MXPA96004965A - Procedure for the manufacturing of dedetergent granules of free fl - Google Patents

Abstract

The present invention relates to a process for the manufacture of free flowing detergent granules having a mass density of at least 600 g / l, characterized in that it comprises the steps of: a) neutralizing acid or anionic surfactants in an excess of alkali to form a paste and optionally mix other surfactants with the paste, to give a total surfactant level in the pulp of at least 40% by weight, b) mix said pulp with at least one spray-dried powder, comprising at least about 10% by weight of each anionic polymer and a cationic surfactant to form a granular product, and c) optionally drying the granular product.

Description

^ ROCEDIHIENT PflRfl Lñ MANUFACTURE OF GRANULES OF DETERGENT OF FREE FLOW The present invention relates to a process for the manufacture of free flowing detergent granules having a mass density of at least 600 g / l, which comprises the addition of a spray-dried powder constituted by polymer anionic and cationic surfactant. Cationic surfactants are well-known detergent + detergent ingredients which are used, in particular, to impart a soft feel to the fabrics after they have been washed. The most commonly used cationic surfactants are diponibl.es commercially as aqueous solutions, typically with a surfactant activity of about 35% or 40%. Anionic polymers, such as polycarboxylates, are also well-known detergent ingredients. It has been found to be particularly beneficial to incorporate such polymers into surfactant pastes during the process of preparing high density detergent granules. EP5085 3, published on April 12, 199.1, describes a process in which a surfactant paste with different agents, including polycarboxylate, is structured (or "conditioned") prior to an agglomeration step. The addition of the polymer allowed to achieve ac + ivities < on? oa + ivas more on + a *) this procedure in + o, producing to the same or more granules of detergen + e of the + a density of mass, of free flow, with a fast speed of dissolution. The preparation of granules of lower density comprising tan + or agen + e cationic surfactant with ammonium polymer has been described. US472409Q, February 9, 1988, describes spray-dried powders comprising ammonium copolymers based on an amide monomer. Although this description provides a method for the treatment of commercially available solutions of cationic surfactants, it is not suitable for use in today's compact detergen + ee because the bulk density of the spray-dried product is too high. low. Alternatively, the simple addition of cationic surfactant in the form of a fine powder to a granular matrix +, significantly impairs the dispensing properties of the product. The present invention provides a process for the incorporation of aqueous solutions of high-density surfactants in detergent granules of high activity, high bulk density, and free flow. The objective of the present invention is achieved by complexing polymer to oxide with agen + e ca + i surfactant in solution. The solution is then spray-dried and mixed with high-activity tensile pulps, preferably in a double-screw extruder, «Reversion to the agglomeration giving as a result agglomerate two high active surfactants of desirable properties.

BRIEF DESCRIPTION OF THE INVENTION The present invention provides a process for the manufacture of free flowing detergent granules which have a handle density of at least 600 g / l, comprising. steps of: a) neutralizing acid or ammonium surfactants in an excess of alkali to form paste, and optionally mixing other surfactants with the paste to give a total surfactant level in the pulp of at least 40% by weight; b) mixing said pas + a with one or more powders to form a granular product; and c) optionally drying the granular product, wherein at least one of the powders in step b) is spray-dried and comprises ammonium polymer and ca + ionic surfactant. In a preferred process, step b) comprises the steps of: b) (i) mixing said pulp with a spray-dried powder comprising ammonium polymer and cationic cationic agent + te-ens? Oac + iovo to form a homogenous pasty mixture; and subsequently L > ) (n) mix the homogeneous slurry mixture with > Additional olvos in an al + o effort mixer <; or < n + < > to form the granular product. The spray-dried powder added in step b) comprises preferably + e: (I) from 10 to 90%, most preferably from 10 to 70% by weight of a ca + lomeo surfactant; and (II) from 10 to 90%, most preferably from 30 to 90% by weight of a polymer, said polymer comprising functional groups that are unique. Furthermore, it is preferred that the spray-dried powder comprises less than 10% by weight, preferably less than 5% by weight (on anhydrous basis) of inorganic components. Inorganic components are present, however, the component dried by asp > The product should include less than 5% by weight (on an anhydrous basis) of alkylsilicate, carbonate, and tppolium phosphate. It is also preferred that the spray-dried powder contains less than 10%, most preferably less than 1% by weight ammonium surfactant. A useful ammonium polymer (II) is one that comprises carboxylate functional groups. Such a polymer can be selected from the group consisting of water-soluble salts of furnace and copolymers of aliphatic carboxylic acids such as acrylic acid, rnalide acid, vimlico acid, itaconic acid, rnesaconic acid, fumaric acid, acoustic acid, acid ci + racomco, acid met ilenmalo co, aspar-tico acid and mixtures of the same. Especially useful are the Hydrophobically modified olicarboxylates (are partially M with long-chain alcohols). Most preferably the ammonium co-polymer (TI) is a copolymer of maleic and acrylic acid having a molecular weight of from 2,000 to 100,000. A useful cata-ionic surfactant (I) is a quaternary ammonium salt such as dirnethylammonium chloride. Disodium or dirnetyletoxiarnome chloride of coconut.

DETAILED DESCRIPTION OF THE INVENTION The Pastes One or more aqueous pastes of the ammonium surfactant salts, and optionally nonionic surfactants for use in the present invention are preferred, preferably comprising the sodium salt of the ammonium surfactant. In a preferred embodiment, the ammonium surfactant, or mixture of anionic / nonionic surfactants is preferably as concentrated as possible (ie, with the moisture content as low as possible allowing it to flow in the form of a liquid), so that it can be pumped at temperatures at which it remains stable. Although granulation is known using various pure or mixed surfactants, for the present invention to be of practical use in industry and to give as a result some of the physical properties suitable for incorporation into granular detergents, a vjen + e tensí oac + j vo should be part of the paste at a concentration of preferably 40 to 95%, most preferably 60 to 85% by weight. It is preferred that the moisture in the paste < u: tensive surfactant is as low as possible, while maintaining the flow of the paste, since the low humidity produces a higher concentration of the surfactant in the finished particle. Preferably, the paste contains between 0 and 40% water, preferably between 5 and 30% water and most preferably between 5 and 20% water. A highly attractive form of operation to reduce the humidity of the paste prior to entering the agglomerator without problems with very high viscosities, is the installation in line of an atmospheric or vacuum dryer whose outlet is connected to the agglomerator. It is preferable to use high activity surfactant pastes to minimize the total water level in the system during mixing, granulation and drying. Lower water levels allow: (1) a higher activity surfactant for the ratio of the improver, for example 1: 1; (?) high levels of other liquids in the formula without causing granular- or mass glutinosity; and (3) granular drying methods to meet the final moisture limits. Two parameters i carry + os of the surfactant pastes that can affect the step of granulation and mixing are the temperature and the viscosity of the paste. The Viscosity is a function, among others, of concentration and temperature, with a scale in this application of up to 10,000 Pas, approximately. Preferably, the viscosity of the paste entering the system is from about 1 Pas to 100 Pas. And most preferably from 10 Pas to approximately 70 Pas. The viscosity of the paste of this invention is measured at a temperature of 70 ° C and at a cutting rate of 25 s_1- The paste can be introduced into the mixer- at an initial temperature between its softening point (generally in the range of 20 to 60 ° C) and its degradation point (depending on the chemical nature of the pas + a, for example, alkyl sulphate pastes tend to degrade above 75-85 ° C). High temperatures reduce the viscosity by simplifying pumping of the pulp, but as a result agglomerates of less activity. The use of cooling steps in the line is the preferred way to increase the agglomerate activity. The use of moisture reduction steps in the line (for example flash drying), however, requires the use of higher temperatures (above 100 ° C). In the present invention, the activity of the agglomerates is kept high due to the removal of moisture. The introduction of the paste into the mixer can be done in many ways, from simple emptying to pumping at high pressure through small holes in the end of the duct, before entering the mixer. Although «All these forms are viable for manufacturing agglomerates < On certain physical properties, it has been found that, in a preferred embodiment of the present invention, the extrusion of the paste results in a better distribution in the mixer which improves the yield of particles with the desired size. The amount of high pumping pressures prior to entering the mixer results in increased activity in the final agglomerates. Combining both effects, and introducing the paste through holes (extrusion) small enough to allow the desired flow rate but maintaining the pump pressure at a maximum allowed in the system, highly advantageous results are achieved.

High Activity Tensioactive Paste The activity of the pasta + ens? Oacti is watery is at least 40% and can go up to 95% aproximadament; preferred activities are 60 to 85%, most preferred 70 to 85% ..

At higher concentrations of activity, little or no improver is required for cold granulation of the pulp, the resulting high activity surfactant granules can be added to dry builders or powders or used in conventional agglomeration operations. The aqueous surfactant paste contains an organic surfactant selected from the group consisting of ammonium, non-ionic, zwitterionic, ampholytic and cathic surfactants, and mixtures. 'you the same ones. Ammonium salts and ammonium and nonionic mixtures are preferred. Agen + is useful surfactants herein are listed in U.S. Patent No. 3,664,961, Norris, issued May 23, 1972, and U.S. Patent No. 3,919,678, Laughlin et al., Issued in US Pat. December 30, 1975. The following are representative examples of surfactants useful in the present compositions. Water-soluble salts of the higher fatty acids, that is, "soaps", are useful ammonium surfactants in the present compositions. These include alkali metal soaps such as the sodium, potassium, ammonium salts and alkylammonium 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 fatty acids. Particularly useful are the sodium and potassium salts of the fatty acid mixtures derived from coconut oil and tallow, that is, sodium or potassium soap from tallow and coconut. Useful ammonium surfactants also include the water soluble salts, preferably the alkali metal, ammonium and alkylammonium salts, of organic sulfuric reaction products having in their molecular structure an alkyl group containing from 10 to 20 carbon atoms, approximately, and an oster group of acid or only acid or Sulfuric. (Included in the term "alkyl" is the alkyl portion of the acyl groups). Examples of this group of synthetic surfactants are sodium and potassium alkylsulfates, especially those obtained by sulfation of higher alcohols (8 to 18 carbon atoms) such as those produced by reduction of tallow glycerides or coconut oil.; and the sodium and potassium alkyl benzene sulphonates in which the alkyl group contains from about 15 carbon atoms, in straight or branched chain configuration, for example, those of the type described in U.S. Patent Nos. 2,220,099 and 2,477,383 . Especially valuable are linear straight-chain alkyl benzene sulphonates in which the average number of carbon atoms in the alkyl group is 11 to 13, abbreviated as LAS of C11-C13. Other useful ammonium surfactants herein include the water soluble salts of fatty acid esters to α-sulfonates containing from 6 to 20 carbon atoms in the fatty acid group and from 1 to 10 carbon atoms in the the group; the water-soluble salts of 2-ac? lox acid? -al an- 1-sulfomco, which contain approximately 2 to 9 carbon atoms in the acyl group and approximately 9 to 23 carbon atoms in the alkane entity; alkyl ether fat containing approximately 10 to 20 carbon atoms in the alkyl group and from 1 to 30 moles, approximately, of ethylene oxide; water-soluble salts of olefin sulfonates containing from 12 to 24 carbon atoms; and heta-alkyloxy - ^ Icans? Lfonatos containing 1 to 3 carbon atoms in the alkyl group and from R to 20 carbon atoms in the alkane entity. Although the acid salts are typically discussed and used, the acid neutralization can be carried out as part of the fine dispersion mixture step. Water-soluble nonionic surfactants are also useful as surfactants in the compositions of the invention. Actually, the preferred processes use ammonium / nonionic mixtures. A particularly preferred paste comprises a mixture of nonionic and ammonium surfactants having a ratio of 0.01: 1 to 4: 1, approximately. Such nonionic materials include compounds produced by the condensation of alkylene oxide groups (hydrophilic 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 quickly adjusted to produce a water-soluble compound having the desired degree of balance between the hydrophilic and hydrophobic elements. Suitable nonionic surfactants include the polyethylene oxide condensates of alkylphenols, for example, the alkyl phenol condensation products having an alkyl group having 6 to 16 carbon atoms, either in straight or branched chain configuration, with about 4 to 25 moles of ethylene oxide per mole of alkyl phenol.

Preferred nonionic surfactants are the water-soluble condensation products of aliphatic alcohols containing from 8 to 22 carbon atoms, either in straight or branched chain configuration, with 2 to 25 moles of ethylene oxide. per mole of alcohol. Particularly preferred are the condensation products of alcohols having an alkyl group containing from 9 to 15 carbon atoms with approximately 2 to 25 moles of ethylene oxide per mole of alcohol, and condensation products of propylene glycol with ethylene oxide . Other preferred nonionic surfactants are the polyhydroxy fatty acid amides, such as tallow N-methygi ucosarnide, and alkyl polylucoside. Semi-polar non-ionic surfactants include water-soluble amine oxides containing an alkyl moiety of from 10 to 18 to + about carbon atoms + 2 and 2 selected from the group consisting of alkyl groups and hydroxyalkyl groups containing 1 to 20 carbon atoms. to 3 carbon atoms, approximately; water-soluble foefma oxides containing an alkyl entity of approximately 10 to 18 carbon atoms, and 2 entities selected from the group consisting of alkyl and hydroxyalkyl groups containing from 1 to about 3 carbon atoms; and water-soluble sulfoxides which have an alkyl entity of about 10 to about 18 carbon atoms, and an entity selected from the group consisting of alkyl or alkyl groups. n "1-to-3-atomized hydroxyl-alkyl atoms." Ampholytic surfactants include aliphatic thio-ivatides of heterocyclic secondary and tertiary amines on which the aliphatic entity may be either rec + a or branched chain and where One of the aliphatic substrates + contains from 8 to 18 carbon atoms and at least one aliphatic substituent contains an ammonium group of water solubilization Zwitterionic surfactants include phosphorus derivatives of quaternary ammonium to the phatic, and compounds of sulfonyl in which one of the aliphatic substituents contains from 8 to 18 carbon atoms.

Incorporation of the spray-dried powder The preferred cationic surfactants are water-soluble quaternary ammonium salts containing 1 or 2 long alkyl groups with 10 to 14 carbon atoms, and 2 to 3 short alkyl groups each of which contains no more than 2 carbon atoms and optionally have ethoxy groups. Useful cationic surfactants include water-soluble quaternary ammonium compounds of the form R4 Re Rß R? N + X-, wherein R is alkyl having from 10 to 20, preferably from 12 to 18 carbon atoms, and Rs is Ci to C20, Rβ and R7 are each Ci-C7 alkyl, preferably methyl; * ~ is an anion, for example chloride. Millions of such compounds of tpmet llamon 10 include chloride.

J-cyclopethylammonium of Ci2-i4, C12-14 alkyldi ethylethylammonium chloride and inetosulfato of < ocalquil t rirnetilarnomo. Other useful cationic surfactants are described in U.S. Patent No. 4,222,905, Cockrell, issued September 16, 1990 and U.S. Patent No. 4,239,659, Murphy, issued December 16, 1980. Useful organic polymers can also function as detergency enhancers. Included among such polymers there may be mentioned lower alkyl carboxycelluloses, lower alkyl sodium celluloses and sodium hydroxylacid celluloses, such as sodium carboxy ethylcellulose, sodium methylcellulose or sodium hydroxypropylcellulose, polyacrylates and different copolymers such as those of rnalé co and acpl ico acid. Molecular weights for such polymers go widely but most are within the range of 2,000 to 100,000. Polymeric polycarboxylate enhancers are disclosed in U.S. Patent No. 3,308,067, Diehl, issued March 7, 1967. Such materials include water-soluble furnace salts and euphoners of aliphatic carboxylic acids such as acrylic acid, rnaleic acid, vinyl acid, itaconic acid, mesacom acid, fumaric acid, aconitic acid, citracóco acid, acid rnet 1 lenrnaló co and aspar ico acid. The spray-dried powder comprising the agent catiomco and the f > Ammonium oxide can be prepared by any conventional method, such as spray drying using pressure nozzle, double fluid nozzle or rotating disk atomizer. The rotating disk atomizer and the dual fluid nozzle are preferred. The spray-dried powder is preferably mixed with the high activity surfactant paste to form a uniform pasty mixture. Optional + e, the high activity paste can also be thickened or "structured". Suitable thickeners or structuring agents are fatty acids, fatty acid soaps, silicates and polymers. It is preferred that the mixture in this step be treated in an extruder.

The extruder The extruder fulfills the functions of pumping and mixing the viscous surfactant paste in a continuous base. A basic extrusion consists of a barrel with a smooth inner cylindrical surface. Mounted inside this barrel is the extrusion extrusion helix. There is a gateway for the high activity pulp which, when the propeller is turned, causes the pulp to move along the length of the barrel. Additional doors in the barrel may allow other ingredients, including spray-dried powder, to be added directly into the barrel. A preferred extruder is the double-screw extruder. k ^ G type of extruder has two helices mounted in parallel within the same barrel, which are rotated either in the direction (co-ro + ac on) or in directions as + as (cont ra-rotation). The most preferred piece of equipment to be used in this invention is the double-screw extruder. Double helix extruders suitable for use in the present invention include those provided by: APV Baker, (CP series); Uerner and Pfleiderer, (Sene continuous); - Wenger, (SerieTF); Leist itz, (Series ZSE); and Buse, (Sene LR).

High Shear Blend and Granulate The term "high shear mix" as used herein means mixing and / or granulating the past pasty mixture with powders in a high shear mixer at a peak rate of palette from 5rn / sec to 50 n / sec, approximately, unless otherwise specified.

The total residence time of the mixing and granulating processes is preferably in the order of 0.1 to 10 minutes, preferably 0.1 to 5 minutes and preferably 0.2 to 4 minutes. The preferred peak rates of mixing and granulation are 10-45 m / sec, and 15-40 rn / sec, approximately. The mixture ratio of pasty to powder should be chosen to maintain discrete particles at all stages of the process. These particles can be sticky but must flow substantially in free form, so that the steps of L7 Sizing and granulation can be carried out simul- taneously, or immediately sequentially without causing blockage of the finisher / granulator. Any suitable apparatus, plant or unit for the treatment of surfactants can be used to carry out the process according to the invention. Suitable apparatuses include, for example, film drop sulfonation reactors, digestion tanks, fuel reactors, etc. For mixing / agglomeration, any of several mixers / agglomerators can be used. In a preferred embodiment, the method of the invention is carried out continuously. Especially preferred are the mixers of the FukaeR FS-G series, manufactured by Fukae Powtech Kogyo Co., Japan; this apparatus is essentially in the form of a cup-shaped container, accessible through an upper door, provided near its base with a stirrer having a substantially vertical axis, and a cutter positioned on a side wall. The agitator and the cutter can operate independently of each other and at variable speeds separately. The container can be adapted with a cooling jacket or, if necessary, a cryogenic unit. Other similar mixers that are suitable for use in the process of the invention include Diosna "Sene V ex LDierks ft Smile, Germany, and the Pharrna Matrix R ex T K Fielder I td., England.

Suitable mixers for use in the process of the invention are the Fuj? R series VG-C ex Fuji Sangyo Co. , Jap n -y RotoR ex Zanchetta 8¡ Co srl, Itlia. Other suitable suitable equipment could include - EipchR, RV series, manufactured by Gustau E rich Hartlhe rn, Germany; Lod? GeR, series CB and KM, in series for continuous mixing / agglomeration, manufactured by Lbdige Machmenbau GmbH, Paderborn Germany; Dra? SR series T160, manufactured by Dra s Uer- e GmbH, Mannheim Germany; and U? nk orthR series RT 25, manufactured by Winkwor-th Machinery Ltd., Bershire, England. Two examples of suitable mixers are the Littleford mixer, model # FM-130-D-12, with pal + as internal mincers and the Cuisinart food processor, model # DCX-Plus, with 7.75-inch (19.7 crn) pallets. Any other mixer with granulation and fine dispersion mixing capability and having a residence time of the order of 0.1 to 10 minutes can be used. The "turbine-type" mixer-propeller is preferred, which has several vanes on an axis of rotation. The invention can be practiced as a continuous or intermittent process.

Operating temperatures The preferred operating temperatures should also be low as is possible because this causes a concentration of surfactants more than in the finished particle. Preferably, the heat during the The pressure is less than 100 ° C, preferably no more than 10 and 90 ° C and very preferably between 25 and 80 ° C. Useful operating temperatures lower than the procedure of the present invention can be achieved. by a variety of methods known in the art such as nitrogen cooling, cold water equipment chamfering, addition of solid CO2, and the like, with solid CO2 being a preferred method, and nitrogen being the preferred method.

Powders Many powders are suitable for use in the granulation step of the present process. Preferred powders for use in the process and compositions of the present invention are compatible detergency builder or combination of builders or powder. The detergent compositions herein may contain ion exchange material of the crystalline mosicalic acid of the formula Naz [(AIO2)? - (S? 02) and l-xH20 where z and y are at least about 6, the molar ratio z to y is from about 1.0 to 0.4 and z is from about 10 to about 264. Materials of amorphous hydrated alumina, which are useful herein, have the Mn (, 'A102-y? 02) ernpile formula wherein M is .odium, potassium, ammonium or substi tuted ammonium, z is ^ 0.5 to 2, approximately, and y is l, said material having a magnesium ion exchange capacity of at least about 50 milligrams equivalent of CaC 3 hardness per gram of anhydrous inosilicate alum. Sodium hydrated zeolite A with a particle size of about 1 to 10 microns is preferred. The improved ionic alkylsilica ion exchange materials herein are in the hydrated form and • "* contain from 10 to 28% by weight of water, approximately, if they are crystalline, and potentially even greater amounts of water if they are amorphous. The highly preferred crystalline exchange materials have 18-22% in water. In its crystalline matrix, the ion-exchange materials of crystalline algae are further characterized by a particle size diameter of from 0.1 to 10 microns, and amorphous materials are often smaller, for example, below 0.01 microns. Preferred ion exchange materials have a particle size diameter of about 0.2 to 4 microns.The term "particle diameter +" is represented herein as the size diameter of the average particle by weight of a material. of ion exchange, as determined by conventional analytical techniques such as for example microscopic determination or Using an electron microscope has scrutiny. The ion exchange materials of crystalline alosilicate in the present if) too often characterized by its calcium ion exchange capacity, which is at least 200 g of water hardness equivalent of CaCO3 / g of alummosilica + o, calculated on anhydrous basis, and which is generally in the scale of 300 mg eq./ga approximately 352 g eq./g. The ionic inosilicate ion exchange materials herein are also characterized by their calcium ion exchange ratio which is at least 2 grains of -? Ca + + / 3.78 liters / rn? Nuto / grarno / 3.78 liters of aluminosilicate (anhydrous base), and is generally within the range of approximately 2 grains / 3.78 l Ltros / m? Nuto / gram / .78 liters a approximately 6 grains / 3.78 liters / punuto / grarno / 3.78 liters, based on the calcium ion hardness. The alumina, or optimum for detergency improvement purposes, exhibits a calcium ion exchange ratio of at least about 4 grains / 3.78 liters / minute / gram / 3.78 liters. The amorphous aluminosilicate ion exchange materials usually have an Mg ++ exchange of at least about 50 mg eq. CaC 3 / g (12 mg Mg ++ / g), and an exchange ratio of Mg ++ of at least about 1 grain / 3.78 liters / rn? Nuto / gram / 3.7B liters. Amorphous materials do not exhibit an observable diffraction pattern when examined with Cu radiation (1.54 Angstrom units). The ion exchange materials of alternosi 1 ica + or useful in the practice of this invention are 0 0 ^ commercial ples bios. The useful alu i nosilicatos in '- t,! The invention can be of crystalline or pure nature and can be of natural occurrence or synthetically derived. A method for the production of ionic exchange materials is the inosilicate is discussed in U.S. Patent No. 3,985,669, Kru mel et al., Issued October 12, 1976, incorporated herein by reference. Preferred ion exchange materials of synthetic crystalline allufosilicum, useful herein, are available under the names of Zeolite A, Zeolite B, Zeolite P, Zeolite MAP and Zeoite X. In an especially preferred embodiment, the ion exchange material of aluminosilicate crystalline has the formula Na? 2r (A102] i2 (Sl02)? 2] -xH2? where x is from 20 to 30 approximately, especially near 27 and has a generally smaller particle size of 5 microns. of the present invention may contain alkaline or neutral salts having a solution pH of 7 or higher, and may be either organic or inorganic in nature.The builder salt helps to provide the desired density and volume to the detergent granules in the present Although some of the salts are inert, many of them also function as detergent-improving materials in the laundry solution.

Examples of neutral water-soluble salts include chlorides, fluorides and sulfates of alkali metal, ammonium or substituted ammonium. Preference is given to the above alkali metal salts, especially sodium. Sodium sulfate is typically used in detergent granules and is a particularly preferred salt. Citric acid and, in general, any other organic or inorganic acid can be incorporated into the granular detergents of the present invention as long as they are chemically compatible with it. rest of the agglomerate composition. Other useful water-soluble salts include the compounds commonly known as builders. The detergency builders are generally selected from the various alkali metal, ammonium or substituted ammonium phosphates, poly phosphates, phosphonates, polyphosphonates, carbonates, silicates, borates, citrates, silicas and polyhydroxysulfonates. Preference is given to the above alkali metal salts, especially sodium. Specific examples of inorganic phosphate builders are tripolyphosphate, pyrophosphate, polymeric metaphosphate, having a degree of polymerization tie 6 to 2.1. approximately, and orthophosphate, sodium and potassium. Examples of poly detergency builders. Phosphonate are the potassium and sodium salts of ethylene-osphonic acid, the sodium and potassium salts of ethane-1-hydroxy-1,1-diphosphonic acid, and the sodium and potassium salts of ethane-1, 1, - trifosfon? co.

Other phosphorus builders, detergency builders, are disclosed in U.S. Patent Nos. 3,159,581; 3,213,030; 3,422,021; 3,422,137; 3,400,175 and 3,400,140, incorporated herein by reference. Examples of non-phosphorus inorganicdetergency builders are carbonate, bicarbonate, sesquicarbonate, tetraborate decahydrate and sodium and potassium silicate having a SiO 2 molar ratio to alkaline metal oxide of about 0.5 to 4.0, preferably about 1.0 to about 2.4. Highly preferred materials in the silicate class are the crystallized statified sodium silicates of the general formula: wherein M is sodium or hydrogen, x is a number from 1.9 to 4, and is a number from 0 to 20. Crystallized statified sodium silicas of this type are described in EP-A-0164514, and methods for their preparation are described in DE-A-3417649 and DE-A-3742043. For the purposes of the present invention, x in the above general formula has a value of 2, 3 or 4 and is preferably 2. Most preferably M is sodium and y is 0, and preferred examples of this formula comprise the t and 6 Na 2 forms Í2? S. These materials are available from Hoechst AG FRG, such as NaSKS-11 and NaSKS-6, respectively. The preferred material is 6 ~ Na2? 2? S, (NaSKS-6). The crystalline stained silicates are incorporated either as dry mixed solids, or as solid agrometer components with other solids. ?? t mponentes The compositions made by the proceed meen * < > d < the present invention does not require excess carbonate-treatment, and preferably does not contain more than 2% finely divided calcium carbonate as described in U.S. Patent No. 4,196,093, Clarke et al., issued April 1, 1980, and preferably it's free of the same.

EXAMPLES All% are percentages by weight unless otherwise specified.

Example 1 a) Formulation of the spray-dried particle The following free-flowing powder composition was prepared: Acrylic / rnaleic copolymer (MW = 50,000) 61% Alkyl chloride with hydroxy fatty acid 30% Water 9% 100% The composition was prepared by mixing an active 40% solution of the sodium salt of the copolymer and a 40% solution. • otiva of loruro of al quildimet ilhidrox et ílarno or of fat, to give a well mixed suspension. Then the suspension is treated through a continuous spray dryer with a concurrent inlet and a rotating disk (15000 rpm) in the upper part of the tower.

After the exit from the bottom of the tower, the product is further dried and cooled in a fluidized bed dryer and a fluidized bed fluid cooler. After classification (removal of fine and coarse particles) by vibration screens, the resulting spray-dried powder has an apparent bulk density of 250 g / 1. b) Incorporation of the spray-dried powder into a high density granule An aqueous tenective active paste was prepared comprising: -62.5% by weight of sodium alkyl sulfate having substantially C12, C14 and C15 alkyl chains; 15.5% by weight sodium alkyl ethoxysulfate having substantially alkyl chains of C12 to Cl 5 and an average of 3 ethoxy groups per molecule; 17% by weight has water and the rest being comprised mainly of alcohol and unreacted sulphates. The aqueous surfactant paste and the powder compound described in Example 1 were intimately mixed in a double helix extruder (manufactured by Uerner &P leiderer, 170). The resulting viscous paste was extruded (at a temperature of 60 ° C) directly into a Loedig CB30 high speed mixer (trademark), which contained a mixture of 2 parts of zeolite A to 1 part light carbonate finely divided . The mixer operates on a continuous base and unloads directly into a continuous grate mixer Loedige KM 300 (Commercial brand). The resulting agglomerates are transferred to / a fluid bed dryer, cooled in a fluidized bed cooler and then sorted through mesh screens to remove coarse and fine particles. The agglomerates formed have an ammonium surfactant content of 40% by weight, a polymer level of 14%, a level of cationic surfactant of 7% and a relative humidity level of 10% at room temperature. The granules have an apparent handle density of 680 g / l, and have excellent flow and handling properties.

Example 2 The following flow-free powder composition was prepared with the same procedure described in Example 1 (a).

Acrylic / Nale Copolymer (MW = 50000) 45% Alkyldimethylhydroxyethylammonium chloride 45% Water 10% 100% This powder has a mass density of 300 g / l. This powder was then incorporated into a free-flowing high-density particle, with the same procedure as described in example 1 (b), (except that the composition of the powder mixture entering the high-speed mixer was: zeolLta A, 42%, 58% light sodium carbonate) to give a granular free-flowing product having an ammonium surfactant content of 40%, a polymer content of 7%, - a level of cationic surfactant of 7% and a relative humidity level in equilibrium of 10% at room temperature. The granules have an apparent bulk density of 700 g / 1 and have excellent flow and handling properties.

Claims (12)

NOVELTY OF THE INVENTION CLAIMS

1. - A process for the manufacture of free flowing detergent granules having a mass density of at least 600 g / 1, comprising the steps of: a) neutralizing acid or ammonium surfactant acids in an excess Alkali to form paste, and optionally mix other surfactants with the paste, to give a total surfactant level in the pulp of at least 40% by weight, b) mix said pulp with one or more powders to form a granular product, and c) optionally drying the granular product, characterized in that at least one of the powders in step b) is spray dried and comprises ammonium polymer and cationic surfactant. to claim 1 wherein step b) comprises the steps of: b) (i) mixing said pulp with at least one spray-dried powder consisting of ammonium polymer and cationic surfactant to form a homogeneous slurry, and subsequently , b) (n) mixing the homogeneous slurry with additional powders in a high shear mixer to form the granular product 3. A process according to any of the claims 2, characterized furthermore because the 10 • lvo spray drying comprises T) from 10 to 90% by weight of a cationic surfactant; TI) of 10 to 90% in e or of a polymer, said polymer comprising functional groups that are unique. 4. A method according to claim 3, further characterized in that the spray-dried powder comprises 10% by weight (in anhydrous basis) of inorganic components. 5. A process according to claim 4, further characterized in that the spray-dried powder comprises less than 5% by weight (based on anhydrous) of inorganic conponentee. 6. A method according to claim 4 or 5, further characterized in that the spray-dried powder comprises less than 5% by weight (on anhydrous basis) of aluminosilicate, carbonate and t-polyphosphate. 7. A method according to claim 3, further characterized in that the spray-dried powder comprises less than 10% by weight of ammonia surfactant. 8. A method according to claim 7, further characterized in that the spray-dried powder comprises 10% by weight tons of ammonium tonsion. 9. A method according to claim 3, further characterized in that the polymer (TI) , ornprende carboxy lato functional groups. 10. A method according to claim 9, further characterized in that the polymer (II) is selected from the group consisting of water-soluble salts of homo- and copolymers of aliphatic carboxylic acids such as acrylic acid, maleic acid, vinyl acid , itaconic acid, rnesaconic acid, fumaric acid, aconitic acid, citraconic acid, methylene-alonic acid, aspartic acid and / _ ezclas of the same. 11. A method according to claim 10, further characterized in that the polymer (II) is a copolymer of maleic acid and acrylic having a molecular weight of 2,000 to 100,000. 12.- A procedure according to the claim 3, further characterized in that the cationic surfactant (I) is a quaternary ammonium salt.