EP2300586B1 - Verbesserungen im zusammenhang mit stoffreinigung - Google Patents

Verbesserungen im zusammenhang mit stoffreinigung Download PDF

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Publication number
EP2300586B1
EP2300586B1 EP09765764.7A EP09765764A EP2300586B1 EP 2300586 B1 EP2300586 B1 EP 2300586B1 EP 09765764 A EP09765764 A EP 09765764A EP 2300586 B1 EP2300586 B1 EP 2300586B1
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EP
European Patent Office
Prior art keywords
surfactant
composition
soap
better
lipase
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Revoked
Application number
EP09765764.7A
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English (en)
French (fr)
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EP2300586A1 (de
Inventor
Julie Bennett
Paul Kravchuk
Donna Macnab
Anthony Mckee
Alyn James Parry
Patricia Revell
Becky Zhou
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Unilever PLC
Unilever NV
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Unilever PLC
Unilever NV
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Priority claimed from GBGB0810881.3A external-priority patent/GB0810881D0/en
Application filed by Unilever PLC, Unilever NV filed Critical Unilever PLC
Priority to PL09765764T priority Critical patent/PL2300586T3/pl
Priority to EP09765764.7A priority patent/EP2300586B1/de
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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
    • C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
    • C11D3/16—Organic compounds
    • C11D3/37—Polymers
    • C11D3/3703—Macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
    • C11D3/3723—Polyamines or polyalkyleneimines
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
    • C11D3/16—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
    • 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
    • C11D3/38681—Chemically modified or immobilised enzymes
    • C11D2111/12—

Definitions

  • the present invention is concerned with improvements relating to fabric cleaning and, in particular, with an improved process for laundering fabrics using a concentrated detergent.
  • Isotropic liquid detergents for use in laundry comprise varying concentration levels of surfactant. 10 to 15 %wt is commonplace in Portugal and Spain, 18 to 27 %wt typical in the Benelux countries, Germany and Italy, while levels of 35 to 40 %wt surfactant have been used in the UK and France.
  • Concentrated products also offer the advantages of taking up less shelf and storage space. Concentrated products deliver the same level of surfactant into the wash liquor from a smaller volume of product, and they are generally formulated by taking water out.
  • a "four times" concentrate has been launched in Australia under the brand name “Orange power” and is described as "a 4x concentrate enzyme liquid detergent”. Its dosage recommendation is 25 ml (a cupful) for top loading washing machines and 3 ⁇ 4 of a cap for front loaders.
  • Unit dosage has been suggested to overcome some of the known problems but this can lead to dissolution problems.
  • rising cost of surfactants, especially those from oil-based materials has led to pressures to remove surfactant as well.
  • WO 2004/074419 suggests the replacement of part of the surfactant, builder, bleach, and fillers in a detergent with enzymes. This is said to result in a significant reduction of the volume and weight of the detergent necessary for one wash.
  • levels of surfactant of less than 30 wt% preferably 4 to 20wt%, more preferably 5 to 15 wt% are disclosed.
  • Any soil suspending polymer is said to be reduced to 0 to 6 wt% after it too is partially or fully replaced by enzymes. Lipase is used to boost oily soil detergency.
  • non-soap surfactant levels as low as 0.18 g/L are disclosed.
  • WO 2006/113314 discloses a liquid laundry detergent composition comprising:
  • alkyl ethoxy sulfate surfactant may be present in the composition from about 5% to about 30%; or from about 7% to 16% by weight of the composition.
  • Additional surfactants include up to 7% of nonionic and/or anionic co-surfactants.
  • Aqueous washing solutions are disclosed to comprise 500 to 7,000 ppm (0.5 to 7 g/L) of the composition, preferably 1000 to 3000 ppm. If the non-soap surfactant level varies from 11 to 21 wt%, as in the examples, this would provide a preferred wash solution non-soap surfactant concentration of from 0.1 to 0.6 g/l.
  • the general disclosure allows for high levels of EPEI, the actual levels used are too low to realise the benefit from the low dose of surfactant to the wash from a low volume dose of the composition.
  • a first aspect of the present invention provides a method of laundering fabric which comprises the steps of:
  • pourable means that it can be poured.
  • it has a shear viscosity (at 25 Celcius) of below preferably below 2 Pa.s at a shear rate of 21s -1 .
  • Preferred viscosities are in the range 1.0 - 0.1 Pa.s.
  • the composition may be shear thinning.
  • the dose is less than 35 ml, more preferably less than 30 ml, and most preferably less than 25 ml per wash, even being 20 ml or less per wash.
  • the wash liquor obtained comprises 0.25 to 0.55 g/l of non-soap surfactant, for example 0.4 g/L or lower.
  • Doses may be measured by hand, more preferably metered by a suitable device or provided as pre-measured unit doses. The use of a container with metering means to deliver a dose with a dose to dose variability of less than 20 %wt and preferably less than 10 %wt is preferred.
  • the Calcium Tolerance Test used herein is that defined in EP1771543 .
  • a surfactant blend is prepared at a concentration of 0.7 g/l in water containing sufficient calcium ions to give a French Hardness of 40 degrees.
  • Other electrolytes such as sodium chloride, sodium sulphate, sodium hydroxide are added as necessary to adjust the ionic strength to 0.5M and the pH to 10.
  • the absorption of light of wavelength 540 nm through 4 mm of sample is measured 15 minutes after sample preparation. Ten measurements are made and an average value is calculated. Samples that give an absorption value of less than 0.08 are deemed to be calcium tolerant.
  • the dilution factor in the method of the first aspect of the present invention is by a factor of at least 500, by which is meant that one volume of composition is mixed with at least 500 volumes of water.
  • the dilution factor is preferably less than 2500.
  • Particularly preferred dilution factors fall in the range of 500 to 1500, most preferably 500 to 1000.
  • the detergent composition comprises not more than 35 %wt, even more preferably not more than 30 %wt, of non-soap surfactant.
  • the total surfactant will be a mixture of nonionic and anionic surfactant.
  • the anionic surfactant is predominately, and more preferably essentially, a non-soap anionic surfactant.
  • the anion of the anionic surfactant is selected from the group consisting of linear alkyl benzene sulphonate (LAS), primary alkyl sulphate (PAS), alkyl ether sulphate (AES) and mixtures thereof.
  • zwitterionic surfactants are used as part of the surfactant mixture. Zwitterionics, in particular betaines, improve particulate soil detergency in the compositions of the invention.
  • surfactant system 10% MEA and 10% of a hydrotrope such as MPG is required to achieve a stable composition with the desired pH. This would be impossible even with zero water present if the other ingredients already add up to over 80 wt%.
  • a particularly advantageous benefit of the reduction of surfactant levels in the wash using the method and composition of the invention is that shading dyes are better deposited.
  • the method of the invention is conducted in a washing machine, more preferably in a non-vertical axis machine, most preferably in a horizontal-axis machine with a drawer dispensing system.
  • compositions in the method according to the invention may be further improved by the presence of one or more of enzymes, further polymers and shading dyes.
  • Lipase is a particularly preferred enzyme.
  • the composition prior to the dilution step (b) preferably contains from about 5 to about 20000 LU/g of a lipase.
  • Preferred lipase enzymes include those of bacterial or fungal origin. Chemically modified or protein engineered mutants are included. Examples of 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 lanuginose , most preferably strain DSM 4109.
  • lipase enzymes show a single-wash benefit.
  • the amount of lipase enzyme protein used in the wash is set to be at the high side of what is normal (>5mg, pref greater than 8mg per wash). This means that 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.
  • a range of possible polymers may be employed to improve the performance of the compositions used in the method of the present invention. Again, the efficacy of these polymers is much improved by the reduction in the level of surfactant present in the wash.
  • the ratio of polymer to surfactant is also set to be higher than normal.
  • One polymer is the fabric-substantive polymers comprising at least one of (i) saccharide or (ii) dicarboxylic acid and polyol monomer units. Typically these have soil release properties while they can have a primary detergency effect the generally assist in subsequent cleaning. Preferably these should be present at a level of at least 2%wt preferably at least 3% of the composition.
  • 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 bisulfite, sulfuric 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.
  • these comprise a polyethyleneimine backbone of about 300 to about 10000 weight average molecular weight; wherein the modification of the polyethyleneimine backbone is:
  • the polyethyleneimine polymer is present in the composition provided in step (a), prior to the dilution step (b), preferably at a level of between 0.01 and 25 wt%, but more preferably at a level of at least 3 wt% and/or less than 9,5 wt%, most preferably from 4 to 9 wt% and with a ratio of non-soap surfactant to EPEI of from 2:1 to 7:1, preferably from 3:1 to 6:1, or even to 5:1.
  • the invention while using less surfactant per wash than fully formulated commercial compositions exhibit at least parity in performance and on many stains and dirt show improved performance.
  • compositions of step (a) of the process may be provided either in a multidose container or in the form of a liquid unit dose in a soluble sachet.
  • the concentrated composition is prediluted with a small amount of water to enable the normal volume to be dosed (e.g. 35 ml).
  • a small amount of water to enable the normal volume to be dosed (e.g. 35 ml).
  • This retains the advantages of a low amount of chemical dosed per wash and if the dilution step is carried out when the composition is bottled it can aid in the stability of the formulation on storage.
  • the dilution factor will be adjusted to compensate for the greater dose of more dilute material added to the wash.
  • the extent of dilution can be as low as 280 volumes of water to one dose from the bottle of the concentrate with extra make up water in a multi-dose bottle.
  • the dose in step (b) further comprises at least 0.01 g active lipase protein (or greater than 2500 LU).
  • the dose, prior to dilution, should contain 5 to 20 000 LU/g when lipase is present.
  • Surfactants assist in removing soil from the textile materials and also assist in maintaining removed soil in solution or suspension in the wash liquor.
  • Anionic and/or nonionic surfactants preferably in a calcium tolerant blend, are an essential feature of the present invention.
  • Surfactant systems which consist only of linear alkyl benzene sulphonate (LAS) are generally calcium intolerant.
  • surfactant systems should generally avoid having levels of LAS above 90 %wt.
  • Nonionic-free systems with 95 %wt LAS can be made provided that some zwitterionic surfactant, such as sulphobetaine, is present.
  • Preferred alkyl ether sulphates are C 8 -C 15 alkyl and have 2-10 moles of ethoxlation.
  • Preferred alkyl sulphates 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. Suitable anionic surfactant materials are available in the marketplace as the 'Genapol'TM range from Clariant.
  • 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.
  • shading dye can be used to improve the performance of the compositions used in the method of the present invention.
  • the deposition of shading dye onto fabric is improved when they are used in compositions of the invention and according to the process of the invention.
  • Preferred dyes are violet or blue. It is believed that the deposition on fabrics of a low level of a dye of these shades, masks yellowing of fabrics.
  • a further advantage of shading dyes is that they can be used to mask any yellow tint in the composition itself.
  • Direct dyes are the class of water soluble dyes which have a affinity for fibres and are taken up directly. Direct violet and direct blue dyes are preferred.
  • the dye are bis-azo or tris-azo dyes are used.
  • the direct dye is a direct violet of the following structures: or wherein:
  • Preferred dyes are direct violet 7, direct violet 9, direct violet 11, direct violet 26, direct violet 31, direct violet 35, direct violet 40, direct violet 41, direct violet 51, and direct violet 99.
  • Bis-azo copper containing dyes such as direct violet 66 may be used.
  • the benzidene based dyes are less preferred.
  • the direct dye is present at 0.000001 to 1 wt% more preferably 0.00001 wt% to 0.0010 wt% of the composition.
  • the direct dye may be covalently linked to the photo-bleach, for example as described in WO2006/024612 .
  • Cotton substantive acid dyes give benefits to cotton containing garments.
  • Preferred dyes and mixes of dyes are blue or violet.
  • Preferred acid dyes are:
  • Preferred azine dyes are: acid blue 98, acid violet 50, and acid blue 59, more preferably acid violet 50 and acid blue 98.
  • non-azine acid dyes are acid violet 17, acid black 1 and acid blue 29.
  • the acid dye is present at 0.0005 wt% to 0.01 wt% of the formulation.
  • the composition may comprise one or more hydrophobic dyes selected from benzodifuranes, methine, triphenylmethanes, napthalimides, pyrazole, napthoquinone, anthraquinone and mono-azo or di-azo dye chromophores.
  • Hydrophobic dyes are dyes which do not contain any charged water solubilising group. Hydrophobic dyes may be selected from the groups of disperse and solvent dyes. Blue and violet anthraquinone and mono-azo dye are preferred.
  • Preferred dyes include solvent violet 13, disperse violet 27 disperse violet 26, disperse violet 28, disperse violet 63 and disperse violet 77.
  • the hydrophobic dye is present at 0.0001 wt% to 0.005 wt% of the formulation.
  • Basic dyes are organic dyes which carry a net positive charge. They deposit onto cotton. They are of particular utility for used in composition that contain predominantly cationic surfactants. Dyes may be selected from the basic violet and basic blue dyes listed in the Colour Index International.
  • Preferred examples include triarylmethane basic dyes, methane basic dye, anthraquinone basic dyes, basic blue 16, basic blue 65, basic blue 66, basic blue 67, basic blue 71, basic blue 159, basic violet 19, basic violet 35, basic violet 38, basic violet 48; basic blue 3, basic blue 75, basic blue 95, basic blue 122, basic blue 124, basic blue 141.
  • Reactive dyes are dyes which contain an organic group capable of reacting with cellulose and linking the dye to cellulose with a covalent bond. They deposit onto cotton.
  • the reactive group is hydrolysed or reactive group of the dyes has been reacted with an organic species such as a polymer, so as to the link the dye to this species.
  • Dyes may be selected from the reactive violet and reactive blue dyes listed in the Colour Index International.
  • Preferred examples include reactive blue 19, reactive blue 163, reactive blue 182 and reactive blue, reactive blue 96.
  • Dye conjugates are formed by binding direct, acid or basic dyes to polymers or particles via physical forces. Dependent on the choice of polymer or particle they deposit on cotton or synthetics. A description is given in WO2006/055787 . Particularly preferred dyes are: direct violet 7, direct violet 9, direct violet 11, direct violet 26, direct violet 31, direct violet 35, direct violet 40, direct violet 41, direct violet 51, direct violet 99, acid blue 98, acid violet 50, acid blue 59, acid violet 17, acid black 1, acid blue 29, solvent violet 13, disperse violet 27 disperse violet 26, disperse violet 28, disperse violet 63, disperse violet 77 and mixtures thereof.
  • compositions of the invention preferably further comprises a fluorescent agent (optical brightener).
  • Fluorescent agents are well known and many such fluorescent agents are available commercially. Usually, 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 0.1 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 fluoxescers are: sodium 2 (4-styryl-3-sulfophenyl)-2H-napthol[1,2-d]trazole, 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.
  • Shading dye can be used in the absence of fluorescer, but it is specially 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 present invention provides a method of laundering fabric which comprises the steps of:
  • composition optionally comprises fluorescer, preferably at a level of 0.005 to 2 wt %, and,
  • the composition comprises polymers.
  • Polymers can assist in the cleaning process by helping to retain soil in solution or suspension and/or preventing the transfer of dyes. Polymers can also assist in the soil removal process. Dye transfer, anti-redeposition and soil-release polymers are described in further detail below.
  • Detergent compositions often employ polymers as so-called 'dye-transfer inhibitors'. These prevent migration of dyes, especially during long soak times.
  • Any suitable dye-transfer inhibition agents may be used in accordance with the present invention.
  • dye-transfer inhibiting agents include polyvinyl pyrrolidone polymers, polyamine N-oxide polymers, copolymers of N-vinylpyrrolidone and N-vinylimidazole, manganese phthalocyanine, peroxidases, and mixtures thereof.
  • Nitrogen-containing, dye binding, DTI polymers are preferred. Of these polymers and co-polymers of cyclic amines such as vinyl pyrrolidone (PVP), and/or vinyl imidazole (PVI) are preferred.
  • Preferred polyamine N-oxides are those wherein R is a heterocyclic group such as pyridine, pyrrole, imidazole, pyrrolidine, piperidine and derivatives thereof.
  • the amine oxide unit of the polyamine N-oxides has a pK a ⁇ 10, preferably pK a ⁇ 7, more preferably pK a ⁇ 6.
  • Any polymer backbone can be used provided the amine oxide polymer formed is water-soluble and has dye transfer inhibiting properties.
  • suitable polymeric backbones are polyvinyls, polyalkylenes, polyesters, polyethers, polyamides, polyimides, polyacrylates and mixtures thereof. These polymers include random or block copolymers where one monomer type is an amine N-oxide and the other monomer type is an N-oxide.
  • the amine N-oxide polymers typically have a ratio of amine to the amine N-oxide of 10:1 to 1:1,000,000. However, the number of amine oxide groups present in the polyamine oxide polymer can be varied by appropriate copolymerization or by an appropriate degree of N-oxidation.
  • the polyamine oxides can be obtained in almost any degree of polymerization. Typically, the average molecular weight is within the range of 500 to 1,000,000; more preferably 1,000 to 500,000; most preferably 5,000 to 100,000. This preferred class of materials is referred to herein as "PVNO".
  • a preferred polyamine N-oxide is poly(4-vinylpyridine-N-oxide) which as an average molecular weight of about 50,000 and an amine to amine N-oxide ratio of about 1:4.
  • Copolymers of N-vinylpyrrolidone and N-vinylimidazole polymers are also preferred.
  • the PVPVI has an average molecular weight range from 5,000 to 1,000,000, more preferably from 5,000 to 200,000, and most preferably from 10,000 to 20,000, as determined by light scattering as described in Barth, et al., Chemical Analysis, Vol. 113. "Modern Methods of Polymer Characterization ".
  • the preferred PVPVI copolymers typically have a molar ratio of N-vinylimidazole to N-vinylpyrrolidone from 1:1 to 0.2:1, more preferably from 0.8:1 to 0.3:1, most preferably from 0.6:1 to 0.4:1. These copolymers can be either linear or branched. Suitable PVPVI polymers include Sokalan ( TM ) HP56, available commercially from BASF, Ludwigshafen, Germany.
  • PVP polyvinylpyrrolidone polymers
  • Suitable PVP polymers include Sokalan ( TM ) HP50, available commercially from BASF.
  • Compositions containing PVP can also contain polyethylene glycol (PEG) having an average molecular weight from about 500 to about 100,000, preferably from about 1,000 to about 10,000.
  • PEG polyethylene glycol
  • the ratio of PEG to PVP on a ppm basis delivered in wash solutions is from about 2:1 to about 50:1, and more preferably from about 3:1 to about 10:1.
  • modified polyethyleneimine polymers are water-soluble or dispersible, modified polyamines.
  • Modified polyamines are further disclosed in US-A-4,548,744 ; US-A-4,597,898 ; US-A- 4,877,896 ; US-A- 4,891 , 160 ; US-A- 4,976,879 ; US-A-5,415,807 ; GB-A-1,537,288 ; GB-A-1,498,520 ; DE-A-28 29022 ; and JP-A-06313271 .
  • the modified ethoxylated polyamines are described above and are generally linear or branched poly (>2) amines.
  • the amines may be primary, secondary or tertiary.
  • a single or a number of amine functions are reacted with one or more alkylene oxide groups to form a polyalkylene oxide side chain.
  • the alkylene oxide can be a homopolymer (for example ethylene oxide) or a random or block copolymer.
  • the terminal group of the alkylene oxide side chain can be further reacted to give an anionic character to the molecule (for example to give carboxylic acid or sulphonic acid functionality).
  • the composition according to the present invention comprises a dye transfer inhibition agent selected from polyvinylpyrridine N-oxide (PVNO), polyvinyl pyrrolidone (PVP), polyvinyl imidazole, N-vinylpyrrolidone and N-vinylimidazole copolymers (PVPVI), copolymers thereof, and mixtures thereof.
  • a dye transfer inhibition agent selected from polyvinylpyrridine N-oxide (PVNO), polyvinyl pyrrolidone (PVP), polyvinyl imidazole, N-vinylpyrrolidone and N-vinylimidazole copolymers (PVPVI), copolymers thereof, and mixtures thereof.
  • the amount of dye transfer inhibition agent in the composition according to the present invention will be from 0.01 to 10 %, preferably from 0.02 to 8, or even to 5 %, more preferably from 0.03 to 6, or even to 2 %, by weight of the composition. It will be appreciated that the dye transfer inhibition agents will assist in the preservation of whiteness by preventing the migration of dyes from place to place. This preservation of whiteness assists in cleaning and counteracts the reduction in surfactants present in the wash liquor.
  • Anti-redeposition polymers are:
  • Anti-redeposition polymers are typically polycarboxylate materials.
  • Polycarboxylate materials which can be prepared by polymerizing or copolymerizing suitable unsaturated monomers, are preferably admixed in their acid form.
  • Unsaturated monomeric acids that can be polymerized to form suitable polycarboxylates include acrylic acid, maleic acid (or maleic anhydride), fumaric acid, itaconic acid, aconitic acid, mesaconic acid, citraconic acid and methylenemalonic acid.
  • the presence in the polycarboxylates herein of monomeric segments, containing no carboxylate radicals such as vinylmethyl ether, styrene, ethylene, etc. is suitable provided that such segments do not constitute more than about 40% by weight of the polymer.
  • Particularly suitable polycarboxylates can be derived from acrylic acid.
  • acrylic acid-based polymers which are useful herein are the water-soluble salts of polymerized acrylic acid.
  • the average molecular weight of such polymers in the acid form preferably ranges from about 2,000 to 10,000, more preferably from about 4,000 to 7,000 and most preferably from about 4,000 to 5,000.
  • Water-soluble salts of such acrylic acid polymers can include, for example, the alkali metal, ammonium and substituted ammonium salts. Soluble polymers of this type are known materials.
  • Use of polyacrylates of this type in detergent compositions has been disclosed, for example, in Diehl, U.S. Pat. No. 3,308,067, issued Mar. 7, 1967 .
  • the preferred polycarboxylate is sodium polyacrylate.
  • Acrylic/maleic-based copolymers may also be used as a preferred component of the anti-redeposition agent.
  • Such materials include the water-soluble salts of copolymers of acrylic acid and maleic acid.
  • the average molecular weight of such copolymers in the acid form preferably ranges from about 2,000 to 100,000, more preferably from about 5,000 to 75,000, most preferably from about 7,000 to 65,000.
  • the ratio of acrylate to maleate segments in such copolymers will generally range from about 30:1 to about 1: 1, more preferably from about 10:1 to 2:1.
  • Water-soluble salts of such acrylic acid/maleic acid copolymers can include, for example, the alkali metal, ammonium and substituted ammonium salts.
  • Soluble acrylate/maleate copolymers of this type are known materials which are described in European Patent Application No. 66915, published Dec. 15, 1982 , as well as in EP 193,360, published Sep. 3, 1986 , which also describes such polymers comprising hydroxypropylacrylate. Still other useful polymers maleic/acrylic/vinyl alcohol terpolymers. Such materials are also disclosed in EP 193,360 , including, for example, the 45/45/10 terpolymer of acrylic/maleic/vinyl alcohol.
  • Polyethylene glycol (PEG) can act as a clay soil removal-antiredeposition agent. Typical molecular weight ranges for these purposes range from about 500 to about 100,000, preferably from about 1,000 to about 50,000, more preferably from about 3,000 to about 10,000. Polyaspartate and polyglutamate dispersing agents may also be used.
  • polymeric soil release agent Any polymeric soil release agent known to those skilled in the art can optionally be employed in compositions according to the invention.
  • Polymeric soil release agents are characterized by having both hydrophilic segments, to hydrophilize the surface of hydrophobic fibres, such as polyester and nylon, and hydrophobic segments, to deposit upon hydrophobic fibres and remain adhered thereto through completion of washing and rinsing cycles and, thus, serve as an anchor for the hydrophilic segments. This can enable stains occurring subsequent to treatment with the soil release agent to be more easily cleaned in later washing procedures.
  • the amount of anti redeposition polymer in the composition according to the present invention will be from 0.01 to 10 %, preferably from 0.02 to 8 %, more preferably from 0.03 to 6 %, by weight of the composition.
  • the soil release polymers for polyester will comprise polymers of aromatic dicarboxylic acids and alkylene glycols (including polymers containing polyalkylene glycols).
  • the polymeric soil release agents useful herein especially include those soil release agents having:
  • the polyoxyethylene segments of (a)(i) will have a degree of polymerization of from about 200, although higher levels can be used, preferably from 3 to about 150, more preferably from 6 to about 100.
  • Suitable oxy C 4 -C 6 alkylene hydrophobe segments include, but are not limited to, end-caps of polymeric soil release agents such as MO 3 S(CH 2 ) n OCH 2 CH 2 O--, where M is sodium and n is an integer from 4-6, as disclosed in U.S. Pat. No. 4,721,580, issued Jan. 26, 1988 to Gosselink .
  • Soil release agents characterized by poly(vinyl ester) hydrophobe segments include graft copolymers of poly(vinyl ester), e.g., C 1 -C 6 vinyl esters, preferably poly(vinyl acetate) grafted onto polyalkylene oxide backbones, such as polyethylene oxide backbones.
  • poly(vinyl ester) e.g., C 1 -C 6 vinyl esters
  • poly(vinyl acetate) grafted onto polyalkylene oxide backbones such as polyethylene oxide backbones.
  • Commercially available soil release agents of this kind include the SOKALAN type of material, e.g., SOKALAN HP-22, available from BASF (West Germany).
  • One type of preferred soil release agent is a copolymer having random blocks of ethylene terephthalate and polyethylene oxide (PEO) terephthalate.
  • the molecular weight of this polymeric soil release agent is in the range of from about 25,000 to about 55,000. See U.S. Pat. No. 3,959,230 to Hays, issued May 25, 1976 and U.S. Pat. No. 3,893,929 to Basadur issued Jul. 8, 1975 .
  • Another preferred polymeric soil release agent is a polyester with repeat units of ethylene terephthalate units contains 10-15% by weight of ethylene terephthalate units together with 90-80% by weight of polyoxyethylene terephthalate units, derived from a polyoxyethylene glycol of average molecular weight 300-5,000.
  • this polymer include the commercially available material ZELCON 5126 (from DuPont) and MILEASE T (from ICI). See also U.S. Pat. No. 4,702,857, issued Oct. 27, 1987 to Gosselink .
  • Another preferred polymeric soil release agent is a sulfonated product of a substantially linear ester oligomer comprised of an oligomeric ester backbone of terephthaloyl and oxyalkyleneoxy repeat units and terminal moieties covalently attached to the backbone.
  • These soil release agents are described fully in U.S. Pat. No. 4,968,451, issued Nov. 6, 1990 to J.J. Scheibel and E. P. Gosselink .
  • Other suitable polymeric soil release agents include the terephthalate polyesters of U.S. Pat. No. 4,711,730, issued Dec. 8, 1987 to Gosselink et al , the anionic end-capped oligomeric esters of U.S. Pat. No. 4,721,580, issued Jan. 26, 1988 to Gosselink , and the block polyester oligomeric compounds of U.S. Pat. No. 4,702,857, issued Oct. 27, 1987 to Gosselink .
  • Preferred polymeric soil release agents also include the soil release agents of U.S. Pat. No. 4,877,896, issued Oct. 31, 1989 to Maldonado et al , which discloses anionic, especially sulfoarolyl, end-capped terephthalate esters.
  • Soil release agents will generally comprise from about 0.01% to about 10.0%, by weight, of the detergent composition, typically greater than or equal to 0.2 wt% even from 3 wt% to 9 wt%, but more preferably they are used at greater than 1 wt%, even greater than 2 wt% and most preferably greater than 3 wt%, even more preferably greater than 5 wt%, say 6 to 8 wt% in the composition.
  • Still another preferred soil release agent is an oligomer with repeat units of terephthaloyl units, sulfoisoterephthaloyl units, oxyothyleneoxy and oxy-1,2-propylene units.
  • the repeat units form the backbone of the oligomer and are preferably terminated with modified isethionate end-caps.
  • a particularly preferred soil release agent of this type comprises about one sulfoisophthaloyl unit, 5 terephthaloyl units, oxyethyleneoxy and oxy-1,2-propyleneoxy units in a ratio of from about 1.7 to about 1.8, and two end-cap units of sodium 2-(2-hydroxyethoxy)-ethanesulfonate.
  • Said soil release agent also comprises from about 0.5% to about 20%, by weight of the oligomer, of a crystalline-reducing stabilizer, preferably selected from the group consisting of xylene sulfonate, cumene sulfonate, toluene sulfonate, and mixtures thereof.
  • a crystalline-reducing stabilizer preferably selected from the group consisting of xylene sulfonate, cumene sulfonate, toluene sulfonate, and mixtures thereof.
  • Suitable soil release polymers are described in WO 2008095626 (Clariant); WO 2006133867 (Clariant); WO 2006133868 (Clariant); WO 2005097959 (Clariant); WO 9858044 (Clariant); WO 2000004120 (Rhodia Chimie); US 6242404 (Rhodia Inc); WO 2001023515 (Rhodia Inc); WO 9941346 (Rhodia Chim); WO 9815346 (Rhodia Inc); WO 9741197 (BASF); EP 728795 (BASF); US 5008032 (BASF); WO 2002077063 (BASF); EP 483606 ( BASF); EP 442101 (BASF); WO 9820092 (Proctor & Gamble ); EP 201124 (Proctor & Gamble ); EP 199403 (Proctor & Gamble ); DE 2527793 (Proctor & Gamble ); WO 9919429 (Proctor & Gamble ); WO 985
  • the most preferred soil release polymers are the water soluble/miscible or dispersible polyesters such as: linear polyesters sold under the Repel-O-Tex brand by Rhodia (gerol), lightly branched polyesters sold under the Texcare brand by Clariant, especially Texcare SRN170, and heavily branched polyesters such as those available from Sasol and described in US 7119056 .
  • One or more enzymes may be present in a composition of the invention and when practicing a method of the invention.
  • suitable lipases include those of bacterial or fungal origin. Chemically modified or protein engineered mutants are included. Examples of useful lipases include lipases from Humicola (synonym Thermomyces), e.g. from H. lanuginosa (T. lanuginosus) as described in EP 258 068 and EP 305 216 or from H. insolens as described in WO 96/13580 , a Pseudomonas lipase, e.g. from P . alcaligenes or P . pseudoalcaligenes ( EP 218 272 ), P . cepacia ( EP 331 376 ), P .
  • lipase variants such as those described in WO 92/05249 , WO 94/01541 , EP 407 225 , EP 260 105 , WO 95/35381 , WO 96/00292 , WO 95/30744 , WO 94/25578 , WO 95/14783 , WO 95/22615 , WO 97/04079 and WO 97/07202 .
  • 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. However lipase is particularly preferred.
  • the presence of relatively high levels of calcium in the poorly built or unbuilt compositions of the invention has a beneficial effect on the turnover of certain enzymes, particularly lipase enzymes and preferably lipases from Humicola.
  • the preferred lipases include first wash lipases which comprise a polypeptide having an amino acid sequence which has at least 90% sequence identity with the wild-type lipase derived from Humicola lanuginosa strain DSM 4109 and compared to said wild-type lipase, comprises a substitution of an electrically neutral or negatively charged amino acid within 15 A of E1 or Q249 with a positively charged amino acid; and may further comprise:
  • phospholipase classified as EC 3.1.1.4 and/or EC 3.1.1.32.
  • phospholipase is an enzyme which has activity towards phospholipids.
  • Phospholipids such as lecithin or phosphatidylcholine, consist of glycerol esterified with two fatty acids in an outer (sn-1) and the middle (sn-2) positions and esterified with phosphoric acid in the third position; the phosphoric acid, in turn, may be esterified to an amino-alcohol.
  • Phospholipases are enzymes which participate in the hydrolysis of phospholipids.
  • phospholipases A 1 and A 2 which hydrolyze one fatty acyl group (in the sn-1 and sn-2 position, respectively) to form lysophospholipid
  • lysophospholipase or phospholipase B
  • Phospholipase C and phospholipase D release diacyl glycerol or phosphatidic acid respectively.
  • proteases include those of animal, vegetable or microbial origin. Microbial origin is preferred. Chemically modified or protein engineered mutants are included.
  • the protease may be a serine protease or a metallo protease, preferably an alkaline microbial protease or a trypsin-like protease.
  • Preferred commercially available protease enzymes include AlcalaseTM, SavinaseTM, PrimaseTM, DuralaseTM, DyrazymTM, EsperaseTM, EverlaseTM, PolarzymeTM, and KannaseTM, (Novozymes A/S), MaxataseTM, MaxacalTM, MaxapemTM, ProperaseTM, PurafectTM, Purafect OxPTM, FN2TM, and FN3TM (Genencor International Inc.).
  • the method of the invention may be carried out in the presence of cutinase. classified in EC 3.1.1.74.
  • the cutinase used according to the invention may be of any origin.
  • Preferably cutinases are of microbial origin, in particular of bacterial, of fungal or of yeast origin.
  • Suitable amylases include those of bacterial or fungal origin. Chemically modified or protein engineered mutants are included. Amylases include, for example, alpha-amylases obtained from Bacillus, e.g. a special strain of B. licheniformis, described in more detail in GB 1,296,839 , or the Bacillus sp. strains disclosed in WO 95/026397 or WO 00/060060 .
  • amylases are DuramylTM, TermamylTM, Termamyl UltraTM, NatalaseTM, StainzymeTM, FungamylTM and BANTM (Novozymes A/S), RapidaseTM and PurastarTM (from Genencor International Inc.).
  • Suitable cellulases include those of bacterial or fungal origin. Chemically modified or protein engineered mutants are included. Suitable cellulases include cellulases from the genera Bacillus, Pseudomonas, Humicola, Fusarium, Thielavia, Acremonium, e.g. 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., (1995) Mol. Plant-Microbe Interact. 8: 331-334 and Henrissat et al., (1995) Plant Physiol. 107: 963-976 .
  • pectatel lyases are disclosed in WO 99/27083 and WO 99/27084 .
  • pectate lyases derived from Bacillus licheniformis
  • US patent no. 6,284,524 which document is hereby incorporated by reference
  • pectate lyase variants are disclosed in WO 02/006442 , especially the variants disclosed in the Examples in WO 02/006442 (which document is hereby incorporated by reference).
  • alkaline pectate lyases examples include BIOPREPTM and SCOURZYMETM L from Novozymes A/S, Denmark.
  • Mannanase examples include mannanases of bacterial and fungal origin.
  • the mannanase is derived from a strain of the filamentous fungus genus Aspergillus, preferably Aspergillus niger or Aspergillus aculeatus ( WO 94/25576 ).
  • WO 93/24622 discloses a mannanase isolated from Trichoderma reseei. Mannanases have also been isolated from several bacteria, including Bacillus organisms. For example, Talbot et al., Appl. Environ. Microbiol., Vol.56, No. 11, pp.
  • JP-A-03047076 discloses a beta-mannanase derived from Bacillus sp.
  • JP-A-63056289 describes the production of an alkaline, thermostable beta-mannanase.
  • JP-A-63036775 relates to the Bacillus microorganism FERM P-8856 which produces beta-mannanase and beta-mannosidase.
  • JP-A-08051975 discloses alkaline beta-mannanases from alkalophilic Bacillus sp. AM-001.
  • a purified mannanase from Bacillus amyloliquefaciens is disclosed in WO 97/11164 .
  • WO 91/18974 describes a hemicellulase such as a glucanase, xylanase or mannanase active.
  • mannanases derived from Bacillus agaradhaerens, Bacillus licheniformis, Bacillus halodurans, Bacillus clausii, Bacillus sp., and Humicola insolens disclosed in WO 99/64619 .
  • Bacillus sp. mannanases concerned in the Examples in WO 99/64619 .
  • mannanases examples include MannawayTM available from Novozymes A/S Denmark.
  • the enzyme and any perfume/fragrance or pro-fragrance present may show some interaction and should be chosen such that this interaction is not negative. Some negative interactions may be avoided by encapsulation of one or other of enzyme and pro-fragrance and/or other segregation within the product.
  • Any enzyme present in the composition may be stabilized using conventional stabilizing agents, e.g., a polyol such as propylene glycol or glycerol, a sugar or sugar alcohol, lactic acid, boric acid, or a boric acid derivative, e.g., an aromatic borate ester, or a phenyl boronic acid derivative such as 4-formylphenyl boronic acid, and the composition may be formulated as described in e.g. WO 92/19709 and WO 92/19708 .
  • a polyol such as propylene glycol or glycerol
  • a sugar or sugar alcohol lactic acid, boric acid, or a boric acid derivative, e.g., an aromatic borate ester, or a phenyl boronic acid derivative such as 4-formylphenyl boronic acid
  • Detergent compositions according to the invention may comprise a bleach system.
  • 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 WO02/48301
  • 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 method of the present invention preferably used 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.
  • deposition aids include those which are substantive to cellulose.
  • the deposition aid is a polysaccharide.
  • the polysaccharide is a ß-1,4-linked backbone and is substantive to cellulose.
  • the polysaccharide is a cellulose, a cellulose derivative, or another ß-1,4-linked polysaccharide having an affinity for cellulose, such as polymannan, polyglucan, polyglucomannan, polyxyloglucan and polygalactomannan or a mixture thereof.
  • the polysaccharide is selected from the group consisting of polyxyloglucan and polygalactomannan.
  • Particularly preferred polysaccharides are locust bean gum, tamarind xyloglucan, guar gum or mixtures thereof.
  • the deposition aid is locust bean gum.
  • Cationic polymer can also be used as deposition aids.
  • cationic polymers used as coatings are cationically modified starch and cationically modified guar, polymers comprising poly diallyl dimethyl ammonium halides (PolyDADMAC), and copolymers of DADMAC with vinyl pyrrolidone, acrylamides, imidazoles, imidazolinium halides, and the like.
  • PolyDADMAC poly diallyl dimethyl ammonium halides
  • acrylamides vinyl pyrrolidone
  • acrylamides vinyl pyrrolidone
  • imidazoles imidazolinium halides
  • Cationic polysaccharides are preferred.
  • Particularly preferred cationic starches have a molecular weight of from about 100,000 to about 500,000,000, preferably from about 200,000 to about 10,000,000 and most preferably from about 250,000 to about 5,000,000.
  • Particularly preferred cationic starch products are HI-CAT CWS42 and HI-CAT 02 and are commercially available from ROQUETTE AMERICA, Inc.
  • Preferred cationic guars have a molecular weight of from about 50,000 to about 0.5,000,000.
  • Suitable cationic polymeric deposition aids include cationic guar polymers such as Jaguar (ex Rhone Poulenc), cationic cellulose derivatives such as Celquats (ex National Starch), Flocaid (ex National Starch), cationic potato starch such as SoftGel (ex Aralose), cationic polyacrylamides such as PCG (ex Allied Colloids).
  • the preferred cationic guars are Jaguar C-162 and Jaguar C-17 and are commercially available from Rhodia Inc.
  • the polyester-substantive deposition aid is a polymer derivable from dicarboxylic acids and polyols, particularly a phthalate containing polymer, more preferably a polymer comprising units derived from (poly)ethylene glycol and terephthalate.
  • the polymer is a selected from the group comprising PET/POET, PEG/POET, PET/PEG and phthalate/glycerol/ethylene glycol polymers. Materials of this type are widely available to the laundry formulator as they are commonly used as soil-release polymers (as discussed above). Given the more efficient deposition of certain benefit ingredients from the compositions of the present invention it is possible to deliver more expensive benefit agents than would otherwise be economic, these can include materials having a benefit other than a pleasant odour, such as an aromatherapeutic benefit.
  • compositions of the invention may contain one or more other ingredients.
  • ingredients include viscosity modifiers, preservatives (e.g. bactericides), pH buffering agents, hydrotropes, polyelectrolytes, anti-shrinking agents, anti-wrinkle agents, anti-oxidants, sunscreens, anti-corrosion agents, drape imparting agents, anti-static agents and ironing aids.
  • preservatives e.g. bactericides
  • pH buffering agents e.g., hydrotropes, polyelectrolytes, anti-shrinking agents, anti-wrinkle agents, anti-oxidants, sunscreens, anti-corrosion agents, drape imparting agents, anti-static agents and ironing aids.
  • hydrotropes e.g. bactericides
  • polyelectrolytes e.g. bactericides
  • anti-shrinking agents e.g. bactericides
  • anti-wrinkle agents e.g., anti-oxidants
  • sunscreens e.
  • the detergent compositions herein may also optionally contain relatively low levels of organic detergent builder material.
  • organic detergent builder 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, C 10 -C 22 fatty acids and citric acid.
  • DEQUESTTM organic phosphonate type sequestering agents sold by Monsanto and alkahehydroxy phosphonates. Citrate salts and C 12 -C 18 fatty acid soaps are highly preferred.
  • 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 (other than soaps) is less and 10 wt% and preferably less than 5 wt% of the composition.
  • overall builder levels of less than 10 wt% are preferred, as this not only reduces the quantity of product required per wash but also maintains a level of calcium which assists in the activity of certain enzymes.
  • Such low builder (or zero builder) levels are also useful when pre-softened water is used for the dilution step.
  • compositions according to the invention Two ingredients that are very much preferred to be present in compositions according to the invention are buffers and hydrotropes.
  • buffers are borax, MEA, and TEA. They are used in the composition at levels of from 5 to 15 wt%.
  • Preferred liquids will comprise some hydrotrope, although the minimum amount consistent with the need for concentration should be used.
  • Suitable hydrotropes include MPG (monopropylene glycol). This and/or other conventionally employed hydrotropes may be used in the composition at levels of from 2 to 10 wt%.
  • Example 1 Calcium tolerant surfactant blends
  • the surfactant blends listed in Table 1a were prepared at a concentration of 0.7 g/l in water containing sufficient Calcium ions to give a French Hardness of 40 degrees. Following the method disclosed in EP1771543 other electrolytes such as sodium chloride, sodium sulphate, sodium hydroxide were added as necessary to adjust the ionic strength to 0.5M and the pH to 10. The absorption of light of wavelength 540nm through 4mm of sample was measured 15 minutes after sample preparation. Ten measurements are made and an average value is calculated. Samples that give an absorption value of less than 0.08 are deemed to be calcium tolerant.
  • the washes were conducted in a European Miele washing machine using its standard 40°C cotton wash cycle.
  • the main wash intake was 15 1 of ambient temperature water of 26°FH water (Ca:Mg 3:1) and the total wash time (including rinses) was 1hour 56 mins.
  • a mixed ballast load of 3kg (40% woven polycotton, 30% woven cotton, 30% knitted cotton) was also included in each cycle to better mimic real wash use conditions. Examples 2 to 5 were dosed at a total product volume of 20 ml/wash, whilst the control used was (Persil "Small and Mighty” TM) it was dosed at 35 ml/wash, as per manufacturer's recommendation.
  • Active lipase protein level is 100 000 LU/g Novozymes Texcare SRN170 Soil release polymer Clariant Sokolan CP5 Soil release polymer BASF Empigen BB Non-soap surfactant (Betaine) Huntsman Notes on ingredients in table 2b
  • compositions of Examples 2 to 5 were determined to be as follows:
  • compositions 6-9 which are all embodiments of the invention.
  • the Linitest pots were filled with 6°FH water (2:1 Ca2+:Mg2+) and then the required surfactant and polymer solutions such that the final wash liquor volume was 100ml. Using either 0.1M NaOH or 0.1M HCl the wash liquor pH was adjusted to 7. To each Lintiest pot 2 woven cotton and 2 knitted polyester yellow pottery clay stains plus 4 ballast cloths (2 cotton and 2 knitted polyester) were then added with liquor to cloth ratios of 8:1. Finally, fifty metal ball bearings were added before closing the Linitest pot and washing the cloths for 15 minutes at 25°C and 100rpm.
  • the colour of the stains was measured both before and after washing on a Hunter lab reflectometer and expressed in terms of the difference between the stain and clean cloth giving ⁇ E*before wash or ⁇ E*after wash values respectively.
  • the ⁇ E values are colour differences defined as the Euclidian distance between the stain and clean cloth in L*a*b* colour space.
  • EPEI is more effective at lower in wash non-soap surfactant levels for this type of soil and EPEI is even more effective at low non-soap surfactant concentrations if it is used with betaine as part of the surfactant system.
  • composition used was as detailed below. No other ingredients were used. 19.11% NI, 7EO 12.73% LAS acid 6.37% SLES 4.54% Fatty acid 2.25% Betaine
  • Test pieces were subjected to a 15 minute wash in linitest with a liquor to cloth ratio of 8:1 at a temperature of 25°C.
  • the water hardness used was 6°FH (2:1 Ca:Mg).
  • the wash was followed by two 3 minute rinses in the linitest.
  • Key Marker stain for EPEI performance is Red Pottery clay on knitted polyester.
  • the wash conditions used were European FLA Washing Machines with normal 40°C Cotton Wash Cycle. 3kg of mixed standard ballast was included in the 15 Litre fill.
  • the monitors comprised stains on knitted cotton and knitted polyester, together with Lard on blue knitted cotton.
  • Table 10 Eg 21 30% active + Lipex Eg 22 30% active + EPEI+Lipex Eg 23 30% active + EPEI + lipolase Eg 24 30% active + EPEI + SRP Eg 25 30% active + EPEI+Lipex+ SRP Eg 26 30% active + EPEI + lipolase +SRP Glycerol 3.17 3.17 3.17 3.17 3.17 3.17 MPG 5.7 5.7 5.7 5.7 5.7 5.7 NaOH 2.13 2.13 2.13 2.13 2.13 2.13 TEA 2.05 2.05 2.05 2.05 2.05 2.05 2.05 Neodol 7EO 12.74 12.74 12.74 12.74 12.74 12.74 12.74 F dye 0.18 0.18 0.18 0.18 0.18 0.18 Citric acid 1.71 1.71 1.71 1.
  • lipex For the knitted polyester addition of lipex produces significant wins over base on particulate, fatty and food sauce stains. Addition of lipolase shows surprisingly improved first wash performance on the particulate and fatty stains, as seen with lipex, which is sold as a first wash lipase enzyme.
  • a combination of enzyme and SRN170 shows significant increase in performance of all stain groups, except bleachable.
  • a liquid detergent composition comprising surfactant including betaine, EPEI at more than 5 wt%, and Lipase enzyme was made up into a wash solution for testing and buffered to pH9 (full composition details are given in table 16). The amount used was equivalent to a 20 ml dose to a front loading automatic washing machine. Cotton terry test pieces and various amounts of LBG-silicone were added into the wash liquor. And the swatches were subjected to Linitest washes at 40°C for a 45 minute main wash, followed by 2x10 min rinses, and, line drying. Softness of the test pieces was assessed by two trained panellists.
  • LBG-Silicone gives perceivable softening from this liquid detergent composition. There is no appreciable difference in softening below 3.5 wt% LBG silicone. Above that, the amount of softening perceived increased with increasing levels of LBG silicone. LBG is thus shown to act as a very effective deposition aid for the silicone softening benefit agent in the compositions used according to the invention.

Claims (14)

  1. Verfahren zum Waschen von Textilerzeugnissen,
    das die folgenden Schritte aufweist:
    a) Bereitstellen einer gießfähigen flüssigen Waschmittelzusammensetzung, die ethoxyliertes Polyethylenimin, schmutzlösendes Polymer, 10 bis 40 Gew.-% Tensid, das im Wesentlichen aus nichtionischem und/oder anionischem und/oder zwitterionischem Tensid besteht, wobei vorzugsweise 10 bis 40 Gew.-% des Tensids den hier beschriebenen Calciumtoleranztest bestehen, und außerdem nicht mehr als 15 Gew.-%, vorzugsweise nicht mehr als 10 Gew.-% einer Seife aufweist, mit der Maßgabe, dass irgendeine vorhandene Seife als geringfügiger Bestandteil vorliegt, und zwar auf die Gew.-% des gesamten Tensids bezogen, wobei das Verhältnis zwischen seifenfreiem Tensid und ethoxyliertem Polyethylenimin 2:1 bis 7:1 beträgt;
    b) Verdünnen einer Dosis der Waschmittelzusammensetzung in Wasser mit einem Faktor mit mehr als 500, um eine Waschflüssigkeit zu erhalten, die 0,8 bis 0,035 g/l seifenfreies Tensid aufweist; und
    c) Waschen von Textilerzeugnissen mit der so erzeugten Waschflüssigkeit.
  2. Verfahren zum Waschen von Textilerzeugnissen,
    das die folgenden Schritte aufweist:
    a) Bereitstellen eines Behälters mit mehreren Dosen, der eine gießfähige flüssige Waschmittelzusammensetzung enthält, die ethoxyliertes Polyethylenimin, schmutzlösendes Polymer, 10 bis 40 Gew.-% Tensid, das im Wesentlichen aus nichtionischem und/oder anionischem und/oder zwitterionischem Tensid besteht, und außerdem nicht mehr als 15 Gew.-%, vorzugsweise nicht mehr als 10 Gew.-% einer Seife aufweist, mit der Maßgabe, dass irgendeine vorhandene Seife als geringfügiger Bestandteil vorliegt, und zwar auf die Gew.-% des gesamten Tensids bezogen;
    b) Mischen einer Dosis der Waschmittelzusammensetzung, die 4 bis 8 g seifenfreies Tensid, mindestens 0,5 g schmutzlösendes Polymer und mindestens 0,5 g des ethoxylierten Polyethylenimins aufweist, mit Wasser, um eine Waschflüssigkeit zu erhalten, wobei das Verhältnis zwischen seifenfreiem Tensid und ethoxyliertem Polyethylenimin 2:1 bis 7:1 beträgt; und
    c) Waschen von Textilerzeugnissen mit der so erzeugten Waschflüssigkeit.
  3. Verfahren nach Anspruch 2,
    wobei die Dosis mindestens 0,01 g aktives Protein in Form von Lipase aufweist.
  4. Verfahren nach einem der vorstehenden Ansprüche,
    wobei die Zusammensetzung 5 bis 20000 LU/g Lipase aufweist.
  5. Verfahren nach einem der vorstehenden Ansprüche,
    wobei die Zusammensetzung ethoxyliertes Polyethylenimin in einer Menge von 0,01 bis 25 Gew.-%, vorzugsweise von mehr als 3 und/oder weniger als 9,5 Gew.-% der Zusammensetzung, besonders bevorzugt von 4 bis 9 Gew.-% der Zusammensetzung aufweist.
  6. Verfahren nach einem der vorstehenden Ansprüche,
    wobei die Zusammensetzung ein schmutzlösendes Polymer in einer Menge von vorzugsweise 3 bis 9,0 Gew.-%, vorzugsweise von 6 bis 8,0 Gew.-% der Zusammensetzung aufweist.
  7. Verfahren nach einem der vorstehenden Ansprüche,
    wobei 10 bis 40 Gew.-% des seifenfreien Tensids in der Zusammensetzung weniger als 90 Gew.-% LAS und mindestens 10 Gew.-% nichtionisches Tensid aufweisen.
  8. Verfahren nach einem der vorstehenden Ansprüche,
    wobei die Zusammensetzung einen Nuancierfarbstoff, der einen blau-violetten Farbstoff aufweist, vorzugsweise mit einem Lichtadsorptionpeak im Bereich von 540 bis 600 nm, vorzugsweise einen Bisazo-Direktfarbstoff, vorzugsweise in einer Menge von 0,000001 bis 1 Gew.-% der Zusammensetzung aufweist.
  9. Verfahren nach einem der vorstehenden Ansprüche,
    wobei die Zusammensetzung einen Aufheller, vorzugsweise in einer Menge von 0,005 bis 2 Gew.-% der Zusammensetzung aufweist.
  10. Verfahren nach einem der vorstehenden Ansprüche,
    wobei die Zusammensetzung ein die Farbstoffübertragung hemmendes Polymer, vorzugsweise in einer Menge von 0,01 bis 10 Gew.-%, stärker bevorzugt von 0,02 bis 8 Gew.-%, besonders bevorzugt von 0,03 bis 6 Gew.-% der Zusammensetzung aufweist.
  11. Verfahren nach einem der vorstehenden Ansprüche,
    wobei die Zusammensetzung einen Vergrauungsinhibitor in Form von Polycarboxylat, vorzugsweise in einer Menge von 0,01 bis 10 Gew.-%, stärker bevorzugt von 0,02 bis 8 Gew.-%, besonders bevorzugt von 0,03 bis 6 Gew.-% der Zusammensetzung aufweist.
  12. Verfahren nach einem der vorstehenden Ansprüche,
    wobei die Zusammensetzung eine Lipase für den ersten Waschgang aufweist, die ein Polypeptid mit einer Aminosäuresequenz aufweist, die eine Sequenzübereinstimmung mit der Lipase vom Wildtyp von mindestens 90 % hat, die vom Stamm Humicola lanuginosa DSM 4109 abgeleitet ist, und im Vergleich mit der Lipase vom Wildtyp eine Substitution einer elektrisch neutralen oder negativ geladenen Aminosäure innerhalb von 15 A der EI oder Q249 mit einer positiv geladenen Aminosäure aufweist; und die ferner:
    a) eine Peptid-Addition am C-Terminus aufweist, und/oder
    b) eine Peptid-Addition am M-Terminus aufweist, und/oder
    c) den folgenden Einschränkungen entspricht:
    i) sie weist eine negativ geladene Aminosäure in der Position E210 der Lipase vom Wildtyp auf;
    ii) sie weist eine negativ geladene Aminosäure in der Region auf, die den Positionen 90 - 101 der Lipase vom Wildtyp entspricht; und
    iii) sie weist eine neutrale oder negativ geladene Aminosäure in der Position auf, die N94 der Lipase vom Wildtyp entspricht; und/oder iii) sie weist eine negative Ladung oder eine neutrale Ladung in der Region auf, die den Positionen 90 - 101 der Lipase vom Wildtyp entspricht.
  13. Verfahren nach einem der vorstehenden Ansprüche,
    wobei die Zusammensetzung ein Ablagerungshilfsmittel aufweist, wobei das Ablagerungshilfsmittel ein Polysaccharid, stärker bevorzugt ein [β]-1,4 gebundenes Polysaccharid ist, besonders bevorzugt ist das Ablagerungshilfsmittel Johannisbrotkernmehl.
  14. Verfahren nach einem der vorstehenden Ansprüche,
    wobei die Zusammensetzung ein schmutzlösendes Polymer aufweist, das aus wasserlöslichem/mit Wasser mischbarem oder in Wasser dispergierbarem Polyester ausgewählt ist.
EP09765764.7A 2008-06-16 2009-06-08 Verbesserungen im zusammenhang mit stoffreinigung Revoked EP2300586B1 (de)

Priority Applications (2)

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PL09765764T PL2300586T3 (pl) 2008-06-16 2009-06-08 Ulepszenia dotyczące czyszczenia tkanin
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GBGB0810881.3A GB0810881D0 (en) 2008-06-16 2008-06-16 Improvements relating to fabric cleaning
EP08171961A EP2135934B1 (de) 2008-06-16 2008-12-17 Verwendung einer Waschmittelzusammensetzung
EP09765764.7A EP2300586B1 (de) 2008-06-16 2009-06-08 Verbesserungen im zusammenhang mit stoffreinigung
PCT/EP2009/057019 WO2009153184A1 (en) 2008-06-16 2009-06-08 Improvements relating to fabric cleaning

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