MXPA99007936A - Process for making a detergent composition by adding co-surfactants - Google Patents

Abstract

A process for continuously preparing a free flowing agglomerate having a reduced level of resulting undesirable oversized granules is provided. The process comprises the steps of (a) thoroughly mixing a crystalline anionic surfactant paste with a sufficient amount of fine powders of starting detergent materials to form a free flowing agglomerate, then (b) thoroughly mixing a product of the step (a) with a non-crystalline anionic surfactant paste so as to form a free flowing agglomerate.

Description

PROCEDURE FOR MANUFACTURING A DETERGENT COMPOSITION BY ADDING SURFACTANT AGENTS FIELD OF THE INVENTION The present invention relates generally to a process for producing a detergent composition. More particularly, the invention is directed to a non-tower process during which the detergent granules are produced by adding co-surfactants. The process produces a free-flowing detergent composition, whose density can be adjusted for a wide range of consumer needs, and which can be sold commercially.

BACKGROUND OF THE INVENTION Recently, there has been considerable interest within the detergent industry to produce modern detergent compositions for flexibility in the final density of the final composition. In general, there are three main types of procedures by which detergent granules or powders can be prepared. The first type of process involves spray drying a sharp aqueous detergent paste in a spray drying tower to produce highly porous detergent granules (eg, tower procedures for low density detergent compositions). The second type of process involves spray drying an aqueous detergent slurry in a spray-drying tower as the first step, then the resulting granules are agglomerated with a binder such as a non-ionic or anionic surfactant, finally, various detergent components they are dry blended to produce detergent granules (eg, tower process plus towerless process [agglomeration] for high density detergent compositions). In the third type of process, the different detergent components are mixed dry after which they are agglomerated with a binder such as a nonionic or anionic surfactant, to produce high density detergent compositions (non-tower process [agglomeration] for detergent compositions) high density). In the three above processes, the important factors that govern the density of the resulting detergent granules are the shape, porosity and particle size distribution of said granules, the density of the different starting materials, the shape of the different starting materials. , and its respective chemical composition. It is often desirable, for performance reasons, to use a mixture of surfactants. Such surfactants are typically prepared in the form of aqueous pastes (typically 25-70% active). When agglomerated granules are prepared from mixtures of said surfactant pastes, there are two generally used methods. A typical method is; surfactant agents in the form of pulp are mixed as to form a co-surfactant paste, followed by agglomeration of the pulp in a mixer, or in a series of mixers with dry ingredients as builders (for example sodium tripolyphosphate) , inorganic fillers (for example sodium sulphate), bleaches, etc. This method is not always desirable in terms of finished product quality. For example, blending even a relatively small amount of a non-crystalline surfactant paste, (ie the paste of a type of surfactant that is typically tacky and difficult to be applied in an agglomeration process), with a paste of crystalline surfactant, (ie, a type that is typically easy to apply in an agglomeration process), results in a co-surfactant paste having the nature of the paste of a non-crystalline surfactant. In other words, this type of method typically causes tackiness of a co-surfactant paste, when the co-surfactants include a non-crystalline surfactant, because said non-crystalline surfactant is generally tacky. Consequently, granules made by this method generally include a large amount of undesirable oversized agglomerates. Some reduction in the amount of oversized agglomerates can be achieved by using relatively large amounts of flow aids such as zeolites and silicates in the agglomeration step. This, however, results in added expenses. Another typical method is that each type of surfactant is formulated in separate agglomerates and then both agglomerates are mixed. This method is typically not desirable because the cost for parallel agglomeration is rather expensive. Accordingly, a need remains in the art to have a process for producing a detergent composition which reduces the level of resulting undesirable oversized agglomerates, when the starting detergent materials include a co-surfactant which is not crystalline. In addition, there is a need for a process that is more efficient, flexible and economical to facilitate the large-scale production of detergents for flexibility in the final density of the final composition.

TECHNICAL BACKGROUND The following references are directed to the densification of 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 the production of detergents by agglomeration: Beerse et al., U.S. Patent No. 5,108,646 (Procter &Gamble); Capeci et al., U.S. Patent No. 5,366,652 (Procter &Gamble); Hollingsworth et al., European Patent Application 351, 937 (Unilever), and Swatling et al., U.S. Patent No. 5,205,958. Japanese Laid-Open Patent Application, No. H5-171 199 (Lion), discloses a bulk high density granular detergent composition comprising a fatty acid lower alkyl ester sulfonate ("co-surfactant 1") and an agent anionic surfactant except that co-surfactant 1, silicate, and carbonate. This composition is described as preventing the hydrolysis of co-surfactant 1 after long-term storage.

BRIEF DESCRIPTION OF THE INVENTION The present invention meets the needs mentioned above in the art by providing a towerless process, especially an agglomeration process, which produces a granular detergent composition having a final density of the final granular composition. The present process is stable in terms of flowability and cost effectiveness, because the process reduces the level of undesirable oversized granules and / or the level of process flow aids, such as zeolites and / or silicates, which prevent over agglomeration. Accordingly, the process of the present invention is more efficient, economical and flexible in relation to obtaining detergent compositions having less oversized granules (ie agglomerates). As used herein, the term "agglomerates" refers to particles formed by the agglomeration of starting materials with binders such as surfactants and / or inorganic solutions / organic solvents and polymer solutions. As used herein, the term "crystalline (anionic) surfactant paste" refers to the surfactant (anionic) paste having a crystalline structure, generally having 50-100%, preferably 65-100% , more preferably 80-100% crystallinity, as measured by X-ray defraction (XRD). As used herein, the term "non-crystalline (anionic) surfactant paste" refers to the surfactant (anionic) paste that is not a crystalline (anionic) surfactant paste as defined above. All percentages used herein are expressed as "percentage by weight" unless otherwise indicated. The present invention provides a process for preparing a granular detergent composition, the process consisting of: (a) thoroughly mixing a paste of crystalline anionic surfactant with a sufficient amount of fine powders of starting detergent materials to form a free flowing agglomerate; (b) intensively mixing a product of step (a) with a paste of non-crystalline anionic surfactant to form a free-flowing agglomerate; It is provided.

An agglomerate from the process of the present invention has a reduced level of undesirable oversized granules resulting. Also provided are the granular detergent compositions produced by any of the process modalities described herein. Accordingly, it is an object of the invention to provide a method for continuously producing a free flowing agglomerate, which reduces the level of undesired oversized granules resulting. It is also an object of the invention to provide a method that is more efficient, flexible and economical to facilitate the large-scale production of detergents of low as well as high dosage levels. These and other objects, features and concomitant advantages of the present invention will be apparent to those skilled in the art from a reading of the following detailed description of the preferred embodiment and the appended claims.

DETAILED DESCRIPTION OF THE PREFERRED MODALITY The present invention is directed to a process that produces granular, free-flowing detergent composition, by controlling the tackiness derived from a paste of non-crystalline surfactant.

PROCESS First step In the first step of the process, a paste of crystalline anionic surfactant and finely ground detergent ingredients (hereinafter, fine powders), as builders, are supplied into a mixing equipment and then agglomerated by dispersing the surfactant agent paste on the fine powders, so as to form a free flowing agglomerate. Optionally, other starting detergent materials can also be supplied within the equipment in this step. In this step, the amount of fine powders required in the first step depends on the amount of crystalline anionic surfactant paste and the water content of the paste. The equipment examples for the first step can be any type of agglomeration equipment known to those skilled in the art. A suitable example may be a mixer, such as Lddige CB Mixer, Lódige KM Mixer, or Drais K-TTP. The agglomeration condition including the time for the first step depends on the type of equipment used for the first step, such as to produce an agglomerated homogeneous mixture. Such conditions can also be decided based on the design of the final composition from the process of the present invention.

Sequence step In the second step of the process, the resultant of the first step, a slurry of crystalline anionic surfactant and fine powders are mixed together further to form a free flowing agglomerate. Optionally, other starting detergent materials can also be supplied within the equipment in this step. In this step, the amount of fine powders required to the second step depends on the amount of the anionic surfactant paste (ie, the unreacted paste in the first step and the non-crystalline anionic surfactant paste), and the content of water in the pasta. Optionally, fine powders can be added to the second process. In the second step of the process, a paste of non-crystalline anionic surfactant is added to a resultant of the first step, subsequently, the paste and the resultant are agglomerated further as to form granules / agglomerates. In the second step, fine powders, either used in the first step or other fine powders, can be added additionally to the resultant. The second step can be carried out in the equipment for the first step or in another equipment (second) for agglomeration. The examples of the equipment may be any type of mixer known to those skilled in the art. A suitable example can be a mixer, such as a mixer model Schugi Flexomic, Lódige CB Mixer, Lódige KM Mixer or Drais K-T. Generally, the process of the present invention allows the mixed crystalline anionic surfactant paste of the first step to settle for at least 0.1 second before adding the non-crystalline anionic surfactant paste in the second step. The agglomerated materials during the second step, which include the crystalline anionic surfactant paste and the non-crystalline anionic surfactant paste, have a similar nature to the agglomerates formed from crystalline anionic surfactant paste, ie, less of oversized agglomerates that agglomerates formed from non-crystalline anionic surfactant paste or formed from a mixture of crystalline surfactant paste and amorphous anionic surfactant paste. Accordingly, the second step can be carried out uniformly because the agglomerated material has less amount of oversized agglomerates. In general, the agglomerates of the present process include less than 20% of particles whose diameter is greater than 1180 μm. Preferably, the agglomerates of the present process include less than 15% particles whose diameter is larger than 1 180 μm. More preferably, the agglomerates of the present process include less than 10% particles having a larger diameter of 1 180 μm. The resultant of the second step can be processed for further agglomeration which is well known to those skilled in the art.

In the present invention, the amount (as an active weight ratio) of the fine powders to the amount of crystalline anionic surfactant in the paste can be from 2.0% to 3.2%, preferably from 2.4% to 2.8%. In the present invention, the amount (as an active weight ratio) of the crystalline anionic surfactant in the pulp to the amount of the non-crystalline anionic surfactant in the pulp can be from 4% to 14%, preferably from 6% to 12%. %, more preferably from 8% to 10%.

DETERGENT DETERGENT MATERIALS The starting detergent materials for a granular detergent composition that is made in accordance with the process of the present invention, except for crystalline anionic surfactant agent (s), non-crystalline anionic surfactant (s) and fine powders for the present invention, can be added at any time during or after the previous two steps. Such other starting detergent materials are fully described below.

Detergent surfactant (aqueous / non-aqueous) The total amount of detergent surfactant (ie crystalline anionic surfactant agent (s), non-crystalline anionic surfactant (s) and other surfactants for the final product of the present invention) which can to be used for the present process, may be from 5% to 60%, more preferably from 12% to 40%, more preferably from 15% to 35%, in the total amount of the final product obtained by the process of the present invention. The surfactant itself is preferably selected from anionic, non-ionic, switerionic, ampholitic and cationic classes and compatible mixtures thereof. The detergent surfactants useful herein are disclosed in US Pat. No. 3,664,961 to Norris, May 23, 1972, and in the U.S. Patent. 3,929,678, Laughiin et al., Of December 30, 1975, both of which are incorporated herein by reference. Useful cationic surfactants also include those described in U.S. Patent No. 4,222,905 of September 16, 1980, and in U.S. Pat. 4,239,659, dated December 16, 1980, both of which are also incorporated herein by reference. Of the surfactants, anionics and nonionics are preferred and anionics are most preferred. Non-limiting examples of the preferred anionic surfactants useful in the present invention include the C 11 -C 18 alkyl benzene sulfonates ("LAS"), primary C 10 -C 20 alkyl, branched chain and random alkyl sulfates ("AS"), the alkyl secondary C? 0-C18 sulfates (2,3) of the formula CH3 (CH2) x (CHOS? 3"M +) CH3 and CH3 (CH2) and (CHOSO3" M +) CH2CH3 where x and (y +1) are whole of at least 7, preferably at least 9, and M is a water-solubilizing cation, especially sodium, unsaturated sulfates such as oleyl sulfate, and C10-C? 8 alkyl alkoxy sulfates ("AExS", especially EO ethoxy sulfates) 1-7). Useful anionic surfactants also include water-soluble salts of 2-acyloxy-alkane-1-sulfonic acids containing from 2 to 9 carbon atoms in the acyl group and from 9 to 23 carbon atoms in the alkane portion; water-soluble salts of olefin sulfonates containing from 12 to 24 carbon atoms; and beta-alkyloxy alean sulfonates containing from 1 to 3 carbon atoms in the alkyl group and from 8 to 20 carbon atoms in the alkane portion. Among those anionic surfactants, preferable examples such as crystalline anionic surfactant paste (s) of the present invention include; alkyl sulfates either natural or synthetic, preferably sulfates of coconut fatty alcohol of C? 2-C? 8 or synthetic C-14-C15 alkyl sulfates. Preferable examples such as non-crystalline anionic surfactant paste (s) of the present invention include; alkyl alkoxy sulfates (AExS), alkyl benzene sulphonates (LAS). Optionally, other illustrative surfactants useful in the paste of the invention include C10-C18 alkyl alkoxycarboxylates (especially the EO 1-5 ethoxy carboxylates), the glycerol ethers of C-io-C-18, the alkyl polyglycosides of C10-C 8 and the corresponding sulfated polyglycosides, and the alpha sulfonated fatty acid esters of C 12 -C 8. If desired, conventional non-ionic and amphoteric surfactants such as the C 12 -C 8 alkyl ethoxylates ("AE") including the so-called narrow peak alkyl ethoxylates and the alkyl phenol C 6 -C 6 alkoxylates (especially ethoxylates) and mixed ethoxy / propoxy), C10-C18 amine oxides, and the like, may also be included in the total compositions. The N-alkyl polyhydroxy fatty acid amides of C-io-Cis can also be used. Typical examples include the N-methylglucamides of C12-C? 8. See WO 9,206,154. Other surfactants derived from sugar include the N.alkoxy polyhydroxy fatty acid amides, such as N- (3-methoxypropyl) glucamide of C? O-C-t8. The glucosides of N-propyl to N-hexyl of C? 2-C-? 8 can be used for low foam. Conventional C10-C20 soaps can also be used. If high foaming is desired, branched-chain C10-Ciß soaps can be used. Mixtures of anionic and nonionic surfactants are especially useful. Other conventional useful surfactants are listed in the standard texts. The cationic surfactants can also be used as a detergent surfactant herein and the suitable quaternary ammonium surfactants are selected from N-alkyl or alkenyl ammonium surfactants of Cß-Ciß, preferably Cß-C-io, in where the remaining N positions are substituted by methyl, hydroxyethyl or hydroxypropyl groups. Amfolitic surfactants can also be used as a detergent surfactant herein, which include aliphatic derivatives of heterocyclic secondary and tertiary amines; zwitterionic surfactants including aliphatic quaternary ammonium derivatives, phosphonium and sulfonium compounds; water-soluble salts of alpha sulfonated fatty acid esters; alkyl ether sulfates; water soluble salts of olefin sulphonates, beta-alkyloxy alean sulfonates; Betaines having the formula R (R1) 2N + R2COO-, wherein R is a hydrocarbyl group of C-C-is, preferably a C10-C-? 6 alkyl group or a C10-Ci6 alkyl acylamido group, each R1 is typically C 1 -C 3 alkyl, preferably methyl, and R 2 is a C 1 -C 5 hydrocarbyl group, preferably a C 1 -C 3 alkylene group, more preferably an alkylene group of dC 2. Examples of suitable betaines include coconut acylamidopropyl dimethylbetaine; hexadecyl dimethyl betaine; C-12-C14 acylamidopropyl betaine; acylamidoexildietilbetaine of Cs-14; 4 [C? 4-? 6-acylmethylamidodimethylammonium] -1-carboxybutane; C-iß-C-is acylamidodimethylbetaine, C? 2-C? 6 acylamidopentanediethylbetaine; and C12-C16 acylmethylamidodimethylbetaine. Preferred betaines are dimethyl-ammonium hexanoate of C? 2? 8 and acyl amidopropane (or ethane) dimethyl (or diethyl) betaines of C? 0-C? 8; and the sultaines having the formula (R (R 1) 2 N + R 2 SO 3 - wherein R is a C 1 -C 7 hydrocarbyl group, preferably a C 0 -C 6 alkyl group, more preferably an alkyl C group -? 2-C13, each R1 is typically C1-C3 alkyl, preferably methyl, and R2 is a C-Cβ hydrocarbyl group, preferably a C1-C3 alkylene or, preferably hydroxy-alkylene group Examples of suitable sultaines include dimethylammonium- 2- C12-C14 hydroxypropyl sulfonate, amido propyl ammonium-2-hydroxypropyl sultaine of C12-C14, dihydroxyethylammonium propane sulfonate of C12-C-14, dimethylammonium hexane sulfonate of C- | 6-Ci8, with amido propylammonium-2-hydroxypropyl sultaine of C12-C14 being preferred.

FINE DUSTS The fine powders of the present process preferably selected from the group consisting of milled anhydrous sodium carbonate, sodium tripolyphosphate powder (STPP), hydrotreated tripolyphosphate, ground sodium sulphates, aluminosilicates, crystalline layered silicates, nitryl triacetates (NTA), phosphates , precipitated silicates, polymers, carbonates, citrates, powder surfactants (such as alloy sulfonic acids in powder) and recycle fines that occur from the process of the present invention, wherein the average diameter of the powder is 0.1 to 500 microns, preferably from 1 to 300 microns, more preferably from 5 to 100 microns. In the case of using hydrated STPP like the fine powders of the present invention, it is preferable that STPP be hydrated at a level of not less than 50%. The aluminosilicate ion exchange materials used herein as detergent builders preferably have a high calcium ion exchange capacity and a high exchange rate. Without attempting to be limited by theory, it is believed that such calcium ion exchange rate and high capacity are a function of several interrelated factors that derive from the method by which the aluminosilicate ion exchange material is produced. In this regard, the aluminosilicate ion exchange materials used herein are preferably produced in accordance with Corkill and others of the U.S. Patent. No. 4,605,509 (Procter &Gamble), the disclosure of which is incorporated herein by reference. Preferably, the aluminosilicate exchange material is in the "sodium" form because the potassium and hydrogen forms of the aluminosilicate at the time do not exhibit a rate of exchange and capacity as high as that provided by the sodium form. Additionally, the aluminosilicate exchange material is preferably in an undissolved form to facilitate the production of brittle detergent agglomerates as described herein. The aluminosilicate ion exchange materials used herein preferably have particle size diameters that optimize their effectiveness as detergent builders. The term "particle size diameter" as used herein represents the average particle size diameter of a given aluminosilicate ion exchange material as determined by conventional analytical techniques, such as microscopic determination and scanning electron microscope. (SEM). The preferred particle size diameter of the aluminosilicate is from 0.1 microns to 10 microns, more preferably from 0.5 microns to 9 microns. More preferably, the particle size diameter is from 1 micron to 8 micron.

Preferably, the ionium exchange material of aminosilicate has the formula Naz [(AIO2) z. (SiO2) and] xH2O where z and are integers of at least 6, the molar ratio of zay is from 1 to 5 and x is from 10 to 264. More preferably, the aluminosilicate has the formula Na 12 [(Al ?2) i2. (Si ?2) i2] xH2O wherein x is from 20 to 30, preferably 27. These preferred aluminosilicates are commercially available, for example under designations Zeolite A, Zeolite B and Zeolite X. Alternatively, the naturally occurring aluminosilicate ion exchange materials or synthetically suitable derivatives for use herein may be made as described in Krummel et al., of the U.S. Patent. No. 3,985,669, the description of which is incorporated herein by reference. The aluminosilicates used herein are further characterized by their exchange capacity of Ion which is at least 200 mg hardness equivalent of CaCO3 / gram, calculated on an anhydrous basis, and which is preferably on a scale of 300 to 352 mg hardness equivalents of CaCO3 / gram. Additionally, the aluminosilicate ion exchange materials of the moment are further characterized by their calcium ion exchange rate which is at least 2 grains Ca ++ / 3.785 liters / minute / -gmo / 3.785 liters, and more preferably in one scale of 2 grains Ca ++ / 3.785 liters / minute / -gram / 3J85 liters to almost 6 grains Ca ++ / 3J85 liters / minute / -gram / 3J85 liters.

Liquid Polymers The starting detergent material for the present process may include liquid polymers. The liquid polymers can be selected from aqueous or non-aqueous polymer solutions, water and mixtures thereof. The amount of liquid polymers of the present process can be lower than 10% (active base), preferably lower than 6% (active base) in the total amount of the final product obtained by the process of the present invention. Preferable examples of the aqueous or non-aqueous polymer solutions which can be used in the present invention are modified polyamines which consist of a polyamine base structure corresponding to the formula H i [H2N-R] n + 1- [N-R] m- [N-R] n-NH2 which has a modified polyamine formula V (n + i) WmYnZ or a polyamine base structure corresponding to the formula H R I [H2N-R] n.k + 1- [N-R] m- [N-R] n- [N-R] k-NH2 having a modified polyamine formula V (n-k + i) WmYnY'kZ, where k is less than or equal to n, said polyamine base structure before modification has a molecular weight greater than 200 daltons, in where i) the units V are terminal units that have the formula: t? - O t E- N- R E- N + -R- E- N- R- I I I E E E ii) The units W are units of base structures that have the formula: O -N- R - or -N + -R- -N- R - I E Ii) Y units are branched units that have the formula: OR E X- t - N - R - - N + - R - N - R -; iv) The Z units are terminal units that have the formula: -N- E N I E E wherein the base structure chaining the R units is selected from the group consisting of C2-C12 alkylene, C4-C12 alkenylene, C3-C12 hydroxyalkylene, C4-C12 dihydroxyalkylene, C8-C12 dialkylarylene, - (R1O) ) xR1-, - (R10) xR5 (OR1) x-.

(CH2CH (OR2) CH2O) z (R1O) and R1 (OCH2CH (OR2) CH2) w-, -C (O) (R4) rC (O) -, - CH2CH (OR2) CH2-, and mixtures thereof, wherein R 1 is C 2 -C 6 alkylene and mixtures thereof, R 2 is hydrogen, - (R 10) xB, and mixtures thereof, R 3 is C 1 -C 18 alkyl, C 7 -Ci arylalkyl, aryl substituted by alkyl of C7-C? 2, C6-C12 aryl, and mixtures thereof; R4 is C1-C12 alkylene, C4-C12 alkenylene, C8-Ci2 arylalkylene, C6-C6 arylene, and mixtures thereof; R5 is C1-C12 alkylene, C3-C12 hydroxyalkylene, C4-C12 dihydroxy-alkylene, C8-C12 dialkylarylene, -C (O) -, -C (O) NHR6NHC (O) -, -R1 (OR1 ) -, -C (O) (R4) rC (O) -, -CH2CH (OH) CH2-, -CH2CH (OH) CH2? (R10) and R1OCH2CH (OH) CH2-, and mixtures thereof; R6 is C2-C12 alkylene or C6-C2 arylene; the E units are selected from the group consisting of hydrogen, C1-C22 alkyl, C3-C22 alkenyl, C7-C22 arylalkyl, C2-C22 hydroxyalkyl, - (CH2) PCO2M, - (CH2) qSO3M, -CH ( CH2CO2M) C02M, - (CH2) pPO3M, - (R1O) xB, -C (0) R3, and mixtures thereof; oxide; B is hydrogen, C? -C6 alkyl, - (CH2) qSO3M, - (CH2) pCO2M, - (CH2) q (CHS? 3M) CH2S? 3M, - (CH2) q- (CHS? 2M) CH2SO3M, - (CH2) pPO3M, - PO3M, and mixtures thereof; M is hydrogen or a cation soluble in water in an amount sufficient to satisfy the charge equilibrium; X is a water soluble anion; m has the value 4 to 400; n has the value from 0 to 200; p has the value of 1 to 6, q has the value of 0 to 6; r has the value of 0 or 1; w has the value of 0 or 1; x has the value of 1 to 100; and has the value from 0 to 100; z has the value of 0 or 1. An example of the most preferred polyethylene imines would be a polyethylenimine having a molecular weight of 1800 which is further modified by ethoxylation to a degree of about 7 ethyleneneoxy residues per nitrogen (PEI 1800, E7). It is preferable that the above polymer solution be precomplex with anionic surfactant such as NaLAS. Other preferable examples of the aqueous or non-aqueous polymer solutions which can be used as liquid polymers in the present inventions are polymeric polycarboxylate dispersants which can be prepared by polymerizing or copolymerizing suitable unsaturated monomers., preferably in its acid form. The unsaturated monomeric acids which can be polymerized to form suitable polymeric polycarboxylates include acrylic acid, maleic acid (maleic anhydride), fumaric acid, itaconic acid, aconitic acid, mesaconic acid, citraconic acid and methylenemalonic acid. The presence in polymeric polycarbomylates in the present of monomeric segments, which do not contain carboxylate radicals such as vinyl methyl ether, styrene, ethylene, etc. it is suitable with the proviso that said segments do not constitute more than 40% by weight. The homo-polymeric polycarboxylates having molecular weights above 4,000, such as those described below, are preferred. Particularly suitable homo-polymeric polycarboxylates can be derived from acrylic acid. Such acrylic acid-based polymers which are useful herein are the water-soluble salts of polymerized acrylic acid. The average molecular weight of such polymers in acid form is preferably in the range of from 4,000 to 10,000, preferably from above 4,000 to 7,000, and more preferably from above 4,000 to 5,000. Water-soluble salts of such acrylic acid polymers may include, for example, the alkali metal, ammonium and substituted ammonium salts. The co-polymeric polycarboxylates such as acrylic / maleic-based copolymers can also be used. Such materials include the water soluble salts of copolymers of acrylic acid and maleic acid. The average molecular weight of such copolymers in acid form is preferably in the range of 2,000 to 100,000, more preferably 5,000 to 75,000, more preferably 7,000 to 65,000. The ratio of acrylate to maleate segments in such copolymers will generally be in the range of 30: 1 to 1: 1, more preferably 10: 1 to 2: 1. The water-soluble salts of such acrylic acid / maleic acid copolymers may include, for example, the alkali metal, ammonium and substituted ammonium salts. It is preferable that the above polymer solution be pre-complexed with anionic surfactant such as LAS.

Attached detergent ingredients The starting detergent materials in the present process may include additional detergent ingredients and / or any number of additional ingredients may be incorporated into the detergent composition during subsequent steps of the present process. These adjunct ingredients include other detergent builders, bleaches, bleach activators, foam impellers or foam suppressors, antioxidants and anti-corrosion agents, soil suspending agents, soil release agents, germicides, pH adjusting agents, alkalinity sources no detergents, chelating agents, smectite clays, enzymes, enzyme stabilizing agents and perfumes. See the patent of E.U. 3,936,537 of February 3, 1976 to Baskerville, Jr. et al., Incorporated herein by reference. Other builders can generally be selected from various alkali metal, ammonium or substituted ammonium phosphates, polyphosphates, phosphonates, polyphosphonates, carbonates, borates, polyhydroxy sulfonates, polyacetates, carboxylates, and water soluble polycarboxylates. Preferred are the alkali metal salts, especially sodium, of the foregoing. Preferred for use herein are the phosphates, carbonates, fatty acids of C-io-is, polycarboxylates and mixtures thereof. More preferred are sodium tripolyphosphate, tetrasodium pyrophosphate, citrate, tartrate mono- and di-succinates, and mixtures thereof. Bleaching and activating agents are described in the US patent. 4,412,934, Chung et al., November 1, 1983 and in the U.S. patent. 4,483,781, Hartman, November 20, 1984, both of which are incorporated herein by reference. Chelating agents are also described in the US patent. 4,663,071, Bush and others, from column 17 row 54 to column 18 row 68, incorporated herein by reference. Foam modifiers are also optional ingredients and are described in the US patents. 3,933,672 from January 20, 1976 to Bartoletta et al., And 4,136,045 from January 23, 1979 to Gault et al., Both incorporated herein by reference. Smectite clays suitable for use herein are described in the US patent. 4,762,645, Tucker et al., From August 9, 1988, column 6, line 3 to column 7 line 24, incorporated herein by reference. Additional suitable detergent builders for use herein are listed in the Baskerville patent column 13, row 54 through column 16, row 16 and in the US patent. 4,663,071, Bush et al., May 5, 1987, both incorporated herein by reference.

Optional process steps An optional step after the second step of the present invention is an additional agglomeration process. Examples that can be used as the additional procedures are described in such as USP-5,486,303, USP-5,516,448, USP-5,554,587 and USP-5,574,005. Another optional step in the process is drying, if it is desired to reduce the moisture level of the present process. This can be achieved by a variety of apparatuses, well known to those skilled in the art. The fluid bed apparatus is preferred, and will be referred to in the discussion that follows.

In another optional step of the present process, the detergent granules emerging from the fluid bed dryer are additionally conditioned by additional cooling in cooling apparatuses. The preferred apparatus is a fluid bed. Another optional process step includes adding a coating agent to improve flowability in one or more of the following locations in the current process. The coating agent is preferably selected from the group consisting of aluminosilicates, silicates, carbonates and mixtures thereof. The coating agent not only improves the free flowability of the resulting detergent composition which is desirable by consumers in that it allows easy collection of the detergent during use, but also serves to control the agglomeration by preventing or minimizing over-agglomeration, especially when Add directly to the moderate speed mixer. As those skilled in the art will be aware, over-agglomeration can lead to very undesirable flow and aesthetic properties of the final detergent product. Optionally, the method may consist of the step of spraying an additional binder in the process for the present invention or fluid bed dryers and / or fluid bed coolers. A binder is added for objects to improve agglomeration by providing a "binder" or "adherent" agent for the detergent components. The binder is preferably selected from the group consisting of water, anionic surfactants, nonionic surfactants, liquid silicates, polyethylene glycol, polyvinyl pyrrolidone polyacrylates, citric acid and mixtures thereof. Other suitable binding materials including those listed herein are described in Beerse et al., Of the U.S. patent. 5,108,646 (Procter &; Gamble Co), the description of which is incorporated herein by reference. Other optional steps contemplated by the present method include the selection of large-sized detergent granules, the amount of which is minimized by the present method, in a screening apparatus which may have a variety of shapes including but not limited to conventional selectors chosen for the size of the desired particle of the finished detergent product. Another optional step of the instant process includes terminating the resulting detergent agglomerates by a variety of methods including spraying and / or blending with other conventional detergent ingredients. For example, the finishing step encompasses spraying perfumes, brighteners and enzymes onto the finished agglomerates to provide a more complete detergent composition. Such techniques and ingredients are well known in the art. The optional other step in the process includes a very active paste structuring process, for example, curing an aqueous anionic surfactant paste incorporating a paste hardening material using an extruder, prior to the process of the present invention. The details of the highly active paste structuring process are described in the application No. PCT / US 96/15960 (of October 4, 1996). In order to make the present invention more easily understood, reference is made to the following examples, which are designed to be illustrative only and not designed to limit their scope.

EXAMPLES EXAMPLE 1 The following is an example * (*: batch size) to obtain agglomerates using a bank mixer dimensioned at the Lódige CB scale (hereinafter CB mixer). 232 g of CFAS pulp (coconut C12-C18 fatty alcohol sulfate) (72% active) are dispersed by the bolt tools of a CB mixer for 7.25 seconds, together with 179 g of STPP powder (average particle size) of 40-75 microns), 119 g of milled anhydrous sodium carbonate (average particle size of 10-20 microns), 92 g of sodium sulfate (average particle size of 70-120 microns), 37 g of zeolite and 140 g of recycled fines After a short interval (1-2 seconds), 26 g of AE3S paste (C12-C15 alkyl ethoxy sulphate) (70% active) are dispersed by the CB blender pernpo tools for 1 second. After the addition of the AE3S paste, the contents in the CB mixer are mixed for 3 seconds in order to obtain free flowing agglomerates. The condition of the mixer CB is as follows: Mixer speed: 800 rpm Paste temperature: 45-47 ° C Sleeve temperature: 30 ° C Bolt length: 18.9 cm Diameter of the mixer: 20 cm The agglomerate of the CB mixer, has Free-flowing density 640-700 g / l. The agglomerates include only 5.2% of oversized granules (ie larger than 1 180 μm).

EXAMPLE 2 The following is an example * (*: batch size) to obtain agglomerates using a bank mixer dimensioned on the Lódige CB scale (hereinafter CB mixer), followed by a bench mixer sized on the Lódige KM scale (from here on forward KM mixer). 234 g of CFAS paste (coconut C12-C-18 fatty alcohol sulfate) (72% active) are dispersed by the CB binder bolt tools for 7.5 seconds, together with 197 g of STPP powder (size of average particle of 40-75 microns), 152 g of anhydrous sodium carbonate ground (average particle size of 10-20 microns), 66 g of sodium sulfate (average particle size of 10-20 microns) and 136 g of recycled fines. The contents in the CB mixer are mixed for 4 seconds in order to obtain free flowing agglomerates. The conditions of the CB-30 mixers are as follows: Mixer speed: 800 rpm Paste temperature: 45-47 ° C Sleeve temperature: 30 ° C Bolt length: 18.9 cm Diameter of the mixer: 20 cm 750 g of the agglomerates of the CB mixer are added to the KM mixer. 29 g of LAS acid precursor (linear C 8 alkyl benzene sulfonate (= average)) at 50-60 ° C are added to a KM mixer for 1.5 seconds. After the addition of the LAS acid precursor, 8 g of zeolite (average particle size of 4-7 microns) and 50 g of milled anhydrous sodium carbonate (average particle size of 10-20 microns) are added. The contents are mixed in the KM mixer for 4-5 seconds, for particle growth objects. In this mixing step, optionally, one or more conventional grinders may be adhered within the KM mixer. The conditions of the KM mixer are as follows: Mixer speed: 150 rpm Sleeve temperature: 35 ° C The agglomerates obtained from the KM mixer are dried in a batch-scale fluid bed dryer at 95 ° C for 3 minutes, and subsequently cooled in a batch-scale fluid bed cooler. The agglomerates of the cooler are free flowing with a cake resistance of 0.7 Kgf, and have a density of 750-800 g / l. The average particle size of the agglomerates is 400-500 μm. The agglomerates include 20% unacceptable oversized agglomerates (ie larger than 1180 μm).

EXAMPLE 3 The following is an example for obtaining agglomerates using a Lódige mixer CB-30 (hereinafter a CB mixer), followed by a mixer Lódige KM-600 (hereinafter KM mixer). 340 kg / hr of CFAS paste (C-? 2-C? 8 coconut fatty alcohol sulphate) (72% active) are dispersed by the bolt tools of a CB mixer together with 250 kg / hr of STPP in powder (average particle size of 40-75 micras), 185 kg / hr of milled anhydrous sodium carbonate (average particle size of 10-20 microns) 195 kg / hr of ground sulphate (average particle size of 10-20 microns), 200 kg / hr of recycled fines and kg / hr of zeolite. The conditions of the mixer CB-30 are as follows. Mixer speed: 620 rpm Paste temperature: 45-48 ° C Sleeve temperature: 30 ° C Bolt length: 28.9 cm Mixer diameter: 30 cm Retention time: 7-15 seconds Mixer power condition: 2.1 kj / kg The agglomerates of the mixer CB are added to the mixer KM. 37 kg / hr of AE3S paste (C12-C15 alkyl ethoxy sulphate) (70% active) are dispersed to the KM mixer by means of the bolt tools of the CB mixer. 5-10 kg / hr of zeolite are added to the KM mixer. In the mixing step in the KM mixer, conventional shredders (4 numbers of "Christmas Tree Shredders") can be stuck inside the KM mixer. The conditions of the KM mixer are as follows: Mixer speed: 100 rpm Sleeve temperature: 40 ° C Retention time: 2.0-6.0 minutes Mixer power conditions: 1.5-3.0 kj / kg Grinders condition: 1, 600 rpm The agglomerates obtained from the KM mixer have only 2-10% unacceptable oversized agglomerates (ie larger than 1180 μm). The agglomerates of the KM mixer (having a diameter no larger than 1180 μm) are dried in a fluid bed dryer at 95 ° C, and subsequently cooled to 10-12 ° C in a fluid bed cooler.

The agglomerates of the cooler are in free flow, and have a density of 750-850 g / l. The average particle size of the agglomerates is 500-650 μm. Having thus described the invention in detail it will be obvious to those skilled in the art that various changes can be made without departing from the scope of the invention and that the invention should not be considered limited to what is described in the specification.

Claims (10)

NOVELTY OF THE INVENTION CLAIMS

1. - A process for preparing a granular detergent composition The process consists of: (a) Deeply mixing a paste of crystalline anionic surfactant with a sufficient amount of fine powders of starting detergent materials to form a free flowing agglomerate; (b) Deeply mixing a product from step (a) with a paste of non-crystalline anionic surfactant to form a free-flowing agglomerate.

2. The process according to claim 1 further characterized in that one or more starting detergent materials selected from the group consisting of detergent surfactants, liquid polymers, and adjunct detergent ingredients, are added during step (a).

3. The process according to claim 1, further characterized in that one or more starting detergent materials selected from the group consisting of detergent surfactants, fine powders, liquid polymers, and adjunct detergent ingredients, are added during step (b) .

4. The process according to claim 1 further characterized in that the crystalline anionic surfactant paste is an alkyl sulfate or a mixture of alkyl sulphates, selected from the group consisting of coconut C12-C18 fatty alcohol sulfates, sulfates of alkyl of synthetic Cu.Ci5 and mixtures thereof.

5. The process according to claim 1 further characterized in that the paste of non-crystalline anionic surfactant is selected from the group consisting of alkyl ethoxy sulfates, alkyl benzene sulphonates and mixtures thereof.

6. The process according to claim 1 further characterized in that the fine powders are selected from the group consisting of anhydrous sodium carbonate, powdered sodium tripolyphosphate, hydrated tripolyphosphate, sodium sulfates, aluminosilicates, crystalline layered silicates, phosphates, silicates precipitates, polymers, carbonates, citrates, nitrilotriacetates (NTA), powder surfactants, recycled fines from step (b) and mixtures thereof.

7. The process according to claim 1 further characterized in that the agglomerate of step (b) includes less than 20% granules having a larger diameter of 1180 μm.

8. The process according to claim 1 further characterized in that an active weight ratio of the crystalline anionic surfactant paste to the fine powders in step (a) is from 2.0 to 3.2.

9. The process according to claim 1 further characterized in that an active weight ratio of the crystalline anionic surfactant paste in step (a) to the paste of the non-crystalline anionic surfactant in step (b) is 4% to 14%.

10. A granular detergent composition manufactured in accordance with the method of claim 1.