EP2486118A1

EP2486118A1 - Fabric conditioners

Info

Publication number: EP2486118A1
Application number: EP10752341A
Authority: EP
Inventors: Christopher Boardman; Lesley Ebbrell; David Andrew Ross Jones
Original assignee: Unilever PLC; Unilever NV
Current assignee: Unilever PLC; Unilever NV
Priority date: 2009-10-07
Filing date: 2010-09-07
Publication date: 2012-08-15
Anticipated expiration: 2030-09-07
Also published as: EP2486118B1; AR078523A1; CN102712876B; CN102712876A; ZA201202104B; PH12012500657A1; ES2531835T3; BR112012007756A2; WO2011042275A1

Abstract

Use of a metal oxide as an ingredient in a fabric conditioner composition enables the fabrics treated with the composition to deliver a cool feel benefit to the wearer, wherein the fabric conditioner composition comprises a softening active and the metal oxide has a particle size in the range of from 1 to 400 nm, and is present in an amount of from 2.5 to 40 wt %, based on the weight of the total composition.

Description

FABRIC CONDITIONERS

Technical Field The present invention relates to the use of fabric treatment compositions containing white metal oxide materials to achieve cool feel to the wearer of fabrics treated therewith.

Background and Prior Art

Fabrics and fabric articles such as clothes can absorb significant amounts of heat, particularly on hot days and in hot climates, contributing to feelings of heat and discomfort for the wearer. Laundry treatment compositions containing metal oxides are known, providing a variety of benefits.

WO2008/058831 (Hindustan Unilever Ltd) discloses fabric softening compositions comprising a fabric softening compound and from 5 to 50 wt % of a material capable of changing its hydrophobic/hydrophilic properties, such as zinc oxide and titanium oxide, in response to an activation step, such as exposure to UV light. The transport of water through the fabric is thereby increased, thus leading to drier feel. DE10159000 A1 (Henkel KGaA) discloses softener compositions comprising polyalkylene glycol diesters for improved fabric wettability, an optional further softening material and an optional UV absorber, which may be zinc oxide or titanium oxide, to improve the light-resistance of fibres and/or of other ingredients in the formulation. DE102004 020015 A1 (Henkel KGaA) discloses textile care compositions comprising cellulose ether quats to reduce fluffing, pilling and creasing, an optional further softening material and an optional UV absorber, which may be zinc oxide or titanium oxide, to improve the light stability of the fibres and/or other ingredients in the composition.

XP002474825 & JP1 1061652 (JSR Kabushiki Kaisha) disclose an industrial coating for a fibre comprising a polyorganosiloxane and photocatalytically active inorganic particles to confer weather resistance, stain resistance, mildew proofing and antibacterial property to fibres.

We have now found that by treating a fabric with a composition comprising a white metal oxide material, the wearer feels cooler. This cool feel is especially desirable on sunny and hot days.

Statement of the Invention

In a first aspect of the invention there is provided the use of a white metal oxide as an ingredient in a rinse added aqueous fabric conditioner composition to enable the fabric conditioner composition to render fabrics treated with the composition capable of delivering a cool feel benefit to the wearer of the treated fabric, wherein the fabric conditioner composition comprises a softening active and the metal oxide is present in an amount of from 2.5 to 40 wt %, based on the weight of the total composition. Detailed Description of the Invention

The metal oxide material Any white metal oxide may be used, for example aluminium oxide, zinc oxide and titanium oxide. Mixtures of metal oxides and/or mixed oxides may be used, for example, a mixture of zinc oxide and titanium oxide.

Preferably the white metal oxide is a transition metal oxide such as oxides of Scandium (III), Titanium (IV), Zinc (II), Yttrium (III), Zirconium (IV), Niobium (V), Lanthanum (III), Hafnium (IV), Tantalum (V) - oxidation states are shown in parentheses. Hafnium (IV) Oxide and Zinc (ll)Oxide are preferred.

The metal oxide is preferably used in the form of a fine dispersion in a solvent, which is preferably water. The metal oxide is preferably added to the fabric conditioner base in the form of a nano dispersion, wherein the particles of metal oxide have sub-micron particle size.

The average particle size of the metal oxide is preferably less than 1 micron and is preferably in the range of from 1 to 400 nm, more preferably from 20 to 300 nm, most preferably from 60 to 250 nm. A suitable method for measuring the average particle size is BET (nitrogen gas adsorption), which is used to determine the specific surface area (square meters per gram), and converts this to an Average Particle Diameter (APD). See for example, Particle Size Characterization of Ultrafine Tungsten Powder, LIAO JIQIAO; HUANG BAIYUN; International Journal of Refractory Metals & Hard Materials, ISSN 0958-061 1 ,

2001 , vol. 19, n°2, pp. 89-98. The metal oxide is present in an amount of from 2.5 to 40 wt %, preferably from 4 to 15 wt % and most preferably from 5 to 12wt %, based on the total weight of the composition. A particularly preferred amount is 10 wt %. The Fabric Conditioning Agent

The conditioning agents (also referred to herein as fabric softening actives) may be cationic or non-ionic. The fabric conditioning compositions for use in the invention may be dilute or concentrated. Dilute products typically contain up to about 8 %, preferably from 2 to 8 % by weight of softening active, whereas concentrated products may contain from about 8 to about 50 %, preferably from 9 to 25 % by weight active.

Compositions of more than about 25 % by weight of active are defined as "super concentrated", depending on the active system, and are also intended to be covered by the present invention. The fabric conditioning agent may, for example, be used in amounts of from 0.5 % to 35 %, preferably from 2 % to 30 % more preferably from 5 % to 25 % and most preferably from 8 % to 20 % by weight of the composition.

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 %, e.g. 55 %, or 45 % of the fabric softening compound and at least 10 % of the monoester linked component, for example 1 1 % monoester. A preferred hardened type of active has a typical mono:di:tri ester distribution of from 18 to 22 mono: from 58 to 62 di: from 18 to 22 tri; for example 20:60:20. 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 triethanolammoniunn 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), Ceca Noramine, 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 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):-

R¹

(IV) R¹ N R² χ

R² 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 for use in 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 monosaturated 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 from 1 to 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. 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. Without being bound by theory it is believed that the fatty complexing material improves the viscosity profile of the composition by complexing with mono-ester component of the fabric conditioner material thereby providing a composition which has relatively higher levels of di-ester and tri-ester linked components. The di-ester and tri-ester linked components are more stable and do not affect initial viscosity as detrimentally as the mono-ester component.

It is also believed that the higher levels of mono-ester linked component present in compositions comprising quaternary ammonium materials based on TEA may destabilise the composition through depletion flocculation. By using the fatty complexing material to complex with the mono-ester linked component, depletion flocculation is significantly reduced.

In other words, the fatty complexing agent at the increased levels, as required by the present invention, "neutralises" the mono-ester linked component of the quaternary ammonium material. This in situ di-ester generation from mono-ester and fatty alcohol also improves the softening 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).

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 for use in 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; 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. Direct Dyes

Direct dyes (otherwise known as substantive dyes) are the class of water soluble dyes which have a 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.

M t 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;

F¾ 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 are: (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 for use in 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. Perfume

The compositions for use in 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 logarithm to base 10 of the octanol/water partition coefficient (P). The

octanol/water partition coefficient of a 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, Coumarone, 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 for use in 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 for use in 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, antioxidants, sunscreens, anti-corrosion agents, drape imparting agents, anti-static agents, ironing aids 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 for use in the present invention are aqueous rinse-added softening compositions.

The compositions typically 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 for use in the invention may also contain pH modifiers such as hydrochloric acid or lactic acid. A composition for use in the invention 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 Of The Compositions Of The Invention

The compositions for use in the invention may typically be made by combining a melt comprising the fabric softening active 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. 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 of Composition 1 and Comparative Example A

A fabric conditioner composition was prepared, for use in the present invention, which contained zinc oxide in an amount of 10 wt %.

A comparative fabric conditioner product was prepared using the same method, which did not comprise a metal oxide. These two compositions were prepared using the following process:-

1 . The water was heated to about 50 °C.

2. The acid was then added and the mixture was mixed thoroughly.

3. The minor ingredients (antifoam, salt (CaC^) and preservative) were then added.

4. The softening active and fatty alcohol were melted together at 55 °C to

form a co-melt.

5. The co-melt was then added to the heated water.

6. The resulting product was then mixed for 1 batch volume (using a flow rate of 580ml/min at 4kg scale)

7. The product was cooled to 30°C and perfume and zinc oxide added. 8. The composition was then mixed for 1 batch volume (at a flow rate of 580ml/min at 4kg scale).

The resulting compositions are shown in Table 1 below.

Table 1 : Compositions of the liquid fabric softeners 1 and A

¹ Stepantex SP90 (ex Stepan)

² Stenol 1618L (ex Cognis)

3 Dequest 2010

422 % HCI

⁵ NanoShield ZN-2000, ex Alfa Aesar. The average particle size is 60nm (as determined by BET N₂ adsorption).

Example 2:- Effect of use of Composition 1 and Comparative Example A on heat transfer through fabric

The effect of the use of Composition 1 and Comparative Example A on heat transfer through fabrics was assessed as follows:

The test composition (1 or A) was applied to 100 % knitted cotton using the following method that simulated a domestic machine wash:-

1 . Cotton fabric (10 g) was treated in water (100 ml) containing Composition 1 or Comparative Example A (0.2g).

2. The fabric and liquor were then treated in a SDL Atlas Rotowash pot

washer at 20°C for 10 minutes.

3. The fabric was then spun in a Creda Debonair Autopump spin drier for 30 seconds and allowed to dry in air.

Heat transfer was determined using an IR heat lamp (Interhatch 470IR-456, 250 watt) and a data logging temperature recorder (Fluke 189 true RMS multimeter) attached to a surface mounted K type thermocouple. The thermocouple was taped to the under side ("non-exposed surface") of the fabric to enable temperature measurement on the upper side ("exposed surface"). The lamp was used to radiate the upper side fabric for 5 minutes from a distance of 52 cm. The temperature of the non-exposed surface was measured every 10 seconds until at least 200 measurements had been made. The measurements were carried out in an air conditioned laboratory controlled to 20 °C and 65 % RH.

The results are shown in table 1 (Maximum temperature of non-exposed surface) and Figures 1 and 2 (Temperature profile vs. time). Maximunn temperature at the non-exposed fabric surface (after approx 5

It can be seen from Table 1 that the maximum temperature reached at the non- exposed surface of the fabric is lower for fabric treated in accordance with the invention, than for fabric treated with a standard fabric conditioner composition.

It will be seen from Figures 1 and 2 that the treatment in accordance with the invention significantly reduces the temperature at the non-exposed surface of the fabric throughout the period of the test.

Claims

Use of a white metal oxide as an ingredient in a rinse added aqueous fabric conditioner composition to enable the fabric conditioner composition to render fabrics treated with the composition capable of delivering a cool feel benefit to the wearer of the treated fabric, wherein the fabric conditioner composition comprises a softening active and the white metal oxide is present in an amount of from 2.5 to 40 wt %, based on the weight of the total composition.

Use as claimed in claim 1 , wherein the metal oxide has an average particle size in the range of from 1 to 400 nm.

Use as claimed in claim 1 , wherein the metal oxide has an average particle size in the range of from 60 to 250 nm.

Use as claimed in any preceding claim, wherein the metal oxide is present in an amount of from 5 to 12 wt %, based on the weight of the total

composition.

Use as claimed in any preceding claim, wherein the softening active is a quaternary ammonium compound.

Use as claimed in claim 5, wherein the quaternary ammonium compound is an ester-linked compound comprising a distribution of monoester, diester and triester compounds.

7. Use as claimed in claim 6, wherein the ester-linked compound is an ester- linked triethanolamine quaternary ammonium compound.

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

9. Use as claimed in any preceding claim, wherein the metal oxide is selected from zinc oxide and titanium oxide.