MXPA97003683A - Compounds of peroxiacide whitening precursor hydrophobic stabilized with a soluble caboxylic acid in a - Google Patents

Abstract

A peroxyacid bleach precursor composition and a detergent composition containing it are provided and consist of: a) a peroxyacid bleach precursor of size less than 100æm and selected from precursors that are produced under the perhydrolysis of the peroxyacid hydrophobic whose parent carboxylic acid has a critical micelle concentration of less than 0.5 moles / liter, and a) a water-soluble organic acid compound, wherein said organic precursor and acid are in close physical proximity, the compositions of the invention show a Improved storage stability, as well as a perhydrolysis rate improves

Description

COMPOSITIONS OF PEROXYNIDE BLOCKING PRECURSOR HYDROFOBIC STABILIZED WITH A SOLUBLE CARBOXYLIC ACID IN WATER TECHNICAL FIELD The present invention relates to peroxyacid bleach precursor compositions and detergent compositions containing them, which have an improved perhydrolysis rate as well as improved storage stability. More particularly, it relates to bleach activators that produce hydrophobic peroxyacids in aqueous media.

BACKGROUND OF THE INVENTION Under alkaline conditions, the bleach activators are susceptible to hydrolysis under alkaline conditions, which thereby reduces the storage stability, as well as the rate of perhydrolysis when in an aqueous wash liquid. The prior art includes numerous examples of organic peroxyacid presurers coated or agglomerated to thereby increase their storage stability in detergent compositions and / or to influence their behavior in solution.

EP-R-0070474 describes granulated organic peroxyacid bleach precursors prepared by spray drying an aqueous pumpable dispersion containing an N-acyl or 0-acyl compound together with at least one water soluble cellulose ether, starch or starch derivative in a weight ratio of activator to coating of 98: 2 to 90:10. GB-R-1507312 discloses the coating of organic peroxyacid bleach precursors with a mixture of alkali metal C8-C22 fatty acid salts mixed with the corresponding fatty acids. GB-A-1381121 employs a molten coating of, inter alia, mixtures of C14-Cie fatty acid to protect solid organic peroxyacid bleach precursors. GB-A-1441416 discloses a similar procedure using a mixture of C12-C14 fatty acids and C10-C20 aliphatic alcohols. EP-fl-0375241 discloses organic peroxyacid bleach precursor extrudates in which the C5-C18 alkyl peroxycarboxylic acid precursors are blended with a binder selected from anionic and nonionic surfactants, fatty acids of polymer forming film or mixtures of such binders. EP-fl-0356700 discloses compositions consisting of an organic peroxyacid bleach precursor, a water soluble film-forming polymer and 2-15% of a C3-Cβ polyvalent carboxylic acid or hydroxycarboxylic acid for improved stability and ease of dispersion / solubility. The carboxylic acid, of which a preferred example is citric acid, is dry blended with the organic peroxyacid bleach precursor and subsequently granulated with the film-forming polymer. A granule consisting of 88.1% TAED of average particle size from 0.01 to 0.8 mm, 10.4% citric acid, 0.5% polyacrylate and 1.0% water is specifically described. It is stated that the citric acid provides an improved dissolution rate of the organic peroxyacid bleach precursor granules. EP-A-0382464 relates to a process for coating or encapsulating solid particles including bleaching compounds and organic peroxyacid bleach precursors in which a substance of coating material is formed in which the particles form a dispersed phase, the substance is destabilized and then caused to disintegrate into a particulate material in which the dispersed phase particles are embedded in the continuous phase (coating). A variety of coating materials are disclosed and certain materials such as polyacrylic acid and cellulose acetate phthalate are shown as useful wherein release of the coated material depends on the pH. Notwithstanding the advances in the art represented by the foregoing descriptions, difficulties have still been encountered in providing peroxyacid precursor particles having acceptable physical characteristics for bulk storage and rate of perhydrolysis, wherein the peroxyacid precursor is selected from those that produce hydrophobic peroxyacid in aqueous wash liquor. Moreover, when hydrophobic yellow-opaque spot cleaning is needed, the use of precursors that are idrophobic by nature is necessary to provide excellent performance in opaque spots. Examples of such precursors are 3,5,5-tri-methyl hexanoyl oxybenzenesulfonate, nonanoyl oxybenzenesulfonate and caproyl oxybenzene sulphonate derivatives. However, due to its hydrophobic character, a solubility problem is encountered with the use of such activators. In addition, when the caproyl oxybenzene sulfonate derivatives such as 6-octanamido-caproyl oxybenzenesulfonate, 6-nonanamidocaproyl oxybenzenesulfonate, 6-decanamido-caproyl oxybenzenesulfonate and mixtures thereof are used, applicants have found that these problems are exacerbated . Applicants have discovered that the aforementioned problems can be particularly troublesome when said peroxyacid bleach precursor is used under conditions of high hardness resulting from dissolution in the formation of insoluble calcium salts. Applicants have now discovered that these problems can be overcome by providing a peroxyacid bleach precursor of a specific maximum size together with a water soluble organic acid compound, in which the peroxyacid is selected from those produced by p >hydrophobic peroxyacid erhidrolysis.

BRIEF DESCRIPTION OF THE INVENTION According to the invention, a peroxyacid bleach precursor composition is provided which consists of: a) a peroxyacid bleach precursor of a size less than 100μm and selected from precursors that are produced under the perhydrolysis of the hydrophobic peroxyacid; Relative carboxylic acid has a critical concentration of less than 0.5 moles / liter, and b) a water soluble organic acid compound; wherein the precursor diho and said organic acid are in close physical proximity. For the purpose of the present invention, the term close physical proximity means one of the following: i) an algorithm or extrudate in which said precursor and said organic acid are in intimate mixing; ii) a bleach precursor particle material coated with one or more layers in which at least one layer contains the organic acid; iii) an organic acid compound coated with one or more layers in which at least one layer contains the bleach activator. It should be understood by close physical proximity that the precursor and the organic acid are not two discrete discrete particles in the detergent composition.

DETAILED DESCRIPTION OF THE INVENTION A key feature of the invention is a peroxyacid bleach precursor that is produced by the perhydrolysis of a hydrophobic peroxyacid whose parent carboxylic acid has a critical micelle concentration of less than 0.5 moles / liter and wherein said critical micelle concentration Measure in aqueous solution at 20 ° -50 ° C. Preferably, the base structure chain of the perioxy acid contains at least 7 carbons which may be partially or fully branched, chained or cyclic and any mixture thereof.

Peroxyacid bleach precursor Peroxyacid bleach precursor compounds typically contain one or more N- or 0-acyl groups, whose precursors can be selected from a wide range of classes.

Peroxyacid bleach precursors suitable for the purpose of the invention are the substituted amide compounds of the following general formulas: R 1 N (R 5) C (0) R 2 C (0) LOR * C (0) N (R 5) R 2 C (0) ) L in which R * is an aryl or alkaryl group with from about 1 to about 14 carbon atoms, R 2 is an alkylene, arylene and alkarylene group with from about 1 to about 14 carbon atoms and RS is H or a group alkyl, aryl or alkaryl with 10 carbon atoms and L may be essentially any starting group. * preferably contains about 6 to 12 carbon atoms. R2 preferably contains from about 4 to 8 carbon atoms. R 1 can be straight or branched chain alkyl, aryl or alkylaryl substituted with branching, substitution or both and can be obtained either from synthetic or natural sources, including, for example, tallow grease. Analogous structural variations for R are permissible. R 2 may include alkyl, aryl, wherein said R 2 may also contain halogen, nitrogen, sulfur and other typical substituent groups or organic compounds. Rs is preferably H or methyl. Ri and s must not contain more than 18 carbon atoms in total. The substituted amide bleach activator compounds of this type are described in EP-A-0170386. The starting group, hereinafter group L, must be reactive enough for the perhydrolysis reaction to occur within an optimal time frame (e.g., a wash cycle). However, if L is very reactive, this activator will be difficult to stabilize for use in a bleaching composition. The preferred L groups are selected from the group consisting of: and mixtures thereof, wherein Ri is an alkyl, aryl or alkaryl group containing 14 carbon atoms, R3 is an alkyl chain containing 1 to 8 carbon atoms, R * is H or R3, and Y is H or a solubilizing group. Any of Ri, R3 and 4 can be essentially substituted by any functional group including, for example, alkyl, hydroxy, alkoxy, halogen, amine, niilosyl, amide and ammonium groups or alkylammonium groups. The preferred solubilizing groups are -S03-M +, -CO2 -M +, -S? 4-m, -N + (R3 U ~ and 0 <-N (R3) 3 and most preferably -SO3 -M * and -C02 ~ M + in which R3 is an alkyl chain containing from 1 to 4 carbon atoms, M is a cation that provides solubility to the bleach activator and X is an anion that provides solubility to the bleach activator. Preferably, M is an alkali metal, ammonium or substituted ammonium cation, with sodium and potassium being most preferred, and X being a halide, hydroxide, methylsulfate or acetate anion. Preferred examples of bleach activates of the above formulas include caproyl oxybenzene sulfonate derivatives selected from 6-octanamidocaproyl oxybenzenesulfonate, 6-nonanarnidocaproyl oxybenzenesulfonate, 6-decanamido caproyl oxybenzenesulfonate and mixtures thereof, as described in EP- A-0170386. Also another preferred class of bleach activator is the class of alkyl percarboxylic acid bleach effectors. Preferred alkyl percarboxylic acid precursors include nonanoyl oxybenzenesulfonate (NOBS described in US 4,412,934) and 3,5,5-tri-rnethyl hexanoyl oxybenzenesulfonate (ISONOBS described in EP120,591) and salts thereof. The mixture of any of the peroxyacid bleach precursors described hereinabove can also be used. The peroxyacid bleach precursors are usually incorporated at a level of from 20% to 95% by weight of the bleach precursor composition, preferably at least 50% and most preferably at least 60% by weight thereof. In absolute terms the peroxyacid bleach precursor is typically from 1% to 20% by weight, most preferably from 1% to 10% by weight and most preferably from 1% to 7% by weight of the detergent compositions.

Water-soluble organic acid compound The composition of the invention contains as another essential component a water-soluble organic acid compound. The organic acid compounds suitable for incorporation as binding agents of the particles of the invention consist of aliphatic or aromatic carboxylates.

The carboxylates can be onorneric, oligomeric or polymeric in nature and preferably consist of aliphatic carboxylic acids. Examples of onomeric aliphatic acid compounds are glycolic, glutamic, citraconic, succinic, 1-lactic, malonic, glutaric, adipic, maleic, rnical, tartaric, citric, diglycolic and carboxymethyl succinic acids. Examples of polymeric acid compounds include polymethacrylic acids and copolymeric derivatives with maleic anhydride. Preferably, the organic acid is a monomeric or oligomeric carboxylate and most preferably a monomeric aliphatic carboxylic acid. Preferred monomeric aliphatic acids are 1-lactic, citric and glycolic acids, while preferred polymeric acids include polyacrylic acids of PMt 3000-5000, especially about 4500 and copolymers of maleic anhydride acrylic acid of MWt 40,000-90,000. A preferred organic acid is citric acid. The organic acid is incorporated at levels of from 5% or 50% by weight of the particle material to be agglomerated, most preferably from 5% to 25% by weight and most preferably from 7% to 20% by weight. The incorporation of other additional ingredients into the organic peroxyacid bleach precursor compound and the organic acid compound can be particularly advantageous in the processing of the bleach precursor particle materials and also to improve the stability of the detergent compositions in which particle materials are included. In particular, certain types of agglomerates may require the addition of one or more binding agents to assist in agglutinating the organic peroxyacid bleach precursor compound and the organic acid compound to thereby produce acceptable physical characteristic particle materials. The binding agents can be present at a level of from 0% to 40% by weight of the particle material. Preferably, the binding agents will be intimately mixed with the organic peroxyacid bleach precursor compound and the organic acid compound. Preferred binding agents have a melting point between 30 ° C and 70 ° C. Binders are preferably present in amounts of 1-30% by weight of the particle material and most preferably 2-20% by weight of the particle material. Preferred binding agents include the C10-C20 alcohol ethoxylates containing from 5-100 moles of ethylene oxide per mole of alcohol and most preferably the ethoxylates of primary C15-C20 alcohol containing from 20-100 moles of ethylene per mole of alcohol. Of these, ethoxylated tallow alcohol with 25 moles of ethylene oxide per mole of alcohol (TAE25) or 50 moles of ethylene oxide per mole of alcohol (TAE50) is preferred. Other preferred binding agents include certain polymeric materials. Polyvinyl pyrrolidones with an average molecular weight of from 12,000 to 700,000 and polyethylene glycols with an average molecular weight of 600 to 10,000 are examples of such polyrnepic materials. Copolymers of maleic anhydride with ethylene, methyl vinyl ether, methacrylic acid or acrylic acid are additional examples of poly-epic materials useful as binding agents. Of these, the copolymers of aleic anhydride with acrylic acid are preferred. These polymeric materials can be used as such or in combination with solvents such as water, propylene glycol and the aforementioned CIO-C20 alcohol ethoxylates containing -100 moles of oxide ethylene per mole Additional examples of binding agents include the C10-C20 mono- and diglycerol ethers and also the C10-C20 fatty acids. Also for use in this purpose are the solutions of certain inorganic salts which include sodium silicate. Cellulose derivatives such as carboxymethylcellulose and furnace or copolymer polycarboxylic acid or their salts are other examples of suitable binding agents. Other additives that are compatible with the peroxyacid precursors can be included in the detergent additive compositions according to the invention. Examples of such additives include surfactants, fluorescers, enzymes, foam suppressors, dye transfer inhibiting agents, soil suspending agents, water soluble builders and quenching agents. The specific embodiments of such additives and their levels of composition are described hereinafter, but the total level of the additives is usually in the range of from 5% to 50% by weight of the additive composition. The peroxyacid precursors should substantially form the main component of the precursor composition, ie from 20% to 95% by weight of the agglomerate, preferably at least 50% by weight and most preferably at least 60% by weight of the isomer. . In the preferred agglomerate embodiments of the invention the diameter of the pores forming the spaces between the agglomerated particles is selected by controlling the levels of compaction and shear applied during the aglomerization process. A very large pore size results in an agglomerate of inadequate strength and a tendency to disintegrate during handling. A very small pore size results in an agglomerate having a slow dissolution rate. It has been found that a satisfactory agglomerate has a porosity percentage of at least 12 corresponding to an average pore diameter of at least 0.5 u and preferably in the range of 0.6 to 5 micras. The porosity is measured in accordance with the following technique, using a Micromeritics Poresizer 9320. This equipment is manufactured by Micromeritics Instruments Corporation, One Micro erythics Drive, Norcross GA 30093-1877, E.U.A. and consists of a penetrator, analyzer and printer. For this analysis the penetromer bulb is filled with a known weight (at 4 dp) of particle material. The penetrometer is then completely assembled with the insulator seal, the retension collar and the spring. This is then equipped inside the low pressure port of the porosity analyzer. The penetrometer is subsequently evacuated and the sample analyzed under the following reference point conditions: Maximum measurable volume 0.387 ml Total total stem volume 0.4.12 ML Main stop pressure 0.329 kg / tfi (porosity pressure readings) Penetrometer constant 10.79 1 /? F (liter / peak farad) at the following pressures: 0.140, 0.210, 0.281, 0.386, 0.492, 0. 597, 0.738, 0.913, 1.124, 1.406, 1.616, 1.757 kg / c t a After this analysis the penetrometer bulb is installed in the high pressure chamber and analyzed under the same conditions of point and the printer then gives the average pore diameter and the pore intrusion volumes for the sample. For the preferred pore diameter of at least 0.5 microns, the pore intrusion volume is at least 0.2 ml / g. Detergent compositions incorporating the peroxyacid bleach precursor particles will typically contain from 1% to 20% of the precursor, most often from 1% to 10% and most preferably from 1% to 7% on a weight basis of the composition. Such detergent compositions will, of course, contain a source of alkaline hydrogen peroxide necessary to form a peroxy bleach species in the wash solution and preferably will also contain other conventional components in the detergent compositions. The precise nature of these additional components and the levels of incorporation thereof will depend on the physical form of the composition, as well as on the nature of the cleaning operation for which it will be used. The compositions of the invention can, for example, be formulated with detergent compositions for manual or machine laundry, including additive laundry compositions and compositions suitable for use in the pretreatment of soiled fabrics and machine dishwashing compositions. When incorporated into compositions suitable for use in a machine washing method, eg, machine laundry and machine dishwashing methods, the compositions of the invention will preferably provide one or more additional detersive components. In this way, the preferred detergent compositions will incorporate one or more surfactants, organic and inorganic builders, suspending and anti-redeposition agents, foam suppressors, enzymes, fluorescent whitening agents, photoactivated whiteners, perfumes and colorants. Detergent compositions that incorporate the particulate peroxyacid preci- sters of the present invention will include an inorganic perhydrate bleach, usually in the form of the sodium salt, as the source of alkaline hydrogen peroxide in the wash liquor. This perhydrate is normally incorporated at a level of from 3% to 40% by weight, most preferably from 5% to 35% by weight and still most preferably from 8% to 30% by weight of the composition. The perhydrate can be any of the inorganic alkali metal salts such as nonohydrate salts or perborate tetrahydrate, percarbonate, perfosphate and persilicate, but is conventionally an alkali metal perborate or percarbonate. Sodium percarbonate, which is the preferred perhydrate, is an addition compound having the formula 2 a2C? 3.3H2O2, and is commercially available as a crystalline solid. Most of the commercially available material includes a low level of a heavy metal sequestrant such as EDTA, 1-hydroxyethylidene 1,1-diphosphonic acid (HEDP) or an amino osphonate, which is incorporated during the manufacturing process. For the purposes of the detergent composition aspect of the present invention, the percarbonate can be incorporated into the detergent compositions without further protection, but preferred embodiments of such compositions utilize a coated form of the material. A variety of coatings can be used, including borate, boric acid and sodium silicate or citrate in a ratio of Si? 2: a2? from 1.6: 1 to 3.4: 1, preferably 2.8: 1, applied as an aqueous solution to give a level of from 2% to 10%, (typically 3% to 5%) of silicate solids by weight of the percarbonate. However, the most preferred coating is a mixture of sodium carbonate and sodium sulfate or chloride. The particle size scale of crystalline percarbonate is from 350 microns to 1500 microns with an average of approximately 500-1000 microns. A broad scale of surfactants can be used in detergent compositions. A typical list of anionic classes, non-ionic, amholytic and zwitterionic, as well as species of these surfactants, is given in USP 3,929,678 issued to Laughlin and Heuring on December 30, 1975. A list of suitable cationic surfactants is given in the USP document 4,259,217 issued to Murphy on March 31, 1981. Non-limiting examples of additional, non-amide surfactants, useful herein include the conventional Cn-Ciß alkylbenzene sulphonates ("LAS") and the C10-alkylsulfatoe C20 ("AS") primary, branched chain and random, the secondary sulfates (2,3) of Cio-Ciß of the formula CH3 (CH2) x (CH0S03-M +) CH3 and CH3 (CH2) and (CH0S03 ~ M + ) CH2CH3 where xy (y + 1) are integers of at least 7, preferably at least about 9, and M is a cation of solubilization in water, especially sodium, unsaturated sulaphthates such as oleylsulfate, alkylalkoxysulphates of C? or ~ Ci8 ("AExS"; especially ethoxysulfates EO 1-7), alkylalkoxycarboxylates of Cι-Ciß (especially the ethoxycarboxylates EO 1-5), the glycolic ethers of Cι-Ciß, the alkyl polyglycosides of Cι-Ciß and their corresponding sulphated polyglycosides, and esters of fatty acid alphasulfonated of C12-C18. If desired, conventional non-ionic amphoteric surfactants such as Ci 2 -C 6 alkylethylates ("AE") including the so-called narrow peak alkylethoxylates and the C 6 -C 12 alkyl phenylalkoxylates (especially ethoxylates and ethoxy / mixed propoxy), C12-C18 betaines and sulfobetaines ("sultaines"), Cio-Ciß amine oxides, and the like can also be included in the overall compositions. The N-alkyl polyhydroxy fatty acid amides of Cio-Ciß can also be used. Typical examples include the C12-C18 N-methylglucamides. See UO 9,206,154. Other surfactants derived from sugar include the N-alkoxy polyhydroxy fatty acid amides, such as C?-C-18 N (3-methoxypropyl) glucamide. N-propyl glucans through C12-C18 N-hexyl can be used for low foam formation. Conventional C10-C20 soaps can also be used. If high foaming is desired, C? O ~ Ci6 soaps of branched chains can be used. Other surfactants useful for the purpose of the invention are the anionic alkali metal sarcosinates of the formula: R-C0N (R1) CH2C00M wherein R is a linear or branched C9-C17 alkyl or alkenyl group, I is a group Ci-C4 alkyl and N is an alkali metal ion. Preferred examples are lauroyl, cocoyl (Ci2-C?), Myristyl and oleyl methyl sarcosinates in the form of their sodium salts. Mixtures of anionic and nonionic surfactants are especially useful. Other conventional surfactants are listed in normal texts. The compositions herein may optionally include one or more other additional detergent compounds or other compounds to assist or improve the cleaning performance, the treatment of the substrate to be cleaned, or to modify the aesthetics of the detergent composition (e.g., perfumes) , dyes, dyes, etc.). The following are illustrative examples of such additional compounds for detergents.

Detergency builders Builders may optionally be included in the compositions herein to help control the hardness of minerals. Inorganic and organic builders can be used. Detergency builders are typically used in fabric washing compositions to help remove particulate soils. The level of builder can vary widely depending on the final use of the composition and its desired physical form. When present, the compositions will typically comprise at least about 1% builder. Liquid formulations typically comprise from about 5% to about 50%, very typically from about 5% to about 30%, by weight builder. Granulated formulations typically comprise from about 10% to about 80%, very typically from about 15% to about 50% by weight of the builder. However, lower or higher detergency builder levels are not excluded. Inorganic or phosphate-containing builders include, but are not limited to, the alkali metal, ammonium and alkanolammonium salts of polyphosphates (illustrated by tripoli phosphates, pyrophosphates and vitreous polymeric metamates). detergency that are not phosphate. These may include, but are not restricted to, phytic acid, silicates, alkali metal carbonates (including bicarbonates and sesquicarbonates), sulfates, alurninosilicates, monomeric polycarboxylates, homo or copolymeric polycarboxylic acids or their salts in which the polymeric acid consists of at least two radicals separated from each other by no more than two carbon atoms, organic phosphonates and poly (alke phosphonates) of aminoalke. Importantly, the compositions herein work surprisingly well even in the presence of so-called "weak" detergent builders (as compared to phosphate builders) such as citrates, or in the so-called "lower builder" condition that It can occur with zeolite builders or stratified silicate. Examples of silicate builders are alkali metal silicates, particularly those having a Si 2: Na 2 ratio. in the scale from 1.6: 1 to 3.2: 1 and layered silicates, such as the layered sodium silicates described in US Pat. No. 4,664,839, issued May 12, 1987 to H. P. Rieck. NaSKS-6 is the trade name for a crystalline layered silicate sold by Hoechst (commonly abbreviated as "SKS-6"). Unlike zeolite builders, the NaSKS-6 silicate builder does not contain aluminum. The NaSKS-6 has the morphological form of laye-Na? SiOe of stratified silicate. It can be prepared by methods such as those described in German Application DE-A-3, 417,649 and DE-A-3, 742, 043. SKS-6 is a highly preferred layered silicate for use herein, but others stratified silicates, such as those that have the general formula NaMSi ?? 2x +? yl-teO wherein M is sodium or hydrogen, x is a number from 1.9 to 4, preferably 2, and y is a number from 0 to 20, preferably 0 can be used herein. Some other stratified silicates from Hoechst include NaSKS-5, NaSKS-7 and NaSKS-11 as the alpha, beta and gamma forms. As indicated above, the delta-Na? SiOs (NaSK? -6) form is most preferred for use herein. Other silicates can also be used such as for example magnesium silicate, which can serve as a tightening agent in granulated formulations, as an oxygen bleach stabilizing agent, and as a component of foam control system. Examples of carbonate builders are the alkali metal and alkali metal carbonates as described in German Patent No. 2, 321,001 published November 15, 1973. Aluminosilicate builders are useful in the present invention. Aluminosilicate detergent builders are of great importance in most co-positioned heavy duty granular detergents currently commercialized, and can also be an important detergency builder ingredient in liquid detergent formulations. The aluminosilicate detergency enhancers include those that have the empirical formula: Mz (zA102) and]? H20 where z and y are integers of at least 6, the molar ratio of zay is on the scale of about 1.0 to about 0.5, and x is an integer from about 15 to about 264. Useful aluminosilicate ion exchange materials are commercially available. These alurninosilicatoe can be of crystalline or amorphous structure and can be alurainosilicatos that occur naturally or synthetically derived. A method for producing alkynyl silicate ion exchange materials is disclosed in US Patent 3,985,669, Krummel et al. Issued October 12, 1976. Preferred synthetic crystalline aluminosilicate ion exchange materials useful herein are available under US Pat. designations Zeolite A, Zeolite P (B), Zeolite MAP and Zeolite X. In an especially preferred embodiment, the ion exchange material of crystalline aluminosilicate has the formula: Na? 2pA102) 12 (Si02 i23 H20 where x is around from 20 to about 30, specie of about 27. The material is known as Zeolite A. Dehydrated zeolites (x = 0-10) can also be used herein Preferably, the aluminosilicate has a particle size of about 0.1-10 microns in diameter Organic builders suitable for the purposes of the present invention include, but are not limited to, a Wide variety of polycarboxylate compounds. As used herein, "polycarboxylates" refers to compounds having a plurality of carboxylate groups, preferably at least 3 carboxylates. Polycarboxylate builders can generally be added to the composition in acid form, but can also be added in the form of a neutralized salt. When used in the salt form, alkali metals such as sodium, potassium and lithium, or alkanola onium salts are preferred. Included among the polycarboxylate detergent builders are a variety of useful material categories. An important category of polycarboxy builders include the polycarboxylates of ether, including oxydisuccinate, as described in US Patent 3,128,287 and in the Patent of EUR 3,635,830. See also "TMS / TDS" detergency builders of U.S. Patent 4,663,071. Suitable ether polycarboxylates also include cyclic compounds, particularly alicyclic compounds, such as those described in US Patent 3,923,679.; 3,835,163; 4,158,635; 4,120,874 and 4,102,903. Other useful detergency builders include the ether idroxypolicarboxylates, copolymers of maleic anhydride with ethylene or vinyl ethyl ether, 1,3,5-tphydroxybenzene, 6-trisulonic acid, and carboxymethyloxyuccinic acid, various alkali metal salts, ammonium and substituted ammonium of polyacetic acids such as ethylenediaenotetracetic acid and nitrilotri acetic acid, as well as polycarboxylates such as mellitic acid, succinic acid, isuccinic acid, polymaleic acid, benzene-1,3,5-tricarboxylic acid, carboxymethyloxysuccinic acid and soluble salts of the misinos. Citrate detergent builders, e.g., citric acid and soluble salts thereof (particularly sodium salt), are polycarboxylate builders of particular importance for heavy duty liquid detergent formulations because of their availability from renewable resources and their biodegradability. The citrates can also be used in granular compositions, especially in combination with aeolith detergency builder and / or layered silicate. Oxydisuccinates are also especially useful in said compositions and combinations. Also suitable in the detergent compositions of the present invention are the 3,3-dicarboxy-4-oxa-1, 6-hexanodiates and the related compounds described in the Patent of EUR 4,566,984. Useful succinic acid builders include the C5-C20 alkyl and alkenyl succinic acids and salts thereof. A particularly preferred compound of this type is dodecenylsuccinic acid. Specific examples of succinate builders include: laurylsuccinate, myriethylsuccinate, palrnitylsuccinate, 2-dodecenylsuccinate (preferred), 2-pentadecenylsuccinate, and the like. Lauryl succinates are the preferred detergency builders of this group, and are described in EP 0,200,263. Other suitable polycarboxylates are described in U.S. Patent 4,144,226 and U.S. Pat. 3,308,067, Diehl, issued March 7, 1967. See also Diehl, U.S. Patent. 3,723,322.

The fatty acids, e.g., C12-C18 mononocarboxylic acids, can also be incorporated into the compositions by themselves, or in combination with the aforementioned builders, especially citrate and / or succinate builders, to provide additional detergency builder activity. Such use of fatty acids will generally result in decreased foaming, which would be considered by the formulator. In situations where phosphorus-based detergency builders can be used, and especially in bar formulations used for hand washing operations, various alkali metal phosphates such as the well-known sodium tripolyphosphites, pyrophos, can be used. sodium atoate and sodium orthophosphate. Phosphonate builders such as ethane-1-hydroxy-1,1-diphosphonate and other known phosphonates can also be used (see, for example, US Patents 3,159,581, 3,213,030, 3,422,021, 3,400,148 and 3,422,137).

Chelating Agents The detergent compositions herein may also optionally contain one or more iron and / or manganese chelating agents. Such chelating agents can be selected from the group consisting of incarboxylates, aminophosphate, polyfunctionally substituted aromatic chelating agents and mixtures thereof, all as defined below. Without intending to be limited by theory, it is believed that the benefit of these materials is due in part to their exceptional ability to remove iron ions and rnanganese from the washing solutions by forming soluble chelates. The aminocarboxylates useful as optional chelating agents include ethylenediaminetetracetates, N-hydroxyethylenediylenediazine, nitrilotriacetates, ethylenediamonotetraproprionates, triethylenetetramine-hexacetates, diethylenetriaminepentaacetates and ethanololdiglicines, substituted alkali metal, ammonium and ammonium salts thereof and mixtures thereof. The aminophosphates are also useful for use as chelating agents in the compositions of the invention when at least they allow low levels of total phosphorus in the detergent compositions and include ethylenediaminetetrakis (methylenephosphonates) as DEQUEST. Preferably, these aminophosphonates do not contain alkyl or alkenyl groups with more than about 6 carbon atoms. The substituted polyfunctional aromatic chelating agents are also useful in the compositions herein. See U.S. Pat. 3,812,044. Preferred compounds of this type in acid form are dihydroxydisulfobenzenes such as 1,2-dihydroxy-3,5-dis? Lfobenzene. Preferred biodegradable non-phosphorus chelators for use herein are ethylenedia inodisuccinate ("EDDS"), especially the isomer IIS, S,] as described in US Pat. 4,704,223, N, N'-diglytamine of ethylenediamine (EDDG) and composed of N, N'-dieuccinate of 2-hydroxy-oleo-diamine (HPDDS). If used, these chelating agents generally should comprise from about 0.1% to about 10% by weight of the detergent compositions herein. Most preferably, if used, the chelating agents should comprise from about 0.1% to about 3.0% by weight of said co-positions, t Clay Remover / Anti-Deposition Agents The co-poliectors of the present invention may also optionally contain water-soluble ethoxylated amines having clay dirt removal and anti-redeposition properties. The granular detergent compositions containing these compounds typically contain from about 0.01% to about 10.0% by weight of the water soluble ethoxylated amines; Liquid detergent compositions typically contain about 0.01% to about 5%. The preferred soil repellent and anti-redeposition agent is tetraethylene pentane ethoxylated. Example ethoxylated amines are described more widely in the Patent of E.U.A. 4,597,898, VanderMeer, issued July 1, 1986. Another group of clay soil removal / anti-redeposition agents are the cationic compounds described in European Patent Application 111,965, Oh and Gosselink, published June 27, 1984. Other clay dirt remover / anti-redeposition agents that can be used include the ethoxylated amine polymers described in European Patent Application 111,984, Gosselink, published June 27, 1984; the zwitterionic polymers described in European Patent Application 112,592, Gosselink, published July 4, 1984; and the amine oxides described in the U.S. Patent. No. 4,548,744, Connor, issued October 22, 1985. Other clay removers and / or anti-redeposition agents known in the art can be used in the compositions herein. Another type of preferred anti-redeposition agent includes the carboxylmethylcellulose (CMC) materials. These materials are well known in the art.

Polymeric Dirt Release Agent Any polymeric dye releasing agent known to those skilled in the art may optionally be employed in the compositions and methods of this invention. The polymeric soil release agents are characterized by having both hydrophilic segments to hydrophilize the surface of hydrophobic fibers such as polyester and nylon, and hydrophobic segments to deposit on hydrophobic fibers and remain adhered to the same haeta that the washing and rinsing cycles are completed. and thus serve as an anchor for the hydrophilic segments. This allows stains that appear after treatment with the soil release agent to be cleaned more easily in subsequent washing procedures. Dirt release agents characterized by hydrophobic poly (vinyl ester) segments include poly (vinyl ester) graft copolymers, V.gr., vinyl esters of Ci-Cß preferably poly (vinylacetate) grafted to base structures of polyalkylene, such as polyethylene oxide base structures. See European Patent Application 0 219 048 published on April 22, 1987 by Kud, and others. Commercially available soil release agents include the material type SOKALAN, V.gr., SOKALAN HP-22, available from BASF (Rlernania Western). One type of preferred soil release agent is a copolymer having random blocks of ethylene terephthalate and polyethylene terephthalate oxide (PEO). The molecular weight of this polymeric soil release agent is in the range of about 25,000 to about 55,000. See U.S. Pat. 3,959,230 to Hays, and the U.S. Patent. 3,893,929. Another preferred polymeric soil release agent is a polyester with repeat units of ethylene terephthalate units containing 1.0-15% by weight of ethylene terephthalate units together with 90-80% by weight of polyoxyethylene terephthalate units, derived from a polyethylene glycol of molecular weight average of 300-5,000. Examples of this polymer include the commercially available material ZELCON 5126 (from Dupont) and MILEASE T (from ICI). See also the U.S. Patent. 4,702,857. Another preferred polymeric soil release agent is a sulfonated product of an euletanially linear ether oligomer consisting of an oligomeric ester base structure of terephthaloyl and oxyalkylenoxy repeating units and terminal portions covalently attached to the base structure. These soil release agents are described extensively in the U.S. Patent. 4,968,451. Other suitable polyrnerous soil release agents include the terephthalate polyesters of US Pat. 4,711,730, the oligoeric esters blocked at their anion ends from the U.S. Patent. 4,721,580 and the block oligomeric polyester compounds of the U.S. Patent. 4702,857. Polymeric soil release agents also include the soil release agents of US Pat. No. 4,877,896, which describes the anionic compounds, especially sulfoarolyl, esters of terephthalate blocked at their ends. If used, soil release agents generally comprise from about 0.01% to about 10.0% by weight of the detergent compositions herein, typically from about 0.1% to about 5%, preferably from about 0.2% to about 3.0. %. Another preferred soil release agent is an oligomer with repeating terephthaloyl units, sulfoisoterephthaloyl units and oxyethyleneoxy and oxy-1,2-propylene units. The repeating units form the base structure of the oligomer and are preferably terminated with modified isethionate end blocks. A particularly preferred soiling agent of this type consists of a sulfoisophthaloyl unit, terephthaloyl units and oxyethyleneoxy and oxy-1,2-propyleneoxy units in a ratio of 1.7 to 1.8, and two end block units of 2- (2). sodium hydroxyethoxy) -ethane-sulfonate. Said soil release agent also comprises 0.5% to 20% by weight of the oligomer, of a crietalium reducing stabilizer, preferably selected from xylene sulfonate, eumeno sulfonate, toluene sulfonate and mixtures thereof.

Dye transfer inhibiting agents The compositions of the present invention may also include one or more materials effective to inhibit the transfer of dyes from one fabric to another during the cleaning process. Typically, said dye transfer inhibiting agents include polyvinylpyrrolidone polymers, polyamine N-oxide polymers, copolymers of N-vinylpyrrolidone and N-vinylnitridazole, manganese phthalocyanine, peroxidases and mixtures thereof. If used, these agents typically comprise from about 0.01% to about 10% by weight of the composition, preferably from about 0.01% to about 5%, and most preferably from about 0.05% to about 2%. Very specifically, the preferred polyamine N-oxide polymers for use herein contain units having the following structural formula: R-A "-P; wherein P is a polymerizable unit to which a group N-0 can be attached or group N-0 can form part of the polymerizable unit or group N-0 can be attached to both units; A is one of the following structures: -NC (0) -, -C (0) 0-, -S-, -O-, -N =; x is 0 or 1; and R is aliphatic, ethoxylated, aromatic, heterocyclic or alicyclic aliphatic or any combination thereof to which the nitrogen of the group N-0 can be attached or the group N-0 is part of these groups. Preferred polyamine N-oxides are those wherein R is a heterocyclic group such as pyridine, pyrrole, irnidazole, pyrroline, piperidine and derivatives thereof. The group > or N-0 may be represented by the following general structures: wherein Ri, R2, R3 are aliphatic, aromatic, heterocyclic or alicyclic groups or combinations thereof; x, y and z are 0 or 1; and the nitrogen of the group N-0 can be attached or forms part of any of the aforementioned groups. The amine oxide unit of the polyamine N-oxides has a pKa < 10, preferably pKa < 7, very preferably still pKa < 6. Any polymer base structure can be used as long as the amine oxide polymer formed is soluble in water and has dye transfer inhibiting properties. Examples of suitable polymeric base structures are p »olyvinyls, polyalkylene, polyesters, polyethers, polyamide, polyamides, polyacrylates and mixtures thereof. These polymers include random or block copolymers wherein one type of monomer is an amine N-oxide and the other type of monomer is an N-oxide. The amine N-oxide polymers typically have an amine to amine N-oxide ratio of 10: 1 to 1: 1,000,000. However, the number of amine oxide groups present in the polyamine oxide polymer can be varied by appropriate copolymerization or by an appropriate degree of N-oxidation. Polyamine oxides can be obtained in almost any degree of polymerization. Typically, the average molecular weight is within the range of 500 to 1,000,000; u and preferred 1,000 to 500,000; Still preferred is 5,000, 000 to 100,000. This preferred class of materials can be referred to as "PVNO". The preferred polyamine N-oxide useful in the detergent compositions herein is the N-oxide of poly-4-v? N? Lp? dina that has an average molecular weight of about 500,000 and an amine to N-xx? amine ratio of about 1: 4. Copolymer polymers of N-v? N? Lp > orrol? dona and N-vinylimidazole (also known as "PVPVI") are also preferred for use herein. Preferably, the PVPVI has an average molecular weight in the range of 5,000 to 1,000,000, most preferably 5,000 to 200,000 and most preferably even 10,000 to 20,000. (The average molecular weight scale is determined by light scattering as described in Barth, and other Chemical Analysis, Vol. 113. "Modern Methods of Polymer Characterization", the descriptions of which are incorporated herein by reference). PVPVI copolymers typically have a molar ratio of N-vinyloxyzole to N-vinylpyrrolidone from 1: 1 to 0.2: 1, most preferably from 0.8: 1 to 0.3: 1, most preferably from 0.6: 1 to 0.4: 1. These copol írneros can be either linear or branched. The compositions of the present invention may also employ a polyvinylpyrrolidone ("PVP") having an average molecular weight of from about 5,000 to about 400,000, preferably from about 5,000 to about 200,000, and most preferably still from about 5,000 to about 50,000 PVP's are known to the experts in the field of detergents; see, for example, EP-A-262, S97 and EP-A-256, 696, incorporated herein by reference. The PVP-containing compositions may also contain polyethylene glycol ("PEG") having an average molecular weight of from about 500 to about 100,000, preferably from about 1,000 to about 10,000. Preferably, the ratio of PEG to PVP on a ppm basis stocked in wash solutions ee of from about 2: 1 to about 50: 1, and most preferably from about 3: 1 to about 10: 1. The detergent compositions herein may also optionally contain from about 0.005% to 5% by weight of certain types of hydrophilic optical brighteners that also provide a dye transfer inhibiting action. If used, the compositions herein will preferably comprise from about 0.01% to 1% by weight of said optical brighteners. The hydrophilic optical brighteners useful in the present invention are those having the structural formula: wherein Ri is selected from anilino, N-2-bis-hydroxyethyl and NH-2-hydroxyethyl; R 2 is selected from N-2-bis-hydroxyethio, N-2-hydroxyethyi-N-methylamino, orylfino, chloro and amino; and M is an eal-forming cation such as eodium or potassium. When in the previous formula, Ri is aniline, R2 is N-2-bis-hydroxyethyl and M is a cation such as sodium, the brightener is 4,4 'acid, bisC (4-anilino-6- (N-2-bis-hydroxyethyl) -s-triazin-2-yl ) arnino] -2,2'-stilbene-sulfonic acid and disodium salt. This particular brightener species is commercially marketed under the trade name Tinopal-UNPA-GX by Ciba-Geigy Corporation. Tinopal-UNPA-GX is the preferred hydrophilic optical brightener useful in the detergent compositions of the present invention. When in the above formula R1 is anilino, R2 is N-2-hydroxyethyl-N-2-methylamino and M is a cation such as sodium, the brightener is the disodium salt of 4,4'-bis [4- anilino-6- (N-2-hydroxyethyl-N-rnetilarnino) -s-triazin-2-yl-kinnino] -2,2'-stilbenedisulfonic This particular brightener species is commercially marketed under the trade name Tinopal 5BM-GX by Ciba-Geigy Corporation When in the above formula R1 is anilino, R2 is morphino and M is a cation such as sodium, the brightener is the sodium salt of 4,4 -bisC (4-anilino-6-morphino-s -triazin-2 ~ il) arnino32, 2'-stilbendisulonic This particular brightener species is sold commercially under the tradename Tinopal AMS-GX by Ciba-Geigy Corporation.

Other specific optical brightener species selected for use in the present invention provide effective specilizing dye transfer inhibition performance benefits when used in combination with the selected polyrninic dye transfer inhibiting agents described above. The combination of said selected polymeric materials (e.g., PVNO and / or PVPVI) with said selected optical brighteners (e.g., Tinopal UNPA-GX, Tinopal 5BM-GX and / or Tinop "to AMS-GX) provides significantly better dye transfer inhibition in aqueous wash solutions than either of those two components of detergent composition when used alone. Without being limited to the theory, it is believed that such brighteners work in this way because they have high affinity for fabrics in the wash solution and therefore they deposit relatively quickly on these fabrics. The degree to which the brighteners are deposited on the fabrics in the wash solution can be defined by a parameter called "exhaustion coefficient". The depletion coefficient is in general the ratio of a) the polishing material deposited on the cloth to b) the initial polish concentration in the wash liquor. Brighteners with relatively high depletion coefficients are most suitable for inhibiting dye transfer in the context of the present invention. Of course, it will be appreciated that the other types of optional composite optical brightener may be present in the compositions herein to provide conventional "brightness" benefits to the fabrics, rather than a true dye transfer inhibiting effect. Said use is conventional and well known for detergent formulations. Conventional optical brighteners or other brightening or bleaching agents known in the art can be incorporated at levels typically from 0.05% to 1.2% by weight, within the detergent compositions herein. Commercial optical brighteners that may be useful in the present invention can be classified into subgroups including, but not necessarily limited to, stilbene, pyrazoline, curnarin, carboxylic acid, metinocyanin, 5, 5-dibenzotifen dioxide, azoles, heterocycles, ring of 5 and 6 members, and other diverse agents. Examples of such brighteners are described in "The Production and Application of Fluorescent Brightening Agents", "Zahradnik," Published by John Uiley at Sons, New York (1982) Specific examples of optical brighteners that are useful in the present compositions are those identified in US Patent 4,790,856.These brighteners include the PHORUHITE series from Verona. polishes described in this reference includes: Tinopal UNPA, Tinopal CBS and Tinopal 5BM; available from Ciba-Geigy; Arctic lhite CC and Artic Uhite CID, available from Hilton-Davis, located in Italy; loe 2- (4-styryl-phenyl) -2H-naphtholl.1,2-dltriazoles; 4, '-bis- (1, 2, 3-triazol-2-yl) -styl-benzenes; 4,4'-bis (styryl) bis-phenyls; and the y-aminocoumarins. Specific examples of these brighteners include 4-methyl-7-diethyl-aminocu arine; 1, 2-bis (-benzimidazol-2-yl) etiieno; 1,3-diphenylpyrazolines; 2,5-bis (benzoxazol-2-yl) thiophene; 2-styryl-n-ftii-Ci, 2-s] oxazole and 2- (stilben-4-yl) -2H-naphtho-Cl, 2-d] triazole See also US Patent 3,646,015 Anionic brighteners are preferred herein.

Foam suppressors Compounds for reducing or suppressing foaming can be incorporated into the compositions of the present invention. The suppression of foams can be of particular importance in the "high concentration cleaning procedure" and in European front-loading washing machines. A wide variety of materials can be used as foam suppressors, and foam suppressors are well known to those skilled in the art. See, for example, Kirk Othrner Encyclopedia of Chemical Technology, 3a. Edition, Volume 7, pages. 430-447 (-John Uiley to Sons, Inc., 1979). A category of foam suppressant of particular interest includes monocarboxylic fatty acids and salts soluble therein. See U.S. Patent 2,954,347, issued September 27, 1960 to Uayne St. Dohn. The nonocarboxylic fatty acids and salts thereof used as a foam suppressant typically have hydrocarbyl chains of 10 to about 24 carbon atoms, preferably 12 to 18 carbon atoms. Suitable salts include the alkali metal salts such as sodium, potassium and lithium, as well as ammonium and alkanolammonium salts. The detergent co-sites herein may also contain foam suppressors which are not surfactants. These include, for example: high molecular weight hydrocarbons such as paraffin, fatty acid esters (e.g., fatty acid triglycerides), fatty acid esters of monovalent alcohols, aliphatic ketones of C? e.g., stearone), etc. Other foam inhibitors include N-alkylated arninotriazines such as tri- to hexa-alkylmelarnins or di- to tetra-alkyldiaminocrotriazines formed as products of cyanuric chloride with doe or three moles of a primary or secondary amine containing from 1 to 24 atoms of carbon. propylene oxide and monostearyl phosphate such as alcohol phosphate ester, onostyloaryl and alkali metal di phosphates (e.g., K, Na and Li) rnonoestearílicoe and phosphate ester. Hydrocarbons such as par-refine and halogenoparaffins can be used in liquid form. The liquid hydrocarbons will be liquid at room temperature and at atmospheric pressure, and will have a pour point on the scale of about -40 ° C to about 50 ° C, and a minimum boiling point not less than about 110 ° C (atmospheric pressure) ). It is also known to use waxy hydrocarbons, preferably having a melting point below about 100 ° C. Hydrocarbons constitute a preferred category of foam suppressant for detergent compositions. . The hydrocarbon foam suppressors are described, for example, in U.S. Patent 4,265,779. The hydrocarbons, therefore, include saturated or unsaturated aliphatic, alicyclic, aromatic and heterocyclic hydrocarbons having from about 12 to about 70 carbon atoms. The term "paraffin" as used in the discussion of suds suppressors, is intended to include mixtures of true paraffins and cyclic hydrocarbons. Another preferred category of foam suppressors which are not surfactants comprise silicone foam suppressors. This category includes the use of poiorganosiloxane oils such as polydi-ethylsiloxane, dispersions or emulsions of polyorganosiloxane oils or reeins.and combinations of polyorganosiloxane with silica particles wherein the polyorganosiloxane is absorbed or fused onto the silica. Silicone foam suppressors are well known in the art and are described, for example, in U.S. Patent 4,265,779 and EP 35401.6. Other silicone foam suppressors are described in U.S. Patent 3,455,839 which relate to compositions and processes for defoaming aqueous solutions incorporating thereto small amounts of polyethylsiloxane fluids. Silica and silanated silica mixtures are described, for example, in German Patent Application DOS 2,124,526. Silicone foam scavengers and foam controlling agents in granular detergent compositions are described in U.S. Patent 3,933,672 and U.S. Patent 4,652,392. An exemplary silicone-based foam suppressant for use herein is a foaming suppressant amount of a foaming-controlling agent essentially comprising: (i) polydimethylsiloxane fluid having a viscosity of from about 20 is to about 1,500. it is at 25 ° C; (ii) from about 5 to about 50 parts per 100 parts by weight of (i) siloxane resin composed of units of (CH 3) 3 SiO 2/2 units of SiO 2 in a ratio of units of (CH 3) 3 SiQ? 2 to SIO2 units of about 0.6: 1 to about 1.2: 1; and (iii) from about 1 to about 20 parts per 100 parts by weight of (i) of a solid silica gel. In the preferred silicone foam suppressant used herein, the solvent for a continuous phase is made of certain polyethylene glycols or polyethylene-polypropylene glycol copolymers or mixtures thereof (preffered) and non-polypropylene glycol. The primary silicone foam suppressor is branched / interlaced and non-linear. To further illustrate this point, typical liquid laundry detergent compositions with optionally controlled sprays will comprise from about 0.001 to about 1, preferably about 0.01. to about 0.7, most preferably from about 0.05 to about 0.5,% by weight of said silicone foam suppressor, comprising (1) a non-aqueous emulsion of a primary foam anti-foaming agent which is a mixture of (a) a polyorganosiloxane, (b) a resinous eosine or a silicone resin-producing silicone compound, (c) a finely divided filler material and (d) a catalyst to promote the reaction of mixture components (a), (b) and (c) to form silanolates; (2) p > or at least one nonionic silicone surfactant; and (3) polyethylene glycol or a polyethylene-polypropylene glycol copolymer having a solubility in water at room temperature of more than about 2% by weight; and without polypropylene glycol. Similar amounts can be used in granulated gels, etc. See also US Patents 4,978,471 and 4,983,316; 5,288,431 and US Patents 4,639,489 and 4,749,740, Aizawa and others in column 1, line 46 to column 4, line 35. The silicone foam suppressor of the present preferably comprises polyethylene glycol and a polyethylene glycol / polypropylene glycol copolymer, all having an average molecular weight of less than about 1,000, preferably between about 100 and 800. The polyethylene glycol and polyethylene / polypropylene copolymers herein have a solubility in water at room temperature other than about 2% by weight, preferably more than about 5% in weight. The preferred solvent herein is polyethylene glycol having an average molecular weight of less than about 1,000, most preferably between about 100 and 800, most preferably still between 200 and 400, and a copolymer of p > olyethylene glycol / polypropylene glycol, preferably PPG 200 / PEG 300. A weight ratio of between about 1: 1 and 1:10, most preferably between 1: 3 and 1: 6, of polyethylene glycol: polyethylene copolymer is preferred. -polypropylene glycol. The preferred silicone foam suppressors used herein do not contain polypropylene glycol, particularly of molecular weight of 4,000. Preferably they also do not contain block copolymers of ethylene oxide and propylene oxide, such as PLURONIC L101. Other foam euphorpressants useful herein contain the secondary alcohols (v.gr-, 2-alkylalkanols) and mixtures of said alcohols with silicone oils, such as the silicones described in US Pat. No. 4,798,679, 4,075,118 and EP 150,872. Secondary alcohols include Cß-Ciß alkyl alcohols having a Ci-Ciß chain. A preferred alcohol is 2-butyloctanol, which is available from Condea under the trade name ISOFOL 12. Mixtures of secondary alcohols are available under the tradename ISRLCHEM 123 from Enichern. Mixed foam suppressors typically comprise alcohol + silicone blends at a weight ratio of 1: 5 to 5: 1. For any detergent compositions to be used in automatic washing machines, the foams should not be formed to the extent that they overflow from the washing machine. The foam suppressors, when used, are preferably present in an amount of foam suppression. By "foam suppression amount" is meant that the compost formulator can select an amount of this foam controlling agent that will sufficiently control the foams p >to result in a low-spatter laundry detergent for use in automatic washing machines. The compositions herein will generally comprise from 0% to about 5% foam suppressant. When used as suds suppressors, the monocarboxylic fatty acids, and salts thereof, will typically be present in amounts up to about 5%, at p > that, of the detergent composition. Preferably, about 0.5% to about 3% fat suppressant of fatty monocarboxylate foams is used. Silicone foam suppressors are typically used in amounts of up to about 2.0%, by weight, of the detergent composition, although higher amounts may be used. This upper limit is practical in nature, mainly due to the interest of keeping costs reduced to a minimum and the effectiveness of lower quantities to effectively control foaming. Preferably from about 0.01% to about 1% silicone foam suppressant is used, most preferably from about 0.25% to about 0.5%. As used herein, these weight percent values include any silica that may be used in combination with polyorganosiloxane, as well as any auxiliary materials that may be used. The monostearyl phosphate foam suppressors are generally used in amounts ranging from about 0.01% to about 02% by weight of the composition. The hydrocarbon foam suppressors are typically used in amounts ranging from about 0.01% to about 5.0%, although higher levels can be used. The alcohol foam suppressors are typically used at 0.2% -3% by weight of the finished compositions.

Enzymes Another optional ingredient. Useful in the present invention is one or more enzymes. Preferred enzymatic materials include the amylases, neutral and alkaline proteases, lipases, peroxidases, esterases and cellulases commercially available and conventionally incorporated in detergent compositions. Suitable proteolytic enzymes are described in GB-A-1243784, EP-A-013075B and USP 5185250 and 5204015. Suitable amylases are described in GB-A-1296839 while cellulases are described in USP 4435307, GB-A-2075028 and 2095275. Lipases for use in detergent co-detergents are described in GB-A-1372034 and EP-A-0341947. A suitable peroxidase is described by IO89 / 099813. A wide variety of enzyme materials and means for incorporation into synthetic detergent granules is also described in the U.S. Patents. 3,519,570 and 3,533,139.

Fabric softeners Various fabric softeners may optionally be used through washing, especially the impalpable smectite clays of the U.S. patent. 4,062,647, as well as other softening clays known in the art, typically at levels of 0.5% to 10% by weight in the present compositions to provide fabric softening benefits concurrently with fabric cleaning. Clay softeners can be used in combination with amine and cationic softeners as described, for example, in US Pat. 4,375,416 and the patent of E.U.A. 4,291,071.

Other Ingredients A wide variety of other useful ingredients in detergent compositions can be included in the compositions herein, including other active ingredients, carriers, hydrotropes, processing aids, dyes or pigments, solvents for liquid formulations, solid fillers for compjosicionee for bar , etc. If high foam formation is desired, foam increments such as C10-C16 alkanolamides, typically at levels of 1% -10%, can be incorporated into the compositions. Cío-Cu's methanol and diethanolamides illustrate a typical class of such foam boosters. The use of foam enhancers with high foaming surfactants such as the amine oxides, betaines and sultaines mentioned above is also advantageous. If desired, the soluble magnesium salts such as MgCl2, MgSO4 and the like can be added at typically 0.1% -2% levels to provide additional foam and to improve the fat removal performance. Various detersive ingredients employed in the present compositions may optionally be further stabilized by absorbing said ingredients on a porous hydrophobic substrate, subsequently coating said substrate with a hydrophobic coating. Preferably, the detersive ingredient is mixed with a surfactant before being absorbed into the porous substrate. During use the detersive ingredient is released from the substrate in the aqueous washing liquid, where it performs its desired detersive function. To illustrate this technique in more detail, a porous hydrophobic silica (trade name SIPERNRT DIO, Degussa) is mixed with a proteolytic enzyme solution containing 3% -5% nonionic ethoxylated alcohol surfactant of C13-15 (EO 7 ). Typically, the enzyme / surfactant solution is 2.5X the weight of the silica. The resulting powder is dispersed with agitation in silicone oil (various viscosities of silicone oil can be used in the range of 500-12,500). The resulting silicone oil dispersion is emulsified or otherwise added to the final detergent matrix. By this means, ingredients such as enzymes, bleaches, bleach activators, bleach catalysts, photoactivators, colorants, fluorescers, fabric conditioners and above-mentioned hydrolysable surfactants can be "protected" for use in detergents, including liquid laundry detergent compositions. The liquid detergent compositions may contain water and other solvents such as vehicles. The low molecular weight primary and secondary alcohols illustrated by methanol, ethanol, propanol and isopropanol are suitable. Monohydric alcohols are preferred for solubilizing surfactant, but polyols such as those containing 2 to 6 carbon atoms and 2 to 6 hydroxyl groups (eg, 1,3-? -panpanediol, ethylene glycol) can also be used. , glycerin and 1,2-propanediol). The compositions may contain from 5% to 90%, typically from 10% to 50% of said vehicles. The detergent compositions herein will preferably be formulated such that during use in aqueous cleaning operations, the wash water has a pH between 6.5 and 11, preferably between 7.5 and 10.5. The formulations of automatic dishwashing products preferably have a pH between 6.8 and 9.0. Laundry products typically have a pH of 9 to 11. The techniques p >To control the pH at recommended usage levels include the use of pH, alkali, acid, etc. regulators, and they are well known to those skilled in the art. The overall density of the granular detergent compositions is typically at least 450 g / liter, usually at least 600 g / liter and most preferably from 650 g / liter to 1000 g / liter. The invention is illustrated in the following non-limiting examples, in which all percentages are on a weight basis unless indicated otherwise. In detergent compositions, abbreviated component identifications © have the following meaning: XYAS C sodium alkyl sulfate ?? -C ?? 25EY A predominantly linear C12-1S primary alcohol condensed with an average Y moles of C12 ethylene oxide Sulfonate of sodium alkylbenzene linear of C12 TAS Alcohol sulphate of sodium-tallow TAEn tallow alcohol ethoxylated with n moles of oxide ethylene per alcohol C25 E3 S C12-C15 branched sodium alkyl sulphate condensed with three moles of ethylene oxide 45E7 A primary alcohol of C14-15 predominantly lienal condensed with an average of 7 moles of ethylene oxide TFAA: N-methyl alkyl glycol of Cie-Cía Si li cato: Amorphous sodium silicate (normally follows a ratio of SÍO2: Na2?) NaSKS- 6: Layered sodium silicate of formula -Na2 S12 O5 Carbonate: Anhydrous sodium carbonate CMC: Carboxymethylcellulose of sodium Zeolite R: Hydrated sodium aluminosilicate of formula Nai2 (AIO2SÍO2) i2 - 27H2O having a primary particle size on the scale of 1 to 10 microns Polyacrylate Acrylic acid homopolymer of PMt 4000 Citrate: Tri-sodium citrate dihydrate MR / flfl: Maleic acid / acrylic copolymer 1: 4 average molecular weight of about 70,000 Perborate tetrahydrated sodium perborate of nominal formula NaB? 2.3H2O. H2O2 Perborate Monohydrate Perborate Anhydrous Sodium Perborate Bleach Empirical Formula NaB? 2.H2O2 Percarbonate Sodium Percarbonate of nominal formula 2 a2C? 3.3H O2 Savinase: Proteolytic Enzyme Activity 4KNPU / g Alcalase 3T Proteolytic Enzyme Activity 3AU / g Cellulase IT Cellulite enzyme activity 1000 SCEVU / g Lipalase: Lipolitic enzyme activity lOOkLU / g, all sold by NOVO Industries AS DETPMP: Diethylene tria penta (methylene foephonic acid), marketed by Monsanto under the trade name Deq? est 2060: Ethylene diamine disuccinate PVNO: Poly (4-vinylpyridine) N-oxide copolymer of vinylimidazole and vinipyrrolidone having a molecular weight Average rating of 10,000 Foam suppressor mixed 25% paraffin wax tpf 50 ° C, 17% hydrophobic silica and 58% paraffin oil.

EXAMPLE 1 An agglomerate was formed having the following formula of food Kenwood% by weight O ibencenosul fonate 60 of 6-octanarnidocaproyl / oxybenzenesulphonate 6-decanamide caproyl citric acid 25 TAE 25 15 100 A mixture of 6-octanamido-caproyl oxybenzenesulfonate / 6-decanamido-caproyl oxybenzene sulfonate in the form of fine powder (particle size less than 100 microns) and citric acid were added to the Kenwood food mixer and pre-mixed. The temperature of the powders was 25 ° C. The melted non-ionic binder TAE25 was added to the powder mixture over a period of 2 minutes. The resulting loop was mixed additionally for 30 seconds. The mixing was then stopped and stirred into the agglomerate of the Kenwood food mixer to cool it to room temperature. The product was subsequently sieved and materials that were greater than 11.80 microns and less than 250 microns were removed.

EXAMPLE 2 The same procedure was repeated with the exception that the 6-octanarnide-caproyl oxybenzenesulfonate / 6-decanamido-caproyl oxybenzenesulfonate mixture was replaced in the same amounts by benzoyl caprolactam.

EXAMPLE 3 An additional experiment was carried out with the peroxyacid bleach precursor of Example 1 and 2 taken respectively in its raw material form.

EXAMPLE 4 For the purpose of the present invention, unrestricted dissolution conditions are defined as those that exist in the beaker perihdrolysis test which is carried out using a Sotax dislocation tester model AT6 supplied by Sotax AG CH-4008 BASEL Switzerland. This apparatus consists of an arrangement of polycarbonate beakers, each capable of holding 1 liter of water, supported in a thermostatically controlled water bath. Each beaker is provided with a paddle stirrer whose speed can be controlled. Two beakers in the Sotax tester are used in the perhydrolysis procedure using the following method: 1- Adjust the water bath to the required temperature (40 ° C). 2- Add 1 liter of water (12 ° Clark) to each Sotax beaker and allow it to equilibrate to the required temperature. 3- Precisely sample 2 x lOg samples of detergent and precursor. 4- Prepare a number of titration beakers by adding: 25 ml of glacial acetic acid and 3: 2 distilled water solution together with two ice cubes. 5- Adjust the agitation speed of the Sotax at 150 rpm. 6- Add the first sample to the Sotax No. 1 beaker and turn on the clock (t = 0 minutes). Add 5 ml of potassium iodide solution to the first titration beaker. 7- Take a 10 nl aliquot of the Sotax No. 1 beaker and discharge it into the first titration beaker at t-1 minute. 8.- Add the second sample to the Sotax No. 2 beaker at t = 1 mL and add 5 rnl of potassium iodide to a second beaker of titration. 9- Titrate the first aliquot against a sodium thiosulfate solution of 0.005 M until the solution is first decolorized (the color is slowly regenerated when the solution is warmed and the perhydrate reacts with the iodide).

- Take an aliquot of 10 ml from the Sotax beaker No. 2 at t = 2 minutes and discharge it into the second titration beaker and repeat the step. 11- Take additional aliquots at the following times (t = minutes) The aliquots of beaker No. 1 at 1 minute and beaker No. 2 at 2 minutes are replicated and the results are averaged to give a figure of which% per-hydrolysis is calculated.

Material of each example was subsequently incorporated into a detergent formulation model having the composition in% by weight.

The four formulations were subsequently subjected to a beaker perhydrolysis test as described hereinabove and gave the peroxyacid yields shown in table 1. The results are given for 1.3.5 and 10 minutes of lapses of time and are expressed in percent of the theoretically available peracid weight.

It can be seen that the perhydrolysis rate of the 6-octanamido-caproyl oxybenzenesulfonate / 6-decanamido-caproyl oxybenzenesulfonate mixture is significantly improved by agglomeration with citric acid. An improvement can not be observed when the benzoylcaprolactam is similarly agglomerated.

EXAMPLE 5 The same experiment was carried out as above but in a hard water environment (25 ° Clarck) at 60 ° C with only product with peroxyacid fraction of example 3 (C8: C10 oxybenzenesulfonate) and 1. The two formulations were subsequently subjected to the beaker perhydrolysis test as described hereinabove and gave the peroxyacid yields shown in Table II. The results are given for 1,3,5 and 10 minutes of time lapse and are expressed in percent of the theoretically available peracid weight.

It can be seen that the improvement in the perhydrolysis of the 6-octanamido-caproyl oxybenzenesulfonate / 6-decanamido-caproyl oxybenzenesulfonate mixture is consistent on the temperature scale and also in very hard water.

EXAMPLE 6 The same experiment as in EXAMPLE 5 was carried out in a hard water environment (25 ° Clarck) at 30 ° C with the exception that the peroxyacid bleach precursor was replaced by 6-decanaride-caproyl oxybenzenesulfonate with different % porosity and different average pore diameter. The two formulations were subsequently subjected to the beaker perhydrolysis test as described hereinabove and gave the peroxyacid yields shown in Table III. The results are given for 3.5 and 10 minutes of time lapse and are expressed in percent of the theoretically available peracid weight. * according to example 3 ** as was done according to example 1 It can be seen that the 6-decanamido-caproyl oxybenzenesulfonate in the form of agglomerate produces a way to improve the perhydrolicity against the 6-decanamido-caproyl oxybenzenesulfonate in raw material form. Furthermore, it can also be observed that the 6-decanamido-caproyl oxybenzenesulfonate particles having a% porosity > 12 and a mean pore diameter > 0.5 um show improved perhydrolysis.

EXAMPLE 7 The following detergent compositions are in accordance with the invention.

A B. C D LASC12 6.5 6.5 7.6 6.9 TAS 3.0 3.0 1.3 2.0 C2SE3 0.15 0.15 0.15 0.1 C «E7 4.0 5.0 1.3 4.0 Zeolite 1.8.0 17.0 17.0 20 Citrate - - 1.5 5.5 Citric acid 2.3 1.8 2.6 - SKS-6 8.7 6.5 9.5 - Carbonate 16.0 15.5 7.0 15. 4 Silicate (re. 2.0) 0.5 0.5 0.5 3.0 Bicarbonate 4.5 7.5 1.5 - Copolymer MA / AA 4.0 4.5 3.2 4.0 CMC 0.3 0.3 0.2 0.3 Savinase 0.4 - 0.4 1.4 Lipolase 0.2 0.1 0.1 0.3 Celulase 0.15 0.15 - 0.1 Alcalase - 0.3 _ _ Perborate 9.0 11. 6 \ Perborate Monohydrate 5.0 8.7 Percarbonate 17.5 16.5 - - DETPMP 0.4 0.4 0.4 0.4 MgSO? 0.4 0.4 0.4 0.4 Fluorescedor 0.19 0.19 0.15 0.1 9 Foam suppressor 0.8 0.8 0.8 0.8 Perfume: 0.35 0.4 0.35 0.4 Peroxyacid precursor composition (1): 4.5 - 3.4 Peroxyacid precursor composition (2): - 2.5 - 5.0 Sul ato Minors, etc. a: 100 100 100 100 (1) as in example 1 (2) as in example 6, agglomerate of 6-decanamido-caproyl oxybenzenesulfonate having a porosity% = 15.2 and a mean pore diameter = 0.8 μm)

Claims (12)

NOVELTY OF THE INVENTION CLAIMS

1. - A peroxyacid bleach precursor composition consisting of: a) a peroxyacid bleach precursor of a size of less than 100 μ and selected from precursors that produce under hydrophobic peroxyacid perhydrolysis whose parent carboxylic acid has a concentration of critical micelle less than 0.5 moles / liter; and b)? composed of organic acid soluble in water; wherein said precursor and said organic acid are in close physical proximity.

2. A peroxyacid bleach precursor composition according to claim 1, wherein the basic structure chain of the peroxyacid contains more than 7 carbons.

3. A peroxyacid bleach precursor composition according to any of claims 1 or 2, wherein said organic acid com- pound is present in an amount of 5% to 50% by weight of the bleach precursor composition. of peroxyacid.

4. A peroxyacid bleach precursor composition according to claim 1, wherein said bleach precursor is selected from those containing one or more N- or 0-acyl groups.

5. A peroxyacid bleach precursor composition according to claim 1, wherein said bleach precursor is selected from 3,5,5-tri-methyl hexanoyl oxybenzenesulfonate, nonanoyl oxybenzenesulfonate, caproyl oxybenzenesulfonate derivatives and any mix of them.

6. A peroxyacid bleach precursor composition according to claim 1, wherein said bleach activator is a caproyl oxybenzene sulfonate derivative selected from 6-octanamido-caproyl oxybenzenesulfonate, 6-nonanamidocaproyl oxybenzenesulfonate, oxybenzenesulfonate. of 6-decanamido-caproyl and mixtures of the types.

7. A peroxyacid bleach precursor composition according to claim 1, wherein said organic acid compound is monomeric or oligomeric carboxylate.

8. A peroxyacid bleach precursor composition according to claim 1, wherein said organic acid compound is a monomeric aliphatic carboxylic acid selected from glycolic, l-lactic and citric acids, preferably citric acid.

9. A peroxyacid bleach precursor composition according to claim 1, wherein said bleach precursor composition is further agglomerated bound with a binder.

10. A peroxyacid bleach precursor composition according to claim 1, wherein said bleach precursor composition is an agglomerate having an average pore diameter of at least 0.5 microns.

11. A detergent composition consisting of a material, a source of alkaline hydrogen peroxide and further comprising a peroxyacid bleach precursor composition according to claim 1.

12. A detergent composition in accordance with the claim 11, wherein said source of alkaline hydrogen peroxide is an inorganic perhydrate salt, preferably sodium perborate or sodium percarbonate.