MXPA96004671A - Method for whitening fabrics using whitening catalysts that contain mangan - Google Patents

Abstract

The present invention relates to a method for reducing the transfer of bleaching catalyst from laundry bleaching compositions containing manganese-containing bleach catalysts, said composition having less than about 40 ppm of manganese, originated by the catalyst; method being characterized in that it comprises contacting the impregnated fabrics with the manganese-containing bleach catalysts with an aqueous solution having a pH below about 4.

Description

METHOD FOR BLANKING FABRICS USING MANGANESE CONTAINING WHITENING CATALYSTS TECHNICAL FIELD 5 The present invention relates to bleaching compositions (e.g., granular detergent compositions, liquid bleaching additive compositions) useful for fabric laundry comprising a manganese bleach catalyst at a level below approx. approximately 40 pprn of manganese, originated by the catalyst. The present invention also relates to all acid washing methods, especially all useful for industrial and institutional washing processes, for the decontamination of impregnated fabrics. with metal-containing bleach catalysts, as a result of having previously been bleached with bleach compositions comprising a metal-containing bleach catalyst (eg, a complex containing manganese). Said method comprises contacting the fabrics that > ,and needs to decontaminate with an acidic aqueous solution that has a pH below about 4.0.

BACKGROUND OF THE INVENTION The catalysts that contain 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 5,246,621, 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 stains.Much of these bleaching systems are purportedly effective for use in the washing and bleaching of substrates, including hard and washing surfaces. (such as in a dish washer, cleaning in general) and in the wood pulp, paper and textile industries, it has been found that these metal-containing bleach catalysts, especially the manganese-containing catalysts, have the property in particular unwanted, when used in cellulosic textiles, to damage the fabric resulting in loss of tensile strength d e the fibers and / or cause damage to the LOIOG of the fabric. Obviously, such properties for compositions are a great disadvantage for the general use of these compositions in the area of laundering. Furthermore, it has been discovered that a substantial metal quality originated by the metal bleach catalysts is retained in the Fabric after the washing process, even if low levels of the catalyst were used, thereby leading to catalytic activity in subsequent washing procedures that involve bleach-containing compositions. This transfer property of metal-containing bleach catalysts through washing has been previously recognized, for example, described in Examples 9-12 of U.S. Patent No. 4,892,555 to Le gh et al., Issued on 9 January 1990. By using compositions containing metal bleach catalyst, accumulation can occur by several washes. The catalytic activity transferred from previous washings can also have the aforementioned harmful effects on the fabrics even if the subsequent washes no longer use laundry compositions containing bleach with metal-containing bleach catalyst. It is not a desirable result for manufacturers of such catalyst-free laundry compositions. It has now surprisingly been found that laundry compositions comprising bleach catalysts containing manganese, at a level of less than about 40 pprn manganese, reduce damage to the fabric resulting from these catalysts in the process of laundry. It has also been surprisingly discovered that the deleterious transfer effect can be reduced by decontaminating fabrics impregnated with the metals, originated by the metal-containing bleaching devices, by contacting these fabrics with aqueous acid solutions having a pH below about 4.0. . Such contact may be by soaking the fabric that needs to be decontaminated in an aqueous acid bath immediately after the washing procedure (for example during the rinse cycle) or after, including the pre-wash of the fabric in a just acid bath. before the next wash. These and other objects are insured here, as will be seen from 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 benzoxazm 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 patents. North American: 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; FP 549,271 01; EP 544,490; fll; EP 54,272 Al; and EP 544,440 A2. In U.S. Patent No. 4,892,555, Leigh et al., Issued January 9, 1990 and U.S. Patent No. 4,786,421, utter oi th et al., Published November 22, 1988, are incorporated by reference. describes the use of fabric softening compositions containing metal-containing bleach cata lycers during the rinse cycle of the laundry process which results in the impregnation of fabrics with the tasting! Metal initiators and catalytic bleaching activity the next time the fabric is washed. These Patents also describe the transfer effect 5 in the next wash from the use of laundry detergent compositions containing metal-containing bleach catalysts used during the wash cycle of the laundry processes.

U) BRIEF DESCRIPTION OF THE INVENTION The present invention relates to laundry bleaching compositions having a reduced effect of damage to the fabric induced by the bleaching catalyst containing manganese L5, said compositions comprising: (a) • peroxide compound present in an effective amount to cause bleaching; (b) a manganese-containing bleach catalyst, present in an effective amount to activate ol 2 (1 peroxide compound, wherein said concentration of manganese in said composition is less than about 40 ppm of manganese originating from the catalyst.The present invention also relates to the methods for the reduction of catalyst carry over from the 25 laundry bleach compositions containing metal-containing bleach catalysts, said method comprising contacting the impregnated fabrics with the metal-containing bleach catalysts with an aqueous acidic solution having a pH below about 4.0. are methods wherein the fabric is soaked in an aqueous acid solution having a pH of less than about 3.0, for at least 15 minutes ap- proximately, preferably for at least about 60 minutes, followed by washing the fabric in an alkaline composition, laundry detergent, catalyst-free. alkaline catalyst-free laundry detergent - optimally improves the color brilliance or whiteness of the fabric after soaking in an acid bath. Here, all percentages, ratios and proportions are by weight, unless otherwise specified. All documents cited are, in relevant detail, incorporated in the present and reference.

DETAILED DESCRIPTION OF THE INVENTION Bleaching Catalysts Containing Manganese Bleaching catalysts useful herein 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 Uni v2 (u-0) 3 (1, 4, 7 -t rirnet 11-1, 4, 7-t pazac? Clononane) 2 - (F &) 2, M iit2 (u-0)? (? ~ 0Ac) 2 (l, 4,7-tr? Rnet? L- 1, 4,7-tr? Azac? Clonone o) 2 (C? O4 -, MnIV4 (uO)? (L, 4,7- triazacyclonanoU (C1O-1, Mn? 1? ni v. (? -O)? (u-OOc) 2 (1,4,7-t prnetyl-], 4, 7-tr-? azac? clonone) 2 CCÍOÍV) 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-tmetmet-1, 1, 5, 8-tpazacyclododecane, 2-methι, 4,6-tpazací clononane, 2-rnetι-1,4 , 7-tpazac? clononane, 1,2,4, 7-tetrarnet and 1-1,4,7-tpazacyclononane and mixtures thereof. Also included are rnonuclear (IV) manganese complexes, such as Mniv (i, 4,7-tr? Met? Ll, 4,7-pazac? Clononane), (OCH3) 3 (PF-y) as described in the North American application for 5,194,416. Another type of bleaching catalyst, as described in US Pat. No. 5,114,606, is a water soluble complex of manganese (TI), (III), and / or (TV) with a ligand which is a polyhydroxy compound without carboxylate which has at least 3 consecutive grups of C OH. The preferred gandes include sorbitol, iditol, dulsitol, inanitol, xylitol, arabitol, adonitol, rneso-y itp tol, rneso-i nos t ol, lactose, and mixtures thereof. U.S. Patent 5,114,611 shows a bleach catalyst consisting of a transition metal compound, including Mn, Co, Fe, or Cu, with a ligand q? E not being nacrocylic 1 co. Said ligands are of the formula: R2 R3 Rl-N? CBC = NR * wherein R1, R2, R3 and R * each may be selected from H, ar-yl and substituted alkyl groups, so that each Ri-N = C-R2 and R3- C = NR¿ for-man a ring of 5 or 6 members, said ring can also be replaced. B is a bridge-forming group selected from 0, S. CR5R6, NR? , and C = 0, where R *) R6, and R7 each may be a group of H, alkyl, or aplo, including substituted or non-substituted groups. Preferred ligands include pindin, pyridazole, piprnidma, pyrazam, irnidazole, pyrazole and tnazole rings. Optionally, said rings can be substituted with subsites such as alkyl, aplo, alkoxy, alide, and nitro. Par-ticularly preferred is ligand 2, '-bispi ridilarnma. Preferred bleach catalysts include complexes of Co, Cu, Mn, Fe, -bi spi idi nmet no and -bisp-ridylamine. Highly preferred catalysts include Co (2, 2 '-bi spi r? D? L? -? In? Na) Cl.sub.2 di (isot? Oc? Anato) b? Sp? Pd? Lam? Nacobalt (II), perclor-ato de trisdi pin di Lami nabalco or (II), C0 (2, 2 -bi spi ridi lamina)? -2C1O4, Bis- (2, 2 '- bispi pdilarnina) -coppery TI) perchlorate, tp s perchlorate (d? -2-p? P dilamin) -fiber (TT) and mixtures of Los Husmos. Other examples include Mn gluconate, (CF3? 3) 2, 0o (NI-l3) sCl, and the bnuclear Mn complex with l gandos of tetra-N-denatura and bis-N-dentato u mcluyenN ^ IInlII (u ~ 0) 2Mniv) + and TB? Py2 niii (u-0) 2 Mni vh? Py2] - (CIO4) 3 - The bleach catalysts of the present invention can also be prepared by combining a water soluble ligand with a water soluble manganese salt in aqueous medium and concentrating the resulting mixture by means of evaporation. Any convenient water soluble salt of manganese can be used herein. Manganese (II), (ITT), (IV) and / or (V) is already available on a commercial scale. In some cases, sufficient manganese may be present in the liquid for washing, but, in general, Mn additions are preferred 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 MnS0, Mn (C10.) 2 or MnCl2 (less preferred) are dissolved in water at molar ratios of ligand: Mn salt in the scale of about 1: 4 to 4: 1 at light or neutral alkaline pH. The water can initially be deoxygenated by boiling-and cooling-by means of nitrogen spraying. The resulting solution is evaporated (ba or 2, if desired) and the resulting solids are used in the detergent and bleach compositions in the present without further purification. In an alternate form, the manganese source soluble in water, such as n 04, is added to the cleaning / bleaching composition or to the water cleaning / bleaching bath consisting of the ligand. Some type of complex apparently is formed 1 itu, and the performance of improved bleaching is assured. In a situ method, 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 with decomposition. A possible system is described in the European patent application publication No. 549,271. While the structures of the manganese bleach catalyst complexes of the present invention have not been illustrated, it can be speculated that they consist of chelating agents or other complexes of hydrated coordination resulting from the interaction of the carboxyl and nitrogen atoms of the ligand with cation of manganese. Likewise, the oxidation state of the manganese cation during the catalytic process is known with certainty, and may be the valence state of (+ TT), Í + TTI), (+ TV) or (+ V). Due to the possible 6 fixation points of the ligands with the manganese cation, it can reasonably be speculated that very nuclear species and / or "cage" structures may exist- in the aqueous bleaching medium. Whichever is 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 the like. . Other manganese bleach catalysts are described, for example, in U.S. Patent No. 4,728,455 (manganese / multidentate ligand catalyst), U.S. Patent No. 4,711,748, and European Patent Application, publication No. 224,952, (manganese catalyst absorbed on aluminosilicate), U.S. Patent No. 4,601,845 (support of aluminosil icato with manganese and zinc or magnesium salt), U.S. Patent No. 4,626,373 (manganese catalyst / ligand), U.S. Patent No. 4,430,243 (chelators with manganese cations and non-catalytic metal cations), and U.S. Patent No. 4,728,455 (catalysts Manganese gluconate builders) The catalyst-manganese bleach it is used in a catalytically effective amount in the compositions and processes herein. "Catalytically effective amount" means an amount that is sufficient, under whatever test comparison condition 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 habits of the user. Foresto, the front-loading laundry scrubbers of the type used in Europe, 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 hot rnuy 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 species of bleaching catalysts in the aqueous wash liquor. , and preferably provide from about 0.1 ppm to about 700 pprn, most preferably from about L ppm to about 500 ppm, of the catalyst species in washing liquid. To illustrate this point - furthermore, manganese catalyst of the order of 3 micro-inolar is effective at 40 ° C, pH 10 ba or European conditions using per-borate and a bleach activator (for example, benzyl lcaprolactane). 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 manganase catalyst with per orate can allow the formulator to match bleaching at lower perborate use levels-that is, the products without the manganese catalyst. However, for the purpose of the present invention, to reduce the damage of felling associated with such manganese-containing bleach catalysts, it has been found that these benefits can be obtained by using a catalyst in concentrations, in the laundry composition, by - below about 40 ppm of manganese originated by catalyst (therefore, it does not include the non-catalytic manganese in the compositions or the manganese randomly present in the washing solution), preferably less than about 35 ppm, preferably less than about 25 ppm, most preferably less than about 20 ppm, and preferably less than about 15 ppm or less, (about less than 10 pprn). Par-a the preferred manganese bleach catalyst used here, MnIV2 (u-0) 3 (1, 4, 7-t rimett1-1, 4, 7-tpazac? Clononane) ~ (PFe) 2H2 ?, this is? a concentration of the catalyst material of less than about 100 pprn (preferably from about 1 to 300 ppin), preferably less than about 250 pprn (preferable of the 250 pprn), with less than about 180 ppin being preferred (preferably from L to 180 ppm approximately) and less than about 150 Pp, (preferably from 1 to 150 ppm approximately), and less than about 110 ppm (preferably from about 3 to about 110 pprn) and less than about 85 pprn (from 5 to 05 ppm approximately).

The bleach-containing compositions and the processes that result in the catalyst-impregnation of the fabrics typically comprise from about 1 to 1200 ppm of the metal-containing bleach catalyst, typically from about 5 pprn to about 800 ppm, and more typically from about 10 ppm. at approximately 600 ppm. Commercial compositions (for example, PERSIL POUER, sold by Lever), can comprise the bleaching catalyst Mn1 v (u-0) 3 (1, 4, 7-tr? Rnet? L-1, 4, 7-tr-? azac? clononane) 2 - (PFd) 2, at a concentration of 40 to 400 pprn to approximation e. However, it is preferred that the catalyst-containing bleaching compositions, for the acid washing methods present, comprise the lower levels of manganese catalyst of the present invention. Compounds of but i It should be noted * that the bleach catalyst * does not work as a bleach on its own. Rather, it is used as a catalyst to improve the performance of conventional bleaching agents and, in particular, oxygen bleaching agents such as perborate, percarbonat, 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 stain or spots of interest (for example, spots of tea, spots of vi o). 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 that is a source of hydrogen peroxide and one or more bleach activators. , and mixtures thereof. Furthermore, when a bleaching agent which is a source of hydrogen peroxide is present in the composition of the present invention, said compositions additionally have a molar ratio of hydrogen peroxide to bleach activator minor * of 4: 1. Bleaching 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. Bleach and pre-bleach 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 bleaching agent or bleach activator. 1. Bleaching agents: The bleaching agents used herein may be any of the bleaching agents useful for bleaching or detergent compositions in textLl cleaning, hard surface cleaning, or other cleaning purposes which are already known or 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. Peroxygen bleaching agents are preferably used in the compositions. Suitable peroxygen bleach compounds include perox th drato of sodium carbonate and equivalent "perc rbonate" bleaches, sodium pyrophosphate peroxyhydrate, urea peroxyhydrate, and sodium peroxide. Persulfate bleach (for example, OXONE, manufactured commercially by DuPont) can also be used. A preferred percarbonate bleach consists of dry particles having an average particle size on the scale of about 500 micro-networks to about 1000 micro-networks, no more than about 10% by weight of said particles being less than about 200 micro-networks. and no greater than about 10% by weight of said particles being less than about 1250 micrometers- Optionally, the percarbonate can be coated with water-soluble, borate or silicate surfactants. Percarborate is available from several commercial sources such as FMC, olvay and Tol-ai Den a. As used herein, bleaching agents also consist of preformed organic peroarboxy acids. Said bleaching agents, which can be used without restriction, surround percarboxylic acid bleaching agents and salts thereof. Suitable examples of such a class of agents include magnesium rnononoperoxy-talate magnesium hexahydrate (INTFROX), the magnesium salt of permethic acid rnetachlor, 4-non-larn-non-4-oxoperox-but-ipco acid and di-di-dodecanedioic acid. Such bleaching agents are disclosed in U.S. Patent 4,483,701, Hartrnan, issued November 20, 1984, U.S. Patent Application 340,446, Burns et al., Filed on U.S. 13, 1985, European Patent Application 0,133,354, Banl. 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-non? lam? no-6-oxoper * ox acid. CA (CA) as described in U.S. Patent 4,634,551, issued January 6, 1987 to Burns et al. Said materials usually have a genetically formulated formula: HO-O-CÍOJ-RY wherein R is a substituted alkylene or alkylene group containing from 1 to approximately 22 carbon atoms or a group of substituted femlene or femlene and Y is hydrogen, halogen, alkyl, aplo or -Cio) -OH or -C (0) -0-OH The organic percarboxylic acids useful in the present invention may contain either one or two peroxy groups and may be * aliphatic or aromatic. When the organic perearboxyl acid is aliphatic, the unsubstituted acid has the general formula: H0-0-C (0) - (CH2) n "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 form The general: H0-0-0 (0) ~ C6H., - Y where Y is hydrogen, alkyl, to the quilhalogeno, halogen, or COOH or C000H. The typical rnonoperoxy carboxylic acids used herein include percarboxyl-1-alkyl acids and two such pereo-rings such as: (I) benzoic peroxy acid and peroxybenzoic acids substituted by a ring, for example, aliphatic peroxy-o-naph-1-ylco- (II) acid, substituted phenyl- and aliphatic rnonoperoxy acids, for example, peroxy laupco acid, peroxystearic acid, and N, N-t-lolaminoperoxycaproic acid (PAP). of typical diperoxy useful herein include chiraliperoids and aryldiperoxy acids, such as: (111) l, 12 ~ d? perox? dodecanedioic acid; dv) acid 1,9-d? perox? azela? co; (v) Depoxy-rubic acid, diperoxy-isbacic acid and diperoxnsophthalic acid, (vi) 2-dec? ld? perox? butane-l, 4-d? o? co (vile) acid 4,4 '-sulfom bi-speroxybenzoic acid. invention may also include bleaching compositions consisting of an effective amount of a bleaching agent. eo of insoluble organic percarboxylic acid having the general formula: 0 0 0 0 R, 1-C uN-R2-C ??-00H R, l -NC ??-R2, -C ??-00H R5 R5 wherein l is an alkyl group, aplo, or alloy which contains from about * 1 to about 14 atoms of carbon, is R2 an alkylene, apleno or alcar-ilen group? which contains from about 1 to approximately 14 carbon atoms, and R5 is H or an alkyl, aplo, or alkaline group containing from about 1 to about 10 carbon atoms. The peroxygen bleaching agents, the carbohydrates, the percarbonates, etc., preferably combine with bleach activators, which lead to the in situ production in aqueous solution (ie, during the washing process) of the perc box acid. i li co 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 4,575,393. One class of bleach activator 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: Et i l-4-sulfofen? 1 carbonate 2- (N, N, N-tprnet 11 ammonium) - (SPCC); N-octyl chloride, N, N-dirnetl-N-10-carbofenox idecil-amor or - (ODC); 4-sulfofen? Icar bonate of 3- (N, N, N ~ trimeti larnomo) --- (SPCC); and tolui loxibencenesulfonato of N, N, N, -tprnet ilarnomo. Other activators include 4-benzo? Lox? sodium benzenesulfonate; N, N, N ', N' -tetracet ilet lendiarnin; 1-met? I-2-benzo? Lox? Benzene-4-sulfonate; Sodium 4-methyl-3-benzoyloxybenzoate; sodium nonanoyloxybenzene fonate; 3, 5,5, -tpmethylhexanoiloxibencensulon sodium; glucose pentaacetate and teraceous protein xylose. Bleach activators also useful in the present invention are substituted amide compounds of the general formulas: 0 0 0 0 R1-CN-R2-CL, R1-NC-R2-CL RS R5 or mixtures thereof, wherein R1 is an alkyl, aplo, or alean group containing about 1 to about 14 volumes of carbon, R2 is an alkylene, aplene or alkarylene group containing about 1 to about L4 carbon atoms, R5 is H or an alkyl group, aplo or alloy which contains about 1 to about 10. Car-bond tomes, and the essential entity can be any suitable group. A residual group is any group that is displaced from the bleach activator as a consequence of the nucleophilic attack on the bleach activator by peroxide peroxide. This reaction of perohi drolysis 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 peroxidase ani. The L group must be reactive enough for the reaction to occur within the optimal time frame (for example, a wash cycle). However, if L is very reactive, this activator will be difficult to stabilize for use in a bleaching composition. These characteristics are generally paralleled by the pKa of the conjugated 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 approximately 13, preferably from about 6 to about 11 and most preferred about 8 to about 10%. 11. Preferred bleach activators are those of the above general formula wherein R 1, R 2 and RS are defined for the peroxy acid and L is selected from a group consisting of -N-C-R1 -N? N -N-C-CH-R4 A »U 1 I R3 and Y R3 YI -O-CH = C-CH = CH2 -O-CH = C ~ CH = CH2 and mixtures thereof wherein Ri is an alkyl, aryl or alkaryl group, containing about 1 to approximately 14 atoms of carbon, R3 is an alkyl chain containing from about 1 to about 8 carbon atoms, R * is 011 or R3, and Y is H or a ubiquitizing sun-group. Preferred solubilizers are -S03 ~ M +, - CÜ2-M + -S0 /; - M +, - N + (R3) ¿X ~ Y 0 < --N (R3) 3 and most preferred -SO3- 11+ and -C? 2 ~ M + where R3 is an alkyl chain containing about 1 to about 4 carbon atoms, M is a 5 cation which 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, methylsulphate or acetate anion. It should be emphasized that the bleach activators with a residual group that do not contain solubilizing groups should be diverted into the bleaching solution to aid in their dissolution. Preferred bleach activators are those 5 of the above general formula wherein L is selected from the group consisting of: where R is defined as shown before and Y is -S? 3_M +, -C? 2 ~ M + where M is as defined above. Preferred examples of the bleach activators of the above formula include 6-octanarn-docapro? Loxi Péncensulfonate, 6-nonanarn? Doca? Ro? Lox? Benzenesulfonat or, 6 -lecanarnide do-caproyloxybenzene fonate and mixtures thereof. Another important class-? of bleach actives provides organic perfects as described herein by means of a ring opening as a consequence of the cleophilic attack on the carbonyl carbon of the cyclic ring by means of the perhydrated ring. For example, this ring opening reaction in certain activators involves an ata < What about the lactam ring oarbonyl by means of hydrogen peroxide or its anion. Because the attack on an aeil-lactam by hydrogen peroxide or its anion occurs primarily in the exocyclic carbom, 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 the North American patent. 4,966,723, Hodge et al., Issued October 30, 1990.

Said activating compounds described by Hodge include the activators of the tPO benzoxaz no, which has the formula: including the substituted benzoxazines «I read type in which Ri is H, alkyl, alearyl, aplo, ap lalkyl, and wherein R2 R3, R1 and R5 may be the same substituents selected from H, halogen, alkyl, alkenyl, aplo, hydroxyl, alkoxyl, ammo, alkylammo, OOORe (where Re is H or a group to the?) and functions cai'boni Lo). A preferred activator of the bonzoxa type a is: When the activators are used, optimum bleaching performance is obtained on the surface with washing solutions wherein the pH of said solution is between about 8.5 and 10.5 and preferably between 9.5 and 10.5 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. Yet another class of preferred bleach activator includes the activators of acyl-lactarna, acylcaprolactate and acylvalerolact branching spheres of the f rmul: in «Jonde R6 is H, alkyl, aplo, alkoxy-ilo, or alkaryl« with about 10 carbon atoms, or a group «Je fen substituted that contains about * 6 to about 18 car-bonds . See also U.S. Patent 4,545,784, issued to Sanderson, October 8, 1985, incorporated herein by "reference, which describes acyl caprolactans, including benzoyl caprolactans, absorbed in sodium perborate. Vanos eje plos <: ue do not limit additional activators which may consist of bleaching compositions described herein include those in La page 2? No. 4,915,854, issued April 10, "Je 1990 to Mao et al., North American patent 4,412,934. The activators of nonanoi, i-sulphonate (NOBS), and tetracycimetiylene 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 top action of 1 cleaning / bleaching of the present compositions is also preferably achieved with certain parts of natural rubber machine and other natural rubber articles, including fabrics containing natural rubber and elastic natural rubber materials. The bleaching mechanism and, in particular, the bleaching mechanism of the surface are not fully understood. However, it is generally believed that the bleach activator suffers nucleophilic attack by a pep < 1rox i do, which is generated to belong < Jel hydrogen peroxide developed by the peroxygen bleach, to compound acid perox icarbox il LCO. This reaction is commonly known as pendro! ts s. The activators "Bleeding lactate and derivatives" in the present can also be used in combination with activators preferably hydrophilic, above followed, of safe rubber, such as TAED, typically, weight ratios of actives. caprolactarna or "he derived from arnido: TAED in the scale of 1: 5 to 5: 1, preferably approximately 1: 1.

Aqueous Acid Solutions and Methods The acid washing methods of the present invention require the use of aqueous acid solutions for decontaminants impregnated with metals originated by the metal-containing bleach catalysts. These metal-containing bleach catalysts as well as the components of the laundry compositions used to wash fabrics resulting in the impregnation of the fabric are described in detail herein. Such aqueous acid solutions preferably have a pH of less than about 4.0, and very preferred blenders have a pH within the range of about 1.0 to about 3.0. Acidifying agents useful for these solutions include, for example, sulfonic acid, rnaleic acid, citric acid, polyacrylic acids, but any acidifying agent can be used as long as it is safe to contact the fabric to be treated. Common acid solutions such as lemon juice and vinegar are also used. Acid rinsing solutions such as VTAKAL (sold by The Procter S Gamble Company, comprising 16% maleic acid and 3% citric acid) are useful for the present acid washing methods. Typical aqueous acid solutions comprise at least about 0.8% acidifying agent, preferably about 2 to 20% by weight of the solution to be contacted with the fabric to be treated. Useful compositions for the preparation of these solutions will typically be concentrated liquids containing at least 10% of the acidifying agent, or solid or granular compositions that dissolve in water to form the solution, and these compositions typically comprise at least about of 10% of the acidifying agent. The compositions are exemplified below. The method for bringing the fabric into contact with the aqueous acid solution includes any method by which all the fabric or substantially all the surface of it comes into contact with the solution. Typically this includes soaking the fabric in the solution, preferably for at least about 60 minutes. Another is to contact the fabric with the solution in the rinse cycle of the laundry procedures, with or without accompanying agitation. The spray of the fabric is also contemplated to saturate the fabric with the solution just before < Wash the fabric (preferably leaving at least approximately 15 minutes after the spray treatment before starting the washing procedure). Higher solution temperatures are allowed but are not necessary. Laundry compositions containing bleach catalysts <;: That they contain metal are distributed commercially, for example PERSTL POUER sold by * l.ever * (the catalyst being a complex that has manganese). Metal-containing bleach catalysts, and typical ingredients of the alkaline laundry detergent composition used in the present preferred methods are then provided.

Auxiliary ingredients The compositions herein may optionally include one or more other auxiliary detergent materials or other materials to aid * or improve cleaning performance, treatment of the substrate to be lightened, or to modify the aesthetics of the composition. detergent (for example, per-fumes, colorants, 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.

Antioxidant materials free radical scavengers: "Antioxidant materials radical scavengers "Free", as used herein, means those materials which act to prevent oxidation in products by functioning as free radical scavengers Examples of "antioxidants" may be added to the compositions of this invention include a mixture of ascorbic acid, ascorbic palmitate, propyl gallate, "Jispombles from Eastman Chemical Products., Inc., under the tradenames Tenox® PG and Tenox Sl, a mixture of BHT (hydrox L-toluene betylated), BHA (butylated hydroxyanisole), propyl gallate and citric acid, available from Eastman Chemical Products, Inc. under the tradename Tenox-6, hydroxy toluene butylated, available by UOP Process DiviSLon under the tradename Sustane® BHT; butyl dr-tertiary acid, Eastman Chemical Products, Inc., such as Tenox TBHQ, natural tocopherols, Eastman Chemical Pro <Jucts Tnc., such as Tenox GT-l / GT-2 and hydroxyamylated sol; Tlastrnan Chemical Products, Inc., such as BHA; rga (C8-C22), of a glic acid, for example, dodecyl gallate; Trganox® 1010; Trganox.RTM. L035, Trganox.RTM. B 1171; Irganox® 1425; Irganox® 3114; Irganox® 3125; mono, tert -butylhydroquinone ((MTDHQ), benzoic acid and salts thereof, toluic acids and salts of the same, t-buty 1 cat ecol, 1,1, 3-t ps (2-met? l-4- h? rox? -5- -buti phenyl) butaní topan l CA "available by * TCT); rnononoalkyl ethers of hydrotininone (eg, 4-methoxyphenol), and mixtures thereof. Preferred are BHT, BHA, TBHQ, propyl gallate, ascorbic acid and mixtures thereof. It should be recognized that for purposes of the present invention, materials useful on the contrary as antioxidants do not act as free radical scavengers, such as "material materials", which only work by chelating metals that can initiate oxidation reactions. "free radical scavenger anti-oxidant materials" herein, but are optional preferred material for use with anti-free radical scavenging materials. The term "antioxidant effective amount" as used herein, means an amount of free radical scavenger material to reduce the amount of the comparative test used, the degree of damage to fabrics. (including, for example, loss of tensile strength and / or damage in the color *) observed by the presence of a bleach catalyst containing metal in the composition. Such damage in the fabric can be evaluated under any typical washing condition. , including common washing conditions in Europe over 40 ° C. The preferred levels of antioxidant free radical scavengers that will be used in the products, therefore, are easily determined, and are typically present in the compositions according to the present invention within the scale of about 1 pprn. about 2%, preferably from about 20 pprn to about 6000 pprn, and most preferred from about 50 ppm to about 2000 ppm. Also, in a powder formation, the ant? Ox? Dante can be introduced into the formulation as a powder or through agglomeration or granulation or <; Any other procedure to keep the catalyst and antioxidant close to each other and also allow for rapid interaction in the process. Detergency builders - Builders can 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 desires "Ja. When present, the compositions will typically comprise at least about 1% detergency builder. Liquid formulations typically range from about 5% to about 50%, and typical of about * 5% to about 30%, or by weight of an orgin improver. Granulated formulations typically comprise from about 10% to about 80%, typically from about 15% to about 50% by weight of the detergent-enhancer. However, lower or higher detergency builder levels are not excluded. Examples "Silicate detergent builders are alkali metal silicates, particularly those which have a ratio of 2: N 2? in the scale from 1.5: 1 to 3.2: 1 and estratified silicates, such as the sodium silicates strati fi cally 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 the zeolite detergent builders, the NaSKS-6 silicate builder does not contain aluminum. NaSKS-6 has the morphological form of delta-a2S? 0s 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 in the present, but others stratified silicates, such as those having the general formula NaMS? x02x +? 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 in l < -\ I presented. Some other stratified silicates "Je Hoechst include NaSKS-5, NaSKS-7 and NaSKS-11 as the alpha, beta and gamma forms. As indicated above, the delta-Na2 S1O5 (NaSKS-6) form is the preferred ace to be used herein. Other silicates can also be used, such as magnesium silicate, which can serve as a tightening agent * in granular formulations, as a stabilizing agent for bleach and oxygen, and as a component of foam control systems. Examples of carbonate letergency enhancers are the alkali metal and alkaline metal carbons as described in German Patent Application No. 2,321,001 published on November 15, 1973. The aluminosilicate detergent builders are useful herein. invention. The alurinosilicate detergent builders are of great importance in the majority of heavy duty granular detergent compositions currently commercialized, and can also be a "major" detergent ingredient in formulations < He liquid detergents. The 111 cato pot detergency builders include those that have the empirical formula: Mz (zA102) and 3xH2? where z and y are integers of at least 6, the molar-zay relation is on the scale around LO to about 0.5, and x is an integer of about 15 to apr-ox of 264. The exchange materials ions of useful ions are commercially available. These alu- miniums may be crystalline or amorphous in structure and may be naturally occurring or synthetically derived alurninosiicates. A method for producing alumina ion exchange materials is described in US Patent 3, 985,669, Krummel et al. Issued on October 12, 1976. The preferred synthetic crystalline aluminosilicate ion exchange materials useful in the present are available under the designations Zeolite A, Zeol ta P (B), Zeolite MAP and 7eol? Ta X. In an especially preferred embodiment, the crystalline aiurninosilicate ion exchange material has the formula: Nai2T (AIO2) l2 (SiO2) l23 H2? wherein x is from about 20 to about 30, a specie of about 27. The material is known as Zeolite A. Dehydrated zeolites (x = 0-10) can also be used herein. Preferably, the aluminosilicate has a particle size of about 0.1-10 microns in diameter. Suitable organic builders 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. The polycarboxylagen detergent builders can generally be added to the composition as an 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 det ergents are a variety of useful material categories. An important category of polycarboxylate builders comprises ether polycarboxylates *, including oxydisuccinate, as described in Berg, Patent US 3,128,287, issued April 7, 1964, and Larnberti et al., Patent US. 3,635,830, issued January 18, 1972. See also "Jetergencia de" TMS / TDS "of US Pat. No. 4,663,071, issued to Bush et al. On May 5, 1987. Suitable ether poly carboxylates also they include cyclic compounds, particularly alicyclic compounds, such as <;, which are described in U.S. Patents 3,923,679; 3,835,163; 4,158,635; 4,120,874 and 4,102,903. The citrate detergent builders, e.g., citric acid and soluble salts thereof (par- ticularly sodium salt), are polycarboxylate builders of particular importance for heavy duty liquid detergent formulations because of their availability of renewable resources and their biodegradability. The citrates can also be used in granular compositions, especially in combination with aeolith and / or silicate builders. The oxides are also especially useful in said compositions and combinations. The fatty acids, e.g., rnonocarboxylate acids of C1-C18, can also be incorporated into the compositions by themselves, or in combination with the detergency builders above, "nene? Ona < Especially citrate and / or succinate detergent builders, to provide additional builder activity, such use of gr-asos will generally result in decreased foaming, which would be considered by the manufacturer. In situations where phosphorus-based detergency builders can be used, and especially in bar formulations used for hand-washing operations, various alkali metal phosphates such as sodium thio-phosphates can be used. known, sodium pyrophosphate and sodium orthophosphate Chelating agents - Although detergency builders can be used, the presently preferred compositions do not contain those manganese chelating agents that abstract the manganese from the catalyst complex. In particular, phosphates, phosphates and chelating agents of am ono fonat or such as DEQUEST are preferably not used in compositions However, the "nitrogen-based manganese chelating agents, such as ethylene-N, N'-disuccinate (FDDS), are useful. Surfactants - Non-limiting examples of non-knotted surfactants, additional, useful herein include the conventional Cn-Ciß quilbencelsulfonates ("LAS") and the primary C10-C20 alkyl sulfates ("AS"), of branched and random chain, the alkylsui to (2,3) secondary of Cio-Cis of the formula OH3 (CH2) x (CH0S03-M +) CH3 and CH3 (CH2) and (CHOSO3- M +) CH2 CH3 where xy (and «-l) are integers of at least 7, preferably at least about 9, and M is a cation of solubilization in water, especially sodium, saturated sulaphthanes such as oleosulfate, the alkylalkoxysulphates of Cio-Ciß (" AEX ", especially EO 1-7 ethoxysulfates), Cι-Oιβ alkylalkoxycarboxylates (especially the EO 1-5 ethoxy carboxylates), the Cι-Ciß glycol ethers, the Cpol-Cßß alkyl polyglycosides and their corresponding sulfated poly-glycosides , and alphasulfonated fatty acid esters of C12-C18. If desired, conventional non-ionic amphoteric surfactants such as C12-18 alkyl ethoxylates ("AE") including the so-called narrow-spun alkyloxylates and the C6-C12 alkylphenolalkolates (especially 0x1 latos and ethoxy). mixed propoxy), C12-C18 betaines and sulfobetaines ("sultaines"), C10-C18 amine oxides, and similes, can also be included in the overall compositions. It is also possible to use amides of fatty acid N-to the cholyl polyhydroxol. Typical examples include N-rnet 1 lglucams of C12-18- See UO 9,206,154. Other surfactants derived from sugar include the N-al coxy pol 1 ludroxilico fatty acid amides, such as N- (3-rneto-xyl) glucanone from Cío-Cie - M-proptl to N-hexylglucamides «Je C12-C18 can be used for low foaming. Conventional C10-Q20 soaps can also be used. Mixtures of ammonium and non-ionic surfactants are especially useful. Other conventional useful tonsional agents are listed in the normal texts. Particularly suitable nonionic surfactants for dishwashing are straight-boiled ethoxylated alcohols of low foaming or non-spurring such as Plurafac ™ of the RA, its inurated by Eurane Co., LutensolTM LF series, its supplied by BASF Co., TntonTM DF series, supplied by Roh 8 Haas Co., and SynperonicTM LF series, supplied by * TCI Co. Clay dirt removal agents / anti-reposition. - The compositions of the present invention may also optionally contain water-soluble ethoxylated amines having clay dirt removal and anti-redeposition properties. Detergent compositions in granules containing these compounds typically contain from about 0.01% to about 10.0% in weight of water soluble ethoxylated amines.; Liquid detergent compositions typically contain about 0.01% to about 5%. The preferred preservative and anti-fouling agent is tetraethylene pentane ethoxylated. The ethoxylated amines of example are described more extensively in the patent of E.U.A. No. 4,597,898, Vander-Meer, issued July 1, 1986. Another group of removers / anti-redeposition agents • The clay filings are the cationic compounds described in European Patent Application 111,965, Oh and Gosselinl--, published on 27 June 1984. Other renderers / anti-redeposition of clay soils which can be used include the ethoxylated amine polymers described in European Patent Application 111,984, Gossel n, published June 27, 1984; the zwitterionic polymers described in the Application < 1e European Patent 112,592, Gosselink, published on July 4, 1984; and the amine oxides described in the U.S. Patent. No. 4,548,744, Connor, issued October 22, 1985. Other clay replenishing and / or anti-redeposition agents known in the art can be used in the compositions herein. Another type of preferred antiretroviral agent includes carboxycellulose Icelulose (CMC) materials. These materials are well known in the art. Polymeric Dispersing Agents - Polimeric 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 and / or silicate builders. stratified Suitable polymeric dispersing agents include polyne carboxylates and polyethylene glycols, although other techniques known in the art can also be used. It is believed, although not intended to be limited by theory, that polyaromatic dispersing agents increase the performance of the global detergent-reduction agent, which amount is used in combination with other detergency builders (including lower carboxylic carboxylic acid). by inhibition of crystal growth, peptisation of release of dirt into particles and anti- redeposition.

Polyarboxylate polyarboxylate materials can be prepared by polishing or copolymerizing suitable unsaturated monomers, preferably in their acid form. Unsaturated monomeric acids which can be polymerized to form suitable polycarboxylic polycarboxylates include acrylic acid, aleic acid (or maleic anhydride), fumaric acid, itaconic acid, aconitic acid, mesacomco acid, eitracomco acid, methylene-nonane. The presence of the polycarboxylic polycarboxylates in the present or polyrnery segments, which do not contain carboxylate radicals such as vinyl ether, tin, ethylene, etc., is suitable provided that said segments do not constitute more than about 40%. % in weigh. Particularly suitable polydrug polycarboxylates can be prepared from acrylic acid. Said acrylic acid polymer polymers which are useful herein are the water soluble salts of polyrneized acrylic acid. The average molecular weight of polymers in the permutably acidic form ranges 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 may include, for example, the alkali metal, ammonium and substituted ammonium salts. Soluble polymers of this type are known materials. The use of such polyacrylates in detergent compositions has been described, for example, in Diehl, U.S. Pat. 3,308,067, issued March 7, 1967. Copolymers based on acrylic / maleic acid may also be used as a preferred component of the dispersing / anti-redeposition agent. Such materials include the water soluble salts of copolymers of acrylic acid and aleic acid. The average molecular weight of said copolymers in the formulation 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 acrylic segments to the maleate 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 / inaleic acid copolymers may include, for example, the alkali metal, ammonium and substituted ammonium salts. Soluble acrylate / rnaleate agents of this type are known materials which are described in the Application "European Patent No. 66915, published on 15 January" 1982. Other polyphenolic material which may be included is polyethylene glycol (PEG). . PEG can exhibit dispersing agent performance and can act as a dirt removal / anti-redeposition agent for clay. 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. The dispersing agents of polyaspartate and polyglutamate can also be used, especially in conjunction with improved < Zeres of detergency of zeolite. Dispersing agents such as those of preferable polyaspartate have a molecular weight (pro.) Of about 10,000. In images. - 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, carbohydrate-based or liquefied-based spots, 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, nicotonic and yeast origin. However, your choice is governed by many factors such as pH activity and / or optimal stability, thermostat 11, stability against active detergents, builders, etc. In this regard, bacterial and enzymatic enzymes, such as bacterial arnilases and proteases and mycotic cellulases, are preferred. Enzymes are normally incorporated at levels sufficient to provide up to about 5 weight per cent, very typically about 0.01 to about 3 mg of active enzyme per gram of the composition. In other words, the compositions herein typically comprise from about 0.001% to about 5%, preferably from 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 units of Anson (AU) activity per gram of composition. Suitable examples of pro houses are subtii? O? which are obtained from particular strains of B.subtil and B. licheniforms. Another suitable protease is obtained from a strain of Bacillus that has maximum activity throughout the pH range of 8-12, developed by Novo Tndud ies 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 most commercially available proteolytic enzymes suitable for removing protein-based stains include those sold under the registered trademarks "Ja ALCALASE and SAVTNASE" Je Novo Industries A / S (Denmark) and MAXATASE of Alternative Lonal B? o ~ Synthet? cs , Inc. (Netherlands). Other proteases include Protease A (see European Patent Application 130,756 published on 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).

Arnilases include, for example, cr-amylase 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 5. The lipase enzymes suitable for use in detergents include those produced by microorganisms of the Pseudomonas group, such as Pseudornona 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 is available from Amano Pharmaceuti cal Co. Ltd., Nagoya, Japan, under the registered trademark Lipasa P "Amano", which is hereinafter referred to as "Amano-P". Other commercial lipasae include Amano-CES, Lipases' Ex ex Chromobacter v scos? N, v.gr. Chroinobacter viscosum var * .. lipolyctuin NRRLB 3573, commercially available from Toyo Jozo Co., Tagata, Japan; and also the Chromo acter viscosum lipases from U.S. Boichemical Corp., E.U.A. and Disoynth Co., The Netherlands, and lipases from ex Pseudomonas gla iol. the LIPOLASE enzyme derived from Huricola lanugosa and which is commercially available from Novo (see also EPO 341,947) is a preferred lipase for use herein. Enzymes of perox and asa are used in combination oxygen supplies, V.gr *., Percarbonate, perborate, per-sulfate, hydrogen peroxide, etc. They are used for "blanejicaciónras 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 halogenperoxidase such as chloroperoxidase and broperoperoxidase. Detergent compositions containing peroxidase are described, for example, in PCT International Application WO 89/099813, published October 19, 1989 by O. Kirk. assigned to Novo Indudt r *? is A / S. A wide variety of enzyme materials and minerals are disclosed for incorporation into synthetic detergent compositions in US Pat. 3,553,139 issued January 5, 1971 to McCarty and others 9d? Cyanoinly described enzymes in the patent of E.U.A. 4,101,457, Place et al., Issued July 18, 1978 and in the U.S. Patent. 4,507,219, Hughes, both issued on March 26, 1985. Useful enzyme materials for formulations of liquid detergents and their incorporation into such formulations are described in the Patent of F.U.A. 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 on August 7, 1971 to Gedge, et al., And in European Patent Application Publication No. O 199 405, Application No.86200586.5, published on October 29, 1986, Venegas. Enzyme stabilization systems are also described, for example, in the U.S. Patent. 3,519,570. Stabilizers «Je enzymes.- The enzymes used in The present are typically stabilized by the presence of water-soluble supplies of calcium and / or magnesium ions in the finished compositions which provide 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 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 8 to about 12 my limones of calcium ions per liter of finished composition. This of some odo can 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 complex compounds with builders, fatty acids, etc., to form 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 naleate, calcium hydroxide, Calcium and acetate acetate, calcium and the corresponding magnesium salts A small amount of calcium ions, usually from about 0.05 to about 0.4 mmol per liter, is also present in the composition due to calcium present in the enzyme suspension and water of the formula In solid detergent compositions the formulation may include a sufficient amount of a supply of calcium ions soluble in water to provide such amount in the liquor «He washed. Alternatively, the hardness of the natural water may be sufficient. It should be understood <The above-mentioned levels of calcium and / or magnesium ions are not sufficient to provide stability of the enzyme. Additional calcium and / or magnesium ions can be added to the compositions to provide an additional measure of fat removal performance. If used for such purposes, the compositions herein should typically comprise from about 1% to about 2% by weight of a water-soluble supply of calcium or magnesium ions or both. The amount can vary, of course, according to the amount and type of enzyme used in the composition.

The composition may also optionally, but preferably, contain several additional stabilizers, especially stabilizers, such as borate. 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%, preferably from about 0.75% to about 3% by weight of boric acid. 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 metaborate and sodium piperate and sodium pentorate) are suitable. Substituted boric acids (v.gr-., Feml -boronic acid, butanobor oni co acid and p-bromopheni lboronic acid) may 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, "Jepvados" Je eeti lbeno, pyrazolma, curnapna, carhoxyl acid, metmoc amnas, 5,5-dioxide of dibenzothiophene, azoles, heterocyclics of 5 and 6 members, and other diverse agents. Examples of such brighteners are described in "The Production and Application of Fluorescent Bpghtemng Agents," M. Zahradnik, published by John Uiley S 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 Wixon on December 3, 1988. These brighteners include the PHOROWHITE series of brighteners from Verona. Other brighteners described in this reference include Tinopal UNPA, Tinopal CBS and T opal 5BM; available from Ciba-Geigy; Art c Uhite CC and Artic CJhite CUD, available from H lton-Davis, headquartered in Italy; the 2- (4-stp -feml) -2H-naphtholCl, 2 dütpazoles; 4,4'-b? S (1, 2, 3- < pazol- 2-2-? L) -esti Ibenos; 4,4'-b? S (sterile) b? Sfem; and the occurrences. Specific examples of these brighteners include 4-rnet? L-7-diet ti -arninocurnapna; 1, 2-bts (-benz? Rn?) Jazol-2-l ethylene; 1,3-d? Fm 1 -frazole; 2,5-b? S (benzoxazol-2-l) t of no; is r-l-naph-L-1, 2-dloxazole, and 2 - (est-lben-4-l) -2H-naphtho-p, 2 -duetriazole. See also US Patent 3,646,015, issued on 29 February, 1972 to Ha ilton, Anion i eos polishers are preferred here Foam suppressants - Compounds for reducing or suppressing the formation of foams can be incorporated into the compositions of the present invention. importance in the "high-concentration cleaning procedure" and in front-loading European-style washing machines A wide variety of materials can be used * as foam suppressors, and foam suppressors are well known to those skilled in the art See, for example, Kirl-Oth er Encyclopedia of Chemical Technology, 3rd Edition, Volume 7, pp. 430-447 (John Uiley S Sons, Inc., 1979) A category of suppressor Particular foam of 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 nonocarboxylic fatty acids and salts of the same as a foam suppressant typically have hydrocarbyl chains of from 10 to about 24 carbon atoms, preferably from 12 to 18 carbon atoms. Suitable salts include alkaline metal salts such as sodium, potassium and lithium, as well as ammonium and alkanol monium salts. The detergent compositions herein may also contain suds suppressants which are not surfactants. These include, for example: high molecular weight hydrocarbons such as pair refines, fatty acid esters (eg, fatty acid ligands), fatty acid esters of monovalent alcohols, aliphatic ketones of (eg, stearone) ), etc. Other foam inhibitors include N-alkylated arninotpazines such as tp- to hexa-alkylrnelamines or di- to tetra-alkyldia inoclothnazines formed as products of cyanuric chloride with two or three moles of a primary or secondary amine containing from 1 to 24 atoms of carbon. propylene oxide and monostearate phosphates such as inosteroaryl alcohol phosphate ester and alkali metal diphosphates (e.g., K, Na and Li) rnonoestearí 1 icos and ester phosphates. Hydrocarbons such as paraffin and hai oxygen paraffins can be used in the form Liquida. The liquid hydrocarbons will be liquids 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 corozal hydrocarbons, preferably having a melting point below about J00 ° C. Hydrocarbons constitute a preferred category of foam suppressant for detergent compositions. ., The hydrocarbon foam suppressors are described, for example, in U.S. Patent 4,265,779 issued May 5, 1981 to Gandolfo et al. The hydrocarbons, therefore, include saturated or saturated to the phthalic, alicyclic, aromatic and heterocyclic hydrocarbons having from about 12 to about 70 carbon atoms. The term "paraffin", as used in the discussion of suppressants, is intended to include mixtures of true paraffins and cyclic hydrocarbons. Another preferred category of suppressors is that foam which are not surfactants comprise ilicon foam suppressors. This category includes the use of polorganosiloxane oils such as polydimethylsiloxane, dispersions or emulsions of polyorganosiloxane oils or resins, and combinations of polyorganosi loxane with silica particles wherein the polyorganosiloxane is chemoabsorbed or fused onto the silica. Suppressors of silicone foams are well known in the art and are described, for example, in US Pat. No. 4,265,779, issued on May 5, 1981 to Gandolfo et al. And European Patent Application No. 89307851.9, published on February 7 «Je 1,990 by Starch, MS Other silicone foam suppressors are described in U.S. Patent 3,455,839 which relate to compositions and processes for defoaming aqueous solutions by incorporating therein small amounts of fluids of polydimethylsiloxane. Silica and silanated silica mixtures are described, for example, in German Patent Application DOS 2,124,526. Silicone foam scavengers with and foam controlling agents in granular detergent compositions are described in US Patent 3,933,672, Bartolotta et al. And in US Patent 4,652,392, Bag si et al., Issued March 24, 1987. An illustrative silicon-based foam suppressant to be used herein is a suppressive amount of foams of a foaming agent which consists essentially of: (i) polydirnetyl-siloxane fluid having a viscosity of about 20 is at approximately 1,500 it is at 25 ° C; (11) of about 5 to about 50 parts per 100 parts by weight of (i) compound siloxane resin "units of (CH3) 3S? 0? 2 units of S1O2 in a unit ratio of (CH3) 3 * 5? O? 2 to S1O2 units of about 0.6: 1 to about 1.2: 1; and (111) from about 1 to about 20 parts per 100 parts by weight of (1) of a solid silica gel. In the preferred ilicon foam suppressant used in the present, the solvent for a continuous phase is made of certain full polyethylene glycols or polyetherien-polypropylene glycol copolymers or mixtures thereof (prefixes) and nonpolypropylene glycol. The suppressor of sii foams with primary is ramified / in relative and non-linear To illustrate this point further, the typical liquid laundry detergent compositions with controlled spraying optionally comprised of about 0.001 to about L, I preferred from about 0.01 to about 0.7, preferably from about 0.05 to about 0.5,% by weight of said silicone foam suppressor, comprising (1) a non-aqueous emulsion of a primary foam-forming agent which is a mixture "Je (a) a polyorganosiloxane, (b) a resinous siloxane or a silicone compound producing silicone ream, (c) a finely divided filler material and (d) u n catalyst to promote the reaction of mixture components (a), (b) and (c) to form ilanolates; (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% in peeo; and without polypropylene coi. Similar amounts can be used in granulated gels, etc. See also Patents of E.U.A. 4,978,471, Starch, issued on 18 December 1990 and 4,983,316, Starch, issued on 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 pressor of the present preferably comprises polyethylene glycol and a polyethylene glycol / polypropylene glycol copolymer, all having a average molecular weight less than 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 of about 2% by weight, preferably more than about 5% by weight. The preferred solvent herein is polyethylene glycol having a molecular weight of less than about 1,000, most preferably between about 100 and 800, most preferably even between 200 and 400, and a polyethylene glycol / polypropylene glycol copolymer, preferably PPG 200 / PEG 300. A weight ratio of between about 1: 1 and 1:10, preferably between 1: 3 and 1: 6, of polyethylene glycol: polyethylene battery is preferred. -polipropí lenglicol. The preferred silicone foam suppressors used herein do not contain polypropylene glycol, particularly of molecular weight of 4,000. Preferably they also do not contain block copolymers of ethylene oxide and propylene oxide, such as PLURONIC L101. Other foam suppressants useful therein 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 Ce-C alkyl alcohols that have an Oi-Cis chain - an alcohol "preferred is 2-but? loctanol, which is available from Condea under the trade name ISOFOL 12. Mixtures of secondary alcohols are available under the tradename TSALCHEM 123 from Emchern.The suppressors" Je mixed foams typically corn? ren "Jen mixtures of alcohol + silicon 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 a suppressing amount of foam. By "" amount of foam suppression "it is understood that the formulator of the composition may select an amount of this foam controlling agent that will sufficiently control the foams to result in a laundry detergent "Je ba a foaming for use in automatic washing machines." The compositions of the present general nte to understand «Je 0% to approximately 5%« Je supressor- of foams. When used as foam suppressors, monomeric 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 fat suppressant is used. The silicone foam suppressors are typically used in amounts 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% silicone foam suppressant, most preferably from 0.25% to about 0.5%, is used. As used herein, these values in percent by weight include any silica that can be used in combination with polorganosiloxane, as well as any auxiliary materials that can be used. The rnonoesteapl phosphate foam suppressors are generally used in amounts ranging from about 0.01% to about 02% by weight of the composition. The "foam" suppressants 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 smectite clays of the US 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 about 0.5% to about 10% by weight in the compositions of this par. -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 Crtsp et al., March 1, 1983 and The Patent of E.U.A. 4,291,071 to Harris et al., Issued September 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 polymers of polyvinylpyrrolidone, polyarynin N-oxide polymers, copolymers of N-vinylpyrrolidone and N-VLnilimidazole, manganese phthalocyan, 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 polyarnide N-oxide polymers for use herein contain units having the following structural formula: R-A "-P; where P is a polynomial unit to which a N-0 group can be attached or the N-0 group can form part of the poly-pzable unit or group N-0 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 group N-0 can be attached * or the group N-0 is part of these groups. The preferred polyarynin N-oxides are those in which R is a hoterocyclic group such as pipd a, pyrrole, irnidazole, pyrrole, pipe pdma and derivatives of the same. The group N-0 can be represented by the following general structures: OR O (Ri)? -N- (R2) y; = N- (R?)? (R3)? 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 linked * or be part of any of the aforementioned groups. The amine oxide unit of the polyane N-oxides has? N pKa < 10, preferably? Ka < 7, very pre-eminently still pKa < 6. Any polymer base structure can be used as long as the amine oxide polymer formed is soluble in water and has dye transfer inhibiting properties. Examples of suitable polymeric base structures are polymers, polyalkylenes, polyesters, polyethers, polyalpha, polynides, polyaptates and mixtures of the isms. These polymers include random block copolymers in which one type of monomer is a N-oxide of arnine 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 grups present in the polyolefin polymer can be varied by appropriate copolymerization or by an appropriate degree of N-oxidation. Polyamine oxides can be obtained in almost any degree of polymerization.

Typically, the average molecular weight is within the range of 500 to 1,000,000; I preferred "1,000 to 500,000; I still prefer 5,000 to 100,000. The most preferred N-oxide polyamine useful in the detergent compositions herein is N-oxide or poly-4-vm? L? R? D? Na having an average molecular weight of about 500,000. and an amine to amine N-oxide ratio of about 1: 4. Polymer copolymers of N-vini lporrol idone and N-vim lirnidazole (known as "PVPVT") are also preferred for use herein. Preferably, the PVPVI has an average molecular weight in the range of 5,000 to 1,000,000, most preferably 5,000 to 200,000 and most preferably even 10,000 to 20,000. (The average molecular weight scale is determined by Light scattering as described in Barth, and other Chemical Analysis, Vol. 113. "Modern Methods of Polymer 'Charactepzation", the descriptions of which are incorporated herein by reference). Copolymers of PVPVT typically have a molar ratio of N-vmilimi dazol to N-vinylpyrrolidone from 1: 1 to 0.2: 1, most preferably from 0.8: 1 to 0.3: 1, preferably preferably "Je 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 about 5,000 to about 400,000, preferably from about 5,000 to about 200,000, and most preferably even from about 5,000 to about 50,000. PVP's are known to those skilled in the art of 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 a prized 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 pprn assorted in wash solutions is from about 2: 1 to about 50: 1, and most preferably from about 3: 1 to about 10: 1. Latent detergent compositions herein may also optionally contain from about 0.005% to 5% by weight of certain types of hydrophilic optical brighteners which also provide a dye transfer inhibiting action. If used, the compositions herein will preferably comprise from about 0.01% to L% by weight of said optical ablators. The optical drillary brighteners useful in the present invention are those which have the structural formula: R, t S-O3? M SO3Mt where Ri is selected from anilino, N -? - b? S-hydrox? Et? what and NH-2-h? drox? et? the; R2 is selected from N-2-b? S-hydrox? Et? Io, N-2-hydrox? Et? L-N-rnet? Lam? No, morphyl, chlorine and ino; and M is a salt forming cation * such as sodium or potassium. When in the previous formula, Ri is aniline, R2 is N-2-b? Sh? Drox? Et? Lo and M ee a cation such as sodium, the brightener is acid 4, ', bisC (4-an? L? No-d- (N-2-b? S -hydroxyethyl) -s- tr? az? n-2-ylamino] -2,2 '-est phonyl ester and disodium salt This particular kind of brightener is commercially marketed under the tradename T opal- UNPA-GX by Ciba-Geigy Corporation T opal-UNPA-GX is the preferred hydrophilic optical brightener preferred in the detergent compositions of the present invention When in the above formula Rl is aml, R2 is N-2-h? DrOx? et? iN-2-rnet? larn? no and M is? n cation such as sodium, the brightener is the disodium salt of acid, 4 '- b 1 sC (4 -a ni linen- 6- (N-2 -h? dro iet 1] -N-meti lamino) - st nazi n-2-? l) arn? no.l-2, 2 '-est ilbendisul f nico.This particular kind of brightener * is marketed cornercílamente bajo the commercial name Tinopal 5BM-6X by Ciba -Geigy Corporat ion.When in the previous formula Rl is amlino, R2 is inorphilino and M is an ac such as sodium, the brightener * is the sodium salt of acid 4, 4'-bisT (4-aml? no-6-? norf il? no ~ st naz? n-2 ~? l) arn? noJ2, 2 '-It is lbendisul phonic. This particular brightener species is sold separately under the trade name Tinopal AMS-GX by Ciba-Geigy Corporation. 55 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 abovementioned polymecopyl dye transfer inhibiting agents described above. The combination of said selected polymetallic materials (e.g., PVNO and / or PVPVI) with said selected optical brighteners (e.g., Tinopal UNPA-GX, Tinopal 5BM-GX and / or T opal 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 coefficient of depletion is in general the ratio of a) the polishing material deposited on the cloth to b) the initial polish concentration in the wash liquor. The openings with relatively high depletion coefficients are most suitable for inhibiting dye transfer in the context of the present invention. It will be appreciated, of course, that the other types of conventional optical brightener of compound may optionally be present in the present invention. 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? Ngr *? D? entities - A wide variety of other ingredients useful in cao detergent positions can be included herein, including other active ingredients, vehicles, hydrotropes, processing aids, dyes and pigments, solvents for liquid formulations, sunscreens for bar compositions , etc. If high ospharnation is present, foaming enhancers such as C10-C16 alkanolamines can be incorporated into the compositions, typically at levels of 1% -10%. "The inonoet nol and" Jietanolarní of C10-C14 illustrate a typical class. of said foam increments. The use of such increments «Foam with auxiliary surfactants with high spurious such as amine oxides, beta plus and sultamas previously mentioned is also advantageous. If desired, the soluble magnesium salts such as MgCl, MgSO-4 and the like, can be added at typically 0.1% -2% levels, to provide additional sputtering and to increase the fat-burning 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 substrate with a hydrophobic coating. Preferably, the detersive ingredient is mixed with a surfactant before it is 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 with more detail, a porous hydrophobic silica (trade name SIPERNAT DIO, Degussa) is mixed with a solution of the proteolytic enzyme containing 3% -5% nonionic alcohol ethoxylated side-by-side 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 silite oil with (various viscosities of silicone oil in the range of 500-12,500 can be used). The resulting silicone oil dispersion is emulsified or otherwise added to the final detergent matrix. For this reason, ingredients such as enzymes, bleach, bleach activators, bleach catalysts, foactives, dyes, fLuorescers, fabric conditioners and above-mentioned hydrolysable surfactants can be "protected" for use in detergents. , including liquid laundry detergent compositions. The liquid detergent compositions may 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. Rnonohydric alcohols are preferred for soluble Lysol surfactant, but polyols such as those containing 2 to 6 carbon atoms and 2 to 6 hydroxyl groups (e.g., 1,3-propanediol, ethyl glycol) can also be used. , glycepna and 1, 2-? ro? anod? ol). 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 formulations of washing products (automatic tableware) have a pH between approximately H and approximately 11. Laundry products typically have a pH of 9 to 11. The techniques for controlling the pH to levels of use Recommendations include the use of pH regulator, 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.; | ue that are Limiters of it.

EXAMPLE I A dry laundry bleach is as follows: Ingredient% (p) Per-sodium carbonate 20.0 Activator of Benzoyl-caprolactam LO.O Catalyst of Mn * 85ppm Water-soluble filler ** Remainder * Mniv2 (? -0) 3 ( 1,4, 7-t rimeti1-1, 4,7-t pazac clononane) 2 (PFß) 2, as described in US Pat. No. 5,246,621 and 5,244,594. ** Carbonate blend «Je sodium, sodium silicate (1: 1). In the above composition, the sodium percarbonate can be replaced by an equivalent amount of per-borate. In the above composition, the bleach catalyst can be replaced by an equivalent amount of the following catalysts: MnHi2 (? - 0)? (u-0Ac) 2 (1, 4, 7-t pinet? L-1, 4,? -triazac clononane) 2 (CIO4) 2; iv ^ (u-0) ß (1, 4, 7 -tpazací clononane) «(CIO)«; niU niV; (u-O)? (u-0Ac) 2 (1,4,7- + r? rnet? l-l, 4, 7-t r *? azac? clononane) 2 (CIO;) 3; MnIV (1,4, 7-tr? Rnet? L - L, 4, i'-t pazac? Clononane (0CH3) 3 (PFe); Gluconate of Mn, (CF3 & 03) 2; Mn Lunuclear complexed with li « ja do tetra-N- "Jentato and bi-N-dentato,? ncluyen" Jo N «i 11 (u-0) niVN.v) + and í" B ?? y2 nin (u-0) 2 niv b? py21- (CIO) 3, and mixtures of the same .. In addition, in the above composition, the bleach activator can be replaced by an equivalent amount of the following activators: valerolacta ato «Je benzoyl, nonanoyl caprolactarnate, valerolactamate of nonanoyl, 4-n-trobenzoyl caprolactamate, 4-methylbenzoyl valerolactane, caprolactamate "octa octane, octanoyl valerolactane, caprol ketone" Je "Jecanoyl, decanoyl valerolactanate, undecanoyl caprolactamate, valeroLactamate" Un undecanoyl, 3,5,5-trirnethylhexanoyl caprolactam, 3,5,5-tr? rnet? hexane, valeroyactamate, dinitrobenzoyl caprolactam, valerolactanate, (Jim trobenzoyl, terephthaloyl dicapr-olactamate, terephthaloyl divalerolactam, (6-octanadine dockel) -oxybenzensul fonate, (6-nonanam? Docapr-o? L) ox? Benzensul fonate, (6-decanarn? Docapro? L) ox? Benzensul fonato, and mixtures of the same. The compositions of Example I can be used per a bleacher, or they can be added to a detergent composition of rinsing or containing surfactant to impart a whitening benefit therein. In the following laundry detergent compositions, the abbreviated component designations have the following meanings: LAS - C12 Sodium alkylbenzene fonate TAS - Sodium tallow alkyl sulfate TAEn - tallow alcohol ethoxy «Jo con n moles of filled ef oxide per mole of alcohol 25EY - A predominantly linear primary alcohol of C12-15 condensed with a mean "Je Y moles ethylene oxide TAED - Etilendiam or tertraacet i lo Silicato - Amorphous sodium silicate (S? 2 ~ Na2 - normally in the following proportion) NaSKS-6 - Laminated crystalline silicate Carbonate - Anhydrous sodium carbonate CMC - Carboxymethyl sodium cellulose Zeol ita A - Hydrated sodium aluminosilicate (it has a primary particle size on the scale of 10 hours Citrate - Trisodium citrate dehydrated Ma / AA - Copolymer of aleic acid / acrylic 11 co 1: 4, average molecular weight 80,000 approximately Enzyme - Enzyme proteol Mixed paper and mill sold by Novo Industries AS. Brightener - 4 '4-b? S (2-rnorfol ino-l -ani lino-s-tr? Az? N-6-1 lamino) est? Lben-2,2' -disodonate disodium. Foam suppressant - Paraffin wax 25% mp 50 ° C, hydrophobic silica 17%, fine oil 58%. Sulfate - Dur-anhydrous sodium sulfate Dur-before use for fabric cleaning, the compositions are used conventionally and in conventional concentrations. Thus, in a typical mode, the compositions are placed in an aqueous liquor at levels that can range from about 100 ppm to about 10,000 ppm, depending on the dirt load and the stained fabrics that are agitated there.

EXAMPLE II The following detergent compositions (parts by weight) were prepared 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 Ci 6.5 6.5 6.5 - MA / AA 4.25 4.25 4.25 4.25 4.25 aSKS-6 10.01 JO. neither Citric acid - - ~ - 2.73 2.73 GAESO - - - 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 Caprolact amazo de benzol lo 10.0 10.0 __ 5.0 ~ - TAED __ 5.0 5.0 5.0 5.0 Catcher of Mn (pprn Mn) 35 25 18 8 14 CMC 0.48 0.48 0.48 0.48 0.40 S? Presor- de esi Du a 0, .5 0 .5 0, .5 0 .5 0 .5 Brightener 0.24 0.24 0.24 0.24 0.24 Enzyme 1.4 1.4 1.4 J.4 1.4 Silicate (proportion 2.0) 4.38 4.38 4.38 MgS0.i 0.43 0.43 0.43 0.43 0.43 Perfume 0.43 0.43 0.43 0.43 0.43 Sulfate 4.10 4.10 4.10 11.67 11.67 Water and miscellanies to adjust. * Mni v2 (u-0) 3 (1/4, 7-tpmet? L-l, 4,7-tpazacyclononane) 2 (PFß) 2 The above compositions can be modified with the addition of lipase enzymes. The above compositions can also be modified by replacing the catalyst with bleaching with an equivalent amount of bleach catalysts identified in Example T,. The above compositions can also be modified by repeating the < or the benzoyl caprolactam with an equivalent amount of the bleach activators identified in Example T. The above compositions can also be modified by replacing the TAED with an equivalent amount of NOBS, or "Dyeing the TAED out of the formulation. The above compositions can also be modified by replacing the perborate with an equivalent amount of perchloridate.

EXAMPLE III A laundry bar with bleach was prepared with normal extrusion procedures and comprises: LAS of C12-13 (20%); tripolyphosphate «Je sodium (20%), sodium silicate (7%), perborate monohydrate« Je sodium (10%), (6-decanami docaproyl) ox? bencensul fonate (10%); Mn1 v2 (u-0) 3 (1,4,7-tr? Rnet? L-1,4, 7-t pazac? Clononane) 2 (PF?) 2 (100 ppm); MgS0 «or alco-filling; and water (5%). The above compositions can be modified with The addition of lipase enzymes. The above compositions can also be modified by replacing the bleach catalyst * with an equivalent amount of the bleach catalysts identified in Example J. The above compositions can also be modified by replacing the bleach activator (6-decanamidocaproyl) or oxbenezenesulphonate with an amount equivalent of the bleach activators identified in Example T. The above compositions can also be modified by replacing the perborate with an equivalent amount of percarbonate. All the granular compositions herein can be provided as spray dried granules or granules or high density agglomerates (above 600 g / 1). If desired, the Mn catalyst can be adsorbed on and in water-soluble granules to keep the catalyst separated from the rest of the compositions, thus providing storage stability. Such granules (which should not contain oxygen components) may comprise, for example, water-soluble silicates, caronates and the like. Although the above compositions are typical of those which are useful herein, it is preferred that: L) the compositions do not contain STPP builder; (2) that the proportion of nonionic surfactants: ammonia is greater than 1: 1, preferably 1.5: 1, and (3) that at least 1% of perborate or other chlorine scrubber is present in the compositions for Minimize the formation of n? 2 during use.

EXAMPLE IV % by weight Zeolit 38.0% Silicate 2.0R 6.0% Carbonate (Sodium) 7.0% Energetic etra-ethi Jen fos fonato 0.2% Brightener 47 (Tinopal DMS) 0.1% Brightener 49 (Tmopal CBS) 0.05% Percarbonate 14.0% TAED 3.0% Catalyst of Mn * (p? m) 7 Savmasa (4.0 KNPU / g) 2.0% Lipolase (100,000 LU / g) 0.22% Alkylsulfate of C12-14 5.6% AE4.2 nonionic «Je C12-14 11.6% Habon 1.0% Ingredients < J? Verses / humidity to adjust 100% * Mniv2 (? -0) 3 (l, 4,7-tpmet? L-l, 4,7-r? Azac? Clonane) 2 (PFe) 2 This composition is used to prepare a laundry solution for washing fabrics. The solution is prepared by dissolving the composition in water (to provide a concentration of 0.1 pprn of manganese originating from the catalyst), and then washing the fabrics in a washing machine at 60 ° C.

EXAMPLE V Fabrics washed 30 times in a detergent composition < The laundry (conte contema the bleaching catalyst MnIV (u-0) 3 (1, 4,7-tpmet? Ll, 4, 7-tp azaciclononanoh (PFd) 2 (PERSIL POUER, sold by Lever-), were analyzed for «Jeter inar the level of impregnation« Je Fabrics by this catalyst This fabric is then soaked for 60 minutes in a solution of 11 VIAKAL at 5% (sold by The Procter * S Gamble Company) (it contained a pH of 2.0) Analysis of the fabrics after soaking and drying indicate that the level of the catalyst present in the fabric had been reduced. then washed with an alkaline-free alkaline laundry detergent product such as ARIEL COLOR (sold by The Procter- &Gamble Cornpany) Simulated results were obtained when the fabrics were soaked for 15 minutes in a 30% active solution. FLASH EATHROOM (sold by The Procter S Ga ble Company, pH - 3.8 comprising 4% citric acid) or in a 20% aqueous solution of vinegar for 30 minutes.

Claims (11)

NOVELTY OF THE INVENTION CLAIMS

1. - A method for reducing the transfer of bleach catalyst from laundry bleach compositions containing metal-containing bleach catalysts, said method comprising contacting the impregnated fabrics with the metal-containing bleach catalysts with an aqueous citric acid solution which it has a pH below "Je 4.0 approximately.

2. The method according to claim 1, further characterized in that the fabric impregnated with the bleach catalyst is in contact with the aqueous acid solution for at least about 15 minutes.

3. The method according to claim 2, further characterized in that the acid solution comprises an acidifying agent selected from the group consisting of sulfuric acid, maleic acid, citric acid, polyacrylic acids and mixtures thereof.

4. The method according to claim 1, further characterized in that the fabric is impregnated with the bleaching catalyst MnIV2 (u-0) 3 (l, 7-t rirnet l -1, 4, 7 -tnazac? Clononane ) 2 (PFß) 2 or its byproducts of manganese decomposition.

5. A method for reducing the transfer of metal originated by the bleaching catalyst from laundry bleaching compositions containing the metal-containing bleaching catalyst, MnIV2 (u-0) 3 (1, 4,7- tpmet? ll, 4,7-tr? azac? clononane) 2 (PF?) 2 said method comprising contacting the impregnated fabrics with the metal-containing bleach catalyst MnIV2 (u-0) 3 (1, 4, 7- t rirnetyl-1,4,7-tzazacyclononane) 2 (PFß) 2 or manganese-containing decomposition products thereof, with an aqueous acid solution having a pH below about 4.0.

6. The method according to claim 5, characterized by "jerns" because the fabric that is impregnated with the bleach catalyst * is brought into contact with the aqueous acid solution at least 15 mm approximately.

7. The method according to claim 6, character *? Furthermore, the acid solution comprises an acidifying agent selected from the group consisting of sulfoic acid, aleic acid, citric acid, polyacrylic acids, and mixtures of the same.

8. The method according to claim 7, further characterized in that the fabric is subsequently washed with an alkaline detergent-free laundry detergent composition.

9. A method for bleaching fabrics, said method comprising the steps of: a) washing one or more times the fabrics that need to be bleached with laundry bleaching compositions comprising: i) a peroxide compound present in an effective amount to cause - bleaching; and 11) a manganese-containing bleach catalyst present in an amount effective to activate the peroxide compound; followed by; b) contacting the fabrics of step a) with an aqueous acid solution having a pH below 4.0 μg / μm; optional entity followed by; c) washing the fabric from step b) in an alkaline detergent composition of Catalyst-Free Laundry «Jor.

10. A method according to claim 9, further characterized in that the concentration of manganese in said laundry bleaching composition is less than 40 pprn, approximately manganese originating from the catalyst *.

11. The method according to claim 9, further characterized in that the manganese-containing bleach catalyst used in the composition for step a) is the bleaching catalyst Mn1 v2 (U-0Í3 (1, 4, 7). -t pinet il-l, 4, 7-tpazac? clononane) 2 (P? &) 2 • 12.- The method according to claim 10, further characterized in that the catalyst "Je blan" | io containing manganese used in the composition for step a) is the bleaching catalyst Mn * v2 (u-0) 3 (1,, 7- r et i 1 - 1, 4, 7- r? azac? clononane) 2 (PF? )2 -