WO2009080570A1

WO2009080570A1 - Fabric treatment active

Info

Publication number: WO2009080570A1
Application number: PCT/EP2008/067456
Authority: WO
Inventors: Mansur Sultan Mohammadi; Kenneth Stuart Lee
Original assignee: Unilever Plc; Unilever N.V.; Hindustan Unilever Limited
Priority date: 2007-12-21
Filing date: 2008-12-12
Publication date: 2009-07-02
Also published as: EP2222829A1; ATE544840T1; CN101952404A; ZA201003054B; PL2222829T3; CN101952404B; EP2222829B1; AR069791A1; BRPI0821304A2; GB0724863D0; ES2382256T3

Abstract

Use of an HH material in a fabric softener composition, comprising a fabric softening compound, to increase comfort of fabric, wherein the HH material is capable of changing its hydrophobic/hydrophilic properties in response to an activation step, and wherein the HH material is a terpene having the general formula:- (C5H8)n where n is from 3 to 8.

Description

FABRIC TREATMENT ACTIVE

Technical Field

The present invention relates to the use of a hydrophobic/hydrophilic material in a laundry treatment composition. More specifically, the present invention relates to the use of a HH material in a laundry treatment composition to increase comfort of laundered fabrics.

Background and Prior Art

The uncomfortable feel of clothes associated with perspiration can take one of two forms depending on the level of sweat production. Under conditions of high sweat production, clothes can become saturated with sweat. Damp areas of clothing then contact the skin causing discomfort through local cooling and cling.

Under conditions of low sweat production there is sweat or high humidity in any space between the skin and first layer of clothing and within the clothing immediately adjacent the skin. Water vapour will gradually diffuse through the clothing into the surrounding air.

The textile literature identifies a high humidity level in the space between the skin and the first layer of clothing as one of the key drivers of discomfort under ambient, low exercise conditions. Similarly, discomfort can arise from the build up of liquid water on the inside surface of apparel textiles. A known approach to this problem is to increase the rate of liquid water transport through textile by increasing the rate of wicking or wetting. This is achieved by decreasing the contact angle of water on the fibre surface. This approach has the disadvantage of also increasing the total amount of water held in the textile. This leads to increased thermal conductivity and increased cling when these areas touch the skin. Both of these effects increase the discomfort experienced in wear.

It is known that certain materials, such as Zinc Oxide (ZnO) and Titanium Oxide (TiO₂) have the ability to change between hydrophobic and hydrophilic properties under different environmental conditions, see for example J. Am. Chem. Soc 2004, 126, 62-63 and Soft Matter 2005, 1, 55-61. There are various publications describing the effect of ZnO and Tiθ2 as hydrophobic/hydrophilic switchable surfaces. WO2004108846 describes the use of Tiθ2 as a coating in combination with a siloxane for an easy clean surface and discloses that it can be applied to fabrics. US2005/0186871 Al discloses a gas permeable apparatus comprising a structure including a plurality of surfaces, at least another of the surfaces comprising electrets, at least one light source for exposing the at least one of the surfaces comprising the photocatalyst to light photons sufficient to activate the photocatalyst, the structure allowing for filtering particulates, wicking liquids, disinfecting, and deodarizing the surfaces.

Photocatalysts such as Tiθ2 are incorporated into the surfaces of apparel products such as goggles to decompose and oxidize absorbed chemicals on the photocatalyst surfaces with absorption of light with sufficient energy to generate and electron hole pair in the photocatalyst . The electron hole pair leads to decomposition of surface contact with water and subsequent reactive chemicals on the surface of the photocatalysts . The coated surfaces also can function as air filters, air vents, wicking surfaces, protective covers, layers, over underlying materials, and act as ultraviolet light protective filters for the underlying materials and body.

WO2008/058831 (Unilever) discloses a fabric softening composition comprising a fabric softening compound and from 5 to 50 % by weight, preferably 5 to 25 % by weight of the composition of a material (HH material) capable of changing its hydrophobic/hydrophilic properties in response to an activation step.

Our as yet unpublished co-pending application PCT/EP2008/059818 discloses a laundry cleaning and/or care composition comprising a photo-bleach and a pro-fragrance.

We have now found that the use of a material having hydrophobic/hydrophilic properties in a laundry treatment composition can increase in-wear comfort of fabric. An increased moisture transport away from the skin and a reduction in humidity in the space between the skin and first layer of clothing and within the clothing immediately adjacent the skin are also achieved. Statement of the Invention

In a first aspect of the invention there is provided the use of an HH material in a fabric softener composition, comprising a fabric softening compound, to increase comfort of fabric, wherein the HH material is capable of changing its hydrophobic/hydrophilic properties in response to an activation step, and wherein the HH material is a terpene having the general formula :- (C₅Hg)_n where n is from 3 to 8.

Summary of the Invention

The idea of the invention is to reduce the level of water held in the region of the textile next to the skin, at the same time as facilitating the movement of water through the textile, in order to increase comfort of the fabric. This is achieved by creating different surface properties on fibres in different regions of the textile (either different regions of the garment, or different sides of the textile) . Areas of the textile which are close to the skin are made hydrophobic, while the areas of the textile which are away from the skin are made hydrophilic. In this manner it is possible to increase water transport without increasing the water holding properties of the textile. Increasing water transport while also decreasing the amount of water held at the surface of the textile closest to the skin provides a beneficial effect. It is possible to maintain comfort for the wearer under conditions of low sweat production i.e. under low exercise conditions, with warm climate etc, or at least delay the outset of discomfort when the wearer is exposed to such conditions.

The key to this approach is to generate different local fibre properties following uniform treatment of the textile with a laundry product. By depositing the HH material onto the textile from the laundry treatment, areas which are close to the skin can be made hydrophobic, whereas areas of textile away from the skin may be rendered hydrophilic by an activation step. It is preferred the activation step uses local environmental conditions. For example, in a preferred embodiment the HH material is photosensitive and the outside of the garment is exposed to light, particularly UV light, and is rendered hydrophilic, whilst the inside of the garment close to the skin and therefore shielded from the sunlight remains hydrophobic.

Important aspects of comfort include the increase in moisture transport away from the skin and the reduction of humidity in any space between the skin and first layer of clothing and within the clothing immediately adjacent the skin .

Hydrophobic/Hydrophilic Material (HH material)

In principle any material which can be deposited on a fabric from a rinse conditioner which can "switch" properties from hydrophobic to hydrophilic or visa versa upon exposure to certain conditions may be employed in the invention. The activation step causing the switch in properties may be based upon photosensitivity, pH change, temperature change, heat flow, change in ionic strength, enzymatic activity etc. The most convenient activation step is based upon photosensitivity, particularly UV light, since it is readily possible to expose the outside of a garment to sunlight, during wear and or drying, whilst shielding the inside of the garment .

Preferred HH materials are those that undergo photo-fission to generate more hydrophilic fragments from a hydrophobic precursor. Aliphatic carbonyl compounds (which undergo Norrish Type II photoreaction) are one class of such materials, lipids with at least one C=C double bond form another class. Other suitable photosensitive materials include those which undergo:

1) structural rearrangement to increase hydrophilicity (e.g. Ketoenol tautomerism or cis-trans isomerism resulting in breaking intra-molecular hydrogen bonds and favouring inter-molecular hydrogen bonds) ; or

2) degradation to more polar species (e.g. UV unstable dyes, or sunscreens) .

The HH materials are generally deposited to apply from 0.2 to 1 %, preferably 0.2 to 0.5 % by weight of the fabric after drying. The HH materials are generally present in an amount of from 0.5 to 15 %, preferably 1 to 10 % in the fabric softening composition.

We have now determined that a broad class of lipids act as

HH materials upon exposure to light. The rate of the photo- fission can be controlled by the presence of photo-bleaches. In the context of the present invention a HH material is any chemical species, which is a precursor to more hydrophilic species (or a further precursor thereof) upon exposure to light in the presence or absence of an active photo-bleach. Preferred HH materials contain at least one, non-aromatic, C-C double-bond, more preferably at least two C-C double- bonds. Preferably, the HH material is a lipid.

Preferred lipids contain mono- or di-unsaturated fatty acids (or their esters) .

Particularly preferred HH materials comprise the structure (I) below:

It is believed that this structure is the site of the reaction with the photo-bleach. Ri and R₂ are selected such that fragmentation of the molecule following exposure to the photo-bleach leads to the production of hydrophilic compounds .

One suitable class of HH materials comprises food lipids. Food lipids typically contain structural units with pronounced hydrophobicity . The majority of lipids are derived from fatty acids. In these ^λacyl' lipids the fatty acids are predominantly present as esters and include mono-, di-, triacyl glycerols, phospholipids, glycolipids, diol lipids, waxes, sterol esters and tocopherols.

Plant lipids have the necessary complement of antioxidants to prevent their oxidation. During the isolation of oils from plants some of these antioxidants are reduced but sufficient level remains. These antioxidants, including vitamins A and its several forms (retinol, retinal and retinoic acid and its carotenoid precursors, provitamin A) and vitamin E can be a added to HH material to control the rate of photo-fragmentation.

Preferred food lipids include amaranth oil, olive oil, palm oil, canola oil, sunflower seed oil, wheat germ oil, almond oil, coconut oil, grape seed oil, rapeseed oil, castor oil, corn oil, cottonseed oil, safflower oil, evening primrose oil, groundnut oil, poppy seed oil, palm, palm kernel oil, rice bran oil, sesame oil, soybean oil, and jojoba oil.

Preferred food lipids also include oils and fats of animal source including squalene (also present in olive oil and wheat germ oil) butter, and ghee. To avoid allergic reaction, certain nut oils (peanut oil, for example) are less preferred.

A particularly preferred class of HH materials are the terpenes .

Terpenes are derived from units of isoprene, which has the molecular formula CsHg. The basic molecular formulae of terpenes are given by the formula:- ( C₅Hg ) _n

where n is the number of linked isoprene units. The isoprene units may be linked together "head to tail" to form linear chains or they may be arranged to form rings. Those suitable for use in the present invention are preferably linear .

Terpenes preferred in the present invention are those in which n = from 3 to 8.

The number of carbon to carbon double bonds is from 3 to 8, preferably 6.

The most preferred terpene is squalene, in which n = 6. Squalene is a triterpene, has 6 double bounds and a linear structure .

Preferred oils may be selected from the group consisting of soy oil, grapeseed oil, castor oil, hexadecane and squalene, preferably squalene.

Another class of preferred lipids are the oily sugar esters described below under fabric softening materials.

The most preferred HH materials contain at least 20 wt% of a compound which comprises the moiety

Where Rl and R2 are organic groups containing carbon, hydrogen and oxygen. A preferred example is linoleic acid.

Particularly preferred fatty acid containing lipids contain 10 wt% or less of moieties containing three double bonds, (such as linolenic acid) . Also the most preferred lipids contain less than 15 wt% saturated acids and less than 15 wt% of acids with less than 14 carbon atoms. Within these preferred limits branched-chain and hydroxyl acid moieties are included

Most preferred oils exclude those of high linolenic content (preferred < 10%) , such as hemp oil (~25%wt linolenic acid) , and oils of nut origin.

According to the present invention there is provided a laundry care composition comprising a photo-bleach and a HH material.

In the context of the present invention a "photo-bleach" is any chemical species which forms a reactive bleaching species on exposure to sunlight, and preferably is not permanently consumed in the reaction. Preferred photo- bleaches include singlet oxygen photo-bleaches and radical photo-bleaches. Suitable photo-bleaches are described in more detail below. Preferred levels of photo-bleach present in the composition are from 0 to 0.01 wt% preferably 0.00005 to 0.05%.

Some of the photo-bleaches impart colour to the fabric. To give the clothes an appealing white hue, it is preferred if blue or violet shading dyes are used in combination with the photo-bleaches. In the alternative a combination of photo- bleaches is used to generate a white hue.

Preferred dyes are as described in WO2005/003274 (Unilever) and WO2005/003277 (Unilever) . Particularly preferred shading dyes are bis azo direct dyes, particularly those of the direct violet 9, 35 and 99 type and acid azine dyes such as acid violet 50 and acid blue 98. Alternative shading dyes are described below. Dyes can sometimes act as a photo- sentisiser .

Bleach Catalysts

As noted above the photo-bleaches suitable for use in the present invention include singlet oxygen photo-bleaches and radical photo-bleaches.

Singlet Oxygen Photo-bleaches:

Singlet oxygen photo-bleaches (PB) function as follows:

PB + l i gh t → PB ^' PB * + ³O₂ → PB + ¹O, The photo-bleach molecule absorbs light and attains an electronical excited state, PB*. This electronically excited state is quenched by triplet oxygen, ³θ2, in the surroundings to form singlet ¹O∑. Singlet oxygen is a highly reactive bleach.

Suitable singlet oxygen photo-bleaches may be selected from, water soluble phthalocyanine compounds, particularly metallated phthalocyanine compounds where the metal is Zn or Al-Zl where Zl is a halide, sulphate, nitrate, carboxylate, alkanolate or hydroxyl ion. Preferably the phthalocyanin has 1-4 SO3X groups covalently bonded to it where X is an alkali metal or ammonium ion. Such compounds are described in WO2005/014769 (Ciba) .

Xanthene type dyes are preferred, particularly based on the structure :

where the dye may be substituted by halogens and other elements/groups. Particularly preferred examples are Food Red 14 (Acid Red 51), Rose Bengal, Phloxin B and Eosin Y. Other singlet oxygen producing compounds include chlorophyll, coumarin, porphyrins, myoglobin, riboflavin, bilirubin, and methylene blue.

The singlet oxygen photo-bleaches generally impart some colour to the fabric. To give the clothes an appealing white hue, it is preferred if blue or violet photo-bleach dyes are used in combination with the shading dyes as described in WO2005/003274 (Unilever) and WO2005/003277 (Unilever) . Particularly preferred shading dyes are bis azo direct dyes of the direct violet 9, 35 and 99 type and acid azine dyes such as acid violet 50 and acid blue 98.

Radical Photo-bleaches:

Radical photo-bleaches (radical photo-initiators) are well known chemicals in the plastics and curing industry. These application have been widely discussed in the literature see e.g. H. F. Gruber Prog. Polym. Sci. 17 (1992), 953-1044 and references therein. They are organic chemicals which on exposure to light react to form neutral radicals that may initiate the polymerization of alkenes. Recently they have been found to be effective laundry photo-bleaches: UK patent application 9917451.8 teaches their use from main wash detergent powders and liquids, where the photo-initiators are intimately mixed into the powder or liquids. Radical photo-bleaches are molecules that absorb light (typically 290-400nm) to produce organic carbon-centered radicals . Radical photo-bleaches may function by intermolecular hydrogen abstraction or by intramolecular alpha or beta bond cleavage .

Suitable radical photo-bleaches may be selected from quinones, ketones, aldehydes, and phosphine oxides. Preferably the maximum extinction coefficient is between 290 and 400 nm (measured in ethanol) is greater 10, more preferably greater than 100 mol^"1 L cm^"1.

A particularly preferred class of radical photo-bleaches are based on the structure:

Where

Rl may be H, OH, Oalkyl preferably methoxy or ethoxy R2 may be H, Cl- C9 alkyl branched or linear R3 may be H, Cl- C9 alkyl

Preferably Rl, R2 and R3 are hydrogen

The phenyl ring, A, may be substitute at the 3,4 and 5 position by:

C1-C9 alkyl branched of linear, preferably methyl, ethyl, OR4 where R4 may be C1-C9 alkyl branched of linear, preferably methyl, ethyl,

Preferred examples of this type are acetophenone, 4 methyl acetophenone, 4 methoxy acetophenone. Benzophenone and vitamin K3 are also preferred radical photo-bleach.

Other suitable bond cleavage radical photo initiators may be selected from the following groups:

(a) alpha amino ketones, particularly those containing a benzoyl moiety, otherwise called alpha-amino acetophenones, for example 2-methyl 1- [4-phenyl] -2- morpholinopropan-1-one (Irgacure 907, trade mark), (2- benzyl-2-dimethyl amino-1- (4-morpholinophenyl) -butan-1- one (Irgacure 369, trade mark);

(b) alphahydroxy ketones, particularly alpha-hydroxy acetophenones, eg (1- [4- (2-hydroxyethoxy) -phenyl] -2- hydroxy-2-methyl-l-propan-l-one) (Irgacure 2959, trade mark), 1-hydroxy-cyclohexyl-phenyl-ketone (Irgacure 184, trade mark) ;

(c) phosphorus-containing photoinitiators, including monoacyl and bisacyl phosphine oxide and sulphides, for example 2-4-6- (trimethylbenzoyl) diphenyl-phosphine oxide, bis (2,4, 6-trimethylbenzoyl) -phenyl-phosphine oxide (Irgacure 819, trade mark), (2,4,6- trimethylbenzoyl) phenyl phosphinic acid ethyl ester (Lucerin TPO-L (trade mark) ex BASF) ;

(d) dialkoxy acetophenones; (e) alpha-haloacetophenones; and

(f) trisacyl phosphine oxides.

(g) benzoin and benzoin based photoinitiators

(h) thioxanthene based photoinitiators

Further suitable radical photo-bleaches are disclosed in

WO 9607662 (treacly phosphate oxides), US 5399782 (phosphine sulphides), US 5410060, EP-A-57474, EP-A-73413 (phosphine oxides), EP-A-088050, EP-A-0117233, EP-A-0138754, EP-A- 0446175 and US 4559371.

Yet further suitable photo-bleaches are disclosed for example in EP-A-0003002 in the name of Ciba Geigy, EP-A-0446175 in the name of Ciba Geigy, GB 2259704 in the name of Ciba Geigy (alkyl bisacyl phosphine oxides) , US 4792632 (bisacyl phosphine oxides), US 5554663 in the name of Ciba Geigy (alpha amino acetophenones) , US 5767169 (alkoxy phenyl substituted bisacyl phosphine oxides) and US 4719297 (acylphosphine compounds) .

Radical photo-bleaches are discussed in general in A. F. Cunningham, V. Desorby, K. Dietliker, R. Husler and D. G. Leppard, Chemia 48 (1994) 423-426. They are discussed in H. F. Gruber Prog. Polym. Sci. 17(1992) 953-1044.

In the context of the present invention the photo-bleach will typically have a cleaning function as well as reacting with the HH material. Inorganic photo-bleaches, including titanium dioxide are also preferred because they are HH material in their own right .

Fabric Softening Compound

The fabric softening compound which is different from the HH material. Suitable fabric softening compounds are described below.

(i) Oily sugar derivative

The oily sugar derivative is a liquid or soft solid derivative of a cyclic polyol or of a reduced saccharide, 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.

The oily sugar derivatives of the invention are also referred to herein as "derivative-CP" and "derivative-RS" dependent upon whether the derivative is a product derived from a cyclic polyol or from a reduced saccharide starting material respectively.

Preferably the derivative-CP and derivative-RS contain 35% by weight tri or higher esters, e.g. at least 40%.

Preferably 35 to 85% most preferably 40 to 80%, even more preferably 45 to 75%, such as 45 to 70% of the hydroxyl groups in said cyclic polyol or in said reduced saccharide are esterified or etherified to produce the derivative-CP and derivative-RS respectively.

For the derivative-CP and derivative-RS, the tetra, penta etc prefixes only indicate the average degrees of esterification or etherification . The compounds exist as a mixture of materials ranging from the monoester to the fully esterified ester. It is the average degree of esterification as determined by weight that is referred to herein.

The derivative-CP and derivative-RS used do not have substantial crystalline character at 2O⁰C. Instead they are preferably in a liquid or soft solid state, as hereinbelow defined, at 2O⁰C.

The starting cyclic polyol or reduced saccharide material is esterified or etherified with C8-C22 alkyl or alkenyl chains to the appropriate extent of esterication or etherification so that the derivatives are in the requisite liquid or soft solid state. These chains may contain unsaturation, branching or mixed chain lengths .

Typically the derivative-CP or derivative-RS has 3 or more, preferably 4 or more, for example 3 to 8, e.g. 3 to 5, ester or ether groups or mixtures thereof. It is preferred if two or more of the ester or ether groups of the derivative-CP and derivative-RS are independently of one another attached to a Cs to C22 alkyl or alkenyl chain. The alkyl or alkenyl groups may be branched or linear carbon chains. The derivative-CPs are preferred for use as the oily sugar derivative. Inositol is a preferred cyclic polyol, and Inositol derivatives are especially preferred.

In the context of the present invention the terms derivative-CP and derivative-RS encompass all ether or ester derivatives of all forms of saccharides, which fall into the above definition, and are especially preferred for use. Examples of preferred saccharides for the derivative-CP and derivative-RS to be derived from are monosaccharides and disaccharides .

Examples of monosaccharides include xylose, arabinose, galactose, fructose, sorbose and glucose. Glucose is especially preferred. An example of a reduced saccharide is sorbitan. Examples of disaccharides include maltose, lactose, cellobiose and sucrose. Sucrose is especially preferred.

If the derivative-CP is based on a disaccharide it is preferred if the disaccharide has 3 or more ester or ether groups attached to it. Examples include sucrose tri, tetra and penta esters.

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

Examples of suitable derivative-CPs include esters of alkyl (poly) glucosides, in particular alkyl glucoside esters having a degree of polymerisation from 1 to 2. The HLB of the derivative-CP and derivative-RS is typically between 1 and 3.

The derivative-CP and derivative-RS may have branched or linear alkyl or alkenyl chains (of varying degrees of branching), mixed chain lengths and/or unsaturation . Those having unsaturated and/or mixed alkyl chain lengths are preferred.

One or more of the alkyl or alkenyl chains (independently attached to the ester or ether groups) may contain at least one unsaturated bond.

For example, predominantly unsaturated fatty chains may be attached to the ester/ether groups, e.g. those attached may be derived from rape oil, cotton seed oil, soybean oil, oleic, tallow, palmitoleic, linoleic, erucic or other sources of unsaturated vegetable fatty acids. The alkyl or alkenyl chains of the derivative-CP and derivative-RS are preferably predominantly unsaturated, for example 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 trioleate, glucose tetraoleate, xylose trioleate, or sucrose tetra-, tri-, penta- or hexaesters with any mixture of predominantly unsaturated fatty acid chains. Unsaturation as mentioned earlier can help fragmentation of molecules into more hydrophilic components by photoreaction . In this context the softener plays the dual role of softening and HH material.

As the primary softener some derivative-CPs and derivative- RSs may be based on alkyl or alkenyl chains derived from polyunsaturated fatty acid sources, e.g. sucrose tetralinoleate . It is preferred that most, if not all, of the polyunsaturation has been removed by partial hydrogenation if such polyunsaturated fatty acid chains are used.

The most highly preferred liquid derivative-CPs and derivative-RSs are any of those mentioned in the above three paragraphs but where the polyunsaturation has been removed through partial hydrogenation. However as a HH material polyunsaturation with limited < 10% linolenic fatty acids is acceptable .

Especially good softening results are obtained when the alkyl and/or alkenyl chains of the derivative-CPs and derivative-RSs are obtained by using a fatty acid mixture (to react with the starting cyclic polyol or reduced saccharide) which comprises a mixture of tallow fatty acid and oleyl fatty acid in a weight ratio of 10:90 to 90:10, more preferably 25:75 to 75:25, most preferably 30:70 to 70:30. A fatty acid mixture comprising a mixture of tallow fatty acid and oleyl fatty acid in a weight ratio of 60:40 to 40:60 is most preferred. Especially preferred are fatty acid mixtures comprising a weight ratio of approximately 50 wt% tallow chains and 50wt% oleyl chains. It is especially preferred that the fatty acid mixture consists only of a mixture of tallow fatty acid and oleyl fatty acid.

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

Other oily sugar derivatives suitable for use in the compositions include sucrose pentalaurate, sucrose pentaerucate and sucrose tetraerucate . Suitable materials include some of the Ryoto series available from Mitsubishi Kagaku Foods Corporation.

Another class of suitable oily sugar derivatives are those disclosed in our recent WO2006076952 (Al) such as Emanon SCR-PK (ex KAO) , which is a palm kernel derived SPE containing mainly C12-C14 with about 20% C18 mono unsaturatation and SPE-THSBO (ex Clariant) , which is derived from touch hardened soy bean oil, having mainly C16-C18 chains with about 80% mono and di unsaturation . The average degree of esterification of the above preferred SPEs is between 4.2-4.7.

The liquid or soft solid derivative-CPs and derivative-RSs are characterised as materials having a solid: liquid ratio of between 50:50 and 0:100 at 20⁰C 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 NMR signal with a T2 of less than 100 microsecond is considered to be a solid component and any component with T2 greater than 100 microseconds is considered to be a liquid component.

The liquid or soft solid derivative-CPE and derivative-RSE can be prepared by a variety of methods well known to those skilled in the art. These methods include acylation of the cyclic polyol or of a reduced saccharide with an acid chloride; trans-esterification of the cyclic polyol or of a reduced saccharide material with short chain fatty acid esters in the presence of a basic catalyst (e.g. KOH); acylation of the cyclic polyol or of a reduced saccharide with an acid anhydride, and, acylation of the cyclic polyol or of a reduced saccharide with a fatty acid. Typical preparations of these materials are disclosed in US 4 386 213 and AU 14416/88 (Procter and Gamble) .

When an oily sugar derivative is present the compositions preferably comprise between 0.5%-30% wt of the oily sugar derivatives, more preferably 1-20% wt, most preferably 1.5- 20% wt, e.g. 3-15% wt %, based on the total weight of the composition.

(ii) Cationic Fabric Softening Compounds

The preferred cationic fabric softening compound (s) are those having two or more alkyl or alkenyl chains each having an average chain length equal to, or greater than Cs, especially C12-28 alkyl or alkenyl chains connected to a nitrogen atom. The alkyl or alkenyl groups are preferably connected via at least one ester link, more preferably via two or more ester linkages.

The cationic fabric softening compounds may be ester-linked quaternary ammonium fabric softening compounds or non-ester linked quaternary ammonium fabric softening compounds. The ester-linked quaternary ammonium fabric softening compounds are herein referred to as "the ester-softening compound". The non-ester linked quaternary ammonium fabric softening compounds are herein referred to as "the non-ester softening compound" .

Especially suitable compounds have two or more alkyl or alkenyl chains each having an average chain length equal to, or greater than Ci₄, more preferably, equal to or greater C16. Most preferably at least 50% of the total number of alkyl or alkenyl chains have a chain length equal to, or greater than C18 •

It is advantageous for environmental reasons if the ester- softening compound is biologically degradable. It is also preferred if the alkyl or alkenyl chains of the ester- softening compound are predominantly linear.

One preferred type of ester-softening compound is a quaternary ammonium material represented by formula (I) : TR^Z

(R¹J₃ N⁺- (CH₂) _n CH X^" (I)

(CH₂UTR"

O O

Il Il wherein T is -O-C- or -C-O-; each R¹ group is independently selected from C₁-₄, alkyl or hydroxyalkyl or C₂-₄ alkenyl groups; and wherein each R² group is independently selected from C8-₂8 alkyl or alkenyl groups, X^~ is any suitable anion including a halide, acetate or lower alkosulphate ion, such as chloride or methosulphate, n is O or an integer from 1-5, and m is from 1-5.

Preferred materials of this class such as 1,2 bis [hardened tallowoyloxy] -3- trimethylammonium propane chloride and their method of preparation are, for example, described in US 4 137 180 (Lever Brothers) . Preferably these materials comprise small amounts of the corresponding monoester as described in US 4 137 180 for example 1-hardened tallowoyloxy -2-hydroxy 3-trimethylammonium propane chloride.

A second preferred type of ester-softening compound is represented by the formula (II) : R¹

R¹ N⁺ ^■ ( CH₂ ) _n-T-ir X^" ( i i :

( CH₂ ) _n-T-R²

wherein T, R¹, R², n, and X are as defined above.

In this class di (tallowoyloxyethyl) dimethyl ammonium chloride and methyl bis-[ethyl (tallowoyl) ]- 2-hydroxyethyl ammonium methyl sulphate are especially preferred. The tallow chains in these compounds may be hardened and may even be fully unsaturated, i.e. preferred compounds also include di (hardened tallowoyloxy ethyl) dimethyl ammonium chloride and methyl bis- [ethyl (hardened tallowoyl) ] -2- hydroxyethyl ammonium methyl sulphate. Commercially available compounds include those in the Tetranyl range (ex Kao) and Stepantex range (ex Stepan) .

Also suitable are derivatives of the above formula where one or more of the (CH₂) _n chain (s) has at least one pendent alkyl chain e.g. a methyl chain. Examples include the cationic quaternary ammonium compounds described in WO 99/35223 and WO 99/35120 (Witco) .

A third preferred type of ester-softening compound is a quaternary ammonium material represented by the formula (III) : O O R"

( R -C-O- ) ; A ( -O-C-B-N⁺-R⁵ ) _n X^" : i i i )

R^s

wherein X is as defined above, A is an (m+n) valent radical remaining after the removal of (m+n) hydroxy groups from an aliphatic polyol having p hydroxy groups and an atomic ratio of carbon to oxygen in the range of 1.0 to 3.0 and up to 2 groups per hydroxy group selected from ethylene oxide and propylene oxide, m is 0 or an integer from 1 to p-n, n is an integer from 1 to p-m, and p is an integer of at least 2, B is an alkylene or alkylidene group containing 1 to 4 carbon atoms, R³, R⁴, R⁵ and R⁶ are, independently from each other, straight or branched chain C1-C48 alkyl or alkenyl groups, optionally with substitution by one or more functional groups and/or interruption by at most 10 ethylene oxide and/or propylene oxide groups, or by at most two functional groups selected from;

O O O O 0

-C-O-, -0-C-, -C-N-, -N-C-, and -0-C-O-

or R⁴ and R⁵ may form a ring system containing 5 or 6 atoms in the ring, with the proviso that the average compound either has at least one R group having 22-48 carbon atoms, or at least two R groups having 16-20 carbon atoms, or at least three R groups having 10-14 carbon atoms. Preferred compounds of this type are described in EP 638 639 (Akzo) . The non-ester softening compound preferably has the alkyl or alkenyl chain lengths referred to above (in respect of the non-ester softening compounds) .

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

R¹

R N R X

2

^R (IV)

wherein each R¹ group is independently selected from C1-4 alkyl, hydroxyalkyl or C2-4 alkenyl groups; each R² group is independently selected from Cs-28 alkyl or alkenyl groups, and X^~ is as defined above.

A preferred material of formula (IV) is di-hardened tallow- dimethyl ammonium chloride, sold under the Trademark ARQUAD 2HT by Akzo Nobel.

The compositions preferably comprise a total amount of from 0.5% to 50% by weight of the cationic fabric softening compounds, preferably from 3% to 50%, more preferably from 4% to 40%, most preferably from 5% to 25%, based on the total weight of the composition, for example from 0.5 to 30 wt %, 1 to 25 wt %, 1.5 to 22 wt % and 2 to 20 wt %. 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 . Typical ester quat ratios of these materials are in the range of from 25 to 45% mono ester quat, from 45 to 60 % diester quat and from 5 to 20 % triester quat, preferably from 30 to 40 % mono ester quat, from 50 to 55 % diester quat and from 10 to 15 % triester quat .

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, 1136 (1962) Johnson and Shoolery.

As mentioned above softener materials with sufficient unsaturation can play the dual role of softener and HH material .

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. no more than 55%, or even no more than 45% 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 of 18-22 mono: 58-62 di : 18-22 tri, for example 20:60:20. A soft TEA quat may have a typical mono : di : tri ester distribution of 25-45 mono: 45-60 di : 5-25 tri, for example 40: 60:10.

Non-Ionic Surfactant

A non-ionic surfactant may be present in order to stabilise the composition, or perform other functions such as emulsifying any oil that may be present.

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

Preferred materials are of the general formula:

R-Y-(CH₂CH₂O)₂H Where R is a hydrophobic moiety, typically being an alkyl or alkenyl group, said group being linear or branched, primary or secondary, and preferably having from 8 to 25, more preferably 10 to 20, and most preferably 10 to 18 carbon atoms; R may also be an aromatic group, such as a phenolic group, substituted by an alkyl or alkenyl group as described above; Y is a linking group, typically being O, CO. O, or CO-N(R¹), where R¹ is H or a Ci_₄ alkyl group; and z represents the average number of ethoxylate (EO) units present, said number being 8 or more, preferably 10 or more, more preferably 10 to 30, most preferably 12 to 25, e.g. 12 to 20.

Examples of suitable non-ionic surfactants include the ethoxylates of mixed natural or synthetic alcohols in the "coco" or "tallow" chain length. Preferred materials are condensation products of coconut fatty alcohol with 15-20 moles of ethylene oxide and condensation products of tallow fatty alcohol with 10-20 moles of ethylene oxide.

The ethoxylates of secondary alcohols such as 3-hexadecanol, 2-octadecanol, 4-eicosanol, and 5-eicosanol may also be used. Exemplary ethoxylated secondary alcohols have formulae Ci₂-EO(20); Ci₄-EO(20); Ci₄-EO(25); and Ci₆-EOOO) . Especially preferred secondary alcohols are disclosed in PCT/EP2004/003992 and include Tergitol-15-S-3.

Polyol-based non-ionic surfactants may also be used, examples including sucrose esters (such as sucrose monooleate) , alkyl polyglucosides (such as stearyl monoglucoside and stearyl triglucoside) , and alkyl polyglycerols . Fatty Complexing Agent

A preferred additional component in the compositions of the present invention is a fatty complexing agent. Such agents typically have a Cs to C22 hydrocarbyl chain present as part of their molecular structure. Suitable fatty complexing agents include Cs to C22 fatty alcohols and Cs to C22 fatty acids; of these, the Cs to C22 fatty alcohols are most preferred. A fatty complexing agent is particularly valuable in compositions comprising a QAC having a single C12-28 group connected to the nitrogen head group, such as mono-ester associated with a TEA ester quat . or a softening agent of formula II, for reasons of product stability and effectiveness .

Preferred fatty acid complexing agents include hardened tallow fatty acid (available as Pristerene, ex Uniqema) .

Preferred fatty alcohol complexing agents include Ciε/Cis fatty alcohols (available as Stenol and Hydrenol, ex Cognis, and Laurex CS, ex Albright and Wilson) and behenyl alcohol, a C22 fatty alcohol, available as Lanette 22, ex Henkel.

The fatty complexing agent may be used at from 0.1% to 10%, particularly at from 0.2% to 5%, and especially at from 0.4 to 2% by weight, based on the total weight of the composition . Perfume

The compositions of the invention typically comprise one or more perfumes. The perfume is preferably present in an amount from 0.01 to 10% by weight, more preferably 0.05 to 5% by weight, most preferably 0.5 to 4.0% by weight, based on the total weight of the composition.

Viscosity Modifiers

The Fabric softening compositions may comprise viscosity modifiers. Suitable viscosity modifiers are disclosed, for example, in WO 02/081611, US 2004/0214736, US 6827795, EP 0501714, US 2003/0104964, EP 0385749 and EP 331237.

Further Optional Ingredients

The compositions of the invention may contain one or more other ingredients. Such ingredients include preservatives (e.g. bactericides), pH buffering agents, perfume carriers, fluorescers, colourants, hydrotropes, antifoaming agents, anti-redeposition agents, soil-release agents, electrolytes including polyelectrolytes, enzymes, optical brightening agents, anti-shrinking agents, anti-wrinkle agents, anti- spotting agents, anti-oxidants, sunscreens, anti-corrosion agents, drape imparting agents, anti-static agents, ironing aids and dyes. Product Use

The compositions of the present invention are preferably rinse conditioner compositions and may be used in the rinse cycle of a domestic laundry process.

The composition is preferably used 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, though less desirable, for the compositions of the present invention to be used in industrial laundry.

Embodiments of the invention will be described with reference to the following Examples.

Examples

Apparatus

A Tergotometer (US Testing CO. Inc., Hobken, N.J.) was used to simulate the rinse stage of a washing machine.

Light Source : Atlas Xenon Weatherometer S3000

Spin dryer: Creda debonair spindryer Materials

Fabric: 100% Polyester (Knit 140gm ) in red colour. 100% cotton white colour (jersey knit (175gm -2,

Fabric Softener Examples: set 1

ARQUAD 2HT is a di-hardened tallow-dimethyl ammonium chloride.

Procedure

Treatment

Samples of clean polyester or cotton were cut into 20cm x 20cm pieces. Two such monitor pieces were placed in a

Tergotometer with 1 litre of tap water to which 0.48g of the compositions in Set 1 was added and agitated for 15 minutes. Then one monitor was removed and O.Olg of Acid Red 51 (AR51) photo-sentisiser was added and agitated for another 15 minutes before removing from Tergotometer. The fabric monitors were then spun for 1 minute in the spin dryer.

This procedure delivered 0.16 μg/g fabric of AR51 and 8 mg/g fabric of the fabric conditioner. The treated fabric monitors were allowed to dry on line in a drying room over night (in dim fluorescent light during day but dark during night) .

Light Exposure

The treated dried monitors were then cut in 15x7 cm x cm rectangles and placed in the Atlas Weatherometer mounting frames ready for light exposure.

The fabric samples were then exposed to a 2kW Xenon light source for 30 minutes with a relative humidity between 50- 60%, at the start of the test reaching 20% RH by the end of the 30 minutes period.

Once the exposure was complete the monitors were assessed for their wetting behaviour on the exposed side (Front) and the reverse side (Back) .

Wetting Test

Exposed and unexposed samples were assessed for wetting by placing several 50 mg droplets across the surface of the fabric and recording the times taken for the droplets to fully penetrate the surface. This was completed on both sides of the exposed monitors. Results

Table 1. Average wetting times in seconds for the front (exposed to UV) and back (dark) of the Weather-o-meter polyester monitors with and without photosentisiser Acid Red 51.

Wetting time 600+ means greater than 10 minutes. In the above cases in fact greater than 30 minutes A wetting time of > 10 minutes represents a quite hydrophobic surface.

It will be seen from examples 4 and 4 + AR51, squalene oil with eight double bonds in the molecule, that a higher hydrophobicity is conferred on the back of the cloth than on the front of the cloth in presence of photobleach, which translates into greater comfort due to moisture transport away from the skin.

Knitted cotton under similar treatment remained hydrophilic for all the treatments. Fabric Softener Examples : set 2

Examples 5 6 7 8 9

Stepantex UL 85 4.4 0.4 2.35 0 0 (ex Stepan)

Stepantex VT90 0 0 0 0. 4 4. 4 (ex Stepan)

Stenol 16/18 L 0.5 0.04 0.23 0. 04 0. 5 (ex Cognis)

Genapol C200 0.1 0.1 0.1 0. 1 0. 1 (ex Clariant

Squalene 0 4 2.2 4 0 (ex Sigma) water to 100 to 100 to 100 to 100 to 100

Stepantex UL 85 is a hard tallow TEA quat with 20% mono-, 50% di- and 30% tri-ester. It contains 85% active and 15% IPA. Stepantex VT90 is a soft tallow TEA quat containing 90% active and 10% IPA. Stenol 16/18 L is a fatty alcohol (complexing agent) with a mixture of C16 and C18 saturated chains. Genapol C200 is a coco based ethoxylated non-ionic surfactant with 20EO.

Knit polyester monitors were treated with Set 2 composition in Tergotometer following the same protocol. The amount of fabric conditioner added to the Tergotometer were 2g/litre which delivers same weight of treatment per weight of fabric as in Set 1. The amount of photo-bleach was similar at O.Olg/1 of solution.

Table 2. Wetting times in seconds for the front (exposed to UV) and back (dark) of the Weather-o-meter monitors with and without photosentisiser Acid Red 51.

Wetting Time/s

Treatments for F/B

Control (water) ± AR51 600+/600+

Example 5 :b AR51 600+/600+

Example 6 129/22

Example 6 -h AR51 142/600+

Example 7 404/600

Example 7 -h AR51 83/137

Example 8 600+/290

Example 8 -h AR51 400/251

Example 9 285/600+

Example 9 -h AR51 38/27

Wetting time of 600+ means it has taken greater than 10 minutes.

In Example 6 without photobleach and in Example 8 with or without photobleach the differential hydrophobicity is the reverse of the desired order. In other Examples the desired order is achieved. In Example 9 + AR51 the process of photo-fragmentation has gone too far resulting in hydrophilicity on both sides of the monitors. This may be because of the excess un-saturation in the composition coming both from VT90 and squalene.

Claims

1. Use of an HH material in a fabric softener composition, comprising a fabric softening compound, to increase comfort of fabric, wherein the HH material is capable of changing its hydrophobic/hydrophilic properties in response to an activation step, and wherein the HH material is a terpene having the general formula :-

(C₅Hg)_n where n is from 3 to 8.

2. Use as claimed in claim 1, wherein increase moisture transport away from the skin is increased.

3. Use as claimed in claim 1, wherein humidity in any space between the skin and first layer of clothing and within the clothing immediately adjacent the skin is reduced.

4. Use as claimed in any preceding claim, wherein the HH material is present at a level of from 0.5 to 15 % by weight .

5. Use as claimed in any preceding claim in which the HH material is hydrophobic but becomes hydrophilic upon exposure to light, particularly UV light.

6. Use as claimed in any preceding claim in which the HH material changes its hydrophobic/hydrophilic properties in response to light in the presence of one or more photo-bleaches .

7. Use as claimed in claim 6 in which the photo-bleach is a singlet oxygen or radical photo-bleach from 0 to 0.05 w%.

8. Use as claimed in any preceding claim in which the HH material changes its hydrophobic/hydrophilic properties in response to change in pH, temperature change, heat flow, change in ionic strength or presence of an enzyme .

9. Use as claimed in any preceding claim, in which n = 6.

10. Use as claimed in any preceding claim, in which the terpene is squalene.

11. Use as claimed in any preceding claim in which the fabric softening compound is selected from an oily sugar derivative, a cationic fabric softening compound and mixtures thereof.

12. Use as claimed in claim 11 in which the cationic fabric softening compound is a quaternary ammonium compound derived from fatty feed stock having an Iodine Value of from 0 to 140, preferably from 0 to 45.

13. A composition according to claim 11 or claim 12, wherein the quaternary ammonium compound is an ester- linked triethanolammonium (TEA) quaternary ammonium compound.

14. A composition according to any preceding claim, wherein the fabric softening compound is present at a level of from 3 to 50 %, preferably 4 to 40, more preferably 5 to 25, by weight of the total composition.

15. Use as claimed in any preceding claim in which the HH material changes its hydrophobic/hydrophilic properties which additionally comprises one or more ingredients selected from perfume, non-ionic surfactant, fatty acid, fatty alcohol and viscosity modifier.