EP0509302A1 - Procédé pour le transfert de colorants méthiniques - Google Patents
Procédé pour le transfert de colorants méthiniques Download PDFInfo
- Publication number
- EP0509302A1 EP0509302A1 EP92105403A EP92105403A EP0509302A1 EP 0509302 A1 EP0509302 A1 EP 0509302A1 EP 92105403 A EP92105403 A EP 92105403A EP 92105403 A EP92105403 A EP 92105403A EP 0509302 A1 EP0509302 A1 EP 0509302A1
- Authority
- EP
- European Patent Office
- Prior art keywords
- alkyl
- alkoxy
- phenyl
- dyes
- formula
- 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
- 239000000975 dye Substances 0.000 title claims abstract description 57
- 238000000034 method Methods 0.000 title claims abstract description 18
- 238000012546 transfer Methods 0.000 title claims abstract description 18
- 125000001434 methanylylidene group Chemical group [H]C#[*] 0.000 title claims abstract description 8
- 238000009792 diffusion process Methods 0.000 claims abstract 2
- -1 phenylcarbamoyl Chemical group 0.000 claims description 94
- 125000004178 (C1-C4) alkyl group Chemical group 0.000 claims description 35
- 125000000229 (C1-C4)alkoxy group Chemical group 0.000 claims description 28
- 229910052736 halogen Chemical group 0.000 claims description 19
- 150000002367 halogens Chemical group 0.000 claims description 18
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims description 18
- 150000002431 hydrogen Chemical group 0.000 claims description 12
- 239000001257 hydrogen Substances 0.000 claims description 12
- 229910052739 hydrogen Inorganic materials 0.000 claims description 12
- 125000004430 oxygen atom Chemical group O* 0.000 claims description 10
- 125000004209 (C1-C8) alkyl group Chemical group 0.000 claims description 9
- 125000001033 ether group Chemical group 0.000 claims description 9
- 125000003944 tolyl group Chemical group 0.000 claims description 8
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims description 7
- 125000004174 2-benzimidazolyl group Chemical group [H]N1C(*)=NC2=C([H])C([H])=C([H])C([H])=C12 0.000 claims description 6
- 125000001797 benzyl group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C([H])([H])* 0.000 claims description 6
- 125000004093 cyano group Chemical group *C#N 0.000 claims description 6
- 125000005117 dialkylcarbamoyl group Chemical group 0.000 claims description 6
- 125000000956 methoxy group Chemical group [H]C([H])([H])O* 0.000 claims description 6
- 125000004454 (C1-C6) alkoxycarbonyl group Chemical group 0.000 claims description 5
- 125000000449 nitro group Chemical group [O-][N+](*)=O 0.000 claims description 5
- 125000003236 benzoyl group Chemical class [H]C1=C([H])C([H])=C(C([H])=C1[H])C(*)=O 0.000 claims description 4
- 150000001875 compounds Chemical class 0.000 claims description 4
- 125000000113 cyclohexyl group Chemical group [H]C1([H])C([H])([H])C([H])([H])C([H])(*)C([H])([H])C1([H])[H] 0.000 claims description 4
- 125000002861 (C1-C4) alkanoyl group Chemical group 0.000 claims description 3
- 125000004769 (C1-C4) alkylsulfonyl group Chemical class 0.000 claims description 3
- 125000004760 (C1-C4) alkylsulfonylamino group Chemical group 0.000 claims description 3
- 125000004169 (C1-C6) alkyl group Chemical group 0.000 claims description 3
- 125000003917 carbamoyl group Chemical group [H]N([H])C(*)=O 0.000 claims description 3
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 claims description 3
- 125000001301 ethoxy group Chemical group [H]C([H])([H])C([H])([H])O* 0.000 claims description 3
- MCSAJNNLRCFZED-UHFFFAOYSA-N nitroethane Chemical compound CC[N+]([O-])=O MCSAJNNLRCFZED-UHFFFAOYSA-N 0.000 claims description 3
- LYGJENNIWJXYER-UHFFFAOYSA-N nitromethane Chemical compound C[N+]([O-])=O LYGJENNIWJXYER-UHFFFAOYSA-N 0.000 claims description 3
- 125000006678 phenoxycarbonyl group Chemical group 0.000 claims description 3
- 125000003170 phenylsulfonyl group Chemical group C1(=CC=CC=C1)S(=O)(=O)* 0.000 claims description 3
- 239000004033 plastic Substances 0.000 claims description 3
- 229920003023 plastic Polymers 0.000 claims description 3
- 125000001544 thienyl group Chemical group 0.000 claims description 3
- 125000004453 alkoxycarbonyl group Chemical group 0.000 claims description 2
- STRDCKXOEFPOCT-UHFFFAOYSA-N 2-(1h-benzimidazol-2-yl)acetamide Chemical compound C1=CC=C2NC(CC(=O)N)=NC2=C1 STRDCKXOEFPOCT-UHFFFAOYSA-N 0.000 claims 1
- 125000004356 hydroxy functional group Chemical group O* 0.000 claims 1
- 239000011092 plastic-coated paper Substances 0.000 abstract description 3
- 239000011230 binding agent Substances 0.000 description 9
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 8
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 6
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 6
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 6
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 6
- 238000010521 absorption reaction Methods 0.000 description 5
- 239000011248 coating agent Substances 0.000 description 4
- 238000000576 coating method Methods 0.000 description 4
- 239000000203 mixture Substances 0.000 description 4
- 238000007639 printing Methods 0.000 description 4
- 150000003254 radicals Chemical class 0.000 description 4
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 description 3
- 230000008033 biological extinction Effects 0.000 description 3
- 238000010438 heat treatment Methods 0.000 description 3
- 238000013508 migration Methods 0.000 description 3
- 230000005012 migration Effects 0.000 description 3
- 239000003960 organic solvent Substances 0.000 description 3
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 3
- PAYRUJLWNCNPSJ-UHFFFAOYSA-N Aniline Chemical compound NC1=CC=CC=C1 PAYRUJLWNCNPSJ-UHFFFAOYSA-N 0.000 description 2
- 241001295925 Gegenes Species 0.000 description 2
- SIKJAQJRHWYJAI-UHFFFAOYSA-N Indole Chemical compound C1=CC=C2NC=CC2=C1 SIKJAQJRHWYJAI-UHFFFAOYSA-N 0.000 description 2
- SMWDFEZZVXVKRB-UHFFFAOYSA-N Quinoline Chemical compound N1=CC=CC2=CC=CC=C21 SMWDFEZZVXVKRB-UHFFFAOYSA-N 0.000 description 2
- 230000005540 biological transmission Effects 0.000 description 2
- 239000000969 carrier Substances 0.000 description 2
- MVPPADPHJFYWMZ-UHFFFAOYSA-N chlorobenzene Chemical compound ClC1=CC=CC=C1 MVPPADPHJFYWMZ-UHFFFAOYSA-N 0.000 description 2
- HVYWMOMLDIMFJA-DPAQBDIFSA-N cholesterol Chemical compound C1C=C2C[C@@H](O)CC[C@]2(C)[C@@H]2[C@@H]1[C@@H]1CC[C@H]([C@H](C)CCCC(C)C)[C@@]1(C)CC2 HVYWMOMLDIMFJA-DPAQBDIFSA-N 0.000 description 2
- JHIVVAPYMSGYDF-UHFFFAOYSA-N cyclohexanone Chemical compound O=C1CCCCC1 JHIVVAPYMSGYDF-UHFFFAOYSA-N 0.000 description 2
- BGTOWKSIORTVQH-UHFFFAOYSA-N cyclopentanone Chemical compound O=C1CCCC1 BGTOWKSIORTVQH-UHFFFAOYSA-N 0.000 description 2
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 2
- ZXEKIIBDNHEJCQ-UHFFFAOYSA-N isobutanol Chemical compound CC(C)CO ZXEKIIBDNHEJCQ-UHFFFAOYSA-N 0.000 description 2
- 229920000728 polyester Polymers 0.000 description 2
- 229920006267 polyester film Polymers 0.000 description 2
- 239000000243 solution Substances 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 125000000547 substituted alkyl group Chemical group 0.000 description 2
- 238000010023 transfer printing Methods 0.000 description 2
- RAIPHJJURHTUIC-UHFFFAOYSA-N 1,3-thiazol-2-amine Chemical compound NC1=NC=CS1 RAIPHJJURHTUIC-UHFFFAOYSA-N 0.000 description 1
- RUFPHBVGCFYCNW-UHFFFAOYSA-N 1-naphthylamine Chemical compound C1=CC=C2C(N)=CC=CC2=C1 RUFPHBVGCFYCNW-UHFFFAOYSA-N 0.000 description 1
- 125000004343 1-phenylethyl group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C([H])(*)C([H])([H])[H] 0.000 description 1
- HYZJCKYKOHLVJF-UHFFFAOYSA-N 1H-benzimidazole Chemical compound C1=CC=C2NC=NC2=C1 HYZJCKYKOHLVJF-UHFFFAOYSA-N 0.000 description 1
- PXNJGLAVKOXITN-UHFFFAOYSA-N 2-(4-nitrophenyl)acetonitrile Chemical compound [O-][N+](=O)C1=CC=C(CC#N)C=C1 PXNJGLAVKOXITN-UHFFFAOYSA-N 0.000 description 1
- 125000003541 2-chlorobenzoyl group Chemical group ClC1=C(C(=O)*)C=CC=C1 0.000 description 1
- 125000004182 2-chlorophenyl group Chemical group [H]C1=C([H])C(Cl)=C(*)C([H])=C1[H] 0.000 description 1
- 125000001731 2-cyanoethyl group Chemical group [H]C([H])(*)C([H])([H])C#N 0.000 description 1
- 125000004200 2-methoxyethyl group Chemical group [H]C([H])([H])OC([H])([H])C([H])([H])* 0.000 description 1
- 125000004204 2-methoxyphenyl group Chemical group [H]C1=C([H])C(*)=C(OC([H])([H])[H])C([H])=C1[H] 0.000 description 1
- 125000006179 2-methyl benzyl group Chemical group [H]C1=C([H])C(=C(C([H])=C1[H])C([H])([H])*)C([H])([H])[H] 0.000 description 1
- 125000005916 2-methylpentyl group Chemical group 0.000 description 1
- 125000000094 2-phenylethyl group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C([H])([H])C([H])([H])* 0.000 description 1
- CMLFRMDBDNHMRA-UHFFFAOYSA-N 2h-1,2-benzoxazine Chemical compound C1=CC=C2C=CNOC2=C1 CMLFRMDBDNHMRA-UHFFFAOYSA-N 0.000 description 1
- 125000004179 3-chlorophenyl group Chemical group [H]C1=C([H])C(*)=C([H])C(Cl)=C1[H] 0.000 description 1
- 125000004801 4-cyanophenyl group Chemical group [H]C1=C([H])C(C#N)=C([H])C([H])=C1* 0.000 description 1
- 125000004172 4-methoxyphenyl group Chemical group [H]C1=C([H])C(OC([H])([H])[H])=C([H])C([H])=C1* 0.000 description 1
- 125000006418 4-methylphenylsulfonyl group Chemical group 0.000 description 1
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical compound [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 description 1
- FERIUCNNQQJTOY-UHFFFAOYSA-M Butyrate Chemical compound CCCC([O-])=O FERIUCNNQQJTOY-UHFFFAOYSA-M 0.000 description 1
- FERIUCNNQQJTOY-UHFFFAOYSA-N Butyric acid Natural products CCCC(O)=O FERIUCNNQQJTOY-UHFFFAOYSA-N 0.000 description 1
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 1
- 229920000896 Ethulose Polymers 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
- 239000001859 Ethyl hydroxyethyl cellulose Substances 0.000 description 1
- PXGOKWXKJXAPGV-UHFFFAOYSA-N Fluorine Chemical compound FF PXGOKWXKJXAPGV-UHFFFAOYSA-N 0.000 description 1
- 238000005299 abrasion Methods 0.000 description 1
- 125000002777 acetyl group Chemical group [H]C([H])([H])C(*)=O 0.000 description 1
- 230000004913 activation Effects 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 125000003545 alkoxy group Chemical group 0.000 description 1
- 125000000217 alkyl group Chemical group 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- 125000003277 amino group Chemical group 0.000 description 1
- 229950003476 aminothiazole Drugs 0.000 description 1
- 150000001448 anilines Chemical class 0.000 description 1
- IOJUPLGTWVMSFF-UHFFFAOYSA-N benzothiazole Chemical class C1=CC=C2SC=NC2=C1 IOJUPLGTWVMSFF-UHFFFAOYSA-N 0.000 description 1
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Substances BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 description 1
- 229910052794 bromium Inorganic materials 0.000 description 1
- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 125000004744 butyloxycarbonyl group Chemical group 0.000 description 1
- 125000004063 butyryl group Chemical group O=C([*])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 238000012512 characterization method Methods 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 229910052801 chlorine Inorganic materials 0.000 description 1
- 239000000460 chlorine Substances 0.000 description 1
- 235000012000 cholesterol Nutrition 0.000 description 1
- 239000008199 coating composition Substances 0.000 description 1
- 239000003086 colorant Substances 0.000 description 1
- 238000002425 crystallisation Methods 0.000 description 1
- 230000008025 crystallization Effects 0.000 description 1
- 125000000582 cycloheptyl group Chemical group [H]C1([H])C([H])([H])C([H])([H])C([H])([H])C([H])(*)C([H])([H])C1([H])[H] 0.000 description 1
- 125000001511 cyclopentyl group Chemical group [H]C1([H])C([H])([H])C([H])([H])C([H])(*)C1([H])[H] 0.000 description 1
- 238000004043 dyeing Methods 0.000 description 1
- 125000003754 ethoxycarbonyl group Chemical group C(=O)(OCC)* 0.000 description 1
- 229920001249 ethyl cellulose Polymers 0.000 description 1
- 235000019325 ethyl cellulose Nutrition 0.000 description 1
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 1
- 235000019326 ethyl hydroxyethyl cellulose Nutrition 0.000 description 1
- 125000006125 ethylsulfonyl group Chemical group 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- 229910052731 fluorine Inorganic materials 0.000 description 1
- 239000011737 fluorine Substances 0.000 description 1
- 239000011888 foil Substances 0.000 description 1
- 125000002485 formyl group Chemical group [H]C(*)=O 0.000 description 1
- 125000003187 heptyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 125000004051 hexyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 125000005935 hexyloxycarbonyl group Chemical group 0.000 description 1
- PZOUSPYUWWUPPK-UHFFFAOYSA-N indole Natural products CC1=CC=CC2=C1C=CN2 PZOUSPYUWWUPPK-UHFFFAOYSA-N 0.000 description 1
- RKJUIXBNRJVNHR-UHFFFAOYSA-N indolenine Natural products C1=CC=C2CC=NC2=C1 RKJUIXBNRJVNHR-UHFFFAOYSA-N 0.000 description 1
- 229910052740 iodine Inorganic materials 0.000 description 1
- 125000000959 isobutyl group Chemical group [H]C([H])([H])C([H])(C([H])([H])[H])C([H])([H])* 0.000 description 1
- 125000001972 isopentyl group Chemical group [H]C([H])([H])C([H])(C([H])([H])[H])C([H])([H])C([H])([H])* 0.000 description 1
- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 1
- 125000005928 isopropyloxycarbonyl group Chemical group [H]C([H])([H])C([H])(OC(*)=O)C([H])([H])[H] 0.000 description 1
- 125000000040 m-tolyl group Chemical group [H]C1=C([H])C(*)=C([H])C(=C1[H])C([H])([H])[H] 0.000 description 1
- 125000001160 methoxycarbonyl group Chemical group [H]C([H])([H])OC(*)=O 0.000 description 1
- JIQNWFBLYKVZFY-UHFFFAOYSA-N methoxycyclohexatriene Chemical compound COC1=C[C]=CC=C1 JIQNWFBLYKVZFY-UHFFFAOYSA-N 0.000 description 1
- 125000004170 methylsulfonyl group Chemical group [H]C([H])([H])S(*)(=O)=O 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 125000001971 neopentyl group Chemical group [H]C([*])([H])C(C([H])([H])[H])(C([H])([H])[H])C([H])([H])[H] 0.000 description 1
- 230000007935 neutral effect Effects 0.000 description 1
- 125000003261 o-tolyl group Chemical group [H]C1=C([H])C(*)=C(C([H])=C1[H])C([H])([H])[H] 0.000 description 1
- 125000002347 octyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 230000003287 optical effect Effects 0.000 description 1
- 125000003854 p-chlorophenyl group Chemical group [H]C1=C([H])C(*)=C([H])C([H])=C1Cl 0.000 description 1
- 125000000636 p-nitrophenyl group Chemical group [H]C1=C([H])C(=C([H])C([H])=C1*)[N+]([O-])=O 0.000 description 1
- 125000001037 p-tolyl group Chemical group [H]C1=C([H])C(=C([H])C([H])=C1*)C([H])([H])[H] 0.000 description 1
- 125000001147 pentyl group Chemical group C(CCCC)* 0.000 description 1
- 125000001148 pentyloxycarbonyl group Chemical group 0.000 description 1
- 229920000515 polycarbonate Polymers 0.000 description 1
- 239000004417 polycarbonate Substances 0.000 description 1
- 239000002861 polymer material Substances 0.000 description 1
- 229920002689 polyvinyl acetate Polymers 0.000 description 1
- 239000011118 polyvinyl acetate Substances 0.000 description 1
- BDERNNFJNOPAEC-UHFFFAOYSA-N propan-1-ol Chemical compound CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 description 1
- 125000001501 propionyl group Chemical group O=C([*])C([H])([H])C([H])([H])[H] 0.000 description 1
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 125000004742 propyloxycarbonyl group Chemical group 0.000 description 1
- ZZYXNRREDYWPLN-UHFFFAOYSA-N pyridine-2,3-diamine Chemical compound NC1=CC=CN=C1N ZZYXNRREDYWPLN-UHFFFAOYSA-N 0.000 description 1
- 229920005989 resin Polymers 0.000 description 1
- 239000011347 resin Substances 0.000 description 1
- 229920006395 saturated elastomer Polymers 0.000 description 1
- 125000002914 sec-butyl group Chemical group [H]C([H])([H])C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 230000003595 spectral effect Effects 0.000 description 1
- 125000001424 substituent group Chemical group 0.000 description 1
- 125000001973 tert-pentyl group Chemical group [H]C([H])([H])C([H])([H])C(*)(C([H])([H])[H])C([H])([H])[H] 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- GLQWRXYOTXRDNH-UHFFFAOYSA-N thiophen-2-amine Chemical compound NC1=CC=CS1 GLQWRXYOTXRDNH-UHFFFAOYSA-N 0.000 description 1
- MWOOGOJBHIARFG-UHFFFAOYSA-N vanillin Chemical compound COC1=CC(C=O)=CC=C1O MWOOGOJBHIARFG-UHFFFAOYSA-N 0.000 description 1
- FGQOOHJZONJGDT-UHFFFAOYSA-N vanillin Natural products COC1=CC(O)=CC(C=O)=C1 FGQOOHJZONJGDT-UHFFFAOYSA-N 0.000 description 1
- 235000012141 vanillin Nutrition 0.000 description 1
- 229920002554 vinyl polymer Polymers 0.000 description 1
- 239000001043 yellow dye Substances 0.000 description 1
Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B41—PRINTING; LINING MACHINES; TYPEWRITERS; STAMPS
- B41M—PRINTING, DUPLICATING, MARKING, OR COPYING PROCESSES; COLOUR PRINTING
- B41M5/00—Duplicating or marking methods; Sheet materials for use therein
- B41M5/26—Thermography ; Marking by high energetic means, e.g. laser otherwise than by burning, and characterised by the material used
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B41—PRINTING; LINING MACHINES; TYPEWRITERS; STAMPS
- B41M—PRINTING, DUPLICATING, MARKING, OR COPYING PROCESSES; COLOUR PRINTING
- B41M5/00—Duplicating or marking methods; Sheet materials for use therein
- B41M5/26—Thermography ; Marking by high energetic means, e.g. laser otherwise than by burning, and characterised by the material used
- B41M5/382—Contact thermal transfer or sublimation processes
- B41M5/385—Contact thermal transfer or sublimation processes characterised by the transferable dyes or pigments
- B41M5/39—Dyes containing one or more carbon-to-nitrogen double bonds, e.g. azomethine
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
- Y10S—TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10S428/00—Stock material or miscellaneous articles
- Y10S428/913—Material designed to be responsive to temperature, light, moisture
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
- Y10S—TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10S428/00—Stock material or miscellaneous articles
- Y10S428/914—Transfer or decalcomania
Definitions
- the present invention relates to a new method for transferring methine dyes from a support to a plastic-coated paper using an energy source.
- a transfer sheet containing a thermally transferable dye in one or more binders, optionally together with suitable auxiliaries is supported on a support with an energy source, e.g. with a heating head or a laser, heated by short heating impulses (duration: fractions of a second) from the back, whereby the dye migrates from the transfer sheet and diffuses into the surface coating of a recording medium.
- an energy source e.g. with a heating head or a laser
- short heating impulses duration: fractions of a second
- the color recording is carried out using the three subtractive primary colors yellow, magenta, cyan (and possibly black).
- JP-A-229 786/1985, JP-A-84 390/1990 and EP-A-258 856 describe aniline derivatives for this purpose which have the tricyanovinyl radical in the para position to the amino group.
- JP-A-32 164/1990 describes dyes which have 4-nitrophenylacetonitrile as a CH-acidic component.
- the object of the present invention was therefore to provide a new method for the transmission of methine dyes with absorption in the blue-green or green spectral range, the dyes used having the properties mentioned at the outset.
- Aromatic carbocyclic or heterocyclic radicals K are derived, for example, from the aniline, aminonaphthalene, indole, quinoline, benzoxazine, aminothiazole, diaminopyridine, aminothiophene, benzimidazole or benzothiazole series.
- substituted alkyl or phenyl groups occur in the formulas mentioned above, these are generally mono- to trisubstituted.
- the substituents e.g. Cyano, phenyl, tolyl, C1-C6-alkanoyloxy, C1-C4-alkoxycarbonyl or C1-C4-alkoxycarbonyloxy, in which case the alkoxy group can be substituted by phenyl, tolyl or C1-C4-alkoxy.
- Suitable radicals X2, X4, X5, R3, R4, R6 and R8 are e.g. Methyl, ethyl, propyl, isopropyl, butyl, isobutyl or sec-butyl.
- R3, R4 and R6 are also e.g. Pentyl, isopentyl, neopentyl, tert-pentyl, hexyl or 2-methylpentyl.
- R3 and R4 are further examples of heptyl, octyl, 2-ethylhexyl, 2-methoxyethyl, 2- or 3-methoxypropyl, 2-ethoxyethyl, 2- or 3-ethoxypropyl, 2-propoxyethyl, 2- or 3-propoxypropyl, 2- Butoxyethyl, 2- or 3-butoxypropyl, 3,6-dioxaheptyl, 3,6-dioxaoctyl, 2-cyanoethyl, 2- or 3-cyanopropyl, 2-acetyloxyethyl, 2- or 3-acetyloxypropyl, 2-isobutyryloxyethyl, 2- or 2-isobutyryloxypropyl, 2-methoxycarbonylethyl, 2- or 3-methoxycarbonylpropyl, 2-ethoxycarbonylethyl, 2- or 3-ethoxycarbonylpropyl 2-methoxycarbonylpropyl,
- Residues X2 and R8 are further e.g. Methoxy, ethoxy, propoxy, iospropoxy, butoxy, sec-butoxy, methylthio, ethylthio, propylthio, isopropylthio or butylthio.
- Residues R8 are still e.g. Fluorine, chlorine or bromine.
- R1 are e.g. Methylsulfonylamino, ethylsulfonylamino, propylsulfonylamino, isopropylsulfonylamino, butylsulfonylamino, mono- or dimethylaminosulfonylamino, mono- or diethylaminosulfonylamino, mono- or dipropylaminosulfonylamino, mono- or diisopropylaminosulfonylamino-nylamino or n-aminobutylamino-sulfonylamino-methyl-n-aminosulfonylamino-nyl-aminosulfonylamino-naphonamino-n-aminosulfonylamino-n-aminosulfonylamino-n-aminosulfonylamino-naphonamino-n-aminosulfony
- X1, X3 and R7 are e.g. Methoxycarbonyl, ethoxycarbonyl, propoxycarbonyl, isopropoxycarbonyl or butoxycarbonyl.
- X1 and R7 are further e.g. Pentyloxycarbonyl, hexyloxycarbonyl, mono- or dimethylcarbamoyl, mono- or diethylcarbamoyl, mono- or dipropylcarbamoyl, mono- or diisopropylcarbamoyl, mono- or dibutylcarbamoyl or N-methyl-N-ethylcarbamoyl.
- Residues X1 are furthermore, for example, 2-methoxyethoxycarbonyl, 2-ethoxyethoxycarbonyl, 3,6-dioxaheptyloxycarbonyl, cyclopentyloxycarbonyl, cyclohexyloxycarbonyl, cycloheptyloxycarbonyl, formyl, acetyl, propionyl, butyryl, isobutyryl, benzoyl, 2-methylbenzoyloxy, 2,4-dimethylbenzoyloyl, 2,4-dimethylbenzoyloxy , 2,4-dimethoxybenzoyl, 2-chlorobenzoyl, 2,4-dichlorobenzoyl, methylsulfonyl, ethylsulfonyl, propylsulfonyl, isopropylsulfonyl, butylsulfonyl, phenylsulfonyl, 2- or 4-
- a process is particularly preferred in which there are one or more dyes of the formula I on the support, in which B represents the residue of a CH-acidic compound which is derived from a compound of the formula IIa or IIb.
- the methine dyes of the formula I can be prepared by methods known per se, as described, for example, in JP-A-32 164/1990, in the earlier application EP-A-416 434 or in the earlier German patent application P 41 05 197.1 will.
- the dyes of the formula I which are transferred in the process according to the invention are generally distinguished by improved migration properties in the recording medium at room temperature, easier thermal transferability, higher thermal and photochemical stability, easier technical accessibility, better resistance to moisture and chemical substances, higher color strength, better solubility or better suitability for the subtractive color mixture (higher color purity, less blue absorption, more favorable form of the absorption band, eg small half-width or greater edge steepness on the short-wave side). They are also particularly advantageous for dye mixtures with red or reddish-violet dyes.
- Such dyes are for example from EP-A-216 483, EP-A-209 990, EP-A-312 211, US-A-4 698 651, EP-A-346 729 or the earlier applications EP-A-416 434, EP-A-441 208 or EP-A-460 463.
- the dyes of the formula I in combination with violet dyes, produce highly brilliant magenta stains and, in combination with cyan dyes, highly brilliant, reddish blue stains. At the same time, a deep, neutral black is achieved in combination with suitable yellow dyes.
- the dyes are processed into a printing ink in a suitable organic solvent or in mixtures of solvents with one or more binders, if appropriate with the addition of auxiliaries.
- a printing ink in a suitable organic solvent or in mixtures of solvents with one or more binders, if appropriate with the addition of auxiliaries.
- the printing ink can be applied to the inert support using a doctor blade and the dyeing can be dried in air.
- Suitable organic solvents for the dyes I are e.g. those in which the solubility of the dyes I at room temperature is greater than 1% by weight, preferably greater than 5% by weight.
- Examples include ethanol, propanol, isobutanol, tetrahydrofuran, methylene chloride, methyl ethyl ketone, cyclopentanone, cyclohexanone, toluene, chlorobenzene or mixtures thereof.
- binders All resins or polymer materials which are soluble in organic solvents and are capable of binding the dye to the inert support in an abrasion-resistant manner are suitable as binders. Preference is given to those binders which, after the printing ink has dried in air, absorb the dye in the form of a clear, transparent film without any visible crystallization of the dye occurring.
- Preferred binders are ethyl cellulose, ethyl hydroxyethyl cellulose, polyvinyl butyrate, polyvinyl acetate or saturated linear polyesters.
- the weight ratio of binder: dye is generally 1: 1 to 5: 1.
- auxiliaries are release agents, such as those mentioned in the earlier application EP-A-441 282 or the corresponding patent applications cited therein. They are also particularly organic To name additives which prevent the transfer dyes from crystallizing out during storage or when the ribbon is heated, for example cholesterol or vanillin.
- Suitable inert carriers are e.g. described in the earlier application EP-A-441 282 or in the corresponding patent applications cited therein.
- the thickness of the dye carrier is generally 3 to 30 microns, preferably 5 to 10 microns.
- all temperature-stable plastic layers with affinity for the dyes to be transferred can be used as the dye-receiving layer, e.g. modified polycarbonates or polyester. Further details can e.g. from the earlier application EP-A-441 282 or the corresponding patent applications cited therein.
- the transmission takes place by means of an energy source, e.g. by means of a laser or by means of a thermal head, which must be able to be heated to a temperature of ⁇ 300 ° C. so that the dye transfer can take place in the time range t: 0 ⁇ t ⁇ 15 msec.
- the dye migrates from the transfer sheet and diffuses into the surface coating of the recording medium.
- the dyes listed in the following table were processed according to ⁇ ) and the resulting, dye-coated supports were tested for transfer behavior according to ⁇ ).
- the table shows the thermal transfer parameters T * and ⁇ E T , the absorption maxima of the dyes ⁇ max (measured in methylene chloride) and the binders used.
Landscapes
- Physics & Mathematics (AREA)
- Optics & Photonics (AREA)
- Thermal Transfer Or Thermal Recording In General (AREA)
- Coloring (AREA)
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| DE4112654 | 1991-04-18 | ||
| DE4112654A DE4112654A1 (de) | 1991-04-18 | 1991-04-18 | Verfahren zur uebertragung von methinfarbstoffen |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| EP0509302A1 true EP0509302A1 (fr) | 1992-10-21 |
| EP0509302B1 EP0509302B1 (fr) | 1997-01-29 |
Family
ID=6429850
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| EP92105403A Expired - Lifetime EP0509302B1 (fr) | 1991-04-18 | 1992-03-28 | Procédé pour le transfert de colorants méthiniques |
Country Status (6)
| Country | Link |
|---|---|
| US (1) | US5256624A (fr) |
| EP (1) | EP0509302B1 (fr) |
| JP (1) | JP3272393B2 (fr) |
| KR (1) | KR920019548A (fr) |
| CA (1) | CA2064340A1 (fr) |
| DE (2) | DE4112654A1 (fr) |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0792757A1 (fr) * | 1996-02-27 | 1997-09-03 | Agfa-Gevaert N.V. | Elément donneur de colorant pour utilisation dans un procédé pour l'impression par le transfert thermique |
| US6302924B1 (en) | 1996-03-22 | 2001-10-16 | Basf Aktiengesellschaft | Dye mixtures containing thienyl and/or thiazolazo dyes |
| WO2011045253A1 (fr) | 2009-10-13 | 2011-04-21 | Basf Se | Mélanges pour produire des couches photoactives pour des cellules solaires organiques et des photodétecteurs organiques |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0279467A2 (fr) * | 1987-02-20 | 1988-08-24 | Dai Nippon Insatsu Kabushiki Kaisha | Feuille pour transfert par la chaleur |
| EP0416434A2 (fr) * | 1989-09-07 | 1991-03-13 | BASF Aktiengesellschaft | Colorants triazolopyridiniques ainsi qu'un procédé de transfert thermique de colorants méthiniques |
| EP0444327A1 (fr) * | 1990-03-01 | 1991-09-04 | Agfa-Gevaert N.V. | Colorants pour utilisation en transfert de colorants thermique |
Family Cites Families (17)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS60229786A (ja) * | 1984-04-27 | 1985-11-15 | Matsushita Electric Ind Co Ltd | 転写型感熱記録方法 |
| DE3676245D1 (de) * | 1985-07-23 | 1991-01-31 | Ici Plc | Thermouebertragungsdruck. |
| GB8521327D0 (en) * | 1985-08-27 | 1985-10-02 | Ici Plc | Thermal transfer printing |
| JPH0749535B2 (ja) * | 1985-09-12 | 1995-05-31 | 三井東圧化学株式会社 | 新規な色素体生成法 |
| US4698651A (en) * | 1985-12-24 | 1987-10-06 | Eastman Kodak Company | Magenta dye-donor element used in thermal dye transfer |
| DE3630279A1 (de) * | 1986-09-05 | 1988-03-17 | Basf Ag | Verfahren zur uebertragung von farbstoffen |
| GB8724028D0 (en) * | 1987-10-13 | 1987-11-18 | Ici Plc | Thermal transfer printing |
| DE3820313A1 (de) * | 1988-06-15 | 1989-12-21 | Basf Ag | Verfahren zur uebertragung von azofarbstoffen mit einer pyridin-kupplungskomponente |
| JPH0232164A (ja) * | 1988-07-20 | 1990-02-01 | Sumitomo Chem Co Ltd | α−シアノアゾメチン系化合物、その製法及びそれを用いてなる光情報記録媒体 |
| JPH0284390A (ja) * | 1988-09-21 | 1990-03-26 | Hitachi Ltd | 熱転写シート |
| JP2844345B2 (ja) * | 1989-05-02 | 1999-01-06 | 大日本印刷株式会社 | 熱転写シート |
| US5223476A (en) * | 1989-05-02 | 1993-06-29 | Dai Nippon Insatsu Kabushiki Kaisha | Heat transfer sheet |
| JPH02292371A (ja) * | 1989-05-02 | 1990-12-03 | Sankyo Kagaku Kk | 感熱転写記録用色素 |
| DE4003780A1 (de) * | 1990-02-08 | 1991-08-14 | Basf Ag | Verwendung von azofarbstoffen fuer den thermotransferdruck |
| DE4004612A1 (de) * | 1990-02-15 | 1991-08-22 | Basf Ag | Neue bichromophore methin- und azamethinfarbstoffe und ein verfahren zu ihrer uebertragung |
| DE4018067A1 (de) * | 1990-06-06 | 1991-12-12 | Basf Ag | Verwendung von azofarbstoffen fuer den thermotransferdruck |
| DE4105197A1 (de) * | 1991-02-20 | 1992-08-27 | Basf Ag | Bichromophore methinfarbstoffe |
-
1991
- 1991-04-18 DE DE4112654A patent/DE4112654A1/de not_active Withdrawn
-
1992
- 1992-03-23 CA CA002064340A patent/CA2064340A1/fr not_active Abandoned
- 1992-03-28 DE DE59207973T patent/DE59207973D1/de not_active Expired - Lifetime
- 1992-03-28 EP EP92105403A patent/EP0509302B1/fr not_active Expired - Lifetime
- 1992-03-30 US US07/860,156 patent/US5256624A/en not_active Expired - Fee Related
- 1992-04-10 KR KR1019920005961A patent/KR920019548A/ko active IP Right Grant
- 1992-04-16 JP JP09620292A patent/JP3272393B2/ja not_active Expired - Fee Related
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0279467A2 (fr) * | 1987-02-20 | 1988-08-24 | Dai Nippon Insatsu Kabushiki Kaisha | Feuille pour transfert par la chaleur |
| EP0416434A2 (fr) * | 1989-09-07 | 1991-03-13 | BASF Aktiengesellschaft | Colorants triazolopyridiniques ainsi qu'un procédé de transfert thermique de colorants méthiniques |
| EP0444327A1 (fr) * | 1990-03-01 | 1991-09-04 | Agfa-Gevaert N.V. | Colorants pour utilisation en transfert de colorants thermique |
Non-Patent Citations (5)
| Title |
|---|
| CHEMICAL ABSTRACTS, vol. 112, no. 1, 1. Januar 1990, Columbus, Ohio, US; abstract no. 6938Q, H.MUSTROPH ET AL: 'Different substituent effects on the absorption maxima of azomethines and hydrazones.' Seite 682 ;Spalte RECHT ; * |
| PATENT ABSTRACTS OF JAPAN vol. 11, no. 262 (C-442)(2709) 25. August 1987 & JP-A-62 062 866 ( MITSUI TOATSU CHEM INC ) 19. März 1987 * |
| PATENT ABSTRACTS OF JAPAN vol. 15, no. 65 (M-1082)15. Februar 1991 & JP-A-2 292 090 ( DAI NIPPON PRINTING CO LTD ) 3. Dezember 1990 * |
| WORLD PATENTS INDEX LATEST Week 9011, Derwent Publications Ltd., London, GB; AN 90-079267 * |
| WORLD PATENTS INDEX LATEST Week 9103, Derwent Publications Ltd., London, GB; AN 91-019242 & JP-A-2 292 371 (SANKYO KAGAKU KK) 3. Dezember 1990 * |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0792757A1 (fr) * | 1996-02-27 | 1997-09-03 | Agfa-Gevaert N.V. | Elément donneur de colorant pour utilisation dans un procédé pour l'impression par le transfert thermique |
| US6302924B1 (en) | 1996-03-22 | 2001-10-16 | Basf Aktiengesellschaft | Dye mixtures containing thienyl and/or thiazolazo dyes |
| WO2011045253A1 (fr) | 2009-10-13 | 2011-04-21 | Basf Se | Mélanges pour produire des couches photoactives pour des cellules solaires organiques et des photodétecteurs organiques |
| US9368729B2 (en) | 2009-10-13 | 2016-06-14 | Basf Se | Mixtures for producing photoactive layers for organic solar cells and organic photodetectors |
Also Published As
| Publication number | Publication date |
|---|---|
| DE4112654A1 (de) | 1992-10-22 |
| EP0509302B1 (fr) | 1997-01-29 |
| CA2064340A1 (fr) | 1992-10-19 |
| DE59207973D1 (de) | 1997-03-13 |
| JPH05104863A (ja) | 1993-04-27 |
| KR920019548A (ko) | 1992-11-19 |
| US5256624A (en) | 1993-10-26 |
| JP3272393B2 (ja) | 2002-04-08 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| EP0416434B1 (fr) | Colorants triazolopyridiniques ainsi qu'un procédé de transfert thermique de colorants méthiniques | |
| EP0582579B1 (fr) | Colorants a base de n-aminopyridone | |
| DE3630279A1 (de) | Verfahren zur uebertragung von farbstoffen | |
| EP0441282A1 (fr) | Colorants méthiniques et azaméthiniques bichromophores et un procédé pour leur transfert | |
| EP0346729B1 (fr) | Procédé de transfert de colorants azoiques avec un composant de couplage pyridine | |
| EP0569785B1 (fr) | Mélanges de colorants pour le transfert de colorants | |
| EP0569784A1 (fr) | Mélanges de cyan pour le transfert de colorants | |
| EP0439200B1 (fr) | Procédé pour le transfert des colorants méthiniques bichromophores contenant des groupes cyanos | |
| EP0480252B1 (fr) | Colorants pyridones et un procédé pour leur transfert thermique | |
| EP0479076B1 (fr) | Procédé pour le transfert des colorants indoanilines | |
| EP0509302B1 (fr) | Procédé pour le transfert de colorants méthiniques | |
| EP0680834B1 (fr) | Thermotransfert de colorants pyridone | |
| EP0480281B1 (fr) | Colerants du type indophenol et un procédé pour leurs transfert thermique | |
| DE4003780A1 (de) | Verwendung von azofarbstoffen fuer den thermotransferdruck | |
| EP0344592A2 (fr) | Procédé de transfert de colorants azoiques | |
| EP0449109B1 (fr) | Colorants d'indonaphtol et un procédé pour leur transfert thermique | |
| EP0763571A1 (fr) | Mélanges de colorants contenant des colorants méthiniques et anthraquinoniques | |
| DE4105197A1 (de) | Bichromophore methinfarbstoffe | |
| EP0761464B1 (fr) | Transfert thermique de mélanges de colorants comportant des colorants azaméthiniques | |
| EP0479068A1 (fr) | Colorants de type chinolineméthine et procédé pour leur transformation thermique | |
| DE4114456A1 (de) | N-aminopyridonfarbstoffe | |
| WO1996016820A1 (fr) | Transfert thermique de colorants a l'azamethine a base de pyridone | |
| DE4134805A1 (de) | N-acylaminopyridonfarbstoffe |
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 |
|
| AK | Designated contracting states |
Kind code of ref document: A1 Designated state(s): CH DE FR GB IT LI NL |
|
| 17P | Request for examination filed |
Effective date: 19921001 |
|
| 17Q | First examination report despatched |
Effective date: 19951018 |
|
| GRAG | Despatch of communication of intention to grant |
Free format text: ORIGINAL CODE: EPIDOS AGRA |
|
| GRAH | Despatch of communication of intention to grant a patent |
Free format text: ORIGINAL CODE: EPIDOS IGRA |
|
| GRAH | Despatch of communication of intention to grant a patent |
Free format text: ORIGINAL CODE: EPIDOS IGRA |
|
| GRAA | (expected) grant |
Free format text: ORIGINAL CODE: 0009210 |
|
| AK | Designated contracting states |
Kind code of ref document: B1 Designated state(s): CH DE FR GB IT LI NL |
|
| REG | Reference to a national code |
Ref country code: CH Ref legal event code: EP |
|
| GBT | Gb: translation of ep patent filed (gb section 77(6)(a)/1977) |
Effective date: 19970214 |
|
| REF | Corresponds to: |
Ref document number: 59207973 Country of ref document: DE Date of ref document: 19970313 |
|
| ITF | It: translation for a ep patent filed | ||
| ET | Fr: translation filed | ||
| 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 |
|
| 26N | No opposition filed | ||
| PGFP | Annual fee paid to national office [announced via postgrant information from national office to epo] |
Ref country code: CH Payment date: 19980311 Year of fee payment: 7 |
|
| PGFP | Annual fee paid to national office [announced via postgrant information from national office to epo] |
Ref country code: NL Payment date: 19980312 Year of fee payment: 7 |
|
| PG25 | Lapsed in a contracting state [announced via postgrant information from national office to epo] |
Ref country code: LI Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES Effective date: 19990331 Ref country code: CH Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES Effective date: 19990331 |
|
| 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 NON-PAYMENT OF DUE FEES Effective date: 19991001 |
|
| REG | Reference to a national code |
Ref country code: CH Ref legal event code: PL |
|
| NLV4 | Nl: lapsed or anulled due to non-payment of the annual fee |
Effective date: 19991001 |
|
| REG | Reference to a national code |
Ref country code: GB Ref legal event code: IF02 |
|
| PGFP | Annual fee paid to national office [announced via postgrant information from national office to epo] |
Ref country code: FR Payment date: 20020214 Year of fee payment: 11 |
|
| PGFP | Annual fee paid to national office [announced via postgrant information from national office to epo] |
Ref country code: DE Payment date: 20020309 Year of fee payment: 11 |
|
| PGFP | Annual fee paid to national office [announced via postgrant information from national office to epo] |
Ref country code: GB Payment date: 20020315 Year of fee payment: 11 |
|
| 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: 20030328 |
|
| 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 THE APPLICANT RENOUNCES Effective date: 20030415 |
|
| GBPC | Gb: european patent ceased through non-payment of renewal fee |
Effective date: 20030328 |
|
| PG25 | Lapsed in a contracting state [announced via postgrant information from national office to epo] |
Ref country code: FR Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES Effective date: 20031127 |
|
| REG | Reference to a national code |
Ref country code: FR Ref legal event code: ST |
|
| 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;WARNING: LAPSES OF ITALIAN PATENTS WITH EFFECTIVE DATE BEFORE 2007 MAY HAVE OCCURRED AT ANY TIME BEFORE 2007. THE CORRECT EFFECTIVE DATE MAY BE DIFFERENT FROM THE ONE RECORDED. Effective date: 20050328 |