Title of Invention	"A PROCESS FOR PREPARING A LOW DENSITY DETERGENT COMPOSITION"
Abstract	A process for continuously preparing low density detergent agglomerates is provided. The process comprises the steps of: (a) spray drying an aqueous mixture of sodium sulfate, sodium carbonate and a minor amount of a surfactant so as to form spray dried granules containing an inorganic double salt having the formula Na2SO4•Na2CO3 and a minor amount of the surfactant; (b) agglomerating the spray dried granules with a detergent surfactant paste or precursor thereof and adjunct detergent material initially in a high speed mixer and subsequently in a moderate speed mixer to obtain detergent agglomerates, wherein the adjunct detergent material includes an adjunct sodium carbonate material; and (c) drying or cooling the detergent agglomerates so as to form the detergent composition having a density of below about 500 g/1.

Title of Invention

"A PROCESS FOR PREPARING A LOW DENSITY DETERGENT COMPOSITION"

Abstract

A process for continuously preparing low density detergent agglomerates is provided. The process comprises the steps of: (a) spray drying an aqueous mixture of sodium sulfate, sodium carbonate and a minor amount of a surfactant so as to form spray dried granules containing an inorganic double salt having the formula Na2SO4•Na2CO3 and a minor amount of the surfactant; (b) agglomerating the spray dried granules with a detergent surfactant paste or precursor thereof and adjunct detergent material initially in a high speed mixer and subsequently in a moderate speed mixer to obtain detergent agglomerates, wherein the adjunct detergent material includes an adjunct sodium carbonate material; and (c) drying or cooling the detergent agglomerates so as to form the detergent composition having a density of below about 500 g/1.

Full Text	FIELD OF THE INVENTION The present invention generally relates to a process for producing a low density detergent composition. More particularly, the invention is directed to a process during which low density detergent agglomerates are produced by agglomerating a surfactant paste or liquid acid precursor of anionic surfactant with spray dried granules containing an inorganic double salt of sodium carbonate and sodium sulfate and a surfactant. The process produces a free flowing, low density detergent composition which can be commercially sold as a conventional non-compact detergent composition or used as an admix in a low dosage, "compact" detergent product. BACKGROUND OF THE INVENTION Recently, there has been considerable interest within the detergent industry for laundry detergents which are "compact" and therefore, have low dosage volumes. To facilitate production of these so-called low dosage detergents, many attempts have been made to produce high bulk density detergents, for example with a density of 600 g/1 or higher. The low dosage detergents are currently in high demand as they conserve resources and can be sold in small packages which are more convenient for consumers. However, the extent to which modern detergent products need to be "compact" in nature remains unsettled. In fact, many consumers, especially in developing countries, continue to prefer a higher dosage levels in their respective laundering operations. Consequently, there is a need in the art of producing modern detergent compositions for flexibility in the ultimate density of the final composition. Generally, there are two primary types of processes by which detergent granules or powders can be prepared. The first type of process involves spray-drying an aqueous detergent slurry in a spray-drying tower to produce highly porous detergent granules. In the second type of process, the various detergent components are dry mixed after which they are agglomerated with a binder such as a nonionic or anionic surfactant. In both processes, the most important factors which govern the density of the resulting detergent granules are the density, porosity and surface area, shape of the various starting materials and their respective chemical composition. These parameters, however, can only be varied within a limited range. Thus, flexibility in the substantial bulk density can only be achieved by additional processing steps which lead to lower density of the detergent granules. There have been many attempts in the art for providing processes which increase the density of detergent granules or powders. Particular attention has been .given to densification of spray-dried granules by post tower treatment. For example, one attempt involves a batch process in which spray-dried or granulated detergent powders containing sodium tripolyphosphate and sodium sulfate are densified and spheronized in a Marumerizer®. This apparatus comprises a substantially horizontal, roughened, rotatable table positioned within and at the base of a substantially vertical, smooth walled cylinder. This process, however, is essentially a batch process and is therefore less suitable for the large scale production of detergent powders. More recently, other attempts have been made to provide continuous processes for increasing the density of "post-tower" or spray dried detergent granules. Typically, such processes require a first apparatus which pulverizes or grinds the granules and a second apparatus which increases the density of the pulverized granules by agglomeration. While these processes achieve the desired increase in density by treating or densifying "post tower" or spray dried granules, they do not provide a process which has the flexibility of providing lower density granules. Moreover, all of the aforementioned processes are directed primarily for densifying or otherwise processing spray dried granules. Currently, the relative amounts and types of materials subjected to spray drying processes in the production of detergent granules has been limited. For example, it has been difficult to attain high levels of surfactant in the resulting detergent composition, a feature which facilitates production of detergents in a more efficient manner. Thus, it would be desirable to have a process by which detergent compositions can be produced without having the limitations imposed by conventional spray drying techniques. To that end, the art is also replete with disclosures of processes which entail agglomerating detergent compositions. For example, attempts have been made to agglomerate detergent builders by mixing zeolite and/or layered silicates in a mixer to form free flowing agglomerates. While such attempts suggest that their process can be used to produce detergent agglomerates, they do not provide a mechanism by which starting detergent materials in the form of pastes, liquids and/or dry materials can be effectively agglomerated into crisp, free flowing detergent agglomerates having low densities (i.e. less than 500 g/1) rather than higher densities. Accordingly, there remains a need in the art to have a process for continuously producing a low density detergent composition directly from starting detergent ingredients. Also, there remains a need for such a process which is more efficient, flexible and economical to facilitate large-scale production of detergents of low as well as high dosage levels. BACKGROUND ART The following references are directed to densifying spray-dried granules: Appel et al, U.S. Patent No. 5,133,924 (Lever); Bortolotti et al,U.S. Patent No. 5,160,65,7 (Lever); Johnson et al, British patent No. 1,517,713 (Unilever); and Curtis, European Patent Application 451,894. The following references are directed to producing detergents by agglomeration: Beerse et al, U.S. Patent No. 5,108,646 (Procter & Gamble); Capeci et al, tl.S. Patent No. 5,366,652 (Procter & Gamble); Hollingsworth et al, European Patent Application 351,937 (Unilever); and Swatling et al, U.S. Patent No. 5,205,958. The following references are directed to inorganic double salts: Evans et al, U.S. Patent No. 4,820,441 (Lever); Evans et al, U.S. Patent No. 4,818,424 (Lever); and Atkinson et al, U.S. Patent No. 4,900,466 (Lever). SUMMARY OF THE INVENTION The present invention meets the aforementioned needs in the art by providing a process which produces a low density (below about 500 g/1) detergent composition from a surfactant paste or precursor thereof, adjunct detergent ingredients and spray dried granules containing an inorganic double salt and a minor amount of a surfactant. The process incorporates an agglomeration process which unexpectedly produces a low density rather than high density agglomerates. As used herein, the term "agglomerates" refers to particles formed by agglomerating detergent granules or particles which typically have a smaller mean particle size than the formed agglomerates. As used herein, the phrase "a minor amount of a surfactant" means an amount sufficient to aid in lowering the density of the resulting spray dried granules formed in the process, which, will be typically on the order of from about 0.1% to about 15%, more preferably from about 6% to about 10%, by weight of the total amount of materials spray dried. As used herein, the phrase "dry detergent material" means detergent materials generally in powdered, granular, flaked, or agglomerated form which are substantially devoid of liquids or moisture (i.e., less than 5% by weight). All percentages used herein are expressed as "percent-by-weight" unless indicated otherwise. All documents, including patents and publications cited herein, are incorporated herein by reference. All viscosities described herein are measured at 70°C and at shear rates between about 10 to 50 sec-1, preferably at 25 sec'l. In accordance with one aspect of the invention, a process for preparing low density detergent agglomerates is provided. The process comprises the steps of: (a) spray drying an aqueous mixture of sodium sulfate, sodium carbonate and a minor amount of a surfactant so as to form spray dried granules containing an inorganic double salt of the sodium carbonate and the sodium sulfate and the minor amount of the surfactant; (b) agglomerating the spray dried granules with a detergent surfactant paste and adjunct dry detergent material in a high speed mixer to obtain detergent agglomerates, wherein the adjunct dry detergent material includes an adjunct sodium carbonate material; and (c) drying the detergent agglomerates so as to form the detergent composition having a density of below about 500 g/1. In accordance with another aspect of the invention, another process for preparing low density detergent agglomerates is provided. The process comprises the steps of: (a) spray drying an aqueous mixture of sodium sulfate, sodium carbonate and a minor amount of a surfactant so as to form spray dried granules containing an inorganic double salt of the sodium carbonate and the sodium sulfate and the minor amount of the surfactant; (b) agglomerating a liquid acid precursor of anionic surfactant, the spray dried granules-and adjunct dry detergent material in a high speed mixer to obtain detergent agglomerates, wherein the adjunct dry detergent material includes an adjunct sodium carbonate material; and (c) cooling the detergent agglomerates so as to form the detergent composition having a density of below about 500 g/1. In accordance with yet another aspect of the invention, another process for preparing a low density detergent composition is provided. This process comprises the steps of: (a) spray drying an aqueous mixture of sodium sulfate, sodium carbonate and a minor amount of a C12-15 alkyl ethoxylated sulfate surfactant having an average degree of ethoxylation of about 3 so as to form spray dried granules containing an inorganic double salt having the formula Na2SO4•Na2CO3 and the minor amount of the alkyl ethoxylated sulfate surfactant; (b) agglomerating the spray dried granules with a detergent surfactant paste or precursor thereof and adjunct detergent material initially in a high speed mixer and subsequently in a moderate speed mixer to obtain detergent agglomerates, wherein the adjunct detergent material includes an adjunct sodium carbonate material; and (c) drying or cooling the detergent agglomerates so as to form the detergent composition having a density of below about 500 g/1. Accordingly, it is an object of the invention to provide a process for continuously producing a low density detergent composition directly from starting detergent ingredients. It is also an object of the invention to provide a process which is more efficient, flexible and economical to facilitate large-scale production of detergents of low as well as high dosage levels. These and other objects, features and attendant advantages of the present invention will become apparent to those skilled in the art from a reading of the following detailed description of the preferred embodiment and the appended claims. DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENT The present invention is directed to a process which produces free flowing, low density detergent agglomerates having a density of less than about 500 g/1, most preferably from about 300 g/l to about 480 g/1. The process produces low density detergent, agglomerates from a highly viscous surfactant paste or a liquid acid precursor of anionic surfactant which is then neutralized with the sodium carbonate used as an adjunct dry detergent ingredients during the agglomeration step. Generally speaking, the present process is used in the production of normal as opposed to low dosage detergents whereby the resulting detergent agglomerates can be used as a detergent or as a detergent additive. It should be understood that the process described herein can be continuous or batch depending upon the desired application. Process In the first step of the process, an aqueous mixture of sodium sulfate, sodium carbonate and a minor amount of a surfactant are spray dried so as to form spray dried granules containing an inorganic double salt of the sodium carbonate and the sodium sulfate and a surfactant. This step may be performed in any known spray drying apparatus including conventional spray drying towers of varying height and size depending upon the desired production capacity. As mentioned previously, the minor amount of surfactant will be on the order of from about 0.1% to about 15%, and most preferably from about 6% to about 10%, by weight of the total aqueous mixture prior to spray drying. Generally speaking, the surfactant is preferably selected from anionic, nonionic, zwitterionic, ampholytic and cationic classes and compatible mixtures thereof. Detergent surfactants useful herein are described in KS Palent 3,664.961, Morris, issued May 23, 1972, and in U.S. Patent 3,919,678, Laughlin et al., issued December 30, 1975, both of which are incorporated herein by reference. Useful cationic surfactants also include those described in U.S. Patent 4,222,905, Cockrell, issued September 16, 1980, and in U.S. Patent 4,239,659, Murphy, issued December 16, 1980, both of which are also incorporated herein by reference. Of the surfactants, anionics, cationics, zwitterionics and nonionics are preferred and anionics are most preferred. Nonlimiting examples of the preferred anionic surfactants useful include the conventional C11-C18 alkyl benzene sulfonates ("LAS"), primary, branched-chain and random CiQ-C20 alkyl sulfates ("AS"), the C10-C18 secondary (2,3) alkyl sulfates of the formula CH3(CH2)X(CHOSO3"M+) CH3 and CH3 (CH2)y(CHOSO3"M+) CH2CH3 where x and (y + 1) are integers of at least about 7, preferably at least about 9, and M is a water-solubilizing cation, especially sodium, unsaturated sulfates such as oleyl sulfate, and the C10-C18 alkyl alkoxy sulfates ("AEXS"; especially EO 1-5 ethoxy sulfates). Other exemplary surfactants useful in the invention include and C10-C18 alkyl alkoxy carboxylates (especially the EO 1-5 ethoxycarboxylates), the C10-18 glycerol ethers, the C10-C18 alkyl polyglycosides and their corresponding sulfated polyglycosides, and Cj2-Cjg alpha-sulfonated fatty acid esters. If desired, the conventional nonionic and amphoteric surfactants such as the C12-C18 alkyl ethoxylates ("AE") includingjhe so-called narrow peaked alkyl ethoxylates and C6-C12 alkyl phenol alkoxylates (especially ethoxylates and mixed ethoxy/propoxy), C12-C18 betaines and sulfobetaines ("sultaines"), C10-C18 amine oxides, and the like, can also be included in the overall compositions. The C10-C18 N-alkyl polyhydroxy fatty acid amides can also be used. Typical examples include the C12-C18 N-methylglucamides. See WO 9,206,154. Other sugar-derived surfactants include the N-alkoxy polyhydroxy fatty acid amides, such as C10-C18 N-(3-methoxypropyl) glucamide. The N-propyl through N-hexyl C12-C18 glucamides can be used for low sudsing. C10-C20 conventional soaps may also be used. If high sudsing is desired, the branched-chain C10-C16 soaps may be used. Mixtures of anionic and nonionic surfactants are especially useful. Other conventional useful surfactants are listed in standard texts. While any of the aforementioned specific surfactants can be used in the present process, it has been found that C10-15 alkyl ethoxylated sulfate surfactant having an average degree of ethoxylation per mole of from about 1 to about 5 is preferred with C12-15 alkyl ethoxylated sulfate surfactant having an ethoxylation of 3 is most preferred. While not intending to be bound by theory, it is believed that this minor amount of surfactant unexpectedly leads to the formation of lower density spray dried granules containing the inorganic double salt of sodium carbonate and sodium sulfate. As a consequence of the formation of unexpectedly lower dense spray dried granules, the ultimate density of the agglomerates is lower. By varying the exact amount of surfactant used in the aqueous mixture to be spray dried, the ultimate density of the agglomerates in the overall process can be controlled, thereby providing an effective lever to control the desired density. This certainly is cost advantageous in that the process can be more easily controlled to produce agglomerates within the desired density range, thereby minimizing the need for excessive recycling. In the second step of the process, the spray dried granules, a surfactant paste or precursor thereof and adjunct dry detergent materials preferably including an adjunct sodium carbonate material are fed into a high speed mixer for agglomeration. To achieve the desired density of less than about 500 g/1, the agglomeration step is carried forth in a high speed mixer after which an optional moderate speed mixer may be used for further agglomeration, if necessary. Preferably, the inorganic double salt in the granules is substantially anhydrous and has the formula Na2SO4•Na2CO3 (Burkeite), although other inorganic salts as noted below may be used. The weight ratio of Na2SO4 to Na2CO3 in Burkeite is preferably about 70:30, but a ratio of about 30:70 can be used without departing from the scope of the invention. While the inorganic salts listed herein are suitable for use in the instant process, other salts which have not been listed can be used. The preferred input weight ratio of the spray dried granules to adjunct dry detergent ingredients is from about 1:10 to about 10:1, more preferably from about 1:5 to about 5:1, and most preferably from about 1:2 to about 3:1. The nature and composition of the adjunct detergent materials can vary as described in detail hereinafter. Preferably, the median residence time of the starting detergent materials in the high speed mixer (e.g. Lodige Recycler CB 30 or other similar equipment) is from about 2 to 45 seconds while the residence time in low or moderate speed mixer (e.g. Lodige Recycler KM 600 "Ploughshare" or other similar equipment), if used, is from about 0.5 to 15 minutes. A highly viscous surfactant paste or a liquid acid precursor of anionic surfactant is also inputted into the high speed mixer as mentioned, the components of which are described more fully hereinafter. For purposes of facilitating the production of low density or "fluffy" detergent agglomerates, the adjunct detergent material includes sodium carbonate which, in combination with the inorganic double salt and surfactant in the granules, have been surprisingly found to lower the density of the agglomerates produced in the process. While not intending to be bound by theory, it is believed that the inorganic double salt in the granules and the adjunct sodium carbonate if combined in an optimally selected weight ratio enhances the "fluffing" of the agglomerates as they are produced in the instant process. This leads to the production of agglomerates having even lower densities. To that end, the instant process preferably entails mixing from about 1% to about 60%, more preferably from about 20% to about 45% of the spray dried granules containing the inorganic double salt, and from about 0.1% to about 50%, more preferably of 5% to about 10% of sodium carbonate, both of which are contained in the aforementioned weight ratio range. The other essential step in the process involves conditioning the agglomerates by drying and/or cooling the agglomerates exiting the high speed mixer or the moderate speed mixer if it is optionally used. This can be completed in a wide variety of apparatus including but not limited to fluid bed dryers. The drying and/or cooling steps enhance the free flowability of the agglomerates and continues the "fluffing" or "puffing" physical characteristic formation of the resulting agglomerates. While not intending to be bound by theory, it is believed that during the agglomeration step of the instant process, the inorganic double salt becomes embodied in the agglomerates and "puffs" the agglomerates into a fluffy, light, low density agglomerate particle. The inorganic double salt, such as Na2SO4•Na2CO3 (Burkeite), is preferably a high void volume, high integrity carrier particle that can absorb the surfactant while maintaining its shell-forming properties. The detergent agglomerates produced by the process preferably have a surfactant level of from about 10% to about 30%, more preferably from about 15% to about 25% and, most preferably from about 20% to about 25%. The particle porosity of the resulting detergent agglomerates produced according to the process of the invention has relatively high porosity which unexpectedly results in a low density detergent compos4tion in the form of low density agglomerates. In addition, an attribute of a particulate detergent composition is its relative particle size. The present process typically provides detergent agglomerates having a median particle size of from about 250 microns to about 1000 microns, and more preferably from about 400 microns to about 600 microns. As used herein, the phrase "mean particle size" refers to individual agglomerates and not individual particles or ingredients in the agglomerates. The combination of the above-referenced porosity and particle size results in agglomerates having density values of less than 500 g/1. Such a feature is especially useful in the production of laundry detergents having varying dosage levels as well as other granular compositions such as dishwashing compositions. Optional Process Steps In an optional step of the present process, the detergent agglomerates exiting the drying and/or cooling steps are further conditioned by additional cooling or drying in similar apparatus as are well known in the art. Another optional process step involves adding a coating agent to improve flowability and/or minimize over agglomeration of the detergent composition in one or more of the following locations of the instant process: (1) the coating agent can be added directly after the fluid bed cooler or dryer; (2) the coating agent may be added between the fluid bed dryer and the fluid bed cooler; (3) the coating agent may be added between the fluid bed dryer and the optional moderate speed mixer; and/or (4) the coating agent may be added directly to the optional moderate speed mixer and the fluid bed dryer. The coating agent is preferably selected from the group consisting of aluminosilicates, silicates, carbonates and mixtures thereof. The coating agent not only enhances the free flowability of the resulting detergent composition which is desirable by consumers in that it permits easy scooping of detergent during use, but also serves to control agglomeration by preventing or minimizing over agglomeration, especially when added directly to the moderate speed mixer. As those skilled in the art are well aware, over agglomeration can lead to very undesirable flow properties and aesthetics of the final detergent product. Optionally, the process can comprise the step of spraying an additional binder in one or both of the mixers or fluid bed dryers. A binder is added for purposes of enhancing agglomeration by providing a "binding" or "sticking" agent for the detergent components. The binder is preferably selected from the group consisting of water, anionic surfactants, nonionic surfactants, polyethylene glycol, polyvinyl pyrrolidone polyacrylates, citric acid and mixtures thereof. Other suitable binder materials including those listed herein are described in Beerse et al, U.S. Patent No. 5,108,646 (Procter & Gamble Co.), the disclosure of which is incorporated herein by reference. Other optional steps contemplated by the present process include screening the oversized detergent agglomerates in a screening apparatus which can take a variety of forms including but not limited to conventional screens chosen for the desired particle size of the finished detergent product. Other optional steps include conditioning of the detergent agglomerates by subjecting the agglomerates to additional drying by way of apparatus discussed previously. Another optional step of the instant process entails finishing the resiling detergent agglomerates by a variety of processes including spraying and/or admixing other conventional detergent ingredients. For example, the finishing step encompasses spraying perfumes, brighteners and enzymes onto the finished agglomerates to provide a more complete detergent composition. Such techniques and ingredients are well known in the art. Detergent Surfactant Paste The detergent surfactant paste used in the process is preferably in the form of an aqueous viscous paste, although other forms are also contemplated by the invention. This so-called viscous surfactant paste has a viscosity of from about 5,000 cps to about 100,000 cps, more preferably from about 10,000 cps to about 80,000 cps, and contains at least about 10% water, more typically at least about 30% water. The viscosity is measured at 70°C and at shear rates of about 10 to 100 sec.'l. Furthermore, the surfactant paste, if used, preferably comprises a detersive surfactant in the amounts specified previously and the balance water and other conventional detergent ingredients. In an alternative embodiment of the process invention, the liquid acid precursor of anionic surfactant is used during the agglomeration step. This liquid acid precursor will typically have a viscosity of from about 500 cps to about 100,000 cps. The liquid acid is a precursor for the anionic surfactants described in detail previously. Adjunct Detergent Material The adjunct detergent materials used in the present process preferably comprises the sodium carbonate as mentioned earlier, especially when the liquid acid precursor is used as a neutralizing agent in the agglomeration step. The adjunct detergent material may also include a detergent aluminosilicate builder which are referenced as aluminosilicate ion exchange materials and sodium carbonate. The aluminosilicate ion exchange materials used herein as a detergent builder preferably have both a high calcium ion exchange capacity and a high exchange rate. Without intending to be limited by theory, it is believed that such high calcium ion exchange rate and capacity are a function of several interrelated factors which derive from the method by which the aluminosilicate ion exchange material is produced. In that regard, the aluminosilicate ion exchange materials used herein are preferably produced in accordance with Corkill et al, U.S. Patent No. 4,605,509 (Procter & Gamble), the disclosure of which is incorporated herein by reference. Preferably, the aluminosilicate ion exchange material is in "sodium" form since the potassium and hydrogen forms of the instant aluminosilicate do not exhibit the as high of an exchange rate and capacity as provided by the sodium form. Additionally, the aluminosilicate ion exchange material preferably is in over dried form so as to facilitate production of crisp detergent agglomerates as described herein. The aluminosilicate ion exchange materials used herein preferably have particle size diameters which optimize their effectiveness as detergent builders. The term "particle size diameter" as used herein represents the average particle size diameter of a given aluminosilicate ion exchange material as determined by conventional analytical techniques, such as microscopic determination and scanning electron microscope (SEM). The preferred particle size diameter of the aluminosilicate is from about 0.1 micron to about 10 microns, more preferably from about 0.5 microns to about 9 microns. Most preferably, the particle.size diameter is from about 1 microns to about 8 microns. Preferably, the aluminosilicate ion exchange material has the formula (Formula Removed) wherein z and y are integers of at least 6, the molar ratio of z to y is from about 1 to about 5 and x is from about 10 to about 264. More preferably, the aluminosilicate has the formula (Formula Removed) wherein x is from about 20 to about 30, preferably about 27. These preferred aluminosilicates are available commercially, for example under designations Zeolite A, Zeolite B, Zeolite P, Zeolite MAP and Zeolite X. Alternatively, naturally-occurring or synthetically derived aluminosilicate ion exchange materials suitable for use herein can be made as described in Krummel et al, U.S. Patent No. 3,985,669, the disclosure of which is incorporated herein by reference. The aluminosilicates used herein are further characterized by their ion exchange capacity which is at least about 200 mg equivalent of CaCO3 hardness/gram, calculated on an anhydrous basis, and which is preferably in a range from about 300 to 352 mg equivalent of CaCO3 hardness/gram. Additionally, the instant aluminosilicate ion exchange materials are still further characterized by their calcium ion exchange rate which is at least about 2 grains Ca++/gallon/minute/-gram/gallon, and more preferably in a range from about 2 grains Ca++/gallon/minute/-gram/gallon to about 6 grains Ca++/gallon/minute/-gram/gallon . Additional adjunct materials include bleaches, bleach activators, suds boosters or suds suppressors, anti-tarnish and anticorrosion agents, soil suspending agents, soil release agents, germicides, pH adjusting agents, non-builder alkalinity sources, chelating agents, smectite clays, enzymes, enzyme-stabilizing agents and perfumes. See U.S. Patent 3,936,537, issued February 3, 1976 to Baskerville, Jr. et al., incorporated herein by reference. Other builders can be generally selected from the various water-soluble, alkali metal, ammonium or substituted ammonium phosphates, polyphosphates, phosphonates, polyphosphonates, carbonates, borates, polyhydroxy sulfonates, polyacetate_s, carboxylates, and polycarboxylates. Preferred are the alkali metal, especially sodium, salts of the above. Preferred for use herein are the phosphates, carbonates, C10-18 fatty acids, polycarboxylates, and mixtures thereof. More preferred are sodium tripolyphosphate, tetrasodium pyrophosphate, citrate, tartrate mono- and di-succinates, and mixtures thereof (see below). In comparison with amorphous sodium silicates, crystalline layered sodium silicates exhibit a clearly increased calcium and magnesium ion exchange capacity. .In addition, the layered sodium silicates prefer magnesium ions over calcium ions, a feature necessary to insure that substantially all of the "hardness" is removed from the wash water. These crystalline layered sodium silicates, however, are generally more expensive than amorphous silicates as well as other builders. Accordingly, in order to provide an economically feasible laundry detergent, the proportion of crystalline layered sodium silicates used must be determined judiciously. The crystalline layered sodium silicates suitable for use herein preferably have the formula wherein M is sodium or hydrogen, x is from about 1 .9 to about 4 and y is from about 0 to about 20. More preferably, the crystalline layered sodium silicate has the formula (Formula Removed) wherein M is sodium or hydrogen, and y is from about 0 to about 20. These and other crystalline layered sodium silicates are discussed in Corkill et al, U.S. Patent No. 4,605,509, previously incorporated herein by reference. Specific examples of inorganic phosphate builders are sodium and potassium tripolyphosphate, pyrophosphate, polymeric metaphosphate having a degree of polymerization of from about 6 to 21, and orthophosphates. Examples of polyphosphonate builders are the sodium and potassium salts of ethylene diphosphonic acid, the sodium and potassium salts of ethane 1-hydroxy-l, 1 -diphosphonic acid and the sodium and potassium salts of ethane, 1 , 1 ,2-triphosphonic acid. Other phosphorus builder compounds are disclosed in U.S. Patents 3,159,581; 3,213,030; 3,422,021; 3,422,137; 3,400,176 and 3,400,148, all of which are incorporated herein by reference. Examples of nonphosphorus, inorganic builders are tetraborate decahydrate and silicates having a weight ratio of SiO- to alkali metal oxide'of from about 0.5 to about 4.0, preferably from about 1.0 to about 2.4. Water-soluble, nonphosphorus organic builders useful herein include the various alkali metal, ammonium and substituted ammonium polyacetates, carboxylates, polycarboxylar.es and polyhydroxy sulfonates. Examples of polyacetate and polycarboxylate builders are the sodium, potassium, lithium, ammonium and substituted ammonium salts of ethylene diamine tetraacetic acid, nitrilotriacetic acid, oxydisuccinic acid, mellitic acid, benzene polycarboxylic acids, and citric acid. Polymeric polycarboxylate builders are set forth in U.S. Patent 3,308,067, Diehl, issued March 7, 1967, the disclosure of which is incorporated herein by reference. Such materials include the water-soluble salts of homo- and copolymers of aliphatic carboxylic acids such as maleic acid, itaconic acid, mesaconic acid, fumaric acid, aconitic acid, citraconic acid and methylene malonic acid. Some of these materials are useful as the water-soluble anionic polymer as hereinafter described, but only if in intimate admixture with the non-soap anionic surfactant. Other suitable polycarboxylates for use herein are the polyacetal carboxylates described in U.S. Patent 4,144,226, issued March 13, 1979 to Crutchfield et al, and U.S. Patent 4,246,495, issued March 27, 1979 to Crutchfield et al, both of which are incorporated herein by reference. These polyacetal carboxylates can be prepared by bringing together under polymerization conditions an ester of glyoxylic acid and a polymerization initiator. The resulting polyacetal carboxylate ester is then attached to chemically stable end groups to stabilize the polyacetal carboxylate against rapid depolymerization in alkaline solution, converted to the corresponding salt, and added to a detergent composition. Particularly preferred polycarboxylate builders are the ether carboxylate builder compositions comprising a combination of tartrate monosuccinate and tartrate disuccinate described in U.S. Patent 4,663,071, Bush et al., issued May 5, 1987, the disclosure of which is incorporated herein by reference. Bleaching agents and activators are described in U.S. Patent 4,412,934, Chung et al., issued November 1, 1983, and in U.S. Patent 4,483,781, Hartman, issued November 20, 1984, both of which are incorporated herein by reference. Chelating agents are also described in U.S. Patent 4,663,071, Bush et al., from Column 17, line 54 through Column 18, line 68, incorporated herein by reference. Suds modifiers are also optional ingredients and are described in U.S. Patents 3,933,672, issued January 20, 1976 to Bartoletta et al., and 4,136,045, issued January 23, 1979 to Gault et al., both incorporated herein by reference. Suitable smectite clays for use herein are described in U.S. Patent 4,762,645, Tucker et al, issued August 9, 1988, Column 6, line 3 through Column 7, line 24, incorporated herein by reference. Suitable additional detergency builders for use herein are enumerated in the Baskerville patent, Column 13, line 54 through Column 16, line 16, and in U.S. Patent 4,663,071, Bush et al, issued May 5, 1987, both incorporated herein by reference. In order to make the present invention more readily understood, reference is made to the following examples, which are intended to be illustrative only and not intended to be limiting in scope. EXAMPLES A - B This Example illustrates a batch mode of the instant process. A low density agglomerated detergent composition is prepared using a lab tilt-a-pin (available from Processall, Inc.) mixer. The spray dried granules are made in a Niro spray dryer by spraying a 25% by weight aqueous solution of Na2SO4•Na2CO3 ("Burkeite") and C12-15 alkyl ethoxylated (EO = 3) sulfate surfactant ("AE3S") (wt. ratio 63/27/10) in the spray dryer where the inlet air is 250 °C. The spray dried granules have a bulk density of 154 g/1 and a median particle size of 27 microns. The lab mixer is first charged with a mixture of powders, namely sodium carbonate (median particle size 5-40 microns made via Air Classifier Mill available from Hosokawa Powder Systems), light density, granular sodium tripolyphosphate (supplied by FMC Corp. and referenced as "STPP")), zeolite type A (supplied by Ethyl Corp. and noted below as "Zeolite A") and the spray dried granules containing the inorganic double salt Burkeite and AE3S. During the agglomeration process, the liquid acid precursor of sodium alkylbenzene sulfonate (C12H25-C6H4-SO3-H or "HLAS" as noted below) is then added on top of the powder mixture while the mixer was being operated for 15 seconds at 700 rpm until discrete agglomerates are formed in the mixer. It has been found that these conditions result in agglomerates unexpectedly acceptable for use in dry laundry detergent products. The composition of the agglomerates are given below in Table I. TABLE I (Table Removed) Unexpectedly, the resulting agglomerates have a bulk density below 500 g/L and show excellent cake strength and flowability. COMPARATIVE EXAMPLES C-E These Examples describe compositions made by the process described in the Examples A-B with the exception that no surfactant (e.g. AE3S) is included in the spray dried granules and either sodium carbonate or the inorganic double salt ( Burkeite) is omitted. The following compositions are made as shown in Table II. TABLE II (Table Removed) The bulk density of the resulting agglomerates considerably higher than 500 g/1, sticky and not free-flowing as a result of the exclusion of sodium carbonate or granules containing Burkeite and surfactant. Thus, this process produces compositions C-E which are outside the scope of the instant process invention. COMPARATIVE EXAMPLES F-G The compositions in these Examples are made by the batch mode process described in Examples A-B but do not contain Burkeite. Rather the compositions contain separate amounts of spray-dried sodium sulfate and spray-dried sodium carbonate. The compositions are shown in Table III. TABLE III (Table Removed) Comparative Example F did not form acceptable agglomerates having the desired low density. While comparative Example G has a low density, the resulting agglomerates are sticky and not free-flowing. EXAMPLE H-I These Examples illustrate a batch mode of the instant process. A low density agglomerated detergent composition is prepared using a Braun® Type 4262 (available from the Braun Company) food processor. Initially, spray dried granules containing the inorganic double salt (Na2SO4•Na2CO3 or Burkeite) and C12-15 alkyl ethoxylated (EO = 3) sulfate surfactant ("AE3S") are prepared in a large scale 10 foot tower operated at an inlet air temperature of 288 °C and a liquid feed temperature of 80 °C. A 25% by weight aqueous solution of Na2SO4'Na2CO3 and AE3S (wt. ratio 63/27/10) is spray.dried in the 10 foot spray drying tower. The spray dried granules exiting from the spray drying tower have a bulk density of 455 g/1 and a median particle size of 90 microns. The Braun® Type 4262 mixer is first charged with a mixture of powders, namely sodium carbonate (mean particle size 5-40 microns made via Air Classifier Mill), light density granular or high density powder sodium tripolyphosphate (both supplied by FMC Corp. and referenced as "STPP"), zeolite type A (supplied by Ethyl Corp. and noted as below as "Zeolite A") and spray dried granules containing the inorganic double salt ("Burkeite") and ("AE3S"). During the agglomeration process, the liquid acid precursor of sodium alkylbenzene sulfonate (C12H25-C6H4-SO3-H or "HLAS" as noted below) is then added on top of the powder mixture while the mixer is operated until discrete agglomerates are formed in the mixer. The composition of the agglomerates is given below in Table IV. TABLE IV (Table Removed) Unexpectedly, the resulting agglomerates have a bulk density below 500 g/L and show good cake strength and flowability. COMPARATIVE EXAMPLES J-K The compositions in these Examples are made by the batch mode process described in Examples H-I but do not contain granules containing Burkeite and AE3S. The composition of the agglomerates is given below in Table V. TABLE V (Table Removed) The resulting agglomerates of comparative Examples J and K. do not have the desired low density. Having thus described the invention in detail, it will be clear to those skilled in the art that various changes may be made without departing from the scope of the invention and the invention is not to be considered limited to what is described in the specification. WE CLAIM: 1. A process for preparing a low density detergent composition which comprises the steps of: (a) spray drying an aqueous mixture of sodium sulfate, sodium carbonate and from 0.1% to 15% by weight of a surfactant so as to form spray dried granules containing an inorganic double salt of said sodium carbonate and said sodium sulfate and said minor amount of said surfactant; (b) agglomerating said spray dried granules with a detergent surfactant paste or its precursor and adjunct dry detergent material in the ratio of the spray dried granules to adjunct dry detergent ingredients from 1:10 to 10:1 in a high speed mixer to obtain detergent agglomerates, wherein said adjunct dry detergent material includes an adjunct sodium carbonate material; and (c) drying said detergent agglomerates so as to form said detergent composition having a density of below 500 g/1. 2. A process as claimed in claim 1, wherein said adjunct dry material is a builder selected from the group consisting of aluminosilicates, crystalline layered silicates, phosphates, and mixtures thereof. 3. A process as claimed in any of the preceding claims, wherein said inorganic double salt has the formula Na2 SO4 •Na2CO3 in a weight ratio of Na2 SO4 to Na2 CO3 of 70:30. 4. A process as claimed in any of the preceding claims wherein the median residence time of said detergent agglomerates in said high speed mixer is in range from 2 seconds to 45 seconds. 5. A process as claimed in any of the preceding claims the steps of agglomerating said detergent agglomerates in a moderate speed mixer following said high speed mixer. 6. A process as claimed in claim 5 wherein the median residence time said detergent agglomerates in said moderate speed mixer is in range from 0.5 minutes to 15 minutes. 7. A process as claimed in any of the preceding claims wherein said surfactant is a C12-15 alkyl ethoxylated sulfate having an average degree of ethoxylation of from 1 to 5. 8. A process as claimed in any of the preceding claims wherein said weight ratio of said spray dried granules to said adjunct sodium carbonate is from 1:5 to 5:1. 9. A process for preparing a low density detergent composition as claimed in any of the preceding claims wherein the surfactant employed in step (a) is a C-12-15 alkyl ethoxylated sulfate surfactant having an average degree of ethoxylation of 3. 10. A process for preparing a low density detergent composition substantially as hereinbefore described in any of the Examples.

Full Text

FIELD OF THE INVENTION
The present invention generally relates to a process for producing a low density detergent composition. More particularly, the invention is directed to a process during which low density detergent agglomerates are produced by agglomerating a surfactant paste or liquid acid precursor of anionic surfactant with spray dried granules containing an inorganic double salt of sodium carbonate and sodium sulfate and a surfactant. The process produces a free flowing, low density detergent composition which can be commercially sold as a conventional non-compact detergent composition or used as an admix in a low dosage, "compact" detergent product.
BACKGROUND OF THE INVENTION
Recently, there has been considerable interest within the detergent industry for laundry detergents which are "compact" and therefore, have low dosage volumes. To facilitate production of these so-called low dosage detergents, many attempts have been made to produce high bulk density detergents, for example with a density of 600 g/1 or higher. The low dosage detergents are currently in high demand as they conserve resources and can be sold in small packages which are more convenient for consumers. However, the extent to which modern detergent products need to be "compact" in nature remains unsettled. In fact, many consumers, especially in developing countries, continue to prefer a higher dosage levels in their respective laundering operations. Consequently, there is a need in the art of producing modern detergent compositions for flexibility in the ultimate density of the final composition.
Generally, there are two primary types of processes by which detergent granules or powders can be prepared. The first type of process involves spray-drying an aqueous detergent slurry in a spray-drying tower to produce highly porous detergent granules. In the second type of process, the various detergent components are dry mixed after which they are agglomerated with a binder such as a nonionic or anionic surfactant. In both processes, the most important factors which govern the density of the resulting detergent granules are the density, porosity and surface area, shape of the various starting materials and their respective chemical composition. These parameters, however, can only be varied
within a limited range. Thus, flexibility in the substantial bulk density can only be achieved by additional processing steps which lead to lower density of the detergent granules.
There have been many attempts in the art for providing processes which increase the density of detergent granules or powders. Particular attention has been .given to densification of spray-dried granules by post tower treatment. For example, one attempt involves a batch process in which spray-dried or granulated detergent powders containing sodium tripolyphosphate and sodium sulfate are densified and spheronized in a Marumerizer®. This apparatus comprises a substantially horizontal, roughened, rotatable table positioned within and at the base of a substantially vertical, smooth walled cylinder. This process, however, is essentially a batch process and is therefore less suitable for the large scale production of detergent powders. More recently, other attempts have been made to provide continuous processes for increasing the density of "post-tower" or spray dried detergent granules. Typically, such processes require a first apparatus which pulverizes or grinds the granules and a second apparatus which increases the density of the pulverized granules by agglomeration. While these processes achieve the desired increase in density by treating or densifying "post tower" or spray dried granules, they do not provide a process which has the flexibility of providing lower density granules.
Moreover, all of the aforementioned processes are directed primarily for densifying or otherwise processing spray dried granules. Currently, the relative amounts and types of materials subjected to spray drying processes in the production of detergent granules has been limited. For example, it has been difficult to attain high levels of surfactant in the resulting detergent composition, a feature which facilitates production of detergents in a more efficient manner. Thus, it would be desirable to have a process by which detergent compositions can be produced without having the limitations imposed by conventional spray drying techniques.
To that end, the art is also replete with disclosures of processes which entail agglomerating detergent compositions. For example, attempts have been made to agglomerate detergent builders by mixing zeolite and/or layered silicates in a mixer to form free flowing agglomerates. While such attempts suggest that their process can be used to produce detergent agglomerates, they do not provide a mechanism by which starting detergent materials in the form of pastes, liquids and/or dry materials can be effectively agglomerated into crisp, free flowing detergent agglomerates having low densities (i.e. less than 500 g/1) rather than higher densities.
Accordingly, there remains a need in the art to have a process for continuously producing a low density detergent composition directly from starting detergent ingredients. Also, there remains a need for such a process which is more efficient, flexible and
economical to facilitate large-scale production of detergents of low as well as high dosage levels.
BACKGROUND ART
The following references are directed to densifying spray-dried granules: Appel et al, U.S. Patent No. 5,133,924 (Lever); Bortolotti et al,U.S. Patent No. 5,160,65,7 (Lever); Johnson et al, British patent No. 1,517,713 (Unilever); and Curtis, European Patent Application 451,894. The following references are directed to producing detergents by agglomeration: Beerse et al, U.S. Patent No. 5,108,646 (Procter & Gamble); Capeci et al, tl.S. Patent No. 5,366,652 (Procter & Gamble); Hollingsworth et al, European Patent Application 351,937 (Unilever); and Swatling et al, U.S. Patent No. 5,205,958. The following references are directed to inorganic double salts: Evans et al, U.S. Patent No. 4,820,441 (Lever); Evans et al, U.S. Patent No. 4,818,424 (Lever); and Atkinson et al, U.S. Patent No. 4,900,466 (Lever).
SUMMARY OF THE INVENTION
The present invention meets the aforementioned needs in the art by providing a process which produces a low density (below about 500 g/1) detergent composition from a surfactant paste or precursor thereof, adjunct detergent ingredients and spray dried granules containing an inorganic double salt and a minor amount of a surfactant. The process incorporates an agglomeration process which unexpectedly produces a low density rather than high density agglomerates.
As used herein, the term "agglomerates" refers to particles formed by agglomerating detergent granules or particles which typically have a smaller mean particle size than the formed agglomerates. As used herein, the phrase "a minor amount of a surfactant" means an amount sufficient to aid in lowering the density of the resulting spray dried granules formed in the process, which, will be typically on the order of from about 0.1% to about 15%, more preferably from about 6% to about 10%, by weight of the total amount of materials spray dried. As used herein, the phrase "dry detergent material" means detergent materials generally in powdered, granular, flaked, or agglomerated form which are substantially devoid of liquids or moisture (i.e., less than 5% by weight). All percentages used herein are expressed as "percent-by-weight" unless indicated otherwise. All documents, including patents and publications cited herein, are incorporated herein by reference. All viscosities described herein are measured at 70°C and at shear rates between about 10 to 50 sec-1, preferably at 25 sec'l.
In accordance with one aspect of the invention, a process for preparing low density detergent agglomerates is provided. The process comprises the steps of: (a) spray drying an aqueous mixture of sodium sulfate, sodium carbonate and a minor amount of a surfactant so as to form spray dried granules containing an inorganic double salt of the
sodium carbonate and the sodium sulfate and the minor amount of the surfactant; (b) agglomerating the spray dried granules with a detergent surfactant paste and adjunct dry detergent material in a high speed mixer to obtain detergent agglomerates, wherein the adjunct dry detergent material includes an adjunct sodium carbonate material; and (c) drying the detergent agglomerates so as to form the detergent composition having a density of below about 500 g/1.
In accordance with another aspect of the invention, another process for preparing low density detergent agglomerates is provided. The process comprises the steps of: (a) spray drying an aqueous mixture of sodium sulfate, sodium carbonate and a minor amount of a surfactant so as to form spray dried granules containing an inorganic double salt of the sodium carbonate and the sodium sulfate and the minor amount of the surfactant; (b) agglomerating a liquid acid precursor of anionic surfactant, the spray dried granules-and adjunct dry detergent material in a high speed mixer to obtain detergent agglomerates, wherein the adjunct dry detergent material includes an adjunct sodium carbonate material; and (c) cooling the detergent agglomerates so as to form the detergent composition having a density of below about 500 g/1.
In accordance with yet another aspect of the invention, another process for preparing a low density detergent composition is provided. This process comprises the steps of: (a) spray drying an aqueous mixture of sodium sulfate, sodium carbonate and a minor amount of a C12-15 alkyl ethoxylated sulfate surfactant having an average degree of ethoxylation of about 3 so as to form spray dried granules containing an inorganic double salt having the formula Na2SO4•Na2CO3 and the minor amount of the alkyl ethoxylated sulfate surfactant; (b) agglomerating the spray dried granules with a detergent surfactant paste or precursor thereof and adjunct detergent material initially in a high speed mixer and subsequently in a moderate speed mixer to obtain detergent agglomerates, wherein the adjunct detergent material includes an adjunct sodium carbonate material; and (c) drying or cooling the detergent agglomerates so as to form the detergent composition having a density of below about 500 g/1.
Accordingly, it is an object of the invention to provide a process for continuously producing a low density detergent composition directly from starting detergent ingredients. It is also an object of the invention to provide a process which is more efficient, flexible and economical to facilitate large-scale production of detergents of low as well as high dosage levels. These and other objects, features and attendant advantages of the present invention will become apparent to those skilled in the art from a reading of the following detailed description of the preferred embodiment and the appended claims.
DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENT
The present invention is directed to a process which produces free flowing, low density detergent agglomerates having a density of less than about 500 g/1, most preferably from about 300 g/l to about 480 g/1. The process produces low density detergent, agglomerates from a highly viscous surfactant paste or a liquid acid precursor of anionic surfactant which is then neutralized with the sodium carbonate used as an adjunct dry detergent ingredients during the agglomeration step. Generally speaking, the present process is used in the production of normal as opposed to low dosage detergents whereby the resulting detergent agglomerates can be used as a detergent or as a detergent additive. It should be understood that the process described herein can be continuous or batch depending upon the desired application.
Process
In the first step of the process, an aqueous mixture of sodium sulfate, sodium carbonate and a minor amount of a surfactant are spray dried so as to form spray dried granules containing an inorganic double salt of the sodium carbonate and the sodium sulfate and a surfactant. This step may be performed in any known spray drying apparatus including conventional spray drying towers of varying height and size depending upon the desired production capacity. As mentioned previously, the minor amount of surfactant will be on the order of from about 0.1% to about 15%, and most preferably from about 6% to about 10%, by weight of the total aqueous mixture prior to spray drying.
Generally speaking, the surfactant is preferably selected from anionic, nonionic, zwitterionic, ampholytic and cationic classes and compatible mixtures thereof. Detergent surfactants useful herein are described in KS Palent 3,664.961, Morris, issued May 23, 1972, and in U.S. Patent 3,919,678, Laughlin et al., issued December 30, 1975, both of which are incorporated herein by reference. Useful cationic surfactants also include those described in U.S. Patent 4,222,905, Cockrell, issued September 16, 1980, and in U.S. Patent 4,239,659, Murphy, issued December 16, 1980, both of which are also incorporated herein by reference. Of the surfactants, anionics, cationics, zwitterionics and nonionics are preferred and anionics are most preferred.
Nonlimiting examples of the preferred anionic surfactants useful include the conventional C11-C18 alkyl benzene sulfonates ("LAS"), primary, branched-chain and random CiQ-C20 alkyl sulfates ("AS"), the C10-C18 secondary (2,3) alkyl sulfates of the formula CH3(CH2)X(CHOSO3"M+) CH3 and CH3 (CH2)y(CHOSO3"M+) CH2CH3 where x and (y + 1) are integers of at least about 7, preferably at least about 9, and M is a water-solubilizing cation, especially sodium, unsaturated sulfates such as oleyl sulfate, and the C10-C18 alkyl alkoxy sulfates ("AEXS"; especially EO 1-5 ethoxy sulfates).
Other exemplary surfactants useful in the invention include and C10-C18 alkyl alkoxy carboxylates (especially the EO 1-5 ethoxycarboxylates), the C10-18 glycerol
ethers, the C10-C18 alkyl polyglycosides and their corresponding sulfated polyglycosides, and Cj2-Cjg alpha-sulfonated fatty acid esters. If desired, the conventional nonionic and amphoteric surfactants such as the C12-C18 alkyl ethoxylates ("AE") includingjhe so-called narrow peaked alkyl ethoxylates and C6-C12 alkyl phenol alkoxylates (especially ethoxylates and mixed ethoxy/propoxy), C12-C18 betaines and sulfobetaines ("sultaines"), C10-C18 amine oxides, and the like, can also be included in the overall compositions.
The C10-C18 N-alkyl polyhydroxy fatty acid amides can also be used. Typical examples include the C12-C18 N-methylglucamides. See WO 9,206,154. Other sugar-derived surfactants include the N-alkoxy polyhydroxy fatty acid amides, such as C10-C18 N-(3-methoxypropyl) glucamide. The N-propyl through N-hexyl C12-C18 glucamides can be used for low sudsing. C10-C20 conventional soaps may also be used. If high sudsing is desired, the branched-chain C10-C16 soaps may be used. Mixtures of anionic and nonionic surfactants are especially useful. Other conventional useful surfactants are listed in standard texts.
While any of the aforementioned specific surfactants can be used in the present process, it has been found that C10-15 alkyl ethoxylated sulfate surfactant having an average degree of ethoxylation per mole of from about 1 to about 5 is preferred with C12-15 alkyl ethoxylated sulfate surfactant having an ethoxylation of 3 is most preferred.
While not intending to be bound by theory, it is believed that this minor amount of surfactant unexpectedly leads to the formation of lower density spray dried granules containing the inorganic double salt of sodium carbonate and sodium sulfate. As a consequence of the formation of unexpectedly lower dense spray dried granules, the ultimate density of the agglomerates is lower. By varying the exact amount of surfactant used in the aqueous mixture to be spray dried, the ultimate density of the agglomerates in the overall process can be controlled, thereby providing an effective lever to control the desired density. This certainly is cost advantageous in that the process can be more easily controlled to produce agglomerates within the desired density range, thereby minimizing the need for excessive recycling.
In the second step of the process, the spray dried granules, a surfactant paste or precursor thereof and adjunct dry detergent materials preferably including an adjunct sodium carbonate material are fed into a high speed mixer for agglomeration. To achieve the desired density of less than about 500 g/1, the agglomeration step is carried forth in a high speed mixer after which an optional moderate speed mixer may be used for further agglomeration, if necessary. Preferably, the inorganic double salt in the granules is substantially anhydrous and has the formula Na2SO4•Na2CO3 (Burkeite), although other inorganic salts as noted below may be used. The weight ratio of Na2SO4 to Na2CO3 in Burkeite is preferably about 70:30, but a ratio of about 30:70 can be used without departing
from the scope of the invention. While the inorganic salts listed herein are suitable for use in the instant process, other salts which have not been listed can be used. The preferred input weight ratio of the spray dried granules to adjunct dry detergent ingredients is from about 1:10 to about 10:1, more preferably from about 1:5 to about 5:1, and most preferably from about 1:2 to about 3:1.
The nature and composition of the adjunct detergent materials can vary as described in detail hereinafter. Preferably, the median residence time of the starting detergent materials in the high speed mixer (e.g. Lodige Recycler CB 30 or other similar equipment) is from about 2 to 45 seconds while the residence time in low or moderate speed mixer (e.g. Lodige Recycler KM 600 "Ploughshare" or other similar equipment), if used, is from about 0.5 to 15 minutes. A highly viscous surfactant paste or a liquid acid precursor of anionic surfactant is also inputted into the high speed mixer as mentioned, the components of which are described more fully hereinafter.
For purposes of facilitating the production of low density or "fluffy" detergent agglomerates, the adjunct detergent material includes sodium carbonate which, in combination with the inorganic double salt and surfactant in the granules, have been surprisingly found to lower the density of the agglomerates produced in the process. While not intending to be bound by theory, it is believed that the inorganic double salt in the granules and the adjunct sodium carbonate if combined in an optimally selected weight ratio enhances the "fluffing" of the agglomerates as they are produced in the instant process. This leads to the production of agglomerates having even lower densities. To that end, the instant process preferably entails mixing from about 1% to about 60%, more preferably from about 20% to about 45% of the spray dried granules containing the inorganic double salt, and from about 0.1% to about 50%, more preferably of 5% to about 10% of sodium carbonate, both of which are contained in the aforementioned weight ratio range.
The other essential step in the process involves conditioning the agglomerates by drying and/or cooling the agglomerates exiting the high speed mixer or the moderate speed mixer if it is optionally used. This can be completed in a wide variety of apparatus including but not limited to fluid bed dryers. The drying and/or cooling steps enhance the free flowability of the agglomerates and continues the "fluffing" or "puffing" physical characteristic formation of the resulting agglomerates. While not intending to be bound by theory, it is believed that during the agglomeration step of the instant process, the inorganic double salt becomes embodied in the agglomerates and "puffs" the agglomerates into a fluffy, light, low density agglomerate particle. The inorganic double salt, such as Na2SO4•Na2CO3 (Burkeite), is preferably a high void volume, high integrity carrier particle that can absorb the surfactant while maintaining its shell-forming properties.
The detergent agglomerates produced by the process preferably have a surfactant level of from about 10% to about 30%, more preferably from about 15% to about 25% and, most preferably from about 20% to about 25%. The particle porosity of the resulting detergent agglomerates produced according to the process of the invention has relatively high porosity which unexpectedly results in a low density detergent compos4tion in the form of low
density agglomerates. In addition, an attribute of a particulate detergent composition is its relative particle size. The present process typically provides detergent agglomerates having a median particle size of from about 250 microns to about 1000 microns, and more preferably from about 400 microns to about 600 microns. As used herein, the phrase "mean particle size" refers to individual agglomerates and not individual particles or ingredients in the agglomerates. The combination of the above-referenced porosity and particle size results in agglomerates having density values of less than 500 g/1. Such a feature is especially useful in the production of laundry detergents having varying dosage levels as well as other granular compositions such as dishwashing compositions.
Optional Process Steps
In an optional step of the present process, the detergent agglomerates exiting the drying and/or cooling steps are further conditioned by additional cooling or drying in similar apparatus as are well known in the art. Another optional process step involves adding a coating agent to improve flowability and/or minimize over agglomeration of the detergent composition in one or more of the following locations of the instant process: (1) the coating agent can be added directly after the fluid bed cooler or dryer; (2) the coating agent may be added between the fluid bed dryer and the fluid bed cooler; (3) the coating agent may be added between the fluid bed dryer and the optional moderate speed mixer; and/or (4) the coating agent may be added directly to the optional moderate speed mixer and the fluid bed dryer. The coating agent is preferably selected from the group consisting of aluminosilicates, silicates, carbonates and mixtures thereof. The coating agent not only enhances the free flowability of the resulting detergent composition which is desirable by consumers in that it permits easy scooping of detergent during use, but also serves to control agglomeration by preventing or minimizing over agglomeration, especially when added directly to the moderate speed mixer. As those skilled in the art are well aware, over agglomeration can lead to very undesirable flow properties and aesthetics of the final detergent product.
Optionally, the process can comprise the step of spraying an additional binder in one or both of the mixers or fluid bed dryers. A binder is added for purposes of enhancing agglomeration by providing a "binding" or "sticking" agent for the detergent components. The binder is preferably selected from the group consisting of water, anionic surfactants, nonionic surfactants, polyethylene glycol, polyvinyl pyrrolidone polyacrylates, citric acid and mixtures thereof. Other suitable binder materials including those listed herein are described in Beerse et al, U.S. Patent No. 5,108,646 (Procter & Gamble Co.), the disclosure of which is incorporated herein by reference.
Other optional steps contemplated by the present process include screening the oversized detergent agglomerates in a screening apparatus which can take a variety of
forms including but not limited to conventional screens chosen for the desired particle size of the finished detergent product. Other optional steps include conditioning of the detergent agglomerates by subjecting the agglomerates to additional drying by way of apparatus discussed previously.
Another optional step of the instant process entails finishing the resiling detergent agglomerates by a variety of processes including spraying and/or admixing other conventional detergent ingredients. For example, the finishing step encompasses spraying perfumes, brighteners and enzymes onto the finished agglomerates to provide a more complete detergent composition. Such techniques and ingredients are well known in the art.
Detergent Surfactant Paste
The detergent surfactant paste used in the process is preferably in the form of an aqueous viscous paste, although other forms are also contemplated by the invention. This so-called viscous surfactant paste has a viscosity of from about 5,000 cps to about 100,000 cps, more preferably from about 10,000 cps to about 80,000 cps, and contains at least about 10% water, more typically at least about 30% water. The viscosity is measured at 70°C and at shear rates of about 10 to 100 sec.'l. Furthermore, the surfactant paste, if used, preferably comprises a detersive surfactant in the amounts specified previously and the balance water and other conventional detergent ingredients.
In an alternative embodiment of the process invention, the liquid acid precursor of anionic surfactant is used during the agglomeration step. This liquid acid precursor will typically have a viscosity of from about 500 cps to about 100,000 cps. The liquid acid is a precursor for the anionic surfactants described in detail previously.
Adjunct Detergent Material
The adjunct detergent materials used in the present process preferably comprises the sodium carbonate as mentioned earlier, especially when the liquid acid precursor is used as a neutralizing agent in the agglomeration step. The adjunct detergent material may also include a detergent aluminosilicate builder which are referenced as aluminosilicate ion exchange materials and sodium carbonate. The aluminosilicate ion exchange materials used herein as a detergent builder preferably have both a high calcium ion exchange capacity and a high exchange rate. Without intending to be limited by theory, it is believed that such high calcium ion exchange rate and capacity are a function of several interrelated factors which derive from the method by which the aluminosilicate ion exchange material is produced. In that regard, the aluminosilicate ion exchange materials used herein are preferably produced in accordance with Corkill et al, U.S. Patent No. 4,605,509 (Procter & Gamble), the disclosure of which is incorporated herein by reference.

Preferably, the aluminosilicate ion exchange material is in "sodium" form since the potassium and hydrogen forms of the instant aluminosilicate do not exhibit the as high of an exchange rate and capacity as provided by the sodium form. Additionally, the aluminosilicate ion exchange material preferably is in over dried form so as to facilitate production of crisp detergent agglomerates as described herein. The aluminosilicate ion exchange materials used herein preferably have particle size diameters which optimize their effectiveness as detergent builders. The term "particle size diameter" as used herein represents the average particle size diameter of a given aluminosilicate ion exchange material as determined by conventional analytical techniques, such as microscopic determination and scanning electron microscope (SEM). The preferred particle size diameter of the aluminosilicate is from about 0.1 micron to about 10 microns, more preferably from about 0.5 microns to about 9 microns. Most preferably, the particle.size diameter is from about 1 microns to about 8 microns.
Preferably, the aluminosilicate ion exchange material has the formula
(Formula Removed)
wherein z and y are integers of at least 6, the molar ratio of z to y is from about 1 to about 5 and x is from about 10 to about 264. More preferably, the aluminosilicate has the formula
(Formula Removed)
wherein x is from about 20 to about 30, preferably about 27. These preferred aluminosilicates are available commercially, for example under designations Zeolite A, Zeolite B, Zeolite P, Zeolite MAP and Zeolite X. Alternatively, naturally-occurring or synthetically derived aluminosilicate ion exchange materials suitable for use herein can be made as described in Krummel et al, U.S. Patent No. 3,985,669, the disclosure of which is incorporated herein by reference.
The aluminosilicates used herein are further characterized by their ion exchange capacity which is at least about 200 mg equivalent of CaCO3 hardness/gram, calculated on an anhydrous basis, and which is preferably in a range from about 300 to 352 mg equivalent of CaCO3 hardness/gram. Additionally, the instant aluminosilicate ion exchange materials are still further characterized by their calcium ion exchange rate which is at least about 2 grains Ca++/gallon/minute/-gram/gallon, and more preferably in a range from about 2 grains Ca++/gallon/minute/-gram/gallon to about 6 grains Ca++/gallon/minute/-gram/gallon .
Additional adjunct materials include bleaches, bleach activators, suds boosters or suds suppressors, anti-tarnish and anticorrosion agents, soil suspending agents, soil release agents, germicides, pH adjusting agents, non-builder alkalinity sources, chelating agents, smectite clays, enzymes, enzyme-stabilizing agents and perfumes. See U.S. Patent
3,936,537, issued February 3, 1976 to Baskerville, Jr. et al., incorporated herein by reference.
Other builders can be generally selected from the various water-soluble, alkali metal, ammonium or substituted ammonium phosphates, polyphosphates, phosphonates, polyphosphonates, carbonates, borates, polyhydroxy sulfonates, polyacetate_s, carboxylates, and polycarboxylates. Preferred are the alkali metal, especially sodium, salts of the above. Preferred for use herein are the phosphates, carbonates, C10-18 fatty acids, polycarboxylates, and mixtures thereof. More preferred are sodium tripolyphosphate, tetrasodium pyrophosphate, citrate, tartrate mono- and di-succinates, and mixtures thereof (see below).
In comparison with amorphous sodium silicates, crystalline layered sodium silicates exhibit a clearly increased calcium and magnesium ion exchange capacity. .In addition, the layered sodium silicates prefer magnesium ions over calcium ions, a feature necessary to insure that substantially all of the "hardness" is removed from the wash water. These crystalline layered sodium silicates, however, are generally more expensive than amorphous silicates as well as other builders. Accordingly, in order to provide an economically feasible laundry detergent, the proportion of crystalline layered sodium silicates used must be determined judiciously.
The crystalline layered sodium silicates suitable for use herein preferably have the formula
wherein M is sodium or hydrogen, x is from about 1 .9 to about 4 and y is from about 0 to about 20. More preferably, the crystalline layered sodium silicate has the formula
(Formula Removed)
wherein M is sodium or hydrogen, and y is from about 0 to about 20. These and other crystalline layered sodium silicates are discussed in Corkill et al, U.S. Patent No. 4,605,509, previously incorporated herein by reference.
Specific examples of inorganic phosphate builders are sodium and potassium tripolyphosphate, pyrophosphate, polymeric metaphosphate having a degree of polymerization of from about 6 to 21, and orthophosphates. Examples of polyphosphonate builders are the sodium and potassium salts of ethylene diphosphonic acid, the sodium and potassium salts of ethane 1-hydroxy-l, 1 -diphosphonic acid and the sodium and potassium salts of ethane, 1 , 1 ,2-triphosphonic acid. Other phosphorus builder compounds are disclosed in U.S. Patents 3,159,581; 3,213,030; 3,422,021; 3,422,137; 3,400,176 and 3,400,148, all of which are incorporated herein by reference.
Examples of nonphosphorus, inorganic builders are tetraborate decahydrate and silicates having a weight ratio of SiO- to alkali metal oxide'of from about 0.5 to about 4.0,
preferably from about 1.0 to about 2.4. Water-soluble, nonphosphorus organic builders useful herein include the various alkali metal, ammonium and substituted ammonium polyacetates, carboxylates, polycarboxylar.es and polyhydroxy sulfonates. Examples of polyacetate and polycarboxylate builders are the sodium, potassium, lithium, ammonium and substituted ammonium salts of ethylene diamine tetraacetic acid, nitrilotriacetic acid, oxydisuccinic acid, mellitic acid, benzene polycarboxylic acids, and citric acid.
Polymeric polycarboxylate builders are set forth in U.S. Patent 3,308,067, Diehl, issued March 7, 1967, the disclosure of which is incorporated herein by reference. Such materials include the water-soluble salts of homo- and copolymers of aliphatic carboxylic acids such as maleic acid, itaconic acid, mesaconic acid, fumaric acid, aconitic acid, citraconic acid and methylene malonic acid. Some of these materials are useful as the water-soluble anionic polymer as hereinafter described, but only if in intimate admixture with the non-soap anionic surfactant.
Other suitable polycarboxylates for use herein are the polyacetal carboxylates described in U.S. Patent 4,144,226, issued March 13, 1979 to Crutchfield et al, and U.S. Patent 4,246,495, issued March 27, 1979 to Crutchfield et al, both of which are incorporated herein by reference. These polyacetal carboxylates can be prepared by bringing together under polymerization conditions an ester of glyoxylic acid and a polymerization initiator. The resulting polyacetal carboxylate ester is then attached to chemically stable end groups to stabilize the polyacetal carboxylate against rapid depolymerization in alkaline solution, converted to the corresponding salt, and added to a detergent composition. Particularly preferred polycarboxylate builders are the ether carboxylate builder compositions comprising a combination of tartrate monosuccinate and tartrate disuccinate described in U.S. Patent 4,663,071, Bush et al., issued May 5, 1987, the disclosure of which is incorporated herein by reference.
Bleaching agents and activators are described in U.S. Patent 4,412,934, Chung et al., issued November 1, 1983, and in U.S. Patent 4,483,781, Hartman, issued November 20, 1984, both of which are incorporated herein by reference. Chelating agents are also described in U.S. Patent 4,663,071, Bush et al., from Column 17, line 54 through Column 18, line 68, incorporated herein by reference. Suds modifiers are also optional ingredients and are described in U.S. Patents 3,933,672, issued January 20, 1976 to Bartoletta et al., and 4,136,045, issued January 23, 1979 to Gault et al., both incorporated herein by reference.
Suitable smectite clays for use herein are described in U.S. Patent 4,762,645, Tucker et al, issued August 9, 1988, Column 6, line 3 through Column 7, line 24, incorporated herein by reference. Suitable additional detergency builders for use herein are enumerated in the Baskerville patent, Column 13, line 54 through Column 16, line 16,
and in U.S. Patent 4,663,071, Bush et al, issued May 5, 1987, both incorporated herein by reference.
In order to make the present invention more readily understood, reference is made to the following examples, which are intended to be illustrative only and not intended to be limiting in scope.
EXAMPLES A - B
This Example illustrates a batch mode of the instant process. A low density agglomerated detergent composition is prepared using a lab tilt-a-pin (available from Processall, Inc.) mixer. The spray dried granules are made in a Niro spray dryer by spraying a 25% by weight aqueous solution of Na2SO4•Na2CO3 ("Burkeite") and C12-15 alkyl ethoxylated (EO = 3) sulfate surfactant ("AE3S") (wt. ratio 63/27/10) in the spray dryer where the inlet air is 250 °C. The spray dried granules have a bulk density of 154 g/1 and a median particle size of 27 microns. The lab mixer is first charged with a mixture of powders, namely sodium carbonate (median particle size 5-40 microns made via Air Classifier Mill available from Hosokawa Powder Systems), light density, granular sodium tripolyphosphate (supplied by FMC Corp. and referenced as "STPP")), zeolite type A (supplied by Ethyl Corp. and noted below as "Zeolite A") and the spray dried granules containing the inorganic double salt Burkeite and AE3S. During the agglomeration process, the liquid acid precursor of sodium alkylbenzene sulfonate (C12H25-C6H4-SO3-H or "HLAS" as noted below) is then added on top of the powder mixture while the mixer was being operated for 15 seconds at 700 rpm until discrete agglomerates are formed in the mixer. It has been found that these conditions result in agglomerates unexpectedly acceptable for use in dry laundry detergent products. The composition of the agglomerates are given below in Table I.
TABLE I
(Table Removed)
Unexpectedly, the resulting agglomerates have a bulk density below 500 g/L and show excellent cake strength and flowability.
COMPARATIVE EXAMPLES C-E
These Examples describe compositions made by the process described in the Examples A-B with the exception that no surfactant (e.g. AE3S) is included in the spray dried granules and either sodium carbonate or the inorganic double salt ( Burkeite) is omitted. The following compositions are made as shown in Table II.
TABLE II
(Table Removed)
The bulk density of the resulting agglomerates considerably higher than 500 g/1, sticky and not free-flowing as a result of the exclusion of sodium carbonate or granules containing Burkeite and surfactant. Thus, this process produces compositions C-E which are outside the scope of the instant process invention.
COMPARATIVE EXAMPLES F-G
The compositions in these Examples are made by the batch mode process described in Examples A-B but do not contain Burkeite. Rather the compositions contain separate amounts of spray-dried sodium sulfate and spray-dried sodium carbonate. The compositions are shown in Table III.
TABLE III
(Table Removed)
Comparative Example F did not form acceptable agglomerates having the desired low density. While comparative Example G has a low density, the resulting agglomerates are sticky and not free-flowing.
EXAMPLE H-I
These Examples illustrate a batch mode of the instant process. A low density agglomerated detergent composition is prepared using a Braun® Type 4262 (available from
the Braun Company) food processor. Initially, spray dried granules containing the inorganic double salt (Na2SO4•Na2CO3 or Burkeite) and C12-15 alkyl ethoxylated (EO = 3) sulfate surfactant ("AE3S") are prepared in a large scale 10 foot tower operated at an inlet air temperature of 288 °C and a liquid feed temperature of 80 °C. A 25% by weight aqueous solution of Na2SO4'Na2CO3 and AE3S (wt. ratio 63/27/10) is spray.dried in the 10 foot spray drying tower. The spray dried granules exiting from the spray drying tower have a bulk density of 455 g/1 and a median particle size of 90 microns. The Braun® Type 4262 mixer is first charged with a mixture of powders, namely sodium carbonate (mean particle size 5-40 microns made via Air Classifier Mill), light density granular or high density powder sodium tripolyphosphate (both supplied by FMC Corp. and referenced as "STPP"), zeolite type A (supplied by Ethyl Corp. and noted as below as "Zeolite A") and spray dried granules containing the inorganic double salt ("Burkeite") and ("AE3S"). During the agglomeration process, the liquid acid precursor of sodium alkylbenzene sulfonate (C12H25-C6H4-SO3-H or "HLAS" as noted below) is then added on top of the powder mixture while the mixer is operated until discrete agglomerates are formed in the mixer. The composition of the agglomerates is given below in Table IV.
TABLE IV
(Table Removed)
Unexpectedly, the resulting agglomerates have a bulk density below 500 g/L and show good cake strength and flowability.
COMPARATIVE EXAMPLES J-K
The compositions in these Examples are made by the batch mode process described in Examples H-I but do not contain granules containing Burkeite and AE3S. The composition of the agglomerates is given below in Table V.
TABLE V
(Table Removed)
The resulting agglomerates of comparative Examples J and K. do not have the desired low
density.
Having thus described the invention in detail, it will be clear to those skilled in the art that various changes may be made without departing from the scope of the invention and the invention is not to be considered limited to what is described in the specification.

WE CLAIM:
1. A process for preparing a low density detergent composition which comprises the steps
of:
(a) spray drying an aqueous mixture of sodium sulfate, sodium carbonate and from 0.1%
to 15% by weight of a surfactant so as to form spray dried granules containing an
inorganic double salt of said sodium carbonate and said sodium sulfate and said
minor amount of said surfactant;
(b) agglomerating said spray dried granules with a detergent surfactant paste or its
precursor and adjunct dry detergent material in the ratio of the spray dried granules
to adjunct dry detergent ingredients from 1:10 to 10:1 in a high speed mixer to obtain
detergent agglomerates, wherein said adjunct dry detergent material includes an
adjunct sodium carbonate material; and
(c) drying said detergent agglomerates so as to form said detergent composition having a
density of below 500 g/1.

2. A process as claimed in claim 1, wherein said adjunct dry material is a builder
selected from the group consisting of aluminosilicates, crystalline layered silicates,
phosphates, and mixtures thereof.
3. A process as claimed in any of the preceding claims, wherein said inorganic double
salt has the formula Na2 SO4 •Na2CO3 in a weight ratio of Na2 SO4 to Na2 CO3 of 70:30.
4. A process as claimed in any of the preceding claims wherein the median residence
time of said detergent agglomerates in said high speed mixer is in range from 2 seconds to 45
seconds.
5. A process as claimed in any of the preceding claims the steps of agglomerating said
detergent agglomerates in a moderate speed mixer following said high speed mixer.
6. A process as claimed in claim 5 wherein the median residence time said detergent
agglomerates in said moderate speed mixer is in range from 0.5 minutes to 15 minutes.
7. A process as claimed in any of the preceding claims wherein said surfactant is a
C12-15 alkyl ethoxylated sulfate having an average degree of ethoxylation of from 1 to 5.
8. A process as claimed in any of the preceding claims wherein said weight ratio of said
spray dried granules to said adjunct sodium carbonate is from 1:5 to 5:1.
9. A process for preparing a low density detergent composition as claimed in any of the
preceding claims wherein the surfactant employed in step (a) is a C-12-15 alkyl ethoxylated
sulfate surfactant having an average degree of ethoxylation of 3.
10. A process for preparing a low density detergent composition substantially as
hereinbefore described in any of the Examples.

Documents:

341-del-1997-abstract.pdf

341-del-1997-assignment.pdf

341-del-1997-claims.pdf

341-del-1997-correspondence-others.pdf

341-del-1997-correspondence-po.pdf

341-del-1997-description (complete).pdf

341-del-1997-form-1.pdf

341-del-1997-form-19.pdf

341-del-1997-form-2.pdf

341-del-1997-form-3.pdf

341-del-1997-form-4.pdf

341-del-1997-form-6.pdf

341-del-1997-gpa.pdf

341-del-1997-petition-137.pdf

341-del-1997-petition-138.pdf

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Patent Number

232805

Indian Patent Application Number

341/DEL/1997

PG Journal Number

13/2009

Publication Date

27-Mar-2009

Grant Date

21-Mar-2009

Date of Filing

12-Feb-1997

Name of Patentee

THE PROCTER & GAMBLE COMPANY

Applicant Address

ONE PROCTER & GAMBLE PLAZA, CINCINNATI, OHIO 45202, U.S.A.

Inventors:

#	Inventor's Name	Inventor's Address
1	CHAPMAN, BENJAMIN EDGAR	9469 GALECREST DRIVE, CINCINNATI, OHIO, 45231, U.S.A.
2	ROGERS, STEVEN BARRETT	4489 HUBBLE ROAD, CINCINNATI, OHIO, 45247, U.S.A.
3	FRANCE, PAUL AMAAT	8331 SUMMERBRIDGE WAY, WEST CHESTER, OHIO, 45069, U.S.A.
4	BEIMESCH, WAYNE EDWARD	711, RED BUD DRIVE, COVINGTON, KY, 41015, U.S.A.

PCT International Classification Number

C11D 9/06

PCT International Application Number

N/A

PCT International Filing date

PCT Conventions:

#	PCT Application Number	Date of Convention	Priority Country
1	08/601,638	1996-02-14	U.S.A.