorber is added and mixed.
  • the pigmentation of the polymer is generally carried out via a color concentrate (masterbatch) or compound.
  • the mixture thus obtained can then be processed directly in an extruder or an injection molding machine.
  • the shaped bodies formed during processing show a very homogeneous distribution of the absorber.
  • the laser marking takes place with a suitable laser.
  • the invention also provides a process for the preparation of the doped polymeric materials according to the invention, characterized in that a polymeric material is mixed with the absorber and then deformed under the action of heat.
  • the inscription with the laser takes place in such a way that the specimen is brought into the beam path of a pulsed laser, preferably an Nd: YAG laser. Furthermore, a lettering with an excimer laser, for example via a mask technique, possible. However, the desired results are also to be achieved with other conventional laser types which have a wavelength in a range of high absorption of the pigment used.
  • the label obtained is replaced by the time (or pulse rate in pulse lasers) and irradiation power of the laser and the plastic system used. The power of the laser used depends on the particular application and can be determined in individual cases by the skilled person readily.
  • the laser used generally has a wavelength in the range of 157 nm to 10.6 ⁇ m, preferably in the range of 532 nm to 10.6 ⁇ m.
  • a wavelength in the range of 157 nm to 10.6 ⁇ m, preferably in the range of 532 nm to 10.6 ⁇ m.
  • CO 2 lasers (10.6 ⁇ m) and Nd: YAG lasers (1064 or 532 nm) or pulsed UV lasers.
  • the excimer lasers have the following wavelengths: F 2 excimer laser (157 nm), ArF excimer laser (193 nm), KrCl excimer laser (222 nm), KrF excimer laser (248 nm), XeCl excimer laser (308 nm), XeF excimer laser (351 nm), frequency-multiplied Nd: YAG lasers with wavelengths of 355 nm (frequency tripled) or 265 nm (frequency-quadrupled). Particular preference is given to using Nd: YAG lasers (1064 or 532 nm) and CO 2 lasers.
  • the energy densities of the lasers used are generally in the range of 0.3 mJ / cm 2 to 50 J / cm 2 , preferably 0.3 mJ / cm 2 to 10 J / cm 2 .
  • the pulse frequency is generally in the range of 1 to 30 kHz.
  • Corresponding lasers which can be used in the process according to the invention are commercially available.
  • the laser welding is carried out in such a way that a laser-transparent material is welded to a laser-absorbing material.
  • the boride compound may be added in a concentration of 0.001 to 10% by weight, preferably 0.001 to 7% by weight, and more preferably 0.01 to 3% by weight, based on the polymer.
  • CW diode lasers or Nd: YAG lasers are preferably suitable at wavelengths of 800-1100 nm, preferably 808-1080 nm.
  • the energy densities of the lasers used are generally in the range from 0.3 mJ / cm 2 to 200 J. / cm 2 , preferably 0.5 J / cm 2 to 150 J / cm 2 .
  • inventively doped polymer can be done in all areas where hitherto customary welding processes or Druckver ⁇ used for labeling or for joining plastics become.
  • molding compounds, semi-finished products and finished parts of the polymer according to the invention can be used in the electrical, electronics and motor vehicle industries.
  • the marking and labeling of eg cables, wires, trim strips or functional parts in the heating, ventilation and cooling area or switches, plugs, levers and handles, which consist of the inventively doped polymers can be marked even in hard to reach places with the help of laser light become.
  • the polymer system according to the invention can be used in packaging in the food sector or in the toy sector.
  • the markings on the packaging are characterized by the fact that they are wipe and scratch resistant, stable in subsequent sterilization processes, and hygienically pure in the marking process can be applied.
  • Complete label images can be permanently applied to the packaging for a reusable system.
  • the polymer system according to the invention finds application in medical technology, for example in the labeling of petri dishes, microtiter plates, disposable syringes, ampoules, sample containers, supply hoses and medical collection bags or storage bags.
  • a barcode system stores the information that is specific to the animal. These can be recalled when needed with the help of a scanner.
  • the label must be very durable, because the mark sometimes remain on the animals for several years.
  • the plates show a dark and abrasion-resistant lettering with high contrast.
  • PP-HD Stamylen PPH 10 from DSM
  • PP-HD Stamylen PPH 10 from DSM
  • PP-HD Stamylen PPH 10 from DSM
  • 0.01% magnesium boride of particle size 50 ⁇ m from HC Starck
  • Colortek OT-0005-BON processed by injection molding. After labeling with a 12 W Nd: YAG laser (SHT at 300 mm / s and 0.03 mm beam width, 40-90% lamp energy and a frequency of 5-15 kHz), the plates show a dark and abrasion-resistant lettering high contrast.
  • PVC (Decelith 87700 crystal clear from Eilenburger Compound Werk GmbH) is injection molded by addition of 0.01% lanthanum hexaboride of particle size 50 ⁇ m (from HC Starck) and 0.02% Colortek OT-0005-BON , After labeling with a 12 W Nd: YAG laser (SHT at 300 mm / s and 0.03 mm beam width, 40-90% lamp energy and a frequency of 5-15 kHz), the plates show a dark and abrasion-resistant lettering high contrast.
  • PC (Makrolon 2807 from Bayer AG) is injection-molded by addition of 0.01% lanthanum hexaboride of particle size 50 ⁇ m (H.C. Starck Co.) and 0.02% Colortek OT-0005-BON.
  • Lanthanum hexaboride (HC Starck) is ground with a bead mill to a particle size of about 50 nm and incorporated as a paste preparation in PMMA 1 plexiglass Plexiglas 7N granules (Röhm, Darmstadt). The preparation contains about 0.01% LaB 6 .
  • injection molding 1, 5 mm thick plates are produced. After labeling with a 12W Nd: YAG laser (SHT at 300 mm / s and 0.03 mm beam width, 40-90% lamp energy and a frequency of 5-15 kHz), the plates already show a light gray at the lowest lamp energy , almost white abrasion-resistant lettering with good edge definition on clear transparent background. Reference plates without LaB 6 additive show only a weak fuzzy mark at the highest lamp energy.
  • PP-HD Stamylen PPH 10 from DSM
  • PP-HD Stamylen PPH 10 from DSM
  • the lanthanum hexaboride (H. C. Starck) is ground with a bead mill to a particle size of about 50 nm and incorporated as a paste preparation in PC.
  • a PC (Makrolon 2807 Fa. Bayer AG) is by
  • PP granules (Metocene X50081, Basell) are mixed with 0.1% titanium diboride particle size 2-6 microns (ABCR, Düsseldorf) and 0.2% Colortek OT 0005-BON (product of Colortek, adhesives based on of fatty acid and fatty acid esters) and processed by injection molding. It will receive a transparent approximately 1, 5 mm thick plate with a slight gray haze. After labeling with a 12W Nd: YAG laser (SHT at 300 mm / s and 0.03 mm beam width, 40-90% lamp energy and a frequency of 5-15 kHz), the plates show a dark and abrasion-resistant lettering with high Contrast.
  • YAG laser SHT at 300 mm / s and 0.03 mm beam width, 40-90% lamp energy and a frequency of 5-15 kHz
  • silanized pyrogenic silica (Cab-O-Sil TS610, Cabot Co.) are stirred into the suspension. The suspension is then drawn dry in vacuo. This gives a finely powdered residue which consists of finely divided SiO 2 , the protective colloid and finely divided lanthanum hexaboride. From this preparation, 5 g are mixed with 5 kg of PP granules (Metocene X50081, Basell). Samples of the mixture are injection-molded into 1, 5 mm thick plates. The plastic plates contain about 0.01% LaB 6 and appear colorless and highly transparent, with an eightfold magnifying glass no particles are recognizable.
  • PP-HD Stamylen PPH 10 from DSM
  • PP-HD Stamylen PPH 10 from DSM
  • Adhesives based on fatty acid and fatty acid esters are processed by injection molding.
  • the platelets are welded with PP platelets in the transmission process.
  • a 100W Nd: YAG laser (Rofin-Sinar) one obtains a load-bearing weld seam with a high welding depth (1500 ⁇ m) at line energies of approx. 85 J / cm.

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  • Physics & Mathematics (AREA)
  • Optics & Photonics (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical & Material Sciences (AREA)
  • Mechanical Engineering (AREA)
  • Engineering & Computer Science (AREA)
  • Toxicology (AREA)
  • Electromagnetism (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Thermal Transfer Or Thermal Recording In General (AREA)
  • Lining Or Joining Of Plastics Or The Like (AREA)

Abstract

L'invention concerne des polymères pouvant être marqués et soudés au laser, caractérisés en ce qu'ils contiennent au moins un composé de borure comme agent d'absorption.
PCT/EP2005/008677 2004-09-16 2005-08-10 Materiaux polymeres pouvant etre marques et soudes au laser WO2006029677A1 (fr)

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DE102004045305A DE102004045305A1 (de) 2004-09-16 2004-09-16 Lasermarkierbare und laserschweißbare polymere Materialien
DE102004045305.5 2004-09-16

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Cited By (12)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2007107407A1 (fr) * 2006-03-20 2007-09-27 Basf Se Composition de borure metallique nanoparticulaire et son utilisation pour le marquage de pieces en matiere plastique
WO2009000252A2 (fr) * 2007-06-22 2008-12-31 Grafe Color Batch Gmbh Produit synthétique thermoplastique à renforcement mécanique pour procédés d'assemblage laser
DE102008049595A1 (de) 2008-09-30 2010-04-01 Merck Patent Gmbh Infrarotabsorbierende Druckfarben
CN102417646A (zh) * 2011-10-24 2012-04-18 上海交通大学 一种可激光标记的聚乙烯组合物
US8318262B2 (en) 2006-12-22 2012-11-27 Eckart Gmbh Use of spherical metal particles as laser-marking or laser-weldability agents, and laser-markable and/or laser-weldable plastic
US8778494B2 (en) 2009-03-18 2014-07-15 Merck Patent Gmbh Pigment for laser marking
EP1944152B2 (fr) † 2007-01-11 2014-08-13 Sumitomo Metal Mining Co., Ltd. Composition de résine absorbant la lumière pour soudage au laser, moulage en résine absorbant la lumière, et procédé de fabrication d'un moulage en résine absorbant la lumière
US8877332B2 (en) 2007-11-30 2014-11-04 Eckart Gmbh Use of a mixture comprising spherical metal particles and metal flakes as laser-marking or laser-weldability agents and laser markable and/or laser weldable plastic
WO2015188917A1 (fr) * 2014-06-10 2015-12-17 Merck Patent Gmbh Matériaux polymères marquables et soudables au laser
US9745465B2 (en) 2012-06-06 2017-08-29 Mitsubishi Engineering-Plastics Corporation Resin composition for laser direct structuring, resin-molded article, and method for manufacturing molded article with plated layer
DE102016213372A1 (de) 2016-07-21 2018-01-25 Few Chemicals Gmbh NIR-Absorber Additive für das Laserstrahlschweißen von Kunststoffen
CN113025969A (zh) * 2019-12-09 2021-06-25 斯沃奇集团研究和开发有限公司 制造装饰表面的方法

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US20090130451A1 (en) * 2007-11-19 2009-05-21 Tony Farrell Laser-weldable thermoplastics, methods of manufacture, and articles thereof
CN103154135B (zh) * 2011-03-18 2014-10-15 三菱化学欧洲合资公司 生产电路载体的方法
JP5912704B2 (ja) 2011-03-18 2016-04-27 三菱エンジニアリングプラスチックス株式会社 熱可塑性樹脂組成物、樹脂成形品、及びメッキ層付樹脂成形品の製造方法
DE102014008963A1 (de) * 2014-06-23 2016-01-07 Merck Patent Gmbh Additiv für LDS-Kunststoffe

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US20040071957A1 (en) * 2002-09-25 2004-04-15 Sumitomo Metal Mining Co., Ltd. Heat radiation shielding component dispersion, process for its preparation and heat radiation shielding film forming coating liquid, heat radiation shielding film and heat radiation shielding resin form which are obtained using the dispersion

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EP0580393A2 (fr) * 1992-07-20 1994-01-26 Presstek, Inc. Plaque pour l'impression lithographique
EP0770495A1 (fr) * 1995-10-24 1997-05-02 Agfa-Gevaert N.V. Procédé pour la fabrication d'une plaque lithographique avec développement sur presse
US6569601B1 (en) * 2000-09-14 2003-05-27 Alcoa Inc. Radiation treatable printing plate
WO2002060988A1 (fr) * 2000-11-14 2002-08-08 Solutia, Inc. Composition et plaque butyralpolyvinyliques absorbant les infrarouges (ir), ainsi que lamine comprenant ladite plaque
DE10101240A1 (de) * 2001-01-11 2002-07-18 Basf Ag Verfahren zur Herstellung laserverschweißter Verbundformteile sowie diese Verbundformteile
EP1319683A1 (fr) * 2001-12-11 2003-06-18 Asahi Glass Co., Ltd. Film de polymère fluoré utilisé comme agent de blocage de rayonnement thermique
US20040071957A1 (en) * 2002-09-25 2004-04-15 Sumitomo Metal Mining Co., Ltd. Heat radiation shielding component dispersion, process for its preparation and heat radiation shielding film forming coating liquid, heat radiation shielding film and heat radiation shielding resin form which are obtained using the dispersion

Cited By (15)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2007107407A1 (fr) * 2006-03-20 2007-09-27 Basf Se Composition de borure metallique nanoparticulaire et son utilisation pour le marquage de pieces en matiere plastique
US8318262B2 (en) 2006-12-22 2012-11-27 Eckart Gmbh Use of spherical metal particles as laser-marking or laser-weldability agents, and laser-markable and/or laser-weldable plastic
EP1944152B2 (fr) † 2007-01-11 2014-08-13 Sumitomo Metal Mining Co., Ltd. Composition de résine absorbant la lumière pour soudage au laser, moulage en résine absorbant la lumière, et procédé de fabrication d'un moulage en résine absorbant la lumière
WO2009000252A2 (fr) * 2007-06-22 2008-12-31 Grafe Color Batch Gmbh Produit synthétique thermoplastique à renforcement mécanique pour procédés d'assemblage laser
WO2009000252A3 (fr) * 2007-06-22 2009-02-19 Grafe Color Batch Gmbh Produit synthétique thermoplastique à renforcement mécanique pour procédés d'assemblage laser
US8877332B2 (en) 2007-11-30 2014-11-04 Eckart Gmbh Use of a mixture comprising spherical metal particles and metal flakes as laser-marking or laser-weldability agents and laser markable and/or laser weldable plastic
DE102008049595A1 (de) 2008-09-30 2010-04-01 Merck Patent Gmbh Infrarotabsorbierende Druckfarben
US8778494B2 (en) 2009-03-18 2014-07-15 Merck Patent Gmbh Pigment for laser marking
CN102417646A (zh) * 2011-10-24 2012-04-18 上海交通大学 一种可激光标记的聚乙烯组合物
US9745465B2 (en) 2012-06-06 2017-08-29 Mitsubishi Engineering-Plastics Corporation Resin composition for laser direct structuring, resin-molded article, and method for manufacturing molded article with plated layer
WO2015188917A1 (fr) * 2014-06-10 2015-12-17 Merck Patent Gmbh Matériaux polymères marquables et soudables au laser
CN106459483A (zh) * 2014-06-10 2017-02-22 默克专利股份有限公司 可激光标记和可激光焊接的聚合物材料
CN106459483B (zh) * 2014-06-10 2019-03-08 默克专利股份有限公司 可激光标记和可激光焊接的聚合物材料
DE102016213372A1 (de) 2016-07-21 2018-01-25 Few Chemicals Gmbh NIR-Absorber Additive für das Laserstrahlschweißen von Kunststoffen
CN113025969A (zh) * 2019-12-09 2021-06-25 斯沃奇集团研究和开发有限公司 制造装饰表面的方法

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