EP0199403A2 - Compositions détergentes liquides stables - Google Patents
Compositions détergentes liquides stables Download PDFInfo
- Publication number
- EP0199403A2 EP0199403A2 EP86200584A EP86200584A EP0199403A2 EP 0199403 A2 EP0199403 A2 EP 0199403A2 EP 86200584 A EP86200584 A EP 86200584A EP 86200584 A EP86200584 A EP 86200584A EP 0199403 A2 EP0199403 A2 EP 0199403A2
- Authority
- EP
- European Patent Office
- Prior art keywords
- alkyl
- composition
- group
- surfactant
- formula
- 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
- 239000000203 mixture Substances 0.000 title claims abstract description 94
- 239000003599 detergent Substances 0.000 title claims abstract description 29
- 239000007788 liquid Substances 0.000 title claims abstract description 25
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims abstract description 58
- 239000004094 surface-active agent Substances 0.000 claims abstract description 51
- 239000002689 soil Substances 0.000 claims abstract description 35
- 239000002736 nonionic surfactant Substances 0.000 claims abstract description 25
- 150000001412 amines Chemical class 0.000 claims abstract description 22
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 17
- 125000001453 quaternary ammonium group Chemical group 0.000 claims abstract description 16
- 239000003945 anionic surfactant Substances 0.000 claims abstract description 15
- 229920005862 polyol Polymers 0.000 claims abstract description 15
- 150000003077 polyols Chemical class 0.000 claims abstract description 15
- 150000001408 amides Chemical class 0.000 claims abstract description 12
- 238000006386 neutralization reaction Methods 0.000 claims abstract description 9
- -1 alkenyl radical Chemical group 0.000 claims description 43
- 125000000217 alkyl group Chemical group 0.000 claims description 42
- 125000004432 carbon atom Chemical group C* 0.000 claims description 31
- 229920005646 polycarboxylate Polymers 0.000 claims description 24
- 150000001875 compounds Chemical class 0.000 claims description 18
- IAYPIBMASNFSPL-UHFFFAOYSA-N Ethylene oxide Chemical group C1CO1 IAYPIBMASNFSPL-UHFFFAOYSA-N 0.000 claims description 17
- 239000000463 material Substances 0.000 claims description 17
- 239000002253 acid Substances 0.000 claims description 16
- DNIAPMSPPWPWGF-UHFFFAOYSA-N Propylene glycol Chemical compound CC(O)CO DNIAPMSPPWPWGF-UHFFFAOYSA-N 0.000 claims description 12
- 229920000642 polymer Polymers 0.000 claims description 12
- BDHFUVZGWQCTTF-UHFFFAOYSA-M sulfonate Chemical compound [O-]S(=O)=O BDHFUVZGWQCTTF-UHFFFAOYSA-M 0.000 claims description 12
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 claims description 11
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 claims description 9
- 229910052739 hydrogen Inorganic materials 0.000 claims description 9
- 239000001257 hydrogen Substances 0.000 claims description 8
- 150000004671 saturated fatty acids Chemical class 0.000 claims description 8
- 125000002768 hydroxyalkyl group Chemical group 0.000 claims description 7
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical group C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 claims description 6
- 239000005977 Ethylene Substances 0.000 claims description 6
- 239000004064 cosurfactant Substances 0.000 claims description 6
- 238000000034 method Methods 0.000 claims description 6
- 150000003254 radicals Chemical class 0.000 claims description 5
- HZAXFHJVJLSVMW-UHFFFAOYSA-N 2-Aminoethan-1-ol Chemical compound NCCO HZAXFHJVJLSVMW-UHFFFAOYSA-N 0.000 claims description 4
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 4
- 125000003342 alkenyl group Chemical group 0.000 claims description 4
- 125000005211 alkyl trimethyl ammonium group Chemical group 0.000 claims description 4
- 150000002431 hydrogen Chemical class 0.000 claims description 4
- JZMJDSHXVKJFKW-UHFFFAOYSA-M methyl sulfate(1-) Chemical compound COS([O-])(=O)=O JZMJDSHXVKJFKW-UHFFFAOYSA-M 0.000 claims description 4
- 125000004178 (C1-C4) alkyl group Chemical group 0.000 claims description 3
- 125000000954 2-hydroxyethyl group Chemical group [H]C([*])([H])C([H])([H])O[H] 0.000 claims description 3
- QOXOZONBQWIKDA-UHFFFAOYSA-N 3-hydroxypropyl Chemical group [CH2]CCO QOXOZONBQWIKDA-UHFFFAOYSA-N 0.000 claims description 3
- CPELXLSAUQHCOX-UHFFFAOYSA-M Bromide Chemical compound [Br-] CPELXLSAUQHCOX-UHFFFAOYSA-M 0.000 claims description 3
- 125000002252 acyl group Chemical group 0.000 claims description 3
- 125000006177 alkyl benzyl group Chemical group 0.000 claims description 3
- 150000008051 alkyl sulfates Chemical class 0.000 claims description 3
- 150000001450 anions Chemical class 0.000 claims description 3
- 125000001797 benzyl group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C([H])([H])* 0.000 claims description 3
- 150000001768 cations Chemical class 0.000 claims description 3
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 claims description 3
- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 claims description 3
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims description 3
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 claims description 3
- 125000002853 C1-C4 hydroxyalkyl group Chemical group 0.000 claims description 2
- 125000000843 phenylene group Chemical group C1(=C(C=CC=C1)*)* 0.000 claims description 2
- 239000003125 aqueous solvent Substances 0.000 claims 1
- 230000001376 precipitating effect Effects 0.000 claims 1
- 235000014113 dietary fatty acids Nutrition 0.000 abstract description 15
- 239000000194 fatty acid Substances 0.000 abstract description 15
- 229930195729 fatty acid Natural products 0.000 abstract description 15
- 150000004665 fatty acids Chemical class 0.000 abstract description 14
- 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 abstract description 11
- 229910052708 sodium Inorganic materials 0.000 abstract description 11
- 239000011734 sodium Substances 0.000 abstract description 11
- 239000003795 chemical substances by application Substances 0.000 abstract description 10
- 239000011591 potassium Substances 0.000 abstract description 9
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 abstract description 8
- 229910052700 potassium Inorganic materials 0.000 abstract description 7
- 239000002904 solvent Substances 0.000 abstract description 7
- 229920000728 polyester Polymers 0.000 abstract description 4
- 150000007942 carboxylates Chemical class 0.000 abstract description 2
- 125000001140 1,4-phenylene group Chemical group [H]C1=C([H])C([*:2])=C([H])C([H])=C1[*:1] 0.000 description 13
- 108090000790 Enzymes Proteins 0.000 description 12
- 102000004190 Enzymes Human genes 0.000 description 12
- 229940088598 enzyme Drugs 0.000 description 12
- 150000003839 salts Chemical class 0.000 description 10
- 235000010338 boric acid Nutrition 0.000 description 8
- KGBXLFKZBHKPEV-UHFFFAOYSA-N boric acid Chemical compound OB(O)O KGBXLFKZBHKPEV-UHFFFAOYSA-N 0.000 description 7
- 239000004327 boric acid Substances 0.000 description 7
- BHPQYMZQTOCNFJ-UHFFFAOYSA-N Calcium cation Chemical compound [Ca+2] BHPQYMZQTOCNFJ-UHFFFAOYSA-N 0.000 description 6
- 229910001424 calcium ion Inorganic materials 0.000 description 6
- 230000000694 effects Effects 0.000 description 6
- 239000007859 condensation product Substances 0.000 description 5
- RTZKZFJDLAIYFH-UHFFFAOYSA-N ether Substances CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 5
- RZVAJINKPMORJF-UHFFFAOYSA-N Acetaminophen Chemical compound CC(=O)NC1=CC=C(O)C=C1 RZVAJINKPMORJF-UHFFFAOYSA-N 0.000 description 4
- 150000001734 carboxylic acid salts Chemical class 0.000 description 4
- 229920001577 copolymer Polymers 0.000 description 4
- 238000002425 crystallisation Methods 0.000 description 4
- 230000008025 crystallization Effects 0.000 description 4
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 4
- 239000000047 product Substances 0.000 description 4
- 238000006467 substitution reaction Methods 0.000 description 4
- 150000003871 sulfonates Chemical class 0.000 description 4
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 3
- 235000013162 Cocos nucifera Nutrition 0.000 description 3
- 244000060011 Cocos nucifera Species 0.000 description 3
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 3
- 108091005804 Peptidases Proteins 0.000 description 3
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 3
- 125000000129 anionic group Chemical group 0.000 description 3
- 235000003441 saturated fatty acids Nutrition 0.000 description 3
- 241000894007 species Species 0.000 description 3
- 125000001424 substituent group Chemical group 0.000 description 3
- 108010065511 Amylases Proteins 0.000 description 2
- 102000013142 Amylases Human genes 0.000 description 2
- BDAGIHXWWSANSR-UHFFFAOYSA-M Formate Chemical compound [O-]C=O BDAGIHXWWSANSR-UHFFFAOYSA-M 0.000 description 2
- VZCYOOQTPOCHFL-OWOJBTEDSA-N Fumaric acid Chemical compound OC(=O)\C=C\C(O)=O VZCYOOQTPOCHFL-OWOJBTEDSA-N 0.000 description 2
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 description 2
- IGFHQQFPSIBGKE-UHFFFAOYSA-N Nonylphenol Natural products CCCCCCCCCC1=CC=C(O)C=C1 IGFHQQFPSIBGKE-UHFFFAOYSA-N 0.000 description 2
- 102000035195 Peptidases Human genes 0.000 description 2
- 229930182556 Polyacetal Natural products 0.000 description 2
- 229920002873 Polyethylenimine Polymers 0.000 description 2
- 239000004365 Protease Substances 0.000 description 2
- 108010056079 Subtilisins Proteins 0.000 description 2
- 102000005158 Subtilisins Human genes 0.000 description 2
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 2
- GSEJCLTVZPLZKY-UHFFFAOYSA-N Triethanolamine Chemical compound OCCN(CCO)CCO GSEJCLTVZPLZKY-UHFFFAOYSA-N 0.000 description 2
- 150000001298 alcohols Chemical class 0.000 description 2
- 229910052783 alkali metal Inorganic materials 0.000 description 2
- 125000004450 alkenylene group Chemical group 0.000 description 2
- 125000005037 alkyl phenyl group Chemical group 0.000 description 2
- 125000002947 alkylene group Chemical group 0.000 description 2
- 235000019418 amylase Nutrition 0.000 description 2
- 125000000732 arylene group Chemical group 0.000 description 2
- 239000007844 bleaching agent Substances 0.000 description 2
- 238000004140 cleaning Methods 0.000 description 2
- ZBCBWPMODOFKDW-UHFFFAOYSA-N diethanolamine Chemical compound OCCNCCO ZBCBWPMODOFKDW-UHFFFAOYSA-N 0.000 description 2
- 238000009826 distribution Methods 0.000 description 2
- 150000002148 esters Chemical class 0.000 description 2
- 229940044170 formate Drugs 0.000 description 2
- 235000021588 free fatty acids Nutrition 0.000 description 2
- 230000008014 freezing Effects 0.000 description 2
- 238000007710 freezing Methods 0.000 description 2
- 238000010348 incorporation Methods 0.000 description 2
- 239000004615 ingredient Substances 0.000 description 2
- 238000004900 laundering Methods 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
- POULHZVOKOAJMA-UHFFFAOYSA-N methyl undecanoic acid Natural products CCCCCCCCCCCC(O)=O POULHZVOKOAJMA-UHFFFAOYSA-N 0.000 description 2
- SNQQPOLDUKLAAF-UHFFFAOYSA-N nonylphenol Chemical compound CCCCCCCCCC1=CC=CC=C1O SNQQPOLDUKLAAF-UHFFFAOYSA-N 0.000 description 2
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 description 2
- 239000012188 paraffin wax Substances 0.000 description 2
- 239000012071 phase Substances 0.000 description 2
- 238000005191 phase separation Methods 0.000 description 2
- HXITXNWTGFUOAU-UHFFFAOYSA-N phenylboronic acid Chemical compound OB(O)C1=CC=CC=C1 HXITXNWTGFUOAU-UHFFFAOYSA-N 0.000 description 2
- 235000002949 phytic acid Nutrition 0.000 description 2
- 229920006324 polyoxymethylene Polymers 0.000 description 2
- 229910001414 potassium ion Inorganic materials 0.000 description 2
- ULWHHBHJGPPBCO-UHFFFAOYSA-N propane-1,1-diol Chemical compound CCC(O)O ULWHHBHJGPPBCO-UHFFFAOYSA-N 0.000 description 2
- 230000002797 proteolythic effect Effects 0.000 description 2
- 229940024999 proteolytic enzymes for treatment of wounds and ulcers Drugs 0.000 description 2
- CYIDZMCFTVVTJO-UHFFFAOYSA-N pyromellitic acid Chemical compound OC(=O)C1=CC(C(O)=O)=C(C(O)=O)C=C1C(O)=O CYIDZMCFTVVTJO-UHFFFAOYSA-N 0.000 description 2
- 229910001415 sodium ion Inorganic materials 0.000 description 2
- HLZKNKRTKFSKGZ-UHFFFAOYSA-N tetradecan-1-ol Chemical compound CCCCCCCCCCCCCCO HLZKNKRTKFSKGZ-UHFFFAOYSA-N 0.000 description 2
- 238000010257 thawing Methods 0.000 description 2
- VZCYOOQTPOCHFL-UHFFFAOYSA-N trans-butenedioic acid Natural products OC(=O)C=CC(O)=O VZCYOOQTPOCHFL-UHFFFAOYSA-N 0.000 description 2
- GSEJCLTVZPLZKY-UHFFFAOYSA-O triethanolammonium Chemical class OCC[NH+](CCO)CCO GSEJCLTVZPLZKY-UHFFFAOYSA-O 0.000 description 2
- GETQZCLCWQTVFV-UHFFFAOYSA-N trimethylamine Chemical class CN(C)C GETQZCLCWQTVFV-UHFFFAOYSA-N 0.000 description 2
- IQVLXQGNLCPZCL-UHFFFAOYSA-N (2,5-dioxopyrrolidin-1-yl) 2,6-bis[(2-methylpropan-2-yl)oxycarbonylamino]hexanoate Chemical compound CC(C)(C)OC(=O)NCCCCC(NC(=O)OC(C)(C)C)C(=O)ON1C(=O)CCC1=O IQVLXQGNLCPZCL-UHFFFAOYSA-N 0.000 description 1
- QBLFZIBJXUQVRF-UHFFFAOYSA-N (4-bromophenyl)boronic acid Chemical compound OB(O)C1=CC=C(Br)C=C1 QBLFZIBJXUQVRF-UHFFFAOYSA-N 0.000 description 1
- WRIDQFICGBMAFQ-UHFFFAOYSA-N (E)-8-Octadecenoic acid Natural products CCCCCCCCCC=CCCCCCCC(O)=O WRIDQFICGBMAFQ-UHFFFAOYSA-N 0.000 description 1
- 239000001124 (E)-prop-1-ene-1,2,3-tricarboxylic acid Substances 0.000 description 1
- DNIAPMSPPWPWGF-GSVOUGTGSA-N (R)-(-)-Propylene glycol Chemical compound C[C@@H](O)CO DNIAPMSPPWPWGF-GSVOUGTGSA-N 0.000 description 1
- CIOXZGOUEYHNBF-UHFFFAOYSA-N (carboxymethoxy)succinic acid Chemical compound OC(=O)COC(C(O)=O)CC(O)=O CIOXZGOUEYHNBF-UHFFFAOYSA-N 0.000 description 1
- 125000001989 1,3-phenylene group Chemical group [H]C1=C([H])C([*:1])=C([H])C([*:2])=C1[H] 0.000 description 1
- 125000004955 1,4-cyclohexylene group Chemical group [H]C1([H])C([H])([H])C([H])([*:1])C([H])([H])C([H])([H])C1([H])[*:2] 0.000 description 1
- 125000004958 1,4-naphthylene group Chemical group 0.000 description 1
- QPKFVRWIISEVCW-UHFFFAOYSA-N 1-butane boronic acid Chemical compound CCCCB(O)O QPKFVRWIISEVCW-UHFFFAOYSA-N 0.000 description 1
- FNRRHKQTVNDRSJ-UHFFFAOYSA-N 2,3-bis(6-methylheptyl)phenol Chemical compound CC(C)CCCCCC1=CC=CC(O)=C1CCCCCC(C)C FNRRHKQTVNDRSJ-UHFFFAOYSA-N 0.000 description 1
- JKTAIYGNOFSMCE-UHFFFAOYSA-N 2,3-di(nonyl)phenol Chemical compound CCCCCCCCCC1=CC=CC(O)=C1CCCCCCCCC JKTAIYGNOFSMCE-UHFFFAOYSA-N 0.000 description 1
- CFPOJWPDQWJEMO-UHFFFAOYSA-N 2-(1,2-dicarboxyethoxy)butanedioic acid Chemical compound OC(=O)CC(C(O)=O)OC(C(O)=O)CC(O)=O CFPOJWPDQWJEMO-UHFFFAOYSA-N 0.000 description 1
- JAHNSTQSQJOJLO-UHFFFAOYSA-N 2-(3-fluorophenyl)-1h-imidazole Chemical compound FC1=CC=CC(C=2NC=CN=2)=C1 JAHNSTQSQJOJLO-UHFFFAOYSA-N 0.000 description 1
- LVVZBNKWTVZSIU-UHFFFAOYSA-N 2-(carboxymethoxy)propanedioic acid Chemical compound OC(=O)COC(C(O)=O)C(O)=O LVVZBNKWTVZSIU-UHFFFAOYSA-N 0.000 description 1
- MPNXSZJPSVBLHP-UHFFFAOYSA-N 2-chloro-n-phenylpyridine-3-carboxamide Chemical compound ClC1=NC=CC=C1C(=O)NC1=CC=CC=C1 MPNXSZJPSVBLHP-UHFFFAOYSA-N 0.000 description 1
- CYEJMVLDXAUOPN-UHFFFAOYSA-N 2-dodecylphenol Chemical compound CCCCCCCCCCCCC1=CC=CC=C1O CYEJMVLDXAUOPN-UHFFFAOYSA-N 0.000 description 1
- PSZAEHPBBUYICS-UHFFFAOYSA-N 2-methylidenepropanedioic acid Chemical compound OC(=O)C(=C)C(O)=O PSZAEHPBBUYICS-UHFFFAOYSA-N 0.000 description 1
- LQJBNNIYVWPHFW-UHFFFAOYSA-N 20:1omega9c fatty acid Natural products CCCCCCCCCCC=CCCCCCCCC(O)=O LQJBNNIYVWPHFW-UHFFFAOYSA-N 0.000 description 1
- MMINFSMURORWKH-UHFFFAOYSA-N 3,6-dioxabicyclo[6.2.2]dodeca-1(10),8,11-triene-2,7-dione Chemical group O=C1OCCOC(=O)C2=CC=C1C=C2 MMINFSMURORWKH-UHFFFAOYSA-N 0.000 description 1
- GDTSJMKGXGJFGQ-UHFFFAOYSA-N 3,7-dioxido-2,4,6,8,9-pentaoxa-1,3,5,7-tetraborabicyclo[3.3.1]nonane Chemical compound O1B([O-])OB2OB([O-])OB1O2 GDTSJMKGXGJFGQ-UHFFFAOYSA-N 0.000 description 1
- QSBYPNXLFMSGKH-UHFFFAOYSA-N 9-Heptadecensaeure Natural products CCCCCCCC=CCCCCCCCC(O)=O QSBYPNXLFMSGKH-UHFFFAOYSA-N 0.000 description 1
- 239000004382 Amylase Substances 0.000 description 1
- 229910011255 B2O3 Inorganic materials 0.000 description 1
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 description 1
- CBOCVOKPQGJKKJ-UHFFFAOYSA-L Calcium formate Chemical compound [Ca+2].[O-]C=O.[O-]C=O CBOCVOKPQGJKKJ-UHFFFAOYSA-L 0.000 description 1
- BCZXFFBUYPCTSJ-UHFFFAOYSA-L Calcium propionate Chemical compound [Ca+2].CCC([O-])=O.CCC([O-])=O BCZXFFBUYPCTSJ-UHFFFAOYSA-L 0.000 description 1
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 description 1
- CXRFDZFCGOPDTD-UHFFFAOYSA-M Cetrimide Chemical compound [Br-].CCCCCCCCCCCCCC[N+](C)(C)C CXRFDZFCGOPDTD-UHFFFAOYSA-M 0.000 description 1
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 1
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 1
- QEVGZEDELICMKH-UHFFFAOYSA-N Diglycolic acid Chemical compound OC(=O)COCC(O)=O QEVGZEDELICMKH-UHFFFAOYSA-N 0.000 description 1
- 229940120146 EDTMP Drugs 0.000 description 1
- 241000196324 Embryophyta Species 0.000 description 1
- 239000004593 Epoxy Substances 0.000 description 1
- IMQLKJBTEOYOSI-GPIVLXJGSA-N Inositol-hexakisphosphate Chemical class OP(O)(=O)O[C@H]1[C@H](OP(O)(O)=O)[C@@H](OP(O)(O)=O)[C@H](OP(O)(O)=O)[C@H](OP(O)(O)=O)[C@@H]1OP(O)(O)=O IMQLKJBTEOYOSI-GPIVLXJGSA-N 0.000 description 1
- QPCDCPDFJACHGM-UHFFFAOYSA-N N,N-bis{2-[bis(carboxymethyl)amino]ethyl}glycine Chemical compound OC(=O)CN(CC(O)=O)CCN(CC(=O)O)CCN(CC(O)=O)CC(O)=O QPCDCPDFJACHGM-UHFFFAOYSA-N 0.000 description 1
- 239000005642 Oleic acid Substances 0.000 description 1
- ZQPPMHVWECSIRJ-UHFFFAOYSA-N Oleic acid Natural products CCCCCCCCC=CCCCCCCCC(O)=O ZQPPMHVWECSIRJ-UHFFFAOYSA-N 0.000 description 1
- 235000019482 Palm oil Nutrition 0.000 description 1
- IMQLKJBTEOYOSI-UHFFFAOYSA-N Phytic acid Natural products OP(O)(=O)OC1C(OP(O)(O)=O)C(OP(O)(O)=O)C(OP(O)(O)=O)C(OP(O)(O)=O)C1OP(O)(O)=O IMQLKJBTEOYOSI-UHFFFAOYSA-N 0.000 description 1
- 229920003171 Poly (ethylene oxide) Polymers 0.000 description 1
- OFOBLEOULBTSOW-UHFFFAOYSA-N Propanedioic acid Natural products OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 description 1
- 102100037486 Reverse transcriptase/ribonuclease H Human genes 0.000 description 1
- 239000004280 Sodium formate Substances 0.000 description 1
- 229920004890 Triton X-100 Polymers 0.000 description 1
- 229920004892 Triton X-102 Polymers 0.000 description 1
- 229920004929 Triton X-114 Polymers 0.000 description 1
- 229920004897 Triton X-45 Polymers 0.000 description 1
- 150000007513 acids Chemical class 0.000 description 1
- 229940091181 aconitic acid Drugs 0.000 description 1
- 230000002411 adverse Effects 0.000 description 1
- 125000001931 aliphatic group Chemical group 0.000 description 1
- 150000001340 alkali metals Chemical class 0.000 description 1
- 150000004996 alkyl benzenes Chemical class 0.000 description 1
- 229940025131 amylases Drugs 0.000 description 1
- 230000003625 amylolytic effect Effects 0.000 description 1
- 230000000844 anti-bacterial effect Effects 0.000 description 1
- 239000003963 antioxidant agent Substances 0.000 description 1
- 239000003899 bactericide agent Substances 0.000 description 1
- QNSOHXTZPUMONC-UHFFFAOYSA-N benzene pentacarboxylic acid Natural products OC(=O)C1=CC(C(O)=O)=C(C(O)=O)C(C(O)=O)=C1C(O)=O QNSOHXTZPUMONC-UHFFFAOYSA-N 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 229910021538 borax Inorganic materials 0.000 description 1
- 125000005619 boric acid group Chemical class 0.000 description 1
- 239000011575 calcium Substances 0.000 description 1
- 229910052791 calcium Inorganic materials 0.000 description 1
- VSGNNIFQASZAOI-UHFFFAOYSA-L calcium acetate Chemical compound [Ca+2].CC([O-])=O.CC([O-])=O VSGNNIFQASZAOI-UHFFFAOYSA-L 0.000 description 1
- 239000001639 calcium acetate Substances 0.000 description 1
- 235000011092 calcium acetate Nutrition 0.000 description 1
- 229960005147 calcium acetate Drugs 0.000 description 1
- 239000004281 calcium formate Substances 0.000 description 1
- 235000019255 calcium formate Nutrition 0.000 description 1
- 229940044172 calcium formate Drugs 0.000 description 1
- 239000004330 calcium propionate Substances 0.000 description 1
- 235000010331 calcium propionate Nutrition 0.000 description 1
- 159000000007 calcium salts Chemical class 0.000 description 1
- 229910002091 carbon monoxide Inorganic materials 0.000 description 1
- 239000000460 chlorine Substances 0.000 description 1
- 229910052801 chlorine Inorganic materials 0.000 description 1
- GTZCVFVGUGFEME-IWQZZHSRSA-N cis-aconitic acid Chemical compound OC(=O)C\C(C(O)=O)=C\C(O)=O GTZCVFVGUGFEME-IWQZZHSRSA-N 0.000 description 1
- HNEGQIOMVPPMNR-IHWYPQMZSA-N citraconic acid Chemical compound OC(=O)C(/C)=C\C(O)=O HNEGQIOMVPPMNR-IHWYPQMZSA-N 0.000 description 1
- 229940018557 citraconic acid Drugs 0.000 description 1
- 229940096386 coconut alcohol Drugs 0.000 description 1
- 239000003240 coconut oil Substances 0.000 description 1
- 235000019864 coconut oil Nutrition 0.000 description 1
- 230000001010 compromised effect Effects 0.000 description 1
- 150000001924 cycloalkanes Chemical class 0.000 description 1
- KAOPHVRFVWFGRN-UHFFFAOYSA-M decyl(trimethyl)azanium;methyl sulfate Chemical compound COS([O-])(=O)=O.CCCCCCCCCC[N+](C)(C)C KAOPHVRFVWFGRN-UHFFFAOYSA-M 0.000 description 1
- JKWMSGQKBLHBQQ-UHFFFAOYSA-N diboron trioxide Chemical compound O=BOB=O JKWMSGQKBLHBQQ-UHFFFAOYSA-N 0.000 description 1
- 229940090960 diethylenetriamine pentamethylene phosphonic acid Drugs 0.000 description 1
- 229940079919 digestives enzyme preparation Drugs 0.000 description 1
- DDXLVDQZPFLQMZ-UHFFFAOYSA-M dodecyl(trimethyl)azanium;chloride Chemical compound [Cl-].CCCCCCCCCCCC[N+](C)(C)C DDXLVDQZPFLQMZ-UHFFFAOYSA-M 0.000 description 1
- DUYCTCQXNHFCSJ-UHFFFAOYSA-N dtpmp Chemical compound OP(=O)(O)CN(CP(O)(O)=O)CCN(CP(O)(=O)O)CCN(CP(O)(O)=O)CP(O)(O)=O DUYCTCQXNHFCSJ-UHFFFAOYSA-N 0.000 description 1
- 239000000975 dye Substances 0.000 description 1
- NFDRPXJGHKJRLJ-UHFFFAOYSA-N edtmp Chemical compound OP(O)(=O)CN(CP(O)(O)=O)CCN(CP(O)(O)=O)CP(O)(O)=O NFDRPXJGHKJRLJ-UHFFFAOYSA-N 0.000 description 1
- 125000004185 ester group Chemical group 0.000 description 1
- 150000002191 fatty alcohols Chemical class 0.000 description 1
- 239000000835 fiber Substances 0.000 description 1
- 150000004675 formic acid derivatives Chemical class 0.000 description 1
- 238000009472 formulation Methods 0.000 description 1
- 239000001530 fumaric acid Substances 0.000 description 1
- 235000011187 glycerol Nutrition 0.000 description 1
- 238000005984 hydrogenation reaction Methods 0.000 description 1
- 239000003752 hydrotrope Substances 0.000 description 1
- 150000007529 inorganic bases Chemical class 0.000 description 1
- QXJSBBXBKPUZAA-UHFFFAOYSA-N isooleic acid Natural products CCCCCCCC=CCCCCCCCCC(O)=O QXJSBBXBKPUZAA-UHFFFAOYSA-N 0.000 description 1
- 239000002655 kraft paper Substances 0.000 description 1
- VZCYOOQTPOCHFL-UPHRSURJSA-N maleic acid Chemical compound OC(=O)\C=C/C(O)=O VZCYOOQTPOCHFL-UPHRSURJSA-N 0.000 description 1
- 239000011976 maleic acid Substances 0.000 description 1
- HNEGQIOMVPPMNR-NSCUHMNNSA-N mesaconic acid Chemical compound OC(=O)C(/C)=C/C(O)=O HNEGQIOMVPPMNR-NSCUHMNNSA-N 0.000 description 1
- 108010003855 mesentericopeptidase Proteins 0.000 description 1
- LVHBHZANLOWSRM-UHFFFAOYSA-N methylenebutanedioic acid Natural products OC(=O)CC(=C)C(O)=O LVHBHZANLOWSRM-UHFFFAOYSA-N 0.000 description 1
- HNEGQIOMVPPMNR-UHFFFAOYSA-N methylfumaric acid Natural products OC(=O)C(C)=CC(O)=O HNEGQIOMVPPMNR-UHFFFAOYSA-N 0.000 description 1
- 229940043348 myristyl alcohol Drugs 0.000 description 1
- ZQPPMHVWECSIRJ-KTKRTIGZSA-N oleic acid Chemical compound CCCCCCCC\C=C/CCCCCCCC(O)=O ZQPPMHVWECSIRJ-KTKRTIGZSA-N 0.000 description 1
- 239000003605 opacifier Substances 0.000 description 1
- 150000007530 organic bases Chemical class 0.000 description 1
- 239000012074 organic phase Substances 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 125000000963 oxybis(methylene) group Chemical group [H]C([H])(*)OC([H])([H])* 0.000 description 1
- 239000003346 palm kernel oil Substances 0.000 description 1
- 235000019865 palm kernel oil Nutrition 0.000 description 1
- 239000002540 palm oil Substances 0.000 description 1
- VPOLVWCUBVJURT-UHFFFAOYSA-N pentadecasodium;pentaborate Chemical compound [Na+].[Na+].[Na+].[Na+].[Na+].[Na+].[Na+].[Na+].[Na+].[Na+].[Na+].[Na+].[Na+].[Na+].[Na+].[O-]B([O-])[O-].[O-]B([O-])[O-].[O-]B([O-])[O-].[O-]B([O-])[O-].[O-]B([O-])[O-] VPOLVWCUBVJURT-UHFFFAOYSA-N 0.000 description 1
- 229960003330 pentetic acid Drugs 0.000 description 1
- 239000002304 perfume Substances 0.000 description 1
- 239000003208 petroleum Substances 0.000 description 1
- 229940068041 phytic acid Drugs 0.000 description 1
- 239000000467 phytic acid Substances 0.000 description 1
- 159000000001 potassium salts Chemical class 0.000 description 1
- ROSDSFDQCJNGOL-UHFFFAOYSA-N protonated dimethyl amine Natural products CNC ROSDSFDQCJNGOL-UHFFFAOYSA-N 0.000 description 1
- 229920006395 saturated elastomer Polymers 0.000 description 1
- HLBBKKJFGFRGMU-UHFFFAOYSA-M sodium formate Chemical compound [Na+].[O-]C=O HLBBKKJFGFRGMU-UHFFFAOYSA-M 0.000 description 1
- 235000019254 sodium formate Nutrition 0.000 description 1
- 239000004328 sodium tetraborate Substances 0.000 description 1
- 235000010339 sodium tetraborate Nutrition 0.000 description 1
- 230000003381 solubilizing effect Effects 0.000 description 1
- 239000003381 stabilizer Substances 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 150000003467 sulfuric acid derivatives Chemical class 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- FBWNMEQMRUMQSO-UHFFFAOYSA-N tergitol NP-9 Chemical compound CCCCCCCCCC1=CC=C(OCCOCCOCCOCCOCCOCCOCCOCCOCCO)C=C1 FBWNMEQMRUMQSO-UHFFFAOYSA-N 0.000 description 1
- 108010075550 termamyl Proteins 0.000 description 1
- TUNFSRHWOTWDNC-HKGQFRNVSA-N tetradecanoic acid Chemical compound CCCCCCCCCCCCC[14C](O)=O TUNFSRHWOTWDNC-HKGQFRNVSA-N 0.000 description 1
- FAGUFWYHJQFNRV-UHFFFAOYSA-N tetraethylenepentamine Chemical group NCCNCCNCCNCCN FAGUFWYHJQFNRV-UHFFFAOYSA-N 0.000 description 1
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 1
- JZBRFIUYUGTUGG-UHFFFAOYSA-J tetrapotassium;2-[2-[bis(carboxylatomethyl)amino]ethyl-(carboxylatomethyl)amino]acetate Chemical compound [K+].[K+].[K+].[K+].[O-]C(=O)CN(CC([O-])=O)CCN(CC([O-])=O)CC([O-])=O JZBRFIUYUGTUGG-UHFFFAOYSA-J 0.000 description 1
- GTZCVFVGUGFEME-UHFFFAOYSA-N trans-aconitic acid Natural products OC(=O)CC(C(O)=O)=CC(O)=O GTZCVFVGUGFEME-UHFFFAOYSA-N 0.000 description 1
- JEVFKQIDHQGBFB-UHFFFAOYSA-K tripotassium;2-[bis(carboxylatomethyl)amino]acetate Chemical compound [K+].[K+].[K+].[O-]C(=O)CN(CC([O-])=O)CC([O-])=O JEVFKQIDHQGBFB-UHFFFAOYSA-K 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
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
- C11D3/3703—Macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
- C11D3/3715—Polyesters or polycarbonates
-
- 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
- C11D1/86—Mixtures of anionic, cationic, and 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
- C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
- C11D3/0005—Other compounding ingredients characterised by their effect
- C11D3/0036—Soil deposition preventing compositions; Antiredeposition agents
-
- 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
-
- 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
- C11D1/02—Anionic compounds
- C11D1/12—Sulfonic acids or sulfuric acid esters; Salts thereof
- C11D1/29—Sulfates of polyoxyalkylene ethers
-
- C—CHEMISTRY; METALLURGY
- C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
- C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
- C11D1/00—Detergent compositions based essentially on surface-active compounds; Use of these compounds as a detergent
- C11D1/38—Cationic compounds
- C11D1/42—Amino alcohols or amino ethers
- C11D1/44—Ethers of polyoxyalkylenes with amino alcohols; Condensation products of epoxyalkanes with amines
-
- C—CHEMISTRY; METALLURGY
- C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
- C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
- C11D1/00—Detergent compositions based essentially on surface-active compounds; Use of these compounds as a detergent
- C11D1/38—Cationic compounds
- C11D1/52—Carboxylic amides, alkylolamides or imides or their condensation products with alkylene oxides
- C11D1/521—Carboxylic amides (R1-CO-NR2R3), where R1, R2 and R3 are alkyl or alkenyl groups
-
- C—CHEMISTRY; METALLURGY
- C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
- C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
- C11D1/00—Detergent compositions based essentially on surface-active compounds; Use of these compounds as a detergent
- C11D1/38—Cationic compounds
- C11D1/52—Carboxylic amides, alkylolamides or imides or their condensation products with alkylene oxides
- C11D1/523—Carboxylic alkylolamides, or dialkylolamides, or hydroxycarboxylic amides (R1-CO-NR2R3), where R1, R2 or R3 contain one hydroxy group per alkyl group
-
- C—CHEMISTRY; METALLURGY
- C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
- C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
- C11D1/00—Detergent compositions based essentially on surface-active compounds; Use of these compounds as a detergent
- C11D1/38—Cationic compounds
- C11D1/62—Quaternary ammonium compounds
-
- C—CHEMISTRY; METALLURGY
- C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
- C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
- 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
- C11D1/66—Non-ionic compounds
- C11D1/75—Amino oxides
Definitions
- the present invention relates to heavy-duty liquid detergent compositions containing a soil release agent; anionic surfactant (preferably comprising a sulfonate surfactant and alcohol ethoxylate sulfate surfactant); ethoxylated nonionic surfactant; an optional quaternary ammonium, amine, amide, or amine oxide surfactant; preferably, saturated fatty acid and polycarboxylate builders; a neutralization system preferably comprising sodium, potassium and/or low levels of alkanolamines; and a solvent system preferably comprising ethanol, polyol and water.
- the compositions are isotropic liquids which provide a high level of detergency performance.
- liquid detergents capable of providing superior cleaning under a wide variety of laundering conditions.
- Such compositions generally require a number of ingredients which tend to separate into discrete phases.
- Isotropic liquid detergents are desired for both consistency of performance and aesthetic reasons.
- the compositions should remain isotropic during shipping and storage, where temperatures of 55°F (12.8°C) or lower are often encountered. They preferably are also formulated to recover, after freezing and thawing, to an isotropic phase prior to consumer use.
- Liquid detergents desirably contain a soil release agent to enhance performance.
- soil release agents are difficult to incorporate in liquid detergents.
- an isotropic liquid detergent with a soil release agent capable of providing superior cleaning, bleach compatibility and product stability.
- the compositions are preferably liquid detergents which additionally contain ethoxylated nonionic surfactants and polycarboxylate builders.
- the compositions have a pH of from about 6.0 to about 7.5.
- the present invention encompasses heavy-duty liquid detergent compositions comprising, by weight:
- compositions preferably contain from about 20% to about 40% of (a), (b), (c) and (d); said components being selected to provide an isotropic liquid at 55°F (12.8°C) having an initial pH of from about 7.5 to about 9, preferably from about 8.4 to about 8.8, at a concentration of about 10% by weight in water at 68°F (20°C).
- the liquid detergents of the present invention contain anionic surfactant, preferably a mixture of sulfonate and alcohol ethoxylate sulfate anionic surfactants; ethoxylated nonionic surfactant; optional quaternary ammonium, amine, amide, and/or amine oxide surfactants; builders, preferably saturated fatty acid and/or, polycarboxylate builders; a neutralization system, preferably comprising sodium, potassium and preferably low levels of aI- kanolamines; and a solvent system, preferably comprising ethanol, polyol and/or water.
- anionic surfactant preferably a mixture of sulfonate and alcohol ethoxylate sulfate anionic surfactants
- ethoxylated nonionic surfactant optional quaternary ammonium, amine, amide, and/or amine oxide surfactants
- builders preferably saturated fatty acid and/or, polycarboxylate builders
- a neutralization system
- compositions herein are formulated to provide a high level of detergency performance under a wide variety of laundering conditions.
- Preferred compositions herein are isotropic liquids at 50°F - (10°C). They preferably also recover, after freezing and thawing, to an isotropic form by 55°F (12.8°C), more preferably by 50°F (10°C).
- compositions preferably comprise a neutralization system comprising mixed potassium and sodium ions.
- Complete sodium neutralization tends to cause crystallization of the polycarboxylate builder and poor incorporation of the soil release polymer, whereas all potassium neutralization results in an unacceptably high gel point.
- the total level of organic and inorganic bases should also be selected to provide a sufficiently high product pH to minimize the level of poorly-soluble free fatty acids, without being so high that pH sensitive stain removal, enzyme stability, soil release polymer stability, and greasyioily soil removal are compromised.
- compositions also preferably have a solvent system comprising water and a mixture of ethanol and polyol.
- Polyols such as propylene glycol are especially good at solubilizing the soil release polymer. Crystallization occurs without the polyol and unacceptably high gel points tend to occur without the ethanol.
- the amount of ethanol and polyol must also be sufficient to prevent organic phase separation (i.e., keep free fatty acids and poorly soluble surfactants in solution), and yet not be so high as to cause lye phase separation and/or crystallization by limiting the amount of water available.
- the soil release component has the generic formula in which X can be any suitable capping group, with each X being selected from the group consisting of H, and alkyl or acyl groups containing from 1 to about 4 carbon atoms, preferably 1 to 2 carbon atoms, most preferably alkyl.
- n is selected for water solubility and is a range of values which generally averages from about 10 to about 50, preferably from about 10 to about 25.
- the selection of u is critical to formulation in a liquid detergent having a relatively high ionic strength. There should be very little material, preferably less than about 10 mol %, more preferably less than 5 mol %, most preferably less than 1 mol %, in which u is greater than 5. Furthermore there should be at least 20 mol %, preferably at least 40 mol %, of material in which u ranges from 3 to 5.
- the R' moieties are essentially 1,4-phenylene moieties.
- the term "the R' moieties are essentially 1,4-phenylene moieties” refers to compounds where the R' moieties consist entirely of 1,4-phenylene moieties, or are partially substituted with other arylene or alkarylene moieties, alkylene moieties, alkenylene moieties, or mixtures thereof.
- Arylene and alkarylene moieties which can be partially substituted for 1,4-phenylene include 1,3-phenylene, 1,2-phenylene, 1,8-naphthylene, 1,4-naphthylene, 2,2-biphenylene, 4,4'-biphenylene and mixtures thereof.
- Alkylene and alkenylene moieties which can be partially substituted include ethylene, 1,2-propylene, 1,4-butylene, 1,5-pentylene, 1,6-hexamethylene, 1,7-heptamethylene, 1,8-octamethylene, 1,4-cyclohexylene, and mixtures thereof.
- the degree of partial substitution with moieties other than 1,4-phenylene should be such that the soil release properties of the compound are not adversely affected to any great extent.
- the degree of partial substitution which can be tolerated will depend upon the backbone length of the compound, i.e., longer backbones can have greater partial substitution for 1,4-phenylene moieties.
- compounds where the R' comprise from about 50% to 100% 1,4-phenylene moieties (from 0 to about 50% moieties other than 1,4-phenylene) have adequate soil release activity.
- polyesters made according to the present invention with a 40:60 mole ratio of isophthalic (1,3-phenylene) to terephthalic - (1,4-phenylene) acid have adequate soil release activity.
- the R' moieties consist entirely of (i.e., comprise 100%) 1,4-phenylene moieties, i.e. each R' moiety is 1,4-phenylene.
- suitable ethylene or substituted ethylene moieties include ethylene, 1,2-propylene, 1,2-butylene, 1,2-hexylene, 3-methoxy-1,2-propylene and mixtures thereof.
- the R 2 moieties are essentially ethylene moieties, or, preferably, 1,2-propylene moieties or mixtures thereof.
- inclusion of a greater percentage of ethylene moieties tends to improve the soil release activity of the compounds, the percentage included is limited by water solubility.
- inclusion of a greater percentage of 1,2-propylene moieties tends to improve the water solubility of the compounds and consequently the ability to formulate isotropic aqueous detergent compositions without significantly harming soil release activity.
- 1,2-propylene moieties or a similar branched equivalent is extremely important for maximizing incorporation of a substantial percentage of the soil release component in the heavy duty liquid detergent compositions.
- soil release components which are soluble in cool (15°C) ethanol are also useful in compositions of the invention.
- n averages at least about 10, but a distribution of n values is present.
- the value for each n usually ranges from about 10 to about 50.
- the value for each n averages in the range of from about 10 to about 25.
- a preferred process for making the soil release component comprises the step of extracting a polymer having a typical distribution in which a substantial portion comprises a material in which u is equal to or greater than 6 with essentially anhydrous ethanol at low temperatures, e.g. from about 10°C to about 15°C, preferably less than about 13°C.
- the ethanol soluble fraction is substantially free of the longer polymers and is much easier to incorporate into isotropic heavy duty liquids. especially those with higher builder levels.
- the polymers wherein u is less than about 3 are essentially of no value in providing soil release effects, they can be more easily incorporated than higher u values.
- a more preferred process for making the soil release component is by direct synthesis.
- the anionic surfactant herein can comprise any of the synthetic anionic surfactants conventionally used in heavy duty laundry detergents including alkyl benzene sulfonates, alkyl sulfates, alkyl polyethoxylate sulfates, olefin sulfonates, paraffin sulfonates, etc. Mixtures can also be used. Suitable synthetic anionic surfactants are disclosed in detail in U.S. Patent 3,929,678, Laughlin et al, issued December 30, 1975 and incorporated herein by reference.
- Preferred synthetic anionic surfactants include .the sulfonates, the alkyl sulfates, and alkyl- polyethoxylate ether sulfates discussed more specifically below.
- the detergent compositions herein preferably contain from about 5% to about 15%, more preferably from about 6% to about 12%, by weight (on an acid basis) of an anionic sulfonate surfactant containing a C 10 -C 16 alkyl or alkenyl group.
- Anionic sulfonate surfactants useful herein are disclosed in U.S. Patent 4,285,841, Barrat et al, issued August 25, 1981, and in U.S. Patent 3,919,678, Laughlin et al, issued December 30, 1975, both incorporated herein by reference.
- Preferred sulfonate surfactants are the water-soluble salts, particularly the alkali metal, and alkanolammonium (e.g., monoethanolammonium or triethanolammonium) salts of alkylbenzene sulfonates in which the alkyl group contains from about 10 to about 15 carbon atoms, in straight chain or branched chain configuration, e.g., those of the type described in U.S. Patents 2,220,099 and 2,477,383, incorporated herein by reference.
- Especially valuable are linear straight chain alkylbenzene sulfonates in which the average number of carbon atoms in the alkyl group is from about 11 to about 13.
- water-soluble salts of paraffin sulfonates olefin sulfonates, alkyl glyceryl ether sulfonates, esters of a-sulfonated fatty acids containing from about 1 to 10 carbon atoms in the ester group.
- 2-acyloxy-alkane-1-sulfonates containing from about 2 to 9 carbon atoms in the acyl group, and B-alkyloxy alkane sulfonates containing from about 1 to 3 carbon atoms in the alkyl group.
- compositions also preferably contain an alcohol polyethoxylate ether sulfate surfactant of the formula RO(C 2 H 4 O) m SO 3 M, wherein R is a C 10 -C 16 alkyl (preferred) or hydroxyalkyl group, m is from about 0.5 to about 4, and M is a compatible cation.
- This surfactant preferably represents from about 5% to about 18%. more preferably from about 9% to about 14%, by weight (on an acid basis) of the composition.
- Preferred alcohol ethoxylate sulfate surfactants of the above formula are those wherein the R substituent is a C 12-15 alkyl group and m is from about 1.5 to about 3. Examples of such materials are C 12 - 15 alkyl polyethoxylate (225) sulfate (C 12 . 15E225S); C 14-15 E 2.25 S; C 12-13 Et 1.5 S; C 14-15 E 3 S; and mixtures thereof.
- the sodium, potassium, monoethanolammonium, and triethanolammonium salts of the above are preferred.
- compositions also preferably contain from about 2% to about 15%, more preferably from about 4% to about 12%, by weight of an ethoxylated nonionic surfactant of the formula R 1 (OC 2 H 4 )- n OH, wherein R' is a C 10 -C 16 alkyl group or a C t -C,2 alkyl phenyl group, n is from about 3 to about 9, and said nonionic surfactant has an HLB - (hydrophile-lipophile balance) of from about 10 to about 13.
- Particularly preferred are condensation products of C 12 -C 14 alcohols with from about 3 to about 8 moles of ethylene oxide per mole of alcohol, e.g., C 12 -C 13 alcohol condensed with about 6.5 moles of ethylene oxide per mole of alcohol.
- the ethoxylated nonionic surfactants herein have an HLB (hydrophilic-lipophilic balance) of from about 5 to about 17, preferably from about 6 to about 13.
- HLB hydrophilic-lipophilic balance
- Suitable ethoxylated nonionic surfactants herein are as follows:
- Preferred ethoxylated nonionic surfactants are of the formula R 1 (OC 2 H 4 ) n OH, wherein R' is a C, o -C,6 alkyl group or a C.-C, 2 alkylphenyl group, n is from about 3 to about 9, and said nonionic surfactants has an HLB (hydrophile-lipophile balance) of from about 9 to about 13, preferably from about 10 to about 13.
- HLB hydrophile-lipophile balance
- compositions herein can also contain from 0% to about 15%, preferably from about 0.5% to about 3%, by weight of a cosurfactant selected from certain quaternary ammonium, amine, amide and/or amine oxide surfactants.
- a cosurfactant selected from certain quaternary ammonium, amine, amide and/or amine oxide surfactants.
- the quaternary ammonium and amide surfactants are particularly preferred.
- R 2 is an alkyl or alkyl benzyl group having from about 6 to about 16 carbon atoms in the alkyl chain; each R is selected from the group consisting of -CH 2 CH 2 -, -CH 2 CH(CH 3 )-, -CH 2 CH(CH 2 OH)-, - CH 2 CH 2 CH 2 -, and mixtures thereof; each R' is selected from the group consisting of C 1 -C 4 alkyl, C,-C4 hydroxyalkyl, benzyl, and hydrogen when y is not 0; R S is the same as R' or is an alkyl chain wherein the total number of carbon atoms of R 2 plus R 5 is from about 8 to about 16; each y is from 0 to about 10 and the sum of the y values is from 0 to about 15; and X is any compatible anion.
- alkyl quaternary ammonium surfactants especially the mono-long chain alkyl surfactants described in the above formula when R S is selected from the same groups as R'.
- the most preferred quaternary ammonium surfactants are the chloride, bromide and methylsulfate C 8-16 alkyl trimethylammonium salts, C 8-16 alkyl di(hydroxyethyl)methylammonium salts, the C 8-16 alkyl hydroxyethyldimethylammonium salts, C 8- 16 alkyloxypropyl trimethylammonium salts, and the C 8-16 alkyloxypropyl dihdroxyethylmethylammonium salts.
- the C 10 -C 14 alkyl trimethylammonium salts are preferred, e.g., decyl trimethylammonium methylsulfate, lauryl trimethylammonium chloride, myristyl trimethylammonium bromide and coconut trimethylammonium chloride and methylsulfate.
- the C 8-10 alkyl trimethylammonium surfactants are particularly preferred since they have lower Kraft boundaries and crystallization temperatures than the longer chain quaternary ammonium surfactants.
- Amine surfactants useful herein are of the formula: wherein the R 2 , R 3 , R 4 , R 5 and y substituents are as defined above for the quaternary ammonium surfactants- Particularly preferred are the C 12 - 16 alkyl dimethyl amines.
- Amine oxide surfactants useful herein are of the formula: wherein the R 2 , R 3 , R 4 , R 5 and y substituents are also as defined above for the quaternary ammonium surfactants. Particularly preferred are the C 12 - 16 alkyl dimethyl amine oxides.
- Amine and amine oxide surfactants are preferably used at higher levels than the quaternary ammonium surfactants since they are only partially protonated in the present systems.
- preferred compositions herein can contain from about 0.5% to about 1.5% of the quaternary ammonium surfactant. or from about 1% to about 3% of the amine or amine oxide surfactants.
- Amide surfactants herein are of the formula
- R" is an alkyl, hydroxyalkyl or alkenyl radical containing from about 8 to about 20 carbon atoms
- R 7 and R 8 are selected from the group consisting of hydrogen, methyl, ethyl, propyl, isopropyl, 2-hydroxyethyl, 2-hydroxypropyl, 3-hydroxypropyl, and said radicals additionally containing up to about 5 ethylene oxide units, provided at least one of R 7 and R 8 contains a hydroxyl group.
- Preferred amides are the C 8 -C 20 fatty acid aI- kylol amides in which each alkylol group contains from 1 to 3 carbon atoms, and additionally can contain up to about 2 ethylene oxide units.
- compositions of the present invention preferably contain from 0% to about 20%, more preferably from about 8% to about 18%, most preferably from about 10% to about 16%, by weight of a saturated fatty acid containing from about 10 to about 14 carbon atoms.
- weight ratio of C 10 -C 12 fatty acid to C,, fatty acid is preferably at least 1, more preferably at least 1.5.
- Suitable saturated fatty acids can be obtained from natural sources such as plant or animal esters (e.g., palm kernel oil, palm oil and coconut oil) or synthetically prepared (e.g., via the oxidation of petroleum or by hydrogenation of carbon monoxide via the Fisher-Tropsch process).
- suitable saturated fatty acids for use in the compositions of this invention include capric, lauric, myristic, coconut and palm kernel fatty acid.
- Preferred are saturated coconut fatty acids, from about 5:1 to 1:1 (preferably about 3:1) weight ratio mixtures of lauric and myristic acid, mixtures of the above with minor amounts (e.g., 10%-50% of total fatty acid) of oleic acid; and palm kernel fatty acid.
- compositions herein also preferably contain from about 3% to about 20%, more preferably from about 3% to about 6%, more preferably from about 3.5% to about 5% by weight on an acid basis, of a water-soluble polycarboxylate detergent builder material.
- Polycarboxylate builders are described in U.S. Patent 4,284,532, Leikhim et al, issued August 18, 1981, incorporated herein by reference.
- aminopolycarboxylates cycloalkane polycarboxylates, ether polycarboxylates, alkyl polycarboxylates, epoxy polycarboxylates, tetrahydrofuran polycarboxylates, benzene polycarboxylates, and polyacetal polycarboxylates are suitable for use herein.
- polycarboxylate builders are sodium and potassium ethylenediaminetetraacetate; sodium and potassium nitrilotriacetate; the water-soluble salts of phytic acid, e.g., sodium and potassium phytates, disclosed in U.S. Patent 1,739.942, Eckey, issued March 27, 1956, incorporated herein by reference; the polycarboxylate materials described in U.S. Patent 3,364,103, incorporated herein by reference; and the water-soluble salts of polycarboxylate polymers and copolymers described in U.S. Patent 3,308,067, Diehl, issued March 7, 1967, incorporated herein by reference.
- Useful detergent builders also include the water-soluble salts of polymeric aliphatic polycarboxylic acids having the following structural and physical characteristics: (a) a minimum molecular weight of about 350 calculated as to the acid form; (b) an equivalent weight of about 50 to about 80 calculated as to acid form; (3) at least 45 mole percent of the monomeric species having at least two carboxyl radicals separated from each other by not more than two carbon atoms; (d) the site of attachment of the polymer chain of any carboxyl- containing radical being separated by not more than three carbon atoms along the polymer chain from the site of attachment of the next carboxyl- containing radical.
- Specific examples of such builders are the polymers and copolymers of itaconic acid, aconitic acid, maleic acid, mesaconic acid, fumaric acid, methylene malonic acid, and citraconic acid.
- Suitable polycarboxylate builders include the water-soluble salts, especially the sodium and potassium salts, of mellitic acid, citric acid, pyromellitic acid, benzene pentacarboxylic acid, oxydiacetic acid, carboxymethyloxysuccinic acid, carboxymethyloxymalonic acid, cis-cyclohex- anehexacarboxylic acid, cis-cyclopentanetetracarboxylic acid and oxydisuccinic acid.
- water-soluble salts especially the sodium and potassium salts, of mellitic acid, citric acid, pyromellitic acid, benzene pentacarboxylic acid, oxydiacetic acid, carboxymethyloxysuccinic acid, carboxymethyloxymalonic acid, cis-cyclohex- anehexacarboxylic acid, cis-cyclopentanetetracarboxylic acid and oxydisuccinic acid.
- polycarboxylates for use herein are the polyacetal carboxylates described in U.S. Patent 4,144,226, issued March 13, 1979 to Crutchfield et al, and U.S. Patent 4,146,495, issued March 27, 1979 to Crutchfield et al, both incorporated herein by reference.
- Citric acid is a highly preferred polycarboxylate builder.
- the present compositions can contain from about 0 to about 0.04 moles, preferably from about 0.01 to about 0.035 moles, more preferably from about 0.015 to about 0.03 moles, per 100 grams of composition of an alkanolamine selected from the group consisting of monoethanolamine, diethanolamine, triethanolamine, and mixtures thereof. Low levels or none of the alkanolamines, particularly monoethanolamine, are preferred to enhance product stability, detergency performance, and odor. The amount of alkanolamine should be minimized for best chlorine bleach compatibility and stability of the soil release component. While the present compositions can contain mixtures of the alkanolamines, best color stability is obtained using single alkanolamines.
- the solvent system for the compositions is preferably comprised of ethanol, a polyol, e.g., propanediol, and water.
- Ethanol is preferably present at a level of from about 2% to about 10%, more preferably from about 5% to about 9%, by weight of the composition.
- Any polyol containing from 2 to 6 carbon atoms and from 2 to 6 hydroxy groups can be used in the present compositions.
- examples of such polyols are ethylene glycol, propanediol, propylene glycol and glycerine. Propylene glycol is particularly preferred.
- the polyol preferably represents from about 2% to about 15%, more preferably from about 3% to about 10%, by weight of the composition.
- compositions also preferably contain from about 25% to about 40%, more preferably from about 28% to about 37%, by weight of water.
- the ethanol and polyol together preferably represent from about 8% to about 20%, more preferably about 11 % to about 16%, by weight of the composition.
- the ethanol, polyol and water preferably total from about 35% to about 55%, more preferably about 40% to about 50%, by weight of the composition.
- compositions of the present invention preferably have the following limits, in which all percentages and ratios are calculated on an acid basis where anionic materials are involved.
- the sulfonate, alcohol ethoxylate sulfate, ethoxylated non- ionic and quaternary ammonium, amine, amide and/or amine oxide surfactants, together, preferably represent from about 20% to about 40%, more preferably from about 23% to about 30%, by weight of the composition.
- the fatty acid and polycarboxylate builder together preferably represent from about 5% to about 30%, more preferably from about 10% to about 25%, by weight of the composition.
- the fatty acid, polycarboxylate builder and above surfactants preferably represent. a total of from about 33% to about 50%, more preferably from about 36% to about 48%, by weight of the composition.
- all of the above components are selected to provide an isotropic liquid detergent at 55°F (12.8°C), preferably at 50°F (10°C).
- the components are also selected to provide an initial pH of from about 7.5 to about 9.0, preferably from about 7.8 to about 8.8, at a concentration of 10% by weight in water at 68°F (20°C).
- Optional components for use in the liquid detergents herein include enzymes, enzyme stabilizing agents. polyacids, soil removal agents, anti-redeposition agents suds regulants, hydrotropes, opacifiers, antioxidants, bactericides, dyes, perfumes, and brighteners described in the U.S. Patent 4,285,841, Barrat et al, issued August 25, 1981, incorporated herein by reference.
- Such optional components generally represent less than about 15%, preferably from about 2% to about 10%, by weight of the composition.
- Enzymes are highly preferred optional ingredients and are incorporated in an amount of from about 0.025% to about 2%, preferably from about 0.05% to about 1.5%.
- Preferred proteolytic enzymes should provide a proteolytic activity of at least about 5 Anson units (about 1,000,000 Delft units) per liter, preferably from about 15 to about 70 Anson units per liter, most preferably from about 20 to about 40 Anson units per liter.
- a proteolytic activity of from about 0.01 to about 0.05 Anson units per gram of product is desirable.
- Other enzymes, including amylolytic enzymes are also desirably included in the present compositions.
- Suitable proteolytic enzymes include the many species known to be adapted for use in detergent compositions. Commercial enzyme preparations such as “Alcalase” sold by Novo Industries, and “Maxatase” sold by Gist-Brocades, Delft, The Netherlands, are suitable. Other preferred enzyme compositions include those commercially available under the tradenames SP-72 (“Esperase”) manufactured and sold by Novo Industries, A/S, Copenhagen, Denmark and "AZ-Protease” manufactured and sold by Gist-Brocades, Delft, The Netherlands.
- Suitable amylases include “Rapidase” sold by Gist-Brocades and “Termamyl” sold by Novo Industries.
- enzymes When enzymes are incorporated in the detergent compositions of this invention, they are desirably stabilized by using a mixture of a short chain carboxylic acid salt and calcium ion, such as disclosed in U.S. Patent 4.318.818, Letton et al, issued March 9, 1982. incorporated herein by reference.
- the short chain carboxylic acid salt is preferably water-soluble, and most preferably is a formate, e.g., sodium formate.
- the short chain carboxylic acid salt is used at a level from about 0.25% to about 10%, preferably from about 0.3% to about 3%, more preferably from about 0.5% to about 1.5%.
- Any water-soluble calcium salt can be used as a source of calcium ion, including calcium acetate, calcium formate and calcium propionate.
- the composition should contain from about 0.1 to about 30 millimoles of calcium ion per liter, preferably from about 0.5 to about 15 millimoles of calcium ion per liter. When materials are present which complex calcium ion, it is necessary to use high levels of calcium ion so that there is always some minimum level available for the enzyme.
- Enzymes are preferably stabilized in the present compositions by the addition of from about 025% to about 10%, preferably from about 0.5% to about 5%, more preferably from about 0.75% to about 3%, by weight of boric acid or a compound capable of forming boric acid in the composition - (calculated on the basis of the boric acid).
- Boric acid is preferred, although other compounds such as boric oxide, borax and other alkali metal borates (e.g., sodium ortho-, meta-and pyroborate, and sodium pentaborate) are suitable.
- Substituted boric acids e.g., phenylboronic acid, butane boronic acid, and p-bromo phenylboronic acid
- boric acid and formate provides improved protease stability, although amylase stability appears to be slightly less than that obtained using boric acid alone.
- Preferred compositions also contain from about 0.01% to about 1% of a polyacid or salt thereof, to enhance pretreatment performance.
- Preferred polyacids for use herein are ethylenediamine tetramethylenephosphonic acid, diethylene triamine pentamethylenephosphonic acid, and diethylenetriamine pentaacetic acid, or the salts thereof. These polyacids/salts are preferably used in an amount from about 0.1% to about 0.8%.
- compositions herein further contain from about 0.5% to about 3%, preferably from about 1% to about 2%, by weight of a highly ethoxylated polyethyleneamine or polyethyleneimine soil removal and antiredeposition agent.
- a particularly preferred species of the like soil removal and anti-redeposition agent is tetraethylenepentamine ethoxylated with about 15-18 moles of ethylene oxide at each hydrogen site.
- a liquid detergent composition of the present invention is as follows:
- a liquid detergent composition of the present invention is as follows:
Landscapes
- Chemical & Material Sciences (AREA)
- Life Sciences & Earth Sciences (AREA)
- Engineering & Computer Science (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- Wood Science & Technology (AREA)
- Organic Chemistry (AREA)
- Detergent Compositions (AREA)
Priority Applications (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
AT86200584T ATE98674T1 (de) | 1985-04-15 | 1986-04-07 | Stabile fluessige reinigungsmittel. |
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
US72312085A | 1985-04-15 | 1985-04-15 | |
US723120 | 1985-04-15 |
Publications (3)
Publication Number | Publication Date |
---|---|
EP0199403A2 true EP0199403A2 (fr) | 1986-10-29 |
EP0199403A3 EP0199403A3 (en) | 1989-07-05 |
EP0199403B1 EP0199403B1 (fr) | 1993-12-15 |
Family
ID=24904937
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
EP86200584A Expired - Lifetime EP0199403B1 (fr) | 1985-04-15 | 1986-04-07 | Compositions détergentes liquides stables |
Country Status (4)
Country | Link |
---|---|
EP (1) | EP0199403B1 (fr) |
AT (1) | ATE98674T1 (fr) |
AU (1) | AU601679B2 (fr) |
DE (1) | DE3689385T2 (fr) |
Cited By (36)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
EP0241985A2 (fr) * | 1986-04-15 | 1987-10-21 | The Procter & Gamble Company | Polyesters du type 1,2-propylène téréphtalate-polyoxyéthylène téréphtalate, coiffés, utilisés comme agents anti-salissures |
EP0629690A1 (fr) * | 1993-06-09 | 1994-12-21 | The Procter & Gamble Company | Emulsions aqueuses stables d'agents tensioactifs non-ioniques |
WO1995020640A1 (fr) * | 1994-01-31 | 1995-08-03 | Henkel Kommanditgesellschaft Auf Aktien | Melanges detergents |
WO1996016150A1 (fr) * | 1994-11-17 | 1996-05-30 | Henkel Kommanditgesellschaft Auf Aktien | Detergent anti-salissures ayant une association de tensioactifs determinee |
US5597795A (en) * | 1992-10-27 | 1997-01-28 | The Procter & Gamble Company | Detergent compositions inhibiting dye transfer |
EP0776965A2 (fr) | 1995-11-30 | 1997-06-04 | Unilever N.V. | Compositions de polymères |
WO1997044419A3 (fr) * | 1996-05-17 | 1997-12-31 | Procter & Gamble | Composition detergente |
WO1997043365A3 (fr) * | 1996-05-17 | 1998-01-08 | Procter & Gamble | Composition detersive |
US5789367A (en) * | 1995-11-30 | 1998-08-04 | Lever Brothers Company, Division Of Conopco, Inc. | Detergent compositions containing soil release polymers |
WO1998020092A3 (fr) * | 1996-11-01 | 1998-10-08 | Procter & Gamble | Compositions detergentes pour lessive a la main et contenant une combinaison d'agents tensio-actifs et de detachant avant-lavage sous forme de polymere |
CN1047619C (zh) * | 1992-10-27 | 1999-12-22 | 普罗格特-甘布尔公司 | 消除染料转移的洗涤剂组合物 |
WO2003102119A1 (fr) * | 2002-05-31 | 2003-12-11 | Akzo Nobel N.V. | Compositions de premelange de nettoyage et de degraissage a faible teneur en composes organiques volatils (voc) |
WO2011120799A1 (fr) | 2010-04-01 | 2011-10-06 | Unilever Plc | Procédé de structuration de liquides détergents à l'aide d'huile de ricin hydrogénée |
EP2476743A1 (fr) | 2011-04-04 | 2012-07-18 | Unilever Plc, A Company Registered In England And Wales under company no. 41424 of Unilever House | Procédé de lavage du linge |
WO2012104158A1 (fr) | 2011-01-31 | 2012-08-09 | Unilever Plc | Polymères antisalissures |
WO2012104156A1 (fr) | 2011-01-31 | 2012-08-09 | Unilever Plc | Polymères antisalissures |
EP2495300A1 (fr) | 2011-03-04 | 2012-09-05 | Unilever Plc, A Company Registered In England And Wales under company no. 41424 of Unilever House | Structuration de liquides détergents avec de l'huile de ricin hydrogénée |
WO2013092052A1 (fr) * | 2011-12-20 | 2013-06-27 | Unilever Plc | Détergents liquides isotropes comprenant un polymère détachant |
WO2013139702A1 (fr) | 2012-03-21 | 2013-09-26 | Unilever Plc | Particules de détergent à lessive |
WO2016155993A1 (fr) | 2015-04-02 | 2016-10-06 | Unilever Plc | Composition |
WO2017133879A1 (fr) | 2016-02-04 | 2017-08-10 | Unilever Plc | Liquide détergent |
WO2017211697A1 (fr) | 2016-06-09 | 2017-12-14 | Unilever Plc | Produits de lessive |
WO2017211700A1 (fr) | 2016-06-09 | 2017-12-14 | Unilever Plc | Produits de blanchisserie |
WO2018127390A1 (fr) | 2017-01-06 | 2018-07-12 | Unilever N.V. | Composition d'élimination de taches |
WO2018224379A1 (fr) | 2017-06-09 | 2018-12-13 | Unilever Plc | Système de distribution de lessive liquide |
WO2019038186A1 (fr) | 2017-08-24 | 2019-02-28 | Unilever Plc | Perfectionnements se rapportant au nettoyage de tissus |
WO2019038187A1 (fr) | 2017-08-24 | 2019-02-28 | Unilever Plc | Perfectionnements se rapportant au nettoyage de tissus |
US10240107B2 (en) | 2014-11-11 | 2019-03-26 | Clariant International Ltd. | Laundry detergents containing soil release polymers |
WO2019063402A1 (fr) | 2017-09-29 | 2019-04-04 | Unilever Plc | Produits de lessive |
WO2019068473A1 (fr) | 2017-10-05 | 2019-04-11 | Unilever Plc | Produits de lessive |
EP3489340A1 (fr) | 2017-11-28 | 2019-05-29 | Clariant International Ltd | Polyesters éliminant les salissures provenant d'une source renouvelable |
EP3489338A1 (fr) | 2017-11-28 | 2019-05-29 | Clariant International Ltd | Compositions détergentes contenant des polyesters antisalissures provenant de ressources renouvelables |
US10351802B2 (en) | 2014-11-11 | 2019-07-16 | Clariant International Ltd. | Laundry detergents containing soil release polymers |
WO2019224030A1 (fr) | 2018-05-24 | 2019-11-28 | Clariant International Ltd | Polyester d'élimination de salissures, à utiliser dans des compositions de détergent |
WO2021233987A1 (fr) | 2020-05-20 | 2021-11-25 | Clariant International Ltd | Polyester anti-salissures, à utiliser dans des compositions de détergent |
WO2024126303A1 (fr) | 2022-12-12 | 2024-06-20 | Clariant International Ltd | Polyesters |
Families Citing this family (18)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
IN166313B (fr) * | 1985-08-05 | 1990-04-07 | Colgate Palmolive Co | |
GB8609806D0 (en) * | 1986-04-22 | 1986-05-29 | Unilever Plc | Cleaning composition |
GB8617255D0 (en) * | 1986-07-15 | 1986-08-20 | Procter & Gamble Ltd | Laundry compositions |
GB8629936D0 (en) * | 1986-12-15 | 1987-01-28 | Procter & Gamble | Laundry compositions |
US4721580A (en) * | 1987-01-07 | 1988-01-26 | The Procter & Gamble Company | Anionic end-capped oligomeric esters as soil release agents in detergent compositions |
GB8722540D0 (en) * | 1987-09-24 | 1987-10-28 | Unilever Plc | Composition for softening fabrics |
US4976879A (en) * | 1987-10-05 | 1990-12-11 | The Procter & Gamble Company | Sulfoaroyl end-capped ester oligomers suitable as soil-release agents in detergent compositions and fabric-conditioner articles |
US4877896A (en) * | 1987-10-05 | 1989-10-31 | The Procter & Gamble Company | Sulfoaroyl end-capped ester of oligomers suitable as soil-release agents in detergent compositions and fabric-conditioner articles |
FR2636961B1 (fr) * | 1988-09-29 | 1994-09-09 | Vitalis Bernard | Composition pour le nettoyage du reseau aeraulique, des installations de ventilation mecanique controlee et des installations similaires |
US4908150A (en) * | 1989-02-02 | 1990-03-13 | Lever Brothers Company | Stabilized lipolytic enzyme-containing liquid detergent composition |
US5082585A (en) * | 1989-02-02 | 1992-01-21 | Lever Brothers Company, Division Of Conopco, Inc. | Enzymatic liquid detergent compositions containing nonionic copolymeric stabilizing agents for included lipolytic enzymes |
US5196133A (en) * | 1989-10-31 | 1993-03-23 | The Procter & Gamble Company | Granular detergent compositions containing peroxyacid bleach and sulfobenzoyl end-capped ester oligomers useful as soil-release agents |
US5182043A (en) * | 1989-10-31 | 1993-01-26 | The Procter & Gamble Company | Sulfobenzoyl end-capped ester oligomers useful as soil release agents in granular detergent compositions |
US5256168A (en) * | 1989-10-31 | 1993-10-26 | The Procter & Gamble Company | Sulfobenzoyl end-capped ester oligomers useful as soil release agents in granular detergent compositions |
DE69224376T2 (de) * | 1992-06-29 | 1998-09-03 | Procter & Gamble | Polyvinylpyrrolidon und schmutzabweisendes Polymer auf Basis von Polyterephthalate enthaltende konzentrierte wässrig-flüssige Waschmittelzusammensetzungen |
US5500153A (en) * | 1994-07-05 | 1996-03-19 | The Procter & Gamble Company | Handwash laundry detergent composition having improved mildness and cleaning performance |
CA2268672C (fr) * | 1996-10-18 | 2004-02-17 | The Procter & Gamble Company | Compositions detergentes |
US6462014B1 (en) | 2001-04-09 | 2002-10-08 | Akzo Nobel N.V. | Low foaming/defoaming compositions containing alkoxylated quaternary ammonium compounds |
Citations (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US4125370A (en) * | 1976-06-24 | 1978-11-14 | The Procter & Gamble Company | Laundry method imparting soil release properties to laundered fabrics |
EP0001305A1 (fr) * | 1977-09-23 | 1979-04-04 | THE PROCTER & GAMBLE COMPANY | Compositions détergentes contenant des agents tensioactifs anioniques et ayant des propriétés de libération des saletés |
EP0185427B1 (fr) * | 1984-12-21 | 1992-03-04 | The Procter & Gamble Company | Polyesters blocs et composés similaires utiles comme agents de détachage dans les compositions de détergent |
Family Cites Families (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US4713194A (en) * | 1986-04-15 | 1987-12-15 | The Procter & Gamble Company | Block polyester and like compounds having branched hydrophilic capping groups useful as soil release agents in detergent compositions |
-
1986
- 1986-04-07 EP EP86200584A patent/EP0199403B1/fr not_active Expired - Lifetime
- 1986-04-07 AT AT86200584T patent/ATE98674T1/de active
- 1986-04-07 DE DE3689385T patent/DE3689385T2/de not_active Expired - Fee Related
- 1986-04-15 AU AU56120/86A patent/AU601679B2/en not_active Expired - Fee Related
Patent Citations (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US4125370A (en) * | 1976-06-24 | 1978-11-14 | The Procter & Gamble Company | Laundry method imparting soil release properties to laundered fabrics |
EP0001305A1 (fr) * | 1977-09-23 | 1979-04-04 | THE PROCTER & GAMBLE COMPANY | Compositions détergentes contenant des agents tensioactifs anioniques et ayant des propriétés de libération des saletés |
EP0185427B1 (fr) * | 1984-12-21 | 1992-03-04 | The Procter & Gamble Company | Polyesters blocs et composés similaires utiles comme agents de détachage dans les compositions de détergent |
Cited By (46)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
EP0241985A3 (en) * | 1986-04-15 | 1988-07-06 | The Procter & Gamble Company | Capped 1,2-propylene terephthalate-polyoxyethylene terephthalate polyesters useful as soil release agents |
EP0241985A2 (fr) * | 1986-04-15 | 1987-10-21 | The Procter & Gamble Company | Polyesters du type 1,2-propylène téréphtalate-polyoxyéthylène téréphtalate, coiffés, utilisés comme agents anti-salissures |
US5597795A (en) * | 1992-10-27 | 1997-01-28 | The Procter & Gamble Company | Detergent compositions inhibiting dye transfer |
CN1047619C (zh) * | 1992-10-27 | 1999-12-22 | 普罗格特-甘布尔公司 | 消除染料转移的洗涤剂组合物 |
EP0629690A1 (fr) * | 1993-06-09 | 1994-12-21 | The Procter & Gamble Company | Emulsions aqueuses stables d'agents tensioactifs non-ioniques |
WO1995020640A1 (fr) * | 1994-01-31 | 1995-08-03 | Henkel Kommanditgesellschaft Auf Aktien | Melanges detergents |
WO1996016150A1 (fr) * | 1994-11-17 | 1996-05-30 | Henkel Kommanditgesellschaft Auf Aktien | Detergent anti-salissures ayant une association de tensioactifs determinee |
EP0776965A2 (fr) | 1995-11-30 | 1997-06-04 | Unilever N.V. | Compositions de polymères |
US5789367A (en) * | 1995-11-30 | 1998-08-04 | Lever Brothers Company, Division Of Conopco, Inc. | Detergent compositions containing soil release polymers |
US6136769A (en) * | 1996-05-17 | 2000-10-24 | The Procter & Gamble Company | Alkoxylated cationic detergency ingredients |
WO1997044419A3 (fr) * | 1996-05-17 | 1997-12-31 | Procter & Gamble | Composition detergente |
WO1997043365A3 (fr) * | 1996-05-17 | 1998-01-08 | Procter & Gamble | Composition detersive |
WO1998020092A3 (fr) * | 1996-11-01 | 1998-10-08 | Procter & Gamble | Compositions detergentes pour lessive a la main et contenant une combinaison d'agents tensio-actifs et de detachant avant-lavage sous forme de polymere |
WO2003102119A1 (fr) * | 2002-05-31 | 2003-12-11 | Akzo Nobel N.V. | Compositions de premelange de nettoyage et de degraissage a faible teneur en composes organiques volatils (voc) |
WO2011120799A1 (fr) | 2010-04-01 | 2011-10-06 | Unilever Plc | Procédé de structuration de liquides détergents à l'aide d'huile de ricin hydrogénée |
WO2012104158A1 (fr) | 2011-01-31 | 2012-08-09 | Unilever Plc | Polymères antisalissures |
WO2012104156A1 (fr) | 2011-01-31 | 2012-08-09 | Unilever Plc | Polymères antisalissures |
EP2495300A1 (fr) | 2011-03-04 | 2012-09-05 | Unilever Plc, A Company Registered In England And Wales under company no. 41424 of Unilever House | Structuration de liquides détergents avec de l'huile de ricin hydrogénée |
EP2476743A1 (fr) | 2011-04-04 | 2012-07-18 | Unilever Plc, A Company Registered In England And Wales under company no. 41424 of Unilever House | Procédé de lavage du linge |
WO2012136427A1 (fr) | 2011-04-04 | 2012-10-11 | Unilever Plc | Procédé de lavage d'un tissu |
AU2012358647B2 (en) * | 2011-12-20 | 2015-01-15 | Unilever Plc | Isotropic liquid detergents comprising soil release polymer |
WO2013092052A1 (fr) * | 2011-12-20 | 2013-06-27 | Unilever Plc | Détergents liquides isotropes comprenant un polymère détachant |
WO2013139702A1 (fr) | 2012-03-21 | 2013-09-26 | Unilever Plc | Particules de détergent à lessive |
US10240107B2 (en) | 2014-11-11 | 2019-03-26 | Clariant International Ltd. | Laundry detergents containing soil release polymers |
US10351802B2 (en) | 2014-11-11 | 2019-07-16 | Clariant International Ltd. | Laundry detergents containing soil release polymers |
WO2016155993A1 (fr) | 2015-04-02 | 2016-10-06 | Unilever Plc | Composition |
WO2017133879A1 (fr) | 2016-02-04 | 2017-08-10 | Unilever Plc | Liquide détergent |
WO2017211697A1 (fr) | 2016-06-09 | 2017-12-14 | Unilever Plc | Produits de lessive |
WO2017211700A1 (fr) | 2016-06-09 | 2017-12-14 | Unilever Plc | Produits de blanchisserie |
WO2018127390A1 (fr) | 2017-01-06 | 2018-07-12 | Unilever N.V. | Composition d'élimination de taches |
WO2018224379A1 (fr) | 2017-06-09 | 2018-12-13 | Unilever Plc | Système de distribution de lessive liquide |
WO2019038187A1 (fr) | 2017-08-24 | 2019-02-28 | Unilever Plc | Perfectionnements se rapportant au nettoyage de tissus |
WO2019038186A1 (fr) | 2017-08-24 | 2019-02-28 | Unilever Plc | Perfectionnements se rapportant au nettoyage de tissus |
WO2019063402A1 (fr) | 2017-09-29 | 2019-04-04 | Unilever Plc | Produits de lessive |
WO2019068473A1 (fr) | 2017-10-05 | 2019-04-11 | Unilever Plc | Produits de lessive |
DE212018000292U1 (de) | 2017-10-05 | 2020-04-15 | Unilever N.V. | Waschmittelprodukte |
EP3489338A1 (fr) | 2017-11-28 | 2019-05-29 | Clariant International Ltd | Compositions détergentes contenant des polyesters antisalissures provenant de ressources renouvelables |
WO2019105939A1 (fr) | 2017-11-28 | 2019-06-06 | Clariant International Ltd | Compositions détergentes contenant des polyesters facilitant le lavage, d'origine renouvelable |
WO2019105938A1 (fr) | 2017-11-28 | 2019-06-06 | Clariant International Ltd | Polyesters antisalissure de source renouvelable |
EP3489340A1 (fr) | 2017-11-28 | 2019-05-29 | Clariant International Ltd | Polyesters éliminant les salissures provenant d'une source renouvelable |
US20200407494A1 (en) | 2017-11-28 | 2020-12-31 | Clariant International Ltd. | Renewably Sourced Soil Release Polyesters |
US11884775B2 (en) | 2017-11-28 | 2024-01-30 | Clariant International Ltd. | Renewably sourced soil release polyesters |
WO2019224030A1 (fr) | 2018-05-24 | 2019-11-28 | Clariant International Ltd | Polyester d'élimination de salissures, à utiliser dans des compositions de détergent |
US12030984B2 (en) | 2018-05-24 | 2024-07-09 | Clariant International Ltd | Soil release polyesters for use in detergent compositions |
WO2021233987A1 (fr) | 2020-05-20 | 2021-11-25 | Clariant International Ltd | Polyester anti-salissures, à utiliser dans des compositions de détergent |
WO2024126303A1 (fr) | 2022-12-12 | 2024-06-20 | Clariant International Ltd | Polyesters |
Also Published As
Publication number | Publication date |
---|---|
DE3689385T2 (de) | 1994-05-19 |
AU601679B2 (en) | 1990-09-20 |
ATE98674T1 (de) | 1994-01-15 |
EP0199403B1 (fr) | 1993-12-15 |
AU5612086A (en) | 1986-10-23 |
DE3689385D1 (de) | 1994-01-27 |
EP0199403A3 (en) | 1989-07-05 |
Similar Documents
Publication | Publication Date | Title |
---|---|---|
EP0199403B1 (fr) | Compositions détergentes liquides stables | |
US4507219A (en) | Stable liquid detergent compositions | |
JP2968340B2 (ja) | 柔軟化性の改良された安定な洗濯用水性洗浄剤組成物 | |
US4747977A (en) | Ethanol-free liquid laundry detergent compositions | |
US4561998A (en) | Near-neutral pH detergents containing anionic surfactant, cosurfactant and fatty acid | |
JP2994039B2 (ja) | 柔軟化性の改良された安定な洗濯用水性洗浄剤組成物 | |
US5030378A (en) | Liquid detergents containing anionic surfactant, builder and proteolytic enzyme | |
CA1244362A (fr) | Detergents liquides contenant de l'acide borique destine a stabiliser les enzymes | |
EP0342177B1 (fr) | Compositions détergentes liquides renforcées, contenant des surfactants anioniques et nonioniques, des agents de renforcement et un enzyme protéolitique | |
EP0095205B1 (fr) | Compositions détergentes contenant de l'acide gras | |
WO1997016517A1 (fr) | Compositions detergentes liquides epaissies, tres aqueuses, economiques | |
JPH07116472B2 (ja) | 酵素を安定化するためにホウ酸およびホルメートを含有する液体洗剤 | |
CA2216855A1 (fr) | Compositions detergentes liquides epaissies, hautement aqueuses, economiques | |
EP0348183A2 (fr) | Produit détergents liquides contenant un enzyme | |
WO1998029526A1 (fr) | Compositions detersives liquides epaissies, fortement aqueuses, bon marche, contenant des tensioactifs aromatiques | |
CA1302924C (fr) | Detergents liquides renfermant un surfactif anionique, un adjuvant et une enzyme proteolytique | |
US4321166A (en) | Liquid detergent compositions containing corrosion inhibiting system | |
US5501820A (en) | Aqueous enzymatic detergent compositions | |
US5419853A (en) | Liquid detergents containing anionic surfactant, carboxylate builder, proteolytic enzyme, and alkanolamine | |
JPS61252300A (ja) | 陰イオン界面活性剤、エトキシ化非イオン界面活性剤およびアミド界面活性剤を含有するビルダ−入り液体洗剤 | |
EP0162033B1 (fr) | Détergents liquides contenant de l'acide borique pour la stabilisation d'enzymes | |
US5236612A (en) | Detergent compositions comprising alkyl glycerate cosurfactants | |
GB2131826A (en) | Liquid detergent composition with mixed enzyme formulation |
Legal Events
Date | Code | Title | Description |
---|---|---|---|
PUAI | Public reference made under article 153(3) epc to a published international application that has entered the european phase |
Free format text: ORIGINAL CODE: 0009012 |
|
AK | Designated contracting states |
Kind code of ref document: A2 Designated state(s): AT BE CH DE FR GB IT LI LU NL SE |
|
RBV | Designated contracting states (corrected) |
Designated state(s): AT BE CH DE FR GB IT LI LU NL |
|
PUAL | Search report despatched |
Free format text: ORIGINAL CODE: 0009013 |
|
AK | Designated contracting states |
Kind code of ref document: A3 Designated state(s): AT BE CH DE FR GB IT LI LU NL |
|
17P | Request for examination filed |
Effective date: 19891228 |
|
17Q | First examination report despatched |
Effective date: 19901102 |
|
GRAA | (expected) grant |
Free format text: ORIGINAL CODE: 0009210 |
|
AK | Designated contracting states |
Kind code of ref document: B1 Designated state(s): AT BE CH DE FR GB IT LI LU NL |
|
REF | Corresponds to: |
Ref document number: 98674 Country of ref document: AT Date of ref document: 19940115 Kind code of ref document: T |
|
ITF | It: translation for a ep patent filed | ||
REF | Corresponds to: |
Ref document number: 3689385 Country of ref document: DE Date of ref document: 19940127 |
|
ET | Fr: translation filed | ||
EPTA | Lu: last paid annual fee | ||
PLBE | No opposition filed within time limit |
Free format text: ORIGINAL CODE: 0009261 |
|
STAA | Information on the status of an ep patent application or granted ep patent |
Free format text: STATUS: NO OPPOSITION FILED WITHIN TIME LIMIT |
|
26N | No opposition filed | ||
PGFP | Annual fee paid to national office [announced via postgrant information from national office to epo] |
Ref country code: AT Payment date: 19950412 Year of fee payment: 10 |
|
PGFP | Annual fee paid to national office [announced via postgrant information from national office to epo] |
Ref country code: CH Payment date: 19950413 Year of fee payment: 10 |
|
PGFP | Annual fee paid to national office [announced via postgrant information from national office to epo] |
Ref country code: LU Payment date: 19950601 Year of fee payment: 10 |
|
PG25 | Lapsed in a contracting state [announced via postgrant information from national office to epo] |
Ref country code: LU Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES Effective date: 19960407 Ref country code: AT Effective date: 19960407 |
|
PG25 | Lapsed in a contracting state [announced via postgrant information from national office to epo] |
Ref country code: LI Effective date: 19960430 Ref country code: CH Effective date: 19960430 |
|
REG | Reference to a national code |
Ref country code: CH Ref legal event code: PL |
|
PGFP | Annual fee paid to national office [announced via postgrant information from national office to epo] |
Ref country code: BE Payment date: 20000512 Year of fee payment: 15 |
|
PG25 | Lapsed in a contracting state [announced via postgrant information from national office to epo] |
Ref country code: BE Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES Effective date: 20010430 |
|
BERE | Be: lapsed |
Owner name: THE PROCTER & GAMBLE CY Effective date: 20010430 |
|
REG | Reference to a national code |
Ref country code: GB Ref legal event code: IF02 |
|
PGFP | Annual fee paid to national office [announced via postgrant information from national office to epo] |
Ref country code: NL Payment date: 20030318 Year of fee payment: 18 |
|
PGFP | Annual fee paid to national office [announced via postgrant information from national office to epo] |
Ref country code: DE Payment date: 20030430 Year of fee payment: 18 |
|
PG25 | Lapsed in a contracting state [announced via postgrant information from national office to epo] |
Ref country code: NL Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES Effective date: 20041101 |
|
PG25 | Lapsed in a contracting state [announced via postgrant information from national office to epo] |
Ref country code: DE Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES Effective date: 20041103 |
|
NLV4 | Nl: lapsed or anulled due to non-payment of the annual fee |
Effective date: 20041101 |
|
PGFP | Annual fee paid to national office [announced via postgrant information from national office to epo] |
Ref country code: GB Payment date: 20050314 Year of fee payment: 20 |
|
PGFP | Annual fee paid to national office [announced via postgrant information from national office to epo] |
Ref country code: FR Payment date: 20050401 Year of fee payment: 20 |
|
PG25 | Lapsed in a contracting state [announced via postgrant information from national office to epo] |
Ref country code: IT Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES;WARNING: LAPSES OF ITALIAN PATENTS WITH EFFECTIVE DATE BEFORE 2007 MAY HAVE OCCURRED AT ANY TIME BEFORE 2007. THE CORRECT EFFECTIVE DATE MAY BE DIFFERENT FROM THE ONE RECORDED. Effective date: 20050407 |
|
PG25 | Lapsed in a contracting state [announced via postgrant information from national office to epo] |
Ref country code: GB Free format text: LAPSE BECAUSE OF EXPIRATION OF PROTECTION Effective date: 20060406 |
|
REG | Reference to a national code |
Ref country code: GB Ref legal event code: PE20 |