EP2408890B1 - Method of industrial or institutional laundry for a polyester load - Google Patents

Method of industrial or institutional laundry for a polyester load Download PDF

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Publication number
EP2408890B1
EP2408890B1 EP10708481.6A EP10708481A EP2408890B1 EP 2408890 B1 EP2408890 B1 EP 2408890B1 EP 10708481 A EP10708481 A EP 10708481A EP 2408890 B1 EP2408890 B1 EP 2408890B1
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EP
European Patent Office
Prior art keywords
load
weight
polyester
laundry
wash
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EP10708481.6A
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German (de)
French (fr)
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EP2408890A1 (en
Inventor
Francesco De Buzzaccarini
Raphael Angeline Alfons Ceulemans
Matthew Thomas Heisey
Edward Robert Offshack
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Procter and Gamble Co
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Procter and Gamble Co
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Classifications

    • CCHEMISTRY; METALLURGY
    • C11ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11DDETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D3/00Other compounding ingredients of detergent compositions covered in group C11D1/00
    • C11D3/0005Other compounding ingredients characterised by their effect
    • C11D3/0026Low foaming or foam regulating compositions
    • CCHEMISTRY; METALLURGY
    • C11ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11DDETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D1/00Detergent compositions based essentially on surface-active compounds; Use of these compounds as a detergent
    • C11D1/66Non-ionic compounds
    • C11D1/83Mixtures of non-ionic with anionic compounds
    • CCHEMISTRY; METALLURGY
    • C11ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11DDETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D3/00Other compounding ingredients of detergent compositions covered in group C11D1/00
    • C11D3/02Inorganic compounds ; Elemental compounds
    • C11D3/12Water-insoluble compounds
    • C11D3/124Silicon containing, e.g. silica, silex, quartz or glass beads
    • CCHEMISTRY; METALLURGY
    • C11ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11DDETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D3/00Other compounding ingredients of detergent compositions covered in group C11D1/00
    • C11D3/16Organic compounds
    • C11D3/37Polymers
    • C11D3/3703Macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
    • C11D3/373Macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds containing silicones
    • CCHEMISTRY; METALLURGY
    • C11ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11DDETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D1/00Detergent compositions based essentially on surface-active compounds; Use of these compounds as a detergent
    • C11D1/02Anionic compounds
    • C11D1/12Sulfonic acids or sulfuric acid esters; Salts thereof
    • C11D1/22Sulfonic acids or sulfuric acid esters; Salts thereof derived from aromatic compounds
    • CCHEMISTRY; METALLURGY
    • C11ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11DDETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D2111/00Cleaning compositions characterised by the objects to be cleaned; Cleaning compositions characterised by non-standard cleaning or washing processes
    • C11D2111/10Objects to be cleaned
    • C11D2111/12Soft surfaces, e.g. textile

Definitions

  • the present invention is in the field of laundry.
  • it relates to a method of industrial or institutional laundry for a polyester load using a silicone suds suppressor during the wash process.
  • detergents for household (or home) and professional (including institutional and industrial) laundries are similar, detergents for large-scale institutional or industrial use generally differ insofar as they must be designed to meet the special circumstances associated with laundry on an industrial scale and/or in an institutional context. Contrary to home laundry, professional laundries have to deal with large volumes of textile items and require therefore completely automatic processing with microprocessor-controlled machines and dosing units. The length of the washing process differs from that of home laundry and in some cases the washing is performed with soft water.
  • Soil levels can be significantly lower in certain types of loads of professional laundry (for example towels and bed linen in a hotel which have ninimal use and soiling before being re-washed) than in household laundry and the loads and the machines are considerably bigger.
  • the composition of the loads is more uniform, in terms of both, types of fabrics and soils.
  • a typical commercial laundry load will consist of only towels, only bed linen or only table linen (tablecloths and napkins).
  • Soft water also promotes sudsing. Under these circumstances, it is difficult to perform a good cleaning.
  • Fatty acids or fatty soaps are commonly used as suds suppressors in laundry. They rely on the presence of water hardness ions to work. When water hardness ions are present they can form salts which can disrupt the suds. If there are no water hardness ions, as the case is with soft water, then the soap might even cause additional suds. It has been found that if a load of polyester is washed in soft water, using a normal amount of detergent, the level of suds can be so high that it can overflow the machine, this seems to be worse when the level of soil is low.
  • polyester load is understood a load comprising at least 50%, preferably at least 60%, more preferably at least 80% and more preferably at least 95% by weight of the load of polyester items.
  • the level of anionic surfactant is greater than 12%, more preferably greater than 15% and especially greater than 20% by weight of the detergent composition. This provides an outstanding cleaning over a great range of soils.
  • the detergent composition comprises non-ionic surfactant and anionic surfactant.
  • the level of anionic surfactant is higher than the level of non-ionic surfactant, by "higher” is herein meant that the level of anionic surfactant is at least 1% by weight more than the level of non-ionic surfactant, preferably at least 5%, more preferably at least 15% and especially at least 20%.
  • the level of non-ionic surfactant is less than 10% by weight of the detergent composition.
  • the method of the invention also allows for flexibility in terms of detergent formulation.
  • Polyester with low level of soil and new polyester items can be even more prone to sudsing than highly soiled items.
  • the method of the invention performs very well even in the case of loads with low level of soil (typically towels or bed linen) or new items.
  • low soiled items is herein understood items free from visible stains.
  • new items is herein understood items that have not been subjected to a washing process.
  • the water of the wash liquor of the method of the invention preferably the water of the liquor of each cycle, has a hardness, i.e., Ca and Mg ions concentration, of less than 1, preferably less than 0.5 and especially less than 0.2 mmoles/litre.
  • the method of the invention involves the step of heating the cleaning water using steam, in particular steam injection.
  • the level of active suds suppressor in the wash liquor is from 0.1 to 10, more preferably from 0.2 to 5 and especially from 0.8 to 3 ppm.
  • the suds suppressor for use herein is a polydimethlysiloxane compounded with silica.
  • the wash liquor preferably the wash liquor of the main wash, has a pH of from 7 to 9, preferably from 8 to 9, as measured at room temperature (20°C) this allows not only for good cleaning but also for good care of the washed articles.
  • the detergent composition comprises anionic surfactant, in a level of at least 12% by weight of the detergent composition, and at least 80% by weight of the anionic surfactant is sodium lauryl benzene sulfonate.
  • anionic surfactant is sodium lauryl benzene sulfonate.
  • the method of the invention comprises the step of contacting the load with a soil release polymer, in any of the wash cycles, preferably during the main-wash or a rinse cycle.
  • a soil release polymer is added as part of an additive rather than as part of a detergent composition. This not only obviates the process challenges found to make the soil release polymer part of a base detergent but also eliminates the interaction between some of the base detergent ingredients and the polymer and gives flexibility in terms of dosing.
  • the present invention envisages a method of professional laundry of a polyester load.
  • the method involves contacting the load with a detergent comprising a silicone suds suppressor.
  • the method provides improved cleaning. It has been found that the problem of high suds is more acute in the case of a load with low level of soil, ie. a load with less than 10 g of soil per kilogram of load, preferably with less than 5 g of soil per kilogram of load.
  • the polyester load used in the method of the present invention is a load with low level of soil.
  • Institutional laundry refers to textile washing operations usually run in business sites, normally referred to as On-Premise or In-House Laundry Operations. Typical businesses can be for instance hotels, restaurants, care homes, hospitals, spas, health or sport clubs, schools, and similar institutions.
  • Industrial laundry refers to textile washing operations carried out in dedicated places typically for the above businesses.
  • professional laundry machine is herein meant a laundry machine which a capacity higher than 25 kg of dry laundry.
  • front load which operate in a batch mode or tunnel washing machines that operate in continuous mode.
  • the professional laundry machines for use herein, in the case of front load have a drum volume of at least about 0.15 m 3 , preferably at least 0.2 m 3 , more preferably at least 0.3 m 3 and especially at least 0.5 m 3 .
  • the professional laundry machines for use herein, in the case of front load have a drum diameter of at least about 0.5 m, preferably at least 0.8 m and more preferably at least 1 m.
  • the tunnel has a diameter of at least about 1.5 m, preferably at least 3m and more preferably at least 5 m.
  • Silicone suds suppressor is defined herein as an antifoam compound that is a polydimethylsiloxane compounded with silica.
  • the polydimethylsiloxane is a relatively high molecular weight polymer containing siloxane units and methyl groups that is chemisorbed or fused onto silica.
  • Silicone suds suppressers are well known in the art and are, for example, disclosed in U.S. Pat. No. 4,265,779 , and EP 354 016 .
  • Other silicone suds suppressers are disclosed in U.S. Pat. No. 3,455,839 which relates to compositions and processes for defoaming aqueous solutions by incorporating therein small amounts of polydimethylsiloxane fluids.
  • Silicone defoamers and suds controlling agents in granular detergent compositions are disclosed in U.S. Pat. No. 3,933,672 and in U.S. Pat. No. 4,652,392 .
  • Suitable polydimethylsiloxanes compounded with silica particles are commercially available from Dow Coming, Wacker Chemie and General Electric.
  • the Silicone suds suppressor is utilized in amounts up to about 2% by weight of the detergent composition. This upper limit is practical in nature, due primarily to concern with keeping costs minized and effectiveness of lower amounts for effectively controlling sudsing. Preferably from 0.01 % to 1% of active silicone suds suppressor is used, more preferably from 0.05% to 0.5% by weight of the detergent composition.
  • active excludes water and inactive ingredients (in terms of suds suppression).
  • compositions suitable for use herein comprise from 20% to 50% by weight of a certain kind of detersive surfactant component.
  • a certain kind of detersive surfactant component Such an essential detersive surfactant component must comprise a combination of anionic surfactant and nonionic surfactant.
  • Suitable anionic surfactants useful herein can comprise any of the conventional anionic surfactant types typically used in liquid detergent products. These include the alkyl benzene sulfonic acids and their salts as well as alkoxylated or un-alkoxylated alkyl sulfate materials.
  • Preferred anionic surfactants are the alkali metal salts of C 10-16 alkyl benzene sulfonic acids, preferably C 11-14 alkyl benzene sulfonic acids.
  • the alkyl group is linear and such linear alkyl benzene sulfonates are known as "LAS".
  • Alkyl benzene sulfonates, and particularly LAS, are well known in the art.
  • Such surfactants and their preparation are described for example in U.S. Patents 2,220,099 and 2,477,383 .
  • Especially preferred are the sodium and potassium linear straight chain alkylbenzene sulfonates in which the average number of carbon atoms in the alkyl group is from about 11 to 14.
  • Sodium C 11 -C 14 e.g., C 12
  • LAS is especially preferred.
  • At least 80% by weight of the anionic surfactant is sodium lauryl benzene sulfonate.
  • anionic surfactant comprises ethoxylated alkyl sulfate surfactants.
  • Such materials also known as alkyl ether sulfates or alkyl polyethoxylate sulfates, are those which correspond to the formula: R'-O-(C 2 H 4 O) n -SO 3 M wherein R' is a C 8 -C 20 alkyl group, n is from about 1 to 20, and M is a salt-forming cation.
  • R' is C 10 -C 18 alkyl, n is from about 1 to 15, and M is sodium, potassium, ammonium, alkylammonium, or alkanolammonium.
  • R' is a C 12 -C 16 , n is from about 1 to 6 and M is sodium.
  • Preferred unalkoyxylated, e.g., unethoxylated, alkyl ether sulfate surfactants are those produced by the sulfation of higher C 8 -C 20 fatty alcohols.
  • Conventional primary alkyl sulfate surfactants have the general formula: ROSO 3 - M + wherein R is typically a linear C 8 -C 20 hydrocarbyl group, which may be straight chain or branched chain, and M is a water-solubilizing cation.
  • R is a C 10 -C 15 alkyl
  • M is alkali metal.
  • R is C 12 -C 14 and M is sodium.
  • Suitable nonionic surfactants useful herein can comprise any of the conventional nonionic surfactant types typically used in liquid detergent products. These include alkoxylated fatty alcohols, ethylene oxide (EO)-propylene oxide (PO) block polymers, and amine oxide surfactants. Preferred for use in the liquid detergent products herein are those nonionic surfactants which are normally liquid.
  • Alcohol alkoxylates are materials which correspond to the general formula: R 1 (C m H 2m O) n OH wherein R 1 is a C 8 - C 16 alkyl group, m is from 2 to 4, and n ranges from about 2 to 12.
  • R 1 is an alkyl group, which may be primary or secondary, that contains from about 9 to 15 carbon atoms, more preferably from about 10 to 14 carbon atoms.
  • the alkoxylated fatty alcohols will be ethoxylated materials that contain from about 2 to 12 ethylene oxide moieties per molecule, more preferably from about 3 to 10 ethylene oxide moieties per molecule.
  • the alkoxylated fatty alcohol materials useful in the liquid detergent compositions herein will frequently have a hydrophilic-lipophilic balance (HLB) which ranges from about 3 to 17. More preferably, the HLB of this material will range from about 6 to 15, most preferably from about 8 to 15.
  • HLB hydrophilic-lipophilic balance
  • Alkoxylated fatty alcohol nonionic surfactants have been marketed under the tradenames Neodol and Dobanol by the Shell Chemical Company.
  • EO ethylene oxide
  • PO propylene oxide
  • Materials of this type are well known nonionic surfactants which have been marketed under the tradename Pluronic. These materials are formed by adding blocks of ethylene oxide moieties to the ends of polypropylene glycol chains to adjust the surface active properties of the resulting block polymers.
  • Pluronic ethylene oxide moieties to the ends of polypropylene glycol chains to adjust the surface active properties of the resulting block polymers.
  • EO-PO block polymer nonionics of this type are described in greater detail in Davidsohn and Milwidsky; Synthetic Detergents, 7th Ed.; Longman Scientific and Technical (1987) at pp. 34-36 and pp. 189-191 and in U.S. Patents 2,674,619 and 2,677,700 .
  • Nonionic surfactant useful herein comprises the amine oxide surfactants.
  • Amine oxides are mateials which are often referred to in the art as "semi-polar" nonionics. Amine oxides have the formula: R(EO) x (PO) y (BO) z N(O)(CH 2 R') 2 .qH 2 O.
  • R is a relatively long-chain hydrocarbyl moiety which can be saturated or unsaturated, linear or branched, and can contain from 8 to 20, preferably from 10 to 16 carbon atoms, and is more preferably C 12 -C 16 primary alkyl.
  • R' is a short-chain moiety preferably selected from hydrogen, methyl and -CH 2 OH. When x+y+z is different from 0, EO is ethyleneoxy, PO is propyleneneoxy and BO is butyleneoxy. Amine oxide surfactants are illustrated by C 12-14 alkyldimethyl amine oxide.
  • the weight ratio of anionic surfactant to nonionic surfactant is from 20:1 to 1:20.
  • the detergent compositions herein which are in liquid form, comprise from 0.1% to 30% by weight, preferably from 0.5% to 20% by weight, more preferably from 1% to 10% by weight, of one or more of certain kinds of laundry washing adjuncts.
  • laundry washing adjuncts can be selected from detersive enzymes, builders, chelants, soil release polymers, soil suspending polymers, optical brighteners, dye transfer inhibition agents, bleach, whitening agents, suds suppressors, fabric care benefit agents, solvents, stabilizers, buffers, structurants, dyes and perfumes and combinations of these adjunct types. All of these materials are of the type conventionally utilized in laundry detergent products.
  • Soil release polymers enhance the laundry cleaning efficacy by improving release of grease and oil during the laundry process. See soil release agents' definition, p.278-279, "Liquid Detergents" by Kuo-Yann Lai .
  • preferred level of soil release polymer per kilogram of load is from about 0.01 to about 0.8 grams, more preferably the level of polymer is less than 0.2 grams especially from about 0.05 to about 0.15 grams. Contrary to what one would expect higher levels of soil release polymer do not enhance removal. In some cases removal is worse than with lower levels.
  • the soil release polymer is a copolymer having the formula: wherein :
  • w 0.
  • Preferred soil release polymer for use herein is a copolymer comprising propylene glycol derived moieties, terephthalate moieties and capped polyethylene glycol derived moieties.
  • the capped polyethylene glycol used is CH3O(CH2CH2O)nOH, wherein n is an integer from 12 to 44, preferably from 20 to 42 and more preferably from 25 to 41 and especially 40. Improved performance is obtained with this kind of copolymers.
  • the preferred copolymer for use herein has the following formula:
  • the soil release polymer has a molecular weight above about 2,000, more preferably above about 3,000 and more preferably above about 4,000. Methods in which soil release polymers having molecular weight above 4,000 have been used provide outstanding results in terms of stain removal.
  • the molecular weight is below about 20,000.
  • the term "molecular weight” is the weight-average molecular weight as determined using gel permeation chromatography according to the protocol found in Colloids and Surfaces A. Physico Chemical & Engineering Aspects, Vol. 162, 2000, pg. 107-121 . The units are Daltons.
  • the soil release polymer is added as part of an additive.
  • the additive is in liquid form so it can be easily delivered by means of a displacement pump, for example a peristaltic pump.
  • the additive is preferably an aqueous structured liquid, usually the soil release polymer is insoluble in aqueous solution and it is suspended by means of an external structurant.
  • Structured liquids can either be internally structured, whereby the structure is formed by primary ingredients (e.g. surfactant material) and/or externally structured by providing a three dimensional matrix structure using secondary ingredients (e.g. polymers, clay and/or silicate material).
  • the additive comprises the soil release polymer, preferably in an amount of from about 1% to about 50%, more preferably from about 5% to about 20% by weight of the additive.
  • the additive can further comprise an external structurant to keep the soil release polymer suspended.
  • levels of external structurants of from about 0.05 to about 5%, more preferably from about 0.1 to about 2% and especially from about 0.1 to about 1% by weight of the additive have been found particularly suitable to keep the polymer suspended.
  • Preferred external structurant for use herein is xanthan gum.
  • the additive comprises a preservative, more preferred in a level of from about 0.05 to about 3% and especially from about 0.1 to about 1% by weight of the additive.
  • a dye is another prefer component of the additive of the invention.
  • the additive is free of builders and/or surfactants.
  • suitable enzymes include, but are not limited to, hemicellulases, peroxidases, proteases, cellulases, xylanases, lipases, phospholipases, esterases, cutinases, pectinases, keratanases, reductases, oxidases, phenoloxidases, lipoxygenases, ligninases, pullulanases, tannases, mannanases, pentosanases, malanases, ⁇ -glucanases, arabinosidases, hyaluronidase, chondroitinase, laccase, and known amylases, or combinations thereof.
  • a preferred enzyme combination comprises a cocktail of conventional detersive enzymes like protease, lipase, cutinase and/or cellulase in conjunction with amylase.
  • detersive enzymes are described in greater detail in U.S. Patent No. 6,579,839 .
  • the aqueous liquid detergent compositions herein can typically comprise from 0.001% to 5%, preferably from 0.01% to 1% by weight, of a commercial enzyme preparation.
  • Protease enzymes for example, are usually present in such commercial preparations at levels sufficient to provide from 0.005 to 0.1 Anson units (AU) of activity per gram of detergent composition.
  • the detergent may also include from about 0.05 to about 0.5% of preservatives non-limiting examples of which include didecyl dimethyl ammonium chloride which is available under the tradeneme UNIQUAT (from Lonza of Basel Switzerland), 1,2-benzisothiozolin-3-one, which is available under the tradename PROPEL (from Arch Chemicals of Norwalk, Connecticut), dimethylol-5,5-dimethylhydantoin which is available under the tradeneme DANTOGUARD (from Lonza of Basel Switzerland), 5- Chloro-2- methyl-4- isothiazolin-3-one / 2-methyl-4-isothiazolin-3-one, which is available under the tradename KATHON (from Rohm and Haas of Philadelphia, Pennsylvania), and mixtures thereof.
  • preservatives non-limiting examples of which include didecyl dimethyl ammonium chloride which is available under the tradeneme UNIQUAT (from Lonza of Basel Switzerland), 1,2-benzisothiozolin-3-one
  • the detergent composition for use herein may also comprise additional fabric care or benefit agents which can be deposited onto fabrics being laundered and which thereupon provide one or more types of fabric care or treatment benefits.
  • Such benefits can include, for example, fabric softness, anti-static effects, ease-of-ironing benefits, anti-abrasion benefits, anti-pilling effects, color protection, wrinkle removal or improved resistance to wrinkling, fabric substantive perfume or odor benefits, malodor protection benefits, and the like.
  • Such materials can include, for example, clays; starches; polyamines; un-functionalized and functionalized silicones such as aminosilicones and quaternary nitrogen-containing cationic silicones; cellulosic polymers, and the like. Materials of these types are described in greater detail in one or more of the following publications: US 6,525,013 ; US 4,178,254 ; WO 02/40627 ; WO 02/18528 ; WO 00/71897 ; WO 00/71806 ; WO 98/39401 ; and WO 98/29528 .
  • such additional fabric care benefit agents polymers can typically be incorporated into the liquid laundry detergent compositions herein in concentrations ranging from 0.05% to 20%, by weight, depending upon the nature of the materials to be deposited and the benefit(s) they are to provide. More preferably, such fabric care benefit agents can comprise from 0.1% to 10%, by weight of the composition.
  • the detergent used had the following composition and it was used at a dosage of 48 grams/ machine (or 9.6 ml/kg fabric). The detergent was delivered into the main-wash cycle.
  • Table 1 Ingredient % by weight C12-alkylbenxene sulfonic acid 12.2 Non-ionic surfactant 8.75 C12-alkyl trimethyl amine N-oxide 1.5 C12-14 fatty acid 8.3 Citric acid 3.4 Triethyleneimine penta phosphonic acid 0.19 Ethoxylated polymine polymer 1.1 Enzyme 0.53 1,2 propandiol 4.9 Ethanol 2.8 Monethanolamine 0.83 Monoethanaolamine borate 2.4 Cumene sulfonic acid 1.9 BF20 plus silicone suds suppressor Ex Dow Coming 0.13 Hydrogenated castor oil 0.10 Perfume and minors 0.5 Sodium hydroxide to pH 8.0 water Balance
  • a low suds profile was obtained using the exemplified detergent.

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Description

    TECHNICAL FIELD
  • The present invention is in the field of laundry. In particular, it relates to a method of industrial or institutional laundry for a polyester load using a silicone suds suppressor during the wash process.
  • BACKGROUND OF THE INVENTION
  • Even though the principles that determine the effectiveness of detergents for household (or home) and professional (including institutional and industrial) laundries are similar, detergents for large-scale institutional or industrial use generally differ insofar as they must be designed to meet the special circumstances associated with laundry on an industrial scale and/or in an institutional context. Contrary to home laundry, professional laundries have to deal with large volumes of textile items and require therefore completely automatic processing with microprocessor-controlled machines and dosing units. The length of the washing process differs from that of home laundry and in some cases the washing is performed with soft water. Soil levels can be significantly lower in certain types of loads of professional laundry (for example towels and bed linen in a hotel which have ninimal use and soiling before being re-washed) than in household laundry and the loads and the machines are considerably bigger. The composition of the loads is more uniform, in terms of both, types of fabrics and soils. For example a typical commercial laundry load will consist of only towels, only bed linen or only table linen (tablecloths and napkins).
  • Due to the size of the washing equipment, professional laundry involves higher mechanical action than home laundry and this promotes foaming. Foaming is also promoted in the case of laundry loads consisting mainly of synthetic fabrics, in particular polyester fabrics. Polyester items are hydrophobic and they are not capable to absorb surfactants. During the washing process, polyester items seem to be less densily packed than cotton items, being more prone to sudsing. Suds negatively affect the laundry cleaning performance because contributes to the suspension of items in the wash liquor precluding the free rise and fall of the items, leading to reduction of mechanical action which is one of the major elements contributing to cleaning.
  • Low sudsing in washing polyester loads could be achieved through the selection of inherently low sudsing surfactants, primarily non-ionics, versus the use of anionics, for example. However this leads to poor performance on certain varieties of soils, because this limits the selection to potentially compromised-in-performance surfactants. An approach to overcome this lost of performance is the addition of high levels of alkalinity, as alkalinity itself can help drive soil removal. For example, patent application Wo 96/24657 discloses highly alkaline solid detergent compositions for use in professional laundry. But alkalinity can drive (alkaline) hydrolysis of the polyester molecules that comprise the fibers, and thus damage the very fabrics intended for cleaning. The alkalinity can also drive mineral salt encrustation and many other issues.
  • Some of the professional laundry systems involve the use of soft water. Soft water also promotes sudsing. Under these circumstances, it is difficult to perform a good cleaning.
  • Fatty acids or fatty soaps are commonly used as suds suppressors in laundry. They rely on the presence of water hardness ions to work. When water hardness ions are present they can form salts which can disrupt the suds. If there are no water hardness ions, as the case is with soft water, then the soap might even cause additional suds. It has been found that if a load of polyester is washed in soft water, using a normal amount of detergent, the level of suds can be so high that it can overflow the machine, this seems to be worse when the level of soil is low.
  • SUMMARY OF THE INVENTION
  • According to a first aspect of the invention, there is provided a method of cleaning a polyester load in a professional laundry machine as defined in the claims.
  • By polyester load is understood a load comprising at least 50%, preferably at least 60%, more preferably at least 80% and more preferably at least 95% by weight of the load of polyester items.
  • It has been found that textile loads containing a high level of polyester items give rise to high suds that impact negatively in the cleaning process. The method of the invention provides improved cleaning.
  • The level of anionic surfactant is greater than 12%, more preferably greater than 15% and especially greater than 20% by weight of the detergent composition. This provides an outstanding cleaning over a great range of soils. The detergent composition comprises non-ionic surfactant and anionic surfactant. The level of anionic surfactant is higher than the level of non-ionic surfactant, by "higher" is herein meant that the level of anionic surfactant is at least 1% by weight more than the level of non-ionic surfactant, preferably at least 5%, more preferably at least 15% and especially at least 20%. Preferably the level of non-ionic surfactant is less than 10% by weight of the detergent composition. The method of the invention also allows for flexibility in terms of detergent formulation.
  • Polyester with low level of soil and new polyester items can be even more prone to sudsing than highly soiled items. The method of the invention performs very well even in the case of loads with low level of soil (typically towels or bed linen) or new items. By the term "low soiled items" is herein understood items free from visible stains. By the term "new items" is herein understood items that have not been subjected to a washing process.
  • As mentioned above, soft water further contributes to aggravate the suds problem. The water of the wash liquor of the method of the invention, preferably the water of the liquor of each cycle, has a hardness, i.e., Ca and Mg ions concentration, of less than 1, preferably less than 0.5 and especially less than 0.2 mmoles/litre.
  • Another factor that further aggravates the suds problem is heating by steam means. The method of the invention involves the step of heating the cleaning water using steam, in particular steam injection.
  • Excellent cleaning is obtained with the method of the invention, even when using soft water and when the water is heated by steam means.
  • Good cleaning performance is obtained when the level of active suds suppressor in the wash liquor is from 0.1 to 10, more preferably from 0.2 to 5 and especially from 0.8 to 3 ppm. The suds suppressor for use herein is a polydimethlysiloxane compounded with silica.
  • The wash liquor, preferably the wash liquor of the main wash, has a pH of from 7 to 9, preferably from 8 to 9, as measured at room temperature (20°C) this allows not only for good cleaning but also for good care of the washed articles.
  • The detergent composition comprises anionic surfactant, in a level of at least 12% by weight of the detergent composition, and at least 80% by weight of the anionic surfactant is sodium lauryl benzene sulfonate. Detergents rich in sodium lauryl benzene sulfonate, used according to the method of the invention, provide not only good cleaning but also have a low suds profile.
  • In preferred embodiments the method of the invention comprises the step of contacting the load with a soil release polymer, in any of the wash cycles, preferably during the main-wash or a rinse cycle. Preferably the soil release polymer is added as part of an additive rather than as part of a detergent composition. This not only obviates the process challenges found to make the soil release polymer part of a base detergent but also eliminates the interaction between some of the base detergent ingredients and the polymer and gives flexibility in terms of dosing.
  • DETAILED DESCRIPTION OF THE INVENTION
  • The present invention envisages a method of professional laundry of a polyester load. The method involves contacting the load with a detergent comprising a silicone suds suppressor. The method provides improved cleaning. It has been found that the problem of high suds is more acute in the case of a load with low level of soil, ie. a load with less than 10 g of soil per kilogram of load, preferably with less than 5 g of soil per kilogram of load. The polyester load used in the method of the present invention is a load with low level of soil.
  • Professional laundry includes institutional and industrial (sometimes also referred to as commercial) laundry. Institutional laundry refers to textile washing operations usually run in business sites, normally referred to as On-Premise or In-House Laundry Operations. Typical businesses can be for instance hotels, restaurants, care homes, hospitals, spas, health or sport clubs, schools, and similar institutions. Industrial laundry refers to textile washing operations carried out in dedicated places typically for the above businesses.
  • By "professional laundry machine" is herein meant a laundry machine which a capacity higher than 25 kg of dry laundry.
  • There are two main types of professional laundry machines: front load which operate in a batch mode or tunnel washing machines that operate in continuous mode. The professional laundry machines for use herein, in the case of front load have a drum volume of at least about 0.15 m3, preferably at least 0.2 m3, more preferably at least 0.3 m3 and especially at least 0.5 m3. The professional laundry machines for use herein, in the case of front load have a drum diameter of at least about 0.5 m, preferably at least 0.8 m and more preferably at least 1 m. In the case of tunnel washing machines the tunnel has a diameter of at least about 1.5 m, preferably at least 3m and more preferably at least 5 m.
  • Silicone suds suppressor is defined herein as an antifoam compound that is a polydimethylsiloxane compounded with silica. The polydimethylsiloxane is a relatively high molecular weight polymer containing siloxane units and methyl groups that is chemisorbed or fused onto silica. Silicone suds suppressers are well known in the art and are, for example, disclosed in U.S. Pat. No. 4,265,779 , and EP 354 016 . Other silicone suds suppressers are disclosed in U.S. Pat. No. 3,455,839 which relates to compositions and processes for defoaming aqueous solutions by incorporating therein small amounts of polydimethylsiloxane fluids. Mixtures of silicone and silanated silica are described, for instance, in German Patent Application DOS 2,124,526 . Silicone defoamers and suds controlling agents in granular detergent compositions are disclosed in U.S. Pat. No. 3,933,672 and in U.S. Pat. No. 4,652,392 .
  • Suitable polydimethylsiloxanes compounded with silica particles are commercially available from Dow Coming, Wacker Chemie and General Electric.
  • The Silicone suds suppressor is utilized in amounts up to about 2% by weight of the detergent composition. This upper limit is practical in nature, due primarily to concern with keeping costs minized and effectiveness of lower amounts for effectively controlling sudsing. Preferably from 0.01 % to 1% of active silicone suds suppressor is used, more preferably from 0.05% to 0.5% by weight of the detergent composition. As used herein, the term "active" excludes water and inactive ingredients (in terms of suds suppression).
  • Detergent composition Detersive Surfactant
  • Compositions suitable for use herein comprise from 20% to 50% by weight of a certain kind of detersive surfactant component. Such an essential detersive surfactant component must comprise a combination of anionic surfactant and nonionic surfactant.
  • Suitable anionic surfactants useful herein can comprise any of the conventional anionic surfactant types typically used in liquid detergent products. These include the alkyl benzene sulfonic acids and their salts as well as alkoxylated or un-alkoxylated alkyl sulfate materials.
  • Preferred anionic surfactants are the alkali metal salts of C10-16 alkyl benzene sulfonic acids, preferably C11-14 alkyl benzene sulfonic acids. Preferably the alkyl group is linear and such linear alkyl benzene sulfonates are known as "LAS". Alkyl benzene sulfonates, and particularly LAS, are well known in the art. Such surfactants and their preparation are described for example in U.S. Patents 2,220,099 and 2,477,383 . Especially preferred are the sodium and potassium linear straight chain alkylbenzene sulfonates in which the average number of carbon atoms in the alkyl group is from about 11 to 14. Sodium C11-C14, e.g., C12, LAS is especially preferred. At least 80% by weight of the anionic surfactant is sodium lauryl benzene sulfonate.
  • Another preferred type of anionic surfactant comprises ethoxylated alkyl sulfate surfactants. Such materials, also known as alkyl ether sulfates or alkyl polyethoxylate sulfates, are those which correspond to the formula:

            R'-O-(C2H4O)n-SO3M

    wherein R' is a C8-C20 alkyl group, n is from about 1 to 20, and M is a salt-forming cation. Preferably, R' is C10-C18 alkyl, n is from about 1 to 15, and M is sodium, potassium, ammonium, alkylammonium, or alkanolammonium. Most preferably, R' is a C12-C16, n is from about 1 to 6 and M is sodium.
  • The alkyl ether sulfates will generally be used in the form of mixtures comprising varying R' chain lengths and varying degrees of ethoxylation. Frequently such mixtures will inevitably also contain some unethoxylated alkyl sulfate materials, i.e., surfactants of the above ethoxylated alkyl sulfate formula wherein n=0. Unethoxylated alkyl sulfates may also be added separately to the compositions of this invention and used as or in any anionic surfactant component which may be present.
  • Preferred unalkoyxylated, e.g., unethoxylated, alkyl ether sulfate surfactants are those produced by the sulfation of higher C8-C20 fatty alcohols. Conventional primary alkyl sulfate surfactants have the general formula:

            ROSO3 -M+

    wherein R is typically a linear C8-C20 hydrocarbyl group, which may be straight chain or branched chain, and M is a water-solubilizing cation. Preferably R is a C10-C15 alkyl, and M is alkali metal. Most preferably R is C12-C14 and M is sodium.
  • Suitable nonionic surfactants useful herein can comprise any of the conventional nonionic surfactant types typically used in liquid detergent products. These include alkoxylated fatty alcohols, ethylene oxide (EO)-propylene oxide (PO) block polymers, and amine oxide surfactants. Preferred for use in the liquid detergent products herein are those nonionic surfactants which are normally liquid.
  • Preferred nonionic surfactants for use herein include the alcohol alkoxylate nonionic surfactants. Alcohol alkoxylates are materials which correspond to the general formula:

            R1(CmH2mO)nOH

    wherein R1 is a C8 - C16 alkyl group, m is from 2 to 4, and n ranges from about 2 to 12.
  • Preferably R1 is an alkyl group, which may be primary or secondary, that contains from about 9 to 15 carbon atoms, more preferably from about 10 to 14 carbon atoms. Preferably also the alkoxylated fatty alcohols will be ethoxylated materials that contain from about 2 to 12 ethylene oxide moieties per molecule, more preferably from about 3 to 10 ethylene oxide moieties per molecule.
  • The alkoxylated fatty alcohol materials useful in the liquid detergent compositions herein will frequently have a hydrophilic-lipophilic balance (HLB) which ranges from about 3 to 17. More preferably, the HLB of this material will range from about 6 to 15, most preferably from about 8 to 15. Alkoxylated fatty alcohol nonionic surfactants have been marketed under the tradenames Neodol and Dobanol by the Shell Chemical Company.
  • Another type of nonionic surfactant which is liquid and which may be utilized in the compositions of this invention comprises the ethylene oxide (EO) - propylene oxide (PO) block polymers. Materials of this type are well known nonionic surfactants which have been marketed under the tradename Pluronic. These materials are formed by adding blocks of ethylene oxide moieties to the ends of polypropylene glycol chains to adjust the surface active properties of the resulting block polymers. EO-PO block polymer nonionics of this type are described in greater detail in Davidsohn and Milwidsky; Synthetic Detergents, 7th Ed.; Longman Scientific and Technical (1987) at pp. 34-36 and pp. 189-191 and in U.S. Patents 2,674,619 and 2,677,700 .
  • Yet another suitable type of nonionic surfactant useful herein comprises the amine oxide surfactants. Amine oxides are mateials which are often referred to in the art as "semi-polar" nonionics. Amine oxides have the formula: R(EO)x(PO)y(BO)zN(O)(CH2R')2.qH2O. In this formula, R is a relatively long-chain hydrocarbyl moiety which can be saturated or unsaturated, linear or branched, and can contain from 8 to 20, preferably from 10 to 16 carbon atoms, and is more preferably C12-C16 primary alkyl. R' is a short-chain moiety preferably selected from hydrogen, methyl and -CH2OH. When x+y+z is different from 0, EO is ethyleneoxy, PO is propyleneneoxy and BO is butyleneoxy. Amine oxide surfactants are illustrated by C12-14 alkyldimethyl amine oxide.
  • In the liquid detergent compositions herein, the weight ratio of anionic surfactant to nonionic surfactant is from 20:1 to 1:20.
  • Laundry washing adjuncts
  • The detergent compositions herein, which are in liquid form, comprise from 0.1% to 30% by weight, preferably from 0.5% to 20% by weight, more preferably from 1% to 10% by weight, of one or more of certain kinds of laundry washing adjuncts. Such laundry washing adjuncts can be selected from detersive enzymes, builders, chelants, soil release polymers, soil suspending polymers, optical brighteners, dye transfer inhibition agents, bleach, whitening agents, suds suppressors, fabric care benefit agents, solvents, stabilizers, buffers, structurants, dyes and perfumes and combinations of these adjunct types. All of these materials are of the type conventionally utilized in laundry detergent products.
  • Soil release polymer
  • Soil release polymers enhance the laundry cleaning efficacy by improving release of grease and oil during the laundry process. See soil release agents' definition, p.278-279, "Liquid Detergents" by Kuo-Yann Lai. For use herein, preferred level of soil release polymer per kilogram of load is from about 0.01 to about 0.8 grams, more preferably the level of polymer is less than 0.2 grams especially from about 0.05 to about 0.15 grams. Contrary to what one would expect higher levels of soil release polymer do not enhance removal. In some cases removal is worse than with lower levels.
  • Improved stain removal is achieved when the soil release polymer is a copolymer having the formula:
    Figure imgb0001
    wherein :
    • each R1 moieties is a 1,4-phenylene moiety;
    • the R2 moieties are each selected from the group consisting of ethylene moieties, 1,2-propylene moieties, 1,2 butylene moieties, 1,2 hexylene moieties, 3-methoxy-1,2 propylene moieties or mixture thereof, provided that said R2 are not exclusively 1,2 butylene moieties, 1,2 hexylene moieties, 3-methoxy-1,2 propylene moieties or mixture thereof; preferably R2 is a 1,2-propylene moiety.
    • the R3 moieties are each selected from the group consisting of substituted 1,3-phenylene moieties having the substituent
      Figure imgb0002
      at the 5 position;
    • the R4 moieties are R1 or R3 moieties, or mixtures thereof;
    • each X is C1-C4 alkyl; each n is from 12 to 43;
    • when w is 0, u+v is from 3 to 10;
    • when w is at least 1, u+v+w is from 3 to 10.
  • Preferably w is 0.
  • Preferred soil release polymer for use herein is a copolymer comprising propylene glycol derived moieties, terephthalate moieties and capped polyethylene glycol derived moieties. Preferably the capped polyethylene glycol used is CH3O(CH2CH2O)nOH, wherein n is an integer from 12 to 44, preferably from 20 to 42 and more preferably from 25 to 41 and especially 40. Improved performance is obtained with this kind of copolymers.
  • The preferred copolymer for use herein has the following formula:
    Figure imgb0003
  • Preferably the soil release polymer has a molecular weight above about 2,000, more preferably above about 3,000 and more preferably above about 4,000. Methods in which soil release polymers having molecular weight above 4,000 have been used provide outstanding results in terms of stain removal. Preferably the molecular weight is below about 20,000. With reference to the polymers described herein, the term "molecular weight" is the weight-average molecular weight as determined using gel permeation chromatography according to the protocol found in Colloids and Surfaces A. Physico Chemical & Engineering Aspects, Vol. 162, 2000, pg. 107-121. The units are Daltons.
  • Preferably the soil release polymer is added as part of an additive. The additive is in liquid form so it can be easily delivered by means of a displacement pump, for example a peristaltic pump. The additive is preferably an aqueous structured liquid, usually the soil release polymer is insoluble in aqueous solution and it is suspended by means of an external structurant. Structured liquids can either be internally structured, whereby the structure is formed by primary ingredients (e.g. surfactant material) and/or externally structured by providing a three dimensional matrix structure using secondary ingredients (e.g. polymers, clay and/or silicate material). The additive comprises the soil release polymer, preferably in an amount of from about 1% to about 50%, more preferably from about 5% to about 20% by weight of the additive. The additive can further comprise an external structurant to keep the soil release polymer suspended. Levels of external structurants of from about 0.05 to about 5%, more preferably from about 0.1 to about 2% and especially from about 0.1 to about 1% by weight of the additive have been found particularly suitable to keep the polymer suspended. Preferred external structurant for use herein is xanthan gum. Preferably the additive comprises a preservative, more preferred in a level of from about 0.05 to about 3% and especially from about 0.1 to about 1% by weight of the additive. A dye is another prefer component of the additive of the invention. Preferably the additive is free of builders and/or surfactants.
  • Detersive Enzymes
  • Examples of suitable enzymes include, but are not limited to, hemicellulases, peroxidases, proteases, cellulases, xylanases, lipases, phospholipases, esterases, cutinases, pectinases, keratanases, reductases, oxidases, phenoloxidases, lipoxygenases, ligninases, pullulanases, tannases, mannanases, pentosanases, malanases, β-glucanases, arabinosidases, hyaluronidase, chondroitinase, laccase, and known amylases, or combinations thereof. A preferred enzyme combination comprises a cocktail of conventional detersive enzymes like protease, lipase, cutinase and/or cellulase in conjunction with amylase. Detersive enzymes are described in greater detail in U.S. Patent No. 6,579,839 .
  • If employed, enzymes will normally be incorporated into the base detergent compositions herein at levels sufficient to provide up to 10 mg by weight, more typically from about 0.01 mg to about 5 mg, of active enzyme per gram of the composition. Stated otherwise, the aqueous liquid detergent compositions herein can typically comprise from 0.001% to 5%, preferably from 0.01% to 1% by weight, of a commercial enzyme preparation. Protease enzymes, for example, are usually present in such commercial preparations at levels sufficient to provide from 0.005 to 0.1 Anson units (AU) of activity per gram of detergent composition.
  • The detergent may also include from about 0.05 to about 0.5% of preservatives non-limiting examples of which include didecyl dimethyl ammonium chloride which is available under the tradeneme UNIQUAT (from Lonza of Basel Switzerland), 1,2-benzisothiozolin-3-one, which is available under the tradename PROPEL (from Arch Chemicals of Norwalk, Connecticut), dimethylol-5,5-dimethylhydantoin which is available under the tradeneme DANTOGUARD (from Lonza of Basel Switzerland), 5- Chloro-2- methyl-4- isothiazolin-3-one / 2-methyl-4-isothiazolin-3-one, which is available under the tradename KATHON (from Rohm and Haas of Philadelphia, Pennsylvania), and mixtures thereof.
  • Other Fabric Care Benefit Agents
  • The detergent composition for use herein may also comprise additional fabric care or benefit agents which can be deposited onto fabrics being laundered and which thereupon provide one or more types of fabric care or treatment benefits. Such benefits can include, for example, fabric softness, anti-static effects, ease-of-ironing benefits, anti-abrasion benefits, anti-pilling effects, color protection, wrinkle removal or improved resistance to wrinkling, fabric substantive perfume or odor benefits, malodor protection benefits, and the like.
  • A wide variety of materials which are suitable for providing such benefits and which can be deposited onto fabrics being laundered are known in the art. Such materials can include, for example, clays; starches; polyamines; un-functionalized and functionalized silicones such as aminosilicones and quaternary nitrogen-containing cationic silicones; cellulosic polymers, and the like. Materials of these types are described in greater detail in one or more of the following publications: US 6,525,013 ; US 4,178,254 ; WO 02/40627 ; WO 02/18528 ; WO 00/71897 ; WO 00/71806 ; WO 98/39401 ; and WO 98/29528 .
  • If employed, such additional fabric care benefit agents polymers can typically be incorporated into the liquid laundry detergent compositions herein in concentrations ranging from 0.05% to 20%, by weight, depending upon the nature of the materials to be deposited and the benefit(s) they are to provide. More preferably, such fabric care benefit agents can comprise from 0.1% to 10%, by weight of the composition.
  • Example:
  • 45 pounds of a polyester load was washed in a Milnor commercial washing machine (model # 30022V6J (55-60 pound capacity)) at 60°C and using soft water (0 mmoles/liter).
  • The detergent used had the following composition and it was used at a dosage of 48 grams/ machine (or 9.6 ml/kg fabric). The detergent was delivered into the main-wash cycle. Table 1
    Ingredient % by weight
    C12-alkylbenxene sulfonic acid 12.2
    Non-ionic surfactant 8.75
    C12-alkyl trimethyl amine N-oxide 1.5
    C12-14 fatty acid 8.3
    Citric acid 3.4
    Triethyleneimine penta phosphonic acid 0.19
    Ethoxylated polymine polymer 1.1
    Enzyme 0.53
    1,2 propandiol 4.9
    Ethanol 2.8
    Monethanolamine 0.83
    Monoethanaolamine borate 2.4
    Cumene sulfonic acid 1.9
    BF20 plus silicone suds suppressor Ex Dow Coming 0.13
    Hydrogenated castor oil 0.10
    Perfume and minors 0.5
    Sodium hydroxide to pH 8.0
    water Balance
  • A low suds profile was obtained using the exemplified detergent.
  • The dimensions and values disclosed herein are not to be understood as being strictly limited to the exact numerical values recited. Instead, unless otherwise specified, each such dimension is intended to mean both the recited value and a functionally equivalent range surrounding that value. For example, a dimension disclosed as "40 mm" is intended to mean "about 40 mm"

Claims (3)

  1. A method of cleaning a polyester load comprising at least 50% of polyester items in a professional laundry machine having a capacity higher than 25 kg of dry laundry, the method comprising:
    subjecting the load to main-wash, rinse and optionally pre-wash cycles wherein the method comprises the step of contacting the load with an aqueous wash liquor containing a liquid detergent composition comprising up to 2% of silicone suds suppressor by weight of the detergent composition and from 20% to 50% by weight of a combination of anionic surfactant and nonionic surfactant;
    wherein the detergent composition comprises at least 12% of anionic surfactant by weight of the detergent composition;
    wherein at least 80% by weight of the anionic surfactant is sodium lauryl benzene sulfonate;
    wherein the weight ratio of anionic surfactant to nonionic surfactant is from 20:1 to 1:20;
    wherein the suds suppressor is a polydimethylsiloxane compounded with silica;
    wherein the wash liquor has a pH of from 7 to 9;
    wherein the level of suds suppressor in the wash liquor is from 0.1 ppm to 10 ppm;
    wherein the water of the wash liquor, preferably the water of the liquor of each cycle, has a hardness of less than 1 mmole/litre;
    wherein the method involves the step of steam heating to heat the wash liquor;
    and wherein the polyester load comprises less than 10 g of soil per kg of load.
  2. The method of cleaning according to claim 1 wherein the polyester load comprises new items.
  3. The method of cleaning according to claim 1 or 2 comprising the step of contacting the load with a soil release polymer delivered into any of the main wash or rinse cycles.
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US20100229312A1 (en) 2010-09-16

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