EP2627751B1 - Verfahren für von oben befüllbare wäschebehälter - Google Patents

Verfahren für von oben befüllbare wäschebehälter Download PDF

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Publication number
EP2627751B1
EP2627751B1 EP11763944.3A EP11763944A EP2627751B1 EP 2627751 B1 EP2627751 B1 EP 2627751B1 EP 11763944 A EP11763944 A EP 11763944A EP 2627751 B1 EP2627751 B1 EP 2627751B1
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EP
European Patent Office
Prior art keywords
surfactant
process according
particle
water
dyes
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EP11763944.3A
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English (en)
French (fr)
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EP2627751A1 (de
Inventor
Stephen Thomas Keningley
Benjamin Jesukumar Rajapandian
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Unilever PLC
Unilever NV
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Unilever PLC
Unilever NV
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Classifications

    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D17/00—Detergent materials or soaps characterised by their shape or physical properties
    • C11D17/0039—Coated compositions or coated components in the compositions, (micro)capsules
    • 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
    • C11D3/02—Inorganic compounds ; Elemental compounds
    • C11D3/04—Water-soluble compounds
    • C11D3/046—Salts
    • 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
    • C11D3/02—Inorganic compounds ; Elemental compounds
    • C11D3/04—Water-soluble compounds
    • C11D3/08—Silicates
    • 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
    • C11D3/02—Inorganic compounds ; Elemental compounds
    • C11D3/04—Water-soluble compounds
    • C11D3/10—Carbonates ; Bicarbonates

Definitions

  • the present invention relates to laundry cleaning methods using shaped laundry detergent particles.
  • Liquid detergents do not have these same residue problems, but as they are largely un-built systems, they can suffer cleaning disadvantages especially in hard-water areas. Liquids have other advantages over powders, for example they do not have the caking problems of solids.
  • WO1999/32599 describes a method of manufacturing laundry detergent particles, by extrusion of a builder and surfactant to form noodles.
  • a composition with a major component of a sulphated or sulphonated anionic surfactant is fed into an extruder, mechanically worked at a temperature of at least 40 °C, preferably at least 60°C, and extruded through an extrusion head having a multiplicity of extrusion apertures.
  • the surfactant is fed to the extruder along with builder in a weight ratio of more than 1 part builder to 2 parts surfactant.
  • the extruded material apparently required further drying.
  • PAS paste was dried and extruded.
  • Such PAS noodles are well known in the prior art.
  • the noodles are typically cylindrical in shape and their length exceeds their diameter, as described in example 2.
  • EP application 09158717.0 ( WO 2010/122051 ) discloses high active detergent particles with a low surface roughness produced by extrusion of an anionic surfactant rich composition, and cutting of the extruded product to form slices which are thinner than they are wide. These slices are then spray-coated with, for example, an aqueous solution of sodium carbonate, to form smooth-surfaced, free-flowing particles which may look like "lentils".
  • a builder salt such as sodium carbonate is advantageous because it buffers the pH at a level where the anionic surfactant is particularly effective, and increases the ionic strength.
  • the particles are also said to dissolve well in water and are suitable for use in a front loading washing machine (page 6, line 19).
  • coated extruded particles with a particular shape and formulation show exceptionally good cleaning and care as perceived by a panel of users.
  • the particles do not exhibit a "hot on hands" feeling when used.
  • the present invention provides a laundry process which comprises the steps of:
  • the surfactant to builder ratio in the detergent particles is in the range 1.5-2.5:1, more preferably 1.8-2.2:1. As the ratio shifts further towards high builder levels the wash liquor becomes too alkaline and as it shifts towards high surfactant levels buffering capacity is lost.
  • the builder present as a coating encasing the surfactant, which is soft and sticky, a particulate concentrate with the preferred ratio of surfactant to builder can be provided.
  • the absence of other materials reduce the unit dose required for a wash and therefore reduces transportation costs and increases shelf-use efficiency.
  • the coated laundry detergent particle has a non-spherical surface. Preferably this surface is in part curved.
  • the coated laundry detergent particle may be described as disk-like, lenticular or an oblate spheroid/ellipsoid, where z and y are the equatorial diameters and x is the polar diameter. It is preferred that y and z are similar in value, although with some methods of manufacture they may differ slightly due to pressures exerted during slicing of an extruded product.
  • the particles have an axis of rotational symmetry along the polar axis.
  • the coated laundry detergent particle does not have any holes; that is to say, the coated laundry detergent particle has a topologic genus of zero.
  • y and z are independently in the range 3 to 8 mm. This moves the shape further from a sphere and increases the ratio of surface area to volume, improving solubility.
  • the thickness of coating obtainable by use of a particular coating level is significantly greater than would be achieved on typically sized detergent granules (0.5-2mm diameter sphere). This makes for a more robust coating and reduces the tendency of the surfactant to bleed through the coating and make the particles sticky. It is also the case that a significant proportion of the builder will dissolve before the surfactant starts to dissolve so that the wash liquor will be at least partially built before the surfactant is dissolved.
  • a further advantage of these relatively large particles in the top-loader is that they sink rapidly and come into contact with the impeller at an early stage in the wash.
  • this surface area to volume ratio must be greater than 3 mm -1 .
  • the coating thickness is inversely proportional to this coefficient and hence for the coating the ratio "Surface area of coated particle" divided by "Volume of coated particle” should be less than 15 mm -1 .
  • the coated laundry detergent particle is such that at least 90 to 100% of the coated laundry detergent particles in the in the average x, y and z dimensions of individual particles are within a 20%, preferably 10%, variable from the largest to the smallest coated laundry detergent particle.
  • These aggregations of particles with similar sizes show good flow properties, can be,packaged in bottles and can be dosed like a liquid.
  • the detergent particles comprise from 0.0001 to 0.1 wt % dye, preferably 0.001 to 0.01 wt % dye, wherein the dye is selected: from anionic dyes; and, non-ionic dyes.
  • Dyes serve several useful functions. They may assist the user in recognising different products, and/or may act as shading agents to mask yellowness of articles being laundered. If is preferable that not all of the particles are of the same colour, and that two or more colours of particles are present, for example white and blue, white and pink or white and orange.
  • wt % refer to the total percentage in the particle as dry weights (including water of hydration where present).
  • a top loading washing vessel is any vessel which is used by end-users to launder clothes.
  • such vessels have a capacity in excess of 4 litres.
  • Such vessels include, and preferentially comprise, top loading semi-automatic and automatic washing machines, preferably with means to agitate the wash liquor within them, and, in addition or in the alternative, other vessels where the agitation is manual, preferably a bath, tub, bucket, basin, bowl or sink.
  • Machines include machines such as and similar to a Brazilian “Tanquinho".
  • the vessel is open at the top during the washing operation and at least part of the agitation is provided by hand.
  • the coated laundry detergent particle comprises between 50 to 90 wt% of a surfactant, most preferably 70 to 90 wt%.
  • a surfactant most preferably 70 to 90 wt%.
  • the nonionic and anionic surfactants of the surfactant system may be chosen from the surfactants described " Surface Active Agents" Vol. 1, by Schwartz & Perry, Interscience 1949 , Vol. 2 by Schwartz, Perry & Berch, Interscience 1958 , in the current edition of "McCutcheon's Emulsifiers and Detergents” published by Manufacturing Confectioners Company or in " Tenside-Taschenbuch", H. Stache, 2nd Edn., Carl Hauser Verlag, 1981 .
  • the surfactants used are saturated.
  • Suitable anionic detergent compounds which may be used are usually water-soluble alkali metal salts of organic sulphates and sulphonates having alkyl radicals containing from about 8 to about 22 carbon atoms, the term alkyl being used to include the alkyl portion of higher acyl radicals.
  • suitable synthetic anionic detergent compounds are sodium and potassium alkyl sulphates, especially those obtained by sulphating higher C 8 to C 18 alcohols, produced for example from tallow or coconut oil, sodium and potassium alkyl C 9 to C 20 benzene sulphonates, particularly sodium linear secondary alkyl C 10 to C 15 benzene sulphonates; and sodium alkyl glyceryl ether sulphates, especially those ethers of the higher alcohols derived from tallow or coconut oil and synthetic alcohols derived from petroleum.
  • anionic surfactants are sodium lauryl ether sulfate (SLES), particularly preferred with 1 to 3 ethoxy groups, sodium C 10 to C 15 alkyl benzene sulphonates (LAS) and sodium C 12 to C 18 alkyl sulphates (PAS).
  • Alkyl ester suphonates such as Methyl ester sulphonates (MES) may be used in whole or part replacement for the other anionics.
  • surfactants such as those described in EP-A-328 177 (Unilever), which show resistance to salting-out, the alkyl polyglycoside surfactants described in EP-A-070 074 , and alkyl monoglycosides.
  • the chains of the surfactants may be branched or linear.
  • the fatty acid soap used preferably contains from about 16 to about 22 carbon atoms, preferably in a straight chain configuration.
  • the anionic contribution from soap is preferably from 0 to 30 wt% of the total anionic.
  • At least 50 wt % of the anionic surfactant is selected from: sodium C 11 to C 15 alkyl benzene sulphonates; and, sodium C 12 to C 18 alkyl sulphates. Even more preferably, the anionic surfactant is sodium C 11 to C 15 alkyl benzene sulphonates.
  • the anionic surfactant is present in the coated laundry detergent particle at levels between 15 to 85 wt%, more preferably 50 to 80wt% on total surfactant.
  • Suitable nonionic detergent compounds which may be used include, in particular, the reaction products of compounds having a hydrophobic group and a reactive hydrogen atom, for example, aliphatic alcohols, acids, amides or alkyl phenols with alkylene oxides, especially ethylene oxide either alone or with propylene oxide.
  • Preferred nonionic detergent compounds are C 6 to C 22 alkyl phenol-ethylene oxide condensates, generally 5 to 25 EO, i.e. 5 to 25 units of ethylene oxide per molecule, and the condensation products of aliphatic C 8 to C 18 primary or secondary linear or branched alcohols with ethylene oxide, generally 5 to 50 EO.
  • the non-ionic is 10 to 50 EO, more preferably 20 to 35 EO.
  • Alkyl ethoxylates are particularly preferred, most particularly those with 25-35 EO, as these give a particularly good foam profile.
  • the nonionic surfactant is present in the coated laundry detergent particle at levels between 5 to 75 wt% on total surfactant, more preferably 10 to 40 wt% on total surfactant.
  • Cationic surfactant may be present as minor ingredients at levels preferably between 0 to 5 wt% on total surfactant.
  • surfactants are mixed together before being dried. Conventional mixing equipment may be used.
  • the surfactant core of the laundry detergent particle may be formed by extrusion or roller compaction and subsequently coated with an inorganic salt.
  • Foam boosters such as betaines, amine oxides and/or other zwitterionic and aphphoteric surfactants are optional as the compositions of the invention generally show adequate foaming.
  • the surfactant system used is calcium tolerant and this is a preferred aspect because this reduces the need for builder.
  • Surfactant blends that do not require builders to be present for effective detergency in hard water are preferred. Such blends are called calcium tolerant surfactant blends if they pass the test set out hereinafter. However, the invention may also be of use for washing with soft water, either naturally occurring or made using a water softener. In this case, calcium tolerance is no longer important and blends other than calcium tolerant ones may be used.
  • the surfactant blend in question is prepared at a concentration of 0.7 g surfactant solids per litre of water containing sufficient calcium ions to give a French hardness of 40 (4 x 10 -3 Molar Ca 2+ ).
  • Other hardness ion free electrolytes such as sodium chloride, sodium sulphate, and sodium hydroxide are added to the solution to adjust the ionic strength to 0.05M and the pH to 10.
  • the adsorption 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.
  • Suitable calcium tolerant co-surfactants include SLES 1-7EO, and alkyl-ethoxylate nonionic surfactants, particularly those with melting points less than 40°C.
  • a LAS/SLES surfactant blend has a superior foam profile to a LAS nonionic surfactant blend and is therefore preferred for hand washing formulations requiring high levels of foam.
  • SLES may be used at levels of up to 30wt% of the surfactant blend.
  • the water-soluble inorganic salts are preferably selected from water soluble salts of carbonate, chloride, silicate and sulphate, or mixtures thereof, most preferably, 70 to 100 wt% sodium carbonate on total water-soluble inorganic salts.
  • the water-soluble inorganic salt is present as a coating on the particle.
  • the amount of coating should lay in the range 1 to 40 wt% of the particle, preferably 20 to 40 wt%, more preferably 25 to 35 wt% for the best results in terms of anti-caking properties of the detergent particles.
  • the coating is preferably applied to the surface of the surfactant core, by deposition from an aqueous solution of the water soluble inorganic salt.
  • an aqueous solution of the water soluble inorganic salt can be performed using a slurry.
  • the aqueous solution preferably contains greater than 50g/L, more preferably 200 g/L of the salt.
  • An aqueous spray-on of the coating solution in a fluidised bed has been found to give good results and may also generate a slight rounding of the detergent particles during the fluidisation process. Drying and/or cooling may be needed to finish the process.
  • a preferred calcium tolerant coated laundry detergent particle comprises 15 to 100 wt% on surfactant of anionic surfactant of which 20 to 30 wt% on surfactant is sodium lauryl ether sulphate.
  • a highly preferred water soluble inorganic salt for inclusion in the coating is sodium carbonate monohydrate. Where, during the wash process, the coated detergent particles contact both water and the skin of the user, this confers the distinct benefit that upon exposure to water the particles do not generate as much heat as they would if the carbonate was anhydrous. This is an important preferred feature as users often mix detergent products with water by hand, and describe products which employ anhydrous sodium carbonate as having a "hot on hands" feeling.
  • the inorganic salts in the coating is 100% by weight sodium carbonate monohydrate. This gives the best protection against moisture.
  • the level of sodium carbonate monohydrate can be as low as 50% by weight of the inorganic salts in the coating.
  • Dyes are a highly preferred component of the present invention. Suitable dyes are described in Industrial Dyes edited by K. Hunger 2003 Wiley-VCH ISBN 3-527-30426-6 .
  • Dyes for use in the current invention are selected from anionic and non-ionic dyes
  • Anionic dyes are negatively charged in an aqueous medium at pH 7.
  • anionic dyes are found in the classes of acid and direct dyes in the Color Index (Society of Dyers and Colourists and American Association of Textile Chemists and Colorists).
  • Anionic dyes preferably contain at least one sulphonate or carboxylate groups.
  • Non-ionic dyes are uncharged in an aqueous medium at pH 7, examples are found in the class of disperse dyes in the Color Index.
  • the dyes may be alkoxylated.
  • Alkoxylated dyes are preferably of the following generic form: Dye-NR 1 R 2 .
  • the NR 1 R 2 group is attached to an aromatic ring of the dye.
  • R 1 and R 2 are independently selected from polyoxyalkylene chains having 2 or more repeating units and preferably having 2 to 20 repeating units. Examples of polyoxyalkylene chains include ethylene oxide, propylene oxide, glycidol oxide, butylene oxide and mixtures thereof.
  • a preferred alkoxylated dye for use in the invention is:
  • the dye is selected from acid dyes; disperse dyes and alkoxylated dyes.
  • the dye is a non-ionic dye.
  • the dye is selected from those having: anthraquinone; mono-azo; bis-azo; xanthene; phthalocyanine; and, phenazine chromophores. More preferably the dye is selected from those having: anthraquinone and, mono-azo chromophores.
  • the dye is added to the coating solution or slurry and agitated before applying to the core of the particle.
  • Application may be by any suitable method, preferably spraying on to the core particle as detailed above.
  • the dye may be any colour, preferable the dye is blue, violet, green or red. Most preferably the dye is blue or violet.
  • the dye is selected from: acid blue 80, acid blue 62, acid violet 43, acid green 25, direct blue 86, acid blue 59, acid blue 98, direct violet 9, direct violet 99, direct violet 35, direct violet 51, acid violet 50, acid yellow 3, acid red 94, acid red 51, acid red 95, acid red 92, acid red 98, acid red 87, acid yellow 73, acid red 50, acid violet 9, acid red 52, food black 1, food black 2, acid red 163, acid black 1, acid orange 24, acid yellow 23, acid yellow 40, acid yellow 11, acid red 180, acid red 155, acid red 1, acid red 33, acid red 41, acid red 19, acid orange 10, acid red 27, acid red 26, acid orange 20, acid orange 6, sulphonated Al and Zn phthalocyanines, solvent violet 13, disperse violet 26, disperse violet 28, solvent green 3, solvent blue 63, disperse blue 56, disperse violet 27, solvent yellow 33, disperse blue 79:1.
  • the dye is preferably a shading dye for imparting a perception of whiteness to a laundry textile.
  • the dye may be covalently bound to polymeric species. A combination of dyes may be used.
  • the particle preferably comprises from 0 to 15 wt% water, more preferably 0 to 10 wt%, most preferably from 1 to 5 wt% water, at 293K and 50% relative humidity. This facilitates the storage stability of the particle and its mechanical properties.
  • adjuncts as described below may be present in the coating or the core of the particle.
  • the coated laundry detergent particle preferably 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 %. Suitable fluorescer for use in the invention are described in chapter 7 of Industrial Dyes edited by K. Hunger 2003 Wiley-VCH ISBN 3-527-30426-6 .
  • Preferred fluorescers are selected from the classes of distyrylbiphenyls, triazinylaminostilbenes, bis(1,2,3-triazol-2-yl)stilbenes, bis(benzo[b]furan-2-yl)biphenyls, 1,3-diphenyl-2-pyrazolines and courmarins.
  • the fluorescer is preferably sulfonated.
  • Preferred classes of fluorescer are: Di-styryl biphenyl compounds, e.g. Tinopal (Trade Mark) CBS-X, Di-amine stilbene di-sulphonic acid compounds, e.g. Tinopal DMS pure Xtra and Blankophor (Trade Mark) HRH, and Pyrazoline compounds, e.g. Blankophor SN.
  • Di-styryl biphenyl compounds e.g. Tinopal (Trade Mark) CBS-X
  • Di-amine stilbene di-sulphonic acid compounds e.g. Tinopal DMS pure Xtra and Blankophor (Trade Mark) HRH
  • Pyrazoline compounds e.g. Blankophor SN.
  • Preferred fluorescers are: sodium 2 (4-styryl-3-sulfophenyl)-2H-napthol[1,2-d]triazole, disodium 4,4'-bis ⁇ [(4-anilino-6-(N methyl-N-2 hydroxyethyl) amino 1,3,5-triazin-2-yl)]amino ⁇ stilbene-2-2' disulfonate, disodium 4,4'-bis ⁇ [(4-anilino-6-morpholino-1,3,5-triazin-2-yl)]amino ⁇ stilbene-2-2' disulfonate, and disodium 4,4'-bis(2-sulfostyryl)biphenyl.
  • Tinopal® DMS is the disodium salt of disodium 4,4'-bis ⁇ [(4-anilino-6-morpholino-1,3,5-triazin-2-yl)]amino ⁇ stilbene-2-2' disulfonate.
  • Tinopal® CBS is the disodium salt of disodium 4,4'-bis(2-sulfostyryl)biphenyl.
  • the composition comprises a perfume.
  • the perfume is preferably in the range from 0.001 to 3 wt%, most preferably 0.1 to 1 wt%.
  • CTFA Cosmetic, Toiletry and Fragrance Association
  • Many suitable examples of perfumes are provided in the CTFA (Cosmetic, Toiletry and Fragrance Association) 1992 International Buyers Guide, published by CFTA Publications and OPD 1993 Chemicals Buyers Directory 80th Annual Edition, published by Schnell Publishing Co .
  • compositions of the present invention it is envisaged that there will be four or more, preferably five or more, more preferably six or more or even seven or more different perfume components.
  • top notes are defined by Poucher (Journal of the Society of Cosmetic Chemists 6(2):80 [1955 ]).
  • Preferred top-notes are selected from citrus oils, linalool, linalyl acetate, lavender, dihydromyrcenol, rose oxide and cis-3-hexanol.
  • the composition may comprise one or more polymers.
  • polymers are carboxymethylcellulose, poly (ethylene glycol), poly(vinyl alcohol), polyethylene imines, ethoxylated polyethylene imines, water soluble polyester polymers polycarboxylates such as polyacrylates, maleic/acrylic acid copolymers and lauryl methacrylate/acrylic acid copolymers.
  • One or more enzymes are preferred present in a composition of the invention.
  • the level of each enzyme is from 0.0001 wt% to 0.5 wt% protein on product.
  • enzymes include proteases, alpha-amylases, cellulases, lipases, peroxidases/oxidases, pectate lyases, and mannanases, or mixtures thereof.
  • Suitable lipases include those of bacterial or fungal origin. Chemically modified or protein engineered mutants are included. Examples of useful lipases include lipases from Humicola (synonym Thermomyces), e.g. from H. lanuginosa (T. lanuginosus) as described in EP 258 068 and EP 305 216 or from H. insolens as described in WO 96/13580 , a Pseudomonas lipase, e.g. from P. alcaligenes or P. pseudoalcaligenes ( EP 218 272 ), P. cepacia ( EP 331 376 ), P. stutzeri ( GB 1,372,034 ), P .
  • lipase variants such as those described in WO 92/05249 , WO 94/01541 , EP 407 225 , EP 260 105 , WO 95/35381 , WO 96/00292 , WO 95/30744 , WO 94/25578 , WO 95/14783 , WO 95/22615 , WO 97/04079 and WO 97/07202 , WO 00/60063 , WO 09/107091 and WO09/111258 .
  • LipolaseTM and Lipolase UltraTM LipexTM (Novozymes A/S) and LipocleanTM.
  • 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).
  • Combinations of enzymes may be used. It is particularly preferred to use a combination of lipase, protease and one or both of amylase and mannanase.
  • 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
  • Sequesterants for ions other than calcium and magnesium may be present in the coated laundry detergent particles.
  • Citrate is preferably present at a level of 5-15%wt on total particle. Citrate can be present either as the salt, or as the acid. When present as the acid evolved gas is generated on exposure of the particles to water. This can generate local turbulence which promotes dissolution and acts as a cue for cleaning.
  • Phosphonates, for example such as DequestTM 2010 can also be used as sequestering agents.
  • the coated laundry detergent particle does not contain a peroxygen bleach, e.g., percarbonate, perborate, and other peracids.
  • a peroxygen bleach e.g., percarbonate, perborate, and other peracids.
  • Preferred "chassis” formulations comprise:
  • Either of the LAS/NI based or LAS/PAS/SLES based options can be combined with citrate/citric acid at a level of 5-10 wt%.
  • Either formulation may comprise a soil release polymer, preferably a polyester material, for example Texcare SRN170 at a level of 1-5 wt%.
  • the extruded product was cut after the die-plate using a high speed cutter set up to produce particle with a thickness of ⁇ 1.1 mm.
  • the cutter deforms the discs cut from the extruded product to give a slight difference between dimensions y and z.
  • the coating solution was fed to the spray nozzle of the Strea 1 via a peristaltic pump (Watson-Marlow model 101 U/R) at an initial rate of 3.3g/min, rising to 9.1 g/min during the course of the coating trial.
  • a peristaltic pump Wood-Marlow model 101 U/R
  • the Fluid bed coater was operated with an initial air inlet air temperature of 55°C increasing to 90°C during the course of the coating trial whilst maintaining the outlet temperature in the range 45-50°C throughout the coating process.
  • compositions of the present invention show significant improvement over the standard and while they are pourable composition they are also significantly better performing than conventional liquids.
  • SkipTM powder (ex Argentina) and the composition of the present invention was sewn into a black cotton cloth sachet. Washes were performed using the cycles mentioned in the table below. Before preparing the sachets the black cotton was prewashed 3 times at 60°C to prevent dye transfer during the black sachet test (Miele professional 350 g Robijn, 8 kg black cotton). Sachets were filled with 10 gram of the different detergent products. Results are shown below.
  • the temperature rise on dissolution of a composition of the present invention was compared with the temperature rise of commercial laundry compositions in both a tub formed from a plastics material and a glass jar. In both cases 75g of product was added to 70g of water. The temperature rise was monitored at intervals for 300 seconds. In all cases the temperature rise using the particles of the present invention was significantly less than that using the commercial products.

Claims (15)

  1. Waschverfahren,
    das die folgenden Schritte aufweist:
    a) Bereitstellen von beschichteten Waschmittelteilchen mit den senkrechten Abmessungen x, y und z, wobei x zwischen 1 mm und weniger als 2 mm liegt, y zwischen mehr als 2 mm und 8 mm liegt und z zwischen mehr als 2 mm und 8 mm liegt, wobei das Teilchen Folgendes aufweist:
    i) 50 bis 90 Gew.-% Tensid, das aus anionischem Tensid, nichtionischem Tensid und Gemischen davon ausgewählt ist;
    ii) 1 bis 40 Gew.-% wasserlösliche anorganische Salze;
    iii) 0 bis 20 Gew.-% andere Bestandteile, wozu weniger als 15 Gew.-% wasserunlösliche Materialien, einschließlich Duftstoff, gehören; und wobei die anorganischen Salze auf dem Waschmittelteilchen als Beschichtung vorliegen und das Tensid als Kern vorliegt;
    b) Lösen der beschichteten Waschmittelteilchen in Wasser, um eine Waschlauge zu erzeugen;
    c) Behandeln von Gegenständen mit der Waschlauge;
    d) Trennen der Gegenstände von der Waschlauge; und
    e) Spülen und Trocknen der Gegenstände;
    wobei zumindest der Schritt c) in einem von oben zu befüllenden Waschgefäß durchgeführt wird.
  2. Verfahren nach Anspruch 1,
    wobei die beschichteten Waschmittelteilchen ferner einen oder mehrere Farbstoffe aufweisen, die vorzugsweise ausgewählt sind aus Säurefarbstoffen; Dispersionsfarbstoffen und alkoxylierten Farbstoffen, stärker bevorzugt aus denen ausgewählt sind, die Anthrachinon-, Monoazo-, Bisazo-, Xanthen-, Phthalocyanin- und Phenazin-Chromophore aufweisen, besonders bevorzugt aus denen ausgewählt sind, die Anthrachinon- und Monoazo-Chromophore aufweisen.
  3. Verfahren nach Anspruch 1 oder 2,
    wobei die anorganischen Salze, die auf den Waschmittelteilchen als Beschichtung vorliegen, Natriumcarbonat aufweisen.
  4. Verfahren nach einem der vorstehenden Ansprüche,
    wobei das anionische Tensid Alkylbenzolsulfonate, vorzugsweise Natrium-C10-C15-alkylbenzolsulfonate; Alkylethersulfate, vorzugsweise Natriumlaurylethersulfat mit 1 bis 3 Ethoxygruppen; und/oder Alkylsulfate, vorzugsweise Natrium-C12-C18-alkylsulfate, aufweisen.
  5. Verfahren nach einem der Ansprüche 1 bis 4,
    wobei das Tensid 15 bis 100 Gew.-% anionisches Tensid aufweist, wovon 20 bis 30 Gew.-% Natriumlaurylethersulfat sind, und zwar auf das gesamte Tensid bezogen.
  6. Verfahren nach einem der Ansprüche 1 bis 4,
    wobei das Tensid 15 bis 85 Gew.-% anionisches Tensid und 5 bis 75 Gew.-% nichtionisches Tensid aufweist, und zwar auf das gesamte Tensid bezogen.
  7. Verfahren nach einem der Ansprüche 1 bis 4 und 6,
    wobei das nichtionische Tensid Alkoholethoxylat mit 10 bis 50 EO ist.
  8. Verfahren nach Anspruch 7,
    wobei das nichtionische Tensid die Kondensationsprodukte von aliphatischen, primären oder sekundären, linearen oder verzweigten C8-C18-Alkoholen mit 20 bis 35 Ethylenoxidgruppen ist.
  9. Verfahren nach einem der vorstehenden Ansprüche,
    wobei die beschichteten Waschmittelteilchen 20 bis 40 Gew.-%, vorzugsweise 25 bis 35 Gew.-% der anorganischen Gerüststoffsalze als Beschichtung aufweisen.
  10. Verfahren nach einem der vorstehenden Ansprüche,
    wobei die Teilchen 0 bis 15 Gew.-%, vorzugsweise 1 bis 5 Gew.-% Wasser aufweisen.
  11. Verfahren nach einem der vorstehenden Ansprüche,
    wobei mindestens 90 bis 100 %, auf die Anzahl bezogen, der beschichteten Waschmittelteilchen bei den Abmessungen x, y und z innerhalb einer Variablen vom größten zum kleinsten beschichteten Waschmittelteilchen von 20, vorzugsweise 10 %, auf die Anzahl bezogen, liegen.
  12. Verfahren nach einem der vorstehenden Ansprüche,
    wobei das von oben zu befüllende Waschgefäß aus halbautomatischen oder automatischen Toplader-Waschmaschinen ausgewählt ist.
  13. Verfahren nach Anspruch 12,
    wobei die Maschine mit einer Vorrichtung zum Rühren der Waschlauge ausgestattet ist.
  14. Verfahren nach einem der Ansprüche 1 bis 11,
    wobei das von oben zu befüllende Waschgefäß ein Bad, eine Wanne, einen Behälter, ein Becken, eine Trommel oder ein Spülbecken aufweist.
  15. Verfahren nach einem der vorstehenden Ansprüche,
    wobei die beschichteten Waschmittelteilchen beim Waschprozess sowohl mit Wasser als auch der Haut des Anwenders in Kontakt kommen.
EP11763944.3A 2010-10-14 2011-09-30 Verfahren für von oben befüllbare wäschebehälter Active EP2627751B1 (de)

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EP10187500 2010-10-14
PCT/EP2011/067159 WO2012049033A1 (en) 2010-10-14 2011-09-30 Top-loading laundry vessel method
EP11763944.3A EP2627751B1 (de) 2010-10-14 2011-09-30 Verfahren für von oben befüllbare wäschebehälter

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WO2012049033A1 (en) 2012-04-19
CN103282477A (zh) 2013-09-04
CN103282477B (zh) 2015-04-01
ZA201302655B (en) 2014-06-25
BR112013009127B1 (pt) 2020-05-26
BR112013009127A2 (pt) 2016-07-19

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