WO2012052349A1 - Improvements relating to fabric conditioners - Google Patents

Abstract

A liquid rinse added fabric treatment composition comprising (a) a fabric treatment active in an amount of from 5 to 50 wt %, based on the total weight of the composition, (b) an antifoam in an amount of from 0.025 to 0.45 wt %, by weight of the total composition and 100 % antifoam activity, and (c) an antifreeze active wherein, the antifreeze active is an alkoxylated non-ionic surfactant having an average alkoxylation value of from 4 to 22 and a ClogP of from 3 to 6.

Description

IMPROVEMENTS RELATING TO FABRIC CONDITIONERS Technical Field The present invention relates to a fabric treatment composition, in particular a fabric softening composition, comprising an antifoam and an antifreeze agent, which show superior freeze-thaw recovery without compromising product performance. Background and Prior Art

The presence of anionic surfactant carry-over from a wash stage of a laundry process (particularly under hand washing conditions) can result in the presence of suds in the rinse. It is important to control suds in both machine and hand rinse conditions. In the case of machine-rinse conditions, uncontrolled sudsing can lead to temporary machine failure, known as suds lock. In the case of hand rinse conditions, sudsing is an undesirable user experience because it is a signal to the user that the laundry has not been effectively rinsed. The user will continue to rinse fabrics until suds are abated thereby wasting water, energy and time.

There is demand, therefore, for a fabric care composition that reduces and preferably eliminates suds, preferably during a first rinse step. There is also a continuing need to provide a fabric softening product that can be used in a first rinse solution without forming floes. Floes (e.g., scum residue), can be formed by the presence of some cationic fabric softener actives in the presence of anionic surfactant, negatively affecting the softness and visual performance.

The consumer perceives that fabrics are easier to rinse when foam quenching is improved and/or superior clarity of the liquor is evident. Foam quenching can be achieved by the inclusion of antifoam (for example silicone antifoam) in the composition and/or the addition of a surfactant scavenger (for example a monoalkyl quaternary ammonium compound). Such an approach is disclosed in EP 1370634 B1 (Procter & Gamble). Rinse-added fabric treatment compositions, which comprise a peroxygen bleaching agent, for improving the colour and/or clarity of the rinse water, are known from US2006/0030515 and US 2003/0216282 (both Procter & Gamble).

Reduced-rinse or single-rinse fabric treatment products (hereinafter referred to as "easy rinse" products) can save consumers time, effort and, where mains water is charged by usage, money. Reducing water usage also has an environmental benefit, particularly in countries such as China and India where water is in short supply.

A further problem that must be considered by the manufacturer of liquid fabric treatment products is the "freeze-thaw" phenomenon. In some parts of the world, where temperatures are very cold for part or all of the year, household products can be exposed to freezing conditions, particularly whilst in the supply chain. Freezing can occur overnight or for extended periods depending on the prevailing weather conditions. When the temperature rises, the behaviour of the product as it thaws is of critical importance to its performance and commercial viability. This so-called "freeze-thaw" behaviour can be particularly problematic for liquid products, for example fabric conditioners. In Russia and northern and inland parts of China, for example, during winter months, fabric conditioners can experience temperatures below minus 10°C causing products to freeze. Successful formulations for these markets must show good freeze recovery.

It is known to use antifreeze agents in fabric conditioners in parts of the world where freeze-thaw behaviour is an issue. Alcohol ethoxylates (nonionic surfactants) as antifreeze components are known, for example, from EP 0280550 B1 (Unilever), which discloses the addition of a non-ionic surfactant to a composition containing a cationic fabric softening agent and a fatty acid in order to obtain a composition that is stable after one and multiple freeze thaw cycles without the necessity of adding additional alcohol. US 5409621 (Unilever) discloses fabric conditioner compositions comprising 1 -80 % of a water insoluble cationic fabric conditioning material and 0.1 to 10 % of a non-ionic stabilising agent comprising a linear C8-C22 alcohol alkoxylated with 10 to 20 moles of alkylene oxide to provide a composition which is temperature stable.

EP 0922 755 A1 (Procter and Gamble) discloses the use of non-ionic alkoxylated stabilising agents in a liquid fabric softening composition as a freeze-thaw recovery agent. The compositions are not foam resistant. US2010/0144585 discloses a fabric softening composition, which maintains physical stability upon freeze-thaw, comprising a softening active, about 0.5 to 10 wt % of polydimethyl silicone, about 0.005 to 4 wt % of a non-ionic alkoxylated surfactant and about 0.005 to 15 wt% of a polyol. US5404621 (Ellis Simon R et al) discloses a process for making a liquid fabric softening composition comprising the steps of: (a) mixing and heating 1 -80 wt % of a water insoluble cationic fabric conditioning material of a defined formula and 0.1 -10 wt% of a non-ionic stabilising agent comprising a linear C8-22 alcohol alkoxylated with 10-20 moles of alkylene oxide to form a melt; and dispersing the melt in water to provide a fabric conditioning composition which is temperature stable at < 10°C and >25°C.

Many antifreeze agents, however, have foaming properties, which makes them unsuitable for use in easy rinse products, where foam must be kept to a minimum.

There is a need for the provision of easy rinse fabric conditioners which have acceptable freeze-thaw recovery properties as well as excellent foam quenching and rinse clarity performance. We have now surprisingly found that the inclusion of certain antifreeze additives in easy rinse compositions leads to excellent freeze-thaw properties whilst retaining the easy rinse functionality, despite the foaming nature of the additive - nonionic surfactants give persistent foam, which is difficult to rinse. Furthermore, the easy rinse property of rinse water clarity is unexpectedly improved. This combination of exceptional freeze-thaw attributes with superior easy rinse functionality in a fabric conditioner has not been achieved before.

Statement of the Invention

In a first aspect of the invention there is provided a liquid rinse added fabric treatment composition comprising

(a) a fabric treatment active in an amount of from 5 to 50 wt %, based on the total weight of the composition,

(b) an antifoam in an amount of from 0.025 to 0.45 wt %, by weight of the total composition and 100 % antifoam activity, and (c) an antifreeze active wherein, the antifreeze active is an alkoxylated non-ionic surfactant having an average alkoxylation value of from 4 to 22 and a ClogP of from 3 to 6. In a second aspect, there is provided a use of an antifreeze agent in a

composition as defined by the first aspect of the invention to improve freeze recovery of the composition. Detailed Description of the Invention

The Fabric Treatment Active The fabric treatment active can be in any suitable treatment composition, for example, a pre-treatment composition or a post-wash composition. A non-limiting example of a post wash composition is a rinse added fabric conditioner. A preferred fabric treatment composition is a fabric conditioner composition. Suitable fabric conditioner compositions for use in the invention comprise a fabric conditioning active. Suitable fabric conditioning compositions, are described below:-

The Fabric Conditioning Active

Preferably the fabric conditioning active is a fabric softening agent. The fabric softening agent may be cationic or non-ionic.

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

Fabric conditioning compositions which may comprise the fabric conditioning active in accordance with the invention may be dilute or concentrated, preferably concentrated. Products of the invention contain from 5 to about 50 %, preferably from 6 to about 25 % by weight of softening active, more preferably from about 7 to about 22 %, most preferably from 8 to 20 % by weight active.

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

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

Typically, TEA-based fabric softening compounds comprise a mixture of mono, di- and tri-ester forms of the compound where the di-ester linked component comprises no more than 70 % by weight of the fabric softening compound, preferably no more than 60 wt % of the fabric softening compound and at least 10 % of the monoester linked component. A preferred hardened type of active has a typical mono:di:tri ester distribution in the range of from 12 to 25 mono: from 55 to 65 di: from 15 to 27 tri. A soft TEA quat may have a typical mono:di:tri ester distribution of from 25 to 45 %, preferably from 30 to 40 % mono: from 45 to 60 %, preferably from 50 to 55 % di: and from 5 to 25 %, preferably from 10 to 15 % tri; for example 40:60: 10.

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

[(CH₂)_n(TR)]_m

I

R¹-N⁺-[(CH₂)n(OH)]₃-_m X- (I) wherein each R is independently selected from a C5-35 alkyl or alkenyl group; R¹ represents a Ci_-4 alkyl, C2- alkenyl or a Ci_-4 hydroxyalkyl group; T is generally O- CO. (i.e. an ester group bound to R via its carbon atom), but may alternatively be CO-O (i.e. an ester group bound to R via its oxygen atom); n is a number selected from 1 to 4; m is a number selected from 1 , 2, or 3; and X^" is an anionic counter- ion, such as a halide or alkyl sulphate, e.g. chloride or methylsulphate. Di-esters variants of formula I (i.e. m = 2) are preferred and typically have mono- and tri- ester analogues associated with them. Such materials are particularly suitable for use in the present invention.

Especially preferred agents are preparations which are rich in the di-esters of triethanolammonium methylsulphate, otherwise referred to as "TEA ester quats".

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

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

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

Also, soft quaternary ammonium actives such as Stepantex VK90, Stepantex VT90, SP88 (ex-Stepan), Prapagen TQ (ex-Clariant), Dehyquart AU-57 (ex- Cognis), Rewoquat WE18 (ex-Degussa) and Tetranyl L190 P, Tetranyl L190 SP and Tetranyl L190 S (all ex-Kao) are suitable.

A second group of QACs suitable for use in the invention is represented by formula (II): (R¹)₃N⁺-(CH₂)_n-CH-TR² X^" (II)

I

CH₂TR² wherein each R¹ group is independently selected from Ci_-4 alkyl, hydroxyalkyl or C2- alkenyl groups; and wherein each R² group is independently selected from C8-28 alkyl or alkenyl groups; and wherein n, T, and X^" are as defined above.

Preferred materials of this second group include 1 ,2 Jb/s[tallowoyloxy]-3- trimethylammonium propane chloride, 1 ,2 £>/s[hardened tallowoyloxy]-3- trimethylammonium propane chloride, 1 ,2-Jb/s[oleoyloxy]-3-trimethylammonium propane chloride, and 1 ,2 Jb/s[stearoyloxy]-3-trimethylammonium propane chloride. Such materials are described in US 4, 137, 180 (Lever Brothers).

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

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

(R¹)₂-N⁺-[(CH₂)n-T-R²]₂ X- (III) wherein each R¹ group is independently selected from Ci_-4 alkyl, or C_2-4 alkenyl groups; and wherein each R² group is independently selected from Cs-₂8 alkyl or alkenyl groups; and n, T, and X^" are as defined above. Preferred materials of this third group include bis(2-tallowoyloxyethyl)dimethyl ammonium chloride, partially hardened and hardened versions thereof.

The iodine value of the quaternary ammonium fabric conditioning material is preferably from 0 to 80, more preferably from 0 to 60, and most preferably from 0 to 45. The iodine value may be chosen as appropriate. Essentially saturated material having an iodine value of from 0 to 5, preferably from 0 to 1 may be used in the compositions of the invention. Such materials are known as "hardened" quaternary ammonium compounds.

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

wherein each R¹ group is independently selected from Ci_-4 alkyl, hydroxyalkyl or C2- alkenyl groups; R² group is independently selected from C8-28 alkyl or alkenyl groups, and X^" is as defined above.

Nonionic Softening Agents

The compositions of the invention may contain a non-cationic softening material, which is preferably an oily sugar derivative. An oily sugar derivative is a liquid or soft solid derivative of a cyclic polyol (CPE) or of a reduced saccharide (RSE), said derivative resulting from 35 to 100 % of the hydroxyl groups in said polyol or in said saccharide being esterified or etherified. The derivative has two or more ester or ether groups independently attached to a C8-C22 alkyl or alkenyl chain. Advantageously, the CPE or RSE does not have any substantial crystalline character at 20°C. Instead it is preferably in a liquid or soft solid state as herein defined at 20°C. The liquid or soft solid (as hereinafter defined) CPEs or RSEs suitable for use in the present invention result from 35 to 100% of the hydroxyl groups of the starting cyclic polyol or reduced saccharide being esterified or etherified with groups such that the CPEs or RSEs are in the required liquid or soft solid state. These groups typically contain unsaturation, branching or mixed chain lengths.

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

Preferably 35 to 85 % of the hydroxyl groups, most preferably 40-80 %, even more preferably 45-75 %, such as 45-70 % are esterified or etherified. Preferably the CPE or RSE contains at least 35 % tri or higher esters, e.g. at least 40 %.

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

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

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

The most highly preferred liquid CPEs or RSEs are any of the above but where the polyunsaturation has been removed through partial hydrogenation. Preferably 40 % or more of the fatty acid chains contain an unsaturated bond, more preferably 50 % or more, most preferably 60% or more. In most cases 65 % to 100 %, e.g. 65 % to 95 % contain an unsaturated bond.

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

In the context of the present invention, the term cyclic polyol encompasses all forms of saccharides. Indeed saccharides are especially preferred for use with this invention. Examples of preferred saccharides for the CPEs or RSEs to be derived from are monosaccharides and disaccharides. Examples of monosaccharides include xylose, arabinose, galactose, fructose, sorbose and glucose. Glucose is especially preferred. Examples of

disaccharides include maltose, lactose, cellobiose and sucrose. Sucrose is especially preferred. An example of a reduced saccharide is sorbitan.

The liquid or soft solid CPEs can be prepared by methods well known to those skilled in the art. These include acylation of the cyclic polyol or reduced

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

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

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

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

The length of the unsaturated (and saturated if present) chains in the CPE or RSE is C8-C22, preferably C-I2-C22- It is possible to include one or more chains of d-Cs, however these are less preferred. The liquid or soft solid CPEs or RSEs which are suitable for use in the present invention are characterised as materials having a solid: liquid ratio of between 50:50 and 0: 100 at 20°C as determined by T₂ relaxation time NMR, preferably between 43:57 and 0: 100, most preferably between 40:60 and 0: 100, such as, 20:80 and 0: 100. The T₂ NMR relaxation time is commonly used for

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

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

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

Where present, the CPE or RSE is preferably present in the composition in an amount of 0.5-50% by weight, based upon the total weight of the composition, more preferably 1 -30% by weight, such as 2-25%, e.g. 2-20%.

The CPEs and RSEs for use in the compositions of the invention include sucrose tetraoleate, sucrose pentaerucate, sucrose tetraerucate and sucrose pentaoleate. The Antifoam

The antifoam is present in an amount of from 0.025 to 0.45 wt %, preferably 0.03 to 0.4 wt %, most preferably from 0.05 to 0.35 wt %, for example 0.07 to 0.4 wt %, by weight of the total composition and based on 100 % antifoam activity. A wide variety of materials may be used as anitfoams, and antifoams are well known to those skilled in the art. See, for example, Kirk Othmer Encyclopedia of Chemical Technology, Third Edition, Volume 7, pages 430-447 (John Wiley & Sons, Inc., 1979).

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

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

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

European Patent Application No. 89307851. 9, published February 7, 1990, by Starch, M. S. Other silicone antifoams are disclosed in U. S. Patent 3, 455, 839 which relates to compositions and processes for defoaming aqueous solutions by incorporating therein small amounts of polydimethylsiloxane fluids. Mixtures of silicone and silanated silica are described, for instance, in German Patent Application DOS 2, 124, 526. Silicone defoamers and suds controlling agents in granular detergent compositions are disclosed in U. S. Patent 3, 933, 672, 35 Bartolotta et al, and in U. S. Patent 4, 652, 392, Baginski et al, issued March 24, 1987. Examples of suitable silicone antifoam compounds are the combinations of polyorganosiloxane with silica particles commercially available from Dow Corning, Wacker Chemie and Momentive.

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

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

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

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

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

Other antifoams useful herein comprise the secondary alcohols (e.g. , 2-alkyl alkanols as described in DE 40 21 265) and mixtures of such alcohols with silicone oils, such as the silicones disclosed in US 4,798,679, US 4,075, 1 18 and EP 150,872. The secondary alcohols include the C6-C16 alkyl alcohols having a CI-C16 chain like the 2-Hexyldecanol commercially available under the trade name ISOFOL16, 2-Octyldodecanol commercially available under the tradename ISOFOL20, and 2-butyl octanol, which is available under the trademark ISOFOL 12 from Condea. A preferred alcohol is 2-butyl octanol, which is available from Condea under the trademark ISOFOL 12. Mixtures of secondary alcohols are available under the trademark ISALCHEM 123 from Enichem. Mixed antifoams typically comprise mixtures of alcohol to silicone at a weight ratio of about 1 :5 to about 5: 1 . Further preferred antifoam agents are Silicone SRE grades and Silicone SE 47M, SE39, SE2, SE9 and SE10 available from Wacker Chemie; BF20+, DB310, DC1410, DC1430, 22210, HV495 and Q2-1607 ex Dow Corning; FD20P and BC2600 supplied by Basildon; and SAG 730 ex Momentive. Other suitable antifoams, described in the literature such as in Hand Book of Food Additives, ISBN 0-566-07592-X, p. 804, are selected from dimethicone,

poloxamer, polypropyleneglycol, tallow derivatives, and mixtures thereof.

Preferred among the antifoams described above are the silicone antifoams, in particular the combinations of polyorganosiloxane with silica particles.

The Antifreeze Component

The antifreeze agent as described below is used to improve freeze recovery of the composition.

The antifreeze active is an alkoxylated non-ionic surfactant having an average alkoxylation value of from 4 to 22, preferably from 5 to 20 and most preferably from 6 to 20. The alkoxylated non-ionic surfactant has a ClogP of from 3 to 6, preferably from 3.5 to 5.5. Mixtures of such non-ionic surfactants may be used.

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.

Suitable nonionic surfactants which can be used as the antifreeze component include in particular the reaction products of compounds having a hydrophobic group and a reactive hydrogen atom, for example aliphatic alcohols, acids, or alkyl phenols with alkylene oxides, preferably ethylene oxide either alone or with propylene oxide.

Suitable surfactants are substantially water soluble surfactants of the general formula:

R-Y-(C₂H₄0)_z-CH2-CH2-OH where R is selected from the group consisting of primary, secondary and branched chain alkyl and/or acyl hydrocarbyl groups (when Y = -C(0)0, R≠ an acyl hydrocarbyl group); primary, secondary and branched chain alkenyl hydrocarbyl groups; and primary, secondary and branched chain alkenyl- substituted phenolic hydrocarbyl groups; the hydrocarbyl groups having a chain length of from 8 to about 22, preferably 9 to 20, e.g. 10 to 18 carbon atoms.

In the general formula for the ethoxylated nonionic surfactant, Y is typically:

-O- , -C(0)0- , -C(0)N(R)- or -C(0)N(R)R- in which R has the meaning given above or can be hydrogen; and Z is from 4 to 15, preferably from 5 to 12, most preferably from 5 to 9.

Specific non-ionic surfactants are alkyl (C6-C22) phenols-ethylene oxide

condensates, up to 15 EO, i.e. up to 15 units of ethylene oxide per molecule, the condensation products of aliphatic (C8-C22) primary or secondary linear or branched alcohols with ethylene oxide, generally up to 22 EO, and products made by condensation of ethylene oxide with the reaction products of propylene oxide and ethylenediamine. The non-ionic surfactants may be linear or branched. Preferred non-ionic surfactants include Emulan TO 2080, supplied by BASF; Neodol™ 91 -6, supplied by Shell; Dehydol™ LT7 and Dehydol 2407, both available from Cognis; Synperonic™ A7, supplied by Croda and Genapol™ C-050 ex Clariant.

The amount of non-ionic surfactant is preferably in the range of from 0.1 to 4.5 wt % by weight, more preferably from 0.2 to 4.5 wt %, even more preferably from 0.6 to 4.0 wt %, still more preferably from 1 .0 to 4.0 wt % and most preferably from 1 .2 to 3.5 wt % by weight of the total composition.

The mole ratio of the cationic fabric softening agent to the antifreeze active is within the range from 40: 1 to about 1 : 1 preferably within the range from 18:1 to about 3: 1 . Further Optional Ingredients

Additional Antifreeze Materials

Additional antifreeze materials that may be added to the compositions of the invention include alcohols and diols. Suitable materials are given in

WO 2006 124338 A1 (Procter & Gamble) including polyols e.g. glycerol, pentaerythritol, glucose, fructose and maltose. Also momo propylene glycol, ethylene glycol, diethylene glycol and dipropylene glycol. Further suitable antifreeze materials are given in EP 2008 084206 and EP 2008 135 333 (both Henkel), including glycerine and glycerine in combination with compounds of the formula REO e.g. where

with 5EO or 7EO units; where R=Tallow with 20EO, or EO/PO mixtures of these.

Preferred additional antifreeze actives are selected from alcohols, diols and esters. A particularly preferred additional antifreeze is monopropylene glycol (MPG). Other non-ionic antifreeze materials, which are outside the scope of the non-ionic antifreeze component of the present invention but which may be additionally included in the compositions of the invention include alkyl polyglycosides, ethoxylated castor oils, and sorbitan esters.

Further suitable additional antifreeze agents are those disclosed in EP 0018039 (Procter & Gamble) including paraffins, long chain alcohols and several esters for example glycerol mono stearate, iso butyl stearate and iso propyl palmitate. Also materials disclosed in US 6063 754 (Quest) such as C10-12 isoparaffins, isopropyl myristate and dioctyladapate.

Thickening Polymers

Thickening polymers may be added to the compositions of the invention for further thickening. Any suitable thickener polymer may be used.

Suitable polymers are water soluble or dispersable. A high M.Wt, (for example, in the region of about 100,000 to 5,000,000) which can be achieved by crosslinking, is advantageous. Preferably, the polymer is cationic.

Polymers particularly useful in the compositions of the invention include those described in WO2010/078959 (SNF S.A.S.). These are crosslinked water swellable cationic copolymers having at least one cationic monomer and optionally other non-ionic and/or anionic monomers. Preferred polymers of this type are copolymers of acrylamide and trimethylaminoethylacrylate chloride.

Preferred polymers comprise less than 25 % of water soluble polymers by weight of the total polymer, preferably less than 20 %, and most preferably less than 15 %, and a cross-linking agent concentration of from 500 ppm to 5000 ppm relative to the polymer, preferably from 750 ppm to 5000 ppm, more preferably from 1000 to 4500 ppm. The cross-linking agent concentration must be higher than about 500 ppm relative to the polymer, and preferably higher than about 750 ppm when the crosslinking agent used is the methylene bisacrylamide, or concentrations of other cross-linking agents that lead to equivalent cross-linking levels of from 10 to 10,000 ppm.

Suitable cationic monomers are selected from the group consisting of the following monomers and derivatives and their quaternary or acid salts:

dimethylaminopropylmethacrylamide, dimethylaminopropylacrylamide, diallylamine, methyldiallylamine, dialkylaminoalkyl-acrylates and methacrylates, dialkylaminoalkyl-acrylamides or -methacrylamides.

Following is a non-restrictive list of monomers performing a non-ionic function: acrylamide, methacrylamide, N-Alkyl acrylamide, N-vinyl pyrrolidone, N-vinyl formamide, N-vinyl acetamide, vinylacetate, vinyl alcohol, acrylate esters, ally I alcohol.

Following is a non-restrictive list of monomers performing an anionic function: acrylic acid, methacrylic acid, itaconic acid, crotonic acid, maleic acid, fumaric acid, as well as monomers performing a sulfonic acid or phosphonic acid functions, such as 2-acrylamido-2-methyl propane sulfonic acid (ATBS) etc.

The monomers may also contain hydrophobic groups. Following is a non-restrictive list of cross-linking agents: methylene bisacrylamide (MBA), ethylene glycol diacrylate, polyethylene glycol dimethacrylate,

diacrylamide, triallylamine, cyanomethylacrylate, vinyl oxyethylacrylate or methacrylate and formaldehyde, glyoxal, compounds of the glycidyl ether type such as ethyleneglycol diglycidyl ether, or the epoxydes or any other means familiar to the expert permitting cross-linking. By way of preeminent preference the cross-linking rate preferably ranges from 800 to 5000 ppm (on the basis of MBA) relative to the polymer or equivalent cross-linking with a cross-linking agent of different efficiency. As described in US 2002/0132749 and Research Disclosure 4291 16, the degree of non-linearity can additionally be controlled by the inclusion of chain transfer agents (such as isopropyl alcohol, sodium hypophosphite, mercaptoethanol) in the polymerisation mixture in order to control the polymeric chain's length and the cross-linking density.

The final polymer has a water-soluble polymer fraction ranging below about 25 % by weight of the total polymer (as determined by a metering method such as that described on page 8 of patent EP 343840). The amount of polymer used in the compositions of the invention is suitably from 0.001 to 0.5 wt %, preferably from 0.005 to 0.4 wt %, more preferably from 0.05 to 0.35 wt % and most preferably from 0.1 to 0.25 wt %, by weight of the total composition. An example of the preferred polymer is Flosoft 270LS ex SNF. Organo-silicones

The compositions of the present invention may comprise an emulsified organo- silicone, which are useful as co-softeners. The terms silicones and organo- silicones are used interchangeably herein.

The organo-silicones which may be employed herein have a organic content of about 25 percent to about 90 weight percent. Preferably, the organo-silicone is in the form of an oil-in-water emulsion. In the emulsion, the silicone droplets are then preferably from 0.39 micrometres to 25 micrometres, preferable 1 micrometer to 15 micrometers, most preferably 2 micrometers to 10 micrometers. The droplet size may be determined based on volume measurements using by any suitable equipment, for example a Malvern X Mastersizer.

The silicone may be of any structure which gives rise to one or more of the desired benefits in use of the fabric softener formulation.

The silicone can be a polydi-Ci-6alkyl siloxane, which have the general formula R_aSiO(4-a) 2 wherein each R is the same or different and is selected from

hydrocarbon and hydroxyl groups, 'a' being from 0 to 3 and in the bulk material; 'a' has an average value of from 1 .85-2.2. The R group can be selected from the group C1 -22 alkyl, C2-22 alkenyl, C6-22 alkylaryl, aryl, cycloalkyl,

polyalkyleneoxide, and mixtures thereof.

In another embodiment of the invention the organosilicone can contain amino groups, with R selected from alkylamino and alkyldiamino groups.

The silicone fluid has a viscosity before emulsification (as measured on a

Brookfield RV4 viscometer at 25 degrees centigrade using spindle No.4 at 100 rpm) of from 350cSt to 750,000cSt, more preferably from 1 ,000cSt to 400,000cSt, most preferably 9,000cSt to 250,000cSt, e.g. 10,000cSt to 200,000 cSt.

Preferably, emulsification is effected using one or more cationic surfactants, preferably having a non-halogen counter-ion.

The cationic emulsifiers are believed to enhance deposition of the silicone during use of the fabric softening composition. Preferred counter-ions include methosulphate, ethosulphate, tosylate, phosphate and nitrate. If a halogen counter-ion is used, it is preferably chloride.

For example, mixtures of one or more cationic and one or more non-ionic surfactants can be used, or even non-ionic surfactant(s) alone.

Preferably, the total of amount of emulsifying surfactant(s) is from 0.5 percent to 20 percent, preferably from 2 percent to 12 percent, more preferably from 3 percent to 10 percent by weight of the silicone.

The emulsified silicone (as 100 percent active silicone) may be included in the fabric softener compositions in an amount of 0.5 percent to 15 percent by weight of the total composition (including the emulsion product containing the silicone emulsion), preferably 1 percent to 12 percent, more preferably 2 percent to 10 percent, most preferably 3 percent to 10 percent. However, it may be possible to include up to 20 percent by weight if it can be incorporated into the fabric softening composition without instability occurring therein.

Shading Dyes

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

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

Preferably the dye are bis-azo or tris-azo dyes are used.

Most referably, the direct dye is a direct violet of the following structures:

wherein:

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

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

R₂ is selected from: hydrogen, C1 -C4-alkyl, substituted or unsubstituted phenyl and substituted or unsubstituted naphthyl, preferably phenyl; R₃ and R₄ are independently selected from: hydrogen and C1 -C4-alkyl, preferably hydrogen or methyl;

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

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

The benzidene based dyes are less preferred.

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

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

Cotton substantive acid dyes give benefits to cotton containing garments.

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

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

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

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

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

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

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

Preferred azine dyes are: acid blue 98, acid violet 50, and acid blue 59, more preferably acid violet 50 and acid blue 98.

Other preferred non-azine acid dyes are acid violet 17, acid black 1 and acid blue 29.

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

The composition may comprise one or more hydrophobic dyes selected from benzodifuranes, methine, triphenylmethanes, napthalimides, pyrazole, napthoquinone, anthraquinone and mono-azo or di-azo dye chromophores. Hydrophobic dyes are dyes which do not contain any charged water solubilising group. Hydrophobic dyes may be selected from the groups of disperse and solvent dyes. Blue and violet anthraquinone and mono-azo dye are preferred. Preferred dyes include solvent violet 13, disperse violet 27 disperse violet 26, disperse violet 28, disperse violet 63 and disperse violet 77.

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

Basic Dyes

Basic dyes are organic dyes which carry a net positive charge. They deposit onto cotton. They are of particular utility for used in composition that contain

predominantly cationic surfactants. Dyes may be selected from the basic violet and basic blue dyes listed in the Colour Index International.

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

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

Preferably the reactive group is hydrolysed or reactive group of the dyes has been reacted with an organic species such as a polymer, so as to the link the dye to this species. Dyes may be selected from the reactive violet and reactive blue dyes listed in the Colour Index International. Preferred examples include reactive blue 19, reactive blue 163, reactive blue 182 and reactive blue, reactive blue 96.

Dye Conjugates

Dye conjugates are formed by binding direct, acid or basic dyes to polymers or particles via physical forces.

Dependent on the choice of polymer or particle they deposit on cotton or synthetics. A description is given in WO2006/055787. They are not preferred.

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

Perfume The compositions of the present invention may comprise one or more perfumes if desired. The perfume is preferably present in an amount from 0.01 to 10 % by weight, more preferably from 0.05 to 5 % by weight, even more preferably from 0.05 to 2 %, most preferably from 0.05 to 1 .5 % by weight, based on the total weight of the composition.

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

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

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

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

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

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

Preferred non-encapsulated perfume ingredients are those hydrophobic perfume components with a ClogP above 3. As used herein, the term "ClogP" means the logarithm to base 10 of the octanol/water partition coefficient (P). The

octanol/water partition coefficient of a PRM is the ratio between its equilibrium concentrations in octanol and water. Given that this measure is a ratio of the equilibrium concentration of a PRM in a non-polar solvent (octanol) with its concentration in a polar solvent (water), ClogP is also a measure of the

hydrophobicity of a material-the higher the ClogP value, the more hydrophobic the material. ClogP values can be readily calculated from a program called "CLOGP" which is available from Daylight Chemical Information Systems Inc., Irvine Calif., USA. Octanol/water partition coefficients are described in more detail in U.S. Pat. No. 5,578,563. Perfume components with a ClogP above 3 comprise: Iso E super, citronellol, Ethyl cinnamate, Bangalol, 2,4,6-Trimethylbenzaldehyde, Hexyl cinnamic aldehyde, 2,6-Dimethyl-2-heptanol, Diisobutylcarbinol, Ethyl salicylate, Phenethyl isobutyrate, Ethyl hexyl ketone, Propyl amyl ketone, Dibutyl ketone, Heptyl methyl ketone, 4,5-Dihydrotoluene, Caprylic aldehyde, Citral, Geranial, Isopropyl benzoate, Cyclohexanepropionic acid, Campholene aldehyde, Caprylic acid, Caprylic alcohol, Cuminaldehyde, 1 -Ethyl-4-nitrobenzene, Heptyl formate, 4- Isopropylphenol, 2-lsopropylphenol, 3-lsopropylphenol, Allyl disulfide, 4-Methyl-1 - phenyl-2-pentanone, 2-Propylfuran, Allyl caproate, Styrene, Isoeugenyl methyl ether, Indonaphthene, Diethyl suberate, L-Menthone, Menthone racemic, p-Cresyl isobutyrate, Butyl butyrate, Ethyl hexanoate, Propyl valerate, n-Pentyl propanoate, Hexyl acetate, Methyl heptanoate, trans-3,3,5-Trimethylcyclohexanol, 3,3,5- Trimethylcyclohexanol, Ethyl p-anisate, 2-Ethyl-1 -hexanol, Benzyl isobutyrate, 2,5-Dimethylthiophene, Isobutyl 2-butenoate, Caprylnitrile, gamma-Nonalactone, Nerol, trans-Geraniol, 1 -Vinylheptanol, Eucalyptol, 4-Terpinenol, Dihydrocarveol, Ethyl 2-methoxybenzoate, Ethyl cyclohexanecarboxylate, 2-Ethylhexanal, Ethyl amyl carbinol, 2-Octanol, 2-Octanol, Ethyl methylphenylglycidate, Diisobutyl ketone, Coumarone, Propyl isovalerate, Isobutyl butanoate, Isopentyl propanoate, 2-Ethylbutyl acetate, 6-Methyl-tetrahydroquinoline, Eugenyl methyl ether, Ethyl dihydrocinnamate, 3,5-Dimethoxytoluene, Toluene, Ethyl benzoate, n- Butyrophenone, alpha-Terpineol, Methyl 2-methylbenzoate, Methyl 4- methylbenzoate, Methyl 3, methylbenzoate, sec. Butyl n-butyrate, 1 ,4-Cineole, Fenchyl alcohol, Pinanol, cis-2-Pinanol, 2,4, Dimethylacetophenone, Isoeugenol, Safrole, Methyl 2-octynoate, o-Methylanisole, p-Cresyl methyl ether, Ethyl anthranilate, Linalool, Phenyl butyrate, Ethylene glycol dibutyrate, Diethyl phthalate, Phenyl mercaptan, Cumic alcohol, m-Toluquinoline, 6-Methylquinoline, Lepidine, 2-Ethylbenzaldehyde, 4-Ethylbenzaldehyde, o-Ethylphenol, p- Ethylphenol, m-Ethylphenol, (+)-Pulegone, 2,4-Dimethylbenzaldehyde,

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

It is commonplace for a plurality of perfume components to be present in a formulation. In the compositions of the present invention it is envisaged that there will be four or more, preferably five or more, more preferably six or more or even seven or more different perfume components from the list given of delayed blooming perfumes given above and/or the list of perfume components with a ClogP above 3 present in the perfume.

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

Co-Softeners And Fatty Complexing Agents

Co-softeners may be used, such as fatty acids. 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). Preferred fatty acids include hardened tallow fatty acid (available under the tradename Pristerene™, ex Uniqema). Preferred fatty alcohols include hardened tallow alcohol (available under the tradenames Stenol™ and Hydrenol™, ex Cognis and Laurex™ CS, ex Albright and Wilson).

The compositions for use in the present invention may comprise a fatty

complexing agent.

Especially suitable fatty complexing agents include fatty alcohols.

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

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.

Further Optional Ingredients

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

The compositions of the present invention are liquid rinse added fabric treatment compositions suitable for use in a laundry process.

The compositions of the invention may also contain pH modifiers such as hydrochloric acid or lactic acid. The liquid compositions preferably have a pH of 2.0 to 3.5, preferably about 2.5 to 3.0. The composition is preferably for use in the rinse cycle of a home textile laundering operation, where, it may be added directly in an undiluted state to a washing machine, e.g. through a dispenser drawer or, for a top-loading washing machine, directly into the drum. The compositions may also be used in a domestic hand-washing laundry operation.

It is also possible for the compositions of the present invention to be used in industrial laundry operations, e.g. as a finishing agent for softening new clothes prior to sale to consumers. Preparation Of The Compositions Of The Invention

The compositions of the invention may be made by combining a melt comprising the fabric softening active with an aqueous phase. A preferred method of preparation for a dilute is as follows:-

1 . Heat water to about 40 to 50°C.

2. Add any minor ingredients, such as acid, sequestrants and preservatives.

3. Melt the softening active, antifreeze and any co-active together to form a co-melt. 4. Add the co-melt to the heated water phase.

5. Add dyes and remaining minor ingredients.

6. Cool.

7. Add perfume and antifoam.

Examples

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

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

Unless otherwise stated, amounts of components are expressed as a percentage of the total weight of the composition.

Example 1 :- Preparation of Composition 1 and Comparative Examples A to C and X A fabric conditioner composition was prepared, which contained an antifoam and a non-ionic antifreeze in accordance with the invention. This was designated "composition 1 ".

A comparative composition was prepared, containing an antifoam and an antifreeze compound, mono propylene glycol (MPG), which is outside the scope of the invention. This was designated "composition A."

Comparative fabric conditioner compositions were prepared, which also contained an antifoam, but which did not comprise an antifreeze agent. These were designated "composition B and composition C". Comparative example X was also prepared, which represents a prior art composition.

The compositions were prepared using the following process (for compositions B and C, no antifreeze was added at step 4):-

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

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

3. The preservative and sequestrant were then added.

4. The softening active, antifreeze and fatty alcohol were melted together at ca. 65°C to form a co-melt.

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

6. Dyes, pearlescer and salt were then added and mixed.

7. The resulting was cooled.

8. The perfume and antifoam were added at about 35°C.

The compositions of the fabric conditioners are given in Table 1 .

Table 1 : Composition (wt %) of the Fabric Conditioners 1, A-C and X

¹Palm based soft TEA Quat

²Pearlescer, preservative, sequestrant, etc

³Based on 100 % activity

Example 2:- Freeze/Thaw Recovery Of Compositions 1 , A and B

The freeze/thaw recovery behaviour of Compositions 1 , A and B was assessed as follows:

Dispersion and viscometer measurements were carried out on freshly made compositions prior to the freeze-thaw tests (to give "initial" values). I) Freeze Thaw

1 ) The compositions were stored at minus 18°C for 8 hours.

2) The compositions were then thawed at room temperature (20-25°C) for 16 hours.

3) This freeze/thaw cycle was repeated 5 times.

4) The compositions were then thawed for 48 hours at room temperature and dispersion and viscometer measurements were carried out and compared to initial measurements. ll) - 5°C and -10°C

The compositions were stored at minus 5°C or minus 10 °C for 5 days and the visual properties assessed daily. The compositions were then thawed for 48 hours at room temperature before the "final" dispersion and viscometer measurements were carried out.

The following visual assessments of the compositions were carried out over the duration of the test. The following scales were used, where properties progressively worsen up the scale, starting from 1 :-

1 ) Pouring characteristics

1 = Good, homogenous fluid properties

2 = Stringy or elastic

3 = Lumpy

4 = Distinct low and high viscosity regions 2) Dispersion Test

This was determined by dispersion of 20 ml of product in 1 litre of water at 20°C. Instant dispersion (designated herein "instant dispersion") was assessed using the following scale. A further assessment may be carried out after agitation of the dispersion (designated herein "agitated dispersion").

1 = Excellent

2 = Good

3 = Medium

4 = Poor

5 = Very poor

3) Separation

1 = No separation

2 = Cracked

3 = Evidence of some phase separation can be seen.

4 = Extensive phase separation has occurred

4) Visual Viscosity

1 = Good, the same as the initial viscosity

2 = Thick

3 = Very thick

4 = Gel / soft solid

5 = Solid 5) Appearance

1 = Good, the same as the original colour

2 = Pearlesced or marbled

3 = Opaque / white

Viscometer Viscosity Measurement

Viscosities of compositions 1 , A and B were measured using a Thermo Fisher RS600. Each sample was measured with a "cup and bob" geometry and the viscosity continuously measured under shear at 2s^"1 for 60 seconds, followed by 60 seconds at 20s^"1, followed by 60 seconds at 106s^"1, at 25°C.

The results of these assessments are given in Tables 2 and 3 below:-

Table 2: Viscosity and dispersion properties of compositions 1, A and B at initial and following 5 freeze-thaw cycles

It will be seen that the final viscosities of composition 1 were consistently lower ^' comparison to that of A and B.

The dispersion tests also showed better overall performance for composition 1 before and after the tests. Table 3: Pouring Characteristics of compositions 1 , A and B at initial and following 1 -5 freeze-thaw cycles

Pouring characteristics: 1 = Good, homogenous fluid properties; 2 = Thick, stringy or elastic; 3 = Lumpy and/or jelly-like; 4 = Distinct low and high viscosity regions

All samples were found to freeze within 24 hours at -10°C.

Control without any antifreeze additives showed poor recovery from freezing: product became highly viscous and attained a lumpy and stringy texture on pouring.

The addition of Neodol 91 -6 showed a full recovery after each cycle - product retained its low viscosity and had excellent pouring characteristics.

Overall, it will be seen that the products with nonionic recovered faster i.e.

achieved a liquid and pourable state sooner than products without the additive.

Example 3:- Foaming properties of Compositions 1 , A-C and X

The foam quenching properties of Compositions 1 , A, B, C and X were assessed as follows: Visual assessments of the compositions were carried out over the duration of the test. The following scales were used, where properties progressively worsen up the scale. 1 ) Surface foam

1 = No bubbles, clean surface

2 = 100 % coverage with very small bubbles

3 = 100 % coverage with medium sized bubbles

4 = 100 % coverage with large foamy bubbles

2) Solution clarity

0 = Clear

1 = Slightly Hazy

2 = Hazy

3 = Cloudy

4 = Very Cloudy

5 = Opaque

I) Intrinsic lathering properties in water

Each composition 1 , A-C and X was added to water and shaken to assess intrinsic lathering properties. The procedure was as follows:-

1 . The composition was dosed into water at a concentration of 4g/litre (5g/l was used for C).

2. 500ml of the resulting mixture was placed in a 750ml container and shaken vertically 5 times. 3. The container was then left to stand (at time = 0) and the time taken for the lather to disappear was measured. This was designated "time to lather kill".

The results are given in Table 4 below.

Table 4:- Lathering properties (time to lather kill, surface foam and solution clarity) for compositions 1, A, B, C and X

¹ 0= Clear; 1 = Slightly Hazy; 2 = Hazy; 3 = Cloudy; 4 = Very Cloudy; 5 = Opaque ²1 = No bubbles, clean surface; 2 = 100% coverage with very small bubbles; 3 = 100% coverage with medium sized bubbles; 4 = 100% coverage with large foamy bubbles

It will be seen that the composition in accordance with the invention provides dramatically better lather resistance properties than those out with the scope of the invention.

II) Resistance to lathering under anionic carryover conditions

Anionic carryover conditions (from wash to rinse bath) were simulated by adding aliquots of an aqueous solution of washing powder to water. Each composition 1 , A, B, C and X was then added to this water and shaken to assess intrinsic anti- lathering properties. The procedure was as follows:-

1 . A main wash detergent powder (Omo Powder) was dosed into water at a concentration of 2g/litre. 2. Meanwhile, each fabric conditioner composition was dosed into water at a concentration of 4g/litre, as above.

3. A 2 ml aliquot of the main wash detergent solution of step 1 was then

added to the solution of step 2.

4. 500ml of the resulting mixture was placed in a 750ml container and shaken vertically 5 times.

5. The container was then left to stand (at time = 0) and the time taken for the lather to disappear was measured. This was designated "time to lather kill".

6. Steps 3 to 5 were repeated up to four times.

The results are given in Table 5 below.

Table 5:- Lathering properties (time to lather kill, surface foam and solution clarity) for compositions 1, A, B, C and X

¹ 0= Clear; 1 = Slightly Hazy; 2= Hazy; 3= Cloudy; 4= Very Cloudy; 5 = Opaque ²1 = No bubbles, clean surface; 2 = 100% coverage with very small bubbles; 3 = 100% coverage with medium sized bubbles; 4 = 100% coverage with large foamy bubbles. Surprisingly, all the antifoam properties are better for the composition in accordance with the invention, particularly for solution clarity, which shows a synergistic benefit. A, containing the antifreeze MPG, does not show any improvement over B for antifoam benefits. In summary the presence of the non-ionic antifreeze agent, in accordance with the invention, leads to faster, more efficient foam kill, improved appearance of the solution surface (and in fact enables a foam free benefit), improved solution clarity and improved resistance to main wash product, providing consistently better foam kill and clarity throughout.

Example 4:- Preparation of Compositions 2 and 3 in accordance with the invention and Comparative Examples D, E, F and G

A further six fabric conditioner formulations were prepared using the following method:

1 . The softening active and non-ionic surfactants (where present) were melted together at about 65°C to form a co-melt

2. The water was heated to about 45 °C with stirring.

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

4. The preservative, acid and sequestrant were then added with mixing.

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

6. Dyes, pearlescer and salt were then added and mixed.

7. The resulting product was cooled.

8. The perfume and antifoam were added at about 35°C.

9. Mix and cool product. A fabric conditioner, designated "Composition 2"', was prepared with the same composition as Composition 1 in Table 1 above. This composition contained the non-ionic surfactant Dehydol LT7, which has an ethoxylation value of 7. Composition 3 contained the non-ionic surfactant Emulan TO 2080, which has an ethoxylation value of 20.

A comparative fabric conditioner, designated "Comparative Example D", was prepared, with no antifreeze active and containing the non-ionic surfactant Lutensol AT25, having an ethoxylation value of 25.

Comparative Example E contained no non-ionic surfactant.

Comparative Example F contained a high level of Lutensol AT25.

Comparative Example G contained a non-ionic surfactant, having an alkoxylation value of 8 and a ClogP of 6.65.

The compositions of the fabric conditioners are given in Table 6.

Table 6: Composition (wt %) of the Fabric Conditioners 2, 3, D, E, F and G

¹ Palm based soft TEA Quat, ex FXG

2Pearlescer, preservative, sequestrant, dye, etc

3Based on 100 % activity

Emulan TO 2080 (Ci₂-u; 20 EO; Clog P 3.87), ex BASF

5Dehydol LT7 (Ci₂-u; 7 EO; ClogP 5.37), ex Cognis

6Myrj S8 (Ci₈; 8 EO; ClogP 6.65), ex Croda

7Lutensol AT25 (25 EO; ClogP 5.41 ), ex BASF

Example 5:- Freeze/thaw recovery of Compositions 2 and 3 in accordance with the invention and Comparative Examples D, E, F and G

The freeze/thaw recovery behaviour of Compositions 2, 3, D, E, F and G was assessed as described in Example 2 above. The results are shown in Table 7 below.

Table 7: Visual dispersion (agitated) scores of compositions 2, 3, D, E, F and G at initial and following 5 freeze-thaw cycles

All samples froze within 24 hours.

Compositions D, E, F and G, without antifreeze additives in accordance with the invention, showed less effective recovery from freezing. It was further found these products became highly viscous and attained a lumpy and stringy texture on pouring, whereas those compositions in accordance with the invention, however, showed a good recovery after each cycle, with the products retaining acceptable pouring characteristics. Example 6:- Foaming properties of Compositions 2, 3, D, E, F and G

The foam quenching properties of Compositions 2, 3, D, E, F and G were assessed as described above in Example 3, and visual assessments of the compositions were carried out over the duration of the test.

I) Intrinsic lathering properties in water

Each composition was added to water and shaken to assess intrinsic lathering properties. The procedure was as follows:-

1 . The composition was dosed into water at a concentration of 4g/litre.

2. 500ml of the resulting mixture was placed in a 750ml container and shaken vertically 5 times.

3. The container was then left to stand (at time = 0) and the time taken for the lather to disappear was measured. This was designated "time to lather kill".

The results are given in Table 8 below. Table 8:- Lathering properties (time to lather kill, surface foam and solution clarity) for compositions 2, 3, D, E, F and G

' 0= Clear; 1 = Slightly Hazy; 2= Hazy; 3= Cloudy; 4= Very Cloudy; 5 = Opaque

²1 = No bubbles, clean surface; 2 = 100% coverage with very small bubbles; 3 = 100% coverage with medium sized bubbles; 4 = 100% coverage with large foamy bubbles It will be seen that the compositions in accordance with the invention provide better lather resistance properties than comparative examples D and E.

Comparative examples F and G exhibit good lather resistance but poor freeze recovery (Table 7).

II) Resistance to lathering under anionic carryover conditions

Anionic carryover conditions (from wash to rinse bath) were simulated by adding aliquots of an aqueous solution of washing powder to water. Each composition 2, 3, D, E, F and G was then added to this water and shaken to assess intrinsic anti- lathering properties.

The procedure was as given in Example 3 above. The results are given in Table 9 below.

Table 9:- Lathering properties (time to lather kill, surface foam and solution clarity) for compositions 2, 3, D, E, F and G

2d 1 _ = No bubbles, clean surface; 2 = 100% coverage with very small bubbles; 3 = 100% coverage with medium sized bubbles; 4 = 100% coverage with large foamy bubbles

The compositions in accordance with the invention exhibit a combination of superior freeze/thaw properties and excellent foam quenching properties, unlike the comparative examples, which only exhibit good performance in one area or the other.

Claims

1 . A liquid rinse added fabric treatment composition comprising

(a) a fabric treatment active in an amount of from 5 to 50 wt %, based on the total weight of the composition,

(b) an antifoam in an amount of from 0.025 to 0.45 wt %, by weight of the total composition and 100 % antifoam activity, and

(c) an antifreeze active wherein, the antifreeze active is an alkoxylated non-ionic surfactant having an average alkoxylation value of from 4 to 22 and a ClogP of from 3 to 6.

2. A composition as claimed in claim 1 , wherein the fabric treatment

composition is a rinse added fabric softening composition and wherein the fabric treatment active is a fabric softening active. 3. A composition as claimed in claim 2, wherein the fabric softening active is an ester-linked quaternary ammonium active compound. 4. A composition as claimed in claim 3, wherein the ester-linked quaternary ammonium active compound is selected from those represented by formula

[(CH₂)_n(TR)] |m

R¹-N⁺-[(CH₂)n(OH)]₃-_m X- (I) wherein each R is independently selected from a C5-35 alkyl or alkenyl group; R¹ represents a Ci_-4 alkyl, C2- alkenyl or a Ci_-4 hydroxyalkyl group; T is generally O-CO. (i.e. an ester group bound to R via its carbon atom), but may alternatively be CO-0 (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; and those represented by formula (III): (R¹)₂-N⁺-[(CH₂)n-T-R²]₂ X- (III) wherein each R¹ group is independently selected from Ci_-4 alkyl, or C_2-4 alkenyl groups; and wherein each R² group is independently selected from Cs-₂8 alkyl or alkenyl groups; and n, T, and X^" are as defined above.

A composition as claimed in any preceding claim, wherein the fabric treatment active is present in an amount of from 6 to 25 wt %, by weight of the total composition.

A composition as claimed in any preceding claim, wherein the antifoam comprises silicone.

7. A composition as claimed in any preceding claim, wherein the antifoam comprises silica.

8. A composition as claimed in any preceding claim, wherein the antifoam is present in an amount of from 0.03 to 0.4 wt %, by weight of the total composition and 100 % antifoam activity.

9. A composition as claimed in any preceding claim, wherein the alkoxylated non-ionic surfactant is present in an amount of from 0.1 to 4.5 % by weight of the total composition.

10. A composition as claimed in any preceding claim, wherein the alkoxylated non-ionic surfactant has an average EO value of from 5 to 20 EO.

1 1 . A composition as claimed in any preceding claim, wherein the alkoxylated non-ionic surfactant has a ClogP of from 3.5 to 5.5.

12. A composition as claimed in any preceding claim, which further comprises an additional antifreeze active selected from alcohols, diols and esters.

13. A composition as claimed in claim 12, which further comprises mono

propylene glycol.

14. Use of an antifreeze agent in a composition as defined in any one of claims 1 to 13 to improve freeze recovery of the composition.