DETERGENT

Abstract

The detergent preparation is in the form of an object with a maximum linear diameter ranging from 0.2 mm to 300 mm, in which the detergent preparation contains: microcapsules in the range of 0.01% to 20% by weight, hydrocolloids in the range of 0.5% to 10% by weight, salt, and water in the range of 50% to 99% by weight, and in which the microcapsules have a microcapsule shell, and this microcapsule shell contains proteins and / or polysaccharide polymers.

Description

[0001] LAUNDRY COMPOSITION

[0002] Field of the Invention

[0003] The present invention relates to ancillary laundry compositions for use in the laundry process.

[0004] Background of the Invention

[0005] Laundry products are used for various reasons, traditionally detergents are used for cleaning and fabric conditioners are used for softening and perfuming fabrics. However, there is an increased demand for laundry compositions which provide fabric care benefits to fabrics.

[0006] Various ingredients have been added to laundry products to provide fabric care. However, the addition of ingredients to a laundry composition has the drawback of increased complexity in formulations, increased cost and ingredients which may not meet the environmental credentials desired by the consumers.

[0007] Microcapsules are used in various laundry applications to deliver active materials to fabrics. Microcapsules are known to provide various benefits, such as delayed release of the active material or protection of the active material from other ingredients in the laundry composition. Conventional microcapsules typically have a microcapsule wall formed of a synthetic polymer such as a melamine formaldehyde polymer or polyacrylate polymer.

[0008] There remains a need for laundry compositions which provide fabric care to fabrics.

[0009] US 2020 / 325419 A1 discloses liquid detergent compositions comprising a continuous liquid phase that is transparent or translucent; and solid particles made of a polymeric matrix material that are dispersed in the continuous liquid phase and comprise a plurality of microcapsules. of the Invention

[0010] It has been found that the use of a microcapsules comprising protein or polysaccharides in hydrogel laundry compositions leads to improved fabric care, in particular fabric care attributes such as improved hand of fabrics, improved softening, reduced friction, improved elasticity. Accordingly in a first aspect of the present invention is provided a laundry composition in the form of an article having a diameter maximum linear diameter of 0.2 mm to 300 mm, wherein the laundry composition comprises: a. 0.01 to 20 wt.% microcapsules; b. 0.5 to 10 wt.% hydrocolloid; c. salt; and d. 50 to 99 wt.% water; wherein the microcapsules have a microcapsule wall and the microcapsule wall comprises protein and / or polysaccharide polymers.

[0011] Additionally, the present invention is provides a method of using a laundry composition as described herein to provide fabric care, wherein the particle is added to the wash stage of the laundry process.

[0012] In a further aspect of the present invention is a use of a laundry composition as described herein to provide fabric care to a laundered fabric.

[0013] Detailed Description of the Invention

[0014] These and other aspects, features and advantages will become apparent to those of ordinary skill in the art from a reading of the following detailed description and the appended claims. For the avoidance of doubt, any feature of one aspect of the present invention may be utilised in any other aspect of the invention. The word “comprising” is intended to mean “including” but not necessarily “consisting of’ or “composed of.” In other words, the listed steps or options need not be exhaustive. It is noted that the examples given in the description below are intended to clarify the invention and are not intended to limit the invention to those examples per se. Similarly, all percentages are weight / weight percentages unless otherwise indicated. Except in the operating and comparative examples, or where otherwise explicitly indicated, all numbers in this description indicating amounts of material or conditions of reaction, physical properties of materials and / or use are to be understood as modified by the word “about”. Numerical ranges expressed in the format "from x to y" are understood to include x and y. When for a specific feature multiple preferred ranges are described in the format "from x to y", it is understood that all ranges combining the different endpoints are also contemplated. When the “laundry composition” is referred to this is the final, cured product comprising the salt.

[0015] By microcapsule it is herein understood to mean the microcapsule (wall and core) i.e. , without a solvent or slurry.

[0016] The laundry compositions of the present invention comprise 0.01 to 20 wt.% microcapsules, by weight of the composition. More preferably 0.05 to 15 wt.% microcapsules, most preferably 0.1 to 12 wt.% microcapsules.

[0017] The microcapsules may be provided simply as microcapsules or may be provided in a slurry. The microcapsules comprise a microcapsule core comprising an active ingredient and microcapsule wall encapsulating the core. The microcapsule wall comprises a wall polymer comprising protein and / or polysaccharide polymers and preferably a crosslinking agent. Typically, the microcapsules comprise 10 wt.% to 98 wt.% core materials, 1 wt.% to 20 wt.% wall polymer and optionally 0.2 wt.% to 6 wt.% crosslinking agent.

[0018] The microcapsules may be prepared by any suitable process including those exemplary processes described here.

[0019] Microcapsule wall materials

[0020] The microcapsule wall may also be referred to as the microcapsule shell. The microcapsule wall comprises protein polymers, polysaccharide polymers or a combination thereof. The protein and / or polysaccharide may be treated by various processes to provide derivatives, including but not limited to hydrolysis, condensation, functionalising such as ethoxylating, crosslinking, etc.

[0021] Without wishing to be bound by theory, it is believed that the use of proteins and / or polysaccharides improves the ‘hand’ of a fabric when treated with the laundry compositions described herein. The microcapsule wall materials are preferably in an aqueous solution. The microcapsule wall preferably comprises 20 wt.% to 100 wt.% protein and / or polysaccharide, more preferably 30 wt.% to 98 wt.%, more preferably 35 wt.% to 95 wt.%, and most preferably 65 wt.% to 90 wt.% by weight of the microcapsule wall.

[0022] As is conventional in the art, a “protein”, also known as a “polypeptide” is a linear organic polymer composed of amino acid residues bonded together in a chain, forming part of (or the whole of) a protein molecule. “Polypeptide” or “protein” as used herein means a natural polypeptide, polypeptide derivative, and / or modified polypeptide. The protein may exhibit an average molecular weight of from 1 ,000 Da to 40,000,000 Da, preferably greater than 10,000 Da, more preferably, 100,000 Da, most preferably greater than 1 ,000,000 Da and preferably less than 3,000,000 Da.

[0023] Suitable proteins for use in this invention include whey proteins, plant proteins and gelatine. Preferably plant proteins are used. Suitable preferred proteins include proteins selected from: pea, potato proteins, brown rice, white rice, wheat, egg, barley, pumpkin seed, oat, almond, whey, casein, silk, gelatin, algae, rye, spelt, gluten, rapeseed, sunflower, corn, soybean, bean, chickpea, lentil, lupin, peanut, alfalfa, hemp and combinations thereof. Particularly preferred proteins include proteins selected from chickpea, pea proteins, potato proteins, brown rice proteins, white rice proteins, wheat proteins, barley proteins, pumpkin seed proteins, oat proteins, almond proteins, and combinations thereof. This includes derivatives of the aforementioned proteins.

[0024] As used herein, whey protein refers to the protein contained in whey, a dairy liquid obtained as a supernatant of curds when milk or a dairy liquid containing milk components, is processed into cheese curd to obtain a cheese-making curd as a semisolid. Whey protein is generally understood in principle to include the globular proteins b-lactoglobulin and a-lactalbumin at various ratios such as 1: 1 to 5: 1 (e.g., 2: 1). It may also include lower amounts of serum albumin, immunoglobulin and other globulins. The term whey protein is also intended to include partially or completely modified or denatured whey proteins. Purified b-lactoglobulin and / or a- lactalbumin polypeptides may also be used in preparation of microcapsules of this invention.

[0025] Gelatin refers to a mixture of proteins produced by partial hydrolysis of collagen extracted from the skin, bones, and connective tissues of animals. Gelatin can be derived from any type of collagen, such as collagen type I, II, III, or IV. Such proteins are characterized by including Gly- Xaa-Yaa triplets wherein Gly is the amino acid glycine and Xaa and Yaa can be the same or different and can be any known amino acid. At least 40% of the amino acids are preferably present in the form of consecutive Gly-Xaa-Yaa triplets.

[0026] A preferred class of proteins are plant proteins. Plant proteins are proteins that accumulate in various plant tissues. Preferred plant proteins can be classified into two classes: seed and grain proteins or vegetable proteins. Seed / grain proteins are a set of proteins that accumulate to high levels in seeds / grains during the late stages of seed / grain development, whereas vegetable proteins are proteins that accumulate in vegetative tissues such as leaves, stems and, depending on plant species, tubers.

[0027] Preferred examples of seed / grain / legumes storage proteins are proteins from: soya, lupine, pea, chickpea, alfalfa, horse bean, lentil, and haricot bean; from oilseed plants such as colza, cottonseed and sunflower; from cereals like wheat, maize, barley, malt, oats, rye and rice (e.g., brown rice protein), or a combination thereof.

[0028] Preferred examples of vegetable protein are proteins form: potato or sweet potato tubers.

[0029] The term plant protein is intended to include a plant protein isolate, plant protein concentrate, or a combination thereof. Plant protein isolates and concentrates are generally understood to be composed of several proteins. For example, pea protein isolates and concentrates may include legumin, vicilin and convicilin proteins. Similarly, brown rice protein isolates may include albumin, globulin and glutelin proteins. The term “plant protein” is also intended to include a partially or completely modified or denatured plant storage protein. Individual polypeptides (e.g., legumin, vicilin, convicilin, albumin, globulin or glutelin) may also be used in preparation of microcapsules of this invention.

[0030] A native protein maybe preferred. However, the process may include a step of denaturing the protein by pH adjustment, heat, or adding a chaotropic agent to the oil-in-water emulsion or to the protein before adding to the oil-in-water emulsion.

[0031] Denaturation is a process in which proteins (polypeptides) lose the quaternary structure, tertiary structure, and secondary structure present in their native state, by application of a denaturation condition. During denaturation, proteins change their conformational structure by unfolding, thereby making amine and hydroxyl groups available for crosslinking (such as crosslinking with polyisocyanate) to form a microcapsule wall. Exemplary conditions for protein denaturation include, but are not limited to, radiation, exposure to heat or cold, changes in pH with an acid or base, exposure to denaturing agents such as detergents, inorganic salt, organic solvent (e.g., alcohol, ethyl acetate, and chloroform), urea, or other chaotropic agents, or mechanical stress including shear. Exemplary chaotropic agents are guanidine salts (e.g., guanidine hydrochloride and guanidine carbonate), urea, polysorbate, sodium benzoate, vanillin, o-cresol, phenol, propanol, formamide, ethanol, fructose, ammonium sulfate, ammonium chloride, ammonium nitrate, ammonium phosphate, potassium sulfate, potassium chloride, potassium iodide, potassium nitrate, potassium phosphate, sodium sulfate, sodium chloride, sodium bromide, sodium nitrate, sodium phosphate, guanidine thiocyanate, xylose, glycerol, benzyl alcohol, ethyl acetate, triton X-100, ethyl acetate, cetyltrimethylammonium halide, acetone, sodium dodecyl sulfate (SDS), hydrochloric acid, sulfuric acid, polyethylene glycol, glutaraldehyde, and combinations thereof. Any amount of the chaotropic agent can be used.

[0032] It may be preferred that the protein is denatured with a chaotropic agent so that 20 wt. % to 100 wt.% preferably 40 wt. % to 100 wt. %, more preferably 60 wt.% to 100 wt.%, most preferably 90 wt.% to 100 wt.% of the protein used in the preparation of the microcapsules is denatured. The protein used in the microcapsule can also be derivatized or modified (e.g., derivatized or chemically modified). For example, the protein can be modified by covalently attaching sugars, lipids, cofactors, peptides, or other chemical groups including phosphate, acetate, methyl, and other natural or unnatural molecule.

[0033] Polysaccharides are a class of carbohydrates comprising multiple monosaccharide units. “Polysaccharide” as used herein means a natural polysaccharide, polysaccharide derivative, and / or modified polysacharide. Suitable polysaccharides maybe selected from the group consisting of fibres, starch, sugar alcohols, sugars and mixtures thereof.

[0034] Examples of suitable fibres include: particular cellulose, cellulose derivatives such as hydroxyethyl cellulose, in particular quaternized hydroxyethyl cellulose, carboxymethylcellulose (CMC) and microcrystalline cellulose (MCC), hemicelluloses, lichenin, chitin, chitosan, lignin, xanthan, plant fibers, in particular cereal fibers, potato fibers, apple fibers, citrus fibers, bamboo fibers, extracted sugar beet fibers; oat fibers and soluble dietary fibers, in particular inulin, especially native inulin, highly soluble inulin, granulated inulin, high performance inulin, pectins, alginates, agar, carrageenan, gum arabic (Senegal type, Seyal type), konjac gum, gellan gum, curdlan (paramylon), guar gum, locust bean gum, xanthan gum, raffinose, xylose, polydextrose and lactulose and combinations thereof. This includes derivatives of the aforementioned polysaccharides.

[0035] Examples of suitable starches include starch from: wheat, potatoes, corn, rice, tapioca and oats, modified starch, and starch derivatives, e.g., dextrins or maltodextrins, in particular dextrins and maltodextrins from wheat, potatoes, corn, rice, pea, chickpea and oats, oligosaccharides, in particular oligofructose. Preferred starches are selected from: corn starch, potato starch, rye starch, wheat starch, barley starch, oat starch, rice starch, pea starch, chickpea starch, tapioca starch, and mixtures thereof.

[0036] Examples of suitable sugar alcohols include: sorbitol, mannitol, isomalt, maltitol, maltilol syrup, lactitol, xylitol, erythritol.

[0037] An example of suitable sugar includes: glucose.

[0038] Particularly preferred polysaccharides include: gum Arabic, dextrins, maltodextrins and combinations thereof.

[0039] The polysaccharide used in the microcapsule can also be derivatized or modified (e.g., derivatized or chemically modified). For example, the protein can be modified by covalently attaching sugars, lipids, cofactors, peptides, or other chemical groups including phosphate, acetate, methyl, and other natural or unnatural molecule. Examples of suitable polysaccharide derivatives include: starch glycolate, carboxymethyl starch, hydroxyalkyl cellulose and crosslinked modified cellulose.

[0040] The microcapsules as described herein may optionally comprise additional polymers in the microcapsule walls. Such additional polymers may include: a sol-gel polymer (e.g., silica), polyacrylate, polyacrylamide, poly(acrylate-co-acrylamide), polyurea, polyurethane, starch, gelatin and gum Arabic, poly(melamine-formaldehyde), poly(urea- formaldehyde), and combinations thereof. However preferably the microcapsule wall polymers consist essentially of proteins, polysaccharides and combinations thereof.

[0041] The microcapsule preferably comprises from 0.1 wt.% to 30 wt.% microcapsule wall, preferably 0.5 wt.% to 25 wt.%, more preferably 1 wt.% to 20 wt.% and 2 wt.% to 15 wt.% microcapsule wall by weight of the microcapsule.

[0042] The microcapsule wall polymers described herein are preferably crosslinked. Suitable methods of crosslinking include: isocyanate crosslinking, salt bridge cross linking and internal crosslinking within the microcapsule wall polymer structures (including the formation of a coacervate). Where a cross linking agent is used, such as polyisocyanate crosslinking agents or ionic crosslinking agents, the crosslinking agent is preferably present at a level of 0.1 wt.% to 10 wt.% by weight of the microcapsule, preferably 0.5 wt.% to 9 wt.% by weight of the microcapsule, even more preferably 1 to 8 wt.% by weight of the microcapsule.

[0043] One preferred method of cross linking is using polyisocyanates. Without wishing to be bound by theory, the selection of an isocyanate cross linking agent improves the softening of a fabric treated with a composition comprising the microcapsules.

[0044] Polyisocyanates each have at least two isocyanate (-NCO) groups reactive towards proteins or polysaccharides. The polyisocyanate can be aromatic, aliphatic, linear, branched, or cyclic, preferably the polyisocyanate comprises polyisocyanates selected from aliphatic, cycloaliphatic, hydroaromatic, aromatic or heterocyclic polyisocyanate, their substitution products and mixtures thereof, most preferably selected from aromatic, aliphatic polyisocyanate and combinations thereof. It is particularly preferred, that more than one polyisocyanate is present. The isocyanate may be, water soluble or water dispersible, alternatively, it can be soluble in an organic solvent or fragrance oil. Preferably, the polyisocyanate is water insoluble. Preferably, the polyisocyanate comprises, 2 to 4 isocyanate groups. More preferably, the polyisocyanate comprises 3 to 4 isocyanate functional groups.

[0045] Examples of suitable polyisocyanate include a trimer of hexamethylene diisocyanate, a trimer of isophorone diisocyanate, a biuret of hexamethylene diisocyanate, a polyisocyanurate of toluene diisocyanate, a trimethylol propane-adduct of toluene diisocyanate, a trimethylol propane - adduct of xylylene diisocyanate, and combinations thereof.

[0046] Preferably the polyisocyanate used in this invention is an aromatic poly isocyanate. Preferably, the aromatic polyisocyanate includes a phenyl, tolyl, xylyl, naphthyl or diphenyl moiety as the aromatic component. Particularly preferably, the aromatic polyisocyanate is a polyisocyanurate of toluene diisocyanate, a trimethylol propane -adduct of toluene diisocyanate or a trimethylol propane -adduct of xylylene diisocyanate.

[0047] One class of suitable aromatic polyisocyanates are those having the generic structure shown below, and its structural isomers wherein n can vary from zero to a desired number (e.g., 0-50, 0-20, 0-10, and 0-6) depending on the type of crosslinker used. Preferably, the number of n is limited to less than 6. The starting polyisocyanate may also be a mixture of polyisocyanates where the value of n can vary from 0 to 6. In the case where the starting polyisocyanate is a mixture of various polyisocyanates, the average value of n preferably falls in between 0.5 and 1.5. Commercially-available polyisocyanates include products under the trade names of LUPRANATE® M20 (chemical name: polymeric methylene diphenyl diisocyanate, i.e.,“PMDI”; commercially available from BASF containing isocyanate group “NCO” 31.5 wt%), where the average n is 0.7; PAPI™ 27 (PMDI commercially available from Dow Chemical having an average molecular weight of 340 and containing NCO 31.4 wt%) where the average n is 0.7; MON DUR® MR (PMDI containing NCO at 31 wt% or greater, commerciallyavailable from Covestro, Pittsburg, Pennsylvania) where the average n is 0.8; MONDUR® MR Light (PMDI containing NCO 31.8 wt%, commercially available from Covestro) where the average n is 0.8; MONDUR® 489 (PMDI commercially available from Covestro containing NCO 30-31.4 wt%) where the average n is 1 ; poly[(phenylisocyanate)-co-formaldehyde] (Aldrich Chemical, Milwaukee, Wl), other isocyanate monomers such as DESMODUR® N3200 (poly(hexamethylene diisocyanate) commercially available from Covestro), and Takenate™ D-l 10N (trimethylol propane -adduct of xylylene diisocyanate, Mitsui Chemicals America, Inc., Rye Brook, NY, containing NCO 11.5 wt%), DESMODUR® L75 (a polyisocyanate base on toluene diisocyanate commercially available from Covestro), and DESMODUR® IL (another polyisocyanate based on toluene diisocyanate commercially available from Covestro).

[0048] An alternate suitable class of polyisocinates are diisocyanates with the general structure O=C=N-R-N=C=O, wherein R represents aliphatic, alicyclic or aromatic radicals, are used. Preferably, the radicals have five or more carbon atoms.

[0049] Other examples of the aromatic polyisocyanate include 1,5-naphthylene diisocyanate, 4,4'- diphenylmethane diisocyanate (MDI), hydrogenated MDI, xylylene diisocyanate (XDI), tetramethylxylol diisocyanate, 4,4'-diphenyldimethylmethane diisocyanate, di- and tetraalkyldiphenylmethane diisocyanate, 4,4'-dibenzyl diisocyanate, 1,3-phenylene diisocyanate, 1,4- phenylene diisocyanate, the isomers of tolylene diisocyanate (TDI), 4,4'-diisocyanatophenyl- perfluoroethane, phthalic acid bisisocyanatoethyl ester, also polyisocyanates with reactive halogen atoms, such as 1 -chloromethylphenyl 2,4-diisocyanate, 1 -bromomethyl -phenyl 2,6- diisocyanate, and 3,3-bischloromethyl ether 4,4'-diphenyldiisocyanate, and combinations thereof. The weight average molecular weight of useful polyisocyanates is preferably from 200 Da to 2500 Da, more preferably 250 Da to 1000 Da and most preferably from 275 Da to 500 Da.

[0050] The polyisocyanate is preferably present in the wall in an amount of 0.1 wt.% to 40 wt.%, more preferably 0.2 wt.% to 25 wt.%, even more preferably 0.25 wt.% to 15 wt.%, and most preferably 0.5 wt.% to 5 wt.%, by weight of the microcapsule wall. Preferably the ratio of polysaccharide and / or protein to polyisocyanate is 1 : 1 to 10: 1.

[0051] During the process of preparing the microcapsule composition of this invention, polyisocyanate can be added to the aqueous phase, the oil phase, or the oil-in-water emulsion.

[0052] More suitable polyisocyanate examples can be found in WO 2004 / 054362 and WO 2017 / 192648.

[0053] An alternative crosslink agent suitable for use in the present invention are ionic crosslinking agents. Ionic crosslinking agents are multivalent ions which are capable of forming salt bridges with the functional groups of the protein or polysaccharide polymers. Without wishing to be bound by theory, it is believed that the use of an ionic crosslinking agent leads to improved drape and resilience of a fabric treated with a composition comprising a microcapsule as described herein.

[0054] Suitable ionic crosslinking agents include calcium, copper, aluminum, magnesium, strontium, barium, zinc, tin, organic cations, poly(amino acids), poly(ethyleneimine), poly(vinylamine), poly(allyl amine) and polysaccharides, and multivalent anions are selected from the group consisting of dicarboxylic acids, sulfate ions, carbonate ions, poly(acrylic acids), poly(methacrylic acids), copolymers of acrylic acid or methacrylic acid, sulfonated poly(styrene) and poly(styrene) with carboxylic acid groups and mixtures thereof. Particularly preferred are calcium salts, magnesium, sodium, potassium, strontium, barium, zinc and combinations thereof.

[0055] Internal cross linking is cross linking between the microcapsule wall polymers, without the use of a crosslinking agent. The internal crosslinking maybe crosslinking with the same polymer (i.e. a polymer with both positive and negative charges) or between two different polymers forming the microcapsule wall. When two different polymers of opposite charges are utilised, this is referred to as a coacervate formed by coacervation. Preferably a coacervate is formed between a first protein or polysaccharide of one charge and a second protein or polysaccharide of an opposite charge. The ratio between polymer with a positive charge and polymer with a negative charge is preferably between 10 / 0.1 to 0.1 / 10, more preferably between 10 / 1 and 1 / 10 and most preferably between 6 / 1 and 1 / 6.

[0056] An example of a protein with a positive charge maybe gelatin and the protein or polysaccharide with a negative charge maybe selected from the group consisting of gum arabic, xanthan, alginate salts, pectinate salts, carrageenan, polyacrylic and methacrylic acid, xanthan gum and plant gums and / or mixtures thereof.

[0057] Microcapsules which are internally cross linked, i.e. have electrostatic interaction between positive and negative monomers within the microcapsule wall polymers, can be further crosslinked or ‘hardened’ using salt bridges or isocyanate as described above.

[0058] The microcapsule may optionally comprise further crosslinking agents. The further crosslinking agent maybe selected from the group consisting of transglutaminase, peroxidase, secondary plant substances selected from the group consisting of polyphenols, in particular tannin, gallic acid, ferulic acid, hesperidin, cinnamaldehyde, vanillin, carvacrol, and mixtures of two or more of the aforementioned crosslinking agents.

[0059] Microcapsule core materials

[0060] The core may also be referred to as the internal phase. The core of the microcapsule comprises active material and optionally further comprises solvents and / or crosslinking agents as described above. The core is preferably non-aqueous.

[0061] Exemplary active materials include: fragrance; malodour agents for example: uncomplexed cyclodextrin, odor blockers, reactive aldehydes, flavonoids, zeolites, activated carbon, and mixtures thereof; dye transfer inhibitors; shading dyes; silicone oils, resins, and modifications thereof such as linear and cyclic polydimethylsiloxanes, amino-modified, allcyl, aryl, and alkylaryl silicone oils, which preferably have a viscosity of greater than 50,000 cst; insect repellents; organic sunscreen actives, for example, octylmethoxy cinnamate; antimicrobial agents, for example, 2-hydroxy-4, 2,4- trichlorodiphenylether; ester solvents, for example isopropyl myristate; lipids and lipid like substance, for example, cholesterol; hydrocarbons such as paraffins, petrolatum, and mineral oil; fish and vegetable oils; hydrophobic plant extracts; waxes; pigments including inorganic compounds with hydrophobically- modified surface and / or dispersed in an oil or a hydrophobic liquid; sugar-esters, such as sucrose polyester (SPE); and combinations thereof.

[0062] The benefit agents may be dissolved in a solvent. Examples of suitable solvents include vegetable oils, glycerides, esters of fatty acids and branched alcohols, hydrocarbon, etc. specific examples include: diethyl phthalate, isopropyl myristate, Abalyn® (rosin resins, available from Eastman), benzyl benzoate, ethyl citrate, limonene or other terpenes, triacetin or isoparaffins, preferably Abalyn®, benzyl benzoate, limonene or other terpenes, isoparaffins, or combinations thereof. Preferably, if present, the solvent is 0 to 30 wt.% of the active material, more preferably 0 to 20 wt.% and most preferably 0 to 10 wt.% of the active material.

[0063] Most preferably the active material comprises fragrance. Perfume components are well known in the art. Useful perfume components may include materials of both natural and synthetic origin. They include single compounds and mixtures. Specific examples of such components may be found in the current literature, e.g., in Fenaroli's Handbook of Flavor Ingredients, 1975, CRC Press; Synthetic Food Adjuncts, 1947 by M. B. Jacobs, edited by Van Nostrand; or Perfume and Flavor Chemicals by S. Arctander 1969, Montclair, N.J. (USA). These substances are well known to the person skilled in the art of perfuming, flavouring, and / or aromatizing consumer products.

[0064] Particularly preferred perfume components are blooming perfume components and substantive perfume components. Blooming perfume components are defined by a boiling point less than 250°C and a LogP greater than 2.5. Preferably encapsulated perfume compositions comprise at least 20 wt.% blooming perfume ingredients, more preferably at least 30 wt.% and most preferably at least 40 wt.% blooming perfume ingredients. Substantive perfume components are defined by a boiling point greater than 250°C and a LogP greater than 2.5. Preferably encapsulated perfume compositions comprise at least 10 wt.% substantive perfume ingredients, more preferably at least 20 wt.% and most preferably at least 30 wt.% substantive perfume ingredients. Boiling point is measured at standard pressure (760 mm Hg). Preferably a perfume composition will comprise a mixture of blooming and substantive perfume components. The perfume composition may comprise other perfume components.

[0065] It is commonplace for a plurality of perfume components to be present in a microcapsule. In the compositions for use in the present invention it is envisaged that there will be three or more, preferably four or more, more preferably five or more, most preferably six or more different perfume components in a microcapsule. An upper limit of 300 perfume components may be applied.

[0066] Preferably the amount of encapsulated active material is from 5 wt.% to 95 wt.%, preferably 10 wt.% to 90 wt.% more preferably 15 wt.% to 85 wt.%, and most 20 wt.% to 80 wt.% by weight of the microcapsule.

[0067] Additional microcapsule ingredients

[0068] The microcapsule composition may comprise further ingredients. A preferred further ingredient are polyphenols. Particularly preferred are phenols having a 3,4,5-trihydroxyphenyl group or 3,4-dihydroxypheny group such as tannic acid. In additional to polyphenols, other polyols can also be used to prepare the microcapsule compositions of this invention. Examples include pentaerythritol, dipentaerythritol, glycerol, polyglycerol, ethylene glycol, polyethylene glycol, trimethylolpropane, neopentyl glycol, sorbitol, erythritol, threitol, arabitol, xylitol, ribitol, mannitol, galactitol, fucitol, iditol, inositol, volemitol, isomalt, maltitol, lactitol, maltotriitol, maltotetraitol, polyglycitol, polyphenol, and combinations thereof.

[0069] Polyphenols, polyols, and multi-functional aldehydes are preferably present at a level of 0 wt.% to 40 wt.%, preferably 1 wt.% to 35 wt.% more preferably 5 wt.% to 35 wt.% and most preferably 10 wt.% to 30 wt.%.

[0070] Microcapsule composition

[0071] The microcapsules described herein preferably have a diameter of 0.1 microns to 1000 microns, more preferably 0.5 microns to 500 microns, even more preferably 1 micron to 200 microns, and most preferably 1 micron to 100 microns.

[0072] The microcapsules can be positively or negatively charged with a zeta potential of preferably - 200 mV to +200 mV, more preferably 25 mV to 200 mV, and most preferably 40 mV to 100 mV. Preferably, the microcapsules are positively charged. Zeta potential is a measurement of electrokinetic potential in the microcapsule. From a theoretical viewpoint, zeta potential is the potential difference between the water phase (i. e., the dispersion medium) and the stationary layer of water attached to the surface of the microcapsule. The zeta potential can be calculated using theoretical models and an experimentally-determined electrophoretic mobility or dynamic electrophoretic mobility. The zeta potential is conventionally measured by methods such as microelectrophoresis, or electrophoretic light scattering, or electroacoustic phenomena. For more detailed discussion on measurement of zeta potential, see Dukhin and Goetz, "Ultrasound for characterizing colloids", Elsevier, 2002.

[0073] The microcapsule composition of this invention can be a slurry containing a solvent, preferably water. The microcapsules are preferably present in the slurry as 0.1 wt.% to 80 wt.%, more preferably 1 wt.% to 65 wt.% and most preferably 5 wt.% to 45 wt.% by weight of the microcapsule composition. The slurry may comprise a thickening or suspending agent such as xanthan gum, carboxymethyl cellulose (CMC), microcrystalline cellulose (MCC) or guar gum.

[0074] Alternatively, the microcapsule composition of this invention can also be dried, e.g., spray dried, heat dried, and belt dried, to a solid form.

[0075] The microcapsule composition maybe purified by washing the capsule slurry with water until a neutral pH (pH of 6 to 8) is achieved. For the purposes of the present invention, the capsule suspension can be washed using any conventional method including the use of a separatory funnel, filter paper, centrifugation and the like. The capsule suspension can be washed one, two, three, four, five, six, or more times until a neutral pH, e.g., pH 6-8 and 6.5-7.5, is achieved. The pH of the purified capsules can be determined using any conventional method including, but not limited to pH paper, pH indicators, or a pH meter. In certain embodiments of this invention, the purification of the capsules includes the additional step of adding a salt to the capsule suspension prior to the step of washing the capsule suspension with water. Exemplary salts of use in this step of the invention include, but are not limited to, sodium chloride, potassium chloride or bi-sulphite salts. See US 2014 / 0017287.

[0076] Preparation of the microcapsules

[0077] When preparing the microcapsule, the polymers may be provided in a solvent. Suitable solvents for preparing the microcapsule wall include water or mixtures of water with at least one water- miscible organic solvent. Suitable organic solvents include glycerol, 1 ,2-propanediol, 1 ,3- propanediol, ethanediol, diethylene glycol, triethylene glycol, and other analogues. Preferably the solvent is water. A stabiliser may also be present. A stabiliser maybe be selected from acrylic co-polymers, preferably with sulphonate groups, copolymers of acrylamides and acrylic acid, copolymers of alkyl acrylates and N-vinylpyrrolidone, such as LUVISKOL® K15, K30 or K90 (BASF); sodium polycarboxylates, sodium polystyrene sulfonates, vinyl and methyl vinyl ether-maleic acid anhydride copolymers as well as ethylene, isobutylene or styrene-maleic acid anhydride copolymers, microcrystalline cellulose, which is commercially available, for example, under the name VIVAPUR®, diutan gum, xanthan gum or carboxymethyl celluloses.

[0078] The crosslinking of the microcapsule preferably involves a catalyst. The catalyst may be present in the microcapsule core active material or added separately to the oil-in-water emulsion or dispersion. A preferred catalyst for the formation of microcapsules according to the present invention is diazabicyclo[2.2.2]octane (DABCO), also known as triethylenediamine (TEDA). Also suitable are catalysts based on bismuth or tin, transglutaminase, peroxidase, secondary plant compounds selected from the group, which consists of polyphenols, in particular tannin, gallic acid, ferulic acid, hesperidin, cinnamaldehyde, vanillin, carvacrol, and mixtures thereof.

[0079] Alternatively, or additionally the formation of the microcapsules may be catalyst by heating the oil-in-water emulsion or dispersion. For example, heating to a temperature range of a temperature in the range of 60 °C to 90 °C.

[0080] Various suitable methods of production may be implemented to produce the microcapsules suitable for use in the present invention.

[0081] One suitable method is interfacial polymerization. An example of interfacial polymerization involves the steps of:

[0082] (i) Providing the microcapsule core materials including at least one first crosslinking agent, wherein the crosslinking agent is substantially dissolved together with the core materials, this is the oil phase. A non-aqueous solvent many optionally be present;

[0083] (ii) Providing the microcapsule wall materials comprising at least one protein and / or at least one polysaccharide. This is the aqueous phase. An aqueous solvent many optionally be present; (iii) Emulsifying or dispersing the microcapsule core materials with the microcapsule wall materials. Preferably in a ratio of from 70 : 30 to 60 : 40, preferably in a range from 30 : 70 to 60 : 40. Optionally an emulsifier may be used. Emulsification may be achieved by use of high-speed mixing. After completion of this stage, an oil-in-water emulsion or dispersion is present in which the internal phase with the active materials to be encapsulated is finely emulsified or dispersed in the external wall material phase in the form of droplets;

[0084] (v) First crosslinking optionally by the addition of at least one catalyst to obtain a microcapsule slurry, optionally with the addition of further protein and / or polysaccharide polymers;

[0085] (vi) Curing the microcapsule slurry, preferably at a temperature of at least 60 °, preferably for at least 30 minutes, followed by cooling;

[0086] (v) Optionally drying, using methods such as spray drying, filtration, or freeze drying.

[0087] An alternative method involves 3D printing the microcapsules. Both the microcapsule shell and microcapsule core can be printed using a printing system. See WO2016172699A1. The printing steps generally include depositing the active materials and the microcapsule shell material in a layer-by-layer fashion, preferably through separate printer heads.

[0088] Hydrocolloid

[0089] The laundry composition comprises a hydrocolloid. Hydrocolloids are polymers characterised by their property of forming viscous dispersions and / or gels when dispersed in water.

[0090] “Hydrocolloids” (“hydrophilic colloids”) are macromolecules that have a largely linear shape and have intermolecular interaction forces that provide for secondary and main valence bonds between the individual molecules and thus provide for the formation of a net-like structure. Preferably the hydrocolloid comprises a polysaccharide, protein, modified polysaccharide, modified protein, or combinations thereof.

[0091] Hydrocolloids are natural or synthetic polymers that form gels or viscous solutions in aqueous systems. Hydrocolloids increase the viscosity of the water by either binding water molecules (hydration) or absorbing and enveloping the water in their interconnected macromolecules, while at the same time restricting the mobility of the water. Examples of suitable hydrocolloids include: fully synthetic compounds, such as polyacrylic and polymethacrylic compounds, vinyl polymers, polycarboxylic acids, polyethers, polyimines and polyamides, natural compounds, such as agar-agar, carrageenan, tragacanth, gum arabic, alginates, pectins, polyoses, guar flour, alginate, locust bean gum, starch, dextrins, gelatin, xanthan gum and casein, modified natural substances, such as carboxymethyl cellulose and other cellulose ethers, hydroxyethyl and hydroxypropyl cellulose, and inorganic compounds, such as polysilicic acids, clay minerals such as montmorillonites, zeolites and silicic acids.

[0092] Preferably the hydrocolloid of the present invention is derived from a natural source (modified or unmodified), i.e. vegetable (including seaweeds), animal or microbial derived polymers. In other words the hydrocolloid is isolated from vegetable sources (including seaweeds), animal sources or bacterial sources.

[0093] Preferably the hydrocolloid comprises natural polymers selected from: agar, carrageenan, tragacanth, gum arabic, alginates, pectins, polyoses, guar flour, alginate, locust bean gum, starch, dextrins, gelatin and / or casein, xanthan gum, carboxymethyl cellulose and other cellulose ethers, hydroxyethyl and hydroxypropyl cellulose and combinations thereof.

[0094] More preferably the hydrocolloids comprises a material selected from: agar, gelatin, carrageenan, alginate, locust bean gum, pectin, xanthan gum, carboxymethyl cellulose, micorcrystaline cellulose and combinations thereof. Most preferably the hydrocolloid comprises carrageenan, more preferably the hydrocolloid comprises kappa carrageenan.

[0095] The laundry compositions of the present invention comprise 0.5 to 10 wt.% hydrocolloid by weight of the laundry composition, more preferably 1 to 7 wt.% hydrocolloid, most preferably 1.25 wt.% to 5 wt.% hydrocolloid, most preferably 0.15 to 4 wt.% hydrocolloid by weight of the laundry composition.

[0096] Salt

[0097] The compositions described herein comprise salt. The salt preferably comprises monovalent salt. Preferably the cation is selected from sodium, potassium, calcium, lithium and combinations thereof. Preferably the anion comprises chloride. More preferably the salt comprises salt selected from: sodium chloride, potassium chloride, calcium chloride, lithium chloride and combinations thereof. Most preferably the salt comprises salt selected from sodium chloride and / or potassium chloride. The combination of sodium chloride and potassium chloride provide the optimal dissolution and product robustness.

[0098] The salt may be added directly to the composition neat or in a solution for example a salt water solution. Alternatively, the composition maybe dropped into a curing bath comprising the salt wherein the salt ‘cures’ the composition and becomes part of the composition.

[0099] The laundry compositions preferably comprise 0.00001 to 3 wt. % salt by weight of the laundry composition, more preferably 0.00005 to 2 wt.% salt, even more preferably 0.0001 to 1 wt.% salt, most preferably 0.0005 to 0.5 wt.% salt.

[0100] Water

[0101] The laundry compositions described here comprise 50 to 99 wt.% water, by weight of the laundry composition. More preferably 65 to 98 wt.% water, more preferably 70 to 97 wt.% water, even more preferably 75 to 96 wt.% water, even more preferably 80 to 95 wt.% water, most preferably 85 to 95 wt.% water, by weight of the laundry composition.

[0102] Other ingredients

[0103] The laundry compositions described herein may comprise further ingredients. Preferred additional ingredients maybe selected from: free (unencapsulated) perfumes, film forming polymers, fluorescers, dye-transfer inhibitors, natural oils, fabric softening actives (such as quaternary ammonium compounds), enzymes, shading dyes, antibacterial agents and combinations thereof.

[0104] Articles

[0105] The laundry compositions produced by the method described herein may be in the form of form of an article having a diameter maximum linear diameter of 0.2 mm to 300 mm, preferably 0.5 mm to 200mm and most preferably 1 mm to 150 mm. The maximum linear dimension is the largest cross-sectional diameter of the article and may be measured in any suitable way, for example using calipers. The article may be in the form of particles, sheets, supplied in a unit dose package or any other suitable form for use in the homecare applications, in particular the laundry process. Preferably the compositions are in the form of particles or unit dose. Preferred unit dose packages comprise a water-soluble film such as PVOH or a non-soluble pack from which the consumer dispenses the contents. Particles are preferably defined as objects having a maximum linear dimension in any direction of 1 to 50 mm. The particles may be any suitable shape, for example spheres, hemispheres, cubes, oblongs, elliptical, or recognisable shapes such as leaves or flowers, such shapes are obtained from different shaped molds. The articles may be supplied to the consumer alone or incorporated into another homecare product, such as a distinct particle in a liquid homecare composition or mixed into a homecare powder.

[0106] Sheets refer to large thin composition, such compositions preferably have a maximum linear dimension of 300 mm, more preferably 200mm and most preferably 150mm. Such compositions preferably have a maximum depth of 3 mm, more preferably 2 mm, most preferably 1 mm.

[0107] Preferably the laundry composition is in the form of particles, the particles may be free flowing or packaged within a unit dose package. Preferably the particles have a maximum linear dimension in any direction of 1 to 40 mm, more preferably 1.5 mm to 30 mm and most preferably 2 mm to 20mm.

[0108] The laundry compositions described herein may be used in any stage of the laundry process and may be used in hand washing or in a washing machine. Preferably the compositions are used in the wash stage of the laundry process.

[0109] The compositions described herein may be made by any suitable method. Generally, the composition may be made by: i) mixing a salt curing composition with the other ingredients in the composition; or ii) preparing a composition containing all ingredients other than the salt, then exposing this mixture to a salt curing solution.

[0110] When preparing particles, the following method may be followed.

[0111] Preferably a curing composition is prepared. For process i) the curing composition may simply comprise salt. Preferably the curing composition comprises water and salt. The solution preferably comprises salt in a concentration of 0.01 to 10 Molar, more preferably 0.05 to 5 Molar, even more preferably 0.01 to 4 Molar and most preferably 0.01 to 2.5 Molar. Separately the hydrocolloid may be dispersed in water. The hydrocolloid solution is preferably prepared by dispersing the hydrocolloid in water. The hydrocolloid may be dispersed in water before heating, during heating the water or once the water has reached maximum heating temperature. The water or water and hydrocolloid are preferably heated to 40°C to 100°C, more preferably 45°C to 95°C and most preferably 50°C to 80°C. The concentration of hydrocolloid in water is preferably 0.1 to 10 wt.% by weight of the solution, more preferably 0.25 to 5 wt.% by weight of the solution, most preferably 1 to 2 wt.% by weight of the solution. All remaining ingredients maybe added to the solution, for example microcapsules, softening agents, dyes, etc. and thoroughly mixed. This mix is referred to as the hydrocolloid solution. It is preferred to disperse the hydrocolloid in water before adding any other ingredients, however alternative orders of addition are possible.

[0112] Following process i) the curing composition is mixed into the hydrocolloid solution. The curing composition may be added at any stage, however it is preferred that the curing composition is the last ingredient to be added. The curing composition is added to deliver the preferred quantity of salt. Once all ingredients are mixed, the mixture is dispensed (preferably dripped or poured) onto a surface or into a mould, where the solution solidifies and forms a particle. Preferably the mixture is at a temperature of 35°C to 70°C, more preferably 40°C to 70°C and most preferably 45°C to 65°C when dropped onto a surface or into a mould. The temperature of the surface or mould is preferably 15°C to 30°C, more preferably 17°C to 27°C.The solidified composition is allowed to dry.

[0113] Process i) described herein may be carried out using any suitable equipment. On a small scale the method may be carried out manually using a pipette to dispense droplets of the composition onto a surface or into moulds. On a larger scale, traditional casting methods may be applied.

[0114] Following process ii) the hydrocolloid solution is dripped into the curing salt solution. Preferably the hydrocolloid solution is at a temperature of 35°C to 70°C, more preferably 40°C to 70°C and most preferably 45°C to 65°C when dropped into the curing composition. The temperature of the curing composition is preferably 15°C to 30°C, more preferably 17°C to 27°C. The solidified beads are then removed from the curing composition and allowed to dry.

[0115] Process ii) described herein may be carried out using any suitable equipment. On a small scale the method may be carried out manually using a pipette to dispense droplets of the hydrocolloid solution into the curing composition. On a larger scale, the droplet formation may be by co-axial 5 air flow, vibration such as a vibrating membrane, electrostatic interactions or mechanical cutting to break a liquid jet into droplets such as a cutting wheel. Manufacturers of suitable equipment include Nisco Engineering, geniaLab, and Maag Group under the trade name DROPPO®.

[0116] Examples

[0117] Table 1 - Microcapsules synthesized via interfacial polymerization: The following compositions were produced: Table 2: Ancillary compositions prepared for testing:

[0118] All of the materials used to create the microcapsules and the ancillary compositions were sourced from Europe.

[0119] The above compositions were converted into beads by a process as described previously in the description. The mixture was stirred at a temperature of 65°C and the temperature of the mould was around 20°C.

[0120] This process resulted in a range of particle sizes, but a selection were measured and the average longest dimension was found to be around 6mm.

[0121] The dried beads made from compositions A, 1 and 2 were then each washed in a Tergotometer wash study. The Tergotometer is model wash system comprising multiple open metal beakers that can be stirred via the use of a mechanical stirring arm. During an experiment each beaker can be setup to contain a specific combination of laundry ingredients. Since the fabrics used in each beaker are known specific liquor : cloth ratios can be achieved. Furthermore, the water used for the laundry process can also be controlled.

[0122] Such a system provides for good testing of laundry compositions that is representative of performance in full scale washing machines.

[0123] The standard experimental protocol for all the wash experiments can be summarised as follows: a) 11 of municipal water was added to each Tergotometer pot (12°FH) b) 1.125g of each bead composition was added to a separate Tergotometer pot. c) The wash temperature was set at 25°C. d) The Tergotometer stirrer speed was set at ~100rpm. e) Stirring proceeded for approximately 10 minutes such that the beads appeared fully dissolved. f) 3 “Terry toweling” monitors were then added to each of the pots (3 cloths have a mass of 40g to the nearest gram, such that the material to liquor ratio was 1 :25 by weight). g) The mixture was stirred for a further 10 minutes. h) Mixing was then stopped and the cloths removed. They were hand squeezed to remove excess water and allowed to dry naturally in a drying cabinet overnight.

[0124] The above process was repeated 4 times to ensure experimental robustness, and the mixtures were varied across each Tergotometer pot. This resulted in 12 cloths being washed for each composition.

[0125] 10 out of 12 cloths for each test condition were randomly selected and the resulting dried cloths were then assessed on a PhabrOmeter® supplied by Nu Cybertek, Inc. Measurements for Resilience, Softness and Relative Hand Value using a method according to AATCC TM202- 2012 (2020), Relative Hand Value of Textiles: Instrumental Method.

[0126] The average results obtained are shown below in table 2 and normalized with respect to the control microcapsules comprising melamine formaldehyde shells. Table 3 - performance assessment

[0127] A lower Resilience Score is desired because this is a measure of how much effort is required for the end user to bend the fabric with their fingers.

[0128] An increased Softness Score is desired because softer fabrics are preferred by consumers.

[0129] An increased Relative Hand Value is desired because this gives a value based on the three underlying measurements of softness, stiffness and smoothness (as further detailed in the article by N Pan in the International Journal of Design and Nature, Vol. 1 , Issue 1, Pages 48-60) and so is a good guide for overall fabric preference by consumers.

[0130] The results clearly demonstrate that compositions according to the invention are superior to those instead comprising microcapsules with a melamine formaldehyde shell.

Claims

Claims1. A laundry composition in the form of an article having a diameter maximum linear diameter of 0.2 mm to 300 mm, wherein the laundry composition comprises: a. 0.01 to 20 wt.% microcapsules; b. 0.5 to 10 wt.% hydrocolloid; c. salt; and d. 50 to 99 wt.% water; and wherein the microcapsules have a microcapsule wall and the microcapsule wall comprises protein polymer, polysaccharide polymer or combinations thereof.

2. A laundry composition according to any preceding claim wherein the microcapsules encapsulate fabric benefit agents comprising perfume.

3. A laundry composition according to any preceding claim wherein the laundry composition comprises 0.01 to 20 wt.% microcapsules by weight of the laundry composition.

4. A laundry composition according to any proceeding claim, wherein the microcapsules comprise 20 wt.% to 98 wt.% protein polymer, polysaccharide polymer or combinations thereof, by weight of the microcapsule.

5. A laundry composition according to any proceeding claim, wherein the microcapsule wall comprises: pea protein, potato protein, brown rice protein, white rice protein, wheat protein, egg protein, barley protein, pumpkin seed protein, oat protein, almond protein, whey, casein, silk protein, gelatin, algae protein, rye protein, spelt protein, gluten, rapeseed protein, sunflower protein, corn protein, soybean protein, bean protein, chickpea protein, lentil protein, lupin protein, peanut protein, alfalfa protein, hemp protein, chitosan protein, fiber polysaccharides, starch, sugar alcohols, sugars and mixtures thereof.

6. A laundry composition according to any proceeding claim, wherein the microcapsule wall polymers are crosslinked.

7. A laundry particle according to claim 6, wherein the microcapsules comprise a crosslinking agent selected from: isocyanate crosslinking, salt bridge cross linking, internal crosslinking and combinations thereof.

8. A laundry particle according to claim 6, wherein the microcapsules comprise 0.1 wt.% to 10 wt.% crosslinking agent by weight of the microcapsule.

9. A laundry composition according to any preceding claim, wherein the hydrocolloid comprises polymers selected from: agar, carrageenan, tragacanth, gum arabic, alginates, pectins, polyoses, guar flour, alginate, locust bean gum, starch, dextrins, gelatin and / or casein, xanthan gum, carboxymethyl cellulose and other cellulose ethers, hydroxyethyl and hydroxypropyl cellulose and combinations thereof.

10. A laundry composition according to any preceding claim, wherein the salt comprises monovalent salt.

11. A laundry composition according to any preceding claim, wherein the composition comprises 0.00001 to 3 wt. % salt.

12. A laundry composition according to any proceeding claim, wherein the composition is in the form of particles, sheet, or unit dose.

13. A laundry composition according to any proceeding claim, wherein the composition is in the form of particles having a maximum linear dimension in any direction of 1 to 40 mm.

14. A method of using a laundry composition according to any preceding claim to provide fabric care, wherein the particle is added to the wash stage of the laundry process.

15. A use of a laundry composition according to claims 1 to 13 to provide fabric care to a laundered fabric.