ES2655979T3 - Detergent composition in particulate form, concentrated packaging - Google Patents

Abstract

A packaged particulate detergent composition, contained in a package, wherein the package comprises at least one transparent portion and the composition comprises more than 50% by weight of detergent surfactant and at least 70% by number of the particles comprises (i ) a core comprising mainly surfactant and 0.0001 to 0.1% pigment, preferably 0.001 to 0.01% pigment, where the pigment is selected from anionic pigments and non-ionic pigments; and (ii) a cover, comprising water-soluble inorganic salt deposited by crystallization from an aqueous solution, where the particles have substantially the same shape and size of each other, characterized in that each particle has particular dimensions x, y and z, in which x is 0.2 to 2 mm, and is 2.5 to 8 mm (preferably 3 to 8 mm), and z is 2.5 to 8 mm (preferably 3 to 8 mm).

Description

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DESCRIPTION

Detergent composition in particulate form, concentrated packaging

The present invention relates to a particulate detergent composition, concentrated packaging with high visual appeal. In particular, it refers to a product used in low dosage levels, for example less than 40g of dosage per wash. In particular, it relates to detergent compositions concentrated in the form of particles, formed by extrusion and coating, in particular with those formed by extrusion of a dry mixture of surfactant, cutting the extruded products into particles having a diameter of at least two times its thickness and the coating of the particles thus formed, by atomizing an aqueous solution of an inorganic salt in a fluid bed, and drying to form a hard shell.

Compact or concentrated compositions offer the advantage that the size of the package is small, which is environmentally desirable. However, the visual impact on the shelf at retail outlets, for example in crowded supermarket shelves, can also be reduced as a result of the small product size. Visual appeal can be improved by increasing packaging, but this is counterproductive from an environmental point of view.

EP2166077A1 discloses a particle for use in a composition, comprising a first coating layer, which includes a coating material selected from a surfactant, surfactant precursor, wash aid, film-forming polymer and mixtures thereof, and a core, where at least a portion of said core is covered by said cover, in which the particle further comprises a pigment that gives hue.

It is an object of the present invention to provide a particulate detergent composition, concentrated, packed, which has a visual appeal and even storage stability, as far as the visual features are concerned.

In accordance with the present invention, a packaged particulate detergent composition is provided, contained in a package according to claim 1.

With the previous arrangement, the product of particles is colored but the dye, the pigment, has greater stability against visible light, and can be stored in transparent packages, thereby improving the stability of the same feature, providing notoriety in the shelf .

Transparent packaging

As far as packaging is concerned, "transparent" indicates that the light transmission is greater than 25% at the wavelength of approximately 410-800 nm.

The transparent layer of the package according to the invention preferably has a transmission of more than 25%, more preferably more than 30%, more preferably more than 40%, more preferably more than 50% in the visible part of the spectrum (approx. 410 -800 nm).

Alternatively, the absorbance of the transparent layer may be measured as less than 0.6 (equivalent to approximately 25% transmission) or for having transmission greater than 25% in which% transmission is equal to:

1 x 100%

-JO absorbance

On the contrary, the absorbance of the opaque layer can be measured as greater than 0.6. For purposes of the invention, as long as a wavelength in the range of visible light has a transmission greater than 25%, the container is considered transparent.

Unless stated otherwise, all percentages are indicated as percentages by weight.

Suitable materials for the transparent inner layer of the packaging include, but are not limited to: polypropylene (PP), polyethylene (PE), polycarbonate (PC), polyamides (PA) and / or polyethylene terephthalate (PETE), polyvinyl chloride (PVC); and polystyrene (PS). The container can be formed by extrusion, molding, for example blow molding from a previous mold or by thermoforming or by injection molding. So

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alternatively, the absorbance of the bottle can be measured as less than 0.6 (approximately equivalent to 25% transmission) or by having transmission greater than 25% in which% of transmission is equal to: 1/10 absorbance x 100% and corresponds to absorbance levels for the previous remaining preferred levels.

Pigment

The pigment is added to the surfactant mixture in the core, preferably the pigment is dissolved in the surfactant before the core is formed.

In Industrial Dyes edited by K. Hunger 2003 Wiley-VCH ISBN 3-527-30426-6, pigments are described.

The pigments for use in the present invention are selected from anionic and non-ionic pigments. Anionic pigments have a negative charge in an aqueous medium at pH 7. Examples of anionic pigments are found in the acid and direct pigment classes in the Color Index (Society of Dyers and Colourists and American Association of Textile Chemists and Colorists). The anionic pigments preferably contain at least one sulfonate or carboxylate group. Anionic pigments have no charge in an aqueous medium at pH 7, examples are found in the class of pigments dispersed in the Color Index.

The pigments can be alkoxylated. The alkoxylated pigments are preferably in the following generic form: pigment-NR1R2. The NR1R2 group is attached to an aromatic ring of the pigment. R1 and R2 are independently selected from polyoxyalkylene chains that have 2 or more repetitive units and preferably that have 2 to 20 repetitive units. Examples of polyoxyalkylene chains include ethylene oxide, propylene oxide, glycidol oxide, butylene oxide and mixtures thereof.

A preferred polyoxyalkylene chain is [(CH2CR3HO) x (CH2CR4HO) and R5) in which x + y <5 in which y> 1 and z = 0 to 5, R3 is selected from: H; CH3; CH2O (CH2CH2O) zH and mixtures thereof; R4 is selected from: H; CH2O (CH2CH2O) zH and mixtures thereof; and R5 is selected from: H; and, CH3

A preferred alkoxylated pigment for use in the invention is:

image 1

Preferably the pigment is selected from acid pigments; dispersed pigments and alkoxylated pigments. More preferably the pigment is a non-ionic pigment.

Preferably the pigment is selected from those that have: anthraquinone chromophores; mono-azo; bis-azo; xanthene; phthalocyanine; Phenazine More preferably the pigment is selected from those that have: anthraquinone and mono-azo chromophores.

The pigment is added to the cover paste and is stirred before application to the core of the particle. The application can occur by any suitable procedure, preferably atomization on a core particle, as detailed above.

The pigment can be any color, preferably the pigment is blue, violet, green or red. More preferably the pigment is blue or violet.

Preferably the pigment is selected from: acid blue 80, acid blue 62, acid violet 43, acid green 25, direct blue 86, acid blue 59, acid blue 98, direct violet 9, direct violet 99, direct violet 35, direct violet 51 , acid violet 50, acid yellow 3, acid red 94, acid red 51, acid red 95, acid red 92, acid red 98, acid red 87, acid yellow 73, acid red 50, acid violet 9, acid red 52, black food 1, food black 2, acid red 163, acid black 1, acid orange 24, acid yellow 23, acid yellow 40, acid yellow 11, acid red 180, acid red 155, acid red 1, acid red 33, acid red 41 , acid red 19, acid orange 10, acid red 27, acid red 26, acid orange 20, acid orange 6, sulfonated Al and Zn phthalocyanines, solvent violet 13, dispersed violet 26, dispersed violet 28, solvent green 3, solvent blue 63, dispersed blue 56, dispersed violet 27, solvent yellow 33, dispersed blue 79 :one.

The pigment is preferably a shaded pigment to impart a perception of whiteness to a textile.

The pigment may be covalently bound to polymeric species.

A combination of pigments can be used.

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Each particle has particular dimensions x, yyz, in which x is 0.2 to 2 mm, and is 2.5 to 8 mm (preferably 3 to 8 mm), and z is 2.5 to 8 mm (preferably 3 to 8 mm ).

The amount of coverage in each covered particle is advantageously from 10 to 45, more preferably 20 to 35% by weight of the particles.

The numerical percentage of the packaged particle composition comprising the core and the coverage is preferably at least 85%.

The coated particles preferably comprise 0.001 to 3% by weight of perfume.

The core of the covered particles preferably comprises less than 5% by weight, even more preferably less than 2.5% by weight of inorganic materials.

The coating is preferably sodium carbonate, optionally in admixture with a smaller amount of SCMC and more optionally in admixture with one or more of sodium silicate, water soluble fluorescent substance, water soluble or water dispersible shaded pigment and colored pigment or pigment.

Desirably, the particles are flattened spheroids at the poles with a diameter of 3 to 6 mm and a thickness of 1 to 2 mm.

At least something, and preferably a majority portion in number of the particles may have a different color than the white, since this may highlight the colored particles. It has also been found that particles of various colors, for example some blue and some white, provide even greater visual definition for optimal dosage control.

It can be supplied with a handle and / or a measuring device, or spoon. The measuring device can be a lid. More preferably, it is a screw cap since it provides more reliable protection against the ingress of large amounts of water, caused by improper placement of the cap in use.

Manufacture

The composition can be manufactured according to the process described in documents PCT / EP2010 / 055256 and PCT / EP2010 / 055257, that is, it includes the steps of:

a) formation of a mixture of liquid surfactant comprising a major amount of surfactant and a minor amount of water, where the part of surfactant consists of at least 51% by weight of linear alkylbenzene sulphonate and at least one co-surfactant, the mixture of surfactant consists of at most 20% by weight of non-ionic surfactant;

b) drying the liquid surfactant mixture from step (a) in an evaporator or dryer to a moisture content of less than 1.5% by weight and cooling the evaporator or dryer outlet;

c) feeding the cold material, whose output comprises at least 93% by weight of surfactant mixture, with a majority of LAS, to an extruder, optionally together with less than 10% by weight of other materials such as perfume, agent fluorescent, and extrusion of the surfactant mixture to form an extruded product, while periodically cutting the extruded product to form hard detergent particles with a diameter through the extruder greater than 2 mm and a thickness along the axis of the extruder greater at 0.2 mm, as long as the diameter is greater than the thickness;

d) optionally, coating the extruded particles of hard detergent, with up to 30% by weight of cover material, preferably selected from inorganic material and mixtures of such materials and non-ionic material with a melting point in the range 40 to 90 ° C.

To facilitate extrusion it may be advantageous that the cold dry outlet product of the evaporator or dryer stage (b), comprising at least 95% by weight preferably 96% by weight, more preferably 97% by weight, more preferably 98 % by weight of surfactant, be transferred to a mill and ground to particles of less than 1.5 mm, preferably less than 1 mm in average diameter, before it is fed to the extrusion stage (c).

To modify the properties of the ground material, a powder flow aid can be added to the mill, such as Aerosil®, Alusil®, or Microsil®, with a particle diameter of 0.1 to 10 mm, in an amount 0.5 at 5% by weight, preferably 0.5 to 3% by weight (based on mill outlet) and mixed into the particles during milling.

The output product of step b, or the intermediate milling step, if used, is fed to the extruder,

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optionally together with smaller amounts (less than 10% by weight of the total) of other materials such as perfume and / or fluorescent agent, and the mixture of materials fed to the extruder is extruded to form an extruded product with a diameter greater than 2 mm, preferably greater than 3 mm, more preferably greater than 4 mm and preferably with a diameter less than 7 mm, more preferably less than 5 mm, while periodically cutting the extruded product to form hard detergent particles with a maximum thickness greater than 0, 2 mm and less than 3 mm, preferably less than 2 mm, more preferably less than about 1.5 mm and greater than about 0.5 mm, even 0.7 mm. While the preferred extruded product is circular cross-sectional, the invention also encompasses other cross-sections such as triangular, rectangular and even complex cross-sections, such as imitation of a flower with rotationally symmetrical "petals". In truth, the invention can be operated on any extruded product that can be forced through a hole in the extruder or extruder plate; The key is that the average thickness of the extruded product should be kept below the level where the dissolution is slow. As discussed above, this is a thickness of approximately 2 mm. Desirably, multiple extrusions are made simultaneously and they can all have the same cross section or they can have different cross sections. Normally they will have all the same length since they are cut with the knife. The cutting knife should be as thin as possible, to allow high extrusion speed and minimal distortion of the extruded product, during cutting. The extrusion should preferably take place at a temperature below 45 ° C, more preferably below 40 ° C, to avoid adhesion and facilitate cutting. The extruded products according to the present process are cut so that their greatest dimension is through the extruder and the smallest dimension is along the axis of the extruder. This is opposite to the normal extrusion of surfactants. Cutting in this way increases the surface area that is on a "cutting" surface. This also allows the extruded particle to expand considerably along its axis after cutting, while maintaining a relatively high surface-to-volume ratio, which is believed to increase its solubility and also results in an attractive biconvex appearance, or lenticular Elsewhere, this form is referred to as a spheroid flattened at the poles. This is essentially a rotation of an ellipse on its minor axis.

It is surprising that at very low water contents, LAS containing surfactant mixtures can be extruded to make solid detergent particles that are hard enough to be used without any need to be structured by inorganic materials or other structural materials, as found commonly in detergent particles extruded by prior art. Thus, the amount of surfactant in the detergent particle can be much greater and the amount of auxiliary washing substance in the detergent particle can be much smaller.

Preferably the mixture in step (a) comprises at least about 60% by weight, more preferably at least about 70% by weight of surfactant and preferably at most about 40% by weight, more preferably at most 30% by weight. water weight, where the surfactant portion consists of at least 51% by weight of linear alkylbenzene sulphonate salt (LAS) and at least one co-surfactant.

Preferably, the co-surfactant is chosen from the group consisting of: SLES, and non-ionic, together with optional soap and mixtures thereof. The only condition is that when non-ionic is used, it has been found that the upper limit for the amount of non-ionic surfactant is 20% by weight of the total surfactant, to prevent the dry material from being too soft and cohesive to extrude, because it has a hardness value of less than 0.5 MPa.

Preferably, the surfactant mixture is dried in step (b) to a moisture content of less than 1.2% by weight, more preferably less than 1.1% by weight, and more preferably less than 1% by weight.

Drying can be carried out suitably using a swept film evaporator or a Chemithon Turbo Tube® dryer.

Hard extruded particles of detergent can be covered by transferring them to a fluid bed and atomizing up to 40% by weight (based on the covered detergent particle) of inorganic material in aqueous solution and drying the water by drying.

If the cover material does not contribute to the washing performance of the composition, then it is desirable to keep the level of coverage as low as possible, preferably less than 35% by weight, even less than 30% by weight, especially for extruded particles. large with a surface area to volume ratio greater than 4 mm-1.

Surprisingly, it has been found that the appearance of the particles covered in a package is very pleasant. Without wishing to be bound by theory, it is believed that this appearance of high quality coverage is due to the smoothness of the underlying extruded and cut particle. Starting with a smooth surface, it has been found

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Unexpectedly, it is easy to obtain a high quality coated finish (as measured by light reflectance and smoothness) using simple covering techniques.

The detergent composition preferably comprises at least 85% by weight of coated particles. However, compositions with up to 100% by weight of the particles are possible, when basic additives are incorporated into the extruded particles, or within their coverage. The composition may also comprise, for example, an antifoam granule.

Particles of different colors may be used in admixture, or they may be mixed with contact powder. Of course, particles of the same color from each other can also be used to form a complete composition. As described above, the coverage quality and appearance are very good, due to the excellent surface of the cut extrudates, on which the coating is applied, in association with the large particle size and S / V ratios of the particles. preferred.

It is particularly preferred that the detergent particles include perfume. The perfume can be added inside the extruder or previously mixed with the surfactant mixture in the mill, or in a mixer placed after the mill, either as a liquid or as encapsulated perfume particles. In an alternative process, the perfume can be mixed with a non-ionic material and mixed. Such a mixture can be applied alternatively by covering the extruded particles, for example by atomizing it mixed with molten non-ionic surfactant. The perfume can also be introduced into the composition by means of a separate perfume granule and then the detergent particle need not include any perfume.

The surfactant mixture

Surfactant mixtures that do not require the presence of auxiliary fillers are preferred for effective detergency in hard water. If they pass the test set forth below, such mixtures are called calcium-tolerant surfactant mixtures. Thus, it can be advantageous if the extruded core is made using a mixture of calcium tolerant surfactant, in accordance with the test described herein. However, the invention can also be used for washing in soft water, either naturally occurring or using a water softener. In this case, calcium tolerance is no longer important and mixtures other than calcium tolerant can be used.

The LAS may be replaced at least partially by MES, or, less preferably, partially replaced by this 20% by weight PAS.

Mixture

The surfactants are mixed before being introduced into the dryer. Conventional mixing equipment is used.

Drying

To achieve the very low moisture content of the surfactant mixture, scraped film devices can be used. A preferred form of scraped film device is a swept film evaporator. A suitable swept film evaporator is the "Dryex system" based on a swept film evaporator available from Ballestra SpA. Alternative drying equipment includes tube type dryers, such as a Chemithon Turbo Tube® dryer, and soap dryers. .

Cooling and grinding

Then the hot material that comes out of the scraped film dryer is cooled and broken to particles of the appropriate size, to feed the extruder. Simultaneous cooling and breaking to flakes can be conveniently carried out using a cold roller. If the cold roll flakes are not suitable for direct feeding of the extruder, they can be ground in a grinding apparatus and / or can be mixed with other liquid or solid ingredients, in a mixing and grinding apparatus, such as a mill headband. Such ground or mixed material desirably has a particle size 1 mm or less, to feed the extruder.

It is particularly advantageous to add a grinding aid at this point in the process. As a grinding aid, particulate material with an average particle size of 10 nm to 10 µm is preferred for use. Among such materials, there may be mentioned, by way of example: aerosil®, alusil®, and microsil®.

Extrusion and cutting

The extruder provides additional opportunities to mix different ingredients to surfactants, or even to add additional surfactants. However, it is generally preferred that the entire surfactant

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anionic, or other surfactant supplied in admixture with water; that is, as a paste or solution, it is added to the dryer to ensure that the water content can then be reduced and that the material fed to and through the extruder is sufficiently dry. The additional materials that can be mixed within the extruder are thus mainly those that are used at very low levels in the detergent composition: such as a fluorescent agent, a shaded pigment, enzymes, perfume, silicone antifoams, polymeric additives and preservatives. It has been found that the limit on such additional materials mixed in the extruder is approximately 10% by weight, but for the quality of products it is preferred that it is ideally maintained at a maximum of 5% by weight. In general, solid additives are preferred. Liquids, such as perfume, can be added at levels of up to 2.5% by weight, preferably up to 1.5% by weight. Preferably, solid particulate materials, which give structure, or fillers (which absorb liquids) such as zeolites, carbonate, silicate are not added to the mixture being extruded. These materials are not required due to the self-structuring properties of the very dry LAS-based feedstock. If any is used, the total amount should be less than 5% by weight, preferably less than 4% by weight, more preferably less than 3% by weight. At such levels no significant structure formation occurs and the inorganic particulate material is added for a different purpose, for example as a flow aid, to improve the feeding of particles to the extruder.

The extruder outlet product has the shape that the used extrusion die imparts. The extruded material has a tendency to swell in the center, relative to the periphery. It has been found that if a cylindrical extruded product is regularly chopped as it leaves the extruder, the resulting shapes are short cylinders with two convex ends. These particles are described here as spheroids with the flattened poles, or lentils. This form is visually pleasing.

Coverage

An advantageous variant of the process takes the chopped extruded particles and cuts them. This allows the particles to be easily colored. It also additionally reduces the adhesiveness of the hygroscopic surfactant core, to a point where the particles flow freely. The coverage makes them more suitable for use in detergent compositions that can be exposed to high humidity for long periods.

Covering such large extruded particles, the thickness of the coverage obtainable using a coating level of, say 5% by weight, is much greater than would be achieved on detergent granules of typical size (0.5-2 mm diameter spheres ).

Extruded particles can be considered as spheroids with flattened poles, with a larger radius "a" and smaller radius "b". Therefore, the ratio of surface area (S) to volume (V) can be calculated:

l = ± + ^ _ i „íl ± £ l

V 2b 4 g at ejmm-1

where e is the eccentricity of the particle.

For optimal dissolution properties, this ratio of surface area to volume must be greater than 3 mm-1. However, the thickness of the coverage is inversely proportional to this coefficient, and therefore for the coverage the ratio "surface area of covered particle" divided by "volume of covered particle" should be less than 15 mm-1.

Although the skilled person should assume that any known coverage, for example organic, including polymers, can be used, it has been found that it is particularly advantageous to use an inorganic coating deposited by crystallization from an aqueous solution, since it seems that this gives positive dissolution benefits. and the coverage gives a good color to the detergent particle, even for low levels of coverage. An aqueous atomization of the cover solution in a fluid bed can also generate a slight additional rounding of the detergent particles during the fluidization process.

Suitable inorganic coating solutions include sodium carbonate, possibly in admixture with sodium sulfate, and sodium chloride. Food dyes, shaded dyes, fluorescent agents and other optical modifiers can be added to the coverage, dissolving them in the spray solution or dispersion. The use of an auxiliary washing salt, such as sodium carbonate, is particularly advantageous because it allows the detergent particle to perform even better, damping the system in use, at an ideal pH for maximum detergency of the anionic surfactant system. This also increases the ionic strength, which is known to improve cleanliness in hard water, and is compatible with other detergent ingredients that may be mixed with the coated extruded detergent particles. If a fluidized bed is used to apply the coverage solution, the skilled worker will know how to adjust the atomization conditions, in

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terms of Stokes number and possibly Akkermans number (FNm), so that the particles are covered and not agglomerated significantly. In documents EP1187903, EP993505 and Powder technology 65 (1991) 257-272 (Ennis) suitable teaching can be found to help in this.

Those skilled in the art will notice that hedges of several layers, of the same or different cover materials, could be applied, but an individual layer of coverage is preferred, for the simplicity of operation, and to maximize the thickness of the cover. The amount of coverage should be in the range of 3 to 50% by weight of the particle, preferably 20 to 40% by weight, for the best results in terms of anti-agglomeration properties of the detergent particles.

The extruded composition of particulate detergent

The covered particles dissolve easily in water and leave very little residue or leave no residue by dissolution, due to the absence of insoluble structure materials, such as zeolite. The covered particles have an exceptional visual appearance, due to the softness of the coverage, coupled with the softness of the underlying particles, which is also believed to be a result of the absence of structural material in the form of particles in the extruded particles. .

Shape

The covered detergent particle is curved. The coated detergent particle is preferably lenticular (similar to that of a dried whole lentil), an ellipsoid with flat poles, where z and y are the equatorial diameters and x is the polar diameter; preferably y = z.

The size is such that y and z are at least 3 mm, preferably 4 mm, more preferably 5 mm and x is in the range of 1 to 2 mm.

The laundry detergent particle may have the shape of a disk.

Core composition

The core is mainly surfactant. It may also include detergency additives, such as perfume, shaded pigments, enzymes, cleaning polymers and dirt release polymers.

Surfactant

The laundry detergent coated particle comprises between 50 and 90% by weight of a surfactant, more preferably 70 to 90% by weight. In general, the anionic and non-ionic surfactants of the surfactant system can be chosen from among the surfactants described in "Surface Active Agents" vol. 1, by Schwartz & Perry, Interscience 1949, vol. 2 by Schwartz, Perry & Berch, Interscience 1958, in the current edition of "McCutcheon's Emulsifiers and Detergents" published by Manufacturing Confectioners Company or in "Tenside Taschenbuch", H. Stache, 2nd ed., Carl Hauser editorial, 1981. Preferably Used surfactants are saturated.

1) Anionic surfactants

Suitable anionic detergent compounds that can be used are usually water soluble alkali metal salts, organic sulfates and sulphonates having alkyl radicals containing from about 8 to about 22 carbon atoms, where the term "alkyl" is used to include the portion alkyl of higher acyl radicals. Examples of suitable synthetic anionic detergent compounds are sodium and potassium alkyl sulfates, especially those obtained by sulfation of higher C8 to C18 alcohols, produced for example from tallow or coconut oil, C9 to C20 alkyl, sodium benzene sulphonates and potassium, in particular C10 to C15 alkyl benzene linear secondary sodium sulfonates; and sodium glyceryl ether sulfate alkyl, especially those ethers of the higher alcohols derived from tallow or coconut oil and synthetic petroleum-derived alcohols. The most preferred anionic surfactants are sodium lauryl ether sulfate (SLES), particularly preferred with 1 to 3 ethoxy groups, C10 to C15 alkyl sodium benzene sulphonates and C12 to C18 alkyl sodium sulfates. Also applicable are surfactants such as those described in EP-A-328 177 (Unilever), which show resistance to salt separation, alkyl polyglycoside surfactants described in EP-A-070 074, and alkyl monoglycosides. The chains of the surfactants can be branched or linear.

Soaps may also be present. The fatty acid soap used preferably contains about 16 to about 22 carbon atoms, preferably in a straight chain configuration. The anionic contribution of soap can be from 0 to 30% by weight of the total anionic. The use of more than 10% by weight soap is not preferred.

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Preferably, at least 50% by weight of the anionic surfactant is selected from: C11 to C15 alkyl sodium benzene sulfonates; and C12 to C18 alkyl sodium sulfates.

Preferably, the anionic surfactant is present in the laundry detergent coated particle, at levels between 15 to 85% by weight, more preferably 50 to 80% by weight.

2) Nonionic surfactants

Suitable non-ionic detergent compounds that can be used include, in particular, the reaction products of compounds having a hydrophobic group and a hydrogen reactive atom, for example, aliphatic alcohols, acids, amides or alkyl phenols, with alkylene oxides , especially ethylene oxide, either alone or with propylene oxide. Preferred non-ionic detergent compounds are condensates of ethylene oxide with C6 to C22 alkyl phenol, generally 5 to 25 EO, ie 5 to 25 units of ethylene oxide per molecule, and condensation products of C8 to C18 aliphatic alcohols primary or secondary, linear or branched with ethylene oxide, in general 5 to 50 EO. Preferably, the nonionic is 10 to 50 EO, more preferably 20 to 35 EO. Particularly preferred are alkyl ethoxylates.

Preferably the nonionic surfactant is present in the laundry detergent coated particle at levels between 5 to 75% by weight, more preferably 10 to 40% by weight.

The cationic surfactant may be present in minor ingredients, at levels preferably between 0 to 5% by weight.

Preferably all surfactants are mixed together before being dried. Conventional mixing equipment can be used. The surfactant core of the laundry detergent particle can be formed by roller compaction and subsequent coating with an inorganic salt.

Calcium tolerant surfactant system

In another aspect, the core is calcium tolerant and this is a preferred aspect because it reduces the need for an auxiliary washing agent.

Surfactant mixtures that do not require the presence of auxiliary washing agents are preferred for effective detergency in hard water. Such mixtures are called calcium tolerant surfactant mixtures, if they pass the test set forth herein below. However, the invention can also be used for washing with soft water, whether natural occurrence or using a water softener. In this case, calcium tolerance is no longer important and mixtures other than calcium tolerant can be used.

The calcium tolerance of the surfactant mixture is tested as follows:

The surfactant mixture in question is prepared at a concentration of 0.7 g of surfactant solids per liter of water, which contains enough calcium ions for a French hardness of 40 (4 x 10-3 molar Ca2 +). Other ionic hardness free electrolytes, such as sodium chloride, sodium sulfate and sodium hydroxide, are added to the solution to adjust the ionic strength to 0.05M and the pH to 10. The light absorption of length of 540 nm wave through 4 mm of sample, 15 minutes after sample preparation. Ten measurements are made and an average value is calculated. It is estimated that samples giving an absorption value of less than 0.08 are calcium tolerant.

Examples of surfactant mixtures that satisfy the above test for calcium tolerance include those that have a majority of LAS surfactant (which is not itself calcium tolerant) mixed with one or more other surfactants (co-surfactants) that are tolerant. if necessary, to give a mixture that is sufficiently tolerant to calcium to be usable with little or no auxiliary washing agent and to pass the given test. Suitable calcium tolerant co-surfactants include SLES 1-7 EO, and nonionic alkyl ethoxylate surfactants, in particular those with melting points below 40 ° C.

A mixture of LAS / SLES surfactant has a foam profile superior to a mixture of non-ionic LAS surfactant and is therefore preferred for hand washing formulations, which require high levels of foam. SLES can be used at levels up to 30%.

A mixture of LAS / NI surfactant provides a harder particle and its lower foam profile makes it more suitable for use in automatic washing machines.

Coverage

The main component of the cover is the water-soluble inorganic salt. Other coverage may be included.

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Water compatible ingredients. For example fluorescent agents, SCMC, additional pigments, for example shaded pigments, pigments, silicates.

Water soluble inorganic salts

The water-soluble inorganic salts are preferably selected from sodium carbonate, sodium chloride, sodium silicate and sodium sulfate, or mixtures thereof, more preferably 70 to 100% by weight of sodium carbonate. The water soluble inorganic salt is present as a coverage on the particle. The water-soluble inorganic salt is preferably present at a level that reduces the adhesiveness of the laundry detergent particle, to a point where the particles flow freely.

Those skilled in the art will notice that hedges of several layers, of the same or different cover materials, could be applied, but an individual layer of coverage is preferred, for simplicity of operation and to maximize the thickness of the cover. The amount of coverage should be in the range of 1 to 40% by weight of the particle, preferably 20 to 40% by weight, even more preferably 25 to 35% by weight, for the best results in terms of particle agglomeration properties. of detergent

The coverage is applied to the surface of the surfactant core, by crystallization from an aqueous solution of the water-soluble inorganic salt. The aqueous solution preferably contains more than 50g / L, more preferably 200g / L of the salt. It has been found that an aqueous atomization of the coating solution in a fluid bed gives good results and can also generate a slight rounding of the detergent particles during the fluidization process. Drying and / or cooling may be required to complete the process.

By covering the large detergent particles of the present invention, the thickness of coverage obtainable by using a cover layer of, say 5% by weight, is much greater than would be achieved on detergent granules having typical size (spheres with diameter of 0.5-2 mm).

For optimal dissolution properties, this ratio of surface area to volume must be greater than 3 mm-1. However, the coverage thickness is inversely proportional to this coefficient, and therefore for coverage the ratio "surface area of covered particle" divided by "volume of covered particle" should be less than 15 mm-1.

A preferred detergent particle coated with calcium tolerance comprises 15 to 100% by weight of anionic surfactant, of which 20 to 30% by weight is sodium lauryl ether sulfate.

The covered detergent particle

Preferably, the coated detergent particle comprises 70 to 100% by weight, more preferably 85 to 90% by weight, of a detergent composition in a package.

Preferably, the detergent coated particles have substantially the same shape and size, therefore it is understood that at least 90 to 100% of the laundry detergent coated particles in the dimensions x, y and z are within 20%, preferably 10%, variable from the detergent particle covered for the largest to the smallest laundry, in the corresponding dimension.

Water content

The particle preferably comprises 0 to 15% by weight in water, more preferably 0 to 10% by weight, more preferably 1 to 5% by weight in water, at 293 K and 50% relative humidity. This facilitates the storage stability of the particle and its mechanical properties.

Other ingredients

The ingredients described below may be present in the cover or core.

Fluorescent agent

The laundry detergent particle covered preferably comprises a fluorescent agent (optical brightener). Fluorescent agents are well known and many such fluorescent agents are commercially available. Usually, these fluorescent agents are supplied and used in the form of their alkali metal salts, for example sodium salts. The total amount of fluorescent agent or agents used in the composition is generally from 0.005 to 2% by weight, more preferably 0.01 to 0.1% by weight. Fluorescent agents suitable for use in the invention are described in Chapter 7 of Industrial Dyes edited by K. Hunger 2003 Wiley-VCH ISBN 3-527-30426-6.

Preferred fluorescent agents are selected from the classes of diethyrylbiphenyls, triazinylaminostilbenes,

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bis (1,2,3-triazol-2-yl) stilbenes, bis (benzo [b] furan-2-yl) biphenyls, 1,3-diphenyl-2-pyrazolines and curmarines. The fluorescent agent is preferably sulfonated.

Preferred classes of fluorescent agents are: di-styryl biphenyl compounds, for example Tinopal (registered trademark) CBS-X, di-aminestylbeno di-sulfonic acid compounds, for example Tinopal DMS pure Xtra and Blankophor (registered trademark) HRH, and Pyrazoline compounds, for example Blankofor SN. Preferred fluorescent agents are: 2 (4-styryl-3-sulfophenyl) -2H-naphthol [1,2-d] triazole sodium, 4,4'-bis {[(4-anilino-6- (N methyl-N -2 hydroxyethyl) amino 1,3,5-triazin-2-yl)] amino} stilbene-2-2 'disodium disulfonate, 4,4'-bis {[(4-anilino-6-morpholino-1,3 , 5- triazin-2-yl)] amino} stilben-2-2 'disodium disulfonate, and 4,4'-bis (2-sulfoestyryl) biphenyl disodium.

Tinopal® DMS is the disodium salt of 4,4'-bis {[(4-anilino-6-morpholino-1,3,5-triazin-2-yl)] amino} stilben-2-2 'sodium disulfonate. Tinopal® CBS is the disodium salt of 4,4'-bis (2-sulfoestyryl) biphenyl disodium.

Fragrance

Preferably, the composition comprises a perfume. The perfume is preferably in the range of 0.001 to 3% by weight, more preferably 0.1 to 1% by weight. The CTFA (Cosmetic, Toiletry and Fragrance Association) 1992 International Buyers Guide, published by CFTA Publications and OPD 1993 Chemicals Buyers Directory 80th Annual Edition, published by Schnell Publishing Co provides many suitable examples of perfumes.

It is common for a plurality of perfume components to be present in a formulation. In the compositions of the present invention, it is anticipated that there will be four or more, preferably five or more, more preferably six or more or even seven or more different perfume components.

In perfume mixtures, preferably 15 to 25% by weight are top notes. Head notes are defined by Poucher (Journal of the Society of Cosmetic Chemists 6 (2): 80 [1955]). Preferred head notes are selected from citrus oils, linalool, linalyl acetate, lavender, dihydromyrcenol, rose oxide and cis-3-hexanol.

It is preferred that the laundry detergent coated particles do not contain a peroxygen bleach, for example sodium percarbonate, sodium perborate and peracid.

Polymers

The composition may comprise one or more additional polymers. Examples are carboxymethyl cellulose, poly (ethylene glycol), poly (vinyl alcohol), polyethylene imines, ethoxylated polyethyleneimines, water soluble polyester polymers, polycarboxylates such as polyacrylates, maleic acid / acrylic acid copolymers and lauryl methacrylate / acrylic acid copolymers.

Enzymes

One or more enzymes are preferably present in the composition.

Preferably the level of each enzyme is from 0.0001% by weight to 0.5% by weight protein.

Specially contemplated enzymes include proteases, alpha-amylases, cellulases, lipases, peroxidases / oxidases, pectate liases, and mananases, or mixtures thereof.

Suitable lipases include those of bacterial or fungal origin. Mutants modified by chemical or protein engineering are included. Examples of useful lipases include Humicola lipases (synonym Thermomyces), for example of H. lanuginosa (T. lanuginosus) as described in EP 258 068 and EP 305 216 or H. insolens as described in WO 96/13580, a Pseudomonas lipase, for example of P. alkalgenes or P. pseudoalcaligenes (EP 218 272), P. cepacia (EP 331 376), P. stutzeri (GB 1,372,034), P. fluorescens, strain Pseudomonas sp. SD 705 (WO 95/06720 and WO 96/27002), P. wisconsinensis (WO 96/12012), a lipase of Bacillus, for example of B. subtilis (Dartois et al. (1993), Biochemica et Biophysica Acta, 1131 , 253-360), B. stearothermophilus (JP 64/744992) or B. pumilus (WO 91/16422).

Other examples are lipase variants such as those written in WO 92/05249, WO 94/01541, EP 407 225, EP 260 105, WO 95/35381, WO 96/00292, WO 95/30744, WO 94/25578 , WO 95/14783, WO 95/22615, WO 97/04079 and WO 97/07202, WO 00/60063, WO 09/107091 and WO09 / 111258.

Preferred lipase enzymes include LipolaseMR and Lipolase UltraMR, Lipex ™ (Novozymes A / S) and LipocleanMR.

The process of the invention can be carried out in the presence of phospholipase classified as EC 3.1.1.4 and / or EC 3.1.1.32. As used herein, the term phospholipase is an enzyme that has activity towards phospholipids.

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Phospholipids, such as lecithin or phosphatidylcholine, consist of glycerol esterified with two fatty acids in an outer position (sn-1) and the central position (sn-2) and esterified with phosphoric acid in the third position; in turn, the phosphoric acid may be esterified with an amino alcohol. Phospholipases are enzymes that participate in the hydrolysis of phospholipids. Various types of phospholipase activity can be distinguished, including phospholipases A1 and A2 that hydrolyse a fatty acyl group (in the sn-1 and sn-2 position, respectively) to form lysophospholipid; and lysophospholipase (or phospholipase B) which can hydrolyze the fatty acyl group remaining in lysophospholipid. Phospholipase C and phospholipase D (phosphodiesterase) release diacyl glycerol or phosphatidic acid respectively.

Suitable proteases include those of animal, plant or microbial origin. Microbial origin is preferred. Mutants modified by chemical or protein engineering are included. The protease can be a serine protease or a metalloase protease, preferably an alkaline microbial protease or a trypsin-like protease. Suitable protease enzymes include AlcalaseMR, SavinaseMR, PrimaseMR, DuralaseMR, DyrazymMR, EsperaseMR, EverlaseMR, PolarzymeMR, and KannaseMR, (Novozymes A / S), MaxataseMR, MaxacalMR, MaxapemMR, ProperaseMR, FRNMM, FFNMM, FFNMR, ProperaseMR, ProperaseMR, FRNMR, ProperaseMR, ProperaseMR, ProperaseMR, ProperaseMR, ProperaseMR, ProperaseMR, ProperaseMR, ProperaseMR, ProperaseMR, ProperaseMR, ProperaseMR, ProperaseMR, ProperaseMR, ProperaseMR, ProperaseMR, ProperaseMR, ProperaseMR, ProperaseMR, ProperaseMR, ProperaseMR Genencor International Inc.).

The process of the invention can be carried out in the presence of cutinase classified in EC 3.1.1.74. The cutinase used according to the invention can be of any origin. Preferably, the cutinases are of microbial origin, in particular of bacterial, fungal or yeast origin.

Suitable amylases (alpha and / or beta) include those of bacterial or fungal origin. Mutants modified by chemical or protein engineering are included. Amylases include, for example, alpha-amylases obtained from Bacillus, for example a special strain of B. licheniformis, described in more detail in GB 1,296,839, or Bacillus sp. disclosed in WO 95/026397 or WO 00/060060. Suitable amylases are DuramylMR, TermamylMR, Termamyl UltraMR, NatalaseMR, StainzymeMR, Fungamyl MR and BANMR (Novozymes A / S), RapidaseMR and PurastarMR (from Genencor International Inc.).

Suitable cellulases include those of bacterial or fungal origin. Mutants modified by chemical or protein engineering are included. Suitable cellulases include cellulases of the genera Bacillus, Pseudomonas, Humicola, Fusarium, Thielavia, Acremonium, for example fungal cellulases produced from Humicola insolens, Thielavia terrestris, Myceliophthora thermophila, and Fusarium oxysporum, disclosed in documents30, 307, 430.30 published in US 5,648,263, US 5,691,178, US 5,776,757, WO 89/09259, WO 96/029397, and WO 98/012307. Cellulases include CelluzymeMR, CarezymeMR, EndolasaMR, RenozymeMR (Novozymes A / S), ClazinasaMR and Puradax HAMR (Genencor International Inc.), and KAC-500 (B) MR (Kao Corporation).

Suitable peroxidases / oxidases include those of plant, bacterial or fungal origin. Mutants modified by chemical or protein engineering are included. Examples of useful peroxidases include Coprinus peroxidases, for example from C. cinereus, and variants thereof such as those described in WO 93/24618, WO 95/10602, and WO 98/15257. Peroxidases include GuardzymeMR and NovozymMR 51004 (Novozymes A / S).

Other suitable enzymes are disclosed in WO2009 / 087524, WO2009 / 090576, WO2009 / 148983 and WO2008 / 007318.

Enzyme stabilizers

Any enzyme present in the composition can be stabilized, using conventional stabilizing agents, for example a polyol such as propylene glycol or glycerol, a sugar or sugar alcohol, lactic acid, boric acid, or a boric acid derivative, for example an ester borate aromatic, or a phenyl boronic acid derivative such as 4-formylphenyl boronic acid, and the composition can be formulated as described for example in WO 92/19709 and WO 92/19708.

Sequestrants may be present in the detergent particles.

The invention will be described in more detail with reference to the following examples that are not limiting. Examples

Example 1: (particle manufacturing)

A coated detergent particle color was created, containing acid violet 50 in the core.

The particles were ellipsoids with the flattened poles, which had the following dimensions x = 1.1 mm y = 4.0 mm z = 5.0 mm. The particles weighed ~ 0.013g each. To the eye, the particle looked like a colorful violet.

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1,962.5 g of dry mixture of ground surfactant (LAS / NI 85/15 by weight) were thoroughly mixed with 37.38 g of perfume oil and 0.124 g of 50 violet acid pigment. The mixture was then subjected to extrusion using a ThermoFisher 24HC double screw extruder, operated at a rate of 8kg / hr. The extruder inlet temperature was adjusted to 20 ° C, rising to 40 ° C just before the die plate. The die plate used was perforated with 6 circular holes with a diameter of 5mm.

The extruded product was cut after the die plate, using a high speed cutter adjusted to produce particles with a thickness of ~ 1.1 mm.

Particle Coverage

764 g of the extruded products prior to the fluidization chamber of a Strea 1 laboratory fluid bed dryer (Aeromatic-Fielder AG) were charged and spray coated using 1,069 g of a solution containing 320.7 g of carbonate carbonate. sodium in 748.3 g of water, using an atomization configuration from above.

The coverage solution was fed to the spray nozzle of Strea 1 by a peristaltic pump (Watson-Marlow model 101U / R) at an initial rate of 3.3 g / min, increasing to 9.1 g / min during the course of the coverage test.

The fluid bed cover apparatus was operated with an initial air inlet temperature of 55 ° C increasing to 90 ° C in the course of the coverage test, while maintaining the outlet temperature in the range of 45-50 ° C during the coverage process.

Example 2: (color of covered detergent particle)

The color of the particles of Example 1 was measured, using a reflectometer (excluding UV) and expressed as the CIE value L * a * b * The results are shown below

 L * a * b *

 Particle: pigment in the nucleus

 76.2 2.9 -7.9

 L * is the luminosity, as the object becomes colored, L * falls to * is the red-green axis with + ve values indicating a red color and -ve a green color

 b * is the yellow-blue axis with values + see indicating a yellow color and

 -see a blue color

Clearly, the particle is violet with a negative b * value.

Example 3: (liquor color)

2.25 g of the example particle was dissolved in 100 ml of demineralized water. The solutions were centrifuged for 15 minutes at 11,000 rpm and the color of the liquid was measured in a UV-VIS absorption spectrometer. The liquid looked violet in sight.

The UV-VIS spectrum gave the acid violet spectrum 50 for both solutions, with a maximum absorption at 570 nm. The optical densities are given below in the table.

 Optical density (5cm) at 570 nm

 Particle: pigment in the nucleus

 0.175

 Both particles effectively deliver acid violet 50 to the solution.

Claims (14)

5 10 fifteen twenty 25 30 35 1. A packaged particulate detergent composition, contained in a package, wherein the package comprises at least one transparent portion and the composition comprises more than 50% by weight of detergent surfactant and at least 70% by number of particles comprises (i) a core comprising mainly surfactant and 0.0001 to 0.1% pigment, preferably 0.001 to 0.01% pigment, where the pigment is selected from anionic pigments and non-ionic pigments; Y (ii) a cover, comprising water-soluble inorganic salt deposited by crystallization from an aqueous solution, where the particles have substantially the same shape and size of each other, characterized in that each particle has particular dimensions x, y and z, in which x it is 0.2 to 2 mm, and is 2.5 to 8 mm (preferably 3 to 8 mm), and z is 2.5 to 8 mm (preferably 3 to 8 mm). 2. A packaged composition according to any preceding claim, wherein the at least one transparent portion has a transmission greater than 25%, more preferably more than 30%, more preferably more than 40%, more preferably more 50%, in the visible part of the spectrum. 3. A packaged composition according to any preceding claim, wherein the at least one transparent portion comprises an opening in an opaque portion. 4. A packaged composition according to any preceding claim, wherein the at least one transparent portion comprises the entire package, which may include one or more opaque labels. 5. A packaged composition according to any preceding claim, wherein the pigment is selected from those having: anthraquinone chromophores; mono-azo; bis-azo; xanthene; phthalocyanine; and, phenazine. 6. A packaged composition according to any preceding claim, wherein the pigment is selected from those having: anthraquinone and mono-azo chromophores. 7. A packaged composition according to any preceding claim in which the percentage by number of the packaged composition of particles comprising the core and coverage is at least 85%. 8. A packaged composition according to any preceding claim, wherein the pigment is selected from acid pigments; dispersed pigments and alkoxylated pigments. 9. A packaged composition according to any preceding claim, wherein the coverage comprises sodium carbonate. 10. A packaged composition according to any preceding claim, in which the coated particles are spheroids with flattened poles, with a diameter of 3 to 6 mm and a thickness of 1 to 2 mm. 11. A packaged composition according to any preceding claim, wherein a majority portion in number of the particles in the composition has colors other than white. 12. A packaged composition according to any preceding claim, in which the package is resealable. 13. A packaged composition according to claim 12, wherein the package is resealable by means of a screw cap, which also serves as a dosage measurement. 14. A packaged composition according to any preceding claim, which is a laundry detergent composition.