WO2012140413A1

WO2012140413A1 - Coated fabric care agent

Info

Publication number: WO2012140413A1
Application number: PCT/GB2012/050770
Authority: WO
Inventors: Philip Smith; Victoria BURKITT; Paul John Duffield; John Chiama WASONGA
Original assignee: Reckitt & Colman (Overseas) Limited
Priority date: 2011-04-15
Filing date: 2012-04-05
Publication date: 2012-10-18
Also published as: GB201106391D0

Abstract

The present invention relates to a fabric cleaning formulation comprising a composite comprising one or more core units. Each core unit comprises a benefit agent and having a pH responsive, acrylic copolymer coating. Said active agent is selected from the group consisting of bleaching agents, anti-foaming agents, anti-redeposition aids, anti-microbials and biocides, enzymes, bleach catalysts, dye transfer inhibitors, optical brighteners, dyes, pigments, anti-scale and corrosion inhibiting ingredients, fragrances and perfumes, and mixtures thereof.

Description

COATED FABRIC CARE AGENT

The present invention relates to a fabric care formulation containing a novel composite comprising one or more core units, each core unit comprising a specified benefit agent and having a pH responsive, acrylic copolymer coating, said formulations having use in a variety of applications.

By way of example, the composites of the fabric care formulation of the invention may be employed in solid and liquid products, including those for in-wash stain removal, spot/stain removal, ironing aids, fabric treatments, pre and post wash treatments, carpet cleaners and treatments. The benefit agents included in these fabric care formulations may include bleaching compositions. Bleaching compositions frequently contain peroxy acid oxidising (or bleaching) agents of general formula (1):

where R is a linear, branched or cyclic, aliphatic or aromatic, saturated or unsaturated, substituted or unsubstituted organic moiety containing two or more carbon atoms. Peroxy acids act as bleaching agents upon decomposition to afford oxygen radicals or "active oxygen" as follows:

2 R-COO-O-H _ 2 R-CO-OH + 20.

Decomposition may be initiated by exposure to various physical (mechanical and/or thermal) stresses, is facilitated by the presence of water and may be strongly exothermic.

Phthalimido peroxy alkanoic acids of formula (2) are an example of a class of commercially available peroxy acids that are commonly used in cleaning formulations

(2)

where X is a linear or branched, substituted or unsubstituted hydrocarbon chain having at least one carbon atom and n is an integer, typically in the range from 1 to 5.

Phthalimido peroxy hexanoic acid (PAP) of formula (3):

is an example of a phthalimido peroxy alkanoic acid that has been shown to possess particularly good bleaching properties ("PAP: the bleaching agent for low temperature washing"; Elena Negri, Ausimont S.pA, Italy - page 29 of "comitato itallano dei derivati tensioattivP - ATT1 delle 9e Giornate CID, Venezia, 13-15 giugno 2001 ).

Peroxy acid bleaching agents are employed in a variety of cleaning formulations including laundry cleaning compositions. Such compositions typically comprise, in addition to a bleaching agent, a number of other active and non-active components such as surfactants, enzymes and mixtures thereof. The compositions may be in liquid or solid form.

The inclusion of bleaching agents such as peroxy acids in the same composition with enzymes and other components sensitive to oxidation, although desirable from a cleaning perspective, is problematic since these species tend to react with one another resulting in the loss of active oxygen from the bleaching agent and denaturing of the enzyme.

This incompatibility problem has previously been addressed by formulating and packaging the bleaching agent and the enzyme in such a way that the two components are separated (so-called two chamber products) and only mixed either upon dispensing or upon dissolution of a protective pouch. This technology is used in a number of commercially available home care products; examples with utility outside the scope of the current invention include Fairy Platinum (Proctor & Gamble, Cincinnati, USA) and Finish Quantum (Reckitt Benckiser, Hull, UK) dishwasher tablets. Although such products have the capability to act upon both bleach- able and enzymatically degradable stains, this is only achieved with significant additional manufacturing and packaging costs compared to single chamber products.

Packaging methods of this type place many practical constraints on total product design; limiting freedom in benefit agent selection and the need to incorporate benefit agents into specific compartments.

It would be highly desirable to provide a single chamber product capable of housing two or more otherwise incompatible benefit agents such as bleaching agent and an enzyme, whilst maintaining or improving the properties possessed by the product, such as providing enhanced cleaning properties.

The coating and encapsulation of detergent components with various inorganic and organic materials has been documented in the art. For example, WO94/15010 (The Proctor & Gamble Company) discloses a solid peroxyacid bleach precursor composition in which particles of peroxyacid bleach precursor are coated with a water-soluble acid polymer, defined on the basis that a 1 % solution of the polymer has a pH of less than 7.

WO94/03568 (The Proctor & Gamble Company) discloses a granular laundry detergent composition having a bulk density of at least 650 g/l, which comprises discrete particles comprising from 25-60 % by weight of anionic surfactant, inorganic perhydrate bleach and a peroxyacid bleach precursor, wherein the peroxyacid bleach precursor is coated with a water soluble acidic polymer.

US6225276 (Henkel Kommanditgesellschaft auf Aktien) discloses a solid particulate detergent composition comprising a coated bleaching agent that dissolves in water irrespective of pH, a bleach activator coated with a polymeric acid that only dissolves at pH values above 8, and an acidifying agent.

US5972506 (BASF Aktiengesellschaft) discloses microcapsules containing bleaching agents. The microcapsules are obtained by polymerizing a mixture of monomers in the oil phase of a stable oil-in-water emulsion in the presence of free radical polymerization initiators.

WO97/14780 (Unilever NV) discloses an encapsulated bleach particle comprising a coating including a gelled polymer material, and a core material which is selected from a peroxygen bleach compound, a bleach catalyst and a bleach precursor. The gelled polymer has a molecular structure that is partially or fully cross-linked, such as for example, agar, alginate, car- rageenan, casein, gellan gum, gelatine, pectin, whey proteins, egg protein gels and the like.

W098/16621 (Warwick International Group Ltd) discloses a process for encapsulating a solid detergent component from an oil-in-water emulsion by forming a polymer film at the oil/water interface by condensation polymerisation. Suitable polymer films include polyamide, polyester, polysulphonamide, polyurea and polyurethane.

WO98/00515 (The Proctor & Gamble Company) discloses non-aqueous, particulate containing liquid laundry cleaning compositions which are in the form of a suspension of particulate material comprising peroxygen bleaching agents and coated peroxygen bleach activators. The coating material is soluble in water, but insoluble in non-aqueous liquids, and is selected from water soluble citrates, sulphates, carbonates, silicates, halides and chromates.

WO93/24604 (BP Chemicals Ltd) discloses an encapsulated benefit agent substrate comprising a bleach and/or a bleach activator releasably encapsulated in a coating of an alkali metal carbonate or bicarbonate and an outer encapsulating coating of a metal salt of an inorganic salt.

US6107266 (Clariant GmbH) discloses a process for producing coated bleach activating granules in which bleach activator base granules are coated with a coating substrate and are simultaneously and/or subsequently thermally conditioned. The coating substance is selected from C8-C31 fatty acids, C8-C31 fatty alcohols, polyalkylene glycols, non-ionic surfactants and anionic surfactants.

According to a first aspect of the present invention there is provided a fabric care formulation comprising a composite comprising one or more core units, each core unit comprising an benefit agent and having a pH responsive, acrylic copolymer coating, wherein said benefit agent is selected from the group consisting of bleaching agents, anti-foaming agents, anti- redeposition aids, anti-microbials and biocides, enzymes, bleach catalysts, dye transfer inhibitors, optical brighteners, dyes, pigments, anti-scale and corrosion inhibiting ingredients, fragrances and perfumes, and mixtures thereof.

According to a second aspect of the present invention there is provided fabric care formulation comprising a composite comprising one or more core units, each core unit comprising an active agent and having a coating comprising a pH responsive, acrylic copolymer and a hydrophobic material, wherein said active agent is selected from the group consisting of bleaching agents, anti-foaming agents, anti-redeposition aids, anti-microbials and biocides, enzymes, bleach catalysts, dye transfer inhibitors, optical brighteners, dyes, pigments, anti- scale and corrosion inhibiting ingredients, fragrances and perfumes, glass protectors, and mixtures thereof.

In the second aspect of the invention it has been found that the benefit of this hydrophobic material aids in the coating process of water soluble granulate materials providing a water repellent surface which can be delivered using non-aqueous means, thus allowing delivery of a water based polymer coating to particles which would otherwise be dissolved during processing. There is also be a benefit to the stability of the end composite particle. The aciylic copolymer and the hydrophobic material may be present as an amorphous composition. Preferably the acrylic copolymer and the hydrophobic material are arranged in layers. In the latter case preferably the hydrophobic material is present as the innermost layer.

The thickness of the hydrophobic layer may be in the range of 0.01 - 100 pm, more preferably 0.1 - 50 pm, more preferably 3 - 30 μιη and most preferably in the range of 5 - 25 pm.

The coat weight of the hydrophobic material as a percentage of total mass of the particle is preferably in the range of 0.1 - 50% and most preferably in the range of 5 - 30%.

The thickness of the acrylic copolymer layer may be in the range of 0.01 - 100 pm, more preferably 0.1 - 50 pm, more preferably 3 - 30 pm and most preferably in the range of 5 - 25 pm.

The coat weight of the acrylic copolymer as a percentage of total mass of the particle is preferably in the range of 0.1 - 50% and most preferably in the range of 5 - 30%.

Preferably the fabric care formulation is intended to be used, for in-wash stain removal, for spot/stain removal, as an ironing aid, as a fabric treatment, as a pre and post wash treatments and / or carpet cleaners and treatments. Namely the formulation is for use as a laundry formulation and / or a laundry additive formulation.

Such composites may be placed in liquid product environments of pH < 7.5 in which the polymeric coating is indefinitely stable. When the liquid and solid products are dispersed or diluted in water, to realise conditions of greater alkalinity, i.e. pH >7.5, the protective polymeric coating is compromised, by dissolution, dissolving, rupturing or swelling, and the core benefit agent is released into the surrounding environment. The novel composites of the present invention are of potential value to numerous consumer and industrial products as further detailed herein.

In one embodiment of the invention the benefit agent is a bleaching agent or a mixture thereof. As used herein the term "bleaching agent" means a liquid or solid chemical compound that may be used to whiten or brighten various substrates and/ or remove soil from them. Examples of suitable bleaching agents include mono- and diperoxy acids and mixtures thereof.

Examples of suitable monoperoxy acids include peroxybenzoic acid, ring-substituted peroxy- benzoic acids, aliphatic monoperoxy acids, substituted aliphatic monoperoxy acids, mono- peroxyphthalic acids, and mixtures thereof. Preferred examples of monoperoxy acids include peroxy-alpha-naphthoic acid, peroxylauric acid, peroxystearic acid, peroxyformic acid, per- oxyacetic acid, peroxypropionic acid, peroxyhexanoic acid, peroxybenzoic acid, nonylami- doperoxyadipic acid, 6-hydroxyperoxyhexanoic acid, 4-phthalimidoperoxybutanoic acid, 5- phthalimidoperoxypentanoic acid, 6-phthalimidoperoxyhexanoic acid (PAP), 7- phthalimidoperoxyheptanoic acid, N,N_-terephthaloyl-di-6-aminoperoxyhexanoic acid, and mixtures thereof.

Examples of suitable diperoxy acids include alkyl and aryl diperoxy acids, including diper- oxyphthalic acids, and mixtures thereof. Preferred examples of diperoxy acids include 1 ,12- diperoxydodecanedioic acid, 1 ,9-diperoxyazelaic acid, diperoxybrassylic acid, diperoxyse- abacic acid, diperoxyoxyiso-phthalic acid, 2-decyldiperoxybutane-1 ,4-dioic acid and mixtures thereof. In a preferred embodiment, the bleaching agent is a peroxy acid as defined in formula (1 ) above or a mixture thereof. More preferably, the peroxy acid bleaching agent is a phthalimido peroxy aikanoic acid bleaching agent as defined in formula (2) above or a mixture thereof. Most preferably, the bleaching agent is PAP.

In an alternative embodiment of the invention, the benefit agent is an anti-foaming agent or a mixture thereof. Examples of suitable anti-foaming agent examples include soaps of natural or synthetic origin which have a high content of C18-C24 fatty acids; organopolysiloxanes and mixtures thereof with microfine, optionally silanized silica; alkyl ethoxylate non-ionic surfactants; and paraffins, waxes, microcrystalline waxes and mixtures thereof with silanized silica or bis-stearyl ethylenediamide, and mixtures thereof. In a preferred embodiment of the invention, the anti-foaming agent is a paraffin, a bis-stearyl ethylenediamide, or a mixture thereof. The anti-foaming agent is preferably loaded onto a granular, water-soluble or dispersible carrier material.

In an alternative embodiment of the invention, the benefit agent is an anti-redeposition aid or a mixture thereof. Examples of suitable anti-redeposition aids include organic polymeric compounds such as, but not limited to, ethoxylated polyamines, polycarboxylic acids, modified polyoamoxylates or their salts or copolymers with any suitable other monomer unite including modified acrylic, fumaric, maleic, itaconic, aconitic, mesaconic, citraconic and me- thylenemalonic acid or their salts, maleic anhydride, acrylamide, alkylene, vinylmethyl ether, styrene, and mixtures thereof. Preferred commercially available anti-redeposition aids include TexCare® anionic polyester polymers (Clariant), Sokalan® polyacrylate copolymers (BASF) and Acusol® acrylic acid polymers (The Dow Chemical Co.).

In an alternative embodiment of the invention, the benefit agent is an antimicrobial agents or a mixture thereof. Examples of suitable antimicrobial agents include, but are not limited to, ophenylphenol, bromonitropropane diol, tris(hydroxymethyl)nitromethane, octadecylaminidi- methyltrimethoxysilylpropylammonium chloride, silver zeolite, benzoimidazole, 2-(4- thiazolyl)-2,6-dimethyl-1 ,3-dioxan-4-ol acetate, Hinokitiol, propene nitriles, 2,4,4'-trichloro-2'- hydroxydiphenylether, cyclopropyl-N'-(1 ,1 -dimethylethyl)-6-(methylthio)-1 ,3,5-triazine-2,4- diamine, zinc oxide, 1-aza-3,7-dioxa-5-ethyl-bicyclo-(3,3,0)-octane, 2-bromo-2-nitro-1 ,3- propanediol, 2-(hydroxylmethyl)-2-nitro-1 ,3-propanediol, 2,2-dibromo-propanediamide, 2,4,4'-trichloro-2-hydroxydiphenyl ether, 4,4'-dichloro-2-hydroxydiphenyl ether, tetrakis(hydroxymethyl)phosphonium sulphate, and mixtures thereof.

In an alternative embodiment of the invention, the benefit agent is an enzyme or a mixture thereof. Examples of suitable enzymes include amylases, arabinosidases, bluco-amulases, cellulases, chondroitinases, cutinases, esterases, hydrolases, hemicellulases, isomerases, keratinases, lassases, lignases, lipases, lipooxygenases, lyases, malanases, mannanase, oxidases, oxidoreductases, pectinases, pentosanases, peroxidases, phenoloxidases, phos- pholipases, proteases, pullulanases, reductases, R-glucanases, tannases, transferases, xy- lanases, and mixtures thereof.

"Enzyme variants" produced, for example, by recombinant techniques are also included within the meaning of the term "enzyme" as used herein. Examples of suitable enzyme variants include those compounds disclosed in EP0251446A (Genencor), WO91/00345 (Novo Nordisk), EP0525610A (Solvay) and WO94/02618 (Gist-Brocades).

Core units comprising one or more enzymes may be produced by a variety of techniques known in the art. Suitable methods include those disclosed in DE2137042 (Novo Terapeutisk Laboratorium), US4087368 (Colgate Palmolive), US4016040 (Colgate Palmoiive), US4242219 (Gist-Brocades), US4009076 (Lever Brothers), US4689297 (Miles Laboratories), UK1361387A (Novo Terapeutisk Laboratorium), US3749671 (P&G), US5324649 (Genencor) and US3277520 (Fuji Denki Kogyo Kabushiki Kar).

A number of suitable enzyme-containing core materials are commercially available; examples include Stainzyme® (amylase), Esperase_^ (protease), Alcalase_ (protease), Termamyl_ (amylase), Fungamyl_ (amylase) and Lipolase_ (lipase) which are available from No- vozymes. Further examples include Purafect_ (protease), Properase_ (protease), Purastar_^ (Amylase), Puradex_ (Cellulase) and Purabrite_ (Mannanase), which are available from Genencor.

In an alternative embodiment of the invention, the benefit agent is a bleach catalyst or a mixture thereof. Examples of suitable bleach catalysts include transition metal bleach catalysts containing either manganese or cobalt. A preferred bleach catalyst is penta amine acetatco- balt (III) nitrate (PAAN). Further preferred types of bleach catalysts include the manganese- based complexes disclosed in US246621 and US5244594 and those described in EP0549272A. Preferred ligands for use in preparing transition metal based bleach catalysts include 1 , 5, 9-trimethyl-1 , 5, 9- triazacyclododecane, 2-methyl-1 , 4, 7-triazacyclononane, 2- methyl-1 , 4,7-triazacyclononane, 1 ,2, 4,7-totramcthyl- 1 ,4, 7-liia at yclononane, and mixtures thereof.

In an alternative embodiment of the invention, the benefit agent is a polymeric dye transfer inhibiting agent or a mixture thereof. Examples of suitable polymeric dye transfer inhibiting agents include polyamine N-oxide polymers, copolymers of N-vinylpyrrolidone and N- vinyiimidazole, poly(vinylpyrrolidone) polymers, and mixtures thereof.

In an alternative embodiment of the invention, the benefit agent is an optical brighter or a mixture thereof. Examples of suitable optical brighteners include 4,4'-bis[(4-anilino-6-(N-2- hydroxyethyl-N-methylamino)-s-triazine-2-yl)amino]2,2'-stiibenedisulfonic acid, disodium salt (Tinopal 5BM-GX, Ciba-Geigy Corporation), 4,4',-bis[(4-anilino-6-(N-2-bis-hydroxyethyl)- striazine-2-yl)amino]-2,2'-stilbenedisulfonic acid, disodium salt (Tinopal-UNPA-GX, Ciba- Geigy Corporation), 4,4'-bis[(4-anilino-6-morphilino-s-triazine-2-yl)amino]2,2'- stilbenedisulfonic acid, sodium salt (Tinopal AMS-GX, Ciba-Geigy Corporation) and mixtures thereof.

In an alternative embodiment of the invention, the benefit agent is a dye or a mixture thereof. Examples of suitable dyes include dyes that have high aesthetic effect but do not discolour laundered textiles; such as azo dyes, anthraquinone dyes, benzofuranone dyes, polycycli- caromatic carbonyl dyes containing one or more carbonyl groups linked by a quinoid system, indigoid dyes, polymethine and related dyes, styryl dyes, di- and tri- aryl carbonium and related dyes, such as diphenylmethane, methylene blue, oxazine and xanthene types; phthalo- cyanines, such as those di- and trisulfonated deriavtives; quinophthalones, sulphur dyes and nitro-dyes, and mixtures thereof. Preferred dyes are those which possess low fastness to textiles, i.e. "no n -staining" dyes.

In an alternative embodiment of the invention, the benefit agent is a pigment or a mixture thereof. Examples of suitable pigments include titanium dioxide, natural or synthetic mica, silica, tin oxide, iron oxide, rutile, chromium dioxide, aluminum oxide, zirconium oxide, bismuth oxychloride and mixtures thereof.

In an alternative embodiment of the invention, the benefit agent is an anti-scale or corrosion inhibition ingredient, or a mixture thereof. Examples of suitable anti-scale or corrosion inhibition ingredients include amino trimethylene phosphonic acid, 1 -hydroxy ethylidene-1 ,1 - diphosphonic acid, ethylene diamine tetra (methylene phosphonic acid) sodium, ethylene diamine tetra (methylene phosphonic acid), diethylene triamine penta (methylene phosphonic acid), polyaspartic acid sodium salt, polyepoxysuccinic acid, polyacrylic acid, acrylic acid-2-acrylamido-2-methylpropane sulfonic acid copolymer, acrylic acid-2-hydroxypropyl acrylate copolymer, and mixtures thereof.

In an alternative embodiment of the invention, the benefit agent is a fragrance or perfume, or a mixture thereof. Examples of suitable fragrances or perfumes include those disclosed in US4534891 , US5112688, US5145842 and "Perfumes Cosmetics and Soaps", Second Edition, edited by W. A. Poucher, 1959. Preferred examples include acacia, cassie, chypre, cylamen, fern, gardenia, hawthorn, heliotrope, honeysuckle, hyacinth, jasmine, lilac, lily, magnolia, mimosa, narcissus, freshly-cut hay, orange blossom, orchids, reseda, sweet pea, trefle, tuberose, vanilla, violet, wallflower, and mixtures thereof.

The composites used in the formulations may be used in a wide variety of fabric care applications including in-wash stain removal, spot/stain removal, ironing aid, fabric treatments, pre and post wash treatments, carpet cleaners and treatments.

In a preferred embodiment of the invention the composite in the formulalion thereof comprises a bleaching agent, in particular a peroxy acid, and/or an enzyme. Such composites and formulations thereof may be used in fabric care products such as those intended to remove stains from fabrics. .

In a further preferred embodiment of the invention, there is provided a fabric care formulation containing a composite comprising one or more core units, each core unit comprising an benefit agent and having a pH responsive, acrylic copolymer coating,

One preferred format for the formulations of the invention is as liquid anhydrous fabric care compositions, which are added to washing machines as a unit dose product (supplied as a liquid filled pouch) or by means of a dosing device.

One preferred format for the formulations of this invention is low water content (5 to 25%) liquid fabric care compositions, which are added to washing machines as a unit dose product (supplied as a liquid filled pouch) or by means of a dosing device.

One preferred format for the formulations of this invention is medium water content (25 to 60%) liquid fabric care compositions, which are introduced to washing machines by means of a dosing device or as a bulk liquid.

One preferred format for the formulations of this invention is high water content (60 to 95%) liquid fabric care compositions, which are introduced to washing machines by means of a dosing device or as a bulk liquid.

A preferred embodiment of the invention relates to a fabric care composition such as an in- wash stain removal product or pre-wash treatment. Preferably, the in-wash stain removal product or pre-wash treatment is an acidic or neutral liquid product, more preferably, an acidic in-wash stain removal product or pre-wash treatment.

In another preferred embodiment of the invention, there is provided a solid or liquid fabric care product comprising from about 0.5% to about 25% by weight of the composite. Preferably, said product comprises a benefit agent selected from a bleaching agent, enzyme, fragrance or perfume, or a mixture thereof. In one preferred embodiment of the invention, the fabric care product is a spot/stain removal composition. Typically, the liquid spot/stain removal composition will include water (from 0% to 95%).

In one preferred embodiment of the invention, the fabric care product is an ironing aid composition. Typically, the ironing aid composition will include water (from 0% to 95%).

In one preferred embodiment of the invention, the fabric care product is a fabric treatment composition. Typically, the fabric treatment composition will include water (from 0% to 95%).

In one preferred embodiment of the invention, the fabric care product is a pre and / or post wash treatment. Typically, the pre and / or post wash treatment composition will include water (from 0% to 95%).

In one preferred embodiment of the invention, the fabric care product is a carpet cleaner and / or treatment. Typically, the carpet cleaner and / or treatment composition will include water (from 0% to 95%).

In another preferred embodiment of the invention, the fabric care product is a solid product , more preferably, a powdered or tableted composition.

Fabric care compositions will typically contain from about 0.5% to about 25.0% of the composite of the invention, more preferably from about 1 .0% to about 12.5% and even more preferably from about 1.0% to about 10.0% by weight of the total composition.

In a further preferred embodiment of the invention, the fabric care product further comprises one or more of an anionic surfactant, a non-ionic surfactant and a cationic surfactant.

Typically, alcohol alkoxylate non-ionic surfactants are preferably present in an amount of from about 1 % to about 60% by weight of the composition, more preferably from about 5% to about 50%, even more preferably from about 5% to about 30%.

Fabric care compositions of the present invention may also optionally include anti- redeposition and soil suspension agents, foam control agents, thickeners, perfumes and colours, as well as other ingredients known to be useful in laundry products.

The following ingredients may be present in the formulation either in the composite or the remainder of the formulation or both.

Generally the formulation comprises a bleach activator. The bleach activator is possibly in particulate form.

Where the bleach activator is in particulate form generally it has a particle size of 0.0001 to 2mm, e.g. such as 1 mm.

Preferably the bleach activator is selected from tetraacetylethylendiamine (TAED), acetylated triazine derivatives, in particular 1 ,5-Diacetyl-2,4-dioxohexahydro-1 ,3,5-triazine (DADHT), acetylated glycoluriles, in particular Tetraacetylglycolurile (TAGU), acylimides, in particular n- nonanoylsuccinimide (NOSI), acetylated phenolsu!fonates, in particular n-nonanoyloxi or n- lauroyloxibenzolsulfonate (NOBS and/or PRAISE), acetylated phenol carbonic acids, in particular nonanoyloxi or decanoyloxibenzoesaeure (NOBA and/or DOBA), carbonic acid anhydrides, acetylated sugar derivatives, in particular pentaacetylglucose (PAG), pentaacetylfruc- tose, tetraacetylxylose and octaacetyllactose as well as acetylated N-alkylated glucamine and gluconolactone, and/or N- acetylated lactams, for example N-Benzoylcaprolactam. Hy- drophi!ically substituted ecy! acetals and ecyi lactams are likewise preferentially used. Particularly preferential bleach activators are TAED and DOBA.

Bleaching catalysts may be present. Preferred examples include complexes of manganese, iron, cobalt, ruthenium, molybdenum, titanium or vanadium.

When using metal salts in particular manganese salts are in the oxidation state +2 or +3 preferentially, for example manganese halides, whereby the chloride is preferential. Manganese sulfate, manganese salts of organic acids such as manganese acetates, acetylaceto- nate, oxalates as well as manganese nitrates are suitable.

Metal complex with macromolecular ligands may be used such as1 ,4,7-Trimethyl-1 ,4,7- triazacyclononane (me-TACN), 1 ,4,7-Triazacyclononane (TACN), 1 ,5,9-Trimethy ,5,9- triazacyclododecane (me-TACD), 2-Methyl-1 ,4,7 trimethyl-1 ,4,7-triazacyclononane (Me- MeTACN) and/or 2-MethyI-1 ,4,7 triazacyclononane (Me TACN) or ligands such as 1 ,2-bis (4,7-Dimethyl 1 ,4,7-triazacyclonono-i-yl) ethane (Me4-DTNE).

The bleaching agent is usually a source of active oxygen, e.g. urea / hydrogen peroxide. The bleaching agent may be based on alternative chemistry, e.g. chlorine based bleaching agents, such as hypochlorite bleaches.

Some bleaching agents, such as phthalimido-peroxy-hexanoic-acid (PAP) per-salts such as; perborate, percarbonate, persulphate; are substantially insoluble in water (e.g. having a solubility of less than 0.6g/litre of demineralised water at 25°C. .

Where the bleaching agent is in particulate form generally it has a particle size of 0.0001 to 2mm, e.g. such as 1 mm.

Examples of bleaches that may be used are oxygen bleaches.

Peroxygen bleaching actives are: perborates, peroxides, peroxyhydrates, persulfates. A preferred compound is sodium percarbonate and especially the coated grades that have better stability. The percarbonate can be coated with silicates, borates, waxes, sodium sulfate, sodium carbonate and surfactants solid at room temperature.

Optionally, the compositions may additionally comprise from 0.01 to 30 %wt, preferably from 2 to 20 %wt of bleach precursors. Suitable bleach precursors are peracid precursors, i.e. compounds that upon reaction with hydrogen peroxide product peroxyacids. Examples of peracid precursors suitable for use can be found among the classes of anhydrides, amides, imides and esters such as acetyl triethyl citrate (ATC), tetra acetyl ethylene diamine (TAED), succinic or maleic anhydrides.

When a surfactant is present in the composition, it may be present in an amount of, for example, from 0.01 to 50 %wt, ideally 0.1 to 30 %wt and preferably 0.5 to 10 %wt.

Suitable surfactants that may be employed include anionic or nonionic surfactants or mixture thereof. The nonionic surfactant is preferably a surfactant having a formula RO(CH₂CH₂0)_nH wherein R is a mixture of linear, even carbon-number hydrocarbon chains ranging from C₁₂H₂5 to C₁₆H₃₃ and n represents the number of repeating units and is a number of from about 1 to about 12. Examples of other non-ionic surfactants include higher aliphatic primary alcohol containing about twelve to about 16 carbon atoms which are condensed with about three to thirteen moles of ethylene oxide per mole of alcohol (i.e. equivalents). Other examples of nonionic surfactants include primary alcohol ethoxylates (available under the Neodol tradename from Shell Co.), such as alkanol condensed with 9 equivalents of ethylene oxide (Neodol 1 -9), C₁₂-i₃ alkanol condensed with 6.5 equivalents ethylene oxide (Neodol 23-6.5), C₁₂.₁₃ alkanol with 9 equivalents of ethylene oxide (Neodol 23-9), C_1Z.₁₅ alkanol condensed with 7 or 3 equivalents ethylene oxide (Neodol 25-7 or Neodol 25-3), C_1<M5 alkanol condensed with 13 equivalents ethylene oxide (Neodol ethoxy- lated alcohol, averaging 2.5 moles of ethylene oxide per mole

91 -2.5), and the like.

Other examples of nonionic surfactants suitable for use include ethylene oxide condensate products of secondary aliphatic alcohols containing 11 to 18 carbon atoms in a straight or branched chain configuration condensed with 5 to 30 equivalents of ethylene oxide. Examples of commercially available non-ionic detergents of the foregoing type are C_11-15 secondary alkanol condensed with either 9 equivalents of ethylene oxide (Tergitol 15-S-9) or 12 equivalents of ethylene oxide (Tergitol 15-S-12) marketed by Union Carbide, a subsidiary of Dow Chemical.

Octylphenoxy polyethoxyethanol type nonionic surfactants, for example, Triton X-100, as well as amine oxides can also be used as a nonionic surfactant.

Other examples of linear primary alcohol ethoxylates are available under the Tomadol tradename such as, for example, Tomadol 1 -7, a C linear primary alcohol ethoxylate with 7 equivalents EO; Tomadol 25-7, a C_12-i₅ linear primary alcohol ethoxylate with 7 equivalents EO; Tomadol 45-7, a C₁₄.₁₅ linear primary alcohol ethoxylate with 7 equivalents EO; and Tomadol 91 -6, a

linear alcohol ethoxylate with 6 equivalents EO.

Other nonionic surfactants are amine oxides, alkyl amide oxide surfactants.

Preferred anionic surfactants are frequently provided as alkali metal salts, ammonium salts, amine salts, aminoalcohol salts or magnesium salts. Contemplated as useful are one or more sulfate or sulfonate compounds including: alkyl benzene sulphates, alkyl sulphates, alkyl ether sulphates, alkylamidoether sulphates, alkylaryl polyether sulphates, monoglyc- eride sulphates, alkylsulfonates, alkylamide sulfonates, aikylarylsulfonates, olefinsulfonates, paraffin sulfonates, alkyl sulfosuccinates, alkyl ether sulfosuccinates, alkylamide sulfosucci- nates, alkyl sulfosuccinamate, alkyl sulfoacetates, alkyl phosphates, alkyl ether phosphates, acyl sarconsinates, acyl isethionates, and N-acyl taurates. Generally, the alkyl or acyl radical in these various compounds comprise a carbon chain containing 12 to 20 carbon atoms.

Other surfactants which may be used are alkyl naphthalene sulfonates and oleoyl sarcosi- nates and mixtures thereof.

Any suitable soil catcher may be employed. Unlike detergents or surfactants, which simply aid in the removal of soils from surfaces, the soil catcher actively binds to the soil allowing it to be removed from the surface of the laundry. Once bound, the soil is less likely to be able to redeposit onto the surface of the laundry. Preferred soil catchers have a high affinity to both oily and water-soluble soil. Preferably, the soil catcher is a mixture of two or more soil catchers, each soil catcher may have a different affinity for different soils. Preferred soil catchers for oily soils have a non polar structure with high absorption capability. Preferred water based soil catchers are generally charged and have a high surface area in order to attract the soil by electrostatic charge and collect it.

Suitable soil catchers include polymers, such as acrylic polymers, polyesters and polyvinylpyrrolidone (PVP). The polymers may be crosslinked, examples of which include crosslinked acrylic polymers and crosslinked PVP. Super absorbing polymers are mainly acrylic polymers and they are useful for the scope of this patent.

Other important polymers are ethylidene norbene polymers, ethylidene norbene/ethylene copolymers, ethylidene norbene/propylene/ethylidene ter-polymers. Inorganic materials may also be employed. Examples include zeolites, talc, bentonites and active carbon. The latter may be used to absorb and/or degrade coloured parts of stain and/or absorb odours. Alginates, carrageneans and chitosan may also be used. Preferred water insoluble agents are selected from at least one of acrylic polymer, polyester, poiy(vinylpyrrolidone) (PVP), silica, silicate, zeolite, talc, bentonites, active carbon, alginates, carrageneans, ethylidene mor- bene/propylene/ethylidene ter-polymers and chitosan in the manufacture of a detergent composition as an active agent for binding soil. Preferably the detergent composition is a laundry cleaning composition or stain-removing composition.

Preferred examples of water-insoluble soil catcher compounds comprise a solid cross-linked polyvinyl N-oxide, or chitosan product or ethylidene norbene/propylene/ethylidene ter- polymers or blend of the same, as discussed more fully hereafter.

Water soluble polymeric soil catcher agontc that aro ouitablc to be bound to insoluble carriers, or to be made insoluble via cross-linking are those polymers known in the art to inhibit the transfer of dyes from coloured fabrics onto fabrics washed therewith. These polymers have the ability to complex or adsorb the fugitive dyes washed out of dyed fabrics before the dyes have the opportunity to become attached to other articles in the wash. Especially suitable polymeric soil catcher agents are polyamine N-oxide polymers, polymers and copolymers of N-vinylpyrrolidone and N-viny!imidazole, vinyloxazolidones, vinylpyridine, vinylpyri- dine N-oxide, other vinylpyridine derivatives or mixtures thereof.

The soil catcher may be present in the detergent composition in an amount of 0.01 to 100 %wt of the composition, preferably from 1 to 90 %wt, more preferably from 5 to 50 %wt.

The composition advantageously additionally comprises cleaning agents selected from the group consisting of, fillers, builders, chelating agents, activators, fragrances, enzymes or a mixture thereof. These active agents are generally water soluble, so dissolve during the wash. Thus the additional active agents are released over a period of time when exposed to water in the laundry washing machine.

Suitable fillers include bicarbonates and carbonates of metals, such as alkali metals and alkaline earth metals. Examples include sodium carbonate, sodium bicarbonate, calcium carbonate, calcium bicarbonate, magnesium carbonate, magnesium bicarbonate and sesqui- carbonates of sodium, calcium and/or magnesium. Other examples include metal carboxy glycine and metal glycine carbonate. Chlorides, such as sodium chloride; citrates; and sulphates, such as sodium sulfate, calcium sulfate and magnesium sulfate, may also be employed.

The filler may be present in an amount of 0.1 to 80 %wt, preferably 1 to 60 %wt.

The composition may comprise at least one builder or a combination of them, for example in an amount of from 0.01 to 80%wt, preferably from 0.1 to 50%wt. Builders may be used as chelating agents for metals, as anti-redeposition agents and/or as alkalis.

Examples of builders are described below: - the parent acids of the monomeric or oligomeric polycarboxylate chelating agents or mixtures thereof with their salts, e.g. citric acid or citrate/citric acid mixtures are also contemplated as useful builder components.

- borate builders, as well as builders containing borate -forming materials than can produce borate under detergent storage or wash conditions can also be used.

- iminosuccinic acid metal salts.

- polyaspartic acid metal salts.

- ethylene diamino tetra acetic acid and salt forms.

- water-soluble phosphonate and phosphate builders are useful. Examples of phosphate builders are the alkali metal tripolyphosphates, sodium potassium and ammonium pyrophosphate, sodium and potassium and ammonium pyrophosphate, sodium and potassium orthophosphate sodium polymeta/phosphate in which the degree of polymerisation ranges from 6 to 21 , and salts of phytic acid. Specific examples of water-soluble phosphate builders are the alkali metal tripolyphosphates, sodium, potassium and ammonium pyrophosphate, sodium, potassium and ammonium pyrophosphate, sodium and potassium orthophosphate, sodium polymeta/phosphate in which the degree of polymerization ranges from 6 to 21 , and salts of phytic acid. Such polymers include polycarboxylates containing two carboxy groups, water-soluble salts of succinic acid, malonic acid, (ethylenedioxy)dlacetic acid, maleic acid, diglycolic acid, tartaric aoid, tartronic acid and fumaric acid, as well as the ether carboxylates and the sulfinyl carboxylates.

Polycarboxylates containing three carboxy groups include, in particular, water-soluble citrates, aconitrates and citraconates as well as succinate derivates such as the carboxymeth- loxysuccinates described in GB-A-1 ,379,241 , lactoxysuccinates described in GB-A- 1 ,389,732, and aminosuccinates described in NL-A-7205873, and the oxypolycarboxylate materials such as 2-oxa-1 ,1 ,3-propane tricarboxylates described in GB-A-1 ,387,447.

Polycarboxylates containing four carboxy groups include oxydisuccinates disclosed in GB-A- 1 ,261 ,829, 1 ,1 ,2,2-ethane tetracarboxylates, 1 ,1 ,3,3-propane tetracarboxylates and 1 ,1 ,2,3- propane tetracarobyxlates. Polycarboxylates containing sulfo substituents include the su!fo- succinate derivatives disclosed in GB-A-1 ,398,421 , GB-A-1 ,398,422 and US- A-3, 936448, and the sulfonated pyrolysed citrates described in GB-A-1 ,439,000.

Alicylic and heterocyclic polycarboxylates include cyclopentane-cis,cis,cis-tetracarboxylates, cyclopentadienide pentacarboxylates, 2,3,4,5,6-hexane - hexacarboxylates and carboxy- methyl derivates of polyhydric alcohols such as sorbitol, mannitol and xylitol. Aromatic polycarboxylates include mellitic acid, pyromellitic acid and the phthalic acid derivatives disclosed in GB-A-1 ,425,343.

Of the above, the preferred polycarboxylates are hydroxycarboxylates containing up to three carboxy groups per molecule, more particularly citrates.

Suitable water-soluble polymeric compounds include the water soluble monomeric polycarboxylates, or their acid forms, homo or copolymeric polycarboxylic acids or their salts in which the polycarboxylic acid comprises at least two carboxyiic radicals separated from each other by not more than two carbon atoms, carbonates, bicarbonates, borates, phosphates, and mixtures of any of the foregoing.

The carboxylate or polycarboxylate builder can be monomeric or oligomeric in type although monomeric polycarboxylates are generally preferred for reasons of cost and performance.

Suitable carboxylates containing one carboxy group include the water soluble salts of lactic acid, glycolrc acid and ether derivatives thereof. Polycarboxylates containing two carboxy groups include the water-soluble salts of succinic acid, malonic acid, (ethylenedioxy) diacetic acid, maleic acid, diglycolic acid, tartaric acid, tartronic acid and fumaric acid, as well as the ether carboxylates and the sulfinyl carboxylates. Polycarboxylates containing three carboxy groups include, in particular, water-soluble citrates, aconitrates and citraconates as well as succinate derivates such as the carboxymethloxysuccinates described in GB-A-1 ,379,241 , lactoxysuccinates described in GB-A-1 ,389,732, and aminosuccinates described in NL-A- 7205873, and the oxypolycarboxylate materials such as 2-oxa-1 ,1 ,3-propane tricarboxylates described in GB-A-1 ,387,447.

Polycarboxylate containing four carboxy groups include oxydisuccinates disclosed in GB-A- 1 ,261 ,829, 1 ,1 ,2,2-ethane tetracarboxylates, 1 ,1 ,3,3-propane tetracarboxylates and 1 ,1 ,2,3- propane tetracarobyxlates. Polycarboxylates containing sulfo substituents include the sulfo- succinate derivatives disclosed in GB-A-1 ,398,421 , GB-A-1 ,398,422 and US-A-3 ,936448, and the sulfonated pyrolysed citrates described in GB-A-1 ,439,000.

Alicylic and heterocyclic polycarboxylates include cyclopentane-cis.cis.cis-tetracarboxylates, cyclopentadienide pentacarboxylates, 2,3,4,5,6-hexane - hexacarboxylates and carboxy- methyl derivates of polyhydric alcohols such as sorbitol, mannitol and xylitol. Aromatic polycarboxylates include mellitic acid, pyromellitic acid and the phthalic acid derivatives disclosed in GB-A-1 ,425,343.

Of the above, the preferred polycarboxylates are hydroxy carboxylates containing up to three carboxy groups per molecule, more particularly citrates.

More preferred polymers are homopolymers, copolymers and multiple polymers of acrylic, fluorinated acrylic, sulfonated styrene, maleic anhydride, methacrylic, iso-butylene, styrene and ester monomers.

Examples of these polymers are Acusol supplied from Rohm & Haas, Syntran supplied from Interpolymer and the Versa and Alcosperse series supplied from Alco Chemical, a National Starch & Chemical Company.

The parent acids of the monomeric or oligomeric polycarboxylate chelating agents or mixtures thereof with their salts, e.g. citric acid or citrate/citric acid mixtures are also contemplated as useful builder components.

Examples of bicarbonate and carbonate builders are the alkaline earth and the alkali metal carbonates, including sodium and calcium carbonate and sesqui-carbonate and mixtures thereof. Other examples of carbonate type builders are the metal carboxy glycine and metal glycine carbonates.

In the context of the present application it will be appreciated that builders are compounds that sequester metal ions associated with the hardness of water, e.g. calcium and magnesium, whereas chelating agents are compounds that sequester transition metal ions capable of catalysing the degradation of oxygen bleach systems. However, certain compounds may have the ability to perform both functions.

Suitable chelating agents to be used herein include chelating agents selected from the group of phosphonate chelating agents, amino carboxylate chelating agents, polyfunctionally- substituted aromatic chelating agents, and further chelating agents like glycine, salicylic acid, aspartic acid, glutamic acid, malonic acid, or mixtures thereof. Chelating agents when used, are typically present herein in amounts ranging from 0.01 to 50 %wt of the total composition and preferably from 0.05 to 10 %wt. Suitable phosphonate chelating agents to be used herein may include ethydronic acid as well as amino phosphonate compounds, including amino alkylene poly (alkylene phosphonate), alkali metal ethane 1 -hydroxy diphosphonates, nitrilo trimethylene phosphonates, ethylene diamine tetra methylene phosphonates, and diethylene triamine penta methylene phosphonates. The phosphonate compounds may be present either in their acid form or as salts of different cations on some or all of their acid functionalities. Preferred phosphonate chelating agents to be used herein are diethylene triamine penta methylene phosphonates. Such phosphonate chelating agents are commercially available from Monsanto under the trade name DEQUEST TM.

Polyfunctionally-substituted aromatic chelating agents may also be useful in the compositions herein. See U.S. patent 3,812,044, issued May 21 , 1974, to Connor et al. Preferred compounds of this type in acid form are dihydroxydisulfobenzenes such as 1 ,2-dihydroxy - 3,5-disulfobenzene.

A preferred biodegradable chelating agent for use herein is ethylene diamine Ν,Ν'-disuccinic acid, or alkali metal, or alkaline earth, ammonium or substituted ammonium salts thereof or mixtures thereof. Ethylenediainirie Ν,Ν'-disucuinic acids, especially the (S,S) Isomer have been extensively described in US patent 4, 704, 233, November 3, 1987, to Hartman and Perkins. Ethylenediamine Ν,Ν'-disuccinic acid is, for instance, commercially available under the tradename ssEDDS TM from Palmer Research Laboratories.

Suitable amino carboxylates to be used herein include ethylene diamine tetra acetates, diethylene triamine pentaacetates, diethylene triamine pentaacetate (DTPA), N- hy- droxyethylethylenediamine triacetates, nitrilotri-acetates, ethylenediamine tetrapropionates, triethylenetetraaminehexa-acetates, ethanol-diglycines, propylene diamine tetracetic acid (PDTA) and methyl glycine diacetic acid (MGDA), both in their acid form, or in their alkali metal, ammonium, and substituted ammonium salt forms. Particularly suitable amino carboxylates to be used herein are diethylene triamine penta acetic acid, propylene diamine tetracetic acid (PDTA) which is, for instance, commercially available from BASF under the trade name Trilon FS TM and methyl glycine di-acetic acid (MGDA).

The fabric care compositions may comprise a solvent. Solvents can be used in amounts from 0.01 to 30 %wt, preferably in amounts of 0.1 to 3 %wt. The solvent constituent may include one or more alcohol, glycol, acetate, ether acetate, glycerol, polyethylene glycol with molecular weights ranging from 200 to 1000, silicones or glycol ethers. Exemplary alcohols useful in the compositions include C₂* primary and secondary alcohols which may be straight chained or branched, preferably pentanol and hexanol.

Preferred solvents are glycol ethers. Examples include those glycol ethers having the general structure R_a-O-[CH₂-CH(R)-(CH₂)-0]_n-H, wherein R_a is C^._ZQ alkyl or alkenyl, or a cyclic alkane group of at least 6 carbon atoms, which may be fully or partially unsaturated or aromatic; n is an integer from 1 to 10, preferably from 1 to 5; and each R is selected from H or CH₃. Specific and preferred solvents are selected from propylene glycol methyl ether, dipro- pylene glycol methyl ether, tripropylene glycol methyl ether, propylene glycol n-propyl ether, ethylene glycol n-butyl ether, diethylene glycol n-butyl ether, diethylene glycol methyl ether, propylene glycol, ethylene glycol, isopropanol, ethanol, methanol, diethylene glycol mono- ethyl ether acetate, and, especially, propylene glycol phenyl ether, ethylene glycol hexyl ether and diethylene glycol hexyl ether.

The fabric care composition of the invention may, for example, comprise one enzyme or a combination of them, for example in an amount of from 0.01 to 10 %wt, preferably from 0.1 to 2 %wt. Enzymes in granular form are preferred. Examples of suitable enzymes are proteases, modified proteases stable in oxidisable conditions, amylases, lipases and cellulases.

Claims

1. A fabric care formulation comprising a composite comprising one or more core units, each core unit comprising a benefit agent and having a pH responsive, acrylic copolymer coating, wherein said benefit agent is selected from the group consisting of bleaching agents, anti- foaming agents, anti-redeposition aids, anti-microbials and biocides, enzymes, bleach catalysts, dye transfer inhibitors, optical brighteners, dyes, pigments, anti-scale and corrosion inhibiting ingredients, fragrances and perfumes, and mixtures thereof.

2. A fabric care formulation comprising a composite comprising one or more core units, each core unit comprising an active agent and having a coating comprising a pH responsive, acrylic copolymer and a hydrophobic material, wherein said active agent is selected from the group consisting of bleaching agents, anti-foaming agents, anti-redeposition aids, antimicrobials and biocides, enzymes, bleach catalysts, dye transfer inhibitors, optical brighteners, dyes, pigments, anti-scale and corrosion inhibiting ingredients, fragrances and perfumes, glass protectors, and mixtures thereof.

3. A lunnulaliuii a uidiny lo claim 2, wherein the acrylic copolymer and the hydrophobic material are arranged in layers.

4. A formulation according to claim 1 , 2 or 3, wherein the core units are solid.

5. A formulation according to any one of claims 1-4, wherein the core units comprise single discrete particles, agglomerated particles, matrix particles and/or spheronised compositions.

6. A formulation according to any one of claims 1 -5, wherein the benefit agent is a bleaching agent.

7. A formulation according to claim 6, wherein the bleaching agent is a mono- or diperoxy acid, or a mixture thereof.

8. A formulation according to claim 7, wherein the bleaching agent is phthalimido peroxy hexanoic acid.

9. A formulation according to any one of claims 1 to 5, wherein the benefit agent is an enzyme.

10. A formulation according to claim 9, wherein the enzyme is selected from amylases, ara- binosidases, bluco-amulases, cellulases, chondroitinases, cutinases, esterases, hydrolases, hemicellulases, isomerases, keratinases, lassases, lignases, lipases, lipooxygenases, lyases, malanases, mannanase, oxidases, oxidoreductases, pectinases, pentosanases, peroxidases, phenoloxidases, phospholipases, proteases, pullulanases, reductases, R- glucanases, tannases, transferases, xylanases, and mixtures thereof.

11. A formulation according to any preceding claim, wherein the hydrophobic material comprises an organic carbon based polymer; a haloalkane; a silicone / silicate based material; a fluorocarbon / fluoropolymer; a fatty acid; a fat / triglyceride; a fat or wax (including natural waxes, animal waxes, vegetable waxes, mineral waxes, petroleum waxes or synthetic waxes), preferably with a melting point in the range of 20°C to 200°C and more preferably in the range of 35°C to 85°C; or a mixture thereof.

12. A formulation according to any preceding claim, wherein the pH responsive, acrylic copolymer is insoluble at acidic and neutral pH values and soluble at basic pH values.

13. A formulation according to claim 12, wherein the pH responsive, acrylic copolymer is soluble at pH >7.5.

141. A formulation according to any preceding claim wherein the pH responsive, acrylic copolymer is prepared from monomers having only one polymerisable double bond.

15. A formulation according to claim 14, wherein the pH responsive, acrylic copolymer is prepared from one or more of the following monomers: acrylic acid (AA), methacrylic acid ( AA), beta carboxy ethyl acrylate (BCEA), itaconic acid, maleic acid, maleic anhydride, ita- conic anhydride, styrene and substituted styrenes such as -methyl styrene, methyl styrene, t-butyl styrene, alkyl esters of mono-olefinically unsaturated dicarboxylic acids such as di-n- butyl maleate and di-n-butyl fumarate; vinyl esters of carboxylic acids such as vinyl acetate, vinyl propionate, vinyl laurate and vinyl esters of versatic acid such as VeoVa_ 9 and VeoVa_ 10; acrylamides such as methyl acrylamide and ethyl acrylamide; methacrylamides such as methyl methacrylamide and ethyl methacrylamide; nitrile monomers such as acrylonitrile and methacrylonitrile; and esters of aciylic and methacrylic acid, preferably optionally substituted Ci-2.alkyl and O-socycloalky esters of acrylic and methacrylic acid, such as methyl acrylate, ethyl acrylate, n-butyl acrylate, 2-ethylhexyi acrylate, i-propyl acrylate, and n-propyl acrylate, methyl methacrylate, ethyl methacr ylate, n-butyl methacrylate, 2-ethylhexyl methacrylate, i- propyl methacrylate, n-propyl acrylate, hydroxyethy] acrylate, hydroxyethyl methacrylate, hydroxy! butyl methacrylate, N,Ndimethylaminoethyl acrylate and N,N-dimethylaminoethyl methacrylate, diacetone acrylamide, glycidyl methacrylate, aceto acetoxy ethyl methacrylate, and mixtures thereof.

16. A formulation according to claim 15, wherein the pH responsive, acrylic copolymer is prepared from one or more of the following monomers: methyl methacrylate (MMA), ethyl methacrylate (EMA), n-butyl methacrylate (BMA), iso-butyl methacrylate (iBMA), 2-ethylhexyl methacrylate (EHMA), 2-ethylhexyl acrylate (EHA), iso-bornyl methacrylate (iBoMA), methyl acrylate (MA), ethyl acrylate (EA), n-butyl acrylate (BA), styrene (STY), acrylic acid (AA), methacrylic acid (MAA), -carboxy ethyl acrylate (_-CEA), and sodium acrylate (SAA), and mixtures thereof.

17. A formulation according to any one of claims 1 to 13, wherein the pH responsive, acrylic copolymer is a meth(acrylic) copolymer of general formula I:

wherein:

-(X)x-(Y)_y-(Z)z- is a polymer backbone formed from the polymerization of X', Y' and Z' monomers;

X' is a first non-dissociating monomer of formula

Y' is a second no n -dissociating monomer of form

R6; Z' is a dissociating monomer of formula

or formula R3R4C=CRs-CO-0-

each independently hydrogen or an inert aliphatic or aromatic organic moiety;

Re is an inert aliphatic or aromatic organic moiety;

x is an integer from 30 to 90; y is an integer from 0 to 50;

z is an integer from 10 to 60;

wherein x, y and z represent the % molar composition of components X, Y and Z

respectively and the sum of x + y + z = 100%.

18. A formulation according to claim 17, wherein Ffe, FU, Rs are each independently hydrogen or an inert aliphatic or aromatic organic moiety selected from O to C2o alkyl or Ceto Cs aryl moieties, which moieties may be optionally substituted by a Ci to Celinear or branched alkyl group, or a C6 to Cioaryl group.

19. A formulation according to claim 17 or claim 18, wherein Ft6 is an inert aliphatic or aromatic organic moiety selected from Ci to C20 alkyl or Ce to Ce aryl moieties, which moieties may be optionally substituted by a O to Ce linear or branched alkyl group, or a Ceto Cio aryl group.

20. A fabric care formulation comprising, a composite according to any one of claims 1 -19, plus one or more active and/or non-active agents.

21. A fabric care formulation comprising from about 0.5% to about 25% by weight of a composite according to any one of claims 1 to 19.

22. A solid or liquid fabric care product comprising from about 0.5% to about 25% by weight of a composite according to any one of claims 1 to 19.

23. A solid or liquid fabric care according to claim 22, comprising a benefit agent selected from a bleaching agent, enzyme, fragrance or perfume, or a mixture thereof.