EP1504149B1 - Verfahren zum aufhellen von textilen materialien - Google Patents
Verfahren zum aufhellen von textilen materialien Download PDFInfo
- Publication number
- EP1504149B1 EP1504149B1 EP03717323A EP03717323A EP1504149B1 EP 1504149 B1 EP1504149 B1 EP 1504149B1 EP 03717323 A EP03717323 A EP 03717323A EP 03717323 A EP03717323 A EP 03717323A EP 1504149 B1 EP1504149 B1 EP 1504149B1
- Authority
- EP
- European Patent Office
- Prior art keywords
- weight
- compound
- oder
- alkyl
- compounds
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired - Lifetime
Links
- 238000000034 method Methods 0.000 title claims abstract description 43
- 239000004753 textile Substances 0.000 title claims abstract description 30
- 238000005282 brightening Methods 0.000 title claims abstract description 29
- 239000000463 material Substances 0.000 title claims abstract description 25
- 150000001875 compounds Chemical class 0.000 claims abstract description 74
- HTSGKJQDMSTCGS-UHFFFAOYSA-N 1,4-bis(4-chlorophenyl)-2-(4-methylphenyl)sulfonylbutane-1,4-dione Chemical compound C1=CC(C)=CC=C1S(=O)(=O)C(C(=O)C=1C=CC(Cl)=CC=1)CC(=O)C1=CC=C(Cl)C=C1 HTSGKJQDMSTCGS-UHFFFAOYSA-N 0.000 claims abstract description 17
- 230000003287 optical effect Effects 0.000 claims abstract description 12
- 239000000203 mixture Substances 0.000 claims description 43
- -1 2-ethylhexyl Chemical group 0.000 claims description 29
- 239000000975 dye Substances 0.000 claims description 28
- 239000002270 dispersing agent Substances 0.000 claims description 15
- 229920000728 polyester Polymers 0.000 claims description 15
- 238000009472 formulation Methods 0.000 claims description 10
- 239000000987 azo dye Substances 0.000 claims description 8
- 239000000654 additive Substances 0.000 claims description 7
- 150000004056 anthraquinones Chemical class 0.000 claims description 7
- 125000001434 methanylylidene group Chemical group [H]C#[*] 0.000 claims description 7
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 7
- 235000019239 indanthrene blue RS Nutrition 0.000 claims description 3
- NLFBCYMMUAKCPC-KQQUZDAGSA-N ethyl (e)-3-[3-amino-2-cyano-1-[(e)-3-ethoxy-3-oxoprop-1-enyl]sulfanyl-3-oxoprop-1-enyl]sulfanylprop-2-enoate Chemical compound CCOC(=O)\C=C\SC(=C(C#N)C(N)=O)S\C=C\C(=O)OCC NLFBCYMMUAKCPC-KQQUZDAGSA-N 0.000 claims 1
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 31
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 20
- 229910052739 hydrogen Inorganic materials 0.000 description 19
- 239000001257 hydrogen Substances 0.000 description 17
- 125000004178 (C1-C4) alkyl group Chemical group 0.000 description 12
- 125000000229 (C1-C4)alkoxy group Chemical group 0.000 description 12
- 125000004430 oxygen atom Chemical group O* 0.000 description 12
- 125000001033 ether group Chemical group 0.000 description 11
- 150000002431 hydrogen Chemical class 0.000 description 11
- 229910052736 halogen Inorganic materials 0.000 description 10
- 150000002367 halogens Chemical class 0.000 description 10
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 10
- 150000003254 radicals Chemical class 0.000 description 10
- AKEJUJNQAAGONA-UHFFFAOYSA-N sulfur trioxide Chemical compound O=S(=O)=O AKEJUJNQAAGONA-UHFFFAOYSA-N 0.000 description 10
- 125000004093 cyano group Chemical group *C#N 0.000 description 9
- 230000000694 effects Effects 0.000 description 8
- 125000000217 alkyl group Chemical group 0.000 description 7
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 6
- 239000000460 chlorine Substances 0.000 description 6
- 229910052801 chlorine Inorganic materials 0.000 description 6
- 239000004744 fabric Substances 0.000 description 6
- 125000001544 thienyl group Chemical group 0.000 description 6
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical compound [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 description 5
- IAYPIBMASNFSPL-UHFFFAOYSA-N Ethylene oxide Chemical class C1CO1 IAYPIBMASNFSPL-UHFFFAOYSA-N 0.000 description 5
- 150000002989 phenols Chemical class 0.000 description 5
- 239000011734 sodium Substances 0.000 description 5
- 125000004454 (C1-C6) alkoxycarbonyl group Chemical group 0.000 description 4
- 125000004209 (C1-C8) alkyl group Chemical group 0.000 description 4
- KEQGZUUPPQEDPF-UHFFFAOYSA-N 1,3-dichloro-5,5-dimethylimidazolidine-2,4-dione Chemical compound CC1(C)N(Cl)C(=O)N(Cl)C1=O KEQGZUUPPQEDPF-UHFFFAOYSA-N 0.000 description 4
- PAYRUJLWNCNPSJ-UHFFFAOYSA-N Aniline Chemical compound NC1=CC=CC=C1 PAYRUJLWNCNPSJ-UHFFFAOYSA-N 0.000 description 4
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 4
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 4
- 125000001797 benzyl group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C([H])([H])* 0.000 description 4
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Substances BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 description 4
- 229910052794 bromium Inorganic materials 0.000 description 4
- XTHPWXDJESJLNJ-UHFFFAOYSA-N chlorosulfonic acid Substances OS(Cl)(=O)=O XTHPWXDJESJLNJ-UHFFFAOYSA-N 0.000 description 4
- QPJDMGCKMHUXFD-UHFFFAOYSA-N cyanogen chloride Chemical compound ClC#N QPJDMGCKMHUXFD-UHFFFAOYSA-N 0.000 description 4
- 125000005117 dialkylcarbamoyl group Chemical group 0.000 description 4
- 150000002148 esters Chemical class 0.000 description 4
- 125000000623 heterocyclic group Chemical group 0.000 description 4
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 4
- 229910052760 oxygen Inorganic materials 0.000 description 4
- 239000001301 oxygen Substances 0.000 description 4
- 125000003170 phenylsulfonyl group Chemical group C1(=CC=CC=C1)S(=O)(=O)* 0.000 description 4
- 238000002360 preparation method Methods 0.000 description 4
- 239000000126 substance Substances 0.000 description 4
- 125000001424 substituent group Chemical group 0.000 description 4
- 125000000008 (C1-C10) alkyl group Chemical group 0.000 description 3
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 3
- PJOUURZOYJMYPA-UHFFFAOYSA-N OClC#N Chemical compound OClC#N PJOUURZOYJMYPA-UHFFFAOYSA-N 0.000 description 3
- 241001085205 Prenanthella exigua Species 0.000 description 3
- 229910052799 carbon Inorganic materials 0.000 description 3
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 3
- 238000006243 chemical reaction Methods 0.000 description 3
- 239000003795 chemical substances by application Substances 0.000 description 3
- 230000000052 comparative effect Effects 0.000 description 3
- 229920001577 copolymer Polymers 0.000 description 3
- 238000002474 experimental method Methods 0.000 description 3
- 229910052757 nitrogen Inorganic materials 0.000 description 3
- 125000000951 phenoxy group Chemical group [H]C1=C([H])C([H])=C(O*)C([H])=C1[H] 0.000 description 3
- 125000003837 (C1-C20) alkyl group Chemical group 0.000 description 2
- 125000004769 (C1-C4) alkylsulfonyl group Chemical group 0.000 description 2
- 125000006700 (C1-C6) alkylthio group Chemical group 0.000 description 2
- 125000004105 2-pyridyl group Chemical group N1=C([*])C([H])=C([H])C([H])=C1[H] 0.000 description 2
- 125000003349 3-pyridyl group Chemical group N1=C([H])C([*])=C([H])C([H])=C1[H] 0.000 description 2
- 0 CC1SC(N(C)*)=NC1* Chemical compound CC1SC(N(C)*)=NC1* 0.000 description 2
- MYMOFIZGZYHOMD-UHFFFAOYSA-N Dioxygen Chemical compound O=O MYMOFIZGZYHOMD-UHFFFAOYSA-N 0.000 description 2
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 2
- PXGOKWXKJXAPGV-UHFFFAOYSA-N Fluorine Chemical compound FF PXGOKWXKJXAPGV-UHFFFAOYSA-N 0.000 description 2
- KIAAMJMIIHTGBH-KQQUZDAGSA-N N#Cc1ccc(/C=C/c2ccc(/C=C/c(cc3)ccc3C#N)cc2)cc1 Chemical compound N#Cc1ccc(/C=C/c2ccc(/C=C/c(cc3)ccc3C#N)cc2)cc1 KIAAMJMIIHTGBH-KQQUZDAGSA-N 0.000 description 2
- WHNWPMSKXPGLAX-UHFFFAOYSA-N N-Vinyl-2-pyrrolidone Chemical compound C=CN1CCCC1=O WHNWPMSKXPGLAX-UHFFFAOYSA-N 0.000 description 2
- UFWIBTONFRDIAS-UHFFFAOYSA-N Naphthalene Chemical compound C1=CC=CC2=CC=CC=C21 UFWIBTONFRDIAS-UHFFFAOYSA-N 0.000 description 2
- ATUOYWHBWRKTHZ-UHFFFAOYSA-N Propane Chemical compound CCC ATUOYWHBWRKTHZ-UHFFFAOYSA-N 0.000 description 2
- GOOHAUXETOMSMM-UHFFFAOYSA-N Propylene oxide Chemical compound CC1CO1 GOOHAUXETOMSMM-UHFFFAOYSA-N 0.000 description 2
- KAESVJOAVNADME-UHFFFAOYSA-N Pyrrole Chemical compound C=1C=CNC=1 KAESVJOAVNADME-UHFFFAOYSA-N 0.000 description 2
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 2
- YTPLMLYBLZKORZ-UHFFFAOYSA-N Thiophene Chemical compound C=1C=CSC=1 YTPLMLYBLZKORZ-UHFFFAOYSA-N 0.000 description 2
- 239000002253 acid Substances 0.000 description 2
- 229910052783 alkali metal Inorganic materials 0.000 description 2
- 125000000129 anionic group Chemical group 0.000 description 2
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 2
- ZYGHJZDHTFUPRJ-UHFFFAOYSA-N benzo-alpha-pyrone Natural products C1=CC=C2OC(=O)C=CC2=C1 ZYGHJZDHTFUPRJ-UHFFFAOYSA-N 0.000 description 2
- 239000003139 biocide Substances 0.000 description 2
- 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 2
- 125000003917 carbamoyl group Chemical group [H]N([H])C(*)=O 0.000 description 2
- 239000003054 catalyst Substances 0.000 description 2
- 125000001309 chloro group Chemical group Cl* 0.000 description 2
- 235000001671 coumarin Nutrition 0.000 description 2
- 125000000332 coumarinyl group Chemical class O1C(=O)C(=CC2=CC=CC=C12)* 0.000 description 2
- 230000008878 coupling Effects 0.000 description 2
- 238000010168 coupling process Methods 0.000 description 2
- 238000005859 coupling reaction Methods 0.000 description 2
- 125000000113 cyclohexyl group Chemical group [H]C1([H])C([H])([H])C([H])([H])C([H])(*)C([H])([H])C1([H])[H] 0.000 description 2
- 125000005202 dialkylaminocarbonyloxy group Chemical group 0.000 description 2
- 125000000664 diazo group Chemical group [N-]=[N+]=[*] 0.000 description 2
- 229910052731 fluorine Inorganic materials 0.000 description 2
- 239000011737 fluorine Substances 0.000 description 2
- 125000002485 formyl group Chemical group [H]C(*)=O 0.000 description 2
- 125000000524 functional group Chemical group 0.000 description 2
- 125000001972 isopentyl group Chemical group [H]C([H])([H])C([H])(C([H])([H])[H])C([H])([H])C([H])([H])* 0.000 description 2
- 125000000956 methoxy group Chemical group [H]C([H])([H])O* 0.000 description 2
- 125000004108 n-butyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 2
- 125000000449 nitro group Chemical class [O-][N+](*)=O 0.000 description 2
- HVAMZGADVCBITI-UHFFFAOYSA-N pent-4-enoic acid Chemical compound OC(=O)CCC=C HVAMZGADVCBITI-UHFFFAOYSA-N 0.000 description 2
- 125000003356 phenylsulfanyl group Chemical group [*]SC1=C([H])C([H])=C([H])C([H])=C1[H] 0.000 description 2
- 239000004033 plastic Substances 0.000 description 2
- 229920003023 plastic Polymers 0.000 description 2
- 229920001983 poloxamer Polymers 0.000 description 2
- BBEAQIROQSPTKN-UHFFFAOYSA-N pyrene Chemical compound C1=CC=C2C=CC3=CC=CC4=CC=C1C2=C43 BBEAQIROQSPTKN-UHFFFAOYSA-N 0.000 description 2
- 125000004076 pyridyl group Chemical group 0.000 description 2
- 150000003839 salts Chemical class 0.000 description 2
- 229910052708 sodium Inorganic materials 0.000 description 2
- 238000004611 spectroscopical analysis Methods 0.000 description 2
- 239000000979 synthetic dye Substances 0.000 description 2
- 125000000999 tert-butyl group Chemical group [H]C([H])([H])C(*)(C([H])([H])[H])C([H])([H])[H] 0.000 description 2
- 125000002023 trifluoromethyl group Chemical group FC(F)(F)* 0.000 description 2
- 125000004191 (C1-C6) alkoxy group Chemical group 0.000 description 1
- WIJQCPIRWXSWQG-UHFFFAOYSA-N 1,2-benzothiazol-3-amine Chemical class C1=CC=C2C(N)=NSC2=C1 WIJQCPIRWXSWQG-UHFFFAOYSA-N 0.000 description 1
- NGQSLSMAEVWNPU-YTEMWHBBSA-N 1,2-bis[(e)-2-phenylethenyl]benzene Chemical class C=1C=CC=CC=1/C=C/C1=CC=CC=C1\C=C\C1=CC=CC=C1 NGQSLSMAEVWNPU-YTEMWHBBSA-N 0.000 description 1
- IYCKMNAVTMOAKD-UHFFFAOYSA-N 1,2-thiazol-3-amine Chemical class NC=1C=CSN=1 IYCKMNAVTMOAKD-UHFFFAOYSA-N 0.000 description 1
- 150000000183 1,3-benzoxazoles Chemical class 0.000 description 1
- RAIPHJJURHTUIC-UHFFFAOYSA-N 1,3-thiazol-2-amine Chemical class NC1=NC=CS1 RAIPHJJURHTUIC-UHFFFAOYSA-N 0.000 description 1
- IJAAWBHHXIWAHM-UHFFFAOYSA-N 1,4-bis(2-phenylethenyl)benzene Chemical class C=1C=CC=CC=1C=CC(C=C1)=CC=C1C=CC1=CC=CC=C1 IJAAWBHHXIWAHM-UHFFFAOYSA-N 0.000 description 1
- KZYAYVSWIPZDKL-UHFFFAOYSA-N 1,4-diamino-2,3-dichloroanthracene-9,10-dione Chemical compound O=C1C2=CC=CC=C2C(=O)C2=C1C(N)=C(Cl)C(Cl)=C2N KZYAYVSWIPZDKL-UHFFFAOYSA-N 0.000 description 1
- HXWQJYVUJPBQEW-UHFFFAOYSA-N 1-phenyl-4-[2-(4-phenylphenyl)ethenyl]benzene Chemical class C=1C=C(C=2C=CC=CC=2)C=CC=1C=CC(C=C1)=CC=C1C1=CC=CC=C1 HXWQJYVUJPBQEW-UHFFFAOYSA-N 0.000 description 1
- 238000005160 1H NMR spectroscopy Methods 0.000 description 1
- TXSHHSFIYJYWKR-UHFFFAOYSA-N 2-[1-(1,3-benzoxazol-2-yl)naphthalen-2-yl]-1,3-benzoxazole Chemical class C1=CC=C2OC(C3=C4C=CC=CC4=CC=C3C=3OC4=CC=CC=C4N=3)=NC2=C1 TXSHHSFIYJYWKR-UHFFFAOYSA-N 0.000 description 1
- PHBSPYGHSRVOHY-UHFFFAOYSA-N 2-[2-(1,3-benzoxazol-2-yl)thiophen-3-yl]-1,3-benzoxazole Chemical class C1=CC=C2OC(C3=C(C=4OC5=CC=CC=C5N=4)C=CS3)=NC2=C1 PHBSPYGHSRVOHY-UHFFFAOYSA-N 0.000 description 1
- 125000000954 2-hydroxyethyl group Chemical group [H]C([*])([H])C([H])([H])O[H] 0.000 description 1
- 125000003229 2-methylhexyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])(C([H])([H])[H])C([H])([H])* 0.000 description 1
- 125000003542 3-methylbutan-2-yl group Chemical group [H]C([H])([H])C([H])(*)C([H])(C([H])([H])[H])C([H])([H])[H] 0.000 description 1
- MPIFMUARWKUNQZ-UHFFFAOYSA-N 4-[2-(2-phenylethenyl)phenyl]-2h-benzo[e]benzotriazole Chemical class C=1C=CC=C(C=2C=3N=NNC=3C3=CC=CC=C3C=2)C=1C=CC1=CC=CC=C1 MPIFMUARWKUNQZ-UHFFFAOYSA-N 0.000 description 1
- WEKUJYSPUDQAEH-UHFFFAOYSA-N Cc(cc1)cc2c1[o]c(-c1ccc(-c3nc(cc(C)cc4)c4[o]3)c3c1cccc3)n2 Chemical compound Cc(cc1)cc2c1[o]c(-c1ccc(-c3nc(cc(C)cc4)c4[o]3)c3c1cccc3)n2 WEKUJYSPUDQAEH-UHFFFAOYSA-N 0.000 description 1
- VKRZNAWSCAUDRQ-BQYQJAHWSA-N Cc(cc1)cc2c1[o]c(/C=C/c1nc(cc(C)cc3)c3[o]1)n2 Chemical compound Cc(cc1)cc2c1[o]c(/C=C/c1nc(cc(C)cc3)c3[o]1)n2 VKRZNAWSCAUDRQ-BQYQJAHWSA-N 0.000 description 1
- QQKFUTGTZXPBGA-PLNGDYQASA-N Cc1ccc2[o]c(-c3ccc(/C=C\c(cc4)ccc4C(OC)=O)cc3)nc2c1 Chemical compound Cc1ccc2[o]c(-c3ccc(/C=C\c(cc4)ccc4C(OC)=O)cc3)nc2c1 QQKFUTGTZXPBGA-PLNGDYQASA-N 0.000 description 1
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 1
- 239000005977 Ethylene Substances 0.000 description 1
- AVXURJPOCDRRFD-UHFFFAOYSA-N Hydroxylamine Chemical class ON AVXURJPOCDRRFD-UHFFFAOYSA-N 0.000 description 1
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 1
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 1
- 229920002257 Plurafac® Polymers 0.000 description 1
- 239000004952 Polyamide Substances 0.000 description 1
- FZWLAAWBMGSTSO-UHFFFAOYSA-N Thiazole Chemical compound C1=CSC=N1 FZWLAAWBMGSTSO-UHFFFAOYSA-N 0.000 description 1
- XTXRWKRVRITETP-UHFFFAOYSA-N Vinyl acetate Chemical compound CC(=O)OC=C XTXRWKRVRITETP-UHFFFAOYSA-N 0.000 description 1
- 241001106476 Violaceae Species 0.000 description 1
- 238000007239 Wittig reaction Methods 0.000 description 1
- 239000006096 absorbing agent Substances 0.000 description 1
- 125000000738 acetamido group Chemical group [H]C([H])([H])C(=O)N([H])[*] 0.000 description 1
- 230000002378 acidificating effect Effects 0.000 description 1
- 150000007513 acids Chemical class 0.000 description 1
- 150000001298 alcohols Chemical class 0.000 description 1
- 125000001931 aliphatic group Chemical group 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 150000008044 alkali metal hydroxides Chemical class 0.000 description 1
- 150000001340 alkali metals Chemical class 0.000 description 1
- 125000005236 alkanoylamino group Chemical group 0.000 description 1
- 125000003545 alkoxy group Chemical group 0.000 description 1
- 125000004453 alkoxycarbonyl group Chemical group 0.000 description 1
- 125000003282 alkyl amino group Chemical group 0.000 description 1
- 125000004656 alkyl sulfonylamino group Chemical group 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- CJDPJFRMHVXWPT-UHFFFAOYSA-N barium sulfide Chemical compound [S-2].[Ba+2] CJDPJFRMHVXWPT-UHFFFAOYSA-N 0.000 description 1
- XJHABGPPCLHLLV-UHFFFAOYSA-N benzo[de]isoquinoline-1,3-dione Chemical class C1=CC(C(=O)NC2=O)=C3C2=CC=CC3=C1 XJHABGPPCLHLLV-UHFFFAOYSA-N 0.000 description 1
- 230000033228 biological regulation Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 239000004305 biphenyl Substances 0.000 description 1
- 235000010290 biphenyl Nutrition 0.000 description 1
- 125000006267 biphenyl group Chemical group 0.000 description 1
- VCCBEIPGXKNHFW-UHFFFAOYSA-N biphenyl-4,4'-diol Chemical compound C1=CC(O)=CC=C1C1=CC=C(O)C=C1 VCCBEIPGXKNHFW-UHFFFAOYSA-N 0.000 description 1
- 239000001045 blue dye Substances 0.000 description 1
- CODNYICXDISAEA-UHFFFAOYSA-N bromine monochloride Chemical compound BrCl CODNYICXDISAEA-UHFFFAOYSA-N 0.000 description 1
- 150000001735 carboxylic acids Chemical class 0.000 description 1
- ZCDOYSPFYFSLEW-UHFFFAOYSA-N chromate(2-) Chemical compound [O-][Cr]([O-])(=O)=O ZCDOYSPFYFSLEW-UHFFFAOYSA-N 0.000 description 1
- 238000004587 chromatography analysis Methods 0.000 description 1
- 235000014113 dietary fatty acids Nutrition 0.000 description 1
- 239000000986 disperse dye Substances 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- UIWXSTHGICQLQT-UHFFFAOYSA-N ethenyl propanoate Chemical compound CCC(=O)OC=C UIWXSTHGICQLQT-UHFFFAOYSA-N 0.000 description 1
- 125000001301 ethoxy group Chemical group [H]C([H])([H])C([H])([H])O* 0.000 description 1
- 229930195729 fatty acid Natural products 0.000 description 1
- 239000000194 fatty acid Substances 0.000 description 1
- 150000004665 fatty acids Chemical class 0.000 description 1
- 150000002191 fatty alcohols Chemical class 0.000 description 1
- 239000000835 fiber Substances 0.000 description 1
- GVEPBJHOBDJJJI-UHFFFAOYSA-N fluoranthrene Natural products C1=CC(C2=CC=CC=C22)=C3C2=CC=CC3=C1 GVEPBJHOBDJJJI-UHFFFAOYSA-N 0.000 description 1
- 125000005059 halophenyl group Chemical group 0.000 description 1
- 125000005842 heteroatom Chemical group 0.000 description 1
- 125000002883 imidazolyl group Chemical group 0.000 description 1
- UHOKSCJSTAHBSO-UHFFFAOYSA-N indanthrone blue Chemical compound C1=CC=C2C(=O)C3=CC=C4NC5=C6C(=O)C7=CC=CC=C7C(=O)C6=CC=C5NC4=C3C(=O)C2=C1 UHOKSCJSTAHBSO-UHFFFAOYSA-N 0.000 description 1
- 150000002475 indoles Chemical class 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
- 125000004491 isohexyl group Chemical group C(CCC(C)C)* 0.000 description 1
- NYGZLYXAPMMJTE-UHFFFAOYSA-M metanil yellow Chemical group [Na+].[O-]S(=O)(=O)C1=CC=CC(N=NC=2C=CC(NC=3C=CC=CC=3)=CC=2)=C1 NYGZLYXAPMMJTE-UHFFFAOYSA-M 0.000 description 1
- 238000010137 moulding (plastic) Methods 0.000 description 1
- SYSQUGFVNFXIIT-UHFFFAOYSA-N n-[4-(1,3-benzoxazol-2-yl)phenyl]-4-nitrobenzenesulfonamide Chemical class C1=CC([N+](=O)[O-])=CC=C1S(=O)(=O)NC1=CC=C(C=2OC3=CC=CC=C3N=2)C=C1 SYSQUGFVNFXIIT-UHFFFAOYSA-N 0.000 description 1
- 125000003136 n-heptyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 125000001280 n-hexyl group Chemical group C(CCCCC)* 0.000 description 1
- 125000000740 n-pentyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 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
- 238000006386 neutralization reaction Methods 0.000 description 1
- 125000004433 nitrogen atom Chemical group N* 0.000 description 1
- 239000004745 nonwoven fabric Substances 0.000 description 1
- NFBAXHOPROOJAW-UHFFFAOYSA-N phenindione Chemical class O=C1C2=CC=CC=C2C(=O)C1C1=CC=CC=C1 NFBAXHOPROOJAW-UHFFFAOYSA-N 0.000 description 1
- ZUOUZKKEUPVFJK-UHFFFAOYSA-N phenylbenzene Natural products C1=CC=CC=C1C1=CC=CC=C1 ZUOUZKKEUPVFJK-UHFFFAOYSA-N 0.000 description 1
- 125000000843 phenylene group Chemical group C1(=C(C=CC=C1)*)* 0.000 description 1
- 229920002647 polyamide Polymers 0.000 description 1
- 229920002635 polyurethane Polymers 0.000 description 1
- 239000004814 polyurethane Substances 0.000 description 1
- 229910052700 potassium Inorganic materials 0.000 description 1
- 159000000001 potassium salts Chemical class 0.000 description 1
- 239000001294 propane Substances 0.000 description 1
- 150000003219 pyrazolines Chemical class 0.000 description 1
- ZZYXNRREDYWPLN-UHFFFAOYSA-N pyridine-2,3-diamine Chemical class NC1=CC=CN=C1N ZZYXNRREDYWPLN-UHFFFAOYSA-N 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
- 125000003548 sec-pentyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 150000001629 stilbenes Chemical class 0.000 description 1
- 125000005504 styryl group Chemical group 0.000 description 1
- 239000004094 surface-active agent Substances 0.000 description 1
- 230000002195 synergetic effect Effects 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- KUCOHFSKRZZVRO-UHFFFAOYSA-N terephthalaldehyde Chemical compound O=CC1=CC=C(C=O)C=C1 KUCOHFSKRZZVRO-UHFFFAOYSA-N 0.000 description 1
- CUWHXIJMTMMRTI-UHFFFAOYSA-N thiadiazol-4-amine Chemical class NC1=CSN=N1 CUWHXIJMTMMRTI-UHFFFAOYSA-N 0.000 description 1
- 150000003557 thiazoles Chemical class 0.000 description 1
- GLQWRXYOTXRDNH-UHFFFAOYSA-N thiophen-2-amine Chemical class NC1=CC=CS1 GLQWRXYOTXRDNH-UHFFFAOYSA-N 0.000 description 1
- 229930192474 thiophene Natural products 0.000 description 1
- 125000004306 triazinyl group Chemical group 0.000 description 1
- 239000000984 vat dye Substances 0.000 description 1
- YKSGNOMLAIJTLT-UHFFFAOYSA-N violanthrone Chemical compound C12=C3C4=CC=C2C2=CC=CC=C2C(=O)C1=CC=C3C1=CC=C2C(=O)C3=CC=CC=C3C3=CC=C4C1=C32 YKSGNOMLAIJTLT-UHFFFAOYSA-N 0.000 description 1
- 230000002087 whitening effect Effects 0.000 description 1
- 238000004383 yellowing Methods 0.000 description 1
Classifications
-
- D—TEXTILES; PAPER
- D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
- D06P—DYEING OR PRINTING TEXTILES; DYEING LEATHER, FURS OR SOLID MACROMOLECULAR SUBSTANCES IN ANY FORM
- D06P1/00—General processes of dyeing or printing textiles, or general processes of dyeing leather, furs, or solid macromolecular substances in any form, classified according to the dyes, pigments, or auxiliary substances employed
- D06P1/02—General processes of dyeing or printing textiles, or general processes of dyeing leather, furs, or solid macromolecular substances in any form, classified according to the dyes, pigments, or auxiliary substances employed using azo dyes
- D06P1/04—General processes of dyeing or printing textiles, or general processes of dyeing leather, furs, or solid macromolecular substances in any form, classified according to the dyes, pigments, or auxiliary substances employed using azo dyes not containing metal
- D06P1/08—General processes of dyeing or printing textiles, or general processes of dyeing leather, furs, or solid macromolecular substances in any form, classified according to the dyes, pigments, or auxiliary substances employed using azo dyes not containing metal cationic azo dyes
-
- D—TEXTILES; PAPER
- D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
- D06L—DRY-CLEANING, WASHING OR BLEACHING FIBRES, FILAMENTS, THREADS, YARNS, FABRICS, FEATHERS OR MADE-UP FIBROUS GOODS; BLEACHING LEATHER OR FURS
- D06L4/00—Bleaching fibres, filaments, threads, yarns, fabrics, feathers or made-up fibrous goods; Bleaching leather or furs
- D06L4/60—Optical bleaching or brightening
-
- C—CHEMISTRY; METALLURGY
- C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
- C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
- C11D1/00—Detergent compositions based essentially on surface-active compounds; Use of these compounds as a detergent
- C11D1/38—Cationic compounds
- C11D1/62—Quaternary ammonium compounds
-
- C—CHEMISTRY; METALLURGY
- C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
- C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
- C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
- C11D3/39—Organic or inorganic per-compounds
-
- C—CHEMISTRY; METALLURGY
- C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
- C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
- C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
- C11D3/40—Dyes ; Pigments
- C11D3/42—Brightening agents ; Blueing agents
-
- D—TEXTILES; PAPER
- D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
- D06L—DRY-CLEANING, WASHING OR BLEACHING FIBRES, FILAMENTS, THREADS, YARNS, FABRICS, FEATHERS OR MADE-UP FIBROUS GOODS; BLEACHING LEATHER OR FURS
- D06L4/00—Bleaching fibres, filaments, threads, yarns, fabrics, feathers or made-up fibrous goods; Bleaching leather or furs
- D06L4/60—Optical bleaching or brightening
- D06L4/614—Optical bleaching or brightening in aqueous solvents
- D06L4/636—Optical bleaching or brightening in aqueous solvents with disperse brighteners
-
- D—TEXTILES; PAPER
- D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
- D06L—DRY-CLEANING, WASHING OR BLEACHING FIBRES, FILAMENTS, THREADS, YARNS, FABRICS, FEATHERS OR MADE-UP FIBROUS GOODS; BLEACHING LEATHER OR FURS
- D06L4/00—Bleaching fibres, filaments, threads, yarns, fabrics, feathers or made-up fibrous goods; Bleaching leather or furs
- D06L4/60—Optical bleaching or brightening
- D06L4/657—Optical bleaching or brightening combined with other treatments, e.g. finishing, bleaching, softening, dyeing or pigment printing
-
- D—TEXTILES; PAPER
- D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
- D06P—DYEING OR PRINTING TEXTILES; DYEING LEATHER, FURS OR SOLID MACROMOLECULAR SUBSTANCES IN ANY FORM
- D06P1/00—General processes of dyeing or printing textiles, or general processes of dyeing leather, furs, or solid macromolecular substances in any form, classified according to the dyes, pigments, or auxiliary substances employed
- D06P1/13—General processes of dyeing or printing textiles, or general processes of dyeing leather, furs, or solid macromolecular substances in any form, classified according to the dyes, pigments, or auxiliary substances employed using azomethine dyes
-
- D—TEXTILES; PAPER
- D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
- D06P—DYEING OR PRINTING TEXTILES; DYEING LEATHER, FURS OR SOLID MACROMOLECULAR SUBSTANCES IN ANY FORM
- D06P1/00—General processes of dyeing or printing textiles, or general processes of dyeing leather, furs, or solid macromolecular substances in any form, classified according to the dyes, pigments, or auxiliary substances employed
- D06P1/16—General processes of dyeing or printing textiles, or general processes of dyeing leather, furs, or solid macromolecular substances in any form, classified according to the dyes, pigments, or auxiliary substances employed using dispersed, e.g. acetate, dyestuffs
- D06P1/18—Azo dyes
-
- D—TEXTILES; PAPER
- D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
- D06P—DYEING OR PRINTING TEXTILES; DYEING LEATHER, FURS OR SOLID MACROMOLECULAR SUBSTANCES IN ANY FORM
- D06P1/00—General processes of dyeing or printing textiles, or general processes of dyeing leather, furs, or solid macromolecular substances in any form, classified according to the dyes, pigments, or auxiliary substances employed
- D06P1/16—General processes of dyeing or printing textiles, or general processes of dyeing leather, furs, or solid macromolecular substances in any form, classified according to the dyes, pigments, or auxiliary substances employed using dispersed, e.g. acetate, dyestuffs
- D06P1/20—Anthraquinone dyes
Definitions
- the present invention relates to a process for brightening textile materials by treatment with optical brighteners in aqueous liquor, characterized in that 20 to 80 wt .-%, each based on the sum of all brightening compounds of the compound I wherein up to 40 mol% of I may be present as a cis isomer, and 80 to 20 wt .-% of at least one compound II selected from and 0 to 30 wt .-% of at least one compound of general formula III wherein R is selected from C 4 -C 10 alkyl, wherein the treatment is optionally carried out in the presence of one or more blue or violet Nuancierfarbstoffe from the class of anthraquinones, azo dyes or methine dyes.
- Optical brighteners are of great economic importance as aids for the textile industry and for the plastics industry. Many compounds are known for their ability to give a white color to textiles or plastics. However, most of these known compounds also have disadvantages. Thus, compounds of general formula 1 from EP 0 023 026, where, for example, the radicals R 1 and R 2 may be, for example, hydrogen, fluorine, chlorine, phenyl, trifluoromethyl, alkyl or numerous other radicals and wherein V is selected from
- EP 0 023 026 discloses mixtures of optical brighteners containing from 0.05 to 0.95 parts by weight of one or more compounds of the formula 2 p wherein A represents a phenyl group substituted by an ortho- or para-cyano group, and 0.95 to 0.05 parts by weight of one or more other compounds selected from a wide variety of other compounds.
- radicals R 1 and R 2 can denote: hydrogen, fluorine, chlorine, phenyl, trifluoromethyl, C 1 -C 9 -alkyl, alkoxy, alkylamino and numerous further radicals which are listed on page 2, lines 14-21, and V is as defined above, or with compounds of the formula 3b-4b wherein B is a functional group, R 1 and R 2 are as defined above, n is an integer, R 3 is hydrogen and C 1 -C 4 alkoxy, R 4 is C 1 -C 4 alkoxy and R 5 is, for example is selected from C 1 -C 6 -alkyl and B is preferably a functional group, or further with compounds of the formulas 5b to 6b the radicals R 6 to R 10 are each selected from different groups and V is defined as above.
- the brighteners thus defined are made according to different methods applied and give a good whiteness to CIE.
- EP-A 0 023 028 claims mixtures comprising from 0.05 to 0.95 parts by weight of a mixture consisting of from 20 to 100% by weight of 2 p, o ' and 0 to 80% by weight of the compounds 2 p, p 'and 2 o, o' respectively and 0.05 to 0.95 parts by weight of one or more derivatives of the formulas 1a and 3a to 6a, can be used as optical brighteners, wherein 1a and 3a to 6a are defined substantially analogously to EP-A 0 023 026.
- the mixtures show a synergistic effect, which is the whiteness according to CIE, and good lightfastness.
- EP-A 0 321 393 the use of compounds of the type 1 b, in which D denotes a C 1 -C 4 -alkyl group, and compounds of the formula 2 in brightener dispersions.
- the compounds of the type 1 b or 2 either alone or as specific mixtures, referred to in the cited document as mixtures 1 to 6 (pages 6-8) are disclosed. It is essential to the invention in EP-A 0 321 393 that the mixture contains a copolymer of 2-vinylpyrrolidone with 3-vinylpropionic acid (page 9, line 18).
- a bright white is available on a wide range of products from of great economic importance, for example in textiles and in plastic moldings.
- the brightener a have better yield, i. you reach with less Brightener an equal or greater effect.
- the textile exist Materials of synthetic polyester or mixtures containing 45 to 90% by weight of polyester.
- aqueous liquors in the context of the present invention are also understood such fleets, in addition to water as the main component up to 40% by volume of one or more further solvents contain, for example, alcohols such as ethanol.
- the pH the liquors used in the invention is preferably from 3 to 12, preferably from 3 to 8.
- textile materials are treated with from 20 to 80, preferably from 20 to 70,% by weight and more preferably from 30 to 50% by weight of the compound of the formula I. wherein up to 40 mol% of I may be present in the form of the corresponding cis isomer, and 80 to 20 wt .-% of at least one of the compounds II and 0 to 30 wt .-% of a compound of general formula III wherein R is selected from C 4 -C 10 alkyl, for example n-butyl, iso-butyl, sec-butyl, tert-butyl, n-pentyl, iso-pentyl, sec-pentyl, neo-pentyl, 1 , 2-dimethylpropyl, iso-amyl, n-hexyl, iso-hexyl, sec-hexyl, n-heptyl, iso-heptyl, n-o
- DicyanostyrylENSen II p, o ', II m, p', II p, p 'or II o, o' are used in the form of their trans isomers. They usually contain 0.01 to 10, preferably 0.1 to 5 mol% of isomers having at least one cis double bond, wherein the Proportion of cis isomers by spectroscopic Methods is determined. You are through a double Wittig reaction from terephthalaldehyde and the corresponding cyanobenzylphosphorylidene easily accessible.
- Suitable Nuancierfarbstoffe usually come from the class of disperse dyes and vat dyes. These are common names. In the color index are such Dyes, e.g. under the name Disperse Blue or Disperse Violet or Vat Blue or Vat Violet listed.
- blue dyes from the class of anthraquinones, Azo dyes or methine dyes are particularly suitable.
- Dyes of the formula A2 are e.g. in the US-A 2,628,963, US-A 3,835,154, DE-A 12 66 425 or DE-A 20 16 794 described.
- Dyes which obey the formulas A1, A3 and A4 are e.g. from K. Venkataraman, "The Chemistry of Synthetic Dyes ", Vol. 3, pages 391 to 423, 1970.
- Suitable azo dyes are in particular monoazo dyes with a diazo component from the aniline or heterocyclic series and a coupling component of the aniline or heterocyclic Line.
- Suitable heterocycles of which the diazo components derived, e.g. from the class of aminothiophenes, aminothiazoles, Aminoisothiazoles, aminothiadiazoles or aminobenzisothiazoles.
- Suitable heterocycles of which the coupling components derived, e.g. from the class of thiazoles or diaminopyridines.
- dyes of formula B1 and B2 are e.g. in US 5,283,326 or US 5,145,952. From EP-A 0 087 616, EP-A 0 087 677, EP-A 0 121 875, EP-A 0 151 287 and US Pat. No. 4,960,873 are dyes the formula B3 known. From US 5,216,139 are dyes the formula B4 known. US 5,132,412 describes dyes of the type of formula B5. Dyes of the formulas B6 and B7 are e.g. in US Pat. No. 3,981,883, DE-A 31 12 427, EP-A 0 064 221 or in Venkataraman's "The Chemistry of Synthetic Dyes," Volume 3, Pages 444 to 447, described or may be mentioned after the there Methods are obtained.
- substituted alkyl radicals occur in formula C, as substituents, unless otherwise stated, for example phenyl, C 1 -C 4 -alkylphenyl, C 1 -C 4 -alkoxyphenyl, halophenyl, C 1 -C 8 -alkanoyloxy, C 1 - C 8 -alkylaminocarbonyloxy, C 1 -C 20 -alkoxycarbonyl, C 1 -C 20 -alkoxycarbonyloxy, wherein the alkyl chain of the last two radicals optionally interrupted by 1 to 4 oxygen atoms in ether function and / or substituted by phenyl or phenoxy, halogen, hydroxy or cyano.
- the alkyl radicals generally have 1 or 2 substituents.
- alkyl radicals occur in formula C, which are represented by oxygen atoms are interrupted in ether function, so are, unless otherwise mentions such alkyl radicals which are substituted by 1 to 4 oxygen atoms, in particular 1 to 2 oxygen atoms, in ether function are interrupted.
- substituted phenyl or pyridyl radicals occur in formula C, suitable substituents are, for example, C 1 -C 8 -alkyl, C 1 -C 8 -alkoxy, halogen, in particular chlorine or bromine, or carboxyl.
- the phenyl or pyridyl radicals generally have 1 to 3 substituents.
- Residues Z 19 can be derived, for example, from components of pyrrole, thiazole, thiophene or indole series.
- Important radicals Z 19 are, for example, those of the formulas C 1 to C 4
- Such methine dyes are e.g. in the older German Patent application DE-A 44 03 083 described.
- the lightening of the textile materials is usually after the exhaust or thermosol process.
- the exhaust process usually works in an aqueous liquor Temperatures from 90 to 135, usually around 130 ° C. In the case of Application above 100 ° C must in an autoclave, a high pressure apparatus or a high pressure machine.
- the thermosol process is used at atmospheric pressure.
- the aufhellende textile Material In the exhaust process is usually the aufhellende textile Material at a temperature of 10 to 35 ° C in an aqueous Fleet brought that the optically brightening acting Compounds, optionally a blue or purple Nuancierfarbstoff or a mixture thereof and optionally Aggregate, e.g. Dispersants, carboxylic acids or alkali donors, contains and its pH is usually 3 to 12, preferably 3 to 8, is.
- the liquor ratio weight ratio of textiles Material: liquor
- the bath will then be within 15 to 30 minutes to a temperature of 90 to 130 ° C, preferably 95 to 100 ° C, heated and held at this temperature for 15 to 60 minutes. After that The lightened textile material is rinsed and dried.
- thermosol process is usually brightening textile material with an aqueous liquor that is the optical lightening substances, possibly a blue or purple Nuancierfarbstoff or mixtures thereof and optionally Contains aggregate (s.o.), padded.
- the fleet intake is generally 50 to 100%.
- the textile Dried material and at a temperature of 150 to 200 ° C for Fixed for 5 to 60 seconds.
- the dispersants used are preferably those dispersants, which are colorless and at temperatures up to at least 210 ° C stable against yellowing.
- Particularly suitable dispersants are e.g. anionic or nonionic, especially those from the class of ethylene oxide adducts with fatty alcohols, higher fatty acids or alkylphenols or ethylene diamine-ethylene oxide-propylene oxide adducts.
- the phenols of the formula VI or VII can be obtained by reacting bisphenol A (2,2- (p, p'-bishydroxydiphenyl) propane) or phenol with 4 or 2 mol of styrene in the presence of acid as catalyst.
- the alkoxylation can be carried out, for example, by the process described in US Pat. No. 2,979,528.
- the sulfuric acid half esters are obtained by reaction of the alkoxylation products made with chlorosulfonic acid or sulfur trioxide, the amount of chlorosulfonic acid or sulfur trioxide is chosen so that all free hydroxyl groups or only one a certain percentage is sulfated. In the latter case arise Mixtures of compounds of formula IV or V, the free and Contain sulfated hydroxyl groups.
- For use as surfactants become the obtained in the reaction half ester of sulfuric acid converted into water-soluble salts.
- the alkali metal salts e.g. the sodium or potassium salts
- chlorosulfonic acid are two Equivalent, one equivalent of basic sulfur trioxide Connections required. As the latter, it is expedient to use aqueous alkali metal hydroxide. In neutralization the temperature should not exceed 70 ° C.
- the obtained salts may be in the form of aqueous solutions or else be isolated as such and used in solid form.
- dispersants IV and V Preference is given to dispersants IV and V, in which a 0 to im Mean 2.5, b average 25 to 250 and d 0 to average 0.5. Particularly preferred are dispersants IV and V, in which a 0 to on average 2.5, b on average 50 to 100 and d on average 0.5 is.
- optional additives to be added are, for example commonly used in the textile industry biocides or Water retention agents.
- Other optional additives to be added are the copolymers described in EP-A 0 321 393 of N-vinylpyrrolidone with 3-vinylpropionic acid.
- a formulation is used containing next to water, in each case based on the weight the preparation, 1 to 40 wt .-%, preferably 3 to 10 wt .-%, the above-described mixture of brightener and Nuancierfarbstoff, From 3 to 12% by weight of anionic or nonionic Dispersant, 1 to 15 wt .-% copolymers of N-vinylpyrrolidone with vinyl acetate or vinyl propionate or mixtures thereof, and 1 to 25% by weight of other additives (e.g., water retention agents or biocides).
- additives e.g., water retention agents or biocides
- aqueous liquor for the preparation of the aqueous liquor described above can be the individual predispersed optically brightening substances as well as the shading dye (s) optionally used, Dispersants and / or other additives dose separately.
- Formulations according to the invention generally contain water and, in each case based on the weight of the preparation, 1 to 40 Wt .-%, preferably 3 to 25 wt .-%, the above-specified Mixtures of lightening compounds, optionally 0.001 to 0.1% by weight shading dye, optionally 0.5 to 40 Wt .-% dispersant and 5 to 60 wt .-%, preferably 5 bis 52 wt .-%, of aggregates.
- Another object of the present invention is the Use of the formulation according to the invention for brightening textile materials, in particular polyester or polyester mixtures.
- the isomer distribution was as follows: I trans-cis, 95: 5 mol%; II p, o ', II mp', II o, o ', in each case more than 95 mol% trans, determined in each case by 1 H-NMR spectroscopy.
- the inventive method is in each case with a smaller Amount of lightening compounds a stronger Effect achieved as by the literature methods. Also can be the maximum lightening effect after the inventive method at lower concentrations of optically reach lightening substances.
- the comparative experiments V 2.13 to V 2.16 were carried out analogously to the examples according to the invention, but 1.5 g / l of a mixture of 70 wt .-% II o, p 'and 30 wt .-% II o, o' were used.
- Brightening compounds [% by weight] Fixing temperature [° C] Whiteness to CIE I II p, o ' II m, p ' II o, o ' 4 b.1 2.1 45 55 - - - 140 133 2.2 45 55 - - - 150 139 2.3 45 55 - - - 160 142 2.4 45 55 - - - 170 144 2.5 40 40 20 - - 140 135 2.6 40 40 20 - - 150 139 2.7 40 40 20 - - 160 142 2.8 40 40 20 - - 170 143 V 2.9 - 50 - - 50 140 128 V 2.10 - 50 - - 50 150 132 V 2.11 - 50 - - 50 160 136 V 2.12 - 50 - - 50 170 137 V 2.13 - 70 - 30 - 140 130 V 2.14 - 70 - 30 - 150 135 V 2.15 - 70 - 30 - 160 136 V 2.16
Landscapes
- Engineering & Computer Science (AREA)
- Textile Engineering (AREA)
- Chemical & Material Sciences (AREA)
- Dispersion Chemistry (AREA)
- Life Sciences & Earth Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- Wood Science & Technology (AREA)
- Organic Chemistry (AREA)
- Inorganic Chemistry (AREA)
- Coloring (AREA)
- Treatments For Attaching Organic Compounds To Fibrous Goods (AREA)
- Chemical Or Physical Treatment Of Fibers (AREA)
- Diaphragms For Electromechanical Transducers (AREA)
- Detergent Compositions (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Compounds Of Unknown Constitution (AREA)
Applications Claiming Priority (3)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
DE10219993 | 2002-05-03 | ||
DE10219993A DE10219993A1 (de) | 2002-05-03 | 2002-05-03 | Verfahren zum Aufhellen von textilen Materialien |
PCT/EP2003/004497 WO2003093565A2 (de) | 2002-05-03 | 2003-04-30 | Verfahren zum aufhellen von textilen materialien |
Publications (2)
Publication Number | Publication Date |
---|---|
EP1504149A2 EP1504149A2 (de) | 2005-02-09 |
EP1504149B1 true EP1504149B1 (de) | 2005-08-24 |
Family
ID=29265083
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
EP03717323A Expired - Lifetime EP1504149B1 (de) | 2002-05-03 | 2003-04-30 | Verfahren zum aufhellen von textilen materialien |
Country Status (15)
Country | Link |
---|---|
US (1) | US20050235429A1 (zh) |
EP (1) | EP1504149B1 (zh) |
JP (1) | JP2005529245A (zh) |
KR (1) | KR100973535B1 (zh) |
CN (1) | CN1333129C (zh) |
AT (1) | ATE302871T1 (zh) |
AU (1) | AU2003222312A1 (zh) |
BR (1) | BR0309642B1 (zh) |
DE (2) | DE10219993A1 (zh) |
ES (1) | ES2246470T3 (zh) |
HR (1) | HRPK20041141B3 (zh) |
MX (1) | MXPA04010130A (zh) |
TW (1) | TWI279468B (zh) |
WO (1) | WO2003093565A2 (zh) |
ZA (1) | ZA200409769B (zh) |
Families Citing this family (18)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
ES2316862T3 (es) * | 2002-12-10 | 2009-04-16 | Ciba Holding Inc. | Mezclas de agentes de blanqueo fluorescentes. |
AR049538A1 (es) * | 2004-06-29 | 2006-08-09 | Procter & Gamble | Composiciones de detergentes para lavanderia con colorante entonador eficiente |
PL1794276T3 (pl) * | 2004-09-23 | 2009-10-30 | Unilever Nv | Kompozycje do obróbki bielizny do prania |
EP2009088B1 (en) * | 2004-09-23 | 2010-02-24 | Unilever PLC | Laundry treatment compositions |
DE102005039971A1 (de) * | 2005-08-23 | 2007-03-08 | Basf Ag | Flüssigwaschmittelformulierung |
US20070174972A1 (en) * | 2005-11-14 | 2007-08-02 | Invista North America S.A R.I. | Spandex having enhanced whiteness, and fabrics and garments comprising the same |
EP1974006A1 (en) * | 2006-01-18 | 2008-10-01 | Ciba Specialty Chemicals Holding Inc. | Process for the treatment of fiber materials |
BRPI0706732B1 (pt) * | 2006-01-23 | 2017-06-06 | Milliken & Co | agente branqueador para composições de cuidado de lavanderia, que é um corante tiazólio |
US20080177089A1 (en) | 2007-01-19 | 2008-07-24 | Eugene Steven Sadlowski | Novel whitening agents for cellulosic substrates |
US7642282B2 (en) | 2007-01-19 | 2010-01-05 | Milliken & Company | Whitening agents for cellulosic substrates |
WO2009074488A1 (en) * | 2007-12-10 | 2009-06-18 | Basf Se | Dye formulation and process for the treatment of fiber materials |
BRPI0821867A2 (pt) * | 2008-01-11 | 2015-07-28 | Unilever Nv | Composição de tratamento para lavagem de tecidos, processo doméstico para o tratamento de tecidos e corante de tiazol |
BR112012027594A2 (pt) * | 2010-04-29 | 2016-08-09 | Unilever Nv | composição de tratamento de roupa e método de tratamento de um têxtil para roupa |
US8715368B2 (en) | 2010-11-12 | 2014-05-06 | The Procter & Gamble Company | Thiophene azo dyes and laundry care compositions containing the same |
MX349259B (es) * | 2011-01-20 | 2017-07-18 | Huntsman Advanced Mat (Switzerland) Gmbh | Formulaciones de agentes blanqueadores fluorescentes en forma dispersa. |
US9163146B2 (en) | 2011-06-03 | 2015-10-20 | Milliken & Company | Thiophene azo carboxylate dyes and laundry care compositions containing the same |
US9796952B2 (en) | 2012-09-25 | 2017-10-24 | The Procter & Gamble Company | Laundry care compositions with thiazolium dye |
CN112048075B (zh) * | 2020-08-26 | 2022-11-08 | 盐城工学院 | 一种光致变色萘酰亚胺基Cd-MOF、其制备方法、光致变色印花浆及应用 |
Family Cites Families (10)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
DE2060762A1 (de) * | 1970-12-10 | 1972-06-22 | Henkel & Cie Gmbh | Mittel zur Herstellung von Kaltbleichflotten,insbesondere von kaltbleichwirksamen Waschlaugen |
DE2929687A1 (de) * | 1979-07-21 | 1981-02-12 | Hoechst Ag | Mischungen von optischen aufhellern |
DE2929591A1 (de) * | 1979-07-21 | 1981-02-05 | Hoechst Ag | Mischungen von optischen aufhellern |
DE3104992A1 (de) * | 1981-02-12 | 1982-08-26 | Hoechst Ag, 6000 Frankfurt | "mischungen von optischen aufhellern" |
EP0240461B1 (de) * | 1986-04-02 | 1991-04-17 | Ciba-Geigy Ag | Mischungen von optischen Aufhellern |
DE3878550D1 (de) * | 1987-11-27 | 1993-03-25 | Ciba Geigy Ag | Aufhellerdispersion. |
DE3878540D1 (de) * | 1987-11-27 | 1993-03-25 | Ciba Geigy Ag | Aufhellerdispersion. |
PT682145E (pt) * | 1994-05-12 | 2005-01-31 | Ciba Sc Holding Ag | Trtamento textil |
EP0724012A1 (en) * | 1995-01-27 | 1996-07-31 | The Procter & Gamble Company | Detergent compositions comprising bleaching agent and brightener |
DE19732109A1 (de) * | 1997-07-25 | 1999-01-28 | Clariant Gmbh | Mischungen von optischen Aufhellern |
-
2002
- 2002-05-03 DE DE10219993A patent/DE10219993A1/de not_active Withdrawn
-
2003
- 2003-04-30 AU AU2003222312A patent/AU2003222312A1/en not_active Abandoned
- 2003-04-30 KR KR1020047017647A patent/KR100973535B1/ko active IP Right Grant
- 2003-04-30 ES ES03717323T patent/ES2246470T3/es not_active Expired - Lifetime
- 2003-04-30 JP JP2004501695A patent/JP2005529245A/ja active Pending
- 2003-04-30 MX MXPA04010130A patent/MXPA04010130A/es active IP Right Grant
- 2003-04-30 DE DE50301054T patent/DE50301054D1/de not_active Expired - Lifetime
- 2003-04-30 EP EP03717323A patent/EP1504149B1/de not_active Expired - Lifetime
- 2003-04-30 WO PCT/EP2003/004497 patent/WO2003093565A2/de active IP Right Grant
- 2003-04-30 TW TW092110165A patent/TWI279468B/zh not_active IP Right Cessation
- 2003-04-30 CN CNB038100355A patent/CN1333129C/zh not_active Expired - Fee Related
- 2003-04-30 BR BRPI0309642-4B1A patent/BR0309642B1/pt not_active IP Right Cessation
- 2003-04-30 AT AT03717323T patent/ATE302871T1/de not_active IP Right Cessation
- 2003-04-30 US US10/512,636 patent/US20050235429A1/en not_active Abandoned
-
2004
- 2004-11-30 HR HR20041141A patent/HRPK20041141B3/xx not_active IP Right Cessation
- 2004-12-02 ZA ZA200409769A patent/ZA200409769B/en unknown
Also Published As
Publication number | Publication date |
---|---|
US20050235429A1 (en) | 2005-10-27 |
CN1650064A (zh) | 2005-08-03 |
DE10219993A1 (de) | 2003-11-20 |
WO2003093565A3 (de) | 2004-03-04 |
HRPK20041141B3 (en) | 2006-12-31 |
KR20040106453A (ko) | 2004-12-17 |
ES2246470T3 (es) | 2006-02-16 |
JP2005529245A (ja) | 2005-09-29 |
AU2003222312A8 (en) | 2003-11-17 |
EP1504149A2 (de) | 2005-02-09 |
DE50301054D1 (de) | 2005-09-29 |
BR0309642A (pt) | 2005-03-01 |
BR0309642B1 (pt) | 2013-11-05 |
CN1333129C (zh) | 2007-08-22 |
WO2003093565A2 (de) | 2003-11-13 |
HRP20041141A2 (en) | 2005-06-30 |
MXPA04010130A (es) | 2005-03-31 |
KR100973535B1 (ko) | 2010-08-03 |
ZA200409769B (en) | 2006-06-28 |
ATE302871T1 (de) | 2005-09-15 |
TWI279468B (en) | 2007-04-21 |
TW200407483A (en) | 2004-05-16 |
AU2003222312A1 (en) | 2003-11-17 |
Similar Documents
Publication | Publication Date | Title |
---|---|---|
EP1504149B1 (de) | Verfahren zum aufhellen von textilen materialien | |
EP0074335B1 (de) | Lagerstabile Mottenschutzformulierungen | |
DE4425359A1 (de) | Motten- und Käferschutzmittel | |
EP0017618B1 (de) | Verfahren zum optischen Aufhellen von Polyesterfasern im Ausziehverfahren | |
EP0350449A2 (de) | Optische Aufheller enthaltende Flüssigwaschmittel | |
CH432119A (de) | Verwendung von Halogen-o-hydroxy-diphenyläthern als antimikrobielle Mittel | |
EP0772708B1 (de) | Verfahren zum optischen aufhellen von polyamiden | |
DE19732109A1 (de) | Mischungen von optischen Aufhellern | |
EP0590438A2 (de) | Mischungen von Azofarbstoffen für marineblaue bis schwarze Farbtöne | |
DE2539349C2 (de) | Wäschenachbehandlungsmittel | |
EP0475907B1 (de) | Verfahren zur Herstellung mouldingechter Artikel | |
EP0011824A1 (de) | Benzofuranyl-benzimidazole, Verfahren zu ihrer Herstellung sowie ihre Verwendung zum optischen Aufhellen von organischen Materialien | |
WO1996016129A1 (de) | Mischungen von azofarbstoffen für schwarze farbtöne | |
EP0540471A1 (de) | Mittel und Verfahren zur Herstellung mouldingechter Artikel | |
EP1032637B1 (de) | Waschverfahren und zubereitung zu seiner durchführung | |
DE1302051B (de) | Verwendung von Benzimidazolylstilben-Verbindungen als optische Aufhellungsmittel | |
EP0890671A2 (de) | Verwendung von modifizierten Fettaminen zur Verhinderung von Ablagerungen von niedermolekularen Nebenprodukten auf textilen Materialien | |
DE19509956A1 (de) | Mischungen von Reaktivfarbstoffen | |
DE1545895B2 (de) | Pyrazolinverbindungen | |
DE2502234A1 (de) | Zubereitung und verfahren zum knitterfreien faerben von polyesterfasern | |
DE1953068C3 (de) | Hilfsmittel für das Färben von Cellulosefasern, stickstoffhaltigen Fasern, synthetischen Fasern und deren Fasermischungen und dessen Verwendung | |
AT162913B (de) | Verfahren zum Veredeln von Fasermaterialien | |
DE1220381B (de) | Verfahren zum Aufhellen von Polyesterfasermaterial | |
DE2348363A1 (de) | Carrier-zubereitung und verfahren zum faerben und bedrucken | |
CH361002A (de) | Verfahren zur Herstellung oxydierter Azoverbindungen |
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: 20041203 |
|
AK | Designated contracting states |
Kind code of ref document: A2 Designated state(s): AT BE BG CH CY CZ DE DK EE ES FI FR GB GR HU IE IT LI LU MC NL PT RO SE SI SK TR |
|
AX | Request for extension of the european patent |
Extension state: AL LT LV MK |
|
GRAP | Despatch of communication of intention to grant a patent |
Free format text: ORIGINAL CODE: EPIDOSNIGR1 |
|
GRAS | Grant fee paid |
Free format text: ORIGINAL CODE: EPIDOSNIGR3 |
|
GRAA | (expected) grant |
Free format text: ORIGINAL CODE: 0009210 |
|
AK | Designated contracting states |
Kind code of ref document: B1 Designated state(s): AT BE BG CH CY CZ DE DK EE ES FI FR GB GR HU IE IT LI LU MC NL PT RO SE SI SK TR |
|
DAX | Request for extension of the european patent (deleted) | ||
PG25 | Lapsed in a contracting state [announced via postgrant information from national office to epo] |
Ref country code: FI Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT Effective date: 20050824 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: 20050824 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: 20050824 Ref country code: IE Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT Effective date: 20050824 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: 20050824 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: 20050824 |
|
REG | Reference to a national code |
Ref country code: GB Ref legal event code: FG4D Free format text: NOT ENGLISH |
|
REG | Reference to a national code |
Ref country code: CH Ref legal event code: EP |
|
REG | Reference to a national code |
Ref country code: IE Ref legal event code: FG4D Free format text: LANGUAGE OF EP DOCUMENT: GERMAN |
|
REF | Corresponds to: |
Ref document number: 50301054 Country of ref document: DE Date of ref document: 20050929 Kind code of ref document: P |
|
GBT | Gb: translation of ep patent filed (gb section 77(6)(a)/1977) |
Effective date: 20051003 |
|
PG25 | Lapsed in a contracting state [announced via postgrant information from national office to epo] |
Ref country code: GR Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT Effective date: 20051124 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: 20051124 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: 20051124 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: 20051124 |
|
NLV1 | Nl: lapsed or annulled due to failure to fulfill the requirements of art. 29p and 29m of the patents act | ||
REG | Reference to a national code |
Ref country code: ES Ref legal event code: FG2A Ref document number: 2246470 Country of ref document: ES Kind code of ref document: T3 |
|
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 Effective date: 20060225 |
|
REG | Reference to a national code |
Ref country code: IE Ref legal event code: FD4D |
|
ET | Fr: translation filed | ||
PG25 | Lapsed in a contracting state [announced via postgrant information from national office to epo] |
Ref country code: MC Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES Effective date: 20060430 Ref country code: BE Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES Effective date: 20060430 Ref country code: AT Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES Effective date: 20060430 |
|
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 |
Effective date: 20060526 |
|
PGFP | Annual fee paid to national office [announced via postgrant information from national office to epo] |
Ref country code: CZ Payment date: 20070326 Year of fee payment: 5 |
|
PGFP | Annual fee paid to national office [announced via postgrant information from national office to epo] |
Ref country code: PT Payment date: 20070427 Year of fee payment: 5 |
|
REG | Reference to a national code |
Ref country code: CH Ref legal event code: PL |
|
BERE | Be: lapsed |
Owner name: BASF A.G. Effective date: 20060430 |
|
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: 20070430 Ref country code: LI Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES Effective date: 20070430 |
|
PG25 | Lapsed in a contracting state [announced via postgrant information from national office to epo] |
Ref country code: EE Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT Effective date: 20050824 |
|
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: 20060430 |
|
REG | Reference to a national code |
Ref country code: PT Ref legal event code: MM4A Free format text: LAPSE DUE TO NON-PAYMENT OF FEES Effective date: 20081031 |
|
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: 20050824 |
|
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 NON-PAYMENT OF DUE FEES Effective date: 20081031 |
|
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 NON-PAYMENT OF DUE FEES Effective date: 20080430 |
|
REG | Reference to a national code |
Ref country code: FR Ref legal event code: PLFP Year of fee payment: 14 |
|
PGFP | Annual fee paid to national office [announced via postgrant information from national office to epo] |
Ref country code: GB Payment date: 20160502 Year of fee payment: 14 |
|
REG | Reference to a national code |
Ref country code: DE Ref legal event code: R079 Ref document number: 50301054 Country of ref document: DE Free format text: PREVIOUS MAIN CLASS: D06L0003120000 Ipc: D06L0004600000 |
|
REG | Reference to a national code |
Ref country code: FR Ref legal event code: PLFP Year of fee payment: 15 |
|
GBPC | Gb: european patent ceased through non-payment of renewal fee |
Effective date: 20170430 |
|
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: 20170430 |
|
REG | Reference to a national code |
Ref country code: FR Ref legal event code: PLFP Year of fee payment: 16 |
|
PGFP | Annual fee paid to national office [announced via postgrant information from national office to epo] |
Ref country code: TR Payment date: 20180409 Year of fee payment: 16 Ref country code: IT Payment date: 20180420 Year of fee payment: 16 Ref country code: FR Payment date: 20180426 Year of fee payment: 16 |
|
PGFP | Annual fee paid to national office [announced via postgrant information from national office to epo] |
Ref country code: DE Payment date: 20190621 Year of fee payment: 17 Ref country code: ES Payment date: 20190524 Year of fee payment: 17 |
|
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: 20190430 |
|
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: 20190430 |
|
REG | Reference to a national code |
Ref country code: DE Ref legal event code: R119 Ref document number: 50301054 Country of ref document: DE |
|
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: 20201103 |
|
REG | Reference to a national code |
Ref country code: ES Ref legal event code: FD2A Effective date: 20210906 |
|
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: 20200501 |
|
PG25 | Lapsed in a contracting state [announced via postgrant information from national office to epo] |
Ref country code: TR Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES Effective date: 20190430 |