CN112567013A

CN112567013A - Benefit agent delivery particles

Info

Publication number: CN112567013A
Application number: CN201980047653.6A
Authority: CN
Inventors: C·W·琼斯; A·P·帕克
Original assignee: Unilever IP Holdings BV
Current assignee: Unilever IP Holdings BV
Priority date: 2018-07-17
Filing date: 2019-07-15
Publication date: 2021-03-26
Anticipated expiration: 2039-07-15
Also published as: ZA202100030B; BR112021000737A2; BR112021000737B1; EP3824061B1; CN112567013B; EP3824061A1; WO2020016194A1

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 holes in the shell are at least partially blocked by a wash-off coating disposed at an outer surface of the shell; characterised in that the wash-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 a benefit agent delivery particle 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 them.

Background

In laundry treatment compositions such as laundry detergents, the fragrance perceived by the consumer is one of the most important attributes. Effective delivery of a suitable fragrance to fabrics during the laundering process, and release of the fragrance at critical consumer times, is critical to delivering clean, fresh laundered garments.

Delivering fragrance at strategic points is a difficult task because laundry detergents are typically designed to carry oily substances or particulate solids away from the washed fabric. While fragrances are also typical oily substances.

Encapsulation of the fragrance results in improved deposition of the fragrance onto the fabric and delayed release of the fragrance while wearing the consumer garment.

Yet another important moment for the consumer is when the laundry is in the "wet" phase, which extends from when it is removed from the washing machine to when it is almost dry. There is a need for compositions that deliver a good fragrance experience during this stage without significant impairment of fragrance performance in other stages, such as in pre-use packaged compositions and when laundered laundry is dried.

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 holes in the shell are at least partially blocked by a wash-off coating disposed at an outer surface of the shell; characterised in that the wash-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 a benefit agent delivery particle as defined above.

Detailed Description

The core of the benefit agent delivery particle of the present invention is typically formed in the interior region of the particle 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 particle of the present invention, the presence of the wash-off 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 entrapped benefit agent.

The term "laundering operation" as used herein generally refers to a process for laundering fabrics with a laundry treatment composition according to the present invention.

The wash-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 in the wash.

In a preferred process for making the benefit agent delivery particles of the present invention, the cationic surfactant is first mixed with an aqueous slurry of preformed particles having a core-shell structure in which a porous shell of polymeric material surrounds a core containing the benefit agent (hereinafter "preformed core-shell particles"). The cationic surfactant is deposited on the outer surface of the shell of the pre-formed 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 100 mg/L.

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

R¹R²R³R⁴N⁺X^- (I)

wherein R is¹Selected from linear or branched alkyl or alkenyl chains containing 6 to 24 carbon atoms and 0 or 1 double bond, R²、R³And R⁴Each independently selected from C1 to C3 alkyl and- (C)_nH_2nO)_xA H group, wherein n is 2 or 3, X is 1 to about 3, and X is an anion selected from the group consisting of chloride, bromide, iodide, nitrate, sulfate, methylsulfate, ethylsulfate, acetate, and phosphate.

Preferably, in the above general formula (I), R¹Selected from C16 to C22 straight chain saturated alkyl chains, R²、R³And R⁴Each independently selected from CH₃And CH₂CH₂OH, more preferably CH₃。

Specific examples of preferred cationic surfactants for forming complexes include cetyltrimethylammonium chloride (CTAC), stearyltrimethylammonium chloride (STAC), behenyltrimethylammonium chloride (BTAC), and mixtures thereof.

Suitable anionic surfactants for forming the complex may be selected from the group consisting of organic sulfates and sulfonates having an alkyl group containing from about 8 to about 22 carbon atoms, the term "alkyl" being used to include the alkyl portion of higher acyl groups. 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 sulfates may contain from one to ten ethylene oxide or propylene oxide units per molecule, and preferably contain from 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 ammonia-containing counterion such as Monoethanolamine (MEA), Diethanolamine (DEA) or Triethanolamine (TEA). Mixtures of such counterions can also be used.

Preferred anionic surface active for complex formationAgents include alkyl benzene sulphonates, especially linear alkyl benzene sulphonates (LAS) having alkyl chain lengths of 10 to 18 carbon atoms. Commercial LAS are a mixture of closely related isomers and homologues of homologous 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, with the primary material having about C₁₂The chain length of (a). Each alkyl chain homologue, except the 1-phenyl isomer, consists of a mixture of all possible sulfophenyl isomers.

Also suitable are alkyl ether sulfates having a linear or branched alkyl group of 10 to 18, more preferably 12 to 14 carbon atoms and containing an average of 1 to 3EO units per molecule. One preferred example is Sodium Lauryl Ether Sulfate (SLES), in which predominantly C12 lauryl alkyl has been ethoxylated, averaging 3EO units per molecule.

Preferred preformed core-shell particles have a negative charge at the outer surface of their shell and 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 at 25 ℃ by Dynamic Light Scattering (DLS) method Using Zetasizer Nano^TMZS90(Malvern Instruments Ltd, UK) was 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.

The 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 precipitation of a colloidal material onto the surface of droplets of the material to encapsulate the core material, which is typically water-insoluble. Agglomeration can be simple, for example using a single colloid, such as gelatin, or a complex of two or possibly more colloids of opposite charge, such as gelatin and gum arabic or gelatin and carboxymethylcellulose, under carefully controlled conditions of pH, temperature and concentration.

Interfacial polymerization generally continues with the formation of a fine dispersion of oil droplets (which contain a core material) in an aqueous continuous phase. The dispersed droplets form the core of the virgin core-shell particles, and the size of the dispersed droplets directly determines the size of the virgin core-shell particles. Shell-forming materials (monomers or oligomers) are 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 polymeric wall around the oil droplets, thereby encapsulating the droplets. One example of a core-shell particle produced by this method has a polyurea shell formed by reacting a diisocyanate or polyisocyanate with a diamine 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 appropriate 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 coherent film and the desired particles. One example of core-shell particles produced by this method has an aminoplast shell formed from the polycondensation product of melamine (2,4, 6-triamino-1, 3, 5-triazine) or urea with formaldehyde. Suitable crosslinking 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 particle 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 constitutes up to 20 wt% based on the total weight of the benefit agent delivery particle.

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 go into the visible range. Examples of particles in the submicron range include latexes and microemulsions having an average particle size in the range of 100 to 600 nanometers. The average size of the core-shell particles suitable for use in the present invention is preferably from 0.6 to 50 microns, more preferably from 2 to 30 microns, most preferably from 5 to 25 microns. The particle size distribution may be narrow, broad or multimodal. If necessary, the initially produced particles can be filtered or screened to produce a product with greater size uniformity.

As used herein, "size" refers to diameter, unless otherwise specified. For samples having a particle diameter of not more than 1 micron, diameter refers to the z-average particle size measured, for example, using dynamic light scattering (as described in international standard ISO 13321) and instruments such as Zetasizer Nano^TMZS90(Malvern Instruments Ltd, UK). For samples with particle diameters greater than 1 micron, diameter refers to the apparent volume median diameter (D50), and can be determined, for example, by laser diffraction (as described in International Standard ISO 13320) and instruments such as Mastersizer^TM2000(Malvern Instruments Ltd, UK).

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 modify the properties of the outer surface of the shell, 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 by covalent bonding, either directly or via a linking species.

The deposition aid used in the present invention may suitably be 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 sugar) backbone structure with at least 4 and preferably at least 10 backbone residues that are beta 1-4 linked, 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 β 1-4 linked polysaccharides include xyloglucan, glucomannan, mannan, galactomannan, β (1-3), (1-4) glucan, and the family of xylans comprising glucuronyl (glucorono) -, arabinoyl (arabino) -and glucuronosyl xylans. Preferred β 1-4 linked polysaccharides for use in the present invention may be selected from plant derived xyloglucans such as pea xyloglucan and tamarind seed xyloglucan (TXG) having a β 1-4 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 plant-derived galactomannans, such as Locust Bean Gum (LBG) (which has a mannan backbone with β 1-4 linked mannose residues, with single unit galactose side chains with α 1-6 linked to the backbone).

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

The deposition aid used in the present invention may also be selected from phthalate containing polymers having an affinity for polyesters. Such phthalate-containing polymers may have one or more nonionic hydrophilic segments comprising oxyalkylene groups, such as oxyethylene, polyoxyethylene, oxypropylene or polyoxypropylene groups, and one or more hydrophobic segments comprising terephthalate groups. Typically, 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 aids useful 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 particle of the present invention, the core comprises a benefit agent. In the case of fabric washing preferred benefit agents include fragrance agents, clays, enzymes, antifoams, fluorescers, bleaches and precursors thereof 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), colour and light protection agents (including sunscreens), antioxidants, ceramides, reducing agents, chelants, colour care additives (including dye fixing agents), unsaturated oils, lubricants, humectants, insect repellents and/or pheromones, drape modifiers (e.g. polymer latex particles such as PVA) and anti-microbial or microbe control agents.

Mixtures of any of the above materials may also be suitable. In the context of the present invention, the most preferred benefit agents are fragrance formulations.

The fragrance formulations used in the present invention will generally comprise a mixture of selected fragrance components, optionally mixed with one or more excipients. The combined odor of the various fragrance components produces a pleasant or desirable scent.

In the context of the present invention, the term "fragrance component" refers to a material used essentially for its ability, alone or in admixture with other such materials, to impart a pleasant odor to a composition (into which it is incorporated) and/or a surface (to which it is applied). 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 ionizing 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 aroma component will have a molecular structure containing only atoms from the following (but not necessarily all): hydrogen, carbon and oxygen.

Examples of the aromatic component 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 nitriles, aliphatic nitriles and araliphatic nitriles having a molecular weight of from 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, aliphatic, and araliphatic lactones having a molecular weight of about 130 to about 290; aromatic aldehydes, aliphatic aldehydes, 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 used 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, bisabolene (bisabolene), camphene, caryophyllene, cedrene, farnesene, longifolene, myrcene, ocimene, valencene (valenene), (E, Z) -1,3, 5-undecatriene, styrene, and diphenylmethane;

ii) aliphatic and araliphatic alcohols, such as, for example, benzyl alcohol, 1-phenylethyl alcohol, 2-phenylethyl alcohol, 3-phenylpropyl alcohol, 2-phenoxyethanol, 2-dimethyl-3-phenylpropyl alcohol, 2-dimethyl-3- (3-methylphenyl) propanol, 1-dimethyl-2-phenylethyl alcohol, 1-dimethyl-3-phenylpropyl alcohol, 1-ethyl-1-methyl-3-phenylpropyl alcohol, 2-methyl-5-phenylpentanol, 3-phenyl-2-propen-1-ol, 4-methoxybenzyl alcohol, 1- (4-isopropylphenyl) ethanol, 1-phenylpropyl alcohol, 2-methyl-5-phenylpentanol, 3-phenyl-2-propen-, Hexanol, octanol, 3-octanol, 2, 6-dimethylheptanol, 2-methyl-2-heptanol, 2-methyl-2-octanol, (E) -2-hexenol, (E) -and a mixture of (Z) -3-hexenol, 1-octen-3-ol, 3,4,5,6, 6-pentamethyl-3/4-hepten-2-ol and 3,5,6, 6-tetramethyl-4-methylenehept-2-ol, (E, Z) -2, 6-nonadienol, 3, 7-dimethyl-7-methoxyoct-2-ol, 9-decenol, 10-undecenol and 4-methyl-3-decen-5-ol;

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

iv) aliphatic aldehydes and acetals thereof, such as, for example, hexanal, heptanal, octanal, nonanal, decanal, undecanal, laurnal, tridecanal, 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-undecenal, heptanal-diethyl acetal, 1-dimethoxy-2, 2, 5-trimethyl-4-hexene and citronellyloxyacetaldehyde (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 2,4,4, 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-nonene nitrile, 2-tridecene nitrile, 2, 12-tridecene nitrile, 3, 7-dimethyl-2, 6-octadiene nitrile and 3, 7-dimethyl-6-octene nitrile;

viii) aliphatic carboxylic acids and esters thereof, such as, for example, (E) -and (Z) -3-hexenyl formate, ethyl acetoacetate, isoamyl acetate, hexyl 3,5, 5-trimethylacetate, 3-methyl-2-butenyl acetate, (E) -2-hexenyl acetate, (E) -and (Z) -3-hexenyl acetate, octyl acetate, 3-octyl acetate, 1-octen-3-yl acetate, ethyl butyrate, butyl butyrate, isoamyl butyrate, hexyl butyrate, (E) -and (Z) -3-hexenyl isobutyrate, hexyl crotonate, ethyl isovalerate, ethyl-2-methylvalerate, ethyl hexanoate, allyl hexanoate, ethyl heptanoate, allyl heptanoate, Ethyl octanoate, ethyl- (E, Z) -2, 4-decanedioate, methyl-2-octanoate, methyl-2-nonanoate, allyl-2-isopentyloxy-acetate, and methyl-3, 7-dimethyl-2, 6-octanedioate;

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, caproates, crotonates, tiglates (tiglinites), 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-undecenal, α -sinal, β -sinal, geranylacetone, and the 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), vetiverol, guaiol, and alpha-terpineol, terpinen-4-ol, menthan-8-ol, menthane-1-ol, menthane-7-ol, borneol, isoborneol, linalool oxide, nopol, cedrol, ambergris octahydronaphthalenol, vetiver and guaiol, formate, acetate, propionate, isobutyrate, butyrate, isovalerate, valerate, hexanoate, crotonate, tiglate and 3-methyl-2-butenoate;

xii) cyclic terpene aldehydes and ketones, such as, for example, menthone, isomenthone, 8-mercaptomenthan-3-one, carvone, camphor, fenchone, α -ionone, β -ionone, α -n-methylionone, β -n-methylionone, α -isomethyl ionone, β -isomethyl ionone, α -irone, α -damascone, β -damascone, δ -damascone, γ -damascone, 1- (2,4, 4-trimethyl-2-cyclohexen-1-yl) -2-buten-1-one, 1,3,4,6,7,8 a-hexahydro-1, 1,5, 5-tetramethyl-2H-2, 4 a-methanonaphthalen-8 (5H) -one, nootkatone, dihydronootkatone, and cedryl methyl ketone;

xiii) cyclic and cycloaliphatic ethers, such as, for example, eucalyptol, cedryl methyl ether, cyclododecyl methyl ether, (ethoxymethoxy) cyclododecane; α -cedrene epoxide, 3a,6,6,9 a-tetramethyldodecahydronaphtho [2,1-b ] furan, 3 a-ethyl-6, 6,9 a-trimethyldodecahydronaphtho [2,1-b ] furan, 1,5, 9-trimethyl-13-oxabicyclo [10.1.0] -trideca-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) -3,3,5, 5-tetramethylcyclohexanone, 4-tert-amylcyclohexanone, 5-cyclohexadecen-1-one, 6, 7-dihydro-1, 1,2,3, 3-pentamethyl-4 (5H) -indanone, 5-cyclohexadecen-1-one, 8-cyclohexadecen-1-one, 9-cyclohexadecen-1-one, and cyclopentadecanone;

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

xvi) esters of cyclic alcohols, such as, for example, 2-tert-butylcyclohexylacetate, 4-tert-butylcyclohexylacetate, 2-tert-amylcyclohexylacetate, 4-tert-amylcyclohexylacetate, decahydro-2-naphthylacetate, 3-pentyltetrahydro-2H-pyran-4-ylacetate, decahydro-2, 5,5,8 a-tetramethyl-2-naphthylacetate, 4, 7-methano-3 a,4,5,6,7,7 a-hexahydro-5-or 6-indenylacetate, 4, 7-methano-3 a,4,5,6,7,7 a-hexahydro-5-or 6-indenylpropionate, 4, 7-methano-3 a,4,5,6,7,7 a-hexahydro-5 or 6-indenyl isobutyrate and 4, 7-methanooctahydro-5-or 6-indenyl acetate;

xvii) esters of cycloaliphatic carboxylic acids, such as, for example, allyl 3-cyclohexyl-propionate, allyl cyclohexyloxyacetate, methyl dihydrojasmonate, methyl jasmonate, methyl 2-hexyl-3-oxocyclopentanecarboxylate, ethyl 2-ethyl-6, 6-dimethyl-2-cyclohexenecarboxylate, ethyl 2,3,6, 6-tetramethyl-2-cyclohexenecarboxylate 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-phenylethyl acetate, 2-phenylethyl propionate, 2-phenylethyl isobutyrate, 2-phenylethyl isovalerate, 1-phenylethyl acetate, α -trichloromethyl benzyl acetate, α -dimethylbenzyl butyrate, cinnamyl acetate, 2-phenoxyethyl isobutyrate and 4-methoxybenzyl acetate;

xix) araliphatic ethers and acetals thereof, such as, for example, 2-phenylethylmethyl ether, 2-phenylethylisoamyl ether, 2-phenylethylcyclohexyl ether, 2-phenylethyl-1-ethoxyethyl ether, phenylacetaldehyde dimethyl acetal, phenylacetaldehyde diethyl acetal, 2-phenylpropionaldehyde 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-phenylpropylaldehyde, 2-phenylpropylaldehyde, 4-methylbenzaldehyde, 4-methylphenylaldehyde, 3- (4-ethylphenyl) -2, 2-dimethylpropionaldehyde, 2-methyl-3- (4-isopropylphenyl) propionaldehyde, 2-methyl-3- (4-tert-butylphenyl) propionaldehyde, cinnamaldehyde, α -butylcinnamaldehyde, α -pentylcinnamaldehyde, α -hexylcinnamaldehyde, 3-methyl-5-phenylpentanal, 4-methoxybenzaldehyde, 4-hydroxy-3-ethoxybenzaldehyde, 3, 4-methylene-dioxybenzaldehyde, phenylglyoxal, 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-dimethylacetophenone, 4-phenyl-2-butanone, 4- (4-hydroxyphenyl) -2-butanone, 1- (2-naphthyl) ethanone, benzophenone, 1,2,3,3, 6-hexamethyl-5-indanyl methyl ketone, 6-tert-butyl-1, 1-dimethyl-4-indanyl methyl 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-naphthaleneacetone;

xxi) aromatic and araliphatic carboxylic acids and esters thereof, 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, 2, 4-dihydroxy-3, 6-dimethylbenzoic acid methyl ester, 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-butylbenzone, cinnamonitrile, 5-phenyl-3-methyl-2-pentenenitrile, 5-phenyl-3-methylpentanenitrile, methyl anthranilate, methyl N-methylanthranilate, methyl anthranilate with 7-hydroxy-3, 3, 7-dimethyloctanal, 2-methyl-3- (4-tert-butylphenyl) propanal or the Schiff base of 2, 4-dimethyl-3-cyclohexenecarbaldehyde, 6-isopropylquinoline, 6-isobutylquinoline, 6-cyclohexylquinoline, 2-tert-butyl-benzaldehyde, 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, syringyl methyl ether, isoeugenol, isoeugenyl methyl ether, thymol, carvacrol, diphenyl ether, β -naphthyl methyl ether, β -naphthyl ethyl ether, β -naphthyl isobutyl 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-octanolactone (octanolactone), 3-methyl-1, 4-octanolactone, 1, 4-nonalactone, 1, 4-decalactone, 8-decene-1, 4-lactone, 1, 4-undecalactone, 1, 4-dodecalactone, 1, 5-decalactone, 1, 5-dodecalactone, 1, 15-pentadecanolide, cis-and trans-1' -pentadecan-1, 15-lactone, cis-and trans-12-pentadecan-1, 15-lactone, 1, 16-hexadecanolide, 9-hexadecanolide, 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 aroma component in the present invention. Essential oils are usually extracted by steam distillation, solid phase extraction, cold pressing, solvent extraction, supercritical fluid extraction, water distillation or simultaneous distillation-extraction. Essential oils may be derived from several different parts of a plant, including, for example, leaves, flowers, roots, buds, twigs, rhizomes, heartwood, bark, resin, seeds, and fruits. The major plant families from which essential oils are extracted include the family Compositae (Asteraceae), the family Myrtaceae (Myrtaceae), the family Lauraceae (Lauraceae), the family Labiatae (Lamiaceae), the family Myrtaceae (Myrtaceae), the family Rutaceae (Rutaceae), and the family Zingiberaceae (Zingiaceae). The oil is "essential" in the sense that it carries the unique aroma 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 skeleton 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 to be a single component. Thus, individual essential oils may be considered as a single fragrant component for the purposes of the present invention.

Specific examples of the essential oils used as the fragrant component of the present invention include cedar wood oil, juniper oil, cumin oil, cinnamon oil, camphor oil, rosewood oil, ginger oil, basil oil, eucalyptus oil, lemongrass oil, peppermint oil, rosemary oil, spearmint oil, tea tree oil, frankincense 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 rosin oil (galbanum oil), geranium oil, grapefruit oil, pine leaf oil, wormwood oil, labdanum oil (labdanum oil), strigose oil, thyme oil, verbena oil, marjoram oil, mandarin oil, sage oil, nutmeg oil, myrtle oil, clove oil, neroli oil, patchouli oil, sandalwood oil, thyme oil, verbena oil, vetiver oil (wintergreen oil), and wintergreen oil.

The number of different fragrance components comprised 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 "aroma formulation" refers to an aroma component as defined above, plus any optional excipients. Excipients may be included in the fragrance formulation for various purposes, such as solvents for insoluble or poorly soluble components, as diluents for more effective components, or to control the vapor pressure and evaporation characteristics of the fragrance formulation. Excipients may have many of the characteristics of aromatic components, but do not themselves have a strong odor. Thus, excipients can be distinguished from fragrance components in that they can be added to fragrance formulations in high proportions (e.g., 30% or even 50% by weight 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: a hydrocarbon i); aliphatic and araliphatic alcohols ii); aliphatic aldehydes and their acetals iv); aliphatic carboxylic acids and esters viii thereof); acyclic terpene alcohols ix); cyclic terpene aldehydes and ketoxii); cyclic and cycloaliphatic ethers xiii); ester xvi) of a cyclic alcohol; esters of araliphatic alcohols and aliphatic carboxylic acids xviii); araliphatic ethers and their acetals xix); aromatic and araliphatic aldehydes and ketones xx), and aromatic and araliphatic carboxylic acids and esters xxi) thereof; as further described and illustrated above.

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

The fragrance formulation typically comprises 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 particle. The amount of fragrance formulation can be measured by taking a slurry of the 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 laundry treatment compositions in all physical forms.

In a typical laundry treatment composition according to the present invention, the benefit agent delivery particle is typically present at a level 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 particle may also be formed in situ during the manufacture of, for example, a liquid laundry detergent comprising an anionic surfactant. In a typical process, the cationic surfactant is first deposited on the outer surface of the shell of the pre-formed core-shell particle. The mixture of granules is then combined with a liquid laundry detergent ingredient (including anionic surfactant) (as described further below). 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 granule. The charged heads of the respective surfactants are neutralized during the compounding process. If desired, additional ingredients can 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^-1The viscosity of the composition may suitably be in the range of from about 200 to about 10,000 mPa-s at the shear rate of (a). The shear rate is the shear rate that is typically applied to a liquid as it is poured from a bottle. The pourable liquid compositions generally have a viscosity of from 200 to 2,500 mPa-s, preferably from 200 to 1500 mPa-s.

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

Type of product

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

Laundry detergent

In the context of the present invention, the term "laundry detergent" refers to a formulated composition intended for and capable of wetting and cleaning household clothing, such as clothes, linen and other household fabrics. The term "linen" is often used to describe certain types of laundry items, including sheets, pillowcases, towels, tablecloths, napkins, and uniforms. Textiles may include woven, non-woven, and knitted fabrics; and may comprise natural or synthetic fibers such as silk fibers, flax 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 detergents used in 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 cleaning benefits, the laundry detergents according to the present invention typically 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 will depend on the intended use of the laundry detergent. For example, different surfactant systems may be selected for hand washing products and for products used in different types of automatic washing machines. The total amount of surfactant present also depends on the intended end use and can be as high as 60% (by weight based on the total weight of the composition) in a fully formulated product in a composition for hand washing fabrics. In compositions for machine washing fabrics, an amount of from 5 to 40%, for example from 15 to 35% (by weight based on the total weight of the composition) is generally suitable.

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

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

Non-soap anionic surfactants are primarily used to promote 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 wash-off coating, particularly linear alkyl benzene sulphonates (preferably C₁₁-C₁₅Linear alkylbenzene sulfonate) and sodium lauryl ether sulfate (preferably ethoxylated C of 1-3EO on average)₁₀-C₁₈Alkyl sulfates) and mixtures thereof.

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

Nonionic surfactants can provide enhanced performance for removing very hydrophobic oily soils and for cleaning hydrophobic polyester and polyester/cotton blends.

The nonionic surfactants useful in the present invention are typically polyoxyalkylene compounds, i.e., the reaction product of an alkylene oxide, such as ethylene oxide or propylene oxide or mixtures thereof, with a starter molecule 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 heteric (random) structures. For example, they may contain a single block of alkylene oxide, or they may be diblock alkoxylate or triblock alkoxylate. Within the block structure, the blocks may be all ethylene oxide or all propylene oxide, or the blocks may contain a heteric mixture of alkylene oxides. Examples of such materials include C with an average of 5 to 25 moles of ethylene oxide per mole of alkylphenol₈To C₂₂An alkylphenol ethoxylate; and fatty alcohol ethoxylates, e.g. C with an average of 2 to 40 moles of ethylene oxide per mole of alcohol₈To C₁₈Primary or secondary linear or branched alcohol ethoxylates.

A preferred type of nonionic surfactant for use in the present invention comprises aliphatic C's having an average of from 3 to 20, more preferably from 5 to 10 moles of ethylene oxide per mole of alcohol₈To C₁₈More preferably C₁₂To C₁₅Primary linear alcohol ethoxylates.

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

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

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

The liquid laundry detergents according to the present invention may typically comprise from 5 to 95%, preferably from 10 to 90%, more preferably from 15 to 85% of water (by weight based on the total weight of the composition). The composition may also comprise non-aqueous carriers 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 (e.g., monopropylene glycol and dipropylene glycol); c3 to C9 triols (such as glycerol); polyethylene glycol having a weight average molecular weight (Mw) of about 200-600; 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 xylene, sodium and potassium toluene, sodium and potassium ethylbenzene, and sodium and potassium isopropylbenzene (cumene) sulfonate).

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

When included in the liquid laundry detergents according to the present 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

The laundry detergent according to the present 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 (sequestration) or chelation (sequestration) (keeping the hard mineral in solution), by precipitation (formation of insoluble substances) or by ion exchange (exchange of charged particles).

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

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

Hydroxide builders suitable for use herein 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 amorphous and/or crystalline forms of alkali metal (e.g. sodium) silicates. Preference is given to crystalline layered sodium silicates (phyllosilicates) of the general formula (I):

NaMSi_xO_2x+1·yH₂O (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, referred to as alpha, beta, gamma and delta phases, with delta-sodium disilicate being most preferred.

The zeolite is naturally occurring or synthetic comprising (SiO)₄)^4-And (AlO)₄)^5-Tetrahedral crystalline aluminosilicates which share oxygen-bridge vertices in crystalline form and form cage-like structures. The ratio between oxygen, aluminum and silicon is 2:1 (Al + Si). The backbones gain their negative charge by replacing some of the Si with Al. The negative charge is neutralized by the cation and, under normal conditions, the backbone is sufficiently open to contain mobile water molecules. Suitable zeolite builders for use in the present invention can be defined by the general formula (II):

Na_x[(AlO₂)_x(SiO₂)_y]·zH₂O (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 herein may be selected from zeolites (having the general formula (II) above), sodium carbonate, delta-sodium disilicate and mixtures thereof.

Suitable organic non-phosphate builders for use herein include polycarboxylic acids in acid and/or salt form. When a salt form is used, alkali metal (e.g., sodium and potassium) or alkanolammonium salts are preferred. Specific examples of such materials include sodium and potassium citrate, tartrate, sodium and potassium tartrate monosuccinate, sodium and potassium tartrate disuccinate, sodium and potassium ethylenediaminetetraacetic acid, sodium and potassium N- (2-hydroxyethyl) -ethylenediaminetriacetic acid, sodium and potassium nitrilotriacetic acid, and sodium and potassium N- (2-hydroxyethyl) -nitrilotriacetic acid. Polymeric polycarboxylates may also be used, such as polymers of unsaturated monocarboxylic acids (e.g., acrylic, methacrylic, vinylacetic and crotonic acids) and/or unsaturated dicarboxylic acids (e.g., maleic, fumaric, itaconic, mesaconic and citraconic acids and their anhydrides). 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 acid esters in acid and/or salt form (e.g. citric acid esters) and mixtures thereof.

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

Preferably, the laundry detergent of the present invention contains phosphate builder 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 further comprise one or more polymeric cleaning enhancing agents, such as anti-redeposition polymers, soil release polymers and mixtures thereof.

The anti-redeposition polymer stabilizes soils in the wash solution, thereby preventing soil redeposition. Suitable anti-redeposition polymers for use in the present invention include alkoxylated polyethyleneimines. The polyethyleneimine being a polyethyleneimine comprising ethyleneimine units-CH₂CH₂NH-, and when branched, the hydrogen on the nitrogen is replaced by an ethyleneimine unit of the other chain. Preferred alkoxylated polyethyleneimines for use in the present invention have a weight average molecular weight (M) of about 300 to about 10000_w) A polyethyleneimine backbone. The polyethyleneimine backbone may be linear or branched. It may be branched to the extent that it is a dendrimer. The alkoxylation can 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. Preferred materials are ethoxylated polyethyleneimines 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 level of antiredeposition polymer may be 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 fabric surface during the laundering process. The affinity between the chemical structure of the SRP and the target fibers promotes the adsorption of the SRP on the fabric surface.

The SRPs used in the present invention may comprise 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 modify polymer properties, such as surface activity. Weight average molecular weight (M) of SRP_w) May suitably range from about 1000 to about 20,000, and preferably from about 1500 to about 10,000.

The SRP used in the present invention may suitably be selected from copolyesters of dicarboxylic acids (e.g. adipic acid, phthalic acid or terephthalic acid), diols (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-capped oligoesters, such as oligomers from ethylene glycol ("EG"), PG, DMT, and Na-3, 6-dioxa-8-hydroxyoctanesulfonic acid; non-ionic end-capped block polyester oligomeric compounds, such as those produced from DMT, Me-capped PEG and EG and/or PG, or a combination of DMT, EG and/or PG, Me-capped PEG and Na-dimethyl-5-sulfoisophthalate, and co-blocks of ethylene terephthalate or propylene terephthalate with 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 to 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 terephthalate and a glycol (preferably 1, 2-propanediol), and further comprise end caps formed from repeat units of alkylene oxides capped with alkyl groups. Examples of such materials have a structure corresponding to general formula (I):

wherein R is¹And R²Independently of one another X- (OC)₂H₄)_n-(OC₃H₆)_m；

Wherein X is C_1-4Alkyl, 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 4-9.

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

Transition metal ion chelating agents

Liquid or granular laundry detergents according to the invention may comprise one or more chelating agents for transition metal ions (e.g. iron, copper and manganese). Such chelating agents may help improve the stability of the composition and prevent the decomposition of certain ingredients, for example, transition metal catalysis.

Suitable transition metal ion chelating agents include phosphonates in acid and/or salt form. When a salt form is used, alkali metal (e.g., sodium and potassium) or alkanolammonium salts are preferred. Specific examples of such materials include aminotris (methylenephosphonic Acid) (ATMP), 1-hydroxyvinyl diphosphonic 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 can be present in an amount in the range of 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 acids

The 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_12-18Fatty acids, such as lauric acid, myristic acid, palmitic acid, or stearic acid; and wherein 50 to 100% (by weight based on the total weight of the mixture) of C is saturated_12-18Fatty acid mixtures of fatty acid compositions. 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 the purpose of structural formula interpretation, the fatty acid and/or salt thereof (as defined above) is not included in the content of the surfactant or the content of the builder in the formulation.

Rheology modifier

The liquid laundry detergent according to the present invention may comprise one or more rheology modifiers. Examples of such materials include polymeric thickeners and/or structurants, such as hydrophobically modified alkali swellable emulsions (HASE)) A copolymer. 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 the ethylenically unsaturated moiety and the hydrophobic moiety. Preferred HASE copolymers for use in the present invention comprise (meth) acrylic acid and (i) a monomer selected from linear or branched C₈-C₄₀Alkyl (preferably straight chain C)₁₂-C₂₂Alkyl) polyethoxylated (meth) acrylates; and (ii) is selected from (meth) acrylic acid C₁-C₄Linear or crosslinked copolymers prepared by addition polymerization of at least one additional monomer of an alkyl ester, a polyacid vinyl monomer (e.g., maleic acid, maleic anhydride, and/or salts thereof), and mixtures thereof. The polyethoxylated portion of associative monomer (i) typically comprises from about 5 to about 100, preferably from about 10 to about 80, and more preferably from about 15 to about 60, oxyethylene repeat 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).

Liquid laundry detergents according to the present invention may also have their rheology modified 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, microfibrillar cellulose and citrus pulp fiber. The presence of the external structurant can provide shear thinning rheology and can also enable the material (e.g., encapsulates and visual cues) to be stably suspended in the liquid.

Enzyme

The laundry detergent according to the present invention may comprise an effective amount of one or more enzymes selected from pectate lyases, proteases, amylases, cellulases, lipases, mannanases and mixtures thereof. The enzyme is preferably present together with a corresponding enzyme stabilizer.

The liquid laundry detergent according to the present invention preferably has 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) with demineralized water.

Additional optional ingredients

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

Packaging and dosing

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

The method of treating fabrics with 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 usually placed in a dispenser and from there is flushed into the machine by the water flowing into the machine, thereby forming a washing liquid. 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 range of about 10ml to about 60ml, preferably about 15 to 40 ml. Typical top loading washing machines (using 40-60 litres of water to form the wash liquor) may be dosed much higher, for example up to about 100 ml. Lower doses of detergent (e.g. 50ml or less) can be used in the hand wash process (about 1 to 10 litres of water is used to form the wash liquor). The subsequent water rinsing step and drying of the laundry are preferred. Any water input during any optional rinsing step is not included in determining the volume of the wash liquor.

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 percents are based on the total weight unless otherwise specified. Embodiments according to the present invention are represented by numbers; 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 a model fragrance containing 15 ingredients, an average particle diameter of about 13 μm, and a zeta potential of about-20 mV (measured as described above). The particles are obtained in an aqueous slurry having a solids content of about 30% by weight. A laundry liquid having the ingredients shown in table 1 was prepared separately.

Composition (I)	(active ingredient)
		C_12-14Linear alkyl benzene sulphonic acid (LAS)	11.2
C_12-15Alcohol ethoxylate (7EO)	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% by weight aqueous particle slurry and mixing for 30 minutes. A 1ml sample of the thus obtained CTAC treated granule slurry was then mixed with 9ml of laundry liquor to form the example 1 formulation. A control formulation was also prepared by adding 1ml of a sample of 10 wt% aqueous particle slurry (not mixed with CTAC) to 9ml of laundry liquor.

To test for fragrance leakage from the core-shell particles, test samples of the control and example 1 formulations were placed on the drum 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 at 40 ℃ for 10 minutes on a combiplal autosampler. 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 fragrance are added to give the total fragrance content. A calibration graph constructed by adding known amounts of free fragrance to a model laundry detergent allows conversion of the results to a leakage percentage graph.

The results are shown in Table 2.

TABLE 2

Preparation	Leakage of fragrance%
		Control (uncoated)	52.09
Example 1	22.40

The particles of example 1 according to the invention showed a significantly lower percentage of fragrance leakage when added to a laundry liquor compared to the uncoated control particles. When the laundry liquor is diluted in the washing operation (typically 35ml of liquor to 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

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 holes in the shell are at least partially blocked by a wash-off coating disposed at an outer surface of the shell; characterised in that the wash-removable coating is formed from deposited particles of a complex of a cationic surfactant and an anionic surfactant.

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; aliphatic aldehydes and acetals thereof; aliphatic carboxylic acids and esters thereof; acyclic terpene alcohols; cyclic terpene aldehydes and ketones; cyclic and cycloaliphatic ethers; esters of cyclic alcohols; esters of araliphatic alcohols and aliphatic carboxylic acids; araliphatic ethers and acetals thereof; aromatic and araliphatic aldehydes and ketones; and aromatic and araliphatic carboxylic acids and esters thereof.

3. A particle according to claim 1 or claim 2, wherein the fragrance formulation comprises 20-40 wt% based on the total weight of the benefit agent delivery particle.

4. The particle of any one of claims 1 to 3, wherein the solubility of the complex in distilled water (at 25 ℃ and atmospheric pressure) is less than 10 mg/L.

5. A process for making a benefit agent delivery particle according to any of claims 1 to 4 wherein the 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; 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.

6. The method of claim 5, wherein the cationic surfactant used to form the complex is selected from Cetyl Trimethyl Ammonium Chloride (CTAC), Stearyl Trimethyl Ammonium Chloride (STAC), Behenyl Trimethyl Ammonium Chloride (BTAC), and mixtures thereof.

7. A process according to claim 5 or claim 6, wherein the anionic surfactant used to form the complex is selected from Linear Alkylbenzene Sulphonate (LAS) having an alkyl chain length of 10-18 carbon atoms and mixtures thereof.

8. A laundry treatment composition comprising a benefit agent delivery particle as defined in any one of claims 1 to 4.

9. A laundry treatment composition according to claim 8, 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.

10. A laundry treatment composition according to claim 9, which is a liquid comprising from 5 to 95% (by weight based on the total weight of the composition) water.