EP3234086A1

EP3234086A1 - Pourable liquid fabric conditioner compositions

Info

Publication number: EP3234086A1
Application number: EP15798483.2A
Authority: EP
Inventors: Christopher Boardman; Elizabeth Ann Clowes; Peter Graham; David Stephen Grainger; Robert Allan Hunter; Janette Perry
Original assignee: Unilever PLC; Unilever NV
Current assignee: Unilever PLC; Unilever NV
Priority date: 2014-12-15
Filing date: 2015-11-25
Publication date: 2017-10-25
Anticipated expiration: 2035-11-25
Also published as: TR201815223T4; CN107109297B; BR112017012522A2; WO2016096347A1; CN107109297A; EP3234086B1

Abstract

A pourable liquid fabric conditioning composition comprising: a) a cationic fabric softening active; b) viscosity increasing particles, having a volume average particle size of 25 to 5000 microns, the particles comprising less than 50 wt%, based on the particle, of crosslinked water swellable polymer, and at least 50 wt%, based on the particle, of absorbed water the amount of polymer being at least 0.1 wt% of the fabric conditioning composition; and c) further water, the composition having a viscosity in the range of from 60 to 3500 mPas at 106s^-1at25 °C.

Description

POURABLE LIQUID FABRIC CONDITIONER COMPOSITIONS

TECHNICAL FIELD The present invention relates to pourable liquid fabric conditioner compositions comprising viscosity modifying polymers.

BACKGROUND AND PRIOR ART Consumer preference is for fabric conditioners to have a viscosity of at least 30 mPas at 25°C and 106s^"1. The higher the concentration of conditioning active (cationic) and the lower the recommended dose, the higher the inherent composition viscosity becomes and the more it becomes an issue for effective dispensing. The viscosity of liquid compositions that would otherwise be too thin for consumer preference can be increased by addition of a thickening polymer. One such additive consists of polymer gels <10 microns in diameter when swollen with water. These particles display strong colloidal interactions and increase viscosity at the expense of reduced dispersibility. This poor dispersibility leads to major problems if the product is to be dispensed from a washing machine drawer and is also perceived as unsatisfactory when hand washing. Poor dispersion leads to poor fabric conditioning.

A structured fabric conditioning liquid comprises multiple phases in which a cationic softening active (typically a quaternary ammonium compound) is suspended in water. Water and a dispersion of immiscible softening active typically exist as a structured bi- layer microstructure, e.g. multilayer vesicles. The resulting liquid exhibits complex flow behaviour (non Newtonian flow) and short to medium range ordering within the liquid.

GB1428062 discloses fabric softening compositions comprising a cationic softener compound and a water-insoluble particulate material having an average particle size of 1 to 50 microns. The addition of this insoluble particulate material is said to enhance the properties of the softened fabric. Glass beads and micro balloons, starch and other low swelling materials are exemplified. It is taught that particulate materials with high swelling power (>15) should be avoided as such swelling detracts from the benefits. Deposition of such a large mass of solid particles onto clothing is not desirable.

WO2010/079100 discloses fabric conditioner compositions comprising cationic polymeric thickeners exhibiting a low fraction of water soluble polymers and a relatively high level of cross-linking, which results in a markedly improved weight efficiency and reduction in the re-deposition of soil. These polymers comprise particles that are too small to provide the desired dispersion improvements. SUMMARY OF THE INVENTION

According to the invention there is provided a pourable liquid fabric conditioning composition comprising: a) a cationic fabric softening active;

b) viscosity increasing particles, having a volume average particle size of 25 to 5000 microns, the particles comprising less than 50 wt%, based on the particle, of crosslinked water swellable polymer, and at least 50 wt%, based on the particle, of absorbed water the amount of polymer being at least 0.1 wt% of the fabric conditioning composition; and

c) further water,

the composition having a viscosity in the range of from 60 to 3500 mPas at 106s^"1 at

25 °C.

Also according to the invention there is a method of providing a liquor for the conditioning of fabrics comprising the step of dispersing a composition according to the invention in water. DETAILED DESCRIPTION OF THE INVENTION

The Composition The composition is a dispersible, pourable liquid fabric conditioner composition. By dispersible is meant that the particles separate throughout a liquid to form a dispersion on addition of water. Good dispersion is characterised by good, uniform separation of the particles in the liquid, and by the speed of the separation. A suitable method for dispersion assessment is described below. This gives a Dispersion Index (Dl) on a scale of 1 to 5.

17 ml of a composition to be tested is poured from a container into 1000 ml of cold tap water in a 2000 ml beaker. After 30 seconds the resultant mix is visually assessed and ranked on a scale of 1 - 5, using half scores where appropriate. The scale is defined as follows:-

Rating 1 : the solution is uniformly dispersed with no lumps or bits. Rating 2: The product disperses giving an even dispersion with only a few small lumps or bits.

Rating 3: The product disperses to give mainly small lumps or bits, but the dispersion is fine and gives lightly cloudy/coloured solution.

Rating 4: The product breaks up into a few medium and/or large sized lumps with no fine dispersion; the water remains substantially clear and colourless.

Rating 5: The product does not break up at all on entering the water. It typically forms one or two large lumps in clear water.

If desired, the mixture may be stirred by performing 5 revolutions at a rate of one per second with a flat spatula before being re-assessed using the same rating scale. Fabric conditioners of the present invention are dispersed in water prior to or during use.

The compositions have a viscosity that is preferably in the range of from 80 to 1000 mPas, more preferably from 120 to 500, even more preferably from 180 to 350 mPas at 25°C and 106s^"1. Any suitable viscometer can be used, for example, a Haake VT550, or a Thermo Fisher RS600.

The composition is preferably substantially free from conventional thickening polymers, meaning 0 to 1 wt% conventional thickening polymer may be used in the composition, preferably 0 to 0.05 wt %, more preferably 0 to 0.01 wt %, most preferably zero wt %. By conventional thickening polymers, in the context of this invention is meant extended polymer molecules that reach across long-length scales within the solution phase (for example, modified cellulose materials such as hydroxyl-ethyl cellulose (HEC), sodium carboxy-methyl cellulose (SCMC), or Xanthan gum), associative thickeners which link between surfactant micelles or liquid crystal domains (e.g. hydrophobically modified polyacrylates (hydrophobic alkali swellable emulsions - HASE)), and small particle microgels which occupy sufficient phase-volume to increase the viscosity of the solution phase as described by the Krieger-Dougherty equation (e.g. polyacrylates (carbomers)). The microgel particles of conventional thickeners are much smaller (<10 micron) in the composition than the particles used in the present invention, and display a strong colloidal interaction which further enhances their capacity to make viscous dispersions but has the disadvantage that dispersion gets worse as viscosity increases.

The compositions of the current invention not only have the benefit of improved thickening and improved dispersion on dilution with water, but also have an

environmental and sustainable benefit arising from the large viscosity increasing particles. In the composition the majority of the mass of these particles is water, which allows the composition to deliver the desired consumer benefits without using unnecessary chemicals. Furthermore in the event that any particles deposit onto the fabric being conditioned then they will have a very low mass and impact when dried. The viscosity increasing particles

The particles are added to a base liquid with a low inherent viscosity and associated good dispersibility in order to provide it with a viscosity boost for as long as it remains undiluted. The particles are formed from water swellable cross linked polymer and are swollen to some extent by having absorbed some of the water in the composition. Such swollen particles fill more space.

These viscosity increasing particles have an average dry size of 10 to 400 microns. However, in the presence of water the polymer swells so that the particles have a volume average size of from 25 to 5000 microns, preferably from 25 to 1000 microns and more preferably from 50 to 500 microns, even from 60 to 300 microns or from 100 to 225 and especially from 140 to 200 microns. Unless stated otherwise all size measurements will be stated as the size in the presence of water, i.e. swollen. In general the preferred polymers absorb approximately 50 times their own weight of water to form the viscosity increasing particles. This is lower than would be the case if the cationic were absent and the swelling took place in pure water. Then the same polymer might absorb up to 450 times its own weight. It is preferred that the amount of particles in the composition will absorb less than 50% of the available water in the composition.

All particles sizes have been calculated as volume averages. By dry particles is meant that residual moisture in the particles is less than 10 wt%, (as determined by weight loss after 2 hours in an oven drying at 105°C). The polymer in the particle is insoluble in water. In the context of the invention, water- insoluble is defined as materials having a solubility of less than 1 x 10^"3 wt% in demineralised water at 20°C, preferably less than 1 x 10^"4 wt%, more preferably from less than 1 x 10^"8 to 1 x 10^"6 wt%. The polymer material should be chosen so that the particle is not reactive with other materials within the composition; in other words it is inert in the context of the

composition. Whilst the polymer in the formed particles is insoluble, the polymer raw material may contain some soluble components, arising mainly from incomplete crosslinking. The amount of soluble components is preferably less than 15 wt %, more preferably less than 10 wt %, and most preferably less than 7.5 wt %, by weight of polymer.

Preferred swellable polymer particles for use in the compositions of the invention are present in a crosslinked swellable polymer containing at least one cationic monomer and optionally non-ionic and or anionic monomers; wherein said polymer has an extractable (soluble) polymer content, as defined herein, lower than 15 %, and a cross-linking agent concentration of from 500 ppm to 10,000 ppm relative to the polymer, said polymer being obtained by gel polymerization. In a preferred embodiment, the extractable content of the polymer is preferably below 10 percent, and more preferably below 7.5 percent based on the total weight of polymer before hydration. A preferred crosslinked swellable polymer forms a polymer gel in the wet state, i.e. when combined with a suitable solvent such as water.

The polymers may be homopolymers or co-polymers. It is advantageous to use gel polymerization to manufacture the polymer to be used to make the particles. This type of polymerisation produces dry particles of the large size required. The polymer mass produced by gel polymerisation may be broken into smaller fragments and, if necessary, classified to obtain three dimensional polymer particles in the required size range, e.g. by sieving. The skilled worker will have access to other polymerisation methods that produce polymer particles within the required size range to obtain the large viscosity increasing particles when combined with water.

The crosslinked polymers for have a three dimensional network in which water can be absorbed. As the water penetrates in the network, the volume of the particle increases from 10 to 100 times the initial volume of the particle when a cationic material is present. The resulting particle is the viscosity increasing particle. Inclusion of these particles filled with water in the base composition leads to increased viscosity of the composition. The overall performance of fabric softening compositions comprising the particles is improved versus the same base composition including conventional smaller size cationic polymeric thickeners. In particular they have been found to have higher stability upon aging and more desirable rheology.

Cationic crosslinked swellable polymers suitable for use in the compositions of the invention may be prepared by means of gel polymerization, by polymerizing: at least one cationic monomer,

- and optionally other non-ionic and/or anionic monomers,

in the presence of a crosslinking agent and optionally of a chain transfer agent.

The overall charge of the polymer is preferably cationic, although nonionic polymers may also be suitable. A cationic polymer necessarily contains at least one cationic monomer. In other words, when the polymer contain anionic and/or non-ionic monomers, the amount of cationic charges is greater than the amount of anionic charges.

Gel polymerization is a well-known polymerization technique consisting of polymerizing water soluble monomers in an aqueous media in order to obtain a gel which is then generally cut or sliced, and dried so as to obtain a polymer in powder form. The resulting polymer may be pre-added in water or in another solvent before use. It may also be used as a powder.

Crosslinked polymers may be prepared using a gel polymerization process comprising the following steps: adding in an aqueous media, generally water, at least one cationic monomer, and optionally other non-ionic and/or anionic monomers, in the presence of a crosslinking agent and optionally of a chain transfer agent;

- starting the polymerization;

obtaining a gel;

transforming the gel in solid particles, generally a powder. The resulting gel is converted to powder by conventional manner, for instance by cutting the mass of gel into pieces and/or by extruding a mass of gel through coarse orifices, optionally cutting the gel before or after the extrusion, and by drying the pieces of gel. Jet milling may also be used.

The crosslinked swellable polymer can be added to the softening composition as a powder, or as a liquid dispersion. The added amount is preferably comprised between 0.1 % and 10% in weight, more preferably between 0.2 and 7%. This amount

corresponds to the polymer in dry powder form which has not yet absorbed water.

The polymerization is generally a radical polymerization generally induced by a redox couple, for instance sodium persulfate and sodium metabisulfite.

The crosslinking agent concentration is comprised in the range of 500 ppm to 10000 ppm in weight relative to the total amount of monomers.

Following is a non-restrictive list of crosslinking agents: methylene bisacrylamide (MBA), ethylene glycol diacrylate, polyethylene glycol dimethacrylate, diacrylamide, triallylamine, glyoxal, compounds of the glycidyl ether type such as ethyleneglycol diglycidyl ether, allylpentaerythritol, trimethylolpropane diallylether, or any other means familiar to the expert permitting crosslinking.

Preferred crosslinking agents are methylene bisacrylamide (MBA), triallylamine and allylpentaerythritol.

When the crosslinking agent used is the methylene bisacrylamide, its concentration is preferably between of 500 ppm and 5000 ppm by weight relative to the monomers.

When the crosslinking agent used is the triallylamine, its concentration is preferably between of 1000 and 10000 ppm by weight relative to the monomers.

Suitable cationic monomers for use in the preparation of the crosslinked swellable polymer are preferably selected from the group consisting of the following monomers and quaternized or salified derivatives: dimethylaminopropylmethacrylamide, dimethylaminopropylacrylamide, diallylamine, methyldiallylamine, dialkylaminoalkyl- acrylate, dialkylaminoalkyl-methacrylate, dialkylaminoalkyl-acrylamide, and

dialkylaminoalkyl-methacrylamide. It has been found that certain cationic monomers have an optimum performance in terms of dispersibility properties. Thus a preferred cationic monomer is selected from the group consisting of dimethylaminoethyl-methacrylate and its quaternized or salified derivatives and/or dimethylaminopropylmethacrylamide and its quaternized or salified derivatives. In a most preferred embodiment, the cationic monomer is dimethylaminoethyl methacrylate methyl chloride salt or dimethylaminoethyl methacrylate quaternary salt.

The crosslinked polymer for use in the composition of the invention may be prepared by polymerizing: more than 50 mol% of cationic monomers, preferably more than 70 mol%, most preferably more than 80 mol%;

optionally, other non-ionic and/or anionic monomers;

in the presence of crosslinking agent in an amount comprising between 500 ppm to 10000 ppm relative to the total weight of monomers, the total amount of monomers being 100%.

These percentages are based on the total amount of monomers. However, the amount of a crosslinking agent and the amount of chain transfer agent are in ppm in weight relative to the weight of total monomers i.e. relative to the above mentioned 100 mol% of monomers.

Chain transfer agents, such as isopropyl alcohol, sodium hypophosphite,

mercaptoethanol, may be used in the polymerization mixture in order to control the polymeric chain's length and the crosslinking density.

When a chain transfer agent is used, its concentration is in the range of 10 ppm to 1000 ppm in weight relative to the total amount of monomers. Preferred non-ionic monomers for use in preparing the crosslinked polymer for use in the compositions of the invention are selected from the group consisting of acrylamide, methacrylamide, N-Alkyl acrylamide, N-vinyl pyrrolidone, N-vinyl formamide, N-vinyl acetamide, vinylacetate, vinyl alcohol, acrylate esters and allyl alcohol. A preferred non- ionic monomer is acrylamide.

Preferred anionic monomers for use in preparing the crosslinked polymer for use in the compositions of the invention are selected from the group consisting of 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) said anionic monomers being acid, or partially or totally salified. More preferred anionic monomers are acrylic acid and 2-acrylamido-2- methyl propane sulfonic acid (ATBS) said anionic monomers being acid, or partially or totally salified.

Optionally, the crosslinked polymer may also contain monomers having hydrophobic character.

A preferred crosslinked water swellable cationic polymer is obtained by gel polymerization of dimethyl aminoethyl methacrylate quaternized with methyl chloride (cationic monomer), acrylamide (non-ionic monomer), and methylene bisacrylamide (crosslinking agent).

The water extractable polymer content is the ratio between the mass of the polymer which can be extracted when the polymer is submitted to dispersion in water and the total mass of the polymer.

The method for determining water extractable polymer content of the crosslinked polymer is based on the basic principle of colloidal titration which is well-known by the chemists and the skilled man of the art.

The method consists of separation of the water-soluble part ("extractable" polymer) from the water-insoluble part of the polymer to obtain a filtrate containing only the water- soluble part, and then measurement by colloidal titration of the water-soluble polymer content in the filtrate. The water extractable polymer content is the ratio between the mass of the polymer in the filtrate and the total mass of the polymer.

Stepl : Polymer extraction

This step consists in separating insoluble polymer (swollen particles) from water soluble polymer: 0.5 g (mo in g) of polymer is added to a beaker containing 800 ml of deionised water. The mixture is gently stirred with a magnetic stirrer for 6 hours. Then, 8 g of NaCI are added to complete the extraction. The salt solution is stirred for a further 1 hour. The polymer mixture is then filtered over a 100 μηη screen, and 15 minutes later the filtrate is then recovered in order to measure its weight (Mo in g). The "water extractables" polymer content in the filtrate is then titrated.

Step 2: Polymer titration

The titration principle is a well-known colloidal titration used to determine charge density of cationic polymers. The colloidal titration is performed as follows: A potassium polyvinyl sulphate (PVSK) solution is prepared by dissolving in deionised water a PVSK polymer having a molecular weight of 243,300 g/mol, so as to obtain a solution having a concentration of 0.0025 N (N/400).

A 0,1 N solution of hydrochloric acid is prepared in deionised water.

Titration is carried out on 30 g of polymer solution (filtrate) acidified with hydrochloric acid (pH=4) and coloured with 2 to 3 droplets of blue indicator. The PVSK solution is slowly added until the colour turns from blue to violet (equilibrium).

The water extractable polymer content (percentage of "extractables") is then determined according to (i) the volume of PVSK measured at equilibrium, (ii) the polymer

composition, (iii) the polymer weight and (iv) the reagents molarity thanks to the following equation: N Mo mo x x

% "Extractables" = Veq X X X 100

400 30 y

Veq: volume in ml of PVSK solution added at the equilibrium.

N/400: concentration of PVSK in the PVSK solution (N=1 ).

Mo: mass in grams of the total filtrate recovered in step 1 .

"mo": mass in grams of polymer added in water in step 1.

x correspond to the percentage in weight of cationic monomers based on total amount of monomers.

y corresponds to the molecular weight of the cationic monomer.

The expert will know how to vary the amount of crosslinking in order to obtain a final polymer having a low enough fraction of water-soluble polymer and the desired rheology. It is known, for example, that an increase of the concentration of crosslinking agent, other parameters being identical, leads to a decrease the extractable polymer content. The reverse is also true.

Cationic fabric softening active

The compositions of the present invention contain a cationic fabric softening active.

The fabric conditioning compositions of the invention may be dilute or concentrated. Dilute products typically contain up to about 8 wt%, preferably from 2 to 8 wt% softening active, whereas concentrated products may contain from about 8 to about 50 wt%, preferably from 8 to 25 wt% active. Compositions of more than about 25 wt% of active are defined as "super concentrated", depending on the active system, and are also intended to be covered by the present invention. The fabric softening active may, for example, be used in amounts of from 0.5 % to 35 wt%, preferably from 2 % to 30 wt% more preferably from 5 % to 25 wt% and most preferably from 8 % to 20 wt% of the composition. The preferred softening active for use in rinse conditioner compositions of the invention is a quaternary ammonium compound (QAC). The preferred quaternary ammonium compounds for use in compositions of the present invention are the so called "ester quats" comprising an ester link. Particularly preferred materials are the ester-linked triethanolamine (TEA) quaternary ammonium compounds comprising a mixture of mono-, di- and tri-ester linked components. Most preferably the ester-linked quaternary ammonium compound is an ester-linked triethanolamine quaternary ammonium compound comprising unsaturated fatty chains. Typically, TEA-based fabric softening actives comprise a mixture of mono, di- and tri- ester forms of the compound where the di-ester linked component comprises no more than 70 % by weight of the fabric softening compound, preferably no more than 60 %, e.g. 55 %, or 45 % of the fabric softening compound and at least 10 % of the monoester linked component, for example 1 1 % monoester. A preferred hardened type of active has a typical mono:di:tri ester distribution of from 18 to 22 monoester: from 58 to 62 diester: from 18 to 22 triester; for example 20:60:20. A soft TEA quat may have a typical mono:di:tri ester distribution of from 25 to 45 %, preferably from 30 to 40 % monoester: from 45 to 60 %, preferably from 50 to 55 % diester: and from 5 to 25 %, preferably from 10 to 15 % triester; for example 40:50:10.

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

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 C1-4 alkyl, C2-4 alkenyl or a C1-4 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. 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 methylsulfate, otherwise referred to as "TEA ester quats".

Commercial examples include Stepantex™ UL85, e 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 Evonik.

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

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

wherein each R¹ group is independently selected from C1-4 alkyl, hydroxyalkyl or C2-4 alkenyl groups; and wherein each R² group is independently selected from

Ce-28 alkyl or alkenyl groups; and wherein n, T, and X^" are as defined above.

Preferred materials of this second group include 1 ,2 fc>/^'s[tallowoyloxy]-3- trimethylammonium propane chloride, 1 ,2 fc>/^'s[hardened tallowoyloxy]-3- trimethylammonium propane chloride, 1 ,2-t)/^'s[oleoyloxy]-3-trimethylammonium propane chloride, and 1 ,2 b/^'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 C1-4 alkyl, or C2-₄ alkenyl groups; and wherein each R² group is independently selected from Cs-28 alkyl or alkenyl groups; and n, T, and X^" are as defined above. Preferred materials of this third group include bis(2-tallowoyloxyethyl)dimethyl ammonium chloride and hardened versions thereof. The iodine value of the quaternary ammonium fabric conditioning material is preferably from 0 to 80, more preferably from 0 to 60, and most preferably from 0 to 45. The iodine value may be chosen as appropriate. Essentially saturated material having an iodine value of from 0 to 5, preferably from 0 to 1 may be used in the compositions of the invention. Such materials are known as "hardened" quaternary ammonium compounds.

A further preferred range of iodine values is from 20 to 60, preferably 25 to 50, more preferably from 30 to 45. A material of this type is a "soft" triethanolamine quaternary ammonium compound, preferably triethanolamine di-alkylester methylsulphate. Such ester-linked triethanolamine quaternary ammonium compounds 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):

R

5

R N R X (IV)

wherein each R¹ group is independently selected from Ci-4 alkyl, hydroxyalkyl or C2-4 alkenyl groups; each R² group is independently selected from Cs-28 alkyl or alkenyl groups, and X^" is as defined above. The compositions of the invention may optionally 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 from 1 to 2.

The length of the unsaturated (and saturated if present) chains in the CPE or RSE is Cs- C22, preferably C12-C22. It is possible to include one or more chains of Ci-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 μβ is considered to be a solid component and any component with T2 > 100 μβ 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. Silicone based fabric softening agents (and other non quat softening compounds)

The compositions of the invention may further contain a silicone based fabric softening agent. Preferably the fabric softening silicone is a polydimethylsiloxane.

The fabric softening silicones include but are not limited to 1 ) non-functionalized silicones such as polydimethylsiloxane (PDMS) or alkyl (or alkoxy) functional silicones 2) functionalized silicones or copolymers with one or more different types of functional groups such as amino, phenyl, polyether, acrylate, siliconhydride, carboxylic acid, quaternized nitrogen, etc.

Suitable silicones may be selected from polydialkylsiloxanes, preferably

polydimethylsiloxane more preferably amino functionalised silicones; anionic silicones and carboxyl functionalised silicone.

An amino silicone that may also be used, for example, Arristan 64, ex CHT or Wacker CT45E, ex Wacker.

In terms of silicone emulsions, the particle size can be in the range from about

1 nm to 100 microns and preferably from about 10 nm to about 10 microns including microemulsions ( < 150 nm), standard emulsions (about 200 nm to about 500 nm) and macroemulsions (about 1 micron to about 20 microns).

Polyalkyl wax emulsions, for example polyethylene wax may also be used as softening agents in the composition of the invention.

Co-softeners and fatty complexing agents

Co-softeners may be used. When employed, they are typically present at from 0.1 to 20% and particularly at from 0.5 to 10%, based on the total weight of the composition. Preferred co-softeners include fatty esters, and fatty N-oxides. Fatty esters that may be employed include fatty monoesters, such as glycerol monostearate, fatty sugar esters, such as those disclosed WO 01/46361 (Unilever). The compositions of the present invention may comprise a fatty complexing agent.

Especially suitable fatty complexing agents include fatty alcohols and fatty acids. Of these, fatty alcohols are most preferred.

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

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

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

Preferred fatty acids include hardened tallow fatty acid (available under the trade name Pristerene™, ex Croda). Preferred fatty alcohols include hardened tallow alcohol

(available under the trade names Stenol™ and Hydrenol™, ex BASF and Laurex™ CS, ex Huntsman).

The fatty complexing agent is preferably present in an amount greater than 0.3 to 5% by weight based on the total weight of the composition. More preferably, the fatty component is present in an amount of from 0.4 to 4%. The weight ratio of the mono-ester component of the quaternary ammonium fabric softening material to the fatty complexing agent is preferably from 5:1 to 1 :5, more preferably 4:1 to 1 :4, most preferably 3:1 to 1 :3, e.g. 2:1 to 1 :2. Non-ionic surfactant

The compositions may further comprise a nonionic surfactant. Typically these can be included for the purpose of stabilising the compositions. 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 (V): R-Y-(C2H₄0)z-CH2-CH₂-OH (V) 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(0)0- , -C(0)N(R)- or -C(0)N(R)R- in which R has the meaning given above for formula (V), or can be hydrogen; and Z is at least about 8, preferably at least about 10 or 1 1. Preferably the nonionic surfactant has an HLB of from about 7 to about 20, more preferably from 10 to 18, e.g. 12 to 16. Genapol™ C200 (Clariant) based on coco chain and 20 EO groups is an example of a suitable nonionic surfactant. If present, the nonionic surfactant is present in an amount from 0.01 to 10%, more preferably 0.1 to 5 by weight, based on the total weight of the composition.

A class of preferred non-ionic surfactants include addition products of ethylene oxide and/or propylene oxide with fatty alcohols, fatty acids and fatty amines. These are preferably selected from addition products of (a) an alkoxide selected from ethylene oxide, propylene oxide and mixtures thereof with (b) a fatty material selected from fatty alcohols, fatty acids and fatty amines.

Suitable surfactants are substantially water soluble surfactants of the general formula (VI):

R-Y-(C2H₄0)z-CH2-CH₂-OH (VI) 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 10 to 60, preferably 10 to 25, e.g. 14 to 20 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 for formula (VI), or can be hydrogen; and Z is at least about 6, preferably at least about 10 or 1 1.

Lutensol™ AT25 (BASF) based on coco chain and 25 EO groups is an example of a suitable non-ionic surfactant. Other suitable surfactants include Renex 36 (Trideceth-6), ex Croda; Tergitol 15-S3, ex Dow Chemical Co.; Dihydrol LT7, ex Thai Ethoxylate ltd; Cremophor CO40, ex BASF and Neodol 91 -8, ex Shell. Further Optional Ingredients

The compositions may comprise other ingredients of fabric conditioner liquids as will be known to the person skilled in the art. Among such materials there may be mentioned: antifoams, perfumes and fragrances (both free oil and encapsulated material), insect repellents, shading or hueing 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, dyes, colorants, sunscreens, anti-corrosion agents, drape imparting agents, anti-static agents,

sequestrants and ironing aids. The products of the invention may contain pearlisers and/or opacifiers. A preferred sequestrant is HEDP, an abbreviation for Etidronic acid or 1 -hydroxyethane 1 ,1 -diphosphonic acid.

Product Form

The compositions are rinse-added softening compositions suitable for use in a laundry process. The compositions are pourable liquids.

The liquid compositions have a pH ranging from about 2.0 to 6, preferably from about 2.2 to 4.5, most preferably about 2.5 to 2.8. The compositions of the invention may also contain pH modifiers preferably hydrochloric acid or lactic acid.

The composition is preferably a ready-to-use liquid comprising an aqueous phase. The aqueous phase may comprise water-soluble species, such as mineral salts or short chain (C1-4) alcohols.

The composition is preferably for use in the rinse cycle of a home textile laundering operation, where, it may be added directly in an undiluted state to a washing machine, e.g. through a dispenser drawer or, for a top-loading washing machine, directly into the drum. The compositions may also be used in a domestic hand-washing laundry operation. Preparation of the compositions of the invention

The compositions of the invention may be made by preparing a fabric conditioning composition and adding the particles. Alternatively the polymer may be added dry to the composition and allowed to hydrate in situ. The functional compositions are preferably made in the conventional way, as known to the person skilled in the art, and then combined with preformed particles of the invention to form the composition of the invention. In one embodiment, the compositions of the invention are made by combining at least the cationic softener active ingredient in water, with the preformed particles.

The compositions of the invention may typically be made by combining a melt comprising the fabric softening active with an aqueous phase. The polymer may be combined with the water phase, or it may be post dosed into the composition after combination of the melt and water phase.

A preferred method of preparation is as follows:-

1 . Heat water to about 40 to 80°C.

2. Add any minor ingredients, such as antifoams, sequestrants and preservatives. 3. Melt the softening active and optional fatty alcohol together to form a co-melt.

4. Add the co-melt to the heated water.

5. Add acid to the preferred pH, if required.

6. Add dyes and perfumes.

7. Cool.

The formed particles may be post dosed or added in the batch water.

The invention will be further described with reference to the following non limiting examples and with reference to the drawings which are briefly described as:

Figure 1 is a graph showing the particle size distribution for Example 1 ; Figure 2 is a graph showing the particle size distribution for Example A; Figure 3 is a graph showing the particle size distribution for Example 2; Figure 4 is a graph showing the particle size distribution for Example B;

Figure 5 is a graph showing a comparison of Polymer 1 and the comparative Flosoft 270LS thickening polymer in the absence of cationic; and

Figure 6 is a graph showing the resulting particle size distribution for Example C.

Examples

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

Example 1 :- Synthesis of cationic polymer, Polymer 1 , by gel polymerization

A monomer solution was prepared by adding and stirring the following ingredients in a glass beaker:

9.0 parts of acrylamide solution (concentration in weight 50%, said monomer had a molecular weight of 71 g/mol) i.e. 4.5 parts of acrylamide

71.0 parts of dimethyl aminoethyl methacrylate quaternized with methyl chloride (concentration in weight 75%, said monomer had a molecular weight of 207.7 g/mol), i.e. 53.25 parts of said monomer

20.0 parts of deionised water

800 ppm of methylene bis acrylamide (ppm relative to the weight of the monomers) 7550 ppm of sodium formate (ppm relative to the weight of the monomers) pH was adjusted with phosphoric acid : [3. 4 to 3. 8]

The polymer composition (monomer ratio) in weight was 92.0% of dimethyl aminoethyl methacrylate quaternized and 8.0% acrylamide. After 30 minutes of stirring, the monomer solution was cooled down to 10°C, transferred in a Dewar flask, and then sparged with nitrogen for 15 minutes to remove oxygen. The polymerization was run in an adiabatic manner by addition of a redox couple of sodium persulfate (20 ppm / Total weight of monomers) and Mohr salt (10 ppm / Total weight of monomers). The salt was pre-diluted in water at 25 g/L tether with addition of azobisisobutironitrile, dispersed at 500 ppm/ Total weight of monomers.

The temperature of the solution rose spontaneously to 75°C in 2 hours, and was then held for 2 additional hours at 75°C. The resulting mixture was a sticky gel. This gel was sliced into pieces of 2 to 5 mm and then dried in an oven for 24 hours at 80°C. The dried slices were then jet milled or ground to give a dry powder. This powder was then filtered to remove particles less than 10 micron diameter by passing them through a sieve. The residual moisture of this powder was < 10.0%, as determined by weight loss after 2 hours in a drying oven at 105°C. The particle size of the dry powder was measured to fall between 10 and 60 microns using a Malvern Mastersizer Scirocco 2000 at 2.0 bar pressure (standard pressure).

Examples 1 & 2 and A & B: Fabric conditioner compositions Fabric conditioning compositions were made with the ingredients in Table 1.

Table 1

Examples 1 and A were prepared by the following process:

Batch water was heated to 50°C; Polymer (either Polymer 1 , or Flosoft 270LS a polymer substantially as disclosed in WO2010/079100) was added with milling;

Minors were added, followed by the molten active (SP88 an ester linked TEA quaternary ammonium material from Stepan and Lutensol AT25, a nonionic from BASF) and CaC ;

The mix was milled and cooled to 36°C and a free oil perfume composition was added and mixed further for a final period.

Examples 2 and B were prepared by the following process:

Batch water was held at 50°C;

- Minors were added followed by Lutensol AT25;

Polymer 1 or Flosoft 270LS was added with milling;

Molten SP88 was then added with further milling and CaC addition;

The mix was milled and cooled to 36°C at which point the free oil perfume was added and mixed further for a final period. Dispersion properties of Example Compositions 1 & 2 and A & B

Method of measuring dispersion

Instrument: TA Instruments DHR2 Rheometer (or any similarly capable rheometer).

Measuring Geometry: A concentric cylinder type system consisting of a rotor (cross bladed vane with square edged vertical blades) and stator (jacketed cylinder). The cylinder had an internal diameter of 26 mm and an axial depth of 35 mm; the jacket was connected to an external circulating water bath to control the temperature to 25°C. The blade diameter for the cross bladed vane was 20 mm while the blade height was 20 mm.

Method: With the measuring geometry installed on the instrument and with the cross bladed vane positioned 0.5 mm above the base of the cylinder the displaced volume to the top of the blades was about 9 cm³. This volume was half filled with the fabric conditioning composition being tested. The experimental procedure consisted of three parts: i) The rheometer was started at 54 rad/s and viscosity was recorded every second for a total of 300 s. After 20 s an equal volume of water (to that of the composition) was injected into the measuring geometry and the dispersion signal was recorded to the end of the 300 s. ii) At this point there was no guarantee that the product was completely dispersed into the water so the mixing was therefore taken to completion by running the rheometer at 90 rad/s for a further 300 s. iii) The final viscosity reading under the original measurement condition was now taken by measuring at 54 rad/s for a further 300 s.

Data Analysis: The T90 point (time taken to reach 90% dispersion) was taken as being the time at which the viscosity values from step (i) first exceed 90% of the final viscosity value obtained in step (iii). The times were adjusted to take account of the time before the water addition.

Results

The T90 dispersion test results are shown in Table 2. Smaller numbers indicate the mixture reaches full equilibrium faster. Also shown in Table 2 are the viscosities as measured using a cup and bob viscometer at a shear rate of 106s^"1 at 25°C.

Table 2

The samples made with Polymer 1 take a much shorter time to reach equilibrium on mixing with water (disperse) than the known polymer of the prior art. In both cases this is despite the fact that the viscosities of the two compositions comprising the large particle viscosity increasing polymer are higher than the prior art Flosoft 270LS compositions. Particle Size Characterisation of Example Compositions 1 & 2 and A & B

Particles size was characterised using a Malvern Mastersizer Scirocco 2000.

Figure 1 shows the particle size distribution for Example 1 . The lower peak is due to the presence of the vesicles of cationic softener material. It can be seen that the swollen crosslinked polymer particles in the composition are mostly (by volume%) over 100 microns in diameter.

Figure 2 shows the corresponding data for Example A. Like Example 1 there is a first peak indicating small particles of cationic, then a second peak showing that most of the polymer is present in this composition as particles smaller than 12 microns.

Figure 3 shows the data for Example 2. The plot is an average of three measurements. Figure 4 shows the data for Example B. Both the individual measurements and the average of the three are shown to show that there is little variation between the different measurements. As with Example A, the dominant peaks occur at 0.5 to 1 micron and 4 to 12microns. Figure 5 shows a comparison of Polymer 1 and the comparative Flosoft 270LS thickening polymer in the absence of the cationic and other components of the fabric conditioning compositions. The curve with the smaller peak below 1 micron is the prior art Flosoft polymer at 0.2 wt% in water and the one with the larger peak above 100 micron is Polymer 1 at 0.5 wt% in water. The different concentrations do not affect the position of the peaks.

To demonstrate that some of the peaks seen in the fabric conditioning compositions are not due to the presence of polymer Comparative Example C was made without any polymer present. Otherwise it was the same as Examples 2 and B. Figure 6 shows the resulting particle size distribution. Comparative Example C with no polymer demonstrates that the low particle size peaks found in the inventive and comparative examples above are a result of other components in the composition, not the crosslinked polymer particles. Example 3: Fabric conditioning Compositions 3 & D

An ester quat based fabric softener base formulation was prepared, which comprised 20 wt % partially hardened TEAQ (Stepantex SP88 (ex-Stepan)) by weight of the total base composition, the remainder being minors and water. 50 % (by volume of the final composition) of the fabric softener base formulation was combined with 50 % by volume of a polymer gel comprising the large polymer viscosity increasing particles of the invention (Polymer 1 ) to produce Composition 3. The concentration of Polymer 1 within the 50 % vol was 2 wt % by weight of the polymer as supplied. Thus, Composition 1 comprised 50 % by volume of the fabric softener formulation and 50 % by volume of the polymer gel, by volume of the final composition.

Composition D was made in the same way, but using a pre-hydrated prior art thickening polymer (Flosoft 270LS ex SNF) instead of Polymer 1 . The thickening polymer portion made up 50 % by volume of the final composition. The concentration of the polymer within the 50 % vol was 2 wt % by weight of the polymer as supplied.

The ingredients used for Compositions are shown in Table 3.

Table 3: Compositions 3 & D, showing amount (wt %) of components

Material Composition 3 Composition D

Stepantex SP88 10 10

Flosoft 270LS - 1 .0

Polymer 1 1 .0 -

Minors & Water Up to 100 wt % Up to 100 wt % Dispersion properties of Compositions 3 & D

Method of measuring dispersion 17 ml of the composition to be tested was poured from a standard Comfort™ bottle cap into 1000 ml of cold tap water in a 2000 ml beaker. After 30 seconds the resultant mix was visually assessed and ranked on a scale of 1 to 5, using half scores where appropriate. The scale was defined as follows:- Rating 1 : the solution is uniformly dispersed with no lumps or bits.

Rating 2: The product disperses giving an even dispersion with only a few small lumps or bits. Rating 3: The product disperses to give mainly small lumps or bits, but the dispersion is fine and gives lightly cloudy/coloured solution.

If desired, the mixture may be stirred by performing 5 revolutions at a rate of one per second with a flat spatula before being re-assessed using the same rating scale. The results are given in Table 4.

Table 4: Viscosity and dispersion scores for Example Compositions 3 & D

Viscosity Dispersion score

@ 106s ¹ Pre stir Post stir

D 694 4.5 3.5

3 682 3 1 .5 It will be seen that, Composition 3, in accordance with the invention, has dramatically improved dispersion properties over the similar composition D comprising the

conventional thickening polymer. Example 4: Prior art polymer thickeners in fabric conditioning compositions: E to G

An ester quat based fabric softener base formulation was prepared with a conventional thickening polymer, which comprised 12 wt % partially hardened TEAQ (Stepantex SP88 (ex-Stepan)) by weight of the total base composition, the remainder being minors and water.

The compositions were made by combining the polymer with the water phase prior to adding the melt and minors. The ingredient used for these Compositions are shown in Table 5.

Table 5: Compositions E to G, showing amount (wt %) of components

Dispersion properties of Compositions E to G

The results are given in Table 6.

Table 6: Viscosity and dispersion scores for Compositions E to G

Viscosity Dispersion score

@ 106s ¹ Pre stir Post stir

E 441 4.5 3.5

F 329 3.5 2.5

G 232 3.5 2.5 This shows the unwanted trade off between viscosity and dispersion that applies to the prior art polymeric thickeners when added to a fabric conditioning composition. It can be seen that the higher the composition viscosity, the poorer its dispersion rating.

Examples 4 to 6

An ester quat based fabric softener base formulation was prepared, which comprised 20 wt % partially hardened TEAQ (Stepantex VT90 (ex-Stepan)) by weight of the total base composition, the remainder being minors and water.

60 % (by volume of the final composition) of the fabric softener base formulation, was combined with 40 % by volume of a cross linked polymer gel (Polymer 1 , ex SNF) to produce Compositions 4 to 6. The concentration of the Polymer 1 within the 40 % vol was 2 wt % by weight of the polymer as supplied. The amount of the 2 wt % polymer in composition was varied as shown in Table 7, as wt % of the compositions.

Table 7: Compositions 4 to 6 (wt %)

Dispersion properties of Compositions 4 to 6 The results are given in Table 8. Table 8: Viscosity and dispersion scores for Compositions 4 to 6

This demonstrates the dispersion improvement over a range of viscosities for the invention. A comparison of the properties of Composition 5 with those of Composition G; and of

Composition 6 with that of Composition F shows improved dispersion at similar viscosities for the compositions in accordance with the invention.

Examples 7 & H

An ester quat based fabric softener base formulation was prepared, which comprised 20 wt % partially hardened TEAQ (Stepantex SP88 (ex-Stepan)) by weight of the total base composition, the remainder being minor ingredients and water. 50 % (by volume of the final composition) of the fabric softener base formulation, was combined with 50 % by volume of a polymer gel comprising the large polymer particles of the invention (Polymer 1 , ex SNF) to produce Example Composition 7. The concentration of the Polymer 1 within the 50 % vol was 1 wt % by weight of the polymer as supplied. Thus, Composition 7 comprised 50 % by volume of the fabric softener formulation and 50 % by volume of the polymer gel, by volume of the final composition.

Composition H was a commercially available fabric conditioner, under the brand name Molto, ex Unilever, Indonesia containing a conventional thickening polymer instead of Polymer 1 . Dispensing drawer properties of Compositions 7 & H

Method of measuring dispersion An accurate measurement of the residue remaining in the dispenser drawer of a front loading washing machine was achieved using a standard gravimetric and refractive index method using the BRIX function.

(i) The dispenser drawer of the washing machine was pre-weighed, and fabric

conditioner composition added (35 g) to the fabric conditioner compartment of the drawer.

(ii) The washing machine was set to the "rinse" cycle. (iii) When siphoning was complete, the machine drawer was removed and weighed, thus recording the weight of remaining residue.

(iv) Demineralised water was added to rinse out the residue to a fixed volume of

100 ml.

(v) Using a disposable pipette the residue and water were mixed together, ensuring that residue clinging to the sides of the drawer was mixed in with the water.

(vi) The aqueous mixture was then transferred using a disposable pipette to a 125 ml powder glass bottle, which was sealed and shaken to mix.

(vii) The refractive index of the composition was measured against a reference

standard. Each composition was tested in duplicate

A standard representing 100% residue remaining in the dispenser drawer was prepared for each sample screened (35 % solution of the composition in demineralised water). % residue remaining = BRIX of test sample

BRIX of ref. standard

The results are given in Table 9.

Table 9

It will be seen that, Composition 7 has dramatically improved dispensing properties over a similar product comprising conventional thickening polymer.

Claims

A pourable liquid fabric conditioning composition comprising:

a) a cationic fabric softening active;

c) further water,

the composition having a viscosity in the range of from 60 to 3500 mPas at 106s^"1 at 25 °C, wherein the polymer in the particle is insoluble in water and the particle is inert.

A composition according to claim 1 , wherein the particles have a volume average particle size of from 35 to 1000 microns.

A composition according to claim 2, wherein the particles have a volume average particle size of from 50 to 500 microns, preferably from 60 to 300 microns.

A composition according to any preceding claim wherein the polymer is a crosslinked swellable polymer containing at least one cationic monomer and optionally non-ionic and/or anionic monomers.

A composition according to any preceding claim wherein the polymer has an extractable polymer content lower than 15 %, and a cross-linking agent

concentration of from 500 ppm to 10,000 ppm by weight relative to the polymer.

A composition according to any preceding claim wherein the polymer is obtained by gel polymerization. A composition according to claim 6, wherein the cationic monomer is selected from the group consisting of the following monomers and their quaternized or salified derivatives: dimethylaminopropylmethacrylamide; dimethylaminopropylacrylamide; diallylamine; methyldiallylamine; dialkylaminoalkyl-acrylate; dialkylaminoalkyl methacrylate; dialkylaminoalkyl-acrylamide; and dialkylaminoalkyl-methacrylamide.

A composition as claimed in claim 7, wherein cationic monomer is selected from the group consisting of dimethylaminoethyl-methacrylate and derivatives and their quaternary or salified derivatives and/or dimethylaminopropylmethacrylamide and derivatives and their quaternary or salified derivatives.

A composition according to any one of claims 4 to 8, wherein the crosslinking agent is selected from the group consisting of methylene bisacrylamide (MBA), ethylene glycol diacrylate, polyethylene glycol dimethacrylate, diacrylamide, triallylamine, glyoxal, and glycidyl ether compounds.

A composition according to any preceding claim wherein the polymer comprises non-ionic monomers selected from the group consisting of: acrylamide,

methacrylamide, N-Alkyl acrylamide, N-vinyl pyrrolidone, N-vinyl formamide, N-vinyl acetamide, vinylacetate, vinyl alcohol, acrylate esters, and allyl alcohol.

A composition according to any preceding claim wherein the cationic fabric softening active is an ester-linked quaternary ammonium compound.

A composition according to claim 1 1 wherein the ester-linked quaternary

ammonium compound is an ester-linked triethanolamine quaternary ammonium compound comprising unsaturated fatty chains.

13. A composition according to any preceding claim wherein the cationic fabric

softening active is present in an amount of from 2 to 25 wt% of the total

composition.

14. A method of providing a liquor for the conditioning of fabrics comprising the step of dispersing a composition, as defined in any one of claims 1 to 13, in water.

15. A method according to claim 14 wherein the composition is added to a dispensing drawer of a washing machine.

16. A method according to claim 14 where the composition is added to a container in which the water is already present and dispersal takes place by movement of the water.