MXPA00000154A - Bleach compatible alkoxylated polyalkyleneimines - Google Patents

Abstract

The present invention relates to laundry detergent compositions which comprise bleach compatible hydrophobic soil dispersants. The dispersants are polyalkyleneimines having a backbone molecular weight of from about 2000 to about 5000 daltons and having most of the N-H unit hydrogens, preferably all N-H unit hydrogens substituted with from about 20 to about 50, alkyleneoxy units.

Description

ALCOXYLATED POLYALYKYLENIMINES COMPATIBLE WITH BLEACHER FIELD OF THE INVENTION The present invention relates to alkoxylated polyalkyleneimines which are compatible with bleach. The alkoxylated polyalkyleneimines are also useful as hydrophobic soil dispersants which are suitable for use in laundry detergent compositions comprising a bleaching agent. The alkoxylated polyalkyleneimines are also suitable for use as soil dispersants in bleach and pre-soaking agents for laundry containing bleach.

BACKGROUND OF THE INVENTION Without a suitable dispersant, the hydrophobic dirt (eg oil, soot, soot) and hydrophilic (eg mud) that is removed during the washing step of the laundry process can be redeposited on the washed fabric. The dirt dispersants act by sequestering the dirt once it has dissolved or dispersed in the wash solution and keeps the dirt suspended in the wash solution from where it can be removed during the normal rinse procedure. s ^^^ 2 = ^! i í S? ^ == ^ = _ = ^^^^^ s * ^^^^^^ ^ s ^^^^^^^^ g? ^ = j Normally, if bleaching agents, especially peroxygen bleaches which are formulated in liquid and granular laundry detergent compositions are presented, the formulator should take into account the instability of a particular dirt dispersant towards a bleach. Many suitable dispersants contain polyalkyleneamine or polyalkyleneimine base structures that are susceptible to oxidation in the amine functionalities and potential to break or fragmentation by bleaching agents that may occur. From another point of view, the interaction of bleaching agents with these dispersants based on polyalkyleneimine reduces the amount of bleach present, thus affecting the bleaching performance. Also, the need persists in the art for obtaining highly effective hydrophobic soil dispersants compatible with bleach. Surprisingly, it has been found that certain polyalkyleneimines of higher molecular weight when highly alkoxylated, are compatible with bleach in laundry compositions and additionally provide hydrophobic soil dispersion. It has also been found to be beneficial that the alkoxylated dispersants comprise in the alkylene oxide substituent group, mixtures of ethylene oxide and propylene oxide.

BACKGROUND OF THE PREVIOUS TECHNIQUE The following describes various dirt dispersants or modified polyamines; the Patent of E.U.A. No. 5,565,145, Watson et al., 5 issued October 15, 1996; the Patent of E.U.A. No. 4,891, 160, Vander Meer, issued on January 2, 1990; the Patent of E.U.A. No. 4,726,909, Otten et al., Issued February 23, 1988; the Patent of E.U.A. No. 4,676,921, Vander Meer, issued June 30, 1987; the Patent of E.U.A. No. 4,548,744, Connor, issued October 22, 1985; 10 the Patent of E.U.A. No. 4,597,898, Vander Meer, issued July 1, 1986; European Patent Application 0 206 515, published on December 30, 1986.

BRIEF DESCRIPTION OF THE INVENTION The present description covers the above needs by the fact that it has been found that the ethoxylated polyalkyleneimines having a base structure of molecular weight of more than about 2,000 daltons, and an average degree of alkylenoxylation per unit NH of about 20 to about 50 alkylenoxy units, provide a hydrophobic soil dispersant that is compatible with bleach. The alkoxylated polyalkyleneimines of the present invention are suitable for use in granular compositions of high and low density, compositions liquid heavy and light work, as well as detergent compositions in laundry bar. A first aspect of the present invention relates to a hydrophobic soil dispersant having the formula: E B [E2N-R] n + 1- [N-R] m- [N-R] n-NE2 wherein R is linear C2-C6 alkylene, branched C3-C6 alkylene, and mixtures thereof; E is an alkylenoxy unit having the formula: - (R10) xR2 wherein R1 is linear C2-C alkylene, branched C3-C4 alkylene, and mixtures thereof; R2 is hydrogen, C1-C4 alkyl, and mixtures thereof; m is from about 10 to about 70; n is from about 5 to about 35; and x is from 20 to about 50; and B represents a continuation of the structure by branching. The present invention also relates to laundry detergent compositions comprising: a) at least about 0.01% to about 95%, preferably about 0.1% to about 60%, most preferably about 0.1% to about 30% by weight, of a detersive surfactant selected from the group consisting of anionic, nonionic, cationic, zwitterionic, and ampholytic surfactants, and mixtures thereof; b) from about 0.05% to about 30%, most preferably from about 1% to about 30%, still very preferably from about 5% to about 20%, by weight, of an oxygen bleaching agent, said Oxygen bleaching agent is selected from the group consisting of alkali metal percarbonate, perborate, monoperftalate, pyrophosphate peroxy hydrate, peroxy hydrated urea and mixtures thereof; 10 c) from about 0.01 to about 10% by weight, of a water-soluble or dispersible alkoxylated polyamine, according to the present invention; and d) auxiliary ingredients and balance vehicles wherein the auxiliary ingredients are selected from the group consisting of improvers Detergency detergents, optical brighteners, bleaches, bleach catalysts, bleach activators, dirt release polymers, dye transfer agents, dispersants, enzymes, foam suppressants, dyes, perfumes, dyes, filler salts, hydrotropes, enzymes, photoactivators, fluorescers, fabric conditioners, agents hydrolysable surfactants, preservatives, antioxidants, chelators, stabilizers, anti-shrinkage agents, anti-wrinkle agents, germicides, fungicides, anti-corrosion agents, and mixtures thereof.

Another aspect of the present invention relates to a laundry bleaching composition comprising: a) from about 0.05% to about 30%, most preferably from about 1% to about 30%, still most preferably about 5% a about 20% by weight, of an oxygen bleaching agent said oxygen bleaching agent is selected from the group consisting of alkali metal percarbonate, perborate, monoperftalate, pyrophosphate peroxyhydrate, urea peroxyhydrate and mixtures thereof; b) from about 0.05% to about 50%, preferably from about 1% to about 60%, most preferably from about 5% to about 30% by weight, of a bleach activator; c) from about 0.01% to about 10% by weight, of a water-soluble or dispersible alkoxylated polyamine according to the present invention; and d) vehicles and auxiliary ingredients. These and other objects, features and advantages will be apparent to those skilled in the art from the following detailed description and the appended claims. All percentages, ratios and proportions herein are by weight, unless otherwise specified. All temperatures are given in degrees Celsius (° C) unless otherwise indicated. All documents cited herein are incorporated herein by reference.

DETAILED DESCRIPTION OF THE INVENTION The alkoxylated polyalkyleneimines compatible with bleach of the present invention comprise base structures that are typically branched, although linear base structures are also suitable. In general, the polyamine base structures described herein were modified in such a way that each nitrogen of the polyamine chain having a hydrogen atom linked has that hydrogen atom replaced with alkyleneoxy unit, for example, an ethyleneoxy unit or propyleneoxy units or mixtures thereof. The polyamines to which almost all of the hydrogen atoms with an alkylenoxy unit have been replaced are defined herein as "modified". The polyamine base structures of the present invention have the general formula: H B I [H2N-] n + 1- [N-R] m- [N-R] n-NH2 said base structures, before being modified, comprise primary, secondary or tertiary amine nitrogen connected by "binding" units R. The base structures mainly comprise three types of units, which can be distributed randomly along the chain.

The primary amine units have the formula: H2N-R] - and - NH2 terminating the main base structure and any branching chain, the secondary amine units have the formula: and which, after being modified, have their hydrogen atom substituted by an alkylenoxy unit, and the tertiary amine units have the formula: which are the branch points of the main and secondary base structure chains, B represents a continuation of the chain structure by branch. The tertiary units do not have replaceable hydrogen atoms and therefore are not modified by substitution with an alkylenoxy unit. During the formation of the polyamine base structures, cyclization can occur, and in this way, a quantity of cyclic polyamine can be present in the mixture of the main polyalkyleneimine base structure. Each secondary and primary amine unit of the cyclic alkyleneimines undergo modification by the addition of alkyleneoxy units in the same manner as the linear and branched polyalkyleneimines. The cyclic polyalkyleneimines are the least preferred. R is linear C2-C6 alkylene, branched C3-C6 alkylene, and mixtures thereof, preferably ethylene or propylene, which may be 1,2-propylene or 1,3-propylene or mixtures thereof, or mixtures thereof. propylene and ethylene. Preferred polyalkylene imines of the present invention have base structures comprising the same unit R, for example, all units are ethylene. The preferred base structure comprises R groups wherein all are ethylene units. The polyalkyleneimines of the present invention are modified by substitution of the majority, preferably each hydrogen unit N-H with an alkyleneoxy unit having the formula: - (R10) xR2 wherein R1 is linear C2-C4 alkylene, branched C3-C4 alkylene, and mixtures thereof, preferably ethylene and / or propylene, which may be 1,2-propylene or 1,3-propylene or mixtures thereof , and it is preferred that the ethylene and propylene blends are presented. R2 is hydrogen, d-C4 alkyl, and mixtures thereof, preferably hydrogen or methyl, most preferably hydrogen. For the purpose of the present invention it is preferable that the alkyleneoxy unit comprises a mixture of groups R1, being ethylene or propylene, wherein the ratio of propylene to ethylene groups R1 is preferably from 1: 100 to 1: 4, most preferably from 1:50 a 1: 5, most preferably from 1: 15 to 1: 7. Therefore, it is preferable that 80% to 95% of the R1 groups is ethylene and 5% to 20% of the R1 groups is propylene. It has been found that in particular dispersants of this type, having one or more propylene R1 groups directly substituted to the N-H unit, followed by ethylene R1 groups are very compatible with bleach. The value of the index x is around 20, preferably around 25; to about 50, preferably approximately 40, most preferably x is 30. The relative number of primary, secondary and tertiary amine units in the base structure before modifying them is reflected in the values of the m and n indices. In general, the polyamines of the present invention will have a ratio of primary amine: secondary amine: tertiary amine of about 1: 2: 1 to about 1: 1: 1, i.e. the starting polyamines have the general formula: HB [ H2N-R] n + 1- [NR] m- [NR] n-NH2 wherein R is an alkylene unit defined above, which generally have the values of n + 1, m, and n in the ratio of about 1: 2: 1 to about 1: 1: 1. The preferred molecular weight for the polyamine base structures is around 2000, preferably around 2500, most preferably from about 3000 to about 5000, preferably around 4500, very Preferably, about 4000 daltons, most preferably 3000 daltons. The indices m and n will vary depending on the portion R comprising the base structure. For example, when R is ethylene one unit of the base structure has an average of about 43 g and when R is 5 hexylene one unit of base structure has an average of about 99 g. By way of illustration and not limitation, a polyalkyleneimine base structure having an average molecular weight of about 3000 where R is ethylene and the man ratio is about 2: 1 has a value of m equal to 35. and the value of n equal to approximately 17. In this For example, the secondary amine units comprise about 35 base structure units, the tertiary amine units comprise about 17 units and the primary amine units comprise about 18 units. Typically, for polyamines having a ratio of 1: 2: 1, the value for m varies from about 10, preferably around 24, most preferably around 30; to about 70, preferably to about 60, most preferably to about 40; the value for n varies from about 5, preferably about 10, most preferably about 15; at about 35, preferably at about 25, most preferably at approximately 20. The polyamines of the present invention can be prepared, for example, by polymerizing ethylene imine in the presence of a catalyst such as carbon dioxide, sodium bisulfite, sulfuric acid, hydrogen peroxide, hydrochloric acid, acetic acid, etc. Specific methods are described for preparing these polyamine base structures 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; Patent 5 of U.S.A. No. 2,208,095, Esselmann et al., Issued July 16, 1940; the Patent of E.U.A. 2,806,8349, issued September 17, 1957; and the U.S. Patent. No. 2,553,696, Wilson, issued May 21, 1951; all of these are incorporated herein by reference. The following is an example of a preferred embodiment of the present invention, polyethyleneimine (R equal to ethylene) having a molecular weight of average base structure of about 3000 and having the formula: PEÍ 3000 E30 wherein E is - (R 1 O) xR 2 wherein R 1 is ethylene, R 2 is hydrogen and x is equal to about 30 (example 1). Another example of the preferred embodiment of the invention is a dispersant of the following formula: PEÍ 3000 P3E27 where G is a unit having the formula - (R1 0) and (R "0) R2 where R1 is 1, 2-propylene, R" is ethylene, R2 is hydrogen and x is about 3 and y is about 27 (example 2).

Alkoxylated Polyalkyleneimine Compositions The present invention also relates to laundry detergent compositions comprising: a) at least about 0.01% to about 95%, preferably about 0.1% to about 60%, most preferably about 0.1% to about 30% by weight, of a detersive surfactant selected from the group consisting of anionic, nonionic, cationic, zwitterionic, and ampholytic surfactants, and mixtures thereof; b) from about 0.05% to about 1%, most preferably from about 5% to about 30%, still most preferably to about 20%, by weight, of an oxygen bleaching agent, said oxygen bleaching agent being selects from the group consisting of alkali metal percarbonate, perborate, monoperftalate, pyrophosphate peroxy hydrate, peroxy hydrate urea and mixtures thereof; c) from about 0.01% to about 10% by weight, of a water-soluble or dispersible alkoxylated polyamine, according to the present invention; and d) auxiliary ingredients and balance vehicles wherein the auxiliary ingredients are selected from the group consisting of detergency builders, optical brighteners, bleaches, bleach catalysts, bleach activators, soil release polymers, dye transfer agents, dispersants , enzymes, foam suppressors, dyes, perfumes, dyes, filler salts, hydrotropes, enzymes, photoactivators, fluorescers, fabric conditioners, hydrolyzable surfactants, preservatives, antioxidants, chelators, stabilizers, anti-shrinking agents, anti-wrinkle agents, germicides, fungicides, anti-corrosion agents, and mixtures thereof. Preferred laundry detergent compositions according to the present invention comprise: a) at least about 0.01% to about 95%, preferably about 60%, most preferably about 30% by weight, of a selected detersive surfactant from the group consisting of anionic, nonionic, cationic, zwitterionic, and ampholytic surfactants, and mixtures thereof; b) about 0.01%, preferably about 0.01%, most preferably about 0.5% to about 10%, preferably at about 5%, most preferably at about 2% by weight, of a soil release polymer; c) from about 0.05% to about 30%, most preferably from about 1% to about 30%, still most preferably from about 5% to about 20%, by weight, of an oxygen bleaching agent, said agent Oxygen bleaching is selected from the group consisting of alkali metal percarbonate, perborate, monoperftalate, pyrophosphate peroxy hydrate, peroxy hydrate urea and mixtures thereof; d) from about 0.01% to about 10% by weight, of a water-soluble or dispersible alkoxylated polyamine, according to the present invention; e) of 0.05%, preferably from about 1% to about 50% by weight, preferably to about 20%, most preferably to about 10%, still most preferably 5% by weight of one or more bleach activators, selected from activators hydrophobic and hydrophilic bleaching agents, preferably a mixture of hydrophobic and hydrophilic bleach activators, preferably TAED and alkanoyloxybenzenesulfonate such as nonailoxybenzenesulfonate; and f) auxiliary ingredients and balance vehicles wherein the auxiliary ingredients are selected from the group consisting of detergency builders, optical brighteners, bleaches, bleach catalysts, bleach activators, soil release polymers, dye transfer agents, dispersants , enzymes, foam suppressors, dyes, perfumes, dyes, filler salts, hydrotropes, enzymes, photoactivators, fluorescers, fabric conditioners, hydrolyzable surfactants, preservatives, antioxidants, chelators, stabilizers, anti-shrinking agents, anti-wrinkle agents, germicides, fungicides, anti-corrosion agents, and mixtures thereof. It is preferable that the laundry detergent compositions according to the present invention comprise: a) at least about 0.01%, preferably from 0.1% to about 95%, preferably about 60%, most preferably about 30% in weight, of a detersive surfactant selected from the group consisting of anionic, nonionic, cationic, zwitterionic, and ampholytic surfactants, and mixtures thereof; b) from about 0.01% to about 10%, preferably from about 0.1% to about 5%, most preferably from about 0.5% to about 2% by weight, of a soil release polymer; c) from about 0.05% to about 30%, most preferably from about 1% to about 30%, still most preferably from about 5% to about 20%, by weight, of an oxygen bleaching agent, said agent Oxygen bleaching is selected from the group consisting of alkali metal percarbonate, perborate, monoperftalate, pyrophosphate peroxy hydrate, peroxy hydrate urea and mixtures thereof; d) from about 0.05% to about 50%, preferably from 0.1% to about 5% by weight, of bleach activators, preferably bleach activators having the formula: O O O O 1 II II R 11- C "- N- R 9¿- C i '- L R1- N- C-R2- C- L R * R * and mixtures thereof, wherein R 1 is alkyl, aryl, alkylaryl C C? and mixtures thereof; R2 is alkylene, arylene, alkylarylene and mixtures thereof; R5 is hydrogen, alkyl, aryl, C? -C10 alkylaryl and mixtures thereof; L is any suitable leaving group; e) from about 0.01% to about 10% by weight, of a water-soluble or dispersible alkoxylated polyamine, according to the present invention; and f) auxiliary ingredients and balance vehicles wherein the auxiliary ingredients are selected from the group consisting of detergency builders, optical brighteners, bleaches, bleach catalysts, bleach activators., dirt release polymers, dye transfer agents, dispersants, enzymes, suds suppressors, dyes, perfumes, dyes, filler salts, hydrotropes, enzymes, photoactivators, fluorescers, fabric conditioners, hydrolyzable surfactants, preservatives, antioxidants, chelators, stabilizers, anti-shrinkage agents, anti-wrinkle agents, germicides, fungicides, anti-corrosion agents, and mixtures thereof. The present invention also relates to laundry bleaching compositions comprising: a) from about 0.05% to about 30%, most preferably from about 1% to about 30%, still most preferably from about 5% to about 20% , by weight, of an oxygen bleaching agent, said oxygen bleaching agent is selected from the group consisting of alkali metal percarbonate, perborate, monoperftalate, pyrophosphate peroxy hydrate, peroxy-hydrated urea and mixtures thereof; b) from about 0.05% to about 50%, preferably from 0.1% to about 5% by weight, of bleach activators, preferably bleach activators having the formula: L and mixtures thereof, wherein R1 is alkyl, aryl, alkylaryl of C-i-Cu and mixtures thereof; R2 is alkylene, arylene, alkylarylene and mixtures thereof; R5 is hydrogen, alkyl, aryl, alkylaryl of C-I-C-IO and mixtures thereof; L is any suitable leaving group; c) from about 0.01% to about 10% by weight, of a water-soluble or dispersible alkoxylated polyamine, according to the present invention; and d) auxiliary ingredients and balance vehicles.

Detersive Surfactants The detersive surfactants suitable for use in the present invention are cationic, anionic, nonionic, ampholytic, zwitterionic, and mixtures thereof, which are described further below. The laundry detergent composition can be presented in any suitable form, for example, high density liquid, light liquid or other pourable forms as well as granules or bars for washing. The cotton soil release polymers of the present invention can be formulated in any detersive matrix selected by the formulator. Laundry detergent compositions according to the present invention may additionally comprise about 0.01%, preferably about 0.1%, most preferably about 1% to about 95%, preferably about 60%, most preferably about 30% on weight, of the following detersive surfactants. Non-limiting examples of additional surfactants that can be used in the present typically at levels of 1% to 55% by weight, include the conventional C- | - | -C- | 8 alkylbenzenesulfonates ("LAS") and the alkyl sulfates of C10-C20 ("AS") primary, branched chain and random, the secondary alkyl sulfates (2,3) of C10-C18 of the formula CH3 (CH2) x (CHOS? 3-M +) CH3 and CH3 (CH2) and (CHOSO3-M +) CH2CH3 wherein 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, alkylalkoxy sulfates of C <? oC- | 8 ("AEXS", especially EO-1-7 ethoxysulfates), C-10-C13 alkylalkoxycarboxylates (especially the EO 1-5 ethoxycarboxylates), the glycerol ethers of C < | o_Ci8. The alkyl polyglycosides of C- | n-Ci8 and their corresponding sulfated polyglycosides, and alphasulfonated fatty acid esters of C- | 2-C - If desired, conventional amphoteric and nonionic surfactants such as C 2 -C 8 alkylethoxylates ("AE") including the so-called narrow peak alkylethoxylates and the C 6 -C 2 alkylphenolalkoxylates (especially ethoxylates and ethoxy / mixed propoxy), C- | 2-C- | 8 betaines and sulfobetaines ("sultaines"), amine oxides of C < | rj-Ci8. and the like, can also be included in the overall compositions. The N-alkyl polyhydroxy fatty acid amides of C < | rj-Ci8- Typical examples include the 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) glucamide of C- | Q- C-) 8- The N-propyl glucamides through N-hexyl of C- | 2-C- | 8 can be used for a low foam formation. Also conventional C? O_C2 soaps can be used? - If high foaming is desired, branched chain C- | or ~ C- | 6 soaps can be used. Mixtures of anionic and nonionic surfactants are especially useful. Other conventional surfactants are listed in normal texts. Preferred compositions of the present invention comprise at least about 0.1%, preferably 1%, most preferably from 1% to about 95%, still most preferably from about 1% to about 80% by weight, of a detersive surfactant anionic The alkyl sulfate surfactantseither primary or secondary, they are a type of anionic surfactant important for use in the present. The alkylsulfates have the general formula ROSO3M where R is preferably a hydrocarbyl of C? O-C24, preferably a straight or branched alkyl or hydroxyalkyl chain having a C10-C20 alkyl component, most preferably an alkyl or hydroxyalkyl of C? 2- Ci8, and M is hydrogen or a water soluble cation, for example, an alkali metal cation (eg, sodium, potassium, lithium), substituted or unsubstituted ammonium cations such as methyl, dimethyl and trimethyl ammonium and cations of quaternary ammonium, for example, tetramethylammonium and dimethylpiperidino, and alkanolamine-derived cations such as ethanolamine, diethanolamine, triethanolamine, and mixtures thereof, and the like. Normally, the C? 2-C ?β alkyl chains are preferred for lower wash temperatures (e.g., less than about 50 ° C) and C- ?6-C? Alkyl chains are preferred for temperature of higher washings (for example, around 50 ° C). Alkoxylated alkylsulphate surfactants are another preferred anionic surfactant category. These surfactants are water or acid soluble salts typically of the formula RO (A) mS03M where R is an unsubstituted C? Or C 24 alkyl or hydroxyalkyl group having a C 10 -C 24 alkyl component, preferably an alkyl or hydroxyalkyl C10-C20. preferably alkyl or hydroxyalkyl of C-? or C-? 8, A is an ethoxy or propoxy unit, m is greater than zero, typically between 0.5 and about 6, most preferably between 0.5 and about 6, most preferably between 0.5 and about 3 , and M is hydrogen or a water-soluble cation which can be, for example, a metal cation (for example sodium, potassium, lithium, calcium, magnesium, etc.), ammonium or substituted ammonium. The ethoxylated alkyl sulfates as well as the ethoxylated alkyl sulfates as well as the propoxylated alkyl sulphates are understood herein. Specific examples of substituted ammonium cations include methyl, dimethyl, trimethylammonium and quaternary ammonium cations, such as tetramethylammonium, dimethyl piperdinium and alkanolamine-derived cations, for example, monoethanolamine, for example, diethanolamine, and triethanolamine, and mixtures thereof. Exemplary surfactants are polyethoxylated C 2 -C 8 alkyl sulfate (1.0), polyethoxylated C 12 -C 18 alkyl sulfate (2.25), and polyethoxylated C 2 -C 12 alkyl sulfate (4.0) wherein M is conveniently selected from sodium and potassium. The laundry detergent compositions according to the present invention may additionally comprise at least 0.01%, preferably at least 0.1%, most preferably about 1% by weight of conventional Cn-C-is alkylbenzenesulfonate ("LAS"), preferably in bar compositions for laundry and granular laundry detergent compositions. Preferred compositions of the present invention also comprise at least 0.01%, preferably at least 0.1%, most preferably from about 1% to about 95%, most preferably from about 1% to about 80% by weight, of a nonionic detersive surfactant. Preferred nonionic surfactants such as C12-C18 alkyl ethoxylates ("AE") including the so-called narrow-peak alkyl ethoxylates and alkoxylated alkyl phenol of CQ-C2 (especially ethoxylated and mixed ethoxy / propoxy), condensed alkyl alkylene oxide of alkylphenols of C6 to C-? 2, condensates of alkylene oxides of Cs-C22 alkanols and propylene oxide / ethylene oxide blocking polymers (Pluronic ™ -BASF Corp.), as well as Semi-polar ionics (eg, amine oxides and phosphine oxides) can be used in the present compositions. An extensive description of this type of surfactants is found in the patent of E.U.A. 3929,678 Á ^^^^ A ^^^^ > Laughlin et al., Issued December 30, 1975, incorporated herein by reference. The alkylpolysaccharides such as those described in the U.S.A. No. 4,565,647 Filling (incorporated herein by reference) are also preferred nonionic surfactants in the compositions of the invention. Other preferred nonionic surfactants are the polyhydroxy fatty acid amines having the formula: O R8 7 'i i R7- C-N- Q wherein R7 is C5-C3 alkyl? preferably straight chain alkyl or alkenyl of C7-C? g, most preferably straight chain alkyl or alkenyl of C9-C? 7 > most preferably C11-C15 straight chain alkyl or alkenyl, or mixtures thereof; R8 is selected from the group consisting of hydrogen, C1-C4 alkyl, hydroxyalkyl of CrC4, preferably methyl or ethyl, most preferably methyl. Q is a polyhydroxyalkyl portion having a linear alkyl chain with at least 3 hydroxyls directly connected to the chain, or an alkoxylated derivative thereof; the preferred alkoxy is ethoxy or propoxy, and mixtures thereof. The Q is derived from a reducing sugar in a reductive amination reaction. Most preferably Q is a glycityl moiety. Suitable reducing sugars include glucose, fructose, maltose, lactose, galactose, mannose, and xylose. As raw materials, high dextrose corn syrup, high fructose corn syrup, and high maltose corn syrup can be used as well as individual sugars listed above. These corn syrups can produce a mixture of sugar components for Q. It should be understood that no attempt is made to exclude other suitable raw materials. Q is preferably selected from the group consisting of -CH2 (CHOH) nCH2OH, -CH (CH2OH) (CHOH) n-? CH2OH, -CH2 (CHOH) 2- (CHOR ') (CHOH) CH2OH, and alkoxylated derivatives of the same, wherein n is an integer from 3 to 5, inclusive, and R 'is hydrogen or a cyclic or aliphatic monosaccharide. The most preferred substituents for the Q portion are glycityls wherein n is 4, particularly -CH2 (CHOH) 4CH2OH. R7CO-N < it can be, for example, cocamide, stearamide, oleamide, lauramide, myristamide, capricamide, palmitamide, ceboamide, etc. R8 can be, for example, methyl, ethyl, propyl, isopropyl, butyl, 2-hydroxyethyl, or 2-hydroxypropyl. Q can be 1-deoxyglucityl, 2-deoxyfructityl, 1-deoxymaltityl, 1-deoxylactityl, 1-deoxygalactityl, 1-deoxyanityl, 1-deoxymalototriotityl, etc. A particularly desirable surfactant of this type for use in the compositions is alkyl-N-methyl glucamide, a compound of the above formula wherein R7 is alkyl (preferably C-n-C? 3), R8 is methyl and Q is 1-deoxyglucityl.

Other jelly-derived surfactants include the N-alkoxylated polyhydroxy fatty acid amides, such as glucamide N- (3-3). methoxypropyl) of C-IO-C-IS- The N-propyl to N-hexyl glucanes of C12-Ci8 can be used for low foaming. Conventional C-io-C2o soaps can also be used. If high foaming is desired, the branched chain soaps of C? O-C-? 6 can be used. Bleaching compounds - Bleaching agents and bleach activators The detergent compositions herein may comprise bleaching agents or bleaching compositions containing a bleaching agent and one or more bleach activators.

When presented, the bleaching agents will have levels of from about 0.05% to about 30%, most preferably from about 1% to about 30%, still most preferably from about 5% to about 20%, of the detergent composition, especially for washing fabrics. If present, the amount of bleach activators will typically be from about 0.1% to about 60%, typically from about 0.5% to about 40% of the bleaching composition comprising the bleach activator plus the bleaching agent. The peroxygen bleach compounds useful herein are also capable of producing hydrogen peroxide in an aqueous solution. These compounds are known in the art and include -arifiimp i - ^ üü ^ Üi ^ MMMaiüMh ^ hydrogen peroxide and alkali metal peroxides, organic peroxide bleaching compounds such as urea peroxide, and bleaching compounds of inorganic salts, such as alkali metal perborates, percarbonates, perfosphates, and similar. It is also possible to use blends of two or more bleaching compounds, if desired. Preferred peroxygen bleach compounds include sodium perborate, commercially available in the form of mono-, tri-, and tetrahydrate, sodium peroxyhydrate pyrophosphate, urea peroxyhydrate, sodium peroxide, peroxyphthalate, and sodium percarbonate. Particularly preferred is sodium perborate tetrahydrate, sodium perborate monohydrate and sodium percarbonate. Sodium percarbonate is especially preferred because of its stable storage and therefore dissolves rapidly in the bleaching solution. It is believed that such rapid dissolution results in the formation of higher levels of percarboxylic acid and thus increases the surface bleaching performance. Another category of bleaching agent that can be used without restriction comprises percarboxylic acid bleaching agents and salts thereof. Suitable examples of this class of agents include monoperoxyphthalate magnesium hexahydrate, the magnesium salt of metabenzene perbenzoic acid, 4-nonylamino-4-oxoperoxybutyric acid and diperoxydecanedioic acid. Said bleaching agents are described in the patent of E.U.A. do not. 4,483,781, Hartman, issued November 20, 1984, the patent application of E.U.A. 740,446, Burns et al. Issued June 3, 1985, European patent application 0,133,354, Banks et al., Published February 20, 1985, and the US patent. do not. 4,412,934, Chung et al., Issued November 1, 1983. Highly preferred bleaching agents also include 6-nonylamino-6-oxoperoxycaproic acid as described in U.S. Pat. do not. 4,634,551, issued January 6, 1987 by Burns et al. A preferred percarbonate bleach comprises dry particles having an average particle size in the range of about 500 microns to about 1,000 microns, no more than about 10% by weight of said particles being less than 200 microns and no more of 10% by weight of said particles is greater than about 1.250 microns. Optionally, the percarbonate can be coated with silicate, borate or water soluble surfactants. Percarbonate is available from several commercial sources such as FMC, Solvay and Tokai Denka. It is also possible to use mixtures of bleaching agents. The peroxygen bleaching agents, perborates, percarbonates, etc., are preferably combined with bleach activators, which lead to the production in situ in aqueous solution (ie during the washing process) of the peroxy acid corresponding to the bleach activator. Several non-limiting examples of activators are described in the U.S. patent. do not. 4,915,854, issued April 10, 1990 to Mao et al., And the US patent. do not. 4,412,934. He f | .r? . . r. -. r,, ^^^ || MÉaiiM ^ _ ^ M | aBMÍM ^^ Érifc | ^^^ i ^ nonanoiloxibencensulfonato (NOBS) and tetraacetylethylenediamine (TAED) are typical, and mixtures thereof are also preferred. See also E.U.A. 4,634,551 for other typical bleaches and activators used herein. Another class of bleach activators comprises the benzoxazine-type activators described by Hodge et al. In the U.S. patent. do not. 4,966,723, issued October 30, 1990, incorporated herein by reference. A highly preferred activator of the benzoxazine type is: Yet another class of bleach activators that is preferred includes the acyl-lactam activators, especially acylcaprolactams and acylvalerolactams of the formulas: ^^^^^^ H ^ ^^ g A > , Mfa-A ^ t ^ "-" A ^^ i where R6 is H or an alkyl, aryl or alkaryl group containing from 1 to about 12 carbon atoms. Highly preferred lactam activators include benzoylcaprolactam, octanoylcaprolactam, 3,5,5-trimethyl-hexanoylcaprolactam, nonanoylcaprolactam, decanoylcaprolactam, undecenoylcaprolactam, benzoylvalerolactam, octanoylvalerolactam, decanoylvalerolactam, undecenoylvalerolactam, nonanoylvalerolactam, 3,5,5-trimethylhexanoylvalerolactam and mixtures thereof. See also the patent of E.U.A. No. 4,545,784 issued to Sanderson on October 8, 1985, incorporated herein by reference, which discloses acylcaprolactams, including benzoylcaprolactam, adsorbed to sodium perborate. For the compositions according to the present invention comprising a bleach, peroxygen bleaching agents are preferred, of which amide substituted peroxyacid precursor compounds are preferred, including those having the formula: O O O O 1 II or II 1 II or II R1- C- N- R2- C- L R1- N- C- R2- C- ¿5 wherein R1 is alkyl, aryl, C1-C14 alkylaryl and mixtures thereof; R2 is alkylene, arylene, alkylarylene and mixtures thereof; R5 is hydrogen, alkyl, aryl, C1-C10 alkylaryl and mixtures thereof; L is any suitable leaving group (a leaving group which is preferred is phenylsulfonate). R1 preferably contains from 6 to 12 carbon atoms. R2 preferably contains from 4 to 8 carbon atoms. R1 may contain, when applicable, branching, substitution or both and may be obtained from synthetic or natural sources, including, for example, tallow fat. Analogous structural variations for R2 are permissible. The substitution may include alkyl, aryl, halogen, nitrogen, sulfur and other substituent groups or typical organic compounds. R5 is preferably H or methyl. R1 and R5 preferably should not contain more than 18 carbon atoms in total.

The amide-substituted bleach activator compounds of this type are described in EP-A-0170386. Examples of bleach precursors of the above formulas that are preferred include (6-octanamido-caproyl) oxybenzenesulfonate, (6-nonanamidocaproyl) oxybenzenesulfonate, (6- 15 decanamido-caproyl) oxybenzenesulfonate, and mixtures thereof as described in the US patent No. 4,634,551, incorporated herein by reference. Bleaching agents other than bleaching agents are also known in the art and can be used herein. oxygenates. One type of non-oxygenated bleaching agent of particular interest includes photoactivated bleaching agents such as sulfonated zinc and / or aluminum phthalocyanines. See the patent of E.U.A. 4,033,718 issued July 5, 1977 to Holcombe et al. If they are used, Detergent compositions typically should contain about 0.025% to about 1.25% by weight of said bleaches, especially sulfonated zinc phthalocyanine. If desired, the bleaching compounds can be catalyzed by means of a manganese compound. Such compounds are well known in the art and include, for example, the manganese-based catalysts described in the U.S.A. No. 5,246,621, patent of E.U.A. No. 5,244,594, patent of E.U.A. No. 5,114,606 and you are from pat. European pub. Nos. 549.271 A1, 549.272A1, 544.440A2 and 544.490A1.

Preferred examples of these catalysts include Mn'V2 (u-0) 3 (1, 4,7-trimethyl-l, 4,7-triazacyclononane) 2- (PF6) 2. Mn '|| 2 (u-0) < | (u-OAc) (1, 4,7-trimethyl-1, 4,7-triazacyclononane) 2- (Cl 4) 2, MnIV 4 (uO) β (1, 4,7-triazacyclononane) 4- (Cl 2) 4) 2, Mn '|| Mn'V4 (uO)? (u-OAc) 2 (1, 4,7-trimethyl-l, 4,7-triazacyclononane) - (Cl? 4) 3, Mn'Vil ^ J -trimethyl-I ^ -triazaciclononanoHOCHs ^ íPFe) and mixtures thereof. Other metal-based catalysts include those described in the U.S.A. 4,430,243 and patent of E.U.A. 5,114,611. The use of manganese with several complex ligands to improve bleaching is also reported in the following United States Patents: 4,728,455; 5,284,944; 5,246,612; 5,256,779; 5,280,117; 5,274,147; 5,153,161 and 20 5,227,084. As practical, and not by way of limitation, the compositions and methods herein may be adjusted for ^^^^^ gj jgjj »provide in the order of at least one part per ten million of the active bleach catalyst species in the aqueous wash liquor, and will preferably provide about 0.1 ppm to about 700 ppm, most preferably about 1 ppm to about 500 ppm of the catalyst species in the wash liquor. Various detersive ingredients employed in the present compositions can be further stabilized by absorbing said ingredients on a porous hydrophobic substrate, then coating said substrate with a hydrophobic coating. Preferably, the ingredient The detersive is mixed with a surfactant before being absorbed into the porous substrate. During use, the detersive ingredient is released from the substrate in the aqueous wash liquor, where it performs its intended detersive function. To illustrate this technique in more detail, a hydrophobic silica porous (trademark SIPERNAT D10, DeGussa) is mixed with a proteolytic enzyme solution containing 3% -5% nonionic surfactant of ethoxylated alcohol of C? 3_i5 (EO 7). Typically, the enzyme / surfactant solution is 2.5X the weight of the silica. The resulting powder is dispersed with stirring in silicone oil (various viscosities of silicone oil can be used in the range of 500-12,500). The resulting silicone oil dispersion is emulsified or otherwise added to the final detergent matrix. By this means, ingredients such as enzymes, bleaches, bleach activators, bleach catalysts, Photoactivators, dyes, fluorescers, fabric conditioners and hydrolyzable surfactants mentioned above can be "protected" for use in detergents, including liquid laundry detergent compositions. The liquid detergent compositions may contain water and other solvents such as vehicles. The low molecular weight primary and secondary alcohols illustrated by methanol, ethanol, propanol and isopropanol are suitable. Monohydric alcohols are preferred as a solubilizing surfactant, but polyols such as Those containing 2 to 6 carbon atoms and 2 to 6 hydroxyl groups (e.g., 1,3-propanediol, ethylene glycol, glycerin and 1,2-propanediol). The compositions may contain from 5% to 90%, typically from 10% to 50% of said vehicles. The detergent compositions herein preferably will be formulated such that during use in aqueous cleaning operations, the wash water has a pH of between about 6.5 and about 11, preferably between about 7.5 and 10.5. Laundry products typically have a pH of 9-11. Techniques for controlling pH at recommended levels of use include the use of regulators of pH, alkalis, acids, etc., and are well known to those skilled in the art. ltM.-nl rí - Dirt release polymers The compositions according to the present invention may optionally comprise soil release polymers. If used, the soil release agents will generally comprise about 0.01%, preferably about 0.1, most preferably about 0.2% to about 10%, preferably about 3%, by weight of the composition. Polymeric soil release agents are characterized in that they have both hydrophilic segments to hydrophilize the surface of the hydrophobic fibers, such as polyester and nylon, and hydrophobic segments to be deposited on hydrophobic fibers and remain adhered thereto throughout the wash cycle , thus serving as an anchor for the hydrophilic segments. This can make it possible for stains that occur after treatment with the soil release agent to be more easily cleaned in subsequent washing procedures. Suitable for use in the laundry detergent compositions of the present invention are soil release polymers comprising: a) a base structure comprising: i) at least one portion having the formula: ii) at least one portion that has the formula: wherein R9 is linear C6 alkylene, branched C3-C6 alkylene, C5-C7 cyclic alkylene and mixtures thereof; R10 is selected independently of hydrogen or -L-SO 3"M +; wherein L is a side chain portion selected from the group consisting of alkylene, oxyalkylene, alkyleneoxyalkylene, arylene, oxyarylene, alkyleneoxyarylene, poly (oxyalkylene), oxyalkylene oxide, poly (oxyalkylene) oxyarylene , alkylenepoly (oxyalkylene) and mixtures thereof, M is hydrogen or a salt-forming cation, i has the value of 0 or 1, iii) at least one ester-forming and trifunctional branching portion, iv) at least a 1, 2-oxyalkyleneoxy moiety, and b) one or more blocking units comprising: i) ethoxylated or propoxylated hydroxyethanesulfonate or propoxylated hydroxyethane or ethoxylated or propoxylated hydroxypropanesulfonate of the formula (M03S) (CH2) m (R1 10) n-, wherein M is a salt-forming cation such as sodium or tetralkylammonium, R11 is ethylene or propylene or a mixture thereof, m is 0 or 1, and n is from 1 to 20; . ~ U ^. . ^^. ^ «^ ..« l- ^ J. - JMMMfc * - »- ^ - -, ^ a.-. ^^. ^ F ^? HlU? Im.- ii) sulfoaroyl units of the formula - (O) C (C6H4) (SO3- M +), wherein M is a salt forming cation; iii) Modified polyoxyethyleneoxymonoalkyl ether units of the formula R12O (CH CH20) k-, wherein R12 contains from 1 to 4 carbon atoms and k is from about 3 to about 100; and iv) ethoxylated or propoxylated phenolsulfonate end block units of the formula M03S (C6H4) (0Rl3) n0-, where n is from 1 to 20; M is a salt forming cation and R 13 is ethylene, propylene and mixtures thereof. The most preferred block end unit is the isethionate-type end blocking unit which is a hydroxyethane portion, (M03S) (CH2) m (R1 1) n-, preferably R11 is ethyl, m is equal to 0 and n is from 2 to 4. An example of this preferred soil release agent has the formula: The following documents, all included herein by way of reference, disclose suitable soil release polymers for use in the present invention. E.U. 5,691, 298 Gosselink et al., Issued November 25, 1997; E.U. 5,599,782 Pan et al., 5 issued on February 4, 1997; E.U. 5,415,807 Gosselink et al., Issued May 16, 1995; E.U. 5,182,043 Morrall et al., Issued January 26, 1993; E.U. 4,956,447 Gosselink et al., Issued September 11, 1990; E.U. 4,976,879 Maldonado et al., Issued December 11, 1990; E.U. 4,968,451 Scheibel et al., Issued on 6 November 10, 1990; E.U. 4,925,577 Borcher, Sr. et al., Issued May 15, 1990; E.U. 4,861, 512 Gosselink et al., Issued August 29, 1989; E.U. 4,877,896 Maldonado et al., Issued October 31, 1989; E.U. 4,771, 730 Gosselink et al., Issued October 27, 1987; E.U. 711, 730 Gosselink et al., Issued December 8, 1987; E.U. 15, 4,721, 580 Gosselink, issued January 26, 1988; E.U. 4,000,093 Nicol et al., Issued December 28, 1976; E.U. 3,959,230 Hayes, issued May 25, 1976; E.U. 3,893,929 Basadur, issued July 8, 1975 and European patent application 0 219 048, published April 22, 1987 by Kud et al. Additional soil release agents are described in E.U. 4,201, 824 Voilland et al .; E.U. 4,240,918 Lagasse et al .; E.U. 4,525,524 Tung et al .; E.U. 4,579,681 Ruppert et al .; E.U. 4,220,918; E.U. 4,787,989, EP 279,134 A, 1988 to Rhone-Poulenc chemie; EP 457.205 A a BASF (1991) and DE 2,335,044 to 1974; all incorporated herein by way of reference. The detergent compositions herein will preferably be formulated such that during use in aqueous cleaning operations, the wash water has a pH of between about 6.5 and about 11, preferably between about 7.5 and 10.5. Laundry products typically have a pH of 9-11. Techniques for controlling pH at recommended levels of use include the use of pH, alkali, acid regulators, etc., and are well known to those skilled in the art.

Granulated Compositions The bleach stable polyalkyleneimines of the present invention can be used in both low density (less than 550 grams / liter) and high density granular detergent compositions, in which the granule density is at least 550 grams / liter. . The granular compositions are typically designed to provide a pH in the wash from about 7.5 to about 11.5, preferably about 9.5 to about 10.5. The low density compositions can be prepared by standard spray drying methods. Various means and equipment are available for preparing high density granular detergent compositions. Current commercial practice in the field employs spray-drying towers for making granular laundry detergents which commonly have a density of less than about 500 g / l. Accordingly, if spray drying is used as part of the general procedure, the resulting spray dried detergent particles should be densified using the means and equipment described hereinafter. Alternatively, the formulator can eliminate spray drying using mixing, densifying and granulating equipment that is commercially available. The following is a non-limiting description of such equipment suitable for use herein. Various means and equipment are available for preparing high density granular detergent compositions (ie, more than about 550, preferably more than about 650 grams / liter or "g / l"), high solubility and free flow in accordance with the present invention. Current commercial practice in the field employs drying towers by spray to make granular laundry detergents that commonly have a density of less than about 500 g / l. In this process, an aqueous suspension of various heat-stable ingredients in the final detergent composition are configured to create homogeneous granules by passing them through a spray-drying tower, using conventional techniques, at temperatures from about 175 ° C to about 225 ° C. However, if spray drying is used as part of the overall process herein, additional processing steps such as those described hereinafter should be used to obtain aStamstr aafceafcfe - fc sjU ^ Aj the level of density (ie required by the modern compact detergent products of low dosage For example, the spray-dried granules of a tower can be further densified by charging a liquid such as water or an agent. nonionic surfactant in the pores of the granules and / or by subjecting them to one or more high speed mixers / densifiers A high speed mixer / densifier suitable for this process is a device marketed under the trade name "Lódige CB 30" or " Lódige CB 30 Recycler "comprising a static cylindrical mixing drum that has a central rotating shaft with mixing / cutting blades mounted thereon. During use, the ingredients for the detergent composition are introduced into the drum and the arrow / blade assembly rotates at speeds in the range of 100-2500 rpm to provide thorough mixing / densification. See Jacobs et al., US patent. No. 5,149,455, issued on September 22, 1992. The preferred residence time in the high-speed mixer / densifier is from about 1 to 60 seconds. Other apparatuses of this type include the devices marketed under the trade name "Shugi Granulator" and under the trade name "Drais K-TTP 80". Another processing step that can be used to densify more spray-dried granules includes grinding and agglomerating or deforming the spray-dried granules in a moderate speed mixer / densifier to thereby obtain particles having a porosity. -a, a "ifcrt- '' - • '- ^^ - ^ *» - ^ between particles lower equipment such as the one marketed under the name mixers / densifiers "Lódige KM" (Series 300 or 600) or " Lódige Ploughshare "are suitable for this processing step, which typically operates at 40-160 rpm.The residence time of the detergent ingredients in the moderate speed mixer / densifier is approximately 0.1 to 12 minutes. device that is available under the trade name "Drais KT 160." This processing step employing a moderate speed mixer / densifier (eg, Lódige KM) can be used on its own or sequentially with the aforementioned high speed mixer / densifier. above (eg Lödige CB) to achieve the desired density. Other types of manufacturing apparatus useful herein include granules apparatus disclosed in US 2,306,898 to GL Heller, December 29 1 942. Although it may be more appropriate to use a high speed mixer / densifier followed by the low speed mixer / densifier, the inverse sequential configuration of mixer / densifier is also contemplated by the invention. One or a combination of various parameters including residence times in the mixer / densifier, equipment operating temperatures, temperature and / or composition of the granules, the use of auxiliary ingredients such as liquid binders and flow aids, can be used for optimize the densification of the spray-dried granules in the process of the invention. By way of example, see the procedures in Appel et al., US patent. 5,133,924, issued July 28, 1992 (the granules are brought to a deformable state before densification); Delwel et al., Patent of E.U. 4,637,891, issued January 20, 1987 (formation of spray-dried granules with a liquid binder and aluminosilicate); Kruse et al., Patent of E.U. 4,726,908, issued February 23, 1988 (formation of spray dried granules with a liquid binder and aluminosilicate) and Bortolotti et al patent E.U. 5,160,657, issued November 3, 1992 (coating densified granules with a liquid binder and aluminosilicate). In situations where detergent ingredients that are particularly sensitive to heat or highly volatile (i.e., perfume ingredients) are to be incorporated into the final detergent composition, processes that do not include spray towers are preferred. The formulator can eliminate the drying step fed spray, either continuously or intermittently, starting detergent ingredients directly into mixing equipment / densification is commercially available. A particularly preferred embodiment includes charging a surfactant paste and an anhydrous builder material in a high speed mixer / densifier (e.g., Lódige CB), followed by a moderate speed mixer / densifier (e.g., Lódige KM) to form high density detergent agglomerates. See Capeci et al., US patent. 5,366,652, issued on November 22, 1994 and Capeci et al., Patent of E.U. 5,486,303, ^ '^ Ji ^ SU "g ^^^^^^^^ | ^^' ^ issued January 23, 1996. Optionally, the liquid / solids ratio of the starting detergent ingredients in such a process can be sele for high density agglomerates that are more free flowing and crisp. Optionally, the method may include one or more recycle streams of undersized particles produced by the process which are fed back to the mixer / densifiers for further agglomeration or build-up. The oversized particles produced by this process can be sent to a grinding apparatus and fed back to the mixing / densifying equipment. These additional recirculation process steps facilitate the agglomeration and accumulation of the starting detergent ingredients, resulting in a finished composition having a uniform distribution of particle size (400-700 microns) and density (>); 550 g / l) desired. See Capeci et al., US patent. 5,516,448, issued May 14, 1996 and Capeci et al., US patent. 5,489,392, issued February 6, 1996. Other suitable methods that do not make use of spray-drying towers are described by Bollier et al., U.S. 4,828,721, issued May 9, 1989; Beerse et al., Patent of E.U. 5,108,649, issued April 28, 1992 and Jolicoeur, US patent. 5,178,798, issued January 12, 1993. In yet another embodiment, the high density detergent composition of the invention can be produced using a bed mixer. ^ r? A r - ** - ^. . - WM «^^^. ._- - .. ^^^ Elfe. fluidized In this process, the different ingredients of the finished composition are combined in an aqueous suspension (with a solids content typically of 80%) and sprayed in a fluidized bed to provide the finished detergent granules. Prior to the fluidized bed, the method may optionally include the step of mixing the suspension using the Lódige CB mixer / densifier mentioned above or a "Flexomix 160" mixer / densifier, available from Shugi. The fluidized bed or moving beds of the type available under the trade name "Escher Wyss" can be used in such processes. Another suitable method that can be used herein includes feeding a liquid acid precursor of an anionic surfactant, an alkaline inorganic material (eg, sodium carbonate) and optionally other detergent ingredients into a high speed mixer / densifier (time of residence 5-30 seconds) to form agglomerates containing a partial or fully neutralized anionic surfactant salt and the other starting detergent ingredients. Optionally, the contents in the high speed mixer / densifier can be sent to a moderate speed mixer / densifier (eg, Lódige KM) for further agglomeration, resulting in the detergent composition. high density finished. See Appel and other US patent. No. 5,164,108 issued November 17, 1992. For the purpose of the invention, it may be preferred that the dispersants be premixed with anionic surfactants or a dough comprising anionic surfactants, such as sulphonate and sulfate surfactants, before the addition of, or to the other detergent ingredients. It may be preferred that the dispersant of the invention or a composition comprising the dispersant, preferably a laundry detergent composition, be comprised in a detergent tablet or in the form of a detergent tablet. The tablets can be manufactured by any method known in the art. It may be preferred that the compositions are first formed by any of the methods described herein, in particular agglomeration, prior to the formation of the tablet.

EXAMPLE 1 PEI 3000 Ean 15 A portion of 90 g polyethylenimine (PEI) having an average listed molecular weight of 3000 (equivalent to about 0.03 moles of polymer and about 2.1) is added to a 7.56 liter autoclave equipped to agitate small liquid volumes. moles of 20 nitrogen functions). The autoclave is then sealed and purged of air (applying vacuum to minus 711 mm Hg followed by pressurization 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 92 grams of ethylene oxide has been loaded 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 stir for an additional hour. At this point, vacuum is applied to remove any residual unreacted ethylene oxide. After, vacuum is continuously applied while the autoclave is cooled to approximately 50 ° C by introducing 11.3 g of a 25% sodium methoxide solution in methanol (0.21 mol, to achieve a catalyst load of 10% based on the nitrogen functions of PEÍ). 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 values of power and temperature of the agitator increase gradually when 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 further stirred under vacuum for an additional 30 minutes. 5 The vacuum is removed and the autoclave is cooled to 105 ° C while it is charged 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 speed of the flow of ethylene oxide from 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 a total of 2772 g of ethylene oxide (resulting in a total of 30 moles of ethylene oxide per mole of PEI nitrogen function) for several hours, the temperature is increased to 110 ° C and the mixture is stirred for an additional hour. The reaction mixture is then collected in nitrogen purged containers and optionally transferred to a 22-liter, three-necked round bottom flask equipped with heating and stirring. He The strong alkaline catalyst is neutralized by adding 20.2 g of methanesulfonic acid (0.21 mol). The reaction mixture is then deodorized by passing approximately 2,831 dm3 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 achieved in the rector before discharging the product.

EXAMPLE 2 PEÍ 3000 P3 E27 A portion of 90 g of polyethylenimine (PEI) having an average listed molecular weight of 3000 (equivalent to about 0.03 moles of polymer and about 2.1 moles of nitrogen functions) is added to a 7.56-liter autoclave equipped to agitate small liquid volumes. ). The autoclave is then sealed and purged of air 15 (applying vacuum to minus 711 mm Hg followed by pressurization 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. Then add propylene oxide to the autoclave in increments over time while carefully monitoring the pressure, temperature and flow rate of propylene oxide from the autoclave. The propylene oxide pump is turned off and cooling is applied to limit ^^^ Hj ^^ j. ^ y jj | ^^ | ^^ ü áírn * s ... - ~ ^. - ^ * t * ^ any increase in temperature resulting from 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 122 grams of propylene oxide 5 has been loaded into the autoclave (almost equivalent to one mole of propylene oxide per function of PEI nitrogen), the temperature is increased to 110 ° C and the autoclave is left shake for an additional hour. At this point, vacuum is applied to remove any residual unreacted ethylene oxide. Afterwards, vacuum is applied continuously while the autoclave is cooled to approximately 50 ° C by introducing 11.3 g of a 25% sodium methoxide solution in methanol (0.21 mole, to achieve a catalyst load of 10% based on the PEI nitrogen functions). 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 values of power and temperature of the agitator increase gradually when 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 it is charged with nitrogen at 17.57 kg / cm2 and then ventilated under pressure ambient. The autoclave is charged at 14.06 kg / cm2 with nitrogen. Propylene oxide is again added to the autoclave in increments as mentioned above, carefully monitoring the pressure, temperature and propylene oxide flow rate of 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 a total of 244 g of propylene oxide (resulting in a total of 3 moles of propylene oxide per mole of nitrogen function of PEI) for several hours, the temperature is increased to 110 ° C and The mixture is stirred for an additional hour. At this point vacuum is applied to remove any residual unreacted propylene oxide. Ethylene oxide is then added to the autoclave in increments, carefully monitoring the pressure, temperature and flow velocity of ethylene oxide, 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 a total of 2495 g of ethylene oxide (resulting in a total of 27 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 stirred for an additional hour. The reaction mixture is then collected in nitrogen purged containers and optionally transferred to a 22-liter, three-necked round bottom flask equipped with heating and stirring. The strong alkaline catalyst is neutralized by adding 20.2 g of acid "- ^ - -" "^ J **" - ¡^ - ^ H & ^? S ^ methanesulfonic (0.21 moles). The reaction mixture is then deodorized by passing about 2,831 drr 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 achieved in the rector before unloading the product. The following discloses high density liquid detergent compositions comprising alkoxylated polyamine dispersants according to the present invention: TABLE I 1. - Minors - includes optical brighteners and enzymes (protease, lipase, cellulase, and amylase). 2.- Dirt release polymer for non-cotton fabrics according to the patent of E.U.A. No. 4,968,451, Scheibel et al. 3.- PEÍ 3000 E30 as described in example 1.

TABLE II 1. - Alkyl C12-C13 ethoxylate E9 as sold by Shell Oil Co. 2.- Subtilisin Bacillus amiloliquefaciens as described in O 95/10615 published on April 20, 1995 by Genencor International. 3. - Derived from Humicola lanuginosa and commercially available in Novo. 4.- Described in WO 9510603 A and available in Novo. 5.- PEI 3000 E30 as described in example 1. 6.- Terephthalate copolymer as described in the patent of E.U.A. No. 4,968,451, Scheibel et al, issued November 6, 1990. 7.- Dirt release polymer according to the U.S. patent. No. 5,415,807, Gosselink et al, issued May 16, 1995. 8.- Dirt release polymer according to the U.S. patent. No. 4,702,857, Gosselink issued October 27, 1987.

¡^ ¡^ ^ Aj ^ ¡¡¡¡¡TABLE lll Ingredients Percent by weight 10 11 12 13 14 1. - Alkyl C12-C13 ethoxylate E9 as sold by Shell Oil Co. 2.- Subtilisin Bacillus amiloliquefaciens as described in WO 95/10615 published on April 20, 1995 by Genencor International. 3.- Derivative of Humicola lanuginosa and commercially available from Novo. 4.- Described in WO 9510603 A and available in Novo.

* Mmf ~ 3 .. ^ g ^^^ * ^^ ¡^ -t "áhMh *" ^ "^ 5.- PEÍ 3000 E30 as described in example 1. 6.- Copolymer of terephthalate as described in U.S. Patent No. 4,968,451, Scheibel et al, issued November 6, 1990.

EXAMPLES 15-21 The compositions of the present invention are also made by preparing high density granular formulas according to this example using the alkoxylated polyamine dispersants alone or in combination with other soil release polymers.

TABLE IV 1. - Dirt release polymer for non-cotton fabrics according to the U.S. patent. No. 4,968,451, Scheibel et al, issued November 6, 1990. 2.- Dirt release polymer for non-cotton fabrics of the U.S. patent. No. 5,415,807, Gosselink, Pan, Kellett and Hall, issued May 16, 1995. 3.- Dirt release polymer for non-cotton fabrics according to the U.S. patent. No. 4,702,857, Gosselink, issued October 27, 1987. 4.- PEI 3000 E30 as described in example 1. 5.- PEÍ 3000 P3 E27 as described in example 2. 6.- The remainder for the 100% may, for example, include minors such as optical brighteners, perfume, suds suppressors, dirt dispersant, protease, lipase, cellulase, chelating agents, dye transfer inhibiting agents, additional water, and fillers, including CaCO3, talc, silicates, etc.

EXAMPLES 22-25 Granular laundry detergent compositions comprising the alkoxylated polyamine dispersants of the present invention can be formulated without linear alkylbenzene sulphonates (LAS), for example: TABLE V 1. - As sold by Shell oil Co. 2. - Dirt release polymer according to the patent E.U.A. No. 4,968,451, Scheibel et al, issued November 6, 1990. 3. - Dirt release polymer of the U.S.A. No. 5,415,807, Gosselink, Pan, Kellett and Hall, issued May 16, 1995. 4.- Soil release polymer according to the U.S. patent. No. 4,702,857, Gosselink, issued October 27, 1987. 5.- PEÍ 3000 E30 as described in example 1. 6.- The remainder for 100% may, for example, include minors such as optical brighteners, perfume, foam suppressors, dirt dispersant, protease, lipase, cellulase, chelating agents, dye transfer inhibiting agents, additional water, and fillers, including CaCO3, talc, silicates, etc.

Claims (17)

NOVELTY OF THE INVENTION CLAIMS

1. - A dirt dispersant having the formula: E B [E2N-R] n + 1- [N-R] m- [N-R] n-NE2 wherein R is linear C2-C6 alkylene. branched alkylene of C3-C6. and mixtures thereof; E is an alkylenoxy unit having the formula: wherein R1 is linear C2-C4 alkylene, branched C3-C4 alkylene, and mixtures thereof; R2 is hydrogen, C1-C4 alkyl, and mixtures thereof; m is from 10 to 70; n is from 5 to 35; x is from 20 to 50; and B represents a continuation of the structure by branching.

2. A compound according to claim 1, further characterized in that R is ethylene, 1, 2-propylene, 1,3-propylene, and mixtures thereof.

3. A compound according to any of claims 1 or 2, further characterized in that R is ethylene, R1 is ethylene, and R2 is hydrogen.

4. A compound according to any of claims 1 or 2, further characterized in that R is ethylene, from 80% to 95% of the units R1 are ethylene and from 5% to 20% of the units R1 is 1, 2 -propylene, R2 is hydrogen.

5. A compound according to any of claims 1 to 4, further characterized in that m and n have values such that the molecular weight of the base structure before modification is from 2000 to 5000 daltons.

6. A compound according to any of claims 1 to 5, further characterized in that x is from 25 to 40.

7. A laundry detergent composition comprising: a) at least 0.01% to 95% by weight, of a detersive surfactant selected from the group comprising anionic, nonionic, cationic, zwitterionic, and ampholytic surfactants, and mixtures thereof; b) from 0.05 to 30% by weight of a bleach; c) from 0.01 to 10% by weight of a water-soluble or dispersible alkoxylated polyamine, having the formula: E B [E2N-R] n + 1- [N-R] m- [N-R] n-NE2 wherein R is linear C2-C6 alkylene. branched alkylene of C3-C6. and mixtures thereof; E is an alkylenoxy unit having the formula: wherein R1 is linear C2-C4 alkylene, branched C3-C4 alkylene, and mixtures thereof; R2 is hydrogen, C1-C4 alkyl, and mixtures thereof; m is from 10 to 70; n is from 5 to 35; x is from 20 to 50; and B represents a .., ... j.; ^^ ^^ á ^^ _ ^^ i ^^^ A, g ^ ^ continuation of the structure by ramification; and d) the vehicles and auxiliary ingredients.

8. A compound according to claim 7, further characterized in that R is ethylene, R1 is ethylene, and R2 is hydrogen.

9. A compound according to claim 7, further characterized in that R is ethylene, from 80% to 95% of the R1 units are ethylene and from 5% to 20% of the R1 units is 1, 2-propylene, R2 is hydrogen. 10. A compound in accordance with any of the

10 claims 7 to 9, further characterized in that myn has values such that the molecular weight of the base structure before modification is from 2000 to 5000 daltons, and x is from 25 to 40.

11. A composition in accordance with any of claims 7 to 10, further characterized in that the ingredients 15 auxiliaries are selected from the group consisting of detergency builders, optical brighteners, bleaches, bleach enhancers, bleach catalysts, bleach activators, soil release polymers, dye transfer agents, dispersants, enzymes, foam suppressors, dyes, perfumes, filler salts, 20 hydrotropes, ezymes, photoactivators, fluorescence, fabric conditioners, hydrolyzable surfactants, preservatives, antioxidants, chelators, stabilizers, anti-shrinkage agents, anti-aging agents MiSKiMÉ ^ BteiMüllii wrinkles, germicides, fungicides, anticorrosion agents and mixtures thereof.

12. A composition according to any of claims 7-11, further characterized in that it comprises at least 5 0.01% to 60% by weight, of a detersive surfactant selected from the group comprising anionic, nonionic, cationic, zwitterionic, and ampholytic surfactants, and mixtures thereof.

13. A composition according to any of claims 7-12, further characterized in that it comprises an agent Oxygen bleach selected from the group consisting of alkali metal percarbonate, perborate, monoperftalate, pyrophosphate peroxyhydrate, urea peroxyhydrate and mixtures thereof.

14. A composition according to any of claims 7-13, further characterized in that it comprises at least 15.01% by weight of a bleach activator wherein the oxygen bleach activator has the formula: R And mixtures thereof, wherein R 1 is C 1 -C 14 alkyl, aryl, alkylaryl, and mixtures thereof; R2 is C1-C14 alkylene, arylene, alkylarylene, and mixtures thereof; R5 is hydrogen, C1-C10 alkyl, aryl, alkylaryl, and mixtures thereof; L is any suitable leaving group. ^^ m t m? m g | j | j g & *

15. - A composition according to any of claims 7-14, further characterized in that it comprises at least 0.1% by weight of TAED and bleach activator of alkanoyloxybenzenesulfonate.

16. A detergent tablet comprising the composition according to any of claims 7-15.

17. A laundry bleaching composition comprising: a) from 0.05% to 30% by weight of a peroxygen bleach; b) from 0.05 to 50% by weight of a bleach activator; c) from 0.01 to 10% by weight, of a water-soluble or dispersible alkoxylated polyamine having the formula: E B [E2N-R] n + 1- [N-R] m- [N-R] n-NE2 wherein R is linear C2-C6 alkylene. branched alkylene of C3-C6. and mixtures thereof; E is an alkylenoxy unit having the formula: - (R10) R2 wherein R1 is linear C2-C4 alkylene, branched C3-C4 alkylene, and mixtures thereof; R2 is hydrogen, C1-C4 alkyl, and mixtures thereof; m is from 10 to 70; n is from 5 to 35; x is from 20 to 50; and B represents a continuation of the structure by branching; and d) the vehicles and auxiliary ingredients. Ji ^ i = ^^ a'fefei ^^ * - - ^^ "" - * »• -