JP2006526695A - Detergent formulation comprising alkali peroxide and organic acid - Google Patents

Abstract

The present invention provides a particulate detergent composition comprising an alkali peroxide salt and an organic peracid precursor, a method of treating stains with the composition, and a method of making the composition. The composition has long-term stability afforded by coating with an alkali peracid salt. The method of formulating the composition to include this coating is relatively easy and inexpensive.

Description

  The present invention relates to the field of cleaning compositions comprising a combination of an alkali peroxide and a peracid precursor activator in a formulation having long-term storage stability.

  Although bleaching agents for fabrics containing chlorine have excellent cleaning properties, they can only wash suitable fabrics and cannot be used for colored fabrics. Further, the bleaching agent has a characteristic odor, and when used at a high concentration, the odor may adhere depending on the cloth. For these reasons, there is a strong demand for the development of oxygen-containing bleaches that are not subject to the above limitations.

  Among oxygen-containing bleaches, sodium percarbonate and sodium perborate are particularly useful because of their bleaching ability and stability. Peroxygen bleaching is safe with respect to fabric color, and yellowing of a white fabric is relatively difficult to occur. It also gives the fabric a good feel and absorbency without compromising the physical strength of the fabric. Such peroxygen bleaching is mainly used to remove stains and dirt in two different laundry environments. The first environment utilizes high cleaning temperatures, particularly above 185 ° F. (about 85 ° C.), is commonly used in commercial laundry, and is sometimes found in European homes. In such a high temperature environment, peroxygen substances such as hydrogen peroxide or perboric acid or sodium percarbonate can be added to the washing mixture to increase the bleaching effect. US home washing machines typically use lower temperatures. For low temperatures, hydrogen peroxide has been successfully combined with an activator. To enhance bleaching from low to medium temperatures, a wide range of materials have been proposed as activators for peroxygen bleaching.

  The combination of peroxygen bleach activators is selected by a complex balance of two conflicting properties. The combination is storage stable and its activity is not subject to significant loss (eg, no more than 10-20% for 90 days at 59 ° F. to 86 ° F. (about 15 ° C. to about 30 ° C.)). ) Must be done. On the other hand, cold water (50 ° F. to 86 ° F. (about 15 ° C. to about 30 ° C.)) laundry solution so that it can be effective during most of the 10-12 minute wash time of a household automatic washing machine cycle. The combination should have sufficient reactivity so that it can react within 1-2 minutes after the addition. Thus, the combination of a peroxygen compound and an activator needs to exhibit a reaction rate 10,000 to 100,000 times higher than the decomposition rate that can withstand storage in a washing machine.

  U.S. Pat. No. 6,057,049 to Fries et al. Describes a stabilized bleaching aid suitable for addition to cleaning and bleaching compositions comprising an activator for active oxygen and a mixture of fatty acids and polyethylene glycol. Teaches. The disclosed activators are carboxylic acid derivatives that increase the bleaching action of the mixture by reacting with per compounds to form peracids or permitting bleaching at low washing temperatures. The bleaching aid formulation is stabilized by spraying a combination of active agent, fatty acid, and polyethylene glycol onto the solidification zone to form particles less than 1 mm in diameter. However, in a stability test conducted with this product, the effectiveness of the active borate perborate drops below 90% after storage for 21-28 days, and after 6 weeks the effectiveness is 40%. Has fallen to less than. Thus, it can be seen that the above compounding method is technically complex and expensive and that the resulting product is insufficiently stable for storage, transportation and consumer use.

U.S. Pat. No. 6,053,096, granted to Trani and Ricci, for granulated laundry containing percarbonate with increased stability, coated or agglomerated with a hydrophobic acylated ester of citric acid A detergent is disclosed. The acylated ester of citric acid coats the detergent particles to increase the stability of the percarbonate during storage and acts as a bleach activator under water washing conditions. This composition is composed of an acylated ester of citric acid, after combining all other ingredients, on a granular percarbonate particle, or a complete composition containing percarbonate and other additives. Manufactured by spraying. However, such acylated esters of citric acid are highly hydrophobic, thus limiting the selectivity of the formulation and negatively affecting the dissolution rate of the coated product in water.

U.S. Patent No. 6,057,049 to MacBeath discloses a laundry detergent comprising a percarbonate bleach coated with a mixed salt comprising an alkali metal carbonate and an alkali metal sulfate. This detergent also includes a peroxyacid bleach precursor, an acidifying agent, and a means for delaying the release of the acidifying agent. Since the coated percarbonate has storage stability and the acidifying agent is gradually released, the pH of the laundry is suppressed to less than 9.5 in the final washing solution. The coating that provides sustained release of the acidifying agent is a double coating consisting of an inner wax and outer silica, formed by a functional multi-layer coating process, which makes the coating and the dry detergent formulation complex and expensive It ’s a good thing.
U.S. Pat. No. 3,833,506 US Pat. No. 5,702,635 US Pat. No. 5,716,923

  Accordingly, there is a need for fabric detergent formulations that combine peroxygen bleach detergency and peroxygen bleach activators in a storage stable composition that can be formulated relatively easily and inexpensively.

  The present invention relates to a particulate detergent composition having a peroxygen bleach coated with a surfactant and a peroxygen bleach activator, and easily and inexpensively so that the detergent composition has long-term storage stability. Methods for formulating and using these detergent compositions to treat fabric stains are provided. The composition includes an alkali peroxide salt coated with a surfactant and a peracid precursor composed of a carboxylic acid and its salt. Preferably, the alkali peroxide salt present in an amount of about 20% to about 80% by weight of the composition is sodium percarbonate or sodium perborate. Preferably, the peracid precursor is present in an amount from about 0.1% to about 10% by weight of the composition, eg, oxalic acid, malonic acid, succinic acid, glutaric acid, adipic acid, pimelic acid, tannin. Dicarboxylic or tricarboxylic acids, such as acids, tartaric acid, or citric acid, or combinations thereof. Preferred surfactants are at least one nonionic surfactant, in particular a 11-16 carbon alcohol ethoxylate or a mixture of these alcohol ethoxylates.

  Composition is optional, surfactant substrate such as sodium carbonate and / or sodium sulfate, metal protective agent such as sodium metasilicate, dispersant such as acrylic derived polymer and rosin soap, dipropylene glycol methyl ether and / or ethylene glycol Contains other cleaning aids, including water-soluble solvents such as butyl ether, enzyme stain removers, fluorescent brighteners, fluorescent agents, buffers, colorants, fragrances, cleaning builders, peroxide stabilizers and extenders .

The method of formulating the solid detergent composition of the present invention provides an inexpensive method of mixing and coating the detergent ingredients to produce a composition with enhanced storage stability. The method includes mixing a surfactant with a solvent to form a solution and coating an alkali peroxide salt with the solution to produce a coated alkali peroxide salt. The peracid precursor is then added to the coated alkali peroxide salt. Preferably, the composition comprises a surfactant substrate, and the surfactant substrate is first coated with the solution and then the alkali peroxide so that the alkali peroxide salt absorbs the solution from the surface of the surfactant substrate. Mixed with salt.

  The present invention provides a detergent formulation comprising an alkali peroxide salt and an organic acid bleach activator that has a long shelf life, high stability, and is particularly useful for fabric cleaning. The formulation includes an alkali peroxide salt and a peracid precursor coated with a surfactant.

  Alkali peroxides are oxygen-containing bleaching agents such as sodium percarbonate and sodium perborate. Preferably, the peroxide salt is sodium percarbonate. In this application, the term “alkali peroxide salt” refers to hydrates of alkali peroxide salts and other cations. The alkali peroxide salt may consist of one chemical species, or may consist of a combination of different chemical species. The peroxide salt is present in the formulation in the range of about 1% to about 99% by weight of the formulation. Preferably, the peroxide salt is present in the range of about 20% to about 80% by weight. More preferably, the peroxide salt is present in the range of about 40% to about 60% by weight. Even more preferably, the peroxide salt is present in the range of about 50% to about 60% by weight. Most preferably, the peroxide salt is present at about 56% by weight.

  The peracid precursor activates an alkali peroxide salt in the solution to generate an organic peroxide. The peracid precursor may consist of one chemical species or a combination of different chemical species. The peracid precursor of the present invention is selected from organic acids and salts thereof. For peracid precursors having different isomers, all isomers are effective 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. An effective tricarboxylic acid is citric acid. More preferably, the peracid precursor comprises tartaric acid, adipic acid, and / or citric acid, with tartaric acid being most preferred. The peracid precursor is typically present in the formulation in the range of about 0.1% to about 10% by weight of the formulation. Preferably, the peracid precursor is present in the range of about 0.5% to about 5% by weight. More preferably, the peracid precursor is present in the range of about 0.7% to about 2% by weight. Most preferably, the peracid precursor is present at about 1% by weight.

  Other peracid precursors (such as tetraacetylethylenediamine (TAED) and sulfonic nonalloyoxybenzene (NOBS)) are also known in the art, but the peracid precursors of the present invention are known peracid precursors. Has significant advantages over materials. In contrast to TAED and NOBS, many organic acid peracid precursors of the present invention are widely recognized in nature and are recognized as being environmentally friendly. In addition, many organic acid peracid precursors are inexpensive and can be used economically at the specific concentrations described above, thus providing a more cost effective system.

  The formulation of the present invention may contain a water-soluble solvent. Many water-soluble solvents are known by those skilled in the art, but preferred water-soluble solvents include dipropylene glycol methyl ether (1- (2-methoxyisopropoxy) -2-propanol) and ethylene glycol butyl ether (2-butoxy). Ethanol). The water soluble solvent is typically present in the formulation in the range of about 0.1% to about 10% by weight. Preferably, the water soluble solvent is present in the range of about 0.2% to about 5% by weight. More preferably, the water soluble solvent is present in the range of about 0.3% to about 0.5% by weight. Most preferably, the water soluble solvent is present at about 0.4% by weight.

  The formulations of the present invention may include at least one surfactant to help dissolve the water-insoluble material. For example, useful nonionic surfactants include linear 10-14 carbon alcohol ethoxylates or 11 carbon alcohol ethoxylates. The concentration of surfactant in the formulations of the present invention can vary widely. Typically, the surfactant is present in the formulation in the range of about 0.1% to about 20% by weight. Preferably, the surfactant is present in the range of about 0.2% to about 5% by weight. More preferably, the surfactant is present in the range of about 0.6% to 3% by weight.

  In the past, it has been difficult to incorporate alkaline peroxide salts into dry particulate laundry detergents at an effective level. This was because these bleaches were unstable during storage. Sodium percarbonate rapidly loses its available oxygen in the presence of ions or heavy metals such as iron, copper, manganese, most importantly in the presence of moisture. Such effects are accelerated at temperatures above about 30 ° C. (about 85 ° F.).

  Moisture and ions are components that cannot be avoided with conventional granule laundry treatment compositions. In addition, laundry processed products are often stored in humid environments, and the products take up moisture in such environments, so decomposition of alkali peroxides due to moisture during storage becomes increasingly problematic. As a result, in laundry detergents containing alkali peroxide salts shipped to warm and humid areas, the stability of the bleach is barely acceptable.

  The decomposition of percarbonate accelerated by such temperature also occurs in the final product manufacturing process. In some conditions, mixing the individual components increases the temperature of the mixture and accelerates the decomposition of the alkali peroxide salt. Furthermore, the temperature rise is greater when mixing is performed under humid conditions.

  In addition, when alkali peroxide salts are mixed with bleach activators, stability during storage and manufacture becomes a greater problem. In fact, mixing alkaline alkali salts and bleach activators during the preparation of dry granular detergents can cause rapid degradation during manufacture or storage when the detergent composition is placed in a humid environment. There is.

  Accordingly, by coating alkali peroxide particles with a surfactant, a dry granular detergent comprising an alkali peroxide and a carboxylic acid peracid precursor can be formulated to have a relatively long and stable shelf life. What we have done is an unexpected and useful discovery. Surfactants usually function as agents that activate the surface by filling the interface between the hydrophilic and hydrophobic compounds. Therefore, given the reactivity of alkali peroxides with water, especially with the combination of water and peracid precursors, it is difficult to use alkali peroxides in particulate detergents. It is unexpected that the formulation can be stabilized by combining alkali peroxide with a substance that enhances contact with water. However, it has been found that coating the alkali peroxide salt with a surfactant greatly increases the stability and thus increases the shelf life of the particulate detergent composition of the present invention. This makes it possible to produce a stable particulate bleaching composition that includes a peracid bleach activator and an alkali peroxide salt that is a source of hydrogen peroxide.

From a stability test conducted using the detergent composition of the present invention, which measures the available oxygen content of the detergent, immediately after preparation of the detergent formulation and at each point during storage, the composition is about 50% humidity, about It can be seen that after storage at 36 ° C. (96 ° F.) for 60 days, it retains more than about 90% of available oxygen. Preferably, the detergent compositions of the present invention are stable enough to retain more than about 60% available oxygen after 60 days storage under the above conditions. More preferably, the detergent composition of the present invention is stable enough to retain more than about 70% available oxygen after 60 days storage under the above conditions. More preferably, the detergent composition of the present invention comprises
It is stable enough to retain more than about 80% available oxygen after 60 days storage under the above conditions. More preferably, the detergent compositions of the present invention are stable enough to retain more than about 90% available oxygen after 60 days storage under the above conditions. Most preferably, the detergent compositions of the present invention are stable enough to retain more than about 95% available oxygen after 60 days storage under the above conditions.

  For the purposes of this disclosure, the coating of the alkaline peroxide salt component of the detergent refers to the alkaline peroxide so that at least one surface of the alkaline peroxide salt is in contact with the surfactant in the final detergent composition after formulation. Refers to contacting salt with a surfactant. Preferably, the surfactant coats at least half of the individual alkali peroxide particles or agglomerates on at least half of the particles. Most preferably, the surfactant coats or adheres to the entire surface of the individual alkali peroxide salt particles.

  The coated particulate particles of the present invention can be obtained by various methods known in the art such as, for example, spraying, agglomeration, or coating. For example, surfactant or a combination of surfactants may be used as either an agglomeration agent or a coating to coat or coagulate particles of alkali peroxide salt. The preferred method of coating the alkali peroxide particles is to mix the selected surfactant with a solvent to form a surfactant solution, which is mixed with the alkali peroxide to produce individual alkali salt particles. Coating or adhering. After coating or adhesion, the surfactant exhibits a non-flowable consistency that acts as a barrier to water. In order to prepare alkali peroxide particles coated or agglomerated in this way, the solvent is mixed with a surfactant to form a solution and the consistency is adjusted during or after the formulation of the coated particles. Must be chosen to undergo change.

  After the alkali peroxide salt is added and mixed thoroughly to obtain a coating, the surfactant solution exhibits a “rubbery” non-flowable consistency. This is thought to increase the protective power of the alkali peroxide particles. Without being bound by any theory, the consistency of the surfactant solution changes as some of the solvent present in the surfactant solution evaporates and some is absorbed by the surfactant substrate. Thus, it is considered that a non-fluid protective barrier is formed on the surface of the alkali peroxide salt particles.

  The most preferred method of making the detergent composition of the present invention is to produce a solution of one or more nonionic surfactants using a water soluble solvent. This solution is then mixed with the surfactant substrate in such a ratio that a surfactant substrate coated with the surfactant solution is obtained and the remaining surfactant solution remains. Immediately thereafter, the alkali peroxide salt is added to the mixture and mixed until the remaining surfactant solution is absorbed from the surfactant substrate surface to the surface of the alkali peroxide salt, thereby coating the alkali peroxide salt particles. . This method of mixing the above ingredients is thin enough to allow full activity of the alkaline peroxide salt while protecting the alkaline peroxide salt from water when the detergent composition is added to domestic wash water. A mild coating of at least one surfactant on the alkali peroxide salt can be obtained easily and inexpensively. Any other desirable ingredients may be added to the mixture to produce the detergent formulation of the present invention.

A preferred surfactant substrate for use in the compositions of the present invention is sodium carbonate (soda ash), and the most preferred coating solution is a straight chain such as GENOPOL LA060 ™ mixed with the water soluble solvent dipropylene glycol methyl ether. Contains a mixture of nonionic surfactants such as 12-16 carbon alcohol ethoxylates and 11 carbon alcohol ethoxylates such as GENOPOL UD-030 ™. This surfactant solution is mixed and used to coat sodium carbonate. The alkali peroxide is then added to the mixture and mixed until the light coating of the surfactant solution is absorbed onto the surface of the alkali peroxide particles. During and after this mixing, the consistency of the coating changes from a liquid to a non-flowable form. Then any additional cleaning aids are added to the mixture and mixed.

  This combination of surfactant-coated alkali peroxide salts is further advantageous because the surfactant is known to aid in fabric cleaning when introduced into the wash water. Thus, the surfactant acts to protect and stabilize the particulate detergent of the present invention containing the alkaline peroxide salt and the peracid precursor during formulation and storage, and is introduced into the wash water. When activated, it acts to liberate alkali peroxide salts and peracids, and then functions to assist in washing the fabric and removing stains, apart from the activated bleach compound. These dual functions increase the detergency of the detergent of the present invention and facilitate manufacturing, transportation and handling conditions for the dry formulation.

  The formulations of the present invention may include a surfactant substrate that also functions as a bulking agent. For example, the surfactant substrate can be sodium carbonate (soda ash) or sodium sulfate. Sodium carbonate is preferred because it functions as a buffer and is more absorbent than sodium sulfate. Typically, the surfactant substrate is present in the range of about 1% to about 60% by weight. Preferably, the surfactant substrate is present in the range of about 10% to about 50% by weight. More preferably, the surfactant substrate is present in the range of 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 may include a metal protective agent that may also function as a soil dispersant and / or a pH buffer. For example, the metal protective agent is sodium metasilicate, a polymeric metal protective agent or a cationic metal protective agent. Sodium metasilicate is more preferable because it is easier to formulate than a molecular metal protective agent or a cationic metal protective agent. Sodium metasilicate is typically present in the formulation in the range of about 0.1% to about 10% by weight. Preferably, the sodium metasilicate is present in the range of about 0.5% to about 5% by weight. More preferably, the sodium metasilicate is present in the range of about 0.7% to about 2% by weight. Most preferably, the sodium metasilicate is present at about 1% by weight.

  The formulations of the present invention may contain a dispersant. Many dispersants are known to those skilled in the art, but preferred dispersants include acrylic derived polymers such as acrylic acid copolymers, and rosin soaps. A preferred acrylic acid copolymer is a maleic acid / acrylic acid copolymer. The dispersant is typically present in the formulation in the range of about 0.1% to about 10% by weight. Preferably, the dispersant is present in the range of about 0.2% to about 5% by weight. More preferably, the dispersant is present at about 0.25% by weight. Preferred formulations of the present invention are shown in Table 1.

本発明の組成物は、任意でさらなる洗浄補助剤を含んでいてもよい。代表的な洗浄補助剤としては、酵素しみ抜き剤が挙げられる。そのような物質としては、たとえば布の染みなどの基質を加水分解できるような酵素が挙げられる。国際生化学連合（Ｉｎｔｅｒｎａｔｉｏｎａｌ Ｕｎｉｏｎ ｏｆ Ｂｉｏｃｈｅｍｉｓｔｒｙ）においては、こうした種類の酵素に対して許容されている名称はヒドラーゼである。ヒドラーゼとしては、限定はされないが、プロテアーゼ、アミラーゼ（カルボヒドラーゼ）、リパーゼ（エステラーゼ）、セルラーゼ、およびそれらの混合物が挙げられる。プロテアーゼ、特にいわゆるアルカリプロテアーゼが、洗剤補助剤としてよく用いられる。これはそれらのプロテアーゼが、例えば血液や草などの厄介な汚れであるタンパク質物質を攻撃して分解するためである。様々な本発明の調合物において、酵素を不活性化することがない範囲まで溶液のｐＨを下げるのに十分なだけ組成物が希釈されている場合には、任意で酵素しみ抜き剤を加えることができる。

The compositions of the present invention may optionally contain further cleaning aids. A typical cleaning aid is an enzyme stain remover. Examples of such substances include enzymes that can hydrolyze a substrate such as a fabric stain. In the International Union of Biochemistry, the accepted name for this type of enzyme is hydrase. Hydrases include, but are not limited to, proteases, amylases (carbohydrases), lipases (esterases), cellulases, and mixtures thereof. Proteases, especially so-called alkaline proteases, are often used as detergent adjuvants. This is because these proteases attack and degrade protein substances that are troublesome soils such as blood and grass. In various formulations of the present invention, an enzyme stain remover may optionally be added if the composition is sufficiently diluted to lower the pH of the solution to the extent that it does not inactivate the enzyme. it can.

Other classes of detergent adjuncts that can benefit from the practice of the present invention are fluorescent brighteners and fluorescent agents, but in principle these materials are more effective than enzyme stain removers. As shown, it is less susceptible to attack by the rapid generation of active oxygen. Representative optical brighteners include naphthol triazole stilbene and distyryl biphenyl sold by Ciba-Geigy Corporation under the names Tinopal ™ RBS and Tinopal ™ CBS-X, respectively. An optical brightener, as well as a stilbene material sold by Ciba-Geigy under the name Tinopal ™ 5BMX. Tinopal ™ CBS-X brightener is the preferred whitening additive in the formulations of the present invention because it is the most stable brightener for peroxides. Other useful brighteners are disclosed in US Pat. No. 3,393,153, which is hereby incorporated by reference, and more useful brighteners are available from the American Society for Test Materials (ASTM) publication D- 553A, List of Fluorescent Whitening
Agents for the Soap and Detergent Industry).

  If necessary, the composition of the present invention may contain further components such as a buffer, a coloring agent, a fragrance, a primary cleaning agent (surfactant), a cleaning builder and a bulking agent. In addition, peroxide stabilizers such as heavy metal chelate ligands such as EDTA may be added as needed.

  Representative surfactants include conventional nonionic, cationic, anionic and amphoteric surfactants as described in the art. Examples of suitable surfactants for use in these formulations are Kirk-Othmer, Encyclopedia of Chemical Technology, 3rd edition, volume 22, pages 247-387 (1983) and Described in McCutcheon's Detergents and Emulsifiers, North American Edition (1983). One generally preferred group of surfactants includes nonionic surfactants such as those described on Kirkusmer, pages 360-377. Nonionic materials include alcohol ethoxylate, alkylphenol ethoxylate, carboxylic acid ester, glycerol ester, polyoxyethylene ester, anhydrous sorbitol ester, ethoxylated anhydrous sorbitol ester, natural fat ethoxylate, oil and wax, fatty acid glycol Examples include esters, carboxylic acid amides, diethanolamine condensates, monoalkanolamine condensates, polyoxyethylene fatty acid amides, polyalkylene oxide block copolymers, poly (oxyethylenecooxypropylene) nonionic surfactants, and the like. A wide variety of materials are commercially available, including Shell Chemical Neodols ™, the Union Carbide Tergitols ™, the ICI Tween's ™ and Spans ™.

  Cleaning builders that may optionally be added to the bleaching composition can be selected from among the cleaning builders commonly added to detergent formulations. Useful builders are any conventional inorganic and organic water-soluble builder salts. Useful inorganic builder salts include, for example, water-soluble salts such as phosphates, pyrophosphates, orthophosphates, polyphosphates, silicates, carbonates, and the like. Examples of the organic builder include water-soluble phosphonate, polyphosphonate, polyhydroxysulfonate, polyacetate, carboxylate, polycarboxylate, and succinate.

  Specific examples of inorganic phosphate builders include triphosphate, pyrophosphate, and sodium and potassium salts of hexametaphosphate. Specific examples of the organic polyphosphonate include sodium and potassium salts of ethane-1-hydroxy-1,1-diphosphonic acid and sodium and potassium salts of ethane-1,1,2-triphosphonic acid. . Examples of these and other phosphate builder compounds are disclosed in U.S. Pat. Nos. 3,213,030, 3,422,021, 3,422,137 and 3,400,176. Yes. Trisodium tripolyphosphate and tetrasodium pyrophosphate are particularly preferred water-soluble inorganic builders.

  Specific examples of non-phosphate inorganic builders include water-soluble inorganic carbonates, dicarbonates, and silicates. Alkali metal carbonates, dicarbonates, and silicates such as sodium and potassium are particularly useful in the formulations of the present invention.

Water-soluble organic builders are also useful. For example, alkali metal, ammonium and substituted ammonium polyacetates, carboxylates, polycarboxylates and polyhydroxysulfates are useful builders for the compositions and processes of the present invention. Specific examples of polyacetate and polycarboxylate builders include ethylenediaminetetraacetic acid, nitrilotriacetic acid, benzene polycarboxylic (ie penta or tetra) acid, carboxymethoxysuccinic acid and citric acid sodium, potassium, lithium, ammonium and substituted An ammonium salt is mentioned.

  Water-insoluble builders, particularly sodium silicate alumino complexes such as zeolite 4A, which is a kind of zeolite molecular sieve having a monovalent cation of sodium and a pore size of about 4 mm, may be used. The preparation of this type of zeolite is described in US Pat. No. 3,114,603. The zeolite may be either amorphous or crystalline and may have water of hydration as is well known in the art.

  The bleaching composition of the present invention may further include a filler or a bulking agent. Common filler salts are alkali metal sulfates such as potassium sulfate or sodium sulfate, the latter being preferred. The most preferred filler for use in the composition of the present invention is sodium carbonate (soda ash).

  The composition of the present invention is useful for a wide range of stain types including spaghetti, mustard, salad dressing, dirty motor oil, blood, grass, make-up supplies, wine, juice, spices, fruit fillings, fruit jams, etc. It is.

  The cleaning composition of the present invention can be formulated into a variety of fabric cleaning products, particularly including laundry cleaners, carpet cleaners, upholstery cleaners and automotive interior cleaners. One skilled in the art can formulate the compositions disclosed herein into various types of products.

  Further objects, advantages and novel features of the present invention will become apparent to those skilled in the art upon review of the following examples, which are not intended to be limiting.

Example 1
In this example, in the removal of various types of stains from cotton, poly / cotton, and cotton knitted fabrics for 1 hour, 3 hours, or 5 hours of soaking time, the detergent compositions shown in Table 1 (hereinafter , Called "improved formulation").

  A 6 inch square fabric consisting of pre-washed and cut cotton fabric, polyester / cotton fabric, and cotton knit fabric was obtained from Testfabrics, Inc. (West Pittston, PA). Five different stains were investigated: spaghetti, mustard, salad dressing, dirty motor oil and blood. Two material cloths were used for each point.

  The stain was deposited as follows. For spaghetti, 0.25 mL of RAGU ™ Original was attached to each material fabric. For the mustard, a small amount of mustard was placed on the back of the rubber pipette valve, and the mustard was rubbed against the material cloth, thereby attaching KROGER (trademark) Traditional Yellow to each material cloth. Similar to a salad dressing stain, 0.25 mL KRAFT FREE ™ Catalina dressing was attached to each material fabric. For dirty motor oil stains, 2 drops of used motor oil were adhered to each material cloth. Finally, for blood stains, 0.25 mL of bovine blood was attached to each material cloth.

After the stain was applied, the material cloth was allowed to pass overnight. 7.6 liters (2 gallons) of approximately 46 ° C. (115 ° F. ± 2 °) water, with 29.6 mL (cc) of the improved formulation, each in a 19 liter (5 gallon) soak bucket Was added. The solution was stirred to dissolve the solid, and then the material cloth was added. Soaking in buckets for 1 hour, 3 hours, or 5 hours, as specified. Each bucket was stirred by hand again after 15 minutes and after 30 minutes. After the specified time, the solution in the bucket is discarded, and each group of material cloths is KENMORE (TM) 80 Series using 1/3 cup Ultra Concentrated PUREX (TM) laundry detergent and ballast load. 3.2 Cu. ft. Washed using a washing machine and dried in a KENMORE ™ Elite dryer.

  After drying, all material fabrics were evaluated by two different evaluators. The following evaluation procedure was used. The material cloth soaked for 3 hours was compared with the material cloth soaked for 1 hour, and the material cloth soaked for 5 hours was compared with the material cloth soaked for 1 hour. The following evaluation system was used. 4 = remarkably good; 3 = very good; 2 = good; 1 = slightly good; 0 = equivalent to the control (star if the stain has been completely removed); −1 = slightly inferior; −2 = -3 = considerably poor; -4 = markedly inferior; Table 3 shows the results for cotton, poly / cotton, and cotton knit compared to those soaked for 3 hours compared to those soaked for 1 hour, and Table 4 shows the results for cotton, poly / cotton, and cotton. It is the result of comparing the knit soaked for 5 hours with the knit soaked for 1 hour. 1a to 1c are graphs showing the results shown in Tables 2 and 3. FIG.

  These results indicated that the performance of the improved formulation increased with increasing soaking time. Compared to a soak time of 1 hour, the soak time is 3 hours for all types of stains on poly / cotton and all but the blood on cotton and cotton knit. For the type of stain, some improvement was seen when the soaking time was 3 hours rather than 1 hour. Furthermore, an improvement in stain removal performance was observed even at a soaking time of 5 hours. However, for most stains, the most dramatic improvement in stain removal occurred in the 1 to 3 hour soak time rather than the 1 to 5 hour soak time. These results show that the formulations of the present invention with peracid precursors provide improved cleaning results for most stain types evaluated compared to formulations without peracid precursors. It is shown.

(Example 2)
In this example, the stain removal effect of the two detergent formulations of the present invention containing different peracid precursors was compared to the formulations without peracid precursors shown in Table 4 (hereinafter referred to as “Comparative Formulas”). ).

予洗し、裁断した綿布、ポリエステル／綿布、および綿ニット布の６インチ四方の材料布は、テストファブリックス（Ｔｅｓｔｆａｂｒｉｃｓ）より入手した。異なる４種類の染み、すなわちスパゲッティ、マスタード、汚れたモータオイルについて調べた。各染みは、実施例１に記載したようにして各布の６枚の材料布に付着させた。同じ染みを付着させた材料布のうちの２枚を、酒石酸（Ｓｉｇｍａ Ｃｏｒｐ．ミズーリー州セントルイス）を最終重量パーセントが酒石酸塩当量で１重量％となるように加えた比較調合物で処理し、同じ染みを付着させた材料布のうちの２枚を、酒石酸カリウムナトリウム（Ｓｉｇｍａ Ｃｏｒｐ．ミズーリー州セントルイス）を最終重量パーセントが酒石酸塩当量で１重量％となるように加えた改良調合物で処理した。過酸前駆物質は標準的な工業的手順によって加えた。

Pre-washed and cut cotton fabric, polyester / cotton fabric, and cotton knitted fabric 6 inch square material fabrics were obtained from Testfabrics. Four different stains were examined: spaghetti, mustard, and dirty motor oil. Each stain was deposited on the six material cloths of each cloth as described in Example 1. Two of the fabrics with the same stain were treated with a comparative formulation with tartaric acid (Sigma Corp. St. Louis, MO) added to a final weight percent of 1% by weight of the tartrate equivalent, and the same Two of the stain-applied material fabrics were treated with an improved formulation in which sodium potassium tartrate (Sigma Corp. St. Louis, Mo.) was added to a final weight percent of 1% by weight of the tartrate equivalent. The peracid precursor was added by standard industrial procedures.

  After the stain was applied, the material cloth was allowed to pass overnight. In each 19 liter (5 gallon) soak bucket, 7.6 liters (2 gallons) of about 46 ° C. (115 ° F. ± 2 °) water with 29.6 cc of the appropriate detergent additive. added. The solution was stirred to dissolve the solid, and then the material cloth was added. After soaking in the bucket for 1 hour, each bucket was stirred by hand again after 15 minutes and 30 minutes. After the specified time, the solution in the bucket was discarded and each group of material fabrics was washed and dried as described in Example 1.

  A detergent formulation containing either tartaric acid or potassium sodium tartrate was compared and evaluated against a comparative formulation as described in Example 1. Table 5 shows the results for various types of stains in comparison with tartaric acid-containing detergent formulations, and Table 6 shows the results for the same type of stains with potassium sodium tartrate-containing formulations. Compared to things. 2a to 2c are graphs showing the results shown in Table 5 and Table 6. FIG. These results show that on all fabrics examined, for most stain types, the performance of the detergent formulation containing the peracid precursor additive is improved compared to the comparative formulation. It is shown. Furthermore, these results demonstrate that there is no significant difference between using tartaric acid and potassium sodium tartrate as a source of tartrate peracid precursor in solution. It is.

Example 3
This example compares the stain removal performance of an improved formulation, a comparative formulation and several commercial laundry pretreatment agents.
Pre-washed and cut cotton fabrics and polyester / cotton 6 inch square fabrics were obtained from Testfabrics. Six different stains were examined: coffee, grapes, spaghetti, blood, dressing, grass, make-up and pie filling. Each stain was deposited on two material fabrics for each fabric for each pretreatment type. In order to deposit the stain, the following stain deposition procedure was used. The starting materials for each stain are those commonly used in the laundry additive field. The starting materials for grass and pie filling were homogenized. All stains were deposited in an amount sufficient to form a saturated 1 inch circle stain on each fabric. After allowing the soaked material cloth to pass overnight, the material cloth was processed by the specified process. The processing conditions are as follows. For the improved formulation, comparative formulation and SHOUT ™, 8 grams of detergent was dissolved per liter of water. CLOROX ™ was used in an amount of 10 g per liter of water. Water having a temperature of 40 ° C. (104 ° F.) and a hardness of 150 ppm was used. The soaking time was 60 minutes. After the specified time, the solution in the bucket was discarded and each group of material cloths was washed and dried as described in Example 1.

After drying, the removal of stains on the material cloth was evaluated. The color difference was described as a ΔE value. Colorimetric values were obtained using an industry standard colorimeter (Minolta Corp, Ramsey, NJ), and ΔE was L * (brightness), a *, (green to magenta axis), and b *, (yellow~
The blue axis) was calculated using the method of measuring. Here, ΔE describes a vector difference between points in the space. The smallest color difference has the smallest ΔE value. The reported ΔE values are relative to a fabric with no stain.

  The results are shown in Tables 7 to 8 and FIG. Tables 7 and 8 show the performance of each treatment for each stain for each fabric type and are reported as ΔE units. The “Overall” column is the sum of the ΔE measurements across all stain types and indicates the overall stain removal capability of each treatment type. FIG. 3 is a graph showing the sum of the total ΔE for each stain for cotton and the total ΔE for each stain obtained for both poly / cotton and cotton. These results demonstrate that the improved formulation has the best overall stain removal performance compared to the comparative formulations, SHOUT ™ and CLOROX ™.

(Example 4)
In this example, the stain removal performance of the detergent compositions of the present invention containing various peracid precursors is compared.
Test cloths, stains, and other application procedures are as described in the three examples above, but in this example, dirty motor oil (DMO) is added to the stains to be examined. The detergent formulations shown in Table 1 were prepared in large quantities without the addition of peracid precursor. To different batches of this detergent formulation, each of the various peracid precursors was added as follows. Citric acid (Sigma Corp., St. Louis, MO) was added to a final concentration of 1% by weight. Adipic acid (Sigma Corp., St. Louis, MO) was added to a final concentration of 0.8% by weight. Tartaric acid (Sigma Corp., St. Louis, MO) was added to a final concentration of 1% by weight. For one aliquot of the detergent formulation, as a “no acid” formulation, no peracid precursor was included for comparison.

  After the stain was applied, the material cloth was allowed to pass overnight. The processing conditions are as follows. For all treatments, 8 grams of each detergent was dissolved per liter of water. Water having a temperature of 40 ° C. (104 ° F.) and a hardness of 150 ppm was used. The soaking time was 60 minutes. After the specified time, the solution in the bucket was discarded and each group of material cloths was washed and dried as described in Example 1.

  After drying, the removal of stains on the material cloth was evaluated as described in Example 3. The results are shown in Table 9 and Table 10, and FIG. Tables 9 and 10 show the performance of each treatment for each stain for each fabric type and are reported as ΔE units. The “Overall” column is the sum of the ΔE measurements across all stain types and indicates the overall stain removal capability for each treatment type. FIG. 4 is a graph showing the sum of the total ΔE for each stain for cotton and the total ΔE for each stain obtained for poly / cotton. These results demonstrate that all types of peracid precursors investigated improve the stain removal ability of the detergent formulations listed in Table 1.

(Example 5)
This example demonstrates formulations of the present invention containing adipic acid, tartaric acid, and L-tartaric acid, and stain removal as shown by the commercial formulations SHOUT ™, OXYPOWER ™ and CLOROX ™ Oxygen Action. Compare performance.

  The test cloth, treatment conditions, stains and other application procedures are similar to those described in Example 3 except that in this example only spaghetti, blood, grass, make-up and mustard were examined. . Adipic acid was tested for concentrations of 1% and 0.8% in the detergent composition formulated as described in Example 4. Both the tartaric acid treatment and the L-tartaric acid treatment are constituted by mixing the additives so that the final concentration is 1% by weight of tartrate, and performing the preparation as shown in Table 1.

  After the stain was applied, the material cloth was allowed to pass overnight. The processing conditions are as follows. For all treatments, except CLOLOX ™, 8 grams of each detergent was dissolved per liter of water. CLOROX ™ dissolved 10 grams per liter of water. Water having a temperature of 40 ° C. (104 ° F.) and a hardness of 150 ppm was used. The soaking time was 60 minutes. After the specified time, the solution in the bucket was discarded and each group of material cloths was washed and dried as described in Example 1.

  After drying, the removal of stains on the material cloth was evaluated as described in Example 3. The results are shown in Tables 11 and 12 and FIG. Tables 11 and 12 show the performance of each treatment for each stain and are reported as ΔE units. The “Overall” column is the sum of the ΔE measurements across all stain types and indicates the overall stain removal capability of each treatment type. FIG. 5 is a graph showing the sum of the total ΔE for each stain for cotton and the total ΔE for each stain obtained for poly / cotton. These results show that SHOUT ™ Oxy when all types of peracid precursors examined were used at the concentrations indicated in the detergent formulations of Table 1, as measured by ΔE. It shows better removal of stains compared to Power and CLOROX ™ Oxygen Action.

(Example 6)
In this example, comparative and commercially available formulations SHOUT ™ Oxypower, TIDE ™ With Bleach and CLOROX ™ for dye fading performance demonstrated by the formulations of the present invention comprising adipic acid and tartaric acid. Compare with Oxygen Action.

  A pre-dyed fabric is obtained from Testfabrics, Inc. and is supplied with the following industrial standard dyes: acid blue 113 for polyamide, direct blue 71 for cotton, and cotton for cotton. Reactive Blue 225, Reactive Brown 7 for cotton, Sulfur Blue 19 for cotton, Direct Blue 1 for cotton, Direct Red 80 for cotton, and Acid Red for nylon A cloth was prepared. Adipic acid was added to the comparative formulation to a final weight of 1%. Tartaric acid was added to the comparative formulation so that the final weight was 1% by weight of the tartaric acid equivalent.

  The processing conditions for the dyed material cloth are as follows. For all treatments, except CLOLOX ™, 8 grams of each detergent was dissolved per liter of water. CLOROX ™ dissolved 10 grams per liter of water. Water having a temperature of 40 ° C. (104 ° F.) and a hardness of 150 ppm was used. The soaking time was 60 minutes. After the specified time, the solution in the bucket was discarded and each group of material cloths was washed and dried as described in Example 1.

  After drying, the removal of stains on the material cloth was evaluated. The color difference was described as a ΔE value as described in Example 3. The smallest color difference has the smallest ΔE value. That is, the smaller ΔE is, the smaller the observed fading is. The reported ΔE values are compared to the untreated dyed fabric.

  The results are shown in Table 13 and FIG. Table 13 shows the fading performance of each treatment type for each dye as ΔE units. The “Overall” column is the sum of ΔE measurements across all dye types and indicates the overall fading performance of each treatment type. FIG. 6 is a graph showing the total of all ΔE for each dye type. These results show that the addition of the peracid precursors adipic acid and tartaric acid to the comparative formulation shows only a slight increase in fading compared to the comparative formulation and causes more fading than TIDE ™ with Bleach. It is difficult.

(Example 7)
In this example, the oxidation potential generated in water is compared between the comparative formulation and the improved formulation. In both the comparative and improved formulations, 8 g of each detergent composition was dissolved per liter of water at 40 ° C. (104 ° F.) and 150 ppm hardness. The pH was about 10.8. The measurement of ORP (oxidation-reduction potential) in millivolts was performed using an ORP electrode (Beckman Instruments, Fullerton, Calif.).

  The results are shown in FIG. 7, which is a graph showing the ORP produced by the comparative formulation and the improved formulation by logarithmic curve fitting. FIG. 7 demonstrates that the improved formulation provides an increase in the ORP in water and also increases the bleaching power as compared to the comparative formulation.

(Example 8)
This example demonstrates the storage stability of the particulate detergent formulation of the present invention. Two detergent formulations having the composition described in Table 14 were prepared for stability testing. One of these formulations further included sodium carbonate to compensate for the lack of sodium metasilicate metal protectant.

  The two formulations were prepared by mixing a sodium carbonate surfactant substrate with a solution containing two nonionic surfactants and a water-soluble substrate within 1 minute. The formulation was mixed for an additional 7 minutes to give a smooth and uniform material with most of the liquid absorbed in the powder. The remaining ingredients were then added and the mixture was mixed for an additional 3.5 minutes until a uniform mixture was obtained.

  Each of the two formulations was divided into two, their effective oxygen content was measured, and at 50% humidity, either about 22 ° C. (72 ° F.) or about 36 ° C. (96 ° F.), 60 Stored for days. FIG. 8 shows the results of the stability test as an exponential decay of the effective oxygen content of the two formulations over a 60 day storage period.

Example 9
This example compares two detergent formulations of the present invention with either an acid or neutralized peracid precursor source. Two test detergent formulations having the composition described in Table 15 were prepared.

  In this composition, the peracid precursor of tartaric acid, either in the acid state (tartaric acid) or in the neutralized state (potassium sodium tartrate), has a concentration of 1.5% by weight (ie 1.5% by weight tartaric acid). And 2.15 wt% sodium potassium tartrate). Each formulation was examined for stain cleaning ability on various fabrics in the test protocol described in the previous example. In any case, there was no significant difference in the cleaning performance of the two formulations with peracid precursors of tartaric acid in either acid or neutralized state.

  The above discussion of the present invention has been presented for purposes of illustration and description. The above is not intended to limit the invention to the forms disclosed. While the description of the invention includes one or more embodiments and specific variations and modifications, other variations and modifications are within the scope of the invention, for example, after understanding the disclosure of the present invention, It may fall within the common sense of those skilled in the art. Whether or not disclosed herein, and is not intended to provide any patentable subject matter to the public, alternative, interchangeable and / or equivalent structures, functions, scope or It is intended to obtain the right to include an acceptable range of alternative embodiments, including steps.

The figure which shows the result of the cloth washing | cleaning as described in Example 1 which compares the immersion for 1 hour, 3 hours, and 5 hours by the detergent composition of this invention. The figure which shows the result of the cloth washing | cleaning as described in Example 1 which compares the immersion for 1 hour, 3 hours, and 5 hours by the detergent composition of this invention. The figure which shows the result of the cloth washing | cleaning as described in Example 1 which compares the immersion for 1 hour, 3 hours, and 5 hours by the detergent composition of this invention. The results of the fabric test described in Example 2 for various stains on fabrics compared between the detergent composition of the present invention with a peracid precursor additive and a similar composition without a peracid precursor. FIG. The results of the fabric test described in Example 2 for various stains on fabrics compared between the detergent composition of the present invention with a peracid precursor additive and a similar composition without a peracid precursor. FIG. The results of the fabric test described in Example 2 for various stains on fabrics compared between the detergent composition of the present invention with a peracid precursor additive and a similar composition without a peracid precursor. FIG. A graph showing the total ΔE for various stains on cotton and poly / cotton when treated with the composition of the present invention and when treated with a commercial detergent. 3 is a graph showing the total ΔE for various stains treated with the detergent composition of the present invention compared to a composition lacking a peracid precursor. A graph showing the total ΔE for various stains on cotton or cotton blend compared with a formulation of the invention having various peracid precursors and a commercial detergent. FIG. 2 is a graph showing the total ΔE for various standard dyes on fabrics treated with detergent compositions of the present invention with various peracid precursors compared to commercial detergents. The graph which compared the oxidation-reduction potential generate | occur | produced with the detergent composition of this invention with the thing by the similar composition which does not contain an acid precursor by performing exponential curve fitting.

Claims (57)

a. An alkali peroxide salt coated with a surfactant;
b. A particulate solid detergent composition having improved storage stability, comprising a peracid precursor selected from carboxylic acids and salts thereof.   The detergent composition according to claim 1, wherein the alkali peroxide is selected from sodium percarbonate and sodium perborate.   The detergent composition of claim 1, wherein the alkali peroxide salt is present in an amount of about 20 wt% to about 80 wt%.   The detergent composition according to claim 1, wherein the peracid precursor is selected from dicarboxylic acids and tricarboxylic acids.   The peracid precursor is selected from oxalic acid, malonic acid, succinic acid, glutaric acid, adipic acid, pimelic acid, tannic acid, tartaric acid, and citric acid, and combinations thereof. The detergent composition according to 1.   The detergent composition of claim 5, wherein the peracid precursor is tartaric acid.   The detergent composition of claim 1, wherein the peracid precursor is present in an amount of about 0.1 wt% to about 10 wt%.   The detergent composition of claim 1, wherein the peracid precursor is present in an amount of about 0.7 wt% to about 2 wt%.   The detergent composition according to claim 1, wherein the surfactant comprises at least one nonionic surfactant.   The detergent composition according to claim 9, wherein the nonionic surfactant comprises 11 to 16 carbon alcohol ethoxylate. Alcohol ethoxylates are GENOPOL LA060 (TM), GENOPOL
11. Detergent composition according to claim 10, selected from UD-030 (TM) and combinations thereof.   The detergent composition of claim 1, wherein the composition further comprises a surfactant substrate.   The detergent composition according to claim 12, wherein the surfactant substrate is selected from sodium carbonate, sodium sulfate and combinations thereof.   The detergent composition according to claim 1, further comprising a metal protective agent.   The detergent composition according to claim 12, wherein the metal protective agent is sodium metasilicate.   The detergent composition according to claim 1, further comprising a dispersant.   The detergent composition according to claim 16, wherein the dispersant is selected from among acrylic-derived polymers and rosin soaps.   The detergent composition according to claim 16, wherein the dispersant is a maleic acid / acrylic acid copolymer.   The detergent composition according to claim 1, further comprising a water-soluble solvent.   The detergent composition according to claim 19, wherein the water-soluble solvent is selected from dipropylene glycol methyl ether, ethylene glycol butyl ether, and combinations thereof. A method for treating stains on a cloth,
Contacting the stained fabric with a detergent composition comprising an alkaline peroxide salt coated with a surfactant and a peracid precursor selected from carboxylic acids and salts thereof.   The method of claim 21, wherein the alkali peroxide is selected from sodium percarbonate and sodium perborate.   The method of claim 21, wherein the alkali peroxide is selected from sodium percarbonate and sodium perborate.   The method of claim 21, wherein the alkali peroxide salt is present in an amount of about 20 wt% to about 80 wt%.   The method of claim 21, wherein the peracid precursor is selected from among dicarboxylic acids and tricarboxylic acids.   The peracid precursor is selected from oxalic acid, malonic acid, succinic acid, glutaric acid, adipic acid, pimelic acid, tannic acid, tartaric acid, and citric acid, and combinations thereof. The method according to 21.   27. The method of claim 26, wherein the peracid precursor is tartaric acid.   The method of claim 21, wherein the peracid precursor is present in an amount of about 0.1 wt% to about 10 wt%.   The method of claim 21, wherein the peracid precursor is present in an amount of about 0.7 wt% to about 2 wt%.   The method of claim 21, wherein the surfactant comprises at least one nonionic surfactant.   32. The method of claim 30, wherein the nonionic surfactant comprises 11-16 carbon alcohol ethoxylate.   32. The method of claim 31, wherein the alcohol ethoxylate is selected from GENOPOL LA060 (TM), GENOPOL UD-030 (TM), and combinations thereof.   The method of claim 21, wherein the composition further comprises a surfactant substrate.   34. The method of claim 33, wherein the surfactant substrate is selected from sodium carbonate, sodium sulfate, and combinations thereof.   The method of claim 21, wherein the composition further comprises a metal protective agent.   36. The method of claim 35, wherein the metal protectant is sodium metasilicate.   The method of claim 21, wherein the composition further comprises a dispersant.   38. The method of claim 37, wherein the dispersant is selected from acrylic derived polymers and rosin soaps.   40. The method of claim 38, wherein the dispersant is a maleic acid / acrylic acid copolymer.   The method of claim 21, wherein the composition further comprises a water soluble solvent.   41. The method of claim 40, wherein the water soluble solvent is selected from dipropylene glycol methyl ether, ethylene glycol butyl ether, and combinations thereof. a. About 50% to about 60% by weight alkali peroxide salt coated with a surfactant;
b. A detergent composition comprising from about 0.7% to about 2% by weight of a peracid precursor selected from among carboxylic acids and salts thereof. a. About 30% to about 40% by weight sodium carbonate;
b. About 0.7 wt.% To about 2 wt.% Sodium metasilicate;
c. From about 0.2% to about 5% by weight of a maleic acid / acrylic acid copolymer;
d. About 0.3% to about 0.5% by weight of dipropylene glycol methyl ether;
e. About 0.2% to about 5% by weight of a linear 10-14 carbon alcohol ethoxylate;
f. 43. The detergent composition of claim 42, further comprising about 0.2 wt% to about 5 wt% 11 carbon alcohol ethoxylate. A method for producing a particulate solid detergent, comprising:
a. Contacting the alkali peroxide salt with a solution comprising a surfactant to form a coated alkali peroxide salt;
b. Adding an acid precursor to the coated alkali peroxide salt to form a particulate solid composition with improved storage stability.   45. The method of claim 44, wherein the surfactant is a nonionic surfactant.   46. The method of claim 45, wherein the nonionic surfactant comprises 11-16 carbon alcohol ethoxylate. Alcohol ethoxylates are GENOPOL LA060 (TM), GENOPOL
The method of claim 46, wherein the method is selected from UD-030 ™ and combinations thereof.   45. The method of claim 44, wherein the solvent is water soluble.   45. The method of claim 44, wherein the solvent is dipropylene glycol methyl ether. The contact step includes
a. Contacting the surfactant substrate with the solution;
b. 45. The method of claim 44, comprising mixing an alkali peroxide salt with a surfactant substrate, wherein the alkali peroxide salt absorbs the solution from the surface of the surfactant substrate.   45. The method of claim 44, wherein the alkali peroxide is selected from sodium percarbonate and sodium perborate.   45. The method of claim 44, wherein the alkali peroxide salt is present in the particulate solid detergent in an amount from about 20% to about 80% by weight.   45. The method of claim 44, wherein the peracid precursor is selected from among dicarboxylic acids and tricarboxylic acids.   The peracid precursor is selected from oxalic acid, malonic acid, succinic acid, glutaric acid, adipic acid, pimelic acid, tannic acid, tartaric acid, and citric acid, and combinations thereof. 45. The method according to 44.   55. The method of claim 54, wherein the peracid precursor is tartaric acid.   Following the addition of peracid precursors, nonionic surfactants, surfactant substrates, metal protectants, dispersants, enzyme stain removers, fluorescent brighteners, fluorescent agents, buffers, colorants, fragrances, 45. The method of claim 44, further comprising the additional step of adding a component selected from a detergent builder, a peroxide stabilizer and a bulking agent to the coated alkali peroxide salt. A dry particulate detergent composition comprising an alkali peroxide salt, a solvent, and a peracid precursor selected from among carboxylic acids and salts thereof,
a. Creating a solution by combining a surfactant with a solvent;
b. Contacting an alkali peroxide with a solution to form an alkali peroxide salt;
c. A dry particulate detergent composition produced by a method comprising a step of obtaining a particulate solid composition having improved storage stability in addition to an alkali peroxide coated with a peracid precursor.

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