MXPA99007990A - Soaker compositions - Google Patents

Abstract

Soaking compositions are disclosed which comprise oxygen bleach, a sorbitan ester in combination with a highly alkoxylated nonionic surfactant. Said compositions are diluted in water to form soaking liquors. The invention is particularly effective in removing particulate soils like silt and clay from fabrics as well as enzymatic stains and/or bleachable stains.

Description

REMOVAL COMPOSITIONS TECHNICAL FIELD The present invention relates to the cleaning of fabrics under soaking conditions, that is, in conditions where the fabrics are allowed to soak in a soaking solution consisting of water and detergent ingredients, typically without undergoing any mechanical agitation, either as a first step before a typical washing operation, or as a single step.

BACKGROUND OF THE INVENTION The fabric soaking operations have been described in the art. In such soaking operations, the fabrics are left in contact with a soaking solution for a prolonged period, typically in the range of a few minutes to overnight or even 24 hours. This washing procedure has the advantage that it maximizes the contact time between the fabrics and the key active ingredients of the soaking solution. It also has the advantage that it reduces or eliminates the need for a typical laundry operation that involves the need for mechanical agitation, or that improves the efficiency of the typical subsequent laundry operation.

Such soaking operations are typically desirable to remove dirt difficult to remove from fabrics, such as particulate soils such as sludge, mud sludge and / or clays. For example, clays usually have a microcrystalline mineral structure (for example, hydrated aluminum silicate such as lita, montmorillonite, kaolinite and the like) in the presence of an organic fraction. The organic fraction can contain a variety of compounds (for example humic acid, fulvic acid, plant / animal biomass and the like). The clays may also contain various kinds of metals (eg, magnesium, calcium, potassium, iron and the like). However, such particulate stains are particularly difficult to remove from fabrics. In fact, it is believed that very fine grains of grit such as clays or sludge from sludge, typically below 0.002 mm in size, can be embedded between the fibers of the fabrics and adhere firmly to the surface of the fibers. The problem is particularly acute with the socks that are the most exposed to pick up silt and clay. Furthermore, said soaking operations are not completely satisfactory considering the stain removal performance supplied on enzymatic stains or even bleach stains. Enzymatic spots are typically composed of carbohydrates and proteinaceous soils, such as blood. It has now been observed that enzymatic stains can act as a glue for particulate soils on fabrics, whereby the removal of such enzymatic stains can facilitate the removal of particle stains from fabrics. It is therefore an object of the present invention to improve the removal of dirt stains from particles, mud and / or clay, as well as from enzymatic stains and / or bleaching spots. It has been discovered that this object can be accomplished by soaking fabrics in an aqueous soaking solution consisting of an effective amount of a soaking detergent composition consisting of an oxygen bleach and a highly alkoxylated nonionic surfactant, as defined in US Pat. present previously. In fact, it has been discovered that said highly alkoxylated nonionic surfactant and oxygen bleach, in a soaking composition, provides improved stain removal performance on grime difficult to remove such as particulate soils, enzymatic stains and / or low bleaching spots. soaking conditions (i.e., when left in contact for extended period typically from more than 1 hour to 24 hours), compared to the stain removal performance supplied with the same composition that is free of said highly nonionic surfactant alkoxylated. Thus, in its broadest aspect, the present invention encompasses a process for soaking fabrics, wherein said fabrics are submerged for more than one hour in a soaking solution consisting of water and an effective amount of a composition consisting of a highly alkoxylated nonionic surfactant and an oxygen bleach, as defined herein , and then removed from the soaking solution. An advantage of the present invention is that the stain removal performance, when soaking a fabric in the presence of a soaking composition consisting of an oxygen bleach and a highly alkoxylated nonionic surfactant as defined herein, is improves even in the presence of relatively high levels of hardness ions. In fact, the presence of hardness ions (calcium or magnesium ions), which occur naturally in the soaking solution, in particular, can reduce the yield of the surfactant and, if necessary, precipitate the surfactants from the solution Soak as a calcium or magnesium salt. This phenomenon occurs less when an alkoxylated nonionic surfactant is used as defined herein. Accordingly, the manufacturer of the soaking detergent can make use of detergency builders which are not the ones that work the most by sequestering free hardness ions, and in this way can use less expensive builders in said soaking composition. In addition, it has been discovered that the performance of removing stains on particulate soils, enzymatic stains and / or bleaching stains is further improved by combining said highly alkoxylated nonionic surfactant and oxygen bleach with a sorbitan ester as defined in present later, in a detergent composition for soaking. In this manner, the present invention encompasses a detergent composition for soaking consisting of a sorbitan ester as defined herein, a highly alkoxylated nonionic surfactant as described herein, and an oxygen bleach, as well as a process for soaking fabrics in a soaking solution formed with said detergent composition for soaking. An advantage of the present invention is that it not only provides improved particulate removal performance, but also the redeposition of soils on fabrics under prolonged soaking conditions is avoided. In addition, the soaking compositions of the present invention which consist of a sorbitan ester, said highly alkoxylated nonionic surfactant and oxygen bleach also provide effective stain removal performance over other types of stains such as greasy stains, eg oil dirty motor, spaghetti sauce.

TECHNICAL BACKGROUND EP-A-736 594 discloses soaking compositions consisting of a sorbitan ester in combination with a high amount of a builder and a soil suspension system consisting of a compound selected from citric acid or citrates, silicates , zeolites, polycarboxylates, phosphates and mixtures thereof. Oxygen bleach is included among the optional ingredients. Alkoxylated nonionic surfactants are not disclosed or exemplified.

BRIEF DESCRIPTION OF THE INVENTION The present invention encompasses a granular soaking composition comprising: from 0.001% to 15% by weight of the total composition of a sorbitan ester according to the formula CsHg? 2 (C2H4?)? R1R2 3 where x is an integer from 0 to 40, R ^ R2 are independently OH or (CnH2n +?) COO, and R3 is a group (CnH2p +?) COO, where n is an integer of 11 to 17. From 0.001% to 20% by weight of the total composition of a non-ionic akoxylated surfactant according to the formula RO- (A) nH, wherein R is a straight or branched hydrocarbon chain, saturated or unsaturated, substituted or unsubstituted having from 6 to 40 carbon atoms, A is an alkoxy group having from 2 to 10 carbon atoms, and wherein n is an integer from 9 to 100. And an oxygen bleach.

The present invention further encompasses a process for soaking fabrics, wherein said fabrics are immersed in a soaking solution consisting of water and an effective amount of a composition as described herein, for an effective time, and then removed from the fabric. said soaking solution. In its broadest aspect, the present invention encompasses a process for soaking fabrics, wherein said fabrics are immersed for more than one hour in a soaking solution consisting of water and an effective amount of a composition consisting of an oxygen bleach. and an alkoxylated nonionic surfactant as defined herein, and then removed from said soaking solution.

DETAILED DESCRIPTION OF THE INVENTION The present invention encompasses a composition and a process for soaking fabrics. The composition, hereinafter referred to as the soaking composition, is used in the soaking process.

A. The Composition: The granular compositions herein comprise at least one sorbitan ester, a particular non-ionic alkoxylated surfactant as defined herein and an oxygen bleach.

The sorbitan ester Accordingly, the first essential ingredient of the compositions of the present invention is a sorbitan ester according to the formula C5H9? 2 (C2H4?)? R1R2R3 where x is an integer from 0 to 40, R1: R2 are independently OH or (CnH2n +?) COO, and R3 is a group (CnH2n-n) COO, where n is an integer from 11 to 17. In the preferred compositions herein, x is 0 or 20, and the most preferred composition herein consists of polyethoxylated sorbitan tristerate (20), ie C5H9O2 (C2H4O) 2o (C-i7H35COO) 3- or polyethoxylated sorbitan monostearate ( 20), ie C5H9O2 (C2H4?) 2o (OH) 2 (C17H35COO), or sorbitan monostearate, is dcir C5H9? 2 (OH) 2 (C17H35COO), or sorbitan monopalmitate, ie, C5H9? 2 (OH ) 2 (Ci5H3iCOO), or mixtures thereof. All these materials are commercially available under various trade names, such as Glicosperse TS 20 of lonza (polyethoxylated sorbitan sorbate), Glicosperse S 20 of Lonza (polyethoxylated sorbitan monostearate), Radiasurf 7145 of Fina (sorbitan monostearate), Radiasurf 7135 of Fina (sorbitan monopalmitate), Armotan MP from Akzo (sorbitan monopalmitate). It has also been discovered that combining ethoxylated sorbitan esters with non-ethoxylated sorbitan esters provides better performance than any type alone.

The soaking compositions herein consist of 0.001% to 15% by weight of the total composition of said sorbitan ester or mixtures thereof, preferably from 0.01% to 10%, more preferably from 0.1% to 5% and more preferably from 0.5% to 4%.

The nonionic surfactant The second main ingredient of the compositions of the present invention is an alkoxylated nonionic surfactant according to the formula RO- (A) nH, wherein R is a straight or branched hydrocarbon chain, saturated or unsaturated, substituted or not Substituted having from 6 to 40 carbon atoms, A is an alkoxy group having from 2 to 10 carbon atoms, and wherein n is an integer from 9 to 100 or a mixture thereof. Preferably R is an alkyl group or branched or linear, saturated or unsaturated, substituted or unsubstituted aryl group having from 6 to 40 carbon atoms, preferably from 8 to 25, more preferably from 12 to 20. Typical aryl groups include the C12-C18-benzene alkyl groups. Preferably n is an integer from 9 to 100, more preferably from 10 to 80 and more preferably from 10 to 30. A preferably is an alkoxy group having from 2 to 8 carbon atoms, preferably from 2 to 5 and more preferably is propoxy and / or ethoxy.

Accordingly, the alkoxylated nonionic surfactants suitable for use in the present invention are Dobanoid® 91-10 (R is a mixture of C9 to C11 alkyl chains, A is ethoxy, n is 10) Luthensol AR® or agents AO® surfactants (wherein R is a mixture of unbranched C18 or C13-C15 alkyl chain, A is ethoxy, and n may be 11, 18, 25, 50 or 80), or mixtures thereof. These Dobanoi® surfactants are commercially available from SHELL, while the Luthensol® surfactants are available from BASF. Suitable chemical processes for preparing the alkoxylated nonionic surfactants for use herein include the condensation of the corresponding alcohols with alkylene oxide, in the desired proportions. Such methods are well known to the person skilled in the art and have been extensively described in the art. Such alkoxylated nonionic surfactants are particularly suitable for use herein as they provide improved particulate removal performance. In fact, it is speculated that they act as a suspending agent for soils, that is, they allow the suspension of particulate soils and prevent / prevent redeposition of said soils. The soaking compositions herein consist of 0.001% to 20% by weight of the total of the composition of said alkoxylated nonionic surfactant, as defined herein, or a mixture thereof, preferably from 0.01% to 15%, more preferably from 0.1% to 10%, and more preferably from 0.5% to 5%.

Oxygen bleach As a third essential ingredient, the compositions according to the present invention consist of an oxygen bleach or a mixture thereof. In fact, oxygen bleaches provide a lot of benefits such as bleaching stains, deodorization as well as disinfectant. The sorbitan esters and the alkoxylated nonionic surfactants as defined herein have a further particular advantage that they are resistant to oxidation by oxygen bleaches. The oxygen bleach in the composition may come from a variety of sources, such as hydrogen peroxide or any of the hydrogen peroxide addition compounds, or organic peroxyacid, or mixtures thereof. By hydrogen peroxide addition compounds, it means compounds that are formed by the addition of hydrogen peroxide to a second chemical compound, which may be for example an inorganic salt, urea or organic carboxylate to provide the addition compound. Examples of the hydrogen peroxide addition compounds include inorganic perhydrate salts, the compounds that hydrogen peroxide forms with organic carboxylates, urea, and the compounds in which hydrogen peroxide has clathrinthines.

Examples of inorganic perhydrate salts include perborate salts, percarbonate, perfosphate and persilicate. The inorganic perhydrate salts are usually the alkali metal salts. The alkali metal salts of percarbonate, perborate or mixtures thereof, are the preferred inorganic perhydrate salts for use herein. The preferred alkali metal salt of percarbonate is sodium percarbonate. Other suitable oxygen bleaches include persulfates, particularly potassium persulfate K2S2O8 and sodium persulfate.

Na2S2? S. Examples of inorganic perhydrate salts include perborate, percarbonate, perphosphate and persilicate salts. The inorganic perhydrate salts are usually the alkali metal salts. Typically, the soaking compositions in the present invention comprise from 0.01% to 80% by weight of the total composition of an oxygen bleach or mixtures thereof, preferably from 5% to 45% and more preferably from 10% to 40%. %. The soaking compositions of the present invention are granular compositions. These compositions can be made by a variety of methods well known in the art, including dry blending, spray drying, agglomeration and granulation and combinations thereof. The compositions herein can be prepared with different bulk densities, from conventional granulated products to so-called "concentrated" products (ie, with a bulk density above 600 g / l).

Optional ingredients The soaking compositions of the present invention may further comprise a variety of other ingredients. Preferably the compositions herein further comprise a bleach activator or a mixture thereof of up to 30% by weight of the total composition. Examples of suitable compounds of this type are described in British patent GB 1 586 769 and GB 2 143 231. Preferred examples of said compounds are tetracetyl-tilenediamine, (TAED) sulfonate 3,5,5-trimethyl hexanoyloxybenzene sodium, acid diperoxy dodecanoic, as described for example in US Pat. No. 4,818,425 and peroxyadipic acid nonyl amide as described for example in US Patent 4 259 201 and n-nonacryloxybenzenesulfonate (NOBS), and acetyl triethyl citrate (ATC) as is described in European patent application 91870207.7. Also particularly preferred is N-acyl caprolactam selected from the group consisting of benzoyl caprolactam, octanil caprolactam, nonanoyl caprolactam, hexanoyl caprolactam, decanoyl caprolactam, undecanoyl caproiactam, formyl caprolactam, acetyl caprolactam, propanoyl caprolactam, butanoyl caprolactam, pentanoyl caprolactam substituted or unsubstituted . The soaking compositions herein may consist of blends of said bleach activators. Preferred blends of said bleach activators herein consist of n-n-nyloxy-oxybenzene sulfonate (NOBS) together with a second bleach activator having a low tendency to generate diacyl peroxide, but supplying mainly peracid. The said second bleach activators may include tetracetyl-tilenediamine, (TAED), acetyl triethyl citrate (ATC), acetyl caprolactam, benzoyl caprolactam and the like or mixtures thereof. In fact, it has been discovered that mixtures of bleach activators consisting of n-nonacryloxybenzensulfonate and the said second bleach activators, contribute to further boost the removal performance of particulate soils while at the same time exhibiting good performance on sensitive soils. to the diacyl peroxide (for example beta-carotene) and on peracid-sensitive soils (for example body stains). Accordingly, the soaking compositions herein may comprise from 0% to 15% by weight of the total n-n-n-octaoxybenzenesulfonate composition, preferably from 1% to 10% and more preferably from 3% to 1% and from 0% to 15% by weight of the total composition of said second bleach activator preferably from 1% to 10% and more preferably from 3% to 7%. The compositions herein may consist of an acidifier system among the preferred optional ingredients. The object of said acidifier system is to control the alkalinity generated by the available oxygen source and any alkaline compounds present in the wash solution. Said system consists of an anhydrous acidifying agent, or mixtures thereof, which needs to be incorporated into the product in an anhydrous form, and have good stability in an oxidizing environment. Acidic acidifying agents suitable for use herein are carboxylic acids such as citric acid, adipic acid, glutaric acid, ketoglutaric acid, citralic acid, tartaric acid and maleic acid or their salts or mixtures thereof. Other suitable acidifying agents include sodium bicarbonate, sodium sesquicarbonate and silicic acid. The most preferred acidifying systems for use herein consist of citric acid and / or sodium citrate. In fact citric acid can be used in its acidic form or in the form of its salts (mono-, di-, tri-, salts) and in all its anhydrous and hydrated forms, or mixtures thereof. It can act additionally as a builder and detergent, and is biodegradable. The compositions according to the present invention comprise up to 20% by weight of the total of the anhydrous citric acid composition, preferably from 5% to 15%, more preferably almost 10%. The compositions herein may consist of a silicate alkali metal salt, or mixtures thereof, among the preferred optional ingredients. The preferred silicate alkali metal salt to be used herein is sodium silicate. In the preferred embodiment herein wherein the soaking compositions consist of an oxygen bleach, it has been discovered that the decomposition of the available oxygen produced in the soaking solutions with the solution of the soaking solution is reduced by the presence of minus 40 parts per million of sodium silicate in said soaking solutions. Any type of alkali silicate metal salt can be used herein, including crystalline forms as well as amorphous forms of said silicate alkali metal salt or mixtures thereof. The suitable crystalline forms of sodium silicate to be used are the crystalline layered silicates of the granular formula: NaMSi 2? + ?. and H2O Where M is sodium or hydrogen, x is a number from 1.9 to 4 and y is a number from 0 to 20, or mixtures thereof. Crystalline layered sodium silicates of this type are described in EP-A-164 514 and methods for their preparation are described in DE-A-34 17 649 and DE-A-37 42 043. For objects of the present invention, x in the above general formula has a value of 2, 3 or 4 and is preferably 2. More preferably M is sodium and y is 0 and the preferred examples of this formula consist of the forms a, b, g and d of Na 2 Si 2 - 5 These materials are available from Hoechst AG FRG as NaSKS-5, NaSKS-7, NaSKS-11 and NaSKS-6 respectively. The most preferred material is d- Na 2 Si 2, NaSKS-6. The crystalline layered silicates are incorporated in the soaking compositions herein, either as dry mixed solids, or as solid components of agglomerates with other components. Suitable amorphous forms of sodium silicate for use herein have the following general formula: wherein M is sodium or hydrogen and x is a number from 1.9 to 4, or mixtures thereof. Preferred to be used herein are amorphous forms of Si2? SNa2 ?. Suitable zeolites for use herein are aluminosilicates including those having the empirical formula: Mz (zAIO2.ySiO2) Where M is sodium, potassium, ammonium, or substituted ammonium, z is 0.5 to 2; and y is 1; this material has a magnesium ion exchange capacity of at least 50 milligrams equivalent of CaCO3 hardness per gram of anhydrous aluminosilicate. Zeolites having the formula are preferred: Nazi (AIO2) z (siO2) yú.xH2O) Where z and y are integers of at least 6, the molar ratio of z to y is on the scale of 1.0 to 0.5, and x is an integer of 15 to 264. Useful materials are commercially available. These aluminosilicates may be of amorphous or crystalline structure and may be naturally occurring aluminosilicates or synthetically derived. A method for producing aluminosilicate ion exchange materials is described in the U.S.A. 3,985,669 to Krumme! and others, from October 12, 1976. The synthetic crystalline aluminosilicate ion exchange materials useful herein are described under the designations Zeolite A, Zeolite P (B), and Zeolite X. In an especially preferred embodiment, the material of crystalline aluminosilicate ion exchange has the formula: Na12i (AIO2) 12 (SiO2) 12u.xH2O Where x is from 20 to 30, especially nearly 27. This material is known as Zeolite A. Preferably, the aluminosilicate has a particle size of 0.1 -10 microns in diameter. Typically, compositions herein may comprise from 0.5% to 15% by weight of the total composition of a silicate alkali metal salt or mixtures thereof, preferably from 1% to 10% and more preferably from 2% to 7% The composition herein may also consist of a builder among preferred optional ingredients. All detergency builders known to those skilled in the art can be used herein. Phosphate builders suitable for use herein include sodium potassium tripolyphosphate, pyrophosphate, polymeric metaphosphate having a degree of polymerization of 6 to 21, and orthophosphate. Other phosphorus builder compounds are described in the U.S. Patents. Nos. 3,159,581; 3,213,030; 3,422,021; 3,422,137; 3,400,176; and 3,400,148, incorporated herein by reference. Polycarboxylate builders suitable for use herein include ether polycarboxylates, including oxydisucinate, as described in Berg, U.S. Patent 3,128,287, April 7, 1964, and Lambrti et al., In U.S. Pat. 3,635,830, dated January 18, 1972. See also detergent builders "TMS / TDS" of the U.S. patent. No. 4,663,071 issued to Bush et al., May 5, 1987. Suitable ether polycarboxylates also include cyclic compounds, particularly alicyclic compounds, such as those described in U.S. Pat. 3,923,679; 3,835,163; 4,120,874 and 4,102,903. Other useful builders include ether hydroxypolycarboxylates, 1,3-trihydroxybenzene-2,4,6-trisulfonic acid, ammonium and substituted ammonium salts of polyacetic acids such as etiiendiamine tetraacetic acid and nitrilotriacetic acid, as well as polycarboxylates such as acid mellitic, succinic acid, oxydisuccinic acid, polymaleic acid, benzen 1, 3,5-tricarboxylic acid, carboxymethyloxysuccinic acid. and soluble salts thereof. Also suitable in the soaking compositions of the present invention are the 3,3-dicarboxy-oxa-1,6-hexanedioates and the related compounds described in the US patent. 4,566,984, Bush, January 28, 1986. Succinic acid builders include the C5-C20 succinic alkyl and aikenyl acids and salts thereof. A particularly preferred compound of this type is dodecenylsuccinic acid. Specific examples of succinate builders include lauryl succinate, myristiisuccinate, palmitylsuccinate, 2-dodecenylsuccinate (preferred), 2-pentadecenylsuccinate, and the like. Lauryl succinates are the preferred builders of this group, and are described in European patent application 86200690.5 / 0,200,263, November 5, 1986. Other suitable polycarboxylate builders are described in the U.S.A. 4,144,226, Crutchfield et al., March 13, 1979 and in the U.S. patent. 3,308,067, Diehl, March 7, 1967. See also Diehl, U.S. Patent. 3,723,322. Other polycarboxylate builders suitable for use herein include builders according to the formula: R1 _Yp. _ (_ CH2-CR3_J R2 CO2M n wherein Y is a comonomer or mixture of comonomers; R1 and R2 are end groups of stable polymer in bleach and alkali; R3 is H, OH or C- alkyl; M is H, alkali metal, alkaline earth metal; ammonium or substituted ammonium; p is from 0 to 2; and n is at least 10; or mixtures thereof. Preferred polymers for use herein fall into two categories. The first category belongs to the class of copolymeric polymers that are formed from unsaturated polycarboxylic acid such as maleic acid, citraconic acid, itaconic acid, tamaronic acid and salts thereof as a first monomer, and a monocarboxylic acid unsaturated as acid acrylic or a C1-C4 acrylic alkyl-acrylic acid as the second monomer. With reference to formula I above, the polymers belonging to said first class are those in which p is not 0 and Y is selected from the acids listed hereinabove. Preferred polymers of this class are those according to formula I above, wherein Y is maleic acid. Further, in the preferred embodiment, R3 and M are H, and n is such that the polymers have a molecular weight of from 1000 to 400,000 atomic mass units. The second category of preferred polymers for use herein belongs to the class of polymers in which, with reference to formula I above, p is 0 and R3 is H or C? - alkyl. In a preferred embodiment n is such that the polymers have a molecular weight of from 1000 to 400,000 units of atomic mass. In a most preferred embodiment, R3 and M are H.

The alkali stable polymer end groups R1 and R2 in formula I above include suitably alkyl groups, oxyalkyl groups and alkyl carboxylic acid groups and salts and esters thereof. In the above, n, the degree of polymerization of the polymer can be determined from the average weight of the polymer molecular weight by dividing the latter by the average molecular weight of the monomer. Thus, for a maleic-acrylic copolymer having an average molecular weight of 15,500 and consisting of 30 mol% of units derived from maleic acid, n is 182 (ie 15,500 / (116 x 0.3 + 72 x 0.7)). Columns of controlled temperature at 40 ° C against the standards of polystyrene-sodium sulfonate polymer, available from Polymer Laboratories Ltd., Shropshire, UK, polymer standards being 0. 15M sodium dihydrogen phosphate and 0.02M tetramethylammonium hydroxide at pH 7.0 in 80/20 water / acetonitrile. Of all the above, the most preferred polymers for use in the present invention are those of the first category wherein n is on average 100 to 800, preferably 120 to 400. Preferred builders for use herein are polymers of maleic or acrylic acid, or maleic acid and acrylic copolymers. Typically, the compositions of the present invention consist of up to 50% by weight of the total composition of a builder or mixtures thereof, preferably from 0.1% to 20% and more preferably from 0.5 to 11%. Preferably the soaking compositions herein also comprise a chelating agent or mixtures thereof. Chelating agents are desired herein since they help to control the level of free heavy metal ions in the soaking solutions, thus avoiding the rapid decomposition of the oxygen released by the oxygen bleach. Suitable aminocarboxylate chelating agents which can be used herein include diethylene diamine pentaacetic acid, ethylenediamine tetraacetates (EDTA), N-hydroxyethylethylenediamine triacetates, nitrilotriacetates, ethylenediamine tetrapropionates, triethylenetetraamine hexaacetates, and ethanoldiglicins, metalalkaline ammonium salts and substituted ammonium thereof, or mixtures thereof. Particularly suitable EDDS compounds are the free acid forms and the sodium or magnesium salts or complexes thereof. Other suitable chelating agents can also be organic phosphonates, including amino alkylene poly (alkylene phosphonate), ethane 1-hydroxy metal alkaline diphosphonates, nitrile trimethylene phosphonates, ethylenediamine tetramethylene phosphonates and diethylenetriamine pentamethylene phosphonates. The phosphorus compounds may be present either in their acid form or in the form of their alkali metal salt. Preferably the organic phosphonate compounds where they are present are in the form of their magnesium salt.

The soaking compositions in the present invention can accordingly consist of from 0% to 5% by weight of the total composition of said chelating agents, preferably from 0% to 3%, more preferably from 0.05% to 2%. The compositions herein may also consist of other surfactants on the sorbitan ester and the alkoxylated nonionic surfactant as described herein above. Such surfactants may be desirable as they additionally contribute to the benefit of the present composition: ie, improved stain removal on particulate soils as well as other types of soils such as enzymatic and / or grease. Said surfactants may be present in the soaking compositions according to the present invention, on the sorbitan ester and the alkoxylated nonionic surfactant as described hereinbefore, in amounts of 0.1% to 50% by weight of the total of the composition, preferably from 0.1% to 20%, and more preferably from 1% to 10%. The surfactants to be used herein include nonionic surfactants, anionic surfactants, cationic surfactants, amphoteric surfactants, zwitterionic surfactants, and mixtures thereof. Suitable surfactant for use herein includes water soluble salts or acids of the formula ROSO3M wherein R is preferably a C10-C24 hydrocarbyl, preferably an alkyl or hydroxyalkyl having a C10-C20 alkyl component, more preferably a C12-C18 alkyl or hydroxyalkyl, and M is H or a cation, for example an alkali metal cation (for example sodium, potassium, lithium), or ammonium or substituted ammonium (for example methyl-, dimethyl-, and trimethyl ammonium and quaternary ammonium cations derived from alkylamines such as ethylamine, diethylamine, triethylamine, and mixtures thereof, and the like). Typically, the C12-16 alkyl chains are preferred for lower wash temperatures (for example below 50 ° C) and the C16-18 alkyl chains are preferred for higher wash temperatures (for example above) 50 ° C). Other suitable anionic surfactants for use herein are the water soluble salts or acids of the formula RO (A) mS? 3M wherein R is an unsubstituted C10-C24 alkyl or hydroxyalkyl group having an alkyl component of C10 -C24, preferably a C12-C20 alkyl or hydroxyalkyl, more preferably a C12-C18 alkyl or hydroxyalkyl, A is an ethoxy or propoxy unit, m is larger than zero, typically between 0.5 and 6, more preferably between 0.5 and 3, and M is H or a cation which may be, for example, a metal cation (eg, sodium, potassium, lithium, calcium, magnesium, etc.), ammonium cation or substituted ammonium cation. The ethoxylated alkyl sulfates as well as the propoxylated alkyl sulfates are contemplated herein. Specific examples of substituted ammonium cations include methyl-, dimethyl-, trimethylammonium and quaternary ammonium cations, such as tetramethylammonium, dimethyl pipiridinium and cations derived from alkanolamines such as ethylamine, diethylamine, triethylamine, mixtures thereof and the like. Illustrative surfactants are polyethoxylate sulfate (1.0) of C12-C18 alkyl, C12-C? 8E (1.0) M), polyethoxylate sulfate (2.25) of C12-C18 alkyl, C12-C? 8E (2.25) M) , polyethoxylate sulfate (3.0) of C12-C18 alkyl, C? 2-C? 8E (3.0), and polyethoxylate sulfate (4.0) of C12-C18 alkyl, C? 2-C18E (4.0) M), where M is conveniently selected from sodium and potassium.

Other surfactants useful for detersive objects can be used herein. These may include salts (including, for example, sodium, potassium, ammonium, and substituted ammonium salts, such as mono-, di-, and triethanolamine) soap, linear C9-C20 alkylbenzenesulfonates, C8-C24 olefinsulfonates. , sulfonated polycarboxylic acids prepared by sulfonation of the pyrolyzed product of alkali earth metal citrates, for example, as described in British Patent Specification No. 1, 082,179, C8-C24 alkyl polyglycol ether sulphates (containing up to 10 moles of ethylene oxide); alkyl ester sulphonates such as C14-16 methyl sulfonate ester; acylglycerol sulfonates, fatty oleylglycerol sulphates, alkylphenolthylene oxide ether sulfates, alkyl phosphates, setionates such as acyl isethionates, N-acyl taurates, alkyl sucinamates and sulfosucinates, sulfosucinate monoesters (especially saturated C12-C18 monoesters and unsaturated), sulfosucinate diesters (especially saturated and unsaturated C3-C14 diesters), acyl sarcosinates, alkylpolysaccharide sulfates such as alkylpolyglucoside sulfates (the non-sulphonated nonionic compounds described below), branched primary alkyl sulfates polyethoxy alkyl carboxylates such as those of the formula RO (CH 2 CH 2?) kCH 2 COO-M + wherein R is a C 8 -C 22 alkyl, k is an integer from 0 to 10, and M is a soluble salt-forming cation. Resin acids and hydrogenated resin acids are also suitable, such as rosin, hydrogenated rosin, and resin acids and hydrogenated resin acids present in or derived from wood oil. Additional examples are given in "Surface Active Agents and Detergents" (Vol. I and II by Schwartz, Perry and Berch). A variety of such surfactants is also generally described in the US patent. 3,929,678, from December 30, 1975 to Laughlin et al., In column 23 row 58 through column 29, row 23 (incorporated herein by reference).

Other anionic surfactants suitable for use herein may also include those of the formula R-SO3M, wherein R is a substituted or unsubstituted, saturated or unsaturated, straight or branched hydrocarbon chain, having from 6 to 40 carbon atoms and M is H or a cation. Preferably, R is a substituted or unsubstituted, saturated or unsaturated, linear or branched alkyl group having from 6 to 40 carbon atoms, preferably from 8 to 30, more preferably from 10 to 25 and more preferably from 12 to 18. Preferably M is a cation which may be for example a metal cation (for example, sodium, potassium, lithium, calcium, magnesium, etc.), ammonium or substituted amionium (for example, methyl-, dimethyl-, and cationic cations). trimethyl ammonium and quaternary ammonium cations, such as tetramethylammonium and dimethyl piperidinium cations and quaternary ammonium cations derived from alkylamines such as ethylamine, diethylamine, triethylamine and mixtures thereof and the like). Anionic sulfonates suitable for use herein are sodium paraffin sulfonates. These may be commercially available from Hoescht under the Hostapur® or Hostatat® trademark.

The compositions herein may additionally comprise a filler, such as inorganic filler salts such as alkali metal carbonates, bicarbonates and sulfates. Such fillers, for example sodium bicarbonate, can also act as acidifying agents, as described hereinafter. Accordingly, sodium bicarbonate and sodium sulfate are the preferred fillers for use herein.

Typically, the compositions of the present invention comprise up to 50% by weight of the total composition of a filler or mixtures thereof, preferably from 0.1% to 20%, and more preferably from 0.5% to 10%.

The compositions herein typically also consist of an enzyme or a mixture thereof, preferably the compositions herein consist of a protase or mixtures thereof. Protease enzymes are normally present in preferred embodiments of the invention at levels sufficient to provide 0.005 to 0.2 Anson units (AU) of activity per gram of composition. The proteolytic enzyme can be of animal, vegetable, or preferably microorganism origin. More preferred is a serine proteolytic enzyme of bacterial origin. Purified or non-purified forms of the enzyme can be used. Proteolytic enzymes produced by chemically or genetically modified mutants are included by definition, since they are variants of nearby structural enzyme. Particularly preferred as a proteolytic enzyme is the bacterial serine proteolytic enzyme obtained from Bacillus, Bacillus subtilis, and / or Bacillus licheniformis. Suitable commercial proteolytic enzymes include Alcalase®, Esperase®, Durazym®, Savinase®, Maxatase®, Maxacal® and Maxapem® (genetically engineered Maxacal protein); Purafec® and subtilisin BPN and BPN 'are also commercially available. Preferred proteolytic enzymes also include modified bacterial serine proteases, such as those described in European Patent Application Serial No. 87303761, 8 of April 28, 1987 (particularly pages 17, 24 and 98) and which is called in the present "Protease B", and in the European patent application 199,404, Venegas, published on October 29, 1986, which refers to a modified bacterial serine proteolytic enzyme, which is called "Protease A" herein. More preferred is the so-called "Protease C", which is a triple variant of an alkaline serine protease from Bacillus in which valine is replaced by tyrosine at position 104, asparagine replaced by serine at position 123 and threonine replaced by alanine at position 274. Protease C is described in EP 90915958.4, corresponding to WO 91/06637, published May 16, 1991, which is incorporated herein by reference. Genetically modified variants, particularly Protease C, are also included herein.

Also suitable for use herein is a protease referred to as "Protease D" which is a variant of carbonyl hydrolase having an amino acid sequence that is not found in nature, which is derived from a carbonyl hydrolase precursor substituting a different amino acid for a plurality of amino acid residues at a position in said carbonyl hydrolase equivalent to the +76 position in combination with one or more amino acid residue positions equivalent to those selected from the group consisting of +99, +101, + 103, +107, and +123 in Bacillus amyloliauefaciens subtilisin as described in concurrently filed patent applications of A. Baeck, CK Ghosh, P.P. Greycar, R.R. Bott and L.J. Wilson, entitled "Protease-Containing Cleaning Compositions" which has the serial number of E.U.A. No. 08 / 136,797 (P & G Case 5040), and "Bleaching Compositions Comprising Protease Enzymes" having the serial number of E.U.A 08 / 136,626, which are incorporated herein by reference.

Some preferred proteolytic enzymes are selected from the group consisting of Savinase®, Esperase®, Maxacal®, Purafec®, BPN ', Protease A and Protease B, and mixtures thereof. Bacterial serine protease enzymes obtained from Bacillus subtilis and / or Bacillus licheniformis are preferred. Particularly preferred are Savinase®, Alcalase®, Protease A and Protease B.

Typically the compositions herein also consist of an amylase or mixtures thereof. The genetic design of enzymes for improved stability, for example oxidative stability, is known. See, for example, J. Biologila Chem., Vol. 260, No. 11, June 1985, pp 6518-6521. "Reference amylase" hereinafter refers to an amylase outside the scope of the amylase component of this invention and against which the stability of any amylase within the invention can be calculated.

The present invention thus makes use of amylases having improved stability in detergents, especially improved oxidative stability. A convenient benchmark of absolute stability against which the amylases used in the present invention represent a calculable improvement is the stability of TERMAMYL® in commercial use in 1993 and available from Novo Nordisk A / S. This TERMAMYL® amylase is a "reference amylase". Amylases within the spirit and scope of this invention share the characteristic of being "improved stability" amylases, characterized, at least, by a calculable improvement in one or more of: oxidative stability, for example to hydrogen peroxide / tetraacetylethylenediamine in pH regulating solution at pH 9-10; thermal stability, for example at common washing temperatures, such as 60 ° C; or alkaline stability, for example at a pH of 8 to 11, all measured against the reference amylases identified above. Preferred amylases herein can demonstrate further improvements against more competitive reference amylases, the latter reference amylases being illustrated by any of the amylase precursors of which the amylases within the invention are variants. Such amylase precursors may themselves be natural or be the product of genetic design. The stability can be measured using any of the technical tests described in the art. See the references described in WO 94/02597, itself and the documents referred to therein being incorporated by reference.

In general, amylases of improved stability with respect to the invention may be obtained from Novo Nordisk A / S, or from Genencor International.

Preferred amylases herein have the common ability to be derived using site-directed mutagenesis from one or more of the Bacillus amylases, especially Bacillis alpha-amylases, regardless of whether one, two or multiple strains of amylases are the precursors. immediate.

As noted, amylases of "improved oxidative stability" are preferred for use herein. Said amylases are illustrated in a non-limiting manner by the following: (a) An amylases according to the document incorporated herein above WO / 94/02597, Novo Nordisk A / S, published on February 3, 1994, as further illustrated by a mutant in which substitution has been made, using alanine or threonine (preferably threonine), the methionine residue located at position 197, or the variation of the homologous position of a similar original amylase, such as Bacillus amyloliquefaciens, Bacillus subtilis, or Bacillus stearothermophilus; (b) The improved stability amylases as described by Genencor International in a document entitled "Oxidatively Resistant alpha-Amylases" presented at the 20th National Meeting of the American Chemical Society, March 13-7, 1994, by C. Mitchinson. It was noted that the bleaches in automatic dishwashing detergents inactivate alpha-amylases but that amylases of improved oxidative stability have been made by Genencor from Bacillus licheniformis NCIB8061. Methionine (Met) was identified as the residue most likely to be modified. Met was substituted, one at a time, at positions 8, 15, 197, 256, 304, 366 and 438 leading to specific mutants, with M197L and M197T being particularly important with the M197T variant being the most stable expressed variant. The stability was measured in CASCADE ® and SUNLIGHT ®; Such enzymes are commercially available from Genencor under the trade name Plurafact Oxam®. (c) Particularly preferred herein are the amylase variants having further modification in the immediate original available from Novo Nordisk A / S. These amylases do not yet have a commercial name but are those to which the supplier refers as QL-37 + M197T. Such enzymes are commercially available under the trade name SP 703 from Novo.

Any other amylase of improved oxidative stability can be used, for example as derived by site-directed mutagenesis from original known chimeric, hybrid or simple mutant forms of available amylases.

The soaking compositions herein may also consist of a soil suspending agent, or a mixture thereof, typically at a level of up to 20% by weight, preferably from 0.1% to 10%, more preferably from 0.5% to 2%. %. Suitable soil suspending agents include ethoxylated diamines, ethoxylated polyamines, ethoxylated amine polymers as described in EP-A-112 593, incorporated herein by reference. Preferred soiling agents to be used herein include ethoxylated polyethyleneamine having a molecular weight of from 140 to 310 before ethoxylation, ethoxylated 15-18 tetraethylenepentamine, ethoxylated 15-18 polyethyleneamine, ethoxylated 15-18 ethylenediamine. , ethoxylated polyethyleneimine having a molecular weight of from 600 to 1800 before ethoxylation, and mixtures thereof.

The soaking compositions herein may additionally consist of other optional ingredients such as optical brighteners, other enzymes, other chelators, dispersants, soil release agents, photoactivated whiteners such as Zn phthalocyanine sulfopate, colorants, dye transfer inhibitors, pigments, perfumes and the like. Said optional ingredients may be added in varying amounts as desired.

B.- The Procedure: The present invention encompasses a process for soaking fabrics. In fact, the present invention encompasses a process for soaking fabrics, wherein said fabrics are immersed in a soaking solution consisting of water and an effective amount of a composition as described hereinbefore, for an effective period of time, and then remove from said soaking solution.

As used herein, the term "fabric soaking process" refers to the action of leaving the fabrics to soak in a soaking solution consisting of water and a composition as described herein above, for a period of time enough to clean such fabrics. In contrast to the typical washing operation of laundry using a washing machine, the soaking procedure of the present allows a prolonged contact time between the fabrics and the soaking solution, typically up to 24 hours. The soaking process can be performed independently of any other procedure, such as a typical laundry operation, or a first step before a second, typical washing step. In the preferred soaking process of the invention, the fabrics are left to soak for a period of time in the range of 10 minutes to 24 hours, preferably 30 minutes to 24 hours, more preferably more than 1 hour to 24 hours, yet more preferably 2 hours to 24 hours, and even more preferably 4 hours to 24 hours. After the fabrics have been immersed in said soaking solution for a sufficient period of time, they can be removed and rinsed with water. The fabrics can also be washed in a normal laundry operation after they have been soaked, with or without being rinsed between the soaking operation and the subsequent washing operation.

In the soaking process of the present, a soaking composition described herein above is diluted in a suitable amount of water to produce a soaking solution. Suitable doses may be in the range of 40 to 55 grams of soaking composition in 3.5 to 5 liters of water, up to 90 to 100 grams of soaking composition in 20 to 45 liters of water. Typically a dose is 40-55 grams in 3.5 to 5 liters for a concentrated soak (bucket / sink). To soak in washing machine, the dose in 90-100 grams in almost 20 (Europe) to 45 (USA) liters of water. The fabrics to be soaked are then immersed in the soaking solution for an adequate period of time. There are factors that can influence the total performance of the procedure on dirt / particulate dirt. Such factors include prolonged soaking time. In fact, the longer the soaking time, the better the final results. Ideally, the soaking time is night, that is, from 8 to 24 hours, preferably from 12 to 24 hours. Another factor is the initial warm or warm temperature. In fact, the high initial temperatures of the soaking solutions ensure great performance benefits.

The process herein is suitable for cleaning a variety of fabrics, but finds a preferred application in the soaking of socks, which are particularly exposed to collecting mud and clay.

In its broadest aspect the present invention encompasses a process for soaking fabrics, wherein said fabrics are soaked in a soaking solution consisting of water and an effective amount of a composition consisting of an oxygen bleach and a nonionic surfactant. alkoxylated according to the formula RO- (A) nH, wherein R is a substituted or unsubstituted, saturated or unsaturated, linear or branched hydrocarbon chain having from 6 to 40 carbon atoms, A is an alkoxy group has from 2 to 10 carbon atoms and wherein n is an integer from 9 to 100, for more than 1 hour, preferably from 2 to 24 hours, more preferably from 4 to 24 hours, and then removed from said soaking solution . In fact, it has been discovered that when said highly alkoxylated nonionic surfactant is added in a soaking composition containing oxygen bleach, improved improved particle fouling removal as well as removal of enzymatic spots is obtained.

The stain removal performance test method: The stain removal performance of a given composition on a soiled fabric under soaking conditions, can be evaluated by the following test method. The soaking solutions are formed by diluting for example 45 g of the soaking composition of the present in 3.78 liters of water or 90 g of the soaking composition in 45 liters of water. The fabrics are then immersed in the resulting soaking solution for a time in the scale of more than 1 hour to 18 hours. Finally, the fabrics are removed from the soaking solutions, rinsed with water and washed with a regular washing procedure, hand wash or washing machine, with a regular detergent, with or without re-use the soaking solution , then said fabrics are allowed to dry.

For example, soiled fabrics typically to be used in the stain removal performance test may be commercially available from EMC (Empirical Manufacturing Company) Cincinnati, Ohio, USA, such as clay, grass, spaghetti sauce, sauce, dirty oil motor, makeup, barbecue sauce, tea, blood on two different substrates, cotton (CW120) and polycotton (PCW28).

The stain removal performance can be evaluated by comparing side by side the soiled fabrics treated with the soaking composition according to the present invention with those treated with the reference, for example the same composition without said highly alkoxylated nonionic surfactant according to the invention. with the present invention. A visual grading scale can be used to assign differences in the dial units panel (psu), on a scale of 0 to 4.

The following examples will further illustrate the present invention.

EXAMPLES The following compositions are prepared by mixing the ingredients listed in the listed proportions. 2 3 Inqredients (% P / P) (% P / P) (% P / P) Sorbitan monostearate (SMS) 0.5 0.5 0.5 Citric acid 11 11 11 NOBS 6 Polyacrylate (Acusol 445ND®) 11 11 11 Sodium percarbonate 31 31 31 C14-C16 ethoxylated alcohol EO25 C12-C16 ethoxylated alcohol EO11 C12- ethoxylated alcohol C16 EO50 Anionic (LAS / AS / AES) 8 8 8 DTPA 0.2 0.2 0.2 TAED Minor and inert Up to 100 Up to 100 Up to 100 TAED is tetracetyl ethylene.

NOBS is n-nonanoyloxybenzensulfonate NaPS is parafin sodium sulfonate DTPA is diethylenetriamine penta acetic acid.

Soaking solutions are formed by diluting each time 5 g of the above compositions in between 3.5 liters to 5.0 liters of water. 0.5 to 2 Kg. Fabrics are then submerged each time in said soaking solution. The soaking periods for the soaking solutions consisting of any of the above soaking compositions 1 to 6 or 9 are typically from 10 minutes to 24 hours. For the soaking solution consisting of the soaking compositions 7 or 8 described hereinabove, the soaking time according to the soaking process of the present invention is more than 1 hour and preferably 4 to 24 hours. Finally, the fabrics are removed from the soaking solutions, rinsed with water and washed in a regular washing procedure, washed by hand or washing machine, with a regular detergent, with or without re-using the soaking solution , then said fabrics are allowed to dry. An excellent stain removal performance is obtained with these compositions on various stains including mud / clay stains as well as enzymatic stains and / or bleach stains and the like.

Claims (13)

NOVELTY OF THE INVENTION CLAIMS

1. - A granular soaking composition consisting of:

0. 001% to 15% by weight of the total composition of a sorbitan ester according to the formula C6H9? 2 (C2H O)? R1R2R3 where x is an integer from 0 to 40, R1, R2 are independently OH or (CnH2r,? -?) COO, and R3 is a group (CnH2n +?) COO, where n is an integer from 1 to 17 , from 0.001% to 20% by weight of the total composition of an alkoxylated nonionic surfactant according to the formula RO- (A) nH, wherein R is a straight or branched hydrocarbon chain, saturated or unsaturated, substituted or unsubstituted having from 6 to 40 carbon atoms, A is an alkoxy group having from 2 to 10 carbon atoms, and wherein n is an integer from 9 to 100, and an oxygen bleach.

2. A composition according to claim 1 comprising 0.01% to 10% by weight of the total composition of said sorbitan ester or a mixture thereof, preferably from 0.1% to 5% and more preferably from 0.5 % to 4%.

3. A composition according to any of the preceding claims characterized in that said sorbitan ester is polyethoxylated sorbitan sorbate (20), or polyethoxylated sorbitan monostearate (20) or sorbitan monostearate, or sorbitan monopalmitate, or mixtures thereof. same.

4. A composition according to any of the preceding claims comprising a non-ethoxylated sorbitan ester and an ethoxylated sorbitan ester.

5. A composition according to any of the preceding claims comprising from 0.01% to 15% of said alkoxylated nonionic surfactant or a mixture thereof, preferably from 0.1% to 10%, and more preferably from 0.5% to 5%.

6. A composition according to any of the preceding claims characterized in that in said alkoxylated nonionic surfactant according to the formula RO- (A) nH, R is an alkyl group or linear or branched aryl group, saturated or unsaturated , substituted or unsubstituted having from 6 to 40 carbon atoms, preferably from 8 to 25, more preferably from 10 to 20, n is an integer from 9 to 100, more preferably from 10 to 80 and more preferably from 10 to 30 , and A is an alkoxy group having from 2 to 8 carbon atoms, and preferably is propoxy and / or ethoxy.

7 '.- A composition according to any of the preceding claims comprising 0.01% to 80% by weight of the total composition of an oxygen bleach or mixtures thereof, preferably from 5% to 45% and more preferably from 10% to 40%.

8. - A composition according to any of the preceding claims characterized in that said oxygen bleach is percarbonate metalalkaline salt.

9. A composition according to any of the preceding claims which further comprises an activator for the bleach up to a level of 30% by weight of the total composition.

10. A composition according to any of the preceding claims further comprising at least one optional ingredient selected from the group consisting of acidifying agents, silicate metalalkaline salt, detergency builders, soil suspending agents, fillers, other surfactants, optical brighteners, enzymes, chelating agents, dispersants, dirt release agents, colorants, dye transfer inhibitors, pigments, perfumes and mixtures thereof.

11. A process for soaking fabrics, characterized in that said fabrics are immersed in a soaking solution consisting of water and an effective amount of a composition according to any of the preceding claims, for an effective period of time, then they are removed of said soaking solution.

12. A method according to claim 11 characterized in that said time is in the range of 10 minutes to 24 hours, preferably from 30 minutes to 24 hours, more preferably from 1 hour to 24 hours and more preferably from 4 hours to 24 hours. hours.

13. - A process for soaking fabrics, characterized in that said fabrics are immersed in a soaking solution consisting of water and an effective amount of a composition consisting of an oxygen bleach and a non-ionic alkoxylated surfactant according to the formula RO- (A) nH, wherein R is a linear or branched, saturated or unsaturated, substituted or unsubstituted hydrocarbon chain having from 6 to 40 carbon atoms, A is an alkoxy group having from 2 to 10 carbon atoms , and wherein n is an integer from 9 to 100, for more than 1 hour, preferably 2 hours to 24 hours and more preferably 4 hours to 24 hours, then removed from the soaking solution.