MXPA99001905A - Agglomeration process for producing detergent compositions involving premixing modified polyamine polymers - Google Patents

Abstract

A process is provided in which selected modified polyamines are incorporated into fully formulated detergent compositions in a manner that unexpectedly results in enhanced cleaning performance. The process involves premixing the modified polyamine with a detersive surfactant or acid precursor thereof, and thereafter, agglomerating with dry detergent materials such as builders.

Description

AGGLOMERATION PROCEDURE TO PRODUCE DETERGENT COMPOSITIONS INCLUDING PREMIDIZE PQLIAMINE POLYMERS MODIFIED FIELD OF THE INVENTION The present invention relates to an agglomeration process for producing laundry detergent compositions containing modified polyamines, especially useful as cotton dirt release and / or dispersing agents. More specifically, the process includes premixing the modified polyamine with a surfactant paste or an acid precursor thereof prior to subsequent agglomeration with a builder and optional auxiliary detergent ingredients. The premix is subjected to an agglomeration step which can be carried out in two mixers / densifiers placed in series, in such a way as to provide an agglomerated detergent composition having improved performance.

BACKGROUND OF THE INVENTION Various fabric surface modifying agents have been marketed and are currently used in detergent compositions and articles and fabric softening / antistatic compositions. Examples of surface modifying agents are soil removal polymers. The soil removal polymers typically comprise a "backbone" of oligomeric or polymeric ester, and are generally very effective on polyester or other synthetic fabrics where the similar hydrophobic grease or stains form a fixed film that is not easily removed in a process. of aqueous wash. Soil-removing polymers have a less drastic effect on "mixed" fabrics, that is, on fabrics comprising a mixture of cotton and synthetic material, and have little or no effect on cotton articles. Extensive research in this area has produced significant improvements in the effectiveness of polyester dirt removal agents by producing materials with improved product formulation and performance. Modifications of the polymer skeleton as well as the selection of suitable end blocking groups, has produced a wide variety of polyester dirt remover polymers. For example, block end modifications, such as the use of sulfoaroyl moieties, and especially low cost isethionate derivative blockers, have increased the solubility and compatibility scale of the auxiliary ingredient of these polymers without sacrifice the effectiveness to remove dirt. Many polyester dirt remover polymers can now be formulated into both liquid and solid (ie, granular) detergents. As in the case of polyester soil removal agents, the production of an oligomeric or polymeric material that simulates the structure of the cotton has not resulted in a cotton soil removal polymer. Although the cotton and polyester fabrics are both comprised of long-chain polymeric materials, they are very different chemically. Cotton is comprised of cellulose fibers consisting of anhydroglucose units linked by 1-4 bonds. These glycosidic linkages characterize cotton cellulose as a polysaccharide, while polyester dirt remover polymers are generally a combination of terephthalate and ethylene / propylene oxide residues. These differences in composition account for the difference between the properties of the cotton fabric and the polyester fabric. Cotton is hydrophilic in relation to polyester. Polyester is hydrophobic and attracts oily or greasy soils and can be "dry-cleaned" easily. Importantly, the terephthalate and ethyleneoxy / propyleneoxy skeleton of the polyester fabric does not contain reactive sites, such as the hydroxyl portions of the cotton that react with the stains in different ways than the synthetic ones. Many spots of cotton are "fixed" and can only be removed by bleaching the fabric. So far the development of a cotton dirt remover has not been achieved, effective for use in a laundry detergent. Attempts by others to apply the paradigm of matching the structure of a soil removal polymer with the structure of the fabric, a successful method in the field of polyester dirt removal polymers, have however produced marginal results when applied to dirt removal agents from cotton fabrics. The use of methylcellulose, a cotton polysaccharide with modified oligomeric units, proved to be more effective in polyesters than in cotton. Additionally, detergent formulators have faced the task of designing products to remove a wide spectrum of stains and dirt from fabrics. Varieties of stains and soils vary within a spectrum that ranges from polar soils such as proteinaceous, clay and inorganic soils, to non-polar soils such as soot, carbon black, byproducts of incomplete combustion of hydrocarbons and organic soils. To that end, the detergent compositions have become more complex as the formulators attempt to provide products that can deal with all sorts of soils concurrently. The formulators have been successful in the development of traditional dispersants that are particularly useful in the suspension of highly charged, hydrophilic polar particles, such as clay. However, until now it has been difficult to develop dispersants designed to disperse and suspend dirt and non-polar suspended particles, of the hydrophobic type.

It has now surprisingly been discovered that effective soil removal agents can be prepared for cotton articles and dispersants, starting from certain modified polyamines. This unexpected result has produced compositions that are key to providing these dirt removal benefits only available once for synthetic or combined synthetic-cotton fabrics. However, the manner in which said modified polyamines can be included in fully formulated detergent compositions, in order to retain and, preferably, improve performance, has remained unresolved. The detergent compositions containing these modified polyamines, and are produced by the processes of the prior art, do not have the desired performance. Accordingly, there remains a need in the art for a detergent preparation process that provides a means by which selected modified polyamines can be incorporated into fully formulated detergent compositions having improved cleaning action.

TECHNICAL BACKGROUND U.S. Patent No. 1,314,897, issued April 26, 1973, teaches a hydroxypropylmethylcellulose material for the prevention of redeposition of wet soils and improvement of removal of dirt from the washed fabric. The patent of E.U. No. 3,897,026 issued to Kearney, discloses cellulose textile materials having improved soil removal and stain resistance properties, obtained by the reaction of an ethylene-maleic anhydride copolymer with the hydroxyl portions of the cotton polymers. The patent of E.U. No. 3,912,681 issued to Dickson teaches a composition for applying a non-permanent dirt removal finish comprising a polycarboxylate polymer to a cotton cloth. The patent of E.U. No. 3,984,838, issued to Hinton et al., Discloses high molecular weight polyacrylic polymers (500,000 to 1,500,000) for dirt removal. The patent of E.U. No. 4,559,056, issued to Leigh et al., Discloses a process for treating cotton or synthetic fabrics with a composition comprising an organopolysiloxane elastomer, an organosiloxane oxyalkylene copolymer crosslinking agent and a siloxane cure catalyst. See also the US patents Nos. 4,579,681 and 4,614,519. These patents disclose vinylcaprolactam materials that have their effectiveness limited to polyester fabrics, cotton and polyester blends, and cotton fabrics made hydrophobic by finishing agents. In addition to the aforementioned prior art, the following describe different modified polymers or polyamines soil removers: U.S. Patent 4,548,744, Connor, issued October 22, 1985; U.S. Patent 4,597,898, Vander Meer, issued July 1, 1986; U.S. Patent 4,877,896, Mandolado et al., issued October 31, 1989; U.S. Patent 4,891,160, Vander Meer, issued January 2, 1990; U.S. Patent 4,976,879, Mandolado et al., issued December 11, 1990; U.S. Patent 5,415,807, Gosselink, issued May 16, 1995; U.S. Patent 4,235,735, Marco et al., issued November 25, 1980; WO 95/32272, published November 30, 1995; U.S. Patent 1,537,288, published December 29, 1978; U.S. Patent 1,498,520, published January 18, 1978; German patent DE 28 29 022, issued on January 10, 1980; Japanese Kokai patent, published on April 27, 1994. The following references are directed to the densification of spray-dried granules: Appel et al., Patent of E.U.A. No. 5,133,924 (Lever); Bortolotti et al., Patent of E.U.A. No. 5,160,657 (Lever); Johnson et al., British Patent No. 1,517,713 (Unilever); and Curtis, European Patent Application No. 451,894. The following references are directed to the production of detergents by agglomeration: Beerse et al., U.S. Pat. No. 5,108,646 (Procter £ _ Gamble); Capeci et al., Patent of E.U.A. No. 5,366,652 (Procter __ Gamble); Capeci et al., Patent of E.U.A. No. 5,486,303 (Procter &Gamble); Capeci et al., Patent of E.U.A. No. 5,489,392 (Procter fi Gamble); Hollingsworth et al., European Patent Application No. 351,937 (Unilever); and Swatling et al., U.S. Patent. No. 5,205,958.

BRIEF DESCRIPTION OF THE INVENTION The needs mentioned above in the art are covered by the present invention, which provides a process in which selected modified polyamines are incorporated in fully formulated detergent compositions, which unexpectedly exhibit improved cleaning and dispersing action, especially in relation to fabrics containing cotton. In essence, the process of the invention involves premixing the modified polyamine with a detersive surfactant or an acid precursor thereof, and then agglomerating the premix in a high speed mixer / densifier, followed by a moderate speed mixer / densifier with improvers. of detergency and optional auxiliary detergent ingredients.

In accordance with one aspect of the invention, a process for an agglomerated detergent composition is provided. The process comprises the steps of: (a) premixing a detersive surfactant paste, dry detergent material and a modified polyamine soluble or water dispersible in a premixer to form a premix, the modified polyamine has a polyamine backbone corresponding to the formula: H [H2N-R] n + 1- [N-R] m-I [N-R] n-INH2, having a modified polyamine formula V (n + i) WmYnZ, or a polyamine skeleton corresponding to the formula: H R I I I [H2N-R] n-k + l- [N-R] m- [N-R] n- [N-R] k-NH2, having a modified polyamine formula V (n_k + l) wm? n? 'k Z' wherein k is less than or equal to n, said polyamine skeleton, before modification, has a molecular weight greater than about 200 daltons, where: i) units V are terminal units that have the formula: E X "0 t- E - N - R - H - N + - R - E - N - R - ii) the units W are skeleton units that have the formula: iii) Y units are branching units that have the formula: E X "0 1 --N - R or -N + -R- or - -N- -R and iv) the Z units are terminal units that have the formula: E X "O --N - E or --Nl ++ - E or --N» - E wherein the skeletal linker units R are selected from the group consisting of C2-C2 alkylene, C4-C2 alkenylene, C3-C12 hydroxyalkylene, C4-C2-dihydroxyalkylene / dialkylarylene of s-C12, ( R10) xR1-, - (R10) xR5 (OR1) x, - (CH2CH (OR2) CH20) 2 (R10) and R1- (OCH2CH (OR2) CH2) w ~, -C (0) (R4) rC (0 ) -, -CH2CH (OR2) CH2-, and mixtures thereof; wherein R1 is C2-Cg alkylene, and mixtures thereof; R is hydrogen, - (R 0) XB, and mixtures thereof; R3 is alkyl of -C ^ g, arylalkyl of C? -C ^, aryl substituted with C7-C-alkyl] 2, aryl of Cg-C] _2 and mixtures thereof; R4 is alkylene of C] _-C_2, C4-C2 alkenylene] 2, arylalkylene of CQ-C] _2, arylene of Cg-C] _o and mixtures thereof; R 5 is C 1 -C 2 alkylene, C 3 -C 4 hydroxyalkylene, C 4 -C 12 dihydroxyalkylene, C 8 -C 20 dialkylarylene, -C (O) -, -C (0) NHR 6 NHC (0) -, -R 1 (OR1) -, -C (O) (R4) rC (O) -, CH2CH (OH) CH2-, CH2CH (OH) CH20- (R10) and R1OCH2CH (OH) CH2-, and mixtures thereof; R 6 is C 2 -C 2 alkylene] or arylene of Cg-C] _ 2; the E units are selected from the group consisting of hydrogen, C_-C2 alkyl, C3-C22 alkenyl, C7-C22 arylalkyl, C2-C22 hydroxyalkyl, - (CH2) pC02M, - (CH2) qS03M, -CH (CH2C02M) C02M, (CH2) pP03M, - (R10) xB, -C (0) R3, and mixtures thereof; oxide; B is hydrogen, Ci-Cg alkyl, - (CH2) gS03M, - (CH2) pC0 M, (CH2) q (CHS03M) CH2S03M, - (CH2) q- (CHS02M) CH2S03M, - (CH2) pP03M, - PO3M, and mixtures thereof; M is hydrogen or a cation soluble in water in an amount sufficient to satisfy the balance of the charge; X is a water soluble anion; m has the value of 4 to about 400; n has the value from 0 to about 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; "y" has the value of 0 to 100; z has the value of 0 or 1; and (b) agglomerating the premix initially in a high speed mixer / densifier and subsequently in a moderate speed mixer / densifier., so as to form agglomerates, thereby resulting in the detergent composition. In accordance with another aspect of the invention, a process for producing an agglomerated detergent composition is provided. This method comprises the steps of: (a) premixing an acid precursor of a detersive surfactant, dry detergent material and a modified polyamine soluble or dispersible in water, in a mixer to form a premix, wherein the modified polyamine has a skeleton of polyamine as described above; (b) introducing the premix into a high speed mixer / densifier and neutralizing the acid precursor to form agglomerates; and (c) further agglomerating the agglomerates in a moderate speed mixer / densifier, so as to form the detergent composition. Also, the present invention provides detergent compositions prepared by any of the methods described herein. As used herein, the term "agglomerate" refers to particles formed by agglomeration of granules or detergent particles that typically have a smaller average particle size than the agglomerates formed. All documents cited herein are incorporated by reference, and percentages and ratios used herein are expressed as "percentages by weight" unless otherwise indicated. All the viscosities referred to herein are measured at 70 ° C, and at cutting speeds of about 10 to 100 sec-1. Accordingly, an object of the invention is to provide a process for producing an agglomerated detergent composition that provides a means for incorporating selected modified polyamine into fully formulated detergent compositions. Also, an object of the invention is to provide said process that reduces or eliminates the degradation of the modified polyamines selected as a result of the process of preparing the fully formulated detergent, in such a way as to provide improved cleaning action. These and other objects, features and concomitant advantages of the present invention will become apparent to the person 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 process of the present invention involves premixing selected modified polyamines and a surfactant paste, prior to neutralization of an acid precursor of a surfactant, or during said neutralization. Although not wishing to be bound by theory, it is considered that the selected modified polyamines described in more detail below, form a complex with the detersive surfactant in the surfactant paste or liquid acid precursor thereof. To achieve the maximum benefits of the process, the surfactant paste will preferably comprise an anionic surfactant and optionally a nonionic surfactant, but preferably will not contain a cationic surfactant. This complex of polyamine and surfactant typically has a higher oxidative degradation temperature as compared to the degradation temperature of the modified polyamines by themselves. As a consequence of this complex formation, the selected modified polyamines unexpectedly cause improved performance of the fully formulated granular detergent composition in which these modified polyamines are incorporated. For this purpose, the modified polyamine and the surfactant paste or acid precursor thereof is mixed for at least 5 seconds, preferably from about 5 seconds to about 1 minute, in any acceptable known mixing apparatus, such as static mixer in line, double worm extruder, stirred mixing tanks and the like. The temperature at which the premix step is performed using the surfactant paste is typically a temperature of about 25 ° C to about 80 ° C. Also, it is preferred to maintain the pH of the premix from about 8 to about 10, with no other detergent ingredients apart from the surfactant paste and the modified polyamine. In the case of using an acid precursor, the pH typically is from about 1 to about 3, and the temperature is typically from about 50 ° C to about 90 ° C. The modified polyamine is preferably present in an amount of from about 0.01% to about 10%, preferably from about 0.05% to about 5%, and from about 0.1% to about 1.0% by weight of the total detergent composition is highly preferred. In addition, in the premix step, the detersive surfactant paste preferably comprises from about 1% to about 70%, preferably from about 20% to about 60%, and from about 25% to about 50% by weight is most preferred. a detersive surfactant, the remainder being water and other minor ingredients. The preferred surfactants used in the surfactant paste are anionic surfactants as detailed below. With the selections mentioned above, the process provides a detergent composition that unexpectedly exhibits improved cleaning action compared to the direct addition of the modified polyamine to the composition. In the embodiment that includes the surfactant paste, the modified polyamine premix and paste are initially agglomerated in a high speed mixer / densifier, followed by a moderate speed mixer / densifier. The high speed mixer / densifier is a Lódige CB 30 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 plow-shaped vanes are attached. Preferably, the shaft rotates at a speed of about 100 rpm to about 2500 rpm, preferably from about 300 rpm to about 1600 rpm. Preferably, the average residence time of the detergent ingredients in the high speed mixer / densifier, is on the scale from about 2 seconds to about 45 seconds, and preferably from about 5 seconds to about 15 seconds. Preferably, the resulting detergent agglomerates formed in the high speed mixer / densifier are then loaded in a lower or moderate speed mixer / densifier during which additional agglomeration and densification is effected. This particular moderate speed mixer / densifier used in the present method must include tools for liquid distribution and agglomeration in such a way that both techniques can occur simultaneously. It is preferable to have the moderate speed mixer / densifier, for example a Lódige Mixer KM 600 (Ploughshare), Drais® K-T 160 mixer or similar brand mixer. The residence time in the moderate speed mixer / densifier is preferably from about 0.5 minutes to about 15 minutes, preferably the residence time is from about 1 to about 10 minutes. The liquid distribution can be made by cutters, generally smaller than the rotating shaft, which preferably operates at approximately 3600 rpm. It should be understood that although the process described herein is related to the formation of high density agglomerates, the same equipment and process steps can be used to produce less dense or moderately dense agglomerates. Of course, the agglomerates produced by the process regardless of their density can be mixed with less dense spray-dried granules in the final detergent product, if desired. The detergent agglomerates produced by the process preferably have a level of surfactant of from about 25% to about 55%, preferably from about 35% to about 55%, and preferably from about 45% to about 55%. The particle porosity of the detergent agglomerates produced according to the process of the invention is preferably in the range of about 5% to about 20%, preferably about 10%. In addition, one attribute of dense or densified agglomerates is the relative particle size. The present process typically provides detergent agglomerates having an average particle size of about 400 microns to about 700 microns, and preferably about 400 microns to about 600 microns. As used herein, the phrase "average particle size" refers to individual agglomerates and not to individual particles or detergent granules. The combination of the aforementioned porosity and particle size results in agglomerates having density values of 650 g / 1 and greater. Alternatively, the particle size and porosity can be adjusted to also produce agglomerates having lower densities (e.g., 300 g / 1 to 500 g / 1). Said features are especially useful in the production of low and high or conventional dosage laundry detergents, as well as other granular compositions such as dishwashing compositions. In the embodiment that includes the acid precursor of a surfactant, the premix of acid precursor and modified polyamine is neutralized with a neutralizing agent, preferably a dry agent selected from the group consisting of carbonates, silicates and mixtures thereof, with the preferred sodium carbonate. This neutralization occurs in the high speed mixer / densifier mentioned above. If the surfactant paste is used, the neutralization step is not necessary, and the dry detergent material is introduced into the high-speed mixer / densifier with the premix. In both embodiments, agglomerates are formed in the high speed mixer / densifier. Nevertheless, it is preferable to send these agglomerates to the aforementioned moderate speed mixer / densifier for the final formation of particle size and further agglomeration. Preferably, the dry detergent material includes sodium sulfate and a builder selected from the group consisting of aluminosilicates, carbonates, phosphates and mixtures thereof. The optional auxiliary detergent ingredients, as described more fully below, can be added at any step of the process to provide a more fully formulated detergent composition.

Optional Process Steps In an optional step of the present process, the detergent agglomerates formed by the process are dried in a fluid bed dryer and / or further conditioned by cooling the agglomerates in a fluid bed cooler or similar apparatus, as is known in the art. Another optional step of the process involves adding a coating agent to improve the flowability and / or reducing excess agglomeration of the detergent composition at one or more of the following points of the present process: (1) the coating agent can be added directly after the fluid bed cooler or dryer; (2) the coating agent can be added between the fluid bed dryer and the fluid bed cooler; (3) the coating agent can be added between the fluid bed dryer and the mixer / densifier; and / or (4) in coating agent can be added directly to one or more of the mixers / densifiers. 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 flow of the resulting detergent composition, which is convenient according to the consumers, since it allows the detergent to be easily taken during use, but also serves to control the agglomeration by avoiding or minimizing excessive agglomeration , especially when it is added directly to the mixer / densifier. As is well known to those skilled in the art, excess agglomeration can lead to very inconvenient flow and aesthetic properties of the final detergent product. Other optional steps in the present process include recycling the larger and smaller sized agglomerates, as described in Capeci et al., U.S. Pat. Nos. 5,489,392 and 5,516,448 (Procter &Gamble). Also, the inclusion step of an anhydrous material can be incorporated in selected points in the process, as described by Capeci et al., US patent. No. 5,366,652 and 5,486,303 (Procter &Gamble). Optionally, the agglomerates leaving the moderate speed mixer / densifier can be dried in a spray drying tower as described in Capeci et al., US Pat. 5,496,487 (Proter &Gamble). Optionally, the process may comprise the steps of sprinkling an additional binder in the mixer / densifiers used in the agglomeration step, to facilitate the production of the desired detergent agglomerates. A binder is added in order to increase the agglomeration by providing a "binder" or "adhesion" agent for the detergent components. The binder is preferably selected from the group consisting of water, anionic surfactants, nonionic surfactants, polyethylene glycol, polyacrylates, citric acid and mixtures thereof. Other suitable binding materials, including those listed herein, are described in Beerse et al., U.S. Pat. No. 5,108,646 (Procter &Gamble Co.), the disclosure of which is incorporated herein by reference. Another optional step of the present method comprises terminating the resulting detergent agglomerates by a variety of methods including spraying and / or mixing with other conventional detergent ingredients. For example, the finishing step encompassing the sprinkling of perfumes, and the addition of brighteners and enzymes to the finished agglomerates to provide a more complete detergent composition. Such techniques and ingredients are well known in the art.

Modified polyamines The modified polyamines used in the process of the present invention are soluble or dispersible in water, they are especially useful for cleaning fabrics containing cotton, or as a dispersant. These polyamines comprise skeletons which can be either linear or cyclic. The polyamine skeletons may also comprise, to a greater or lesser degree, polyamine branching chains. In general, the polyamine backbones described herein are modified such that each nitrogen of the polyamine chain is described below in terms of a unit that is substituted, quaternized, oxidized, or combinations thereof. For the purposes of the present invention, the term "modification" is defined as the replacement of a hydrogen atom of -NH of the backbone with an E unit (substitution), the quaternization of a skeleton nitrogen (quaternization) or oxidation of a Nitrogen from the skeleton to the N-oxide form (oxidation). The terms "modification" and "substitution" are used interchangeably when referring to the process of replacing a hydrogen atom attached to the nitrogen of the backbone, with an E. The quaternization or oxidation may take place in some circumstances without substitution, but preferably the substitution is accompanied by oxidation or quaternization of at least one nitrogen of the skeleton. The linear or non-cyclic polyamine skeletons comprising the polymers used in the process have the general formula: H I I [H2N-R] n + 1- [N-R] m- [N-R] n-NH2 said skeletons, before subsequent modification, comprise primary, secondary and tertiary amine nitrogens, linked by "linker" units R. The cyclic polyamine skeletons have the following general formula: H R [H2N-R] n_k +? - [N-R] m-I [N-R] n-I [N-R] k-INH2 said backbones prior to subsequent modification, comprise primary, secondary and tertiary amine nitrogens, linked by "linker" units R. For the purpose of the present invention, the primary amine nitrogens comprising the backbone or branching chain, once modified, they are defined as "terminal" V or Z units. For example, when a portion of primary amine, located at the end of the main skeleton or branching chain of the polyamine, having the structure: H2N-R] - is modified in accordance with the present invention, is subsequently defined as a "terminal" V unit, or simply a V unit. However, for the purposes of the present invention, some or all of the primary amine portions they may remain unmodified, subject to the restrictions described later herein. These unmodified primary amine portions, by virtue of their position in the skeleton chain, remain as "terminal" units. Also, when a portion of primary amine located at the end of the main polyamine skeleton, which has the structure: -NH2 it is modified in accordance with the present invention, it is subsequently defined as a "terminal" Z unit, or simply a unit Z. This unit may remain unmodified, subject to the restrictions described hereinafter. Similarly, the secondary amine nitrogens comprising the backbone or branching chain once modified, are defined as "skeleton" units W. For example, when a secondary amine portion, the main constituent of the skeletons and branching chains of the present invention, having the structure is modified in accordance with the present invention, is then defined as a "skeleton" unit W, or simply a unit W. However, for the purposes of the present invention, some or all of the secondary amine portions may remain unmodified . These unmodified secondary amine portions, by virtue of their position in the skeleton chain, remain as "skeleton" units. In a similar manner, the tertiary amine nitrogens comprising the backbone or branching chain, once modified, are further referred to as "branching" Y units. For example, when a tertiary amine portion, which is a chain branching point of the polyamine skeleton or other branching chains or rings, having the structure: - [NR] - modified in accordance with the present invention, is then defined as a "branching" Y unit or simply a Y unit. However, for the purposes of the present invention, some or all portions of Tertiary amine may remain unmodified. These unmodified tertiary amine portions, by virtue of their position in the skeleton chain, remain as "branching" units. The R units associated with the nitrogens of the units V, W and Y, which serve to connect the polyamine nitrogens, are described hereinafter. The final modified structure of the polyamines of the present invention can therefore be represented by means of the general formula V (n + l) WmYn z for linear polyamine polymers; and by means of the general formula di- + D m nY'kZ for cyclic polyamine polymers. For the case of polyamines comprising rings, a unit Y 'of the formula: R - [N-R] serves as a branching point for a skeleton or branching ring. For each unit Y ', there exists a unit Y that has the formula: ° - [N-R] - which forms the connection point of the ring with the polymer backbone or branching. In the only case in which the skeleton is a complete ring, the polyamine skeleton has the formula: H [H2N-R] n- [N-R] m-I [N-R] n-I therefore, it does not comprise terminal Z unit and has the formula: Vn_kWmYnY'k where k is the number of branching units forming the ring. Preferably, the polyamine backbones of the present invention do not comprise rings. In the case of non-cyclic polyamines, the ratio of the index n to the index m, refers to the relative degree of branching. A linear modified polyamine completely unbranched according to the present invention has the formula: VWm Z that is, n is equal to 0. The higher the value of n (the smaller the proportion of m to n), the greater the degree of branching in the molecule. Typically, the value of m varies from a minimum value of 4 to about 400, however, larger values of m are also preferred, especially when the value of the index n is very low or close to 0. Each polyamine nitrogen, and whether primary, secondary or tertiary, once modified in accordance with the present invention, it is subsequently defined as a member of one of three general classes; replaced, quaternized or oxidized. The unmodified polyamine nitrogen units are classified into units V, W, Y or Z, depending on whether they are primary, secondary or tertiary nitrogens. That is, the unmodified primary amine nitrogens are V or Z units, the unmodified secondary amine nitrogens are units W, and the unmodified tertiary amine nitrogens are Y units, for the purposes of the present invention. Modified portions of primary amine are defined as "terminal" V units, and have one of three forms: a) simple substituted units that have the structure: b) quaternized units that have the structure: X " where X is an adequate counter-ion that provides load balance; and c) oxidized units having the structure: 0 t E - N-R- Modified secondary amine moieties are defined as "skeleton" W units having one of three forms: a) simple substituted units having the structure: -N-R- b) quaternized units that have the structure: E X "--N + -R- I in which X is a suitable counterion that provides load balance; and c) oxidized units having the structure: O t --N-R- The modified tertiary amine moieties are defined as Y "branching" units having one of three forms: a) unmodified units having the structure: -N-R- I b) quaternized units that have the structure: E X "--NT-R- where X is an adequate counter-ion that provides load balance; and c) oxidized units having the structure: OR • -N-R- Certain portions of modified primary amine are defined as "terminal" Z units that have one of three forms: a) simple substituted units that have the structure: b) quaternized units that have the structure: X " where X is an adequate counter-ion that provides load balance; and c) oxidized units having the structure: 0 t -N-E E I When any position on a nitrogen is not substituted or is not modified, it is understood that E will be replaced by hydrogen. For example, a primary amine unit comprising an E unit in the form of a hydroxyethyl portion, is a V terminal unit having the formula (HOCH2CH2) HN-. For the purposes of the present invention, there are two types of chain terminator units, the V and Z units. The "terminal" Z unit is derived from a terminal primary amine portion of the -NH2 structure. The non-cyclic polyamine skeletons according to the present invention comprise only one unit Z, while the cyclic polyamines may not comprise units Z. The "terminal" Z unit may be substituted with any of the units E described below in the I presented, except when unit Z is modified to form an N-oxide. In the case in which the nitrogen of unit Z is oxidized to an N-oxide, the nitrogen must be modified and therefore E can not be a hydrogen. The polyamines of the present invention comprise skeleton "linker" units R serving to join the nitrogen atoms of the backbone. The R units comprise units which for the purpose of the present invention are called "R hydrocarbyl" units and "R oxy" units. The "hydrocarbyl" R units are C 2 -C 2 alkylene, C 4"C 2 alkylene and C 3 -C 2 hydroxyalkylene, in which the hydroxyl portion can take any position on the R unit, except the carbon atoms directly linked to the nitrogens of the polyamine skeleton; C 4 -C 2 dihydroxyalkylene wherein the hydroxyl portions can occupy any two of the carbon atoms of the chain of the R unit, except those carbon atoms directly connected to the nitrogens of the polyamine skeleton; dialkylarylene of Cg-C] _2 which for the purpose of the present invention are arylene portions having two alkyl substituent groups as part of the linker chain. For example, a dialkylarylene unit has the formula: although the unit does not need to be 1, 4 -substituted, but it can also be 1,2- or 1,3-substituted with C 2 -C 2 alkylene], preferably ethylene, 1,2-propylene and mixtures thereof, very preferably ethylene. The units R "oxy" comprise - (R1)) 5 5 (OR1) x-, -CH2CH (OR2) CH20) z (R10) and R1- (OCH2CH (OR2) CH2) w-, CH2CH (OR2) CH2-, - ( R ^ -O ^ R1- and mixtures thereof Preferred R-units are C -C] _2 alkylene, 3-C12 hydroxyalkylene, 4-C] dihydroxyalkylene, C8-C12 dialkylarylene, - (R ^ .xR1-, -CH2CH (OR2) CH2-, (CH2CH (OH) CH20) z- (R10) and R1 (OCH2CH- (OH) CH2) w-, - (R1 ©) XR5 (OR1) X-; most preferred R units are alkylene of c 2"c 12 'hydroxyalkylene of 3 ~ C] _2, dihydroxyalkylene of 4 ~ C 2, (R10) XR1-, - (R10) xR5 (OR1)? -, (CH2CH (OH) CH20) z (R10) and R1 (OCH2CH- (OH) CH2) w-, and mixtures thereof, R units even more Preferred are C2-C2 alkylene], C3 hydroxyalkylene and mixtures thereof, much more preferred are C-Cg alkylene. The skeletons that are most preferred in the present invention comprise at least 50% of R units that are ethylene. The R1 units are C2-Cg alkylene and mixtures thereof, preferably ethylene. R 2 is hydrogen and - (R -'- OJxB, preferably hydrogen R 3 is C 1 -C 4 alkyl, C 7 -C arylalkylene] 2, C 7 -C 2 alkyl substituted aryl, Cg-C 2 aryl, and mixtures thereof, preferably C 7 -C 12 alkylarylene C 7 -C 12 alkyl, most preferably C 1 -C 2 alkyl, more preferably methyl R units serve as part of the E units described below R 4 is C 1 alkylene ] -C- 2, 4-C-alkenylene] -2, aryl-C-C 1 -C arylene-2-arylene of Cg-CiQ preferably C 1 -C 1 alkylene / c 8"c 12 'arylalkylene, preferably C 2 -C 4 alkylene, more preferably ethylene or butylene R 5 is C 1 -C 2 alkylene, C 3 -C 12 hydroxyalkylene C 4 -C 2 dihydroxyalkylene, C 3 -C 2 dialkylarylene, -C (0) -, -C (0) NHR6NHC (0) -, -C (O) (R4) rC (O) -, R1 (OR1) -, (CH2CH (OH) CH20 (R10) and R1OCH2CH (OH) CH2-, -C (O) (R4) rC (0) -, (CH2CH (OH) CH2-; R5 is preferably ethylene, -C (0) -, C (0) NHR6NHC (0) -, R1 (OR1) -, -CH2CH (OH) CH2 -, (CH2CH (OH) CH20 (R10) and R1OCH2CH- (O H) CH2-, most preferably CH2CH (OH) CH2-. R6 is C2-C2 alkylene or C -C2 arylene. The preferred R "oxy" units are further defined in terms of the units R 1, R_? and R5. The preferred R "oxy" units comprise the preferred R, R ^ and R3 units. The preferred cotton soil removal agents of the present invention comprise at least 50% of R units that are ethylene. The units R 1, R_? and preferred R5 are combined with the R "oxy" units to produce the preferred R "oxy" units in the following manner. i) by substituting the preferred R5 in (CH2CH20) xR5 (OCH2CH2) x-, (CH2CH20) xCH2CHOHCH2- (OCH2CH2) x- is produced. -ip ii) by substituting the preferred R and R ^ in (CH2CH (OR2) CH20) z- (R10) and R10 (CH2CH (OR2) CH2) w-, (CH2CH (OH) CH20) z- (CH2CH20) and CH2CH20 is produced (CH2CH (OH) CH2) w-. iii) by substituting the preferred R2 in -CH2CH (OR2) CH2-, -CH2CH (OH) CH2- is produced. The units E are selected from the group consisting of hydrogen, C?-C22 alkyl, C3-C22 alkenyl, C7-C22 arylalkyl, C-C22 hydroxyalkyl, - (CH2) pC0 M, - (CH) qS03M, -CH (CH2C02M) C02M, - (CH2) nP03M, - (R10) mB, -C (0) R3, preferably hydrogen, C2-C22 hydroxyalkylene, benzyl, C] -C-alkylene alkylene of Cx-C22, - (R ^ O.mB, -C (0) R3, - (CH2) pC02M, (CH2) qS03M, -CH (CH2C02M) C02M, most preferably C1-C22 alkylene, - (R ^ .xB, -C ( 0) R3, - (CH2) pC02M, - (CH2) qS03M, CH (CH2C02M) C02M, more preferably alkylene of Cj_-C22, (R -'- OíxB and -C (0) R. When no modification is made or substitution on a nitrogen, then the hydrogen atom will remain as the portion representing E. The units E do not comprise hydrogen atoms when the units V, W or Z are oxidized, that is, the nitrogens are N-oxides. , the skeleton chain or the branching chains do not comprise units of the following structure: 0 0 0 t T t N- -R O H- -N- -R or - -N- -H H H H Additionally, the units E do not comprise carbonyl moieties directly attached to a nitrogen atom when the units V, W or Z are oxidized, that is, the nitrogens are N-oxides. According to the present invention, the portion -C (0) R3 of the unit E is not bound to a nitrogen modified in N-oxide, that is, there is no N-oxide of amides having the structure: 0 0 0 0 0 3 II t N- -R or RJ -C- -N- -R O f II 3 - -N- -C-RJ or combinations thereof. B is hydrogen, alkyl of C] _- Cg, - (CH2) qS03M, (CH2) pC02M, (CH2) q- (CHSO3M) CH2S03M, (CH2) q (CHS02M) CH2S03M, (CH2) pP03M, -PO3M, preferably hydrogen, - (CH2) qS03M, (CH2) q (CHS03M) CH2S03M, (CH2) q- (CHS02M) CH2S03M, most preferably hydrogen or - (CH2) qS03M. M is hydrogen or a cation soluble in water in an amount sufficient to satisfy the charge balance. For example, a sodium cation also satisfies - (CH2) pC02M and - (CH2) qS? 3M, resulting in portions (CH2) pC02Na and (CH2) qS? 3Na. More than one monovalent cation can be combined (sodium, potassium, etc.) to satisfy the required chemical charge balance. However, the charge of more than one anionic group can be balanced by means of a divalent cation, or more than one monovalent cation may be necessary to satisfy the loading requirements of a polyanionic radical. For example, a portion - (CH2) pP? 3 substituted with sodium atoms has the formula - (CH2) pP? 3Na3. Divalent cations such as calcium (Ca2 +) or magnesium (Mg +) can be substituted by, or combined with, other suitable water-soluble monovalent cations. The preferred cations are sodium and potassium, and sodium is very preferred.

X is a water-soluble anion such as chlorine (Cl ~), bromine (Br ~) and iodine (I ~), or X can be any negatively charged radical such as sulfate (S? 4 _) and methosulfate (CH3S? 3_) ). The indexes of the formulas have the following values: 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 0 or 1; m has the value of 4 to 400, n has the value of 0 to 200; m + n has the value of at least 5. Preferred modified polyamines comprise polyamine backbones in which less than about 50% of the R groups comprise R "oxy" units, preferably less than about 20%, preferably less of 5%, most preferably the R units do not comprise R "oxy" units. Highly preferred polyamines that do not comprise R "oxy" units, comprise polyamine backbones in which less than 50% of the R groups comprise more than 3 carbon atoms. For example, ethylene, 1,2-propylene, and 1,3-propylene comprise 3 carbon atoms or less, and are the preferred "hydrocarbyl" R units. That is, when the skeleton R units are C 2 -C 2 alkylene, C 2 -C 3 alkylene, preferably ethylene, is preefers. The polyamines of the present invention comprise homogeneous and non-homogeneous polyamine backbones in which 100% or less of the -NH units are modified. For the purpose of the present invention, the term "homogeneous polyamine skeleton" is defined as a polyamine skeleton having the same R units (ie, all are ethylene). However, this definition of equality does not exclude polyamines comprising other foreign units comprising the polymer backbone, which are present due to an artifact of the chosen chemical synthesis method. For example, those skilled in the art know that ethanolamine can be used as an "initiator" in the synthesis of polyethylene imines, therefore a polyethylene imine sample comprising a hydroxyethyl portion originating from the polymerization "primer" would be considered, comprises a homogeneous polyamine skeleton for the purposes of the present invention. A polyamine skeleton comprising all R units of ethylene in which no branching Y units are present, it is a homogeneous skeleton. A polyamine skeleton comprising all R units of ethylene is a homogeneous skeleton regardless of the degree of branching or the number of cyclic branches present. For the purposes of the present invention, the term "non-homogeneous polymer backbone" refers to polyamine skeletons which are a mixture of various lengths of unit R and types of unit R. For example, an inhomogeneous backbone comprises R units which they are a mixture of ethylene and 1,2-propylene units. For purposes of the present invention, a mixture of "hydrocarbyl" and "oxy" R units is not necessary to provide a non-homogeneous skeleton. Proper handling of these "chain lengths of unit R" provides the formulator with the ability to modify the solubility and substantivity in the fabric of the modified polymers. Preferred polyamines of the present invention comprise homogeneous polyamine backbones which are fully or partially substituted with polyethyleneoxy moieties, total or partially quaternized amines, nitrogens totally or partially oxidized to N-oxides, and mixtures thereof. However, not all nitrogens of the skeletal amine must be modified in the same way, leaving the choice of modification to the specific needs of the formulator. The degree of ethoxylation is also determined by the specific requirements of the formulator. Preferred polyamines comprising the backbone of the compounds of the present invention are generally polyalkyleneamines (PAA's), polyalkyleneimines (PAI's), preferably. polyethyleneamine (PEA's), polyethyleneimines (PEI's), or PEA's or PEI's connected by portions that have longer R units than the original PAA's, PAI's, PEA's or PEI's. A common polyalkyleneamine (PAA) is tetrabutylenepentamine. PEA's are obtained by reactions that include ammonia and ethylene dichloride, followed by fractional distillation. The common PEA's obtained are triethylenetetramine (TETA) and tetraethylenepentamine (TEPA). Above the pentamines, ie the hexamines, heptamines, octamines and possibly nonamines, the cogently derived mixture does not appear to be separated by distillation and may include other materials such as cyclic amines and particularly piperazines. Cyclic amines with side chains in which nitrogen atoms appear may also be present. See the patent of E.U.A. 2,792,372, Dickinson, issued May 14, 1957, which describes the preparation of PEA's. Preferred amine polymer backbones comprise R units which are C2 alkylene units (ethylene), also known as polyethylene imines (PEI's). Preferred PEI's have at least moderate branching, that is, the ratio of m to n is less than 4: 1, however, PEI's that have a m to n ratio of 2: 1 are preferred. The preferred skeletons, before modification, have the general formula: H I I [H2NCH2CH2] n- [NCH2CH2] m- [NCH2CH2] n-NH2 where m and n are the same defined above.

Preferred PEI's, before modification, will have a molecular weight of more than about 200 daltons. The relative proportions of the primary, secondary and tertiary amine units in the polymer skeleton, especially in the case of PEI's, will vary, depending on the form of preparation. Each hydrogen atom attached to each nitrogen atom of the polyamine backbone chain represents a potential site for subsequent substitution, quaternization or oxidation. These polyamines can be prepared, for example, by polymerizing ethyleneimine in the presence of a catalyst such as carbon dioxide, sodium bisulfite, sulfuric acid, hydrogen peroxide, hydrochloric acid, acetic acid, etc. The specific methods for preparing these polyamine skeletons are described in the U.S. patent. No. 2,182,306, Ulrich et al., Issued December 5, 1939; the patent of E.U.A. No. 3,033,746, Mayle et al., Issued May 8, 1962; the patent of E.U.A. No. 2,208,095, Esselman et al., Issued July 16, 1940; the patent of E.U.A. No. 2,806,839, Crowther, issued September 17, 1957; and the patent of E.U.A. No. 2,553,696, Wilson, issued May 21, 1951; all incorporated herein by reference. Examples of modified polyamines of the present invention comprising PEI's, are illustrated in formulas I-IV: Formula I represents a polymer comprising a PEI backbone in which all substitutable nitrogens are modified by hydrogen replacement with a polyoxyalkylenoxy unit , - (CH2CH20) 7H, having the formula: Formula I This is an example of a polymer that is completely modified with a type of portion. Formula II illustrates a polymer comprising a PEI skeleton in which all substitutable primary amine nitrogens are modified by hydrogen replacement with a polyoxyalkylenoxy unit, - (CH2CH20) 7H, the molecule is then modified by subsequent oxidation of all the primary and secondary nitrogens oxidizable to N-oxides; said 5 polymer has the formula: Formula II Formula III represents a polymer comprising a PEI skeleton wherein all of the hydrogen atoms in the backbone are substituted and some amine units in the backbone are quaternized. The substituents are polyoxyalkylenoxy units, - (CH 2 CH 20) 7 H, or methyl groups. The modified PEI polymer has the formula Formula III Formula IV represents a polymer comprising a PEI backbone wherein the nitrogens of the backbone are modified by substitution (i.e., with - (CH 2 CH 20) 7 H, or methyl), quaternized, or oxidized to N-oxides, or combinations thereof. The resulting polymer has the formula: Formula IV In the above examples, not all nitrogens of a unit class comprise the same modification. The present invention allows the formulator to have ethoxylated a portion of the secondary amine nitrogens, while having other secondary amine nitrogens oxidized in N-oxides. This also applies to the primary amine nitrogens, since the formulator may choose to modify all or a portion of the primary amine nitrogens with one or more substituents before oxidation or curing. Any possible combination of E groups may be substituent on the primary and secondary amine nitrogens, except for the restrictions described above.

Detersive surfactant paste or acid precursor The process employs a surfactant paste in which a detersive surfactant and water are included. This surfactant paste typically has a viscosity from about 5,000 cps to about 100,000 cps, preferably from about 10,000 cps to about 80,000 cps, and contains at least about 10% water, usually at least about 30% water. The viscosity is measured at 70 ° C and cutting speeds of about 10 to 100 sec "1. Alternatively, the process can employ a liquid acid precursor of an anionic detersive surfactant which is ultimately neutralized in the process to contain the surfactant salt and water. Typically, this anionic surfactant will be linear alkylbenzene sulfonate Optionally, other structure forming agents, viscosity modifiers, and various other secondary agents can be included in the surfactant paste or acid precursor thereof Non-limiting examples of useful surfactants in the paste surfactants include the conventional Cn-Ci8 alkylbenzenesulfonates ("LAS") and the branched and randomized primary chain alkyl ("AS") alkyl sulphates ("AS"), the secondary alkyl sulfates (2,3) of the C18-C18 the formula CH3 (CH2) x (CHOS03 ~ M +) CH3 and CH3 (CH2) and (CHOS03"M +) CH2CH3, where xy (y + 1) are integers of at least about 7, preferably at least about 9, and M is a cation of solubilization in water, especially sodium, unsaturated sulfates such as oleyl sulfate, the alkylalkoxy sulfates of c10 ~ c18 ("AEXS"; especially ethoxysulfates of 1-7 EO), alkylalkoxycarboxylates of C] _o-Ci8 (especially the ethoxycarboxylates of 1-5 of EO), the glycerol ethers of C] _Q-CIQ, the alkyl polyglycosides of C? o-Ci8 and their corresponding sulphated polyglycosides, and alphasulfonated fatty acid esters of C] _2-Ci8 mixtures thereof. If desired, additional surfactants in the surfactant paste may also be included as conventional amphoteric and nonionic surfactants such as alkylethoxylates ("AE") of the C 1 -C 8 including the so-called narrow peak alkylethoxylates and the C 1 -C 2 alkylphenylalkoxylates ( especially mixed ethoxylates and ethoxy / propoxy), betaines and sulfobetaines ("sultaines") of? 2-C_8 'amine oxides of C] _o-Ci8, and the like. N-alkyl polyhydroxylic acid amides can also be used. Typical examples include N-methylglucamides of C] _2-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 D-glucamide). The N-propyl to N-hexylglucamides of C] _2 can be used for low foaming. -C? 8- Conventional C? O-C20 soaps can also be used - if high foaming is desired, branched-chain soaps of C] _Q-C] _g can be used. Mixtures of anionic and nonionic surfactants are especially Useful Other useful surfactants are listed in the standard texts.

Dry detergent material Dry detergent material such as sodium sulfate or other filler and a detergency builder is also used in the process. provide fully formulated detergent compositions. The detergency builder controls the effects of mineral hardness during normal washing operations. Inorganic and organic improvers can be used. Builders are commonly used in laundry washing compositions to aid in the removal of particulate soils. The level of builder can vary widely depending on the final use of the composition and its desired physical form. When they are present, the compositions will typically comprise at least about 1% builder. Granular formulations typically comprise from about 10% to about 80%, very typically from about 15% to about 50%, by weight builder. However, lower or higher detergency builder levels are not excluded. Inorganic or P-containing builders include, but are not limited to, alkali metal, ammonium and alkanolammonium salts of polyphosphates (illustrated by tripolyphosphates, pyrophosphates and vitreous polymeric metaphosphates), phosphonates, phytic acid, silicates, carbonates (including bicarbonates and sesquicarbonates), sulfates and aluminosilicates. However, non-phosphate builders are required in certain places. Importantly, the compositions herein work surprisingly well even in the presence of so-called "weak" detergency builders (as compared to phosphate builders) such as citrates, or in the so-called "lower detergency enhancement" situation that It can occur with zeolite builders or stratified silicate. Examples of silicate builders are alkali metal silicates, particularly those having a ratio of SiO2: Na20 in the range of 1.6: 1 to 3.2: 1 and layered silicates, such as the layered sodium silicates described in the patent. US 4,664,839, issued May 12, 1987 to HP Rieck. NaSKS-6 is the trade name for a crystalline layered silicate sold by Hoechst (commonly abbreviated as "SKS-6"). Unlike zeolite builders, the NaSKS-6 silicate builder does not contain aluminum. NaSKS-6 has the morphological form of delta-Na2Si? 5 layered silicate. It can be prepared by methods such as those described in German Application DE-A-3, 417, 649 and DE-A-3, 742, 043. SKS-6 is a highly preferred layered silicate for use herein, but other layered silicates, such as those having the general formula NaMSix02x +] _ and H20 where M is sodium or hydrogen, x is a number from 1.9 to 4, preferably 2, and "y" is a number may be used herein. from 0 to 20, preferably 0. Some other stratified silicates from Hoechst include NaSKS-5, NaSKS-7 and NaSKS-11 as the alpha, beta and gamma forms. As indicated above, the delta-Na2Si? 5 (NaSKS-6) form is most preferred for use herein. Other silicates can also be used such as for example magnesium silicate, which can serve as a tightening agent in granulated formulations, as a stabilizing agent for oxygen bleaches, and as a component of foam control systems. Examples of carbonate builders are alkaline earth metal and alkaline carbonates as described in German Patent Application No. 2,321,001 published November 15, 1973.

Aluminosilicate builders are useful in the present invention. Aluminosilicate builders are of great importance in most of the heavy duty granular detergent compositions currently marketed, and can also be an important detergency builder ingredient in liquid detergent formulations. The aluminosilicate builders include those that have the empirical formula: Mz (zAl02) and] xH20 where z and "y" are integers of at least 6, the molar ratio of zay is in the range of about 1.0 to about 0.5, and x is an integer of about 15 to about 264. Useful exchange materials are commercially available. of aluminosilicate ions. These aluminosilicates may be of crystalline or amorphous structure and may be aluminosilicates of natural origin or synthetically derived. A method for producing aluminosilicate ion exchange materials is described in the U.S. Patent. 3,985,669, Krummel et al. Issued October 12, 1976. Preferred synthetic crystalline aluminosilicate ion exchange materials useful herein are available under the designations Zeolite A, Zeolite P (B), Zeolite MAP and Zeolite X. In a Especially preferred embodiment, the crystalline aluminosilicate ion exchange material has the formula: Na12 [(A102) 12 (Si02) 12] xH20 wherein x is from about 20 to about 30, especially about 27. The material is known as Zeolite A. Dehydrated zeolites (x = 0-10) can also be used herein. Preferably, the aluminosilicate has a particle size of approximately 0.1-10 microns in diameter. Organic builders suitable for the purposes of the present invention include, but are not limited to, a wide variety of polycarboxylate compounds. As used herein, "polycarboxylate" refers to compounds having a plurality of carboxylate groups, preferably at least 3 carboxylates. The polycarboxylate builder can usually be added to the composition in acid form, but can also be added in the form of a neutralized salt. When used in salt form, alkali metal salts such as sodium, potassium and lithium, or alkanolammonium are preferred. Included among the polycarboxylate builders are a variety of useful material categories. An important category of polycarboxylate builders encompasses ether polycarboxylates that include oxydisuccinate, as described by Berg in the U.S. patent. 3,128,287, issued April 7, 1964, and Lamberti et al., US patent. 3,635,830, issued January 18, 1972. See also the "TMS / TDS" detergency builders of the U.S. patent. No. 4,663,071, issued to Bush et al. On May 5, 1987. Suitable ether polycarboxylates also include cyclic compounds, particularly alicyclic compounds such as those described in US Patents. 3,923,679, 3,835,163; 4,158,635; 4,120,874, and 4,102,903. Other useful builders include ether hydroxypolycarboxylates, maleic anhydride copolymers with ethylene or vinyl methyl ether, 1,3,5-trihydroxybenzene-2,4,6-trisulfonic acid, and carboxymethyloxy-succinic acid, the different alkali metal salts , ammonium and substituted ammonium of polyacetic acids such as ethylenediaminetetraacetic acid and nitrilotriacetic acid, as well as polycarboxylates such as melific acid, succinic acid, oxydisuccinic acid, polymaleic acid, benzene-1,3,5-tricarboxylic acid, carboxymethyloxysuccinic acid, and salts soluble of them. Citrate builders, eg, citric acid and soluble salts thereof (particularly sodium salt), are polycarboxylate builders of particular importance for heavy duty liquid detergent formulations because of their availability from renewable resources and their biodegradability. The citrates can also be used in granular compositions, especially in combination with zeolite builders and / or layered silicate. Oxydisuccinates are also especially useful in said compositions and combinations. Also suitable in the detergent compositions of the present invention are the 3,3-dicarboxy-4-oxa-1, 6-hexanodiates and the related compounds described in the U.S. Patent. No. 4,566,984, Bush, issued January 28, 1986. Useful succinic acid builders include alkyl and C5-C20 alkenyl succinic acids and salts thereof. A particularly preferred compound of this type is dodecenylsuccinic acid. Specific examples of succinate builders include: laurylsuccinate, myristylsuccinate, palmitylsuccinate, 2-dodecenylsuccinate (preferred), 2-pentadecenylsuccinate, and the like. Lauryl succinates are the preferred builders of this group, and are described in European Patent Application 86200690.5 / 0,200,263, published November 5, 1986. Other suitable polycarboxylates are described in US Pat. 4,144,226, Crutchfield et al., Issued March 13, 1979, and in the US patent. 3,308,067 to Diehl, issued March 7, 1967. See also Diehl, US patent. 3,723,322. The fatty acids, e.g., monocarboxylic acids of C_12"c18 can also be incorporated into the compositions alone, or in combination with the aforementioned builders, especially the citrate and / or succinate builders, to provide additional builder activity, said use of fatty acids will generally give The decrease in foaming results, which should be considered by the formulator In situations where phosphorus-based builders can be used, and especially in bar formulations used for hand-washing operations, various phosphates can be used. of alkali metal such as the well-known sodium tripolyphosphates, sodium pyrophosphate and sodium orthophosphate.Posphonate builders such as ethan-1-hydroxy-1,1-diphosphonate and other known phosphonates can also be used (see, for example, example, US Patents 3,159,581, 3,213,030, 3,422,021, 3,400,148 and 3,422,137).

Auxiliary detergent ingredients One or more auxiliary detergents may be incorporated in the detergent composition during subsequent steps of the process of the present invention. These auxiliary ingredients include other surfactants such as cationic surfactants, other builders, foam enhancers or foam suppressors, anti-rust and anti-corrosion agents, soil suspending agents, soil removal agents, germicides, pH adjusting agents. , alkalinity sources without detergent improver, chelating agents such as diethylenetriaminepentaacetic acid (DTPA) and diethylenetriamine-pentamentylene phosphonic acid, smectite clays, enzymes, enzyme stabilizing agents, dye transfer inhibitors and perfumes. See U.S. Patent No. 3,936,537, issued February 3, 1976 to Baskerville, Jr., et al., Incorporated herein by reference. Other builders can generally be selected from various water-soluble alkali metal, ammonium or substituted ammonium phosphates, polyphosphates, phosphonates, polyphosphates, carbonates, borates, polyhydroxysulfonates, polyacetates, polycarboxylates and carboxylates. The alkali metal, especially sodium, salts of the above are preferred. It is preferred to use herein the phosphates, carbonates, fatty acids of C] _Q-i8 polycarboxylates and mixtures thereof. Sodium tripolyphosphate, tetrasodium pyrophosphate, citrate, tartrate, mono- and di-succinates, and mixtures thereof are preferred (see below). Compared to amorphous sodium silicates, the crystalline layered sodium silicates exhibit a clearly increased calcium and magnesium ion exchange capacity. In addition, stratified sodium silicates prefer magnesium ions over calcium ions, a feature necessary to ensure that substantially all of the "hardness" is removed from the wash water. These crystalline stratified sodium silicates, however, are generally more expensive than amorphous silicates as well as other enhancers. Therefore, to provide an economically feasible laundry detergent, the proportion of crystalline sodium silicates used should be conveniently determined. The crystalline stratified sodium silicates suitable for use herein preferably have the formula: NaMSix02x + ?. yH20 wherein M is sodium or hydrogen, x is from about 1.9 to about 4 and "y" is from about 0 to about 20. Preferably, the crystalline layered sodium silicate has the formula NaMSi205.yH20 wherein M is sodium or hydrogen, and "and" is from about 0 to about 20. These and other crystalline stratified sodium silicates are discussed in Corkill et al., U.S. Patent No. 4,605,509, previously incorporated herein by reference. reference. Specific examples of inorganic phosphate builders are tripolyphosphate, pyrophosphate, polymeric metaphosphate having a degree of polymerization of about 6 to 21, and sodium and potassium orthophosphates. Examples of polyphosphonate builders are the sodium and potassium salts of ethylene diphosphonic acid, the sodium and potassium salts of ethan-1-hydroxy-1,1-diphosphonic acid, and the sodium and potassium salts of ethan-1 acid, 1, 2-triphosphonic. Other phosphorus-improving compounds are described in U.S. Patent No. 3,159,581; 3,213,030; 3,422,021; 3,422,137; 3,400,176 and 3,400,148, all of which are incorporated herein by reference. Examples of non-phosphorus inorganic builders are tetraborate decahydrate and silicates having a weight ratio of SiO2 to alkali metal oxide of from about 0.5 to about 4.0, preferably from about 1.0 to about 2.4. Water-soluble organic phosphorus-free builders, useful herein include the various alkali metal, ammonium and ammoniosubstituted polyacetates, carboxylates, polycarboxylates and polyhydroxysulfonates. Examples of polyacetate and polycarboxylate builders are the sodium, potassium, lithium, ammonium and substituted ammonium salts of ethylenediaminetetraacetic acid, nitrilotriacetic acid, oxydisuccinic acid, melific acid, benzenedicarboxylic acids and citric acid. Polymeric polycarboxylate builders are indicated in U.S. Patent No. 3,308,067, Diehl, issued March 7, 1967, the disclosure of which is incorporated herein by reference. Such materials include the water-soluble salts of homo- and copolymers of aliphatic carboxylic acids such as maleic acid, itaconic acid, mesaconic acid, fumaric acid, aconitic acid, citraconic acid and methylenemalonic acid. Some of these materials are useful as the water-soluble anionic polymer as described hereinafter, only if it is in intimate admixture with the non-soap anionic surfactant. Other polycarboxylates suitable for use herein are the polyacetalcarboxylates described in U.S. Patent No. 4,144,226, issued March 13, 1979 to Crutchfield et al., And U.S. Patent No. 4,246,495, issued March 27, 1979 to Crutchfield and others, both incorporated herein by reference. These polyacetalcarboxylates can be prepared by mixing a glyoxylic acid ester and a polymerization initiator under polymerization conditions. The resulting polyacetal carboxylate ester is then attached to chemically stable end groups to stabilize the polyacetal carboxylate against rapid depolymerization in alkaline solution, converted to the corresponding salt, and added to a detergent composition. Particularly preferred polycarboxylate builders are ether carboxylate builder compositions comprising a combination of monosuccinatotartrate and disuccinatotartrate described in U.S. Patent No. 4,663,071, Bush et al., Issued May 5, 1987, the disclosure of which is incorporated herein by reference. reference. Smectite clays suitable for use herein are described in U.S. Patent 4,762,645, Tucker et al., Issued August 9, 1988, column 6, line 3 to column 7 line 24, incorporated herein by reference. Additional detergency builders suitable for use herein are cited in the Baskerville patent, column 13, line 54 to column 16 line 16, and in U.S. Patent No. 4,663,071, Bush et al., Issued May 5, 1987, both incorporated herein by reference. In order to make the present invention more easily understandable, reference is made to the following examples which are intended to be illustrative only and not limiting in scope.

EXAMPLE I Preparation of PEÍ 1800 E7 This example illustrates a method by which one of the selected modified polyamines is prepared. The ethoxylation is carried out in a 7.56 liter stirred stainless steel autoclave equipped for temperature measurement and control, pressure measurement, vacuum and inert gas purging, sampling, and for the introduction of ethylene oxide as a liquid. A cylinder of 7.5 kg net of ethylene oxide (ARC) is installed to supply ethylene oxide as a liquid by means of a pump to the autoclave placing the cylinder on a scale to be able to monitor the changes in the weight of the cylinder. A 750 g portion of polyethylenimine (PEI) (Nippon Shokubai, Epomin SP-018 having a listed average molecular weight of 1800, equivalents to about 0.417 moles of polymer and 17.4 moles of nitrogen functions) is added to the autoclave. The autoclave is sealed and then purged of air (applying a vacuum to minus 711 mm Hg followed by applying pressure with nitrogen at 17.57 kg / cm2, then ventilating at atmospheric pressure). The contents of the autoclave are heated to 130 ° C while vacuum is applied. After about one hour, the autoclave is charged with nitrogen at about 17.57 kg / cm while the autoclave is cooled to about 105 ° C. Ethylene oxide is then added to the autoclave in increments over time while carefully monitoring the pressure, temperature and flow rate of ethylene oxide in the autoclave. The ethylene oxide pump is turned off and cooling is applied to limit any increase in temperature caused by any reaction exotherm. The temperature is maintained between 100 and 110 ° C while the total pressure is allowed to gradually increase during the course of the reaction. After a total of 750 grams of ethylene oxide has been charged into the autoclave (almost equivalent to one mole of ethylene oxide per function of PEI nitrogen), the temperature is increased to 110 ° C and the autoclave is allowed to shake for an additional hour. At this point, vacuum is applied to remove any residual ethylene oxide that did not react. Then vacuum is applied continuously while the autoclave is cooled to approximately 50 ° C, introducing 376 g of a 25% sodium methoxide solution in methanol (1.74 moles) to achieve a catalyst load of 10% based on the functions of PEI nitrogen). The methoxide solution is sucked into the autoclave under vacuum and then the programming point of the autoclave temperature controller is increased to 130 ° C. A device is used to monitor the energy consumed by the agitator. The power of the agitator is monitored together with the temperature and pressure. The power and temperature values of the agitator increase gradually as the methanol is removed from the autoclave, and the viscosity of the mixture increases and stabilizes in about one hour indicating that most of the methanol has been removed. The mixture is heated and stirred under vacuum for an additional 30 minutes. The vacuum is removed and the autoclave is cooled to 105 ° C while it is charged with nitrogen at 17.57 kg / cm and then ventilated at ambient pressure. The autoclave is charged at 14.06 kg / cm2 with nitrogen. Ethylene oxide is again added to the autoclave in increments as mentioned above, carefully monitoring the pressure, temperature and flow rate of ethylene oxide in the autoclave, while maintaining the temperature between 100 and 110 ° C and limiting any increase in temperature due to the exotherm of the reaction. After achieving the addition of 4,500 g of ethylene oxide (resulting in a total of 7 moles of ethylene oxide per mole of nitrogen function of PEI) for several hours, the temperature is increased to 110 ° C and the mixture is Shake for an additional hour. The reaction mixture is then collected in containers purged with nitrogen and is finally transferred to a 22-liter three-necked round bottom flask equipped with heating and stirring. The strong alkaline catalyst is neutralized by adding 167 g of methanesulfonic acid (1.74 mol). The reaction mixture is then deodorized by passing about 2.8 m 3 of inert gas (argon or nitrogen) through a gas dispersion frit and through the reaction mixture while stirring and heating the mixture to 130 ° C. The final product of the reaction is cooled gently and collected in glass containers purged with nitrogen. In other preparations, neutralization and deodorization are carried out in the reactor before discharging the product.

EXAMPLE II Quaternization of PEÍ 1800 E7 This example illustrates another method by which one of the selected modified polyamines is prepared. To a 500 ml Erlenmeyer flask, equipped with a magnetic stir bar, is added polyethyleneimine having a molecular weight of 1800, and is ethoxylated to a degree of about 7 ethoxy groups per nitrogen (PEI 1800, E7) (209 g. , 0.595 moles of nitrogen, prepared as in example I) and hydrogen peroxide (120 g of a 30% by weight solution in water, 1.06 moles). The flask is capped, and after an initial exotherm, the solution is stirred at room temperature overnight. The spectrum obtained from H-NMR (D20) on a sample of the reaction mixture indicates complete conversion. The resonances attributed to methylene protons adjacent to non-oxidized nitrogens have shifted from the original position to -2.5 ppm, down to -3.5 ppm. To the solution of the reaction is added approximately 5 g of 0.5% Pd on aluminum pellets, and the solution is allowed to stand at room temperature for about 3 days. The solution is analyzed and it is negative for peroxide according to indicator paper. The material obtained is conveniently stored as a solution in water at a concentration of 51.1%.

EXAMPLE III Preparation of PEÍ 1200 E7 This example illustrates another method by which one of the selected modified polyamines is prepared. The ethoxylation is carried out in a stirred stainless steel autoclave of 7.56 liters, equipped for measurement and temperature control, pressure measurement, vacuum and inert gas purging, sampling, and for the introduction of ethylene oxide as a liquid. A cylinder of 7.5 kg net of ethylene oxide (ARC) is installed to supply ethylene oxide as a liquid by means of a pump to the autoclave placing the cylinder on a scale to be able to monitor the changes in the weight of the cylinder. A 750 g portion of polyethylenimine (PEI) (having a listed average molecular weight of 1200, equivalents to 0.625 moles of polymer and 17.4 moles of nitrogen functions) is added to the autoclave. The autoclave is then sealed and purged of air (applying vacuum to minus 711 mm Hg followed by applying pressure with nitrogen at 17.57 kg / cm2, then ventilating at atmospheric pressure). The contents of the autoclave are heated to 130 ° C while vacuum is applied. After about one hour, the autoclave is charged with nitrogen at about 17.57 kg / cm2 while the autoclave is cooled to about 105 ° C. Ethylene oxide is then added to the autoclave in increments over time while carefully monitoring the pressure, temperature and flow rate of ethylene oxide in the autoclave. The ethylene oxide pump is turned off and cooling is applied to limit any increase in temperature that results from any reaction exotherms. The temperature is maintained between 100 and 110 ° C while the total pressure is allowed to gradually increase during the course of the reaction. After a total of 750 grams of ethylene oxide has been charged into the autoclave (almost equivalent to one mole of ethylene oxide per function of PEI nitrogen), the temperature is increased to 110 ° C and the autoclave is allowed to shake for an additional hour. At this point, vacuum is applied to remove any residual ethylene oxide that did not react. Then vacuum is applied continuously while the autoclave is cooled to approximately 50 ° C by introducing 376 g of a 25% sodium methoxide solution in methanol (1.74 moles) to achieve a catalyst load of 10% based on the functions of PEI nitrogen). The methoxide solution is sucked into the autoclave under vacuum and then the programming point of the autoclave temperature controller is increased to 130 ° C. A device is used to monitor the energy consumed by the agitator. The power of the agitator is monitored together with the temperature and pressure. The power and temperature values of the agitator increase gradually as the methanol is removed from the autoclave, and the viscosity of the mixture increases and stabilizes in approximately one hour indicating that most of the methanol has been removed. The mixture is heated and further stirred under vacuum for an additional 30 minutes. The vacuum is removed and the autoclave is cooled to 105 ° C while charging with nitrogen at 17.57 kg / cm2 and then ventilated at ambient pressure. The autoclave is charged at 14.06 kg / cm2 with nitrogen. Ethylene oxide is added again to the autoclave in increments as mentioned above, carefully monitoring the pressure, temperature and flow rate of ethylene oxide in the autoclave, while maintaining the temperature between 100 and 110 ° C, and limiting any increase in temperature due to the exotherm of the reaction. After achieving the addition of 4,500 g of ethylene oxide (resulting in a total of 7 moles of ethylene oxide per mole of nitrogen function of PEI) for several hours, the temperature is increased to 110 ° C and the mixture is Shake for an additional hour. The reaction mixture is then collected in nitrogen purged containers and finally transferred to a 22-liter, three-necked round bottom flask equipped with heating and stirring. The strong alkaline catalyst is neutralized by adding 167 g of methanesulfonic acid (1.74 mol). The reaction mixture is then deodorized by passing about 2.8 m 3 of inert gas (argon or nitrogen) through a gas dispersion frit and through the reaction mixture while stirring and heating the mixture to 130 ° C. The final reaction product is cooled slightly and collected in glass containers purged with nitrogen. In other preparations, neutralization and deodorization are performed in the rector before unloading the product.

EXAMPLE IV A modified polyamine is prepared according to Example I ("PEI180 E7"), and is used in the process of the present invention to form an agglomerated detergent composition. An in-line static mixer is used in which PEI1800 E7 is continuously added, together with a linear sodium alkylbenzenesulfonate surfactant paste ("LAS") (60% LAS and the rest water) at approximately 60 ° C to completely mix the ingredients, where the pH of the mixture is maintained at about 7 to 10. After, the premix is continuously loaded to a high mixer / densifier. speed (Lódige CB-30, commercially available from Lódige) together with sodium aluminosilicate (zeolite) and sodium carbonate. The speed of rotation of the arrow in the Lódige CB-30 mixer / densifier is approximately 1400 rpm and the average residence time is approximately 10 seconds. The content of the mixer / diluent Lódige CB-30 is continuously fed to a mixer / densifier Lódige KM 600 for subsequent agglomeration, during which the average residence time is about 6 minutes. Then, the detergent agglomerates are screened with conventional screening apparatus, resulting in a uniform distribution of particle size. The composition of the resulting detergent agglomerates is indicated in Table I below.

TABLE I Component% by weight Linear alkylbenzenesulfonate of C_2_t.3 29.1 Sodium aluminosilicate 34.4 Sodium carbonate 17.5 Polyethylene glycol (MW 4000) 1.3 PEI1800 E7 1.0 Miscellaneous (water, etc.) 15.7 100. 0 The performance test for maintenance of whiteness in multiple cycles is carried out using standard washing analysis techniques with test samples of fabrics of different fiber contents. Unexpectedly, the agglomerated detergent compositions prepared by means of a process according to the invention, wherein the PEI1800 E7 is premixed with LAS in the pre-mixer, exhibits significantly improved cleaning action compared to the compositions prepared by processes outside the scope of the present invention. invention.

EXAMPLE V A modified polyamine polymer is prepared in accordance with Example I ("PEI1800 E7") and is used in another aspect of the present invention to form an agglomerated detergent composition. A static in-line mixer is used in which PEI1800E7 is continuously added together with the acid form of the linear alkylbenzene sulfonate ("HLAS") to form a completely combined premix. The premix is then continuously fed to a high-speed mixer / disinfector (Lódige CB-30, commercially available from Lódige), together with sodium carbonate and other dry detergent materials. Non-limiting examples of useful dry detergent materials include sodium aluminosilicate (zeolite), sodium tripolyphosphate (STPP) and sodium sulfate. The rotation speed of the arrow in the Lódige mixer / densifier CB-30 is approximately 1400 rpm, and the average residence time is approximately 10 seconds. The content of the mixer / dilutor Lódige CB-30 is continuously fed to a mixer / densifier Lódige KM-600 for further agglomeration during which the average residence time is about 6 minutes. The detergent agglomerates are then sieved with a conventional screening apparatus, resulting in a uniform distribution of particle size. The composition of the resulting detergent agglomerates is indicated in Table 2 below: TABLE 2 Component% by weight C 2-13 linear alkylbenzenesulfonate 20.0% Sodium carbonate 18.0% PEI1800E7 0.5% Sodium aluminosilicate 16.0% Sodium tripolyphosphate 35.0% Sodium sulphate 3.5% Miscellaneous (water, etc.) 7.0% 100. 0% The performance test for maintenance of whiteness in multiple cycles is carried out using standard washing analysis techniques with test samples of fabrics of different fiber contents. Unexpectedly, the agglomerated detergent compositions prepared by means of a process in accordance with this aspect of the invention, wherein the PEI1800 E7 is premixed with HLAS in the pre-mixer, exhibits significantly improved cleaning action compared to the compositions prepared by processes outside the scope of the present invention. Having described the invention in this manner in detail, it will be clear to the man skilled in the art that various changes can be made without departing from the scope of the invention, and this is not considered limited to what is described in the specification.

Claims (20)

NOVELTY OF THE INVENTION CLAIMS

1. - A process for producing an agglomerated detergent composition comprising the steps of: (a) premixing a detersive surfactant paste, dry detergent material and a modified water soluble or dispersible polyamine in a pre-mixer to form a premix, said modified polyamine having a polyamine skeleton corresponding to the formula: H [H2N-R] n + i- [NR] mI [NR] n-INH2, which has a modified polyamine formula V (n +?) WmYnZ, or a polyamine skeleton which corresponds to the formula: [H2N-R] n_k +? - [NR] NH2, which has a modified polyamine formula V (n_k +?) WmYnY'k Z, wherein k is less than or equal to n, said polyamine backbone, before modification, has a molecular weight greater than about 200 daltons, wherein: i) the units V are terminal units having the formula: EX "O or E - N - R - or H - N + - R - or E-- N - R - ooo ii) the units W are skeleton units having the formula: EX "0 --N - R or --N l ++ - R- or --N - R - III EEE iii) units Y are branching units that have the formula: EX "O | --N - R or --N + -R- or --N - R- and iv) Z units are terminal units that They have the formula: wherein the skeletal linker units R are selected from the group consisting of C2-C alkylene, 4"c12 alkenylene C3-C2 hydroxyalkylene, C4-Ci2 dihydroxyalkylene, C8-C2 dialkylarylene, - (R ^ -OJxR1-, - (R1 ^ XR5 (OR1) ^ - (CH2CH (OR2) CH20) z (R10) and R1- (OCH2CH (OR2) CH2) w ", -C (0) (R4) rC ( 0) -, -CH2CH (OR) CH2-, and mixtures thereof, wherein R1 is C-Cg alkylene, and mixtures thereof, R2 is hydrogen, - (R -'- OJxB, and mixtures thereof). R3 is C1-C18 alkyl, C7-C2 arylalkyl, aryl substituted with C7-C2alkyl, Cg-C2aryl, and mixtures thereof; R4 is C? ~ 12alkylene; C4 ~ C2 alkenylene, C8 ~ C2 arylalkylene, Cg-Cio arylene, and mixtures thereof, R5 is C?-C 2 alkylene, C 3 -C 2 hydroxyalkylene, 4 ~ C-dihydroxyalkylene; 2, dialkylarylene of C8-C12, -C (O) -, -C (0) NHR6NHC (O) -, -R1 (OR1) -, -C (O) (R4) rC (0) -, CH2CH (OH CH2-, CH2CH (OH) CH20- (R10) and R1OCH2CH (OH) CH2-, and mixtures thereof; R6 is C-alkylene -C? 2 or arylene of Cg-C? 2; the E units are selected from the group consisting of hydrogen, C?-C22 alkyl, c3"c22 alkenyl, C7-C22 arylalkyl, C2-C22 hydroxyalkyl, (CH2) pC02M, - (CH2) qS03M, -CH (CH2C02M) C02M, - (CH2) pP03M, (R- ^ - Ojj? B, -C (0) R3, and mixtures thereof; oxide; B is hydrogen, C-Cg alkyl, - (CH2) qS03M , - (CH2) pC02M, (CH2) q (CHS03M) CH2S03M, - (CH2) q- (CHS02M) CH2S03M, - (CH2) pP03M, -PO3M, and mixtures thereof, M is hydrogen or a soluble cation in water in sufficient quantity to satisfy the charge balance, X is a water soluble anion, m has the value of 4 to about 400, n has the value of 0 to about 200, p has the value of 1 to 6, 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, "y" has the value of 0 to 100, z has the value of 0 or 1, and (b) agglomerating said premix initially in a high speed mixer / densifier and subsequently in a speed mixer / densifier. moderate, so as to form agglomerates, thus producing the detergent composition.

2. - The method according to claim 1, characterized in that the pH of said premix is in the range from about 8 to about 10.

3. - The method according to claim 1, characterized in that said modified polyamine is present in an amount of about

0. 01% to about 10% by weight of said detergent composition. 4. The method according to claim 1, characterized in that said pre-mixing step is carried out for at least about 5 seconds.

5. - The method according to claim 1, characterized in that said surfactant paste has a viscosity of about 5,000 cps to about 100,000 cpas, and contains about 70% to 95% by weight of said surfactant paste, a detersive surfactant and the balance is water and auxiliary ingredients.

6. - The method according to claim 1, characterized in that said dry detergent material includes a builder selected from the group consisting of carbonates, phosphates, citrates, aluminosilicates and mixtures thereof.

7. The method according to claim 1, further characterized in that it comprises the step of drying said agglomerates.

8. The method according to claim 1, characterized in that said agglomerates have a density of approximately 650 g / 1.

9. The process according to claim 1, characterized in that R is C 2 -C 2 alkylene.

10. A process for producing an agglomerated detergent composition comprising the steps of: (a) premixing an acid precursor of a detersive surfactant, dry detergent material and a modified polyamine soluble or dispersible in water, in a pre-mixer to form a premix , said modified polyamine has a polyamine skeleton corresponding to the formula: H I I [H2N-R] n +? - [N-R] m- [N-R] n-NH2, having a modified polyamine formula V (n + i) WmYnZ, or a polyamine skeleton corresponding to the formula: I HR [H2N-R] n-k +? - [NR] m I- [NR] nI- [NR] kI-NH2, which has a modified polyamine formula V (n_ +) WmYnY 'k Z, where k is less than or equal to n, said polyamine skeleton, prior to modification, has a molecular weight greater than about 200 daltons, wherein: i) units V are terminal units having the formula: EX "O or E - N --R- or H - N + - R - O E - N - R - ooo EEE ii) units W are skeleton units having the formula: EX "O - N - R or --N + -R- or -N-R- iii) the Y units are branching units having the formula: EX "0 --N - R or - -N 1 + -R- or - -N- -R - III and iv) the Z units are terminal units that have the formula: EX "O --N - E or --N + -E or --N - EIII EEE wherein the skeletal linker units R are selected from the group consisting of C2-C2 alkylene, c4-c12 alkenylene C3-C2 hydroxyalkylene, C4-C2 dihydroxyalkylene, C8-C2 dialkylarylene , - (R10) xR1-, - (R10) XR5 (OR1) x, - (CH2CH (OR2) CH20) z (R10) and R1- (OCH2CH (OR2) CH2) w ", -C (O) (R) rC (0) -, -CH2CH (0R) CH2-, and mixtures thereof, wherein R1 is C2-Cg alkylene, and mixtures thereof, R2 is hydrogen, - (R10) xB, and mixtures thereof R3 is 1-C18 alkyl, C7-C2 arylalkyl, aryl substituted with C7-C2 alkyl, Cg-C2 aryl, and mixtures thereof; R4 is C'122 alkylene; ~ C2, C8 ~ C2 arylalkylene, c6"c10 arylene, and mixtures thereof; R5 is C? -C? 2 alkylene, 3-C? 2 hydroxyalkylene, 4-C? 2 dihydroxyalkylene, C8-C? 2 dialkylarylene. -C (0) -f -C (0) NHR6NHC (0) -, -R1 (0R1) -, -C (0) (R4) rC (0) -, CH2CH (0H) CH2-, CH2CH (OH) CH20- (R10) and R10CH2CH (0H) CH2-, and mixtures thereof; R6 is C2-C2 alkylene or Cg-C2 arylene; the units E are selected from the group consisting of hydrogen, C?-C22 alkyl, c3"c22 alkenyl, C7-C2 arylalkyl, C2-C22 hydroxyalkyl, (CH2) pC02M, - (CH2) qS03M, - CH (CH2C02M) C02M, - (CH2) pP03M, (R- ^ OJxB, -C (0) R, and mixtures thereof; oxide; B is hydrogen, Ci-Cg alkyl, - (CH2) qS03M, - (CH2) pC02M, (CH2) q (CHS03M) CH2S03M, - (CH2) q- (CHS02M) CH2S03M, - (CH2) pP03M, -PO3M, and mixtures thereof; M is hydrogen or a cation soluble in water in an amount sufficient to satisfy the balance of the charge; X is a water soluble anion; m has the value of 4 to about 400; n has the value from 0 to about 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; "y" has the value of 0 to 100; z has the value of 0 or 1; and (b) introducing said premix into the high speed mixer / densifier and neutralizing said acid precursor to form agglomerates; and (c) agglomerating said agglomerates further in a moderate speed mixer / densifier, so as to form said detergent composition.

11. - The method according to claim 10, characterized in that the pH of said premix is in the range from about 1 to about 3. 12. The process according to claim 10, characterized in that said modified polyamine is present in an amount approximately

0. 01% to about 10% by weight of said detergent composition.

13. - The method according to claim 10, characterized in that said pre-mixing step is carried out on a temperature scale from about 50 ° C to about 90 ° C.

14. - The method according to claim 10, characterized in that said step of introduction includes the step of adding a neutralization agent selected from the group consisting of sodium carbonate, sodium hydroxide, sodium silicate and mixtures thereof, to said high speed mixer / densifier, in such a way as to neutralize said acid precursor.

15. The process according to claim 14, characterized in that said neutralizing agent is sodium carbonate.

16. The method according to claim 10, further characterized in that it comprises the step of drying said agglomerates.

17. - The method according to claim 10, characterized in that said agglomerates have a density of at least about 650 g / 1.

18. The process according to claim 10, characterized in that R is C2-C12 alkylene.

19. An agglomerated detergent composition prepared according to the process of claim 1.

20. An agglomerated detergent composition prepared in accordance with with the method of claim 10.