MXPA96004672A - Whitening compositions that understand blasting agents and deblanq catalysts - Google Patents

Abstract

The present invention relates to bleaching and cleaning compositions comprising a bleaching compound, one or more bleach activators and a bleach catalyst. Thus, laundry detergent compositions and automatic dishwashing compositions comprising perborate, percarbonate and activators such as benzoyl caprolactam, exhibit improved stain removal performance in the presence of the white catalyst.

Description

WHITENING COMPOSITIONS THAT COMPRISE WHITENING ACTIVATORS AND WHITENING CATALYSTS TECHNICAL FIELD The present invention relates to cleaning and bleaching compositions employing manganese complexes to increase the yield. Compositions of . lanqueo, wash of fabrics, automatic washing of tableware and sanitary compositions with activity of bleaching of improved oxygen.

BACKGROUND OF THE INVENTION It is a common practice for formulators of cleaning compositions to include bleaching agents such as 'as sodium perborate or sodium percarbonate in said compositions for its bleaching effect. These bleaches are widely recognized for their ability to remove various stains and dirt from fabrics. Similarly, the formulators for automatic dishwashing compositions have discovered that various bleaching agents can aid in the removal of tea stains, proteinaceous soils and the like, from the dishes. Various bleaching and / or pre-bleaching compositions also comprise percarbonate or perborate bleach. Sanitizers for bathrooms, drainages and / -similar may also comprise several bleaches. Unfortunately, many bleaching agents do not work optimally under all conditions of use. As a general proposition, perborate and percarbonate bleaches are more effective in hot water than in cold water. In fact, many consumers now drive the washing of fabrics and other cleaning operations under moderate water temperatures tending to cold. To improve the performance of perborate and percarbonate bleach, manufacturers have returned to so-called "bleach activators". Such activators typically comprise organic molecules that interact with perborate or percarbonate to release "per-acid" bleaching species. The combination of bleach-plus-activator functions act well on a large scale of water temperatures and conditions of use. It is also known that many transition metal cations, such as manganese, have the potential to function as bleach activators or catalysts, presumably by virtue of their catalytic interaction with peroxide bleaching or per-acid species. Unfortunately, many transition metals react so easily with the percompounds that very rapidly destroy the bleaching species under conventional cleaning conditions. Attempts to catalyze and improve bleaching with manganese cations have been especially problematic, since That, if done improperly, the deposition of unsightly brown spots of M 2 on the surface that is being bleached may occur. Several manganese bleach catalysts have been suggested. U.S. Patent 4,430,243, Bragg teaches bleach catalysis using various chelators and a mixture of manganese cations and non-catalytic metal cations. The catalysis of manganese gluconate is described in E.U.A. 4,728,455. Said bleaches of the prior art have not had commercial acceptance. More recently, a series of manganese bleach catalysts having quite complex ligands have been reported (mentions below). It has now been discovered that compositions comprising N-acyl lactam activators or amido derivative derivatives in combination with bleach catalysts, especially metal bleach catalysts, can be used to provide effective and improved bleaching. Accordingly, it is an object of the present invention to provide improved cleaning and bleaching compositions using bleach activators and bleach catalysts. It is another object of the present to provide means for removing dirt and stains from fabrics and tableware using the catalyzed bleaching systems of this invention. These and other objectives are ensured herein, as will be evident from the following descriptions.

TECHNICAL BACKGROUND The use of amido-derived bleach activators in laundry detergents is described in the US patent. No. 4,534,551. Another class of bleach activators consists of activators of the benzoxazine type described by Hodge et al. In the U.S. patent. No. 4,955,723, issued October 30, 1990. The use of manganese with various complex ligands to improve bleaching is reported in the following U.S. Patents: 4,430,243; 4,728,455; 5,246,621; 5,244,594; 5,284,944; 5,194,416; 5,246,612; 5,256,779; 5,280,117; 5,274,147 :; 5,153,161; 5,227,084; 5,114,606; 5,114,611. See also; EP 549,271 Al; EP 544,490; To the; EP 54,272 Al; and EP 544,440 A2.

BRIEF DESCRIPTION OF THE INVENTION The present invention encompasses bleaching compositions, comprising a bleaching agent, especially a bleach which is a member selected from the group consisting of H2O2, perborate, percarbonate, persulfate and per-acid bleach, one or more selected bleach activators, and a catalytically effective amount of one or more bleach catalysts, especially metal bleach catalysts. Preferred compositions comprise a percarbonate or perborate blender, or mixtures thereof, and a bleach activator selected from activators of the acrylatelactam type, amido derivative activators, benzoaxin type activators and mixtures thereof. Additionally, the bleaching compositions of this invention may further comprise a second bleach or peracid activator selected from tetraacetylethylenediamine (TAED), nonanoyloxybenzene sulfonate (NOBS) and magnesium onoperoxyphthalate. Preferred bleach activators are selected from the following: a) an amido bleach activator derived from the general formula: ## STR4 ## Or mixtures thereof, wherein R * is an alkyl, aryl or alkaryl group containing from 1 to 14 carbon atoms, R 2 is an alkylene or alkylene group containing from 1 to 14 carbon atoms, R 5 is H or an alkyl, aryl or alkaryl group containing from 1 to 10 carbon atoms and L is a residual group; b) benzoxazine bleach activators of the general formula: wherein Ri is H, alkyl, alkaryl, aryl, arylalkyl, and wherein R 2, R 3, R *, and Rs can be the same or different substituents selected from H, halogen, alkyl, alkenyl, aryl, hydroxyl, alkoxy, amino, alkylamino, COORß (where Re is H or an alkyl group) and carbonyl functions; and c) N-acyl lactam bleach activators of the formula: wherein n is from 0 to 8, preferably from 0 to 2, and R6 is H, an alkyl, aryl, alkoxyaryl or alkaryl group containing from 1 to 12 carbons, or a substituted phenyl group containing from 1 to 12 carbon atoms; to 18 carbon atoms (see co-pending applications 08 / 064,562 and 08 / 082,270.); and d) mixtures of a), b) and c). Preferably, the molar ratio of the relaxed hydrogen peroxide to the peroxygen bleaching compound • The bleach activator is greater than approximately 1.0. More preferably, the molar ratio of the hydrogen peroxide to the bleach activator is at least about 1.5. Preferred bleach activators of type a) are those in which R1 is an alkyl group containing from 6 to 12 carbon atoms, R2 contains from 1 to 8 carbon atoms, and RS is H or methyl. Particularly preferred bleach activators are those of the above general formulas, wherein R * is an alkyl group containing from 7 to 10 carbon atoms and R2 contains from 4 to 5 carbon atoms. Preferred bleach activators of type b) are those wherein R2, Ra, R * and Rs are H and Ri is a phenyl group. Preferred acyl portions of said N-acyl lactam bleach activators of type c) have the formula R * -C0- wherein Rβ is H, an alkyl, aryl, alkoxyala or alloyl group containing from 1 to up 12 carbons, or a substituted phenyl group containing from 6 to 18 carbons. In highly preferred embodiments, R6 is a member selected from the group consisting of phenyl, heptyl, octii, nonyl, 2,4,4, -tpmet? Lfen? L and substituted and substituted quinine, and mixtures of the miarns.

Highly preferred aActivators include benzoyl -caprolactane, nonanoyl caprolactan, benzoyl valerolact ma, nonanoyl valerolactam, 3,5,5-tprnethylhexane, caprolactam, 3,5,5-tmetmethexane, valerolactarn, octanoyl caprolactane, octane Ll valerolactam, decano.l caprolactam, decanoyl valerolactam, undecenoyl caprolactam, undecenoyl valerolactam, (6-octanamidocaproi) oxybenzenesulphonate, (6-nonanarnidocaproiDoxibencensulphonate, (6-decanarnidocaproyl) -oxibenzenesulfonate, and mixtures thereof Examples of highly preferred substituted benzoylactans include rnethylbenzoyl caprolactam, rnetilbenzoil valerolactam, ethylbenzoyl caprolactam, ethylbenzoyl valerolactam, propilbenzoil caprolactam, propilbenzoil valerolactam, isopropylbenzoyl caprolactam, isopropyl valerolactam, butylbenzoyl caprolactam, butylbenzoyl valerolactam, tert-butylbenzoyl caprolactam, tert-butylbenzoyl valerolactarna, pentiibenzoil caprolactam, pentilbenzoil valerolactam, caprolactam hexylbenzoyl, hexylbenzoyl valerolactam, ethoxy benzoyl caprolactam, ethoxybenzoyl valerolactam, propoxybenzoyl caprolactam, propoxybenzoyl valerolactam, isopropoxybenzoyl caprolactarna, isopropoxybenzoyl valerolactam, butoxybenzoyl caprolactam, butoxybenzoyl valerolactam, tert-butoxybenzoyl caprolactam, butoxybenzoyl valerolactam tert-, pentoxibenzoil caprolactam, valerolatana pentoxibenzoil, caprolactarna hexoxibenzoil, hexoxibenzoil valerolactam, 2,4, 6-trichlorobenzole caprolactarna, 2, 6-tpclorobenzo l valerolactarna, caprolactarna pentafluorobenzoyl, pentafluorobenzoyl valerolactam, dichlorobenzoyl caprolactam, caprolactarna dirnetoxibenzo.il, 4chlorobenzoyl caprolactam, 2,4-dichlorobenzoyl caprolactarna, terephthaloyl dicaprolactama, pentafluorobenzoyl caprolactam, pentafluorobenzoilvalerolactama, dichlorobenzoyl valero.lactama, di ethoxybenzoyl valerolactam, 4chlorobenzoyl valerolactam, 2, 4-dichlorobenzoyl valerolactam, terephthaloyl divalerolactam, 4-nitrobenzoyl caprolactam, 4-nitrobenzoyl valerolactar, dinitrobenzoyl caprolactam, dinitrobenzoyl valerolactam, and mixtures thereof. Particularly preferred are bleach activators selected from the group consisting of benzoyl caprolactam, bezoyl valerolactam, nonanoyl caprolactam, nonanoyl valerolactam, 4-nitrobenzoyl caprolactane, 4-nitrobenzoyl valerolactam, octanoyl caprolactam, octanoyl valerolactam, decanoyl caprolactam, decanoyl valerolactam, undecanoyl caprolactam , undecanoil valerolactarna, 3,5,5-trirnethylhexanoyl caprolactam, 3,5,5-tr.imethylhexanoyl valerolactarna, dinitrobenzoyl caprolactam, dinitrobenzoyl valerolactam, terephthalaloyl dicaprolactam, terephthaloyl diva.Ierolactam (6-octanamidocaproyl) oxybenzenesulfonate, (6-nonane idocaprol) oxybenzenesulfonate, (6-decanamido-caproyl) oxybenzenesulfonate, and mixtures thereof. Preferred compositions herein are those in which the bleach catalyst is a metal base catalyst.

The invention also encompasses detergent compositions, especially laundry detergents, which further comprise conventional surfactants and other detersive and bleaching ingredients, and a catalytically effective amount of a bleach catalyst. Again, in such compositions the bleach preferably comprises a member selected from the group consisting of percarbonate, perborate and mixtures thereof with bleach activators, especially bleach activators selected from N-acyl caprolactates, N-acyl valerolactants, activators of benzoxazino type, amido derivatives derivatives and mixtures thereof. The invention also encompasses detergent or bleach compositions comprising a bleach, a bleach activator and a catalytically effective amount of a water soluble manganese salt. The invention also encompasses a method for improving the bleaching performance of oxygen bleaching or per-acid compositions, comprising adding thereto a catalytically effective amount of manganese cations in the presence of selected ligands. This provides a method for removing fabric stains, comprising contacting said fabrics with an aqueous medium comprising said compositions. The bleach catalyst is used in a catalytically effective amount in the compositions and processes of the --orient. The term "catalytically effective amount" means an amount that is sufficient, under any comparative test condition that is employed, to enrich the bleaching and removal of the stain or spots of interest of the sample substrate. Thus, in a fabric washing operation, the substrate shown will typically be a stained fabric with, for example, several food stains. For automatic dishwashing, the sample substrate may be, for example, a porcelain teacup or dish, or a polyethylene dish soaked with tomato soup. The test conditions will vary, depending on the type of washing application used and the user's habits. Thus, front-load laundry washing machines of the type employed in Europe, generally use less water and more detergent concentrations higher than those used by top-loading machines of the E.U.A. Some machines have significantly longer wash cycles than others. Some users choose to use very hot water; others use warm or even cold water in fabric washing operations. Of course, the catalytic performance of the bleach catalyst will be affected by such considerations, and the levels of bleach catalyst used in wholly formulated bleach and detergent compositions can be adjusted appropriately. As a practical matter and not by way of limitation, the compositions and processes herein may be adjusted to provide in the order of at least one - aOrte for 10 million species of active bleach catalyst in the aqueous washing liquid, and preferably will provide from 0.1 ppm to 700 ppm, more preferably, from 1 ppm to 500 ppn, of the catalyst species in the liquid laundry To illustrate this point more broadly, the order of 3 micrornolar manganese catalyst is effective at 40 ° C, pH 10 under European conditions, using perborate and a bleach activator (for example, benzoyl caprolactam). A concentration increase of 3 to 5 times may be required under conditions of E.U.A. to achieve the same results. Conversely, the use of a bleach activator and manganese catalyst with perborate may allow the formulator to achieve equivalent bleaching, at lower levels of use of perborate, than products without the manganese catalyst. All percentages, ratios and proportions herein are by weight, unless otherwise specified. All the documents cited are, in part relevant, incorporated herein by reference.

DETAILED DESCRIPTION OF THE INVENTION BLEACH CATALYST The bleach catalyst material used herein may comprise the acid free form, the salts, and the like.

One type of bleach catalyst is a catalyst system comprising a heavy metal cation of defined bleach catalytic activity, such as copper, iron, or manganese cations, an auxiliary metal cation having little or no catalytic activity, such as the z nc and aluminum cations, and a sequesterant having stability constants defined by the catalytic and auxiliary metal cations, particularly ethylend to intetraacetic acid, ethylenediarin-tetrahydne-lensphonic acid) and water-soluble salts thereof. Said catalysts are described in the patent of E.U.A. No. 4,430,243. Other types of bleach catalysts include the manganese-based complexes described in the U.S.A. No. 5,245,621 and in the patent of E.U.A. No. 5,244,594. Preferred examples of these catalysts include Mnlv2 (u-0) 3 (l; 4,7-tr? Met l-l, 4,7-tpazac? Clononane) 2- (PF6) 2, nHi2 (? -0)? (u-0Ac) 2 (1,4,7-tpmet? ll, 4,7-tr? azac? clononane) 2 (CIO4) 2, Mnivi (uO)? (1,4,7-tr? azac? clononane (CIO;, Mn * 11 Mniv «(u-0)? (U-OAc) 2- (l / 4,7-tper? Ll, 4,7-tr? Azac? Chonanone) 2 (CIO.;) 3, and mixtures thereof Others are described in European Patent Application Publication No. 549,272. Other ligands suitable for use herein include 1,5,9-tnrnet? I-1, 5, 9 -tnazac? clododecane, 2-met? ll, 4, 7-tnazac? clononane, 2-rnet? l-1, 4, 7-tr? azac? clononane, 1, 2,4, 7-tretramet? l 1, 4,7-tzazacyclononane and mixtures thereof The bleach catalysts useful for - Dishwashing machine compositions and concentrated powder detergent compositions can also be selected as appropriate for the present invention. For examples of such suitable bleach catalysts see U.S. Pat. No. 4,246,612 and US patent. No. 5,227,084. See also the patent of E.U.A. No. 5,194,416 which teaches mononuclear (IV) manganese complexes such as Nniv (1, 4,7-trimethyl-1, 4,7-triazacyclononane) (OCH 3) 3 (PFß). Still another type of bleaching catalyst, such as that described in the patent of E.U.A. No. 5,114,606, is a manganese complex soluble in water (II), (III), and / or (IV) with a ligand that is a non-carboxylated polyhydroxy compound having at least three consecutive groups of C-OH. Preferred igandos include sorbitol, iditol, dulsitol, anitol, xylitol, arabitol, adonitol, eso-erythritol, rneso-inositol, lactose, and mixtures thereof. The patent of E.U.A. No. 5,114,611 teaches a bleach catalyst comprising a complex of transition metals, including Mn, Co, Fe or Cu, with a noncyclic cyclic ligand. Said ligands are of the formula: R2 R3 R1-N = c-B-C = N ~ R4 wherein R1, R2, R3 and R? can each be selected from H, substituted alkyl and aryl groups so that each R? -N = C- - R2 and form a ring of five or six members. Said ring can be subsequently replaced. B is a bridging group selected from 0, S. CR5, R6, NR7 and C = 0, wherein R5, R6, and R7, each may be H, alkyl, or aryl groups, including substituted or unsubstituted groups. Preferred ligands include pyridine, pyridazine, pyrirnidine, pyrazine, imidazole, pyrazole, and triazole rings.

Optionally, said rings can be substituted with substituents such as alkyl, aryl, alkoxy, halide and nitro. Particularly preferred is the 2,2'-bispyridyl ina ligand. Preferred bleach catalysts include Co, Cu, Mn, Fe, -bispyridimethane and -bispyridylane complexes. Highly preferred catalysts include CI2 Co (2,2'-bispydylamine), Di (isothiocinate) bispiri and laminácobalto (II), trisdipyridylane-cobalt (II) perchlorate, Co (2,2'-bispyridylamine) 2? 2C10 « , Bis (2-2 '~ bispirdylamine) copper (II) perchlorate, tris (di-2-pyridylamine) iron (II) perchlorate and mixtures thereof. Other examples include Mn gluconate, Mn (CF3S? 3_) 2, Co (NH3) sCl, and the binuclear Mn co-folded with ligands of tetra-N-dentate and bi-N-dentate, including N4MN1 n (u-0) 2_ nivN_D + y CBi? Y2 iu (u-0) 2Mni bipi23- (CIO4) 3. The bleach catalysts of the present invention can also be prepared by combining a water soluble ligand with a water soluble manganese salt in an aqueous medium, and concentrating the resulting mixture by - evaporation. Any convenient water-soluble manganese salt can be used herein. Manganese (II), (III), (IV) and / or (V) is readily available on a commercial scale. In some instances, sufficient manganese may be present in the wash liquid, but, in general, it is preferred to add Mn cations in the compositions to ensure their presence in catalytically effective amounts. Thus, the sodium salt of the ligand and a member selected from the group consisting of MnS? _, N (C104) 2 or MnCl2 (less preferred) are dissolved in water at molar ratios of ligand: salt of Mn on the scale of about 1: 4 to 4: 1 at a neutral or slightly alkaline pH. The water can be first deoxygenated by boiling it, and cooled by rolling it with nitrogen. The resulting solution is evaporated (under N2, if desired) and the resulting solids are used in the detergent and bleach compositions herein without any further purification. In an alternate phase, the source of water-soluble manganese, such as MnSO $, is added to the bleach / cleaner composition or to the bleached / cleansing aqueous solution comprising the ligand. Some type of complex is apparently formed in situ, and an improved bleaching performance is ensured. In said in situ process, it is convenient to use a considerable molar excess of the ligand over the manganese, and mol ratios of ligand: Mn are typically 3: 1 to 15: 1. The additional ligand also serves to sweep- vague metal ions such as iron and copper, thus protecting the bleach from decomposition. Such a possible system is described in the European patent application, publication No. 549,271. Although the structures of the manganese bleach catalyst complexes of the present invention have not been clarified, it can be speculated that these comprise chelators or other hydrated coordination complexes resulting from the interaction of the carboxyl and nitrogen atoms of the ligand with the cation of manganese. Likewise, the oxidation state of the manganese cation during the catalytic process is not known with certainty, and it can be the valence state of (+11), (+ III) or (+ V). Due to the possible 6 fixation points of the ligand with the manganese cation it can be reasonably speculated that multinuclear species and / or "framework" structures may exist in the aqueous bleach medium. Whichever form of the active Mn-ligand species actually exists, it functions in an apparently catalytic manner to provide improved bleaching performance in difficult spots such as tea, ketchup, coffee, blood and the like. Other bleach catalysts are described, for example, in European Patent Application Publication No. 408,131 (Cobalt Complex Catalysts), European Patent Applications Nos. 384,503 and 306,089 (metallo-porfrin catalysts), E.U.A. 4,728,455 (catalyst - anganese / multidentate ligand), E.U.A. 4,711,748 and European patent application publication No. 224,952 (manganese absorbed in aluminosilicate catalyst), E.U.A. 4,601,845 (support of aluminum silicate with manganese and zinc or magnesium salt), E.U.A. 4,626,373 (manganese / ligand catalyst), E.U.A. 4,119,557 (ferric complex catalyst), German patent specification 2,054,019 (cobalt chelator catalyst), Canadian 866,191 (transition salts containing metals), E.U.A. 4,430,243 (chelators with manganese cations and non-catalytic metal cations), and E.U.A. 4,728,455 (manganese gluconate catalysts).

WHITENING COMPOUNDS AND WHITENING AGENTS It should be appreciated that the bleaching catalyst does not function as a bleach itself. Preferably, it is used as a catalyst to improve the performance of conventional bleaches and, in particular, oxygen bleaches such as perborate, percarbonate, persulfate and the like, especially in the presence of bleach activators. Accordingly, the compositions herein also contain bleaching agents or bleaching mixtures containing a bleaching agent and one or more bleach activators, in an amount sufficient to provide bleaching of the stain or spots of interest. Bleaching agents - typically will be at levels of from almost 1% to up to 80%, more typically from 5% to up to 20%, of the composition of detergents, especially for fabric washing. The bleach and pre-soaking compositions may comprise from 5% to 99% of the bleaching agent. If present, the amount of bleach activators will typically be from 0.1% to up to 60%, more typically from 0.5% to up to 40% of the bleaching mixture comprising the bleaching agent plus the bleach activator. The bleaching agents used herein may be any of the bleaching agents useful for detergent compositions in washing textiles, cleaning hard surfaces, and other cleaning purposes that are now known or have become known. These include oxygen bleaches, as well as other bleaching agents. Perborate whiteners, for example, sodium perborate (e.g., mono or tetrahydrate) may be used herein. Peroxygen bleaching agents are preferably used in the compositions. Suitable peroxygen bleach compounds include sodium carbonate peroxyhydrate, and equivalent "percarbonate" bleaches, sodium pyrophosphate peroxyhydrate, urea peroxyhydrate, and sodium peroxide. Persulfate bleach (for example OXONE, commercially manufactured by DuPont) can also be used.

A preferred percarbonate bleach comprises dry particles having an average particle size in the range from 500 microns to 1,000 microns, not more than 10%, the weight of said particles being less than 200 microns and not more than 10%. by weight of said particles being larger than up to 1250 microns. Optionally, the percarbonate can be coated with silicate, borate or water soluble surfactants. Percarbonate is available from several commercial sources such as FMA, Solvay and To ai Denka. The compositions of the present invention also comprise mixtures of bleach activators. Peroxygen bleaching agents, perborates, percarbonates, etc., are preferably combined with bleach activators, which lead to production in situ in the aqueous solution (eg, during the washing process) of the peroxyacid corresponding to the bleach activator.

AMIDO DERIVED WHITENING ACTIVATORS Bleach activators of the type a) used in the present invention are substituted amide compounds of the general formulas 0 0 0 0 R1-C-N-R2-C-L, R1-N-C-R2-C-L R IS RIS - or mixtures thereof, wherein R *, R2 and RS are co or defined above and L may be essentially any residual group. A residual group is any group that is displaced from the bleach activator as a consequence of the nucleophilic attack in the bleach activator by the perihydroxide anion. This, the perhydrolysis reaction, results in the formation of peroxycarboxylic acid. Generally, for a group to be a suitable residual group, it has to exert an electron-attracting effect. It must also form a stable entity so that the speed of the counter-reaction is negligible. This facilitates the nucleophilic attack by the perhydroxide anion. The group L must be sufficiently reactive for the reaction to occur within the optimum time period (for example, a wash cycle). However, if L is very reactive, this activator will be difficult to stabilize for use in a bleaching composition. These characteristics are generally parallelised by the pKa of the conjugate acid of the residual group, although exceptions to this convention are known. Ordinarily, the residual groups exhibiting said behavior are those in which their conjugated acid has a pKa on the scale of from about 4 to 13, preferably from 6 to 11 and more preferably from 8 to 11. The activators Preferred bleaching agents are those of the aforementioned general formula, wherein R *, R2, and R5 are -corno are defined by the peroxyacid and L is selected from the group consisting of: and mix it, aryl or alkaryl, containing from 1 to 14 carbon atoms, R3 is an alkyl chain containing from 1 to 8 carbon atoms, R * is H or R3 and Y is H or a solubilizing group. The preferred solubilizing groups are -S? 3-M +, -S0 «-M +, -N + (R3 x- and 0 <-N (R3) 3 and more preferably -S? 3" + and -C? 2 ~ M + wherein R3 is an alkyl chain containing from 1 to 4 carbon atoms, M is a cation that provides solubility to the bleach activator and X is an anion that provides • '-solubility to the bleach activator. Preferably, M is an alkali metal, ammonium or an ammonium cation substituted with sodium and potassium being more preferred, and X is a halide, hydroxide, methylsulfate or acetate anion. It should be noted that bleach activators with a residual group that does not contain solubilizing groups can be well dispersed in the bleaching solution to assist in their dissolution. Preferred bleach activators are those of the general formula described above wherein L is selected from the group consisting of: wherein R3 is as previously defined and Y is -S? 3_ M + o - C? 2"M + where M is as defined above.Warned examples of bleach activators of the above formula incl. octanarnido- cap roi D ox i benzenesul fonate, (6-nonanarnidocarbon) oxbenzene sulphonate, (6- decanamidocaproi) oxybenzenesulphonate, and mixtures thereof Another important class of bleach activators, including those of the type b) and type c), provide per organic acids such as those described herein by opening rings as a consequence of the attack -nucleophilic in the carbonylcarbon of the cyclic ring by the perhydroxide anion. For example, this ring-opening reaction in activators of type c) leads to the lactose ring carbonyl by the hydrogen peroxide or its anion. Since the attack of an acylactam by hydrogen peroxide or its anion occurs preferably in the hexocyclic carbonyl, obtaining a significant fraction of the ring opening may require a catalyst. Another example of ring opening bleaching activators can be found in activators type b) such as those described in the patent of E.U.A.

No. 4,966,723 Hodge et al., Issued October 30, 1990. Said activating compounds described by Hodge include activators of the benzoxazine type, which have the formula including the benzoxazinae substituted of the type where Ri is H, alkyl, alkaryl, aryl, arylalkyl, and where -2, R =. / R * and Rs may be the same or different substituents selected from H, halogen, alkyl, alkenyl, aryl, hydroxyl, alkoxy, amino, alkylamino, COORß (where Re is H or an alkyl group) and carbonyl functions.

A preferred activator of the benzoxazine type is: When the activators are used, optimum performance in the bleaching of the surface with washing solutions wherein the pH of said solution is between about 8.5 and 10.5 and preferably between 9.5 and 10.5 in order to facilitate the perhydrolysis reaction is obtained. Such a pH can be obtained with commonly known substances as pH regulating agents, which are optional components of the bleaching systems herein. Also > another class of preferred bleach activators include acylactane activators, especially acyl caprolactam ace and acyl valerolactamae of the formulas: wherein Rβ is H, an alkyl, aryl, alkoxyaryl, or alkaryl group containing from 1 to 12 carbon atoms, or a substituted phenyl group containing from 6 to 18 carbons. See also applications of E.U.A. copending 08 / 064,562 and 08 / 082,270, which describe substituted benzollactams. See also Patent of E.U.A. No. 4,545,784 issued to Sanderson, October 8, 1985, incorporated herein by reference, which discloses acyl caprolactates, including benzoyl caprolactam, absorbed in a sodium perborate. Additional bleach activators several non-limiting examples of additional activators which may optionally comprise the bleaching compositions described herein including those in the U.S. Patent. No. 4,915,854, issued April 10, 1990 to Mao et al, and the U.S. Patent. No. 4,412,934. Activators of nonanoyloxybenzene fonate (NOBS) and tetraacetyl ethylene diamine (TAED) are typical, and mixtures thereof may also be used. See also E.U.A. No. 4,634,551 for other typical bleaches and activators that may be used herein. Bleaching agents Another optional and more preferable category of bleaching agent that can be used without restriction, encompasses percarboxylic acid bleaching agents and you come out of them. Suitable examples of this class of agents include magnesium hexahydrate onoperoxi phthalate (INTEROX), the magnesium salt of metachloroperbenzoic acid, 4-non larn non-4-oxoperox? But? R? Co and diperoxydodecanedioic acid. Said bleaching agents are described in the patent of E.U.A. 4,483,781, Hartrnan, issued November 20, 1984, U.S. Patent Application. 740,446, Burns et al, filed June 3, 1985, European Patent Application No. 0,133,354, Banks eta al, published February 20, 1985, and Patent of E.U.A. No. 4,412,934, Chung et al, issued November 1, 1983. Highly preferred bleaching agents also include 6-nomla acid? No-6-oxoperoxicapro? Co as described in U.S.A. Patent No. 4,634,551, issued January 6, 1987 to Burns et al. The present invention may also optionally comprise bleaching compositions comprising an effective amount of a substantially soluble organic peroxyacid having the general formula. "- wherein R, R2, and Rs are as defined for type a of the aforementioned bleach activator.The superior cleaning / bleaching action of the present compositions is also preferably achieved safely at rubber machine parts. natural and other natural rubber articles, including fabrics containing natural rubber and elastic natural rubber materials.The bleaching mechanism and, in particular, the surface bleaching mechanism are not fully understood. that the bleach activator undergoes the nucleophilic attack by a peridroxide anion, which is generated from the hydrogen peroxide developed by the peroxygen bleach, to form a peroxycarboxylic acid.This reaction is commonly known as peridrolisis. amino derivatives herein may also be used in combination with preferably hydrophilic activators, of over then, of safe rubber, such as TAED, typically at weight ratios of caprolactarine activators or amido derivatives: TAED on a scale of 1: 5 to 5: 1, preferably about 1: 1.

Auxiliary Ingredients The compositions herein may optionally include one or more other auxiliary detergent materials or other materials to aid or improve the performance of Cleaning, treatment of the substrate to be cleaned, or to modify the aesthetics of the detergent composition (for example, perfumes, dyes, dyes, etc). Preferably, the auxiliary ingredients should have good stability with the bleaches employed herein. Preferably the detergent compositions herein must be boron-free and phosphate-free. Additionally, dishwashing formulations are preferably free of chlorine. The following are illustrative examples of said auxiliary materials. Detergency builders - Builders may optionally be included in the compositions herein to help control the hardness of minerals. Inorganic and organic builders can be used. Detergent detergents are typically used in fabric washing compositions to help remove particulate soils. The level of detergency detergent may vary depending on the final use of the composition and its desired physical form. When present, the compositions will typically comprise at least about 1% detergency builder. Liquid formulations typically comprise from about 5% to about 50%, and typically from about 5% to about 30%, by weight of detergency builder. Granulated formulations typically comprise about 10% a - about 80%, very typically from about 15% to about 50% by weight of the builder. However, lower or higher detergency builder levels are not excluded. Examples of silicate builders are alkali metal silicates, particularly those having a Si? 2: N 2? Ratio. in the scale from 1.6: 1 to 3.2: 1 and layered silicates, such as the layered sodium silicates described in US Pat. No. 4,664,839, issued May 12, 1987 to H. P. Rieck. NaSKS-6 is the trade name for a crystalline layered silicate sold by Hoechst (commonly abbreviated as "? KS-6"). Unlike zeolite builders, the NaSKS-6 silicate detergent builder does not contain aluminum. NaSKS-6 has the morphological form of layered silicate delta-a2Si0e. It can be prepared by methods such as those described in German Application DE-A-3,417,649 and DE-A-3, 742, 043. SKS-6 is a highly preferred layered silicate for use herein, but other layered silicates , such as those that have the general formula NaMSix? 2x +? 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-11 co or the alpha, beta and gamma forms. As indicated above, the delta-Na2 SiOs form - (Na KS-6) is most preferred for use in the present. Other silicates can also be used such as magnesium silicate, for example, which can serve as a tightening agent in granulated formulations, as a stabilizing agent for oxygen bleaches, and as a component of foam control systems. Examples of carbonate builders are the alkali metal and alkali metal carbonates as described in German Patent Application No. 2,321,001 published November 15, 1973. Aluosilicate builders are useful in the present invention. Alososilicate detergent builders are of great importance in the majority of heavy duty granulated commercially charged detergent compositions, and can also be an important detergency builder ingredient in liquid detergent formulations. Alu inosilicate builders include those that have the empirical formula: Mz (zA102) and]? H2? where z and y are integers of at least 6, the molar ratio of zay is on the scale of about 1.0 to about 0.5, and x is an integer of about 15 to about 264. The useful alurninosilicate ion exchange materials are commercially available. These Alurninosilicates may be of crystalline or amorphous structure and may be naturally occurring or synthetically derived aluminosilicates. A method for producing alkynyl silicate ion exchange materials is described in US Patent 3,985,669, Krurnmel et al. Issued October 12, 1976. Preferred synthetic crystalline aluminosilicate ion exchange materials useful herein are available under the designations Zeolite A, Zeolite P (B), Zeolite MAP and Zeolite X. In an especially preferred embodiment, the ion exchange material of crystalline aluminosilicate has the formula: Nai2 C (A102) l2 (YES02) l2] xH2? wherein x is from about 20 to about 30, especially about 27. The material is known as Zeolite A. Dehydrated zeolites (x = 0-10) can also be used herein. Preferably, the aluminosilicate has a particle size of about 0.1-10 microns in diameter. Organic builders suitable for the purposes of the present invention include, but are not limited to, a wide variety of polycarboxylate compounds. As used herein, "polycarboxylates" refers to compounds having a plurality of carboxylate groups, preferably at least 3 carboxylates. Polycarboxylate builders can generally be added to the composition in acid form, but can also be added in the form of a neutralized salt. When used in the salt form, alkali metals such as sodium, potassium and lithium, or alkanolammonium salts are preferred. Included among the polycarboxylate builders are a variety of useful material categories. An important category of polycarbonate detergency builder includes ether polycarboxylates, including oxydisuccinate, as described in Berg, US Patent 3,128,287, issued April 7, 1964, and Lamberti et al., US Patent 3,635,830. , issued January 18, 1972. See also "TMS / TDS" detergency builders of US Pat. No. 4,663,071, issued to Bush et al. on May 5, 1987. Suitable ether polycarboxylates also include cyclic compounds, particularly alicyclic compounds, such as those described in US Patents 3,923,679; 3,835,163; 4,158,635; 4,120,874 and 4,102,903. Citrate builders, eg, citric acid and soluble salts thereof (particularly sodium salt), are polycarboxylate builders of particular importance for heavy duty liquid detergent formulations because of their availability from renewable resources and their biodegradability. Citrate can also be used in granular compositions, especially in combination with aeolith and / or layered silicate builders. Oxydisuccinates are also especially useful in said compositions and combinations. The fatty acids, e.g., C12-C18 monocarboxylic acids, can also be incorporated into the compositions by themselves, or in combination with the aforementioned builders, especially citrate and / or succinate builders, to provide additional detergency activity. Such use of fatty acids will generally result in decreased foaming, which would be considered by the for ulator. In situations where phosphorus-based builders can be used, and especially in the bar formulations used for hand washing operations, various alkali metal phosphates such as the well-known sodium tripolyphosphates, sodium pyrophosphate, can be used. and sodium orthophosphate. Chelating Agents - Although detergency builders can be used, the detergent compositions herein preferably do not contain those manganese chelating agents that abstract the manganese from the bleach catalyst complex. In particular, phosphonates, phosphates and aminophosphonate chelating agents such as DEQUEST are preferably not used in the compositions. However, nitrogen-based manganese chelating agents, such as ethylene diamine, are useful.

, N, N'-disuccinate (EDDS). Detersive Surfactants - Non-limiting examples of additional, non-amide surfactants, useful herein include conventional Cn-Ciß alkylbenzene sulphonates ("LAS") and primary C10-C20 alkyl sulfates ("AS"), branched and random chain, the secondary C 1 -Ciß alkylene sulphates (2,3) of the formula CH 3 (CH 2) x (CH 0 S0 3 ~ M +) CH 3 and CH 3 (CH) and (CH 0 S 0 3 M) CH 2 CH 3 wherein x and (y + 1) are integers of at least 7, preferably at least about 9, and M is a water solubilizing cation, especially sodium, unsaturated sulaphthates such as oleyl sulfate, Cι-Ciß alkylalkoxysulfates ("AEKS", especially ethoxysulfates EO 1-7 ), Cι-Ciß alkylalkoxycarboxylates (especially the EO 1-5 ethoxycarboxylates), the glycolic ethers of Cι-Ciß, the Cι-Ciß alkyl polyglycosides and their corresponding sulfated polyglycosides, and C 12 -C 18 aliphatic fatty acid esters. If desired, conventional non-ionic amphoteric surfactants such as C12-C18 alkyl ethoxylates ("AE") including the so-called narrow peak alkyl ethoxylates and the C6-C12 alkyl phenoalkoxylates (especially mixed ethoxylates and ethoxy / propoxy), C12 betaines C18 and sulfobetaines ("sultaines"), Cι-Ciß amine oxides, and the like, can also be included in the overall compositions. N-alkyl polyhydroxyl fatty acid amides can also be used. Typical examples include N- C12-C18 rnethylglucans (see) 0 9,206,154 Other sugar-derived surfactants include the N-alkoxy polyhydroxy fatty acid amides, such as N ~ (3-rnetoxipropiDglucamine of Cι-Ciß- N-propyl to N-hexylglucamides of C12-C18 can be used for low sputtering.C10-C20 conventional soaps can also be used Mixtures of anionic and nonionic surfactants are especially useful Other conventional useful surfactants are listed in the normal texts. Particularly suitable ionics for dishwashing are the straight-chain ethoxylated low spurnation or non-spurring alcohols such as Plurafac ™ of the RA series, supplied by Eurane Co., Lutensol ™ LF series, supplied by BASF Co., TritontM DF series, supplied by Rohm to Haas Co., and SynperonicTM LF series, supplied by ICI Co. Replenishing agents / anti-redeposition of clay dirt. The compositions of the present invention may also optionally contain water-soluble ethoxylated amines having clay dirt removal and anti-redeposition properties. Detergent compositions in granules 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%.

The remover and anti-redeposition agent of preterm dirt is tetraetiienpentapuna ethoxylated. Example ethoxy 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 111,965, Oh and Gosselmk, published on June 27, 1984. Other clay dirt remover / anti-redeposition agents that can be used include the ethoxylated amine polymers described in European Patent Application 111,984, Gosselin, published June 27, 1984; the zwitterionic polymers described in European Patent Application 112,592, Gosselink, published 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 preferred type of anti-redeposition agent includes the carboxyl-phenyl-cellulose (CMC) materials. These materials are well known in the art. Polymer dispersion agents - The polymer dispersion agents can be advantageously used at levels of from about 0.1% to about 7%, by weight, in the compositions herein, especially in the presence of detergents of zeol ta and / or silicate The suitable polymeric dispersing agents include polycarboxylic 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 polymeric dispersing agents increase the performance of the detergent builder. Overall, when used in combination with other detergency builders (including lower molecular weight polycarboxylates) by inhibition of crystal growth, peptization of particulate and anti-redeposition release, polymeric polycarboxylate materials can be prepared by polymerizing or copolying containing suitable unsaturated monomers, preferably in their acid form, unsaturated monomeric acids which can be polimerized to form suitable polymeric polycarboxylates include acrylic acid, maleic acid (maleic anhydride), fumaric acid, itaconic acid, aconitic acid , esaconic acid, citraconic acid, methylenemalonic. The presence of the polymeric polycarboxylates in the present or polymeric segments, which do not contain carboxylate radicals such as ethyl vinyl 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 polymers based on acrylic acid which are useful in the present are the water-soluble salts of polyrnened acrylic acid. The average molecular weight of said polymers in the permutatible acid form varies from about 2,000 to 10,000, 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, U.S. Pat. 3,308,067, issued March 7, 1967. Copolymers based on acrylic / aleic 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 from about 5,000 to 75,000 and most preferably from about 7,000 to 65,000. The ratio of the acrylate segments to those of rnaleate in said copolymers generally ranges from about 30: 1 to about 1: 1, most preferably from 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. The '"" soluble acrylate / random alloy copolymers of this type are known materials which are described in the Application European Patent No. 655915, published on December 15, 1982. Another polymeric material that can be included is polyethylene glycol (PEG). PEG can exhibit performance of dispersing agent and can act as an anti-redeposition agent for clay soiling. The typical molecular weight scales for these purposes vary from around 500 to about 100,000, more preferably from about 1,000 to about 50,000 and most preferably from about 1,500 to about 10,000. The polyaspartate and polyglutamate dispersing agents can also be used, especially in conjunction with zeolite detergency enhancement. Dispersing agents such as those of preferable polyaspartate have a molecular weight (avg.) Of about 10,000. Enzymes.- Enzymes can be included in the formulations herein for a wide variety of laundry purposes of fabrics, including, for example, the removal of protein-based stains, based on carbohydrates or triglycerides, and to avoid the transfer of migratory dyes and the restoration of fabrics. Enzymes to be incorporated include proteases, ilasae, lipaeas, cellulaeae and peroxidases, as well as mixtures thereof. Other types of enzymes can also be included. They can be of any suitable origin, such as origin 'vegetable, animal, bacterial, icotic and yeast. However, its choice is governed by several factors such as pH activity and / or optimal stability, thermostability, stability against active detergents, builders, etc. In this regard, bacterial and icotic enzymes, such as bacterial amylases and proteases and fungal cellulase, are preferred. Enzymes are normally incorporated at levels sufficient to provide up to about 5 mg by weight, very typically from about 0.01 mg to about 3 mg of active enzyme per gram of the composition. Stated otherwise, the compositions herein typically comprise from about 0.001% to about 5%, preferably 0.01% -1% by weight of a commercial enzyme preparation. Protease enzymes are usually present in such commercial preparations at levels sufficient to provide 0.005 to 0.1 Anson units (AU) of activity per gram of composition. Suitable examples of proteases are the subtilicins that are obtained from particular strains of B.subtilis and B.lichem orms. Another suitable protease is obtained from a strain of Bacillus that has maximum activity throughout the pH regime of 8-12, developed by Novo Indudtpes A / S under the trademark ESPERASE. The preparation of this enzyme and analogous enzymes is described in British Patent Specification No.1,243, 784 by Novo. The proteolytic enzymes "Commercially available suitable for removing protein-based stains include those sold under the trademarks ALCALASE and SAVINASE of Novo Industries A / S (Denmark) and MAXATASE of International Bio-Synthetics, Inc. (Netherlands) Other Proteases include Protease A (see European Patent Application 130,756 published January 9, 1985) and Protease B (see European Patent Application Serial No. 87303761.8, filed April 28, 1987 and European Patent Application 130,756, Bott et al. , published January 9, 1985.) Arnilases include, for example, α-amylase described in British Patent Specification No. 1,296, 839 (Novo), RAPIDASE, International Bio-Synthetics, Inc. and TERMAMYL. The cellulase usable in the present invention includes both bacterial and fungal cellulase.Preferably, they should have an optimum pH of between 5 and 9.5 The lipase enzymes suitable for use in detergents include those produced by microorganisms of the Pseudornonas group, such as Pseudomona stutzeri ATCC 19. 154, as described in British Patent 1,372,034. See also lipases in Japanese Patent Application 53,20487, open for public inspection on February 24, 1987. This lipase is available from Amano Pharmaceutical Co. Ltd., Nagoya, Japan, under the registered trademark Lipasa P "Amano" , which is hereinafter referred to as "Amano-P".

Other commercial lipases include Amano-CES, lipases ex Chrornobacter viscosum, e.g. Chromobacter viscosum var. lipolyctum NRRLB 3673, commercially available from Toyo Jozo Co., Tagata, Jap > ón and also the lipaeas of Chrornobacter viscosurn from U.S. Boichemical Corp., E.U.A. and Dieoynth Co., the Netherlands, and the lipases of ex Pseudomonas gladioli. The LIPOLASE enzyme derived from Humicola lanuginosa and which is commercially available from Novo (see also EPO 341,947) is a preferred lipase for use herein. Peroxidase enzymes are used in combination oxygen supplies, V.gr., percarbonate, eg. > orato, persulfate, hydrogen peroxide, etc. They are used for "bleaching solutions", that is, to avoid transfer of dyes or pigments removed from the substrates during washing operations to other substrates in the washing solution. Peroxidase enzymes are known in the art and include, for example, horseradish peroxidase, ligninase, and halogen-peroxidase such as chloroperoxidase and broperoperoxidase. Detergent compositions containing per idase are described, for example, in PCT International Application WO 89/099813, published October 19, 1989 by 0. Kirk. assigned to Novo Indudtries A / S. A wide variety of enzyme materials and means for their incorporation into synthetic detergent compositions are described in the U.S. Patent. 3,553,139 issued on January 5, 1971 to McCarty and others Additionally, enzymes are described in the U.S. Patent. 4,101,457, Place et al., Issued July 18, 1978 and in the U.S. Patent. 4,507,219, Hughes, both issued March 26, 1985. Enzyme materials useful for liquid detergent formulations and their incorporation into such formulations are described in the U.S. Patent. 4,261,868, Hora et al., Issued April 14, 1981. Enzymes for detergents can be stabilized by various techniques. Lae enzyme stabilization techniques are described and illustrated in the U.S. Patent. 3,600,319 issued August 7, 1971 to Gedge, et al., And in European Patent Application Publication No. O 199 405, Application No.86200586.5, published October 29, 1986, Venegae. Enzyme stabilization systems are also described, for example, in U.S. Pat. 3,519,570. Enzyme Stabilizers.- The enzymes employed herein are typically stabilized by the presence of water-soluble calcium ion and / or magnesium ions in the finished compositions that supply said ions to the enzymes. (Calcium ions are in some way generally more effective than magnesium ions and are preferred in the present if only one type of cation is being used). Additional stability can be provided by the presence of several other stabilizers described in the art, especially borate species: see Sverson, E.U.A. 4,537,706. Typical detergents, especially liquids, comprise from about 1 to about 30, preferably from about 2 to about 20, most preferably from about 5 to about 15 and preferably from about 8 to about 12 ilies of calcium ion per liter of finished composition. This may vary somewhat, depending on the amount of enzyme present and its response to calcium or magnesium ions. The level of calcium or magnesium ionee should be selected so that there is always a minimum level available for the enzyme after allowing it to form complexes with builders., fatty acids, etc., in the composition. Any water soluble calcium or magnesium salt can be used as the calcium or magnesium ion supply, including, but not limited to, calcium chloride, calcium sulfate, calcium malate, calcium maleate, calcium hydroxide, calcium formate, calcium and calcium acetate and the corresponding magnesium salts. Frequently, a small amount of calcium ions, generally from about 0.05 to about 0.4 millimoles per liter, is also present in the composition due to the calcium present in the enzyme suspension and the formula water. In solid detergent compositions the formulation may include a sufficient amount of a supply of water soluble calcium ions to provide such an amount in the wash liquor. Alternatively, the hardness of the natural water may be sufficient.

It should be understood that the aforementioned levels of calcium and / or magnesium ions are sufficient to provide enzyme stability. Additional calcium and / or magnesium ions may be added to the compositions to provide an additional measure of fat removal performance. If used for such purposes, the compositions herein should typically comprise from about 0.05% to about 2% by weight of a water-soluble supply of calcium or magnesium ions or both. The amount may vary, of course, depending on the amount and type of enzyme used in the composition. The composition herein may also optionally, but preferably, contain several additional stabilizers, especially borate type stabilizers. Typically, such stabilizers are used in the compositions at levels of from about 0.25% to about 10%, preferably from about 0.5% to about 5%, most preferably from about 0.75% to about 3% by weight of boric acid or other a borate compound capable of forming boric acid in the composition (calculated on the basis of boric acid). Boric acid is preferred, although other compounds such as boric oxide, borax and other alkali metal borates (eg sodium orthoborate, sodium metaborate and sodium pyroborate and sodium pentaborate) are suitable. Substituted boric acids (e.g., phenyl boronic acid, butane boronic acid and p-bromophenylboronic acid) can also be used in place of boric acid.

Brightener - any optical brighteners or brighteners or whitening agents known in the art can be incorporated at levels typically from about 0.05% to about 1.2% by weight, in the detergent compositions herein. Commercial optical brighteners that may be useful in the present invention can be classified into subgroups, including, but not necessarily limited to, stilbene derivatives, pyrazoline, coumarin, carboxylic acid, methinocyanins, 5-dibenzothiophene dioxide, azoles , heterocyclics of 5 and 6 membersj and other diverse agents. Examples of such brighteners are described in "The Production and Application of Fluorescent Brightening Agents," M. Zahradnik, published by John Uiley & Sons, New York (1982). Specific examples of optical brighteners that are useful in the present compositions are those identified in the U.S.A. 4,790,865 issued to Uixon on December 3, 1988. These brighteners include the Verona PHOROUHITE polishing series. Other brighteners described in this reference include Tinopal UNPA, Tinopal CBS and Tinopal 5BM; available from Ciba-Geigy; Artic Uhite CC and Artic Uhite CUD, available from Hilton-Davis, with headquarters in Italy; the 2- (4-estri-phenyl) -2H-naphtholCl, 2-diatriazoles; 4,4'-bis (1, 2, 3-triazol-2-2-yl) -stilbenes; 4,4'-bis (eetril Jbiefeniloe) and lae aminocurnarin s Specific examples of these brighteners include 4-methyl-7-diethyl- arninocurnari a; 1,2-bis (-benzimidazol-2-yl) ethylene; 1,3-diphenyl-frazolines; 2,5-bis (benzoxazol-2-yl) thiophene; 2-estryl-naf-Cl, 2-d -oxazole; and 2- (stilben-4-yl) -2H-naphtho-L "1, 2-d] triazole See also US Patent 3,646,015 issued to Hanilton on February 29, 1972. Here, the aniline brighteners are preferred. Foam suppressants - Compounds to reduce or suppress foam formation can be incorporated into the compositions of the present invention.Suppression of foams may be of particular importance in the "high concentration cleaning process" and in style washing machines. European front loading 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 Oth er Encyclopedia of Chemical Technology, 3rd Edition, Volume 7, pages 430-447 (John Uiley a Sons, Inc., 1979) A category of foam suppressant of particular interest includes monocarboxylic fatty acids and soluble salts thereto., 954,347, issued on September 27, 1960 to Uayne St. John. The monocarboxylic fatty acids and salt salts used as foam suppressors 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 salts of ammonium and alkanolamome. The detergent compositions herein may also contain suds suppressants which are not surfactants. Examples include, for example: high molecular weight hydrocarbons such as fine couple, fatty acid ester (eg, fatty acid glycerides), fatty acid esters of monovalent alcohols, C18-C40 aliphatic ketones (v. gr., stearone), etc. Other foam inhibitors include N-alkylated arninotnazines such as tri- to hexa-alkylamman or di- to tetra-alkyldiaminoclrotpazines formed as cyanuric chloride products with two or three moles of a primary or secondary amine containing from 1 to 24 carbon atoms. propylene oxide and rnonoeetearyl phosphates such as rhono-stethyl alcohol phosphate ester and alkali metal (e.g., K, Na and Li) nono-isosaryl phosphates and ester phosphates. Hydrocarbons such as parafma and halogenoparatins can be used in liquid form. The 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 (atmospheric pressure ). 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 Suppressors of hydrocarbon foams are described, for example, in the patent of US Pat. No. 4,265,779 issued May 5, 1981 to Gandolfo et al. The hydrocarbons, therefore, include aliphatic, alicyclic, aromatic, and heterocyclic saturated or unsaturated hydrocarbons having from about 12 to about 70 carbon atoms. The term "paraffin" as used in the discussion of foam suppressors, is intended to include mixtures of true paraffins and cyclic hydrocarbons. Another preferred category of eepu suppressors ae that are not surfactants comprises silicone foam suppressors. This category includes the use of poiorganosiloxane oils such as polydimethylsiloxane, dispersions or emulsions of polyorganosiloxane oils or resins, and combinations of polyorganosiloxane with silica particles wherein the polyorganosiloxane is absorbed or fused onto the silica. Silicone foam suppressors are well known in the art and are described, for example, in U.S. Patent 4,265,779, issued May 5, 1981 to Gandolfo et al. And European Patent Application No. 89307851.9, published on 7 February 1990 by Starch, MS Other silicone foam suppressors are described in U.S. Patent 3,455,839 which relate to compositions and processes for defoaming aqueous solutions by incorporating therein small amounts of polydi-ethylsiloxane fluids. . 1 Silica and silanated silica mixtures are described, for example, in German Patent Application DOS 2,124,526. The eliminators of silicone foams and the controlling agents of eepumae in comp > Granulated detergent compositions are described in US Patent 3,933,672, Bartolotta et al. and in US Patent 4,652,392, Baginski et al., issued March 24, 1987. An illustrative silicone-based foam suppressant to be used herein is a foam suppressing amount of a foam controlling agent which connects essentially: (i) polydimethylsiloxane fluid having a volatility of about 20 is to about 1,500 is at 25 ° C; (ii) from about 5 to about 50 parts per 100 parts by weight of (i) siloxane resin composed of (CH3) 3? i0? / 2 units of SiO2 units in a ratio of (CH3) 3Si0 units ? 2 to SIO2 units 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 (pretrides) and not polypropylene glycol. The suppressor of foams of primary silicone is branched / interlaced and non-linear. To illustrate this point, typical liquid laundry detergent compositions with controlled spraying will optionally 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 suppressor, comprising (1) a non-aqueous emulsion of a primary foam-forming agent which is a mixture of (a) a polyorganosiloxane, (b) a resinous siloxane or a silicone compound producing resin silicone, (c) a finely divided filler material and (d) a catalyst for promoting the reaction of blend 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 granulated gels, etc. See also Patents of E.U.A. 4,978,471, Starch, issued December 18, 1990 and 4,983,316, Starch, issued January 8, 1991, 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 eupune former of the present preferably comprises polyethylene glycol and a copolymer of polyethylene glycol / polypropylene glycol, all having a weight molecular average less than about 1,000, preferably between about 100 and 800. The polyethylene glycol and polystyrene / polypropylene copolymers herein have a solubility in water at room temperature other than about 2% in? that? preferably, 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 glycol: copolymer of p > olyethylene-polypropylene glycol. The preferred silicone eepurnas supresoree used herein does 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-alkylaleneols) and mixtures of said alcohols with silicone oils, such as the siliconee described in US Pat. No. 4,798,679, 4,075,118 and EP 150,872. The secondary alcohols include Cß-Ciß alkyl alcohols having a Ci-Ciß chain. An alcohol preferred is 2-butyloctanol, which is available from Condea under the trade name ISOFOL 12. Mixtures of secondary alcohols are available under the trade name IS LCHEM 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 euphorres, 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 5% foam suppressant. When used as foam suppressors, the monocarbon fatty acids, and salts thereof, will typically be present in amounts up to about 5%, by weight, of the detergent composition. Preferably, from about 0.5% to about 3% of the nonacarboxylate fatty acid suppressant is used. Silicone foam supresoree are typically used in amounts up to about 2.0%, by weight, of the detergent composition, although higher amounts can be emitted. This upper limit is practical in nature, mainly due to the interest of keeping costs reduced to a minimum and the effectiveness of lower quantities to effectively control the sputum. Preferably from about 0.01% to about 1% silicone foam suppressant is used, most preferably from about 0.25% to about 0.5%. As used herein, 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 ee generally used in amounts ranging from about 0.01% to about 02% at p > that of 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 euphorres are typically used at 0.2% -3% by weight of the finished compositions. Fabric softeners.- Various fabric softeners that soften during washing, especially the impalpable srnectite clays of the U.S. Patent. 4,062,647, Storm and Nirschl, issued December 13, 1977, as well as other softening clays known in the art, can optionally be used at levels of about 0.5% a about 10% by weight in the compositions herein to provide softening benefits concurrently with fabric cleaning. Clay-based softeners may be used in combination with amine and cationic softeners as described, for example, in the US Patent. 4,375,416, to Crisp et al., March 1, 1983 and the U.S. Patent. 4,291,071 to Harris et al., Issued Sep. 22, 1981. Dye transfer inhibiting agents - The compositions of the present invention optionally, but preferably, include one or more materials effective to inhibit the transfer of dyes from one fabric to another during the cleaning procedure. Generally, said dye transfer inhibiting agents include polyvinylpyrrolidone polymers, polyamine N-oxide polymers, copolymers of N-vinylpyrrolidone and N-vinylimidazole, manganese phthalocyanine, peroxidases and mixtures of the rniemoe. 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-A? -P; where P is a polymerizable unit to which a group N-0 can be attached or group N-0 can form part of the unit polimerizable or group N-0 can be attached to both units; A is one of the following structures: -NC (O) -, -C (0) 0-, -S-, -0-, -N =; x is 0 or 1; and R is aliphatic, aliphatic, ethoxylated, aromatic, heterocyclic or alicyclic groups or any combination of the same to which the nitrogen of the group N-0 can be attached or the group N-0 is part of these groups. Preferred polyane N-oxides are those wherein R is a heterocyclic group such as pyridine, pyrrole, irnidazole, pyrroline, piperidine and derivatives thereof. The group N-0 can be represented by the following general structures: wherein Ri, R2, R3 are aliphatic, aromatic, heterocyclic or alicyclic groups or combinations thereof; x, y and z are 0 or 1; and the nitrogen of the group N-0 can be attached or forms part of any of the aforementioned groups. The amine oxide unit of the polyane 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, polyamide, polyrnidae, polyacrylates and mixtures thereof. These polymers include random or block copolymers in which one type of nonordinate 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. Polyarnine 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. 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 500,000 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.) The coppers of PVPVI typically have a molar ratio of N-vinylimidazole to N-vinylpyrrolidone from 1: 1 to 0.2: 1, most 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 can also employ a polyvinylpyrrolidone ("PVP") having an average molecular weight of about 5,000 to about 400,000, preferably about 5,000 to about 200,000, and most preferably still about 5,000 to about 50,000 PVPs are known to those skilled in the detergent field art, see, for example, EP-A-262,897 and EP-A-256, 696, incorporated herein by reference, The compositions containing PVP may also contain polyethylene glycol ("PEG") having an average molecular weight of about 500 to about 10. 0.000, preferably from about 1,000 to about 10,000. Preferably, the ratio of PEG to PVP on a basis of pprn 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 transfer inhibitory action of Colorant. If used, the compositions herein will preferably comprise from about 0.01% to 1% by weight of said optical brighteners. The useful hydrophilic optical brighteners in the present invention are those having the structural formula: wherein Ri is selected from anilino, N-2-bis-hydroxyethyl and NH-2-hydroxyethyl; R 2 is selected from N-2-bis-hydroxyethio, N-2-hydroxyethyl-N-methylamino, oryphino, 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-bie-hydroxyethyl and M is a cation such as sodium, the brightener is acid 4,4 ', bisC (4-anilino-6- (N-2- bis-hydroxyeti 1) -s-triazin-2-yl) amino] -2, 2'-styptic isylbenzene 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? Itl in the detergent compositions of the present invention. 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'-bisC (4-a-ylino-6- (N-2-hydroxyethyl-rhamnilarnino) • -s- triazin-2-yl lamino] -2, 2 ' This type of brightener is commercially marketed under the tradename Tinopal 5BM-6X by Ciba-Geigy Corporation When in the above formula Rl is anilino, R 2 is rnorfilino and M is a cation such as sodium, the brightener is the sodium salt of 4,4'-bisC (4-anilino-6-morphino-s-triazin-2-yl) arnino] 2, 2'-styrylisulfonic acid This particular kind of brightener is sold commercially under the trade name Tinopal AMS-GX by Ciba-Geigy Corporation The speci fi c optical brightener species selected for use in the present invention provides speci fi cally effective dye transfer inhibition performance benefits when used in combination with the polyrnic dye transfer inhibiting agents selected above. des 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 significantly better dye transfer inhibition 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 so both are deposited relatively quickly on these fabrics. The degree to which the brighteners are deposited on the fabrics in the washing solution can be defined by a p "arnerne called" depletion 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. Of course, it will be appreciated that other types of conventional optical brightener compounds may optionally be present in the compositions herein 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. Other ingredients - A wide variety of other ingredients useful in caomposicionee detergents can be included in the present, including other active ingredients, vehicles, hydrotropes, processing aids, colorantee and pigmentoe, solvents for liquid formulations, sunscreens for bar compositions, etc. . If high sputtering is desired, eepurnase increments such as Cι-Ciß alkanolanes can be incorporated into the compositions, typically at levels of 1% -10%. The nonoethanol and Cno-Cm dietnolarninae illustrate a typical class of said foam improvers. The use of said eepurine enhancers with auxiliary surfactants with high foaming such as amine oxides, betaines and sultaines noted above is also advantageous. If desired, soluble magnesium salts such as MgCl 2, MgSO 4 and the like, can be added at typically 0.1% -2% levels, to provide additional sputtering and to increase fat removal performance. Various detersive ingredients employed in the present compositions can be further stabilized by absorbing said ingredients on a porous hydrophobic subetrato, then coating said substrate with a hydrophobic coating. Preferably, the detersive ingredient is mixed with a surfactant before being absorbed into the porous substrate. During use, the detersive ingredient is released from the substrate in the aqueous wash liquor, where it performs its intended detersive function. To illustrate this technique in more detail, a porous hydrophobic silica (trade name SIPERNAT DIO, Degussa) is mixed with a proteolytic enzyme solution containing 3% -5% nonionic ethoxylated alcohol surfactant of C13-15 (EO 7 ). Typically, the enzyme / surfactant solution is 2.5X of the silica pee. The re-emerging powder with stirring in silicone oil (Various viscosities of silicone oil can be used on the scale of 500-12,500). The resulting silicone oil dispersion is e ulsified or otherwise added to the final detergent matrix. By this means, ingredients such as the aforementioned enzymes, bleaches, bleach activators, bleach catalysts, photoactivators, dyes, fluorescers, fabric conditioners and hydrolyzable surfactants can be "protected" for use in detergents, including liquid detergents laundry. The liquid detergent compositions may contain water and other solvents such as vehicles. The low molecular weight primary and secondary alcohols illustrated by netanol, ethanol, propanol and isopropanol are suitable. Monohydric alcohols are preferred for solubilizing surfactant, but polyols such as those containing 2 to 6 carbon atoms and 2 to 6 hydroxyl groups (e.g., 1,3-propanediol, ethylene glycol, glycerin and 1,2-propanediol). The compositions may contain from 5% to 90%, typically from 10% to 50% of said vehicles. The detergent compositions herein will preferably be formulated such that during use in aqueous cleaning operations, the wash water has a pH of between about 6.5 and about 11, preferably between about 7.5 and 10.5. The Automatic dishwashing product formulations preferably have a pH between about 8 and about 11. Laundry products typically have a pH of 9 to 11. Techniques for controlling pH at recommended levels of use include the use of regulators. pH, alkalies, acids, etc., and are well known to those skilled in the art. The following examples illustrate co-position according to the invention, but are not intended to be limiting of the ism. EXAMPLE 1 A dry-clean bleach is co or follows. Ingredients Percentage (weight) Sodium percarbonate 20.0 Benzoyl caprolactam activator 10.0 Mn catalyst 0.1 Water soluble filler Balance * Mn? V2 (U -?) 3 (1, 4,7-TRIMETHYL-1, 4,7-TRIAZACICLONONAN) 2 (PF6) 2, as described in the US Patents Nos. 5,246,621 and 5,244,594. ** Mix of sodium silicate, sodium carbonate (1: 1). In the above composition, the sodium percarbonate can be replaced by an equivalent amount of perborate. In the previous composition, the catalyst Bleaching can be replaced by an equivalent amount of the following catalysts: ni H2 (u-O)? -OAC) -2 (1,4,7-trirnethyl-i, 4,7-triazacyclononane) 2 (C10") 2; MnIV <; (uO) e (1,4,7-triazacyclononane (CIO4; n * n MnIV «(uO)? (u-0Ac) 2 (1, 4,7-trirnethyl-l, 4,7-triazacyclononane) 2 (CIO) .) 3; MnIV (1,4, 7 -trimet.il-1, 4,7-triazacyclononane (OCH 3) 3 (PFs); CO (2,2'-bis? Idylamine) Cl 2; Di (isothiocyanate) bispyridylamin -cobalt (II), trisdi-iridylamin-cobalt perchlorate (II), 2O2CIO4 Co (2,2-biepyridylarnine), Bis ~ (2,2'-biepyridylamine) copper (II) perchlorate: tris (di- 2-pyridylamine) iron), Mn gluconate, Mn (CF3-03) 2, "Co (NH3) sCl, binuclear Mn conplexed with tetra-N-dentate ligand and bi-N-dentate, including N-4MnIII (u - 0) 2MniV | v | #;) + y [BipÍ2 nin (u-0) 2Mnivb pi2] - { Ci? «) 3 and rnezclae of them In addition, in the previous composition, the bleach activator can be replaced by an equivalent amount of the following activators: benzoyl valerolactam, nonaoyl caprolactam, nonanoyl valerolactam, 4-nitrobenzoyl caprolactam, 4-nitrobenzoyl valero.lactam, octanoyl caprolactam, octanoyl valerolac tama, decanoyl caprolactam, decanoyl valerolactam, undecanoyl caprolactam, undecanoyl valerolactam, 3,5,5, -trimethylhexanoyl caprolactam, 3,5,5-trimethexanoyl valerolactam, dinitrobenzoyl caprolactam, dinitrobenzoyl valerolactam, terephthaloyl dicaprolactam, terephthaloyl divalerolactam, (6- OctananidocapropiDioxybenzenesulphonate, (6-nonane-nanocaproyl) oxybenzenesulfonate, (6-decanamidocaproicroxybenzene sulfonate and mixtures thereof) The compositions of example 1 may be used per se as a bleach, or they may be added to a pre-soaking or containing detergent composition. surfactant agents for imparting a whitening benefit therein In the laundry detergent compositions herein, the abbreviated component identifications have the following meanings: sodium C12-alkyl-sodium-sulfonate sulfonate sodium TAS-alkyl sodium sulfate TAEn-alcohol ethoxylated bait with n rnolee of ethylene oxide per mole of alcohol 25EY-a predominantly linear C12-15 primary alcohol condensed with an average of Y moles of ethylene oxide TAED- tetraacetyl ethylene diamine NOBS-Nonanoyloxybenzenesulphonate silicate-silicate Amorphous sodium (the Si? 2: Na2? ratio normally follows) NaSKS-6 silicate stratifi crystal clear Anhydrous sodium carbonate-carbonate CMC-carboxymethyl cellulose sodium Zeolite A-hydrated eodium alurninoeilicate with a primary particle size in the range of 1 to 10 micrae.

Polyacrylate- homopolymer of acrylic acid of molecular weight of 4000 citrate-trisodium citrate dihydrate. Ma / AA- Copolymer of 1: 4 alic acid / acrylic, p > that average molecular of 80,000 Enzirna-proteolytic and mixed amyolitic enzyme, sold by Novo Industries As. Rinse aid - 4,4'-bis (2-rnorfolin-4-anilin-e-triazin-6-ylamino) stilbene-2: 2'-disulphonate disodium. Foam suppressor-25% paraffin wax P.f. 50 ° C, 17% hydrophobic silica, 58% paraffin oil. Anhydrous sodium sulfate sulfate. In its use for fabric cleaning, the compositions are employed in a conventional manner and in conventional concentrations. Thus in a typical way, the compositions are placed in an aqueous liquid at levels that can range from 100 ppm to 10,000 ppm, depending on the load of dirt and the stained fabrics are agitated therein.

EXAMPLE II The following detergent compositions are prepared (parts by weight).

? S C D LAS 7.71 7.71 7.71 7.71 AS - - - _- - 6.80 N-Glucoeamine - - - - 1.50 TAS 2.43 2.43 2.43 2.43 2.43 APR11 1.10 1.10 1.10 1.10 1.10 25E3 3.26 3.26 3.26 3.26 3.26 Zeolite A 19.5 19.5 19.5 13.0 13.0 Citrate 6.5 6.5 6.5 - - MA / AA 4.25 4.25 4.25 4 4..2255 4 4..2255 NaSKS-6 - 10.01 .1.0.01 Acico Cítrico - 2.73 2.73 TAE50 - 0.26 0.26 Carbonate 11.14 11.14 6.00 9.84 4.00 Perborato 16.0 16.0 18.0 16.0 16.0 Benzoil-ccaapprroollaaccttaammaa 1100..0000 3.00 10.00 5.00 15.00 TAED - 0 5.0 0 NOBS - 3.00 Catalyst Mn * (? P > m) 0.50 1.00 0.22 0.02 0.22 CCMMCC 00..4488 0.48 0.48 0.48 0.48 Eepurna Supreeor 0.5 0.5 0.5 0.5 0.5 Brightener 0.24 0.24 0.24 0.24 0.24 Enzyme 1.4 1.4 1.4 1.4 1.4 Silicate (redaction 2.0) 4.38 4.38 4.38 tlgSOü 0.43 0.43 0.43 0.43 0.43 Perfume 0.43 0.43 0.43 0.43 0.43 Sulfate 4.10 4.10 4.10 11.67 11.67 Water and various components, the rest. * niv2 (u-0) 3 (1, 4,7-trimethyl-1,4,7-triazacylclononane) 2 (PFß) 2, The above compositions can be modified with the addition of lipase enzymes. The above compositions can further be modified by replacing the bleach catalyst with an equivalent amount of bleach catalysts identified in Example 1. The above compositions can also be modified by replacing the benzoylcaprolactam with an equivalent amount of bleach activators identified in Example 1. The above compositions can also be modified by replacing the TAED with an equivalent amount of NOBS or leaving TAED outside the formulation. The above compositions can also be modified by replacing the perborate with an equivalent amount of percarbonate.

EXAMPLE III A laundry bar with bleach is prepared by normal extrusion processes and comprises (20%) LAS of Ci2-i3 / trip > ol i sodium phosphate (20%), sodium silicate (7%); sodium perborate nonohydrate (10%); (6-decanarnidocaproyl) oxybenzenesulfonate (10%), niv2 (u-0) 3 (1, 4, 7-trirnetii-?, 4, 7-triazacylclononane) 2- (PF6) 2, (1.0%); MgSO «or talc filler; and water (5%). The above compositions can be modified with the addition of lipase enzymes. The above conpoeiclones can also be modified by replacing the bleach catalyst with an equivalent amount of bleach catalysts identified in example 1. The above compositions can also be modified by replacing the bleach activator of (6-decanamidrocaproiDoxibenzene sulfonate with an equivalent amount of activators of bleach. bleach identified in Example 1. The above compositions can also be modified by replacing the perborate with an equivalent amount of percarbonate.

EXAMPLE IV An automatic dishwashing composition is as follows: Ingredient Percentage (weight) Trisodium citrate 15 Sodium carbonate 20 Silicate * g Nonionic surfactant2 3 Sodium polyacrylate (p.4000) 3 5 Thermamyl enzyme (60T) 1.1 Savi- nasa enzyme (12T) 3.0 Sodium perborate monohydrate 10 Benzoyl caprolactam 2 Mn catalyst * 0.03 Menoree The remainder 1BRITESIL, PO Corporation 2 low polyethylene oxide / polypropylene oxide foam 3ACCUSOL, Rohrn and Haas 4 mol ratio 1: 1 Mn cation and ligand to form Mniv2 (u-0) 3 (1,4,7-trimethyl-1, 4,7-triazacylclononane) 2 (PFβ) -2, in situ In the above composition, the perborate can be replaced by an equivalent amount of percarbonate. In the above composition, the bleach catalyst can be replaced with an equivalent amount of preformed bleach catalyst, as identified in Example 1, or with metal cations and ligand to form the bleach catalysts identified in Example 1. Previous compositions can also be modified by replacing the benzoylcaprolactate with an equivalent amount of bleach activators identified in example 1. In the above composition, the surfactant it can be replaced by an equivalent amount of any low foaming nonionic surfactant. The example includes straight-chain, low-foam or non-foam ethoxylated alcohols with Plurafact ™ i RA series, sold by Eurane Co., Lutensol ™? F series, sold by BASF Co., Triton ™ DF series, sold by Rohm to Haas Col, and SynperonicTM LF seriee, sold by ICI Co. Lae co-productions for automatic dishwashers can be in granular form, tablet, bar, or rinse aid.Methods for making granules, tablets, bars, or auxiliaries of rinsing are known in the art See, for example, US Patent Series Nos. 08 / 106,022, 08 / 147,222, 08 / 147,224, 08 / 147,219, 08 / 052,860, 07 / 867,941., All the granular compositions The above can be provided as spray-dried granules or granules of high density (600 g / 1 rnáe) or agglomerated.If desired, the Mn catalyst can be absorbed on and inside water-soluble granules, to keep the catalyst separated. of the balance of the compositions, thus providing stable additional storage capacity. Said granules (which should not contain oxidizable components) may comprise, for example, water-soluble silicates, carbonates and the like. Although the above arrangements are typical of those useful herein, it is more preferred that: (1) the Composition not contain detergent builder STPP; (2) that the nonionic: anionic nonionic agent ratio is greater than 1: 1, preferably at least 1.5: 1; and (3) that at least 1% p-erborate or other chlorine scavenger is present in the compositions to minimize the formation of MNO2 in use. While the previous examples illustrate the use of the present technology in cleaning / bleaching compositions designed for use in laundry and tableware care, it will be appreciated by those skilled in the art that the catalyzed bleaching systems herein may be employed under any circumstances in which improved oxygen bleaching is desired. Thus, the technology of this invention can be used, for example to whiten paper pulp, to whiten hair, to clean or sanitize aesthetic devices such as dentures, in tooth compositions to clean teeth and kill oral bacteria, and in any other circumstance in the that the bleaching is advantageous for the user.

Claims (8)

NOVELTY OF THE INVENTION CLAIMS

1. - A detergent composition comprising a catalytically effective amount of one or more bleach catalysts, a bleaching compound capable of relaxing hydrogen peroxide in an aqueous liquid, and one or more bleach activators, further characterized in that said bleach activators are members selected from the group consisting of: a) an amido bleach activator derived from the general formula: or mixtures thereof, wherein R1 is an alkyl, aryl, or alkaryl group containing from 1 to 14 carbon atoms, R2, ee an alkylene, arylene, or alkarylene group containing from 1 haeta 14 carbon atoms, RS is H or an alkyl, aryl or alkaryl group containing from 1 to 10 carbon atoms, and L is a residual group; b) a benzoxazine type bleach activator of the formula: wherein R 1 ee H, alkyl, alkaryl, aryl, arylalkyl, and wherein R 21 R 3, R "and R 5 may be the same or different substituents selected from H, halogen, alkyl, alkenyl, aryl, hydroxyl, alkoxy, amino, alkylamino , -COORβ, wherein RS is H or an alkyl group and carbonyl functions; c) N-acyl-lactam bleach activators of the formula: wherein n is from 0 to 8, preferably from 0 to 2, and RS ee H, an alkyl, aryl, alkoxyaryl, alkaryl group containing 1 to 12 carbons, or a substituted phenyl group containing from 6 to to up to 18 carbon atoms; and d) mixtures of a), b) and c).

2. A composition according to claim 1, comprising a bleaching compound of percarbonate or perborate, or mixtures thereof, and a bleach activator selected from the group consisting of benzoyl caprolactam, benzoyl valerolactam, nonaoyl caprolactam, nonanoyl valerolactam, 4-nitrobenzoyl caprolactam, 4-nitriobenzoyl valerolactam, octanoyl caprolactam, octanoyl valerolactam, decanoyl caprolactam, decano.il valerolactam, undecano.il caprolactam, undecanoil valerolactam, 3,5,5-trimethylhexanoyl caprolactam, 3,5,5-trimethylhexanoyl valerolactam, dinitrobenzoyl caprolactam, dinitrobenzoyl valerolactam, terephthaloyl dicaprolactarna, terephthaloyl divalerolacta a, (6-octanamidocapropil) oxybenzenesulfonate, (6-nonanamidocaproi.l) oxibencensul fonato, (6-decanamidocaproiDoxibenceneul fonate, and mixtures thereof)

3. A composition according to claim 2 further characterized in that the bleach catalyst is selected from a group consisting of Mniy2 (u-0) 3 (1.4 , 7-trimethyl-1,4,7-triazacyclononane) 2 (PFß) 2, MniII2 (u-0)? (U-0Ac) 2 (1, 4,7-trimethyl-1, 4,7-triazacyclononane) 2 (CIO. )2; Mniv4 (? -O) ß (1, 4,7-triazacyclononane) «(C10«) «; Mn * 11 rmlv (u-0)? (u-0Ac) 2 (1,4,7-trimethyl-1,4-7-triazacyclononane) 2 (CIO4) 3; Mniv (1,4,7-trimethyl-1,4,7-triazacyclononane (0CH3) 3 (PFß); C0 (2,2'-bispyridylarnine) Cl21 Di (isothiocyanate) bispyridylamin-cobalt (II); trisdipyridyl perchlorate in -cobaltoí II); Co (2,2-bispyridylamine) 2O2CIO4; Bis- (2,2'-bispyridylamine) copper (II) perchlorate: tris (di-2-pyridylarnine) iron (II) perchlorate; Mn gluconate; n (CF3S? 3) 2, " Co (NH3) sCl; Binuclear Mn complexed with ligand of tetra-N- dentate and bi-N-toothed, including N-4MniH (u-0) 2 niVN4) + yCBipÍ2 nin (u-0) 2 niVbipi2] _ (ci? 4) 3 and mixtures of the renderers.

4. A laundry detergent co-product comprising conventional surface active agents, other detersive ingredients, and a bleaching composition according to claim 1.

5. A composition according to claim 4 further characterized in that the compound of Bleaching is selected from a group consisting of percarbonate, perborate and mixtures thereof, a bleach activator selected from the group consisting of benzoyl caprolactam, benzoyl valerolactam, nonaoyl caprolactam, nonnanoyl valerolactam 4-nitrobenzoyl caprolactar, 4-nitriobenzoyl valerolactam, octanoyl caprolactam, octanoyl valero.lactam, decanoyl caprolactam, decano.il valerolactam, undecanoyl caprolactam, undecano.il valerolactam, 3,5,5-trirnethylhexanoyl caprolactam, 3,5,5-trirnetiihexanoyl valerolactam, dinitrobenzoyl caprolactam , dinitrobenzoyl valerolactam, terephthaloyl dicaprolactane, terephthaloyl divalerolactam, (6-octanamidocapropyl) oxybenzenesulfonate, (6-nonanamidocaproyl) oxybenzenesulfonate, (6-decanarnidocaproiDoxibenceneul fonate, and mixtures thereof) 6.- A method to improve the performance of bleaching bleaching compositions comprising an oxygen or per-acid bleach or a bleaching compound capable of relax peroxide of hydrogen in an aqueous liquid and one or more bleach activators, further characterized in that said bleach activators are members selected from the group consisting of: a) an amine bleach activator derived from the general formula: or mixtures thereof, wherein R1 is an alkyl, aryl, or alkaryl group containing from 1 to 14 carbon atoms, R2, is an alkylene, arylene, or alkarylene group, containing from 1 to 14 carbon atoms RS is H or an alkyl, aryl or alkaryl group containing from 1 to 10 carbon atoms, and L is a residual group; b) a benzoxazine type bleach activator of the formula: wherein R1 is H, alkyl, alkaryl, aryl, arylalkyl, and wherein R2, R3, R * and Rs may be the same or different substituents selected from H, halogen, alkyl, alkenyl, aryl, hydroxyl, alkoxy, amino, alkylamino, -COORβ, wherein R6 is H or an alkyl group and carbonyl functions; c) N-acyl lactam bleach activators of the formula: wherein n is from 0 to 8, preferably from 0 to 2, and is H, an alkyl, aryl, alkoxyaryl, alkaryl group containing 1 to 12 carbons, or a substituted phenyl group containing from 6 to up to 18 carbon atoms; and d) mixtures of a), b) and c); wherein said improvement comprises adding thereto a catalytically effective amount of manganese cations in the presence of a ligand. 7. A method for removing stains from fabrics, hard surfaces, or dishes comprising contacting said fabrics, hard surfaces, or dishes with an aqueous medium comprising a bleaching composition in accordance with claim 1. 8.- A automatic dishwashing composition comprising a low foaming nonionic surfactant and a bleaching composition in accordance with claim 1.