WO2013189661A1

WO2013189661A1 - Improvements relating to fabric conditioners

Info

Publication number: WO2013189661A1
Application number: PCT/EP2013/059788
Authority: WO
Inventors: Christopher Boardman; Kenneth Stuart Lee
Original assignee: Unilever Plc; Unilever N.V.; Conopco, Inc., D/B/A Unilever
Priority date: 2012-06-21
Filing date: 2013-05-13
Publication date: 2013-12-27

Abstract

A fabric conditioning composition, which comprises: (i) an encapsulated phase change active, which undergoes a phase change from solid to liquid, or from liquid to solid, having a phase change temperature of from 24 to 39°C; (ii) a non-encapsulated volatile benefit agent; (iii) at least one softening agent selected from a cationic softening agent, a non-ionic softening agent and mixtures thereof; and (iv) an encapsulated volatile benefit agent comprising a capsule comprising a core and a shell, wherein the core comprises the volatile benefit agent; and the shell comprises from 50 to 100 wt % of a hydrophilic polymer; wherein the encapsulated phase change material comprises a shell that is permeable to the non-encapsulated volatile benefit agent, leads to a surprising viscostability benefit.

Description

IMPROVEMENTS RELATING TO FABRIC CONDITIONERS

Technical Field

The present invention relates to fabric conditioning compositions comprising an encapsulated volatile benefit agent with a hydrophilic shell in combination with an encapsulated phase change material, non-encapsulated volatile benefit agent and a cationic or nonionic softening active.

Background

Fragrances are a valuable and ubiquitously employed benefit agent in home and personal care applications. The use of perfumes in laundering signals to the consumer that the washing process has been achieved to an acceptable level.

Encapsulated perfume technologies are known for use in laundry products.

Fragrances are a highly valuable and ubiquitously employed benefit agent in home and personal care applications. Their use in laundering confirms to the consumer that the washing process has been achieved to an acceptable level.

Encapsulated perfumes can be used to aid perfume deposition and to ensure that perfume is released at the correct time to provide a perceivable benefit to the wearer of the garments - i.e. to provide a boost in perfume intensity at the correct time during wear.

However, the addition of fragrance encaps into fabric conditioning compositions can often cause high temperature instabilities resulting in significant thickening of the product. US7338928 describes a capsule for releasing one or more active ingredients from a composition comprising one or more oil absorbing polymers and a coating comprising one or more water sensitive, surface active polymers. The active ingredients may be oils, oil soluble compounds, hydrophobic compounds, flavours, fabric softeners, bleaches or detergents. The active ingredients are released from cosmetic, personal care and household products, for delivery to skin, hair, fabric and textiles, upon contact with water.

US 71 19060, US 6531444, WO2003/091379, WO2002/038713 relate to controlled delivery systems for fabric, based on a solid, substantially spherical particle comprising a hydrophobic material, for example a co-polymer, a so-called cationic charge booster and a cationic fabric softening agent, which assists in adhering the particles onto fabric. Our earlier patent application WO2007/062733 describes perfume deposition using a particle with a hydrophobic core and a non-ionic deposition aid. The deposition aid may be a polysaccharide having β-1 ,4 linkages.

Our previously published application, WO2003/014278 describes a water- dispersible particle wherein the material comprises (a) one or more polymeric deposition materials having an average repeat unit of formula (I) in which at least one or more R groups are independently selected from H, a hydrolysable group or a linker group in which when R is a hydrolysable group; the degree of substitution is 0 to 3 and when R is a linker group the degree of substitution is 0.01 to 3; and (b) a benefit agent attached to the deposition enhancing part; characterised in that the water-dispersible particle has a particle size from 20 to 5,000 nm. The polymeric deposition material can be cellulose units or β-1 ,4 linked polysaccharide units. Our co-pending application, EP1 1 193974.0, as yet unpublished, describes a fabric conditioning composition, comprising a volatile benefit agent in encapsulated and non-encapsulated forms; an encapsulated phase change active; and at least one cationic or non-ionic softening agent. A significant increase in the shear release effect of the encapsulated benefit agent is obtained. We have now found that the inclusion of a low level of encapsulated phase change material can significantly increase the time of storage viscostability at elevated temperatures of a fabric conditioning formulation containing volatile benefit agents, for example perfume, encapsulated with a hydrophilic shell. Definition of the Invention

In a first aspect, the present invention provides a fabric conditioning composition, which comprises:

(i) an encapsulated phase change active, which undergoes a phase change from solid to liquid, or from liquid to solid, having a phase change temperature of from 24 to 39°C;

(ϋ) a non-encapsulated volatile benefit agent;

(iii) at least one softening agent selected from a cationic softening agent, a non-ionic softening agent and mixtures thereof; and

(iv) an encapsulated volatile benefit agent comprising a capsule

comprising a core and a shell, wherein the core comprises the volatile benefit agent; and the shell comprises from 50 to 100 wt % of a hydrophilic polymer;

wherein the encapsulated phase change material comprises a shell that is permeable to the non-encapsulated volatile benefit agent.

In a second aspect of the present invention there is provided a process for treating fabric comprising the step of treating a fabric article with a composition as defined by the first aspect. Detailed Description of the Invention

The Encapsulated Volatile Benefit Agent The encapsulated volatile benefit agent comprises a capsule comprising a core and a shell, wherein the core comprises the volatile benefit agent; and the shell comprises from 50 to 100 wt % of a hydrophilic polymer. Mixtures of hydrophilic polymers may be used. Mixtures of capsules in accordance with the invention may be used.

The Core

The core of the capsule comprises the volatile benefit agent (as described below) and may also comprise an additional component, which is a hydrophobic polymer. In one, less preferred embodiment, the core is free from the hydrophobic polymer. Preferably, the volatile benefit agent, which is described below, is partitioned to the hydrophobic polymer. In the context of the present invention, this includes an embodiment where the volatile benefit agent is held within the hydrophobic polymer. As such, the volatile benefit agent may be wholly encapsulated or partially encapsulated by the hydrophobic polymer. It is also possible that the volatile benefit agent may remain associated with the hydrophobic core by chemical affinity. Thus, the volatile benefit agent is held in the hydrophobic polymer due to a greater affinity of the volatile benefit agent for the polymer than, for example, the aqueous product. The partition coefficient for the system is therefore in favour of the benefit agent being retained with the hydrophobic core.

Hydrophobic polymers usefully employed in accordance with the invention are aqueous emulsion polymers prepared from water insoluble, hydrophobic monomers and are described in US5521266 (at column 5, lines 7 to 25) and EP1209213AI (especially paragraphs [0005] to [0021 ]). "Hydrophobic monomers" refer to monoethylenically unsaturated monomers which have low or very low water solubility under the conditions of emulsion

polymerization, as described in US5521266 (particularly the passages referred to above).

As used herein, monomers having "low water solubility" or "very low water solubility" refers to monoethylenically unsaturated monomers having a water solubility at 25 to 50°C of no greater than 200 millimoles per litre of water or 50 millimoles per litre of water respectively, and the hydrophobic monomers employed in this invention are monomers having low water solubility.

Preferably the hydrophobic polymer comprises alkyl methacrylate, preferably an alkyl methacrylate copolymer, for example an acrylate polymer/Ci2-22 alkyl methacrylate copolymer.

According to one embodiment, the hydrophobic polymer is prepared as a terpolymer, wherein monomer A is a residue of (meth)acrylic acid, monomer B is a residue selected from Cs to C20 alkyl (meth)acrylates, and monomer C is a residue selected from Ci to C2₄ alkyl (meth)acrylates. The terpolymer also may include initiators and chain transfer residues, respectively. The terpolymer is prepared from relatively high levels (as wt %) of hydrophobic monomers and relatively low levels (as wt %) of ionic monomers in the form of (meth)acrylic acid or acrylic acid. The terpolymer includes from 80 % to 98 % by weight of a combination of one or more hydrophobic monomers in the form of C₄ to C2₄ alkyl (meth) acrylates and from 0.01 % to 20 % by weight of one or more ionic monomers.

According to a separate embodiment, a cross-linking polyethylenically unsaturated monomer is used in making the hydrophobic polymer. As used herein, the terms "polyethylenically" and "multi-ethylenically" refer to monomers having a plurality of ethylenically unsaturated groups. "Ionic monomers" refer to monoethylenically unsaturated monomers which are water soluble under the conditions of emulsion polymerization, as described in US4880842. The weight average molecular weight of the backbone, as measured on the polymer product after exhaustive hydrolysis, consisting of polymerized units of A, B and C, ranges from 1 , 000 to 100, 000. Weight average molecular weights may be measured using gel permeation chromatography (GPC) with styrene as a standard and are expressed as weight average molecular weight.

Hydrophobic polymers are prepared by free radical polymerization of hydrophobic and ionic monomers using conventional solution, suspension and emulsion polymerization processes, including those processes disclosed in US4427836; US4469825; US4594363; US4677003; US4910229; US4920160; US5157084; US5521266 and EP0267 726; EP0331421 , EP0915108 and EP1209213A1 .

According to one embodiment, the hydrophobic polymers are prepared by emulsion polymerization. Emulsion polymerization techniques for preparing aqueous dispersions of polymeric particles from ethylenically unsaturated monomers are well known in the polymer art. Single and multiple shot batch emulsion processes can be used, as well as continuous emulsion polymerization processes. In addition, if desired, a monomer mixture can be prepared and added gradually to the polymerization vessel. Similarly, the monomer composition within the polymerization vessel can be varied during the course of the polymerization, such as by altering the composition of the monomer being fed into the

polymerization vessel. Both single and multiple stage polymerization techniques can be used. The polymer particles can be prepared using a seed polymer emulsion to control the number of particles produced by the emulsion

polymerization as is known in the art. The particle size of the polymer particles can be controlled by adjusting the initial surfactant charge as is known in the art.

The hydrophobic emulsion polymers of the present invention have an average particle diameter that ranges from 20 nm to 1000 nm, including from 100 nm to 600 nm. Particle sizes herein are those determined using a Brookhaven Model BI-90 particle sizer manufactured by Brookhaven Instruments Corporation, Holtsville N. Y., and polymer particle diameters are reported as "effective diameter". The Shell

The shell comprises a hydrophilic polymer. By hydrophilic polymer is meant, in the context of the present invention, a polymer derived from water soluble or water dispersible monomers. In other words, the hydrophilic polymer is a polymer derived from hydrophilic monomers, thus, the hydrophilic polymer comprises hydrophilic groups. Mixtures of hydrophilic polymers may be used, that is to say one or more hydrophilic polymers, for example from one to ten hydrophilic polymers. As used herein, the term "water soluble", as applied to monomers, indicates that the monomer has a solubility of at least 1 gram per 100 grams of water, preferably at least 10 grams per 100 grams of water and more preferably at least about 50 grams per 100 grams of water. Hydrophilic polymers suitable for use in the present invention include natural and synthetic polymers and copolymers, starch derivatives, polysaccharides, hydrocolloids, natural gums, proteins, and mixtures thereof.

Examples of preferred natural and synthetic polymers and copolymers which are useful as hydrophilic polymers in the context of the invention include polyvinyl pyrrolidone, polyvinyl alcohol (PVOH), ethylene maleic anhydride copolymer, methylvinyl ether maleic anhydride copolymer, acrylic acid copolymers, anionic polymers of methacrylic acid and methacrylate, cationic polymers with dimethyl- aminoethyl ammonium functional groups, polyethylene oxides and water soluble polyamide or polyester. Preferably, the hydrophilic polymer is selected from polyvinylalcohol and hydrolysed corn starch, preferably polyvinyl alcohol.

Polyvinyl alcohol useful in the practice of the invention is partially and fully hydrolyzed polyvinyl acetate, termed "polyvinyl alcohol" with polyvinyl acetate as hydrolyzed to an extent, also termed degree of hydrolysis, of from about 75% up to about 99%. Such materials are prepared by means of any of Examples l-XIV as described in US5051222. A polyvinyl alcohol usefully employed in the present invention is Mowiol 3-83, having a molecular weight of about 14,000 daltons (Da) and a degree of hydrolysis of about 83 %. Also useful is Mowiol 3-98, a fully hydrolyzed (98 %) polyvinyl alcohol having a molecular weight of 16,000 daltons (Da); both are commercially available from Gehring-Montgomery, Inc. of Warminister Pa. Other suitable polyvinyl alcohols are: AIRVOL 205, having a molecular weight of about 15,000 to 27,000 Da and a degree of hydrolysis of about 88%, and VINEX 1025, having a molecular weight of 15,000 to 27,000 Da with a degree of hydrolysis of about 99% and commercially available from Air Products & Chemicals, Inc. of Allentown, Pa. ; ELVANOL 51 -05, having a molecular weight of about 22,000 to 26,000Da and a degree of hydrolysis of about 89% and commercially available from the Du Pont Company, Polymer Products Department, Wilmington, Del. ; ALCOTEX 78 having a degree of hydrolysis of about 76% to about 79%,

ALCOTEX F88/4 having a degree of hydrolysis of about 86% to about 88% and commercially available from the Harlow Chemical Co. Ltd. of Templefields, Harlow, Essex, England CM20 2BH; and GOHSENOL GL-03 and GOHSENOL KA-20 commercially available from Nippon Gohsei K. K. , The Nippon Synthetic Chemical Industry Co. , Ltd. , of No. 9-6, Nozaki Cho, Kita-Ku, Osaka, 530 Japan. Suitable polysaccharides are polysaccharides of the non-sweet, coloidally-soluble types, such as starch derivates, dextrinized and hydrolyzed starches, and the like. Preferred starches for use in the present invention include those derived from corn, tapioca, wheat, potato, rice, sweet potato, sago and mung bean, preferably corn starch. Most preferred are Zea Mays(corn) starch, hydrolyzed corn starch and hydrolyzed corn starch octenylsuccinate.

A suitable polysaccharide is a water dispersible, modified starch commercially available as Capsul, N-Lok, commercially available from the National Starch and Chemical Company of Bridgewater, N. J. ; Pure-Cote™, commercially available from the Grain Processing Corporation of Muscatine, Iowa. Suitable hydrocolloids are xanthan and maltodextrin, preferably maltodextrins such as Maltrin™ M100, and Maltrin™ M150, commercially available from the Grain Processing

Corporation of Muscatine, Iowa.

Suitable capsules for use in the present invention are the HydroSal range, particularly HydroSal 1 and HydroSal 2, available from Salvona, Daton, NJ. The Phase Change Active

Phase change actives are materials that can absorb, store and release heat whilst the material changes its physical form. This is known as a phase change. Water changing from solid (ice) to liquid is an example of this phenomenon. During these phase changes large amounts of heat are absorbed or released.

The phase change active has a thermal phase transition temperature (TPTT) in the range 24 to 39°C. The TPTT may conveniently be measured by the Perkin & Elmer thermal analysis system.

The Perkin & Elmer thermal analysis system measures the heat flow into a material to be heated as a function of the temperature of the material. By investigating a material at various temperatures, a temperature profile is obtained. Such a temperature profile usually has one or more peaks, each peak

corresponding to a maximum for the heat flow into the material at a specific temperature. The temperature corresponding to the major peak in the temperature profile is referred to as the thermal phase transition temperature. Generally a high TPTT corresponds to a high softening temperature of the material. The material has a TPTT in the range 24 to 39°C, preferably from 25 to 39°C, more preferably from 26 to 38°C and most preferably from 26 to 30°C.

Phase change actives possess a latent heat and show a phase transition phenomena between phases at a phase transition temperature. In the present invention, phase transitions are solid to liquid phase or liquid to solid phase changes. At these phase changes, PTMs reversibly absorb or release heat from the environment at around the phase transition temperature, which is

accompanied with a corresponding change in the ambient temperature.

The phase change active is not intended to be a perfume, or formaldehyde. The phase change active may be in the form of a composition provided that the total composition has a TPTT in the range 24 to 39°C, preferably from 25 to 39°C, more preferably from 26 to 38°C and most preferably from 26 to 30°C.

Suitable compositions comprise may hydrocarbon materials comprising a linear or branched alkyl chain and preferably comprising an average of from 12 to 50 carbon atoms per molecule, preferably from 12 to 30 carbon atoms. Preferably, the hydrocarbon materials are either alkanes or alkenes. Relatively small amounts of non-alkyl substituent groups may be present provided the

hydrocarbon nature of the product is not substantially affected.

Examples of suitable hydrocarbon materials for use in the hydrocarbon

composition are the liquid hydrocarbon materials of natural source. Other liquid hydrocarbon materials including the liquid fractions derived from crude oil, such as mineral oil or liquid paraffins and cracked hydrocarbons. A preferred material is paraffin wax (n-Octadecane). Examples of solid or semi-solid hydrocarbon materials are the paraffinic materials of longer chain length, and hydrogenated versions of some of the liquid materials mentioned above. A particularly useful combination of hydrocarbon materials is a mixture of mineral oil (for example, M85 ex Daltons Company) and petroleum jelly (for example, Silkolene 910 ex Daltons), wherein the weight ratio of mineral oil to petroleum jelly is chosen such that the TPTT of the mixture is in the range of from 24 to 39°C. In our experiments this result was obtained by using a ratio of mineral oil to petroleum jelly of less than 3:1 , preferably from 2:1 to 1 :3. Mineral oil is a liquid mixture of linear and branched hydrocarbons having an average number of carbon atoms per molecule of 26. Petroleum jelly is a semi-solid mixture of linear and branched hydrocarbons having an average number of carbon atoms per molecule of 26, and having a softening temperature of about 50°C.

The phase change active is encapsulated in a polymer shell to form encapsulated particles having a preferred particle size of from 10 nm to 1000 μιτι, preferably 50 nm to 100 μιτι, more preferably 0.2 to 30 μιτι. The use of encapsulated materials has the advantage that the materials may be readily dispersed without

interference or interaction with the fabric softener compound. An additional advantage in that the encapsulated material does not cause a "messiness" feeling when deposited on the fabric which may be present with materials of a semi-liquid nature. Suitable encapsulating polymers include those formed from melamine- formaldehyde or urea formaldehyde condensates, as well as similar types of aminoplasts. Additionally, capsules made via the simple or complex coacervation of gelatin are also preferred for use with the coating. Capsules having shell walls comprised of polyurethane, polyamide, polyolefin, polysaccaharide, protein, silicone, lipid, modified cellulose, gums, polyacrylate, polyphosphate, polystyrene, and polyesters or combinations of these materials are also functional. Further examples of suitable phase change actives are those materials disclosed in WO 03/0144460 having a phase transition temperature of from 24 to 39°C, referred to therein as "Phase Transition Materials" or "PTM's" at page 6, final paragraph to the penultimate line on page 8.

A preferred material is Lurapret TX PMC 28 commercially available from BASF which is a material, specifically paraffin wax (comprising n-Octadecane), encapsulated in polymethylmethacrylate having a particle size in the range 0.2 to 20μηη. This material has a phase transition temperature of about 28°C.

The phase change actives are generally deposited to apply from 0.2 to 1 %, preferably 0.2 to 0.5 % by weight of the fabric after drying. The encapsulated phase change actives are preferably present in an amount of from 0.01 to 15 wt %, more preferably 0.05 to 10 wt %, most preferably from 0.1 to 8 wt % by weight of the fabric softening composition.

The encapsulated phase change material comprises a shell that is permeable to the unconfined volatile benefit agent in the composition. Suitable encapsulating polymers include those formed from melamine-formaldehyde or urea

formaldehyde condensates, as well as similar types of aminoplasts. Additionally, capsules made via the simple or complex coacervation of gelatin are also preferred for use with the coating. Capsules having shell walls comprised of polyurethane, polyamide, polyolefin, polysaccaharide, protein, silicone, lipid, modified cellulose, gums, polyacrylate, polyphosphate, polystyrene, and polyesters or combinations of these materials are also suitable. A preferred material is polymethylmethacrylate.

The Volatile Benefit Agent The volatile benefit agent is an agent which is volatile and which confers a benefit to fabric. Suitable volatile benefit agents include but are not limited to perfumes, insect repellents, essential oils, sensates and aromatherapy actives, preferably perfumes. Mixtures of volatile benefit agents may be used. The total amount of volatile benefit agent is preferably from 0.01 to 10 % by weight, more preferably from 0.05 to 5 % by weight, even more preferably from 0.1 to 4.0 %, most preferably from 0.15 to 4.0 % by weight, based on the total weight of the composition. The preferred volatile benefit agent is a perfume. The compositions of the compositions of the invention also comprise an unconfined (also called non- encapsulated) volatile benefit agent. Where the volatile benefit agent is a perfume, the perfumes described below are suitable for use as the encapsulated volatile benefit agent and also as the unconfined perfume component.

Any suitable perfume or mixture of perfumes may be used. Useful components of the perfume include materials of both natural and synthetic origin. They include single compounds and mixtures. Specific examples of such components may be found in the current literature, e.g., in Fenaroli's Handbook of Flavor Ingredients, 1975, CRC Press; Synthetic Food Adjuncts, 1947 by M. B. Jacobs, edited by Van Nostrand; or Perfume and Flavor Chemicals by S. Arctander 1969, Montclair, N.J. (USA). These substances are well known to the person skilled in the art of perfuming, flavouring, and/or aromatizing consumer products, i.e., of imparting an odour and/or a flavour or taste to a consumer product traditionally perfumed or flavoured, or of modifying the odour and/or taste of said consumer product.

By perfume in this context is not only meant a fully formulated product fragrance, but also selected components of that fragrance, particularly those which are prone to loss, such as the so-called 'top notes'.

Top notes are defined by Poucher (Journal of the Society of Cosmetic Chemists 6(2):80 [1955]). Examples of well known top-notes include citrus oils, linalool, linalyl acetate, lavender, dihydromyrcenol, rose oxide and cis-3-hexanol. Top notes typically comprise 15-25%wt of a perfume composition and in those embodiments of the invention which contain an increased level of top-notes it is envisaged at that least 20%wt would be present within the encapsulate.

Some or all of the perfume or pro-fragrance may be encapsulated, typical perfume components which it is advantageous to encapsulate, include those with a relatively low boiling point, preferably those with a boiling point of less than 300, preferably 100-250 Celsius and pro-fragrances which can produce such

components.

It is also advantageous to encapsulate perfume components which have a low Clog P (ie. those which will be partitioned into water), preferably with a Clog P of less than 3.0. These materials, of relatively low boiling point and relatively low Clog P have been called the "delayed blooming" perfume ingredients and include the following materials:

Allyl Caproate, Amyl Acetate, Amyl Propionate, Anisic Aldehyde, Anisole,

Benzaldehyde, Benzyl Acetate, Benzyl Acetone, Benzyl Alcohol, Benzyl Formate, Benzyl Iso Valerate, Benzyl Propionate, Beta Gamma Hexenol, Camphor Gum, Laevo-Carvone, d-Carvone, Cinnamic Alcohol, Cinamyl Formate, Cis-Jasmone, cis-3-Hexenyl Acetate, Cuminic Alcohol, Cyclal C, Dimethyl Benzyl Carbinol, Dimethyl Benzyl Carbinol Acetate, Ethyl Acetate, Ethyl Aceto Acetate, Ethyl Amyl Ketone, Ethyl Benzoate, Ethyl Butyrate, Ethyl Hexyl Ketone, Ethyl Phenyl Acetate, Eucalyptol, Eugenol, Fenchyl Acetate, Flor Acetate (tricyclo Decenyl Acetate), Frutene (tricyclco Decenyl Propionate), Geraniol, Hexenol, Hexenyl Acetate, Hexyl Acetate, Hexyl Formate, Hydratropic Alcohol, Hydroxycitronellal, Indone, Isoamyl Alcohol, Iso Menthone, Isopulegyl Acetate, Isoquinolone, Ligustral, Linalool, Linalool Oxide, Linalyl Formate, Menthone, Menthyl Acetphenone, Methyl Amyl Ketone, Methyl Anthranilate, Methyl Benzoate, Methyl Benyl Acetate, Methyl Eugenol, Methyl Heptenone, Methyl Heptine Carbonate, Methyl Heptyl Ketone, Methyl Hexyl Ketone, Methyl Phenyl Carbinyl Acetate, Methyl Salicylate, Methyl-N-Methyl Anthranilate, Nerol, Octalactone, Octyl Alcohol, p-Cresol, p- Cresol Methyl Ether, p-Methoxy Acetophenone, p-Methyl Acetophenone, Phenoxy Ethanol, Phenyl Acetaldehyde, Phenyl Ethyl Acetate, Phenyl Ethyl Alcohol, Phenyl Ethyl Dimethyl Carbinol, Prenyl Acetate, Propyl Bornate, Pulegone, Rose Oxide, Safrole, 4-Terpinenol, Alpha-Terpinenol, and/or Viridine.

Preferred non-encapsulated perfume ingredients are those hydrophobic perfume components with a ClogP above 3. As used herein, the term "ClogP" means the calculated logarithm to base 10 of the octanol/water partition coefficient (P). The octanol/water partition coefficient of a perfume raw material (PRM) is the ratio between its equilibrium concentrations in octanol and water. Given that this measure is a ratio of the equilibrium concentration of a PRM in a non-polar solvent (octanol) with its concentration in a polar solvent (water), ClogP is also a measure of the hydrophobicity of a material-the higher the ClogP value, the more

hydrophobic the material. ClogP values can be readily calculated from a program called "CLOGP" which is available from Daylight Chemical Information Systems Inc., Irvine Calif., USA. Octanol/water partition coefficients are described in more detail in U.S. Pat. No. 5,578,563.

Perfume components with a ClogP above 3 comprise: Iso E super, citronellol, Ethyl cinnamate, Bangalol, 2,4,6-Trimethylbenzaldehyde, Hexyl cinnamic aldehyde, 2,6-Dimethyl-2-heptanol, Diisobutylcarbinol, Ethyl salicylate, Phenethyl isobutyrate, Ethyl hexyl ketone, Propyl amyl ketone, Dibutyl ketone, Heptyl methyl ketone, 4,5-Dihydrotoluene, Caprylic aldehyde, Citral, Geranial, Isopropyl benzoate, Cyclohexanepropionic acid, Campholene aldehyde, Caprylic acid, Caprylic alcohol, Cuminaldehyde, 1 -Ethyl-4-nitrobenzene, Heptyl formate, 4- Isopropylphenol, 2-lsopropylphenol, 3-lsopropylphenol, Allyl disulfide, 4-Methyl-1 - phenyl-2-pentanone, 2-Propylfuran, Allyl caproate, Styrene, Isoeugenyl methyl ether, Indonaphthene, Diethyl suberate, L-Menthone, Menthone racemic, p-Cresyl isobutyrate, Butyl butyrate, Ethyl hexanoate, Propyl valerate, n-Pentyl propanoate, Hexyl acetate, Methyl heptanoate, trans-3,3,5-Trimethylcyclohexanol, 3,3,5- Trimethylcyclohexanol, Ethyl p-anisate, 2-Ethyl-1 -hexanol, Benzyl isobutyrate, 2,5-Dimethylthiophene, Isobutyl 2-butenoate, Caprylnitrile, gamma-Nonalactone, Nerol, trans-Geraniol, 1 -Vinylheptanol, Eucalyptol, 4-Terpinenol, Dihydrocarveol, Ethyl 2-methoxybenzoate, Ethyl cyclohexanecarboxylate, 2-Ethylhexanal, Ethyl amyl carbinol, 2-Octanol, 2-Octanol, Ethyl methylphenylglycidate, Diisobutyl ketone, Counnarone, Propyl isovalerate, Isobutyl butanoate, Isopentyl propanoate, 2-Ethylbutyl acetate, 6-Methyl-tetrahydroquinoline, Eugenyl methyl ether, Ethyl dihydrocinnamate, 3,5-Dimethoxytoluene, Toluene, Ethyl benzoate, n- Butyrophenone, alpha-Terpineol, Methyl 2-methylbenzoate, Methyl 4- methylbenzoate, Methyl 3, methylbenzoate, sec. Butyl n-butyrate, 1 ,4-Cineole, Fenchyl alcohol, Pinanol, cis-2-Pinanol, 2,4, Dimethylacetophenone, Isoeugenol, Safrole, Methyl 2-octynoate, o-Methylanisole, p-Cresyl methyl ether, Ethyl anthranilate, Linalool, Phenyl butyrate, Ethylene glycol dibutyrate, Diethyl phthalate, Phenyl mercaptan, Cumic alcohol, m-Toluquinoline, 6-Methylquinoline, Lepidine, 2-Ethylbenzaldehyde, 4-Ethylbenzaldehyde, o-Ethylphenol, p- Ethylphenol, m-Ethylphenol, (+)-Pulegone, 2,4-Dimethylbenzaldehyde,

Isoxylaldehyde, Ethyl sorbate, Benzyl propionate, 1 ,3-Dimethylbutyl acetate, Isobutyl isobutanoate, 2,6-Xylenol, 2,4-Xylenol, 2,5-Xylenol, 3,5-Xylenol, Methyl cinnamate, Hexyl methyl ether, Benzyl ethyl ether, Methyl salicylate, Butyl propyl ketone, Ethyl amyl ketone, Hexyl methyl ketone, 2,3-Xylenol, 3,4, Xylenol, Cyclopentadenanolide and Phenyl ethyl 2 phenylacetate 2.

It is commonplace for a plurality of perfume components to be present in a formulation. In the compositions of the present invention it is envisaged that there will be four or more, preferably five or more, more preferably six or more or even seven or more different perfume components from the list given of delayed blooming perfumes given above and/or the list of perfume components with a ClogP above 3 present in the perfume. The volatile benefit agent may be an insect repellent. In chemical terms, most repellent actives belong to one of four groups: amides, alcohols, esters or ethers. Those suitable for use in the present invention are liquids or solids with a relatively low melting point and a boiling point above 150 °C, preferably liquids. They evaporate slowly at room temperature. Where the volatile benefit agent is an insect repellent, the repellents described below are suitable for use as the encapsulated volatile benefit agent and also as the unconfined repellent component. Many suitable insect repellents are related to perfume species (many fall into both classes). The most commonly used insect repellents include: DEET (N,N-diethyl- m-toluamide), essential oil of the lemon eucalyptus (Corymbia citriodora) and its active compound p-menthane-3,8-diol (PMD), lcaridin, also known as Picaridin, D- Limonene, Bayrepel, and KBR 3023, Nepetalactone, also known as "catnip oil", Citronella oil, Permethrin, Neem oil and Bog Myrtle.

Known insect repellents derived from natural sources include: Achillea alpina, alpha-terpinene, Basil oil (Ocimum basilicum), Callicarpa americana

(Beautyberry), Camphor, Carvacrol, Castor oil (Ricinus communis), Catnip oil (Nepeta species), Cedar oil (Cedrus atlantica), Celery extract (Apium graveolens), Cinnamon (Cinnamomum Zeylanicum, leaf oil), Citronella oil (Cymbopogon fleusus), Clove oil (Eugenic caryophyllata), Eucalyptus oil (70%+ eucalyptol, also known as cineol), Fennel oil (Foeniculum vulgare), Garlic Oil (Allium sativum), Geranium oil (also known as Pelargonium graveolens), Lavender oil (Lavandula officinalis), Lemon eucalyptus (Corymbia citriodora) essential oil and its active ingredient p-menthane-3,8-diol (PMD), Lemongrass oil (Cymbopogon flexuosus), Marigolds (Tagetes species), Marjoram (Tetranychus urticae and Eutetranychus orientalis), Neem oil (Azadirachta indica), Oleic acid, Peppermint (Mentha x piperita), Pennyroyal (Mentha pulegium), Pyrethrum (from Chrysanthemum species, particularly C. cinerariifolium and C. coccineum), Rosemary oil

(Rosmarinus officinalis), Spanish Flag Lantana camara (Helopeltis theivora), Solanum villosum berry juice, Tea tree oil (Melaleuca alternifolia) and Thyme (Thymus species) and mixtures thereof.

Preferred encapsulated insect repellents are mosquito repellents available from Celessence, Rochester, England. Celessence Repel, containing the active ingredient Saltidin™and Celessence Repel Natural, containing the active

Citrepel™ 75. Saltidin is a man made molecule developed originally by the Bayer Corporation. Citrepel is produced from eucalyptus oils and is high in p-menthane- 3,8-diol (PMD). A preferred non-encapsulated repellent is Citriodiol™ supplied by Citrefine.

Another group of volatile benefit agents with which the present invention can be applied are the so-called 'aromatherapy' materials. These include components of essential oils such as Clary Sage, Eucalyptus, Geranium, Lavender, Mace

Extract, Neroli, Nutmeg, Spearmint, Sweet Violet Leaf and Valerian.

The Fabric Softening Compound

The composition of the invention comprises a fabric softening active.

The fabric softening active is preferably different from the phase change active. Suitable fabric softening compounds are described below.

The fabric conditioning agents (also referred to herein as a fabric softening active or compound) may be cationic, non-ionic or mixtures thereof.

Fabric conditioning compositions in accordance with the invention may be dilute or concentrated. Dilute products typically contain up to about 8 %, generally about 2 to 8 % by weight of softening active, whereas concentrated products may contain up to about 50 wt %, preferably from about 8 to about 50 %, more preferably from 8 to 25 % by weight active. Overall, the products of the invention may contain from 2 to 50 wt %, preferably from 3 to 25 wt % of softening active.

The preferred softening active for use in rinse conditioner compositions of the invention is a quaternary ammonium compound (QAC). The preferred quaternary ammonium fabric conditioner for use in compositions of the present invention are the so called "ester quats".

Particularly preferred materials are the ester-linked triethanolamine (TEA) quaternary ammonium compounds comprising a mixture of mono-, di- and tri- ester linked components.

Typically, TEA-based fabric softening compounds comprise a mixture of mono, di- and tri-ester forms of the compound where the di-ester linked component comprises no more than 70 % by weight of the fabric softening compound, preferably no more than 60 wt % of the fabric softening compound and at least 10 % of the monoester linked component.

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

[(CH₂)_n(TR)]_m

I

R¹-N⁺-[(CH₂)n(OH)]_3-m X- (I) wherein each R is independently selected from a C_5-3₅ alkyl or alkenyl group; R¹ represents a Ci_-4 alkyl, C_2-4 alkenyl or a Ci_-4 hydroxyalkyl group; T is generally O- CO. (i.e. an ester group bound to R via its carbon atom), but may alternatively be CO-O (i.e. an ester group bound to R via its oxygen atom); n is a number selected from 1 to 4; m is a number selected from 1 , 2, or 3; and X^" is an anionic counter- ion, such as a halide or alkyl sulphate, e.g. chloride or methylsulphate. Di-esters variants of formula I (i.e. m = 2) are preferred and typically have mono- and tri- ester analogues associated with them. Such materials are particularly suitable for use in the present invention. Especially preferred agents are preparations which are rich in the di-esters of triethanolammonium methylsulphate, otherwise referred to as "TEA ester quats".

Commercial examples include Stepantex™ UL85, ex Stepan, Prapagen™ TQL, ex Clariant, and Tetranyl™ AHT-1 , ex Kao, (both di-[hardened tallow ester] of triethanolammonium methylsulphate), AT-1 (di-[tallow ester] of

triethanolammonium methylsulphate), and L5/90 (di-[palm ester] of

triethanolammonium methylsulphate), both ex Kao, and Rewoquat™ WE15 (a di- ester of triethanolammonium methylsulphate having fatty acyl residues deriving from C10-C20 and C16-C18 unsaturated fatty acids), ex Witco Corporation.

Also, soft quaternary ammonium actives such as Stepantex VK90, Stepantex VT90, SP88 (ex-Stepan), Prapagen TQ (ex-Clariant), Dehyquart AU-57 (ex- Cognis), Rewoquat WE18 (ex-Degussa) and Tetranyl L190 P, Tetranyl L190 SP and Tetranyl L190 S (all ex-Kao) are suitable. A second group of QACs suitable for use in the invention is represented by formula (II):

(R¹)₃N⁺-(CH₂)_n-CH-TR² X^" (II)

CH₂TR² wherein each R¹ group is independently selected from Ci_-4 alkyl, hydroxyalkyl or C2_-4 alkenyl groups; and wherein each R² group is independently selected from Cs- 28 alkyl or alkenyl groups; and wherein n, T, and X^" are as defined above. Preferred materials of this second group include 1 ,2 £>/s[tallowoyloxy]-3- trimethylammonium propane chloride, 1 ,2 £>/s[hardened tallowoyloxy]-3- trimethylammonium propane chloride, 1 ,2-i /s[oleoyloxy]-3-trimethylammonium propane chloride, and 1 ,2 i /s[stearoyloxy]-3-trimethylammonium propane chloride. Such materials are described in US 4,137,180 (Lever Brothers).

Preferably, these materials also comprise an amount of the corresponding mono- ester.

A third group of QACs suitable for use in the invention is represented by formula (III):

(R¹ )2-N⁺-[(CH₂)n-T-R²]₂ X^" (III) wherein each R¹ group is independently selected from Ci_-4 alkyl, or C2_-4 alkenyl groups; and wherein each R² group is independently selected from Cs-28 alkyl or alkenyl groups; and n, T, and X^" are as defined above. Preferred materials of this third group include bis(2-tallowoyloxyethyl)dimethyl ammonium chloride, partially hardened and hardened versions thereof. The iodine value of the quaternary ammonium fabric conditioning material is preferably from 0 to 80, more preferably from 0 to 60, and most preferably from 0 to 45. The iodine value may be chosen as appropriate. Essentially saturated material having an iodine value of from 0 to 5, preferably from 0 to 1 may be used in the compositions of the invention. Such materials are known as "hardened" quaternary ammonium compounds.

A further preferred range of iodine values is from 20 to 60, preferably 25 to 50, more preferably from 30 to 45. A material of this type is a "soft" triethanolamine quaternary ammonium compound, preferably triethanolamine di-alkylester methylsulphate. Such ester-linked triethanolamine quaternary ammonium compound comprise unsaturated fatty chains. lodine value as used in the context of the present invention refers to the measurement of the degree of unsaturation present in a material by a method of nmr spectroscopy as described in Anal. Chem., 34, 1 136 (1962) Johnson and Shoolery.

A further type of softening compound is a non-ester quaternary ammonium material represented by formula (IV):-

wherein each R¹ group is independently selected from Ci_-4 alkyl, hydroxyalkyl or C2_-4 alkenyl groups; R² group is independently selected from Cs-28 alkyl or alkenyl groups, and X^" is as defined above. Oily sugar derivatives

The compositions of the invention may contain a non-cationic softening material, which is preferably an oily sugar derivative. An oily sugar derivative is a liquid or soft solid derivative of a cyclic polyol (CPE) or of a reduced saccharide (RSE), said derivative resulting from 35 to 100 % of the hydroxyl groups in said polyol or in said saccharide being esterified or etherified. The derivative has two or more ester or ether groups independently attached to a C8-C22 alkyl or alkenyl chain.

Advantageously, the CPE or RSE does not have any substantial crystalline character at 20°C. Instead it is preferably in a liquid or soft solid state as herein defined at 20°C. The liquid or soft solid (as hereinafter defined) CPEs or RSEs suitable for use in the present invention result from 35 to 100% of the hydroxyl groups of the starting cyclic polyol or reduced saccharide being esterified or etherified with groups such that the CPEs or RSEs are in the required liquid or soft solid state. These groups typically contain unsaturation, branching or mixed chain lengths.

Typically the CPEs or RSEs have 3 or more ester or ether groups or mixtures thereof, for example 3 to 8, especially 3 to 5. It is preferred if two or more of the ester or ether groups of the CPE or RSE are independently of one another attached to a Cs to C22 alkyi or alkenyl chain. The Cs to C22 alkyi or alkenyl groups may be branched or linear carbon chains.

Preferably 35 to 85 % of the hydroxyl groups, most preferably 40-80 %, even more preferably 45-75 %, such as 45-70 % are esterified or etherified.

Preferably the CPE or RSE contains at least 35 % tri or higher esters, e.g. at least 40 %.

The CPE or RSE has at least one of the chains independently attached to the ester or ether groups having at least one unsaturated bond. This provides a cost effective way of making the CPE or RSE a liquid or a soft solid. It is preferred if predominantly unsaturated fatty chains, derived from, for example, rape oil, cotton seed oil, soybean oil, oleic, tallow, palmitoleic, linoleic, erucic or other sources of unsaturated vegetable fatty acids, are attached to the ester/ether groups.

These chains are referred to below as the ester or ether chains (of the CPE or RSE).

The ester or ether chains of the CPE or RSE are preferably predominantly unsaturated. Preferred CPEs or RSEs include sucrose tetratallowate, sucrose tetrarapeate, sucrose tetraoleate, sucrose tetraesters of soybean oil or cotton seed oil, cellobiose tetraoleate, sucrose trioleate, sucrose triapeate, sucrose pentaoleate, sucrose pentarapeate, sucrose hexaoleate, sucrose hexarapeate, sucrose triesters, pentaesters and hexaesters of soybean oil or cotton seed oil, glucose tiroleate, glucose tetraoleate, xylose trioleate, or sucrose tetra-,tri-, penta- or hexa- esters with any mixture of predominantly unsaturated fatty acid chains. The most preferred CPEs or RSEs are those with monounsaturated fatty acid chains, i.e. where any polyunsaturation has been removed by partial

hydrogenation. However some CPEs or RSEs based on polyunsaturated fatty acid chains, e.g. sucrose tetralinoleate, may be used provided most of the polyunsaturation has been removed by partial hydrogenation.

The most highly preferred liquid CPEs or RSEs are any of the above but where the polyunsaturation has been removed through partial hydrogenation.

Preferably 40 % or more of the fatty acid chains contain an unsaturated bond, more preferably 50 % or more, most preferably 60% or more. In most cases 65 % to 100 %, e.g. 65 % to 95 % contain an unsaturated bond.

CPEs are preferred for use with the present invention. Inositol is a preferred example of a cyclic polyol. Inositol derivatives are especially preferred.

In the context of the present invention, the term cyclic polyol encompasses all forms of saccharides. Indeed saccharides are especially preferred for use with this invention. Examples of preferred saccharides for the CPEs or RSEs to be derived from are monosaccharides and disaccharides.

Examples of monosaccharides include xylose, arabinose, galactose, fructose, sorbose and glucose. Glucose is especially preferred. Examples of

disaccharides include maltose, lactose, cellobiose and sucrose. Sucrose is especially preferred. An example of a reduced saccharide is sorbitan. The liquid or soft solid CPEs can be prepared by methods well known to those skilled in the art. These include acylation of the cyclic polyol or reduced

saccharide with an acid chloride; trans-esterification of the cyclic polyol or reduced saccharide fatty acid esters using a variety of catalysts; acylation of the cyclic polyol or reduced saccharide with an acid anhydride and acylation of the cyclic polyol or reduced saccharide with a fatty acid. See for instance US 4 386 213 and AU 14416/88 (both P&G).

It is preferred if the CPE or RSE has 3 or more, preferably 4 or more ester or ether groups. If the CPE is a disaccharide it is preferred if the disaccharide has 3 or more ester or ether groups. Particularly preferred CPEs are esters with a degree of esterification of 3 to 5, for example, sucrose tri, tetra and penta esters.

Where the cyclic polyol is a reducing sugar it is advantageous if each ring of the CPE has one ether or ester group, preferably at the Ci position. Suitable examples of such compounds include methyl glucose derivatives.

Examples of suitable CPEs include esters of alkyl(poly)glucosides, in particular alkyl glucoside esters having a degree of polymerisation of 2.

The length of the unsaturated (and saturated if present) chains in the CPE or RSE is C8-C22, preferably Ci2-C22- It is possible to include one or more chains of C Cs, however these are less preferred. The liquid or soft solid CPEs or RSEs which are suitable for use in the present invention are characterised as materials having a solid:liquid ratio of between 50:50 and 0:100 at 20°C as determined by T₂ relaxation time NMR, preferably between 43:57 and 0:100, most preferably between 40:60 and 0:100, such as, 20:80 and 0:100. The T₂ NMR relaxation time is commonly used for

characterising solid:liquid ratios in soft solid products such as fats and margarines. For the purpose of the present invention, any component of the signal with a T₂ of less than 100 με is considered to be a solid component and any component with T₂ > 100 με is considered to be a liquid component.

For the CPEs and RSEs, the prefixes (e.g. tetra and penta) only indicate the average degrees of esterification. The compounds exist as a mixture of materials ranging from the monoester to the fully esterified ester. It is the average degree of esterification which is used herein to define the CPEs and RSEs.

The HLB of the CPE or RSE is typically between 1 and 3.

Where present, the CPE or RSE is preferably present in the composition in an amount of 0.5-50% by weight, based upon the total weight of the composition, more preferably 1 -30% by weight, such as 2-25%, e.g. 2-20%. The CPEs and RSEs for use in the compositions of the invention include sucrose tetraoleate, sucrose pentaerucate, sucrose tetraerucate and sucrose pentaoleate.

Optional Ingredients Co-softeners and fatty complexing agents

Co-softeners may be used. When employed, they are typically present at from 0.1 to 20% and particularly at from 0.5 to 10%, based on the total weight of the composition. Preferred co-softeners include fatty esters, and fatty N-oxides. Fatty esters that may be employed include fatty monoesters, such as glycerol monostearate, fatty sugar esters, such as those disclosed WO 01/46361

(Unilever).

The compositions of the present invention may comprise a fatty complexing agent. Especially suitable fatty complexing agents include fatty alcohols and fatty acids. Of these, fatty alcohols are most preferred.

Fatty complexing material may be used to improve the viscosity profile of the composition.

Preferred fatty acids include hardened tallow fatty acid (available under the tradename Pristerene™, ex Uniqema). Preferred fatty alcohols include hardened tallow alcohol (available under the tradenames Stenol™ and Hydrenol™, ex Cognis and Laurex™ CS, ex Albright and Wilson). Ginol™ 1618 TA, ex Godrej is a further preferred material.

The fatty complexing agent is preferably present in an amount greater than 0.3 to 5% by weight based on the total weight of the composition. More preferably, the fatty component is present in an amount of from 0.4 to 4%. The weight ratio of the mono-ester component of the quaternary ammonium fabric softening material to the fatty complexing agent is preferably from 5:1 to 1 :5, more preferably 4:1 to 1 :4, most preferably 3:1 to 1 :3, e.g. 2:1 to 1 :2. Non-ionic surfactant

The compositions of the present invention may further comprise a nonionic surfactant. Typically these can be included for the purpose of stabilising the compositions. These are particularly suitable for compositions comprising hardened quaternary ammonium compounds.

Suitable nonionic surfactants include addition products of ethylene oxide and/or propylene oxide with fatty alcohols, fatty acids and fatty amines. Any of the alkoxylated materials of the particular type described hereinafter can be used as the nonionic surfactant. Suitable surfactants are substantially water soluble surfactants of the general formula:

R-Y-(C₂H₄O)_z-CH2-CH₂-OH where R is selected from the group consisting of primary, secondary and branched chain alkyl and/or acyl hydrocarbyl groups (when Y = -C(O)O, R≠ an acyl hydrocarbyl group); primary, secondary and branched chain alkenyl hydrocarbyl groups; and primary, secondary and branched chain alkenyl- substituted phenolic hydrocarbyl groups; the hydrocarbyl groups having a chain length of from 8 to about 25, preferably 10 to 20, e.g. 14 to 18 carbon atoms.

In the general formula for the ethoxylated nonionic surfactant, Y is typically: -O- , -C(O)O- , -C(O)N(R)- or -C(O)N(R)R- in which R has the meaning given above or can be hydrogen; and Z is at least about 8, preferably at least about 10 or 1 1 . Preferably the nonionic surfactant has an HLB of from about 7 to about 20, more preferably from 10 to 18, e.g. 12 to 16. Genapol™ C200 (Clariant) based on coco chain and 20 EO groups is an example of a suitable nonoionic surfactant.

If present, the nonionic surfactant is present in an amount from 0.01 to 10%, more preferably 0.1 to 5 by weight, based on the total weight of the composition.

Antifoam

An antifoam may be present as a processing aid, preferably in an amount of from 0.001 to 0.1 wt%, more preferably 0.001 to 0.05 wt %, most preferably from 0.0015 to 0.04 wt %. Additionally or alternatively, an antifoam may be present as a suds suppression aid, in order to reduce foam during the rinse, in an amount of from 0.025 to 0.45 wt %, preferably 0.03 to 0.4 wt %, most preferably from 0.05 to 0.35 wt %, for example 0.07 to 0.4 wt %, by weight of the total composition and based on 100 % antifoam activity.

A wide variety of materials may be used as antifoams, and antifoams are well known to those skilled in the art. See, for example, Kirk Othmer Encyclopedia of Chemical Technology, Third Edition, Volume 7, pages 430-447 (John Wiley & Sons, Inc., 1979).

Suitable antifoams include, for example, silicone antifoam compounds, alcohol antifoam compounds, for example 2-alkyl alcanol antifoam compounds, fatty acids, paraffin antifoam compounds, and mixtures thereof. By antifoam

compound it is meant herein any compound or mixtures of compounds which act such as to depress the foaming or sudsing produced by a solution of a detergent composition, particularly in the presence of agitation of that solution.

Particularly preferred antifoam compounds for use herein are silicone antifoam compounds defined herein as any antifoam compound including a silicone component. Many such silicone antifoam compounds also contain a silica component. The term "silicone" as used herein, and in general throughout the industry, encompasses a variety of relatively high molecular weight polymers containing siloxane units and hydrocarbyl group of various types like the polyorganosiloxane oils, such as polydimethyl-siloxane, dispersions or emulsions of polyorganosiloxane oils or resins, and combinations of polyorganosiloxane with silica particles wherein the polyorganosiloxane is chemisorbed or fused onto the silica. Silica particles are often hydrophobed, e.g. as Trimethylsiloxysilicate. Silicone antifoam agents are well known in the art and are, for example, disclosed in U. S. Patent 4, 265, 779, issued May 5, 25 1981 to Gandolfo et al and

European Patent Application No. 89307851 . 9, published February 7, 1990, by Starch, M. S. Other silicone antifoams are disclosed in U. S. Patent 3, 455, 839 which relates to compositions and processes for defoaming aqueous solutions by incorporating therein small amounts of polydimethylsiloxane fluids. Mixtures of silicone and silanated silica are described, for instance, in German Patent

Application DOS 2, 124, 526. Silicone defoamers and suds controlling agents in granular detergent compositions are disclosed in U. S. Patent 3, 933, 672, 35 Bartolotta et al, and in U. S. Patent 4, 652, 392, Baginski et al, issued March 24, 1987. Examples of suitable silicone antifoam compounds are the combinations of polyorganosiloxane with silica particles commercially available from Dow Corning, Wacker Chemie and Momentive.

Other suitable antifoam compounds include the monocarboxylic fatty acids and soluble salts thereof. These materials are described in US Patent 2, 954, 347. The monocarboxylic fatty acids, and salts thereof, for use as antifoam agents typically have hydrocarbyl chains of about 10 to about 24 carbon atoms, preferably about 12 to about 18 carbon atoms like the tallow

amphopolycarboxyglycinate commercially available under the trade name TAPAC. Suitable salts include the alkali metal salts such as sodium, potassium, and lithium salts, and ammonium and alkanolammonium salts.

Other suitable antifoam compounds include, for example, high molecular weight hydrocarbons such as paraffin, light petroleum odourless hydrocarbons, fatty esters (e. g. fatty acid triglycerides, glyceryl derivatives, polysorbates), fatty acid esters of monovalent alcohols, aliphatic C18-C40 ketones (e. g. stearone) N- alkylated amino triazines such as tri- to hexa- 10 alkylmelamines or di- to tetra alkyldiamine chlortriazines formed as products of cyanuric chloride with two or three moles of a primary or secondary amine containing 1 to 24 carbon atoms, propylene oxide, bis stearic acid amide and monostearyl phosphates such as monostearyl alcohol phosphate ester and monostearyl di-alkali metal (e. g. , K, Na, and Li) phosphates and phosphate esters, and nonionic polyhydroxyl derivatives. The hydrocarbons, such as paraffin and 15 haloparaffin, can be utilized in liquid form. The liquid hydrocarbons will be liquid at room temperature and atmospheric pressure, and will have a pour point in the range of about -40°C and about 5°C, and a minimum boiling point not less than about 1 10°C

(atmospheric pressure). It is also known to utilize waxy hydrocarbons, preferably having a melting point below about 100°C. Hydrocarbon suds suppressers are described, for example, in U. S. Patent 4, 265, 779. The hydrocarbons, thus, include aliphatic, alicyclic, aromatic, and heterocyclic saturated or unsaturated hydrocarbons having from about 12 to about 70 carbon atoms. The term

"paraffin", as used in this suds suppresser discussion, is intended to include mixtures of true paraffins and cyclic hydrocarbons. Copolymers of ethylene oxide and propylene oxide, particularly the mixed ethoxylated/propoxylated fatty alcohols with an alkyl chain length of from about 10 to about 16 carbon atoms, a degree of ethoxylation of from about 3 to about 30 and a degree of propoxylation of from about 1 to about 10, are also suitable antifoam compounds for use herein.

Other antifoams useful herein comprise the secondary alcohols (e.g. , 2-alkyl alkanols as described in DE 40 21 265) and mixtures of such alcohols with silicone oils, such as the silicones disclosed in US 4,798,679, US 4,075,1 18 and EP 150,872. The secondary alcohols include the C6-C16 alkyl alcohols having a CI-C16 chain like the 2-Hexyldecanol commercially available under the trade name ISOFOL16, 2-Octyldodecanol commercially available under the tradename ISOFOL20, and 2-butyl octanol, which is available under the trademark ISOFOL 12 from Condea. A preferred alcohol is 2-butyl octanol, which is available from Condea under the trademark ISOFOL 12. Mixtures of secondary alcohols are available under the trademark ISALCHEM 123 from Enichem. Mixed antifoams typically comprise mixtures of alcohol to silicone at a weight ratio of about 1 :5 to about 5:1 .

Further preferred antifoam agents are Silicone SRE grades and Silicone SE 47M, SE39, SE2, SE9 and SE10 available from Wacker Chemie; BF20+, DB310, DC1410, DC1430, 22210, HV495 and Q2-1607 ex Dow Corning; FD20P and BC2600 supplied by Basildon; and SAG 730 ex Momentive.

Other suitable antifoams, described in the literature such as in Hand Book of Food Additives, ISBN 0-566-07592-X, p. 804, are selected from dimethicone,

poloxamer, polypropyleneglycol, tallow derivatives, and mixtures thereof.

Preferred among the antifoams described above are the silicone antifoams, in particular the combinations of polyorganosiloxane with silica particles. Non-ionic ethoxylated surfactant

A non-ionic ethoxylated surfactant may be present in order to improve the appearance of the rinse liquor. It prevents the formation of scum which could potentially lead to deposition of scummy deposits on the laundered fabric. In particular it disperses the reaction product of the anionic surfactant from the wash and monoquat compound preventing flocculation and formation of scum resulting in a translucent dispersion.

Suitable non-ionic surfactants are alkoxylated materials, particularly addition products of ethylene oxide and/or propylene oxide with fatty alcohols, fatty acids and fatty amines.

Preferred materials are of the general formula: R-Y-(CH₂CH₂O)_zH

Where R is a hydrophobic moiety, typically being an alkyl or alkenyl group, said group being linear or branched, primary or secondary, and preferably having from 8 to 25, more preferably 10 to 20, and most preferably 10 to 18 carbon atoms; R may also be an aromatic group, such as a phenolic group, substituted by an alkyl or alkenyl group as described above; Y is a linking group, typically being O, CO.O, or CO.N(R¹), where R¹ is H or a Ci_-4 alkyl group; and z represents the average number of ethoxylate (EO) units present, said number being 20 or more, preferably at least 25, more preferably at least 30. Examples of suitable non-ionic surfactants include the ethoxylates of mixed natural or synthetic alcohols in the "coco" or "tallow" chain length. Preferred materials are condensation products of coconut fatty alcohol with 20-50 moles of ethylene oxide and condensation products of tallow fatty alcohol with 20-50 moles of ethylene oxide.

The ethoxylates of secondary alcohols such as 3-hexadecanol, 2-octadecanol, 4- eicosanol, and 5-eicosanol may also be used. Exemplary ethoxylated secondary alcohols have formulae Ci₂-EO(20); Ci₄-EO(20); C_M-EO(25); and Ci₆-EO(30). Suitable commercially available non-ionic surfactants include Lutensol AT25, Lutensol AT50 and Unitol CE 200F.

Optionally, the composition comprises an emulsifier that has an HLB of from 7 to 20, more preferably from 10 to 20, and most preferably from 15 to 20. A particular surfactant may be useful in the present compositions alone or in combination with other surfactants. The preferred amounts of non-ionic surfactant indicated below refer to the total amount of such materials that are present in the composition. The non-ionic surfactant is generally from 0.05 to 10%, usually 0.1 to 5%, and often 3 to 4% by weight, based on the total weight of the composition.

Shading Dyes Optional shading dyes can be used. Preferred dyes are violet or blue. Suitable and preferred classes of dyes are discussed below. Moreover the unsaturated quaternary ammonium compounds are subject to some degree of UV light and/or transition metal ion catalysed radical auto-oxidation, with an attendant risk of yellowing of fabric. The presence of a shading dye also reduces the risk of yellowing from this source.

Different shading dyes give different levels of colouring. The level of shading dye present in the compositions of the present invention depend, therefore, on the type of shading dye. Preferred overall ranges, suitable for the present invention are from 0.00001 to 0.1 wt %, more preferably 0.0001 to 0.01 wt %, most preferably 0.0005 to 0.005 wt % by weight of the total composition.

Direct Dyes

Direct dyes (otherwise known as substantive dyes) are the class of water soluble dyes which have an affinity for fibres and are taken up directly. Direct violet and direct blue dyes are preferred.

Preferably the dye are bis-azo or tris-azo dyes are used. Most preferably, the direct dye is a direct violet of the following structures:

or

wherein:

ring D and E may be independently naphthyl or phenyl as shown;

Ri is selected from: hydrogen and C1 -C4-alkyl, preferably hydrogen;

R2 is selected from: hydrogen, C1 -C4-alkyl, substituted or unsubstituted phenyl and substituted or unsubstituted naphthyl, preferably phenyl;

R3 and R₄ are independently selected from: hydrogen and C1 -C4-alkyl, preferably hydrogen or methyl;

X and Y are independently selected from: hydrogen, C1 -C4-alkyl and C1 -C4- alkoxy; preferably the dye has X= methyl; and, Y = methoxy and n is 0, 1 or 2, preferably 1 or 2.

Preferred dyes are direct violet 7, direct violet 9, direct violet 1 1 , direct violet 26, direct violet 31 , direct violet 35, direct violet 40, direct violet 41 , direct violet 51 , and direct violet 99. Bis-azo copper containing dyes such as direct violet 66 may be used.

The benzidene based dyes are less preferred.

Preferably the direct dye is present at 0.00001 wt% to 0.0010 wt% of the formulation.

In another embodiment the direct dye may be covalently linked to the photo- bleach, for example as described in WO2006/024612. Acid dyes

Cotton substantive acid dyes give benefits to cotton containing garments.

Preferred dyes and mixes of dyes are blue or violet. Preferred acid dyes

(i) azine dyes, wherein the dye is of the following core structure:

wherein R_a, R_b, R_c and R_d are selected from: H, a branched or linear C1 to C7- alkyl chain, benzyl a phenyl, and a naphthyl;

the dye is substituted with at least one SO3^" or -COO^" group;

the B ring does not carry a negatively charged group or salt thereof;

and the A ring may further substituted to form a naphthyl;

the dye is optionally substituted by groups selected from: amine, methyl, ethyl, hydroxyl, methoxy, ethoxy, phenoxy, CI, Br, I, F, and NO2.

Preferred azine dyes are: acid blue 98, acid violet 50, and acid blue 59, more preferably acid violet 50 and acid blue 98. Other preferred non-azine acid dyes are acid violet 17, acid black 1 and acid blue 29.

Preferably the acid dye is present at 0.0005 wt% to 0.01 wt% of the formulation. Hydrophobic dyes

The composition of the invention may comprise one or more hydrophobic dyes selected from benzodifuranes, methine, triphenylmethanes, napthalimides, pyrazole, napthoquinone, anthraquinone and mono-azo or di-azo dye

chromophores. Hydrophobic dyes are dyes which do not contain any charged water solubilising group. Hydrophobic dyes may be selected from the groups of disperse and solvent dyes. Blue and violet anthraquinone and mono-azo dye are preferred.

Preferred dyes include solvent violet 13, disperse violet 27 disperse violet 26, disperse violet 28, disperse violet 63 and disperse violet 77.

Preferably the hydrophobic dye is present at 0.0001 wt% to 0.005 wt% of the formulation.

Basic dyes

Basic dyes are organic dyes which carry a net positive charge. They deposit onto cotton. They are of particular utility for used in composition that contain predominantly cationic surfactants. Dyes may be selected from the basic violet and basic blue dyes listed in the Colour Index International.

Preferred examples include triarylmethane basic dyes, methane basic dye, anthraquinone basic dyes, basic blue 16, basic blue 65, basic blue 66, basic blue 67, basic blue 71 , basic blue 159, basic violet 19, basic violet 35, basic violet 38, basic violet 48; basic blue 3, basic blue 75, basic blue 95, basic blue 122, basic blue 124, basic blue 141 . Reactive dyes

Reactive dyes are dyes which contain an organic group capable of reacting with cellulose and linking the dye to cellulose with a covalent bond. They deposit onto cotton.

Preferably the reactive group is hydrolysed or reactive group of the dyes has been reacted with an organic species such as a polymer, so as to the link the dye to this species. Dyes may be selected from the reactive violet and reactive blue dyes listed in the Colour Index International.

Preferred examples include reactive blue 19, reactive blue 163, reactive blue 182 and reactive blue 96. Dye conjugates

Dye conjugates are formed by binding direct, acid or basic dyes to polymers or particles via physical forces. Dependent on the choice of polymer or particle they deposit on cotton or synthetics. A description is given in WO2006/055787. They are not preferred.

Particularly preferred dyes are: direct violet 7, direct violet 9, direct violet 1 1 , direct violet 26, direct violet 31 , direct violet 35, direct violet 40, direct violet 41 , direct violet 51 , direct violet 99, acid blue 98, acid violet 50, acid blue 59, acid violet 17, acid black 1 , acid blue 29, solvent violet 13, disperse violet 27 disperse violet 26, disperse violet 28, disperse violet 63, disperse violet 77 and mixtures thereof. Further Optional Ingredients

The compositions of the invention may contain one or more other ingredients. Such ingredients include further preservatives (e.g. bactericides), pH buffering agents, perfume carriers, hydrotropes, anti-redeposition agents, soil-release agents, polyelectrolytes, anti-shrinking agents, anti-wrinkle agents, anti-oxidants, sunscreens, anti-corrosion agents, drape imparting agents, anti-static agents, ironing aids, silicones, antifoams, colourants, pearlisers and/or opacifiers, natural oils/extracts, processing aids, eg electrolytes, hygiene agents, eg anti-bacterials and antifungals, thickeners and skin benefit agents.

The Fabric softening compositions may also comprise viscosity modifiers.

Suitable viscosity modifiers are disclosed, for example, in WO 02/08161 1 , US 2004/0214736, US 6827795, EP 0501714, US 2003/0104964, EP 0385749 and EP 331237.

Product Form

The compositions of the present invention are preferably rinse-added softening compositions.

The compositions have a pH ranging from about 2.5 to 6, preferably from about 2.5 to 4.5, most preferably about 2.5 to 2.8. The compositions of the invention may also contain pH modifiers such as hydrochloric acid or lactic acid.

A composition of the invention is preferably in liquid form. The composition may be a concentrate to be diluted in a solvent, including water, before use. The composition may also be a ready-to-use (in-use) composition. Preferably the composition is provided as a ready to use liquid comprising an aqueous phase. The aqueous phase may comprise water-soluble species, such as mineral salts or short chain (Ci_-4) alcohols. The composition is preferably for use in the rinse cycle of a home textile laundering operation, where, it may be added directly in an undiluted state to a washing machine, e.g. through a dispenser drawer or, for a top-loading washing machine, directly into the drum. Alternatively, it can be diluted prior to use. The compositions may also be used in a domestic hand-washing laundry operation. It is also possible for the compositions of the present invention to be used in industrial laundry operations, e.g. as a finishing agent for softening new clothes prior to sale to consumers. Preparation

Compositions of the invention can be prepared by any method suitable for preparing dispersed, emulsified systems. One method involves the forming of a molten premixture of the active materials in water at an elevated temperature, adding additional water to obtain the desired active concentration, and then cooling to ambient temperature. When desired, some minor ingredients such as electrolytes, colouring agents, etc. may be post-dosed. A second method involves the forming of the product by phase inversion of a water in hydrocarbon emulsion, wherein the cationic material is either part of the hydrocarbon phase or added as a separate predispersion. This method is advantageous, because this provides very finely divided hydrocarbon particles in the final product. In an alternative method the encapsulated phase change active may be post dosed in the form of an aqueous slurry. The capsules can be combined with the composition at any time during the preparation of the laundry treatment composition. The encapsulated phase change material and the encapsulated volatile benefit agent may be added at the same point in the preparation, or each at separate steps in the process. The capsules can be added to the composition comprising the unconfined volatile benefit agent or vice versa. For example, the capsules may be post dosed to a pre-made composition comprising the unconfined volatile benefit agent or may be combined with other ingredients such as water, during the preparation of the composition comprising the unconfined benefit agent.

Examples

Embodiments of the invention will now be illustrated by the following non-limiting examples. Further modifications will be apparent to the person skilled in the art.

Examples of the invention are represented by a number. Comparative examples are represented by a letter.

Unless otherwise stated, amounts of components are expressed as a percentage of the total weight of the composition. Example 1 :- Preparation and composition of Fabric Conditioner 1 , in accordance with the invention, and Comparative Examples A and B.

Conditioner 1 and Comparative Examples A and B were concentrated liquid fabric conditioners, comprising about 12 % of softening active.

A is an aqueous fabric conditioner, containing encapsulated perfume but no encapsulated phase change material.

B is an aqueous fabric conditioner, containing encapsulated phase change material but no perfume capsule comprising a hydrophilic polymer.

Encapsulated phase change material, Lurapret TX PMC 28, available from BASF was added during the making of the liquid formulations, to the water phase prior to the addition of the melt. Similarly, HydroSal 1 encapsulates, available from Salvona, and containing perfume as the volatile benefit agent were added to the water phase prior to the addition of the melt. Process for preparation of Conditioner 1 and Comparative Examples A and B:-

1 . The fabric softening active and the fatty alcohol were heated to about 65°C to form a melted premix.

2. The water was heated to about 50°C with stirring.

3. In samples 1 and B, Lurapret TX PMC 28 was added to the heated water phase.

4. The polymer was added to the water and mixed thoroughly.

5. Minor ingredients (preservative, sequestrant) were added.

6. If present, perfume encap slurry was then added with stirring.

7. Hydrochloric acid was added to the desired pH.

8. The melted premix was then combined with the water phase.

9. Any further minor ingredients and CaC^ were then added to the vessel.

10. The product was then cooled to 35°C.

1 1 . Perfume oil was then added to the cooled product with stirring.

Table 1 : Compositions of Conditioner 1 and Comparative Examples A and B

¹ Palm based soft TEA Quat, ex FXG

² ex Godrej

3 ex SNF

⁴ ex Salvona

5 ex BASF

6 ex IFF

⁷ Preservative, sequestrant, antifoam

Example 2:- Storage Stability of Conditioner 1 and Comparative Examples A and B Storage test

Samples were stored at 45°C for up to 12 weeks. Viscosity was measured as an indication of the storage stability over the storage period.

Viscosity was measured on a cup and bob viscometer; the viscosity being continuously measured under shear at 106s^"1 for 60 seconds, at 25°C. The results are given in Table 2 below. Table 2: Viscosities (at shear rate 106^s"1 and 25°C) of Conditioner 1 and

Connparative Examples A and B upon preparation (initial), and after storage at 45 °C for 1 , 4, 8 and 12 weeks.

It will be seen that fabric conditioner in accordance with the invention provided greatly improved storage viscostability over the storage period.

Claims

1 . A fabric conditioning composition, which comprises:

(i) an encapsulated phase change active, which undergoes a phase

change from solid to liquid, or from liquid to solid, having a phase change temperature of from 24 to 39°C;

(ii) a non-encapsulated volatile benefit agent;

(iv) an encapsulated volatile benefit agent comprising a capsule

2. A composition according to any preceding claim, wherein the cationic

softening agent is a quaternary ammonium compound.

3. A composition according to claim 2, wherein the quaternary ammonium

compound is an ester-linked triethanolamine (TEA) quaternary ammonium compound comprising a mixture of mono-, di- and tri-ester linked

components.

4. A composition according to claim 1 , wherein the nonionic softening agent is a sugar polyester.

5. A composition according to any preceding claim, wherein the volatile

benefit agent is selected from a perfume, insect repellent, aromatherapy oil, a sensate and an essential oil.

6. A composition according to claim 5, wherein the volatile benefit agent is a perfume.

7. A composition according to any preceding claim, wherein the volatile

benefit agent is present in an amount of from 0.01 to 10 % by weight, based on the total weight of the composition.

8. A composition according to any preceding claim, wherein the encapsulated phase change material is present in an amount of from 0.01 to 15 wt % by total weight of the composition.

9. A composition according to any preceding claim, wherein the phase change material has a phase transition temperature of from 26 to 30°C.

10. A composition according to any preceding claim, wherein the encapsulated phase change material has a particle size of from 10 nm to 1000 microns.

1 1 . A composition according to any preceding claim, wherein the phase change material is a hydrocarbon material comprising a linear or branched alkyl chain.

12. A composition according to any preceding claim, wherein the phase change material is selected from a mineral oil, a liquid paraffin and a cracked hydrocarbon.

A composition according to any preceding claim, wherein the phase change material is a mixture of mineral oil and petroleum jelly, wherein the weight ratio of mineral oil to petroleum jelly is chosen such that the TPTT of the mixture is in the range of from 26 to 39°C.

14. A composition according to any preceding claim, which is an aqueous fabric conditioning composition.

15. A process for treating fabric comprising the step of treating a fabric article with a composition as defined in any preceding claim.