EP1805290A1 - Flüssigwaschmittel enthalthend farbfixiermitteln - Google Patents
Flüssigwaschmittel enthalthend farbfixiermittelnInfo
- Publication number
- EP1805290A1 EP1805290A1 EP05798492A EP05798492A EP1805290A1 EP 1805290 A1 EP1805290 A1 EP 1805290A1 EP 05798492 A EP05798492 A EP 05798492A EP 05798492 A EP05798492 A EP 05798492A EP 1805290 A1 EP1805290 A1 EP 1805290A1
- Authority
- EP
- European Patent Office
- Prior art keywords
- detergents
- cleaning agents
- agents according
- alkyl
- cyanamides
- 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
- 239000003599 detergent Substances 0.000 title claims abstract description 56
- 239000007788 liquid Substances 0.000 title claims abstract description 31
- 239000003795 chemical substances by application Substances 0.000 title claims abstract description 27
- -1 olefin sulfonate Chemical class 0.000 claims abstract description 59
- 239000004094 surface-active agent Substances 0.000 claims abstract description 20
- RTZKZFJDLAIYFH-UHFFFAOYSA-N ether Substances CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims abstract description 19
- 239000002736 nonionic surfactant Substances 0.000 claims abstract description 17
- 229920000768 polyamine Polymers 0.000 claims abstract description 15
- 150000001912 cyanamides Chemical class 0.000 claims abstract description 12
- KWIUHFFTVRNATP-UHFFFAOYSA-N Betaine Natural products C[N+](C)(C)CC([O-])=O KWIUHFFTVRNATP-UHFFFAOYSA-N 0.000 claims abstract description 11
- 150000001299 aldehydes Chemical class 0.000 claims abstract description 10
- 229960003237 betaine Drugs 0.000 claims abstract description 10
- NJSSICCENMLTKO-HRCBOCMUSA-N [(1r,2s,4r,5r)-3-hydroxy-4-(4-methylphenyl)sulfonyloxy-6,8-dioxabicyclo[3.2.1]octan-2-yl] 4-methylbenzenesulfonate Chemical compound C1=CC(C)=CC=C1S(=O)(=O)O[C@H]1C(O)[C@@H](OS(=O)(=O)C=2C=CC(C)=CC=2)[C@@H]2OC[C@H]1O2 NJSSICCENMLTKO-HRCBOCMUSA-N 0.000 claims abstract description 9
- 239000007795 chemical reaction product Substances 0.000 claims abstract description 9
- 238000005406 washing Methods 0.000 claims abstract description 9
- 150000008051 alkyl sulfates Chemical class 0.000 claims abstract description 7
- 150000003863 ammonium salts Chemical class 0.000 claims abstract description 7
- 229920001577 copolymer Polymers 0.000 claims abstract description 7
- BRLQWZUYTZBJKN-UHFFFAOYSA-N Epichlorohydrin Chemical compound ClCC1CO1 BRLQWZUYTZBJKN-UHFFFAOYSA-N 0.000 claims abstract description 6
- IIACRCGMVDHOTQ-UHFFFAOYSA-N sulfamic acid Chemical compound NS(O)(=O)=O IIACRCGMVDHOTQ-UHFFFAOYSA-N 0.000 claims abstract description 3
- KWIUHFFTVRNATP-UHFFFAOYSA-O N,N,N-trimethylglycinium Chemical compound C[N+](C)(C)CC(O)=O KWIUHFFTVRNATP-UHFFFAOYSA-O 0.000 claims abstract 3
- 239000000203 mixture Substances 0.000 claims description 29
- 239000003945 anionic surfactant Substances 0.000 claims description 25
- 239000012459 cleaning agent Substances 0.000 claims description 16
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 15
- 239000004753 textile Substances 0.000 claims description 13
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 claims description 11
- 239000002904 solvent Substances 0.000 claims description 5
- 230000000694 effects Effects 0.000 claims description 4
- ULWHHBHJGPPBCO-UHFFFAOYSA-N propane-1,1-diol Chemical compound CCC(O)O ULWHHBHJGPPBCO-UHFFFAOYSA-N 0.000 claims description 4
- 230000002401 inhibitory effect Effects 0.000 claims description 2
- 229920006317 cationic polymer Polymers 0.000 claims 1
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 abstract description 4
- 239000000470 constituent Substances 0.000 abstract description 2
- 229920001519 homopolymer Polymers 0.000 abstract description 2
- 150000004996 alkyl benzenes Chemical class 0.000 abstract 1
- 229940077388 benzenesulfonate Drugs 0.000 abstract 1
- 239000000975 dye Substances 0.000 description 22
- 125000000217 alkyl group Chemical group 0.000 description 20
- 239000000194 fatty acid Substances 0.000 description 18
- 235000014113 dietary fatty acids Nutrition 0.000 description 17
- 229930195729 fatty acid Natural products 0.000 description 17
- 150000003839 salts Chemical class 0.000 description 15
- 150000004665 fatty acids Chemical class 0.000 description 14
- 239000000834 fixative Substances 0.000 description 14
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 description 13
- 125000004432 carbon atom Chemical group C* 0.000 description 12
- 150000001875 compounds Chemical class 0.000 description 12
- 239000011734 sodium Substances 0.000 description 12
- 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 10
- 239000002253 acid Substances 0.000 description 10
- 150000001768 cations Chemical class 0.000 description 10
- 238000009472 formulation Methods 0.000 description 10
- 229910052708 sodium Inorganic materials 0.000 description 10
- IAYPIBMASNFSPL-UHFFFAOYSA-N Ethylene oxide Chemical compound C1CO1 IAYPIBMASNFSPL-UHFFFAOYSA-N 0.000 description 9
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 9
- 229910052700 potassium Inorganic materials 0.000 description 9
- 239000011591 potassium Substances 0.000 description 9
- 239000004480 active ingredient Substances 0.000 description 8
- 239000003112 inhibitor Substances 0.000 description 8
- 150000007513 acids Chemical class 0.000 description 7
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 description 6
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 description 6
- 229910000323 aluminium silicate Inorganic materials 0.000 description 6
- 125000000129 anionic group Chemical group 0.000 description 6
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 description 6
- 239000007859 condensation product Substances 0.000 description 6
- 239000003205 fragrance Substances 0.000 description 6
- GSEJCLTVZPLZKY-UHFFFAOYSA-O triethanolammonium Chemical compound OCC[NH+](CCO)CCO GSEJCLTVZPLZKY-UHFFFAOYSA-O 0.000 description 6
- ROSDSFDQCJNGOL-UHFFFAOYSA-N Dimethylamine Chemical compound CNC ROSDSFDQCJNGOL-UHFFFAOYSA-N 0.000 description 5
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 5
- 150000001412 amines Chemical class 0.000 description 5
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 description 5
- 230000002209 hydrophobic effect Effects 0.000 description 5
- 239000011777 magnesium Substances 0.000 description 5
- 229910052749 magnesium Inorganic materials 0.000 description 5
- 239000000047 product Substances 0.000 description 5
- 239000000243 solution Substances 0.000 description 5
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 description 4
- 239000004215 Carbon black (E152) Substances 0.000 description 4
- QUSNBJAOOMFDIB-UHFFFAOYSA-N Ethylamine Chemical compound CCN QUSNBJAOOMFDIB-UHFFFAOYSA-N 0.000 description 4
- PIICEJLVQHRZGT-UHFFFAOYSA-N Ethylenediamine Chemical compound NCCN PIICEJLVQHRZGT-UHFFFAOYSA-N 0.000 description 4
- 150000001298 alcohols Chemical class 0.000 description 4
- 239000011575 calcium Substances 0.000 description 4
- 229910052791 calcium Inorganic materials 0.000 description 4
- 230000000052 comparative effect Effects 0.000 description 4
- 150000002191 fatty alcohols Chemical class 0.000 description 4
- 239000006260 foam Substances 0.000 description 4
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 4
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 4
- 239000002304 perfume Substances 0.000 description 4
- 229920006395 saturated elastomer Polymers 0.000 description 4
- 239000000344 soap Substances 0.000 description 4
- 239000000126 substance Substances 0.000 description 4
- 239000010457 zeolite Substances 0.000 description 4
- 239000002888 zwitterionic surfactant Substances 0.000 description 4
- 108090000790 Enzymes Proteins 0.000 description 3
- 102000004190 Enzymes Human genes 0.000 description 3
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 3
- 229910019142 PO4 Inorganic materials 0.000 description 3
- ABLZXFCXXLZCGV-UHFFFAOYSA-N Phosphorous acid Chemical class OP(O)=O ABLZXFCXXLZCGV-UHFFFAOYSA-N 0.000 description 3
- 229920003171 Poly (ethylene oxide) Polymers 0.000 description 3
- DNIAPMSPPWPWGF-UHFFFAOYSA-N Propylene glycol Chemical compound CC(O)CO DNIAPMSPPWPWGF-UHFFFAOYSA-N 0.000 description 3
- GOOHAUXETOMSMM-UHFFFAOYSA-N Propylene oxide Chemical compound CC1CO1 GOOHAUXETOMSMM-UHFFFAOYSA-N 0.000 description 3
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- ULUAUXLGCMPNKK-UHFFFAOYSA-N Sulfobutanedioic acid Chemical class OC(=O)CC(C(O)=O)S(O)(=O)=O ULUAUXLGCMPNKK-UHFFFAOYSA-N 0.000 description 3
- 229910021536 Zeolite Inorganic materials 0.000 description 3
- 125000001931 aliphatic group Chemical group 0.000 description 3
- 239000003513 alkali Substances 0.000 description 3
- 229910052783 alkali metal Inorganic materials 0.000 description 3
- ZTQSAGDEMFDKMZ-UHFFFAOYSA-N butyric aldehyde Natural products CCCC=O ZTQSAGDEMFDKMZ-UHFFFAOYSA-N 0.000 description 3
- 238000006243 chemical reaction Methods 0.000 description 3
- 229940088598 enzyme Drugs 0.000 description 3
- 150000002148 esters Chemical class 0.000 description 3
- 235000011187 glycerol Nutrition 0.000 description 3
- 229930195733 hydrocarbon Natural products 0.000 description 3
- 229910052739 hydrogen Inorganic materials 0.000 description 3
- 239000001257 hydrogen Substances 0.000 description 3
- 125000002768 hydroxyalkyl group Chemical group 0.000 description 3
- 239000004615 ingredient Substances 0.000 description 3
- 229910052744 lithium Inorganic materials 0.000 description 3
- 239000003921 oil Substances 0.000 description 3
- 235000019198 oils Nutrition 0.000 description 3
- 230000003287 optical effect Effects 0.000 description 3
- 235000021317 phosphate Nutrition 0.000 description 3
- 229920005646 polycarboxylate Polymers 0.000 description 3
- 159000000000 sodium salts Chemical class 0.000 description 3
- 150000003467 sulfuric acid derivatives Chemical class 0.000 description 3
- WRIDQFICGBMAFQ-UHFFFAOYSA-N (E)-8-Octadecenoic acid Natural products CCCCCCCCCC=CCCCCCCC(O)=O WRIDQFICGBMAFQ-UHFFFAOYSA-N 0.000 description 2
- GAWAYYRQGQZKCR-REOHCLBHSA-N (S)-2-chloropropanoic acid Chemical compound C[C@H](Cl)C(O)=O GAWAYYRQGQZKCR-REOHCLBHSA-N 0.000 description 2
- PSBDWGZCVUAZQS-UHFFFAOYSA-N (dimethylsulfonio)acetate Chemical compound C[S+](C)CC([O-])=O PSBDWGZCVUAZQS-UHFFFAOYSA-N 0.000 description 2
- OSSNTDFYBPYIEC-UHFFFAOYSA-N 1-ethenylimidazole Chemical compound C=CN1C=CN=C1 OSSNTDFYBPYIEC-UHFFFAOYSA-N 0.000 description 2
- XHZPRMZZQOIPDS-UHFFFAOYSA-N 2-Methyl-2-[(1-oxo-2-propenyl)amino]-1-propanesulfonic acid Chemical compound OS(=O)(=O)CC(C)(C)NC(=O)C=C XHZPRMZZQOIPDS-UHFFFAOYSA-N 0.000 description 2
- LQJBNNIYVWPHFW-UHFFFAOYSA-N 20:1omega9c fatty acid Natural products CCCCCCCCCCC=CCCCCCCCC(O)=O LQJBNNIYVWPHFW-UHFFFAOYSA-N 0.000 description 2
- QSBYPNXLFMSGKH-UHFFFAOYSA-N 9-Heptadecensaeure Natural products CCCCCCCC=CCCCCCCCC(O)=O QSBYPNXLFMSGKH-UHFFFAOYSA-N 0.000 description 2
- HGINCPLSRVDWNT-UHFFFAOYSA-N Acrolein Chemical compound C=CC=O HGINCPLSRVDWNT-UHFFFAOYSA-N 0.000 description 2
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical class N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 2
- NLXLAEXVIDQMFP-UHFFFAOYSA-N Ammonia chloride Chemical compound [NH4+].[Cl-] NLXLAEXVIDQMFP-UHFFFAOYSA-N 0.000 description 2
- PAYRUJLWNCNPSJ-UHFFFAOYSA-N Aniline Chemical compound NC1=CC=CC=C1 PAYRUJLWNCNPSJ-UHFFFAOYSA-N 0.000 description 2
- 235000013162 Cocos nucifera Nutrition 0.000 description 2
- 244000060011 Cocos nucifera Species 0.000 description 2
- 229920000742 Cotton Polymers 0.000 description 2
- RPNUMPOLZDHAAY-UHFFFAOYSA-N Diethylenetriamine Chemical compound NCCNCCN RPNUMPOLZDHAAY-UHFFFAOYSA-N 0.000 description 2
- DBVJJBKOTRCVKF-UHFFFAOYSA-N Etidronic acid Chemical compound OP(=O)(O)C(O)(C)P(O)(O)=O DBVJJBKOTRCVKF-UHFFFAOYSA-N 0.000 description 2
- 235000010469 Glycine max Nutrition 0.000 description 2
- 244000068988 Glycine max Species 0.000 description 2
- WHNWPMSKXPGLAX-UHFFFAOYSA-N N-Vinyl-2-pyrrolidone Chemical compound C=CN1CCCC1=O WHNWPMSKXPGLAX-UHFFFAOYSA-N 0.000 description 2
- 239000005642 Oleic acid Substances 0.000 description 2
- ZQPPMHVWECSIRJ-UHFFFAOYSA-N Oleic acid Natural products CCCCCCCCC=CCCCCCCCC(O)=O ZQPPMHVWECSIRJ-UHFFFAOYSA-N 0.000 description 2
- 239000004435 Oxo alcohol Substances 0.000 description 2
- GLUUGHFHXGJENI-UHFFFAOYSA-N Piperazine Chemical compound C1CNCCN1 GLUUGHFHXGJENI-UHFFFAOYSA-N 0.000 description 2
- NBBJYMSMWIIQGU-UHFFFAOYSA-N Propionic aldehyde Chemical compound CCC=O NBBJYMSMWIIQGU-UHFFFAOYSA-N 0.000 description 2
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 description 2
- 229920002125 Sokalan® Polymers 0.000 description 2
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- 230000002378 acidificating effect Effects 0.000 description 2
- 150000001340 alkali metals Chemical class 0.000 description 2
- 150000001336 alkenes Chemical class 0.000 description 2
- 150000003973 alkyl amines Chemical class 0.000 description 2
- 239000002280 amphoteric surfactant Substances 0.000 description 2
- 239000007864 aqueous solution Substances 0.000 description 2
- HUMNYLRZRPPJDN-UHFFFAOYSA-N benzaldehyde Chemical compound O=CC1=CC=CC=C1 HUMNYLRZRPPJDN-UHFFFAOYSA-N 0.000 description 2
- QMKYBPDZANOJGF-UHFFFAOYSA-N benzene-1,3,5-tricarboxylic acid Chemical compound OC(=O)C1=CC(C(O)=O)=CC(C(O)=O)=C1 QMKYBPDZANOJGF-UHFFFAOYSA-N 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- FOCAUTSVDIKZOP-UHFFFAOYSA-N chloroacetic acid Chemical compound OC(=O)CCl FOCAUTSVDIKZOP-UHFFFAOYSA-N 0.000 description 2
- 229940106681 chloroacetic acid Drugs 0.000 description 2
- 238000009833 condensation Methods 0.000 description 2
- 230000005494 condensation Effects 0.000 description 2
- PAFZNILMFXTMIY-UHFFFAOYSA-N cyclohexylamine Chemical compound NC1CCCCC1 PAFZNILMFXTMIY-UHFFFAOYSA-N 0.000 description 2
- QGBSISYHAICWAH-UHFFFAOYSA-N dicyandiamide Chemical compound NC(N)=NC#N QGBSISYHAICWAH-UHFFFAOYSA-N 0.000 description 2
- 150000005690 diesters Chemical class 0.000 description 2
- HPNMFZURTQLUMO-UHFFFAOYSA-N diethylamine Chemical compound CCNCC HPNMFZURTQLUMO-UHFFFAOYSA-N 0.000 description 2
- 125000000118 dimethyl group Chemical group [H]C([H])([H])* 0.000 description 2
- IUNMPGNGSSIWFP-UHFFFAOYSA-N dimethylaminopropylamine Chemical compound CN(C)CCCN IUNMPGNGSSIWFP-UHFFFAOYSA-N 0.000 description 2
- UKMSUNONTOPOIO-UHFFFAOYSA-N docosanoic acid Chemical compound CCCCCCCCCCCCCCCCCCCCCC(O)=O UKMSUNONTOPOIO-UHFFFAOYSA-N 0.000 description 2
- LEQAOMBKQFMDFZ-UHFFFAOYSA-N glyoxal Chemical compound O=CC=O LEQAOMBKQFMDFZ-UHFFFAOYSA-N 0.000 description 2
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 2
- MTNDZQHUAFNZQY-UHFFFAOYSA-N imidazoline Chemical class C1CN=CN1 MTNDZQHUAFNZQY-UHFFFAOYSA-N 0.000 description 2
- 150000002500 ions Chemical class 0.000 description 2
- QXJSBBXBKPUZAA-UHFFFAOYSA-N isooleic acid Natural products CCCCCCCC=CCCCCCCCCC(O)=O QXJSBBXBKPUZAA-UHFFFAOYSA-N 0.000 description 2
- YDSWCNNOKPMOTP-UHFFFAOYSA-N mellitic acid Chemical compound OC(=O)C1=C(C(O)=O)C(C(O)=O)=C(C(O)=O)C(C(O)=O)=C1C(O)=O YDSWCNNOKPMOTP-UHFFFAOYSA-N 0.000 description 2
- 150000007522 mineralic acids Chemical class 0.000 description 2
- 239000000178 monomer Substances 0.000 description 2
- 230000007935 neutral effect Effects 0.000 description 2
- 229910052757 nitrogen Inorganic materials 0.000 description 2
- ZQPPMHVWECSIRJ-KTKRTIGZSA-N oleic acid Chemical compound CCCCCCCC\C=C/CCCCCCCC(O)=O ZQPPMHVWECSIRJ-KTKRTIGZSA-N 0.000 description 2
- 150000007524 organic acids Chemical class 0.000 description 2
- 235000005985 organic acids Nutrition 0.000 description 2
- MPQXHAGKBWFSNV-UHFFFAOYSA-N oxidophosphanium Chemical class [PH3]=O MPQXHAGKBWFSNV-UHFFFAOYSA-N 0.000 description 2
- 235000019832 sodium triphosphate Nutrition 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
- 229940117986 sulfobetaine Drugs 0.000 description 2
- 150000003871 sulfonates Chemical class 0.000 description 2
- 150000003462 sulfoxides Chemical class 0.000 description 2
- AKEJUJNQAAGONA-UHFFFAOYSA-N sulfur trioxide Chemical compound O=S(=O)=O AKEJUJNQAAGONA-UHFFFAOYSA-N 0.000 description 2
- 238000003786 synthesis reaction Methods 0.000 description 2
- 239000003760 tallow Substances 0.000 description 2
- QEMXHQIAXOOASZ-UHFFFAOYSA-N tetramethylammonium Chemical compound C[N+](C)(C)C QEMXHQIAXOOASZ-UHFFFAOYSA-N 0.000 description 2
- 125000005208 trialkylammonium group Chemical group 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- 239000004711 α-olefin Substances 0.000 description 2
- CIOXZGOUEYHNBF-UHFFFAOYSA-N (carboxymethoxy)succinic acid Chemical compound OC(=O)COC(C(O)=O)CC(O)=O CIOXZGOUEYHNBF-UHFFFAOYSA-N 0.000 description 1
- ILAPVZVYHKSGFM-UHFFFAOYSA-N 1-(carboxymethoxy)ethane-1,1,2-tricarboxylic acid Chemical class OC(=O)COC(C(O)=O)(C(O)=O)CC(O)=O ILAPVZVYHKSGFM-UHFFFAOYSA-N 0.000 description 1
- VILCJCGEZXAXTO-UHFFFAOYSA-N 2,2,2-tetramine Chemical compound NCCNCCNCCN VILCJCGEZXAXTO-UHFFFAOYSA-N 0.000 description 1
- QQGRFMIMXPWKPM-UHFFFAOYSA-N 2,3,4-tributylphenol Chemical compound CCCCC1=CC=C(O)C(CCCC)=C1CCCC QQGRFMIMXPWKPM-UHFFFAOYSA-N 0.000 description 1
- VJSWLXWONORKLD-UHFFFAOYSA-N 2,4,6-trihydroxybenzene-1,3,5-trisulfonic acid Chemical compound OC1=C(S(O)(=O)=O)C(O)=C(S(O)(=O)=O)C(O)=C1S(O)(=O)=O VJSWLXWONORKLD-UHFFFAOYSA-N 0.000 description 1
- CFPOJWPDQWJEMO-UHFFFAOYSA-N 2-(1,2-dicarboxyethoxy)butanedioic acid Chemical class OC(=O)CC(C(O)=O)OC(C(O)=O)CC(O)=O CFPOJWPDQWJEMO-UHFFFAOYSA-N 0.000 description 1
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 description 1
- RRBZUCWNYQUCTR-UHFFFAOYSA-N 2-(aminoazaniumyl)acetate Chemical class NNCC(O)=O RRBZUCWNYQUCTR-UHFFFAOYSA-N 0.000 description 1
- HZAXFHJVJLSVMW-UHFFFAOYSA-N 2-Aminoethan-1-ol Chemical compound NCCO HZAXFHJVJLSVMW-UHFFFAOYSA-N 0.000 description 1
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 1
- AGBXYHCHUYARJY-UHFFFAOYSA-N 2-phenylethenesulfonic acid Chemical compound OS(=O)(=O)C=CC1=CC=CC=C1 AGBXYHCHUYARJY-UHFFFAOYSA-N 0.000 description 1
- HRPVXLWXLXDGHG-UHFFFAOYSA-N Acrylamide Chemical compound NC(=O)C=C HRPVXLWXLXDGHG-UHFFFAOYSA-N 0.000 description 1
- 102000013142 Amylases Human genes 0.000 description 1
- 108010065511 Amylases Proteins 0.000 description 1
- 235000021357 Behenic acid Nutrition 0.000 description 1
- 102100032487 Beta-mannosidase Human genes 0.000 description 1
- BVKZGUZCCUSVTD-UHFFFAOYSA-M Bicarbonate Chemical class OC([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-M 0.000 description 1
- 125000002853 C1-C4 hydroxyalkyl group Chemical group 0.000 description 1
- CLJMMUQFMUBGRG-UHFFFAOYSA-N CCCCCCCCCCCCC1=NCC[N+]1(CCOCC([O-])=O)CC(O)=O Chemical compound CCCCCCCCCCCCC1=NCC[N+]1(CCOCC([O-])=O)CC(O)=O CLJMMUQFMUBGRG-UHFFFAOYSA-N 0.000 description 1
- 102000005575 Cellulases Human genes 0.000 description 1
- 108010084185 Cellulases Proteins 0.000 description 1
- KRKNYBCHXYNGOX-UHFFFAOYSA-K Citrate Chemical compound [O-]C(=O)CC(O)(CC([O-])=O)C([O-])=O KRKNYBCHXYNGOX-UHFFFAOYSA-K 0.000 description 1
- XZMCDFZZKTWFGF-UHFFFAOYSA-N Cyanamide Chemical compound NC#N XZMCDFZZKTWFGF-UHFFFAOYSA-N 0.000 description 1
- 229920000858 Cyclodextrin Polymers 0.000 description 1
- MYMOFIZGZYHOMD-UHFFFAOYSA-N Dioxygen Chemical compound O=O MYMOFIZGZYHOMD-UHFFFAOYSA-N 0.000 description 1
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- JFLKFZNIIQFQBS-FNCQTZNRSA-N trans,trans-1,4-Diphenyl-1,3-butadiene Chemical group C=1C=CC=CC=1\C=C\C=C\C1=CC=CC=C1 JFLKFZNIIQFQBS-FNCQTZNRSA-N 0.000 description 1
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Classifications
-
- 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
- C11D3/16—Organic compounds
- C11D3/37—Polymers
- C11D3/3746—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
- C11D3/3769—(Co)polymerised monomers containing nitrogen, e.g. carbonamides, nitriles or amines
- C11D3/3773—(Co)polymerised monomers containing nitrogen, e.g. carbonamides, nitriles or amines in liquid compositions
-
- 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
- C11D1/66—Non-ionic compounds
- C11D1/83—Mixtures of non-ionic with anionic compounds
-
- C—CHEMISTRY; METALLURGY
- C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
- C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
- C11D1/00—Detergent compositions based essentially on surface-active compounds; Use of these compounds as a detergent
- C11D1/66—Non-ionic compounds
- C11D1/83—Mixtures of non-ionic with anionic compounds
- C11D1/831—Mixtures of non-ionic with anionic compounds of sulfonates with ethers of polyoxyalkylenes without phosphates
-
- 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
- C11D1/88—Ampholytes; Electroneutral compounds
- C11D1/94—Mixtures with anionic, cationic or non-ionic compounds
-
- C—CHEMISTRY; METALLURGY
- C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
- C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
- C11D10/00—Compositions of detergents, not provided for by one single preceding group
- C11D10/04—Compositions of detergents, not provided for by one single preceding group based on mixtures of surface-active non-soap compounds and soap
-
- 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
- C11D3/16—Organic compounds
- C11D3/37—Polymers
- C11D3/3703—Macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
- C11D3/3719—Polyamides or polyimides
-
- 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
- C11D1/04—Carboxylic acids or salts thereof
-
- 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
- C11D1/04—Carboxylic acids or salts thereof
- C11D1/06—Ether- or thioether carboxylic acids
-
- 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
- C11D1/14—Sulfonic acids or sulfuric acid esters; Salts thereof derived from aliphatic hydrocarbons or mono-alcohols
- C11D1/143—Sulfonic acid esters
-
- 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
- C11D1/14—Sulfonic acids or sulfuric acid esters; Salts thereof derived from aliphatic hydrocarbons or mono-alcohols
- C11D1/146—Sulfuric acid esters
-
- 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
- C11D1/22—Sulfonic acids or sulfuric acid esters; Salts thereof derived from aromatic compounds
-
- C—CHEMISTRY; METALLURGY
- C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
- C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
- C11D1/00—Detergent compositions based essentially on surface-active compounds; Use of these compounds as a detergent
- C11D1/66—Non-ionic compounds
- C11D1/72—Ethers of polyoxyalkylene glycols
-
- 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
- C11D1/88—Ampholytes; Electroneutral compounds
- C11D1/90—Betaines
-
- 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
- C11D1/88—Ampholytes; Electroneutral compounds
- C11D1/92—Sulfobetaines ; Sulfitobetaines
Definitions
- the invention relates to liquid laundry detergents and cleaners for textiles containing one or more color fixing agents.
- Liquid detergents contain surfactants as their main constituent. As a rule, several surfactants are used simultaneously in modern detergents.
- anionic surfactants are linear alkylbenzenesulfonates (LAS),
- Fatty Acid Sulfates Fatty Acid Sulfates (FAS), secondary alkanesulfonates (SAS) and in part also
- Fatty alcohol ether sulfates (FAES) used. Come as nonionic surfactants
- Ethoxylates of long-chain synthetic alcohols e.g. the oxo alcohols, or of native fatty alcohols used.
- builders such as e.g., sodium metabisulfite, sodium metabisulfite, sodium metabisulfite, sodium metabisulfite, sodium metabisulfite, sodium metabisulfite, sodium metabisulfite, sodium metabisulfite, sodium metabisulfite, sodium metabisulfite, sodium metabisulfite, sodium metabisulfite, sodium metabisulfite, sodium metabisulfite, sodium metabisulfite, sodium metabisulfite, sodium metabisulfite, sodium metabisulfite, sodium metabisulfite, sodium metabisulfite, sodium metabisulfite, sodium metabisulfite, sodium metabisulfite, sodium metabisulfite, sodium metabisulfite, sodium metabisulfite, sodium metabisulfite, sodium metabisulfite, sodium metabisulfite, sodium metabisulfite, sodium metabisulfite, sodium metabisulfite, sodium metabisulfite, sodium metabisulfite, sodium metabisulfite
- Polycarboxylates and solubilizers such as e.g. Ethanol, glycerine or propanediol.
- washing aids and the so different groups of active ingredients as foam regulators,
- Color transfer inhibitors and dye fixatives are color transfer inhibitors and dye fixatives.
- the color fixatives prevent the fading of colored textiles, which is especially in dark-colored textiles made of cotton and
- Cotton blends occur over several wash cycles. In the case of high-quality dyed textiles, the colors fade over a longer period of use.
- the dye fixatives act simultaneously as Color transfer inhibitors and prevent staining mitge Why wanten, other colored or white textiles.
- dye fixing agents in liquid detergents in practice is limited to nonionic formulations, that is, to formulations which contain no anionic surfactants.
- the reason for this is the lack of compatibility of the anionic surfactants with the color fixing agents, which leads to flocculation, precipitation or phase separation of the components.
- the purpose of the present invention is to provide liquid washing and cleaning agent formulations for textiles which contain one or more color fixing agents in combination with an anionic surfactant and which, in spite of the potential incompatibility of the components, are physically and chemically stable.
- the anionic surfactant is linear alkylbenzenesulfonate and / or olefinsulfonate and / or alkylsulfate in combination with alkylethercarboxylates and / or betaines and a nonionic surfactant.
- the invention relates to liquid detergents and cleaners containing a1) alkylbenzenesulfonate, a2) olefin sulfonate, a3) alkyl sulfate or mixtures thereof, b1) ether carboxylate and / or b2) betaine, c) a nonionic surfactant and d) a color fixing agent from the group of
- alkylbenzenesulfonate a1 alkylbenzenesulfonate.
- the preferred alkylbenzenesulfonates contain linear alkyl chains of about 9 to 25 carbon atoms, preferably from about 10 to about 13 carbon atoms, the cation being sodium, potassium, ammonium, mono-, di- or triethanolammonium, calcium or magnesium and mixtures thereof.
- Magnesium is preferred as a cation for mild surfactant systems, but sodium is preferred for standard washing applications.
- Olefinsulfonates are obtained by sulfonation of C 8 -C 24 -, preferably Ci 4 - Ci 6 - ⁇ -olefins with sulfur trioxide and subsequent neutralization. Due to the preparation process, these olefin sulfonates may contain minor amounts of hydroxyalkanesulfonates and alkanedisulfonates. Specific blends of alpha-olefin sulfonates are described in U.S. 3,332,880.
- Alkyl sulfates here are water-soluble salts or acids of the formula ROSO 3 M, wherein R is a C 1 oC 24 hydrocarbon radical, preferably a Cio-C 2 o-alkyl or hydroxyalkyl radical, particularly preferably a C 12 -C 18 alkyl or Hydroxyalkyl radical.
- M is hydrogen or a cation, for example an alkali metal cation (for example sodium, potassium, lithium) or ammonium or substituted ammonium, for example methyl, dimethyl and trimethylammonium cations, alkanolammonium, for example triethanolammonium and quaternary ammonium cations, such as tetramethylammonium and dimethylpiperidinium cations and quaternary ammonium cations derived from alkylamines such as ethylamine, diethylamine, triethylamine and mixtures thereof.
- Alkyl chains of C 12 -C 16 are preferred for lower wash temperatures (eg below about 50 0 C) and alkyl chains of C 16 -C- 18 for higher wash temperatures (eg above about 5O 0 C).
- the components a1, a2 and a3 are used individually or in combination in concentrations of from 3 to 30% by weight, preferably from 5 to 20% by weight, more preferably from 7 to 17% by weight and most preferably from 7 used to 15 wt .-%.
- Ether carboxylates preferably have the general formula
- R n-alkyl, iso-alkyl, cycloalkyl, alkylaryl, arylalkyl, and / or aryl.
- the radical R preferably contains 8 to 18 C atoms and is derived from
- Alkylphenols from. Preference is given to Cs to C-alkyl ether carboxylates, and
- radicals R are C 8 -AIRyI-, C 12 / i 4 alkyl, iso-C 13 alkyl,
- Ci 4/15 -oxoalkyl C 16 / i 8 - alkyl, lauryl, oleyl, and / or Talgfettalkyl-.
- the index n 1 to 20, preferably 1 to 15, particularly preferably 1 to 12 and very particularly preferably 2 to 10.
- X is hydrogen, sodium, potassium, ammonium and / or
- Alkanolammonium in particular triethanolammonium.
- Betaines can be both carbobetaines and sulfobetaines.
- the carboxymethyl ammoniumbetaine are, in particular Cs to C-i ⁇ - alkyl-dimethyl-carboxymethyl-ammoniumbetaine, Cs to C-is-Alkylamidopropyl- dimethyl-carboxymethyl-ammoniumbetaine and C 8 - to C 8 alkyl-carboxymethyl d ⁇ polyethoxy- -ammoniumbetaine.
- betaines are, for example, the N-carboxyethyl-ammoniumbetains analogous to the compounds listed above, for the synthesis of which instead of chloroacetic acid or salts thereof the chloropropionic acid and its salts are used.
- examples of these are the Ci 2 -Ci 8 alkyl aminopropionate and C 1 -C 6 -alkyl-iminodipropionates as alkali and mono-, di- and trialkylammonium
- a preferred sulfobetaine is C 1 -C 6 alkyl-dimethyl-suifopropyl-betaine.
- the ether carboxylates and / or betaines described above can be used in amounts of from 1 to 30% by weight, preferably from 3 to 20% by weight and more preferably from 5 to 15% by weight.
- Suitable nonionic surfactants are in particular the ethoxylates of long-chain, aliphatic, synthetic or native alcohols having a C 8 - to C 22 -alkyl radical. These may contain about 1 to about 25 moles of ethylene oxide.
- the alkyl chain of the aliphatic alcohols may be linear or branched, primary or secondary, saturated or unsaturated.
- the alcohol ethoxylates may have a narrow range ("narrow range ethoxylates") or a broad Homologenverteilu ng of ethylene oxide ("Broad Range Ethoxylates").
- the ethoxylated alcohols preferably have an HLB value of 10 to 15, preferably 11 to 14.
- the use concentration is generally from 5 to 35 wt .-%, preferably 10 to 30 wt .-%, particularly preferably 15 to 25 wt .-% and most preferably 16 to 23 wt .-%.
- the mass ratio of anionic surfactants to nonionic surfactants is generally from 1: 4 to 4: 1, preferably 1: 2 to 2: 1, more preferably 0.8: 1 to 1, 5: 1.
- the color fixing agents which can be incorporated in liquid detergents according to the invention are nonionic or cationic and are described below:
- Polycondensates which can be used as dye fixing agents are prepared by reacting cyanamides with aldehydes and ammonium salts and / or monoamines (eg dye fixing agent FFM 3), by reacting monoamines and / or polyamines with epichlorohydrin (eg dye fixing agents FFIVI 2 and FFM A). , or by the reaction of polyamines with cyanamides and amidosulfuric (eg color fixing FFM 1) obtained.
- the monoamines used may be primary, secondary and tertiary amines. These may be aliphatic amines, e.g. Dialkylamines, especially dimethylamine, alicyclic amines, e.g. Cyclohexylamine and aromatic amines such as e.g. Aniline act. However, the amines used can also have aliphatic, alicyclic and aromatic substituents at the same time. Furthermore, heterocyclic compounds such as e.g. Pyridine can be used.
- polyamines in this case comprises e.g. Diamines, triamines, tetraamines, etc., as well as the analogous N-alkyl polyamines or the N, N-dialkyl-polyamines.
- Examples of these are ethylenediamine, propylenediamine, butylenediamine,
- Particularly preferred polyamines are ethylenediamine, diethylenetriamine and
- ammonium salts are salts of ammonia, in particular ammonium chloride or the above-mentioned Armine or
- the cyanamides may be cyanamide or dicyandiamide.
- Aldehydes that can be used to synthesize the color fixing agents include, for example, aliphatic aldehydes such as formaldehyde, acetaldehyde, propionaldehyde, butyraldehyde; Dialdehydes such as glyoxal; unsaturated aldehydes such as acrolein, crotonaldehyde and aromatic aldehydes such as Benzaldehyde. Particularly preferred are the aliphatic AJdehyde, in particular formaldehyde.
- DADMAC Diallyl dimethyl ammonium chloride
- Copolymers based on DADMAC contain as further components other vinylic monomers such as e.g. Vinylimidazole, vinylpyrrolidone, vinyl alcohol,
- Vinyl acetate (meth) acrylic acid (ester), acrylamide, styrene, styrenesulfonic acid,
- Homopolymers based on DADMAC are also available under the trade names
- Dodigen 3954 ®, Dodigen 4033 and Genamin ® PDAC (Fa. Clariant).
- the dye fixing agents are generally used in the liquid detergents to 0.1 to 5 wt .-%, preferably 0.5 to 3 wt .-% and particularly preferably 0.5 to 1 wt .-%.
- the liquid detergents according to the invention are preferably liquid and have a viscosity of max. 500 mPas. But they can also be higher viscosity, still flowable gels or spreadable pastes.
- the detergents and cleaners according to the invention contain as solvent propanediol, glycerol or ethanol in a concentration of 1 to 10% by weight, preferably 1 to 5% by weight.
- the pH of the formulations is adjusted to a value between 5 and 12 by the addition of acidic or alkaline substances.
- Acidic substances may be, for example, inorganic or organic acids, such as sulfuric acid, phosphonic acids, citric acid.
- Alkaline substances are, for example, caustic soda, potassium hydroxide solution and soda.
- Acid to neutral liquid detergents are, for example, wool detergents, neutral to weakly alkaline liquid detergents are, for example, mild detergents and alkaline detergents are so-called heavy-duty detergents.
- Liquid detergents and cleaners containing the surfactant-dye fixative combination of the present invention may further contain other ingredients as are conventional in such compositions. These are described below.
- the total surfactant content of the detergent formulations according to the invention may be from 10 to 70% by weight, preferably from 10 to 55% by weight and very particularly preferably from 20 to 50% by weight.
- anionic surfactants are sulfates, sulfonates, carboxylates, phosphates and mixtures thereof.
- Suitable cations here are alkali metals, e.g. Sodium or potassium or alkaline earth metals, e.g. Calcium or magnesium, as well as ammonium, substituted ammonium compounds, including mono-, di- or triethanolammonium cations, and mixtures thereof.
- anionic surfactants are particularly preferred: alkanesulfonates, alkyl ester sulfonates and alkyl ether sulfates as described below.
- the alkyl group may be either saturated or unsaturated, branched or linear and optionally substituted with a hydroxyl group.
- the sulfo group can be located at any position of the C chain, the primary methyl groups at the beginning and end of the chain have no sulfonate groups.
- the preferred secondary alkanesulfonates contain linear alkyl chains of about 9 to 25 carbon atoms, preferably about 10 to about 20 carbon atoms, and more preferably about 13 to 17 carbon atoms.
- the cation is, for example, sodium, potassium, ammonium, mono-, di- or triethanolammonium, calcium or magnesium. It is also possible to use mixtures of different cations.
- Very particularly preferred secondary alkane sulfonate C 3 -i 7, Na salt which is obtainable for example under the trade name Hostapur ® SAS (Clariant), Leuna-alkanesulfonate or emulsifier E30 (Leuna GmbH surfactants) or Marion ® PS (Sasol) is.
- Alkyl ester sulfonates include linear esters of Cs-Cao-carboxylic acids (ie, fatty acids) which are sulfonated with gaseous SO 3.
- Suitable starting materials are natural fats such as tallow, coconut oil and palm oil, but may also be synthetic in nature.
- Preferred alkyl ester sulfonates are compounds of the formula
- R 1 is a C 8 -C 2 o-hydrocarbon radical, preferably alkyl, and R is a CrC 6 hydrocarbon radical, preferably alkyl.
- M is a cation which forms a water-soluble salt with the alkyl ester sulfonate. Suitable cations are sodium, potassium, lithium or ammonium cations, such as monoethanolamine, diethanolamine and triethanolamine.
- R 1 is preferably C 1 -C 18 -alkyl and R is methyl, ethyl or isopropyl. Particularly preferred are methyl ester sulfonates in which R 1 is C 1 -Ci-C 6 alkyl.
- Alkyl ether sulfates are water-soluble salts or acids of the formula RO (A) m SO 3 M, in which R is an unsubstituted C 10 -C 24 -alkyl or hydroxyalkyl radical, preferably a C 12 -C 20 -alkyl or hydroxyalkyl radical, particularly preferably C 12 -C 18 - Alkyl or hydroxyalkyl represents.
- A is an ethoxy or propoxy moiety
- m is a number greater than 0, preferably between about 0.5 and about 6, more preferably between about 0.5 and about 3
- M is a hydrogen atom or a cation such as Sodium, potassium, lithium, calcium, magnesium, ammonium or a substituted ammonium cation.
- substituted ammonium cations are methyl, dimethyl, trimethylammonium and quaternary ammonium cations such as tetramethylammonium and dimethylpiperidinium cations and those derived from alkylamines such as ethylamine, diethylamine, triethylamine or mixtures thereof.
- alkylamines such as ethylamine, diethylamine, triethylamine or mixtures thereof.
- Examples which may be mentioned are C 12 -C 8 -fatty alcohol ether sulfates where the content of EO is 1, 2, 2.5, 3 or 4 mol per mol of the fatty alcohol ether sulfate and in which M is sodium or potassium. Due to their strong foam development, the use concentration of the alkyl ether sulfates depends on the intended use. Detergent laundry detergents use lower concentrations than laundry detergents. The concentrations encountered in practice are between 1 and 20% by weight. Concentrations of from 1 to 10% by weight and preferably
- acylaminocarboxylic acids which are acylsarcosinates formed by reaction of fatty acid chlorides with sodium sarcosinate in an alkaline medium; Fatty acid-protein condensation products obtained by reaction of fatty acid chlorides with oligopeptides; Salts of alkylsulfamidocarboxylic acids; Alkyl and Alkenylglycerinsulfate such as oleylglycerol sulfates, alkylphenol ether sulfates, alkyl phosphates, alkyl ether phosphates, isethionates such as acyl isethionates, N-acyl taurides, alkyl succinates, sulfosuccinates, monoesters of sulfosuccinates (especially saturated and unsaturated C 2 -C 8 monoesters) and diesters of sulfosuccinates (especially saturated and unsaturated C 2 -C 8 monoesters) and diesters
- Soaps are the salts of long-chain, native fatty acids.
- Suitable fatty acid soaps for liquid detergents in particular coconut fatty acid, which constitutes mainly a mixture of C 12 - fatty acid represents - and Ci. 4
- longer-chain fatty acids such as oleic acid, soybean fatty acid, tallow fatty acid, stearic acid, behenic acid or mixtures thereof.
- the fatty acids can be used as soaps in the form of their sodium, potassium, ammonium, mono-, di- or triethanolammonium salts.
- Particularly preferred for liquid detergents are the K, ammonium, mono-, di- or triethanolammonium salts of coconut fatty acid, of soybean fatty acid, of oleic acid and of their mixtures with one another or optionally with other fatty acids.
- Nonionic surfactants which can be used in addition to those mentioned above.
- the hydrophobic part of these compounds preferably has a molecular weight between about 1500 and about 1800.
- the addition of ethylene oxide to this hydrophobic part leads to an improvement in water solubility.
- the product is liquid up to a polyoxyethylene content of about 50% of the total weight of the condensation product, which corresponds to a condensation with up to about 40 moles of ethylene oxide.
- Commercially available examples of this product class are the Pluronic ® brands from BASF and the ® Genapol PF brands from Clariant GmbH.
- the hydrophobic moiety of these compounds consists of the reaction product of ethylenediamine with excess propylene oxide and generally has a molecular weight of about 2500 to 3000. Ethylene oxide is added to this hydrophobic unit to a content of about 40 to about 80 wt .-% polyoxyethylene and a molecular weight of about 5000 to 11000.
- this class of compounds are the ® Tetronic brands of BASF and the
- Polyethylene, polypropylene and polybutylene oxide condensates of alkylphenols.
- These compounds include the condensation products of alkylphenols having a CQ to C 2 o alkyl group, which may be either linear or branched, with alkene oxides. Preference is given to compounds having about 5 to 25 mol of alkene oxide per mole of alkylphenol.
- Commercially available surfactants of this type include Igepal ® CO-630, Triton ® X-45,
- Alkylphenolalkoxilate eg Alkylphenolethoxilate.
- nonionic compounds includes water-soluble amine oxides, water-soluble phosphine oxides and water-soluble sulfoxides, each having an alkyl group of from about 8 to about 18 carbon atoms.
- Semi-polar nonionic surfactants are also amine oxides of the formula
- R here is an alkyl, hydroxyalkyl or alkylphenol group having a chain length of about 8 to about 22 carbon atoms
- R 2 is an alkylene or hydroxyalkylene group having about 2 to 3 carbon atoms or mixtures thereof
- each R 1 is an alkyl - or hydroxy-alkyl group with about 1 to approx. 3 carbon atoms or a polyethylene oxide group having about 1 to about 3 ethylene oxide units and x is a number from 0 to about 10.
- the R 1 -Grup groups may be connected to each other via an oxygen or nitrogen atom and thus form a ring.
- Amine oxides Particularly preferred are C 8 -C 18 alkyl dimethyl amine oxides and C 8 -C 2 -Alkoxiethyl-dihydroxyethyl amine oxides and C 8 -C 8 -Fettklareamidoalkyl- dimethyl-amine oxide.
- Amine oxides can be used in use concentrations of 0.5 to 10 wt .-%, and preferably between 1 and 5 wt .-%.
- Fatty acid amides have the formula
- R is an alkyl group having from about 7 to about 21, preferably from about 9 to about 17 carbon atoms
- each R 1 is hydrogen, C 1 -C 4 alkyl, C 1 -C 4 hydroxyalkyl or (CaH 4 O) x H means where x varies from about 1 to about 3.
- the Cs-C ⁇ o-fatty acid amides in particular the corresponding monoethanolamides, diethanolamides and isopropanolamides. These can be used in concentrations between 0.5 to 5 wt .-% and in particular from 0.5 to 3 wt .-%.
- nonionic surfactants are alkyl and Alkenyloligoglycoside and Fettchurepolyglykolester or Fettaminpolyglykolester having in each case 8 to 2C, preferably 12 to 18 carbon atoms in the fatty alkyl radical, alkoxylated triglycamides, mixed ethers or Mischformyle, Alkyloligoglycoside, Alkenyloligoglycoside, fatty acid N-alkylglucamides, phosphine oxides, dialkyl sulfoxides and protein.
- amphoteric or zwitterionic surfactants are carbobetaines, sulfobetaines, aminoglycinates and amphoteric imidazolinium compounds.
- Preferred zwitterionic surfactants for use in the liquid detergents according to the invention are the carboxymethylammonium betaines, in particular C 8 - to cis-alkyl-dimethyl-carboxymethyl-ammonium betaines, C 8 - to CI 8 -
- Alkyl dipolyethoxycarboxymethylammonium betaines Alkyl dipolyethoxycarboxymethylammonium betaines.
- N-carboxyethyl-ammoniumbetaine for their synthesis instead of chloroacetic acid or salts thereof, the chloropropionic acid and its salts are used.
- Examples thereof are the C 2 -C 8 alkyl-aminopropionates, and C 2 -C 8 alkyl iminodipropionates as alkali metal and mono-, di- and trialkylammonium Safee.
- a preferred sulfobetaine is C 1 -C 4 -alkyl-dimethyl-sulfopropyl-betaine.
- Amphoteric surfactants based on imidazoline are supplied under the trade name Miranol ® and Steinapon.RTM ®. Preference is given to the sodium salt of 1- (carboxymethyloxyethyl) -1- (carboxymethyl) -2-laurylimidazolinium.
- the zwitterionic surfactants are used as co-surfactants. Your
- Use concentration is 1 to 10 wt .-%, preferably 3 to 5 wt .-%.
- detergent ingredients that may be included in the present invention include inorganic and / or organic builders to reduce the degree of hardness of the water.
- Inorganic builders include, for example, alkali, ammonium and alkanolammonium salts of polyphosphates such as tripolyphosphates, pyrophosphates and glassy polymeric metaphosphates, phosphonates, silicates, carbonates including bicarbonates and sesquicarbonates and aluminosilicates as described below:
- Aluminosilicate builders in particular zeolites having the formula Na z [(Al 2 O) z (SiO 2) y] -xH 2 O, where z and y are integers of at least 6, that ratio of z to y is between 1.0 to 0.5, and x is an integer from about 15 to about 264.
- Suitable aluminosilicate-based ion exchangers are commercially available. These aluminosilicates may be of crystalline or amorphous structure and may be naturally occurring or synthetically produced. Preferred ion exchangers based on synthetic crystalline aluminosilicates are available under the name zeolite A, zeolite P (B) and zeolite X. Preference is given to aluminosilicates having a particle diameter between 0.1 and 10 microns.
- Suitable organic builders include polycarboxylic compounds such as ether polycarboxylates and oxydisuccinates. Reference should also be made to "TMS / TDS" equipment from US 4,663,071.
- Suitable builders include the ether hydroxypolycarboxylates, copolymers of maleic anhydride with ethylene or vinyl methyl ether, 1,3,5-trihydroxybenzene-2,4,6-trisulfonic acid and carboxymethyloxbernic acid, the alkali, ammonium and substituted ammonium salts of polyacetic acids such as e.g. Ethylenediamine tetraacetic acid and nitrilotriacetic acid, and polycarboxylic acids, such as mellitic acid, succinic acid, oxydibemic acid, polymaleic acid, benzene-1, 3,5-tricarboxylic acid, carboxymethyloxysuccinic acid, and their soluble salts.
- polyacetic acids such as e.g. Ethylenediamine tetraacetic acid and nitrilotriacetic acid
- polycarboxylic acids such as mellitic acid, succinic acid, oxydibemic acid,
- Preferred organic builders are polycarboxylates based on acrylic acid and / or maleic acid, such as Sokalan ® CP brands (BASF) or Acusol ® brands (Rhom and Haas), as well as builders based on citrate, for example citric acid and its soluble salts , in particular the sodium salt.
- Sokalan ® CP brands BASF
- Acusol ® brands Rhom and Haas
- citrate for example citric acid and its soluble salts , in particular the sodium salt.
- Phosphorus-based builders are alkali metal phosphates such as sodium tripolyphosphate, sodium pyrophosphate and sodium orthophosphate.
- phosphonates such as ethane-1-hydroxy-1, 1-diphosphonate (HEDP) and other known phosphonates come into question for the present invention.
- the liquid detergents according to the invention may further contain the usual auxiliaries which enhance the cleaning action, serve to care for the textile to be washed or change the performance properties of the detergent composition.
- Suitable adjuvants include, for example, enzymes, in particular proteases, lipases, cellulases, amylases and mannanases; Enzyme stabilizers; Foam boosters; Foam inhibitors, such as silicone oils or paraffins; Corrosion inhibitors; Color transfer inhibitors; optical brighteners; UV absorber; Bleach; Preservatives; alkalis; hydrotrope compounds; antioxidants; Solvents or solubilizers, such as ethanol, glycerol, propanediol; dispersant; Anti-redeposition agents; Graying inhibitors; plasticizers; antistatic agents; Dyes and perfumes.
- dyes here includes both water-soluble dyes and insoluble color pigments. Water-soluble dyes are preferred in
- Liquid detergents used include the groups of acid dyes,
- Direct dyes and reactive dyes These groups can be e.g. Represent representatives of azo dyes, metal complex dyes and polycyclic dyes.
- fragrance or perfume oils individual fragrance compounds, e.g. the synthetic products of the ester, ether, aldehyde, ketone, alcohol and hydrocarbon type are used. Preference is given to using mixtures of different fragrances which together form an attractive
- Perfume oils may also contain natural fragrance mixtures and ethereal oils of lower volatility.
- polyamine N-oxides such as poly (4-vinylpyridine-N-ox: id), poly (4-vinylpyridine-betaine), polyvinylpyrrolidone and copolymers of N-vinylpyrrolidone with N-vinylimidazole and optionally other monomers, polyvinylimidazole, also cyclodextrins and cyclodextrin derivatives.
- the detergents and cleaning agents according to the invention are characterized in that they are clear or at least opaque translucent to slightly cloudy. It is essential that these formulations are stable and do not flocculate. They provide a color-retaining and color transfer inhibiting effect, a softening effect, an anti-wrinkle effect and protection of mechanical wear.
- Comparative Examples 1 to 4 demonstrate the incompatibility of anionic surfactants with the color fixing agents (FFM) and the problem of preparing stable anionic liquid detergents.
- Examples 1 and 2 describe stable, liquid detergent formulations based on the anionic surfactant alkylbenzenesulfonate and polymeric color fixing agents (FFM) according to the invention.
- anionic surfactants used were alkylbenzenesulfonate and alkyl ether carboxylate, the nonionic surfactant Ci 2 / u-alkyl-7EO-ethoxylate and the dye-fixing agent FFM 5.
- anionic surfactants were linear alkylbenzenesulfonate and alkyl ether carboxylate or betaine, as nonionic surfactant Ci 2 / i 4 -alkyl-7EO-ethoxylate and as
- FFM 1 reaction product of diethylenediamine, dicyandiarnid and
- FFM 2 reaction product of dimethylamine and epichlorohydrin.
- FFM 3 reaction product of dicyandiamide, ammonium diloride and
- FFM 4 reaction product of dimethylaminopropylamine
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Abstract
Description
Claims
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| DE102004051714A DE102004051714A1 (de) | 2004-10-23 | 2004-10-23 | Anionische Flüssigwaschmittel mit Farbfixiermitteln |
| PCT/EP2005/011179 WO2006045481A1 (de) | 2004-10-23 | 2005-10-18 | Flüssigwaschmittel enthalthend farbfixiermitteln |
Publications (3)
| Publication Number | Publication Date |
|---|---|
| EP1805290A1 true EP1805290A1 (de) | 2007-07-11 |
| EP1805290B1 EP1805290B1 (de) | 2008-03-19 |
| EP1805290B8 EP1805290B8 (de) | 2008-08-13 |
Family
ID=34638887
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| EP05798492A Expired - Lifetime EP1805290B8 (de) | 2004-10-23 | 2005-10-18 | Flüssigwaschmittel enthaltend farbfixiermittel |
Country Status (6)
| Country | Link |
|---|---|
| US (1) | US7541327B2 (de) |
| EP (1) | EP1805290B8 (de) |
| JP (1) | JP2008517120A (de) |
| DE (2) | DE102004051714A1 (de) |
| ES (1) | ES2303278T3 (de) |
| WO (1) | WO2006045481A1 (de) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103975049A (zh) * | 2011-12-12 | 2014-08-06 | 荷兰联合利华有限公司 | 洗衣组合物 |
Families Citing this family (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20100050346A1 (en) * | 2008-08-28 | 2010-03-04 | Corona Iii Alessandro | Compositions and methods for providing a benefit |
| EP2857489A3 (de) * | 2008-08-28 | 2015-04-29 | The Procter and Gamble Company | Verfahren zur Herstellung einer Textilpflegezusammensetzung |
| ES2809176T3 (es) * | 2008-12-04 | 2021-03-03 | Ecolab Usa Inc | Composiciones de lavandería y métodos de uso |
| CN104152291A (zh) * | 2014-08-20 | 2014-11-19 | 浙江神英商贸有限公司 | 一种防染洗衣液及其制作方法 |
| EP3421583A1 (de) | 2017-06-26 | 2019-01-02 | Basf Se | Verwendung von kationischen vinylcarboxamid-/vinylamincopolymeren als farbschonende mittel für waschformulierungen |
| EP4217452A1 (de) | 2020-09-28 | 2023-08-02 | The Procter & Gamble Company | Waschmittelzusammensetzung enthaltend ein farbstofffixiermittel und aminoxid |
| EP4217453A1 (de) * | 2020-09-28 | 2023-08-02 | The Procter & Gamble Company | Waschmittelzusammensetzung enthaltend ein farbstofffixiermittel und lineares alkylbenzolsulfonat |
| WO2022062756A1 (en) * | 2020-09-28 | 2022-03-31 | The Procter & Gamble Company | Water-soluble unit dose article comprising amine oxide surfactant with dominant non-aqueous solvent |
Family Cites Families (14)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3332880A (en) | 1965-01-04 | 1967-07-25 | Procter & Gamble | Detergent composition |
| GB1082179A (en) | 1965-07-19 | 1967-09-06 | Citrique Belge Nv | Unsaturated carboxylic salt materials and derivatives thereof |
| US4663071A (en) | 1986-01-30 | 1987-05-05 | The Procter & Gamble Company | Ether carboxylate detergent builders and process for their preparation |
| CA2001927C (en) | 1988-11-03 | 1999-12-21 | Graham Thomas Brown | Aluminosilicates and detergent compositions |
| DE4116807A1 (de) | 1991-05-23 | 1992-11-26 | Henkel Kgaa | Konzentriertes waessriges fluessigwaschmittel |
| US5783548A (en) | 1992-11-06 | 1998-07-21 | The Procter & Gamble Company | Stable liquid detergent compositions inhibiting dye transfer |
| EP0704523A1 (de) | 1994-09-30 | 1996-04-03 | The Procter & Gamble Company | Betain enthaltende Zusammensetzungen zur Verhinderung der Farbstoffübertragung |
| CA2377017C (en) | 1999-06-29 | 2006-05-30 | The Procter & Gamble Company | Fabric enhancement compositions having improved color fidelity |
| EP1239025A3 (de) | 2001-03-03 | 2003-09-03 | Clariant GmbH | Waschmittel und Wäschebehandlungsmittel enthaltend farbübertragungsinhibierend Farbfixiermittel |
| DE10150724A1 (de) * | 2001-03-03 | 2003-04-17 | Clariant Gmbh | Waschmittel und Wäschebehandlungsmittel enthaltend ein oder mehrere farbübertragungsinhibierende Farbfixiermittel |
| GB0126280D0 (en) | 2001-11-01 | 2002-01-02 | Unilever Plc | Liquid detergent compositions |
| DE102004018051A1 (de) | 2004-04-08 | 2005-11-10 | Clariant Gmbh | Wasch- und Reinigungsmittel enthaltend Farbfixiermittel und Soil Release Polymere |
| DE102004043728A1 (de) | 2004-09-10 | 2005-06-30 | Clariant Gmbh | Flüssigwaschmittel enthaltend Farbfixiermittel |
| DE102004051010A1 (de) * | 2004-10-20 | 2005-06-23 | Clariant Gmbh | Flüssigwaschmittel enthaltend anionische Tenside und Farbfixiermittel |
-
2004
- 2004-10-23 DE DE102004051714A patent/DE102004051714A1/de not_active Withdrawn
-
2005
- 2005-10-18 JP JP2007537182A patent/JP2008517120A/ja not_active Withdrawn
- 2005-10-18 US US11/666,038 patent/US7541327B2/en not_active Expired - Fee Related
- 2005-10-18 WO PCT/EP2005/011179 patent/WO2006045481A1/de not_active Ceased
- 2005-10-18 ES ES05798492T patent/ES2303278T3/es not_active Expired - Lifetime
- 2005-10-18 EP EP05798492A patent/EP1805290B8/de not_active Expired - Lifetime
- 2005-10-18 DE DE502005003389T patent/DE502005003389D1/de not_active Expired - Fee Related
Non-Patent Citations (1)
| Title |
|---|
| See references of WO2006045481A1 * |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103975049A (zh) * | 2011-12-12 | 2014-08-06 | 荷兰联合利华有限公司 | 洗衣组合物 |
Also Published As
| Publication number | Publication date |
|---|---|
| DE102004051714A1 (de) | 2005-07-07 |
| US7541327B2 (en) | 2009-06-02 |
| ES2303278T3 (es) | 2008-08-01 |
| JP2008517120A (ja) | 2008-05-22 |
| EP1805290B1 (de) | 2008-03-19 |
| WO2006045481A1 (de) | 2006-05-04 |
| DE502005003389D1 (de) | 2008-04-30 |
| EP1805290B8 (de) | 2008-08-13 |
| US20080103081A1 (en) | 2008-05-01 |
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