LAUNDRY ADDITIVE PRODUCTS

Abstract: A laundry additive product comprising a solid laundry additive composition containing discrete agglomerated par­ ticles of storage sensitive detergency additive dispersed in a matrix of organic materials having a melting completion temperature of less than 85°C, the additive composition being in water-releasable combination with a unitary, water-­ insoluble carrier. A preferred storage-sensitive additive is a detergency enzyme. The compositions have improved stor­ age-stability, dust control, reproducibility and convenience of use.

Description: LAUNDRY ADDITIVE PRODUCTS 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. 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 cat ionic 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. 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. British Patents 1,204,123, 1,441,416 and 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. 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. Accordingly, the present invention provides a laundry additive product characterized by (a) a solid laundry additive composition 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 about 850C, the laundry additive composition being in water-releasable combination with (b) a unitary water-insoluble carrier. 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: Additive Antagonist i) Detergency Enzymes Bleaches, Sequestrants, Acids, Bases or Surfactants ii) Bleaches Bleach Activators or Catalysts, Acids or Bases iii) Bleach Activators or Bleaches, Acids or Bases Bleach Catalysts iv) Photoactivators Nonionic Surfactants v) Dyes Nonionic Surfactants vi) Fluorescers Bleaches or Cationic Surfactants vii) Suds controllers Surfactants viii) Perfumes Bleaches ix) Fabric Conditioning Agents Anionic Surfactants x) Hydrolysable Surfactants Acids or Bases The laundry additive composition preferbly 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 850C. These in turn each preferably have a melting completion temperature of less than about 750C, more preferably less than about 700C. The additive composition itself desirably has a softening temperature of at least about 350C, more preferably at least about 40"C, especially at least about 500C, and a penetrometer hardness of less than about 10, more preferably less than about 7. In it preferred embodiments, the laundry additive product contains at least about 5%, preferably at least about 15% by weight of composition of water-soluble or water-dispersible organic binding agent having a melting-onset temperature of at least about 350C and a melting completion temperature of less than about 850C. Preferably, the binding agent is selected from polyethylene glycols of molecular weight greater than about 1000, C12-C24 fatty acids and esters and amides thereof, polyvinyl pyrrolidone of molecular weight in the range from about 40,000 to about 700,000, and C14-C24 fatty alcohols ethoxylated with from about 14 to about 100 moles of ethylene oxide. Highly preferred binding agents comprise at least about 40%, especially at least about 50% thereof of polyethyleneglycol having a molecular weight greater than about 4000. The agglomerate component of the additive product generally 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 about 150 microns, more preferably less than 100 microns, especially less than 50 microns. 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 about 100 microns, more preferably from about 150 microns to about 2000 microns. The agglomerating agent can take the form of a carrier in which the detergency additive and, if present, diluent are dispersed, or the agglomerating agent can simply act to promote physical adhesion of the component particles of the agglomerate. Alternatively the agglomerating agent can function as an encapsulating or coating agent for the detergency additive. Preferred carriers are water-soluble or water-dispersible organic materials having a melting onset temperature of at least 35 CC, more preferably at least about 450C, especially at least about 500C and a melting completion temperature of at least about 400C, more preferably at least about 450C, especially at least 550C, and of less than about 1000C, more preferably less than about 850C, especially less than about 750C. Desirably, the melting completion temperature of the carrier is at least about 50C greater than the softening temperature of the additive composition. Suitable organic carriers are again selected from polyethylene glycols of molecular weight greater than about 1000, C12-94 fatty acids and esters and amides thereof, polyvinyl pyrrolidone of molecular weight in the range from about 40,000 to about 70D,000, and C14-C24 fatty alcohols- ethoxylated with from about 14 to about 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, polyvinylalcohol, 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%. 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 (ie loading ratio) of at least about 3:1, more preferably at least 5:1, especially at least about 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 waterfrangible pouch. The laundry additive products of the invention suitably contain at least about 5%, preferably at least about 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 about 850C and form part of the matrix of organic materials. Preferred cationic surfactants have melting onset temperatures of at least about 350C 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 about 1000C and are dispersed in the organic matrix. Surfactants which are sensitive to alkaline or acid hydrolysis (eg 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 cat ionic surfactants and mixtures of these anionic and/or cat ionic surfactants with water-soluble ethoxylated nonionic surfactants. In a process embodiment of the invention, there is provided a process of making the laundry additive product defined herein comprising 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. The laundry additive products of the invention will no be discussed in detail. 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. Specific examples of carbohydrases are maltase, saccharase, amylases, cellulase, pectinase, lysozyme, i-glucosidase, and B-glucosidase. Preferred ared-amylases of mould, cerial or bacterial origin. Specific examples of esterases are gastric lipase, pancreatic lipase, plantlipases, phospholipases, cholineesterases and phosphotases. 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 about 0.001 to about 0.5, more preferably from about 0.003 to about O.lg of enzyme per unit of product (enzyme expressed in pure form). For protease and < -amylase specifically, the laundry additive products preferably comprise from about 0.075 to about 15, more preferably from about 0.15 to about 4.5 Anson units of protease per unit of product, and from about 2,000, to about 400,000, more preferably from about 4,000 to about 120,000 maltose units ofo(-amylase per unit of product. Protease activity is measured against Novo Alcalase protease as standard using the method of Dunn & BR< 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 (4.18)/acetic acid buffer solution, a sample concentration of 0.05g/litre or a multiple dilution thereof, a digestion temperature of 370C and a digestion time of 5 minutes. The amylase then has one activity unit for each 0.4mg of maltose hydrate produced during hydrolysis. 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 4Na2SO4:2H202:1NaCl. Suitable organic bleaches include peroxylauric acid, peroxyactanoic acid, peroxynonanoic acid, peroxydecanoic acid, diperoxydodecanedioic acid, diperoxyazelaic acid, mono- and diperoxyphthalic acid and mono- and diperoxyisopthalic 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 O-acetoxy benzoate. Bleach precursors can be used at a precursor: unitary carrier ratio within the range from about 30:1 to about 1:10, preferably from about 8:1 to about 1:2, while bleaches can be used at a bleach:unitary carrier ratio from about 30:1 to about 1:4, preferably from about 10:1 to about 1:1. Bleach catalyst systems suitable for use herein include chelated transition metal catalysts as described in British Patent Application 8215890. 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 mm2ys, preferably from about 3000 to about 30,000mh2/s, and mixtures of siloxanes and hydrophobic silanated (preferably trimethylsilanated) silica having a particle size in the range from about 10 millimicrons to about 20 millimicrons and a specific surface area above about 50 m2/g. Suitable waxes include microcrystalline waxes having a melting point in the range from about 650C to about 1000C, a molecular weight in the range from about 400-1000, and a penetration value of at least 6, measured at 770C by ASTM-D1321, and also paraffin waxes, synthetic waxes and natural waxes. Suitable phosphate esters include mono- and/or di-C16-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. Other storage-sensitive detergency additives include bleach-sensitive flourescers such as Blackophor MBBH (Bayer AG) and Tinopal CES and EMS (Ciba Geigy); nonionic surfactant-soluble dyes and photoactivators as disclosed in European Application No 82300309, highly preferred materials being zinc phthalocyanine tri- and tetrasulphonates; bleach-sensitive perfumes; anionic surfactant-sensitive fabric conditioning agents such as di-C12-C24 alkyl or alkenyl amines and ammonium salts; and hydrolysable surfactants such as the C10-C16 alkyl and alkyl ether sulphonates. The agglomerates of storage-sensitive detergency additive can be prepared by any appropriate agglomeration technique, for example by extrusion with a molten organic carrier or by dispersing liquid organic carrier or adhesive 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. Turning to the laundry additive composition, this is in solid form at ambient temperatures (250C and below) and preferably has a softening temperature of at least about 350C, more preferably at least about 400C, especially at least about 500 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 can be determined by standard methods, for example, by the penetrometer-based technique of IP49 (or the technically equivalent ASTM-D5 -or BS4691). Thus, laundry additive compositions preferred for use wherein have a penetration under a 100g load at 250C after 15 seconds under IP49 of less than about 10 (measured in tenths of a millimetre), more preferably less than about 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 about 30. 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 20-300C/min) to -700C. Thermal analysis is then carried out a a heating rate of 100C/min using sufficient amplification ofa T signal (ie 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 t6 the sample temperature axis, through the highest temperature endotherm peak. The organic materials constituting the matrix have a melting completion temperature of less than about 850C. In addition, the laundry additive products of the invention preferably contain at least about 5% by weight of composition of binding agent defined as organic material having a melting completion temperature of less than 850C, preferably less than about 800C, especially less than about 700C, and a melting onset temperature of at least 350C, preferably at least 400C, especially at least 500C. 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. 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 of at least about 3:1, preferably at least about 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. 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. 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 8mm to about 20mm, in length and are from about 1 to about 5 denier (Denier is an internationally recognised unit in yarn measure, corresponding to the weight in grams of a 9,000 meter length of yarn). 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. The flexible 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 0.5mm to about 5mm and a length of from about 0.8mm to about Smm, 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 (ie they have mirror symmetry) and preferably have, on average, a width of from about 0.7 to about 2.5mm and a length of from about 1.7mm to about 4mm. The area of the apertures, on the other hand, is preferably from about 0.7mm2 to about 7mm2, more preferably from about 0.8mm2 to about 3.5mm2, and the ratio of length:width is from 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 apartures and the complete filling of coated apertures from one surface of the substrate to the other. 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 0.8mm to about 1.5mm and a length of from about 2mm to about 3.5mm.In preferred embodiments, however, the apertures are generally square-shaped with a side dimension of from about 1 to 2.5mm. As used herein, "length" refers to the dimension of the principal (ie longest) longitudinal axis, and "width" is the maximum dimension perpendicular to this axis. As far as loading ratio is concerned (ie the weight ratio of composition:substrate) this preferably is at least about 6:1 and more preferably at least 7:1 r 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. An example of an apertured non-woven substrate suitable herein is a regenerated cellulose sheet of 1.5 denier fibres bonded with Rhoplex HA 8 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 ellipitical in shape and are in side-by-side arrangement. The apertures have a width of about 0.9mm and a length of about 2.3mum measured in a relaxed condition. Another highly preferred substrate based on 1.5 denier regenerated cellulose fibres-with Rhoplex HA8 binder has a fibre:binder ration of about 82:18, a basis weight of about 35g/m2, and about 22 apertures/cm2. In this example, the apertures are generally square-shaped with a width (relaxed) of about l.lmm. The apertures are again disposed in side-by-side arrangement. 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 . In 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. The laundry additive products qf the invention can be supplemented by all manner of laundering and detergency components. Suitably, the additive products can contain at least about 5%, preferably from about 20% to about 90%, more preferably from about 35% to about 75% of organic detergent selected from anionic, nonionic and cationic surfactants and mixtures thereof. Anionic surfactants preferably comprise from about 7% to about 38%, more preferably from about 15% to about 30% by weight of composition; nonionic surfactants from about 8% to about 32%, more preferably from about 12% to about 25% by weight of composition; and cationic surfactants from about 5% to about 30%, more preferably from about 8% to about 20% by weight of composition. The anionic surfactant can be any bne 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-l-sulphonate, and beta-alkyloxy alkane sulphonate. A particularly suitable class of anionic surfactants includes water-soluble salts, particularly the alkali metal, ammonium and alkanolammonium salts 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 (C8 18) 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 U.S.P. 2,220,099 and 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 C118 LAS, and C12-C15 methyl branched alkyl sulphates. 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 soil; 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. Other useful anionic detergent compounds herein include the water-soluble salts or esters or c-sulphonated fatty acids containing from about 6 to 20 carbon atoms in the fatty acid group and from abou-t 1 to 10 carbon atoms in the ester group; water-soluble salts of 2-acyloxy-alkane-l-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 oleo in sulphonates containing from about 12 to 24, preferably aout 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 andj3-alkyloxy 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. 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 syntbeti,cally 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. Napthenic 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. 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. 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-lipophilit 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. 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 or secondary 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 between 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, Dobanols and Neodols which have about 25% 2methyl branching (Lutensol being a Trade Name of BASF, Dobanol and Neodol being Trade Names of Shell), or Synperonics, which are understood to have 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, Dobanol 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 carbon atoms. Secondary linear alkyl ethoxylates are also suitable in the present compositions, especially those ethoxylates of the Tergitol 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. The compounds formed by condensing ethylene oxide with a hydrophobic base formed by the condensation 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 Wame of "Pluronicw supplied by Wyandotte Chemicals Corporation. Especially preferred nonionic surfactants for use herein are the Cg-Cl5 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. Cationic surfactants suitable for use herein include quaternary ammonium surfactants and surfactants of a semi-polar nature, for example amine oxides. Suitable surfactants of the amine oxide class have the general formula I EMI20.1 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 -(CnH2n0)mH 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 CnH2n0 groups in a molecule being no more than 7. In a preferred embodiment R1 has from 10 to 14 carbon atoms and each R2 is independently selected from methyl and (CnH2nO)mH wherein m is from 1 to 3 and the sum total of CnH 2n0 groups in a molecule is no more than 5, preferably no more than 3. In a highly preferred embodiment, j is O and each is methyl, and R is C12-C14 alkyl. Another suitable class of amine oxide species is represented by bis-amine oxides having the following substituents. j: 1 R1: tallow C16-Cl8 alkyl; palmityl; oleyl; stearyl R2: hydroxyethyl i : 2 or 3 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. Suitable quaternary ammonium surfactants for use in the present composition can be defined by the general formula II: EMI21.1 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 C14 alkyl, C1-4 alkaryl and ¯(CnH2n0)m wherein i is an integer from 1 to 6, j is 0 or 1, n is 2 or 3 and mis from 1 to 7, the sum total of CnH2n0 groups in a molecule being no more than 7, and wherein Z represents counteranion in number to give electrical neutrality, In a preferred embodiment, R3 has from 10 to 14 carbon atoms and each R4 is independently selected from methyl and (CnH2n0)mH wherein m is from 1 to 3 and the sum total of CnH 2n0 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 R3is C12-C14 alkyl. Particularly preferred surfactants of this class include C12 alkyl trimethylammonium salts, C14 alkyltrimethylammonium salts, coconutalkyltrimethylammonium salts, coconutalkyldimethylhydroxyethylammonium salts, coconutalkyldimethylhydroxypropylammonium salts, and C12 alkyldihydroxyethylmethyl ammonium salts. Another group of useful cat ionic compounds are the diammonium salts of formula II in which j is 1, R3 is C12-Cl4 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. 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 Diehl US Patent No. 3,213,030 issued 19 October, 1965; Roy US Patent No. 3,433,021 issued 14 January, 1968, Gedge US Patent No. 3,292,121 issued 9 January, 1968; and Bersworth US Patent No. 2,599,807 issued 10 June, 1952, and carboxylic acid builder salts such as those disclosed in Diehl US Patent No. 3,308,067 issued 7 March, 1967. 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. Antiredeposition and soil suspension agents also constitute preferred components of the additive product of the invention. Cellulose derivatives such as methylcelulose, carboxymethylcellulose and hydroxyethylcellulose are examples of soil suspension agents and suitable antiredeposition agents are provided by homo- or co-polymcric polycarboxylic acids or their salts in which at least two carboxyl radicals are present separated by not more than two carbon atoms. 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. A further description of suitable polymeric polycarboxylic acids is provided in the Applicants1 European Patent Application No. 82301776.9. 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 disintergrate to provide, after dispersion, an average agglomerate size of at least 100 microns, preferably from about 150 to about 300 microns. In a preferred process embodiment, the dispersion temperature is at least 50C above the softening point of the composition and, where the agglomerate incorporates a carrier, at least 5"C beneath the melting completion temperature and more preferably at least 50C 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 400C to about 750C, preferably from about 500C to about 700C. 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 microns, more preferably from about 150 to about 300 microns, the substrate being arranged for movement counter to one of the rollers and in contact therwith, 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 microns, preferably from about 120 to about 220 microns. Finally, the coated substrate is cooled in-a current of air. The invention is illustrated in the following non-limitative Examples in which parts and percentages are by weight unless otherwise specified. In the Examples, the abbreviations used have the following designation: LAS : Linear C12 alkyl benzene sulphonate C12/14AS : Sodium C12-C14 alkyl sulphate TAEn : Hardened tallow alcohol ethoxylated with n moles of ethylene oxide per mole of alcohol MAO : C12-C14 alkyl dimethyl amine amide C12TMAB : C12 alkyl trimethyl ammonium bromide C12 Amide : Coconut monoethanolamide Dobanol 45-E-7 : A C14-C15 primary alcohol condensed with 7 moles of ethylene oxide, marketed by Shell Clay : Sodium montmorillonite PEG : Polyethylene glycol (MWt normally follows) TAED : Tetraacetylethylenediamine Silicone/Silica : 20:1 mixture of polydimethylsiloxane and silanated silica Wax : Microcrystalline wax - Witodur 272-M.pt870C Porphine : Tri/tetra sulphonated zinc phthalocyanine Gantrez ANll9 : Maleic anhydride/yinyl methyl ether copolymer, believed to have an average molecular weight of 240,000, marketed by GAF. This material was prehydrolysed with NaOH before addition. Perborate : Anhydrous sodium perborate bleach of empirical formula NaBO2.H202 MA/AA : Maleic acid/acrylic acid copolymer, 1:4 mole ratio, m.wt 80,000. EDTA : Sodiumethylenediaminetetraacetate Brightener 1 : Disodium 4,4'-bis(2-morpholino-4 anilino-s-triazin-6-ylamino) stilbene-2:2'-disulphonate Brightener 2 : Disodium 4,4'-bis(2-sulphonato styryl)biphenyl DETPMP : Diethylenetriamine -penta(methylene phosphonic acid), marketed by Monsanto under the Trade name Dequest 2060 EDTMP : Ethylenediamine tetra(methylene phosphonic acid), marketed by Monsanto, under the Trade name Dequest 2041 Substrate 1 : Non-woven fabric formed of 100% unbleached crimped rayon fibres of 1.5 denier bonded with 23% polyacylate binder; basis weight 35 g/m;17 elliptical apertures/cm2; aperture width 0.9mm; aperture length 2.5mm Substrate 2 : Non-woven fabric formed of 100% unbleached crimped rayon fibres of 1.5 denier bonded with 18% polyacylate binder; basis weight 35g/m2; 22 square-shaped apertures/cm ; side dimension l.lmm EXAMPLES 1 to 6 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 600C and passed through a Fryma 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 microns. The melt is then fed through a pair of counterrotating rolls heated to 760C.and having a nip setting of 250 microns and is transferred to substrate moving counter td one of the rollers by wiping. The coated substrate is finally passed between a pair of static plates having a spacing of 180 microns, air-cooled, and cut into sheets of size 35.X 23cm. EXAMPLES 1 2 3 4 5 6 LAS - - - 2 - C12/14A5 6 4 2 - - 3 25 - 3 3 - 2 - C12TMAB 3 - - - 3 1 Dobanol 45E7 5 3 6 8 4 5 MAO - - . - 3 - PEG 8000 7 - - 8 - 2 PEG 4000 - 5 6 - 3 3 Silicone/Silica 0.3 0.3 - - 0.3 Gantrez ANll9 - 0.3 - - 0.3 MA/AA - - 0.5 - - 0.3 Perborate - 5 - - 4 7 EDTA 1 - - 0.5 0.4 Aluminium Sulphate - - - - - 0.3 Brightener 1 0.1 0.3 - 0.2 - Brightener 2 - 0.1 0.2 0.2 - 0.2 Tetrasodium DETPMP - 1 - - 0.6 Tetrasodium EDTMP - - 1 0.5 - Moisture 0.02 0.01 0.03 0.02 0.01 0.02 Substrate 1 2.8 - 2.8 - 2.8 Substrate 2 - 2.8 - 2.8 - 2.8 Agglomerate 1 1 0.5 1 1.5 1 0.5 Agglomerate 2 - 3 - - - Agglomerate 3 - - 1 1 - Agglomerate 4 - - - 1 - Agglomerate 5 - - - - 5 Agglomerate 6 - - - - - 2 In the above Examples, the agglomerates have the following composition: AGGLOMERATE 1 2 3 4 5 6 Protease 9 - - - - Amylase 3 - - - - TAED - 86 - - 20 - Silicone/silica - - 11 - - 10 Porphine - - - 0.2 - Brightener 1 - - - 10 Brightener 2 - - - - 1 Cu 2+ EDTA complex (1: :1 molar) - - -. - - 10 TiO2 10 - - - - TAE80 - 14 6 - 27 10 PEG 8000 - - 6 10 - 10 PEG 4000 1 - - - - C12 Amide 5 - - - - - Polyvinylpyrrolidone 1 - - - - Clay - - - - 42 Dextrin 4 - - - - Wax - - 6 - - Sodium sulphate 13 - - - - Sodium chioride 54 - - - - Sodium tripolyphosphate - - 56 80 - 47 Water - - 15 98 - 13 In the above, Agglomerate 1 is prepared by extrusion and has a protease activity of 2 Anson units/g and an amylase activity of 48,000 maltose units/g; Agglomerate 2 is prepared by extrusion in a radial extruder as described in European Patent Application No 82301775.1; Agglomerates 3 and 6 are prepared by spray-on of storage-sensitive ingredient and organic carrier onto a fluidized bed of granular sodium tripolyphosphate (hydrated); and Agglomerates 4 and 5 and prepared by spray-on of organic carrier and, where appropriate water, onto the remaining granular components in a drum agglomerator. The compositions of Examples 1 to 6 have excellent storage-stability, convenience and reproducibility in use, and improved dust control.

Claims: CLAIMS 1. A laundry additive product characterized by: (a) a solid laundry additive composition comprising dis crete 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 850C, the laundry additive composition being in water-releasable combination with (b) a unitary water-insoluble carrier. 2. A product according to Claim 1 characterized in that 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: Additive Antagonist i) Detergency Enzymes Bleaches, Sequestrants, Acids, Bases or Surfactants ii) Bleaches Bleach Activators or Catalysts, Acids or Bases iii) Bleach Activators or Bleaches, Acids or Bases Bleach Catalysts iv) Photoactivators Nonionic Surfactants v) Dyes Nonionic Surfactants vi) Fluorescers Bleaches or Cationic Surfaciants vii) Suds controllers Surfactants viii) Perfumes Bleaches ix) Fabric Conditioning Agents Anionic Surfactants Hydrolysable Surfactants Acids or Bases 4. A product according to any of Claims 1 to 3 characterized in that 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 characterized by a softening temperature of at least 350C, a 15 second penetrometer hardness of less than 10, and comprising at least 40% of said organic matrix materials. 6. A product according to any of Claims 1 to 5 characterized in that the agglomerated particles comprise an agglomerating agent and optionally a solid inorganic diluent, the agglomerating agent being in the form of a water-soluble or water-dispersible organic carrier, an adhesive, or an encapsulating or coating agent. 7. A product according to any of Claims 1 to 6 characterized in that the organic matrix comprises at least about 5%, preferably at least about 15% of water-soluble or water-dispersible organic binding agent having a melting onset temperature of at least about 350C and a melting completion temperature of less than about 850C. 8. A product according to Claim 7 characterized in that the binding agent is selected from polyethylene glycols of molecular weight greater than about 1000, C12-C24 fatty acids and esters and amides thereof, polyvinyl pyrrolidone of molecular weight in the range from about 40,000 to about 700,000, and C14-C24 fatty alcohols ethoxylated with from about 14 to about 100 moles of ethylene oxide. 9. A product according to Claim 8 characterized in that the binding agent comprises at least about 40t, preferably at least about 50% thereof of polyethyleneglycol having a molecular weight greater than about 4000. 10. A product according to any of Claims 1 to 9 characterized in that the additive composition is coated on or impregnated into a flexible, sheet-like substrate at a weight ratio of composition:substrate of at leas 3:1, preferably at least 5:1. 11. A product according to any of Claims 1 to 9 characterized in that 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 any of Claims 1 to 11 characterized in that the particles of storage-sensitive detergency additive have an average particle size of less than about 150 microns, preferably less than about 100 microns, and than the agglomerates have an average particle size of at least about 100 microns, preferably from about 150 to about 2000 microns. 13. A product according to any of Claims 1 to 12 characterized by 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 characterized in that the organic detergent is selected from anionic sulphonate or sulphate surfactants and/or water-soluble cationic surfactants and mixtures of said anionic or cat ionic surfactants with water-soluble ethoxylated nonionic surfactants.

Inventors: BROOKS, MAXIM COURTNEY, CASSIDY, STEPHEN PAUL
Applicants: PROCTER & GAMBLE LIMITED, THE PROCTER & GAMBLE COMPANY
Application year: 1983
Main classification: C11D17
IPC codes: C11D17, C11D3