MXPA99002760A - Detergent compositions - Google Patents

Abstract

The present invention relates to granular detergent compositions or components thereof, which comprise a hydrophobic organic peroxyacid bleaching system, capable of providing a hydrophobic organic peroxyacid compound and one or more cationic compounds, which are cationic, (partially) quaternized ethoxylated (poly) amine compounds with clay-soil removal/anti-redeposition properties, for use in laundry and dish washing processes. Preferably, also a non-hydrophobic bleach system is present.

Description

DETERGENT COMPOSITIONS TECHNICAL FIELD The present invention relates to compositions or components thereof containing cationic compounds with removal / antiredeposition properties of particulate clay soil and a hydrophobic organic peroxyacid bleach system for use in laundry and dishwashing processes.

BACKGROUND OF THE INVENTION A particularly important property of a detergent composition is its ability to remove particulate-like dirt from a variety of fabrics during washing. Perhaps the most important type of dirty particles is clay-like dirt. The clayey dirt particles generally contain negatively charged aluminosilicate residues, and positively charged cations (eg, calcium) which are positioned between and bound together with the negatively charged deposits. A variety of models can be proposed for compounds that would have clay grime removal properties. A model requires that the compound have two distinct characteristics. The first is the ability of the compound to adsorb in the negatively charged deposits of the clay particle; and the compound's ability, once adsorbed, to remove (distend) the negatively charged deposits so that the clay particle loses its cohesive force and can be eliminated in the wash water. In addition to the removal of clay soil, it is necessary to keep the dirt removed during the laundry cycle (or dishwashing). The dirt that is removed from the fabric and suspended in the wash water can be redeposited on the surface of the fabric. This redeposited grime causes an effect of percudido or "graying" that is especially noticeable in the white fabrics. To minimize the problem, anti-redeposition agents may be included in the detergent composition. For example, EP-B-111 965 discusses the use of cationic compounds in detergents, which have both clay loosening properties and anti-redeposition properties. US 4,659,802 and 4,664,848 disclose the quaternized amines which have clay removal and anti-redeposition properties and which can be used in combination with anionic surfactants. A proposed model for anti-redeposition action of 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 clay particles the dispersion properties of the molecule. While more and more of these compounds are adsorbed on the suspended particles of clayey dirt, the latter are encased in a hydrophilic layer provided by the ethoxy units.

Attached Thus, the hydrophilically enclosed dirt is prevented from being redeposited on hydrophobic fabrics, such as polyester, during the laundry or dishwashing cycle. Another component traditionally used in detergents is bleach, to remove blemishes or grime from the fabric. A disadvantage of the use of most bleaches is that several other detergent components are sensitive to bleach and can be oxidized by bleach, so their original properties can be diminished. Thus, not all detergent components are compatible with bleaches. Applicants have found that ethoxylated (partially) quaternized cationic poly (poly) amines having clay loam removal / anti-rejection properties are fully compatible with the bleaches formulated therewith. It has also been found that the use in bleach detergent compositions (or components thereof) of bleach (oxygen release) in combination with fully quatemized ethoxylated (poly) amines provides a greater improvement in cleaning or maintenance of whiteness than the use of bleach ( oxygen release) in combination with partially quaternized ethoxylated (poly) amines. However, even partially quaternized (poly) ethoxylated amines provide an improvement in cleaning or maintenance of whiteness in combination with the bleach.

Without wishing to be caught by theory, the bleach compatibility of the quaternized cationic ethoxylated (poly) amines can be explained as follows. It is believed that the quaternization of the nitrogen groups of these molecules has a dual purpose. It provides a cationic charge on the molecule, improving the adsorption on the clay particles or on the surface of the fabric or dispersed in the washing water, and eliminates the oxidizable solitary pair of the nitrogen groups of the attack of bleaching species, in this way makes the stable molecule in laundry detergents that contains bleach. Bleaching systems based on hydrophobic peroxyacids are newly developed bleaching species. It has been found that a problem with hydrophobic bleaches is that despite their tendency to migrate to stains or grime from the surface of the fabric, they do not necessarily interact fully with them. It has been found that hydrophobic bleaches can be prevented from migrating to whitish hydrophobic stains / grime by clay grime particles deposited on the fabric. Consequently, its whitening performance can be decreased. This results in a decrease in the cleaning performance of bleachable / percured dirt of the hydrophobic bleach. It has also been found that the removal of blemishes or grime on negatively charged fabric (such as high pH cloth, cotton cloth or cloth surfaces containing negatively charged particles / compounds, as anionic surfactants) by bleaching agents Hydrophobic is not always satisfactory. This is thought to be due to a decreased tendency of negatively charged bleaches to migrate to negatively charged cloth surfaces. It has also been found that the removal of certain bleachable hydrophilic stains (such as beverage stains) by hydrophobic bleach is not always satisfactory, which is believed to be due to the limited interaction between the hydrophilic stains and the hydrophobic bleach. Applicants have found that these problems can be alleviated by the inclusion of one or more compounds that have clay grime removal / antiredeposition properties (as mentioned above) in a detergent composition containing a hydrophobic bleach. It has been found that in detergent compositions containing both components the bleaching efficacy of the organic peroxyacid hydrophobic bleach system is broadened. Moreover, it has been found that bleaching efficacy can also or will be further enhanced by the inclusion of non-hydrophobic bleach in the bleaching system. In both situations, the total cleaning performance of the detergent is improved. First, it is believed that the interaction between the cationic compound and the anionic, hydrophobic (and also non-hydrophobic) bleach facilitates the migration and / or interaction of the bleach to a negative surface. Second, the interaction between the cationic compound and the bleach (hydrophobic) makes the bleach much more hydrophobic, thus facilitating the migration or interaction of the bleach with the hydrophilic, whitish dirt. All documents cited in the present description are, in part relevant, incorporated herein by reference.

BRIEF DESCRIPTION OF THE INVENTION The present invention relates to granular detergent compositions or components thereof, which contain an organic hydrophobic peroxyacid bleach system, capable of providing a hydrophilic organic peroxyacid compound and one or more cationic compounds, which are cationic (poly) amines compounds ethoxylated, (partially) quaternized with removal / antiredeposition properties of particulate clay soil. In more detail, the present invention relates to granular detergent compositions or components thereof, which comprise (a) an organic hydrophobic peroxy acid bleach system, capable of providing a peroxyacid compound; and (b) a water soluble cationic compound having removal properties / antiredeposition of clayey soil, which is selected from the group consisting of: 1) ethoxylated cationic monoamines having the formula: R2 R2 N + X R2 2) ethoxylated cationic diamines having the formula: wherein M1 is a group N + or N; each M2 is a group N + or N, and M2 is a group N +; 3) ethoxylated cationic polyamines having the formula: 4) mixtures thereof; where A1 is R is H or alkyl or hydroxyalkyl of 1 to 4 carbon atoms, R1 is alkylene of 2 to 12 carbon atoms, hydroxyalkylene, alkenylene, arylene or alkarylene, or an oxyalkylene portion of 2 to 3 carbon atoms of 2 to about 20 oxyalkylene units, provided that NO bonds are not formed; each R2 is alkyl or hydroxyalkyl of 1 to 4 carbon atoms, the -LX portion, or two R2 together form the portion - (CH2) r-A2- (CH2) s-, where A2 is -O- or -CH2 -, r is 1 or 2, s is 1 or 2 and r + s is 3 or 4; each R3 is alkyl or hydroxyalkyl of 1 to 8 carbon atoms, benzyl, the L-X portion, or two R3 or an R2 and R3 together form the - (CH2) r-A2- (CH2) s- portion; R 4 is an alkyl, hydroxyalkyl, alkenyl, aryl or substituted alkaryl group of 3 to 12 carbon atoms having p substitution sites; R5 is alkenyl, hydroxyalkylene, alkenylene, arylene or alkarylene of 1 to 12 carbon atoms, or an oxyalkylene portion of 2 to 3 carbon atoms having from 2 to about 20 oxyalkylene units provided no bond is formed OO or ON; X is a non-ionic group selected from the group consisting of H, alkyl groups of 1 to 4 carbon atoms, hydroxyalkyl ester or ether, and mixtures thereof; L is a hydrophilic chain containing the polyoxyalkylene moiety - [(R60) m (CH2CH2?) N] -; wherein R6 is alkylene or hydroxyalkylene of 3 to 4 carbon atoms and m and n are numbers such that the - (CH2CH2?) n- portion comprises at least about 50% by weight of said polyoxyalkylene portion; d is 1 when M2 is N + and 0 when M2 is N; n is at least about 16 for the said cationic monoamines, is at least about 6 for the said cationic diamines and is at least about 3 for the said cationic polyamines; p is from 3 to 8; q is 1 or 9; t is 1 or 0, provided that t is 1 when q is 1. In a preferred aspect said organic hydrophobic peroxy acid bleach system comprises (1) a source of hydrogen peroxide and (ii) a hydrophobic peroxy acid organic bleach precursor compound. In another preferred embodiment a non-hydrophobic bleaching system is present which preferably comprises: (i) a source of hydrogen peroxide; and (ii) a non-hydrophobic bleach precursor compound.

DETAILED DESCRIPTION OF THE INVENTION An essential feature of the present invention is a water-soluble cationic compound having removal / antiredeposition properties of particulate clay loam and which is selected from the group consisting of mono-di and cationic polyamines.

In detergent compositions, the water-soluble cationic compound is preferably present at a level of from 0.01% to 30%, more preferably from 0.1% to 15%, much more preferably from 0.2% to 3.0% by weight of the detergent composition. The proportion of hydrophobic organic peroxyacid compound (provided by the hydrophobic organic peroxyacid bleach) to water-soluble cationic compound preferably is from 20: 1 to 1: 2, more preferably from : 1 to 1: 1, much more preferable from 7: 1 to 1: 1.

CATIÓNIC AMINAS The water-soluble cationic compounds of the present invention useful in the granular detergent compositions or components according to the present invention include ethoxylated cationic monoamines, ethoxylated cationic diamines and ethoxylated cationic polyamines as previously defined. In the preceding formulas for cationic amines, R1 can be branched cyclic (for example ()). or much more preferably (for example - CH2CH2-, - CH2CH2CH2-) Alkylene, hydroxyalkylene, alkenylene, alkarylene or linear oxyalkylene R1 preferably is alkylene of 2 to 6 carbon atoms for the ethoxylated cationic diamines. Each R2 is preferably methyl of the portion -L-X; each R3 preferably is alkyl or hydroxyalkyl of 1 to 4 carbon atoms, and much more preferably methyl. The positive charge of the N + groups is compensated by the appropriate number of opposite anions. Suitable counter anions include Cl-, Br-, SO3"2, PO4" 2, MeOSO3- and the like, particularly preferred counterions are Cl- and Br-. X can be a nonionic group selected from hydrogen (H), alkyl of 1 to 4 carbon atoms or hydroxyalkyl ester or ether groups, or mixtures thereof. The preferred esters or ethers are the acetate ester and the methyl ether, respectively. Particularly preferred nonionic groups are H and methyl ether.

In the preceding formulas, the hydrophilic chain L usually consists entirely of the polyoxyalkylene portion - [(R60) m (CH2CH2-On) -]. The - (R6O) m- and - (CH2CH2O) n- portions of the polyoxyalkylene portion can be mixed together or preferably in blocks of - (R6O) m - and portions - (CH2CH2O) n -R6 preferably is C3H6 (propylene); m is preferably from 0 to about 5 and is much more preferably 0, ie, the polyoxyalkylene portion consists entirely of the - (CH2CH2O) n- portion. The - (CH 2 CH 2 O) n - portion preferably comprises at least about 85% by weight of the polyoxyalkylene portion and much more preferably 100% by weight (m is O). In the preceding formulas, M1 and each M2 are preferably a N + group for the cationic diamines and polyamines. Preferred ethoxylated cationic monoamines and diamines have the formula: wherein X and n are defined above, a is from 0 to 20, preferably from 0 to 4 (for example 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 range from about 20 up to about . For the preferred cationic diamines (b = 1), n is at least about 12 with a typical range of about 12 to 42. In the preceding formula for the ethoxylated cationic polyamines, R 4 (linear, branched or cyclic) is preferably a alkyl group substituted by 3 to 6 carbon atoms, hydroxyalkyl or aryl; Al is preferably O -CN-; H n is preferably at least about 12, with a typical range of about 12 to 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 alkylene of 2 to 3 carbon atoms. When R4 is a substituted alkyl, hydroxyalkyl or alkenyl group, and when q is 0, R5 is preferably an oxyalkylene portion of 2 to 3 carbon atoms; when q is 1, R5 is preferably alkylene of 2 to 3 carbon atoms. These ethoxylated cationic polyamines can be derived from polyamine amides such as: These ethoxylated cationic polyamines can also be derived from polyamino-propylene oxide derivatives such as: (OC3H6) c - NH2 CH3 (OC3H6) c ~ NH2 (OC3H6) c --NH2 where each c is a number from 2 to around 20.

PEROXIDIZED ORGANIC HYDROPHOBIC WHITENING SYSTEM An essential characteristic of the detergent compositions or components of the present invention is an organic hydrophobic peroxyacid bleach system, capable of providing a hydrophobic organic peroxyacid compound. By "hydrophobic organic peroxyacid compound" is meant here an organic peroxyacid whose originating carboxylic acid has a critical micelle concentration of less than 0.5 moles / liter and wherein said critical micelle concentration is measured in aqueous solution at 20 ° -50 ° C. Preferably the peroxyacid organic hydrophobic bleach system comprises a source of hydrogen peroxide and a hydrophobic peroxy acid organic bleach precursor compound. The production of the hydrophobic organic peroxyacid occurs by an in situ reaction of the precursor with a source of hydrogen peroxide. Preferred sources of hydrogen peroxide include inorganic perhydrate bleaches. In a preferred alternative embodiment the inorganic peroxyacid bleach system comprises a preformed organic hydrophobic peroxyacid, which is incorporated directly into the composition. Also contemplated are compositions containing mixtures of a source of hydrogen peroxide and an organic peroxyacid precursor in combination with a preformed hydrophobic organic peroxyacid.opr Preferably, the hydrophobic organic peroxyacid contains at least 7 carbon atoms, more preferably at least 9 carbon atoms, most preferably at least 11 carbon atoms. In a preferred aspect the peroxyacid has an alkyl chain comprising at least 7 carbon atoms, more preferably, at least 8 carbon atoms, most preferably at least 9 carbon atoms. The ratio of the hydrophobic organic peroxyacid compound (provided by the hydrophobic organic peroxyacid bleach) to the water-soluble cationic compound is preferably from 20: 1 to 1: 2, more preferably from 10: 1 to 1: 1, very preferable , from 7: 1 to 1: 1.

INORGANIC PERHYDRATE BLEACHERS 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 from 1% to 40% by weight, more preferably from 2% to 30% by weight and much more preferably from 5% to 25% by weight of The compositions. Examples of inorganic perhydrate salts include perborate, percarbonate, perphosphate, persulfate and persilicate salts. The inorganic perhydrate salts can be included as the crystalline solid without additional protection. However, for certain perhydrate salts the preferred versions of these granular compositions use a coated form of the material that provides better storage stability for the perhydrate salt in the granular product. Suitable covers comprise inorganic salts such as alkali metal silicate salts, carbonate or borate or mixtures thereof, or organic materials such as waxes, oils and fatty soaps. Sodium perborate is the preferred perhydrate salt and may be in the form of the monohydrate or nominal formula NaBO2H2? 2 of the tetrahydrate NaBO2H2? 2.3H2O. Alkali metal percarbonates, particularly sodium percarbonate, are the preferred perhydrates herein. Sodium percarbonate is an additional compound having a formula corresponding to 2Na2CO3.3H2? 2, and is commercially available as a crystalline solid. Potassium peroximonopersulfate is another inorganic perhydrate salt for use in the detergent compositions or components herein.

PEROXIÁCIDO WHITENING PRECURSOR Peroxyacid bleach precursors are compounds that react with hydrogen peroxide in a perhydrolysis reaction to produce a peroxyacid. Generally peroxy acid whitening precursors can 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 peroxyacid produced is O X-C-OOH For the purposes of the present invention X will thus contain at least 6 carbon atoms. The hydrophobic peroxyacid bleach precursor compounds are preferably incorporated at a level of from 0.05% to 20% by weight, more preferably from 0.1% to 15% by weight, most preferably from 0.2% to 10% by weight of the compositions detergents Apprate hydrophobic peroxy acid bleach precursor compounds typically contain one or more N- or O-acyl groups, whose precursors can be selected from a wide range of classes. Suitable classes include anhydrides, esters, midas, lactase and acylated derivatives of imidazoles and oxines. Examples of useful materials within these Classes are discussed in GB-A-1586789. Apprate esters are discussed in GB-A-836988, 864798, 1147871, 2143231 and EP-A-0170386.

RESIDUAL GROUPS The residual group, hereafter group L, must be sufficiently reactive so that the perhydrolysis reaction occurs within the optimum time period (for example, a wash cycle). However, if L is too 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 R3 O and mixtures thereof, wherein R 1 is an alkyl, aryl or alkaryl group containing 1 to 14 carbon atoms, R 3 is an alkyl chain containing 1 to 8 carbon atoms, R 4 is H or R 3, R 5 is a alkylene chain containing from 1 to 8 carbon atoms and is H or a solubilizing group. Any of R1, R3 and R4 can be substituted by essentially any functional group including, for example, alkyl, hydroxy, alkoxy, halogen, amine, nitrosyl, amide, and ammonium or alkylammonium groups. Preferred solubilizing groups are -SO3"M +, -CO2" M +, S? 4"M +, -N + (R3) 4X" and O < -N (R3) 3 and much more preferably -SO3"M + and -CO2" M +, wherein R3 is an alkyl chain containing 1 to 4 carbon atoms, M is a cation that provides solubility to the whiteness activator and X is an anion that provides solubility to the whiteness activator. Preferably, M is an alkali metal, ammonium cation or substituted ammonium, with sodium and potassium being most preferred, and X being a halide, hydroxide, methylsulfate or acetate anion.

PRECURSORS SUBSTITUTEED ALKYL RETOXYAIDS Preferred peroxyacid precursors are the alkylperoxyacid substituted amide precursor compounds, including those of the following general formula: R1-C-N-R2-C-L R1-N-C-R2-C-L OR R5 O or R5 0 O wherein R1 is an aryl or alkaryl group with about 1 to 14 carbon atoms, R 2 is an alkylene, arylene and alkarylene group containing 1 to 14 carbon atoms, and R 5 is H or an alkyl, aryl or alkaryl group containing 1 to 10 carbon atoms and L can be essentially any residual group. R1 preferably contains about 6 to 12 carbon atoms. R2 preferably contains from 4 to 8 carbon atoms. R1 can be straight or branched chain alkyl, aryl or substituted alkylaryl which contains branches, substitutions or both, and can be fed by synthetic or natural sources including, for example, tallow grease. Analogous structural variations are permissible for R2. R 2 may include alkyl, aryl, wherein said R 2 may also contain halogen, nitrogen, sulfur, and other typical substituent groups or organic compounds. R5 preferably is H or methyl. R1 and R5 must not contain more than 18 atoms carbon in total. The substituted amide whiteness activating compounds of this type are described in EP-A-0170386. Preferred examples of bleach precursors of this type include the peroxyacid substituted amide precursor compounds selected from (6-octamido-caproyl) oxybenzenesulfonate, (6-decanamido-caproyl) oxybenzenesulfonate, and the most preferred (6-nonanoamidocaproyl) oxybenzenesulfonate) , and mixtures thereof as described in EP-A-0170386.

PEROXIACIDO ORGANIC BENZOXAZINE PRECURSORS Benzoxazine type precursor compounds are also suitable, as discussed, for example, in EP-A-332,294 and EP-A-482,807, particularly those having the formula: wherein R 1 is an alkyl, alkaryl, aryl or arylalkyl containing at least 5 carbon atoms.

BLEACHING PRECURSORS OF ACID ALQUILPERCARBOXÍLICO The bleach precursors of alkylpercarboxylic acid form percarboxylic acids in perhydrolysis. Preferred percarboxylic acid precursor compounds of the imide type include the alkylene diamines N-, N, N1 N1 tetra acetylated wherein the alkylene group contains at least 7 carbon atoms. Other preferred alkylpercarboxylic acid precursors include sodium 3,5,5-trimethyl hexanoyloxybenzenesulfonate (iso-NOBS) and sodium nonanoyloxybenzenesulfonate (NOBS).

LACTAN PRECURSORS N-ACILADOS Yet another class of hydrophobic whiteness activators are the N-acylated precursor compounds of the lactate class discussed generally in GB-A-955735. Preferred materials of this class include caprolactans. Suitable decaprolactane bleach precursors have the formula: wherein R1 is an alkyl, aryl, alkoxyaryl or alkaryl group containing from 6 to 12 carbon atoms. The hydrophobic whiteness precursor materials N-acyl caprolactane are selected from benzoyl caprolactan, octanoyl caprolactan, nonanoyl caprolactan, decanoyl caprolactan, undecenoyl caprolactan, 3,5,5-trimethylhexanoyl caprolactan, decanoyl caprolactan, undecenoyl caprolactan, 3,5,5-trimethylhexanoyl caprolactane and mixtures thereof. One highly preferred is nonanoyl caprolactane. The appropriate lactate valenols have the formula: wherein R1 is an alkyl, aryl, alkoxyaryl or alkaryl group containing 6 to 12 carbon atoms. Most preferably, R1 is selected from phenyl, heptyl, octyl, nonyl, 2,4,4-trimethylpentyl, tenio, and mixtures thereof. Mixtures of any of the peroxy acid whitening precursors, described above, can also be used.

PREFORMED ORGANIC PEROXIDE The 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 0.05% to 20% by weight, more preferably from 1% to 10% by weight. % by weight of the composition. A preferred class of hydrophobic organic peroxyacid compounds are the substituted amide compounds of the following general formula: R 1 N R 2 C OOH O R 5 O or R 1 NC R 2 C OOH R 5 OO wherein R 1 is an aryl or alkaryl group with about 1 to 14 carbon atoms, R 2 is an alkylene, arylene, and alkarylene group containing about 1 to 14 carbon atoms, and R5 is H or an alkyl, aryl or alkaryl group containing from 1 to 10 carbon atoms. R1 preferably contains about 6 to 12 carbon atoms. R2 preferably contains about 4 to 8 carbon atoms. R1 may be straight or branched chain alkyl, aryl or substituted alkylaryl, which contains branching, substitution or both, and may be fed from synthetic or natural sources including, for example, tallow grease. For R2, R2, analogous structural variations are permissible which may include alkyl, aryl, wherein said R 2 may also contain halogen, nitrogen, sulfur and other substituent groups or typical organic compounds. R5 preferably is H or methyl. R1 and R5 must not contain more than 18 carbon atoms in total. The substituted amide whiteness activating compounds of this type are described in EP-A-0170386.

Suitable examples of this class of agents include (6-octylamino) -6-oxo-caproic acid, (6-nonylamino) -6-oxo-caproic acid, (6-decylamino) -6-oxo-caproic acid, monoperoxy phthalate hexahydrate of magnesium, the magnesium salt or metabenzene perbenzoic acid, 4-nonylamino-4-oxoperoxybutyric acid and diperoxidedecanodioic acid. These bleaching agents are discussed in the US 4,483,781, US 4,634,551, EP 0,133,354, US 4,412,934 and EP 0,170,386. A preferred hydrophobic preformed peroxy acid bleaching compound for the purpose of the invention is monononylamido percarboxylic acid. Other suitable organic peroxyacids include diperoxyalkanedioic acids having more than 7 carbon atoms, such as diperoxydecanedioic acid, diperoxytetradecanedioic acid and diperoxyhexadecanedioic acid. Other suitable organic peroxyacids include the diaminoperoxy acids, which are discussed in WO 95/03275, with the following general formula: O O O O MOCR- (R1N) n-C (NR2) n.-R3- (R2N) m-C (NR1) m-RCOOM wherein: R is selected from the group consisting of alkylene of 1 to 12 carbon atoms, cycloalkylene of 5 to 12 carbon atoms, arylene of 6 to 12 carbon atoms and radical combinations thereof. R1 and R2 are independently selected from the group consisting of H, alkyl radicals of 1 to 16 carbon atoms and aryl of 6 to 12 carbon atoms, and a radical that can form a ring of 3 to 12 carbon atoms together with R3 and both nitrogens; R3 is selected from the group consisting of alkylene radicals of 1 to 12 carbon atoms, cycloalkylene of 5 to 12 carbon atoms and arylene of 6 to 12 carbon atoms; n and n 'are each an integer chosen in such a way that the sum of them is 1; and m and m 'are each an integer chosen in such a way that the sum of them is 1; and M is selected from the group consisting of H, cations and radicals of alkali metals, alkaline steams, ammonium, alkylammonium and combinations thereof. Other suitable organic peroxyacids are those which include the amide peroxyacids which are discussed in WO 95/16673, with the following general structure: X-Ar-CO-NY-R (Z) -CO-OOH wherein X represents hydrogen or a compatible substituent, Ar is an aryl group, R represents (CH2) n in which n = 2 or 3, and Y and Z represent each independently a substituent selected from hydrogen or an alkyl or aryl or alkaryl group or an aryl group substituted by a compatible substituent provided that at least one of Y and Z is not hydrogen is n = 3. The substituent X in the benzene nucleus preferably is a hydrogen or a meta or para substituent, selected from the group comprising halogen, typically chlorine atom, or some non-interfering non-released species such as an alkyl group, conveniently up to 6 carbon atoms , for example a methyl, ethyl or propyl group. Alternatively, X may represent a second amido-percarboxylic acid substituent of formula: -CO-NY-R (Z) -CO-OOH wherein R, Y, Z and n are as defined above.

MOOC-R1CO-NR2-R3-NR4-CO-R5COOOM wherein R1 is selected from the group consisting of alkylene of 1 to 12 carbon atoms, cycloalkylene of 5 to 12 carbon atoms, arylene of 6 to 12 carbon atoms and radical combinations thereof; R.

NON-HYDROPHOBIC PEROXYACY WHITENING PRECURSOR Preferably a non-hydrophobic peroxyacid bleach precursor is present in the detergent compositions or components of the present. This can be any peroxyacid bleach precursor, not being a hydrophobic peroxy acid bleach precursor as defined above. Preferably the non-hydrophobic peroxyacid contains less than 7 carbon atoms, more preferably less than 5, much more preferable 2. Other peroxyacid bleach precursors are those which can be a precursor for both hydrophobic and non-hydrophobic peroxyacids. Bleaching precursors of non-hydrophobic peroxyacids are preferably incorporated at a level of from 0.5% to 20% by weight, more preferably from 1% to 15% by weight, much more preferably from 1.5% to 10% by weight of the compositions. The proportion of non-hydrophobic peroxyacid bleach precursor to cationic compound is preferably from 20: 1 to 1: 10, more preferably from 10: 1 to 1: 1, much more preferably from 7: 1 to 1: 1. Suitable peroxy acid bleach precursors typically contain one or more N- or O-acyl groups, whose precursors can be selected from a wide variety of classes. Appropriate classes include anhydrides, esters, imides and adiated derivatives of imidazoles and oxines. Examples of useful materials within these classes are discussed in GB-A-1586789, the appropriate esters are discussed in GB-A-836988, 864798, 1147871, 2143231 and EP-A-0170386. Preferred non-hydrophobic peroxyacid bleach precursors are alkyl peroxyacid fatty acid whitening precursors, precursor of perbenzoic acid, precursors derived from perbenzoic acid and precursors of cationic peroxyacids.

PRECURSORS BLEACHERS FOR PEROXYACY FATS OF RENT A most preferred additional peroxy acid bleach precursor is a bleach precursor of alkyl fatty peroxyacid. The peroxyacid fatty acid whitening precursors of alkyl form alkyl peroxyacids in perhydrolysis. Preferred precursors of this type reach the peracetic acids in perhydrolysis. Preferred alkyl acid peroxyacid precursor compounds of the metric type include the tetra acetylated N-, N, N 1 N 1 alkylene diamines wherein the alkylene group contains from 1 to 6 carbon atoms. particularly those compounds in which the alkylene group contains 1, 2 and 6 carbon atoms. Tetraacetyl ethylenediamine (TAED) is particularly preferred.

PERBENZOIC ACID PRECURSOR Essentially any perbenzoic acid precursors are suitable here, including those of the N-acylated lactam class, which are preferred.

Suitable O-acylated perbenzoic acid precursor compounds include substituted and unsubstituted benzoyl oxybenzene sulfonates, including for example benzoyl oxybenzene sulfonate: Also suitable are the benzoylation products of sorbitol, glucose, and all saccharides with benzoylating agents, including for example: Ac = COCH3; Bz = Benzoil Preferred perbenzoic acid precursor compounds of the imide type include N-benzoyl succinimide, tetrabenzoyl ethylenediamine and the urea N-benzoyl substituted. Suitable imidazole perbenzoic acid precursors include N-benzoyl imidazole and N-benzoyl benzimidazole and others useful perbenzoic acid precursors containing N-acyl groups including N-benzoyl pyrrolidone, dibenzoyl taurinic acid and benzoyl pyroglutamic acid. Preferred perbenzoic acid precursors include benzyl diacyl peroxides, benzoyl tetraacyl peroxides, and the compound having the formula: The italic anhydride is another suitable perbenzoic acid precursor compound herein.

PRECURSORS OF PERBENZOIC ACID DERIVATIVES Suitable prebenders of perbenzoic acid derivatives include any of the perbenzoic precursors discussed herein, in which the perbenzoic group is substituted by essentially any functional group including alkyl groups.

PRECURSORS OF CATIONIC PEROXYACY Cationic peroxyacid precursor compounds are also suitable herein. Typically, these cationic peroxyacid precursors are formed by replacing the peroxyacid moiety with an ammonium or alkylammonium group, preferably an ethyl or methylammonium group. Cationic peroxyacid precursors are described in US Patents 4,904,406; 4,751, 015; 4,988,451; 4,397,757; 5,269,962; 5,127,852; 5,093,022; 5,106,528; UK 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 Patent Application No. 9407944.9 and in the Requests for Patent US 08/298903, 08/298650, 08/298904 and 08/298906. Suitable cationic peroxyacid precursors include any of ammonium or alkylammonium, substituted alkyl or benzoyl oxybenzene sulfonates, N-acylated caprolactans and benzoyl peroxides of monobenzoyltetraacetyl glucose. A preferred cationically substituted benzoyl oxybenzene sulfonate is 4- (trimethylammonium) methyl derivative of benzoyl oxybenzene sulfonate: A preferred cationically substituted alkyloxybenzene sulfonate is the methylammonium derivative of 2,3,3-tri-trimethylhexanoyloxybenzenesulfonate. Preferred cationic peroxyacid precursors of the N-acylated caprolactam class include the trialkylammonium methylenebenzoylcaprolactams, particularly the trimethylammonium methylenebenzoylcaprolactam: Another preferred cationic peroxyacid precursor is 2- (N, N, N-trimethylammonium) ethyl sodium-4-sulfophenyl chloride.

CATIONIC POLYMERS The detergent composition or component thereof may contain additional polymeric cationic ethoxylated amine compounds with removal / anti-rejection of particulate clay soil, selected from the group consisting of water soluble cationic polymers. These polymers comprise a polymeric backbone, at least 2M groups and at least one L-X group, wherein M is a cationic group connected to or integrated with the backbone; X is a nonionic group selected from the group consisting of H, alkyl of 1 to 4 carbon atoms or hydroxyalkyl ester groups or ether, and mixtures thereof; and L is a hydrophilic chain that links M and X groups or joins X to the polymeric backbone. The cationic polymeric ethoxylated amine compounds may be present in the detergent compositions at a level of from 0.01% to 30%, more preferably from 0.1% to 15%, much more preferably from 0.2% to 3% by weight of the detergent composition. As used herein, the term "polymeric backbone" refers to the polymer portion to which groups M and L-X are connected or are an integral part thereof. Within this term are included the oligomeric main structures (2 to 4 units) and the true polymeric main structures (5 or more units). As used herein, the term "attached to" means that the group is dependent on a polymeric backbone, examples of which are represented by the following general structures A and B: 1 1 1 M M L 1 1 1 1 L X | 1 X A B As used herein, the term "integrated with" means that the group forms part of the polymeric backbone, examples of which are represented by the following general structures C and D: - M - - M - - I I L L I I X X C D Any polymeric backbone can be used as long as the cationic polymer formed is soluble in water and has removal properties / anti-redeposition of clayey dirt. Suitable primary polymeric structures can be derivatives of polyurethanes, polyesters, polyethers, polyamides, polyimides and the like, polyacrylates, polyacrylamides, polyvinyl ethers, polyethylenes, polypropylenes and the like to polyalkylenes, polystyrenes and the like to polyalkarylenes, polyalkyleneamines, polyalkyleneimines, polyvinylamines, polyallylamines, polydiallylamines, polyvinylpyridines, polyaminetriazoles, polyvinyl alcohol, aminopolyureylenes, and mixtures thereof. M can be any compatible cationic group comprising a N + (quaternary) with positively charged center. The positively charged quaternary center can be represented by the following general structures E and F: Particularly preferred M groups are those which contain a quaternary center represented by the general structure E. The cationic group is preferably positioned close to or integrated with the polymer structure. The positive charge of the N + centers is compensated by the appropriate number of opposite anions. Suitable counter anions include CI ", Br", SO32", SO42", PO42 ~, MeOSO3- and the like. Particularly preferred counterions are CI "and Br". X can be a nonionic group selected from hydrogen (H), alkyl or hydroxyalkyl of 1 to 4 carbon atoms, or ester or ether groups, and mixtures thereof. Preferred ester or ether groups are the acetate ester and the methyl ether, respectively. Particularly preferred nonionic groups are H and methyl ether. Cationic polymers suitable for use in granular detergent components according to the present invention typically have a ratio of cationic groups M to nonionic groups X from approximately 1: 1 to about 1: 2. However, for example, by appropriate copolymerization of cationic, non-ionic monomers (ie, those containing the L-X group) and cationic / non-ionic mixtures, the ratio of M groups to X groups may be varied. The ratio of groups M to groups X can usually reach approximately from 2: 1 to 1: 10. In preferred cationic polymers, the ratio is from about 1: 1 to 1: 5.

The polymers formed from this copolymerization are typically random, that is, the cationic, nonionic monomers and cationic / nonionic mixtures are copolymerized in a non-repeating sequence. The units containing M groups and L-X groups may contain 100% of the cationic polymers of the present invention. However, the inclusion of other units (preferably non-ionic) in the polymers is also permissible. Examples of other units include acrylamides, vinyl ethers and those containing tertiary non-quaternized amine groups (M1) containing a N center. These other units may comprise from 0% to about 90% of the polymer (being from about 10% to 100% of the polymer units containing M and LX groups, including M1-LX groups) Normally, these other units comprise from 0% to about 50% of the polymer (being from about 50% to 100% of the polymer, units that they contain groups M and LX). The number of groups M and L-X usually reaches each approximately 2 to 200. Typically the number of groups M and L-X are each approximately from 3 to 100. Preferably, the number of groups M and LX are each from about 3 to 40. Unlike the portions for groups M and X, or to be attached to the main polymer structure, the hydrophilic chain L usually consists entirely of the polyoxyalkylene moiety - [(RO) m (CH2CH2?) N] -. The portions - (R'O) m- and - (CH2CH2O) n- of the polyoxyalkylene portion can be mixed together, or preferably form blocks of - (R'O) m- and portions - (CH2CH2O) n-. R 'preferably is C3Hβ (propylene); m preferably is from 0 to about 5, and most preferably 0; that is, the polyalkylene portion consists entirely of the - (CH2CH2?) n- portion. The - (CH2CH2O) n -preferably comprises at least about 85% by weight of the polyoxyalkylene portion, and more preferably 100% by weight (m is 0). For the portion - (CH2CH2O) n-, n is usually from about 3 to 100. Preferably, n is from about 12 to about 42. A plurality (2 or more) of portions LX can also be connected together, and attached to the group M of the main polymer structure, examples of which are represented by the following general structures G and H: M L L L L X X X X H Structures such as G and H can be formed, for example, by reacting glycidol with an M group or with the main polymer structure, and ethoxylating the hydroxy groups formed subsequently. The representative classes of cationic polymers of the present invention are the following: A. Polyurethane, Polyester, Polyether, Polyamide or Similar Polymers. An appropriate class of cationic polymers are derivatives of polyurethanes, polyesters, polyethers, polyamides and the like. These polymers comprise units selected from those having formulas I, II and II: < R62) k - (A '- A? 1')? - _Rz -N + - -R? (R5) k [(C3H60) m (CH2CH20) n] X where A1 is 0 0 0 0 0 -NC-, -CN-, -CO-, -OC- or -C-; R R XesOol; ResHo alkyl or hydroxyalkyl of 1 to 4 carbon atoms; R1 is alkylene of 2 to 12 carbon atoms, hydroxyalkylene, alkenylene, cycloalkylene, arylene or alkarylene, or an oxyalkylene portion of 2 to 3 carbon atoms having from 2 to about 20 oxyalkylene units provided O-O or O-N bonds are not formed with A1; when x is 1, R2 is -R5- except when A1 is O - C -, or is - (OR8) and or -OR5- provided OO or ON links are not formed with A1, and R3 is -R5- except when A1 is O-C-, or is - (R8O) -yo -R50- provided that no 0-0 or ON links are formed with A1; when x is 0, R2 is - (OR8) y-, - OR5-, COR5-, -OCR5-, -OCR5, O O O -NCR5-, - NCOR5-, -CNR5- or - OCNR5- RO RO OR OR and R3 is -R5-; R4 is alkyl or hydroxyalkyl of 1 to 4 carbon atoms, or the portion - (R5) k- [(C3H6?) M (CH2CH20) n] -X; R5 is alkylene of 1 to 12 carbon atoms, hydroxyalkylene, alkenylene, arylene, or alkarylene; every R6 is alkyl or hydroxyalkyl of 1 to 4 carbon atoms, or the - (CH2) rA2- (CH2) S- moiety, wherein A2 is -O- or -CH2-; R7 is H or R4; R8 is alkylene or hydroxyalkylene of 2 to 3 carbon atoms; X is H, O - CR9, -R9 or a mixture thereof, wherein R9 is alkyl or hydroxyalkyl of 1 to 4 carbon atoms; k is 0 or 1; m and n are numbers such that the - (CH2CH2O) n- portion comprises at least about 85% by weight of the - [(CH3H6O) m (CH2CH2O) n] - portion; m is from 0 to about 5; n is at least about 3; r is 1 or 2, s is 1 or 2, and r + s is 3 or 4; and it's from 2 to about 20; the number of u, v and w are such that there are at least two centers N + and at least two groups X. In the above formulas, A1 is preferably O O II II -NC- or -CN-; I I R R A2 is preferably -O-; x is preferably 1; and R is preferably H. R1 may be linear (for example -CH2CH2-CH2-, CH-, C alkylene, hydroxyalkylene, alkenylene, cycloalkylene, alkarylene or branched oxyalkylene; when R1 is an oxyalkylene portion of 2 to 3 carbon atoms, the number of oxyalkylene units is preferably from about 2 to 12; R1 is preferably alkylene of 2 to 6 carbon atoms or phenylene, and most preferably alkylene of 2 to 6 carbon atoms (for example, ethylene, propylene, hexamethylene). R2 is preferably -OR5- or ~ (OR8) and-; R3 is preferably -R50- or - (OR8) and-; R4 and R6 are preferably methyl. Analogously, R1, R5 can be linear or branched, and is preferably alkylene of 2 to 3 carbon atoms; R7 is preferably H or alkyl of 1 to 3 carbon atoms; 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 centers N + and groups X is 2 or 3; n is much more preferable at least about 12, with a typical range of about 12 to about 42 for all ranges of u + v + w. For homopolymers (v and w are 0), u is preferably from about 3 to about 20. For random copolymers (u is at least 1 or preferably 0), v and w are each preferably from about 3 to about 40.

B. POLYACRYLATE, Polyacrylamide, Polyvinyl Ether or Similar Polymers.

Another class of suitable cationic polymers are derivatives of polyacrylates, polyacrylamides, polyvinyl ethers and the like. These polymers comprise units selected from those having the formulas IV, V and VI.

[(CsHßOJmíCHzCH-jOjJ X IV V (VI) where A1 is o o O O 0 -OCM- - - --OC- -, - -OCO- -, - -CO- -, or - -NCN R R R R is H or alkyl or hydroxyalkyl of 1 to 4 carbon atoms; R1 is substituted alkylene of 2 to 12 carbon atoms, hydroxyalkylene, alkenylene, arylene or alkarylene, or oxyalkylene of 2 to 3 carbon atoms; each R2 is alkylene of 1 to 12 carbon atoms, hydroxyalkylene, alkenylene, arylene or alkarylene; each R3 is alkyl or hydroxyalkyl of 1 to 4 carbon atoms, the portion - (R2) k - [(C3H6?) m (CH2CH2O) r?] - X, or joint forming the portion - (CH2) rA2- (CH2 ) S-, where A2 is -O- or -CH2-; each R4 is alkyl or hydroxyalkyl of 1 to 4 carbon atoms, or two R4 together form the portion - (CH2) rA2- (CH2) s-; X is H, O -CRS -R5 or mixture thereof, wherein R5 is alkyl or hydroxyalkyl of 1 to 4 carbon atoms; j is 1 or 0; k is 1 or 0; m and n are numbers such that the - (CH2CH2O) n- portion comprises at least about 85% by weight of the - [(C3H6O) m (CH2CH2?) n] - portion; m is from 0 to about 5; n is at least about 3; r is 1 or 2, s is 1 or 2 and r + s is 3 or 4; the numbers of u, v and w are such that there are at least 2 N + centers and at least 2 X groups. In the above formulas, A1 is preferably OR II II - CN-, - CO- or -O-; I R A2 is preferably -O-; R is preferably H, R1 may be linear (e.g. -CH - -CH- -CH, •) or or branched (v.gr. substituted alkylene, hydroxyalkylene, alkenylene, alkarylene or oxyalkylene; R1 is preferably substituted alkylene of 2 to 6 carbon atoms or substituted oxyalkylene of 2 to 3 carbon atoms, and much more preferably CH3 -CH2CH- or - CH2-C- Each R2 is preferably alkylene of 2 to 3 carbon atoms, each R3 and R4 preferably is methyl; R5 is preferably methyl; X is preferably H or methyl; j preferably is 1; k preferably is 0; m is preferably 0; r and s are each 2 preferably. 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 derivatives of polyalkyleneamines, polyalkyleneimines and the like. These polymers comprise units selected from those having the formulas VII and VIII and IX.

(R) d - (R1 -M ' (R3) k [(C3H6O) m (CH2CH2O) n] X (R3) k [(C3H6O) m (CH2CH2O) n] X wherein R1 is alkylene of 2 to 12 carbon atoms, hydroxyalkylene, alkenylene, cycloalkylene, arylene or alkarylene, or an oxyalkylene portion of 2 to 3 carbon atoms having from 2 to about 20 oxyalkylene units provided no bonds are formed ON; each R2 is alkyl or hydroxyalkyl of 1 to 4 carbon atoms, or the portion - (R3) k - [(C3H6O) m (CH2CH2O) n] -X; R3 is alkylene of 1 to 12 carbon atoms, hydroxyalkylene, alkenylene, arylene or alkarylene; M 'is a center N + or N, X is H, - CR4, O -R4 or mixture thereof, wherein R4 is alkyl or hydroxyalkyl of 1 to 4 carbon atoms; d is 1 when M '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 - (CH2CH2O) n- portion contains at least 85% by weight of the portion - [(C3H6?) m (CH2CH2?) n] -; m is from 0 to about 5; n is at least about 3; the numbers of x, y and z are such that there are at least 2 groups M ', at least 2 centers N + and at least 2 groups X. In the above formulas, R1 can be varied as the R1 of polyurethane and similar polymers; each R2 is preferably methyl or the portion - (R3) k - [(C3H6O) m (CH2CH2O) n] -X; R3 is preferably alkylene of 2 to 3 carbon atoms; 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 much preferable to at least about 12, with a typical range from about 12 to about 42 for all ranges of x + y + z. Typically, x + y + z is from 2 to about 40 and preferably from 2 to about 20. For short polymer chain lengths, x + and + z can reach from 2 to 9 with 2 to 9 N + centers from 2 to 11 X groups. For polymers with long chain length, x + y + z is at least , with a preferred range of 10 to about 42. For polymers of short and long chain lengths, the M 'groups are typically a mixture of about 50 to 100% N + centers and from 0 to about 50% N centers The preferred cationic polymers within this are derivatives of polyalkyleneamines of 2 to 3 carbon atoms (x + y + z is 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 polyethyleneamines (PEA) and polyethyleneimines (PEI). These preferred cationic polymers contain units having the general formula: (R2) d (R2) d (M) a- - (CH2- CH2M) ^ - [(CH2CH2O ') n -X] 2 (R2) d (R2) d - [CH2CH2M] and- - [ChfeChfeMk- ( CH2CH2O) n- X [(CH2CH2O) n-X] 2 wherein R2 (preferably methyl), M ', X, d, x, y, z and n are defined above; a is 1 or 0.

Prior to ethoxylation, the PEAs used for the preparation of cationic polymers of the present invention have the following general formula: [H2N] to [CH2CH2N] X [CH2CH2N] and [CH2CH2NH2] Z H where x + y + z is from 2 to 9, and a is 0 or 1 (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 preferred PEAs, x + and + z is about 3 to 7 (the molecular weight is about 140 to 310). These PEA can be obtained by reactions involving ammonium and dichloroethylene, followed by fractional distillation. The commonly obtained PEAs are triethylenetetramine (TETA) and tetraethylenepentamine (TEPA). In the aforementioned pentamines, ie the hexamines, heptamines, octamines and possibly nonamines, the cogently derived mixture is not present for distillative separation and may include other materials such as cyclic amines and particularly piperazines. Cyclic amines with side chains in which nitrogen atoms are present may also be present. See US Patent 2,792,372 to Dickson, issued May 14, 1957, which describes the preparation of PEA.

The minimum degree of ethoxylation required for the preferred removal / anti-redeposition performance of clay soil may vary depending on the number of units in the PEA. Where y + z is 2 or 3, n is preferably at least near 6. Where y + z is from 4 to 9, the corresponding benefits are obtained when n is at least close to 3. For the preferred cationic PEAs, n is at least about 12, with a typical range of about 12 to about 42. The PEIs used in the preparation of the polymers of the present invention have a molecular weight of at least about 440 before ethoxylation, which represents at least 10 units. The preferred PEIs used in the preparation of these polymers have a molecular weight of about 600 to about 1800. The main polymer structure of these PEIs can be represented by the general formula: H H2N - [- CH2CH2N -] - x - [- CH2CH2N -] - and - [- CH2CH2NH2-] Z wherein the sum of x, y and z represents a number of sufficient magnitude to produce a polymer having the molecular weights specified previously. Although the main linear polymer structures are possible, branched chains may also occur. The relative proportions of primary, secondary and tertiary amine groups present in the polymer may vary, depending on the manner of preparation. The distribution of amine groups is typically 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 PEI can be prepared, for example, by polymerizing ethyleneimine in the presence of a catalyst such as carbon dioxide, sodium bisulfite, sulfuric acid, hydrogen peroxide, hydrochloric acid, acetic acid, etc. The specific methods for preparing PEI are discussed in U.S. Patent 2,182,306 to Ulrich and co-inventors, issued December 5, 1939, U.S. Patent 3,033,746 to Mayle and co-inventors, issued May 8, 1962, U.S. Patent 2,208,095 to Esselmann and co-inventors, Issued on July 16, 1940, US Patent 2,806,839 to Crowther, issued September 17, 1957; and Wilson's US Patent 2,533,696, issued May 21, 1951 (all incorporated herein by reference). As defined in the preceding formulas, n is at least about 3 for the cationic PEIs. However, it should be noted that the minimum degree of ethoxylation required for the acceptable removal / antiredeposition performance of clay soil can be increased as that the molecular weight of the PEI increases, especially well beyond about 1800. Also, the degree of ethoxylation for the preferred polymers increases as the molecular weight of the PEI increases. For PEs having a molecular weight of at least about 600, n is preferably at least about 12, with a typical range of about 12 to 42. For PEI having a molecular weight of at least 1800, n is preferably at least about 24, with a typical range of about 24 to about 42.

D. Dialylaminic polymers Another class of suitable cationic polymers are the derivatives of the diallylamines. These polymers contain units selected from those that have the formulas X and XI: wherein R1 is alkyl or hydroxyalkyl of 1 to 4 carbon atoms, or the portion - (R2) k- [(C3H60) m (CH2CH2O) n] -X; R2 is alkylene of 1 to 12 carbon atoms, hydroxyalkylene, alkylene, arylene or alkarylene; each R3 is alkyl or hydroxyalkyl of 1 to 4 carbon atoms, or together they form the portion - (CH2) rA- (CH2) S-, where A is -O- or -CH2-; X is H, -CR4 OR -R4 or mixture thereof, wherein R4 is alkyl or hydroxyalkyl of 1 to 4 carbon atoms, k is 1 or 0; m and n are numbers such that the - (CH2CH2O) n- portion comprises at least about 85% by weight of the portion - [(C3H6?) m (CH2CH2?) n] -; m is from 0 to about 5; n is at least about 3; r is 1 or 2, s is 1 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 numbers of u and v are such that there are at least 2 centers N + and at least 2 groups X. In the above formulas, A is preferably -O-; R1 is preferably methyl; each R2 preferably is alkylene of 2 to 3 carbon atoms; each R3 is preferably methyl; R 4 is preferably methyl; X preferably is H; k preferably is 0, m preferably is 0; r and s 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 preferably it is at least 12, with a typical range of about 12 to about 42 for the whole scale of u + v. Typically, v is 0, and a is from 2 to about 40, and preferably from 2 to about 20.

ADDITIONAL DETERGENT COMPONENTS The 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 or component, and the precise nature of the washing operation for which they will be used. The compositions or components thereof of the invention preferably contain one or more additional detergent components selected from among additional surfactants, additional bleaches, bleach catalysts, alkalizing systems, builders, organic polymer compounds, enzymes, suds suppressants, dispersants. of lime soap, additional suspending and anti-redeposition agents, dirt removing agents, perfumes and corrosion inhibitors.

ADDITIONAL SURGICAL AGENT 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. In US Patent 3,929,678 issued to Laughlin and Heuring on December 30, 1975, a typical list of anionic, nonionic, ampholytic and zwitterionic classes, and the species of these surfactants are shown. Additional examples are presented in "Active Surface Agents and Detergents" (Vol.l and II by Schwartz, Perry and Berch). A list of suitable surfactants is shown in US Patent 4,259,217 issued to Murphy on March 31, 1981. Where present, ampholytic, anophthous and zwitterionic surfactants are generally used in combination with one or more anionic and / or nonionic surfactants.

ANION SURGICAL AGENT The detergent compositions or components thereof preferably contain an additional anionic surfactant. Essentially any surfactant useful for detersive purposes may be comprised in the detergent composition. These can 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. The anionic sulfate surfactants are preferred. Other anionic surfactants include the isethionates such as acyl isethionates, N-acyl taurates, fatty acid or methyl tauride amides, succinates, and alkyl sulfosuccinates, sulfosuccinate monoesters (especially monoesters of 12 to 18 saturated and unsaturated carbon atoms) ) diesters of sulfosuccinate (especially diesters of 6 to 14 carbon atoms saturated and unsaturated), N-acyl sarcosinates. Resin acids and hydrogenated resin acids are also suitable, such as rosin, hydrogenated rosin, and resin acids and hydrogenated resin acids present in or derived from tallow oil.

SURGICAL AGENT ANONYMOUS SULFATE Suitable anionic sulfate surfactants for use herein include linear and branched primary and secondary alkyl sulfates, alkyl ethoxysulfates, oleoyl glycerol fatty sulfates, alkylphenol ether sulphates, ethylene oxide sulfates, acyl-N- (alkyl) from 1 to 4 carbon atoms) of 5 to 17 carbon atoms and sulfates of -N- (hydroxyalkyl of 1 to 2 carbon atoms) glucamine and sulfates of alkylpolysaccharides such as the alkyl polyglycoside sulphates (the non-sulfated nonionic compounds described herein) ).

The alkyl sulfate surfactants are preferably selected from the linear and branched primary alkyl sulphates of to 18 carbon atoms, more preferably the branched chain alkyl sulfates of 11 to 15 carbon atoms and the straight chain alkyl sulfates of 12 to 14 carbon atoms. The alkyl ethoxysulfate surfactants are preferably selected from the group consisting of alkyl sulfates of 10 to 18 carbon atoms which have been ethoxylated with 0.5 to 20 moles of ethylene oxide per molecule. More preferably, the alkyl ethoxysulfate surfactant is 11 to 18 carbon atoms, much more preferably alkyl sulfate of 11 to 15 carbon atoms, which has been ethoxylated with 0.5 to 7, preferably 1 to 5, moles. of ethylene oxide per molecule. A particularly preferred aspect of the invention employs mixtures of the surfactants alkyl sulfate and alkyl ethoxysulfate. These mixtures have been discussed in PCT Patent Application WO 93/18124.

SURGICAL ANTI-SULPHONATE AGENT The anionic sulfonate surfactants for use herein include salts of linear alkylbenzene sulfonates of 5 to 20 carbon atoms, alkyl ester sulfonates, primary or secondary alkane sulfonates of 6 to 22 carbon atoms, olefin sulfonates from 6 to 24 carbon atoms, sulfonated polycarboxylic acids, sulfonates alkylglycerolics, fatty acylglycerol sulfonates, oleylglycerol fatty sulfonates, and mixtures thereof.

ANESSIONAL CARBOXYLATE ANTI-AGING AGENT Suitable anionic carboxylate surfactants include alkyl ethoxy carboxylates, alkyl polyethoxy polycarboxylate surfactants, and soaps ('alkylcarboxyls'), especially certain secondary soaps as described herein. Suitable alkyl ethoxycarboxylates include those having the formula RO (CH 2 CH 20) x, CH 2 COO-M + wherein R is an alkyl group of 6 to 18 carbon atoms, x ranges from 0 to 10, and the ethoxylated distribution is such that, based on the weight, the amount of material where x is 0 is less than 20% and M is a cation. Suitable alkyl polyethoxy polycarboxylate surfactants include those having the formula RO-CHR1-CHR2-O) -R3 wherein R is an alkyl group of 6 to 18 carbon atoms, x is from 1 to 25, R1 and R2 are selected from the group consisting of hydrogen, methyl acid radical, succinic acid radical, hydrosuccinic acid radical, and mixtures thereof, and R3 is selected from the group consisting of hydrogen, substituted or unsubstituted hydrocarbon with 1 to 8 carbon atoms, and mixtures thereof. Suitable soap surfactants include secondary soap surfactants containing a carboxyl unit connected to a secondary carbon. Soap surfactants Preferred secondary ones for use herein, are the water-soluble members selected from the group consisting of water-soluble salts of 2-methyl-1-undecanic acid, 2-ethyl-1-decanoic acid, 2-propyl-1-nonannoic acid , acid 2-butyl-1-octanoic and 2-phenyl-1-heptanoic acid. Certain soaps can also be included as suds suppressors.

THERMOACTIVE AGENT SARCOSINATE OF ALKALINE METAL Other suitable anionic surfactants are alkali metal sarcosinates of the formula R-CON (R 1) CH 2 COOM, wherein R is a linear or branched alkyl or alkenyl group of 5 to 17 carbon atoms, R 1 is an alkyl group of 1 to 4 carbon atoms and M is an alkali metal ion. The myristyl and oleoylmethyl sarcosinates are preferred examples in the form of their sodium salts.

ALCOXYLATED NON-IONIC SURGERY AGENT Essentially any alkoxylated nonionic surfactants are suitable here. Preferred are non-ionic ethoxylated and propoxylated surfactants. The preferred alkoxylated surfactants can be selected from the classes of nonionic condensates of alkylphenols, ethoxylated nonionic alcohols, ethoxylated / propoxylated fatty alcohols not ionics, condensed with nonionic ethoxylated / propoxylated propylene glycol, and nonionic condensation products ethoxylated with propylene oxide / ethylene diamine adducts.

ALCOHOL SURELY NON-IONIC ALCOHOL SURGICAL AGENT The condensation products of aliphatic alcohols with 1 to 25 moles of alkylene oxide, particularly ethylene oxide and / or pfopylene oxide, are suitable for use herein. The alkyl chain of the aliphatic alcohol may be straight or branched, primary or secondary, and generally contains from 6 to 22 carbon atoms. The condensation products of alcohols having an alkyl group containing from 8 to 22 carbon atoms with 2 to 10 moles of ethylene oxide per mole of alcohol are particularly preferred.

AGENT SURFACTANT OF AMID OF POLYHYDROXYLIC FATTY ACID NO ION The polyhydroxy fatty acid amides suitable for use herein, and those having the structure formula R2CONR1Z wherein: R1 is H, hydrocarbyl of 1 to 4 carbon atoms, 2-hydroxyethyl, 2-hydroxypropyl, ethoxy, propoxy, or a mixtures thereof, preferably alkyl of 1 to 4 carbon atoms, more preferably alkyl of 1 to 2 carbon atoms, much more preferable alkyl of 1 carbon atom (ie, methyl); and R 2 is a hydrocarbyl of 5 to 31 carbon atoms, preferably straight-chain alkyl or alkenyl of 5 to 19 carbon atoms, more preferably straight-chain alkyl or alkenyl of 9 to 17 carbon atoms, much more preferably alkyl or straight chain alkenyl of 11 to 17 carbon atoms, or 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 reduced sugar in a reductive amination reaction; much more preferably Z is a glycryloyl.

NON-IONIC SURFACTANT AGENT OF AMID FATTY ACID Suitable fatty acid amide surfactants include those having the following formula: R6CON (R7) 2 wherein R6 is an alkyl group containing from 7 to 21, preferably from 9 to 17 carbon atoms and each R7 is selected from a group consisting of hydrogen, alkyl of 1 to 4 carbon atoms, hydroxyalkyl of 1 to 4 carbon atoms, and - (CH2H4?) xH, wherein x is within the range of 1 to 3.

NON-IONIC SURGERY AGENT The alkylpolysaccharides suitable for use herein are discussed in US Pat. No. 4,565,647, to Llenado, issued January 21, 1986, with a hydrophobic group containing from 6 to 30 carbon atoms and a polysaccharide, for example, a polyglycoside, group hydrophilic containing from 1.3 to 10 saccharide units. Preferred alkyl polyglycosides have the formula R2O (CnH2nO) t (glycosyl) x wherein R2 is selected from the group consisting of alkyl, alkylphenyl, hydroxyalkyl, hydroxyalkylphenium, 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 glycosyl is derived from glucose, preferably.

ANTI-THERAPY SURGICAL AGENT Suitable amphoteric surfactants 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, acylamidopropoyl and alkylphenyl group, or mixtures thereof, with 8 to 26 carbon atoms. carbon; 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 1 to 3; or a polyethylene oxide group containing 1 to 3 ethylene oxide groups. Preferred are alkyldimethylamine oxide of 10 to 18 carbon atoms, and acylamido alkyldimethylamine oxide of 10 to 18 carbon atoms. A suitable example of an alkylamphodicarboxylic acid is Miranol (TM) C2M Conc. Manufactured by Miranol, Inc., Daytona, N.J.

ION HYBRID SURFACTANT AGENT The zwitterionic surfactants can also be incorporated into the detergent compositions or components thereof according to the invention. 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 betaine and sultaine are exemplary zwitterionic surfactants for use herein.

The appropriate betaines are the compounds that have the formula R (R ') 2N + R2COO- wherein R is a hydrocarbyl group of 6 to 18 carbon atoms, each R1 is typically alkyl of 1 to 3 carbon atoms, and R2 is a hydrocarbyl group of 1 to 5 carbon atoms . Preferred betaines are dimethylammonium hexanoate of 12 to 18 carbon atoms and dimethyl (or diethyl) betaines of acylamidopropane (or ethane) of 10 to 18 carbon atoms.

Also suitable for use herein are complex betaine surfactants.

CATIÓNICOS SURFACTANT AGENTS Cationic surfactants suitable for use in the detergent compositions or components thereof described herein include the quaternary ammonium surfactants selected from N-alkyl or alkenyl ammonium mono-surfactants having from 6 to 16 carbon atoms, preferably from 6 to 10. carbon atoms wherein the remaining N positions are substituted with methyl, hydroxyethyl or hydroxypropyl groups. Another suitable group of cationic surfactants that can be used in the detergent compositions or components thereof are the cationic ester surfactants. The cationic ester surfactant is a compound preferably dispersible in water, which has surfactant properties and contains 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 422,8042, 4239660 and 4260529. In a preferred aspect the ester linkage and the cationically charged group are separated from one another in the surfactant molecule by a spacer group consisting of a chain comprising at least three atoms (ie chain with length of three atoms), preferably of 3 to 8 atoms, more preferably 3 to 5 atoms, much more preferably three atoms. The atoms that form the chain of the spacer group are selected from the group consisting of carbon atoms, nitrogen and oxygen, and any mixtures thereof, with the proviso that any nitrogen or oxygen atom in said chain is connected only with carbon atoms in the chain. In this way, spacer groups having, for example, links -OO- (ie, peroxide), -NN, and -NO-, are excluded, while spacer groups having, for example, CHson links included. In a preferred aspect the spacer group contains only carbon atoms, much more preferably the chain is a hydrocarbyl chain.

COMPOSITE DETERGENT IMPROVEMENT SOLUBLE IN WATER The detergent compositions or components thereof according to the present invention preferably contain a water soluble builder compound, typically present in the detergent compositions at a level of 1% to 70% by weight, preferably 10% to 70% by weight, much more preferably 20% to 60% by weight of the composition. Suitable 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 contains 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 ethers derived therefrom. Polycarboxyiates 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, also ether carboxylates and sulfinylcarboxylates. Carboxylates containing three carboxy groups include, in particular, water-soluble citrates, aconitrates and citraconates, as well as succinate derivatives such as carboxymethyloxysuccinates described in British Patent 1, 3379,241, Lactoxysuccinates described in British Patent 1, 389,732, and aminosuccinates described in Dutch Application 7205873, and the oxypolycarboxylate materials such as trica 2-oxa-1,1,3-propane rboxylates described in British Patent 1, 387,447. Polycarboxylates containing four carboxy groups include oxydisuccinates discussed in British Patent No. 1, 261, 829, 1, 1, 2,2-ethane, tetracarboxylates of 1,1, 3,3-propane and tetracarboxylates of 1, 1, 2,3-propane. Polycarboxylates containing sulfo substituents include the sulfosuccinate derivatives discussed in British Patents 1, 398,421 and 1,398,422 and in US Patent 3,936,448, and the sulfonated pyrolysed citrates described in British Patent 1, 439,000. Preferred polycarboxylates are hydroxycarboxylates containing up to three carboxy groups per molecule, more particularly citrates. Acids originating from monomeric or oligomeric polycarboxylate chelating agents or mixtures thereof with their salts, for example citric acid or citrate / citric acid mixtures 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 washing conditions, are water soluble builders useful herein. The tripolyphosphates of alkali metals, sodium, potassium and ammonium pyrophosphate, sodium pyrophosphate, potassium and ammonium, sodium and potassium orthophosphate, polymetallic sodium phosphate in which the degree of polymerization reaches about 6 to 21, and salts of picalic acid, are suitable examples of water-soluble phosphate builders.

COMPOSITE DETERGENT IMPROVEMENT PARTIALLY SOLUBLE OR INSOLUBLE The detergent compositions or compositions thereof according to the present invention may contain a partially soluble or insoluble builder compound, typically present in detergent compositions at a level of 1% to 80% by weight, preferably 10% to 70% by weight, much more preferably from 20% to 60% by weight of the composition. Examples of mostly water-insoluble detergency builders include sodium aluminosilicates. Suitable aluminosilicate zeolites have the unit cell formula Naz [(AIO2) z (SiO2) y] xH2O where z and y are 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, more preferable from 10 to 264. The aluminosilicate materials are in hydrated form and preferably are crystalline, and contain from 10% to 28%, more preferably from 18% to 22% water in agglutinated form. The aluminosilicate zeolites may be natural materials, but preferably they are synthetically derived. Synthetic change materials of crystalline aluminosilicate are available under the designations Zeolite A, Zeolite B, Zeolite P, Zeolite X, Zeolite HS and mixtures thereof. Zeolite A has the formula Nai2 [AIO2) i2 (Si? 2) i2] .xH2O wherein x is from 20 to 30, especially 27. Zeolite X has the formula Na86 [(AIO2) 86 (SiO2) 106] .276H2O. Another preferred aluminosilicate zeolite is the zeolite MAP builder. Zeolite MAP can be present at a level of 1% to 80%, more 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 P-type zeolite having a silicon to aluminum ratio not greater than 1.33, preferably within the range of 0.9 to 1.33 and more preferably within the range of 0.9 to 1.2. Of particular interest is zeolite MAP which has a silicon to aluminum ratio not greater than 1.15 and, more particularly, not greater than 1.07. In a preferred aspect the zeolite MAP builder has a particle size expressed as a d50 value from 1.0 to 10.0 microns, more preferably from 2.0 to 7.0 microns, much more preferably from 2.5 to 5.0 microns. The d50 value indicates that 50% by weight of the particles have a smaller diameter than they appear. The particle size in particular can be determined by conventional analytical techniques such as microscopic determination using a scanning electron microscope or by means of a laser granulometer. Other methods of establishing d50 values are discussed in EP 384070A.

HEAVY METAL ION SEQUESTRANT The detergent compositions of the invention preferably contain as an optional component a heavy metal ion sequestrant. By heavy metal ion sequestrant is meant herein components that act to sequester (chelate) heavy metal ions. These components may also have calcium and magnesium chelating capacity, but preferably show selectivity for binding heavy metal ions such as iron, manganese and copper. Heavy metal ion sequestrants are generally present at a level from 0.005% to 20%, preferably from 0.1% to 10%, more preferably from 0.25% to 7.5% and much more preferably from 0.5% to 5% by weight of the compositions Heavy metal ion sequestrants for use herein include organic phosphonates, such as the amino polyalkylenes (alkylene phosphonates), alkali metal ethane-1-hydroxy diphosphonates, and nitrile trimethylene phosphonates. Preferred among the above species are the penta triamine diethylene (methylene phosphonate), ethylene tri-diamine (methylene phosphonate), tetra diamine of hexamethylene (methylene phosphonate) and 1,1-hydroxyethylene diphosphonate. Other heavy metal ion sequestrants for use herein include nitrilotriacetic acid and polyaminocarboxylic acids such as ethylene diamine tetraacetic acid, teylenetriamine pentacetic acid, ethylene diamine disuccinic acid, ethylene diamine digultárico acid, 2-hydroxypropylenediamine disuccinic acid, or any salts thereof. Especially preferred is ethylene diamine N, N-disuccinic acid (EDDS) of 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 methanediacetic acid, described in EP-A-317,542 and EP-A-399,133. The N-2-hydroxypropylsulfonic acid iminodiacetic acid and N-carboxymethyl N-2-hydroxypropyl-3-sulfonic acid aspartic acid sequestrants described in EP-A-516,102 are also suitable here. The sequestrants ß-alanine-N, N'-diacetic acid, N-N'N'-diacetic aspartic acid, N-monoacetic acid aspartic acid and iminodisuccinic acid described in EP-A-509,382 are also suitable. EP-A-476,257 describes the appropriate amine-based sequestrants. EP-A-510,331 describes suitable sequestrants derived from collagen, keratin or casein. EP-A-528,859 discloses an appropriate alkyliminodiacetic acid sequestrant. Dipicolinic acid and 2-phosphonobutane- 1, 2,4-tricarboxylic are also suitable. Glycinamido-N, N'-disuccinic acid (GADS), ethylenediamine-N, N'-diglutaric acid (EDDG) and 2-hydroxypropylenediamine-N, N'-disuccinic acid (HPDDS) are also suitable.

BLANCURA CATALYST The oxygen bleach system may contain a transition metal containing whiteness catalyst. An appropriate type of whiteness catalyst is a catalyst system containing a transition metal cation of defined brightness catalytic activity, such as copper, iron or manganese cations, an auxiliary metal cation having little or no catalytic whiteness activity, as zinc or aluminum cations, and a sequestrant having defined stability constants for the catalytic and auxiliary metal cations, particularly ethylenediaminetetraacetic acid, ethylenediaminetetra (methylenephosphoric acid) and water soluble salts thereof. These catalysts are discussed in US 4,430,243. Other types of whiteness catalysts include the manganese-based complexes discussed in US Patents 5,246,621 and US 5,244,594. Preferred examples of these catalysts include Mn? V2 (uO) 3 (1, 4,7-trimethyl-1, 4,7-triazacyclononane) 2- (PF6) 2, Mn ", 2 (uO) 1 (u-OAc) 2 (1, 4,7-trimethyl-1, 4,7-triazacyclononane) 2- (CIO4) 2, Mnlv4 (uO) 6 (1, 4,7-triazacyclononane) 4- (CIO4) 2, MnlM Mn ? v 4 (uO) 1 (u-OAc) 2 (1, 4,7-trimetyl-1, 4,7-triazacyclononane) 2- (CIO 4) 3, and mixtures thereof. Others are described in European patent application publication 549,272. Other ligands suitable for use herein include 1, 5,9-trimethyl-1, 5,9-triazacyclododecane, 2-methyl-1,4,7-triazacyclononane, 2-methyl-1, 4,7-triazacyclononane, 1, 2,4,7-tetramethyl-1,4,7-triazacyclononane, and mixtures thereof. Others are described in European patent application publication 549,272. Other ligands suitable for use herein include, 5,9-trimethyl-1, 5,9-triazacyclododecane, 2-methyl-1,4,7-triazacyclononane, 2-methyl-1, 4,7-triazacyclononane, 1, 2,4,7-tetramethyl-1,4,7-triazacyclononane, and mixtures thereof. The whiteness catalysts useful herein may also be selected as suitable for the present invention. For examples of suitable whiteness catalysts see US Pat. Nos. 4,246,612 and 5,227,084. See also US 5,194,416 which teaches manganese (IV) mononuclear complexes such as Mn (1,4,7-trimethyl-1,4,7-triazacyclononane) (OCH 3) 3- (PF 6). Still another type of whiteness catalyst, such as that discussed in US Pat. No. 5,114,606, is a water soluble complex of manganese (III) and / or (IV) with a ligand that is a non-carboxylated polyhydroxy compound having at least three groups Consecutive C-OH. Preferred ligands include sorbitol, iditol, dulsitol, mannitol, xylitol, arabitol, adonitol, mesoleritritol, lactose, and mixtures thereof.

US Patent 5,114,611 shows a whiteness catalyst containing a complex of transition metals, including Mn, Co, Fe, or Cu, with a non- (macro) -cyclic ligand. These ligands have the formula: R2 R3 R1-N = C-B-C = N-R4 wherein R1, R2, R3 and R4 are each selected from H, alkyl and aryl groups substituted such that each of R1-N = C-R2 and R3-C = N-R4 form a ring of five or six members. Said ring can be substituted later. B is a linking group selected from O, S, CR5R6, NR7 and C = 0, wherein R5, R6 and R7 may each be H, alkyl or aryl groups, including substituted or unsubstituted groups. Preferred ligands include pyridine, pyridazine, pyrimidine, pyrazine, imidazole, pyrazole, and triazole rings. Optionally, said rings can be substituted with substituents such as alkyl, aryl, alkoxy, halide, and nitro. The ligand 2,2'-bispyridylamine is particularly preferred. Preferred whiteness catalysts include Co, Cu, Mn, Fe, -bispyridylmethane and -bispyridylamine complexes. Highly preferred catalysts include Co (2,2'-bispyridyl amine) CI2, Di (isothiocyanate) bispyridylamine-cobalt (II), trisdipyridylamine-cobalt (II) percoyrate, Co (2,2-bispyridylamine) 2O2Cl? 4, copper bis- (2,2'-bispyridylamine) perchlorate (ll), iron (II) tris (di-2-pyridylamine) perchlorate, and mixtures thereof.

Other examples include binuclear Mn complexes with tetra-N-toothed and bi-N-toothed ligands, including ^ Mn '^ u-O ^ Mn1 ^) - and [Bipy2) Mnlll (u-0) 2Mnlvbipy2] - (Cl? 4) 3. Other whiteness catalysts are described, for example, in European patent application publication 408,131 (cobalt composite catalysts), publications of European patent applications 384,503 and 306,089 (metallo-porphyrin catalysts), US 4,728,455 (Manganese catalyst / multidentate ligand), US 4,711,748 and European patent application publication 224,952 (absorbed manganese or aluminosilicate catalyst), US 4,601, 845 (aluminosilicate support with manganese and zinc or magnesium salt), US 4,626,373 magnesium catalyst / ligand ), US 4,119,557 (ferric complex catalyst), German patent specification 2,054,019 (cobalt chelating catalyst), Canadian 866,191 (transition metals containing salts), US 4,430,243 (chelants with manganese cations and non-catalytic metal cations), and US 4,728,455 (manganese gluconate catalysts). The whiteness catalyst is typically used in a catalytically effective amount in the compositions and methods herein. By "catalytically effective amount" is meant an amount that is sufficient, under whatever comparative test conditions are employed, to improve the whiteness and removal of dirt or dirty of interest from the target substrate. These test conditions may vary, depending on the type of washing application used and the user's habits. Some users choose to use very hot water; others use warm water or even cold water in the washing operations, of course, the catalytic performance of the whiteness catalyst will be affected by these considerations, and the whiteness catalyst levels used in the fully formulated detergent and whitening compositions can be adjusted appropriately. As a practical matter, and not as a form of limitation, the compositions and processes herein can be adjusted to provide at least one part per ten million of the active whiteness catalyst species in the wash solution. To illustrate this point further, on the order of 3 micromolar the manganese catalyst is effective at 40 ° C, pH 10 under European conditions using perborate and a bleaching precursor. An increase in concentration of 3-5 folds may be required to achieve the same results.

ENZYME Another preferred preferred ingredient in detergent compositions or components thereof is an additional or more enzyme. Additional preferred enzyme materials include the commercially available lipases, cutinases, amylases, neutral and alkaline proteases, cellulases, endolases, esterases, pectinases, lactases and peroxidases and conventionally incorporated into the detergent compositions. Suitable enzymes are discussed in US Patents 3,519,570 and 3,533,139.

Preferred commercially available protease enzymes include those marketed under the trademarks Alcalase, Savinase, Primase, Durazym, and Esperase by Industrias Novo A / S (Denmark), which are sold under the commercial names Maxtase, Maxacal, and Maxapem by Gist-Brocades, those marketed by Genencor International, and those sold under the trade name Opticlean and Optimase by Solvary Enzimes. The protease enzyme may be incorporated in the compositions according to the invention at a level of 0.0001% to 4% active enzyme per weight of the composition. Preferred amylases include, for example, O-amylases obtained from a special strain of B licheniformis, described in greater detail in GB-1, 269,839 (Novo). Preferred commercial amylases include, for example, those sold under the trademark Rapidase by Gist-Brocades, and those marketed under the trade name Termamyl and BAN by Novo Industries A / S. The amylase enzyme can be incorporated into the composition according to the invention at a level of 0.0001% to 2% of active enzyme per weight of the composition. The lipolytic enzyme may be present at active lipolytic enzyme levels of 0.0001% to 2% by weight, preferably 0.001% to 1% by weight, much more preferably 0.001% to 0.5% by weight of the compositions. The lipase can be of fungoid or bacterial origin, being obtained, for example, from the lipase-producing strain of Humicola sp., Thermomvces sp. or Pseudomonas sp., including Pseudomonas pseudoalcaligenes or Pseudomas fluorescens. Lipases from chemically or genetically modified mutants of these strains are also useful herein.

A preferred lipase is derived from Pseudomonas pseudoalkali. which is described in the European Patent Conferred, EP-B-0218272. Another preferred lipase here is obtained by cloning the Humicholum lanqinosa and expressing the gene in Aspergillus oryza, as host, as described in the European Patent Application, EP-A-0258 068, which is commercially available from Novo Industries A / S, Bagsvaerd, Denmark, under the trade name Lipolase Lipase is also described in US Pat. No. 4,810,414, to Huge-Jensen and coauthors, issued March 7, 1989.

ORGANIC POLYMERIC COMPOSITE Organic polymeric compounds are preferred additional components of the detergent compositions or components thereof according to the present invention, and are preferably present as components of any particulate components where they can act to bind the particulate component together . By organic polymeric compound is meant here essentially any organic polymeric compound commonly used as dispersants and anti-redeposition agents and slurry suspending agents in detergent compositions, including any of the high molecular weight organic polymeric compounds described herein as clay flocculating agents , not being an ethoxylated quaternized clay (poly) amine remover / anti-redeposition agent according to 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%, much more preferably from 1% to 10% by weight of the compositions. Examples of organic polymeric compounds include the organic homo- or co-polymeric water-soluble polycarboxylic acids or their salts in which the polycarboxylic acid comprises at least two carboxyl radicals separated from one another by not more than two carbon atoms. The polymers of the latter type are discussed in GB-A-1, 596,756. Examples of these salts are the polyacrylates of PMt 1000-5000 and their copolymers with maleic anhydride, such as copolymers having a molecular weight of 2000 to 100,000, especially 40,000 to 80,000. The polyamine compounds are useful herein, including those aspartic acid derivatives such as those discussed in EP-A-305282, EP-A-305283 and EP-A-351629. Terpolymers containing selected monomer units of maleic acid, acrylic acid, polyaspartic acid and vinyl alcohol, particularly those having an average molecular weight of ,000 to 10,000, are also appropriate here. Other organic polymeric compounds suitable for incorporation into the compositions detergents of the present invention include cellulose derivatives, such as methylcellulose, carboxymethylcellulose, hydroxypropylmethylcellulose and hydroxyethylcellulose. Additional useful organic polymeric compounds are polyethylene glycols, particularly those of molecular weight 1000-10000, more particularly 2000 to 8000 and much more preferable about 4000.

FOAM SUPPRESSION SYSTEM When the detergent components or compositions are formulated for use in washing machine compositions, they preferably contain a foam suppressant system present at a level of from 0.01% to 15%, preferably from 0.05% to 10%, much more preferably from 0.1% to 5% by weight of the composition. The foam suppressor systems for use herein may contain essentially any known antifoam compound, including for example, silicone anti-foaming compounds and 2-alkylalcanol antifoaming compounds. "By antifoaming compound" is meant here any compound or mixtures of compounds that act in such a way as to reduce the foam or soapy water activity produced by a solution of detergent composition, particularly in the presence of agitation of that solution.

Preferred defoaming compounds for use herein are the antifoam silicone compounds defined herein as any compound that includes a silicone component. These silicone defoaming compounds also typically contain a silica component. The term "silicone" as used herein, and in general within the industry, comprises a variety of relatively high molecular weight polymers containing siloxane units and hydrocarbyl groups of various types. The preferred antifoam silicone compounds are the siloxanes, particularly the polydimethylsiloxanes having trimethylsilyl units with closed ends. Other suitable defoaming compounds include the monocarboxylic fatty acids and soluble salts thereof. These materials are described in US Patent 2,954,347, issued September 27, 1960 to Wayne St. John. The monocarboxylic fatty acids, and salts thereof, for use as foam supersores, 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 sodium, potassium and lithium salts, and ammonium and alkanolammonium salts. Other suitable antifoaming compounds include, for example, high molecular weight fatty esters (for example, fatty acid triglycerides), fatty acid esters of monovalent alcohols, aliphatic ketones of from 18 to 40 carbon atoms (for example stearone), aminotriazines N-alkylated as tri- to hexa-alkylmelamines or di- to tetra-alkyldiamino- chlortriazines formed as cyanuric chloride products with two or three moles of a primary or secondary amine containing 1 to 24 carbon atoms, propylene oxide, bi-stearic amido acid and monostearyl phosphates of di-alkali metals (eg, sodium, potassium) , lithium) and phosphate esters. A preferred foam suppression system comprises: (a) antifoam compound, preferably a silicone antifoam compound, much more preferably a silicone antifoam compound containing in combination (i) polydimethyl siloxane, at a level of 50% to 99%, preferably 75% to 95% by weight of the anti-foaming silicone compound; and (ii) silica, at a level of 1% to 50%, preferably 5% to 25% by weight of the silicone / antifoam compound. wherein said silica / antifoam silicone compound is incorporated at a level of 5% to 50%, preferably 10% to 40% by weight; (b) a dispersant compound, which much more preferably contains a polyamide silicone glycol copolymer with a polyoxyalkylene content of 72% -78% and a ratio of ethylene oxide to propylene oxide of 1: 09 to 1: 1.1, at a 0.5% to 10% level, preferably 1% to 10% by weight; a particularly preferred polyamide silicone glycol copolymer of this type is DCO544, commercially available from DOW Corning under the tradename DCO544; (c) an inert fluid carrier compound, which much more preferably contains an ethoxylated alcohol of 16 to 18 carbon atoms, with a degree of ethoxylation from 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 suppressant system is described in EP-A-0210731 and contains an antifoam silicone compound and an organic carrier material having a melting point in the range of 50 ° C to 85 ° C, wherein the material Organic carrier contains a monoester of glycerol and a fatty acid with a carbon chain containing 12 to 20 carbon atoms. EP-A-0210721 discusses other preferred particulate foam suppressor systems wherein the organic carrier material is fatty acid or alcohol with a carbon chain containing from 12 to 20 carbon atoms, or a mixture thereof, with a point of fusion of 45 ° C to 80 ° C.

POLYMERIC AGENTS OF COLOR TRANSFER INHIBITION The detergent components or compositions may also contain from 0.01% to 10%, preferably from 0.05% to 0.5% by weight of color transfer inhibiting polymeric agents. Polymeric color transfer inhibiting agents are preferably selected from N-oxide polymers, N-vinylpyrrolidone and N-vinylimidazole copolymers, polyvinylpyrrolidone polymers or combinations thereof, wherein these polymers can be cross-linked polymers. a) POLYMER N-OXIDE POLYAMINE The N-oxide polyamine polymers suitable for use herein, contain units having the following structural formula: P (I) Ax R where P is a polymerizable unit, and O O O A is NC, CO, C, -O-, -S-, -N-; x is 0 or 1; R are aliphatic, aliphatic, ethoxylated, aromatic, heterocyclic or alicyclic groups or any combination thereof wherein the nitrogen of the N-O group may be attached or where the nitrogen of the N-O group is part of these groups. The N-O group can be represented by the following general structures: O O (R1) x-N- (R2) y; or N- (R?) x (R3) z wherein R1, R2 and R3 are aliphatic, aromatic, heterocyclic or alicyclic groups or combinations thereof, xo / yyo / yz is 0 or 1 and wherein the nitrogen of the NO group may be attached or wherein 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 connected to the polymeric backbone or a combination of both. The appropriate polyamine N-oxides wherein the N-O group forms part of the polymerizable unit contain N-polyamine oxides wherein R is selected from aliphatic, aromatic, alicyclic or heterocyclic groups. A class of said polyamine N-oxides comprises the group of N-oxides of poiiamine wherein 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 as pyrridine, pyrrole, imidazole, pyrrolidine, piperidine, quinoline, acridine and derivatives thereof. Other suitable polyamine N-oxides are the polyamine acids in which the N-O group is connected 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, heterocyclic or alicyclic group wherein the nitrogen of the functional group N-O is part of said group R. Examples of these classes are the polyamine oxides wherein R is a heterocyclic compound such as pyrridine, pyrrole, imidazole and derivatives thereof. The polyamine N-oxides can be obtained in at least some degree of polymerization. The degree of polymerization is not critical as long as the material has the solubility power in water and suspension of desired grime. Typically, the average molecular weight is within the range of 500 to 1,000,000. b) COPOLYMERS OF N-VINILPIRROLIDONE AND N-VINYLIMIDAZOLE The copolymers of N-vinylimidazole and N-vinylpyrrolidone with an average molecular weight range of 5,000 to 50,000 are appropriate herein. Preferred copolymers have a molar ratio of N-vinylimidazole to N-vinylpyrrolidone from 1 to 0.2. c) Polyvinylpyrrolidone The detergent compositions herein can also use polyvinyl pyrrolidone ("PVP") with an average molecular weight of 2,500 to 400,000. Suitable polyvinylpyrrolidones are those commercially available from ISP Corporation, New York, NY and Montreal, Canada under the product names PVP K-15 (viscosity of molecular weight of 10,000), PVP K-30 (weight 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 that are commercially available from BASF Cooperation include Sokalan HP 165 and Sokalan HP 12. d) POUVINYLOXAZOLIDONE The detergent compositions herein can also use polyvinyloxazolidones as polymeric color transfer inhibiting agents. 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 color transfer inhibiting agent. Said polyvinylimidazoles preferably have an average molecular weight of 2,500 to 400,000.

OPTICAL POLISHER The detergent compositions herein also optionally contain from 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 R1 is selected from anilino, N-2-bis-hydroxyethyl and NH-2-hydroxyethyl; R 2 is selected from N-2-bis-hydroethyl, N-2-hydroxyethyl-N-methylamino, morphino, chloro and amino; and M is a salt-forming cation such as sodium or potassium. When in the above formula, R1 is anilino, R2 is N-2-bis-hydroxyethyl and M is a cation like sodium, the brightener is acid 4,4 ', - bis [(4-anilino-6- (n-2 -b.s-hydroxyethyl) -s-triazine-2-yl) amino] -2,2'-stilbenedisulfonic acid and disodium salt. This particular species of brighteners 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 R1 is anilino, R2 is N-2-hydroxyethyl-N-2-methylamino and M is a cation such as sodium, the brightener is disodium salt of 4,4'-bis [(4-anilino-6 - (N-2-hydroxyethyl-N-methylamino) -s-triazine-2-yl) amino] 2,2'-stilbenedisulfonic. This particular kind of brightener is marketed under the trade name Tinopal AMS-GX by Ciba Geigy Corporation. When in the above formula R1 is anilino, R2 is morpholine and M is a cation such as sodium, the brightener is disodium salt of 4,4'-bis - [(4-anilino-6-morpholino-s-triazine-2- ilo) amino] 2,2'-stilbenedisulfonic acid. This particular kind of brightener is marketed under the trade name Tinopal AMS-GX by Ciba Geigy Corporation.

POLIMERIC AGENT ELIMINATOR OF MUGRE Known polymeric soil removal agents, hereinafter "SRA" can optionally be employed in the present detergent compositions. If they are used, the SRAs will generally contain 0. 01% to 10.0%, typically from 0.1% to 5%, preferably from 0.2% to 3.0% by weight, of the compositions. Preferred SRAs typically have hydrophilic segments to hydrophilize the surface of the hydrophobic fibers such as polyester and nylon, and hydrophobic segments to deposit on the hydrophobic fibers and remain attached to them during the execution of the washing and rinsing cycles, thus serving as an anchor for the hydrophilic segments. This can cause spots that occur subsequent to SRA treatment to be more easily cleansed in subsequent washing procedures. Preferred SRAs include oligomeric terphthalate esters, typically prepared by methods involving at least one transesterification / oligomerization, often with a metal catalyst such as a titanium (IV) alkoxide. These esters can be produced by using additional monomers capable of being incorporated into the ester structure through one, two, three, four or more positions, without, of course, forming a global dense cross-linking structure. Suitable SRAs include a sulphonated product of a substantially linear oligomeric ester consisting of an oligomeric ester backbone of terephthaloyl and oxyalkylenoxy repeat units and sulfonated end portions derived from allyl covalently connected to the backbone, for example, as described in US 4,968,451 from November 6, 1990 to JJ Scheibel and E.P. Gosselink. These oligomeric esters can be prepared by: (a) ethoxylation of allyl alcohol; (b) reacting the product of (a) with dimethylterephthalate ("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 SRAs include end polyesters coated with polyesters of 1, 2-propylene / polyethylene terephthalate from US 4,711, 730, December 8, 1987 to Gosseiink and co-inventors, for example those produced by transesterification / oligomerization of poly (ethylene glycol) methyl ether, DMT, PG and poly (ethylene glycol) ("PEG"). Other examples of SRA include: partially and fully anionic oligomeric esters of US covered terminals 4,721, 580, January 26, 1988 to Gosselink, such as ethylene glycol oligomers ("EG"), PG, DMT, and Na ~ 3,6-dioxa-8-hydroxyoctanesulfonate; the non-ionic polyester block oligomeric compounds covered in US 4,702,857, October 27, 1987 to Gosselink, for example produced from DMT, PEG methyl (Me) -coated and EG and / or PG, or a combination of DMT, EG and / or PG, ME-coated PEG and Na-dimethyl-5-sulfoisophthalate, and the anionic esters of covered terminal terphthalates, especially sulfoaroil, from US 4,877,896, October 31, 1989, to Maldonado, Gosselink and co-inventors, the last typical SRAs useful in both laundry and fabric conditioning products, one example being an ester composition made of monosodium salt of m-sulfobenzoic acid, PG and DMT, optionally but preferably containing additional added PEG, for example, PEG 3400. SRAs also include: simple copolymer blocks of ethylene terephthalate or propylene terephthalate with polyethylene oxide or polypropylene oxide terephthalate, see US 3,959,230 to Hays, May 25, 19 76 and US 3,893,929 to Bassadur, July 8, 1975; cellulose derivatives such as hydroxyether cellulosic polymers available as METHOCEL from Dow; the alkyl celluloses of 1 to 4 carbon atoms and celluloses of hydroxyalkyl of 4 carbon atoms, see US 4,000,093, dated December 28, 1976 to Nicol, and co-inventors; and the methyl cellulose ethers having an average degree of substitution (methyl) per anhydroglucose unit of 1.6 to about 2.3 and a solution viscosity of about 80 to 120 centipoise measured at 20 ° C as a 2% aqueous solution. These materials are available as METOLOSA SM100 and METOLOSA SM200, which are the commercial names of the methyl cellulose ethers manufactured by Shin-etsu Kagaku Kogyo KK. Additional classes of SRAs include (I) nonionic terephthalates which use dissociative coupling agents to link the polymeric ester structures, see US 4,201, 824, Violland and co-inventors, and US 4,240,918 to Lagasse and co-inventors; and (II) SRA with groups ends! carboxylates made by addition of trimethylic anhydride to known SRAs to convert terminal hydroxyl groups into trimellitate esters. With the proper selection of catalyst, trimellitic anhydride forms bonds to the polymer terminals through an isolated carboxylic acid ester or trimellitic anhydride rather than by opening the anhydride linkage. Nonionic or anionic SRAs can be used as starting materials as long as they have hydroxyl end groups that can be esterified. See US 4,525,524 to Tung and co-inventors. Other classes include: (III) anionic terephthalate-based SRA of the urethane linkage variety, see US 4,201, 824, Violland and co-inventors.

OTHER OPTIONAL INGREDIENTS Other optional ingredients suitable for inclusion in the compositions of the invention include perfumes, colors and filler salts, with sodium sulfate being the preferred filler salt.

DETERGENT FORMULATION WITH WASH pH ALMOST NEUTRAL While the detergent compositions of the present invention are operative within a wide range of wash pH (eg, from about 5 to 12), they are particularly suitable when formulated to provide an almost neutral wash pH, ie, a pH of about 7 to 10.5 at a concentration of about 0.1 to 2% by weight in water at 20 ° C. The formulations with almost neutral wash pH are better for the stability of the enzymes and to prevent stains from settling. In these formulations, the washing pH is preferably from about 7.0 to 10.5, more preferable from 8.0 to 10.5, much preferable from 8.0 to 9.0. Preferred detergent formulations with almost neutral wash pH are discussed in European patent application 83.200688.6, registered on May 16, 1983, by J.H.M. Wertz and P.C.E. Goffinet. Extremely preferred compositions of this type also preferably contain about 2 to 10% by weight of citric acid and minor amounts (eg, less than about 20% by weight) of neutralizing agents, stabilizing agents, phase regulators, hydrotropes, enzymes, enzyme stabilizing agents, polyacids, foam regulators, opacifiers, antioxidants, bactericides, dyes, perfumes and brighteners, such as those described in US Patent 4,285,841 to Barrat and co-inventors, issued August 25, 1981 (incorporated herein by reference).

FORM OF COMPOSITIONS The detergent component of the invention can be produced by a variety of methods, including dry blending and agglomeration of the various components contained in the detergent component. The detergent component preferably forms part of a detergent composition. The compositions according to the invention can take a variety of physical forms including granular forms, tablets, flakes, and bars. The compositions are particularly so-called concentrated granular detergent compositions adapted to be added to a washing machine by means of a dispensing device placed in the drum of the machine with the laundry load dirty. The compositions according to the present invention can also be used in, or in combination with bleaching additive compositions, for example with chlorine bleach content.

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 removal / antiredeposition agent of clayey dirt 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 water-soluble cationic compounds for removal / anti-redeposition of clay soil, should preferably be such that no more than 15% of the particles are larger than 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 10% to 50% of the particles have a particle size of 0.2 mm to 0.7 mm in diameter. The term "average particle size" as defined herein is calculated by sieving a sample of the composition in a number of fractions (typically 5 fractions) over a series of sieves, preferably Tyler's sieve. The weight of the fractions thus obtained is plotted against the size of the opening of the sieves. The average particle size is taken by the size of the sieve aperture in which 50% by weight of the sample would pass.

The bulk density of the granular detergent compositions is typically at least 600 g / liter, more preferably from 650 g / liter to 1200 g / liter. The volumetric density is measured by means of a simple funnel and a cup device consisting of a conical funnel rigidly molded on a base and provided with a flap valve at its lower end to allow the contents of the funnel to be emptied into a cup axially aligned cylindrical arranged 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 end 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 the measurement, the funnel is filled with dust by manual emptying, the flap valve opens allowing the powder to fill the cup. The full cup is removed from the frame and excess powder is removed from the cup by passing a sharp straight implement, eg, a knife, through the top edge. The filled cup is then weighed and the value obtained for the powder weight is bent to provide the mass density in g / liter. The measurements are repeated if required. The compacted solids can be manufactured using any suitable compaction process, such as tabletting, briquetting or extrusion, preferably tableting. Preferred tablets for use in dishwashing processes, are manufactured using a press standard rotary tapping using compression forces of 5 to 13 KN / cm2, much more preferable from 5 to 11 KN / cm2 so that the compacted solid has a minimum hardness of 176N to 275N, preferably 195N to 245N, measured by a test hardness C100 as supplied by I. Holland Instuments. This process 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 aqueous solution.

WASHING METHOD FOR LAUNDRY The washing machine washing methods of the present invention typically comprise a laundry grime treatment with an aqueous washing solution in a washing machine, an effective amount of a laundry detergent composition having been dissolved or dispensed thereinto according to the invention. . By effective amount of the detergent composition, it is to be understood that from 10 g to 300 g of product dissolved or dispersed in a washing solution with a volume of 5 to 65 liters, as are the typical product doses and volumes of washing solution commonly used in conventional methods of washing in the washing machine. In a preferred use aspect, a dispensing device is employed in the washing method. The dispensing device is charged with the detergent product, and is used to introduce the product directly into the drum of the detergent. washing machine before starting the washing cycle. Its volume capacity must be such that it is capable of containing sufficient detergent product as would normally be used in the washing method. The dispensing device containing the detergent product is placed inside the drum before the start of the washing, before, or simultaneously with or after the washing machine has been loaded with clothes. At the beginning of the washing cycle of the washing machine, the water is introduced into the drum and it rotates periodically. The design of the dispensing device should be such as to allow the dry detergent product to be contained but to allow the supply of this product during the wash cycle in response to its agitation while the drum is rotating and also as a result of its contact with the wash water. To allow the supply of the detergent product during washing, the device must possess a number of openings through which the product can pass. Alternatively, the device may be made of a liquid permeable material, but impermeable to the solid product, which will allow the delivery of the dissolved product. Preferably, the detergent product will be released rapidly at the beginning of the wash cycle, whereby it will temporarily provide high localized concentrations of product in the drum of the washing machine in this phase of the washing cycle. Preferred dispensing devices are reusable and are 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 dispensing 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 1989, pages 41-46 also discloses especially preferred dispensing devices for use with granular laundry products which are of a type commonly known as the "granulette" Another preferred dispensing device for use with compositions of this invention is discussed in PCT Patent Application No. WO94 / 11562. Especially preferred dispensing devices are discussed in European Patent Application Publication Nos. 0343069 and 0343070. This latter application discusses a device containing a flexible cover in the form of a bag extending from a support ring delimiting an orifice, adapted the orifice to admit in the bag the sufficient product for a washing cycle in a washing procedure. A portion of the washing medium flows through the hole in the bag, dissolves the product, and the solution then passes out through the orifice into the washing medium. The support ring is provided with a sealing configuration to prevent the exit of the wet product, not dissolved. This configuration typically contains radially extending walls extending from a central core in a radiated wheel configuration, or a similar structure in which the walls will be helical in shape. Alternatively, the dispensing device may be a flexible container, such as a bag or sack. The bag can be fibrous construction covered with a waterproof protective material in such a way that retain the content, such as those discussed in Published European Patent Application No. 0018678. Alternatively, it may be formed of a water-insoluble synthetic polymeric material, provided with a seal at the edge or closure designed to break in aqueous medium, as those discussed in European Patent Application Publication Nos. 0011500, 0011501, 0011502, and 0011968. A convenient form of brittle water closure comprises a water soluble adhesive disposed along and sealing an edge of a sack formed by a film water-impermeable polymer such as polyethylene or polypropylene.

WASHING METHOD IN WASHER WASHING MACHINE Any suitable methods are considered for dishwashing in dishwashers, or cleaning dirty dishes, particularly silver. A preferred method for dishwashing in a dishwashing machine, comprises the treatment of the dirty articles selected from earthenware, glassware, concave containers, silverware, and coverings and mixtures thereof, with an aqueous liquid in which a liquid has been dissolved or dispensed. amount of component for washing in dishwashing machine, according to the invention. For an effective amount of the composition for dishwashing machine it should be understood that from 8 g to 60 g of dissolved or dispersed product in a washing solution of volume of 3 to 10 liters, as are the typical doses and volumes of wash solution commonly employed in conventional methods in dishwashers.

PACKAGING FOR COMPOSITIONS The commercially marketed versions of the bleaching compositions can be packaged in any suitable package, including those made of paper, cardboard, plastic materials and any suitable laminate. A preferred packaging version is described in European application 94921505.7.

ABBREVIATIONS USED IN THE EXAMPLES In detergent compositions, the abbreviated component identifications have the following meanings: LAS = Sodium alkyl benzene sulfonate of 12 carbon atoms TAS = Sodium tallow alkyl sulfate CxyAS = Sodium alkylsulphate of 1x to 1y carbon atoms C46SAS = (2,3) Sodium alkylsulphate secondary of 14 to 16 carbon atoms CxyEzS Sodium alkylsulphate of 1x to 1y carbon atoms condensed with z moles of ethylene oxide CxyEz Primary predominantly linear alcohol of 1x to 1y condensed carbon atoms with an average of z moles of ethylene oxide QAS R2-N + (CH3) 2 (C2H4OH) with R2 = 12 to 14 carbon atoms Linear sodium alkylcarboxylate soap derived from an 80/20 mixture of tallow and coconut oils CFAA (Coco) alkyl N-methyl glucamide of 12 to 14 carbon atoms TFAA Alkyl N-methyl glucamide of 16 to 18 carbon atoms TPKFA Fatty acids of whole cut exceeded of 12 to 14 carbon atoms STPP Anhydrous sodium tripolyphosphate TSPP Pyrophosphate Tetrasodium Zeolite A Hydrated sodium aluminosilicate of formula Na? 2 (AIO2SiO2) i2.27H2O with a primary particle size in the range of 0.1 to 10 micrometers Zeolite MAP = Hydrated sodium aluminosilicate MAP zeolite with a silica to aluminum ratio of 1.07 NaSKS-6 = Stratified crystalline silicate of formula - Na2Si2O5 Citric acid = Anhydrous citric acid Borate = Sodium borate Carbonate = Sodium carbonate anhydrous with a size of particle between 200μm and 900μm Bicarbonate = Anhydrous sodium bicarbonate with a particle size distribution between 400μm and 1200μm Silicate = Amorphous sodium silicate (Si02: Na20 = 2.0: 1) Sulphate = Anhydrous sodium sulfate Citrate = Citrate dihydrate trisodium activity 86.4% with a particle size distribution between 425μm and 850μm MA / AA = Maleic acid / acrylic copolymer 1: 4, average molecular weight around 70,000 AA = Sodium polyacrylate polymer of average molecular weight 4,500 CMC = Sodium carboximethylcelulose Ether cellulose Ether of methylcellulose with a degree of polymerization of 650 available from Shin Etsu Chemicals Protease Proteolytic enzyme activity of 4KNPU / g sold by NOVO Industries A / S under the trade name Savinase. Alcalase Proteolytic enzyme activity 3AU / g sold by NOVO Industries A / S Cellulase Activity cellulite enzyme 1000 CEVU / g sold by NOVO Industries A / S under the trade name Carezyme. Amylase Activity amylolytic enzyme 120KNU / g sold by NOVO Industries A / S, under the trade name Termamyl 120T Lipase Lipolytic enzyme activity 100KLU / g sold by NOVO Industries A / S under the trade name Lipolase Endolase Enzyme endoglucanase with activity 3000 CEVU / g sold by NOVO Industries A / S PB4 Sodium perborate tetrahydrate of nominal formula NaBO2.3H2O.H2O2 PB1 Anhydrous sodium perborate bleach of nominal formula NaBO2.H2O2 Percarbonate = Sodium percarbonate of nominal formula 2Na2CO3.3H2O2 NAC-OBS = Nonanamido hydroxybenzene sulfonate caproil) in the sodium salt form. NACA = 6-Nonylamino-6-oxo-caproic acid NOBS = Nonanoyloxybenzene sulfonate in the form of sodium salt TAED = Tetraacetylethylenediamine DTPA = Diethylenetriamine pentaacetic acid DTPMP = Penta-diethylenetriamine (methylene phosphonate), marketed by Monsanto under the trademark Dequest 2060 Photoactivated = Sulfonated zinc phthalocyanine encapsulated in dextrin soluble polymer bleach Brightener 1 = 4,4'-bis (2-sulphotyryl) biphenyl disodium Brightener 2 = 4,4'-bis (4-anilino-6-morpholino-1, 3,5-triazin-2-yl) amino) stilbene Disodium 2,2'-disulfonate HEDP = 1, 1-hydroxyethane diphosphonic acid EDDS = N, N'-disuccinic acid of ethylenediamine QEAI = bis ((C2H5O) (C2H4O) n) (CH3) -N + -C6H12-N + - (CH3) bs (( C2H5O) - (C2H4O) n), where n = from 20 to 30 QEA2 b1s ((C2H5O) - (C2H4O) n) (CH3) -N + R ?, where Ri is an alkyl group of 4 to 12 carbon atoms and n = 20 to 30 QEA3 tri (bis ((C2H5O) - (C2H4O) n) (CH3) -N +) - (CONC3H6)) - C3H6O, where n = from 20 to 26 PEGx Polyethylene glycol, with a molecular weight of x PEO Polyethylene oxide, with an average molecular weight of 50,000 TEPAE Tetraethylene pentaidine ethoxylate PVP Polyvinylpyrrolidone polymer PVNO N-oxide of polyvinylpyridine PVPVI Copolymer of polyvinylpyrrolidone and vinylimidazole SRP1 Sulfobenzoil and esters coated with oxyethyleneoxy and main structure terftaloil SRP2 Short block polymer dietoxylated poly (1, 2 propylene terphthalate) Defoaming Silicone Poiidimethylsiloxane foam controller with siloxane-oxyalkylene copolymer as a dispersing agent with a ratio of said foam controller to said dispersing agent from 10: 1 to 100: 1 Wax Paraffin Wax In the following examples all the levels are calculated as% by weight of the composition: EXAMPLE 1 The following high density granular laundry detergent compositions A to F of particular utility under European laundry washing conditions are examples according to the present invention: EXAMPLE 2 The following granular laundry detergent compositions G a I of particular utility under European laundry washing conditions were prepared according to the invention: EXAMPLE 3 The following detergent formulations of particular utility under the European washing machine conditions were prepared according to the invention.

EXAMPLE 4 The following granular detergent formulations were prepared according to the invention. The formulation N is particularly suitable for use under washing conditions in Japanese clothes washers. Formulations O to S are particularly suitable for use under the conditions of American clothes washers.

EXAMPLE 5 The following granular detergent formulations were prepared according to the invention. Formulations W and X are particularly useful under US washing machine conditions. And it is particularly useful under Japanese conditions of washing in a washing machine.

EXAMPLE 6 The following granular detergent formulations of particular utility under European washing conditions were prepared according to the invention: EXAMPLE 7 The following detergent compositions were prepared according to the present invention: EXAMPLE 8 The following detergent formulations were prepared according to the invention: EXAMPLE 9 The following high density granular laundry detergent compositions FF to KK were prepared according to the invention: EXAMPLE 10 The following detergent compositions were prepared according to the invention:

Claims (27)

NOVELTY OF THE INVENTION CLAIMS

1. - A granular detergent composition, containing: (a) an organic peroxyacid hydrophobic bleach system, capable of providing a hydrophobic organic peroxyacid compound; and (b) a water soluble cationic compound having removal properties / antiredeposition of clayey dirt, which is selected from the group consisting of: 1) ethoxylated cationic monoamines with the formula: R2 R2-N + -L-X R2

2) ethoxylated cationic diamines with the formula: (R3) d R3 (R3) d R3 X- L- M1- R1- N + - L- X or R3- M1- R1- N + - R or / / L L L L L X X X X X (R3) d 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 R4- [(A1) q - (R5) t-M2- L- X] p R2 4) mixtures thereof; O O O O O where A1 is - NC-, -NCO-, - NCN-, - CN-, - OCN-, R R R R R O O O O O - CO-, -OCO-, - OC-, - CNC- or - O- R R is H or alkyl or hydroxyalkyl of 1 to 4 carbon atoms, R1 is alkylene of 2 to 12 carbon atoms, hydroxyalkylene, alkenylene, arylene or alkarylene, or an oxyalkylene portion of 2 to 3 carbon atoms having 2 to about 20 oxyalkylene units, as long as NO bonds are not formed; each R2 is alkyl or hydroxyalkyl of 1 to 4 carbon atoms, the -L-X portion, or two R2 together form the portion - (CH2) rA2- (CH2) s-, where A2 is -O- or -CH2-, r is 1 or 2, s is 1 or 2 and r + s is 3 or 4; each R3 is alkyl or hydroxyalkyl of 1 to 8 carbon atoms, benzyl, the L-X portion, or two R3 or an R2 and R3 together form the - (CH2) rA2- (CH2) s- portion; R 4 is an alkyl, hydroxyalkyl, alkenyl, aryl or substituted alkaryl group of 3 to 12 carbon atoms having p substitution sites; R5 is alkenyl, hydroxyalkylene, alkenylene, arylene or alkarylene of 1 to 12 carbon atoms, or an oxyalkylene portion of 2 to 3 carbon atoms having from 2 to about 20 oxyalkylene units provided no bond is formed OO or ON; X is a non-ionic group selected from the group consisting of H, alkyl or hydroxyalkyl ester or alkyl groups of 1 to 4 carbon atoms, and mixtures thereof; L is a hydrophilic chain containing the polyoxyalkylene moiety - [(RdO) m (CH2CH2O) n] -; wherein R6 is alkylene or hydroxyalkylene of 3 to 4 carbon atoms and m and n are numbers such that the - (CH2CH2O) n- portion comprises at least about 50% by weight of said polyoxyalkylene portion; d is 1 when M2 is N + and 0 when M2 is N; n is at least about 16 for the said cationic monoamines, is at least about 6 for the said cationic diamines and is at least about 3 for the said cationic polyamines; p is from 3 to 8; q is 1 or 0; t is 1 or 0, provided t is 1 when q is 1; 2. A granular detergent composition according to claim 1, further characterized in that the proportion of said organic peroxyacid hydrophobic compound to said water-soluble cationic compound is from 20: 1 to 1: 2.

3. - A granular detergent composition according to claim 1 further characterized in that said cationic compound is present at a level of 0.1% 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 according to claim 1, further characterized in that said cationic compound is an ethoxylated cationic mopoamine and is characterized in that one R2 is methyl, two r2 are the portion LX, m is 0 and n is at least about 10%. 20.

6. A granular detergent composition according to any of claims 1 to 4, further characterized in that said cationic compound is an ethoxylated cationic diamine and is characterized in that R1 is an alkylene of 2 to 6 carbon atoms.

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

8. A granular detergent composition according to claim 6, further characterized in that the cationic compounds are characterized in that each R2 is methyl or the -L-X portion, each R3 is methyl and M1 and each M2 is a N + group.

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

10. - A detergent composition according to claim 1 further characterized in that said cationic compound is an ethoxylated cationic polyamine and is characterized in that R 4 is an alkyl, hydroxyalkyl or aryl group of 3 to 6 carbon atoms; A1 is

O -CNH and p is from 3 to 6. 11. A granular detergent composition 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 a cationic polymer remover / antiredeposition of clayey dirt is present, characterized in that it has a main structure, at least 2 M groups and at least one LX group, where M is a cationic group attached or integrated to the structure main and contains a positively charged N + center; and L connects groups M and X or connects group X to the polymeric backbone; X is a nonionic group selected from the group consisting of H, alkyl or hydroxyalkyl ester or alkyl groups of 1 to 4 carbon atoms, and mixtures thereof; and L is a hydrophobic chain containing the polyoxyalkylene moiety - [(R6O) m (CH2CH2O) n] -;

13. - A granular detergent composition according to claim 12, further characterized in that said cationic polymer is an ethoxylated cationic polymer having a main structure, selected from the group consisting of polyurethanes, polyesters, polyethers, polyimides, polyalkyleneimines and mixtures thereof.

14. A detergent composition according to claim 1 further characterized in that said hydrophobic organic peroxyacid compound has at least 7 carbon atoms.

15. A detergent composition according to claim 1, further characterized in that said hydrophobic organic peroxyacid bleach system comprises a source of hydrogen peroxide and a hydrophobic organic peroxyacid precursor.

16. A detergent composition according to claim 15, further characterized in that said hydrophobic organic peroxyacid precursor is present at a level of 0.2% to 10% by weight of the detergent composition.

17. A detergent composition according to claim 15, further characterized in that the organic peroxyacid precursor compound is a substituted amide peroxy acid precursor selected from the group consisting of R1-C-N-R2-C-L R1-N-C-R2-C-L O R5 O and R5 O O Where N may be essentially any residual group, R1 is an aryl or alkaryl group with 1 to 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 group containing 1 to 10 carbon atoms such that R1 and R5 in total do not contain more than 18 carbons.

18. A detergent composition according to claim 1 further characterized in that said hydrophobic organic peroxyacid bleach system comprises a preformed organic peroxyacid.

19. A detergent composition according to the claim 18, further characterized in that said preformed organic peroxyacid is present at a level of 1% to 10% by weight of the detergent composition.

20. A detergent composition according to claim 18, further characterized in that the preformed organic peroxyacid is selected from the group consisting of: R1-C-N-R2-C-OOH R1-N-C-R2-C-OOH O R5 O and R5 O O wherein R1 is an aryl or alkaryl group with about 1 to 14 carbon atoms, R 2 is an alkylene, arylene and alkarylene group containing about 1 to 14 carbon atoms, and R 5 is H or an alkyl, aryl group or alkaryl containing from 1 to 14 carbon atoms in such a way that R1 and R5 do not contain more than 18 carbon atoms in total.

21. A granular detergent composition according to claim 1, further characterized in that a non-hydrophobic bleach precursor compound is present.

22. A granular detergent composition according to claim 21, further characterized in that the ratio of said non-hydrophobic bleach precursor compound to the water-soluble cationic compound is from 10: 1 to 1: 1.

23. A granular detergent composition according to claim 21, further characterized in that the precursor compound of non-hydrophobic bleach is an N, N, N1, N1-tetraacetylated aiylenediamine.

24. 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.

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

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

27. - A washing method for domestic laundry, further characterized in that an effective amount of a granular detergent composition according to claim 1 is introduced into the drum of the washing machine, erably before the start of washing, by the use of a device dispenser that allows progressive release of said granulated detergent composition in the washing liquid during washing.