MXPA96004643A - Bleaching compositions which consist of whitening catalysts that contain me - Google Patents

Abstract

Bleaching compositions for laundry having reduced fabric damage induced by bleaching catalyst containing metal selected from the group consisting of preformed organic carboxylic acids, bleaching blends containing a bleaching agent which is a source of hydrogen peroxide and one or more bleach activators , and mixtures thereof present in an amount effective to produce bleaching, a metal-containing bleach catalyst (preferably a manganese bleach catalyst) is present in an amount effective to activate the proximal compound, and wherein also the molar ratio of the hydrogen peroxide, of the preformed organic percarboxylic acids or the bleach activator, is less than about 4

Description

"" WHITENING COMPOSITIONS WHICH CONSIST OF METAL CONTAINING WHITENING CATALYSTS TECHNICAL FIELD The present invention relates to bleaching compositions (eg, granular detergent compositions and liquid bleaching additive compositions) useful for fabric washing, consisting of a metal bleach catalyst and a peroxy compound, wherein the molar ratio from hydrogen peroxide to peracids is less than about 4: 1 BACKGROUND OF THE INVENTION Catalysts containing metal have been described in bleaching compositions, including manganese-containing catalysts such as those described in EP 549,271 EP 549,272; EP 458,397; US 5,244,594; US 5,246,521; EP 458,398; US 5,194,416 and US 5,114,611. These bleach catalysts are described as active to catalyze the bleaching action of peroxy compounds against various spots. Several of these bleaching systems are purportedly effective for use in the washing and bleaching of substrates, including hard and washing surfaces (such as in dishwashers, general cleaning) and in the wood pulp, paper and textile industries . It has been found that these metal-containing bleach catalysts, especially manganese-containing catalysts, have the particularly undesired property, when used in textiles, of damaging the fabric which results in loss of tensile strength of the fibers and / or produce damage to the color of the fabric. Obviously, said properties for compositions are a great disadvantage for the - general use of these compositions in the washing area. Surprisingly, it has now been discovered that by controlling the bleaching agent ratio, which is a source of hydrogen peroxide for the bleach activator in said laundry compositions consisting of metal-containing bleach catalysts, the damage in the fabrics that results from these catalysts in the washing process. These and other objects are ensured in the present, as will be seen in the following descriptions.

TECHNICAL BACKGROUND The use of bleach activators derived from arid in laundry detergents is described in U.S. Patent 4,634,551. Another class of bleach activators consists of activators of the benzoxazine type described by Hodge et al. In U.S. Patent 4,966,723, issued October 30, 1990. The use of manganese with various complex ligands to improve bleaching is reported in the following North American 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 02.

BRIEF DESCRIPTION OF THE INVENTION The present invention relates to laundry bleaching compositions having reduced damage to fabrics induced by metal-containing bleach catalyst, said compositions consisting of: a) a peroxy compound selected from a group consisting of preformed organic percarboxylic acids, mixtures bleach containing a bleaching agent which is a source of hydrogen peroxide and one or more bleach activators, and mixtures thereof, present in an effective amount p > to give money; b) a metal-containing bleach catalyst (preferably a manganese bleach catalyst) present in an amount effective to activate the peroxy compound; and wherein furthermore the molar ratio of hydrogen peroxide to peracid, of the preformed organic percarboxylic acids or the bleach activator, is less than about 4: 1. All percentages, ratios and proportions herein are by weight, unless otherwise specified. All the documents cited, in part relevant, are incorporated herein by reference.

DETAILED DESCRIPTION OF THE INVENTION Metal-containing bleach catalyst A type of bleach catalyst is a catalyst system consisting of a heavy metal cation of defined bleach catalytic activity, such as copper, manganese iron or cations, an auxiliary metal cation having little or no catalytic bleaching activity, such as zinc or aluminum cations, and a separator having defined stability constants for the auxiliary and catalytic metal cations, particularly ethylenedia inetetraacetic acid, ethylenediaminetetr phonic acid and water soluble salts thereof. Said catalysts are described in U.S. Patent 4,430,243. Other types of bleach catalysts include the manganese-based complexes described in U.S. Patent 5,246,621 and U.S. Patent 5,244,594. Preferred examples of these catalysts include Í1niv2 (u-0) 3 (1, 4,7-trimethyl-1, 4,7-triazacyclononane) 2 - (PFβ, (u-0) α (u-OAc (1, 4, 7-trimethyl-l, 4,7-triazacyclononane) 2 (CiO_,) 2, "tlniv ^ (uO) ß (l, 4,7-triazaciclonano) 4 (CÍO)", riniUMniv ^ (u - O)? (u-0Ac) 2 (1,4, 7-trirnethyl-1,4,7-triazacyclonone) 2 (CIO *) 3 and mixtures thereof Others are described in European Patent Application Publication No. 549,272. Other suitable ligands for use herein include 1, 5,9-trirnethyl- 1, 5, 8-tr.iazacyclododecane, 2-methyl-1,4, d-triazacyclononane, 2-rnethyl, 4,7-triazacyclononane. 1,2,4,7-triazacyclononane and mixtures thereof are also included. - rnonuclear (IV) manganese complexes, such as Hniv (1, 4,7-trimethyl-1, 4,7-triazacyclononane), (OCH 3 b (PF-6) as described in the US application 5,194,416. of bleach catalyst, as described in U.S. Patent 5,114,606 is a water-soluble complex of manganese (II), (III), and / or (IV) with a ligand that is a polyhydroxy compound without carboxylate which has at minus 3 consecutive groups of C-OH ligands Preferred include sorbitol, iditol, dulsitol, mannitol, xylitol, arabitol, adonitol, eso-erythritol, eso-inositol, lactose, and mixtures thereof. U.S. Patent 5,114,611 shows a bleach catalyst consisting of a transition metal complex, which includes Mn, Co, Fe, or Cu, with a ligand that is not rnacrocyclic. These ligands are from the equation: R2 R3 R1-N = CBC = N-R4 wherein R1, R2, R3 and R4 each may be selected from groups of H, aryl and substituted alkyl, such that each Ri-N = C-R2 and R3-C = NR form a ring of 5 or 6 members, said ring can also be replaced. B is a bridging group selected from 0, S. CRSR6, wherein S, Rβ, and R7 each may be a group of H, alkyl, or aryl, including - substituted or unsubstituted groups. Preferred ligands include pyridine, pyridazino, pyrimidine, pyrazine, imidazole, pyrazole and triazole rings. Optionally, said rings can be substituted with substituents such as alkyl, aryl, alkoxy, alida, and nitro. Particularly preferred is the 2,2'-bispyridylarnine ligand. Preferred bleach catalysts include Co, Cu, Mn, Fe, -bispyridinethane and -bispyridyl ina complexes. The catalysts - highly preferred include Co (2,2'-bispyridylamine) Cl 2 of Di (isothiocyanato) bis? Iridylamine-cobalt (II), trisdipyridylamine-cobalt (II) perchlorate, CO (2,2-bispyridylarnine) 2? - 2CÍO4, bis- (2,2'-bispyridylamine) -cop? er (II), tris (di-2-pyridylamine) -fiber (II) perchlorate and mixtures thereof. Other examples include Mn gluconate, n (CF3S03) 2, Co (NH3) sCl, and the binuclear Nn complex with ligands of tetra-N-dendrite and bis-N-dentate including N4MnIII (u-0) 2MnivN4) + Bi? Y2Mnin (u-ObMniv bi? y2] - (C10 «) 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 aqueous medium and concentrating the resulting mixture by evaporation. Any convenient water soluble salt of manganese can be used herein. Manganese (II), (III), (IV) and / or (V) is now available on a commercial scale. In some cases, 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 MnSO_v, Mn (C10 «) 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 light or neutral alkaline pH. Water can initially be deoxygenated by boiling and cooling by means of nitrogen sparging. The resulting solution is evaporated (under N2, if desired) and the resulting solids are used in the detergent and bleach compositions herein without further purification. In an alternative embodiment, the source of water soluble manganese, such as MnSO.,, Is added to the cleaning / bleaching composition or to the aqueous cleaning / bleaching bath consisting of the ligand. Some type of complex apparently is formed in situ, and the performance of improved bleaching is assured. In an in situ procedure as such, it is convenient to use a considerable molar excess of the ligand over manganese, and the molar ratios of the ligand: Mn are typically from 3: 1 to 15: 1. The additional ligand also serves to purify non-fixed metal ions such as iron and copper, thus protecting the bleach against decomposition. A possible system is described in the European patent application publication No. 549,271. While the structures of the complexes of manganese bleach catalysts of the present invention have not been illustrated, it can be speculated that they consist of chelators? other hydrated coordination complexes that result from the interaction of the carboxyl and nitrogen atoms of the ligand with manganese cation. Also, the oxidation state of the manganese cation during the catalytic process is known with certainty, and it can be the valence state of (+11), (+ III), (+ IV) or (+ V). Due to the possible 6 fixation points of the ligand with the manganese cation, it can reasonably be speculated which nultinuclear species and / or "cage" structures may exist in the aqueous bleach medium. Whatever the form of the active Mn ligand species that actually exist, it functions in an apparently catalytic manner to provide improved bleaching performance in difficult to clean stains such as tea, tomato sauce, coffee, blood and the like. Other bleach catalysts are described, for example, in the European patent application, publication No. 408, 131 (cobalt complex catalysts), European patent applications, publication Nos. 384,503, and 306,089 (etaloporphyrin catalysts), US 4,728,455 (manganese ligand / multidentate catalyst), US 4,711,748 and European patent application, publication No. 224,952, (manganese absorbed in aluminosilicate catalyst), U.S. 4,601,845 (aluminosilicate support with manganese and zinc or magnesium salt), U.S. 4,626,373 (manganese / ligand catalyst), U.S. 4,119,557 (ferric complex catalyst), German patent specification 2,054,019 (cobalt chelator catalyst) Canadian patent 866,191 (salts containing transition metal), U.S. 4,430,243 (chelators with manganese cations and non-catalytic metal cations), and U.S. 4,728,455 (manganese gluconate catalysts). The bleach catalyst is used in a catalytically effective amount in the compositions and methods herein. "Catalytically effective amount" means an amount that is sufficient, under any condition of comparison test to be used, to improve the bleaching and removal of the stain or spots of importance of the desired substrate. Thus, in a fabric washing operation, the typical desired substrate will be a stained fabric, for example, with several food stains. The test conditions will vary, depending on the type of washing application used and the user's habits. Because of this, the front-loading laundry washing machines of the type used in Europe, generally use less water and higher detergent concentrations than the American-style washing machines sup >erior. Some machines have considerably longer wash cycles than others. Some users choose to use very hot water; Another uses warm and even cold water in fabric washing operations. Of course, the catalytic performance of the bleach catalyst will be affected by such considerations, and the bleach catalyst levels used in fully formulated bleach and detergent compositions can be adjusted appropriately. As a practical matter, and not by way of limitation, the compositions and methods herein may be adjusted to provide in the order of at least one part per ten million of the bleach catalyst species in the aqueous wash liquor, and preferably they will provide from about 0.1 ppm to about 700 pprn, most preferred from about 1 pprn to about 500 ppm, of the catalyst species in washing liquid. To illustrate this point further, manganese catalyst of the order of 3 rnicromolar is effective at 40 ° C, pH 10 under European conditions using perborate and a bleach activator (e.g., benzoylcaprolactam). An increase in concentration of 3 to 5 times may be required under North American conditions to achieve the same results. Conversely, the use of a bleach activator and the perganite anganase catalyst may allow the forger to achieve bleaching at lower perborate use levels than products without the manganese catalyst. The compositions herein, therefore, will typically consist of from about 1 ppm to about 1200 pprn of the bleach catalyst containing metal, preferably from about 5 ppm to about 800 pprn, and most preferred of about 10 pprn at approximately 600 pprn. The highly preferred compositions consist of bleaching catalyst Mn v (u-0) 3 (1, 4,7-trirnetyl-l, 4,7-triazacyclononane) 2 (PFß) 2 in a concentration of about 30 ppm to about 1000 ppm, preferably from about 50 ppm to about 650 pp, most preferred from about 50 ppm to about 500 ppm, and most preferred from about 120 ppm to about 400 ppm.

Peroxy compounds It should be appreciated that the bleaching catalyst does not function as a bleach by itself. Rather, co or a catalyst is used to improve the performance of conventional bleach and, in particular, oxygen bleaching agents such as perborate, percarbonate, persulfate, and the like, especially in the presence of bleach activators. Accordingly, the compositions herein also contain peroxy compounds which, used herein, include bleaching agents and 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 (for example, tea stains, wine stains). However, for purposes of the present invention, the peroxy compound should be selected from the group consisting of preformed organic percarboxylic acids, bleaching mixtures containing a bleaching agent which is a source of hydrogen peroxide and one or more bleach activators, and mixtures thereof. In addition, when a bleaching agent which is a source of hydrogen peroxide is present in the composition of the present invention, said compositions furthermore have a molar ratio of hydrogen peroxide to bleach activator less than 4: 1. The bleaching agents will typically be at levels of from about 1% to about B0%, more typically from about 5% to about 20%, of the detergent composition, especially for fabric washing. Bleach and pre-release compositions may consist of 5% to 99% bleaching agent. If present, the amount of bleach activators will typically be from about 0.1% to about 60%, more typically from about 0.5% to about 40% of the bleaching mixture consisting of the whitest bleach activating agent. 1. Bleaching agents: The bleaching agents used herein can be any of the bleaching agents useful for bleaching or detergent compositions in textile cleaning, hard surface cleaning,? other cleaning purposes that are already known or become known, and are useful for bleaching compositions as used in the "" "present invention for treating fabrics. These include oxygen bleaches as well as bleaching agents. Perborate bleaches, for example, sodium perborate (for example, mono- or tetrahydrate) may be used herein. to. Bleaching agent which is a source of hydrogen peroxide: Peroxygen bleaching agents which are a source of hydrogen peroxide can be 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 consists of dry particles having an average particle size in the range of about 500 microns to about 1000 microns, no more than about 10% by weight of said particles being less than about 200 microns and not greater than about 10% by weight of said particles being less than about 1250 microns. Optionally, the percarbonate can be coated with water soluble, borate or silicate surfactants. The percarborate is available from several commercial sources such as FMC, Solvay and To ai Denka. b. Preformed organic percarboxylic acids: As used herein, the bleaching agents also consist of preformed organic percarboxylic acids. Said bleaching agents, which can be used without restriction, surround percarboxylic acid bleaching agents and salts of the rnisrnoe. Suitable examples of this class of agents include magnesium onoperoxy phthalate hexahydrate (INTEROX), the magnesium salt of perbenzoic acid rnetachlor, 4-nonylamino-4-oxoperoxybutyric acid and diperoxydecanedioic acid. Such bleaching agents are described in U.S. Patent 4,483,781, Hartman, issued November 20, 1984, U.S. Patent Application 340,446, Burne et al, filed June 13, 1985, European Patent Application 0,133,354, Banks and others. , published February 20, 1985, and U.S. Patent 4,412,934, Chung et al., issued November 1, 1983. Highly preferred bleaching agents also include 6-nonylamino-6-oxoperoxycaproic acid (NAPAA) as described in US Pat. U.S. Patent 4,634,551, issued January 6, 1987 to Burns et al. Such materials usually have a general equation: HO-0-C (0) -RY wherein R is a substituted alkylene or alkylene group containing from 1 to about 22 carbon atoms or a substituted phenylene or phenylene group. and Y is hydrogen, halogen, alkyl, aryl or -C (0) -0H or -C (0) ~ 0-0H The organic percarboxylic acids useful in the present invention may contain either one or two peroxy groups and may be aliphatic or aromatics. When the organic percarboxylic acid is aliphatic, the unsubstituted acid has the general equation: H0-0-C (0) - (CH2) n ~ Y where Y, for example, can be H, CH3, CH2Cl, COOH, or C000H; and n is an integer from 10 to 20. When the organic percarboxylic acid is aromatic, the unsubstituted acid has the general equation: H0 ~ 0-C (0) -C6H4-Y wherein Y is hydrogen, alkyl, alkylhalogen, halogen, or COOH or C000H. Typical rnonoperoxy percarboxylic acids useful herein include alkyl percarboxylic acids and aryl percarboxylic acids such as: (i) peroxybenzoic acid and peroxybenzoic acids substituted by a ring, for example, peroxy-o-naphthoic acid; (ii) aliphatic, substituted arylalkyl and aliphatic onoperoxy acids, for example, peroxylauric acid, peroxystearic acid, and N, N-phthalolaminoperoxylic acid (POP). Typical diperoxy percarboxylic acids useful herein include alkyldiperoxy acids and aryldiperoxy acids, such as: (iii) 1,12-diperoxydecanedioic acid; (iv) 1,9-di-eroxyazelaic acid; (v) deperoxy-fibrous acid; diperoxysebacic acid and diperoxyisophthalic acid; (vi) 2-decyliperoxy uta or l, 4-dioic acid; (vii) 4,4 '-sulfonbisperoxybenzoic acid. The present invention may further include bleaching compositions which consist of an effective amount of an insoluble organic percarboxylic acid bleaching agent having the general equation: 0 0 0 0 R1-CN-R2-C-00H R1 -NC-R2 -C-00H RS RS Where R * is? N alkyl, aryl, or alkaryl group containing d? About 1 to about 14 carbon atoms; carbon, R 2 is an alkylene, arylene or alkarylene group containing from about 1 to about 14 carbon atoms, and R 5 is H or an alkyl, aryl, or alkaryl group containing from about 1 to about 10 carbon atoms. carbon. Peroxygen bleaching agents, perborates, percarbonates, etc., are preferably combined with bleach activators, which lead to in situ production. in aqueous solution (ie, during the "" washing procedure) of the percarboxylic acid corresponding to the bleach activator. 2. Bleach Activators Bleach activators are known and widely described in the literature, such as in GB 836,988; 864,798; 907,356; 1,003,301 and 1,519,351; German Patent 3,337,921; EP-A-0185522; EP-A-0174132; EP-A-0120591 and U.S. Patent Nos. 1,246,339; 3,332,882; 4,128,494; 4,412,934 and 4,675,393. One class of bleach activators is that of peroxyacid activators substituted with quaternary ammonia as described in U.S. Patent Nos. 4,751,015 and 4,397,757, in EP-A-284292, EP-A-331,229 and EP-A-03520. Examples of peroxyacid bleach activators of this class are: 2- (N, N, N-trirnethyl ammonia) ethyl-4-s-l-phenylphenylcarbonate - (SPCC); N-octyl chloride, N, N-dirnethyl-N-10-carbofenoxidecil-arnoniaco ~~ (ODC); 3- (N, N, N-tri ethylammoniaco) -3-eulpheno-carbonate - (SPCC); and N, N, N, -trimelamoniaco toliloxybenzene sulfate. Other activators include sodium 4-benzoyloxybenzenes; N, N, N ', N' -tetracetylethylenediarnine; Sodium 1-rnethyl-2-benzoyloxybenzene-4-sulfonate; Sodium 4-methyl-3-benzoyloxybenzoate; sodium nonanoyloxybenzene fonate; 3,5,5, -trimethylhexanoyloxybenzenesulfonate sodium; glucose pentaacetate and tetraacetyl xylose. The bleach activators also useful in the present invention are substituted amide compounds of the general equations: 0 0 0 0 R -C -N-R2 -C-00H Rl -N-CII-R.2 -C -00H RS RS or mixtures thereof, wherein R1 is an alkyl, aryl, or alkaryl group contains about 1 to about 14 carbon atoms, R 2 is an alkylene, arylene or alkarylene group containing about 1 to about 14 carbon atoms, RS is H or n alkyl, aryl or alkaryl group containing about 1 to about 10 carbon atoms, and L may essentially be any suitable 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 dry oxide anion. This, the reaction of μerohydrolysis, results in the formation of peroxy carboxylic acid. Generally, for a group to be an adequate residual group, it must exert an electron-attracting effect. It must also form a stable entity so that the speed of the reaction is negligible. This facilitates the nucleophilic attack by means of the anion perohidróxido. The L group must be reactive enough for the reaction to occur within the optimal time frame (eg,? N 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 paralleled by the pKa of the conjugated acid of the starting group, although exceptions to this invention are known. Commonly, residual groups exhibiting said behavior are those in which their conjugate acid has a pKa on the scale of about 4 to about 13, preferably about 6 to about 11 and most preferred about + 8 about 11. The preferred bleach activators are those of the above general equation wherein R, R2 and RS are defined for the peroxy acid and L is selected from a group consisting of and mixtures thereof wherein R 1 is an alkyl, aryl or alkaryl group, which contains about 1 to about 14 carbon atoms, R 3 is an alkyl chain containing from about 1 to about 8 carbon atoms , R * is H or R3, and Y is H or a solubilizing group.

Preferred solubilizing groups are -S03_M +, - C? 2"M +, -S04- +, -N-MR3) _, X- Y 0 <--N (R3) 3 and most preferred -SO3- M + and -C02"M +" wherein R3 is an alkyl chain containing about 1 to about 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 a substituted ammonia cation or alkali metal ammonia, with sodium and potassium being most preferred, and X is a halide, hydroxide, rnetylsulfate or acetate anion. It should be emphasized that the bleach activators with a residual group that do not contain solubilizing groups must deviate in the bleaching solution to aid in their dissolution. Preferred bleach activators are those of the above general equation wherein L is selected from the group q? E consisting of: where R3 is defined as shown above and Y is -S03 ~ M +, -C02 ~ M + where M is as defined earlier. Preferred examples of bleach activators of the above equation include 6-octancanecaproi lox ibencen- 00 sulfonate, 6-nonanamidocaproyloxybenzenesulfonate, d-decanaride-caproyloxybenzene, and fonate and mixtures thereof. Another important class of bleach activators provides organic peroxides as described herein by means of a ring opening as a consequence of the nucleophilic attack on the carbonyl carbon of the cyclic ring by means of the perhydroxide anion. For example, this ring opening reaction in certain activators involves an attack on the lactam ring carbonyl by means of hydrogen peroxide or its anion. Because the attack on an acyl-lactam by hydrogen peroxide or its anion occurs preferably in the exocyclic carbonyl, obtaining a significant fraction of the ring opening may require a catalyst. Another example of ring opening bleach activators can be found in other activators, such as those described in U.S. Patent 4,966,723, Hodge et al., Issued October 30, 1990. Said activating compounds described by Hodge include activators of the benzoxazin type. , which has the equation: including the benzoxazinoe substituted of the type wherein Ri is H, alkyl, alkaryl, aryl, arylalkyl, and wherein R2 R3, * 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 carbonyls functions.) A preferred activator of the benzoxazine type is: when the activators are used, optimum performance of surface bleaching is obtained 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 to facilitate the perhydrolysis reaction. Said pH can be obtained with substances commonly known as regulating agents, which are optional components of the bleaching systems herein.

Still another class of preferred bleach activators includes acyl-lactarine activators, especially acylcaprolactam ace and acylvalerolactrarnes of the formula: wherein R6 is H, alkyl, aryl, alkoxyaryl, or alkaryl containing from 1 to about 10 carbon atoms, or a group > or substituted phenyl containing from about 6 to about 18 carbons. See also U.S. Patent 4,545,784, issued to Sanderson, October 8, 1985, incorporated herein by reference, which discloses acyl caprolactams, including benzoyl caprolactans, -sorbed in sodium perborate. Various non-limiting examples of additional activators which may consist of bleaching compositions described herein include those in U.S. Patent 4,915,854, issued April 10, 1990 to Mao et al., P >American attempt 4,412,934. The activators of nonanoyloxybenzenesitone (NOBS) and tetraacetylmethylene diamine (TAED) are typical, and mixtures thereof can also be used. See also U.S. 4,634,551 for other typical bleaches and activators useful in the present. The superior cleaning / bleaching action of the present compositions is also preferably safely achieved to natural rubber machine parts 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. However, it is generally believed that the bleach activator undergoes the nucleophilic attack by an anion p > eridroxide, which is generated from the hydrogen peroxide developed by the peroxygen bleach, to form a peroxycarboxylic acid. This reaction is commonly known as peridrolysis. The lactase bleach activators and derivatives of arnine herein can also be used in combination with activators preferably hydrophilic, above followed, of safe rubber, such as TAED, typically at weight ratios of activators of caprolactam or of amido derivatives: TAED in the scale from 1: 5 to 5: 1, preferably approximately 1: 1.

Component Relations: For purposes of the present invention, it is important to control the molar ratio of hydrogen peroxide to peracids (preformed or from bleach activators) is less than about 4: 1 and is preferably within a specific limit, for obtaining the desired reduction in fabric damage of the metal-containing bleach catalyst: it is further preferred that the molar ratio of hydrogen peroxide to heavy metal ions of the bleach catalyst be controlled. The molar ratio of hydrogen peroxide to peracid is defined herein to be the molar concentration of hydrogen peroxide obtained from the bleaching agent which is -a source of hydrogen peroxide (CH202)) at the theoretical molar concentration of p > eracts generated by the bleach activator plus any preformed peracid compound present in the composition ([peracid]) for example, a mole of percarbonate will provide 1.5 moles of hydrogen peroxide and a mole of perborate will generate a hydrogen peroxide template; [H202] of said sources p > They are therefore calculated based on these values and the molar concentration of the bleaching agent which is a source of hydrogen peroxide are used. Similarly, for the bleach activators used in the compositions, the [peracid] is calculated by recognizing that, for example, a TAED mole will theoretically provide 2 peracids; for this the [peracid] is twice the molar concentration of TAED. The molar ratio of [H202] [peracid] is therefore less than about 4: 1, preferably between 1: 1 and 3: 1, and u and preferably between 1.02: 1 2.5: 1. Also preferred for the present compositions, when the compositions contain more than about 20 ppm of heavy metal ions provided by the bleach channel (therefore, it does not include non-catalytic heavy metal ions in the compounds or ions of heavy metal fortuitously present in the wash solution), is the control of the molar ratio of hydrogen peroxide to metal ions p > provided by the bleach catalyst ([H202]: [HMI]) to less than about 1200: 1. Also preferred is the control of the ratio of peracid to heavy metal ions of the bleach catalyst ([perished]: [MNI]) greater than about 350: 1, preferably greater than about 500: 1, and much preferred over around 700: 1. The molar concentration of the heavy metal ions of the bleach catalyst ([HMI]) is obtained from the molar concentration of the bleach catalyst by the number of heavy metal ions per catalyst. By - "example, the preferred catalyst Mn * v2 (u-0) 3 (1,, 7-trimetil- 1, 4, 7-triazaciclononano) 2 - (PFß provides two moles of MN per catalyst rnol, hence the [ Finally, for the Mn caused by the catalyst is equivalent to twice the molar concentration of the catalyst Finally, it is further preferred for the present invention that the compositions consist of less than about 50 ppm of heavy metal ions caused by the catalyst. , and very preferred of less than about 40 pprn.

Auxiliary ingredients The compositions herein may optionally include one or more other detergent auxiliary materials or other materials to aid or improve cleaning performance, treatment of the substrate to be cleaned, or to modify the aesthetics of the detergent composition (e.g. , 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, the dishwashing formulations are preferably free of chlorine. The following are illustrative examples of said auxiliary materials.

Radical free radical antioxidant materials: "Antioxidant free radical scavenging materials", as used herein, means those materials that act to prevent oxidation in products by functioning as free radical scavengers. Examples of antioxidants that can be added to the compositions of this invention include a mixture of ascorbic acid, ascorbic palmitate, propyl gallate, available from Eastman Chemical Products., Inc., under the trade names Tenox® PG and Tenox Sl, a blend of BHT. (butylated hydroxytoluene), BHA (butylated hydroxyanisole), propyl gallate and citric acid, available from Eastman Chemical Products, Inc. under the tradename Tenox-6, butylated hydroxytoluene, available from UOP Proceee Divieion under the tradename Sustane® BHT; tertiary butyl ironquinone, Eastman Chemical Products, Inc., as Tenox TBHQ; natural tocopherols, Eastman Chemical Products Inc. as Tenox GT-1 / GT-2 and butylated hydroxyanisole; Eastman Chemical Prod? Ctce, Inc., as BHA; esters in long chain (C8-C22), of gallic acid, for example, dodecyl gallate; Irganox® 1010; Irganox® 1035, Irganox® B 1171; Irganox® 1425; Irganox® 3114; Irganox® 3125; or tert-butylhydroquinone ((MTBHQ), benzoic acid and salts thereof, tucumic acids and salts of the same, t-butylcatechol; 1,1-tris (2-methyl-4-hiroxy-5-t- butiphenyl) butan (topanol CA available from ICI), hydroquinone (or 4-methoxy phenol) onoalkylethers, and mixtures thereof Preferred are BHT, BHA, TBHQ, propyl gallate, ascorbic acid and mixtures thereof. It should be recognized that for the purposes of the present invention, materials otherwise useful as antioxidants that do not act as free radical scavengers, such as those materials that only work by chelating metals that can initiate oxidation reactions are not "antioxidant materials". free radical scavengers "herein, but are optional preferred material for use with free radical scavenging antioxidant materials The term" antioxidant effective amount "as used herein, means a quantity d of free radical scavenging antioxidant material effective to reduce, under any comparative test condition employed, the degree of any damage to fabrics (including, for example, loss of tensile strength and / or color damage) observed by the presence of bleach catalyst containing metal in the composition. Such damage to the fabric can be evaluated under any typical washing condition, including washing conditions common in Europe above 40 ° C. The levels of free radical scavenging antioxidant materials q will be used in the products, therefore they are easily determined, and are typically present in the compositions according to the present invention within the range of about 1 ppm to about 2. %, preferably from about 20 ppm to about 6000 ppm, and most preferred from about 50 ppm to about 2000 ppm. In addition, in a powder formation, the antioxidant can be introduced into the formulation as a powder or through agglomeration or granulation or any other method to keep the catalyst and antioxidant close to each other and also allow rapid interaction in the wash. 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. Detergency builders are typically used in fabric washing compositions to help remove particulate soils. The level of builder can vary widely depending on the final use of the composition and its desired physical form. When present, the compositions will typically comprise at least about 1% builder. Liquid formulations typically comprise from about 5% to about 50%, very typically from about 5% to about 30%, by weight of builder. Granulated formulations typically comprise from about 10% to about 80%, very typically from about 1.5% 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: Na 2 ratio. in the scale of 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 "SKS-6"). Unlike zeolite builders, the NaSKS-6 silicate detergent builder does not contain aluminum. NaSKS-6 has the morphological form of stratified silicate delta-Na2Si0s. 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 NaMSi 2x +? and H2" wherein M is sodium or hydrogen, x is a number from 1.9 to 4, preferably 2, and y is a number from 0 to 20, preferably 0 can be used here Some other stratified silicates from Hoechst include NaSKS-5, NaSKS-7 and NaSKS-11 as the alpha, beta and gamma forms As noted above, the delta-Na2Si0s form (NaSKS-6) Other silicates can also be used such as for example magnesium silicate, which can serve as a tightening agent in granulated formulations, as a stabilizing agent for oxygen bleaches, and as a component of systems. of foam control. Carbonate builders are the alkali metal and alkali metal carbonates as described in German Patent No. 2,321,001 published November 15, 1973. The detergents of aluminosilicate are useful in the present invention. Aluminosilicate builders are of great importance in most heavy duty granular detergent compositions currently co-cilated, and can also be an important detergency builder ingredient in liquid detergent formulations. The aluminosilicate 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 aluminosilicates can be of crystalline or amorphous structure and can be alu inosilicates that occur naturally or synthetically derived. A method for producing aluminosilicate ion exchange materials is described in U.S. Patent 3,985,669, Kr? Nnel and others 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 crystalline aluminosilicate ion exchange material has the formula: ai2 Í (A102) 12 (SIO2) l 2 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 approximately 0.1-10 microns in diameter. Organic builders suitable for the purposes of the present invention include, but are not '*' * are re-labeled 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 detergents can generally be added to the compound in acid form, but they can also be added in the form of a neutralized salt.When used in salt form, the alkali metals such as sodium, potassium and lithium, or alkanolamine salts Onium are preferred. Included among polycarboxylate builders are a variety of categories of useful materials An important category of polycarboxylate builders include 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 19, 19 72. 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 They are described in U.S. Patent 3,923,679; 3,835,163; 4,158,635; 4,120,874 and 4,102,903. Citrate detergency builders, e.g., citric acid and soluble salts thereof (particularly "sodium salt", are polycarboxylate detergent enhancers of particular importance for the formulation of heavy duty liquid detergents due to their availability from renewable resources and their biodegradability. The citrates 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. Fatty acids, e.g., C12-C18 onocarboxylic acids / can also be incorporated into the compositions by themselves, or in combination with the aforementioned detergency builders, especially citrate and / or succinate builders, to provide additional detergency activity. Said use of fatty acids will generally result in the decrease of spurnation, which would be considered by the fornulator. 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 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. Nevertheless, nitrogen-based manganese quenching agents, such as ethylenediamine-N, N'-disuccinate (EDDS), are useful. Detersive Surfactants - Non-limiting examples of additional amide non-amide surfactants, useful herein include the conventional Cn-Ciß alkylbenzenes? Lonates ("LAS") and the C10-C20 alkyl lactates ( "AS") primary, branched chain and random, the alkylsul fatoe (2,3) secondary Cío-Ciß of the formula CH3 (CH2) x (CH0S03-M +) CH3 and CH3 (CH2) and (CH0S03 ~ M +) CH2CH3 wherein xy (y + 1) are integers of at least 7, preferably at least about 9, and M is a soli cation cation in water, especially sodium, unsaturated sulaphthates such as oleum sulfate, alkylalkoxysulphates of Cio -Ciß ("AE? S"; especially ethoxysulfates EO 1-7), alkylalkoxycarboxylates of Cι-Ciß (especially the ethoxycarboxylate EO 1-5), the glycolic ethers of Cι-Ciß, the alkyl polyglycosides of Cι-Ciß and their corresponding sulfated polyglycosides, and alphasulfonated fatty acid esters of C12-C18. If desired, conventional non-ionic amphoteric surfactants such as C12-C18 alkyl ethoxylate ("AE") including the so-called narrow peak alkyl ethoxylates and the C6-C12 alkyl phenoalkoxylates (especially mixed ethoxylates and ethoxy / propoxy), betaines of C12-C18 and sulfobetaines ("s? Ltains"), amine oxides of C? O ~ C? ß, and the like, can also be included in the overall compositions. N-alkyl polyhydroxyl fatty acid amides can also be used. Typical examples include C12-C18 N-rnethylglucarnines. See UO 9,206,154. Other surfactants derived from sugar include the N-alkoxy polyhydric fatty acid amides, such as N- (3-methoxypropyl dihydro-Cys-Ciß- N-propyl to C12-C18 N-hexylglucamides can be used for low spurnation. Conventional C10-C20 soaps can also be used Mixtures of anionic and nonionic surfactants are especially useful Other conventional useful surfactants are listed in the standard texts Nonionic surfactants particularly suitable for dishwashing are alcoholic alcohols. Straight chain low foaming or non-foaming ethoxylates such as? Plurafac ™ of the RA series, supplied by Eurane Co., Luteneol ™ LF series, supplied by BASF Co., TritonTM DF series, supplied by Rohm »Haas Co., and Synperonic ™ LF series, supplied by ICI Co. Clay soil removal / anti-redeposition agents.- The compositions of the present invention can also be It can optionally contain water-soluble ethoxylated amines that have clay 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 preferred soil repellent and anti-redeposition agent is tetraethylene pentane ethoxylated. Example ethoxylated amines are more fully described in the U.S. Patent. 4,597,898, VanderMeer, issued July 1, 1986. Another group of clay removing / anti-redeposition agents with the cationic compounds described in European Patent Application 111,965, Oh and Gosselink, published June 27, 1984. Other clay soil removers / anti-redeposition agents that can be used include the ethoxylated amine polymers described in European Patent Application 111,984, Gosselink, published June 27, 1984; the zwitterionic polymers described in the Europ 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 type of anti-redep agent > Preferred composition includes the carboxyl ethyl cellulose (CMC) materials. These materials are well known in the art. Polymeric Dispersing Agents - Polymeric dispersing 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 zeolite builders and / or layered silicate. . Suitable polymeric dispersing agents include polymeric polycarboxylates and polyethylene glycols, although others known in the art may also be used. It is believed, although it is not intended to limit the theory, that polymeric dispersing agents increase the performance of the overall detergency builder, when used in combination with other detergency builders (including lower molecular weight polycarboxylates) by inhibition of crystal growth, peptization of particulate and anti-dirt release. -redeposition. Polymeric polycarboxylate materials can be prepared by spraying or copolyzing suitable nitrite monomers, preferably in their acid form. The unsaturated monomeric acids which can be polimerized to form suitable polymeric polycarboxylates include acrylic acid, rnaleic acid (or rnaleic anhydride), fumaric acid, itaconic acid, aconitic acid, mesaconic acid, citraconic acid, methylene allyl. The presence of the polyarmer polycarboxylates in the present or polymeric segments, which do not contain carboxylate radicals such as 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 acrylic acid-based polymers which are useful herein are the water-soluble salts of polymerized acrylic acid. The average molecular weight of such polymers in the acid form perferably varies from about 2,000 to 10,000, most preferably from about 4,000 to 7,000 and most preferably from about 4,000 to 5,000. The water-soluble salts of said acrylic acid polymers can include, for example, the alkali metal, ammonium and substituted ammonium salts. Soluble polymers of this type are known materials. The use of polyacrylates of this type in detergent compositions has been described, for example, in Diehl, U.S. Pat. 3,308,067, issued on March 7, 1967.

Acrylic / aleic acid-based copolymers can also be used as a preferred component of the dispersing / anti-redeposition agent. Such materials include the water-soluble saltse of copolymers of acrylic acid and rnaleic 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 the maleate loe 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. Soluble acrylate / maleate copolymers of this type are known materials which are described in the Application European Patent No. 66915, published December 15, 1982. Another polymeric material that can be included is polyethylene glycol (PEG). The PEG can exhibit dispersing agent performance and can act as a clay dirt removal / anti-redeposition agent. Typical molecular weight scales for this purpose vary from about 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 detergent builders. Dispersing agents such as those of preferable polyaspartate have a molecular weight (avg.) Of about 10,000. Enzymes.- Enzymes may 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, amylases, lipases, cellulases and peroxidases, as well as mixtures thereof. Other types of enzymes can also be included. They can be of any suitable origin, such as plant, animal, bacterial, mycotic and yeast origin. However, its choice is governed by several factors such as pH activity and / or optimum stability, stability, stability against active detergents, builders, etc. In this regard bacterial and fungal enzymes are preferred, such as bacterial amylases and proteases and fungal cells. 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. lichenifor s. Another suitable protease is obtained from a strain of Bacillus that has maximum activity throughout the pH regime of 8-12, developed by Novo Indudtries 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 commercially available proteolytic enzymes suitable for removing protein-based stains include those sold under the registered trademarks ALCALASE and SAVINASE by Novo Industries A / S (Denmark) and MAXATASE by 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 on April 28, 1987 and the European Patent Application. 130,756, Bott et al., Published January 9, 1985). The arnilasae include, for example, a-arnilasa described in British Patent Specification No. 1,296,839 (Novo), RAPIDASE, International Bio-Synthetics, Inc. and TERMAMYL. Novo Industries 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. Suitable lipase enzymes for use in detergents include those produced by microorganisms of the Pseudomonas 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, lipaeas of ex Chromobacter viscosu, e.g. Chromobacter viscos? M var. lipolyctum NRRLB 3673, commercially available from Toyo Jozo Co., Tagata, Japan; and in addition the Chromobacter viscosum lipases from U.S. Boiche ical Corp., E.U.A. and Disoynth Co., The Netherlands, and the lipases of ex Pseudomonas gladioli. The LIPOLASE enzyme derived from Humicola lan? Ginosa 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, perborate, 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.The peroxidase enzymes are known in the art and include, for example , horseradish peroxidase, ligninase and halogenoperoxidase such as chloroperoxidase and bromoperoxidase Detergent compositions containing peroxidase are described, for example, in International Application PCT UO 89/099813, published on October 19, 1989 by Kirk. Novo Indudtriee A / S A wide variety of enzyme materials and means for their incorporation into synthetic detergent compositions are described in US Patent 3,553,139 issued January 5, 1971 to McCarty et al. Additionally, enzymes are described in the US Patent. 4,101,457, Place et al., Issued July 18, 1978 and in US Patent 4,507,219, Hughes, both issued on March 26. 1985. Useful enzyme materials for liquid detergent formulations and their incorporation into such formulations are described in the U.S. Pat. 4,261,868, Hora et al., Issued April 14, 1981. Enzymes p > For detergents can be stabilized by various techniques. 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, Venegas. Enzyme stabilization systems are also described, for example, in the U.S. Patent. 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 most preferably from about d to 8 to about 12 millimoles of calcium per liter of finished composition. This may somehow vary, depending on the amount of enzyme present and its response to calcium or magnesium ions. The level of calcium or magnesium ions should be selected in such a way 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 rnalate, calcium maleate, calcium hydroxide, calcium and calcium acetate and the corresponding magnesium salts. Frequently, a small amount of calcium ions, usually around 0.05 to about 0.4 millimoles p >or liter, is also present in the composition due to the calcium present in the enzyme suspension and the water of the formula. 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 typically should comprise from about 0.05% to about 2% by weight of a water soluble supply 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 rnetaborate 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 instead 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 may be classified into subgroups, including, but not necessarily limited to, stilbene, pyrazoline, cuino, carboxylic acid, rhetinocyanin, 5,5-dibenzothiophene dioxide derivatives, azoles, 5- and 6-membered heterocyclics, and various other agents. Examples of such brighteners are described in "The Production and Application of Fluorescent Brightening Agents," M. Zahradnik, published by John Uiley in 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 PHOROUHITE series of brighteners from Verona. 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, based in Italy; the 2- (4-estri-phenyl) -2H-naphthol [1,2-dHriazoles; 4,4'-bis (1, 2, 3-triazol-2-2-yl) -stilbenes; 4,4'-bisbistriD bisphenyls; and the inocumarinas. Specific examples of these brighteners include 4-rnethyl-7-diethyl-a -nocoumarin; 1, 2-bie (-benzimidazol-2-yl) ethylene; 1,3-diphenyl-frazolines; 2,5-bis (benzoxazol-2-yl) thiophene; 2-Stryl-naph- [1,2-d] oxazole; and 2- (eethylben-4-yl) -2H-naphtho- [1,1 l, 2-d] triazole. See also patent of E.U.A. 3,646,015, issued on February 29, 1972 to Hamilton. Anionic brighteners are preferred here. Eepurnas Suppressants - Compounds to reduce or suppress the formation of foams can be incorporated into the compositions of the present invention. The suppression of foams can be of particular importance in the "high concentration cleaning procedure" and in European front-loading washing machines.

A wide variety of materials can be used as foam suppressors, and foam suppressors are well known to those skilled in the art. See, for example, Kirk Othrner Encyclopedia of Chemical Technology, 3a. Edition, Volume 7, pages. 430-447 (John Uiley dt Sone, Inc., 1979). A category of spurnae suppressant of particular interest includes monocarboxylic fatty acids and soluble salts thereto. See U.S. Patent 2,954,347, issued September 27, 1960 to Uayne St. John. The monocarboxylic fatty acids and salts thereof 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 ammonium and alkanola onium salts. The detergent ingredients herein may also contain foam suppressors which are not surfactants. These include, for example: high molecular weight hydrocarbons such as paraffin, fatty acid esters (e.g., triglyceride fatty acid), fatty acid esters of monovalent alcohols, C18-C40 aliphatic ketones (e.g. , stearone), etc. Other foam inhibitors include N-alkylated aminotriazines such as tri- to hexa-alkylmelamines or di- to tetra-alkyldiarninoclotriazines 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 rnononetearyl phosphates such as rnonostearyl alcohol phosphate ester and alkali metal (eg, K, Na and Li) diphosphates monostearyl and ester phosphates. Hydrocarbons such as paraffin and halogenoparaffins 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 hydrocarbon foam suppressors are described, p > or example, in the Patent of U.S.A. 4,265,779 issued on August 5, 1981 to Gandolfo et al. The hydrocarbons, therefore, include saturated or unsaturated aliphatic, alicyclic, aromatic and heterocyclic hydrocarbons having from about 12 to about 70 carbon atoms. The term "paraffin" as used in the discussion of suds suppressors, is intended to include mixtures of true paraffins and cyclic hydrocarbons. Another preferred category of foam suppressors that are not surfactants comprise silicone foam suppressors. This category includes the use of oiorganosiloxane oils such as polydimethylsiloxane, dispersions or emulsions of polyorganosiloxane oils or resins, and combinations of polyorganosiloxane with silica particles wherein the polyorganosiloxane is chemoabsorbed or fused onto the silica. Silicone foam suppressors are well known in the art and are described, for example, in 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 US Patent 3,455,839 which refers to compositions and processes for the dewatering of aqueous solutions incorporating thereto small amounts of polydimethylsiloxane fluids. Silica and silanated silica mixtures are described, for example, in German Patent Application DOS 2,124,526. Silicone foam scavengers and foam controlling agents in granular detergent compositions are set forth in US Pat., 933,672, Bartolotta et al. And in U.S. Patent 4,652,392, Baginski et al., Issued March 24, 1987. An illustrative silicone-based foam suppressant to be used herein is a suppressive amount of foam from a controlling agent. of foams which consists essentially of: (i) polydirnethylsiloxane fluid having a capacity of about 20 is at 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) 3Si0? / 2 units of SiO units? in a ratio of units of (CH3) 3SiO? / 2 to units of SIO2 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 suppressor used herein, the solvent for a continuous phase is made of certain polyethylene glycols or copolymers of polyethylene-polypropylene glycol or mixtures thereof (preffered) and non-polypropylene glycol. The primary silicone foam suppressor is branched / interlaced and non-linear. To illustrate this point further, typical liquid laundry detergent compositions with optionally controlled sprays will comprise from about 0.001 to about 1, preferably from about 0.01 to about 0.7, most preferably from about 0.05 to about 0.5,% by weight of said s? silicone foam pressor, 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 resin-producing silicone compound of 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) ptolyethylene 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 foam suppressant of the present preferably comprises polyethylene glycol and a polyethylene glycol / polypropylene glycol copolymer, all having a lower average molecular weight of about 1,000, preferably between about 100 and 800. Polyethylene glycol and polyethylene copolymers / p > olipropylene of the present have a solubility in water at room temperature other than about 2% by weight, preferably more than about 5% by weight. The preferred solvent herein is polyethylene glycol having an average molecular weight of 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 about 1: 1 and 1:10, most preferably between 1: 3 and 1: 6, of polyethylene glycol: polyethylene-polypropylene glycol copolymer is preferred. Preferred silicone foam suppressors used herein do not contain polypropylene glycol, particularly of molecular weight of 4,000. Preferably they also do not contain block copolymers of ethylene oxide and propylene oxide, such as PLURONIC L101. Other supreeorea of foams useful herein contain the secondary alcohols (e.g., 2-alkylalkanols) and mixtures of said alcohols with silicone oils, such as the silicones described in US Pat. No. 4,798,679, 4,075,118 and EP 150,872. Secondary alcohols include Cß-Ciß alkyl alcohols having a Ci-Cid chain. A preferred alcohol is 2-butyloctanol, which is available from Condea under the trade name ISOFOL 12. Ethanol secondary alcohol mixtures available under the trade name ISALCHEM 123 from Enichern. The mixed foam suppressors typically comprise alcohol + silicone blends at a weight ratio of 1: 5 to 5: 1. For any detergent compositions to be used in automatic washing machines, the foams should not be formed to the extent that they overflow from the washing machine. The foam suppressors, when used, are preferably present in an amount of spurious suppression. By "foam eupressure 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 suds suppressors, the monocarboxylic 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 monocarboxylate fatty acid suppressant is used. Silicone foam suppressors are typically used in amounts of up to about 2.0%, by weight, of the detergent composition, although higher amounts may be used. 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 foaming. Preferably from about 0.01% to about 1% suppressant d is used silicone foams, 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. Ultrasonic phosphate foam suppressors are generally used in amounts ranging from about 0.01% to about 02% by weight of the composition. The hydrocarbon foam suppressors are typically used in amounts ranging from about 0.01% to about 5.0%, although higher levels can be used. The alcohol foam suppressors are typically used at 0.2% -3% by weight of the finished compositions. Fabric softeners.- Various fabric softeners that soften during washing, especially the impalpable srnectite clays of the U.S. Patent. 4,062,647, Stor and Nirschl, issued December 13, 1977, as well as other softening clays known in the art, optionally they can be used typically at levels of from about 0.5% to 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 U.S. Patent. 4,375,416, to Criep 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, cop >N-vinylpyrrolidone and N-vinylnidazole olifers, manganese phthalocyanine, peroxidases and mixtures thereof. If used, these agents typically comprise from about 0.01% to about 10% by weight of the composition, preferably from about 0.01% to about 5%, and most preferably from about 0.05% to about 2%. Very specifically, the preferred polyamine N-oxide polymers for use herein contain units having the following structural formula: R-A? -P; wherein P is a polymerizable unit to which a group N-0 may be attached or group N-0 may form part of the polymerizable unit or group N-0 may be attached to both units; A is one of the following structures: -NC (0) -, -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 thereof to which the nitrogen of the group N-0 can be attached or the group N-0 is part of these groups. The preferred polyarynin N-oxides are those wherein R is a heterocyclic group such as pyridine, pyrrole, imidazole, pyrroline, piperidine and derivatives thereof. The group N-0 can be represented by the following general structures: O O (Rl) X-N- (R2) y = N- (R?)? I R3) x 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 N-oxides of the polyamine has a? Ka < 10, preferably? Ka < 7, very preferably still? Ka < 6. Any polymer base structure can be used as long as the amine oxide polymer formed is soluble in water and has dye transfer inhibiting properties. Examples of suitable polymeric base structures are polyvinyls, polyalkylenes, polyesters, polyethers, polyamides, polyamides, polyacrylates and mixtures of - the same. These polymers include random or block copolymers in which one type of rnonomer is an N-oxide amine 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 polyarynn oxide polymer can be varied by appropriate copolymerization or by an appropriate degree of N-oxidation. The polyamine oxides can be obtained in almost any degree of polymerization. Typically, the average molecular weight is within the range of 500 to 1,000,000; very preferred from 1,000 to 500,000; even more preferred 5,000 to 100,000. The N-oxide of p > Most preferred oliarnine useful in the detergent compositions herein is the poly-4-vinylpyridine N-oxide which has 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 (known as "PVPVI") are also preferred for use in the present. Preferably, the PVPVI has an average molecular weight in the range of 5,000 to 1,000,000, most preferably 5,000 to 200,000 and most preferably even 10,000 to 20,000. (The average molecular weight scale is determined by light scattering as described in Barth, and other Chemical Analysis, Vol. 113. "Modern Methods of Polymer Characterization", the descriptions of which are incorporated herein by reference). PVPVI copolymers typically have a molar ratio of N-vinylimidazole to N-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 may also employ a polyvinylpyrrolidone ("PVP") which has an average molecular weight of from about 5,000 to about 400,000, preferably from about 5,000 to about 200,000, and most preferably still from about 5,000 to approximately 50,000. PVP's 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 PVP-containing compositions may also contain polyethylene glycol ("PEG") having an average molecular weight of from about 500 to about 100,000, preferably from about 1,000 to about 10,000. Preferably, the ratio of PEG to PVP on a basis of ppm assorted in wash solutions is from about 2: 1 to about 50: 1, and most preferably from about 3: 1 to about 10: 1. The detergent compositions herein may also optionally contain from about 0.005% to 5% by weight of certain types of hydrophilic optical brighteners that also provide a dye transfer inhibiting action. If used, the compositions herein will preferably comprise from about 0.01% to 1% by weight of said optical brighteners. The hydrophilic optical brighteners useful in the present invention are those which have the structural formula: wherein Ri is selected from anilino, N-2-bie-hydroxyethyl and NH-2-hydroxyethyl; R 2 is selected from N-2-bis-hydroxyethyl, N-2-hydroxyethyl-N-methylamino, morphino, chloro and amino; and M is a salt-forming cation such as sodium or potassium. When in the above formula, Ri is anilino, R2 is N-2-bis-hydroxyethyl and M ee a cation such as sodium, the brightener is acid 4,4 ', bis [(4-anilino-6- (N-2 bis-hydroxyethyl) -s-triazin-2-yl) ami or] -2,2'-stilbenedisulfonic acid and disodium salt. This particular brightener species is commercially marketed under the trade name Tinopal-UNPA-GX by Ciba-Geigy Corporation. Tinopal-UNPA-GX is the preferred hydrophilic optical brightener? Itl in the detergent compositions of the present invention. When in the above formula R1 is anilino, R2 is N-2-hydroxyethyl-N-2-rnetilarnino and M is a cation such as sodium, the brightener is the disodium salt of 4,4'-bis [4- anilino-6- (N-2-hydroxyethyl-N-methylamino) -s-triazin-2-yl) arnino] -2,2'-stilbenedisulfonic acid. This particular brightener species is traded commercially under the trade name Tinopal 5BM-6X by Ciba-Geigy Corporation. When in the above formula R1 is anilino, R2 is morphino and M is a cation such as sodium, the brightener is the sodium salt of 4,4'-bis [(4-anilino-6-morphino-s-triazin- 2-yl) amino] 2,2'-stilbenedisulfonic acid. This particular kind of brightener is sold commercially under the trade name Tinopal AMS-GX by Ciba-Geigy Corporation. The kind of optical brightener esp > selected for use in the present invention provides speci? cally effective dye transfer inhibition performance benefits when used in combination with the selected polymeric dye transfer inhibiting agents described above. The combination of said selected polymeric materials (e.g., PVNO and / or PVPVI) with said selected optical brighteners (e.g., Tinopal UNPA-GX, Tinopal 5BM-GX and / or Tinopal AMS-GX) provides inhibition of dye transfer significantly better in aqueous wash solutions than either of those two components of detergent composition when used alone. Without being limited to the theory, it is believed that such brighteners work in this way because they have high affinity for fabrics in the wash solution and therefore they deposit relatively quickly on these fabrics. The degree to which the brighteners are deposited on the fabrics in the wash solution can be defined by a parameter called "exhaustion coefficient". The depletion coefficient is in general the ratio of a) the polishing material deposited on the cloth to b) the initial polish concentration in the wash liquor. Brighteners with relatively high depletion coefficients are most suitable for inhibiting dye transfer in the context of the present invention. Of course, it will be appreciated that other types of conventional optical brightener of compound 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 detergent caompositions can be included herein, including other active ingredients, vehicles, hydrotropes, processing aids, dyes and pigments, solvents p > for liquid formulations, solar filters for bar compositions, etc. If high foaming is desired, foaming enhancers such as Cio-Ciß alkanolamines can be incorporated into the compositions, typically at levels of 1% -10%. The Cno-Ci * mononoethanol and diethanolamines illustrate a typical class of such cycloallergens. foam. The use of said foam boosters with high foaming auxiliary surfactants such as amine, betaine and sultaine oxides previously described is also advantageous. If desired, the soluble magnesium salts such as MgCl? , MgSO-4 and similaree, can be added at typically 0.1% -2% levels, to provide additional foaming and to increase fat removal performance. Various detersive ingredients used in lae presentee comp >Items are p > They can then be stabilized by absorbing said ingredients on a porous hydrophobic substrate, 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 the weight of the silica. The resulting powder is dispersed with stirring in silicone oil (several silicon oil viscosities in the 500-12,500 scale can be used). 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, colorants, fluorescers, fabric conditioners and hydrolysable surface active agents can be "protected" for use in detergents, including liquid detergent compositions for laundry. Lae liquid detergent compositions can contain water and other solvents such as vehicles. The low molecular weight primary and secondary alcohols illustrated by methanol, ethanol, propanol and isopropanol are suitable. Monohydric alcohols are preferred for solubilizing surfactant, but talee polyols can also be used as those containing from 2 to 6 carbon atoms and from 2 to 6 hydroxyl groups (e.g., 1,3-azo-anodiol, ethylene glycol, glycerin, and 1, 2? -panpanediol). 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 instant dishwashing detergent formulations preferably have a pH between about 8 and approximately 11. The laundry products typically have a pH of 9 to 11. The techniques for controlling the pH at recommended usage levels include use of pH, alkali, acid regulators, etc., and are well known to those skilled in the art. The following examples illustrate compositions according to the invention, but are not intended to be limiting thereof. The following detergent compositions are prepared (pair + is in weight).

EXAMPLE I % in weigh Zeolite 38.0% Silicate 2.0R 6.0% Carbonate (Sodium) 9.0% Ethylenediaminetetranetilenefoefonate 0.2% Rinse aid 47 (Tinopal DMS) 0.1% Rinse aid 49 (Tinopal CBS) 0.05% Percarbonate 8.0% TAED 7.0% Mn Catalyst - * (ppm) 350 Savinase (4.0 KNPU / g) 2.0% Lipolaea (100,000 LU / g) 0.22% C12-14 alkylene sulfate 5.6% AE4.2 nonionic of C12-1-4 11.6% Soap 1.0% Various ingredients / humidity The rest 100% * iV2 (u-0) 3 (1, 4,7-trimethyl-1, 4,7-triazacyclonan) 2 (PFd b EXAMPLE II % in weigh Zeolite 38.0% Silicate 2.0R 6.0% Carbonate (Sodium) 7.0% Etilendiaminotetranetylene-phosphonate 0.2% Rinse aid 47 (Tinopal DMS) 0.1% Rinse aid 49 (Tinopal CBS) 0.05% Percarbonate 5.0% TAED 2.0% Catalyst of Mn * (ppm) 350 Savinase (4.0 KNPU / g) 2.0% Lipolase (100,000 LU / g) 0.22% C12-14 alkylene sulfate 5.6% AE4.2 nonionic of C12-14 11.6% Soap 1.0% Persulfate 10.0% Miscellaneous ingredients / moisture The remainder 100 * Mniv2 (? -0) 3 (1, 4,7-trimethyl-l, 4,7-triazacyclonanob (PFß b EXAMPLE III % in weigh Zeolite 38.0% Silicate 2.0R 6.0% Carbonate (Sodium) 7.0% Ethylenediaminetetranetilenefoefonate 0.2% Brightener 47 (Tinopal DMS) 0.1% Brightener 49 (Tinopal CBS) 0.05% Percarbonate 5.0% TAED 2.0% Catalyst Mn * (ppm) 350 Savinase (4.0 KNPU / g) 2.0% Lipolase (100,000 LU / g) 0.22% C12-14 alkylsulfate 5.6% C12-14 non-ionic AE4.2 11.6% Soap 1.0% PAP * "* 10.0 Miscellaneous ingredients / hr. rest 100 * Mniv2 (u-0) 3 (l, 4,7-trirnethyl-l, 4,7-triazacyclonanob (PFß b ** N, N-phthaloylamino? Eroxycaproic acid All of the above granulated compositions can be provided as spray-dried granules or granules or high density agglomerates (above 600 g / liter). In Example III, PAP can be replaced by 6-nonylamino-6-oxoperoxycaproic acid (NAPAA).

Claims (17)

NOVELTY OF THE INVENTION CLAIMS

1. - Laundry bleaching compositions having reduced damage to fabrics induced by metal-containing bleach catalyst, said compositions consist of: (a) a peroxy compound selected from a group consisting of pre-organed organic percarboxylic acids, bleach blends which they contain a bleaching agent which is a source of hydrogen peroxide and one or more bleach activators and mixtures thereof present in an amount effective to produce bleaching; (b) a bleach catalyst containing metal present in an amount effective to activate the peroxy compound; and further characterized in that the molar ratio of the hydrogen peroxide to the peracid, of the preformed organic percarboxylic acids or the bleach activator, is less than about 4: 1.

2. The laundry bleaching composition according to claim 1, further characterized in that the peroxy compound is a preformed organic percarboxylic acid.

3. The bleaching composition for laundry according to claim 1, further characterized in that the peroxy compound is a bleaching mixture containing a bleaching agent which is a source of selected urea peroxide of perborate, percarbonate, and mixtures thereof.

4. The bleaching composition for laundry according to claim 3, further characterized in that the bleach activator is TAED.

5. The bleaching composition for laundry according to claim 3, further characterized in that the molar ratio of hydrogen peroxide to peracid is from 1: 1 to about 3: 1.

6. The bleaching composition for laundry according to claim 3, further characterized in that the molar ratio of p > Hydrogen oxide to heavy metal ions in the bleach catalyst is less than about 1200: 1.

7. The laundry bleaching composition according to claim 3, further characterized in that the molar ratio of the peracid to metal ions p > The catalyst in a bleaching catalyst is greater than about 350: 1.

8. The bleaching composition for laundry according to claim 6, further characterized in that the molar ratio of peracid to heavy metal ions in the bleaching catalyst is greater than about 350: 1.

9. The laundry bleaching composition according to claim 2, further characterized in that the preformed organic percarboxylic acid is selected from 6-nonylamino-6-oxo-eroxycaproic acid, N, N-phthaloylamino-eroxic acid, and mixtures thereof. thereof.

10. A method for washing fabrics that consists in contacting the fabric that needs to be washed with a laundry solution of a composition according to claim 1, in a concentration such that said laundry solution has a concentration of catalyst - bleaching that contains metal in the surrounding scale- from 0.1 ppm to approximately 700 ppm.

11. A method for washing fabrics which consists of contacting the fabric that needs to be washed with a laundry solution of a composition according to claim 2, in a concentration such that said laundry solution has a concentration of bleach catalyst containing manganese in a ratio of about 0.1 ppm to about 700? p > m. 12.- A method for the. washing fabrics that consist of contacting the fabric that needs to be washed with a laundry solution of a composition according to claim 3, in a concentration such that said laundry solution has a concentration of bleach catalyst that They contain manganese on the scale of about 0.1 ppm to about 700 ppm. 13. A method for washing fabrics consisting of contacting the fabric that needs to be washed with a laundry solution of a composition according to claim 4, in a concentration such that said laundry solution has a concentration of metal-containing bleach catalyst in the range of about 0.01 ppm to about 700 pprn. 14. A method for washing fabrics consisting of contacting the fabric that needs to be washed with a laundry solution of a composition according to claim 5, in a concentration such that said laundry solution has a concentration of bleaching catalyst containing manganese in the scale of about 0.1 ppm to about 700 ppm. 15. A method for washing fabrics that consists of contacting the fabric that needs to be washed with a laundry solution of a composition according to claim 6, in a concentration such that said laundry solution has a concentration d) bleach catalyst containing manganese in the range of about 0.1 ppm to about 700 ppm. 16. A method for washing fabrics consisting of the contact of the fabric that needs to be washed with a laundry solution of a composition according to claim 7, in a concentration such that said laundry solution has a concentration of catalyst Bleach contains metal on the scale of about 0.1 ppm to about 700 ppm. 17. A method for washing fabrics consisting of contacting the fabric that needs to be washed with a laundry solution of a composition according to claim 8, at a concentration such that said laundry solution has a concentration of catalyst of bleaching containing manganese on the scale of about 0.1 ppm to about 700 ppm.