METHOD OF IMPROVING FABRIC CARE

Field of the Invention

The present invention relates to fabric sprays.

Background of the Invention

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 compositions which provide fabric care benefits to fabrics.

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

Microcapsules are used in various 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.

There remains a need for fabric sprays which provide fabric care to fabrics.

Summary of the Invention

It has been found that the use of a microcapsules comprising protein or polysaccharides in fabric spray compositions leads to improved fabric care, in particular improved hand of fabrics.

Accordingly in a first aspect of the present invention is provided a method of improving fabric care wherein 0.1 to 20 ml per m ² of an aqueous fabric spray composition comprising: a Microcapsules; and b Free perfume; wherein the microcapsules have a microcapsule wall and the microcapsule wall comprises protein polymers, polysaccharide polymers, or combinations thereof; is sprayed onto a fabric.

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

Detailed Description of the Invention

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.

By microcapsule composition it is herein understood to mean the composition comprising microcapsules which is added to a laundry composition. The microcapsule composition may comprise only microcapsules or may be in the form of a slurry comprising microcapsules.

By microcapsule it is herein understood to mean the microcapsule (wall and core) without the present of a solvent or slurry.

The fabric sprays for use in the present invention comprise microcapsules. The microcapsules may be provided simply as microcapsules but preferably are provided in a microcapsule composition comprising microcapsules 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 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.

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

Microcapsule wall materials

The microcapsule wall may also be referred to as the microcapsule shell. The microcapsule wall comprises protein polymers, polysaccharide polymers, or combinations 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. Without wishing to be bound by theory, it is believed that the use of proteins or polysaccharides improves the ‘hand’ of a fabric when treated with compositions comprising the microcapsules described herein. The microcapsule wall materials are preferably in an aqueous solution. The microcapsule wall preferably comprises 20 wt.% to 100 wt.% protein, polysaccharide, or combinations thereof, 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.

As is conventional in the art, a “polypeptide” or “protein” 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 polypeptide 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.

Suitable proteins for use in this invention include whey proteins, plant proteins and gelatine. Preferably the 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, proteins resulting from fermentation, proteins from food waste 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. 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.

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.

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 or grain proteins and 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.

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.

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

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.

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.

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.

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.

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.

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.

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.

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

An example of suitable sugar includes: glucose.

Particularly preferred polysaccharides include: gum Arabic, dextrins and maltodextrins are particularly preferred.

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.

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 or combinations thereof.

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.

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 cross linking 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.

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.

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.

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. 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.

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). 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.

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.

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.

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.

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

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.

Suitable ionic crosslinking agents maybe selected from: calcium, copper, aluminum, magnesium, strontium, barium, zinc, tin, organic cations, poly(amino acids), poly(ethyleneimine), poly(vinylamine), poly(allyl amine), 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.

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.

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 mixtures thereof.

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.

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.

Microcapsule core materials

The core may also be referred to as the internal phase. The core of the microcapsule comprises active material and optionally further comprises solvents, crosslinking agents as described above, or combinations thereof. The core is preferably non-aqueous. The internal non-aqueous phase may preferably comprise from 20 to 80 wt.%, preferably from 25 to 75 wt.% and even more preferably from 33 to 50 wt.% active material to be encapsulated and preferably from 0.1 to 5 wt.%, preferably from 0.15 to 3.5 wt.% and even more preferably from 0.5 to 2.5 wt.% crosslinking agent and the remaining composition solvent.

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.

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.

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. 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 comprises 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.

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.

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.

Additional microcapsule ingredients

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.

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.%. Microcapsule composition

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.

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 (/. 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.

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.

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

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.

Preparation of the microcapsules

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.

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.

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.

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

One suitable method if interfacial polymerization. An example of interfacial polymerization involves the steps of: (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;

(ii) Providing the microcapsule wall materials comprising at least one protein, one polysaccharide, or combinations thereof. 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;

(iv) First crosslinking optionally by the addition of at least one catalyst to obtain a microcapsule slurry, optionally with the addition of further protein polymers, polysaccharide polymers, or combinations thereof;

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

(vi) Optionally drying, using methods such as spray drying, filtration, or freeze drying.

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.

Spray compositions

The fabric spray compositions for use in the present invention comprise 0.01 to 20 wt.% microcapsules, by weight of the composition. More preferably 0.05 to 10 wt.% microcapsules, most preferably 0.1 to 5 wt.% microcapsules.

The compositions for use in the present invention are aqueous fabric sprays. Preferably at least 60 wt.% of the composition is water, more preferably at least 70 wt.%. The compositions for use in the present invention comprise free perfume in addition to any perfume contained in microcapsules.

Free perfume may be present at a level selected from: less than 10 wt.%, less than 8 wt.%, and less than 5 wt.%, by weight of the spray composition. Free perfume may be present at a level selected from: more than 0.0001 wt.%, more than 0.001 wt.%, and more than 0.01 wt.%, by weight of the spray composition. Suitably free perfume is present in the spray composition in an amount selected from the range of from about 0.0001 wt.% to about 10 wt.%, preferably from about 0.001 wt.% to about 8 wt.%, more preferably from about 0.01 wt.% to about 5 wt.%, by weight of the spray composition.

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.

A wide variety of chemicals are known for perfume use including materials such as aldehydes, ketones, esters and the like. More commonly, naturally occurring plant and animal oils and exudates comprising complex mixtures of various chemical components are known for use as perfume, and such materials can be used herein. Typical perfumes can comprise e.g. woody/earthy bases containing exotic materials such as sandalwood oil, civet and patchouli oil. The perfume also can be of a light floral fragrance e.g. rose or violet extract. Further the perfume can be formulated to provide desirable fruity odours e.g. lime, lemon or orange.

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. Substantive perfume components are defined by a boiling point greater than 250°C and a LogP greater than 2.5. Preferably a perfume composition will comprise a mixture of blooming and substantive perfume components. The perfume composition may comprise other perfume components. It is commonplace for a plurality of perfume components to be present in a free oil perfume composition. 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. An upper limit of 300 perfume components may be applied.

The free perfume of the present invention is preferably in the form of an emulsion. The particle size of the emulsion can be in the range from about 1 nm to 30 microns and preferably from about 100 nm to about 20 microns. The particle size is measured as a volume mean diameter, D[4, 3] , this can be measured using a Malvern Mastersizer 2000 from Malvern instruments.

Free oil perfume may form an emulsion in the present compositions. The emulsions may be formed outside of the composition or in situ. When formed in situ, at least one emulsifier is preferably added with the free oil perfume to stabilise the emulsion. Preferably the emulsifier is anionic or non-ionic. Examples suitable anionic emulsifiers for the free oil perfume are alkylarylsulphonates, e.g., sodium dodecylbenzene sulphonate, alkyl sulphates e.g., sodium lauryl sulphate, alkyl ether sulphates, e.g., sodium lauryl ether sulphate nEO, where n is from 1 to 20 alkylphenol ether sulphates, e.g., octylphenol ether sulphate nEO where n is from 1 to 20, and sulphosuccinates, e.g., sodium dioctylsulphosuccinate. Examples of suitable nonionic surfactants used as emulsifiers for the free oil perfume are alkylphenol ethoxylates, e.g., nonylphenol ethoxylate nEO, where n is from 1 to 50, alcohol ethoxylates, e.g., lauryl alcohol nEO, where n is from 1 to 50, ester ethoxylates, e.g., polyoxyethylene monostearate where the number of oxyethylene units is from 1 to 30 and PEG-40 hydrogenated castor oil.

The compositions for use in the present invention may comprise one or more perfume compositions. The perfume compositions may be in the form of a mixture of free perfumes compositions or a mixture of encapsulated and free oil perfume compositions.

The spray composition for use in the present invention preferably comprises a non-ionic surfactant. Preferably the spray comprises 0.01 to 15 wt.% non-ionic surfactant, more preferably 0.1 to 10 wt.% non-ionic surfactant, most preferably 0.1 to 5 wt.% non-ionic surfactant. The correct amount of non-ionic surfactant is important can be important for achieving the desired delivery of the perfume. The spray may require sufficient surfactant to carry the surfactant, however too much surfactant will interfere with the action of the spray. The non-ionic surfactants will preferably have an HLB value of 12 to 20, more preferably 14 to 18.

Examples of non-ionic surfactant materials include: ethoxylated materials, polyols such as polyhydric alcohols and polyol esters (including glycerol esters), alkyl polyglucosides, EO-PO block copolymers (Poloxamers). Preferably, the non-ionic surfactant is selected from ethoxylated materials.

Preferred ethoxylated materials include: fatty acid ethoxylates, fatty amine ethoxylates, fatty alcohol ethoxylates, nonylphenol ethoxylates, alkyl phenol ethoxylate, amide ethoxylates, Sorbitan(ol) ester ethoxylates, glyceride ethoxylates (castor oil or hydrogenated castor oil ethoxylates) and mixtures thereof.

More preferably, the non-ionic surfactant is selected from ethoxylated surfactants having a general formula:

RIO(R ₂ O) _X H

RI = hydrophobic moiety.

R ₂ = C ₂ H ₄ or mixture of C ₂ H ₄ and C3H6 units x = 4 to 120

R1 preferably comprises 8 to 25 carbon atoms and mixtures thereof, more preferably 10 to 20 carbon atoms and mixtures thereof most preferably 12 to 18 carbon atoms and mixtures thereof. Preferably, R is selected from the group consisting of primary, secondary and branched chain saturated and/or unsaturated hydrocarbon groups comprising an alcohol, carboxy or phenolic group. Preferably R is a natural or synthetic alcohol.

R2 preferably comprises at least 50% C2H4, more preferably 75% C2H4, most preferably R2 is C2H4. x is preferably 8 to 90 and most preferably 10 to 60. Examples of commercially available, suitable non-ionic surfactants include: Genapol C200 ex.

Clariant and Eumulgin CO40 ex. BASF.

Malodour ingredients

Compositions for use in the present invention preferably comprise anti-malodour ingredient(s). Malodour ingredients maybe in addition to traditional free perfume ingredients.

Anti-malodour agent may be present at a level selected from: less than 20%, less than 10%, and less than 5%, by weight of the spray composition. Suitably anti-malodour agent are present in the spray composition in an amount selected from the range of from about 0.01% to about 5%, preferably from about 0.1% to about 3%, more preferably from about 0.5% to about 2%, by weight of the spray composition.

Any suitable anti-malodour agent may be used. Indeed, an anti-malodour effect may be achieved by any compound or product that is effective to “trap”, “absorb” or “destroy” odour molecules to thereby separate or remove odour from the garment or act as a "malodour counteractant". The odour control agent may be selected from the group consisting of: uncomplexed cyclodextrin; odour blockers; reactive aldehydes; flavanoids; zeolites; activated carbon; a mixture of zinc ricinoleate or a solution thereof and a substituted monocyclic organic compound; and mixtures thereof.

Lubricants:

The spray compositions for use in the present invention preferably comprise lubricants. Lubricants may be silicone based lubricants or non-silicone based lubricants.

Lubricant materials may be present at a level selected from: less than 10 %, less than 8 %, and less than 6 %, by weight of the spray composition. Lubricant materials may be present at a level selected from: more than 0.5 %, more than 1 %, and more than 1.5 %, by weight of the spray composition. Suitably Lubricant materials are present in the spray composition in an amount selected from the range of from about 0.5 % to about 10 %, preferably from about 1 % to about 8 %, more preferably from about 1.5 % to about 6 %, by weight of the spray composition. Any lubricants are present in addition to the ester oil. Examples of non-silicone based lubricants include fabric softening quaternary ammonium compounds, amines, fatty acid esters, clays, waxes, polyolefins, polymer latexes, synthetic and natural oils.

Preferably the lubricant is a fabric softening quaternary ammonium compounds or a silicone- based lubricant. Most preferably the lubricant is a silicone based lubricant.

For the purposes of the present invention, fabric softening quaternary ammonium compounds are so called "ester quats". Particularly preferred materials are the ester-linked triethanolamine (TEA) quaternary ammonium compounds comprising a mixture of mono-, di- and tri-ester linked components.

A first group of quaternary ammonium compounds (QACs) suitable for use in the present invention is represented by formula (I):

[(CH _? ) _n (TR)] _m wherein each R is independently selected from a C5 to C35 alkyl or alkenyl group; R1 represents a C1 to C4 alkyl, C2 to C4 alkenyl or a C1 to C4 hydroxyalkyl group; T may be either O-CO. (i.e. an ester group bound to R via its carbon atom), or may alternatively be CO-O (i.e. an ester group bound to R via its oxygen atom); n is a number selected from 1 to 4; m is a number selected from 1, 2, or 3; and X- is an anionic counter-ion, such as a halide or alkyl sulphate, e.g. chloride or methylsulfate. Di-esters variants of formula I (i.e. m = 2) are preferred and typically have mono- and tri-ester analogues associated with them. Such materials are particularly suitable for use in the present invention.

Suitable actives include soft quaternary ammonium actives such as Stepantex VT90, Rewoquat WE18 (ex-Evonik) and Tetranyl L1/90N, Tetranyl L190 SP and Tetranyl L190 S (all ex- Kao).

A second group of QACs suitable for use in the invention is represented by formula (III): wherein each R1 group is independently selected from C1 to C4 alkyl, or C2 to C4 alkenyl groups; and wherein each R2 group is independently selected from C8 to C28 alkyl or alkenyl groups; and n, T, and X- are as defined above. Preferred materials of this third group include bis(2-tallowoyloxyethyl)dimethyl ammonium chloride, partially hardened and hardened versions thereof.

A particular example of the second group of QACs is represented the by the formula:

A second group of QACs suitable for use in the invention are represented by formula (V)

R1 and R2 are independently selected from C10 to C22 alkyl or alkenyl groups, preferably C14 to C20 alkyl or alkenyl groups. X- is as defined above.

The iodine value of the quaternary ammonium fabric conditioning material is preferably from 0 to 80, more preferably from 0 to 60, and most preferably from 20 to 50.

Silicones and their chemistry are described in, for example in The Encyclopaedia of Polymer Science, volume 11 , p765.

Silicones suitable for the present invention are fabric softening silicones. Non-limiting examples of such silicones include:

• Non-functionalised silicones such as polydimethylsiloxane (PDMS),

• Functionalised silicones such as alkyl (or alkoxy) functionalised, alkylene oxide functionalised, amino functionalised, phenyl functionalised, hydroxy functionalised, polyether functionalised, acrylate functionalised, siliconhydride functionalised, carboxy functionalised, phosphate functionalised, sulphate functionalised, phosphonate functionalised, sulphonic functionalised, betaine functionalised, quarternized nitrogen functionalised and mixtures thereof.

• Copolymers, graft co-polymers and block co-polymers with one or more different types of functional groups such as alkyl, alkylene oxide, amino, phenyl, hydroxy, polyether, acrylate, siliconhydride, carboxy, phosphate, sulphonic, phosphonate, betaine, quarternized nitrogen and mixtures thereof.

Suitable non-functionalised silicones have the general formula:

Ri - Si (R ₃ ) ₂ - O - [- Si (R ₃ ) ₂ - O -] _x - Si(R ₃ ) ₂ - R ₂

Ri = hydrogen, methyl, methoxy, ethoxy, hydroxy, propoxy, and aryloxy group. R2 = hydrogen, methyl, methoxy, ethoxy, hydroxy, propoxy, and aryloxy group. R ₃ = alkyl, aryl, hydroxy, or hydroxyalkyl group, and mixtures thereof

A suitable example of a PDMS polymer is E22 ex. Wacker Chemie.

Suitable functionalised silicones may be anionic, cationic, or non-ionic functionalised silicones. The functional group(s) on the functionalised silicones are preferably located in pendent positions on the silicone i.e. the composition comprises functionalised silicones wherein the functional group(s) are located in a position other than at the end of the silicone chain. The terms ‘terminal position’ and ‘at the end of the silicone chain’ are used to indicate the terminus of the silicone chain.

When the silicones are linear in nature, there are two ends to the silicone chain. In this case the anionic silicone preferably contains no functional groups located on a terminal position of the silicone. When the silicones are branched in nature, the terminal position is deemed to be the two ends of the longest linear silicone chain. Preferably no functional group(s) are located on the terminus of the longest linear silicone chain.

Preferred functionalised silicones are those that comprise the anionic group at a mid-chain position on the silicone. Preferably the functional group(s) of the functionalised silicone are located at least five Si atoms from a terminal position on the silicone. Preferably the functional groups are distributed randomly along the silicone chain. For best performance, it is preferred that the silicone is selected from: carboxy functionalised silicone; anionic functionalised silicone; non-functionalised silicone; and mixtures thereof. More preferably, the silicone is selected from: carboxy functionalised silicone; amino functionalised silicone; polydimethylsiloxane (PDMS) and mixtures thereof. Preferred features of each of these materials are outlined herein. Most preferably the silicone is selected from amino functionalised silicones; polydimethylsiloxane (PDMS) and mixtures thereof.

A carboxy functionalised silicone may be present as a carboxylic acid or an carbonate anion and preferably has a carboxy group content of at least 1 mol% by weight of the silicone polymer, preferably at least 2 mol%. Preferably the carboxy group(s) are located in a pendent position, more preferably located at least five Si atoms from a terminal position on the silicone. Preferably the caboxy groups are distributed randomly along the silicone chain. Examples of suitable carboxy functional silicones include FC 220 ex.

Wacker Chemie and X22-3701 E ex. Shin Etsu.

An amino functionalised silicone means a silicone containing at least one primary, secondary or tertiary amine group, or a quaternary ammonium group. The primary, secondary, tertiary and/or quaternary amine groups are preferably located in a pendent position, more preferably located at least five Si atoms from a terminal position on the silicone. Aminosilicones suitable for use in the invention will preferably have an amine content of the composition of 0.001 to 3 meq/g, more preferably 0.01 to 2.5 meq/g, most preferably 0.05 to 1.5 meq/g, which is measured as the consumption of 1 N hydrochloric acid in ml/g by the composition on titration to the neutral point. Peferably the amino groups are distributed randomly along the silicone chain.

Examples of suitable amino functional silicones include FC222 ex. Wacker Chemie and EC218 ex. Wacker Chemie.

The molecular weight of the silicone polymer is preferably from 1 ,000 to 500,000, more preferably from 2,000 to 250,000 even more preferably from 5,000 to 200,000.

Setting polymers

The fabric spray for use in the present invention may preferably further comprise one or more setting polymers, “setting polymer” means any polymer which refers to polymer having properties of film-formation, adhesion, or coating deposited on a surface on which the polymer is applied. The setting polymer may be present at a level selected from: less than 10 %, less than 7.5 %, and less than 5 %, by weight of the spray composition. The setting polymer may be present at a level selected from: more than 0.5 %, more than 1 %, and more than 1.5 %, by weight of the spray composition. Suitably the setting polymer is present in the spray composition in an amount selected from the range of from about 0.5 % to about 10 %, preferably from about 1 % to about 7.5 %, more preferably from about 1.5 % to about 5 %, by weight of the fabric spray composition.

The molecular weight of the setting polymer is preferably from 1 ,000 to 500,000, more preferably from 2,000 to 250,000 even more preferably from 5,000 to 200,000.

The setting polymer for use in the present invention may be any water-soluble or water dispersible polymer. Preferably the polymer is a film-forming polymer or mixture of such polymers. This includes homopolymers or copolymers of natural or synthetic origin having functionality rendering the polymers water-soluble such as hydroxyl, amine, amide or carboxyl groups. The setting polymers may be cationic, anionic, non-ionic or amphoteric.

The polymers make be a single species of polymer or a mixture thereof. Preferably the setting polymer is selected from: anionic polymers, non-ionic polymers, amphoteric polymers and mixtures thereof. For all polymers herein described it is intended to cover both the acids and salts thereof.

Suitable cationic setting polymers are preferably selected from the group consisting of: quaternized acrylates or methacrylates; quaternary homopolymers or copolymers of vinylimidazole; homopolymers or copolymers comprising a quaternary dimethdiallyl ammonium chloride; cationic polysaccharides; cationic cellulose derivatives; chitosans and derivatives thereof; and mixtures thereof. For example, hydroxyethylcellulose dimethyldiallyammonium chloride [PCM] sold as Celquat L200 ex. Akzo Nobel, Quaternized hydroxyethylcellulose [PQ10] sold as LICARE JR125 ex Dow Personal Care, Hydagen HCMF ex. Cognis and N-Hance 3269 ex Ashland.

Suitable anionic setting polymers may be selected from polymers comprising groups derived from carboxylic or sulfonic acids. Copolymers containing acid units are generally used in their partially or totally neutralized form, more preferably totally neutralized. Suitable anionic setting polymer may comprise: (a) at least one monomer derived from a carboxylic acid or sulfonic acid such or their salts and (b) one or more monomers selected from the group consisting of: esters of acrylic acid and/or methacrylic acid, acrylate esters grafted onto a polyalkylene glycol, hydroxyesters acrylate, acrylamides, methacrylamides which may or may not be substituted on the nitrogen by lower alkyl groups, hydroxyalkylated acrylamide, amino alkylated, alkylacrylamine, alkylether acrylate, monoethylenic monomer, styrene, vinyl esters, allyl esters or methallyl esters, vinyllactams, alkyl maleimide, hydroxyalkyl maleimide, and mixtures thereof. When present the anhydride functions of these polymers can optionally be monoesterified or monoamidated. Alternatively, the anionic setting polymer may be selected from a water-soluble polyurethane, anionic polysaccharides and combinations thereof.

Preferred anionic setting polymers may be selected from: copolymers derived from acrylic acid such as the acrylic acid.

Non-ionic setting polymers may be natural, synthetic or mixtures thereof. Synthetic non-ionic setting polymers are selected from: homopolymers and copolymers comprising: (a) at least one of the following main monomers: vinylpyrrolidone; vinyl esters grafted onto a polyalkylene glycol; acrylate esters grafted onto a polyalkylene glycol or acrylamide and (b) one or more other monomers such as vinyl esters, alkylacrylamine, vinylcaprolactam, hydroxyalkylated acrylamide, amino alkylated acrylamide, vinyl ether; alkyl maleimide, hydroxyalkyl maleimide, and mixtures thereof. Suitable natural non-ionic setting polymers are water-soluble. Preferred natural non-ionic polymers are selected from: non-ionic polysaccharides including: non-ionic cellulose, non-ionic starches, non-ionic glycogens, non- ionic chitins and non-ionic guar gums; cellulose derivative, such as hydroxyalkylcelluloses and mixtures thereof. The non-ionic setting polymers are preferably selected from vinylpyrrolidone/vinyl acetate copolymers and such as vinylpyrrolidone homopolymer.

Amphoteric setting polymers may be natural, synthetic or a mixture thereof. Suitable synthetic amphoteric setting polymers include those comprising: an acid and a base like monomer; a carboxybetaine or sulfobetaine zwitterionic monomer; and an alkylamine oxide acrylate monomer. An example of such an amphoteric setting polymer is acrylates/ethylamine oxide methacrylate sold as Diaformer Z 731 N by Clariant; and mixtures thereof.

Preferably the setting polymer is selected from acrylate polymers, co-polymers comprising acrylate monomers, starches, celluloses, derivatives of cellulose and mixtures thereof. Most preferably the setting polymer is selected from the group consisting of: acrylates and copolymers of two or more acrylate monomers such as:(meth)acrylic acid or one of their simple esters; octylacrylamide/acrylate/butylaminoethyl methacrylate copolymers; acrylates/hydroxyesters acrylates copolymers of butyl acrylate, methyl methacrylate, methacrylic acid, ethyl acrylate and hydroxyethyl methacrylate; polyurethane- 14/AMP-acrylates copolymer blend; and mixtures thereof. This includes both the acids and salts thereof.

The compositions of the present invention may contain further optional laundry ingredients. Such ingredients include preservatives (including biocides) pH buffering agents, perfume carriers, hydrotropes, polyelectrolytes, anti-shrinking agents, anti-oxidants, anti-corrosion agents, drape imparting agents, anti-static agents, ironing aids, antifoams, colorants, pearlisers and/or opacifiers, natural oils/extracts, processing aids, e.g. electrolytes, hygiene agents, e.g. anti-bacterials, antivirals and antifungals, thickeners and skin benefit agents.

Spray bottle

The compositions are sprayed by any suitable spraying device.

Preferably the spray device is a manually operable spray device in the sense that the spray mechanism is manually operable to discharge a dose of said composition from the nozzle. The spray mechanism may be operated by an actuator. The actuator can be a push actuator or a pull actuator. The actuator may comprise a trigger. The spray mechanism may comprise a hand-operable pump. Optionally, said pump is one of: a positive displacement pump; a selfpriming pump; a reciprocating pump. Suitable spray devices include trigger sprays, continuous I semi-continuous sprays, finger pump sprays, vibrating mesh device output sprays.

Preferably the spray device is operable without the use of a propellant. Indeed, propellant-free spray devices are preferred. This allows the spray to maintain the integrity and purity of the product, uncontaminated with propellant and is preferably environmentally.

Preferably the spray device is pressurised. This can improve spray duration and velocity. Preferably the spray device is pressurised by a gas chamber, separate from the reservoir containing the composition. The gas is preferably air or nitrogen. The spray device may comprise an outer container containing the composition and a pressurizing agent, wherein the composition is segregated from the pressurizing agent by containment (preferably hermetically sealed) in a flexible pouch. This which maintains complete formulation integrity so that only pure (i.e. excludes pressurising agent) composition is dispensed. Preferred systems are the so-called ‘bag-in-can’ (or BOV, bag-on-valve technology). Alternatively, the spray device may comprise piston barrier mechanism, for example EarthSafe by Crown Holdings.

Preferably the spray device comprises a biodegradable plastic material.

The spray mechanism may further comprise an atomiser configured to break up said liquid dose into droplets and thereby facilitate creation of said fine aerosol in the form of a mist.

Conveniently, said atomiser may comprise at least one of: a swirl chamber and a lateral dispersion chamber. Suitably, the atomiser functions to mix air with the aqueous fabric spray composition.

The particle size of the formulation when sprayed is preferably no more than 300pm, preferably no more than 250pm, preferably no more than 150pm, preferably no more than 125pm, preferably no more than 100pm. The particle size of the formulation when sprayed is preferably at least 5pm, preferably at least 10pm, preferably at least 15pm, preferably at least 20pm, preferably at least 30pm, preferably at least 40pm. Suitably the spray comprises droplets having an average diameter in the range of preferably 5 to 300 pm, more preferably 10 to 250pm, most preferably 15 to 150pm. This size allows for homogeneous distribution and a balance between sufficient wetting of the fabric, without potential fabric damage caused by excessive dosing of certain ingredients. Droplet size may be measured on a Malvern Spraytec instrument, with the peak maximum corresponding to the average droplet size. The parameter droplet size is the volume mean diameter, D[4,3],

Suitably, following actuation, the spray has a duration in the range of at least 0.4 seconds. Preferably the spray has a duration of at least 0.8 seconds. A longer duration minimises the effort by maximising coverage per actuation of a spray device. This is an important factor for products designed to be used over the full area of garments. Preferably the spray duration is directly linked to actuation such that the spray output continues only as long as the actuator is activated (e.g. as long as a button or trigger is pressed).

Spray reservoirs may be non-pressurised, manually or mechanically pre-pressurised devices. The above also to removable I refillable reservoirs.

According to a further aspect of the present invention, there is provided a replacement reservoir for a garment refresh product according to the above aspect(s), the replacement reservoir being pre-filled with a volume of said spray composition for replenishment of said product. A suitable “refill kit” comprises one or more reservoirs. In the case of more than one reservoir, for example two, three, four, five, or more reservoirs, the contents (aqueous fabric spray composition) of each reservoir may the same as or different from the other reservoirs.

In use

Conveniently, the spray composition is provided as a liquid, and said spray mechanism is operable to discharge a dose of at least 0.1ml, preferably at least 0.2ml, more preferably at least 0.25ml, more preferably at least 0.3ml, more preferably at least 0.35ml, more preferably at least 0.35ml, more preferably at least 0.4ml, more preferably at least 0.45ml, and most preferably at least 0.5ml.

Suitably the dose is no more than 2ml, preferably no more than 1.8ml, preferably no more than 1.6ml, more preferably no more than 1.5ml, more preferably no more than 1.4ml, more preferably no more than 1.3ml, and most preferably no more than 1.2ml.

Suitably the dose is between 0.1 and 2ml of said liquid spray composition, preferably between 0.2 and 1.8ml, more preferably 0.25 to 1.6ml, more preferably 0.25 to 1.5ml, and most preferably 0.25 to 1.2ml.

These doses have been found to be particularly effective at achieving the desired garment refresh effect without unsightly and wasteful large droplet formation.

The dose may alternatively be defined as ml per m ² of fabric. The spray composition of the present invention is dosed as 0.1 to 20 ml per m ² . More preferably 0.5 to 15 ml per m ² and most preferably 1 to 10 ml per m ² .

The fabric spray compositions described herein provide improved fabric care, in particular improved hand of fabrics. Accordingly, there is provided a method of using the fabric spray composition to provide fabric care, wherein the composition is added to the rinse stage of the laundry process. Also provided is a use of the fabric spray composition to provide fabric care to a laundered fabric. Alternatively this may be expressed as the use of the microcapsules as described herein in a method as described herein to provides fabric care to a laundered fabric. Fabric care may be defined by various parameters, in particular fabric hand, softness and resilience. These are measures which decrease as a fabric is damaged. In other words fabric care may be considered the prevention of damage or the maintenance of fabric. Fabric hand is defined as the estimated quality of a fabric, evaluated when a consumer touches a fabric. Important components of fabric hand include smoothness, compressibility and elasticity of the textile sample. The compositions described herein may also provide improved softening and/or resilience to fabrics treated with the composition. Resilience is the ability of a fiber to spring back to its natural position after folding, creasing or deformation. An improvement in fabric hand, resilience or softening may be measured using a sensorial evaluation. Alternatively, machine measurements can be used. Suitable machines for measuring the relative hand value, resilience or softness are a PhabrOmeter® supplied by Nu Cybertek, Inc. An improvement in fabric hand can be measured using AATCC TM202-2012 (2020), Relative Hand Value of Textiles: Instrumental Method.

The following microcapsules as suitable for use in compositions of the present invention were used to assess the effects of the compositions described herein:

• Microcapsules 1 - Pea protein and sodium alginate mix and with salt crosslinking

• Microcapsules 2 - Pea protein and crosslinked with polyisocyanate (Poly[(phenyl isocyanate-co-formaldehyde])

Microcapsule 1 was prepared as follows: a 10% w/v solution of pea protein was prepared in demineralised water and the pH was adjusted to pH9 using a few drops of sodium carbonate solution. This was heated to 85 °C and mixed at 300RPM mixed on a tornado mixer for 2hrs. After 2hrs the pH was dropped to pH7 with a few drops of 2M HCI solution and 1.5g of sodium alginate was added.

This was further mixed at 300RPM for 90min until homogeneous and then was left overnight to cool down. Once cool the next day 22.5g of fragrance oil was added and mixed at 300RPM for 1 hr. The prepolymer mix was then added into a 80ml solution containing tween 80, calcium chloride and DI water at varying concentrations. The solution was homogenised to produce a suspension. Table 1: Microcapsule 1 composition

Microcapsule 2 was prepared as follows: an oil phase was first prepared by mixing 23.2g of a model fragrance and 4.8g of caprylic/capric triglyceride, 0.38g of benzyl benzoate and an aromatic polyisocyanate 0.38g. In a separate beaker, an aqueous solution was obtained by mixing 1.182g of a pea protein isolate in 170g of water. The oil phase was then emulsified into the aqueous phase to form an oil-in-water emulsion using an ultra turrax mixer at a shear rate of 5000 Revolutions Per Minute (RPM). The oil-in-water emulsion was then cured at 55°C for 2 hours.

Table 2: Microcapsule 2 composition Table 3: Example composition These compositions may be prepared by charging a vessel with water and maintaining the temperature at 20°C ± 5°C. Adding the silicone emulsion and minors, with stirring. Preparing a pre-mix by blending melted non-ionic surfactant (45°C) with free oil perfume and the anti- malodour technology whilst keeping the blend at 45°C. Adding the premix to the vessel with mixing.