MXPA96004673A - Whitening compositions which comprise metallic which contain metal, yantioxidan - Google Patents

Abstract

The present invention relates to bleaching compositions for laundry that have fabric damage induced by metal-containing bleaching catalyst, said compositions characterized in that they comprise: a) from about 0.5% to about 40% by weight of the composition of a peroxy compound b) from about 50 ppm to about 500 ppm of a metal-containing bleach catalyst, and c) from about 50 ppm to about 2000 ppm of an antioxidant free radical scavenger material selected from the group consisting of BHT, BHA, TBHQ, gallate and propyl, ascorbic acid, and mixtures thereof, whereby the damage to fabrics associated with the metal-containing bleach catalyst is reduced

Description

WHITENING COMPOSITIONS COMPRISING METAL CONTAINING WHITENING CATALYZERS, AND ANTIOXIDANTS TECHNICAL FIELD The present invention relates to bleaching compositions (e.g., granular detergent compositions and liquid bleaching additive compositions) useful for fabric washing, comprising a metal bleach catalyst and an effective amount of an antioxidant.

BACKGROUND OF THE INVENTION Metal-containing catalysts 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 5,246,621; 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 surfaces and washing surfaces (such as dishwashing machines, cleaning in general) and in the wood pulp, paper and textile industries . It has been found that metal-containing bleach catalysts, especially manganese-containing catalysts, have the property, particularly when used in textiles, of damaging the tel which results in loss of tensile strength of the fibers and / or cause 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. In addition, said catalysts increase the compatibility concern for said bleaching sites which include certain typical ingredients for washing such as perfumes, brighteners and enzymes. Surprisingly, it has now been discovered that the inclusion of free radical scavenging antioxidants in laundry compositions comprising metal-containing bleach catalysts reduces the damage to the fabrics resulting from these catalysts in the washing process, without stop the catalytic activity of the metallic catalyst. An additional goal of this invention is to provide stable compositions containing ingredients otherwise incompatible with the metal catalyst. 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 comprises 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 A2.

BRIEF DESCRIPTION OF THE INVENTION The present invention relates to laundry bleaching compositions having reduced damage to fabrics induced by bleaching catalyst containing metal, said compositions comprising: a) a peroxy compound selected from a group comprising 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, present in an amount effective to give bleaching, - b) a bleaching catalyst containing metal (preferably a manganese bleach catalyst) present in an amount effective to activate the peroxy compound; and c) an antioxidant free radical scavenger material in an amount effective to reduce damage to fabrics associated with the metal-containing bleach catalyst. 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 Bleach Catalyst Containing Metal A type of bleach catalyst useful herein is a catalyst system comprising a heavy metal cation of defined bleach catalytic activity, such as copper, iron or manganese cations, a cation auxiliary metal 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 ethylenedianetetraacetic acid, ethylenediaminetetraphosphonic 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 Hniv2 (u-0) 3 (1, 4,7-trimethyl-1, 4,7-triazacyclononane) 2 - (PFß) 2 / MniH2 (? -0)? (? -0Ac) 2 (1, 4,7-trimethyl-1, 4,7-triazacyclononane) 2 (CIO 4) 2, Mniv? (uO) ß í 1,4,7-triazaciclonano) * (CiO «U, ni" M iv * (uO)? (u-0Ac) 2 (l 4,7-trimethyl-l, 4,7-triazaciclonona) 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-trimethyl-1,5, 8-triazacyclododecane, 2-methyl-1, 4,6-triazacyclononane, 2-rnethyl-1, 4,7-triazacyclononane, 1, 2,4,7-tetramethyl-1, 4,7-triazacyclononane and mixtures thereof Also included are mononuclear (IV) manganese complexes, such as Mniv (i, 4,7-trimethyl-1, 4,7-triazacyclononane), (0CH3) 3 (PF-6) as described in US application 5,194,416 Another type of bleaching catalyst, as described in US Pat. No. 5,114,606, is a water-soluble complex of manganese (II), (III), and / or (IV) with a ligand q? e is a compound of polyhydroxy without carboxylate having at least 3 consecutive groups of C-OH. Preferred ligands include sorb tol, iditol, d? lsitol, mannitol, xylitol, arabitol, adonitol, meso-erythritol, meso-inositol, lactose, and mixtures thereof. U.S. Patent 5,114,611 shows a bleach catalyst which comprises a transition metal complex, which includes Mn, Co, Fe, or C ?, with a ligand which is not rnacrocyclic. Said ligands are from the equation: R2 3 R 1 -N = C ~ BC = N-R 4 wherein R 1, R 2, R 3 and R 1 each may be selected from groups of H, aryl and substituted alkyl, so that each Ri ~ N = C-R2 and R3-C = NR * form a ring of 5 or 6 members, said ring can also be substituted. B is a bridge-forming group , - selected from 0, S. CRSR6,? , and C = 0, wherein R5, 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 complexes of Co, Cu, Mn, Fe, -bispiridinmethane and -bispyridyl ina. Highly preferred catalysts include Co (2,2'-bispyridylamine) Cl2 of Di (isothiocyanato) bispyridylamine-cobalt (II), trisdipyridylamine-cobalt (II) perchlorate, C0 (2,2-bispyridyl.amine) 2? - 2C.i0U, bis- (2,2'-bispyridylamine) -co? Er (II) perchlorate, tris (di-2-pyridylamine) -fiber (II) perchlorate and mixtures thereof. Other examples include Mn gluconate, Mn (CF3503) 2, Co (NH3) sCl, and the binuclear Mn complex with ligands of tetra-N- in + ra + oy his-N-den + ato that i cluyen ^ nlII (u-0) M i VN *) + and CB? Py2M m (u-0) 2 neither vb ?? and I-icio *) 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 (IT), (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 comprising MnSO ", Mn (C10") 2 or MnCl2 (less preferred) are dissolved in water in molar ratios of l: gand: salt of Mn on the scale from 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 + an + e is evaporated (under 2, 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 MnSOu, is added to the cleaning / bleaching composition or to the aqueous cleaning / bleaching bath comprising the ligand. Some type of complex is apparently formed in situ, and the improved bleaching performance is ensured. 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 manganese complexes bleach catalysts of the present invention have not been illustrated, it can be speculated that they comprise chelators or other complexes of hydrated coordination resulting 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 ligands with the manganese cation, it can reasonably be speculated which multi-nuclear species and / or "cage" structures may exist in the aqueous bleaching medium. Whatever the form of the active Mn ligand species that actually exist, it functions in a seemingly catalytic manner to provide improved bleaching performance in difficult to clean stains such as tea, tomato sauce, coffee, blood and Similar. 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 (e + aloporphyrin catalysts) , US 4,728,455 (manganese ligand catalyst / rn? L + identate), US 4,711,748 and European patent application, publication No. 224,952, (manganese absorbed in aluminosilicate catalyst), U.S. 4,601,845 (support of alurninosilicate 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 (q? Elatators with manganese cations and non-catalytic metal cations), and U.S. 4,728,455 (gl? Cona + or manganese 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 that is 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, front-loading laundry washers of the type used in F? Ropa generally use less water and higher concentrations of detergent than North American top-load washers. Some machines considerably have longer wash cycles than others. Some users choose to use water-n and hot; others use 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 ppm, preferably from about 1 ppm to about 500 ppm, of the catalyst species in washing liquid. To illustrate this point further, manganese catalyst in the order of 3 micrornolar is effective at 40 ° C, pH 10 under European conditions using perborate and bleach activator (eg, 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 formulator to match bleaching at lower perborate use levels than products without the manganese catalyst. The compositions herein, therefore, will typically consist of from about 1 pprn to about 1200 ppm of the bleach catalyst containing metal, preferably from about 5 ppm to about 800 ppm, and most preferred of about 10 ppm. at approximately 600 ppm. Highly preferred compositions comprise bleaching catalyst M v (? -0) 3 (1,4, 7-trimethyl-l, 4,7-triazacyclononane) 2 (PFß) 2 in a concentration of about 30 pprn to about 1000 ppm, preferably from about 50 pp to about 650 pprn, most preferred from about 50 ppm to about 500 ppm, and most preferred from about 120 ppm to about 400 pprn.Peroxy Compounds It should be appreciated that the bleach catalyst does not function as a bleach by itself. Rather, it is used as a catalyst to improve the performance of conventional bleaching agents and, in particular, oxygen bleaching agents such as perborate, percarbonate, persulphate, 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). Bleaching agents will typically be at levels of from about 1% to about 80%, more typically from about 5% to about 20%, of the detergent composition, especially for fabric washing. Bleaching and pre-bleaching 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 50%, more typically from about 0.5% to about 40% of the bleaching mixture comprising the bleaching agent more bleach activator. 1. Bleaching agents: The bleaching agents used herein may be any of the bleaching agents useful for bleaching or detergent compositions in textile cleaning, hard surface cleaning, or other cleaning purposes that are already known or are made known, and are useful for bleaching compositions as used in the present invention to treat fabrics. These include oxygen bleaches as well as bleaching agents. Perborate bleaches, for example, sodium perborate (e.g., mono- or tetrahydrate) may be used herein. Preferred peroxygen bleaching agents are used preferably in the compositions. Suitable peroxygen bleach compounds include sodium carbonate peroxyhydrate and equivalent "percarbonate" bleaches, sodium pyrophosphate peroxyhydrate, urea peroxyhydrate, and sodium peroxide. Persulfato bleach (for example, OXONE, manufactured commercially by DuPont) can also be used. A preferred percarbonate bleach comprises 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 millimeters and no greater of 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. Percarborate is available from several commercial sources such as FMC, Solvay and Tokai Denka. As used herein, the bleaching agents also comprise pre-formed organic percarboxylic acids. Said bleaching agents, which can be used without restriction, surround percarboxylic acid bleaching agents and salts thereof. Suitable examples of this class of agents include magnesium monoperoxy 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, Burns et al., Filed June 13, 1985, European Patent Application 0,133,354, Banks et al. , 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-oxoperoxycalcium (NAPAA) acid as described in the North American patent 4, 634,551, issued on January 6, 1987 to Burns et al. Such materials usually have a general equation: H0-0-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, CH2CI, COOH, or CO00H; 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) -C6H «-Y where Y is hydrogen, alkyl, alkylhalogen, halogen , or COOH or C000H. Typical rnonoperoxy percarboxylic acids useful herein include alkyl percarboxylic acids and aryl perearboxyl acids such as: (i) peroxybenzoic acid and ring-substituted peroxybenzoic acids, for example, α-hydroxy-o-naphthoic acid; (ii) aliphatic, substituted arylalkyl and aliphatic onoperoxy acids, for example, peroxylauric acid, peroxystearic acid, and N, N-phthalolaminoperoxycaproic acid (PAP). Typical diperoxy percarboxylic acids useful herein include alipiperoxy and aryldiperoxy acids, such as: (iii) 1,12-diperoxydecanedioic acid; (iv) 1,9-diperoxyazelaic acid; (v) deperoxy-fibrous acid; diperoxysebacic acid and diperoxnsofthal acid co; (vi) acid 2-dec? ld? perox? b? tano-l, 4-d? o? co; (vn) 4,4'-sulfon? b? s? erox? benzoic acid. The present invention may further include bleaching compositions comprising an effective amount of a more soluble organic percarboxylic acid bleaching agent having the general equation: 0 0 0 0 R1-CN-R2-C-00H R -NCR -C-00H RS R5 wherein R1 is an alkyl, aryl, or alkaline group containing from about 1 to about 14 carbon atoms, R2 is an alkylene, aplene or alkarylene group containing from about 1 to about 14 carbon atoms, and R5 is H or an alkyl, aryl, or alkaryl group containing from about 1 to about 10 carbon atoms. 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 process) 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-Q174132; EP-A-0120591 and U.S. Patent Nos. 1,246,339; 3,332,882; 4,128,494; 4,41.2,934 and 4,675,393. One class of bleach activators is that of peroxyacid activators substituted with quaternary ammonia as described in US Pat. Nos. 4,751,015 and 4,397,757, in EP-A-284292, EP-A-331,229 and EP-A-03520. Examples of peroxy acid whitening activators of this class are: 2- (N, N, N-trirnethyl ammonia) ethyl-4-sulfophenylcarbonate - (SPCC); N-octyl chloride, N, N-dimethyl-N-10-carbophenoxyidecyl onylac- (ODC); 4-eul fofen.ilcarbonato of 3- (N, N, N-trirnetilarnoniaco) - (SPCC); and N, N, N, -trimelamoniaco tolyleoxybenzenesulfonate. Other activators include 4-benzoyloxy benzenesulphonate sodium; N, N, N ', N'-tetracetylethylenediarnine; 1-Rethyl-2-benzoyloxybenzene-4-s-1-sodium fonate; Sodium 4-metii-3-benzoyloxybenzoate; nonanoyloxybenzenes, sodium fonate; 3,5,5-trimethylhexanoyloxybenzenes sodium l-fonate; glucose pentaacetate and tetraacetyl xylose.

Bleach activators also useful in the present invention are amide substituents of the general equations: 0 0 0 0 R1-CN-R2-CL R1-NC-R2-CL RS RS or mixtures thereof, wherein R is an alkyl, aryl, or alkaryl group containing about 1 to about 14 carbon atoms R is an alkylene, arylene or alkarylene group containing about 1 to about 14 carbon atoms, RS is H or an alkyl, aryl or alkaryl group containing about 1 to about 10 carbon atoms. carbon, 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 n-cleophilic attack on the bleach activator by the peroxyhydroxy anion. This, the perohydrolysis reaction, results in the formation of the peroxycarboxylic acid. Generally, for which group a suitable residual group should exert an electron-attracting effect. It must also form a stable entity of odo 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, a wash cycle). However, if L is very active, this activator will be difficult to stabilize for use in a bleaching composition. These characteristics are generally in parallel form by the pKa of the conjugate acid of the starting group, although exceptions to this invention are known. Commonly, the residual groups exhibiting said behavior are those in which their conjugated 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 of 11. Preferred bleach activators are those of the above general equation wherein R1, R2 and Rs are defined for the peroxy acid and L is selected from a group q? e comprising R3 Y -O-CH = C-CH = CH2 -O-CH-C-CH-CH2 and mixtures thereof wherein R * is an alkyl, aryl or alkaryl group, containing about 1 to about 14 carbon atoms, R3 is an alkyl chain containing from about 1 to about 8 carbon atoms, R * is H or R3, and Y is H or a solbilizing group. The preferred solubilizing groups are -S? 3 ~ M +, -C02-M +, -S04- +, -N + (R3) 4X- Y 0 < --N (R3) 3 and most preferred - SO3-M + and -C? 2 ~ M + where R3 is an alkyl chain containing about 1 to about 4 carbon atoms, M is a cation that provides solubility to the activator of bleaching and X is an anion that provides solubility to the bleach activator. Preferably, M is a substituted ammonia cation or alkali metal ammonia, with sodium and potassium being the most preferred, and X is a halogen anion, hydroxide, ethyl ester or acetate. 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 comprising: where R3 is defined as shown above and Y is -S? 3 ~ M +, -C? 2 ~ M + where M is as defined earlier. Preferred examples of bleach activators of the above equation include 6-octanarnidocaproyloxybenzene sulphonate, 6-nonanamidocaproyloxybenzenesulfonate, 6-decanamido-caproyloxybenzene, and fonate and mixtures thereof. Another important class of bleach activators provides organic percents 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 substituted benzoxazines of the type wherein Ri is H, alkyl, alkaryl, aryl, arylalkyl, and wherein R 2, R 4 and R 5 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 the acyl-lactarin activators, especially acylcaprolactams and acylvalerolactrarnes of the formula: wherein R * is H, alkyl, aryl, alkoxyaryl, or alkaryl which contains from 1 to about 10 carbon atoms, or a substituted phenyl group 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., absorbed in sodium perborate. Several examples that do not limit 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., U.S. Patent 4,412,934. Activators of nonanoyloxybenzene fonate (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 herein. The superior cleaning / bleaching action of the present compositions is also preferably achieved safely to natural rubber machine parts and other natural rubber articles, including fabrics which contain 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 niphophilic attack by a perhydroxide anion, 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 lactama bleach activators and amino derivatives 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.

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 which can be added to the compositions of this invention include a mixture of ascorbic acid, ascorbic palmitin, propyl gallate, available from Eastman Chemical Products., Inc., under the trade names Tenox® PG and Tenox Sl, a mixture of BHT (butylated hydroxytoluene), BHA (butylated hydroxyanisole), propyl gallate and citric acid, available from Eastman Chemical Products, Inc. under the trade name Tenox-6, butylated hydroxytoluene, available from UOP Process Division under the trade name Sustane® BHT; tertiary butylidene, Eastman Chemical Products, Inc., as Tenox TBHQ; natural tocopherols, Eastman Chemical Products Inc. as Tenox GT-1 / GT-2 and butylated hydroxyanisole; Eastman Chemical Productcs, 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; mono, tert-b-thihydroquinone ((MTBHQ), benzoic acid and salts of the isoe, tucuic acid and salts thereof, t-butylcatechol, 1,1,3-tris (2-methyl-4-hiroxy-5-) t-butyl phenyl) butan (topanol CA available from ICI), monoalkyl ethers of hydroquinone (e.g., 4-methoxyphenol), and mixtures thereof Preferred are BHT, BHA, TBHQ, propyl gallate, ascorbic acid and mixtures It should be recognized that for purposes of the present invention, otherwise useful materials such as antioxydants 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 of free radical scavengers" herein, but are optionally preferred material for use with antioxidant free radical scavenging materials.The term "antioxidant effective amount" as used herein, means an amount of free radical scavenger 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 catalyst bleaching that contains 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 that will be used in the products, therefore, are easily determined, and are typically present in 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 ppn 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.

Auxiliary Ingredients The compositions herein may optionally include one or more detergent auxiliary materials or other materials to assist and improve the cleaning performance, 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 free of boron and phosphate. Additionally, dishwashing formulations are preferably devoid 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. 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 physical form. When present, the compositions will typically comprise at least about 1% 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 from about 10% to 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 ratio of S1O2: Na2? 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. Na? KS-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 delta-Na2Si0s of stratified silicate. 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 as the alpha, beta and gamma forms. As indicated above, the delta-Na2Si0s (NaSKS-6) form is most preferred for use herein. Other silicates can also be used such as for example magnesium silicate, which can serve as a cracking agent in granular formulations, as a stabilizing agent for oxygen bleaches, and as a component of foam control systems. Examples of carbonate builders are alkali metal and alkali metal carbonates as described in German Patent Application No. 2,321,001 published November 15, 1973. Aluminosilicate builders are useful in the present invention. The aluminosilicate detergent detergents are of great importance in most of the heavy-duty granulated detergent solutions currently cornerciled, and can also be an important detergency enhancing ingredient in liquid detergent formulations. Alurinosilicate builders include those that have the empirical formula: Mz (zA102) and 1xH2? where z and y are integers of at least 6, the molar-zay ratio is on the scale of about 1.0 to about 0.5, and x is an integer of about 15 to about 264. The ion exchange materials of alurninosilicate Useful are commercially available. These aluminosilicates can be of crystalline or amorphous structure and can be aluminosilicates that occur naturally or synthetically derived. A method for producing aluminosilicate ion exchange materials is described in US Patent 3, 985,669, Krum et al. Issued October 12, 1976. The 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: Nai2C (Al? 2) l2 (SiO2) l2 ^ lxH2? wherein x is from about 20 to about 30, particularly about 27. The material is referred to 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 detergent 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 alkanolaronium salts are preferred. Included among the polycarboxylate builders are a variety of useful material categories. An important category of polycarboxylate builders includes ether polycarboxylates, including oxydisuccinate, as described in Berg, US Patent 3,128,287, issued April 7, 1964, and Larnberti et al., US Patent 3,635,830, issued on 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 Patent 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. 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. 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 the succinate detergency builders, to provide additional detergency activity. Said use of fatty acids will generally result in decreased foaming, which would be considered by the fornulator. In siting 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 can be ofos sodium and sodium orthophosphate. Chelating Agents - Although detergency enhancement 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 α-inophosphonate chelating agents such as DEQUEST are preferably not used in the compositions. However, nitrogen-based manganese chelating agents, such as ethylene diarynino-N, N'-disuccinate (EDDS), are useful. Detersive Surfactants - Non-limiting examples of non-amide additive surfactants, useful herein include the conventional Cn-Ciß alky? Bublelsulphates ("LAS") and the C10-C20 alkyl sulphates ("AS") primary, branched and random chain, the secondary sulphide (2,3) Cys-Ciß alkylsulfates of the formula CH3 (CH2) x (CH0S03-M +) CH3 and CH3 (CH2) and (CH0S03"M +) CH2CH3 where xy ( and + 1) are integers of at least 7, preferably at least about 9, and M is a solubilization cation in water, especially sodium, unsaturated syllables such as oleoylphosphate, the alkylalkoxy-ether-esters of Cío-Ciß. ("AExS", especially Eto 1-7 isotoxins), Cι-Ciß alkylalkoxycarboxylates (especially the EO 1-5 ethoxycarboxylates), the Cι-Ciß glycol ethers, the Cι-Ciß alkoxy polyglycosides and their corresponding sulfated polyglycosides , and C12-C18 alphasulfonated fatty acid esters. conventional nonionic amphoteric surfactants such as C12-C18 alkyl ethoxylates ("AE") including the so-called narrow peak alkyl ethoxylates and the C6-C12 alkyl phenolalkoxylates (especially mixed ethoxylates and ethoxy / propoxy), C12-C18 betaines and ss Lypbetaines ("sultaines"), Cι-Ciß amine oxides, and the like, may also be included in the overall compositions. N-alkyl polyhydroxyl fatty acid amides can also be used. Typical examples include C12-C18 N-methylglucamines. See UO 9,206,154. Other surfactants derived from sugar include the N-alkoxy polyhydric acid fatty acid amides, such as N- (3-C3-C18-C3-C18-C3-C18-N-propyl) N-hexylglycolates can be used for low foaming 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 normal texts Nonionic surfactants particularly suitable for dishwashing are alcohols Straight chain ethoxylated low sputtering or non-sputtering such as Pl? rafac ™ RA series, supplied by Eurane Co., "" "utensol ™ eerie LF, supplied by BASF Co., TritonTM DF series, supplied by Rohm »Haas Co., and Synperonic ™ LF series, supplied by ICI Co.

Removing / anti-redefining agents for clay dirt. The compositions of the present invention may also optionally contain water-soluble ethoxylated amines having clay dirt removal and anti-redeposition properties. The granular detergent compositions containing these compounds typically contain from about 0.01% to about 10.0% by weight of the water soluble ethoxylated amines; Liquid detergent compositions typically contain about 0.01% to about 5%. The preferred soil remover 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 soil removal / anti-redeposition agents are 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 may be used include the ethoxylated amine polymers described in European Patent Application 111,984, Gosselink, 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 type of preferred anti-redeposition agent includes carboxylmethyl cellulose (CMC) materials. These materials are well known in the art. Polymeric dispersion agents - Polymeric dispersion agents can be used advantageously at levels of from about 0.1% to about 7%, by weight, in the compositions herein, especially in the presence of detergent builders of zeolite 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 not intended to be limited by theory, that polymeric dispersing agents increase the performance of the overall builder, when used in combination with other builders (including lower molecular weight polycarboxylates) by inhibition of growth of crystals, peptization of release of dirt into particles and anti-redeposition. Polymeric polycarboxylate materials can be prepared by polymerizing or copolymerizing suitable unsaturated monomers, preferably in their acid form. Unsaturated monomeric acids which can be polimerized to form suitable polymeric polycarboxylates include acrylic acid, rnaleic acid (or rnaleic anhydride), furric acid, itaconic acid, aconitic acid, n-conconic acid, citraconic acid, methylenemalonic acid. The presence of the polymeric 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 polycarboxylic polycarboxylates can be derived from acrylic acid. Said acrylic acid-based polymers which are useful herein are the water-soluble salts of poly-acrylic 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. Water-soluble lables of said acrylic acid polymers may 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.

Copolymers based on acrylic / maleic acid can also be used as a preferred component of the dieting / 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. Soluble acrylate / randomiate 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 performance of dispersing agent and can act as a remover-anti-redeposition agent of clay dirt. Typical molecular weight scales for these purposes range 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. Polyaspartate and "Voliglutar" dispersing agents can also be used, especially in conjunction with zeolite builders, dispersants such as those of preferred polyaspartate have a molecular weight (avg.) Of about 10,000. These enzymes are present 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 on the basis of tnglicepdos, and to avoid the transfer of migratory dyes and fabric restoration Enzymes to be incorporated include proteases, ilase, lipases, cellulae and peroxidase, as well as mixtures thereof, other types of enzymes may also be included, they may be of any suitable origin, such as of vegetable, animal, bacterial, fungal and yeast origin, however, your choice is governed by many factors such as activity of pH and / or optimum stability, terrnostability, stability against active detergents, builders, etc. In this regard, bacterial and icotic enzymes, such as bacterial amylases and proteases and fungal cellulases, are preferred. Enzymes are normally incorporated at levels sufficient to provide up to about 5 mg by weight, very typically 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 commonly 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 syntacycins which are obtained from particular strains of B. s? Btilis and B. licheniforms. Another suitable protease is obtained from a strain of Bacillus that has maximum activity throughout the pH regime of 8-12, developed by Novo Ind? Dtries 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. Commercially available proteolytic enzymes suitable for removing protein-based stains include those sold under the trademarks ALCALASE and SAVINASE of Novo Industries ñ / 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 on April 28, 1987 and the European Patent Application. 130,756, Bott et al., Published January 9, 1985). Amylases include, for example, α-arylase described in British Patent Specification No. 1,296, 839 4.1.

(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. Enzymes .lipases suitable 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 A ano-CES, lipase from ex Chromobacter viscos? M, e.g. Chromobacter viscos? M var. lipolyct? m NRRLB 3673, commercially available from Toyo Jozo Co., Tagata, Japan; and in addition the Chromobacter lipases viscous from U.S. Boichemical Corp., E.U.A. and Disoynth Co., The Netherlands, and the lipaeas of ex Pse? dornonas 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. Peroxidase enzymes are known in the art and include, for example, horseradish peroxidase, ligninase and haloperoperoxidase such as chloroperoxidase and bromoperoxidase. Detergent compositions containing peroxidase are described, for example, in PCT International Application WO 89/09981.3, 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 January 5, 1971 to McCarty et al. 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. 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, "-Request No.86200586.5, published on October 29, 1986, Venegas. enzyme stabilization are also described, for example, in US Patent 3,519,570.Enzyme Stabilizers.- The enzymes employed herein are typically stabilized by the presence of water-soluble supplies of calcium and / or magnesium ions in the compositions. The 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. presence of several other stabilizers described in the art, especially borate species: see Sverson, US 4,537,706. Typical detergents, especially liquids, comprise of alr 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 8 to about 12 millimoles of calcium ions per liter of finished composition. This may somehow vary, depending on the amount of enzyme present and its respueeta to the 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 complex 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, formate of 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 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. More calcium and / or magnesium ions may be added to the compositions to provide an additional measure of fat removal performance. If used for such purpose, the compositions herein should typically comprise from about 0.05% to about 2% by weight of a water soluble 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 another borate compound capable of forming boric acid in the composition (calculated based on boric acid). Boric acid is preferred, although other compounds such as boric oxide, borax and other alkali metal borates (eg, sodium orthoborate, sodium rnataborate 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, pyrazoline, coumarin, carboxylic acid, rnetinocianinae, dibenzothiophene-5-dioxide, azole derivatives , heterocyclics of 5 and 6 members, and other diverse agents. Examples of such brighteners are described in "The" - "Application 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 US Pat. No. 4,790,865 issued to Lixon 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 Jhite CUD, available from Hilton-Davis, based in Italy; the 2- (4-estri-phenyl) -2H-naphtholCl, 2- d3triazoles; 4,4'-bis (1, 2,3-triazol-2-2-yl) -estilbenoe; 4,4'-bis (steryl) bisphenyls; and the inocumarinas. Specific examples of these brighteners include 4-rnetyl-7-diethyl-arninoc? arina; 1, 2-bis (-benzimidazol-2-yl) ethylene; 1,3-diphenyl-frazolines; 2,5-bis (benzoxazol-2-yl) thiophene; 2-estril-naf-Cl, 2- dUoxazol; and 2- (stilben-4-yl) -2H-naphtho-Cl, 2-d] triazole. See also patent of E.U.A. 3,646,015, issued on February 29, 1972 to Hamilton. Here anionic brighteners are preferred. Foam suppressants - Compounds for reducing or suppressing foaming 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 presses, and foam pressors are well known to those skilled in the art. See, for example, Kirk Othmer Encyclopedia of Chemical Technology, 3a. Edition, Volume 7, pages. 430-447 (John Uiley to Sons, Inc., 1979). A particular category of foam concentrates of particular interest includes monocarboxylic fatty acids and salts soluble therein. See U.S. Patent 2,954,347, issued September 27, 1960 to Uayne St. John. The rnononocarboxylic fatty acids and dusin 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 ammonium and alkanolammonium salts. The detergent compositions herein can also contain foam suppressors which are not surface active agents. These include, for example: high molecular weight hydrocarbons such as paraffin, fatty acid esters (e.g., triglycerides of 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-alkylmelaminae or di- to tetra-alkyldiarninoclotriazines formed as cyanuric chloride products with two or three moles of a primary or secondary amine which contains from 1 to 24"* carbon lathes, propylene oxide and rnonotene phosphates, such as rnonoesteryl alcohol phosphate ester and alkali metal diphosphates (eg, K, Na and Li) rnonoethereal and ester phosphates. -afine and halogenoparaffin 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 point of Minimum boiling is not less than about 110 ° C (atmospheric pressure) It is also known to use waxy hydrocarbons, preferably having melting point below about 100 ° C. Hydrocarbons constitute a preferred category of foam pressor for detergent compositions. . The hydrocarbon foam suppressors are described, for example, in U.S. Patent 4,255,779 issued May 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 s? Presor is foam, is intended to include mixtures of true paraffins and cyclic hydrocarbons. Another preferred category of squeezers of foams that are not surfactants comprise silicone foam suppressors. This category includes the use of iorganosiloxane oils such as polydi ethylsiloxane, dispersions or emulsions of polyorganosiloxane oils or reeins, 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 US Pat. No. 3,455,839 which relate to compositions and processes for the dewatering of aqueous solutions incorporating thereto small amounts of polydi-ethylsiloxane fluids. Silica and silanated silica mixtures are described, for example, in German Patent Application DOS 2,124,526. Eylicon foam scavengers and foam controlling agents in granular detergent compositions are described 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 foamagent to be used herein is a foamsuppressant amount of a eepumae controllagent essentially compris (i) polydimethylsiloxane fluid havan iscocity of from about 20 cs to about 1,500 cs at 25 ° C; (ii) from about 5 to about 50 parts per 100 parts by weight of (i) siloxane resin composed of (CH 3) 3 SiO units? 2 of units of SÍOL2 in a unit ratio of (CH3) 3 Si0? 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 foams pressurizer used herein, the solvent for a continuous phase is made of certain polyethylene glycols or polyethylene-polypropylene glycol copolymers 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 foams will comprise from about 0.001 to about 1, preferably from about 0.01 to about 0.7, most preferably from about 0.05 to about 0.5,% by weight of said The silicone foam pressor, comprising (1) a nonaqueous emulsion of a primary foam anti-foaming agent which is a mixture of (a) a polyorganosiloxane, (b) a resinous siloxane or a silicone compound producing silicone resin, (c) a finely divided filler material and (d)? a catalyst to promote "the reaction of mixture components (a), (b) and (c) to form silanolates; (2) at least one nonionic silicone surfactant; and (3) polyethylene glycol or a polyethylene-polypropylene glycol copolymer having a solubility in water at room temperature of more than about 2% by weight; opylene glycol, similar amounts can be used in gel.es granulated compositions, 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. The polyethylene glycol and polyethylene / polypropylene copolymers of the present have a solubility in water at room temperature other than about 2% in weight, preferably in excess of 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 peeo relationship of p: n is preferred about 1: 1 and 1:10, most preferably between 1: 3 and 1: 6, of polyethylene glycol: polyethylene o-polypropylene glycol copolymer. Preferred silicone foam suppressors used herein do not contain polypropylene glycol, particularly of molecular weight of 4,000. Preferably they also do not contain block copolymers of ethylene oxide and propylene oxide, such as PLURONIC L101. Other foam suppressors useful herein contain the secondary alcohols (e.g., 2-alkylalkanols) and mixtures of said alcohols with silicone oils, such as the silicones described in US Pat. Nos. 4,798,679, 4,075,118 and EP 150,872. Secondary alcohols include Cß-Ciß alkyl alcohols which have a Ci-Cie chain. A preferred alcohol is 2-butyloctanol, which is available from Condea under the trade name ISOFOL 12. Mixtures of secondary alcohols are available under the trade name ISALCHEM 123 of Enichem. Mixed foam suppressors typically comprise mixtures of alcohol + silicone at a peeo ratio of 1: 5 to 5: 1. For any detergent compositions to be used in automatic washing machines, the foams should not be formed to the extent that they overflow from the washing machine. The foam suppressors, when used, are preferably present in an amount of foam suppression. By "foam suppression amount" it is meant that the composition for the composition can select an amount of this foam controlling agent that will sufficiently control the foams to result in a low-spreader laundry detergent for machine operation. automatic washing machines. Compositions herein will generally comprise from 0% to about 5% foam suppressant. When used as foam 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 the nonacarboxylate 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 the sp? ation. 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 orthosilicate phosphate foam oppressors 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 that range 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 ectite clays of the U.S. Patent. 4,062,647, Storrn 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 cleaning fabrics. Clay-based softeners can 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, includes one or more materials effective to inhibit the transfer of dyes from one fabric to another. the cleaning procedure. Generally, said dye transfer inhibiting agents include polyvinylpyrrolidone polymers, polyarynin N-oxide polymers, N-vinylpyrrolidone and N-vinylnitridazole copolymers, 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 N-O group can be attached or the N-O group can be part of the polymerizable unit or the N-O group can be attached to both units; A is one of the following structures: -NC (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 N-O group can be attached or the N-O group is part of these groups. The preferred polyamine N-oxides are those wherein R is a heterocyclic group such as pyridine, pyrrole, irnidazole, pyrroline, piperidine and derivatives thereof. The N-O group can be represented by the following general structures: O O wherein Ri, R2, R3 are aliphatic, aromatic, heterocyclic or alicyclic groups or combinations thereof; x, y and z are 0 or 1; and the. N-O group nitrogen may be attached or forms part of any of the aforementioned groups. The amine oxide unit of the polyamine N-oxide has? N? Ka < 10, preferably? «A < 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 polyvinyl, polyalkylene, polyesters, polyethers, polyamide, polyimides, polyacrylates and mixtures thereof. Eetoe polírneroe include random or block copolymers where one type of monomer is an N-oxide of amine and the other type of monorne 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 copolyzing or by an appropriate degree of N-oxidation. Polyamine oxides can be obtained in almost any degree of polymerization. Typically, the average molecular weight is within the range of 500 to 1,000,000; very preferred from 1,000 to 500,000; Still preferred is 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 a ratio of amine to amine N-oxide of about 1: 4. The polymer copolymer of N-vinylporrolidone and N-vinylimidazole (also known as "PVPVI") are also preferred for use herein. Preferably, the PVPVI has a weight average molecular scale 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 Polyrner Characterization", the descriptions of which are incorporated herein by reference.) PVPVI copolymers typically have a molar ratio of N-vinylimidazole to N-vinylpyrrolidone of 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") having an average molecular weight of from about 5,000 to about 400,000, preferably from about 5,000 to about 200,000, and most preferably still from about 5,000 to about 50,000. . The PVP's are known to those skilled in the detergent field; 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 preferably comprise from about 0.01% to 1% by weight of said optical brighteners. The hydrophilic optical brighteners useful in the present invention are those having the structural formula: wherein Ri is selected from anilino, N-2-bis-hydroxyethyl and NH-2-hydroxyethyl; R2 is selected from N-2-bis-hydroxyethyl, N-2-hydroxyethyl-N-ethylamino, rnorfilino, chloro and amino; and M is a salt-forming cation such as sodium or potassium. When in the above formula, Ri is anilino, R2 ee N-2-bis-hydroxyethyl and M is a cation such as sodium, the brightener is acid 4,4 ', bisC (4-anilino-6- (N-2- bis-hydroxyethyl) -e-triazin-2-yl) arnino_l-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. Tinopai-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-r-nilarinamino and M is a cation such as sodium, the brightener is the disodium salt of 4,4'-bis [4- Nylon-6- (N-2-hydroxyethyl-N-ritylamino) - -tri zin-2-yl) aminoK-2,2'-stilbendis-lfonica. This particular brightener species is commercially marketed under the trade name Tinopal 5BM-GX by Ciba-Geigy Corporation. When in the above formula R1 is an.il.ino, R2 is morphino and M is? N cation such as sodium, the brightener is the sodium salt of acid 4, '-bisC (4-anilino-6-morphino-s) -triazin-2-yl) amino] 2,2'-stilbenedisulfonic acid. This particular type of brightener is sold comely to the trade name Ti nopal AMS-GX by Ciba-Geigy Corporation. The specific optical brightener species 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 poly epic materials (e.g., PVNO and / or PVPVI) with said selected optical brighteners (e.g., Tinopal UNPA-GX, Tinopal 5BM-GX and / or Tmopal 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 washing 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 the transfer of dye 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 detergent caompositions may be included herein, including other active ingredients, vehicles, hydrotropes, processing aids, dyes and pigments, solvents for liquid formulations, filters for bar compoeicionee, etc. . If high foaming is desired, foaming increments such as Cι-Ciß alkanolamines may be incorporated in the compositions, typically at a level of 1% -10%. The rnonoethanol and diethanolamines of Cío -Cu; illustrate a typical class of said foam boosters. The use of said foam boosters with high sputtering auxiliary surfactants such as aforementioned amine oxide, betaines and sultaines is also advantageous. If desired, the soluble magnesium salts such as MgCl 2, MgSO 4 and the like, can be added at typically 0.1% -2% levels, to provide additional foaming and to increase the fat removal performance.

Various detersive ingredients employed in the present compositions can be further stabilized by absorbing said ingredients on a porous hydrophobic substrate, then coating said sheet 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 sub-layer 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 agitation in silicone oil (various viscosities of silicone oil can be used in the range of 500-12,500). The resulting silicone oil dispersion is emulsified or otherwise added to the final detergent matrix. By this means, ingredients such as the enzymes, bleach, bleach activators, bleach catalysts, photoactivators, dyes, fluorescers, fabric conditioners and hydrolyzable surfactants mentioned above can be "protected" for use in detergents, including detergent-compositions. liquid for laundry. Lae liquid detergent compositions can contain water and other solvents such as vehicles. The primary and secondary alcohols of low molecular weight illustrated by methanol, 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-pro? Anodol) can also be used. , ethylene glycol, glycine and 1,2-pro? anodol). 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. Automatic dishwashing product formulations preferably have a pH of between about 8 and about 11. Laundry products typically have a pH of 9 to 11. The techniques for controlling the pH at recommended levels of use include the use of regulators of pH, alkalis, acids, etc., and are well known to those skilled in the art. The following examples illustrate compositions in accordance with the invention, but are not intended to be imitating thereof.

EXAMPLE I A dry bleach is as follows: Ingredient% by weight Sodium percarbonate 20.0 Benzoylcaprolactam activator 10.0 Mn catalyst * 350 prn BHT 0.3 Ascorbic acid 0.3 Water soluble filler ** The rest * MnIV2 (u-0) 3 (1, 4,7-trimethyl-1,4,7-triazacyclononane) 2 (PFß) 2, as described in US Pat. Nos. 5,246,621 and 5,244,594. • "•« Sodium carbonate, sodium silicate mixture (1: 1) In the above composition, the sodium percarbonate can be replaced by an equivalent amount of perborate In the above composition, the bleach catalyst can be replaced by an equivalent amount of the following catalysts: nUi2 (uO)? (? -0Ac) 2 (1,4, 7-trimethyl-1,4,7-triazacyclononane) 2 (CIO *) 2; Mniv «(uO) ß (1,4,7-triazaciclononanoU (CIO * U; nn? I || n? 4 (i, 4,7-trimethyl-l, 4,7-triazacyclononane (OCH3) 3 ( PFß); Co (2,2'-bie? Iridylanine) Cl2; Dis (isothiocyanate) bis-pyridylane-cobalt (II); trisdipyridylarnine-cobalt perchlorate (II); Co (2, -bispyridylamine) 2? 2Cl? 4; perchlorate Bis- (2,2'-biepriridylaniline) - copper (II); trie perchlorate (di ~ "S-pyridylamine) -iron (II); gluconate Mn; Mn (CF3S03) 2; Co (NH3) -5Cl; binuclear Mn complexed with tetra-N-dentate and bi-N-dentate ligands , including N-vMn111 (u-0) 2MnIVNn) + and CBipl2 nilI (u-0) 2MnIV bipY2 J- (Cl? 4) 3 and mixtures thereof In addition, in the above composition, the bleach activator can be replaced by an equivalent amount of the following activators: benzoylvalerolactam, nonanoylcaprolactam, nonanoylvalerolactane, 4-nitrobenzoylcaprolactam, 4-nitrobenzoylvalerolactam, octanoylcaprolactam, octanoylvalerolactam, decanoylcaprolactam, decanoylvalerolactam, undecanolacaprolactam, undecanoylvalerolactam, 3,5,5-trimethylhexanoylcaprolactam , 3,5,5-trimethylhexanoylvalerolactam, dinitrobenzoylcaprolactane, dinitrobenzoylvalerolactane, trephthaloidi-caprolactam, tert-butylldivalerolactane, (6-fonate, (6-decanamidocaproiDoxibencenes-lphonate, and mixtures thereof) The compositions of Example I They may be used per se as a bleach, or they may be added to a pre-soak or a detergent composition containing surfactant to impart bleach benefit thereto. In the laundry detergent compositions hereinafter, the abbreviated identifications of component s have the following meanings: LAS-C12 alkoxybenzene sodium lonate TAS - sodium tallow alkaline phosphate TAEn - tallow alcohol ethoxylated with n moles of thioiene oxide per mole of alcohol. 25EY - A C12-15 predominantly linear primary alcohol condensed with an average of Y moles of ethylene oxide. TAED - tetraacetylethylenediamine Silicate - Amorphous sodium silicate (Normally follows the ratio of Si? 2: a2?) Carbonate - Sodium carbonate anhydrous CMC - Carboxymethylcell? Sodium slab Zeolite A - Hydrated sodium aluminosilicate having? N primary particle size on the scale of 1 to 10 micrometers. Citrate - trisodium citrate dihydrate Ma / AA - Copolymer of 1: 4 maleic / acrylic acid, average molecular weight of around 80,000. Enzyme - Proteolytic and mixed amylolytic enzyme sold by Novo Industries AS. Brightener - Disodium 4,4'-bis (2-morpholino-4-anilino-s-triazin-6-ylamino) stilbene-2: 2'-disulfonate. S? Foam pressurizer - 25% paraffin wax Mpt 50 ° C, 17% hydrophobic silica, 58% paraffin oil. Sulfate - sodium anhydrosulfate In use for fabric cleaning, the compositions are used in a conventional manner and at conventional concentrations. Therefore, in a typical manner, the compositions are placed in aqueous liquid which may vary from about 100 ppm to about 10,000 pprn, depending on the load of the dirt and the stained fabrics are agitated therein.

EXAMPLE II The following detergent compositions are prepared (parts by weight). A B C D E LAS 7.71 7.71 7.71 7.71 7.71 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 4.25 4.25 NaSKS-6 - - - 10.01 1.0.0.1 Acico Cítrico - - - 2.73 2.73 TAE50 - - - 0.26 0.26 Carbonate 11.14 11.14 11.14 9.84 9.84 Perborato 16.0 16.0 16.0 16.0 16.0 Benzoil- 10.0 10.0 - 5.0 --caprolactarna TAED - 5.0 5.0 5.0 5.0 Catalyst 350 350 350 350 350 in * (ppm) CMC 0.48 0.48 0.48 0.48 0.48 Supreeor 0.5 0.5 0.5 0.5 0.5 Eepurna Brightener 0.24 0.24 0.24 0.24 0.24 Enzyme 1.4 1.4 1.4 1.4 1.4 Silicate 4.38 4.38 4.38 - - (2.0 ratio) gS? 4 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 BHT 0.3 0.3 0.3 0.3 0.3 Acid 0.3 0.3 0.3 0.3 0.3 Ascorbic Water and various ingredients to subtract. * niv2 (u-0) 3 (1,4, 7-trimethyl-l, 4,7-triazacyclononane) 2 (PFß) 2 The above compositions can be modified by adding lipase enzymes. The above compositions can be modified by replacing the bleach catalyst with an equivalent amount of bleach catalysts identified in Example I. The above compositions can also be modified by replacing the benzoyl.Icaprolactam with an equivalent amount of bleach activators identified in Example I .

The above compositions can also be modified by replacing the TAED with an equivalent amount of NOBS or leaving the 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: C12-13 LAS (20%); tripoli sodium phosphate (20%); sodium silicate (7%); Sodium perborate monohydrate (10%); (6-decan idocaproiDoxi-benzenes? Lfonate (10%); MnIV2 (u-0) 3 (1,4,7-trirnetyl-l, 4,7-triazacyclononane) 2 - (PFß) 2 (1.0%); BhT (0.5%), MgS0 <talc filler, and water (5%) .The above compositions can be modified by adding lipase enzymes.The above compositions can also be modified by replacing the bleach catalyst with an equivalent amount of the catalyst. bleach identified in Example I. The above compositions can also be modified with an equivalent amount of the bleach activators identified in Example I. The above compositions can also be 7.1"Encoded by replacing the perborate with an equivalent amount of percarbonate, all granular compositions herein may be provided as spray-drying granules or high-density granules or agglomerations (above 600 g / 1). Mn catalyst can be absorbed on and in water-soluble granules to keep the catalyst separated from the rest of the compositions, thus providing additional stability in storage.These granules (which should not contain oxidizable components) can comprise, for example, water-soluble silicates. , carbonates and the like Although the above compositions are typical of those useful herein, the most preferred one is: (1) the compositions that the STPP detergency does not have; (2) the ratio of the nonionic surfactant: anionic is greater than 1: 1, preferably of at least 1.5: 1, and (3) that at least 1% of perborate - another chloride cleaner is p Resent in the compositions to minimize the formation of M 2 when used.

EXAMPLE IV % in weigh Zeolite 38.0% Silicate 2.0R 6.0% Carbonate (Sodium) 7.0% Ethylenediaminetetramethylenephosphonate 0.2% Rinse aid 47 (Tinopal DMS) 0.1% Rinse aid 49 (Tinopal CBS) 0.05% Perearbonate 14.0% TAED 3.0% Catalyst of Mn * (ppm) 350 Savinaea (4.0 KNPU / g) 2.0% Lipolase (100,000 LU / g) 0.22% C12-14 alkyl sulfate 5.4% AE4.2 nonionic of C12-14 11.2% Soap 1.0% BHT 0.3% Ascorbic Acid 0.3% Various ingredients / moisture The 100% r-this * Mniv2 (u-0) 3 (1,4,7-trimethyl-1,4,7-triazacyclonan) 2 (PFß) 2

Claims (20)

NOVELTY OF THE INVENTION CLAIMS

1. - Laundry bleaching compositions that have reduced damage to metal-containing catalyst-induced bleaching fabrics, said compositions comprising: (a) a peroxy compound selected from a group comprising preformed organic percarboxylic acids, bleaching r 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 c) an antioxidant free radical scavenger material in an amount effective to reduce the damage to fabrics associated with the bleach catalyst which contains metal.

2. The bleaching compositions for laundry according to claim 1, further characterized in that the catalyst is a catalyst that contains manganese.

3. The bleaching compositions for laundry according to claim 1, further characterized in that the peroxy compound comprises perborate, percarbonate, and mixtures thereof.

4. The bleaching compositions for laundry V 'in accordance with claim 2, further characterized in that the peroxy compound consists of a bleach activator.

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

6. The bleaching compositions for laundry according to claim 3, further characterized in that the catalyst comprises the ligand 1,4,7-triazacilononano.

7. Lae cornpoeicionee blanqueadorae for laundry according to claim 4, further characterized in that the catalyst is MnIV2 (u-0) 3 (1,4,7-triazaci-clononano) 2 (PFß) 2.

8. The bleaching compositions for laundry according to claim 4, further characterized in that the antioxidant material is selected from BHT, BHA, TBHQ, propyl gallate, ascorbic acid, and mixtures thereof.

9. Laundry bleaching compositions having reduced fabric damage induced by manganese-containing bleach catalyst, said compositions comprising: (a) a peroxy compound present in a bleach-effective amount selected from the group comprising perborate, percarbonate , and mixtures thereof; (b) a manganese-containing bleach catalyst present in an amount effective to activate the peroxy compound; and (c) from about lpprn to about 2% of an antioxidant free radical scavenger material.

10. The bleaching compositions for laundry according to claim 9, further characterized in that the peroxy compound comprises a bleach activator.

11. The bleaching compositions for laundry according to claim 10, further characterized in that the bleach activator is TAED.

12. The bleaching compositions for laundry according to claim, further characterized in that the catalyst comprises the ligand 1,4,7-trirnethyl-1,4,7-triazacyclononane.

13. The laundry bleaching compositions according to claim 12, further characterized in that the catalyst is niv2 (u-0) 3 (1,4,7-trimethyl-1,4,7-triazacyclononane) 2 (PFß) 2 .

14. The bleaching compositions for laundry according to claim 13, further characterized in that the antioxidant material is selected from BHT, BHA, TBHQ, propyl gallate, ascorbic acid, and mixtures thereof present in an effective amount to reduce damage to fabrics associated with the bleach catalyst which contains manganese. 15.- Use of a free radical scavenger antioxidant material in a laundry bleaching composition which comprises a metal-containing bleach catalyst for reducing catalyst-induced damage to fabrics. 16. Use of an antioxidant free radical scavenger material in a laundry bleach composition comprising a manganese-containing bleach catalyst to reduce catalyst-induced damage to fabrics. 17.- Use of an antioxidant scavenger-free radical material in a laundry bleaching composition comprising a bleaching catalyst MnIV2 (u-0) 3 (1), 4, 7-trimethyl-l, 4,7-triazacyclononane) 2 (PFß) 2 to reduce damage to catalyst-induced fabrics. 18. A method for washing fabrics comprising 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 catalyst-bleaching metal containing on the scale of about 0.1 ppm to about 700 ppm. 19. A method for washing fabrics which is a contact of the fabric that needs to be washed with a laundry solution of a composition according to claim 9, in a concentration such that said laundry solution has a concentration of bleach catalyst which contains manganese on the scale of about 0.001 ppm to about 700 pprn. 20. A method for washing fabrics comprising the contact of the fabric that needs to be washed with a laundry solution of a composition according to claim 13, at a concentration such that said laundry solution has a catalyst-bleaching concentration containing metal on the scale of about 0.1 pprn to about 700 pprn.