MXPA99002829A - Detergent composition comprising cationic amines and cellulase enzymes - Google Patents

Abstract

The present invention relates to granular detergent compositions or component thereof containing a cellulolytic enzyme and one or more cationic compounds, which are cationic, (partially) quaternized ethoxylated (poly)amine compounds with clay-soil removal/antiredeposition properties.

Description

COMPOSITION DETERGENT COMPRISING CATIONIC AMINAS AND CELLULAS ENZYMES TECHNICAL FIELD The present invention relates to granular detergent compositions or to components thereof containing cationic compounds with removal / anti-redeposition properties of particulate / clay soils and a cellulolytic enzyme for use in laundry and dishwashing processes.

BACKGROUND OF THE INVENTION A particularly important property of the detergent composition is its ability to remove particle-like soils from a variety of fabrics during washing. Perhaps the most important particulate soils are clay-like soils. The dirt particles of clay generally comprise negatively charged layers of positively charged aluminosilicates and cations (eg, calcium) which are placed between and hold the negatively charged layers together. A variety of models can be proposed for compounds that have the particulate / clay dirt removal properties. A model requires that the compound have two distinct characteristics. The first is the ability of the compound to adsorb onto the negatively charged layers of the clay particle. The second is the capacity of the compound, once adsorbed, to separate (swell) the negatively charged layers so that the clay particle loses its cohesive force and can be removed in the wash water. In addition to the removal of dirt from clay, there is a need to keep the dirt removed during the laundry (or dishwashing cycle). The dirt that is removed from the fabric and suspended in the wash water can be redeposited on the surface of the fabric. The redeposited dirt causes the effect of percussion or "graying" which is especially noticeable on white fabrics. To minimize this problem, anti-redeposition agents may be included in the detergent composition. For example, EP-B-111 965 describes the use of cationic compounds in detergents, which have both removal and anti-redeposition properties of clay soils. US 4,659,802 and US 4,664,848 describe quaternized amines having removal and anti-redeposition properties of clay soils and which can be used in combination with anionic surfactants.

A proposed model for the antiredeposition action of the positively charged anti-redeposition compounds is as follows. The adsorption of the positively charged molecule on the surface of the clay particles in the wash water gives the particles the dispersion properties of the molecule. As more and more of these compounds are adsorbed onto the suspended dirt, it is enclosed within a hydrophilic layer provided by the bound ethoxy units. As a result, hydrophilically enclosed dirt is prevented from being redeposited on fabrics, in particular hydrophobic fabrics such as polyester, during the laundry cycle. Other components frequently used in detergents are cellulase and / or endolase enzymes. It is known that detergent compositions are used as softening aids. The cellulolytic enzymes are responsible for the controlled catalytic removal of the cellulose material contained in the fabrics. This is commonly called "shaved" from the surface of the fabric, which imparts softness to it. The removal of clay soils / body dirt is not satisfactory. It has now been discovered that this problem can be caused by dirt / clays in particles that become trapped in the fibers of the fabric, particularly the cellulose fibers, and which are therefore difficult to remove from the fabric. Applicants have now discovered that this problem can be alleviated by the inclusion of cellulolytic enzymes in a granular detergent composition (or component thereof), comprising (partially) quaternized ethoxylated cationic (poly) amines having removal / anti-redeposition properties of clay soils. Detergent compositions (or components thereof) that employ both quaternized ethoxylated cationic (poly) amines and a cellulolytic enzyme have been shown to provide surprisingly better cleaning and softening performance than detergent compositions employing either of the two components separately . A further advantage of the present invention is that the cleaning benefits can be observed even after the completion of only one wash cycle. All documents cited in the present description are, in a relevant part, incorporated herein by way of reference.

BRIEF DESCRIPTION OF THE INVENTION The present invention relates to granular detergent compositions or components thereof, which comprise a cellulolytic enzyme and one or more cationic compounds, which are compounds of ethoxylated (partially) quaternized cationic (poly) amine with removal / anti-redeposition properties of soils of clay. In more detail, the present invention relates to granular detergent compositions or to components thereof, which comprise: (a) a cellulolytic enzyme; and (b) a water-soluble cationic compound having removal / anti-redeposition properties of clay soils, which is selected from the group consisting of: 1) ethoxylated cationic monoamines having the formula: * 2 3 R2 - N + - L - X 3 R2 2) ethoxylated cationic diamines having the formula: (R3) d R3 (R3) R3 3 3 3 X L M1 R1 N + X R M1 N + R O / 3 3 L L L L 3 3 3 3 X X X X X (R3) R3 (X L) 2 M2 R1 M2 R2 R2 wherein M1 is a group N + or N; each M2 is a group N + or N and at least one M2 is a group N +; 3) ethoxylated cationic polyamines having the formula: (R3) d 3 R4 [(Al) s (R5) t) M2 L X] R2 4) mixtures thereof; 0 O O O O where A1 is NC, NCO, NCN, CON, OCN 3 3 3 3 3 3 R R R R R 0 0 0 o o o o o o o co, OCO, oc, CNC o o R R is H or C1-C4 alkyl or hydroxyalkyl, R1 is alkylene, hydroxyalkylene, alkenylene, arylene or alkylene of C2 - "- 12 '° an oxyalkylene portion of C2-C3 having from 2 to about 20 oxyalkylene units, provided that when NO bonds are formed, each R2 is C1-C4 alkyl or hydroxyalkyl, the -XX portion, or two R2 together form the portion - (CH2) r-A2XCH2) s-, where A2 is -0- or - CH2-, r is l or 2, s is l or 2 and r + s is 3 or 4, each R3 is alkyl or hydroxyalkyl of C] _- Cg, benzyl, the LX portion, or two R3 or one R2 and one R3 together they form the - (CH2) r-A2- (CH2) S-; R4 is a substituted C3 ~ C2 _2 alkyl, hydroxyalkyl, alkenyl, aryl or alkaryl group having substitution sites p; R ^ is alkenyl, hydroxyalkylene, alkenylene, arylene or alkarylene of C] _-C? 2, or an oxyalkylene portion of C2-C3 having from 2 to about 20 oxyalkylene units, as long as no 0-0 or NO bonds are formed; X is a nonionic group selected from the group or consisting of H, C 1 -C 4 alkyl or hydroxyalkyl ester or alkyl groups and mixtures thereof; L is a hydrophilic chain containing the polyoxyalkylene moiety - [(R60) m (CH2CH20) n] -; wherein R6 is C3-C4 alkylene or hydroxyalkylene and m and n are numbers such that the - (CH2CH20) n] - portion comprising at least about 50% is weight of said polyoxyalkylene portion; d is 1 when M2 is N + and is 0 when M2 is N; n is at least about 16 for said cationic monoamines, is at least about 6 for said cationic diamines and is at least about 3 for said cationic polyamines; p is from 3 to 8; q is 1 or 0; t is 1 or 0, as long as t is 1 when q is 1; and wherein the ratio of compound (a) to (b) is from 1: 100 to 100: 1.

DETAILED DESCRIPTION OF THE INVENTION An essential feature of the present invention is a water-soluble cationic compound having removal / anti-redeposition properties of clay soils and which is selected from the group consisting of mono-, di- and cationic polyamines. The ratio of cellulolytic enzyme to water-soluble cationic compound is from 1: 100 to 100: 1, most preferably from 50: 1 to 1:50 and more preferably from 1:10 to 10: 1. The water-soluble cationic compound is preferably present at a level of from 0.01% to 30%, most preferably from 0.1% to 15%, more preferably from 0.2% to 3.0% by weight of the detergent composition.

Cationic amines The water-soluble cationic compounds of the present invention useful in the granular detergent compositions or components thereof according to the present invention include ethoxylated cationic monoamines, ethoxylated cationic diamines and ethoxylated cationic polyamines as defined previously. In the above formulas for the cationic amines, R 1 may be alkylene, hydroxyalkylene, alkenylene, alkarylene or branched oxyalkylene (e.g. cyclical, or very preferably linear (e.g., CH2CH2 CH2CH2CH2) R1 is preferably C2-Cg alkylene for the ethoxylated cationic diamines. Each R2 is preferably methyl or the -L-X portion; each R3 is preferably C1-C4 alkyl or hydroxyalkyl, and most preferably methyl. The positive charge of the N + groups is compensated by the appropriate number of counter-anions. Suitable counter-anions include Cl, Br-, SO3-2, PO4-2, MeOS? 3 ~ and the like. The anti-anions that are particularly preferred are Cl- and Br-. X may be a nonionic group selected from hydrogen (H), C1-C4 alkyl or hydroxyalkyl ester or alkyl ether groups or mixtures thereof. The esters or ethers that are preferred are the acetate ester and the methyl ether, respectively. Particularly preferred nonionic groups are H and methyl ether. In the above formulas, the hydrophilic chain normally consists entirely of the polyoxyalkylene portion - [(R60) m (CH2CH2On) -]. The portions (R6?) M- and - (CH2CH2? N) - of the polyoxyalkylene portion can be mixed or preferably form blocks of portions - (R60) m- and - (CH2CH2On) -. R6 is preferably C3H6 (propylene); m is preferably from 0 to about 5 and is most preferably 0, ie, the polyoxyalkylene portion consists completely of the (CH2CH2On) - portion. The - (CH2CH2? N) - portion preferably comprises at least about 85% by weight of the polyoxyalkylene portion and most preferably 100% by weight (m is O). In the above formulas, M1 and each M2 are preferably a N + group for the cationic diamines and polyamines. The ethoxylated cationic monoamines and diamines that are preferred have the formula: I CH3! CH3 X- (-OCH2CH_2) n - - - | N + - - -CH2 - - -CH2 - (-CH2) a + - -N + - - -CH2CH20) n -X b (CH2CH20) -n-X (CH2CH20) n-X wherein X and n are defined as above, a is from 0 to 20, preferably 0 to 4 (e.g., ethylene, propylene, hexamethylene) b is 1 or 0. For the preferred cationic monoamines (b = 0), n is preferably at least about 16, with a typical scale of about 20 to about 35. For the preferred cationic diamines (b = 1), n is at least about 12 with a typical scale of about 12 to about 42. In the above formula for the ethoxylated cationic polyamines, R4 (linear, branched or cyclic) is preferably an alkyl, hydroxyalkyl or substituted C3-Cg aryl group; A ^ is preferably O • CN - I H n is preferably at least about 12, with a typical scale of about 12 to about 42; p is preferably from 3 to 6. When R 4 is a substituted aryl or alkaryl group, q is preferably 1 and R 5 is preferably C 2 -C 3 alkylene. When R 4 is an alkyl, hydroxyalkyl or substituted alkenyl group, and when q is 0, R 5 is preferably an oxyalkylene portion of C 2 -C 3; when q is 1, R5 is preferably C2-C3 alkylene. These ethoxylated cationic polyamines can be derived from polyaminoamides such as: These ethoxylated cationic polyamines can also be derived from polyaminopropyl oxide derivatives such as: wherein each c is a number from 2 to about 20 Cellulolytic Enzyme Another essential component of the detergent composition or component thereof according to the present invention is a cellulolytic enzyme, i.e., an enzyme having cellulolytic activity. The ratio of cellulolytic enzyme to water-soluble cationic compound is from 1: 100 to 100: 1, preferably from 50: 1 to 1:50 and more preferably from 1:10 to 10: 1. In the detergent compositions of the present invention, the cellulolytic enzyme is preferably present at a level of from 0.01% to 5.0% by weight, most preferably from 0.3% to 4% by weight and more preferably from 0.5% to 3% by weight of the detergent composition, on a basis of 100OOCU / g. At the moment, the terms "cellulase" and "cellulolytic" denote an enzyme with cellulolytic activity. This means that the enzyme catalyzes the hydrolysis of the cellulose, and specifically the cellulose fibers of the fabric. The cellulolytic enzyme can be a component that occurs in a cellulase system produced by a certain microorganism, such as a cellulase system comprising mainly several different cellulolytic enzyme components, including those normally identified as, eg, cellobiohydrolases, exocelobiohydrolases, endoglucanases and ß-glucosidases.

Alternatively, the cellulolytic enzyme can be an individual component, that is, a component essentially free of other cellulase components that normally occur in a cellulase system produced by a certain microorganism, the individual component being a recombinant component, i.e., produced by cloning a DNA sequence that encodes the individual component and subsequently transformed into a cell with the DNA sequence and expressed in a host, cf. e.g., international patent applications WO 91/17243 and WO 91/17244, which are incorporated herein by reference. The host is preferably a heterologous host, but the host may under certain conditions also be the homologous host. It is contemplated that the cellulolytic enzyme may have an exo mode of action; the term "exo mode of action" being designed to mean the degradation of cellulose from the ends of the non-reducing chain by removing the cellobiose units. As an alternative, it is contemplated that the cellulolytic enzyme may have an endo mode of action; the term "endo-acting mode" being designed to mean the hydrolysis of amorphous regions of low crystallinity in the cellulose fibers. The cellulolytic enzyme herein can be obtained from a source of microorganisms by the use of any suitable technique. For example, a preparation of cellulolytic enzymes can be obtained by the fermentation of a microorganism and the subsequent isolation of the preparation of the fermented broth or micro-organism by methods known in the art, but most preferably by the use of recombinant DNA techniques such as those they are known in the art. Said method normally comprises the cultivation of an isopedera cell transformed with a recombinant DNA vector capable of expressing and carrying a DNA sequence encoding the cellulolytic enzyme in question, in a culture medium under conditions that allow the expression of the enzyme and the recovery of the enzyme from the culture. Preferably, the cellulolytic enzyme is a fungal or bancterial cellulase component, i.e. of fungal or bacterial origin. It is contemplated that the cellulolytic enzyme can be derived or isolated and purified from microorganisms known to be capable of producing cellulolytic enzymes, e.g., species of Humicola, Bacillus, Trichoderma, Fusarium, Myceliophtora, Phanerochaete, Schizopyllum, Penicillium, Aspergillus and Geotricum The derivative components can be homologous or heterologous components. Preferably, the components are homologous. However, a heterologous component that is immunoreactive with an antibody developed against a highly purified cellulolytic enzyme component possessing the desired property or properties, and which is derived from a specific microorganism is also preferred. The cellulolytic enzymes which are preferred herein may be any of those described in European Patent Application No. EP-A-271 004, the cellulolytic enzyme having a non-degradation index (NDI) of not less than 500 and being a alkalophilic cellulolytic enzyme having an optimum pH of not less than 7 or whose relative activity at a pH of not less than 8 is 50% or more of the activity under optimum conditions when carboxymethylcellulose (CMC) is used as a substrate; the cellulolytic enzyme being preferably selected from the group consisting of alkaline cellulase K (produced by Bacillus sp.KSM-635, FERM BP 1485); alkaline cellulase K-534 (produced by Bacillus sp.KSM-534, FERM BP 1508); alkaline cellulase K-539 (produced by Bacillus sp. KSM-539, FERM BP 1509); alkaline cellulase K-577 (produced by Bacillus sp.

KSM-577, FERM BP 1510); alkaline cellulase K-521 (produced by Bacillus sp.KSM-521, FERM BP 1507); alkaline cellulase K-580 (produced by Bacillus sp.KSM-580, FERM BP 1511); alkaline cellulase K-588 (produced by Bacillus sp. KSM-588, FERM BP 1513); alkaline cellulase K-597 (produced by Bacillus sp.KSM-597, FERM BP 1514); alkaline cellulase K-522 (produced by Bacillus sp.KSM-522, FERM BP 1512); CNCase I, CMCase II (both produced by Bacillus sp.KSM-635, FERM BP 1485); alkaline cellulase E-II and alkaline cellulase E-III (both produced by Bacillus sp.KSM-522, FERM BP 1512). A convenient and useful cellulolytic enzyme in the detergent composition of the present invention can be a component of endoglucanase that is immunoreactive with an antibody developed against a highly purified -43kD endoglucanase derived from Humicola insolens, DSM 1800, or which is a homologue or endoglucanase derivative of ~ 43kD exhibiting cellulolytic activity. A preferred endoglucanase component has the amino acid sequence described in PCT Patent Application No. WO 91/17243, SEQ ID # 2, which is shown in SEQ ID NO: 4 attached, or a variant of said endoglucanase having an amino acid sequence that is at least 60%, preferably at least 70%, most preferably 75%, more preferably at least 80%, more preferably 85%, especially at least 90% homologous with said sequence. Another endoglucanase component that is preferred comprises an amino acid sequence encoded by the partial DNA sequence described in PCT patent application No. W093 / 11249; SEQ ID # 11, which is shown in SEQ ID NO: 5 attached, or a variant of said endoglucanase having an amino acid sequence that is at least 60%, preferably at least 70%, most preferably 75%, more preferably at least 80%, more preferably 85%, especially at least 90% homologous with said sequence. Another endoglucanase component that is also preferred comprises an amino acid sequence encoded by the partial 7DNA sequence described in PCT Patent Application No. WO 93/11249; SEQ ID # 9, which is incorporated herein by reference. Another component of endoglucanase that is also preferred comprises an amino acid sequence encoded by the partial DNA sequence described in PCT Patent Application No. WO 93/11249; SEQ ID # 7, which is incorporated herein by reference. In example 1 below, the endoglucanase component is called EG III. Alternatively, the cellulolytic enzyme can be a component of endoglucanase that is immunoreactive with an antibody developed against a highly purified ~ 60kD endoglucanase derived from Bacillus lautus, NCIMB 40250, or which is a homologue or derivative of the ~ 60kD endoglucanase that exhibit cellulase activity. A preferred endoglucanase component has the amino acid sequence described in PCT patent application No. WO 91/10732, SEQ ID # 7, which is shown in SEQ ID NO: 6 attached, or a variant of said endoglucanase having an amino acid sequence that is at least 60%, preferably at least 70%, most preferably 75%, more preferably at least 80%, more preferably 85%, especially at least 90% homologous with said sequence.

Cationic Polymers The detergent composition or component thereof may comprise additional polymeric cationic ethoxylated amine compounds with antiredeposition / removal of particulate / clay fouling, selected from the group consisting of water soluble cationic polymers. These polymers comprise a polymer base structure, at least 2 M groups and at least one L-X group, wherein M is a cationic group bonded to, or integral with, the base structure; X is a nonionic group selected from the group consisting of H, C1-C4 alkyl or hydroxyalkyl ester or ester groups and mixtures thereof; and L is a hydrophilic chain connecting the M and X groups or connecting X to the polymer base structure. The polymeric cationic ethoxylated amine compounds may be present in the detergent compositions at a level of from 0.01% to 30%, most preferably from 0.1% to 15%, more preferably from 0.2% to 3% by weight of the detergent composition. As used herein, the term "polymer base structure" refers to the polymer portion to which the M and L-X groups are attached or are integral therewith. This term includes oligomer base structures (2 to 4 units), and true polymer base structures (5 or more units). As used herein, the term "attached to" means that the group depends on the polymer base structure, examples of which are represented by the following general structures A and B: 1 M M 1 L 1 I L X 1 I 1 X A B As used herein, the term "integrals with" means that the group is part of the polymer base structure, examples of which is represented by the following general structures C and D: M -M D Any base structure can be used, as long as the cationic polymer formed is soluble in water and has removal / anti-redeposition properties of clay soils. Suitable polymer base structures can be derived from polyurethanes, polyesters, polyethers, polyamides, polyimides and the like; polyacrylates, polyacrylamides, polyvinyl ethers, polyethylenes, polypropylenes and similar polyalkylene, polystyrenes and polyalkylenes, polyalkyleneamines, polyalkyleneimines, polyvinylamines, polyallylamines, polydiallylamines, polyvinylpyridines, polyaminetriazoles, polyvinyl alcohol, aminopolyureylenes and mixtures thereof. M can be any compatible cationic group comprising a positively charged N + (quaternary) center. The positively charged quaternary center can be represented by the following general structures E and F: The M groups which are particularly preferred are those which contain a quaternary center represented by the general structure E. The cationic group is preferably placed near or integral with the polymer base structure. The positive charge of the N + centers is compensated by the adequate number of counter-anions. Suitable counter-anions include Cl, Br-, SO3-2, PO4-2, MeOS? 3 ~ and the like. The anti-anions that are particularly preferred are Cl- and Br-. X can be a nonionic group selected from hydrogen (H), C1-C4 alkyl or hydroxyalkyl ester or alkyl ether groups and mixtures thereof. The ester or ether groups that are preferred are the acetate ester and the methyl ether, respectively. Particularly preferred nonionic groups are H and methyl ether. Cationic polymers suitable for use in the granular detergent compositions or components thereof according to the present invention typically have a ratio of cationic groups M to nonionic groups X of from about 1: 1 to about 1: 2. However, for example, by suitable copolymerization of cationic monomers, non-ionic (ie, containing the L-X group) and mixed cationic / non-ionic groups, the ratio of cationic groups M to non-ionic groups X may vary. The ratio of groups M to groups X may vary from about 2: 1 to about 1:10. In preferred cationic polymers, the ratio is from about 1: 1 to about 1: 5. The polymers formed from said copolymerization are typically random, that is, the cationic, nonionic and cationic / non-ionic mixed monomers are copolymerized in a non-repeating sequence. The units containing M groups and L-X groups can comprise 100% of the cationic polymers of the present invention. However, the inclusion of other (preferably non-ionic) units in the polymers is also permissible. Examples of other units include acrylamides, vinyl ethers and those containing non-quaternized tertiary amine groups (M1) containing a center N. These other units may comprise from 0% to about 90% of the polymer (from about 10% to 100% of the polymer being units containing M and LX groups, including groups M1-LX). Typically, these other units comprise from 0% to about 50% of the polymer (from about 50% to 100% of the polymer being units containing M and L-X groups). The number of groups M and LX each typically varies from about 2 to about 200. Typically, the number of groups M and LX are each from about 3 to about 100. Preferably, the number of groups M and LX is each from about 3 to about 40. Unlike portions to connect groups M and X, or to bind them to the polymer base structure, the hydrophilic L chain usually consists entirely of the polyoxyalkylene moiety - [(R '?) M (CH2CH20) n] -. The portions - (R '?) M- and - (CH CH 0) n- of the polyoxyalkylene portion can be mixed or preferably form blocks of portions - (R'?) M- and - (CH 2 CH 20) n-. R1 is preferably C3H6 (propylene); m is preferably from 0 to about 5 and is most preferably 0, ie, the polyoxyalkylene portion consists completely of the - (CH 2 CH 20) n- portion. The - (CH2CH20) n- portion preferably comprises at least about 85% by weight of the polyoxyalkylene portion and most preferably 100% by weight (m is O). For the portion - (CH2CH20) n-, n is usually from about 3 to about 100. Preferably, n is from about 12 to about 42.

A plurality (2 or more) of portions -L-X can also be hooked together and attached to the group M or to the other polymer base structure, examples of which are represented by the following general structures G and H: X X X X H Structures such as G and H can be formed, for example, by reacting glycidol with M group or with the base structure of the polymer, and ethoxylating the hydroxyl groups formed subsequently. The representative classes of cationic polymers of the present invention are as follows: A. Polyurethane, polyester, polyether, polyamide or similar polymers. A class of suitable cationic polymers are derived from polyurethanes, polyesters, polyethers, polyamides and the like. These polymers comprise units selected from those having the formulas I, II and III: where A1 is R R X is 0 or 1; R is H or C1-C4 alkyl or hydroxyalkyl; R1 is alkylene, hydroxyalkylene, alkenylene, cycloalkylene, arylene or C2-C2 alkarylene, or an oxyalkylene portion of C-C3 having from 2 to about 20 oxyalkylene units, provided no 0-0 or ON bonds are formed with A ^; when x is 1, R2 is -R5- except when A ^ is O c # o is - (0R8) and- or -OR5- as long as no 0-0 or N-O bonds are formed with A1; and R3 is -R5- except when A1 is 0 I! - C -, or is - (R80) -y or -R50- as long as no links are formed O-O or O-N with A1; when x is 0, R2 is (0R8) and -, - 0R5 - -NCR5-, -NC0R5-, -CNR5- or _0CNR5, II I ß! L R0 RO OR OR and R3 is -R5-; R4 is alkyl or hydroxyalkyl of Ct_-C4, or the portion - (R5)] - [(C3HgO) m (CH2CH20) n] -X; R5 is alkylene, hydroxyalkylene, alkenylene, arylene or alkarylene of Ct_-c12 '* each R6 is C1-C4 alkyl or hydroxyalkyl, or the - (CH2) r-A2- (CH2) s-, where A2 is - O- or -CH2-; R7 is H or R4; R8 is alkylene or hydroxy alkylene of C2-C3, - X is H, -R9 or a mixture thereof, wherein R9 is C1-C4 alkyl or hydroxyalkyl; k is 0 or 1; m and n are numbers such that the portion XCH2CH20) n- comprises at least about 85% by weight of the portion [(C3H5O) m (CH2CH20) n] -; m is from 0 to about 5; n is at least about 3; r is l or 2, s is l or 2 and r + s is 3 or 4; and is from 2 to about 20; the number of u, v and W is such that there are at least 2 centers N + and at least 2 groups X. In the above formulas, A1 is preferably A2 is preferably -0-; x is preferably 1; and R is preferably H. R1 can be alkylene, hydroxyalkylene, alkenylene, cycloalkylene, alkarylene or linear oxyalkylene (e.g., -CH2-CH-CH2-, C when R ^ - is an oxyalkylene portion of C2-C3, the number of oxyalkylene units is preferably from about 2 to about 12; R1 is preferably C2-Cg alkylene or phenylene, and most preferably C2-Cg alkylene (e.g., ethylene, propylene, hexamethylene). R2 is preferably -OR5- or - (0R8) and-; R3 is preferably -R50- or - (OR8) and, - R4 and R6 are preferably methyl. Like R1, R5 can be linear or branched, and is preferably C2-C3 alkylene, - R7 is preferably H or C1-C3 alkyl; R8 is preferably ethylene; R9 is preferably methyl; X is preferably H or methyl; k is preferably 0; m is preferably 0, r and s are each preferably 2; and is preferably from 2 to about 12. In the above formulas, n is preferably at least about 6 when the number of N + centers and X groups is 2 or 3; n is most preferably at least about 12, with a typical scale of about 12 to about 42 for all scales of u + v + w. For homopolymers (vyw are 0), u is preferably about 3 to about 20. For random copolymers (u is at least 1 or preferably 0), v and w are each preferably about 3 to about 40. B. Polyacrylate, polyacrylamide , polyvinyl ether or similar polymers. Another class of suitable cationic polymers is derived from polyacrylates, polyacrylamides, polyvinyl ethers and the like. These polymers comprise units selected from those having the formulas IV, V and VI.

SAW V VI -OC? N- - R is H or alkyl or hydroxyalkyl of C ^ - ^ R1 is alkylene, hydroxyalkylene, alkenylene, arylene or substituted C2-C12 alkarylene or C2-C3 oxyalkylene, - each R2 is alkylene, hydroxyalkylene , alkenylene, arylene or alkarylene of Ct_-C] _; each R3 is alkyl or hydroxyalkyl of the - (R2)] - [(C3HgO) m (CH2CH20) n] -X or together form the - (CH2) r-A2- (CH2) s- , wherein A2 is -0- or -CH2-; each R4 is C1-C4 alkyl or hydroxyalkyl, or two R4 together form the - (CH2) r-A2- (CH2) s- portion; X is H, -R5 or mixture thereof, wherein R5 is C1-C4 alkyl or hydroxyalkyl; j is 1 or 0; k is 1 or 0; m and n are numbers such that the portion (CH2CH20) n- comprises at least about 85% by weight of the portion [(C3HgO) m (CH2CH20) n] -; m is from 0 to about 5; n is at least about 3; r is l or 2, s is l or 2 and r + s is 3 or 4; the number of u, v and w are such that there are at least 2 centers N + and at least 2 groups X. In the above formulas, A1 is preferably A2 is preferably -0-; R is preferably H; R1 may be alkylene, hydroxyalkylene, alkenylene, alkarylene or linear substituted oxyalkylene (e.g., -CH2-CH2-CH2-, * • _ • - -CH, -CH- -CH9 -CH, CH- -) or R1 is preferably C2-Cg alkylene or substituted C-C3 oxyalkylene, and most preferably Each R2 is preferably C2-C3 alkylene, each R3 and R4 are preferably methyl; R5 is preferably methyl; X is preferably H or methyl; j is preferably 1; is preferably 0; m is preferably 0; r and s are each preferably 2.

In the above formulas, n, u, v and w can be varied according to n, u, v and w for polyurethane and similar polymers. C. Polyalkyleneamine, polyalkyleneimine or similar polymers. Another class of suitable cationic polymers are derived from polyalkyleneamines, polyalkyleneimines and the like. These polymers comprise units selected from those having the formulas VII and VIII and IX. wherein R1 is alkylene, hydroxyalkylene, alkenylene, cycloalkylene, arylene or C2-C2 alkarylene], or a C2-C3 oxyalkylene portion having from 2 to about 20 oxyalkylene units, as long as no 0-0 bonds are formed; each R2 is C1-C4 alkyl or hydroxyalkyl, or the - (R3)] - [(C3HO) m (CH2CH2?) n] -X portion; R3 is alkylene, hydroxyalkylene, alkenylene, arylene or alkarylene of C? -C?; M1 is a center N + or N; X is H, - CR4, OR -R4 or mixture thereof, wherein R4 is C1-C4 alkyl or hydroxyalkyl; d is 1 when M1 is N + and is 0 when M 'is N; e is 2 when M 'is N + and is 1 when M' is N; k is 1 or 0; m and n are numbers such that the portion - (CH2CH20) n- comprises at least about 85% by weight of the portion - [(C3HgO) m (CH2CH2?) n] -; m is from 0 to about 5; n is at least about 3; the number of x, y and z is such that there are at least 2 M1 groups, for at least 2 N + centers and at least 2 X groups. In the above formulas, R1 can be varied just like the R1 of polyurethane and polymers Similar; each R2 is preferably methyl or the portion - (R3) ^ - [(C3H6?) m (CH2CH20) n] -X; R3 is preferably C2-C3 alkylene; R 4 is preferably methyl; X is preferably H; k is preferably 0; m is preferably 0. In the above formulas, n is preferably at least about 6 when the number of groups M 'and X is 2 or 3; n is most preferably at least about 12, with a typical scale of about 12 to about 42 for all scales of x + y + z. Typically, x + y + z is from 2 to approximately 40 and preferably from 2 to approximately 20. For short-chain polymers, x + and + z can vary from 2 to 9 with from 2 to 9 N + centers and from 2 to 11. X groups. For long chain polymers, x + y + z is at least 10, with a preferred scale of 10 to approximately 42. For short and long chain polymers, M1 groups are typically a mixture of about 50 to 100% N + centers and from 0 to about 50% N. centers. Preferred cationic polymers within this class are derived from the C2-C3 polyalkyleneamines (x + y + z is from 2 to 9) and polyalkyleneimines (x + y + z is at least 10, preferably from 10 to about 42). Particularly preferred cationic polyalkyleneamines and polyalkyleneimines are the cationic polyethyleneamines (PEA's) and polyethyleneimines (PEI's). These preferred cationic polymers comprise units having the general formula: (R2) d (R2) d [M '] to [CH2 CH2M'] X [(CH2CH20 '] n X] 2 (R2) d (R2) d [CH2CH2M'] and [CH2CH2M '] Z [CH2CH20) n X [(CH2CH20) n X] 2 wherein R2 (preferably methyl), M ', X, d, x, y, z and n are defined as above; a is 1 or 0. Before ethoxylation, the PEAs used to prepare the cationic polymers of the present invention have the following general formula: [H2N] to [CH2CH2N_X [CH2CH2N] and [CH2CH2NH2] Z H wherein x + y + z is from 2 to 9, and a is O or l (molecular weight from about 100 to about 400). Each hydrogen atom attached to each nitrogen atom represents an active site for subsequent ethoxylation. For the PEAs, x + and + z is from about '3 to about 7 (the molecular weight is from about 140 to about 310). These 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). Among 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 US patent. 2,792,372, Dickinson, issued May 14, 1957, which describes the preparation of PEA's. The minimum degree of ethoxylation required for the preferred removal / anti-redeposition performance of clay soils may vary depending on the number of units in the PEA. Where y + z is 2 or 3, n is preferably at least about 6. Where y + z is from 4 to 9, adequate benefits are obtained when n is at least about 3. For cationic PEAs that are preferred , n is at least about 12, with a typical scale of about 12 to about V 42. The PEIs used to prepare the polymers of the present invention have a molecular weight of at least about 440 before ethoxylation, which represents at least about 10 units. The preferred PEIs used to prepare these polymers have a molecular weight of about 600 to about 1800. The polymer base structure of these PEIs can be represented by the general formula: H H2N [CH2CH2N-]? [CH2CH2N-] and [CH2CH2NH2] z wherein the sum of x, y and z represents a number of sufficient magnitude to produce a polymer having the previously specified molecular weights. Although linear polymer base structures are possible, branch chains may also occur. The relative proportions of primary, secondary and tertiary amine groups present in the polymer may vary, depending on the form of preparation. The distribution of the amine groups is as follows: CH2CH2- NH2 30% - CH2CH2 NH 40% CH2CH2 N 30% Each hydrogen atom attached to each nitrogen atom of the PEI represents an active site for the subsequent ethoxylation. These PEIs 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. Specific methods for preparing PEIs are described in the U.S. patent. No. 2,182,306 to Ulrich et al., Issued December 5, 1939; US patent No. 3,033,746, Mayle et al., Issued May 8, 1962; US patent No. 2,208,095, Esselman et al., Issued July 16, 1940; US patent No. 2,806,839 to Crowther, issued September 17, 1957 and US patent. No. 2,553,696, Wilson, issued May 21, 1951 (all incorporated herein by reference). As defined in the above formulas, n is at least about 3 for the cationic PEIs. Nevertheless, it should be noted that the minimum degree of ethoxylation necessary for an adequate removal / anti-redeposition performance of clay soils can increase with increasing molecular weight of the PEI, especially much more than about 1800. Similarly, the degree of ethoxylation for polymers preferred increases with increasing molecular weight of PEI. For PEIs having a molecular weight of at least about 600, n is preferably at least about 12, with a typical scale of about 12 to about 42. For PEIs having a molecular weight of at least 1800, n is preferably at least about 24, with a typical scale of about 24 to about 42. D. Diallylamine polymers Another class of suitable cationic polymers are those derived from diallylamines. These polymers comprise units selected from those having the formulas X and XI: wherein R1 is C1-C4 alkyl or hydroxyalkyl, or the - (R2)] - [(C3HgO) m (CH2CH20) n] -X; R2 is alkylene, hydroxyalkylene, alkenylene, arylene or alkarylene of C] _-C? 2 / 'each R3 is alkyl or hydroxyalkyl of C.-C4, or together they form the portion - (CH) rA- (CH2) s-, wherein A is -O- or -CH2-; X is H, CR4, or -R4 or mixture thereof, wherein R4 is C1-C4 alkyl or hydroxyalkyl; k is 1 or 0; m and n are numbers such that the portion - (CH2CH20) n- comprises at least about 85% by weight of the portion [(C3HgO) m (CH2CH20) n] -; m is from 0 to about 5; n is at least about 3; r is l or 2, s is l or 2 and r + s is 3 or 4; x is 1 or 0; and is 1 when x is 0 and 0 when x is 1; the number of u and v is such that there are at least 2 centers N + and at least 2 groups X. In the above formulas, A is preferably -0-; R1 is preferably methyl; each R2 is preferably C2-C3 alkylene; each R3 is preferably methyl; R 4 is preferably methyl; X is preferably H; k is preferably 0; m is preferably 0 and yrys are each preferably 2. In the above formulas, n is preferably at least about 6 when the number of centers N + and groups X is each 2 or 3, n is preferably at least 12, with a typical scale of approximately 12 to approximately 42 for the entire scale of u + v. Typically, v is 0 and u is from 2 to about 40, and preferably from 2 to about 20.

Additional detergent components The detergent compositions or components thereof according to the invention may also contain additional detergent components. The precise nature of these additional components and the levels of incorporation thereof will depend on the physical form of the composition and the precise nature of the washing operation for which it will be used. The compositions or components thereof according to the invention preferably contain one or more additional detergent components selected from additional surfactants, additional bleach, bleach catalysts, alkalinity systems, builders, bleach, bleach precursors, bleach catalysts. , organic polymeric compounds, additional enzymes, suds suppressors, lime soap dispersants, suspending and anti-redeposition agents for additional soils, perfumes and corrosion inhibitors.

Additional Surfactant The detergent compositions or components thereof according to the invention preferably contain an additional surfactant selected from anionic, nonionic, cationic, ampholytic, amphoteric and zwitterionic surfactants, and mixtures thereof. A typical list of anionic, non-ionic, ampholytic and zwitterionic classes, as well as species of these surfactants, is given in the US patent. No. 3,929,678, issued to Laughlin and Heuring on December 30, 1975. Additional examples are given in "Surface Active Agents and Detergents" (Vols. I and II, by Schwartz, Perry and Berch). A listing of suitable cationic surfactants is given in the 'U. No. 4,259,217, issued to Murphy on March 31, 1981. When present, ampholytic, amphoteric and zwitterionic surfactants are generally used in combination with one or more anionic and / or nonionic surfactants.

Anionic Surfactant The detergent compositions or component thereof according to the present invention preferably comprise an additional anionic surfactant.

Essentially any surfactants useful for detersive purposes may be comprised in the detergent composition. These may include salts (including, for example, sodium, potassium, ammonium and substituted ammonium salts such as mono-, di- and triethanolamine salts) of the anionic sulfate, sulfonate, carboxylate and sarcosinate surfactants. Anionic sulfate surfactants are preferred. Other anionic surfactants include isethionates such as acyl isethionates, N-acyl taurates, fatty acid amides of methyl tauride, alkyl succinates and sulfosuccinates, monoesters of sulfosuccinate (especially saturated and unsaturated] _2- i8 monoesters) sulfosuccinate diesters (especially saturated and unsaturated Cg-Ci4 diesters), N-acyl sarcosinates. Resin acids and hydrogenated resin acids are also suitable, such as rosin, hydrogenated rosin and rosin acids, as well as hydrogenated rosin acids present in tallow oil or derivatives thereof.

Anionic surfactant Sulfate Anionic Suitable sulfate for use in the present surfactants include linear primary and secondary alkyl and branched alkyl ethoxy sulfates, fatty oleilglicerolsulfatos ether sulfates, ethylene oxide alkylphenol, the glucaminsulfatos acyl C5-C17-N - (C 1 -C 4 alkyl) and - N- (hydroxyalkyl of C] _ C), and alkylpolysaccharide sulfates such as alkylpolyglucoside sulphates (nonionic non-sulfate compounds are described herein). Alkyl sulfate surfactants are preferably selected from the linear and branched primary C ^ Q-C ^ Q alkyl sulfates, most preferably the branched chain C ^ -C ^ alkyl sulphates and the straight chain linear alkyl sulphates. The alkyl ethoxy sulfate surfactants are preferably selected from the group consisting of the alkyl sulfates of C 1 -C 7 C 6 C 6 C 6 C 6 C 6 C 6 C 6 C 6 C 6 C 6 C 6 C 6 C 5 C 5 C 5 C 5 C 5 C 5 C 7 C C C C C C C C C C C C C C C C C C P C Most preferably, the alkylethylsulfate surfactant is a C-Cig alkyl sulfate, most preferably Cii-C-? , which has been ethoxylated with from 0.5 to 7, preferably from 1 to 5 moles of ethylene oxide per molecule. A particularly preferred aspect of the invention employs mixtures of the preferred alkyl sulfate and alkyl ethoxylate surfactants. Such mixtures have been described in PCT application No. WO) 3/18124.

Anionic Surfactant sulfonate anionic suitable sulfonate for use in the present surfactants include salts of linear alkylbenzene 5-C20 alquiléstersulfonatos, alkanesulfonates Cg-C22 primary or secondary olefin sulfonates Cg-C24 sulfonated polycarboxylic acids, alquilglicerolsulfonatos, fatty acyl glycerol sulfonates, fatty oleyl glycerol sulfonates and any mixtures thereof.

Anionic Surfactant Anionic carboxylate surfactants carboxylate include alkylethoxycarboxylates, the alkylpolyethoxypolycarboxylate surfactants and soaps ( "alqui1carboxilos"), especially certain secondary soaps as described herein. Suitable alkylethoxycarboxylates include those with the formula RO (CH2CH20) xCH2C00 ~ M + where R is an alkyl group from Cg to C] _g, x ranges from 0 to 10, and the ethoxylate distribution is such that, on a weight basis , the amount of material in which x is 0 is less than 20% and M is a cation. Suitable alkylpolyethoxy polycarboxylate surfactants include those having the formula RO- (CHR) _- CHR2-0) -R3 wherein R is an alkyl group from Cg to C;] _ g, x is from 1 to 25, R_ and R2 are selected from the group consisting of hydrogen, methyl acid radical, succinic acid radical, hydroxysuccinic acid radical and mixtures thereof, and R3 is selected from the group consisting of hydrogen, substituted or unsubstituted hydrocarbon having from 1 to 8 carbon atoms, and mixtures thereof. Suitable soap surfactants include secondary soap surfactants that contain a carboxyl unit connected to a secondary carbon. Preferred secondary soap surfactants for use herein are the water-soluble members selected from the group consisting of the water-soluble salts of 2-methyl-1-undecanoic acid, 2-ethyl-1-decanoic acid, 2-methyl-1-undecanoic acid, -propyl-1-nonanoic acid, 2-butyl-1-octanoic acid and 2-pentyl-1-heptanoic acid. Certain soaps can also be included as suds suppressors.

Alkali metal sarcosinate surfactant agent Other suitable anionic surfactants are the alkali metal sarcosinates of the formula R-CONIR1) CH2C00M, wherein R is a linear or branched C5-C17 alkyl or alkenyl group, R1 is an alkyl group of C] _- C4 and M is an alkali metal ion. Preferred examples are myristyl or oleoyl methylsarcosinates in the form of their sodium salts.

Alkoxylated nonionic surfactant Essentially any alkoxylated nonionic surfactants are suitable herein. Ethoxylated and propoxylated nonionic surfactants are preferred. Preferred alkoxylated surfactants can be selected from the classes of the nonionic condensates of alkylphenols, nonionic ethoxylated alcohols, ethoxylated / propoxylated nonionic fatty alcohols, ethoxylated / propoxylated non-ionic condensates with propylene glycol and the non-ionic ethoxylated condensation products with adducts of propylene oxide / ethylenediamine.

Nonionic surfactant of alkoxylated alcohol The condensation products of aliphatic alcohols with from 1 to 25 moles of alkylene oxide, particularly ethylene oxide and / or propylene oxide, are suitable for use herein. The alkyl chain of the aliphatic alcohol may be either straight or branched, primary or secondary, and generally contains from 6 to 22 carbon atoms. Particularly preferred are the condensation products of alcohols having an alkyl group containing from 8 to 20 carbon atoms with from 2 to 10 moles of ethylene oxide per mole of alcohol.

Nonionic surfactant of polyhydroxy fatty acid amide The polyhydroxy fatty acid amides suitable for use herein are those having the structural formula R2CONR1Z, wherein: R1 is H, C1.-C4, 2-hydroxyethyl hydrocarbyl, -hydroxypropyl, ethoxy, propoxy, or a mixture thereof, preferably C 1 -C 4 alkyl, most preferably C 1 or C 2 alkyl, more preferably Ci alkyl (ie, methyl); and R2 is a C5-C31 hydrocarbyl, preferably straight chain C5-C19 alkyl or alkenyl, most preferably straight chain C9-C17 alkyl or alkenyl, more preferably alkyl or alkenyl of C ^ - ^ -j chain straight or a mixture thereof, and Z is a polyhydroxyhydrocarbyl having a linear hydrocarbyl chain with at least 3 hydroxyls directly connected to the chain, or an alkoxylated derivative (preferably ethoxylated or propoxylated) thereof. Z will preferably be derived from a reducing sugar in a reductive amination reaction; most preferably Z is a glycityl.

Nonionic Fatty Acid Amide Surfactant Suitable fatty acid amide surfactants include those having the formula: R6CON (R7) 2 wherein R6 is an alkyl group containing from 7 to 21, preferably from 9 to 17 atoms of carbon and each R7 is selected from the group consisting of hydrogen, C1-C4 alkyl, C1-C4 hydroxyalkyl, and - (C2H4?) xH, wherein x is on the scale of 1 to 3.

Nonionic Terpolysaccharide Agent of Alkylpolysaccharide Suitable alkylpolysaccharides that are used herein are described in the US patent. No. 4,565,647, Filling, issued January 21, 1986, having a hydrophobic group containing from 6 to 30 carbon atoms, and a polysaccharide, e.g., a polyglucoside, a hydrophilic group containing from 1.3 to 10. saccharide units. Preferred alkyl polyglycosides have the formula R20 (CnH2nO) (glucosyl) x wherein R2 is selected from the group consisting of alkyl, alkylphenyl, hydroxyalkyl, hydroxyalkylphenyl, and mixtures thereof, in which the alkyl groups contain from 10 to 18 carbon atoms; n is 2 or 3; t is from 0 to 10, and x is from 1.3 to 8. The glucosyl is preferably derived from glucose.

Amphoteric Surfactant Amphoteric surfactants suitable for use herein include amine oxide surfactants and alkylamphocarboxylic acids. Suitable amine oxides include those compounds having the formula R3 (OR4) xN ° (R5) 2, wherein R3 is selected from an alkyl, hydroxyalkyl, acylamidopropyl and alkylphenyl group or mixtures thereof, containing from 8 to 26 carbon atoms; R4 is an alkylene or hydroxyalkylene group containing from 2 to 3 carbon atoms, or mixtures thereof; x is from 0 to 5, preferably from 0 to 3; and each R 5 is an alkyl or hydroxyalkyl group containing from 1 to 3 carbon atoms, or a group of polyethylene oxide containing from 1 to 3 ethylene oxide groups. Preferred are the alkyl dimethylamine oxide of C ^ o-Cig and the acrylamidodimethylamine oxide of C10-C18. A suitable example of an alkylamphodicarboxylic acid is Mirano1 (MR) C2M Conc., Manufactured by Miranol, Inc., Dayton, NJ.

Zwitterionic Surfactant Zwitterionic surfactants may also be incorporated into the detergent compositions herein. These surfactants can be broadly described as derivatives of secondary and tertiary amines, derivatives of heterocyclic secondary and tertiary amines or derivatives of quaternary ammonium, quaternary phosphonium or tertiary sulfonium compounds. The surfactants of sultaine and betaine are examples of zwitterionic surfactants that can be used herein. Suitable betaines are those compounds having the formula: R (R ') 2N + R2COO- wherein R is a hydrocarbyl group of CQ-C ^ Q, each R1 is typically C1-C3 alkyl, and R2 is a hydrocarbyl group of C1-C5. The preferred betaines are the betaines of dimethyl ammonium hexanoate of C] _2 ~ ci8 and the acylamidopropane (or ethane) dimethyl (or diethyl) betaines of CI Q-IQ. Also suitable for use herein are complex betaine surfactants.

Cationic Surfactants Suitable cationic surfactants for use in the detergent compositions or components herein include the quaternary ammonium surfactants selected from N-alkyl or alkenyl ammonium mono- or cycloalkyl surfactants, preferably Cg-CiQ at which the remaining N positions are substituted by methyl, hydroxyethyl or hydroxypropyl groups. The cationic ester surfactant is a compound preferably soluble in water having surfactant properties and comprising at least one ester linkage (ie, -COO-) and at least one cationically charged group. Suitable cationic ester surfactants, including choline ester surfactants, have been described, for example, in US Patents. Nos. 422,8042, 4239660 and 4260529. In a preferred aspect, the ester linkage and the cationically charged group are separated from each other in the surfactant molecule by a spacer group consisting of a chain comprising at least three atoms ( that is, with a chain length of three atoms), preferably three to eight atoms, most preferably three to five atoms, more preferably three atoms. The atoms forming the chain of the spacer group are selected from the group consisting of carbon, nitrogen and oxygen atoms, and any mixtures thereof, with the proviso that no nitrogen or oxygen atom in said chain connects only with the atoms of carbon in the chain. In this way, groups that have, for example, links -0-0- (ie, peroxide), -NN- and -N-0- are excluded, but include the separating groups that have, for example, links -CH2-O-CH2- and -CH2-NH-CH2. In a preferred aspect, the chain of the spacer group only comprises carbon atoms, most preferably the chain is a hydrocarbyl chain.

Water-soluble builder composition The detergent compositions or components thereof according to the present invention preferably contain a water-soluble builder compound, typically present at a level of 1% to 80% by weight, preferably 10% to 70% by weight, more preferably from 20% to 60% by weight of the composition. Water-soluble builder compounds include water-soluble monomeric polycarboxylates or their acid forms, homo- or copolymeric polycarboxylic acids or their salts, in which the polycarboxylic acid comprises at least two carboxylic radicals separated from one another by no more of two carbon atoms, borates, phosphates and mixtures of any of the foregoing. The carboxylate or polycarboxylate builder may be of the monomeric or oligomeric type, although monomeric polycarboxylates are generally preferred for reasons of cost and performance.

Suitable carboxylates containing a carboxy group include the water soluble salts of lactic acid, glycolic acid and ether derivatives thereof. Polycarboxylates containing two carboxy groups include the water-soluble salts of succinic acid, malonic acid, (ethylenedioxy) diacetic acid, maleic acid, diglycolic acid, tartaric acid, tartronic acid and fumaric acid, as well as ether carboxylates and sulfinyl carboxylates . Polycarboxylates containing three carboxy groups include, in particular, citrates, aconitrates and water-soluble citraconates, as well as the succinate derivatives such as the carboxymethyloxysuccinates described in British Patent No. 1,379,241, the lactoxysuccinates described in British Patent No. 1,389,732 and the aminosuccinates described in Dutch application 7205873 and oxypolycarboxylate materials such as 2-oxa-1,1,3-propanedicarboxylates described in British Patent No. 1,387,447. Polycarboxylates containing four carboxy groups include the oxydisuccinates described in British Patent No. 1,261,829,11,2, 2-etanttracarboxylates, 1, 1, 3, 3 -propanetracarboxylates and the 1,1,2,3-propanetracarboxylates. Polycarboxylates containing sulfo substituents include the sulfosuccinate derivatives described in British Patents Nos. 1,398,421 and 1,398,422 and the US patent. No. 3,936,448 and the sulfonated pyrolysed citrates described in British Patent No. 1,439,000. Preferred polycarboxylates are hydrocarboxylates containing up to three carboxy groups per molecule, most particularly citrates. The acids of origin of monomeric or oligomeric polycarboxylate chelating agents or mixtures thereof with their salts, eg, mixtures of citric acid or citrate / citric acid are also contemplated as useful builders components. Borate builders, as well as builders that contain borate-forming materials that can produce borate under detergent storage or wash conditions are water soluble builders useful herein. Suitable examples of phosphate builders are alkali metal tripolyphosphates, sodium, potassium and ammonium pyrophosphate, potassium and sodium ammonium pyrophosphate, potassium and sodium orthophosphate, and sodium polymetaphosphate, in which the degree of polymerization varies from about 6 to 21, and the salts of phytic acid.

Partially soluble or insoluble builder compound The detergent compositions of the present invention may contain a partially soluble or insoluble builder compound, typically present at a level of 1% to 80% by weight, preferably 10% to 70% by weight , most preferably from 20% to 60% by weight of the composition. Examples of detergents largely soluble in water include sodium aluminosilicates. Suitable aluminosilicate zeolites have the unit cell formula Naz [(AIO2) z (SiO2) and] -x ^ O wherein z and y are integers of at least 6; the molar ratio of zay is from 1.0 to 0.5 and x is at least 5, preferably from 7.5 to 276, most preferably from 10 to 264. The aluminosilicate material is in hydrated form and is preferably crystalline, containing from 10% to 28%. %, most preferably from 18% to 22% water in bound form. The aluminosilicate zeolites may be materials that occur naturally, but are preferably derived in synthetic form. Synthetic crystalline aluminosilicate ion exchange materials are available under the designations Zeolite A, Zeolite B, Zeolite X, Zeolite HS and mixtures thereof. Zeolite A has the formula: Na12 [(A102) 12 (Si02) 12- -xH20 where x is from 20 to 30, especially 27. Zeolite X has the formula: Nagg [(A102) 86 (Si0)? or] • 276H 0. Another preferred aluminosilicate zeolite is the zeolite MAP builders. . The zeolite MAP can be present at a level of 1% to 80%, most preferably 15% to 40% by weight of the compositions. Zeolite MAP is described in EP 384070A (Unilever). It is defined as an alkali metal aluminosilicate of the zeolite P type having a silicone to aluminum ratio of not more than 1.33, preferably in the range of 0.9 to 1.33 and most preferably in the range of 0.9 to 1.2. Of particular interest is zeolite MAP which has a silicone to aluminum ratio of no more than 1.15, most particularly no more than 1.07. In a preferred aspect, the zeolite MAP builders have a particle size, expressed as a d5_ value of 1.0 to 10.0 microns, most preferably 2.0 to 7.0 microns, more preferably 2. 5 to 5.0 microns. The dso value indicates that 50% by weight of the particles have a diameter smaller than that number. The particle size can be determined in particular by conventional analytical techniques such as microscopic determination using a scanning electron microscope or by means of a laser granulometer. Other methods to establish the dso values are described in EP 384070A.

Heavy metal ion sequestrant The detergent compositions of the invention preferably contain a heavy metal ion sequestrant as an optional component. By heavy metal ion sequestrant is meant here components that act to sequester (chelate) heavy metal ions. These components may also have calcium and magnesium chelating ability, but preferably show selectivity to bind heavy metal ions such as iron, manganese and copper. Heavy metal ion sequestrants are generally present at a level of 0.005% to 20%, preferably 0.1% to 10%, most preferably 0.25% to 7.5% and more preferably 0.5% to 5% by weight of the compositions . Heavy metal ion sequestrants suitable for use herein include organic phosphonates, such as the aminoalkylene poly (alkylene phosphonates), alkali metal ethane-1-hydroxy diphosphonates, and nitrilotrimethylene phosphonates.

Preferred among the above species are diethylenetriaminpenta (methylene phosphonate), ethylenediaminetri- (methylene phosphonate), hexamethylene diamine tetra (methylene phosphonate) and hydroxyethylene 1,1 diphosphonate. Another heavy metal ion sequestrant suitable for use herein includes nitrilotriacetic acid and polyaminocarboxylic acids such as ethylenediaminetetraacetic acid, ethylenetriaminpentaacetic acid, ethylenediamine disuccinic acid, ethylene diamine diglutaric acid, 2-hydroxypropylenediamindisuccinic acid or any salt thereof. Especially preferred is ethylenediamine-N, N'-disuccinic acid (EDDS) or the alkali metal, alkaline earth metal, ammonium or substituted ammonium salts thereof, or mixtures thereof. Other heavy metal ion sequestrants suitable for use herein are iminodiacetic acid derivatives such as 2-hydroxyethyl diacetic acid or glyceryl imino diacetic acid, described in EP-A-317,542 and EP-A-399, 133. Sequestrants of iminodiacetic acid-N-2-hydroxypropyl sulfonic acid and of aspartic acid-N-carboxymethyl N-2-hydroxypropyl-3-sulfonic acid described in EP-A-516,102 are also suitable herein. The b-alanine-N, N'-diacetic acid, aspartic acid-N, N'-diacetic acid, aspartic acid-N-monoacetic acid and iminodisuccinic acid sequestrants described in EP-A-509,382 are also suitable. EP-A-476,257 describes suitable amino-based sequestrants, EP-A-510,331 describes suitable sequestrants derived from collagen, keratin or casein. EP-A-528,859 discloses a suitable alkyl iminodiacetic acid sequestrant. Also suitable are dipicolinic acid and 2-phosphonobutan-1,2,4-tricarboxylic acid. Glycinamide-N-N'-disuccinic acid (GADS), ethylene diamine N-diglytaric acid (EDDG) and 2-hydroxypropylenediamine-N-N'-disuccinic acid (HPDDS) are also suitable.

Organic Peroxyacid Bleach System A preferred feature of the detergent compositions or components thereof according to the invention is an organic peroxyacid bleach system. In a preferred embodiment, the bleaching system contains a source of hydrogen peroxide and an organic peroxyacid bleach precursor compound. The production of the organic peroxyacid occurs by means of an in situ reaction of the precursor with a source of hydrogen peroxide. Preferred hydrogen peroxide sources include the inorganic perhydrate bleaches. In a preferred and alternative embodiment, a preformed organic peroxyacid is incorporated directly into the composition.

Also disclosed are compositions containing mixtures of a source of hydrogen peroxide and an organic peroxyacid precursor in combination with a preformed organic peroxyacid.

Inorganic Perhydrate Bleaches Inorganic perhydrate salts are a preferred source of hydrogen peroxide. These salts are normally incorporated in the alkali metal form, preferably sodium salt at a level of 1% to 40% by weight, most preferably from 2% to 30% by weight and more preferably from 5% to 25% by weight of the salts. compositions Examples of inorganic perhydrate salts include perborate, percarbonate, perphosphate, persulfate and persilicate salts. The inorganic perhydrate salts are usually the alkali metal salts. The inorganic perhydrate salt can be included as the crystalline solid without additional protection. However, for certain perhydrate salts, the preferred embodiments of said granulated compositions use a coated form of the material, which provides better storage stability for the perhydrate salt in the granulated product. Suitable coatings comprise inorganic salts such as alkali metal silicate, carbonate or borate salts or mixtures thereof, or organic materials such as waxes, oils or fatty acids. Sodium perborate is a preferred perhydrate salt and may be in the form of the monohydrate of the nominal formula NaB02H202 or the tetrahydrate NaB02H202.3H20. The alkali metal percarbonates, particularly sodium percarbonate, are the perhydrates that are preferred herein. Sodium percarbonate is an addition compound having a formula corresponding to 2Na2C? 3.3H2O2 and is commercially available as a crystalline solid. Potassium peroximonopersulfate is another inorganic perhydrate salt useful in the detergent compositions herein.

Peroxyacid bleach precursor Peroxyacid bleach precursors are compounds that react with hydrogen peroxide in a perhydrolysis reaction to produce a • peroxyacid. Peroxyacid bleach precursors can generally be represented as: O X-C-L where L is a residual group and X is essentially any functionality, such that in perhydrolysis, the structure of the produced peroxyacid is: OR X-C-OOH The peroxyacid bleach precursor compounds are preferably incorporated at a level of 0. 05% to 20% by weight, most preferably from 1% to 15% by weight, more preferably from 1.5% to 10% by weight of the detergent compositions. Suitable hydrophobic peroxyacid bleach precursor compounds typically contain one or more N- or O-acyl groups, which precursors can be selected from a wide variety of classes. Suitable classes include anhydrides, esters, imides, lactams and acylated derivatives of imidazoles and oximes. Examples of useful materials within these classes are described in GB-A-1586789. Suitable esters are described in GB-A-836988, 864798, 1147871, 2143231 and EP-A-0170386.

Residual groups The residual group, hereinafter group L, must be sufficiently reactive so that the perhydrolysis reaction occurs within the optimum time frame (eg, a wash cycle). However, if L is very reactive, this activator will be difficult to stabilize for use in a bleaching composition. The preferred L groups are selected from the group consisting of: R3 O Y -O-C = CHR4, and - N-S-CH-R4 I M R3O and mixtures thereof, wherein R ^ is an alkyl, aryl or alkaryl group containing from 1 to 14 carbon atoms, R3 is an alkyl chain containing from 1 to 8 carbon atoms, R4 is H or R3, and And it is H or a solubilizing group. Any of R ^, R3 and R4 can be essentially substituted by any functional group including, for example, alkyl, hydroxy, alkoxy, halogen, amine, nitrosyl, amide and ammonium or alkylammonium groups. The preferred solubilizing groups are -S? 3_M +, -C02_M +, -SO4- A -N + (R3) 4X_ and 0 <-N (R3) and most preferably -S? 3 ~ M + and -C? 2 ~ M +, wherein R3 is an alkyl chain containing from 1 to 4 carbon atoms, M is a cation that provides solubility to the activator of bleaching and X is an anion that provides solubility to the bleach activator. Preferably, M is an alkali metal, ammonium or substituted ammonium cation, with more sodium and potassium being preferred, and X is a halide, hydroxide, methylsulfate or acetate anion.

Precursors of bleaching of alkylpercarboxylic acid The bleach precursors of alkylpercarboxylic acid form percarboxylic acids in the perhydrolysis. Preferred precursors of this type provide peracetic acid in the perhydrolysis.

Preferred alkylpercarboxylic type precursor compounds include the N, N, N-tetraacetylated alkylene diamines in which the alkylene group contains 1 to 6 carbon atoms, particularly those compounds in which the alkylene group contains 1, 2 and 6 carbon atoms. Tetraacetylethylenediamine (TAED) is particularly preferred. Other preferred alkylpercarboxylic acid precursors include sodium 3,5-trimethylhexanoyloxybenzenesulfonate (iso-NOBS), sodium nonanoyloxybenzenesulfonate (NOBS), sodium acetoxybenzenesulfonate (ABS) and pentaacetylglucose.

Precursors of alkylperoxyacid substituted with amide Preferred peroxyacid precursors are amide substituted alkylperoxy acid precursor compounds, including those having the following general formulas: R1 C N R2 C L R1 N R2 O R5 OR R5 O O wherein R1 is an aryl or alkaryl group with 1 to 14 carbon atoms, R2 is an alkylene group containing 1 to 14 carbon atoms, and R5 is H or an alkyl group containing 1 to 10 carbon atoms and L can be essentially any residual group. Amide-substituted bleach activating compounds of this type are described in EP-A-0170386.

Perbenzoic acid precursor Perbenzoic acid precursor compounds provide perbenzoic acid in perhydrolysis. Suitable O-acylated perbenzoic acid precursor compounds include the substituted and unsubstituted benzoyl oxybenzenesulfonates and the benzoylation products of sorbitol, glucose and all saccharides with benzoylating agents, and those of the imide type including N-benzoyl succinimide, tetrabenzoylethylenediamine and the N-benzoyl substituted ureas. Suitable imidazole-type perbenzoic acid precursors include N-benzoyl imidazole and N-benzoyl benzimidazole. Other perbenzoic acid precursors containing a useful N-acyl group include N-benzoyl pyrrolidone, dibenzoyl taurine and benzoyl pyroglutamic acid.

Cationic peroxyacid precursors Cationic peroxyacid precursor compounds produce cationic peroxyacids in perhydrolysis.

Typically, cationic peroxyacid precursors are formed by substituting the peroxyacid part of a suitable peroxyacid precursor compound with a positively charged functional group, such as an ammonium or alkylammonium group, preferably an ethyl or methylammonium group. Cationic peroxyacid precursors are typically present in the solid detergent compositions as a salt with a suitable anion, such as a halide ion. The peroxyacid precursor compound which will be so cationically substituted may be a perbenzoic acid precursor compound or a substituted derivative thereof as described hereinabove. Alternatively, the peroxyacid precursor compound may be a precursor alkylcarcarboxylic acid compound or an amide substituted alkylperoxyacid precursor as described hereinafter. Cationic peroxyacid precursors are described in the U.S. Patents. Nos. 4,751,015; 4,988,451; 4,397,757; 5,269,962; 5,127,852; 5,093,022; 5,106,528; R.U. 1,382,594; EP 475,512, 458,396 and 284,292; and in JP 87-318,332. Examples of preferred cationic peroxyacid precursors are described in United Kingdom patent application No. 9407944.9 and in US patent applications. Nos. 08/298903, 08/298650, 08/298904 and 08/298906.

Suitable cationic peroxyacid precursors include any of the substituted ammonium or alkylammonium alkyl or benzoyloxybenzenesulfonates, the N-acylated caprolactams and the benzoylperoxides of monobenzoyltetraacetyl glucose. Preferred cationic peroxyacid precursors of the N-acylated caprolactam class include the trialkylammonium methylehbenzoylcaprolactams and the trialkylammonium methyalkylcaprolactams.

Benzoxazine organic peroxyacid precursors Also suitable are the benzoxazine type precursor compounds such as those described for example in EP-A-332,294 and EP-A-482, 807, particularly those having the formula: wherein R] _ is H, alkyl, alkaryl, aryl or arylalkyl.

Preformed organic peroxyacid The organic peroxyacid bleach system may contain, in addition to, or as an alternative to, an organic peroxyacid bleach precursor compound, a preformed organic peroxyacid, typically at a level of from 1% to 15% by weight, very preferably from 1% to 10% by weight of the composition. A preferred class of organic peroxyacid compounds are the amine substituted compounds of the following general formula: Rl c - N - R2 C - 00H wherein R1 is an alkyl, aryl or alkaryl group with from 14 carbon atoms, R2 is an alkylene, arylene and alkarylene group containing 1 to 14 carbon atoms, and R5 is H or an alkyl, aryl or alkaryl containing 1 to 10 carbon atoms. Amide-substituted organic peroxyacid compounds of this type are described in EP-A-0170386. Other organic peroxyacids include the diacyl and tetraacylperoxides, especially diperoxydodecanoic acid, diperoxytetradecanedioic acid and diperoxyhexadecane-dioic acid. Also suitable here are mono- and diperazelaic acid, mono- and diperbrasyl acid and N-phthaloylaminoperoxycaproic acid.

Enzyme Another preferred ingredient useful in detergent compositions or components thereof, is one or more additional enzymes. Additional preferred enzyme materials include commercially available lipases, cutinases, amylases, neutral and alkaline proteases, esterases, pectinases, lactases and peroxidases and incorporated in conventional manner in detergent compositions. Suitable enzymes are described in the US patents. 3,519,570 and 3,533,139. Preferred commercially available protease enzymes include those sold under the tradenames Alcalase, Savinase, Primase, Durazym and Esperase by Novo Industries A / S (Denmark), those sold under the trade name Maxatase, Maxacal and Maxapem by Gist-Brocades, those sold by Genecor International and those sold under the trade name Opticlean and Optimase by Solvay Enzimes. The protease enzyme can be incorporated in the compositions according to the invention at a level of 0.001% to 4% active enzyme by weight of the composition. Preferred amylases include, for example, alpha-amylases obtained from a special strain of B. licheniformis, described in greater detail in GB-1,269,839 (Novo). Preferred commercially available amylases include, for example, those sold under the tradename Rapidase by Gist-Brocades, and those sold under the trade name Termamyl and BAN by Novo Industries A / S. The amylase enzyme can be incorporated in the composition according to the invention at a level of 0.0001% to 2% enzyme. active in weight of the composition. The lipolytic enzyme may be present at levels of active lipolytic enzyme from 0.0001% to 2% by weight, preferably 0.001% to 1% by weight, most preferably from 0.001% to 0.5% by weight of the compositions. The lipase can be of fungal or bacterial origin, being obtained, for example, from a lipase-producing strain of the Humicola species, the Thermomyces species or the pseudomonas species, including Pseudomonas pseudoalcaligenes or Pseudomas fluorescens. Lipase that comes from chemically or genetically modified mutants of these strains are also useful herein. A preferred lipase is derived from Pseudomonas pseudoalcaligenes, which is described in the European patent granted EP-B-0218272. Another preferred lipase herein is obtained by cloning the Humicola lanuginosa gene and expressing the Aspergillus oryza gene as a host, as described in the European patent application EP-A-0258 068, which is commercially available from Novo Industri A / S, Bagsvaerd, Denmark under the trade name Lipolase. Lipase is also described in the U.S. patent. No. 4,810,414, Huge-Jensen et al., Issued March 7, 1989.

Organic polymeric compound Organic polymeric compounds are preferred additional components of the detergent compositions or components thereof according to the invention, and are preferably present as components of any particulate components, where they can act such as to bind the particulate component each. By "organic polymeric compound" is meant essentially any polymeric organic compound that is not an oligoester or polyamine soil release polymer, and which are commonly used as dispersants and anti-redeposition agents and suspension of soils in detergent compositions , including any of the high molecular weight organic polymeric compounds described as clay flocculating agents herein, not being an anti-fouling / anti-redeposition agent of quaternized ethoxylated (poly) amine clay in accordance with the invention. The organic polymeric compound is typically incorporated in the detergent compositions of the invention at a level of from 0.1% to 30%, preferably from 0.5% to 15%, most preferably from 1% to 10% by weight of the compositions. Examples of organic polymeric compounds include organic homo- or copolymeric water-soluble polycarboxylic acids or their salts in which the polycarboxylic acid comprises at least two carboxyl radicals separated from each other by not more than two carbon atoms. Polymers of the latter type are described GB-A-1, 596, 756. Examples of such salts are polyacrylates of MW 1000-5000 and their copolymers with maleic anhydride, said copolymers have a molecular weight of 2000 to 100,000, especially 40,000 to 80,000. Polyamino compounds are useful herein, including those derived from aspartic acid such as those described in EP-A-305282, EP-A-305283 and EP-A-351629. Also suitable herein are terpolymers containing selected monomeric units of maleic acid, acrylic acid, polyaspartic acid and vinyl alcohol, particularly those having an average molecular weight of 5,000 to 10,000. Other organic polymeric compounds suitable for incorporation into the detergent compositions herein include essentially any charged and uncharged cellulose derivative such as methylcellulose, carboxymethylcellulose, hydroxypropylmethylcellulose and hydroxyethylcellulose. Additional organic polymeric compounds and useful with polyethylene glycols, particularly those with a molecular weight of 1000-10000, very particularly 2000 to 8000 and more preferably around 4000.

Foam suppression system The detergent compositions of the invention, when formulated for use in machine wash compositions, preferably comprise a foam suppression system present at a level of from 0.01% to 15%, preferably from 0.05% to 10%. % and most preferably from 0.1% to 5% by weight of the composition. The foam suppression systems suitable for use herein may comprise essentially any known antifoam compound, including, for example, silicone anti-foam compounds and 2-alkyl alkanol antifoaming compounds. By "antifoaming compound" is meant any compound or mixtures of compounds which act to depress the foaming produced by a solution of a detergent composition, particularly in the presence of the agitation of that solution. Particularly preferred antifoam compounds for use herein are the silicone anti-foam compounds defined herein as any anti-foam compound that includes a silicone component. Said silicone anti-foam compounds also typically contain a silica component. The term "silicone", as used herein and generally in the industry, encompasses a variety of relatively high molecular weight polymers containing siloxane units and a hydrocarbyl group of various types. The silicone antifoams that are preferred are the siloxanes, particularly polydimethylsiloxanes having trimethylsilyl end blocking units. Other suitable antifoam compounds include the monocarboxylic fatty acids and the soluble salts thereof. These materials are described in the U.S. patent. No. 2,954,347, issued September 27, 1960 to Wayne St. John The monocarboxylic fatty acids and salts thereof for use as foam suppressors typically have hydrocarbyl chains of 10 to 24 carbon atoms, preferably 12 to 18 carbon atoms. Suitable salts include the alkali metal salts such as the sodium, potassium and lithium salts, and the ammonium and alkanolammonium salts. Other suitable antifoam compounds include, for example, high molecular weight fatty esters (e.g., fatty acid triglycerides), fatty acid esters of monovalent alcohols, aliphatic C 13 -C 40 ketones (e.g., stearone), N-alkylated amino triazines such as tri- or hexa-alkylmelamines or di- to tetra-alkyldiaminclortriazines formed as cyanuric chloride products with two or three moles of a primary or secondary amine containing 1 to 24 carbon atoms, propylene oxide, amide of bis-stearic acid and the di-alkali metal monostearyl phosphates (e.g., sodium, potassium, lithium) and phosphate esters. A preferred foam suppressor system comprises: (a) an antifoam compound, preferably a silicone antifoam compound, most preferably a silicone antifoam compound comprising in combination: (i) polydimethylsiloxane, at a level of 50% a 99%, preferably 75% to 95% by weight of the silicone antifoam compound; and (ii) silica, at a level of 1% to 50%, preferably 5% to 25% by weight of the silicone / silica antifoam compound; wherein said silica / silicone antifoam compound is incorporated at a level of 5% to 50%, preferably 10% to 40% by weight; (b) a dispersing compound, most preferably comprising a silicone glycol copolymer with a polyoxyalkylene content of 72-78% and a ratio of ethylene oxide to propylene oxide of from 1: 0.9 to 1: 1.1, at a level of 0.5% to 10%, preferably 1% to 10% by weight; a particularly preferred glycol silicone hardener copolymer of this type is DC0544, commercially available from DOW Corning under the tradename DC0544; (c) an inert carrier fluid compound, most preferably comprising a C alcohol? -C? Ethoxylated with an ethoxylation degree of 5 to 50, preferably 8 to 15, at a level of 5% to 80%, preferably 10% to 70% by weight; A highly preferred particulate foam suppression system is described in EP-A-0210731 and comprises a silicone antifoam compound and an organic carrier material having a melting point in the range of 50 ° C to 85 ° C, which The organic carrier material comprises a monoester of glycerol and a fatty acid having a carbon chain containing from 12 to 20 carbon atoms. EP-A-0210721 discloses other preferred particulate foam suppressor systems in which the organic carrier material is a fatty acid or alcohol having a carbon chain containing from 12 to 20 carbon atoms or a mixture thereof , with a melting point of 45 ° C to 80 ° C.

Polymeric Dye Transfer Inhibitory Agents The detergent compositions herein may additionally comprise from 0.01% to 10%, preferably from 0.05% to 0.5% by weight of polymeric dye transfer inhibiting agents. Polymeric dye transfer inhibiting agents are preferably selected from polyamine N-oxide polymers, copolymers of N-vinylpyrrolidone and N-vinylimidazole, polyvinylpyrrolidone polymers or combinations thereof, wherein these polymers can be entangled polymers. a) Polyamide N-oxide polymers Polyamine N-oxide polymers suitable for use herein contain units having the following structural formula: P (I) Ax R I where P is a polymerizable unit, and O A is NC, 1CO, C, -O- -S- -N- x is 0 or 1; R are aliphatic, aliphatic, ethoxylated, aromatic, heterocyclic or alicyclic groups or any combination thereof to which the nitrogen of the N-O group may be attached or in which the nitrogen of the N-O group is part of these groups. The N-O group can be represented by the following general structures: 0 O wherein R 1, R 2 and R 3 are aliphatic groups, aromatic, heterocyclic or alicyclic groups or combinations thereof, x and / oyo / yz is or 1 and wherein the nitrogen of the NO group can be fixed or where the nitrogen of the group NOT part of these groups. The N-O group can be part of the polymerizable unit (P) or it can be attached to the polymeric base structure or to a combination of both. Suitable polyamine N-oxides in which the N-O group forms part of the polymerizable unit comprise the polyamine N-oxides in which R is selected from aliphatic, aromatic, alicyclic or heterocyclic groups. A class of polyamine N-oxides comprises the group of polyamine N-oxides in which the nitrogen of the group NO is part of the group R. The preferred N-oxides of polyamine are those in which R is a heterocyclic group such such as pyrridine, pyrrole, imidazole, pyrrolidine, piperidine, quinoline, acridine and derivatives thereof. Other suitable polyamine N-oxides are the polyamine oxides to which the N-O group is attached to the polymerizable unit. A preferred class of these polyamine N-oxides comprises the polyamine N-oxides having the general formula (I) wherein R is an aromatic group, alicyclic heterocyclic or in which the nitrogen of the functional group N-O is part of said group R. Examples of these classes are the polyamine oxides in which R is a heterocyclic compound such as pyrridine, pyrrole, imidazole and derivatives thereof. The polyamine N-oxides can be obtained in almost any degree of polymerization. The degree of polymerization is not critical, as long as the material has the water solubility and the desired dye suspension power. Typically, the average molecular weight is within the range of 500 to 1,000,000. b) Copolymers of N-vinylpyrrolidone and N-vinylimidazole The copolymers of N-vinylimidazole and N-vinylpyrrolidone suitable in the present invention have an average molecular weight scale of 5,000 to 50,000. Preferred copolymers have a molar ratio of N-vinylimidazole to N-vinylpyrrolidone from 1 to 0.2. c) Polyvinylpyrrolidone The detergent compositions of the present invention can also use polyvinylpyrrolidone ("PVP") having an average molecular weight from 2,500 to 400,000. Suitable polyvinyl pyrrolidones are commercially available from ISP Corporation, New York, NY and Montreal, Canada, under the product names PVP K-15 (viscosity molecular weight of 10,000), PVP K-30 (average molecular weight of 40,000), PVP K-60 (average molecular weight of 160,000) and PVP K-90 (average molecular weight of 360,000). PVP K-15 is also available from ISP Corporation. Other suitable polyvinyl pyrrolidones which are commercially available from BASF Cooperation include Sokalan HP 165 and Sokalan HP 12. d) Polyvinyloxazolidone The detergent compositions herein can also use polyvinyloxazolidones as a polymeric dye transfer inhibiting agent. Said polyvinyloxazolidones have an average molecular weight of 2,500 to 400,000. e) Polyvinylimidazole The detergent compositions herein can also use polyvinylimidazole as a polymeric dye transfer inhibiting agent. Said polyvinylimidazoles have an average molecular weight of 2,500 to 400,000.

Optical brightener The detergent compositions herein also optionally contain from about 0.005% to 5% by weight of certain types of hydrophilic optical brighteners. The hydrophilic optical brighteners useful herein include those having the structural formula: wherein R ^ _ is selected from anilino, N-2-bis-hydroxyethyl and NH-2-hydroxyethyl; R 2 is selected from N-2-bis-hydroxyethyl, N-2-hydroxyethyl-N-methylamino, morphino, chloro and amino; and M is a salt-forming cation such as sodium or potassium. When in the previous formula R ^ is anilino, R2 is N-2-bis-hydroxyethyl and M is a cation such as sodium, the brightener is 4,4 '-bis [(4-anilino-6- (N-2-bis-hydroxyethyl) -s-triazin-2-acid] il) amino] -2,2'-styrylisulfonic acid and the disodium salt. This particular brightener species is marketed under the trade name Tinopal UNPA-GX by Ciba-Geigy Corporation. The Tinopal UNPA-GX is the preferred hydrophilic optical brightener useful in the detergent compositions herein. When in the above formula R] _ is anilino, R2 is N-2-hydroxyethyl-N-2-methylamino and M is a cation such as sodium, the brightener is the disodium salt of 4,4'-bis [4] -anilino-6- (N-2-hydroxyethyl-N-methylamino) -s-triazin-2-yl) amino] -2, 2'-stilbenedisulfonic acid. This particular brightener species is commercially marketed under the trade name Tinopal 5BM-GX by Ciba-Geigy Corporation. When in the above formula R ^ is anilino, R2 is morphino and M is a cation such as sodium, the brightener is the sodium salt of 4,4'-bis [(4-anilino-6-morphino-s-triazin -2-yl) amino] 2,2'-stilbenedisulfonic acid. This particular brightener species is sold commercially under the trade name Tinopal 7 AMS-GX by Ciba-Geigy Corporation.

Polymeric agent for removing dirt The polymeric agents known to release soils, hereinafter "SRA" or "SRA's", can optionally be used in the present detergent compositions. If used, the SRA's will generally comprise from about 0.01% to 10.0%, typically from about 0.1% to 5%, preferably from about 0.2% to 3.0% by weight, of the compositions. Preferred SRA's typically have hydrophilic segments to hydrophilize the surface of the hydrophobic fibers such as polyester and nylon, and the hydrophobic segments to deposit on and remain adhered to the hydrophobic fibers through the completion of the washing and rinsing cycles, thus serving as an anchor for the hydrophilic segments. This can make it possible for stains that occur after treatment with the SRA to be cleansed more easily in subsequent washing procedures. Preferred SRAs include oligomeric terephthalate esters, typically prepared by methods that include at least one transesterification / oligomerization, commonly with a metal catalyst such as a titanium (IV) alkoxide.

Said esters can be manufactured using additional monomers capable of being incorporated into the ester structure through uan, two, three, four or more positions, without, of course, forming a densely intertwined overall structure. Suitable SRA's include a sulphonated product of a substantially linear ester oligomer formed from an oligomeric ester base structure of terephthaloyl and oxyalkylenoxy repeat units and sulfonated terminal portions derived from allyl covalently attached to the base structure, for example, as described in the EU patent 4,968,451, November 6, 1990 by J. J. Scheibel and E.P. Gosselink. Said ester oligomers can be prepared: (a) ethoxylating allyl alcohol; (b) by reacting the product of (a) with dimethyl terephthalate ("DMT") and 1,2-propylene glycol ("PG") in a two-step transesterification / oligomerization process; and (c) reacting the product of (b) with sodium metabisulfite in water. Other SRA's include polyesters of 1,2-propylene / polyoxyethylene terephthalate of non-ionic blocked ends of the U.S. patent. No. 4,711,730, December 8, 1987 to Gosselink et al, for example those produced by the transesterification / oligomerization of polyethylene glycol methyl ether, DMT, PG and polyethylene glycol ("PEG"). Other examples of SRA's include: the oligomeric esters of anionic blocked ends partially and completely of the U.S. patent. No. 4,721,580, Jan. 26, 1988 to Gosselink, such as oligomers of ethylene glycol ("EG"), PG, DMT and Na-3,6-dioxa-8-hydroxyoctansulfonate; the nonionic blocked block polyester oligomeric compounds of the U.S. patent. 4,702,857, from October 27, 1987 to Gosselink, for example produced from DMT, PEG and EG and / or PG (Me) -blocked methyl or a combination of DMT, EG and / or PG, PEG Me-blocked and Na-dimethyl-5-sulfoisophthalate; and the blocked terephthalate esters of the anionic ends, especially of sulfoaroyl of the U.S. patent. No. 4,877,896 of October 31, 1989 to Maldonado Gosselink and others, the latter being a typical SRA's useful in both fabric conditioning and laundry products, one example being an ester composition made from the monosodium salt of the acid m- sulfobenzoic, PG and DMT, optionally but preferably further comprising added PG, e.g., PEG 3400. SRA's also include: simple copolymer blocks of ethylene terephthalate or propylene terephthalate with polyethylene oxide terephthalate or polypropylene oxide, see the EU patent No. 3,959,230 to Hays of May 25, 1976 and the US patent. No. 3,893,929 to Basadur, July 8, 1975, cellulose derivatives such as the cellulosic hydroxyether polymers available as METHOCEL from Dow; the C1-C4 alkylcelluloses and C4 hydroxyalkylcells of the U.S. patent. No. 4,000,093, from December 28, 1976 to Nicol, et al., And methyl cellulosic esters having an average degree of substitution (methyl) per anhydroglucose unit of about 1.6 to about 2.3 and a solution viscosity of from about 80 to about 120 centipoises measured at 20 ° C as a 2% aqueous solution. Such materials are available as METOLOSE SM100 and METOLOSE SM200, which are the commercial brands of the methylcellulose ethers manufactured by Shin-etsu Kagaku Kogyo KK. Additional classes of SRA's include: (I) non-ionic terephthalates using diisocyanate coupling agents to link the polymeric ester structures, see E.U. 4,201,824, Violland et al. And E.U. 4,240,918 Lagasse et al., And (II) SRA's with carboxylate end groups made by adding trimethyl anhydride to known SRA's to convert terminal hydroxyl groups to trimethylate esters. With the proper selection of the catalyst, trimethyl anhydride forms bonds to the polymer terminals through a carboxylic acid ester isolated from the trimethyl anhydride instead of opening the anhydride linkage. You can use either non-ionic or anionic SRAs as starting materials, as long as they have hydroxyl end groups that can be esterified, see E.U. No. 4,525,524 Tung and others. Other classes include (III) non-anionic terephthalate-based SRAs of the urethane-linked variety, see E.U. 4,201,824, Violland and others; Other Optional Ingredients Other optional ingredients suitable for inclusion in the compositions of the invention include perfumes, colors and filler salts, with a preferred filler salt being sodium sulfate.

Detergent formulation with an almost neutral wash pH Although the detergent compositions of the present invention are operative within a wide range of wash pHs (e.g., from about 5 to about 12), they are particularly suitable when formulated to provide an almost neutral wash pH, ie, an initial pH of from about 7.0 to about 10.5 at a concentration of about 0.1 to about 2% by weight in water at 20 ° C. Formulations with an almost neutral wash pH are better for enzyme stability and to prevent stains from depositing. In such formulations, the wash pH is preferably from about 7.0 to about 10.5, most preferably from about 8.0 to about 10.5, more preferably from 8.0 to 9.0. Detergent formulations with an almost neutral wash pH are described in European patent application 83.200688.6, filed on May 16, 1983, J.H.M. Wertz and P.C.E Goffinet. Highly preferred compositions of this type also preferably contain from about 2 to about 10% by weight of citric acid and minor amounts (e.g., less than about 20% by weight) of neutralizing agents, pH regulating agents. , phase regulators, hydrotropes, enzymes, enzyme stabilizing agents, polyacids, foam regulators, opacifiers, antioxidants, bactericides, dyes, perfumes and brighteners, such as those described in the US patent 4,285,841 to Barrat et al., Issued August 25, 1981 (incorporated herein by reference).

Form of the compositions The detergent component of the invention can be manufactured by a variety of methods, including dry blending and agglomeration of the various compounds comprised in the detergent component. The detergent component preferably forms part of a detergent composition. The compositions according to the invention can have a variety of physical forms including the granulated forms, in tablets, flakes, bars and stick. The compositions are particularly so-called concentrated granular detergent compositions adapted to be added to a washing machine by means of a delivery device placed in the tub of the washing machine with the load of laundry. The compositions according to the present invention can also be used in, or in combination with bleaching additive compositions, comprising for example chlorine bleach. In general, the granular detergent compositions according to the present invention can be made by a variety of methods, including dry blending, spray drying, agglomeration and granulation. The quaternized clay soil removal / anti-redeposition agent according to the present invention can be added to the other detergent components by dry mixing, agglomeration (preferably combined with a carrier material) or as a spray-dried component. The average particle size of the components of the granulated compositions according to the invention, comprising the cationic compounds soluble in water removal / anti-redeposition of clay soils, should preferably be such that no more than 15% of the particles measure more 1.8 mm in diameter, and no more than 15% of the particles are less than 0.25 mm in diameter. Preferably, the average particle size is such that from 10% to 50% has a particle size of 0.2 mm to 0.7 mm in diameter. The term "average particle size" as defined herein is calculated by screening a sample of the composition in a number of fractions (typically 5 fractions) in a series of sieves., preferably Tyler sieves. The fractions of weight thus obtained are plotted against the opening size of the sieves. The average particle size is considered the size of the opening through which 50% by weight of the sample would pass. The overall density of the granular detergent compositions according to the present invention is typically an overall density of at least 400, preferably 600 g / liter, most preferably from 650 g / liter to 1200 g / liter. The overall density is measured by means of a simple funnel-cup device consisting of a conical funnel rigidly molded on a base and provided with a butterfly valve on its lower end to allow the contents of the funnel to be emptied into a cylindrical cup aligned axially below the funnel. The funnel is 130 mm high and has internal diameters of 130 mm and 40 mm in its respective upper and lower extremities. It is mounted in such a way that the lower extremity is 140 mm above the upper surface of the base. The cup has a total height of 90 mm, an internal height of 87 mm and an internal diameter of 84 mm. Its nominal volume is 500 ml. To carry out a measurement, the funnel is filled with manually poured dust, the butterfly valve is opened and the powder is allowed to overfill the cup. The full cup is removed from the frame and the excess powder is removed from the cup by passing a straight edge implement, eg, a knife, through its upper edge. The full cup is then weighed and the value obtained for the weight of the powder is doubled to provide a global density in g / liter. Equal measurements are made as required. The compacted solids can be manufactured using any suitable compaction process, such as rattling, agglomeration or extrusion, preferably tableting. Preferably, the tablets that will be used in dishwashing processes are manufactured using a normal rotary tapping press and using compression forces of 5 to 13 KN / cm2, most preferably 5 to 11 KN / cm2 for the solid The compacted material has a minimum hardness of 176N to 275N, preferably 195N to 245N, measured by a ClOO hardness test as provided by I. Holland instruments. This method can be used to prepare homogeneous or stratified tablets of any size or shape. Preferably, the tablets are symmetrical to ensure uniform dissolution of the tablet in the wash solution.

Laundry Washing Method The laundry washing methods of the present invention typically comprise treating the laundry with an aqueous washing solution in a washing machine having dissolved or supplied therein an effective amount of a laundry detergent composition in accordance with the present invention. with the invention For an effective amount of the detergent composition, it is tried to say from 10 to 3OOg of product dissolved or dispersed in a washing solution of a volume of 5 to 65 liters, which are typical doses of product and in volumes of washing solution commonly used in conventional laundry washing methods. The dosage depends on the particular conditions such as water hardness and degree of soiling of the laundry. In one aspect of use, a delivery device is employed in the washing method. The delivery device is loaded with the detergent product and used to introduce the product directly into the drum of the washing machine before starting the washing cycle. Its volume capacity must be such that it is capable of containing sufficient detergent product that would normally be used in the washing method.

The delivery device containing the detergent product is placed inside the drum before the start of the washing cycle, before, simultaneously with or after the washing machine has been loaded with clothes. At the beginning of the washing cycle of the washing machine, water is introduced into the drum and it rotates periodically. The design of the delivery device must be such as to allow the dry detergent product to be contained but then allow this product to be released during the wash cycle in response to its agitation when the drum is rotated and also as a result of its contact with the washing liquid. To allow the release of the detergent product during washing, the device may possess a number of openings through which the product can pass. Alternatively, the device may be made of a material that is liquid permeable but impermeable to the solid product, which will allow the dissolved product to be released. Preferably, the detergent product will be released rapidly at the start of the wash cycle, thereby providing transient localized concentrations of the product in the washing machine drum at this stage of the wash cycle. Preferred delivery devices are reusable and designed in such a way that the integrity of the container is maintained both in the dry state and during the wash cycle. Especially preferred delivery devices for use with the composition of the invention have been described in the following patents: GB-B-2, 157, 717, GB-B-2, 157, 718, EP-A-0201376, EP- A-0288345 and EP-A-0288346. An article by J. Bland, published in Manufacturing Chemist, November 19889, p. 41-46, also discloses especially preferred supply devices for use with granular laundry products, which are of a type commonly known as "granulette". Another preferred delivery device for use with the compositions of this invention is described in PCT patent application No. W094 / 11562. Essentially preferred delivery devices are described in European Patent Application Publication Nos. 0343069 and 0343070. This application describes a device comprising a flexible liner in the form of a pouch extending from a support ring defining a hole, the orifice being adapted to admit sufficient product into the bag for a washing cycle in a washing process. A portion of the washing medium flows through the orifice into the bag, dissolves the product and the solution then passes down through the orifice into the washing medium. The support ring is provided with a masking arrangement to prevent the exit of the moistened and undissolved product, this arrangement typically comprising radial walls extending from a protrusion in a spoke wheel configuration or similar structure., in which the walls have a helical shape. Alternatively, the delivery device may be a flexible container, such as a bag or bag. The bag may be made of a fibrous structure coated with a waterproof protective material to retain the contents, such as that described in published European patent application No. 0018678. Alternatively, it may be formed of a synthetic polymeric material insoluble in water provided with an edge seal or closure designed to break in the aqueous medium as described in published European patent applications Nos. 0011500, 0011501, 0011502 and 0011968. A convenient form of water-curable closure comprises a soluble adhesive in water disposed along and sealing an edge of a sack formed of a waterproof polymeric film such as polyethylene and polypropylene.

Packaging for the compositions Commercially sold executions of the bleaching compositions can be packaged in any suitable container including those constructed of paper, cardboard, plastics and any suitable laminates. A preferred packaging modality is described in European application No. 94921505.7.

Abbreviations used in the examples In the detergent compositions, the abbreviated component identifications have the following meanings: LAS: Linear Sodium alkylbenzenesulfonate of C? 2 TAS: Sodium alkyl sulfate CxyAS: Sodium alkyl sulfate of C? XC? And C46SAS: Alkylsulfate Sodium C14-C 5 secondary (2.3) CxyEzS: Sodium alkylsulfate of C] _x-Ciy condensed with z moles of ethylene oxide CxyEz: A predominantly linear primary alcohol of L-Lly condensed with an average of z moles of oxide of ethylene QAS: R2.N + (CH3) 2 (C2H4OH) with R2 = C12-C14 Soap: Linear sodium alkylcarboxylate derived from a mixture of 80/20 tallow and coconut oils CFAA: N-methylglucamide from (coconut) C alkyl? -C 4 TFAA: alkyl N-methylglucamide of C ^ g-C ^ g TPKFA: C2-C14 whole cut fatty acids STPP: Anhydrous sodium tripolyphosphate TSPP: Tetrasodium pyrophosphate Zeolite A: Hydrated sodium aluminosilicate of the formula ^ a12 (AIO2SÍO2) 12 • 27H2O, which has a primary particle size in the range of 0.1 to 10 microns.

Zeolite MAP: Zeolite MAP of hydrated sodium aluminosilicate having a silicon to aluminum ratio of 1.07 microns. NaSKS-6: Crystalline layered silicate of the formula Ü-Na2SÍ2? 5 Citric acid: Anhydrous citric acid Borate: Sodium borate Carbonate: Anhydrous sodium carbonate with an average particle size of 20Oμm and 90Oμm Bicarbonate: Anhydrous sodium bicarbonate with one Particle size distribution between 400μm and 1200μm Silicate: Amorphous sodium silicate (Si? 2 ratio: Na2? 2. 0) Sodium sulfate: Anhydrous sodium sulfate Citrate: Trisodium citrate dihydrate of 86.4% activity with a particle size distribution between 425μm and 850μm MA / AA: Copolymer of 1: 4 maleic acid / acrylic acid with a weight average molecular weight of approximately 70,000 AA: Sodium polyacrylate polymer with average molecular weight of 4,500 CMC: Sodium carboxymethylcellulose Cellulose ether: Methylcellulose ether with a degree of polymerization of 650 available from Shin Etsu Chemicals Protease: 4KNPU activity proteolytic enzyme / g sold under the trade name Savinase by Novo Industries A / S Alcalase: Proteolytic enzyme activity 3AU / g sold by Novo Industries A / S Cellulase: Activity cellulite enzyme lOOOCEVU / g sold by Novo Industries A / S under the trade name Carezyme Amylase: Activity amyolitic enzyme 120 KNU / g sold by Novo Industries A / S under the trade name Termamyl 12OT Lipase: Lipolytic activity enzyme lOOkLU / g sold by Novo Industries A / S under the trade name Lipolase Endolase Endoglumone enzyme activity 3000CEVU / g sold by Novo Industries A / S PB4 Sodium perborate anhydrous tetrahydrate of nominal formula NaB02.3H2O.H202 PB1: Anhydrous sodium perborate bleach monohydrate of nominal formula NaB02.H202 Percarbonate: Sodium percarbonate of nominal formula 2Na2C? 3.3H2? 2 NOBS: Nonanoyloxybenzenesulfonate in the form of sodium salt TAED: Tetraacetylethylenediamine Mn catalyst: MnIV2 (m-O) 3 (1, 4, 7-trimethyl-1, 4, 7-triazacyclononane) 2 (PF6) 2, as described in the US patents. Nos. 5,246,621 and 5,244,594. DTPA: Diethylenetriaminepentaacetic acid DTPMP: Diethylenetriaminpenta (methylenephosphonate), marketed by Monsanto under the trade name Dequest 2060. Photoactivated bleach: Sulfonated zinc phthalocyanine encapsulated in dextrin-soluble polymer 1: 4, 4'-bis (2-sulphotrisyl) biphenyl disodium brightener Brightener 2: 4,4'-bis (4-anilino-6-morpholino-1,3,5-triazin-2-yl) amino) stilbene-2: 2'-disulfonate disulfonate HEDP: 1, 1-hydroxyethanediphosphonic acid EDDS: Ethylenediamine-N, N-disuccinic acid QEA 1: bis ((C2H50) (C2H4On) (CH3) -N + -CgH12-N + - (CH3) bis ((C H50) - ( C2H4? N), where n = from 20 to 30 QEA 2: bis ((C2H50) (C2H4On) (CH3) N + R1, where Rx is an alkyl group of C4-C12 and n = from 20 to 30 QEA 3: tri. {(Bis ((C2H50) - (C2H4? N) (CH3) -N +) -CONC3H6).}. -C3H O, where n = from 20 to 26 PEGX: Polyethylene glycol with a molecular weight of x PEO: Polyethylene oxide with a molecular weight of 50,000 TEPAE : Ethoxylated tetraethylenepentamine PVP: Polyvinylpyrrolidone polymer PVNO: Polyvinylpyridine N-oxide PVPVI: Copolymer of polyvinylpyrrolidone and vinylimidazole SRP 1: Esters of end blocked with sulfobenzoyl with base structure of oxyethyleneoxy and terephthaloyl SRP 2: Polymer short block polymer (1) , 2-propylene terephthalate) diethoxylated Silicon Anti-Foams: Polydimethylsiloxane foam controller with a siloxane-oxyalkylene copolymer as a dispersing agent with a ratio of said foam controller to said dispersing agent from 10: 1 to 100: 1. Paraffin Wax In the following examples, all levels are quoted as% by weight of the composition: EXAMPLE 1 The following high density granular laundry detergent compositions for laundry A to F of particular utility were prepared under European automatic washing conditions according to the invention: B LAS 8.0 8.0 8.0 8.0 8.0 8.0 C25E3 3.4 3.4 3.4 3.4 3.4 3.4 C46AS 1.0 2.0 2.5 3.0 4.0 C68AS 3.0 2.0 5.0 7.0 1.0 0.5 QAS 0.8 0.8 Zeolite A 18.1 18.1 16.1 18.1 18.1 18.1 Zeolite MAP 4.0 3.5 Carbonate 13.0 13.0 13.0 27.0 27.0 27.0 Silicate 1.4 1.4 1.4 3.0 3.0 3.0 Sodium sulfate 26.1 26.1 26.1 26.1 26.1 26.1 MA / AA 0.3 0.3 0.3 0.3 0.3 0.3 CMC 0.2 0.2 0.2 0.2 0.2 0.2 PB4 9.0 9.0 9.0 9.0 9.0 9.0 TAED 1.5 1.5 1.0 1.5 1.5 Catalyst of Mn 0.03 0.07 _ _ _ DETPMP 0.25 0.25 0.25 0.25 0.25 0.25 HEDP 0.3 0.3 0.2 0.2 0.3 0.3 B D EDDS 0.4 0.2 QEA 1 1.0 0.8 0.7 1.2 0.5 QEA 2 1.0 0.5 Proteas 0.26 0.26 0.26 0.26 0.26 0.26 Amylase 0.1 0.1 0.4 0.3 0.1 0.1 Cellulase 0.3 0.3 0.8 0.4 1.0 2.0 Bleach 15 15 15 15 15 15 photoactivated ppm) ppm ppm ppm ppm ppm ppm Polisher 1 0.09 0.09 0.09 0.09 0.09 0.09 Perfume 0.3 0.3 0.3 0.3 0.3 0.3 Silicone antifoams 0.5 0.5 0.5 0.5 0.5 0.5 Misc / comp minors up to 100% Density in g / l 850 850 850 850 850 850 850 EXAMPLE 2 The following granular laundry detergent compositions G-I were prepared of particular utility under European automatic washing conditions, according to the invention: H I LAS 5.25 5.61 4.76 TAS 1.25 1.86 1.57 C45AS 2.24 3.89 C25E3S 0.76 1.18 C45E7 3.25 _ 5.0 C25E3 5.5 QAS 0.8 2.0 2.0 STPP 19.7 ZZeeoolliittaa AA - 19.5 19.5 Zeolite MAP 2.0 NaSKS -6 / citric acid (79:21) 10.6 10.6 Carbonate 6.1 21.4 21.4 Bicarbonate 2.0 2.0 Silicate 6.8 - - Sodium sulphate 39.8 - 14.3 MA / AA 0.8 1.6 1.6 CMC 0.2 0.4 0.4 PB4 5.0 12.7 __ G H I Percarbonate 5.0 - 12.7 TAED 0.5 3.1 Catalyst of Mn 0.04 DTPMP 0.25 0.2 0.2 HEDP - 0.3 0.3 QEA 1 0.9 1.2 QEA 2 1. u Protease 0.26 0.85 0.85 Lipase 0.15 0.15 0.15 Cellulase 0.28 0.5 0.7 Amylase 0.4 0.1 0.1 PVP 0.9 1.3 0.8 B1activated photoanalyzer (ppm) 15 ppm 27 ppm 27 ppm Polisher 1 0.08 0.19 0.19 Rinse aid 2 - 0.04 0.04 Perfume 0.3 0.3 0.3 Silicone antifoams 0.5 2.4 2.4 Comp. minor / mise, at 100% EXAMPLE 3 The following detergent formulations of particular utility were prepared under European conditions of automatic washing, according to the invention.

K M Blown powder LAS 6.0 5.0 11.0 6.0 TAS 2.0 2.0 Zeolite A 27.0 20.0 STPP 24.0 24.0 Sulphate 9.0 6.0 13.0 - MA / AA 2.0 4.0 6.0 4.0 Silicate 7.0 3.0 3.0 3.0 CMC 1.0 1.0 0.5 0.6 QEA 1 0.8 1.0 1.4 0.5 QEA 2 - - - 0.5 Brightener 0.2 0.2 0.2 0.2 Silicone antifoams 1.0 1.0 1.0 0.3 DTPMP 0.4 0.4 0.2 0.4 Spray C45E7 - - - 5.0 C45E2 2.5 2.5 2.0 C45E3 2.6 2.5 2.0 Perfume 0.3 0.3 0.3 0.2 Silicone antifoams 0.3 0.3 0.3 Dry additives Sulfate 3.0 3.0 5.0 10.0 Carbonate 6.0 13.0 15.0 14.0 PB1 - - - 1.5 PB4 18.0 18.0 10.0 18.5 TAED 3.0 2.0 - 2.0 EDDS - 2.0 2.4 - Proteasa 1.0 1.0 1.0 1.0 Lipase 0.4 0.4 0.4 0.2 Amylase 0.2 0.2 0.2 0.4 Cellulase 0.2 0.5 0.7 0.1 Bleach photo activated - - - 0.15 Total 100.0 100.0 100.0 100.0 EXAMPLE 4 The following granular detergent formulations were prepared according to the invention. The formulation N is particularly suitable for use under Japanese automatic washing conditions. Formulations O to S are particularly suitable for use under US automatic washing conditions.

N 0 P Q R S Blown powder LAS 22.0 5.0 4.0 9.0 8.0 7.0 C45AS 7.0 7.0 6.0 C46AS - 4.0 3.0 C45E35 - 3.0 2.0 8.0 5.0 4.0 Zeolite A 6.0 16.0 14.0 19.0 16.0 14.0 MA / AA 6.0 3.0 3.0 AA 3.0 3.0 2.0 3.0 3.0 Sodium sulphate 7.0 18.3 11.3 24.0 19.3 19.3 Silicato 5.0 1.0 1.0 2.0 1.0 1.0 Carbonate 28.3 9.0 7.0 25.7 8.0 6.0 QEA 1 0.9 0.9 _ _ 0.5 1.1 QEA 2 - - 0.8 1.0 QEA 3 - - 0.4 - PEG 4000 0.5 1.5 1.5 1.0 1.5 1.0 Sodium Oleate 2.0 DTPA 0.4 - 0.5 - - 0.5 Rinse aid 0.2 0.3 0.3 0.3 0.3 0.3 Spray C45E9 1.0 C45E7 - 2.0 2.0 0.5 2.0 2.0 Perfume 1.0 0.3 0.3 1.0 0.3 0.3 Agglomerates C45AS - 5.0 5.0 - 5.0 5.0 LAS - 2.0 2.0 - 2.0 2.0 Zeolite A - 7.5 7.5 - 7.5 7.5 HEDP - 1.0 - - 2.0 Carbonate - 4.0 4.0 - 4.0 4.0 PEG 4000 - 0.5 0.5 - 0.5 0.5 Mise. (water, etc - 2.0 2.0 - 2.0 2.0 Dry Additives NAC OBS 1.0 2.0 3.0 1.0 3.0 2.0 PB4 - 1.0 4.0 - 5.0 0.5 PB1 6.0 Percarbonate 5.0 12.5 Carbonate 5.3 1.8 4.0 4.0 NOBS 4.5 6.0 0.6 Cumenesulfonic acid 2.0 2.0 2.0 2.0 Lipasa 0.4 0.4 0.4 0.4 0.4 Cellulase 0.1 1.8 1.2 0.3 0.2 0.2 Amylase 0.1 0.3 0.3 Protease 1.0 0.5 0.5 0.5 0.5 0.5 PVPVI 0.5 0.5 PVP 0.5 0.5 0.5 PVNO 0.5 0.5 SRP1 0.5 0.5 Silicone antifoams 0.2 0.2 0.2 0.2 Total 100.0 100.0 100.0 100.0 100.0 100.0 EXAMPLE 5 The following granular detergent formulations were prepared according to the invention. Formulations W and X are particularly suitable for use under US automatic washing conditions. And it is of particular utility under Japanese conditions of automatic washing.

UV Powder blown Zeolite A 30.0 22.0 6.0 Sodium sulphate 19.0 5.0 7.0 MA / AA 3.0 2.0 6.0 LAS 14.0 12.0 22.0 C45AS 8.0 7.0 7.0 'Silicate 1.0 5.0 Soap 2.0 Brightener 1 0.2 0.2 0.2 QEA 1 0.6 2.0 1.0 Carbonate 8.0 16.0 20.0 DTPMP 0.4 0.4 Spray 1.0 5.0 C45E7 1.0 1.0 1.0 Dry additives HEDP 1.0 - - PVPVI / PVNO 0.5 0.5 0.5 Protease 1.0 1.0 1.0 Lipase 0.4 0.4 0.4 Amylase 0.1 0.1 0.1 Cellulase 0.1 0.1 0.1 TAED - 6.1 4.5 PB1 1.0 5.0 6.0 Sodium sulfate - 6.0 _ Balance (humidity and miscellaneous) EXAMPLE 6 The following granular detergent compositions of particular utility were prepared under European washing conditions, according to the invention.

W X Powder blown Zeolite A 20.0 STPP 20.0 LAS 6.0 6.0 C68AS 2.0 2.0 Silicate 3.0 8.0 MA / AA 4.0 2.0 CMC 0.6 0.6 QEA 1 0.9 0.6 QEA 3 0.1 Brightener 0.2 0.2 DTPMP 0.4 0.4 Spray C45E7 5.0 5.0 Silicone antifoams 0.3 0.3 Perfume 0.2 0.2 Carbonate Dry Additives 14.0 9.0 PBl 1.5 2.0 PB4 18.5 13.0 TAED 2.0 2.0 Photoactivated bleach 5 ppm 15 ppm Protease 1.0 1.0 Lipase 0.2 0.2 Amylase 0.4 0.4 Cellulase 1.5 0.6 Sulfate 10.0 20.0 Balance (humidity and mise.) Density (g / liter) 700 700 EXAMPLE 7 The following detergent compositions were prepared according to the present invention: AA Blown powder Zeolite A .5.0 15.0 15.0 Sodium sulphate 0.0 5.0 0.0 LAS 3.0 3.0 3.0 QAS - 1.5 1.5 DTPMP 0.4 0.2 0.4 CMC 0.4 0.4 0.4 MA / AA 4.0 2.0 2.0 Agglomerates LAS 5.0 5.0 5.0 TAS 2.0 2.0 1.0 Silicate 3.0 3.0 0.4 QEA 1 1.0 2.5 0.6 Mn catalyst 0.03 - - Zeolite A 8.0 8.0 8.0 Carbonate 8.0 8.0 4.0 Spray 0.3 0.3 0.3 C45E7 2.0 2.0 2.0 C25E3 2.0 Dry additives 10 Citrate 5.0 2.0 Bicarbonate 3.0 Carbonate 8.0 15.0 10.0 Percarbonate 7.0 10.0 TAED 6.0 2.0 5.0 PBl 14.0 7.0 10.0 EDDS 2.0 Polyethylene-25 oxide of PM 5,000,000 0.2 Bentonite Clay 10.0 Protease 1.0 1.0 1.0 '30 Lipasa 0.4 0.4 0.4 Amylase 0.6 0.6 0.6 Cellulasa 0.6 1.8 1.5 Silicone antifoams 5.0 5.0 5.0 40 Dry additives Sodium sulfate 0.0 3.0 0.0 45 Balance (humidity and mise.) At 100% 100. 0 100 0 100 0 Density (g / liter) 850 850 850 EXAMPLE 8 The following detergent formulations were prepared according to the present invention: BB CC DD EE LAS 20.0 14.0 24.0 22.0 QAS 0.7 1.0 0.7 TFAA 1.0 C25E5 / C45E7 2.0 0.5 C45E3S 2.5 STPP 30.0 18.0 30.0 22.0 Silicate 9.0 5.0 10.0 8.0 Carbonate 13.0 7.5 5.0 Bicarbonate 7.5 Percarbonate 5.0 9.0 15.0 DTPMP 0.7 1.0 QEA 1 0.4 1.2 0.5 2.0 QEA 2 0.4 SRP 1 0.3 0.2 0.1 MA / AA 2.0 1.5 2.0 1.0 CMC 0.8 0.4 0.4 0.2 Protease 0.8 1.0 0.5 0.5 Amylase 0.8 0.4 0.25 Lipase 0.2 0.1 0.2 0.1 Cellulase 0.15 0.05 0.4 0.2 Activated photo bleach (ppm) 70 p 10 ppm Rinse aid 1 0.08 0.2 PBl 6.0 2.0 HEDP 2.3 TAED 2.0 1.0 Balance (humidity and mise.) EXAMPLE 9 The following bar laundry detergent compositions are examples of the present invention.

FF GG HH II JJ KK LL MM LAS 19.0 15.0 21.0 6.75 8.8 C C7788AASS 3 300..00 1 133..55 15.75 11.2 22.5 Sodium Laurate 2.5 9.0 Zeo_ lita A 2.0 1.25 - 1.25 1.25 1.25 Carbonate 20.0 3.0 13.0 8.0 10.0 15.0 15.0 10.0 Calcium Carbonate 21.5 - Sulphate 5.0 - TSPP 5.0 - 5.0 - 5.0 5.0 2.5 5.0 STPP 5.0 15.0 5.0 8.0 10.0 Bentonite Clay - 10.0 - 5.0 DTPMP - 0.7 0.6 0.6 0.7 0.7 0.7 MA / AA 0.4 1.0 _ 0.2 0.4 0.5 0.4 SRP1 0.3 0.3 0.3 0.3 0.3 0.3 0.3 0.3 'roteasa - 0.12 - 0.08 0.08 0.1 Lipase 0.1 - 0.1 - Amylase - 0.8 - - 0.1 Cellulase 05 0.15 0.2 0.3 0.15 1.5 1.0 PEO 0.2 - 0.2 0.3 0.3 Perfume 1 .6 _ _ _ _

Claims (20)

NOVELTY OF THE INVENTION CLAIMS

1. - A granular detergent composition or component thereof, comprising: (a) a cellulolytic enzyme; and (b) a water-soluble cationic compound having removal / anti-redeposition properties of clay soils, which is selected from the group consisting of: 1) ethoxylated cationic monoamines having the formula: R2 R2-N + - L -X R2 2) ethoxylated cationic diamines having the formula: (R3) d R3 (R3) d R3 X- L-M3- R1- N + -L-X or R3-M1-R1 -N + -R or / / i I i LLLLL 1 III i XXXXX where M ^ is a group N + or N; each M2 is a group N + or N and at least one M2 is a group N +; 3) ethoxylated cationic polyamines having the formula: 4) mixtures thereof; 0 0 0 0 0 II II II II II where A1 is NC, NCO, NCN, CON, OCN, I I I I I R R R R R 0 0 0 0 0 II II II II II

CO, OCO, OC, CNC 0 R and R is H or C1-C4 alkyl or hydroxyalkyl, R ^ is alkylene, hydroxyalkylene, alkenylene, arylene or C2-C2 alkarylene, or an oxyalkylene portion of C2-C3 it has from 2 to approximately 20 oxyalkylene units, as long as NO bonds are not formed; each R2 is alkyl or hydroxyalkyl of C-C4, the -LX portion, or two R2 together form the portion - (CH) r-A2- (CH2) s-, where A2 is -O- or -CH2-, r is l or 2, s is l or 2 and r + s is 3 or 4; each R3 is alkyl or hydroxyalkyl of C-Cg, benzyl, the L-X portion, or two R3 or one R and one R3 together form the - (CH2) r-A2- (CH) s- portion; R 4 is a substituted C 3 -C 2 alkyl, hydroxyalkyl, alkenyl, aryl or alkaryl group having substitution sites p; R 5 is alkenyl, hydroxyalkylene, alkenylene, arylene or C 1 -C 2 alkarylene, or a C 2 -C 3 oxyalkylene portion having from 2 to about 20 oxyalkylene units, provided no 0-0 or O-N bonds are formed; X is a nonionic group selected from the group consisting of H, C1-C4 alkyl or hydroxyalkyl ester or ester groups and mixtures thereof; L is a hydrophilic chain containing the polyoxyalkylene moiety - [(R60) m (CH2CH0) n] -; wherein Rs is C3-C4 alkylene or hydroxyalkylene and m and n are numbers such that the - (CH2CH20) n] - portion comprises at least about 50% is weight of said polyoxyalkylene portion; d is 1 when M2 is N + and is 0 when M2 is N; n is at least about 16 for said cationic monoamines, is at least about 6 for said cationic diamines and is at least about 3 for said cationic polyamines; p is from 3 to 8; q is 1 or 0; t is 1 or 0, as long as t is 1 when q is 1; and wherein the ratio of compound (a) to (b) is from 1: 100 to 100: 1. 2. - A granular detergent composition or component thereof according to claim 1, further characterized in that said ratio is from 1:10 to 10: 1.

3. - A granular detergent composition according to claim 1, further characterized in that said cationic compound is present at a level of 0.01% to 30% by weight of the detergent composition.

4. - A granular detergent composition according to claim 1, further characterized in that the cationic compound is present at a level of 0.2% to 3% by weight of the detergent composition.

5. - A granular detergent composition or component thereof according to claim 1, further characterized in that said cationic compound is an ethoxylated cationic monoamine and is further characterized in that one R2 is methyl, two R2 are the LX portion, m is 0 and n is at least about 20.

6. A granular detergent composition or component thereof in accordance with the claim 1, characterized in that the cationic compound is an ethoxylated cationic diamine and is also characterized in that R1 is an alkylene of C2-Cg.

7. A granular detergent composition or component thereof according to claim 6, further characterized in that said ethoxylated cationic diamine is further characterized in that R1 is hexamethylene.

8. - A detergent composition or component thereof according to claim 1, further characterized in that the cationic compound is an ethoxylated cationic polyamine and is further characterized in that R4 is an alkyl, hydroxyalkyl or C3-Cg aryl group substituted; Al is O C r H and p is 3 to 6.

9. A granular detergent composition or component thereof in accordance with the claim 6, further characterized in that the cationic compound is further characterized in that each R2 is methyl or the -L-X portion, each R3 is methyl and M3-, and each M2 is a N + group.

10. A granular detergent composition or component thereof according to claim 6, further characterized in that m is 0 and n is at least 12.

11. A granular detergent composition or component thereof according to claim 6. , further characterized in that m is 0 and n is at least 20.

12. - A granular detergent composition according to claim 1, further characterized in that said cellulolytic enzyme is present at a level of 0.01% to 5% by weight of the composition .

13. - A granular detergent composition according to claim 1, further characterized in that said cellulolytic enzyme is present at a level of 0.5% to 3% by weight of the composition.

14. - A granular detergent composition or component thereof according to claim 1, further characterized in that a cationic polymer of removal / anti-redeposition of clay succes is present which is further characterized by having a base structure, at least 2 groups M and at least one group L-X, wherein M is a cationic group attached or integral with the base structure and contains a positively charged N + center; and L connects groups M and X or connects group X to the base structure of the polymer; X is a nonionic group selected from the group consisting of H, C1-C4 alkyl or hydroxyalkyl ester or ester groups and mixtures thereof; and L is a hydrophilic chain containing the polyoxyalkylene moiety - [(R60) m (CH2CH2O) n] -.

15. - A granular detergent composition or component thereof according to claim 14, further characterized in that said cationic compound is an ethoxylated cationic polymer having a base structure, selected from the group consisting of polyurethanes, polyesters, polyethers , polyimides, polyalkyleneimines and mixtures thereof.

16. A granular detergent composition according to claim 1, further characterized in that the composition is formulated in such a way as to provide a wash pH of 8.0 to 10.5.

17. A granular detergent composition according to claim 1, further characterized in that a heavy metal ion sequestrant is present at a level of 0.1% to 10% by weight of the detergent composition.

18. - A granular detergent composition or component thereof according to claim 1, further characterized in that an organic peroxyacid bleach system is present, which contains a source of hydrogen peroxide and an organic peroxyacid precursor compound.

19. A granular detergent composition or component thereof according to claim 1, further characterized in that a surfactant agent selected from the group consisting of anionic, nonionic, cationic, ampholytic, amphoteric and zwitterionic surfactants is present, and mixtures thereof.

20. A method of laundry washing in a domestic washing machine 15, further characterized by introducing an effective amount of a granular detergent composition according to claim 1 into the tub of the washing machine, preferably before the start of washing, by the use of a delivery device that allows the progressive release of said granulated detergent composition in the washing solution during washing.