WO2013026620A1

WO2013026620A1 - Encapsulated benefit agent

Info

Publication number: WO2013026620A1
Application number: PCT/EP2012/063728
Authority: WO
Inventors: Stuart Anthony Barnett; Robert Allan Hunter; Christopher Clarkson Jones; Craig Warren Jones; Xiaoyun Pan; Jinfang Wang
Original assignee: Unilever Plc; Unilever N.V.; Hindustan Unilever Limited
Priority date: 2011-08-25
Filing date: 2012-07-12
Publication date: 2013-02-28
Also published as: ZA201400527B; ES2555456T3; BR112014004266A2; EP2748295B1; EP2748295A1

Abstract

A liquid fabric conditioner composition comprising:- (a) a fabric conditioner base comprising a fabric conditioning active and having a pH of from 2.0 to 5.0; and (b) a particle comprising:- (b1) a capsule, which comprises:- (x) a core comprising a benefit agent; and (y) a shell; and (b2) a coating comprising a modified polyvinyl alcohol; wherein the modified polyvinyl alcohol comprises:- (i) a hydrophobic group, selected from an alkyl chain and an aryl chain having from 4 to 16 carbon atoms; and a hydrophilic group which is selected from an alkyl chain and an aryl chain, said hydrophilic group having from 4 to 16 carbon atoms and comprising an amine group selected from a primary, secondary and tertiary amine; and (iii) a mole ratio of hydrophobic groups to hydrophilic groups of from 1:0.5 to 1:10; and wherein the particle has a weight ratio of the capsule to the coating in the range of from 1:1 to 4:1; and the modified polyvinyl alcohol has a level of hydrophobic modification of from 2.0 to 15.0 mole %, with the proviso that at a weight ratio of capsule to coating of about 1:1, preferably from 1:1 to 1.25:1, the level of hydrophobic modification is from 2 to 10 mol %.

Description

ENCAPSULATED BENEFIT AGENT

Field of the Invention The present invention relates to encapsulated benefit agents, particularly one or more perfume components, and their use in the formulation of fabric conditioning compositions. Compositions containing particles according to the invention provide superior viscostability and compatibility benefits as well as perfume longevity.

Background and Prior Art

Perfume is one of the most expensive components in laundry products and its fragrance is one of the most important attributes and reasons for purchase across laundry brands. A known technology for the provision of long-lasting perfume performance is the use of melamine-formaldehyde perfume capsules. The capsules have a high loading amount of perfume and are able to release perfume upon rubbing. Our prior patent application WO2004/031271 discloses modified PVOH films with a preferred average thickness of from 50 to 500 microns, used to make capsules. The capsules preferably contain from 0.5 ml to 100 ml of a material such as a laundry conditioner. Our co-pending application, WO2009/103576, relates to a particle having a diameter of less than 2 mm comprising a benefit agent, such as a perfume, and a water soluble polymeric film-forming material modified with a charged derivatising group; whereby the film remains substantially intact in the presence of a surfactant and disintegrates when the concentration of the surfactant reduces sufficiently, thereby releasing the benefit agent. Our co-pending application, WO2009/103615, relates to a fabric conditioning composition of pH of less than 7, comprising a quaternary ammonium conditioning agent, an encapsulated benefit agent, which is made, at least in part, from a formaldehyde-based polymer, and at least in part from a non-formaldehyde based polymer, and a formaldehyde scavenger.

However, we have identified a problem when the capsule is added to liquid fabric conditioner formulations. The formulations exhibit poor stability, particularly upon storage, which is manifested as a marked increase in viscosity and the

formulations becoming hard to pour. This problem is exacerbated with storage longevity and under temperature extremes and variations.

We have now found that perfume encaps with a coating technology based upon modified PVOH (mPVOH) can solve the problem. The coated capsules have superior compatibility with fabric conditioners so that the viscosity of the formulation is maintained at an appropriate level. Thus perfume longevity can be achieved without the need to sacrifice the quality of the product itself.

Statement of the Invention

In a first aspect of the present invention there is provided a liquid fabric

conditioner composition comprising:-

(a) a fabric conditioner base comprising a fabric conditioning active and having a pH of from 2.0 to 5.0; and

(b) a particle comprising:-

(b1 ) a capsule, which comprises:- (x) a core comprising a benefit agent; and (y) a shell; and

(b2) a coating comprising a modified polyvinyl alcohol; wherein the modified polyvinyl alcohol comprises:-

(i) a hydrophobic group, selected from an alkyl chain and an aryl chain, having from 4 to 16 carbon atoms; and

(ii) a hydrophilic group which is selected from an alkyl chain and an aryl chain, said hydrophilic group having from 4 to 16 carbon atoms and comprising an amine group selected from a primary, secondary and tertiary amine; and

(iii) a mole ratio of hydrophobic groups to hydrophilic groups of from 1 :0.5 to 1 :10; and wherein the particle has a weight ratio of the capsule to the coating in the range of from 1 :1 to 4:1 ; and the modified polyvinyl alcohol has a level of hydrophobic modification of from 2.0 to 15.0 mole %, with the proviso that at a weight ratio of capsule to coating of about 1 :1 , preferably from 1 :1 to 1 .25:1 , the level of hydrophobic modification is from 2 to 10 mol %.

In a second aspect of the invention, there is provided a method of improving the viscostability of a fabric conditioner, wherein the fabric conditioner comprises a particle comprising a core comprising a benefit agent and a shell; comprising the step of providing the particle with a coating comprising a modified polyvinyl alcohol as defined in the first aspect of the invention, and wherein the particle has a weight ratio of the capsule to the coating in the range of from 1 :1 to 4:1 ; and the modified polyvinyl alcohol has a level of hydrophobic modification of from 2.0 to 15.0 mole %, with the proviso that at a weight ratio of capsule to coating of about 1 :1 , the level of hydrophobic modification is from 2 to 10 mol %. In a third aspect, there is provided a process for conditioning fabrics comprising the step of contacting a composition as defined by the first aspect of the invention.

Detailed Description of the Invention

In order that the invention can be further understood it is described below with particular reference to the preferred features of specific elements of the invention.

The Fabric Conditioning Base

The fabric conditioning base comprises a fabric conditioning active and has a pH of from 2.0 to 5.0, preferably from 2.5 to 4.5, most preferably from 2.5 to 4.0.

The Fabric Conditioning Active

The fabric conditioning active (also referred to herein as the fabric softening active) may be cationic or non-ionic.

Fabric conditioning compositions of the invention may be dilute or concentrated. Products of the invention comprise from 2 to about 50 % of fabric conditioning active. 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 8.5 to about 50 %, more preferably from 8 to 25 % by weight 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 preferred hardened type of active has a typical mono:di:tri ester distribution in the range of from 12 to 25 mono: from 55 to 65 di: from 15 to 27 tri. A soft TEA quat may have a typical mono:di:tri ester distribution of from 25 to 45 %, preferably from 30 to 40 % mono: from 45 to 60 %, preferably from 50 to 55 % di: and from 5 to 25 %, preferably from 10 to 15 % tri; for example 40:60:10.

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, C2_-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)

I 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.

Iodine 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. The Particle

The particle comprises a capsule and a coating. The capsule comprises a core comprising a benefit agent; and a shell; and the coating comprises a modified polyvinyl alcohol.

The particle preferably has a particle size of from 0.2 to 50 microns, more preferably from 2 to 50 microns. The Capsule

The capsule (which is also referred to herein as a "microcapsule") comprises a core and a shell. The shell comprises a suitable encapsulating material, examples of which include aminoplasts, proteins, polyurethanes, polyacrylates, polymethacrylates, polysaccharides and gums.

Preferred encapsulating polymers include those formed from melamine formaldehyde or urea formaldehyde condensates, as well as similar types of aminoplasts. Most preferably the shell comprises melamine formaldehyde.

Additionally, microcapsules made via the simple or complex coacervation of gelatin may also be used. Microcapsules having shells comprised of

polyurethane, polyamide, polyolefin, polysaccaharide, protein, silicone, lipid, gums, polyacrylate, polystyrene, and polyesters or combinations of these materials are also possible.

A representative process used for aminoplast encapsulation is disclosed in U.S. Patent No. 3,516,941 though it is recognized that many variations with regard to materials and process steps are possible. A representative process used for gelatin encapsulation is disclosed in U.S. Patent No, 2,800,457 though it is recognized that many variations with regard to materials and process steps are possible. Both of these processes are discussed in the context of fragrance encapsulation for use in consumer products in U.S. Patent Nos. 4,145,184 and 5,1 12,688 respectively.

Encapsulation can provide pore vacancies or interstitial openings depending on the encapsulation techniques employed.

Fragrance capsules known in the art and suitable for use in the present invention comprise a shell comprising a three-dimensional cross-linked network of an aminoplast resin, more specifically a substituted or un-substituted acrylic acid polymer or co-polymer cross-linked with a urea-formaldehyde pre-condensate or a melamine-formaldehyde pre-condensate.

Microcapsule formation using mechanisms similar to the foregoing mechanism, using (i) melamine-formaldehyde or urea-formaldehyde pre-condensates and (ii) polymers containing substituted vinyl monomeric units having proton-donating functional group moieties (e.g. sulfonic acid groups or carboxylic acid anhydride groups) bonded thereto is disclosed in 44068162 USB U.S. Patent 4,406,816 (2- acrylamido-2-methyl-propane sulfonic acid groups), 2062570 GBA UK published Patent Application GB 2,062,570 A (styrene sulfonic acid groups) and 2006709 GBA UK published Patent Application GB 2,006,709 A (carboxylic acid anhydride groups).

For liquid compositions, the capsules may be used in the form of a slurry, which preferably comprises about 40% solids. The amount of such a 40% capsule slurry to be used in a composition is up to 10 %, preferably from 0.1 to 5 %, more preferably from 0.5 to 2 % by weight of the total composition. Particle size and average diameter of the capsules can vary from about 10 nanometers to about 1000 microns, preferably from about 50 nanometers to about 100 microns, more preferably from about 2 to about 40 microns, even more preferably from about 4 to 15 microns. A particularly preferred range is from about 5 to 10 microns, for example 6 to 7 microns. The capsule distribution can be narrow, broad or multimodal. Multimodal distributions may be composed of different types of capsule chemistries.

The Benefit Agent

In the compositions and methods described herein, benefit agents are

hydrophobic materials that can provide a beneficial effect to the substrate fabric.

The preferred benefit agents according to the present invention have a ClogP greater than 0.5.

Preferred benefit agents include perfumes, lubricants any other oily materials. Particularly preferred benefit agents include, but not limited to, the following: a) silicone oils, resins, and modifications thereof such as linear and cyclic polydimethylsiloxanes, amino-modified, allcyl, aryl, and alkylaryl silicone oils, which preferably have a viscosity of greater than 50,000 est; b) perfume components including fragrance, perfumery, and essential oils and resins, and pro-fragrance materials; c) organic sunscreen actives, for example, octylmethoxy cinnamate; d) antimicrobial agents, for example, 2-hydroxy-4,2,4- trichlorodiphenylether; ester solvents; for example, isopropyl myristate; lipids and lipid like substance, for example, cholesterol hydrocarbons such as paraffins, petrolatum, and mineral oil fish and vegetable oils hydrophobic plant extracts waxes; pigments including inorganic compounds with hydrophobically- modified surface and/ or dispersed in an oil or a hydrophobic liquid, and; sugar-esters, such as sucrose polyester (SPE).

The most preferred benefit agents are perfume components. Perfume

components include both odiferous materials and pro-fragrance materials.

Perfumes

The perfume is typically present in an amount of from 10-85% by total weight of the particle, preferably from 20 to 75% by total weight of the particle. The perfume suitably has a molecular weight of from 50 to 500.

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, flavoring, and/or aromatizing consumer products, i.e., of imparting an odor and/or a flavor or taste to a consumer product traditionally perfumed or flavored, or of modifying the odor 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.

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.

It is also advantageous to encapsulate perfume components which have a low LogP (i.e. those which will be partitioned into water), preferably with a LogP of less than 3.0. These materials, of relatively low boiling point and relatively low LogP 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.

It is commonplace for a plurality of perfume components to be present in a formulation. In the encapsulates 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 present in the encapsulated perfume.

Another group of perfumes with which the present invention can be applied are the so-called 'aromatherapy' materials. These include many components also used in perfumery, including components of essential oils such as Clary Sage, Eucalyptus, Geranium, Lavender, Mace Extract, Neroli, Nutmeg, Spearmint, Sweet Violet Leaf and Valerian. By means of the present invention these materials can be transferred to textile articles that will be worn or otherwise come into contact with the human body (such as handkerchiefs and bed linen). The capsules for use in the invention can also comprise a carrier oil in the core. The oil must be compatible with the benefit agent, which is preferably a perfume. The carrier oils are hydrophobic materials that are miscible in the perfume materials used in the present invention. Suitable oils are those having reasonable affinity for the fragrance chemicals. Suitable materials include, but are not limited to triglyceride oil, mono and diglycerides, mineral oil, silicone oil, diethyl phthalate, polyalpha olefins, castor oil and isopropyl myristate. Preferably, the oil is a triglyceride oil, most preferably a capric/caprylic triglyceride oil.

The capsules can also comprise a filler. Suitable fillers can be inorganic, organic or a mixture of both including but not restricted to, for example, micro-crystalline celluloses, long-chain fatty acids, silicas both precipitated and fumed, clays natural and synthetic, nano-metaols, carbon-black, pigments, zinc sulphide, zince pyrythirone, barium sulphate, aluminium oxides, ligin, lignin sulphates, calcium carbonate and talcs.

The Coating

The coating comprises a modified polyvinyl alcohol. The Modified Polyvinyl Alcohol

The modified polyvinyl alcohol (m-PVOH) is derived from a parent polyvinyl alcohol (also referred to herein as the starting polyvinyl alcohol, and designated PVOH). An example of a suitable PVOH is the Mowiol range (Trade Mark), ex Kuraray Specialities Europe GmBh.

The parent polyvinyl alcohol preferably has a molecular weight of from 1 ,000 to 300,000, preferably from 2,000 to 100,000, most preferably from 2,000 to 75,000.

The modified PVOH comprises:

(a) a hydrophobic group, selected from an alkyl and an aryl chain, having from 4 to 16, preferably from 4 to 8 carbon atoms; preferably the hydrophobic group is an alkyl chain; and

(b) a hydrophilic group which is selected from an alkyl and an aryl chain, said hydrophilic group having from 4 to 16, preferably from 4 to 8 carbon atoms and comprising an amine group selected from a primary, secondary and tertiary amine, preferably a primary amine. The preferred hydrophilic group is an alkyl amine.

In the context of this invention, alkyl is intended to cover saturated and

unsaturated functional groups, preferably saturated.

The mole ratio of hydrophobic groups to hydrophilic groups is from 1 :0.5 to 1 :10, more preferably from 1 :1 .5 to 1 :7 and most preferably from 1 :2 to 1 :7, based on the extent of modification of the OH groups on the starting polyvinyl alcohol.

Hydrophobic Group

The hydrophobic group is attached to the starting polyvinyl alcohol by reaction of the starting PVOH with a suitable parent material (said parent material is also referred to herein as a Type HB parent material). The hydrophobic group is preferably present in the polyvinyl alcohol at a level of from 2.0 mol % to 15 mol %, preferably from 2.0 mol % to 14 mol %, most preferably from 2.0 to 13 mol %. The mole % is based on the number of OH groups present in the starting (unmodified) polyvinyl alcohol.

Preferably, the Type HB parent material is selected from aldehydes, acetals, ketals, esters, fluorinated organic compounds, ethers, alkanes, alkenes and aromatic compounds, which also contain the desired hydrophobic group in accordance with the invention, most preferably aldehydes and acteals.

Hydrophilic Group

The hydrophilic group is attached to the starting polyvinyl alcohol by reaction of the starting PVOH with a suitable parent material (said parent material is also referred to herein as a Type HL parent material).

Preferably, the Type HL parent material is selected from a material having a ClogP of from 0.5 to 6, more preferably from 1 to 6 and most preferably from 2 to 6, e.g. from 3 to 5.

In the context of the present invention, ClogP is calculated using the methods given in: Ghose, Viswanadhan and Wendoloski, Prediction of Hydrophobic (Lipophilic) Properties of Small Organic Molecules Using Fragment Methods: An Analysis of AlogP and CLogP Methods. J. Phys. Chem. A, 1998, 102, 3762-3772. This method is implemented within the software: "Pipeline Pilot", available from SciTegic, a wholly owned subsidiary of Accelrys, Inc.

The hydrophilic group is preferably present in the polyvinyl alcohol at a level of from at least 0.1 mol % to 20 mol %, preferably from 5 mol % to 18 mol %, most preferably from 8 mol % to 15 mol %. The mole % is based on the number of OH groups present in the starting (unmodified) polyvinyl alcohol.

Preferred hydrophilic groups can be derived from Type HL parent materials selected from aldehydes, acetals, ketals, esters, fluorinated organic compounds, ethers, alkanes, alkenes, aromatic compounds, which also contain the desired hydrophilic group in accordance with the invention.

Especially preferred Type HL parent groups are aldehydes such as: amino- butyraldehyde, amino-octyl aldehyde, amino-dodecyl aldehyde, amino-2-ethyl hexanal, amino-cyclohexane carboxy-aldehyde, amino-citral, amino- propionaldehyde, amino(2-methoxyethoxy) acetaldehyde, amino-dimethylacetal and amino-benzaldehyde, although it will be readily apparent to the person skilled in the art that other suitable parent groups having the requisite ClogP are also suitable for use in the invention.

A particularly preferred mPVOH for use in the present invention can be represented by the following formula:

Wherein R is the hydrophobic group and R' is the hydrophilic (amine) group. The hydrophilic group (R') is preferably derived from one or more of:

4-aminobutyraldehyde dimethyl acetal,

aminoacetaldehyde diethyl acetal,

anilinoacetaldehyde diethyl acetal,

Ν,Ν-dimethylformamide dimethyl acetal,

N-benzylaminoacetaldehyde diethyl acetal,

aminoacetaldehyde dimethyl acetal,

pyridine-4-carboxaldehyde,

1 -methylpyrrole-2-carboxaldehyde,

pyridine-2-carboxaldehyde,

4-dimethylaminobenzaldehyde,

4-diethylaminobenzaldehyde,

pyrrole-2-carboxaldehyde,

2-chlorobenzaldehyde thiosemicarbazone,

pyridine-3-carboxaldehyde,

indole-3-carboxaldehyde,

3,5-dinitrosalicylaldehyde,

2-phenylindole-3-carboxaldehyde,

4-dimethylamino-cinnamaldehyde,

4- dimethylaminobutyraldehyde diethyl acetal,

5- chloroindole-3-carboxaldehyde,

indole-5-carboxaldehyde,

1 - methylbenzimidazole-2-carboxaldehyde,

2-(2,2,2-trimethylacetamido)pyridine-3-carboxaldehyde,

2- amino-5-iodopyridine-3-carboxaldehyde,

3- aminopyridine-4-carboxaldehyde,

4- aminopyridine-3-carboxaldehyde,

4-amino-5-iodopyridine-3-carboxaldehyde,

2-chloro-4-iodopyridine-3-carboxaldehyde, 5- bromo-2-methoxypyridine-3-carboxaldehyde,

2-methoxypyridine-3-carboxaldehyde,

2-ethoxypyridine-3-carboxaldehyde,

2-isopropoxypyridine-3-carboxaldehyde,

2-(cyclopropylmethoxy) pyridine-3-carboxaldehyde,

2-chloropyridine-4-carboxaldehyde,

2-n-propoxypyridine-3-carboxaldehyde,

2-cyclopentyloxypyridine-3-carboxaldehyde,

2- (2,2,2-trifluoroethoxy)pyridine-3-carboxaldehyde,

6-(1 -pyrrolidino)pyridine-3-carboxaldehyde,

6- (1 -piperidino)pyridine-3-carboxaldehyde,

6-cyclopentyl-oxypyridine-3-carboxaldehyde,

6-cyclohexyloxypyridine-3-carboxaldehyde,

5-bromopyridine-2-carboxaldehyde,

2-(3-dimethylanninopropoxy)benzaldehyde,

1 ,3,5-trimethyl-1 H-pyrazole-4-carbox-aldehyde,

5-benzyloxy-6-azaindole-3-carboxaldehyde,

3- (p-tolyl)-1 H-pyrazole-4-carboxaldehyde,

N-methylaminoacetaldehyde dimethyl acetal, dimethylaminoacetaldehyde diethyl acetal,

4- Diethylaminosalicylaldehyde,

4-aminobutyraldehyde diethyl acetal,

2-amino-5-chlorobenzaldehyde,

2-bromopyridine-4-carboxaldehyde,

2-aminopyridine-3-carboxaldehyde, and

4-dimethylaminobenzaldehyde.

There will be some acetate groups present in the modified PVOH, which arise from the starting PVOH material. These are typically present in an amount of from 1 to 12 mol %, preferably from 1 to 2 mol %, based on the total amount of OH groups present in the starting PVOH material.

The hydrophobic group (R) is preferably derived one or more of:

butyraldehyde, octyl aldehyde, dodecyl aldehyde, 2-ethyl hexanal, cyclohexane carboxy-aldehyde, citral, propionaldehyde, (2-methoxyethoxy) acetaldehyde dimethylacetal, and benzaldehyde.

The particle has a weight ratio of the capsule to the coating in the range of from 1 :1 to 4:1 , preferably from 1 :1 to 3:1 . In another preferred embodiment, the weight ratio of capsule to coating is in the range of from 2:1 to 4:1 .

The modified polyvinyl alcohol has a level of hydrophobic modification of from 2.0 to 15.0 mol % with the proviso that at a weight ratio of capsule to coating of about 1 :1 , preferably from 1 :1 to 1 .25:1 , the level of hydrophobic modification is from 2 to 10 mol %.

Optional modified PVOH components: It can be advantageous for the modified PVOH to be provided as a cross-linked polymeric structure. The level of cross-linking should be kept low so as to avoid the formation of an insoluble material.

Particularly suitable cross-linking agents include formaldehyde; polyesters;

epoxides; amidoamines; anhydrides; phenols; isocyanates; vinyl esters;

urethanes; polyimides; arylics; bis(methacrylkoxypropyl) tetramethylsiloxane (styrenes, methylnnethacrylates); n-diazopyruvates; phenyboronic acids; cis-platin; divinylbenzene; polyamides; dialdehydes; triallyl cyanurates; N-(-2- ethanesulfonylethyl)pyridinium halides; tetraalkyltitanates; mixtures of titanates and borates or zirconates; polyvalent ions of Cr, Zr, Ti; dialdehydes, diketones; alcohol complexes of organotitanates, zircoates and borates and copper (II) complexes. For PVOH-based films, the preferred cross-linking agent is a metalloid oxide such as borate, tellurate, arsenate, and precursors thereof. Other known cross-linkers include the vanadyl ion, titanium ion in the plus three valence state, or a permanganate ion (disclosed in patent US 3,518,242). Alternative cross-linkers are given in the book: Polyvinylalcohol - Properties and applications, Chapter 9 by C.A. Finch (John Wiley & Sons, New York, 1973).

Manufacturing Process:

The modification of the polymer can be accomplished by a range of known processes. For example in the manufacture of modified PVOH, an acidic solution of PVOH (preferably formed at a temperature of above 80 degrees Celsius) is reacted at around 70 degrees Celsius with an aldehyde/acetal (preferably added dropwise). After the addition of the components the reaction is allowed to proceed for several hours at STP.

The modified PVOH produced as outlined above of the present invention can be added to the encapsulate slurry prior to addition to the final product, or it can be added to the formulation containing the encapsulates. The former process is preferred.

Other 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 for use in 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 La u rex™ CS, ex Albright and Wilson).

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 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 nonionic 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.

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:

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 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. Perfume

The compositions of the present invention may comprise one or more perfumes if desired. The perfume is preferably present in an amount 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.

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 (i.e. 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.

Another group of perfumes with which the present invention can be applied are the so-called 'aromatherapy' materials. These include many components also used in perfumery, including components of essential oils such as Clary Sage, Eucalyptus, Geranium, Lavender, Mace Extract, Neroli, Nutmeg, Spearmint, Sweet Violet Leaf and Valerian.

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, 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, e.g. electrolytes, hygiene agents, e.g. anti-bacterials and antifungals, thickeners and skin benefit agents.

Product Form

The compositions are liquids.

The liquid compositions have a pH ranging from 2.0 to 5.0, preferably from 2.5 to 4.5, most preferably from 2.5 to 4.0. The compositions of the invention may also contain pH modifiers such as hydrochloric acid or lactic acid.

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 compositions of the present invention are preferably rinse-added softening compositions suitable for use in a laundry process. 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 of the Compositions of the Invention The compositions of the invention may typically be made by combining a melt comprising the fabric softening active and optional co-softener with an aqueous phase. Further components may be combined with the water phase, or may be post dosed into the composition after combination of the melt and water phase. In order that the invention may be further understood and carried forth into practice, the invention will now be illustrated by the following non-limiting examples. Further modification within the scope of the present invention will be apparent to the person skilled in the art. Examples

Example 1 : Materials and Methodologies

The reagents used in the experimental procedures described in these examples are listed in Table 1 and used as received without further purification. Table 1 : Reagents used as described in the examples.

General methodology for preparation of modified PVOH polymer

PVOH (Mowiol 10-98; 2 g) and deionised water (20 mL) were introduced to a glass reactor vessel. The mixture was then warmed to 90°C with stirring until the polymer dissolved completely. Thereafter, the solution was cooled to 70°C and HCI catalyst (0.2 mL of a 37% solution in water) was added to the stirred solution. A dilute solution of aldehyde/acetal in deionised water (about 7 %, neutral pH) was prepared and the required amount of the solution was added dropwise slowly to the reactor over about 0.5 hour. After the addition was complete, the reaction mixture was stirred at 70°C for 5 hours and then at room temperature for additional 20 hours. NaOH solution (1 M) (2 ml_) was then added to the reaction mixture to neutralize the pH of the product solution. The resulting product was the modified PVOH.

¹H NMR spectroscopy characterization

Modified PVOH (1 .0 ml_) was taken out from the reactor after the completion of the reaction and freeze-dried. Samples for ¹H NMR spectroscopy characterization were prepared by dissolving polymer powder in d6-DMSO. The spectrum was recorded by Bruker 400 MHz spectrometer.

Example 2: Preparation of modified PVOH coated Melamine Formaldehyde based capsules (S1 - S2)

Using the general methodology for the preparation of modified PVOH described above, six modified PVOH materials (S1 -S6) were prepared, with various types and degrees of hydrophilic and hydrophobic modification. The modification details of the six mPVOH samples are shown in Table 2.

Table 2: Sample information for modified PVOH samples

[1 ] Hydrophobic modification reagent is butyraldehyde;

[2] Hydrophobic modification reagent is hexanal;

[3] Hydrophobic modification reagent is octanal;

[4] Hydrophilic modification reagent is 4-amino-butyraldehyde diethyl acetal.

Example 3: Preparation of fabric conditioner formulations comprising modified PVOH coated capsules (designated E1 to E6 at a weight ratio of capsule to coating of 1 :1 and E1' to E6' at a ratio of 2:1); and preparation of comparative examples (designated A at a ratio of 1 :1 ; A' at a ratio of 2:1 and E1" to E6" and A" at a ratio of 5:1 : and B)

Method of Preparation

Capsule slurry (0.72 g), a 10 % aqueous solution of modified PVOH (0.13 g) (chosen from S1 -S6 as prepared above) and free water (1 .15 g) were mixed together and stirred at 250 rpm for 10 min to make an encapsulation slurry solution. The final weight ratio of modified PVOH to capsule was 1 :1 . Then, the encapsulation slurry solution was added slowly into the fabric conditioner base referred to in Table 1 (38 g) under mechanical stirring at 250 rpm and stirred for another 10 min after addition completed. The formulation sample was then incubated at 40°C for 2 days before measurement. Two further preparations were made in this way, wherein the weight ratio of modified PVOH to capsule was 2:1 and 5:1 respectively.

Samples Prepared In this way, eighteen fabric conditioner formulations were prepared at 3 different weight ratios of capsule to coating (designated E1 to E6 at a ratio of 1 : 1 ; E 1 ' to E6' at a ratio of 2:1 , in accordance with the invention, and comparative examples E1 " to E6" at a ratio of 5:1 ), , which contained the modified PVOH materials S1 -S6 prepared above. Comparative examples (designated A at a ratio of 1 :1 ; A' at a ratio of 2:1 and A" at a ratio of 5:1 ) were also prepared, where A, A' and A" contained capsules coated only with the non-modified starting PVOH material and B contained capsules with no coating. Finally, a control C consisted of the fabric conditioner base alone. The formulations are summarised in Table 3.

Table 3: Sample information for modified PVOH coated capsules

E1 - E6 and E1 ' - E6' are in accordance with the invention.

Example 4: Viscosity properties of fabric conditioners E1 -E6 & E1'-E6', E1 ; comparative examples E1"-E6", A, A', A" and B; and control C

The viscosities of fabric conditioner formulations were evaluated using a rheometer (Physica MCR501 , Anton Paar). The main parameters were as follows: Waiting time before measurement was 180s, shear rate was from

0.1 -200 s^"1 and viscosity data was acquired at 2, 20 and 106 s^~1.

The viscosity results are shown in Tables 4 to 6 as the change in viscosity after storage at 40°C for 2 days. Table 4: Viscosity change of fabric conditioners E1 -E6 & EV-E6'; comparative examples ΕΓ-Ε6", A, A', A" and B; and control C after 2 days storage 40°C.

Fabric particle :coat Viscosity at different shear rate (xlO^)

Lower viscosities are desirable and are associated with positive attributes such as good pourability.

It will be seen that the viscosity of fabric conditioner formulations increased (about 30-60%) after addition of the capsule. It was also found that if capsules were coated with a modified PVOH material in accordance with the invention, before being added to formulation, the viscosity in most cases was lower than that with the unmodified capsule. The results indicate that coating the capsule with modified PVOH is an efficient way to reduce viscosity change in fabric conditioner formulations.

Claims

CLAIMS . A liquid fabric conditioner composition comprising:-

(a) a fabric conditioner base comprising a fabric conditioning active and

having a pH of from 2.0 to 5.0; and

(b) a particle comprising:-

(b1 ) a capsule, which comprises:-

(x) a core comprising a benefit agent; and

(y) a shell; and

(iii) a mole ratio of hydrophobic groups to hydrophilic groups of from

1 :0.5 to 1 :10; and wherein the particle has a weight ratio of the capsule to the coating in the range of from 1 :1 to 4:1 ; and the modified polyvinyl alcohol has a level of hydrophobic modification of from 2.0 to 15.0 mole %, with the proviso that at a weight ratio of capsule to coating of about 1 :1 the level of hydrophobic modification is from 2 to 10 mol %.

A fabric conditioner composition as claimed in claim 1 , wherein the capsule shell comprises melamine formaldehyde.

A fabric conditioner composition as claimed in claim 1 or claim 2, wherein the benefit agent is a perfume.

A fabric conditioner composition as claimed in any preceding claim, wherein the fabric conditioning active is a quaternary ammonium compound.

A fabric conditioner composition as claimed in claim 4, wherein the quaternary ammonium compound is an ester-linked compound comprising a distribution of monoester, diester and triester compounds.

A fabric conditioner composition as claimed in claim 5, wherein the quaternary ammonium compound is an ester-linked triethanolamine quaternary ammonium compound.

A fabric conditioner composition as claimed in any preceding claim, wherein the fabric conditioning active is present in an amount of from 2 to 50 wt % by weight of the total composition.

A fabric conditioner composition as claimed in any preceding claim, wherein the weight ratio of the capsule to the coating is from 1 :1 to 3:1 , by weight of the particle.

A fabric conditioner composition as claimed in any one of claims 1 to 7, wherein the weight ratio of capsule to coating is from 2:1 to 4:1 .

A fabric conditioner composition as claimed in any preceding claim, wherein the particle has a particle size of from 0.2 to 50 microns, preferably from 2 to 50 microns.

A fabric conditioner composition as claimed in any preceding claim, wherein the level of hydrophobic modification is from 2.0 to

13.0 mole %, with the proviso that at a weight ratio of capsule to coating of about 1 :1 , the level of hydrophobic modification is from 2 to 10 mol %.

A fabric conditioner composition according to any preceding claim wherein the hydrophobic group is derived from a parent material, which is selected from the group consisting of aldehydes, acetals, ketals, esters, fluorinated organic compounds, ethers, alkanes, alkenes and aromatic compounds.

A fabric conditioner composition according to claim 12 wherein the hydrophobic group is derived from one or more of the group consisting of butyraldehyde, octyl aldehyde, dodecyl aldehyde, 2-ethyl hexanal, cyclohexane carboxy-aldehyde, citral, propionaldehyde, (2-methoxyethoxy) acetaldehyde dimethylacetal, and benzaldehyde.

14. A fabric conditioner composition according to any preceding claim wherein the modified polyvinyl alcohol is derived from polyvinyl alcohol with a molecular weight of from 1 ,000 to 300,000.

15. A fabric conditioner composition according to any preceding claim wherein the hydrophilic group is derived from a parent material having a ClogP of from 0.5 to 6.0.

16. A method of improving the viscostability of a fabric conditioner, wherein the fabric conditioner comprises a particle comprising a core comprising a benefit agent and a shell; comprising the step of providing the particle with a coating comprising a modified polyvinyl alcohol; wherein the modified polyvinyl alcohol comprises:-

(iii) a mole ratio of hydrophobic groups to hydrophilic groups of from 1 :0.5 to 1 :10; and wherein the particle has a weight ratio of the capsule to the coating in the range of from 1 :1 to 4:1 ; and the modified polyvinyl alcohol has a level of hydrophobic modification of from 2.0 to 15.0 mole %, with the proviso that at a weight ratio of capsule to coating of about 1 :1 , the level of hydrophobic modification is from 2 to 10 mol %.

17. A process for conditioning fabrics comprising the step of contacting a

composition as defined by any of claims 1 -15 with fabric.

18. A process as claimed in claim 17, comprising the steps of contacting a

composition as defined by any of claims 1 -15 with fabric in a rinse liquor and subsequently rinsing the fabrics.