EP2294168B1

EP2294168B1 - Improvements relating to fabric conditioners

Info

Publication number: EP2294168B1
Application number: EP09757364A
Authority: EP
Inventors: Mansur Sultan Mohammadi
Original assignee: Unilever PLC; Unilever NV
Current assignee: Unilever PLC; Unilever NV
Priority date: 2008-06-05
Filing date: 2009-04-24
Publication date: 2012-12-19
Anticipated expiration: 2029-04-24
Also published as: WO2009146981A1; ZA201007840B; CN102057027B; PL2294168T3; AR071932A1; CN102057027A; BRPI0914903A2; ES2398622T3; EP2294168A1

Description

Technical Field

The present invention concerns the use of sugar esters to reduce and eliminate fatty base off-odours in fabric conditioner compositions which contain actives having unsaturated fatty chains.

Background of the Invention

So-called 'soft' fabric softening actives derived from unsaturated fatty acyl or acid feedstock, have the advantages of ease of formulation and manufacture and a greater physical stability under varying climatic storage conditions, when compared to the so-called 'hardened' softeners (i.e. those derived from fully or nearly fully saturated fatty compounds).
However a disadvantage of 'soft' actives is the generation of an objectionable fatty base odour. This odour is believed to arise, at least in part, from rancidification of the double bonds in the fatty acid or fatty acyl chains, due to auto-oxidation. Malodour is detectable in the raw material, in the formulated products and on the substrate itself, such as fabric, during and after treatment with these soft actives.
One general approach to solving malodour problems, found in the prior art, is to mask the malodour with perfume.
Perfume ingredients have been used to counteract the malodours generated on different substrates.
For example, WO 2008/026140 A2 (Firmenich), uses malodour counteracting mixtures of perfume ingredients containing at least one nitrile material in combination with another fragrance material to neutralise tobacco, bathroom or kitchen malodours, animal malodours, etc in a variety of products including textile treatment products such as fabric softeners.
WO 2006/058297 A1 (Procter & Gamble), uses perfume compositions for masking fatty acid odours in a range of cleaning and treatment compositions including laundry and dishwashing detergents, particularly those odours arising from enzyme-generated short chain fatty acids such as butyric acid.
WO 2006/066705 A1 (Unilever), describes a malodour reducing toilet bar composition comprising a pyranone derivative. Use of pyran-4-one derivates as a specific odour masking agent in toilet bars enables the inclusion of reduced levels of perfume in the bar composition.
US 2004/220064 is concerned with imparting fragrance perception to a product and a substrate, such as dry fabric or hair. It discloses a fragrance delivery vehicle comprising a water insoluble oil, a conditioner containing > 0.5 wt % of a cationic active and at least 0.1 wt % of a fragrance composition comprising specific aroma chemicals. Example 1 B discloses a softener composition comprising RYOTO ER290 in combination with HEQ derived from hardened tallow.
WO 01/46361 discloses compositions comprising (i) cationic softening compounds having two or more alkyl or alkenyl chains of at least C8 chain length, (ii) at least one oily sugar derivative and (iii) a deposition aid, which comprises a mixture of nonionic surfactant(s) and cationic polymer(s). Tables 3 and 4 disclose compositions comprising RYOTO ER290 and unsaturated di(tallowoyloxyethyl) dimethyl ammonium chloride.
WO 01/92447 discloses fabric conditioner compositions having defined viscosity properties, comprising a cationic fabric softener and a fatty acid partial ester of a polyhydric alcohol. Example 6 discloses Tetranyl AT-7590, which is a triethanolamine quaternary ammonium compound derived from partially saturated tallow having an iodine value of 34, in combination with ER290 (sucrose tetraerucate).
WO 02/04587 discloses a process for conditioning and fragrancing a substrate, which includes contacting a fragrance delivery vehicle containing a water insoluble oil, a cationic active, and at least 0.1 wt % of a fragrance composition with a substrate in an aqueous solution. The examples disclose compositions comprising HEQ (dialkylyloxy dimethyl ammonium chloride, where the alkyl is hardened tallow) and SPE (Ryoto ER290).
WO 03/087286 discloses a heat activated fabric treatment composition for use in a tumble dryer. The composition comprises a fabric treatment active, water, oil, which may be an oily sugar ester compound and an optional non-ionic surfactant. Example 10 discloses a composition comprising a tallow based TEA quat with an IV of about 35 and the sugar ester oil Emnon SCR-PK.
WO 97/15651 discloses an aqueous fabric softening composition comprising (a) a water insoluble quaternary ammonium compound comprising at least one ester link and two C12-28 alkyl or alkenyl groups, and (b) a sucrose ester or alkyl polyglucoside. Compositions comprising HEQ and sucrose esters of the Crodesta series are exemplified.
However, these approaches tend to be expensive, often requiring increased levels of specialised perfume ingredients. Furthermore, in soft fabric conditioners, the base odour can often still be noticed as a background smell, particularly during in-wear after the perfume has evaporated.
Another approach can be found in the prior art whereby odour masking is achieved by non-perfume ingredients. For example, WO 2008/020058 A2 (Dresden University), describes the use of mono- or di-saccharides for masking odours.
We have found that consumers easily discern base off-odour from under a perfume. There remains a need for ways of eliminating malodour arising from raw-materials which contain unsaturated fatty chains in compositions comprising them.
SPEs have been used as fabric softeners and are known as principle softeners, as co-softeners and as stabilisers.
More recently, SPEs have been found to give a perfume longevity benefit WO2007/078782 A1 (Procter & Gamble).
We have now surprisingly found that the base odour of raw materials containing unsaturated fatty chains can be reduced or eliminated by the use of certain sugar esters (SPEs).

Statement of the Invention

According to the present invention there is provided the use of a sucrose ester to reduce base off-odour in a composition comprising a quaternary ammonium compound having unsaturated fatty chains as described in any one of claim 1 to 9, wherein the sucrose ester is defined by the formula (I):

M(OH)_8-x (OC(O)R')_x

wherein, M(OH)₈ is sucrose in which M is the main backbone of the sucrose and (OH) represents the available hydroxyl groups on a sucrose molecule; x is an integer selected from 1 to 8, preferably 4; R' is a fatty chain and is linear or branched, cyclic or acyclic, saturated or unsaturated, substituted or unsubstituted and is independently selected from (C₈-C₁₈) and (C₂₀-C₂₂) with the proviso that, when R' is C₈-C₁₈, the iodine value of the fatty chains is from 0 to 25, preferably 0 to 20, more preferably from 1 to 5; and when R' is C₂₀-C₂₂, the iodine value of the fatty chains is from 0 to 120, preferably, from 20 to 100, most preferably from 25 to 80.
Further aspects of the invention provide for the use of a sugar ester in a composition to improve freshness of laundered articles, to improve clean smell of laundered articles and to improve the longevity of fragrance of a laundry conditioning product.

Detailed Description of the Invention

Sucrose esters (SPEs)

Sucrose ester is composed of a sucrose moiety having one or more of its hydroxyl groups esterified. Sucrose is a disaccharide. The sucrose molecule can be represented by the formula:

M(OH)₈

wherein M is the disaccharide backbone and there are a total of 8 hydroxyl groups in the molecule.
Thus, a suitable sucrose ester, can be represented by the following formula (I):

M(OH)_8-x(OC(O)R')_x formula (I)

wherein, M(OH)₈ is sucrose in which M is the main backbone of the sucrose and (OH) represents the available hydroxyl groups on a sucrose molecule;
x is an integer selected from 1 to 8, preferably 4 and is the hydroxyl groups that are esterified and (8-x) is the hydroxyl groups that remain unchanged;
R' is a fatty chain and is linear or branched, cyclic or acyclic, saturated or unsaturated, substituted or unsubstituted. Substituent groups can include, for example, hydroxyl, halide, alkoxy, and the like.
R' is independently selected from (C₈-C₁₈, preferably (C₁₂-C₁₈) and (C₂₀-C₂₂) with the proviso that, when R' is C₈-C₁₈, the iodine value of the fatty chains is from 0 to 25, preferably 0 to 20, more preferably from 1 to 5, most preferably from 1 to 2; and when R' is C₂₀-C₂₂, the iodine value of the fatty chains is from 0 to 120, preferably, from 20 to 100, more preferably from 25 to 90, most preferably from 25 to 80.
A mixture of chains may be used in the SPE.
Where R' is C₈-C₁₈, the sucrose ester is preferably solid, or substantially solid in nature, and has an iodine value of from 0 to 15, preferably from 0 to 10, more preferably from 0 to 5 and most preferably from 1 to 5.
The compositions are preferably substantially free and more preferably free from the presence of SPEs that do not conform to the formula (I) given above.
In a further embodiment, the unsaturated R' moieties may comprise a mixture of "cis" and "trans" forms about the unsaturated sites. The "cis" / "trans" ratios may range from about 1:1 to about 50:1, or from about 2:1 to about 40:1, or from about 3:1 to about 30:1, or from about 4:1 to about 20: 1.
The sucrose ester is present in compositions comprising a quaternary ammonium compound having unsaturated fatty chains, at a level of from 0.1 to 5, preferably from 0.2 to 4.5, more preferably from 0.2 to 4 % by weight of the total composition. A particularly preferred range is from 0.1 to 4 %, preferably from 0.2 to 3 %, more preferably from 0.5 to 2 %, even more preferably from 0.6 to 1.5 %.
The SPEs are preferably tallow or plant or vegetable based. Preferred plant and vegetable based SPEs include those derived from palm, canola, high erucate rape and soya bean.
Preferred sucrose esters are the Ryoto range (ex Mitsubishi) of liquid, soft solid or solid from and fully or partially hardened sucrose esters based on vegetable oils.
A further preferred sucrose ester is SCR-PK-H (ex Kao), which is derived from hardened palm kernel oil with a chain length of C₁₆ and mainly C₁₈.

Quaternary Ammonium Compound

The present invention relates to quaternary ammonium compounds having unsaturated chains. Such compounds are typically derived from fatty acyl or fatty acid feed stock having an Iodine Value of from 20 to 140, preferably from 20 to 60, more preferably from 20 to 50, most preferably from 25 to 45. The unsaturated chains come from the unsaturated fatty feed stock.
If there is a mixture of quaternary ammonium materials present in the composition, the iodine value, referred to above, represents the mean iodine value of the parent fatty acyl compounds or fatty acids of all of the quaternary ammonium materials present. Likewise, if there is any saturated quaternary ammonium quaternary ammonium materials present in the composition, the iodine value, referred to above, represents the mean iodine value of the parent fatty acyl compounds or fatty acids of all of the quaternary ammonium materials present.
Such compounds have a strong base odour of parent fatty compound such as tallow or oily smells from other plant sources such as palm. High IV softener materials hence require odour masking perfume and increased perfume levels which this invention circumvents.
Iodine value is defined as the number of grams of iodine absorbed per 100 g of test material. NMR spectroscopy is a suitable technique for determining the iodine value of the softening agents of the present invention, using the method described in Anal. Chem., 34, 1136 (1962) by Johnson and Shoolery and in EP 593,542 (Unilever, 1993).
The quaternary ammonium compound is preferably present in the compositions suitable for use in the invention at a level of from 2 % to 55 %, preferably from 3 % to 50 %, more preferably from 4 % to 40 % preferably from 5 % to 25 %, by weight of the total composition, for example from 6 to 20 % by weight.
In another embodiment, the quaternary ammonium compound may be present at a level of greater than 80 %, preferably 90 % by weight of the total composition.
The preferred quaternary ammonium fabric conditioner for use in compositions suitable for use in the present invention are the so called "ester quats".
Particularly preferred materials are the ester-linked triethanolammonium (TEA) quaternary ammonium compounds comprising a mixture of mono-, di- and tri-ester linked components.
Typically, such TEA-based fabric softening compounds comprise a mixture of mono, di- and tri-ester forms of the compound. Typically 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 first group of quaternary ammonium compounds (QACs) suitable for use in the present invention is represented by formula (I):

[(CH₂)_n(TR)]_m-(R¹).N⁺-(CH₂)_n(OH)]_3-mX^- (I)

wherein each R is independently selected from a C_5-35 alkyl or alkenyl group; R¹ represents a C_1-4 alkyl, C_2-4 alkenyl or a C_1-4 hydroxyalkyl group; T is generally O-CO. (i.e. an ester group bound to R via its carbon atom), but may alternatively be CO.O (i.e. an ester group bound to R via its oxygen atom); n is a number selected from 1 to 4; m is a number selected from 1, 2, or 3; and X^- is an anionic counter-ion, such as a halide or alkyl sulphate, e.g. chloride or methylsulphate. Di-esters variants of formula I (i.e. m = 2) are preferred and typically have mono- and tri-ester analogues associated with them. Such materials are particularly suitable for use in the present invention.
Especially preferred agents are preparations which are rich in the di-esters of triethanolammonium methylsulphate, otherwise referred to as "TEA ester quats".
Commercial examples include Tetranyl™ ex Kao, 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 and the Stepantex (ex Stepan) soft range, Stepantex VT90, VA90 and SP90.
A second group of quaternary ammonium compounds suitable for use in the invention is represented by formula (II):

(R¹)₃N⁺-(CH₂)_n-CH.(CH₂TR²)-TR² X^- (II)

wherein each R¹ group is independently selected from C_1-4 alkyl, hydroxyalkyl or C_2-4 alkenyl groups; and wherein each R² group is independently selected from C_8-28 alkyl or alkenyl groups; and wherein n, T, and X^- are as defined above.
Preferred materials of this second group include 1,2 bis[tallowoyloxy]-3-trimethylammonium propane chloride, 1,2 and 1,2-bis[oleoyloxy]-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 quaternary ammonium compounds 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 C_1-4 alkyl, or C_2-4 alkenyl groups; and wherein each R² group is independently selected from C_8-28 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.

Perfumes

The compositions for use in the invention are preferably free from perfume. The malodour reducing effect of the sugar esters are such that perfume is not required to mask the malodour. The compositions of the invention are preferably free from perfume. The malodour reducing effect of the sugar esters are such that perfume is not required to mask the malodour.
Useful components of the perfume include materials of both natural and synthetic origin. They include single compounds and mixtures. Specific examples of such components may be found in the current literature, e.g., in Fenaroli's Handbook of Flavor Ingredients, 1975, CRC Press; Synthetic Food Adjuncts, 1947 by M. B. Jacobs, edited by Van Nostrand; or Perfume and Flavor Chemicals by S. Arctander 1969, Montclair, N.J. (USA). These substances are well known to the person skilled in the art of perfuming, flavouring, and/or aromatizing consumer products, i.e., of imparting an odour and/or a flavour or taste to a consumer product traditionally perfumed or flavoured, or of modifying the odour and/or taste of said consumer product.
By perfume in this context is not only meant a fully formulated product fragrance, but also selected components of that fragrance, particularly those which are prone to loss, such as the so-called 'top notes'.
Top notes are defined by Poucher (Journal of the Society of Cosmetic Chemists 6(2):80 [1955]). Examples of well known top-notes include citrus oils, linalool, linalyl acetate, lavender, dihydromyrcenol, rose oxide and cis-3-hexanol. Top notes typically comprise 15-25%wt of a perfume composition and in those embodiments of the invention which contain an increased level of top-notes it is envisaged at that least 20%wt would be present within the encapsulate.
Some or all of the perfume or pro-fragrance may be encapsulated, typical perfume components which it is advantageous to encapsulate, include those with a relatively low boiling point, preferably those with a boiling point of less than 300, preferably 100-250 Celsius and pro-fragrances which can produce such components.
It is also advantageous to encapsulate perfume components which have a low Clog P (ie. those which will be partitioned into water), preferably with a Clog P of less than 3.0. These materials, of relatively low boiling point and relatively low Clog P have been called the "delayed blooming" perfume ingredients and include the following materials:

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

Preferred non-encapsulated perfume ingredients are those hydrophobic perfume components with a ClogP above 3. As used herein, the term "ClogP" means the 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-Isopropylphenol, 3-Isopropylphenol, 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, mEthylphenol, (+)-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 suitable 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.
In a further embodiment, the SPEs for use in the invention described above can be used in encapsulated form along with perfume.

Further Components

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 will preferably 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 trade name Pristerene™, ex Uniqema). Preferred fatty alcohols include hardened tallow alcohol (available under the trade names 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.
The compositions may further comprise a nonionic surfactant, especially where the level of quaternary ammonium compound is above about 8 % by weight of the total composition. Typically these can be included for the purpose of stabilising the compositions.
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--

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.
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.
Alternative stabilising agents may be used. Alternative stabilisers include single long chain ethoxylated cationic surfactant with a counter ion which is preferably an alkyl sulphate, such as methyl sulphate and ethyl sulphate, and most preferably is a methylsulphate counter-ion.
The single long chain cationic surfactants alternatives are alkoxylated cationic quaternary ammonium surfactants. Those suitable for use in this invention are generally derived from fatty alcohols, fatty acids, fatty methyl esters, alkyl substituted phenols, alkyl substituted benzoic acids, and/or alkyl substituted benzoate esters, and/or fatty acids that are converted to amines which can optionally be further reacted with another long chain alkyl or alkyl-aryl group; this amine compound is then alkoxylated with one or two alkylene oxide chains each having less than or equal to about 50 moles alkylene oxide moieties (e.g. ethylene oxide and/or propylene oxide) per mole of amine. Typical of this class are products obtained from the quaternization of aliphatic saturated or unsaturated, primary, secondary, or branched amines having one hydrocarbon chain from about 12 to about 22 carbon atoms alkoxylated with one or two alkylene oxide chains on the amine atom each having less than or equal to about 50 alkylene oxide moieties. The amine hydrocarbons for use herein have from about 12 to about 22 carbon atoms, and are preferably in a straight chain configuration. Suitable quaternary ammonium surfactants are made with one or two alkylene oxide chains attached to the amine moiety, in average amounts of less than or equal to about 50 moles of alkylene oxide per alkyl chain, more preferably from about 3 to about 20 moles of alkylene oxide, and most preferably from about 5 to about 12 moles of alkylene oxide per hydrophobic, e.g., alkyl group. Examples of suitable stabilizers of this type include Ethoquad® 18/25, C/25, and O/25 from Akzo and Variquat®-66 (soft tallow alkyl bis(polyoxyethyl) ammonium ethyl sulfate with a total of about 16 ethoxy units) from Goldschmidt.
Preferably, the compounds of the ammonium alkoxylated cationic surfactants have the following general formula:

{R1_m-Y-[(R2-O)_z-H]_p}⁺ X^-,

wherein R1 is selected from the group consisting of saturated or unsaturated, primary, secondary chain alkyl or alkyl-aryl hydrocarbons; said hydrocarbon chain having a length of from 12 to 22; each R2 is selected from the following groups or combinations of the following groups: - (CH₂)n- and/or - [CH(CH₃)CH₂]-; Y is selected from the following groups: = N⁺-(A)_q;-(CH₂)_n-N⁺-(A)_q;-B-(CH₂)_n-N⁺-(A)₂;-(phenyl)-N⁺-(A)_q;-(B-phenyl)-N⁺-(A)_q; with n being from about 1 to about 4.
Each A is independently selected from the following groups: H; R1; -(R2O)_z-H; -(CH₂)_xCH₃; phenyl, and substituted aryl; where 0 ≤ x ≤ about 3; and B is selected from the following groups : -O-; -NA-; -NA₂; -C(O)O-; and -C(O)N(A)-; wherein R2 is defined as hereinbefore; q = 1 or 2; and X^- is and m is from 1 to 4.
Preferred structures are those in which m = 1, p = 1 or 2, and 5 ≤ z ≤ 50, more preferred are structures in which m = 1, p = 1 or 2, and 7 ≤ z ≤ 20, and most preferred are structures in which m = 1, p = 1 or 2, and 9 ≤ z ≤ 12.
Preferred commercial surfactants include Tomah QC-15, cocopoly (15) oxyethylene methyl ammonium chloride (ex Tomah Products); and Rewoquat CPEM, coco pentaethoxymethyl ammonium methosulphate (ex Witco).
Another class of possible alternatives to non-ionic stabilisers are the long chain cationic surfactants based on quaternized amido-amine surfactants of the general structure;

R1-C(:O)-NH-[C(R2) (R3)]_n-N(CH₃) (R4) (R5)⁺ X^-

in which R1 = C12-30-alkyl, -alkenyl, -arylalkyl, and - (cycloalkyl)alkyl; R2 and R3 = H or C1-4-alkyl; R4 and R5 = C1-4-alkyl, -alkoxyalkyl, and -hydroxyalkyl; X^- is a halide or methylsulphate anion, preferably a methylsulphate anion counterion and n = 1-10
Preferred commercial surfactants include Rewoquat V3351, a tallow alkyl amido-amine methyl sulphate quat (ex Goldschmidt), Surfac ARF, a tallow amine ethoxy ammonium methyl sulphate (ex Surfachem).
The amido-amine single long chain cationic surfactants for use in the present invention may be alkoxylated. These alkoxylated amido-amine single chain cationic surfactants comprise one or more alkylene oxide chains each having less than or equal to about 50 moles alkylene oxide moieties (e.g. ethylene oxide and/or propylene oxide) per mole of amine. The preferred alkoxylated surfactants for use in the present invention comprise at least one ethoxylate group.
Yet other class of possible alternatives are given WO 95/27771 and include amphoteric surfactants including betaines and tegobetaines.

Further Optional Ingredients

The compositions for use in the invention may contain one or more other ingredients. Such ingredients include photobleaches, fluorescent agents, dyes, preservatives (e.g. bactericides), pH buffering agents, perfume carriers, hydrotropes, anti-redeposition agents, soil-release agents, polyelectrolytes, anti-shrinking agents, anti-wrinkle agents, anti-oxidants, sunscreens, anti-corrosion agents, drape imparting agents, anti-static agents and ironing aids. The products of the invention preferably contain pearlisers and/or opacifiers.
It is believed that those polymers which deposit on cloth as a part of their activity may assist in the deposition of perfume components present. These include cationic polymeric deposition aids. Suitable cationic polymeric deposition aids include cationic guar polymers such as Jaguar™ (ex Rhone Poulenc), cationic cellulose derivatives such as Celquats™ (ex National Starch), Flocaid™ (ex National Starch), cationic potato starch such as SoftGel™ (ex Aralose), cationic polyacrylamides such as PCG (ex Allied Colloids).

Product Form

A composition for use in the invention may be in dry solid or liquid form. The composition may be a concentrate to be diluted, rehydrated and/or dissolved 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 (C_1-4) alcohols.
The mineral salts may aid the attainment of the required phase volume for the composition, as may water soluble organic salts and cationic deflocculating polymers, as described in EP 41,698 A2 (Unilever). Such salts may be present at from 0.001 to 1% and preferably at from 0.005 to 0.1% by weight of the total composition. Examples of suitable mineral salts for this purpose include calcium chloride and magnesium chloride. The compositions of the invention may also contain pH modifiers such as hydrochloric acid. The short chain alcohols include primary alcohols, such as ethanol, propanol, and butanol, and secondary alcohols such as isopropanol. The short chain alcohol may be added with the cationic softening agent during the preparation of the composition.
The composition is preferably a fabric softener or fabric conditioner composition, and 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.
The compositions used in the invention are not detergent compositions and are preferably substantially free (for example having less than 0.1 weight %, preferably less than 0.05 weight % by weight of the total composition), more preferably free from one or more detersive surfactants such as anionic, ampholytic, zwitterionic surfactants, and cleaning soaps.
It is also possible, though less desirable, for the compositions for use in 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.

Method of Manufacture

In a typical method of manufacture, the cationic softening agent and SPE, and any optional components such as co-softener or complexing agent are heated together until a co-melt is formed. Water and other components are heated and the co-melt is added to the water with stirring.
Alternative methods of addition for the SPE will be to post dose it at the end of the process, as is, or as an emulsion. If the SPE is solid the batch temperature should be above its melting point for its emulsification by the softener active.

Examples

Embodiments of the invention are now illustrated with reference to the following non-limiting examples. Unless stated otherwise, all proportions are given in weight percent by weight of the total composition.

Example 1: Preparation of Compositions 4-7, Comparative Examples 1-3 and Control A

Compositions 4-7, Comparative Examples 1-3 and Control A were prepared in a bench top mixer equipped with a top 3-stage stirrer and a recirculation bath for temperature control. The quaternary softening agent, SPE, and complexing agent were heated together until a co-melt was formed. Water was heated and the co-melt added to the water with stirring. The batch was cooled to room temperature.
The process conditions were as follows:

Batch water temperature = 45 °C;
Co-melt temperature = 60 °C;
Co-melt addition time = 3 minutes;
Mixing time = 8 minutes;
Cooling time by cold water recirculation = 5 minutes;
Mixing speed = 500 RPM;
Batch size = 200 g.

For the purposes of odour assessment, no perfume was included in the compositions.
Three different sugar esters were tested, the details of the fatty acid chains are given in the following table:-

Sugar ester Main Chain length IV of fatty chains

THSBO C16-C18 110

ER290 C22 75

SCR-PK-H C16-18 0
THSBO (ex Clariant) is a pure sucrose polyester based on touch hardened soya bean oil.
ER290 (ex Mitsubishi) is a food grade pure sucrose polyester based on C22:1 erucic acid.
SCR-PK-H (ex KAO) is a sucrose polyester derived from hardened palm kernel oil (C16 and mainly C18) and contains about 20% impurities mainly fatty acids and soaps as specified in WO2006/076952 A1 (Unilever).

The composition of Compositions 4-7, Comparative Examples 1-3 and Control A are given in Table 1 below.

Table 1: Composition of Compositions 4-7, Comparative Examples 1-3 and Control A

Component	Control	Comparative Examples			Compositions
Component	A	1	2	3	4	5	6	7
Stepantex VT90	4.4	4	3.4	3	4	3.4	4	3.4
Stenol 16/18 L	0.48	0.48	0.48	0.48	0.48	0.48	0.48	0.48
THSBO	0	0.4	1	1.4	0	0	0	0
ER290	0	0	0	0	0.4	1	0	0
SCR-PK-H	0	0	0	0	0	0	0.4	1
demineralised water	to 100	to 100	to 100	to 100	to 100	to 100	to 100	to 100

Stepantex VT90 (ex Stepan) is a soft tallow TEA quaternary ammonium softening compound containing 90 % active and 10 % IPA.
Stenol 16/18 L (ex Cognis) is a fatty alcohol (complexing agent) with a mixture of C16 and C18 saturated chains.
Table 2 gives the ester distributions of the ER290 and SCR-PK sucrose polyesters used in these examples. Table 2: Ester distribution in ER290 and SCR-PK sucrose polyesters

Sucrose polyester Mono- di- Tri- Tetra- Penta- Hexa- Hepta- Octa-

ER290 0 5 17.5 19.1 20.5 20.3 10.8 3.8

SCR-PK 0 3.2 14.6 27.5 24.6 10.1 9.0 2.9
Table 3 gives the level of unsaturation and the odour description of the quaternary ammonium compound VT90. Table 3: Chain distribution and odour description of VT90.

Softener material Odour description C10 C12 C14 C14 uns C16 C16:1 C18 C18:1 C18: 2

VT90 Fatty/ tallow 0.1 0.1 2.7 0.3 30.6 2.2 32.6 28.6 2.8
The odour of sucrose polyesters was as follows:-

THSBO - neutral to very slightly oily
ER290 - neutral to very slightly oily
SCR-PK-H - slightly caramel (sucrose caramelised in synthesis process).

Example 2: Evaluation of the base odour from Comparative Examples 1-3

Terry towelling monitors measuring about 20 x 20 cm were desized by twice washing in a washing machine at 90 °C. Sets of two monitors were placed in Tergo pots with 1 litre of demineralised water per pot and agitated for 10 minutes.
The Tergos were dosed with the formulations in the amounts shown in Table 3 below and allowed to agitate for a further 15 minutes. The monitors were then removed and spinned and line dried.
Table 4 shows the amount of product used in each treatment to equalise the amount of VT90 deposited on the monitors. Table 4: Product dosage in Tergo-to-meters and the level of VT90 and sucrose polyester deposited per monitor for Comparative Example A and Compositions 1-3.

A 1 2 3

Product dose/g 2.0 2.28 2.50 2.93

VT90g/monitor 0.044 0.044 0.044 0.044

Sucrose polyester g/monitor 0.0 0.004 0.012 0.020
The monitors were line dried for three days. Then one monitor of each set was presented to an expert panel for odour evaluation whilst the other was kept in a bottle under fluorescent light (for build-up of odour). The odour descriptors used were based on those known in the art. The panel members described the odour and assigned a number to quantify the intensity of the odour they perceived. Table 5 summarises the outcome of this evaluation. Table 5. The average (of eight panellists) odour intensity and odour description of the treated monitors for monitors aged on line for three days.

A 1 2 3

Odour score 1.2 1.5 1.3 1.4

Odour quality Fatty Fatty, oily Fatty, oily Fatty, oily
The panel results show that there is very little difference between Compositions 1-3 and Control A. There was a directional worsening of the smell in presence of soyabean sucrose polyester and the rancid smell of oil was noticed by the panel.
This was reinforced by panelling the monitors kept in bottles (for build-up of odour) after 7 days. The monitors of Compositions 1 to 3 had developed strong rancid smells scoring between 2 to 4.

Evaluation of the base odour of Compositions 4 to 7

This set of experiments evaluated the odours in presence of erucate based ER290 and hard palm kernel sucrose polyesters.
The same procedure was followed as described above. Table 6: The product dosage in Tergo-to-meters and the level of VT90 and sucrose polyesters deposited per monitor.

A 4 5 6 7

Product dose/g 2.00 2.29 2.59 2.29 2.59

VT90 g/monitor 0.044 0.044 0.044 0.044 0.044

ER290 g/monitor 0.000 0.004 0.013 0.004 0.013
The monitors were line dried and on the first day one set presented to the panel and another set stored in bottles for later evaluation. Table 6 summarises the odour quality and scores. Table 7. Average (of 8 panellists) odour intensity and odour quality of day 1 of treated monitors.

A 4 5 6 7

Odour score 1.3 0.2 0.2 0.3 0.2

Odour quality Fatty, stale Clean, fresh Clean, fresh Clean, fresh Clean, fresh A hint sweet
The sucrose esters have efficiently suppressed the base odour of the soft tallow active on the monitors.
The monitors kept in bottles were presented to the panel after five days. The scores are summarised in Table 7. Table 8. Average (of eight panellists) odour intensity and odour quality of monitors kept in bottles for 5 days.

A 4 5 6 7

Odour score 1.6 0.5 0.9 0.6 0.6

Odour quality Fatty, stale Clean, hint green Clean, hint green Clean, fresh, hint green Clean, fresh Hint green
The monitors with sucrose polyesters in accordance with the invention have reduced the base odour efficiently and have a clean smell.
The monitors with SCR-PK-H were surprisingly preferred by the panel for softness.

Claims

Use of a sucrose ester to reduce base off-odour in a composition comprising a quaternary ammonium compound having unsaturated fatty chains; wherein the sucrose ester is defined by the formula (I):

M(OH)_8-x(OC(O)R')_x

wherein, M(OH)₈ is sucrose in which M is the main backbone of the sucrose and (OH) represents the available hydroxyl groups on a sucrose molecule; x is an integer selected from 1 to 8, preferably 4; R' is a fatty chain and is linear or branched, cyclic or acyclic, saturated or unsaturated, substituted or unsubstituted and is independently selected from (C₈-C₁₈) and (C₂₀-C₂₂) with the proviso that, when R' is C₈-C₁₈, the iodine value of the fatty chains is from 0 to 25, preferably 0 to 20, more preferably from 1 to 5; and when R' is C₂₀-C₂₂, the iodine value of the fatty chains is from 0 to 120, preferably, from 20 to 100, most preferably from 25 to 80.
Use according to claim 1, wherein R' is C₈-C₁₈, and the iodine value of the fatty chains is from 0 to 15.
Use according to claim 1 or claim 2, wherein the sucrose ester is solid and has an iodine value of from 0 to 10, preferably from 0 to 5.
Use according to any preceding claim, wherein the quaternary ammonium compound is derived from fatty feed stock having an Iodine Value of from 20 to 140, preferably from 20 to 60, more preferably from 20 to 50, most preferably from 25 to 45.
Use according to any preceding claim, wherein the sucrose ester is present at a level of from 0.1 to 5, preferably from 0.2 to 4.5, more preferably from 0.2 to 4 % by weight of the total composition.
Use according to any preceding claim, wherein the sucrose ester is derived from a source selected from the group consisting of tallow, plant and vegetable sources.
Use according to any preceding claim, wherein the quaternary ammonium compound is an ester-linked triethanolammonium (TEA) quaternary ammonium compound.
Use according to any preceding claim, wherein the quaternary ammonium 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.
Use according to any preceding claim, wherein the composition further comprises a fatty complexing agent.
Use according to any preceding claim, wherein the composition further comprises at least one perfume.
Use according to claim 10, wherein the perfume is present at a level of from 0.01 to 10 % by weight of the total composition.