MXPA01002116A - Granular compositions - Google Patents

Abstract

A granular composition, especially for incorporation in washing powder formulations, comprises at least 40%by weight of an amorphous silica and typically at least 30%by weight of a functional ingredient such as a perfume, the amorphous silica having a surface area of at least 550 m2/g, a pore volume from about 1.0 to about 2.5 ml/g and a particle size of no more than 50 microns, the granules of said composition having a particle size from about 200 to about 2000 microns.

Description

GRANULAR COMPOSITIONS DESCRIPTION OF THE INVENTION The present invention relates to a granular composition, and is particularly concerned with the production of a composition comprising granules with sufficient strength to support normal handling / processing coupled with the ability to carry an active or functional ingredient. volatile organic, substantially free of water in liquid phase, such as fragrances or perfumes, flavors, food ingredients and / or cosmetic ingredients. The functional ingredient may be a malodorous compound, a protein, an enzyme, a polysaccharide, carbohydrate or antibody. Suitable cosmetic ingredients include insect attractants or repellents, sunscreen compounds, or hair treatment compounds such as hair growth promoters, hair removers, hair straightening and permanent waving materials. Granules, for example, can carry perfume, retain the perfume within their pore system when formulated in a powder for washing fabrics and disperse, in contact with water, into sufficiently small particles to prevent es deposition on fabrics or other items when used in a normal wash cycle. Such granules are proposed to allow the intensity of the washing powder perfume to be maintained, to suppress unwanted perfume loss and to function as a supply system to the washing and / or rinsing cycle, fabric or other article. Perfumes capable of modifying or improving the aroma of compositions for washing fabrics, or imparting a more pleasing aroma are well known in the art. US-A-4131555 and 4228026 are illustrative of the prior art which disclose substances that impart a pleasant aroma or fragrance to liquid and granular fabric washing formulations. The described methods of adding the substance are mixed in the liquid formulation or spray on the surface of granular fabric washing compositions. It is well recognized that perfumes are volatile, and many of the ingredients of perfumes may be lost from the product during processing or storage, or destroyed or damaged by contact with alkaline conditions present in fabric washing compositions, or by contact with some of the components of the composition, such as bleaches and enzymes. Attempts to solve these problems have centered around the use of carriers impregnated with perfume. EP-A-332259 (Procter and Gamble) discloses certain perfume particles formed by adsorbing a perfume on silica. EP-A-332260 (Procter and Gamble) describes the use of such particles in fabric softening compositions. International application No. O94 / 16046 (Quest International) describes the use of highly structured and gel-like precipitated silicas to convert liquid perfume to a free-flowing powder that can be easily formulated into a concentrated formulation for fabric washing. In all these examples of the prior art emphasis is placed on the particle size, total pore volume and surface area of the particulate material of the silica, since the adsorption capacity is of the utmost importance. EP-A-332259 and EP-A-332260 describe a wide range of silicas with a particle size from 0.001 microns (fumed silica) to 15 microns (silica gel) and a surface area in the range from 100 to 800 m2 / g. For a fabric washing composition the preferred silica is a fumed silica, with a particle size in the range of 0.007 to 0.025 microns. It is also mentioned that silica gels can be used, the preferred size is 1 to 8 microns. International application No. WO94 / 16046 describes silicas with a particle size of 5-50 microns and a surface area in the range of from 100 to 450 m2 / g. EP-A-820762 (Unilever) describes porous silicas which are useful in fabric washing powders, and having a particle size greater than 50 microns, and a surface area in the range from 100 to 450 m2 / g. All prior art mentioned above does not refer to the ability of the adsorbent to carry and retain the fragrance through the processing step used in the manufacture of a fabric washing powder. EP-A-535942 and EP-A-536942 (Unilever) describe porous inorganic carrier particles, for example silica having at least one pore volume of 0.1 ml / g consisting of pores with a diameter of 7 to 50 A, It states that they are able to carry and retain the fragrance. A wide range of particle size is claimed, from at least 5 microns to 500 microns, and it is also described that the particles in this size range can also be formed into aggregates of two or more particles, to make aggregates of various diameters of particle, for example 1000 microns. However, no mention is made of how this will be achieved, and the properties of the resulting agglomerated particles. It is not true, for example, from the description of the invention that the agglomerated materials of the preferred particles are still capable of retaining fragrance and suppressing the loss thereof through evaporation. What is certain is that the referred inorganic carriers, for example microporous silica gels and zeolite Y, have a low total porosity and hence a poor loading capacity. The formation of granules by the agglomeration of finely divided silica has been described in International Patent Applications Nos. W094 / 12151 (Unilever) and in WO96 / 09033 (Crosfield). The first refers to materials suitable for cleaning the skin and hair, and uses silica particles that can carry but do not retain fragrance or suppress its evaporation, while the latter describes how the silicas of mixed structures can be combined to form suitable agglomerates to impart a sensory effect to the toothpaste.

US-A-5656584 and US5648328 (Procter and Gamble) describe processes for producing a particulate additive composition for laundry in the form of granules or agglomerates. The process includes mixing the porous carrier, zeolite X and / or zeolite Y or mixtures thereof, which typically contain the perfume with an encapsulating material, typically a carbohydrate, and then compact (US-A-565658) or extrude. (US-A-5648328) the mixture to form agglomerated materials. The preferred inorganic materials zeolite X and zeolite Y will retain and suppress the fragrance, but have a poor loading capacity when compared to a high porosity silica (pore volume of at least 1 ml / g). There is a need, therefore, for a granular composition comprising granules that have sufficient strength to withstand normal manufacturing / processing handling, the ability to carry a volatile organic functional ingredient, substantially free of water in liquid phase such as perfume, preferably in fillers of at least 30% by weight, retaining the functional ingredient within its pore structure while suppressing the loss by evaporation and dispersing in particles upon contact with water. According to a first aspect of the present invention, a granular composition is provided for carrying and retaining a volatile organic functional ingredient, substantially free of water in liquid phase, the granular composition comprising at least 40% by weight of an amorphous silica having a surface area of at least 550 m2 / g, a pore volume from about 1.0 to about 2.5 ml / g and a particle size of no more than 50 microns (preferably not more than 40 microns and more preferably no more than 30 microns), the granules of the composition disintegrate when placed in contact with water, and have: A particle size greater than about 200 and up to about 2000 microns , preferably from about 400 to about 1200 microns; and A dry strength such that no more than about 30%, more preferably no more than about 25% and more preferably no more than about 20% by weight passes through a 212 micron sieve when subjected to the friction test defined herein.

Typically the amorphous silica constitutes up to about 70% by weight of the composition, and the functional ingredient comprises at least 30% by weight of the composition, for example the functional ingredient can constitute up to about 60% by weight of the composition. Preferably the granular composition is such that, upon contact with water, from about 50%, preferably from about 60% to about 95% by weight will pass through a sieve of 212 microns. The silica granules preferably have, with respect to the functional ingredient, an absorption capacity of at least 30%, more preferably at least 35%, more preferably at least 40% by weight. The functional ingredient is usually incorporated into the composition by addition to the silica-based granules (preferably while under agitation) until a loading level is obtained. The actual loading is preferably somewhat less than the maximum achievable, and it is preferably such that the addition of the functional ingredient does not exceed the point beyond which the ra granules do not have free flow. I to amorphous silica, which may be either a silica gel or a precipitated silica, or mixtures thereof, has a high surface area (at least 550 m2 / g) and a high pore volume (in the range of 1.0 at 2.5 ml / g) so that its porosity is characterized by the presence of a micropore system within a wider pore mesoporic structure. The silica particles from which the granules are produced preferably have a particle size no greater than about 30 microns, for example from 2 to 30 microns, and a surface area of at least 600 m2 / g, more preferably at less 650 m2 / g, for example up to about 1200 2 / g. When the functional ingredient comprises a perfume, this usually consists of one or more perfume components optionally mixed with a suitable solvent or diluent. The perfume components and mixtures thereof which may be used for the preparation of such perfumes may be natural products such as essential oils, absolutes, resinoid compositions, resins, concretes, etc., and synthetic perfume components such as hydrocarbons, alcohols, aldehydes, ketones, ethers, acids, esters, acetals, ketals, nitriles, etc., including saturated and unsaturated compounds, aliphatic, carbocyclic and heterocyclic compounds. Examples of such perfume components are: geraniol, geranyl acetate, linalool, linalyl acetate, tetrahydrol inalole, citronellol, citronellyl acetate, dihydromyrcenol, dihydromyrcenyl acetate, tetrahydromyrcenol, terpineol, terpinyl acetate, nopol acetate, phenylethanol, 2-phenylethanol acetate, benzyl alcohol, benzyl acetate, benzyl salicylate, benzyl benzoate, styrallyl acetate, amyl salicylate, dimethylbenzylcarbinol, trichloromethylphenylcarbinyl acetate, p-tert-butylcyclohexyl acetate, isononyl, vetyveryl acetate, vetyverol, alpha-n-amylcinnamic aldehyde, alpha-hexyl cinnamic aldehyde, 2-methyl-3- (p-tert-butylphenyl) propanal, 2-methyl-3- (p-isopropylphenyl) -propanal, 3 - (p-tert-butylphenyl) propanal, trichlorodecenyl acetate, tricyclodecenyl propionate, 4- (4-hydroxy-4-methylpentyl) -3-cyclohexencarbaldehyde, 4- (4-methyl-3-pentenyl) -3-cyclohexencarbaldehyde, 4-acetoxy-3-pentyl tetrahydropyran, methyl dihydroxylammonium, 2-n-heptylcyclopentanone, 3-methyl-2-pentyl-cyclopentanone, n-decanal, n-dodecanal, 9-deca-l-ol, phenoxyethyl isobutyrate, phenylacetaldehyde dimethyl acetal, phenylacetaldehyde diethyl acetal, trilobal geranoni, citronelone trile, cedrile acetate, 3-isocanecyclohexanol, methyl cedril ether, isolongifolanone, aubepin nitrile, aubepin , heliotropin, coumarin, eugenol, vanillin, diphenyl oxide, hydroxycitronellane, ionins, methyl ionones, isomethyl ionones, irons, cis-3-hexanol and esters thereof, indane musk fragrances, tetralin musk fragrances, musk fragrances Isochroman, macrocyclic ketones, macrolact ine musk fragrances, ethylene brasilate, aromatic nitroalmi fragrances. Suitable solvents, diluents or carriers for perfumes mentioned above are, for example: ethanol, iso-propanol, diethylene glycol monoethyl ether, dipropylene glycol, diethyl phthalate and triethyl citrate. As indicated above, the granular composition can be conveniently produced by forming the silica-based granules and then mixing the functional ingredient with the granules. The mixing of the functional ingredient and the granules can be carried out in a variety of ways, known to those skilled in the art, for example by spraying the functional ingredient onto the granules in a rotating drum or on a conveyor belt. Non-limiting examples of suitable powder mixers include Nauter conical mixers, double cone mixers, through mixers, fixed bed mixers and various container mixers with rotating knives. In all of these mixers, the powder loading is fluidized by paddles, agitation with screw air or by mechanical rotation. The functional ingredient, such as perfume oil, is sprayed onto the granules and mixing is continued until the uptake of the functional ingredient to the desired degree is complete (usually so that the granules maintain a free-flowing consistency). The granular composition containing the functional ingredient can then be dropped by gravity into suitable containers. When the granules carrying the functional ingredient are proposed for incorporation into a detergent formulation, it is desirable that the granules, upon contact with water or water containing a fabric washing formulation or the like, disintegrate or be easily dispersed in particles that are small enough to prevent excess deposition on fabric or articles during a wash cycle. The disintegration or dispersibility of the particulate granule is advantageously induced and / or improved by the addition of a dispersing agent to the granular composition, to produce a granule with "dry" strength equivalent to a granule which does not contain dispersing agent but which contact with the water, it will disintegrate or at least disintegrate more easily than the free granule of equivalent dispersing agent. For example, in the case of perfume carrying particles incorporated within a detergent formulation, the disintegration of the granules, within a normal wash cycle, is desirably to such an extent that the resulting particles are small enough to prevent deposition. excessive on the fabric or the item being washed. A suitable dispersing agent is one which does not materially affect either the loading capacity of the functional ingredient, or the ability of the granular composition to retain the functional ingredient or suppress the loss by evaporation thereof.

Typically the granular composition ranges from about 2 to about 20% by weight of dispersing agent, usually at the expense of the amorphous silica component of the composition. The dispersing agent is preferably in the form of an organic particulate material that swells with water, which can be selected from the class of materials known as "super absorbent". Such a material preferably has an ability to swell with water of at least 10 ml / g, more preferably 15 ml / g, and more preferably at least 20 ml / g, typically at least 30 ml / g (e.g. 50 ml / g) higher) . The organic particulate material that swells with water may for example be selected from the group consisting of sodium starch glycollates, sodium polyacrylates, cross-linked sodium carboxymethylcelluloses and mixtures thereof. Desirably, the particle size of the organic particulate swelling with water is less than 100 microns, more preferably less than 50 microns, before swelling. The organic particulate material that swells with the water is conveniently mixed with the amorphous silica, and then agglomerated to form granules containing the organic particulate material. The agglomeration of the silica, with or without dispersing agent, can be achieved, for example, by tray granulation, rotating disk, extrusion, spray granulation or by dry compaction. Preferably, the agglomeration is achieved using a roller compactor that includes a Fitzpatrick Chilsonater commercially available from the Fitzpatrick Company, or an Alexanderwerk roller compactor, commercially available from Alexander erk GmbH. Operation conditions are selected on the compactor so that the resulting granule, which only contains amorphous silica or formulated to include the organic particulate material that swells with the water in the required composition, has a friction value (dry strength measurement). ) which is sufficiently low to give the granular composition sufficient strength to survive a normal manufacturing / processing handling. The material to be tested to determine the friction value needs to be within the preferred size range. This is achieved by holding the agglomerated materials that leave the compactor to a grinding / milling device, such as a hammer mill. The resulting particles are screened to provide particles typically in the size range from about 400 to about 1200 microns. After attaching the granules to the friction test (as described hereinafter) typically from about 5 to about 30% by weight it passes through a sieve of 212 microns. Surprisingly, using effective compaction conditions, agglomerated materials can be prepared which contain the organic particulate material that swells with water that are strong enough to withstand the handling of normal manufacture found in the production of detergent formulations, but which disperse, on contact with water, in particles small enough to prevent deposition on fabrics or an article. It is desirable that the granular composition retain the functional ingredient so that losses are minimal during normal manufacturing / processing handling. This benefit can be demonstrated by holding the granular composition at a pressure below the pressure 1 atmospheric for a period of 24 hours, typically at 8.15 x 10"3 to 10.19 x 10" 3 kg / cm2 (8 to 10 mbar), and measuring the loss of functional ingredient gravimetrically. According to a second aspect of the present invention, there is provided a granular composition comprising granules of inorganic material which carry a volatile organic functional ingredient, substantially free of water in liquid phase, the granules have a retention capacity of the functional ingredient such that from at least about 85% by weight, preferably from about 90% to about 100% by weight of the content of the functional ingredient in the granular composition, is retained with the exposure of the granular composition at a pressure of about 10.19 x 10"3 kg / cm2 (10 mbar) for a period of 24 hours Typically the functional ingredient comprises at least about 30% by weight of the composition The inorganic material is preferably a silica which may have the properties, for example surface, pore volume, particle size, referred to above, if desired a dispersing agent can be incorporated into the composition granular for the purpose referred to above, and the granules of the composition may have a particle size greater than about 200 to about 2000 microns, preferably from about 400 to about 1200 microns. A further preferred feature of the granular composition according to the first and second aspects of the invention is that the granular composition is capable of easily delivering or releasing the functional ingredient when brought into contact with water. Thus the granular composition is preferably such that from about 50%, preferably from about 60% to about 95% by weight of the functional ingredient carried by the granular composition is supplied when brought into contact with water, or water containing a fabric washing composition. If colored granules are required, then food grade colorants, suitable colored pigments, for example pigment dispersions under the trade name Monastral (such as Blue BV paste), or Cosmenyl (such as Blue A2R, Green GG) and pigment powders under the Permanent trade name (such as Carmine FBB 02) or water soluble dyes, such as Patent Blue V, Orange II and Ponceau 4RC, can be added to the granular composition without materially affecting the strength of the granule or its ability to carry and retain The fragance. In applications where the granules are used for visual impact, color tone and strength are desirably homogeneous throughout the granular composition. A further aspect of the invention relates to a granular composition comprising particles of an inorganic material such as amorphous silica formed into granules together with a dispersing agent to aid the disintegration of the granules with the exposure of the granules to a liquid medium, such as an aqueous medium (for example water or water containing a fabric washing formulation), at least a major proportion of the inorganic material is constituted by amorphous silica. The particles of inorganic material, preferably silica gel or a precipitated silica, and the dispersing agent can have any one or more of the characteristics discussed above. A granular composition according to the present invention can be used, for example, in the following product areas involving the eventual contact between the granules and a liquid medium such as water; ie solid or liquid products or gel for treating or washing textiles or fabrics, oral care products, products for personal washing, or application to hard surfaces. Examples include, but are not limited to, abrasive and non-abrasive cleaners, bleaching products, fabric conditioners, laundry products, personal washout bars, shampoos, bath gels, foam baths, herbal baths, toothpastes or mouth rinses, bath cubes, bath salts and bath oils. A laundry detergent powder is a particularly preferred application. In a preferred aspect the invention provides a laundry detergent powder comprising a granular composition defined in the aspects of the invention referred to above, the granular composition prefer incorporates a functional ingredient in the form of a perfume. The laundry detergent powder may otherwise be of conventional composition. Laundry detergent powders use a wide range of compositions. Traditional (or "regular") products are typified by a level of detergent surfactant of between 8% and 20% by weight in total, more commonly from 10% to 15%. The surfactant may be anionic, nonionic, cationic, zwitterionic or amphoteric in nature, and commercial products may contain all kinds of surfactant, but the predominant form is generally anionic (ie anionic surfactants typically account for 50% or more of the total surfactants). Typical detergent surfactants are described in detail in "Surfactant Surface Agents and Detergents" volume II by Schwartz, Perry and Birch, Interscience Publishers (1958). The remainder of a laundry detergent composition generally comprises fillers, fillers, moisture, dirt release agents and slurry and anti-redeposition slurries, and other optional adjuncts such as processing aids, optical brighteners, colorants, foam control agents, anti-corrosion agents, perfumes, pH control agents, enzymes, stabilizers, bleaches and bleach activators. The level of solid components in regular laundry detergent compositions is high, usually above 75%, frequently above 85%. Perfume fillers for such compositions are generally within the range of 0.05% to 0.4%, more commonly from 0.1% to 0.3%, and the ratio of solid constituents to liquid organic constituents in a regular detergent composition is usually at minus 30: 1, and is likely to be consider higher in practice, for example at least 150: 1 and up to 500: 1. Concentrates and hyperconcentrates in laundry detergent powder (for the purposes of this specification also referred to as "concentrados") represent a relatively new product segment that is assuming a growing commercial importance worldwide. These commercial products have a composition rather different from those described above. The total level of detergent surfactant in the concentrated products generally lies within the range of 15% to 60% by weight of the powder, more usually 20% to 40%. In addition to the difference in the level of surfactants, another important point of difference concerns the level of low functionality material such as fillers. In concentrated products the level of sodium sulfate, for example, is rarely above 6% or even 2% by weight, while in regular powders levels of 20% to 30% are common. The composition of the active ingredients may be similar to that in regular, ie predominantly anionic, products, but the invention is not restricted thereto, and for example, a high proportion of nonionics can be advantageously used. The use of higher proportions of non-ionic surfactants is reported to be a significant trend in the • detergent industry, at least for Europe, as reported by Smulders and Krings (Chemistry and Industry, March 1990, pages 160 to 163). ). Examples of detergent powder formulations with high levels of non-ionic are described in EP-A-228011, EP-A-168102, EP-A-425277 and EP-A-120492. Many non-ionic surfactants are liquid at room temperature. Yet another difference between "regular" and concentrated is that the percentage of perfume incorporated in the concentrates tends to be higher than that for use in regular powder, or usually falls above 0.1% by weight, usually within the range of 0.2. % to 2.5% by weight of the powder, more typically from 0.4% to 1.5%.

The amount of granular composition of the invention used in laundry detergent powders will typically be to produce perfume levels in the powder in the ranges given above, ie from .05 to 2.5% by weight, and a typical perfume content is about 0.4% by weight. For use in product formulations containing bleaching agents (which are particularly hostile to perfume components) the perfume is preferably one that is resistant to such attack, and retains high efficiency even when stored in the presence of such hostile ingredients. Non-limiting examples of suitable perfumes are described in EP-A-299561 and US-A-4663068.

Standard Procedures The granular compositions of the invention are defined in terms of the properties and texture of amorphous silicas together with the organic particulate that swells with water (if present) used to produce the agglomerated material, and the size distribution particle size, strength and dispersibility. i) Oil Absorption Oil absorption is determined by the ASTM spatula rubbing method (American Society of Test Material Standards D, 281). The test is based on the principle of mixing flaxseed oil with the silica by rubbing with a spatula on a smooth surface until a paste similar to firm putty is formed, which will not break or separate when cut with a spatula. The amount of oil (grams of 0) used is then put in the following equation: Oil absorption = 0 x 100 / Weight of silica sample in grams That is Oil absorption = grams of oil used / 100 grams of silica. ii) Average Weight Particle Size The average weight particle size of the silica is determined using a Malvern Mastersizer model X, with a 45 mm lens and a MS15 sample presentation unit. This instrument, made by Malvern Instruments, Malvern, orcestershire uses the dispersion principle of Wed, using a low power he / Ne laser. Before the measurement the sample is ultrasonically dispersed in water for 5 minutes to form an aqueous suspension. This suspension is agitated before it is subjected to the measurement procedure set out in the instruction manual for the instrument, using a 45 mm lens in the detector system. The Malvern Mastersizer measures the average particle size distribution of the silica or reference material. The average particle size of weight (d50) or 50th percentile, the 10th percentile (dlO) and the 90th percentile (d90) are easily obtained from the data generated by the instrument. iii) Loose Bulk Density Loose bulk density is determined by weighing approximately 180 ml of silica in a dry 250 ml measuring cylinder, inverting the specimen ten times to remove the air pockets and read the final compact volume. Loose bulk density = (Weight x 1000) / Volume g / liter iv) BET Surface Area The surface area is determined using standard nitrogen adsorption methods of Brunauer, Emmett and Teller (BET), using the single point method with a Sorpty 1750 apparatus supplied by the Cario Erba Company of Italy. The sample was degassed under vacuum at 270 °° C for 1 hour before measurement. v) Particle size distribution by sieve analysis The particle size distribution of the granular composition and the dispersing agent is carried out using sieve analysis. 100 g of the sample is placed on the upper sieve of a series of BS sieves, in intervals of approximately 100 microns between 100 and 1500 microns. The sieves are arranged in order with the finest in the bottom and the thickest in the top of the stack. The sieves are placed in a mechanical vibrator, for example, Inclyno Mechanical Sieve Shaker by Pascall Engineering Co. Ltd. Covered with a lid and shaken for 10 minutes. Each fraction of the sieve is weighed exactly, and the results are calculated: % residual = (weight of waste x 100) / weight of the sample To determine the particle size distribution of the organic particulate material swelling with water, sieve sizes in the range of 30 to 110 microns are selected in intervals ranging from 10 to 25 microns. Typically, 10 g is placed in the thicker screen at the top, and the described procedure is repeated to measure the particle size distribution of the granules. vi) Fragrance loading capacity 20.0 g of granules are placed in a 100 ml beaker. Using a disposable pipette, limonin (available from Quest International), a substitute for the perfume, is dripped onto the granules and stirred with a spatula. As the granules absorb the limonin, a point is reached where the granules are saturated with perfume, that is, the point at which they can not absorb more. At this point they rapidly change from a free-flowing powder to a moist, viscous mass in which the granules pile up with each other. The point at which this happens is the end point. The sample is weighed and the weight of added limonin is determined. The result can be expressed as grams of limonin per 100 grams of granules or as% of limonin in the saturated mixture of limonin-granules. vii) Dry Strength (Friction Test) Dry strength is determined by a method based on the friction of the granules in a high shear mixer. First a control is carried out to determine the% by weight of fines (<212 microns) already present or generated by the sieving process. For control, approximately 20 grams of non-scented granules, exactly weighed, are sieved for 10 minutes on a sieve of 212 microns on a laboratory sieve shaker. The% by weight of material that passes the sieve of 212 microns is recorded. For the test, 20.0 grams of unscented granules are placed in a Sirman CV6 food processor (available from Metcalfe Catering Equipment, Bleaunau Ffestiniog, Gwyndd, Wales) and the processing is turned on at full speed (2100 revs / minute) per one minute. The sample is sifted for 10 minutes as before and the% by weight that passes the sieve of 212 microns is measured. The% by weight and less than 212 microns (the control) is subtracted to obtain the friction value. vii) Wet Disintegration Test For. To determine the degree to which the granules disintegrate in water, a control is carried out according to the procedure above, to determine the% by weight of fines less than 212 micras already present, so that it can be deduced from the result of the proof. For the test, the granules are loaded with fragrance at a level close to their maximum load capacity, but without deteriorating the capacity of free flow. The fragrance used for the first method is the "fragrance A" of Quest International. The formulation of this is given in the fragrance retention test section below. The sample is allowed to stand for 12-24 hours to allow the perfume to distribute evenly throughout the granules. Mix 1 gram of the perfumed sample with 9 grams of a washing powder (Radion Automatic) and place it in a 2-liter plastic bottle (about 24 cm high and 12 cm in diameter) and add one liter of hot water (around 40-50 ° C). Four bottles are loaded, in a row, into a box that can be rotated about its longitudinal axis so that the bottles are turned end to end. The rotation of the box is driven at a speed of 34 revolutions per minute by an electric motor. After 20 minutes of this rotary mixing, the bottles and the contents of each pour are removed through a sieve of 212 microns. The bottles are rinsed with water and the rinses are poured through the sieve. The residue on the screen represents the portion of the original sample that has not disintegrated to less than 212 microns. The residue is rinsed in a glass, the excess water is decanted, the sample is dried at 145 ° C and weighed. The result is expressed as% by weight of the granules (less fragrance) that passes the sieve of 212 microns. The higher the number the more the sample has disintegrated in contact with the aqueous medium. ix) Fragrance Retention Two methods have been developed to demonstrate the retention of fragrance by granules. The first method is based on the loss of weight in a vacuum, while the second measures the fragrance that remains after two weeks of storage in a washing powder. The fragrance for the first method used is the "fragrance A" of Quest. This has the composition below: Ingredient% by weight Anther (Q) 1.0 Coumarina 2.0 Gyrane (Q) 0.5 Aldehyde hexyl cinnamic 18.0 Jasmacyclene (Q) 5.0 Jasmopyrane Forte (Q) 4.0 Lilial (G) 10.0 Lixetone (Q) 8.0 Methyl iso alpha ionone 5.0 Acetate 4- tert-butylcyclohexyl 5.0 2-phenylethyl alcohol 15.0 Pivacyclene (Q) 0.5 Tetrahydrolinalol 6.0 Trascolide (Q) 20.0"Q" and "G" respectively denote registered trademarks of the Companies and Givaudan Quest Group. A small sample (approximately 10 grams) of granules loaded to near their loading capacity with "fragrance A" is prepared by dropping the fragrance on the granules and mixing gently, the amount of fragrance used is such that the free flow property of granules is not damaged. The sample is allowed to stand overnight to allow the fragrance to disperse uniformly in the granules. 5.0 grams of the sample are weighed exactly in a Petri dish of 4 cm in diameter and placed in a vacuum desiccator. The desiccator is connected to a high vacuum pump, and evacuated at a pressure of 8.15 x 10"3 to 10.19 x 10" 3 kg / cm2 (8 to 10 mbar), and is maintained at this level. At intervals of 4, 7 and 24 hours the sample is removed to weigh it and then replaced. A rapid weight loss initially occurs, mainly due to the loss of moisture (and to a lesser degree to the loss of the more volatile components of the fragrance). After this, the loss is much more gradual and represents the loss of fragrance with only a minor contribution of wastewater. Experiments with granules without fragrance show that for silicas typically 50-80% of the water is lost in the first 4 hours. Additionally, with granules with fragrance, it is possible to trap volatile compounds that evaporate using liquid nitrogen. By this means it can be shown that the material trapped in the first few hours consists of a mixture of aqueous and organic liquids. In later times only the perfume is collected. As water only constitutes a small percentage of the total content of volatile compounds of perfumed granules (typically <10%), and is lost mainly within the first few hours, the contribution to total weight loss by evaporation of water It will be insignificant after 7 hours. Consequently, it is the loss of weight between the measurements of 7 and 24 hours that produces the most accurate measure of the loss of fragrance by evaporation. Taking the% by weight lost in the 24 hours and subtracting the corresponding value in the 7 hours you get the weight loss during the period of 7-24 hours. Dividing it by 17 (the duration, in hours, of this period) the proportion of perfume loss in% of perfume available per hour is obtained, multiplying it by 24 then gives the% by weight of available perfume lost in the period of 24 hours with The contribution of moisture eliminated for the most part. Subtracting this value of 100% gives the% by weight of retained perfume. The second method uses a mixture of 10 selected fragrance ingredients to cover a range of functionalities and volatilities. The granules were loaded with this ten component fragrance blend. The fragrance mixture was a mixture of equal proportions of common perfume ingredients selected to represent a range of functional groups and to avoid co-elution during gas chromatography (GC) analysis. It was not formulated to have a pleasant smell. The ingredients were: limonin, linalool, alpha terpineol, anisic aldehyde, herbanate, dodecyl nitrile, diethyl phthalate, hexyl salicylate, hexyl cinnamic aldehyde, tonalid 2. These are available from Quest International. To this mixture was added a small amount of a solvent dye (e.g., 0.1% Red 24 of Solvent) to impart a bright color and the colored perfume mixture was then added to the granules to a level close to its capacity of load. The perfumed granules were then mixed in a washing powder formulation. 50 g of the granules / washing powder mixture were stored for two weeks at 45 ° C in sealed glass jars. After this time the bottles were opened and approximately 0.01 g of the granules were collected, identified by their color, using tweezers and analyzed by GC to determine the quantities of the various perfume components that remained in them. The% of each component present as a percentage of the original was determined and a total average value was calculated. The result was expressed as the amount of perfume retained as a percentage of the original. x) Fragrance Release To demonstrate the rapid release of fragrance in water, first "fragrance A" was colored with a little solvent dye (Green No. 6 D &C added in about 40 mg per 100 ml of fragrance) . The granules were loaded to about their loading capacity (but without deterioration of their free flow) with the colored fragrance, and then 10.0 grams of the granules were added to approximately 80 ml of water in a 100 ml test tube. The water quickly displaced the fragrance, which rose to the surface like an oil. The dye imparted an intense blue / green color to the fragrance, making it easily visible as an oily layer on the surface. Stirring with a stiff wire, or blowing bubbles through the mixture with a pipette, helped release the trapped globules of fragrance. After about five minutes of stirring the mixture was allowed to settle for another ten minutes, after which time the volume of the fragrance was read using the graduations on the side of the test piece. From the specific gravity of the fragrance (0.96), the% by weight of the available fragrance that has been released can be calculated. xi) Volume increase of the organic particulate dispersion aid To demonstrate the swelling capacity of the organic dispersion aid, 19.6 g of the material was mixed with 0.4 g of ultramarine pigment and compressed into a tablet using a laboratory tablet press at a time. pressure of about 2583 kg / cm2 (2500 atmospheres) to give a 32 mm diameter tablet. This was crushed and sieved to provide granules 500-1000 microns in size. A glass tube 33 mm in internal diameter and about 30 cm long with a sintered porous glass disc (porosity 1) adapted at one end was dipped vertically, end down, into a large glass with water (a 25 ° C) so that the water level rose to about 14 cm above the sintered glass. 1 g of granules was added to the tube, and allowed to settle on the sintered glass disk. With this arrangement the water has access to the granules from both ends, above and below. The granules immediately begin to swell, forming a jelly-like mass. The ultramarine pigment imparted a blue color to the dough, making it easy to see the top and record its height. The height of the swollen mass was recorded at intervals and showed a rapid initial rise followed by leveling after 20-30 minutes. From the diameter of the tube, the volume of the swollen mass can be calculated. The result can be expressed as ml / g of organic particulate material after a fixed time (for example 20 minutes). The invention will now be illustrated by reference examples based on the prior art, together with the non-limiting Examples of the invention.

Reference Examples 1 to 4 (Prior Art) Examples of the following prior art have been repeated: WO96 / 0903, Composition 3 - Reference Example 2 US-A-5656584, Example 2 - Reference Example 3 JP-A-62072797 , Example - Reference Example 4 All of the highlighted variables were followed as important in the examples of the prior art, as closely as can be achieved by those skilled in the art, according to the teachings of the prior art patents. The compositions used are listed in Table 1, and when more than one component was used, the pulverized materials were mixed together before agglomerating. Reference Examples 1 and 2 were prepared by the so-called "wet" agglomeration. Deionized water was added to the powder mixtures to give a water: solids ratio of 1.33 to 1 and the resulting 200 g mixtures were agglomerated using a Sirman CV6 laboratory scale mixer, supplied by Metcalfe Catering Equipment Ltd., Blaenau Ffestiniog, Wales . The resulting wet agglomerated materials were then dried in an oven at 150 ° C for 4 to 6 hours, they were gently forced through a sieve of 1000 microns and sieved to the required particle size distribution. Reference Examples 3 and 4 were made by "dry" agglomeration. The particles were brought into contact with each other either by compressing the powder bed in a tablet press, or between the rollers of a compactor. In Reference Examples 1, 2 and 4, the perfume was added to the previously made granules. For Reference Example 3, the perfume was already present in the mixture before compacting it into granules, according to the method described in the relevant patent.

Table I The properties of the materials used to prepare the Reference Examples are given in Table II.

Table II Table III lists the properties of the granular compositions of the repeats. In the Reference Examples the loading capacity is expressed as% perfume in granules saturated with perfume; retention is expressed as% of available perfume retained after 24 hours at 8.15 x 10"3 - 10.19 x 10" 3 kg / cm2 (8 - 10 mbar), friction is given as% < 212 microns, the dispersion as% < 212 micras All percentages are% by weight.

It can be seen that none of the Reference Examples has the required balance of properties. Granular compositions containing amorphous silicas have good loading capacity, but are too resistant to dispersing into sufficiently small particles to prevent deposition on the fabric or article. The granular zeolite compositions have a poor loading capacity. Not surprisingly the granular composition of zeolite containing almost 50% sucrose is dispersed when contacted with water, but as will be demonstrated in the examples of this invention its dispersibility is lower than the granular compositions containing the organic particulate material that swells in water.

Specific Description of The Invention Examples of the preparation of the granular compositions will now be given, to illustrate but not limit the invention. Unless stated otherwise, the Examples were prepared by mixing the dry ingredients in a Pek mixer (George Tweedy &Co. De Preston - 281b SA Machine) and compacting in a roller compactor (Alexanderwerk WP50 - manufactured by Alexanderwerk AG , D 5630 Remscheid 1, Germany). The preparative method is now described in detail. The silica and organic particulate material swelling in water were mixed together, in the proper proportions, in a Pek mixer for 30 minutes. Optionally, if a colored product is desired, a master batch of colored silica is first prepared. This masterbatch is then added to the silica and the organic particulate material in the Pek mixer and the ingredients mixed for 30 minutes. The proportion of dye in the masterbatch and the proportion of masterbatch in the total mixture were calculated to give a product with the desired level of dye (typically < 5%, preferably < 1%) using from 1-25%, preferably 2-15% by weight of masterbatch in the total mixture. A minimum of 2 kg of mixed material, prepared as described above, is compacted by feeding it to an Alexanderwerk roller compactor, adapted with a sintered block vacuum deaeration system. The parameters used for the preparation of the Examples in this patent were: roller speed 2, screw feeder 2, vacuum 0.8, speed of agitator 2. The pressure parameter of the roller was varied according to the desired granule strength, pressures Higher ones give rise to stronger granules defined by their friction value. The roll pressure used in the Examples was 101.9 kg / cm2 (100 bar), unless stated otherwise. The compacted material of the compactor was fed to a granulator, which is part of the machine, and was forced through a 1.2 mm screen. The resulting granules were then sieved to the desired particle size range using standard laboratory sieves. The range of particle size used for the Examples below was 500-1000 microns unless stated otherwise. When perfume needs to be added to the granules, it is added drop by drop under gentle agitation until the desired load is secured, the samples are then allowed to equilibrate for 24 hours.

Example 1 Amorphous silica SD 2255 (available from Crosfield Limited of Werrington, England) was mixed together with Vivistar P5000 in the matrix listed in Table IV, agglomerated in the roller compactor, ground and sieved to the particle size specified above. Vivastar P5000 is an available starch and sodium glycolate from J. Reettenmaier & Sohne, Germany.

Table IV The properties of silica and Vivastar P5000 are given in table V. It can be seen that the amorphous silica SD 2255 exhibits both a high surface area and a high pore volume which indicates that the mesoporic structure responsible for this increase observed in porosity contains micropores Table V In the Table above and elsewhere in this specification, NM indicates "not measured." The properties of the agglomerated materials are listed in Table VI. In the table, the loading capacity is expressed as% perfume in granules saturated with perfume; retention is expressed as% of available perfume retained after 24 hours at 8.15 x 10"3 - 10.19 x 10" 3 kg / cm2 (8 - 10 mbar), friction is given as% < 212 microns, the dispersion as% < 212 microns, and the release of perfume as% perfume available after 15 minutes of contact with water. All percentages are% by weight.

Example A does not contain Vivastar P5000. The data obtained from Examples IB to 1E show that the addition of Vivastar P5000 does not have a detrimental effect on particle strength, loading capacity and perfume retention. It can be seen that as the levels of Vivastar P5000 increase, the granular composition is more easily dispersed into particles small enough to pass through a 212 micron sieve. A high level of perfume is released into the aqueous phase independently of both, the strength and dispersibility of the granular composition.

Example 2 Amorphous silica SD2255 (available from Crosfield Limited, UK) was mixed with Vivastar P5000 4 according to the Examples given in table VI and compacted in the roller compactor and sieved to the desired particle size.

Table VII The properties of silica and Vivastar P5000 are given in Table VIII. The silica used in this Example SD 2311 exhibits a higher surface area and a pore volume higher than SD2255, indicating the presence of a wider pore structure containing an even greater presence of micropores.

Table VIII The properties of the agglomerated materials are listed in Table IX. In this table, the carrying capacity is expressed as% perfume in granules saturated with perfume; retention is expressed as% of available perfume retained after 24 hours at 8.15 x 10"3 - 10.19 x 10" 3 kg / cm2 (8 - 10 mbar), friction is given as% < 212 microns, the dispersion as% < 212 microns, and the release of perfume as% perfume available after 15 minutes of contact with water. All percentages are% by weight. Example 2A does not contain Vivastar. The experimental data measured for Compositions 2B to 2D show that the addition of Vivastar P5000 does not have a detrimental effect on particle strength, chargeability and perfume retention. As is the case in Example 1, it can be seen that when the Vivastar levels are increased, the granular composition is more easily dispersed into particles small enough to pass through a 212 micron sieve. A high level of perfume is released into the aqueous phase independently of both, the strength and dispersibility of the granular composition.

EXAMPLE 3 To demonstrate the ability of different kinds of organic particulate materials that swell with water to act as dispersing agents, a range of granular compositions containing 9 parts of SD 2255 and 1 part of organic particulate material was prepared. Table X lists the properties and suppliers of organic particulate materials that swell with the water used to prepare the granular compositions. * in the table above, APS is Average Particle Size The properties of the granular compositions are given in Table XI. In the table the carrying capacity is expressed as% perfume in granules saturated with perfume; retention is expressed as% of available perfume retained after 24 hours at 8.15 x 10"3 - 10.19 x 10" 3 kg / cm2 (8 - 10 mbar), friction is given as% < 212 microns, the dispersion as% < 212 micras All percentages are% by weight. Example 3A does not contain organic particulate material. It can be seen that the granular composition containing Ac-Di-Sol SD-711 (Example 3C) gives the best balance of properties, followed by the granular compositions using Vivastar and Primogel as the dispersion aid (Examples 3B and 3D). All granular compositions containing organic particulate material show improved dispersibility when compared to the control. The high loading capacity of the granular composition 3E is attributable to using a lower compaction pressure, see Example 6.

Table XI Example 4 It is clear from Example 3 that the organic particulate Ac-Di-Sol that swells in water is the most effective dispersion aid of those illustrated. The purpose of Example 4 is to investigate the effect of varying the concentration of the organic particulate material on the properties of the granular compositions. Mixtures of SD2255 were made with Ac-Di-Sol according to the matrix listed in Table XII, compacted in the roller compactor, crushed and sieved to the previously specified particle size.

Table XII The properties of the granular compositions are given in Table XIII. In the table, the loading capacity is expressed as% perfume in granules saturated with perfume; the retention is expressed as% of available perfume retained after 24 hours at 8.15 10 -3 10.19 x 10"3 kg / cm: (8 - 10 mbar), the friction is given as% < 212 microns, the dispersion as% < 212 micras All percentages are% by weight. Example 4A does not contain organic particulate material. It can be seen that even at a concentration of 2%, Ac-Di-Sol gives rise to a reasonable balance of properties.

Table XIII Example 5 The particle size used to prepare the agglomerated material can affect strength and dispersibility. Vivastar P5000 was sieved into several size fractions and combined with two different sizes of the SD 2255 silica in the composition matrix listed in Table XIV. A thicker silica SD 2255 product (available from Crosfield Limited, UK) was obtained by grinding the gel feed to a larger particle size. The granular compositions were prepared in a roller compactor, crushed and sieved to the specified particle size.

Table XIV The properties of the agglomerated materials are listed in Table XV. In the Table the carrying capacity is expressed as% perfume in granules saturated with perfume; retention is expressed as% of available perfume retained after 24 hours at 8.15 x 10"10.19 x 10 ~ 3 kg / cm2 (8 - 10 mbar), the friction is given as% < 212 microns, the dispersion as% < 212 micras All percentages are% by weight.

Table XV Example 5 contains SD2255 and Vivastar P5000 in a particle size used in the previous Examples. The experimental data measured for Examples 5B to 5D show that reducing the particle size of Vivastar has a beneficial effect on the dispersibility of the granular composition. The comparison between the properties of Example 5A and Example 5D shows that the dispersibility of the granular composition increases when the particle size of the amorphous silica is reduced. There is no detrimental effect on friction, and there is an indication that the load capacity improves when the particle size of the amorphous silica increases.

Example 6 In Example 3 reference is made to the effect of the compaction pressure on the roller compactor. Here the effect of the roller compactor pressure, together with the particle size of the amorphous silica and the concentration of the organic particulate material that swells with the water in the granule was investigated in the experimental design matrix listed in Tables XVIA & B, respectively. Amorphous silicas (SD2255, SD2255A) were mixed with Vivastar according to the compositions given in tables XIVA & B and were compacted in the roller compactor at two compaction pressures, 61.14 and 101.9 kg / cm2 (60 and 100 bar), respectively, were crushed and sieved to the specified particle size.

Table XVIA Table XVIB The properties of the granular compositions are listed in Table XVII. In the Table the carrying capacity is expressed as% perfume in granules saturated with perfume; retention is expressed as% of available perfume retained after 24 hours at 8.15 x 10"3 - 10.19 x 10" 3 kg / cm2 (8 - 10 mbar), friction is given as% < 212 microns, the dispersion as% < 212 micras All percentages are% by weight.

It can be seen that in each case increasing the compaction pressure has a beneficial effect on the friction value of the granular composition, but decreases its loading capacity. Surprisingly little effect is seen, if any, on the dispersibility of the granular compositions.

Example 7 To demonstrate the effectiveness of the organic particulate materials swelling with water as dispersion aids, a series of granular compositions was prepared according to the composition matrix listed in Table XVIII.

The granular compositions were prepared in the roller compactor, crushed and sieved to the specified size range.

Table XVIII As described in the methods section for the dispersibility test, the granular composition is contacted with water and stirred for 20 minutes. To illustrate the improved dispersibility imparted to the granular compositions by the organic particulate material the time during which the sample is agitated is reduced in stages from 20 to 2 minutes. The measurements obtained are summarized in Table XIX.

Table XIX It can be seen that in most cases the dispersion is rapid, most of it passes in two minutes of exposure to the test conditions.

EXAMPLE 8 To demonstrate the relationship between the propensity of the swollen particulates with the water to expand when contacted with water and the level of dispersibility imparted to the granular composition, a series of granular compositions containing 1 part was prepared. of organic agent that swells and 9 parts by weight of SD2255. The compositions were compacted in the roller compactor, together with controls that did not contain organic particulate material, were ground and sieved to the specified particle size distribution. The properties of the agglomerated materials, together with the capacity to increase the volume of granules of the pure dispersant as described in the standard procedures, recorded after contacting the organic particulate material with water for 20 minutes, are listed in Table XX . In the table, the dispersibility is expressed as the% by weight that passes through a sieve of 212 microns.

Table XX Arbocel is a registered trademark, the product is available from J. Rettenmaier & Sohne Corn starch can be obtained from the National Starch Corporation, New Jersey, USA. The last two materials are examples of potential organic particulate materials that swell that were found not to work on this application. It can be seen that organic particulates that swell in water having bulking capacities greater than 10 ml / g impart dispersibility levels greater than 50% to the granules. While other factors may also be important, such as particle size and shape, the property of bulking seems to provide adequate guidance in the identification of organic particulate materials that impart the desired levels of dispersion.

EXAMPLE 9 The perfume retention data cited in Examples 1 to 4 have been determined by measuring the weight loss with the exposure of the granular composition containing perfume at a pressure lower than atmospheric pressure. In this example the perfume retention of the granular composition in contact with a typical fabric washing powder is compared to that obtained by exposing the granules to a reduced pressure. To 50 g of a typical wash powder formulation (Table XXI), sufficient granular composition containing perfume was added to give a perfume concentration of 0.4% by weight.

Table XXI * sodium salt of tet raacet iletilen diamine The powder containing the perfumed granules was sealed in jars and stored for 2 weeks at 45 ° C. the amount of perfume remaining in selected granules was determined by gas chromatography. A more detailed description of the method is given under the Standard Procedures. Table XXII summarizes the data obtained by the two methods to determine the retention of perfume. It can be seen that although the values obtained by analyzing the granules that have been in contact with the washing powder are much lower than those determined by measuring the loss of weight under reduced pressure., the data show the same trends, because those compositions that give higher perfume retention values when exposed to a pressure lower than atmospheric pressure also give the highest values in the storage test when they are put in contact with a powder of washing fabrics.

Claims (41)

1. RE IVINDICATIONS 1. A granular composition for carrying and retaining a volatile organic functional ingredient, substantially free of water in liquid phase, the granular composition comprises at least 40% by weight of an amorphous silica, the amorphous silica has a surface area of at least 550 m2 / g, a pore volume of about 1.0 to about 2.5 ml / g, and a particle size of no more than 50 microns (preferably no more than 40 microns, and more preferably no more than 30 microns), the granules of the composition disintegrate when brought into contact with water, and have: a particle size greater than 200 and up to 2000 microns, preferably from 400 to 1200 microns; and a dry strength such that no more than 30%, more preferably no more than 25%, and more preferably no more than 20%, by weight passes through a 212 micron sieve when subjected to the defined friction test at the moment.
2. 2. A granular composition according to claim 1, wherein the granules have a particle size from 400 to 1200 microns.
3. 3. A granular composition according to claim 1 or 2, wherein the amorphous silica constitutes up to 70% by weight of the composition.
4. 4. A granular composition according to claim 1, 2 or 3, wherein a functional ingredient is present in an amount of at least 30% by weight of the composition.
5. 5. A granular composition according to claim 4, wherein the functional ingredient comprises up to 60% by weight of the composition.
6. 6. A granular composition according to any of claims 1 to 5, wherein the silica granules have an absorption capacity of the functional ingredient of at least 35% by weight.
7. 7. A granular composition according to any of claims 1 to 5, wherein the silica granules the silica granules have an absorption capacity of the functional ingredient of at least 40% by weight.
8. 8. A granular composition according to any of claims 4 to 7, wherein the composition is in the form of free-flowing granules carrying the functional ingredient.
9. 9. A granular composition according to any of claims 1 to 8, wherein the granular composition contains a dispersing agent to improve the dispersion of the granules as small particles in contact with water.
10. 10. A granular composition according to claim 9, which, upon contact with water, is dispersed to a degree such that from 50% by weight it will pass through a sieve of 212 microns.
11. 11. A granular composition according to claim 9, which, upon contact with water, is dispersed to a degree such that from 60% to 95% by weight will pass through a 212 micron sieve.
12. 12. A granular composition according to any of claims 9 to 11, wherein the dispersing agent is present in an amount from 2 to 20% by weight of the composition.
13. 13. A granular composition according to any of claims 9 to 12, wherein the dispersing agent is in the form of an organic particulate material that swells in water.
14. 14. A granular composition according to claim 13, wherein the particulate material has an ability to swell in the water of at least 10 ml / g.
15. 15. A granular composition according to claim 13, wherein the particulate material has a swelling capacity in the water of at least 15 ml / g.
16. 16. A granular composition according to claim 13, wherein the particulate material has a swelling capacity in the water of at least 20 ml / g.
17. 17. A granular composition according to any of claims 13 to 16, wherein the organic particulate material comprises a sodium starch glycolate, a sodium polyacrylate, a cross-linked sodium carboxymethyl cellulose or a mixture thereof.
18. 18. A granular composition according to any one of claims 13 to 17, wherein the particle size of the organic particulate material swelling in water is less than 100 microns before volume increase.
19. 19. A granular composition according to any of the preceding claims, wherein the functional ingredient comprises a perfume.
20. 20. A granular composition comprising granules of inorganic material carrying a volatile organic functional ingredient, substantially free of water in liquid phase, the granules have a retention capacity of the functional ingredient such that about 85% by weight of the content of the functional ingredient in the Granular composition is retained with the exposure of the granular composition at a sub-atmospheric pressure of about 10.19 x 10"3 kg / cm2 (10 mbar) for a period of 24 hours.
21. 21. A granular composition according to claim 20, wherein the granules have a retention capacity of the functional ingredient such that about 90% to about 100% by weight of the perfume content in the granular composition is retained upon exposure of the granular composition. Granular composition at sub-atmospheric pressure for a period of 24 hours.
22. 22. A granular composition according to claim 20 or 21, and having the characteristics specified in any one or more of claims 1 to 19.
23. 23. A process for the production of a granular composition, which comprises combining an amorphous silica having a surface area of at least 550 m2 / g, a pore volume of about 1.0 to about 2.5 ml / g, and a particle size of not more than 50 microns with a volatile organic functional ingredient, substantially free of water in liquid phase, to produce a granular composition comprising at least 40% by weight of the amorphous silica, the granules of the composition have: a particle size greater than 200 to 2000 microns; and a dry strength such that no more than 30%, more preferably no more than 25%, and more preferably no more than 20% by weight pass through a 212 micron sieve when subjected to the friction test defined in the present.
24. 24. A process according to claim 23, in which the amorphous silica is initially agglomerated to form granules having a particle size of greater than 200 to 2,000 microns, in which the functional ingredient, for example a perfume, is mixed after this with the granules.
25. 25. A process according to claim 24, in which the granules formed before the addition of the functional ingredient are free-flowing, and in which the amount of functional ingredient mixed with the granules is limited to an amount that allows the retention of the Free flow of the granules that carry the active ingredient.
26. 26. A process according to any of claims 23 to 25, wherein the functional ingredient comprises a perfume.
27. 27. A granular composition comprising particles of an inorganic material formed into granules together with a dispersing agent to aid in the disintegration of the granules with the exposure of the granules to a liquid medium.
28. 28. A granular composition according to claim 27, which, upon contact with the liquid medium, is dispersed to a degree such that from 50% by weight will pass through a sieve of 212 microns.
29. 29. A granular composition according to claim 27, which, upon contact with the liquid medium, is dispersed to a degree such that from 60% to 95% by weight will pass through a 212 micron sieve.
30. 30. A granular composition according to any of claims 27 to 29, wherein the dispersing agent is present in an amount from 2 to 20% by weight of the composition.
31. 31. A granular composition according to any of claims 27 to 30, wherein the dispersing agent is in the form of an organic particulate material that swells in water.
32. 32. A granular composition according to claim 31, wherein the particulate material has a swelling capacity in the water of at least 10 ml / g.
33. 33. A granular composition according to claim 31, wherein the particulate material has a swelling capacity in the water of at least 15 ml / g.
34. 34. A granular composition according to claim 31, wherein the particulate material has a swelling capacity in the water of at least 20 ml / g.
35. 35. A granular composition according to any of claims 31 to 34, wherein the organic particulate material comprises a sodium starch glycolate, a sodium polyacrylate, a cross-linked sodium carboxymethyl cellulose or a mixture thereof.
36. 36. A granular composition according to any of claims 31 to 35, wherein the particle size of the organic particulate material swelling in water is less than 100 microns before the volume increase.
37. 37. A granular composition according to any of claims 27 to 36, wherein the inorganic particles comprise silica.
38. 38. A laundry detergent powder comprising a granular composition according to any of claims 1 to 22, or claims 27 to 37.
39. 39. A laundry detergent powder according to claim 38, wherein the amount of detergent is between and 20% by weight.
40. 40. A laundry detergent powder according to claim 38, wherein the amount of detergent is between 15% and 60% by weight.
41. 41. A laundry detergent powder according to any of claims 38 to 40, wherein the functional ingredient comprises a perfume in an amount within the range of

    0. 05 to 2.5% by weight of the powder.