EP0297673A2 - Compositions détergentes/assouplissantes contenant des argiles d'hectorite - Google Patents
Compositions détergentes/assouplissantes contenant des argiles d'hectorite Download PDFInfo
- Publication number
- EP0297673A2 EP0297673A2 EP88201330A EP88201330A EP0297673A2 EP 0297673 A2 EP0297673 A2 EP 0297673A2 EP 88201330 A EP88201330 A EP 88201330A EP 88201330 A EP88201330 A EP 88201330A EP 0297673 A2 EP0297673 A2 EP 0297673A2
- Authority
- EP
- European Patent Office
- Prior art keywords
- alkyl
- detergent composition
- clay
- composition according
- detergent
- 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 72
- 239000003599 detergent Substances 0.000 title claims abstract description 67
- KWLMIXQRALPRBC-UHFFFAOYSA-L hectorite Chemical compound [Li+].[OH-].[OH-].[Na+].[Mg+2].O1[Si]2([O-])O[Si]1([O-])O[Si]([O-])(O1)O[Si]1([O-])O2 KWLMIXQRALPRBC-UHFFFAOYSA-L 0.000 title claims abstract description 19
- 229910000271 hectorite Inorganic materials 0.000 title claims abstract description 19
- 239000004927 clay Substances 0.000 claims abstract description 43
- 239000004615 ingredient Substances 0.000 claims abstract description 18
- 125000000217 alkyl group Chemical group 0.000 claims description 19
- -1 phosphate ester Chemical class 0.000 claims description 16
- 150000001412 amines Chemical class 0.000 claims description 15
- 239000004094 surface-active agent Substances 0.000 claims description 12
- 235000014113 dietary fatty acids Nutrition 0.000 claims description 8
- 239000000194 fatty acid Substances 0.000 claims description 8
- 229930195729 fatty acid Natural products 0.000 claims description 8
- 150000001408 amides Chemical class 0.000 claims description 7
- 125000004432 carbon atom Chemical group C* 0.000 claims description 7
- 150000004665 fatty acids Chemical class 0.000 claims description 7
- 125000003342 alkenyl group Chemical group 0.000 claims description 6
- 229910019142 PO4 Inorganic materials 0.000 claims description 5
- 125000002877 alkyl aryl group Chemical group 0.000 claims description 5
- 125000003118 aryl group Chemical group 0.000 claims description 5
- 229910052739 hydrogen Inorganic materials 0.000 claims description 5
- 239000001257 hydrogen Substances 0.000 claims description 5
- 229920000742 Cotton Polymers 0.000 claims description 4
- 150000001768 cations Chemical class 0.000 claims description 4
- 229910021645 metal ion Inorganic materials 0.000 claims description 4
- 239000010452 phosphate Substances 0.000 claims description 4
- 125000004435 hydrogen atom Chemical class [H]* 0.000 claims description 3
- MTNDZQHUAFNZQY-UHFFFAOYSA-N imidazoline Chemical compound C1CN=CN1 MTNDZQHUAFNZQY-UHFFFAOYSA-N 0.000 claims description 3
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims description 3
- 125000003837 (C1-C20) alkyl group Chemical group 0.000 claims description 2
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 2
- 125000003368 amide group Chemical group 0.000 claims description 2
- CMFFZBGFNICZIS-UHFFFAOYSA-N butanedioic acid;2,3-dihydroxybutanedioic acid Chemical compound OC(=O)CCC(O)=O.OC(=O)CCC(O)=O.OC(=O)C(O)C(O)C(O)=O CMFFZBGFNICZIS-UHFFFAOYSA-N 0.000 claims description 2
- HXDRSFFFXJISME-UHFFFAOYSA-N butanedioic acid;2,3-dihydroxybutanedioic acid Chemical compound OC(=O)CCC(O)=O.OC(=O)C(O)C(O)C(O)=O HXDRSFFFXJISME-UHFFFAOYSA-N 0.000 claims description 2
- 239000002131 composite material Substances 0.000 claims description 2
- 125000000896 monocarboxylic acid group Chemical group 0.000 claims 1
- 239000004744 fabric Substances 0.000 abstract description 18
- 230000008021 deposition Effects 0.000 abstract description 7
- 239000007844 bleaching agent Substances 0.000 description 14
- 239000000463 material Substances 0.000 description 12
- 239000002245 particle Substances 0.000 description 12
- 150000004965 peroxy acids Chemical class 0.000 description 9
- 238000000034 method Methods 0.000 description 7
- 238000012360 testing method Methods 0.000 description 7
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 description 6
- 239000012190 activator Substances 0.000 description 6
- 238000004140 cleaning Methods 0.000 description 6
- 239000008187 granular material Substances 0.000 description 5
- 239000007788 liquid Substances 0.000 description 5
- 229910052708 sodium Inorganic materials 0.000 description 4
- 239000011734 sodium Substances 0.000 description 4
- 102000004190 Enzymes Human genes 0.000 description 3
- 108090000790 Enzymes Proteins 0.000 description 3
- 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 3
- 150000004996 alkyl benzenes Chemical class 0.000 description 3
- 125000000129 anionic group Chemical group 0.000 description 3
- 150000001875 compounds Chemical class 0.000 description 3
- 229940088598 enzyme Drugs 0.000 description 3
- NLYAJNPCOHFWQQ-UHFFFAOYSA-N kaolin Chemical compound O.O.O=[Al]O[Si](=O)O[Si](=O)O[Al]=O NLYAJNPCOHFWQQ-UHFFFAOYSA-N 0.000 description 3
- 235000021317 phosphate Nutrition 0.000 description 3
- 229910052700 potassium Inorganic materials 0.000 description 3
- 239000000843 powder Substances 0.000 description 3
- 150000003856 quaternary ammonium compounds Chemical class 0.000 description 3
- 239000003352 sequestering agent Substances 0.000 description 3
- 229910021647 smectite Inorganic materials 0.000 description 3
- 239000002689 soil Substances 0.000 description 3
- 239000000758 substrate Substances 0.000 description 3
- 239000010457 zeolite Substances 0.000 description 3
- DLFVBJFMPXGRIB-UHFFFAOYSA-N Acetamide Chemical compound CC(N)=O DLFVBJFMPXGRIB-UHFFFAOYSA-N 0.000 description 2
- 239000004382 Amylase Substances 0.000 description 2
- 102000013142 Amylases Human genes 0.000 description 2
- 108010065511 Amylases Proteins 0.000 description 2
- KXDAEFPNCMNJSK-UHFFFAOYSA-N Benzamide Chemical compound NC(=O)C1=CC=CC=C1 KXDAEFPNCMNJSK-UHFFFAOYSA-N 0.000 description 2
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 description 2
- BAVYZALUXZFZLV-UHFFFAOYSA-N Methylamine Chemical compound NC BAVYZALUXZFZLV-UHFFFAOYSA-N 0.000 description 2
- 108091005804 Peptidases Proteins 0.000 description 2
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 2
- 102100037486 Reverse transcriptase/ribonuclease H Human genes 0.000 description 2
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 2
- 229910021536 Zeolite Inorganic materials 0.000 description 2
- 239000002253 acid Substances 0.000 description 2
- 150000001298 alcohols Chemical class 0.000 description 2
- 150000008051 alkyl sulfates Chemical class 0.000 description 2
- 235000019418 amylase Nutrition 0.000 description 2
- 150000004649 carbonic acid derivatives Chemical class 0.000 description 2
- 238000005341 cation exchange Methods 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- GUJOJGAPFQRJSV-UHFFFAOYSA-N dialuminum;dioxosilane;oxygen(2-);hydrate Chemical compound O.[O-2].[O-2].[O-2].[Al+3].[Al+3].O=[Si]=O.O=[Si]=O.O=[Si]=O.O=[Si]=O GUJOJGAPFQRJSV-UHFFFAOYSA-N 0.000 description 2
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 description 2
- 238000011156 evaluation Methods 0.000 description 2
- 238000011065 in-situ storage Methods 0.000 description 2
- 238000004900 laundering Methods 0.000 description 2
- 150000004682 monohydrates Chemical class 0.000 description 2
- 239000002736 nonionic surfactant Substances 0.000 description 2
- 239000012188 paraffin wax Substances 0.000 description 2
- 239000011591 potassium Substances 0.000 description 2
- 239000000344 soap Substances 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 150000003871 sulfonates Chemical class 0.000 description 2
- 230000008961 swelling Effects 0.000 description 2
- 239000003760 tallow Substances 0.000 description 2
- 239000000080 wetting agent Substances 0.000 description 2
- QLAJNZSPVITUCQ-UHFFFAOYSA-N 1,3,2-dioxathietane 2,2-dioxide Chemical compound O=S1(=O)OCO1 QLAJNZSPVITUCQ-UHFFFAOYSA-N 0.000 description 1
- NLXLAEXVIDQMFP-UHFFFAOYSA-N Ammonium chloride Substances [NH4+].[Cl-] NLXLAEXVIDQMFP-UHFFFAOYSA-N 0.000 description 1
- 108010059892 Cellulase Proteins 0.000 description 1
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 1
- 235000013162 Cocos nucifera Nutrition 0.000 description 1
- 244000060011 Cocos nucifera Species 0.000 description 1
- KCXVZYZYPLLWCC-UHFFFAOYSA-N EDTA Chemical compound OC(=O)CN(CC(O)=O)CCN(CC(O)=O)CC(O)=O KCXVZYZYPLLWCC-UHFFFAOYSA-N 0.000 description 1
- IAYPIBMASNFSPL-UHFFFAOYSA-N Ethylene oxide Chemical group C1CO1 IAYPIBMASNFSPL-UHFFFAOYSA-N 0.000 description 1
- 239000004365 Protease Substances 0.000 description 1
- BGRWYDHXPHLNKA-UHFFFAOYSA-N Tetraacetylethylenediamine Chemical compound CC(=O)N(C(C)=O)CCN(C(C)=O)C(C)=O BGRWYDHXPHLNKA-UHFFFAOYSA-N 0.000 description 1
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 description 1
- 229910052783 alkali metal Inorganic materials 0.000 description 1
- 150000004973 alkali metal peroxides Chemical class 0.000 description 1
- 150000001340 alkali metals Chemical class 0.000 description 1
- 229910052784 alkaline earth metal Inorganic materials 0.000 description 1
- 150000005215 alkyl ethers Chemical group 0.000 description 1
- 125000005211 alkyl trimethyl ammonium group Chemical group 0.000 description 1
- 235000019270 ammonium chloride Nutrition 0.000 description 1
- 239000002280 amphoteric surfactant Substances 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 239000003945 anionic surfactant Substances 0.000 description 1
- 150000001450 anions Chemical class 0.000 description 1
- 230000000844 anti-bacterial effect Effects 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 239000003899 bactericide agent Substances 0.000 description 1
- SVPXDRXYRYOSEX-UHFFFAOYSA-N bentoquatam Chemical compound O.O=[Si]=O.O=[Al]O[Al]=O SVPXDRXYRYOSEX-UHFFFAOYSA-N 0.000 description 1
- 229910052791 calcium Inorganic materials 0.000 description 1
- 229910000019 calcium carbonate Inorganic materials 0.000 description 1
- 235000010216 calcium carbonate Nutrition 0.000 description 1
- 239000004202 carbamide Substances 0.000 description 1
- 125000002915 carbonyl group Chemical group [*:2]C([*:1])=O 0.000 description 1
- 239000003093 cationic surfactant Substances 0.000 description 1
- 238000012512 characterization method Methods 0.000 description 1
- 150000001860 citric acid derivatives Chemical class 0.000 description 1
- 235000011180 diphosphates Nutrition 0.000 description 1
- 238000007580 dry-mixing Methods 0.000 description 1
- 239000000975 dye Substances 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 150000002148 esters Chemical class 0.000 description 1
- RTZKZFJDLAIYFH-UHFFFAOYSA-N ether Substances CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 1
- 229940071106 ethylenediaminetetraacetate Drugs 0.000 description 1
- 239000002979 fabric softener Substances 0.000 description 1
- 125000005842 heteroatom Chemical group 0.000 description 1
- 125000001183 hydrocarbyl group Chemical group 0.000 description 1
- 239000003752 hydrotrope Substances 0.000 description 1
- 125000002768 hydroxyalkyl group Chemical group 0.000 description 1
- 150000002460 imidazoles Chemical class 0.000 description 1
- 150000002462 imidazolines Chemical class 0.000 description 1
- 150000003949 imides Chemical class 0.000 description 1
- 238000010348 incorporation Methods 0.000 description 1
- 239000010423 industrial mineral Substances 0.000 description 1
- 229910052749 magnesium Inorganic materials 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- LUVMRKKWOQTAQD-UHFFFAOYSA-N n-acetyl-n-[6-(diacetylamino)hexyl]acetamide Chemical compound CC(=O)N(C(C)=O)CCCCCCN(C(C)=O)C(C)=O LUVMRKKWOQTAQD-UHFFFAOYSA-N 0.000 description 1
- MGFYIUFZLHCRTH-UHFFFAOYSA-N nitrilotriacetic acid Chemical class OC(=O)CN(CC(O)=O)CC(O)=O MGFYIUFZLHCRTH-UHFFFAOYSA-N 0.000 description 1
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 description 1
- 230000003287 optical effect Effects 0.000 description 1
- 150000007524 organic acids Chemical class 0.000 description 1
- 235000005985 organic acids Nutrition 0.000 description 1
- 150000001451 organic peroxides Chemical class 0.000 description 1
- 150000002923 oximes Chemical class 0.000 description 1
- 239000002304 perfume Substances 0.000 description 1
- 125000005342 perphosphate group Chemical group 0.000 description 1
- HPAFOABSQZMTHE-UHFFFAOYSA-N phenyl-(2,4,6-trimethylphenyl)methanone Chemical compound CC1=CC(C)=CC(C)=C1C(=O)C1=CC=CC=C1 HPAFOABSQZMTHE-UHFFFAOYSA-N 0.000 description 1
- 150000003013 phosphoric acid derivatives Chemical class 0.000 description 1
- 150000003014 phosphoric acid esters Chemical class 0.000 description 1
- 229920005646 polycarboxylate Polymers 0.000 description 1
- 239000003755 preservative agent Substances 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 150000004760 silicates Chemical class 0.000 description 1
- 239000002002 slurry Substances 0.000 description 1
- YQURWNNQBFEBDN-UHFFFAOYSA-M sodium 2-[(14,15-dimethyl-1-bicyclo[9.2.2]pentadeca-11(15),12-dienyl)oxy]benzenesulfonate Chemical compound C12=C(C(C(C=C1)(CCCCCCCCC2)OC1=C(C=CC=C1)S(=O)(=O)[O-])C)C.[Na+] YQURWNNQBFEBDN-UHFFFAOYSA-M 0.000 description 1
- GSYPNDDXWAZDJB-MERQFXBCSA-M sodium 4-[(3R)-3,5,5-trimethylhexanoyl]oxybenzenesulfonate Chemical compound [Na+].C[C@@H](CC(=O)Oc1ccc(cc1)S([O-])(=O)=O)CC(C)(C)C GSYPNDDXWAZDJB-MERQFXBCSA-M 0.000 description 1
- 229910000029 sodium carbonate Inorganic materials 0.000 description 1
- FQENQNTWSFEDLI-UHFFFAOYSA-J sodium diphosphate Chemical compound [Na+].[Na+].[Na+].[Na+].[O-]P([O-])(=O)OP([O-])([O-])=O FQENQNTWSFEDLI-UHFFFAOYSA-J 0.000 description 1
- 229960001922 sodium perborate Drugs 0.000 description 1
- 229940048086 sodium pyrophosphate Drugs 0.000 description 1
- 235000019832 sodium triphosphate Nutrition 0.000 description 1
- GKQFKSWGDUTIRB-UHFFFAOYSA-M sodium;4-(2-chlorooctanoyloxy)benzenesulfonate Chemical compound [Na+].CCCCCCC(Cl)C(=O)OC1=CC=C(S([O-])(=O)=O)C=C1 GKQFKSWGDUTIRB-UHFFFAOYSA-M 0.000 description 1
- YKLJGMBLPUQQOI-UHFFFAOYSA-M sodium;oxidooxy(oxo)borane Chemical compound [Na+].[O-]OB=O YKLJGMBLPUQQOI-UHFFFAOYSA-M 0.000 description 1
- 239000007921 spray Substances 0.000 description 1
- 238000001694 spray drying Methods 0.000 description 1
- 238000005507 spraying Methods 0.000 description 1
- 239000003381 stabilizer Substances 0.000 description 1
- 229910052712 strontium Inorganic materials 0.000 description 1
- 125000005017 substituted alkenyl group Chemical group 0.000 description 1
- 239000000375 suspending agent Substances 0.000 description 1
- 238000010998 test method Methods 0.000 description 1
- 150000004685 tetrahydrates Chemical class 0.000 description 1
- 235000019818 tetrasodium diphosphate Nutrition 0.000 description 1
- 239000001577 tetrasodium phosphonato phosphate Substances 0.000 description 1
- MSLRPWGRFCKNIZ-UHFFFAOYSA-J tetrasodium;hydrogen peroxide;dicarbonate Chemical compound [Na+].[Na+].[Na+].[Na+].OO.OO.OO.[O-]C([O-])=O.[O-]C([O-])=O MSLRPWGRFCKNIZ-UHFFFAOYSA-J 0.000 description 1
- 239000004753 textile Substances 0.000 description 1
- GSEJCLTVZPLZKY-UHFFFAOYSA-O triethanolammonium Chemical class OCC[NH+](CCO)CCO GSEJCLTVZPLZKY-UHFFFAOYSA-O 0.000 description 1
- GETQZCLCWQTVFV-UHFFFAOYSA-N trimethylamine Chemical compound CN(C)C GETQZCLCWQTVFV-UHFFFAOYSA-N 0.000 description 1
- UNXRWKVEANCORM-UHFFFAOYSA-I triphosphate(5-) Chemical compound [O-]P([O-])(=O)OP([O-])(=O)OP([O-])([O-])=O UNXRWKVEANCORM-UHFFFAOYSA-I 0.000 description 1
- AQLJVWUFPCUVLO-UHFFFAOYSA-N urea hydrogen peroxide Chemical compound OO.NC(N)=O AQLJVWUFPCUVLO-UHFFFAOYSA-N 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
- 239000002888 zwitterionic surfactant Substances 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
-
- 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
- C11D3/001—Softening 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
- C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
- C11D3/02—Inorganic compounds ; Elemental compounds
- C11D3/12—Water-insoluble compounds
- C11D3/124—Silicon containing, e.g. silica, silex, quartz or glass beads
- C11D3/1246—Silicates, e.g. diatomaceous earth
- C11D3/1253—Layer silicates, e.g. talcum, kaolin, clay, bentonite, smectite, montmorillonite, hectorite or attapulgite
Definitions
- the present invention relates to detergent compositions. More specifically it relates to detergent compositions containing a fabric-softening amount of a hectorite clay, the clay being in the form of particles having a narrowly-defined layer charge distribution.
- British Patent 1 400 898 discloses detergent compositons comprising, as a fabric-softening ingredient, a smectite-type clay. Any smectite-type clay having a cation exchange capacity of at least 50 meq/100 g is taught to be suitable. Gelwhite GP and Volclay BC, both of which are sodium montmorillonite clays, are disclosed to be preferred for reasons of color and cation exchange capacity.
- an object of the present invention to provide detergent compositions comprising a fabric-softening clay from which the clay particles are more efficiently desposited onto fabrics during the laundry process. It is another object of the present invention to provide detergent compositions from which clay particles are efficiently deposited, regardless of the builder system used. It is a further object of this invention to select clay materials for use in detergent compositions that provide a signficiantly better fabric-softening performance than the clay materials used to date in commercial softeness-through-the-wash detergent compositions.
- the present invention relates to detergent compositions containing a fabric-softening amount of a fabric-softening clay.
- the amount of clay is from 1% to 25% by weight of the detergent composition.
- Said fabric-softening clay is a hectorite clay of natural origin, commonly referred to as trioctahedral smectite.
- the clay is present in the form of particles. The particles have a narrowly defined layer charge distribution, such that at least 50% of the clay has a layer charge of from 0. 23 to 0. 31.
- the detergent compositions of the present invention comprise conventional detersive surfactants, conventional detergent builders and, optionally, other conventional detergent ingredients.
- the compositions further comprise a fabric-softening amount, typically from 1% to 25% by weight of the detergent composition, of a fabric-softening clay.
- the clay which is of the smectite-type, is selected on basis of its layer charge properties.
- the value of (x + y) is the layer charge of the hectorite clay.
- the hectorite clays suitable for the detergent compositions of the present invention have a layer charge distribution such that at least 50% is in the range
- hectorite clays of natural origin having a layer charge distribution such that at least 65% is in the range of from 0. 23 to 0. 31.
- the layer charge distribution of the clay material can be determined using its swelling in the presence of cationic surfactants having specific chain lengths. This method is described in detail by Lagaly and Weiss, Zeitschrift fuer Deernaehrung und Bodentechnik, 130(1), 1971, pages 9-24, the disclosures of which are incorporated herein by reference.
- the method consists of a battery of tests, known in the detergent industry as the KES-F system of Kawabata.
- the method is described in S. Kawabata, "The Standardization and Analysis of Hand Evaluation", 2nd Ed. , Textile Mach. Soc. of Japan, Osaka, 1980, the disclosures of which are incorporated herein by reference.
- the shear hysteresis parameter 2HG5 is particularly useful in the characterization of fabric softening clays.
- Preferred herein are hectorite clays which, when incoporated in detergent compositions at 10% by weight, reduce the shear hysteresis of fabrics laundered therein by at least 32%, more preferably by at least 35%.
- the shear hysteresis parameter 2HG5 is discussed in more detail in Finnimore and Koenig, Melliand Textilberichte 67 (1986) pages 514-516, the disclosures of which are incorporated herein by reference.
- Shear hysteresis is determined on cotton terry towels, with detergent compositions containing 10% (weight) of the clay to be tested. The test is described more fully in the Examples hereinbelow.
- the hectorite clays used in the detergent compositions are further characterized by an unusually great propensity for deposition onto fabrics.
- deposition onto fabrics of the claimed hectorite clays from a detergent composition is greater than the deposition of conventional smectite-type clays or of synthetic hectorites.
- suitable hectorite clays include Bentone EW and Macaloid from NL Chemicals, NJ., and hectorites from Industrial Mineral Ventures.
- compositions of this invention will typically contain organic surface-active agents ("surfactants") to provide the usual cleaning benefits associated with the use of such materials.
- surfactants organic surface-active agents
- Detersive surfactants useful herein include well-known synthetic anionic, nonionic, amphoteric and zwitterionic surfactants. Typical of these are the alkyl benzene sulfonates, alkyl- and alkylether sulfates, paraffin sulfonates, olefin sulfonates, alkoxylated (especially ethoxylated) alcohols and alkyl phenols, amine oxides, alpha-sulfonates of fatty acids and of fatty acid esters, and the like, which are well-known from the detergency art. In general, such detersive surfactants contain an alkyl group in the C9-C18 range.
- the anionic detersive surfactants can be used in the form of their sodium, potassium or triethanolammonium salts; the nonionics generally contain from about 5 to about 17 ethylene oxide groups.
- U. S. Patent 3 995 669 the disclosures of which are incorporated herein by reference, contains detailed listings of such typical detersive surfactants.
- C11-C16 alkyl benzene sulfonates, C12-C18 paraffin-sulfonates and alkyl sulfates, and the ethoxylated alcohols and alkyl phenols are especially preferred in the compositions of the present type.
- surfactant are the water-soluble soaps, e. g. the common sodium and potassium coconut or tallow soaps well-known in the art.
- the surfactant component can comprise as little as 1% of the compositons herein, but preferably the compositions will contain 5% to 40%, preferably 10% to 30%, of surfactant.
- Mixtures of the ethoxylated nonionics with anionics such as the alkyl benzene sulfonates, alkyl sulfates and paraffin sulfonates are preferred for through-the-wash cleansing of a broad spectrum of soils and stains from fabrics.
- anionics such as the alkyl benzene sulfonates, alkyl sulfates and paraffin sulfonates
- Compositions containing 4% or less nonionic surfactant are therefore preferred.
- compositions herein can contain other ingredients which aid in their cleaning performance.
- through-the-wash detergent compositions contain a detergent builder and/or metal ion sequestrant.
- detergent builders include the nitrilotriacetates, polycarboxylates, citrates, carbonates, zeolites, water-soluble phosphates such as tri-polyphosphate and sodium ortho- and pyro-phosphates, silicates, and mixtures thereof.
- Metal ion sequestrants include all of the above, plus materials like ethylenediaminetetraacetate, the aminopolyphosphonates (DEQUEST) and a wide variety of other poly-functional organic acids and salts too numerous to mention in detail here. See U. S. Patent 3 579 454 for typical examples of the use of such materials in various cleaning compositions. In general, the builder/sequestrant will comprise about 0. 5% to 45% of the composition.
- the 1-10 micron size zeolite (e. g. zeolite A) builders disclosed in German patent 2 422 655 are especially preferred for use in low-phosphate compositions.
- Particularly suitable phosphate-free builders are ether carboxylate mixtures comprising
- Typical detergent compositions contain from 5% to 35% of this builder.
- the laundry compositions herein also preferably contain enzymes to enhance their through-the-wash cleaning performance on a variety of soils and stains.
- Amylase and protease enzymes suitable for use in detergents are well-known in the art and in commercially available liquid and granular detergents.
- Commercial detersive enzymes (preferivelyably a mixture of amylase and protease) are typically used at levels of 0. 001% to 2%, and higher, in the present compositions.
- Detergent cellulase enzymes provide both cleaning and softening benefits, particularly to cotton fabrics. These enzymes are highly desirable in the detergent compositions of this invention.
- compositions herein can contain other ingredients which aid in their cleaning performance.
- the compositions herein can advantageously contain a bleaching agent, especially a peroxyacid bleaching agent.
- peroxyacid bleaching agent encompasses both peroxyacids per se and systems which are able to yield peroxyacids in situ .
- Peroxyacids per se are meant to include the alkaline and alkaline-earth metal salts thereof.
- Peroxyacids and diperoxyacids are commonly used; examples are diperoxydodecanoic acid (DPDA) or peroxyphthalic acid.
- Systems capable of delivering peracids in situ consist of a peroxygen bleaching agent and an activator thereof.
- the peroxygen bleaching agents are those capable of yielding hydrogen peroxide in an aqueous solution; these compounds are well-known in the art, and include hydrogen peroxide, alkali-metal peroxides, organic peroxide bleaching agents such as urea peroxide, inorganic persalt bleaching agents such as alkali metal perborates, percarbonates, perphosphates, persilicates, and the like.
- sodium perborate commercially available in the form of mono- and tetra-hydrates, sodium carbonate peroxyhydrate, sodium pyrophosphate peroxyhydrate and urea peroxyhydrate.
- the liberated hydrogen peroxide reacts with a bleach activator to form the peroxyacid bleach.
- bleach activators include esters, imides, imidazoles, oximes, and carbonates.
- preferred materials include methyl o-acetoxy benzoates; sodium-p-acetoxy benzene sulfonates such as sodium 4-nonanoxyloxybenzene sulfonate; sodium-4-octanoyloxybenzene sulfonate, and sodium-4-decanoyloxybenzenesulfonate : biophenol A diacetate; tetra acetyl ethylene diamine; tetra acetyl hexamethylene diamine; tetra acetyl methylene diamine.
- peroxygen bleach activators which are disclosed in U. S. Patents 4 483 778 and 4 539 130, the disclosures of which are incorporated herein by reference, are alpha-substituted alkyl or alkenyl esters, such as sodium-4-(2-chloroctanoyloxy)benzene sulfonate, sodium 4-(3,5,5-trimethyl hexanoyloxy)benzene sulfonate.
- Suitable peroxyacids are also peroxygen bleach activators such as described in published European Patent Application No. 0 116 571, i. e.
- RXAOOH and RXAL compounds of the general type RXAOOH and RXAL, wherein R is a hydroxcarbyl group, X is a hetero-atom, A is a carbonyl bridging group and L is a leaving group, especially oxybenzenesulfonate.
- quaternary ammonium compounds of the formula R4R5R6R7N+X ⁇ , wherein R4 is alkyl having from about 8 to 20, preferably from 12-18 carbon atoms, R5 is alkyl having from l to 10 carbon atoms, and R6 and R7 are each C1 to C4 alkyl preferably methyl : X ⁇ is an anion, e. g. chloride.
- quaternary ammonium compounds include C12-C14 alkyl trimethyl ammonium chloride and cocoalkyl trimethyl ammonium methosulfate.
- the quaternary ammonium compounds can be used at levels from 0. 5% to 5%.
- the detergent compositions of the present invention may further contain, in addition to the clay material, other softening ingredients.
- Suitable examples include amines of the formula R1R2R3N, wherein R1 is C6 to C20 hydrocarbyl, R2 is C1 to C20 hydrocarbyl, and R3 is C1 to C10 hydrocarbyl or hydrogen.
- a preferred amine of this type is ditallowmethylamine.
- the softening amine is present as a complex with a fatty acid of the formula RCOOH, wherein R is a C9 to C20 alkyl or alkenyl. It is desirable that the amine/fatty acid complex be present in the form of microfine particles, having a particle size in the range of from, e. g. , 0. 1 to 20 micrometers. These amine/fatty acid complexes are disclosed more fully in European Patent Application No. 0 133 804, the disclosures of which are incorporated herein by reference. Preferred are compositions that contain from 1% to 10% of the amine.
- Suitable are also complexes of the above described amine and phosphate esters of the formula wherein R8 and R9 are C1-C20 alkyl, or ethoxylated alkyl groups of the general formula alkyl-(OCH2CH2) y , wherein the alkyl substituent is C1-C20, preferably C8-C16, and y is an integer of 1 to 15, preferably 2-10, most preferably 2-5.
- Amine/phosphate ester complexes of this type are more fully disclosed in European Patent Application No 0 168 889, the disclosures of which are incorporated herein by reference.
- optional softening ingredients include the softening amides of the formula R10R11NCOR12, wherein R10 and R11 are independently selected from C1-C22 alkyl, alkenyl, hydroxy alkyl, aryl, and alkyl-aryl groups; R12 is hydrogen, or a C1-C22 alkyl or alkenyl, an aryl or alkyl-aryl group.
- R10 and R11 are independently selected from C1-C22 alkyl, alkenyl, hydroxy alkyl, aryl, and alkyl-aryl groups
- R12 is hydrogen, or a C1-C22 alkyl or alkenyl, an aryl or alkyl-aryl group.
- Preferred examples of these amides are ditallow acetamide and ditallow benzamide. Good results are obtained when the amides are present in the composition in the form of a composite with a fatty acid or with a phosphate ester, as described hereinbefore for the soft
- the amides are present in the composition at 1%-10% by weight.
- the amine and amide softening ingredients may be added to the crutcher mix and spray-dried, or may be added as a dry powder to a detergent granule, or may be sprayed onto the detergent granule or onto a carrier, either in melted or in dissolved form.
- a suitable carrier is perborate monohydrate.
- Suitable softening ingredients are also the amines disclosed in U. K. Patent Application GB 2 173 827, the disclosures of which are incorporated herein by reference, in particular the substituted cyclic amines disclosed therein.
- Suitable are imidazolines of the general formula 1-(higher alkyl) amido (lower alkyl)-2-(higher alkyl) imidazoline wherein higher alkyl is alkyl having from 12 to 22 carbon atoms, and lower alkyl is alkyl having from 1 to 4 carbon atoms.
- Softener materials of this type are preferably added to the composition as particles or agglomerates as disclosed in U. S. Patent Application Serial Number 922 912, filed October 24, 1986 by Baker et al, the disclosures of which are incorporated herein by reference.
- a preferred cyclic amine is 1-tallowamidoethyl-2-tallow imidazoline.
- Preferred compositions contain from 1% to 10% of the substituted cyclic amine.
- compositions herein can contain, in addition to ingredients already mentioned, various other optional ingredients typically used in commercial products to provide aesthetic or additonal product performance benefits.
- Typical ingredients include pH regulants, perfumes, dyes, bleach, optical brighteners, soil suspending agents, hydrotropes and gel-control agents, freeze-thaw stabilizers, bactericides, preservatives, suds control agents, bleach activators and the like.
- compositions are typically used at a concentration of at least 500 ppm, preferably 0. 10% to 1. 5, in an aqueous laundry bath at pH 7-11 to launder fabrics.
- the laundering can be carried out over the range from 5°C to the boil, with excellent results.
- the detergent compositions of the present invention can be formulated as granular or as liquid detergents. It has been found that clays having a high swelling capacity can be easily incoporated in a liquid detergent composition, while maintaining phase stability.
- the clay material can be incorporated in a liquid detergent composition by simple mixing, preferably using a high shear mixer.
- the clay may be added, as a powder or as a slurry, to a crutcher mix of conventional detergent ingredients, mixed, and spray dried to form a detergent granule.
- the clay powder can be agglomerated to a desirable agglomerate size, and then be mixed with granules containing the other detergent ingredients.
- Clay granules for dry mixing can also be obtained by selecting a proper sieve fraction of natural agglomerates, by spraying a clay slurry onto a suitable particulate carrier, by agglomerating clay particles with sodium carbonate, by spray drying a clay slurry, etc.
- the clay particles may also be incorporated in a substrate, like a pouch or a sheet, optionally with other softening ingredients. Substrates of this kind can be added to the laundry together with a conventional laundry detergent.
- a preferred substrate is a pouch comprising the clay particles and particles of an alkyl amido alkyl-2-alkylimidazoline of the type described hereinabove.
- the commercially available material has been treated with a wetting agent.
- a wetting agent The same material without the wetting agent is equally suitable.
- Suitable is also Macaloid (NL Chemicals, NJ), also a hectorite from Hector, CA.
- Each of the compositions was used in a laundry test as follows : 3 kg wash load and desired test swatches (cotton terry towels)* were laundered in a commercial automatic drum washing machine (MIELE W 726) using one wash cycle at 60°C.
- the detergent compositions were used at 1,12% concentration in 0,308 g CaCO3/l water hardness.
- the wash loads were line-dried at 20°C/65% relative humidity.
- the test swatches then were instrumentally assessed for softness, using the Kawabata KES-F system (shear hysteresis at 5 degrees 2HG5 as best correlating parameter with softness on KES-F-1 instrument).
- the sample size was 20 x 20 cm, whereby the area of sample which is actually subjected to shear stress is 20 x 5 cm. From the curves of shear stress against shear angle the shear hysteresis was calculated at 5° (2HG5) in N/m. Each measurement was repeated 8 times to calculate the confidence interval of the mean at 95% confidence level.
- Hectorite clays of the present invention gave a shear hysteresis reduction of 40%, on average.
- liquid detergent composition is prepared.
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- 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)
- Inorganic Chemistry (AREA)
- Detergent Compositions (AREA)
- Treatments For Attaching Organic Compounds To Fibrous Goods (AREA)
- Chemical Or Physical Treatment Of Fibers (AREA)
- External Artificial Organs (AREA)
Priority Applications (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
AT88201330T ATE97691T1 (de) | 1987-06-30 | 1988-06-28 | Hektorittonhaltige waschmittel/weichsp¨lerzusammensetzungen. |
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
US6828187A | 1987-06-30 | 1987-06-30 | |
US68281 | 1987-06-30 |
Publications (3)
Publication Number | Publication Date |
---|---|
EP0297673A2 true EP0297673A2 (fr) | 1989-01-04 |
EP0297673A3 EP0297673A3 (en) | 1990-04-25 |
EP0297673B1 EP0297673B1 (fr) | 1993-11-24 |
Family
ID=22081577
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
EP88201330A Expired - Lifetime EP0297673B1 (fr) | 1987-06-30 | 1988-06-28 | Compositions détergentes/assouplissantes contenant des argiles d'hectorite |
Country Status (15)
Country | Link |
---|---|
EP (1) | EP0297673B1 (fr) |
JP (1) | JP2595052B2 (fr) |
KR (1) | KR950013916B1 (fr) |
CN (1) | CN1025870C (fr) |
AT (1) | ATE97691T1 (fr) |
AU (1) | AU624577B2 (fr) |
DE (1) | DE3885801T2 (fr) |
DK (1) | DK171868B1 (fr) |
EG (1) | EG18674A (fr) |
FI (1) | FI92495C (fr) |
IE (1) | IE61343B1 (fr) |
MX (1) | MX169171B (fr) |
MY (1) | MY103738A (fr) |
NZ (1) | NZ225217A (fr) |
TR (1) | TR24454A (fr) |
Cited By (14)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
GB2224035A (en) * | 1988-09-30 | 1990-04-25 | Unilever Plc | Detergent composition |
EP0387426A2 (fr) * | 1988-12-21 | 1990-09-19 | The Procter & Gamble Company | Composition adoucissante textile contenant une argile hectorite naturelle |
EP0401047A2 (fr) * | 1989-06-02 | 1990-12-05 | Unilever Plc | Composition détergente |
WO1992013053A2 (fr) * | 1991-01-16 | 1992-08-06 | The Procter & Gamble Company | Compositions detergentes comportant une cellulase tres active et des argiles adoucissantes |
US5209857A (en) * | 1988-07-06 | 1993-05-11 | Lever Brothers Company, Division Of Conopco, Inc. | Fabric softening detergent compositions containing smectite clays having a lattice charge deficiency |
US5443750A (en) * | 1991-01-16 | 1995-08-22 | The Procter & Gamble Company | Detergent compositions with high activity cellulase and softening clays |
EP0710712A1 (fr) * | 1994-11-05 | 1996-05-08 | The Procter & Gamble Company | Compositions de blanchiment |
EP0753567A1 (fr) * | 1995-07-14 | 1997-01-15 | The Procter & Gamble Company | Compositions adoucissantes pour le lavage simultané |
WO1997012024A1 (fr) * | 1995-09-29 | 1997-04-03 | The Procter & Gamble Company | Mousse pour le traitement de textiles |
US5981459A (en) * | 1995-09-29 | 1999-11-09 | The Procter & Gamble Company | Foam for treating textile fabrics |
WO2001085887A1 (fr) * | 2000-05-05 | 2001-11-15 | The Procter & Gamble Company | Compositions detergentes liquides |
WO2002024850A1 (fr) * | 2000-09-19 | 2002-03-28 | The Procter & Gamble Company | Compositions detergentes |
US6730656B2 (en) | 2000-09-19 | 2004-05-04 | The Procter & Gamble Company | Detergent compositions |
WO2005063958A1 (fr) * | 2003-12-26 | 2005-07-14 | Kao Corporation | Composition detergente adoucissante |
Families Citing this family (6)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
GB8900027D0 (en) | 1989-01-03 | 1989-03-01 | Procter & Gamble | Rinse-added fabric-softening compositions |
CA2004165C (fr) * | 1988-12-21 | 1997-12-16 | The Procter & Gamble Company | Composes de conditionnement de tissus |
JPH09511533A (ja) * | 1994-09-19 | 1997-11-18 | ザ、プロクター、エンド、ギャンブル、カンパニー | 顆粒状漂白組成物 |
US6150324A (en) * | 1997-01-13 | 2000-11-21 | Ecolab, Inc. | Alkaline detergent containing mixed organic and inorganic sequestrants resulting in improved soil removal |
GB2348435A (en) * | 1999-04-01 | 2000-10-04 | Procter & Gamble | Softening compositions |
CN100554398C (zh) * | 2003-12-26 | 2009-10-28 | 花王株式会社 | 柔软洗涤剂组合物 |
Citations (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
GB1376379A (en) * | 1971-05-24 | 1974-12-04 | Pfizer | Use of synthetic clays containing fluorine and lithium as soil anti-redeposition agents in detergents |
EP0011340B1 (fr) * | 1978-11-20 | 1982-11-24 | THE PROCTER & GAMBLE COMPANY | Composition détergente ayant des propriétés adoucissantes sur les textiles |
EP0225142A1 (fr) * | 1985-11-22 | 1987-06-10 | Unilever Plc | Composition détergente liquide |
Family Cites Families (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
NZ223480A (en) * | 1987-02-20 | 1990-04-26 | Colgate Palmolive Co | Solid, phosphate-free laundry softener/detergent containing diammonium softener |
GB8709057D0 (en) * | 1987-04-15 | 1987-05-20 | Unilever Plc | Composition for softening fabrics |
-
1988
- 1988-06-28 DE DE3885801T patent/DE3885801T2/de not_active Expired - Fee Related
- 1988-06-28 AT AT88201330T patent/ATE97691T1/de active
- 1988-06-28 MY MYPI88000711A patent/MY103738A/en unknown
- 1988-06-28 EP EP88201330A patent/EP0297673B1/fr not_active Expired - Lifetime
- 1988-06-29 FI FI883106A patent/FI92495C/fi not_active IP Right Cessation
- 1988-06-29 NZ NZ225217A patent/NZ225217A/en unknown
- 1988-06-29 IE IE197288A patent/IE61343B1/en unknown
- 1988-06-30 DK DK361688A patent/DK171868B1/da not_active IP Right Cessation
- 1988-06-30 CN CN88104136A patent/CN1025870C/zh not_active Expired - Fee Related
- 1988-06-30 MX MX012110A patent/MX169171B/es unknown
- 1988-06-30 JP JP63164087A patent/JP2595052B2/ja not_active Expired - Fee Related
- 1988-06-30 KR KR1019880008135A patent/KR950013916B1/ko not_active IP Right Cessation
- 1988-06-30 AU AU18585/88A patent/AU624577B2/en not_active Ceased
- 1988-06-30 TR TR88/0528A patent/TR24454A/xx unknown
- 1988-07-03 EG EG366/88A patent/EG18674A/xx active
Patent Citations (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
GB1376379A (en) * | 1971-05-24 | 1974-12-04 | Pfizer | Use of synthetic clays containing fluorine and lithium as soil anti-redeposition agents in detergents |
EP0011340B1 (fr) * | 1978-11-20 | 1982-11-24 | THE PROCTER & GAMBLE COMPANY | Composition détergente ayant des propriétés adoucissantes sur les textiles |
EP0225142A1 (fr) * | 1985-11-22 | 1987-06-10 | Unilever Plc | Composition détergente liquide |
Cited By (20)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US5209857A (en) * | 1988-07-06 | 1993-05-11 | Lever Brothers Company, Division Of Conopco, Inc. | Fabric softening detergent compositions containing smectite clays having a lattice charge deficiency |
GB2224035A (en) * | 1988-09-30 | 1990-04-25 | Unilever Plc | Detergent composition |
EP0387426A2 (fr) * | 1988-12-21 | 1990-09-19 | The Procter & Gamble Company | Composition adoucissante textile contenant une argile hectorite naturelle |
EP0387426A3 (fr) * | 1988-12-21 | 1991-11-21 | The Procter & Gamble Company | Composition adoucissante textile contenant une argile hectorite naturelle |
EP0401047A2 (fr) * | 1989-06-02 | 1990-12-05 | Unilever Plc | Composition détergente |
US5102562A (en) * | 1989-06-02 | 1992-04-07 | Lever Brothers Company, Division Of Conopco, Inc. | Process for preparing a fabric softening lithium exchanged clay |
EP0401047B1 (fr) * | 1989-06-02 | 1996-09-25 | Unilever Plc | Composition détergente |
WO1992013053A2 (fr) * | 1991-01-16 | 1992-08-06 | The Procter & Gamble Company | Compositions detergentes comportant une cellulase tres active et des argiles adoucissantes |
US5443750A (en) * | 1991-01-16 | 1995-08-22 | The Procter & Gamble Company | Detergent compositions with high activity cellulase and softening clays |
WO1992013053A3 (fr) * | 1991-01-16 | 1992-09-17 | Procter & Gamble | Compositions detergentes comportant une cellulase tres active et des argiles adoucissantes |
EP0710712A1 (fr) * | 1994-11-05 | 1996-05-08 | The Procter & Gamble Company | Compositions de blanchiment |
EP0753567A1 (fr) * | 1995-07-14 | 1997-01-15 | The Procter & Gamble Company | Compositions adoucissantes pour le lavage simultané |
WO1997012024A1 (fr) * | 1995-09-29 | 1997-04-03 | The Procter & Gamble Company | Mousse pour le traitement de textiles |
US5981459A (en) * | 1995-09-29 | 1999-11-09 | The Procter & Gamble Company | Foam for treating textile fabrics |
WO2001085887A1 (fr) * | 2000-05-05 | 2001-11-15 | The Procter & Gamble Company | Compositions detergentes liquides |
WO2002024850A1 (fr) * | 2000-09-19 | 2002-03-28 | The Procter & Gamble Company | Compositions detergentes |
US6730656B2 (en) | 2000-09-19 | 2004-05-04 | The Procter & Gamble Company | Detergent compositions |
WO2005063958A1 (fr) * | 2003-12-26 | 2005-07-14 | Kao Corporation | Composition detergente adoucissante |
AU2004309264B2 (en) * | 2003-12-26 | 2008-08-21 | Kao Corporation | Softening detergent composition |
US7928048B2 (en) * | 2003-12-26 | 2011-04-19 | Kao Corporation | Softening detergent composition |
Also Published As
Publication number | Publication date |
---|---|
EP0297673B1 (fr) | 1993-11-24 |
CN1031561A (zh) | 1989-03-08 |
IE881972L (en) | 1988-12-30 |
NZ225217A (en) | 1991-07-26 |
DK361688A (da) | 1988-12-31 |
FI92495B (fi) | 1994-08-15 |
TR24454A (tr) | 1991-10-10 |
FI883106A (fi) | 1988-12-31 |
JPS6465199A (en) | 1989-03-10 |
EG18674A (en) | 1993-10-30 |
DK171868B1 (da) | 1997-07-21 |
AU624577B2 (en) | 1992-06-18 |
DK361688D0 (da) | 1988-06-30 |
DE3885801T2 (de) | 1994-05-19 |
AU1858588A (en) | 1989-01-05 |
FI92495C (fi) | 1994-11-25 |
EP0297673A3 (en) | 1990-04-25 |
KR950013916B1 (ko) | 1995-11-18 |
JP2595052B2 (ja) | 1997-03-26 |
MY103738A (en) | 1993-09-30 |
ATE97691T1 (de) | 1993-12-15 |
KR890000652A (ko) | 1989-03-16 |
IE61343B1 (en) | 1994-11-02 |
CN1025870C (zh) | 1994-09-07 |
FI883106A0 (fi) | 1988-06-29 |
DE3885801D1 (de) | 1994-01-05 |
MX169171B (es) | 1993-06-23 |
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