EP2794832B1 - Détergents liquides isotropes comprenant un polymère détachant - Google Patents

Détergents liquides isotropes comprenant un polymère détachant Download PDF

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Publication number
EP2794832B1
EP2794832B1 EP12790866.3A EP12790866A EP2794832B1 EP 2794832 B1 EP2794832 B1 EP 2794832B1 EP 12790866 A EP12790866 A EP 12790866A EP 2794832 B1 EP2794832 B1 EP 2794832B1
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EP
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Prior art keywords
composition
acid
composition according
bottle
surfactant
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German (de)
English (en)
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EP2794832A1 (fr
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Seema CHOPRA-GANDHI
Andrew David Green
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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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
    • C11D1/00—Detergent compositions based essentially on surface-active compounds; Use of these compounds as a detergent
    • C11D1/02—Anionic compounds
    • C11D1/12—Sulfonic acids or sulfuric acid esters; Salts thereof
    • C11D1/22—Sulfonic acids or sulfuric acid esters; Salts thereof derived from aromatic compounds
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D1/00—Detergent compositions based essentially on surface-active compounds; Use of these compounds as a detergent
    • C11D1/02—Anionic compounds
    • C11D1/12—Sulfonic acids or sulfuric acid esters; Salts thereof
    • C11D1/29—Sulfates of polyoxyalkylene ethers
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D1/00—Detergent compositions based essentially on surface-active compounds; Use of these compounds as a detergent
    • C11D1/02—Anionic compounds
    • C11D1/37—Mixtures of compounds all of which are anionic
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D10/00—Compositions of detergents, not provided for by one single preceding group
    • C11D10/04—Compositions of detergents, not provided for by one single preceding group based on mixtures of surface-active non-soap compounds and soap
    • C11D10/042—Compositions of detergents, not provided for by one single preceding group based on mixtures of surface-active non-soap compounds and soap based on anionic surface-active compounds and soap
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
    • C11D3/16—Organic compounds
    • C11D3/26—Organic compounds containing nitrogen
    • C11D3/30—Amines; Substituted amines ; Quaternized amines
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • 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

Definitions

  • This invention relates to isotropic liquid detergent compositions comprising water, hydrotrope, anionic sulphonate or sulphate surfactant and a polyester based soil release polymer.
  • WO09153184 suggests that a laundry detergent liquid concentrate may be designed by replacing surfactant with a mixture of more weight efficient ingredients selected from polymers and enzymes.
  • a preferred composition uses a combination of ethoxylated polyethylene imine (EPEI) and a polyester soil release polymer (SRP) to achieve excellent oily soil and particulate detergency at significantly lower in-wash surfactant levels than would normally be delivered from a high performance liquid.
  • EPEI ethoxylated polyethylene imine
  • SRP polyester soil release polymer
  • the exemplified compositions comprise anionic surfactant comprising linear alkyl benzene sulphonate neutralised with sodium hydroxide and further comprise soap formed by neutralisation of fatty acid by sodium hydroxide.
  • the compositions are alkaline. It has been found that the SRP used for the examples suffers from alkaline hydrolysis and that this is catalysed by the use of triethanolamine (TEA) in the compositions.
  • TAA triethanolamine
  • a liquid softening and anti-static nonionic detergent composition comprises as essential ingredients a nonionic detergent an anionic detergent a cationic fabric softener-anti-static agent and a soil release promoting polymer of a water-soluble fraction of the polyethylene terephthalate-polyoxyethylene terephthalate type.
  • alkaline material include mono-, di- and trialkanolamines, alkyl amines, ammonium hydroxide and alkali metal hydroxides. Of these the preferred materials are the alkanolamines, preferably the trialkanolamines and of these especially triethanolamine.
  • the pH of the final liquid detergent, containing such a basic material will usually be neutral or slightly basic. Satisfactory pH ranges are from 7 to 10, preferably about 7.5 to 9.5.
  • WO9742286 (P&G) teaches on p3 that laundry detergents typically have a pH greater than 7.5. According to p9 SRP containing compositions it discloses have a pH of from about 7.2 to about 8.9 when measured as a 10% solution in water.
  • US4785060 discloses PET POET SRPs of high molecular weight made using a mixed catalyst system. These SRPs are said to retain their performance at high in wash pH in the presence of a detergency builder. They are taught to be included in both solid and liquid detergent compositions. The disclosure teaches to minimise the inclusion of alkanolamines such as TEA and ionisable salts such as Na. It is taught at column 10 lines 13 to 15 that it is preferred that the neutralizing agent employed, usually to increase the pH of the liquid detergent mixture, will be sodium hydroxide. At lines 17 to 18 it continues that "Triethanolamine salts and free triethanolamine should generally be avoided”. The pH will be in the range of 6 to 10, preferably 6.1 to 8.9 and often more preferably 6.5 to 7.5.
  • US4759876 discloses a soil release promoting liquid detergent composition
  • the composition further comprises a stabilizing proportion of a stabilizer for enzyme(s) which also acts as a buffer for the liquid detergent composition to maintain the pH in a certain neutral or slightly acidic range to stabilize the SRP and the fluorescent brightener. It is said that the composition "substantially retains" its soil hydrolyzing fluorescent brightening and soil release promoting characteristics on storage so that laundry washed with it is effectively cleaned brightened and treated.
  • US5110506 shows that the performance was not as good as suggested by '876. Furthermore it is clear from the disclosure in '876 that the pH drifts to acid on storage.
  • the enzyme stabiliser/ buffer is said to keep the pH at 6.2 or higher.
  • a pH range of 6.2 to 6.5 after storage is given.
  • a further range of pH 5.8 to 7 is also given as one that does not destabilise the polymer.
  • GB1466639 discloses detergent liquids with ethanolamine neutralised surfactant and SRP. Some free TEA is included to keep the wash water alkaline. Two different types of liquids are disclosed. In the first type the specific nonionic surfactant selected gives sufficient physical stability of the composition. In the second type fatty acid (soap) is included to provide long term storage stability.
  • Example 1 appears to be an example of the second type of composition. It comprises oleic acid TEA salt 1.5% and SRP 5% (from table 1). This is found to be an alkaline composition.
  • US4411831 discloses a stable aqueous detergent composition having enhanced soil release properties and consisting essentially of SRP (with LAS and nonionic and a buffer sufficient to maintain the pH of the aqueous composition within the range of 5.0 to 9.0.pref 6.5 to 7.5.
  • the examples used Zelcon 4780 SRP in a main wash composition comprising LAS and nonionic and pH adjusted to 7. SXS was used as hydrotrope. No TEA or soap is used in the examples.
  • the disclosure teaches that the comparative liquids without buffer generate an acid pH on storage. The acid pH is said to be detrimental to brighteners. We understand that the acid pH is generated due to decomposition of the SRP.
  • the solution adopted is to add a buffer to stabilise the pH.
  • Suitable buffers include bicarbonates, orthophosphate borates and alkanolamine hydrochlorides.
  • US4713194 discusses the vulnerability of SRP to degradation in alkaline environments and proposes to protect the SRP by enrobing if it is to be used in granular compositions, or by adjusting the product pH to be between 7.0 and 8.5 if it is to be used in liquid compositions.
  • the examples contain coco fatty acid at high levels.
  • US6262007 describes acidic detergent liquids which include SRP to reduce the increase of viscosity as the temperature drops.
  • Some examples include TEA but not with hydrotrope or fatty acid.
  • the composition has an in-bottle pH of 6.3 to 6.7.
  • in-bottle we mean in whatever container or pack the liquid is stored. It could be a plastic pack in the form of a bottle, squeezable or rigid, stored upright or inverted, or a unit dose format such as a soluble pouch, or a sachet.
  • Fatty acid provides buffering capacity but its inclusion leads to phase separation of acidic compositions at low temperature. Thus it can only be included at relatively low levels. It cannot be totally removed as material used to neutralise the anionic surfactant a), preferably sodium hydroxide or monsethanolamine (MEA), cannot stabilise the composition on its own.
  • the fatty acid is saturated. Most preferably it is used in an amount of from 0.5 to 1.5 wt%.
  • TEA aids the stability of the fatty acid and TEA Is therefore included at as high a level as can be tolerated by the SRP.
  • the amount of TEA is preferably up to 3.7 wt%, and most preferably lies in the range 2.0 to 3.5 wt%.
  • the one or more materials the pKa of whose conjugate acid(s) lies more than 2 units higher than the in-bottle pH of the detergent liquid composition comprises 0.08 to 0.25 wt% NaOH and/or monoethanolamina (mean preferably 0.1 to 0.23 wt% (MEA).
  • MEA monoethanolamina
  • the material used to neutralise anionic surfactant acid to make anionic surfactant a which material the pKa of Whose conjugate acid(s) lies more than 2 units higher than the in-bottle pH of the detergent liquid composition, does not act significantly as a buffer at the in-bottle pH at which the composition is stored, In contrast the TEA does act as a buffer at the mildly acidic in-bottle pH.
  • the SRP is of the type that deposits from a wash solution onto polyester. It preferably has a polyester substantive part formed by condensation of terephthalic acid ester and diol, preferably 1,2 propanediol, and further comprises an and cap hydrophilic part comprising repeat units of ethylene oxide capped with an alkyl group. It may be used in an amount of more than 0.5 wt% and may be present up to a level of 16 wt%. Mixtures of different SRPs may be used.
  • the liquid will typically comprise a hydrotrope.
  • the level of hydrotrope will be at least 5 wt%, preferably at least 9 wt%, more preferably at least 14 wt%.
  • the amount of hydrotrope is preferably less than 25 wt% and most preferably less than 20 wt% of the compositions.
  • a preferred hydrotrope is 1,2 propanediol (MPG).
  • composition comprises at least 3, preferably at least 5 wt% ethoxylated polyethylene imine (EPEI) to improve particulate soil removal.
  • EPEI ethoxylated polyethylene imine
  • compositions of the invention may contain other ingredients.
  • ingredients include viscosity modifiers, foam boosting agents, preservatives (e.g. bactericides), pH buffering agents, polyelectrolytes, anti-shrinking agents, anti-wrinkle agents, anti-oxidants, sunscreens, anticorrosion agents, drape imparting agents, anti-static agents and ironing aids, colorants, pearlisers and/or opacifiers, and shading dye.
  • the amount of detersive surfactant makes up at least 10 wt% of the total liquid composition, preferably it makes up from 12 to 60 wt%.
  • the compositions according to the invention most preferably have total active detersive surfactant levels of at least 15 wt%.
  • compositions may be concentrated compositions designed to be added to a 10 litre wash 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 also be concentrated compositions designed for hand wash or top loading automatic washing machines. In hand wash less water may be used and in top loading automatic washing machines a higher amount of water would normally be used. The dose of detergent liquid is adjusted accordingly to give similar wash liquor concentrations.
  • Surfactants assist in removing soil from the textile materials grid also assist in maintaining removed soil in solution or suspension its the wash liquor.
  • Aniodic 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%.
  • the anionic surfactant forms the majority of the non soap surfactant (a).
  • alkyl sulphonated are alkylbenzene sulphonates, particularly linear alkylbenzene sulphonates having an alkyl chain length of C 8 -C 10 .
  • Preferred linear alkyl benzene sulphonate surfactants are Detal LAS with an alkyl chain length of from 8 to 15, more preferably 12 to 14.
  • the composition comprises an alkyl polyethoxylate sulphate anionic surfactant of the formula (I); RO(C 2 H 1 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 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 launyrl ether sulphate
  • It is the sodium salt of lauryl ether sulphonio 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.
  • composition may comprise up to 10 wt% of an amine oxide of 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 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: 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 carbobetaine, is present.
  • a preferred zwitterionic material is a carbobetaine available from Huntsman under the name Empigen® BB. Carbobetaines, improve particulate soil detergency in the compositions of the invention.
  • compositions comprise at least 1 wt% of amine oxide or carbobetaine or mixtures thereof.
  • surfactants than the preferred LAS, SLES, nonionic and amphoteric (betaine and / or amine oxide) 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.
  • a particularly preferred class of polymer for use in combination with the polyester soil release polymer (SRP) is ethoxylated polyethyleneimine (EPEI).
  • EPEI ethoxylated polyethyleneimine
  • 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.
  • 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 and nonionic.
  • 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 EPEI polymer When used the EPEI polymer is present in the composition preferably at a level of up to 25 wt%, and preferably at a level of at least 3 wt% more preferably from 4 to 15 wt% and most preferably at least 5 wt%.
  • the ratio of non-soap surfactant to EPEI is from 2:1 to 7:1, preferably from 3:1 to 6:1, or even to 5:1.
  • polyester soil release polymer there may be used dye transfer inhibition polymers, anti redeposition polymers and cotton soil release polymers, especially those based on modified cellulosic materials.
  • 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.
  • suitable hydrotropes there may be mentioned as preferred: MPG (monopropylene glycol), glycerol, sodium cumene sulphonate, ethanol, other glycols, e.g. di propylene glycol, diethers and urea.
  • At least one or more enzymes may be present in the compositions.
  • at least two, more preferably at least three different classes of enzymes are used in combination.
  • Lipase is a particularly preferred enzyme.
  • the composition may comprise from about 50 to about 20000 LU/g of a lipase. Preferably at least 800LU/g.
  • 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 Ianuginose, 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 LipocleanTM 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. stutzeri ( GB 1,372,034 ), 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 .
  • LipolaseTM and Lipolase UltraTM LipexTM and LipocleanTM (Novozymes A/S).
  • lipase In addition to, or as an alternative 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.
  • the preferred lipases include first wash lipases derived from Humicola lanuginosa strain DSM 4109 available under the LipexTM brand from Novozymes. A similar enzyme from Novozymes but believed to fall outside of the above definition is sold by Novozymes under the name LipocleanTM and this is also preferred.
  • 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. the fungal cellulases produced from Humicola insolens, Thielavia terrestris, Myceliophthora thermophila, and Fusarium oxysporum disclosed in US 4,435,307 , US 5,648,263 , US 5,691,178 , US 5,776,757 , WO 89/09259 , WO 96/029397 , and WO 98/012307 .
  • cellulases include CelluzymeTM, CarezymeTM, EndolaseTM, RenozymeTM (Novozymes A/S), ClazinaseTM and Puradax HATM (Genencor International Inc.), and KAC-500(B)TM (Kao Corporation).
  • 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., (1996) Mol. Plant-Microbe interact. 8: 331-334 and Henrissat et al., (1995) Plant Physiol, 107: 963-976 .
  • Specifically contemplated pectate lyases are disclosed in WO 99/27083 and WO 99/27084 .
  • pectate lyases derived from Baoillus Ilcheniformis
  • 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 021006442 .
  • 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 94/26576 ).
  • 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
  • a lignin compound may be used in the composition in an amount that can be optimised by trial and error.
  • Lignin is a component of all vascular plants, found mostly between cellular structures but also within the cells and in the cell walls.
  • the lignin compound comprises a lignin polymer and more preferably it is a modified lignin polymer.
  • a modified lignin polymer as used herein is lignin that has been subjected to a chemical reaction to covalently attach chemical moieties to the lignin. The attached chemical moieties are preferably randomly substituted.
  • Preferred modified lignin polymers are lignins that have been substituted with anionic, cationic or alkoxy groups, or mixtures thereof. Preferably the substitution occurs on the aliphatic portion of the lignin and is random.
  • the modified lignin polymer is substituted with an anionic group, and preferably it is a sulfonate.
  • a preferred cationic group is a quanternary amine.
  • Preferred alkoxy groups are polyalkylene oxide chains having repeat units of alkoxy moieties in the range from 5 to 30, most preferably ethoxy.
  • the modified lignin sulfonate is substituted with anionic or alkoxy groups.
  • Modified lignin polymers are discussed in WO/2010/033743 .
  • the modified lignin polymer is lignin sulfonate (lignosulfonate).
  • Lignin sulfonate may be obtained by the Howard process.
  • Exemplary lignin sulfonate may be obtained from a variety of sources including hardwoods, softwoods and recycling or effluent streams.
  • the lignin sulfonate may be utilized in crude or pure forms, e.g., in an "as is” or whole liquor condition, or in a purified lignin sulfonate form from which or in which sugars and other saccharide constituents have been removed or destroyed, or from which or in which inorganic constituents have been partially or fully eliminated.
  • the lignin sulfonate may be utilized in salt forms including calcium lignin sulfonate, sodium lignin sulfonate, ammonium lignin sulfonate, potassium lignin sulfonate, magnesium lignin sulfonate and mixtures or blends thereof.
  • the lignin sulfonate preferably has a weight average molecular weight of from 2000 to 100000.
  • Their basic structural unit is phenylpropane.
  • the degree of sulfonation is preferably from 0.3 and 1.0 sulfate groups per phenylpropane unit.
  • Lignin sulfonate are available from a number of suppliers including Borregaard LignoTech, Georgia-Pacific Corporation, Lenzing AG and Tembec Inc. Lignin sulfonates are discussed in Lauten, R. A., Myrvold, B. O. and Gundersen, S. A. (2010) New Developments in the Commercial Utilization of Lignosulfonates, in Surfactants from Renewable Resources (eds M. Kjellin and I. Johansson), John Wiley & Sons, Ltd, Chichester, UK .
  • 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-sulfoslyryl)biphenyl.
  • Detergent compositions according to the invention may comprise a weight efficient bleach system. Such systems typically do not utilise the conventional percarbonate and 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%.
  • the catalyst may be protected, for example by encapsulation.
  • 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.
  • Suitable and preferred classes of dyes are as described in WO09/153184 .
  • 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.
  • DEQUESTTM organic phosphonate type sequestering agents sold by Thermphos and alkanehydroxy phosphonates.
  • a particularly preferred sequestrant is HEDP sold by Thermphos as Dequest® 2010 and also known as 1-Hydroxyethylidene -1,1,-diphosphonic acid. Also suitable, but less preferred is Dequest® 2066 (Diethylenetriamine penta(methylene phosphonic acid or Heptasodium DTPMP).
  • 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 SOKALANTM.
  • 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.
  • 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 in polymeric film adapted to be insoluble until added to the wash water. More preferred the liquids are supplied in multiuse plastics packs with a top or bottom closure. A dosing measure may be supplied with the pack either as a part of the cap or as an integrated system.
  • liquids according to the invention are intended to 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, the stable soil release polymer and optional additional high efficacy cleaning ingredients, such as EPEI.
  • the invention is also suitable for the more conventional dosage levels of about 35 ml. To obtain suitable liquids of this type all that is necessary is to add further water and possibly perfume to the 20ml type of liquid.
  • the soil release polymers claimed are also stable in these more dilute compositions.
  • MPG mono propylene glycol.
  • TEA triethanolamine.
  • NI 7EO is C12-15 alcohol ethoxylate 7EO nonionic Neodol® 25-7 (ex Shell Chemicals).
  • LAS acid is C12-14 linear alkylbenzene sulphonic acid.
  • Prifac® 5908 is saturated lauric fatty acid ex Croda.
  • SLES 3EO is sodium lauryl ether sulphate with 3 moles EO.
  • Empigen® BB is an alkyl betaine ex Huntsman (Coco dimethyl carbobetaine).
  • EPEI is Sokalan HP20 - ethoxylated polyethylene imine cleaning polymer: PEI(600) 20EO ex BASF.
  • Perfume is free oil perfume.
  • SRP soil release polymer.
  • Prifac® 5908 is saturated lauric fatty acid ex Croda.
  • MEA Monoethanolamine. NaOH is 47% sodium hydroxide solution.
  • Dequest® 2066 is Diethylenetriamine penta(methylene phosphonic acid (or Heptasodium DTPMP).
  • Dequest® 2010 is HEDP (1-Hydroxyethylidene -1,1,-diphosphonic acid).
  • Lipex® is Lipex 100L ex Novozymes.
  • Carezyme® is a cellulase ex Novozymes.
  • Stainzyme 12L is an amylase formulated for liquids ex Novozymes. Mannaway is a mannanase ex Novozymes.
  • a detergent liquid should be pH robust on a plus or minus 5 wt% ingredient to allow for manufacturing variability. To obtain that robustness It is necessary to Include buffer into the liquid, The buffers used are TEA (pKa 7.8) and Prifac 5908 fatty acid (pKa unknown because it is a mixture).
  • Prifac 5908 was used. At this level the fatty acid has a direct Impact on low temperature instability, consequently the level of fatty acid has been reduced to improve the low temperature stability (in 20 ml liquid to 1.71% and correspondingly 0.85% for 35 ml compositions). The impact on antifoaming was checked and found to be acceptable. The impact of reduced Prifac 5908 on buffering and pH control was also checked with the 20ml compositions given in table 3 and found to be acceptable (table 4).
  • the liquid of table 3 has no pH control if there is no Prifac 5908 or TEA. Acceptable pH control can be achieved with 1.5% Prifac 5908 and at least 1 % TEA. With 0% TEA the upper pH region is controlled but the lower pH region drops to significantly below pH 6.0 which results in unacceptable low temperature stability performance.
  • the two low temperature criteria are robustness at 5°C (with recovery at ambient) for up to 12-weeks and freeze/thaw (with recovery at ambient) for 1 -week.
  • the level of fatty acid used is a key aspect of low temperature instability and this is made increasingly worse at lower pHs (as the ratio of fatty acid to soap is increased).
  • the addition of TEA and MPG can overcome this instability if added at the required levels.
  • the starting point for the 20 ml liquid composition based on SRP hydrolytic stability and pH control is a target pH of 6.5 with a minimum of 1% TEA and 1.5% Prifac 5908.
  • the actual TEA requirement is defined in table 5 and the MPG requirement is defined in table 6.
  • the preferred wt% TEA is 3.5% and the preferred wt% MPG is 20% for the liquid as defined in table 1.

Claims (14)

  1. Composition détergente liquide isotropique ayant un pH dans la bouteille situé dans la plage allant de 6,0 à moins de 7, la composition comprenant, en plus de l'eau :
    a) jusqu'à 60 % en poids d'un tensioactif détergent contenant au moins 5 % en poids de tensioactif sulfate et/ou sulfonate anionique comprenant un acide tensioactif neutralisé avec un ou plusieurs matériaux dont le pKa du ou des acides conjugués est supérieur de plus de 2 unités au pH dans la bouteille de la composition liquide détergente ;
    b) au moins 0,3 % en poids d'un acide gras partiellement neutralisé avec un ou plusieurs matériaux dont le pKa du ou des acides conjugués est supérieur de plus de 2 unités au pH dans la bouteille de la composition liquide détergente ;
    c) au moins 1,0 % en poids, de préférence au moins 1,8 % en poids, de triéthanolamine (TEA) ; et
    d) au moins 0,5 % en poids d'un polymère enlevant les salissures (SRP) ;
    sous réserve que la composition ne soit pas l'une des compositions (A), (B) et (C) :
    (A) une composition constituée de 8,49 % en poids d'acide alkylbenzènesulfonique linéaire en C12 à C14, de 4,24 % en poids de lauryléthersulfate de sodium avec 3 moles d'EO, de 1,50 % en poids d'acide gras laurique saturé Prifac® 5908, de 12,74 % en poids d'alcool en C12 à C15 éthoxylé 7EO non-ionique Neodol® 25-7, de 0,15 % en poids de solution à 47 % de NaOH, de 3,50 % en poids de triéthanolamine, de 20,00 % en poids de monopropylèneglycol, de 5,46 % en poids de polymère de polyéthylène-imine éthoxylé Sokalan HP20 (PEI(600) 20 EO), de 3,55 % en poids de polymère enlevant les salissures Texcare SRN 170, de 2,43 % en poids de parfum sans huile, et d'eau jusqu'à 100 % en poids ;
    (B) une composition constituée de 8,49 % en poids d'acide alkylbenzènesulfonique linéaire en C12 à C14, de 4,24 % en poids de lauryléthersulfate de sodium avec 3 moles d'EO, de 1,50 % en poids d'acide gras laurique saturé Prifac® 5908, de 12,74 % en poids d'alcool en C12 à C15 éthoxylé 7EO non-ionique Neodol® 25-7, de 0,15 % en poids de solution à 47 % de NaOH, de 3,50 % en poids de triéthanolamine, de 20,00 % en poids de monopropylèneglycol, de 5,46 % en poids de polymère de polyéthylène-imine éthoxylé Sokalan HP20 (PEI(600) 20 EO), de 3,55 % en poids de polymère enlevant les salissures Texcare SRN 170, de 1,63 % en poids d'acide (coprah-yl)hydroxamique Axis House RK 853, de 2,43 % en poids de parfum sans huile, et d'eau jusqu'à 100 % en poids ;
    (C) une composition constituée de 8,49 % en poids d'acide alkylbenzènesulfonique linéaire en C12 à C14, de 4,24 % en poids de lauryléthersulfate de sodium avec 3 moles d'EO, de 1,50 % en poids d'acide gras laurique saturé Prifac® 5908, de 12,74 % en poids d'alcool en C12 à C15 éthoxylé 7EO non-ionique Neodol® 25-7, de 0,15 % en poids de solution à 47 % de NaOH, de 3,50 % en poids de triéthanolamine, de 20,00 % en poids de monopropylèneglycol, de 5,46 % en poids de polymère de polyéthylène-imine éthoxylé Sokalan HP20 (PEI(600) 20 EO), de 3,55 % en poids de polymère enlevant les salissures Texcare SRN 170, de 1,63 % en poids de sel K+ d'hydroxamate de (coprah-yle) Axis House RK 852, de 2,43 % en poids de parfum sans huile, et d'eau jusqu'à 100 % en poids.
  2. Composition selon la revendication 1, qui a un pH dans la bouteille de 6,3 à 6,7.
  3. Composition selon l'une quelconque des revendications précédentes, dans laquelle l'acide gras est saturé.
  4. Composition selon l'une quelconque des revendications précédentes, dans laquelle l'acide gras est utilisé en une quantité de 0,5 à 1,5 % en poids.
  5. Composition selon l'une quelconque des revendications précédentes, qui comprend jusqu'à 3,7 % en poids de triéthanolamine (TEA), de préférence de 2,0 à 3,5 % en poids.
  6. Composition selon l'une quelconque des revendications précédentes, dans laquelle le ou les matériaux dont le pKa du ou des conjugués acides est supérieur de plus de 2 unités au pH dans la bouteille de la composition liquide détergente comprennent 0,08 à 0,25 % en poids de NaOH et/ou de monoéthanolamine (MEA), de préférence de 0,1 à 0,23 % en poids.
  7. Composition selon la revendication 6, dans laquelle le ou les matériaux dont le pKa du ou des conjugués acides est supérieur de plus de 2 unités au pH dans la bouteille de la composition liquide détergente comprennent 0,08 à 0,25 % en poids de monoéthanolamine (MEA), de préférence de 0,1 à 0,23 % en poids.
  8. Composition selon l'une quelconque des revendications précédentes, dans laquelle le SRP a une partie importante pour les étoffes formée par condensation d'ester d'acide téréphtalique et de diol, de préférence de 1,2-propanediol, et comprend en outre une partie hydrophile de coiffage en bout comprenant des motifs répétitifs d'oxyde d'éthylène coiffés avec un groupe alkyle.
  9. Composition selon l'une quelconque des revendications précédentes, dans laquelle le liquide comprend un hydrotrope en une quantité d'au moins 5 % en poids, de préférence d'au moins 9 % en poids, mieux encore d'au moins 14 % en poids, et qui est tout spécialement le 1,2-propanediol (MPG).
  10. Composition selon l'une quelconque des revendications précédentes, qui comprend au moins 5 % en poids de polyéthylène-imine éthoxylée (EPEI).
  11. Composition selon l'une quelconque des revendications précédentes, dans laquelle le tensioactif anionique a) comprend au moins 5 % en poids d'alkylbenzènesulfonate linéaire (LAS).
  12. Composition selon l'une quelconque des revendications précédentes, qui comprend un tensioactif zwittérionique, de préférence la carbobétaïne.
  13. Composition détergente liquide isotrope conditionnée ayant un pH dans la bouteille situé dans la plage allant de 6,0 à moins de 7, la composition comprenant, en plus de l'eau :
    a) jusqu'à 60 % en poids d'un tensioactif détergent contenant au moins 5 % en poids de tensioactif sulfate et/ou sulfonate anionique comprenant un acide tensioactif neutralisé avec un ou plusieurs matériaux dont le pKa du ou des acides conjugués est supérieur de plus de 2 unités au pH dans la bouteille de la composition liquide détergente ;
    b) au moins 0,3 % en poids d'un acide gras partiellement neutralisé avec un ou plusieurs matériaux dont le pKa du ou des acides conjugués est supérieur de plus de 2 unités au pH dans la bouteille de la composition liquide détergente ;
    c) au moins 1,0 % en poids, de préférence au moins 1,8 % en poids, de triéthanolamine (TEA) ; et
    d) au moins 0,5 % en poids d'un polymère enlevant les salissures (SRP).
  14. Composition détergente liquide isotrope conditionnée selon la revendication 13, dans laquelle le liquide est conditionné en doses unitaires dans un film polymère adapté pour être insoluble avant d'être ajouté à l'eau de lavage, ou dans laquelle les liquides sont fournis dans des emballages plastiques à usage multiple avec une fermeture en haut ou en bas.
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Families Citing this family (13)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
GB201520128D0 (en) * 2015-11-16 2015-12-30 Reckitt Benckiser Vanish Bv Composition
WO2017202922A1 (fr) * 2016-05-27 2017-11-30 Unilever Plc Composition de lavage du linge
EP3472290B1 (fr) * 2016-06-16 2023-05-03 Henkel AG & Co. KGaA Détergents à lessive liquides isotropes concentrés contenant de polymères
EP3472291B1 (fr) * 2016-06-16 2023-12-20 Henkel AG & Co. KGaA Détergents à lessive liquides isotropes concentrés contenant des polymères
US10808206B2 (en) 2017-11-14 2020-10-20 Henkel IP & Holding GmbH Detergent boosters, detergent systems that include a detergent booster, and methods of laundering fabric
WO2022033857A1 (fr) * 2020-08-12 2022-02-17 Unilever Ip Holdings B.V. Composition de détergent à lessive
WO2022033986A1 (fr) 2020-08-12 2022-02-17 Unilever Ip Holdings B.V. Composition de détergent textile
BR112023001052A2 (pt) * 2020-08-12 2023-03-07 Unilever Ip Holdings B V Método para formação de uma composição detergente estável para lavagem de roupas
EP4196562A1 (fr) 2020-08-12 2023-06-21 Unilever IP Holdings B.V. Procédé de préparation d'une composition détergente liquide de blanchisserie
WO2022033997A1 (fr) 2020-08-12 2022-02-17 Unilever Ip Holdings B.V. Procédé de fabrication d'une composition détergente liquide à lessive
EP4196560A1 (fr) 2020-08-12 2023-06-21 Unilever IP Holdings B.V. Composition de détergent à lessive
EP4196565B1 (fr) 2020-08-12 2024-04-17 Unilever IP Holdings B.V. Composition de lessive
CN113481714B (zh) * 2021-06-14 2023-04-25 山东贝润防水材料有限公司 一种防渗水聚酯胎及其制备方法

Citations (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP2522714A1 (fr) * 2011-05-13 2012-11-14 Unilever Plc, A Company Registered In England And Wales under company no. 41424 of Unilever House Compositions de détergent concentré aqueux pour le linge

Family Cites Families (81)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2182306A (en) 1935-05-10 1939-12-05 Ig Farbenindustrie Ag Polymerization of ethylene imines
US2208095A (en) 1937-01-05 1940-07-16 Ig Farbenindustrie Ag Process of producing insoluble condensation products containing sulphur and nitrogen
US2553696A (en) 1944-01-12 1951-05-22 Union Carbide & Carbon Corp Method for making water-soluble polymers of lower alkylene imines
US2806839A (en) 1953-02-24 1957-09-17 Arnold Hoffman & Co Inc Preparation of polyimines from 2-oxazolidone
BE615597A (fr) 1958-06-19
GB1296839A (fr) 1969-05-29 1972-11-22
GB1372034A (en) 1970-12-31 1974-10-30 Unilever Ltd Detergent compositions
CA989557A (en) 1971-10-28 1976-05-25 The Procter And Gamble Company Compositions and process for imparting renewable soil release finish to polyester-containing fabrics
CA1049367A (fr) * 1974-06-25 1979-02-27 The Procter And Gamble Company Detergents liquides capables de deloger les saletes
DK187280A (da) 1980-04-30 1981-10-31 Novo Industri As Ruhedsreducerende middel til et fuldvaskemiddel fuldvaskemiddel og fuldvaskemetode
US4411831A (en) 1981-12-02 1983-10-25 Purex Industries, Inc. Stable liquid anionic detergent compositions having soil, release properties
US4759876A (en) 1985-03-19 1988-07-26 Colgate-Palmolive Company Stable soil release promoting enzymatic liquid detergent composition
DE3689385T2 (de) * 1985-04-15 1994-05-19 Procter & Gamble Stabile flüssige Reinigungsmittel.
WO1987000859A1 (fr) 1985-08-09 1987-02-12 Gist-Brocades N.V. Nouveaux enzymes lipolytiques et leur utilisation dans des compositions de detergents
US4713194A (en) 1986-04-15 1987-12-15 The Procter & Gamble Company Block polyester and like compounds having branched hydrophilic capping groups useful as soil release agents in detergent compositions
JPS6356289A (ja) 1986-07-30 1988-03-10 Res Dev Corp Of Japan β−マンナナ−ゼおよびその製法
JPS6336775A (ja) 1986-07-31 1988-02-17 Res Dev Corp Of Japan β―マンナナーゼおよびβ―マンノシダーゼ生産能を有するアルカリ性バチルス属新菌株
US4785060A (en) 1986-08-28 1988-11-15 Colgate-Palmolive Company Soil release promoting pet-poet copolymer, method of producing same and use thereof in detergent composition having soil release promoting property
US4810414A (en) 1986-08-29 1989-03-07 Novo Industri A/S Enzymatic detergent additive
NZ221627A (en) 1986-09-09 1993-04-28 Genencor Inc Preparation of enzymes, modifications, catalytic triads to alter ratios or transesterification/hydrolysis ratios
EP0294893A3 (fr) 1987-06-10 1989-11-02 The Procter & Gamble Company Agents de conditionnement et compositions les contenant
EP0305216B1 (fr) 1987-08-28 1995-08-02 Novo Nordisk A/S Lipase recombinante de humicola et procédé de production de lipases recombinantes de humicola
JPS6474992A (en) 1987-09-16 1989-03-20 Fuji Oil Co Ltd Dna sequence, plasmid and production of lipase
US5110506A (en) 1987-10-27 1992-05-05 Colgate-Palmolive Company Soil release promoting liquid detergent composition containing a PET-POET copolymer and a narrow range alcohol ethoxylate
JP3079276B2 (ja) 1988-02-28 2000-08-21 天野製薬株式会社 組換え体ｄｎａ、それを含むシュードモナス属菌及びそれを用いたリパーゼの製造法
US5648263A (en) 1988-03-24 1997-07-15 Novo Nordisk A/S Methods for reducing the harshness of a cotton-containing fabric
JP2728531B2 (ja) 1988-03-24 1998-03-18 ノボ ノルディスク アクティーゼルスカブ セルラーゼ調製品
GB8915658D0 (en) 1989-07-07 1989-08-23 Unilever Plc Enzymes,their production and use
JPH0347076A (ja) 1989-08-25 1991-02-28 Res Dev Corp Of Japan β―マンナナーゼおよびその製法
KR100236540B1 (ko) 1990-04-14 2000-01-15 레클로우크스 라우에르 알카리성 바실러스-리파제, 이를 코-딩하는 dna 서열 및 리파제를 생산하는 바실러스 균주
US5290475A (en) 1990-05-08 1994-03-01 Colgate Palmolive Liquid softening and anti-static nonionic detergent composition with soil release promoting PET-POET copolymer
AU8060091A (en) 1990-05-29 1991-12-31 Chemgen Corporation Hemicellulase active at extremes of ph and temperature and the means for the production thereof
AU657278B2 (en) 1990-09-13 1995-03-09 Novo Nordisk A/S Lipase variants
EP0511456A1 (fr) 1991-04-30 1992-11-04 The Procter & Gamble Company Détergents liquides contenant un ester aromatique de l'acide borique pour inhibition d'enzyme protéolitique
EP0583420B1 (fr) 1991-04-30 1996-03-27 The Procter & Gamble Company Detergents liquides contenant un adjuvant et un complexe polyol acide borique qui sert a inhiber l'enzyme proteolytique
US6262007B1 (en) 1991-06-14 2001-07-17 The Procter & Gamble Company Self-thickened cleaning compositions
JP2626662B2 (ja) 1991-10-09 1997-07-02 科学技術振興事業団 新規なβ−マンナナーゼとその製造方法
FI931193A0 (fi) 1992-05-22 1993-03-17 Valtion Teknillinen Mannanasenzymer, gener som kodar foer dem och foerfaranden foer isoleringav generna samt foerfarande foer blekning av lignocellulosahaltig massa
DK72992D0 (da) 1992-06-01 1992-06-01 Novo Nordisk As Enzym
DK88892D0 (da) 1992-07-06 1992-07-06 Novo Nordisk As Forbindelse
EP0652946B1 (fr) 1993-04-27 2005-01-26 Genencor International, Inc. Nouveaux variants de lipase utilises dans des detergents
DK48693D0 (da) 1993-04-30 1993-04-30 Novo Nordisk As Enzym
JP2859520B2 (ja) 1993-08-30 1999-02-17 ノボ ノルディスク アクティーゼルスカブ リパーゼ及びそれを生産する微生物及びリパーゼ製造方法及びリパーゼ含有洗剤組成物
JPH09503664A (ja) 1993-10-13 1997-04-15 ノボ ノルディスク アクティーゼルスカブ Ｈ▲下２▼ｏ▲下２▼安定ペルオキシダーゼ変異体
JPH07143883A (ja) 1993-11-24 1995-06-06 Showa Denko Kk リパーゼ遺伝子及び変異体リパーゼ
DE69527835T2 (de) 1994-02-22 2003-04-10 Novozymes As Methode zur herstellung einer variante eines lipolytischen enzymes
CN1326994C (zh) 1994-03-29 2007-07-18 诺沃奇梅兹有限公司 碱性芽孢杆菌淀粉酶
EP0755442B1 (fr) 1994-05-04 2002-10-09 Genencor International, Inc. Lipases a resistance aux tensioactifs amelioree
AU2884595A (en) 1994-06-20 1996-01-15 Unilever Plc Modified pseudomonas lipases and their use
WO1996000292A1 (fr) 1994-06-23 1996-01-04 Unilever N.V. Pseudomonas lipases modifiees et leur utilisation
BE1008998A3 (fr) 1994-10-14 1996-10-01 Solvay Lipase, microorganisme la produisant, procede de preparation de cette lipase et utilisations de celle-ci.
EP0785994A1 (fr) 1994-10-26 1997-07-30 Novo Nordisk A/S Enzyme a activite lipolytique
JPH08228778A (ja) 1995-02-27 1996-09-10 Showa Denko Kk 新規なリパーゼ遺伝子及びそれを用いたリパーゼの製造方法
NZ303162A (en) 1995-03-17 2000-01-28 Novo Nordisk As Enzyme preparations comprising an enzyme exhibiting endoglucanase activity appropriate for laundry compositions for textiles
WO1997003192A2 (fr) * 1995-07-07 1997-01-30 Darwin Molecular Corporation Gene du chromosome 1 et produits genetiques lies a la maladie d'alzheimer
GB2303146A (en) * 1995-07-08 1997-02-12 Procter & Gamble Detergent compositions
JP4307549B2 (ja) 1995-07-14 2009-08-05 ノボザイムス アクティーゼルスカブ 脂肪分解活性を有する修飾された酵素
JP4068142B2 (ja) 1995-08-11 2008-03-26 ノボザイムス アクティーゼルスカブ 新規の脂肪分解酵素
JPH11514856A (ja) 1995-09-20 1999-12-21 ジェネンコア インターナショナル インコーポレーテッド バチルスアミロリケファシエンスからの精製マンナーゼおよびその調製方法
EP0901516A1 (fr) 1996-05-03 1999-03-17 The Procter & Gamble Company Compositions detergentes liquides pour la lessive contenant des polymeres facilitant le lavage des cotons
EP0906402A1 (fr) 1996-06-19 1999-04-07 Unilever N.V. Activation d'un agent de blanchiment
EP1726644A1 (fr) 1996-09-17 2006-11-29 Novozymes A/S Variants de cellulase
WO1998015257A1 (fr) 1996-10-08 1998-04-16 Novo Nordisk A/S Derives de l'acide diaminobenzoique en tant que precurseurs de matieres tinctoriales
HU226087B1 (en) 1997-03-07 2008-04-28 Procter & Gamble Laundry and cleaning compositions containing bleach catalyst
ZA981883B (en) 1997-03-07 1998-09-01 Univ Kansas Catalysts and methods for catalytic oxidation
DE19725508A1 (de) * 1997-06-17 1998-12-24 Clariant Gmbh Wasch- und Reinigungsmittel
US6124127A (en) 1997-11-24 2000-09-26 Novo Nordisk A/S Pectate lyase
TR200001489T2 (tr) 1997-11-24 2000-11-21 Novo Nordisk A/S Yeni pektat liazlar.
WO1999027083A1 (fr) 1997-11-24 1999-06-03 Novo Nordisk A/S ENZYMES DE DEGRADATION DE LA PECTINE PROVENANT DU $i(BACILLUS LICHENIFORMIS)
ATE528394T1 (de) 1998-06-10 2011-10-15 Novozymes As Neuartige mannasen
AU1522300A (en) 1998-11-13 2000-06-05 Procter & Gamble Company, The Bleach compositions
ES2255992T3 (es) 1999-03-02 2006-07-16 THE PROCTER & GAMBLE COMPANY Composiciones blanqueantes estabilizadas.
DK2011864T3 (en) 1999-03-31 2015-04-07 Novozymes As Polypeptides with alkaline alpha-amylase activity and nucleic acids encoding them
WO2000060045A1 (fr) 1999-04-01 2000-10-12 The Procter & Gamble Company Agents de blanchiment de metaux de transition
AU2001281736A1 (en) 2000-07-19 2002-01-30 Novozymes A/S Cell-wall degrading enzyme variants
GB0030673D0 (en) 2000-12-15 2001-01-31 Unilever Plc Ligand and complex for catalytically bleaching a substrate
CN1863900B (zh) 2003-08-06 2011-01-26 西巴特殊化学制品控股公司 色调改变组合物
US20080015135A1 (en) * 2006-05-05 2008-01-17 De Buzzaccarini Francesco Compact fluid laundry detergent composition
CA2728378A1 (fr) 2008-06-16 2009-12-23 Unilever Plc Une methode de nettoyage des tissus au moyen d'une composition detergente liquide versable a tres faible teneur en savon
WO2010033743A1 (fr) 2008-09-19 2010-03-25 The Procter & Gamble Company Biopolymère de lgnine modifié utilisé dans des compositions de nettoyage
US8900328B2 (en) 2009-03-16 2014-12-02 The Procter & Gamble Company Cleaning method

Patent Citations (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP2522714A1 (fr) * 2011-05-13 2012-11-14 Unilever Plc, A Company Registered In England And Wales under company no. 41424 of Unilever House Compositions de détergent concentré aqueux pour le linge

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ES2587861T3 (es) 2016-10-27
CL2014001603A1 (es) 2014-08-22
BR112014013942B1 (pt) 2021-03-02
BR112014013942A2 (pt) 2017-06-13
CN104011192A (zh) 2014-08-27
AR089289A1 (es) 2014-08-13
EP2794832A1 (fr) 2014-10-29
AU2012358647A1 (en) 2014-07-03
CN104011192B (zh) 2017-08-25
WO2013092052A1 (fr) 2013-06-27
AU2012358647B2 (en) 2015-01-15

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