Colored particles with improved colorant stability

Abstract

The present invention provides colored particles having improved color stability. The colored particles comprise: (a) a colored core comprising a colorant, and (b) a salt coating covering the core, the salt coating constituting 1%-50% w / w of the particle and comprising at least 60% w / w of a salt (sodium sulfate) having a constant relative humidity of at least 60% at 20 DEG C, and the salt coating forming a continuous layer with little or no voids. A solid detergent composition is provided comprising a surfactant, a builder and the colored particles, preferably further comprising a bleaching system component.

Description

Technical Field

[0001] The present invention relates to colored particles that exhibit improved colorant stability. Background Art

[0002] In aqueous applications, small particles are commonly used as delivery carriers for target compounds or simply as small colored particles. Such particles can be whitened or colored to mask a dull gray appearance and thus increase attractiveness to customers.

[0003] The colorants used to provide such particles with a colored appearance must be stable enough to withstand fading in many different environments in which these particles are stored before being used in applications. The present invention describes how to protect such colorants while maintaining the colored appearance. Summary of the Invention

[0004] In a first aspect, the present invention provides a colored particle comprising

[0005] (a) a colored core containing a colorant, and

[0006] (b) a salt coating that coats the core, the salt coating constituting 1% - 50% w / w of the particle and containing at least 60% w / w of a salt having a constant relative humidity of at least 60% at 20°C.

[0007] In an embodiment, the colored particle contains a target compound.

[0008] In another aspect, the present invention provides a solid detergent composition comprising a surfactant and a builder, and one or more colored particles of the present invention.

[0009] Other aspects and embodiments of the present invention are apparent from the specification and examples.

[0010] Unless otherwise specified or otherwise apparent from the context, all percentages are percentages by weight (% w / w).

[0011] As used herein, the term "consisting essentially of" (and its grammatical variants) when applied to the compositions and methods of the present invention means that these compositions / methods can contain additional components, provided that these additional components do not substantially alter the composition / method.

[0012] As used herein, the term "substantially free of" (and its grammatical variants) when applied to the compositions and methods of the present invention means that these compositions / methods can contain a small amount of a particular component, provided that the amount of the component does not substantially alter the composition / method or provide any substantial effect on the composition / method. In an embodiment, "substantially free of" means 0% w / w. Detailed implementation mode

[0013] We have found that simple salt coating can prevent the degradation / fading of colorants in colored particles without significantly reducing the color intensity. This has not been recognized before. Traditionally, particles are colored by applying a colorant coating layer on the outer side of the salt coating. However, contrary to expectations, we found that the salt coating is highly transparent and does not significantly weaken the color of the colorant coating. This has a strong advantage, namely, protecting the colorant from fading due to chemical oxidative degradation and oxidative photodegradation. This is particularly important when using unstable plant-derived colors as natural and sustainable coloring options.

[0014] Colored particles

[0015] The colored particles of the present invention are small particles comprising a colored core containing a colorant and a salt coating covering the core, the salt coating constituting 1%-50% w / w of the total particles and containing at least 60% w / w of a salt having a constant relative humidity of at least 60% at 20°C. Preferably, the colored particles are water-soluble / dispersible.

[0016] The particles can contain a target compound and are used as a delivery carrier when used in applications for releasing the target compound into an aqueous environment. Thus, the particles can be used to temporarily protect such compounds, but they can also be used simply as a convenient way to dispense the target compound, which would otherwise be a dusty powder.

[0017] The particles can contain the target compound in an amount of 0.05%-50% w / w, such as 0.1%-30% w / w, 0.5%-25% w / w, or 1%-20% w / w.

[0018] In the examples, the particles contain less than 10% w / w of a surfactant; preferably less than 5% w / w, or less than 2% w / w of a surfactant.

[0019] The target compound can be a functional or reactive component, for example, a protein such as an enzyme (as described below), or a bleaching catalyst (such as a manganese bleaching catalyst like MnTACN) and / or a bleaching activator (such as TAED, NOBS), or other compounds that need to be isolated from the surrounding environment during storage (such as percarbonate).

[0020] Typically, the particle size of the particles (measured as the equivalent spherical diameter (volume-based average particle size)) is 20-2000 μm, especially 50-1500 μm, 100-1500 μm or 250-1200 μm. Preferably, the particles are (substantially) spherical.

[0021] The color of the colored particles can be described by Hunter L, a, b coordinates. The sum of the numerical values "a" and "b" in the Hunter L, a, b color space (|a| + |b|) can be at least 20; preferably at least 30, at least 40, or at least 50. Alternatively, the square root of the sum of the squares of the "a" and "b" values can be at least 20; preferably at least 30, at least 40, or at least 50.

[0022] Core

[0023] The colored core contains a colorant as described below and may contain additional materials such as fillers, fibrous materials (cellulose or synthetic fibers), stabilizers, solubilizers, suspending agents, viscosity modifiers, light spheres, plasticizers, salts, lubricants, fragrances, and binders such as synthetic polymers, waxes, fats or carbohydrates. The components of the core can be mixed into a homogeneous blend.

[0024] The core can consist of inert particles or inert particles having a target compound applied (coated) to the surface of the inert particles, for example, by granulation via a seed mixer or layering granulation in a fluidized bed. Such inert particles can be organic particulate compounds, such as natural compounds, like aggregated carbohydrates (e.g., sugars, starches, dextrins, flours (e.g., vegetable flours) or nonpareils). Nonpareils are spherical particles made from seeds, which are built up on the sphere and rounded into a sphere. Nonpareils are typically made from a combination of sugar (such as sucrose) and powder (such as corn starch). The inert particles can also be sodium chloride or sodium sulfate crystals (or aggregated crystals), also known as seeds, or other inorganic salt crystals; or sucrose crystals.

[0025] The core can also be prepared by granulating a blend of the components (with or without the target compound), for example, by methods including granulation techniques such as crystallization, precipitation, pan - coating, fluidized bed coating, fluidized bed aggregation, rotary atomization, extrusion, prilling, spheronization, particle size reduction methods, drum granulation, and / or high - shear granulation.

[0026] The colorant can be mixed with other components of the core as long as the resulting core is colored. The colorant can be applied as a coating to the unfinished core, preferably such that the colorant is deposited at the surface of the core.

[0027] The core may further comprise a coating below the colorant layer, which isolates the colorant from any reactive compounds in the core, such as the target compound if possible. Such a coating may be a salt coating, and then the salt coating will be part of the core.

[0028] The method for preparing the core can be found in Handbook of Powder Technology; Particle size enlargement by C.E. Capes; Volume 1; 1980; Elsevier.

[0029] Salt coating

[0030] The colored core is coated with a salt coating (outer layer). The salt coating contains at least 60% w / w of salt, such as at least 65%, at least 70%, at least 75%, at least 80%, at least 85%, at least 90%, at least 95% or at least 99% w / w of salt.

[0031] The salt coating can be applied in an amount of at least 1% w / w of the particles, such as at least 5%, 10% or 15% w / w. This amount can be up to 70%, 50%, 40% or 30% w / w.

[0032] The coating is preferably at least 0.1 μm thick, especially at least 0.5 μm, at least 1 μm or at least 5 μm thick. In a particular embodiment, the thickness of the coating is less than 100 μm. In a more particular embodiment, the thickness of the coating is less than 60 μm. In an even more particular embodiment, the total thickness of the coating is less than 40 μm.

[0033] The coating should coat / enclose the core by forming a substantially continuous layer. A substantially continuous layer should be understood as a coating having very few or no holes (substantially impermeable or poreless), such that the core unit is coated / enclosed with very few or no uncoated areas. The layer or coating should especially be uniform in thickness.

[0034] The salt can be added from a salt solution in which the salt is completely dissolved, or from a salt suspension in which the fine particles are less than 50 μm, such as less than 10 μm or less than 5 μm.

[0035] The salt coating can contain a single salt or a mixture of two or more salts. The salt can be water-soluble, especially having a solubility of at least 0.1 grams in 100 g of water at 20 °C, preferably at least 0.5 g / 100 g of water, such as at least 1 g / 100 g of water, such as at least 5 g / 100 g of water.

[0036] The salt can be an inorganic salt, such as a sulfate, sulfite, phosphate, phosphonate, nitrate, chloride or carbonate, or a salt of a simple organic acid (less than 10 carbon atoms, such as 6 or fewer carbon atoms) like citrate, malonate or acetate. Examples of cations in these salts are alkali or alkaline earth metal ions, ammonium ions or metal ions of the first transition series, such as sodium, potassium, magnesium, calcium, zinc or aluminum. Examples of anions include chloride, bromide, iodide, sulfate, sulfite, bisulfite, thiosulfate, phosphate, dihydrogen phosphate, dibasic phosphate, hypophosphite, pyrophosphate dihydrogen, tetraborate, borate, carbonate, bicarbonate, silicate, citrate, malate, maleate, malonate, succinate, lactate, formate, acetate, butyrate, propionate, benzoate, tartrate, ascorbate or gluconate. In particular, alkali or alkaline earth metal salts of sulfate, sulfite, phosphate, phosphonate, nitrate, chloride or carbonate, or salts of simple organic acids such as citrate, malonate or acetate can be used.

[0037] The salt in the coating can have a constant relative humidity (also known as "humidity fixing point") above 60%, particularly above 70%, above 80% or above 85% at 20 °C, or it can be another hydrate form of such a salt (e.g., anhydrous). The salt coating can be as described in WO 00 / 01793 or WO 2006 / 034710.

[0038] Specific examples of suitable salts are NaCl (CH 20 °C = 76%), Na2CO3 (CH 20 °C = 92%), NaNO3 (CH 20 °C = 73%), Na2HPO4 (CH 20 °C = 95%), Na3PO4 (CH 25 °C = 92%), NH4Cl (CH 20 °C = 79.5%), (NH4)2HPO4 (CH 20 °C = 93.0%), NH4H2PO4 (CH 20 °C = 93.1%), (NH4)2SO4 (CH 20 °C = 81.1%), KCl (CH 20 °C = 85%), K2HPO4 (CH 20 °C = 92%), KH2PO4 (CH 20 °C = 96.5%), KNO3 (CH 20 °C = 93.5%), Na2SO4 (CH 20 °C = 93%), K2SO4 (CH 20 °C = 98%), KHSO4 (CH20 ℃ = 86%), MgSO4(CH 20 ℃ = 90%), ZnSO4(CH 20 ℃ = 90%) and sodium citrate (CH 25 ℃ = 86%). Other examples include NaH2PO4, (NH4)H2PO4, CuSO4, Mg(NO3)2 and magnesium acetate.

[0039] The salt can be in anhydrous form, or it can be a hydrated salt, i.e., a crystalline hydrate salt having one or more bound waters of crystallization, as described, for example, in WO 99 / 32595. Specific examples include anhydrous sodium sulfate (Na2SO4), anhydrous magnesium sulfate (MgSO4), magnesium sulfate heptahydrate (MgSO4 . 7H2O), zinc sulfate heptahydrate (ZnSO4 . 7H2O), disodium hydrogen phosphate heptahydrate (Na2HPO4 . 7H2O), magnesium nitrate hexahydrate (Mg(NO3)2(6H2O)), sodium citrate dihydrate and magnesium acetate tetrahydrate.

[0040] Preferably, the salt is used as a salt solution, for example, using a fluidized bed.

[0041] The salt coating can be supplemented with one or more additional coatings (coating the salt coating), and the additional coating contains, for example, polyethylene glycol (PEG), methyl hydroxypropyl cellulose (MHPC) or polyvinyl alcohol (PVA). One or more such additional coatings can be added to reduce dust generation. In the examples, any one or more coatings coating the salt coating shall not significantly reduce the transparency of the combined coating coating the colored core.

[0042] Colorant

[0043] Colorants for coloring the cores and particles of the present invention include dyes and pigments, which are natural or synthetic substances. Colorants can be naturally occurring colorants, such as colorants of plant origin.

[0044] Generally, dyes are soluble in water (or organic solvents), while pigments are insoluble and are usually in the form of very fine particles. In the context of the present invention, various shades of white, gray and black are not considered colors. Additionally, colorants in the context of the present invention are coloring compounds within the common understanding of colors. In the examples, colorants can be described by their Hunter L,a,b coordinates. The sum of the numerical values "a" and "b" in the Hunter L,a,b color space (|a| + |b|) can be at least 20; preferably at least 30, at least 40, or at least 50. Alternatively, the square root of the sum of the squares of the "a" and "b" values It can be at least 20; preferably at least 30, at least 40, or at least 50.

[0045] In the examples, the colorants used to color the cores and particles of the present invention are listed by their common names and C.I. numbers in the Colour Index TM [Color Index TM (published by the Society of Dyers and Colourists and the American Association of Textile Chemists and Colorists). According to the present invention, the Color Index TM is preferably the version in force as of November 22, 2022.

[0046] The Colour Index Generic Name describes commercial products by their recognized usage class, their hue, and their serial number.

[0047] The colorants can belong to usage classes selected from the group consisting of: acid dyes, basic dyes, direct dyes, food colors, mordant dyes, natural dyes, reactive dyes, solvent dyes, vat dyes, sulfur dyes, disperse dyes, and pigments. Preferred usage classes are acid dyes, basic dyes, direct dyes, food colors, mordant dyes, natural dyes, reactive dyes, and pigments; and in particular, the usage classes are acid dyes, basic dyes, food colors, and natural dyes. The usage class generally refers to a group of colorants having similar chemical structures, and this itself is not limited to the properties of the Color Index TM attributes.

[0048] Preferred hues (colors) are selected from the group consisting of: yellow, orange, red, green, blue, and violet. The hue attribute is not limited to the Color Index TM , as it reflects a common understanding of color hues. Thus, the colorants used in the present invention can have hues that are various nuances of yellow, orange, red, green, blue, or violet.

[0049] Target compound

[0050] The above-mentioned target compound can be a protein, and in particular a protein produced by fermentation. Proteins can cause allergic reactions in humans, and it is generally desirable to encapsulate such compounds in particles to avoid the release of protein dust.

[0051] Proteins are small biomolecules (peptides; <50 amino acids) and large biomolecules (polypeptides; >50 amino acids) that perform a large number of functions in living organisms, including catalyzing reactions, DNA replication, responding to stimuli, providing structure for cells and organisms, and transporting molecules from one location to another. Proteins are composed of polymeric amino acid chains that fold into a very specific three-dimensional structure. This three-dimensional structure is very important for maintaining the function of the protein. Some chemicals can alter the folding or even unfold (denature) the three-dimensional structure, which will result in loss of function, such as loss of enzyme activity.

[0052] In embodiments, these proteins are polypeptides.

[0053] Proteins are divided into at least three different groups, namely enzymes, cell signaling and ligand-binding proteins, and structural proteins.

[0054] Enzymes are described below. For example, cell signaling and ligand-binding proteins include many pharmaceutical proteins, such as receptors, membrane proteins, ion channels, antibodies (e.g., single-domain antibodies), and hormones; while structural proteins provide hardness and stiffness to biological components that are otherwise fluid.

[0055] Preferably, these proteins are enzymes or cell signaling and ligand-binding proteins; more preferably, the proteins are enzymes.

[0056] The target compound can also be other biomolecules or microorganisms. Preferred microorganisms are dehydrated or spore microorganisms, such as Bacillus endospores.

[0057] Enzymes

[0058] The enzymes used as target compounds are catalytic proteins, and the term "active enzyme protein" is defined herein as the amount of one or more catalytic proteins that exhibit enzyme activity. This can be determined using activity-based enzyme assays. In such assays, the enzyme typically catalyzes a reaction that generates a colored compound. The amount of the colored compound can be measured and correlated with the concentration of the active enzyme protein. This technique is well known in the art.

[0059] The one or more enzymes can be selected from the group consisting of: proteases, lipases, cutinases, amylases, carbohydrases, cellulases, pectinases, mannanases, arabinases, galactanases, xylanases, nucleases (DNases, RNases), dispersin, catalase, perhydrolase, and oxidases (such as laccase and / or peroxidase). Preferably, the one or more enzymes are detergent enzymes selected from the group consisting of: proteases, lipases, amylases, cellulases, pectinases, mannanases, xylanases, nucleases (DNases, RNases), dispersin, catalase, perhydrolase, and combinations thereof.

[0060] The protease can be a serine protease, such as subtilisin. The amylase can be an α - amylase or glucoamylase. The cellulase can be an endo - 1,4 - β - glucanase, also known as endoglucanase.

[0061] The enzyme can be an enzyme from a naturally occurring bacterial or fungal source, or it can be a variant derived from one or more naturally occurring enzymes by gene shuffling and / or by substituting, deleting or inserting one or more amino acids. This includes chemically modified mutants or protein - engineered mutants.

[0062] The colored granules of the present invention can contain at least one enzyme in an amount of 0.1% - 25% w / w active enzyme protein; preferably in an amount of 0.5% - 25% w / w active enzyme protein; and more preferably in an amount of 0.5% - 20% w / w active enzyme protein.

[0063] Solid detergent composition

[0064] The present invention also provides a solid detergent composition comprising a combination of the colored granules of the present invention with one or more additional cleaning composition (detergent) components, as described below. The selection of the additional components is within the ability of a person skilled in the art and includes conventional ingredients, including the exemplary non - limiting components set forth below. Such detergent compositions can be substantially free of titanium dioxide.

[0065] The detergent composition can contain the colored granules of the present invention in an amount up to 10% w / w, preferably up to 5% w / w.

[0066] The selection of the additional detergent components can include (for textile care) the type of textile to be cleaned, the type and / or degree of dirt, the temperature at which cleaning is carried out, and considerations of the formulation of the detergent product. Although the components mentioned below are classified under general headings according to specific functionality, this is not to be construed as limiting, as will be understood by a person skilled in the art, since a component can include additional functionality.

[0067] In one embodiment, the present invention relates to an ADW (automatic dishwashing) composition, which comprises one or more additional ADW composition components. The selection of the additional components is within the ability of a person skilled in the art and includes conventional ingredients, including the exemplary non - limiting components set forth below.

[0068] The solid detergent composition may consist essentially of biodegradable materials (substantially bio-based). In a preferred embodiment, the solid detergent composition is >95% bio-based according to USDA-certified bio-based products (measuring bio-based content using ASTM D6866); more preferably >97% bio-based, and most preferably >99% bio-based.

[0069] Surfactant

[0070] The cleaning composition can comprise one or more surfactants, which can be anionic and / or cationic and / or nonionic and / or semi-polar and / or zwitterionic, or mixtures thereof. In certain embodiments, the detergent composition comprises a surfactant system (comprising more than one surfactant), such as a mixture of one or more nonionic surfactants and one or more anionic surfactants. In one embodiment, the detergent comprises at least one anionic surfactant and at least one nonionic surfactant, and the weight ratio of the anionic surfactant to the nonionic surfactant can be from 10:1 to 1:10. In one embodiment, the amount of the anionic surfactant is higher than that of the nonionic surfactant, for example, the weight ratio of the anionic surfactant to the nonionic surfactant can be from 10:1 to 1.1:1 or from 5:1 to 1.5:1. The amounts of the anionic surfactant and the nonionic surfactant can also be equal and the weight ratio is 1:1. In one embodiment, the amount of the nonionic surfactant is higher than that of the anionic surfactant, and the weight ratio can be from 1:10 to 1:1.1. Preferably, the weight ratio of the anionic surfactant to the nonionic surfactant is from 10:1 to 1:10, such as from 5:1 to 1:5, or from 5:1 to 1:1.2. Preferably, the weight fraction of the nonionic surfactant to the anionic surfactant is from 0 to 0.5 or from 0 to 0.2. Thus, if the weight fraction is 0, the nonionic surfactant can be present or absent, but if the nonionic surfactant is present, the weight fraction of the nonionic surfactant is preferably at most 50% or at most 20% of the total weight of the anionic surfactant and the nonionic surfactant. Light-duty detergents typically contain more nonionic surfactants than anionic surfactants, and the fraction of the nonionic surfactant to the anionic surfactant is preferably from 0.5 to 0.9. The total weight of the one or more surfactants typically is present at a level of about 0.1% to about 60% by weight, such as about 1% to about 40%, or about 3% to about 20%, or about 3% to about 10%. The one or more surfactants are selected based on the desired cleaning application, and the one or more surfactants can include any one or more conventional surfactants known in the art. When included therein, the detergent will typically contain about 1% to about 40% by weight of an anionic surfactant, such as about 5% to about 30%, including about 5% to about 15%, or about 15% to about 20%, or about 20% to about 25% of an anionic surfactant.Non-limiting examples of anionic surfactants include sulfates and sulfonates, typically available as sodium or potassium salts, or monoethanolamine (MEA, 2-aminoethanol-1-ol) salts or triethanolamine (TEA, 2,2',2”-nitrilotriethanol-1-ol) salts; in particular linear alkylbenzene sulfonates (LAS), isomers of LAS such as branched alkylbenzene sulfonates (BABS) and phenylalkane sulfonates; olefin sulfonates, in particular α-olefin sulfonates (AOS); alkyl sulfates (AS), in particular fatty alcohol sulfates (FAS), i.e., primary alcohol sulfates (PAS), such as dodecyl sulfate; alcohol ether sulfates (AES or AEOS or FES, also known as alcohol ethoxysulfates or fatty alcohol ether sulfates); paraffin sulfonates (PS), including alkane-1-sulfonates and secondary alkane sulfonates (SAS); ester sulfonates, including sulfonated fatty acid glycerides and α-sulfo fatty acid methyl esters (α-SFMe or SES or MES); alkyl succinic acids or alkenyl succinic acids, such as dodecenyl / tetradecenyl succinic acid (DTSA); diesters and monoesters of sulfosuccinic acid; fatty acid derivatives of amino acids. In addition, fatty acid salts (soaps) may be included.

[0071] When included therein, the detergent will typically contain from about 1% to about 40% by weight of a cationic surfactant, such as from about 0.5% to about 30%, in particular from about 1% to about 20%, from about 3% to about 10%, such as from about 3% to about 5%, from about 8% to about 12% or from about 10% to about 12%. Non-limiting examples of cationic surfactants include alkyldimethyl ethanol quaternary ammonium (ADMEAQ), cetyltrimethylammonium bromide (CTAB), dimethyldistearylammonium chloride (DSDMAC), and alkylbenzyl dimethylammonium, alkyl quaternary ammonium compounds, alkoxylated quaternary ammonium (AQA) compounds, ester quaternaries and combinations thereof.

[0072] When included therein, the detergent will typically contain from about 0.2% to about 40% by weight of a nonionic surfactant, such as from about 0.5% to about 30%, particularly from about 1% to about 20%, from about 3% to about 10%, such as from about 3% to about 5%, from about 8% to about 12% or from about 10% to about 12%. Non-limiting examples of nonionic surfactants include alcohol ethoxylates (AE or AEO) (such as the AEO series like AEO-7), alcohol propoxylates (particularly propoxylated fatty alcohols (PFA), ethoxylated alcohols and propoxylated alcohols), alkoxylated fatty acid alkyl esters (such as ethoxylated and / or propoxylated fatty acid alkyl esters (particularly methyl ethoxylate, MEE)), alkyl polyglycosides (APG), alkoxylated amines, fatty acid monoethanolamides (FAM), fatty acid diethanolamides (FADA), ethoxylated fatty acid monoethanolamides (EFAM), propoxylated fatty acid monoethanolamides (PFAM), polyhydroxyalkyl fatty acid amides, or N-acyl N-alkyl derivatives of glucosamine (glucamides (GA), or fatty acid glucamides (FAGA)), as well as products available under the trade names SPAN and TWEEN, and combinations thereof.

[0073] When included therein, the detergent will typically contain from about 0.01% to about 10% by weight of a semi-polar surfactant. Non-limiting examples of semi-polar surfactants include amine oxides (AO), such as alkyl dimethyl amine oxides, particularly N-(cocoyl alkyl)-N,N-dimethyl amine oxide and N-(tallow alkyl)-N,N-bis(2-hydroxyethyl) amine oxide and combinations thereof.

[0074] When included therein, the detergent will typically contain from about 0.01% to about 10% by weight of an amphoteric surfactant. Non-limiting examples of amphoteric surfactants include betaines, such as alkyl dimethyl betaines, sulfobetaines, and combinations thereof.

[0075] Additional bio-based surfactants can be used, such as nonionic surfactants where the surfactant is sugar-based, which can be hexyl-β-D-maltopyranoside, thiomaltopyranoside or cyclic maltopyranoside, as described, for example, in EP 2516606 B1.

[0076] Builders and cobuilders

[0077] The detergent composition may contain from about 0% to 65% by weight (such as from about 5% to about 50%) of a detergent builder or co-builder, or a mixture thereof. In dishwashing detergents, the level of the builder is typically in the range of 40% - 65%, especially in the range of 50% - 65%. The builder and / or co-builder may in particular be a chelating agent that forms water-soluble complexes with Ca and Mg. Any builder and / or co-builder known in the art for use in cleaning detergents may be utilized.

[0078] Non-limiting examples of builders include zeolites, diphosphates (pyrophosphates), triphosphates such as sodium tripolyphosphate (STP or STPP), carbonates such as sodium carbonate, soluble silicates such as sodium metasilicate, layered silicates (e.g., SKS-6 from Clariant), ethanolamines such as 2-aminoethan-1-ol (MEA), diethanolamine (DEA, also known as 2,2'-iminodiethan-1-ol), triethanolamine (TEA, also known as 2,2',2”-nitrilotriethan-1-ol), and (carboxymethyl) inulin (CMI), and combinations thereof. Preferably, the one or more builders are phosphate-free.

[0079] The detergent composition may further contain from about 0% to 50% by weight, such as from about 5% to about 30% by weight, of a detergent co-builder. The detergent composition may comprise a co-builder alone or in combination with a builder (such as a zeolite builder). Non-limiting examples of co-builders include homopolymers or copolymers of polyacrylates, such as poly(acrylic acid) (PAA) or copoly(acrylic acid / maleic acid) (PAA / PMA). Further non-limiting examples include citrates, chelating agents (such as aminocarboxylates, aminopolycarboxylates and phosphonates), and alkyl succinic acids or alkenyl succinic acids. Further specific examples include nitrilotriacetic acid (NTA), ethylenediaminetetraacetic acid (EDTA), diethylenetriaminepentaacetic acid (DTPA), iminodisuccinic acid (IDS), ethylenediamine-N,N'-disuccinic acid (EDDS), methylglycinediacetic acid (MGDA), glutamic acid-N,N-diacetic acid (GLDA), 1-hydroxyethane-1,1-diylbis(phosphonic acid) (HEDP), ethylenediaminetetramethylenetetra(phosphonic acid) (EDTMPA), diethylenetriaminepentamethylenepenta(phosphonic acid) (DTMPA or DTPMPA), N-(2-hydroxyethyl)iminodiacetic acid (EDG), aspartic acid-N-monoacetic acid (ASMA), aspartic acid-N,N-diacetic acid (ASDA), aspartic acid-N-monopropionic acid (ASMP), iminodisuccinic acid (IDA), N-(2-sulfoethyl)aspartic acid (SEAS), N-(2-sulfoethyl)glutamic acid (SEGL), N-methyliminodiacetic acid (MIDA), serine-N,N-diacetic acid (SEDA), isoserine-N,N-diacetic acid (ISDA), phenylalanine-N,N-diacetic acid (PHDA), anthranilic acid-N,N-diacetic acid (ANDA), sulfamic acid-N,N-diacetic acid (SLDA), taurine-N,N-diacetic acid (TUDA) and sulfomethyl-N,N-diacetic acid (SMDA), N-(2-hydroxyethyl)ethylenediamine-N,N',N”-triacetic acid (HEDTA), diethanolglycine (DEG), aminotrimethylenetri(phosphonic acid) (ATMP), and combinations and salts thereof. Further exemplary builders and / or co-builders are described, for example, in WO 09 / 102854, US 5977053.

[0080] The solid detergent composition of the present invention may comprise a strong chelating builder; such as at least 0.1% w / w, at least 0.5% w / w or at least 1% w / w of a strong chelating builder. Examples of strong chelating builders are EDTA, EDTMP, NTMP, DTPMP, MGDA, NTA, HEDP, STPP, IDS and GLDA.

[0081] Chelating builders differ from precipitating builders in that when initially used in an amount sufficient to complex all of the calcium ions in an aqueous solution having a 7°dH water hardness (German hardness) at neutral pH, no significant amount of precipitate is formed. Strong builders are classified as high-efficiency chelating agents that are capable of strongly complexing divalent cations (such as Ca Ca ) with a cation / chelator complex logarithmic stability constant (Log K 2+ ) of greater than 5, particularly greater than 6 or greater than 7. The stability constant is determined at an ionic strength of 0.1 M and a temperature of 25 °C.

[0082] Bleaching system

[0083] The cleaning composition can contain from 0% to 50% by weight (such as from 1% to 40%, such as from 1% to 30%, such as from about 1% to about 20%) of a bleaching system. Any oxygen-based bleaching system comprising components known in the art for use in cleaning detergents can be utilized. Suitable bleaching system components include a source of hydrogen peroxide; peracids and peracid sources (bleaching activators); and bleaching catalysts or boosters.

[0084] Suitable sources of hydrogen peroxide are inorganic peracids, including alkali metal salts such as sodium percarbonate and sodium perborate (usually the monohydrate or the tetrahydrate), as well as hydrogen peroxide-urea.

[0085] The peracid can be (a) incorporated directly as a preformed peracid, or (b) formed in situ in the wash liquor from hydrogen peroxide and a bleaching activator (perhydrolysis), or (c) formed in situ in the wash liquor from hydrogen peroxide and a perhydrolase and a suitable substrate therefor (such as an ester).

[0086] Suitable preformed peracids include, but are not limited to, peroxycarboxylic acids (such as peroxybenzoic acid) and their ring-substituted derivatives, peroxy-α-naphthoic acid, peroxyphthalic acid, peroxylauric acid, peroxystearic acid, ε-phthalimidoperoxyhexanoic acid [phthalimidoperoxyhexanoic acid (PAP)], and o-carboxybenzamidoperoxyhexanoic acid; aliphatic and aromatic diperoxydicarboxylic acids, such as diperoxydodecanedioic acid, diperoxynonanedioic acid, diperoxydodecanedioic acid, diperoxybrazilic acid, 2-decyldiperoxybutanedioic acid, and diperoxyphthalic, -isophthalic, and -terephthalic acids; perimidic acid; peroxymonosulfuric acid; peroxydisulfuric acid; peroxophosphoric acid; peroxosilicic acid; and mixtures of said compounds. It is understood that in some cases, the peracids mentioned may be preferably added as suitable salts, such as alkali metal salts (e.g., ) or alkaline earth metal salts.

[0087] Suitable bleaching activators include those belonging to the categories of esters, amides, imides, nitriles or acid anhydrides, and, where applicable, their salts. Suitable examples are tetraacetylethylenediamine (TAED), sodium 4-[(3,5,5-trimethylhexanoyl)oxy]benzene-1-sulfonate (ISONOBS), sodium 4-(dodecanoyloxy)benzene-1-sulfonate (LOBS), sodium 4-(decanoyloxy)benzene-1-sulfonate, 4-(decanoyloxy)benzoic acid (DOBA), sodium 4-(nonanoyloxy)benzene-1-sulfonate (NOBS) and / or those disclosed in WO 98 / 17767. A particular family of targeted bleaching activators is disclosed in EP 624154 and within this family, triethyl acetylcitrate (ATC) is particularly preferred. ATC or short-chain triglycerides such as triacetin have the advantage that they are environmentally friendly. In addition, triethyl acetylcitrate and triacetin have good hydrolytic stability in the product during storage and are effective bleaching activators. Finally, ATC is multifunctional because the citrate released during the perhydrolysis reaction can act as a builder.

[0088] Bleaching catalysts and boosters

[0089] The bleaching system may also contain a bleaching catalyst or promoter. Some non-limiting examples of bleaching catalysts that can be used in the compositions of the present invention include manganese oxalate, manganese acetate, manganese collagen, cobalt-amine catalysts, and manganese triazacyclononane (MnTACN) catalysts; particularly preferred are complexes of manganese with 1,4,7-trimethyl-1,4,7-triazacyclononane (Me3-TACN) or 1,2,4,7-tetramethyl-1,4,7-triazacyclononane (Me4-TACN), especially Me3-TACN, such as the binuclear manganese complex [(Me3-TACN)Mn(O)3Mn(Me3-TACN)](PF6)2, and [2,2',2”-iminotris(ethane-1,2-diylazan-1-ylidene-methylidyne)triphenolato-κ3O]manganese(III). These bleaching catalysts can also be other metal compounds: such as iron or cobalt complexes.

[0090] In some embodiments in which a peracid source is included, an organic bleaching catalyst or bleaching promoter having one of the following formulas can be used:

[0091] (i)

[0092] (ii)

[0093] (iii) and mixtures thereof;

[0094] Wherein R1 is independently a branched alkyl group having 9 to 24 carbon atoms or a straight-chain alkyl group having 11 to 24 carbon atoms, preferably R1 is independently a branched alkyl group having 9 to 18 carbon atoms or a straight-chain alkyl group having 11 to 18 carbon atoms, more preferably R1 is independently selected from the group consisting of: 2-propylheptyl, 2-butyl octyl, 2-pentyl nonyl, 2-hexyl decyl, dodecyl, tetradecyl, hexadecyl, octadecyl, isononyl, isodecyl, isotridecyl and isopentadecyl.

[0095] Other exemplary bleaching systems are described in, for example, WO 2007 / 087258, WO 2007 / 087244, WO 2007 / 087259, EP 1 867 708 (vitamin K) and WO 2007 / 087242.

[0096] Polymer

[0097] The detergent may contain from 0.005% to 10% by weight (e.g., 0.5% to 5%, 2% to 5%, 0.5% to 2%, or 0.2% to 1%) of a polymer. Any polymer known in the art for use in detergents can be utilized. The polymer can act as a co-builder as mentioned above, or can provide anti-redeposition, fiber protection, soil release, dye transfer inhibition, grease cleaning, and / or defoaming properties. Some polymers can have more than one of the above-mentioned properties and / or more than one of the motifs mentioned below. Exemplary polymers include (carboxymethyl) cellulose (CMC), poly(vinyl alcohol) (PVA), poly(ethylene glycol) or poly(ethylene oxide) (PEG or PEO), ethoxylated poly(ethyleneimine), (carboxymethyl) inulin (CMI), carboxylic acid ester polymers and polycarboxylic acid esters such as polyacrylate, maleic acid / acrylic acid copolymer, acrylate / styrene copolymer, poly(aspartic acid), and lauryl methacrylate / acrylic acid copolymer, hydrophobically modified CMC (HM-CMC), silicone, copolymers of terephthalic acid and oligomeric ethylene glycol, copolymers of poly(ethylene terephthalate) and poly(oxyethylene terephthalate) (PET-POET), poly(vinyl pyrrolidone) (PVP), poly(vinyl imidazole) (PVI), poly(vinyl pyridine-N-oxide) (PVPO or PVPNO), and copolymer(vinyl imidazole / vinyl pyrrolidone) (PVPVI). Suitable examples include PVP-K15, PVP-K30, ChromaBond S-400, ChromaBond S-403E and ChromaBond S-100 from Aqualon of Ashland, Inc., and HP 165, HP 50 (dispersant), HP 53 (dispersant), HP 59 (dispersant), HP 56 (dye transfer inhibitor), HP 66K (dye transfer inhibitor). Additional exemplary polymers include sulfonated polycarboxylates, polyethylene oxide and polypropylene oxide (PEO - PPO), and diquaternary ammonium ethoxysulfates. Particularly preferred polymers are ethoxylated homopolymers from BASF HP 20, which helps prevent soil redeposition in the wash liquor. Additional exemplary polymers include sulfonated polycarboxylates, ethylene oxide - propylene oxide copolymers (PEO - PPO), copolymers of PEG and vinyl acetate, and diquaternary ammonium ethoxysulfates or quaternized ethoxylated hexamethylenediamine sulfates. Other exemplary polymers are disclosed, for example, in WO 2006 / 130575. Salts of the above - mentioned polymers are also contemplated.

[0098] Auxiliary materials

[0099] Any detergent components known in the art for use in laundry washing / ADW / hard surface cleaning detergents can also be utilized. Other optional detergent components include corrosion inhibitors, shrinkage inhibitors, soil redeposition inhibitors, anti - wrinkle agents, bactericides, binders, corrosion inhibitors, disintegrants / disintegration reagents, dyes, enzyme stabilizers (including boric acid, borates, CMC, and / or polyols such as propylene glycol), fabric conditioners (including clays), fillers / processing aids, fluorescent brighteners / optical brighteners, foam boosters, foam (bubble) regulators, fragrances, soil suspending agents, softeners, defoamers, rust inhibitors, and wicking agents, used alone or in combination. Any ingredients known in the art for use in laundry washing / ADW / hard surface cleaning detergents can be utilized. The selection of such ingredients is entirely within the skill of the art.

[0100] Dispersant

[0101] The detergent compositions of the present invention may also contain dispersants. In particular, powdered detergents may contain dispersants. Suitable water - soluble organic materials include homopolymeric or copolymeric acids or their salts, where the polycarboxylic acid contains at least two carboxyl groups separated from each other by no more than two carbon atoms. Suitable dispersants are described, for example, in Powdered Detergents, Surfactant science series, Volume 71, Marcel Dekker, Inc.

[0102] Dye transfer inhibitor

[0103] The detergent composition of the present invention may also comprise one or more dye transfer inhibitors. Suitable polymeric dye transfer inhibitors include, but are not limited to, polyvinylpyrrolidone polymers, polyamine N-oxide polymers, copolymers of N-vinylpyrrolidone and N-vinylimidazole, polyvinyl oxazolidinone and polyvinylimidazole, or mixtures thereof. When present in the subject composition, the dye transfer inhibitor may be present at a level of from about 0.0001% to about 10%, from about 0.01% to about 5%, or even from about 0.1% to about 3% by weight of the composition.

[0104] Fluorescent whitening agent

[0105] The detergent composition of the present invention will preferably also contain additional components which may color the article being cleaned, such as optical brighteners or fluorescent whitening agents. When present, the level of the brightener is preferably from about 0.01% to about 0.5%. Any suitable optical brightener for use in laundry detergent compositions may be used in the compositions of the present invention. The most commonly used optical brighteners are those belonging to the following classes: diamino stilbene-sulfonic acid derivatives, diaryl pyrazoline derivatives, and diphenyl-bistyryl derivatives. Examples of the diamino stilbene-sulfonic acid derivative type of optical brighteners include the sodium salts of the following: 4,4'-bis-(2-diethanolamino-4-anilino-s-triazin-6-ylamino) stilbene-2,2'-disulfonate, 4,4'-bis-(2,4-dianilino-s-triazin-6-ylamino) stilbene-2,2'-disulfonate, 4,4'-bis-(2-anilino-4-(N-methyl-N-2-hydroxy-ethylamino)-s-triazin-6-ylamino) stilbene-2,2'-disulfonate, 4,4'-bis-(4-phenyl-1,2,3-triazol-2-yl) stilbene-2,2'-disulfonate, and sodium 5-(2H-naphtho[1,2-d][1,2,3]triazol-2-yl)-2-[(E)-2-phenylethenyl]benzenesulfonate. Preferred optical brighteners are Tinopal DMS and Tinopal CBS available from Ciba-Geigy AG, Basel, Switzerland. Tinopal DMS is the disodium salt of 4,4'-bis-(2-morpholino-4-anilino-s-triazin-6-ylamino) stilbene-2,2'-disulfonate. Tinopal CBS is the disodium salt of 2,2'-bis-(phenyl-styryl)-disulfonate. Also preferred optical brighteners are commercially available Parawhite KX, supplied by Paramount Minerals and Chemicals, Mumbai, India. Other fluorescent agents suitable for use in the present invention include 1-3-diaryl pyrazoline and 7-alkamino coumarin.

[0106] Suitable levels of the optical brightener include lower levels from about 0.01, from 0.05, from about 0.1 or even from about 0.2 wt% to higher levels of 0.5 or even 0.75 wt%.

[0107] Soil release polymer

[0108] The detergent compositions of the present invention may also comprise one or more soil release polymers which assist in removing soil from fabrics such as cotton and polyester-based fabrics, especially hydrophobic soil from polyester-based fabrics. The soil release polymers can be, for example, polymers based on nonionic or anionic terephthalates, polyvinylcaprolactam and related copolymers, vinyl graft copolymers, polyester polyamides, see for example Powdered Detergents, Surfactant science series, volume 71, chapter 7, Marcel Dekker Inc. Other types of soil release polymers are amphiphilic alkoxylated oil cleaning polymers comprising a core structure and a plurality of alkoxylated groups attached to the core structure. The core structure can comprise a polyalkylimine structure or a polyalkanolamine structure, as described in detail in WO 2009 / 087523 (incorporated herein by reference). In addition, random graft copolymers are suitable soil release polymers. Suitable graft copolymers are described in more detail in WO 2007 / 138054, WO 2006 / 108856 and WO 2006 / 113314 (all incorporated herein by reference). Other soil release polymers are substituted polysaccharide structures, especially substituted cellulose structures, such as those described in EP 1867808 or WO 2003 / 040279 (both incorporated herein by reference). Suitable cellulose polymers include cellulose, cellulose ethers, cellulose esters, cellulose amides, and mixtures thereof. Suitable cellulose polymers include anionically modified cellulose, nonionically modified cellulose, cationically modified cellulose, zwitterionically modified cellulose, and mixtures thereof. Suitable cellulose polymers include methyl cellulose, carboxymethyl cellulose, ethyl cellulose, hydroxyethyl cellulose, hydroxypropyl methyl cellulose, ester carboxymethyl cellulose, and mixtures thereof.

[0109] Anti-redeposition agent

[0110] The detergent composition of the present invention may further comprise one or more anti-redeposition agents such as carboxymethyl cellulose (CMC), polyvinyl alcohol (PVA), polyvinylpyrrolidone (PVP), polyoxyethylene and / or polyethylene glycol (PEG), homopolymers of acrylic acid, copolymers of acrylic acid and maleic acid, and ethoxylated polyethyleneimine. The cellulose-based polymers described above under soil release polymers may also act as anti-redeposition agents.

[0111] Other suitable auxiliary materials include but are not limited to shrink-proofing agents, anti-wrinkle agents, bactericides, binders, carriers, dyes, enzyme stabilizers, fabric softeners, fillers, foam regulators, hydrotropes, fragrances, pigments, and defoamers.

[0112] Further embodiments of the present invention include:

[0113] Example 1. A colored granule comprising

[0114] (a) a colored core containing a colorant, and

[0115] (b) a salt coating that coats the core, the salt coating constituting 1% - 70% w / w of the granule and containing at least 60% w / w of a salt having a constant relative humidity of at least 60% at 20°C.

[0116] Example 2. The granule according to Example 1, further comprising a target compound.

[0117] Example 3. The granule according to Example 1, wherein the colored core further comprises a target compound.

[0118] Example 4. The granule according to Example 2 or 3, wherein the target compound is present in an amount of 0.05% - 50% w / w of the granule.

[0119] Example 5. The granule according to Example 2 or 3, wherein the target compound is present in an amount of 0.1% - 30% w / w of the granule.

[0120] Example 6. The granule according to Example 2 or 3, wherein the target compound is present in an amount of 0.5% - 25% w / w of the granule.

[0121] Example 7. The granule according to Example 2 or 3, wherein the target compound is present in an amount of 1% - 20% w / w of the granule.

[0122] Example 8. The granule according to any one of Examples 2 - 7, wherein the target compound is a bleaching system component such as a bleach activator, a bleach catalyst, or percarbonate.

[0123] Example 9. The particle according to any one of Examples 2-7, wherein the target compound is a protein.

[0124] Example 10. The particle according to any one of Examples 2-7, wherein the target compound is an enzyme, and the amount is the active enzyme protein.

[0125] Example 11. The particle according to the previous example, wherein the enzyme is selected from the group consisting of: protease, lipase, amylase, cellulase, pectinase, mannanase, xylanase, nuclease, dispersin, catalase, perhydrolase, and combinations thereof.

[0126] Example 12. The particle according to any one of the previous examples, wherein the colored core comprises at least two coatings / layers.

[0127] Example 13. The particle according to any one of the previous examples, wherein the colored core contains a colorant as a coating.

[0128] Example 14. The particle according to the previous example, wherein the colored core contains a salt coating coated with a colorant coating.

[0129] Example 15. The particle according to any one of the previous examples, wherein the colorant is listed in the Color Index.

[0130] Example 16. The particle according to any one of the previous examples, wherein the Color Index hue of the colorant is selected from the group consisting of: yellow, orange, red, green, blue, and violet.

[0131] Example 17. The particle according to any one of the previous examples, wherein the Color Index hue of the colorant is yellow.

[0132] Example 18. The particle according to any one of the previous examples, wherein the Color Index hue of the colorant is orange.

[0133] Example 19. The particle according to any one of the previous examples, wherein the Color Index hue of the colorant is red.

[0134] Example 20. The particle according to any one of the previous examples, wherein the Color Index hue of the colorant is green.

[0135] Example 21. The particle according to any one of the previous examples, wherein the Color Index hue of the colorant is blue.

[0136] Example 22. The particle according to any one of the previous examples, wherein the Color Index hue of the colorant is violet.

[0137] Example 23. The particle according to any one of the foregoing examples, wherein the color index usage category of the colorant is selected from the group consisting of: acid dyes, basic dyes, direct dyes, food colors, mordant dyes, natural dyes, reactive dyes, solvent dyes, vat dyes, sulfur dyes, disperse dyes, and pigments.

[0138] Example 24. The particle according to any one of the foregoing examples, wherein the color index usage category of the colorant is selected from the group consisting of: acid dyes, basic dyes, direct dyes, food colors, mordant dyes, natural dyes, reactive dyes, and pigments.

[0139] Example 25. The particle according to any one of the foregoing examples, wherein the color index usage category of the colorant is selected from the group consisting of: acid dyes, basic dyes, food colors, and natural dyes.

[0140] Example 26. The particle according to any one of the foregoing examples, wherein the colorant is a naturally occurring colorant.

[0141] Example 27. The particle according to any one of the foregoing examples, wherein the colorant is a colorant of plant origin.

[0142] Example 28. The particle according to any one of the foregoing examples, wherein the colorant is a dye.

[0143] Example 29. The particle according to any one of the foregoing examples, wherein the colorant is a pigment.

[0144] Example 30. The particle according to any one of the foregoing examples, further comprising an outermost polymer coating that coats the salt coating.

[0145] Example 31. The particle according to any one of the foregoing examples, further comprising an outermost polymer coating that coats the salt coating, and the outermost polymer coating comprises polyethylene glycol, methylhydroxypropyl cellulose, or polyvinyl alcohol.

[0146] Example 32. The particle according to any one of the foregoing examples, wherein the salt coating comprises at least 70% w / w of salt.

[0147] Example 33. The particle according to any one of the foregoing examples, wherein the salt coating comprises at least 80% w / w of salt.

[0148] Example 34. The particle according to any one of the foregoing examples, wherein the salt coating comprises at least 90% w / w of salt.

[0149] Example 35. The particle according to any one of the preceding examples, wherein the salt coating comprises at least 95% w / w of salt.

[0150] Example 36. The particle according to any one of the preceding examples, wherein the salt of the salt coating has a constant relative humidity of at least 70% at 20 °C.

[0151] Example 37. The particle according to any one of the preceding examples, wherein the salt of the salt coating has a constant relative humidity of at least 80% at 20 °C.

[0152] Example 38. The particle according to any one of the preceding examples, wherein the salt of the salt coating has a constant relative humidity of at least 85% at 20 °C.

[0153] Example 39. The particle according to any one of the preceding examples, wherein the salt coating comprises sodium sulfate.

[0154] Example 40. The particle according to any one of the preceding examples, wherein the salt coating constitutes 1% - 50% w / w of the particle.

[0155] Example 41. The particle according to any one of the preceding examples, wherein the salt coating constitutes 2% - 40% w / w of the particle.

[0156] Example 42. The particle according to any one of the preceding examples, wherein the salt coating constitutes 5% - 40% w / w of the particle.

[0157] Example 43. The particle according to any one of the preceding examples, wherein the thickness of the salt coating is 1 - 100 μm.

[0158] Example 44. The particle according to any one of the preceding examples, wherein the thickness of the salt coating is 1 - 60 μm.

[0159] Example 45. The particle according to any one of the preceding examples, wherein the thickness of the salt coating is 5 - 60 μm.

[0160] Example 46. The particle according to any one of the preceding examples, wherein the volume-based average particle size of the particle is 20 - 2000 μm.

[0161] Example 47. The particle according to any one of the preceding examples, wherein the volume-based average particle size of the particle is 50 - 1500 μm.

[0162] Example 48. The particle according to any one of the preceding examples, wherein the volume-based average particle size of the particle is 100 - 1500 μm.

[0163] Example 49. The particle according to any one of the foregoing examples, wherein the volume-based average particle size of the particle is 250 - 1200 μm.

[0164] Example 50. The particle according to any one of the foregoing examples, which is water-soluble or water-dispersible.

[0165] Example 51. The particle according to any one of the foregoing examples, wherein the colorant has a sum of the numerical values of "a" and "b" of at least 20, preferably at least 30, at least 40, or at least 50 in the Hunter L, a, b color space.

[0166] Example 52. The particle according to any one of the foregoing examples, wherein the color of the particle has a sum of the numerical values of "a" and "b" of at least 20, preferably at least 30, at least 40, or at least 50 in the Hunter L, a, b color space.

[0167] Example 53. A solid detergent composition comprising a surfactant and a builder, and a colored particle according to any one of the foregoing examples.

[0168] Example 54. The solid detergent composition according to the previous example, which further comprises a bleaching system component.

[0169] Example 55. The solid detergent composition according to the previous example, wherein the bleaching system component is a bleach activator, a bleach catalyst, or percarbonate.

[0170] Example 56. The solid detergent composition according to the previous example, wherein the bleach catalyst is a manganese bleach catalyst, such as MnTACN.

[0171] Example 57. The solid detergent composition according to Example 55 or 56, wherein the bleach activator is TAED or NOBS.

[0172] Example 58. The solid detergent composition according to Example 55, wherein the bleaching system component is percarbonate.

[0173] Example 59. The solid detergent composition according to any one of Examples 53 - 58, which is an ADW detergent.

[0174] Example 60. The solid detergent composition according to any one of Examples 53 - 58, which is a laundry detergent.

[0175] Example 61. The solid detergent composition according to any one of Examples 53 - 60, which comprises the colored particles in an amount of up to 10% w / w.

[0176] Example 62. The solid detergent composition as described in the previous example, which contains up to 5% w / w of colored particles.

[0177] Examples

[0178] The chemicals are at least reagent-grade commercial products.

[0179] Example 1

[0180] Example 1.1: Uncoated green granules

[0181] 5 kg of white protease granules (from Novozymes A / S) were fluidized in a coating fluidized bed. The granules were colored green by spraying the following mixture onto the granules:

[0182] 2.50 g of Food Yellow 13 (Puricolor Yellow FYE13 from BASF),

[0183] 0.63 g of Acid Blue 3 (or Food Blue 3),

[0184] 4.00 g of PEG4000 (polyethylene glycol Mw 4000), and

[0185] 396 g of water.

[0186] Example 1.2: Salt-coated green granules

[0187] Green granules were produced as in Ex. 1.1. A mixture of 500 g of Na2SO4 and 1500 g of water was sprayed onto the granules to prepare salt-coated green granules. The color of the granules differed only very slightly from that of the uncoated green granules produced in Example 1.1.

[0188] Example 1.3: Uncoated red granules

[0189] 4 kg of white amylase granules (from Novozymes) were fluidized in a coating fluidized bed. The granules were colored red by spraying the following mixture onto the granules:

[0190] 9.20 g of Acid Red 18 (Food Red 7, Puricolor Red ARE18 from BASF),

[0191] 9.20 g of MHPC (Culminal MHPC 5 from Ashland),

[0192] 0.40 g of sodium thiosulfate, and

[0193] 950 g of water.

[0194] Example 1.4: Salt-coated red granules

[0195] Produce red granules as in Ex. 1.3. Spray a mixture of 320 g of Na2SO4 and 783 g of water onto the granules to prepare salt-coated red granules. After the salt coating, apply a film coating by spraying a mixture of 44 g of MHPC, 36 g of PEG4000, and 836 g of water onto the salt-coated red granules. The color of the final granules is visually indistinguishable from that of the uncoated red granules produced in Example 1.3.

[0196] Example 1.5: Salt-coated red granules

[0197] Produce red granules as in Ex. 1.3. Spray a mixture of 480 g of Na2SO4 and 1175 g of water onto the granules to prepare salt-coated red granules. After the salt coating, apply a film coating by spraying a mixture of 44 g of MHPC, 36 g of PEG4000, and 836 g of water onto the salt-coated red granules. The color of the final granules is visually indistinguishable from that of the uncoated red granules produced in Example 1.3 and the salt-coated red granules produced in Example 1.4.

[0198] Color stability of granules

[0199] Produce an automatic dishwashing (ADW) powder detergent (ADW tablet base) by mixing the following:

[0200] 37.5% w / w Na2SO4

[0201] 19.7% w / w sodium citrate dihydrate

[0202] 16.8% w / w Na2CO3

[0203] 4.9% w / w disodium silicate (Britesil H 265HP)

[0204] 4.9% w / w copolymer of acrylic acid and sulfonic acid (Acusol 588G)

[0205] 4.9% w / w alcohol ethoxylate (Surfac 23-6.5) (liquid, mixed into the powder)

[0206] 9.9% w / w percarbonate granules (13.5% w / w active oxygen)

[0207] 0.4% w / w MnTACN granules (6% w / w MnTACN)

[0208] 1.0% w / w glycerol (liquid, mixed into the powder)

[0209] Mix 3 g of colored enzyme granules (uncoated or salt-coated) with 12 g of ADW powder detergent in an open glass container. Test the accelerated color storage stability by incubating the glass container at 37 °C and 70% relative humidity for 3 days (green granules) or 12 days (red granules), and then compare these samples with reference samples stored at 5 °C.

[0210] After storage, visually compare the glass containers, and measure the residual color by dissolving the samples and measuring the absorbance using a spectrophotometer. For the green granules, the absorbance scan shows maxima at 380 nm (blue) and 630 nm (yellow), and for the red granules, the maximum absorbance is found at 520 nm (red):

[0211] · Dissolve the sample (15 g) in each glass container in 100 g of deionized water (containing 0.1% Catazyme 25L (catalase) from Novozymes to quench hydrogen peroxide).

[0212] · Filter each sample through a 0.45-micron filter and dilute it 1:1 with deionized water.

[0213] · Measure the absorbance using the dissolved ADW powder as a reference, and

[0214] · Calculate the residual absorbance (as a percentage) as the absorbance of the sample stored at 37 °C / 70% RH divided by the absorbance of the sample stored at 5 °C.

[0215] Table 1. Colored granules in ADW powder stored at 37 °C and 70% relative humidity.

[0216]

[0217] As can be seen in Table 1, the coated granules (Example 1.2, Example 1.4, Example 1.5) are much more color-stable than the uncoated granules (Example 1.1, Example 1.3).

[0218] As described above, there is little or no color change for the salt-coated compared to the uncoated red and green granules. Measure the color coordinates of the red granules using a Hunter ColorFlex to obtain Hunter coordinates L, a, b. The "L" value represents white / black, the "a" value represents red / green, and the "b" value represents yellow / blue. Thus, the red color of the red granules (Example 1.3, Example 1.4, Example 1.5) can be evaluated by measuring the Hunter "a" coordinate.

[0219] Table 2.

[0220]

[0221] The change in Hunter "a" value after application of the salt coating was very small such that these changes were not visible by visual inspection.

Claims

1. A colored granule, which comprises (a) a colored core containing a colorant, and (b) a salt coating that coats the core, the salt coating constituting 1%-50% w / w of the granule and containing at least 60% w / w of a salt having a constant relative humidity of at least 60% at 20 °C, and the salt coating forming a continuous layer with few or no pores.

2. The colored granule according to the previous claim, which is water-soluble / dispersible.

3. The colored granule according to any one of the previous claims, wherein The colored core contains from 0.05% to 50% w / w of the target compound of the particle; preferably, the target compound is a protein such as an enzyme.

4. The colored granule according to the previous claim, wherein The colored core contains from 0.1% to 30% w / w, preferably from 0.5% to 25% w / w of the particle, of the target compound.

5. The colored granule according to any one of the previous claims, wherein The colorant or the color of the particle has a sum of "a" and "b" values of at least 20, preferably at least 30, or at least 40 in the Hunter L,a,b color space.

6. The colored granule according to the previous claim, wherein The colorant is listed in the Color Index; preferably, the Color Index hue is selected from the group consisting of: yellow, orange, red, green, blue, and violet.

7. The colored granule according to the previous claim, wherein The Color Index usage category is selected from the group consisting of: acid dyes, basic dyes, direct dyes, food colors, mordant dyes, natural dyes, reactive dyes, solvent dyes, vat dyes, sulfur dyes, disperse dyes, and pigments; preferably acid dyes, basic dyes, direct dyes, food colors, mordant dyes, natural dyes, reactive dyes, and pigments; more preferably acid dyes, basic dyes, food colors, and natural dyes.

8. The colored granule according to any one of the previous claims, wherein The colorant is a naturally occurring colorant, such as a colorant of plant origin.

9. The colored granule according to any one of the previous claims, wherein The colored core contains the colorant as a coating at the surface of the core.

10. The colored granule according to any one of the previous claims, wherein The salt coating constitutes 2% to 40% w / w of the particle and contains at least 80% w / w, preferably at least 90% w / w, of a salt having a constant relative humidity of at least 80% at 20°C.

11. The colored granule according to any one of the previous claims, wherein The salt coating contains sodium sulfate.

12. The colored granule according to any one of the previous claims, wherein The salt has a solubility of at least 0.1 gram in 100 g of water at 20°C, preferably at least 0.5 g / 100 g water, at least 1 g / 100 g water, or at least 5 g / 100 g water.

13. The colored granule according to any one of the previous claims, which contains less than 10% w / w of a surfactant; preferably less than 5% w / w, or less than 2% w / w of a surfactant.

14. The colored granule according to any one of the previous claims, wherein The volume-based average particle size is 100 - 1500 μm, preferably 250 - 1200 μm.

15. A solid detergent composition, which comprises a surfactant and a builder, and a colored granule according to any one of the previous claims; preferably further comprises a bleaching system component.

16. The solid detergent composition according to the previous claim, wherein The bleaching system component is a bleach activator, a bleach catalyst, or a percarbonate.

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