EP0699247A1 - Procede de pretraitement en continu d'un materiau textile contenant de la cellulose - Google Patents
Procede de pretraitement en continu d'un materiau textile contenant de la celluloseInfo
- Publication number
- EP0699247A1 EP0699247A1 EP94917611A EP94917611A EP0699247A1 EP 0699247 A1 EP0699247 A1 EP 0699247A1 EP 94917611 A EP94917611 A EP 94917611A EP 94917611 A EP94917611 A EP 94917611A EP 0699247 A1 EP0699247 A1 EP 0699247A1
- Authority
- EP
- European Patent Office
- Prior art keywords
- acid
- weight
- mixture
- customary
- treatment bath
- 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
- 238000000034 method Methods 0.000 title claims abstract description 55
- 239000004753 textile Substances 0.000 title claims abstract description 48
- 239000000463 material Substances 0.000 title claims abstract description 28
- 229920002678 cellulose Polymers 0.000 title claims description 16
- 239000001913 cellulose Substances 0.000 title claims description 16
- 238000004061 bleaching Methods 0.000 claims abstract description 66
- 238000009990 desizing Methods 0.000 claims abstract description 38
- 239000002253 acid Substances 0.000 claims abstract description 29
- 239000000203 mixture Substances 0.000 claims abstract description 29
- 230000008569 process Effects 0.000 claims abstract description 29
- 238000011282 treatment Methods 0.000 claims abstract description 26
- 239000002270 dispersing agent Substances 0.000 claims abstract description 19
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 claims abstract description 18
- 239000008139 complexing agent Substances 0.000 claims abstract description 17
- 102000004190 Enzymes Human genes 0.000 claims abstract description 14
- 108090000790 Enzymes Proteins 0.000 claims abstract description 14
- 229910021645 metal ion Inorganic materials 0.000 claims abstract description 11
- 239000004094 surface-active agent Substances 0.000 claims abstract description 10
- 150000001991 dicarboxylic acids Chemical class 0.000 claims abstract description 7
- 229920003169 water-soluble polymer Polymers 0.000 claims abstract description 7
- 150000008064 anhydrides Chemical class 0.000 claims abstract description 6
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 6
- 150000002763 monocarboxylic acids Chemical class 0.000 claims abstract description 6
- PTMHPRAIXMAOOB-UHFFFAOYSA-N phosphoramidic acid Chemical compound NP(O)(O)=O PTMHPRAIXMAOOB-UHFFFAOYSA-N 0.000 claims abstract description 5
- 238000004140 cleaning Methods 0.000 claims description 24
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 claims description 14
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 claims description 14
- 238000005406 washing Methods 0.000 claims description 10
- OFOBLEOULBTSOW-UHFFFAOYSA-N Propanedioic acid Natural products OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 claims description 9
- VZCYOOQTPOCHFL-UPHRSURJSA-N maleic acid Chemical compound OC(=O)\C=C/C(O)=O VZCYOOQTPOCHFL-UPHRSURJSA-N 0.000 claims description 9
- 239000011976 maleic acid Substances 0.000 claims description 9
- VZCYOOQTPOCHFL-UHFFFAOYSA-N trans-butenedioic acid Natural products OC(=O)C=CC(O)=O VZCYOOQTPOCHFL-UHFFFAOYSA-N 0.000 claims description 9
- MGFYIUFZLHCRTH-UHFFFAOYSA-N nitrilotriacetic acid Chemical compound OC(=O)CN(CC(O)=O)CC(O)=O MGFYIUFZLHCRTH-UHFFFAOYSA-N 0.000 claims description 7
- DUYCTCQXNHFCSJ-UHFFFAOYSA-N dtpmp Chemical compound OP(=O)(O)CN(CP(O)(O)=O)CCN(CP(O)(=O)O)CCN(CP(O)(O)=O)CP(O)(O)=O DUYCTCQXNHFCSJ-UHFFFAOYSA-N 0.000 claims description 6
- FEWFXBUNENSNBQ-UHFFFAOYSA-N 2-hydroxyacrylic acid Chemical compound OC(=C)C(O)=O FEWFXBUNENSNBQ-UHFFFAOYSA-N 0.000 claims description 5
- 229940090960 diethylenetriamine pentamethylene phosphonic acid Drugs 0.000 claims description 3
- 125000002768 hydroxyalkyl group Chemical group 0.000 claims description 2
- 125000005341 metaphosphate group Chemical group 0.000 claims description 2
- 229920000388 Polyphosphate Polymers 0.000 claims 1
- 239000001205 polyphosphate Substances 0.000 claims 1
- 235000011176 polyphosphates Nutrition 0.000 claims 1
- 229940045916 polymetaphosphate Drugs 0.000 abstract description 2
- 150000002978 peroxides Chemical class 0.000 description 39
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 36
- 229920002472 Starch Polymers 0.000 description 18
- 239000008107 starch Substances 0.000 description 18
- 235000019698 starch Nutrition 0.000 description 18
- 239000000126 substance Substances 0.000 description 17
- 239000000654 additive Substances 0.000 description 16
- 230000000694 effects Effects 0.000 description 16
- 239000004744 fabric Substances 0.000 description 16
- 229920000742 Cotton Polymers 0.000 description 15
- 230000006378 damage Effects 0.000 description 13
- 235000011121 sodium hydroxide Nutrition 0.000 description 12
- 229940088598 enzyme Drugs 0.000 description 11
- 235000002639 sodium chloride Nutrition 0.000 description 11
- 238000010521 absorption reaction Methods 0.000 description 9
- 150000007513 acids Chemical class 0.000 description 8
- -1 anions Carbonate Chemical class 0.000 description 8
- 150000003839 salts Chemical class 0.000 description 8
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 8
- 229920001577 copolymer Polymers 0.000 description 7
- 238000004043 dyeing Methods 0.000 description 7
- 238000005470 impregnation Methods 0.000 description 7
- SNQQPOLDUKLAAF-UHFFFAOYSA-N nonylphenol Chemical class CCCCCCCCCC1=CC=CC=C1O SNQQPOLDUKLAAF-UHFFFAOYSA-N 0.000 description 7
- 239000000243 solution Substances 0.000 description 7
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 description 6
- 239000000835 fiber Substances 0.000 description 6
- 229910001385 heavy metal Inorganic materials 0.000 description 6
- 239000000178 monomer Substances 0.000 description 6
- 230000003647 oxidation Effects 0.000 description 6
- 238000007254 oxidation reaction Methods 0.000 description 6
- 239000011734 sodium Substances 0.000 description 6
- 239000003381 stabilizer Substances 0.000 description 6
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 description 5
- 229920002125 Sokalan® Polymers 0.000 description 5
- 239000003513 alkali Substances 0.000 description 5
- GRWZHXKQBITJKP-UHFFFAOYSA-L dithionite(2-) Chemical compound [O-]S(=O)S([O-])=O GRWZHXKQBITJKP-UHFFFAOYSA-L 0.000 description 5
- 239000012535 impurity Substances 0.000 description 5
- 150000002500 ions Chemical class 0.000 description 5
- 239000011777 magnesium Substances 0.000 description 5
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 4
- 229920000881 Modified starch Polymers 0.000 description 4
- 150000003863 ammonium salts Chemical class 0.000 description 4
- 239000007844 bleaching agent Substances 0.000 description 4
- 239000007853 buffer solution Substances 0.000 description 4
- 239000011575 calcium Substances 0.000 description 4
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 4
- 150000001768 cations Chemical class 0.000 description 4
- 150000001875 compounds Chemical class 0.000 description 4
- 229910052802 copper Inorganic materials 0.000 description 4
- 239000010949 copper Substances 0.000 description 4
- 238000007654 immersion Methods 0.000 description 4
- 229910052742 iron Inorganic materials 0.000 description 4
- 229910052749 magnesium Inorganic materials 0.000 description 4
- 229910052751 metal Inorganic materials 0.000 description 4
- 239000002184 metal Substances 0.000 description 4
- 235000019426 modified starch Nutrition 0.000 description 4
- 239000004584 polyacrylic acid Substances 0.000 description 4
- 239000000047 product Substances 0.000 description 4
- 229920002134 Carboxymethyl cellulose Polymers 0.000 description 3
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 3
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 3
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 description 3
- 229910052784 alkaline earth metal Inorganic materials 0.000 description 3
- 229910052782 aluminium Inorganic materials 0.000 description 3
- 229910052791 calcium Inorganic materials 0.000 description 3
- 238000000354 decomposition reaction Methods 0.000 description 3
- 239000003599 detergent Substances 0.000 description 3
- FPYJFEHAWHCUMM-UHFFFAOYSA-N maleic anhydride Chemical compound O=C1OC(=O)C=C1 FPYJFEHAWHCUMM-UHFFFAOYSA-N 0.000 description 3
- 229910052748 manganese Inorganic materials 0.000 description 3
- 238000004519 manufacturing process Methods 0.000 description 3
- 239000000843 powder Substances 0.000 description 3
- 238000001556 precipitation Methods 0.000 description 3
- 239000011780 sodium chloride Substances 0.000 description 3
- JVBXVOWTABLYPX-UHFFFAOYSA-L sodium dithionite Chemical compound [Na+].[Na+].[O-]S(=O)S([O-])=O JVBXVOWTABLYPX-UHFFFAOYSA-L 0.000 description 3
- 239000000080 wetting agent Substances 0.000 description 3
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Natural products CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 2
- HGINCPLSRVDWNT-UHFFFAOYSA-N Acrolein Chemical compound C=CC=O HGINCPLSRVDWNT-UHFFFAOYSA-N 0.000 description 2
- HRPVXLWXLXDGHG-UHFFFAOYSA-N Acrylamide Chemical compound NC(=O)C=C HRPVXLWXLXDGHG-UHFFFAOYSA-N 0.000 description 2
- NLHHRLWOUZZQLW-UHFFFAOYSA-N Acrylonitrile Chemical compound C=CC#N NLHHRLWOUZZQLW-UHFFFAOYSA-N 0.000 description 2
- 102000013142 Amylases Human genes 0.000 description 2
- 108010065511 Amylases Proteins 0.000 description 2
- 241000894006 Bacteria Species 0.000 description 2
- GAWIXWVDTYZWAW-UHFFFAOYSA-N C[CH]O Chemical group C[CH]O GAWIXWVDTYZWAW-UHFFFAOYSA-N 0.000 description 2
- 206010010219 Compulsions Diseases 0.000 description 2
- RGHNJXZEOKUKBD-SQOUGZDYSA-N D-gluconic acid Chemical compound OC[C@@H](O)[C@@H](O)[C@H](O)[C@@H](O)C(O)=O RGHNJXZEOKUKBD-SQOUGZDYSA-N 0.000 description 2
- BMYNFMYTOJXKLE-UHFFFAOYSA-N DL-isoserine Natural products NCC(O)C(O)=O BMYNFMYTOJXKLE-UHFFFAOYSA-N 0.000 description 2
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 2
- BPQQTUXANYXVAA-UHFFFAOYSA-N Orthosilicate Chemical compound [O-][Si]([O-])([O-])[O-] BPQQTUXANYXVAA-UHFFFAOYSA-N 0.000 description 2
- 239000004372 Polyvinyl alcohol Substances 0.000 description 2
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- 244000274883 Urtica dioica Species 0.000 description 2
- 235000009108 Urtica dioica Nutrition 0.000 description 2
- XTXRWKRVRITETP-UHFFFAOYSA-N Vinyl acetate Chemical compound CC(=O)OC=C XTXRWKRVRITETP-UHFFFAOYSA-N 0.000 description 2
- FGFOSPUUHLJDBD-UHFFFAOYSA-N acetic acid 2-(2-aminoethoxy)ethanamine Chemical compound CC(O)=O.CC(O)=O.CC(O)=O.CC(O)=O.NCCOCCN FGFOSPUUHLJDBD-UHFFFAOYSA-N 0.000 description 2
- XXROGKLTLUQVRX-UHFFFAOYSA-N allyl alcohol Chemical compound OCC=C XXROGKLTLUQVRX-UHFFFAOYSA-N 0.000 description 2
- 102000004139 alpha-Amylases Human genes 0.000 description 2
- 108090000637 alpha-Amylases Proteins 0.000 description 2
- 235000019418 amylase Nutrition 0.000 description 2
- 239000007864 aqueous solution Substances 0.000 description 2
- 230000008901 benefit Effects 0.000 description 2
- 238000009835 boiling Methods 0.000 description 2
- 125000004432 carbon atom Chemical group C* 0.000 description 2
- 239000001768 carboxy methyl cellulose Substances 0.000 description 2
- 235000010948 carboxy methyl cellulose Nutrition 0.000 description 2
- 125000002057 carboxymethyl group Chemical group [H]OC(=O)C([H])([H])[*] 0.000 description 2
- 239000008112 carboxymethyl-cellulose Substances 0.000 description 2
- 230000015556 catabolic process Effects 0.000 description 2
- 239000003638 chemical reducing agent Substances 0.000 description 2
- 235000015165 citric acid Nutrition 0.000 description 2
- 239000006185 dispersion Substances 0.000 description 2
- 238000010011 enzymatic desizing Methods 0.000 description 2
- 150000002148 esters Chemical class 0.000 description 2
- 238000003306 harvesting Methods 0.000 description 2
- 229920001519 homopolymer Polymers 0.000 description 2
- 239000010903 husk Substances 0.000 description 2
- ROBFUDYVXSDBQM-UHFFFAOYSA-N hydroxymalonic acid Chemical compound OC(=O)C(O)C(O)=O ROBFUDYVXSDBQM-UHFFFAOYSA-N 0.000 description 2
- 230000006872 improvement Effects 0.000 description 2
- 229910052500 inorganic mineral Inorganic materials 0.000 description 2
- 238000009940 knitting Methods 0.000 description 2
- JVTAAEKCZFNVCJ-UHFFFAOYSA-N lactic acid Chemical compound CC(O)C(O)=O JVTAAEKCZFNVCJ-UHFFFAOYSA-N 0.000 description 2
- 239000001630 malic acid Substances 0.000 description 2
- 150000002739 metals Chemical class 0.000 description 2
- FQPSGWSUVKBHSU-UHFFFAOYSA-N methacrylamide Chemical compound CC(=C)C(N)=O FQPSGWSUVKBHSU-UHFFFAOYSA-N 0.000 description 2
- 235000010755 mineral Nutrition 0.000 description 2
- 239000011707 mineral Substances 0.000 description 2
- 238000010525 oxidative degradation reaction Methods 0.000 description 2
- 230000001590 oxidative effect Effects 0.000 description 2
- JRKICGRDRMAZLK-UHFFFAOYSA-L peroxydisulfate Chemical compound [O-]S(=O)(=O)OOS([O-])(=O)=O JRKICGRDRMAZLK-UHFFFAOYSA-L 0.000 description 2
- 229920000058 polyacrylate Polymers 0.000 description 2
- 229920000642 polymer Polymers 0.000 description 2
- 238000006116 polymerization reaction Methods 0.000 description 2
- 229920002451 polyvinyl alcohol Polymers 0.000 description 2
- 229910052700 potassium Inorganic materials 0.000 description 2
- 238000007639 printing Methods 0.000 description 2
- RPACBEVZENYWOL-XFULWGLBSA-M sodium;(2r)-2-[6-(4-chlorophenoxy)hexyl]oxirane-2-carboxylate Chemical compound [Na+].C=1C=C(Cl)C=CC=1OCCCCCC[C@]1(C(=O)[O-])CO1 RPACBEVZENYWOL-XFULWGLBSA-M 0.000 description 2
- 230000008961 swelling Effects 0.000 description 2
- 239000002351 wastewater Substances 0.000 description 2
- 229910052725 zinc Inorganic materials 0.000 description 2
- VKZRWSNIWNFCIQ-WDSKDSINSA-N (2s)-2-[2-[[(1s)-1,2-dicarboxyethyl]amino]ethylamino]butanedioic acid Chemical compound OC(=O)C[C@@H](C(O)=O)NCCN[C@H](C(O)=O)CC(O)=O VKZRWSNIWNFCIQ-WDSKDSINSA-N 0.000 description 1
- DCCWEYXHEXDZQW-BYPYZUCNSA-N (2s)-2-[bis(carboxymethyl)amino]butanedioic acid Chemical compound OC(=O)C[C@@H](C(O)=O)N(CC(O)=O)CC(O)=O DCCWEYXHEXDZQW-BYPYZUCNSA-N 0.000 description 1
- GPQBLHIADQOTKU-YFKPBYRVSA-N (2s)-5-amino-2-[bis(carboxymethyl)amino]-5-oxopentanoic acid Chemical compound NC(=O)CC[C@@H](C(O)=O)N(CC(O)=O)CC(O)=O GPQBLHIADQOTKU-YFKPBYRVSA-N 0.000 description 1
- XVOUMQNXTGKGMA-OWOJBTEDSA-N (E)-glutaconic acid Chemical compound OC(=O)C\C=C\C(O)=O XVOUMQNXTGKGMA-OWOJBTEDSA-N 0.000 description 1
- BJEPYKJPYRNKOW-REOHCLBHSA-N (S)-malic acid Chemical compound OC(=O)[C@@H](O)CC(O)=O BJEPYKJPYRNKOW-REOHCLBHSA-N 0.000 description 1
- AZUYLZMQTIKGSC-UHFFFAOYSA-N 1-[6-[4-(5-chloro-6-methyl-1H-indazol-4-yl)-5-methyl-3-(1-methylindazol-5-yl)pyrazol-1-yl]-2-azaspiro[3.3]heptan-2-yl]prop-2-en-1-one Chemical compound ClC=1C(=C2C=NNC2=CC=1C)C=1C(=NN(C=1C)C1CC2(CN(C2)C(C=C)=O)C1)C=1C=C2C=NN(C2=CC=1)C AZUYLZMQTIKGSC-UHFFFAOYSA-N 0.000 description 1
- FXNDIJDIPNCZQJ-UHFFFAOYSA-N 2,4,4-trimethylpent-1-ene Chemical group CC(=C)CC(C)(C)C FXNDIJDIPNCZQJ-UHFFFAOYSA-N 0.000 description 1
- JAHNSTQSQJOJLO-UHFFFAOYSA-N 2-(3-fluorophenyl)-1h-imidazole Chemical compound FC1=CC=CC(C=2NC=CN=2)=C1 JAHNSTQSQJOJLO-UHFFFAOYSA-N 0.000 description 1
- XNCSCQSQSGDGES-UHFFFAOYSA-N 2-[2-[bis(carboxymethyl)amino]propyl-(carboxymethyl)amino]acetic acid Chemical compound OC(=O)CN(CC(O)=O)C(C)CN(CC(O)=O)CC(O)=O XNCSCQSQSGDGES-UHFFFAOYSA-N 0.000 description 1
- UIERETOOQGIECD-UHFFFAOYSA-N 2-methylbut-2-enoic acid Chemical compound CC=C(C)C(O)=O UIERETOOQGIECD-UHFFFAOYSA-N 0.000 description 1
- PSZAEHPBBUYICS-UHFFFAOYSA-N 2-methylidenepropanedioic acid Chemical compound OC(=O)C(=C)C(O)=O PSZAEHPBBUYICS-UHFFFAOYSA-N 0.000 description 1
- SZHQPBJEOCHCKM-UHFFFAOYSA-N 2-phosphonobutane-1,2,4-tricarboxylic acid Chemical compound OC(=O)CCC(P(O)(O)=O)(C(O)=O)CC(O)=O SZHQPBJEOCHCKM-UHFFFAOYSA-N 0.000 description 1
- IWTIBPIVCKUAHK-UHFFFAOYSA-N 3-[bis(2-carboxyethyl)amino]propanoic acid Chemical compound OC(=O)CCN(CCC(O)=O)CCC(O)=O IWTIBPIVCKUAHK-UHFFFAOYSA-N 0.000 description 1
- UWRBFYBQPCJRRL-UHFFFAOYSA-N 3-[bis(carboxymethyl)amino]propanoic acid Chemical compound OC(=O)CCN(CC(O)=O)CC(O)=O UWRBFYBQPCJRRL-UHFFFAOYSA-N 0.000 description 1
- QZPSOSOOLFHYRR-UHFFFAOYSA-N 3-hydroxypropyl prop-2-enoate Chemical compound OCCCOC(=O)C=C QZPSOSOOLFHYRR-UHFFFAOYSA-N 0.000 description 1
- YYPNJNDODFVZLE-UHFFFAOYSA-N 3-methylbut-2-enoic acid Chemical compound CC(C)=CC(O)=O YYPNJNDODFVZLE-UHFFFAOYSA-N 0.000 description 1
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 description 1
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 description 1
- 239000004382 Amylase Substances 0.000 description 1
- 229920003043 Cellulose fiber Polymers 0.000 description 1
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 1
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- RGHNJXZEOKUKBD-UHFFFAOYSA-N D-gluconic acid Natural products OCC(O)C(O)C(O)C(O)C(O)=O RGHNJXZEOKUKBD-UHFFFAOYSA-N 0.000 description 1
- FEWJPZIEWOKRBE-JCYAYHJZSA-N Dextrotartaric acid Chemical compound OC(=O)[C@H](O)[C@@H](O)C(O)=O FEWJPZIEWOKRBE-JCYAYHJZSA-N 0.000 description 1
- KCXVZYZYPLLWCC-UHFFFAOYSA-N EDTA Chemical compound OC(=O)CN(CC(O)=O)CCN(CC(O)=O)CC(O)=O KCXVZYZYPLLWCC-UHFFFAOYSA-N 0.000 description 1
- DSLZVSRJTYRBFB-UHFFFAOYSA-N Galactaric acid Natural products OC(=O)C(O)C(O)C(O)C(O)C(O)=O DSLZVSRJTYRBFB-UHFFFAOYSA-N 0.000 description 1
- 239000004471 Glycine Substances 0.000 description 1
- 229920002488 Hemicellulose Polymers 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- 125000000174 L-prolyl group Chemical group [H]N1C([H])([H])C([H])([H])C([H])([H])[C@@]1([H])C(*)=O 0.000 description 1
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 1
- 240000003183 Manihot esculenta Species 0.000 description 1
- 235000016735 Manihot esculenta subsp esculenta Nutrition 0.000 description 1
- QPCDCPDFJACHGM-UHFFFAOYSA-N N,N-bis{2-[bis(carboxymethyl)amino]ethyl}glycine Chemical compound OC(=O)CN(CC(O)=O)CCN(CC(=O)O)CCN(CC(O)=O)CC(O)=O QPCDCPDFJACHGM-UHFFFAOYSA-N 0.000 description 1
- GXCLVBGFBYZDAG-UHFFFAOYSA-N N-[2-(1H-indol-3-yl)ethyl]-N-methylprop-2-en-1-amine Chemical compound CN(CCC1=CNC2=C1C=CC=C2)CC=C GXCLVBGFBYZDAG-UHFFFAOYSA-N 0.000 description 1
- 240000007594 Oryza sativa Species 0.000 description 1
- 235000007164 Oryza sativa Nutrition 0.000 description 1
- 229910019142 PO4 Inorganic materials 0.000 description 1
- ABLZXFCXXLZCGV-UHFFFAOYSA-N Phosphorous acid Chemical compound OP(O)=O ABLZXFCXXLZCGV-UHFFFAOYSA-N 0.000 description 1
- 239000004952 Polyamide Substances 0.000 description 1
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 1
- 244000061456 Solanum tuberosum Species 0.000 description 1
- 235000002595 Solanum tuberosum Nutrition 0.000 description 1
- LSNNMFCWUKXFEE-UHFFFAOYSA-N Sulfurous acid Chemical compound OS(O)=O LSNNMFCWUKXFEE-UHFFFAOYSA-N 0.000 description 1
- FEWJPZIEWOKRBE-UHFFFAOYSA-N Tartaric acid Natural products [H+].[H+].[O-]C(=O)C(O)C(O)C([O-])=O FEWJPZIEWOKRBE-UHFFFAOYSA-N 0.000 description 1
- 235000021307 Triticum Nutrition 0.000 description 1
- 244000098338 Triticum aestivum Species 0.000 description 1
- 235000005811 Viola adunca Nutrition 0.000 description 1
- 240000009038 Viola odorata Species 0.000 description 1
- 235000013487 Viola odorata Nutrition 0.000 description 1
- 235000002254 Viola papilionacea Nutrition 0.000 description 1
- 244000172533 Viola sororia Species 0.000 description 1
- 239000004164 Wax ester Substances 0.000 description 1
- 240000008042 Zea mays Species 0.000 description 1
- 235000005824 Zea mays ssp. parviglumis Nutrition 0.000 description 1
- 235000002017 Zea mays subsp mays Nutrition 0.000 description 1
- KIDJHPQACZGFTI-UHFFFAOYSA-N [6-[bis(phosphonomethyl)amino]hexyl-(phosphonomethyl)amino]methylphosphonic acid Chemical compound OP(O)(=O)CN(CP(O)(O)=O)CCCCCCN(CP(O)(O)=O)CP(O)(O)=O KIDJHPQACZGFTI-UHFFFAOYSA-N 0.000 description 1
- XRRYGMTXOYFERK-UHFFFAOYSA-N [I].[K].[I] Chemical compound [I].[K].[I] XRRYGMTXOYFERK-UHFFFAOYSA-N 0.000 description 1
- KVUUQMDVROTSNI-UHFFFAOYSA-N [morpholin-4-yl(phosphono)methyl]phosphonic acid Chemical compound OP(O)(=O)C(P(O)(O)=O)N1CCOCC1 KVUUQMDVROTSNI-UHFFFAOYSA-N 0.000 description 1
- AJJJMKBOIAWMBE-UHFFFAOYSA-N acetic acid;propane-1,3-diamine Chemical compound CC(O)=O.CC(O)=O.CC(O)=O.CC(O)=O.NCCCN AJJJMKBOIAWMBE-UHFFFAOYSA-N 0.000 description 1
- 230000002378 acidificating effect Effects 0.000 description 1
- 230000004913 activation Effects 0.000 description 1
- 150000001298 alcohols Chemical class 0.000 description 1
- 229910052783 alkali metal Inorganic materials 0.000 description 1
- 150000001340 alkali metals Chemical class 0.000 description 1
- 150000001447 alkali salts Chemical class 0.000 description 1
- 229910001420 alkaline earth metal ion Inorganic materials 0.000 description 1
- 150000001342 alkaline earth metals Chemical class 0.000 description 1
- 229940024171 alpha-amylase Drugs 0.000 description 1
- BJEPYKJPYRNKOW-UHFFFAOYSA-N alpha-hydroxysuccinic acid Natural products OC(=O)C(O)CC(O)=O BJEPYKJPYRNKOW-UHFFFAOYSA-N 0.000 description 1
- 229940025131 amylases Drugs 0.000 description 1
- 230000001580 bacterial effect Effects 0.000 description 1
- 229910052788 barium Inorganic materials 0.000 description 1
- 230000003139 buffering effect Effects 0.000 description 1
- PVEOYINWKBTPIZ-UHFFFAOYSA-N but-3-enoic acid Chemical compound OC(=O)CC=C PVEOYINWKBTPIZ-UHFFFAOYSA-N 0.000 description 1
- 229910052793 cadmium Inorganic materials 0.000 description 1
- 159000000007 calcium salts Chemical class 0.000 description 1
- BVKZGUZCCUSVTD-UHFFFAOYSA-N carbonic acid Chemical class OC(O)=O BVKZGUZCCUSVTD-UHFFFAOYSA-N 0.000 description 1
- 150000004649 carbonic acid derivatives Chemical class 0.000 description 1
- 150000001732 carboxylic acid derivatives Chemical class 0.000 description 1
- 125000002843 carboxylic acid group Chemical group 0.000 description 1
- HNEGQIOMVPPMNR-IHWYPQMZSA-N citraconic acid Chemical compound OC(=O)C(/C)=C\C(O)=O HNEGQIOMVPPMNR-IHWYPQMZSA-N 0.000 description 1
- 229940018557 citraconic acid Drugs 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 230000000536 complexating effect Effects 0.000 description 1
- 238000010668 complexation reaction Methods 0.000 description 1
- 239000000470 constituent Substances 0.000 description 1
- 239000000356 contaminant Substances 0.000 description 1
- 238000010924 continuous production Methods 0.000 description 1
- 235000005822 corn Nutrition 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- WOSVXXBNNCUXMT-UHFFFAOYSA-N cyclopentane-1,2,3,4-tetracarboxylic acid Chemical compound OC(=O)C1CC(C(O)=O)C(C(O)=O)C1C(O)=O WOSVXXBNNCUXMT-UHFFFAOYSA-N 0.000 description 1
- 239000002837 defoliant Substances 0.000 description 1
- 238000006731 degradation reaction Methods 0.000 description 1
- 238000001514 detection method Methods 0.000 description 1
- 125000001142 dicarboxylic acid group Chemical group 0.000 description 1
- 235000014113 dietary fatty acids Nutrition 0.000 description 1
- 125000004177 diethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 1
- 125000000118 dimethyl group Chemical group [H]C([H])([H])* 0.000 description 1
- 230000009189 diving Effects 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 239000000975 dye Substances 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 235000019441 ethanol Nutrition 0.000 description 1
- UIWXSTHGICQLQT-UHFFFAOYSA-N ethenyl propanoate Chemical compound CCC(=O)OC=C UIWXSTHGICQLQT-UHFFFAOYSA-N 0.000 description 1
- 125000004494 ethyl ester group Chemical group 0.000 description 1
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 1
- 239000003925 fat Substances 0.000 description 1
- 239000000194 fatty acid Substances 0.000 description 1
- 229930195729 fatty acid Natural products 0.000 description 1
- 150000004665 fatty acids Chemical class 0.000 description 1
- 239000002657 fibrous material Substances 0.000 description 1
- 230000004992 fission Effects 0.000 description 1
- 239000012634 fragment Substances 0.000 description 1
- 239000000417 fungicide Substances 0.000 description 1
- DSLZVSRJTYRBFB-DUHBMQHGSA-N galactaric acid Chemical compound OC(=O)[C@H](O)[C@@H](O)[C@@H](O)[C@H](O)C(O)=O DSLZVSRJTYRBFB-DUHBMQHGSA-N 0.000 description 1
- 239000000174 gluconic acid Substances 0.000 description 1
- 235000012208 gluconic acid Nutrition 0.000 description 1
- 150000004679 hydroxides Chemical class 0.000 description 1
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 description 1
- 239000002917 insecticide Substances 0.000 description 1
- 230000002452 interceptive effect Effects 0.000 description 1
- JEIPFZHSYJVQDO-UHFFFAOYSA-N iron(III) oxide Inorganic materials O=[Fe]O[Fe]=O JEIPFZHSYJVQDO-UHFFFAOYSA-N 0.000 description 1
- 239000004310 lactic acid Substances 0.000 description 1
- 235000014655 lactic acid Nutrition 0.000 description 1
- 229920005610 lignin Polymers 0.000 description 1
- 229910052744 lithium Inorganic materials 0.000 description 1
- 230000014759 maintenance of location Effects 0.000 description 1
- 235000011090 malic acid Nutrition 0.000 description 1
- 229920000609 methyl cellulose Polymers 0.000 description 1
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 1
- XJRBAMWJDBPFIM-UHFFFAOYSA-N methyl vinyl ether Chemical compound COC=C XJRBAMWJDBPFIM-UHFFFAOYSA-N 0.000 description 1
- 239000001923 methylcellulose Substances 0.000 description 1
- 235000010981 methylcellulose Nutrition 0.000 description 1
- LVHBHZANLOWSRM-UHFFFAOYSA-N methylenebutanedioic acid Natural products OC(=O)CC(=C)C(O)=O LVHBHZANLOWSRM-UHFFFAOYSA-N 0.000 description 1
- 150000002762 monocarboxylic acid derivatives Chemical class 0.000 description 1
- 229930014626 natural product Natural products 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- 150000007524 organic acids Chemical class 0.000 description 1
- 235000005985 organic acids Nutrition 0.000 description 1
- 239000007800 oxidant agent Substances 0.000 description 1
- 230000004792 oxidative damage Effects 0.000 description 1
- 238000010012 oxidative desizing Methods 0.000 description 1
- 239000001814 pectin Substances 0.000 description 1
- 235000010987 pectin Nutrition 0.000 description 1
- 229920001277 pectin Polymers 0.000 description 1
- HVAMZGADVCBITI-UHFFFAOYSA-N pent-4-enoic acid Chemical compound OC(=O)CCC=C HVAMZGADVCBITI-UHFFFAOYSA-N 0.000 description 1
- 229960003330 pentetic acid Drugs 0.000 description 1
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 description 1
- 239000010452 phosphate Substances 0.000 description 1
- 150000003009 phosphonic acids Chemical class 0.000 description 1
- 239000000049 pigment Substances 0.000 description 1
- 229920002647 polyamide Polymers 0.000 description 1
- 229920000728 polyester Polymers 0.000 description 1
- 229920006149 polyester-amide block copolymer Polymers 0.000 description 1
- 229920001444 polymaleic acid Polymers 0.000 description 1
- 229920006254 polymer film Polymers 0.000 description 1
- 239000011591 potassium Substances 0.000 description 1
- 159000000001 potassium salts Chemical class 0.000 description 1
- WSHYKIAQCMIPTB-UHFFFAOYSA-M potassium;2-oxo-3-(3-oxo-1-phenylbutyl)chromen-4-olate Chemical compound [K+].[O-]C=1C2=CC=CC=C2OC(=O)C=1C(CC(=O)C)C1=CC=CC=C1 WSHYKIAQCMIPTB-UHFFFAOYSA-M 0.000 description 1
- 235000012015 potatoes Nutrition 0.000 description 1
- 239000002244 precipitate Substances 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 238000002203 pretreatment Methods 0.000 description 1
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 description 1
- UIIIBRHUICCMAI-UHFFFAOYSA-N prop-2-ene-1-sulfonic acid Chemical compound OS(=O)(=O)CC=C UIIIBRHUICCMAI-UHFFFAOYSA-N 0.000 description 1
- MRXVCTWDXRBVLW-UHFFFAOYSA-N prop-2-enoylsulfamic acid Chemical compound OS(=O)(=O)NC(=O)C=C MRXVCTWDXRBVLW-UHFFFAOYSA-N 0.000 description 1
- RZKYDQNMAUSEDZ-UHFFFAOYSA-N prop-2-enylphosphonic acid Chemical compound OP(O)(=O)CC=C RZKYDQNMAUSEDZ-UHFFFAOYSA-N 0.000 description 1
- 235000018102 proteins Nutrition 0.000 description 1
- 102000004169 proteins and genes Human genes 0.000 description 1
- 108090000623 proteins and genes Proteins 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 239000005871 repellent Substances 0.000 description 1
- 239000011347 resin Substances 0.000 description 1
- 229920005989 resin Polymers 0.000 description 1
- 235000009566 rice Nutrition 0.000 description 1
- 230000009528 severe injury Effects 0.000 description 1
- 238000004513 sizing Methods 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 159000000000 sodium salts Chemical class 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 238000010186 staining Methods 0.000 description 1
- 239000007858 starting material Substances 0.000 description 1
- 239000011550 stock solution Substances 0.000 description 1
- 229910052712 strontium Inorganic materials 0.000 description 1
- 230000019635 sulfation Effects 0.000 description 1
- 238000005670 sulfation reaction Methods 0.000 description 1
- 239000012209 synthetic fiber Substances 0.000 description 1
- 229920002994 synthetic fiber Polymers 0.000 description 1
- 239000011975 tartaric acid Substances 0.000 description 1
- 235000002906 tartaric acid Nutrition 0.000 description 1
- 238000004448 titration Methods 0.000 description 1
- ZTWTYVWXUKTLCP-UHFFFAOYSA-N vinylphosphonic acid Chemical compound OP(O)(=O)C=C ZTWTYVWXUKTLCP-UHFFFAOYSA-N 0.000 description 1
- NLVXSWCKKBEXTG-UHFFFAOYSA-N vinylsulfonic acid Chemical compound OS(=O)(=O)C=C NLVXSWCKKBEXTG-UHFFFAOYSA-N 0.000 description 1
- 239000001993 wax Substances 0.000 description 1
- 235000019386 wax ester Nutrition 0.000 description 1
- 238000009941 weaving Methods 0.000 description 1
- 238000009736 wetting Methods 0.000 description 1
Classifications
-
- 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
- D06L1/00—Dry-cleaning or washing fibres, filaments, threads, yarns, fabrics, feathers or made-up fibrous goods
- D06L1/12—Dry-cleaning or washing fibres, filaments, threads, yarns, fabrics, feathers or made-up fibrous goods using aqueous solvents
- D06L1/14—De-sizing
-
- 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
- D06L4/10—Bleaching fibres, filaments, threads, yarns, fabrics, feathers or made-up fibrous goods; Bleaching leather or furs using agents which develop oxygen
-
- 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
- D06L4/10—Bleaching fibres, filaments, threads, yarns, fabrics, feathers or made-up fibrous goods; Bleaching leather or furs using agents which develop oxygen
- D06L4/13—Bleaching fibres, filaments, threads, yarns, fabrics, feathers or made-up fibrous goods; Bleaching leather or furs using agents which develop oxygen using inorganic agents
Definitions
- the present invention relates to an improved process for the continuous pretreatment of cellulose-containing textile material
- a three-stage pretreatment is carried out for fabrics, consisting of desizing, decoction and bleaching.
- Each of these three treatment steps is subdivided into an impregnation step, in which the treatment liquor is applied to the textile material, a dwell step, in which the chemicals and auxiliaries applied to the textile material can react, and a washout step.
- the present pretreatment method can be used much more rationally.
- a pre-cleaning is sufficient, in which the treatment liquor (impregnating liquor), which contains certain additives, is applied to the textile goods and then immediately washed out - without dwell time - as well as the bleaching immediately afterwards in order to achieve good bleaching results with a high level of fabric protection to reach.
- Particularly good bleaching results result in particular when working with an increased liquor application when impregnating with the bleaching liquor.
- Such good results which largely correspond to those of the usual three-stage pretreatment, were not to be expected.
- the pre-cleaning liquor in (a) does not contain the additives mentioned below, there will be insufficient bleaching results.
- the desizing effect may not be sufficient in some cases.
- a desizing with additional starch-degrading enzymes can be carried out after the impregnation at (a). In such cases, however, it makes more sense to carry out the present pretreatment process after desizing by adding the additives mentioned below to the first or second washing bath at the end of the desizing process. It is also possible to add the additives mentioned below directly to the desizing liquor, which contains the starch-degrading enzymes.
- the natural product cotton also contains up to 10% by weight of natural impurities which, depending on the origin, provenance, growth conditions and ripeness of the harvest, can fluctuate considerably.
- natural accompanying substances of cotton are in particular proteins, pectin, wax esters and alcohols, hemicellulose, lignin substances, resins, colored pigments, organic acids and mineral salts with the cations of Ca, Mg, Na, K, Fe, Mn, Cu and Al and the anions Carbonate, phosphate, sulfate, chloride and silicate.
- the warp threads must be enveloping through them
- the purpose of the pretreatment is to prepare the textile material in such a way that disruptive accompanying substances are removed as far as possible and, above all, uniformly, without the exposed clean cotton, the ⁇ -cellulose, being damaged too severely. Because of the difference between these substances, both in their physical appearance and in the chemical constitution already mentioned, this cannot be achieved by a simple washing-out process.
- Knitted fabric which is produced by knitting or knitting is normally not sized and therefore, unlike the fabric, does not require a desizing step.
- the object of the present invention was to achieve better bleaching effects in a more rational manner than in the case of a pretreatment according to the prior art.
- the process defined at the outset was found, which is characterized in that the treatment bath at (a) additionally 1 to 10% by weight, preferably 2 to 6% by weight, based on the weight of the textile material, (i) either an aminopolycarboxylic acid, a hydroxyalkyl- or aminophosphonic acid, a polycarboxylic acid, a polyhydroxycarboxylic acid or an inorganic polymetaphosphate or a mixture thereof as a complexing agent for polyvalent metal ions or
- a water-soluble polymer which is composed of 40 to 100% by weight of monoethylenically unsaturated mono- or dicarboxylic acids or their anhydrides or a mixture thereof and has a K value of 8 to 80 as a dispersant or
- the treatment bath in (a) additionally contains 1 to 10% by weight, based on the weight of the textile material, of component (i). In a further preferred embodiment, the treatment bath in (a) additionally contains 1 to 10% by weight, based on the weight of the textile material, of component (ii). In a further preferred embodiment, the treatment bath at (a) additionally contains 1 to 10% by weight, based on the weight of the textile goods, of a mixture (iii) of components (i) and (ii) by weight. Ratio of 10: 1 to 1:10, preferably in a weight ratio of 4: 1 to 1: 4.
- the troublesome accompanying substances are removed so effectively that the subsequent peroxide bleaching with higher amounts of alkali and, if necessary, also higher amounts of peroxide with excellent bleaching results and without significant damage to the goods occur and the alkaline decoction can be dispensed with.
- the dispersants added in accordance with the invention are able to disperse insoluble compounds of an inorganic and organic type, for example also insoluble hydroxides or carbonates of alkaline earth metals or heavy metals, and insoluble salts of these cations with, for example, pectinate, fatty acids or sizes, and thereby, in addition to the improved precleaning effect, precipitate out and to prevent roller coverings.
- complexing agents for polyvalent metal ions according to the invention, alkaline earth and heavy metal ions are also removed from the cotton by complexing, precipitation of insoluble salts of these cations is prevented and thus ideal conditions are created for subsequent, problem-free peroxide bleaching and subsequent dyeing.
- the textile material is freed from interfering substances so well that it bleaches during the subsequent peroxide bleaching (b) behaves much more favorably than without the additives according to the invention, even more favorably than after an additional alkali decoction before the peroxide bleaching.
- Peeling removal is a question of bleaching time, amount of alkali and peroxide.
- Good skin removal normally requires an alkaline decoction with 30 to 60 g / 1 caustic soda and a usual wetting or washing agent at 100 ° C for 2 minutes to 30 minutes after the normal desizing and then a peroxide bleaching with 30 to 50 ml / 1 hydrogen peroxide (35% by weight) and 5 to 10 g / 1 caustic soda, in addition to the usual bleach stabilizers and wetting agents or detergents.
- the peel removal is usually not successful because the high amounts of alkali (> 10 g / 1 caustic soda) required for peel removal promote strong peroxide decomposition and lead to severe damage to the goods.
- the method of operation according to the invention there is a condition of the goods, free of impurities which interfere with the peroxide bleaching, which enables peroxide bleaching even with significantly higher amounts of caustic soda with excellent bleaching results, without damage to the goods and free of trays.
- the bleaching can also be carried out with high amounts of peroxide and with a longer bleaching time (up to 60 min) without significant damage to the goods. Because of the excellent stability of the peroxide and its optimal utilization for bleaching the colored accompanying substances of the cotton
- 25th DE-A 27 35 816 (1) describes a process for desizing and bleaching textile material containing or consisting of cellulose by simultaneous enzymatic desizing and pretreatment with a solution of sodium dithionite ("hydrosulfite") and a customary heavy metal complexing agent with addition
- Sodium dithionite acts as a reducing agent and requires the use of a buffer system, because the oxidation of dithionite produces sulphurous acid in addition to sulfate anions and the pH value drops as a result.
- This acidic running of the treatment bath must be avoided by buffering in order to prevent the self-decomposition of the di-thionite, leaving the optimal pH range for the complexation and the occurrence of S0 odor.
- the sulfate ions formed in the oxidation of the dithionite enter the wastewater, pollute it and, as is known, increase the corrosion of sewer channels and pipes made of concrete, also recognizable by the limit values for sulfations in the wastewater specified by the environmental authorities.
- the method according to the invention does not require a reducing agent or a buffer system and therefore does not have any of the disadvantages mentioned there.
- the starting materials can be handled and used as solutions without problems.
- Complexing agents for polyvalent metal ions can generally also be used with the complexing agents to be used, 15 not just the usual heavy metal complexing agents. Heavy metal ions should be removed as far as possible, but also alkaline earth metal ions or aluminum ions. Thanks to the dispersing effect of the dispersants to be used, insoluble compounds of polyvalent metal ions are also removed from the textile, not just soluble cations.
- DE-B 28 14 354 (2) describes a process for desizing textiles containing or consisting of starch-sized cellulose using a combination of peroxidized
- the process is preferably coupled with the alkaline decoction and at pH values between 12 to 14 and at a temperature of approx.
- EP-B 101 567 (3) relates to the preparation of aqueous concentrated homogeneous 25 to 60% by weight solutions of mixtures having a pH of 3 to 7, preferably in a weight ratio of 7: 1 to 1: 7, from homopolymers of acrylic acid and / or copolymers of acrylic acid with up to 50% by weight of maleic acid and / or maleic anhydride and K values from 10 to 25 and nitrilotriacetic acid, polyaminopolycarboxylic acids, polyaminopolyphosphonic acids and / or hydroxyalkane polyphosphonic acids, the dissolved components completely or at least 20% in the form of the potassium salts and in the latter case the rest in the form of the free acid.
- Their use in pretreatment or dyeing baths for textile material consisting of cellulose or containing cellulose as a combined dispersing agent and metal ion complexing agent is mentioned. There is no mention of a usability for pre-cleaning or desizing baths.
- the sophisticated pre-cleaning (a) of cellulose-containing or cellulose-containing textile goods can be carried out continuously in liquor ratios of approximately 1: 1 or in the case of knitted fabrics also liquor ratios of 1: 5 to 1:20.
- the treatment liquor is applied at immersion times (contact times) of the textile goods of usually 5 to 30 seconds, in particular 10 to 20 seconds, the treatment bath having a temperature between the room temperature (20 ° C.) and 70 ° C. can.
- the goods loaded with the treatment liquor are squeezed to a liquor absorption of approximately 100% (corresponding to a liquor ratio of approximately 1: 1) and then either washed out immediately or with a residence time of 5 minutes subjected to up to 24 hours at room temperature or from 30 seconds to 3 minutes at approx. 100 ° C and only then washed out.
- the treated textile goods are usually washed out hot (at temperatures between 80 to 100 ° C) and then cold, usually in a row in several wash baths.
- the pH of the treatment liquor in (a) should be between 5 and 11, preferably between 6 and 10.
- the pre-cleaning step (a) according to the invention consisting of impregnating the textile material with the treatment liquor and then immediately washing it out, is often sufficient, to get good bleaching results. If the desizing effect is not optimal, a longer dwell time can be allowed after the impregnation step and only then can it be washed out.
- This desizing process with the addition of enzymes can take place immediately after the impregnation process according to the invention at (a) or afterwards, that is to say in the first or second washing bath after the pre-cleaning process (a). It is also possible to add the additives according to the invention directly into the desizing liquor which contains the starch-degrading enzymes.
- Bacterial, malt or pancreatic amylase are mostly used as enzymes, most enzyme types being effective at low temperatures (up to 70 ° C), special types also at higher temperatures (70 ° C to 120 ° C).
- the amounts of enzyme used are generally between 1 and 8 g / l.
- These amylases develop optimal activity mostly in a certain pH range, which lies between the pH values 5 to 11, mostly between 6 and 8.
- residence or reaction times of up to 24 hours at room temperature or even only 1 to 2 minutes at 100 ° C. agile.
- the desizing liquor usually also contains wetting agents and detergents (surfactants) and other customary auxiliaries, such as common salt and minor Amounts of calcium salts (both for enzyme activation), which are either added separately or introduced automatically via the water hardness.
- wetting agents and detergents surfactants
- other customary auxiliaries such as common salt and minor Amounts of calcium salts (both for enzyme activation), which are either added separately or introduced automatically via the water hardness.
- the peroxide bleaching (b) following the pre-cleaning (a) usually takes place continuously at liquor textile to liquor liquor ratios of 1: 0.6 to 1: 1.7, preferably 1: 1 to 1: 1.5 (corresponding to liquor uptake of 60 wt .-%, based on the textile, up to 170 wt .-%, preferably 100 wt .-% to 150 wt .-%).
- Peroxide bleaching is generally carried out at temperatures between 70 to 130 ° C., preferably 98 ° to 120 ° C., for 2 to 60 minutes, preferably 10 to 30 minutes.
- aqueous solution constituents of the bleaching liquor are used, and caustic soda surfactants and other conventional auxiliaries, such as conventional inorganic and organic stabilizers, which ensure sufficient stability of the hydrogen peroxide under bleaching conditions should - and, if necessary, dispersants, which are intended to prevent the precipitation of insoluble compounds and roller coverings.
- caustic soda surfactants and other conventional auxiliaries such as conventional inorganic and organic stabilizers, which ensure sufficient stability of the hydrogen peroxide under bleaching conditions should - and, if necessary, dispersants, which are intended to prevent the precipitation of insoluble compounds and roller coverings.
- the amounts of peroxide and caustic soda to be used depend on the textile material, the chosen method and the desired bleaching result, namely whether colored goods (textile material that is to be dyed or printed) or a solid white (for white goods that are not dyed or printed) is) aimed for.
- the amounts of peroxide used are generally between 10 to 60 g / 1 H 2 O 2 (35% by weight), preferably between 20 to 50 g / 1, the amounts of caustic soda between 5 and 50 g / 1, preferably between 10 and 25 g / 1.
- the preferred procedure in the bleaching step (b) is the continuous mode of operation, in which the textile material is in a wide web after the pre-cleaning (a) and the subsequent washing or rinsing with the bleaching liquor impregnated and bleached in a steamer at 98 to 120 ° C for 10 to 30 minutes and then washed out intensively hot (several times at 95 ° C) and cold in the usual way.
- Suitable complexing agents (i) for polyvalent metal ions are amino polycarboxylic acids, hydroxyalkyl and amino phosphonic acids, poly (hydroxy) carboxylic acids and inorganic polymetaphosphates, as free acids or in neutralized form as alkali or ammonium salts. Examples include:
- Nitrilotriacetic acid ethylenediaminetetraacetic acid, diethylenetriaminepentaacetic acid, ß-hydroxyethylaminodiacetic acid, N, N-di- (ß-hydroxyethyl) -glycine, 1, 3-propylenediamine tetraacetic acid, 1, 2-propylenediamine tetraacetic acid, N-ß-hydroxypropylhydroxy-ethylenediamine-triethyl-hydroxy-ethylenediamine-triethyl-hydroxy-ethylenediamine-hydroxy-triethyl-hydroxy-ethylenedi-hydroxy-triethyl-ethylenediamine-tri-hydroxy-triethyl-ethylenediamine-2-hydroxypropyl-ethylenedi-hydroxy-triethyl-ethylenediamine-2-hydroxypropyl-ethylenedi-hydroxypropyl-ethylenediamin-2-hydroxypropyl-ethylenedi-l, 3-diamine tetraacetic acid, di ( ⁇
- Preferred complexing agents are aminopolycarboxylic acids, phosphonic acids and polyhydroxycarboxylic acids, in particular nitrilotriacetic acid, diethylenetriamine-pentamethylene-phosphonic acid and poly- ⁇ -hydroxyacrylic acid.
- the complexing agents for polyvalent metal ions should have sequestering properties for divalent or trivalent ions of the metals Ca, Mg, Ba, Sr, Mn, Co, Cu, Fe, Ni, Co, Zn, Cd and Al, especially for ions of the metals Ca. , Mg, Fe, Cu, Mn and Zn and AI, which are found more often on raw cotton.
- Suitable dispersants (ii) are water-soluble polymers which polymerize monoethylenically unsaturated mono- and / or dicarboxylic acid units in amounts> .40% by weight, preferably> 60% by weight, in particular> 80% by weight contain and have K values 5 between 8 and 80, preferably between 10 and 40.
- the K values are an approximate measure of the molecular weight or degree of polymerization and are according to H. Fikentscher, Cellulose-Chemie 13, p. 60 (1932) in 2% by weight solutions in dimethylformamide at 25 ° C. certainly.
- Suitable monoethylenically unsaturated monocarboxylic acids are those which contain 3 to 10 carbon atoms in the molecule.
- Acrylic acid or methacrylic acid are particularly mentioned here; however, one can also use ⁇ -hydroxyacrylic acid, vinyl acetic acid, allylacetic acid, pro
- pylideneacetic acid ethylidene propionic acid, dimethylacrylic acid or C 2 - to C 6 -alkyl half-esters of dicarboxylic acids, especially maleic acid.
- Suitable monoethylenically unsaturated dicarboxylic acids in the polymers are, for example, maleic acid, itaconic acid, glutaconic acid, methylene malonic acid and citraconic acid
- acrylamide, methacrylamide, vinyl acetate, acrylonitrile, hydroxyethyl and hydroxypropyl acrylate, methyl vinyl ether and diisobutylene are particularly suitable.
- These comonomers can increase the solubility of the dispersants (ii) in water or in dilute
- the dispersant (ii) is exposed to water-soluble copolymers
- water-soluble polymers based on monomers containing carboxyl groups have proven to be particularly advantageous
- Dispersants (ii) have been proven in which the carboxyl groups are present in the polymer in the form of the sodium salts. But also the lithium, potassium, ammonium and substituted ammonium salts, e.g. Methyl, ethyl, dimethyl, diethyl, trimethyl, triethyl, diethanol, triethanol or triisopropanol ammonium salts can be used.
- textiles made from cellulose and mixtures thereof with other native or synthetic fibers, e.g. Linen, polyester or polyamide.
- native or synthetic fibers e.g. Linen, polyester or polyamide.
- the most important types of fibers are pure cotton and mixtures of cotton and polyester.
- the object of the invention to develop a more rational, economical and ecologically improved pretreatment process is thus achieved by adding dispersants and / or complexing agents for polyvalent metal ions, in each case alone or in mixtures, in amounts of 1% by weight to 10% by weight. %, preferably 2 to 6% by weight, based on the weight of the textile, dissolved in the pre-cleaning liquor and immediately following alkaline peroxide bleaching. ⁇ ⁇ - " '
- the residual peroxide content on the textile goods at the beginning of the bleaching (before the start of bleaching) and at the end of the bleaching time was determined in a known manner using a 0.1 n KMnO solution.
- the pieces of tissue of a certain (equal) weight were placed in aqueous sulfuric acid solution, thereby stopping the peroxide decomposition and determining the peroxide present on the goods by titrimetry.
- Bleach was set to 100% and the amount of residual peroxide at the end of the bleach was based on it, that is to say as a percentage of the initial value. The higher the amount of residual peroxide, the better the stability of the peroxide in bleaching.
- the average degree of polymerization is a measure of the fiber damage; the higher the values or the closer to the DP value of the raw goods, the lower the damage. It was determined viscosimetrically in copper cuoxam solution.
- the 'suction time' was determined as a measure of the hydrophilicity of the textile material.
- a standardized strip of tissue (width 3 cm) is immersed 1 cm deep in the colored water and the time in seconds after which the water has risen exactly 1 cm in the strip of tissue is measured. The suction time
- the strength detection according to the Tegewa method in which the remaining starch on the tissue is indicated by a blue-violet staining by a spot test with iodine-iodine potassium, is generally known.
- the degree of desizing can be determined using the Tegewa Association's violet scale, which shows 9 shades of color. Grade 9 means complete desizing, grade 1 no desizing.
- a twill fabric made of raw cotton of 310 g / m 2 , finished with water-soluble starch derivatives, was impregnated with a liquor of 70 ° C and a liquor absorption of approx. 100% (corresponding to a liquor ratio of approx. 1: 1) (immersion time contact time of the fabric with the fleet was 20 seconds) 5 g / 1 10-fold ethylated nonylphenyl xg / 1 additives according to Table 1
- Example 1a If, in accordance with Example 1a, the product mixture A according to the invention was added to the pre-cleaning liquor, but the subsequent peroxide bleaching was carried out using only 5 g / 1 caustic soda instead of 15 g / 1 caustic soda, the peeling was insufficient and the degree of whiteness according to Berger was only 80.
- the body tissue as in example la-d was impregnated for desizing with a liquor of 60 ° C. and a liquor absorption of approx. 100% (corresponding to a liquor ratio of approx. 1: 1)
- Example 1 contained and had been adjusted to a pH of approx. 8, immediately (without dwell time) washed twice hot and twice cold and then subjected to peroxide bleaching as in Example 1, but with a liquor absorption of 100%.
- Example 1 contained and had been adjusted to a pH of about 7.5, and then immediately washed, as described in Example 1, and bleached.
- NTA nitrilotriacetic acid
Landscapes
- Engineering & Computer Science (AREA)
- Textile Engineering (AREA)
- Chemical & Material Sciences (AREA)
- Inorganic Chemistry (AREA)
- Detergent Compositions (AREA)
- Treatments For Attaching Organic Compounds To Fibrous Goods (AREA)
- Treatment Of Fiber Materials (AREA)
- Chemical Or Physical Treatment Of Fibers (AREA)
Applications Claiming Priority (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| DE4317060A DE4317060A1 (de) | 1993-05-21 | 1993-05-21 | Verfahren zur kontinuierlichen Vorbehandlung von cellulosehaltigem Textilgut |
| DE4317060 | 1993-05-21 | ||
| PCT/EP1994/001507 WO1994028228A1 (fr) | 1993-05-21 | 1994-05-10 | Procede de pretraitement en continu d'un materiau textile contenant de la cellulose |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| EP0699247A1 true EP0699247A1 (fr) | 1996-03-06 |
| EP0699247B1 EP0699247B1 (fr) | 1999-04-21 |
Family
ID=6488666
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| EP94917611A Expired - Lifetime EP0699247B1 (fr) | 1993-05-21 | 1994-05-10 | Procede de pretraitement en continu d'un materiau textile contenant de la cellulose |
Country Status (7)
| Country | Link |
|---|---|
| US (1) | US5820636A (fr) |
| EP (1) | EP0699247B1 (fr) |
| AT (1) | ATE179231T1 (fr) |
| DE (2) | DE4317060A1 (fr) |
| DK (1) | DK0699247T3 (fr) |
| ES (1) | ES2130424T3 (fr) |
| WO (1) | WO1994028228A1 (fr) |
Families Citing this family (11)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH108092A (ja) * | 1996-06-21 | 1998-01-13 | Mitsubishi Paper Mills Ltd | 過酸化物漂白用安定化剤及びそれを用いた繊維系物質の漂白方法 |
| DE10201690A1 (de) * | 2002-01-17 | 2003-07-31 | Basf Ag | Verfahren zur Wiedergewinnung von Schlichten durch eine Kombination von Entschlichtung mit Dispergiermitteln/Komplexbildnern und anschließendem Recycling |
| DE10301535A1 (de) * | 2003-01-17 | 2004-07-29 | Cht R. Beitlich Gmbh | Verfahren zur Veredlung von textilem Fasermaterial |
| JP5122821B2 (ja) | 2003-11-28 | 2013-01-16 | イーストマン ケミカル カンパニー | セルロースインターポリマー及び酸化方法 |
| US20070004849A1 (en) * | 2004-09-24 | 2007-01-04 | Karl Siemensmeyer | Method for the preliminary treatment of cellulose-containing textile |
| EP1876285A1 (fr) * | 2006-07-05 | 2008-01-09 | DyStar Textilfarben GmbH & Co. Deutschland KG | Déminéralisation et désencollage de matériaux textiles en une seule operation |
| WO2013178875A1 (fr) | 2012-05-29 | 2013-12-05 | Kemira Oyj | Procédé de traitement d'un matériau fibreux et nouvelle composition |
| CN102926215A (zh) * | 2012-11-28 | 2013-02-13 | 华纺股份有限公司 | 涤棉混纺织物前处理方法 |
| AT515152B1 (de) | 2013-11-26 | 2015-12-15 | Chemiefaser Lenzing Ag | Verfahren zum Vorbehandeln von rückgewonnenen Baumwollfasern zur Verwendung bei der Herstellung von Formkörpern aus regenerierter Cellulose |
| CN103993485A (zh) * | 2014-04-23 | 2014-08-20 | 江苏华艺服饰有限公司 | 一种适用于羊毛织物退浆剂 |
| CN121593223B (zh) * | 2026-01-29 | 2026-04-28 | 科一(福建)超纤有限责任公司 | 一种具有金属光泽的织物面料及其制备方法 |
Family Cites Families (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US2960383A (en) * | 1958-07-25 | 1960-11-15 | Du Pont | Continuous process for rapidly bleaching woven cotton fabric |
| DE2735816C3 (de) * | 1977-08-09 | 1981-08-13 | Basf Ag, 6700 Ludwigshafen | Verfahren zum Entschlichten und Bleichen von Textilgut |
| US4426203A (en) * | 1981-01-06 | 1984-01-17 | Ciba-Geigy Corporation | Stable anhydrous textile assistant |
| DE3227915A1 (de) * | 1982-07-27 | 1984-02-02 | Basf Ag, 6700 Ludwigshafen | Waessrige konzentrierte loesungen von mischungen aus organischen komplexbildnern und dispergiermitteln auf basis von polymeren aliphatischen carbonsaeuren |
| US4539353A (en) * | 1983-01-25 | 1985-09-03 | Ciba-Geigy Corporation | Aqueous composition of polymaleic acid, surfactants and complexing agents, and its preparation and use as an assistant in the pretreatment of cellulose-containing fibre materials |
| DE4208106B4 (de) * | 1991-03-20 | 2006-10-05 | Clariant Finance (Bvi) Ltd. | Vorbehandlung von Textilfasermaterial |
-
1993
- 1993-05-21 DE DE4317060A patent/DE4317060A1/de not_active Withdrawn
-
1994
- 1994-05-10 ES ES94917611T patent/ES2130424T3/es not_active Expired - Lifetime
- 1994-05-10 DK DK94917611T patent/DK0699247T3/da active
- 1994-05-10 EP EP94917611A patent/EP0699247B1/fr not_active Expired - Lifetime
- 1994-05-10 DE DE59408145T patent/DE59408145D1/de not_active Expired - Fee Related
- 1994-05-10 WO PCT/EP1994/001507 patent/WO1994028228A1/fr not_active Ceased
- 1994-05-10 US US08/537,750 patent/US5820636A/en not_active Expired - Fee Related
- 1994-05-10 AT AT94917611T patent/ATE179231T1/de not_active IP Right Cessation
Non-Patent Citations (1)
| Title |
|---|
| See references of WO9428228A1 * |
Also Published As
| Publication number | Publication date |
|---|---|
| ATE179231T1 (de) | 1999-05-15 |
| ES2130424T3 (es) | 1999-07-01 |
| DE59408145D1 (de) | 1999-05-27 |
| DE4317060A1 (de) | 1994-11-24 |
| DK0699247T3 (da) | 1999-10-25 |
| WO1994028228A1 (fr) | 1994-12-08 |
| EP0699247B1 (fr) | 1999-04-21 |
| US5820636A (en) | 1998-10-13 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| EP0737215B1 (fr) | Copolymerisats greffes de monomeres insatures et composes polyhydroxy, leur procede de preparation et leur utilisation | |
| DE2226784A1 (fr) | ||
| EP0736049B1 (fr) | Copolymeres d'acides carboxyliques insatures, leur procede de fabrication et leur utilisation | |
| EP0699247B1 (fr) | Procede de pretraitement en continu d'un materiau textile contenant de la cellulose | |
| EP0628655B1 (fr) | Adjuvants de blanchiment | |
| DE69709656T2 (de) | Verfahren zum bleichen von papierzellstoff | |
| DE3423452A1 (de) | Stabilisierende mischung zur peroxidbleiche zellulosehaltiger materialien | |
| EP0094656B1 (fr) | Procédé pour le désencollage et le blanchiment simultanés de matières textiles en fibres cellulosiques | |
| DE69604598T2 (de) | Verfahren zum schlichten von fäden | |
| DE4203797A1 (de) | Bleichregulator-zusammensetzungen und bleichverfahren damit | |
| DE3413367C2 (fr) | ||
| DE69636121T2 (de) | Polyvinylalkohol copolymer ionomere, deren herstellung und verwendung zur textilbeschichtung | |
| EP1583861B1 (fr) | Procede pour le finissage de matieres fibreuses textiles | |
| DE2441277C3 (de) | Verfahren zum Schlichten von Cellulosefasern enthaltenden Garnen | |
| EP0801165B1 (fr) | Prétraitement de textiles | |
| EP0220170B1 (fr) | Procédé et composition pour le traitement alcalin de substrats cellulosiques | |
| EP0831165A2 (fr) | Agent pour la prétraitement de fibres | |
| Rowe | Desizing/Scouring with Hydrogen Peroxide. | |
| WO2003069050A1 (fr) | Procédé pour le désencollage et le nettoyage enzymatiques simultanés d'un matériau contenant de la cellulose | |
| DE349655C (de) | Verfahren, um Textilfasern aller Art von ihren staerkeartigen, gummiartigen, gelatineartigen und fetten, von der Appretur oder Versteifung u. dgl. herstammenden Stoffen mit Hilfe von Bakterien zu befreien | |
| EP0759103A1 (fr) | Utilisation de polymeres solubles dans l'eau et de polyhydroxymonocarboxylates ou polyhydroxybicarboxylates dans le blanchiment de textiles | |
| DE1000995B (de) | Verfahren zur Verbesserung der Eigenschaften von geformten Gegenstaenden aus Mischestern der Cellulose, welche ungesaettigte und gesaettigte Saeurereste enthalten | |
| WO2003060225A1 (fr) | Procede de recuperation d'enduits par combinaison de desencollage au moyen d'agents dispersants/complexants et recyclage consecutif | |
| DE2814354B1 (de) | Verfahren zum Entschlichten von Cellulose enthaltenden oder daraus bestehenden Textilien | |
| DE2616261C3 (de) | Wasch- und Reinigungsmittel, die Carboxyl- und Hydroxylgruppen enthaltende Copolymerisate enthalten |
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: 19951024 |
|
| AK | Designated contracting states |
Kind code of ref document: A1 Designated state(s): AT BE CH DE DK ES FR GB IT LI NL PT SE |
|
| 17Q | First examination report despatched |
Effective date: 19960530 |
|
| GRAG | Despatch of communication of intention to grant |
Free format text: ORIGINAL CODE: EPIDOS AGRA |
|
| GRAG | Despatch of communication of intention to grant |
Free format text: ORIGINAL CODE: EPIDOS AGRA |
|
| GRAH | Despatch of communication of intention to grant a patent |
Free format text: ORIGINAL CODE: EPIDOS IGRA |
|
| GRAH | Despatch of communication of intention to grant a patent |
Free format text: ORIGINAL CODE: EPIDOS IGRA |
|
| GRAA | (expected) grant |
Free format text: ORIGINAL CODE: 0009210 |
|
| AK | Designated contracting states |
Kind code of ref document: B1 Designated state(s): AT BE CH DE DK ES FR GB IT LI NL PT SE |
|
| REF | Corresponds to: |
Ref document number: 179231 Country of ref document: AT Date of ref document: 19990515 Kind code of ref document: T |
|
| REG | Reference to a national code |
Ref country code: CH Ref legal event code: EP |
|
| REF | Corresponds to: |
Ref document number: 59408145 Country of ref document: DE Date of ref document: 19990527 |
|
| GBT | Gb: translation of ep patent filed (gb section 77(6)(a)/1977) |
Effective date: 19990524 |
|
| REG | Reference to a national code |
Ref country code: ES Ref legal event code: FG2A Ref document number: 2130424 Country of ref document: ES Kind code of ref document: T3 |
|
| ET | Fr: translation filed | ||
| REG | Reference to a national code |
Ref country code: DK Ref legal event code: T3 |
|
| 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 | ||
| REG | Reference to a national code |
Ref country code: GB Ref legal event code: IF02 |
|
| PGFP | Annual fee paid to national office [announced via postgrant information from national office to epo] |
Ref country code: PT Payment date: 20040503 Year of fee payment: 11 |
|
| PGFP | Annual fee paid to national office [announced via postgrant information from national office to epo] |
Ref country code: NL Payment date: 20040505 Year of fee payment: 11 |
|
| PGFP | Annual fee paid to national office [announced via postgrant information from national office to epo] |
Ref country code: SE Payment date: 20040506 Year of fee payment: 11 |
|
| PGFP | Annual fee paid to national office [announced via postgrant information from national office to epo] |
Ref country code: DK Payment date: 20040517 Year of fee payment: 11 |
|
| PGFP | Annual fee paid to national office [announced via postgrant information from national office to epo] |
Ref country code: BE Payment date: 20040716 Year of fee payment: 11 |
|
| PG25 | Lapsed in a contracting state [announced via postgrant information from national office to epo] |
Ref country code: SE Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES Effective date: 20050511 |
|
| PG25 | Lapsed in a contracting state [announced via postgrant information from national office to epo] |
Ref country code: DK Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES Effective date: 20050531 Ref country code: BE Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES Effective date: 20050531 |
|
| 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: 20051110 |
|
| BERE | Be: lapsed |
Owner name: *BASF A.G. Effective date: 20050531 |
|
| PG25 | Lapsed in a contracting state [announced via postgrant information from national office to epo] |
Ref country code: NL Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES Effective date: 20051201 |
|
| EUG | Se: european patent has lapsed | ||
| NLV4 | Nl: lapsed or anulled due to non-payment of the annual fee |
Effective date: 20051201 |
|
| REG | Reference to a national code |
Ref country code: DK Ref legal event code: EBP |
|
| BERE | Be: lapsed |
Owner name: *BASF A.G. Effective date: 20050531 |
|
| PGFP | Annual fee paid to national office [announced via postgrant information from national office to epo] |
Ref country code: ES Payment date: 20080619 Year of fee payment: 15 Ref country code: DE Payment date: 20080515 Year of fee payment: 15 Ref country code: CH Payment date: 20080616 Year of fee payment: 15 |
|
| PGFP | Annual fee paid to national office [announced via postgrant information from national office to epo] |
Ref country code: AT Payment date: 20080514 Year of fee payment: 15 |
|
| PGFP | Annual fee paid to national office [announced via postgrant information from national office to epo] |
Ref country code: IT Payment date: 20080528 Year of fee payment: 15 |
|
| PGFP | Annual fee paid to national office [announced via postgrant information from national office to epo] |
Ref country code: GB Payment date: 20080514 Year of fee payment: 15 |
|
| REG | Reference to a national code |
Ref country code: CH Ref legal event code: PL |
|
| GBPC | Gb: european patent ceased through non-payment of renewal fee |
Effective date: 20090510 |
|
| PG25 | Lapsed in a contracting state [announced via postgrant information from national office to epo] |
Ref country code: LI Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES Effective date: 20090531 Ref country code: CH Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES Effective date: 20090531 Ref country code: AT Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES Effective date: 20090510 |
|
| REG | Reference to a national code |
Ref country code: FR Ref legal event code: ST Effective date: 20100129 |
|
| 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: 20090602 |
|
| PGFP | Annual fee paid to national office [announced via postgrant information from national office to epo] |
Ref country code: FR Payment date: 20080514 Year of fee payment: 15 |
|
| 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: 20090510 |
|
| 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: 20091201 |
|
| REG | Reference to a national code |
Ref country code: ES Ref legal event code: FD2A Effective date: 20090511 |
|
| 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: 20090511 |
|
| 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: 20090510 |