EP1560715B1 - Verfahren zur beschriftung mit laser - Google Patents

Verfahren zur beschriftung mit laser Download PDF

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Publication number
EP1560715B1
EP1560715B1 EP03783398A EP03783398A EP1560715B1 EP 1560715 B1 EP1560715 B1 EP 1560715B1 EP 03783398 A EP03783398 A EP 03783398A EP 03783398 A EP03783398 A EP 03783398A EP 1560715 B1 EP1560715 B1 EP 1560715B1
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EP
European Patent Office
Prior art keywords
laser
ink
sensitive material
laser sensitive
coating
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EP03783398A
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English (en)
French (fr)
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EP1560715A2 (de
EP1560715B2 (de
Inventor
Olaf Lucas
Dagmar Maria Kroth
Quang Minh Thai
Frank Lange
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Sun Chemical Corp
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Sun Chemical Corp
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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
    • B41M5/40—Thermography ; Marking by high energetic means, e.g. laser otherwise than by burning, and characterised by the material used characterised by the base backcoat, intermediate, or covering layers, e.g. for thermal transfer dye-donor or dye-receiver sheets; Heat, radiation filtering or absorbing means or layers; combined with other image registration layers or compositions; Special originals for reproduction by thermography
    • B41M5/46—Thermography ; Marking by high energetic means, e.g. laser otherwise than by burning, and characterised by the material used characterised by the base backcoat, intermediate, or covering layers, e.g. for thermal transfer dye-donor or dye-receiver sheets; Heat, radiation filtering or absorbing means or layers; combined with other image registration layers or compositions; Special originals for reproduction by thermography characterised by the light-to-heat converting means; characterised by the heat or radiation filtering or absorbing means or layers
    • B41M5/465—Infrared radiation-absorbing materials, e.g. dyes, metals, silicates, C black
    • 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
    • B41M5/24—Ablative recording, e.g. by burning marks; Spark recording
    • 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 present invention relates to a laser marking process for use on thin flexible plastic films of the type commonly used for the packaging of various types of foodstuffs, and especially to such a process using an ink which contains or is associated with a laser sensitive material.
  • Laser marking of plastics materials is now well known [see, for example, " Laser Marking” by Paul D. Hartung, Chapter 17 of "Plastics Finishing and Decoration” edited by Donatas Satas, published by Van Nostrand Reinhold Co., New York, 1986 ]. It is a valuable method of marking which has found many applications. Its advantages include: the laser does not directly contact the item to be marked, and so there is no mechanical wear, neither is there any impact on the contents of the packaging; it allows extremely small characters or symbols to be drawn; accurately and legibly, markings can be made at extremely high speeds; lasers are extremely reliable and require minimal maintenance, and other moving parts on the marking system are limited.
  • Another laser marking technique comprises using a laser to remove thermally a covering layer, thereby exposing a lower layer of a different colour from that of the covering layer, so providing visible markings.
  • An example of such a process, for the marking of optical fibres or electric cables, is described in US Patent No. 5,111,523 .
  • a further laser marking method employs the heat generated by laser radiation striking a substrate to cause a change in the colour of a thermosensitive material, as described, for example, in US Patent No. 5,608, 429 .
  • Another type of laser marking process uses thin aluminium layers which are deposited by vacuum evaporation. Because these absorb in the range of the Nd:YAG-radiation, such aluminium layers can be removed by laser radiation. This can be used to remove coloured ink layers, printed on the aluminium layer or to make contrast forming layers visible, as describe in US Patent No. 6,066,437 .
  • aluminium-coated films are necessary, which are expensive and the deposition of the aluminium requires specialised equipment, which means that it often cannot be done or cannot be done economically at the site where the packages are printed.
  • Laser ablative imaging methods are also known in which a donor sheet containing a material which absorbs at the wavelength of the laser and a dye (rather than the pigment necessary in the present invention) is irradiated with a laser.
  • the absorbing material converts the laser energy to heat, which is transferred to the immediately proximate dye.
  • the dye vaporises and is transferred to the receptor, which is the material to be printed.
  • the present invention consists in processes for marking a flexible plastic film useful for packaging according to the appended claims.
  • the expression "in association with” is here defined to mean that the ink and the laser sensitive material are in sufficiently close physical proximity that the heat induced in the laser sensitive material by the laser radiation is sufficient to cause the thermal removal of the ink.
  • the laser sensitive material and the ink may be applied in separate layers or together in one composition.
  • the layer of ink or layers of ink and laser sensitive material referred to above may cover the entire surface of the substrate, if desired. However, it is a benefit of the present invention that they need not do so. Thus, the layers may, if desired, cover only that portion or those portions of the substrate on which markings are subsequently to be printed, and they may be applied by conventional printing processes with considerable accuracy. For example, if the markings to be printed are "use by" or "best before” information, a single patch of the coating layers may be applied to the substrate in the position where this information is to be inserted. Alternatively, the invention is equally applicable to the printing of statutory information, which may vary from country to country and/or which may need to be in different languages for different countries. In this case, several patches of ink/varnish and laser sensitive material may need to be applied. Similarly, bar codes can be marked on areas that have been selectively coated with laser sensitive material.
  • the laser sensitive material When the laser sensitive material is exposed to the laser radiation, it absorbs the energy of the radiation, becomes hot and generally removes the layer containing it and any other layers above it by thermal action. It therefore follows that the ink or non-pigmented coating should burn, degrade, evaporate or otherwise be thermally removable at a temperature to which the laser heats the laser sensitive material. The majority of inks and coatings currently available will do so, and so the selection of an appropriate ink or coating is not a difficult task.
  • the laser sensitive material is a material which can convert the energy of the laser radiation to thermal energy.
  • the nature of the laser sensitive material used in the present invention will depend on the laser system chosen, as is well known in the field of laser marking.
  • the laser sensitive material is preferably: mica or metal oxide-coated mica particles, such as those sold by Merck KgaA, Darmstadt, Germany under the trade names Iriodin LS 800, Iriodin LS 805, Iriodin LS 810, Iriodin LS 830, Iriodin LS 835 or Iriodin LS 850, or those sold by EMI (BMI Industries, Inc.
  • Ultrastar GX 2550 that sold by Wolstenholme (Wolstenhohne International Ltd., Darwen, Blackburn, England) under the trade name Metasheen 1015 or that sold by Eckart under the trade name Rotosafe 751 or Rotosafe 700; carbon black, such as that sold by Degussa (Degussa AG, Frankfurt, Germany) under the trade name Printex XE2, Printex 3 or Printex L or that sold by Avecia (Avecia, Manchester, England) under the trade name Pro-Jet 900 NP Bx2005; kaolin and other silicates; titanium dioxide; and calcium carbonate.
  • the laser sensitive material is preferably: mica or metal oxide-coated mica particles, such as Iriodin LS 820, Iriodin LS 825, Iriodin LS 830, Iriodin LS 835 or Iriodin LS 850 (all ex Merck), or Laser Flair LS 820, Laser Flair LS 825, Laser Flair LS 830, Laser Flair LS 835 or Laser Flair LS 850 (all ex EMI); aluminium powders, such as Silvet LR10, Silvet LR20, Silvet LR30, Silvet ET917, or Silvet ET1630 (all ex Silberline), Ultrastar GX 2550 (ex Eckart), Metasheen 1015 (ex Wolstenholme) or Rotosafe 751 or Rotosafe 700 (both ex Eckart); carbon black, such as Printex XE2, Print
  • inks there is no particular restriction on the nature of the ink used in the present invention, and any ink known for use in the printing of flexible plastic films may be used, subject only to the restriction, as explained above, that it should be capable of being removed by the heat generated in the laser sensitive material by the laser radiation.
  • Preferred examples of such inks include those comprising: nitrocellulose (NC) based inks, polyvinyl butyrate (PVB) based inks, polyurethane (PUR) based inks, cellulose acetate propionate (CAP) based inks, polyvinyl chloride (PVC) based inks, polyamide (PA) based inks, water based inks.
  • NC nitrocellulose
  • PVB polyvinyl butyrate
  • PUR polyurethane
  • CAP cellulose acetate propionate
  • PVC polyvinyl chloride
  • PA polyamide
  • inks by their very nature, necessarily include at least one pigment.
  • the laser sensitive material may also be applied as part of an essentially transparent pigment-free coating.
  • the formulation of these coatings is essentially similar to that of the inks, but with the coloured pigment absent.
  • the laser sensitive material is incorporated into an ink or into a non-pigmented coating, it is preferably present in an amount from 1 to 40%, more preferably from 5 to 20%, and most preferably from 10 to 15% by weight of the whole composition.
  • compositions which may be used in the present invention are given in the following Table 1 (inks) and Table 2(pigment-free coatings), in which the laser sensitive material referred to may be any of the laser sensitive materials mentioned above.
  • plastic film used as the substrate in the process of the present invention there is no particular restriction on the nature of the plastic film used as the substrate in the process of the present invention, and any plastic materials commonly used in the industry, especially for food wrapping, may be used.
  • materials include synthetic and semi synthetic organic polymers, such as cellulose acetate, cellulose acetate butyrate (CAB), cellophane, polyvinyl chloride (PVC), polyvinyl fluoride, polyvinylidene chloride (PVDC), polyethylene, polypropylene (PP), polyamides, polyesters, polyphenylene oxide, polyethylene terephthalate (PET), polybutylene terephthalate (PET), polymethyl methacrylate, poly(methyl pentene (TPX), polyvinyl acetal, polystyrene, acrylonitrile-butadiene-styrene (ABS), acrylonitrile-styrene-acrylate (ASA), polycarbonate, polystyrene, polyether
  • films made from any of these polymers may be coated with coating materials well known in the art, and/or may be laminated to a film or films made of the same or different polymers. Further examples of such plastic materials may be found in standard reference texts, such as " Plastic Films", 3rd Edition, by J. H. Briston, published by Longman Group in 1989 .
  • the substrate may be coated with a colouring layer impervious to the laser radiation, so as to provide a layer of a contrasting colour to that of the ink subsequently applied.
  • a colouring layer impervious to the laser radiation so as to provide a layer of a contrasting colour to that of the ink subsequently applied.
  • the lower, laser-impervious, layer will be seen as a contrasting colour and will form the printed markings generated by the laser.
  • the coating layer of ink which is selectively removed may be coloured, so that, when it is removed, the native colour of the substrate is seen as a contrast
  • the ink is cured or dried to form a coherent layer on the substrate.
  • one or more further films of plastic material may be laminated to the coated substrate. This may be any of the polymers listed above, but should be transparent to the radiation of the laser employed. If another film is laminated on top of the ink, and the ink emits gases or otherwise undergoes an increase in volume on being heated by the heat resulting from absorption of the laser energy by the laser sensitive material, the portion of the laminated film above the markings will be raised, thus giving an embossed effect which otherwise would be difficult to achieve and which can be very desirable.
  • the present invention can thus provide thin flexible plastic films which may be coated in many ways. Examples of these include:
  • the laser sensitive material is mixed with the ink or that the ink and the laser sensitive material are in separate, but associated, layers, the layer of ink to be removed by the process of the present invention being on the side of the layer of laser sensitive material remote from the substrate.
  • any of the above may be coated with further layers of material, for example, varnish, provided that any such further layers are transparent or essentially transparent, to the laser radiation.
  • the film may be coated with one or more other layers of materials, such as inks, varnishes and the like, prior to being coated with the first layer in accordance with the present invention.
  • a laser sensitive material is or is associated with a material which evolves gas when heated
  • it may be the laser sensitive material which evolves gas.
  • the laser sensitive material may be associated with, e.g. mixed with, another material which evolves gas.
  • the material is then coated with a gas impermeable layer, which can be any such known material.
  • a gas impermeable layer which can be any such known material.
  • the exposed portions emit a gas.
  • this is trapped by the coating layer, and, as a result, forms minute bubbles under the coating layer.
  • a laser sensitive solvent based coating was printed on transparent oriented polypropylene (OPP) film, and then overprinted with a nitrocellulose based cyan ink.
  • the formulation of the laser sensitive coating was (parts by weight): Nitrocellulose, Nitro CA4 A15 ex Bergerac 11 Ethyl acetate 22 Ethanol 32 Methoxypropanol, Dowanol PM ex Dow 15 Plasticiser Plastifiant 1026 ex SNPE 10 Iriodin LS 825 ex Merck 10 Total 100
  • the cyan ink was Europa cyan ex Sun Chemical. After exposure to a Nd:YAG laser, marks were visible as a result of removal of the cyan ink from the regions exposed to the laser beam.
  • a laser sensitive solvent based coating was printed on transparent OPP film, and then overprinted with a nitrocellulose based cyan ink.
  • the formulation of the laser sensitive coating was (parts by weight): Nitrocellulose, Nitro CA4 A15 ex Bergerac 11 Ethyl acetate 22 Ethanol 32 Methoxypropanol, Dowanol PM ex Dow 15 Plasticiser Plastifiant 1026 ex SNPE 10 Iriodin LS 800 ex Merck 10 Total 100
  • the cyan ink was Europa cyan ex Sun Chemical. After exposure to a CO 2 laser, marks were visible as a result of removal of the cyan ink from the regions exposed to the laser beam.
  • a laser sensitive solvent based coating was printed on transparent OPP film, and then overprinted with a nitrocellulose based cyan ink.
  • the formulation of the laser sensitive coating was (parts by weight): Nitrocellulose, Nitro CA4 A15 ex Bergerac 10.0 Ethyl acetate 36.5 Ethanol 36.5 Urethane, Surkopak 5244 ex Tennants Inks 6.0 Adhesion promoter Lutonal M40 ex BASF 1.0 Kaolin 10.0 Total 100.0
  • the cyan ink was Europa cyan ex Sun Chemical. After exposure to a CO 2 laser, marks were visible as a result of removal of the cyan ink from the regions exposed to the laser beam.
  • a laser sensitive solvent based coating was printed on transparent OPP film, and then overprinted with a nitrocellulose based cyan ink.
  • the formulation of the laser sensitive coating was (parts by weight): Polyvinyl butyral, Pioloform BN18 ex Wacker 15 Ethanol 75 Iriodin LS 825 ex Merck 10 Total 100
  • the cyan ink was Europa cyan ex Sun Chemical. After exposure to a Nd:YAG laser, marks were visible as a result of removal of the cyan ink from the regions exposed to the laser beam.
  • a laser sensitive water based coating was printed on transparent OPP film, and then overprinted with a nitrocellulose based cyan ink.
  • the formulation of the laser sensitive coating was (parts by weight): Acrylic Solution Joncryl 678 ex Johnson 59.0 Acrylic Emulsion Joncryl 80 ex Johnson 22.5 Water 5.0 Defoamer TPE714 ex Henkel 0.5 Levelling agent Surfynol SE-F ex Air Products 3.0 Iriodin LS 825 ex Merck 10.0 Total 100.0
  • the cyan ink was Europa cyan ex Sun Chemical. After exposure to a Nd:YAG laser, marks were visible as a result of removal of the cyan ink from the regions exposed to the laser beam.
  • a laser sensitive solvent based coating was printed on transparent OPP film, and then overprinted with a nitrocellulose based yellow ink.
  • the formulation of the laser sensitive coating was (parts by weight): Nitrocellulose, Nitro CA4 A15 ex Bergerac 11 Ethyl acetate 17 Ethanol 27 Methoxypropanol, Dowanol PM ex Dow 15 Plasticiser Plastifiant 1026 ex SNPE 10 Iriodin LS 800 ex Merck 10 Iriodin LS 825 ex Merck 10 Total 100
  • the cyan ink was Europa yellow ex Sun Chemical. After exposure to a Nd:YAG or CO 2 laser, marks were visible as a result of removal of the cyan ink from the regions exposed to the laser beam.
  • a nitrocellulose based white ink was printed on transparent polyethylene terephthalate (PET), and was overprinted with a solvent based laser sensitive magenta ink.
  • the formulation of the laser sensitive magenta ink was (parts by weight): Nitrocellulose, Nitro CA4 A15 ex Bergerac 10.0 Ethyl acetate 18.5 Ethanol 18.5 Methoxypropanol, Dowanol PM ex Dow 10.0 Urethane resin,.
  • a cellulose acetate propionate based orange ink was printed on transparent polypropylene (PP), and then overprinted with a solvent based laser sensitive coating, which, in turn, was overprinted with cellulose acetate propionate based green ink.
  • the formulation of the laser sensitive coating was (parts by weight): Nitrocellulose, Nitro CA4 A15 ex Bergerac 11 Ethyl acetate 22 Ethanol 32 Methoxypropanol, Dowanol PM ex Dow 15 Plasticiser Plastifiant 1026 ex SNPE 10 Iriodin LS 825 10 Total 100
  • the orange ink was Europa orange ex Sun Chemical.
  • the green ink was Europa green ex Sun Chemical.
  • After exposure to a Nd:YAG laser marks were visible since the orange ink was not removed by the laser and gave contrast to the green ink which had been removed.
  • a polyvinyl butyral based laser sensitive coating was printed on PET and overprinted with a polyvinyl butyral based red ink. This film was laminated with a two-pack adhesive onto polyethylene (PE).
  • the formulation of the laser sensitive coating was (parts by weight): Polyvinyl butyral Pioloform BN18 ex Wacker 15 Ethanol 75 Iriodin LS825 10 Total 100
  • the red ink was Optiprint red ex Sun Chemical.
  • the adhesive was Mor-Free 402A/Mor-Free C79 ex Rohm &Haas. After exposure to a Nd:YAG laser, marks were visible as a result of removal (or change in colour) of the red ink from the regions exposed to the laser beam.
  • a nitrocellulose based white ink printed on PET was overprinted with a nitrocellulose based laser sensitive coating and a polyvinyl butyral based yellow ink. This film was laminated with a two-pack solvent free adhesive onto PP.
  • the formulation of the laser sensitive coating was (parts by weight): Nitrocellulose, Nitro CA4 A15 ex Bergerac 10.0 Ethyl acetate 36.5 Ethanol 36.5 Urethane, Surkopak SE-F ex SNPE 6.0 Adhesion promoter, Lutonal M40 ex BASF 1.0 Iriodin LS 825 10.0 Total 100.0
  • the white ink was Europa white ex Sun Chemical.
  • the yellow ink was Optiprint yellow ex Sun Chemical.
  • the solvent based adhesive was Herberts EPS71-72 / KS65 ex Herberts. After exposure to a Nd:YAG laser, marks were visible as a result of removal of the yellow ink from the regions exposed to the laser beam.
  • a nitrocellulose based laser sensitive green was printed on polyamide (PA).
  • the formulation of the laser sensitive green ink was (parts by weight): Nitrocellulose, Nitro CA4 A15 ex Bergerac 10.0 Ethyl acetate 18.5 Ethanol 18.5 Methoxypropanol, Dowanol PM ex Dow 10.0 Urethane resin, Surkopak 5244 ex Tennants Inks 6.0 Adhesion promoter, Lutonal M40 ex BASF 1.0 Plasticiser, Dioctyl phthalate ex BASF 3.0 Green pigment, Sunfast green 264-5504 ex Sun Chemical 18.0 Iriodin LS 825 ex Merck 15.0 Total 100.0 After exposure to a Nd:YAG laser, marks were visible as a result of removal of the green ink from the regions exposed to the laser beam.
  • a nitrocellulose based laser sensitive blue ink was printed on PA.
  • the formulation of the laser sensitive blue ink was (parts by weight): Nitrocellulose, Nitro CA4 A15 ex Bergerac 10.0 Ethyl acetate 18.5 Ethanol 18.5 Methoxypropanol, Dowanol PM ex Dow 10.0 Urethane resin, Surkopak 5244 ex Tennants Inks 6.0 Adhesion promoter, Lutonal M40 ex BASF 1.0 Plasticiser, Dioctyl phthalate ex BASF 3.0 Blue pigment, Fastogen Blue 5412 SD ex DIC PBI 15:4 18.0 Iriodin LS 800 ex Merck 15.0 Total 100.0 After exposure to a CO 2 laser, marks were visible as a result of removal of the blue ink from the regions exposed to the laser beam.
  • a polyvinyl butyral based laser sensitive blue ink was printed on PA.
  • the formulation of the laser sensitive blue ink was (parts by weight): Polyvinyl butyral, Pioloform BN18 ex Wacker 10.0 Adhesion promoter, Lutonal M40 ex BASF 5.0 Ethanol 52.0 Blue pigment, Heliogen blue 7086 ex BASF, Pub115:3 18.0 Iriodin LS 800 ex Merck 15.0 Total 100.0 After exposure to a CO 2 laser, marks were visible as a result of removal of the blue ink from the regions exposed to the laser beam.
  • a water based laser sensitive blue ink was printed on PA.
  • the formulation of the laser sensitive blue ink was (parts by weight): Acrylic Emulsion, Joncryl 80 ex Johnson 50.0 Water 14.5 Defoamer TPE714 ex Henkel 0.5 Levelling agent, Surfynol SE-F ex Air Products 3.0 Pigment, Meghafast Blue BD909 ex Meghmani, PB115:3 17.0 Iriodin LS 825 ex Merck 15.0 Total 100.0
  • Nd:YAG laser marks were visible as a result of removal of the blue ink from the regions exposed to the laser beam.
  • a nitrocellulose based laser sensitive yellow ink was printed on PA.
  • the formulation of the laser sensitive yellow ink was (parts by weight): Nitrocellulose, Nitro CA4 A15 ex Bergerac 10.0 Ethyl acetate 16.0 Ethanol 16.0 Methoxypropanol, Dowanol PM ex Dow 10.0 Urethane resin, Surkopak 5244 ex Tennants Inks 6.0 Adhesion promoter, Lutonal M40 ex BASF 1.0 Plasticiser, Dioctyl phthalate ex BASF 3.0 Yellow pigment Permanent yellow P-GRL06 ex Clariant 18.0 Iriodin LS 825 ex Merck 10.0 Iriodin LS 800 ex Merck 10.0 Total 100.0 After exposure to a Nd:YAG or CO 2 laser, marks were visible as a result of removal of the blue ink from the regions exposed to the laser beam.
  • a laser sensitive nitrocellulose based orange ink was printed on PET.
  • the film was laminated with a two-pack adhesive onto PE.
  • the formulation of the laser sensitive orange ink was (parts by weight): Nitrocellulose, Nitro CA4 A15 ex Bergerac 10.0 Ethyl acetate 18.5 Ethanol 18.5 Methoxypropanol, Dowanol PM ex Dow 10.0 Urethane resin, Surkopak 5244 ex Tennants Inks 6.0
  • the adhesive was Mor-Free 402A/Mor-Free C79 ex Rohm &Haas. After exposure to a Nd:YAG laser, marks were visible as a result of removal of the orange ink from the regions exposed to the laser beam.
  • a polyvinyl butyral based white ink was printed on PE, and was overprinted with laser sensitive polyvinyl butyral based violet ink. This film was laminated with water based adhesive on PP.
  • the formulation of the laser sensitive violet ink was )parts by weight): Polyvinyl butyral, Pioloform BN18 ex Wacker 10 Adhesion promoter, Lutonal M40 ex BASF 5 Ethanol 53 Blue pigment, Heliogen blue BD909 ex BASF 17 Iriodin LS 825 15 Total 100
  • the white ink was Europa white ex Sun Chemical.
  • the water based adhesive was Aqua-LAM 300A/Aquabond 444C ex Rohm & Haas. After exposure to a Nd:YAG laser, marks were visible as a result of removal of the violet ink from the regions exposed to the laser beam.
  • thermochromic ink was a water based flexo ink ex Sun Chemical with irreversible colour change at 90 °C from colourless to dark grey.
  • thermochromic ink After exposure to a NdYAG laser, marks were visible as a result of irreversible colour change of the thermochromic ink, due to energy absorption in the laser sensitive coating and temperature increase to more than 90 °C.
  • the laser power has to be in a range such that there is enough energy to reach the recommended temperature for the colour change but not to remove the ink layer.
  • a laser sensitive solvent based coating was printed on shrinkable PET film, and was then overprinted with a nitrocellulose based white ink.
  • the film was shrunk on a glass bottle where the printed side has contact with the bottle.
  • the formulation of the laser sensitive coating was: Polyvinylbutyral, Pioloform BN18 ex Wacker 15 Ethanol 75 Iriodin LS 825 ex Merck 10 Total 100
  • the white ink was Europa white ex Sun Chemical.
  • dark marks were visible as a result of removal of the white ink from the regions of the film exposed to the laser beam.
  • the ink was transferred to the surface of the bottle, so a copy of the marks was visible after removal of the film. This can be used as a security characteristic.
  • a nitrocellulose based laser sensitive blue ink was printed on shrinkable PET.
  • the film was shrunk on a PET bottle where the printed side was in contact with the bottle.
  • the formulation of the laser sensitive blue ink was: Nitrocellulose, Nitro CA4 A15 ex Bergerac 10.0 Ethyl acetate 18.5 Ethanol 18.5 Methoxypropanol, Dowanol PM ex Dow 10.0 Urethane resin, Surkopak 5244 ex Tennants Inks 6.0 Adhesion promoter, Lutonal M40 ex BASF 1.0 Plasticiser, Dioctyl phthalate ex BASF 3.0 Blue pigment, Fastogen Blue 5412 SD ex DIC PBI 15:4 18.0 Iriodin LS 800 ex Merck 15.0 Total 100.0 After exposure to a CO 2 laser, marks were visible as a result of removal of the blue ink from the regions exposed to the laser beam. The ink was transferred to the surface of the bottle, so a copy of the marks was visible after removal of the film. This can be used as
  • a laser sensitive solvent based coating was printed on transparent OPP film, and was then overprinted with a nitrocellulose based cyan ink. The same coating layers were applied to paper. The printed film over-wrapped the printed paper.
  • the formulation of the laser sensitive coating was: Nitrocellulose, Nitro CA4 A15 ex Bergerac 11 Ethyl acetate 22 Ethanol 32 Plasticiser, Plastifiant 1026 ex SNPE 10 Methoxypropanol, Dowanol PM ex Dow 15 Iriodin LS 825 ex Merck 10 Total 100
  • the cyan ink was Europa cyan ex Sun Chemical.
  • the laser exposure was partly on film and partly on paper. After exposure to a NdYAG laser, marks were visible as a result of removal of the cyan ink from the regions of the film and the paper exposed to the laser beam. This can be used as a security characteristic.
  • a nitrocellulose based yellow ink was printed on polyvinyl acetal film as micro text. It was then overprinted with a solvent based laser sensitive blue ink.
  • the formulation of the laser sensitive blue ink was: Nitrocellulose, Nitro CA4 A15 ex Bergerac 10.0 Ethyl acetate 18.5 Ethanol 18.5 Methoxypropanol, Dowanol PM ex Dow 10.0 Urethane resin, Surkopak 5244 ex Tennants Inks 6.0 Adhesion promoter, Lutonal M40 ex BASF 1.0 Plasticiser, Dioctyl phthalate ex BASF 3.0 Blue pigment, Fastogen Blue 5412 SD ex DIC Pub115:4 18.0 Iriodin LS 800 ex Merck 15.0 Total 100.0 The yellow ink was Europa yellow ex Sun Chemical.
  • marks were visible as a result of removal of the blue ink from the regions exposed to the laser beam. Inside the marks, formed by the removal of the blue ink, the yellow micro text underneath was visible. This can be used as a security characteristic.
  • a nitrocellulose based yellow ink was printed on transparent OPP film as micro text It was then overprinted with a laser sensitive solvent based coating which was overprinted with a nitrocellulose based cyan ink.
  • the formulation of the laser sensitive coating was: Nitrocellulose, Nitro CA4 A15 ex Bergerac 11 Ethyl acetate 22 Ethanol 32 Plasticiser, Plastifiant 1026 ex SNPE 10 Methoxypropanol, Dowanol PM ex Dow 15 Iriodin LS 825 ex Merck 10 Total 100
  • the yellow ink was Europa yellow ex Sun Chemical
  • the cyan ink was Europa cyan ex Sun Chemical.
  • After exposure to a CO 2 laser marks were visible as a result of removal of the blue ink from the regions exposed to the laser beam. In the marks, formed by the removal of the blue ink, the yellow micro text underneath was visible. This can be used as a security characteristic.
  • a polyvinyl butyral based laser sensitive coating was printed on PE. This film was laminated onto PET using a 2-compound adhesive.
  • the formulation of the laser sensitive coating was: Polyvinylbutyral, Pioloform BN18 ex Wacker 15 Ethanol 75 Iriodin LS825 10 Total 100.0
  • marks were visible and tangible as a result of bubbles, formed in between the two plastic films, caused by the thermal destruction of the laser sensitive coating.
  • the intensity of bubble formation can be influenced by the laser power. These marks can also be fdt by blind people. They can, therefore, be used as Braille or Moon script.

Landscapes

  • Physics & Mathematics (AREA)
  • Optics & Photonics (AREA)
  • Thermal Transfer Or Thermal Recording In General (AREA)
  • Dot-Matrix Printers And Others (AREA)
  • Inks, Pencil-Leads, Or Crayons (AREA)
  • Laser Beam Processing (AREA)

Claims (9)

  1. Verfahren zum Beschriften eines flexiblen, zum Verpacken verwendbaren Kunststofffilms unter Verwendung eines Lasers, wobei das Verfahren die Schritte umfasst: Aufbringen auf eine Oberfläche eines Substrats, welches den flexiblen Kunststofffilm umfasst, in einer oder mehreren Schichten einer Tinte in Verbindung mit einem laserempfindlichen Material; Trocknen der Tinte; Aussetzen von Teilen der Tinte einer Laserstrahlung bei einer Wellenlänge, gegenüber welcher das laserempfindliche Material empfindlich ist, so dass Laserstrahlung, die vom laserempfindlichen Material absorbiert wird, die Tinte erwärmt und thermisch entfernt oder einen Farbwechsel der Tinte bewirkt, um so zu bewirken, dass Beschriftungen an den ausgesetzten Teilen erscheinen.
  2. Verfahren gemäß Anspruch 1, wobei das laserempfindliche Material auf das Substrat aufgebracht wird und dann eine Schicht der Tinte über dem laserempfindlichen Material aufgebracht wird.
  3. Verfahren gemäß Anspruch 1, wobei die Tinte das laserempfindliche Material enthält.
  4. Verfahren gemäß einem der Ansprüche 1 bis 3, wobei Erwärmen die Tinte entfernt.
  5. Verfahren zum Beschriften eines flexiblen, zum Verpacken verwendbaren Kunststofffilms unter Verwendung eines Lasers, wobei das Verfahren die Schritte umfasst: Aufbringen eines laserempfindlichen Materials, welches ein Material ist oder mit einem Material verbunden ist, das beim Erwärmen Gas erzeugt, auf eine Oberfläche eines den flexiblen Kunststofffilm umfassenden Substrats; Beschichten des laserempfindlichen Materials mit einer gasundurchlässigen Schicht; Aussetzen von Teilen des laserempfindlichen Materials einer Laserstrahlung bei einer Wellenlänge, gegenüber der das laserempfindliche Material empfindlich ist, so dass durch das laserempfindliche Material absorbierte Laserstrahlung dieses erwärmt und die Erzeugung von Gas verursacht, welches durch die Beschichtung eingeschlossen wird und als Folge davon winzige Blasen unter der Beschichtung bildet, um dadurch erhöhte Beschriftungen zu bilden, welche auf den ausgesetzten Teilen erscheinen.
  6. Verfahren gemäß einem der Ansprüche 1 bis 5, wobei der Laser ein CO2-Laser ist.
  7. Verfahren gemäß Anspruch 6, wobei das laserempfindliche Material Glimmer, Metalloxid-beschichtete Glimmerteilchen, Aluminiumpulver, Ruß, Kaolin oder ein anderes Silikat, Titandioxid oder Calciumcarbonat ist.
  8. Verfahren gemäß einem der Ansprüche 1 bis 5, wobei der Laser ein Nd:YAG Laser ist.
  9. Verfahren gemäß Anspruch 8, wobei das laserempfindliche Material Glimmer, Metalloxid-beschichtete Glimmerteilchen, Aluminiumpulver, Ruß, Titandioxid oder Calciumcarbonat ist.
EP03783398.5A 2002-11-14 2003-11-12 Verfahren zur beschriftung mit laser Expired - Lifetime EP1560715B2 (de)

Applications Claiming Priority (3)

Application Number Priority Date Filing Date Title
GB0226597 2002-11-14
GBGB0226597.3A GB0226597D0 (en) 2002-11-14 2002-11-14 Laser marking process
PCT/US2003/036222 WO2004045857A2 (en) 2002-11-14 2003-11-12 Laser marking process

Publications (3)

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EP1560715A2 EP1560715A2 (de) 2005-08-10
EP1560715B1 true EP1560715B1 (de) 2008-10-22
EP1560715B2 EP1560715B2 (de) 2014-08-20

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EP (1) EP1560715B2 (de)
AT (1) ATE411906T1 (de)
AU (1) AU2003290814A1 (de)
BR (1) BR0307991A (de)
CA (1) CA2506979A1 (de)
DE (1) DE60324311D1 (de)
EC (1) ECSP055842A (de)
ES (1) ES2311747T5 (de)
GB (1) GB0226597D0 (de)
MX (1) MXPA05006190A (de)
WO (1) WO2004045857A2 (de)
ZA (1) ZA200504580B (de)

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US9881714B2 (en) 2014-06-19 2018-01-30 Saint-Gobain Performance Plastics Corporation Laser-markable insulation material for wire or cable assemblies
US10256009B2 (en) 2014-06-19 2019-04-09 Saint-Gobain Performance Plastics Corporation Laser-markable insulation material for wire or cable assemblies

Families Citing this family (25)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20050072335A1 (en) * 2003-10-02 2005-04-07 Zhang Yue S. Primer composition for bonding polymer composites with urethane adhesives and sealants
GB0400813D0 (en) 2004-01-14 2004-02-18 Sherwood Technology Ltd Laser imaging
DE102005000953A1 (de) * 2004-06-09 2005-12-29 Eberhard Wiedenmann Verfahren zum Kennzeichnen von geräucherten Lebensmitteln
GB0611325D0 (en) * 2006-06-08 2006-07-19 Datalase Ltd Laser marking
ATE447476T1 (de) 2007-11-30 2009-11-15 Eckart Gmbh Verwendung einer mischung mit sphärischen metallpartikeln und metallflakes als lasermarkierungs- oder laserschweissbarkeitsmittel sowie lasermarkierbarer und/oder laserschweissbarer kunststoff
DE102008046461A1 (de) 2008-09-09 2010-03-11 Tesa Se Verfahren zur Herstellung einer mehrfarbig laserbeschriftbaren Folie
AT507507A1 (de) * 2008-11-03 2010-05-15 Teich Ag Platine
JP2013544296A (ja) 2010-10-25 2013-12-12 サビック・イノベーティブ・プラスチックス・アイピー・ベスローテン・フェンノートシャップ レーザダイレクトストラクチャリング材料の改善された無電解メッキ性能
ITMO20110225A1 (it) * 2011-09-01 2013-03-02 Swisslog Italia Spa Materiale di confezionamento e confezione
DE102013218752B4 (de) 2013-09-18 2021-01-28 Bundesdruckerei Gmbh Aktivierbares Wert- oder Sicherheitsprodukt, Verfahren zum Aktivieren und Verfahren zum Herstellen des Wert- oder Sicherheitsproduktes
WO2015122894A2 (en) * 2014-02-13 2015-08-20 Spectra Systems Corporation Gas activated changes to light absorption and emission characteristics for security articles
EP2946938B1 (de) * 2014-05-23 2017-04-12 Merck Patent GmbH Verfahren zur laserbehandlung von beschichtungen
MX2019001777A (es) 2016-08-19 2019-12-11 Strauss Levi & Co Acabado laser de prenda de vestir.
CN107437369A (zh) * 2016-12-21 2017-12-05 信码互通（北京）科技有限公司 具有灰度标识的塑料片材及其制造方法
EP3665016B1 (de) 2017-08-09 2021-11-24 Parker-Hannifin Corporation Verbessertes verfahren zum markieren von produkten
MX2020003228A (es) 2017-09-22 2020-09-22 Printpack Illinois Inc Material de empaque con indicio en la capa de metal.
EP3703898A4 (de) 2017-10-31 2021-05-19 Levi Strauss & Co. Laserbearbeitungswerkzeug
CN111527493A (zh) 2017-10-31 2020-08-11 利惠商业有限公司 在创建服饰设计时使用神经网络
CN112272596B (zh) 2018-02-27 2023-06-23 利惠商业有限公司 激光整理服装的按需制造
CN112262363A (zh) 2018-02-27 2021-01-22 利惠商业有限公司 激光整理设计工具
US10883223B2 (en) 2018-08-07 2021-01-05 Levi Strauss & Co. Laser finishing design tool
WO2020113236A1 (en) 2018-11-30 2020-06-04 Levi Strauss & Co. Shadow neutral 3-d garment rendering
CN114423896A (zh) 2019-07-23 2022-04-29 利惠商业有限公司 对激光精加工服装的三维渲染预览
CN111105701A (zh) * 2020-01-31 2020-05-05 北京逸智联科技有限公司 印刷条码标签以及印刷系统
DE102021121059A1 (de) 2021-08-13 2023-02-16 Koenig & Bauer Ag Verfahren zur Herstellung von markiertem Verpackungsmaterial mittels eines Laserstrahls und eine Markierungsvorrichtung zur Herstellung von markiertem Verpackungsmaterial mit einer Laserquelle

Family Cites Families (17)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
GB2083726A (en) 1980-09-09 1982-03-24 Minnesota Mining & Mfg Preparation of multi-colour prints by laser irradiation and materials for use therein
US5035983A (en) 1988-05-31 1991-07-30 Dainippon Ink And Chemicals, Inc. Method and composition for laser-marking
EP0419377B2 (de) * 1989-09-22 2001-04-18 Schneider Electric Sa Verfahren, Vorrichtung und Farbstoff für Laserbeschriftung von Umhüllungen für elektrische Geräte
FR2656734B1 (fr) 1990-01-03 1992-03-20 Filotex Sa Cable electrique ou a fibres optiques marquable par plusieurs types de lasers.
US5061341A (en) * 1990-01-25 1991-10-29 Eastman Kodak Company Laser-ablating a marking in a coating on plastic articles
DE69209185T2 (de) * 1991-07-30 1996-08-01 Ferchim Eng Sa Verfahren zur Herstellung von Gegenständen mit oberflächlichen Relief-Mustern
US5608429A (en) 1993-08-02 1997-03-04 Nippon Kayaku Kabushiki Kaisha Laser marking method, laser marking composition and articles having color developing layer made of said composition
DE69419133T2 (de) † 1994-03-29 2000-03-02 Ge Plastics Japan Ltd., Tokio/Tokyo Harzzusammensetzungen für Laserbeschriftung
DE4415802A1 (de) 1994-05-05 1995-11-09 Merck Patent Gmbh Lasermarkierbare Kunststoffe
DE19522397A1 (de) 1995-06-23 1997-01-02 Merck Patent Gmbh Lasermarkierbare Kunststoffe
EP0761468B1 (de) † 1995-08-30 1999-10-13 Eastman Kodak Company Laseraufzeichnungselement
DE19642040C1 (de) * 1996-10-11 1998-01-15 Schreiner Etiketten Mit einem Laserstrahl beschriftbare Folie
DE19646331C2 (de) * 1996-11-09 2000-08-10 Fraunhofer Ges Forschung Verfahren zur lokalen plastischen Verformung durch einen Laser
US5977514A (en) 1997-06-13 1999-11-02 M.A. Hannacolor Controlled color laser marking of plastics
US6259465B1 (en) * 1998-11-11 2001-07-10 Eastman Kodak Company Laser thermal media with improved abrasion resistance
US6168903B1 (en) † 1999-01-21 2001-01-02 Presstek, Inc. Lithographic imaging with reduced power requirements
JP3913680B2 (ja) † 2001-03-16 2007-05-09 データレイズ・リミテッド レーザマーキング用組成物

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US9881714B2 (en) 2014-06-19 2018-01-30 Saint-Gobain Performance Plastics Corporation Laser-markable insulation material for wire or cable assemblies
US10256009B2 (en) 2014-06-19 2019-04-09 Saint-Gobain Performance Plastics Corporation Laser-markable insulation material for wire or cable assemblies

Also Published As

Publication number Publication date
BR0307991A (pt) 2004-12-21
ES2311747T5 (es) 2014-12-03
GB0226597D0 (en) 2002-12-24
CA2506979A1 (en) 2004-06-03
MXPA05006190A (es) 2005-09-21
DE60324311D1 (de) 2008-12-04
AU2003290814A8 (en) 2004-06-15
EP1560715A2 (de) 2005-08-10
EP1560715B2 (de) 2014-08-20
ZA200504580B (en) 2006-06-28
ECSP055842A (es) 2005-09-20
ATE411906T1 (de) 2008-11-15
AU2003290814A1 (en) 2004-06-15
WO2004045857A2 (en) 2004-06-03
ES2311747T3 (es) 2009-02-16
WO2004045857A3 (en) 2004-07-08

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