EP0453447B1 - Use of monocarboxylic acid polyoxyalkylester sulphonates as low-foam textile conditioning agents - Google Patents
Use of monocarboxylic acid polyoxyalkylester sulphonates as low-foam textile conditioning agents Download PDFInfo
- Publication number
- EP0453447B1 EP0453447B1 EP90900177A EP90900177A EP0453447B1 EP 0453447 B1 EP0453447 B1 EP 0453447B1 EP 90900177 A EP90900177 A EP 90900177A EP 90900177 A EP90900177 A EP 90900177A EP 0453447 B1 EP0453447 B1 EP 0453447B1
- Authority
- EP
- European Patent Office
- Prior art keywords
- monocarboxylic acid
- acid
- low
- acid polyoxyalkyl
- salts
- 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
- 150000002762 monocarboxylic acid derivatives Chemical class 0.000 title claims abstract description 22
- 239000004753 textile Substances 0.000 title claims abstract description 12
- 239000006260 foam Substances 0.000 title claims abstract description 11
- 239000003795 chemical substances by application Substances 0.000 title description 11
- 230000003750 conditioning effect Effects 0.000 title 1
- 125000001273 sulfonato group Chemical group [O-]S(*)(=O)=O 0.000 title 1
- -1 amine salts Chemical class 0.000 claims abstract description 18
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 claims abstract description 5
- AKEJUJNQAAGONA-UHFFFAOYSA-N sulfur trioxide Chemical compound O=S(=O)=O AKEJUJNQAAGONA-UHFFFAOYSA-N 0.000 claims description 24
- 239000000080 wetting agent Substances 0.000 claims description 14
- 150000002148 esters Chemical class 0.000 claims description 12
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 claims description 11
- 229920000742 Cotton Polymers 0.000 claims description 6
- RZXLPPRPEOUENN-UHFFFAOYSA-N Chlorfenson Chemical class C1=CC(Cl)=CC=C1OS(=O)(=O)C1=CC=C(Cl)C=C1 RZXLPPRPEOUENN-UHFFFAOYSA-N 0.000 claims description 5
- 238000006243 chemical reaction Methods 0.000 claims description 5
- 239000013543 active substance Substances 0.000 claims description 4
- 239000002585 base Substances 0.000 claims description 4
- 238000002360 preparation method Methods 0.000 claims description 4
- 239000003513 alkali Substances 0.000 claims description 3
- 159000000003 magnesium salts Chemical class 0.000 claims description 2
- 239000003352 sequestering agent Substances 0.000 claims description 2
- 239000003381 stabilizer Substances 0.000 claims description 2
- 239000000463 material Substances 0.000 claims 2
- 150000001735 carboxylic acids Chemical class 0.000 claims 1
- 239000002253 acid Substances 0.000 abstract description 2
- 239000004094 surface-active agent Substances 0.000 abstract description 2
- 150000007513 acids Chemical class 0.000 abstract 1
- 239000004745 nonwoven fabric Substances 0.000 abstract 1
- HEMHJVSKTPXQMS-UHFFFAOYSA-M sodium hydroxide Inorganic materials [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 20
- ZQPPMHVWECSIRJ-UHFFFAOYSA-N Oleic acid Natural products CCCCCCCCC=CCCCCCCCC(O)=O ZQPPMHVWECSIRJ-UHFFFAOYSA-N 0.000 description 13
- 238000004061 bleaching Methods 0.000 description 13
- ZQPPMHVWECSIRJ-MDZDMXLPSA-N elaidic acid Chemical compound CCCCCCCC\C=C\CCCCCCCC(O)=O ZQPPMHVWECSIRJ-MDZDMXLPSA-N 0.000 description 13
- QXJSBBXBKPUZAA-UHFFFAOYSA-N isooleic acid Natural products CCCCCCCC=CCCCCCCCCC(O)=O QXJSBBXBKPUZAA-UHFFFAOYSA-N 0.000 description 13
- WRIDQFICGBMAFQ-UHFFFAOYSA-N (E)-8-Octadecenoic acid Natural products CCCCCCCCCC=CCCCCCCC(O)=O WRIDQFICGBMAFQ-UHFFFAOYSA-N 0.000 description 12
- LQJBNNIYVWPHFW-UHFFFAOYSA-N 20:1omega9c fatty acid Natural products CCCCCCCCCCC=CCCCCCCCC(O)=O LQJBNNIYVWPHFW-UHFFFAOYSA-N 0.000 description 12
- QSBYPNXLFMSGKH-UHFFFAOYSA-N 9-Heptadecensaeure Natural products CCCCCCCC=CCCCCCCCC(O)=O QSBYPNXLFMSGKH-UHFFFAOYSA-N 0.000 description 12
- 239000005642 Oleic acid Substances 0.000 description 12
- 239000000243 solution Substances 0.000 description 10
- 238000006277 sulfonation reaction Methods 0.000 description 10
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 9
- 239000004744 fabric Substances 0.000 description 9
- 239000000203 mixture Substances 0.000 description 9
- 239000000047 product Substances 0.000 description 9
- BDHFUVZGWQCTTF-UHFFFAOYSA-M sulfonate Chemical compound [O-]S(=O)=O BDHFUVZGWQCTTF-UHFFFAOYSA-M 0.000 description 9
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 8
- 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 8
- 239000011734 sodium Substances 0.000 description 8
- 229910052708 sodium Inorganic materials 0.000 description 8
- 125000004432 carbon atom Chemical group C* 0.000 description 6
- 238000005187 foaming Methods 0.000 description 6
- 239000007844 bleaching agent Substances 0.000 description 5
- 239000007795 chemical reaction product Substances 0.000 description 5
- 238000009736 wetting Methods 0.000 description 5
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 4
- 150000001298 alcohols Chemical class 0.000 description 4
- 150000001412 amines Chemical class 0.000 description 4
- 238000001816 cooling Methods 0.000 description 4
- 125000002704 decyl 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])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 4
- BXWNKGSJHAJOGX-UHFFFAOYSA-N hexadecan-1-ol Chemical compound CCCCCCCCCCCCCCCCO BXWNKGSJHAJOGX-UHFFFAOYSA-N 0.000 description 4
- 229910052757 nitrogen Inorganic materials 0.000 description 4
- GLDOVTGHNKAZLK-UHFFFAOYSA-N octadecan-1-ol Chemical compound CCCCCCCCCCCCCCCCCCO GLDOVTGHNKAZLK-UHFFFAOYSA-N 0.000 description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 4
- DPUOLQHDNGRHBS-UHFFFAOYSA-N Brassidinsaeure Natural products CCCCCCCCC=CCCCCCCCCCCCC(O)=O DPUOLQHDNGRHBS-UHFFFAOYSA-N 0.000 description 3
- URXZXNYJPAJJOQ-UHFFFAOYSA-N Erucic acid Natural products CCCCCCC=CCCCCCCCCCCCC(O)=O URXZXNYJPAJJOQ-UHFFFAOYSA-N 0.000 description 3
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 3
- 239000007864 aqueous solution Substances 0.000 description 3
- DPUOLQHDNGRHBS-KTKRTIGZSA-N erucic acid Chemical compound CCCCCCCC\C=C/CCCCCCCCCCCC(O)=O DPUOLQHDNGRHBS-KTKRTIGZSA-N 0.000 description 3
- 239000007789 gas Substances 0.000 description 3
- 239000007788 liquid Substances 0.000 description 3
- BARWIPMJPCRCTP-UHFFFAOYSA-N oleic acid oleyl ester Natural products CCCCCCCCC=CCCCCCCCCOC(=O)CCCCCCCC=CCCCCCCCC BARWIPMJPCRCTP-UHFFFAOYSA-N 0.000 description 3
- BARWIPMJPCRCTP-CLFAGFIQSA-N oleyl oleate Chemical compound CCCCCCCC\C=C/CCCCCCCCOC(=O)CCCCCCC\C=C/CCCCCCCC BARWIPMJPCRCTP-CLFAGFIQSA-N 0.000 description 3
- 239000011541 reaction mixture Substances 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- 150000003871 sulfonates Chemical class 0.000 description 3
- 150000008053 sultones Chemical class 0.000 description 3
- ALSTYHKOOCGGFT-KTKRTIGZSA-N (9Z)-octadecen-1-ol Chemical compound CCCCCCCC\C=C/CCCCCCCCO ALSTYHKOOCGGFT-KTKRTIGZSA-N 0.000 description 2
- JXNPEDYJTDQORS-HZJYTTRNSA-N (9Z,12Z)-octadecadien-1-ol Chemical compound CCCCC\C=C/C\C=C/CCCCCCCCO JXNPEDYJTDQORS-HZJYTTRNSA-N 0.000 description 2
- KBPLFHHGFOOTCA-UHFFFAOYSA-N 1-Octanol Chemical compound CCCCCCCCO KBPLFHHGFOOTCA-UHFFFAOYSA-N 0.000 description 2
- IAYPIBMASNFSPL-UHFFFAOYSA-N Ethylene oxide Chemical compound C1CO1 IAYPIBMASNFSPL-UHFFFAOYSA-N 0.000 description 2
- CSNNHWWHGAXBCP-UHFFFAOYSA-L Magnesium sulfate Chemical compound [Mg+2].[O-][S+2]([O-])([O-])[O-] CSNNHWWHGAXBCP-UHFFFAOYSA-L 0.000 description 2
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- CNCZDZFOYUXJFI-AWLASTDMSA-N [Na].CCCCCCCC\C=C/CCCCCCCCOC(=O)CCCCCCC\C=C/CCCCCCCC Chemical compound [Na].CCCCCCCC\C=C/CCCCCCCCOC(=O)CCCCCCC\C=C/CCCCCCCC CNCZDZFOYUXJFI-AWLASTDMSA-N 0.000 description 2
- 230000002378 acidificating effect Effects 0.000 description 2
- 125000001931 aliphatic group Chemical group 0.000 description 2
- 229910052783 alkali metal Inorganic materials 0.000 description 2
- 150000008044 alkali metal hydroxides Chemical class 0.000 description 2
- 150000001340 alkali metals Chemical class 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 238000009835 boiling Methods 0.000 description 2
- 229960000541 cetyl alcohol Drugs 0.000 description 2
- MWKFXSUHUHTGQN-UHFFFAOYSA-N decan-1-ol Chemical compound CCCCCCCCCCO MWKFXSUHUHTGQN-UHFFFAOYSA-N 0.000 description 2
- 235000014113 dietary fatty acids Nutrition 0.000 description 2
- NOPFSRXAKWQILS-UHFFFAOYSA-N docosan-1-ol Chemical compound CCCCCCCCCCCCCCCCCCCCCCO NOPFSRXAKWQILS-UHFFFAOYSA-N 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 239000000194 fatty acid Substances 0.000 description 2
- 229930195729 fatty acid Natural products 0.000 description 2
- ZSIAUFGUXNUGDI-UHFFFAOYSA-N hexan-1-ol Chemical compound CCCCCCO ZSIAUFGUXNUGDI-UHFFFAOYSA-N 0.000 description 2
- 230000007062 hydrolysis Effects 0.000 description 2
- 238000006460 hydrolysis reaction Methods 0.000 description 2
- 150000004679 hydroxides Chemical class 0.000 description 2
- WQYVRQLZKVEZGA-UHFFFAOYSA-N hypochlorite Chemical compound Cl[O-] WQYVRQLZKVEZGA-UHFFFAOYSA-N 0.000 description 2
- JXNPEDYJTDQORS-UHFFFAOYSA-N linoleyl alcohol Natural products CCCCCC=CCC=CCCCCCCCCO JXNPEDYJTDQORS-UHFFFAOYSA-N 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 238000000034 method Methods 0.000 description 2
- 150000002763 monocarboxylic acids Chemical class 0.000 description 2
- GOQYKNQRPGWPLP-UHFFFAOYSA-N n-heptadecyl alcohol Natural products CCCCCCCCCCCCCCCCCO GOQYKNQRPGWPLP-UHFFFAOYSA-N 0.000 description 2
- 229940055577 oleyl alcohol Drugs 0.000 description 2
- XMLQWXUVTXCDDL-UHFFFAOYSA-N oleyl alcohol Natural products CCCCCCC=CCCCCCCCCCCO XMLQWXUVTXCDDL-UHFFFAOYSA-N 0.000 description 2
- SECPZKHBENQXJG-FPLPWBNLSA-N palmitoleic acid Chemical compound CCCCCC\C=C/CCCCCCCC(O)=O SECPZKHBENQXJG-FPLPWBNLSA-N 0.000 description 2
- LBIYNOAMNIKVKF-FPLPWBNLSA-N palmitoleyl alcohol Chemical compound CCCCCC\C=C/CCCCCCCCO LBIYNOAMNIKVKF-FPLPWBNLSA-N 0.000 description 2
- LBIYNOAMNIKVKF-UHFFFAOYSA-N palmitoleyl alcohol Natural products CCCCCCC=CCCCCCCCCO LBIYNOAMNIKVKF-UHFFFAOYSA-N 0.000 description 2
- CNVZJPUDSLNTQU-SEYXRHQNSA-N petroselinic acid Chemical compound CCCCCCCCCCC\C=C/CCCCC(O)=O CNVZJPUDSLNTQU-SEYXRHQNSA-N 0.000 description 2
- 229920001296 polysiloxane Polymers 0.000 description 2
- 150000003839 salts Chemical class 0.000 description 2
- 229920002545 silicone oil Polymers 0.000 description 2
- 229940012831 stearyl alcohol Drugs 0.000 description 2
- YZAZXIUFBCPZGB-QZOPMXJLSA-N (z)-octadec-9-enoic acid Chemical compound CCCCCCCC\C=C/CCCCCCCC(O)=O.CCCCCCCC\C=C/CCCCCCCC(O)=O YZAZXIUFBCPZGB-QZOPMXJLSA-N 0.000 description 1
- 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 1
- FRPZMMHWLSIFAZ-UHFFFAOYSA-N 10-undecenoic acid Chemical compound OC(=O)CCCCCCCCC=C FRPZMMHWLSIFAZ-UHFFFAOYSA-N 0.000 description 1
- OXEDXHIBHVMDST-UHFFFAOYSA-N 12Z-octadecenoic acid Natural products CCCCCC=CCCCCCCCCCCC(O)=O OXEDXHIBHVMDST-UHFFFAOYSA-N 0.000 description 1
- SGTNSNPWRIOYBX-UHFFFAOYSA-N 2-(3,4-dimethoxyphenyl)-5-{[2-(3,4-dimethoxyphenyl)ethyl](methyl)amino}-2-(propan-2-yl)pentanenitrile Chemical compound C1=C(OC)C(OC)=CC=C1CCN(C)CCCC(C#N)(C(C)C)C1=CC=C(OC)C(OC)=C1 SGTNSNPWRIOYBX-UHFFFAOYSA-N 0.000 description 1
- FJKROLUGYXJWQN-UHFFFAOYSA-M 4-hydroxybenzoate Chemical compound OC1=CC=C(C([O-])=O)C=C1 FJKROLUGYXJWQN-UHFFFAOYSA-M 0.000 description 1
- ZCYVEMRRCGMTRW-UHFFFAOYSA-N 7553-56-2 Chemical compound [I] ZCYVEMRRCGMTRW-UHFFFAOYSA-N 0.000 description 1
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 description 1
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 1
- KCXVZYZYPLLWCC-UHFFFAOYSA-N EDTA Chemical class OC(=O)CN(CC(O)=O)CCN(CC(O)=O)CC(O)=O KCXVZYZYPLLWCC-UHFFFAOYSA-N 0.000 description 1
- 235000013830 Eruca Nutrition 0.000 description 1
- 241000801434 Eruca Species 0.000 description 1
- KKCBUQHMOMHUOY-UHFFFAOYSA-N Na2O Inorganic materials [O-2].[Na+].[Na+] KKCBUQHMOMHUOY-UHFFFAOYSA-N 0.000 description 1
- 229910019093 NaOCl Inorganic materials 0.000 description 1
- 206010067482 No adverse event Diseases 0.000 description 1
- 229910019142 PO4 Inorganic materials 0.000 description 1
- 235000021319 Palmitoleic acid Nutrition 0.000 description 1
- CNVZJPUDSLNTQU-UHFFFAOYSA-N Petroselaidic acid Natural products CCCCCCCCCCCC=CCCCCC(O)=O CNVZJPUDSLNTQU-UHFFFAOYSA-N 0.000 description 1
- 239000004952 Polyamide Substances 0.000 description 1
- 229920000388 Polyphosphate Polymers 0.000 description 1
- GOOHAUXETOMSMM-UHFFFAOYSA-N Propylene oxide Chemical compound CC1CO1 GOOHAUXETOMSMM-UHFFFAOYSA-N 0.000 description 1
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 description 1
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 description 1
- GSEJCLTVZPLZKY-UHFFFAOYSA-N Triethanolamine Chemical compound OCCN(CCO)CCO GSEJCLTVZPLZKY-UHFFFAOYSA-N 0.000 description 1
- 150000001447 alkali salts Chemical class 0.000 description 1
- 239000012670 alkaline solution Substances 0.000 description 1
- 150000001336 alkenes Chemical class 0.000 description 1
- 150000004996 alkyl benzenes Chemical class 0.000 description 1
- 150000008051 alkyl sulfates Chemical class 0.000 description 1
- 125000002947 alkylene group Chemical group 0.000 description 1
- 239000000908 ammonium hydroxide Substances 0.000 description 1
- 125000000129 anionic group Chemical group 0.000 description 1
- 230000001580 bacterial effect Effects 0.000 description 1
- KHAVLLBUVKBTBG-UHFFFAOYSA-N caproleic acid Natural products OC(=O)CCCCCCCC=C KHAVLLBUVKBTBG-UHFFFAOYSA-N 0.000 description 1
- 150000007942 carboxylates Chemical class 0.000 description 1
- 150000001732 carboxylic acid derivatives Chemical class 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 239000000460 chlorine Substances 0.000 description 1
- 229910052801 chlorine Inorganic materials 0.000 description 1
- XTHPWXDJESJLNJ-UHFFFAOYSA-N chlorosulfonic acid Substances OS(Cl)(=O)=O XTHPWXDJESJLNJ-UHFFFAOYSA-N 0.000 description 1
- SECPZKHBENQXJG-UHFFFAOYSA-N cis-palmitoleic acid Natural products CCCCCCC=CCCCCCCCC(O)=O SECPZKHBENQXJG-UHFFFAOYSA-N 0.000 description 1
- 239000012459 cleaning agent Substances 0.000 description 1
- 229910052681 coesite Inorganic materials 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 238000011109 contamination Methods 0.000 description 1
- 229910052906 cristobalite Inorganic materials 0.000 description 1
- 238000013016 damping Methods 0.000 description 1
- 238000005237 degreasing agent Methods 0.000 description 1
- 230000001419 dependent effect Effects 0.000 description 1
- 239000003599 detergent Substances 0.000 description 1
- ZBCBWPMODOFKDW-UHFFFAOYSA-N diethanolamine Chemical compound OCCNCCO ZBCBWPMODOFKDW-UHFFFAOYSA-N 0.000 description 1
- 229960000735 docosanol Drugs 0.000 description 1
- 238000004043 dyeing Methods 0.000 description 1
- 230000032050 esterification Effects 0.000 description 1
- 238000005886 esterification reaction Methods 0.000 description 1
- BEFDCLMNVWHSGT-UHFFFAOYSA-N ethenylcyclopentane Chemical compound C=CC1CCCC1 BEFDCLMNVWHSGT-UHFFFAOYSA-N 0.000 description 1
- LYCAIKOWRPUZTN-UHFFFAOYSA-N ethylene glycol Natural products OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 1
- 238000001704 evaporation Methods 0.000 description 1
- 230000008020 evaporation Effects 0.000 description 1
- 239000011552 falling film Substances 0.000 description 1
- 239000003925 fat 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
- 238000000227 grinding Methods 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 description 1
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 description 1
- 238000007654 immersion Methods 0.000 description 1
- 239000011261 inert gas Substances 0.000 description 1
- 229910052500 inorganic mineral Inorganic materials 0.000 description 1
- 229910052740 iodine Inorganic materials 0.000 description 1
- 239000011630 iodine Substances 0.000 description 1
- 229910052943 magnesium sulfate Inorganic materials 0.000 description 1
- 235000019341 magnesium sulphate Nutrition 0.000 description 1
- 235000010755 mineral Nutrition 0.000 description 1
- 239000011707 mineral Substances 0.000 description 1
- 230000007935 neutral effect Effects 0.000 description 1
- 238000006386 neutralization reaction Methods 0.000 description 1
- 231100000252 nontoxic Toxicity 0.000 description 1
- 235000021317 phosphate Nutrition 0.000 description 1
- 150000003013 phosphoric acid derivatives Chemical class 0.000 description 1
- 229920002647 polyamide Polymers 0.000 description 1
- 229920000728 polyester Polymers 0.000 description 1
- 239000001205 polyphosphate Substances 0.000 description 1
- 235000011176 polyphosphates Nutrition 0.000 description 1
- 238000004321 preservation Methods 0.000 description 1
- 239000003755 preservative agent Substances 0.000 description 1
- BDERNNFJNOPAEC-UHFFFAOYSA-N propan-1-ol Chemical compound CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 description 1
- 238000007127 saponification reaction Methods 0.000 description 1
- 229920006395 saturated elastomer Polymers 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- 235000012239 silicon dioxide Nutrition 0.000 description 1
- SUKJFIGYRHOWBL-UHFFFAOYSA-N sodium hypochlorite Chemical compound [Na+].Cl[O-] SUKJFIGYRHOWBL-UHFFFAOYSA-N 0.000 description 1
- NTHWMYGWWRZVTN-UHFFFAOYSA-N sodium silicate Chemical compound [Na+].[Na+].[O-][Si]([O-])=O NTHWMYGWWRZVTN-UHFFFAOYSA-N 0.000 description 1
- 229910052938 sodium sulfate Inorganic materials 0.000 description 1
- 235000011152 sodium sulphate Nutrition 0.000 description 1
- 229940075582 sorbic acid Drugs 0.000 description 1
- 235000010199 sorbic acid Nutrition 0.000 description 1
- 239000004334 sorbic acid Substances 0.000 description 1
- 230000006641 stabilisation Effects 0.000 description 1
- 238000011105 stabilization Methods 0.000 description 1
- 239000007858 starting material Substances 0.000 description 1
- 229910052682 stishovite Inorganic materials 0.000 description 1
- 230000019635 sulfation Effects 0.000 description 1
- 238000005670 sulfation reaction Methods 0.000 description 1
- 150000008054 sulfonate salts Chemical class 0.000 description 1
- 150000003460 sulfonic acids Chemical class 0.000 description 1
- 239000012209 synthetic fiber Substances 0.000 description 1
- 229920002994 synthetic fiber Polymers 0.000 description 1
- AQWHMKSIVLSRNY-UHFFFAOYSA-N trans-Octadec-5-ensaeure Natural products CCCCCCCCCCCCC=CCCCC(O)=O AQWHMKSIVLSRNY-UHFFFAOYSA-N 0.000 description 1
- 229910052905 tridymite Inorganic materials 0.000 description 1
- 229960002703 undecylenic acid Drugs 0.000 description 1
- 235000013311 vegetables Nutrition 0.000 description 1
Classifications
-
- D—TEXTILES; PAPER
- D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
- D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
- D06M11/00—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with inorganic substances or complexes thereof; Such treatment combined with mechanical treatment, e.g. mercerising
- D06M11/32—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with inorganic substances or complexes thereof; Such treatment combined with mechanical treatment, e.g. mercerising with oxygen, ozone, ozonides, oxides, hydroxides or percompounds; Salts derived from anions with an amphoteric element-oxygen bond
- D06M11/36—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with inorganic substances or complexes thereof; Such treatment combined with mechanical treatment, e.g. mercerising with oxygen, ozone, ozonides, oxides, hydroxides or percompounds; Salts derived from anions with an amphoteric element-oxygen bond with oxides, hydroxides or mixed oxides; with salts derived from anions with an amphoteric element-oxygen bond
- D06M11/38—Oxides or hydroxides of elements of Groups 1 or 11 of the Periodic Table
-
- 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
- C11D1/02—Anionic compounds
- C11D1/12—Sulfonic acids or sulfuric acid esters; Salts thereof
- C11D1/28—Sulfonation products derived from fatty acids or their derivatives, e.g. esters, amides
-
- 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
- C11D3/0005—Other compounding ingredients characterised by their effect
- C11D3/0026—Low foaming or foam regulating compositions
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- 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
- D06L4/12—Bleaching fibres, filaments, threads, yarns, fabrics, feathers or made-up fibrous goods; Bleaching leather or furs using agents which develop oxygen combined with specific additives
Definitions
- the invention relates to the use of monocarboxylic acid polyoxyalkyl ester sulfonates as low-foaming wetting agents in aqueous alkaline pretreatment agents for textile fabrics.
- wetting agents that are suitable for such alkaline treatment agents must be water-soluble and alkali-stable, and must ensure uniform wetting of the goods.
- wetting agents should be environmentally friendly, i.e. biodegradable and have no toxic effects on aquatic organisms.
- defoamers for example silicones
- the use of defoamers is not only with additional ones Costs associated, but often has undesirable side effects, for example an uneven wetting of the textile fabrics, as well as silicone oil stains that are difficult to remove in the case of silicone-containing defoamers.
- the object of the invention was therefore to develop silicone-free, low-foaming, liquid and thus directly meterable, water-soluble, alkali-stable and readily biodegradable wetting agents for textile fabrics or yarns, which meet all of these product requirements in a uniform substance.
- the invention is based on the surprising finding that the high requirements placed on wetting agents of monocarboxylic acid polyoxyalkyl ester sulfonic acids in the form of their alkali metal, ammonium and / or amine salts are met.
- the invention accordingly relates to the use of alkali metal, ammonium and / or amine salts of carboxylic acid polyoxyalkyl ester sulfonic acids, prepared by reacting monounsaturated monocarboxylic acid polyoxyalkyl esters of the general formula in which R is an alkyl radical with 1 to 22 C atoms or an alkenyl radical with 3 to 22 C atoms, m is a number from 10 to 21, n is 2 and / or 3 and x is a number from 1 to 20, with Sulfur trioxide and subsequent reaction of the sulfonated monocarboxylic acid polyoxyalkyl esters obtained with aqueous alkalis as low-foaming wetting agents in aqueous alkaline pretreatment agents for textile fabrics or yarns.
- R is an alkyl radical with 1 to 22 C atoms or an alkenyl radical with 3 to 22 C atoms
- m is a number from 10 to 21
- n is 2 and /
- the salts of monocarboxylic acid polyoxyalkylester sulfonic acids can be prepared in a manner known per se, in which monounsaturated monocarboxylic acid polyoxyalkyl esters are sulfonated at temperatures between 5 and 120 ° C. with sulfuric acid, oleum, chlorosulfonic acid or SO3-containing gas mixtures.
- the sulfonation temperatures are particularly preferably between 5 and 40 ° C.
- the molar ratio of monounsaturated monocarboxylic acid polyoxyalkyl: SO3 is about 1: 1.
- the sulfonations are carried out continuously or batchwise in conventional reactors suitable and customary for the sulfation of fatty alcohols or for the sulfonation of fatty acid esters, alkylbenzenes or olefins, preferably of the type of falling film reactor (see, for example, in Kirk-Othmer: Encyclopedia of Chemical Technologie 22 , 28 ff (1983)).
- the sulfonation product obtained is then hydrolyzed with an aqueous solution of alkali metal hydroxides, ammonium hydroxide and / or amines, in which the sulfonated reaction mixture is preferably added to the aqueous solution.
- 1 to 1.2 moles of hydroxides and / or amines are used per mole of sulfur trioxide added.
- Excess hydroxide and / or amine is required to neutralize the gaseous SO3 dissolved in the sulfonation product.
- Sodium hydroxide, potassium hydroxide, diethanolamine and / or triethanolamine, particularly preferably sodium hydroxide, are preferably used as neutralization bases.
- the concentration of the hydroxides and / or amines in water is preferably chosen so that the end product forms a low-viscosity solution.
- the reaction product also contains sultones.
- the formation of sultons is a known reaction in the sulfonation of olefinic double bonds.
- hydrolysis in which the reaction products are heated until the sultone groups formed have been completely destroyed while maintaining a pH of 7 by controlled addition of alkali metal hydroxide will.
- the time required for this is dependent on pressure and temperature. For example, a complete hydrolysis can be achieved in 4 to 6 hours at boiling temperature under normal pressure, under pressure at higher temperatures, but in a considerably shorter time.
- the monounsaturated monocarboxylic acid polyoxyalkyl esters of the general formula to be used as starting materials are also accessible using methods known from the literature. They are produced from aliphatic, natural and / or synthetic, saturated alcohols with 1 to 22 carbon atoms and / or aliphatic, natural and / or synthetic, unsaturated alcohols with 3 to 22 carbon atoms, for example methanol, ethanol, propanol, butanol, hexanol, Octanol, decanol, cetyl alcohol, stearyl alcohol, behenyl alcohol, oleyl alcohol, palmitoleyl alcohol, linoleyl alcohol, eruca alcohol or technical alcohol cuts consisting predominantly of cetyl alcohol, stearyl alcohol, oleyl alcohol, palmitoleyl alcohol and / or linoleyl alcohol.
- the alkoxylations of the alcohols with ethylene oxide and / or propylene oxide are carried out using known industrial processes carried out (see, for example, in Chemische Technologie, Volume 7, pages 131 to 132, Carl-Hanser-Verlag, Kunststoff (1986)).
- the average degree of oxalkylation x of the mixtures of homologous oxalkylates obtained corresponds to the molar amount of the alkylene oxides attached and is between 1 and 20, preferably between 2 and 10.
- oxyalkylated alcohols obtained are then reacted with C11 ⁇ 22 monounsaturated monocarboxylic acids in a manner known per se in the presence of esterification catalysts, for example tin grinding.
- Suitable monounsaturated monocarboxylic acids with 11 to 22 carbon atoms are, for example, 10-undecenoic acid, palmitoleic acid, oleic acid, petroselinic acid, elaidic acid and / or erucic acid.
- oleic acid and / or erucic acid are used in pure form or in the form of fatty acid mixtures rich in oleic acid and erucic acid, as can be obtained from fats of animal and / or vegetable origin.
- Preferred monounsaturated monocarboxylic acid polyoxyalkyl esters are those of the general formula used, in which R represents an alkyl radical having 8 to 18 carbon atoms, m 17 and / or 21, n 2 and / or 3 and x is a number between 2 to 10.
- the wetting agents to be used according to the invention are light yellow to light brown, clear, aqueous, alkaline solutions. If desired, these can be bleached with hydrogen peroxide solutions or alkali hypochlorite solutions (chlorine solution) in a manner known per se at temperatures between 40 and 55 ° C. For stabilization against bacterial contamination, preservation with preservatives known from the prior art, for example p-hydroxybenzoate and / or sorbic acid, is recommended.
- the active substance content of monocarboxylic acid polyoxyalkyl ester sulfonate salts in the solutions is between 10 and 50% by weight.
- Monocarboxylic acid polyoxyalkyl ester sulfonate salt-containing wetting agents are distinguished by a particularly low foaming power. This is of particular advantage in strongly alkaline pretreatment agents, for example in alkaline cold bleaching liquors, hot bleaching liquors, mercerizing liquors, alkaline decoction and degreasing agents, since such alkaline pretreatment agents have a particular tendency to form foam.
- the monocarboxylic acid polyoxyalkyl ester sulfonate salts are preferably used as low-foaming wetting agents in aqueous alkaline bleaching liquors. These contain hydrogen peroxide or compounds which form hydrogen peroxide in aqueous solution as a bleaching agent.
- the pH of the bleaching baths is adjusted to 10 to 14 with strong bases, for example with NaOH and / or KOH.
- the known anionic and nonionic wetting agents for example alkyl sulfates, sulfonates, carboxylates, phosphates and / or alkylpolyoxyethylene glycol ethers, which are stable and effective in these media, tend to produce a lot of foam in the high-speed apparatus.
- foam damping agents for example silicone oils
- the salts of monocarboxylic acid polyoxyalkyl ester sulfonic acids to be used according to the invention develop practically no foam in such baths, so that the addition of defoamers is unnecessary.
- the bleaching liquors containing 10 to 100 ml of hydrogen peroxide, 35% by weight, 5 to 20 g of bases from the group of sodium or / or potassium hydroxide, 5 to 50 ml of stabilizers, for example sodium water glass (Na2O: SiO2 1: 2 ; 38 - 40 ° Bé) and / or alkali salts of ethylenediaminetetraacetic acid and / or polyphosphates, 0.1 to 1.0 g of magnesium salts, for example magnesium sulfate, 0.5 to 10 g of sequestering agent, for example Securon R 540, Henkel KGaA and 0.3 to 30 g, based on active substance, of monocarboxylic acid polyoxyalkyl ester sulfonate salts, are used at temperatures between 15 and 90 ° C, preferably at a temperature of about 20 ° C (cold bleach), on textile fabrics or yarns.
- stabilizers for example sodium water glass (Na2O: Si
- the cotton-containing textile fabrics such as woven and / or knitted fabrics, which are preferably treated with bleaching liquors containing monocarboxylic acid polyoxyalkyl sulfonate salt, and yarns are distinguished by good degrees of whiteness and good hydrophilic properties.
- the bleaching liquors were treated with oleic acid 2.9EO decyl ester sodium sulfonate, prepared according to Example 1.1, and for comparison oleic acid oleyl ester sodium sulfonate, prepared according to example 1.2, or oleic acid 2.9EO decyl ester as wetting agent in different Amounts added.
- the wetting effect of these liquors was determined at 20 ° C. in accordance with DIN 53 901 (determination of the immersion wetting power of surfactant solutions). The following network times were obtained:
- the foaming behavior of the cold bleaching solutions (composition analogous to 2.b)), the wetting agent 2.4 g AS / l cold bleaching liquor oleic acid 2.9EO decyl ester sodium sulfonate and for comparison 2.4 g AS / l cold bleaching liquor oleic acid oleylester sodium sulfonate or 2.4 g AS / l cold bleaching liquor containing oleic acid 2.9EO decyl ester was checked at 20 ° C on the Krantz dyeing machine (capacity: 25 l, liquor run-in from the outside in, running time: 15 minutes) (0% means none Foam between the liquid surface and the edge of the container, 100% means that the volume between the liquid surface and the edge of the container is completely filled with foam).
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Abstract
Description
Die Erfindung betrifft die Verwendung von Monocarbonsäurepolyoxyalkylester-sulfonaten als schaumarme Netzmittel in wäßrigen alkalischen Vorbehandlungsmitteln für textile Flächengebilde.The invention relates to the use of monocarboxylic acid polyoxyalkyl ester sulfonates as low-foaming wetting agents in aqueous alkaline pretreatment agents for textile fabrics.
Die meisten zur Vorbehandlung und zum Bleichen von natürlichen Fasern, beispielsweise Baumwolle, oder von Mischungen aus natürlichen und synthetischen Fasern, beispielsweise Baumwolle/Polyester oder Baumwolle/Polyamid, verwendeten Mittel, wie Mercerisierlaugen, Abkochmittel, Reinigungsmittel und Bleichmittel, erfordern den Zusatz von Netzmitteln, um einen rascheren und innigeren Kontakt zwischen dem Behandlungsmittel und dem textilen Flächengebilde zu erzielen. Netzmittel, die für solche alkalischen Behandlungsmittel geeignet sind, müssen wasserlöslich und alkalistabil sein sowie eine gleichmäßige Netzung der Ware gewährleisten. Darüber hinaus sollen solche Netzmittel umweltfreundlich sein, d.h. biologisch abgebaut werden und keine toxische Wirkung gegenüber Wasserorganismen zeigen.Most of the agents used for the pretreatment and bleaching of natural fibers, for example cotton, or of mixtures of natural and synthetic fibers, for example cotton / polyester or cotton / polyamide, such as mercerizing lye, boiling agents, cleaning agents and bleaching agents, require the addition of wetting agents, in order to achieve a quicker and more intimate contact between the treatment agent and the textile fabric. Wetting agents that are suitable for such alkaline treatment agents must be water-soluble and alkali-stable, and must ensure uniform wetting of the goods. In addition, such wetting agents should be environmentally friendly, i.e. biodegradable and have no toxic effects on aquatic organisms.
Da die Vorbehandlung und das Bleichen textiler Flächengebilde auf schnellaufenden Kontinueanlagen sowie Diskontinueanlagen durchgeführt wird, kommt es leicht zu unerwünschter Schaumbildung. Um dies zu vermeiden, werden den Behandlungsmitteln üblicherweise alkalistabile Entschäumer, beispielsweise Silikone zugesetzt. Der Einsatz von Entschäumern ist jedoch nicht nur mit zusätzlichen Kosten verbunden, sondern hat oft unerwünschte Nebenwirkungen zur Folge, zum Beispiel eine ungleichmäßige Benetzung der textilen Flächengebilde, sowie bei silikonhaltigen Entschäumern schwer entfernbare Silikonölflecken.Since the pretreatment and bleaching of textile fabrics are carried out on high-speed continuous systems and discontinuous systems, undesirable foam formation easily occurs. In order to avoid this, alkali-stable defoamers, for example silicones, are usually added to the treatment agents. The use of defoamers is not only with additional ones Costs associated, but often has undesirable side effects, for example an uneven wetting of the textile fabrics, as well as silicone oil stains that are difficult to remove in the case of silicone-containing defoamers.
Die Aufgabe der Erfindung bestand daher in der Entwicklung von silikonfreien, schaumarmen, flüssigen und somit direkt dosierbaren, wasserlöslichen, alkalistabilen und biologisch gut abbaubaren Netzmitteln für textile Flächengebilde oder Garne, die in einer einheitlichen Substanz alle diese Produktanforderungen erfüllen.The object of the invention was therefore to develop silicone-free, low-foaming, liquid and thus directly meterable, water-soluble, alkali-stable and readily biodegradable wetting agents for textile fabrics or yarns, which meet all of these product requirements in a uniform substance.
Die Erfindung geht von der überraschenden Feststellung aus, daß die an Netzmittel gestellten hohen Anfordenungen von Monocarbonsäurepolyoxyalkylestersulfonsäuren in Form ihrer Alkali-, Ammomiumu nd/oder Aminsalze erfüllt werden.The invention is based on the surprising finding that the high requirements placed on wetting agents of monocarboxylic acid polyoxyalkyl ester sulfonic acids in the form of their alkali metal, ammonium and / or amine salts are met.
Gegenstand der Erfindung ist dementsprechend die Verwendung von Alkali-, Ammonium- und/oder Aminsalzen von Carbonsäurepolyoxyalkylestersulfonsäuren, hergestellt durch Umsetzung von einfach ungesättigten Monocarbonsäure-polyoxyalkylestern der allgemeinen Formel
in der R einen Alkylrest mit 1 bis 22 C-Atomen oder einen Alkenylrest mit 3 bis 22 C-Atomen bedeutet, m eine Zahl von 10 bis 21 ist, n 2 und/oder 3 und x eine Zahl von 1 bis 20 ist, mit Schwefeltrioxid und anschließender Umsetzung der erhaltenen sulfonierten Monocarbonsäure-polyoxyalkylester mit wäßrigen Alkalien als schaumarme Netzmittel in wäßrigen alkalischen Vorbehandlungsmitteln für textile Flächengebilde oder Garne.The invention accordingly relates to the use of alkali metal, ammonium and / or amine salts of carboxylic acid polyoxyalkyl ester sulfonic acids, prepared by reacting monounsaturated monocarboxylic acid polyoxyalkyl esters of the general formula
in which R is an alkyl radical with 1 to 22 C atoms or an alkenyl radical with 3 to 22 C atoms, m is a number from 10 to 21, n is 2 and / or 3 and x is a number from 1 to 20, with Sulfur trioxide and subsequent reaction of the sulfonated monocarboxylic acid polyoxyalkyl esters obtained with aqueous alkalis as low-foaming wetting agents in aqueous alkaline pretreatment agents for textile fabrics or yarns.
Die Salze von Monocarbonsäurepolyoxyalkylester-sulfonsäuren lassen sich in an sich bekannter Weise herstellen, in dem einfach ungesättigte Monocarbonsäure-polyoxyalkylester bei Temperaturen zwischen 5 und 120 °C mit Schwefelsäure, Oleum, Chlorsulfonsäure oder SO₃-haltigen Gasgemischen sulfoniert werden. Vorzugsweise werden die Sulfonierungen von einfach ungesättigten Monocarbonsäurepolyoxyalkylestern gemäß DE-A-37 20 000 bei Temperaturen zwischen 5 und 100 °C mit Gasgemischen aus SO₃ und Luft oder Inertgasen, beispielsweise Stickstoff, in denen der SO₃-Gehalt zwischen 1 und 10 Vol.-% liegt, durchgeführt. Die Sulfonierungstemperaturen liegen besonders bevorzugt zwischen 5 und 40 °C. Das molare Verhältnis einfach ungesättigter Monocarbonsäure-polyoxyalkylester : SO₃ liegt bei etwa 1 : 1.The salts of monocarboxylic acid polyoxyalkylester sulfonic acids can be prepared in a manner known per se, in which monounsaturated monocarboxylic acid polyoxyalkyl esters are sulfonated at temperatures between 5 and 120 ° C. with sulfuric acid, oleum, chlorosulfonic acid or SO₃-containing gas mixtures. Preferably, the sulfonations of monounsaturated monocarboxylic acid polyoxyalkyl esters according to DE-A-37 20 000 at temperatures between 5 and 100 ° C with gas mixtures of SO₃ and air or inert gases, for example nitrogen, in which the SO₃ content between 1 and 10 vol .-% lies, carried out. The sulfonation temperatures are particularly preferably between 5 and 40 ° C. The molar ratio of monounsaturated monocarboxylic acid polyoxyalkyl: SO₃ is about 1: 1.
Die Sulfonierungen werden in üblichen für die Sulfatierung von Fettalkoholen oder für die Sulfonierung von Fettsäureestern, Alkylbenzolen oder Olefinen geeigneten und gebräuchlichen Reaktoren, bevorzugt vom Typ des Fallfilmreaktors, kontinuierlich oder diskontinuierlich durchgeführt (s. beispielsweise in Kirk-Othmer: Encyclopedia of Chemical Technologie 22, 28 ff (1983)).The sulfonations are carried out continuously or batchwise in conventional reactors suitable and customary for the sulfation of fatty alcohols or for the sulfonation of fatty acid esters, alkylbenzenes or olefins, preferably of the type of falling film reactor (see, for example, in Kirk-Othmer: Encyclopedia of Chemical Technologie 22 , 28 ff (1983)).
Das erhaltene Sulfonierungsprodukt wird anschließend mit einer wäßrigen Lösung aus Alkalihydroxiden, Ammoniumhydroxid und/oder Aminen hydrolysiert, in dem vorzugsweise das sulfonierte Reaktionsgemisch zu der wäßrigen Lösung gegeben wird. Pro Mol angelagertem Schwefeltrioxid werden 1 bis 1,2 Mol Hydroxide und/oder Amine eingesetzt. Überschüssiges Hydroxid und/oder Amin ist erforderlich, um das im Sulfonierungsprodukt gelöste gasförmige SO₃ zu neutralisieren. Als Neutralisationsbasen werden vorzugsweise Natriumhydroxid, Kaliumhydroxid, Diethanolamin und/oder Triethanolamin, besonders bevorzugt Natriumhydroxid, eingesetzt. Die Konzentration der Hydroxide und/oder Amine in Wasser wird vorzugsweise so gewählt, daß das Endprodukt eine niedrigviskose Lösung bildet.The sulfonation product obtained is then hydrolyzed with an aqueous solution of alkali metal hydroxides, ammonium hydroxide and / or amines, in which the sulfonated reaction mixture is preferably added to the aqueous solution. 1 to 1.2 moles of hydroxides and / or amines are used per mole of sulfur trioxide added. Excess hydroxide and / or amine is required to neutralize the gaseous SO₃ dissolved in the sulfonation product. Sodium hydroxide, potassium hydroxide, diethanolamine and / or triethanolamine, particularly preferably sodium hydroxide, are preferably used as neutralization bases. The concentration of the hydroxides and / or amines in water is preferably chosen so that the end product forms a low-viscosity solution.
Das Reaktionsprodukt enthält neben den gewünschten Sulfonaten auch Sultone. Die Bildung von Sultonen ist bei der Sulfonierung olefinischer Doppelbindungen eine an sich bekannte Reaktion. Zur Überführung der im Reaktionsprodukt unerwünschten Sultone in Hydroxysulfonate und/oder ungesättigte Sulfonate ist es erforderlich, die Sulfonierungsprodukte einer Hydrolyse zu unterwerfen, bei der die Reaktionsprodukte bis zur vollständigen Zerstörung der gebildeten Sultongruppen unter Aufrechterhaltung eines pH-Wertes von 7 durch kontrollierte Zugabe von Alkalihydroxid erwärmt werden. Die hierfür benötigte Zeit ist druck- und temperaturabhängig. So läßt sich beispielsweise bei Siedetemperatur unter Normaldruck in 4 bis 6 Stunden, unter Druck bei höheren Temperaturen, jedoch in erheblich kürzerer Zeit eine vollständige Hydrolyse erreichen.In addition to the desired sulfonates, the reaction product also contains sultones. The formation of sultons is a known reaction in the sulfonation of olefinic double bonds. To convert the sultones which are undesirable in the reaction product into hydroxysulfonates and / or unsaturated sulfonates, it is necessary to subject the sulfonation products to hydrolysis, in which the reaction products are heated until the sultone groups formed have been completely destroyed while maintaining a pH of 7 by controlled addition of alkali metal hydroxide will. The time required for this is dependent on pressure and temperature. For example, a complete hydrolysis can be achieved in 4 to 6 hours at boiling temperature under normal pressure, under pressure at higher temperatures, but in a considerably shorter time.
Die als Edukte einzusetzenden einfach ungesättigten Monocarbonsäure-polyoxyalkylester der allgemeinen Formel
sind ebenfalls nach literaturbekannten Verfahren zugänglich. Ihre Herstellung geht aus von aliphatischen, natürlichen und/oder synthetischen, gesättigten Alkoholen mit 1 bis 22 Kohlenstoffatomen und/oder aliphatischen, natürlichen und/oder synthetischen, ungesättigten Alkoholen mit 3 bis 22 Kohlenstoffatomen, beispielsweise Methanol, Ethanol, Propanol, Butanol, Hexanol, Octanol, Decanol, Cetylalkohol, Stearylalkohol, Behenylalkohol, Oleylalkohol, Palmitoleylalkohol, Linoleylalkohol, Erucaalkohol oder technische, überwiegend aus Cetylalkohol, Stearylalkohol, Oleylalkohol, Palmitoleylalkohol und/oder Linoleylalkohol bestehenden Alkoholschnitten.The monounsaturated monocarboxylic acid polyoxyalkyl esters of the general formula to be used as starting materials
are also accessible using methods known from the literature. They are produced from aliphatic, natural and / or synthetic, saturated alcohols with 1 to 22 carbon atoms and / or aliphatic, natural and / or synthetic, unsaturated alcohols with 3 to 22 carbon atoms, for example methanol, ethanol, propanol, butanol, hexanol, Octanol, decanol, cetyl alcohol, stearyl alcohol, behenyl alcohol, oleyl alcohol, palmitoleyl alcohol, linoleyl alcohol, eruca alcohol or technical alcohol cuts consisting predominantly of cetyl alcohol, stearyl alcohol, oleyl alcohol, palmitoleyl alcohol and / or linoleyl alcohol.
Die Oxalkylierungen der Alkohole mit Ethylenoxid und/oder Propylenoxid werden nach bekannten großtechnischen Verfahren durchgeführt (s. beispielsweise in Chemische Technologie, Band 7, Seite 131 bis 132, Carl-Hanser-Verlag, München (1986)). Der mittlere Oxalkylierungsgrad x der erhaltenen Gemische homologer Oxalkylate entspricht der molaren Menge der angelagerten Alkylenoxide und liegt zwischen 1 und 20, vorzugsweise zwischen 2 und 10.The alkoxylations of the alcohols with ethylene oxide and / or propylene oxide are carried out using known industrial processes carried out (see, for example, in Chemische Technologie, Volume 7, pages 131 to 132, Carl-Hanser-Verlag, Munich (1986)). The average degree of oxalkylation x of the mixtures of homologous oxalkylates obtained corresponds to the molar amount of the alkylene oxides attached and is between 1 and 20, preferably between 2 and 10.
Die erhaltenen oxalkylierten Alkohole werden anschließend mit C₁₁₋₂₂-einfach ungesättigten Monocarbonsäuren in an sich bekannter Weise in Gegenwart von Veresterungskatalysatoren, beispielsweise Zinnschliff, umgesetzt. Als einfach ungesättigte Monocarbonsäuren mit 11 bis 22 C-Atomen eignen sich beispielsweise 10-Undecensäure, Palmitoleinsäure, Ölsäure, Petroselinsäure, Elaidinsäure und/oder Erucasäure. Vorzugsweise werden Ölsäure und/oder Erucasäure in reiner Form oder in Form von ölsäure- und erucasäurereichen Fettsäuregemischen, wie sie aus Fetten tierischen und/oder pflanzlichen Ursprungs gewonnen werden können, eingesetzt.The oxyalkylated alcohols obtained are then reacted with C₁₁₋₂₂ monounsaturated monocarboxylic acids in a manner known per se in the presence of esterification catalysts, for example tin grinding. Suitable monounsaturated monocarboxylic acids with 11 to 22 carbon atoms are, for example, 10-undecenoic acid, palmitoleic acid, oleic acid, petroselinic acid, elaidic acid and / or erucic acid. Preferably, oleic acid and / or erucic acid are used in pure form or in the form of fatty acid mixtures rich in oleic acid and erucic acid, as can be obtained from fats of animal and / or vegetable origin.
Als einfach ungesättigte Monocarbonsäure-polyoxyalkylester werden bevorzugt solche der allgemeinen Formel
eingesetzt, in der R einen Alkylrest mit 8 bis 18 C-Atomen, m 17 und/oder 21, n 2 und/oder 3 und x eine Zahl zwischen 2 bis 10 darstellt.Preferred monounsaturated monocarboxylic acid polyoxyalkyl esters are those of the general formula
used, in which R represents an alkyl radical having 8 to 18 carbon atoms, m 17 and / or 21, n 2 and / or 3 and x is a number between 2 to 10.
Die erfindungsgemäß zu verwendenden Netzmittel sind hellgelbe bis hellbraune, klare, wäßrige, alkalische Lösungen. Gewünschtenfalls können diese mit Wasserstoffperoxidlösungen oder Alkalihypochloritlösungen (Chlorlauge) in an sich bekannter Weise bei Temperaturen zwischen 40 und 55 °C gebleicht werden. Zur Stabilisierung gegen Bakterienbefall empfiehlt sich die Konservierung mit aus dem Stand der Technik bekannten Konservierungsmitteln, beispielsweise p-Hydroxybenzoat und/oder Sorbinsäure. Der Aktivsubstanzgehalt an Monocarbonsäurepolyoxyalkylester-sulfonatsalzen liegt in den Lösungen zwischen 10 und 50 Gew.-%.The wetting agents to be used according to the invention are light yellow to light brown, clear, aqueous, alkaline solutions. If desired, these can be bleached with hydrogen peroxide solutions or alkali hypochlorite solutions (chlorine solution) in a manner known per se at temperatures between 40 and 55 ° C. For stabilization against bacterial contamination, preservation with preservatives known from the prior art, for example p-hydroxybenzoate and / or sorbic acid, is recommended. The active substance content of monocarboxylic acid polyoxyalkyl ester sulfonate salts in the solutions is between 10 and 50% by weight.
Monocarbonsäurepolyoxyalkylester-sulfonatsalzhaltige Netzmittel zeichnen sich durch ein besonders geringes Schaumvermögen aus. Dies ist von besonderem Vorteil in stark alkalischen Vorbehandlungsmitteln, beispielsweise in alkalischen Kaltbleichflotten, Heißbleichflotten, Mercerisierlaugen, alkalischen Abkoch- und Entfettungsmitteln, da solche alkalischen Vorbehandlungsmittel besonders zur Bildung von Schaum neigen.Monocarboxylic acid polyoxyalkyl ester sulfonate salt-containing wetting agents are distinguished by a particularly low foaming power. This is of particular advantage in strongly alkaline pretreatment agents, for example in alkaline cold bleaching liquors, hot bleaching liquors, mercerizing liquors, alkaline decoction and degreasing agents, since such alkaline pretreatment agents have a particular tendency to form foam.
Vorzugsweise werden die Monocarbonsäurepolyoxyalkylester-sulfonatsalze als schaumarme Netzmittel in wäßrigen alkalischen Bleichflotten verwendet. Diese enthalten als bleichendes Agens Wasserstoffperoxid oder Verbindungen, die in wäßriger Lösung Wasserstoffperoxid bilden. Der pH-Wert der Bleichbäder wird mit starken Basen, beispielsweise mit NaOH und/oder KOH, auf 10 bis 14 eingestellt. Die bekannten anionischen und nichtionischen Netzmittel, beispielsweise Alkylsulfate, -sulfonate, -carboxylate, -phosphate und/oder Alkylpolyoxyethylenglycolether, die in diesen Medien beständig und wirksam sind, neigen in den schnellaufenden Apparaturen zu starker Schaumentwicklung. Aus diesem Grunde ist der Einsatz von Schaumdämpfungsmitteln, beispielsweise von Silikonölen, üblich. Die erfindungsgemäß zu verwendenden Salze von Monocarbonsäurepolyoxyalkylester-sulfonsäuren entwickeln in solchen Bädern hingegen praktisch keinen Schaum, so daß sich der Zusatz von Entschäumern erübrigt. Die Bleichflotten, die pro Liter 10 bis 100 ml Wasserstoffperoxid, 35 Gew.-%ig, 5 bis 20 g Basen aus der Gruppe Natrium- oder/oder Kaliumhydroxid, 5 - 50 ml Stabilisatoren, beispielsweise Natronwasserglas (Na₂O : SiO₂ = 1 : 2; 38 - 40 °Bé) und/oder Alkalisalze von Ethylendiamintetraessigsäure und/oder Polyphosphaten, 0,1 bis 1,0 g Magnesiumsalze, beispielsweise Magnesiumsulfat, 0,5 bis 10 g Sequestriermittel, beispielsweise Securon R 540, Henkel KGaA und 0,3 bis 30 g, bezogen auf Aktivsubstanz, Monocarbonsäurepolyoxyalkylester-sulfonatsalze enthalten, werden bei Temperaturen zwischen 15 und 90 °C, vorzugsweise bei einer Temperatur von etwa 20 °C (Kaltbleiche), auf textilen Flächengebilden oder Garnen angewendet. Die mit monocarbonsäurepolyoxyalkylestersulfonatsalz-haltigen Bleichflotten vorzugsweise behandelten baumwollhaltigen textilen Flächengebilde, wie Gewebe und/oder Gewirke, und Garne zeichenen sich durch gute Weißgrade und gute hydrophile Eigenschaften aus.The monocarboxylic acid polyoxyalkyl ester sulfonate salts are preferably used as low-foaming wetting agents in aqueous alkaline bleaching liquors. These contain hydrogen peroxide or compounds which form hydrogen peroxide in aqueous solution as a bleaching agent. The pH of the bleaching baths is adjusted to 10 to 14 with strong bases, for example with NaOH and / or KOH. The known anionic and nonionic wetting agents, for example alkyl sulfates, sulfonates, carboxylates, phosphates and / or alkylpolyoxyethylene glycol ethers, which are stable and effective in these media, tend to produce a lot of foam in the high-speed apparatus. For this reason, the use of foam damping agents, for example silicone oils, is common. In contrast, the salts of monocarboxylic acid polyoxyalkyl ester sulfonic acids to be used according to the invention develop practically no foam in such baths, so that the addition of defoamers is unnecessary. The bleaching liquors containing 10 to 100 ml of hydrogen peroxide, 35% by weight, 5 to 20 g of bases from the group of sodium or / or potassium hydroxide, 5 to 50 ml of stabilizers, for example sodium water glass (Na₂O: SiO₂ = 1: 2 ; 38 - 40 ° Bé) and / or alkali salts of ethylenediaminetetraacetic acid and / or polyphosphates, 0.1 to 1.0 g of magnesium salts, for example magnesium sulfate, 0.5 to 10 g of sequestering agent, for example Securon R 540, Henkel KGaA and 0.3 to 30 g, based on active substance, of monocarboxylic acid polyoxyalkyl ester sulfonate salts, are used at temperatures between 15 and 90 ° C, preferably at a temperature of about 20 ° C (cold bleach), on textile fabrics or yarns. The cotton-containing textile fabrics, such as woven and / or knitted fabrics, which are preferably treated with bleaching liquors containing monocarboxylic acid polyoxyalkyl sulfonate salt, and yarns are distinguished by good degrees of whiteness and good hydrophilic properties.
EO bedeutet Ethylenoxid
AS bedeutet AktivsubstanzEO means ethylene oxide
AS means active substance
In einem Laborstandreaktor wurden 0,5 Mol Ölsäure-2,9EO-decylester auf 30 °C erwärmt und anschließend innerhalb von 50 Minuten 40 g (0,5 Mol) Schwefeltrioxid (erzeugt durch Verdampfen von 65 Gew.-%igem Oleum) verdünnt mit Stickstoff (SO₃-Gehalt im Stickstoffstrom = 5 Vol.-%) eingeleitet. Nach einer 30 minütigen Nachreaktion wurde das saure Sulfonierungsprodukt gleichzeitig mit einer wäßrigen 25 Gew.-%igen Natriumhydroxidlösung in vorgelegtes Wasser gegeben. Danach wurde auf 90 °C erhitzt und so lange NaOH zugegeben, bis sich ein konstanter pH-Wert von 7 einstellte. Das erhaltene Reaktionsprodukt war in Wasser klar löslich und besaß folgende Kenndaten:
Waschaktivsubstanz (DGF-Methode H-III-10) = 19,8 Gew.-%
Natriumsulfatgehalt: = 0,7 Gew.-%
Klettfarbzahl (NaOCl-Bleiche; 1 cm-Küvette) = 45In a laboratory stand reactor, 0.5 mol of oleic acid 2.9EO decyl ester was heated to 30 ° C. and then 40 g (0.5 mol) of sulfur trioxide (produced by evaporation of 65% by weight oleum) were diluted with within 50 minutes Nitrogen (SO₃ content in the nitrogen stream = 5 vol .-%) initiated. After a 30 minute post-reaction, the acidic sulfonation product was added simultaneously to an aqueous 25% by weight sodium hydroxide solution in the water initially introduced. The mixture was then heated to 90 ° C. and NaOH was added until a constant pH of 7 was established. The reaction product obtained was clearly soluble in water and had the following characteristics:
Active detergent substance (DGF method H-III-10) = 19.8% by weight
Sodium sulfate content: = 0.7% by weight
Velcro color number (NaOCl bleach; 1 cm cuvette) = 45
In einem 1-1-Sulfierreaktor mit Gaseinleitungsrohr und Mantelkühlung wurden 539 g (1 Mol) Ölsäure-oleylester (Jodzahl = 98, Verseifungszahl = 105) vorgelegt und bei 40 - 45 °C mit 88 g (1,2 Mol) gasförmigem Schwefeltrioxid umgesetzt. Schwefeltrioxid wurde durch Erhitzen einer entsprechenden Menge Oleum ausgetrieben, mit Stickstoff auf eine Konzentration von 5 Vol.-% verdünnt und innerhalb von 70 Minuten in den Ölsäure-oleylester eingeleitet, wobei die Temperatur des Reaktionsgemisches durch Kühlung unter 60 °C gehalten wurde. Nach der Sulfonierung wurde das saure Reaktionsgemisch auf 10 °C abgekühlt und portionsweise mit 5 Gew.-% einer 35 Gew.-%igen Wasserstoffperoxidlösung gebleicht, wobei die Temperatur der Mischung durch Kühlung ebenfalls unterhalb von 60 °C gehalten wurde. Anschließend wurde das gebleichte Produkt in eine Lösung von 48 g (1,2 Mol) NaOH in 250 ml Wasser eingerührt und 4 Stunden bei 95 °C hydrolisiert, wobei sich das Produkt entmischte. Nach dem Abkühlen wurde die obere Phase (ca. 10 Gew.-%), die unsulfoniertes Produkt enthielt, abgetrennt. Die Ölsäure-oleylester-natriumsulfonat enthaltende untere Phase wurde mit Mineralsäure auf einen pH-Wert von 7 eingestellt.539 g (1 mole) of oleic acid oleic acid (iodine number = 98, saponification number = 105) were placed in a 1-1-sulphonation reactor with gas inlet tube and jacket cooling and reacted at 40-45 ° C. with 88 g (1.2 mol) of gaseous sulfur trioxide . Sulfur trioxide was driven off by heating an appropriate amount of oleum, diluted to a concentration of 5% by volume with nitrogen and dissolved in within 70 minutes initiated the oleic acid oleylester, the temperature of the reaction mixture being kept below 60 ° C. by cooling. After sulfonation, the acidic reaction mixture was cooled to 10 ° C. and bleached in portions with 5% by weight of a 35% by weight hydrogen peroxide solution, the temperature of the mixture also being kept below 60 ° C. by cooling. The bleached product was then stirred into a solution of 48 g (1.2 mol) of NaOH in 250 ml of water and hydrolyzed at 95 ° C. for 4 hours, the product separating. After cooling, the upper phase (approx. 10% by weight), which contained unsulfonated product, was separated off. The lower phase containing oleic acid-oleylester sodium sulfonate was adjusted to a pH of 7 with mineral acid.
Kenndaten des Produktes:
-
a) Das Netzvermögen von 1 g AS/1 Flotte Ölsäure-2,9EO-decylester-natriumsulfonat, hergestellt nach Beispiel 1.1, sowie zum Vergleich von 1 g AS/l Flotte Ölsäureoleylester-natriumsulfonat, hergestellt nach Beispiel 1.2, sowie 1 g AS/I Flotte Ölsäure-2,9EO-decylester wurde in neutralen und alkalischen Medien bei unterschiedlichen Temperaturen nach DIN 53 901 bestimmt. Es wurden folgende Netzzeiten ermittelt:a) The wetting capacity of 1 g of AS / 1 fleet of oleic acid 2.9EO decyl ester sodium sulfonate, prepared according to Example 1.1, and for comparison, of 1 g of AS / l fleet of oleic acid olylester sodium sulfonate, produced according to Example 1.2, and 1 g of AS / I Brisk oleic acid 2.9EO decyl ester was determined in neutral and alkaline media at different temperatures according to DIN 53 901. The following network times were determined:
-
b) Zusammensetzung der alkalischen Kaltbleichlösung:b) Composition of the alkaline cold bleach solution:
Den Bleichflotten wurden Ölsäure-2,9EO-decylester-natriumsulfonat, hergestellt nach Beispiel 1.1, und zum Vergleich Ölsäureoleylester-natriumsulfonat, hergestellt nach Beispiel 1.2, oder Ölsäure-2,9EO-decylester als Netzmittel in unterschiedlichen Mengen zugesetzt. Die Netzwirkung dieser Flotten wurde bei 20 °C nach DIN 53 901 (Bestimmung des Tauchnetzvermögens von Tensidlösungen) bestimmt. Es wurden folgende Netzzeiten erhalten:
Das Schaumverhalten der Kaltbleichlösungen (Zusammensetzung analog 2.b)), die als Netzmittel 2,4 g AS/l Kaltbleichflotte Ölsäure-2,9EO-decylester-natriumsulfonat sowie zum Vergleich 2,4 g AS/l Kaltbleichflotte Ölsäure-oleylester-natriumsulfonat oder 2,4 g AS/l Kaltbleichflotte Ölsäure-2,9EO-decylester enthielten, wurde bei 20 °C auf dem Krantz-Färbeapparat (Fassungsvermögen: 25 l, Flotteneinlauf von außen nach innen, Laufzeit: 15 Minuten) überprüft (0 % bedeutet kein Schaum zwischen Flüssigkeitsoberfläche und Behälterrand, 100 % bedeutet, daß das Volumen zwischen Flüssigkeitsoberfläche und Behälterrand vollständig mit Schaum gefüllt ist).
Claims (4)
- The use of alkali, ammonium and/or amine salts of carboxylic acid polyoxyalkyl ester sulfonic acids prepared by reaction of monounsaturated monocarboxylic acid polyoxyalkyl esters corresponding to the following general formula
with sulfur trioxide and subsequent reaction of the sulfonated monocarboxylic acid polyoxyalkyl esters obtained with aqueous alkalis
as low-foam wetting agents in aqueous alkaline treatment preparations for flat textile materials or yarns. - The use claimed in claim 1, characterized in that R is a C₈₋₁₈ alkyl radical, m is 17 and/or 21, n is 2 and/or 3 and x is a number of 2 to 10.
- The use claimed in one or both of claims 1 and 2, characterized in that monocarboxylic acid polyoxyalkyl ester sulfonate salts are used in aqueous alkaline treatment preparations for cotton-containing flat textile materials or cotton-containing yarns.
- The use claimed in one or more of claims 1 to 3, characterized in that the treatment preparations are alkaline bleaches containing per liter from 10 to 100 ml 35% by weight hydrogen peroxide, from 5 to 20 g bases, from 5 to 50 ml stabilizers, from 0.1 to 1.0 g magnesium salts, from 0.5 to 10 g sequestering agents and from 0.3 to 30 g, based on active substance, of alkali, ammonium and/or amine salts of monocarboxylic acid polyoxyalkyl ester sulfonic acids.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| AT90900177T ATE86292T1 (en) | 1989-01-12 | 1990-01-04 | USE OF MONOCARBON ACID POLYOXYALKYLESTER - SULFONATES AS LOW FOAMING TEXTILE TREATMENT AGENTS. |
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| DE3900699A DE3900699A1 (en) | 1989-01-12 | 1989-01-12 | USE OF MONOCARBONSAFE POLYOXYALKYL SULPHONATES AS A FOAMY NETWORK IN WAESSEN ALKALINE TREATMENT AGENTS FOR TEXTILE FLUID IMAGES |
| DE3900699 | 1989-01-12 |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| EP0453447A1 EP0453447A1 (en) | 1991-10-30 |
| EP0453447B1 true EP0453447B1 (en) | 1993-03-03 |
Family
ID=6371922
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| EP90900177A Expired - Lifetime EP0453447B1 (en) | 1989-01-12 | 1990-01-04 | Use of monocarboxylic acid polyoxyalkylester sulphonates as low-foam textile conditioning agents |
Country Status (7)
| Country | Link |
|---|---|
| US (1) | US5250076A (en) |
| EP (1) | EP0453447B1 (en) |
| JP (1) | JPH04502651A (en) |
| BR (1) | BR9007019A (en) |
| DE (2) | DE3900699A1 (en) |
| ES (1) | ES2054330T3 (en) |
| WO (1) | WO1990008181A1 (en) |
Families Citing this family (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE4039348A1 (en) * | 1990-12-10 | 1992-06-11 | Henkel Kgaa | CARPET CLEANER |
| MY141653A (en) * | 1992-06-17 | 2010-05-31 | Lion Corp | Detergent composition having low skin irritability |
| US5417708A (en) * | 1994-03-09 | 1995-05-23 | Cook Incorporated | Intravascular treatment system and percutaneous release mechanism therefor |
| US5968370A (en) * | 1998-01-14 | 1999-10-19 | Prowler Environmental Technology, Inc. | Method of removing hydrocarbons from contaminated sludge |
| PL442737A1 (en) | 2022-11-04 | 2024-05-06 | Pcc Rokita Spółka Akcyjna | Method for selective preparation of paradichlorobenzene with improved recovery of the catalytic system |
Family Cites Families (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE2243306A1 (en) * | 1972-09-02 | 1974-03-21 | Henkel & Cie Gmbh | FOAM REGULATED DETERGENTS, ESPECIALLY FOR DRUM WASHING MACHINES |
| CH610209A5 (en) * | 1976-04-26 | 1979-04-12 | Ciba Geigy Ag | Wetting agent and foam inhibitor based on anionic surfactants |
| BE1000328A5 (en) * | 1987-02-19 | 1988-10-25 | Interox Sa | PARTICLE STABILIZED peroxygen compounds, METHOD OF MAKING, AND COMPOSITION CONTAINING. |
| US4963157A (en) * | 1987-04-17 | 1990-10-16 | Nippon Peroxide Co., Ltd. | Method for bleaching cellulosic fiber material with hydrogen peroxide |
| DE3720000A1 (en) * | 1987-06-15 | 1988-12-29 | Henkel Kgaa | FATTY ACID POLYOXYALKYLESTER SULFONATES, METHOD FOR THE PRODUCTION THEREOF AND THEIR USE AS A SURFACTANT |
-
1989
- 1989-01-12 DE DE3900699A patent/DE3900699A1/en not_active Withdrawn
-
1990
- 1990-01-04 EP EP90900177A patent/EP0453447B1/en not_active Expired - Lifetime
- 1990-01-04 WO PCT/EP1990/000012 patent/WO1990008181A1/en active IP Right Grant
- 1990-01-04 DE DE9090900177T patent/DE59000985D1/en not_active Expired - Fee Related
- 1990-01-04 US US07/721,585 patent/US5250076A/en not_active Expired - Fee Related
- 1990-01-04 JP JP2501041A patent/JPH04502651A/en active Pending
- 1990-01-04 ES ES90900177T patent/ES2054330T3/en not_active Expired - Lifetime
- 1990-01-04 BR BR909007019A patent/BR9007019A/en not_active Application Discontinuation
Non-Patent Citations (1)
| Title |
|---|
| Chemical Abstracts, Vol. 92, Nr. 18, 5 May 1980 Columbus, Ohio, USA:Skripchemko, E.S. & al.:"Antifrothing agent" page 124; ref. No. 148922 * |
Also Published As
| Publication number | Publication date |
|---|---|
| US5250076A (en) | 1993-10-05 |
| DE3900699A1 (en) | 1990-07-19 |
| EP0453447A1 (en) | 1991-10-30 |
| DE59000985D1 (en) | 1993-04-08 |
| WO1990008181A1 (en) | 1990-07-26 |
| BR9007019A (en) | 1991-11-12 |
| JPH04502651A (en) | 1992-05-14 |
| ES2054330T3 (en) | 1994-08-01 |
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