CN112567013B - Benefit agent delivery particles - Google Patents

Abstract

The present invention provides a benefit agent delivery particle having a core-shell structure wherein a porous shell of polymeric material encapsulates a core comprising the benefit agent; wherein the apertures in the shell are at least partially blocked by a washable, removable coating disposed at an outer surface of the shell; characterized in that the washable removable coating is formed from deposited particles of a complex of a cationic surfactant and an anionic surfactant. The present invention also provides a laundry treatment composition comprising benefit agent delivery particles as defined above.

Description

Benefit agent delivery particles

Technical Field

The present invention relates to benefit agent (e.g., fragrance) delivery particles and compositions (e.g., laundry treatment compositions) comprising the same.

Background

In laundry treatment compositions such as laundry detergents, consumer perceived fragrance is one of the most important attributes. Efficient delivery of the appropriate fragrance to the fabric during laundering and release of the fragrance at critical consumer times is critical to delivering clean, fresh laundered clothing.

Delivery of fragrance at critical times is a difficult task because laundry detergents are typically designed to carry oily substances or particulate solids away from the laundered fabrics. While fragrances are also typical oily substances.

The encapsulation of the fragrance results in improved deposition of the fragrance onto the fabric and delays release of the fragrance when the consumer garment is worn.

However, another important moment for the consumer is when the laundry is in the "wet" phase, which extends from when the laundry is taken out of the washing machine to when the laundry is almost dry. There is a need for compositions that deliver a good fragrance experience during this stage, without causing significant impairment of fragrance performance at other stages (e.g., packaging the composition before use and when the laundered laundry dries).

The present invention solves this problem.

Disclosure of Invention

The present invention provides a benefit agent delivery particle having a core-shell structure wherein a porous shell of polymeric material encapsulates a core comprising the benefit agent; wherein the apertures in the shell are at least partially blocked by a washable, removable coating disposed at an outer surface of the shell; characterized in that the washable removable coating is formed from deposited particles of a complex of a cationic surfactant and an anionic surfactant.

The present invention also provides a laundry treatment composition comprising benefit agent delivery particles as defined above.

Detailed Description

The core of the benefit agent delivery particles of the present invention is typically formed in the interior region of the particles and provides a pool for the benefit agent. The shell generally protects the benefit agent from the external environment and regulates the flow of the benefit agent into and out of the core.

In the benefit agent delivery particles of the present invention, the presence of the washable, removable coating serves to reduce leakage of entrapped benefit agent through the pores in the shell. Removal of the coating during the washing operation helps to release the trapped benefit agent.

The term "laundering operation" as used herein generally refers to a method of laundering fabrics using the laundry treatment composition according to the present invention.

The washable, removable coating is formed from deposited particles of a complex of a cationic surfactant and an anionic surfactant.

Preferably, the solubility of the complex in distilled water (at 25 ℃ and atmospheric pressure) is less than about 10mg/L, preferably less than about 1mg/L, to prevent the coating from being removed too quickly during washing.

In a preferred method for preparing the benefit agent delivery particles of the present invention, a cationic surfactant is first mixed with an aqueous slurry of preformed particles having a core-shell structure, wherein a porous shell of polymeric material surrounds a core comprising the benefit agent (hereinafter "preformed core-shell particles"). The cationic surfactant is deposited on the outer surface of the shell of the preformed core-shell particle. The anionic surfactant is then added to the mixture of particles so that it forms a complex with the cationic surfactant deposited on the outer surface of the shell of the particles. The charged heads of the respective surfactants are neutralized during the compounding process.

The anionic and cationic surfactants used to form the complex typically have a molecular weight of about 1000 or less and a solubility in distilled water (at 25 ℃ and atmospheric pressure) of at least about 10mg/L, preferably at least about 100mg/L.

Suitable cationic surfactants for forming the complex may be selected from mono-long chain quaternary ammonium compounds of formula (I):

R ¹ R ² R ³ R ⁴ N ⁺ X ^- (I)

wherein R is ¹ Selected from linear or branched alkyl or alkenyl chains containing 6 to 24 carbon atoms and 0 or 1 double bond, R ² 、R ³ And R is ⁴ Each independently selected from C1 to C3 alkyl and- (C) _n H _2n O) _x H groups wherein n is 2 or 3, x is 1 to about 3, and x is an anion selected from chloride, bromide, iodide, nitrate, sulfate, methosulfate, ethylsulfate, acetate, and phosphate.

Preferably, in the above general formula (I), R ¹ Selected from C16 to C22 straight saturated alkyl chains, R ² 、R ³ And R is ⁴ Each independently selected from CH ₃ And CH (CH) ₂ CH ₂ OH, more preferably CH ₃ 。

Specific examples of preferred cationic surfactants for forming the complex include cetyltrimethylammonium chloride (CTAC), stearyltrimethylammonium chloride (STAC), behenyl Trimethyl Ammonium Chloride (BTAC), and mixtures thereof.

Suitable anionic surfactants for forming the complex may be selected from organic sulphates and sulphonates having alkyl radicals containing from about 8 to about 22 carbon atoms, the term "alkyl" being used to include the alkyl portion of higher acyl radicals. Examples of such materials include alkyl sulfates, alkyl ether sulfates, alkylaryl sulfonates, alpha olefin sulfonates, and mixtures thereof. The alkyl group preferably contains 10 to 18 carbon atoms and may be unsaturated. The alkyl ether sulfate may contain one to ten ethylene oxide or propylene oxide units per molecule, and preferably contains one to three ethylene oxide units per molecule. The counter ion of the anionic surfactant is typically an alkali metal such as sodium or potassium; or an ammoniated counterion such as Monoethanolamine (MEA), diethanolamine (DEA) or Triethanolamine (TEA). Mixtures of such counterions can also be used.

Preferred anionic surfactants for forming the complex include alkylbenzenesulfonates, particularly Linear Alkylbenzenesulfonates (LAS) having an alkyl chain length of 10 to 18 carbon atoms. Commercial LAS is a mixture of closely related isomers and homologs of alkyl chains, each containing a sulfonated aromatic ring in the "para" position and attached to a linear alkyl chain at any position other than the terminal carbon. The linear alkyl chain typically has a chain length of 11 to 15 carbon atoms, the primary material having about C ₁₂ Chain length of (d) is provided. Each alkyl chain homolog consists of a mixture of all possible sulfophenyl isomers, except the 1-phenyl isomer.

Also suitable are alkyl ether sulphates having linear or branched alkyl groups of 10 to 18, more preferably 12 to 14 carbon atoms and containing an average of 1 to 3EO units per molecule. A preferred example is Sodium Lauryl Ether Sulphate (SLES), in which predominantly C12 lauryl alkyl groups have been ethoxylated, with an average of 3EO units per molecule.

PreferablyHas a negative charge at its shell outer surface and has a zeta potential of from-0.1 meV to-100 meV, more preferably from-10 meV to-80 meV, most preferably from-20 meV to-75 meV. Zeta potential using Zetasizer Nano at 25℃by Dynamic Light Scattering (DLS) method ^TM ZS90 (Malvern Instruments Ltd, UK) is suitably measured. A dispersion of particles having a solids content of about 500ppm and a pH adjusted to about 7 in deionized water was used for this measurement.

Preformed core-shell particles may suitably be prepared using methods known to those skilled in the art, such as coacervation, interfacial polymerization, and polycondensation.

The agglomeration process typically involves depositing a colloidal material onto the surface of droplets of the material to encapsulate a generally water insoluble core material. Coacervation may be simple, for example, using one colloid, e.g. gelatin, under carefully controlled conditions of pH, temperature and concentration, or a complex of two or more of them with opposite charges, e.g. gelatin and gum arabic or gelatin and carboxymethylcellulose.

Interfacial polymerization generally continues as a fine dispersion of oil droplets (which contain the core material) in the aqueous continuous phase. The dispersed droplets form the core of the missing core-shell particles, and the size of the dispersed droplets directly determines the size of the missing core-shell particles. The shell forming material (monomer or oligomer) is contained in both the dispersed phase (oil droplets) and the aqueous continuous phase and they react together at the phase interface to build up a polymer wall around the oil droplets, encapsulating the droplets. An example of a core-shell particle produced by this method has a polyurea shell formed by the reaction of a di-or polyisocyanate with a di-or polyamine.

Polycondensation involves forming a dispersion or emulsion of the core material in an aqueous solution of a precondensate of the polymeric material under suitable agitation conditions to produce a dispersed core material of the desired particle size, and adjusting the reaction conditions to cause condensation of the precondensate by acid catalysis, resulting in the condensate separating from the solution and surrounding the dispersed core material to produce a cohesive film and the desired particles. An example of a core-shell particle produced by this method has an aminoplast shell formed from melamine (2, 4, 6-triamino-1, 3, 5-triazine) or the polycondensation product of urea and formaldehyde. Suitable cross-linking agents (e.g., toluene diisocyanate, divinylbenzene, butanediol diacrylate) may also be used, and second wall polymers, such as polymers and copolymers of anhydrides and derivatives thereof, particularly maleic anhydride, may also be used as appropriate.

In the benefit agent delivery particles of the present invention, the porous shell of polymeric material is preferably an aminoplast shell formed from the polycondensation product of melamine and formaldehyde.

The shell is preferably substantially spherical; and typically comprise up to 20 wt% based on the total weight of the benefit agent delivery particles.

The benefit agent delivery particles of the present invention typically have an average particle size of between 100 nanometers and 50 microns. Particles larger than this range enter the visible range. Examples of particles in the submicron range include latices and microemulsions having average particle sizes in the range of 100 to 600 nanometers. The core-shell particles suitable for use in the present invention preferably have an average size of from 0.6 to 50 microns, more preferably from 2 to 30 microns, and most preferably from 5 to 25 microns. The particle size distribution may be narrow, broad or multimodal. The initially produced particles can be filtered or screened, if necessary, to produce a product with higher dimensional uniformity.

As used herein, unless otherwise indicated, "size" refers to diameter. For samples having particle diameters no greater than 1 micron, diameter refers to the measured z-average particle size, e.g., using dynamic light scattering (as described in International Standard ISO 13321) and instrumentation such as Zetasizer Nano ^TM Measured as ZS90 (Malvern Instruments Ltd, UK). For samples with particle diameters greater than 1 micron, diameter refers to the apparent volume median diameter (D50), for example, by laser diffraction (as described in International Standard ISO 13320) and instrumentation such as a Mastersizer ^TM 2000 (Malvern Instruments Ltd, UK) measurements.

The benefit agent delivery particles of the present invention may be provided with a deposition aid at the outer surface of the shell. Deposition aids are used to alter the properties of the shell outer surface, for example to make the particles more compatible with the desired matrix. Desirable substrates include cellulose (including cotton) and polyester (including those used to produce polyester fabrics).

The deposition aid may suitably be provided at the outer surface of the shell by means of covalent bonding, entanglement or strong adsorption. Preferably, such deposition aids are attached to the shell outer surface directly by covalent bonding or via a linking substance.

The deposition aid used in the present invention may be suitably selected from polysaccharides having affinity for cellulose. Such polysaccharides may be naturally occurring or synthetic and may have an inherent affinity for cellulose, or may have been derivatized or otherwise modified to have an affinity for cellulose. Suitable polysaccharides have a 1-4 linked beta-glycan (generalized saccharide) backbone structure, having at least 4 and preferably at least 10 of them are beta 1-4 linked backbone residues, such as a glucan backbone (consisting of beta 1-4 linked glucose residues), a mannan backbone (consisting of beta 1-4 linked mannose residues) or a xylan backbone (consisting of beta 1-4 linked xylose residues). Examples of such beta 1-4 linked polysaccharides include xyloglucan, glucomannan, mannan, galactomannan, beta (1-3), (1-4) glucan, and xylan families comprising glucuronyl (glucuronono) -, arabinosyl (arabino) -and glucuronoxylomannan. Preferred β1-4 linked polysaccharides for use in the present invention may be selected from xyloglucans of plant origin, such as pea xyloglucan and tamarind seed xyloglucan (TXG) (which has a β1-4 linked glucan backbone with side chains of α -D xylopyranose and β -D-galactopyranosyl- (1-2) - α -D-xylopyranose, both 1-6 linked to the backbone); and galactomannans of plant origin, such as Locust Bean Gum (LBG), which has a mannan backbone with β1-4 linked mannose residues, with single unit galactose side chains with α1-6 linked to the backbone.

Also suitable are polysaccharides that upon hydrolysis can obtain affinity for cellulose (e.g., cellulose monoacetate); or modified polysaccharides having affinity for cellulose such as hydroxypropyl cellulose, hydroxypropyl methylcellulose, hydroxyethyl methylcellulose, hydroxypropyl guar gum, hydroxyethyl ethylcellulose, and methylcellulose.

The deposition aid used in the present invention may also be selected from phthalate-containing polymers having affinity for polyesters. Such phthalate-containing polymers may have one or more nonionic hydrophilic segments comprising an oxyalkylene group, such as an oxyethylene, polyoxyethylene, oxypropylene or polyoxypropylene group, and one or more hydrophobic segments comprising a terephthalate group. Generally, the oxyalkylene groups will have a degree of polymerization of from 1 to about 400, preferably from 100 to about 350, more preferably from 200 to about 300. Suitable examples of phthalate-containing polymers of this type are copolymers having random blocks of ethylene terephthalate and polyethylene oxide terephthalate.

Mixtures of any of the above materials may also be suitable.

The deposition aid used in the present invention will generally have a weight average molecular weight (M) in the range of about 5kDa to about 500kDa, preferably about 10kDa to about 500kDa and more preferably about 20kDa to about 300kDa _w )。

In the benefit agent delivery particles of the present invention, the core comprises a benefit agent. In the case of fabric washing, preferred benefit agents include fragrance, clay, enzymes, antifoam agents, fluorescers, bleaches and their precursors (including photobleaching), dyes and/or pigments, conditioning agents (e.g., cationic surfactants including water insoluble quaternary ammonium materials, fatty alcohols and/or silicones), lubricants (e.g., sugar polyesters), color and photoprotectants (including opacifiers), antioxidants, ceramides, reducing agents, chelating agents, color care additives (including fixing agents), unsaturated oils, lubricants, humectants, insect repellents and/or pheromones, drape modifiers (e.g., polymer latex particles such as PVA), and antimicrobial agents or microbial control agents.

Mixtures of any of the above materials may also be suitable. In the context of the present invention, the most preferred benefit agent is a fragrance formulation.

The fragrance formulation for use in the present invention will generally contain a mixture of selected fragrance components, optionally in admixture with one or more excipients. The combined odor of the various fragrance components produces a pleasant or desired fragrance.

In the context of the present invention, the term "fragrance component" refers to a material used essentially for its ability to impart a pleasant odor to the composition (into which it is incorporated) and/or to the surface (to which it is applied), alone or in combination with other such materials. Materials with these properties are typically small lipophilic molecules with sufficient volatility to be transported to the olfactory system in the upper part of the nose.

The fragrance component for use in the present invention will generally have a molecular weight of less than 325 atomic mass units, preferably less than 300 atomic mass units and more preferably less than 275 atomic mass units. The molecular weight is preferably greater than 100 atomic mass units, more preferably greater than 125 atomic mass units, as lower masses may be too volatile and/or insufficiently lipophilic to be effective.

The fragrance component for use in the present invention will preferably have a molecular structure that is free of halogen atoms and/or strongly ionised functional groups such as sulfonate, sulfate or quaternary ammonium ions.

The fragrance component for use in the present invention will more preferably have a molecular structure containing only atoms from the following (but not necessarily all): hydrogen, carbon, oxygen, nitrogen and sulfur. Most preferably, the aromatic component will have a molecular structure containing only atoms from (but not necessarily all of) the following: hydrogen, carbon and oxygen.

Examples of aromatic components include aromatic hydrocarbons, aliphatic hydrocarbons, and araliphatic (araliphatic) hydrocarbons having a molecular weight of about 90 to about 250; aromatic, aliphatic, and araliphatic esters having a molecular weight of about 130 to about 250; aromatic, aliphatic and araliphatic nitriles having a molecular weight of about 90 to about 250; aromatic, aliphatic, and araliphatic alcohols having a molecular weight of about 90 to about 240; aromatic, aliphatic, and araliphatic ketones having a molecular weight of about 150 to about 270; aromatic lactones, aliphatic lactones and araliphatic lactones having a molecular weight of about 130 to about 290; aromatic, aliphatic, and araliphatic aldehydes having a molecular weight of about 90 to about 230; aromatic, aliphatic, and araliphatic ethers having a molecular weight of about 150 to about 270; and condensation products of aldehydes and amines having a molecular weight of about 180 to about 320.

Specific examples of the fragrance component for use in the present invention include:

i) Hydrocarbons such as, for example, D-limonene, 3-carene (carene), α -pinene, β -pinene, α -terpinene, γ -terpinene, p-cymene, myrrh (bissabolene), camphene, caryophyllene, cedrene, farnesene, longifolene, myrcene, ocimene, valencene (valene), (E, Z) -1,3, 5-undecatriene, styrene and diphenylmethane;

ii) an aliphatic alcohol and an araliphatic alcohol, such as, for example, benzyl alcohol, 1-phenethyl alcohol, 2-phenethyl alcohol, 3-phenylpropanol, 2-phenoxyethanol, 2-dimethyl-3-phenylpropanol, 2-dimethyl-3- (3-methylphenyl) propanol, 1-dimethyl-2-phenethyl alcohol, 1-dimethyl-3-phenylpropanol, 1-ethyl-1-methyl-3-phenylpropanol, 2-methyl-5-phenylpentanol, 3-phenyl-2-propen-1-ol 4-methoxybenzyl alcohol, 1- (4-isopropylphenyl) ethanol, hexanol, octanol, 3-octanol, 2, 6-dimethylheptanol, 2-methyl-2-heptanol, 2-methyl-2-octanol, (E) -2-hexenol, (E) -and (Z) -3-hexenol, 1-octen-3-ol, 3,4,5, 6-pentamethyl-3/4-hepten-2-ol and 3,5,6,6-tetramethyl-4-methylenehept-2-ol, Z) -2, 6-nondienol, 3, 7-dimethyl-7-methoxyoct-2-ol, 9-decenol, 10-undecylenol and 4-methyl-3-decen-5-ol;

iii) Cyclic alcohols and cycloaliphatic alcohols, such as, for example, 4-tert-butylcyclohexanol, 3, 5-trimethylcyclohexanol, 3-isobornylcyclohexanol, 2,6, 9-trimethyl-Z2, Z5, E9-cyclododecatrien-1-ol, 2-isobutyl-4-methyltetrahydro-2H-pyran-4-ol, alpha, 3, 3-trimethylcyclohexylmethanol, 2-methyl-4- (2, 3-trimethyl-3-cyclopent-1-yl) butanol, 2-methyl-4- (2, 3-trimethyl-3-cyclopent-1-yl) -2-buten-1-ol, 2-ethyl-4- (2, 3-trimethyl-3-cyclopent-1-yl) -2-buten-1-ol 3-methyl-5- (2, 3-trimethyl-3-cyclopent-1-yl) -pentan-2-ol, 3-methyl-5- (2, 3-trimethyl-3-cyclopent-1-yl) -4-penten-2-ol, 3-dimethyl-5- (2, 3-trimethyl-3-cyclopent-1-yl) -4-penten-2-ol, 1- (2, 6-trimethylcyclohexyl) pentan-3-ol and 1- (2, 6-trimethylcyclohexyl) hexan-3-ol;

iv) aliphatic aldehydes and acetals thereof, such as, for example, hexanal, heptanal, octanal, nonanal, decanal, undecanal, laural, tridecanol, 2-methyloctanal, 2-methylnonanal, 2-methylundecanal, (E) -2-hexenal, (Z) -4-heptenal, 2, 6-dimethyl-5-heptenol, 10-undecenal, (E) -4-decenal, 2-dodecenal, 2,6, 10-trimethyl-5, 9-10-undecadienal, heptanal-diethyl acetal, 1-dimethoxy-2, 5-trimethyl-4-hexene and citronellyloxy acetaldehyde (citronellyl oxyacetaldehyde);

v) aliphatic ketones and oximes thereof, such as, for example, 2-heptanone, 2-octanone, 3-octanone, 2-nonanone, 5-methyl-3-heptanone oxime and 2,4, 7-tetramethyl-6-octen-3-one;

vi) aliphatic sulfur-containing compounds such as, for example, 3-methylthiohexanol, 3-methylthiohexyl acetate, 3-mercaptohexanol, 3-mercaptohexyl acetate, 3-mercaptohexyl butyrate, 3-acetylthiohexyl acetate and 1-menthene-8-thiol;

vii) aliphatic nitriles such as, for example, 2-nonenenitrile, 2-tridecenenitrile, 2, 12-tridecenenitrile, 3, 7-dimethyl-2, 6-octadienenitrile and 3, 7-dimethyl-6-octenenitrile;

viii) aliphatic carboxylic acids and esters thereof, such as, for example, (E) -and (Z) -3-hexenyl formate, ethyl acetoacetate, isopentyl acetate, hexyl 3, 5-trimethylacetate, ethyl octanoate, ethyl- (E, Z) -2, 4-decadienoate, methyl-2-octanoate, methyl-2-nonanoate, allyl-2-isopentyloxy acetate, methyl-3, 7-dimethyl-2, 6-octadienoate;

ix) acyclic terpene alcohols such as, for example, citronellol; geraniol; nerol; linalool; lavender alcohol; nerolidol; farnesol; tetrahydrolinalool; tetrahydrogeraniol; 2, 6-dimethyl-7-octen-2-ol; 2, 6-dimethyloctan-2-ol; 2-methyl-6-methylene-7-octen-2-ol; 2, 6-dimethyl-5, 7-octadien-2-ol; 2, 6-dimethyl-3, 5-octadien-2-ol; 3, 7-dimethyl-4, 6-octadien-3-ol; 3, 7-dimethyl-1, 5, 7-octatrien-3-ol; 2, 6-dimethyl-2, 5, 7-octatrien-1-ol; and their formates, acetates, propionates, isobutyrates, butyrates, isovalerates, valerates, caproate, crotonates, homozhilates and 3-methyl-2-butenoate;

x) acyclic terpene aldehydes and ketones, such as, for example, geranial, neral, citronellal, 7-hydroxy-3, 7-dimethyloctanal, 7-methoxy-3, 7-dimethyloctanal, 2,6, 10-trimethyl-9-undecylenal, α -sweet-neral, β -sweet-neral, geranylacetone, and dimethyl and diethyl acetals of geranial, neral and 7-hydroxy-3, 7-dimethyloctanal;

xi) cyclic terpene alcohols such as, for example, menthol, isopulegol, alpha-terpineol, terpinen-4-ol, menthan-8-ol, menthan-1-ol, menthan-7-ol, borneol, isoborneol, linalool oxide, nopol, cedrol, ambroxol (ambrinol), vetch alcohol, guaiacol, and alpha-terpineol, terpinen-4-ol, menthan-8-ol, menthan-1-ol, menthan-7-ol, borneol, isoborneol, linalool oxide, nopol, cedrol, ambroxol, petrolatum and guaiacol formates, acetates, propionates, isobutyrates, butyrates, isovalerates, valerates, caproate, crotonates, maleic acid esters and 3-methyl-2-butenoate;

xii) cyclic terpene aldehydes and ketones such as, for example, menthone, isomenthone, 8-mercaptomenthan-3-one, carvone, camphor, fennel ketone, α -ionone, β -ionone, α -n-methylionone, β -isoionone, α -irone, α -damascone, β -damascone Ma Xitong, δ -damascone, γ -damascone, 1- (2, 4-trimethyl-2-cyclohexen-1-yl) -2-butene-1-one, 1,3,4,6,7,8 a-hexahydro-1, 5-tetramethyl-2H-2, 4 a-methanonaphthalene-8 (5H) -one, nocarpus ketone, dihydro-damascenone and beryl methyl ketone;

xiii) cyclic and cycloaliphatic ethers such as, for example, eucalyptol, cedryl methyl ether, cyclododecyl methyl ether, (ethoxymethoxy) cyclododecane; α -cedrene epoxide, 3a,6, 9 a-tetramethyldodecahydronaphtho [2,1-b ] furan, 3 a-ethyl-6, 9 a-trimethyldodecahydronaphtho [2,1-b ] furan, 1,5, 9-trimethyl-13-oxabicyclo [10.1.0] -tridec-4, 8-diene, rose oxide and 2- (2, 4-dimethyl-3-cyclohexen-1-yl) -5-methyl-5- (1-methylpropyl) -1, 3-dioxane;

xiv) cyclic ketones such as, for example, 4-tert-butylcyclohexanone, 2, 5-trimethyl-5-pentylcyclopentanone, 2-heptylcyclopentanone, 2-pentylcyclopentanone, 2-hydroxy-3-methyl-2-cyclopenten-1-one, 3-methyl-cis-2-penten-1-yl-2-cyclopenten-1-one, 3-methyl-2-pentyl-2-cyclopenten-1-one, 3-methyl-4-cyclopentadecanone, 3-methyl-5-cyclopentadecanone, 3-methylcyclopentadecanone, 4- (1-ethoxyvinyl) -3, 5-tetramethylcyclohexanone, 4-tert-pentylcyclohexanone, 5-cyclohexadecen-1-one, 6, 7-dihydro-1, 2, 3-pentamethyl-4 (5H) -indanone, 5-cyclohexaen-1-one, 8-cyclohexaen-1-one, 9-cyclohexadecen-1-one and cyclopentadecanone;

xv) cycloaliphatic aldehydes and ketones, such as, for example, 2, 4-dimethyl-3-cyclohexenecarboxaldehyde, 2-methyl-4- (2, 6-trimethyl-cyclohexen-1-yl) -2-butenal, 4- (4-hydroxy-4-methylpentyl) -3-cyclohexenecarboxaldehyde, 4- (4-methyl-3-penten-1-yl) -3-cyclohexenecarboxaldehyde, 1- (3, 3-dimethylcyclohexyl) -4-penten-1-one, 1- (5, 5-dimethyl-1-cyclohexen-1-yl) -4-penten-1-one, 2,3, 8-tetramethyl-1, 2,3,4,5,6,7, 8-octahydro-2-naphthylenemethyl ketone, methyl-2, 6, 10-trimethyl-2, 5, 9-cyclododecenyl ketone and tert-butyl- (2, 4-dimethyl-3-cyclohexen-1-yl) ketone;

xvi) esters of cyclic alcohols, such as, for example, 2-tert-butylcyclohexyl acetate, 4-tert-butylcyclohexyl acetate, 2-tert-pentylcyclohexyl acetate, 4-tert-pentylcyclohexyl acetate, decahydro-2-naphthylacetate, 3-pentylthetrahydro-2H-pyran-4-ylacetate, decahydro-2, 5,8 a-tetramethyl-2-naphthylacetate, 4, 7-methano-3 a,4,5,6,7 a-hexahydro-5-or 6-indenyl acetate, 4, 7-methano-3 a,4,5,6,7 a-hexahydro-5-or 6-indenyl propionate, 4, 7-methano-3 a,4,5,6,7 a-hexahydro-5 or 6-indenyl isobutyrate and 4, 7-methano-octahydro-5-or 6-indenyl acetate;

xvii) esters of cycloaliphatic carboxylic acids, such as, for example, allyl 3-cyclohexyl-propionate, allyl cyclohexyloxy acetate, methyl dihydrojasmonate, methyl jasmonate, methyl 2-hexyl-3-oxocyclopentanecarboxylate, ethyl 2-ethyl-6, 6-dimethyl-2-cyclohexene carboxylate, ethyl 2,3,6,6-tetramethyl-2-cyclohexene carboxylate and ethyl 2-methyl-1, 3-dioxolane-2-acetate;

xviii) esters of araliphatic alcohols and aliphatic carboxylic acids, such as, for example, benzyl acetate, benzyl propionate, benzyl isobutyrate, benzyl isovalerate, 2-phenethyl acetate, 2-phenethyl propionate, 2-phenethyl isobutyrate, 2-phenethyl isovalerate, 1-phenethyl acetate, α -trichloromethylbenzyl acetate, α -dimethylbenzene ethyl butyrate, cinnamyl acetate, 2-phenoxyethyl isobutyrate and 4-methoxybenzyl acetate;

xix) araliphatic ethers and acetals thereof, such as, for example, 2-phenethyl methyl ether, 2-phenethyl isoamyl ether, 2-phenethyl cyclohexyl ether, 2-phenethyl-1-ethoxyethyl ether, phenylacetaldehyde dimethyl acetal, phenylacetaldehyde diethyl acetal, 2-phenylpropionyl dimethyl acetal, phenylacetaldehyde glycerol acetal, 2,4, 6-trimethyl-4-phenyl-1, 3-dioxane, 4a,5,9 b-tetrahydroindeno [1,2-d ] -m-dioxin and 4,4a,5,9 b-tetrahydro-2, 4-dimethylindeno [1,2-d ] -m-dioxin;

xx) aromatic and araliphatic aldehydes and ketones, such as, for example, benzaldehyde; phenylacetaldehyde, 3-phenylpropionaldehyde, 2-phenylpropionaldehyde, 4-methylbenzaldehyde, 3- (4-ethylphenyl) -2, 2-dimethylpropionaldehyde, 2-methyl-3- (4-isopropylphenyl) propanal, 2-methyl-3- (4-tert-butylphenyl) propanal, cinnamaldehyde, alpha-butylcinnamaldehyde, alpha-pentylmennamaldehyde, alpha-hexylcinnamaldehyde, 3-methyl-5-phenylpentanal, 4-methoxybenzaldehyde, 4-hydroxy-3-ethoxybenzaldehyde, 3, 4-methylene-dioxybenzaldehyde, 3, 4-dimethoxybenzaldehyde, 2-methyl-3- (4-methoxyphenyl) propanal, 2-methyl-3- (4-methylenedioxyphenyl) propanal, acetophenone, 4-methylacetophenone, 4-methoxyacetophenone, 4-tert-butyl-2, 6-dimethyl, 4-phenyl-2-acetophenone, 4- (4-hydroxyphenyl) -2-butanone, 1- (2-naphthyl) ethanone, benzophenone, 1,1,2,3,3,6-hexamethyl-5-indanylmethyl ketone, 6-tert-butyl-1, 1-dimethyl-4-indanylmethyl ketone, 1- [2, 3-dihydro-1,1,2,6-tetramethyl-3- (1-methylethyl) -1H-5-indenyl ] ethanone and 5',6',7',8' -tetrahydro-3 ',5',5',6',8',8' -hexamethyl-2-naphthacenedione;

xxi) aromatic and araliphatic carboxylic acids and their esters, such as, for example, benzoic acid, phenylacetic acid, methyl benzoate, ethyl benzoate, hexyl benzoate, benzyl benzoate, methyl phenylacetate, ethyl phenylacetate, geranyl phenylacetate, phenethyl phenylacetate, methyl cinnamate, ethyl cinnamate, benzyl cinnamate, phenethyl cinnamate, cinnamyl cinnamate, allyl phenoxyacetate, methyl salicylate, isoamyl salicylate, hexyl salicylate, cyclohexyl salicylate, cis-3-hexenyl salicylate, benzyl salicylate, phenethyl salicylate, methyl 2, 4-dihydroxy-3, 6-dimethylbenzoate, ethyl 3-phenylglycerate and ethyl 3-methyl-3-phenylglycerate;

xxii) nitrogen-containing aromatic compounds such as, for example, 2,4, 6-trinitro-1, 3-dimethyl-5-tert-butylbenzene, 3, 5-dinitro-2, 6-dimethyl-4-tert-butylacetophenone, cinnamonitrile, 5-phenyl-3-methyl-2-pentenenitrile, 5-phenyl-3-methylpentanenitrile, methyl anthranilate, methyl N-methylparaben, methyl anthranilate with 7-hydroxy-3,3,7-dimethyloctanal, schiff base of 2-methyl-3- (4-tert-butylphenyl) propanal or 2, 4-dimethyl-3-cyclohexene carboxaldehyde, 6-isopropylquinoline, 6-isobutylquinoline, 6-sec-butylquinoline, indole, methylindole, 2-methoxy-3-isopropylpyrazine and 2-isobutyl-3-methoxypyrazine;

xxiii) phenols, phenyl ethers and phenyl esters, such as, for example, estragole, anethole, eugenol methyl ether, isoeugenol methyl ether, thymol, carvacrol, diphenyl ether, beta-anisole, beta-naphtalene ethyl ether, beta-naphtalibutyl ether, 1, 4-dimethoxybenzene, eugenol acetate, 2-methoxy-4-methylphenol, 2-ethoxy-5- (1-propenyl) phenol and p-cresol phenylacetate;

xxiv) heterocyclic compounds, such as, for example, 2, 5-dimethyl-4-hydroxy-2H-furan-3-one, 2-ethyl-4-hydroxy-5-methyl-2H-furan-3-one, 3-hydroxy-2-methyl-4H-pyran-4-one, 2-ethyl-3-hydroxy-4H-pyran-4-one;

xxv) lactones such as, for example, 1, 4-octanolide, 3-methyl-1, 4-octanolide, 1, 4-nonanolide, 1, 4-decanolide, 8-decen-1, 4-olide, 1, 4-undecanolide, 1, 4-dodecanolide, 1, 5-decanolide, 1, 5-dodecanolide, 1, 15-pentadecanolide, cis-and trans-1' -pentadecanolide-1, 15-lactone, cis-and trans-12-pentadecanolide-1, 15-lactone, 1, 16-hexadecanolide, 9-hexadecene-1, 16-lactone, 10-oxa-1, 16-hexadecanolide, 11-oxa-1, 16-hexadecanolide, 12-oxa-1, 16-hexadecanolide, vinyl-1, 12-dodecanedioate, vinyl-1, 13-tridecanedioate, coumarin, 2, 3-dihydrocoumarin and octahydrocoumarin.

Naturally occurring exudates such as essential oils extracted from plants may also be used as the fragrance component in the present invention. Essential oils are typically extracted by steam distillation, solid phase extraction, cold pressing, solvent extraction, supercritical fluid extraction, water distillation or simultaneous distillation-extraction. Essential oils may originate from several different parts of plants, including for example leaves, flowers, roots, shoots, twigs, rhizomes, heartwood, bark, resins, seeds and fruits. The major plant families from which essential oils are extracted include the Asteraceae (Asteraceae), myrtaceae (Myrtaceae), camphoraceae (Lauraceae), labiaceae (Lamiaceae), myrtaceae (Myrtaceae), rutaceae (Rutaceae) and Zingiberaceae (Zingiberaceae). The oil is "essential" in the sense that it carries the unique fragrance or essence of the plant.

Those skilled in the art understand that essential oils are complex mixtures, typically consisting of tens or hundreds of components. Most of these components have an isoprenoid backbone with 10 carbon atoms (monoterpenes), 15 carbon atoms (sesquiterpenes), or 20 carbon atoms (diterpenes). Smaller amounts of other components such as alcohols, aldehydes, esters and phenols may also be found. However, in the context of practicing fragrance formulations, individual essential oils are generally considered as a single ingredient. Thus, individual essential oils may be considered as a single fragrance component for the purposes of the present invention.

Specific examples of essential oils used as the aromatic component of the present invention include cedar oil, juniper oil, cumin oil, cassia oil, camphor oil, rosewood oil, ginger oil, basil oil, eucalyptus oil, lemon grass oil, peppermint oil, rosemary oil, spearmint oil, tea tree oil, oil of jojoba oil, chamomile oil, clove oil, jasmine oil, lavender oil, rose oil, ylang-ylang oil (ylang-ylang oil), bergamot oil, grapefruit oil, lemon oil, lime oil, orange oil, fir needle oil (fir needle oil), white pine oil (galbanum oil), geranium oil, grapefruit oil, pine leaf oil, caraway oil (labdanum oil), heracleum oil, ganmajoram oil, oregano oil, orange oil, perilla oil, nutmeg oil, myrtle oil, clove oil, orange flower oil, patchouli oil, sandalwood oil, thyme oil, verbena oil, vetiver oil, and bergamot oil.

The amount of different fragrance components included in the fragrance formulation will generally be at least 4, preferably at least 6, more preferably at least 8 and most preferably at least 10, such as from 10 to 200, more preferably from 10 to 100.

Typically, no single fragrance component will comprise more than 70% by weight of the total weight of the fragrance formulation. Preferably, no single fragrance component will comprise more than 60% by weight of the total weight of the fragrance formulation, more preferably no single fragrance component will comprise more than 50% by weight of the total weight of the fragrance formulation.

In the context of the present invention, the term "fragrance formulation" refers to a fragrance component as defined above, plus any optional excipients. Excipients may be included in fragrance formulations for various purposes, for example as solvents for insoluble or poorly soluble components, as diluents for more effective components, or for controlling the vapor pressure and evaporation characteristics of the fragrance formulation. Excipients may have many of the characteristics of the aroma component, but they do not have a strong odor themselves. Thus, excipients can be distinguished from fragrance components in that they can be added to fragrance formulations in high proportions (e.g., 30 wt% or even 50 wt% of the total weight of the fragrance formulation) without significantly altering the odor quality of the fragrance formulation. Some examples of suitable excipients include ethanol, isopropanol, diethylene glycol monoethyl ether, dipropylene glycol, diethyl phthalate and triethyl citrate. Mixtures of any of the above materials may also be suitable.

Suitable fragrance formulations for use in the present invention comprise a mixture of at least 10 fragrance components selected from the group consisting of: hydrocarbon i); aliphatic and araliphatic alcohols ii); aliphatic aldehydes and acetals iv) thereof; aliphatic carboxylic acids and esters viii thereof; acyclic terpene alcohols ix); cyclic terpene aldehydes and ketones xii); cyclic and cycloaliphatic ethers xiii); esters of cyclic alcohols xvi); esters of araliphatic alcohols and aliphatic carboxylic acids xviii); araliphatic ethers and acetals thereof xix); aromatic and araliphatic aldehydes and ketones xx), and aromatic and araliphatic carboxylic acids and esters xxi) thereof; as further described and exemplified above.

The content of the fragrance component is preferably in the range of 50 to 100%, more preferably 60 to 100% and most preferably 75 to 100% by weight based on the total weight of the fragrance formulation; if desired, one or more excipients (as described above) make up the balance of the fragrance formulation.

Fragrance formulations typically comprise from about 10% to about 60%, preferably from about 20% to about 40% by weight, based on the total weight of the benefit agent delivery particles. The amount of fragrance formulation can be measured by taking a slurry of benefit agent delivery particles, extracting into ethanol and measuring by liquid chromatography.

The benefit agent delivery particles of the present invention are suitable for incorporation into all physical forms of laundry treatment compositions.

In a typical laundry treatment composition according to the present invention, the benefit agent delivery particles are typically present in an amount of from 0.01 to 10%, preferably from 0.1 to 5%, more preferably from 0.3 to 3% (by weight based on the total weight of the composition).

The benefit agent delivery particles as described above may be prepared separately and then combined with other ingredients to form the final laundry treatment composition.

The benefit agent delivery particles may also be formed in situ during the preparation of, for example, a liquid laundry detergent comprising an anionic surfactant. In a typical process, cationic surfactant is first deposited on the outer surface of the shell of the preformed core-shell particles. The mixture of particles is then combined with a liquid laundry detergent ingredient (including anionic surfactants) (as described further below). The anionic surfactant from the liquid laundry detergent ingredient then forms a complex with the cationic surfactant deposited on the outer surface of the shell of the particle. The charged heads of the respective surfactants are neutralized during the compounding process. If desired, additional ingredients may be added to the mixture to form the final liquid laundry detergent.

Product form

The laundry treatment composition according to the invention is preferably in liquid form.

The term "liquid" in the context of the present invention means that the continuous phase or major portion of the composition is liquid and that the composition is flowable at 15 ℃ and above. Thus, the term "liquid" may include emulsions, suspensions, and compositions having a flowable but harder consistency, referred to as gels or pastes. At 25℃and 21s ^-1 The viscosity of the composition may suitably be in the range of from about 200 to about 10,000 mpa-s. The shear rate is the shear rate normally applied to a liquid when pouring the liquid from a bottle. The pourable liquid composition generally has a viscosity of 200 to 2,500 mPa-s, preferably 200 to 1500 mPa-s.

The viscosity of the liquid composition as a pourable gel is generally from 1,500 to 6,000 mpa-s, preferably from 1,500 to 2,000 mpa-s.

Product type

Preferably, the laundry treatment composition according to the present invention is a laundry detergent.

Laundry detergents

In the context of the present invention, the term "laundry detergent" refers to formulated compositions intended for and capable of wetting and cleaning household garments such as clothing, linen and other household fabrics. The term "linen" is often used to describe certain types of laundry items, including bedsheets, pillowcases, towels, tablecloths, napkins, and uniforms. Textiles may include woven fabrics, non-woven fabrics, and knit fabrics; and may include natural or synthetic fibers such as silk fibers, linen fibers, cotton fibers, polyester fibers, polyamide fibers such as nylon, acrylic fibers, acetate fibers, and mixtures thereof, including cotton and polyester mixtures.

Examples of laundry detergents include heavy duty (heavies) detergents for the wash cycle of automatic washing machines, as well as fine wash and color care detergents, such as those suitable for washing fine laundry (e.g., those made of silk or wool) by hand or in the wash cycle of automatic washing machines.

To provide a cleaning effect, laundry detergents according to the invention generally comprise at least 3%, for example 5-60% (by weight based on the total weight of the composition) of one or more detersive surfactants. The selection and amount of detersive surfactant present depends on the intended use of the laundry detergent. For example, different surfactant systems may be selected for hand wash products and for products of different types of automatic washing machines. The total amount of surfactant present also depends on the intended end use and can be up to 60% (by weight based on the total weight of the composition) in the composition for hand washing fabrics in fully formulated products. In compositions for machine washing fabrics, amounts of 5 to 40%, for example 15 to 35% (by weight based on the total weight of the composition) are generally suitable.

In the context of the present invention, the term "detersive surfactant" refers to a surfactant that provides a detersive (i.e. cleaning) effect to laundry being treated as part of a domestic laundry process.

Preferred detersive surfactants may be selected from the group consisting of non-soap anionic surfactants, nonionic surfactants, and mixtures thereof.

Non-soap anionic surfactants are mainly used to facilitate particulate soil removal. Examples of suitable non-soap anionic surfactants for use in the present invention include those organic sulphates and sulphonates described above in relation to the washable removable coating, in particular linear alkylbenzenesulphonates (preferably C ₁₁ -C ₁₅ Linear alkylbenzene sulfonate) and sodium lauryl ether sulfate (ethoxylated C with preferably average 1-3EO ₁₀ -C ₁₈ Alkyl sulfates) and mixtures thereof.

In the laundry detergents according to the invention, the total content of non-soap anionic surfactant may suitably be in the range of from 5 to 30% (by weight based on the total weight of the composition).

Nonionic surfactants can provide enhanced performance for removing very hydrophobic greasy stains and for cleaning hydrophobic polyesters and polyester/cotton blends.

The nonionic surfactant used in the present invention is typically a polyoxyalkylene compound, i.e., the reaction product of an alkylene oxide (such as ethylene oxide or propylene oxide or mixtures thereof) with a starter molecule (starter molecules) having a hydrophobic group and a reactive hydrogen atom which reacts with the alkylene oxide. Such starter molecules include alcohols, acids, amides or alkylphenols. When the starter molecule is an alcohol, the reaction product is referred to as an alcohol alkoxylate. The polyoxyalkylene compounds may have a wide variety of block and mixed (random) structures. For example, they may comprise a single block of alkylene oxide, or they may be diblock alkoxylates or triblock alkoxylates. Within the block structure, the blocks may be all ethylene oxide or all propylene oxide, or the blocks may contain a miscible blend of alkylene oxides. Examples of such materials include C with an average of 5 to 25 moles of ethylene oxide per mole of alkylphenol ₈ To C ₂₂ Alkylphenol ethoxylates; and fatty alcohol ethoxylates, e.g. C having an average of 2 to 40 moles of ethylene oxide per mole of alcohol ₈ To C ₁₈ Primary or secondary linear or branched alcohol ethoxylates.

Preferred types of nonionic surfactants for use in the present invention include aliphatic C having an average of 3 to 20, more preferably 5 to 10, moles of ethylene oxide per mole of alcohol ₈ To C ₁₈ More preferably C ₁₂ To C ₁₅ Primary linear alcohol ethoxylates.

Mixtures of any of the above materials may also be used.

In the laundry detergent according to the present invention, the total content of nonionic surfactant may suitably be in the range of from 0 to 25% (by weight based on the total weight of the composition).

The laundry detergents according to the invention are preferably in liquid form.

The liquid laundry detergents according to the invention may generally comprise from 5 to 95%, preferably from 10 to 90%, more preferably from 15 to 85% water (by weight based on the total weight of the composition). The composition may also include a non-aqueous carrier such as hydrotropes, co-solvents, and phase stabilizers. Such materials are typically low molecular weight, water soluble or water miscible organic liquids, such as C1 to C5 monohydric alcohols (e.g., ethanol and n-propanol or isopropanol); c2 to C6 diols (such as monopropylene glycol and dipropylene glycol); c3 to C9 triols (such as glycerol); polyethylene glycols having a weight average molecular weight (Mw) of about 200 to 600; c1 to C3 alkanolamines such as mono-, di-and triethanolamine; and alkylaryl sulfonates having up to 3 carbon atoms in the lower alkyl group (e.g., sodium and potassium xylenes, sodium and potassium toluene, sodium and potassium ethylbenzene and sodium and potassium cumene (cumene) sulfonate).

Mixtures of any of the above materials may also be used.

When included in liquid laundry detergents according to the invention, the non-aqueous carrier may be present in an amount of from 0.1 to 20%, preferably from 1 to 15%, more preferably from 3 to 12% (by weight based on the total weight of the composition).

Builder agent

Laundry detergents according to the invention may comprise one or more builders. Builders enhance or maintain the cleaning efficiency of surfactants, primarily by reducing the hardness of water. This is done by chelation or chelation (holding the hard mineral in solution), by precipitation (forming insoluble materials) or by ion exchange (exchanging charged particles).

The builder used in the present invention may be of an organic or inorganic type, or a mixture thereof. Non-phosphate builders are preferred.

Inorganic non-phosphate builders useful in the present invention include hydroxides, carbonates, silicates, zeolites and mixtures thereof.

Hydroxide builders suitable for use in the present invention include sodium hydroxide and potassium hydroxide.

Suitable carbonate builders for use in the present invention include mixed or individual, anhydrous or partially hydrated alkali metal carbonates, bicarbonates or sesquicarbonates. Preferably, the alkali metal is sodium and/or potassium, sodium carbonate being particularly preferred.

Suitable silicate builders include the amorphous and/or crystalline forms of alkali metal (e.g. sodium) silicate. Preference is given to crystalline layered sodium silicate (phyllosilicate) of the general formula (I):

NaMSi _x O _2x+1 ·yH ₂ O (I)

wherein M is sodium or hydrogen, x is a number from 1.9 to 4, preferably 2 or 3, and y is a number from 0 to 20. Sodium disilicate of the above formula wherein M is sodium and x is 2 is particularly preferred. Such materials can be prepared with different crystal structures, known as the alpha, beta, gamma and delta phases, with delta sodium disilicate being most preferred.

The zeolite is naturally occurring or synthetic containing (SiO ₄ ) ^4- And (AlO) ₄ ) ^5- Tetrahedral crystalline aluminum silicate, which shares oxygen-bridge vertices in the crystalline form and forms a cage-like structure. The ratio between oxygen, aluminum and silicon is O (al+si) =2:1. The backbone acquires their negative charge by substituting some of the Si with Al. The negative charge is neutralized by cations and, under normal conditions, the backbone is open enough to contain mobile water molecules. Suitable zeolite builders for use in the present invention may be defined by the general formula (II):

Na _x [(AlO ₂ ) _x (SiO ₂ ) _y ]·zH ₂ O (II)

wherein x and y are integers of at least 6, the molar ratio of x to y is in the range of about 1 to about 0.5, and z is an integer of at least 5, preferably about 7.5 to about 276, more preferably about 10 to about 264.

Preferred inorganic non-phosphate builders for use in the present invention may be selected from the group consisting of zeolites (having formula (II) above), sodium carbonate, delta sodium disilicate and mixtures thereof.

Suitable organic non-phosphate builders for use in the present invention include polycarboxylic acids in acid and/or salt form. When salt forms are used, alkali metal (e.g., sodium and potassium) or alkanolammonium salts are preferred. Specific examples of such materials include sodium and potassium citrate, sodium and potassium tartrate, sodium and potassium salts of tartaric acid monosuccinic acid, sodium and potassium salts of tartaric acid disuccinic acid, sodium and potassium salts of ethylenediamine tetraacetic acid, N- (2-hydroxyethyl) -ethylenediamine triacetic acidSodium and potassium of nitrilotriacetic acid, sodium and potassium of N- (2-hydroxyethyl) -nitrilodiacetic acid. Polymeric polycarboxylates such as polymers of unsaturated monocarboxylic acids (e.g., acrylic acid, methacrylic acid, vinylacetic acid, and crotonic acid) and/or unsaturated dicarboxylic acids (e.g., maleic acid, fumaric acid, itaconic acid, mesaconic acid, and citraconic acid and anhydrides thereof) may also be used. Specific examples of such materials include polyacrylic acid, polymaleic acid, and copolymers of acrylic acid and maleic acid. The polymer may be in acid, salt or partially neutralized form and may suitably have a molecular weight (M) in the range of from about 1,000 to 100,000, preferably from about 2,000 to about 85,000, more preferably from about 2,500 to about 75,000 _w )。

Preferred organic non-phosphate builders for use in the present invention may be selected from the group consisting of polycarboxylic esters (e.g. citric acid esters) in acid and/or salt form and mixtures thereof.

Mixtures of any of the above materials may also be used.

Preferably, the phosphate builder is present in the laundry detergent of the present invention in an amount of no more than 1%, more preferably no more than 0.1%, most preferably 0% (by weight based on the total weight of the composition). The term "phosphate builder" in the context of the present invention refers to alkali metal, ammonium and alkanolammonium salts of polyphosphates, orthophosphates and/or metaphosphates (e.g. sodium tripolyphosphate).

When included, the total level of builder may be from about 0.1 to about 80%, preferably from about 0.5 to about 50% (by weight based on the total weight of the composition).

Polymeric cleaning enhancers

The laundry detergents according to the present invention may also comprise one or more polymeric cleaning enhancing agents, such as anti-redeposition polymers, soil release polymers and mixtures thereof.

The anti-redeposition polymer stabilizes soil in the wash solution, thereby preventing soil redeposition. Suitable anti-redeposition polymers for use in the present invention include alkoxylated polyethylenimines. The polyethyleneimine is a polymer comprising ethyleneimine units-CH ₂ CH ₂ NH-material and when branched, hydrogen on nitrogen is replaced by anotherSubstitution of ethyleneimine units of the chain. Preferred alkoxylated polyethylenimines for use in the present invention have a weight average molecular weight (M) of from about 300 to about 10000 _w ) Is a polyethyleneimine backbone. The polyethyleneimine backbone may be linear or branched. It can be branched to the extent that it is a dendrimer. Alkoxylation may generally be ethoxylation or propoxylation, or a mixture of both. When the nitrogen atom is alkoxylated, the preferred average degree of alkoxylation per modification is from 10 to 30, preferably from 15 to 25, alkoxy groups. A preferred material is an ethoxylated polyethyleneimine having an average degree of ethoxylation of from 10 to 30, preferably from 15 to 25, ethoxy groups per ethoxylated nitrogen atom in the polyethyleneimine backbone. Another type of suitable anti-redeposition polymer for use in the present invention includes cellulose esters and ethers, such as sodium carboxymethyl cellulose.

Mixtures of any of the above materials may also be used.

When included, the total anti-redeposition polymer may be present in an amount of from 0.05 to 6%, more preferably from 0.1 to 5% (by weight based on the total weight of the composition).

Soil release polymers help improve the separation of stains from fabrics by modifying the surface of the fabric during the wash process. The affinity between the chemical structure of the SRP and the target fibers promotes adsorption of the SRP on the fabric surface.

SRPs useful in the present invention may include various charged (e.g., anionic) and uncharged monomeric units, and the structure may be linear, branched, or star-shaped. The SRP structure may also include end capping groups to control molecular weight or to alter polymer properties, such as surface activity. Weight average molecular weight (M) of SRP _w ) May suitably be in the range of about 1000 to about 20,000, and preferably in the range of about 1500 to about 10,000.

The SRP used in the present invention may be suitably selected from copolyesters of dicarboxylic acids (e.g., adipic acid, phthalic acid, or terephthalic acid), glycols (e.g., ethylene glycol or propylene glycol), and polyglycols (e.g., polyethylene glycol or polypropylene glycol). The copolyester may also include monomer units substituted with anionic groups, such as sulfonated isophthaloyl units. Examples of such materials include oligoesters prepared by transesterification/oligomerization of poly (ethylene glycol) methyl ether, dimethyl terephthalate ("DMT"), propylene glycol ("PG"), and poly (ethylene glycol) ("PEG"); partially and fully anionic end-blocked oligoesters, such as oligomers from ethylene glycol ("EG"), PG, DMT, and Na-3, 6-dioxa-8-hydroxyoctanesulfonic acid; nonionic blocked block polyester oligomeric compounds, such as those produced from DMT, me-blocked PEG and EG and/or PG, or combinations of DMT, EG and/or PG, me-blocked PEG and Na-dimethyl-5-sulfoisophthalate, and copolymerized blocks of ethylene terephthalate or propylene terephthalate and polyethylene oxide or polypropylene oxide terephthalate.

Other types of SRPs useful in the present invention include cellulose derivatives such as hydroxyether cellulose polymers, C1-C4 alkyl celluloses, and C4 hydroxyalkyl celluloses; polymers having poly (vinyl ester) hydrophobic segments, such as graft copolymers of poly (vinyl ester), e.g., C1-C6 vinyl esters (e.g., poly (vinyl acetate)) grafted onto a polyalkylene oxide backbone; poly (vinyl caprolactam) and related copolymers with monomers such as vinyl pyrrolidone and/or dimethylaminoethyl methacrylate; and polyester-polyamide polymers prepared by condensing adipic acid, caprolactam and polyethylene glycol.

Preferred SRPs for use in the present invention include copolyesters formed from the condensation of terephthalates and diols (preferably 1, 2-propanediol) and further comprise end caps formed from repeating units of alkylene oxide capped with an alkyl group. Examples of such materials have a structure corresponding to the general formula (I):

wherein R is ¹ And R is ² X- (OC) independently of one another ₂ H ₄ ) _n -(OC ₃ H ₆ ) _m ；

Wherein X is C _1-4 Alkyl, preferably methyl;

n is a number from 12 to 120, preferably from 40 to 50;

m is a number from 1 to 10, preferably from 1 to 7; and

a is a number from 4 to 9.

Since m, n and a are average values, they are not necessarily integers for a large batch of polymers.

Mixtures of any of the above materials may also be used.

When included, the total content of SRPs may be from 0.1 to 10%, preferably from 0.3 to 7%, more preferably from 0.5 to 5% (by weight based on the total weight of the composition).

Transition metal ion chelating agent

The liquid or particulate laundry detergents according to the present invention may comprise one or more chelants for transition metal ions (e.g. iron, copper and manganese). Such chelating agents can help improve the stability of the composition and prevent decomposition of certain components, such as transition metal catalysis.

Suitable transition metal ion chelators include phosphonates in acid and/or salt form. When salt forms are used, alkali metal (e.g., sodium and potassium) or alkanolammonium salts are preferred. Specific examples of such materials include aminotri (methylenephosphonic Acid) (ATMP), 1-hydroxyvinyldiphosphonic acid (HEDP), and diethylenetriamine penta (methylenephosphonic acid) (DTPMP) and their respective sodium or potassium salts. HEDP is preferred. Mixtures of any of the above materials may also be used.

When included, the transition metal ion chelating agent may be present in an amount ranging from about 0.1 to about 10%, preferably from about 0.1 to about 3% (by weight based on the total weight of the composition).

Fatty acid

Laundry detergents according to the present invention may in some cases comprise one or more fatty acids and/or salts thereof.

In the context of the present invention, suitable fatty acids include aliphatic carboxylic acids of the formula RCOOH, wherein R is a straight or branched alkyl or alkenyl chain containing from 6 to 24, more preferably from 10 to 22, most preferably from 12 to 18 carbon atoms and 0 or 1 double bond. Preferred examples of such materials include saturated C _12-18 Fatty acids such as lauric acid, myristic acid, palmitic acid or stearic acid; and 50 to 100% (based onTotal weight of mixture) by weight of saturated C _12-18 Fatty acid mixture composed of fatty acids. Such mixtures may generally be derived from natural fats and/or optionally hydrogenated natural oils (such as coconut oil, palm kernel oil or tallow).

The fatty acids may be present in the form of their sodium, potassium or ammonium salts and/or in the form of soluble salts of organic bases such as mono-, di-or triethanolamine.

Mixtures of any of the above materials may also be used.

When included, the fatty acid and/or salt thereof may be present in an amount ranging from about 0.25 to 5%, more preferably 0.5 to 5%, most preferably 0.75 to 4% (by weight based on the total weight of the composition).

For purposes of structural formula interpretation, fatty acids and/or salts thereof (as defined above) are not included in the formulation in the surfactant content or builder content.

Rheology modifier

The liquid laundry detergents according to the invention may comprise one or more rheology modifiers. Examples of such materials include polymeric thickeners and/or structuring agents, such as hydrophobically modified alkali swellable emulsion (HASE) copolymers. Exemplary HASE copolymers for use in the present invention include linear or crosslinked copolymers prepared by addition polymerization of a monomer mixture comprising at least one acidic vinyl monomer, such as (meth) acrylic acid (i.e., methacrylic acid and/or acrylic acid); and at least one associative monomer. The term "associative monomer" in the context of the present invention refers to a monomer having an ethylenically unsaturated moiety (for addition polymerization with other monomers in the mixture) and a hydrophobic moiety. A preferred type of associative monomer comprises a polyoxyalkylene moiety between an ethylenically unsaturated moiety and a hydrophobic moiety. Preferred HASE copolymers for use in the present invention comprise a copolymer prepared by reacting (meth) acrylic acid with (i) a polymer selected from the group consisting of linear and branched C ₈ -C ₄₀ Alkyl (preferably straight chain C ₁₂ -C ₂₂ At least one associative monomer of alkyl) polyethoxylated (meth) acrylates; and (ii) is selected from (meth) acrylic acid C ₁ -C ₄ Alkyl esters, polyethylene monomers (e.g. maleic acidMaleic anhydride and/or salts thereof) and mixtures thereof. The polyethoxylated portion of the associative monomer (i) generally comprises from about 5 to about 100, preferably from about 10 to about 80, more preferably from about 15 to about 60, oxyethylene repeating units.

Mixtures of any of the above materials may also be used.

When included, the polymeric thickener may be present in an amount of 0.1 to 5% (by weight based on the total weight of the composition).

The liquid laundry detergents according to the invention may also have their rheology altered by the use of one or more external structurants which form a structured network within the composition. Examples of such materials include hydrogenated castor oil, microfibrils and citrus pulp fibres. The presence of external structurants may provide shear thinning rheology and may also enable materials (e.g., encapsulates and visual cues) to be stably suspended in the liquid.

Enzymes

The laundry detergents according to the present invention may comprise an effective amount of one or more enzymes selected from pectate lyase, protease, amylase, cellulase, lipase, mannanase and mixtures thereof. The enzymes are preferably present together with the corresponding enzyme stabilizers.

The liquid laundry detergents according to the invention preferably have a pH of from 5 to 9, more preferably from 6 to 8, when the composition is diluted to 1% (by weight based on the total weight of the composition) using demineralised water.

Additional optional ingredients

The laundry treatment compositions of the present invention may contain additional optional ingredients that enhance performance and/or consumer acceptability. Examples of such ingredients include foam boosters, preservatives (e.g., bactericides), antioxidants, sunscreens, colorants, pearlescers and/or opacifiers, and hueing dyes. Each of these ingredients is present in an amount effective to achieve its purpose. Typically, these optional ingredients are individually included in amounts up to 5 wt% (by weight based on the total weight of the composition).

Packaging and dosing

The laundry treatment composition of the present invention may be packaged in unit doses in polymeric films that are soluble in wash water. Alternatively, the compositions of the present invention may be provided in multi-dose plastic packages having a top or bottom closure. The dosing measure may be provided as part of the lid or as an integrated system with the package.

The method of treating fabrics using a laundry detergent according to the present invention will often comprise diluting a dose of detergent to obtain a wash liquor, and washing the fabrics with the wash liquor so formed. The method of washing fabrics may suitably be carried out in an automatic washing machine or may be carried out manually.

In automatic washing machines, a dose of detergent is typically placed in a dispenser and from there is flushed into the machine by water flowing into the machine, thereby forming a wash liquor. Alternatively, a dose of detergent may be added directly to the drum. Typical front-loading washing machines (using 10 to 15 litres of water to form the wash liquor) have a dosage in the range of about 10ml to about 60ml, preferably about 15 to 40ml. The dosage of a typical top-loading washing machine (using 40-60 litres of water to form the washing liquid) may be higher, for example up to about 100ml. Lower doses of detergent (e.g., 50ml or less) can be used in the hand washing process (using about 1 to 10 liters of water to form a wash liquor). Subsequent water rinsing steps and drying of the laundry are preferred. In determining the volume of wash liquor, any water input during any optional rinsing step is not included.

The laundry drying step may be performed in an automatic clothes dryer, or may be performed outdoors.

The invention will now be further described with reference to the following non-limiting examples.

Examples

All weight percentages are based on total weight unless otherwise indicated. Embodiments according to the present invention are represented by numerals; comparative examples (not according to the invention) are indicated by letters.

Melamine-formaldehyde core-shell particles were prepared having a melamine-formaldehyde shell and a core of model fragrance containing 15 components, with an average particle diameter of about 13 μm and a zeta potential of about-20 mV (measured as described above). The particles were obtained in an aqueous slurry having a solids content of about 30% by weight. Separately, laundry liquids having the ingredients shown in table 1 were prepared.

Composition of the components	Weight% (active ingredient)
		C 12-14 Linear alkylbenzenesulfonic acid (LAS)	11.2
C 12-15 Alcohol ethoxylate (7 EO)	8.4
		SLES(3EO)	8.4
Monopropylene glycol	8.0
		Monoethanolamine	To pH 8.3
Water, minor ingredients	Proper amount of

The aqueous particle slurry was diluted with water to reduce the solids content to about 10 wt.%. The formulation according to the invention (example 1) was prepared by first adding CTAC (cetyltrimethylammonium chloride) to a 10 wt% aqueous particulate slurry and mixing for 30 minutes. The thus obtained CTAC treated particulate slurry of 1ml of sample was then mixed with 9ml of laundry liquid to form the example 1 formulation. Control formulations were also prepared by adding 1ml of a 10 wt% aqueous particle slurry of the sample (not mixed with CTAC) to 9ml of laundry liquid.

To test for leakage of fragrance from the core-shell particles, test samples of the control and example 1 formulations were placed on a roller for 24 hours, respectively, followed by centrifugation at 11000rpm for 30 minutes. The supernatant was then removed and filtered through a 3.1 μm filter. Then 1ml of the filtrate was placed in a 20ml headspace bottle. The headspace above the filtrate was measured after incubation on a CombiPAL autosampler for 10 minutes at 40 ℃. Sampling was achieved using DMS/Carboxen/DVB fibers with an exposure time of 60 seconds. The fibers were then desorbed at 270 ℃ for 5 minutes at the inlet of an Agilent 6890 gas chromatograph. Separation was achieved using a 30m BPX-5 capillary column. Peak identification was achieved using an Agilent5973N inert mass detector in combination with appropriate software/NIST libraries. The integrals of the peaks of the fragrances are added to give the total fragrance content. Calibration plots constructed by adding a known amount of free fragrance to the model laundry detergent allow the results to be converted to a leakage percentage plot.

The results are shown in Table 2.

TABLE 2

Formulations	Fragrance leakage%
		Control (uncoated)	52.09
Example 1	22.40

The particles in example 1 according to the invention showed a significantly lower percentage of fragrance leakage when added to a laundry liquid than the uncoated control particles. When the laundry liquid is diluted in the washing operation (typically 35ml of liquid into 21L of water), the coating is removed.

In this way, the particles of the present invention provide improved stability of the fragrance to leakage in the product, while providing an enhanced fragrance experience at an early stage after washing.

Claims (11)

1. A benefit agent delivery particle having a core-shell structure wherein a porous shell of polymeric material encapsulates a core comprising the benefit agent; wherein the apertures in the shell are at least partially blocked by a washable, removable coating disposed at an outer surface of the shell; characterized in that said washable removable coating is formed by deposited particles of a complex of cationic surfactant and anionic surfactant; wherein the cationic surfactant used to form the complex is selected from cetyltrimethylammonium chloride, stearyl trimethylammonium chloride, behenyl trimethylammonium chloride, and mixtures thereof; wherein said anionic surfactant used to form said complex is selected from the group consisting of linear alkylbenzenesulfonates having an alkyl chain length of 10 to 18 carbon atoms and mixtures thereof; and wherein the shell comprises up to 20 wt% based on the total weight of the benefit agent delivery particle.

2. The particle of claim 1, wherein the benefit agent is a fragrance formulation comprising a mixture of at least 10 fragrance components selected from the group consisting of: a hydrocarbon; aliphatic and araliphatic alcohols; fatty aldehydes and acetals thereof; aliphatic carboxylic acids and esters thereof; acyclic terpene alcohols; cyclic terpene aldehydes and cyclic terpene ketones; cyclic ethers and cycloaliphatic ethers; esters of cyclic alcohols; araliphatic ethers and acetals thereof; aromatic and araliphatic aldehydes and aromatic and araliphatic ketones; and aromatic and araliphatic carboxylic acids and esters thereof.

3. The particle of claim 2, wherein the ester of an aliphatic carboxylic acid is an ester of an araliphatic alcohol and an aliphatic carboxylic acid.

4. The particle of claim 2 wherein the fragrance formulation comprises 20-40 wt% based on the total weight of the benefit agent delivery particle.

5. The particle of any one of claims 1 to 4, wherein the complex has a solubility in distilled water of less than 10mg/L at 25 ℃ and atmospheric pressure.

6. A method of preparing benefit agent delivery particles according to any one of claims 1 to 5, wherein the cationic surfactant is first mixed with an aqueous slurry of preformed particles having a core-shell structure to form a mixture of particles, wherein a porous shell of polymeric material surrounds a core comprising the benefit agent; the anionic surfactant is then added to the mixture of particles such that it forms a complex with the cationic surfactant deposited on the outer surface of the shell of the particles.

7. The method of claim 6, wherein the cationic surfactant is cetyltrimethylammonium chloride.

8. The method of claim 6 or claim 7, wherein the anionic surfactant is selected from C _12-14 Linear alkylbenzene sulfonates and mixtures thereof.

9. A laundry treatment composition comprising benefit agent delivery particles according to any one of claims 1 to 5.

10. A laundry treatment composition according to claim 9 which is a laundry detergent comprising from 5 to 40% by weight, based on the total weight of the composition, of a detersive surfactant selected from non-soap anionic surfactants, nonionic surfactants and mixtures thereof.

11. A laundry treatment composition according to claim 10 which is a liquid comprising 5-95% by weight of water, based on the total weight of the composition.