EP1560715B1 - Verfahren zur beschriftung mit laser - Google Patents
Verfahren zur beschriftung mit laser Download PDFInfo
- 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
- Authority
- EP
- European Patent Office
- Prior art keywords
- laser
- ink
- sensitive material
- laser sensitive
- coating
- 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.)
- Expired - Lifetime
Links
- 238000000034 method Methods 0.000 title claims abstract description 35
- 238000010330 laser marking Methods 0.000 title abstract description 12
- 239000000463 material Substances 0.000 claims abstract description 76
- 239000000758 substrate Substances 0.000 claims abstract description 17
- 230000005855 radiation Effects 0.000 claims abstract description 16
- 239000002985 plastic film Substances 0.000 claims abstract description 13
- 229920002457 flexible plastic Polymers 0.000 claims abstract description 12
- 238000004806 packaging method and process Methods 0.000 claims abstract description 9
- 238000010438 heat treatment Methods 0.000 claims abstract 4
- 238000000576 coating method Methods 0.000 claims description 42
- 239000011248 coating agent Substances 0.000 claims description 38
- 239000004411 aluminium Substances 0.000 claims description 10
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims description 10
- 229910052782 aluminium Inorganic materials 0.000 claims description 10
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 claims description 8
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims description 8
- 239000010445 mica Substances 0.000 claims description 8
- 229910052618 mica group Inorganic materials 0.000 claims description 8
- 229910000019 calcium carbonate Inorganic materials 0.000 claims description 4
- 239000006229 carbon black Substances 0.000 claims description 4
- 229910044991 metal oxide Inorganic materials 0.000 claims description 4
- 150000004706 metal oxides Chemical class 0.000 claims description 4
- 239000002245 particle Substances 0.000 claims description 4
- 239000000843 powder Substances 0.000 claims description 4
- 239000004408 titanium dioxide Substances 0.000 claims description 4
- 239000005995 Aluminium silicate Substances 0.000 claims description 3
- 235000012211 aluminium silicate Nutrition 0.000 claims description 3
- NLYAJNPCOHFWQQ-UHFFFAOYSA-N kaolin Chemical compound O.O.O=[Al]O[Si](=O)O[Si](=O)O[Al]=O NLYAJNPCOHFWQQ-UHFFFAOYSA-N 0.000 claims description 3
- BPQQTUXANYXVAA-UHFFFAOYSA-N Orthosilicate Chemical compound [O-][Si]([O-])([O-])[O-] BPQQTUXANYXVAA-UHFFFAOYSA-N 0.000 claims 1
- 238000001035 drying Methods 0.000 claims 1
- 239000006100 radiation absorber Substances 0.000 claims 1
- 238000010521 absorption reaction Methods 0.000 abstract description 3
- 206010063562 Radiation skin injury Diseases 0.000 abstract 1
- 239000000976 ink Substances 0.000 description 144
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 45
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 42
- 239000010410 layer Substances 0.000 description 39
- 239000000020 Nitrocellulose Substances 0.000 description 36
- 229920001220 nitrocellulos Polymers 0.000 description 36
- 239000000203 mixture Substances 0.000 description 30
- LHENQXAPVKABON-UHFFFAOYSA-N 1-methoxypropan-1-ol Chemical compound CCC(O)OC LHENQXAPVKABON-UHFFFAOYSA-N 0.000 description 26
- 238000009472 formulation Methods 0.000 description 25
- 239000000126 substance Substances 0.000 description 20
- 229910019655 synthetic inorganic crystalline material Inorganic materials 0.000 description 18
- JCXJVPUVTGWSNB-UHFFFAOYSA-N Nitrogen dioxide Chemical class O=[N]=O JCXJVPUVTGWSNB-UHFFFAOYSA-N 0.000 description 15
- 239000004014 plasticizer Substances 0.000 description 13
- 229920002037 poly(vinyl butyral) polymer Polymers 0.000 description 13
- 239000002904 solvent Substances 0.000 description 13
- 229910002092 carbon dioxide Inorganic materials 0.000 description 12
- 239000002318 adhesion promoter Substances 0.000 description 11
- XJRBAMWJDBPFIM-UHFFFAOYSA-N methyl vinyl ether Chemical compound COC=C XJRBAMWJDBPFIM-UHFFFAOYSA-N 0.000 description 11
- 239000005020 polyethylene terephthalate Substances 0.000 description 11
- 229920000139 polyethylene terephthalate Polymers 0.000 description 11
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 11
- 239000000975 dye Substances 0.000 description 10
- 229920003023 plastic Polymers 0.000 description 10
- 239000004033 plastic Substances 0.000 description 10
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 9
- 239000004952 Polyamide Substances 0.000 description 9
- 239000000853 adhesive Substances 0.000 description 9
- 230000001070 adhesive effect Effects 0.000 description 9
- 239000005026 oriented polypropylene Substances 0.000 description 9
- 229920002647 polyamide Polymers 0.000 description 9
- -1 polyethylene Polymers 0.000 description 8
- MQIUGAXCHLFZKX-UHFFFAOYSA-N Di-n-octyl phthalate Natural products CCCCCCCCOC(=O)C1=CC=CC=C1C(=O)OCCCCCCCC MQIUGAXCHLFZKX-UHFFFAOYSA-N 0.000 description 7
- NIXOWILDQLNWCW-UHFFFAOYSA-N acrylic acid group Chemical group C(C=C)(=O)O NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 7
- BJQHLKABXJIVAM-UHFFFAOYSA-N bis(2-ethylhexyl) phthalate Chemical compound CCCCC(CC)COC(=O)C1=CC=CC=C1C(=O)OCC(CC)CCCC BJQHLKABXJIVAM-UHFFFAOYSA-N 0.000 description 7
- 229920002803 thermoplastic polyurethane Polymers 0.000 description 7
- 239000004698 Polyethylene Substances 0.000 description 6
- 239000004743 Polypropylene Substances 0.000 description 6
- 229920004482 WACKER® Polymers 0.000 description 6
- 239000007789 gas Substances 0.000 description 6
- 229920000573 polyethylene Polymers 0.000 description 6
- 229920001155 polypropylene Polymers 0.000 description 6
- 239000001055 blue pigment Substances 0.000 description 5
- 239000011247 coating layer Substances 0.000 description 5
- 239000000049 pigment Substances 0.000 description 5
- 229920000642 polymer Polymers 0.000 description 5
- 229920008347 Cellulose acetate propionate Polymers 0.000 description 4
- 239000003795 chemical substances by application Substances 0.000 description 4
- 239000000123 paper Substances 0.000 description 4
- 239000002966 varnish Substances 0.000 description 4
- NECRQCBKTGZNMH-UHFFFAOYSA-N 3,5-dimethylhex-1-yn-3-ol Chemical compound CC(C)CC(C)(O)C#C NECRQCBKTGZNMH-UHFFFAOYSA-N 0.000 description 3
- 229920005692 JONCRYL® Polymers 0.000 description 3
- VVOLVFOSOPJKED-UHFFFAOYSA-N copper phthalocyanine Chemical compound [Cu].N=1C2=NC(C3=CC=CC=C33)=NC3=NC(C3=CC=CC=C33)=NC3=NC(C3=CC=CC=C33)=NC3=NC=1C1=CC=CC=C12 VVOLVFOSOPJKED-UHFFFAOYSA-N 0.000 description 3
- 239000013530 defoamer Substances 0.000 description 3
- 239000000839 emulsion Substances 0.000 description 3
- 235000013305 food Nutrition 0.000 description 3
- 238000003384 imaging method Methods 0.000 description 3
- 230000002427 irreversible effect Effects 0.000 description 3
- 229920006255 plastic film Polymers 0.000 description 3
- 229920002554 vinyl polymer Polymers 0.000 description 3
- JOYRKODLDBILNP-UHFFFAOYSA-N Ethyl urethane Chemical compound CCOC(N)=O JOYRKODLDBILNP-UHFFFAOYSA-N 0.000 description 2
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 description 2
- 229920005732 JONCRYL® 678 Polymers 0.000 description 2
- 239000004721 Polyphenylene oxide Substances 0.000 description 2
- 239000004793 Polystyrene Substances 0.000 description 2
- 101001082804 Synechocystis sp. (strain PCC 6803 / Kazusa) Phycobilisome 32.1 kDa linker polypeptide, phycocyanin-associated, rod 2 Proteins 0.000 description 2
- DHKHKXVYLBGOIT-UHFFFAOYSA-N acetaldehyde Diethyl Acetal Natural products CCOC(C)OCC DHKHKXVYLBGOIT-UHFFFAOYSA-N 0.000 description 2
- 150000001241 acetals Chemical class 0.000 description 2
- 229920002877 acrylic styrene acrylonitrile Polymers 0.000 description 2
- 230000008901 benefit Effects 0.000 description 2
- 229920006217 cellulose acetate butyrate Polymers 0.000 description 2
- RBTKNAXYKSUFRK-UHFFFAOYSA-N heliogen blue Chemical compound [Cu].[N-]1C2=C(C=CC=C3)C3=C1N=C([N-]1)C3=CC=CC=C3C1=NC([N-]1)=C(C=CC=C3)C3=C1N=C([N-]1)C3=CC=CC=C3C1=N2 RBTKNAXYKSUFRK-UHFFFAOYSA-N 0.000 description 2
- 150000002611 lead compounds Chemical class 0.000 description 2
- 230000003287 optical effect Effects 0.000 description 2
- 229920002223 polystyrene Polymers 0.000 description 2
- 229920002635 polyurethane Polymers 0.000 description 2
- 239000004814 polyurethane Substances 0.000 description 2
- 239000004800 polyvinyl chloride Substances 0.000 description 2
- 239000002356 single layer Substances 0.000 description 2
- GUYIZQZWDFCUTA-UHFFFAOYSA-N (pentadecachlorophthalocyaninato(2-))-copper Chemical compound [Cu+2].N1=C([N-]2)C3=C(Cl)C(Cl)=C(Cl)C(Cl)=C3C2=NC(C2=C(Cl)C(Cl)=C(Cl)C(Cl)=C22)=NC2=NC(C2=C(Cl)C(Cl)=C(Cl)C(Cl)=C22)=NC2=NC2=C(C(Cl)=C(C(Cl)=C3)Cl)C3=C1[N-]2 GUYIZQZWDFCUTA-UHFFFAOYSA-N 0.000 description 1
- 229920002799 BoPET Polymers 0.000 description 1
- FERIUCNNQQJTOY-UHFFFAOYSA-M Butyrate Chemical compound CCCC([O-])=O FERIUCNNQQJTOY-UHFFFAOYSA-M 0.000 description 1
- FERIUCNNQQJTOY-UHFFFAOYSA-N Butyric acid Natural products CCCC(O)=O FERIUCNNQQJTOY-UHFFFAOYSA-N 0.000 description 1
- YAAQEISEHDUIFO-UHFFFAOYSA-N C=CC#N.OC(=O)C=CC=CC1=CC=CC=C1 Chemical compound C=CC#N.OC(=O)C=CC=CC1=CC=CC=C1 YAAQEISEHDUIFO-UHFFFAOYSA-N 0.000 description 1
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 1
- 229920000298 Cellophane Polymers 0.000 description 1
- 235000013175 Crataegus laevigata Nutrition 0.000 description 1
- 229910052779 Neodymium Inorganic materials 0.000 description 1
- 239000004642 Polyimide Substances 0.000 description 1
- 239000011358 absorbing material Substances 0.000 description 1
- 239000004676 acrylonitrile butadiene styrene Substances 0.000 description 1
- QFFVPLLCYGOFPU-UHFFFAOYSA-N barium chromate Chemical compound [Ba+2].[O-][Cr]([O-])(=O)=O QFFVPLLCYGOFPU-UHFFFAOYSA-N 0.000 description 1
- 239000011230 binding agent Substances 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 239000011111 cardboard Substances 0.000 description 1
- 229920002301 cellulose acetate Polymers 0.000 description 1
- HKQOBOMRSSHSTC-UHFFFAOYSA-N cellulose acetate Chemical compound OC1C(O)C(O)C(CO)OC1OC1C(CO)OC(O)C(O)C1O.CC(=O)OCC1OC(OC(C)=O)C(OC(C)=O)C(OC(C)=O)C1OC1C(OC(C)=O)C(OC(C)=O)C(OC(C)=O)C(COC(C)=O)O1.CCC(=O)OCC1OC(OC(=O)CC)C(OC(=O)CC)C(OC(=O)CC)C1OC1C(OC(=O)CC)C(OC(=O)CC)C(OC(=O)CC)C(COC(=O)CC)O1 HKQOBOMRSSHSTC-UHFFFAOYSA-N 0.000 description 1
- 230000001427 coherent effect Effects 0.000 description 1
- 238000004040 coloring Methods 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 235000009508 confectionery Nutrition 0.000 description 1
- 238000010276 construction Methods 0.000 description 1
- 229920001577 copolymer Polymers 0.000 description 1
- 230000006378 damage Effects 0.000 description 1
- 238000005034 decoration Methods 0.000 description 1
- 230000008021 deposition Effects 0.000 description 1
- 239000002019 doping agent Substances 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 230000003203 everyday effect Effects 0.000 description 1
- 235000013611 frozen food Nutrition 0.000 description 1
- 239000002223 garnet Substances 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 239000001056 green pigment Substances 0.000 description 1
- 229910052734 helium Inorganic materials 0.000 description 1
- 239000001307 helium Substances 0.000 description 1
- SWQJXJOGLNCZEY-UHFFFAOYSA-N helium atom Chemical compound [He] SWQJXJOGLNCZEY-UHFFFAOYSA-N 0.000 description 1
- 238000012423 maintenance Methods 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- QEFYFXOXNSNQGX-UHFFFAOYSA-N neodymium atom Chemical compound [Nd] QEFYFXOXNSNQGX-UHFFFAOYSA-N 0.000 description 1
- 229910052754 neon Inorganic materials 0.000 description 1
- GKAOGPIIYCISHV-UHFFFAOYSA-N neon atom Chemical compound [Ne] GKAOGPIIYCISHV-UHFFFAOYSA-N 0.000 description 1
- 239000001053 orange pigment Substances 0.000 description 1
- 239000011087 paperboard Substances 0.000 description 1
- 229920001643 poly(ether ketone) Polymers 0.000 description 1
- 229920003229 poly(methyl methacrylate) Polymers 0.000 description 1
- 229920001707 polybutylene terephthalate Polymers 0.000 description 1
- 239000004417 polycarbonate Substances 0.000 description 1
- 229920000515 polycarbonate Polymers 0.000 description 1
- 229920000728 polyester Polymers 0.000 description 1
- 229920000570 polyether Polymers 0.000 description 1
- 229920001721 polyimide Polymers 0.000 description 1
- 239000004926 polymethyl methacrylate Substances 0.000 description 1
- 229920000306 polymethylpentene Polymers 0.000 description 1
- 229920006380 polyphenylene oxide Polymers 0.000 description 1
- 229920002620 polyvinyl fluoride Polymers 0.000 description 1
- 239000005033 polyvinylidene chloride Substances 0.000 description 1
- 229920005989 resin Polymers 0.000 description 1
- 239000011347 resin Substances 0.000 description 1
- 150000004760 silicates Chemical class 0.000 description 1
- 235000011888 snacks Nutrition 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 125000001174 sulfone group Chemical group 0.000 description 1
- 229920005613 synthetic organic polymer Polymers 0.000 description 1
- 238000007738 vacuum evaporation Methods 0.000 description 1
- 230000003313 weakening effect Effects 0.000 description 1
- 239000001052 yellow pigment Substances 0.000 description 1
- PRZWBGYJMNFKBT-UHFFFAOYSA-N yttrium Chemical compound [Y][Y][Y][Y][Y][Y][Y][Y][Y][Y][Y][Y][Y][Y][Y][Y][Y][Y][Y][Y][Y][Y][Y][Y][Y][Y][Y][Y][Y][Y][Y][Y][Y][Y][Y][Y][Y][Y][Y][Y][Y] PRZWBGYJMNFKBT-UHFFFAOYSA-N 0.000 description 1
- 229910052727 yttrium Inorganic materials 0.000 description 1
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)
- 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.
- 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.
- Verfahren gemäß Anspruch 1, wobei die Tinte das laserempfindliche Material enthält.
- Verfahren gemäß einem der Ansprüche 1 bis 3, wobei Erwärmen die Tinte entfernt.
- 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.
- Verfahren gemäß einem der Ansprüche 1 bis 5, wobei der Laser ein CO2-Laser ist.
- Verfahren gemäß Anspruch 6, wobei das laserempfindliche Material Glimmer, Metalloxid-beschichtete Glimmerteilchen, Aluminiumpulver, Ruß, Kaolin oder ein anderes Silikat, Titandioxid oder Calciumcarbonat ist.
- Verfahren gemäß einem der Ansprüche 1 bis 5, wobei der Laser ein Nd:YAG Laser ist.
- Verfahren gemäß Anspruch 8, wobei das laserempfindliche Material Glimmer, Metalloxid-beschichtete Glimmerteilchen, Aluminiumpulver, Ruß, Titandioxid oder Calciumcarbonat ist.
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)
Publication Number | Publication Date |
---|---|
EP1560715A2 EP1560715A2 (de) | 2005-08-10 |
EP1560715B1 true EP1560715B1 (de) | 2008-10-22 |
EP1560715B2 EP1560715B2 (de) | 2014-08-20 |
Family
ID=9947832
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
EP03783398.5A Expired - Lifetime EP1560715B2 (de) | 2002-11-14 | 2003-11-12 | Verfahren zur beschriftung mit laser |
Country Status (12)
Country | Link |
---|---|
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)
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)
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)
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 |
-
2002
- 2002-11-14 GB GBGB0226597.3A patent/GB0226597D0/en not_active Ceased
-
2003
- 2003-11-12 DE DE60324311T patent/DE60324311D1/de not_active Expired - Lifetime
- 2003-11-12 CA CA002506979A patent/CA2506979A1/en not_active Abandoned
- 2003-11-12 AT AT03783398T patent/ATE411906T1/de not_active IP Right Cessation
- 2003-11-12 MX MXPA05006190A patent/MXPA05006190A/es unknown
- 2003-11-12 AU AU2003290814A patent/AU2003290814A1/en not_active Abandoned
- 2003-11-12 WO PCT/US2003/036222 patent/WO2004045857A2/en not_active Application Discontinuation
- 2003-11-12 EP EP03783398.5A patent/EP1560715B2/de not_active Expired - Lifetime
- 2003-11-12 BR BR0307991-0A patent/BR0307991A/pt not_active IP Right Cessation
- 2003-11-12 ES ES03783398.5T patent/ES2311747T5/es not_active Expired - Lifetime
-
2005
- 2005-06-03 ZA ZA200504580A patent/ZA200504580B/en unknown
- 2005-06-08 EC EC2005005842A patent/ECSP055842A/es unknown
Cited By (2)
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 |
Similar Documents
Publication | Publication Date | Title |
---|---|---|
EP1560715B1 (de) | Verfahren zur beschriftung mit laser | |
EP0771677B1 (de) | Laserbeschriftung einer laminierten Struktur und laserbeschriftete laminierte Struktur | |
KR101121316B1 (ko) | 착색 레이저 마킹 | |
JP5296374B2 (ja) | プラスチック上の刻印の密封 | |
EP2594405B1 (de) | Lasermarkierungsfilm | |
US9916777B2 (en) | Label | |
CA2281503A1 (en) | Laser marking of articles | |
US20150293437A1 (en) | Laser markable film | |
EP2714413B1 (de) | Verbesserte nahinfrarot-absorptionsmittel | |
US10125275B2 (en) | Film | |
US4520063A (en) | Forgery-proof flat article of a synthetic resin, and process for the production thereof | |
JP6342042B1 (ja) | レーザーマーキング用積層体及び包装材 | |
EP3354477A1 (de) | Druckverfahren für einen getränkebehälter | |
WO2021251456A1 (ja) | 熱転写シート、変消色印画物、及び変消色印画物の製造方法 | |
WO2021251455A1 (ja) | 熱転写シート、変消色印画物、及び変消色印画物の製造方法 | |
US20220080760A1 (en) | Methods for Transferring Colored Markings Onto Plastic Surfaces | |
JP6461610B2 (ja) | 印刷層付き熱収縮性フィルムの製造方法、印刷層付き熱収縮性フィルム、包装体及び包装体の製造方法 | |
CN100500448C (zh) | 有色激光标记 | |
EP3616935B1 (de) | Laminiertes verpackungsmaterial für flüssige lebensmittelprodukte, verfahren zur herstellung davon, verfahren zum drucken darauf und daraus hergestellte verpackung | |
JP2017081109A (ja) | 積層体およびその製造方法 | |
JP2017081142A (ja) | 画像印刷制御システム | |
JPH0513739U (ja) | 発泡化粧材 |
Legal Events
Date | Code | Title | Description |
---|---|---|---|
PUAI | Public reference made under article 153(3) epc to a published international application that has entered the european phase |
Free format text: ORIGINAL CODE: 0009012 |
|
17P | Request for examination filed |
Effective date: 20050603 |
|
AK | Designated contracting states |
Kind code of ref document: A2 Designated state(s): AT BE BG CH CY CZ DE DK EE ES FI FR GB GR HU IE IT LI LU MC NL PT RO SE SI SK TR |
|
AX | Request for extension of the european patent |
Extension state: AL LT LV MK |
|
DAX | Request for extension of the european patent (deleted) | ||
17Q | First examination report despatched |
Effective date: 20061012 |
|
GRAP | Despatch of communication of intention to grant a patent |
Free format text: ORIGINAL CODE: EPIDOSNIGR1 |
|
GRAS | Grant fee paid |
Free format text: ORIGINAL CODE: EPIDOSNIGR3 |
|
GRAA | (expected) grant |
Free format text: ORIGINAL CODE: 0009210 |
|
AK | Designated contracting states |
Kind code of ref document: B1 Designated state(s): AT BE BG CH CY CZ DE DK EE ES FI FR GB GR HU IE IT LI LU MC NL PT RO SE SI SK TR |
|
REG | Reference to a national code |
Ref country code: GB Ref legal event code: FG4D |
|
REG | Reference to a national code |
Ref country code: CH Ref legal event code: EP |
|
REG | Reference to a national code |
Ref country code: IE Ref legal event code: FG4D |
|
REF | Corresponds to: |
Ref document number: 60324311 Country of ref document: DE Date of ref document: 20081204 Kind code of ref document: P |
|
REG | Reference to a national code |
Ref country code: ES Ref legal event code: FG2A Ref document number: 2311747 Country of ref document: ES Kind code of ref document: T3 |
|
NLV1 | Nl: lapsed or annulled due to failure to fulfill the requirements of art. 29p and 29m of the patents act | ||
PG25 | Lapsed in a contracting state [announced via postgrant information from national office to epo] |
Ref country code: AT Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT Effective date: 20081022 Ref country code: BG Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT Effective date: 20090122 |
|
PG25 | Lapsed in a contracting state [announced via postgrant information from national office to epo] |
Ref country code: NL Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT Effective date: 20081022 Ref country code: SI Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT Effective date: 20081022 Ref country code: FI Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT Effective date: 20081022 Ref country code: PT Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT Effective date: 20090323 |
|
PG25 | Lapsed in a contracting state [announced via postgrant information from national office to epo] |
Ref country code: MC Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES Effective date: 20081130 |
|
REG | Reference to a national code |
Ref country code: CH Ref legal event code: PL |
|
PLBI | Opposition filed |
Free format text: ORIGINAL CODE: 0009260 |
|
PG25 | Lapsed in a contracting state [announced via postgrant information from national office to epo] |
Ref country code: RO Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT Effective date: 20081022 Ref country code: DK Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT Effective date: 20081022 Ref country code: BE Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT Effective date: 20081022 Ref country code: EE Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT Effective date: 20081022 |
|
26 | Opposition filed |
Opponent name: GIESECKE & DEVRIENT GMBH Effective date: 20090721 Opponent name: BASF SE Effective date: 20090716 |
|
PG25 | Lapsed in a contracting state [announced via postgrant information from national office to epo] |
Ref country code: SE Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT Effective date: 20090122 Ref country code: CZ Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT Effective date: 20081022 |
|
PLAX | Notice of opposition and request to file observation + time limit sent |
Free format text: ORIGINAL CODE: EPIDOSNOBS2 |
|
PG25 | Lapsed in a contracting state [announced via postgrant information from national office to epo] |
Ref country code: SK Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT Effective date: 20081022 |
|
PG25 | Lapsed in a contracting state [announced via postgrant information from national office to epo] |
Ref country code: CH Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES Effective date: 20081130 Ref country code: IE Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES Effective date: 20081112 Ref country code: LI Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES Effective date: 20081130 |
|
PLAF | Information modified related to communication of a notice of opposition and request to file observations + time limit |
Free format text: ORIGINAL CODE: EPIDOSCOBS2 |
|
PLAF | Information modified related to communication of a notice of opposition and request to file observations + time limit |
Free format text: ORIGINAL CODE: EPIDOSCOBS2 |
|
PLBB | Reply of patent proprietor to notice(s) of opposition received |
Free format text: ORIGINAL CODE: EPIDOSNOBS3 |
|
PG25 | Lapsed in a contracting state [announced via postgrant information from national office to epo] |
Ref country code: LU Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES Effective date: 20081112 Ref country code: HU Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT Effective date: 20090423 Ref country code: CY Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT Effective date: 20081022 |
|
PG25 | Lapsed in a contracting state [announced via postgrant information from national office to epo] |
Ref country code: TR Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT Effective date: 20081022 |
|
PG25 | Lapsed in a contracting state [announced via postgrant information from national office to epo] |
Ref country code: GR Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT Effective date: 20090123 |
|
PLBP | Opposition withdrawn |
Free format text: ORIGINAL CODE: 0009264 |
|
RIC2 | Information provided on ipc code assigned after grant |
Ipc: B41M 5/46 20060101ALI20140324BHEP Ipc: B41M 5/24 20060101AFI20140324BHEP Ipc: B41M 5/26 20060101ALI20140324BHEP |
|
PUAH | Patent maintained in amended form |
Free format text: ORIGINAL CODE: 0009272 |
|
STAA | Information on the status of an ep patent application or granted ep patent |
Free format text: STATUS: PATENT MAINTAINED AS AMENDED |
|
27A | Patent maintained in amended form |
Effective date: 20140820 |
|
AK | Designated contracting states |
Kind code of ref document: B2 Designated state(s): AT BE BG CH CY CZ DE DK EE ES FI FR GB GR HU IE IT LI LU MC NL PT RO SE SI SK TR |
|
REG | Reference to a national code |
Ref country code: DE Ref legal event code: R102 Ref document number: 60324311 Country of ref document: DE |
|
REG | Reference to a national code |
Ref country code: DE Ref legal event code: R102 Ref document number: 60324311 Country of ref document: DE Effective date: 20140820 |
|
REG | Reference to a national code |
Ref country code: ES Ref legal event code: DC2A Ref document number: 2311747 Country of ref document: ES Kind code of ref document: T5 Effective date: 20141203 |
|
REG | Reference to a national code |
Ref country code: FR Ref legal event code: PLFP Year of fee payment: 13 |
|
REG | Reference to a national code |
Ref country code: FR Ref legal event code: PLFP Year of fee payment: 14 |
|
REG | Reference to a national code |
Ref country code: FR Ref legal event code: PLFP Year of fee payment: 15 |
|
PGFP | Annual fee paid to national office [announced via postgrant information from national office to epo] |
Ref country code: FR Payment date: 20221021 Year of fee payment: 20 |
|
PGFP | Annual fee paid to national office [announced via postgrant information from national office to epo] |
Ref country code: IT Payment date: 20221020 Year of fee payment: 20 Ref country code: GB Payment date: 20221021 Year of fee payment: 20 Ref country code: ES Payment date: 20221201 Year of fee payment: 20 Ref country code: DE Payment date: 20221020 Year of fee payment: 20 |
|
P01 | Opt-out of the competence of the unified patent court (upc) registered |
Effective date: 20230520 |
|
REG | Reference to a national code |
Ref country code: DE Ref legal event code: R071 Ref document number: 60324311 Country of ref document: DE |
|
REG | Reference to a national code |
Ref country code: ES Ref legal event code: FD2A Effective date: 20231201 |
|
REG | Reference to a national code |
Ref country code: GB Ref legal event code: PE20 Expiry date: 20231111 |
|
PG25 | Lapsed in a contracting state [announced via postgrant information from national office to epo] |
Ref country code: GB Free format text: LAPSE BECAUSE OF EXPIRATION OF PROTECTION Effective date: 20231111 |
|
PG25 | Lapsed in a contracting state [announced via postgrant information from national office to epo] |
Ref country code: ES Free format text: LAPSE BECAUSE OF EXPIRATION OF PROTECTION Effective date: 20231113 |
|
PG25 | Lapsed in a contracting state [announced via postgrant information from national office to epo] |
Ref country code: GB Free format text: LAPSE BECAUSE OF EXPIRATION OF PROTECTION Effective date: 20231111 Ref country code: ES Free format text: LAPSE BECAUSE OF EXPIRATION OF PROTECTION Effective date: 20231113 |