BR112014030417B1 - DETERGENT COMPOSITION - Google Patents

Abstract

DETERGENT COMPOSITION. Detergent compositions having more than one enzyme, in particular having a multiple enzyme coparticle, and also methods of preparing and using such detergents are described. The compositions also have low levels of phosphate and zeolite-based builders and a moisture dissipator to minimize interaction between enzymes.

Description

[001] FIELD OF INVENTION

[002] This invention relates to detergent compositions comprising more than one enzyme and also to methods of producing and using such detergents.

[003] BACKGROUND OF THE INVENTION

[004] There is increasing pressure on natural resources, specifically energy and water and also the demand for the use of petrochemical compounds continues to grow. Detergent compositions comprising enzymes have been known for many years and offer the opportunity to impart excellent cleaning, care and freshness benefits from detergents particularly in low water consumption and/or low temperature washes, simultaneously reducing the need to rely so intensively from petrochemical materials. Such a formulation approach brings with it considerable challenges associated with how to provide consistently excellent cleanliness from products that need to be stable during storage over many months in an economical manner. This problem is particularly serious in warmer parts of the world.

[005] In IP.com disclosure no. IPCOM000200739D it is disclosed that the uniform distribution of enzyme granules can be improved by incorporating two or more enzymes combined into a co-granule. Each enzyme will then be present in more granules ensuring a more even distribution of enzymes in the detergent. This also reduces the physical segregation of different enzymes due to different particle sizes. However, for detergent compositions stored under conditions of high temperature and/or high humidity, the interaction between enzymes in an enzyme cogranule can lead to loss of enzymatic activity, particularly when one of the enzymes is protease. This problem is particularly serious in detergent compositions comprising low levels of typical strong builders i.e. phosphate and zeolite based builders.

[006] SUMMARY OF THE INVENTION

[007] The present invention relates to a detergent composition comprising (a) a multiple enzyme cogranule; (b) less than 10% by weight zeolite (anhydrous basis); and (c) less than 10% by weight of phosphate salt (anhydrous basis), wherein said enzyme cogranule comprises from 10 to 98% by weight of moisture dissipating component and the composition further comprises from 20 to 80% by weight. weight of detergent moisture dissipating component.

[008] The invention also relates to a method of treating and/or cleaning a surface, preferably a fabric surface comprising the steps of (i) contacting said surface with the detergent composition as claimed herein and described in an aqueous liquid washing process, (ii) rinse and/or dry the surface. preferably a temperature of the aqueous liquid is 5 to 25°C and preferably the aqueous liquid comprises from 0.1 g/l to 3 g/l of surfactant.

[009] DETAILED DESCRIPTION OF THE INVENTION

[010]Definitions

[011] As used herein "detergent composition" means institutional and consumer products, including, but not limited to cleaning and/or treatment compositions, particularly cleaning compositions for washing clothes, washing dishes, and cleaning products of hard surfaces, other cleaning agents, and cleaning systems, all for the treatment and cleaning of inanimate surfaces, and also fabric conditioning products and other products designed specifically for the treatment and maintenance of fabrics. Such detergent compositions are generally intended to be used or consumed in the form in which they are sold. Such products include treatment and/or additives for rinsing and washing clothes, treating and/or cleaning hard surfaces including floor and toilet cleaning agents. Preferably the compositions of the invention are laundry or dishwashing detergents, most preferably laundry detergents. Typically the compositions of the invention are solid, that is, in granular or powder form, which may optionally be incorporated into a unit dose detergent composition such as a tablet or containment bag which may be single-compartment or multi-compartment. However, they can be in the form of a liquid, gel or paste. In a containment bag the composition of the invention will be present within a water-soluble film. If the containment bag is multi-compartment, the composition of the invention will be present in one or more compartments. Other compositions, not in accordance with the invention, may be provided in one or more other compartments of the multi-compartment containment bag. All applicable products of this type may be in conventional, concentrated or even highly concentrated form, even to the extent that such products may, in certain aspects, be non-aqueous.

[012] For use in the present invention, articles such as "a" and "an" when used in a claim, are understood to mean one or more of what is claimed or described. For use herein, the terms "include", "includes" and "including" are intended to be construed as non-limiting. For use in the present invention, the term "solid" includes granular, powder, bar and tablet forms of product. Except where otherwise specified, all component or composition contents refer to the active portion of that component or composition and exclude impurities, for example, residual solvents or by-products, which may be present in commercially available sources of such components. or compositions. All percentages and ratios are calculated by weight unless otherwise noted. All percentages and ratios are calculated based on the total composition, except where otherwise noted.

[013] Multiple enzyme cogranule

[014] The multiple enzyme cogranule comprises at least two enzymes, or at least three or four or more enzymes, preferably selected from the group consisting of first wash lipases, cleaning cellulases, xyloglucanases, perhydrolases, peroxidases, lipoxygenases, lacases, hemicelulases, proteases, celulases para tratamento, celobiose-desidrogenases, xilanases, fosfolipases, esterases, cutinases, pectinases, mananases, pectato-liases, queratinases, redutases, oxidases, fenoloxidases, ligninases, pululanases, tanases, pentosanases, liquenases, glicanases, arabinosidases, hyaluronidase, chondroitinase, amylases, and mixtures thereof. Preferably the co-granule comprises (a) one or more enzymes selected from the group consisting of lipases for first washing, cellulases for cleaning, xyloglucanases, perhydrolases, peroxidases, lipoxygenases, laccases and mixtures thereof. The preferred enzymes of group(a) are first-wash lipases. Furthermore, the cogranule preferably comprises (b) one or more enzymes selected from the group consisting of hemicellulases, proteases, treatment cellulases, cellobiose dehydrogenases, xylanases, phospholipases, esterases, cutinases, pectinases, mannanases, pectate lyases, keratinases, reductases, oxidases, phenoloxidases, ligninases, pullulanases, tannases, pentosanases, lichenases, glycanases, arabinosidases, hyaluronidase, chondroitinase, amylases, and mixtures thereof. Preferably the co-granule comprises a protease enzyme.

[015] The co-granule may comprise, for example, at least two enzymes, for example including: (i) protease and amylase; (ii) protease and cellulase; (iii) first wash protease and lipase; (iv) first wash cellulase and lipase; (v) amylase and cellulase; or (vi) first wash amylase and lipase. Alternatively the co-granule may comprise at least three enzymes, for example including (i) protease, first-wash lipase and cellulase; (ii) protease, amylase and cellulase; (iii) first wash protease, amylase and lipase; (iv) first wash lipase, amylase and cellulase. Alternatively, the co-granule may comprise at least four enzymes, for example including (i) protease, amylase, first-wash lipase and cellulase; (ii) protease, amylase, first wash lipase and mannanase.

[016] The amount of total enzyme protein incorporated into the cogranule typically provides 0.2 to 1.0% by weight of active enzyme in the detergent composition.

[017] Moisture dissipation component

[018] The moisture-dissipating component is present in the co-granule in amounts of 10 to 99% by weight of the co-granule. Preferably the moisture dissipating material is understood here as a material which in its anhydrous form can absorb water to become hydrated and it can easily release the water of hydration when it is placed in a hotter or drier environment. Preferably the moisture-dissipating materials for use in the composition of the invention have a difference in density between the anhydrous form and the hydrated form of at least 0.8 g/cm3, more preferably at least 1 g/cm3, and especially at least less 1.2 g/cm3. This difference in densities provides a mechanism for breaking the particle:particle crystal bridges that formed as a result of water condensation when the temperature of the powder fell below the dew point associated with that of the powder. When the temperature increases after a period of cooling (as in a temperature cycle), the hydrated material that forms a crystal bridge between particles reverts to the anhydrous (or less hydrated) form. The higher crystal density associated with the anhydrous (or less hydrated) form provides a mechanism for breaking these crystal bridges due to the reduction in crystal volume. This allows a period of low temperature not to permanently negatively affect the powder structure and contributes to good handling properties of the composition.

[019] Preferably the moisture dissipating component is present in amounts of 30, 50 or even 60% by weight of the co-granule, up to 90 or 95% by weight based on the co-granule. Examples of suitable moisture-dissipating components are capable of absorbing moisture. Suitable moisture-dissipating components are preferably selected from the group consisting of (a) hydratable salts, (b) desiccated clays, (c) bioburden, and (d) mixtures thereof. Useful as hydratable salts are typically sodium, calcium, magnesium salts, preferably sodium carbonate, sodium chloride, sodium citrate and sodium sulfate salts and mixtures thereof. Anhydrous sodium carbonate may be preferred. Mild sodium carbonate may be preferred.

[020] Examples of suitable clays are talc, calcite, kaolin, dolomite and bentonite. Preferred desiccated clays have a moisture content of 0.1 to 20% by weight free moisture, more preferably 0.1 to 15 or even 0.1 to 10 or even 5% by weight free moisture;

[021] Suitable as bioburden is any water-insoluble or water-soluble agricultural by-product. Examples of water-insoluble agricultural by-products are described in WO2007/147698. Preferred bioburdens have a moisture content of 0.1 to 20% by weight free moisture, more preferably 0.1 to 15 or even 0.1 to 10% by weight or even 5% by weight free moisture;

[022] The particle size of the moisture dissipating component is preferably such that at least 90% by weight of the moisture dissipating component particles have a diameter of less than 700 or even less than 500 or 300 or 250 micrometers or even less than 100 micrometers.

[023] The weight ratio between the moisture dissipating component and the active enzyme protein in the cogranule is preferably 10:1 or 20:1 or 50:1 or 10:1 to 100:1 or 90:1 or 75: 1.

[024] Enzyme cogranules

[025] Enzyme cogranules suitable for use in the present invention include those formed according to any of the technologies below: a) Spray-dried products, in which a liquid solution containing enzymes is atomized in a spray-drying tower to form small droplets that, during their downward journey through the drying tower, dry to form particulate material containing enzymes. Very small particles can be produced in this way (Michael S. Showell (editor); "Powdered detergents"; "Surfactant Science Series"; 1998; vol. 71; pages 140 to 142; Marcel Dekker). b) Layered products, in which the enzyme is coated as a layer around a preformed inert core particle, in which an enzyme-containing solution is atomized, typically in a fluidized bed apparatus, in which the core particles Preformed particles are fluidized, and the enzyme-containing solution adheres to the core particles and dries by evaporation to leave a layer of dried enzyme on the surface of the core particle. Particles of a desired size can be obtained in this way if a useful core particle of the desired size can be found. This type of product is described in, for example, WO 97/23606. c) Absorbed core particles, where instead of coating the enzyme as a layer around the core, the enzyme is absorbed onto and/or into the surface of the core. One such process is described in WO 97/39116. d) Pelleted or extrusion products, in which an enzyme-containing paste is pressed into pellets or under pressure is extruded through a small opening and cut into small particles which are subsequently dried. Such particles are usually of considerable size because the material in which the extrusion opening is produced (usually a plate with holes) sets a limit on the allowable pressure drop relative to the extrusion opening. Also, very high extrusion pressures, when using a small opening, increase heat generation in the enzyme paste, which is harmful to the enzyme. (Michael S. Showell (editor); "Powdered detergents"; "Surfactant Science Series"; 1998; vol. 71; pages 140 to 142; Marcel Dekker) e) Globule products or, in which an enzyme powder is suspended in melted wax and the suspension is atomized, for example by a rotating disc atomizer, into a cooling chamber where droplets rapidly solidify (Michael S. Showell (editor); "Powdered detergents"; "Surfactant Science Series"; 1998 ; vol. 71; pages 140 to 142; Marcel Dekker). The product obtained is one in which the enzyme is evenly distributed throughout the inert material instead of being concentrated on its surface. Also US 4,016,040 and US 4,713,245 are documents related to this technique f) Mixer granulation products, in which an enzyme-containing liquid is added to a dry powder composition of conventional granulation components. The liquid and powder in a suitable proportion are mixed and as the moisture from the liquid is absorbed into the dry powder, the components of the dry powder will begin to stick together and agglomerate and particles will develop, forming granules comprising the enzyme. Such a process is described in US 4,106,991 (NOVO NORDISK) and in related documents EP 170360 B1, EP 304332 B1, EP 304331, WO 90/09440 and WO 90/09428. In a specific product of this process in which high shear mixers can be used as granulators, granulates consisting of the enzyme, fillers and binders etc. they are mixed with cellulose fibers to reinforce the particles to produce so-called T-granules. Reinforced particles, being more robust, release less enzymatic dust.

[026] The preferred enzyme cogranules, for use in the composition of the invention, have a core-shell structure. In preferred core-shell embodiments, the core comprises a central, preferably enzyme-free, part and a surrounding enzyme-containing layer, and the shell comprises a plurality of layers, the outermost layer being a protective layer. In preferred embodiments the central part of the core and at least one of the shell layers comprise a moisture dissipative material. Preferably the central part of the core represents from 1% to 60%, more preferably from 3% to 50% and specifically from 5% to 40% by weight of the total particle. Preferably the layer comprising the moisture dissipating material represents from 0.5% to 40%, more preferably from 1% to 30% and specifically from 3% to 20%, by weight of the total particle. Preferably the outermost layer comprises poly(vinyl alcohol), more preferably titanium oxide (for aesthetic reasons) and specifically a combination thereof. Preferably the protective layer represents from 0.05% to 20%, more preferably from 0.1% to 15% and specifically from 1% to 3% by weight of the total particle. Enzyme granulate may also contain auxiliary materials such as antioxidants, dyes, activators, solubilizers, binders, etc. Enzymes according to this embodiment can be prepared by a fluidized bed layering process similar to that described in US 5,324,649, US 6,602,841 B1 and US2008/0206830A1.

[027] Enzymes according to this modality can also be prepared by a combination of processes. Such enzyme cogranules are produced around a core which may be enzyme-free or contain enzymes (preferably comprising a moisture-dissipating material, most preferably sodium sulfate) which may be prepared using a variety of processes including the use of a mixer granulator or an extruder. The cores are then treated in a fluidized bed process in which the enzyme is atomized onto the core. The core is then coated with a layer, preferably a moisture-dissipating material, and most preferably sodium sulfate, and finally is coated with a polymer selected from the group comprising hydroxypropylmethylcellulose and/or poly(vinyl alcohol) and derivatives thereof, optionally also containing additional titanium dioxide, poly(ethylene glycol) and/or kaolin or any mixture thereof. Suitable processes for manufacturing the enzyme granulate for use in the present invention are described in US 6,348,442 B2, US 2004/0033927 A1, USP 7,273,736, WO 00/01793, US 6,268,329 B1 and US2008/0206830A1. Preferably granulated, the granulate comprises from about 30% to about 75%, preferably from about 40 to about 50% by weight of the granulate of a moisture-dissipating material selected from the group comprising sodium sulfate, sodium citrate, sodium and mixtures thereof, preferably sodium sulfate.

[028] Preferably, the enzyme cogranules have a weighted geometric mean particle size of about 200 μm to about 1200 μm, more preferably from about 300 μm to about 1000 μm and especially from about 400 μm to about 600 μm.

[029] In addition to the co-granule, the compositions of the invention comprise less than 10% by weight of zeolite (anhydrous basis), more preferably less than 7 or 5 or even less than 3% by weight of zeolite. Zeolite may even be completely absent from the detergent compositions of the invention.

[030] In addition to the co-granule, the compositions of the invention comprise less than 10% by weight of phosphate salt (anhydrous basis), more preferably less than 7 or 5 or even less than 3% by weight of phosphate salt. Phosphate salts may even be completely absent from the detergent compositions of the invention.

[031] In addition, the compositions of the invention comprise from 20 to 80% by weight of detergent moisture dissipator, preferably from 25, or 30 or 35 or 40% by weight to 75% by weight of detergent moisture dissipator. Suitable detergent moisture-dissipating components are capable of absorbing moisture and are selected from the group consisting of (a) hydratable sulfate salts, (b) desiccated clays, (c) bioburden, and (d) mixtures thereof. Useful salts are typically hydratable salts of sodium sulfate, calcium sulfate, magnesium sulfate and mixtures thereof. Sodium sulfate is particularly preferred, organic layer in its anhydrous form. Mild salts may also be preferable.

[032] Examples of suitable clays are talc, calcite, kaolin, dolomite and bentonite. Preferred desiccated clays have a moisture content of 0.1 to 20% by weight of free moisture, more preferably 0.1 to 15 or even 0.1 to 10 or even 5% by weight of free moisture.

[033] Suitable as bioburden is any water-insoluble or water-soluble agricultural by-product. Examples of water-insoluble agricultural by-products are described in WO2007/147698. Preferred bioburdens have a moisture content of 0.1 to 20% by weight free moisture, more preferably 0.1 to 15 or even 0.1 to 10% by weight or even 5% by weight free moisture;

[034] Sodium sulfate is the most preferred detergent moisture-dissipating component.

[035] The detergent moisture-dissipating component can be added dry to other detergent auxiliary ingredients or can be incorporated into the detergent composition via a preformed particle such as an agglomerate or blown powder (particulate formed from a spray drying process). , or it can be incorporated via a mixture of these routes. In a preferred composition the detergent moisture-dissipating component is incorporated into the detergent composition as a dry added particulate component comprising at least 80% by weight, or even at least 90% by weight, or even at least 95% by weight of the moisture-dissipating component. of detergent and in addition via a blown powder comprising from 15 to 70% by weight, or from 20 to 60% by weight based on the blown powder, of the detergent moisture dissipating component. Typically if the moisture dissipating component is incorporated via an agglomerated particle and/or a blown powder such particle will comprise at least 10% by weight of surfactant, based on the weight of the particle. In a particularly preferred composition of the invention, the composition will comprise dry added sodium sulfate and blown and/or agglomerated powder, preferably blown powder, comprising sodium sulfate.

[036] According to a preferred aspect of the invention, the detergent composition additionally comprises a dye transfer inhibitor agent and/or a fabric tinting agent.

[037] Auxiliary materials

[038] The detergent compositions of the invention may comprise one or more auxiliary materials (detergents). These can intensify the cleaning performance, for treating the substrate to be cleaned, or modifying the aesthetics of the composition for example as is the case with perfumes, splashes, dyes, dyes or the like. The contents of any such auxiliary incorporated into the composition of the invention in any fabric and home care product are in addition to any of the materials previously mentioned for incorporation. The exact nature of these additional components, as well as the levels of incorporation thereof, will depend on the physical form of the product intended for the consumer and the nature of the cleaning operation in which it will be used. Suitable auxiliary materials include, but are not limited to, surfactants, builders, chelating agents, dye transfer inhibiting agents, dispersants, enzymes, and enzyme stabilizers, catalytic materials, bleach activators, hydrogen peroxide, hydrogen peroxide sources. hydrogen, preformed peracids, polymeric dispersing agents, clay soil removal/anti-redeposition agents, brighteners, foam suppressants, dyes, tinting dyes, perfumes, perfume release systems, structural elasticizing agents, fabric softeners, vehicles , hydrotropes, processing aids, solvents and/or pigments. Examples of suitable auxiliaries are described below. In addition to the description below, suitable examples of these other auxiliary compounds, as well as their levels of use, are found in US Patent Nos. 5,576,282, 6,306,812 B1 and No. 6,326,348 B1, which are incorporated herein by reference .

[039] Fabric tint agents: The composition may comprise a fabric tint agent. Suitable fabric tinting agents include dyes, dye-clay conjugates, and pigments. Suitable dyes include small molecule dyes and polymeric dyes. Suitable small molecule dyes include those selected from the group consisting of dyes that fall within the Color Index (C.I.) classifications of Direct Blue, Direct Red, Direct Violet, Acid Blue, Acid Red, Acid Violet, Basic Blue, Basic Violet and Basic Red or mixtures thereof.

[040] In another aspect, suitable small molecule dyes include small molecule dyes selected from the group consisting of Color Index (Society of Dyers and Colourists, Bradford, United Kingdom) numbers Direct Violet 9, Direct Violet 35, Direct Violet 48, Direct Violet 51, Direct Violet 66, Direct Violet 99, Direct Blue 1, Direct Blue 71, Direct Blue 80, Direct Blue 279, Acid Red 17, Acid Red 73, Acid Red 88, Acid Red 150, Acid Violet 15, Acid Violet 17, Acid Violet 24, Acid Violet 43, Acid Red 52, Acid Violet 49, Acid Blue 15, Acid Blue 17, Acid Blue 25, Acid Blue 29, Acid Blue 40, Acid Blue 45, Acid Blue 75, Acid Blue 80, Acid Blue 83, Acid Blue 90 and Acid Blue 113, Acid Black 1, Basic Violet 1, Basic Violet 3, Basic Violet 4, Basic Violet 10, Basic Violet 35, Basic Blue 3, Basic Blue 16, Basic Blue 22, Basic Blue 47, Basic Blue 66, Basic Blue 75, Basic Blue 159 and their mixtures. In another aspect, suitable small molecule dyes include small molecule dyes selected from the group consisting of the Color Index (Society of Dyers and Colourists, Bradford, United Kingdom) numbers Acid Violet 17, Acid Violet 43, Acid Red 52, Red Acid 73, Acid Red 88, Acid Red 150, Acid Blue 25, Acid Blue 29, Acid Blue 45, Acid Blue 113, Acid Black 1, Direct Blue 1, Direct Blue 71, Direct Violet 51 and mixtures thereof. In another aspect, suitable small molecule dyes include those selected from the group consisting of Color Index numbers (Society of Dyers and Colourists, Bradford, United Kingdom) Acid Violet 17, Direct Blue 71, Direct Violet 51, Blue Direct 1, Acid Red 88, Acid Red 150, Acid Blue 29, Acid Blue 113 or mixtures thereof.

[041] Suitable polymeric dyes include polymeric dyes selected from the group consisting of polymers containing conjugated chromogens (dye-polymer conjugates) and polymers with chromogens copolymerized in the polymer backbone and mixtures thereof.

[042] In another aspect, suitable polymeric dyes include those selected from the group consisting of fabric-adherent dyes commercially available under the name Liquitint® (Milliken, Spartanburg, South Carolina, USA), dye-polymer conjugates formed from hair at least one reactive dye and a polymer selected from the group consisting of polymers comprising a portion selected from the group consisting of a hydroxyl moiety, a primary amine moiety, a secondary amine moiety, a thiol moiety and mixtures thereof. In yet another aspect, suitable polymeric dyes include polymeric dyes selected from the group consisting of Liquitint® (Milliken, Spartanburg, South Carolina, USA) Violet CT, carboxymethylcellulose (CMC) conjugated with a reactive blue, reactive violet or reactive red dye. as CMC conjugated with Reactive Blue C.I. 19, sold by Megazyme, Wicklow, Ireland under the product name AZO-CM-CELLULOSE, product code S-ACMC, alkoxylated triphenylmethane polymeric dyes, alkoxylated thiophene polymeric dyes and mixtures thereof.

[043] Suitable dye-clay conjugates include those selected from the group consisting of at least one cationic/basic dye and a smectite clay, as well as mixtures thereof. In another aspect, suitable dye-clay conjugates include those selected from the group consisting of a cationic/base dye selected from the group consisting of Basic Yellow I.C. 1 to 108, Basic Orange I.C. 1 to 69, Basic Red I.C. 1 to 118 , Basic Violet I.C. 1 to 51, Basic Blue I.C. 1 to 164, Basic Green I.C. 1 to 14, Basic Brown I.C. 1 to 23, Basic Black I.C. 1 to 11, and a clay selected from the group consisting of clay montmorillonite, hectorite clay, and saponite clay, as well as mixtures thereof. In yet another aspect, suitable dye-clay conjugates include dye-clay conjugates selected from the group consisting of: Montmorillonite Basic Blue B7 C.I. 42595 conjugate, Montmorillonite Basic Blue B9 C.I. 52015 conjugate, Montmorillonite Basic Violet V3 C.I. 42555 conjugate , Montmorillonite Basic Green G1 C.I. 42040 conjugate, Montmorillonite Basic Red R1 C.I. 45160 conjugated, Montmorillonite C.I. Basic Black 2 conjugate, Hectorite Basic Blue B7 C.I. 42595 conjugated, Hectorite Basic Blue B9 C.I. 52015 conjugate, Basic Violet of hectorite V3 C.I. 42555 conjugate, Hectorite Basic Green G1 C.I. 42040 conjugate, Hectorite Basic Red R1 C.I. 45160 conjugate, Hectorite Basic Black C.I. 2 conjugate, Saponite Basic Blue B7 C.I. 42595 conjugate, Saponite Basic Blue B9 C.I. 5201 5 conjugate, Basic Violet saponite V3 C.I. 42555 conjugate, Saponite Basic Green G1 C.I. 42040 conjugate, Saponite Basic Red R1 C.I. 45160 conjugate, Saponite Basic Black C.I. Black Basic 2 conjugate and mixtures thereof.

[044] Suitable pigments include those selected from the group consisting of flavanthrone, indanthrone, chlorinated indanthrone containing 1 to 4 chlorine atoms, pyranthrone, dichloropyranthrone, monobromodichloropyranthrone, dibromodichloropyranthrone, tetrabromopyranthrone, perylene acid diimide-3,4,9,10 -tetracarboxylic, wherein the imide groups may be unsubstituted or substituted with C1-C3 alkyl or a phenyl or heterocyclic radical, and wherein the phenyl and heterocyclic radicals may additionally carry substituents that do not confer solubility in water, amides of antrapyrimidinecarboxylic acid, violanthrone, isoviolanthrone, dioxazine-based pigments, copper phthalocyanine which may contain up to 2 chlorine atoms per molecule, polychloro-copper phthalocyanine or polybromochloro-copper phthalocyanine containing up to 14 bromine atoms per molecule, as well as their mixtures.

[045] In another aspect, suitable pigments include those selected from the group consisting of Ultramarine Blue (I.C. Blue Pigment 29), Ultramarine Violet (I.C. Violet Pigment 15) and mixtures thereof.

[046] The previously mentioned fabric tint agents can be used in combination (any mixture of fabric tint agents can be used). Suitable fabric tinting agents can be purchased from Aldrich, Milwaukee, Wisconsin, USA; Ciba Specialty Chemicals, Basel, Switzerland; BASF, Ludwigshafen, Germany; Dayglo Color Corporation, Mumbai, India; Organic Dyestuffs Corp., East Providence, Rhode Island, USA; Dystar, Frankfurt, Germany; Lanxess, Leverkusen, Germany; Megazyme, Wicklow, Ireland; Clariant, Muttenz, Switzerland; Avecia, Manchester, United Kingdom and/or produced in accordance with the examples contained herein. Suitable tinting agents are described in greater detail in US Patent No. 7,208,459 B2.

[047] Encapsulated: The composition may comprise an encapsulated substance. In one aspect, an encapsulant comprising a core and a film having an inner surface and an outer surface is provided, wherein said film encapsulates said core.

[048] In one aspect of said encapsulated, said core may comprise a material selected from the group consisting of perfumes; rinse aids; dyes; insect repellents; silicones; waxes; flavorings; vitamins; fabric softening agents; skin treatment agents, in one aspect, paraffins; enzymes; antibacterial agents; bleaches; sensory elements; as well as their mixtures; and said shell may comprise a material selected from the group consisting of polyethylenes; polyamides; polystyrenes; polyisoprenes; polycarbonates; polyester; polyacrylates; aminated plastics, in one aspect, said aminoplastic may comprise a polyurea, polyurethane and/or polyureaurethane, in one aspect, said polyurea may comprise polyoxymethyleneurea and/or melamine-formaldehyde; polyolefins; polysaccharides, in one aspect, said polysaccharide may comprise alginate and/or chitosan; gelatin; shellac; epoxy resins; vinyl polymers; inorganic compounds insoluble in water; silicone; and their mixtures. In one aspect of said encapsulated, said core may comprise perfume. In one aspect of said encapsulated, said shell may comprise melamine-formaldehyde and/or cross-linked melamine-formaldehyde.

[049] In one aspect, suitable encapsulates may comprise a core material and a capsule, said capsule at least partially surrounding said core material. At least 75%, 85% or even 90% of said encapsulates may have a fracture resistance of about 0.2 MPa to about 10 MPa, of about 0.4 MPa to about 5 MPa, of about 0 .6 MPa to about 3.5 MPa, or even from about 0.7 MPa to about 3 MPa; and a flow of benefit agent from 0% to about 30%, from 0% to about 20%, or even from 0% to about 5%. In one aspect, at least 75%, 85% or even 90% of said encapsulated may have a particle size of from about 1 micrometer to about 80 micrometers, from about 5 micrometers to 60 micrometers, from about 10 micrometers to about 50 micrometers, or even from about 15 micrometers to about 40 micrometers. In one aspect, at least 75%, 85% or even 90% of said encapsulates may have a particle wall thickness of from about 30 nm to about 250 nm, from about 80 nm to about 180 nm, or even from about 100 nm to about 160 nm.

[050] In one aspect, said encapsulated core material may comprise a material selected from the group consisting of a perfume raw material and/or, optionally, a material selected from the group consisting of vegetable oil, including pure vegetable oils and /or mixed, including castor oil, coconut oil, cottonseed oil, grapeseed oil, rapeseed oil, soybean oil, corn oil, babassu oil, linseed oil, safflower oil, olive oil, oil peanut oil, coconut oil, palm kernel oil, castor oil, lemon oil and mixtures thereof; vegetable oil esters, esters including dibutyl adipate, dibutyl phthalate, benzyl and butyl adipate, benzyl and octyl adipate, tricresyl phosphate, trioctyl phosphate and mixtures thereof; straight-chain or branched hydrocarbons, including those straight-chain or branched hydrocarbons that have a boiling point greater than about 80 °C; partially hydrogenated terphenyls, dialkyl phthalates, alkylbiphenyls, including monoisopropylbiphenyl, alkylated naphthalene, including dipropylnaphthalene, petroleum ether, including kerosene, mineral oil and mixtures thereof; aromatic solvents, including benzene, toluene and mixtures thereof; silicone oils; and their mixtures.

[051] In one aspect, the wall material of said encapsulates may comprise a suitable resin including the reaction product of an aldehyde and an amine, suitable aldehydes including formaldehyde. Suitable amines include melamine, urea, benzoguanamine, glycoluryl, and mixtures thereof. Suitable melamines include methylol melamine, methylated methylol melamine, imino melamine and mixtures thereof. Suitable ureas include dimethylol-urea, methylated dimethylol-urea, urea-resorcinol, and mixtures thereof.

[052] In one aspect, suitable formaldehyde sequestrants can be employed with the encapsulates, for example, in an aqueous capsule paste and/or added to a consumer product before, during or after the encapsulates are added to such product. intended for the consumer.

[053] Suitable capsules can be made in accordance with the teachings contained in USPA 2008/0305982 A1; and/or USPA 2009/0247449 A1. Alternatively, suitable capsules can be purchased from Appleton Papers Inc. of Appleton, Wisconsin, USA.

[054] In addition, the materials to produce the aforementioned encapsulates can be obtained from one or more of the following companies: Solutia Inc. (St Louis, Missouri, USA), Cytec Industries (West Paterson, New Jersey, USA), Sigma - Aldrich (St. Louis, Missouri USA), CP Kelco Corp. from San Diego, California, USA; BASF AG of Ludwigshafen, Germany; Rhodia Corp. from Cranbury, New Jersey, USA; Hercules Corp. from Wilmington, Delaware, USA; Agrium Inc. of Calgary, Alberta, Canada, ISP of New Jersey, USA, Akzo Nobel of Chicago, IL, USA; Stroever Shellac Bremen of Bremen, Germany; Dow Chemical Company of Midland, MI, USA; Bayer AG of Leverkusen, Germany; Sigma-Aldrich Corp., St. Louis, Missouri, USA.

[055] Polymers: The product intended for the consumer may comprise one or more polymers. Examples are carboxymethyl cellulose, poly(vinylpyrrolidone), poly(ethylene glycol), poly(vinyl alcohol), poly(vinylpyridine-N-oxide), poly(vinylimidazole), polycarboxylates such as polyacrylates, maleic acid/acrylic copolymers and methacrylate copolymers. lauryl/acrylic acid.

[056] The product intended for the consumer may comprise one or more amphiphilic polymers for cleaning such as the compound that has the following general structure: bis((C2H5O)(C2H4O)n)(CH3)-N+-CxH2x-N+-(CH3) - bis((C2H5O)(C2H4O)n), in which n = from 20 to 30, and x = from 3 to 8, or its sulfated or sulfonated variants.

[057] The consumer product may comprise amphiphilic grease/grease cleaning polymers that have balanced hydrophilic and hydrophobic properties so that they can remove grease/grease particles from fabrics and surfaces. Specific embodiments of the alkoxylated amphiphilic grease cleaning polymers of the present invention comprise a core structure and a plurality of alkoxylate groups attached to the core structure. These may comprise alkoxylated polyalkyleneimines, preferably having an inner polyethylene oxide block and an outer polypropylene oxide block.

[058] Carboxylate polymer - The detergent composition of the present invention may also include one or more carboxylate polymers such as a random maleate/acrylate copolymer or polyacrylate homopolymer. In one aspect, the carboxylate polymer is a polyacrylate homopolymer having a molecular weight of 4,000 Da to 9,000 Da, or 6,000 Da to 9,000 Da.

[059] Soil-releasing polymer - The detergent composition of the present invention may also include one or more dirt-releasing polymers having a structure as defined by one of the following structures (I), (II) or (III): (I ) -[(OCHR1-CHR2)a-O-OC-Ar-CO-]d (II) -[(OCHR3-CHR4)b-O-OC-sAr-CO-]e (III) -[(OCHR5-CHR6)c- OR7]f where: a, b and c are from 1 to 200; d, e and f are from 1 to 50; Ar is a 1,4-substituted phenylene; sAr is phenylene 1,3-substituted in position 5 by SO3Me, Me is Li, K, Mg/2, Ca/2, Al/3, ammonium, mono-, di-, tri- or tetraalkyl-ammonium, with the groups alkyl are C1-C18 alkyl or C2-C10 hydroxyalkyl or mixtures thereof, R1, R2, R3, R4, R5 and R6 are independently selected from H or C1-C18 n or iso-alkyl; and R7 is a C1-C18 linear or branched alkyl or a C2-C30 linear or branched alkenyl, or a cycloalkyl group having 5 to 9 carbon atoms, or a C8-C30 aryl group, or a C6-C30 arylalkyl group.

[060] Suitable soil release polymers are polyester-based soil release polymers such as Repel-o-tex polymers, including Repel-o-tex SF, SF-2 and SRP6 supplied by Rhodia. Other suitable soil release polymers include Texcare polymers, including Texcare SRA100, SRA300, SRN100, SRN170, SRN240, SRN300 and SRN325 supplied by Clariant. Other suitable dirt release polymers are Marloquest polymers such as Marloquest SL supplied by Sasol.

[061] Cellulosic polymer - The detergent composition of the present invention may also include one or more cellulosic polymers including those selected from alkylcellulose, alkylalkoxyalkylcellulose, carboxyalkylcellulose, alkylcarboxyalkylcellulose. In one aspect, the cellulosic polymers are selected from the group comprising carboxymethylcellulose, methylcellulose, methylhydroxyethylcellulose, methylcarboxymethylcellulose, and mixtures thereof. In one aspect, carboxymethylcellulose has a degree of carboxymethyl substitution of 0.5 to 0.9 and a molecular weight of 100,000 Da to 300,000 Da.

[062] Enzymes: In addition to the enzymes present in the cogranule, the detergent composition may comprise one or more additional enzymes that provide cleaning performance and/or fabric treatment benefits. Examples of suitable enzymes include, but are not limited to, hemicellulases, peroxidases, proteases, cellulases, xylanases, lipases, phospholipases, esterases, cutinases, pectinases, mannanases, pectate lyases, keratinases, reductases, oxidases, phenoloxidases, lipoxygenases, ligninases, pullulanases , tannases, pentosanases, malanases, β-glucanases, arabinosidases, hyaluronidase, chondroitinase, laccase and amylases, or mixtures thereof. A typical combination is an enzyme cocktail that may comprise, for example, a protease and a lipase together with amylase. When present in the detergent composition of the invention, the aforementioned additional enzymes may be present in levels of from about 0.00001% to about 2%, from about 0.0001% to about 1% or even from about 0.001% to approximately 0.5% enzyme protein by weight of the product intended for the consumer. The detailed information provided below relates to enzymes suitable for incorporation into the co-granule or detergent composition more generally other than via the co-granule.

[063] In one aspect, preferred enzymes would include a protease. Suitable proteases include metalloproteases and serine proteases, including neutral or alkaline microbial serine proteases such as subtilisins (EC 3.4.21.62). Suitable proteases include those of animal, vegetable or microbial origin. In one aspect, such a suitable protease may be of microbial origin. Suitable proteases include chemically or genetically modified mutants of the aforementioned suitable proteases. In one aspect, the suitable protease may be a serine protease, such as an alkaline microbial protease and/or a trypsin-like protease. Examples of suitable neutral or alkaline proteases include: (a) subtilisins (EC 3.4.21.62), including those derived from bacillus, such as Bacillus lentus, B. alkalophilus, B. subtilis, B. amyloliquefaciens, Bacillus pumilus and Bacillus gibsonii, described in US 6,312,936 B1, US 5,679,630, US 4,760,025, US 7,262,042 and WO09/021867. (b) trypsin-type or chymotrypsin-type proteases, such as trypsin (e.g., of porcine or bovine origin), including the Fusarium protease described in WO 89/06270 and the Cellumonas-derived chymotrypsin proteases described in WO 05/052161 and WO 05/052146. (c) metalloproteases, including those derived from Bacillus amyloliquefaciens described in WO 07/044993A2.

[064] Preferred proteases include those derived from Bacillus gibsonii or Bacillus lentus.

[065] Suitable commercially available protease enzymes include those marketed under the trade names Alcalase®, Savinase®, Primase®, Durazym®, Polarzyme®, Kannase®, Liquanase®, Liquanase Ultra®, Savinase Ultra®, Ovozyme®, Neutrase®, Everlase® and Esperase® by Novozymes A/S (Denmark), those sold under the trade name Maxatase®, Maxacal®, Maxapem®, Properase®, Purafect®, Purafect Prime®, Purafect Ox®, FN3®, FN4®, Excellase® and Purafect OXP® by Genencor International, those sold under the trade name of Opticlean® and Optimase® by Solvay Enzymes, those available from Henkel/Kemira, namely BLAP (sequence shown in Figure 29 of US 5,352,604 with the following mutations S99D + S101 R + S103A + V104I +G159S, later in this document called BLAP), BLAP R (BLAP with S3T + V4I + V199M + V205I + L217D), BLAP X (BLAP with S3T + V4I + V205I) and BLAP F49 (BLAP with S3T + V4I + A194P + V199M + V205I + L217D) - all obtained from Henkel/Kemira; and KAP (Bacillus alkalophilus subtilisin with mutations A230V + S256G + S259N) from Kao.

[066] Suitable alpha-amylases include those of bacterial or fungal origin. Chemically or genetically modified mutants (variants) are included. A preferred alkaline alpha amylase is derived from a strain of bacillus, such as Bacillus licheniformis, Bacillus amyloliquefaciens, Bacillus stearothermophilus, Bacillus subtilis or other Bacillus sp., such as Bacillus sp. NCIB 12289, NCIB 12512, NCIB 12513, DSM 9375 (USP 7,153,818) DSM 12368, DSMZ No. 12649, KSM AP1378 (WO 97/00324), KSM K36 or KSM K38 (EP 1,022,334). Preferred amylases include: (a) the variants described in WO 94/02597, WO 94/18314, WO96/23874 and WO 97/43424, especially the variants with substitutions in one or more of the following positions versus the enzyme mentioned as SEQ ID No. 2 in WO 96/23874: 15, 23, 105, 106, 124, 128, 133, 154, 156, 181, 188, 190, 197, 202, 208, 209, 243, 264, 304, 305, 391 , 408 and 444. (b) the variants described in USP 5,856,164 and WO99/23211, WO 96/23873, WO00/60060 and WO 06/002643, especially the variants with one or more substitutions in the following positions versus the enzyme AA560 mentioned as SEQ ID No. 12 in WO 06/002643: 26, 30, 33, 82, 37, 106, 118, 128, 133, 149, 150, 160, 178, 182, 186, 193, 203, 214, 231 , 256, 257, 258, 269, 270, 272, 283, 295, 296, 298, 299, 303, 304, 305, 311, 314, 315, 318, 319, 339, 345, 361, 378, 383, 4 19 , 421, 437, 441, 444, 445, 446, 447, 450, 461, 471, 482, 484, preferably also containing the D183* and G184* deletions. (c) variants showing at least 90% identity with SEQ ID No. 4 in WO06/002643, the naturally occurring enzyme obtained from Bacillus SP722, especially the variants with deletion at positions 183 and 184 and the variants described in WO 00 /60060, which is incorporated herein by reference. (d) variants that show at least 95% identity with the naturally occurring enzyme obtained from Bacillus sp.707 (SEQ ID No. 7 in US 6,093,562), especially those comprising one or more of the following mutations M202, M208 , S255, R172, and/or M261. Preferably, said amylase comprises one or more of M202L, M202V, M202S, M202T, M202I, M202Q, M202W, S255N and/or R172Q. Particularly preferred are those comprising the M202L or M202T mutations.

[067] Suitable commercially available alpha-amylases include DURAMYL®, LIQUEZYME®, TERMAMYL®, TERMAMYL ULTRA®, NATALASE®, SUPRAMYL®, STAINZYME®, STAINZYME PLUS®, FUNGAMYL® and BAN® (Novozymes A/S, Bagsvaerd, Denmark), KEMZYM® AT 9000 (Biozym Biotech Trading GmbH Wehlistrasse 27b A-1200, Vienna, Austria), RAPIDASE®, PURASTAR®, ENZYSIZE®, OPTISIZE HT PLUS® and PURASTAR OXAM® (Genencor International Inc., Palo Alto, California , USA) and KAM® (Kao, 14-10 Nihonbashi Kayabacho, 1-chome, Chuo-ku, 103-8210, Tokyo, Japan). In one aspect, suitable amylases include NATALASE®, STAINZYME® and STAINZYME PLUS® and mixtures thereof.

[068] In one aspect, these enzymes can be selected from the group consisting of: lipases, including "first wash lipases" such as those described in US patent No. 6,939,702 B1 and US PA 2009/0217464. In one aspect, the lipase is a first wash lipase, preferably a naturally occurring lipase variant obtained from Thermomyces lanuginosus comprising the T231R and N233R mutations. The wild-type sequence consists of the 269 amino acids (amino acids 23 to 291) of Swiss-Prot accession number O59952 (derived from Thermomyces lanuginosus (Humicola lanuginosa)). Preferred lipases would include those sold under the trade names Lipex® and Lipolex®.

[069] In one aspect, other preferred enzymes include microbially derived endoglycanases, endoglycanases that exhibit endo-beta-1,4-glucanase activity (E.C. 3.2.1.4), which includes a bacterial polypeptide endogenous to a member of the genus Bacillus that has a sequence with at least 90%, 94%, 97% and even 99% identity with the amino acid sequence SEQ ID NO:2 in 7,141,403B2) and mixtures thereof. Suitable endoglycanases are sold under the trade names Celluclean® and Whitezyme® (Novozymes A/S, Bagsvaerd, Denmark).

[070] Other preferred enzymes include pectate lyases sold under the trade names Pectawash®, Pectaway®, Xpect® and mannanases sold under the trade names Mannaway® (all available from Novozymes A/S, Bagsvaerd, Denmark), and Purabrite® ( Genencor International Inc., Palo Alto, California, USA).

[071] Bleaching agents: The detergent composition of the present invention may comprise one or more bleaching agents. Suitable bleaching agents other than bleach catalysts include photobleaches, bleach activators, hydrogen peroxide, hydrogen peroxide sources, preformed peracids and combinations thereof. In general, when a bleaching agent is used, the detergent composition of the present invention may comprise from about 0.1% to about 50% or even from about 0.1% to about 25% bleaching agent, by weight. , of this product intended for the consumer. Examples of suitable bleaching agents include: (1) photobleaches, for example sulfonated zinc phthalocyanine, sulfonated aluminum phthalocyanine, xanthene dyes and mixtures thereof; (2) preformed peracids: Suitable preformed peracids include, but are not limited to, compounds selected from the group consisting of percarboxylic acids and salts, percarbonic acids and salts, perimidic acids and salts, peroxymonosulfuric acids and salts, e.g. Oxone®, and its combinations. Suitable percarboxylic acids include hydrophobic and hydrophilic peracids having the formula R-(C=O)OOM, wherein R is an alkyl group, optionally branched, having, when the peracid is hydrophobic, from 6 to 14 carbon atoms, or from 8 to 12 carbon atoms and, when the peracid is hydrophilic, less than 6 carbon atoms or even less than 4 carbon atoms; and M is a counterion, for example sodium, potassium or hydrogen. The preformed peroxyacid or salt thereof is preferably a peroxycarboxylic acid or salt thereof, typically having a chemical structure corresponding to the following chemical formula: wherein: R14 is selected from alkyl, arylalkyl, cycloalkyl, aryl or heterocyclic groups; the group R14 can be linear or branched, substituted or unsubstituted; and Y is any suitable counterion that achieves electrical charge neutrality, preferably Y is selected from hydrogen, sodium or potassium. Preferably, R14 is a linear or branched C6-14 alkyl, substituted or unsubstituted. When the peracid is hydrophobic, preferably R14 has 6 to 14 carbon atoms, or 8 to 12 carbon atoms, and when the peracid is hydrophilic, R14 preferably has less than 6 carbon atoms or even less than 4 atoms. of carbon. Preferably, the peroxyacid or salt thereof is selected from peroxyhexanoic acid, peroxyheptanoic acid, peroxyoctanoic acid, peroxynonanoic acid, peroxidecanoic acid, any salt thereof, or any combination thereof. Particularly preferred peroxyacids are phthalimidoperoxyalkanoic acids, in particular ε-phthalimidoperoxyhexanoic acid (PAP). Preferably, the peroxyacid or salt thereof has a melting point in the range of 30°C to 60°C.

[072] The preformed peroxyacid or its salt can be a peroxysulfonic acid or its salt, typically having a chemical structure that corresponds to the following chemical formula: wherein: R15 is selected from alkyl, arylalkyl, cycloalkyl, aryl or heterocyclic groups; the R15 group may be linear or branched, substituted or unsubstituted; and Z is any suitable counterion that achieves electrical charge neutrality, preferably selected from hydrogen, sodium or potassium. Preferably R15 is a linear or branched C6-9 alkyl, substituted or unsubstituted. Preferably such bleaching components may be present in the compositions of the invention in an amount of 0.01 to 50%, most preferably 0.1% to 20%; (3) sources of hydrogen peroxide, for example, inorganic perhydrate salts, including alkali metal salts such as perborate sodium salts (generally mono- or tetrahydrate), percarbonate, persulfate, perphosphate and persilicate salts, and combinations thereof . In one aspect of the invention, inorganic perhydrate salts are selected from the group consisting of perborate sodium salts, percarbonate salts, and combinations thereof. When used, inorganic perhydrate salts are typically present in amounts of 0.05 to 40% by weight or 1 to 30% by weight of the total fabric treatment and home care product, and are typically incorporated into to these products in the form of a crystalline solid that can be applied as a coating. Suitable coatings include inorganic salts such as alkali metal silicate, carbonate or borate salts or mixtures thereof, or organic materials such as water-soluble or dispersible polymers, waxes, oils or fatty soaps; and (4) bleach activators having R-(C=O)-L wherein R is an alkyl group, optionally branched, which has, when the bleach activator is hydrophobic, from 6 to 14 carbon atoms, or from 8 to 12 carbon atoms and, when the bleach activator is hydrophilic, less than 6 carbon atoms or even less than 4 carbon atoms; and L is leaving group. Examples of suitable leaving groups are benzoic acid and derivatives thereof, especially benzene sulfonate. Suitable bleach activators include dodecanoyloxybenzenesulfonate, decanoyloxybenzenesulfonate, decanoyloxybenzoic acid or its salts, 3,5,5-trimethylhexanoyloxybenzenesulfonate, tetraacetylethylenediamine (TAED) and nonanoyloxybenzenesulfonate (NOBS). Suitable bleach activators are also disclosed in WO 98/17767. Although any suitable bleach activator may be used, in one aspect of the invention, the consumer product in question may comprise NOBS, TAED or mixtures thereof.

[073] When present, the peracid and/or bleach activator is generally present in the consumer product in an amount of from about 0.1 to about 60%, by weight, from about 0.5 to about 40%. % by weight, or even from about 0.6 to about 10% by weight, based on the fabric treatment and home care product. One or more hydrophobic peracids or precursors thereof can be used in combination with one or more hydrophilic peracids or precursors thereof.

[074] The amounts of hydrogen peroxide source and peracid or bleach activator can be selected so that the molar ratio between available oxygen (from the peroxide source) and peracid is from 1:1 to 35:1 or even 2:1 to 10:1. (5) Organic bleaching catalysts - The detergent composition of the present invention may also include one or more bleaching catalysts capable of accepting an oxygen atom from a peroxyacid and/or its salt, and transfer the oxygen atom to an oxidizable substrate. Suitable bleaching catalysts include, but are not limited to: iminium cations and polyions; iminium zwitterions; modified amines; modified amine oxides; N-sulfonylimines; N-phosphonylimines; N-acylimines; thiadiazole dioxides; perfluoroimines; cyclic sugar ketones and mixtures thereof as described in US PA 2007/0173430 A1.

[075] In one aspect, the bleach catalyst has a structure that corresponds to the general formula below: wherein R13 is selected from the group consisting of 2-ethylhexyl, 2-propylheptyl, 2-butyloctyl, 2-pentylnonyl, 2-hexyldecyl, n-dodecyl, n-tetradecyl, n-hexadecyl, n-octadecyl, iso-nonyl, iso-decyl, isotridecyl and isopentadecyl;(6) Metal-based bleaching catalysts - The bleaching component can be provided by a catalytic metal complex. One type of metal-containing bleach catalyst is a catalyst system containing a transition metal cation with defined catalytic activity for bleaching, such as copper, iron, titanium, ruthenium, tungsten, molybdenum or manganese cations, an auxiliary metal cation having little or no catalytic bleaching activity, such as zinc or aluminum cations, and a scavenger that has defined stability constants for the catalytic and auxiliary metal cations, particularly ethylenediaminetetraacetic acid, ethylenediaminetetra(methylenephosphonic) acid, and their water-soluble salts. These catalysts are disclosed in US 4,430,243. Preferred catalysts are described in WO09/839406, US6218351 and WO00/012667. Particularly preferred are the transition metal catalyst or ligands therefor which are cross-bridged polydentate N-donor ligands.

[076] If desired, the compositions of the present invention can be catalyzed using a manganese compound. Such compounds and usage levels are well known in the art and include, for example, the manganese-based catalysts disclosed in U.S. 5,576,282.

[077] Cobalt-based bleaching catalysts used here are known, and are described, for example, in US patent 5,597,936; US 5,595,967. Such cobalt-based catalysts are readily prepared by known procedures, as taught, for example, in US Patent No. 5,597,936 and US Patent No. 5,595,967.

[078] The compositions of the present invention may also stably include a transition metal complex of ligands such as bispidones (U.S. 7,501,389) and/or macropolycyclic rigid ligands - abbreviated as "MRLs". As a practical matter, and not by way of limitation, the compositions and processes of the present invention can be adjusted to provide on the order of at least one part per hundred million of the active MRL species in the aqueous wash medium, and will typically provide from about 0.005 ppm to about 25 ppm, from about 0.05 ppm to about 10 ppm, or even from about 0.1 ppm to about 5 ppm, of the MRL in the wash liquid.

[079] Suitable transition metals in the present transition metal-based bleaching catalyst include, for example, manganese, iron and chromium. Suitable MRLs include 5,12-diethyl-1,5,8,12-tetraazabicyclo[6.6.2]hexadecane.

[080] Suitable transition metal MRLs are readily prepared by known procedures, such as those taught, for example, in U.S. 6,225,464 and WO 00/32601.

[081] Surfactants: The detergent composition according to the present invention may comprise a surfactant or surfactant system in which the surfactant may be selected from nonionic surfactants, anionic surfactants, cationic surfactants, ampholytic surfactants, zwitterionic surfactants, semipolar nonionic surfactants and your mixtures. When present, the surfactant is typically present at a content of from about 0.1% to about 60%, from about 1% to about 50%, or even from about 5% to about 40%. by weight of the product intended for the consumer in question.

[082] Suitable anionic detersive surfactants include sulfate- and sulfonate-based detersive surfactants. Suitable sulfonate-based detersive surfactants include alkylbenzenesulfonate, in one aspect, C10-13 alkyl benzenesulfonate. Suitable alkylbenzenesulfonate (LAS) can be obtained by sulfonation of commercially available linear alkylbenzene (LAB); Suitable LAB includes lower 2-phenyl-LAB, such as those supplied by Sasol under the trade name Isochem® or those supplied by Petresa under the trade name Petrelab®, other suitable LABs include higher 2-phenyl-LAB, such as those supplied by Sasol under the commercial name Hyblene®. A suitable detergent anionic surfactant is alkylbenzenesulfonate which is obtained by the DETAL catalysis process, although other synthesis routes, such as HF, may also be suitable. Suitable sulfate-based detersive surfactants include alkyl sulfate, in one aspect, C8-18 alkyl sulfate or, predominantly, C12 alkyl sulfate. Another suitable sulfate-based detersive surfactant is alkoxylated alkyl sulfate, in one aspect, an ethoxylated alkyl sulfate, in one aspect, an alkoxylated C8-18 alkyl sulfate, in another aspect, an ethoxylated C8-18 alkyl sulfate, typically, the alkoxylated alkyl sulfate having an average degree of alkoxylation of 0.5 to 20, or from 0.5 to 10, typically, the alkoxylated alkyl sulfate is an ethoxylated C8-18 alkyl sulfate that has an average degree of ethoxylation of 0.5 to 10, from 0. 5 to 7, from 0.5 to 5 or even from 0.5 to 3. Alkylsulfate, alkoxylated alkylsulfate and alkylbenzenesulfonates can be linear or branched, substituted or unsubstituted.

[083] The detersive surfactant can be a branched medium chain detersive surfactant, in one aspect, a branched medium chain anionic detersive surfactant, in one aspect, a branched medium chain alkyl sulfate and/or a branched chain alkyl benzene sulfonate branched medium, for example, a branched medium chain alkyl sulfate. In one aspect, the medium chain branches are C1-4 groups, typically methyl and/or ethyl groups.

[084] Suitable nonionic detersive surfactants are selected from the group consisting of: C8-C18 alkyl ethoxylates, such as NEODOL® nonionic surfactants available from Shell; C6-C12 alkyl phenol alkoxylates wherein the alkoxylate units may be oxyethylene units, oxypropylene units or a mixture thereof; C12-C18 alcohol and C6-C12 alkyl phenol condensates with ethylene oxide/propylene oxide block polymers such as Pluronic® from BASF; C14-C22 branched medium-chain alcohols, branched medium-chain C14-C22 alkyl alkoxylates, typically with an average degree of alkoxylation of 1 to 30, alkylpolysaccharides, in one aspect, alkylpolyglycosides; polyhydroxylated fatty acid amides, ether-blocked poly(oxyalkylated) alcohol-based surfactants, and mixtures thereof. Suitable nonionic detersive surfactants include alkylpolyglycoside and/or an alkoxylated alkyl alcohol. In one aspect, nonionic detersive surfactants include alkoxylated alkyl alcohols, in one aspect, alkoxylated C8-18 alkyl alcohol, for example, an ethoxylated C8-18 alkyl alcohol, the alkoxylated alkyl alcohol may have an average degree of alkoxylation of 1 to 50 , from 1 to 30, from 1 to 20, or from 1 to 10. In one aspect, the alkoxylated alkyl alcohol may be an ethoxylated C8-18 alkyl alcohol having an average degree of ethoxylation from 1 to 10, from 1 to 7 , more than 1 to 5 or 3 to 7. The alkoxylated alkyl alcohol may be linear or branched, and substituted or unsubstituted.

[085] Suitable cationic detersive surfactants include alkylpyridinium compounds, quaternary alkylammonium compounds, quaternary alkylphosphonium compounds, ternary alkylsulfonium compounds and mixtures thereof. Suitable cationic detersive surfactants are quaternary ammonium compounds with the following general formula: (R)(R1)(R2)(R3)N+ or unsubstituted, R1 and R2 are independently selected from methyl or ethyl moieties, R3 is a hydroxyl, hydroxymethyl or hydroxyethyl moiety, X is an anion that provides charge neutrality; Preferred anions include: halides, e.g. chloride; sulfate; and sulfonate. Suitable detersive cationic surfactants are quaternary monoalkyl C6-18-monohydroxyethyldimethylammonium chlorides. Highly suitable detersive cationic surfactants are quaternary monoalkyl C8-10-monohydroxyethyldimethylammonium chloride, monoalkyl C10-12-monohydroxyethyldimethylammonium chloride and quaternary monoalkyl C10-monohydroxyethyldimethylammonium chloride.

[086] Chelating agents: The detergent composition of the present invention may contain a chelating agent. Suitable chelating agents include copper, iron and/or manganese chelating agents, and combinations thereof. When a chelating agent is used, the consumer product in question may comprise from about 0.005% to about 15% or even from about 3.0% to about 10% by weight of chelating agent in the consumer product. consumer in question. Suitable chelators include DTPA (diethylenetriaminepentaacetic acid), HEDP (hydroxyethane diphosphonic acid), DTPMP (diethylenetriaminepenta(methylenephosphonic acid)), hydrated disodium salt of 1,2-dihydroxybenzene-3,5-disulfonic acid, ethylenediamine, diethylenetriamine, ethylenediaminedisuccinic acid (EDDS), N-hydroxyethylethylenediaminetriacetic acid (HEDTA), triethylenetetraminehexaacetic acid (TTHA), N-hydroxyethyliminodiacetic acid (HEIDA), dihydroxyethylglycine (DHEG), ethylenediaminetetrapropionic acid (EDTP) and their derivatives.

[087] Dye transfer inhibiting agents: The detergent composition of the present invention may also include one or more dye transfer inhibiting agents. Suitable dye transfer inhibiting polymeric agents include, but are not limited to, polyvinylpyrrolidone polymers, poly(N-amine oxide) polymers, N-vinylpyrrolidone and N-vinylimidazole copolymers, polyvinyloxazolidones and polyvinylimidazoles, or mixtures thereof. When present in a consumer product in question, dye transfer inhibiting agents may be present at levels of from about 0.0001% to about 10%, from about 0.01% to about 5%, or even from around 0.1% to around 3%, by weight, of the product intended for the consumer.

[088] Brighteners: The detergent composition of the present invention may also contain additional components that can tint articles being cleaned, such as fluorescent brighteners.

[089] The composition may comprise fluorescent brightener CI 260 in alpha-crystalline form having the following structure:

[090] In one aspect, the brightener is a cold water-soluble brightener, such as fluorescent brightener C.I. 260 in alpha-crystalline form.

[091] In one aspect, the rinse aid is predominantly in alpha-crystalline form, which means that typically at least 50% by weight, at least 75% by weight, at least 90%, by weight, at least 99 %, by weight, or even substantially all, C.I. 260 fluorescent brightener is in alpha-crystalline form. The rinse aid is typically in the form of micronized particulates, which have a weighted average main particle size of 3 to 30 micrometers, 3 micrometers to 20 micrometers, or 3 to 10 micrometers.

[092] The composition may comprise C.I. 260 fluorescent brightener in beta-crystalline form, and the ratio between the weight of: (i) C.I. 260 fluorescent brightener in alpha-crystalline form, and (ii) C.I. 260 fluorescent brightener in alpha-crystalline form, and (ii) C.I. 260 fluorescent brightener in beta-crystalline form crystalline form- beta can be at least 0.1, or at least 0.6. BE680847 refers to a process for producing fluorescent brightener C.I. 260 in alpha-crystalline form.

[093] Suitable levels of fluorescent brightener range from lower levels of about 0.01, about 0.05, about 0.1 or even about 0.2% by weight to levels higher than 0.5 or even 0.75% by weight.

[094] Silicate salts - The detergent composition of the present invention may also contain silicate salts, such as sodium or potassium silicate. The composition may comprise from 0% by weight, to less than 10% by weight, silicate salt, to 9% by weight, or to 8% by weight, or to 7% by weight, or 6% by weight, or 5% by weight, or 4% by weight, or 3% by weight, or even 2% by weight, and preferably above 0%, by weight, or 0.5% by weight, or even 1% by weight of silicate salt. A suitable silicate salt is sodium silicate.

[095] Dispersants - The detergent composition of the present invention may also contain dispersants. Suitable water-soluble organic materials include homopolymeric or copolymeric acids, or salts thereof, wherein the polycarboxylic acid comprises at least two carboxyl radicals separated from each other by no more than two carbon atoms.

[096] Enzyme stabilizers - Enzymes for use in detergent composition can be stabilized by various techniques. The enzymes used in the present invention can be stabilized by the presence of water-soluble sources of calcium and/or magnesium ions in the final fabric and home care products that provide such ions to the enzymes. In the case of detergent compositions comprising protease, a reversible protease inhibitor, such as a boron compound, or compounds such as calcium formate, sodium formate and 1,2-propanediol can be added to further improve stability.

[097] Solvents - Suitable solvents include water and other solvents, such as lipophilic fluids. Examples of suitable lipophilic fluids include siloxanes, other silicones, hydrocarbons, glycol ethers, glycerin derivatives such as glycerin ethers, perfluorinated amines, perfluorinated and hydrofluoroether-based solvents, low-volatility non-fluorinated organic solvents, diol-based solvents, others. environmentally beneficial solvents and mixtures thereof.

[098] Processes for preparing the detergent composition

[099] The detergent composition of the present invention is preferably in granular form, optionally the granules being incorporated into a unit dose detergent composition as described above.

[100]Usage method

[101] The present invention includes a method of treating and/or cleaning a surface, preferably a fabric surface comprising the steps of (i) contacting said surface with a composition as defined in any one of claims 1 to 11 in a aqueous washing liquid, (ii) rinsing and/or drying the surface, preferably the temperature of the aqueous liquid is 5 to 25°C and preferably the aqueous liquid comprises from 0.1 g/l to 3 g/l of surfactant .

[102]Cogranule Example 1

[103] Enzyme cogranules are prepared according to the process described in example 1 of US2008/0206830A1, however each of the granules comprises the enzymes as described and in the weight ratios in the formulation examples below. Thus the enzyme granules comprise an enzyme core, sucrose/starch and magnesium sulfate heptahydrate (relative weight ratio approximately 6:68:27), and a coating comprising poly(vinyl alcohol), titanium dioxide and non-ionic surfactant (relative weight ratio approximately 40:50:10). The enzyme concentration in the granules is approximately 40 g/kg.

[104]Formulation examples 1 to 7

[105]Granular detergent compositions intended for washing clothes by hand or for top-loading automatic washing machines.

[106]Examples 8 to 13

[107]Granular detergent compositions for washing clothes, designed for front-loading automatic washing machines.

[108] Any of the above compositions is used to wash fabrics at a concentration of 7000 to 10000 ppm in water, at 20 to 90 ° C, and at a water:cloth weight ratio of 5:1. The typical pH is around 10. The fabrics are then subjected to drying. In one aspect, the fabrics are actively subjected to drying using a dryer. In one aspect, the fabrics are actively subjected to drying using an iron. In another aspect, it is possible to simply let the fabrics dry on a clothesline, exposed to air and optionally sunlight.

[109] Raw materials and notes for comparison examples 1 to 20 Alkylbenzenesulfonate, average linear aliphatic carbon chain length C11-C12. AE3S is C12-15 alkyl ethoxy(3)sulfate. AE7 is C12-15 alcohol ethoxylate, with an average degree of ethoxylation of 7. AE9 is C12-13 alcohol ethoxylate with an average degree of ethoxylation of 9. HSAS is a branched medium-chain primary alkylsulfate with carbon chain length of about 16 to 17 Chelators may be diethylenetetraaminepentaacetic acid (DTPA), sodium hydroxyethanediphosphonate (HEDP) or isomer (S,S) of ethylenediamine-N,N-disuccinic acid sodium salt (EDDS) Savinase®, Natalase®, Stainzyme®, Lipex®, Celluclean™, Mannaway® and Whitezyme® are all products of Novozymes, Bagsvaerd, Denmark. Fluorescent Brightener 1 is Tinopal® AMS, Fluorescent Brightener 2 is Tinopal® CBS-X, Sulfonated zinc phthalocyanine NOBS is sodium nonanoyloxybenzenesulfonate. TAED is tetraacetylethylenediamine. Soil release agent is Repel-o-tex® PF, available from Rhodia, Paris, France Acrylic acid/maleic acid copolymer has a molecular weight of 70,000 and an acrylate:maleate ratio of 70:30. HSAS is a medium branched alkyl sulfate as disclosed in US 6,020,303 and US 6,060,443 Liquitint® Violet CT is supplied by Milliken, Spartanburg, South Carolina, USA Random graft copolymer is a copolymer of polyethylene oxide ) grafted with poly(vinyl acetate) having a poly(ethylene oxide) backbone and multiple poly(vinyl acetate) side chains (molecular weight about 6000, weight ratio of poly(ethylene oxide) and poly(vinyl acetate) is about 40 to 60).

[110] The dimensions and values presented in the present invention should not be understood as being strictly limited to the exact numerical values mentioned. Instead, except where otherwise specified, each such dimension is intended to mean both the referenced value and a range of functionally equivalent values around that value. For example, a dimension shown as "40 mm" is intended to mean "about 40 mm".

Claims (6)

1. Detergent composition, characterized by the fact that it comprises: (a) a multiple enzyme co-granule comprising from 10 to 98% by weight of moisture dissipating component; (b) less than 3% by weight zeolite (anhydrous basis); (c) less than 3% by weight of phosphate salt (anhydrous basis); (d) from 5% by weight to 35% by weight sodium percarbonate; (e) a fabric tinting agent selected from solvent, dyes, acid dye, direct dye, pigment or mixtures thereof; (f) a protease enzyme; (g) a lipase enzyme; (h) and the composition further comprises from 40 to 75% by weight of detergent moisture-dissipating component; wherein the multi-enzyme co-granules have a core-shell structure wherein the core comprises an enzyme-free central part and a surrounding layer comprising the enzymes, wherein the shell comprises a plurality of layers, wherein the central part of the core and at least one of the shell layers comprise a moisture dissipative component, the outermost layer is titanium oxide and polyvinyl alcohol and is 1% to 3% by weight of the total particle, wherein the central part of the core is from 5% to 40% by weight of the total particle and the layer comprising the moisture dissipating component is from 3% to 20% by weight of the particle; wherein the detergent moisture-dissipating component is sodium sulfate, wherein the co-granule has a geometric average particle size by weight ranging from 600 microns to 1000 microns. 2. Detergent composition according to claim 1, characterized in that the multi-enzyme co-granule comprises (a) one or more enzymes selected from the group consisting of first-wash lipases, cleaning cellulases, xyloglucanases, perhydrolases, peroxidases, lipoxygenases, laccases and mixtures thereof; and (b) one or more enzymes selected from the group consisting of hemicellulases, treatment cellulases, cellobiose dehydrogenases, xylanases, phospholipases, esterases, cutinases, pectinases, mannanases, pectatolyases, keratinases, reductases, oxidases, phenoloxidases, ligninases, pullulanases , tannases, pentosanases, lichenases, glycanases, arabinosidases, hyaluronidase, chondroitinase, amylases, and mixtures thereof. 3. Detergent composition according to claim 1, characterized by the fact that the moisture dissipating component and the total active enzyme are present in the multi-enzyme co-granule in a weight ratio of 10:1 to 100:1. 4. Detergent composition according to claim 1, characterized in that it additionally comprises a dye transfer inhibiting agent. 5. Detergent composition according to claim 1, characterized by the fact that it comprises one or more of the following auxiliary compounds: (a) an encapsulate comprising a perfume; (b) a surfactant system comprising an anionic surfactant and a nonionic surfactant; (c) a silicate salt selected from the group consisting of sodium silicate, potassium silicate and mixtures thereof; (d) a carboxylate polymer selected from the group consisting of maleate/acrylate random copolymer or polyacrylate homopolymer and mixtures thereof; (e) a soil release polymer selected from the group consisting of terephthalate copolymers and mixtures thereof; (f) a cellulosic polymer selected from the group consisting of alkylcellulose, alkylalkoxyalkylcellulose, carboxyalkylcellulose, alkylcarboxyalkylcellulose and mixtures thereof; (g) a chelator selected from the group consisting of DTPA (Diethylenetriaminepentaacetic acid), HEDP (Hydroxyethanediphosphonic acid), DTPMP (Diethylenetriaminepenta(methylenephosphonic acid)), ethylenediaminedisuccinic acid (EDDS), 1,2-dihydrate disodium salt hydroxybenzene-3,5-disulfonic acid, derived from said chelators; and (h) mixtures thereof. 6. Composition according to claim 1, characterized in that it additionally comprises one or more bleaching particles selected from the group consisting of: (a) a bleaching catalyst comprising a material selected from the group consisting of iminium cations, iminium polyions, iminium; iminium zwitterions; modified amines; modified amine oxides; N-sulfonylimines; N-phosphonylimines; N-acylimines; thiadiazole dioxides; perfluoroimines; cyclic sugar ketones and transition metal-based catalysts and ligands for the formation thereof, or mixtures thereof; (b) a bleach activator comprising a material selected from the group consisting of dodecanoyloxybenzenesulfonate, decanoyloxybenzenesulfonate, decanoyloxybenzoic acid or salts thereof, 3,5,5-trimethylhexanoyloxybenzenesulfonate, tetraacetylethylenediamine (TAED), nonanoyloxybenzenesulfonate (NOBS) and mixtures thereof; (c) a metal catalyst; (d) a photobleach selected from group 15 consisting of aluminum phthalocyanine compounds, zinc phthalocyanine compounds, and mixtures thereof.