MXPA99003607A - Asymmetrical imide bleach activators and compositions employing the same - Google Patents

Abstract

Asymmetrical imide bleach activators are provided. The compounds have general formula (I) wherein R1 is a moiety selected from a specific group, R2 is a C1-C8 linear or branched chain saturated or unsaturated alkyl group and R3 is a C1-C4 linear or branched chain saturated or unsaturated alkyl group. Preferred compounds include the compounds when R2 and R3 are CH3. Bleach additive and bleaching compositions including the asymmetrical bleach activators and methods of cleaning fabrics are also provided.

Description

ACTIVATORS OF ASYMMETRIC 1MIDA WHITENING AND COMPOSITIONS THAT USE THE SAME TECHNICAL FIELD This case relates to asymmetric imide bleach activators and compositions and methods using them. In particular, this case relates to a bleaching additive and bleaching compositions in both liquid and granular form utilizing asymmetric bleach activators. The activators are particularly useful in laundry compositions, automatic dishwashing and hard surface cleaning.

BACKGROUND OF THE INVENTION The formulation of bleaching compositions that effectively remove a wide variety of soils and stains from fabrics under broad range use conditions remains a considerable challenge for the laundry detergent industry. The challenges are also faced by the formulator of hard surface cleaning compositions and automatic dishwashing detergent compositions (ADD), which are expected to efficiently clean and sanitize the ware, often under heavy loads of dirt. The associated challenges with the formulation of truly effective cleaning and bleaching compositions have been increased by laws limiting the use of effective ingredients such as phosphate-based builders in many regions of the world. In recent years oxygen-based bleaching agents, such as hydrogen peroxide, have become very popular in household and personal care products to facilitate the removal of stains and dirt. Bleaching agents are particularly desirable due to their stain removal, stained fabric cleaning, sanitizing and bleaching properties. Oxygen-based bleaching agents have found particular acceptance in laundry products such as detergents, in products for automatic dishwashing and in hard surface cleaners. Oxygen-based bleaching agents, however, are somewhat limited in their effectiveness. Some frequently encountered disadvantages include damage to color on fabrics and surfaces. In addition, oxygen-based bleaching agents tend to be extremely dependent on the temperature regime. In this way, the colder the solution in which they are used, the less effective the bleaching action is. Temperatures above 60 ° C are typically required for an oxygen-based bleaching agent in solution to be effective. To solve the dependence on the temperature regime mentioned above, a class of compounds known as "bleach activators" has been developed. Bleach activators, typically Perhydrolyzable acyl compounds having a leaving group such as oxybenzenesulfonate, react with the active oxygen group, typically hydrogen peroxide or its anion, to form a more effective oxidizing peroxyacid. It is the peroxyacid-based compound which then oxidizes the soiled or stained substrate material. However, bleach activators are also somewhat dependent on the temperature regime. Bleach activators are most effective at warm water temperatures ranging from 40 ° C to about 60 ° C. At water temperatures below 40 ° C the peroxyacid-based compounds lose some of their effectiveness for bleaching. Numerous substances have been described in the art as effective bleach activators. A widely used whitening activator is tetraacetylethylepdiamine (TAED). TAED provides effective hydrophilic cleaning especially on beverage stains, but has limited performance on hydrophobic stains, e.g. ex. yellow spots, dull, such as those that result from body oils. Another type of activator, such as nonanoyloxybenzenesulfonate (NOBS) and other activators that generally include long chain alkyl portions, is hydrophobic in character and provides excellent performance on tarnished soils. However, many of the hydrophobic activators developed demonstrate limited performance on hydrophilic stains. Therefore, the search continues for more effective activating materials, especially those that provide performance satisfactory both in stains and hydrophilic and hydrophobic dirt. The improved activator materials must be safe, effective, and preferably designed to interact with problematic stains and dirt. Several activators have been described in the literature. Many are private and expensive. It has now been determined that certain selected bleach activators are unexpectedly effective in removing both hydrophilic and hydrophobic stains and dirt from fabrics, hard surfaces and tableware. When formulated as herein disclosed, bleaching additives and bleaching compositions are provided so as to utilize the selected bleach activator to remove stains and dirt not only from fabrics but also from dishware in washing compositions. of automatic tableware, hard kitchen and bathroom surfaces, and the like, with excellent results.

TECHNICAL BACKGROUND Bleach activators of various types are described in US Patents. 3,730,902; 4,179,390; 4,207,199; 4,221, 675; 4,772,413; 5,106,528; European Patent 063,017; European Patent 106,584; European Patent 163,331; Japanese patent 08/27487 and PCT publication W.O. 94/18298. Imide compounds of various types are disclosed in the U.S.A. 4,745,103 and 4,851, 138.

BRIEF DESCRIPTION OF THE INVENTION The present invention describes asymmetric imide bleach activators for use in both solid and liquid additives, bleaching compositions and detergent compositions. The asymmetric imide bleach activators of the present invention show their unique ability to form both hydrophilic and hydrophobic bleaching agents in aqueous solutions such as bleaching solutions. Therefore, fabrics, hard surfaces or tableware having hydrophobic stains such as hydrophilic and / or dull stains such as stains from beverages can be effectively cleaned or bleached using the imide bleach activators of the present invention. Accordingly, the imide bleach activators of the present invention provide a unique and superior capacity and a benefit over the activators of the prior art. According to a first embodiment of the present invention, a bleach activating compound is provided. The bleach activator of the present invention is an asymmetric imide having the formula: Where Ri is a portion selected from the group consisting of: wherein n is an integer from 0 to 12, A is a compatible charge counter ion, m is an integer from 1 to 3, R2 is a straight or branched chain saturated or unsaturated Ci-Ca alkyl group, preferably a group linear saturated C1-C4 alkyl and R3 is a straight or branched chain saturated or unsaturated Cid alkyl group. More preferably, R and R3 are CH3. In accordance with another embodiment of the present invention, a bleaching additive composition is provided. The additive composition comprises: i) from 0.1% to 70% by weight of the composition of an asymmetric bleach activator having the formula: wherein R1 is a portion as defined above, R2 is a straight or branched chain saturated or unsaturated C? -C8 alkyl group, preferably a linear saturated C4 alkyl group and R3 is a saturated C1-C4 alkyl group or unsaturated straight or branched chain; and, ii) from 0.1% to 99.9% by weight of the composition of conventional additive ingredients. More preferably, R2 and R3 are CH3. The conventional additive ingredients may include a source of hydrogen peroxide, a surfactant selected from the group consisting of nonionic surfactants, cationic surfactants, anionic surfactants, zwitterionic surfactants, amphoteric surfactants and mixtures thereof. , preferably nonionic surfactants and / or an ingredient selected from the group consisting of chelating agents, polymeric soil release agents, bleach catalysts, enzymes, builders and mixtures thereof. Preferably, the bleaching additive is in liquid form.

When in liquid form, the compositions preferably include from 0.1% to 60% by weight of an emulsifying system or a thickening system. He The emulsifier system preferably has an HLB value ranging from 8 to 15. Preferably, the emulsifying system includes one or more nonionic surfactants and more preferably includes a nonionic surfactant with the nonionic surfactant being a nonionic alkyl ethoxylate. In accordance with another embodiment of the present invention, a bleaching composition is provided. The composition may include: i) from 0.1% to 70% by weight of the composition of an asymmetric imide bleach activator having the formula: R, ^ > Where R1 is a portion as defined above, R2 is a saturated or unsaturated straight or branched chain Cn-Cß alkyl group, preferably a linear saturated C1-C4 alkyl group and R3 is a group C1-C4 saturated or unsaturated straight or branched chain alkyl; and, ii) from 0.1% to 70% by weight of the composition of a source of hydrogen peroxide. More preferably, R2 and R3 are CH3. The conventional additive ingredients may include a source of hydrogen peroxide, a surfactant selected from the group consisting of nonionic surfactants, cationic surfactants, anionic surfactants, zwitterionic surfactants, amphoteric surfactants and mixtures thereof, preferably nonionic surfactants and / or an ingredient selected from the group consisting of chelating agents, polymeric soil release agents, bleach catalysts, enzymes, builders and mixtures thereof. Preferably, the source of hydrogen peroxide includes perborate, percarbonate, hydrogen peroxide and mixtures thereof. The composition can be formulated as a microemulsion of bleach activator in a matrix comprising water, bleach activator, the source of hydrogen peroxide and a hydrophilic surfactant system which includes a nonionic surfactant. Alternatively, the composition can be formulated as an aqueous emulsion comprising at least one hydrophilic surfactant having an HLB above 10 and at least one hydrophobic surfactant having an HLB of up to 9, wherein the bleach activator is emulsified due to the surfactants. Alternatively, the composition is formulated in granulated form. In accordance with another embodiment of the present invention, a method for bleaching soiled fabrics including the steps of contacting the soiled fabrics to be bleached with an aqueous bleaching solution, including the bleaching solution an effective amount of the bleaching composition as described above or with an effective amount of the bleaching additive composition as described above and an effective amount of hydrogen peroxide.

Accordingly, it is an object of the present invention to provide an asymmetric imide bleach activator which can provide both hydrophobic and hydrophilic bleaching agents. It is another object of the present invention to provide an additive bleaching composition, especially in liquid form, which contains an asymmetric imide bleach activator. It is still another object of the present invention to provide a bleaching composition, in both solid and liquid form, containing an asymmetric imide bleach activator and hydrogen peroxide. Finally, it is an object of the present invention to provide a bleaching method for soiled fabrics using an aqueous solution containing asymmetric bleach activators. These and other objects, features and advantages will be clear from the following detailed description and the appended claims. All percentages, ratios and proportions are present on a weight basis unless otherwise indicated. All documents cited herein are incorporated herein by reference. All viscosities are measured at a cutting speed of 10 rpm in a Brookfield viscometer.

DETAILED DESCRIPTION OF THE PREFERRED MODALITIES The present invention relates to asymmetric bleach activators and to solid and liquid compositions utilizing activators of Asymmetric imide bleaching. The compositions, both solid and liquid, can include additive, bleach and detergent compositions and are useful for cleaning fabrics, tableware and hard surfaces. The asymmetric imide activators of the present invention have the formula: Where R1 is a portion selected from the group consisting of: wherein p is an integer from 0 to 12, A is a compatible charge counter ion, m is an integer from 1 to 3, R2 is a straight or branched chain saturated or unsaturated Ci-C alquilo alkyl group, preferably a group linear saturated C1-C4 alkyl and R3 is a straight or branched chain saturated or unsaturated C1-C4 alkyl group. Suitable counter-ions to balance the charges include the hydrogen cation, alkali metal cations, C1-C4 quaternary ammonium, and mixtures thereof. Preferred activators are those in which R 2 is a linear or branched saturated C 4 alkyl group and R 3 is a straight or branched chain saturated or unsaturated C 1 -C 4 alkyl group. More preferably, R2 and R are linear saturated C1-C4 alkyl groups and more preferably are the same. The activators also preferred according to the present invention are the N-acyl acetamides. Activators have the formula (!) Wherein both R2 and R3 are methyl groups. Therefore, the N-acyl-acetamides have the formula: A Me Me (p) where 1 is defined as it was done previously. Without being limited to the theory, it is believed that as the number of carbon atoms in the activators of formula (I) increases, the solubility of the compound decreases. Therefore, since the activators of the present invention are ideally soluble for optimal performance of the activators, it is preferred that the number of atoms in the activating compound be tai that allows the activating compound to show satisfactory solubility profiles. In the present invention, the sum of the coals in Ri, R2 and R3 is preferably less than 19 and more preferably less than 15. The asymmetric measurement bleach activators of the present invention provide superior bleaching performance and capacity with respect to to the bleach activators of the prior art. Without being limited to the theory, it is believed that the asymmetric measurement bleach activators of the present invention provide both hydrophobic and hydrophilic bleaching agents in aqueous solution. It is believed that this is due to the fact that perhydrolysis can occur in any of the carbonyl groups of the activator. In this way, any molecule of the activators of the formula (I) could undergo perhydrothisis in aqueous solution to form either a bleaching agent (R? C (O) OOH) having hydrophobic properties and a bleaching agent (R3C ( 0) OOH) having hydrophilic properties when R1 and R3 are defined as above. Of course, the bleaching agent can be protonated or deprotonated depending on the pH used. Then a bleaching solution will include both the hydrophilic bleaching agent and the hydrophobic bleaching agent. In this way, the bleaching capabilities of a mixed activator system (hydrophobic and hydrophilic) and even an increased yield can be obtained through the use of a single bleach activator. The elimination of mixed activating systems It can provide great potential benefits by eliminating the significant expense of an additional bleach activator.

Compositions Compositions in accordance with the present invention may include liquid, granular and stick compositions in bleaching or additive composition forms. The compositions are preferably laundry compositions, hard surface cleaning compositions and automatic dishwashing compositions. The liquid compositions may include those in gel form. The bleach additives effective herein may include the asymmetric imide bleach activators of the present invention as described above in general form without a source of hydrogen peroxide, but preferably include detersive surfactants and one or more selected members. from the group consisting of automatic surfactant surfactants with low foaming, nonionic surfactants, bleach-stable thickeners, transition metal chelators, builders, whiteners (also known as brighteners) and regulatory agents. For the bleaching compositions according to the present invention the asymmetric imide bleach activators of the present invention as described above are generally used in combination with a source of hydrogen peroxide. The levels of bleach activators herein can vary widely. for example, from 0.1% to 90%, by weight of the composition, although lower levels, eg, from 0.1% to 30%, or from 0.1% to 20% by weight of the composition are more typically used.

Conventional additive ingredients Source of hydrogen peroxide The compositions according to the present invention may further include a source of hydrogen peroxide. A source of hydrogen peroxide herein is any convenient compound or mixture that can under the conditions of consumer use provide an effective amount of hydrogen peroxide. The levels may vary widely and are typically from 0.1% to 70%, more typically from 0.2% to 40% and more typically still from 0.5% to 25%, by weight of the bleaching compositions herein. The source of hydrogen peroxide used herein may be any convenient source, including hydrogen peroxide by itself. For example, perborate, eg, sodium perborate (any hydrate but preferably monohydrate or tetrahydrate), sodium carbonate peroxyhydrate or equivalent percarbonate salts, sodium pyrophosphate peroxyhydrate, urea peroxyhydrate, or sodium peroxide may be used in the present. Mixtures of any suitable hydrogen peroxide source can also be used.

A preferred percarbonate-based bleach comprises dry particles having an average particle size in the range of 500 microns to 1,000 microns, no more than 10% by weight of said particles are smaller than 200 microns and no more than 10 microns. % by weight of said particles are larger than 1, 250 microns. Optionally, the percarbonate can be coated with silicate, borate or water soluble surfactants. Percarbonate is available from vain commercial sources such as FMC, Solvay and Tokai Denlo. The source of hydrogen peroxide and asymmetric bleach activator is typically in a ratio of 1: 3 to 20: 1, as expressed on the basis of peroxide: activator in units of moles of H202 supplied by the peroxide source of hydrogen to the moles of bleach activator. Bleaching compositions and wholly formulated bleach additive compositions, particularly those for use in automatic dishwashing and laundry, will typically comprise other auxiliary ingredients to improve or modify performance. Typical, non-limiting examples of such ingredients are described below for the convenience of the formulator. Bleach catalysts If desired, bleach can be catalyzed by a bleach catalyst. Preferred are bleach catalysts containing metals such as manganese and cobalt or organic bleach catalysts.

One type of metal-containing bleach catalyst is a catalyst system that includes a transition metal cation of defined bleach catalytic activity, such as copper, iron, titanium, ruthenium, tungsten, molybdenum or manganese, an auxiliary metal cation having little or no catalytic activity of bleach, such as zinc or aluminum, and a sequestering agent having the stability constants defined for the auxiliary and catalytic metal cations, particularly diethylene diamine tetraacetic acid, et? lend? amintetra (methylene phosphonic acid), acid S , S-ethylenediamidisuccinic acid and soluble salts thereof. Such catalysts are deciphered in the 4,430,243 patent. Other types of bleach catalyst include the manganese-based complexes described in the U.S.A. 5,246,621 and patent E.U.A. 5,244,594. Preferred examples of these catalysts include Mn'v 2 (u-0) 3 (1, 4,7-trimet? L-1, 4,7-tpazac? Clononane) 2- (PF6) 2 ("MnTACN"), Mn "'2 (u-0)? (U-OAc) 2 (1, 4,7-tpmethyl-1, 4,7-tr? Azac? Clononane) 2- (CI0) 2, Mn? V4 (u-0) ) 6 (1, 4,7-triazacyclononane) 4- (Cl? 4) 2, Mn, MMnIV4 (u-0)? (U-OAc) 2 (1, 4,7-trimethyl-1, 4,7-triazacyclononane) 2- (Cl? 4) 3, Mn '"MnIV4 (u-0) 2 (u-OAc)? (1, 4,7-trimethyl-1, 4,7-triazacyclononane) 2- (Cl? 4) 3 and mixtures See also European Patent Application Publication No. 549,272 Other suitable ligands for use herein include 1, 5,9-trimethyI-1, 5,9-triazacyclododecane, 2-methyl-1, 4. , 7-triazacyclononane, and mixtures thereof Bleach catalysts useful in automatic dishwashing compositions and powder detergent compositions Concentrates can also be selected as bleach catalysts suitable for the present invention. As examples of other suitable bleach catalysts in the present patent see E.U.A. 4,246,612, patent E.U.A. 5,227,084 and WO 95/34628, December 21, 1995, the latter referring to particular types of iron-based catalysts. See also the patent 5,194,416 which shows mononuciear complexes of manganese (IV) such as Mn (1, 4,7-trimethyl-1, 4,7-tpazacyclononane (OCH 3) 3- (PF 6) .Other type of bleach catalyst, as described in US Patent 5,114,606, is a water-soluble complex of manganese (II), (III), and / or (IV) with a ligand that is a non-carboxylated polyhydroxy compound having at least 3 consecutive groups C -OH Preferred ligands include sorbitol, iditol, dulcitol, mannitol, xylitol, arabitol, adonitol, meso-erythritol, meso-lnositol, lactose and mixtures thereof US Patent 5,114,611 shows another useful bleach catalyst which includes a complex of transition metal, including Mn, Co, Fe, or Cu, with a non- (macro) -cyclic ligand The preferred ligands include the pyridine, pyridazine, pyrimidine, pyrazine, midazole, pyrazole, and triazole rings. Optionally, said rings may be substituted with substituents such as alkali. uilo, aryl, alkoxy, halide, and nitro. Particularly preferred is the 2,2'-b.spiridyl amine ligand. Preferred bleach catalysts include Co-, Cu-, Mn-, or Fe-bispyridylmethane and complexes of bispyridylamine. Highly preferred catalysts include Co (2,2'-bispyridylamine) CI2, Di (isot? Ocyanate) b? Cobalt (II) spiridylamine, trisdipyridylamine cobalt (II) perchlorate, Co (2,2- b? spirid? lam? na) 202Cl? 4, Bis- (2,2'-bispyrid? lamna) perchlorate of copper (ll), iron tris (di-2-p? ridyl amine) perchlorate ( ), and mixtures thereof.

Other examples of bleach catalyst include Mn gluconate, Mn (CF3S03) 2, Co (NH3) sCI, and binuclear manganese complexed with tetra-N-toothed and bi-N-toothed ligands, including Mn N4Mn "'( u-0) 2MnlvN4) + and [Bipi2Mn "l (u-0) 2Mnlvb? pi2] - (Cl? 4) 3. The bleach catalysts can also be prepared by combining a water-soluble ligand with a water-soluble manganese salt in an aqueous medium and concentrating the resulting mixture by evaporation. Any convenient water-soluble manganese salt can be used herein. Manganese (II), (III), (IV) and / or (V) can be easily obtained on a commercial scale. In some examples, sufficient manganese may be present in the wash solution, but, in general, the manganese cations in the detergent composition are preferred in the compositions to ensure their presence in catalytically effective amounts. In this way, the sodium salt of the ligand and the member selected from the group consisting of nS? , Mn (CI0) 2 or MnCl2 (less preferred) are dissolved in water in a molar ratio of ligand: Mn salt in the range of 1: 4 to 4: 1 at a slightly alkaline or neutral pH. Water can first be deoxygenated by boiling and then cooled by nitrogen sparging. The solution The resultant is evaporated (under N2 atmosphere, if desired) and the resulting solids are used in the detergent and bleach compositions herein without postpurification. In an alternate form, the source of water-soluble manganese, such as MnSO4, is added to the bleaching / cleaning composition or aqueous bleaching / cleaning bath which includes the ligand. Some types of complexes are formed apparently in situ, and the improved bleaching performance is ensured. In an in situ process as such, it is convenient to use a considerable molar excess of the ligand over manganese, and the ratios of moles of: Mn are typically from 3.1 to 15: 1. The additional ligand also serves to purify stray metal ions such as iron and copper, thus protecting the bleach from decomposition. Such a possible system is described in the European patent application, publication no. 549.271. While the structures of the manganese-based complexes that catalyze the bleach have not been determined, it can be speculated that they include chelates or other hydrated coordination complexes resulting from the interaction of the nitrogen and carboxyl atoms of the ligand with the cation manganese. Similarly, the oxidation state of the manganese cation during the catalytic processes is not known exactly, and may be in the valence state (+ ll), (+ III), (+ IV) or (+ V). Due to the six possible points of binding of the ligand to the manganese cation, it could be rightly speculated that there could be multinuclear species and / or "cage" structures in the aqueous bleaching medium. Whatever the Form of the active Mn-Llgando species that normally exist, they function in a seemingly catalytic manner to provide improved bleaching performance on stubborn stains such as tea stains, tomato sauce, coffee, wine, juice and the like. Other bleach catalysts are described, for example, in the European patent application, publication no. 408,131 (cobalt complex catalysts), European patent applications, publication numbers 384,503, and 306,089 (metal-porphyrin catalysts), patent E.U.A. 4,728,455 (manganese / multidentate ligand catalyst), patent E.U.A. 4,711, 748 and European patent application, publication no. 224,952, (manganese catalysts absorbed on aluminosilicate), patent E.U.A. 4,601, 845 (aluminosilicate support with manganese, zinc or magnesium salts), patent E.U.A. 4,626,373 (manganese / ligand catalyst), patent E.U.A. 4,119,557 (ferric complex catalyst), German patent specification 2,054,019 (cobalt-chelator catalyst), Canadian document 866,191 (salts containing transition metals), patent E.U.A. 4,430,243 (chelators with manganese cations and non-catalytic metal cations), and patent E.U.A. 4,728,455 (catalysts based on manganese gluconate). Cobalt (III) catalysts are preferred having the formula: CoKNHsJnM'mB'bTtQqPplYy where the cobalt has the oxidation state +3; p is an integer from 0 to 5 (preferably 4 or 5, more preferably 5); M 'represents a monodentate ligand; m is an integer ranging from 0 to 5 (preferably 1 or 2; preferably 1); B 'represents a bidentate ligand; b is an integer ranging from 0 to 2; T 'represents a tridentate ligand; t is 0 or 1; Q is a tetradentate ligand; q is 0 or 1; P is a pentadentate ligand; p is 0 or 1; and n + m + 2b + 3t + 4q + 5p = 6; Y is one or more counter-anions appropriately selected in a number y, where y is an integer ranging from 1 to 3 (preferably 2 to 3, more preferably 2 when Y is an anion loaded with -1), to obtain an salt balanced as to fillers, preferred Y's are selected from the group consisting of chloride, nitrate, nitrite, sulfate, citrate, acetate, carbonate, and combinations thereof; and wherein in addition at least one of the coordination sites attached to the cobalt is susceptible under conditions of automatic dishwashing use and the remaining coordination sites stabilize the cobalt under the conditions of automatic dishwashing such that the reduction potential for the cobalt (III) to cobalt (II) under alkaline conditions is less than 0.4 volts (preferably less than 0.2 volts) against a normal hydrogen electrode. Preferred cobalt-based catalysts of this type have the formula [Co (NH3) n (M'm] Yy where n is an integer ranging from 3 to 5 (preferably 4 or 5, more preferably 5); is a labile coordination moiety, preferably selected from the group consisting of chloride, bromide, hydroxide, water, and (when m is greater than 1) combinations thereof, m is an integer from 1 to 3 (preferably 1 or 2; more preferably 1); m + n = 6; and Y is a counter-anion appropriately selected present in a number y, which is an integer ranging from 1 to 3 (preferably 2 or 3, more preferably 2 when Y is an anion with charge -1), to obtain a salt balanced in terms of charge. Preferred cobalt catalysts of this type useful herein are salts of pentaamine-cobalt chloride having the formula [Co (NH3) 5Cl] Yy, and especially [Co (NH3) 5Cl] CI2 The most preferred compositions of the present invention are those using cobalt bleach catalysts (III) having the formula [Co (NH3) n (M) m (B) b] Ty where the cobalt has the oxidation state +3; n is 4 or 5 (preferably 5); M is one or more ligands coordinated to cobalt by a site; m is 0, 1 or 2 (preferably 1); B is a ligand coordinated to cobalt by two sites; b is 0 or 1 (preferably 0), and when b = 0, then m + n = 6, and when b = 1, then m = 0 and n = 4; and T is one or more appropriately selected counter-anions present in a number y, where y is an integer to obtain a salt balanced with respect to charges (preferably y is 1 to 3, more preferably 2 when T is an anion charged with -1 ); and wherein further said catalyst has a base hydrolysis rate constant of less than 0.23 M "1 s" 1 (25 ° C). Preferred T's are selected from the group consisting of chloride, iodide, l3", formate, nitrate, nitrite, sulfate, sulfite, citrate, acetate, carbonate, bromide, PF6", BF4", B (Ph) 4_, phosphate , phosphite, silicate, tosylate, methanesulfonate and combinations thereof Optionally, T may be protonated if there is more than one anionic group in T ,. eg, HPO42", HCO3", H2PCV, etc. In addition T may be selected from the group consisting of non-traditional inorganic anions such as anionic surfactants (eg, linear alkylbenzenesulphonates (LAS), alkyl sulfates (AS), alkylethoxysulfonates (AES), etc.) and / or ammonium polymers ( eg polyacrylates, polymethacrylates, etc.). The M portions include, but are not limited to, for example F ", SO4" 2, NCS ", SCN", S203 ~ 2, NH3, PO43", and carboxylates (which are preferably mono carboxylates, but more than a carboxylate in the portion as long as the cobalt binding is made only by one carboxylate per portion, in which case the other carboxylate in the M portion can be protonated or in its salt form) Optionally, M can be protonated if more than an anionic group in M (eg, HPO42", HC03", H2P04", HOC (0) CH2C (0) 0-, etc.). The preferred M-portions are substituted and unsubstituted C? -C30 carboxylic acids which have the formulas: RC (0) 0- Where R is preferably selected from the group consisting of hydrogen and C?-C30 alkyl (preferably CC ?8) substituted and unsubstituted, C C-C ar ar aryl (preferably Cß-C) ? ß) substituted and unsubstituted, and C3-C30 heteroaryl (preferably C5-C18 substituted and unsubstituted, wherein the substituents on selected from the group consisting of -NR'3, -NRV, -C (0) OR ', -OR', -C (0) NR'2, where R 'is selected from the group consisting of hydrogen and portions C Cß. Such a substituted R includes therefore the portions - (CH2) nOH and - (CH2) nNRY \ where n is an integer that ranges from 1 to 16, preferably from 2 to 10, preferably equal to 2 to 5. Most preferred M are carbonylic acids having the above formula wherein R is selected from the group consisting of hydrogen, methyl, ethyl, propyl , straight or branched alkyl C4-C-? 2, and benzyl. The most preferred R is methyl. The M-moieties of preferred carboxylic acid include formic, benzoic, octanoic, nonanoic, decanoic, dodecanoic, malonic, maleic, succípico, adipic, phthalic, 2-et? Lhexanoic, naphthenic, oleic, palmitic, triflate, tartrate, estepic, butyric , citric, acrylic, aspartic, fumaric, laupco, linoleic, lactic, malic and especially acetic acid. Portions B include carbonate, higher carboxylates and dicarboxylates (eg, oxalate, malonate, malic, succinate, maleate), picolinic acid, and alpha- and beta-amino acids (eg, glycine, alanine, beta-alanine, phenylalanine). The cobalt-based bleach catalysts useful herein are known, being described for example together with their rates of hydrolysis in basic medium, in "Basis hydrolysis of Transition-metal Compiexes", Adv. Inorq. Bioinora Mech .. (1983), 2, pages 1-94. For example, Table 1 on page 17, provides the hydrolysis rates in basic medium (designated there as I OH) for the cobalt pentamine catalysts complexed with oxalate (k0H = 2.5 x 10"4 M" 1 s "1 (25 ° C)), NCS- (k0H = 5.0 x 10"M 's" 1 (25 ° C)), format (k0H = 2.5 x 10"1 M" 1 s-1 (25 ° C)), and acetate (k0H = 9.6 x 10"4 M" 1 s "1 (25 ° C)). The most preferred cobalt-based catalyst to be used herein are the salts of cobalt pentaminacetate having the formula [Co (NH3) 5OAc] Ty, wherein OAc represents an acetate portion, and especially cobalt pentaminacetate chloride, [Co (NH3) 5OAc] CI2 as well as also [Co (NH3) 5OAc] (OAC) 2; [Co (NH3) 5OAc] (PF5) 2; [Co (NH3) 5OAc] (S? 4); [Co- (NH3) 5OAc] (BF4) 2; and [Co (NH3) 5OAc] (N03) 2 (hereinafter "PAC"). These cobalt-based catalysts are readily prepared by known methods, such as those taught for example in the above Tobe article and the references cited in the same document, in US Patent 4,810,410, to Diakun et al., Issued March 7. 1989, L Chem. Ed. (1989), 66 (12), 1043-45; The Synthesis and characterization of Inorganic Compounds, W.L. Jolly (Prentice-Hall, 1970), pp. 461-3; Inoro. Chem., 18, 1407-1502 (1979); inora. Chem. 21, 2881-2885 (1982); Inoro. Chem. 18, 2023-2025 (1979); Inorg. Synthesis, 173-176 (1960); and Journal of Phvsical Chemistrv. 56, 22-25 (1952); as well as also the synthesis examples supplied later. These catalysts can be co-processed with auxiliary materials so that the color impact is reduced if desired, for the aesthetic presentation of the product, or they can be included in particles containing enzyme as exemplified below, or the compositions can be be manufactured in such a way that they contain "specks" of catalyst. Organic bleach catalysts can also be used in the present invention. Organic bleach catalysts are known and include mine compounds and their precursors as disclosed in U.S. Patent Nos. 5,360,568, 5,360,569, and 5,370,826, all of which are incorporated herein by reference and sulfonyl compounds Mine, its precursors and bleaching agents as described in US Pat. Nos. 5,041,232, 5,045,223, 5,047,163, 5,310,925, 5,413,733, 5,429,768 and 5,463,115, whose descriptions of all of them are incorporated herein by reference. Particularly preferred organic bleach catalysts include quaternary imine compounds of the general structure: N KA "R, wherein R1-R4 may be a hydrogen or a substituted or unsubstituted radical selected from the group consisting of phenyl, aplo, heterocyclic ring, alkyl and cycloalkyl radicals except that at least one of R1-R * contains an ammonium charged portion The most preferred organic catalysts have an anionically charged portion linked to the quaternary nitrogen and are represented by the formula: Where: R1-R3 are portions having a total charge from 0 to -; R1-R3 may be a hydrogen or a substituted or unsubstituted radical selected from the group of radicals consisting of phenyl, alkyl, heterocyclic alkyl and cycloalkyl ring; T is selected from the group consisting of - (CH2) b- wherein b ranges from 1 to 8, - (CH (R5)) - wherein R5 is C8 alkyl, -CH2 (C6H4) -, H H II - CH - C - CH - - CH 2 - C - CH - OH and - (CH 2) d (E) (CH 2) r where d goes 2 to 8, f goes from 1 to 3 and E is -C (0) 0-, -C (0) NR6 or wherein R6 is H or C1-C4 alkyl. Z is covalently bound to T and is selected from the group consisting of C02-, -S03- and -OSO3- and a is at least 1. Therefore, since Z is covalently linked to T (when the charge total over R1_R3 is zero), the quaternary imit is a zwitterion when a is 1 or a poly-ion having a negative net charge when a is greater than 1. An even more preferred organic catalyst is a zwiterion of aplimin, a poly- ion of fixation that has a net negative charge around -1 to -3 or mixtures thereof. In this preferred embodiment, R1 and R2 together form part of a common ring. In particular, R1 and R2 together can form one or more rings of five, six or seven members. The most preferred aryliminiums are created from the no-load portion: Accordingly, the preferred binding sites involve R1 and R2 which together form the uncharged portion (III) with T being selected from the group consisting of - (CH2) b- wherein b ranges from 1 to 6, - (CH (R5)) - wherein R5 is methyl, and -CH2 (C6H4) -, with a being 1 and Z being selected from C02- and -S03-. More preferably, the aryliminium zwitterion of the present invention has R1 and R2 together forming the uncharged portion (III) with T being - (CH2) b- or -CH2 (C6H4) -, with a being 1, Z being - SO3- and b being from 2 to 4. The most preferred aryliminium zwitterions are represented by the formula: or 3- (3,4-dihydroisoquilonyl) propane suifonate or 4- (3,4-dihydroisoquinolinio) butane. Practically, and not by way of limitation, the cleaning compositions and cleaning methods described herein may be adjusted to provide in the order of at least one part per hundred million of the active bleach catalyst species in the aqueous washing medium, and preferably will provide from 0.01 ppm to 25 ppm, more preferably from 0.05 ppm to 10 ppm, and more preferably from 0.1 ppm to 5 ppm, of the bleach catalyst species in the wash solution. To suitably obtain such levels in the washing solution of an automatic dishwashing process, the typical automatic dishwashing compositions described herein will include from 0.0005% to 0.2%, more preferably from 0.004% to 0.08%, of catalyst bleach by weight of the cleaning compositions.

Conventional bleach activators. The compositions of the present invention may further include, in addition to the asymmetric imide bleach activators, a conventional bleach activator. The "conventional bleach activators" herein are any bleach activator that does not respect the provisions identified above in the definition of the asymmetric imide bleach activators herein. They know each other numerous conventional bleach activators and are optically included in the present bleaching compositions. Several non-limiting examples of such activators are described in the patent E.U.A. 4,915,854, issued April 10, 1990 to Mao et al., And patent E.U.A. 4,412,934. Activators popanoiloxibepcensulfonato (NOBS) and tetraacetylethylenediamine (TAED) are typical, and mixtures thereof can be used. See also patent E.U.A. 4,634,551 for other typical conventional bleach activators. The known amido deposited bleach activators are those of the formulas: R1N (R5) C (0) R2C (0) L or R1C (0) N (R5) R2C (0) L wherein R1 is an alkyl group containing from 6 to 12 carbon atoms, R 2 is an alkylene containing from 1 to 6 carbon atoms, R 5 is hydrogen or alkyl, ary, or alkaryl containing from 1 to 10 carbon atoms, and L is any appropriate leaving group. Illustrative of optional conventional bleach activators of the above formulas include (6-octanamido-capro? I) oxybenzenesulfonate, (6-nopapamidocaprayl) oxybenzenesulfonate, (6-decanamido-caproyl) oxybenzenesulfonate, and mixtures thereof as described in US Patent 4,634,551 Another class of conventional bleach activators include benzoxazine type activators described by Hodge and others in US Patent 4,966,723, issued October 30, 1990. Examples of optional lactam-based activators include octanoyl caprolactam, 3, 5,5-trimethylhexanoyl caprolactam, nonanoyl caprolactam, decanoyl caprolactam, undecenoyl caprolactam, octanoyl valerolactam, decanoyl valeroiactam, benzoyl caprolactam, pitrobenzoyl caprolactam, undecenoyl valerolactam, nonanoii valerolactam, 3,5,5-trimethylhexanoyl valerolactam and mixtures thereof. Bleaching agents other than hydrogen peroxide sources are also known in the art and can be used herein as auxiliary ingredients. One type of non-oxygenated bleaching agent of particular interest includes the photoactivated bleaching agents such as the sulphonated phthalocyanines of zinc and / or aluminum. See patent E.U.A. 4,033,718, issued July 5, 1977 to Holcombe et al. If used, detergent compositions will typically contain from 0.025% to 1 25%, by weight, of such bleaches, especially sulfonated zinc phthalocyanine.

Organic peroxides, especially diacyl peroxides. These compounds are extensively illustrated in Kirk Othmer, Encyclopedia of Chemical Technology, Vol. 17, John Wiley and Sons, 1982 on pages 27-90 and especially on pages 63-72, all incorporated herein by reference. Suitable organic peroxides, especially diacyl peroxides, are further illustrated in "Initiators for Polymer Product", Akzo Chemicals Inc., Product Catalog, Bulletin No. 88-57, incorporated for reference. The diacyl peroxides preferred herein whether in pure form or formulated for granules, powder or tablets of the bleaching compositions constitute solids at 25 ° C, e.g. eg the product CADET® BPO 78 which is the powder form of dibenzoiio peroxide, from Akzo. Highly preferred organic peroxides, particularly diacyl peroxides, for such bleaching compositions have melting points above 40 ° C, preferably above 50 ° C. Additionally, organic peroxides with SADT (as defined in the preceding Akzo publication) of 35 ° C or higher are preferred., more preferably 70 ° C or higher. Non-limiting examples of diacyl peroxides useful herein include dibenzoyl peroxide, lauroyl peroxide, and dicumyl peroxide. Dibenzoyl peroxide is preferred. In some cases, the diacyl peroxides are commercially available which contain oily substances such as dioctyl phthalate. In general, particularly for automatic dishwashing applications, it is preferred to use diacyl peroxides which are substantially free of oily phthalates, since these can form slides on dishes and glassware.

Substituted quaternary bleach activators. The present compositions may also optionally include conventional, substituted quaternary bleach activators (QSBA). The QSBAs are also illustrated in patent E.U.A. No. 4,539,130, September 3, 1985 and patent E.U.A. No. 4,283,301. British Patent No. 1, 382,594, published on February 5, 1975, discloses a class of QSBA optionally suitable for use herein. The patent E.U.A. 4,818,426 issued April 4, 1989 describes another class of QSBA.

See also patent E.U.A. 5,093,022 issued on March 3, 1992 and patent E.U.A. Additionally, the QSBAs are described in EP 552,812 A1 published on July 28, 1993, and in EP 540,090 A2, published on May 5, 1993. Multi-material bleach activators tai and as they are described in US patent 5,460,747 can also be used.

Preformed Peracids The activators of the present invention can of course be used in conjunction with a preformed peracid compound selected from the group consisting of percarboxylic acids and their salts, percarbonic acids and their salts, perimidic acids and their salts, peroxymonosulfuric acids and their salts, and mixtures thereof. A suitable organic peroxycarboxylic acid group has the general formula: OR YRCO OH wherein R is a substituted alkylene or alkylene group containing from 1 to 22 carbon atoms or a substituted phenylene or phenylene group, and Y is hydrogen, halogen, alkyl, aryl, -C (0) OH or -C ( 0) OOH. Organic peroxyacids suitable for use in the present invention may contain either one or two peroxy groups and may be both aliphatic and aromatic. When the organic peroxycarboxylic acid is aliphatic, the unsubstituted acid has the general formula: Y (CH2) n C O OH wherein Y may be, for example, H, CH 3, CH 2 Cl, C (0) OH, or C (0) OOH; and p is an integer ranging from 1 to 20. When the organic peroxycarboxylic acid is aromatic, the unsubstituted acid has the general formula: And C6H4 c or OH where Y can be, for example, hydrogen, alkyl, aikhylhalogen, halogen, C (0) OH or C (0) OHH. Typical monoperoxy acids useful herein include alkyl peroxy acids and aryl peroxyacids such as: i) peroxybenzoic acid and peroxybenzoic acid substituted on the ring, for example, peroxy-a-naphthoic acid, monoperoxyphthalic acid (magnesium salt hexahydrate), and ortho- carboxybenzamidoperoxyhexanoic (sodium salt); ii) ii) aliphatic monoperoxy acids, aliphatic substituted monoperoxy acids and arylalkylalkoxy monoperoxyacids, for example peroxylauric acid, peroxystearic acid, N-nonanoylaminoperoxycaproic acid (NAPCA), N, N- (3-octylsuccinyl) ammoperoperocaproic acid (SAPA) and N, N-phthaloylaminoperoxycaproic acid (PAP); Ii) aminoperoxyacids, for example the monononylamide of peroxysuccinic acid (NAPSA) or monononylamide of peroxyadipic acid (NAPAA). Typical diperoxy acids useful herein include alkyl diperoxy acids and diplyroxy acids, such as: iv) 1,2-diperoxydodecanedioic acid; v) 1, 9-d? peroxyazelaic acid; vi) diperoxy-fibrous acid; diperoxysebasic acid, and diperoxyisophthalic acid; v¡¡) 2-decyldiperoxybutan-1,4-dioic acid; viii) 4,4'-sulfonylbisperoxybenzoic acid.

Detersive Surfactants The compositions of the present invention may include a detersive surfactant. The detersive surfactant may include from 1%, up to 99.8%, by weight of the composition depending on the particular surfactants used and the effects desired. The most typical levels comprise from 5% to 80% by weight of the composition.

The detersive surfactant can be nonionic, anionic, ampholytic, zwitterionic or cationic. Mixtures of these surfactants can also be used. Preferred detergent compositions comprise anionic detersive surfactants or mixtures of anionic surfactants with other surfactants, especially nonionic surfactants. Non-limiting examples of surfactants useful herein include conventional C 8 -C 8 alkylbenzene sulphonates and primary, secondary and random alkyl sulphates, C 8 -C 8 alkylalkoxy sulfates, C 8 -C 8 alkyl polyglycosides and their corresponding sulfated polyglycosides, esters of alpha sulfonated fatty acids C3-C? ß, alkyl alkoxylates and alkyl feml alkoxylates Cß-C-ia (especially ethoxylated and mixtures ethoxy / propoxy), betaines and sulfobetaines ("sultaines") C8-C18, amine oxides C8- C18, such as branched or unbranched N, N-dimethyl-N-oxides and the like. Other useful conventional surfactants are listed in standard texts such as Surfactants in Consumer Products; Theory, Technology and Application, J. Falbe, Springer-Verlag 1987 and Handbook of Surfactants, M: R. Porter, Blackie & Son, 1991. A class of nonionic surfactants particularly useful in detergent compositions of the present invention are condensates of ethylene oxide with a hydrophobic portion to deliver a surfactant having an average hydrophilic-lipophilic balance (HLB) in the Range from 5 to 17, preferably from 6 to 16, more preferably from 7 to 15.

The hydrophobic (lipophilic) portion may be aliphatic or aromatic in nature. The length of the polyoxyethylene group which is condensed with any particular hydrophobic group can be easily adjusted to yield a water-soluble compound having the desired degree of balance between the hydrophilic and hydrophobic elements. Especially preferred nonionic surfactants of this type are the ethoxylates of C8-Ct5 primary alcohol containing 3-12 moles of ethylene oxide per mole of alcohol, particularly the C1-15 co-terminus alcohols containing 6-8 moles of ethylene per mole of alcohol, the primary C 2 -C 15 alcohols containing 3-5 moles of ethylene oxide per mole of alcohol, the lower alcohols Cg-Cn containing 8-12 moles of ethylene oxide per mole of alcohol, and mixtures thereof. The non-ionic ethoxylated fatty alcohol surfactants suitable for use in the present invention are available under the tradenames DOBANOL and NEODOL supplied by the Shell Oil Company of Houston, Texas. Another suitable class of nonionic surfactants includes the polyhydroxy fatty acid amides of the formula: R2C (0) N (R1) Z wherein: R1 is H, C? -C? Hydrocarbyl, 2-hydroxyethyl, 2-hydroxypropyl, or a mixture thereof, preferably C 1 -C 4 alkyl, more preferably C 1 or C 2 alkyl, more preferably C 1 alkyl (ie, methyl); and R2 is a C5-C32 hydrocarbyl portion, preferably straight chain C7-C19 alkyl or alkenyl, more preferably straight chain C9-C17 alkyl or alchemyl, more preferably straight chain Cn-C19 alkyl or alchemyl, or mixtures thereof; and Z is a polyhydroxyhydrocarbyl moiety having a linear hydrocarbyl chain with at least 2 (in the case of glyceraidehyde) or at least 3 hydroxyls (in the case of other reducing sugars) directly connected to the chain, or an alkoxylated deposit (preferably ethoxylated or propoxylated) thereof. Z will preferably be obtained from a reducing sugar in a reductive amination reaction; more preferably Z is a glycityl moiety. Suitable reducing sugars include glucose, fructose, maltose, lactose, galactose, mannose and xylose, as well as glyceraldehyde. As raw materials, high dextrose corn syrup, high fructose corn syrup, and high maltose corn syrup can be used as well as the individual sugars mentioned above. These corn syrups can yield a mixture of sugar components for Z. It will be understood that by no means is it intended to exclude other suitable raw materials. Preferably Z will be selected from the group consisting of -CH2- (CHOH) "-CH2OH, -CH (CH2-OH) - (CHOH) n -? - CH2OH, -CH2- (CHOH) 2 (CHOR ') ( CHOH) -CH2OH, wherein n is an integer from 1 to 5, inclusive, and R 'is H or a cyclic mono- or polysaccharide, and alkoxylated derivatives thereof. Most preferred are glycyls wherein n is 4, particularly -CH2- (CHOH) 4-CH2OH. In the formula (I), R1 can be, for example, N-methyl, N-ethyl, N-propyl, N-isopropyl, N-butyl, N-isobutyl, N-2-hydroxy ethyl, or N-2- hydroxy propyl.

To obtain a higher foam formation, R1 is preferably methyl or hydroxyalkyl. If a smaller foam formation is desired, R1 is preferably C2-C8 alkyl, especially n-propyl, iso-propyl, n-butyl, iso-butyl, pentyl, hexyl and 2-ethyl hexyl. R2-CO-N < it can be, for example, cocamide, stearamide, oleamide, lauramide, myristamide, cappcamide, palmitamide, seboamide, etc.

Detergency builders Detergent builders can optionally be included in the present compositions to help control mineral hardness. Organic as well as inorganic builders can be used. Detergency builders are typically used in fabric washing and automatic dishwashing compositions to aid in the removal of particulate dirt. The level of builder can vary widely depending on the final use of the composition and its desired physical form. When they are present, the compositions will typically comprise at least 1% builder. High performance compositions will typically comprise from 10% to 80%, more typically from 15% to 50% by weight of the detergent builder. However, higher or lower levels of the detergency builder are not excluded. Inorganic or phosphorus-containing builders include, but are not limited to, metal polyphosphate salts alkali, ammonium and alkanolammonium (exemplified by the glassy polymeric tripolyphosphates, pyrophosphates and metaphosphates), phosphonates, phytic acid, silicates, carbonates (including bicarbonates and sesquicarbonates), sulphates and aluminosilicates. However, in some places, non-phosphate builders are required. Importantly, surprisingly the compositions herein work well even in the presence of so-called "weak" detergency builders (as compared to phosphates) such as citrate, or in the so-called "lower detergency enhancement" situation that may occur with zeolite or detergent builders based on stratified silicate. See patent E.U.A. 4,605,509 for examples of preferred aluminosilicates. Examples of silicate-based detergency builders are alkali metal silicates, particularly those having a SiO2: Na20 ratio in the range of 1.6: 1 to 3.2: 1 and layered silicates, such as the layered sodium silicates described. in the USA patent 4,664,839, issued May 12, 1987 to H. P. Rieck. The compound NaSKS-6R is a crystalline layered silicate sold by Hoechst (commonly abbreviated hereafter as "SKS-6"). Unlike zeolite-based builders, the SKS-6 sodium silicate builder does not contain aluminum. The compound NaSKS-6 is the morphological form delta-Na2SIOs of layered silicate and can be prepared by methods such as those described in German DE-A3,417,649 and DE-A-3,742,043. The SKS-6 compound is a highly preferred stratified silicate to be used herein, but other similar layered silicates, such as those having the general formula NaMS ^ O ^ -n and H20 where M is sodium or hydrogen, x is a number ranging from 1 9 to 4, preferably 2, ey it is a number ranging from 0 to 20, preferably 0 can be used in the present. Other various layered silicates from Hoechst include NaSKS-5, NaSKS-7 and NaSKS-11, such as the alpha-, beta- and gamma- forms. Other silicates may also be useful, such as, for example, magnesium silicate, which can serve as a tightening agent in granulated formulations, as a stabilizing agent for oxygen-based bleaches, and as a component for foam control systems. Silicates useful in automatic dishwashing applications (ADD) include 2-hydro-granulated silicates such as BRITESILRH20 from PQ Corp., and the commonly sought BRITESILRH24 although liquid grades of various silicates may be used when the ADD compositions are in liquid form. Sodium metasilicate or sodium hydroxide alone or in combination with other silicates can be used within safe limits in an ADD context to boost the wash pH to a desired level. Examples of carbonate-based detergency builders are the alkali metal and alkaline earth metal carbonates as disclosed in German Patent Application No. 2,321,001 published November 15, 1973. Various grades and types of sodium carbonate can be used and sodium sesquicarbonate, some of which are particularly useful as vehicles for other ingredients, especially detersive surfactants. Aluminosilicate-based builders are useful in the present invention. Aluminosilicate-based builders are of great importance in most heavy duty granular detergent compositions currently sold, and may also be a significant detergency builder ingredient in liquid detergent formulations. The aluminosilicate-based builders include those having the empirical formula [Mz (zAI02) xH20 where z and y are integers of at least 6, the molar ratio of z a and is in the range of 1.0 to 0.5, and x is an integer ranging from 15 to 264. Useful aluminosilicate ion exchange materials are commercially available. These aluminosilicates can be crystalline or amorphous in their structure and can be aluminosilicates that occur naturally or synthetically derived. A method for the production of ionic exchange materials based on aluminosilicate is described in the patent E.U.A. 3,985,669, Krummel, et al, issued October 12, 1976. The preferred synthetic crystalline aluminosilicate ion exchange materials useful herein are available under the designations Zeolite A, Zeolite P (B), Zeolite MAP and Zeolite X In a particularly preferred embodiment, the ion exchange material based on crystalline aluminosilicate has the formula Nai2 [(AI02)? 2 (S02)? XH20 where x ranges from 20 to 30, especially about 27. This material is known as Zeolite A. Dehydrated zeolites (x = 0-10) can also be used herein. Preferably, the alummosilicate has a particle size of about 0.1-10 microns in diameter. As with other detergency builders such as carbopates, one might wish to use zeolites in any physical or morphological form adapted to promote the vehicle function of the surfactant, and the appropriate particle sizes can be chosen freely by the formulator . Organic builders suitable for the purposes of the present invention include, but are not limited to, a broad vapeity of porecarboxylated compounds. As used herein, "polycarboxylates" refers to compounds having a plurality of carboxylate groups, preferably at least 3 carboxylates. Polycarboxylate-based builders may be added to the composition generally in acid form, but may also be added in the form of a neutralized or "overbased" salt. When used in saline, alkali metal salts, such as the sodium, potassium, and lithium salts, or alkanolammonium salts, are preferred. A variety of categories of useful materials are included within polycarboxylate builders. An important category of builders based on polycarboxylates includes polycarboxylate ethers, including oxydisuccinates, as described in Berg, U.S. 3,128,287, issued April 7, 1964, and Lamberti et al., Patent E.U.A. 3,635,830, issued on January 18, 1972. See also the 'TMS / TDS' detergency builders of U.S. Patent 4,663,071, issued to Bush et al., May 5, 1987. Suitable polycarboxylate ethers further include cyclic compounds, particularly alicyclic compounds, such as those described in US Pat. US Patents 3,923,679, 3,835,163, 4,158,635, 4,120,874 and 4,102,903 Other useful builders include hydroxypolycarboxylate ethers, co-polymers of maleic anhydride with ethylene or vinyl methyl ether, 1, 3,5-tr? Droxibencen-2,4,6-tpsuiphen? co and carboxymethyloxysuccinic acid, the various alkali metal, ammonium and substituted ammonium salts of poly-acetic acids such as ethylenediaminetetraacetic acid and nitriloacetic acid, as well as polycarboxylates such as acid melitic acid, succinic acid, oxydisuccinic acid, poly-maleic acid, 1,3-tricarboxylic acid, carboxymethyloxysuccinic acid and salts soluble thereof Citrate-based builders, eg, citric acid and soluble salts thereof (particularly the sodium salt), are polycarboxylate-based detergency builders of particular importance to the formulations of heavy-duty laundry detergent due to its availability from renewable resources and its capacity for biodegradation. The citrates can also be used in combination with zeolite and / or lauriisuccinates are the preferred builders of this group, and are described in European patent application 86200690.5 / 0,200,263, published on November 5, 1986.

Other suitable polycarboxylates are described in the U.S.A. 4,144,226, Crutchf? Eld et al., Issued March 13, 1979, and in the patent of E.U.A. 3,308,067, Dlehl, issued March 7, 1967. See also the patent of E.U.A. 3,723,322. Fatty acids, for example, monocarboxylic acids of C- | 2- C- | 8. they may also be incorporated into the compositions alone or in combination with the aforementioned builders, especially citrate and / or succinate detergent cleaners, to provide additional builder activity. Said use of fatty acids will generally result in a decrease in the formation of foams, which must be taken into account by the formulator. In situations where phosphorus-based detergency builders can be used, and especially in the formulation of bars used for hand-washing operations, the different alkali metal phosphates, such as the well-known sodium thiophosphites, pyrophosphates, can be used. sodium and sodium orthophosphate. Phosphonate builders such as 1-hydroxy-1,1-diphosphonate of ethane and other known phosphonates can also be used (see, for example, US Patents 3,159,581, 3,213,030, 3,422,021, 3,400,148 and 3,422,137). However, in general, phosphorus-based builders are not suitable. Chelating Agents The compositions herein may also optionally contain one or more heavy metal chelating agents, such as diethylenetriaminepentaacetic acid (DTPA). More generally, chelating agents suitable for use herein may be selected from group consisting of ammocarboxylates, aminophosphonates, polyfunctionally substituted aromatic chelating agents, and mixtures thereof. Without intending to be limited by theory, it is believed that the benefit of these materials is due in part to their exceptional ability to remove heavy metal ions from the wash solutions through the formation of soluble chelates; Other benefits include the prevention of scale formation or inorganic film. Other chelating agents suitable for use herein are the commercial semen DEQUEST and the chelating agents of Monsanto, DuPont and Nalco, Inc. The aminocarboxylates useful as optional chelating agents include ethylenediaminetetraacetates, N-hydroxyethylethylene diaminotriacetates, nitrilotriacetates, ethylenediaminetetrapropionates, triethylene tetraaminohexaacetates, diethylenetriammopentaacetates and ethanoldiglicins, alkali metal, ammonium and substituted ammonium salts thereof, and mixtures thereof. Aminophosphonates are also useful for use as chelating agents in the compositions of the invention when at least low levels of total phosphorus are allowed in the detergent compositions, and include ethylene diamine tetrakis (methylene phosphonates). Preferably, these aminophosphonates do not contain alkyl or alkenyl groups with more than about 6 carbon atoms. Polyfunctionally substituted aromatic chelating agents are also useful in the compositions herein. See the patent of E.U.A. 3,812,044, issued May 21, 1974 to Connor and others.

Preferred compounds of this type in acid phthane are dihydroxydisulfobenzenes such as 1,2-dihydroxy-3,5-d-sulfobenzene. A highly biodegradable chelating agent intended for use herein is ethylenediamine disuccinate ("EDDS"), especially (but not limited to) the isomer [S, S, j, as described in the U.S.A. 4,704,223, issued on November 3, 1987 to Hartman and Perkins. The trisodium salt is preferred, although other forms, such as magnesium salts, are also useful. If used, these selective transition metal chelating agents or sequestrants will preferably comprise from about 0.001% to about 10%, more preferably about 0. 05% to about 1% by weight of the bleaching compositions herein.

Polymeric dirt release agent Any polymeric soil release agent known to those skilled in the art can optionally be employed in the compositions and methods of this invention. Polymeric soil release agents are characterized by having both hydrophilic segments to hydrophilize the surface of hydrophobic fibers such as polyester and nylon, and hydrophobic segments to be deposited on hydrophobic fibers and remain adhered thereto until the washing and rinsing cycles are completed. and thus serve as an anchor for the hydrophilic segments. This allows stains that appear after treatment with the soil release agent to be cleaned more easily in subsequent washing procedures.

The polymeric soil release agents useful herein include especially those soil release agents having: (a) one or more nonionic hydrophilic components consisting essentially of (i) polyoxyethylene segments with a degree of polymerization of at least 2 , or (n) oxypropylene or polyoxypropylene segments with a degree of polymerization of 2 to 10, wherein said hydrophilic segment does not comprise any oxypropylene unit unless it is linked to adjacent portions at each end by ether linkages, or (! ü) a mixture of oxyalkylene units comprising oxyethylene units and from 1 to about 30 oxypropylene units wherein said mixture contains a sufficient amount of oxyethylene units of such form that the hydrophilic component has sufficiently large hydrophilic character to increase the hydrophilic character of the surfaces of synthetic fabrics of conventional polyester over the deposit of the soil release agent on said surface, said hydrophilic segments preferably comprising at least about 25% oxyethylene units and most preferably, especially for the components having approximately 20 to 30 oxypropylene units, at least 50% oxyethylene units; or (b) one or more hydrophobic components comprising (i) oxyalkylene terephthalate C3 segments, wherein, if said hydrophobic component also comprises oxyethylene terephthalate, the ratio of oxyethylene terephthalate to oxyalkylene terephthalate C3 is about 2: 1 or less, (i) segments C4-C6 alkylene or C4-C6 oxyalkylene, or mixtures thereof, (ii) poly (vinyl ester) segments, preferably polyvinyl acetate, having a degree of polymerization of at least 2, or (iv) substituents of C 1 -C 4 alkyl ether or C 4 hydroxyalkyl ether, or mixtures thereof, wherein said substituents are present in the form of cellulose derivatives of C 1 -C 4 alkyl ether or C 4 hydroxyalkyl ether, or mixtures thereof, and said cellulose depots are amphiphilic, so they have a sufficient level of ether units CJ-C4 alkyl and / or C4 hydroxyalkyl ether to be deposited on surfaces of conventional synthetic polyester fabric and retain a sufficient level of hydroxyls, once adhered to said conventional synthetic fiber surface, to increase the hydrophilic character of the surface of cloth, or a combination of (a) and (b). Typically the polyoxyethylene segments of (a) (i) have a degree of polymerization of about 200, although higher levels can be used, preferably from 3 to about 150, most preferably from 6 to about 100. The oxyalkylene segments of suitable C4-C6 hydrophobic agents include, but are not limited to, blocked ends of polymeric soil release agents such as M? 3S (CH2) nOCH2CH2? -, where M is sodium and n is an integer of 4-6, such as it is described in U.S. Patent 4,721, 580 issued on January 26, 1988 to Gosselink. The polymeric soil release agents useful in the present invention also include cellulose derivatives such as hydroxyether cellulosic polymers, copolymer blocks of ethylene terephthalate or propylene terephthalate with polyether terephthalate oxide or polypropylene terephthalate oxide and the like. Such agents are commercially available and include cellulose hydroxyethers such as METHOCEL (Dow). Cellulosic soil release agents for use herein also include those selected from the group consisting of C 1 -C 4 alkylicelulose and C 4 hydroxyalkylcellulose, see U.S. Pat. 4,000,093 issued on December 28, 1976 to Nicol et al.

Dirt release agents characterized by hydrophobic segments of polyester (vinyl ester) include poly (vinyl ester) graft copolymers, For example vinyl esters of Ci-Cß preferably poly (vinylacetate) grafted to oxide base structures of polyalkylene, such as polyethylene oxide base structures. See European Patent Application 0 219 048 published April 22, 1987 by Kud et al. Commercially available soil release agents include SOKALAN type of material, for example, SOKALAN HP-22, available from BASF (West Germany). One type of preferred soil release agent is a copolymer having random blocks of ethylene terephthalate and polyethylene terephthalate oxide (PEO). The molecular weight of this polymeric soil release agent is in the range of about 25,000 to about 55,000. See U.S. Pat. 3,959,230 to Hays issued May 25, 1976 and the Patent of E.U.A. 3,893,929 to Basadur issued July 8, 1975. Another preferred polymeric soil release agent is a polyester with repeating units of ethylene terephthalate units containing 10-15% by weight of ethylene terephthalate units together with 90-80% by weight of polyoxyethylene terephthalate units, derived from a polyethylene glycol of average molecular weight of 300-5,000. Examples of this polymer include the commercially available material ZELCON 5126 (from Dupont) and MILEASE T (from ICI). See also the U.S. Patent. 4,702,857 issued on October 27, 1987 to Gosselink. Another preferred polymeric soil release agent is a sulphonated product of a substantially linear ester oligomer which consists of an ohmomepco ester base structure of terephthaloyl and oxyalkylenoxy repeating units and terminal portions covalently bonded to the base structure These soil release agents are described extensively in US Patent 4 968,451 issued November 6, 1990 a JJ Scheibel and EP Gosselmk Other suitable polymetallic soil release agents include the terephthalate polyesters of US Patent 4,711,730 issued December 8, 1987 to Gosselink et al., the oligomepic esters blocked at their ends to ions from U.S. Patent 4,721,580 issued on January 26, 1988 to Gosselink and the oligomeric block-form compounds of U.S. Patent 4,702,857 issued October 27, 1987 to Gosselink. Polimepic soil release agents also include the soil release agents of US Patent 4,877,896 issued October 31, 1989 to Maldonado et al., Which discloses ammonium compounds, especially sulfoarolyl esters of terephthalate blocked at their ends. polymeric dirt is an oligomer with repeating units of terephthaloyl units, sulfoisoteiftaloyl units, oxyethyleneoxy units and ox? -1, 2-propylene. The repeating units form the base structure of the oligomer and preferably end with modified endings of isethionate A particularly preferred soiling agent of this type consists of apr approximately one sulfoisophthaloyl unit, 5 terephthaloyl units, oxyethyleneoxy units and ox? -1, 2-prop? lenox? in a ratio of from about 17 to about 18, and two end cap units of sodium 2- (2-hydroxyethoxy) -ethansulfonate said soil release agent also consists of from about 0 5% to about 20% by weight of the oligomer, of a crystal reducing stabilizer, preferably selected from the group consisting of xylene sulfonate, eumeno sulfonate, toluene sulfonate and mixtures thereof. If used, the soil release agents generally comprise from about 0.01% to about 10.0% by weight of the detergent compositions herein, typically from about 0.1% to about 5%, preferably from about 0.2% to about 3.0. %.

Enzymes Enzymes may be included in the present detergent compositions for a variety of purposes, including the removal of protein-based stains, based on carbohydrates or on the basis of tglilcéridos of surfaces such as fabrics, for the prevention of dye transfer, for example. in laundry, and for fabric restoration. Enzymes to be incorporated include proteases, amylases, cellulases and peroxidases, and mixtures thereof. Other types of enzymes can also be included. They can be of any suitable origin, such as vegetable, animal, bacterial, fungal and yeast. However, their use is determined by factors such as optimal levels of pH activity and / or stability, thermostability, stability against active detergents, detergency builders, etc. In this regard, bacterial or fungal enzymes are preferred, such as bacterial amylases and proteases and fungal cellulases. Enzymes are normally incorporated at levels sufficient to provide up to about 5 mg by weight, more typically about 0.01 mg to about 3 mg, of active enzyme per gram of the composition. Stated otherwise, the compositions herein will typically consist of from about 0.001% to about 5%, preferably 0.01% -1% by weight of a commercial enzyme preparation. Protease enzymes are present in such commercial preparations at levels sufficient to provide from 0.005 to 0.1 Anson units (AU) of activity per gram of composition. Suitable examples of proteases are the subtilisins that are obtained from particular strains of B.subtilis and B.licheniformis. Other suitable proteases are obtained from a Bacillus strain. having a maximum activity in the entire pH range of 8 to 12, developed and marketed as ESPERASER by Novo Industpes A S of Denmark. The preparation of this enzyme and analogous enzymes is described in the Great Britain patent specification 1, 243,784, by Novo. Proteolytic enzymes suitable for removing spots based on proteins and which are commercially available include those marketed under the names of ALCALASER and SAVINASER by Novo Industries A / S (Denmark), and MAXATASER by International Bio-Synthetics, Inc., The Netherlands. Other proteases include Protease A (see European Patent Application 130,756 A, published January 9, 1985) and Protease B (see European Patent Application Serial No. 87303761.8, filed on April 28, 1987, and European Patent Application 130,756, Bott et al., published Jan. 9, 1985. A particularly preferred protease, called "protease D" is a carbonyl hydrolase variant having an amino acid sequence that is not found in nature, which is derived from a precursor hydrolase carbony replacing a different amino acid by a plurality of amino acid residues at a position in said hydroxylase carbonyl equivalent to position +76, preferably also in combination with one or more amino acid residue positions equivalent to those selected from the group consisting of +99, +101, +103, +104, +107, +123, +27, +105, +109, +126, +128, +135, +156, +166, +195, +197, +204, +206, +210, +216, +217, +218, +222, +260 , +265, and / or +274 according to the numeration of the subtilisin of Bacillus amyloliquefaciens. as described in the patent applications of A. Baeck et al., entitled "Protease-Containing Cleaning Compositions", with No. of senes 08 / 322,676, and Ghosh et al., "Bleaching Compositions Com pping Protease Enzymes", with No. Sene 08 / 322,677, both filed on October 13, 1994, and also in WO 95/10615, published April 20, 1995.

Amylases suitable herein include, for example, α-amylases described in the bptican patent specification No. 1, 296,839 (Novo), RAPlDASER, International Bio-Synthetics, Inc. and TERMAMYLR, from Novo Industries. Enzyme genetic engineering (eg, amylase of improved stability) is well known for improved stability, for example, oxidative stability. See, for example, J. Biological Chem., Vol. 260, No. 11, June 1985, pp. 6518-6521. The "reference amylase" refers to a conventional amylase within the scope of the amylase component of this invention. In addition, the amllasas of improved stability, also within the scope of the invention, are typically compared with these "reference amylases".

The present invention, in certain preferred embodiments, can make use of amloses having improved stability in detergents, especially improved oxidative stability. A convenient absolute stability reference point against which the amllasas used in these preferred embodiments of the present invention represent a measurable improvement, is the stability of TERMAMYLR in commercial use in 1993, and available from Novo Nordisk A S. This amylase, TERMAMYLR , is a "reference amylase", and is itself well suited for use in the ADD (automatic dishwashing detergent) compositions of the invention. Even the most preferred amylases herein share the characteristics of being "improved stability" amylases characterized, to a minimum, by a measurable improvement in one or more of: oxidative stability, for example, to hydrogen peroxide / tetraacetylethylene diamine in regulated solution at its pH at a pH of 9 to 10; thermal stability, for example, at common wash temperatures, such as about 60 ° C; or alkaline stability, for example, at a pH of about 8 to about 11, all measured against the reference amylase identified above. Preferred amylases herein can demonstrate further improvement against most of the reference amylases, the last reference amylases being polished by any of the precursor amylases of which the amylases referred to within the invention are variants. Said precursor amylases may be of natural origin, or the genetically engineered product. Stability can be measured using any of the technical tests described in the art. See the references described in WO 94/02597, and documents referred to herein incorporated by reference. In general, amylases of improved stability with respect to the preferred embodiments of the invention can be obtained from Novo Nordisk A / S or Genencor International. Preferred amllasas of the present have the common characteristic of being derived using site-directed mutagenesis of one or more of the Bacillus amylases, especially the Bacillus α-amylases, regardless of whether one, two or multiple vanishing amylase are the precursors immediate. As noted above, amylases of "improved oxidative stability" are preferred for use herein despite the fact that the invention makes them "optional but preferred" matepals, rather than essential. Said amllasas are illustrated in a non-limiting manner by the following: (a) an amylase according to WO / 94/0297, incorporated above, by Novo Nordisk A / S, published on February 3, 1994, which is best illustrated by a mutant in which a substitution is made, using alanine or threonine (preferably threonine), of the methionine residue located at position 197 of the α-amylase of B. licheniformis. known as TERMAMYLR, or the homologous position variation of a similar progenitor amylase, such as of the B. amyloiiauefaciens species. B ± subtilis. or B. stearothermofilus: (b) amylases of improved stability, as described by Genencor International in an article entitled "Oxidatively Reslstant alpha- Amylases ", presented at the 20th National Meeting of the American Chemical Society, March 13 to 17, 1994, by C. Mltchinson, where it was observed that the bleaches in detergents for automatic dishwashing inactivate the α-amylases, but that amylases of improved oxidative stability have been obtained by Genencor from the NCIB8061 strain of B. licheniformis.Methionine (Met) was identified as the most probable residue to be modified.The Met was substituted, one at a time, in the positions 8, 15, 197, 256, 304, 366 and 438, resulting in specific mulants, with M197L and M197T being particularly important, with variant M197T being the most stable expressed variant.The stability was measured in CASCADER and SUNLIGHTB; c) particularly preferred herein are variants of amylase having further modification in the immediate parent, available from Novo Nordisk A / S. These amiiases include those marketed as DURAMYL by NOVO; Stable stains to bleach are also available commercially from Genencor. Any other amylase of improved oxidative stability can be used, for example, as derived by site-directed mutagenesis from known simple, chimeric or hybrid mutant progenitor forms of available amylases. Usable but not preferred cellulases in the present invention include ceiulases of both bacteria and fungi. Typically, they will have an optimum pH between 5 and 9.5. Suitable cellulases are described in the patent of U.S. 4,435,307, Barbesgoard et al., Issued March 6, 1984, which detects cellulases of fungi produced from Humicola insolens v. Humicola strain DSM1800, or a ceiulase-producing fungus 212 belonging to the genus Aeromonas. and the cellulase extracted from the hepatopancreas of the marine mollusk (Dolabella auricula Solander). Suitable cellulases are also deciphered in GB-A-2,075,028; GB-A-2,095,275 and DE-OS-2,247,832. CAREZYMER (Novo) is especially useful. Lipase enzymes suitable for use in detergents include those produced by microorganisms of the Pseudomonas group, such as ATCC 19,154 of Pseudomonas stutzeri, as described in British Patent 1, 372,034. See also lipases in Japanese Patent Application 53,20487, open to the public for public inspection on February 24, 1978. This lipase is available from Amano Pharmaceutical Co. Ltd., Nagoya, Japan, under the trade name Lipase P "Amano", hereinafter referred to as "Amano-P". Other commercial lipases include Amano-CES, Chromobacter viscosum lipases. for example, NRRLB 3673 of Chromobacter viscosum var. lipolvticum. commercially available from Toyo Jozo Co., Tagata, Japan; and in addition the Chromobacter viscosum lipases from U.S. Biochemical Corp., U.S.A. and Dísoynth Co., Holland, and the lipases of Pseudomonas aladioli. The LIPOLASE enzyme "derived from Humicola lanuainosa and commercially available from Novo (see also EPO 341, 947), is a preferred lipase for use herein, Another preferred lipase enzyme is the D96L variant of the native lipase of Humicola lanuainosa. described in the WO document 92/05249 and the research description No. 35944, of March 10, 1994, both published by Novo. In general, lipolytic enzymes are less preferred than amylases and / or proteases in the automatic dishwashing modalities of the present invention. Peroxidase enzymes can be used in combination with oxygen sources, for example, percarbonate, perborate, persulfate, hydrogen peroxide, etc. They are typically used for "solution bleaching", that is, to avoid the transfer of dyes or pigments Removed from the substrate during washing operations towards other substrates in the washing solution. Peroxidase enzymes are known in the art and include, for example, horseradish peroxidase, ligninase and haloperoxidase such as chloroperoxidase and bromoperoxidase. Peroxidase-containing detergent compositions are described, for example, in PCT International Application WO 89/099813, published October 19, 1989 by O. Kirk, assigned to Novo Industries A / S. The present invention encompasses modalities of compositions for the automatic washing of dishes free of peroxidases. A wide variety of enzyme materials and means for their incorporation into synthetic detergent compositions are also described in the U.S. Patent. 3,553,139, issued January 5, 1971 to McCarty et al. Additionally, enzymes are described in the U.S. Patent. 4,101, 457, Place et al., Issued July 18, 1978, and in the U.S. Patent. 4,507,219, Hughes, both issued March 26, 1985. Enzymes for use in detergents can be stabilized by various techniques. Enzyme stabilization techniques are described and illustrated in the U.S. Patent. 3,600,319, issued August 17, 1971 to Gedge et al., And in the Publication of European Patent Application No. 0 199 405, 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.

Other Ingredients The usual ingredients may include one or more materials to facilitate or improve the cleaning performance, the treatment of the substrate to be cleaned, or to modify the aesthetics of the composition. The usual detersive adjunct ingredients of the detergent compositions include the ingredients described in U.S. Pat. No. 3,936,537, Baskervllle et al. The adjunct ingredients that can also be included in the compositions used in the present invention, at their conventional levels of use established in the art (generally from 0% to about 20% of the detergent ingredients, preferably from about 0.5% to about 10%). %), include other active ingredients such as enzyme stabilizers, anti-rust and / or anti-corrosion agents, dyes, fillers, optical brighteners, germicides, alkalinity sources, hydrothopes, antioxidants, enzyme stabilizing agents, perfumes, dyes, solubilizing agents, agents Removal / anti-redeposition of clay dirt, vehicles, processing aids, pigments, solvents for liquid formulations, fabric softeners, static control agents, solid fillers for stick compositions, etc. Agents may be used dye transfer inhibitors, including polyamine N-oxides such as polyvinyl pyridine N-oxide. The dye transfer inhibiting agents are best illustrated by the polyvinylpyrrolidone and the copolymers of N-vinylimidazole and N-vinylpyrrolidone. If high foaming is desired, foaming enhancers such as C? Or C? 8 alkanolamides, typically at levels of 1% to 10%, can be incorporated into the foam enhancing compositions. C10-C14 monoethanol- and diethanolamides illustrate a typical group of said foaming enhancers. The use of said foaming enhancers with adjunctive surfactants of high foaming formation such as amine oxides, betaines and sultaines described above, is also advantageous. If desired, soluble magnesium salts such as MgCl 2, MgSO 4, and the like, can be added at levels of, typically, 0.1% to 2%, to provide additional foams and to increase the fat removal performance.

Liquid compositions The present invention comprises both liquid and granular compositions that include the aforementioned ingredients. Liquid compositions, including gels, typically contain a certain amount of water and other fluids as carriers. Low molecular weight primary or secondary alcohols exemplified by methanol, ethanol, propanol and isopropanol, are suitable. Monohydric alcohols are preferred to solubilize the surfactant, but polyols such as those containing from 2 to about 6 carbon atoms, and 2 to about 6 hydroxy groups (eg, 1,3-propanediol, ethylene glycol, glycerin and 1,2-propanediol). The compositions may contain from 5% to 90%, typically from 10% to 50% of said vehicles. The liquid compositions according to the present invention can be formulated in acid form to release an alkaline pH during use. The low pH formulation is generally from about 2 to about 5, and preferably from about 2.5 to about 4.5. During use, the pH may range from about 7 to about 11, preferably from about 9.5 to about 10.5.

Emulsification system The liquid compositions of the present invention can also typically include an emulsification system or a thickening system. The emulsification or thickening system provides adequate profiles of stability and storage life. An emulsification system is typically used for activators that are liquid or have been previously dissolved. The emulsification system is generally present in amounts of from about 0.1% to about 60% by weight of the composition, preferably between about 2 and 30%, and more preferably between about 3 and 25% by weight of the composition. The emulsification system is selected to provide an HLB or hydrophilic-llpofilic balance that is compatible with the HLB requirement of the activator Asymmetric as defined above. For the asymmetric activators defined above, the HLB value of the emulsification system of the present invention will typically vary from about 6 to about 16, and more preferably from about 7 to about 15. However, in cases where the asymmetric activator is Dissolve first in a solvent, the HLB value of the emulsification system will be selected to be compatible with the most activating solvent system. The emulsification system of the present invention can be formed by a nonionic surfactant, mixtures of nonionic surfactants, or mixtures of anionic and nonionic surfactants. Preferably, the emulsification system is a nonionic surfactant or mixtures of nonionic surfactants. When mixtures of surfactants are used as the emulsification system, it is the HLB value for the mixture that is used as the HLB of the emulsification system. The hydrophilic-lipophilic balance is an expression of the relative simultaneous attraction of an emulsifier for water and for oil (or the two phases of the emulsion system being considered). The HLB value for a given compound is generally determined by the chemical composition and the degree of ionization. The value can be determined by several ways, the easiest of which is the chemical composition by several formulas. The different methods that are used to calculate the value of HLB are well known to those skilled in the art and are described, for example, in Nonionic Surfactants, Physical Chemistry, by Marcel Dekker, Inc., volume 23, 1987, pp 438-456 and Emulsiops and Emulsion Technology, part I, volume 6 of the Surfactant Science Series, 1974, pp. 264-269. Preferred emulsifiers for use in the emulsification system of the present invention are nonionic alkylalkoxylate surfactants such as alkoxylated fatty alcohols. A large number of alkoxylated fatty alcohols are commercially available with varying values of HLB. The HLB values of said alkoxylated nonionic surfactants depend essentially on the chain length of the fatty alcohol, the alkoxylation nature and the degree of alkoxylation. The nonionic surfactants that are most preferred in the present invention are ethoxylated fatty alcohols. The alcohols can be of natural or petrochemical origin and straight or branched chain. Ethoxylated fatty alcohol nonionic surfactants suitable for use in the emulsification system of the present invention are commercially available under the tradenames DOBANOL and NEODOL, available from The Shell Oil Company of Houston, Texas.

Thickening System The liquid compositions of the present invention may also include a thickening system. Thickening systems are typically used for activators that are solid or in the form of particles. The particle sizes of the activator will generally vary from about 0.1 to about 1,000 microns, preferably from about 1 to about 500 microns, and more preferably from about 1 to about 250 microns. The thickening system thus comprises a rheology capable of suspending the particulate activator in the liquid composition. Those skilled in the art will recognize that, in the simplest case, a rheology capable of suspending solids is simply a viscosity sufficient to prevent sedimentation, creaming, flocculation, etc., of the particles being suspended. The required viscosity will vary according to the particle size, but generally it should be greater than about 300 cps (measured at 10 rpm), preferably greater than 600 cps, and more preferably even higher than 1000 cps. It will also be recognized by those skilled in the art that the rheology will preferably be that of a non-Newtonian fluid of shear thinning. These fluids exhibit very high viscosities at low shearby decreasing the viscosity as the shear increases, for example, a shear thinning fluid may have a viscosity of 2000 cps at 10 rpm, but only 500 cps at 100 rpm. Said shear thinning systems can be obtained in various ways, including the use of associative polymeric thickeners, emulsions and specific surfactant systems.

Coating Various detersive ingredients used in the present compositions can be optionally stabilized by absorbing the ingredients on a porous hydrophobic substrate, and then coating the substrate with a hydrophobic coating. Preferably, the detersive ingredient is mixed with a tepsioactive agent before it is absorbed onto the porous substrate. During use, the detersive ingredient is released from the substrate in the aqueous wash solution, where it carries out its proposed detersive function. To illustrate this technique in more detail, a porous hydrophobic silica (trademark SIPERNATRD10, Degussa) is mixed with a proteolytic enzyme solution containing 3 to 5% ethoxylated alcohol nonionic surfactant (EO 7) of C13.15 . Typically, the enzyme / surfactant solution is 2.5 times the weight of silica. The resulting powder is dispersed with stirring in silicone oil (various viscosities of silicone oil can be used in the range of 500 to 12,500). The resulting silicone oil dispersion is emulsified or otherwise added to the final detergent matrix. By this method, ingredients such as the enzymes, hydrogen peroxide sources, bleach activators, bleach catalysts, photoactivators, dyes, fluorescers, fabric conditioners and hydrolyzable surfactants mentioned above, can be "protected" for use in detergents , including liquid laundry detergent compositions. Alternative forms for coating particles such as, for example, wax encapsulation, are described in U.S. Pat. Nos. 4,087,369, 5,230,822 and 5,200,236.

Bar compositions The bleaching and bleaching additive compositions of the present invention can also be used in the form of a laundry or cleaning bar. The bar forms typically include a surfactant which can include both soap and synthetic detergent, or all of which are synthetic in terms of the surfactant content, in conjunction with a suitable source of hydrogen peroxide and the imide bleach activators of the present invention. In fact, those skilled in the art will recognize that the levels of the peroxide source and imide activator surfactant can Widely vary said stick composition according to the present invention comprises from about 10% to about 90% surfactant (including soap or mixtures thereof with conventional synthetic surfactants), from about 0 1% to about 40% of Sodium perborate as a source of peroxide, from around from 0 1% to about 20% imide activator of the formula (I), from about 0 1% to about 50% builder, and optionally from about 0 1% to about 60% inorganic fillers or organics such as talc, starch or the like. Suitable bar compositions, and the methods of making them, are described in US Pat. Nos. 4,115,105,324,333,333, 5,40492 and 5,496,488, the disclosures of which are incorporated herein by reference. herein as a reference, and in Great Britain patent application 2 096 163A Hard Surface Cleaning Compositions The bleaching and bleach additive compositions of the present invention may also take the form of hard surface cleaning compositions. The hard surface cleaning compositions can be formulated in general identically as the bleaching compositions or bleaching additives described above, or they can be formulated according to the most specialized hard surface cleaning technique using, for example, low content surfactants. of waste. As in the case of other embodiments of the invention, the pH of said compositions can vary widely, depending on the proposed use of the composition. Suitable hard surface cleaning compositions useful in conjunction with the imide activator of the present invention are described in US Patents. 5,536,450; 5,536,451; and 5,538,664, the disclosures of which are incorporated herein by reference. In fact, those skilled in the art will recognize that it is preferable to use ingredients stable to bleaching, provided that a source of hydrogen peroxide is formulated in the compositions.

Granulated Compositions Bleaching compositions and bleaching additives of the present invention can be used in granular compositions of low density (less than 550 grams / liter) and high density, in which the density of the granule is at least 550 grams / liter. The granulated compositions they are typically designed to provide a pH in the wash of about 7.5 to about 11.5, more preferably about 9.5 to about 10.5. The low density compositions can be prepared by standard spray drying procedures. Various media and equipment are available to prepare high density compositions. Current commercial practice in the field uses spray-drying towers to make compositions having a density of less than about 500g / l. Accordingly, if spray drying is used as part of the general procedure, the resulting spray-dried particles should also be densified using the means and equipment described below. In the alternative, the formulator can eliminate spray drying using commercially available mixing, densifying and granulating equipment. The following is a non-limiting description of such equipment suitable for use herein. Various means and equipment are available to prepare high density granular detergent compositions (ie, greater than about 550, preferably greater than about 650, grams / liter or "g / l"), high solubility and free flowing in accordance with the present invention. Current commercial practice in the field uses spray-drying towers to make granular laundry detergents that often have a density of less than about 500 g / l. In this process, an aqueous suspension of various thermostable ingredients in the final detergent composition is formed into homogeneous granules by passing them through a spray-drying tower, using conventional techniques, at temperatures of about 175 ° C to about 225 ° C. However, if spray drying is used as part of the general procedure herein, other process steps as described below should be used to obtain the density level (ie,> 650 g / l) required for the modern compact and low dosage detergent products. For example, the spray-dried granules of a tower can be further densified by charging a liquid such as water or a nonionic surfactant into the pores of the granules, and / or by subjecting them to one or more high-speed mixers / densifiers. A high speed mixer / densifier suitable for this process is a device marketed under the trade name "Lódige CB 30" or "Lódige CB 30 recirculator", which comprises a static cylindrical mixing drum having a central rotating shaft with blades of mixing / cutting mounted on it. During use, the ingredients of the detergent composition are introduced into the drum, and the arrow / blade assembly is rotated at speeds in the range of 100 to 2500 rpm to provide complete mixing / densification. See Jacobs et al., Patent of E.U.A. 5,149,455, issued September 22, 1992. The preferred residence time in the high-speed mixer / densifier is from about 1 to 60 seconds. Other such devices include the devices marketed under the trade name of "Shugi granulator" and under the trade name "Drais K-TTP 80". Another step of the process that can be used to densify even more spray-dried granules involves grinding and agglomerating or deforming the spray dried granules in a moderate speed mixer / densifier to obtain particles having lower intraparticle porosity. Equipment such as that marketed under the trade name of "Lódige KM" (series 300 or 600) or mixer / densifiers "Lodige Ploughsare", is suitable for this step of the procedure. Said equipment is typically operated from 40 to 160 rpm. The residence time of the detergent ingredients in the moderate speed mixer / densifier is from about 0.1 to 12 minutes. Other useful equipment includes the device that is available under the trade name of "Drais K-T 160". This procedure step using a moderate speed mixer / densifier (for example, Lddlge KM) is can be used alone or sequentially with the high speed mixer / densifier mentioned above (eg, Lodige CB) to achieve the desired density. Other types of apparatus for making granules useful herein include the apparatus described in the U.S.A. 2,306,898, by GL Heller, December 29, 1942. Although it may be more convenient to use the high speed mixer / densifier followed by the low speed mixer / densifier, the inverse sequential configuration of mixer / densifier is also contemplated by the invention. One or a combination of several parameters that include residence times in the mixer / densifiers, equipment operating temperatures, temperature and / or composition of the granules, the use of adjunct ingredients such as liquid binders and flow aids, is used to optimize the densification of the dried granules by sprinkling in the process of the invention. By way of example, see the procedures in Appel et al., U.S. Pat. 5,133,924, issued July 28, 1992 (the granules are brought to a deformable state before densification); Delwel et al., Patent of E.U.A. 4,637,891, issued January 20, 1987 (granulation of spray-dried granules with a liquid binder and aluminosilicate); Kruse et al., Patent of E.U.A. 4,726,908, issued February 23, 1988 (granulation of spray-dried granules with a liquid binder and aluminosilicate); and Bortolotti et al., patent of E.U.A. 5,160,657, issued November 3, 1992 (coating densified granules with a liquid binder and aluminosilicate). In those situations in which particularly hot or highly volatile detergent ingredients will be incorporated into the final detergent composition, processes not including spray towers are preferred. The formulator can eliminate the spray drying step by feeding, in an intermittent or continuous mode, starting detergent ingredients directly into commercially available mixing / densifying equipment. A particularly preferred embodiment involves charging a surfactant paste and an anhydrous builder material in a high speed mixer / densifier (e.g., Lódige CB), followed by a moderate speed mixer / densifier (e.g., Lddige KM) to form high density detergent agglomerates. See Capeci et al., Patent of E.U.A. 5,366,652, issued November 22, 1994, and Capeci et al., Patent of E.U.A. No. 5,486,303, issued January 23, 1996. Optionally, the liquid / solids ratio of the starting detergent ingredients in said process can be selected to obtain high tensile agglomerates that are free flowing and crisp. Optionally, the method may include one or more recirculation streams of undersized particles produced by the process, which are fed back to the mixer / densifiers for further agglomeration or accumulation. The oversized particles produced by this process can be sent to a crushing apparatus and fed back to the mixing / densification equipment. These additional steps of recirculating the process facilitate agglomeration of the starting detergent ingredients in the finished composition having a uniform particle size distribution (400 to 700 microns) and density (> 550 g / l) desired. See Capeci et al., Patent of E.U.A. 5,516,448, issued May 14, 1996, and Capeci et al., Patent of E.U.A. 5,489,392, issued February 6, 1996. Other suitable methods that do not require the use of spray-drying towers are described in Bollier et al., U.S. 4,828,721, issued May 9, 1989; Beerse and others, patent of E.U.A. 5,108,646, issued April 28, 1992; and Jolicoeur, patent of E.U.A. 5,178,798, issued January 12, 1993. In yet another embodiment, the high density detergent composition of the invention can be produced using a fluidized bed mixer. In this process, the different ingredients of the finished composition are combined in an aqueous suspension (typically 80% solids content) and sprayed in a fluidized bed to provide the finished detergent granules. Prior to the fluidized bed, this method may optionally include the step of mixing the suspension using the Lodige CB mixer / densifier mentioned above or a "Flexomix 160" mixer / densifier, available from Shugi. In such processes the fluidized event or moving beds of the type available under the trade name of "Escher Wyss" can be used. Another suitable method that can be used herein involves feeding a liquid acid precursor of an anionic surfactant, an alkaline inorganic material (eg, sodium carbonate) and optionally other detergent ingredients into a high speed mixer / densifier (time of residence from 5 to 30 seconds) to form agglomerates containing a partially or fully neutralized apionic surfactant salt and the other starting detergent ingredients. Optionally, the contents of the high speed mixer / densifier can be sent to a moderate speed mixer / densifier (eg, Lodige KM) for further agglomeration, resulting in the composition high density finished detergent See Appel et al., U.S. 5,164,108, issued November 17, 1992. Optionally, high density detergent compositions according to the invention can be produced by mixing conventional or densified spray-dried detergent granules with detergent agglomerates in vain proportions (eg, a weight ratio of 60%). : 40 granules: agglomerates) produced by some or a combination of the processes described herein. Additional adjunct ingredients such as enzymes, perfumes, brighteners and the like, may be sprinkled or mixed with the agglomerates, granules or mixtures thereof produced by the methods described herein. Granulated bleach compositions typically limit the water content, for example, to less than about 7% free water, for better storage stability. The bleaching compositions of the present invention are ideally suited for use in compositions for laundry applications and for automatic dishwashing. It is intended that the bleaching additive compositions be used in conjunction with a source of hydrogen peroxide, such as a bleaching composition including a detergent, for example, TIDER WITH BLEACH. Accordingly, the present invention includes a method for washing soiled fabrics. The method includes contacting a fabric to be washed with an aqueous wash solution. The fabric can mainly comprise any fabric capable of being washed in normal conditions of use by the user. The wash solution includes the bleach additive with the added bleach composition containing an asymmetric activator as described in greater detail above. The washing solution may also include any of the additives described above for the compositions such as source of hydrogen peroxide, detersive surfactants, chelating agents and detersive enzymes. The compositions are preferably used at concentrations of at least about 50 ppm, and typically from about 1000 to about 10,000 ppm in solution. Water temperatures preferably range from about 25 ° C to about 50 ° C. The water-bath ratio is preferably from about 1: 1 to about 15: 1. Methods for washing soiled dishes such as kitchenware, they also include contacting the soiled dishware with an aqueous dishwashing solution. The dishwashing solution Includes the added bleaching additive or bleaching composition containing an asymmetric activator as described in greater detail above. The dishwashing solution can also include any of the additives described above to the compositions, such as source of hydrogen peroxide, detersive surfactants, chelating agents and detersive enzymes. The compositions are preferably used at concentrations of at least about 50 ppm, and typically from about 1000 to about 10,000 ppm in solution. The Water temperatures preferably range from about 25 ° C to about 50 ° C. The present invention will now be described in relation to the following examples. In fact, the person skilled in the art will recognize that the present invention is not limited to the specific examples described herein, or the ingredients and steps contained therein, but rather, can be implemented in accordance with the most important aspects. broad of the description.

EXAMPLE I Preparation of N-cinnamoyl-N-methyl acetamide: A dry 3-neck round bottom flask equipped with a mechanical stirrer is charged under an inert atmosphere with 41.6 g (0.25 mole) of cinnamoyl chloride (available from Aldrich Chemical Company, Inc. of Milwaukee, Wisconsin) and 150 ml of CH2Cl2. (available from Aldrich Chemical Company). The stirred homogenous solution is cooled to -40 ° C (CH3CN / C02 bath), and 22.0 ml (0.275 moles) of pyridipase are added slowly. (available from Aldrich Chemical Company) (maintaining the temperature of the solution below -30 ° C) in one portion. The reaction mixture is stirred for 20 minutes, at which point a precipitate is observed. To the stirred heterogeneous solution is added 19.0 ml (0.25 moles) of N-methyl acetamide (available from Aldrich Chemical Company) in one portion. The resulting reaction mixture is allowed to warm gradually to room temperature, and is stirred overnight. The reaction is diluted with 150 ml of CH 2 Cl 2, and extracted twice with 150 ml of 1 N HCl, twice with aqueous NaOH at 0.1 N, and twice with water. The organic layer is dried over Na 2 S 4, and concentrated by rotary evaporation to give the desired N-cinnamoyl-N-methyl acetamide.

EXAMPLE II Exemplary bleaching compositions are exemplified by the following formulations having the form of granular laundry detergents.

'Bleach actir according to example I.

EXAMPLE III This example illustrates bleaching compositions, more particularly, liquid additive bleaching compositions according to the invention. 1 Alkyl ethoxylate available from The Shell OH Company. 2 Bleach actir according to example I EXAMPLE IV This example illustrates cleaning compositions having an additive form of bleaching, more particularly, liquid additive bleaching compositions without a source of hydrogen peroxide according to the invention.

Alkyl ethoxylate available from I he Shell Oil Company. Bleach actir according to example I.

EXAMPLE V A granular detergent composition for automatic dishwashing, comprises the following: Note 1: Bleach actir in accordance with Example I. Note 2: These sources of hydrogen peroxide are expressed on a wt% basis of available oxygen. To convert to a percentage basis of the total composition, divide by approximately 0.15. Note 3: Transition metal bleach catalyst: Pentaaminoacetatecobalt nitrate (III); it can be replaced by MnTACN.

EXAMPLE VI Cleaning compositions that have liquid form especially useful for cleaning bath tubs and bathroom tiles without being rough on the hands, are the following: Ingredient% by weight A B Bleach actir * 7.0 5.0 Hydrogen peroxide 0.0 10.0 C-? 2AS, acid form, partially 5.0 5.0 neutralized C? 2-14AE3S, acid form, partially 1.5 1.5 neutralized N-dimethylamine oxide of C? 2 1.0 1.0 DEQUEST 2060 0.5 0.5 Citric acid 5.5 6.0 Abrasive (15 to 25 micrometers) 15.0 0 HCl at pH 4 Filler and water I 3alance at 100% 'Bleach actir according to example I.

EXAMPLE VII Liquid bleaching compositions for cleaning typical household surfaces are the following. The hydrogen peroxide is separated as an aqueous solution from the other components by suitable means such as a double chamber container.

'Bleach activator according to example I "Commercially available from Monsanto Co ..

EXAMPLE VIII A laundry bar suitable for hand washing of soiled fabrics is prepared by standard extrusion methods, comprising the following: Component% by weight Bleach activator * 4 Sodium perborate tetrahydrate 12 C-? 2 linear alkyl benzene sulphonate 30 Phostate (as sodium tppoliphosphate) 10 Sodium carbonate 5 Sodium pyrophosphate 7 Coconut monoethanolamide 2 Zeolite A (from 0 1 to 10 microns) 5 Carboxymethylcellulose 0 2 Polyacrylate (pm 1400) 02 Brightener, pefume 02 Protease 0 3 CaS0 1 MgS04 1 Water 4 Filler ** Balance at 100% • Bleach activator according to example i ** Can be selected from suitable materials such as CaCO3, talc, clay, silicates, and the like Acid fillers can be used to reduce PH The fabrics are washed with the bar, obtaining excellent results.

Claims (30)

1. NOVELTY OF THE INVENTION CLAIMS 1.- A bleaching activating compound having the formula: wherein R1 is a portion selected from the group consisting of: wherein n is an integer from about 0 to about 12, A is a compatible counterion in fillers, m is an integer from about 1 to about 3, R2 is a saturated or unsaturated, straight or branched chain alkyl group of C Cs, and R3 is a saturated or unsaturated alkyl group, straight or branched chain of C1-C4.
2. 2. The bleach activating compound according to claim 1, further characterized in that R2 is a saturated linear alkyl group of C1-C4.
3. 3. The bleach activating compound according to claim 2, further characterized in that R2 and R3 are CH3.
4. 4. The bleach activating compound according to claim 1, further characterized in that the sum of the number of carbon atoms in R1, R2 and R3 is less than 19.
5. 5. An additive bleaching composition, characterized in that it comprises: i) from about 0.1% to about 70% by weight of the composition, of an asymmetric bleach activator having the formula: wherein R1 is a portion selected from the group consisting of: CH = CH- A + H3C ^? C wherein n is an integer from about 0 to about 12, A is a compatible counterion in fillers, m is an integer from about 1 to about 3, R2 is a saturated or unsaturated, straight or branched chain alkyl group of CrC8 , and R3 is a saturated or unsaturated, straight or branched chain alkyl group of C? -C4; and (ii) from about 0.1% to about 99.9% by weight of the composition, of conventional additive ingredients.
6. 6. The additive bleaching composition according to claim 5, further characterized in that R2 is a C1-C4 saturated linear alkyl group.
7. 7. The additive bleaching composition according to claim 5, further characterized in that R2 and R3 are CH3.
8. 8. The additive bleaching composition according to claim 5, further characterized in that the sum of the number of carbon atoms in Ri, R2 and R3 is less than 19.
9. 9. The additive bleaching composition according to claim 5, further characterized in that said conventional additive ingredients comprise a surfactant selected from the group consisting of nonionic surfactants, cationic surfactants, anionic surfactants, zwitterionic surfactants, apothermal agents, and mixtures thereof.
10. 10. The additive bleaching composition according to claim 9, further characterized in that said surfactant is a nonionic surfactant.
11. 11. The additive bleaching composition according to claim 5, further characterized in that said conventional additive ingredients are selected from the group consisting of chelating agents, polymeric soil release agents, source of hydrogen peroxide, bleach catalysts, enzymes, detergency builders, and mixtures thereof.
12. 12. The additive bleaching composition according to claim 5, further characterized in that said bleaching additive is in liquid form and further comprises about 0.1% to about 60% by weight of an emulsification system or thickening system.
13. 13. The additive bleaching composition according to claim 12, further characterized in that said emulsification system has a HLB value ranging from about 7 to about 15.
14. 14. The additive bleaching composition according to claim 12, further characterized in that said emulsification system comprises one or more nonionic surfactants.
15. 15. The additive bleaching composition according to claim 12, further characterized in that said emulsification system comprises a nonionic surfactant, and said nonionic surfactant is a nonionic alkyl alkoxylate.
16. 16. A bleaching composition, characterized in that it comprises: i) from about 0.1% to about 70% by weight of the composition, of an asymmetric imide bleach activator having the formula: wherein R1 is a portion selected from the group consisting of: H H, C * H3C r »* ~ ^? . ? ^: N. wherein n is an integer from about 0 to about 12, A is a compatible counterion in fillers, m is an integer from about 1 to about 3, R2 is a saturated or unsaturated alkyl, straight or branched chain of y R3 is a saturated or unsaturated, straight or branched chain alkyl group of C?-C4, and (ii) from about 0.1% to about 70% by weight of the composition, from a source of hydrogen peroxide.
17. 17. The bleaching composition according to claim 16, further characterized in that R2 is a saturated linear alkyl group of C1-C4.
18. 18. The bleaching composition according to claim 16, further characterized in that R2 and R3 are CH3.
19. 19. - The bleaching composition according to claim 16, further characterized in that the sum of the number of carbon atoms in R-, R2 and R3 is less than 19.
20. 20. The bleaching composition according to claim 16, further characterized in that said composition comprises from about 0.1% to about 10% of the composition, of a surfactant selected from the group consisting of nonionic surfactants, cationic surfactants, anionic surfactants, zwitterionic surfactants, amphoteric surfactants , and mixtures thereof.
21. 21. The bleaching composition according to claim 20, further characterized in that said surfactant is a nonionic surfactant.
22. 22. The bleaching composition according to claim 16, further characterized in that said composition further includes an ingredient selected from the group consisting of chelating agents, polymeric soil release agents, bleach catalysts, enzymes, builders, and mixtures. thereof.
23. 23. - The bleaching composition according to claim 16, further characterized in that said source of hydrogen peroxide is selected from the group consisting of perborate, percarbonate, hydrogen peroxide, and mixtures thereof.
24. 24. - The bleaching composition according to claim 16, further characterized in that said composition is formulated as a microemulsion of said bleach activator in a matrix comprising water, said bleach activator, source of hydrogen peroxide and a surfactant system hydrophilic comprising a nonionic surfactant.
25. 25. The bleaching composition according to claim 16, further characterized in that said composition is formulated as an aqueous emulsion comprising at least one hydrophilic surfactant having an HLB value greater than 10, and at least one agent hydrophobic surfactant having a HLB value of up to 9, wherein said bleach activator is emulsified by said surfactants.
26. 26. The confixing bleaching composition with claim 16, further characterized in that said composition is formulated in granulated form.
27. 27. A method for bleaching soiled fabrics, characterized in that it comprises the steps of contacting the soiled fabrics that will be bleached with an aqueous bleaching solution, said bleaching solution comprising an effective amount of the bleaching compound or composition in accordance with
28. 28.- The method according to claim 27, further characterized in that it comprises the step of directly contacting said soiled fabrics with the compound or composition of the present invention. bleaching according to any of claims 1 to 27 before the step of contacting said bleaching solution.
29. 29. The method for bleaching soiled fabrics, further characterized in that it comprises the steps of contacting the soiled fabrics that will be bleached with an aqueous bleaching solution, said bleaching solution comprising an effective amount of the bleaching additive compound or composition according to any of claims 1 to 15, and an effective amount of hydrogen peroxide. The method according to claim 29, further characterized in that it comprises the step of directly contacting said soiled fabrics with the bleaching additive compound or composition according to any of claims 1 to 15, prior to the step of in contact with said bleaching solution.