MXPA99008197A - Bleach compositions containing metal bleach catalyst, and bleach activators and/or organic percarboxylic acids - Google Patents

Abstract

Laundry or cleaning composition comprising:(a) an effective amount, preferably from about 0.0001%to about 99.9%, more typically from about 0.1%to about 25%, of a bleach activator and/or organic percarboxylic acid;(b) a catalytically effective amount, preferably from about 1 ppb to about 99.9%, of a transition-metal bleach catalyst which is a complex of a transition-metal and a cross-bridged macropolycyclic ligand;and (c) at least about 0.1%of one or more laundry or cleaning adjunct materials, preferably comprising an oxygen bleaching agent. Preferred compositions are laundry compositions and automatic dishwashing detergents which provide enhanced cleaning/bleaching benefits through the use of such catalysts in combination with bleach activators and/or organic percarboxylic acids.

Description

WHITENING COMPOSITIONS CONTAINING CATALYST OF TRANSITION METAL WHITENING AND ACTIVATORS WHITENING AND / OR ORCHANIC PERCARBOXILIC ACIDS TECHNICAL FIELD The present invention relates to detergent compositions and additive compositions for detergents and methods for their use. The compositions comprise selected transition metals such as Mn, Fe or Cr, with selected macropolycyclic rigid ligands, preferably crosslinked macropolycyclic ligands in combination with bleach activators and / or organic percarboxylic acids, preferably hydrophobic and / or hydrophilic bleach activators. More specifically, the present invention relates to the catalytic oxidation of soils and stains using cleaning compositions comprising bleach activators and / or organic percarboxylic acids and said metal catalysts, said soils and stains being on surfaces such as fabrics, tableware, counters, dentures and the like; as well as the inhibition of the transfer of dyes in the washing of fabrics. The compositions include bleach activators and / or organic percarboxylic acids, detergent aids and catalysts comprising complexes of manganese, iron, chromium and other suitable transition metals with certain macropolycyclic cross-bridge ligands. Preferred catalysts include transition metal complexes of ligands that are polyazamacropoiicycles, especially including specific azamacrobicikels, such as cyclama cross-bridge derivatives.

BACKGROUND OF THE INVENTION Since the 19th century a damaging effect of manganese on fabrics has been known during bleaching. In the 60's and 70's efforts were made to include simple Mn (ll) salts in detergents, but none was commercially successful. More recently, catalysts containing metal and containing macrocyclic ligands have been described for use in bleaching compositions. Preferred catalysts include those described as manganese-containing catalysts of small macrocycles, especially 1, 4,7-trimethyl-1,4,7-triazacyclononane. These catalysts effectively catalyze the bleaching action of the peroxide compounds against various spots. It is said that several are effective in the washing and bleaching of substrates, including in laundry and cleaning applications and in the textile, paper and wood pulp industries. However, said metal-containing bleach catalysts, especially these manganese-containing catalysts, still have disadvantages, for example a tendency to damage fabrics, relatively high cost, high color and the ability to stain or discolor substrates locally.

The salts of dry cationic metal caver complexes (U.S. Patent No. 4,888,032 to Busch, December 19, 1989) have been described as reversible oxygen complexers, and are shown to be useful for sweeping oxygen away from air. A variety of ligands are shown to be useful, some of which include macrocyclic ring structures and bridging groups. See also: D.H. Busch, Chemical Reviews, (1993), 93, 847-880, for example the description of superstructures on polarized ligands on pgs. 856-857 and references cited therein; B.K. Coltrain et al., "Oxigen Activation by Transition Metal Complexes of Macrbicyclic Cyclidene Ligands" in "The Activation of Dioxygen and Homogeneous Catalyt.tc Oxidation", Ed. By E.H.R. Barton et al. (Plenum Press, NY, 1993), pp. 359-380. The technical literature about azamacrociclos has grown at a rapid pace more recently. Among the several references are Hancock et al., J. Chem. Soc. Chem. Commun., (1987), 1129-1130; Weisman et al., "Synthesis and Transition Metal Complexes of New Cross-Bridged Tetraamine Ligands", Chem. Commun., (1996), 947-948; US patents Nos. 5,428,180; 5,504,075 and 5,126,464, all to Burrows and others; E.U. 5,480,990 to Kiefer et al. And E.U. 5,374,416 to Rousseaux and others. None of the hundreds of these references identify which of the numerous new ligands and / or complexes would be commercially useful in bleaching compositions. This history does not reveal the possibility that catalytic oxidation can alter almost all families of organic compounds to create valuable products, but its successful application as a hard surface of fabric bleaching depends on a complex set of relationships that include the activity of the putative catalyst , its survivability under reaction conditions, its selectivity and the absence of undesirable side reactions or reaction. In view of this long-lasting need, the continuous search for higher bleaching compositions containing transition metal catalysts, and in view of the lack of commercial success at this point, especially in compositions for washing fabrics with metal bleach catalysts. of Transition; in view also of the continuing need for improved cleaning compositions of all types that provide bleaching and removal of superior stains without disadvantages such as a tendency to damage or discolor the material to be cleaned, and also in view of the known technical limitations of the catalysts of existing transition metal bleaching for detergent applications, especially in aqueous solutions at high pH, it would be highly desirable to identify which of the thousands of potential transition metal complexes could be successfully incorporated into laundry and cleaning products. Accordingly, it is an object of the present invention to provide superior cleaning compositions incorporating selected transition metal bleach catalysts with detergent or cleaning aids that resolve one or more of the known limitations of said compositions.

It has now been surprisingly determined that, for use in laundry and hard surface cleaning products, transition metal catalysts having specific cross-linked macropolycylic ligands have exceptional kinetic stability. It has also been surprisingly found that such catalysts in combination with bleach activators and / or organic percarboxylic acids, preferably hydrophobic and / or hydrophilic bleach activators, provide additional benefits and properties of bleaching and cleaning. In this way, the compositions of the present invention can provide one or more important benefits. These include improved effectiveness of the compositions, and in some cases even synergy with one or more primary oxidants such as hydrogen peroxide, hydrogen peroxide, preformed peracids or monopersulfate; cleaning compositions include certain complexes, especially those containing Mn (ll), in which the catalyst matches in color particularly well with other detergent ingredients, the catalyst having little or no color. The compositions offer a great flexibility of the formulation in consumer products in which the aesthetics of the product is very important; and they are effective in many types of soils and dirty substrates, including a variety of dirty or stained fabrics or hard surfaces. The compositions allow the compatible incorporation of many types of detergent auxiliaries with excellent results. In addition, the compositions reduce or even almost eliminate the tendency to stain or damage such surfaces.

These and other objects are ensured in the present, as will be seen from the following descriptions.

TECHNICAL BACKGROUND Laundry bleaching is reviewed in Kirk Othmer's Encyclopedia of Chemical Technology, 3rd and 4th editions, under a number of headings that include "Bleach Agents", "Detergents" and "Peroxy Compounds". The use of amido-bleach activators in laundry detergents is described in the U.S. patent. No. 4,634,551. The use of manganese with various ligands to improve bleaching is reported in the following United States patents: E.U. 4,430,243; E.U. 4,728,455; E.U. 5,246,624; E.U. 5,244,594; E.U. 5,284,944; E.U. 5,194,416; E.U. 5,246,612; E.U. 5,256,779; E.U. 5,280.1 17; E.U. 5,274,147; E.U. 5,153,161; E.U. 5,227,084; E.U. 5,114,606; E.U. 5,114,611. See also EP 549,271 A1; EP 544,490 A1; EP 549,272 A1 and EP 544,440 A2. The patent of E.U. No. 5,580,485 discloses a bleaching and oxidation catalyst comprising an iron complex having the formula A [LfeXn] zYq (A) or precursors thereof, wherein Fe is iron in the oxidation state II, III, IV or V, X represents a coordinating species such as H2O, ROH, NR3) RCN, OH 'OOH-, RS ", RO", RCOO ", OCN", SCN ", N3'_ CN-, F, CI", Br, I ", O2", N03", NO2_, SO42", SO32 \ PO43 'O aromatic N-donors such as pyridines, pyrazines, pyrazoles, imidazoles, benzimidazoles, pyrimidines, triazoles and thiazoles, R being H, optionally substituted alkyl, aryl optionally substituted; n is 0-3; And it is a counterion, the type on which it depends on the charge of the complex; q = z / [Y load]; z denotes the charge of the complex and is an integer that can be positive, zero or negative; if z is positive, Y is an anion such as F ", Cr, Br-, I", NO3", BPh4", CIO4 \ BF4", PF4", RSO3", RSO4-, SO42", CF3SO3", RCOO- etc., if z is negative, Y is a common cation such as an alkali metal, alkaline earth metal or (alkyl) ammonium cation, etc., it is mentioned that L represents a ligand which is an organic molecule containing a number of heterogeneous atoms, for example N, P, O, S, etc., which coordinates by means of all or some of its heterogeneous atoms and / or carbon atoms to the iron center, indicating that the most preferred ligand is N, N-bis (pyridin-2-yl-methyl) -bis (pyridin-2-yl) methylamine, N4Py It is mentioned that the Fe complex catalyst is useful in a bleaching system comprising a peroxy compound or a precursor thereof and is suitable for use in the washing and bleaching of substrates including laundry, dishwashing and hard surface cleaning.Alternatively, the Fe complex catalyst is effectively also n useful in the textile, paper and wood pulp. The technique of transition metal chemistry of macrocycles is huge; see, for example "Heterocyclic Compounds: Aza-crown macrcycles", J.S. Bradshaw et al., Wiley-lnterscience, (1993) which also describes a synthesis number of said ligands. See especially the table starting on p. 604. The document E.U. 4,888,032 discloses salts of dry cavern metal caver complexes. Cross-bridging, that is, bridging through non-adjacent nitrogens, of (1, 4,8,11-tetraazacyclotetradecane) cyclamate is described by Weisman et al., J. Amer. Chem. Soc, (1990), 112 (23), 8604-8605. Most particularly, Weisman et al., Chem. Commun., (1996), 947-948 discloses novel cross bridge tetraamine ligands that are bicyclic systems [6.6.2], [6.5.2] and [5.5.2], and its complexation to Cu (ll) and Ni (ll) demonstrating that the ligands coordinate the metals in a slit. The specific complexes reported include those of ligands 1.1: 1. 1 in which A is hydrogen or benzyl and (a) m = n = 1; or (b) m = 1 and n = 0; or (c) m = n = 0, including a Cu (II) chloride complex of the ligand having A = H and m = n = 1; complexes of Cu perchlorate (ll) where A = H and m = n = 0; a Cu (II) chloride complex of the ligand having A = benzyl and m = n = 0; and a Ni (II) bromide complex of the ligand having A = H and m = n = 1. In some cases, the halide in these complexes is a ligand, and in other cases it is present as an anion. This variety of complexes seems to be the total of those that are known in which the crossed bridging is not through "adjacent" nitrogens. Ramasubbu and Wainwright, J. Chem. Soc. Chem. Commun., (1982), 277-278 in contrast, describe structurally reinforcing cyclic bridging adjacent nitrogen donors. Ni (ll) forms a clear yellow mononuclear diperchlorate complex having one mole of the ligand in a square planar configuration. Kojima et al., Chemistry Letters, (1996), pp. 153-154 describes effectively novel optically active Cu (ll) dinuclear complexes of a structurally reinforced tricyclic macrocycle. Bridging alkylation of saturated polyaza macrocycles as a means of imparting structural rigidity is described by Wainwright, Inorg. Chem., (1980), 19 (5), 1396-8. Mali, Wade and Hancock describe a cobalt complex (III) of a structurally reinforced macrocycle, see J. Chem. Soc, Dalton Trans., (1992), (1), 67-71. Seki et al. Describe the synthesis and structure of chiral copper (li) dinuclear complexes of an effectively novel reinforced hexazamacrocyclic ligand; see Mol. Cryst. Liq. Cryst. Sci. Technol., Sec. A (1996), 276, pp. 79-84; see also a related work by the same authors in the same report in 276, pp. 85-90 and 278, p. 235-240. Complexes of [Mn (lll) 2 (μ-O) (μ-02Cme) 2L2] 2+ and [Mn (IV) 2 (μ-O) 3L2] 2+ derived from a series of 1, 4.7 are described -triazacyclononanes N-substituted by Koek et al., see J. Chem. Soc, Dalton Trans., (1996), 353-362. More important recent works by Wieghardt and co-workers in 1, 4,7-triazacyclononane transition metal complexes, including manganese, are described in Wieghardt et al., Amgew. Chem. Interna. Ed. Engl., (1986), 25, 1030-1031 and Wieghardt et al. J. Amer. Chem. Soc, (1988), 1 10, 7398. Ciampoiini et al., J. Chem. Soc, Dalton Trans., (1984), pp. 1357-1362 describe the synthesis and characterization of the macrocycle 1, 7-dimethyl-1, 4,7,10-tetrazacyclododecane and certain of its Cu (II) and Ni (II) complexes, including both a complex of Ni square and plane as a cis-octahedral complex with the macrocycle coordinated in a configuration bent at four sites around the central nickel atom. Hancock and others, Inorg. Chem., (1990), 29, 1968-1974 describe ligand design approaches for aqueous solution complexation, including chelate ring size as a basis for size-based selectivity control for metal ions. Thermodynamic data for the interaction of macrocycles with cations, anions and neutral molecules is reviewed by Izatt et al., Chem. Rev., (1995), 95, 2529-2586 (478 references). Bryan et al., Inorganic Chemistry, (1975), 14, No. 2, pp. 296-299 describe the synthesis and characterization of complexes of Mn (ll) and Mn (lll) of / 77eso-5,5,7-12,12,14-hexamethyl-1,4,8,11-tetraazacyclotetradecane ([14 ] anoN4] The isolated solids are frequently contaminated with free ligand or "excess metal salt" and attempts to prepare chloride and bromide derivatives gave solids of variable composition that could not be purified by repeated crystallization Costa and delgado, Inorg. Chem., (1993), 32, 5257-5265, describe metal complexes such as complexes of Co (ll), Ni (ll) and Cu (ll), of macrocyclic complexes containing pyridine. cross-linked, such as salts of 4,10-dimethyl-1,4,7,10-tetraazabicyclo [5.5.2] tetradecane, are described by Bencini et al., see Supramolecular Chemistry, 3, pp. 141-146. The patent of E.U. No. 5,428,180 and related work by Cynthia Burrows and collaborators in E.U. 5,272,056 and E.U. 5,504,075 describes the pH dependence of oxidations using cyclama or its derivatives, oxidations of alkenes to epoxides using metal complexes of said derivatives and pharmaceutical applications. Hancock et al., Inorganic Chimica Acta., (1989), 164, 73-84, describe under a heading that includes "complexes of structurally reinforced tetraazamacrocyclic ligands of high field strength of ligand" the synthesis of complexes of Ni (II) of low turn with three novel bicyclic macrocycles. The complexes apparently include almost planar arrangements of the four donor atoms and metals despite the presence of the bicyclic ligand arrangement. Bencini et al., J. Chem. Soc, Chem. Commun., (1990), 174-175 describe the synthesis of a 4,10-dimethyl-1, 4,7,10,15-penta-azabicyclo [5.5.5 ] Aza small cage heptadecane, which "encapsulates" lithium. Hancock and Martell, Chem. Rev., (1989), 89, 1875-1914 review the design of ligands for the selective complexation of metal ions in aqueous solution. Cyclam complex conformers are described on page 1894, including a bent former-see Fig. 18 (cis-V). The paper includes a glossary. In a paper entitled "Structurally Reinforced Macrocyclic Ligands that Show Greatly Enhanced Selectivity for Metal lons on the Basis of the Match and Size Between the Metal Ion and the Macrocyclic Cavity", Hancock et al., J. Chem. Soc. Chem. Commun., (1987), 1129-1130 describe the formation constants for Cu (II), Ni (II) and other metal complexes of some bridged macrocycles having a piperazine type structure. Many other macrocilies are described in the art, including types with pendant groups and a wide range of intracyclic and exocyclic substituents. In short, although the literature of macrocycles and transition metal complexes is vast, it seems that very little has been reported about the macroazines tetraaza- and pentaaza- cross bridge and there is no apparent explanation of these materials from the vast literature, either alone or as their transition metal complexes, to be used in bleaching detergents.

BRIEF DESCRIPTION OF THE INVENTION The present invention relates to a laundry or cleaning composition comprising: (a) an effective amount, preferably about 1 ppm to about 99.9%, very typically about 0.1% to about 25%, of a bleach activator and / or organic percarboxylic acid, preferably a bleach activator selected from hydrophobic bleach activators, hydrophilic bleach activators and mixtures thereof; (b) a catalytically effective amount, preferably about 1 ppb to about 99.9%, very typically about 0.001 ppm to about 49%, preferably about 0.05 ppm to about 500 ppm (where "ppb" denotes parts per billion by weight and "ppm" denotes parts per million by weight), of a transition metal catalyst, wherein said transition metal bleach catalyst comprises a complex of a transition metal selected from the group consisting of Mn (ll), Mn (lll), Mn (IV), Mn (V) Fe (ll), Fe (lll), Fe (IV), Co (l), Co (ll), Co (lll), Ni (l), Ni ( ll), Ni (III), Cu (l), Cu (ll), Cu (lll), Cr (ll), Cr (lll), Cr (IV), Cr (V), Cr (VI), V ( lll), V (IV), V (V), Mo (IV), Mo (V), Mo (VI), W (IV), W (V), W (VI), Pd (ll), Ru ( ll), Ru (lll) and Ru (IV) coordinated with a macropolycyclic ligand, preferably a cross-bridge macropolycyclic ligand, having at least 4 donor atoms, at least two of which are donor heads of bridge; and (c) the remainder, 100%, of one or more auxiliary materials, preferably comprising an oxygenated bleaching agent. Preferred compositions comprise: (a) an effective amount, preferably about 1 ppm to about 99.9%, very typically about 0.1% to about 25%, of a bleach activator selected from the group consisting of hydrophobic bleach activators , such as sodium nonanoyloxybenzenesulfonate, hydrophilic bleach activators, such as N, N, N ', N'-tetraacetylethylenediamine and mixtures thereof; (b) a catalytically effective amount, preferably about 1 ppb to about 99.9%, very typically about 0.001 ppm to about 49%, preferably about 0.05 ppm to about 500 ppm of a transition metal catalyst, said catalyst comprising a transition metal complex and a cross-bridge macropolyicylic ligand, wherein: (1) said transition metal is selected from the group consisting of Mn (ll), Mn (lll), Mn (IV), Fe (ll) , Fe (lll), Cr (ll), Cr (lll), Cr (IV), Cr (V) and Cr (VI); (2) said macropolycyclic cross bridge ligand is coordinated by four or five donor atoms to the same transition metal and comprises: (i) an organic macrocycle ring containing four or more donor atoms selected from N and optionally O and S, by at least two of these donor atoms with N (preferably at least 3, most preferably at least 4, of these donor atoms being N), separated from one another by covalent bonds of 2 or 3 non-donor atoms, two to five ( preferably three or four, most preferably four) of these donor atoms being coordinated to the same transition metal in the complex; (ii) a cross-bridging chain that covalently connects at least 2 non-adjacent N-donor atoms of the organic macrocycle ring, said non-adjacent N-donor atoms being N-bridge donor atoms that are coordinated to the same metal of transition in the complex, and wherein said cross-bridge chain comprises from 2 to about 10 atoms (preferably the cross-bridge chain is selected from 2, 3 or 4 non-donor atoms, and 4-6 non-donor atoms with a donor atom additional, preferably N); and (iii) optionally, one or more non-macropolyclic ligands, preferably selected from the group consisting of H 2 O, ROH, NR 3, RCN, OH ", OOH", RS-, RO ", RCOO", OCN ", SCN", N3 ', CN-, F, CI ", Br", I ", O2", NO3-, NO2", SO42", SO32", PO43 \ organic phosphates, organic phosphonates, organic sulfates, organic sulfonates and aromatic N-donors such as as pyridines, pyrazines, pyrazoles, imidazoles, benzimidazoles, pyrimidines, triazoies and thiazoles, R being H, optionally substituted alkyl, optionally substituted aryl, and (c) the remainder, at 100%, preferably at least about 0. 1% of one or more auxiliary laundry or cleaning materials, preferably comprising an oxygenated bleaching agent. The amounts of the essential transition metal catalyst, bleach activator and / or organic percarboxylic acid and auxiliary materials can vary widely depending on the precise application. For example, the compositions herein may be provided as a concentrate, in which case the catalyst and the bleach activator and / or organic percarboxylic acid may be present in a high proportion, for example 0.01% - 80%, or more, of the composition. The invention also encompasses compositions containing bleach activators and / or organic percarboxylic acid at their use levels; said compositions include those in which the catalyst is diluted, for example at ppb levels. Intermediate level compositions, for example those comprising about 0.01 ppm to about 500 ppm, most preferably about 0.05 ppm to about 50 ppm, most preferably still about 0.1 ppm to about 10 ppm of a transition metal catalyst, from about 1 ppm to about 10,000 ppm, preferably from about 10 ppm to about 5000 ppm of bleach activator and / or organic percarboxylic acid (preferred levels for hydrophilic and hydrophilic bleach activators are from about 1 ppm to about 3000 ppm, most preferably about 10 ppm to about 1000 ppm) and the rest at 100%, preferably at least about 0.1%, typically about 99% or more being auxiliary materials in solid form or in liquid form (eg fillers, solvents and auxiliaries) specially adapted for a particular use). The present invention also relates to a laundry or cleaning composition comprising: (a) an effective amount, preferably about 1 ppm to about 99.9%, very typically about 0.1% to about 25% of a bleach activator and / or organic percarboxylic acid; (b) a catalytically effective amount, preferably about 1 ppb to about 99.9%, of a transition metal catalyst that is a complex of a transition metal and a macropolycyclic cross-linked ligand and (c) the rest, at 100 %, of one or more auxiliary laundry or cleaning materials, preferably comprising an oxygenated bleaching agent. The present invention further relates to laundry or cleaning compositions comprising: (a) an effective amount, preferably about 1 ppm to about 99.9%, very typically about 0.1% to about 25% of a bleach activator and / or organic percarboxylic acid; (b) a catalytically effective amount, preferably about 1 ppb to about 49%, of a transition metal catalyst, said catalyst comprising a complex of a transition metal and a rigid macropolycyclic ligand, preferably a macropolycyclic cross-bridge ligand, wherein: (1) said transition metal is selected from the group consisting of Mn (ll), Mn (lll), Mn (IV), Mn (V), Fe (ll), Fe (lll), Fe (IV) ), Co (l), Co (ll), Co (lll), Ni (l), Ni (ll), Ni (lll), Cu (l), Cu (ll), Cu (lll), Cr (ll) ), Cr (lll), Cr (IV), Cr (V), Cr (VI), V (lll), V (IV), V (V), Mo (IV), Mo (V), Mo (VI) ), W (IV), W (V), W (VI), Pd (ll), Ru (ll), Ru (lll) and Ru (IV); (2) said rigid macropolyclic ligand is coordinated by at least four, preferably four or five donor atoms to the same transition metal and comprises: (i) an organic macrocycle ring containing four or more donor atoms (preferably at least 3) , most preferably at least 4, of these donor atoms are N), separated from one another by covalent bonds of at least one, preferably 2 or 3 non-donor atoms, two to five (preferably three or four, most preferably four) of these donor atoms being coordinated to the same transition metal in the complex; (ii) a linker portion, preferably a cross-bridging chain that covalently connects at least 2 (preferably non-adjacent) donor atoms of the organic macrocycle ring, said donor atoms (preferably non-adjacent) being bridging donor atoms that are coordinated to the same transition metal in the complex, and wherein said linker portion (preferably a cross-bridge chain) comprises from 2 to about 10 atoms (preferably the cross-bridge chain is selected from 2, 3 or 4 non-donor atoms, and 4-6 non-donor atoms with an additional donor atom), including for example a cross-bridge that is the result of a Mannich condensation of ammonia and formaldehyde; and (iii) optionally, one or more non-macropolyclic ligands, preferably monodentate ligands, such as those selected from the group consisting of H 2 O, ROH, NR 3, RCN, OH ", OOH", RS ", RO", RCOO ', OCN \ SCN-, N3-, CN-, F, Cl \ Br ", I", O2", NO3", NO2", SO42", SO32", PO43 ', organic phosphates, organic phosphonates, organic sulphates, organic sulfonates and aromatic N-donors such as pyridines, pyrazines, pyrazoles, imidazoles, benzimidazoles, pyrimidines, triazoles and thiazoles, R being H, optionally substituted alkyl, optionally substituted aryl (specific examples of monodentate ligands including phenolate, acetate or the like); ) at least about 0.1%, preferably B%, of one or more auxiliary laundry or cleaning materials, preferably comprising an oxygenated bleaching agent (wherein B%, the "remainder" of the composition expressed as a percentage, obtains by subtracting the weight of said components (a) and (b) from the p that of the total composition and then expressing the result as a percentage by weight of the total composition). The present invention also preferably relates to laundry or cleaning compositions comprising: (a) an effective amount, preferably about 1 ppm to about 99.9%, very typically about 0.1% to about 25% of a bleach activator and / or organic percarboxylic acid; (b) a catalytically effective amount, preferably about 1 ppb to about 49%, of a transition metal catalyst, of a transition metal bleach catalyst, said catalyst comprising a complex of a transition metal and a macropolycyclic ligand rigid (preferably a cross-bridge macropolyicylic ligand) wherein: (1) said transition metal is selected from the group consisting of Mn (ll), Mn (lll), Mn (IV), Mn (V), Fe (ll) ), Fe (III), Fe (IV), Co (I), Co (ll), Co (lll), Ni (l), Ni (ll), Ni (lll), Cu (l), Cu (ll), Cu (lll), Cr (ll), Cr (lll), Cr (IV), Cr (V), Cr (VI), V (lll), V (IV), V (V), Mo (IV), Mo (V), Mo (VI), W (IV), W (V), W (VI), Pd (ll), Ru (ll), Ru (lll) and Ru (IV), and (2) said rigid macropolycyclic ligand is selected from the group consisting of: (i) the cross-linked macropolycyclic ligand of the formula (I) that has a denticity of 4 or 5: (i); (ii) the macropolycyclic cross bridge ligand of formula (II) having a denticity of 5 or 6: (ii); (iii) the cross-linked macropolycyclic ligand of formula (III) having a denticity of 6 or 7: («I); where in these formulas: - each "E" is the portion (CRn) a-X- (CRn) a '. wherein -X- is selected from the group consisting of O, S, NR and P, or a covalent bond, and preferably X is a covalent bond and for each E the sum of a + a 'is independently selected from 1 to 5 , very preferably 2 and 3; - each "G" is the portion (CRn) b; - each "R" is independently selected from H, alkyl, alkenyl, alkynyl, aryl, alkylaryl (for example, benzyl) and heteroaryl, or two or more R are covalently linked to form an aromatic, heteroaromatic, cycloalkyl or heterocycloalkyl ring; each "D" is a donor atom independently selected from the group consisting of N, O, S and P, and at least two D atoms are bridgehead donor atoms coordinated to the transition metal (in the preferred embodiments, all the designated donor atoms D are donor atoms that coordinate to the transition metal, in contrast to heterogeneous atoms in the structure that are not in D such as those that may be present in E, heterogeneous atoms other than D may be non-coordinating and in fact they are non-coordinators as long as they are present in the preferred modality); - "B" is a carbon atom or "D" donor atom, or a cycloalkyl or heterocyclic ring; - each "n" is an integer selected independently from 1 and 2, completing the valence of the carbon atoms to which the R portions are covalently bound; - each "n" 'is an integer selected independently of 0 and 1, completing the valence of donor atoms D to which the R portions are covalently bound; - each "n" "is an integer selected independently of 0, 1 and 2, by completing the valence of the B atoms to which the R portions are covalently linked - each" a "and" a "'is an independently selected integer of 0-5, preferably a + a 'is equal to 2 or 3, wherein the sum of all "a" plus "a"' in the ligand of formula (I) is on the scale of about 6 (preferably 8) to about 12, the sum of all "a" plus "a" 'in the ligand of formula (II) is on the scale of about 8 (preferably 10) to about 15 and the sum of all "a" "plus" to "'in the ligand of the formula (III) is on the scale of about 10 (preferably 12) to about 18; - each" b "is an integer selected independently from 0-9, preferably 0-5 ( wherein when b = 0, (CRn) or represents a covalent bond), or in any of the above formulas, one or more of the portions (CRn) b covalently attached d from any D to atom B is absent, as long as at least two (CRn) b covalently bind two of the donor atoms D to atom B in the formula, and the sum of all the "b" is on the scale of about 1 to about 5; and (iii) optionally, one or more non-macropolyclic ligands; and (c) one or more laundry or cleaning auxiliary materials, preferably comprising an oxygenated bleaching agent, at suitable levels as identified hereinabove. The present invention also preferably relates to laundry or cleaning compositions comprising: (a) an effective amount, preferably about 1 ppm to about 99.9%, very typically about 0.1% to about 25% of a hydrophobic bleach activator; (b) a catalytically effective amount, preferably about 1 ppb to about 99.9%, of a transition metal catalyst, said catalyst comprising a complex of a transition metal and a macropolycyclic cross-bridge ligand, wherein: (1) said transition metal is selected from the group consisting of Mn (ll), Mn (lll), Mn (IV), Fe (ll), Fe (lll), Cr (ll), Cr (lll), Cr (IV) , Cr (V) and Cr (VI); (2) said macropolycyclic cross bridge ligand is selected from the group consisting of: where in these formulas. - each "R" is independently selected from H, alkyl, alkenyl, alkynyl, aryl, alkylaryl (for example, benzyl) and heteroaryl, or two or more R are covalently linked to form an aromatic, heteroaromatic, cycloalkyl or heterocycloalkyl ring; - each "n" is an integer selected independently from 0, 1 and 2, completing the valence of the carbon atoms to which the R portions are covalently bound; - each "b" is an integer selected independently of 2 and 3; - each "a" is an integer selected independently of 2 and 3 and (3) optionally, one or more non-macropolyclic ligands and (c) at least about 0.1%, preferably B%, of one or more laundry or cleaning auxiliary materials, preferably comprising an oxygenated bleaching agent (wherein B%, the "rest" of the composition expressed as a percentage, is oned by subtracting the weight of said components (a) and (b) from the weight of the total composition and then expressing the result as a percentage by weight of the total composition ). The present invention further relates to a method for cleaning fabrics or hard surfaces, said method comprising contacting a fabric or hard surface requiring cleaning with a catalytically effective amount, preferably about 0.01 ppm to about 500 ppm, of a catalyst. bleaching of transition metal which is a complex of a transition metal and a macropolycyclic cross-bridge ligand, an effective amount, preferably about 1 ppm to about 10,000 ppm, very typically about 10 ppm to about 5000 ppm, of an activator of bleaching and / or preformed organic peracid, and preferably also an oxygenated bleaching agent. Preferred is a method comprising contacting a fabric or hard surface requiring cleaning with an oxygenated bleaching agent, a bleach activator and / or organic percarboxylic acid and a transition metal bleach catalyst, wherein said bleaching catalyst transition metal comprises a complex of a transition metal selected from the group consisting of Mn (ll), Mn (III), Mn (IV), Mn (V), Fe (ll), Fe (lll), Fe (IV) ), Co (l), Co (ll), Co (lll), Ni (l), Ni (ll), Ni (lll), Cu (l), Cu (ll), Cu (III), Cr (ll) ), Cr (lll), Cr (IV), Cr (V), Cr (VI), V (lll), V (IV), V (V), Mo (IV), Mo (V), Mo (VI) ), W (IV), W (V), W (VI), Pd (ll), Ru (ll), Ru (lll) and Ru (IV), preferably Mn (ll), Mn (lll), Mn ( IV), Fe (ll), Fe (lll), Cr (ll), Cr (lll), Cr (IV), Cr (V) and Cr (VI), preferably Mn, Fe and Cr in the state (II) or (III), coordinated with a rigid macropolycyclic ligand, preferably a macropolycyclic cross-bridge ligand, having at least 4 donor atoms, so two of which are bridgehead donor atoms. The present invention also relates to methods for cleaning fabrics or hard surfaces, said method comprising contacting a fabric or hard surface requiring cleaning with a transition metal bleach catalyst which is a complex as described hereinabove, a hydrophobic and / or hydrophilic bleach activator and an oxygenated bleaching agent. All parts, percentages and relationships used herein are expressed as a percentage by weight, unless otherwise specified. All the documents cited are, in part relevant, incorporated herein by reference.

DETAILED DESCRIPTION OF THE INVENTION Bleaching compositions The compositions of the present invention comprise a particularly selected transition metal bleach catalyst comprising a complex of a transition metal and a rigid macropolycyclic ligand, preferably one that is cross-linked. The compositions further comprise essentially a hydrophobic and / or hydrophilic bleach activator (eg, sodium nonanoyloxybenzenesulfonate, N, N, N ', N'-tetraacetylethylenediamine) and / or an organic percarboxylic acid (eg, magnesium monoperoxyphthalate). hexahydrate; 1,2-diperoxydodecanoic acid; 6-Nonylamino-6-oxoperoxycaproic acid). The compositions also comprise at least one auxiliary material, which preferably comprises an oxygenated bleaching agent, preferably one that is a low cost and readily available substance that produces little or no waste, such as a source of hydrogen peroxide. The source of hydrogen peroxide may be H 2 O 2 itself, its solutions or any salt, adduct or common hydrogen peroxide releasing precursor, such as sodium perborate, sodium percarbonate or mixtures thereof. Other sources of available oxygen such as persulfate (e.g., OXONE, manufactured by DuPont), as well as preformed organic peracids and other organic peroxides are also useful.

For reasons of clarity, organic percarboxylic acids and bleach activators are not included in the class of optional oxygenated bleaching agents which are auxiliary materials for the compositions and methods of the present invention. However, blends of oxygenated bleaching agents with bleach activators are preferred in the present invention. In addition, mixtures of oxygenated bleaching agents and organic percarboxylic acids can be used, for example as in mixtures of hydrogen peroxide and peracetic acid or their salts. Most preferably, the auxiliary component includes both an oxygenated bleaching agent and at least one other auxiliary material selected from non-bleaching auxiliaries suitable for laundry detergents or cleaning products. The non-bleaching auxiliaries as defined herein are useful auxiliaries in detergents and cleaning products which do not whiten by themselves, nor are they recognized as auxiliaries used in cleaning, mainly as bleach promoters such as is the case with bleach activators, bleaching catalysts or organic percarboxylic acids. Preferred non-bleaching auxiliaries include detersive surfactants, detergency builders, non-bleaching enzymes having a useful function in detergents, and the like. Preferred compositions herein may incorporate a source of hydrogen peroxide which is any common hydrogen peroxide releasing salt, such as sodium perborate, sodium percarbonate and mixtures thereof. In a hard surface cleaning or fabric washing operation using the compositions of the present invention, the target substrate, i.e. the material to be cleaned, will typically be a stained surface or fabric with, for example, several hydrophilic spots. of food, such as coffee, tea or wine; with hydrophobic spots such as greasy or carotenoid spots; or is a "percured" surface, for example a yellow one by the presence of a fine residue of hydrophobic soils distributed relatively uniformly. In the present invention, a laundry or cleaning composition comprises: (a) an effective amount, preferably about 1 ppm to about 99.9%, very typically about 0.1% to about 25%, of a bleach activator (hydrophobic or hydrophilic) ) and / or organic percarboxylic acid; (b) a catalytically effective amount, preferably about 1 ppb to about 99.9%, of a transition metal catalyst which is a complex of a transition metal and a macropolycyclic cross-bridge ligand and (c) one or more auxiliary materials of laundry or cleaning, preferably comprising an oxygenated bleaching agent, at levels as described hereinabove.

In the laundry compositions that are preferred, auxiliaries such as builders including zeolites and phosphates, surfactants such as anionic and / or nonionic and / or cationic surfactants, dispersing polymers (which modify and inhibit the growth of crystals of calcium and / or magnesium salts, chelators (which control the transition metals introduced into the wash water), alkalis (to adjust the pH), and detersive enzymes.In addition, the present detergent or auxiliary detergent compositions can comprising one or more processing aids, fillers, perfumes, conventional enzyme particle-forming materials including enzyme centers or "core discs", as well as pigments and the like .. In the laundry compositions that are preferred, additional ingredients such as as dirt-releasing polymers, brighteners and / or inhibitors dye transfer agents. The compositions of the invention may include laundry detergents, hard surface cleaners and the like, which include all the components necessary for cleaning; alternatively, the compositions can be made to be used as cleaning additives. A cleaning additive, for example, can be a composition containing the transition metal catalyst, the bleach activator and / or organic percarboxylic acid, a detersive surfactant and a builder, and can be sold to be used as " added ", for use with a conventional detergent containing a perborate, percarbonate or other primary oxidant. The compositions herein may include automatic dishwashing (ADD) compositions and denture cleaners, and thus are not, in general, limited to fabric washing. In general, the materials used for the production of ADD compositions herein are preferably reviewed to verify their compatibility with the reduction of veins / films on glassware. The test methods for verifying the reduction of veins / films are generally described in the literature of detergents for automatic dishwashing, including DIN test methods. Certain oily materials, especially those having longer hydrocarbon chain lengths, and insoluble materials such as clays, as well as long-chain fatty acids or soap-forming soaps are therefore limited or excluded from said compositions. The amounts of essential ingredients may vary within wide limits, however, the preferred cleaning compositions herein (which have a pH of 1% aqueous solution of about 6 to about 13, most preferably about 7.5 to about 1. 1.5 and more preferably less than about 1 1, especially about 7 to about 10.5) are those in which it is present: about 1 ppb to about 99.9%, preferably about 0.01 ppm to about 49% and typically during use, about 0.01 ppm to about 500 ppm, of a transition metal catalyst according to the invention, preferably about 0.0001% to 99.9%, very typically about 0.1% to about 25% and typically during use, about 1 ppm at about 10,000 ppm, of a bleach activator and / or organic percarboxylic acid; and the remainder, typically of at least about 0.01%, preferably at least about 51%, most preferably about 90% to about 100% of one or more laundry or cleaning auxiliaries. In preferred embodiments, it may be present (also expressed as a weight percentage of the entire composition) from 0.1% to about 90%, preferably from about 0.5% to about 50% of an oxygenated bleaching agent, such as a preformed peracid or preferably a source of hydrogen peroxide; from 0% to about 20%, preferably at least about 0.001%, of a conventional bleaching promotion aid, such as a hydrophobic and / or hydrophilic bleach activators, and at least about 0.001%, preferably about 1 % to about 40%, of a laundry or cleaning assistant having a major role in the bleaching, such as a detersive surfactant, a builder, a detergent enzyme, a stabilizer, a detergent pH regulator or mixtures of the same. Such fully formulated embodiments desirably comprise, as non-bleaching auxiliaries, about 0.1% to about 15% of a polymeric dispersant, about 0.01% to about 10% of a chelator and about 0.00001% to about 10% of an enzyme detersive, although auxiliary or additional ingredients may be present, especially colorants, perfumes, pro-perfumes (compounds that release a fragrance when activated by a suitable activator such as heat, enzymatic action or change in pH). The auxiliaries that are preferred herein are selected from stable bleach types, although unstable types in bleach may be commonly included depending on the skill of the formulator. The detergent compositions herein can have any desired physical form; when in granulated form, it is typical to limit the water content, for example to less than about 10%, preferably less than about 7% free water, for better storage capacity. In addition, preferred compositions of this invention include those that are substantially free of chlorine bleach. By "substantially free" chlorine bleach is meant that the formulator does not deliberately add a bleach-containing bleach additive, such as hypochlorite or a source thereof, such as a chlorinated socianurate, to the preferred composition. However, it is recognized that due to factors beyond the control of the formulator, such as the chlorination of the water supply, a certain minimum amount of chlorine bleach may be present in the washing liquid. The term "substantially free" may be similarly considered with reference to the preferred limitation of other ingredients, such as phosphate builder. The term "catalytically effective amount", as used herein, refers to an amount of the transition metal catalyst present in the compositions of the present invention, or during use in accordance with the methods of the present invention, which suffice, under any comparative or use conditions that are employed, to result in at least the partial oxidation of the material that is sought to be oxidized by the composition or method. In the case of use in compositions or methods of laundry or cleaning of hard surfaces, the catalytically effective amount of the transition metal catalyst is that amount which is sufficient to improve the appearance of a soiled surface. In such cases, the appearance is typically improved in one or more aspects of whiteness, brilliance and stain removal; and a catalytically effective amount is one that requires less than a stoichiometric number of moles of catalyst compared to the number of moles of oxidant, such as hydrogen peroxide or peracid, required to produce a measurable effect. In addition to direct observation of the entire surface being bleached or cleaned, the catalytic bleaching effect can (when appropriate) be measured indirectly, such as by measuring the kinetics or final oxidation result of a dye in solution.

As mentioned, the invention encompasses catalysts both at their levels of use and at the levels that could be commercially provided for sale as "concentrates"; thus "catalytically effective amounts" herein include both of those levels at which the catalyst is highly diluted and ready to be used, for example at ppb levels, and compositions having relatively higher concentrations of catalyst, bleach activator and / or organic percarboxylic acid and auxiliary materials. Intermediate level compositions, as mentioned in the brief description, may include those comprising about 0.01 ppm to about 500 ppm, most preferably about 0.05 ppm to about 50 ppm, most preferably still about 0.1 ppm to about 10 ppm of transition metal catalyst and the rest at 100%, typically about 99% or more, being bleach activator and / or percarboxylic acid in solid or liquid form and auxiliary materials (eg fillers, solvents and auxiliaries specially adapted for a particular use, such as auxiliaries for detergents or the like). The levels that are preferred for use in the compositions and methods according to the present invention are provided hereinafter. In a fabric washing operation, the target substrate will typically be a stained fabric with, for example, several food stains. The test conditions will vary, depending on the type of washing device used and the habits of the user. In this way, front-loading clothes washers of the type used in Europe generally use less water and higher detergent concentrations than American-style top-loading washers. Some washing machines have considerably longer wash cycles than others. Certain users choose to use very hot water; others use lukewarm water or even cold water in fabric washing operations. Of course, the catalytic performance of the transition metal bleach catalyst will be affected by such considerations, and the levels of transition metal bleach catalyst used in fully formulated bleach and detergent compositions can be suitably adjusted. As a practical matter, and not by way of limitation, the compositions and methods herein can be adjusted to provide in the order of at least one part per billion of the active transition metal bleach catalyst in the aqueous wash liquor, and will preferably provide about 0.01 ppm to about 500 ppm of the transition metal bleach catalyst in the wash liquor, and will further provide in the order of about 1 ppm to about 10,000 ppm, preferably about 10 ppm to about 5000 ppm of activator of bleaching and / or percarboxylic acid in the washing liquid. By "effective amount", as used herein, it is intended to mean an amount of a material, such as a detergent auxiliary, that is sufficient under whatever comparative or use conditions are employed, to provide the desired benefit in methods of laundry and cleaning to improve the appearance of a dirty surface in one or more cycles of use. A "use cycle" is, for example, a washing of a group of fabrics by a consumer. The visual appearance or effect can be measured by the consumer, by technical observers such as trained panelists or by technical instruments such as spectroscopy or image analysis. The levels of attached materials that are preferred to be used in the compositions and methods of the present invention are provided hereinbelow.

Transition metal bleach catalysts The compositions of the present invention comprise a transition metal bleach catalyst. In general, the catalyst contains a transition metal at least partially covalently bound, and attached thereto is at least one particularly defined rigid macropolycyclic ligand, preferably one having four or more donor atoms (most preferably 4 or 5 donor atoms) and which is cross-linked or otherwise bonded to the ring of primary macrocillo is complexed in a bent conformation around the metal. The catalysts of the present are thus not of the more conventional macrocyclic type: for example, porphyrin complexes, in which the metal can easily adopt a square-planar configuration; nor are they compiejos in which the metal is completely encrypted in a ligand. Instead, the presently useful catalysts represent a selection of all the various complexes, hitherto largely unknown, which have an intermediate state in which the metal is bonded in a "slit". In addition, one or more additional ligands, of a generally conventional type such as chloride covalently bound to the metal, may be present in the catalyst; and, if necessary, one or more counterions, very commonly anions such as chloride, hexafluorophosphate, perchlorate or the like; and additional molecules to complete crystal formation as required, such as water for crystallization. In general, only the transition metal and the rigid macropolyclic ligand are essential. The transition metal bleach catalysts useful in the compositions of the invention can generally include known compounds that conform to the definition of the invention, as well as, most preferably, any of a large number of novel compounds expressly designed for those present. laundry or cleaning uses, and illustrated in a non-limiting manner by any of the following: Dichloro-5,12-dimethyl-1, 5,8,12-tetraazabicyclo [6.6.2] hexadecane Manganese (ll) Dichloro-4,10-dimethyl-1, 4,7,10-tetraazabicyclo [5.5.2] tetradecane Manganese (ll) Diaxa-5,12-dimethyl-1, 5,8,12-tetraazabicyclohexafluorophosphate - [6.6.2] hexadecane Manganese (ll) Acid-hydroxy-5,12-dimethyl-1, 5,8,12-tetraazabicicio- [6.6.2] hexadecane Manganese (lll) Diaxa-4 hexafluorophosphate, 10-dimethyl-1, 4,7,10-tetraazabicyclo- [5.5.2] tetradecane Manganese (II) Diacuo-5,12-dimethyl-1, 5,8,12-tetraazabicyclo- [6.6.2] hexadecane tetrahydrofoborate. Manganese (ll) Diacuo-4,10-dimethyl-1, 4,7,10-tetraazabicyclo- [5.5.2] tetradecane tetrafluoroborate Manganese (ll) Dichloro-5,12-dimethyl-1,5,6 hexafluorophosphate, 12-tetraazabicyclo- [6.6.2] hexadecane Manganese (lll) Dichloro-5,12-di-n-butyl-1, 5,8,12-tetraazabicyclo [6.6.2] hexadecane Manganese (II) Dichloro-5,12 -dibenzyl-1, 5,8,12-tetraazabicyclo [6.6.2] hexadecane Manganese (II) Dichloro-5-n-butyl-12-methyl-1, 5,8,12-tetraazabicyclo [6.6.2] hexa- dean Manganese (ll) Dichloro-5-n-octyl-12-methyl-1, 5,8,12-tetraa zabicyclo [6.6.2] hexadecano Manganese (ll) Dichloro-5-n-butyl-12-methyl-1, 5,8,12-tetraazabicyclo [6.6.2] hexadecano Manganese (II) Dichloro-5, 12-Dimethyl-1, 5,8,12-tetraazabicyclo [6.6.2] hexadecane Iron (II) Dichloro-4,10-dimethyl-1,4,7,10-tetraazabicyclo [5.5.2] tetradecane Iron (II) Dichloro-5,12-dimethyl-1, 5,8,12-tetraazabicyclo [6.6.2] hexadecane Copper (ll) Dichloro-4,10-dimethyl-1, 4,7,10-tetraazabicyclo [5.5.2] tetradecane Copper (ll) Dichloro-5,12-dimethyl-1, 5,8,12-tetraazabicyclo [6.6.2] hexadecane Cobalt (ll) Dichloro-4,10-dimethyl-1, 4,7,10-tetraazabicyclo [5.5.2] tetradecane Cobalt (ll) Dichloro-5,12-dimethyl-4-phenyl-1, 5,8,12 -tetraazabicyclo [6.6.2] hexadecano Manganese (II) Dichloro-4,10-dimethyl-3-phenyl-1, 4,7,10-tetraazabicyclo [5.5.2] tetradecano Manganese (II) Dichloro-5 , 12-dimethyl-4,9-diphenyl-1, 5,8,12-tetraazabicyclo [6.6.2] -hexadecane Manganese (II) Dichloro-4,10-dimethyl-3,8-diphenyl-1, 4,7 , 10-tetraazabicyclo [5.5.2] -tetradecane Manganese (II) Dichloro-5,12-dimethyl-2,11-diphenyl-1, 5,8,12-tetraazabicyclo [6.6.2] -hexadecane Manganese (II) Dichloro-4,10-dimethyl-4,9-diphenyl-1,4,7,10-tetraazabicyclo [5.5.2] -tetradecane Manganese (II) Dichloro-2,4,5,9,11, 12-hexamethyl -1, 5,8,12-tetraazabicyclo [6.6.2] -hexadecane Manganese (II) Dichloro-2,3,5,9,10,16-hexamethyl-1, 5,8,12-tetraazabicyclo [6.6.2 ] -hexadecane Manganese (ll) Dichloro-2,2,4,5,9,9,1 1, 12-octamethyl-1, 5,8,12-tetraazabicyclo- [6.6.2] hexadecane Manganese (II) Dichloro- 2,2,4,5,9,1 1, 1, 12-octamethyl-1, 5,8,12-tetraazabicyclo- [6.6.2] he xadecan Manganese (ll) Dichloro-3,3,5,10,10, 12-hexamethyl-1, 5,8,12-tetraazabicyclo [6.6.2] -hexadecane Manganese (II) Dichloro-3,5,10,12 -tetramethyl-1, 5,8,12-tetraazabicyclo [6.6.2] -hexadecane Manganese (II) Dichloro-3-butyl-5,10,12-trimethyl-1, 5,8,12-tetraazabicyclo [6.6.2] ] -hexadecane Manganese (ll) Dichloro-1, 5,8,12-tetraazabicyclo [6.6.2] -hexadecane Manganese (ll) Dichloro-1,4,7,10-tetraazabicyclo [5.5.2] -tetradecane Manganese (II) ) Dichloro-1, 5,8,12-tetraazabicyclo [6.6.2] -hexadecane Iron (II) Dichloro-1, 4,7,10-tetraazabicyclo [5.5.2] -tetradecane Iron (II) Acuo-chloro-2- (2-hydroxyphenyl) -5,12-dimethyl-1, 5,8,12-tetraazabicyclo- [6.6.2] hexadecane Manganese (ll) Acuo-chloro-10- (2-hydroxybenzyl) -4,10-dimethyl- 1, 4,7,10-tetraaza-bicyclo [5.5.2] tetradecane Manganese (II) Chloro-2- (2-hydroxybenzyl) -5-methyl-1, 5,8,12-tetraazabicyclo [6.6.2] - hexadecane Manganese (ll) Chloro-10- (2-hydroxybenzyl) -4-methyl-1, 4,7,10-tetraazabicyclo [5.5.2] -tetradecane Manganese (II) Chloro-5-methyl-12- ( 2-picolyl) -1, 5,8,12-tetraazabicyclo- [6.6.2] hexadecane Manganese (ll) Chloro-4-methyl-10- (2-picolyl) -1,4,7,10-tetraazabicyclo - [5.5.2] Tetradecane Manganese (ll) Dichloro-5- (2-sulfate) dodecyl-12-methyl-1, 5,8,12-tetraazabicyclo- [6.6.2] hexadecane Manganese (lll) Acuo-chloro- 5- (2-sulfate) dodecyl-12-methyl-1, 5,8,12-tetraazabicyclo- [6.6.2] hexadecane Manganese (II) Acuo-chloro-5- (3-sulfonopropyl) -12-methyl-1 , 5,8,12-tetraazabicyclo- [6.6.2] hexad ecano Manganese (ll) Dichloro-5- (trimethylammoniumpropyl) dodecyl-12-methyl-1 chloride, 5,8,12-tetraazabicyclo [6.6.2] hexadecane Manganese (lll) Dichloro-5, 12-dimethyl-1, 4,7,10, 13-pentaazabicyclo [8.5.2] hepta-decane Manganese (II) Dichloro -14,20-dimethyl-1, 10,14,20-tetraazatricyclo [8.6.6] docosa-3 (8), 4,6-triene Manganese (II) Dichloro-4,1 1 -dimethyl-1, 4, 7,11-tetraazabicyclo- [6.5.2] pentadeca Manganese (ll) Dichloro-5,1, -dimethyl-1, 5,8,12-tetraazabicyclo- [7.6.2] heptadecane Manganese (II) Dichloro-5,13- dimethyl-1, 5,9,13-tetraazabicyclo- [7.7.2] heptadecane Manganese (II) Dichloro-3,10-bis (butylcarboxy) -5,12-dimetii-1, 5,8,12-tetraazabi-cycle [6.6.2] hexadecane Manganese (ll) Dichloro-3,10-dicarboxy-5,12-dimetii-1, 5,8,12-tetraazabicyclo [6.6.2] -hexadecane Manganese (ll) Chlorine-20 hexafluorophosphate methyl-1, 9,20,24,25-pentaazatetracyclo [7.7.7.13J.111 5.] pentacosa-3,5,7 (24), 1 1, 13,15 (25) -hexane Manganese (ll) Trifluoromethanesulfonate of trifluoromethanesulfone-20-methyl-1, 9,20,24,25-pentaazatetracyclo [7.7.7.13'7.111'15.] pentacosa-3,5,7 (24), 1 1, 13,15 (25) -hexaeno Manganese (l I) Tr trifluoromethanesulfone-20-methyl-1, 9,20,24,25-pentaazatetracicio trifluoromethanesulfonate [7.7.7.13'7.111 15.] pentacosa-3,5,7 (24), 11,13,15 (25) -hexaeno Iron (ll) Chloro-5,17,17-trimethyl-1, 5,8,12,17-pentaazabicyclo- [6,6,5] nonadecane hexafluorophosphate Manganese (ll) Chloro-4,10,15-trimethyl hexafluorophosphate -1, 4,7,10,15-pentaazabicyclo- [5.5.5] heptadecane Manganese (II) Chloro-5,12,17-trimethyl-1, 5,8,12,17-pentaazabicyclo- [6.6. 5] nonadecane Manganese (ll) Chloro-4, 10,15-trimethyl-1, 4,7, 10,15-pentaazabicyclo- [5.5.5] heptadecane Manganese (ll) Complexes preferred and useful as bleach catalysts transition metals more generally include not only the monometallic, mononuclear types such as those illustrated above, but also the bimetallic, trimethallic or cluster types, especially when the polymetallic types are metallically transformed in the presence of a primary oxidant to form a species active mononuclear , monometallic. Monometallic and mononuclear complexes are preferred. As defined herein, a monometallic transition metal bleach catalyst contains only one transition metal atom per mole of complex. A mononuclear, mononuclear complex is one in which any donor atoms of the essential macrocyclic ligand are attached to the same transition metal atom, ie, the essential ligand does not "bridge" through two or more transition metal atoms.

Catalyst transition metals Just as the macropolyclic ligand can not vary indefinitely for the present useful purposes, neither can the metal. An important part of the invention is to arrive at a match between the selection of the ligand and the selection of the metal, which results in excellent bleach catalysis. In general, the transition metal bleach catalysts herein comprise a transition metal selected from the group consisting of Mn (II), Mn (III), Mn (IV), Mn (V) Fe (II), Fe (lll), Fe (IV), Co (l), Co (ll), Co (lll), Ni (l), Ni (ll), Ni (lll), Cu (l), Cu (ll), Cu (lll), Cr (II), Cr (lll), Cr (IV), Cr (V), Cr (VI), V (lll), V (IV), V (V), Mo (IV), Mo (V), Mo (VI), W (IV), W (V), W (VI), Pd (ll), Ru (ll), Ru (lll) and Ru (IV). The transition metals that are preferred in the present transition metal bleach catalyst include manganese, iron and chromium, preferably Mn (ll), Mn (III), Mn (IV), Fe (ll), Fe (III), Cr (ll), Cr (III), Cr (IV), Cr (V) and Cr (VI), most preferably manganese and iron, more preferably manganese. The oxidation states that are preferred include the oxidation states (II) and (III). Manganese (ll) is included in both the low spin configuration and the high turn complex. It is worth mentioning that complexes such as low spin Mn (ll) complexes are very rare throughout the coordination chemistry. The designation (II) or (III) denotes a coordinated transition metal having the necessary oxidation state; the coordinate metal atom is not a free ion or one that has only water as a ligand.

Liqandos In general, as used herein, a "ligand" is any portion capable of direct covalent attachment to a metal ion. The ligands may be charged or neutral and may vary widely, including simple monovalent donors, such as chloride, or simple amines that form a single coordinated junction and a single point of attachment to a metal; to oxygen or ethylene, which can form a three-membered ring with a metal and thus can be said to have two potential junctions, to larger portions such as ethylenediamine or aza macrocycles, which form up to the maximum number of individual bonds to one or more metals that are allowed by the available sites on the metal and the number of single pairs or alternative binding sites of the free ligand. Numerous ligands can form bonds other than simple donor junctions, and can have several binding sites. The ligands useful herein may fall into several groups: the essential rigid macropolycyclic ligand, preferably a cross-bridge macropolycycle (preferably there will be one such ligand in a useful transition metal complex, but more, for example two, may be present. , but not in preferred mononuclear complexes); others, optional ligands, which are generally different from the essential rigid macropolycyclic ligand (generally there will be from 0 to 4, preferably from 1 to 3 of these ligands); and ligands transiently associated with the metal as part of the catalytic cycle, the latter typically being related to water, hydroxide, oxygen or peroxides. The ligands of the third group are not essential to define the metal bleach catalyst, which is a stable and isolable chemical compound that can be fully characterized. Ligands that bind to metals through donor atoms each having at least a single pair of electrons available for donation to a metal have a donor capacity, or potential denticity, at least equal to the number of donor atoms. In general, that donor capacity can be exercised completely or only partially.

Rigid macropolycyclic liquids To reach the transition metal catalysts of the present, a rigid macropolycyclic ligand is essential. This is coordinated (connected covalently to any of the transition metals identified above) by at least three, preferably at least four and most preferably four or five donor atoms to the same transition metal. Generally, the rigid macropolycyclic ligands of the present can be seen as the result of imposing additional structural rigids on specifically selected "macrocycles of origin". The term "rigid" has been defined herein as the conversation of contracted flexibility: see D.H. Busch, Chemical Reviews, (1993), 93, 847-860, incorporated by reference. Most particularly, "rigid" as used herein, means that the essential ligand, to be suitable for the purposes of the invention, must be determinably stiffer than a macrocycle ("macrocycle of origin") that is otherwise identical (which have the same ring size and type and number of atoms in the main ring) but lacks the superstructure (especially linker portions or, preferably cross-bridged portions) of the present ligands. To determine the comparative stiffness of macrocycles with and without superstructures, the practitioner will use the free form (not the metal-bonded form) of macrocycles. It is well known that stiffness is useful for comparing macrocycles; suitable tools for determining, measuring or comparing stiffness include computational methods (see, for example, Zimmer, Chemical Reviews, (1995), 95 (38), 2629-2648 or Hancock et al., Inorganic Chimica Acta (1989), 164 , 73-84 A determination of whether a macrocycle is more rigid than another can be done simply by constructing a molecular model, so it is not generally essential to know configurational energies in absolute terms or calculate them accurately. the stiffness of one macrocycle against another using inexpensive computer tools for personal computers, such as ALCHEMY III, commercially available from Tripos Associates.Tripos also has more expensive programs available that allow not only comparative but absolute determinations; alternatively, SHAPES ( see Zimmer, cited above.) An observation that is significant in the context of The present invention is that there is an optimum for the present purposes when the macrocycle of origin is distinctly flexible compared to the cross-bridge shape. Thus, unexpectedly, it is preferred to use origin macrocycles containing at least four donor atoms, such as cyclama derivatives, and cross-bridge them, instead of starting with a macrocycle of more rigid origin. Another observation is that cross-bridge macrocycles are significantly preferred over macrocycles that are bridged in other ways. The macrocyclic ligands of the present are of course not limited to being synthesized from any preformed macrocycle plus a preformed "enrichment" or "conformational modification" element: instead, a wide variety of synthetic media, such as synthesis, are useful. printed. See, for example, Busch et al., Reviewed in "Heterocyclic compounds: Aza-crown macrocycles", J.S. Bradshaw et al., Mentioned above in the background section of the present, for synthetic methods. In one aspect of the present invention, the rigid macropolycidal ligands of the present invention include those comprising: (i) an organic macrocycle ring containing four or more donor atoms (preferably at least 3, most preferably at least 4, of these donor atoms are N), separated from one another by covalent bonds of at least one, preferably 2 or 3 non-donor atoms, two to five (preferably three or four, most preferably four) of these donor atoms being coordinated to the same metal transition in the complex; (I) a linker portion, preferably a cross-bridging chain that covalently connects at least 2 (preferably non-adjacent) donor atoms of the organic macrocycle ring, said (preferably non-adjacent) donor atoms connected covalently to be donor heads bridge which are coordinated to the same transition metal in the complex, and wherein said linker portion (preferably a cross bridge chain) comprises from 2 to about 10 atoms (preferably the cross bridge chain is selected from 2, 3 or 4 atoms) no donors, and 4-6 non-donor atoms with an additional donor atom). In preferred embodiments of the present invention, the cross bridge macropolicicy is coordinated by four or five donor atoms to the same transition metal. These ligands comprise: (i) an organic macrocycle ring containing four or more donor atoms selected from N and optionally O and S, at least two of these donor atoms being N (preferably at least 3, most preferably at least 4, of these donor atoms are N), separated from each other by covalent bonds of 2 or 3 non-donor atoms, two to five (preferably three or four, most preferably four) of these donor atoms being coordinated to the same transition metal in the complex; (ii) a cross-bridging chain that covalently connects at least 2 non-adjacent N-donor atoms of the organic macrocycle ring, said non-adjacent N-donor atoms being N-bridge donor atoms that are coordinated to the same metal of transition in the complex, and wherein said cross-bridge chain comprises from 2 to about 10 atoms (preferably the cross-bridge chain is selected from 2, 3 or 4 non-donor atoms, and 4-6 non-donor atoms with a donor atom additional, preferably N). Although it is clear from the different contexts and illustrations already presented, the practitioner can also benefit if certain terms receive an additional definition and illustration. As used herein, "macrocyclic rings" are rings covalently connected and formed of four or more donor atoms (ie, heterogeneous atoms such as nitrogen or oxygen) with carbon chains connecting them, and any macrocyclic ring as defined. in the present it must contain a total of at least ten, preferably at least twelve, atoms in the macrocyclic ring. A macropolycyclic ligand herein may contain more than one ring of any type per ligand, but at least one macricyclic ring must be identifiable. In addition, in the preferred embodiments, two heterogeneous atoms are not directly connected. Preferred transition metal bleach catalysts are those in which the rigid macropolycyclic ligand comprises an organic macrocyclic ring (main ring) containing at least 10-20 atoms, preferably 12-18 atoms, most preferably about 12 to about 20 atoms, more preferably 12 to 16 atoms. Further, for preferred compounds, as used herein, "macrocyclic rings" are covalently linked rings formed of four or more donor atoms selected from N and optionally O and S, at least two of these donor atoms being N, with chains of C2 or C3 carbon connecting them, and any macrocyclic ring as defined here must contain a total of at least twelve atoms in the macrocyclic ring. A macropolycyclic crosslinker ligand of the present may contain more than one ring of any kind per ligand, but at least one macrocyclic ring must be detectable in the cross-bridge macropolycycle. Moreover, unless specifically stated otherwise, two heterogeneous atoms are not directly connected. Preferred transition metal catalysts are those in which the macropolycyclic cross-bridge ligand comprises an organic macrocyclic ring containing at least 12 atoms, preferably about 12 to about 20 atoms, most preferably about 12 to about 20 atoms. atoms, more preferably 12 to 16 atoms. The "donor atoms" in the present are heterogeneous atoms such as nitrogen, oxygen, phosphorus or sulfur (preferably N, O and S), which when incorporated into a ligand still have at least a single pair of electrons available to form a donor receiving union with a metal. Preferred transition metal bleach catalysts are those in which the donor atoms in the macrocyclic organic ring of the cross-linked macropolycyclic ligand are selected from the group consisting of N, O, S and P, preferably N and O, and most preferably all N. Also preferred are macropolyclic ligands comprising 4 or 5 donor atoms, all of which are coordinated to the same transition metal. The most preferred transition metal bleach catalysts are those in which the macropolycyclic cross-bridge ligand comprises 4 nitrogen donor atoms, all coordinated to the same transition metal, and those in which the macropolycyclic cross-bridge ligand comprises 5 nitrogen atoms all coordinated to the same transition metal. The "non-donor atoms" of the rigid macropolycyclic ligand of the present are very commonly carbon, although a number of atom types may be included, especially in optional exocyclic substituents (such as "hanging" portions, illustrated hereinafter) of macrocycles, which are not donor atoms for essential purposes of forming metal catalysts , nor are they carbon. Thus, in its broadest sense, the term "non-donor atoms" may refer to any atom that is not essential to form donor bonds with the catalyst metal. Examples of such atoms could include heterogeneous atoms such as sulfur as incorporated in a non-coordinating sulfonate group, phosphorus as incorporated in a phosphonium salt portion, phosphorus as incorporated in a P (V) oxide, a non-metal transition or similar. In certain preferred embodiments, all non-donor atoms are carbon.

The term "macropolyclic ligand" is used herein to refer to the essential ligand required to form the essential metal catalyst. As the term indicates, said ligand is both macrocyclic and polycyclic. "Polycyclic" means at least bicyclic in the conventional sense. The essential macropolycyclic ligands must be rigid, and the ligands that are preferred must also be cross-linked. Non-limiting examples of rigid macropolycylic ligands as defined herein include 1.3-1.6: 1 .3 Ligand 1.3 is a rigid macropolycyclic ligand according to the invention which is a cross-linked, methyl-substituted cyclamate derivative (all nitrogen atoms are tertiary) highly preferred. Formally, this ligand is called 5,12-dimethyl-1, 5,8,12-tetraazabicyclo [6.6.2] hexadecane using the extended von Baeyer system. See "A Guide to IUPAC Nomenclature of Organic Compunds: Recommendations 1993", R. Pánico, W.H. Powell and J-C Richer (Eds.), Blackwell Scientific Publications, Boston, 1993; see especially section R-2.4.2.1. In accordance with conventional terminology, N1 and N8 are "bridgehead atoms"; as defined herein, most particularly "bridgehead donor atoms" since they have single pairs capable of donating to a metal. N1 is connected to two donor atoms that are not bridgeheads, N5 and N12, by means of different carbon chains 2,3,4 and 14,13 and to the bridgehead donor atom N8 by a "linker portion" a, b here is a carbon chain saturated with two carbon atoms. N8 is connected to two donor atoms that are not bridgeheads, N5 and N12, by means of chains of different 6.7 and 9.10.11. The string a, b is a "linker portion" as defined herein, and is of the special and preferred type known as a "cross bypass" portion. The "macrocyclic ring" of the ligand above, or "major ring" (IUPAC), includes all four donor atoms and chains 2,3,4; 6.7; 9,10,11 and 13,14 but not a, b. This ligand is conventionally bicyclic. The short bridge or "linker portion" a, b is a "cross bridge" as defined herein, with a, b dissecting the macrocyclic ring. 1. Ligand 1.4 is found in the general definition of rigid macropolyclic ligands as defined herein, but is not a preferred ligand since it is not a "cross-bridge" as defined herein. Specifically, the "linker portion" a, b connects "adjacent" donor atoms N1 and N12, which is outside the preferred embodiment of the present invention; see for comparison the rigid anterior macropolyclic ligand, in which the linker portion a, b is a cross-bridged portion and connects "non-adjacent" donor atoms. 1. 5 Ligand 1.5 falls within the general definition of rigid macrocyclic ligands as defined herein. This ligand can be seen with a "main ring" which is a tetraazamacrocycle having three donor atoms of bridgehead. This macrocycle makes a bridge by means of a "linker portion" that has a more complex structure than a simple chain, containing as it does a secondary ring. The linking portion includes both a "cross bridge" link mode, and a non-cross bridge mode. 1 .6 Ligand 1.6 falls within the general definition of rigid macrocyclic ligands. Five donor atoms are present; two being donor atoms of bridgehead. This ligand is a preferred cross-bridge ligand. It does not contain exocyclic or suspended substituents that have aromatic content. In contrast, for comparison objects, the following ligands (1.7 and 1.8) do not conform to the broad definition of rigid macropolycyclic ligands in the present invention or to the preferred cross-bridge sub-family thereof and therefore are fully outside the present invention. 1. 7 In the supra ligand, no nitrogen atom is a bridgehead donor atom. There are insufficient donor atoms. 1 .8 The ligand supra is also outside the present invention. Nitrogen atoms are not bridgehead donor atoms, and the chaining of two carbons between the two main rings does not meet the invention's definition of a "linker portion" because, instead of chaining through a single ring macrocycle, chains two different rings. The bond therefore does not confer rigidity as used in the term "rigid macropolycyclic ligand". See the definition of "linker portion" here above. Generally, the essential rigid macropolycyclic ligands (and the corresponding transition metal catalysts) herein comprise: (a) at least one major macrocycle ring comprising three or more heterogeneous atoms; and (b) a covalently connected non-metal superstructure capable of increasing the stiffness of the macrocycle, preferably selected from (i) a bridge superstructure, such as a linker portion; (ii) a cross bridge superstructure, such as a cross bridge linker portion; and (iii) combinations thereof. The term "superstructure" is used herein as defined by Busch et al., In the Chemical Reviews article incorporated herein above. The preferred superstructures herein not only improve the stiffness of the original macrocycle, but also favor the bending of the macrocycle so that it coordinates a metal in a cavity. Suitable superstructures can be remarkably simple, for example a linking portion like any of those illustrated in 1.9 and 1.10 can then be used.

(CH2) n 1 -9 wherein n is an integer, for example from 2 to 8, preferably less than 6, typically 2 to 4, or 1.10 where m and n are integers from 1 to 8, more preferably from 1 to 3; Z is N or CH; and T is a compatible substituent, for example H, alkyl, trialkylammonium, halogen, nitro, sulfonate, or the like. The aromatic ring in 1.11 can be replaced by a saturated ring in which the Z atom that connects inside the ring can contain N, O, S or C. Without wishing to be limited by theory, it is believed that the preorganization constructed within the ligands macropolycyclic in the present that leads to extrakinetic and / or thermodynamic stability of their metal complexes arises from either or both topological limitations and improved stiffness (loss of flexibility) compared to the original free macrocycle that has no superstructure. The rigid macropolycyclic ligands as defined herein and their preferred cross-bridge sub-family, which can be said to be "ultra-rigid" combine two sources of fixed pre-organization. In the ligands preferred herein, the linker portions and the original macrocycle rings combine to form ligands that have a significant "double" degree, typically larger than in many known superstructured ligands in which a superstructure adheres to a macrocycle often not saturated, long flat. See, for example D.H. Busch, Chemical Reviews, (1993), 93, 847-880. In addition, the preferred ligands herein have a number of particular properties, including (1) which are characterized by very high affinities to proton, as in the so-called "proton sponges"; (2) They can react slowly with multivalent transition metals, which when combined with (1) above, makes the synthesis of their complexes with certain hydrophilic metal ions difficult in hydroxyl solvents; (3) When coordinating transition metal atoms as identified herein, the ligands result in complexes having exceptional kinetic stability such that metal ions only dissociate extremely slowly under conditions that would destroy complexes with ligands ordinary; and (4) these complexes have exceptional thermodynamic stability; however, the unusual kinetics of ligand dissociation from the transition metal can overcome conventional equilibrium measurements that could quantify this property. Other superstructures suitable for use but more complex for objects of the present invention include those that contain an additional ring, as in 1.5. Other bridge superstructures when added to a macrle include, for example, 1.4. In contrast, cross-bridge superstructures unexpectedly produce a substantial improvement in the utility of a macrlic ligand for use in oxidation catalysis: a preferred cross-bridge superstructure is 1.3. An illustrative superstructure of a bridge combination plus cross-bridging is 1 .11: In 1.1 1, the linking portion (i) is cross-bridged, while the linking portion (ii) is not. 1.1. 1 is less preferred than 1.3. More generally, a "linker portion" as defined herein, is a covalently bonded portion comprising a plurality of atoms that have at least two covalent adhesion points to a macrocycle ring and that are not part of the main ring or macrocycle rings. In other words, with the exception of the bonds formed by adhering it to the original macrocycle, a linker portion is completely in a superstructure. In preferred embodiments of the present invention, a cross bridge macropolicicy is coordinated by four or five donor atoms to the same transition metal. These ligands comprise: (i) an organic macrocycle ring containing four or more donor atoms (preferably at least 3, most preferably at least 4, of these donor atoms are N), separated from one another by covalent bonds of 2 or 3 non-donor atoms, two to five (preferably three or four, most preferably four) of these donor atoms being coordinated to the same transition metal in the complex and (ii) a cross-bridging chain that covalently connects at least 2 atoms non-adjacent donors of the organic macrocycle ring, said covalently connected non-adjacent donor atoms being bridgehead donor atoms that are coordinated to the same transition metal in the complex, and wherein said cross-bridge chain comprises from 2 to about 10 atoms (preferably the cross-bridge chain is selected from 2, 3 or 4 non-donor atoms, and 4-6 non-donor atoms with one atom or additional donor). The terms "cross-bridge" or "cross-bridging" as used herein, refer to covalent ligation, bisection or "bonding" of a macrocycle ring in which two atom ring-donor atoms are covalently linked via a chaining portion, for example, an additional chain other than the macrocycle ring, and furthermore, preferably, which is at least one donor atom of the macrocycle ring in each of the macrocycle ring sections separated by ligation, bisection or binding. Cross bridging is not present in structure 1.4 here above; is present in 1.3, wherein two donor atoms of a preferred macrocycle ring are connected in such a way that there is no donor atom in each of the bisection rings. Of course, with the condition that the cross bridge is present, any other bridge type can be optionally added and the bridge macrocycle will retain the referred property of being "cross bridge": see structure 1.1 1. A "cross bridge chain" "or" cross-bridging chain "as defined herein, is therefore a highly preferred type of chaining portion comprising a plurality of atoms which have at least two points of covalent adhesion to a ring macrocycle and which do not form part of the original macrocycle ring (main ring), and in addition, which are connected to the main ring using the rule identified in the definition of the term "crossed bypass". The term "adjacent" as used herein in connection with donor atoms in a macrocycle ring means that there are no donor atoms intervening between a first donor atom and another donor atom within the macrocycle ring; all atoms involved in the ring are non-donor atoms, typically carbon atoms. The term "non-adjacent" as used herein in connection with donor atoms in a macrocycle ring means that there is at least one donor atom intervening between a first donor atom and another that has been referred to. In preferred cases such as a cross-bridge tetraazamacrocice, there will be at least one pair of non-adjacent donor atoms which are bridgehead atoms, and an additional pair of donor atoms, not bridgeheads. The "bridgehead" atoms herein are atoms of a macropolycyclic ligand which are connected within the structure of the macrocycle such that each non-donor bond to such an atom is a single covalent bond and there are sufficient covalent single bonds for connect the atom called "bridgehead" in such a way that it forms a union of at least two rings, this number being the maximum observable by visual inspection, in the uncoordinated ligand. In general, the metal bleach catalysts of the present invention may contain bridgehead atoms which are carbon, however, and very importantly, in certain preferred embodiments, all the essential bridgehead atoms are heterogeneous atoms, all the atoms heterogeneous are tertiary, and in addition, each of them coordinate through a donation of pair only to metal. The transition metal bleach catalysts which are preferred herein must contain at least two N bridgehead atoms, and in addition, each coordinate through pair donation alone to the metal. In this way, the bridgehead atoms are points of union not only of rings in the macrocycle, but also of chelating rings. The term "an additional donor atom" unless specifically indicated otherwise, as used herein, refers to a donor atom except a donor atom contained in the macrocycle ring of an essential macropolicyl. For example, an "additional donor atom" may be present in an optional exocyclic substituent of a macrocyclic ligand, in a cross-bridge chain thereof. In certain preferred embodiments, an "additional donor atom" is present only in a cross-bridge chain. The term "coordinated with the same transition metal" as used herein is used to emphasize that a particular donor atom or ligand does not bind to two or more different metal atoms, but rather, only to one.

Optional Liqings It should be recognized for the transition metal bleach catalysts useful in the catalyst systems of the present invention that additional non-macropolyclic ligands may also optionally be coordinated to the metal, as is necessary to complete the coordination number of the complexed metal. Said ligands can have any number of atoms capable of donating electrons to the catalyst complex, but the preferred optional ligands have a denticity of 1 to 3, preferably 1. Examples of such ligands are H2O, ROH, NR3, RCN, OH ', OOH- , RS-, RO ", RCOO", OCN ", SCN", N3", CN", F "Cl", Br ", I", O2", NO3", NO2", SO42", PO43- ', phosphates organic, organic phosphonates, organic sulfates, organic sulfonates, and aromatic N-donors such as pyridines, pyrazines, pyrazoles, imidazoles, benzimidazoles, pyrimidines, Mazolas and thiazoles with R being H, optionally substituted alkyl, optionally substituted aryl. Preferred transition metal bleach catalysts consist of one or two non-macropolyclic ligands.

The term "non-macropolicylic ligands" is used herein to refer to ligands such as those illustrated immediately hereinbefore which are generally not essential to form the metal catalyst, and are not cross-bridge macropolicicles. "Non-essential" with reference to such non-macropolyclic ligands means that, in the invention as broadly defined, they can be substituted by a variety of common alternating ligands. In highly preferred embodiments in which the metal, the macropolyclic and non-macropolyclic ligands are finely tuned within a transition metal bleach catalyst, there can, of course, be significant differences in performance when the indicated non-macropolyclic ligand (s) is replaced by alternate ligands, specifically not illustrated, additional. The term "metal catalyst" or "transition metal bleach catalyst" is used herein to refer to the essential catalyst compound of the invention and is commonly used with the "metal" qualifier unless it is absolutely clear from the context . Note that there is a description here above in relation specifically to optional catalyst materials. In them the term "bleach catalyst" may be used without qualification to refer to optional materials, organic (metal-free) catalysts, or metal-containing catalysts that lack the advantages of the essential catalyst: such optional materials, for example, they include metal porphyrins or photobleaches that contain metal. Other optional catalytic materials herein include enzymes. Macropolycyclic cross-bridge ligands include the macropolycyclic cross-bridge ligand selected from the group consisting of: (i) the cross-linked macropolycyclic ligand of formula (I) having denticity of 4 or 5: (i); (ii) the macropolycyclic cross-bridge ligand of formula (II) having denticity of 5 or 6: (N); (iii) the macropolicylic cross-bridge ligand of the formula (III) having denticity of 6 or 7: (I I I); wherein in these formulas: - each "E" is the portion (CRn) aX- (CRn) a-, wherein X is selected from the group consisting of O, S, NR and P, or a covalent bond, and preferably X is a covalent bond and for each E the sum of a + a 'is independently selected from 1 to 5, more preferably 2 and 3; - each "G" is the portion (CRn) b; - each "R" is independently selected from H, alkyl, alkenyl, alkynyl, aryl, alkylaryl (for example benzyl) and heteroaryl, or two or more R are covalently linked to form an aromatic, heteroaromatic, cycloalkyl, or heterocycloalkyl ring; each "D" is a donor atom independently selected from the group consisting of N, O, S and P and at least two D atoms are bridgehead donor atoms coordinated to the transition metal (in preferred embodiments, all atoms D designated donors are donor atoms that coordinate to the transition metal, in contrast to heterogeneous atoms in the structure that are not in D such as those that may be present in E; heterogeneous atoms that are not D may be non-coordinating and in fact are non-coordinating provided they are present in the preferred embodiment); - "B" is a carbon atom or "D" donor atom, or a cycloalkyl or heterocyclic ring; - each "n" is an integer selected independently from 1 and 2, by completing the valence of the carbon atoms to which the R portions are covalently linked; - each "n" 'is an integer independently selected from 0 and 1, completing the valence of donor atoms D to which the R portions are covalently linked; - each "n" "is an integer selected independently of 0, 1, and 2 completing the valence of the B atoms to which the R portions are covalently linked; - each "a" and "a" 'is an integer selected independently from 0-5, preferably a + a' equal to 2 or 3, where the sum of all "a" plus "a" 'in the ligand of Formula (I) is within the range of about 6 (preferably 8) to about 12, the sum of all "a" plus "a" 'in the ligand of formula (II) is within the scale of about 8 (preferably 10) to about 15, and the sum of all "a" plus "a" 'in the ligand of formula (III) is within the range of about 10 (preferably 12) to about 18; - each "b" is an integer selected independently from 0-9, preferably 0-5, or in any of the above formulas, one or more of the portions (CRn) b covalently attached from any atom D to B is absent in both that at least two (CR) covalently bind two of the donor atoms D to atom B in the formula, and the sum of all "b" s is within the range of about 1 to about 5. Bleaching catalysts are preferred of transition metal in which in the cross-bridge macropolycyclic ligand the D and B are selected from the group consisting of N and O, and preferably all D are N. Also preferred are in the cross-linked macropolycyclic ligand all "a" are selected independently of integers 2 and 3, all X are selected from covalent bonds, all "a" 'are 0, and all "b" s are selected independently from integers 0, 1, and 2. The macropolicíclicos ligands of puen you cross tetradentados and pentadentados are most preferred. Unless otherwise specified, the convention herein when referring to denticity, as in "the macropoliciclo has a denticidad of four" will be to refer to a characteristic of the ligand: that is, the maximum number of donor unions that is able to form when a metal is coordinated. Such a ligand is identified as "tetradentate". Similarly, a macropolicicy containing 5 nitrogen atoms each with a single pair is referred to as "pentadentates". The present invention encompasses bleaching compositions in which the rigid macrocyclic ligand exerts its complete denticity, as established, on the transition metal catalyst complexes; moreover, the invention also encompasses any equivalent that can be formed, for example, if one or more donor sites are not coordinated directly to the metal. This can happen, for example, when a pentadentate ligand coordinates through four donor atoms to the transition metal and a donor atom is protonated. Preferred are bleach compositions containing metal catalysts in which the macropolycyclic cross-bridge ligand is a bicyclic ligand; preferably the macropolyicylic cross-bridge ligand is a macropolycylic portion of the formula (I) having the formula: where each "a" is independently chosen from the integers 2 or 3, and each "b" is independently chosen from the integers 0, 1 and 2.

Also preferred are the macropolycyclic cross bridge ligands selected from the group consisting of: (i), and wherein in these formulas: - each "R" is independently selected from H, alkyl, alkenyl, alkyl, aryl, alkylaryl and heteroaryl, or two or more R are covalently linked to form an aromatic, heteroaromatic, cycloalkyl or heterocycloalkyl ring; - each "n" is an integer selected independently of 0, 1 and 2, completing the valence of the carbon atoms to which the R portions are attached; - each "b" is an integer selected independently of 2 and 3; and - each "a" in a selected integer independently of 2 and 3. Also preferred are macropolycyclic cross bridge ligands having the formula: where in this formula: - each "n" is an integer independently chosen from 1 and 2, which completes the valence of the carbon atom to which the R portions are covalently linked; - each "R" and "R1" is independently chosen from H, alkyl, alkenyl, aikinyl, aryl, aikaryl and heteroaryl, or R and / or R1 are covalently linked to form an aromatic, heterocaromatic, cycloalkyl or heterocycloalkyl ring, and wherein preferably all R are H and R1 are independently selected from alkyl, alkenyl or alkynyl of Cr C20 substituted or unsubstituted, linear or branched; - each "a" is an integer chosen independently of 2 or 3; - preferably all the nitrogen atoms in the rings of macropolicicros cross bridge coordinate with the transition metal. Another preferred subgroup of the transition metal complexes useful in the compositions and methods of the present invention include the Mn (ll), Fe (ll) and Cr (lll) complexes of the ligand having the formula: wherein m and n are integers from 0 to 2, p is an integer from 1 to 6, preferably m and n are both 0 or both 1 (preferably both 1), or m is 0 and n is at least 1; and p is 1; and A is a non-hydrogen portion that preferably has no aromatic content; more particularly, each A can vary independently and is preferably selected from methyl, ethyl, propyl, isopropyl, butyl, isobutyl, tert-butyl, C5-C20 alkyl, and one, but not both, of portions A is benzyl, and combinations thereof. In one such complex, an A is methyl and an A is benzyl. This includes the preferred cross-linked macropolycyclic ligands having formula: wherein in this formula "R1" is independently chosen from H, and an alkyl, alkylaryl, alkeniion or alkynyl of C-1-C20. substituted or unsubstituted, linear or branched, most preferably R1 is alkyl or alkylaryl; and preferably all the nitrogen atoms in the macropolyclic rings are coordinated with the transition metal. Also preferred are the macropolycyclic cross bridge ligands having the formula: wherein in this formula: - each "n" is an independently chosen integer of 1 and 2, which completes the valence of the carbon atom to which the R portions are covalently bound; - each "R" and "R1" is independently chosen from H, alkyl, alkenyl, alkynyl, aryl, alkylaryl and heteroaryl, or R and / or R1 are covalently linked to form an aromatic, heteroaromatic, cycloalkyl, or heterocycloalkyl ring, and wherein preferably all R are H and R1 is independently selected from a linear or branched, substituted or unsubstituted alkyl, alkenyl or alkynyl of C1-C20; - each "a" is an independently chosen whole of 2 or 3; - preferably all the nitrogen atoms in the macropolyclic rings are coordinated with the transition metal. These include the macropoicyclic cross-bridge ligands that have the formula: wherein in any of these formulas, "R1" is independently chosen from H, or, preferably substituted or unsubstituted, linear or branched alkyl, alkenyl or alkynyl of C1-C20; and preferably all the nitrogen atoms in the macropolycyclic rings coordinate with the transition metal. The present invention has various variations and alternate modes that do not depart from the spirit and scope thereof. Thus, in the compositions of the present invention, the macropolyclic ligand can be replaced by any of the following: In the foregoing, the portions R, R ', R ", R'" for example may be methyl, ethyl, or propyl. (Note that the above formulas, the short diagonal lines attached to certain N atoms are an alternative representation of a methyl group.) Although the above illustrative structures involve tetra-aza derivatives (four nitrogen donor atoms), they can also be ligands and corresponding complexes according to the present invention, for example from any of the following: In addition, by using only a simple organic macropolycycle, preferably a cyclamate cross bridge derivative, a broad scale of bleach catalyst compounds of the invention can be prepared; it is believed that some of these are novel chemical compounds. The preferred transition metal catalysts of both the cyclam derivatives and the non-cyclam derivatives of the cross-bridge type are illustrated below, without limitation: In other embodiments of the invention, transition metal complexes, such as Mn, Fe or Cr complexes, especially complexes in oxidation state (II) and / or (III), of the metals identified above are also included. the present invention with any of the ligands illustrated below: wherein R1 is independently chosen from H (preferably non-H) and substituted or unsubstituted, linear or branched C-? -C2o alkyl, alkenyl or alkynyl and L is any linking portions provided herein, for example 1.9 or 1.10; where R1 is as defined above, m, n, o and p can vary independently, and are integers that can be 0 or a positive integer and can vary independently while with respect to the provisions that the sum m + n + o + p is from 0 to 8 and L is any of the link portions defined in this document; where X and Y can be any of the R1 defined above, m, n, 0 and p are as defined above and q is an integer, preferably from 1 to 4; or, generally, where L is any of the linking portions indicated in this document, X and Y can be any of the R1 defined above, and m, n, o and p are as defined above. Alternatively, another useful ligand is: where R1 is any of the portions R1 defined above.

Hanging portions The rigid macropolycyclic ligands and corresponding transition metal complexes and compositions herein may also incorporate one or more pendant portions, in addition to, or as a replacement for the portions R1. Such hanging portions are illustrated in a non-limiting manner by any of the following: (CH2) n -CH3 CH2) nC (O) NH2 - (CH2) nCNC CH2) nC (O) OH- (CH2) n- C (O) NR2 - (CH2) n- OH - (CH2) n- C (O) OR wherein R is, for example, a C 1 -C 12 alkyl, most commonly a C 1 -C 4 alkyl, and Z and T are as defined in 1.10. Pending portions may be useful, for example, in the case where it is desired to adjust the solubility of the catalyst in a particular auxiliary solvent. Alternatively, the complexes of any macropolycyclic, cross-linked, highly rigid ligands prior to any indicated metals are equally within the invention. Catalysts are preferred where the transition metal was chosen from manganese or iron, most preferably manganese. Catalysts are also preferred where the molar ratio of the transition metal and the macropolyclic ligand in the transition metal bleach catalyst is 1: 1, and the catalyst comprising a metal per metal bleach catalyst complex is even more preferred. of Transition. Other preferred transition metal bleach catalysts are mononuclear monometallic complexes. The term "mononuclear monometallic complex" is used in the present invention to refer to an essential transition metal bleach catalyst compound for identifying and distinguishing a preferred class of compounds that only contain one metal atom per mole of compound and only one metal atom per mole of cross-bridge macropolycyclic ligand. Preferred transition metal bleach catalysts also include those where at least four of the donor atoms in the rigid macropolyclic ligand, preferably at least four nitrogen donor atoms, two of which form an apical junction angle with the same transition metal of 180 ± 50 ° and two of which form at least one equatorial junction angle 90 ± 20 °. Said catalysts preferably have in total four or five nitrogen donor atoms and also have a geometry of coordination chosen octahedron distorted (including distortion general tetragonai and trigonal antiprismática) and distorted trigonal prisms, and preferably where in addition the macropolicíclico ligand of crossed bridge is in the folded conformation (as described, for example, in Hancock and Martell, Chem. Rev., 1989, 89, on page 1894). A folded conformation of a macropolycyclic cross-bridge ligand in a transition metal complex is also illustrated below: This catalyst is the complex of Example 1 hereafter. The central atom is Mn; the two ligands on the right are chloride, and a Bciclama ligand occupies the left side of the distorted octahedral structure. The complex contains an N-Mn-N angle of 158 ° incorporating the two donor atoms in the "axial" position, the corresponding angle N-Mn-N for the nitrogen donor atoms is 83.2 ° in plane with the two chloride ligands . Alternatively, the preferred synthetic laundry or cleaning compositions herein contain transition metal complexes of a macropolycyclic ligand in which there is a major energy preference of ligand for a folded conformation, different from an "open" and / or "planar" one. and / or "flat". In comparison, for example, a conformation that is not favored may be the trans- structures shown in Hancock and Martell, Chemical Reviews, (1989), 89, on page 1984 (see Figure 18), incorporated herein. by reference.

In view of the above coordination description, the present invention includes bleaching compositions comprising a transition metal bleach catalyst, especially based on Mn (ll) or Mn (III) or correspondingly Fe (II) or Fe (III). ) or Cr (ll) or Cr (III), wherein two of the donor atoms in the rigid macropolyclic ligand, preferably two nitrogen donor atoms, mutually occupy positions trans- of the coordination geometry, and at least two of the donor atoms in the rigid macropolycyclic ligand, preferably at least two nitrogen donor atoms, occupy cis-equatorial positions of the coordination geometry, including in particular those cases in which there is a substantial distortion as illustrated above in the present invention. The present compositions may further include transition metal bleach catalysts in which the number of asymmetric sites can vary widely; in this way, both S- and R- absolute confirmations can be included for any stereochemically active site. Other types of isomerism are also included, such as geometric isomerism. The transition metal bleach catalyst may also include mixtures of geometric isomers or stereoisomers.

Catalyst purification In general, the purity state of the transition metal bleach catalyst can vary, as long as any impurities, such as by-products of the synthesis, free ligand (s), transition metal salt precursors unreacted, colloidal organic or inorganic particles, and the like, are not present in amounts that substantially decrease the usefulness of the transition metal bleach catalyst. It has been found that preferred embodiments of the present invention include those in which the transition metal bleach catalyst is purified by any suitable means, since it does not excessively consume available oxygen (AvO). Excessive consumption of AvO is defined as the inclusion of any situation of exponential decrease in AvO levels of bleaching solutions, oxidants or catalytic solutions with a given time at 20 to 40 °. The preferred transition metal bleach catalysts of the present invention, whether purified or not, when placed in the alkaline aqueous solution with pH regulation, of about 9 (carbonate / bicarbonate pH regulator) at a temperature of about 40 ° C, have a constant decrease relatively in levels of AvO with given time, in the preferred cases, this rate of decrease is linear or approximately linear. In the preferred modalities, there is a consumption speed of AvO at 40 ° C given by a graph slope of% AvO vs. time (in seconds) (hereinafter called "AvO slope") from about -0.0050 to about -0.0500, most preferably -0.0100 to about -0.0200. In this way, a preferred Mn bleaching catalyst (ll) according to the invention has an AvO slope of about -0.0140 to about -0.0182.; in contrast, a somewhat less preferred transition metal catalyst has an AvO slope of -0.0286. Preferred methods for determining the consumption of AvO in aqueous solutions of transition metal bleach catalysts of the present invention include the already known iodometric method, or its variants, such as the methods which are commonly applied for the peroxide of hydrogen. See, for example, Organic Peroxides, Vol. 2, D. Swern (Ed.), Wiley-lnterscience, New York, 1971, for example in the table on page 585 and references therein, including P.D. Bartlett and R. Altscul, J. Amer. Chem. Soc, 67, 812 (1945) and W.E. Cass, J. Amer. Chem. Soc, 68, 1976 (1946). Accelerators such as ammonium molybdate can be used. The general procedure that is used in the present invention for preparing an aqueous solution of catalyst and a hydrogen peroxide in a light alkaline pH regulator, for example carbonate / bicarbonate with a pH of 9, and monitoring the consumption of hydrogen peroxide by the periodic removal of aliquots of the solution that are "stopped" from an additional loss of hydrogen peroxide by acidification, using glacial acetic acid, preferably with cooling (on ice). These aliquots can then be analyzed, by reaction with potassium iodide, optionally, however, ammonium molybdate (especially low-impurity molybdate) is sometimes used, see for example the US patent. 4,596,701) to accelerate the complete reaction, followed by retrotitulation using sodium thiosulfate.

Other variations of the analytical procedure can be used, for example thermometric methods, methods of regulation of potential pH (Ishibashi et al., Anal. Chim Acta (1992), 261 (1-2), 405-10) or photometric methods for determination of peroxide. of hydrogen (EP 485,000 A2, May 13, 1992). Also useful are variations of the methods that allow the determination of fractions, for example peracetic acid and hydrogen peroxide, in the presence or absence of the transition metal bleach catalyst, see for example JP 92-303215 of 16 October 1992. In another embodiment of the present invention, laundry and cleaning compositions incorporating transition metal bleach catalysts that have been purified to such an extent that they exhibit a differential AvO loss reduction relative to untreated catalysts are included. of at least about 10% (the units indicated have no dimensions since they represent the ratio of the AvO slope of the transition metal bleach catalyst treated on the AvO slope of the transition metal bleach catalyst or treated , actually an AvO relationship). In other words, the slope of AvO is improved by purification in such a way that it is brought to the preferred scales identified above. In yet another embodiment of the present invention, two processes have been identified that are particularly effective for improving the adequacy of the transition metal bleach catalysts, while they are being synthesized, for incorporation into laundry and cleaning products or for other cataylation applications. of oxidation. One such method is any process that includes the step of treating the transition metal bleach catalyst, preparing it by extracting the transition metal bleach catalyst, in solid form, with an aromatic hydrocarbon solvent; Suitable solvents are stable to oxidation under conditions of use and include benzene and toluene, preferably toluene. Surprisingly, the toluene extraction can be improved so that the AvO tilt can be measured (see the description included in the present invention in previous paragraphs). Another method that can be used to improve the AvO slope of the transition metal bleach catalyst is to filter a solution thereof using any suitable filtration medium to remove small or colloidal particles. Such means include the use of fine pore filters, centrifugation or coagulation of colloidal solids. In more detail, a complete process for purifying a transition metal bleach catalyst of the present invention may include: (a) dissolving the transition metal bleach catalyst, in preparation, in hot acetonitrile: (b) filtering the resulting solution hot, for example, at about 70 ° C, through glass microfibers (for example a glass microfiber filter paper available from Whatman); (c) if desired, filter the solution of the first filtration through a 0.2 micron membrane (eg, a 0.2 micron filter available from Millipore) or centrifuge to remove the colloidal particles; (d) evaporating the solution from the second filtration to dryness; (e) washing the solids from step (d) with toluene, for example, five times using toluene in an amount twice the volume of solids of the bleach catalyst; (f) drying the product of step (e). Another method that can be used, in any suitable combination with aromatic solvent washes and / or removal of fine particles is recrystallization. Recrystallization, for example from a transition metal bleach catalyst of Mn (II) Bciclama chloride, can be carried out from hot acetonitrile. Recrystallization can have its disadvantagesFor example, it can be very expensive. The present invention has various alternative modalities and ramifications. For example, in the field of laundry detergents and laundry detergent additives, the invention includes all manners of bleach-containing compositions or bleach additives, including for example, fully formulated heavy duty granular detergents containing sodium perborate or sodium percarbonate and / or a preformed peracid derivative such as OXONE as the main oxidant, the transition metal catalyst of the invention, a bleach activator such as tetracetylethylenediamine or a similar compound, with or without sodium salt, nonanoyloxybenzenesulfonate, and the like. Other forms of suitable compositions include laundry bleaching additive powders, automatic dish washing detergents in the form of granules or tablets, scrubbing powders and bath cleaners. In the compositions with solid form, the catalyst system may not have solvent (water), this is added by the user together with the substrate (a dirty surface) to be cleaned (or contains dirt to be oxidized). Other desirable embodiments of the present invention include dentifrice or denture cleaning compositions. Suitable compositions to which the transition metal complexes of the present invention may be added include dentifrice compositions containing stabilized sodium percarbonate, see for example the U.S.A. No. 5,424,060 and denture cleaners of the U.S. patent. No. 5,476,607 which are derived from a mixture containing a pre-granulated compressed mixture of anhydrous perborate, perborate monohydrate and a lubricant, monopersulfate, non-granulated perborate monohydrate, proteolytic enzyme and sequestering agent, although the compositions without enzymes are also very effective. Optionally, excipients, detergency builders, colors, flavors and surfactants can be added to such compositions, being auxiliary materials characteristic for the intended use. RE32,771 discloses another denture cleaning composition to which the transition metal catalysts of the present invention can be usefully added. In this way, by simple mixing of, for example, from about 0.00001% to about 0.1% of the transition metal catalyst of the present invention, a cleaning composition is ensured which is particularly suitable for compaction in the form of a tablet.; this composition also comprises a phosphate salt, a perborate salt mixture wherein the improvement comprises a combination of anhydrous perborate and perborate monohydrate in an amount of about 50% to about 70% by weight of the total cleaning composition, where the combination includes at least 20% by weight of the total cleaning composition of anhydrous perborate, said combination having a portion present in a compact granulated mixture with from about 0.01% to about 0.70% by weight of said combination of a polymeric fluorocarbon, and a chelating or sequestering agent present in amounts greater than about 10% by weight to about 50% by weight of the total composition, said cleaning composition can clean soiled surfaces and the like with a soaking time of five minutes or less upon dissolving it into a solution water and a marked improvement in the clarity of the solution to the disintegration cleaning effectiveness and efficiency over the prior art. Of course, the denture cleaning composition need not extend to the sophistication of such compositions: if desired, auxiliary materials not essential for the provision of catalytic oxidation, for example the fluorinated polymer, can be omitted. In another non-limiting illustration, the present combination of transition metal catalysts and bleach activator and / or percarboxylic acid of the present invention can be added to an effervescent denture cleaning composition comprising monoperphthalate, for example the magnesium salt thereof. , and / or the composition of the US patent No. 4,490,269 incorporated in the present invention by reference. Denture cleaning compositions include those in the form of tablets, wherein the tablet composition is characterized by active oxygen levels on a scale of about 100 to about 200 mg / tablet; and compositions characterized by fragrance retention levels greater than about 50% over a period of 6 hours or greater. See the document of E.U. No. 5,486,304 incorporated by reference for more detailed information with respect especially to the retention of fragrance. The advantages and benefits of the present invention include cleaning compositions that have a superior bleaching compared to compositions that do not have the selected combination of transition metal bleach catalysts and bleach activator and / or organic percarboxylic acid. The superiority in bleaching is obtained using very low levels of a transition metal bleach catalyst. The invention includes embodiments that are especially suitable for washing fabrics, which have a low tendency to damage fabrics in repeated washes. However, numerous other benefits can be obtained; for example, the compositions may be relatively more aggressive, as necessary, for example, in deep cleaning of hard durable surfaces, for example, interiors of ovens, or kitchen surfaces having films or dirt difficult to remove. The compositions can be used both in "pretreatment" mode, for example to loosen dirt in kitchens and bathrooms; as in a "main wash" mode, for example in fully formulated heavy duty laundry detergent granules. In addition to the advantages of bleaching and / or removal of dirt, other advantages of the compositions of the present invention include its effectiveness in improving the sanitary conditions of surfaces ranging from washed textiles to kitchen countertops and bathroom tiles. Without attempting to be limited by theory, it is believed that the compositions can help control or kill a wide variety of microorganisms, including bacteria, viruses, subviral particles and molds; as well as destroying undesirable non-living proteins and / or peptides, such as certain toxins. The transition metal bleach catalysts useful in the present invention can be synthesized by any convenient route. However, the specific synthesis methods are illustrated in a non-limiting manner in details as indicated below.

EXAMPLE 1 Synthesis of rmn (bciclama) cl2. (a) Method 1"Bciclama" (5,12-dimethyl-1, 5,8,12-tetraaza-bicyclo) is prepared [6.6.2] hexadecane) by a synthesis method described by G.R. Weisman, et al., J. Amer. Chem. Soc. (1990), 12 12, 8604. Bciclama (1.00 g, 3.93 mmol) is dissolved in dry CH3CN (35 mL, distilled from CaH2). Subsequently the solution is evacuated to 15 mm until CH3CN begins to boil. Then the flask is subjected to atmospheric pressure with Ar. This degassing procedure is repeated 4 times. Under Ar, Mn (pyridine) 2Cl2 (1.12 g, 3.93 mmol) is added, synthesized according to the procedure of the H.T. Witteveen et al., J. Inorq. Nucí Chem., (1974), 36, 1535. The cloudy reaction solution slowly begins to darken. After stirring overnight at room temperature, the reaction solution turns dark brown with fine suspended particles. The reaction solution is filtered with a 0.2μ filter. The filtrate has a light tan color. This filtrate is evaporated to dry using a rotoevaporator. After drying overnight at 0.05 mm at room temperature, 1.35 g of white solid product was collected, yield 90%. Analysis of elements:% Mn, 14.45; % C, 44.22; % H, 7.95; theoretical for [Mn (Bciclama) CI2], MnC14H3oN4Cl2, MW = 380.26. Found:% Mn, 14.98; % C, 44.48,% H, 7.86; the spray mass spectroscopy of ions shows a main peak at 354 mu corresponding to [Mn (Bciclama) (formate)] +. (b) Method II Freshly distilled bilamine (25.00 g, 0.0984 mol), prepared by the same method above, is dissolved in dry CH3CN (900 ml, distilled from CaH2). Subsequently the solution is evacuated to 15 mm until the CH3CN begins to boil. Then the flask is subjected to atmospheric pressure with Ar. This degassing procedure is repeated 4 times. Under Ar, MnC (11.25 g, 0.0894 mol) is added. The cloudy reaction solution immediately darkens. After stirring for 4 hours at reflux, the reaction solution becomes dark brown with fine suspended particles. The reaction solution is filtered through a 0.2μ filter under dry conditions. The filtrate has a light tan color. This filtrate is evaporated until it is dried using a rotoevaporator. The resulting tan solid is dried overnight at 0.05 mm at room temperature. The solid is suspended in toluene (100 ml) and heated to reflux. The toluene is decanted and the procedure is repeated with an additional 100 ml of toluene. The rest of toluene is removed using a rotoevaporator. After drying overnight at 0.05 mm at room temperature, 37.75 g of a light blue solid product was collected, yield 93.5%. Analysis of elements:% Mn, 14.45; % C, 44.22; % H, 7.95; % N, 14.73% CI, 18.65; theoretical for [Mn (Bciclama) CI2], MnC14H3oN4Cl2, MW = 380.26. Found:% Mn, 14.69; % C, 44.69; % H, 7.99; % N, 14.78; % CI, 18.90 (Karl Fisher Water, 0.68%). The mass spectroscopy by ion spray showed a main peak at 354 mu corresponding to [Mn (Bciclama) (formate)] + - EXAMPLE 2 Synthesis of rmn (c4-bciclama) cl21 where c _? - bciclama = 5-n-butyl-12-methyl- 1, 5, 8, 12-tetraaza-biciclor6.6.2. hexadecane (a) Synthesis of C4-Bciclama -N "N- The tetracyclic adduct i is prepared by the literature method of H. Yamamoto and K. Maruoka, J. Amer. Chem. Soc. (1981), 103, 4194. I (3.00 g, 13.5 mmol) is It is dissolved in dry CH3CN (50 ml, distilled from CaH2), 1-iodobutane (24.84 g, 135 mmol) is added to the stirred solution under Ar.The solution is stirred at room temperature for 5 days, 4-iodobutane (12.42) is added. g, 67.5 mmoies) and the solution is stirred for a further 5 days at room temperature Under these conditions, it is completely monoalkylated with 1-iodobutane as shown by 13 C-NMR Methyl iodide (26.5 g, 187 mmoles) is added and the solution is stirred at room temperature for a further 5 days.The reaction is filtered using Whatman # 4 paper, in addition to vacuum filtration. A white solid was collected, ü, (6.05 g, 82%). 13 C NMR (CDCl 3) 16.3, 21.3, 21.6, 22.5, 25.8, 49.2, 49.4, 50.1, 51.4, 52.6, 53.9, 54.1, 62.3, 63.5, 67.9, 79.1, 79.2 ppm. Electrospray mass spectroscopy (MH + / 2, 147). Dissolve M (6.00 g, 11.0 mmol) in 95% ethanol (500 mL). Sodium borohydride (1.0 g, 290 mmol) is added and the reaction becomes milky white. The reaction is stirred under Ar for 3 days. Hydrochloric acid (100 ml, concentrate) is slowly added to the reaction mixture for 1 hour. The reaction mixture is evaporated until it is dried using a rotoevaporator. The white residue is dissolved in sodium hydroxide (500 ml, 1.00N). This solution is extracted with toluene (2 x 150 mL). The toluene layers are combined and dried with sodium sulfate. After removal of the sodium sulfate using the filtration, the toluene is evaporated until it is dried using a rotoevaporator. This resulting oil is dried at room temperature under high vacuum (0.05 mm) overnight. A colorless oil 2.95 g, 90% is obtained. This oil (2.10 g) is distilled using a short route distillation apparatus (distillation head temperature 1 15 ° C to 0.05 mm). Yield: 2.00 g, 13 C NMR (CDCl 3) 14.0, 20.6, 27.2, 27.7, 30.5, 32.5, 51.2, 51.4, 54.1, 54.7, 55.1, 55.8, 56.1, 56.5, 57.9, 58.0, 59.9 ppm. Mass spectroscopy. (MH +, 297). (b) Synthesis of [Mn (C4-Bciclama) CI?] C4-Bciclama (2.00 g, 6.76 mmol) is suspended in dry CH3CN (75 mL, distilled from CaH2). Then the solution is evacuated to 15 mm until CH3CN begins to boil. Then the flask is subjected to atmospheric pressure with Ar. This degassing procedure is repeated 4 times. MnCl 2 (0.81 g, 6.43 mmol) is added under Ar. The tanned turbid reaction solution immediately darkens. After stirring for 4 hours under reflux, the reaction solution becomes dark brown with fine suspended particles. The reaction solution is filtered through a 0.2 μ membrane filter under dry conditions. The filtrate has a light tan color. This filtrate is evaporated until it is dried using a rotoevaporator. The resulting white solid is suspended in toluene (50 mL) and heated to reflux. The toluene is decanted and the procedure is repeated with additional 100 m of toluene. The rest of toluene is removed using a rotoevaporator. After allowing it to dry overnight at 0.05 mm, at room temperature, 2.4 g of a light blue solid was obtained, yield 88%. The ion spray mass spectroscopy shows a main peak at 396 mu corresponding to [Mn (C4-Bciclama) (formate)] +.

EXAMPLE 3 Synthesis of rMn (Bz-Bciclama) Cb1 where Bz-Bciclama = 5-benzyM 2-methyl-1, 5,8,12-tetraaza-bicyclo.6,6,2. hexadecane (a) Synthesis of Bz-Bciclama This ligand is synthesized in a manner similar to the synthesis of C4-Bciclama described above in Example 2 (a) with the exception that benzyl bromide is used in place of 1-iodobutane 13C NMR ( CDCI3) 27.6, 28.4, 43.0, 52.1, 52.2, 54.4, 55.6, 56.4, 56.5, 56.9, 57.3, 57.8, 60.2, 60.3, 126.7, 128.0, 129.1, 141.0 ppm. Mass spectroscopy. (MH +, 331). (b) Synthesis of fMn (Bz-Bciclama) CI? l This complex is done in a manner similar to the synthesis of [Mn (C4-Bciclama) CI2] described above in example 2 (b) with the exception that it is used Bz-Bciclama instead of C4-Bciclama. The ion spray mass spectroscopy shows a main peak at 430 mu corresponding to [Mn (Bz-Bciciama) (formate)] +.

EXAMPLE 4 Synthesis of rMnfCs-BciclamalCbl where C8-Bciclama = 5-n-octyl-12-methyl-1,5,8,12-tetraaza-bicyclo [6,6,21-hexadecane (a) Synthesis of Cg-Bciclama This ligand is synthesized in a manner similar to the synthesis of C4-Bciclama described above in Example 2 (a) with the exception that 1-iodooctane is used in place of 1-iodobutane. Mass spectroscopy (MH +, 353). (b) Synthesis of [Mn (Cñ-Bciclama) CI7] This complex is done in a manner similar to the synthesis of [Mn (C-BcicIama) CI2] described above in Example 2 (b) with the exception that it is used C8-Bciclama instead of C4-Bciclama. The ion spray mass spectroscopy shows a main peak at 452 mu corresponding to [Mn (B8-Bciclama) (formate)] +.

EXAMPLE 5 Synthesis of rMndHg-BciclamalCIg. where Hg-Bciclama = 1, 5,8,12-tetraazabicyclo.6.6.21hexadecane H2-Bciclama is synthesized in a manner similar to the synthesis of C4-Bciclama described above with the exception that benzyl bromide is used in place of 1-iodobutane and methyl iodide. The benzyl groups are removed by catalytic hydrogenation. In this way, 5,12-dibenzyl-1, 5,8,12-tetraaza-bicyclo [6.6.2] hexadecane and 10% Pd on charcoal is dissolved in 85% acetic acid. This solution is stirred for 3 days at room temperature under an atmosphere of hydrogen gas. The solution is filtered through a 0.2 micron vacuum filter. After evaporation of the solvent using a rotary evaporator, the product is obtained as a colorless oil. Performance: 90 +%. The Mn complex is done in a manner similar to the synthesis of [Mn (Bciclama) Cl2] described in example 1 (b) with the exception that H2-Bciclama is used in place of Bciclama. Analysis of elements:% C, 40.92; % H, 7.44; % N, 15.91; theoretical for [Mn (H2-Bciclama) CI2], MnC- ^ e ^ C, MW = 352.2. Found:% C, 41.00; % H, 7.60; % N, 15.80. The FAB + mass spectroscopy shows a main peak at 317 mu corresponding to [Mn (H2-Bciclama) CI] + and another peak less than 352 mu corresponding to [Mn (H2-Bciclama) CI2] +.

EXAMPLE 6 Synthesis of rFe (H2-Bciclama) CI2l where H2-Bciclama = 1, 5,8,12-tetraazabicyclo.ß.6.21hexadecane The Fe complex is made in a manner similar to the synthesis [Mn (H2Bciclama) CI2] described in Example 5, with the exception that FeC is used instead of MnCI2. Analysis of elements:% C, 40.82%; % H, 7.42; % N, 15.87 theoretical for [Fe (H2-Bciclama) CI2] FeCI2H26N4CI2. PM = 353.1. Found:% C, 39.29%; % H, 7.49; % N, 15.00. The FAB + mass spectroscopy shows a main peak 318 mu corresponding to [Fe (H2-Bciclama) CI] + and another peak lower than 353 mu corresponding [Fe (H2-BciclamaCI2] +.

EXAMPLE 7 Synthesis of: Chloro-20-methyl-1, 9,20,24,25-pentaaza-tetracycle [7.7.7.13'7.111 '5.] pentacosa-3,5,7 (24), 11, 13,14 (25 ) -hexanomanganese (ll) hexafluorophosphate, 7 (b); Trifluoromethanesulfono-20-methyl-1, 9,20,24,25-pentaaza tetracycle [7.7.7.13,7.111, 15.] Pentacosa-3,5,7 (24), 11, 13,14 (25) -hexanomanganese ( II) trifluoromethanesulfonate, 7 (c) and thiocyanate-20-methyl-1, 9,20,24,25-pentaaza-tetracycle [7.7.7.13 .111'15.] Pentacosa-3,5,7 (24), 11 , 13,14 (25) -hexanofierro (ll) thiocyanate, 7 (d) (a) Synthesis of the ligand 20-methyl-1, 9,20,24,25-pentaaza-tetracycle [7.7.7.13,7.111'15.] Pentacosa-3,5,7 (24), 11, 13,14 (25) -hexane.

The ligand 7-methyl-3,7,1,1,17-tetraazabicyclo [1 1.3.1 7] heptadeca-1 (17), 13,15-triene is synthesized by the method of the K.P. Balakrishnan et al., J. Chem. Soc., Dalton Trans. , 1990, 2965. 7-methyl-3, 7, 1 1, 17-tetraazabicyclo [1 1 .3.117] heptadeca-1 (17), 13, 15-triene (1.49g, 6 mmole) and O, O ' bis (methanesulfonate) -2-6-pyridine dimethanol (1.77g, 6 mmol) are dissolved separately in acetonitrile (60 ml). Subsequently they are added by means of a syringe plunger (at a speed of 1.2 ml / hour) to an anhydrous sodium carbonate suspension (53 g, 0.5 mmol) in acetonitrile (1380 ml). The reaction temperature is maintained at 65 ° C for the total reaction time, 60 hours. After cooling, the solvent is removed under reduced pressure and the residue is dissolved in a sodium hydroxide solution (200 ml, 4 M). Subsequently the product is extracted with benzene (6 times, 100 ml) and the combined organic extracts are dried over anhydrous sodium sulfate. After filtration, the solvent is removed under reduced pressure. Subsequently the product is dissolved in a mixture of acetonitrile / trethylamine (95: 5) and passed through a neutral alumina column (2.5 x 12 cm). Removal of the solvent produces a white solid (0.93 g, 44%). This product can be further purified by recrystallization from a mixture of ethanol / diethylether combined with cooling at 0 ° C overnight to produce a white crystalline solid. Analysis Calculated for: C2? H29N5: C, 71.5; H, 8.32; N, 19.93. Found: C, 71.41; H, 8.00; N, 20.00 A mass spectrum shows the expected molecular ion peak [for C2iH3oN5] + at m / z = 352. The 1 H NMR spectrum (400 MHz, in CD3CN) exhibits peaks at d = 1.81 (m, 4H); 2.19 (s, 3H); 2.56 (t, 4H); 3.52 (t, 4H); 3.68 (AB, 4H), 4.13 (AB, 4H), 6.53 (d, 4H) and 7.07 (t, 2H). The 13 C NMR spectrum (75.6 MHz, in CD3CN) shows eight peaks at d = 24.05, 58.52, 60.95, 62.94, 121.5, 137.44 and 159.33 ppm. All the metal complex formation reactions are carried out in a glovebox with inert atmosphere gloves using still and distilled solvents. (b) Formation of ligand complexes L ^ with bis (pyridine) manganese chloride (II) Bis (pyridine) manganese (II) chloride is synthesized according to the literature procedure of H.T .: Witteveen et al., J. Inorg. Nucí Chem, 1974, 36, 1535. Ligand Li (1.24 g, 3.5 mmol), triethylamine (0.35 g, 3.5 mmol) and sodium hexafluorophosphate (0.588 g, 3.5 mmol) are dissolved in pyridine (12 ml). To this is added the bis (pyridine) manganese (II) chloride and the reaction is stirred overnight. After the reaction is filtered to remove a white solid. This solid is washed with acetonitrile until the wash has no color and then the combined organic filtrates are evaporated under reduced pressure. The residue is dissolved in a minimum amount of acetonitrile and allowed to evaporate overnight to produce bright red crystals. Performance: 0.8g (39%). Analysis Calculated for C2iH31H5Mn1CI1P1F6: C, 43.00; H, 4.99 and N, 1 1.95. Found: C, 42.88; H, 4.80 and N 1 1.86. A mass spectrum shows the expected molecular ion peak [for C2? H3? N5Mn? Cl?] At m / z = 441. The electronic spectrum of a solution diluted in water exhibits two absorption bands at 260 and 414nm (e = 1 .47 x 103 and 773 M'1cm "1, respectively.) The IR spectrum (KBr) of the complex shows a band at 1600cm" 1 (pyridine), and strong bands at 840 and 558cm "1 (c) Formation of ligand complexes with manganese trifluoromethanesulfonate (II) Manganese trifluoromethanesulfonate is prepared by the literature method of Bryan and Dabrowiak, Inorg. Chem., 1975, 14, 297. Manganese (II) trifluoromethanesulfonate (0.883 g, 2. 5 mmole) in acetonitrile (5 ml). This is added to a solution of ligand L-i (0.878 g, 2.5 mmol) and triethylamine (0.25 g, 2.5 mmol) in acetonitrile (5 ml). Subsequently it is heated for 2 hours before filtering and after cooling the solvent removal under reduced pressure. The residue is dissolved in a minimum amount of acetonitrile and allowed to evaporate slowly to produce orange crystals. Yield: 1.06 g (60%) Analysis Calculated for: Mn? C23H29N5S2F6O6: H, 4.15 and N, 9.95. Found: C, 38.83; H, 4.35 and N, 10.10. The mass spectrum shows the expected peak for [Mn? C22H29N5S2F3O3] + am / z = 555. The electronic spectrum of a solution diluted in water exhibits two absorption bands at 260 and 412nm (e = 9733 and 67 M "1cm" 1 , respectively). The IR spectrum (KBr) of the complex shows a band at 1600cm "1 (pyridine) and 1260,1160, and 1030cm" 1 (CF3SO3). (d) Formation of ligand complexes with iron trifluoromethanesulfonate (II) Iron trifluoromethanesulfonate (II) is prepared in situ by the literature method of Tait and Busch, Inorg. Synth .. 1978, XVIII, 7. The ligand (0.833 g, 2.5 mmol) and triethylamine (0.505 g, 5 mmol) are dissolved in acetonityl (5 ml). To this is added a solution of trifluoromethanesulfonate hexakis (acetonitrile) of iron (II) (1.5 g, 2.5 mmol) in acetonitrile (5 ml) to produce a dark red solution. Subsequently, sodium thiocyanate (0.406 g, 5 mmol) is added and the reaction is stirred for a further 1 hour. Subsequently the solvent is removed under reduced pressure and the resulting solid is recrystallized from methanol to produce red microcrystals. Yield: 0.65 g (50%) Analysis Calculated for Fe? C23H29N7S2: C, 52.76; H, 5.59 and N, 18.74. Found: C 52.96; H, 5.53; N, 18.55. A mass spectrum shows the expected molecular ion peak [for Fe1C22H29N6S] + at m / z = 465. The 1H NMR (300MHz, CD3CN) d = 1.70 (AB, 2H), 2.0 (AB, 2H), 2.24 (s, 3H), 2.39 (m, 2H), 2.70 (m, 4H), 3.68 (m, 4H), 3.95 (m, 4H), 4.2 (AB, 2H), 7.09 (d, 2H), 7.19 (d, 2H) ), 7.52 (t, 1 H), 7.61 (d, 1 H). The IR spectrum (KBr) of the spectrum shows peaks at 1608 cm "1 (pyridine) and strong peaks at 2099 and 2037 cm" 1 (SCN ").

Bleach activators and organic percarboxylic acids An essential and additional ingredient of the compositions and methods of the present invention is a bleach activator, organic percarboxylic acid or mixtures thereof, organic peroxyacids include, for example, hydrophilic mono- or diperoxy acids hydrophobic These may be peroxycarboxylic acids, peroxyimidic acids, amidoperoxycarboxylic acids or their salts, including calcium, magnesium salts or mixed cation salts. Peracids of various types both in free form and precursors known as "bleach activators" can be used which, when combined with a source of hydrogen peroxide, perhydrolyze to liberate the corresponding peracid. The organic parcarboxylic acids useful in the present invention as an oxygenated bleach include magnesium monoperoxyphthalate hexahydrate, available from Interox, m-chloro perbenzoic acid and its salts, 4-nonylamino-4-oxoperoxybutyric acid and diperoxydecanediodic acid and its salts. Such bleaches are described in the U.S. patent. No. 4,483,781, in the patent application of E.U. No. 740,446, to Burns et al., Filed June 3, 1985, EP-A 133,354, issued February 20, 1985, and the US patent. No. 4,412,934. The most preferred oxidants also include 6-nonylamino-6-oxoperoxycaproic acid (NAPAA) as described in the US patent. No. 4, 634,551 and includes those having the formula HO-OC (O) -RY, where R is a substituted alkylene or alkylene group containing from 1 to about 22 carbon atoms or a group that substituted phenylene or phenylene, and Y is hydrogen, halogen, alkyl, aryl or C (O) -OH or -C (O) -O-OH. The organic percarboxylic acids useful in the present invention include those which contain 1, 2 or more peroxy groups and can be aliphatic or aromatic. When the organic percarboxylic acid is aliphatic, the appropriate unsubstituted acid has the linear formula HO-OC (O) - (CH2) nY, where Y can be, for example, H, CH3, CH2CI, COOH, or C (O) OOH; and n is an integer from 1 to 20. Branched analogs are also acceptable. When the organic percarboxylic acid is aromatic, the suitable unsubstituted acid has the formula HO-O-C (O) -C6H4-Y where Y is hydrogen, alkyl, alkyhalogen, halogen or -COOH or -C (O) OOH. The monoperoxycarboxylic acids useful as oxygenated bleach in the present invention are further illustrated by alkylpercarboxylic acids and arylpercarboxylic acids such as peroxybenzoic acids and substituted ring peroxybenzoic acids, for example, peroxy-alpha-naphthoic acid; aliphatic, substituted aliphatic, and arylalkyl monoperoxy acids, such as peroxylauric acid, peroxystearic acid, and N, N-phthaloylaminoperoxycaproic acid (PAP), and 6-octylamino-6-oxo-peroxyhexanoic acid. The monoperoxycarboxylic acids can be hydrophilic, for example paracetic acid, or they can be relatively hydrophobic. The hydrophobic types include those containing a chain of six or more carbon atoms, the hydrophobic types that are preferred have a linear C8-C aliphatic chain optionally substituted by one or more ether oxygen atoms and / or one or more portions aromatic, located in such a way that the peracid is an aliphatic peracid. More generally, such optional substitution by ether oxygen atoms and / or aromatic portions can be applied to any of the peracids or bleach activators of the present invention. Branched chain peracid types and aromatic peracids having one or more linear or branched long chain C3-C6 substituents may also be useful. The peracids can be used in acid form or as any suitable salt with a stable bleach cation. In the present invention, organic percarboxylic acids having the formula are very useful: , or mixtures thereof, wherein R 1 is alkyl, aryl or alkaryl containing about 1 to about 14 carbon atoms, R 2 is alkylene, arylene or alkarylene containing about 1 to about 14 carbon atoms, and R 5 is H or alkyl, aryl or alkaryl containing from about 1 to about 10 carbon atoms. When these peracids have a sum of carbon atoms in R1 and R2 together of about 6 or more, preferably from about 8 to about 14, they are particularly suitable as hydrophobic peracids for bleaching a variety of relatively hydrophobic or "lipophilic" spots, including types called "percudidos". Calcium, magnesium or substituted ammonium salts may also be useful. Other useful peracids and bleach activators of the present invention are in the family of imidoperacids and bleach activators. These include phthaloylimidoperoxycaproic acid and related substituted arylimido and acyloxynitrogen derivatives. To list such components, the preparations and their incorporation into laundry compositions including both granules and liquids, see U.S. Pat. Nos. 5,487,818; 5,470,988; 5,466,825; 5,419,846; 5,415,796; 5,391, 324; 5,328,634; 5,310,934; 5,279,757; 5,246,620; 5,245,075; 5,294,362; 5,423,998; 5,208,340; 5,132,431 and 5,087,385. Useful diperoxy acids include, for example, 1,2-diperoxydecanedioic acid (DPDA); 1, 9-diperoxyazelaic acid; diperoxy fibers, diperoxysebacic acid and diperoxyisophthalic acid; 2-decyliperoxybutane-1,4-dioic acid and 4,4'-sulfonylbisperoxybenzoic acid. Because of the structures in which two hydrophilic groups are relatively at the ends of the molecule, the diperoxy acids have sometimes been classified separately from hydrophilic and hydrophobic monoperacids, for example as "hydrotropic": some of the diperacids are hydrophobic in a literal sense, especially when they have a long chain portion that separates the peroxyacid portions.

In general, the terms "hydrophilic" and "hydrophobic" which are used in the present invention in connection with any oxidants, especially peracids, and in connection with bleach activators, in the first instance, are based on whether a given oxidant performs effectively bleaching fleeting dyes in a solution, thus avoiding discoloration and turning the fabric grayish and / or removing more hydrophilic stains such as tea, wine and grape juice, in this case called "hydrophilic". When the oxidant or bleach activator has a significant stain removal, improvement of whiteness or cleaning effect in percudid, greasy, carotenoid or other hydrophobic spots, it is called "hydrophobic". The terms are also applicable when referring to peracids or bleach activators that are used in combination with a source of hydrogen peroxide. The current commercial brands for the hydrophilic performance of oxidizing systems are: TAED or peracetic acid, corresponding to hydrophilic bleaching. NOBS or NAPAA are the corresponding marks for hydrophobic bleaching. The terms "hydrophilic", "hydrophobic" and "hydrotropic" with reference to oxidants including peracids and here also have been used somehow extended bleach activators more closely linked to the literature. See especially Kirk Othmer's Encyclopedia of Chemical Technology, Vol. 4, pages 284-285. This reference provides a chromatographic retention time and some criteria based on the important concentration of micelles, and is useful for identifying and / or characterizing the preferred subclasses of hydrophobic, hydrophilic and hydrotropic oxidants and bleach activators that can be used in the present invention. Bleach activators useful in the present invention include amides, imides, esters and anhydrides. Commonly, at least a portion of substituted or unsubstituted acyl connected covalently to a leaving group as in structure RC (O) -L, wherein R is an alkyl, aryl or arylalkyl portion of saturated C2-C18 or unsaturated - In a preferred mode of use, bleach activators are combined with a source of hydrogen peroxide, such as perborates or percarbonates, in a single product. Conveniently, the single product leads to in situ production in an aqueous solution (ie, during the washing process) of the percarboxylic acid corresponding to the bleach activator. The product itself can be hydrated, for example a powder, since the water is controlled in quantity and mobility, in such a way that the storage stability is acceptable. Alternatively, the product may be solid or anhydrous liquid. In another embodiment, the bleach activator or oxygen bleach is incorporated into a pretreatment product, such as a stain remover.; the previously treated, stained substrates can then be exposed to other treatments, for example to a source of hydrogen peroxide. With respect to the structure of the prior bleaching activator RC (O) L, the atom in the leaving group which is connected to the peracid-forming acyl portion R (C) O- is mainly O or N. The bleach activators may be have peracid forming moieties positively or negatively charged and / or residual groups charged positively or negatively. One or more peracid forming moieties or residual groups may be present. See, for example, the patents of E.U.A. Nos. 5,595,967, 5,561, 235, 5,560,862 or the bis- (peroxy-carbonic) system of the U.S. patent. No. 5,534,179. The bleach activators can be replaced with electron donating or electron releasing portions, either in the leaving group or in the peracid forming portion or portions, changing their reactivity and making them more or less adequate at a particular pH for washing conditions . For example, groups that attract electrons such as NO2 improve the effectiveness of bleach activators created for use under light pH scrubber conditions (for example from about 7.5 to about 9.5). Cationic bleach activators include carbamate quaternary, carbonate quaternary, quaternary ester and quaternary amide types, providing a scale of cationic, peroxycarboxy or peroxycarboxylic peroxy acids to the wash. An analogous but non-cationic group of bleach activators is available when the quaternary derivatives are not desired. In more detail, cationic activators include activators substituted with quaternary ammonium from WO 96-06915, U.S. 4,751, 015 and 4,397,757, EP-A-284292, EP-A-331, 229 and EP-A-03520, including ethyl-4-sulfophenyl carbonate- (SPCC) of 2- (N, N, N-trimethyl ammonium); chloride- (ODC) of N-octyl, N, N-dimethyl-N-10-carbofenoxidecylammonium; Sodium 3- (N, N, N, N-trimethylammonium) propyl sulfophenylcarboxylate and N, N, N-trimethylammonium toluoxybenzenesulfonate. Also useful are the cationic nitriles described in EP-A-303,520 and in European Patent Specification No. 458,396 and 464,880. Other types of nitrile have electron-withdrawing substituents as described in U.S. Pat. 5,591, 378; examples including 3,5-dimethoxybenzonitrile and 3,5-dinitrobenzonitrile. Other descriptions of bleach activators are included in GB 836,988; 864,798; 907,356; 1, 003,310 and 1, 519,351; German Patent No. 3,337,921; EP-A-0185522; EP-A-0174132; EP-A-0120591; the patents of E.U.A. Nos. 1, 246,339; 3,332,882; 4,128,494; 4,412,934 and 4,675,393, and sulfonatophenol ester of the alkanoyl amino acids which are described in the U.S.A. 5,523,434. Suitable bleach activators include any type of acetylated diamine, either hydrophilic or hydrophobic in character. Of the above classes of bleach precursors, preferred classes include esters, including acyl phenols sulfonates, acylalkyl phenols sulfonates or acyloxybenzenesulfonates (leaving group OBS); acylamides; and peroxyacid precursors substituted with quaternary ammonium including cationic nitriles. Preferred hydrophilic bleach activators include N, N, N'N'-tetraacetylethylenediamine (TAED) or any of its close relatives including triacetyl or other non-symmetrical derivatives. TAED and acetylated carbohydrates such as pentaacetatoglucose and tetraacetylxylose are preferred hydrophilic bleach activators. Depending on the application, acetyltriethyl citrate, a liquid, as well as phenylbenzoate can also be used. Preferred hydrophobic bleach activators include sodium nonanoyloxybenzenesulfonate (NOBS or SNOBS), substituted amide types that are described in greater detail below, such as NAPAA-related activators., and activators related to certain imidoperacid bleach, for example as described in the US patent. No. 5,061, 807, issued October 29, 1991 and assigned to Hoechst Aktiengesellschaft in Frankfurt, Germany. The Japanese patent application (Kokai) No. 4-28799 for example, discloses a bleaching agent and a bleaching detergent composition comprising an organic peracid precursor described by a general formula and illustrated by compounds that can be summarized in particular with ia formula: wherein L is sodium p-phenosulfonate, R1 is CH3 or C12H25, and R2 is H. Analogs of these compounds having any of the residual groups identified herein and / or having linear or branched R1 may also be used. C6-C? 6. Another group of peracids and bleach activators of the present are those derived from acyclic imidoperoxycarboxylic acids and salts thereof of the formula: cyclic imidoperoxycarboxylic acids and salts thereof of formula and (iii) mixtures of said compounds, (i) and (ii); wherein M is selected from hydrogen and cations compatible with bleach having charge q; y and z are integers for said compound to be electrically neutral; E, A and X comprise hydrocarbyl groups; and said terminal hydrocarbyl groups are contained within E and A. The structure of the corresponding bleach activators is obtained by removing the peroxy portion and the metal and replacing it with a leaving group L, which may be any of the portions of the leaving group defined at the moment. In preferred embodiments, detergent compositions are included wherein, in any such compound, X is linear C3-C8 alkyl; A is selected from: where n is from 0 to about 4, and wherein R1 and E are said terminal hydrocarbyl groups, R2, R3 and R4 are independently selected from H, saturated C? -C3 alkyl, and unsaturated CrC3 alkyl; and wherein said terminal hydrocarbyl groups are alkyl groups comprising at least 6 carbon atoms, usually linear or branched alkyl having from about 8 to about 16 carbon atoms. Other suitable bleach activators include sodium 4-benzoyloxybenzenesulfonate (SBOBS); Sodium 1-methyl-2-benzoyloxybenzene-4-sulfonate; Sodium 4-methyl-3-benzoyloxybenzoate (SPCC); Ammonium trimethyl tolyloxybenzenesulfonate; or sodium 3,5,5-trimethyl-hexanoyloxybenzenesulfonate (STHOBS). Bleach activators can be used in an amount of up to 20%, preferably 0.1-10% by weight, of the composition, however higher levels are acceptable, 40% or more, for example in highly bleaching additive product forms. Concentrates or forms designed for automatic dosing in household appliances. The most preferred bleach activators in the use of the present invention are substituted amides having any of the formulas: O O or O II II R1- -C N R2- -c- R1 N - C H- -R2- -C-L R5 R5 or mixtures thereof, wherein R1 is alkyl, aryl, or alkaryl containing from 1 to about 14 carbon atoms including both hydrophilic types (short R1) and hydrophobic types (R1 is especially about 8 to about 12) , R 2 is alkylene, arylene or alkarylene containing from about 1 to about 14 carbon atoms, R 5 is H, or an alkyl, aryl, or alkaryl containing from about 1 to about 10 carbon atoms, and L is a outgoing group. As defined herein, a leaving group is any group that is displaced from the bleach activator as a consequence of attack by perhydroxide or equivalent reagent capable of releasing a more potent bleach from the reaction. Perhydrolysis is a term used to describe such a reaction. Therefore, bleach activators are perhydrolyzed to release peracid. Residual groups of bleach activators for washing at relatively low pH are suitable electron attractants. Preferred residual groups have slow rates of reassociation with the portion from which they have been displaced. The residual groups of bleach activators are preferably selected so that their removal and peracid formation are in proportions consistent with the desired application, for example, a wash cycle. In practice, the balance must be found so that said residual groups are not released considerably, and the corresponding activators do not hydrolyze or peridrolize considerably, when stored in a bleaching composition. The pK of the conjugate acid of the leaving group is a measure of adequacy, and is typically from about 4 to about 16, preferably from about 6 to about 12, most preferably from about 8 to about 11.

Preferred bleach activators include those of the formulas, for example the substituted amide formulas, shown above, wherein R1, R2 and R5 are as defined for the corresponding peroxyacid and L is selected from the group consisting of: - H R and mixtures thereof, wherein R1 is a linear or branched alkyl, aryl or alkaryl group containing from 1 to about 14 carbon atoms, R3 is an alkyl chain containing from 1 to about 8 carbon atoms, R4 is H or R3, and Y is H or a solubilizing group. These and other known residual groups are generally suitable general alternatives for introduction into any bleach activator herein. Preferred solubilizing groups include -SO3"M +, -CO2" M +, -SO4"M +, -N + (R) 4X- and O-N (R3) 2, most preferably -SO3" M + and -CO2"M + where R3 is an alkyl chain containing from about 1 to about 4 carbon atoms, M is a stable bleach cation and X is a stable bleach anion, each of which is selected to maintain the solubility of the activator. For example, heavy-duty granular detergents in solid form in Europe, any of the foregoing bleach activators are preferably solids having a crystalline character and a melting point above about 50 ° C. In these cases, branched alkyl groups are preferably not included. in the oxygen bleach or bleach activator, in other formulation contexts, heavy-duty liquids with bleach additives or liquid bleaching additives, low melting activators or liquids are preferred, for example. The reduction of the melting point may be favored by incorporating portions of branched alkyl, instead of linear in the oxygen bleach or precursor. When solubilizing groups are added to the leaving group, the activator may have good solubility or dispersibility in water while still being able to deliver a relatively hydrophobic peracid. Preferably, M is alkali metal, ammonium or substituted ammonium, most preferably Na or K, and X is halide, hydroxide, methylisulfate or acetate.

Solubilizer groups can generally be used in any bleach activator herein. Low solubility bleach activators, for example those with a leaving group that does not have a solubilizing group, should be finely divided or dispersed in bleaching solutions to obtain acceptable results. Preferred bleach activators also include those of the above general formula wherein L is selected from the group consisting of: wherein R3 is as defined above and Y is -SO3"M + or -CO2" M + where M is as defined above. Preferred examples of bleach activators of the above formulas include (6-octanamidocaproyl) oxybenzenesulfonate, (6-nonanamidocaproyl) oxybenzenesulfonate, (6-decanamidocaproyl) oxybenzenesulfonate, and mixtures thereof. Other useful activators, described in the patent of E.U.A. No. 4,966,723, are of the benzoxazine type, such as a C6H ring in which a C (O) OC (R1) = N- portion is fused at positions 1, 2. Depending on the activator and the exact application, it is possible to obtain good whitening results from whitening systems which during use have a pH of from about 6 to about 13, preferably from about 9.0 to about 10.5. Normally, for example, activators with electron-withdrawing portions are used for near neutral or subneutral pH scales. Alkalis or pH regulating agents can be used to ensure said pH. Acii-lactam activators are very useful herein, especially the acylcaprolactams (see for example WO 94-28102 A) and acylvalerolactams (see E.U.A. 5,503,639) of the formulas: where R6 is H, alkyl, aryl, alkoxyaryl, an alkaryl group containing from 1 to about 12 carbon atoms, or substituted phenyl containing from about 6 to about 18 carbons. See also E.U.A. 4,545,784 which describes acylcaprolactams, including benzoylcaprolactam adsorbed on sodium perborate. In certain preferred embodiments of the invention, NOBS, lactam activators, imide activators or functional amide activators, especially the more hydrophobic derivatives, are conveniently combined with hydrophilic activators such as TAED, typically in weight proportions of hydrophobic activator: TAED in the ratio from 1: 5 to 5: 1, preferably around 1: 1. Other suitable lactam activators are the modified alpha, see WO 96-22350 A1, July 25, 1996. Lactam activators, especially the most hydrophobic types, are conveniently used in combination with TAED, typically in weight proportions of caprolactam activators or amide derivatives: TAED in the ratio of 1: 5 to 5: 1, preferably about 1: 1. See also bleach activators having a cyclic amidine leaving group described in the US patent. 5,552,556. Non-limiting examples of additional activators that are used herein can be found in E.U. 4,915,854, E.U. 4,412,934 and 4,634,551. The hydrophobic activator of nonanoyloxybenzenesulfonate (NOBS) and the hydrophilic activator of tetraacetylethylenediamine (TAED) are common, and mixtures thereof can also be used. The superior bleaching / cleaning action of the present compositions also preferably achieves safety for parts of the natural rubber machine, for example of certain European washing appliances (see WO 94-28104) and other natural rubber articles, including fabrics They contain natural rubber and natural rubber elastic materials. The complexities of bleaching mechanisms are many and not completely understood. Other additional activators useful herein include those of E.U. 5,545,349. Examples include esters of an organic acid and ethylene glycol, diethylene glycol or glycerin, or the acidic measure of an organic acid and ethylenediamine.; wherein the organic acid is selected from methoxyacetic acid, 2-methoxypropionic acid, p-methoxybenzoic acid, ethoxyacetic acid, 2-ethoxypropionic acid, p-ethoxybenzoic acid, propoxyacetic acid, 2-propoxypropionic acid, p-propoxybenzoic acid, butoxyacetic acid, 2-butoxypropionic acid, p-butoxybenzoic acid, 2-methoxyethoxyacetic acid, 2-methoxy-1-methylethoxyacetic acid, 2-methoxy-2-methylethoxyacetic acid, 2-ethoxyethoxyacetic acid, 2- (2-ethoxyethoxy) propionic acid, p - (2-ethoxyethoxy) benzoic acid, 2-ethoxy-1-methylethoxyacetic acid, 2-ethoxy-2-methylethoxyacetic acid, 2-propoxyethoxyacetic acid, 2-propoxy-1-methylethoxyacetic acid, 2-propoxy-2-methylethoxyacetic acid , 2-butoxyethoxyacetic acid, 2-butoxy-1-methylethoxyacetic acid, 2-butoxy-2-methylethoxyacetic acid, 2- (2-methoxyethoxy) ethoxyacetic acid, 2- (2-methoxy-1-methylethoxy) ethoxyacetic acid, - (2-methoxy-2-methylethoxy) ethoxyacetic acid and 2- (2-ethoxyethoxy) acid i) ethoxyacetic.

Oxygenated Bleaching Agents Preferred compositions of the present invention comprise, as part or all of the laundry or cleaning auxiliary materials, an oxygenated bleaching agent. The oxygenated bleaching agents useful in the present invention may be any of the known oxidizing agents for laundry purposes, hard surface cleaning, automatic dishwashing or denture cleaning. Oxygenated bleaches or mixtures thereof are preferred, although other oxidizing bleaches may also be used, such as an enzyme system producing hydrogen peroxide.

Oxygenated bleaches (including organic percarboxylic acids) provide "available oxygen" (AvO) or "active oxygen" which can typically be measured by standard methods, such as ceric sulfate and / or iodide / thiosulfate titration. See the well-known work of Swern, or Kirk Othmer's Encyclopedia of Chemical Technology on the subject "Bleaching Agents". When oxygenated bleach is a peroxygen compound, it contains -O-O- bonds with an "active" O in each bond. The AvO content of such an oxidizing compound, usually expressed as a percentage, is equal to 100 * the number of active oxygen atoms * (16 / molecular weight of the oxygen bleaching compound). The combination mode of the catalyst, bleach activator and / or organic percarboxylic acid and oxygenated bleach can be varied. For example, the catalyst, bleach activator and / or organic percarboxylic acid and oxygenated bleach can be incorporated into a single product formula, or can be used in various combinations of "pretreatment product" such as "stain remover", "washing product". Main "and even" after-wash "product, such as fabric conditioners or sheets to add to the dryer. The oxygenated bleach of the present invention may have a physical form compatible with the application of intention; More particularly, oxidants are included in liquid form or solid form, as well as auxiliary materials, enhancers or activators. Liquids can be included in solid detergents, for example by absorption in an inert support, and solids can be included in liquid detergents, for example by the use of compatible suspending agents. Peroxygenated common oxygenated bleaches include hydrogen peroxide, inorganic peroxohydrates and organic peroxohydrates. Also useful in the present invention as oxygenated bleaches are inorganic peroxides such as Na 2 O 2, superoxides such as KO 2, organic hydroperoxides such as eumeno hydroperoxide and t-butyl hydroperoxide, and inorganic peroxyacids and their salts such as the salts of peroxosulfuric acid, especially the salts potassium peroxodisulfuric acid and, most preferably, peromonusulfuric acid, including the commercial form of triple salt sold as OXONE from Dupont and also any commercially available form equivalent as CUROX from Akzo or CAROAT from Degussa. Some organic peroxides, such as dibenzoyl peroxide, may be useful, especially as additives and not as a major oxygenated bleach. Mixed oxygenated bleach systems are generally useful, as are blends of any oxygenated bleaching agents with bleaching agents, organic catalysts, known enzymatic catalysts and mixtures thereof; in addition such mixtures may include additional brighteners, photobleaches and dye transfer inhibitors of the types already known in the art.

As mentioned, oxygenated whiteners that are preferred include peroxohydrates, sometimes known as peroxyhydrates or peroxohydrates. They are organic or, more commonly, inorganic salts that can release hydrogen peroxide easily. They include types in which hydrogen peroxide is present as a true crystal hydrate and, types in which hydrogen peroxide is incorporated covalently and chemically released, for example by hydrolysis. Peroxohydrates typically release hydrogen peroxide so easily that it can be extracted in measurable amounts in the ether phase of an ether / water mixture. The peroxohydrates are characterized in that they do not respond to the Riesenfeld reaction, in contrast to some types of oxidants described in the present invention thereafter. Peroxohydrates are the most common examples of "hydrogen peroxide source" materials and include perborates, percarbonates, perfosphates and percilicates. Of course, other useful materials that serve to produce or release hydrogen peroxide are useful. Mixtures of two or more peroxohydrates can be used, for example when it is desired to take advantage of a differential solubility. Suitable peroxohydrates include sodium carbonate peroxyhydrate and commercially equivalent "percarbonate" bleaches, and any of the so-called sodium perborate hydrates, with "tetrahydrate" and "monohydrate" being preferred.; although sodium pyrophosphate peroxyhydrate can be used. Some of these peroxohydrates are available in processed forms with coatings, such as silicate and / or borate and / or waxy materials and / or surfactants, or have a particle geometry, such as compact spheres, that improve storage stability. As organic peroxohydrates, the urea peroxohydrate may also be useful in the present invention. The percarbonate bleach includes, for example, dry particles having an average particle size in the range of about 500 microns to about 1000 microns, not more than about 10% by weight of said particles being smaller than about 200 microns and not larger of about 10% by weight of said particles, being larger than about 1,250 microns. Percarbonates and perborates are widely available in the market, for example from FMc, Solvay and Tokai Denka.

Enzymatic Sources of Hydrogen Peroxide In a different route from the oxygenated bleaching agents illustrated above, another suitable hydrogen peroxide generation system is a combination of a C 1 -C 4 a canyol oxidase and a C 1 -C 4 alkanol, especially a combination of methanol-oxidase (MOX) and ethanol. Said combinations are shown in WO 94/03003. Other enzymatic materials related to bleaching, such as peroxidases, haloperoxidases, oxidases, superoxide dismutases, catalases and their enhancers or, commonly, inhibitors, can be used as optional ingredients in the present compositions.

Oxygen Transfer Agents and Precursors Any of the known organic bleach catalysts, oxygen transfer agents or precursors therefor are also useful. These include the compounds themselves and / or their precursors, for example any ketone suitable for the production of dioxiranes and / or any of the analogs containing hetero atoms of dioxirane precursors or dioxiranes, such as sulfonimines.

R1R2C = NSO2R3, see EP 446 982 A, published in 1991 and sulfonyloxaziridines, for example: see EP 446,981 A, filed in 1991. Preferred examples of such materials include hydrophilic or hydrophobic ketones, used especially in conjunction with monoperoxysulfates to produce dioxiranes in situ, and / or the imines described in E.U. 5,576,282 and references described herein. The oxygen bleaches are preferably used in conjunction with said oxygen transfer agents or precursors include percarboxylic acids and salts, percarbon acids and salts, peroxymonosulfuric acids and salts, and mixtures thereof. See also E.U. 5,360,568; E.U. 5,360,596 and E.U. 5,370,826. In a highly preferred embodiment, the invention relates to a detergent composition incorporating a transition metal bleach catalyst according to the invention, and an organic bleaching catalyst such as one mentioned hereinabove, a primary oxidant such as a source of hydrogen peroxide, and at least one additional detergent, hard surface cleaner or automatic dishwashing aid. Among said preferred compositions are those that also include a precursor for a hydrophobic oxygenated bleach, such as NOBS. Although oxygenated bleaching systems and / or their precursors may be susceptible to decomposition during storage in the presence of moisture, air (oxygen and / or carbon dioxide) and other metals (especially rust or simple salts or colloidal oxides of the transition metals) and when subjected to light, the stability can be improved by adding common sequestrants (chelators) and / or polymeric dispersants and / or a small amount of antioxidant to the bleaching system or product. See, for example, E.U. 5,545,349. Antioxidants are commonly added to detergent ingredients that vary from enzymes to surfactants. Their presence is not necessarily inconsistent with the use of an oxidizing bleach; for example, introduction of a barrier system to stabilize an apparently incompatible combination of an enzyme and an antioxidant, on the one hand, and an oxygenated bleach, on the other, can be used. Although substances commonly known as antioxidants can be used, those which are preferable include phenol-based antioxidants such as 3,5-di-tert-butyl-4-hydroxytoluene and 2,5-di-tert-butylhydroquinone; amine-based antioxidants such as N, N'-diphenyl-p-phenylenediamine and phenyl-4-piperizinyl carbonate; sulfur-based antioxidants such as didodecyl-3,3'-thiodipropionate and ditridecyl-3,3'-thiodipropionate; phosphorus-based antioxidants such as tri (isododecyl) phosphate and triphenyl phosphate and natural antioxidants such as L-ascorbic acid, its sodium salts and DL-alpha-tocopherol. These antioxidants can be used independently or in combinations of two or more. Among these are particularly preferable 3, 5-di-tert-butyl-4-hydroxytoluene, 2,5-di-tert-butylhydrquinone and D, L-alpha-tocopherol. When used, the antioxidants are mixed in the bleaching composition of the present invention preferably at a ratio of 0.01-1.0% by weight of the organic acid peroxide precursor, and particularly preferably at a ratio of 0.05-0.5% by weight. weight. The hydrogen peroxide or peroxide which produces hydrogen peroxide in aqueous solution is combined in the mixture during use, preferably at a ratio of 0.5-98% by weight and particularly preferably at a proportion of 1-50% by weight, so that the effective oxygen concentration is preferably 0.1-3% by weight and particularly preferably 0.2-2% by weight. In addition, the organic acid peroxide precursor is combined in the composition during use, preferably at a ratio of 0.1-50% by weight and particularly preferably at a proportion of 0.5-30% by weight. Without attempting to be limited by theory, antioxidants that function by inhibiting or neutralizing free radical mechanisms to control tissue damage may be particularly desirable.

Although the combinations of ingredients used with the transition metal bleach catalysts of the invention can be broadly permuted, some particularly preferred combinations include those with: one or more detersive surfactants, especially including branched anionic types in the middle region of their chain which have superior solubility at low temperatures, such as branched sodium alkyl sulphates in the middle region of their chain, although the incorporation at high level of nonionic detersive surfactants is also very useful, especially in heavy-duty granular forms in compact form; polymeric dispersants, including especially the biodegradable, hydrophobically modified and / or terpolymer types; sequestrants, for example certain penta (methylenephosphonates) or ethylene diamine disuccinate; fluorescent whitening agents; enzymes, including those capable of generating hydrogen peroxide; photobleaches and / or dye transfer inhibitors. Also, builders, pH regulators or conventional alkalis and combinations of various cleaning promoter enzymes, especially proteases, cellulases, amylases, keratinases and / or lipases, can be added. In such combinations, the transition metal bleach catalyst will preferably be at levels in a suitable proportion to provide wash concentrations (during use) of from about 0.1 to about 10 ppm (catalyst weight); the other components are used at their known levels which can vary widely.

Although there is currently no advantage, the transition metal catalysts of the invention can be used in combination with transition metal bleach or dye transfer inhibition catalysts described above, such as Mn or Fe complexes of triazacyclononanes, the complexes Fe of N, N-bis (pyridin-2-yl-methyl) -bis (pyridin-2-yl) methylamine (EU 5,580,485) and the like. For example, when the transition metal bleach catalyst is one that proves to be particularly effective for the bleaching solution and the inhibition of dye transfer, as is the case for example of certain porphyrin transition metal complexes, it can be combined with another more suitable to promote interfacial bleaching of dirty substrates.

Materials and auxiliary methods for laundry and cleaning In general, an auxiliary for laundry or cleaning is any material that is required to transform a composition containing the bleaching catalyst of transition metal and bleach activator and / or organic percarboxylic acid into a composition used for laundry or cleaning. Auxiliaries in general include stabilizers, diluents, structuring materials, agents having aesthetic effects such as dyes, pro-perfumes and perfumes, and materials having an independent or dependent cleaning function. In preferred embodiments, auxiliaries for laundry or cleaning are widely recognized by those skilled in the art as they are characteristic of laundry or cleaning products, especially laundry or cleaning products that are used directly by the consumer in a domestic environment Although not essential for the purposes of the present invention as it has been very broadly defined, several of said conventional auxiliaries illustrated hereinabove are suitable for use in the present laundry and cleaning compositions and can be desirably incorporated into preferred embodiments of the invention. , for example to help or improve the cleaning performance, for the treatment of the substrate to be cleaned, or to modify the aesthetics of the detergent composition, as is the case with perfumes, dyes, dyes or the like. The precise nature of these additional components, and the levels of incorporation thereof, will depend on the physical form of the composition and the nature of the washing operation for which it will be used. Unless otherwise indicated, the detergent or the detergent additive compositions may be formulated as granular or powder washing agents for all purposes or for "heavy duty", especially laundry detergents; liquid cleaning agents, in the form of gel or paste for all purposes, especially those which are known as heavy duty liquid types; liquid detergents for fine fabrics; manual dishwashing agents or light duty tableware washing agents, especially those of high foaming type; automatic dishwashing agents, including types of agents in the form of tablets, granules, liquids and rinsing aids for institutional or domestic use; liquid cleaning agents and disinfectants, including antibacterial handwashing types, laundry bars, mouth rinses, denture cleaners, car or carpet shampoos, bathroom cleaners; shampoo and conditioner for hair; gels for bath and foam baths and metal cleaners; as well as cleaning aids such as bleach additives and "to remove stains" or types of pretreatment. Preferably, the auxiliary ingredients should have adequate stability with the bleaches employed herein. Certain preferred detergent compositions herein must be free of boron and free of phosphate. Preferred dishware formulations may include chlorine-free types or those containing chlorine bleach. Typical levels of auxiliaries are from about 30% to about 99.9%, preferably about 70% to about 95%, by weight of the compositions. Common auxiliaries include builders, surfactants, enzymes, polymers, bleaches, bleach activators, catalytic materials and the like, excluding any material already defined hereinbefore as part of the essential component of the compositions of the invention. Other auxiliaries of the present invention may include various active ingredients or specialized materials such as dispersing polymers (eg, from BASF Corp. or Rohm &Haas), color spots, silverware cleaners, antifog or anti-corrosion agents, colorants, fillers. , germicides, alkalinity sources, hydrotropes, antioxidants, enzyme stabilizing agents, perfumes, solubilizing agents, vehicles, processing aids, pigments, and, for liquid formulations, solvents, as described in greater detail hereinafter. Typically, the present laundry or cleaning compositions such as laundry detergents, laundry detergent additives, hard surface cleaners, automatic dishwashing detergents, synthetic and soap-based laundry detergent bars. clothing, fabric softeners and liquids and solids for fabric treatment, and treatment articles of all kinds will require several auxiliaries, however, products formulated in a simple manner, such as bleaching additives, may require only metal catalyst and bleach activator and / or organic percarboxylic acid, and a simple support material such as a detergent builder or surfactant that helps to make available to the consumer the potent catalyst in an administrable dose.

Detersive Surfactants The present compositions desirably include a detersive surfactant. Detersive surfactants are widely shown in E.U. 3,929,678, Dec. 30, 1975 Laughlin, et al., And E.U.A. 4,259,217, March 31, 1981, Murphy; in the "Surfactant Science" series, marcel Dekker, Inc., New York and Basel; in "Handbook of Surfactants", M.R. Porter, Chapman and Hall, 2nd Ed., 1994; in "Surfactants in Consumer Products", Ed. J. Falbe, Springer-Verlag, 1987; and in numerous patents related to detergents assigned to Procter & Gamble and other manufacturers of detergent and consumer products. The detersive surfactant herein is in general a partially water soluble surfactant material that forms micelles and has a cleaning function, in particular, it helps to remove grease from fabrics and / or suspend dirt removed from them in a washing operation, although certain detersive surfactants are useful for more specialized purposes, such as co-surfactants to aid in the primary cleansing action of another surfactant component, such as wetting agents or hydrotropes, such as viscosity controllers, such as rinse or rinse agents. lamella formation ", as coating agents, as builders, as fabric softeners or as foam suppressors. The detersive surfactant herein comprises at least one amphiphilic compound, i.e., a compound having a hydrophobic end and a hydrophilic head, which produces foam in water. The foam test of the literature is known and generally includes a test of stirring or stirring a solution or dispersion of the detersive surfactant in distilled water under conditions of concentration, temperature and shear stress designed to simulate those found in fabric washing. Such conditions include concentrations on the scale of about 10"6 molar to about 10" 1 molar and temperatures in the range of about 5 ° C to 90 ° C. The foam test apparatus is described in the patents mentioned above and in Surfactant Science Series volumes. See, for example, Vol. 45. The detersive surfactant herein therefore includes the anionic, nonionic, zwitterionic or amphoteric types of surfactants known to be used as cleaning agents in fabric washing, but do not include completely or completely insoluble foam-free surfactants (although these may be used as optional auxiliaries). Examples of the type of surfactant considered optional for the present purposes are not relatively common in comparison with cleaning surfactants but include, for example, common fabric softening materials such as dioctadecyldimethylammonium chloride. In more detail, detersive surfactants useful herein typically at levels of 1% to 55% by weight, suitably include: (1) alkylbenzene sulfonates, including linear and branched types; (2) olefinsulfonates, including α-olefinsulfonates and sulfonates derived from fatty acids and fatty esters; (3) alkyl or alkenyl sulfosuccinates, including diester and middle ester types, as well as sulfosuccinamates and other types of sulfonate / carboxylate surfactants such as sulfosuccinates derived from ethoxylated alcohols and alkanolamides; (4) the arafin or alcansulfonate and alkyl or alkenylcarboxisulfonate types, including the product of the addition of bisulfite to alpha olefins; (5) alkylnaphthalenesulfonates; (6) alkyl isethionates and alkoxypropanesuifonates, as well as fatty esters of isethionate, fatty esters of ethoxylated isethionate and other ester sulfonates such as the 3-hydroxypropanesulfonate ester or the AVANEL S types; (7) benzene, cumen, toluene, xylene, and naphthalenesulfonates, useful especially for their hydrotrope forming properties; (8) alkyl ether sulfonates; (9) alkyl amide sulfonates; (10) salts or esters of fatty acid a-sulfo and internal sulfo fatty acid esters; (11) alkylglyceryl sulfonates; (12) ligninsulfonates; (13) petroleum sulfonates, sometimes known as heavy alkylates; (14) diphenyl oxide disulfonates; (15) alkyl sulfates or alkenyl sulfates; (16) alkoxylated alkyl or alkylphenol sulfates and the corresponding polyalkoxylates, sometimes known as alkyl ether sulphates, as well as alkenyl alkoxy sulfates or alkenyl polyalkoxysulfates; (17) alkylamide sulfates or alkenyl amide sulfates, including the sulfated alkanolamines and their alkoxylates and polyalkoxylates; (18) sulphated oils, sulfated alkyl glycerides, sulfated alkyl polyglycosides or sulfated sugar derived surfactants, (19) alkylalkoxycarboxylates and alkylpolyalkoxycarboxylates, including salts of galacturonic acid; (20) alkyl estercarboxylates and alkenyl estercarboxylates; (21) alkyl or alkenylcarboxylates, especially conventional soaps and a-, tp-dicarboxylates, also including the alkyl and alkenyl succinates; (22) alkyl or alkenyl amide alkoxy- and polyalkoxycarboxylates; (23) the types of alkyl or alanylamidocarboxylate surfactants, including sarcosinates, taurides, glycinates, aminopropionates and iminopropionates; (24) amide soaps, sometimes called fatty acid cyanamides; (25) alkylpolyaminocarboxylates; (26) phosphorus-based surfactants, including alkenyl or alkyl phosphate esters, alkyl ether phosphates including their alkoxylated derivatives, phosphatidic acid salts, alkyl phosphonic acid salts, alkyldi (polyoxyalkylenealkanol) phosphates, amphoteric phosphates such as lecithins; and the phosphate / carboxylate, phosphate / sulfate and phosphate / sulfonate types; (27) nonionic surfactants of the Pluronic and Tetronic type; (28) the so-called EO / PO block polymers, including the EPE and PEP types of two blocks and three blocks; (29) fatty acid polyglucolic esters; (30) alkyl or alkylphenol ethoxylated, propoxylated and butoxylated end and non-end block, including polyethylene glycol ethers fatty alcohol; (31) fatty alcohols, especially when they are useful as surfactant viscosity modifiers or present as unreacted components of other surfactants; (32) N-alkyl polyhydroxy fatty acid amides, especially the alkyl N-alkylallucamides; (33) nonionic surfactants derived from mono- or polysaccharides or sorbitan, especially alkyl polyglucosides, as well as fatty acid esters of sucrose; (34) ethylene glycol, propylene glycol, glycerol and polyglyceryl esters and their alkoxylates, especially glycerol ethers and the fatty acid / glycerol monoesters and diesters; (35) aldobionamide surfactants; (36) the types of alkylsuccinimide nonionic surfactant; (37) acetylenic alcohol surfactants, such as SURFYNOLS; (38) alkanolamide surfactants and their alkoxylated derivatives including fatty acid alkanolamides and polyglycol fatty acid alkanolamide ethers; (39) alkylpyrrolidones; (40) alkylamine oxides, including alkoxylated or polyalkoxylated amine oxides and amine oxides derived from sugars; (41) alkylphosphine oxides; (42) sulfoxide surfactants; (43) amphoteric sulfonate surfactants, especially sulfobetaines; (44) amphoteric betaine type, including the aminocarboxylate derivative types; (45) amphoteric surfactants such as the alkylammonium polyethoxy sulfates; (46) alkylamines derived from fat and petroleum and amine salts; (47) alkylimidazolines; (48) alkylamidoamines and their alkoxylated and polyalkoxylated derivatives and (49) conventional cationic surfactants including the water-soluble alkyldimethylammonium salts. In addition, the most unusual types of surfactants are included, such as: (50) oxides, carboxylates and quaternary alkylaminoamine salts; (51) sugar-derived surfactants modeled after any of the more conventional non-sugar types mentioned above; (52) fluoride surfactants; (53) surfactant bioagents; (54) organosilicon surfactants; (55) gemini surfactants, other than the diphenyl oxide disulfonates mentioned above, including those derived from glucose; (56) polymeric surfactants, including anfopoiicarboxyglycinates and (57) ball-shaped surfactants. In any of the foregoing detersive surfactants, the length of the hydrophobic chain is typically in the general scale of C8-C2o, with chain lengths being commonly preferred on the C8-Ci6 scale, especially when the fabric wash is to be carried out in cold water. The selection of the chain lengths and the degree of alkoxylation for conventional purposes are shown in the normal texts. When the surfactant is a salt, any compatible cation may be present, including H (ie, the acidic or partially acidic form of a potentially acidic surfactant may be used), NA, K, Mg, ammonium or alkanolammonium, or combinations thereof. cations. Mixes of detersive surfactants having different fillers are especially preferred, especially the anionic / nonionic, anionic / nonionic / cationic, anionic / amphoteric, nonionic / cationic and nonionic / amphoteric mixtures. In addition, any individual detersive surfactant may be substituted, commonly with desirable results for washing in cold water, by mixtures of other similar detersive surfactants having different chain lengths, degree of unsaturation or branching, degree of co-anilation (especially ethoxylation) , insertion of substituents such as ether oxygen atoms in the hydrophobes, or any combinations thereof.

Among the detersive surfactants identified above are preferred: sodium and ammonium alkylbenzenesulfonates C9-C20 acids, particularly C10-Ci5 (1) secondary linear sodium alkylbenzenesulfonates, including straight and branched chain forms; olefin sulphonate salts, (2), that is, material made by the reaction of olefins, in particular α-olefins of C-? 0-C2o, with sulfur trioxide and then neutralizing and hydrolyzing the reaction product; sodium and ammonium dialkylsulfoccinates of C7-C12, (3); alkanomonosulfonates, (4), such as those that are derived by reacting C8-C2o-olefins with sodium bisulfite and those that are derived by reacting paraffins with SO2 and Cl2 and then hydrolyzing with a base to form a random sulfonate; esters or salts of fatty acid a-Suifo, (10); sodium alkyl glyceryl sulphonates, (11), especially those ethers of the higher alcohols which are derived from bait or coconut oil and synthetic alcohols derived from petroleum; alkyl sulfates or alkenyl sulfates, (15), which may be primary or secondary, saturated or unsaturated, branched or unbranched. When said compounds are branched they can be random or regular. When they are secondary, they preferably have the formula CH3 (CH2) x (CHOSO3"M +) CH3 or CH3 (CH2) and (CHOSO3" M +) CH2CH3 where x and (y +1) are integers of at least 7, preferably at least minus 9 and M is a cation soluble in water, preferably sodium. When they are not saturated, sulfates such as oleum sulfate are preferred, although sodium and ammonium alkyl sulfates, especially those produced by sulfatar C8-C8 alcohols, produced for example from bait or coconut oil may also be used; Alkyl ether sulfates or acrylic ether sulphates are also preferred, (16), especially ethoxysulfates having about 0.5 mole or more of ethoxylation, preferably 0.5-8; alkyl ether carboxylates, (19), especially ethoxycarboxylates EO 1-5; soaps or fatty acids (21), preferably the most water-soluble types; amino acid-type surfactants, (23), such as sarcosinates, especially oleylsarcosinate; phosphate esters, (26); alkyl or alkylphenol ethoxylates, propoxylates and butoxylates, (30), especially the ethoxylates "AE", including the so-called straight-chain alkylethoxylates and C6-Ci2 alkylphenol-alkoxylates as well as the products of primary or secondary, linear or branched aliphatic alcohols of C8-C 8 with ethylene oxide, generally 2-30 EO; N-alkylpoxyhydroxy fatty acid amides especially C 12 -C 8 N -methucamides, (32), see WO 9206154, and N-alkoxypolyhydroxy fatty acid amides, such as N- (3-methoxypropyl) glucamide of C? oC- ? 8 while N-propyl to N-exyl C12-C-18 glucamides can be used for low foaming; alkyipoliglucosides, (33); amine oxides, (40), preferably N-alkyldimethylamine oxides and their dihydrates; sulfobetaines or "sultaines", (43); betaines (44); and gemini surfactants. Preferred levels of anionic detersive surfactants herein are in the range of from about 3% to about 30% or more, preferably from about 8% to about 20%, still most preferably from about 9% to about 18%. % by weight of the detergent composition. Preferred levels of nonionic detersive surfactant herein are from about 1% to about 20%, preferably from about 3% to about 18%, most preferably from about 5% to about 15%. Desirable weight ratios of anionic: nonionic surfactants in combination include from 1.0: 9.0 to 1.0: 0.25, preferably 1.0: 1.5 to 1.0: 0.4. Preferred levels of cationic detersive surfactant herein are from about 0.1% to about 10%, preferably from about 1% to about 3.5%, although much higher levels can be used, for example, up to 20% or more, especially in non-ionic formulations: cationic (ie, limited or free of ammonia). When present, amphoteric or zwitterionic detersive surfactants are typically used at levels in the range of about 0.1% to about 20% by weight of the detergent composition. Frequently the levels will be limited to around 5% or less, especially when the amphoteric is expensive.

Enzymes Enzymes may preferably be included in the present detergent compositions for a variety of purposes, including the removal of protein-based, carbohydrate-based or triglyceride-based stains from surfaces such as fabrics or dishes, for the prevention of dye transfer. , for example in laundry, and for fabric restoration. Suitable enzymes include proteases, amylases, lipases, cellulases, peroxidases and mixtures thereof of any suitable origin, such as vegetable, animal, bacterial, fungal and yeast. Preferred selections are influenced by factors such as optimal levels of pH activity and / or stability, thermostability, stability versus active detergents, builders, etc. In this regard, bacterial or fungal enzymes are preferred, such as bacterial amylases and proteases and fungal cellulases. The term "detersive enzyme", as used herein, means any enzyme that has a beneficial effect of cleaning, stain removal or any other beneficial effect in a laundry detergent, hard surface cleaning or personal care composition. Preferred detersive enzymes are hydrolases such as proteases, amylases and lipases. Enzymes that are preferred for laundry purposes include, but are not limited to, proteases, cellulases, lipases and peroxidases. The amylases and / or proteases for automatic dishwashing are widely preferred, including both commercially available types and improved types, which, while becoming increasingly compatible due to successive improvements, still have some degree of susceptibility to deactivation of the bleach. Enzymes are normally incorporated in detergent or detergent additive compositions at levels sufficient to provide an "effective cleaning amount". The term "effective cleaning amount" refers to any amount capable of producing a cleaning, stain removal, dirt removal, whiteness, deodorizing or freshness enhancing effect on substrates such as fabrics, tableware and the like. In practical terms for current commercial preparations, typical amounts are up to about 5 mg by weight, more typically about 0.01 mg to about 3 mg, of active enzyme per gram of composition. Stated otherwise, the compositions herein will typically consist of from about 0.001% to about 5%, preferably 0.01% -1% by weight of a commercial enzyme preparation. Protease enzymes are present in such commercial preparations at levels sufficient to provide from 0.005 to 0.1 Anson units (AU) of activity per gram of composition. For certain detergents, such as automatic dishwashing, it may be desirable to increase the active enzyme content of the commercial preparation to minimize the total amount of non-catalytically active materials and thereby improve splashes / films or other results. final. Higher active levels in highly concentrated detergent formulations may also be desirable. Suitable examples of proteases are the subtilisins that are obtained from particular strains of B.subtilis and B. licheniformis. Other suitable proteases are obtained from a Bacillus strain, having a maximum activity on the entire pH range of 8 to 12, developed and sold as ESPERASE® by Novo Industries A / S of Denmark, hereinafter "Novo". The preparation of this enzyme and analogous enzymes is described in GB 1, 243,784, by Novo. Other suitable proteases include ALCALASE® and SAVINASE® from Novo and MAXATASE® from International Bio-Synthetics, Inc., The Netherlands; as well as Protease A as described in EP 130,756 A, January 9, 1985 and Protease B as described in EP 87303761 A, April 28, 1987 and EP 130,756 A, January 9, 1985. See also a high protease. pH of Bacillus sp. NCIMB 40338 described in WO 9318140 A to Novo. Enzymatic detergents comprising protease, one or more other enzymes and a reversible protease inhibitor are described in WO 9203529 A to Novo. Other proteases that are preferred include those of WO 9510591 A to Procter & amp;; Gamble. When desired, a protease having decreased adsorption and increased hydrolysis is available as described in WO 9507791 to Procter & Gamble. A recombinant trypsin-like protease for detergents suitable herein is as described in WO 9425583 to Novo.

In more detail, a particularly preferred protease, called "protease D" is a carbonyl hydrolase variant having an amino acid sequence that is not found in nature, which is derived from a precursor carbonyl hydrolase by substituting a different amino acid for a plurality of amino acid residues at a position in said carbonyl hydrolase equivalent to the +76 position, preferably also in combination with one or more amino acid residue positions equivalent to those selected from the group consisting of +99, +101, +103 , +104, +107, +123, +27, +105, +109, +126, +128, +135, +156, +166, +195, +197, +204, +206, +210, + 216, +217, +218, +222, +260, +265, and / or +274 according to the numeration of the subtilisin of Bacillus amyloliquefaciens as described in WO 95/10615, published on April 20, 1995 by Genencor International. Useful proteases are also described in the PCT publications: WO 95/30010, published on November 9, 1995 by The Procter & Gamble Company; WO 95/3001 1, published November 9, 1995 by The Procter & Gamble Company and WO 95/29979, published November 9, 1995 by The Procter & Gamble Company. Amylases suitable herein, especially for, but not limited to, automatic dishwashing purposes, include, for example, α-amylases described in GB 1, 296, 839 to Novo; RAPIDASE®, International Bio-Synthetics, Inc. and TERMAMYL®, Novo. FUNGAMYL® by Novo is especially useful. Genetic manipulation of enzymes is known for improved stability, e.g., oxidative stability. See, for example, J. Biological Chem, Vol. 260, No. 1 1, June 1985, pp 6518-6521. Certain preferred embodiments of the present compositions may make use of amylases having improved stability in detergents such as those used for automatic dishwashing, especially improved oxidation stability as measured against a reference point of TERMAMYL® in commercial use in 1993. These preferred amylases of the present share the characteristics of being "improved stability" amylases, characterized, at a minimum, by a measurable improvement in one or more of: oxidative stability, e.g., to hydrogen peroxide / tetraacetylethylene diamine in pH regulated solution at pH 9-10; thermal stability, e.g., at common wash temperatures such as about 60 ° C; or alkaline stability, e.g., at a pH of about 8 to about 1 1, measured against the amylase of the reference point identified above. Stability can be measured using any of the technical tests described in the art. See, for example, the references described in WO 9402597. The improved stability amylases can be obtained from Novo or Genencor International. A class of highly preferred amylases herein has the common property of being derived using the site-directed mutagenesis of one or more of the Bacillus amylases, especially the Bacillus amylases, regardless of whether one, two or multiple strains of amylases are the immediate precursors. It is preferred to use the oxidative amylases of improved stability vs. the aforementioned reference amylase, especially in the bleaching compositions, most preferably oxygenated bleaching, other than chlorine bleaching, of the present invention. Said preferred amylases include a) an amylase according to WO 9402597, Novo, Feb. 3, 1994 incorporated above, as further illustrated by a mutant in which it is substituted, using alanine or threonine, preferably threonine, the residue of methionine located at position 197 of B.lichemiformis alpha-amylase, known as TERMAMYL®, or the variation of the homologous position of a similar progenitor amylase, such as B. amyloliquefaciens, B. subtilis or B. stearothermophilus; b) improved stability amylases as described by Genencor International in a document entitled "Oxidatively Resistant alpha-Amylases", presented at the 207 American Chemical Society National Meeting, March 13-17, 1944, by C. Mitchinson. There it is mentioned that the bleaches in automatic dishwashing detergents inactivate alpha-amylases, but that oxidative amylases of improved stability have been made by Genencor from B. licheniformis NCIB8061. Methionine (Met) was identified as the residue most likely to be modified. The Met was substituted, one at a time, in positions 8, 15, 197, 256, 304, 366 and 438 carrying specific mutants, particularly important being the variants MI97L and MI97T, with the variant M197T being the most stable expressed variant. The stability was measured in CASCADE® and SUNLIGHT®; (c) the particularly preferred amylases herein include the amylase variants having further modification in the immediate parent as described in WO 9510603 A and available from the Novo transferee, such as DURAMYL®. Another oxidizing amylase of improved stability that is preferred includes that described in WO 9418314 to Genencor International and WO 9402597 to Novo. Any other oxidative amylase of improved stability can be used, for example that derived by site-directed mutagenesis of known chimeric, hybrid or simple mutant progenitor forms of available amylases. Other modifications of enzyme that are preferred are also accessible. See WO 9509909 to Novo. Other amylase enzymes include those described in WO 95/26397 and in the co-pending application by Novo Nordisk PCT / DK96 / 00056. Specific amylase enzymes for use in the detergent compositions of the present invention include alpha-amyiases characterized by having a specific activity at least 25% higher than the specific activity of Termamyl® at a temperature range of 25 ° C to 55 ° C and a pH value on the scale of 8 to 10, as measured by the Phadebas® alpha-amylase activity test. Said Phadebas® α-amylase activity test is described on pages 9-10 of WO 95/26397). Also included herein are a-amylases that are at least 80% homologous to the amino acid sequences shown in the SEC ID listings in the references. These enzymes are preferably incorporated into the laundry detergent compositions at a level of about 0.0018% to 0.060% pure enzyme by weight of the total composition, preferably about 0.00024% to 0.048% pure enzyme by weight of the total composition. Cellulases that can be used herein include both bacterial and fungal cellulases, preferably at an optimum pH between 5 and 9.5. The U.S. 4,435,307, Barbesgoard et al., March 6, 1984, describes suitable fungal cellulases of the strain DSM 1800 of Humicola insolens or Humicola, or a cellulase-producing fungus 212 belonging to the genus Aeromonas, and the cellulase extracted from the hepatopancreas of a marine mollusk Dolabella Auricle Solander. Suitable cellulases are also described in GB-A-2,075,028; GB-A-2,095,275 and DE-OS-2,247,832. CAREZYME® and CELLUZYME® (Novo) are especially useful. See also WO 91 17243 to Novo. Suitable lipase enzymes are those produced by microorganisms of the Pseudomonas group, such as Pseudomonas stutzeri ATCC 19,154 as described in GB 1, 372, 034. Also see lipases in Japanese Patent Application 53,20487, open to public inspection on February 24, 1978. This lipase is available from Amano Pharmaceutical Co. Ltd., Nagoya, Japan, under the tradename Lipase P "Amano," or "Amano-P." Other suitable commercial lipases include Amano-CES, lipases ex Chromobacter viscosum, e.g. Chromobacter viscosum var. lipoliticum NRRLB 3673, from Toyo Jozo Co., Tagata, Japan; Chromobacter viscosum lipases from U.S. Biochemical Corp, E.U.A. and Disoynth Co., Holland. The lipase ex Pseudomonas gladioli. The LIPOLASE® enzyme derived from Humicola lanuginosa and commercially available from Novo (see also EP 341, 947) is a preferred lipase for use herein. Variants of lipase and amylase stabilized against peroxidase enzymes are described in WO 9414951 A to Novo. See also WO 9205529 and RD 94359044. Despite the large number of publications about lipase enzymes, only the lipase derived from Humicola lanuginosa and produced in Aspergillus oryzae as a host has so far found wide application as an additive for fabric washing products. This is available from Novo Nordisk under the Lipolase ™ brand, as mentioned above. To optimize the stain removal performance of Lipolase ™, Novo Nordisk has made a number of variants. As described in WO 92/05249, the D96L variant of the native Humicola lanuginosa enzyme improves efficiency in the removal of butter stains by a factor of 4.4 over wild-type lipase (enzymes compared in an amount ranging from 0.075 to 2.5 mg of protein per liter). The research description No. 35944, published on March 10, 1994 by Novo Nordisk, describes that the variant of iipase (D96L) can be added in an amount corresponding to 0.001-100 mg (5-500,000 LU / Iiter) of variant lipase per liter of liquid of washed. The present invention provides the benefit of improved whiteness maintenance on fabrics using D96L variant levels in the detergent compositions containing the average branched-chain primary alkyl surfactants in the manner described herein, especially when using the D96L at on the scale from about 50 LU to about 8500 LU per liter of the wash solution. Suitable cutinase enzymes for use herein are described in WO 8809367 A to Genencor. Peroxidase enzymes are used in combination with oxygen sources, eg, percarbonate, perborate, hydrogen peroxide, etc., for "bleaching in solution" or to avoid the transfer of dyes or pigments removed from the substrates during the washing operations to other substrates in the washing solution. Known peroxidase enzymes include horseradish peroxidase, ligninase and haloperoperoxidase such as chloroperoxidase and bromoperoxidase. Peroxidase-containing detergent compositions are described in WO 89099813 A, October 19, 1989 to Novo and WO 8909813 A to Novo. A wide variety of enzyme materials and means for their incorporation into synthetic detergent compositions are described in WO 9307263 A and WO 9307260 A to Genecor International, WO 8908594 A to Novo and US patent. 3,553,139, January 5, 1971 to McCarty and others. Additionally, enzymes are described in the U.S. patent. 4,101, 457, Place et al., July 18, 1978 and in the US patent. 4,507,219, Hughes, March 26, 1985. Enzyme materials useful for liquid detergent formulations and their incorporation into such formulations are described in the US patent. 4,261, 868, Hora et al., Issued April 14, 1981. Enzymes for detergents can be stabilized by various techniques.

Enzyme stabilization techniques are described and illustrated in the US patent. 3,600,319, August 7, 1971 to Gedge et al., And EP 199,405 and EP 200,586, October 29, 1986, Venegas. Enzyme stabilization systems are also described, for example, in E.U. 3,519,570. A Bacillus sp. Useful AC13 which gives proteases, xylanases and cellulases is described in WO 9401532 A to Novo.

Enzyme stabilization system The compositions containing enzymes herein can also comprise from about 0.001% to about 10%, preferably about 0.005% to about 8%, most preferably about 0.01% to about 6% by weight of a system of enzyme stabilization. The enzyme stabilization system can be any stabilization system that is compatible with the detersive enzyme. Such a system can be inherently provided by other formulation actives, or it can be added separately, eg, by the formulator or by a manufacturer of enzymes ready for detergents. Said enzyme stabilization systems may, for example, comprise calcium ion, boric acid, propylene glycol, short chain carboxylic acids, boronic acids and mixtures thereof, and are desigto satisfy different stabilization problems depending on the type and physical form of the detergent composition. 16 A stabilization approach is the use of water soluble sources of calcium and / or magnesium ions in the finished compositions, which provide said ions to the enzymes. Calcium ions are generally more effective than magnesium ions, and are preferred herein if only one type of cation is being used. Typical detergent compositions, especially liquid, will comprise about 1 to about 30, preferably about 2 to about 20, most preferably about 8 to about 12 millimoles of calcium ion per liter of finished detergent composition, although variation is possible depending of factors that include the multiplicity, type and levels of enzymes incorporated. Preference is given to using the water-soluble caichium or magnesium salts, including, for example, calcium chloride, calcium hydroxide, calcium formate, calcium malate, calcium maleate, calcium hydroxide and calcium acetate; very generally, calcium sulfate or the magnesium salts corresponding to the exemplified calcium salts can be used. Further increased levels of calcium and / or magnesium may of course be useful, for example to promote the fat-cutting action of certain types of surfactant. Another approach to stabilization is through the use of borate species. See Severson, E.U. 4,537,706. Borate stabilizers, when used, can be at levels of up to 10% or more of the composition, although more typically levels of up to about 3% by weight of boric acid or other borate compounds such as borax or orthoborate are suitable for the use of liquid detergents. Substituted boric acids such as phenylboronic acid, butanboronic acid, p-bromophenylboronic acid or the like, may be used in place of boric acid and reduced levels of total boron may be possible in the detergent compositions by the use of said substituted boron derivatives. The stabilization systems of certain cleaning compositions may further comprise from 0 to about 10%, preferably about 0.01% to about 6% by weight, of chlorine bleach scavengers, added to prevent the chlorine bleach species present in many Water sources attack and inactivate enzymes, especially under alkaline conditions. Although the chlorine levels in the water may be small, typically in the range of about 0.5 ppm to about 1.75 ppm, the available chlorine in the total volume of water that comes in contact with the enzyme, for example during the washing of tableware or fabrics, can be relatively large; consequently, the stability of the enzyme to chlorine during use is sometimes problematic. Since percarbonate or perborate, which have the ability to react with chlorine bleach, may be present in some of the present compositions in amounts independent of the stabilization system, the use of additional stabilizers against chlorine may, very generally, not be essential, although improved results can be obtained from its use. Suitable chlorine scavenging anions are widely known and readily available, and, if used, may be salts containing ammonium cations with suifite, bisulfite, thiosulfite, thiosulfate, iodide, etc. Likewise, antioxidants such as carbamate, ascorbate, etc., organic amines such as ethylenediaminetetraacetic acid (EDTA) or an alkali metal salt thereof, monoethanolamine (MEA) and mixtures thereof can be used. Likewise, special enzyme inhibition systems can be incorporated so that the different enzymes have maximum compatibility. If desired, other conventional sweepers such as bisulfate, nitrate, chloride, hydrogen peroxide sources such as sodium perborate tetrahydrate, sodium perborate monohydrate and sodium percarbonate, as well as phosphate, condensed phosphate, acetate, benzoate, citrate can be used. , formate, lactate, malate, tartrate, salicylate, etc. and mixtures thereof. In general, since the chlorine sweeping function can be carried out by separately listed ingredients under better recognized functions (eg, hydrogen peroxide sources), there is no absolute requirement to add a separate chlorine scavenger unless a compound that performs that function to the desired degree is absent in an embodiment of the invention that contains enzymes; Even in that case, the sweeper is added only for optimal results. Moreover, the formulator will exercise a normal chemical ability by avoiding the use of any enzyme scavenger or stabilizer that is primarily incompatible, as formulated, with other reactive ingredients, if used. In connection with the use of ammonium salts, said salts can be simply mixed with the detergent composition, but are prone to adsorb water and / or release ammonia during storage. Accordingly, said materials, if present, are desirably protected in a particle such as that described in E.U. 4,652,392.

Detergency Meters Detergent builders selected from aluminosilicates and silicates are preferably included in the compositions herein, for example to help control mineral hardness, especially Ca and / or Mg in the wash water, or to assist the Removal of particulate dirt from surfaces. Alternatively, certain compositions can be formulated with fully water-soluble builders, either organic or inorganic, depending on the intended use. Suitable silicate builders include the water-soluble and water-soluble types, and include those having a chain, layer or three-dimensional structure, as well as the amorphous-solid or unstructured-liquid types. Alkali metal silicates are preferred, particularly those liquids and solids having a Si 2: Na 2+ ratio. in the scale from 1.6: 1 to 3.2: 1, including, particularly for purposes of automatic dishwashing, 2-ratio solid aqueous silicates marketed by PQ Corp. under the trademark BRITESIL®, e.g., BRITESIL H2O; and stratified sodium silicates, e.g., those described in the US patent. 4,664,839, issued May 12, 1987 to H. P. Rieck.

NaSKS-6, sometimes abbreviated "SKS-6", is silicate of morphology * -Na2Si? 5 crystalline and aluminum-free laminated sold by Hoechst, and is especially preferred in granular laundry compositions. See preparation methods in the German application DE-A-3,417,649 and DE-A-3,742,043. Other layered silicates, such as those having the general formula NaMSix? 2? +? yH2? wherein M is sodium or hydrogen, x is a number from 1.9 to 4, preferably 2, and y is a number from 0 to 20, preferably 0 may be used herein. Some other stratified silicates from Hoechst include NaSKS-5, NaSKS-7 and NaSKS-1 1 as the alpha, beta and gamma forms. Other silicates can also be used such as for example magnesium silicate, which can serve as a tightening agent in granulated formulations, as a stabilizing agent for oxygen bleaches, and as a component of foam control systems. Also suitable for use herein are exchange materials of synthesized crystalline atoms or hydrates thereof having chain structure and a composition represented by the following general formula in the form of aldehyde: xM2? And Si? 2.zM'O wherein M is Na and / or K, M 'is Ca and / or Mg; y / x is 0.5 to 2.0 and z / x is 0.005 to 1.0 as taught in E.U. 5,427.71 1, Sakaguchi et al., June 27, 1995. Aluminosilicate builders are especially useful in granular detergents, but can also be incorporated into liquids, pastes or gels. Suitable for the present purposes are those that have the empirical formula: [Mz (Al? 2) z (Si? 2) v] xH2 ?, where z and v are integers of at least 6, the molar ratio of zav is in ia scale from 1.0 to 0.5, and x is an integer from 15 to 264. Aluminosilicates can be crystalline or amorphous, occurring naturally or synthetically derived. An aluminosilicate production method is described in E.U. 3,985,669, Krummel et al., October 12, 1976. The preferred synthetic crystalline aluminosilicate ion exchange materials are available as Zeolite A, Zeolite P (B), Zeolite X and, as far as is different from Zeolite P, the so-called Zeolite MAP. Natural types, including clinoptilolite, can be used. Zeolite A has the formula: Na- | 2 [(AIC, 2) l2 (if ° 2) l2]? H2 ° where x is from about 20 to about 30, especially around 27. You can also use the Dehydrated zeolites (x = 0-10). Preferably, the aluminosilicate has a particle size of about 0.1-10 microns in diameter. Builders instead of, or in addition to, the silicates and aluminosilicates described hereinabove can optionally be included in the compositions herein to help control mineral hardness, especially the hardness of Ca and / or Mg in the washing water or to help the removal of particulate dirt. The detergency builders can function through a variety of mechanisms including the formation of soluble or insoluble complexes with hardness ions, by ion exchange and offering a more favorable surface for the precipitation of hardness ions than are the surfaces of the ions. Items that are cleaned. The level of builder can vary greatly depending on the final use of the composition and the desired physical form. The builder levels typically comprise at least about 1% builder. Liquid formulations typically comprise about 5% to about 50%, very typically 5% to 35% builder. The granulated formulations typically comprise from about 10% to about 80%, very typically 15% to 50% by weight of the detergent composition. Lower or higher levels of builders are not excluded. For example, certain formulations of detergent additive or high surfactant content may not be improved in detergency. Suitable detergency builders herein can be selected from the group consisting of phosphates and pyrophosphates, especially the sodium salts, carbonates, bicarbonates, sesquicarbonates and carbonate minerals other than sodium carbonate or sesquicarbonate.; organic mono-, di- and tetracarboxylates, especially the carboxylates which are not water-soluble surfactants and in the form of acid, sodium, potassium or alkanolammonium salts, as well as oligomeric or water-soluble low molecular weight polymeric carboxyiates, including the types aliphatic and aromatic; and phytic acid. These may be supplemented with borates, eg, for pH regulation purposes, or by sulfates, especially sodium sulfate and any other fillers or vehicles that may be important for the design of stable detergent compositions containing surfactants and / or detergency builders. Mixtures of builders, sometimes called "builder systems," can be used, and typically comprise two or more conventional builders, optionally supplemented with chelators, pH regulators or fillers, although the latter materials are taken in account separately when describing the quantities of materials herein. In terms of relative amounts of surfactant and builder in the present detergents, the preferred builder systems are typically formulated at a surfactant to builder ratio of from about 60: 1 to about 1: 80 Certain detergents that are preferred have said ratio in the range of 0.90: 1.0 to 4.0: 1.0, preferably 0.95: 1 to 3.0: 1.0. Phosphate-containing builders are commonly preferred when allowed by law, and include, but are not limited to, the alkali metal, ammonium and alkanolammonium salts of polyphosphates, exemplified by the tripolyphosphates, pyrophosphates, crystalline polymeric meta-phosphates. and phosphonates. Carbonate builders include alkali metal and alkali metal carbonates as described in German Patent Application No. 2,321,001 published November 15, 1973, although sodium bicarbonate, sodium carbonate, sodium sesquicarbonate and other carbonate minerals such as trona or any multiple salts of calcium carbonate such as those having the composition 2Na2C? 3-CaC? 3 when they are anhydrous, and even calcium carbonates including calcite, aragonite and vaterite, especially the forms that have high surface areas relative to compact calcite can be very useful, for example as seeds or for use in synthetic detergent bars. Suitable organic builders include polycarboxylate compounds, including dicarboxylates and tricarboxylates that are non-surfactant and water soluble. Very typically, the builder polycarboxylates have a plurality of carboxylate groups, preferably at least 3 carboxylates. The carboxylate builders can be formulated in acid, partially neutral, neutral or overbased form. When they are in salt form, alkali metals such as sodium, potassium and lithium, or alkanolammonium salts are preferred. Polycarboxylate builders include ether polycarboxylates, such as oxydisuccinate, see Berg, E.U. 3,128,287, April 7, 1964, and Lamberti et al., E.U. 3,635,830, January 18, 1972. See also builders of "TMS / TDS" of E.U. 4,663,071, Bush et al., May 5, 1987; and other ether polycarboxylates including cyclic and alicyclic compounds, such as those described in the U.S. Patents. 3,923,679; 3,835,163; 4,158,635; 4,120,874 and 4,102,903. Other useful builders include ether hydroxypolycarboxylates, maleic anhydride copolymers with ethylene or vinyl methyl ether, 1,3-trihydroxybenzene-2,4,6-trisulfonic acid, and carboxymethyloxy-succinic acid, various alkali metal salts, ammonium and substituted ammonium of polyacetic acids such as ethylenediaminetetraacetic acid and nitrilotriacetic acid, as well as meiitic acid, succinic acid, polymaleic acid, benzene-1, 3,5-tricarboxylic acid, carboxymethyloxysuccinic acid and soluble salts thereof. The citrates, e.g., citric acid and soluble salts thereof, are important carboxylate builders, e.g., for heavy duty liquid detergents because of their availability from renewable resources and their biodegradability. The citrates can also be used in granular compositions, especially in combination with zeolite and / or layered silicates. Oxydisuccinates are also especially useful in said compositions and combinations. When allowed, and especially in the formulation of bars used for hand washing operations, the alkali metal phosphates such as sodium tripolyphosphates, sodium pyrophosphate and sodium orthophosphate can be used. They may also be used and may have anti-fouling properties - phosphonate builders such as ethane-1-hydroxy-1,1-diphosphonate and other known phosphonates, eg, those of E.U. 3,159,581; 3,213,030; 3,422,021; 3,400,148 and 3,422,137. Certain detersive surfactants or their short chain homologs also have detergency builder action. For unambiguous formula reasons, when they have surfactant capacity, these materials are taken into account as detersive surfactants. The preferred types of builder functionality are illustrated by: 3,3-dicarboxy-4-oxa-1,6-hexanedioates and the related compounds described in E.U. 4,566,984, Bush, January 28, 1986. Succinic acid builders include alkyl and alkenyl succinic acids of C5-C20 and salts thereof. Succinate builders include: laurylsuccinate, myristylsuccinate, palmitylsuccinate, 2-dodecenylsuccinate (preferred), 2-pentadecenylsuccinate, and the like. Lauryl succinates are described in European patent application 86200690.5 / 0,200,263, published on November 5, 1986. Fatty acids, e.g., monocarboxylic acids of C- | 2- -i 8 > they can also be incorporated into the compositions as surfactant / builder materials alone or in combination with the aforementioned builders, especially citrate and / or succinate builders, to provide additional builder activity. Other suitable polycarboxylates are described in E.U. 4,144,226, Crutchfield et al., March 13, 1979 and in E.U. 3,308,067, Diehl, March 7, 1967. See also Diehl, E.U. 3,723,322. Other types of inorganic builders materials that can be used have the formula (Mx) Cay (C? 3) z wherein xei are integers from 1 to 15, and is an integer from 1 to 10, z is an integer of 2 to 25, M, are cations, at least one of which is soluble in water, and the equation λ = 1-15 (x, multiplied by the valence of M,) + 2y = 2z is satisfied in such a way that the formula has a neutral or "balanced" charge. These builders are called "mineral builders" here. Hydration waters or anions other than carbonate can be added, as long as the total charge is balanced or neutral. The charge or valence effects of said anions must be added to the correct side of the previous equation. Preferably, a water-soluble cation selected from the group consisting of hydrogen, water-soluble metals, hydrogen, boron, ammonium, silicon and mixtures thereof, most preferably sodium, potassium, hydrogen, lithium, ammonium and mixtures thereof, is present. thereof. Non-limiting examples of non-carbonate anions include those selected from the group consisting of chloride, sulfate, fluoride, oxygen, hydroxide, silicon dioxide, chromate, nitrate, borate and mixtures thereof. Detergency builders of this type that are preferred in their simplest forms are selected from the group consisting of Na 2 Ca (C 3) 2, K 2 Ca (CO 3) 2, Na 2 Ca 2 (C 3) 3, NaK Ca (CO 3) 2, NaK Ca 2 ( CO3) 3, K2Ca2 (CO3) 3 and combinations thereof. An especially preferred material for the builder described herein is Na 2 Ca (C 3) 3 in any of its crystalline modifications. Suitable detergency builders of the type defined above are further illustrated by, and include, the natural or synthetic forms of any or combinations of the following minerals: afghanite, andersonite, ashcroftine Y, beyerite, borcharite, burbankite, butschliite, cancrinite, carbocemaite, carletonita, davina, donnaüta And, fairchildita, ferrisurita, franzinita, gaudefroyita, gaylussita, girvasita, gregorita, jouravskita, kampahaugita And, kettnerita, khanneshita, lepersonitaGd, lyotita, mckelveyita And, microsomita, mroseita, natrofairchildita, nierereita, remonditaCe, sacrofanita, schrockingerita , shortita, surita, tunisita, tuscanita, tirolita, vishnevita or zemkorita. The mineral forms that are preferred include niererite, fairchildite and shortita. Many detergent compositions herein will be regulated in their pH, that is, they are relatively resistant to pH drop in the presence of acid soils. However, other compositions herein may have an extremely low pH buffering capacity, or they may be substantially unregulated in their pH. Techniques for controlling or varying the pH to recommended levels of use very generally include the use not only of pH regulators, but also of alkalis, acids, pH leap systems, additional double-compartment containers, etc., and are known well by those skilled in the art. Certain compositions that are preferred herein, such as certain types of ADD, comprise a pH adjusting component selected from water-soluble alkaline inorganic salts and water-soluble organic or inorganic builders. The pH adjustment components are selected such that when the ADD is dissolved in water at a concentration of 1,000-5,000 ppm, the pH remains on the scale of approximately more than 8, preferably around 9.5 to approximately 1 1. The non-phosphate pH adjustment component which is preferred in the invention is selected from the group consisting of: (i) sodium carbonate or sesquicarbonate.; (ii) sodium silicate, preferably hydrated sodium silicate having an SiO2: Na20 ratio of about 1: 1 to about 2: 1 and mixtures thereof with limited amounts of sodium metasilicate; (iii) sodium citrate; (iv) citric acid; (v) sodium bicarbonate; (vi) sodium borate, preferably borax; (vii) sodium hydroxide and (viii) mixtures of (i) - (vii). Preferred embodiments contain low silicate levels (i.e., from about 3% to about 10% SiO 2). Highly illustrative examples of highly preferred pH adjusting component systems are the binary mixtures of granulated sodium citrate with anhydrous sodium carbonate and the three component mixtures of granulated sodium citrate trihydrate, citric acid monohydrate and anhydrous sodium carbonate. The amount of the pH adjustment component in the automatic dishwashing compositions is preferably from about 1% to about 50% by weight of the composition. In a preferred embodiment, the pH adjustment component is present in the composition in an amount of about 5% to about 40%, preferably about 10% to about 30% by weight. For the compositions herein having a pH between about 9.5 and about 11 of the initial wash solution, the ADD modalities that are particularly preferred comprise, by weight of the ADD, from about 5% to about 40%, preferably about 10% to about 30%, most preferably about 15% to about 20% sodium citrate; with about 5% to about 30%, preferably about 7% to about 25%, most preferably about 8% to about 20% sodium carbonate. The essential pH adjustment system can be complemented (i.e., for improved sequestration in hard water) with other optional builder salts selected from the non-phosphate builders known in the art, which include the various borates hydrosoluble, alkali metal, ammonium or substituted ammonium hydroxysulphonates, polyacetates and polycarboxylates. Alkali metal salts, especially the sodium salts of said materials, are preferred. Organic detergency builders other than phosphorus and water soluble alternatives can be used due to their sequestration properties. Examples of polyacetate and polycarboxylate builders are the sodium, potassium, lithium, ammonium and substituted ammonium salts of ethylenediaminetetraacetic acid; nitrilotriacetic acid, tartratomonosuccinic acid, tartrate diuccinic acid, oxydisuccinic acid, carboxymethoxysuccinic acid, melific acid and sodium benzene polycarboxylate salts. The detergent compositions for automatic dishwashing can further comprise water-soluble silicates. The water-soluble silicates herein are any silicate that is soluble to the extent that it does not adversely affect the spot / film reduction characteristics of the ADD composition. Examples of silicates are sodium metasilicates and, more generally, alkali metal silicates, particularly those having an SiO2: Na2O ratio in the range of 1.6: 1 to 3.2: 1; and stratified silicates, such as the layered sodium silicates described in the U.S. patent. 4,664,839, issued May 12, 1987 to H. P. Rieck. NaSKS-6® is a stratified crystalline silicate marketed by Hoechst (commonly abbreviated here as "SKS-6"). Unlike zeolite builders, Na SKS-6 and other water-soluble silicates useful herein do not contain aluminum. NaSKS-6 is the d-Na2OSi? 5 form of layered silicate and can be prepared by methods such as those described in German DE-A-3, 417,649 and DE-A-3, 742,043. SKS-6 is a stratified silicate that is preferred to be used in the present, but other layered silicates can be used, such as those having the general formula NaMSixO2? + ?: and H2? wherein M is sodium or hydrogen, x is a number from 1.9 to 4, preferably 2, and (y) is a number from 0 to 20, preferably 0. Several other stratified silicates from Hoechst include NaSKS-5, NaSKS-7 and NaSKS-1 1, as the forms a-, ß- and? -. Other silicates may also be useful, such as for example magnesium silicate, which may serve as a tightening agent in granulated formulations, as a stabilizing agent for oxygenated bleach and as a component of foam control systems. Silicates particularly useful in automatic dishwashing (ADD) applications include granulated ratio 2 hydrous silicates such as BRITESIL® H20 from PQ Corp., and the commonly obtained BRITESIL® H24, although the liquid grades of various silicates can be used when the ADD composition is in liquid form. Within safe limits, the sodium metasilicate or sodium hydroxide alone or in combination with other silicates can be used in an ADD context to promote washing pH to a desired level.

Polymeric dirt release agent The known polymeric soil release agents, hereinafter "SRA" or "SRA's", can optionally be used in the present detergent compositions. If used, the SRA's will generally comprise from about 0.01% to 10.0%, typically from about 0.1% to 5%, preferably from about 0.2% to 3.0% by weight, of the compositions. Preferred SRA's typically have hydrophilic segments to hydrophilize the surface of the hydrophobic fibers such as polyester and nylon, and the hydrophobic segments to deposit on and remain adhered to the hydrophobic fibers through the completion of the washing and rinsing cycles, thus serving as an anchor for the hydrophilic segments. This can make it possible for stains that occur after treatment with the SRA to be cleansed more easily in subsequent washing procedures. SRA's may include a variety of charged, eg, anionic or even cationic species; see the patent of E.U.A. No. 4,956,447, issued September 11, 1990 to Gosselink et al., As well as monomer uncharged units and their structures which may be linear, branched and even star-shaped. They may include end blocking portions that are especially effective in controlling molecular weight or altering active surface or physical properties. The structures and load distributions can be designed for application to different types of fibers or textiles and for detergent products or various detergent additives. Preferred SRAs include oligomeric terephthalate esters, typically prepared by methods that include at least one transesterification / oligomerization, commonly with a metal catalyst such as a titanium (IV) alkoxide. Said esters can be manufactured using additional monomers capable of being incorporated into the ester structure through uan, two, three, four or more positions, without, of course, forming a densely intertwined overall structure. Suitable SRA's include a sulphonated product of a substantially linear ester oligomer formed from an oligomeric ester base structure of terephthaloyl and oxyalkylenoxy repeat units and sulfonated terminal portions derived from allyl covalently attached to the base structure, for example, as described in the US patent 4,968,451, November 6, 1990 by J. J. Scheibel and E.P. Gosselink. Said ester oligomers can be prepared: (a) ethoxylating allyl alcohol; (b) reacting the product of (a) with dimethyl terephthalate ("DMT") and 1,2-propylene glycol ("PG") in a two step transesterification / oligomerization process; and (c) reacting the product of (b) with sodium metabisulfite in water. Other SRA's include the polyesters of 1, 2-propylene / polyoxyethylene terephthalate of non-ionic blocked ends of the US patent. No. 4,71 1, 730, of December 8, 1987 to Gosselink and others, for example those produced by the transesterification / oligomerization of polyethylene glycol methyl ether, DMT, PG and polyethylene glycol ("PEG"). Other examples of SRA's include: the oligomeric esters of anionic blocked ends partially and completely of the U.S. patent. No. 4,721, 580, of January 26, 1988 to Gosselink, such as oligomers of ethylene glycol ("EG"), PG, DMT and Na-3,6-dioxa-8-hydroxyoctansulfonate; the non-ionic blocked block polyester oligomeric compounds of the U.S.A. 4,702,857, from October 27, 1987 to Gosselink, for example produced from DMT, PEG and EG and / or PG (Me) -blocked methyl or a combination of DMT, EG and / or PG, PEG Me-blocked and Na-dimethyl-5-sulfoisophthalate; and the blocked terephthalate esters of the anionic ends, especially of sulfoaroyl of the U.S. patent. No. 4,877,896 of October 31, 1989 to Maidonado Gosselink and others, the latter being a typical SRA's useful in both fabric conditioning and laundry products with one example being an ester composition made from the monosodium salt of m-suifobenzoic acid, PG and DMT, optionally but preferably also comprising added PG, e.g., PEG 3400. SRA's also include: simple copolymer blocks of ethylene terephthalate or propylene terephthalate with polyethylene oxide terephthalate or polypropylene oxide, see US Patent Do not. 3,959,230 to Hays of May 25, 1976 and the patent of E.U.A. Do not. 3,893,929 to Basadur, July 8, 1975, cellulose derivatives such as the hydroxyether cellulosic polymers available as METHOCEL from Dow; the C-1-C4 alkyl celluloses and C4 hydroxyalkylcells of the U.S. patent. No. 4,000,093, of December 28, 1976 to Nicol, and others. The Suitable SRA's characterized by hydrophobic polyvinylmethyl ether segments include polyvinyl ether graft copolymers, e.g., vinyl ethers of C- \ -CQ, preferably polyvinylacetate, grafted onto polyalkylene oxide base structures. See European patent application 0 219 048, published on April 22, 1987 by Kud et al. Commercially available examples include SOKALAN SRA's such as SOKALAN HP-22, available from BASF, Germany. Other SRAs are polymers with repeating units having 10-15% by weight of ethylene terephthalate together with 80-90% by weight of polyoxyethylene terephthalate derived from polyoxyethylene glycol of an average molecular weight of 300-5000. Commercial examples include ZELCON 5126 from Dupont and MILEASE T from ICI. Another preferred SRA is an oligomer having the empirical formula (CAP) 2 (EG / PG) 5 (t) 5 (SIP) - | , which includes terephthaloyl units (T), sulfoisophthaloyl (SIP), oxyethyleneoxy and oxy-1,2-propylene (EG / PG), and which preferably terminates with end blocks (CAP), preferably modified isethionates, as in an oligomer comprising a sulfoisophthaloyl unit , 5-terephthaloyl units, oxyethyleneoxy and oxy-1, 2-propylenexi units in a defined ratio, preferably from about 0.5: 1 to about 10: 1, and two end blocking units derived from 2- (2-hydroxyethoxy) -ethansulfonate . Said SRA preferably comprises from 0.5% to 20% by weight of the oligomer of a crystallinity reduction stabilizer, for example an anionic surfactant such as linear dodecylbenzenesulfonate or a member selected from xylene, cumene and toluene sulfonate or mixtures thereof, these stabilizers or modifiers being introduced into the synthesis vessel, all as taught in the US patent No. 5,415,807, Gosselink Pan, Lellett and Hall, issued May 16, 1995. Suitable monomers for the above SRA include Na-2 (2-hydroxyethoxy) -ethanesulfonate, DMT, Na-dimethyl-5-sulfoisophthalate, EG and PG. Yet another group of preferred SRA's are oligomeric esters comprising: (1) a base structure comprising (a) at least one unit selected from the group consisting of dihydroxysulfonates, polyhydroxysulfonates, a unit that is at least trifunctional, by whereof ester bonds resulting in a branched oligomeric base structure, and combinations thereof, are formed; (b) at least one unit that is a terephthaloyl moiety; and (c) at least one non-sulfonated unit which is a 1,2-oxyalkylenoxy portion; and (2) one or more blocking units selected from non-ionic blocking units, anionic blocking units such as alkoxylated isethionates, preferably ethoxylated, alkoxylated propansulfonates, alkoxylated propanedisulfonates, alkoxylated phenolsulfonates, sulfoaroyl derivatives, and mixtures thereof. The esters of the empirical formula are preferred:. { (CAP) x (EG / PG) y '(DEG) y "(PEG) y'" (T) z (SIP) z '(SEG) q (B) m} where CAP, EG / PG, PEG, T and SIP are as defined above, (DEG) represents units of di (oxyethylene) oxy, (SEG) represents units derived from the sulfoethyl ether of glycerin and related portion units, (B) represents branching units that are at least trifunctional, whereby ester bonds resulting in a branched oligomer base structure are formed, x is from about 1 to about 12, and 'is from about 0.5 to about 25, and' is from 0 to about 12, and "'is from 0 to about 10, and' + y" + y '"sum in total from about 0.5 to about 25, z is from about 1.5 to about 25, z' is from around 0 to about 12; z + z 'sum total of about 1.5 to about 25, which is about 0.05 to about 12; m is from about 0.01 to about 10, and x, y ', y ", y'", z, z ', q and m represent the average number of moles of the corresponding units per mole of said ester, and said ester has a weight molecular which varies from about 500 to about 5,000. Preferred SEG and CAP monomers for the above esters include sodium 2- (2,3-dihydroxypropoxy) -ethansulfonate ("SEG"), 2-. { 2- (2-hydroxyethoxy) ethoxy} sodium acetate sulfonate ("SE3") and homologs and mixtures thereof, and the products of ethoxylation and sulfonation of allylic alcohol. Preferred SRA esters in this class include the transesterification and oligomerization product of 2-. { 2- (2-hydroxyethoxy) ethoxy} sodium ethane sulfonate and / or 2- [2-. { 2- (2-hydroxyethoxy) ethoxy} sodium ethoxy] ethane sulfonate, DMT, sodium 2- (2,3-dihydroxypropoxy) ethane sulfonate, EG and PG using an appropriate Ti (IV) catalyst, and can be designated as (CAP) 2 (T) 5 (EG /PG)1.4(SEG)2.5(B)0.13, where CAP is (Na +? 3S [CH2CH2?] 3.5) - and B is a glycerin unit, and the mass ratio of EG / PG is about 1.7: 1 measured by conventional gas chromatography after complete hydrolysis. Additional classes of SRA's include: (I) non-ionic terephthalates using diisocyanate coupling agents to link the polymeric ester structures, see E.U. 4,201, 824, Violland et al. And E.U. 4,240,918 Lagasse et al., And (II) SRA's with carboxylate end groups made by adding trimethyl anhydride to known SRA's to convert terminal hydroxyl groups to trimethylate esters. With the proper selection of the catalyst, trimethyl anhydride forms bonds to the polymer terminals through a carboxylic acid ester isolated from the trimethyl anhydride instead of opening the anhydride linkage. Either non-ionic or anionic SRAs can be used as starting materials, as long as they have hydroxyl end groups that can be esterified, see E.U. No. 4,525,524 Tung and others. Other classes include (lll) non-anionic terephthalate-based SRAs of the urethane-linked variety, see E.U. 4,201, 824, Violland et al .; (IV) polyvinylcaprolactam and copolymers related to monomers such as vinyl pyrrolidone and / or dimethylamineth methacrylate, including nonionic and cationic polymers, see E.U. 4,579,681, Rupper et al., (V) graft copolymers, in addition to the SOKALAN types of BASF, manufactured by grafting acrylic monomers to sulfonated polyesters. These SRA's have soil release and antiredeposition activity similar to the known cellulose ethers: see EP 279,134 A. 1988 to Rhone Poulenec Chemie. Other classes also include: (VI) vinyl monomer grafts such as acrylic acid and vinyl acetate in proteins such as caseins, see EP 457,205 A to BASF (1991); and (VII) Polyester-polyamide SRA's prepared by condensing adipic acid, caprolactam and polyethylene glycol, especially for treating polyamide fabrics, see Bevan et al., DE 2,335,044 to Unilever N.V., 1974. Other SRA's useful in the U.S. Patents. Nos. 4,240,918, 4,787,989 and 4,525,524 and 4,877,896.

Clay soil remover / anti-redeposition agents The compositions of the present invention may also optionally contain water-soluble ethoxylated amines having clay dirt removal and anti-redeposition properties. Granular detergent compositions containing these compounds typically contain from about 0.01% to about 10.0% by weight of the water-soluble ethoxylated amines; Liquid detergent compositions typically contain about 0.01% to about 5%. A preferred soil remover and anti-redeposition agent is ethoxylated tetraethylenepentamine. Exemplary ethoxylated amines are more fully described in the U.S. patent. 4,597,898, VanderMeer, issued July 1, 1986. Another group of clay soil removal / anti-redeposition agents are the cationic compounds described in European patent application 1 1 1, 965, Oh and Gosselink, published on 27 June 1984. Other clay soil removal / anti-redeposition agents that may be used include the ethoxylated amine polymers described in European Patent Application 11 1, 984, Gosselink, published June 27, 1984; the zwitterionic polymers described in European patent application 1 12,592, Gosselink, published on July 4, 1984; and the amine oxides described in the U.S. patent. No. 4,548,744, Connor, issued October 22, 1985. Other clay removers and / or anti-redeposition agents known in the art can be used in the compositions herein. Another type of preferred anti-redeposition agent includes the carboxylmethylcellulose (CMC) materials. These materials are well known in the art.

Polymeric dispersion agents Polymeric dispersion agents can be used advantageously at levels of from about 0.1% to about 7%, by weight, in the compositions herein, especially in the presence of zeolite builders and / or layered silicate builders. Suitable polymeric dispersing agents include polymeric polycarboxylates and polyethylene glycols, although others known in the art may also be used. It is believed, although not intended to be limited by theory, that polymer dispersion agents increase the performance of the overall detergency builder, when used in combination with other builders (including lower molecular weight polycarboxylates) by growth inhibition. of crystals, peptization of release of dirt into particles and anti-redeposition. Polymeric polycarboxylate materials can be prepared by polymerizing or copolymerizing suitable unsaturated monomers, preferably in their acid form. Unsaturated monomeric acids which can be polymerized to form suitable polymeric polycarboxylates include acrylic acid, maleic acid (or maleic anhydride), fumaric acid, itaconic acid, aconitic acid, mesaconic acid, citraconic acid, methylenemalonic. The presence of the polymeric polycarboxylates in the present or polymeric segments, which do not contain carboxylate radicals such as vinyl methyl ether, styrene, ethylene, etc., is suitable provided that said segments do not constitute more than about 40% by weight. Particularly suitable polymeric polycarboxylates can be derived from acrylic acid. Said acrylic acid-based polymers which are useful herein are the water-soluble salts of polymerized acrylic acid. The average molecular weight of such polymers in the acid form perferably varies from about 2,000 to 10,000, most preferably from about 4,000 to 7,000 and most preferably from about 4,000 to 5,000. The water-soluble salts of said acrylic acid polymers can include, for example, the alkali metal, ammonium and substituted ammonium salts. Soluble polymers of this type are known materials. The use of polyacrylates of this type in detergent compositions has been described, for example, in Diehl, US Pat. 3,308,067, issued March 7, 1967. Copolymers based on acrylic / maleic acid may also be used as a preferred component of the dispersing / anti-redeposition agent. Such materials include the water soluble salts of copolymers of acrylic acid and maleic acid. The average molecular weight of said copolymers in the acid form preferably ranges from about 2,000 to 100,000, more preferably about 5,000 to 75,000 and most preferably about 7,000 to 65,000. The ratio of acrylate segments to those of maleate in said copolymers generally ranges from about 30: 1 to about 1: 1, most preferably about 10: 1 to 2: 1. The water-soluble salts of said acrylic acid / maleic acid copolymers may include, for example, the alkali metal, ammonium and substituted ammonium salts. Soluble acrylate / maleate copolymers of this type are known materials which are described in European patent application No. 66915, published on December 15, 1982, as well as in EP 193,360, published on September 3, 1986, which also describes polymers comprising hydroxypropylacrylate. Other useful dispersing agents include the maleic / acrylic / vinyl alcohol terpolymers. Such materials are also described in EP 193,360, including, for example, terpolymer 45/45/10 maleic / acrylic / vinyl alcohol.

Another polymeric material that can be included is polyethylene glycol (PEG). The PEG can exhibit dispersing agent performance and can act as a clay dirt removal / anti-redeposition agent. Typical molecular weight scales for these purposes range from about 500 to about 100,000, preferably about 1,000 to about 50,000 and most preferably about 1,500 to about 10,000. The dispersing agents of polyaspartate and polyglutamate, especially in conjunction with zeolite builders, can also be used. Dispersing agents such as those of polyaspartate preferably have a molecular weight (avg.) Of about 10,000. Other types of polymers that may be more desirable for purposes of biodegradability, improved bleach stability or cleaning include various hydrophobically modified terpolymers and copolymers, including those marketed by Rohm & Haas, BASF Corp., Nippon Shokubai and others for all forms of water treatment, textile treatment or detergent applications.

Brightener Any optical brighteners or other brighteners or whitening agents known in the art can be incorporated at levels typically from about 0.01% to 1.2% by weight, in the detergent compositions herein. Commercial optical brighteners that may be useful in the present invention may be classified into subgroups including, but not necessarily limited to, stilbene, pyrazoline, coumarin, carboxylic acid, methinocyanin, dibenzotifen-5-dioxide, azole, heterocyclic ring of 5 and 6 members, and other diverse agents. Examples of such brighteners are described in "The Production and Application of Fluorescent Brightening Agents," M. Zahradnik, published by John Wiley & Sons, New York (1982). Specific examples of optical brighteners that are useful in the present compositions are those identified in the U.S. patent. 4,790,856 issued to Wixon on December 15, 1988. These brighteners include the PHORWHITE series of brighteners from Verona. Other brighteners described in this reference include: Tinopal UNPA, Tinopal CBS and Tinopal 5BM; available from Ciba-Geigy; Artic White CC and Artic White CWD, available from Hilton-Davis, located in Italy; 2- (4-styryl-phenyl) -2H-naphthol [1,2-d] triazoles; 4,4'-bis- (1, 2,3-triazol-2-yl) -stilbenes; 4,4'-bis (styryl) bisphenyls; and the aminocoumarins. Specific examples of these brighteners include 4-methyl-7-diethyl-aminocoumarin; 1, 2-bis (-benzimidazol-2-yl-ethylene; 1,3-diphenylpyrazolines; 2,5-bis (benzoxazol-2-yl) thiophene; 2-styryl-naphthyl- [1,2-s] oxazole; and 2- (stilben-4-yl) -2H-naphtho- [1,2-d] triazole See also U.S. Patent No. 3,646,015, issued February 29, 1972 to Hamilton.

Dye transfer inhibiting agents The compositions according to the present invention can also include one or more effective materials to inhibit the transfer of dyes from one fabric to another during the cleaning process. Generally, said dye transfer inhibiting agents include polyvinyl pyrrolidone polymers, polyamine N-oxide polymers, copolymers of N-vinylpyrrolidone and N-vinylimidazole, manganese phthalocyanine, peroxidases and mixtures thereof. If used, these agents typically comprise from about 0.01% to about 10% by weight of the composition, preferably from about 0.01% to about 5%, and most preferably from about 0.05% to about 2%. Very specifically, the preferred polyamine N-oxide polymers for use herein contain units having the following structural formula: R-Ax-P; wherein P is a polymerizable unit to which a N-O group can be attached or the N-O group can be part of the polymerizable unit or the N-O group can be attached to both units.

; A is one of the following structures: -NC (O) -, -C (O) O-, -S-, -O-, -N =; x is 0 or 1; and R is aliphatic, aliphatic, ethoxylated, aromatic, heterocyclic or alicyclic groups or any combination thereof to which the nitrogen of the N-O group can be attached or the N-O group is part of these groups. Preferred polyamine N-oxides are those wherein R is a heterocyclic group such as pyridine, pyrrole, imidazole, pyrroline, piperidine and derivatives thereof.

The N-O group can be represented by the following general structures: O O (R.,) - N- (R2) y; = N- (R1)? (R3) z wherein Ri, R2, R3 are aliphatic, aromatic, heterocyclic or aiicyclic groups or combinations thereof; x, y and z are 0 or 1; and the nitrogen of the N-O group can be attached or forms part of any of the aforementioned groups. The amine oxide unit of the polyamine N-oxides has a pKa < 10, preferably pKa < 7, very preferably still pKa < 6. Any polymer base structure can be used as long as the amine oxide polymer formed is soluble in water and has dye transfer inhibiting properties. Examples of suitable polymeric base structures are polyvinyls, polyalkylenes, polyesters, polyethers, polyamides, polyimides, polyacrylates and mixtures thereof. These polymers include random or block copolymers wherein one type of monomer is an amine N-oxide and the other type of monomer is an N-oxide. The amine N-oxide polymers typically have an amine to amine N-oxide ratio of 10: 1 to 1: 1,000,000. However, the number of amine oxide groups present in the polyamine oxide polymer can be varied by appropriate copolymerization or by an appropriate degree of N-oxidation. Polyamine oxides can be obtained in almost any degree of polymerization. Typically, the average molecular weight is within the range of 500 to 1,000,000; very preferred from 1,000 to 500,000; even more preferred 5,000 to 100,000. This preferred class of materials can be referred to as "PVNO". The most preferred polyamine N-oxide useful in the detergent compositions herein is the poly-4-vinylpyridine N-oxide having an average molecular weight of about 50,000 and an amine to amine N-oxide ratio of about 1: 4 Polymer copolymers of N-vinylporrolidone and N-vinylimidazole (also known as "PVPVI") are also preferred for use herein. Preferably, the PVPVI has an average molecular weight in the range of 5,000 to 1,000,000, most preferably 5,000 to 200,000 and most preferably even 10,000 to 20,000. (The average molecular weight scale is determined by light scattering as described in Barth, and other Chemical Analysis, Vol. 113. "Modern Methods of Polymer Characterization", the descriptions of which are incorporated herein by reference). PVPVI copolymers typically have a molar ratio of N-vinylimidazole to N-vinylpyrrolldone from 1: 1 to 0.2: 1, preferably from 0.8: 1 to 0.3: 1, most preferably from 0.6: 1 to 0.4: 1. These copolymers can be either linear or branched. The compositions of the present invention may also employ a polyvinylpyrrolidone ("PVP") having an average molecular weight of from about 5,000 to about 400,000, preferably from about 5,000 to about 200,000, and most preferably still from about 5,000 to about 50,000. . The PVP's are known to those skilled in the field of detergents; see, for example, EP-A-262,897 and EP-A-256,696, incorporated herein by reference. The PVP-containing compositions may also contain polyethylene glycol ("PEG") having an average molecular weight of from about 500 to about 100,000, preferably from about 1,000 to about 10,000. Preferably, the ratio of PEG to PVP on a basis of ppm assorted in wash solutions is from about 2: 1 to about 50: 1, and most preferably from about 3: 1 to about 10: 1. The detergent compositions herein may also optionally contain from about 0.005% to 5% by weight of certain types of hydrophilic optical brighteners that also provide a dye transfer inhibiting action. If used, the compositions herein will preferably comprise from about 0.01% to 1% by weight of said optical brighteners. The hydrophilic optical brighteners useful in the present invention are those having the structural formula: wherein R-j is selected from anilino, N-2-bis-hydroxyethyl and NH-2-hydroxyethyl; R 2 is selected from N-2-bis-hydroxyethyl, N-2-hydroxyethyl-N-methylamino, morphino, chloro and amino; and M is a salt-forming cation such as sodium or potassium. When in the above formula, Ri is anilino, R2 is N-2-bis-hydroxyethyl and M is a cation such as sodium, the brightener is acid 4,4 ', bis [(4-anilino-6- (N-2 bis-hydroxyethyl) -s-triazin-2-yl) amino] -2,2'-stilbenedisulfonic acid and disodium salt. This particular brightener species is commercially marketed under the trade name Tinopal-UNPA-GX by Ciba-Geigy Corporation. Tinopal-UNPA-GX is the preferred hydrophilic optical brightener useful in the 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 the disodium salt of 4,4'-bis [4- anilino-6- (N-2-hydroxyethyl-N-methylamino) -s-triazin-2-yl) amino] -2,2'-stilbenedisulfonic acid. This particular brightener species is commercially marketed under the trade name Tinopal 5BM-GX by Ciba-Geigy Corporation. When in the above formula R1 is anilino, R2 is morphino and M is a cation such as sodium, the brightener is the sodium salt of 4,4'-bis [(4-anilino-6-morphino-s- triazin-2-yl) amino] 2,2'-stilbenedisulfonic acid. This particular kind of brightener is sold commercially under the trade name Tinopal AMS-GX by Ciba-Geigy Corporation.

The specific optical brightener species selected for use in the present invention provides especially effective dye transfer inhibition performance benefits when used in combination with the selected polymeric dye transfer inhibiting agents described above. The combination of said selected polymeric materials (e.g., PVNO and / or PVPVI) with said selected optical brighteners (e.g., Tinopal UNPA-GX, Tinopal 5BM-GX and / or Tinopal AMS-GX) provides inhibition of dye transfer significantly better in aqueous wash solutions than either of those two components of detergent composition when used alone. Without being limited to the theory, it is believed that such brighteners work in this way because they have high affinity for fabrics in the wash solution and therefore they deposit relatively quickly on these fabrics. The degree to which the brighteners are deposited on the fabrics in the wash solution can be defined by a parameter called "exhaustion coefficient". The depletion coefficient is in general the ratio of a) the polishing material deposited on the cloth to b) the initial polish concentration in the wash liquor. Brighteners with relatively high depletion coefficients are most suitable for inhibiting dye transfer in the context of the present invention. Other types of conventional optical brightener can optionally be used in the present compositions to provide conventional "brightness" benefits to the fabrics, rather than a true dye transfer inhibiting effect. Said use is conventional and well known for detergent formulations.

Chelating Agents The detergent compositions herein may also optionally contain one or more chelating agents, particularly chelating agents for upstart transition metals. Those commonly found in the wash water include iron and / or manganese in colloidal or water-soluble particulate form, and may be associated as oxides or hydroxides, or found in association with soils such as humic substances. The chelators that are preferred are those that effectively control said transition metals, especially including controlling the deposition of said transition metals or their compounds on fabrics and / or controlling the undesirable reduction oxide reactions in the medium. washing and / or fabric interlining or hard surfaces. Such chelating agents include those that have low molecular weights, as well as polymeric types, typically with at least one, preferably two or more heterogeneous donor atoms such as O or N, capable of coordination to a transition metal. Common chelating agents can be selected from the group consisting of aminocarboxylates, aminophosphates, polyfunctionally substituted aromatic chelating agents and mixtures thereof, all as defined below.

Aminocarboxyiates useful as optional chelating agents include ethylenediaminetetracetates, N-hydroxyethylenediaminetriacetates, nitrilotriacetates, ethylenediamonotetraproprionates, triethylenetetra-aminohexacetates, diethylenetriaminepentaacetates and ethanoldiglicines, their alkali metal, ammonium and substituted ammonium salts and mixtures thereof. The aminophosphonates are also useful for use as chelating agents in the compositions of the invention when at least low levels of total phosphorus are allowed in the detergent compositions and include ethylenediaminetetrakis (methylenephosphonates) as DEQUEST. Preferably, these aminophosphonates do not contain alkyl or alkenyl groups with more than about 6 carbon atoms. Polyfunctionally substituted aromatic chelating agents are also useful in the compositions herein. See the US patent. 3,812,044 issued May 21, 1974 to Connor et al. Preferred compounds of this type in acid form are dihydroxydisulfobenzenes such as 1,2-dihydroxy-3,5-disulfobenzene. A preferred biodegradable chelator for use herein is ethylenediamine disuccinate ("EDDS"), especially the [S, S,] isomer as described in the U.S. patent. 4,704,223 issued November 3, 1987 to Hartman and Perkins. The compositions herein may also contain water-soluble salts (or acid form) of methyl glycine diacetic acid (MGDA) as a useful chelator or co-builder with, for example, insoluble builders such as zeolites, layered silicates and the like. . If used, these chelating agents should generally comprise from about 0.001% to about 15% by weight of the detergent compositions herein. Most preferably, if used, the chelating agents should comprise from about 0.01% to about 3.0% by weight of said compositions.

Foam suppressors Compounds for reducing or suppressing foaming can be incorporated into the compositions of the present invention. The suppression of foam may be of particular importance in "high concentration cleaning procedures" such as those described in E.U. 4,489,455 and 4,489,574, and in front-loading European-style washing machines. A wide variety of materials can be used as foam suppressors, and foam suppressors are well known to those skilled in the art. See, for example, Kirk Othmer Encyclopedia of Chemical Technology, 3a. Edition, Volume 7, pages. 430-447 (John Wiley &Sons, Inc., 1979). A category of foam suppressant of particular interest includes monocarboxylic fatty acids and soluble salts thereto. See the US patent. 2,954,347, issued September 27, 1960 to Wayne St. John. The monocarboxylic fatty acids and salts thereof used as a foam suppressant typically have hydrocarbyl chains of 10 to about 24 carbon atoms, preferably 12 to 18 carbon atoms. Suitable salts include the alkali metal salts such as sodium, potassium and lithium, as well as ammonium and aanolammonium salts. Other suitable suds suppressors include high molecular weight hydrocarbons such as paraffin, fatty acid esters (e.g., fatty acid triglycerides), fatty acid esters of monovalent alcohols, aliphatic ketones of C-18-C40 (cf. gr., stearone), etc. Other foam inhibitors include N-alkylated aminotriazines and monostearyl phosphates such as monostearyl alcohol ester phosphate, monostearyl dialychal metal phosphates (eg, K, Na and Li) or other phosphate esters. Hydrocarbons such as paraffin and halogenoparaffins can be used in liquid form. Liquid hydrocarbons will be liquid at room temperature and at atmospheric pressure, and will have a pour point on the scale of about -40 ° C to about 50 ° C, and a minimum boiling point of not less than about 110 ° C. It is also known to use waxy hydrocarbons, preferably having a melting point below about 100 ° C. Hydrocarbons constitute a preferred category of foam suppressant for detergent compositions. The hydrocarbon foam suppressors are described, for example, in the US patent. No. 4,265,779. The hydrocarbons, therefore, include aliphatic, alicyclic, aromatic and heterocyclic saturated or unsaturated hydrocarbons having from about 12 to about 70 carbon atoms. Paraffins can be used, including mixtures of true paraffins and cyclic hydrocarbons. Foam suppressors may be useful, including polyorganosiloxane oils such as polyhydroxy siloxane, dispersions or emulsions of polyorganosiloxane oils or resins, and combinations of polyorganosiloxane with silica particles wherein the polyorganosiloxane is chemoabsorbed or fused onto the silica. Silicone foam suppressors are well known in the art and are described, for example, in the US patent. 4,265,779, in the European patent application No. 89307851, published on February 7, 1990 by Starch, M.S., and in E.U. 3,455,839. Mixtures of silicone and silanated silica are described, for example, in German patent application DOS 2,124,526. Silicone foam scavengers and foam controlling agents in granular detergent compositions are described in US Pat. 3,933,672 and in E.U. 4,652,392. An illustrative silicone-based foam suppressant for use herein is a foaming suppressant amount of a foaming agent consisting essentially of: (i) polydimethylsiloxane fluid having a viscosity of from about 20 cs to about 1, 500 cs at 25 ° C; (ii) from about 5 to about 50 parts per 100 parts by weight of (i) siloxane resin composed of (CH3) 3SiO- | / 2 units and S1O2 units in a ratio of about 0.6: 1 to about 1.2: 1; and (iii) from about 1 to about 20 parts per 100 parts by weight of (i) of a solid silica gel. In the preferred silicone foam suppressant used herein, the solvent for a continuous phase is made of certain polyethylene glycols or polyethylene-polypropylene glycol copolymers or mixtures thereof (preferred), or polypropylene glycol. The suppressor of primary silicone foams is branched / interlaced. Typical liquid laundry detergent compositions with optionally controlled foams will comprise from about 0.001 to about 1, preferably from about 0.01 to about 0.7, most preferably from about 0.05 to about 0.5,% by weight of said silicone foam suppressant, comprising (1) a non-aqueous emulsion of a primary foaming antiforming agent which is a mixture of (a) a polyorganosiloxane, (b) a resinous siloxane or a silicone resin-producing silicone compound, (c) a filler material finely divided and (d) a catalyst for promoting the reaction of mixture components (a), (b) and (c) to form silanolates; (2) at least one nonionic silicone surfactant; and (3) polyethylene glycol or a polyethylene-polypropylene glycol copolymer having a solubility in water at room temperature of more than about 2% by weight; and without polypropylene glycol. Similar amounts can be used in granular compositions, gels, etc. See also US patents. 4,978,471, Starch, issued December 18, 1990 and 4,983,316, Starch, issued January 8, 1991, 5,288,431, Huber et al., Issued February 22, 1994, and US patents. 4,639,489 and 4,749,740, Aizawa and others in column 1, line 46 to column 4, line 35. The silicone foam suppressant of the present preferably comprises polyethylene glycol and a copolymer of polyethylene glycol / polypropylene glycol, all having a lower average molecular weight of about 1, 000, preferably between about 100 and 800. The polyethylene glycol and polyethylene / polypropylene copolymers herein have a solubility in water at room temperature other than about 2% by weight, preferably more than about 5% by weight. The preferred solvent herein is polyethylene glycol having an average molecular weight less than about 1,000, most preferably between about 100 and 800, most preferably still between 200 and 400, and a polyethylene glycol / polypropylene glycol copolymer, preferably PPG 200 / PEG 300. A weight ratio of between about 1: 1 and 1: 10, most preferably between 1: 3 and 1: 6, of polyethylene-polypropylene glycol polyethylglycol polymer is preferred. The preferred silicone foam suppressors used herein do not contain polypropylene glycol, particularly of molecular weight of 4,000. Preferably they also do not contain block copolymers of ethylene oxide and propylene oxide, such as PLURONIC L101. Other foam suppressors useful herein contain the secondary alcohols (e.g., 2-alkylalkanols) and mixtures of said alcohols with silicone oils, such as the silicones described in E.U. 4,798,679, 4,075.1 18 and EP 150,872. The secondary alcohols include Q-C ^ Q alkyl alcohols having a C-j chain -C- | 6- A preferred alcohol is 2-butyloctanol, which is available from Condea under the trade name ISOFOL 12. Mixtures of secondary alcohols are available under the trade name ISALCHEM 123 from Enichem. Mixed foam suppressors typically comprise alcohol + silicone blends at a weight ratio of 1: 5 to 5: 1. For any detergent compositions to be used in automatic washing machines, the foams should not be formed to the extent that they overflow from the washing machine. The foam suppressors, when used, are preferably present in an amount of foam suppression. By "foam suppression amount" is meant that the formulator of the composition can select an amount of this foam controlling agent that will sufficiently control the foams to result in a low foaming laundry detergent for use in automatic washing machines. The compositions herein will generally comprise from 0% to about 10% foam suppressant. When used as suds suppressors, the monocarboxylic fatty acids, and salts thereof, will typically be present in amounts up to about 5%, preferably 0.5% to 3% by weight of the detergent composition, although higher amounts may be used. Preferably, about 0.01% to about 1% of the silicone foam suppressant is used, most preferably about 0.25% to about 0.5%. These values in percent by weight include any silica that can be used in combination with polyorganosiloxane, as well as any auxiliary materials that can be used. The monostearyl phosphate foam suppressors are generally used in amounts ranging from about 0.1% to about 2% by weight of the composition. The hydrocarbon foam suppressors are typically used in amounts ranging from about 0.01% to about 5.0%, although higher levels can be used. The alcohol foam suppressors are typically used at 0.2% -3% by weight of the finished compositions. The suds suppressor systems are also useful in automatic dishwashing (ADD) embodiments of the invention. The technology of silicone foam suppressors and other defoaming agents useful for all purposes herein are extensively documented in "Defoaming, Theory and Industrial Applications," Ed., P.R. Garret, Marcel Dekker, N.Y., 1973, ISBN 0-8247-8770-6, incorporated herein by reference. See especially the chapters entitled "Foam Control in Detergent Products" (Ferch et al.) And "Surfactant Antifoams" (Blease et al.). See also US patents 3,933,672 and 4,136,045. Highly preferred silicone foam suppressors for application in ADD include the combined types known for use in laundry detergents such as heavy duty granules, although the types used to date in liquid detergents may also be incorporated in the present compositions. hard work. For example, polydimethylsiloxanes having trimethylsilyl units or alternating end blocks such as silicone can be used. These may be combined with silica and / or with non-silicon surfactant components, such as those illustrated by a foam suppressor comprising 12% silicone / silica, 18% stearyl alcohol and 70% starch in granulated form. A suitable commercial source of the active silicone compounds is Dow Corning Corp. If it is desired to use a phosphate ester, suitable compounds are described in the US patent. No. 3,314,891, issued April 18, 1967 to Schmolka et al., Incorporated herein by reference. The alkyl phosphate esters that are preferred contain from 16-10 carbon atoms. Highly preferred alkyl phosphate esters are monostearyl acid phosphate or monooleic acid phosphate, or salts thereof, particularly alkali metal salts, or mixtures thereof. It has been found to be preferable to avoid the use of simple calcium precipitation soaps as antifoams in the ADD compositions, since they tend to be deposited on the dishes. In fact, phosphate esters are not completely exempt from such problems and the formulator will generally choose to minimize the content of potentially depositing antifoams in the use of ADD.

Alkoxylated polycarboxylates The alkoxylated polycarboxylates such as those prepared from polyacrylates are useful herein to provide additional fat removal performance. Such materials are described in WO 91/08281 and PCT 90/01815, p. 4 et seq., Incorporated herein by way of reference. Chemically, these materials comprise polyacrylates that have an ethoxy side chain for every 7-8 acrylate units. The side chains have the formula - (CH2CH2? M (CH2) nCH3 where m is 2-3 and n is 6-12. These side chains are attached by ester to the "base structure" of the polyacrylate to provide a "comb" type polymer structure. The molecular weight may vary, but is typically in the range of about 2000 to about 50,000. Said alkoxylated polycarboxylates may comprise from about 0.05% to about 10% by weight of the compositions herein.

Fabric Softeners Various fabric softeners that soften during washing, especially the impalpable smectite clays of the U.S. Patent may optionally be used. 4,062,647, Storm and Nirschi, issued December 13, 1977, as well as other softening clays known in the art, typically at levels of from about 0.5% to about 10% by weight in the compositions herein to provide softening benefits concurrently with the cleaning of fabrics. Clay-based softeners can be used in combination with amine and cationic softeners as described, for example, in the US patent. 4,375,416, Crisp et al., March 1, 1983 and in the US patent. 4,291, 071, Harris et al., Issued September 22, 1981. In addition, in the laundry washing methods of the present, known fabric softeners, including biodegradable types, can be used in pretreatment, main wash, after washing and in dryer.

Perfumes The perfumes and perfumery ingredients useful in the present compositions and methods comprise a wide variety of natural and synthetic chemical ingredients, including, but not limited to, aldehydes, ketones, esters and the like. Also included are various natural extracts and essences which may include complex mixtures of ingredients such as orange oil, lemon oil, rose extract, lavender, musk, patchouli, balsamic essence, sandalwood oil, pine oil, cedar and the like. The finished perfumes can comprise extremely complex mixtures of said ingredients. The finished products typically comprise from about 0.01% to about 2% by weight of the detergent compositions herein, and the individual perfumery ingredients can comprise from about 0.0001% to about 90% of a finished perfume composition.

Non-limiting examples of perfume ingredients useful herein include: 7-acetyl-1,2,4,4,5,6,7,8-octahydro-1,1,6,7-tetramethylnaphthalene, methyl ionone; ionone gamma methyl; methylredrilone; methyldihydrojasmonate; methyl-1,6,10-trimethyl-2,5,9-cyclododecatrien-1-yl ketone; 7-acetyl-1,1, 3,4,4,6-hexamethyltetralin; 4-acetyl-6-tert-butyl-1,1-dimethylindane; para-hydroxy-phenyl-butanone; benzophenone; methylbeta-naphthyl ketone; 6-acetyl-1,1, 2,3,3,5-hexamethylindane; 5-acetyl-3-isopropyl-1,1,6-tetramethylindane; 1-dodecanal; 4- (4-hydroxy-4-methylpentyl) -3-cyclohexen-1 -carboxaldehyde; 7-hydroxy-3,7-dimethyloctanal; 10-undecen-1 -al; iso-hexylcyclohexenylcarboxaldehyde; formyltriciclodecane; condensation products of hydroxy citronellal and methyl anthranilate; condensation products of hydroxy-citronellal and indole; condensation products of phenylacetaldehyde and indole; 2-methyl-3- (para-tert-butylphenyl) -propionaldehyde; ethylvaniiin; heliotropin; hexyl cinnamic aldehyde; amylcinnamic aldehyde; 2-methyl-2- (para-iso-propylphenyl) -priopionaldehyde; coumarin; decalactone gamma; Cyclopentadecanolide; 16-hydroxy-9-hexadecenoic acid lactone; 1, 3,4,6,7,8-hexahydro-4,6,6,7,8,8-hexamethylcyclopenta-gamma-2-benzopyran; methyl ether of beta-naphthol; ambroxane; dodecahydro-3a, 6,6,9a-tetramethylnaphtho [2,1 b] furan; cedrol; 5- (2,2,3-trimethylcyclopent-3-enyl) -3-methylpentan-2-ol; 2-ethyl-4- (2,2,3-trimethy1-3-cyclopenten-1-yl) -2-buten-1-ol; caryophyllene alcohol; tricyclodecenyl propionate; tricyclodecenyl acetate; benzyl salicylate; Caryl acetate and para- (tert-butyl) cyclohexyl acetate.

Particularly preferred are those perfume materials that provide the greatest improvements in odor to the finished compositions containing cellulases. These perfumes include, but are not limited to: hexyl cinnamic aldehyde; 2-methyl-3- (para-tert-butylphenyl) -propionaldehyde; 7-acetyl-1, 2,3,4,5,6,7,8-octahydro-1,1,6,7-tetramethylnaphthalene; benzyl salicylate; 7-acetyl-1,1, 3,4,4,6-hexamethyltetralin; para- (tert-butyl) cyclohexyl acetate; methyldihydrojasmonate; methyl ether of beta-naphthol; methylbeta-naphthyl ketone; 2-methyl-2- (para-iso-propylphenyl) -priopionaldehyde; 1, 3,4,6,7,8-hexahydro-4,6,6,7,8,8-hexamethylcyclopenta-gamma-2-benzopyran; dodecahydro-3a, 6,6,9a-tetramethylnaphtho [2,1 b] furan; anisaldehyde; coumarin; cedrol; vanillin; Cyclopentadecanolide; tricyclodecenyl acetate and tricyclodecenyl propionate. Other perfume materials include essential oils, resinoids and resins from a variety of sources including, but not limited to: Peruvian balm, frankincense resis, stirax, lavender resin, nutmeg, acasia oil, benzoin resin, corianda and bleach Other perfume chemicals include phenethyl alcohol, terpineol, linalool, linalyl acetate, geraniol, nerol, 2- (1,1-dimethylethyl) -cyclohexanol acetate, benzyl acetate and eugenol. Carriers such as diethyl phthalate can be used in the finished perfume compositions.

Material Care Agents The present compositions, when designed for automatic dishwashing, may contain one or more material care agents that are effective as corrosion inhibitors and / or rust-aids. Said materials are preferred components of automatic dishwashing compositions, especially in certain European countries where the use of electroplated nickel silver and sterling silver are still comparatively common in household kitchenware, or when aluminum protection be a concern and the composition have a low silicate content. In general, said material care agents include metasilicate, silicate, bismuth salts, manganese salts, paraffin, triazoies, pyrazoles, thiols, mercaptans, aluminum fatty acid salts and mixtures thereof. When present, said protective materials are preferably incorporated at low levels, for example, from about 0.01% to about 5% of the ADD composition. Suitable corrosion inhibitors include paraffin oil, typically a predominantly branched aliphatic hydrocarbon having a number of carbon atoms in the range of about 20 to about 50; the paraffin oil that is preferred is selected from predominantly branched C25-45 species with a cyclic to non-cyclic hydrocarbon ratio of about 32:68. A paraffin oil that satisfies these characteristics is sold by Wintershall, Salzbergen, Germany, under the trade name WINOG 70. In addition, the addition of low levels of bismuth nitrate (ie, Bi (NO 3) 3) is also preferred. Other corrosion inhibiting compounds include benzotriazole and comparable compounds; mercaptans or thiols including thiophthol and thioanthranol; and finally divided aluminum fatty acid salts such as aluminum tristearate. The formulator will recognize that such materials can generally be used judiciously and in limited amounts to avoid any tendency to produce stains or films on glassware or compromise the bleaching action of the compositions. For this reason, mercaptan corrosion inhibitors that are quite reactive in bleach and common fatty carboxylic acids that precipitate with calcium in particular are preferably avoided.

Other ingredients A wide variety of other functional ingredients useful in detergent compositions can be included in the compositions herein, including other active ingredients, vehicles, hydrotropes, processing aids, dyes or pigments, solvents for liquid formulations, solid fillers for stick compositions, etc. If high foam formation is desired, foams such as C10-C16 alkanolamides can typically be incorporated into the foam-promoting compositions typically at levels of 1% -10%. The monoethanol and diethanolamides of C-jQ-C-14 illustrate a typical class of such foam boosters. It is also advantageous to use other suds promoters with high sudsing surfactants, such as the amine oxides, betaines and sultaines indicated above. If desired, soluble magnesium salts such as MgCl 2, MgS 4, and the like, can be added, typically, at levels of 0.1% -2%, to provide additional suds and enhance the fat removal capacity. Various detersive ingredients employed in the present invention can optionally be further stabilized, by absorbing said ingredients on a porous hydrophobic substrate, then coating said substrate with a hydrophobic coating. Preferably, a detersive ingredient is mixed with a surfactant before it is absorbed into the porous substrate. In use, the detersive ingredient is released from the substrate into the aqueous wash bath, where it performs its desired detersive function. To illustrate this technique in more detail, a porous hydrophobic silica (trademark SIPERNAT D10, Degussa) is mixed with a proteolytic enzyme solution containing 3% -5% non-ionic ethoxylated alcohol surfactant of C- | 3_- | 5 (EO 7). Typically, the enzyme / surfactant solution is 2.5X the weight of the silica. The resulting powder is dispersed by stirring the silicone oil (various viscosities of silicone oil in the range of 500-12,500 can be used). The resulting dispersion of silicone oil is emulsified or otherwise added to the final detergent matrix. By this means, it is possible to "protect" ingredients such as those mentioned above, enzymes, bleaches, bleach activators, bleach catalysts, photoactivators, dyes, fluorescence formers, fabric conditioners and hydrolyzable surfactants, for use in detergents, including liquid detergent compositions for clothes. The liquid detergent compositions may contain water and other solvents as carriers. Suitable primary or secondary alcohols of low molecular weight are exemplified by methanol, ethanol, propanol and isopropanol. Monohydric alcohols are preferred as a solubilizing surfactant, but polyols such as those containing from 2 to about 6 carbon atoms and from 2 to about 6 hydroxy groups (e.g., 1,3-propanediol, ethylene glycol, glycerin and 1,2-propanediol). The compositions may contain from 5% to 90%, typically from 10% to 50% of such vehicles. The compositions herein will be formulated preferably such that, during use in aqueous cleaning operations, the wash water has a pH of between about 6.5 and about 1 1, preferably between about 7.0 and 10.5, most preferably between about from 7.0 to about 9.5. Liquid formulations of the automatic dishwashing product preferably have a pH of between about 6.8 and about 9.0. Wash products typically have a pH of 9-11. Techniques for controlling pH at recommended levels of use include the use of pH, alkali, acid regulators, etc., and are well known to those skilled in the art.

Form of the compositions The cleaning compositions according to the invention can have a variety of physical forms, including granulated, tablet, bar and liquid forms. The compositions include so-called concentrated granular detergent compositions adapted to be added to a washing machine by means of a supply device placed in the tub of the washing machine with the load of laundry. The average particle size of the components of the granulated compositions according to the invention should preferably be such that no more than 5% of the particles measure more than 1.7 mm in diameter, and that no more than 5% of the particles measure less than 0.15 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) in a series of Tyler sieves. The fractions of weight obtained in this way are plotted against the opening size of the sieves. The average particle size is then taken as the size of the opening through which 50% of the sample would pass. Certain preferred granular detergent compositions in accordance with the present invention are high density type, now common in the market; they typically have an overall density of at least 600 g / liter, most preferably from 650 g / liter to 1200 g / liter.

Agglomerated Surfactant Particles One of the preferred methods for providing surfactant binders in consumer products is to make agglomerated particles of surfactant, which may be in the form of flakes, pellets, discs, noodles, tapes, but preferably have the form of granules. One preferred form for processing the particles is by agglomerating powders (e.g., aluminosilicate, carbonate) with highly active surfactant pastes and controlling the particle size of the resulting agglomerates within specific limits. Said process includes mixing an effective amount of powder with a highly active surfactant paste in one or more agglomerators such as a container agglomerator, a Z-shaped paddle mixer or most preferably an in-line mixer such as those manufactured by Schugi (The Netherlands). ) BV, 29 Chroomstraat 8211 AS, Leyland, The Netherlands, and Gebruder Lddige Maschinebau GmbH, D-4790 Paderbom 1, Elsenerstrasse 7-9, Postfach 2050, Germany. Most preferably a high shear mixer is used, such as a CB Lódige (trade name). A highly active surfactant paste comprising from 50 wt% to 95 wt%, preferably 70 wt% to 85 wt% of surfactant is typically used. The paste can be pumped into the agglomerator at a temperature high enough to maintain a pumpable viscosity, but low enough to prevent degradation of the anionic surfactants used. A pulp operating temperature of 50 ° C to 80 ° C is typical.

Laundry Washing Method The laundry washing methods of the present invention typically comprise treating the laundry with an aqueous washing solution in a washing machine having dissolved or supplied therein an effective amount of a laundry detergent composition in accordance with the present invention. with the invention For an effective amount of the detergent composition is meant from 40g to 300g of product dissolved or dispersed in a washing solution of a volume of 5 to 65 liters, which are typical doses of product and in volumes of washing solution commonly used in conventional laundry washing methods. As noted, the surfactants are used herein in detergent compositions, preferably in combination with other detersive surfactants, at levels that are effective to achieve at least a directional improvement in cleaning performance. In the context of a composition for washing fabrics, said "levels of use" may vary depending not only on the type and severity of the soils and stains, but also on the temperature of the washing water, the volume of the washing water and the type of washing machine. For example, in a vertical-axis, front-loading, automatic American type washing machine that uses approximately 45 to 83 liters of water in the wash bath, a wash cycle of approximately 10 to approximately 14 minutes, and a wash water temperature from about 10 ° C to about 50 ° C, it is preferred to include from about 2 ppm to about 625 ppm, preferably from about 2 ppm to about 550 ppm, most preferably from about 10 ppm to about 235 ppm, of the surfactant in the liquid of washing. Based on usage rates of about 50 ml to about 150 ml per wash load, this results in a product (weight) concentration of the surfactant of from about 0.1% to about 40%, preferably about 0.1% to about 35%. %, most preferably around 0.5% to about 15%, for a heavy-duty liquid laundry detergent. Based on usage rates from about 30 g to about 950 g per wash load, for dense ("compact") laundry compositions (density above about 650 g / l) this results in a concentration in product (weight ) of the surfactant from about 0.1% to about 50%, preferably about 0.1% to about 35%, most preferably about 0.5% to about 15%. Based on usage rates of approximately 80 g to approximately 100 g per load for spray-dried granules (ie, "fluffs"); density below about 650 g / l), this results in a product (weight) concentration of the branched primary alkyl surfactant in the middle region of its chain from about 0.07% to about 35%, preferably about 0.07 to about 25%, most preferably about 0.35% to about 1%. For example, in a European horizontal-axis, front-loading automatic washing machine that uses approximately 8 to 15 liters of water in the wash bath, a wash cycle of approximately 10 to approximately 60 minutes, and a wash water temperature from about 30 ° C to about 95 ° C, it is preferred to include from about 3 ppm to about 14,000 ppm, preferably from about 3 ppm to about 10,000 ppm, most preferably from about 15 ppm to about 4200 ppm, of the surfactant in the liquid of washing. Based on usage rates of about 45 ml to about 270 ml per wash load, this results in a product (weight) concentration of the surfactant from about 0.1% to about 50%, preferably about 0.1% to about 35%, most preferably around 0.5% to about 15%, for a heavy duty liquid laundry detergent. Based on usage rates of about 40 g to about 210 g per wash load, for dense ("compact") laundry compositions (density above about 650 g / l) this results in a concentration in product (weight ) of the surfactant from about 0.12% to about 53%, preferably about 0.12% to about 46%, most preferably about 0.6% to about 20%. Based on usage rates of approximately 140 g to approximately 400 g per load for spray-dried granules (ie, "foamed", density below approximately 650 g / l), this results in a concentration in product (weight) of the surfactant from about 0.03% to about 34%, preferably about 0.03% to about 24%, most preferably about 0.15% to about 10%. For example, in a vertical-load, top-loading Japanese type automatic washing machine that uses approximately 26 to 52 liters of water in the wash bath, a wash cycle of about 8 to about 15 minutes and a wash water temperature from about 5 ° C to about 25 ° C, it is preferred to include from about 0.67 ppm to about 270 ppm, preferably from about 0.67 ppm to about 236 ppm, most preferably from about 3.4 ppm to about 100 ppm, of the surfactant in the liquid of washing. Based on usage rates of about 20 ml to about 30 ml per wash load, this results in a product (weight) concentration of the surfactant of from about 0.1% to about 40%, preferably about 0.1% to about 35%. %, most preferably around 0.5% to about 15%, for a heavy-duty liquid laundry detergent. Based on usage rates of about 18 g to about 35 g per wash load, for dense ("compact") laundry compositions (density above about 650 g / l) this results in a concentration in product (weight ) of the surfactant from about 0.1% to about 50%, preferably about 0.1% to about 35%, most preferably about 0.5% to about 15%. Based on usage rates of approximately 30 g to approximately 40 g per load for spray-dried granules (ie, "foamed", density below approximately 650 g / l), this results in a concentration in product (weight) of the surfactant from about 0.06% to about 44%, preferably about 0.06% to about 30%, most preferably around 0.3% to about 13%. As can be seen from the above, the amount of surfactant used in a machine washing context can vary, depending on the habits and practices of the user, the type of washing machine and the like. In a preferred use aspect, a supply device is used in the washing method. The delivery device is loaded with the detergent product, and is used to introduce the product directly into the drum of the washing machine. Its volume capacity must be such that it can contain sufficient detergent product as would normally be used in the washing method. Once the washing machine has been loaded with clothes, the delivery device containing the detergent product is placed inside the tub. At the beginning of the wash cycle of the washing machine, water is introduced into the tub and it rotates periodically. The design of the delivery device should be such as to allow the dry detergent product to be contained but to allow the release of this product during the wash cycle in response to its agitation while the tub is spinning and also as a result of its contact with the water washed. To allow the release of the detergent product during washing, the device may possess a number of openings through which the product can pass. Alternatively, the device can be made of a material that is liquid permeable but impermeable to the solid product, which will allow the release of the dissolved product. Preferably, the detergent product will be released rapidly at the start of the wash cycle, thereby providing high localized and transient concentrations of product in the drum of the washing machine at this stage of the wash cycle. Preferred delivery devices are reusable and designed in such a way that the integrity of the container is maintained both in the dry state and during the wash cycle. Especially preferred delivery devices for use in accordance with 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, p. 41-46, also discloses especially preferred supply devices for use with granular detergent products which are of a type commonly known as the "granulette". Another preferred delivery device for use in accordance with the invention is described in PCT patent application No. WO94 / 1 1562. Especially preferred delivery devices are described in European patent applications Application Nos. 0343069 and 0343070 This latter application describes a device comprising a flexible liner in the form of a bag extending from a support ring defining a hole, the orifice being adapted to admit sufficient product into the bag for a washing cycle in a process of washed. A portion of the washing medium flows through the orifice into the bag, dissolves the product and the solution then passes down through the orifice into the washing medium. The support ring is provided with a masking arrangement to prevent the exit of the moistened and undissolved product, this arrangement typically comprising radial walls extending from a protrusion in a spoke wheel configuration or similar structure, in which the walls They have a helical shape. Alternatively, the delivery device may be a flexible container, such as a bag or sack. The bag may have a fibrous structure coated with a waterproof protective material to thereby retain the contents, such as that described in published European Patent Application No. 0018678. Alternatively, the bag may be formed of a water-insoluble synthetic polymeric material provided with an edge seal or closure designed to break in the aqueous medium as described in published European patent applications Nos: 0011500, 0011501, 0011502 and 0011968. Convenient form of waterproof closure comprises a water soluble adhesive disposed along and sealing one end of a bag formed of a waterproof polymeric film such as polyethylene or polypropylene.

Automatic dishwashing method Any method suitable for machine washing or cleaning tableware, particularly dirty silverware, is envisioned. A preferred automatic dishwashing method comprises treating selected dirty items of earthenware, glassware, hollow articles, silverware and cutlery and mixtures thereof, with an aqueous liquid having dissolved or supplied therein an effective amount of a composition for washing dishes in a machine according to the invention. For an effective amount of the machine dishwashing composition, it is tried to say from 8 g to 60 g of product dissolved or dispersed in a washing solution with a volume of 3 to 10 liters, which are typical product doses and volumes of washing solution commonly used in conventional automatic dishwashing methods.

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

Compositions and Methods to Assist in Rinsing The present invention also relates to compositions useful in the rinsing cycle of an automatic dishwashing process, said compositions being commonly called "rinsing aids". Although the compositions described hereinabove may also be formulated for use as rinse aid compositions, it is not required for the purposes of use as a rinse aid having a source of hydrogen peroxide present in said compositions (although a source of hydrogen peroxide, at least two levels to at least supplement the rinse). The optional inclusion of a source of hydrogen peroxide in an auxiliary rinse composition is possible in view of the fact that a significant level of residual detergent composition is brought from the wash cycle to the rinse cycle. Thus, when an ADD composition containing a source of hydrogen peroxide is used, the source of hydrogen peroxide for the rinse cycle is taken out of the wash cycle. The catalytic activity provided by the catalyst is thus effective with its supply from the wash cycle. In this manner, the present invention further encompasses automatic dishwashing rinse aid compositions comprising: (a) an effective amount of a bleach activator and / or organic percarboxylic acid, (b) a catalytically effective amount of a catalyst as the one described in this and (c) detergent auxiliary materials for automatic dishwashing. Preferred compositions comprise a low foaming nonionic surfactant. These compositions are also preferably in liquid or solid form. The present invention also encompasses methods for washing tableware in a domestic automatic dishwashing appliance, said method comprising treating the dirty tableware during a washing cycle of an automatic dishwashing machine with an alkaline aqueous bath comprising a source of hydrogen peroxide, followed by treatment of the tabletop article in the subsequent rinse cycle with an aqueous bath comprising a catalyst as described herein.

In the following examples, the abbreviations of the different ingredients used in the compositions have the following meanings: LAS: C-12 linear sodium alkylbenzene sulfonate C45AS: C14-C-15 linear sodium alkyl sulfate CxyEzS: C-] xC- | branched sodium alkyl sulphate and condensed with z moles of ethylene oxide CxyEz: A branched primary alcohol of C-? xC-iy condensed with z moles of ethylene oxide QAS: R2.N + (CH3) 2 (C2H4? H) with R2 = C12-C14 TFAA: Cis-Ci alkyl N-methylglucamide STPP: Tripolyphosphate sodium anhydrate Zeolite A: Hydrated sodium aluminosilicate of the formula Na-j2 (A102Si? 2) 2- 27H2O, which has a primary particle size in the range of 0.1 to 10 microns. NaSKS-6: Crystalline layered silicate of the formula d-Na2Si2? 5 Carbonate: Anhydrous sodium carbonate with an average particle size of 200μm and 900μm Bicarbonate: Anhydrous sodium bicarbonate with a particle size distribution between 400μm and 1200μm Silicate: Amorphous sodium silicate (ratio 2.0; Si? 2: Na2? ) Sodium sulfate: Anhydrous sodium sulfate Citrate: Trisodium citrate dihydrate of 86.4% activity with a particle size distribution of between 425μm and 850μm MA / AA: 1: 4 copolymer of maleic acid / acrylic acid with an average molecular weight of approximately 70,000 CMC: Sodium carboxymethylcellulose Protease: Proteolytic enzyme of activity 4KNPU / g commercialized by Novo Industries AS under the trade name of Savinase Cellulase: Cellulite enzyme of activity 1000CEVU / g marketed by Novo Industries AS under the trade name of Carezyme Amylase: Amylolytic enzyme of 60KNU / g activity marketed by Novo Industries A / S under the trade name of Termamyl 60T Lipase: Lipolytic activity enzyme 100kLU / g marketed by Novo Industries A / S under the trade name of Lipolase PB4: Sodium perborate anhydrous tetrahydrate of nominal formula NaBO2.3H2O.H2O2 PB1: Anhydrous sodium perborate bleach monohydrate of nominal formula NaB? 2-H2? 2 Percarbonate: Sodium percarbonate of nominal formula 2Na2C? 3.3H2? 2 NaDCC: Sodium dichloroisocyanurate NOBS: Nonanoyloxybenzenesulfonate in the form of sodium salt TAED: Tetraacetylethylenediamine DTPMP: Diethylenetriaminepenta (methylenephosphonate), marketed by Monsanto under the trade name Dequest 2060.

Photoactivated bleach: Sulfonated zinc phthalocyanine encapsulated in soluble polymer in dextrin bleach 1: 4,4'-bis (2-sulphotrisyl) biphenyl disodium brightener 2: 4,4'-bis (4-anilino-6-morpholino-1) brightener Disodium .3.5-triazin-2-yl) amino) stilbene-2: 2'-disulfonate HEDP: 1, 1-hydroxydanediphosphonic acid SRP 1: Blocked end esters with oxyethyleneoxy and terephthaloyl base structure Silicon Anti-foam: Foam controller of polydimethylsiloxane with a siloxane-oxyalkylene copolymer as a dispersing agent with a ratio of said foam controller to said dispersing agent of 10: 1 to 100: 1. DTPA: Diethylethiaminepentaacetic acid In the following examples, all levels are cited in% by weight of the composition. The following examples are illustrative of the present invention, but are not intended to limit or otherwise define its scope. All parts, percentages and ratios used herein are expressed as a percentage by weight, unless otherwise specified.

EXAMPLE 1 The following laundry detergent compositions A-F were prepared as follows: Where the amounts are parts by weight, for example kg or ppm. (1) It is the catalyst of any of the above syntheses, for example, of Synthesis Example 1; (2) It is a commercial detergent granule, for example, TIDE or ARIEL that does not have bleach or transition metal catalyst and another conventional detergent powder, for example one of improved detergency with sodium carbonate and / or zeolite A or P; (3) It is perborate of monohydrate or sodium perborate tetrahydrate or sodium percarbonate; (4) It is tetraacetylethylenediamine or any equivalent polyacetylethylenediamine, such as a non-symmetrical derivative; (5) Is any hydrophobic bleach activator having a chain length in the indicated range, for example, NOBS (C9) or an activator that produces NAPAA in perhydrolysis (C9); (6) It is a commercial phosphonate chelator, for example, DTPA, or one of the DEQUEST series, or it is sodium salts of S, S-ethylenediamine disuccinate. The compositions are used to wash soiled fabrics in American, European and Japanese automatic washers at water hardnesses in the range of 0-3.42 g / l and temperatures in the cold scale (ambient) to about 90 ° C, very typically an ambient temperature of approximately 60 ° C. The tabulated quantities can be read in any unit of convenient weight, for example kilograms for formulation purposes or, for a single wash, parts per million in the washing liquid. The pH of the wash solution is in the general scale of about 8 to about 10, depending on the use of the product by washing and the levels of soiling. Excellent results are obtained in several dirty items (nine replicates per spot), such as t-shirts stained with grass, tea, wine, grape juice, meat sauce, beta-carotene or carrot. Evaluations are done by five trained panelists, by a group of approximately 60 consumers or by the use of an instrument such as a spectrometer.

EXAMPLE 2 Laundry detergent compositions G-M are in accordance with the invention: The compositions are used for the textile washer as in the previous examples. In addition, the compositions including, for example, the formulation, G can be used to soak and wash fabrics by hand with excellent results.

EXAMPLE 3 The following granular detergent compositions for laundry A-G according to the invention are prepared: The compositions are used to wash textiles as in the previous examples.

EXAMPLE 4 The following detergent formulations are in accordance with the present invention: Mn (Bicyclamate) CI2 according to synthesis example 1 or synthesis examples 2-7.

EXAMPLE 5 The following high density detergent formulations are in accordance with the invention: * The bleach catalyst is Mn (Bciclama) CI2 according to synthesis example 1 above; Benefits are also observable for compositions containing bleach catalysts according to synthesis examples 2-7.

EXAMPLE 6 A non-limiting example of a non-aqueous laundry liquid detergent, which contains bleach and has the composition as shown in Table 1, is prepared.

TABLE I Component% by weight Scale (% by weight) Liquid phase Linear C12 Na alkylbenzene sulfonate (LAS) 25.3 18-35 Ethoxylated alcohol E05 of C-12-C14 13.6 10-20 Hexylene glycol 27.3 20-30 Perfume 0.4 0-1.0 Solids Protease enzyme 0.4 0-10 Na3 citrate, anhydrous 4.3 3-6 Bleach catalyst * Sodium percborate 3.4 2-7 Sodium nonanoyloxybenzene sulfonate (NOBS) 8.0 2-12 Sodium carbonate 13.9 5-20 Diethylenetriaminepentaacetic acid (DTPA) 0.9 0-1.5 Brightener 0.4 0-0.6 Foam suppressor 0.1 0-0.3 Minor components The rest * The bleach catalyst is Mn (Bciclama) CI2 according to the synthesis example 1 above; Benefits are also observable for compositions containing bleach catalysts according to synthesis examples 2-7. The resulting composition is a heavy-duty, stable, anhydrous laundry detergent liquid that provides excellent stain and dirt removal performance when used in normal laundry operations.

EXAMPLE 7 % by weight of active material INGREDIENTS AB STPP (anhydrous) 1 31 26 Sodium carbonate 22 32 Silicate (ratio 2, hydrated) 9 7 Surfactant (non-ionic, for example, BASF's Plurafac) 3 1.5 Bleach catalyst2 0.01 0.1 Sodium perborate 12 10 TAED - 1.5 Savinase (pellet) - 0.2 Termamyl (pellet) 0.5 Sulfate 25 25 Perfume / c. minors up to 100% up to 100% 1 Sodium Triprolyphosphate 2 The bleaching catalyst is Mn (Bciclama) Cl2 according to synthesis example 1 above; Benefits are also observable for compositions containing bleach catalysts according to synthesis examples 2-7.

EXAMPLE 8 In the following example there is provided an automatic dishwashing compilation which illustrates the combination of the transition metal bleach catalyst according to any of the synthesis examples 1-7 with an inorganic peracid, sodium monopersulfate. % by weight of active material INGREDIENTS A B STPP (anhydrous) 1 31 26 Sodium carbonate 22 32 OXONE 10 monopersulfate Surfactant (non-ionic, for example, Plurafac from BASF) 3 1.5 Bleach catalyst2 0.01 0.1 Sodium perborate 12 1 TAED - 1.5 Savinase (pellet) - 0.2 Termamyl (pellet) 0.5 Sulfate 25 .25 Perfume / c. minor up to 100% up to 100% 1Tipoiiphosphate of sodium EXAMPLE 9 Transition metal catalyst according to synthesis example 1 and magnesium monoperoxyphthalate hexahydrate (0.05% / 10%) is added to a product for manual washing of soaking / washing clothes in other conventional manner.

EXAMPLE 10 Transition metal catalyst is added according to Synthesis Example 1 in the form of an aqueous solution diluted inside a chamber of a double chamber liquid supply bottle. A dilute solution of peracetic acid established in the second compartment is added. The bottle is used to supply a mixture of catalyst and peracetic acid as an additive in a washing operation in another conventional manner in which no other bleach is present.

EXAMPLE 11 Transition metal catalyst according to Synthesis Example 1 to pH 8 is used in combination with a low foaming nonionic surfactant (Plurafac LF404), sodium carbonate, an anionic polymeric dispersant (sodium polyacrylate, p.m. 4,000) and peracetic acid in a low pH cleaner for glass and plastics. The cleaner can be used in institutional as well as domestic contexts.

EXAMPLE 12 A multi-compartment water-soluble plastic film bag having a plurality of separate sealable zones is added with the following components: A. Non-ionic surfactant and dye A (liquid or waxy phase) B. Transition metal bleach catalyst Example 1, premixed with trisodium citrate as a driving promoter diluent C. Perfume D. Polisher E. Sodium perborate monohydrate F. 2,2-Oxydisuccinate, sodium salt + sodium polyacrylate and dye B G. NOBS / SS-premix EDDS 1: 0.5 and C-dye H. Pro-perfume enzymatically hydrolysable (ester or acetal) (which produces "explosion" superior to the end of the wash) I. Fabric care polymer J. Protease enzyme / amylase Ingredient levels can vary but include conventional amounts for Japanese washing conditions. The product is used in a Japanese automatic clothes washer that operates at room temperature at approximately 40 degrees C to wash fabrics, offering pleasure during use, combined with surprising results of bleaching, cleaning and fabric care. The product is preferably pre-dissolved in hot water before being added to the washing apparatus if desired.

EXAMPLE 13 Dithiocyanate manganese (II) Synthesis of 5,8 dimethyl-1, 5, 8, 12-tetraazabiciclori0.3.2.heptadecano Synthesis of 1, 5,9-, 13-TetraazatetracicloF11.2.2.2 Iheptadecano 1, 4,8,12-tetraazacyclopentadecane (4.00 g, 18.7 mmol) is suspended in acetonitrile (30 mL) under nitrogen and glyoxal is added thereto. (3.00 g, 40% aqueous, 20.7 mmoles). The resulting mixture is heated at 65 ° C for 2 hours. The acetonitrile is removed under reduced pressure. Distilled water (5 mL) is added and the product is extracted with chloroform (5x40 mL).

After drying over anhydrous sodium sulfate and filtering, the solvent is removed under reduced pressure. The product is then subjected to chromatography on neutral alumina (15 x 2.5 cm) using chloroform / methanol (97.5: 2.5 which increases to 95: 5). The solvent is removed under reduced pressure and the resulting oil is dried under vacuum, overnight. Yield: 3.80 g, i (87%).

Synthesis of 1, 13-dimethyl-1, 13-diazonia-5.9-diazatetraciclop 1,2.2.25 9 Iheptadecane 1, 5,9,13-tetraazatetracyclo [1 1 .2.2.25-9] heptadecane (5.50 g, 23.3 mmol) is dissolved in acetonitrile (180 mL) under nitrogen. Iodomethane (21.75 mL, 349.5 mmol) is added and the reaction is stirred at room temperature for 10 days. The solution is rotoevaporated to a dark brown oil. The oil is taken up in absolute ethanol (100 mL) and this solution is refluxed for 1 hour. During that time, a tan solid is formed which is separated from the mother liquor by vacuum filtration using Whatman # 1 filter paper. The solid is dried under vacuum, overnight. Yield: 1.79 g, M, (15%). Fab Mass Spec. TG / G, MeOH) M + 266 mu, 60%, Ml + 393 mu, 25%.

Synthesis of 5,8-dimethyl-1, 5,8.12-tetraazabicyclo.10.3,21heptadecane To a stirred solution of I], (1.78 g, 3.40 mmol) in ethanol (100 mL, 95%) is added sodium borohydride (3.78 g, 0.100 mmol). The reaction is stirred under nitrogen at room temperature for 4 days. 10% hydrochloric acid is slowly added until the pH is 1-2 to decompose unreacted NaBH4. Then ethanol (70 mL) is added. The solvent is removed by rotoevaporation under reduced pressure. The product is dissolved in aqueous KOH (125 mL, 20%), resulting in a pH 14 solution. The product is then extracted with benzene (5 x 60 mL) and the combined organic layers are dried over anhydrous sodium sulfate. After filtering, the solvent is removed under reduced pressure. The residue is suspended in crushed KOH and then distilled at 97 ° C at a pressure of ~ 1 mm. Yield: 0.42 g, M 47%. Mass Spec. (D-CI / NH3 / CH2CI2) MH +, 269 mu, 100%.

Synthesis of dithiocyanate manganese (II) 5.8-dimethyl-1, 5,8,12- tetraazabiciclof10.3.21heptadecane Ligand Mj, (0.200 g, 0.750 mmol) is dissolved in acetonitrile (4.0 mL) and added to the dichloride manganese (II) -dipyridine (0.213 g, 0.75 mmol). The reaction is stirred for 4 hours at room temperature to produce a pale gold solution. The solvent is removed under reduced pressure. Sodium thiocyanate (0.162 g, 2.00 mmol) dissolved in methanol (4 mL) is then added. The reaction is heated for 15 minutes. Then, the reaction solution is filtered through celite and allowed to evaporate. The resulting crystals are washed with ethanol and dried under vacuum. Yield: 0.125 g, 38%. This solid contains NaCl to re-crystallize in acetonitrile to yield 0.11 g of an off-white solid. Theoretical analysis of elements:% C, 46.45,% H, 7.34,% N, 19.13. Found:% C, 45.70,% H, 7.10,% N, 19.00.

Claims (9)

NOVELTY OF THE INVENTION CLAIMS

1 .- A composition for laundry or cleaning that includes: (a) an effective amount, preferably from 0.0001% to 99.9%, very typically from 0.1% to 25%, of a bleach activator and / or organic percarboxylic acid; (b) a catalytically effective amount, preferably from 1 ppb to 99.9%, of a transition metal bleach catalyst which is a complex of a transition metal and a macropolycyclic cross-bridge ligand; and (c) the remainder, 100%, of one or more auxiliary laundry or cleaning materials preferably comprising an oxygenated bleaching agent.

2. A laundry or cleaning composition comprising: (a) an effective amount, preferably from 0.0001% to 99.9%, very typically from 0.1% to 25%, of a bleach activator and / or organic percarboxylic acid; (b) a catalytically effective amount, preferably 1% to 49%, of a transition metal bleach catalyst, said catalyst comprising a complex of a transition metal and a cross-bridge macropolycyclic ligand, wherein (1) said transition metal is selected from the group consisting of Mn (ll), Mn (lll), Mn (IV), Mn (V), Fe (ll), Fe (lll), Fe (IV), Co (l), Co (ll), Co (lll), Ni (l), Ni (ll), Ni (lll), Cu (l), Cu (ll), Cu (lll), Cr (ll), Cr (lll), Cr (lV), Cr (V), Cr (VI), V (lll), V (IV), V (V), Mo (IV), Mo (V), Mo (VI), W (IV), W (V), W (VI), Pd (ll), Ru (ll), Ru (lll) and Ru (IV), preferably Mn (ll), Mn (lll), Mn (IV), Fe (ll) , Fe (lll), Fe (IV), Cr (ll), Cr (lll), Cr (IV), Cr (V) and Cr (VI); (2) said cross-bridge macropoicyclic ligand being coordinated by four or five donor atoms to the same transition metal and comprises: (i) an organic macrocyclic ring containing four or more donor atoms (preferably at least 3, most preferably at least minus 4, of these donor atoms are N) separated from each other by covalent bonds of 2 or 3 non-donor atoms, two to five (preferably three to four, most preferably four) of these donor atoms being coordinated with the same metal atom transition in the complex; (ii) a cross-bridge chain, which covalently connects at least 2 non-adjacent donor atoms of the organic macrocyclic ring, said non-adjacent covalently connected donor atoms are bridgehead donor atoms that are coordinated with the same transition metal in the complex, and wherein said cross-bridge chain comprises from 2 to 10 atoms (preferably the cross-linked chain is selected from 2, 3 or 4 non-donor atoms, and 4-6 non-donor atoms with an additional donor atom); and (iii) optionally, one or more non-macropolyclic ligands preferably selected from the group consisting of H20, ROH, NR3, RCN, OH ", OOH", RS ", RO", RCOO ", OCN", SCN ", N3" , CN ", F, Cl", Br-, I ", 02", N03", N02", S042", S032", P043", organic phosphates, organic phosphonates, organic sulfates, organic sulfonates, and aromatic N-donors as pyridines, pyrazines, pyrazoles, imidazoles, benzimidazoles, pyrimidines, triazoles and thiazoles with R being H, optionally optionally substituted alkyl, optionally substituted aryl, and (c) at least 0.1% of one or more auxiliary laundry or cleaning materials, preferably comprising an oxygenated bleaching agent

3. The composition according to any of claims 1 or 2, further characterized in that said bleach activator is a hydrophobic bleach activator, preferably sodium nonanoiioxybenzenesulfonate, or a hydrophilic bleach activator such like N, N, N ', N'-tetraacetylethylenediamine.

4. A laundry or cleaning composition comprising: (a) an effective amount, preferably from 0.0001% to 99.9%, very typically from 0.1% to 25%, of a bleach activator and / or organic percarboxylic acid; (b) a catalytically effective amount, preferably from 1 ppb to 49% of a transition metal bleach catalyst, said catalyst comprises a complex of a transition metal and a macropolycyclic cross bridge ligand, wherein: (1) said transition metal is selected from the group consisting of Mn (ll), Mn (lll), Mn (IV) , Mn (V), Fe (ll), Fe (lll), Fe (IV), Co (l), Co (ll), Co (lll), Ni (I), Ni (ll), Ni (lll) , Cu (l), Cu (ll), Cu (lll), Cr (ll), Cr (lll), Cr (IV), Cr (V), Cr (VI), V (lll), V (IV) , V (V), Mo (IV), Mo (V), Mo (VI), W (IV), W (V), W (VI), Pd (ll), Ru (ll), Ru (lll) , and Ru (IV) and; (2) said macropolyicylic cross-bridge ligand is selected from the group consisting of: (i) the rigid macropolycyclic ligand of formula (I) having denticity of 4 or 5: (i); (ii) the macropolycyclic cross-bridge ligand of formula (II) having denticity of 5 or 6: (ii); (iii) the cross-linked macropolycyclic ligand of formula (III) having denticity of 6 or 7: (N i); wherein in these formulas: each "E" is the portion (CRn) aX- (CRn) a ', wherein X is selected from the group consisting of O, S, NR and P, or a covalent bond, and preferably X is a covalent bond and for each E the sum of a + a 'is independently selected from 1 to 5, most preferably 2 and 3; each "G" is the portion (CRn) b; each "R" is independently selected from H, alkyl, alkenyl, alkynyl, aryl, alkylaryl, alkylaryl, and heteroaryl, or one or more R are covalently linked to form an aromatic, heteroaromatic, cycloalkyl, or heterocycloalkyl ring; each "D" is a donor atom independently selected from the group consisting of N, O, S, and P, and at least two D atoms are donor bridgehead atoms coordinated with the transition metal; "B" is a carbon atom or "D" donor atom or a cycloalkyl or heterocyclic ring; each "n" is an independently selected integer of 1 and 2, completing the valence of the carbon atoms to which the R portions are covalently bound; each "n" 'is an integer independently selected from 0 and 1, completing the valence of donor atoms D to which the R portions are covalently bound; each "n" "is an integer independently selected from 0, 1, and 2 by completing the valence of the B atoms to which the R portions are covalently bound, each" a "and" a "'being an independently selected integer of 0 -5, preferably a + a 'is equal to 2 or 3, where the sum of all "a" plus "a"' in the ligand of formula (I) is within the range of 8 to 12, the sum of all "a" plus "a" 'in the ligand of formula (II) is within the scale of 10 to 15, and the sum of all "a" plus "a"' in the formula ligand (lll) is within the range of 12 to 18, each "b" is an integer independently selected from 0-9, preferably 0-5, or in any of the above formulas, one or more of the portions (CRn) b covalently linked from any atom D to B are absent as long as at least two (CRn) b covalently bind two of the donor atoms D to atom B in the formula, and the sum of all "b" s is found within 1 to 5; and (iii) optionally, one or more non-macropolyclic ligands, preferably selected from the group consisting of H20, ROH, NR3, RCN, OH 'OOH ", RS", RO ", RCOO", OCN ", SCN", N3", CN", F, CI ", Br", I ", 02", N03", N02", SO42". S032", PO43", organic phosphates, organic phosphonates, organic sulfates, organic sulfonates and N-donors aromatics such as pyridines, pyrazines, pyrazoles, midazoles, benzimidazoles, pyrimidines, triazoles and thiazoles, R being H, optionally substituted alkyl, optionally substituted aryl, and (c) at least 0.1% of one or more auxiliary laundry materials or

5. The compositions according to any of claims 1-4, comprising a bleach activator selected from the group consisting of cationic bleach activators, preferably cationic bleach activators, quaternary carbamate type. , carbonate cuate rnario, quaternary ester and quaternary amide, ester phenol sulfonate of alkanoyl amino acids, acyl phenols sulfonates, acylalkyl phenols sulfonates, acyloxybenzenesulfonates and bleach activators having the formulas: and RC (0) -L, wherein R is an alkyl, aryl or arylalkyl portion of saturated or unsaturated C2-C- | 8, R1 is alkyl, aryl, or alkaryl containing from 1 to 14 carbon atoms, R and R1 are especially 8 to 12 carbon atoms, R2 is alkylene, arylene or alkarylene containing 1 to 14 carbon atoms, R5 is H, or an alkyl, aryl, or alkary containing 1 to 10 carbon atoms , and L is a leaving group preferably selected from the group consisting of: and mixtures thereof, wherein R1 is a linear or branched alkyl, aryl or alkaryl group containing from 1 to 14 carbon atoms, R3 is an alkyl chain containing from 1 to 8 carbon atoms, R4 is H or R3, and Y is H or a solubilizing group, wherein the preferred preferred solubilizing groups are selected from the group consisting of -S03"M +, -C02" M +, -S04"M +, -N + (R) 4X "and 0 < -N (R3) 2, most preferably -S03"M + and -C02" M + wherein R3 is an alkyl chain containing from 1 to 4 carbon atoms, M is a stable cation in bleach and X is a stable anion in bleach, and bleach activators that have the formulas: wherein R6 is H, alkyl, aryl, alkoxyaryl, an alkaryl group containing 1 to 12 carbon atoms, or substituted phenyl containing from 6 to 18 carbons.

6. The compositions according to any of claims 1-5, comprising a bleach activator selected from the group consisting of ethyl-4-sulfofenii carbonate of 2- (N, N, N-trimethyl ammonium); N-octyl chloride, N, N-dimethyl-N 10-carbofenoxidecilamor._o; 3- (N, N, N-trimethylammonium) propylsodium 4-sulfophenylcarboxylate, N, N, N-trimethylammonium toluyloxybenzenesulfonate, N, N, N ', N'-tetraacetylethylenediamine, sodium nonanoyloxybenzenesulfonate, sodium 4-benzyloxybenzenesulfonate; Sodium 1-methyl-2-benzyloxybenzenesulfonate; Sodium 4-methyl-3-benzyloxybenzoate; trimethylammonium toluoxybenzenesulfonate, sodium 3,5,5-trimethylhexanoyloxybenzenesulfonate, (6-octanamidocaproyl) oxybenzenesulfonate, (6-nonanamidocaproyl) oxybenzenesulfonate, (6-decanamidocaproyl) oxybenzenesulfonate, and mixtures thereof.

7. The compositions according to any of claims 1-6, comprising an organic percarboxylic acid selected from the group consisting of magnesium monoperoxyphthalate hexahydrate; m-chloroperbenzoic acid, 4-nonylamino-4-oxoperoxybutyric acid, 6-nonylamino-6-oxoperoxycaproic acid, peroxybenzoic acid and substituted ring peroxybenzoic acids, preferably peroxy-alpha-naphthoic acid; aliphatic, substituted aliphatic and arylalkyl monoperoxy acids, preferably peroxylauric acid, peroxystearic acid, N, N-phthaloylaminoperoxycaproic acid, 6-octylamino-6-oxo-peroxyhexanoic acid, paracetic acid, phthaloimidoperoxycaproic acid and arylimido substituted derivatives and acyloxynitrogen, acid 1,2-diperoxydodecanoic acid, 1,9-diperoxyazelaic acid, diperoxybrassyl acid, diperoxysebacic acid, diperoxyisophthalic acid, 2-decyldiperoxybutane-1,4-dioic acid, 4,4'-sulphonylbisperoxybenzoic acid and salts thereof.

8. A laundry and cleaning composition comprising: (a) an effective amount, preferably from 1 ppm to 9

9.9%, very typically from 0.1% to 25%, of a bleach activator; (b) a catalytically effective amount, preferably from 1 ppb to 99.9%, very typically from 0.001 ppm to 49%, preferably from 0.05 ppm to 500 ppm, of a transition metal bleach catalyst, said catalyst comprising a molar complex 1: 1 of a catalytic manganese metal is selected from the group consisting of Mn (ll), Mn (lll), Mn (IV), and a tetradentate cross-bridge macropolycyclic ligand having the formula: wherein in this formula "R1" is independently selected from H, and linear or branched, substituted or unsubstituted C1-C20 aicyn, alkenyl or alkynyl and all the nitrogen atoms in the macropolycyclic rings are coordinated with the transition metal and optionally one or more non-macropolyclic ligands; and (c) the remainder, at 100%, preferably at least 0.1%, of one or more laundry and cleaning auxiliary materials comprising an oxygenated bleaching agent, preferably selected from the group consisting of hydrogen peroxide, perborate and percarbonate.