EP2758249A1 - Recording material for offset printing - Google Patents
Recording material for offset printingInfo
- Publication number
- EP2758249A1 EP2758249A1 EP12745873.5A EP12745873A EP2758249A1 EP 2758249 A1 EP2758249 A1 EP 2758249A1 EP 12745873 A EP12745873 A EP 12745873A EP 2758249 A1 EP2758249 A1 EP 2758249A1
- Authority
- EP
- European Patent Office
- Prior art keywords
- recording layer
- layer
- recording
- coating
- recording material
- 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.)
- Granted
Links
- 239000000463 material Substances 0.000 title claims abstract description 42
- 238000007645 offset printing Methods 0.000 title claims abstract description 14
- 239000010410 layer Substances 0.000 claims abstract description 110
- 239000011247 coating layer Substances 0.000 claims abstract description 39
- 239000000758 substrate Substances 0.000 claims abstract description 25
- 238000000034 method Methods 0.000 claims abstract description 21
- 239000008199 coating composition Substances 0.000 claims description 46
- 239000011230 binding agent Substances 0.000 claims description 13
- -1 Carboxy- Chemical class 0.000 claims description 11
- 238000001035 drying Methods 0.000 claims description 11
- 238000004519 manufacturing process Methods 0.000 claims description 10
- 238000000576 coating method Methods 0.000 claims description 8
- 238000004132 cross linking Methods 0.000 claims description 8
- 229920002451 polyvinyl alcohol Polymers 0.000 claims description 8
- 229920000219 Ethylene vinyl alcohol Polymers 0.000 claims description 7
- 239000011248 coating agent Substances 0.000 claims description 7
- 239000000049 pigment Substances 0.000 claims description 7
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 claims description 6
- 239000004372 Polyvinyl alcohol Substances 0.000 claims description 6
- 239000000203 mixture Substances 0.000 claims description 3
- 229920005989 resin Polymers 0.000 claims description 3
- 239000011347 resin Substances 0.000 claims description 3
- ZNZYKNKBJPZETN-WELNAUFTSA-N Dialdehyde 11678 Chemical compound N1C2=CC=CC=C2C2=C1[C@H](C[C@H](/C(=C/O)C(=O)OC)[C@@H](C=C)C=O)NCC2 ZNZYKNKBJPZETN-WELNAUFTSA-N 0.000 claims description 2
- MGJKQDOBUOMPEZ-UHFFFAOYSA-N N,N'-dimethylurea Chemical compound CNC(=O)NC MGJKQDOBUOMPEZ-UHFFFAOYSA-N 0.000 claims description 2
- IBVAQQYNSHJXBV-UHFFFAOYSA-N adipic acid dihydrazide Chemical compound NNC(=O)CCCCC(=O)NN IBVAQQYNSHJXBV-UHFFFAOYSA-N 0.000 claims description 2
- KGBXLFKZBHKPEV-UHFFFAOYSA-N boric acid Chemical compound OB(O)O KGBXLFKZBHKPEV-UHFFFAOYSA-N 0.000 claims description 2
- 239000004327 boric acid Substances 0.000 claims description 2
- 239000003822 epoxy resin Substances 0.000 claims description 2
- 239000004715 ethylene vinyl alcohol Substances 0.000 claims description 2
- 229920000768 polyamine Polymers 0.000 claims description 2
- 229920000647 polyepoxide Polymers 0.000 claims description 2
- 229920000877 Melamine resin Polymers 0.000 claims 1
- IVJISJACKSSFGE-UHFFFAOYSA-N formaldehyde;1,3,5-triazine-2,4,6-triamine Chemical compound O=C.NC1=NC(N)=NC(N)=N1 IVJISJACKSSFGE-UHFFFAOYSA-N 0.000 claims 1
- 238000007639 printing Methods 0.000 description 9
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 description 8
- 239000011241 protective layer Substances 0.000 description 8
- 239000000975 dye Substances 0.000 description 6
- 235000019422 polyvinyl alcohol Nutrition 0.000 description 6
- HHVIBTZHLRERCL-UHFFFAOYSA-N sulfonyldimethane Chemical compound CS(C)(=O)=O HHVIBTZHLRERCL-UHFFFAOYSA-N 0.000 description 6
- 239000000370 acceptor Substances 0.000 description 5
- 239000001023 inorganic pigment Substances 0.000 description 5
- 239000002243 precursor Substances 0.000 description 5
- 231100000489 sensitizer Toxicity 0.000 description 5
- VPWNQTHUCYMVMZ-UHFFFAOYSA-N 4,4'-sulfonyldiphenol Chemical compound C1=CC(O)=CC=C1S(=O)(=O)C1=CC=C(O)C=C1 VPWNQTHUCYMVMZ-UHFFFAOYSA-N 0.000 description 4
- IISBACLAFKSPIT-UHFFFAOYSA-N bisphenol A Chemical compound C=1C=C(O)C=CC=1C(C)(C)C1=CC=C(O)C=C1 IISBACLAFKSPIT-UHFFFAOYSA-N 0.000 description 4
- 229910000019 calcium carbonate Inorganic materials 0.000 description 4
- 229920001577 copolymer Polymers 0.000 description 4
- 239000000126 substance Substances 0.000 description 4
- XAAILNNJDMIMON-UHFFFAOYSA-N 2'-anilino-6'-(dibutylamino)-3'-methylspiro[2-benzofuran-3,9'-xanthene]-1-one Chemical compound C=1C(N(CCCC)CCCC)=CC=C(C2(C3=CC=CC=C3C(=O)O2)C2=C3)C=1OC2=CC(C)=C3NC1=CC=CC=C1 XAAILNNJDMIMON-UHFFFAOYSA-N 0.000 description 3
- 229920001131 Pulp (paper) Polymers 0.000 description 3
- LYRFLYHAGKPMFH-UHFFFAOYSA-N octadecanamide Chemical compound CCCCCCCCCCCCCCCCCC(N)=O LYRFLYHAGKPMFH-UHFFFAOYSA-N 0.000 description 3
- 239000012860 organic pigment Substances 0.000 description 3
- 239000005995 Aluminium silicate Substances 0.000 description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 2
- 229920002472 Starch Polymers 0.000 description 2
- 235000012211 aluminium silicate Nutrition 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 229910001593 boehmite Inorganic materials 0.000 description 2
- 239000000470 constituent Substances 0.000 description 2
- MCPKSFINULVDNX-UHFFFAOYSA-N drometrizole Chemical compound CC1=CC=C(O)C(N2N=C3C=CC=CC3=N2)=C1 MCPKSFINULVDNX-UHFFFAOYSA-N 0.000 description 2
- FAHBNUUHRFUEAI-UHFFFAOYSA-M hydroxidooxidoaluminium Chemical compound O[Al]=O FAHBNUUHRFUEAI-UHFFFAOYSA-M 0.000 description 2
- 238000010348 incorporation Methods 0.000 description 2
- 239000000976 ink Substances 0.000 description 2
- NLYAJNPCOHFWQQ-UHFFFAOYSA-N kaolin Chemical compound O.O.O=[Al]O[Si](=O)O[Si](=O)O[Al]=O NLYAJNPCOHFWQQ-UHFFFAOYSA-N 0.000 description 2
- 239000004816 latex Substances 0.000 description 2
- 229920000126 latex Polymers 0.000 description 2
- 230000003287 optical effect Effects 0.000 description 2
- 239000003960 organic solvent Substances 0.000 description 2
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 description 2
- IWDCLRJOBJJRNH-UHFFFAOYSA-N p-cresol Chemical compound CC1=CC=C(O)C=C1 IWDCLRJOBJJRNH-UHFFFAOYSA-N 0.000 description 2
- 239000012188 paraffin wax Substances 0.000 description 2
- 239000002245 particle Substances 0.000 description 2
- 239000008107 starch Substances 0.000 description 2
- 235000019698 starch Nutrition 0.000 description 2
- 229920003048 styrene butadiene rubber Polymers 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- WCOXQTXVACYMLM-UHFFFAOYSA-N 2,3-bis(12-hydroxyoctadecanoyloxy)propyl 12-hydroxyoctadecanoate Chemical compound CCCCCCC(O)CCCCCCCCCCC(=O)OCC(OC(=O)CCCCCCCCCCC(O)CCCCCC)COC(=O)CCCCCCCCCCC(O)CCCCCC WCOXQTXVACYMLM-UHFFFAOYSA-N 0.000 description 1
- JHOPNNNTBHXSHY-UHFFFAOYSA-N 2-(4-hydroxyphenyl)phenol Chemical group C1=CC(O)=CC=C1C1=CC=CC=C1O JHOPNNNTBHXSHY-UHFFFAOYSA-N 0.000 description 1
- FPIAKQHHSBQHDE-UHFFFAOYSA-N 2-methylprop-2-enoic acid;prop-2-enamide;prop-2-enoic acid Chemical compound NC(=O)C=C.OC(=O)C=C.CC(=C)C(O)=O FPIAKQHHSBQHDE-UHFFFAOYSA-N 0.000 description 1
- PYSRRFNXTXNWCD-UHFFFAOYSA-N 3-(2-phenylethenyl)furan-2,5-dione Chemical class O=C1OC(=O)C(C=CC=2C=CC=CC=2)=C1 PYSRRFNXTXNWCD-UHFFFAOYSA-N 0.000 description 1
- 229920002134 Carboxymethyl cellulose Polymers 0.000 description 1
- 108010010803 Gelatin Proteins 0.000 description 1
- 229920000663 Hydroxyethyl cellulose Polymers 0.000 description 1
- 239000004354 Hydroxyethyl cellulose Substances 0.000 description 1
- 241000294754 Macroptilium atropurpureum Species 0.000 description 1
- 229920003171 Poly (ethylene oxide) Polymers 0.000 description 1
- 239000004698 Polyethylene Substances 0.000 description 1
- 229920000147 Styrene maleic anhydride Polymers 0.000 description 1
- 239000002174 Styrene-butadiene Substances 0.000 description 1
- 238000003848 UV Light-Curing Methods 0.000 description 1
- HEVGMYPGMWZOBU-UHFFFAOYSA-N [3-[(4-methylphenyl)sulfonylcarbamoylamino]phenyl] 4-methylbenzenesulfonate Chemical compound C1=CC(C)=CC=C1S(=O)(=O)NC(=O)NC1=CC=CC(OS(=O)(=O)C=2C=CC(C)=CC=2)=C1 HEVGMYPGMWZOBU-UHFFFAOYSA-N 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 229910052783 alkali metal Inorganic materials 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- 230000004888 barrier function Effects 0.000 description 1
- 239000000440 bentonite Substances 0.000 description 1
- 229910000278 bentonite Inorganic materials 0.000 description 1
- SVPXDRXYRYOSEX-UHFFFAOYSA-N bentoquatam Chemical compound O.O=[Si]=O.O=[Al]O[Al]=O SVPXDRXYRYOSEX-UHFFFAOYSA-N 0.000 description 1
- VCCBEIPGXKNHFW-UHFFFAOYSA-N biphenyl-4,4'-diol Chemical group C1=CC(O)=CC=C1C1=CC=C(O)C=C1 VCCBEIPGXKNHFW-UHFFFAOYSA-N 0.000 description 1
- MTAZNLWOLGHBHU-UHFFFAOYSA-N butadiene-styrene rubber Chemical compound C=CC=C.C=CC1=CC=CC=C1 MTAZNLWOLGHBHU-UHFFFAOYSA-N 0.000 description 1
- CJZGTCYPCWQAJB-UHFFFAOYSA-L calcium stearate Chemical compound [Ca+2].CCCCCCCCCCCCCCCCCC([O-])=O.CCCCCCCCCCCCCCCCCC([O-])=O CJZGTCYPCWQAJB-UHFFFAOYSA-L 0.000 description 1
- 239000008116 calcium stearate Substances 0.000 description 1
- 235000013539 calcium stearate Nutrition 0.000 description 1
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 1
- 239000001768 carboxy methyl cellulose Substances 0.000 description 1
- 235000010948 carboxy methyl cellulose Nutrition 0.000 description 1
- 239000008112 carboxymethyl-cellulose Substances 0.000 description 1
- 239000005018 casein Substances 0.000 description 1
- BECPQYXYKAMYBN-UHFFFAOYSA-N casein, tech. Chemical compound NCCCCC(C(O)=O)N=C(O)C(CC(O)=O)N=C(O)C(CCC(O)=N)N=C(O)C(CC(C)C)N=C(O)C(CCC(O)=O)N=C(O)C(CC(O)=O)N=C(O)C(CCC(O)=O)N=C(O)C(C(C)O)N=C(O)C(CCC(O)=N)N=C(O)C(CCC(O)=N)N=C(O)C(CCC(O)=N)N=C(O)C(CCC(O)=O)N=C(O)C(CCC(O)=O)N=C(O)C(COP(O)(O)=O)N=C(O)C(CCC(O)=N)N=C(O)C(N)CC1=CC=CC=C1 BECPQYXYKAMYBN-UHFFFAOYSA-N 0.000 description 1
- 235000021240 caseins Nutrition 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- SWXVUIWOUIDPGS-UHFFFAOYSA-N diacetone alcohol Chemical compound CC(=O)CC(C)(C)O SWXVUIWOUIDPGS-UHFFFAOYSA-N 0.000 description 1
- 235000014113 dietary fatty acids Nutrition 0.000 description 1
- 238000006073 displacement reaction Methods 0.000 description 1
- 238000007606 doctor blade method Methods 0.000 description 1
- 239000000194 fatty acid Substances 0.000 description 1
- 229930195729 fatty acid Natural products 0.000 description 1
- 150000004665 fatty acids Chemical class 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- 239000000945 filler Substances 0.000 description 1
- 229920000159 gelatin Polymers 0.000 description 1
- 239000008273 gelatin Substances 0.000 description 1
- 235000019322 gelatine Nutrition 0.000 description 1
- 235000011852 gelatine desserts Nutrition 0.000 description 1
- 235000019447 hydroxyethyl cellulose Nutrition 0.000 description 1
- 239000004615 ingredient Substances 0.000 description 1
- 239000000314 lubricant Substances 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 229920000609 methyl cellulose Polymers 0.000 description 1
- 239000001923 methylcellulose Substances 0.000 description 1
- 235000010981 methylcellulose Nutrition 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 229920005615 natural polymer Polymers 0.000 description 1
- 235000014593 oils and fats Nutrition 0.000 description 1
- 239000004014 plasticizer Substances 0.000 description 1
- 229920001495 poly(sodium acrylate) polymer Polymers 0.000 description 1
- 229920000573 polyethylene Polymers 0.000 description 1
- 229920000098 polyolefin Polymers 0.000 description 1
- 230000008092 positive effect Effects 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 230000004043 responsiveness Effects 0.000 description 1
- 238000007761 roller coating Methods 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- SCPYDCQAZCOKTP-UHFFFAOYSA-N silanol Chemical compound [SiH3]O SCPYDCQAZCOKTP-UHFFFAOYSA-N 0.000 description 1
- 229910052710 silicon Inorganic materials 0.000 description 1
- 239000010703 silicon Substances 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- 239000011115 styrene butadiene Substances 0.000 description 1
- 229920001059 synthetic polymer Polymers 0.000 description 1
- 239000000454 talc Substances 0.000 description 1
- 229910052623 talc Inorganic materials 0.000 description 1
- 229920001897 terpolymer Polymers 0.000 description 1
- 238000011144 upstream manufacturing Methods 0.000 description 1
- 239000003232 water-soluble binding agent Substances 0.000 description 1
- 239000001993 wax Substances 0.000 description 1
- XOOUIPVCVHRTMJ-UHFFFAOYSA-L zinc stearate Chemical compound [Zn+2].CCCCCCCCCCCCCCCCCC([O-])=O.CCCCCCCCCCCCCCCCCC([O-])=O XOOUIPVCVHRTMJ-UHFFFAOYSA-L 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
- B41M5/50—Recording sheets characterised by the coating used to improve ink, dye or pigment receptivity, e.g. for ink-jet or thermal dye transfer recording
- B41M5/502—Recording sheets characterised by the coating used to improve ink, dye or pigment receptivity, e.g. for ink-jet or thermal dye transfer recording characterised by structural details, e.g. multilayer materials
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B41—PRINTING; LINING MACHINES; TYPEWRITERS; STAMPS
- B41M—PRINTING, DUPLICATING, MARKING, OR COPYING PROCESSES; COLOUR PRINTING
- B41M2205/00—Printing methods or features related to printing methods; Location or type of the layers
- B41M2205/04—Direct thermal recording [DTR]
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B41—PRINTING; LINING MACHINES; TYPEWRITERS; STAMPS
- B41M—PRINTING, DUPLICATING, MARKING, OR COPYING PROCESSES; COLOUR PRINTING
- B41M2205/00—Printing methods or features related to printing methods; Location or type of the layers
- B41M2205/38—Intermediate layers; Layers between substrate and imaging layer
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B41—PRINTING; LINING MACHINES; TYPEWRITERS; STAMPS
- B41M—PRINTING, DUPLICATING, MARKING, OR COPYING PROCESSES; COLOUR PRINTING
- B41M2205/00—Printing methods or features related to printing methods; Location or type of the layers
- B41M2205/40—Cover layers; Layers separated from substrate by imaging layer; Protective layers; Layers applied before imaging
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B41—PRINTING; LINING MACHINES; TYPEWRITERS; STAMPS
- B41M—PRINTING, DUPLICATING, MARKING, OR COPYING PROCESSES; COLOUR PRINTING
- B41M2205/00—Printing methods or features related to printing methods; Location or type of the layers
- B41M2205/42—Multiple imaging layers
-
- 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
- B41M5/50—Recording sheets characterised by the coating used to improve ink, dye or pigment receptivity, e.g. for ink-jet or thermal dye transfer recording
- B41M5/52—Macromolecular coatings
- B41M5/5227—Macromolecular coatings characterised by organic non-macromolecular additives, e.g. UV-absorbers, plasticisers, surfactants
-
- 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
- B41M5/50—Recording sheets characterised by the coating used to improve ink, dye or pigment receptivity, e.g. for ink-jet or thermal dye transfer recording
- B41M5/52—Macromolecular coatings
- B41M5/5254—Macromolecular coatings characterised by the use of polymers obtained by reactions only involving carbon-to-carbon unsaturated bonds, e.g. vinyl polymers
Definitions
- the invention relates to a recording material suitable for offset printing even at higher printing speeds, which in particular does not have process as raw material cost intensive protective layers on at least one recording layer formed below.
- the present invention is directed to recording materials having at least one heat and / or pressure sensitive recording layer and / or having an ink jet receiving layer as the respective recording layer.
- the invention also aims to the same extent to a method for producing such a recording material, suitable for offset printing, even at higher printing speeds
- Recording materials especially heat-sensitive recording materials, which should be suitable for offset printing, even at higher printing speeds, usually have a heat-sensitive recording layer over the entire surface covering protective layer.
- Such a protective layer ensures on the one hand higher resistance to organic solvents, plasticizers, optionally photoinitiators, such as those used in printing with UV-curing printing inks, oils and fats: heat-sensitive recording materials with such protective layers are partially considered to be extremely well-tried and are subject to EP 1 333 991, EP 1 663 662 and also other patents in which the protective layer does not have to be a central subject of the inventive idea.
- the provision of chemical resistance to be emphasized by protective layers to be formed on a given heat- and / or pressure-sensitive recording layer is not the subject matter of the present invention. Such resistance may not be necessary or absent from the given recording layer in the recording materials used herein.
- the present invention now provides a first aspect of the task to provide the public with a suitable for offset printing with higher printing speeds recording material available, in which it depends on ensuring chemical resistance of a trainee protective layer less and yet on a convincing Layer seal as defined in the second bullet point of the previous paragraph.
- the new recording material should ideally and preferably have improved scratch resistance as a second task aspect.
- Such scratch resistance implies that mutual displacement of the recording material to be proposed here in the stack does not result in visible scratch marks on the surface of the recording material and / or visible color reaction in the heat and / or pressure sensitive recording layer of the recording material to be proposed here.
- the recording material to be proposed here has to be as particularly favorable in production as possible, in order to be still competitively priced with superior product characteristics in the current market situation.
- the inventors are interested in the fact that the recording material to be proposed should have a good stampability, which means for the purposes of the present invention that a stamp imprint, as it is preferably used for devaluation in public transport, after 10 seconds exposure time can not be wiped dry or damp without residue.
- a web-shaped substrate comprising a front side and a rear side opposite the front side
- the novel recording material is characterized in that the at least one coating layer covering the entire recording layer has a weight per unit area of between 0.05 and 0.8 g / m 2 .
- the flea even within a range of 0.08 and 0.5 g / m 2 or even more limited within a range of 0.15 and 0.35 g / m 2 .
- the coating composition for forming a coating layer covering the recording layer over the entire area and also the coating layer itself mainly comprises binders preferably selected from the list comprising ethylene-vinyl alcohol copolymer (EVOH), carboxyl group, silanol or diacetone -modified polyvinyl alcohol and unmodified polyvinyl alcohol, wherein the previously enumerated as preferred binder in a first particularly preferred embodiment alone, in a second particularly preferred embodiment in admixture with each other or in a third embodiment in admixture with other binders in the coating layer be involved should.
- binders preferably selected from the list comprising ethylene-vinyl alcohol copolymer (EVOH), carboxyl group, silanol or diacetone -modified polyvinyl alcohol and unmodified polyvinyl alcohol, wherein the previously enumerated as preferred binder in a first particularly preferred embodiment alone, in a second particularly preferred embodiment in admixture with each other or in a third embodiment in admixture
- binders a proportion of 50 wt .-% up to 100 wt .-%, most preferably a share of 75 wt .-% to 98 wt .-% , each based on the total weight of the coating composition to form a coating layer covering the recording layer over its entire area.
- the coating composition for forming a coating layer covering the recording layer over its entire area and also the coating layer itself preferably contains at least one crosslinking assistant selected from the list comprising: boric acid, polyamine, epoxy resin, dialdehyde, formaldehyde oligomers, epiochlorohydrin resin, adipic dihydrazide, dimethylurea, Melaminformaldehyde, wherein the above-enumerated crosslinking aids should preferably be included alone or in admixture with each other in the coating layer. Also, a mixture of enumerated crosslinking aids with other crosslinking aids not mentioned here is conceivable. In total, the crosslinking aids preferably constitute from 3% to 20% by weight, based on the total weight of the coating composition, of a coating layer which covers the entire surface of the recording layer.
- pigments in particular inorganic pigments
- the coating composition for forming a coating layer which covers the recording layer over its entire surface and likewise into the coating layer itself, but it represents a clearly favored embodiment if The coating layer remains pigment-free.
- possible further ingredients of the coating composition for forming a coating layer covering the recording layer over its entire area and also the coating layer itself are optical brighteners, optionally defoamers and flow improvers in the case of a possible application of the coating layer by means of a curtain coater.
- a coating layer as proposed in the previous paragraphs [0004] to [0008] is able to reduce the pick resistance of the proposed recording material on the side on which the coating layer is at least applied, with little or even justifiable economic outlay Increase manner and thus to improve the offset printability. At the same time, the scratch resistance of the proposed recording material is significantly improved on the side on which the coating layer is at least applied.
- the invention is directed to a recording material having at least one recording layer on at least one side of the substrate, the recording layer preferably being selected from the list heat-sensitive recording layer, pressure-sensitive recording layer, inkjet-receiving layer.
- ⁇ is used as at least one side provided with a polyolefin coating paper.
- the invention also relates to the same extent a method for producing a recording material for offset printing in all the embodiments and variants already proposed here.
- Such a method comprises at least the following method steps:
- the new method for producing a recording material for offset printing is characterized in that the at least one coating layer covering the recording layer over the entire area has a basis weight of between 0.05 and 0.8 g / m 2 , very particularly preferably between 0.15 and 0 , 35 g / m 2 .
- the proposed method initially provides for the formation of the web-like substrate, for example and in a preferred embodiment, on a paper machine in which a paper pulp of different pulps, optionally mechanical pulp, fillers and water is applied in at least one upstream mixing chest and where for this paper pulp prior to its feeding to the paper machine, further constituents, such as, for example, resin size for massaging, and other customary additives, such as pigments, shading dyes and / or optical brighteners, are preferably added.
- the proposed method further provides for preparing a coating composition for forming a recording layer on at least one side of the substrate, in which this recording layer is preferably selected from the list, comprising: heat-sensitive recording layer, pressure-sensitive recording layer, inkjet-receiving layer.
- the coating composition to be prepared for this purpose comprises at least one dye precursor and at least one color acceptor, wherein the dye precursor and color acceptor react color-forming with one another under the action of heat.
- At least one of the substances selected from the list is preferred, comprising: ⁇ 2,2 bis (4-hydroxyphenyl) -propane - also known as bisphenol A,
- N- (p-toluenesulphonyl) -N ' -3- (p-toluenesulphonyl-oxy-phenyl) urea is also known as Pergafast® 201 BASF Corporation and is representable as the following formula (1), wherein in some representations the CH3 groups are also omitted.
- 4,4'-dihydroxydiphenyl sulfone is also often referred to as 4,4'-sulfonyldiphenol and is also known under the trade name 4.4 bisphenol S.
- 4,4'-Dihydroxydiphenylsulfone has the chemical formula C12H10O4S and can be represented as the following formula (3):
- the coating composition for forming the heat-sensitive recording layer preferably comprises, as a dye precursor, those selected from the list, comprising:
- ODB-2 3-dibutylamino-6-methyl-7-anilinofluoran
- the coating composition for forming the heat-sensitive recording layer has more than one dye precursor, then preferably each selected from the dye precursors listed in the above paragraph.
- the coating composition for forming the heat-sensitive recording layer most preferably contains at least one sensitiser selected from the list, including stearic acid amide, dimethylsulfone and 2- (2H-benzotriazol-2-yl), with the aim of increasing thermal responsiveness.
- p-cresol which according to a first preferred embodiment alone, that is, not used in combination with another sensitizer, in particular not with such from the three mentioned sensitizers of the above list.
- two sensitizers selected from the list comprising stearic acid amide, dimethylsulfone and 2- (2H-benzotriazol-2-yl) -p-cresol, in the coating composition for forming the heat-sensitive Drawing layer integrated.
- dimethylsulfone is very particularly preferred.
- Suitable binders for incorporation into the coating composition for forming the heat-sensitive recording layer are, for example, water-soluble binders such as starch, hydroxyethyl cellulose, methyl cellulose, carboxymethyl cellulose, gelatin, casein, polyvinyl alcohols, modified polyvinyl alcohols, ethylene-vinyl alcohol copolymers, sodium polyacrylates, acrylamide acrylate Copolymers, acrylamide-acrylate-methacrylate terpolymers and alkali metal salts of styrene-maleic anhydride copolymer or ethylene-maleic anhydride copolymer, which binders may be used alone or in combination with one another; Water-insoluble latex binders such as styrene-butadiene copolymers, acrylonitrile-butadiene copolymers and methyl acrylate-butadiene copolymers are also suitable as binders for incorporation into the heat-sensitive recording layer.
- polyvinyl alcohol, ethylene-vinyl alcohol copolymers or polyvinyl alcohol in combination with ethylene-vinyl alcohol copolymers are particularly preferred binders which together in a range from 10 to 20% by weight, based on the total weight of the heat-sensitive recording layer. are incorporated in the heat-sensitive recording layer.
- the coating composition for forming the thermosensitive recording layer may further contain lubricants and release agents such as metal salts of higher fatty acids, for example, zinc stearate, calcium stearate and waxes such as for example, paraffin, oxidized paraffin, polyethylene, polyethylene oxide, stearamides and castor wax.
- Further constituents of the recording layer are, if appropriate, for example pigments, preferably inorganic pigments such as, for example, aluminum (hydr) oxide, silica and calcium carbonate.
- calcium carbonate which is preferably incorporated in an amount of 0 to 45 wt .-%, most preferably in an amount of 10 to 40 wt .-%, each based on the total weight of the recording layer in the recording layer , as preferred.
- the coating composition for forming the recording layer in particular selected from the list, comprising:
- the coating composition used to form the recording layer is preferably aqueous.
- the subsequent drying of the coating composition is usually done by a method in which heat is supplied, as is done by hot-air floating dryer or contact dryer. Proven is also a combination of the listed dry processes.
- the basis weight of the recording layer is preferably between 2 and 6 g / m 2 in the case of the recording material proposed here.
- the coating composition for forming a coating layer covering the recording layer over the entire area is most preferably applied by means of a coating unit selected from the list, comprising: roller coater, curtain coater (in the embodiment as slot coater or sliding surface coater) and air brush. Subsequently, this applied coating composition is crosslinked depending on the given component entry and / or dried by means of heat.
- a coating unit selected from the list, comprising: roller coater, curtain coater (in the embodiment as slot coater or sliding surface coater) and air brush.
- the proposed method preferably provides that
- the application of a prepared coating composition to form a coating layer covering the recording layer over its entire surface is carried out in the context of exactly one machine pass.
- This can be done in the context of a first preferred embodiment such that on a paper or coater first the coating composition for forming the recording layer is applied and dried and then the coating composition for forming those of the recording layer over the entire area covering coating layer is applied and dried.
- the coating composition for forming the recording layer and immediately thereafter the coating composition is applied first to form the coating layer which covers the recording layer over the entire area. The joint drying of the two applied layers follows it.
- the coating composition for forming the recording layer and the coating composition for forming the coating layer covering the recording layer over the entire area are co-applied, using a curtain coater in the form of a slip surface caster.
- the coating units preferably used for the formation of the pigmented intermediate layer are, in particular, leveling coating units selected from the list, comprising: roller coating, doctor blade or doctor blade coating unit.
- leveling coating units selected from the list, comprising: roller coating, doctor blade or doctor blade coating unit.
- Such a pigmented intermediate layer can have a positive effect. contribute to the leveling of the substrate surface, which reduces the amount of applied mass of a usually expensive coating composition for forming the recording layer.
- the subsequent drying of the coating composition to form the pigmented intermediate layer takes place again and here usually by a method in which heat is supplied, as is done by hot-air floating dryer or contact dryer. Proven is also a combination of the listed dry processes.
- For the basis weight of the pigmented intermediate layer a preferred range between 5 and 20 g / m 2 and even better between 7 and 12 g / m 2 has proven.
- This coating composition for forming the pigmented intermediate layer contains binders and preferably a mixture of organic pigments and inorganic pigments.
- the inorganic pigments are preferred, individually or in combination with one another, selected from the list, comprising: silicon (di) oxide, bentonite, talc, calcined kaolin, calcium carbonate and aluminum oxide and here especially boehmite.
- the above inorganic pigments, individually or in combination with one another, selected from the list above, are quoted as one of the list comprising: calcined kaolin, calcium carbonate and aluminum oxide, and here especially boehmite.
- the coating composition for forming the pigmented intermediate layer at least one binder preferably based on a synthetic polymer, for example, styrene-butadiene latex provides particularly good results.
- a synthetic binder with the admixture of at least one natural polymer, such as particularly preferred starch, represents a particularly suitable embodiment.
Landscapes
- Heat Sensitive Colour Forming Recording (AREA)
Abstract
Description
Claims
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
DE201110114129 DE102011114129A1 (en) | 2011-09-23 | 2011-09-23 | Recording material for offset printing |
PCT/EP2012/065775 WO2013041302A1 (en) | 2011-09-23 | 2012-08-12 | Recording material for offset printing |
Publications (2)
Publication Number | Publication Date |
---|---|
EP2758249A1 true EP2758249A1 (en) | 2014-07-30 |
EP2758249B1 EP2758249B1 (en) | 2016-04-13 |
Family
ID=46642556
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
EP12745873.5A Active EP2758249B1 (en) | 2011-09-23 | 2012-08-12 | Recording material for offset printing |
Country Status (3)
Country | Link |
---|---|
EP (1) | EP2758249B1 (en) |
DE (1) | DE102011114129A1 (en) |
WO (1) | WO2013041302A1 (en) |
Family Cites Families (4)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JP2000318319A (en) * | 1998-12-02 | 2000-11-21 | Mitsubishi Paper Mills Ltd | Information recording material |
DE10051294C1 (en) | 2000-10-16 | 2002-04-18 | Mitsubishi Hitec Paper Flensbu | Thermographic material useful for ticket, especially lottery ticket, has protective coating of water-insoluble, self-crosslinking acrylic polymer and crosslinker pigmented (mainly) with highly purified, alkali-treated bentonite |
DE10341168A1 (en) | 2003-09-06 | 2005-04-07 | Mitsubishi Hitec Paper Flensburg Gmbh | Heat-sensitive recording material and its use |
ATE458621T1 (en) * | 2007-09-10 | 2010-03-15 | Mitsubishi Hitec Paper Flensbu | HEAT SENSITIVE RECORDING MATERIAL |
-
2011
- 2011-09-23 DE DE201110114129 patent/DE102011114129A1/en not_active Withdrawn
-
2012
- 2012-08-12 WO PCT/EP2012/065775 patent/WO2013041302A1/en active Application Filing
- 2012-08-12 EP EP12745873.5A patent/EP2758249B1/en active Active
Non-Patent Citations (1)
Title |
---|
See references of WO2013041302A1 * |
Also Published As
Publication number | Publication date |
---|---|
DE102011114129A1 (en) | 2013-03-28 |
WO2013041302A1 (en) | 2013-03-28 |
EP2758249B1 (en) | 2016-04-13 |
Similar Documents
Publication | Publication Date | Title |
---|---|---|
EP2033799B1 (en) | Heat-sensitive recording material | |
EP2329959B1 (en) | Heat-sensitive recording material with barrier coating | |
EP2279877B1 (en) | Heat sensitive recording material | |
DE60222210T2 (en) | Heat-sensitive recording material | |
EP2033801B1 (en) | Heat sensitive recording material | |
WO2016016084A1 (en) | Heat-sensitive recording material with salicylic acid derivative as (colour) developer reactive with a dye precursor | |
EP2033802B1 (en) | Heat sensitive recording material with reverse coating | |
EP2329955B1 (en) | Heat-sensitive recording material with authenticity characteristic | |
EP2758249B1 (en) | Recording material for offset printing | |
EP2112000B1 (en) | Heat sensitive recording material | |
EP2765007B1 (en) | Heat-sensitive recording material | |
EP2487043B1 (en) | Method for producing a heat-sensitive recording material | |
EP2505374B1 (en) | Heat-sensitive recording material, method for its manufacture and application | |
EP1543984B1 (en) | Heat-sensitive recording material for double-sided printing | |
EP2329958B1 (en) | Heat sensitive recording material with reverse coating | |
EP2033800B1 (en) | Heat-sensitive recording material | |
DE102006050420B3 (en) | Heat-sensitive recording material, useful for printing tickets, has recording layer containing fluoran derivative color former and sulfonyl-urea and diphenyl sulfone derivative dye acceptors | |
EP2480415B1 (en) | Heat-sensitive recording material with reverse face coating | |
EP2636533B1 (en) | Method for producing a recording material with an authentication feature | |
EP2414173B1 (en) | Heat-sensitive recording material | |
DE102006056003A1 (en) | Heat-sensitive recording material with authentication feature |
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: 20140423 |
|
AK | Designated contracting states |
Kind code of ref document: A1 Designated state(s): AL AT BE BG CH CY CZ DE DK EE ES FI FR GB GR HR HU IE IS IT LI LT LU LV MC MK MT NL NO PL PT RO RS SE SI SK SM TR |
|
DAX | Request for extension of the european patent (deleted) | ||
GRAP | Despatch of communication of intention to grant a patent |
Free format text: ORIGINAL CODE: EPIDOSNIGR1 |
|
RIC1 | Information provided on ipc code assigned before grant |
Ipc: B41M 5/52 20060101ALN20151022BHEP Ipc: B41M 5/50 20060101AFI20151022BHEP |
|
INTG | Intention to grant announced |
Effective date: 20151113 |
|
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): AL AT BE BG CH CY CZ DE DK EE ES FI FR GB GR HR HU IE IS IT LI LT LU LV MC MK MT NL NO PL PT RO RS SE SI SK SM 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: AT Ref legal event code: REF Ref document number: 789690 Country of ref document: AT Kind code of ref document: T Effective date: 20160415 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 |
|
REG | Reference to a national code |
Ref country code: DE Ref legal event code: R096 Ref document number: 502012006729 Country of ref document: DE |
|
REG | Reference to a national code |
Ref country code: ES Ref legal event code: FG2A Ref document number: 2577778 Country of ref document: ES Kind code of ref document: T3 Effective date: 20160718 |
|
REG | Reference to a national code |
Ref country code: LT Ref legal event code: MG4D |
|
REG | Reference to a national code |
Ref country code: FR Ref legal event code: PLFP Year of fee payment: 5 |
|
REG | Reference to a national code |
Ref country code: NL Ref legal event code: MP Effective date: 20160413 |
|
PG25 | Lapsed in a contracting state [announced via postgrant information from national office to epo] |
Ref country code: PL 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: 20160413 Ref country code: NO 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: 20160713 Ref country code: LT 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: 20160413 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: 20160413 |
|
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: 20160816 Ref country code: HR 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: 20160413 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: 20160413 Ref country code: RS 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: 20160413 Ref country code: LV 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: 20160413 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: 20160714 |
|
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: 20160831 Ref country code: IT 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: 20160413 |
|
REG | Reference to a national code |
Ref country code: DE Ref legal event code: R097 Ref document number: 502012006729 Country of ref document: DE |
|
PG25 | Lapsed in a contracting state [announced via postgrant information from national office to epo] |
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: 20160413 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: 20160413 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: 20160413 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: 20160413 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: 20160413 |
|
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: SM 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: 20160413 |
|
26N | No opposition filed |
Effective date: 20170116 |
|
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 FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT Effective date: 20160413 |
|
REG | Reference to a national code |
Ref country code: CH Ref legal event code: PL |
|
GBPC | Gb: european patent ceased through non-payment of renewal fee |
Effective date: 20160812 |
|
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: 20160831 Ref country code: LI Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES Effective date: 20160831 |
|
PG25 | Lapsed in a contracting state [announced via postgrant information from national office to epo] |
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: 20160413 |
|
REG | Reference to a national code |
Ref country code: IE Ref legal event code: MM4A |
|
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: 20160812 Ref country code: IE Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES Effective date: 20160812 |
|
REG | Reference to a national code |
Ref country code: FR Ref legal event code: PLFP Year of fee payment: 6 |
|
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: 20160812 |
|
REG | Reference to a national code |
Ref country code: DE Ref legal event code: R082 Ref document number: 502012006729 Country of ref document: DE |
|
PG25 | Lapsed in a contracting state [announced via postgrant information from national office to epo] |
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; INVALID AB INITIO Effective date: 20120812 |
|
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: 20160413 Ref country code: MK 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: 20160413 Ref country code: IS 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: 20160413 Ref country code: MT 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: 20160413 |
|
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: 20160413 |
|
REG | Reference to a national code |
Ref country code: FR Ref legal event code: PLFP Year of fee payment: 7 |
|
REG | Reference to a national code |
Ref country code: AT Ref legal event code: MM01 Ref document number: 789690 Country of ref document: AT Kind code of ref document: T Effective date: 20170812 |
|
PG25 | Lapsed in a contracting state [announced via postgrant information from national office to epo] |
Ref country code: AL 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: 20160413 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: 20160413 |
|
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: 20170812 |
|
PGFP | Annual fee paid to national office [announced via postgrant information from national office to epo] |
Ref country code: FI Payment date: 20230824 Year of fee payment: 12 Ref country code: ES Payment date: 20230901 Year of fee payment: 12 |
|
PGFP | Annual fee paid to national office [announced via postgrant information from national office to epo] |
Ref country code: FR Payment date: 20230824 Year of fee payment: 12 Ref country code: DE Payment date: 20230831 Year of fee payment: 12 |