EP2809762B1 - Détergents liquides comprenant une lipase et un catalyseur de blanchiment - Google Patents

Détergents liquides comprenant une lipase et un catalyseur de blanchiment Download PDF

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Publication number
EP2809762B1
EP2809762B1 EP12788520.0A EP12788520A EP2809762B1 EP 2809762 B1 EP2809762 B1 EP 2809762B1 EP 12788520 A EP12788520 A EP 12788520A EP 2809762 B1 EP2809762 B1 EP 2809762B1
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Prior art keywords
composition
alkyl
catalyst
lipase
surfactant
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German (de)
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EP2809762A1 (fr
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Jan Klugkist
Alyn James Parry
John Francis Wells
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Unilever PLC
Unilever NV
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Unilever PLC
Unilever NV
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    • 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
    • C11D3/168—Organometallic compounds or orgometallic complexes
    • 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
    • C11D3/38627—Preparations containing enzymes, e.g. protease or amylase containing lipase

Definitions

  • This invention relates to a liquid detergent composition
  • a liquid detergent composition comprising anionic surfactant, lipase enzyme and a bleach catalyst and to the use of the composition for the removal of curcuminoid stains from surfaces, for example from fabrics.
  • WO 2009/153184 suggests that an improved laundry detergent liquid concentrate may be obtained by replacing surfactant with a mixture of more weight efficient ingredients selected from polymers and enzymes.
  • a preferred composition uses lipase enzyme in combination with EPEI and a polyester soil release polymers to achieve excellent oily soil and particulate detergency at significantly lower in-wash surfactant levels than would normally be delivered from such a high performance laundry liquid.
  • a bleach catalyst may be included. A long list of such catalysts is given.
  • the non-bridged air bleaching catalyst preferred in WO2002/048307 (Unilever ) is specifically mentioned as being preferred for use in WO 2009/153184 .
  • Air bleaching catalysts as described and claimed in WO 002/48301 are referenced on page 48 lines 1-2 of WO 2009/153184 where it says "suitable bispidon catalyst materials and their action are described in WO 02/48301 ".
  • the combination of a specific amount of the selected air bleaching catalyst with a specific amount of lipase is not exemplified in WO 2009/153184 .
  • WO 02/48301 (Unilever) disclosed a group of bridged ligand air bleaching catalysts that included N2Py3o on page 30. There is no disclosure of this catalyst in combination with lipase, nor any suggestion that the combination would have synergistic effects on the air bleaching of curcuminoid (yellow and green curry) stains.
  • WO 2004/111174 discloses the use of anti-oxidant to protect the catalyst in liquids during storage.
  • the example showing improved perfume stability uses a bridged bleach catalyst of the correct type, but no lipase is present.
  • WO 02/50229 (Unilever ) that discloses to air bleach with a combination of metal catalyst and an air bleaching facilitator (unsaturated soap).
  • the presently claimed catalyst is not exemplified or used with lipase.
  • US 2003/0166485 discloses a combination of a lipase, lipogenase and bleach catalyst used in air bleaching mode.
  • the examples show the effect with a non- bridged ligand type of catalyst (MeN4Py)FeCl Cl.
  • the examples without any lipogenase show some benefit of the combination of a lipase with this non bridged bleach catalyst compared to use of the lipase alone or the catalyst alone.
  • a detergent liquid comprising:
  • R1 and R2 are independently selected from:
  • the catalyst is ([Fe(N2py3o)Cl]Cl) with structure (II):
  • Iron(1+) chloro[rel-1,5-dimethyl (1R,2S,4R,5S)-9,9-dihydroxy-3-methyl-2,4-di(2-pyridinyl- ⁇ N)-7-[(2-pyridinyl-KN)methyl]-3,7-diazabicyclo[3.3.1]nonane-1,5-dicarboxylate- ⁇ N3, ⁇ N7]-, chloride (1:1), (OC-6-63)-[CAS Registry Number 478945-46-9].
  • the composition further comprises ethoxylated polyethyleneimine (EPEI).
  • EPEI ethoxylated polyethyleneimine
  • SRP polyester soil release polymer
  • the in-bottle pH of the composition is acidic and lies in the range 6 to less than 7, preferably 6.1 to 6.9 and more preferably 6.3 to 6.7.
  • the bleach catalyst may be encapsulated.
  • the composition preferably comprises at least two further enzymes selected from protease, mannanase, amylase, cellulase and pectate lyase. Most preferably the composition comprises protease.
  • the composition may be a laundry detergent.
  • the anionic surfactant preferably comprises linear alkyl benzene sulphonate.
  • composition surfactant system may further comprise one or more of ethoxylated nonionic surfactant, amphoteric surfactant and ethoxylated anionic surfactant.
  • the amphoteric surfactant may be selected from carbobetaine and amine oxide and mixtures thereof.
  • the composition may be aqueous with a water content of greater than 20 wt%.
  • it may be non aqueous with a water content of less than 15 wt%, preferably less than 10 wt%.
  • Such a non aqueous composition may conveniently be contained in a water soluble sachet that can be added to water by a consumer.
  • the sachet is desirably made from a conventional water soluble film, for example a poly vinyl alcohol as is known in the art.
  • a method of air bleaching a surface on which there is a curcuminoid stain comprising treating the surface with a composition according to the invention any preceding claim and then exposing the surface to atmospheric air, preferably the exposure to air has a duration of at least 1 hour.
  • the composition may be applied to the surface in undiluted, from the bottle, form. Consumers prefer many types of cleaning composition to be offered as a liquid, hard surface cleaners and fabric washing liquids being leading examples.
  • the method may be performed by taking an aliquot of the composition and diluting it by at least 600 times its own weight of water to form a wash liquor and then contacting the surface with the wash liquor so formed.
  • the surface is cloth fabric and most preferably it is cotton.
  • the method involving dilution may take place in a front loading automatic washing machine.
  • the preferred catalyst used in this invention is given a shorthand code of [Fe(N2py3o)Cl]Cl - see WO 20/48301 .
  • the structure (II) for it is:
  • Iron(1+) chloro[rel-1,5-dimethyl (1R,2S,4R,5S)-9,9-dihydroxy-3-methyl-2,4-di(2-pyridinyl- ⁇ N)-7-[(2-pyridinyl- ⁇ N)methyl]-3,7-diazabicyclo[3.3.1]nonane-1,5-dicarboxylate- ⁇ N3,KN7]-, chloride (1:1), (OC-6-63)- [CAS Registry Number 478945-46-9].
  • a particular type of air bleaching catalyst as described in WO02/48301 has a surprisingly strong synergistic effect with lipase in terms of the visual removal of yellow curry (curcuminoid) stains when a washed stain is dried in contact with a liquid comprising the catalyst and the lipase (air bleaching effect).
  • the effect is particularly strong when high levels of the catalyst (and lipase) and low levels of surfactant are used. This may be due to the higher efficacy of the lipase when anionic surfactant is reduced.
  • the lipase catalyst synergy is therefore particularly suited to the low surfactant compositions of the type described in WO09153184 .
  • the amount of lipase should be at least 1 wt% to obtain the synergistic effect. 1 wt% is equivalent to 1000 LU per gram of the detergent composition. Preferably the lipase is 2000-20,000 LU per gram of the detergent composition.
  • Suitable lipase enzyme is obtainable from Humicola lanuginosa, Pseudomonas pseudoalcaligenes, or Rhizomucor miehei. Preferred lipase enzymes include those of bacterial or fungal origin. Chemically modified or protein engineered mutants are included. Most preferred lipases are obtainable from Humicola lanuginose.
  • the detergent compositions preferably comprise 2500-4,000 LU per gram of the detergent composition, of lipase enzyme. In this specification LU or lipase units are defined as they are in EP-A-258 068 (Novo Nordisk).
  • a further method of assessing the enzymatic activity is by measuring the reflectance at 460 nm according to standard techniques.
  • lipases examples include lipases from Humicola which comprise a polypeptide having an amino acid sequence which has at least 90% sequence identity with the wild-type lipase derived from Humicola lanuginose, 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.
  • lipases examples 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. stutzeri ( GB 1,372,034 ), P. fluorescens, Pseudomonas sp.
  • strain SD 705 ( WO 95/06720 and WO 96/27002 ), P. wisconsinensis ( WO 96/12012 ), a Bacillus lipase, e.g. from B. subtilis ( Dartois et al. (1993), Biochemica et Biophysica Acta, 1131, 253-360 ), B. stearothermophilus ( JP 64/744992 ) or B. pumilus ( WO 91/16422 ).
  • the preferred lipases have a high degree of homology with the wild-type lipase derived from Humicola lanuginose.
  • 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 .
  • LipolaseTM and Lipolase UltraTM LipexTM and LipocleanTM (Novozymes A/S).
  • lipase In addition to lipase one or more other enzymes may be present.
  • the presence of relatively high levels of calcium in the compositions of the invention has a beneficial effect on the turnover of certain enzymes, particularly lipase enzymes and preferably lipases from Humicola.
  • Suitable enzymes for the compositions of the invention can be found in the enzyme classes of the esterases and lipases, (EC 3.1.1. *, wherein the asterisk denotes any number).
  • Cutinases differ from classical lipases in that they do not possess a helical lid covering the catalytic binding site. Cutinases belong to a different subclass of enzymes (EC 3.1.1.50) and are regarded to be outside the scope of the present invention.
  • the enzyme to be used in the detergent compositions according to the invention can be produced by cloning the gene for the enzyme into a suitable production organism, such as Bacilli, or Pseudomonaceae, yeasts, such as Saccharomyces, Kluyveromyces, Hansenula or Pichia, or fungi like Aspergillus.
  • a suitable production organism such as Bacilli, or Pseudomonaceae, yeasts, such as Saccharomyces, Kluyveromyces, Hansenula or Pichia, or fungi like Aspergillus.
  • the preferred production organism is Aspergillus with especial preference for Aspergillus oryzae.
  • the lipase enzyme can be stabilised for use in a liquid detergent by various techniques as for example disclosed in US-A-4 261 868 and US-A-4 318 818 .
  • the selected bleach catalyst is a cross-bridged polydentate N-donor ligand capable of forming a complex with a transition metal, wherein said complex is capable of catalysing the bleaching of stains on fabrics by means of atmospheric oxygen.
  • the bleach catalyst is a very specific complex of Iron and a multicyclic organic ligand as described already in WO 02/48301 .
  • the preferred material is [Fe(N2py3o)Cl]Cl- see WO 02/48301 . Its structure (II) is:
  • Iron(1+) chloro[rel-1,5-dimethyl (1R,2S,4R,5S)-9,9-dihydroxy-3-methyl-2,4-di(2-pyridinyl- ⁇ N)-7-[(2-pyridinyl- ⁇ N)methyl]-3,7-diazabicyclo[3.3.1]nonane-1,5-dicarboxylate- ⁇ N3, ⁇ N7]-, chloride (1:1), (OC-6-63)- [CAS Registry Number 478945-46-9].
  • the bridged ligand catalysts are more stable under acidic conditions and the detergent liquids are therefore preferably acidic.
  • Such liquids are compatible with SRPs that suffer from hydrolysis when included in alkaline liquids (especially if TEA is present).
  • Texcare SRN170 has been found to be susceptible to alkaline hydrolysis in laundry liquids.
  • the composition preferably comprises from 0.005 to 2 wt% of anti-oxidant. More preferably, the anti-oxidant is present at a concentration in the range of 0.01 to 0.08 wt%.
  • Anti-oxidants are substances as described in Kirk-Othmer (Vol 3, pg 424) and in Uhlmans Encyclopaedia (Vol 3, pg 91 ).
  • One class of anti-oxidants used in the present invention is alkylated phenols.
  • hindered phenolic compounds of alkylated phenols according to this formula is 2,6-di-tert-butyl-hydroxy- toluene (BHT).
  • the antioxidant used in the composition of the invention may be selected from the group consisting of a-, y-, 8-tocopherol, ethoxyquin, 2,2,4-trimethyl-1,2- dihydroquinoline, 2,6-di-tert-butyl hydroquinone, tert-butyl- hydroxy anisole, lignosulphonic acid and salts thereof, and mixtures thereof.
  • Ethoxyquin (1,2-dihydro-6- ethoxy-2,2,4-trimethylchinolin) is marketed under the name RaluquinTM by the company Rashig.
  • antioxidants 6 hydroxy-2, 5, 7, 8-tetra-methylchroman-2-carboxylic acid (TroloxTM) and 1, 2-benzisothiazoline-3-one (Proxel GXL).
  • a further class of anti-oxidants which may be suitable for use in the present invention is a benzofuran or benzopyran derivative.
  • Anti-oxidants such as tocopherol sorbate, butylated hydroxy benzoic acids and their salts, gallic acid and its alkyl esters, uric acid and its salts and alkyl esters, sorbic acid and its salts, and dihydroxy fumaric acid and its salts may also be used.
  • anti-oxidants for use in the present invention are 2,6-di-tert-butyl-hydroxy-toluene (BHT), ⁇ , ⁇ , ⁇ , ⁇ -, tocopherol and mixtures thereof, 6-hydroxy-2, 5, 7, 8-tetra-methylchroman-2- carboxylic acid (TroloxTM), 1, 2-benzisothiazoline-3-one (Proxel GXL) and mixtures thereof.
  • BHT 2,6-di-tert-butyl-hydroxy-toluene
  • TroloxTM 6-hydroxy-2, 5, 7, 8-tetra-methylchroman-2- carboxylic acid
  • Proxel GXL 2-benzisothiazoline-3-one
  • the most preferred anti-oxidants are 2,6-di-tert-butyl-hydroxy-toluene (BHT, 1, 2 benzisothiazoline-3-one (Proxel GXL TM) and mixtures thereof.
  • Surfactants assist in removing soil from the textile materials and also assist in maintaining removed soil in solution or suspension in the wash liquor. Blends of anionic and nonionic surfactants are a preferred feature of the present invention.
  • the amount of anionic surfactant is at least 5 wt% and preferably at least 10 wt%. Preferably, anionic surfactant forms the majority of the surfactant (a).
  • the anionic surfactant may comprise at least 5 wt% linear alkyl benzene sulphonate.
  • anionic surfactants are alkylbenzene sulphonates, particularly linear alkylbenzene sulphonates 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.
  • 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 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.
  • 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.
  • 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.
  • the composition may comprise up to 10 wt% of a carbobetaine or an amine oxide or mixtures thereof.
  • the amine oxide has the formula: R 1 N(O)(CH 2 R 2 ) 2
  • R 1 is a long chain moiety each CH 2 R 2 are short chain moieties.
  • 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.
  • Preferred amine oxides have R 1 is C 8 -C 18 alkyl, and 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 dodecyidimethylamine oxide or DDAO. Such an amine oxide material is commercially available from Huntsman 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: 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.
  • a preferred zwitterionic carbobetaine material is available from Huntsman under the name Empigen® BB. Betaines, improve particulate soil detergency in the compositions of the invention.
  • the surfactant system may comprise, in addition to at least 5 wt% linear alkyl benzene sulphonate, at least 5 wt% ethoxylated nonionic surfactant and at least 1 wt% of surfactant selected from amine oxide, carbobetaine and mixtures thereof and ethoxylated anionic surfactant.
  • surfactants than the preferred LAS, SLES, nonionic and amine oxide/ carbobetaine may be added to the mixture of detersive surfactants.
  • cationic surfactants are preferably substantially absent.
  • alkyl sulphate surfactant may be used, especially the non-ethoxylated C 12-15 primary and secondary alkyl sulphates.
  • compositions are as described in WO 2009/153184 .
  • EPEI and polyester soil release polymer are most preferred components of the detergent liquids and are advantageously used in combination and at high levels.
  • a particularly preferred class of polymer for use in the present invention is polyethylene imine, preferably modified polyethylene imine.
  • 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. 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 of about 300 to about 10000 weight average molecular weight; 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 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.
  • the polyethyleneimine polymer is present in the composition preferably at a level of between 0.01 and 25 wt%, but more preferably at a level of at feast 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.
  • a soil release polymer preferably of the PET POET type
  • Acidic compositions according to the invention are particularly suited to the types of soil release polymers disclosed in WO09153184 since they tend to decompose when stored under alkaline conditions.
  • an alkaline stable type of polyester soil release polymer may be used.
  • the composition may comprise at least 2 wt% polyester soil release polymer.
  • Dye transfer inhibition polymers, anti redeposition polymers and cotton soil release polymers, especially those based on modified cellulosic materials may also be used in the compositions of the present invention.
  • the Detergent liquids preferably do not contain any additional conventional bleach system.
  • peroxy bleach compounds for example, inorganic persalts or organic peroxyacids, capable of yielding hydrogen peroxide in aqueous solution are absent.
  • composition may comprise other ingredients as set forth in WO 2009/153184 .
  • Prototype fabric washing liquids were prepared according to the compositions given in table 1. Knitted cotton fabric swatches stained with yellow curry supplied by Warwick Equest Ltd. - where the stain is applied to washed but otherwise untreated cotton - were washed at 25°C for 30 minutes with unstained polyester and cotton ballast such that the liquor/cloth ratio was 25/1, using 1.3g fabric washing liquid with composition as shown in Table 1 in one litre of 26°FH (26 degrees French Hardness according to the Internationally recognised hardness scale where 1 degree French is defined as 10 milligrams of calcium carbonate per litre of water, equivalent to 10 ppm). After removing the swatches from the wash liquor, they were rinsed twice in water at 25°C, each rinse being of thirty seconds duration. After the second rinse the swatches were removed from the rinse and wrung out by hand, to remove excess water before being laid flat and allowed to air dry for two days.
  • ⁇ E values were measured before washing, and after washing and drying for the two days, using a Hunterlab XE reflectance spectrophotometer. ⁇ E is measured relative to a clean unstained piece of cotton (of the same type as used for making the stains). The difference between the before wash and after drying values of ⁇ E is recorded as ⁇ ( ⁇ E), such that higher numbers denote better cleaning.
  • Table 1 - Concentrated Liquid Compositions Ingredient Ingredient Level (100%) Composition A B C 1 Demin water To 100 To 100 To 100 MPG 20.00 20.00 20.00 20.00 NaOH to pH 6.5 to pH 6.5 to pH 6.5 to pH 6.5 TEA 2.00 2.00 2.00 2.00 Fluorescer 0.1 0.1 0.1 0.1 NI 7EO 12.74 12.74 12.74 12.74 LAS acid 8.49 8.49 8.49 8.49 8.49 Fatty acid 1.5 1.5 1.5 1.5 1.5 SLES 3EO 4.24 4.24 4.24 4.24 Empigen® BB 1.5 1.5 1.5 1.5 EPEI 5.5 5.5 5.5 5.5 SRP 3.75 3.75 3.75 Perfume 2.43 2.43 2.43 2.43 Protease enzyme 1.75 1.75 1.75 Amylase enzyme 0.70 0.70 0.70 0.70 Mannanase enzyme 0.70 0.70 0.70 0.70 Patent Blue V85 0.00068 0.00068 0.00068 0.00068 Acid Yellow 23 0.0001 0.0001 0.0001 0.0001 Bleach Catalyst - - 0.07 0.07 Lipas
  • the molecular weight of the bridged ligand catalyst with structure (II) according to the invention is 641.85 and the molecular weight of the catalyst of structure (III) is 507.85. It would be expected that the prior art catalyst of structure (III) would be more effective on an equal weight basis if it was an alternative as suggested by US2003/166485 . Testing was done using the concentrated liquid composition given in Table 3. The lipase used was Lipex 100L ex Novozymes and it was added over the side to each tergo pot, including the zero catalyst control (equivalent to 1.75% Lipex in product)
  • test protocol was otherwise the same as for example 1 except that the test cloths were knitted cotton fabric swatches stained with Rogan Josh supplied by Warwick Equest Ltd. - where the stain is applied to washed but otherwise untreated cotton.
  • the Rogan Josh used contained turmeric as one of the spices. Curcumin is a component of turmeric and is responsible for its yellow colour. Table 3 Component % as 100% Demin.
  • the stain removal data (expressed as ⁇ ( ⁇ E)) for each catalyst at different levels of inclusion is given in Table 4.
  • the catalyst according to the invention provides superior air bleaching with lipase compared to the one in the prior art.
  • Table 4 Catalyst Level used wt% Structure (III) Structure (II) 0.000 16.8 16.8 0.014 19.3 21.8 0.028 19.3 21.6 0.042 19.4 21.8 0.056 21.8 22.9 0.070 21.0 22.6
  • Example 2 The comparative testing done in Example 2 was also carried out using Lipoclean as the Lipase enzyme, as was used for Example 1. Again, the catalyst according to the invention outperformed that of the prior art when used with the lipase to air bleach yellow curry stains.

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Claims (16)

  1. Composition liquide de détergent comprenant :
    a) de 20 à 70 % en masse de tensioactif, comprenant au moins 5 % en masse (rapporté à la composition liquide totale) de tensioactif anionique,
    b) au moins 1 000 LU par gramme de la lipase de composition liquide,
    c) de 0,05 à 0,3 % en masse d'un catalyseur de métal de transition, le catalyseur étant un ligand de la formule (I) complexé avec un métal de transition, choisi parmi Fe(II) et Fe(III),
    Figure imgb0010
    où R1 et R2 sont indépendamment choisis parmi :
    un groupe alkyle en C1-C4,
    un groupe aryle en C6-C10, et
    un groupe contenant un hétéroatome capable de coordination à un métal de transition, dans lequel au moins un de R1 et R2 est le groupe contenant l'hétéroatome ; de préférence au moins un de R1 ou R2 est le groupe pyridin-2-ylméthyle, encore mieux R1 est le groupe pyridin-2-yl-méthyle et R2 est le groupe méthyle ;
    R3 et R4 sont indépendamment choisis parmi l'hydrogène, un groupe alkyle en C1-C8, (alkylène en C1-C8)-O-(alkyle en C1-C8), (alkylène en C1-C8)-O-(aryle en C6-C10), aryle en C6-C10, hydroxyalkyle en C1-C8, et -(CH2)nC(O)OR5,
    où R5 est indépendamment choisi parmi : l'hydrogène, un groupe alkyle en C1-C4, n est égal à de 0 à 4, et des mélanges de ceux-ci ; de préférence R3=R4-C(O)OMe ; et,
    chaque R est indépendamment choisi parmi : l'hydrogène, F, CI, Br, un groupe hydroxyle, (alkylène en C1-C4)O-, -NH-CO-H, -NH-CO-(alkyle en C1-C4), -NH2, -NH-(alkyle en C1-C4), et alkyle en C1-C4 ; de préférence chaque R est l'hydrogène ;
    X est choisi parmi C=O, -[C(R6)2]y- où Y est égal à de 0 à 3, de préférence 1, chaque R6 est indépendamment choisi parmi l'hydrogène, un groupe hydroxyle, alcoxy en C1-C4 et alkyle en C1-C4, de préférence X est C=O.
  2. Composition selon la revendication 1, dans laquelle R1 est le groupe pyridin-2-ylméthyle.
  3. Composition selon l'une quelconque des revendications précédentes, dans laquelle le catalyseur est ([Fe(N2py3o)Cl]Cl) avec la structure (II) :
    Figure imgb0011
     également connue comme fer(1+), chloro[rel-1,5-diméthyl(1R, 2S, 4R, 5S)-9,9-dihydroxy-3-méthyl-2,4-di(2-pyridinyl-κN)-7-[(2-pyridinyl-κN)méthyl]-3,7-diazabicyclo[3.3.1]nonane-1,5-dicarboxylate-κN3, κN7]-, chlorure (1:1), (OC-6-63)- [numéro CAS 478945-46-9].
  4. Composition selon l'une quelconque des revendications précédentes dans laquelle, la composition comprend de plus au moins 3 % en masse de polyéthylèneimine éthoxylée (EPEI).
  5. Composition selon l'une quelconque des revendications précédentes dans laquelle, la composition comprend de plus au moins 2 % en masse de polymère libérant la saleté de polyester.
  6. Composition selon l'une quelconque des revendications précédentes, dans laquelle la composition en bouteille est acide avec un pH dans l'intervalle de 6,0 à moins de 7, de préférence de 6,3 à 6,7.
  7. Composition selon l'une quelconque des revendications précédentes, dans laquelle la composition comprend de plus au moins deux autres enzymes choisies parmi une protéase, mannanase, amylase, cellulase et pectate lyase, de préférence une protéase est présente.
  8. Composition selon l'une quelconque des revendications précédentes, dans laquelle le tensioactif anionique comprend au moins 5 % en masse de benzènesulfonate d'alkyle linéaire.
  9. Composition selon la revendication 8, dans laquelle le système de tensioactif comprend de plus au moins 5 % en masse de tensioactif non ionique éthoxylé, au moins 1 % en masse de tensioactif choisi parmi un oxyde d'amine, une carbobétaïne et des mélanges de ceux-ci, et un tensioactif anionique éthoxylé.
  10. Procédé de blanchiment à l'air d'une surface sur laquelle il existe une tache de curcuminoïde le procédé comprenant le traitement de la surface avec une composition selon l'une quelconque des revendications précédentes et l'exposition subséquente de la surface à de l'air atmosphérique pendant au moins 1 heure.
  11. Procédé selon la revendication 10, dans lequel la composition est appliquée non diluée.
  12. Procédé selon la revendication 10, dans lequel la composition est diluée au moins 600 fois avec de l'eau avant d'être mise en contact avec la surface.
  13. Procédé selon la revendication 10, dans lequel la surface est un textile de vêtement.
  14. Procédé selon la revendication 13, dans lequel le textile comprend du coton.
  15. Procédé selon la revendication 12, dans lequel le contact avec la composition diluée se fait dans une machine de lavage automatique à chargement frontal.
  16. Utilisation d'une combinaison du catalyseur selon la revendication 3 et d'une lipase pour un blanchiment à l'air d'une tache de curcuminoïde.
EP12788520.0A 2011-12-20 2012-11-19 Détergents liquides comprenant une lipase et un catalyseur de blanchiment Not-in-force EP2809762B1 (fr)

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EP12788520.0A EP2809762B1 (fr) 2011-12-20 2012-11-19 Détergents liquides comprenant une lipase et un catalyseur de blanchiment
PCT/EP2012/072973 WO2013092051A1 (fr) 2011-12-20 2012-11-19 Détergents liquides comprenant une lipase et un catalyseur de blanchiment

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CN118871559A (zh) * 2021-12-21 2024-10-29 诺维信公司 包含脂肪酶和加强剂的组合物
EP4299703A1 (fr) 2022-06-27 2024-01-03 The Procter & Gamble Company Composition de détergent de blanchisserie particulaire solide à écoulement libre
EP4299701B1 (fr) * 2022-06-27 2025-03-26 The Procter & Gamble Company Composition de détergent de blanchisserie particulaire solide à écoulement libre
EP4299702A1 (fr) * 2022-06-27 2024-01-03 The Procter & Gamble Company Composition de détergent de blanchisserie particulaire solide à écoulement libre
EP4299704B1 (fr) * 2022-06-27 2026-01-07 The Procter & Gamble Company Procédé de lavage et de séchage de tissus
DE102023109600A1 (de) 2023-04-17 2024-10-17 Gertraud Scholz Anionische Soil Release Polyester und deren Verwendung

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ZA201403702B (en) 2015-12-23
EP2809762A1 (fr) 2014-12-10
CN103998593B (zh) 2017-05-03
ES2569052T3 (es) 2016-05-06
BR112014014724A8 (pt) 2017-07-04
BR112014014724A2 (pt) 2017-06-13
WO2013092051A1 (fr) 2013-06-27
CN103998593A (zh) 2014-08-20

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