Laundry additive products

Description

[0001] This invention relates to laundry additive products. In particular, it relates to laundry additive products for cleaning clothes and the like in domestic and commercial washing machines, the additive product containing a storage-sensitive detergency additive material.

[0002] It is widely recognized that the function of a detergency additive material can be significantly impaired in detergent and other laundry compositions by interaction between the additive material and other components of the composition or even with air. For example, detergency enzymes can be deleteriously effected by interaction with bleaches, sequestrants, acids and bases, surfactants and air; perfumes and bleach activators can be deleteriously effected by interaction with bleaches; cationic fabric conditioners can be deleteriously effected by interaction with anionic surfactants; fluorescers can be deleteriously effected by interaction with bleaches and cationic surfactants; and suds-suppressors can also be deleteriously effected by interaction with surfactants. Moreover, the consumer acceptibility of a product can also be significantly reduced as the result of physical interactions between a laundry additive material and other components of a composition. For instance, a speckled detergent containing a water-soluble dye can lose its aesthetic appeal as a result of migration of the dye into the detergent base formula, an effect which can be significantly enhanced by the presence in the detergent composition of a nonionic surfactant component.

[0003] One approach adopted in the art for minimizing storage-stability problems for sensitive ingredients is to agglomerate the sensitive ingredient, for example by extrusion, wet agglomeration, etc and to add the resulting agglomerate to a detergent base powder. GB-A-1,204,123, GB-A-1,441,416 and GB-A-1,395,006 are representative of this general approach. The technique suffers a number of disadvantages, however. For example, physical segregation problems caused by differences in particle size and/or bulk density between the agglomerate and the base powder can contribute to reduced aesthetic appeal and reproducibility of-performance. More importantly, the agglomerates are prone to interparticle abrasion which can lead to partial or even total disintegration of the agglomerates with concomitant problems of reduced storage stability and increased dust formation.

[0004] The Applicants have now discovered that laundry additive materials having improved storage-stability can be provided by dispersing agglomerated particles of the additive material in an organic matrix of defined thermal characteristics and which is combined in water-releasable manner with a water-insoluble, unitary carrier. The resulting laundry additive products have improved storage-stability, convenience and reproducibility in use and reduced problems of dust formation.

[0005] Accordingly, the present invention provides a laundry additive product comprising:

(a) a'laundry additive composition in the form of a plastic solid comprising discrete agglomerated particles of storage-sensitive detergency additive dispersed in a water-soluble or water-dispersible matrix of organic materials having a melting completion temperature of less than 85°C, the laundry additive composition having an IP49 penetrometer hardness of less than 1 mm (100 g, 15 sec, 25°C) and a softening temperature defined as the temperature at which the penetrometer hardness first exceeds 3 mm, of at least 35°C, the storage-sensitive detergency additive being agglomerated with a water-soluble or water-dispersible organic carrier having a melting-completion temperature of at least 5°C greater than the softening temperature of the laundry additive composition, the laundry additive composition being in water-releasable combination with (b) a unitary water-insoluble carrier.

[0006] The storage-sensitive detergent additive is suitably selected from detergency enzymes, bleaches, bleach activators and bleach catalysts, photoactivators, dyes, fluorescers, suds suppressors, perfumes, fabric conditioning agents, and hydrolysable surfactants. Highly preferred are detergency enzymes, especially proteases, amylases and mixtures thereof. The laundry additive product will also usually incorporate an antagonist material responsible for the deleterious effect on storage stability of the additive; alternatively, the additive material will be sensitive to storage in the presence of some environmental factor such as air, moisture, or sunlight. Preferred laundry additive materials and their specific antagonists are listed below:

[0007] The laundry additive composition preferably comprises at least about 40%, more preferably at least about 50%, especially at least about 60% of organic matrix materials having a melting completion temperature of less than about 85°C. These in turn each preferably have a melting completion temperature of less than about 75°C, more preferably less than about 70°C. The additive composition itself has a softening temperature of at least 35°C, preferably at least 40°C, especially at least 50°C, and a penetrometer hardness of less than 10, preferably less than 7.

[0008] In preferred embodiments, the laundry additive product contains at least 5%, preferably at least 15% by weight of composition of water-soluble or water-dispersible organic binding agent having a melting-onset temperature of at least 35°C and a melting completion temperature of less than 85°C. Preferably, the binding agent is selected from polyethylene glycols of molecular weight greater than 1000, C,₂-C₂₄ fatty acids and esters and amides thereof, polyvinyl pyrrolidone of molecular weight in the range from 40,000 to 700,000, and C₁₄―C₂₄ fatty alcohols ethoxylated with from 14 to 100 moles of ethylene oxide. Highly preferred binding agents comprise at least 40%, especially at least 50% thereof of polyethyleneglycol having a molecular weight greater than 4000.

[0009] The agglomerate component of the additive product comprises the detergency additive material together with an agglomerating agent. In addition, the agglomerate can contain a solid diluent. The detergency additive and diluent are both preferably particulate in form with an average particle size of less than 150 pm, more preferably less than 100 pm, especially less than 50 pm. A small particle size contributes to improved dispersability of the agglomerate. The physical integrity of the agglomerate should be such, however, to prevent disintegration during dispersion in the organic matrix. The average particle size of the agglomerate after dispersion is preferably at least 100 um, more preferably from 150 µm to 2000 pm. The agglomerating agent takes the form of a carrier in which the detergency additive and, if present, diluent are dispersed. Preferred carriers are water-soluble or water-dispersible organic materials having a melting onset temperature of at least 35°C, more preferably at least 45°C, especially at least 50°C and a melting completion temperature of at least 40°C, more preferably at least 45°C, especially at least 55°C, and of less than 100°C, more preferably less than 85°C, especially less than 75°C. Moreover, the melting completion temperature of the carrier is at least 5°C greater than the softening temperature of the additive composition. Suitable organic carriers are again selected from polyethylene glycols of molecular weight greater than 1000, C,₂ C₂₄ fatty acids and esters and amides thereof, polyvinyl pyrrolidone of molecular weight in the range from 40,000 to 700,000, and C₁₄―C₂₄ fatty alcohols ethoxylated with from 14 to 100 moles of ethylene oxide. Preferred diluents herein are inorganic and include alkali metal, alkaline earth metal and ammonium sulphates and chlorides, neutral and acid alkali metal carbonates, orthophosphates and pyrophosphates, and alkali metal crystalline and glassy polyphosphates. Suitable water-insoluble but dispersible diluents include the finely-divided natural and synthetic silicas and silicates, especially smectite-type and kaolinite-type clays such as sodium and calcium montomorillonite, kaolinite itself, aluminosilicates, and magnesium silicates and fibrous and microcrystalline celluloses. Suitable adhesive materials include the organic carrier materials described above, water, aqueous solutions or dispersions of the inorganic diluent materials described above, polymer solutions and latexes such as aqueous solutions of sodium carboxymethylcellulose, methylcellulose, polyvinylacetate, polyvinyl alcohol, dextrins, ethylene vinylacetate copolymers and acrylic latexes. In the case of hydrolysable and moisture sensitive additives such as enzymes, however, the final moisture content of the agglomerate should be no more than about 3%.

[0010] In a highly preferred embodiment, the additive composition is coated on or impregnated into a flexible, sheet-like substrate at a weight ratio of composition: substrate (i.e. loading ratio) of at least 3:1. more preferably at least 5: 1, especially at least 6: 1. Alternatively, however, the additive composition can take the form of an aggregate of physically discrete solid bodies having the agglomerated particles of storage-sensitive detergency additive material dispersed therein, the aggregate being incorporated in a water-permeable or water-frangible pouch.

[0011] The laundry additive products of the invention suitably contain at least 5%, preferably at least 20% of additive composition of organic detergent selected from anionic, nonionic and cationic surfactants and mixtures thereof. Preferred nonionic surfactants have melting completion temperatures of less than 85°C and form part of the matrix of organic materials. Preferred cationic surfactants have melting onset temperatures of at least 35°C and can either form part of the organic binding agent or be dispersed in the organic matrix. Preferred anionic surfactants have melting completion temperatures in excess of 100°C and are dispersed in the organic matrix. Surfactants which are sensitive to alkaline or acid hydrolysis (e.g. alkyl sulphates), however, can be incorporated in the organic matrix in the form of agglomerates. Of the above surfactants, highly preferred from the viewpoint of optimum detergency and agglomerate stability are anionic sulphonate and sulphate surfactants and/or water-soluble cationic surfactants and mixtures of these anionic and/or cationic surfactants with water-soluble ethoxylated nonionic surfactants.

[0012] A process of making the laundry additive product defined herein comprises the step of dispersing the agglomerated particles of storage sensitive detergency additive in the matrix of organic materials under high shear conditions and at a temperature above the softening point of the additive composition but beneath the temperature and shear at which the agglomerated particles melt, decompose, or disintegrate.

[0013] The laundry additive products of the invention will now be discussed in detail.

[0014] A preferred class of detergency additive material is a detergency enzyme. The enzyme is preferably a hydrolysing enzyme and can be selected generally from proteases, esterases, carbohydrases, and mixtures thereof. Examples of proteases suitable for use herein are pepsin, trypsin, chymotrypsin, collagenase, keratinase, elastase, subtilisin, papain, bromelin, carboxypeptidase A and B, aminopeptidase, and aspergillopeptidase A and B. Preferred proteases are serine proteases which are active in the neutral to alkaline pH range and are produced from microorganisms such as bacteria, fungi or mould. A highly preferred protease is prepared by fermentation of a strain of Bacillus Subtilis.

[0015] Specific examples of carbohydrases are maltase, saccharase, amylases, cellulase, pectinase, lysozyme, a-glucosidase, and (3-glucosidase. Preferred are a-amylases of mould, cereal or bacterial origin.

[0016] Specific examples of esterases are gastric lipase, pancreatic lipase, plantlipases, phospholipases, cholineesterases and phosphotases.

[0017] A valuable feature of the enzyme embodiments of the invention is that the laundry additive product provides, in unitary form, the entire enzyme dosage for a single laundering operation. This is highly beneficial from the viewpoint of enzyme handling and stability. Accordingly, the laundry additive products preferably comprise from 0.001 to 0.5, more preferably from 0.003 to 0.1 g of enzyme per unit of product (enzyme expressed in pure form). For protease and a-amylase specifically, the laundry additive products preferably comprise from 0.075 to 15, more preferably from 0.15 to 4.5 Anson units of protase per unit of product, and from 2,000 to 400,000, more preferably from 4,000 to 120,000 maltose units of a-amylase per unit of product. Protease activity is measured against Novo Alcalase protease as standard using the method of Dunn & Brotherton, Analyst, 96,159-163 (1971). Amylase activity is measured as described in P. Bernfeld, Adv. in Enzymol, 12, 379 (1959), but using starch substrate buffered to pH 6 with a sodium acetate (4.1%)/acetic acid buffer solution, a sample concentration of 0.05 g/litre or a multiple dilution thereof, a digestion temperature of 37°C and a digestion time of 5 minutes. The amylase then has one activity unit for each 0.4 mg of maltose hydrate produced during hydrolysis.

[0018] The storage-sensitive detergency additive can also be represented by bleaches, bleach activators and bleach catalysts. Suitable inorganic peroxygen bleaches include sodium perborate mono- and tetrahydrate, sodium percarbonate, sodium persilicate and urea-hydrogen peroxide addition products and the clathrate 4Na₂S0₄:2H₂0₂:1NaCl. Suitable organic bleaches include peroxylauric acid, peroxyactanoic acid, peroxynonanoic acid, peroxydecanoic acid, diperoxydodecanedioic acid, diperoxyazelaic acid, mono-and diperoxyphthalic acid and mono- and diperoxyisophthalic acid. Peroxyacid bleach precursors suitable herein are disclosed in UK-A-2040983, highly preferred being peracetic acid bleach precursors such as tetraacetylethylenediamine, tetraacetylmethylenediamine, tetraacetylhexylenediamine, sodium p-acetoxybenzene sulphonate, tetraacetylglycouril, pentaacetylglucose, octaacetyllactose, and methyl 0-acetoxy benzoate. Bleach precursors can be used at a precursor: unitary carrier ratio within the range from 30:1 to 1:10, preferably from 8:1 to 1:2, while bleaches can be used at a bleach:unitary carrier ratio from 30:1 to 1:4, preferably from 10:1 to 1:1. Bleach catalyst systems suitable for use herein include chelated transition metal catalysts as described in EP-A-0072166.

[0019] The storage sensitive detergency additive can also be represented by sud-suppressors, especially materials of the silicone, wax, vegetable and hydrocarbon oil and phosphate ester varieties. Suitable silicone suds controlling agents include polydimethylsiloxanes having a molecular weight in the range from about 200 to about 200,000 and a kinematic viscosity in the range from about 20 to about 2,000,000 mm²s, preferably from about 3000 to about 30,000 mm²/s, and mixtures of siloxanes and hydrophobic silanated (preferably trimethylsilanated) silica having a particle size in the range from about 10 nm to about 20 nm and a specific surface area above about 50 m²/g. Suitable waxes include microcrystalline waxes having a melting point in the range from about 65°C to about 100°C, a molecular weight in the range from about 400-1000, and a penetration value of at least 6, measured at 77°C by ASTM-D1321, and also paraffin waxes, synthetic waxes and natural waxes. Suitable phosphate esters include mono- and/or di-C,₆₇-C₂₂ alkyl or alkenyl phosphate esters, and the corresponding mono- and/or di alkyl or alkenyl ether phosphates containing up to 6 ethoxy groups per molecule.

[0020] Other storage-sensitive detergency additives include bleach-sensitive fluorescers such as Blackophor (RTM) MBBH (Bayer AG) and Tinopal (RTM) CBS and EMS (Ciba Geigy); nonionic surfactant-soluble dyes and photoactivators as disclosed in EP-A-0057088, highly preferred materials being zinc phthalocyanine tri- and tetrasulphonates; bleach-sensitive perfumes; anionic surfactant-sensitive fabric conditioning agents such as di-C,₂-C₂₄ alkyl or alkenyl amines and ammonium salts; and hydrolysable surfactants such as the C₁₀-C_l6 alkyl and alkyl ether sulphates.

[0021] The agglomerates of storage-sensitive detergency additive can be prepared by any appropriate agglomeration technique, for example by extrusion with the molten organic carrier or by dispersing liquid organic carrier onto a moving bed of the storage sensitive additive, optionally in admixture with a solid diluent, in for example a pan agglomerator, Schugi mixer or fluidized bed apparatus.

[0022] Turning to the laundry additive composition, this is in solid form at ambient temperatures (25°C and below) and has a softening temperature of at least 35°C, preferably at least 40°C, especially at least 50°C. By softening temperature is meant the temperature at which there is transition from plastic-flow to viscous-flow properties; at ambient temperatures, therefore, the composition takes the form of a plastic solid having a non-zero yield stress. The hardness of the compositions at ambient temperatures is determined by the penetrometer-based technique of IP49. Thus, laundry additive compositions herein have a penetration under a 100 g load at 25°C after 15 seconds under IP49 of less than 10 (measured in tenths of a millimetre), preferably less than 7. The softening temperature of the composition, on the other hand, is taken herein to be the temperature at which the IP49 15 second penetration exceeds 30.

[0023] The laundry additive composition herein comprises a matrix of organic materials of defined melting characteristics. Melting completion temperatures are determined using a Dupont 910 Differential Scanning Calorimeter with Mechanical Cooling Accessory and R90 Thermal Analyser as follows. A 5-10 mg sample of the organic material containing no free water or solvent is encapsulated in a hermetically sealed pan with an empty pan as reference. The sample is initially heated until molten and then rapidly cooled (at about 20-30°C/min) to -70°C. Thermal analysis is then carried out at a heating rate of 10°C/min using sufficient amplification ofΔT signal (i.e. temperature difference between sample and reference-vertical axis) to obtain an endotherm-peak signal:baseline noise ratio of better than 10:1. The melting completion temperature is then the temperature corresponding to the intersection of the tangential line at the steepest part of the endotherm curve at the high temperature end of the endotherm, with the horizontal line, parallel to the sample temperature axis, through the highest temperature endotherm peak.

[0024] The organic materials constituting the matrix have a melting completion temperature of less than 85°C. In addition, the laundry additive products of the invention preferably contain at least 5% by weight of composition of binding agent defined as organic material having a melting completion temperature of less than 85°C, preferably less than 80°C, especially less than 70°C, and a melting onset temperature of at least 35°C, preferably at least 40°C, especially at least 50°C. The melting onset temperature can once again be determined by thermal analysis as described above and is taken to be the sample temperature at the point of intersection of the base line with a tangent to the steepest part of the endotherm nearest the low temperature end of the endotherm.

[0025] In a highly preferred embodimenf, the additive composition is coated on or impregnated into a flexible sheet-like substrate at a weight ratio of composition:substrate of at least 3:1, preferably at least 5:1. Preferred substrates for use herein are apertured nonwoven fabrics which can generally be defined as adhesively bonded fibrous or filamentous products, having a web or carded fibre structure (where the fibre strength is suitable to allow carding) or comprising fibrous mats, in which the fibres or filaments are distributed haphazardly or in random array (i.e. an array of fibres in a carded web wherein partial orientation of the fibres is frequently present as well as a completely haphazard distributional orientation) or substantially aligned. The fibres or filaments can be natural (e.g. wool, silk, wood pulp, jute, hemp, cotton, linen, sisal, or ramie), synthetic (e.g. rayon, cellulose, ester, polyvinyl derivatives, polyolefins, polyamides, or polyesters) or mixtures of any of the above.

[0026] Generally, non-woven cloths are made by air or water laying processes in which the fibres or filaments are first cut to desired lengths from long strands, passed into a water or air stream, and then deposited onto a screen through which the fibre-laden air or water is passed. The deposited fibres or filaments are then adhesively bonded together, dried, cured and otherwise treated as desired to form the non-woven cloth.

[0027] Preferably, the non-woven cloth is made from cellulosic fibres, particularly from regenerated cellulose or rayon, which are lubricated with standard textile lubricant such as sodium oleate. Preferably the fibres are from about 4 to about 50 mm, especially from about 8 mm to about 20 mm, in length and are from 0.111 to 0.556 Tex (1 to 5 denier). Preferably the fibres are at least partially orientated haphazardly, particularly substantially haphazardly, and are adhesively bonded together with hydrophobic or substantially hydrophobic binder-resin, particularly with a nonionic self-crosslinking acrylic polymer or polymers. In highly preferred embodiments, the cloth comprises from about 75% to about 88%, especially from about 78% to about 84% fibre and from about 12% to about 25%, especially from about 16% to about 22% hydrophobic binder-resin polymer by weight and has a basis weight of from about 10 to about 70, preferably from 20 to 50 g/m². Suitable hydrophobic binder-resins are ethylacrylate resins such as Primal HA24 Rhoplex HA8 and HA16 (Rohm and Haas, Inc) and mixtures thereof.

[0028] The fiexible substrate for use herein is preferably an apertured substrate having an aperture density of from about 10 to about 30, preferably from about 13 to about 26, more preferably from 16 to about 23 apertures per sq cm of sheet, wherein the apertures, on average, have a width of from about 0.5 mm to about 5 mm and a length of from about 0.8 mm to about 5 mm, the substrate carrying a water releasable coating of the laundry additive composition and having areas of uncoated apertures and areas wherein the coating covers the apertures and extends between opposing surfaces of the substrate, the ratio of areas of uncoated to coated apertures being in the range from about 15:1 to about 1:3. The apertures themselves are generally symmetrical about a longitudinal axis (i.e. they have mirror symmetry) and preferably have, on average, a width of from about 0.7 to about 2.5 mm and a length of from about 1.7 mm to about 4 mm. The area of the apertures, on the other hand, is preferably from about 0.7 mm² to about 7 mm², more preferably from about 0.8 nim2 to about 3.5 mm², and the ratio of length:width is from 1:1 1 up to preferably about 6:1, more preferably about 4:1. These parameters are highly preferred from the viewpoint of achieving the optimum ratio of areas of uncoated to coated apertures and the complete filling of coated apertures from one surface of the substrate to the other.

[0029] The substrate apertures herein can be elongate in shape (for example, generally elliptical or diamond-shaped) in which case the apertures preferably have a width of from about 0.8 mm to about 1.5 mm and a length of from about 2 mm to about 3.5 mm. In preferred embodiments, however, the apertures are generally square-shaped with a side dimension of from about 1 to 2.5 mm. As used herein, "length" refers to the dimension of the principal (i.e. longest) longitudinal axis, and "width" is the maximum dimension perpendicular to this axis.

[0030] As far as loading ratio is concerned (i.e. the weight ratio of composition:substrate) this preferably is at least about 6:1 and more preferably at least 7:1. Moreover the ratio of the areas of uncoated to coated apertures in the final product is preferably from about 6:1 to about 1:2, more preferably from about 4:1 to about 1:1.

[0031] An example of an apertured non-woven substrate suitable herein is a regenerated cellulose sheet of 1.5 denier fibres bonded with Rhoplex HA8 binder (fibre:binder ratio of about 77:23) having a basis weight of about 35 g/m² and about 17 apertures/cm2. The apertures are generally elliptical in shape and are in side-by-side arrangement. The apertures have a width of about 0.9 mm and a length of about 2.5 mm measured in a relaxed condition. Another highly preferred substrate based on 0.165 tex (1.5 denier) regenerated cellulose fibres with Rhoplex HA8 binder has a fibre: binder ratio of about 82:18, a basis weight of about 35 g/m², and about 22 apertures/cmz. In this example, the apertures are generally square-shaped with a width (relaxed) of about 1.1 mm. The apertures are again disposed in side-by-side arrangement.

[0032] The size and shape of the substrate sheet for each unit of product is a matter of choice and is determined principally by factors associated with the convenience of its use. Thus the sheet should not be so small as to become trapped in the crevices of the machine or the clothes being washed or so large as to be awkward to package and dispense from the container in which it is sold. For the purposes of the present invention sheets ranging in plan area from about 130 cm² to about 1300 cm² are acceptable, the preferred area lying in the range of from about 520 _CM² to about 780 cm².

[0033] In another embodiment, the laundry additive composition takes the form of an aggregate of physically discrete solid bodies having the agglomerated particles of storage-sensitive detergency additive dispersed therein, the aggregate being incorporated in a water permeable or water-frangible pouch. Suitable pouch materials include apertured substrates as described above, the relative dimensions of the aggregate and substrate apertures being such as to prevent "sifting" of laundry additive composition through the apertures during mechanical handling. Alternatively, the pouch material can contain a water-frangible seam or regions of low wet strength which rupture to allow egress of the additive composition during the wash cycle.

[0034] The laundry additive products of the invention can be supplemented by all manner of laundering and detergency components. Suitably, the additive products can contain at least 5%, preferably from 20% to 90%, more preferably from 35% to 75% of organic detergent selected from anionic, nonionic and cationic surfactants and mixtures thereof. Anionic surfactants preferably comprise from 7% to 38%, more preferably from 15% to 30% by weight of composition; nonionic surfactants from 8% to 32%, more preferably from 12% to 25% by weight of composition; and cationic surfactants from 5% to 30%, more preferably from 8% to 20% by weight of composition.

[0035] The anionic surfactant can be any one or more of the materials used conventionally in laundry detergents. Suitable synthetic anionic surfactants are water-soluble salts of alkyl benzene sulphonates, alkyl sulphates, alkyl polyethoxy ether sulphates, paraffin sulphonates, alpha-olefin sulphonates, alpha-sulpho-carboxylates and their esters alkyl glyceryl ether sulphonates, fatty acid monoglyceride sulphates and sulphonates, alkyl phenol polyethoxy ether sulphates, 2-acyloxy alkane-1-sulphonate, and beta-alkyloxy alkane sulphonate.

[0036] A particularly suitable class of anionic surfactants includes water-soluble salts, particularly the alkali metal, ammonium and alkanolammonium xalts or organic sulphuric reaction products having in their molecular structure an alkyl or alkaryl group containing from about 8 to about 22, especially from about 10 to about 20 carbon atoms and a sulphonic acid or sulphuric acid ester group. (Included in the term "alkyl" is the alkyl portion of acyl groups). Examples of this group of synthetic detergents which form part of the detergent compositions of the present invention are the sodium and potassium alkyl sulphates, especially those obtained by sulphating the higher alcohols (C_S-_1s) carbon atoms produced by reducing the glycerides of tallow or coconut oil and sodium and potassium alkyl benzene sulphonates, in which the alkyl group contains from about 9 to about 15, especially about 11 to about 13, carbon atoms, in straight chain or branched chain configuration, e.g., those of the type described in US-A-2,220,099 and US-A-2,477,383 and those prepared from alkylbenzenes obtained by alkylation with straight chain chloroparaffins (using aluminium trichloride catalysis) or straight chain olefins (using hydrogen fluoride catalysis). Especially valuable are linear straight chain alkyl benzene sulphonates in which the average of the alkyl group is about 11.8 carbon atoms, abbreviated as C11.8 LAS, and C,2-C,5 methyl branched alkyl sulphates.

[0037] Other anionic detergent compounds herein include the sodium C₁₀-₁₈ alkyl glyceryl ether sulphonates, especially those ethers of higher alcohols derived from tallow and coconut oil; sodium coconut oil fatty acid monoglyceride sulphonates and sulphates; and sodium or potassium salts of alkyl phenol ethylene oxide ether sulphate containing about 1 to about 10 units of ethylene oxide per molecule and wherein the alkyl groups contain about 8 to about 12 carbon atoms.

[0038] Other useful anionic detergent compounds herein include the water-soluble salts or esters of a-sulphonated fatty acids containing from about 6 to 20 carbon atoms in the fatty acid group and from about 1 to 10 carbon atoms in the ester group; water-soluble salts of 2-acyloxy-alkane-1-sulphonic acids containing from about 2 to 9 carbon atoms in the acyl group and from about 9 to about 23 carbon atoms in the alkane moiety; alkyl ether sulphates containing from about 10 to 18, especially about 12 to 16, carbon atoms in the alkyl group and from about 1 to 12, especially 1 to 6, more especially 1 to 4 moles of ethylene oxide; water-soluble salts of olefin sulphonates containing from about 12 to 24, preferably about 14 to 16, carbon atoms, especially those made by reaction with sulphur trioxide followed by neutralization under conditions such that any sultones present are hydrolysed to the corresponding hydroxy alkane sulphonates; water-soluble salts of paraffin sulphonates containing from about 8 to 24, especially 14 to 18 carbon atoms, and (3-atkytoxy alkane sulphonates containing from about 1 to 3 carbon atoms in the alkyl group and from about 8 to 20 carbon atoms in the alkane moiety.

[0039] The alkane chains of the foregoing non-soap anionic surfactants can be derived from natural sources such as coconut oil or tallow, or can be made synthetically as for example using the Ziegler or Oxo processes. Water solubility can be achieved by using alkali metal, ammonium or alkanolammonium cations; sodium is preferred. Suitable fatty acid soaps can be selected from the ordinary alkali metal (sodium, potassium), ammonium, and alkylolammonium salts of higher fatty acids containing from about 8 to about 24, preferably from about 10 to about 22 and especially from about 16 to about 22 carbon atoms in the alkyl chain. Suitable fatty acids can be obtained from natural sources such as, for instance, from soybean oil, castor oil, tallow, whale and fish oils, grease, lard and mixtures thereof). The fatty acids also can be synthetically prepared (e.g., by the oxidation of petroleum, or by hydrogenation of carbon monoxide by the Fischer-Tropsch process). Resin acids are suitable such as rosin and those resin acids in tall oil. Naphthenic acids are also suitable. Sodium and potassium soaps can be made by direct saponification of the fats and oils or by the neutralization of the free fatty acids which are prepared in a separate manufacturing process. Particularly useful are the sodium and potassium salts of the mixtures of fatty acids derived from tallow and hydrogenated fish oil.

[0040] Mixtures of anionic surfactants are particularly suitable herein, especially mixtures of sulfonate and sulfate surfactants in a weight ratio of from about 5:1 to about 1:5, preferably from about 5:1 to about 1:1, more preferably from about 5:1 to about 1.5:1. Especially preferred is a mixture of an alkyl benzene sulfonate having from 9 to 15, especially 11 to 13 carbon atoms in the alkyl radical, the cation being an alkali metal, preferably sodium; and either an alkyl sulfate having from 10 to 20, preferably 12 to 18 carbon atoms in the alkyl radical or an ethoxy sulfate having from 10 to 20, preferably 10 to 16 carbon atoms in the alkyl radical and an average degree of ethoxylation of 1 to 6, having an alkali metal cation, preferably sodium.

[0041] The nonionic surfactants useful in the present invention are condensates of ethylene oxide with a hydrophobic moiety to provide a surfactant having an average hydrophilic-lipophilic balance (HLB) in the range from about 8 to 17, preferably from about 9.5 to 13.5, more preferably from about 10 to about 12.5. The hydrophobic moiety may be aliphatic or aromatic in nature and the length of the polyoxyethylene group which is condensed with any particular hydrophobic group can be readily adjusted to yield a water-soluble compound having the desired degree of balance between hydrophilic and hydrophobic elements.

[0042] Examples of suitable nonionic surfactants include:

1. The polyethylene oxide condensates of alkyl phenol, e.g. the condensation products of alkyl phenols having an alkyl group containing from 6 to 12 carbon atoms in either a straight chain or branched chain configuration, with ethylene oxide, the said ethylene oxide being present in amounts equal to 3 to 30, preferably 5 to 14 moles of ethylene oxide per mole of alkyl phenol. The alkyl substituent in such compounds may be derived, for example, from polymerised propylene, di-isobutylene, octene and nonene. Other examples include dodecylphenol condensed with 9 moles of ethylene oxide per mole of phenol; dinonylphenol condensed with 11 moles of ethylene oxide per mole of phenol; nonylphenol and di-isooctylphenol condensed with 13 moles of ethylene oxide.

2. The condensation product of primary orsecondary aliphatic alcohols having from 8 to 24 carbon atoms, in either straight chain or branched chain configuration, with from 2 to about 40 moles, preferably 2 to about 9 moles of ethylene oxide per mole of alcohol. Preferably, the aliphatic alcohol comprises bewteen 9 and 18 carbon atoms and is ethoxylated with between 2 and 9, desirably between 3 and 8 moles of ethylene oxide per mole of aliphatic alcohol. The preferred surfactants are prepared from primary alcohols which are either linear (such as those derived from natural fats or, prepared by the Ziegler process from ethylene, e.g., myristyl, cetyl, stearyl alcohols), or partly branched such as the Lutensols (RTM), Dobanols (RTM) and Neodols (RTM) which have about 25% 2-methyl branching (Lutensol being a Trade Name of BASF, Dobanol and Neodol being Trade Names of Shell), or Synperonics (RTM), which are understood to nave about 50% 2-methyl branching (Synperonic is a Trade Name of I.C.I.) or the primary alcohols having more than 50% branched chain structure sold under the Trade Name Lial by Liquichimica. Specific examples of nonionic surfactants falling within the scope of the invention include Dobanol 45-4, Dobanol 45-7, Dobanol 45-9, Dobanol 91-2.5, Dobanol 91-3, Dibanol 91-4, Dobanol 91-6, Dobanol 91-8, Dobanol 23-6.5, Synperonic 6, Synperonic 14, the condensation products of coconut alcohol with an average of between 5 and 12 moles of ethylene oxide per mole of alcohol, the coconut alkyl portion having from 10 to 14 carbon atoms, and the condensation products of tallow alcohol with an average of between 7 and 12 moles of ethylene oxide per mole of alcohol, the tallow portion comprising essentially between 16 and 22 :arbon atoms. Secondary linear alkyl ethyoxylates are also suitable in the present compositions, especially those ethoxylates of the Tergitol (RTM) series having from about 9 to 15 carbon atoms in the alkyl group and up to about 11, especially from about 3 to 9, ethoxy residues per molecule.3.

[0043] The compounds formed by condensing ethylene oxide with a hydrophobic base formed by the condnesation of propylene oxide with propylene glycol. The molecular weight of the hydrophobic portion generally falls in the range of about 1500 to 1800. Such synthetic nonionic detergents are available on the market under the Trade Name of "Pluronic (RTM)" supplied by Wyandotte Chemicals Corporation.

[0044] Especially preferred nonionic surfactants for use herein are the C₉―C₁₅ primary alcohol ethoxylates containing 3-8 moles of ethylene oxide per mole of alcohol, particularly the C₁₂―C₁₅ primary alcohols containing 6-8 moles of ethylene oxide per mole of alcohol.

[0045] Cationic surfactants suitable for use herein include quaternary ammonium surfactants and surfactants of a semi-polar nature, for example amine oxides.

[0046] Suitable surfactants of the amine oxide class have the general formula I

[0047] 

wherein R¹ is a linear or branched alkyl or alkenyl group having 8 to 20 carbon atoms, each R² is independently selected from C_1-4 alkyl and ―(C_nH_2nO)_m H where i is an integer from 1 to 6, j is 0 or 1, n is 2 or 3 and m is from 1 to 7, the sum total of C_nH_2nO groups in a molecule being no more than 7. '

[0048] In a preferred embodiment R¹ has from 10 to 14 carbon atoms and each R² is independently selected from methyl and ―(C_nH_2nO)_mH wherein m is from 1 to 3 and the sum total of C_nH_2nO groups in a molecule is no more than_.5, preferably no more than 3. In a highly preferred embodiment, j is 0 and each R² is methyl, and R¹ is C₁₂-C₁₄ alkyl.

[0049] Another suitable class of amine oxide species is represented by bis-amine oxides having the following substituents.

j:1 R¹:tallow C₁₆―C₁₈ alkyl; palmityl; oleyl; stearyl

R₂: hydroxyethyl

i: 2 or 3

[0050] A specific example of this preferred class of bis-amine oxides is: N-hydrogenated C₁₆―C₁₈ tallow alkyl-N,N',N'tri-(2-hydroxyethyl)-propylene-1,3-diamine oxide.

[0051] Suitable quaternary ammonium surfactants for use in the present composition can be defined by the general formula II:

wherein R³ is a linear or branched alkyl, alkenyl or alkaryl group having 8 to 16 carbon atoms and each R⁴ is independently selected from C₁-₄ alkyl, C_1-4 alkaryl and ―(C_nH_2nO)_m wherein i is an integer from 1 to 6, j is 0 or 1, n is 2 or 3 and m is from 1 to 7, the sum total of C_nH_2nO groups in a molecule being no more than 7, and wherein Z represents counteranion in number to give electrical neutrality.

[0052] In a preferred embodiment, R³ has from 10 to 14 carbon atoms and each R⁴ is independently selected from methyl and (C_nH_2nO)_mH wherein m is from 1 to 3 and the sum total of C_nH_2nO groups in a molecule is no more than 5, preferably no more than 3. In a highly preferred embodiment j is 0, R⁴ is selected from methyl, hydroxyethyl and hydroxypropyl and R³ is C₁₂―C₁₄ alkyl. Particularly preferred surfactants of this class include C₁₂ alkyl trimethylammonium salts, C₁₄ alkyltrimethylammonium salts, coconutalkyltrimethylammonium salts, coconutalkyldimethylhydroxyethylammonium salts, coconut- alkyldimethylhydroxypropylammonium salts, and C₁₂ alkyldihydroxyethylmethyl ammonium salts.

[0053] Another group of useful cationic compounds are the diammonium salts of formula II in which j is 1, R³ . is C₁₂―C₁₄ alkyl, each R⁴ is methyl, hydroxyethyl or hydroxypropyl and i is 2 or 3. In a particularly preferred surfactant of this type, R³ is coconut alkyl, R⁴ is methyl and i is 3.

[0054] Chelating agents that can be incorporated include citric acid, nitrolotriacetic and ethylene diamine tetra acetic acids and their salts, organic phosphonate derivatives such as those disclosed in US-A-3,213,030, US-A-3,433,021, US-A-3,292,121 and US-A-2,599,807, and carboxylic acid builder salts such as those disclosed in US-A-3,308,067. Preferred chelating agents include nitrilotriacetic acid (NTA), nitrilotrimethylene phosphonic acid (NTMP), ethylene diamine tetra methylene phosphonic acid (EDTMP) and diethylene triamine penta methylene phosphonic acid (DETPMP), and these are incorporated in amounts such that the substrate chelating agent weight ratio. lies in the range from about 20:1 to about 1:5, preferably from about 5:1 to about 1:5 and most preferably 3:1 to 1:1.

[0055] Antiredeposition and soil suspension agents also constitute preferred components of the additive product of the invention. Cellulose derivatives such as methylcellulose, carboxymethylcellulose and hydroxyethylcellulose are examples of soil suspension agents and suitable antiredeposition agents are provided by homo- or co-polymeric polycarboxylic acids or their salts in which at least two carboxyl radicals are present separated by not more than two carbon atoms.

[0056] Highly preferred polymeric polycarboxylic acids are copolymers of maleic acid or maleic anhydride with methyl vinyl ether, ethyl vinyl ether, ethylene or acrylic acid, the polymers having a molecular weight in the range from 12,000 to 1,500,000.

[0057] A further description of suitable polymeric polycarboxylic acids is provided in EP-A-0063017.

[0058] In a method of making the laundry additive products of the invention, agglomerated particles of storage-sensitive detergency additive are dispersed in the matrix of organic materials under high-shear mixing conditions and at a temperature above the softening point of the additive composition but beneath the temperature and shear at which the agglomerates melt, decompose or disintegrate to provide, after dispersion, an average agglomerate size of at least 100 microns, preferably from about 150 to about 300 pm. In a preferred process embodiment, the dispersion temperature is at least 5°C above the softening point of the composition and at least 5°C beneath the melting completion temperature and more preferably at least 5°C below the melting onset temperature of the carrier for the agglomerated particles. The actual temperature of the organic matrix during the dispersing step can range from about 40°C to about 75°C, preferably from about 50°C to about 70°C. Thereafter, in the case of laundry additive products comprising an impregnated or coated substrate, a current of the laundry-additive composition is dispensed onto moving substrate at an application rate of from about 120 to about 400 g/m², preferably from about 120 to about 320 g/m² of substrate. The melt can be dispensed from the nip of a pair of counter-rotating, heated rollers having a nip setting greater than the average size of the agglomerates, but preferably less than about 400 µm, more preferably from about 150 to about 300 µm, the substrate being arranged for- movement counter to one of the rollers and in contact therewith, whereby the melt is transferred to the substrate by a wiping action. Thereafter, the substrate passes through smoothing and distributing means, for example a pair of plates stationed on opposite sides of the substrate at a spacing of less than about 300 pm, preferably from about 120 to about 220 pm. Finally, the coated substrate is cooled in a current of air.

[0059] The invention is illustrated in the following non-limitative Examples in which parts and percentages are by weight unless otherwise specified.

[0060] In the Examples, the abbreviations used have the following designation:

Examples 1 to 4

[0061] Laundry additive products according to the invention are prepared as follows. For each product, the components of the laundry additive composition are mixed at a temperature of about 60°C and passed through a Fryma (RTM) Colloid Mill, Model MK95-R/MZ 80R (made by M.M. Process Equipment Ltd. of M.M. House, Frogmore Road, Hemel Hempstead, Hertfordshire, United Kingdom) in which the grinding faces are set to a separation of about 180 µm. The melt is then fed through a pair of counterrotating rolls heated to 76°C and having a nip setting of 250 µm and is transferred to substrate moving counter to one of the rollers by wiping. The coated substrate is finally passed between a pair of static plates having a spacing of 180 µm, air-cooled, and cut into sheets of size 35x23 cm.

In the above Examples, the agglomerates have the following composition:

[0062] In the above, Agglomerate 1 is prepared by extrusion in a radial extruder as described in EP-A-0062523 Agglomerates 2 and 4 are prepared by spray-on of storage-sensitive ingredient and organic carrier onto a fluidized bed of granular sodium tripolyphosphate (hydrated); and Agglomerate 3 is prepared by spray-on of organic carrier, onto the remaining granular components in a drum agglomerator.

[0063] The compositions of Examples 1 to 4 have excellent storage-stability, convenience and reproducibility in use, and improved dust control.

Claims

1. A laundry additive product comprising:

(a) a laundry additive composition in the form of a plastic solid comprising discrete agglomerated particles of storage-sensitive detergency additive dispersed in a water-soluble or water-dispersible matrix of organic materials having a melting completion temperature of less than 85°C, the laundry additive composition having an IP49 penetrometer hardness of less than 1 mm (100 g, 15 sec, 25°C) and a softening temperature defined as the temperature at which the penetrometer hardness first exceeds 3 mm, of at least 35°C, the storage-sensitive detergency additive being agglomerated with a water-soluble or water-dispersible organic carrier having a melting-completion temperature of at least 5°C greater than the softening temperature of the laundry additive composition, the laundry additive composition being in water-releasable combination with

(b) a unitary water-insoluble carrier.

2. A product according to Claim 1 wherein the storage-sensitive detergency additive is selected from detergency enzymes, bleaches, bleach activators, bleach catalysts, photoactivators, dyes, fluorescers, suds suppressors, perfumes, fabric conditioning agents, and hydrolysable surfactants.

3. A product according to Claim 1 or 2 incorporating therein an antagonist for the storage-sensitive detergency additive, and wherein the detergency additive/antagonist combination are selected from at least one of the following:

4. A product according to any of Claims 1 to 3 wherein the storage-sensitive detergency additive is an enzyme selected from proteases, amylases and mixtures thereof.

5. A product according to any of Claims 1 to 4 wherein the laundry additive composition comprises at least 40% of said organic matrix materials.

6. A product according to any of Claims 1 to 5 wherein the agglomerated particles comprise a solid inorganic diluent in addition to the water-soluble or water-dispersible organic carrier.

7. A product according to any of Claims 1 to 6 wherein the organic matrix comprises at least 5%, preferably at least 15% of water-soluble or water-dispersible organic binding agent having a melting onset temperature of at least 35°C and a melting completion temperature of less than 85°C.

8. A product according to Claim 7 wherein the binding agent is selected from polyethylene glycols of molecular weight greater than 1000, C_'2-C₂₄ fatty acids and esters and amides thereof, polyvinyl pyrrolidone of molecular weight in the range from 40,000 to 700,000 and C₁₄―C₂₄ fatty alcohols ethoxylated with from 14 to 100 moles of ethylene oxide.

9. A product according to Claim 8 wherein the binding agent comprises at least 40%, preferably at least 50% thereof of polyethyleneglycol having a molecular weight greater than about 4000.

10. A product according to Claims 1 to 9 wherein the additive composition is coated on or impregnated into a flexible, sheet-like substrate at a weight ratio of composition:substrate of at least 3:1 preferably at least 5:1.

11. A product according to any of Claims 1 to 9 wherein the additive composition is in the form of an aggregate of physically discrete solid bodies having the agglomerated particles of storage-sensitive detergency additive dispersed therein, the aggregate being incorporated in a water-permeable or water-frangible pouch.

12. A product according to Claims 1 to 11 wherein the particles of storage-sensitive detergency additive have an average particle size of less than 150 µm, preferably less than 100 _lim, and that the agglomerates have an average particle size of at least 100 pm, preferably from 150 to 2000 µm.

13. A product according to any of Claims 1 to 12 comprising at least 5%, preferably at least 20% of organic detergent selected from anionic, nonionic and cationic surfactants and mixtures thereof.

14. A product according to Claim 13 wherein the organic detergent is selected from anionic sulphonate or sulphate surfactants and/or water-soluble cationic surfactants and mixtures of said anionic or cationic surfactants with water-soluble ethoxylated nonionic surfactants.

Ansprüche

1. Ein Wäschenzusatzprodukt, enthaltend

(a) eine Wäschezusatzzusammensetzung in der Form eines plastischen Feststoffes, der diskrete, agglomierte Teilchen von lagerungsempfindlichem Detergenszusatz, dispergiert in einer wasserlöslichen oder wasserdispergierbaren Matrix aus organischen Materialien mit einer Schmelzvollendungstemperatur von weniger als 85°C, enthält, wobei die Wäschezusatzzusammensetzung eine IP49 Penetrometerhärte von weniger als 1 mm (100 g, 15 s, 25°C) und eine Erweichungstemperatur, definiert als die Temperatur, bei welcher die Penetrometerhärte erstmals 3 mm übersteigt, von wenigstens 35°C aufweist, der lagerungsempfindliche Detergenszusatz mit einem wasserlöslichen oder wasserdispergierbaren, organischen Träger agglomeriert ist, der eine um wenigstens 5°C höhere Schmelzvollendungstemperatur als die Erweichungstemperatur der Wäschezusatzzusammensetzung aufweist, und die Wäschezusatzzusammensetzung in wasserfreisetzbarer Kombination mit

(b) einem einheitlichen, wasserunlöslichen Träger vorliegt.

2. Ein Produkt nach Anspruch 1, wobei der lagerungsempfindliche Detergenszusatz aus Detergensenzymen, Bleichmitteln, Bleichmittelaktivatoren, Bleichmittelkatalysatoren, Photoaktivatoren, Farbstoffen, Fluoreszenzstoffen, Schaumunterdrücken, Parfums, Textilkonditioniermitteln und hydrolysierbaren grenzflächenaktiven Mitteln ausgewählt ist.

3. Ein Produkt nach Anspruch 1 oder 2, welches einen Antagonisten für den lagerungsempfindlichen Detergenszusatz einverleibt aufweist, und bei welchem die Detergenszusatz-/Antagonistenkombination aus wenigstens einer der folgenden ausgewählt ist:

4. Ein Produkt nach einem der Ansprüche 1 bis 3, wobei der lagerungsempfindliche Detergenszusatzt ein Enzym ist, das aus Proteasen, Amylasen, und Gemischen davon, ausgewählt ist.

5. Ein Produkt nach einem der Ansprüche 1 bis 4, wobei die Wäschezusatzzusammensetzung wenigstens 40% an den genannten organischen Matrixmaterialien enthält.

6. Ein Produkt nach einem der Ansprüche 1 bis 5, wobei die agglomerierten Teilchen zusätzlich zu dem wasserlöslichen oder wasserdispergierbaren, organischen Träger ein festes, anorganisches Verdünnungsmittel enthalten.

7. Ein Produkt nach einem der Ansprüche 1 bis 6, wobei die organische Matrix wenigstens 5%, vorzugsweise wenigstens 15%, an wasserlöslichem oder wasserdispergierbarem, organischem Bindemittel mit einer Schmeizeinsatztemperatur von wenigstens 35°C und einer Schmelzvollendungstemperatur von weniger als 85°C enthält.

8. Ein Produkt nach Anspruch 7, wobei das Bindemittel aus Polyethylenglykolen mit einem Molekulargewicht von mehr als 1000, C₁₂-C₂₄-Fettsäuren und Estern und Amiden davon, Polyvinylpyrrolidon mit einem Molekulargewicht im Bereich von 40.000 bis 700.000 und C14-C24-Fettalkoholen, die mit 14 bis 100 Mol Ethylenoxid ethoxyliert sind, ausgewählt ist.

9. Ein Produkt nach Anspruch 8, wobei das Bindemittel wenigstens 40%, vorzugsweise wenigstens 50%, desselben an Polyethylenglykol mit einem Molekulargewicht von mehr als etwa 4000 enthält.

10. Ein Produkt nach den Ansprüchen 1 bis 9, wobei die Zusatzzusammensetzung als Überzug auf oder als Imprägnierung in einem biegsamen, blattartigen Substrat bei einem Gewichtsverhältnis von Zusammensetzung:Substrat von wenigstens 3:1, vorzugsweise wenigstens 5:1, vorliegt.

11. Ein Produkt nach einem der Ansprüche 1 bis 9, wobei die Zusatzzusammensetzung in der Form eines Aggregates von physikalisch diskreten, festen Körpern vorliegt, in denen die agglomierten Teilchen von lagerungsempfindlichem Detergenszusatz dispergiert sind, und wobei das Aggregat einem wasserdurchlässigen oder in Wasser zerbrechlichen Beutel einverliebt ist.

12. Ein Produkt nach den Ansprüchen 1 bis 11, wobei die Teilchen von lagerungsempfindlichem Detergenszusatz eine mittlere Teilchengröße von weniger als 150 um, vorzugsweise weniger als 100 um, haben, und wobei die Agglomerate eine mittlere Teilchengröße von wenigstens 100 pm, vorzugsweise von 150 bis 2000 um, aufweisen.

13. Ein Produkt nach einem der Ansprüche 1 bis 12, enthaltend wenigstens 5%, vorzugsweise wenigstens 20%, organisches Detergens, ausgewählt aus anionischen, nichtionischen und kationischen grenzflächenaktiven Mitteln, und Gemischen davon.

14. Ein Produkt nach Anspruch 13, wobei das organische Detergens aus anionischen Sulfonat- oder Sulfat-grenzflächenaktiven Mitteln und/oder wasserlöslichen, kationischen grenzflächenaktiven Mitteln, und Gemischen der genannten anionischen oder kationischen grenzflächenaktiven Mitteln, mit wasserlöslichen, ethoxylierten, nichtionischen grenzflächenaktiven Mitteln ausgewählt ist.

Revendications

1. Produit additif pour lessive, comprenant:

(a) une composition d'additif pour lessive, sous la forme d'un solide plastique comprenant des particules agglomérées discrètes d'un additif pour détergent sensible au stockage, en dispersion dans une matrice, soluble dans l'eau ou dispersible dans l'eau, de substances organiques ayant une température de fin de fusion inférieure à 85°C, la composition d'additif pour lessive ayant une dureté, au pénétromètre IP49, inférieure à 1 mm (100 g, 15 s, 25°C) et une température de ramollissement, définie comme étant la température à laquelle la dureté au pénétromètre dépasse pour la première fois 3 mm, d'au moins 35°C, l'additif pour détergent sensible au stockage étant aggloméré avec un support organique soluble dans l'eau ou dispersible dans l'eau ayant une température de fin de fusion d'au moins 5°C plus élevée que la température de ramollissement de la composition d'additif pour lessive, la composition d'additif pour lessive étant une combinaison pouvant se libérer dans l'eau, avec

(b) un support unitaire insoluble dans l'eau.

2. Produit selon la revendication 1, dans lequel l'additif pour détergent sensible au stockage est choisi parmi les enzymes pour-détergent, les agents de blanchiment, les activateurs de blanchiment, les catalyseurs de blanchiment, les photoactivateurs, les colorants, les agents fluorescents, les régulateurs de mousse, les parfums, les agents de conditionnement des tissus et les tensioactifs hydrolysables.

3. Produit selon la revendication 1 ou 2, comprenant un antagoniste de l'additif pour détergent sensible au stockage, et dans lequel la combinaison additif pour détergent/antagoniste est choisie parmi au moins l'une des combinaisons suivantes:

4. Produit selon l'une quelconque des revendications 1 à 3, dans lequel l'additif pour détergent sensible au stockage est une enzyme choisie parmi les protéases, les amylases et leurs mélanges.

5. Produit selon l'une quelconque des revendications 1 à 4, dans lequel la composition d'additif pour lessive comprend au moins 40% desdites substances de matrice organique.

6. Produit selon l'une quelconque des revendications 1 à 5, dans lequel les particules agglomérées comprennent un diluant inorganique solide, en plus du support organique soluble dans l'eau ou dispersible dans l'eau.

7. Produit selon l'une quelconque des revendications 1 à 6, dans lequel la matrice organique comprend au moins 5%, de préférence 15% d'un agent liant organique soluble dans l'eau ou dispersible dans l'eau, ayant une température de début de fusion d'au moins 35°C et une température de fin de fusion inférieure à 85°C.

8. Produit selon la revendication 7, dans lequel l'agent liant est choisi parmi les polyéthylèneglycols ayant une masse moléculaire supérieure à 1000, les acides gras en C₁₂―C₂₄, et leurs esters et amides, la polyvinylpyrrolidone ayant une masse moléculaire dans l'intervalle de 40000 à 700 000, et les alcools gras en C₁₄―C₂₄ éthoxylés par 14 à 100 moles d'oxyde d'éthylène.

9. Produit selon la revendication 8, dans lequel l'agent liant comprend au moins 40%, de préférence au moins 50% de cet agent, d'un polyéthylèneglycol ayant une masse moléculaire supérieure à environ 4000.

10. Produit selon les revendications 1 à 9, dans lequel la composition d'additif est appliquée sur ou imprégnée dans un substrat souple, du type feuille, selon une proportion pondérale composition:substrat d'au moins 3:1, de préférence d'au moins 5:1.

11. Produit selon l'une quelconque des revendications. 1 à 9, dans lequel la composition d'additif se présente sous la forme d'un agrégat de corps solides physiquement discrets dans lequel sont dispersées les particules agglomérées de l'additif pour détergent sensible au stockage, l'agrégat étant placé dans une poche perméable à l'eau ou pouvant se briser sous l'effet de l'eau.

12. Produit selon la revendications 1 à 11, dans lequel les particules de l'additif pour détergent sensible au stockage ont une granulométrie moyenne inférieure à 150 pm, de préférence inférieure à 100 ^pm, et les agglomérats ont une granulométrie moyenne d'au moins 100 um, de préférence de 150 à 2000 pm.

13. Produit selon l'une quelconque des revendications 1 à 12, comprenant au moins 5%, de préférence au moins 20% d'un détergent organique choisi parmi les tensioactifs anioniques, non-ioniques et cationiques, et leurs mélanges.

14. Produit selon la revendication 13, dans lequel le détergent organique est choisi parmi les tensioactifs anioniques sulfonates ou sulfates et/ou les tensioactifs cationiques solubles dans l'eau, et les mélanges desdits tensioactifs anioniques ou cationiques avec des tensioactifs non-ioniques éthoxylés solubles dans l'eau.