FORM - 2
THE PATENTS ACT, 1970
(39 of 1970)
&
The Patents Rules, 2003
COMPLETE SPECIFICATION
(See Section 10 and Rule 13)
SURFACE-ACTIVE MATERIAL AND ITS APPLICATIONS
HINDUSTAN UNILEVER LIMITED, a company incorporated under
the Indian Companies Act, 1913 and having its registered office
at 165/166, Backbay Reclamation, Mumbai -400 020, Maharashtra, India
The following specification particularly describes the invention and the manner in which it is to be performed

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SURFACE-ACTIVE MATERIAL AND ITS APPLICATIONS
FIELD OF THE INVENTION
5 The invention relates to a new surface-active material and its applications in the areas of foam and emulsion formation and stabilisation, coatings, encapsulation. More in particular, it relates to a surface-active material comprising fibres made of a waxy material and to a method for preparing said surface-10 active material, as well as to products comprising said surface-active material.
BACKGROUND TO THE INVENTION
A surface-active agent or surfactant is a substance that 15 lowers the surface tension of the medium in which it is
dissolved, and/or the interfacial tension with other phases. Accordingly, it is positively adsorbed at the liquid/vapour and/or at other interfaces.
20 Surface-active agents are widely used industry, for instance in foods, cleaning compositions and personal care products. In foods, they are used to achieve emulsions of oily and water-phases, such as in fat spreads or mayonnaise. In laundry cleaning applications, they are used to solubilise dirt and
25 keep it is solution, so that it can be effectively removed from the fabric.
For cleaning applications, the surface-active compounds may be chosen from anionic, cationic, nonionic, amphoteric and 30 zwitterionic surfactants. Many suitable surface-active compounds are available and are fully described in the literature, for example, in "Surface-Active Agents and Detergents", Volumes I and II, by Schwartz, Perry and Berch.

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The most commonly used detergent-active compounds are soaps and synthetic non-soap anionic and nonionic compounds. Examples of anionic surfactants include alkylbenzene sulphonates, particularly linear alkylbenzene sulphonates 5 having an alkyl chain length of Cg-Cis; primary and secondary alkylsulphates, particularly CB-CI5 primary alkyl sulphates; alkyl ether sulphates; olefin sulphonates; alkyl xylene sulphonates; dialkyl sulpho-succinates; and fatty acid ester sulphonates. Sodium salts are generally preferred. 10
Examples of nonionic surfactants include the primary and secondary alcohol ethoxylates, especially the Ca-C2o aliphatic alcohols ethoxylated with an average of from 1 to 20 moles of ethylene oxide per mole of alcohol, and more especially the 15 Cio-Ci5 primary and secondary aliphatic alcohols ethoxylated with an average of from 1 to 10, preferably 3 to 7 moles of ethylene oxide per mole of alcohol. Non-ethoxylated nonionic surfactants include alkylpolyglycosides, glycerol monoethers, and polyhydroxy-amides (glucamide). 20
The choice of the surface-active material (surfactant), and the amount present, will depend on the intended use of the detergent composition. For fabric washing compositions, different surfactant systems may be chosen, as is well known 25 to the skilled formulator, than for handwashing products or mechanical dishwashing products.
In foods, surface-active materials are commonly used to prepare emulsions. Edible emulsions are used as a base for 30 many types of food products. Mayonnaise compositions, for
example, comprise edible oil-in-water emulsions that typically contain between 80 to 85% by weight oil, and egg yolk, salt, vinegar and water. Mayonnaise compositions are enjoyed by many consumers, and particularly, on sandwiches, in dips, with fish

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and other food applications. The oil present in the edible emulsions used in such food products is generally present as droplets dispersed in the water phase. In addition to droplet size and the amount of droplets dispersed, the close packing 5 of the oil droplets results in the characteristic rheological behaviour of the emulsions used to make the desired food product, such as mayonnaise or margarine.
The surface-active agents that are most commonly used in food 10 applications comprise low molecular weight emulsifiers that are primarily based on fatty acid derivatives. Examples include: lecithin's, monoglycerides {saturated and unsaturated), polysorbate esters (Tweens), sorbitan esters (Spans), polyglycerol esters, propylene glycol monostearate, 15 sodium and calcium stearoyl lactylates, sucrose esters,
organic acid (lactic, acetic, tartaric, succinic) esters of monoglycerides. Proteins and other surface-active biopolymers can also be used for this purpose. Typical examples of food proteins include milk proteins (caseins and whey proteins), 20 soy protein, egg protein, lupin protein, pea protein, wheat protein. Examples of other surface-active biopolymers include gum Arabic, modified surface active pectin and OSA modified starch.
25 Recently, the interest in the study of solid particles as
emulsifiers of dispersed systems has been re-awakened. Much of this activity has been stimulated by the research of Binks and co-workers (Binks, B. P. Curr. Opin. Colloid Interface Sci. 2002, 7, 21), though the principles of such stabilisation were
30 observed at least 100 years ago (Ramsden, W. Proc. R. Soc.
London 1903, 72, 156). The advantage of particle stabilisation is that it is almost impossible to displace an adsorbed particle once adsorbed to an interface. This gives particle stabilised emulsions and foams excellent stability, especially

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with respect to ripening mechanisms such as dis-proportionation.
Whilst the use of particles to stabilise o/w, w/o and duplex 5 emulsions and foams has been amply demonstrated in recent years, much less research has been carried out on non-spherical structures with respect to the stabilisation of interfaces. Furthermore, it has recently been demonstrated by Alargova et al. (Langmuir, 2006, 22, 765-774) that polymer 10 rods can be used to provide interfacial stabilisation to emulsions and foams.
WO-A-06/007393 (North Carolina State University) discloses a process for preparing micro-rods using liquid-liquid
15 dispersion. The method comprises mixing a polymer dissolved in a first solvent with a second solvent to form a dispersed phase of polymer solution droplets and subsequently introducing shear stress such that the polymer solution droplets form micro-rods.
20
Notwithstanding the fact that many surface-active materials are known and available, there is a continuous need for new alternative or improved surface-active materials, especially environmentally friendly surface-active materials having good
25 biodegradability properties. It is therefore an object of the present invention to provide such surface-active materials. It is a further object to provide surface-active materials that are useful in the stabilisation of emulsions- and foams.
30 Surprisingly, it has now been found that one or more of the above-mentioned objects can be achieved by the surface-active material according to the invention, which is characterised in that it comprises fibres made of food-grade waxy material,

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said material having a contact angle at the air/water or the oil/water interfacebetween 60° and 120°.
The present inventors have found that the shape and size are 5 of critical importance for the colloidal stability of foams and emulsions. Rod-like (fibril) shapes are much more efficient then spherical particles. Another key factor for good foam and emulsion stabilisation is the particle contact angle at oil/water or air/water interface, which must be as 10 close to 90° as possible. The rod-like structures must
therefore be amphiphathic in design (o/w and w/o stabilisation depends on the relative balance between hydrophobicity and hydrophilicity).
15 Waxy materials such Carnauba wax. Shellac or Bee wax are
currently used in foods, mainly as coatings because of their very good moisture barrier properties. Their main application is in the confectionary industry: for instance the top coating of Tick-Tack candies is made from Carnauba wax, while top
20 coating of M&M candies is made from Shellac.
SUMMARY OF THE INVENTION
According to a first aspect, the invention provides a surface-25 active material which is characterised in that it comprises
fibres made of a waxy material, said material having a contact angle at the air/water interface or the oil/water interface of between 60° and 120°.
30 According to a second aspect, there is provided a process for preparing such a surface-active material.
According to a third aspect, there is provided a product comprising said surface-active material for the purpose of

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foam and emulsion formation and stabilisation, coatings, encapsulation and drug delivery. The fourth aspect involves the application of said surface-active material in home and personal care, foods, oilfield, agriculture, textile, 5 construction, emulsion polymerisation, leather, plastic, pulp, paper and pharma.
DETAILED DESCRIPTION OF THE INVENTION
In its first aspect, the invention relates to a surface-active 10 material comprising fibres made of a waxy material, said
material having a contact angle at the air/water interface or the oil/water interface of between 60° and 120°, giving them surface-active properties and affinity to adsorb at air/water or oil/water surfaces. 15
By the word "fibre", we mean in the context of the present invention, any structure made of solidified waxy material, wherein the ratio between the length and the diameter ranges from 10 to infinite. Here, the diameter means the largest 20 distance of the cross-section. The fibre topology might be liner or branched (star-like). The aspect ration in this case is defined as aspect ratio of the longest branch.
The fibres used in the present invention have a length of 0.1 25 to 100 micrometer, preferably from 1 to 50 micrometer. Their diameter is in the range of 0.01 to 10 micrometer. The aspect ratio (length / diameter) is generally more than 10, preferably more than 20 up to 100 or even 1,000.
30 The fibres used in the present invention are made of a waxy material, preferably of a wax, more preferably a food-grade wax, A wax is a non-glyceride lipid substance having the following characteristic properties:
• plastic (malleable) at normal ambient temperatures;

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• a melting point above approximately 45 °C (which differentiates waxes from fats and oils);
• a relatively low viscosity when melted (unlike many plastics);
5 • insoluble in water but soluble in nonpolar organic solvents;
• hydrophobic.
Waxes may be natural or artificial, but natural waxes, 10 especially food-grade waxes are preferred. Beeswax, carnauba (a vegetable wax) and paraffin (a mineral wax) are commonly encountered waxes which occur naturally. Some artificial materials that exhibit similar properties are also described as wax or waxy. 15
Chemically speaking, a wax may be an ester of ethylene glycol (ethane-1,2-diol) and two fatty acids, as opposed to a fats which are esters of glycerine (propane 1,2,3-triol) and three fatty acids. It may also be a combination of other fatty 20 alcohols with fatty acids. It is a type of lipid.
A second aspect of the present invention is a process for the preparation of such a surface-active material, comprising the steps of selecting a waxy material, dissolving it in a first
25 solvent, mixing the solution of the waxy material in the first solvent with a second solvent having an appropriate viscosity, whereby the second solvent is miscible with the first solvent and the waxy material is not soluble in the second solvent, while continuously introducing shear stress, to form a
30 dispersed phase of elongated wax solution droplets which solidify due to dissolution of the first solvent into the second solvent, to form fibres having a contact angle at the

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air/water interface or the oil/water interface between 60° and 120°.
In the process of the invention, small particles are made from 5 waxy materials to form fibres having a contact angle at the air/water interface between 60° and 120° for stabilisation of foams, or having a contact angle at the oil/water interface between 60° and 120° for stabilisation of emulsions. The oil in the oil/water interface is any triglyceride oil, such as 10 palm oil. Up to now waxy materials have not been used for preparation of micro particulate fiber materials.
Examples of a suitable source for the waxy material are the food-grade waxes carnauba wax, shellac wax or bee wax. This
15 food-grade waxy material can be transformed into micro-
particulate fibres by inducing precipitation of a wax solution via solvent change under shear. For instance, the food-grade waxy material is dissolved in high concentration in ethanol and a small amount of this solution is added to a viscous
20 liquid medium and subjected to shearing. This procedure results in the emulsification of the wax solution in the viscous medium, the shear driven elongation of the emulsion drops their successive solidification into rod-like particles due to escape of ethanol into continuous liquid medium, which
25 is assisted by the fact that ethanol is soluble in the liquid medium, while the waxy material is not or poorly soluble therein. After the fibres have been formed they can be extracted and purified by using the natural buoyancy of the wax. In order to facilitate this process the viscosity of
30 continuous liquid phase should be decreased. The inclusion of water effectively thins the solution so that the rods will rise much quicker and a clear separation is seen between the rods and most of the solution. The liquid phase can then be taken and replaced by water several times in order to remove

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all solvents other than water. Due the fact that waxy materials have a contact angle at the air-water interface or oil/water interface between 60° and 120°, the micro particulate fibres have affinity for adsorbing at air/water or 5 oil/water surfaces. Therefore, dispersions containing fibres made from food-grade waxy materials can be used for the stabilisation of foams and emulsions, without need to add other surface-active materials as surfactants, proteins or di-block co-polymers such as Pluronics, as discussed above.
10
If the contact angle is not already in the specified range of between 60° and 120°, the material may optionally be modified so as to give it the correct contact angle between 60° and 120°. The modification of the fibres can be achieved by
15 chemical or physical means. Chemical modification involves esterification or etherification, by means of hydrophobic groups, such like stearate and ethoxy groups, using well-known techniques. Physical modification includes coating of the fibres with hydrophobic materials, for example ethylcellulose
20 or hydroxypropyl-cellulose. Fat and fatty acids such as
stearic acid may also be used. The coating can be done using colloidal precipitation using solvent or temperature change, for instance. The physical modification may also involve "decoration" of rod like materials using hydrophobic nano-
25 particles, for instance silica.
The contact angle of fibres can be measured using the gel-trapping technique as described by technique as described by Paunov (Langmuir, 2003, 19, 7970-7976) or alternatively by 30 using commercial contact angle measurement apparatus such as the Dataphysics OCA20.
The parameters that affect the formation of the waxy fibers, are a.o. the viscosity and the composition of continuous

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liquid phase, the shearing rate, the initial droplet size, the wax concentration into ethanol solution and the total solution volume. Of these, the parameters with noticeable affects were changes to the stirring media and to the concentration of wax 5 in ethanol. Changes to the standard solvent ratio resulted in greater or lesser shear which had a limited effect on the size of the rods produced. A larger influence is held by the type of solvent used. The inclusion of a small amount of ethanol to the viscous stirring media resulted in shorter but better
10 defined micro rods with much lower flaking. It is thought that the inclusion of ethanol in the stirring media may slow the rate of precipitation of waxy material resulting in smaller micro emulsion droplets, thus giving shorter micro rods. For the influence of the various parameters that affect the
15 formation of the waxy fibers, reference is made to WO-A-06/007393 (North Carolina State University).
A third aspect of the present invention is a product comprising said surface-active material for the purpose of
20 foam and emulsion formation and stabilisation, for instance as foam stabilisers for ice cream, as emulsion stabilisers for mayonnaise or margarine, as foam formation agent and stabiliser for home and personal care products such as toothpaste, and as flotation agent, for instance in the mining
25 industry.
The industries where the surface-active material of the present invention could be applied include home and personal care, foods, oil industry, agriculture, textile, construction, 30 polymer industry (emulsion polymerisation), leather, plastic, pulp, paper and pharma. Accordingly, a fourth aspect involves the application of said surface-active material in home and personal care, foods, oil industry, agriculture, textile, construction, emulsion polymerisation, leather, plastic, pulp,

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paper and pharma. They may also be used for coatings, encapsulation and drug delivery.
The invention will now be further illustrated by means of the 5 following non-limiting examples.
Example 1 Materials:
Shellac Wax: Supplied by NB Entrepreneurs, lOOg of refined 10 shellac wax. This was then purified by dissolving the wax in-boiling ethanol with removal of insoluble materials via centrifugation. The ethanol was then removed under vacuum with gentle heating yielding the purified shellac crystals. Glycerol: Alfa Aesar, 99+%. 15 Ethanol: Fischer Scientific
Ethylene Glycol: Fischer Scientific
Shellac rods were precipitated by dropping droplets containing 50%wt shellac in ethanol into 40ml solution consisting of 20 60:30:10 glycerol/ethylene glycol/ethanol stirred at speed 5.7 on an IK A RH KT/C magnetic stirrer/hotplate. 170ul of 50%wt shellac solution in ethanol was added in lOul increments to the viscous stirring media, which equates to 0.085g of wax. After dropping has been finished the total solution was 25 stirred for 10 additional minutes to insure solidification of the fibre. The waxy micro rods prepared as described above were extracted and purified by using the natural buoyancy of the wax: 40ml solution containing waxy fibres as described above was transferred into three sample tubes (75mm x 25mm) , 30 with washings (milli-Q), and then topped up with milli-Q water till % full. The tubes were then inverted, but not shaken, several times in order to mix the solvents. The inclusion of water effectively thinned the solution so that the rods would rise much quicker and a clear separation was seen between the

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rods and most of the solution. The liquid phase can then be taken and replaced by water several times in order to remove all solvents other than water, finally the rods can be re-dispersed in a known volume of water thus giving a solution 5 with an approximate concentration of rods. The concentration is approximate due to the fact that in the cleaning and separating process some rods will be lost; this is estimated to be of the order of 5% of the initial weight of wax solution dropped into the stirring liquid. Thus, when cleaned and re-
10 dispersed in 20ml of water in a sample tube, with an
approximate 5% loss, gave a 0.4%wt concentration of shellac fibres in water with average length of 120um and diameter of 2pm. When the solution is manually shaken for 30 sec it produces a foam that is stable for more then one week. Using
15 confocal microscopy, a dense network of shellac fibres could be clearly seen on the bubble surface.
Example 2
Shellac rods were precipitated from 17.5%wt shellac in ethanol 20 into 40ml of 60:30:10 glycerol/ethylene glycol/ethanol stirred at speed 5.7 on an IK A RH KT/C magnetic stirrer/hotplate: 480ul of 17.5%wt shellac solution was added in lOul increments to the viscous stirring media, this again equates to 0.084g of wax. When cleaned and re-dispersed in 25 20ml of water in a sample tube, with an approximate 5% loss, gave a 0.4%wt concentration of shellac in water. The rod length produced using this method was 30um on average. When the solution is manually shaken for 30 sec it produces a foam that is stable for more then one week. Using confocal 30 microscopy, a dense network of shellac fibers could be clearly seen on the bubble surface.

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Example 3
Three separate concentrations of rods in milli-Q water were produced, 0.$%wt, 1.2%wt and 2.0%wt. They were produced in the same way as in example 1 except for the amount of shellac &zkted, also the solutions were now in 10ml measuring cylinders, SQ that foam volume can be measured directly, and the rods needed to be in 4ml of water. However, during the cleaning process the rods are never completely out of solution and so this Provides a problem with having an accurate volume of water in the final dispersion. To overcome this problem the volume of water is deduced by weight. The measuring cylinder is weighed when empty and then the wet rods are transferred to the cylinder along with washings, the cylinder is then weighed again and water is added until the final weight is 4g, plus the weight ot the wax, more than the empty measuring cylinder. Thus there is 4ml of milli-Q water in the dispersion. Dispersions with three different concentrations of shellac fibers were Prepared as described above using following conditions and concentrations:
• 0.5%wt-li0ul in lOul increments of the 20%wt shellac in ethanol was pippetted into a 40ml stirring solution of 85:15 glycerol/water at speed 6.0.
• 1.2%wt-250ul in lOul increments of the 20%wt shellac in ethanol was pippetted into a 40ml stirring solution of 85:15 glycerol/water at speed 6.0.
• 2.0%wt-420pl in lOul increments of the 20%wt shellac in ethanol was pippetted into a 40ml stirring solution of 85:15 glycerol/water at speed 6.0.
All rod dispersions were cleaned and separated and finally transferred as previously stated. The resulting dispersions were shaken as before, 30secs using manual shaking. Resulting foams were measured in mis and monitored at the same time intervals as before, Oh, lh, 2h, 5h, 24h, 48h, 72h, 96h, 120h, 144h, and 168h. For all foams produced, the most rapid

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reduction in foam volume was observed in the first 5 hours, which is manly due to liquid drainage, after which a near plateau in stability is observed for at more then 7 days. Furthermore, it was found that there is an approximately 5 linear relationship between the concentration of the rods in solution and the volume of foam produced.

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CLAIMS
1. Surface-active material comprising fibres made of a waxy
material, said material having a contact angle at the
5 air/water interface or the oil/water interface of between 60° and 120°.
2. Surface-active material according to claim 1, having a
contact angle between 70° and 110°, preferably between 80° and
10 100°.
3. Surface-active material according to any one of the
preceding claims, wherein the fibres are made of a food grade
waxy material.
15
4. Surface-active material according to any one of the
preceding claims, wherein the fibres have a length of 0.1 to
100 micrometer, preferably from 1 to 10 micrometer.
20 5. Surface-active material according to any one of the
preceding claims, wherein the fibres have an aspect ratio of more than 10 to 100 or even 1,000.
6. Surface-active material according to any one of the
25 preceding claims, wherein the fibres are made of carnauba or shellac wax or bee wax.
7. Process for the preparation of a surface-active material
according to any one of the preceding claims, comprising the
30 steps of selecting a waxy material, dissolving it in a first solvent, mixing the solution of the waxy material in the first solvent with a second solvent having an appropriate viscosity, whereby the second solvent is miscible with the first solvent and the waxy material is not soluble in the second solvent,

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while continuously introducing shear stress, to form a dispersed phase of elongated wax olution droplets which
solidify due to dissolution of the first solvent into the second solvent to form fibres. 5
8. Food product comprising the surface-active material
according to any one of claims 1-6, wherein the food product
is selected from foamed products such as foams, mousses, ice
cream, or emulsified products such as fat-spreads or
10 dressings.
9. Food product according to claim 8, in the form of a
liquid product selected from the group consisting of sauces,
soups and drinks.
15
10. Process for the preparation of a stabilised food product
according to claims 8-9, comprising the step of adding the
surface-active material according to claims 1 to 6 to a food
product.
20
11. Use of the surface-active material according to claims 1-
6 for foam and emulsion formation and stabilisation, coatings,
encapsulation and drug delivery.
25 12. Use according to claim 11, in the following industries: home and personal care, foods, oilfield, agriculture, textile, construction, emulsion polymerisation, leather, plastic, pulp, paper and pharma..
Dated this 12th day of January 2009