PROCESSES FOR MAKING A GRANULAR DETERGENT COMPOSITION CONTAINING MODIFIED CARBOXY METHYL CELLULOSE

Abstract: A process for continuously preparing detergent agglomerates comprising the steps of continuously mixing a liquid binder comprising of a mixture of surfactants and a copolymer of epichlorohydrin and a cyclic amine moiety and dry detergent materials into a high speed mixer/densifier to obtain detergent agglomerates. The ratio of the liquid binder to the dry detergent material is from about 1:10 to about 10:1, and the dry detergent materials comprise modified carboxy methyl cellulose. The agglomerates are then optionally mixed in a moderate speed mixer/densifier to further densify them. Finally, the detergent agglomerates are dried so as to increase their density.

Description: PROCESSES FOR MAKING A GRANULAR DETERGENT COMPOSITION CONTAINING MODIFIED CARBOXY METHYL CELLULOSE FIELD OF THE INVENTION The present invention generally relates to processes for producing a granular detergent composition. More particularly, the invention is directed to processes during which detergent granules or agglomerates are produced from starting detergent materials, one of which is a modified carboxy methyl cellulose BACKGROUND OF THE INVENTION Today's fabrics are made of an increasingly wide variety of materials, and they come in a multitude of colors. These various fabπc and color combinations present new and challenging laundering problems for the consumer Specifically, consumers want their clothes and other fabric articles to retain, for as long as possible the "new" look and feel that these fabrics have when they are purchased. But normal laundering processes can slowly degrade the texture of the fabrics and vividness of the color. This slow loss of a fabric's luster is caused part by the normal wear and tear associated with the fabric's use, but laundering also takes it toll on the appearance of fabrics. In an effort to appease consumers' desires to slow, or preferably, eliminate the degradation of a fabric's appearance, formulators have searched for detergent additives that will aid in maintaining a fabric's appearance over its normal life cycle. As new detergent additives are developed, formulators must find a way to incorporate the additives into detergent compositions without adversely affecting the physical or chemical properties of the existing composition. That is, an additive that maintains fabric appearance should not reduce the cleaning efficacy of the detergent, nor should it cause the detergent to clump or otherwise have undesirable physical charactenstics in the eyes of the average consumer. Often, the challenges associated with the introduction of a new detergent additive can be met with adjustments to the detergent manufacturing process. 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 m a spray-drymg 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 of the various starting materials and their respective chemical composition. Moreover, there has been interest m the art for providing processes which increase the density of detergent granules or powders Particular attention has been given to densifϊcation 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 tπpolyphosphate and sodium sulfate are densified and spheromzed in a Marumeπzer®. 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 processes have developed 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. These processes achιe\ e the desired increase m density by treating or densifymg "post tower" or spray dried granules 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 m a mixer to form free flowing agglomerates. Furthermore, it has been long-established practice for detergent formulators to use surfactants and combinations thereof m detergent compositions. By way of example, various anionic surfactants, especially the alkyl benzene sulfonates, alkyl sulfates, alkyl alkoxy sulfates and various nonionic surfactants, such as alkyl ethoxylates and alkylphenol ethoxylates are commonly used m detergent formulations. Surfactants have found use as detergent components capable of the removal of a wide variety of soils and stains. A consistent effort, however, is made by detergent manufacturers to improve detersive properties of detergent compositions by providing new and improved surfactants. A problem commonly associated with anionic surfactants is their sensitivity to cold water and/or hard water. Improved cleaning performance above and beyond current standards, especially for granular detergent compositions to be used under colder wash water conditions and/or in hard water, has been difficult to attain Therefore, it would be desirable to have a process for making a detergent composition which exhibits improved cleaning performance over a wide variety of soils and stams. Accordingly, there remains a need in the art for a process which produces a granular and/or agglomerated detergent composition from starting detergent ingredients including a surfactant which exhibits improved fabπc appearance protection without any loss m cleaning performance. Also, there remains a need for such a process which is more efficient and economical to facilitate large-scale production of low dosage or compact detergents. BACKGROUND ART The following references are directed to densifymg spray-dried granules: Appel et al, U.S. Patent No. 5,133,924 (Lever); Bortolotti et al, U.S. Patent No. 5,160,657 (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), Holhngsworth et al, European Patent Application 351,937 (Unilever); Swatlmg et al, U.S. Patent No. 5,205,958, and Capeci et al, U.S. Patent No. 5,366,652 (Procter & Gamble). SUMMARY OF THE INVENTION The present invention meets the aforementioned needs in the art by providing a process for continuously preparing detergent agglomerates comprising the steps of: (A) continuously mixing a liquid binder and dry detergent materials into a high speed mixer/densifier to obtain detergent agglomerates, wherein the ratio of the liquid binder to the dry detergent material is from about 1 : 10 to about 10: 1, wherein the dry detergent materials comprise modified carboxy methyl cellulose; (B) optionally mixing the detergent agglomerates in a moderate speed mixer/densifier to further densify and agglomerate the detergent agglomerates; and (C) drying the detergent agglomerates so as to increase their density. In one preferred embodiment of this invention, the dry detergent materials consist essentially of modified carboxy methyl cellulose. In another preferred aspect of this invention, the liquid binder comprises water and a polymer selected from the group consisting of dye transfer agents, polyammes, homopolymers and copolymers of polyacrylates, homopolymers and copolymers of polyacrylamides, homopolymers and copolymers of polyvinyl alcohol, homopolymers and copolymers of polyvinyl pyrrohdone, polymaleates, aliphatic polyesters, natural proteins, synthetic non- crystallme polyammoacids, water soluble nylons, polyethylene glycol, polyacrylate and mixtures thereof. Even more preferably, the liquid binder comprises a polymer selected from the group consisting of a polyvinyl N-Oxide, a copolymer of epichlorohydrm and a cyclic amine moiety, and mixtures thereof A preferred aspect of the invention includes the use of a surfactant paste m addition to the polymer-based liquid binder The paste includes surfactants selected from branched and linear anionics, nonionic, zwitterionic, ampholytic and cationic classes and compatible mixtures thereof. Even more preferably the surfactant paste is selected from the group consisting of linear straight chain alkylbenzene sulfonates m which the average number of carbon atoms in the alkyl group is from about 1 1 to 13, abbreviated as Ci 1.13 LAS, Sodium ethoxysulphate based on a biodegradable C12/14 synthetic or natural primary alcohol ethoxylate made with a nominal 3 moles of ethylene oxide In another embodiment of this invention there is provided a process for preparing a high density detergent composition, wherein additional detergent ingredients are formulated into separate agglomerates or granules and then admixed with the modified carboxy methyl cellulose containing agglomerates defined above Specifically, second detergent agglomerates can be made by a process comprising the steps of (A) continuously mixing a detergent surfactant paste and additional dry detergent materials into a high speed mixer/densifier to obtain second detergent agglomerates, wherein the ratio of the surfactant paste to the additional dry detergent material is from about 1 T 0 to about 10 1, (B) optionally mixing the second detergent agglomerates m a moderate speed mixer/densifier to increase their density, (C) drying the second detergent agglomerates to further increase their density The second detergent agglomerates can then be mixed with the first detergent agglomerates to form the high density detergent composition. In another aspect of this embodiment, the surfactant paste can be replaced by, or supplemented with an acid precursor of an anionic surfactant and additional dry detergent materials which contain an alkaline inorganic material capable of neutralizing the acid precursor. Moreover, detergent granules can be admixed with the modified carboxy methyl cellulose containing agglomerates defined above to form a high density detergent composition. These granules can be formed by spray drying an aqueous slurry containing adjunct detergent ingredients to form spray dried granules Then the granules and the detergent agglomerates can be blended together to form the high density detergent composition. It has been surprisingly found that certain modified carboxy methyl cellulose materials provide fabric appearance benefits Unfortunately, the modified carboxy methyl cellulose materials are sometimes supplied as a sticky powder, which when added to a detergent composition can cause the resulting detergent agglomerates to be sticky as well Sticky agglomerates often cause clumps m the detergent composition which is a strong consumer negative. In addition to the stickiness we have also found that these modified carboxy methyl cellulose materials are not always dispersed satisfactorily, resulting in reduced performance and moreover localised residues of the material m the washing machine and on the fabrics. Furthermore, the inventors also found that other detergent ingredients can become entrapped in the cellulosic material, causing further residue problems, reduced performance of these other ingredients. The stickiness and the poor dispersabihty of the modified carboxy methyl cellulose, and its deleterious effect on the detergent composition, can be counter-acted by the processing conditions and constituents defined herein Accordingly, it is an object of the present invention to provide a process for producing a granular and/or agglomerated detergent composition directly from starting detergent ingredients which includes a surfactant and a modified carboxy methyl cellulose having improved fabric integrity performance. It is also an object of the invention to provide such a process which is not limited by unnecessary process parameters so that large-scale production of low dosage or compact detergents is more economical and efficient. 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 invention and the appended claims. DETAILED DESCRIPTION OF THE INVENTION The present process is used m the production of detergent compositions wherein two separate agglomerates particles are prepared. A first agglomerate is prepared from using a liquid binder comprising a mixture of surfactant selected from the group of LAS, preferably C j .13 LAS or Sodium ethoxysulphate, wherein the ethoxysulate is preferably based on a biodegradable C12/14 synthetic or natural primary alcohol ethoxylate made with a nominal 3 moles of ethylene oxide and mixtures thereof; this liquid binder is used in combination with a polymer selected from the group of a copolymer of epichlorohydπn and a cyclic amine moiety or polyvinyl N- Oxide, and mixtures thereof m combination with dry detergent materials that include a modified carboxy methyl cellulose. A second agglomerate is prepared using a surfactant paste and dry starting materials that do not include modified carboxy methyl cellulose. The two separate agglomerates are admixed to form a detergent composition that is free flowing. Moreover, the separate detergent particles of this invention can be formed by spray drying techniques which can include further processing of the "post-tower" detergent granules. By "post-tower" detergent granules, it is meant those detergent granules which have been processed through a conventional spray-drymg tower or similar apparatus. Dry Detergent Materials The compositions of the invention contain, in addition to a modified carboxy methyl cellulose material, at least one suitable adjunct dry detergent ingredient is preferably included m the detergent composition. The resulting detergent compositions preferably comprises from about 0.01% to about 4%, more preferably from about 0.05% to about 2%, and most preferably from about 0.1% to about 1%, by weight of the modified carboxy methyl cellulose. The adjunct dry detergent ingredient is preferably selected from the group consisting of builders, enzymes, bleaching agents, bleach activators, suds suppressors, soil release agents, bπghteners, perfumes, hydrotropes, dyes, pigments, polymeric dispersing agents, pH controlling agents, chelants, processing aids, crystallization aids, and mixtures thereof. The following disclosure of modified carboxy methyl cellulose materials and adjunct detergent ingredients and mixtures thereof for use in the compositions herein is representative of the detergent ingredients, but is not intended to be limiting. As discussed above, certain modified carboxy methyl cellulose materials, which are m the form of cellulosic based polymers or oligomers, can provide substantive and unexpected cleaning benefits when added to a laundry composition. But these materials can also pose certain processing problems for granular detergent formulators. The modified carboxy methyl cellulose materials that are suitable for use in laundry operations and provide the desired fabric appearance and integrity benefits can be characterized by the following general formula: wherein each R is selected from the group consisting of 2, Re, and wherein: each R2 is independently selected from the group consisting of H and C1 -C4 alkyl; O - each R i s -^ -C-OZ wherein each Z is independently selected from the group consisting of M, R2, Re, and R H ; each R H is independently selected from the group consisting of C5 -C20 alkyl, C5-C7 cycloalkyl, C7-C20 alkylaryl, C -C20 arylalkyl, substituted alkyl, hydroxyalkyl, C1 -C20 alkoxy-2-hydroxyalkyl, C7-C20 alkylaryloxy-2-hydroxyalkyl, (R4)2N-alkyl, (R4)2N-2- hydroxyalkyl, ^4)3 N-alkyl, (R4J3 N-2-hydroxyalkyl, C6-C12 aryloxy-2-hydroxyalkyl, O R 5 O R 5 O R 5 O I I I I I I II I II — C CH C CH 2 — C CH 2 CH C-OM and O R 5 O II I II — C — CH— CH 2 — C-OM each R4 is independently selected from the group consisting of H, CJ-C20 alkyl, C5-C7 cycloalkyl, C7-C20 alkylaryl, C7-C20 arylalkyl, aminoalkyl, alkylammoalkyl, dialkylammoalkyl, prpeπdinoalkyl, morphohnoalkyl, cycloalkylammoalkyl and hydroxyalkyl; each R5 is independently selected from the group consisting of H, C1 -C20 alkyl, C5-C7 cycloalkyl, C7-C20 alkylaryl, C7-C20 arylalkyl, substituted alkyl, hydroxyalkyl, (R 4 ) 2 N-alkyl, and (R 4 ) 3 N-alkyl. wherein: M is a suitable cation selected from the group consisting of Na, K, l/2Ca, and l/2Mg; each x is from 0 to about 5, each y is from about 1 to about 5; and provided that: the Degree of Substitution for group R H is between about 0.001 and 0.1, more preferably between about 0.005 and 0.05, and most preferably between about 0.01 and 0.05; the Degree of Substitution for group Re wherein Z is H or M is between about 0.2 and 2.0, more preferably between about 0 3 and 1.0, and most preferably between about 0.4 and 0.7; if any R H bears a positive charge, it is balanced by a suitable amon; and two R4's on the same nitrogen can together form a ring structure selected from the group consisting of pipeπdme and morpholme. Preferably the carboxy methyl cellulose is modified with an ester linkage, ether linkage or combinations thereof. Modified carboxy methyl cellulose materials suitable for use in this invention are described in greater detail in two co-pending applications entitled "Laundry Detergent Compositions With Cellulosic Based Polymers to Provide Appearance and Integrity Benefits to Fabrics Laundered Therewith", PCT Ser No. PCT/US98/19139 and PCT Ser. No. PCT/US98/19142. Both of these applications were filed in the PCT on September 15, 1998, in the name of Jennifer A. Leupin et al , and they claim the benefit of U.S. provisional application 60/058,892, filed on September 15, 1997 The entire disclosures of PCT Ser. No. PCT/US98/19139 and PCT Ser. No. PCT/US98/19142 are incorporated herein by reference One or more builders can be used to further improve the performance of the compositions described herein. For example, the builder can be selected from the group consisting of aluminosihcates, crystalline layered silicates, MAP zeolites, citrates, amorphous silicates, polycarboxylates, sodium carbonates and mixtures thereof. The sodium carbonate ingredient can serve as the inorganic alkaline material when a liquid acid precursor of the mid- chain branched surfactant is used. Other suitable auxiliary builders are described hereinafter. Preferred builders include aluminosihcate ion exchange materials and sodium carbonate. The aluminosihcate 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 aluminosihcate ion exchange material is produced. In that regard, the aluminosihcate ion exchange materials used herein are preferably produced m 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 aluminosihcate ion exchange material is in "sodium" form since the potassium and hydrogen forms of the instant aluminosihcate do not exhibit as high of an exchange rate and capacity as provided by the sodium form. Additionally, the aluminosihcate ion exchange material preferably is m over dried form so as to facilitate production of crisp detergent agglomerates as described herein. The aluminosihcate 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 aluminosihcate 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 aluminosihcate 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 aluminosihcate ion exchange material has the formula Na z [(A10 2 ) z .(Sι0 2 ) y ]xH 2 0 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 aluminosihcate has the formula Na 12 [(A10 2 ) 12 .(Sιθ2)i2]xH2θ 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 and Zeolite X. Alternatively, naturally-occurring or synthetically derived aluminosihcate 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 CaCθ3 hardness/gram, calculated on an anhydrous basis, and which is preferably m a range from about 300 to 352 mg equivalent of CaQ hardness/gram. Additionally, the instant aluminosihcate ion exchange materials are still further characterized by their calcium ion exchange rate which is at least about 2 grains Ca ++ /gallon/mιnute/-gram/gallon, and more preferably in a range from about 2 grains Ca ++ /gallon/mιnute/-gram/gallon to about 6 grains Ca ++ /gallon/mmute/-gram/gallon . Liquid Binder To form the desired agglomerates of the present invention, the dry starting materials are mixed with a liquid binder. A binder is added for purposes of enhancing agglomeration by providing a "binding" or "sticking" agent for the detergent components. The preferred liquid binder for use in this invention comprises water, surfactant paste and a polymer. The paste includes surfactants selected from branched and linear anionics, nonionic, zwitterionic, ampholytic and cationic classes and compatible mixtures thereof. The viscosity, rheology and chemical composition of the surfactant pastes are described in more detail below. The polymer is selected from the group consisting of dye transfer agents, polyammes, homopolymers and copolymers of polyacrylates, homopolymers and copolymers of polyacrylamides, homopolymers and copolymers of polyvinyl alcohol, homopolymers and copolymers of polyvinyl pyrrohdone, polymaleates, aliphatic polyesters, natural proteins, synthetic non-crystallme polyammoacids, water soluble nylons, polyethylene glycol, polyacrylate and mixtures thereof. Detergent compositions made with the agglomerates of this invention preferably comprise from about 0.01% to about 4%, more preferably from about 0.05% to about 2%, and most preferably from about 0.1% to about 1%, by weight of the liquid binder. Preferably the surfactant paste is selected from the group consisting of linear straight chain alkylbenzene sulfonates, preferably linear straight chain alkylbenzene sulfonates in which the average number of carbon atoms in the alkyl group is from about 11 to 13 (abbreviated as Ci ι .ι 3 LAS), sodium ethoxysulphate. preferably based on a biodegradable C12/14 synthetic or natural primary alcohol ethoxylate made with a nominal 3 moles of ethylene oxide, and mixtures thereof. Preferably the dye transfer agent is a polyvinyl N-Oxide such as poly(4-vιnylpyπdme-N- oxide) "PVNO". Copolymers of N-vmylpyrrohdone and N-vmyhmidazole are also acceptable for use herein. Polyvinyl N-oxide materials are disclosed in U.S. Patent No. 5,804,543, which issued on September 8, 1998, to Wertz and Panandiker. The entire disclosure of U.S. Patent No. 5,804,543 is incorporated herein by reference. Additionally preferred liquid binders for use m this invention are polyammes, and even more preferred are copolymers of epichlorohydπn and a cyclic amine moiety. Descriptions and example of the preferred polyammes for use in this invention can be found in the following PCT Patent Applications: PCT/US98/19143. PCT/US98/19141, and PCT/US98/19144, all three of these applications were filed internationally on September 15, 1998 and they all claim the benefit of U.S Provisional Application No. 60/058,931, which was filed on September 15, 1997. The entire disclosures of PCT/US98/19143. PCT US98/19141, and PCT/US98/19144 are incorporated herein by reference. Moreover, U.S. Provisional Application No. 60/103,978, which was filed on October 13, 1998. discloses a detergent composition comprising copolymers of epichlorohydrm and a cyclic amine moiety with modified carboxy methyl cellulose materials. The entire disclosure of U.S. Provisional Application No. 60/103,978 is incorporated herein by reference. Optionally, the process comprises the step of spraying an additional binder m one or both of the mixer/densifiers. The additional binder is preferably selected from the group consisting of water, anionic surfactants, nonionic surfactants, polyethylene glycol, polyvinyl pyrrohdone 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. Surfactant Paste The viscoelastic surfactant paste used herein has viscoelastic fluid properties which can be described by a commonly used mathematical model that accounts for the shear thinning nature of the paste. The mathematical model is called the Power Law Model and is described by the following relation: σ = Kγ n where σ = Shear Stress (dynes/cm^), K = Consistency (Poise-sec"-' ), γ = Shear Rate (sec -1 ), and n = Rate Index (dimensionless). The rate index n vanes from 0 to 1. The closer n is to 0, the more shear thinning the fluid. The closer n is to 1. the closer it is to simple Newtonian behavior, i.e. constant viscosity behavior. K can be interpreted as the apparent viscosity at a shear rate of 1 sec " ' . In this context, the viscoelastic surfactant paste used in the process has a consistency K at 70°C of from about 50,000 to about 450,000 cPoise sec" " 1 (500 to 2,500 Poise-sec"" 1 ), more preferably from about 100,000 to about 195,000 cPoise-sec" " 1 (1 ,000 to 1,950 Poise-sec"" 1 ), and most preferably from about 120,000 to about 180,000 cPoise-sec" "1 (1,200 to 1,800 Poise-sec" " 1 ). Preferably, the surfactant paste has a shear index n of from about 0.05 to about 0.25, more preferably from about 0.08 to about 0.20 and most preferably from about 0.10 to about 0.15. The paste includes surfactants selected from branched and linear anionics, nonionic, zwitterionic, ampholytic and cationic classes and compatible mixtures thereof. Detergent surfactants useful herein are described in U.S. Patent 3,664,961, Norris, issued May 23, 1972, and in U.S. Patent 3,919,678, Laughhn 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. The following are representative examples of detergent surfactants useful m the present surfactant paste Water-soluble salts of the higher fatty acids, i.e , "soaps", are useful anionic surfactants in the compositions herein. This includes alkali metal soaps such as the sodium, potassium, ammonium, and alkylolammonium salts of higher fatty acids containing from about 8 to about 24 carbon atoms, and preferably from about 12 to about 18 carbon atoms. Soaps can be made by direct saponification of fats and oils or by the neutralization of free fatty acids. Particularly useful are the sodium and potassium salts of the mixtures of fatty acids derived from coconut oil and tallow, i.e., sodium or potassium tallow and coconut soap. Additional anionic surfactants that are suitable for use herein include the water-soluble salts, preferably the alkali metal, ammonium and alkylolammonium salts, of organic sulfuπc reaction products having m their molecular structure a straight-chain alkyl group containing from about 10 to about 20 carbon atoms and a sulfonic acid or sulfuπc acid ester group. (Included m the term "alkyl" is the alkyl portion of acyl groups.) Examples of this group of synthetic surfactants are the sodium and potassium alkyl sulfates, especially those obtained by sulfatmg the higher alcohols (C„ 1 _ carbon atoms) such as those produced by reducing the glyceπdes of tallow or coconut oil; and the sodium and potassium alkylbenzene sulfonates m which the alkyl group contains from about 9 to about 15 carbon atoms, in straight chain, e.g., those of the type described in U.S. Patents 2,220,099 and 2,477,383. Especially valuable are linear straight chain alkylbenzene sulfonates in which the average number of carbon atoms in the alkyl group is from about 11 to 13, abbreviated as C 1 1.13 LAS Other anionic surfactants suitable for use herein are the sodium alkyl glyceryl ether sulfonates, especially those ethers of higher alcohols derived from tallow and coconut oil; sodium coconut oil fatty acid monoglyceπde sulfonates and sulfates; sodium or potassium of ethylene oxide per molecule and wherein the alkyl groups contain from about 8 to about 12 carbon atoms; and sodium or potassium salts of alkyl ethylene oxide ether sulfates containing about 1 to about 10 units of ethylene oxide per molecule and wherein the alkyl group contains from about 10 to about 20 carbon atoms In addition, suitable anionic surfactants include the water-soluble salts of esters of alpha-sulfonated fatty acids containing from about 6 to 20 carbon atoms the fatty acid group and from about 1 to 10 carbon atoms in the ester group; water-soluble salts of 2-acyloxyalkane- 1 -sulfomc acids containing from about 2 to 9 carbon atoms m the acyl group and from about 9 to about 23 carbon atoms in the alkane moiety; alkyl ether sulfates containing from about 10 to 20 carbon atoms in the alkyl group and from about 1 to 30 moles of ethylene oxide; water-soluble salts of olefin and paraffin sulfonates containing from about 12 to 20 carbon atoms; and beta-alkyloxy alkane sulfonates containing from about 1 to 3 carbon atoms in the alkyl group and from about 8 to 20 carbon atoms in the alkane moiety. Preferred adjunct anionic surfactants are C. „ . „ linear alkylbenzene sulfonate and C, „ . „ alkyl sulfate. If desired, low moisture (less than about 25% water) alkyl sulfate paste can be the sole ingredient in the surfactant paste. Most preferred are C. » 1 „ alkyl sulfates, linear or branched, and any of primary, secondary or tertiary. A preferred embodiment of the present invention is wherein the surfactant paste comprises from about 20% to about 40% of a mixture of sodium C. „ 1 _ linear alkylbenzene sulfonate and sodium C. „ . , alkyl sulfate m a weight ratio of about 2: 1 to 1 :2. Another preferred embodiment of the detergent composition includes a mixture of Ci Q_\g alkyl sulfate and C1 Q- 18 alkyl ethoxy sulfate m a weight ratio of about 80:20. Water-soluble nonionic surfactants are also useful in the instant invention. Such nonionic materials include compounds produced by the condensation of alkylene oxide groups (hydrophihc in nature) with an organic hydrophobic compound, which may be aliphatic or alkyl aromatic in nature. The length of the polyoxyalkylene 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 hydrophihc and hydrophobic elements. Suitable nonionic surfactants include the polyethylene oxide condensates of alkyl phenols, e.g., the condensation products of alkyl phenols having an alkyl group containing from about 6 to 15 carbon atoms, in either a straight chain or branched chain configuration, with from about 3 to 12 moles of ethylene oxide per mole of alkyl phenol Included are the water-soluble and water-dispersible condensation products of aliphatic alcohols containing from 8 to 22 carbon atoms, in either straight chain or branched configuration, with from 3 to 12 moles of ethylene oxide per mole of alcohol An additional group of nonionics suitable for use herein are semi-polar nonionic surfactants which include water-soluble amine oxides containing one alkyl moiety of from abut 10 to 18 carbon atoms and two moieties selected from the group of alkyl and hydroxyalkyl moieties of from about 1 to about 3 carbon atoms; water-soluble phosphme oxides containing one alkyl moiety of about 10 to 18 carbon atoms and two moieties selected from the group consisting of alkyl groups and hydroxyalkyl groups containing from about 1 to 3 carbon atoms; and water-soluble sulfoxides containing one alkyl moiety of from about 10 to 18 carbon atoms and a moiety selected from the group consisting of alkyl and hydroxyalkyl moieties of from about 1 to 3 carbon atoms. Preferred nonionic surfactants are of the formula R (OC,H .) OH, wherein R is a 2 4 y n C, -C, alkyl group or a C n -C. » alkyl phenyl group, and n is from 3 to about 80. Particularly preferred are condensation products of C. ~-C, - alcohols with from about 5 to about 20 moles of ethylene oxide per mole of alcohol, e g., C. ~-C. , alcohol condensed with about 6.5 moles of ethylene oxide per mole of alcohol. Additional suitable nonionic surfactants include polyhydroxy fatty acid amides. Examples are N-methyl N- 1 -deoxyglucityl cocoamide and N-methyl N- 1 -deoxyglucityl oleamide. Processes for making polyhydroxy fatty acid amides are known and can be found in Wilson, U.S. Patent No. 2,965,576 and Schwartz, U.S. Patent No 2,703,798, the disclosures of which are incorporated herein by reference. Ampholytic surfactants include derivatives of aliphatic or aliphatic derivatives of heterocychc secondary and tertiary ammes in which the aliphatic moiety can be straight chain or branched and wherein one of the aliphatic substituents contains from about 8 to 18 carbon atoms and at least one aliphatic substituent contains an anionic water-solubihzmg group Zwitterionic surfactants include derivatives of aliphatic, quaternary, ammonium, phosphomum, and sulfomum compounds in which one of the aliphatic substituents contains from about 8 to 18 carbon atoms. Cationic surfactants can also be included in the present invention Cationic surfactants comprise a wide variety of compounds characterized by one or more organic hydrophobic groups in the cation and generally by a quaternary nitrogen associated with an acid radical Pentavalent nitrogen ring compounds are also considered quaternary nitrogen compounds. Suitable anions are halides, methyl sulfate and hydroxide Tertiary ammes can have characteristics similar to catiomc surfactants at washing solution pH values less than about 8.5. A more complete disclosure of these and other cationic surfactants useful herein can be found in U.S. Patent 4,228,044, Cambre, issued October 14, 1980, incorporated herein by reference. Cationic surfactants are often used m detergent compositions to provide fabric softening and/or antistatic benefits. Antistatic agents which provide some softening benefit and which are preferred herein are the quaternary ammonium salts described m U.S. Patent 3,936,537, Baskerville, Jr. et al., issued February 3. 1976, the disclosure of which is incorporated herein by reference. Agglomeration Process As used herein, the term "agglomerates" refers to particles formed by build-up agglomeration of starting detergent ingredients (particles) which typically have a smaller median particle size than the formed agglomerates. All percentages and ratios used herein are expressed as percentages by weight (anhydrous basis) unless otherwise indicated. All documents are incorporated herein by reference. All viscosities referenced herein are measured at 70°C (±5°C) and at shear rates of about 10 to 100 sec ' 1 . In the first step of the process, the invention entails continuously mixing into a high speed mixer/densifier several streams of starting detergent ingredients which include a liquid binder comprising a mix of a liquid polymer and asurfactant paste. Dry detergent materials, which may include a modified carboxy methyl cellulose material, are also added continuously into the high speed mixer/densifier. In one embodiment of the process the dry starting detergent material comprises from about 10% to about 50%, preferably from about 15% to about 45% and, most preferably from about 20% to about 40% of an aluminosihcate or zeolite builder and from about 10% to about 40%, preferably from about 15% to about 30% and, most preferably from about 15% to about 25% of a sodium carbonate. It should be understood that additional starting detergent ingredients several of which are described hereinafter may be mixed into high speed mixer/densifier without departing from the scope of the invention. In another embodiment of the process, the dry starting detergent material comprises from about 10% to about 50%, preferably from about 15% to about 45% and, most preferably from about 20% to about 40% of an aluminosihcate or zeolite builder and from about 10% to about 40%, preferably from about 15% to about 30% and, most preferably from about 15% to about 25% of an ester modified carboxy methyl cellulose. It should be understood that additional starting detergent ingredients several of which are described hereinafter may be mixed into high speed mixer/densifier without departing from the scope of the invention. However, it has been found that when the liquid binder comprising of liquid polymer and surfactant paste and the dry starting detergent material are continuously mixed within the ratio ranges described herein the desired free flowing, crisp, high density detergent composition are produced. Preferably, the ratio of the surfactant paste or liquid binder to the dry starting detergent material is from about 1 : 10 to about 10 1, more preferably from about 1 -4 to about 4:1 and, most preferably from about 2: 1 to about 2:3. Also, it has been found that the first processing step can be successfully completed, under the process parameters described herein, in a high speed mixer/densifier which preferably is a Lbdige CB mixer or similar brand mixer. These types of mixers essentially consist of a horizontal, hollow static cylinder having a centrally mounted rotating shaft around which several plough-shaped blades are attached. Preferably, the shaft rotates at a speed of from about 300 rpm to about 2500 rpm, more preferably from about 400 rpm to about 1600 rpm Preferably, the mean residence time of the detergent ingredients in the high speed mixer/densifier is preferably m range from about 2 seconds to about 45 seconds, and most preferably from about 5 seconds to about 15 seconds. The mean residence time can be conveniently and accurately measured by dividing the tear weight of the mixer/densifier by the throughput (e.g., kg/hr). The resulting detergent agglomerates formed in the high speed mixer/densifier are then fed into a lower or moderate speed mixer/densifier during which further agglomeration and densification is carried forth. This particular moderate speed mixer/densifier used in the present process should include liquid distribution and agglomeration tools so that both techniques can be carried forth simultaneously. It is preferable to have the moderate speed mixer/densifier to be, for example, a Lodige KM (Ploughshare) mixer, Drais® K-T 160 mixer or similar brand mixer. The mam centrally rotating shaft speed is from about 30 to about 160 rpm, more preferably from about 50 to about 100 rpm. The mean residence time in the moderate speed mixer/densifier is preferably from about 0.25 minutes to about 15 minutes, most preferably the residence time is about 0.5 to about 10 minutes This mean residence time also can be conveniently and accurately measured by dividing the tear weight of the mixer/densifier at steady state by the throughput (e.g., kg/hr). The liquid distribution is accomplished by cutters, generally smaller in size than the rotating shaft, which preferably operate at about 3600 rpm. In accordance with the present process, the high speed mixer/densifier and moderate speed mixer/densifier in combination preferably impart a requisite amount of energy to form the desired agglomerates. More particularly, the instant process imparts from about 5 x lO 1 ^ erg/kg to about 2 x lO ^ erg/kg at a rate of from about 3 x 10° erg/kg-sec to about 3 x lθ" erg/kg-sec to form free flowing high density detergent agglomerates. The energy input and rate of input can be determined by calculations from power readings to the moderate speed mixer/densifier with and without granules, residence time of the granules in the mixer/densifier, and the mass of the granules in the mixer/densifier Such calculations are clearly withm the scope of the skilled artisan Thereafter, the detergent agglomerates are dried in a fluid bed dryer or similar apparatus The density of the resulting detergent agglomerates exiting the fluid bed dryer is at least 400 g/1, more preferably from about 500 g/1 to about 600 g/1 The particle porosity of the resulting detergent agglomerates of the composition is preferably in a range from about 5% to about 20%, more preferably at about 10% As those skilled m the art will readily appreciate a low porosity detergent agglomerate provides a dense or low dosage detergent product, to which the present process is primarily directed In addition, an attribute of dense or densified detergent agglomerates is the relative particle size The present process typically provides agglomerates having a median particle size of from about 400 microns to about 700 microns, and more preferably from about 475 microns to about 600 microns As used herein, the phrase "median particle size" refers to individual agglomerates and not individual particles or detergent granules The combination of the above-referenced porosity and particle size results in agglomerates mg density values of 600 g/1 and higher Such a feature is especially useful in the production of low dosage laundry detergents 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 fluid bed dryer are further conditioned by cooling the agglomerates in a fluid bed cooler or 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, (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 moderate speed mixer/densifier, and/or (4) the coating agent may be added directly to the moderate speed mixer/densifier and the fluid bed dryer It should be understood that the coating agent can be added in any one or a combination of streams, see Capeci et al, U S Patent 5,516,448, issued May 14, 1996 and Capeci et al, U S Patent 5,489,392, issued February 6, 1996 The coating agent is preferably selected from the group consisting of aluminosilicates, silicates, carbonates and mixtures thereof However, the coating agent may be one or more combinations of the builder material, aluminosilicates, carbonates, silicates and the like 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/densifier. 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. Other optional steps contemplated by the present process include screening the oversized detergent agglomerates m 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. Another optional step of the instant process entails finishing the resulting detergent agglomerates by a variety of processes including spraying and/or admixing other conventional detergent ingredients. For example, this step encompasses spraying perfumes, bπghteners and enzymes onto the finished agglomerates to provide a more complete detergent composition. Such techniques and ingredients are well known in the art. Spray Drying Process One or more spray drying techniques can be used alone, or in combination with the aforementioned agglomeration processes, to make detergent compositions m accordance with the instant invention. One or more spray-drymg towers may be employed to manufacture granular laundry detergents which often have a density of about 500 g/1 or less In this procedure, an aqueous slurry of various heat-stable ingredients in the final detergent composition are formed into homogeneous granules by passage through a spray-drymg tower, using conventional techniques, at temperatures of about 175°C to about 225°C If spray drying is used as part of the overall process herein, additional process steps as described herein can be optionally used to obtain the level of density (i.e., > 650 g/1) required by modern compact, low dosage detergent products. For example, spray-dπed granules from a tower can be densified further by loading a liquid such as water or a nonionic surfactant into the pores of the granules and/or subjecting them to one or more high speed mixer/densifiers A suitable high speed mixer/densifier for this process is the aforementioned "Lodige CB 30" or "Lodige CB 30 Recycler" which comprises a static cylindrical mixing drum having a central rotating shaft with mixing/cutting blades mounted thereon. In use, the ingredients for the detergent composition are introduced into the drum and the shaft/blade assembly is rotated at speeds in the range of 100-2500 rpm to provide thorough mixing/densification. See Jacobs et al, U S. Patent 5,149,455, issued September 22, 1992. Other such apparatus includes the devices marketed under the trade name "Shugi Granulator" and under the tradename "Drais K-TTP 80) Another process step which can be used to densify further spray-dried granules involves grinding and agglomerating or deforming the spray-dried granules in a moderate speed mixer/densifier so as to obtain particles having lower porosity. Equipment such as the aforementioned "Lodige KM" (Series 300 or 600) or "Lodige Ploughshare" mixer/densifiers are suitable for this process step. Other useful equipment includes the device which is available under the tradename "Drais K-T 160". This process step which employs a moderate speed mixer/densifier (e.g. Lodige KM) can be used by itself or sequentially with the aforementioned high speed mixer/densifier (e g Lodige CB) to achieve the desired density. Other types of granules manufacturing apparatus useful herein include the apparatus disclosed in U.S. Patent 2,306,898, to G. L. Heller, December 29, 1942. While it may be more suitable to use the high speed mixer/densifier followed by the low speed mixer/densifier, the reverse sequential mixer/densifier configuration is also contemplated by the invention. One or a combination of various parameters including residence times m the mixer/densifiers, operating temperatures of the equipment, temperature and/or composition of the granules, the use of adjunct ingredients such as liquid binders and flow aids, can be used to optimize densification of the spray-dπed granules in the process of the invention. By way of example, see the processes m Appel et al, U S Patent 5,133,924, issued July 28, 1992 (spray- dried granules are brought into a deformable state prior to densification); Delwel et al, U.S. Patent 4,637,891, issued January 20, 1987 (granulating spray-dried granules with a liquid binder and aluminosihcate); Kruse et al, U.S. Patent 4,726,908, issued February 23, 1988 (granulating spray-dried granules with a liquid binder and aluminosihcate); and, Bortolotti et al, U.S. Patent 5,160,657, issued November 3, 1992 (coating densified spray-dried granules with a liquid binder and aluminosihcate). Admixing Process Specifically, other aspects of the process invention include admixing additional detergent materials with the various agglomerates, spray dried granules and combinations thereof. This admixing step may be enhanced by combining the agglomerates, granules, or combinations thereof with additional detergent materials and a liquid binder m a mixing drum or other similar device. Optionally, the additional detergent materials may be coated with a nonionic surfactant or other liquid binder as described previously before the admixing step so as to preclude any deleterious interaction with the other detergent ingredients (e.g. anionic surfactants) prior to immersion m the washing solution (i.e. during processing and storage). This liquid binder or nonionic surfactant coating also improves the flow properties of the detergent composition m which the builder material is included. Other Processes In yet another process embodiment, the high density detergent composition can be produced by feeding a liquid acid precursor of an anionic surfactant, an alkaline inorganic material (e.g. sodium carbonate) and optionally other detergent ingredients into a high speed mixer/densifier (residence time 5-30 seconds) so as to form agglomerates containing a partially or totally neutralized anionic surfactant salt and the other starting detergent ingredients. Subsequently, the contents in the high speed mixer/densifier can be sent to a moderate speed mixer/densifier (e.g. Lodige KM) for further agglomeration resulting in the finished high density detergent composition. In another process embodiment, the surfactant paste is premixed or extruded m a mixing or extruding apparatus such as a twm-screw extruder (e.g., Werner and Pfleiderer, Contmua Series) to structure the paste for easier agglomeration. Additionally, structuring agents such as polymers, sodium hydroxide, sodium chloride, postassium hydroxide sihcates and the like can be used to render the paste more suitable for loading higher amounts of surfactant. See Aouad et al, U.S. Patent 5,451,354, issued September 19, 1995. Optionally, high density detergent compositions can be produced by blending conventional or densified spray-dried detergent granules with detergent agglomerates in various proportions (e.g. a 60:40 weight ratio of granules to agglomerates) produced by one or a combination of the processes discussed herein. Additional adjunct ingredients such as enzymes, perfumes, bπghteners and the like can be sprayed or admixed with the agglomerates, granules or mixtures thereof produced by the processes discussed herein. Another process of the invention involves cooling a molten surfactant paste and forming flakes on a chill roll, after which the flakes are ground to the desired particle size. The cooled flakes can be dried further using a rotary drum dryer. 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. EXAMPLE I This Example illustrates the process of the invention which produces free flowing, crisp, high density detergent composition. Two feed streams of various detergent starting ingredients are continuously fed, at a rate of 2800 kg/hr, into a Lodige CB-30 mixer/densifier. One stream comprises a liquid binder containing water and PVNO the other stream containing dry detergent materials containing an ester modified carboxy methyl cellulose, aluminosihcate and sodium carbonate. The rotational speed of the shaft in the Lodige CB-30 mixer/densifier is about 1400 rpm and the mean residence time is about 10 seconds. The contents from the Lodige CB-30 mixer/densifer are continuously fed into a Lodige KM 600 mixer/densifer for further agglomeration during which the mean residence time is about 30 seconds. The resulting detergent agglomerates are then fed to a fluid bed dryer and then to a fluid bed cooler, the mean residence time being about 10 minutes and 15 minutes, respectively. A coating agent, aluminosihcate, is fed after the Lodige KM 600 mixer/densifier to control and prevent over agglomeration. The detergent agglomerates are then screened with conventional screening apparatus resulting in a uniform particle size distribution. The composition of the detergent agglomerate mixture exiting the fluid bed cooler for three process runs are set forth in Table I below: TABLE I Component % Weight of Total Feed A B C Ester Modified Carboxy Methyl Cellulose 5.0 5 0 3.0 PVNO 36.0 41.0 22.0 Aluminosihcate 25.4 24.0 34.0 Sodium carbonate 26.3 24.0 34.0 Polyethylene glycol (MW 4000) 1.1 1.7 2.0 Misc. (water, etc.) 62 eL 100.0 100.0 100.0 EXAMPLE II-V Several detergent compositions made in accordance with the invention and specifically for top-loading washing machines are exemplified below. The base granule is prepared by a conventional spray drying process in which the starting ingredients are formed into a slurry and passed though a spray drying tower having a counter current stream of hot air (200-300°C) resulting in the formation of porous granules. The admixed agglomerates are formed from two feed streams of various starting detergent ingredients which are continuously fed, at a rate of 1400 kg/hr, into a Schugi high shear granulator (1000-4000 RPM) or a Lodige CB-30 mixer/densifier, one of which comprises a liquid binder containing either: 1) PVNO and water or 2) a coploymer of epichlorohydπn and a cyclic amme moiety (IME) and water or 3) the IME material, alkyl ethoxy sulfate surfactant paste and water; and the other stream containing starting dry detergent containing a premixed mixture of either: 1) an ester modified carboxy methyl cellulose, aluminosihcate and sodium carbonate or 2) ester modified carboxy methyl cellulose and aluminosihcate. The rotational speed of the shaft in the Lodige CB-30 mixer/densifier is about 1400 rpm and the median residence time is about 5-10 seconds. The contents from the Lodige CB-30 mixer/densifier are continuously fed into a Lodige KM-600 mixer/densifier for further agglomeration during which the mean residence time is about 1-2 minutes. The resulting detergent agglomerates are then fed to a fluid bed dryer and to a fluid bed cooler before being admixed with the spray dried granules. These agglomerates are then admixed with agglomerates made with a surfactant paste that contains surfactant and water and dry detergent ingredients containing dry detergent material containing aluminosihcate and sodium carbonate. The remaining adjunct detergent ingredients are sprayed on or dry added to the blend of agglomerates and granules. II III IV V Base Granule C\ 5 alkyl sulfate, Na 6.0 19.0 6.0 6.0 Aluminosihcate 15.0 2.0 15.0 15.0 Sodium sulfate 10.0 10.0 10.0 10.0 Sodium polyacrylate polymer 3 0 3.0 3.0 3.0 PolyethyleneGlycol (MW=4000) 2.0 2.0 2.0 2.0 Ci 2_i3 linear alkylbenzene sulfonate, Na 6.0 6.0 6.0 6.0 C14.15 alkyl ethoxylated sulfate, Na 3.0 3.0 3.0 3.0 Sodium silicate 1.0 1.0 1.0 1.0 Bπghtener 24 6 0.3 0.3 0.3 0.3 Sodium carbonate 7.0 7.0 7.0 7.0 DTPA 1 0.5 0.5 0.5 0.5 Admixed Agglomerates Ester Modified Carboxy Methyl Cellulose 0.4 0.4 2.3 2.0 AE3S 8 — — — 0.7 PVNO 1.9 1.9 — — Aluminosihcate 1.3 1.3 2.3 2.1 Sodium Carbonate 1.3 1.3 PolyethyleneGlycol (MW=4000) 0.1 0.1 IME 7 — 0.2 0.2 Sodium Polyacrylate (MW=4500) — 0.2 — Admix c 12-15 alk y J ethoxylate (EO = 7) 2.0 2.0 2.0 2.0 Perfume 0.3 0.3 0.3 0.3 Polyvmylpyrπhdone 0.5 0.5 0.5 0.5 Polyvmylpyπdme N-oxide 0.5 0.5 0.5 0.5 Polyvmylpyrrolidone-polyvinyhmidazole 0.5 0.5 0.5 0.5 Distearylarmne & Cumene sulfonic acid 2.0 2.0 2.0 2.0 Soil Release Polymer 2 0.5 0.5 0.5 0.5 Lipolase Lipase (100.000 LU/I) 4 0.5 0.5 0.5 0.5 Termamyl amylase (60 KNU/g)^ 0.3 0.3 0.3 0.3 CAREZYME® cellulase (1000 CEVU/g) 4 0.3 0.3 0.3 0.3 Protease (40mg/g) 5 0.5 0.5 0.5 0.5 NOBS 3 5.0 5.0 5.0 5.0 Sodium Percarbonate 12.0 12.0 2.0 2.0 Polydimethylsiloxane 0.3 0.3 0.3 0.3 Miscellaneous (water, etc.) balance balance balance balance Total 100.0 100.0 100.0 100.0 1 Diethylene Tnamine Pentaacetic Acid 2 Made according to U.S. Patent 5,415,807, issued May 16, 1995 to Gosselmk et al 3 Nonanoyloxybenzenesulfonate 4 Purchased from Novo Nordisk A/S -> Purchased from Genencor " Purchased from Ciba-Geigy 7 Copolymer of epichlorohydrm and a cyclic am e moiety o Alkyl Ethoxy Sulphate 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.

Claims: WHAT IS CLAIMED IS 1 A process for continuously preparing detergent agglomerates characterized by the steps of (A) continuously mixing a liquid binder and dry detergent materials into a high speed mixer/densifier to obtain detergent agglomerates, wherein the ratio of the liquid binder to the dry detergent material is from 1 : 10 to 10:1 , wherein the dry detergent materials comprise modified carboxy methyl cellulose; (B) optionally mixing the detergent agglomerates in a moderate speed mixer/densifier to further densify and agglomerate the detergent agglomerates; and (C) drying the detergent agglomerates so as to increase their density 2 A process for preparing a high density detergent composition characterized by the steps of: (A) continuously mixing a liquid binder and dry detergent materials into a high speed mixer/densifier to obtain first detergent agglomerates, wherein the ratio of the liquid binder to the dry detergent material is from 1 :10 to 10: 1 , wherein the dry detergent materials comprise modified carboxy methyl cellulose; (B) optionally mixing the first detergent agglomerates in a moderate speed mixer/densifier to increase their density, (C) drying the first detergent agglomerates to further increase their density; (D) continuously mixing a detergent surfactant paste and additional dry detergent materials into a high speed mixer/densifier to obtain second detergent agglomerates, wherein the ratio of the surfactant paste to the additional dry detergent mateπal is (E) mixing the second detergent agglomerates m a moderate speed mixer/densifier to increase their density; (F) drying the second detergent agglomerates to further increase their density; and (G) mixing the first detergent agglomerates and the second detergent agglomerates to form the high density detergent composition. 3. A process according to any of claims 1 -2, wherein the liquid binder is characterized by water, surfactant paste selected from branched and linear anionics, nonionic, zwitteπonic, ampholytic and cationic classes and compatible mixtures thereof, and a polymer selected from the group consisting of dye transfer agents, polyammes, homopolymers and copolymers of polyacrylates, homopolymers and copolymers of polyacrylamides, homopolymers and copolymers of polyvinyl alcohol, homopolymers and copolymers of polyvinyl pyrrohdone, polymaleates, aliphatic polyesters, natural proteins, synthetic non-crystalline polyammoacids, water soluble nylons, polyethylene glycol. polyacrylate and mixtures thereof. 4. A process according to any of claims 1-3, wherein the liquid binder is characterized by: (1) a mixture of surfactant selected from the group of LAS, sodium ethoxysulphate and mixtures thereof; and (2) a polymer selected from the group consisting of a polyvinyl N-Oxide, a copolymer of epichlorohydπn and a cyclic amme moiety, homopolymers and copolymers of polyacrylates and mixtures thereof. 5. A process according to any of claims 1-4, wherein the surfactant paste has a viscosity of from 5,000 cps to 450,000 cps and further is characterized by water and adjunct surfactant selected from the group consisting of nonionic, zwitteπonic, ampholytic and cationic surfactants and mixtures thereof. 6. A process for continuously preparing a high density detergent composition characterized by the steps of: (A) spray drying an aqueous slurry containing adjunct detergent ingredients to form spray dried granules; (B) continuously mixing a liquid binder and dry detergent materials into a high speed mixer/densifier to obtain detergent agglomerates, wherein the ratio of the liquid binder to the dry detergent materials is from 1 : 10 to 10: 1, wherein the dry detergent materials comprise modified carboxy methyl cellulose; (C) optionally mixing the detergent agglomerates in a moderate speed mixer/densifier to increase their density; (D) drying the detergent agglomerates to further increase their density; and (E) blending the granules and the detergent agglomerates together so as to form the high density detergent composition. 7. A process for continuously preparing a high density detergent composition characterized by the steps of: (A) continuously mixing a liquid binder and dry detergent materials into a high speed mixer/densifier to obtain first detergent agglomerates, wherein the ratio of the liquid binder to the dry detergent material is from 1 : 10 to 10.1, wherein the dry detergent materials comprise modified carboxy methyl cellulose; (B) optionally mixing the first detergent agglomerates in a moderate speed mixer/densifier to increase their density; (C) drying the first detergent agglomerates to further increase their density; (D) continuously mixing an acid precursor of an anionic surfactant and additional dry detergent materials which contain an alkaline inorganic material capable of neutralizing the acid precursor into a high speed mixer/densifier to obtain second detergent agglomerates, wherein the ratio of the anionic surfactant to the additional dry detergent materials is from 1 :10 to 10: 1; (E) optionally mixing the second detergent agglomerates in a moderate speed mixer/densifier to increase their density, (F) drying the second detergent agglomerates to increase their density; and mixing the first detergent agglomerates and the second detergent agglomerates to form the high density detergent composition. A process for continuously preparing detergent agglomerates characterized by the steps of: (A) continuously mixing a liquid binder and dry detergent materials into a high speed mixer/densifier to obtain detergent agglomerates, wherein the ratio of the liquid binder to the dry detergent material is from 1:10 to 10:1, wherein the dry detergent materials consist essentially of modified carboxy methyl cellulose; (B) optionally mixing the detergent agglomerates in a moderate speed mixer/densifier to further densify and agglomerate the detergent agglomerates; and (C) drying the detergent agglomerates so as to increase their density. 9. A process according to any of claims 1-8, wherein the liquid binder is characterized by water, surfactant paste selected from branched and linear anionics, nonionic, zwitterionic, ampholytic and cationic classes and compatible mixtures thereof, and a polymer selected from the group consisting of dye transfer agents, polyammes, homopolymers and copolymers of polyacrylates, homopolymers and copolymers of polyacrylamides, homopolymers and copolymers of polyvinyl alcohol, homopolymers and copolymers of polyvinyl pyrrohdone, polymaleates, aliphatic polyesters, natural proteins, synthetic non-crystalline polyammoacids, water soluble nylons, polyethylene glycol, polyacrylate and mixtures thereof. 10 A process according to any of claims 1 -9, wherein the liquid binder is characterized by: (1) a mixture of surfactant selected from the group of LAS, sodium ethoxysulphate and mixtures thereof; and (2) a polymer selected from the group consisting of a polyvinyl N-Oxide, a copolymer of epichlorohydrin and a cyclic amme moiety, homopolymers and copolymers of polyacrylates and mixtures thereof.

Inventors: JONES RICCI JOHN, LEUPIN JENNIFER ANN, SHERRINGTON PAUL RICHARD, TATSUNO TERUAKI, JONES, RICCI, JOHN, LEUPIN, JENNIFER, ANN, SHERRINGTON, PAUL, RICHARD, TATSUNO, TERUAKI
Applicants: PROCTER & GAMBLE, THE PROCTER AND GAMBLE COMPANY
Application year: 1999
Main classification: C11D3
IPC codes: B01J2, C11D1, C11D3, C11D11, C11D17