EP2694635B1 - Procédé de lavage du linge - Google Patents
Procédé de lavage du linge Download PDFInfo
- Publication number
- EP2694635B1 EP2694635B1 EP12707100.9A EP12707100A EP2694635B1 EP 2694635 B1 EP2694635 B1 EP 2694635B1 EP 12707100 A EP12707100 A EP 12707100A EP 2694635 B1 EP2694635 B1 EP 2694635B1
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- EP
- European Patent Office
- Prior art keywords
- surfactant
- composition
- ppm
- acid
- wash
- 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.)
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- 229920000578 graft copolymer Polymers 0.000 description 1
- 230000002650 habitual effect Effects 0.000 description 1
- 150000004820 halides Chemical class 0.000 description 1
- 229940059442 hemicellulase Drugs 0.000 description 1
- 108010002430 hemicellulase Proteins 0.000 description 1
- 125000003187 heptyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 230000007062 hydrolysis Effects 0.000 description 1
- 238000006460 hydrolysis reaction Methods 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 description 1
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 description 1
- CBOIHMRHGLHBPB-UHFFFAOYSA-N hydroxymethyl Chemical compound O[CH2] CBOIHMRHGLHBPB-UHFFFAOYSA-N 0.000 description 1
- 150000002462 imidazolines Chemical class 0.000 description 1
- 230000001771 impaired effect Effects 0.000 description 1
- 230000005764 inhibitory process Effects 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 238000010409 ironing Methods 0.000 description 1
- SUMDYPCJJOFFON-UHFFFAOYSA-N isethionic acid Chemical class OCCS(O)(=O)=O SUMDYPCJJOFFON-UHFFFAOYSA-N 0.000 description 1
- 239000004310 lactic acid Substances 0.000 description 1
- 235000014655 lactic acid Nutrition 0.000 description 1
- 239000000787 lecithin Substances 0.000 description 1
- 229940067606 lecithin Drugs 0.000 description 1
- 235000010445 lecithin Nutrition 0.000 description 1
- 229910003002 lithium salt Inorganic materials 0.000 description 1
- 159000000002 lithium salts Chemical class 0.000 description 1
- 230000014759 maintenance of location Effects 0.000 description 1
- 150000002690 malonic acid derivatives Chemical class 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 125000001434 methanylylidene group Chemical group [H]C#[*] 0.000 description 1
- 125000000956 methoxy group Chemical group [H]C([H])([H])O* 0.000 description 1
- 125000000325 methylidene group Chemical group [H]C([H])=* 0.000 description 1
- 244000005700 microbiome Species 0.000 description 1
- 230000003278 mimic effect Effects 0.000 description 1
- 239000000178 monomer Substances 0.000 description 1
- BZDOEVMUXJTHPS-UHFFFAOYSA-N n,n-bis(2-hydroxyethyl)hexadecan-1-amine oxide Chemical compound CCCCCCCCCCCCCCCC[N+]([O-])(CCO)CCO BZDOEVMUXJTHPS-UHFFFAOYSA-N 0.000 description 1
- CBLJNXZOFGRDAC-UHFFFAOYSA-N n,n-bis(2-hydroxyethyl)octadecan-1-amine oxide Chemical compound CCCCCCCCCCCCCCCCCC[N+]([O-])(CCO)CCO CBLJNXZOFGRDAC-UHFFFAOYSA-N 0.000 description 1
- IBOBFGGLRNWLIL-UHFFFAOYSA-N n,n-dimethylhexadecan-1-amine oxide Chemical compound CCCCCCCCCCCCCCCC[N+](C)(C)[O-] IBOBFGGLRNWLIL-UHFFFAOYSA-N 0.000 description 1
- 125000004433 nitrogen atom Chemical group N* 0.000 description 1
- 229920000847 nonoxynol Polymers 0.000 description 1
- 239000003605 opacifier Substances 0.000 description 1
- 125000000962 organic group Chemical group 0.000 description 1
- 125000005702 oxyalkylene group Chemical group 0.000 description 1
- 239000003002 pH adjusting agent Substances 0.000 description 1
- 239000006179 pH buffering agent Substances 0.000 description 1
- 238000004806 packaging method and process Methods 0.000 description 1
- 238000012856 packing Methods 0.000 description 1
- 229940071144 palm kernelate Drugs 0.000 description 1
- HWGNBUXHKFFFIH-UHFFFAOYSA-I pentasodium;[oxido(phosphonatooxy)phosphoryl] phosphate Chemical compound [Na+].[Na+].[Na+].[Na+].[Na+].[O-]P([O-])(=O)OP([O-])(=O)OP([O-])([O-])=O HWGNBUXHKFFFIH-UHFFFAOYSA-I 0.000 description 1
- 150000004965 peroxy acids Chemical class 0.000 description 1
- QQBPIHBUCMDKFG-UHFFFAOYSA-N phenazopyridine hydrochloride Chemical group Cl.NC1=NC(N)=CC=C1N=NC1=CC=CC=C1 QQBPIHBUCMDKFG-UHFFFAOYSA-N 0.000 description 1
- HXITXNWTGFUOAU-UHFFFAOYSA-N phenylboronic acid Chemical class OB(O)C1=CC=CC=C1 HXITXNWTGFUOAU-UHFFFAOYSA-N 0.000 description 1
- WTJKGGKOPKCXLL-RRHRGVEJSA-N phosphatidylcholine Chemical compound CCCCCCCCCCCCCCCC(=O)OC[C@H](COP([O-])(=O)OCC[N+](C)(C)C)OC(=O)CCCCCCCC=CCCCCCCCC WTJKGGKOPKCXLL-RRHRGVEJSA-N 0.000 description 1
- UEZVMMHDMIWARA-UHFFFAOYSA-M phosphonate Chemical compound [O-]P(=O)=O UEZVMMHDMIWARA-UHFFFAOYSA-M 0.000 description 1
- 229920003023 plastic Polymers 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- 229920000233 poly(alkylene oxides) Polymers 0.000 description 1
- 239000004584 polyacrylic acid Substances 0.000 description 1
- 229920001515 polyalkylene glycol Polymers 0.000 description 1
- 229920000768 polyamine Polymers 0.000 description 1
- 229920005646 polycarboxylate Polymers 0.000 description 1
- 229920000867 polyelectrolyte Polymers 0.000 description 1
- 229920006254 polymer film Polymers 0.000 description 1
- 230000000379 polymerizing effect Effects 0.000 description 1
- 229920001451 polypropylene glycol Polymers 0.000 description 1
- 229910052700 potassium Inorganic materials 0.000 description 1
- 239000011591 potassium Substances 0.000 description 1
- 239000002243 precursor Substances 0.000 description 1
- 230000002335 preservative effect Effects 0.000 description 1
- 238000002203 pretreatment Methods 0.000 description 1
- 125000002572 propoxy group Chemical group [*]OC([H])([H])C(C([H])([H])[H])([H])[H] 0.000 description 1
- 230000005588 protonation Effects 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 150000003219 pyrazolines Chemical class 0.000 description 1
- 125000001453 quaternary ammonium group Chemical group 0.000 description 1
- 150000003254 radicals Chemical class 0.000 description 1
- KUIXZSYWBHSYCN-UHFFFAOYSA-L remazol brilliant blue r Chemical compound [Na+].[Na+].C1=C(S([O-])(=O)=O)C(N)=C2C(=O)C3=CC=CC=C3C(=O)C2=C1NC1=CC=CC(S(=O)(=O)CCOS([O-])(=O)=O)=C1 KUIXZSYWBHSYCN-UHFFFAOYSA-L 0.000 description 1
- 238000012552 review Methods 0.000 description 1
- 238000000518 rheometry Methods 0.000 description 1
- 238000005204 segregation Methods 0.000 description 1
- 239000004289 sodium hydrogen sulphite Substances 0.000 description 1
- 235000010267 sodium hydrogen sulphite Nutrition 0.000 description 1
- 229940057950 sodium laureth sulfate Drugs 0.000 description 1
- 229910052938 sodium sulfate Inorganic materials 0.000 description 1
- 235000011152 sodium sulphate Nutrition 0.000 description 1
- SZINDZNWFLBXKV-UHFFFAOYSA-M sodium;2-(2-hydroxyethoxy)ethanesulfonate Chemical group [Na+].OCCOCCS([O-])(=O)=O SZINDZNWFLBXKV-UHFFFAOYSA-M 0.000 description 1
- SXHLENDCVBIJFO-UHFFFAOYSA-M sodium;2-[2-(2-dodecoxyethoxy)ethoxy]ethyl sulfate Chemical compound [Na+].CCCCCCCCCCCCOCCOCCOCCOS([O-])(=O)=O SXHLENDCVBIJFO-UHFFFAOYSA-M 0.000 description 1
- GIPRGFRQMWSHAK-UHFFFAOYSA-M sodium;2-propan-2-ylbenzenesulfonate Chemical compound [Na+].CC(C)C1=CC=CC=C1S([O-])(=O)=O GIPRGFRQMWSHAK-UHFFFAOYSA-M 0.000 description 1
- QUCDWLYKDRVKMI-UHFFFAOYSA-M sodium;3,4-dimethylbenzenesulfonate Chemical compound [Na+].CC1=CC=C(S([O-])(=O)=O)C=C1C QUCDWLYKDRVKMI-UHFFFAOYSA-M 0.000 description 1
- MWNQXXOSWHCCOZ-UHFFFAOYSA-L sodium;oxido carbonate Chemical compound [Na+].[O-]OC([O-])=O MWNQXXOSWHCCOZ-UHFFFAOYSA-L 0.000 description 1
- 239000011343 solid material Substances 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 239000000992 solvent dye Substances 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 125000001424 substituent group Chemical group 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 150000003900 succinic acid esters Chemical class 0.000 description 1
- 150000005846 sugar alcohols Chemical class 0.000 description 1
- 239000001117 sulphuric acid Substances 0.000 description 1
- 235000011149 sulphuric acid Nutrition 0.000 description 1
- 230000000475 sunscreen effect Effects 0.000 description 1
- 239000000516 sunscreening agent Substances 0.000 description 1
- 108010075550 termamyl Proteins 0.000 description 1
- 239000004753 textile Substances 0.000 description 1
- 238000012546 transfer Methods 0.000 description 1
- 230000009466 transformation Effects 0.000 description 1
- 229910052723 transition metal Inorganic materials 0.000 description 1
- 150000003624 transition metals Chemical group 0.000 description 1
- 150000003852 triazoles Chemical class 0.000 description 1
- 150000004961 triphenylmethanes Chemical class 0.000 description 1
- 230000007306 turnover Effects 0.000 description 1
- 235000013311 vegetables Nutrition 0.000 description 1
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 1
- 239000004034 viscosity adjusting agent Substances 0.000 description 1
- 229940071104 xylenesulfonate Drugs 0.000 description 1
- 229910052725 zinc Inorganic materials 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
- C11D3/3723—Polyamines or polyalkyleneimines
-
- 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
- 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
- C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
- C11D3/16—Organic compounds
- C11D3/38—Products with no well-defined composition, e.g. natural products
- C11D3/386—Preparations containing enzymes, e.g. protease or amylase
-
- 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
- C11D3/38—Products with no well-defined composition, e.g. natural products
- C11D3/386—Preparations containing enzymes, e.g. protease or amylase
- C11D3/38645—Preparations containing enzymes, e.g. protease or amylase containing cellulase
-
- 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
- C11D2111/00—Cleaning compositions characterised by the objects to be cleaned; Cleaning compositions characterised by non-standard cleaning or washing processes
- C11D2111/10—Objects to be cleaned
- C11D2111/12—Soft surfaces, e.g. textile
Definitions
- This invention relates to a method of laundering fabric onto which a quaternary ammonium fabric softening compound has been deposited and dried.
- Cationic rinse conditioners are known to exhaust almost completely onto fabrics during the rinsing process. It is known, for example from “Liquid detergents", published 2006, CRC press page 490, that anionic surfactants will complex with cationic actives and that the resulting complex may deposit onto fabrics and, as a result, the stain removal performance of detergent products comprising anionic surfactant may be reduced. At lower in-wash surfactant levels it is expected that this loss of performance will become more significant. This expectation is supported by the teaching in WO93/018124 (P&G ) which, although relating mainly to granular detergent compositions, should be expected to apply also to liquids because the effect occurs in-wash.
- P&G WO93/018124
- WO93/018124 claims a detergent composition comprising low levels (5% to 10% combined weight) of a combination of water soluble alkyl ethoxysulphate anionic surfactant and alkyl sulphate anionic surfactant in combination at specific weight ratios.
- this document discloses "robust detergency performance", of the composition even in the presence of cationic fabric softener components in the wash solution, the examples use an imidazoline based cationic fabric conditioner and show reduced yellowing (whiteness loss) rather than improved soil (stain) removal. It is well documented that imidazoline actives have yellowing issues (see. Levinson. J. Surfactants and Detergents vol 2 (2) 223-235 (see table 4 p230)).
- WO2009/153184 describes a method of laundering fabrics that uses very low levels of in-wash surfactant, preferably comprising anionic surfactant. Wash performance is boosted by inclusion of high levels of specific polymers and enzymes. The skilled person would expect that compositions delivering such low in-wash levels of anionic surfactant would be more affected by the carry over of cationic on the fabric from previous washes/rinses than compositions and laundry processes which deliver higher levels of in-wash anionic surfactant.
- Fabric conditioner is widely used by consumers. It would be advantageous to identify a washing composition that could be used in a laundry detergent process such that the wash performance is less compromised by previous use of a fabric conditioner.
- a method of laundering fabric onto which a cationic fabric softening active has been deposited and dried comprising the step of contacting the fabric with an aqueous wash liquor having the following composition:
- the level of non-soap surfactant (a) is from 200 to 400 ppm.
- the non-soap surfactant (a) comprises at least 50 ppm of anionic surfactant.
- the EPEI is nonionic.
- the cationic fabric softening active is preferably a quaternary ammonium compound.
- the polyester soil release polymer (c) is preferably nonionic and most preferably comprises a polyester substantive midblock of terephthalate repeat units and one or more end blocks of polyethylene glycol capped with a lower alkyl or hydrogen moiety.
- the wash liquor may be formed by dosing 15 to 40 ml of an aqueous liquid detergent composition to water and diluting by a factor of at least 600.
- the non-soap surfactant most preferably comprises linear alkyl benzene sulphonate (LAS), sodium lauryl ether sulphate (SLES) and ethoxylated fatty alcohol nonionic, even more preferably the non-soap surfactant further comprises carbobetaine.
- LAS linear alkyl benzene sulphonate
- SLES sodium lauryl ether sulphate
- ethoxylated fatty alcohol nonionic even more preferably the non-soap surfactant further comprises carbobetaine.
- the low surfactant composition used in this method may still suffer a reduction in detergency performance on some stains when the load to be washed has been pre-exposed to rinse conditioner.
- this reduction is much smaller relative to the losses noted for prior art detergent liquids used at their recommended doses. This is surprising because it was expected that higher detergent levels would lead to less effect and lowering of the in-wash detergent levels, particularly anionic detergent levels would increase any problems caused by cationic rinse conditioner carry over.
- a concentrated laundry liquid with lower than expected levels of surfactant is used as described in WO2009/153184 .
- a low volume, less than 25 ml and preferably around 20 ml of the concentrated liquid is dosed to a wash load and diluted with water to form the wash liquor for use in the process.
- suitable compositions for use in the process according to the invention may comprise the ingredients described below at the levels detailed below.
- compositions for use in the method of the invention comprise detersive surfactant.
- the non soap detersive surfactant makes up at least 10 wt% of the liquid composition, preferably it makes up from 12 to 60 wt%.
- the compositions for use according to the invention most preferably have total active detersive surfactant levels of at least 15 wt%.
- compositions are used in small doses that require them to be diluted in at least 500 times their own volume of water to form a main-wash liquor comprising at most 0.5 g/l surfactant.
- They may be concentrated compositions designed for front loading automatic washing machines, hand washing or top loading automatic washing machines. In hand washing less water may be used and in top loading automatic washing machines a higher amount of water would normally be used than for a front loading automatic machine.
- the dose of detergent liquid is adjusted accordingly to give similar wash liquor concentrations.
- Surfactants assist in removing soil from the textile materials and also assist in maintaining removed soil in solution or suspension in the wash liquor.
- Anionic, or blends of anionic and nonionic, surfactants are a preferred feature of the present invention.
- the amount of anionic surfactant is preferably at least 5 wt%.
- anionic surfactants form the majority of the non-soap surfactant (a).
- Preferred alkyl sulphonates are alkylbenzene sulphonates, particularly linear alkylbenzene sulphonates (LAS) having an alkyl chain length of C 8 -C 15 .
- the counter ion for anionic surfactants is generally an alkali metal, typically sodium, although other counter-ions such as MEA, TEA or ammonium can be used. Suitable anionic surfactant materials are available in the marketplace as the 'Genapol'TM range from Clariant.
- Preferred linear alkyl benzene sulphonate surfactants are Detal LAS with an alkyl chain length of from 8 to 15, more preferably 12 to 14.
- composition further comprises an alkyl polyethoxylate sulphate anionic surfactant of the formula (I): RO(C 2 H 4 O) x SO 3 - M + (I) where R is an alkyl chain having from 10 to 22 carbon atoms, saturated or unsaturated, M is a cation which makes the compound water-soluble, especially an alkali metal, ammonium or substituted ammonium cation, and x averages from 1 to 15.
- R is an alkyl chain having from 12 to 16 carbon atoms
- M is Sodium and x averages from 1 to 3, preferably x is 3;
- SLES sodium lauryl ether sulphate
- It is the sodium salt of lauryl ether sulphonic acid in which the predominantly C12 lauryl alkyl group has been ethoxylated with an average of 3 moles of ethylene oxide per mole.
- alkyl sulphate surfactant may be used, especially the non-ethoxylated C 12-15 primary and secondary alkyl sulphates.
- PAS is preferably used in admixture with LAS and most preferably in admixture with LAS and SLES.
- a preferred SLES/AO/LAS/PAS liquid has a detersive surfactant system comprising 60 parts SLES, 20 parts amine oxide, 10 parts LAS and 10 parts PAS.
- Nonionic surfactants include primary and secondary alcohol ethoxylates, especially C 8 -C 20 aliphatic alcohol ethoxylated with an average of from 1 to 20 moles of ethylene oxide per mole of alcohol, and more especially the C 10 -C 15 primary and secondary aliphatic alcohols ethoxylated with an average of from 1 to 10 moles of ethylene oxide per mole of alcohol.
- Non-ethoxylated nonionic surfactants include alkyl polyglycosides, glycerol monoethers and polyhydroxy amides (glucamide). Mixtures of nonionic surfactant may be used.
- the composition contains from 0.2 wt% to 40 wt%, preferably 1 wt% to 20 wt%, more preferably 5 to 15 wt% of a non-ionic surfactant, such as alcohol ethoxylate, nonylphenol ethoxylate, alkylpolyglycoside, alkyldimethylamineoxide, ethoxylated fatty acid monoethanolamide, fatty acid monoethanolamide, polyhydroxy alkyl fatty acid amide, or N-acyl N-alkyl derivatives of glucosamine (“glucamides").
- a non-ionic surfactant such as alcohol ethoxylate, nonylphenol ethoxylate, alkylpolyglycoside, alkyldimethylamineoxide, ethoxylated fatty acid monoethanolamide, fatty acid monoethanolamide, polyhydroxy alkyl fatty acid amide, or N-acyl N-alkyl derivatives of glucosamine (“glucamides”).
- Nonionic surfactants that may be used include the primary and secondary alcohol ethoxylates, especially the C 8 -C 20 aliphatic alcohols ethoxylated with an average of from 1 to 35 moles of ethylene oxide per mole of alcohol, and more especially the C 10 -C 15 primary and secondary aliphatic alcohols ethoxylated with an average of from 1 to 10 moles of ethylene oxide per mole of alcohol.
- composition may comprise up to 10 wt% of an amine oxide of the formula (2): R 1 N(O)(CH 2 R 2 ) 2 (2)
- R 1 is a long chain moiety and each CH 2 R 2 is a short chain moiety.
- R 2 is preferably selected from hydrogen, methyl and -CH 2 OH.
- R 1 is a primary or branched hydrocarbyl moiety which can be saturated or unsaturated, preferably, R 1 is a primary alkyl moiety.
- R 1 is a hydrocarbyl moiety having chain length of from about 8 to about 18.
- R 1 is C 8 -C 18 alkyl
- R 2 is H.
- These amine oxides are illustrated by C 12-14 alkyldimethyl amine oxide, hexadecyl dimethylamine oxide, octadecylamine oxide.
- a preferred amine oxide material is Lauryl dimethylamine oxide, also known as dodecyldimethylamine oxide or DDAO. Such an amine oxide material is commercially available from Hunstman under the trade name Empigen® OB.
- Amine oxides suitable for use herein are also available from Akzo Chemie and Ethyl Corp. See McCutcheon's compilation and Kirk-Othmer review article for alternate amine oxide manufacturers.
- R 2 is H
- R 2 may be CH 2 OH, such as: hexadecylbis(2-hydroxyethyl)amine oxide, tallowbis(2-hydroxyethyl)amine oxide, stearylbis(2-hydroxyethyl)amine oxide and oleylbis(2- hydroxyethyl)amine oxide.
- Preferred amine oxides have the formula (3): O - - N + (Me) 2 R 1 (3) where R 1 is C 12-16 alkyl, preferably C 12-14 alkyl; Me is a methyl group.
- Nonionic-free systems with up to 95 %wt LAS can be made provided that some zwitterionic surfactant, such as sulphobetaine, is present.
- a preferred zwitterionic material is a betaine available from Huntsman under the name Empigen® BB. Betaines, improve particulate soil detergency in the compositions of the invention.
- Cationic surfactants are preferably substantially absent.
- compositions may comprise soap which can act as a builder and/or as an antifoam.
- the amount of non-soap anionic surfactant must exceed the amount of soap.
- the amount of soap must be less than or equal to 15wt% of the total liquid composition.
- the composition comprises an ethoxylated polyethyleneimine polymer (EPEI) for cleaning.
- EPEI ethoxylated polyethyleneimine polymer
- the EPEI is nonionic. That means it does not have any quaternary nitrogens, or nitrogen oxides or any ionic species other than possible pH affected protonation of nitrogens.
- Polyethylene imines are materials composed of ethylene imine units -CH2CH2NH- and, where branched, the hydrogen on the nitrogen is replaced by another chain of ethylene imine units.
- These polyethyleneimines can be prepared, for example, by polymerizing ethyleneimine in the presence of a catalyst such as carbon dioxide, sodium bisulphite, sulphuric acid, hydrogen peroxide, hydrochloric acid, acetic acid, and the like.
- a catalyst such as carbon dioxide, sodium bisulphite, sulphuric acid, hydrogen peroxide, hydrochloric acid, acetic acid, and the like.
- Specific methods for preparing these polyamine backbones are disclosed in U.S. Pat. No. 2,182,306, Ulrich et al., issued Dec. 5, 1939 ; U.S. Pat. No.
- the EPEI comprises a polyethyleneimine backbone wherein the modification of the polyethyleneimine backbone is intended to leave the polymer without quaternisation.
- Such nonionic EPEI may be represented as PEI(X)YEO where X represents the molecular weight of the unmodified PEI and Y represents the average moles of ethoxylation per nitrogen atom in the polyethyleneimine backbone.
- the ethoxylation number Y may range from 9 to 40 ethoxy moieties per modification, preferably it is in the range of 16 to 26, most preferably 18 to 22.
- X is selected to be from about 300 to about 10000 weight average molecular weight and is preferably about 600.
- the ethoxylated polyethyleneimine polymer (EPEI) is present in the composition preferably at a level of between 0.01 and 25 wt%, but more preferably at a level of at least 2 wt% and/or less than 9.5 wt%, most preferably from 3 to 9 wt% and with a ratio of non-soap surfactant to EPEI of from 2:1 to 7:1, preferably from 3:1 to 6:1, or even to 5:1.
- the composition comprises at least 0.5 wt% of a soil release polymer for oily soil removal, especially from polyester.
- Soil release polymers improve the main wash performance of the compositions when used in the low in wash surfactant process of the present invention.
- One preferred class of polymer is the fabric-substantive polymers comprising at least one of (i) saccharide or (ii) dicarboxylic acid and polyol monomer units. Typically these have soil release properties and while they can have a primary detergency effect they generally assist in subsequent cleaning. Preferably these should be present at a level of at least 2% wt preferably at least 3 wt% of the composition.
- the soil release polymer will generally comprise up to 10.0 wt%, of the detergent composition, preferably from 3 wt% to 9 wt%, but more preferably they are used at greater than 2 wt% and most preferably greater than 3 wt%, even more preferably greater than 5 wt%, say 6 to 8 wt% in the composition.
- the soil release polymers for polyester will comprise polymers of aromatic dicarboxylic acids and alkylene glycols (including polymers containing polyalkylene glycols).
- the polymeric soil release agents useful herein especially include those soil release agents having:
- the polyoxyethylene segments of (a)(i) will have a degree of polymerization of from about 200, although higher levels can be used, preferably from 3 to about 150, more preferably from 6 to about 100.
- Suitable oxy C 4 -C 8 alkylene hydrophobic segments include, but are not limited to, end-caps of polymeric soil release agents such as MO 3 S(CH 2 ) n OCH 2 CH 2 O--, where M is sodium and n is an integer from 4-6, as disclosed in U.S. Pat. No. 4,721,580, issued Jan. 26, 1988 to Gosselink .
- Soil release agents characterized by poly(vinyl ester) hydrophobic segments include graft copolymers of poly(vinyl ester), e.g., C 1 -C 6 vinyl esters, preferably poly(vinyl acetate) grafted onto polyalkylene oxide backbones, such as polyethylene oxide backbones.
- poly(vinyl ester) e.g., C 1 -C 6 vinyl esters
- poly(vinyl acetate) grafted onto polyalkylene oxide backbones such as polyethylene oxide backbones.
- Commercially available soil release agents of this kind include the SOKALAN type of material, e.g., SOKALAN HP-22, available from BASF (West Germany).
- One type of preferred soil release agent is a copolymer having random blocks of ethylene terephthalate and polyethylene oxide (PEO) terephthalate.
- the molecular weight of this polymeric soil release agent is in the range of from about 25,000 to about 55,000. See U.S. Pat. No. 3,959,230 to Hays, issued May 25, 1976 and U.S. Pat. No. 3,893,929 to Basadur issued Jul. 8, 1975 .
- Another preferred polymeric soil release agent is a polyester with repeat units of ethylene terephthalate units containing 10 to 15 wt% of ethylene terephthalate units together with 90 to 80 wt% weight of polyoxyethylene terephthalate units, derived from a polyoxyethylene glycol of average molecular weight 300-5,000.
- this polymer include the commercially available material ZELCON 5126 (from DuPont) and MILEASE T (from ICI). See also U.S. Pat. No. 4,702,857, issued Oct. 27, 1987 to Gosselink .
- Another preferred polymeric soil release agent is a sulphonated product of a substantially linear ester oligomer comprised of an oligomeric ester backbone of terephthaloyl and oxyalkyleneoxy repeat units and terminal moieties covalently attached to the backbone.
- These soil release agents are described fully in U.S. Pat. No. 4,968,451, issued Nov. 6, 1990 to J.J. Scheibel and E. P. Gosselink .
- Other suitable polymeric soil release agents include the terephthalate polyesters of U.S. Pat. No. 4,711,730, issued Dec. 8, 1987 to Gosselink et al , the anionic end-capped oligomeric esters of U.S. Pat. No. 4,721,580, issued Jan. 26, 1988 to Gosselink , and the block polyester oligomeric compounds of U.S. Pat. No. 4,702,857, issued Oct. 27, 1987 to Gosselink .
- Preferred polymeric soil release agents also include the soil release agents of U.S. Pat. No. 4,877,896, issued Oct. 31, 1989 to Maldonado et al , which discloses anionic, especially sulfoarolyl, end-capped terephthalate esters.
- Still another preferred soil release agent is an oligomer with repeat units of terephthaloyl units, sulfoisoterephthaloyl units, oxyethyleneoxy and oxy-1,2-propylene units.
- the repeat units form the backbone of the oligomer and are preferably terminated with modified isethionate end-caps.
- a particularly preferred soil release agent of this type comprises about one sulfoisophthaloyl unit, 5 terephthaloyl units, oxyethyleneoxy and oxy-1,2-propyleneoxy units in a ratio of from about 1.7 to about 1.8, and two end-cap units of sodium 2-(2-hydroxyethoxy)-ethanesulphonate.
- Said soil release agent also comprises from about 0.5% to about 20%, by weight of the oligomer, of a crystalline-reducing stabilizer, preferably selected from the group consisting of xylene sulfonate, cumene sulfonate, toluene sulfonate, and mixtures thereof.
- a crystalline-reducing stabilizer preferably selected from the group consisting of xylene sulfonate, cumene sulfonate, toluene sulfonate, and mixtures thereof.
- Suitable soil release polymers are described in WO 2008095626 (Clariant ); WO 2006133867 (Clariant ); WO 2006133868 (Clariant ); WO 2005097959 (Clariant ); WO 9858044 (Clariant ); WO 2000004120 (Rhodia Chimie); US 6242404 (Rhodia Inc); WO 2001023515 (Rhodia Inc); WO 9941346 (Rhodia Chim); WO 9815346 (Rhodia Inc); WO 9741197 (BASF); EP 728795 (BASF); US 5008032 (BASF); WO 2002077063 (BASF); EP 483606 ( BASF); EP 442101 (BASF); WO 9820092 (Proctor & Gamble ); EP 201124 (Proctor & Gamble ); EP 199403 (Proctor & Gamble ); DE 2527793 (Proctor & Gamble ); WO 9919429 (Proctor & Gamble
- EPEI is nonionic, most preferably it comprises no propoxy moieties.
- the most preferred soil release polymers are the water soluble/miscible or dispersible polyesters such as: linear polyesters sold under the Repel-O-Tex brand by Rhodia (Gerol), or the Texcare brand by Clariant, especially Texcare SRN170, and heavily branched polyesters such as those available from Sasol and described in US 7119056 .
- the polyesters are preferably nonionic and comprise a mid block of spaced apart terephthalate repeat units and at least one end block based on polyethylene glycol with a lower alkyl or hydrogen termination.
- compositions may further comprise dye transfer inhibition polymers, anti redeposition polymers and cotton soil release polymers, especially those based on modified cellulosic materials.
- At least one or more enzymes may be present in the compositions for cleaning boost.
- Lipase is a particularly preferred enzyme.
- the composition preferably contains from about 5 to about 20000 LU/g of a lipase.
- Preferred lipase enzymes include those of bacterial or fungal origin. Chemically modified or protein engineered mutants are included.
- useful lipases include lipases from Humicola , more preferably ones which comprise a polypeptide having an amino acid sequence which has at least 90% sequence identity with the wild-type lipase derived from Humicola lanuginosa , most preferably strain DSM 4109. The amount in the composition is higher than typically found in liquid detergents. This can be seen by the ratio of non-soap surfactant to lipase enzyme, in particular.
- a particularly preferred lipase enzyme is available under the trademark Lipoclean TM from Novozymes.
- suitable lipases include those of bacterial or fungal origin. Chemically modified or protein engineered mutants are included. Examples of useful lipases include lipases from Humicola (synonym Thermomyces ), e.g. from H . lanuginosa ( T . lanuginosus ) as described in EP 258 068 and EP 305 216 or from H . insolens as described in WO 96/13580 , a Pseudomonas lipase, e.g. from P . alcaligenes or P . pseudoalcaligenes ( EP 218 272 ), P . cepacia ( EP 331 376 ), P .
- lipase variants such as those described in WO 92/05249 , WO 94/01541 , EP 407 225 , EP 260 105 , WO 95/35381 , WO 96/00292 , WO 95/30744 , WO 94/25578 , WO 95/14783 , WO 95/22615 , WO 97/04079 and WO 97/07202 .
- Preferred commercially available lipase enzymes include LipolaseTM and Lipolase UltraTM, LipexTM and Lipoclean TM (Novozymes A/S).
- lipase In addition to or as an alternative to lipase one or more other enzymes may be present. However, lipase is particularly preferred.
- the presence of relatively high levels of calcium in the poorly built or unbuilt compositions of the invention has a beneficial effect on the turnover of certain enzymes, particularly lipase enzymes and preferably lipases from Humicola .
- the preferred lipases include first wash lipases which comprise a polypeptide having an amino acid sequence which has at least 90% sequence identity with the wild-type lipase derived from Humicola lanuginosa strain DSM 4109 and compared to said wild-type lipase, comprises a substitution of an electrically neutral or negatively charged amino acid within 15 A of E1 or Q249 with a positively charged amino acid; and may further comprise:
- phospholipase classified as EC 3.1.1.4 and/or EC 3.1.1.32.
- phospholipase is an enzyme which has activity towards phospholipids.
- Phospholipids such as lecithin or phosphatidylcholine, consist of glycerol esterified with two fatty acids in an outer (sn-1) and the middle (sn-2) positions and esterified with phosphoric acid in the third position; the phosphoric acid, in turn, may be esterified to an amino-alcohol.
- Phospholipases are enzymes which participate in the hydrolysis of phospholipids.
- phospholipases A 1 and A 2 which hydrolyze one fatty acyl group (in the sn-1 and sn-2 position, respectively) to form lysophospholipid
- lysophospholipase or phospholipase B
- Phospholipase C and phospholipase D release diacyl glycerol or phosphatidic acid respectively.
- proteases include those of animal, vegetable or microbial origin. Microbial origin is preferred. Chemically modified or protein engineered mutants are included.
- the protease may be a serine protease or a metallo protease, preferably an alkaline microbial protease or a trypsin-like protease.
- Preferred commercially available protease enzymes include AlcalaseTM, SavinaseTM, PrimaseTM, DuralaseTM, DyrazymTM, EsperaseTM, EverlaseTM, PolarzymeTM, and KannaseTM, (Novozymes A/S), MaxataseTM, MaxacalTM, MaxapemTM, ProperaseTM, PurafectTM, Purafect OxPTM, FN2TM, and FN3TM (Genencor International Inc.).
- the method of the invention may be carried out in the presence of cutinase. classified in EC 3.1.1.74.
- the cutinase used according to the invention may be of any origin.
- Preferably cutinases are of microbial origin, in particular of bacterial, of fungal or of yeast origin.
- Suitable amylases include those of bacterial or fungal origin. Chemically modified or protein engineered mutants are included. Amylases include, for example, alpha-amylases obtained from Bacillus , e.g. a special strain of B. licheniformis , described in more detail in GB 1,296,839 , or the Bacillus sp. strains disclosed in WO 95/026397 or WO 00/060060 .
- amylases are DuramylTM, TermamylTM, Termamyl UltraTM, NatalaseTM, StainzymeTM, FungamylTM and BANTM (Novozymes A/S), RapidaseTM and PurastarTM (from Genencor International Inc.).
- Suitable cellulases include those of bacterial or fungal origin. Chemically modified or protein engineered mutants are included. Suitable cellulases include cellulases from the genera Bacillus , Pseudomonas , Humicola , Fusarium , Thielavia , Acremonium , e.g.
- Suitable peroxidases/oxidases include those of plant, bacterial or fungal origin. Chemically modified or protein engineered mutants are included. Examples of useful peroxidases include peroxidases from Coprinus , e.g. from C . cinereus , and variants thereof as those described in WO 93/24618 , WO 95/10602 , and WO 98/15257 . Commercially available peroxidases include GuardzymeTM and NovozymTM 51004 (Novozymes A/S).
- Pectate lyases also called polygalacturonate lyases
- pectate lyases include pectate lyases that have been cloned from different bacterial genera such as Erwinia, Pseudomonas, Klebsiella and Xanthomonas, as well as from Bacillus subtilis ( Nasser et al. (1993) FEBS Letts. 335:319-326 ) and Bacillus sp. YA-14 ( Kim et al. (1994) Biosci. Biotech. Biochem. 58:947-949 ).
- the pectate lyase comprises the pectate lyase disclosed in Heffron et al., (1995) Mol. Plant-Microbe Interact. 8: 331-334 and Henrissat et al., (1995) Plant Physiol. 107: 963-976 .
- pectate lyases are disclosed in WO 99/27083 and WO 99/27084 .
- pectate lyases derived from Bacillus licheniformis
- US patent no. 6,284,524 Specifically contemplated pectate lyase variants are disclosed in WO 02/006442 , especially the variants disclosed in the Examples in WO 02/006442 .
- alkaline pectate lyases examples include BIOPREPTM and SCOURZYMETM L from Novozymes A/S, Denmark.
- Mannanase examples include mannanases of bacterial and fungal origin.
- the mannanase is derived from a strain of the filamentous fungus genus Aspergillus, preferably Aspergillus niger or Aspergillus aculeatus ( WO 94/25576 ).
- WO 93/24622 discloses a mannanase isolated from Trichoderma reseei. Mannanases have also been isolated from several bacteria, including Bacillus organisms. For example, Talbot et al., Appl. Environ. Microbiol., Vol.56, No. 11, pp.
- JP-A-03047076 discloses a beta-mannanase derived from Bacillus sp.
- JP-A-63056289 describes the production of an alkaline, thermostable beta-mannanase.
- JP-A-63036775 relates to the Bacillus microorganism FERM P-8856 which produces beta-mannanase and beta-mannosidase.
- JP-A-08051975 discloses alkaline beta-mannanases from alkalophilic Bacillus sp. AM-001.
- a purified mannanase from Bacillus amyloliquefaciens is disclosed in WO 97/11164 .
- WO 91/18974 describes a hemicellulase such as a glucanase, xylanase or mannanase active.
- mannanases derived from Bacillus agaradhaerens, Bacillus licheniformis, Bacillus halodurans, Bacillus clausii, Bacillus sp., and Humicola insolens disclosed in WO 99/64619 .
- Bacillus sp. mannanases concerned in the Examples in WO 99/64619 .
- mannanases examples include MannawayTM available from Novozymes A/S Denmark.
- the enzyme and any perfume/fragrance or pro-fragrance present may show some interaction and should be chosen such that this interaction is not negative. Some negative interactions may be avoided by encapsulation of one or other of enzyme and pro-fragrance and/or other segregation within the product.
- Any enzyme present in the composition may be stabilized using conventional stabilizing agents, e.g., a polyol such as propylene glycol or glycerol, a sugar or sugar alcohol, lactic acid, boric acid, or a boric acid derivative, e.g., an aromatic borate ester, or a phenyl boronic acid derivative such as 4-formylphenyl boronic acid, and the composition may be formulated as described in e.g. WO 92/19709 and WO 92/19708 .
- a polyol such as propylene glycol or glycerol
- a sugar or sugar alcohol lactic acid, boric acid, or a boric acid derivative, e.g., an aromatic borate ester, or a phenyl boronic acid derivative such as 4-formylphenyl boronic acid
- compositions of the invention may contain one or more other ingredients.
- Such ingredients include viscosity modifiers, foam boosting agents, preservatives (e.g. bactericides), pH buffering agents, polyelectrolytes, anti-shrinking agents, anti-wrinkle agents, anti-oxidants, sunscreens, anti-corrosion agents, drape imparting agents, anti-static agents and ironing aids.
- the compositions may further comprise, colorants, pearlisers and/or opacifiers, and shading dye.
- fluorescer in the compositions.
- these fluorescent agents are supplied and used in the form of their alkali metal salts, for example, the sodium salts.
- the total amount of the fluorescent agent or agents used in the composition is generally from 0.005 to 2 wt %, more preferably 0.01 to 0.5 wt %.
- Preferred classes of fluorescer are: Di-styryl biphenyl compounds, e.g. Tinopal (Trade Mark) CBS-X, Di-amine stilbene di-sulphonic acid compounds, e.g. Tinopal DMS pure Xtra and Blankophor (Trade Mark) HRH, and Pyrazoline compounds, e.g. Blankophor SN.
- Di-styryl biphenyl compounds e.g. Tinopal (Trade Mark) CBS-X
- Di-amine stilbene di-sulphonic acid compounds e.g. Tinopal DMS pure Xtra and Blankophor (Trade Mark) HRH
- Pyrazoline compounds e.g. Blankophor SN.
- Preferred fluorescers are: sodium 2 (4-styryl-3-sulfophenyl)-2H-napthol[1,2-d]triazole, disodium 4,4'-bis ⁇ [(4-anilino-6-(N methyl-N-2 hydroxyethyl) amino 1,3,5-triazin-2-yl)]amino ⁇ stilbene-2-2' disulfonate, disodium 4,4'-bis ⁇ [(4-anilino-6-morpholino-1,3,5-triazin-2-yl)]amino ⁇ stilbene-2-2' disulfonate, and disodium 4,4'-bis(2-sulfostyryl)biphenyl.
- Detergent compositions according to the invention may comprise a weight efficient bleach system. Such systems typically do not utilise the conventional percarbonate or peracid and/or bleach activator approach.
- the present invention may be used in a formulation that is used to bleach via air, or an air bleach catalyst system.
- Suitable complexes and organic molecule (ligand) precursors for forming complexes are available to the skilled worker, for example, from: WO 98/39098 ; WO 98/39406 , WO 97/48787 , WO 00/29537 ; WO 00/52124 , and WO00/60045 , incorporated by reference.
- An example of a preferred catalyst is a transition metal complex of MeN4Py ligand (N,N-bis(pyridin-2-yl-methyl)-1-,1-bis(pyridin-2-yl)-1-aminoethane).
- MeN4Py ligand N,N-bis(pyridin-2-yl-methyl)-1-,1-bis(pyridin-2-yl)-1-aminoethane.
- Suitable bispidon catalyst materials and their action are described in WO02/48
- Photobleaches may also be employed.
- a "photobleach” is any chemical species that forms a reactive bleaching species on exposure to sunlight, and preferably is not permanently consumed in the reaction.
- Preferred photo-bleaches include singlet oxygen photo-bleaches and radical photo-bleaches.
- Suitable singlet oxygen photo-bleaches may be selected from, water soluble phthalocyanine compounds, particularly metallated phthalocyanine compounds where the metal is Zn or Al-Z1 where Z1 is a halide, sulphate, nitrate, carboxylate, alkanolate or hydroxyl ion.
- the phthalocyanin has 1-4 SO 3 X groups covalently bonded to it where X is an alkali metal or ammonium ion. Such compounds are described in WO2005/014769 (Ciba).
- the bleach catalyst is typically incorporated at a level of about 0.0001 to about 10wt%, preferably about 0.001 to about 5wt%.
- composition of the present invention is designed to be used at very low levels of product dosage, it is advantageous to ensure that perfume is employed efficiently.
- a particularly preferred way of ensuring that perfume is employed efficiently is to use an encapsulated perfume.
- Use of a perfume that is encapsulated reduces the amount of perfume vapour that is produced by the composition before it is diluted. This is important when the perfume concentration is increased to allow the amount of perfume per wash to be kept at a reasonably high level.
- the perfume is not only encapsulated but also that the encapsulated perfume is provided with a deposition aid to increase the efficiency of perfume deposition and retention on fabrics.
- the deposition aid is preferably attached to the encapsulate by means of a covalent bond, entanglement or strong adsorption, preferably by a covalent bond or entanglement.
- Shading dye can be used to improve the performance of the compositions used in the method of the present invention.
- the deposition of shading dye onto fabric is improved when they are used in compositions of the invention and according to the process of the invention.
- Preferred dyes are violet or blue. It is believed that the deposition on fabrics of a low level of a dye of these shades, masks yellowing of fabrics.
- a further advantage of shading dyes is that they can be used to mask any yellow tint in the composition itself.
- Direct dyes are the class of water soluble dyes which have an affinity for fibres and are taken up directly. Direct violet and direct blue dyes are preferred. Preferably bis-azo or tris-azo dyes are used.
- the direct dye is a direct violet of the following structures: or wherein:
- Preferred dyes are direct violet 7, direct violet 9, direct violet 11, direct violet 26, direct violet 31, direct violet 35, direct violet 40, direct violet 41, direct violet 51, and direct violet 99.
- Bis-azo copper containing dyes such as direct violet 66 may be used.
- the benzidene based dyes are less preferred.
- the direct dye may be covalently linked to the photo-bleach, for example as described in WO2006/024612 .
- the direct dye is present at 0.000001 to 1 wt% more preferably 0.00001 wt% to 0.0010 wt% of the composition.
- Cotton substantive acid dyes give benefits to cotton containing garments.
- Preferred dyes and mixes of dyes are blue or violet.
- Preferred acid dyes are:
- Preferred azine dyes are: acid blue 98, acid violet 50, and acid blue 59, more preferably acid violet 50 and acid blue 98.
- Other preferred non-azine acid dyes are acid violet 17, acid black 1 and acid blue 29.
- the acid dye is present at 0.0005 wt% to 0.01 wt% of the formulation.
- the composition may comprise one or more hydrophobic dyes selected from benzodifuranes, methine, triphenylmethanes, napthalimides, pyrazole, napthoquinone, anthraquinone and mono-azo or di-azo dye chromophores.
- Hydrophobic dyes are dyes which do not contain any charged water solubilising group. Hydrophobic dyes may be selected from the groups of disperse and solvent dyes. Blue and violet anthraquinone and mono-azo dye are preferred.
- Preferred dyes include solvent violet 13, disperse violet 27 disperse violet 26, disperse violet 28, disperse violet 63 and disperse violet 77.
- the hydrophobic dye is present at 0.0001 wt% to 0.005 wt% of the formulation.
- Basic dyes are organic dyes which carry a net positive charge. They deposit onto cotton. They are of particular utility for used in composition that contain predominantly cationic surfactants. Dyes may be selected from the basic violet and basic blue dyes listed in the Colour Index International. Preferred examples include triarylmethane basic dyes, methane basic dye, anthraquinone basic dyes, basic blue 16, basic blue 65, basic blue 66, basic blue 67, basic blue 71, basic blue 159, basic violet 19, basic violet 35, basic violet 38, basic violet 48; basic blue 3, basic blue 75, basic blue 95, basic blue 122, basic blue 124, basic blue 141.
- Reactive dyes are dyes which contain an organic group capable of reacting with cellulose and linking the dye to cellulose with a covalent bond. They deposit onto cotton.
- the reactive group is hydrolysed or reactive group of the dyes has been reacted with an organic species such as a polymer, so as to the link the dye to this species.
- Dyes may be selected from the reactive violet and reactive blue dyes listed in the Colour Index International.
- Preferred examples include reactive blue 19, reactive blue 163, reactive blue 182 and reactive blue 96.
- Dye conjugates are formed by binding direct, acid or basic dyes to polymers or particles via physical forces. Dependent on the choice of polymer or particle they deposit on cotton or synthetics. A description is given in WO2006/055787 .
- Particularly preferred dyes are: direct violet 7, direct violet 9, direct violet 11, direct violet 26, direct violet 31, direct violet 35, direct violet 40, direct violet 41, direct violet 51, direct violet 99, acid blue 98, acid violet 50, acid blue 59, acid violet 17, acid black 1, acid blue 29, solvent violet 13, disperse violet 27 disperse violet 26, disperse violet 28, disperse violet 63, disperse violet 77 and mixtures thereof.
- Shading dye can be used in the absence of fluorescer, but it is especially preferred to use a shading dye in combination with a fluorescer, for example in order to reduce yellowing due to chemical changes in adsorbed fluorescer.
- the detergent compositions may also optionally contain relatively low levels of organic detergent builder or sequestrant material.
- organic detergent builder or sequestrant material examples include the alkali metal, citrates, succinates, malonates, carboxymethyl succinates, carboxylates, polycarboxylates and polyacetyl carboxylates. Specific examples include sodium, potassium and lithium salts of oxydisuccinic acid, mellitic acid, benzene polycarboxylic acids, and citric acid.
- DEQUEST TM organic phosphonate type sequestering agents sold by Monsanto and alkanehydroxy phosphonates.
- suitable organic builders include the higher molecular weight polymers and copolymers known to have builder properties.
- such materials include appropriate polyacrylic acid, polymaleic acid, and polyacrylic/polymaleic acid copolymers and their salts, such as those sold by BASF under the name SOKALAN TM .
- the organic builder materials may comprise from about 0.5% to 20 wt%, preferably from 1 wt% to 10 wt%, of the composition.
- the preferred builder level is less than 10 wt% and preferably less than 5 wt% of the composition.
- a preferred sequestrant is HEDP (1-Hydroxyethylidene -1,1,-diphosphonic acid), for example sold as Dequest 2010. Also suitable but less preferred as it gives inferior cleaning results is Dequest® 2066 (Diethylenetriamine penta(methylene phosphonic acid or Heptasodium DTPMP).
- compositions preferably comprise one or more hydrotropes; although the minimum amount consistent with the need for concentration should be used.
- Suitable hydrotropes include MPG (monopropylene glycol). This and/or other conventionally employed hydrotropes may be used in the composition at levels of from 2 to 10 wt%.
- a hydrotrope is a solvent that is neither water nor conventional surfactant that aids the solubilisation of the surfactants and other components in the aqueous liquid to render it isotropic.
- MPG monopropylene glycol
- suitable hydrotropes there may be mentioned as preferred: glycerol, sodium cumene sulphonate, ethanol, other glycols, e.g. di propylene glycol, diethers and urea.
- buffers are MEA, and TEA. If present they are preferably used in the composition at levels of from 5 to 15 wt%.
- compositions may have their rheology modified by use of a material or materials that form a structuring network within the composition.
- Suitable structurants include hydrogenated castor oil, microfibrous cellulose and natural based structurants such as citrus pulp fibre. Citrus pulp fibre is particularly preferred especially if lipase enzyme is included in the composition.
- compositions may, and preferably do, comprise visual cues of solid material that is not dissolved in the composition. Preferably they are used in combination with an external structurant to ensure that they remain in suspension.
- visual cues are lamellar cues formed from polymer film and possibly comprising functional ingredients that may not be as stable if exposed to the alkaline liquid. Enzymes and bleach catalysts are examples of such ingredients. Also perfume, particularly microencapsulated perfume.
- the liquids may be packaged as unit doses. To allow greater flexibility in dosing the liquids are preferably supplied in multiuse plastics packs with a top or bottom closure. A dosing system may be supplied with the pack either as a part of the cap or as an integrated system.
- liquids according to the invention may be formulated to allow them to be dosed to a typical front loading automatic washing machine at a dosage level of 20ml.
- the low in wash surfactant level being compensated by the presence of enzymes, soil release polymer and EPEI together with further optional high efficacy cleaning ingredients, such as enzymes.
- the invention is also suitable for the more conventional dosage levels of about 35 ml. To obtain suitable detergent liquids of this type all that is necessary is to add further water and possibly perfume to the 20ml composition before it is packaged.
- the fabric conditioning active may be any of the known cationic softening actives, particularly quaternary ammonium compounds including the biodegradable ester quaternary ammonium actives; preferably hardened tallow triethanolamine quaternary.
- Fabric conditioners comprising imidazolines will also complex with anionic surfactant and the invention extends also to washing of fabrics that have previously been treated with fabric conditioner comprising this type of fabric conditioning active.
- LAS acid is C12-14 linear alkylbenzene sulphonic acid.
- Fatty acid is saturated lauric fatty acid Prifac® 5908ex Croda.
- SLES 3EO is sodium lauryl ether sulphate with 3 moles EO.
- Empigen® BB is an alkyl betaine ex Huntsman (Coco dimethyl carbobetaine).
- NI 7EO is C12-15 alcohol ethoxylate 7EO nonionic Neodol® 25-7 (ex Shell Chemicals).
- Stenol 1618L is C16/18 fatty alcohol nonionic ex Cognis.
- Genepol C200 is coco 20 EO nonionic ex Clariant.
- HTTEAQ is hardened tallow triethanolamine quaternary (cationic fabric softening active).
- MPG is mono propylene glycol.
- TEA is triethanolamine.
- NaOH is 47% sodium hydroxide solution.
- EPEI Sokalan HP20 - ethoxylated polyethylene imine cleaning polymer: PEI(600) 20EO ex BASF.
- SRP soil release polymer (Texcare SRN170 ex Clariant)
- Dequest® 2066 is Diethylenetriamine penta(methylene phosphonic acid (or Heptasodium DTPMP) ex Thermphos Perfume is free oil perfume.
- the fabric conditioner The fabric conditioner
- the fabric conditioner used for the examples was a commercially available concentrated fabric conditioner composition sold under the "Comfort” brand in the UK and based on Hardened Tallow TEAQ.
- the formulation of the fabric conditioner is given in table 1.
- the fabric conditioner was used at the recommended dose for this concentrated fabric conditioner of 55mls.
- Table 1 - Fabric conditioner composition Ingredient Amount %(100% active) HTTEAQ 12.7 Stenol 1618L 1.00 Genepol C200 0.38 Perfume (free oil) 0.79 Minors and water Including preservative, anti-foam, pH modifier To 100
- compositions 1 to 4 for use in the invention are given in table 2.
- Comparative Composition A Ariel Excel gel with Biological action
- Comparative Composition B Persil Small and Mighty Biological
- a commercially available detergent liquid sold in the UK has the composition given in Table 4. It is recommended to be dosed at 35ml per wash.
- Table 2 Compositions 1 - 4 35ml dose liquids 20ml dose liquids Example 1 2 3 4 % active 24 17.1 24 17.1 Ingredient b 24% a 17.10% b 24% a 17.10% MPG 20 20 20 20 TEA 0 0 0 0 Citric Acid 0 0 0 0 NaOH 1.5 1.01 2.625 1.7675 NI 7 EO 10.55 7.28 18.4625 12.74 LAS acid 7.02 4.85 12.285 8.4875 Fatty acid 2.46 1.7 4.305 2.975 SLES (3EO) 3.5 2.42 6.125 4.235 Empigen® BB 0.86 0.86 1.505 1.505 EPEI 3.1 3.1 5.425 5.425 SRP 2.1 2.1 3.675 3.675 Dequest® 2066 0 0 0 0 Perfume 1.39 1.39 2.4325 2.4325 Protease 1.35 1.35 2.3625 2.3625 Amylase 0.54 0.54 0.945 0.945 Mannanase 0.4 0.4 0.7 0.7 Table 3 - Compar
- the surfactant system is believed to be made up from MEA-Dodecylbenzenesulfonate (LAS neutralised with MEA), Sodium Laureth Sulfate (SLES) and, MEA-Palm Kernelate.
- MEA-Dodecylbenzenesulfonate LAS neutralised with MEA
- SLES Sodium Laureth Sulfate
- MEA-Palm Kernelate MEA-Dodecylbenzenesulfonate
- composition further includes: MEA Citrate, C12-14 Pareth-7 (nonionic/emulsifier), PEI-Ethoxylate, Trimonoethanolamine Etidronate, Propylene Glycol, MEA-Borate, Glycosidase, Sodium Sulfate, Disodium Distyrylbiphenyl Disulfonate, Ethanolamine, Protease, Calcium Chloride, Colorant, and perfume.
- Washes were conducted in a European Miele washing machine using the standard 30°C cotton wash cycle.
- the main wash intake was 15 L of ambient temperature water of 26°FH water (Ca:Mg 3:1) and the total wash time (including rinses) was 1 hour 56 minutes.
- Each of the products in Table 5 was used to wash a ballast load as described above together with a series of cotton and polyester swatches that were to be subsequently stained. After washing all fabrics were tumble dried. After two complete wash cycles, the swatches were soiled using a range of soils. A final wash treatment was then conducted on the stained swatches using the same ballast and wash conditions as before.
- Each of the products in Table 5 was used to wash a ballast load as described above together with a series of cotton and polyester swatches that were to be subsequently stained.
- 55ml of the fabric conditioner detailed in Table 1 was added to the final rinse of each wash. After washing all fabrics were tumble dried. After two complete wash cycles, the swatches were soiled using a range of soils. A final wash treatment was then conducted on the stained swatches using the same ballast and wash conditions as before. No rinse conditioner was used after the final wash.
- the impact of rinse conditioner treatment was determined by measuring the loss of performance of each composition tested product when used in conjunction with rinse conditioner (Process 2) relative to that in the absence of rinse conditioner (Process 1).
- Table 6 shows the SRIs without use of Rinse conditioner.
- Table 7 shows the revised SRI when rinse conditioner is used as part of the pretreatment and the change in SRI (Process 1 - Process 2) is given for the full set of stains in Table 8.
- KC means knitted cotton.
- KP means knitted polyester.
- Fatty/oily stains Ragu/Sunflower Oil, Tomato (Pomarola) / Sunflower Oil, Red Pepper/oil/water, Red Curry (Osman), Face Make-up. Mechanical Grease
- Particulate stains 1:1 Garden Soil : Water, Yellow Pottery Clay 2:1, Red Pottery Clay 2:1
- Enzymatic stains Cocoa / milk, Choc Pudding (Heinz), Choc Ice Cream (Economy), Blood (haemoglobin).
- compositions used according to the invention exhibit a much greater robustness to rinse conditioner presence than the prior art comparative compositions with higher in wash surfactant levels. Where there are reductions in performance on adding conditioner, these are reduced. Where there are benefits on adding conditioner, these are amplified. There are several significant wins with oily/fatty stains on Polyester. There is approximate parity on enzymatic and particulate stains. The performance on sequestrant stains is unexpectedly as good as, or better, than the comparative compositions.
- composition 2 there are significant wins with oily/fatty stains, especially on Polyester. There are significant wins on particulate stains and there is parity on enzymatic/ bleachable/ sequestrant stains. The effects are biggest with Oily/Fatty stains on Polyester.
- Composition 2 versus Comparative composition A shows superiority with fatty/oily stains on polyester. The same slight downward trend as compared with B is observed on cotton (2 significant results). Enzymatic and particulate stains give approximate parity.
- composition 1 When the higher surfactant levels used in Composition 1 are compared with the results obtained for Composition 2 the benefit of using the lower in-wash non soap surfactant levels is seen. Composition 2 is outperforming composition 1 when used after rinse conditioner.
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Claims (9)
- Procédé de lavage d'un textile sur lequel un actif adoucissant de textile cationique a été déposé et séché comprenant l'étape de mise en contact du textile avec une liqueur de lavage aqueuse présentant la composition suivante :a) de 15 à 600 ppm de tensioactif de non-savon,b) au moins 50 ppm de polyéthylène imine éthoxylée,c) au moins 25 ppm d'un polymère libérant la saleté de polyester,
la teneur totale en polymère (b+c) étant d'au moins 20 % en poids de la teneur en tensioactif de non-savon (a),d) de 0,1 à 100 ppm d'enzyme choisie parmi une protéase, une amylase, une cellulase,e) éventuellement, une enzyme de lipase. - Procédé selon la revendication 1, dans lequel la teneur en tensioactif de non-savon (a) est de 200 à 400 ppm.
- Procédé selon l'une quelconque des revendications précédentes, dans lequel le tensioactif de non-savon (a) comprend au moins 50 ppm de tensioactif anionique.
- Procédé selon l'une quelconque des revendications précédentes, dans lequel l'EPEI est non ionique.
- Procédé selon l'une quelconque des revendications précédentes, dans lequel l'actif d'adoucissant de tissu cationique est un composé d'ammonium quaternaire.
- Procédé selon l'une quelconque des revendications précédentes, dans lequel le polymère de libération de saleté de polyester (c) est non ionique et comprend une séquence milieu substantive de polyester d'unités répétitives de téréphtalate et une ou plusieurs séquences terminales de polyéthylène glycol coiffées avec une moitié alkyle inférieur ou hydrogène.
- Procédé selon l'une quelconque des revendications précédentes, dans lequel la liqueur de lavage est formée par dosage de 15 à 40 ml d'une composition de détergent liquide aqueuse à de l'eau et dilution par un facteur d'au moins 600.
- Procédé selon l'une quelconque des revendications précédentes, dans lequel le tensioactif de non-savon comprend LAS, SLES et un non ionique d'alcool gras éthoxylé.
- Procédé selon l'une quelconque des revendications précédentes, dans lequel le tensioactif de non-savon comprend de la carbo-bétaïne.
Priority Applications (2)
Application Number | Priority Date | Filing Date | Title |
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EP12707100.9A EP2694635B1 (fr) | 2011-04-04 | 2012-03-05 | Procédé de lavage du linge |
PL12707100T PL2694635T3 (pl) | 2011-04-04 | 2012-03-05 | Sposób prania tkanin |
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EP11160937.6A EP2476743B1 (fr) | 2011-04-04 | 2011-04-04 | Procédé de lavage du linge |
EP12707100.9A EP2694635B1 (fr) | 2011-04-04 | 2012-03-05 | Procédé de lavage du linge |
PCT/EP2012/053709 WO2012136427A1 (fr) | 2011-04-04 | 2012-03-05 | Procédé de lavage d'un tissu |
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EP2694635A1 EP2694635A1 (fr) | 2014-02-12 |
EP2694635B1 true EP2694635B1 (fr) | 2015-11-25 |
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EP11160937.6A Revoked EP2476743B1 (fr) | 2011-04-04 | 2011-04-04 | Procédé de lavage du linge |
EP12707100.9A Revoked EP2694635B1 (fr) | 2011-04-04 | 2012-03-05 | Procédé de lavage du linge |
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EP11160937.6A Revoked EP2476743B1 (fr) | 2011-04-04 | 2011-04-04 | Procédé de lavage du linge |
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EP (2) | EP2476743B1 (fr) |
CN (1) | CN103459577B (fr) |
AR (1) | AR085771A1 (fr) |
AU (1) | AU2012238950B2 (fr) |
BR (1) | BR112013025674B1 (fr) |
CL (1) | CL2013002817A1 (fr) |
ES (1) | ES2421162T3 (fr) |
MX (1) | MX2013011464A (fr) |
MY (1) | MY161793A (fr) |
PL (1) | PL2694635T3 (fr) |
WO (1) | WO2012136427A1 (fr) |
ZA (1) | ZA201306447B (fr) |
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EP2767582A1 (fr) | 2013-02-19 | 2014-08-20 | The Procter and Gamble Company | Procédé de lavage d'un textile |
EP2767579B1 (fr) * | 2013-02-19 | 2018-07-18 | The Procter and Gamble Company | Procédé de lavage d'un textile |
CN105647687A (zh) * | 2015-09-17 | 2016-06-08 | 陕西天瑞生物科技有限公司 | 一种聚氨酯表面预处理清洁剂 |
KR101905888B1 (ko) | 2016-08-18 | 2018-10-10 | 주식회사 영신물산 | 욕중유연제의 제조방법 및 그 제조방법에 의한 욕중유연제 |
CN109790491B (zh) | 2016-09-27 | 2021-02-23 | 荷兰联合利华有限公司 | 家用洗衣方法 |
HUE046460T2 (hu) * | 2016-10-21 | 2020-02-28 | Procter & Gamble | Kationosan töltött lágyítóval felülkezelt textilek mosására alkalmas módszer |
EP3312264B1 (fr) * | 2016-10-21 | 2019-08-21 | The Procter & Gamble Company | Procédé de lavage de tissu avec dépôt d'un adoucissant actif déposé sur celui-ci |
EP3342849B1 (fr) | 2016-12-28 | 2024-06-19 | The Procter & Gamble Company | Article en dose unitaire soluble dans l'eau comprenant un polyéthylènéimine ethoxylaté |
EP3342850A1 (fr) | 2016-12-28 | 2018-07-04 | The Procter & Gamble Company | Article en dose unitaire soluble dans l'eau comprenant une polyamine zwitterionique |
EP3668960B1 (fr) * | 2017-08-18 | 2021-08-11 | The Procter & Gamble Company | Procédé de traitement de tissus |
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 |
CN112243455B (zh) | 2018-06-26 | 2022-04-29 | 宝洁公司 | 液体衣物洗涤剂组合物 |
JP7144911B2 (ja) | 2018-06-28 | 2022-09-30 | ザ プロクター アンド ギャンブル カンパニー | ポリマー系を含む布地処理組成物及び関連方法 |
WO2020058024A1 (fr) * | 2018-09-17 | 2020-03-26 | Unilever Plc | Composition détergente |
BR112021022167A2 (pt) * | 2019-05-16 | 2022-01-18 | Unilever Ip Holdings B V | Composição de lavanderia auxiliar, método para administrar enzimas a tecidos, método para aprimorar o benefício amaciante de um condicionador de tecido e uso de uma composição de lavanderia auxiliar |
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BRPI9911086B1 (pt) | 1998-06-10 | 2016-08-02 | Novozymes As | composição de limpeza, processo para tratar tecidos a máquina, e uso de uma mananase |
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EP1157088B1 (fr) | 1999-03-02 | 2006-01-11 | The Procter & Gamble Company | Compositions de blanchiment stabilisees |
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DE102005027604A1 (de) | 2005-06-15 | 2006-12-28 | Clariant Produkte (Deutschland) Gmbh | Reinigungsmittel für harte Oberflächen |
DE102005027605A1 (de) | 2005-06-15 | 2006-12-28 | Clariant Produkte (Deutschland) Gmbh | Geschirrspülmittelformulierungen enthaltend Oligoester |
DE102007005532A1 (de) | 2007-02-03 | 2008-08-07 | Clariant International Limited | Wässrige Oligo- und Polyesterzubereitungen |
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2011
- 2011-04-04 ES ES11160937T patent/ES2421162T3/es active Active
- 2011-04-04 EP EP11160937.6A patent/EP2476743B1/fr not_active Revoked
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- 2012-03-05 MY MYPI2013701844A patent/MY161793A/en unknown
- 2012-03-05 BR BR112013025674-5A patent/BR112013025674B1/pt active IP Right Grant
- 2012-03-05 WO PCT/EP2012/053709 patent/WO2012136427A1/fr active Application Filing
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- 2012-03-05 AU AU2012238950A patent/AU2012238950B2/en not_active Ceased
- 2012-03-05 EP EP12707100.9A patent/EP2694635B1/fr not_active Revoked
- 2012-03-05 CN CN201280016945.1A patent/CN103459577B/zh active Active
- 2012-03-30 AR ARP120101100A patent/AR085771A1/es not_active Application Discontinuation
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2013
- 2013-08-27 ZA ZA2013/06447A patent/ZA201306447B/en unknown
- 2013-09-30 CL CL2013002817A patent/CL2013002817A1/es unknown
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Also Published As
Publication number | Publication date |
---|---|
EP2694635A1 (fr) | 2014-02-12 |
PL2694635T3 (pl) | 2016-05-31 |
MX2013011464A (es) | 2013-10-17 |
EP2476743A1 (fr) | 2012-07-18 |
CN103459577A (zh) | 2013-12-18 |
AR085771A1 (es) | 2013-10-23 |
AU2012238950B2 (en) | 2014-11-20 |
MY161793A (en) | 2017-05-15 |
EP2476743B1 (fr) | 2013-04-24 |
CN103459577B (zh) | 2015-05-27 |
WO2012136427A1 (fr) | 2012-10-11 |
CL2013002817A1 (es) | 2014-08-22 |
ZA201306447B (en) | 2014-10-29 |
ES2421162T3 (es) | 2013-08-29 |
AU2012238950A1 (en) | 2013-09-19 |
BR112013025674B1 (pt) | 2021-02-02 |
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