MXPA05012934A - Detergent formulations containing alkaline peroxide salts and organic acids. - Google Patents

Abstract

The invention provides particulate detergent compositions containing alkaline peroxide salts and organic peracid precursors, methods of treating stains with these compositions and methods of making the compositions. The compositions have long term storage stability imparted by a coating to the alkaline peroxide salt. The methods of formulating the compositions to include this coating are relatively easy and inexpensive.

Description

DETERGENT FORMULATIONS CONTAINING ALKALINE PEROXIDE SALTS AND ORGANIC ACIDS FIELD OF THE INVENTION The invention resides in the field of cleaning compositions having a combination of alkaline peroxide salts and peracid precursor activators, in a formulation having long-term storage stability.

BACKGROUND OF THE INVENTION Bleaching agents for fabrics containing chlorine have superior cleaning properties, but are limited to cleaning compatible fabrics, and can not be used to clean colored or patterned fabrics. Additionally, these agents have a peculiar odor that can be imparted to certain fabrics when used in high concentrations. For these reasons, there has been great interest in the development of bleaching agents that contain oxygen, which do not have these limitations. Among the oxygen-containing bleaching agents, sodium percarbonate and sodium perborate are particularly useful by virtue of their whitening capacity and their stability. Peroxygen bleaches are safe for colored fabrics, and are relatively non-yellowing for white fabrics.

These bleaches are not destructive to the physical resistance of the fabric, and they impart good handling and absorbency to the fabric. These peroxygen bleaches have been used mainly for stain removal and dirty in two different laundry configurations. The first configuration employs high wash temperatures, particularly above 85 ° C, which are frequently found in commercial laundries and in some European domestic laundries At these high temperatures, a peroxygen material such as hydrogen peroxide or perborate can be added. of sodium, or sodium percarbonate, to the washing mixture, and will give an effective whitening.In domestic washing machines in the United States, lower temperatures are typically found.For these lower temperatures, the peroxide combination has been successfully used. of hydrogen with activators A range of materials has been proposed as activators for peroxygen bleach to improve bleaching at low to moderate temperatures The selection of peroxygen bleach - activator combinations is a complex balancing of two contradictory characteristics. combination must be stable in storage It must not suffer a significant loss of activity (for example, no more than 10 to 20% during a period of 90 days at between 15 ° C and 30 ° C). On the other hand, the combination must be reactive enough to react within 1 to 2 minutes after being added to the solution for washing in cold water (10 ° C - 30 ° C), so that it is effective for the most time part of the washing period of 10 to 12 minutes of a cycle of residential automatic washing machine. Thus, a peroxygen-activator composite combination must show a reaction rate in the washer that is 10,000 to 1,000,000 times faster than the rate of decomposition that is tolerable during storage. U.S. Patent No. 3,833,506 to Fries and co-inventors, teaches a stabilized bleach auxiliary suitable for addition to washing and bleaching compositions, containing an activator for active oxygen and a mixture of fatty acids and polyethylene glycol. The activators described are carboxylic acid derivatives which react with the percompounds to form peracids, and consequently increase the bleaching action of the blends or make it possible to bleach them at low wash temperatures. The auxiliary whitening formulation is stabilized by spraying a combination of the activator, a fatty acid and a polyethylene glycol in a solidification zone, to form particles having a diameter of less than 1 mm. However, the stability test performed with this product showed that the perborate bleaching active ingredient fell below 90% efficacy after storage for 21 to 28 days, and fell below 40% efficacy after six weeks. Thus, this formulation method is technically complex and expensive, and the resulting product still shows insufficient stability for storage, shipment and use by the customer.

U.S. Patent No. 5,702,635 to Trani and Ricci discloses a granular laundry detergent containing percarbonate coated or agglomerated with acrylic hydrophobic esters of citric acid, which has increased stability. The acylated citric acid esters coat the detergent particles to stabilize the percarbonate during storage, while acting as a bleach activator during the aqueous washing conditions. The composition is formed by spraying the acylated esters of citric acid on the granular particles of percarbonate, or on the finished composition including percarbonate and other additives after all the other ingredients have been combined. However, these acylated esters of citric acid are strongly hydrophobic, which limits the formulation options and negatively impacts the dissolution rates of the coated product in the water. U.S. Patent No. 5,716,923 to MacBeath, teaches a laundry detergent having a percarbonate bleach coated with a mixed salt containing an alkali metal carbonate and an alkali metal sulfate salt. The detergent also contains a peroxyacid bleach precursor, an acidifying agent and a means for delaying the release of the acidifying agent. The coated percarbonate is stable in storage, while the delayed acidification lowers the pH of the laundry to less than 9.5 in the final wash solution. The coating that affects the delayed release of the acidifying agent is a dual coating of an inner wax and an outer silica, produced in a multi-layer functional coating process, which makes the coating and formulation of these dry detergents complex and expensive. Thus, there is a need for fabric detergent formulations that combine the cleansing activity of peroxygen bleach and peroxygen bleach activator in a stable storage composition whose formulation is relatively simple and inexpensive.

BRIEF DESCRIPTION OF THE INVENTION The present invention provides particulate detergent compositions, which combine peroxygen bleaches having a surfactant coating and peroxygen bleach activators, as well as methods for easily and inexpensively formulating these detergent compositions to have long-term storage stability, and methods for using these detergent compositions to treat fabric stains. The compositions contain an alkaline peroxide salt, coated with a surfactant and a peracid precursor containing carboxylic acids and salts thereof. Preferably, the alkaline peroxide salt is sodium percarbonate or sodium perborate, present in an amount of about 20% to about 80% of the composition by weight. Preferably, the peracid precursors are dicarboxylic or tricarboxylic acids such as oxalic acid, malonic acid, succinic acid, ruthuaric acid, adipic acid, pimelic acid, tannic acid, tartaric acid or citric acid, or combinations thereof present in an amount from about 0.1. % up to 10% of the composition by weight. The preferred surfactant is at least one nonionic surfactant, particularly an ethoxylated alcohol of 11 to 16 carbon atoms, or mixtures of these ethoxylated alcohols. The composition optionally contains other auxiliaries for washing, including surface-active substrates such as sodium carbonate, and / or sodium sulfate, protective metals such as sodium metasilicate, dispersing agents such as acrylic-derived polymers and rosin soaps, water-soluble solvents. , such as dipropylene glycol methyl ether, and / or ethylene glycol butyl ether, enzymatic stain removers, fluorescent whitening agents, optical brighteners, regulators, colorants, fragrances, detergency constituents, peroxide stabilizers and binding agents. The processes for formulating the solid detergent compositions of the present invention provide inexpensive methods for combining and coating the detergent components to form compositions having increased storage stability. These methods include combining a surfactant with a solvent to form a solution or coating an alkaline peroxide salt with the solution to form a coated alkaline peroxide salt. A peracid precursor is then added to the coated alkaline peroxide salt. Preferably, the composition contains a surfactant substrate which is first coated with the solution, and then mixed with an alkaline peroxide salt such that the alkaline peroxide salt absorbs the solution from the surface of the surfactant substrate.

BRIEF DESCRIPTION OF THE DRAWINGS Figures 1 (a-c) show the results of the fabric cleaning test described in example 1, comparing a pre-soaking of one hour, three hours and five hours, with a detergent composition of the present invention. Figures 2 (a-c) show the results of the fabric test described in example 2, comparing detergent compositions of the present invention having a peracid precursor additive with similar compositions having no peracid precursor, on various fabric spots. Figure 3 is a graphical representation of the total Delta E for different spots on cotton and poly / cotton comparing treatment with compositions of the present invention and commercially available detergents. Figure 4 is a graphical representation of the total Delta E for different spots treated with detergent compositions of the present invention compared to compositions lacking a peracid precursor. Figure 5 is a graphic representation of the total Delta E for different spots on cotton fabrics or cotton blends, comparing formulations of the present invention having different peracid precursors, with commercially available detergents. Figure 6 shows a graphic representation of the total Delta E for different types of standard dyes on fabrics treated with detergent compositions of the present invention having different peracid precursors, compared to commercially available detergents. Figure 7 is a graphical representation comparing the oxidation-reduction potential developed by the detergent compositions of the present invention, with similar compositions lacking peracid precursors, with an exponentially performed curve fitting.

DETAILED DESCRIPTION OF THE INVENTION The present invention provides detergent formulations containing alkaline peroxide salts and bleaching activators with organic acid, which have long shelf life and high stability, and are particularly useful for cleaning fabrics. These formulations contain an alkaline peroxide salt and a peracid precursor coated with a surfactant. The alkaline peroxide salts are oxygen-containing bleaching agents, including sodium percarbonate and sodium perborate. Preferably, the peroxide salt is sodium percarbonate. As used in the present application, the term "alkaline peroxide salts" refers to hydrates and other cations of the alkali metal peroxide salts. The alkaline peroxide salt may comprise a single chemical species, or a combination of different chemical species. The peroxide salt is present in the formulation on a scale from about 1% to about 99% of the formulation by weight. Preferably, the peroxide salt is present on a scale from about 20% to about 80% by weight. More preferably, the peroxide salt is present on a scale of about 40% to about 60% by weight. Even more preferably, the peroxide salt is present on a scale from about 50% to about 60% by weight. Most preferably, the peroxide salt is present at about 56% by weight. The peracid precursor activates the alkaline peroxide salts in solution to produce organic peroxides. The peracid precursor may contain a single chemical species or a combination of different chemical species. The peracid precursor of the invention is selected from organic acids and their salts. For the peracid precursors having different isomeric forms, all isomers may be functional in the compositions of the present invention. Preferred dicarboxylic acids include oxalic acid, malonic acid, succinic acid, glutaric acid, adipic acid, pimelic acid, tannic acid and tartaric acid. A functional tricarboxylic acid is citric acid. More preferably, the peracid precursors include tartaric acid, adipic acid and / or citric acid, with tartaric acid being most preferred. Peracid precursors are commonly present in the formulation, on a scale from about 0.1% to about 10% of the formulation by weight. Preferably, the peracid precursor is present on a scale from about 0.7% to about 2% by weight. Most preferably, the peracid precursor is present at about 1% by weight. While other peracid precursors are known in the art (such as tetraacetylethylene diamine (TAED), and nonanoyloxybenzene sulfonate (NOBS), the peracid precursors of the present invention have significant advantages over known peracid precursors. Per acid organic acid precursors of the present invention appear widely in nature, and are recognized as being benign to the environment.In addition, many organic acid peracid precursors are inexpensive and can be used economically at the concentrations identified above, thus providing a more cost-effective system The formulations of the present invention may also include a water-soluble solvent.While many water-soluble solvents are familiar to those in the field, preferred water-soluble solvents include dipropylene glycol methyl ether ( 1- (2-methoxy opropoxy) -2-propanol) and ethylene glycol butyl ether (2-butoxyethanol). The water soluble solvent is commonly present in the formulation on a scale from about 0.1% to about 10% by weight. Preferably, the water soluble solvent is present on a scale from about 0.2% to about 5% by weight. More preferably, the water soluble solvent is present on a scale from about 0.3% to about 0.5% by weight. Much more preferably, the water soluble solvent is present at approximately 0.4% by weight. The formulations of the present invention may also include a surfactant or surfactants to aid the solubilization of materials not soluble in water. For example, useful nonionic surfactants include ethoxylated alcohols of 10 to 14 carbon atoms, or ethoxylated alcohols of 11 carbon atoms. Surfactants can vary widely in concentration within the formulations of the present invention. Typically, surfactants are present on a scale from about 0.1% to about 20% by weight. Preferably, the surfactants are present on a scale from about 0.2% to about 5% by weight. More preferably, the surfactants are present on a scale from about 0.6% to 3% by weight. Previously, it has been difficult to incorporate alkaline peroxide salts at effective levels in dry detergents into laundry particles, due to the instability of these bleaches in storage. Sodium percarbonate loses its available oxygen at a significant rate in the presence of heavy metal ions, such as iron, copper and manganese, and more importantly in the presence of moisture; these effects are accelerated to temperatures above approximately 29.4 ° C (85 ° F). Moisture and ions are inevitable components of granular compositions for laundry treatment. Also the decomposition of alkaline peroxide salts due to humidity becomes more of a problem during storage, since the laundry treatment products are often stored in humid environments in which the product absorbs moisture, resulting in a acceptable bleach stability only marginally, for laundry detergents containing alkaline peroxide salts shipped to hot and humid regions. This decomposition of accelerated percarbonate with temperature also occurs during the manufacture of the finished product. Under some conditions, since the individual ingredients are mixed together, the temperature of the mixture can increase, accelerating the decomposition of the alkaline peroxide salt. In addition, the increase in temperature is greater if the mixture occurs in wet conditions. Additionally, when an alkaline peroxide salt is combined with a bleach activator, stability during storage and production becomes an even greater problem. Undoubtedly, mixing an alkaline peroxide salt with a bleach activator during the formulation of a dry particulate detergent can cause rapid decomposition during manufacture or storage if the detergent composition is subjected to wet environments. It is therefore an unexpected and advantageous discovery that a dry particulate detergent containing an alkaline peroxide salt and a peracid carboxylic acid precursor can be formulated so as to have a relatively long stable shelf life, coating the particles of alkaline peroxide salt with a surfactant. The surfactants normally function as surface active agents, connecting the interface between the hydrophilic and hydrophobic compounds. Thus, given the difficulty to use alkaline peroxide salts in particulate detergents due to their reactivity with water and especially because of their reactivity with the combination of water and peracid precursors, it is unexpected that combining the alkaline peroxide salt with a substance that can improve contact with water stabilizes the formulation. However, it has been found that coating the alkaline peroxide salt with a surfactant leads to greatly improved stability, and therefore increases the shelf life of the particulate detergent compositions of the present invention. This allows the production of a stable particulate bleaching composition, which contains an alkaline peroxide hydrogen peroxide salt source, together with a peracid bleach activator. Stability tests performed with the detergent compositions of the present invention, which measure the available oxygen content of the detergents immediately after formulation and at time points during the storage of the detergent formulations, show that the compositions can retain more than approximately 90% of its available oxygen after 60 days of storage under conditions of 50% humidity at 35.5 ° C. Preferably, the detergent compositions of the present invention are sufficiently stable to retain more than about 60% of their available oxygen after 60 days of storage under those conditions. More preferably, the detergent compositions of the present invention are sufficiently stable to retain more than about 70% of their available oxygen after 60 days of storage under those conditions. More preferably, the detergent compositions of the present invention retain more than about 80% of their available oxygen after 60 days of storage under these conditions. More preferably, the detergent compositions of the present invention retain more than about 90% of their available oxygen after 60 days of storage under these conditions. Most preferably, the detergent compositions of the present invention retain more than about 95% of their available oxygen after 60 days of storage under these conditions. For the purposes of this description, coating the alkaline peroxide salt component of the detergent refers to contacting the alkaline peroxide salt with a surfactant such that at least one surface of the alkaline peroxide salt is in contact with the alkaline peroxide salt. contact with the surfactant in the final detergent composition after the formulation. Preferably, the surfactant coats or agglomerates at least half of each particle of alkaline peroxide salt. Most preferably, the surfactant coats or agglomerates the entire surface of each particle of alkaline peroxide salt. The coated particles of the present invention can be obtained by various methods known in the art, such as, for example, spraying or agglomeration or coating methods. For example, the surfactant or a combination of surfactants can be used either as a binder or as a coating agent to agglomerate or to coat the alkaline peroxide salt particles. A preferred method for coating the alkaline peroxide salt particles is to mix the chosen surfactants with a solvent, to form a surfactant solution which is then combined with the alkaline peroxide salt to agglomerate or coat each particle of alkaline peroxide salt. After coating or agglomeration, the surfactant takes on a non-fluid consistency that acts as a barrier to water. To prepare the alkaline peroxide salt particles coated or agglomerated in this way, the solvent must be chosen by the characteristics of combination with the surfactant to form a solution and undergo a change in consistency during or after the formulation of the coated particles. . After the alkaline peroxide salt is added and sufficiently mixed to obtain a coating, the surfactant solution assumes a non-flowing "gummy" consistency, which is believed to improve the protection of the alkaline peroxide salt particles. Without intending to be bound by any theory, it is believed that the solvent present in the surfactant solution is partially evaporated, and is partially absorbed by the surfactant substrate, thereby causing the change in the consistency of the surfactant solution forming the non-fluid protective barrier. on the surface of the alkaline peroxide salt particles. The most preferred method for forming the detergent compositions of the present invention is to form a solution of one or more nonionic surfactants with a water soluble solvent. This solution is then mixed with a surfactant substrate in a proportion that results in the surfactant substrate coated with the surfactant solution with a residual amount of the remaining surfactant solution. Immediately after this, the alkaline peroxide salt is added to the mixture, and mixed until the alkaline peroxide salt particles become coated by absorbing any residual surfactant solution from the surface of the surfactant substrate onto the surfaces of the surfactant. alkaline peroxide salt. This method of mixing these ingredients ensures an easy and inexpensive method to obtain a light coating of at least one surfactant on the alkaline peroxide salt, sufficient to protect the alkaline peroxide salt from the water, while remaining sufficiently thin to allow the Total activity of the alkaline peroxide salt when the detergent composition is added to residential laundry water. Any other desired ingredients can then be added to the mixture to form detergent formulations of the present invention. The preferred surfactant substrate for use in compositions of the present invention is sodium carbonate (partner ash), and the most preferred coating solution contains a mixture of nonionic surfactants, including an ethoxylated alcohol of 12 to 16 carbon atoms, such as GENOPOL LA060 ™ and an ethoxylated alcohol of 11 carbon atoms, such as GENOPOL UD-030 ™ mixed with the water soluble solvent dipropylene glycol methyl ether. This surfactant solution is mixed and used to coat the sodium carbonate. An alkaline peroxide salt is then added to the mixture, and mixed until a light coating of the surfactant solution has been absorbed onto the surface of the alkaline peroxide salt particles. During mixing and immediately thereafter, the consistency of the coating changes from a liquid form to a non-fluid form. Then any additional washing aid is added and mixed into the mixture. This combination of an alkaline peroxide salt coated with a surfactant is further advantageous, because the surfactant has well-known functions to aid in the cleaning of fabrics when the surfactants are introduced into the laundry water. Thus, the surfactant acts to protect and stabilize the particulate detergents of the present invention, which comprise alkaline peroxide salts and peracid precursors during formulation and storage, while acting to release the alkaline peroxide salt and the peracid, when introduced. in the laundry water, and then operate separately from the activated bleaching compounds to help clean and remove stains from the fabrics present. These dual functions improve the cleaning power of the detergents of the present invention, while facilitating manufacturing, shipping and handling conditions for dry formulations. The formulations of the present invention may also include a substrate for the surfactants, which also function as a binding agent. For example, the surfactant substrate may be sodium carbonate (soda ash), or sodium sulfate. Sodium carbonate functions as a regulator and is more absorptive than sodium sulfate, and is therefore preferred. Typically, the surfactant substrate is present on a scale from about 1% to about 60% by weight. Preferably, the surfactant substrate is present on a scale from about 10% to about 50% by weight. More preferably, the surfactant substrate is present on a scale from about 30% to about 40% by weight. Most preferably, the surfactant substrate is present at about 37% by weight. The formulations of the present invention can also include a metal protector that can also function as a soil dispersing agent and / or as a pH regulator. For example, metal shields can be sodium metasilicate, a polymeric metal shield or a cationic metal shield. Sodium metasilicate is more preferred because of its ease of formulation compared to a polymeric or cationic metal protector. Sodium metasilicate is commonly present in the formulation, on a scale from about 0.1% to about 10% of the formulation by weight. Preferably, the sodium metasilicate is present in the range from about 0.7% to about 2% by weight. Much more preferably, sodium metasilicate is present at approximately 1% by weight. The formulations of the present invention may also include a dispersing agent. While many dispersing agents are familiar to those skilled in the art, preferred dispersing agents include acrylic-derived polymers, such as copolymers of acrylic acid, and rosin soaps. Preferred acrylic acid copolymers are maleic / acrylic acid copolymers. The dispersing agent is typically present in the formulation on a scale from about 0.1% to about 10% by weight. Preferably, the dispersing agent is present on a scale from about 0.2% to about 5% by weight. More preferably the dispersing agent is present at about 25% by weight. A preferred formulation of the present invention is shown in Table 1.

TABLE 1 Component% CAS Weight # Name Substrate 37.17 497-19-8 Sodium Carbonate Surfactant Surfactant 2.95 68551-12-2 GENOPOL LA060 ™; linear ethoxylated nonionic alcohol of 12 to 16 carbon atoms (3 moles EO); Clariant Corporation Surfactant 0.65 127036-24- GENOPOL UD-030 ™; non-ionic ethoxylated alcohol of 1 carbon atoms (3 moles EO); Clariant Corporation Solvent 0.40 34590-94-8 Dipropylene glycol methyl ether soluble in (1- (2-methoxyisopropoxy) -2- water propanol); Lyonell Peroxide salt 56.58 15630-89-4 Sodium percarbonate; alkaline Solvay-lnterox Agent 0.25 68479-09-4 Acrylic acid copolymer ~ dispersive 4500 moles of weight; neutralized with sodium; Rohm and Haas Precursor 1.00 133-37-9 D, L-tartaric acid; Shengyu Peracid Chemical Protector 1.00 6834-92-0 Blue Meta; Metal metasilicate / sodium anhydrous agent 100.00; Dispersive PQ Corporation.

The composition of the present invention optionally may include additional wash aids. Additional representative wash aids include enzymatic spot removers. These materials include enzymes capable of hydrolyzing substrates, for example, stains on fabrics. Under the International Union of Biochemistry, the accepted nomenclature for these types of enzymes is hydrolases. Hydrolases include, without limitation, proteases, amylases (carbohydrases), lipases (esterases), cellulases and mixtures thereof. Proteases, especially the so-called alkaline proteases, are commonly used as washing aids, since they attack protein substrates and digest them, for example, in problematic spots such as blood and grass. In various formulations of the present invention, enzymatic stain removers may optionally be included, if the dilution of the composition is large enough to reduce the pH of the solution to a scale that does not inactivate the enzyme. Another class of washing aid which can benefit from the practice of the invention is that of fluorescent whitening agents, or optical brighteners, although, as a rule, these materials have an effect more quickly than enzymatic stain removers, and that is less prone to attack by a rapid onset of active oxygen. Representative fluorescent whitening agents include naphtholtriazole stilbene and distribyl biphenyl bleach agents, marketed by Ciga-Geigy Corporation under the names Tinopal ™ RBS and Tinopal ™ CBS-X, respectively, and stilbene materials are also marketed by Ciba-Geigy under the name Tinopal ™ 5B X. Tinopal ™ CBS-X brightener is the most stable peroxide brightener and is therefore the preferred brightening agent as an additive in the formulations of the present invention. Other useful brighteners are described in the ASTM D-533A publication, List of Fluorescent Bleaching Agents for the Soap and Detergent Industry. The compositions of the present invention, if desired, may contain additional components such as regulators, colorants, fragrances, primary cleaning agents (surfactants), detergency builders and binding agents. In addition, peroxide stabilizers, such as heavy metal chelating ligands, for example EDTA, can be added. Representative surfactants include conventional nonionic, cationic, ammonic, amphoteric surfactants, as described in the art. Examples of surfactants suitable for use in these formulations can be found in Kirk-Othmer, Encyclopedia of Chemical Technology, 3rd. edition, volume 22, patinas 247-387 (1983) and in McCutcheon's Detergent and Emulsifiers, Edition for North America (1983). A group of generally preferred surfactants are nonionic surfactants such as those described on pages 360-377 of Kirk-Othmer. Non-ionic materials include non-ionic surfactants ethoxylated alcohols, alkyl phenol ethoxylates, carboxylic acid esters, glycerol esters, polyoxyethylene esters, anhydrosorbitol esters, ethoxylated esters of anhydrosorbitol, ethoxylates of fats, oils and natural waxes, glycol esters of fatty acids, carboxylic amides, diethanolamine condensates, condensates of monoalkanolamine, polyoxyethylene fatty acid amides, block polyalkylene oxide copolymers, poly (oxyethylene-co-oxypropylene) and the like. A wide range of these materials is commercially available, including Neodols ™ from Shell Chemical, Tergitols ™ from Union Carbide, Tween ™ and Span ™ from ICI, and the like. The detergency builders that may optionally be added to the bleaching compositions may be selected from detergency builders commonly added to detergent formulations. Useful builders include any of the conventional water-soluble organic and inorganic salts, phosphates, pyrophosphates, orthophosphates, polyphosphates, silicates, carbonates, and the like. Organic builders include phosphonates, polyphosphonates, polyhydroxysilphonates, polyacetates, carboxylates, polycarboxylates, succinates, water soluble, and the like. Specific examples of inorganic phosphate builders include sodium and potassium triphosphates, pyrophosphates and hexametaphosphates. Organic polyphosphonates specifically include, for example, the sodium and potassium salts of ethane-1-hydroxy-1,1-diphosphonic acid, and the sodium and potassium salts of ethane-1, 1, 2-triphosphonic acid. Examples of these and other phosphorous improver compounds are described in U.S. Patent Nos. 3,213,030; 3,422,021; 3,422,137; and 3,400,176. Pentasodium tripolyphosphate and tetrasodium pyrophosphate are particularly preferred water-soluble inorganic builders. Specific examples of non-phosphorus inorganic builders include water-soluble inorganic carbonate, bicarbonate and silicate salts. The alkali metals, for example, sodium and potassium, carbonates, bicarbonates and silicates, are particularly useful in the formulations of the present invention. Water soluble organic improvers are also useful. For example, the ammonium and substituted ammonium polycarboxylates, carboxylates and polycarboxylates, and polyhydroxysulfonates, are useful builders for the compositions and processes of the invention. Specific examples of polyacetate and polycarboxylate builders include sodium, potassium, lithium, ammonium and substituted ammonium salts, ethylenediaminetetraacetic acid, nitrolotriacetic acid, benzene polycarboxylic acids (ie, penta- and tetra-), carboxymethoxysuccinic acid, and citric acid, Water-insoluble improvers can also be used, particularly the sodium silicate aluminum complex, such as zeolites, for example, zeolite 4A, a type of zeolite molecular sieve wherein the univalent cation is sodium, and the pore size is about 4 Á. The preparation of a zeolite of this type is described in U.S. Patent No. 3,114,603. The zeolite can be amorphous or crystalline, and have hydration waters as is known in the art. The fillers or binder agents may also be included in the bleaching compositions of the invention. A common filler salt is an alkali metal sulfate, such as potassium or sodium sulfate, the latter being preferred. The most preferred filler for use in the compositions of the present invention is sodium carbonate (soda ash). The compositions of the present invention are useful in a wide spectrum of types of stains, including spaghetti, mustard, salad dressing, dirty motor oil, blood, grass, makeup, wine, juices, condiments, fruit filling, and preservatives. fruits. The cleaning compositions of the present invention can be formulated into a variety of cleaning products, particularly for fabrics, including laundry cleaners, carpet cleaners, upholstery cleaners, and cleaners for the interior of vehicles. Those skilled in the art can formulate the compositions described herein, in a variety of types of products. New objects, advantages and characteristics of this invention will become apparent to those skilled in the art when examining the following examples thereof, which are not intended to be limiting.

EXAMPLES EXAMPLQ1 This example demonstrates the improved efficacy of the detergent composition described in Table 1 (hereinafter referred to as "improved formulation") for the removal of various types of stains from cotton, polyester / cotton and braided cotton fabrics, during a pre-soaking One, three or five hours. Samples of 15.24 cm square fabric, cotton cloth, polyester / cotton fabric, and prewashed cotton braid were obtained at Testfabrics, Inc. (West Pittston, Philadelphia). Different spots were tested: spaghetti, mustard, salad dressing, dirty motor oil, and blood. For each time point, fabric samples were used in duplicate. The spots were applied in the following manner. For spaghetti, 0.25 mL of original RAGU ™ was applied to each cloth sample. For the mustard, traditional yellow KROGER ™ was applied to each sample of cloth, placing a small amount of the mustard on the back of the bulb of a rubber pipette, then rubbing the mustard over the cloth sample. To approach the salad dressing stains, 0.25 ml_ of RAFT FREE ™ Catalina dressing was applied to each cloth sample. For stains of dirty engine oil, two drops of used motor oil were applied to each fabric sample. Finally, for blood stains, 0.25 ml_ of cow blood was applied to each cloth sample. After the application of the spots, the fabric samples were left to rest overnight. To each soaking bucket of 18.9 L (5 gallons) was added 7.5 L (2 gallons) of water at 46.1 ° C (115 ° F) + 1.1 ° C (2 ° F), along with 29.6 cc of the improved formulation . After the solution was stirred and the solid dissolved, the fabric samples were added. They were left soaking in the cubes for one hour, three hours or five hours, depending on their designations. Each cube was stirred by hand after fifteen minutes and again at thirty minutes. After the designated time, the buckets were emptied, and each group of logging samples was washed using three quarts of a cup of ultra concentrated PUREX ™ laundry detergent, and a ballast load, using a 90-liter Kenmore ™ 80-well washer ( 3.2 cubic feet), and dried in a KENMORE ™ Elite dryer. After drying, all fabric samples were graded by two different qualifiers. The following qualification procedure was used. The fabric samples with the three-hour soak time were compared with the fabric samples with the one-hour soak time, and the fabric samples with the five-hour soak time were compared with the fabric samples with the soaking time of one hour. The following rating system was used: 4 = significantly better; 3 = noticeably better; 2 = better; 1 = slightly better; 0 = equal to the control (Star if the stain was completely removed); -1 = slightly worse; -2 = worse; -3 = noticeably worse; and 4 = significantly worse. Table 3 shows the results of soaking for three hours in cotton, polyester / cotton and braided cotton, compared to the soaking times of one hour, and table 4 shows the results of soaking five hours in cotton, polyester / cotton, and braided cotton, compared to one-hour soaking times. Figures 1 (a) through (c) provide a graphic representation of the results found in Tables 2 and 3. The results indicated that the performance of the improved formulation increases with a longer soaking time. A soaking time of three hours compared to one hour, showed some improvement for each type of polyester / cotton stain, and for each type of stain, except blood in cotton and braided cotton. An additional improvement in stain removal performance was seen five hours prior soaking. These results illustrated that formulations of the present invention having a peracid precursor generally provide improved cleaning results compared to formulations without a peracid precursor for most of the types of spots evaluated.

TABLE 2: ELIMINATION OF STAINS OF VARIOUS TYPES OF FABRICS WITH IMPROVED FORMULATION. IN A THREE-HOUR PRIOR-TREATMENT TREATMENT, COMPARED WITH A PRE-HOUR ONE-HOLE TREATMENT TABLE 3: ELIMINATION OF STAINS OF VARIOUS TYPES OF FABRICS WITH IMPROVED FORMULATION. IN A FINE REMOVAL TREATMENT OF FIVE HOURS. COMPARED WITH A PREMIUM ONE HOUR REMOVAL TREATMENT Mustard Sauce Blood Oil Dressing spaghetti dirty motor salad Polyester / cotton 2.25 2.125 2 2 2.5 Cotton 2 2.875 -1.75 1.25 2.25 Braided cotton 1.875 1.5 0.625 2.5 1.25 EXAMPLE 2 This example compares the effectiveness in stain removal of two detergent formulations of the present invention, containing different peracid precursors, with a formulation that does not contain peracid precursors, which is described in Table 4 (hereinafter referred to as the "formulation"). of comparison ").

TABLE 4 COMPONENTS OF THE COMPARISON FORMULATION Component% CAS # Name Weight Substrate 38.17 497-19-8 Sodium carbonate surfactant Surfactant no 2.95 68551-12-2 GENOPOL LA060 ™; linear ethoxylated ionic alcohol of 12 to 16 carbon atoms (3 moles EO); Clariant Corporation Surfactant no 0.65 127036-24- GENOPOL UD-030 ™; ionic alcohol 2 ethoxylated of 11 carbon atoms (3 moles EO); Clariant Corporation Solvent 0.40 34590-94-8 DPM; methyl ether soluble in dipropylene glycol (1- (2-methoxy-water isopropoxy) -2-propanol); Lyonell Peroxide salt 56.58 15630-89-4 Sodium percarbonate; Solvay- alkaline Interox Agent 0.25 68479-09-4 Acrylic acid copolymer ~ dispersive 4500 moles of weight; neutralized with sodium; Rohm and Haas Protector of 1.00 6834-92-0 Blue Meta; Metal metasilicate sodium / anhydrous agent 100.00; PQ Corporation. dispersive Six square inch (15.24 cm square) cloth samples of cotton fabric, polyester / cotton fabric, and prewashed braided cotton fabric were obtained from Testfabrics, Inc. Four different spots were tested: spaghetti, mustard, oil dirty engine and blood. Each spot was applied to six samples of each fabric as described in Example 1. Two of the samples with the same spots were treated with the comparison formulation to which tartaric acid had been added (Sigma Corp., St. Louis, MO), in a percentage by final weight equivalent to 1 percent by weight of tartrate, and two of the samples with the same spot were treated with the improved formulation to which potassium sodium tartrate was added (Sigma Corp. , St Louis, MO), in a percentage by final weight equivalent to 1 percent by weight of tartrate. Peracid precursors were added using standard procedures in the industry. After the application of the spots, the samples were allowed to rest overnight. To each soaking bucket of 18.9 L (5 gallons), 7.5 L (2 gallons) of water at 46.1 ° C (115 ° F) ± 1.1 ° C (2 ° F) was added, together with 29.6 ce of the detergent additive appropriate. After the solution was stirred and the solid dissolved, the fabric samples were added. It was allowed to soak in the cubes for one hour, and each cube was stirred manually, after fifteen minutes and again at thirty minutes. After the designated time, the cubes were emptied, and each group of samples was washed and dried, as described in Example 1. Detergent formulations containing tartaric acid or potassium tartrate, were compared against the comparison formulation, and were graded as described in Example 1. Table 5 provides the results of the comparison with the detergent formulation containing tartaric acid on various types of spots, and Table 6 provides the results of the comparison with the formulation containing Potassium sodium tartrate on the same types of spots. Figures 2 (a) through (c) provide a graphical presentation of the results shown in Tables 5 and 6. These results demonstrate the improved performance of the detergent formulations having a peracid precursor additive, compared to the comparison formulation for the most types of stains on all fabrics tested. additionally, these results show that there are no significant differences between the use of tartaric acid and the use of potassium sodium tartrate as a source of the peracid precursor in the solution.

TABLE 5: ELIMINATION OF VARIOUS TYPES OF STAINS OF THE FABRIC, BY FORMULATING COMPARISON WITH TARTARIC ACID ADDITIVE TABLE 6: ELIMINATION OF VARIOUS TYPES OF STAINS OF THE CLOTH. FOR THE FORMULATION OF COMPARISON WITH POTASSIUM SODIUM TARTRATE ADDITIVE Mustard Sauce Blood Dirty motor spaghetti oil Polyester / cotton 1.75 0.875 0 2 Cotton 0.75 1 2 1 Braided cotton 1 -0.375 0.75 1.25 EXAMPLE 3 This example compares the performance of the improved formulation, the comparison formulation and various commercially available laundry pretreatments, in stain removal. 6-inch square samples of cotton fabric, polyester / cotton fabric, and pre-washed braided cotton fabric were obtained from Testfabrics, Inc. Nine different types of spots were tested: coffee, grape , spaghetti, blood, dressing, grass, makeup, mustard, and cake filling. Each spot was applied to samples in duplicate of each fabric, for each type of pre-treatment. To apply the spots, the following procedures were used. The initial materials for each spot were those used in general in the laundry additive technique. The initial materials for pasture and cake filling were homogenized. All stains were applied in a sufficient amount to create a saturated circle of 1 inch (2.54 cm) of stain on each fabric. The stained fabric samples were left to age overnight, after which the fabric samples were treated with the indicated treatments. The treatment conditions were as follows. For the improved formulation, the comparison formulation and SHOUT ™, 8 grams of detergent per 1 liter of water was dissolved. CLOROX ™ was used in 10 g / L of water. The water was applied at a temperature of 40 ° C (104 ° F) and a hardness of 150 ppm. The soaking time was sixty minutes. After the designated time, the cubes were drained, and each group of fabric samples was washed and dried as described in Example 1. After drying, the fabric samples were evaluated for stain removal. The color difference was described as the Delta E value. The spectrophotometric values were obtained using an industry-standard colorimeter (Minolta Corp., Ramsey, NJ), and Delta E was calculated using a method that measures L * (lightness), a * (green-magenta axis), and b * (yellow-blue axis), where Delta E describes the vector difference between the points in this space. The smallest color difference has the smallest Delta E value. The Delta E values reported are related to the non-stained cloth. The results are shown in Tables 7 - 8 and in Figure 3. Tables 7 and 8 show the performance of each type of treatment on each spot by fabric type, reported as Delta E units. The "Total" column is the sum of the Delta E measurements of all types of stains, indicating the general stain removal performance, of each type of treatment. Figure 3 is a graphical representation showing the sum of total Delta E for each spot for cotton, plus the Delta e total for each spot obtained for both polyester / cotton and cotton. These results demonstrate that the improved formulation has the best overall performance for stain removal relative to the comparison formulation, SHOUT ™ and CLOROX ™.

TABLE 7: COMPARISON OF THE ELIMINATION OF VARIOUS TYPES OF STAINS IN COTTON FABRIC BY VARIOUS PRETREATMENT COMPOSITIONS FOR FABRICS. MEASURED BY DELTA E TABLE 8: COMPARISON OF THE ELIMINATION OF VARIOUS TYPES OF SPOTS IN POLYSTYLE FABRIC R / COTTON BY VARIOUS COMPOSITIONS OF PRE-TREATMENT FOR FABRICS, MEASURED BY DELTA E Polyester / Cotton Coffee Grape Spaghetto AderePaqui MaquiMostaFill of full gueti zolaje pastel CLOROX "" 1.47 1.66 29.66 2.54 7.41 8.81 7.02 10.64 3.08 72.29 SHOUT "1 1.3 1.24 24.9 2.04 6.83 7.44 5.68 10.7 2.39 62.7 Formulation 1.41 1.08 21.92 2.04 6.27 4.64 4.19 1.78 2.40 Improved 54.73 Formulation of 1.38 0.76 26.64 2.73 7.12 7.55 5.81 11.05 2.11 65.15 comparison EXAMPLE 4 This example compares the stain removal performance of the detergent compositions of the present invention containing different peracid precursors. Test fabrics, spots, and their application procedures were described in Example 3 above, with the addition of a dirty engine oil (DMO) stain to the spots tested here. The detergent formulation shown in Table 1 was prepared in bulk without the addition of the peracid precursor. Each of the various peracid precursors was then added to separate batches of this detergent formulation as follows: Citric acid (Sigma Corp., St. Louis, MO) was added to a final concentration of 1 percent by weight. The adipic acid (Sigma Corp., St. Louis, MO) was added for a final concentration of 0.8 percent by weight. Tartaric acid (Sigma Corp., St. Louis MO) was added to a final concentration of 1 percent by weight. An aliquot of the detergent formulation remained free of peracid precursor for comparison as an "acid-free" formulation added. After the application of the spots, the fabric samples were left to rest overnight. The treatment conditions were as follows. For all treatments, 8 grams of each cleanser was dissolved in 1 liter of water. The water was at 40 ° C and with a hardness of 150 ppm. The soaking time was sixty minutes. After the designated time, the cubes were emptied, and each group of fabric samples was washed and dried as described in Example 1. After drying, the samples were evaluated for stain removal, as described. described in Example 3. The results are shown in Tables 9 and 10 and in Figure 4. Tables 9 and 10 show the performance of each type of treatment on each spot, reported as Delta E units. The "Total" column is the sum of the Delta E measurements of all types of stains, indicating the overall stain removal performance for each type of treatment. Figure 4 is a graphical representation showing the sum of total Delta E for each spot in cotton, plus the total Delta E for each spot, obtained from polyester / cotton. These results demonstrate that all types of peracid precursor tested improve the ability of the detergent formulations described in Table 1 to remove stains.

TABLE 9: COMPARISON OF ELIMINATION OF STAINS IN COTTON BY DETERGENT FORMULATIONS CONTAINING OR NOT VARIOUS PERACTICIAN PRECURSORS, MEASURED BY DELTA E TABLE 10: COMPARISON OF DISPOSAL OF STAINS IN POLYESTER / COTTON FOR DETERGENT FORMULATIONS THAT CONTAIN OR NOT VARIOUS PERACTICIAN PRECURSORS. MEASURED BY DELTA E Polyester Coffee Grape EspaSanAderePurchase MaquiMostaFull DMO Total Cotton gueti gre zo assoza de pastel Acid 0.68 0.82 23.93 0.86 7.14 5.20 6.09 13.46 2.76 29.22 90.2 citrus 0.17 0.82 23.53 1.73 6.97 5.71 5.54 13.34 2.46 29.50 90.43 Acid 0.77 0.78 21.53 1.15 7.27 5.24 5.99 12.52 2.74 29.20 87.17 Adipic acid 0.69 0.84 22.84 1.04 6.99 5.16 6.63 12.83 3.07 29.90 89.98 tartaric EXAMPLE 5 This example compares the stain removal performance demonstrated by the formulations of the present invention containing adipic acid, tartaric acid and L-tartaric acid, and the commercial formulations SHOUT ™, OXYPOWER ™ and CLOROX ™ Oxygen Action. The fabrics for the tests, the treatment conditions, the stains and the procedures for their application, were described in Example 3, with the difference that only the spaghetti, blood, grass, make-up and mustard stains were tested in this example. The adipic acid was tested in concentrations of 1% and 0.8% in the formulated detergent compositions as described in example 4. Both the treatments with tartaric acid and the treatments with L-tartaric acid, consisted of the detergent formulation shown in Table 1 with the mixed additives for a final concentration of 1 percent by weight of tartrate. After the application of the spots, the fabric samples were allowed to age overnight. The treatment conditions were as follows. For all treatments, 8 grams was dissolved in 1 liter of water, except for CLOROX ™, where 10 g per liter of water was dissolved. The water was at 40 ° C, with hardness of 150 ppm. The soaking time was sixty minutes.

After the designated time, the cubes were emptied, and each group of fabric samples was washed and dried as described in Example 1. After drying, the fabric samples were evaluated for stain removal, as as described in Example 3. The results are shown in Tables 11 and 12, and in Figure 5. Tables 11 and 12 show the performance of each type of treatment on each spot, reported as Delta E units. The column "Total" is the sum of the measurement of Delta E in all types of spots, indicating the overall performance in the elimination of spots, of each type of treatment. Figure 5 is a graphical representation showing the sum of total Delta E for each spot corresponding to cotton, plus the total Delta E for each "spot obtained from polyester / cotton." These results demonstrate that all types of peracid precursors, when used in the detergent formulations of Table 1 at the indicated concentrations, show improved stain removal in relation to the SHOUT ™ OxyPower and the CLOROX ™ Oxygen Action.

TABLE 11: COMPARISON OF ELIMINATION OF VARIOUS TYPES OF STAINS IN COTTON FOR DETERGENT FORMULATIONS CONTAINING SEVERAL PERACTICIAN PRECURSORS. COMPARED WITH SHOUT ™ OXY POWER and CLOROX ™ OGYGEN ACTION, MEASURED BY DELTA E.

TABLE 12: COMPARISON OF ELIMINATION OF VARIOUS TYPES OF STAINS IN POLYESTER / COTTON FOR DETERGENT FORMULATIONS CONTAINING SEVERAL PERACTICIAN PRECURSORS. COMPARED WITH SHOUT ™ OXY POWER and CLOROX ™ OGYGEN ACTION, MEASURED BY DELTA E.

Polyester / Cotton Spaghetti Blood Pasture Makeup Total Mustard SHOUT ™ Oxy 26.06 1.59 17.35 12.42 1.36 68.77 Power CLOROX ™ 29.59 2.09 18.06 12.22 12.13 74.09 Oxygen Action Acid 24.30 1.50 6.59 5.63 10.36 48.39 Adipic acid at 1% Acid 24.07 1.53 6.59 5.42 11.16 48.76 Adipic at 0.8% Acid 24.30 1.43 6.76 5.66 10.94 49.09 Tartaric at 1% Acid L- 24.98 1.54 7.34 5.92 10.52 50.30 tartaric at 1% EXAMPLE 6 This example compares the color fading performance demonstrated by the formulations of the present invention, which contain adipic acid and tartaric acid, compared to the comparison formulation and with the commercial formulations SHOUT ™ Oxypower, TIDE ™ with bleach and CLOROX ™ Oxygen Action. Previously dyed test fabrics were obtained from Testfabrics, Inc., and consisted of fabric samples dyed with the following industry-standard dyes: Acid blue 113 in polyamide, direct blue 71 in cotton, reactive blue 225 in cotton, coffee reagent 7 in cotton, sulfur blue 19 in cotton, direct blue 1 in cotton, direct red 80 in cotton, and acid red in nylon. Adipic acid was added to the comparison formulation in a percentage by final weight equivalent to 1 percent by weight of tartrate. The treatment conditions for the stained samples were as follows. For all treatments, 8 grams of each cleaner was dissolved in 1 liter of water, except for CLOROX ™, where 10 g per liter of water was dissolved. The water was at 40 ° C, with hardness of 150 ppm. The soaking time was sixty minutes. After the designated time, the cubes were emptied, and each group of fabric samples was washed and dried as described in Example 1. After drying, the fabric samples were evaluated for dye removal. The color difference was described as a Delta E value, as described in Example 3. The smallest color difference has the smallest Delta E value, that is, the lower the value of Delta E, it is observed less fading The Delta E values reported refer to untreated, dyed fabric. The results are shown in Table 13 and Figure 6. Table 13 shows the fading performance, with each type of treatment for each color, reported as Delta E units. The "Total" column is the sum of the measurements of Delta E in all types of colors, indicating the overall performance in the color fading of each type of treatment. These results demonstrate that the addition of peracid precursors of adipic acid and tartaric acid to the comparison formulation shows only an increase in color fading relative to the comparison formulation, and causes less fading than TIDE ™ with bleach.

TABLE 13: COMPARISON OF COLOR RENDERING WITH DETERGENTS CONTAINING SEVERAL PERACTICIAN PRECURSORS, COMPARED WITH COMPARING FORMULATION, SHOUT ™ OXY POWER. TIDE ™ WITH WHITENER AND CLOROX ™ OXYGEN ACTION, MEASURED BY DELTA E Blue Blue Blue Coffee Blue Blue Red Red Total direct acid reagent reactive direct sulfur acid 113 in 71 in 225 in 7 in 19 in 1 in 80 in in polyamide cotton cotton cotton cotton cotton cotton nylon CLOROX ™ 0.59 0.96 0.81 2.08 3.51 2.96 7.48 0.93 19.32 Acid 0.63 0.89 1.12 1.81 5.12 4.11 6.78 0.82 21.28 Adipic acid 0.74 0.95 1.12 1.79 4.84 4.01 5.25 0.88 19.58 Tartaric Formulation 0.72 1.01 1.38 1.63 3.45 3.12 6.11 1.13 18.55 improved SHOUT ™ 0.58 0.47 1.14 2.21 4.11 2.12 6.32 0.95 17.89 TIDE ™ with 0.72 0.96 1.06 2.29 9.20 4.60 5.27 0.60 24.71 bleach EXAMPLE 7 This example compares the oxidation potential developed in water, with the addition of the comparison formulation, compared to the improved formulation. For both the comparison formulation and the improved formulation, 8 grams of each detergent composition was dissolved in 1 liter of water at 40 ° C (104 ° F), with a hardness of 150 ppm. The pH was about 10.8. The measurement of the ORP (oxidation reduction potential) in millivolts (mV) was performed with an ORP electrode (Beckman Instruments, Fullerton, CA). The results are shown in Figure 7, which is a graphical representation comparing the ORP of the comparison formulation with the improved formulation, with an exponentially performed curve fitting. Figure 7 demonstrates that the improved formulation increases the ORP developed in water, compared to the comparison formulation, indicating increased bleaching power.

EXAMPLE 8 This example demonstrates the storage stability of the particulate detergent formulations of the present invention. Two detergent formulations were prepared for the stability test, with a composition described in Table 14. Additional sodium carbonate was included in one of the formulations to compensate for the absence of metal metasilicate sodium protectants.

TABLE 14: FORMULATION FOR STABILITY TEST IN STORAGE Component% CAS Weight # Name Substrate 36.75 497-19-8 Sodium Carbonate Surfactant Surfactant 2.95 68551-12-2 GENOPOL LA060 ™; linear ethoxylated nonionic alcohol of 12 to 16 carbon atoms (3 moles EO); Clariant Corporation Surfactant 0.65 127036-24-2 GENOPOL UD-030 ™; non-ionic ethoxylated alcohol of 11 carbon atoms (3 moles EO); Clariant Corporation Solvent 0.40 34590-94-8 DPM; methyl ether soluble in dipropylene glycol (1- (2-methoxy-water isopropoxy) -2-propanol); Lyonell Salt 56.58 15630-89-4 Sodium percarbonate; peroxide Solvay-lnterox alkaline Agent 0.25 68479-09-4 Copolymer of acrylic acid ~ dispersive 4500 moles of weight; neutralized with sodium; Rohm and Haas Precursor 1.00 133-37-9 Tartaric acid; American Perácido International Protector of 1.42 6834-92-0 Blue Meta; Metal metasilicate / anhydrous sodium agen 100.00; PQ Dispersive Corporation.

The two formulations were prepared by mixing a solution of sodium carbonate surfactant substrate with a solution containing two nonionic surfactants and a water soluble substrate, for less than one minute. The formulation was mixed for an additional 7 minutes to achieve a smooth, consistent material, in which most of the liquid was absorbed by the powder. The rest of the materials were then added, and the mixture was stirred for an additional 3.5 minutes, until a uniform mixture was obtained. Each of the two formulations was divided into two batches, of which their available oxygen content was measured and then stored at a humidity of 50% and a temperature of 22.2 ° C or 35.5 ° C, for a period of 60 days . Figure 8 shows the results of the stability test as the exponential decrease in the available oxygen content of the two formulations during the storage period of 60 days.

EXAMPLE 9 This example compares the reaction of two detergent formulations of the present invention having an acid or neutral source of peracid precursor. Two formulations were prepared for testing, with a composition described in Table 15.

Component% Weight Name Surface-active substrate 31.5 Sodium carbonate Non-ionic surfactant 2.75 GENOPOL 26-L-45; Clariant Corporation Nonionic surfactant 1.0 Acusol 445N Solvent soluble in 0.50 Dipropylene glycol methyl ether water (1- (2-metosiisopropoxy) -e-propanol); Lyonell Peroxide salt 62.0 Sodium percarbonate; Solvay-alkaline Interox To this composition were added precursors of tartaric peracid, either in acid form (tartaric acid) or in neutralized form (potassium sodium tartrate) in a concentration equivalent to 1.5% by weight of acid (ie 1.5 % by weight of tartaric acid and 2.15% by weight of potassium sodium tartrate). Both formulations were tested to investigate their ability to clean stains on different fabrics in the test procedures described in the preceding examples. In each case, there was no significant difference in the cleansing ability of the two formulations that had an acidic or neutral form of the tartaric acid precursor. The foregoing description of the invention has been presented for purposes of illustration and description. The foregoing is not intended to limit the invention to the form or forms described herein. While the description of the invention has included the description of one or more embodiments and certain variations and modifications, other variations and modifications are within the scope of the invention, for example, those that may be within the skill and knowledge of the connoisseur of the subject, after understanding the present description. This is aimed at obtaining rights that include alternative modalities in the permitted extension, including structures, functions, ranges or alternate steps, interchangeable and / or equivalent to those described here, and without pretending to publicly dedicate any subject subject to patentability.

Claims (57)

1. CLAIMS 1. A detergent composition in solid particles having increased storage stability, which contains: a. an alkaline peroxide salt coated with a surface active agent; and b. a peracid precursor selected from the group consisting of carboxylic acids and salts thereof. 2. The detergent composition of claim 1, further characterized in that the alkaline peroxide salt is selected from the group consisting of sodium percarbonate and sodium perborate. 3. The detergent composition of claim 1, further characterized in that the alkaline peroxide salt is present in an amount from about 20% to about 80% by weight. 4. The detergent composition of claim 1, further characterized in that the peracid precursor is selected from the group consisting of dicarboxylic and tricarboxylic acids. The detergent composition of claim 1, further characterized in that the peracid precursor is selected from the group consisting of oxalic acid, malonic acid, succinic acid, glutaric acid, adipic acid, pimelic acid, tannic acid, tartaric acid and citric acid, and combinations of them. 6. The detergent composition of claim 5, further characterized in that the peracid precursor is tartaric acid. The detergent composition of claim 1, further characterized in that the peracid precursor is present in an amount from about 0.1% to about 10% by weight. 8. The detergent composition of claim 1, further characterized in that the peracid precursor is present in an amount from about 0.7% to about 2% by weight. 9. The detergent composition of claim 1, further characterized in that the surfactant includes at least one nonionic surfactant. 10. The detergent composition of claim 9, further characterized in that the nonionic surfactant includes an ethoxylated alcohol of 11 to 16 carbon atoms. 11. The detergent composition of claim 10, further characterized in that the ethoxylated alcohol is selected from the group consisting of GENOPOL LA060 ™, GENOPOL UD-030 ™ and combinations thereof. 12. The detergent composition of claim 1, further characterized in that the composition further contains a surfactant substrate. 13. The detergent composition of claim 12, further characterized in that the surfactant substrate is selected from the group consisting of sodium carbonate, sodium sulfate, and combinations thereof. 14. The detergent composition of claim 1, further characterized in that the composition further contains a metal shield. 15. The detergent composition of claim 12, further characterized in that the metal protector is sodium metasilicate. 16. The detergent composition of claim 1, further characterized in that the composition further contains a dispersing agent. 17. The detergent composition of claim 16, further characterized in that the dispersing agent is selected from the group consisting of polymers derived from acrylic and rosin soaps. 18. The detergent composition of claim 16, further characterized in that the dispersing agent is a maleic / acrylic acid copolymer. 19. The detergent composition of claim 1, further characterized in that the composition further contains a water soluble solvent. 20. The detergent composition of claim 19, further characterized in that the water-soluble solvent is selected from the group consisting of dipropylene glycol methyl ether, ethylene glycol butyl ether, and combinations thereof. 21. A process for treating a stain on a fabric, comprising contacting the stained fabric with a detergent composition containing an alkaline peroxide salt coated with a surfactant and a peracid precursor selected from the group consisting of carboxylic acids. and its salts. 22. The process of claim 21, further characterized in that the alkaline peroxide salt is selected from the group consisting of sodium percarbonate and sodium perborate. 23. The process of claim 21, further characterized in that the alkaline peroxide salt is selected from the group consisting of sodium percarbonate and sodium perborate. The process of claim 21, further characterized in that the alkaline peroxide salt is present in an amount from about 20% to about 80% by weight. 25. The process of claim 21, further characterized in that the peracid precursor is selected from the group consisting of dicarboxylic and tricarboxylic acids. The process of claim 21, further characterized in that the peracid precursor is selected from the group consisting of oxalic acid, malonic acid, succinic acid, glutaric acid, adipic acid, pimelic acid, tannic acid, tartaric acid and citric acid, and combinations of them. 27. The process of claim 26, further characterized in that the peracid precursor is tartaric acid. The process of claim 21, further characterized in that the peracid precursor is present in an amount from about 0.1% to about 10% by weight. 29. The process of claim 21, further characterized in that the peracid precursor is present in an amount from about 0.7% to about 2% by weight. 30. The process of claim 21, further characterized in that the surfactant comprises at least one nonionic surfactant. 31. The process of claim 30, further characterized in that the nonionic surfactant includes an ethoxylated alcohol of 11 to 16 carbon atoms. 32. The process of claim 31, further characterized in that the ethoxylated alcohol is selected from the group consisting of GENOPOL LA060 ™, GENOPOL UD-30 ™ and combinations thereof. 33. The process of claim 21, further characterized in that the composition further contains a surfactant substrate. 34. The process of claim 33, further characterized in that the surfactant substrate is selected from the group consisting of sodium carbonate, sodium sulfate and a combination thereof. 35. The process of claim 21, further characterized in that the composition further contains a metal protector. 36. The process of claim 35, further characterized in that the metal protector is sodium metasilicate. 37. The process of claim 21, further characterized in that the composition further contains a dispersing agent. 38. The process of claim 37, further characterized in that the dispersing agent is selected from the group consisting of acrylic derived polymers and rosin soaps. 39. The process of claim 38, further characterized in that the dispersing agent is a maleic / acrylic acid copolymer. 40. The process of claim 21, further characterized in that the composition further comprises a water soluble solvent. 41. The process of claim 40, further characterized in that the water-soluble solvent is selected from the group consisting of dipropylene glycol methyl ether, ethylene glycol butyl ether, and a combination thereof. 42. A detergent composition, which contains: a. from about 50% to about 60% by weight of an alkaline peroxide salt, characterized in that said alkaline peroxide salt is coated by a surfactant; b. from about 0.7% to about 2% by weight of a peracid precursor selected from the group consisting of carboxylic acids and salts thereof. 43. The detergent composition of claim 42, further comprising: a. from about 30% to about 40% by weight of sodium carbonate: b. from about 0.7% to about 2% by weight of sodium metasilicate; c. from about 0.2% to about 5% by weight of maleic / acrylic acid copolymer; d. from about 0.3% to about 0.5% by weight of dipropylene glycol methyl ether; and. from about 0.2% to about 5% by weight of linear ethoxylated alcohol of 10 to 14 carbon atoms; and f. from about 0.2% to about 5% by weight of an ethoxylated alcohol of 11 carbon atoms. 44. A method for making a solid particulate detergent, comprising: a. contacting an alkaline peroxide salt with a solution containing a surfactant to form a coated alkaline peroxide salt; and b. adding a peracid precursor to the coated alkaline peroxide salt to form a solid particulate composition having improved storage stability. 45. The method of claim 44, further characterized in that the surfactant is a nonionic surfactant. 46. The method of claim 45, further characterized in that the nonionic surfactant includes an ethoxylated alcohol of 11 to 16 carbon atoms. 47. The process of claim 46, further characterized in that the ethoxylated alcohol is selected from the group consisting of GENOPOL LA060 ™, GENOPOL UD-030 ™ and combinations thereof. 48. The method of claim 44, further characterized in that the solvent is soluble in water. 49. The method of claim 44, further characterized in that the solvent is dipropylene glycol methyl ether. 50. The method of claim 44, further characterized in that the step of contacting comprises: a. contacting a surfactant substrate with the solution; and b. mixing an alkaline peroxide salt with the surfactant substrate, characterized in that the alkaline peroxide salt absorbs the solution from a surface of the surfactant substrate. 51. The method of claim 44, further characterized in that the alkaline peroxide salt is selected from the group consisting of sodium percarbonate and sodium perborate. 52. The method of claim 44, further characterized in that the alkaline peroxide salt is present in the particulate solid detergent, in an amount of from about 20% to about 80 percent by weight. 53. The method of claim 44, further characterized in that the peracid precursor is selected from the group consisting of dicarboxylic and tricarboxylic acids. 54. The method of claim 44, further characterized in that the peracid precursor is selected from the group consisting of oxalic acid, malonic acid, succinic acid, glutaric acid, adipic acid, pimelic acid, tannic acid, tartaric acid and citric acid, and combinations of them. 55. The method of claim 54, further characterized in that the peracid precursor is tartaric acid. 56. The method of claim 44, further characterized in that it comprises the additional step of adding an ingredient selected from the group consisting of nonionic surfactants, surfactant substrates, metal protectants, dispersants, enzyme spot removers, fluorescent whitening agents, optical brighteners , regulators, colorants, fragrances, detergency builders, peroxide stabilizers, and binding agents, to the coated alkaline peroxide salt, after the addition of the peracid precursor. 57. A dry particulate detergent composition containing an alkaline peroxide salt, a solvent, a peracid precursor selected from the group consisting of carboxylic acids and salts thereof, made by the method comprising: a. combining a surfactant with a solvent to form a solution; b. contacting an alkaline peroxide salt with the solution to form an alkaline peroxide salt; c. adding a peracid precursor to the coated alkaline peroxide salt to form a solid particulate composition having improved storage stability.