EP1527373B1 - Procede de production de formes flexographiques par gravure directe au laser - Google Patents
Procede de production de formes flexographiques par gravure directe au laser Download PDFInfo
- Publication number
- EP1527373B1 EP1527373B1 EP03738040A EP03738040A EP1527373B1 EP 1527373 B1 EP1527373 B1 EP 1527373B1 EP 03738040 A EP03738040 A EP 03738040A EP 03738040 A EP03738040 A EP 03738040A EP 1527373 B1 EP1527373 B1 EP 1527373B1
- Authority
- EP
- European Patent Office
- Prior art keywords
- relief
- laser
- flexographic printing
- layer
- forming layer
- 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
- 238000007639 printing Methods 0.000 title claims abstract description 102
- 238000004519 manufacturing process Methods 0.000 title claims description 10
- 238000000034 method Methods 0.000 claims abstract description 46
- 239000004014 plasticizer Substances 0.000 claims abstract description 35
- 238000010147 laser engraving Methods 0.000 claims abstract description 23
- 239000011230 binding agent Substances 0.000 claims abstract description 19
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 18
- 230000002209 hydrophobic effect Effects 0.000 claims abstract description 12
- 239000000976 ink Substances 0.000 claims abstract description 11
- 239000007858 starting material Substances 0.000 claims abstract description 11
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims abstract description 6
- 238000004132 cross linking Methods 0.000 claims description 23
- 239000006096 absorbing agent Substances 0.000 claims description 20
- 229920000642 polymer Polymers 0.000 claims description 19
- 230000005855 radiation Effects 0.000 claims description 19
- 239000012459 cleaning agent Substances 0.000 claims description 8
- 239000002480 mineral oil Substances 0.000 claims description 8
- 239000004372 Polyvinyl alcohol Substances 0.000 claims description 4
- 125000003118 aryl group Chemical group 0.000 claims description 4
- 229920000578 graft copolymer Polymers 0.000 claims description 4
- 229920002451 polyvinyl alcohol Polymers 0.000 claims description 4
- 229920001169 thermoplastic Polymers 0.000 claims description 4
- 239000004416 thermosoftening plastic Substances 0.000 claims description 4
- 239000002202 Polyethylene glycol Substances 0.000 claims description 3
- 239000003125 aqueous solvent Substances 0.000 claims description 3
- 229920002678 cellulose Polymers 0.000 claims description 3
- 229920001223 polyethylene glycol Polymers 0.000 claims description 3
- 239000000758 substrate Substances 0.000 claims description 3
- 239000001913 cellulose Substances 0.000 claims description 2
- 229920000036 polyvinylpyrrolidone Polymers 0.000 claims description 2
- 239000001267 polyvinylpyrrolidone Substances 0.000 claims description 2
- 235000013855 polyvinylpyrrolidone Nutrition 0.000 claims description 2
- 235000010446 mineral oil Nutrition 0.000 claims 1
- 239000010410 layer Substances 0.000 description 117
- 239000003921 oil Substances 0.000 description 13
- 239000000203 mixture Substances 0.000 description 12
- 239000010408 film Substances 0.000 description 11
- 229920001400 block copolymer Polymers 0.000 description 9
- 229920001971 elastomer Polymers 0.000 description 7
- 229920000139 polyethylene terephthalate Polymers 0.000 description 7
- 239000005020 polyethylene terephthalate Substances 0.000 description 7
- 238000004140 cleaning Methods 0.000 description 6
- 230000000052 comparative effect Effects 0.000 description 6
- 238000000354 decomposition reaction Methods 0.000 description 6
- 239000000463 material Substances 0.000 description 6
- -1 polyethylene terephthalate Polymers 0.000 description 6
- 239000000047 product Substances 0.000 description 6
- 230000001681 protective effect Effects 0.000 description 6
- 238000005406 washing Methods 0.000 description 6
- 239000000178 monomer Substances 0.000 description 5
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 4
- 239000005062 Polybutadiene Substances 0.000 description 4
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 4
- ISAOCJYIOMOJEB-UHFFFAOYSA-N benzoin Chemical compound C=1C=CC=CC=1C(O)C(=O)C1=CC=CC=C1 ISAOCJYIOMOJEB-UHFFFAOYSA-N 0.000 description 4
- 239000000975 dye Substances 0.000 description 4
- 150000002148 esters Chemical class 0.000 description 4
- 238000007645 offset printing Methods 0.000 description 4
- 239000003960 organic solvent Substances 0.000 description 4
- 229920002857 polybutadiene Polymers 0.000 description 4
- 230000035945 sensitivity Effects 0.000 description 4
- 239000000654 additive Substances 0.000 description 3
- 230000002411 adverse Effects 0.000 description 3
- 238000009835 boiling Methods 0.000 description 3
- 239000003795 chemical substances by application Substances 0.000 description 3
- 239000003086 colorant Substances 0.000 description 3
- 239000000470 constituent Substances 0.000 description 3
- 239000013039 cover film Substances 0.000 description 3
- 238000011161 development Methods 0.000 description 3
- 238000001035 drying Methods 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 239000000806 elastomer Substances 0.000 description 3
- 238000002844 melting Methods 0.000 description 3
- 230000008018 melting Effects 0.000 description 3
- 229910052751 metal Inorganic materials 0.000 description 3
- 239000002184 metal Substances 0.000 description 3
- 239000005060 rubber Substances 0.000 description 3
- 239000002904 solvent Substances 0.000 description 3
- 229920003048 styrene butadiene rubber Polymers 0.000 description 3
- ROGIWVXWXZRRMZ-UHFFFAOYSA-N 2-methylbuta-1,3-diene;styrene Chemical compound CC(=C)C=C.C=CC1=CC=CC=C1 ROGIWVXWXZRRMZ-UHFFFAOYSA-N 0.000 description 2
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 2
- 229920002943 EPDM rubber Polymers 0.000 description 2
- 229920002633 Kraton (polymer) Polymers 0.000 description 2
- 244000028419 Styrax benzoin Species 0.000 description 2
- 235000000126 Styrax benzoin Nutrition 0.000 description 2
- 239000002174 Styrene-butadiene Substances 0.000 description 2
- 235000008411 Sumatra benzointree Nutrition 0.000 description 2
- 238000010521 absorption reaction Methods 0.000 description 2
- 150000001298 alcohols Chemical class 0.000 description 2
- 229910052782 aluminium Inorganic materials 0.000 description 2
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 2
- 239000002585 base Substances 0.000 description 2
- 229960002130 benzoin Drugs 0.000 description 2
- 230000001680 brushing effect Effects 0.000 description 2
- MTAZNLWOLGHBHU-UHFFFAOYSA-N butadiene-styrene rubber Chemical compound C=CC=C.C=CC1=CC=CC=C1 MTAZNLWOLGHBHU-UHFFFAOYSA-N 0.000 description 2
- 238000003490 calendering Methods 0.000 description 2
- 239000006229 carbon black Substances 0.000 description 2
- 235000019241 carbon black Nutrition 0.000 description 2
- 238000005266 casting Methods 0.000 description 2
- 238000006243 chemical reaction Methods 0.000 description 2
- 239000002131 composite material Substances 0.000 description 2
- 239000010949 copper Substances 0.000 description 2
- 229910052802 copper Inorganic materials 0.000 description 2
- 239000002270 dispersing agent Substances 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 238000002474 experimental method Methods 0.000 description 2
- 238000001125 extrusion Methods 0.000 description 2
- 239000004744 fabric Substances 0.000 description 2
- 239000003365 glass fiber Substances 0.000 description 2
- 235000019382 gum benzoic Nutrition 0.000 description 2
- 238000003384 imaging method Methods 0.000 description 2
- 239000003999 initiator Substances 0.000 description 2
- 239000001023 inorganic pigment Substances 0.000 description 2
- 239000000155 melt Substances 0.000 description 2
- 229910052759 nickel Inorganic materials 0.000 description 2
- 239000003208 petroleum Substances 0.000 description 2
- 239000004033 plastic Substances 0.000 description 2
- 229920003023 plastic Polymers 0.000 description 2
- 239000011112 polyethylene naphthalate Substances 0.000 description 2
- 150000004053 quinones Chemical class 0.000 description 2
- 238000010526 radical polymerization reaction Methods 0.000 description 2
- 230000002787 reinforcement Effects 0.000 description 2
- 239000011115 styrene butadiene Substances 0.000 description 2
- 239000004094 surface-active agent Substances 0.000 description 2
- VZCYOOQTPOCHFL-UHFFFAOYSA-N trans-butenedioic acid Natural products OC(=O)C=CC(O)=O VZCYOOQTPOCHFL-UHFFFAOYSA-N 0.000 description 2
- 238000012546 transfer Methods 0.000 description 2
- 229920000428 triblock copolymer Polymers 0.000 description 2
- SJLLJZNSZJHXQN-UHFFFAOYSA-N 1-dodecylpyrrole-2,5-dione Chemical compound CCCCCCCCCCCCN1C(=O)C=CC1=O SJLLJZNSZJHXQN-UHFFFAOYSA-N 0.000 description 1
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 description 1
- GOXQRTZXKQZDDN-UHFFFAOYSA-N 2-Ethylhexyl acrylate Chemical compound CCCCC(CC)COC(=O)C=C GOXQRTZXKQZDDN-UHFFFAOYSA-N 0.000 description 1
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 1
- DIVXVZXROTWKIH-UHFFFAOYSA-N 2-hydroxy-1,2-diphenylpropan-1-one Chemical compound C=1C=CC=CC=1C(O)(C)C(=O)C1=CC=CC=C1 DIVXVZXROTWKIH-UHFFFAOYSA-N 0.000 description 1
- 125000003903 2-propenyl group Chemical group [H]C([*])([H])C([H])=C([H])[H] 0.000 description 1
- QISOBCMNUJQOJU-UHFFFAOYSA-N 4-bromo-1h-pyrazole-5-carboxylic acid Chemical compound OC(=O)C=1NN=CC=1Br QISOBCMNUJQOJU-UHFFFAOYSA-N 0.000 description 1
- JHWGFJBTMHEZME-UHFFFAOYSA-N 4-prop-2-enoyloxybutyl prop-2-enoate Chemical compound C=CC(=O)OCCCCOC(=O)C=C JHWGFJBTMHEZME-UHFFFAOYSA-N 0.000 description 1
- SAPGBCWOQLHKKZ-UHFFFAOYSA-N 6-(2-methylprop-2-enoyloxy)hexyl 2-methylprop-2-enoate Chemical compound CC(=C)C(=O)OCCCCCCOC(=O)C(C)=C SAPGBCWOQLHKKZ-UHFFFAOYSA-N 0.000 description 1
- FIHBHSQYSYVZQE-UHFFFAOYSA-N 6-prop-2-enoyloxyhexyl prop-2-enoate Chemical compound C=CC(=O)OCCCCCCOC(=O)C=C FIHBHSQYSYVZQE-UHFFFAOYSA-N 0.000 description 1
- PGDIJTMOHORACQ-UHFFFAOYSA-N 9-prop-2-enoyloxynonyl prop-2-enoate Chemical compound C=CC(=O)OCCCCCCCCCOC(=O)C=C PGDIJTMOHORACQ-UHFFFAOYSA-N 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 description 1
- 239000001856 Ethyl cellulose Substances 0.000 description 1
- ZZSNKZQZMQGXPY-UHFFFAOYSA-N Ethyl cellulose Chemical compound CCOCC1OC(OC)C(OCC)C(OCC)C1OC1C(O)C(O)C(OC)C(CO)O1 ZZSNKZQZMQGXPY-UHFFFAOYSA-N 0.000 description 1
- VZCYOOQTPOCHFL-OWOJBTEDSA-N Fumaric acid Natural products OC(=O)\C=C\C(O)=O VZCYOOQTPOCHFL-OWOJBTEDSA-N 0.000 description 1
- 244000043261 Hevea brasiliensis Species 0.000 description 1
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 1
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 description 1
- 229920000459 Nitrile rubber Polymers 0.000 description 1
- 241000765083 Ondina Species 0.000 description 1
- 239000004952 Polyamide Substances 0.000 description 1
- OFOBLEOULBTSOW-UHFFFAOYSA-N Propanedioic acid Natural products OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 description 1
- 229910000639 Spring steel Inorganic materials 0.000 description 1
- 229910000831 Steel Inorganic materials 0.000 description 1
- DAKWPKUUDNSNPN-UHFFFAOYSA-N Trimethylolpropane triacrylate Chemical compound C=CC(=O)OCC(CC)(COC(=O)C=C)COC(=O)C=C DAKWPKUUDNSNPN-UHFFFAOYSA-N 0.000 description 1
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 1
- 239000012790 adhesive layer Substances 0.000 description 1
- 239000000443 aerosol Substances 0.000 description 1
- 150000001408 amides Chemical class 0.000 description 1
- 150000001412 amines Chemical class 0.000 description 1
- 150000001414 amino alcohols Chemical class 0.000 description 1
- 125000000751 azo group Chemical group [*]N=N[*] 0.000 description 1
- WURBFLDFSFBTLW-UHFFFAOYSA-N benzil Chemical class C=1C=CC=CC=1C(=O)C(=O)C1=CC=CC=C1 WURBFLDFSFBTLW-UHFFFAOYSA-N 0.000 description 1
- 238000007664 blowing Methods 0.000 description 1
- CQEYYJKEWSMYFG-UHFFFAOYSA-N butyl acrylate Chemical compound CCCCOC(=O)C=C CQEYYJKEWSMYFG-UHFFFAOYSA-N 0.000 description 1
- 229920005549 butyl rubber Polymers 0.000 description 1
- 229920003086 cellulose ether Polymers 0.000 description 1
- 239000007795 chemical reaction product Substances 0.000 description 1
- UOUJSJZBMCDAEU-UHFFFAOYSA-N chromium(3+);oxygen(2-) Chemical class [O-2].[O-2].[O-2].[Cr+3].[Cr+3] UOUJSJZBMCDAEU-UHFFFAOYSA-N 0.000 description 1
- 229920001577 copolymer Polymers 0.000 description 1
- 239000012043 crude product Substances 0.000 description 1
- 239000007857 degradation product Substances 0.000 description 1
- 210000003298 dental enamel Anatomy 0.000 description 1
- 229920000359 diblock copolymer Polymers 0.000 description 1
- 150000001993 dienes Chemical group 0.000 description 1
- TVWTZAGVNBPXHU-FOCLMDBBSA-N dioctyl (e)-but-2-enedioate Chemical compound CCCCCCCCOC(=O)\C=C\C(=O)OCCCCCCCC TVWTZAGVNBPXHU-FOCLMDBBSA-N 0.000 description 1
- 238000007598 dipping method Methods 0.000 description 1
- 238000010894 electron beam technology Methods 0.000 description 1
- 239000003995 emulsifying agent Substances 0.000 description 1
- 239000000839 emulsion Substances 0.000 description 1
- 239000003822 epoxy resin Substances 0.000 description 1
- 229920001249 ethyl cellulose Polymers 0.000 description 1
- 235000019325 ethyl cellulose Nutrition 0.000 description 1
- 239000000945 filler Substances 0.000 description 1
- 239000011888 foil Substances 0.000 description 1
- 235000013305 food Nutrition 0.000 description 1
- 238000009472 formulation Methods 0.000 description 1
- 239000012634 fragment Substances 0.000 description 1
- 239000001530 fumaric acid Substances 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 150000002432 hydroperoxides Chemical class 0.000 description 1
- 229920001600 hydrophobic polymer Polymers 0.000 description 1
- 229920013821 hydroxy alkyl cellulose Polymers 0.000 description 1
- 238000010348 incorporation Methods 0.000 description 1
- UQSXHKLRYXJYBZ-UHFFFAOYSA-N iron oxide Inorganic materials [Fe]=O UQSXHKLRYXJYBZ-UHFFFAOYSA-N 0.000 description 1
- 235000013980 iron oxide Nutrition 0.000 description 1
- VBMVTYDPPZVILR-UHFFFAOYSA-N iron(2+);oxygen(2-) Chemical class [O-2].[Fe+2] VBMVTYDPPZVILR-UHFFFAOYSA-N 0.000 description 1
- 229920003049 isoprene rubber Polymers 0.000 description 1
- 238000010030 laminating Methods 0.000 description 1
- PBOSTUDLECTMNL-UHFFFAOYSA-N lauryl acrylate Chemical compound CCCCCCCCCCCCOC(=O)C=C PBOSTUDLECTMNL-UHFFFAOYSA-N 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 229910052749 magnesium Inorganic materials 0.000 description 1
- 239000011777 magnesium Substances 0.000 description 1
- VZCYOOQTPOCHFL-UPHRSURJSA-N maleic acid Chemical compound OC(=O)\C=C/C(O)=O VZCYOOQTPOCHFL-UPHRSURJSA-N 0.000 description 1
- 239000011976 maleic acid Substances 0.000 description 1
- 239000000434 metal complex dye Substances 0.000 description 1
- 239000013528 metallic particle Substances 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 229920000609 methyl cellulose Polymers 0.000 description 1
- 239000001923 methylcellulose Substances 0.000 description 1
- 229920003052 natural elastomer Polymers 0.000 description 1
- 229920001194 natural rubber Polymers 0.000 description 1
- 230000006855 networking Effects 0.000 description 1
- 229920001220 nitrocellulos Polymers 0.000 description 1
- 239000004745 nonwoven fabric Substances 0.000 description 1
- 238000004806 packaging method and process Methods 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 150000002978 peroxides Chemical class 0.000 description 1
- 229920003207 poly(ethylene-2,6-naphthalate) Polymers 0.000 description 1
- 229920000636 poly(norbornene) polymer Polymers 0.000 description 1
- 229920002647 polyamide Polymers 0.000 description 1
- 229920001707 polybutylene terephthalate Polymers 0.000 description 1
- 229920000515 polycarbonate Polymers 0.000 description 1
- 239000004417 polycarbonate Substances 0.000 description 1
- 229920000647 polyepoxide Polymers 0.000 description 1
- 229920006267 polyester film Polymers 0.000 description 1
- 229920001195 polyisoprene Polymers 0.000 description 1
- 239000003505 polymerization initiator Substances 0.000 description 1
- 229920005862 polyol Polymers 0.000 description 1
- 150000003077 polyols Chemical class 0.000 description 1
- 239000004540 pour-on Substances 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 239000011164 primary particle Substances 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 229920005989 resin Polymers 0.000 description 1
- 239000011347 resin Substances 0.000 description 1
- 239000000779 smoke Substances 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 230000003595 spectral effect Effects 0.000 description 1
- 238000001228 spectrum Methods 0.000 description 1
- 238000005507 spraying Methods 0.000 description 1
- 229910001220 stainless steel Inorganic materials 0.000 description 1
- 239000010935 stainless steel Substances 0.000 description 1
- 239000010959 steel Substances 0.000 description 1
- 229920001935 styrene-ethylene-butadiene-styrene Polymers 0.000 description 1
- 150000003440 styrenes Chemical class 0.000 description 1
- 238000004381 surface treatment Methods 0.000 description 1
- 230000008961 swelling Effects 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- 238000012719 thermal polymerization Methods 0.000 description 1
- 239000003017 thermal stabilizer Substances 0.000 description 1
- 229920001187 thermosetting polymer Polymers 0.000 description 1
- JSPLKZUTYZBBKA-UHFFFAOYSA-N trioxidane Chemical class OOO JSPLKZUTYZBBKA-UHFFFAOYSA-N 0.000 description 1
- 238000005292 vacuum distillation Methods 0.000 description 1
- 229910052725 zinc Inorganic materials 0.000 description 1
- 239000011701 zinc Substances 0.000 description 1
Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B41—PRINTING; LINING MACHINES; TYPEWRITERS; STAMPS
- B41N—PRINTING PLATES OR FOILS; MATERIALS FOR SURFACES USED IN PRINTING MACHINES FOR PRINTING, INKING, DAMPING, OR THE LIKE; PREPARING SUCH SURFACES FOR USE AND CONSERVING THEM
- B41N1/00—Printing plates or foils; Materials therefor
- B41N1/12—Printing plates or foils; Materials therefor non-metallic other than stone, e.g. printing plates or foils comprising inorganic materials in an organic matrix
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B41—PRINTING; LINING MACHINES; TYPEWRITERS; STAMPS
- B41C—PROCESSES FOR THE MANUFACTURE OR REPRODUCTION OF PRINTING SURFACES
- B41C1/00—Forme preparation
- B41C1/02—Engraving; Heads therefor
- B41C1/04—Engraving; Heads therefor using heads controlled by an electric information signal
- B41C1/05—Heat-generating engraving heads, e.g. laser beam, electron beam
Definitions
- the invention relates to a process for the production of flexographic printing plates by means of direct laser engraving, in which a flexographic printing element is used as the starting material, the relief-forming layer comprising a combination of a substantially hydrophobic elastomeric binder and an inert plasticizer.
- the invention further relates to flexographic printing plates obtainable by this process and to the use of the flexographic printing plates for flexographic printing with printing inks based on water or alcohol.
- Lasers are now used both in the field of offset printing plates as in the field of relief printing plates for various steps of the manufacturing process.
- the photosensitive layers of offset printing plates by means of suitable laser printers.
- the photosensitive layer is chemically altered by the laser, for example crosslinked.
- the finished offset printing plate is obtained from the imaged crude product by means of a suitable development process (see, for example, US Pat Imaging Technology, Chap. 3.4.1.2., Ullmann's Encyclopedia of Industrial Chemistry, 6th Edt., 2000 Electronic release ).
- the thickness of said photosensitive layers of offset printing plates is usually 0.3 to 5 ⁇ m.
- IR ablative masks for imaging of flexographic printing plates instead of photographically created masks, such as in EP-A 654 150 disclosed.
- a thin IR-sensitive, opaque layer is applied to the photopolymerizable layer.
- the thickness of such IR-ablative layers is usually only a few microns.
- the IR ablative layer is imagewise described with an IR laser, ie removed at the points where it is hit by the laser beam.
- the actual printing relief is produced in a conventional manner: through the mask produced is exposed to actinic light and thus selectively crosslinks the relief-forming layer.
- a printing relief is engraved by a laser directly into the relief-forming layer of a flexographic printing element.
- a subsequent development step as conventional plates or the mask method is no longer necessary.
- Typical relief layer thicknesses of flexographic printing plates are between 0.5 to 7 mm, with special thin-layer plates possibly only 0.2 mm.
- the non-printing depressions in the relief amount to at least 0.03 mm in the grid area, significantly more in the case of other negative elements and can assume values of up to 3 mm for thick plates. With the laser so large amounts of material must be removed.
- EP-A 640 043 and EP-A 640 044 disclose single-layered or multi-layered elastomeric laser-engravable flexographic printing elements for the production of flexographic printing plates by means of laser engraving.
- the elements consist of "reinforced" elastomeric layers.
- Elastomeric binders are used to produce the layer.
- the so-called reinforcement increases the mechanical strength of the layer to allow flexographic printing.
- the reinforcement is achieved either by incorporation of suitable fillers, photochemical or thermochemical crosslinking or combinations thereof.
- US-A-2001/0044076 describes laser-engravable flexographic printing elements containing graft polymers as binders and plasticizers.
- US 5,259,311 discloses a method in which in a first step, a commercially available flexographic printing element photochemically crosslinked by full-surface irradiation by means of UV / A, the release layer is then removed with a flexo wash and engraved in a second step by means of a laser, a printing relief. Subsequently, a cleaning step is carried out by means of a flexo-washing agent followed by final drying of the plate.
- the relief layers of flexographic printing plates are naturally soft and have relatively low melting or softening points. Therefore, they are highly prone to laser engraving around the engraved elements in laser engraving. At the edge of the engraved elements, the layer melts under the influence of the laser beam, but is no longer or no longer completely decomposed. Such melt edges can not usually be removed by washing or at least not completely removed and lead to an unclean pressure. Unwanted melting of the layer also results in a reduced resolution of the print motif compared to the digital record.
- EP-A 1 136 254 proposes to solve this problem, to use polyoxyalkylene / polyethylene glycol graft copolymers as binders for relief-forming layers.
- these copolymers are water-soluble, such relief printing forms are disadvantageously usable only to a limited extent.
- the relief layer swells too much in flexographic inks based on water, so that unwanted effects occur during printing, such as an intolerable tone value increase.
- Such printing forms are therefore essentially used only for printing with UV inks.
- Decomposition products which have reacted again with the surface, can not be removed at all and can therefore be seen in print. It would be highly desirable to have a flexographic printing element in which any deposits can be easily removed with water or aqueous cleaning agents without swelling the plate.
- the fastest possible engraving is required for economical production of flexographic printing plates by means of laser engraving.
- the speed of the engraving depends on the one hand on the selected laser system.
- the sensitivity of the relief-forming layer should be as high as possible with respect to the respectively selected laser radiation.
- the relief layer gives the flexographic printing plate both the elastomeric properties and the printing-typical properties. Measures to improve the sensitivity must therefore not impair the properties mentioned.
- the object of the invention was therefore to provide a process for the production of flexographic printing plates by direct laser engraving, in which the occurrence of melt edges is significantly reduced, any deposits of decomposition products can be removed by simply treating the plate with water or aqueous cleaning agents, as fast as possible
- engraving in high resolution is enabled, and the resulting flexographic printing plates are also suitable for printing with water-based flexographic inks.
- flexographic printing plates were found, which are obtainable by the described method, and the use of these flexographic printing plates for flexographic printing with water-based inks and / or alcohol-based.
- suitable dimensionally stable supports for the flexographic printing elements used as starting material for the process are sheets, films and conical and cylindrical tubes made of metals such as steel, aluminum, copper or nickel or plastics such as polyethylene terephthalate (PET), polyethylene naphthalate (PEN), polybutylene terephthalate , Polyamide, polycarbonate, if appropriate also fabrics and nonwovens, such as glass fiber fabric and composite materials, for example of glass fibers and plastics.
- Dimensionally stable substrates are above all dimensionally stable carrier films such as polyester films, in particular PET or PEN films or flexible metallic substrates, such as thin metal sheets or metal foils, preferably of stainless steel, magnetizable spring steel, aluminum, zinc, magnesium, nickel; Chrome or copper into consideration.
- the flexographic printing element further comprises at least one laser-engravable, crosslinkable relief-forming layer.
- the crosslinkable relief-forming layer can be applied directly to the support. However, other layers may also be present between the carrier and the relief-forming layer, for example adhesion layers and / or elastic underlayers.
- the crosslinkable relief-forming layer comprises at least one substantially hydrophobic elastomeric binder, crosslinkable components and at least one inert plasticizer.
- the crosslinkable relief-forming layer as a whole already has elastomeric properties, but it is sufficient for the invention if only the crosslinked layer has the elastomeric properties typical of a flexographic printing plate.
- the substantially hydrophobic elastomers are those elastomers which are commonly used for the production of organic developable conventional flexographic printing plates and which are neither soluble nor swellable in water. Examples include natural rubber, polybutadiene, polyisoprene, styrene-butadiene rubber, nitrile-butadiene rubber, butyl rubber, styrene-isoprene rubber, polynorbornene rubber or ethylene-propylene-diene rubber (EPDM).
- natural rubber polybutadiene, polyisoprene, styrene-butadiene rubber, nitrile-butadiene rubber, butyl rubber, styrene-isoprene rubber, polynorbornene rubber or ethylene-propylene-diene rubber (EPDM).
- the substantially hydrophobic elastomer is a thermoplastic elastomeric block copolymer of alkenylaromatics and 1,3-dienes.
- the block copolymers may be both linear block copolymers and radial block copolymers. These are usually ABA-type triblock copolymers, but they can also be AB-type diblock polymers, or those having multiple alternating elastomeric and thermoplastic blocks, eg, ABABA. It is also possible to use mixtures of two or more different block copolymers. Commercially available triblock copolymers often contain certain proportions of diblock copolymers.
- the diene units may be 1,2- or 1,4-linked.
- block copolymers of styrene-butadiene and of styrene-isoprene type can be used. They are available, for example under the name Kraton ® commercially. Furthermore possible to employ thermoplastic-elastomeric block copolymers having end blocks of styrene and a random styrene-butadiene middle block, which are available under the name Styroflex ®.
- the block copolymers may also be fully or partially hydrogenated, as in SEBS rubbers.
- the total amount of binders is usually 40 to 80 wt.% With respect to the sum of all components of the relief layer, preferably 40 to 70 wt.% And particularly preferably 45 to 65 wt.%.
- the substantially hydrophobic binder in admixture with at least one inert plasticizer according to claim 1 is used for the process according to the invention.
- Plasticizers in the sense of this invention means that the plasticizers have no or at least substantially no polymerizable groups which can react in the course of radical crosslinking of the relief layer in such a way that the plasticizers are incorporated into the polymeric network of the relief-forming layer.
- inert plasticizers have substantially no ethylenically unsaturated double bonds, according to the group of aromatic, naphthenic or paraffinic solvents.
- inert plasticizers include high boiling paraffinic, naphthenic and aromatic mineral oils. Such mineral oils are obtained by vacuum distillation from petroleum.
- Such mineral oils are also referred to as white oils, the skilled person distinguishing between technical white oils, which may still have a low aromatics content, and medicinal white oils, which are essentially free of aromatics. They are commercially available, for example Shell Risella (technical white oil) or Shell Ondina (medicinal white oil).
- the amount of inert plasticizer is used by those skilled in effective amounts depending on the desired properties of the layer. As a rule, at least 5% by weight of inert plasticizer with respect to the sum of all components of the relief layer is required. Of course, this does not exclude that in exceptional cases, even with smaller amounts effective effects can be achieved in the bearing engraving. As a rule, the amount of the inert plasticizer is 5 to 40% by weight with respect to the sum of all components of the layer, preferably 10 to 40% by weight and particularly preferably 20 to 40% by weight.
- the type and amount of the components for crosslinking the layer depend on the desired crosslinking technique and are selected accordingly by the person skilled in the art.
- the full-surface crosslinking of the crosslinkable relief layer is carried out photochemically or thermochemically.
- the crosslinking is carried out photochemically.
- the relief-forming layer comprises at least one photoinitiator or a photoinitiator system and suitable monomers or oligomers.
- benzoin or benzoin derivatives such as ⁇ -methylbenzoin or benzoin ethers, benzil derivatives, e.g. Benzylketale, Acylarylphosphinoxide, Acylarylphosphinklareester or multinuclear quinones suitable without the list should be limited thereto.
- the monomers have at least one polymerizable, olefinically unsaturated group.
- Particularly advantageous are esters or amides of acrylic acid or methacrylic acid with mono- or polyfunctional alcohols, amines, amino alcohols or hydroxy ethers and esters, styrene or substituted styrenes. Esters of fumaric or maleic acid or allyl compounds proved.
- Suitable monomers include butyl acrylate, 2-ethylhexyl acrylate, lauryl acrylate, 1,4-butanediol diacrylate, 1,6-hexanediol diacrylate, 1,6-hexanediol dimethacrylate, 1,9-nonanediol diacrylate, trimethylolpropane triacrylate, dioctyl fumarate, N-dodecylmaleimide. It is also possible to use suitable oligomers with olefinic groups. Of course, it is also possible to use mixtures of different monomers or oligomers, provided that no undesired effects occur. The total amount of monomers will be determined by one skilled in the art according to the desired properties of the layer. As a rule, however, 20% by weight should not be exceeded with respect to the amount of all constituents of the laser-engravable relief-forming layer.
- thermal crosslinking can be carried out analogously to photochemical crosslinking by using a thermal polymerization initiator instead of a photoinitiator.
- thermal polymerization initiator instead of a photoinitiator.
- commercially available commercial thermal initiators for free-radical polymerization such as, for example, peroxides, hydroperoxides or azo compounds, are suitable in principle.
- the thermal crosslinking may also be carried out by adding a thermosetting resin such as an epoxy resin as the crosslinking component to the layer.
- the crosslinkable relief-forming layer may further comprise an absorber for laser radiation.
- an absorber for laser radiation It is also possible to use mixtures of different absorbers for laser radiation. Suitable absorbers for laser radiation have a high absorption in the range of the laser wavelength. In particular, absorbers are suitable which have high absorption in the near infrared and in the longer wavelength VIS range of the electromagnetic spectrum. Such absorbers are particularly suitable for absorbing the radiation of Nd-YAG lasers (1064 nm) and IR diode lasers, which typically have wavelengths between 700 and 900 nm and between 1200 and 1600 nm.
- suitable absorbers for laser radiation are dyes which absorb strongly in the infrared spectral range, for example phthalocyanines, naphthalocyanines, cyanines, quinones, metal complex dyes, for example dithiolenes or photochromic dyes.
- Further suitable absorbers are inorganic pigments, in particular intensively colored inorganic pigments such as, for example, chromium oxides, iron oxides, carbon black or metallic particles.
- Particularly suitable absorbers for laser radiation are finely divided carbon blacks having a primary particle size between 10 and 50 nm.
- the amount of optionally added absorber is selected by the skilled person depending on the respective desired properties of the laser-engravable flexographic printing element.
- the skilled person will take into account that the added absorber not only influence the engraving of the elastomeric layer by laser, but also other properties of the obtained as the end product of the process relief printing such as their hardness, elasticity, thermal conductivity or ink transfer behavior. As a rule, it is therefore advisable not to use more than 20% by weight, preferably not more than 10% by weight, of absorber for the laser radiation with regard to the sum of all constituents of the layer.
- relief-forming layers which are to be photochemically crosslinked, absorbers for laser radiation, which also absorb in the UV range, since this at least severely impairs the photopolymerization and possibly makes it completely impossible. It is advisable regularly to thermally crosslink such relief layers containing laser absorber.
- the relief-forming layer can furthermore also comprise additives and auxiliaries, such as, for example, dyes, dispersing agents or antistatics.
- additives and auxiliaries such as, for example, dyes, dispersing agents or antistatics.
- the amount of such additives should as a rule not exceed 5% by weight with respect to the amount of all components of the crosslinkable, laser-engravable layer of the recording element.
- the crosslinkable relief-forming layer can also be composed of several partial layers. These crosslinkable partial layers can be of the same, approximately the same or of different material composition.
- the thickness of the laser-engravable, elastomeric relief-forming layer is at least 0.2 mm.
- the thickness is preferably 0.3 to 7 mm, particularly preferably 0.5 to 5 mm and very particularly preferably 0.7 to 4 mm.
- the thickness is suitably selected by the person skilled in the art, depending on the intended use of the flexographic printing plate.
- the starting material comprises an additional, water-soluble or at least swellable laser-engravable polymer layer which is arranged on the laser-engravable relief layer and which comprises at least one polymer which is soluble or swellable in aqueous solvents.
- a layer serves to facilitate a post-cleaning step to be optionally performed. Solid decomposition products formed in the course of laser engraving can deposit on this auxiliary layer and be detached more easily.
- polystyrene resin examples include polyvinyl alcohol, polyvinyl alcohol / polyethylene glycol graft copolymers, polyvinylpyrrolidone and its derivatives or cellulose derivatives, especially cellulose esters and cellulose ethers such as methylcellulose, ethylcellulose, benzylcellulose, hydroxyalkylcelluloses, or nitrocelluloses.
- polyvinyl alcohol polyvinyl alcohol / polyethylene glycol graft copolymers
- polyvinylpyrrolidone and its derivatives or cellulose derivatives especially cellulose esters and cellulose ethers such as methylcellulose, ethylcellulose, benzylcellulose, hydroxyalkylcelluloses, or nitrocelluloses.
- mixtures of several polymers can be used.
- the additional laser-engravable polymer layer may also contain additives and auxiliaries, for example plasticizers or laser absorbers. If it is intended to photochemically crosslink the laser-engravable relief layer, then the additional polymer layer should be as transparent as possible in the UV range. For other meshing techniques this is not essential.
- the thickness of the additional polymer layer should be as low as possible. It depends essentially on the depth of focus of the laser used for engraving in the process. It is limited so that there is no significant broadening of the focus on the surface of the relief layer.
- the thickness of such an additional polymer layer should as a rule not exceed 100 ⁇ m. As a rule, no satisfactory results are achieved with larger thicknesses.
- the thickness should not exceed 50 microns. More preferably, the thickness is 1 - 40 microns, and most preferably 5 - 25 microns.
- the laser-engravable flexographic printing element may optionally include further layers.
- Such layers include an elastomeric sub-layer of another formulation located between the carrier and the laser-engravable layer (s) and which does not necessarily have to be laser engravable. With such sub-layers, the mechanical properties of the relief printing plates can be changed without affecting the properties of the actual printing relief layer.
- the so-called elastic substructures which are located under the dimensionally stable support of the laser-engravable flexographic printing element, ie on the side of the support facing away from the laser-engravable layer, serve the same purpose.
- adhesive layers that bond the backing to overlying layers or to different layers.
- the laser-engravable flexographic printing element can be protected against mechanical damage by a protective film, for example made of PET, also called cover film, which is located on the uppermost layer and which has to be removed with lasers before engraving.
- the protective film may be suitably surface-treated to facilitate peeling, for example by siliconization, provided that the surface treatment does not adversely affect the relief top layer in its printing properties.
- the flexographic printing element used as starting material for the process can be prepared, for example, by dissolving or dispersing all components in a suitable solvent and pouring onto a support.
- a suitable solvent for example, a solvent for a support.
- several layers can be cast on one another in a manner known in principle.
- the cover sheet can be applied to protect it from damage to the starting material. It is also possible, conversely, to pour on the cover film and finally laminate the carrier.
- the casting method is particularly recommended when thermally crosslinked.
- the production of the flexographic printing element can be particularly advantageous in a manner known in principle by melt extrusion between a carrier film and a cover sheet or a cover element and calendering of the resulting composite, such as EP-A 084 851 disclosed. This method is particularly recommended when photochemical or electron beam crosslinking is required. In this way, even thick layers can be produced in a single operation.
- Multilayer elements can be produced by coextrusion. Flexographic printing elements with metallic supports can preferably be obtained by pouring or extruding onto a temporary support, and then laminating the layer to the metallic support.
- the additional polymer layer can be applied, for example, by dissolving the constituents in a suitable solvent and pouring onto the relief-forming layer.
- the cover film is preferably coated with the additional polymer layer and laminated onto the relief layer or used as a film for the extrusion process.
- the starting material in the first process step (a) is first crosslinked over the entire surface.
- the full-surface crosslinking of the crosslinkable relief layer can be carried out photochemically, in particular by irradiation with UV-A radiation having a wavelength between 320 and 400 nm, or UV-A / VIS radiation having a wavelength of about 320 to 700 nm.
- Full-surface thermochemical crosslinking is effected by uniform, temperature-constant heating of the relief-forming layer.
- Photochemical crosslinking is particularly suitable for layers which do not contain strongly colored absorbers for laser radiation and which are transparent or at least substantially transparent in the UV / VIS range.
- transparent layers can also be thermochemically crosslinked.
- Dyed laser absorber-containing layers can advantageously be thermochemically crosslinked.
- the full-surface crosslinking can also be carried out by means of electron radiation.
- the flexographic printing element used as the starting material for the process is usually produced by a printing plate manufacturer, while the laser engraving is done by a cliché or printing works.
- the full-surface networking (a) can be done on the one hand by the cliché institution itself.
- the photochemical crosslinking can be carried out in commercially available flexographic printers.
- the crosslinking can of course also be carried out by or at the manufacturer of the flexographic printing element.
- a printing relief is engraved in the crosslinked relief-forming layer by means of a laser. If a protective film is present, it is removed before the engraving.
- the term "laser engravable” is to be understood as meaning that the relief layer has the property of absorbing laser radiation, in particular the radiation of an IR laser, so that it is removed or at least exposed at those points where it is exposed to a laser beam of sufficient intensity is replaced.
- the layer is thereby vaporized without premelting or thermally or oxidatively decomposed, so that its decomposition products in the form of hot gases, vapors, smoke or small particles are removed from the layer.
- IR laser For engraving are in particular IR laser.
- a CO 2 laser with a wavelength of 10.6 microns can be used.
- Nd-YAG lasers (1064 nm), IR diode lasers or solid-state lasers can be used. It is also possible to use lasers with shorter wavelengths, provided the laser has sufficient intensity. For example, it is also possible to use a frequency-doubled (532 nm) or frequency-tripled (355 nm) Nd-YAG laser or also excimer lasers (eg 248 nm).
- absorbers for laser radiation depends essentially on the type of laser to be used for engraving.
- the essentially hydrophobic elastomeric binders used for the relief-forming layer generally absorb the radiation of CO 2 lasers to a sufficient extent, so that additional IR absorbers are generally not required in the relief layer when using this type of laser.
- UV lasers such as excimer lasers.
- Nd-YAG lasers and IR diode lasers the addition of a laser absorber is usually required.
- the image information to be engraved can be transferred directly from the lay-out computer system to the laser apparatus.
- the lasers can be operated either continuously or pulsed.
- Relief elements are engraved advantageous in which the flanks of the elements initially fall vertically and widen only in the lower area. As a result, a good Versockelung the relief points is achieved with still low dot gain. But it can also be engraved differently shaped flanks.
- the depth of the elements to be engraved depends on the total thickness of the relief and the type of elements to be engraved and is determined by the person skilled in the art according to the desired properties of the printing form.
- the depth of the engraved relief elements is at least 0.03 mm, preferably at least 0.05 mm - is called here the minimum depth between individual halftone dots.
- Printing plates with too low relief depths are generally unsuitable for printing by means of flexographic printing technology because the negative elements are filled with printing ink.
- Individual negative points should usually have greater depths; for those of 0.2 mm diameter, a depth of at least 0.07 to 0.08 mm is usually recommended.
- For weggrav convinced surfaces is recommended a depth of more than 0.15 mm, preferably more than 0.4 mm. The latter is of course only possible with a correspondingly thick relief.
- the resulting flexographic printing plate is subsequently cleaned after the laser engraving in a further process step (c). In some cases, this can be done by simply blowing off with compressed air or brushing.
- liquid cleaning agent for subsequent cleaning in order to be able to remove polymer fragments completely. This is particularly recommended, for example, if the flexographic printing form is to be used to print food packaging in which particularly strict requirements with respect to volatile components apply.
- the post-purification can be carried out very advantageously by means of water or an aqueous cleaning agent.
- Aqueous cleaning agents consist essentially of water and optionally small amounts of alcohols and can aid in supporting the cleaning process, such as surfactants, emulsifiers, dispersants or bases. Mixtures commonly used to develop conventional water-developable flexographic printing plates can also be used. Since the relief layer with the substantially hydrophobic elastomeric binder is not swellable in water, the use of water or aqueous cleaning agents avoids time-consuming drying of the printing plate.
- the post-cleaning can be done for example by simply dipping or spraying the relief printing form or in addition by mechanical means, such as brushes or plushes are supported. It is also possible to use conventional flexo washers.
- any deposits as well as the residues of the additional polymer layer are removed.
- this layer prevents, or at least hampers, the fact that polymer droplets formed in the course of the laser engraving again firmly connect to the surface of the relief layer. Deposits can therefore be removed particularly easily. It is regularly recommended to carry out the post-wash step immediately after the laser engraving step.
- mixtures of organic solvents for post-cleaning in particular those mixtures which usually serve as washout agents for conventionally produced flexographic printing plates.
- washout agents based on high boiling, dearomatized petroleum fractions such as EP-A 332,070 or also "water-in-oil" emulsions, such as from EP-A 463 016 disclosed.
- This variant can be used especially if no additional polymer layer is present. If an additional polymer layer is present but not removable with the organic solvent used, it must be additionally cleaned with water or an aqueous cleaning agent.
- the resulting flexographic printing plates are particularly suitable for printing with water colors and alcohol colors. Of course, they are also suitable for printing with UV inks or flexographic inks containing low levels of esters.
- photochemically crosslinkable laser-engravable relief-forming layer of 55 wt.% (In terms of the sum of all components) of a hydrophobic elastomeric binder (Kraton D-1102, SBS block copolymer), 32 wt.% Of a plasticizer, 10 wt.% Hexandioldiacrylat, 2 Wt.% Photoinitiator and 1% dye and thermal stabilizer produced.
- the components were processed with an extruder (ZSK 53) at 140 ° C, introduced by means of a slot die between a dimensionally stable carrier film made of PET and a protective film of PET and then calendered by means of a two-roll calender.
- the layer thickness of the crosslinkable, laser-engravable layer obtained was 1.14 mm in each case.
- plasticizers used were the plasticizers listed in Table 1.
- examples 1 and 2 inert plasticizers of substantially paraffinic mineral oils were used, which have no ethylenically unsaturated double bonds, for the comparative examples polybutadiene oils were used which have in the chain or pendant ethylenically unsaturated double bonds.
- Table 1 Plasticizers used for experiments and comparative experiments Type example 1 White oil S 5000 (BASF) Example 2 Medicinal white oil (Ondina oil G 34, Shell) Comparative Example 1 Polybutadiene oil (Nisso PB 1000, Nippon Soda Co., Ltd.) Comparative Example 2 Polybutadiene oil (Polyol 130, Degussa)
- the PET protective film was peeled off. In a first process step, they were crosslinked over the entire surface by irradiation with UVA light for 20 minutes. In Examples 1 and 2, an additional crosslinking of the uppermost region of the relief layer with UVC light was carried out.
- ALE ALE meridian finesse
- the power on the disk surface was about 150 watts at maximum power.
- a test motif consisting of various representative, positive and negative elements was engraved on the flexographic printing element.
- the motif also contains various screen areas with tonal values between 1% and 98% and 40 ⁇ m wide negative lines in the axial and transversal direction to the cylinder axis of rotation.
- the engraving depth was between 0.64 and 0.685 mm for all flexographic printing plates.
- the panels of Examples 1 and 2 made according to the invention with inert plasticizers had essentially no melt edges, whereas the panels of Comparative Examples 1 and 2 with reactive plasticizers had distinct enamel edges by comparison.
- the resulting flexographic printing plates were rinsed for two minutes with a mixture of water and a surfactant, with simultaneous brushing of the surface.
- a nyloprint ® WASHER device combination "CW 22 x 30", BASF Printing Systems GmbH.
- the resulting flexographic printing plates are well suited for printing with alcohol and water colors.
Landscapes
- Engineering & Computer Science (AREA)
- Physics & Mathematics (AREA)
- Optics & Photonics (AREA)
- Plasma & Fusion (AREA)
- Manufacturing & Machinery (AREA)
- Manufacture Or Reproduction Of Printing Formes (AREA)
- Printing Plates And Materials Therefor (AREA)
- Laser Beam Processing (AREA)
- Laser Beam Printer (AREA)
Claims (11)
- Procédé de production de formes flexographiques par gravure laser, dans lequel est employé comme matériau de départ un élément flexographique réticulable pouvant être gravé par laser, et qui comporte, agencés l'un sur l'autre, au minimum,• un substrat dimensionnellement stable,• une couche en relief qui peut être gravée par laser et réticulée, d'une épaisseur d'au moins 0,2 mm, comportant au moins un liant élastomère essentiellement hydrophobe, un plastifiant ainsi que des agents de réticulation,et le procédé comportant au moins les étapes suivantes :(a) réticulation de toute la couche en relief,(b) gravure d'une impression dans la couche en relief réticulée à l'aide d'un laser, la profondeur des éléments en relief gravés avec le laser étant égale au moins à 0,03 mm,caractérisé en ce que le plastifiant est un plastifiant inerte, choisi dans le groupe des huiles minérales aromatiques, naphténiques et paraffiniques.
- Procédé selon la revendication 1 caractérisé en ce que le plastifiant inerte est une huile minérale paraffinique et/ou naphténique.
- Procédé selon l'une des revendications 1 ou 2, caractérisé en ce que le plastifiant est employé en une quantité de 5 à 40 % en poids par rapport à la quantité de tous les composants de la couche formant le relief.
- Procédé selon la revendication 3, caractérisé en ce que le plastifiant est employé en une quantité de 20 à 40 % en poids par rapport à la quantité de tous les composants de la couche formant le relief.
- Procédé selon l'une des revendications 1 à 4, caractérisé en ce que le liant est un liant élastomère thermoplastique.
- Procédé selon l'une des revendications 1 à 5, caractérisé en ce que la réticulation totale (a) est réalisée photochimiquement ou thermiquement.
- Procédé selon l'une des revendications 1 à 6, caractérisé en ce que la couche formant le relief comporte en outre un absorbeur de rayon laser.
- Procédé selon l'une des revendications 1 à 7, caractérisé en ce que l'élément flexographique comporte une couche supplémentaire pouvant être gravée par laser, soluble dans l'eau, qui est disposée sur la couche formant le relief pouvant être gravée par laser et qui comporte au moins un polymère soluble ou gélifiable dans des solvants aqueux, et qui peut être enlevé après l'étape du procédé (b), par une nouvelle étape (c) avec de l'eau ou un détergent aqueux.
- Procédé selon la revendication 8, caractérisé en ce que le polymère est au moins un polymère choisi dans le groupe des alcools polyvinyliques, des copolymères d'alcool polyvinylique/polyéthylène-glycol greffé, de polyvinyl-pyrrolidone ou de dérivés de cellulose.
- Forme flexographique obtenue par un procédé selon l'une des revendications 1 à 9.
- Utilisation d'une forme flexographique selon la revendication 10 pour l'impression flexographique avec des encres à base d'eau ou d'alcool.
Applications Claiming Priority (3)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
DE10227189 | 2002-06-18 | ||
DE10227189A DE10227189A1 (de) | 2002-06-18 | 2002-06-18 | Verfahren zur Herstellung von Flexdruckformen mittels Laser-Direktgravur |
PCT/EP2003/006331 WO2003107092A1 (fr) | 2002-06-18 | 2003-06-16 | Procede de production de formes flexographiques par gravure directe au laser |
Publications (2)
Publication Number | Publication Date |
---|---|
EP1527373A1 EP1527373A1 (fr) | 2005-05-04 |
EP1527373B1 true EP1527373B1 (fr) | 2008-01-16 |
Family
ID=29719216
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
EP03738040A Expired - Lifetime EP1527373B1 (fr) | 2002-06-18 | 2003-06-16 | Procede de production de formes flexographiques par gravure directe au laser |
Country Status (7)
Country | Link |
---|---|
US (1) | US7290487B2 (fr) |
EP (1) | EP1527373B1 (fr) |
JP (1) | JP4372002B2 (fr) |
AT (1) | ATE384283T1 (fr) |
AU (1) | AU2003245950A1 (fr) |
DE (2) | DE10227189A1 (fr) |
WO (1) | WO2003107092A1 (fr) |
Families Citing this family (19)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
DE102004025364A1 (de) | 2004-05-19 | 2005-12-08 | Basf Drucksysteme Gmbh | Verfahren zur Herstellung von Flexodruckformen mittels Laser-Direktgravur |
US20100015870A1 (en) * | 2008-07-18 | 2010-01-21 | Chien-Hung Lin | Printed fabric and a manufacturing process thereof |
US20110067585A1 (en) * | 2008-07-18 | 2011-03-24 | Ampro Co., Ltd. | Fabric printing method |
JP2011093308A (ja) | 2009-09-30 | 2011-05-12 | Fujifilm Corp | レーザー彫刻用樹脂組成物、レーザー彫刻用レリーフ印刷版原版とその製造方法、及び、レリーフ印刷版とその製版方法 |
US20110236705A1 (en) * | 2010-03-29 | 2011-09-29 | Ophira Melamed | Flexographic printing precursors and methods of making |
JP5174134B2 (ja) | 2010-11-29 | 2013-04-03 | 富士フイルム株式会社 | レーザー彫刻用樹脂組成物、レーザー彫刻用レリーフ印刷版原版、レリーフ印刷版の製版方法及びレリーフ印刷版 |
US8920692B2 (en) | 2011-03-22 | 2014-12-30 | Eastman Kodak Company | Method for recycling relief image elements |
US20120240802A1 (en) * | 2011-03-22 | 2012-09-27 | Landry-Coltrain Christine J | Laser-engraveable flexographic printing precursors |
US9156299B2 (en) | 2011-06-30 | 2015-10-13 | Eastman Kodak Company | Laser-imageable flexographic printing precursors and methods of imaging |
US8900507B2 (en) | 2011-06-30 | 2014-12-02 | Eastman Kodak Company | Laser-imageable flexographic printing precursors and methods of imaging |
US8563087B2 (en) | 2011-09-27 | 2013-10-22 | Eastman Kodak Company | Method of making laser-engraveable flexographic printing precursors |
US9027476B2 (en) | 2011-09-27 | 2015-05-12 | Eastman Kodak Company | Laser-engraveable flexographic printing precursors and methods of imaging |
US20130101834A1 (en) | 2011-10-20 | 2013-04-25 | Dana Barshishat | Laser-imageable flexographic printing precursors and methods of imaging |
US9156241B2 (en) | 2011-12-12 | 2015-10-13 | Eastman Kodak Company | Laser-imageable flexographic printing precursors and methods of relief imaging |
DE102012006558B4 (de) | 2012-04-02 | 2019-09-12 | Hell Gravure Systems Gmbh & Co. Kg | Verfahren zur Herstellung einer Flexodruckform |
US20130288006A1 (en) | 2012-04-26 | 2013-10-31 | Anna C. Greene | Laser-engraveable elements and method of use |
US9180654B2 (en) | 2012-04-26 | 2015-11-10 | Eastman Kodak Company | Reactive fluoropolymer and laser-engraveable compositions and preparatory methods |
US9522523B2 (en) | 2012-04-30 | 2016-12-20 | Eastman Kodak Company | Laser-imageable flexographic printing precursors and methods of imaging |
JP6051920B2 (ja) * | 2013-02-20 | 2016-12-27 | 東洋紡株式会社 | フレキソ印刷原版用感光性樹脂組成物及びフレキソ印刷原版 |
Family Cites Families (13)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JPS53127004A (en) * | 1977-04-11 | 1978-11-06 | Asahi Chemical Ind | Photosensitive elastomer composition |
US5798202A (en) * | 1992-05-11 | 1998-08-25 | E. I. Dupont De Nemours And Company | Laser engravable single-layer flexographic printing element |
US5804353A (en) * | 1992-05-11 | 1998-09-08 | E. I. Dupont De Nemours And Company | Lasers engravable multilayer flexographic printing element |
US5259311A (en) * | 1992-07-15 | 1993-11-09 | Mark/Trece Inc. | Laser engraving of photopolymer printing plates |
US5719009A (en) * | 1992-08-07 | 1998-02-17 | E. I. Du Pont De Nemours And Company | Laser ablatable photosensitive elements utilized to make flexographic printing plates |
US5262275A (en) * | 1992-08-07 | 1993-11-16 | E. I. Du Pont De Nemours And Company | Flexographic printing element having an IR ablatable layer and process for making a flexographic printing plate |
JPH1031303A (ja) * | 1994-09-29 | 1998-02-03 | Nippon Zeon Co Ltd | 感光性組成物及び感光性ゴム版 |
US6238837B1 (en) * | 1995-05-01 | 2001-05-29 | E.I. Du Pont De Nemours And Company | Flexographic element having an infrared ablatable layer |
DE19536805A1 (de) | 1995-10-02 | 1997-04-03 | Basf Lacke & Farben | Zur Herstellung von Flexodruckplatten durch digitale Informationsübertragung geeignetes mehrschichtiges Aufzeichnungselement |
DE19908528A1 (de) * | 1999-02-26 | 2000-08-31 | Agfa Gevaert Ag | Strahlungsempfindliches Aufzeichnungsmaterial zur Herstellung von Wasserlos-Offsetdruckplatten |
DE50100265D1 (de) | 2000-03-23 | 2003-07-03 | Basf Drucksysteme Gmbh | Verwendung von Pfropfcopolymeren zur Herstellung lasergravierbarer Reliefdruckelementen |
DE10100514A1 (de) * | 2001-01-08 | 2002-07-11 | Basf Drucksysteme Gmbh | Verfahren zur Herstellung von thermisch vernetzten, lasergravierbaren Flexodruckelementen |
DE10241851A1 (de) * | 2002-09-09 | 2004-03-18 | Basf Drucksysteme Gmbh | Verfahren zur Herstellung von Flexodruckformen durch thermische Entwicklung |
-
2002
- 2002-06-18 DE DE10227189A patent/DE10227189A1/de not_active Withdrawn
-
2003
- 2003-06-16 JP JP2004513845A patent/JP4372002B2/ja not_active Expired - Fee Related
- 2003-06-16 DE DE50309036T patent/DE50309036D1/de not_active Expired - Lifetime
- 2003-06-16 EP EP03738040A patent/EP1527373B1/fr not_active Expired - Lifetime
- 2003-06-16 US US10/513,757 patent/US7290487B2/en not_active Expired - Lifetime
- 2003-06-16 AU AU2003245950A patent/AU2003245950A1/en not_active Abandoned
- 2003-06-16 WO PCT/EP2003/006331 patent/WO2003107092A1/fr active IP Right Grant
- 2003-06-16 AT AT03738040T patent/ATE384283T1/de not_active IP Right Cessation
Also Published As
Publication number | Publication date |
---|---|
DE10227189A1 (de) | 2004-01-08 |
JP4372002B2 (ja) | 2009-11-25 |
AU2003245950A1 (en) | 2003-12-31 |
JP2005534525A (ja) | 2005-11-17 |
ATE384283T1 (de) | 2008-02-15 |
US20050166779A1 (en) | 2005-08-04 |
DE50309036D1 (de) | 2008-03-06 |
US7290487B2 (en) | 2007-11-06 |
WO2003107092A1 (fr) | 2003-12-24 |
EP1527373A1 (fr) | 2005-05-04 |
Similar Documents
Publication | Publication Date | Title |
---|---|---|
EP1527373B1 (fr) | Procede de production de formes flexographiques par gravure directe au laser | |
EP1423280B1 (fr) | Procede de production de formes flexographiques par gravure directe au laser | |
EP1613484B1 (fr) | Element pour impression flexographique grave au laser, renfermant du noir de fumee de conductibilite, et procede de production de formes pour flexographie | |
EP1451014B1 (fr) | Elements d'impression flexographique pouvant etre graves au laser, servant a la production de cliches flexographiques contenant des melanges de polymeres hydrophiles et d'elastomeres hydrophobes | |
EP1315617B1 (fr) | Procede pour produire des plaques d'impression flexographique par gravure au laser | |
EP1400857B1 (fr) | Procédé de fabrication de plaques flexographiques par développement thermique | |
DE60027475T2 (de) | Mit laser belichtete druckplatten, einen mehrschichtigen gleitfilm enthaltend | |
EP1381511B1 (fr) | Element d'impression par flexographie pouvant etre grave au laser comprenant des couches elastomeres en relief renfermant du 1,2-polybutadiene syndiotactique | |
WO2002049842A1 (fr) | Procede de fabrication de blocs d'impression flexographique par gravure laser | |
EP3304203B1 (fr) | Plaque d'impression flexographique imageable de manière numérique pourvu d'une couche barrière intégrale | |
EP1213615A2 (fr) | Elément d'impression flexographique photosensible ayant au moins deux couches décomposables par infrarouge | |
DE102006028640A1 (de) | Fotopolymerisierbarer Schichtenverbund zur Herstellung von Flexodruckelementen | |
DE102007006378A1 (de) | Fotopolymerisierbare zylindrische endlos-nahtlose Flexodruckelemente und daraus hergestellte harte Flexodruckformen | |
EP1414647B1 (fr) | Procede de production de blocs d'impression flexographique par reticulation par faisceau electronique et par gravure laser | |
EP1578605A1 (fr) | Procede de fabrication de formes imprimantes flexographiques par gravure au laser a l'aide d'elements flexographiques photopolymeres et element flexographique photopolymerisable | |
WO2018141644A1 (fr) | Mélange durcissable par rayonnement contenant un poly(acétate de vinyle) partiellement saponifié faiblement fonctionnalisé | |
WO2002076738A1 (fr) | Procede pour produire des plaques d'impression en relief par gravure au laser |
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: 20050302 |
|
AK | Designated contracting states |
Kind code of ref document: A1 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) | ||
RAP1 | Party data changed (applicant data changed or rights of an application transferred) |
Owner name: XSYS PRINT SOLUTIONS DEUTSCHLAND GMBH |
|
GRAP | Despatch of communication of intention to grant a patent |
Free format text: ORIGINAL CODE: EPIDOSNIGR1 |
|
RAP1 | Party data changed (applicant data changed or rights of an application transferred) |
Owner name: FLINT GROUP GERMANY GMBH |
|
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 Free format text: NOT ENGLISH |
|
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 Free format text: LANGUAGE OF EP DOCUMENT: GERMAN |
|
REF | Corresponds to: |
Ref document number: 50309036 Country of ref document: DE Date of ref document: 20080306 Kind code of ref document: P |
|
GBT | Gb: translation of ep patent filed (gb section 77(6)(a)/1977) |
Effective date: 20080427 |
|
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: 20080116 |
|
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: 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: 20080116 Ref country code: ES 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: 20080427 |
|
PG25 | Lapsed in a contracting state [announced via postgrant information from national office to epo] |
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: 20080416 |
|
ET | Fr: translation filed | ||
PG25 | Lapsed in a contracting state [announced via postgrant information from national office to epo] |
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: 20080616 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: 20080116 |
|
REG | Reference to a national code |
Ref country code: IE Ref legal event code: FD4D |
|
PG25 | Lapsed in a contracting state [announced via postgrant information from national office to epo] |
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: 20080116 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: 20080416 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: 20080116 Ref country code: IE 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: 20080116 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: 20080116 |
|
PLBE | No opposition filed within time limit |
Free format text: ORIGINAL CODE: 0009261 |
|
STAA | Information on the status of an ep patent application or granted ep patent |
Free format text: STATUS: NO OPPOSITION FILED WITHIN TIME LIMIT |
|
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: 20080116 |
|
26N | No opposition filed |
Effective date: 20081017 |
|
BERE | Be: lapsed |
Owner name: FLINT GROUP GERMANY G.M.B.H. Effective date: 20080630 |
|
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: 20080630 |
|
REG | Reference to a national code |
Ref country code: CH Ref legal event code: PL |
|
PG25 | Lapsed in a contracting state [announced via postgrant information from national office to epo] |
Ref country code: BE Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES Effective date: 20080630 |
|
PG25 | Lapsed in a contracting state [announced via postgrant information from national office to epo] |
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: 20080116 |
|
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: 20080630 Ref country code: LI Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES Effective date: 20080630 |
|
PG25 | Lapsed in a contracting state [announced via postgrant information from national office to epo] |
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: 20080116 |
|
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 NON-PAYMENT OF DUE FEES Effective date: 20080616 |
|
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: 20080616 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: 20080717 |
|
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: 20080116 |
|
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: 20080417 |
|
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 |
|
REG | Reference to a national code |
Ref country code: FR Ref legal event code: PLFP Year of fee payment: 16 |
|
PGFP | Annual fee paid to national office [announced via postgrant information from national office to epo] |
Ref country code: IT Payment date: 20190619 Year of fee payment: 17 |
|
PGFP | Annual fee paid to national office [announced via postgrant information from national office to epo] |
Ref country code: FR Payment date: 20190626 Year of fee payment: 17 |
|
PGFP | Annual fee paid to national office [announced via postgrant information from national office to epo] |
Ref country code: GB Payment date: 20190624 Year of fee payment: 17 Ref country code: DE Payment date: 20190828 Year of fee payment: 17 |
|
REG | Reference to a national code |
Ref country code: DE Ref legal event code: R119 Ref document number: 50309036 Country of ref document: DE |
|
GBPC | Gb: european patent ceased through non-payment of renewal fee |
Effective date: 20200616 |
|
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 NON-PAYMENT OF DUE FEES Effective date: 20200616 Ref country code: FR Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES Effective date: 20200630 |
|
PG25 | Lapsed in a contracting state [announced via postgrant information from national office to epo] |
Ref country code: DE Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES Effective date: 20210101 |
|
PG25 | Lapsed in a contracting state [announced via postgrant information from national office to epo] |
Ref country code: IT Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES Effective date: 20200616 |