EP0672540A1 - Matériau d'enregistrement sensible à la préssion contenant des huiles naturelles ou leur dérivés - Google Patents
Matériau d'enregistrement sensible à la préssion contenant des huiles naturelles ou leur dérivés Download PDFInfo
- Publication number
- EP0672540A1 EP0672540A1 EP95103166A EP95103166A EP0672540A1 EP 0672540 A1 EP0672540 A1 EP 0672540A1 EP 95103166 A EP95103166 A EP 95103166A EP 95103166 A EP95103166 A EP 95103166A EP 0672540 A1 EP0672540 A1 EP 0672540A1
- Authority
- EP
- European Patent Office
- Prior art keywords
- methyl
- hydrogen
- methoxy
- chlorine
- ethyl
- 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 34
- 239000003921 oil Substances 0.000 title claims abstract description 34
- -1 pyrrolidino, piperidino Chemical group 0.000 claims abstract description 149
- 239000002904 solvent Substances 0.000 claims abstract description 54
- 125000004573 morpholin-4-yl group Chemical group N1(CCOCC1)* 0.000 claims abstract description 34
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims abstract description 27
- 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 abstract description 25
- 125000001797 benzyl group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C([H])([H])* 0.000 claims abstract description 23
- 150000002148 esters Chemical class 0.000 claims abstract description 12
- 229910052736 halogen Inorganic materials 0.000 claims abstract description 12
- 150000002367 halogens Chemical class 0.000 claims abstract description 12
- 125000002147 dimethylamino group Chemical group [H]C([H])([H])N(*)C([H])([H])[H] 0.000 claims abstract description 11
- 125000000217 alkyl group Chemical group 0.000 claims abstract description 8
- 235000014113 dietary fatty acids Nutrition 0.000 claims abstract description 6
- 239000000194 fatty acid Substances 0.000 claims abstract description 6
- 229930195729 fatty acid Natural products 0.000 claims abstract description 6
- 150000004665 fatty acids Chemical class 0.000 claims abstract description 6
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims description 90
- 229910052739 hydrogen Inorganic materials 0.000 claims description 76
- 239000001257 hydrogen Substances 0.000 claims description 76
- 125000000956 methoxy group Chemical group [H]C([H])([H])O* 0.000 claims description 49
- 150000002431 hydrogen Chemical group 0.000 claims description 48
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 47
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 claims description 45
- 239000000203 mixture Substances 0.000 claims description 44
- 229910052801 chlorine Inorganic materials 0.000 claims description 43
- 239000000460 chlorine Substances 0.000 claims description 43
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 claims description 35
- 235000019198 oils Nutrition 0.000 claims description 31
- 239000003094 microcapsule Substances 0.000 claims description 22
- 125000004178 (C1-C4) alkyl group Chemical group 0.000 claims description 12
- 125000003903 2-propenyl group Chemical group [H]C([*])([H])C([H])=C([H])[H] 0.000 claims description 12
- 239000003086 colorant Substances 0.000 claims description 12
- 125000001511 cyclopentyl group Chemical group [H]C1([H])C([H])([H])C([H])([H])C([H])(*)C1([H])[H] 0.000 claims description 12
- 125000002541 furyl group Chemical group 0.000 claims description 12
- 125000004076 pyridyl group Chemical group 0.000 claims description 12
- 125000000168 pyrrolyl group Chemical group 0.000 claims description 12
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims description 11
- GTYZDORKFFSTLS-UHFFFAOYSA-N 2h-3,1-benzoxazine Chemical class C1=CC=CC2=NCOC=C21 GTYZDORKFFSTLS-UHFFFAOYSA-N 0.000 claims description 10
- 125000000051 benzyloxy group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C([H])([H])O* 0.000 claims description 9
- 150000001875 compounds Chemical class 0.000 claims description 9
- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 claims description 9
- 125000004108 n-butyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 claims description 9
- 125000004123 n-propyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])* 0.000 claims description 9
- 125000002914 sec-butyl group Chemical group [H]C([H])([H])C([H])([H])C([H])(*)C([H])([H])[H] 0.000 claims description 9
- 125000004400 (C1-C12) alkyl group Chemical group 0.000 claims description 6
- 125000006274 (C1-C3)alkoxy group Chemical group 0.000 claims description 6
- 125000004209 (C1-C8) alkyl group Chemical group 0.000 claims description 6
- 125000004493 2-methylbut-1-yl group Chemical group CC(C*)CC 0.000 claims description 6
- 125000000339 4-pyridyl group Chemical group N1=C([H])C([H])=C([*])C([H])=C1[H] 0.000 claims description 6
- PXGOKWXKJXAPGV-UHFFFAOYSA-N Fluorine Chemical compound FF PXGOKWXKJXAPGV-UHFFFAOYSA-N 0.000 claims description 6
- 125000002490 anilino group Chemical group [H]N(*)C1=C([H])C([H])=C([H])C([H])=C1[H] 0.000 claims description 6
- 125000004093 cyano group Chemical group *C#N 0.000 claims description 6
- 125000004210 cyclohexylmethyl group Chemical group [H]C([H])(*)C1([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C1([H])[H] 0.000 claims description 6
- FWQHNLCNFPYBCA-UHFFFAOYSA-N fluoran Chemical compound C12=CC=CC=C2OC2=CC=CC=C2C11OC(=O)C2=CC=CC=C21 FWQHNLCNFPYBCA-UHFFFAOYSA-N 0.000 claims description 6
- 125000001972 isopentyl group Chemical group [H]C([H])([H])C([H])(C([H])([H])[H])C([H])([H])C([H])([H])* 0.000 claims description 6
- 125000003538 pentan-3-yl group Chemical group [H]C([H])([H])C([H])([H])C([H])(*)C([H])([H])C([H])([H])[H] 0.000 claims description 6
- 125000001424 substituent group Chemical group 0.000 claims description 6
- 235000019484 Rapeseed oil Nutrition 0.000 claims description 5
- 229930195733 hydrocarbon Natural products 0.000 claims description 5
- 150000002430 hydrocarbons Chemical class 0.000 claims description 5
- 235000019482 Palm oil Nutrition 0.000 claims description 4
- 150000004945 aromatic hydrocarbons Chemical class 0.000 claims description 4
- 239000003240 coconut oil Substances 0.000 claims description 4
- 235000019864 coconut oil Nutrition 0.000 claims description 4
- 229910052731 fluorine Inorganic materials 0.000 claims description 4
- 239000011737 fluorine Substances 0.000 claims description 4
- 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 claims description 4
- 239000002540 palm oil Substances 0.000 claims description 4
- 239000008159 sesame oil Substances 0.000 claims description 4
- 235000011803 sesame oil Nutrition 0.000 claims description 4
- 239000003549 soybean oil Substances 0.000 claims description 4
- 235000012424 soybean oil Nutrition 0.000 claims description 4
- 125000004200 2-methoxyethyl group Chemical group [H]C([H])([H])OC([H])([H])C([H])([H])* 0.000 claims description 3
- 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 claims description 3
- CMLFRMDBDNHMRA-UHFFFAOYSA-N 2h-1,2-benzoxazine Chemical compound C1=CC=C2C=CNOC2=C1 CMLFRMDBDNHMRA-UHFFFAOYSA-N 0.000 claims description 3
- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 claims description 3
- 125000001664 diethylamino group Chemical group [H]C([H])([H])C([H])([H])N(*)C([H])([H])C([H])([H])[H] 0.000 claims description 3
- 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 claims description 3
- 125000001037 p-tolyl group Chemical group [H]C1=C([H])C(=C([H])C([H])=C1*)C([H])([H])[H] 0.000 claims description 3
- 125000001147 pentyl group Chemical group C(CCCC)* 0.000 claims description 3
- 125000000951 phenoxy group Chemical group [H]C1=C([H])C([H])=C(O*)C([H])=C1[H] 0.000 claims description 3
- 229920000768 polyamine Polymers 0.000 claims description 3
- 229920001228 polyisocyanate Polymers 0.000 claims description 3
- 239000005056 polyisocyanate Substances 0.000 claims description 3
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 claims description 3
- 125000002023 trifluoromethyl group Chemical group FC(F)(F)* 0.000 claims description 3
- 125000004182 2-chlorophenyl group Chemical group [H]C1=C([H])C(Cl)=C(*)C([H])=C1[H] 0.000 claims description 2
- 235000019483 Peanut oil Nutrition 0.000 claims description 2
- 235000019486 Sunflower oil Nutrition 0.000 claims description 2
- 125000002777 acetyl group Chemical group [H]C([H])([H])C(*)=O 0.000 claims description 2
- 239000004359 castor oil Substances 0.000 claims description 2
- 235000019438 castor oil Nutrition 0.000 claims description 2
- 235000012343 cottonseed oil Nutrition 0.000 claims description 2
- 239000002385 cottonseed oil Substances 0.000 claims description 2
- 235000021323 fish oil Nutrition 0.000 claims description 2
- ZEMPKEQAKRGZGQ-XOQCFJPHSA-N glycerol triricinoleate Natural products CCCCCC[C@@H](O)CC=CCCCCCCCC(=O)OC[C@@H](COC(=O)CCCCCCCC=CC[C@@H](O)CCCCCC)OC(=O)CCCCCCCC=CC[C@H](O)CCCCCC ZEMPKEQAKRGZGQ-XOQCFJPHSA-N 0.000 claims description 2
- 239000000944 linseed oil Substances 0.000 claims description 2
- 235000021388 linseed oil Nutrition 0.000 claims description 2
- 125000000449 nitro group Chemical group [O-][N+](*)=O 0.000 claims description 2
- 125000003261 o-tolyl group Chemical group [H]C1=C([H])C(*)=C(C([H])=C1[H])C([H])([H])[H] 0.000 claims description 2
- 239000004006 olive oil Substances 0.000 claims description 2
- 235000008390 olive oil Nutrition 0.000 claims description 2
- 125000003854 p-chlorophenyl group Chemical group [H]C1=C([H])C(*)=C([H])C([H])=C1Cl 0.000 claims description 2
- 239000000312 peanut oil Substances 0.000 claims description 2
- 239000002600 sunflower oil Substances 0.000 claims description 2
- 125000001309 chloro group Chemical group Cl* 0.000 claims 4
- 150000003254 radicals Chemical class 0.000 description 15
- 230000032683 aging Effects 0.000 description 8
- 239000002775 capsule Substances 0.000 description 8
- 239000000243 solution Substances 0.000 description 6
- 150000005130 benzoxazines Chemical class 0.000 description 5
- 238000010521 absorption reaction Methods 0.000 description 4
- 239000006185 dispersion Substances 0.000 description 4
- 238000004519 manufacturing process Methods 0.000 description 4
- 238000000034 method Methods 0.000 description 4
- 244000060011 Cocos nucifera Species 0.000 description 3
- 235000013162 Cocos nucifera Nutrition 0.000 description 3
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- 238000005562 fading Methods 0.000 description 3
- 235000019197 fats Nutrition 0.000 description 3
- 230000007935 neutral effect Effects 0.000 description 3
- 125000005506 phthalide group Chemical group 0.000 description 3
- 150000001735 carboxylic acids Chemical class 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- 230000007423 decrease Effects 0.000 description 2
- DOIRQSBPFJWKBE-UHFFFAOYSA-N dibutyl phthalate Chemical class CCCCOC(=O)C1=CC=CC=C1C(=O)OCCCC DOIRQSBPFJWKBE-UHFFFAOYSA-N 0.000 description 2
- 238000004945 emulsification Methods 0.000 description 2
- KDQIFKKWPMBNOH-UHFFFAOYSA-N methyl 16-methylheptadecanoate Chemical compound COC(=O)CCCCCCCCCCCCCCC(C)C KDQIFKKWPMBNOH-UHFFFAOYSA-N 0.000 description 2
- 239000003960 organic solvent Substances 0.000 description 2
- 229920002451 polyvinyl alcohol Polymers 0.000 description 2
- 238000002360 preparation method Methods 0.000 description 2
- 238000003825 pressing Methods 0.000 description 2
- 150000003839 salts Chemical class 0.000 description 2
- RMAQACBXLXPBSY-UHFFFAOYSA-N silicic acid Chemical compound O[Si](O)(O)O RMAQACBXLXPBSY-UHFFFAOYSA-N 0.000 description 2
- 238000003860 storage Methods 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- YJTKZCDBKVTVBY-UHFFFAOYSA-N 1,3-Diphenylbenzene Chemical group C1=CC=CC=C1C1=CC=CC(C=2C=CC=CC=2)=C1 YJTKZCDBKVTVBY-UHFFFAOYSA-N 0.000 description 1
- OVYMWJFNQQOJBU-UHFFFAOYSA-N 1-octanoyloxypropan-2-yl octanoate Chemical compound CCCCCCCC(=O)OCC(C)OC(=O)CCCCCCC OVYMWJFNQQOJBU-UHFFFAOYSA-N 0.000 description 1
- FXSFKECPPGDGBN-UHFFFAOYSA-N 3,3-bis(1h-indol-2-yl)-2-benzofuran-1-one Chemical compound C12=CC=CC=C2C(=O)OC1(C=1NC2=CC=CC=C2C=1)C1=CC2=CC=CC=C2N1 FXSFKECPPGDGBN-UHFFFAOYSA-N 0.000 description 1
- HIQIXEFWDLTDED-UHFFFAOYSA-N 4-hydroxy-1-piperidin-4-ylpyrrolidin-2-one Chemical compound O=C1CC(O)CN1C1CCNCC1 HIQIXEFWDLTDED-UHFFFAOYSA-N 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
- 244000215068 Acacia senegal Species 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- RPNUMPOLZDHAAY-UHFFFAOYSA-N Diethylenetriamine Chemical compound NCCNCCN RPNUMPOLZDHAAY-UHFFFAOYSA-N 0.000 description 1
- 108010010803 Gelatin Proteins 0.000 description 1
- 229920000084 Gum arabic Polymers 0.000 description 1
- 229920000877 Melamine resin Polymers 0.000 description 1
- 241001465754 Metazoa Species 0.000 description 1
- JCXJVPUVTGWSNB-UHFFFAOYSA-N Nitrogen dioxide Chemical class O=[N]=O JCXJVPUVTGWSNB-UHFFFAOYSA-N 0.000 description 1
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 1
- 239000004952 Polyamide Substances 0.000 description 1
- 229920002396 Polyurea Polymers 0.000 description 1
- 239000004372 Polyvinyl alcohol Substances 0.000 description 1
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 1
- 239000002174 Styrene-butadiene Substances 0.000 description 1
- 229920001807 Urea-formaldehyde Polymers 0.000 description 1
- 241000231697 Zelus means Species 0.000 description 1
- 239000000205 acacia gum Substances 0.000 description 1
- 235000010489 acacia gum Nutrition 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 230000004913 activation Effects 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- KXDGDQAPIYAGLD-UHFFFAOYSA-N benzhydrylbenzene;methanol Chemical compound OC.C1=CC=CC=C1C(C=1C=CC=CC=1)C1=CC=CC=C1 KXDGDQAPIYAGLD-UHFFFAOYSA-N 0.000 description 1
- 239000011230 binding agent Substances 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 235000010290 biphenyl Nutrition 0.000 description 1
- 150000004074 biphenyls Chemical class 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
- 229910052799 carbon Inorganic materials 0.000 description 1
- 239000001913 cellulose Substances 0.000 description 1
- 229920002678 cellulose Polymers 0.000 description 1
- 239000004927 clay Substances 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 229940071160 cocoate Drugs 0.000 description 1
- 238000002425 crystallisation Methods 0.000 description 1
- 230000008025 crystallization Effects 0.000 description 1
- GHVNFZFCNZKVNT-UHFFFAOYSA-M decanoate Chemical compound CCCCCCCCCC([O-])=O GHVNFZFCNZKVNT-UHFFFAOYSA-M 0.000 description 1
- 238000002845 discoloration Methods 0.000 description 1
- 239000000975 dye Substances 0.000 description 1
- QYDYPVFESGNLHU-UHFFFAOYSA-N elaidic acid methyl ester Natural products CCCCCCCCC=CCCCCCCCC(=O)OC QYDYPVFESGNLHU-UHFFFAOYSA-N 0.000 description 1
- 239000003995 emulsifying agent Substances 0.000 description 1
- 230000001804 emulsifying effect Effects 0.000 description 1
- 239000000839 emulsion Substances 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 150000002170 ethers Chemical class 0.000 description 1
- 238000011156 evaluation Methods 0.000 description 1
- 235000019387 fatty acid methyl ester Nutrition 0.000 description 1
- 230000002349 favourable effect Effects 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
- 239000008240 homogeneous mixture Substances 0.000 description 1
- 238000003384 imaging method Methods 0.000 description 1
- 150000002596 lactones Chemical class 0.000 description 1
- 239000004816 latex Substances 0.000 description 1
- 229920000126 latex Polymers 0.000 description 1
- JDSHMPZPIAZGSV-UHFFFAOYSA-N melamine Chemical compound NC1=NC(N)=NC(N)=N1 JDSHMPZPIAZGSV-UHFFFAOYSA-N 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- 239000002184 metal Chemical class 0.000 description 1
- QYDYPVFESGNLHU-KHPPLWFESA-N methyl oleate Chemical compound CCCCCCCC\C=C/CCCCCCCC(=O)OC QYDYPVFESGNLHU-KHPPLWFESA-N 0.000 description 1
- 229940073769 methyl oleate Drugs 0.000 description 1
- 150000002790 naphthalenes Chemical class 0.000 description 1
- 229930014626 natural product Natural products 0.000 description 1
- 230000003287 optical effect Effects 0.000 description 1
- 229920001568 phenolic resin Polymers 0.000 description 1
- 150000002989 phenols Chemical class 0.000 description 1
- 229920000058 polyacrylate Polymers 0.000 description 1
- 229920002647 polyamide Polymers 0.000 description 1
- 229920000515 polycarbonate Polymers 0.000 description 1
- 239000004417 polycarbonate Substances 0.000 description 1
- 229920000728 polyester Polymers 0.000 description 1
- ODGAOXROABLFNM-UHFFFAOYSA-N polynoxylin Chemical compound O=C.NC(N)=O ODGAOXROABLFNM-UHFFFAOYSA-N 0.000 description 1
- 239000004814 polyurethane Substances 0.000 description 1
- 229920002635 polyurethane Polymers 0.000 description 1
- 239000011877 solvent mixture Substances 0.000 description 1
- 125000006850 spacer group Chemical group 0.000 description 1
- 230000003595 spectral effect Effects 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 239000011115 styrene butadiene Substances 0.000 description 1
- 229920003048 styrene butadiene rubber Polymers 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- AAAQKTZKLRYKHR-UHFFFAOYSA-N triphenylmethane Chemical compound C1=CC=CC=C1C(C=1C=CC=CC=1)C1=CC=CC=C1 AAAQKTZKLRYKHR-UHFFFAOYSA-N 0.000 description 1
- 235000013311 vegetables Nutrition 0.000 description 1
- 238000011179 visual inspection Methods 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
- B41M5/124—Duplicating or marking methods; Sheet materials for use therein using pressure to make a masked colour visible, e.g. to make a coloured support visible, to create an opaque or transparent pattern, or to form colour by uniting colour-forming components
- B41M5/132—Chemical colour-forming components; Additives or binders therefor
- B41M5/136—Organic colour formers, e.g. leuco dyes
- B41M5/145—Organic colour formers, e.g. leuco dyes with a lactone or lactam ring
-
- 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
- B41M5/124—Duplicating or marking methods; Sheet materials for use therein using pressure to make a masked colour visible, e.g. to make a coloured support visible, to create an opaque or transparent pattern, or to form colour by uniting colour-forming components
- B41M5/132—Chemical colour-forming components; Additives or binders therefor
- B41M5/136—Organic colour formers, e.g. leuco dyes
-
- 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
- B41M5/124—Duplicating or marking methods; Sheet materials for use therein using pressure to make a masked colour visible, e.g. to make a coloured support visible, to create an opaque or transparent pattern, or to form colour by uniting colour-forming components
- B41M5/165—Duplicating or marking methods; Sheet materials for use therein using pressure to make a masked colour visible, e.g. to make a coloured support visible, to create an opaque or transparent pattern, or to form colour by uniting colour-forming components characterised by the use of microcapsules; Special solvents for incorporating the ingredients
- B41M5/1655—Solvents
-
- 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
- B41M5/124—Duplicating or marking methods; Sheet materials for use therein using pressure to make a masked colour visible, e.g. to make a coloured support visible, to create an opaque or transparent pattern, or to form colour by uniting colour-forming components
- B41M5/132—Chemical colour-forming components; Additives or binders therefor
- B41M5/136—Organic colour formers, e.g. leuco dyes
- B41M5/145—Organic colour formers, e.g. leuco dyes with a lactone or lactam ring
- B41M5/1455—Organic colour formers, e.g. leuco dyes with a lactone or lactam ring characterised by fluoran compounds
Definitions
- the present invention relates to a pressure-sensitive recording material which contains color donors in microencapsulated form, the solvent for the color donors containing natural oils and / or derivatives thereof.
- Pressure-sensitive recording material consists, for example, of at least one pair of (paper) sheets which contain a color former or a color former mixture, dissolved or dispersed in a non-volatile organic solvent, and a developer.
- paper paper sheets which contain a color former or a color former mixture, dissolved or dispersed in a non-volatile organic solvent, and a developer.
- a color former or a color former mixture dissolved or dispersed in a non-volatile organic solvent, and a developer.
- such a pressure-sensitive recording material can consist of two sheets of paper, the upper sheet being, for example, CB (Coated Back) paper which is coated on its underside with microcapsules which contain the color former and an organic solvent.
- the lower sheet is then designed as CF paper (coated front), the top of which is coated with the developer.
- SC paper Self Contained
- microcapsules which contain colorants and solvents and developers are applied together on the top of a sheet and covered with an uncoated sheet of paper.
- Suitable capsule material is e.g. Gelatin / gum arabic, polyamides, polyurethanes, polyureas, polysulfonamides, polyesters, polycarbonates, polysulfonates, polyacrylates and phenol, melamine and urea-formaldehyde condensates as described, for example, in M. Gutcho, Capsule Technology and Microencapsulation, Noyes Data Co. 1972; G. Baster, Microencapsulation, Processes and Applications, editor J.E. Vandegaar, and in DE-A 2 237 545 and 2 119 933 are described. Microcapsules whose shells consist of polyadducts of polyisocyanates and polyamines are particularly advantageous. Polyisocyanates, polyamines, solvents and suitable production processes for the last-mentioned microcapsules are described, for example, in DE-A 3 203 059.
- Suitable developers are clays, acid-modified clays, oxides and acid salts, and monomeric, resinous and polymeric phenols, carboxylic acids or metal salts of carboxylic acids.
- 3,1-benzoxazines are used as color formers e.g. known from DE-A 3 500 361, DE-A 3 622 262 and EP-A 316 277.
- Mixtures of 3,1-benzoxazines with color formers from the series of the fluoranes and diindolyllactones are e.g. known from DE-A 3 841 668 and DE-A 4 010 641.
- Aromatic hydrocarbons, alkylated aromatic hydrocarbons, esters and aliphatic chlorinated hydrocarbons are usually used as solvents for the color formers in microcapsules, e.g. partially hydrogenated terphenyl, alkylated naphthalenes and biphenyls, dibutyl phthalate and partially chlorinated paraffins. These solvents can be mixed with one another and, if appropriate, also with other solvents.
- Color formers with good application properties are 3,1-benzoxazines, fluoranes and diindolyllactones. However, these are connections with distinctly polar structural elements. It was therefore to be expected that, in contrast to the almost non-polar triphenylmethane carbinol bases and ethers, these color formers would only dissolve inadequately in natural oils.
- the recording materials according to the invention surprisingly give an image which has a significantly more neutral shade after exposure of the CF or CB side.
- the image shows a higher intensity after exposure of the CB side than when using conventional solvents.
- recording materials according to the invention are surprisingly more stable to aging processes, in particular in wet-heat aging. After storage for several days under 70 ° C / 75% relative humidity, they produce more intensive images than when using conventional solvents.
- microcapsules in recording materials according to the invention are denser and can be produced with less emulsifying energy than conventional microcapsules.
- Natural oils are those of vegetable and animal origin such as coconut oil (oil), palm oil, sunflower oil, rapeseed oil, olive oil, sesame oil, soybean oil, linseed oil, castor oil, cottonseed oil, peanut oil or fish oil.
- esters of fatty acids on which such oils are based such as rapeseed oil fatty acid methyl ester, methyl oleate, 2-ethylhexyl cocoate, isopropyl myristate, propylene glycol dicaprylate / caprate or methyl isostearate.
- These oils and / or esters can be used individually, in mixtures with one another and / or in mixtures with paraffinic and / or aromatic hydrocarbons. Mixtures with hydrocarbons preferably contain at least 50% by weight of natural oils or esters of the fatty acids on which such oils are based.
- Preferred natural oils are coconut fat (oil), palm oil, rapeseed oil, sesame oil and soybean oil.
- Preferred hydrocarbons are paraffinic, in particular branched, paraffinic hydrocarbons, for example so-called white oil.
- Coconut fat (oil) and coconut fat / white oil mixtures are particularly preferred.
- the proportion of white oil in such mixtures can e.g. be between 1 and 50% by weight, preferably between 10 and 40% by weight.
- Such mixtures preferably contain at least 50% by weight, preferably at least 65% by weight, of 3,1-benzoxazines of the formula (I) and a maximum of 2 compounds from the group of the fluoranes of the formulas (V) and (VI) and the diindolyllactones of formula (VII).
- recording materials according to the invention which, as colorants, contain mixtures of black-developing benzoxazines and black-developing fluoranes or mixtures of black-developing benzoxazines, green-developing fluoranes and red-developing benzoxazines or diindolyllactones or mixtures of green-developing benzoxazines, black-developing Contain fluorans and red-developing benzoxazines or diindolyl lactones.
- Such mixtures are characterized by a more intensive imaging ability compared to the individual components.
- a paper can be coated with microcapsules which contain color formers or color form mixtures to be used according to the invention in solvents or solvent mixtures to be used according to the invention, so produce a CB paper and this with commercially available CF paper that is coated with a developer. It is also possible to apply such microcapsules together with one of the developers mentioned above to the top of a paper in a customary manner and thus to contain an SC paper which can be used in a conventional way in a carbon copy set. The copy is created with imagewise, mechanical pressure on the surface by developing the color former solution emerging from the destroyed capsules on the surface of the CF or SC paper.
- the quality of such copies can be determined, for example, by measuring the reflectance. For example, a large-area impression can be made by destroying the capsules of a CB paper on the front side of a CF paper containing the color developer.
- the impression CF fading
- CB Decline the CB side coated with microcapsules
- the intensity of the exposed impression (CF fading) can be determined as indicated above and the color tone can be compared with the original by visual inspection.
- CB Decline When exposing the capsule-coated side of a CB paper, a copy can then be made by applying pressure. Their intensity (CB Decline) can be determined as indicated above and, together with the color, compared with the copy of an unexposed CB paper in an analog manner.
- this can e.g. stored at 70 ° C and 75% relative humidity for 12 days.
- a print can then be made by applying pressure, the intensity (aging) of which is determined as above and compared with the color tone to the copy of a CB paper stored at room temperature in a dry place.
- Copies resulting from the color formers or color picture mixtures to be used according to the invention in the solvents to be used according to the invention show a more neutral shade after aging and with CF fading and CB declining, ie a smaller color shift, and after aging and with the CB-Decline a higher color intensity than when using conventional solvents and / or other color formers.
- the emulsification in the production of microcapsules to be used according to the invention requires considerably less energy than the emulsification in the production of conventional color formers and solvent-containing microcapsules.
- a commercially available laboratory emulsifier of the type MT 48/260 manufactured by the manufacturer of the production of the production of the invention. It was observed that to produce a droplet size of 7 ⁇ m instead of the otherwise usual 9000 revolutions per minute, only about 6000 revolutions per minute in the production according to the invention using microcapsules were required.
- microcapsules to be used according to the invention also have a higher tightness.
- a microcapsule dispersion obtained according to Example A was added 2.1 g of a conventional cellulose-based spacer, e.g. Albocell® BE 600/30, 2.0 g of a conventional binder, e.g. a styrene-butadiene latex, and 16.3 g of water were stirred in.
- This mixture was applied to a base paper (40 g / m2) using a 40 ⁇ m doctor blade and dried. This gave a CB paper with a coating weight of approximately 5.5 g / m 2.
- the intensity was determined from the remission of the fourth copy of a set, in which sheets 1 to 3 were made from a base paper (46 g / m 2), sheet 4 from the one prepared according to Example B.
- CB paper and sheet 5 consisted of a commercially available CF paper, calculated according to the formula given above.
- Example C A copy made according to Example C or a CB paper made according to Example B was irradiated for 48 hours in a box with four 18 W fluorescent tubes (Sylvania-Luxline® ES, daylight de luxe).
- a CB paper produced according to Example B was stored in a commercially available climatic cabinet at a temperature of 70 ° C. and a relative atmospheric humidity of 75%. After a storage time of 12 days, a sample of the aged paper was written through onto a commercially available, fresh CF paper and measured as described in Example C.
- 5.7 parts by weight of a microcapsule dispersion prepared in accordance with Example A were mixed with 8.5 parts by weight of water and 13.3 parts by weight of silica sol (silica sol F 300 from Bayer AG or Ludox® HS 40 from Dupont). Approx. 5 ml of the homogeneous mixture were applied to a standard base paper (approx. 40 g / m2) by means of a wire knife, as described in Example B, and then dried using warm air. The discoloration of the paper was measured optically, as described above. The following applies to the evaluation: The lower the measured absorption value, the higher the tightness of the microcapsule wall.
Landscapes
- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- General Chemical & Material Sciences (AREA)
- Color Printing (AREA)
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| DE4409265A DE4409265A1 (de) | 1994-03-18 | 1994-03-18 | Druckempfindliches Aufzeichnungsmaterial, das natürliche Öle und/oder Derivate davon enthält |
| DE4409265 | 1994-03-18 |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| EP0672540A1 true EP0672540A1 (fr) | 1995-09-20 |
| EP0672540B1 EP0672540B1 (fr) | 1997-08-06 |
Family
ID=6513156
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| EP95103166A Expired - Lifetime EP0672540B1 (fr) | 1994-03-18 | 1995-03-06 | Matériau d'enregistrement sensible à la préssion contenant des huiles naturelles ou leur dérivés |
Country Status (6)
| Country | Link |
|---|---|
| US (1) | US5552365A (fr) |
| EP (1) | EP0672540B1 (fr) |
| JP (1) | JPH07276797A (fr) |
| CA (1) | CA2144683A1 (fr) |
| DE (2) | DE4409265A1 (fr) |
| ES (1) | ES2105793T3 (fr) |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0697292A1 (fr) * | 1994-07-20 | 1996-02-21 | The Wiggings Teape Group Limited | Matériau d'enregistrement sensible à la pression |
| WO1997045273A1 (fr) * | 1996-05-30 | 1997-12-04 | Minnesota Mining And Manufacturing Company | Composes chromogenes a base de sultine et leur utilisation dans des papiers autocopiants sans carbone |
| WO2000016985A1 (fr) * | 1998-09-23 | 2000-03-30 | The Mead Corporation | Microcapsules contenant du solvant pour de la matiere chromogene |
| EP2065459A3 (fr) * | 2007-11-05 | 2010-08-25 | Sunbelt Corporation | Formulations liquides de colorants dans des systèmes de solvants non dérivés du pétrole |
Families Citing this family (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5925595A (en) * | 1997-09-05 | 1999-07-20 | Monsanto Company | Microcapsules with readily adjustable release rates |
| DE10336044A1 (de) * | 2003-08-01 | 2005-02-17 | Beiersdorf Ag | Tensidfreie Rasierhilfszubereitung |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0316277A2 (fr) * | 1987-11-12 | 1989-05-17 | Ciba-Geigy Ag | 2,4-Benzoxazines substituées en position 1 par un hétérocycle, chromogènes |
| DE4010641A1 (de) * | 1990-04-03 | 1991-10-10 | Bayer Ag | Farbbildner-mischung fuer druck- und waermeempfindliche aufzeichnungssysteme |
| EP0573210A2 (fr) * | 1992-06-04 | 1993-12-08 | The Wiggins Teape Group Limited | Matériau d'enregistrement sensible à la pression |
Family Cites Families (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| AU5960380A (en) * | 1979-08-30 | 1981-03-05 | A. Ehrenreich G.m.b.H. & Co. KG | Bellows seal and retaining ring |
| DE3622262A1 (de) * | 1986-07-02 | 1988-01-07 | Bayer Ag | Chromogene 3,1-benzoxazine |
| DE3633116A1 (de) * | 1986-09-30 | 1988-04-07 | Feldmuehle Ag | Druckempfindliches aufzeichnungsmaterial |
| DE3841668A1 (de) * | 1988-12-10 | 1990-06-13 | Bayer Ag | Mischung aus 3.1-benzoxazinen und fluoranen |
-
1994
- 1994-03-18 DE DE4409265A patent/DE4409265A1/de not_active Withdrawn
-
1995
- 1995-03-06 EP EP95103166A patent/EP0672540B1/fr not_active Expired - Lifetime
- 1995-03-06 ES ES95103166T patent/ES2105793T3/es not_active Expired - Lifetime
- 1995-03-06 DE DE59500455T patent/DE59500455D1/de not_active Expired - Fee Related
- 1995-03-10 US US08/401,841 patent/US5552365A/en not_active Expired - Fee Related
- 1995-03-15 CA CA002144683A patent/CA2144683A1/fr not_active Abandoned
- 1995-03-15 JP JP7083300A patent/JPH07276797A/ja active Pending
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0316277A2 (fr) * | 1987-11-12 | 1989-05-17 | Ciba-Geigy Ag | 2,4-Benzoxazines substituées en position 1 par un hétérocycle, chromogènes |
| DE4010641A1 (de) * | 1990-04-03 | 1991-10-10 | Bayer Ag | Farbbildner-mischung fuer druck- und waermeempfindliche aufzeichnungssysteme |
| EP0573210A2 (fr) * | 1992-06-04 | 1993-12-08 | The Wiggins Teape Group Limited | Matériau d'enregistrement sensible à la pression |
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0697292A1 (fr) * | 1994-07-20 | 1996-02-21 | The Wiggings Teape Group Limited | Matériau d'enregistrement sensible à la pression |
| WO1997045273A1 (fr) * | 1996-05-30 | 1997-12-04 | Minnesota Mining And Manufacturing Company | Composes chromogenes a base de sultine et leur utilisation dans des papiers autocopiants sans carbone |
| WO2000016985A1 (fr) * | 1998-09-23 | 2000-03-30 | The Mead Corporation | Microcapsules contenant du solvant pour de la matiere chromogene |
| EP2065459A3 (fr) * | 2007-11-05 | 2010-08-25 | Sunbelt Corporation | Formulations liquides de colorants dans des systèmes de solvants non dérivés du pétrole |
| US7842102B2 (en) | 2007-11-05 | 2010-11-30 | Sunbelt Corporation | Liquid dye formulations in non-petroleum based solvent systems |
| US8529639B2 (en) | 2007-11-05 | 2013-09-10 | Sunbelt Corporation | Liquid dye formulations in non-petroleum based solvent systems |
Also Published As
| Publication number | Publication date |
|---|---|
| EP0672540B1 (fr) | 1997-08-06 |
| DE59500455D1 (de) | 1997-09-11 |
| JPH07276797A (ja) | 1995-10-24 |
| CA2144683A1 (fr) | 1995-09-19 |
| US5552365A (en) | 1996-09-03 |
| DE4409265A1 (de) | 1995-09-21 |
| ES2105793T3 (es) | 1997-10-16 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| DE3789574T2 (de) | Wärmeempfindliches Farbe-Aufzeichnungsmaterial mit Mikrokapseln. | |
| DE2834711A1 (de) | Chromogene verbindungen und deren verwendung als farbbildner in kopier- oder aufzeichnungsmaterialien | |
| DE3045022A1 (de) | Bildaufzeichnungsmaterialien | |
| DE2163658C3 (de) | 3-<2-Alkoxy-4-amino-phenyl)-3-(3-indolyl)-phthalide sowie druckempfindliche Kopierpapiere, die diese enthalten | |
| DE2618264C3 (de) | Druckempfindliches Aufzeichnungsmaterial und farbbildende Lösung zur Verwendung darin | |
| DE2025816B2 (de) | Waermeempfindliche kopierblaetter | |
| CH644551A5 (de) | Chromogene zusammensetzung. | |
| DE3438083C2 (fr) | ||
| DE1421395B2 (de) | Aufzeichnungsverfahren und Vervielfältigungssatz | |
| EP0672540B1 (fr) | Matériau d'enregistrement sensible à la préssion contenant des huiles naturelles ou leur dérivés | |
| DE3116815C2 (fr) | ||
| DE19717651B4 (de) | Kohlenstoff-freies, druckempfindliches Kopierpapier und dessen Verwendung | |
| DE2156371A1 (de) | Farbbildnermasse für druckempfindliche Aufzeichnungen | |
| DE2530464C3 (de) | Druckempfindliches Kopiermaterial | |
| EP0018537A1 (fr) | Matériau d'enregistrement sensible à la pression et à la chaleur | |
| DE3243945A1 (de) | Waermeempfindliches aufzeichnungsmaterial | |
| DE4010641C2 (de) | Farbbildner-Mischung für druck- und wärmeempfindliche Aufzeichnungssysteme | |
| DE3804437C2 (de) | Leukofarbstoff und ihn enthaltendes Aufzeichnungsmaterial | |
| DE2262127C3 (de) | 6-(N-Alkyl-N-arylamino)-fluorane und deren Verwendung als Farbbildner in druck- und wärmeempfindlichen Kopiermaterialien | |
| EP0373416B1 (fr) | Mélange de 3,1-benzooxazines et de fluoranes | |
| DE3018546A1 (de) | Neue fluorane, verfahren zu deren herstellung und markierungssysteme | |
| DE3015655A1 (de) | Fluoranverbindungen, verfahren zu deren herstellung und deren anwendung in aufzeichnungsboegen | |
| DE3119053A1 (de) | Waermeempfindliches aufzeichnungsmaterial | |
| DE69410102T2 (de) | Druckempfindliche aufzeichnungsmaterialien | |
| DE3618562A1 (de) | Fluoranverbindung und sie enthaltende farbbildende aufzeichnungsmaterialien |
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): BE DE ES FR GB IT |
|
| 17P | Request for examination filed |
Effective date: 19951009 |
|
| GRAG | Despatch of communication of intention to grant |
Free format text: ORIGINAL CODE: EPIDOS AGRA |
|
| 17Q | First examination report despatched |
Effective date: 19961119 |
|
| 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): BE DE ES FR GB IT |
|
| GBT | Gb: translation of ep patent filed (gb section 77(6)(a)/1977) |
Effective date: 19970808 |
|
| REF | Corresponds to: |
Ref document number: 59500455 Country of ref document: DE Date of ref document: 19970911 |
|
| ITF | It: translation for a ep patent filed | ||
| REG | Reference to a national code |
Ref country code: ES Ref legal event code: FG2A Ref document number: 2105793 Country of ref document: ES Kind code of ref document: T3 |
|
| 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: DE Payment date: 20000214 Year of fee payment: 6 |
|
| PGFP | Annual fee paid to national office [announced via postgrant information from national office to epo] |
Ref country code: GB Payment date: 20000301 Year of fee payment: 6 |
|
| PGFP | Annual fee paid to national office [announced via postgrant information from national office to epo] |
Ref country code: ES Payment date: 20000306 Year of fee payment: 6 |
|
| PGFP | Annual fee paid to national office [announced via postgrant information from national office to epo] |
Ref country code: FR Payment date: 20000315 Year of fee payment: 6 |
|
| PGFP | Annual fee paid to national office [announced via postgrant information from national office to epo] |
Ref country code: BE Payment date: 20000329 Year of fee payment: 6 |
|
| 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: 20010306 |
|
| PG25 | Lapsed in a contracting state [announced via postgrant information from national office to epo] |
Ref country code: ES Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES Effective date: 20010307 |
|
| 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: 20010331 |
|
| BERE | Be: lapsed |
Owner name: BAYER A.G. Effective date: 20010331 |
|
| GBPC | Gb: european patent ceased through non-payment of renewal fee |
Effective date: 20010306 |
|
| 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: 20011130 |
|
| 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: DE Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES Effective date: 20020101 |
|
| REG | Reference to a national code |
Ref country code: ES Ref legal event code: FD2A Effective date: 20030303 |
|
| 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: 20050306 |