MXPA00000164A - Non-aqueous, particulate-containing detergent compositions containing bleach precursor compositions - Google Patents

Abstract

A non-aqueous liquid detergent composition comprising a bleach precursor composition comprising:a) a bleach precursor;and b) a surfactant system;and c) salt of an organic acid.

Description

NON-AQUEOUS DETERGENT COMPOSITIONS CONTAINING PARTICLES AND CONTAINING PRECURSOR COMPOSITIONS OF BLEACH FIELD OF THE INVENTION This invention relates to non-aqueous laundry detergent products which are in the form of a liquid and which are in the form of stable dispersions of particulate material, such as bleaching agents and bleach precursor.

BACKGROUND OF THE INVENTION Detergent products in liquid form are commonly considered more convenient to use than detergent products in dry or particulate powder. Therefore, said detergents have found a substantial acceptance of the consumers. Said detergent products can be easily measured, they dissolve rapidly in the wash water, they are capable of being easily applied in concentrated solutions or dispersions to soiled areas on garments that will be washed and do not form dust. They also normally occupy less storage space than granulated products. In addition, said detergents may have incorporated in their formulations materials that could not support drying operations without deterioration, operations that are commonly used in the manufacture of detergent products in particles or granulates. Although said detergents have several advantages over granular detergent products, they also inherently possess several disadvantages. In particular, the components of the detergent composition which may be compatible with each other in granulated products may tend to interact or react with one another. In this way, components such as enzymes, surfactants, perfumes, brighteners, solvents and especially bleach and bleach activators can be especially difficult to incorporate into liquid detergent products which then have a degree of acceptable chemical stability. One approach to improving the chemical compatibility of detergent composition components in detergent products has been to formulate non-aqueous (or anhydrous) detergent compositions. In such non-aqueous products, at least some of the normally solid detergent composition components tend to remain insoluble in the liquid product and are therefore less reactive with each other than if they had been dissolved in the liquid matrix. Non-aqueous liquid detergent compositions, including those containing reactive materials such as peroxygen bleaching agents, have been described, for example, in Hepworth et al., U.S. Pat. 4,615,820, issued October 17, 1986; Schultz et al., Patent of E.U.A. 4,929,380, issued May 29, 1990; Schultz et al., Patent of E.U.A. do not. 5,008,031, issued April 16, 1991; Eider and ? ^ g others, EP-A-030,096, published June 10, 1981; Hall et al., WO 92/09678, published June 11, 1992 and Sanderson et al., EP-A-565,017, published October 13, 1993. A particular problem that has been observed with the incorporation of bleach precursors in non-aqueous detergents, includes the chemical stability of the bleach precursor. EP 339 995 discloses a non-aqueous liquid detergent composition comprising a persal bleach and a precursor therefor, the composition containing a non-ionic alkoxylated surfactant of blocked ends. EP 540 090 proposes the use of a bleach precursor that is relatively insoluble in the non-aqueous liquid phase of the liquid detergent composition. One difficulty associated with improving the chemical stability of the bleach precursor is that, after dilution in the wash liquid, the bleach precursors still need to have a certain degree of solubility high enough to be effective as bleaching species in the washing liquid. In view of the foregoing, there is clearly a continuing need to identify and provide non-aqueous detergent compositions containing bleach precursor in the form of liquid products having a high degree of chemical stability in the concentrate., together with an efficient bleaching performance in the washing liquid. Accordingly, an object of the present invention is to provide a non-aqueous detergent composition in which the bleach precursors have improved chemical stability in the concentrate, while still being effective as bleach species in the wash liquor. According to the present invention, a non-aqueous detergent composition is provided which is in the form of a liquid, which contains a bleaching agent and a bleach precursor composition.

BRIEF DESCRIPTION OF THE INVENTION The present invention provides a heavy-duty non-aqueous detergent composition which is in the form of a liquid, said composition comprising a bleaching agent and a bleach precursor composition.

DETAILED DESCRIPTION OF THE INVENTION Bleach precursor composition In accordance with the present invention, the bleach precursor composition comprises: a) a bleach precursor; b) a surfactant system and c) salt of an organic acid. According to a preferred embodiment of the present invention, the bleach precursor composition comprises: = w ^ j j «a) a bleach precursor; b) a surfactant system comprising a non-ethoxylated anionic surfactant and / or a nonionic surfactant and c) an organic acid salt, wherein said surfactant, said precursor and said organic acid are in the form of an agglomerate, granule or Extruded material, and wherein said precursor, said surfactant system and the salt of the organic acid are optionally coated in an intimate mixture. a) Bleach precursor An essential component of the invention is a bleach precursor. Suitable bleach precursors for inclusion in the composition according to the invention typically contain one or more N- or O-acyl groups, precursors that can be selected from a wide range of classes. Suitable classes include anhydrides, esters, imides, nitriles and acylated derivatives of imidazoles and oximes, and examples of useful materials within these classes are described in GB-A-1586789. Suitable esters are described in GB-A-836988, 864798, 147871, 2143231 and EP-A-0170386. The acylation products of sorbitol, glucose and all saccharides with benzoylating agents and acetylating agents are also suitable. Specific O-acylated precursor compounds include 3,5,5-tri-methylhexanoyloxybenzenesulfonates, benzoyloxybenzenesulfonates, cationic derivatives of benzoyloxybenzenesulfonates, nonanoyl-6-aminocaproyloxybenzenesulfonates, monobenzoyltetraacetylglucose and pentaacetylglucose. Phthalic anhydride is a suitable anhydride-type precursor. Suitable and useful N-acyl compounds are described in GB-A-855735, 907356 and GB-A-1246338. Preferred imide-type precursor compounds include N-benzoylsuccinimide, tetrabenzoylethylenediamine, N-benzoyl-substituted ureas and the N, N-N'N'-tetraacetylated alkylenediamines in which the alkylene group contains 1 to 6 carbon atoms, particularly the compounds in which the alkylene group contains 1, 2 and 6 carbon atoms. A most preferred precursor compound is N, N-N ', N'-tetraacetylethylenediamine (TAED). The N-acylated precursor compounds of the lactam class are generally described in GB-A-955735. Although the broader aspect of the invention contemplates the use of any lactam useful as a peroxyacid precursor, the preferred materials comprise the caprolactams and valerolactams. Suitable caprolactam bleach precursors have the formula: .J & Éi &Jii **. ",, .. ^" wherein R1 is H or an alkyl, aryl, alkoxyaryl or alkaryl group containing from 1 to 12 carbon atoms, preferably from 6 to 12 carbon atoms. Suitable valerolactams have the formula: wherein R1 is H or an alkyl, aryl, alkoxyaryl or alkaryl group containing from 1 to 12 carbon atoms, preferably from 6 to 12 carbon atoms. In highly preferred embodiments, R is selected from phenyl, heptyl, octyl, nonyl, 2,4,4-trimethylpentyl, decenyl and mixtures thereof. The materials that are most preferred are those that are normally solid to < 30 ° C, particularly the phenyl derivatives, ie, benzoylvalerolactam, benzoylcaprolactam and its substituted benzoyl analogs such as chloro, amino, nitro, alkyl, alkyl, aryl and alkyloxy derivatives. The caprolactam and valerolactam precursor materials in which the portion R1 contains at least 6, preferably from 6 to about 12 carbon atoms, provide peroxyacids in hydrophobic perhydrolysis which produce a nucleophilic cleansing and dirtiness of the body. The precursor compounds in which R1 comprises from 1 to 6 atoms i & | ^^ of carbon provide hydrophilic bleaching species that are particularly efficient for bleaching beverage stains. Mixtures of "hydrophobic" and "hydrophilic" caprolactams and valerolactams, typically at weight ratios of 1: 5 to 5: 1, preferably 1: 1, can be used herein for mixed stain removal benefits. Another class of bleach precursor materials that is preferred includes cationic bleach activators, derivatives of the valerolactam and acylcaprolactam compounds of the formula: wherein x is 0 or 1, the substituents R, R 'and R "are each C1-C10 alkyl or C2-C4 hydroxyalkyl groups, or [(CyH2y) O] nR" \ where y = 2-4 , n = 1-20 and R '"is a C1-C4 alkyl group or hydrogen, and X is an anion Suitable imidazoles include N-benzoyl-imidazole and N-benzoylbenzimidazole, and other peroxyacid precursors containing N group Useful acyl include N-benzoyl pyrrolidone, dibenzoyltaurine and benzoyl pyrglutamic acid Another preferred class of bleach activator compounds are the amide substituted compounds of the following general formulas: R1N (R5) C (O) R2C (O) L or R1C (O) N (R5) R2C (O) L wherein R 1 is an alkyl, alkylene, aryl or alkaryl group with about 1 to about 14 carbon atoms, R 2 is an alkylene, arylene and alkarylene group containing from about 1 to 14 carbon atoms and R 5 is H or an alkyl group , aryl or alkaryl containing 1 to 10 carbon atoms and L can be essentially any leaving group. R1 preferably contains about 6 to about 12 carbon atoms. R 2 preferably contains about 4 to about 8 carbon atoms. R 1 may be straight or branched chain alkyl, substituted aryl or alkylaryl containing branching, substitution or both, and may be obtained either from synthetic sources or from natural sources, including for example, tallow grease. Analogous structural variations for R2 are permissible. The substitution may include alkyl, aryl, halogen, nitrogen, sulfur and other substituent groups or typical organic compounds. R5 is preferably H or methyl. R1 and R5 preferably should not contain more than 18 carbon atoms in total. Examples of bleach precursors of the above formulas that are preferred include the amide substituted peroxyacid precursor compounds selected from (6-octanamido-caproyl) oxybenzenesulfonate, (6-nonanamidocaproyl) oxybenzenesulfonate, (6-decanamido-caproyl) oxybenzenesulfonate, and mixtures thereof as described in EP-A-0170386.

Benzoxazine type precursor compounds are also suitable, such as those described for example in EP-A-332,294 and EP-A-482,807, particularly those having the formula: including the substituted benzoxazines type wherein Ri is H, alkyl, alkaryl, aryl, arylalkyl, secondary or tertiary amines, and wherein R 2, R 3, R 4 and R 5 can be the same or different substituents selected from H, halogen, alkyl, alkenyl, aryl, hydroxyl, alkoxy, amino, alkyl, amino, COOR6 (wherein Re is H or an alkyl group) and carbonyl functions. A benzoxazine-like precursor which is especially preferred is: The particles of the particulate bleach activator component preferably have a particle size of 250 microns at 2000 microns. These bleach precursors can be partially replaced by preformed peracids such as N, N-phthaloylaminoperoxy acid (PAP), peroxyadipic acid nonyl amide (NAPAA), acid 1,2-diperoxydodecanoic acid (DPDA) and trimethylammonium propenylimidoperoxymethyl acid (TAPIMA). Among the bleach precursors described above that are most preferred are the amide substituted bleach precursor compounds. Most preferably, the bleach precursors are the amide substituted bleach precursor compounds selected from (6-octanamido-caproyl) oxybenzenesulfonate, (6-nonamidocaproyl) oxybenzenesulfonate, (6-decanamidocaproyl) oxybenzenesulfonate and mixtures thereof. The bleach precursors are normally incorporated at a level of 20% to 95%, preferably 50% to 90% by weight of the bleach activating component, and most preferably at least 60% by weight thereof. b) Surfactant system Surfactants are useful in the bleach precursor compositions of the present invention, in particular as solubilizing agents. Anionic, nonionic, cationic, amphoteric and / or zwitterionic surfactants are useful. Non-limiting examples of surfactants useful herein include the conventional C 11 -C 18 alkylbenzenesulfonates ("LAS") and the branched and random chain C 10 -C 20 primary alkyl sulfates ("AS"), the secondary alkyl sulfates (2,3) of C10-C18 of the formula CH3 (CH2) x (CHOSO3- M +) CH3 and CH3 (CH2) and (CHOSO3-M +) CH2CH3 where x and (y +1) are integers of at least 7, preferably at least about 9, and M is a water-soluble cation, especially sodium, unsaturated sulfates such as oleyl sulfate, C10-C18 alkylalkoxy sulfates ("AExS", especially EO-1-7 ethoxysulfates), C10-C18 alkylalkoxycarboxylates (especially ethoxycarboxylates) EO 1-7), the C10-C18 glycerol ethers, the C10-C18 alkyl polyglycosides and their corresponding sulphated polyglucosides, the sulfonated alpha fatty acid esters of C12-C18, methyl ester sulfonate ("MES") and oleoylsarcosinate. A preferred embodiment of the present invention is a surfactant system comprising an anionic surfactant and / or a nonionic surfactant. The surfactant system will typically be present in an amount of 0.1% to 50% by weight of the precursor composition, most preferably in an amount of 5-15%. Preferred anionic surfactants are the non-ethoxylated anionic surfactants. These may include salts (including, for example, sodium, potassium, ammonium and substituted ammonium salts such as mono-, di- and triethanolamine salts) of the anionic sulfate, sulfonate, carboxylate and sarcosinate surfactants.

Other anionic surfactants include the isethionates such as acyl isethionates, N-acyltaurates, fatty acid amides of methyl tauride, alkyl succinates and sulfosuccinates, sulfosuccinate monoesters (especially saturated and unsaturated C? 2-C? 8 monoesters), sulfosuccinate diesters (especially C-C saturated and unsaturated diesters), N-acyl sarcosinates. The rosin acids and hydrogenated rosin acids are also suitable, such as rosin, hydrogenated rosin and rosin acids and hydrogenated rosin acids present in or derived from tallow oil. Suitable anionic sulfate surfactants for use herein include linear and branched primary alkyl sulphates, fatty oleyl glycerol sulfates, acyl-N-C-C4 alkyl and acyl-N- (C? -C4 alkyl) sulfates of C5-C-? and -N- (hydroxyalkyl of C? -C-? 2) glucamine and alkylpolysaccharide sulfates such as the alkyl polyglycoside sulphates (the non-sulfated nonionic compounds are described herein) The alkyl sulfate surfactants are preferably selected from the group consisting of of C10-C20 alkylsulphates of branched and random chain ("AS"), the alkyl sulfates (2,3) secondary of C10-C18 of the formula CH3 (CH2) x (CHOSO3-M +) CH3 and CH3 (CH2) and ( CHOSO3-M +) CH2CH3 wherein 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 sulfates such as oleyl sulfate. Sulfonate anionic surfactants suitable for use herein include salts of linear alkylbenzene sulphonates of C- * ^^ ^ w? ^^^^ C20, alkylestersulfonates, primary or secondary C6-C22 alkanesulfonates, C6-C24 olefinsulfonates, sulfonated polycarboxylic acids, alkyl glycerol sulfonates, fatty acyl glycerol sulfonates, fatty oleyl glycerol sulfonates and any mixture thereof. Suitable anionic carboxylate surfactants for use herein include soaps ('alkylcarboxyls'), especially certain secondary soaps such as those described herein. The preferred soap surfactants are secondary soap surfactants containing a carboxyl unit connected to a secondary carbon. The secondary carbon may be in a ring structure, for example, as in p-octylbenzoic acid, or as in alkyl-substituted cyclohexylcarboxylates. The secondary soap surfactants preferably should not contain ether bonds, ester bonds or hydroxyl groups. Preferably there should be no nitrogen atoms in the upper group (amphiphilic portion). Secondary soap surfactants typically contain 11-15 total carbon atoms, although they may be tolerated slightly more (eg, up to 16), for example, p-octylbenzoic acid. The following general structures best illustrate some of the secondary soap surfactants that are preferred: A. A highly preferred class of secondary soaps comprises the secondary carboxyl materials of the formula R 3 CH (R 4) COOM, wherein R 3 is CH 3 (CH 2) ) X and R4 is CH3 (CH2) y, where (y) can be O or an integer from 1 to 4, x is an integer from 4 to 10 and the sum of (x + y) is 6-10, preferably 7-9, most preferably 8. B. Another preferred class of secondary soaps comprises carboxyl compounds in which the carboxyl substituent is on a ring hydrocarbyl unit, ie, secondary soaps of the formula R5-R6-COOM, wherein R5 is C7-C10 alkyl or alkenyl, preferably C8-C9 and R6 it is a ring structure, such as benzene, cyclopentane and cyclohexane. (Note: R5 may be in the ortho, meta or para position relative to the carboxyl in the ring). C. Still another preferred class of secondary soaps comprises the secondary carboxyl compounds of the formula: CH3 (CHR) k- (CH2) m- (CHR) n -CH (COOM) (CHR) 0- (CH2) p - (CHR) q-CH3, where each R is C? -C4 alkyl, where k, n, o, q are integers on the 0-8 scale, as long as the total number of carbon atoms ( including the carboxylate) is on the scale of 10 to 18. In each of the formulas A, B and C above, the M species can be any counterion soluble in water suitable. The secondary soap surfactants which are especially preferred for use herein are the water-soluble members selected from the group consisting of the water-soluble salts of 2-methyl-1-undecanoic acid, 2-ethyl-1-decanoic acid, 2- propyl-1-nonanoic acid, 2-butyl-1-octanoic acid and 2-pentyl-1-heptanoic acid.

Other suitable anionic surfactants are the alkali metal sarcosinates of the formula R-CON (R 1) CH 2 COOM, wherein R is a linear or branched C 5 -C 7 alkylene or alkenyl group, R 1 is an alkyl group of C -? - C4 and M is an alkali metal ion. Preferred examples are the myristyl and oleyl methyl sarcosinates in the form of their sodium salts. Among the non-ethoxylated anionic surfactants described above, anionic sulfate surfactants, anionic sulfonate surfactants or mixtures thereof are preferred. Most preferably, the anionic surfactant is selected from C ?2-C-I5 (AS) salts, linear C5-C2o alkylbenzenesulfonates and mixtures thereof, and most preferably is the linear alkylbenzenesulfonate salt of Cs-C2o. Preferably, the anionic surfactant is present in an amount of 1-25%, most preferably 5-15%.

Nonionic Surfactant Essentially any nonionic surfactant useful for detersive purposes can be included in the compositions, such as polyhydroxy fatty acid amide surfactants, alkylphenol condensates, ethoxylated alcohol surfactants, ethoxylated / propoxylated fatty alcohol surfactant, condensates of ethylene oxide / propylene oxide with propylene glycol, condensation products of ethylene oxide with propylene oxide / ethylene diamine adducts, alkylpolysaccharide surfactants, fatty acid amide surfactants and mixtures thereof. Exemplary and non-limiting classes of useful nonionic surfactants are listed below. The polyhydroxy fatty acid amides suitable for use herein are those having the structural formula R2CONR1Z wherein: R1 is H, CrC4 hydrocarbyl, 2-hydroxyethyl, 2-hydroxypropyl or a mixture thereof, preferably C? -C4, most preferably Ci or C2 alkyl, more preferably Ci alkyl (ie, methyl); and R2 is a C5-C3 hydrocarbyl, preferably straight chain C5-C19 alkyl or alkenyl, most preferably straight chain Cg-C? 7 alkyl or alkenyl, more preferably Cn-C? 7 alkyl or alkenyl of Straight chain, or mixtures thereof; and Z is a polyhydroxyhydrocarbyl having a linear hydrocarbyl chain with at least 3 hydroxyls directly connected to the chain, or an alkoxylated derivative (preferably ethoxylated or propoxylated) thereof. Z will preferably be derived from a reducing sugar in a reductive amination reaction; most preferably Z is a glucitol. The polyethylene oxide, polypropylene and polybutylene condensates of alkylphenols are suitable for use herein. In general, polyethylene oxide condensates are preferred. These compounds include the condensation products of alkylphenols having an alkyl group containing about 6 to about 18 carbon atoms in either a straight or branched chain configuration with the alkylene oxide. The alkylethoxylated condensation products of aliphatic alcohols with from about 1 to about 25 moles of ethylene oxide are suitable for use herein. The alkyl chain of the aliphatic alcohol may be straight or branched, primary or secondary, and generally contains from 6 to 22 carbon atoms. Particularly preferred are the condensation products of alcohols having an alkyl group containing from 8 to 20 carbon atoms with from about 2 to about 10 moles of ethylene oxide per mole of alcohol. As ethoxylated / propoxylated fatty alcohol surfactants, the ethoxylated C6-C-? 8 fatty alcohols and the mixed ethoxylated / propoxylated Cβ-C-is fatty alcohols are suitable surfactants for use herein, particularly when they are soluble in water. Water. Preferably, the ethoxylated fatty alcohols are ethoxylated fatty alcohols of C-? Or C? 8 with an ethoxylation degree of 3 to 50, most preferably are ethoxylated fatty alcohols of C? 2-C? 8 with an ethoxylation degree of 3. to 40. Preferably, mixed ethoxylated / propoxylated fatty alcohols have an alkyl chain length of 10 to 18 carbon atoms, a degree of ethoxylation of 3 to 30 and a degree of propoxylation of 1 to 10. The condensation products of Ethylene oxide with a hydrophobic base formed by the condensation of propylene oxide with propylene glycol are suitable for use herein. The hydrophobic portion of these compounds preferably has a molecular weight of from about 1500 to about 1800 and exhi insolubility in water. Examples of compounds of this type include certain of the commercially available Pluronic ™ surfactants and sold by BASF.

The condensation products of ethylene oxide with the product resulting from the reaction of propylene oxide and ethylenediamine are suitable for use herein. The hydrophobic portion of these products consists of the reaction product of ethylenediamine and excess propylene oxide, and generally have a molecular weight of about 2500 to about 3000. Examples of this type of nonionic surfactant include certain of the Tetronic ™ compounds available commercially and sold by BASF. Alkypolysaccharides suitable for use herein are described in the U.S.A. 4,565,647, Filling, issued January 21, 1986, having a hydrophobic group containing about 6 to about 30 carbon atoms, preferably about 10 to about 16 carbon atoms and a hydrophilic group of polysaccharide, for example a polyglucoside, containing from about 1.3 to about 10, preferably from about 1.3 to about 3, most preferably from about 1.3 to about 2.7 units of saccharide. Any reducing saccharide containing 5 or 6 carbon atoms can be used; for example, the glycosyl moieties can be replaced by glucose, galactose and galactosyl moieties. (Optionally, the hydrophobic group is attached at positions 2-, 3-, 4-, etc., thus giving a glucose or galactose unlike a glycoside or gaiactoside). The linkages between saccharides can be, for example, between position one of the additional saccharide units and positions 2-, 3-, 4- and / or 6- in the preceding saccharide units. The alkyl polyglucosides that are preferred have the formula: R20 (CnH2nO) t (glucosyl) x E n where R2 is selected from the group consisting of alkyl, alkylphenyl, hydroxyalkyl, hydroxyalkylphenyl and mixtures thereof, wherein the alkyl groups contain from 10 to 18, preferably 12 to 14 carbon atoms; carbon; n is 2 or 3, t is from 0 to 11, preferably 0, and X is from 1.3 to 8, preferably 1.3 to 3, most preferably from 1.3 to 2.7. The glucosyl is preferably derived from glucose. Suitable fatty acid amide surfactants for use herein are those having the formula: R6CON (R7) 2, wherein R6 is an alkyl group containing from 7 to 21, preferably from 9 to 17 carbon atoms, and each R7 is selected from the group consisting of hydrogen, C? -C4 alkyl, hydroxyalkyl of CC and - (C2H0) xH, where x is on the scale of 1 to 3. Among the nonionic surfactants described above preferred are ethoxylated surfactants, preferably selected from ethoxylated alcohol surfactants, ethoxylated / propoxylated fatty alcohol surfactant, ethylene oxide / propylene oxide condensates with propylene glycol, oxide condensation products Ethylene oxide with propylene oxide / ethylene diamine adducts and mixtures thereof, most preferably ethoxylated alcohol surfactants. The most preferred ethoxylated alcohol surfactants are the condensation products of alcohols having an alkyl group containing from 8 to 20 carbon atoms with from 2 to 10 moles of ethylene oxide per mole of alcohol, in particular alcohol linear primary (C12 / C14) condensed with an average of 3 moles of ethylene oxide. c) Organic acid or salt thereof Organic acid compounds suitable for the purposes of the present invention comprise aliphatic or aromatic monomeric or oligomeric carboxylates, and preferably comprise monomeric aliphatic carboxylic acids. Examples of said aliphatic acid compounds are glycolic, glutamic, citraconic, succinic, 1-lactic and citric acids. Citric acid is a surface treatment agent that is particularly preferred. Typical levels of said acids are 1-30%, preferably 2-20%, most preferably 5-15% by weight of the bleach precursor composition. It has surprisingly been found that the salt of the organic acid increases the chemical stability of the bleach precursor in the non-aqueous liquid detergent and reduces the tendency for the bleach activator to solubilize in the matrix. In addition, the rheological stability of the product is improved.

HÉÉM ^ Form of the bleach precursor composition The bleach precursor composition may be in any particulate form suitable for incorporation into a detergent composition, such as agglomerate, granule, extruded material or extruded material in spheres. Preferably, the bleach precursor composition is in the form of an extruded spherical material. Preferably, the process for manufacturing the extruded material in bleach activator spheres comprises the steps of: (i) preparing a mixture of solids, and optionally liquids, comprising the bleach activator; (ii) extruding the mixture through a die under a pressure to form an extruded material, the pressure being less than 25 bar and (iii) fragmenting the extruded material to form the extruded material into spheres. Preferably, the mixing step (i) is carried out using a Loedige® mixer, the extrusion step (ii) using a dome extruder such as a Fuji Paudal model DGL-1, most preferably with a die having holes that measure < 1 mm and extruded at a pressure of approximately 20 bar. Step (iii) is preferably carried out using a rotating disk spheronizer such as a Fuji Paudal QJ-400 wherein the extruded materials are fragmented into short lengths and shaped into substantially spherical particles.

Preferably, the non-ethoxylated anionic surfactant is mixed in step (i) with the bleach precursor component. The non-aqueous liquid detergent compositions incorporating the peroxyacid bleach precursor will usually contain from 1% to 25% of the precursor particles, very frequently from 1% to 20% and more preferably from 1% to 15% on a weight basis of the composition. Surprisingly, it has now been found that the bleach precursors of the present invention are physically and chemically stable in the concentrate (the non-aqueous liquid detergent), while at the same time they are more effective as a kind of bleaching in the liquid of washed. The non-aqueous detergent compositions of this invention may further comprise a surfactant and a liquid phase containing solvent of low polarity and having dispersed therein the bleach precursor composition. The components of the liquid and solid phases of the detergent compositions herein, as well as the form, preparation and use of the composition are described in greater detail as follows: All concentrations and ratios are on a weight basis, a unless otherwise indicated.

Surfactant The amount of the surfactant mixture component of the non-aqueous liquid detergent compositions herein may vary It is dependent on the nature and amount of the other components of the composition and depending on the desired rheological properties of the finally formed composition. In general, this surfactant mixture will be used in an amount comprising from about 10% to 90% by weight of the composition. Most preferably, the surfactant mixture will comprise about 15% to 50% by weight of the composition. A typical list of anionic, nonionic, ampholytic and zwitterionic surfactants, and species of these surfactants, is given in the U.S. patent. 3,664,961 issued to Norris on May 23, 1972. The highly preferred anionic surfactants are linear alkylbenzenesulfonate (LAS) materials. Said surfactants and their preparation are described for example in the patents of E.U.A. 2,220,099 and 2,477,383 incorporated herein by reference. Linear straight sodium and potassium alkylbenzenesulfonates in which the average number of carbon atoms in the alkyl group is from 11 to about 14 are especially preferred. Cu-C sodium LAS is preferred., for example, LAS of C-? 2. Preferred anionic surfactants include the alkyl sulfate surfactants which are water soluble salts or acids of the formula ROSO 3M, wherein R is preferably a C 1 or C 24 hydrocarbyl, preferably an alkyl or hydroxyalkyl having one component C? 0-C? 8 alkyl, most preferably an alkyl or hydroxyalkyl of C12-C? 5, and M is H or a cation, for example, an alkali metal cation (sodium, potassium, lithium) or cations of ammonium or substituted ammonium (quaternary ammonium cations such as tetramethylammonium cations and dimethylpiperidinium). Highly preferred anionic surfactants include ethoxylated alkyl sulfate surfactants which are salts or water soluble acids of the formula RO (A) mSO3M wherein R is an unsubstituted C? Or C 24 alkyl or hydroxyalkyl group having one component C-io-C24 alkyl, preferably an alkyl or hydroxyalkyl of C-? 2-C18, most preferably alkyl or hydroxyalkyl of C-? 2-C-i5, A is an ethoxy or propoxy unit, m is greater than zero, typically between about 0.5 and about 6, most preferably between about 0.5 and about 3, and M is H or a cation which may be, for example, a metal cation (eg, sodium, potassium, lithium, calcium, magnesium, etc.), ammonium or substituted ammonium cation. Ethoxylated alkyl sulfates as well as propoxylated alkyl sulphates are contemplated herein. Specific examples of substituted ammonium cations include quaternary ammonium cations such as tetramethylammonium cations and dimethylpiperidinium. Exemplary surfactants are polyethoxylated alkyl sulfate (1.0) of C12-C5 (C12-C15E (1.0) M) polyethoxylated alkyl sulfate (2.25) of C12-C15 (C12-C15E (2.25) M), polyethoxylated alkyl sulfate (3.0) of C12-C? 5 (d2-C? 5E (3.0) M) and polyethoxylated alkyl sulfate (4.0) of C12-C? 5 (C12-C15E (4.0) M), wherein M is conveniently selected from sodium and potassium. Other suitable anionic surfactants to be used are the alkyl ether sulfonate surfactants which include linear esters of C8-C2o carboxylic acids (ie, fatty acids) which are sulphonated with g *? g = jX S03 gaseous according to "The Journal of the American Oil Chemists Society", 52 (1975), p. 323-329. Suitable starting materials may include natural fatty substances such as those derived from tallow, palm oil, etc. The alkyl ether sulfonate surfactant which is preferred, especially for washing applications, comprises the alkyl ether sulfonate surfactants of the structural formula: OR R3- CH- C-OR4 S03M wherein R3 is a C8-C2o hydrocarbyl, preferably an alkyl, or combination thereof, R4 is a Ci-Cβ hydrocarbyl, preferably an alkyl or combination thereof, and M is a cation forming a water-soluble salt with the alkyl ether sulfonate. Suitable salt-forming cations include metals such as sodium, potassium and lithium and ammonium and substituted ammonium cations. Preferably, R3 is C10-C16 alkyl and R4 is methyl, ethyl or isopropyl. Methyl ester sulfonates in which R3 is C10-C16 alkyl. Other anionic surfactants useful for detersive purposes may also be included in the laundry detergent compositions of the present invention. These may include salts (including, for example, sodium, potassium, ammonium, and substituted ammonium salts such as mono-, di- and triethanolamine salts) of soap, linear alkylbenzenesulfonates of C9-C20l primary or secondary alkanesulfonates of C8-C22 , C8-C2 olefinsulfonates, sulfonated polycarboxylic acids prepared by sulfonation of the pyrolyzed product of alkaline earth metal citrates, for example, as described in the specification of British Patent No. 1, 082,179, C8-C24 alkyl polyglycol ether sulphates (which contain up to 10 moles of ethylene oxide); alkyl glycerol sulfonates, fatty acyl glycerol sulfonates, fatty oleyl glycerol sulphates, alkyl phenol ether sulphonates of alkylphenol, paraffinsulfonates, alkyl phosphates, isethionates such as acyl isethionates, N-acyltaurates, alkylsuccinamates and sulfosuccinates, monoesters of sulfosuccinates (especially monoesters of C-? 2-C-? 8 saturated and unsaturated) and diesters of sulfosuccinates (especially saturated and unsaturated Ce-C? 2 diesters), alkylpolyacharide sulfates such as the alkyl polyglycoside sulfates (described below, nonionic non-sulfate compounds) and alkylpolyethoxycarboxylates such as those of the formula RO (CH 2 CH 2 O) k-CH 2 COO-M +, wherein R is a C 8 -C 22 alkyl, k is an integer from 1 to 10 and M is a soluble salt-forming cation. The rosin acids and hydrogenated rosin acids are also suitable, such as rosin, hydrogenated rosin and rosin acids and hydrogenated rosin acids present in or derived from tallow oil. Additional examples are described in "Surface Active Agents and Detergents" (Vol. I and II by Schwartz, Perry and Berch). A variety of such surfactants are also generally described in the US patent. 3,929,678, issued on December 30, 1975 to Laughlin and "MHÜHádiÍÉdi others, column 23, row 58 to column 29, row 23 (incorporated herein by reference). When included therein, the detergent compositions of the present invention typically comprise about 1% to about 40%, preferably about 5% to about 25%, by weight of said anionic surfactants. One class of nonionic surfactants useful in the present invention are condensates of ethylene oxide with a hydrophobic portion to provide a surfactant having an average hydrophilic-lipophilic balance (HLB) in the range of 8 to 17, preferably of 9.5 to 14, most preferably 12 to 14. The hydrophobic (lipophilic) portion can be aliphatic or aromatic in nature, and the length of the polyoxyethylene group that condenses with any particular hydrophobic group can be easily adjusted to produce a water-soluble compound that have the desired degree of balance between the hydrophilic and hydrophobic elements. Especially preferred nonionic surfactants of this type are the C9-C15 primary alcohol ethoxylates containing 3-12 moles of ethylene oxide per mole of alcohol, particularly primary C 2 -C 15 alcohols containing 5-8 moles of ethylene oxide per mole of alcohol. Another class of nonionic surfactants comprises the alkylpolyglucoside compounds of the general formula jrafigjjS ^ ^ RO (CnH2nO) tZx. wherein Z is a portion derived from glucose; R is a saturated hydrophobic alkyl containing from 12 to 18 carbon atoms; t is from 0 to 10 and n is 2 or 3; X is from 1.3 to 4, the compounds include less than 10% of the unreacted fatty alcohol and less than 50% of short chain alkyl polyglycosides. Compounds of this type and their use in detergents are described in EP-B 0 070 077, 0 075 996 and 0 094 118. Also suitable as nonionic surfactants are the polyhydroxy fatty acid amine surfactants of the formula: wherein R1 is H, or R1 is C1 hydrocarbyl. , 2-hydroxyethyl, 2-hydroxypropyl or a mixture thereof, R2 is C5-3 hydrocarbyl ?, and Z is a polyhydroxyhydrocarbyl having a linear hydrocarbyl chain with at least 3 hydroxyl directly connected to the chain, or a derivative alkoxylated thereof. Preferably, R1 is methyl, R2 is an alkyl or alkenyl chain of Cu. 15 straight such as coconut alkyl or mixtures thereof, and Z is derived from a reducing sugar such as glucose, fructose, maltose, lactose in a reductive amination reaction.

NON-AQUEOUS LIQUID DILUENT To form the liquid phase of the detergent compositions, the surfactant (mixture) described hereinabove can be combined with a non-aqueous liquid diluent such as a liquid alcohol alkoxylated material or a non-aqueous low polarity organic solvent. .

Alkoxylated Alcohol A component of the liquid diluent suitable for forming the compositions herein comprises an alkoxylated alcohol material. Said materials are in turn also nonionic surfactants. These materials correspond to the general formula: R1 (CmH2mO) nOH wherein R1 is an alkyl group of C8-Ci6, m is from 2 to 4, and n ranges from about 2 to 12. Preferably, R1 is an alkyl group, which may be primary or secondary, containing about 9 to 15 carbon atoms, most preferably about 10 to 14 carbon atoms. Preferably, also the alkoxylated fatty alcohols will be ethoxylated materials containing about 2 to 12 portions of ethylene oxide per molecule, most preferably about 3 to 10 portions of ethylene oxide per molecule. The alkoxylated fatty alcohol component of the liquid diluent will often have a hydrophilic-lipophilic balance (HLB) ranging from about 3 to 17. Most preferably, the HLB of this material will vary from about 6 to 15, more preferably about 8 to 15. Examples of alkoxylated fatty alcohols useful as one of the essential components of non-aqueous liquid diluent in the compositions herein will include those which are made from alcohols of 12 to 15 carbon atoms containing about 7 moles of ethylene oxide. These materials have been marketed under the trade names Neodol 25-7 and Neodol 23-6.5 by Shell Chemical Company. Other useful Neodoles include Neodol 1-5, an ethoxylated fatty alcohol having an average of 11 carbon atoms in its alkyl chain with about 5 moles of ethylene oxide; Neodol 23-9, an ethoxylated primary C? 2-C? 3 alcohol having about 9 moles of ethylene oxide and Neodol 91-10, an ethoxylated Cg-C-n primary alcohol having about 10 moles of ethylene oxide. Ethoxylated alcohols of this type have also been marketed by Shell Chemical Company under the tradename Dobanol. Dobanol 91-5 is a fatty alcohol of Cg-Cn ethoxylated with an average of 5 moles of ethylene oxide and Dobanol 25-7 is a fatty alcohol of C12-C15 ethoxylated with an average of 7 moles of ethylene oxide per mole of fatty alcohol. Other examples of suitable ethoxylated alcohols include Tergitol 15-S-7 and Tergitol 15-S-9 both of which are ethoxylated linear secondary alcohols which have been marketed by Union Carbide Corporation. The first is a mixed ethoxylation product of secondary alkanol of C-11-C15 ^ Linear Hgí with 7 moles of ethylene oxide and the last one is a similar product but with 9 moles of ethylene oxide being reacted. Other types of ethoxylated alcohols useful in the present compositions are the higher molecular weight nonionic alcohols, such as Neodol 45-11, which are similar condensation products of ethylene oxide of higher fatty alcohols, being the fatty alcohol higher than 14. -15 carbon atoms and the number of ethylene oxide groups per mole being about 11. Said products have also been marketed by Shell Chemical Company. The alkoxylated alcohol component when used as part of the liquid diluent in the non-aqueous compositions herein will generally be present to the extent of about 1% to 60% by weight of the composition. Preferably, the alkoxylated alcohol component will comprise about 5% to 40% by weight of the compositions herein. More preferably, the alkoxylated alcohol component will comprise from about 10% to 25% the weight of the detergent compositions herein.

Low-polarity non-aqueous organic solvent Another component of the liquid diluent that can be part of the detergent compositions herein comprises non-aqueous, low polarity organic solvents. The term "solvent" is used herein to denote the non-surfactant vehicle or diluent portion of the liquid phase of the composition. Although one of the essential and / or optional components of the ^^ g ^^^^^^^^^^^^^^ j msi ^ a ^^^^^^ usm? The present compositions can actually be dissolved in the phase containing "solvent", other components will be present as dispersed particulate material in the phase containing "solvent". In this way, the term "solvent" is not designed to require that the solvent material be capable of actually dissolving all of the detergent composition components added thereto. The non-aqueous organic materials that are used as solvents herein are those that are low polarity liquids. For the purposes of this invention, "low polarity" liquids are those that have very little, if any, tendency to dissolve one of the preferred types of particulate material used in the compositions herein, i.e., the agents Peroxygenated bleach, sodium perborate or sodium percabonate. In this way, relatively polar solvents such as ethanol should not be used. Suitable types of low polarity solvents useful in the non-aqueous liquid detergent compositions herein include lower alkylene glycol monoalkyl ethers, lower molecular weight polyethylene glycols, lower molecular weight methyl esters and amides, and the like. One type of non-aqueous solvent of low polarity which is preferred for use herein comprises the C2-C6 monoalkyl ethers of C2-C3 mono-, di-, tri- or tetraalkylene. Specific examples of such compounds include diethylene glycol monobutyl ether, tetraethylene glycol monobutyl ether, dipropylene glycol monobutyl ether and dipropylene glycol monobutyl ether. Diethylene glycol monobutyl ether and monobutyl ether are particularly preferred.

MHMIHÍlMIMI? Illll dipropilenglicol. Compounds of this type have been marketed under the trade names Dowanol, Carbitol and Cellosolve. Another preferred type of non-aqueous low polarity organic solvent useful herein comprises the lower molecular weight polyethylene glycols (PEGs). Said materials are those having molecular weights of at least about 150. PEGs of molecular weight ranging from about 200 to 600 are more preferred. Another type of non-aqueous and non-polar solvent that is also preferred comprises the methyl esters of weight lower molecular Said materials are those having the general formula: R1-C (O) -OCH3, wherein R1 varies from 1 to about 18. Examples of suitable lower molecular weight methyl esters include methyl acetate, methyl propionate, methyl octanoate and methyl dodecanoate. The non-aqueous low polarity organic solvents employed must, of course, be compatible and non-reactive with other components of the composition, for example, bleach and / or activators, used in the liquid detergent compositions herein. Said solvent component will generally be used in an amount of about 1% a 60% by weight of the composition. Most preferably, the non-aqueous, low polarity organic solvent will comprise about 5% to 40% by weight of the composition, more preferably about 10% to 25% by weight of the composition.

Concentration of the liquid diluent As with the concentration of the surfactant mixture, the amount of the total liquid diluent in the compositions herein will be determined by the type and amounts of the other components of the composition, and by the desired properties of the composition. . Generally, the liquid diluent will comprise about 20% to 95% by weight of the compositions herein. Most preferably, the liquid diluent will comprise about 50% to 70% by weight of the composition.

Solid phase The non-aqueous detergent compositions herein may further comprise a solid phase of particulate material which is dispersed and suspended in the liquid phase. In general, said particulate material will vary in size from about 0.1 to 1500 microns. Most preferably, said material will vary in size from about 5 to 500 microns. The particulate material used herein may comprise one or more types of detergent composition components which, in particulate form, are substantially insoluble in the nonaqueous liquid phase of the composition. The types of particulate materials that can be used are described in detail as follows: Sources of Nidrocene Peroxide A preferred particulate material that can be suspended is hydrogen peroxide or a source thereof. Preferred sources of hydrogen peroxide include prehydrated bleaches. The perhydrate is typically a perhydrated inorganic bleach, usually in the form of the sodium salt, as the source of alkaline hydrogen peroxide in the wash liquor. This perhydrate is usually incorporated at a level of from 0.1% to 60%, preferably from 3% to 40% by weight, most preferably from 5% to 35% by weight and more preferably from 8% to 30% by weight of the composition. The perhydrate may be any inorganic alkali metal salt such as monohydrated perborate or tetrahydrate, percabonate, perfosphate and persilicate salts, but is conventionally an alkali metal perborate or percarbonate. Sodium percarbonate is an addition compound having a formula corresponding to 2Na2CO3.3H202, and is commercially available as a crystalline solid. The most commercially available material includes a low level of heavy metal sequestrant such as EDTA, 1-hydroxyethylidene-1,1-diphosphonic acid (HEDP) or an amino phosphonate, which is incorporated during the manufacturing process. For the purposes of the detergent composition aspect of the present invention, the percarbonate may be incorporated into the detergent compositions without additional protection, but preferred embodiments of said compositions utilize a coated form of the material. A variety of coatings can be used, including borate, boric acid and citrate or sodium silicate with an SiO2: Na2O ratio of about 1.6: 1 to 3.4: 1, preferably 2.8: 1, applied as an aqueous solution to give a level of 2% to 10%, (usually 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.

Surfactants Another type of particulate material that can be suspended in the non-aqueous liquid detergent compositions herein includes anionic surfactants which are completely or partially insoluble in the non-aqueous liquid phase. The most common type of anionic surfactant with said solubility properties comprises primary or secondary alkyl sulfate anionic surfactants. Said surfactants are those produced by sulfation of higher C8-C20 fatty alcohols. The conventional primary alkyl sulfate surfactants have the general formula: ROS03"M + g | gg | -Z ^^ wherein R is typically a C8-C2o linear idrocarbyl grups, which may be straight or branched chain, and M is a water-solubilizing cation. Preferably, R is a C10-C14 alkyl, and M is alkali metal. Most preferably, R is approximately C-? 2 and M is sodium. The conventional secondary alkyl sulfates can also be used as the essential anionic surfactant component of the solid phase of the compositions herein. Conventional secondary alkyl sulfate surfactants are those materials that have the sulfate portion distributed randomly along the hydrocarbyl "base structure" of the molecule. Such materials can be illustrated by the structure: CH3 (CH2) n (CHOSO3 M +) (CH2) mCH3 where m and n are integers of 2 or more and the sum of m + n is typically from about 9 to 15, and M is a solubilizing cation in water. If used as all or part of the necessary particulate material, auxiliary anionic surfactants such as alkyl sulphates will generally comprise about 1% to 10% by weight of the composition, most preferably about 1% to 5% by weight of the composition . The alkyl sulfate used as all or part of the particulate material is prepared and added to the compositions herein separately from the non-alkoxylated alkylsulphate material which can be part of the alkyl ether sulfate surfactant component used essentially as part of the liquid phase of the present.

Organic detergency material Another possible type of particulate material that can be suspended in the non-aqueous liquid detergent compositions herein comprises an organic builder that counteracts the effects of calcium, or other ion, and the hardness of the water found during the washing / bleaching use of the compositions herein. Examples of such materials include the alkali metals, citrates, succinates, malonates, fatty acids, carboxymethyl succinates, carboxylates, polycarboxylates and polyacetyl carboxylates. Specific examples include the sodium, potassium and lithium salts of oxydisuccinic acid, mellitic acid, benzenepolycarboxylic acids and citric acid. Other examples of organic phosphonate sequestering agents are those that have been sold by Monsanto under the trade name Dequest and alkanehydroxyphosphonates. Citrate salts are much preferred. Other suitable organic builders include the higher molecular weight polymers and copolymers known to have builder properties. For example, such materials include polyacrylic acid, polymaleic acid and suitable polyacrylic / polymaleic acid copolymers and their salts, such as those sold by BASF under the trademark Sokalan. Another suitable type of organic builder comprises the water soluble salts of higher fatty acids, ie, "soaps". These include alkali metal soaps such as the sodium, potassium, ammonium and alkylolammonium salts of higher fatty acids containing from about 8 about 24 carbon atoms, and preferably about 12 to about 18 carbon atoms. Soaps can be made by direct saponification of fats and oils, or by neutralization of free fatty acids. Particularly useful are the sodium and potassium salts of the fatty acid mixtures derived from coconut oil and tallow, that is, sodium or potassium tallow and coconut soap. If they are used as all or part of the necessary particulate material, the insoluble organic builders may generally comprise about 1% to 20% by weight of the compositions herein. Most preferably, said builder material may comprise about 4% to 10% by weight of the composition.

Inorganic Sources of Alkalinity Another possible type of particulate material that can be suspended in the non-aqueous liquid detergent compositions herein may comprise a material that serves to make the aqueous wash solutions formed from said compositions generally of an alkaline nature. Said materials may or may not also act as builders, that is, as materials that counteract the adverse effect of water hardness on the detergency performance. Examples of suitable alkalinity sources include the water soluble alkali metal carbonates, bicarbonates, borates, silicates and metasilicates.

Although not preferred for ecological reasons, water-soluble phosphate salts can also be used as sources of alkalinity. These include the alkali metal pyrophosphates, orthophosphates, polyphosphates and phosphonates.

Of all these alkalinity sources, alkali metal carbonates such as sodium carbonate are preferred. The source of alkalinity, if it is in the form of a hydratable salt, can also serve as a desiccant in the non-aqueous liquid detergent compositions herein. The presence of an alkalinity source that is also a desiccant can provide benefits in terms of chemically stabilizing components of the composition such as the peroxygen bleaching agent that may be susceptible to water deactivation. If used as all or part of the particulate component, the source of alkalinity will comprise about 1% to 15% by weight of the compositions herein. Most preferably, the source of alkalinity may comprise about 2% to 10% by weight of the composition. Said materials, although water-soluble, will generally be insoluble in the non-aqueous detergent compositions herein. In this way, said materials will generally be dispersed in the non-aqueous liquid phase in the form of discrete particles.

Optional components of the composition In addition to the components of the liquid and solid phase of the composition as described hereinabove, the detergent compositions herein may, and preferably, contain various optional components. Such optional components may be in liquid or solid form. The optional components can be dissolved in the liquid phase or they can be dispersed within the liquid phase in the form of fine particles or droplets. Some of the materials that may optionally be used in the compositions herein are described in greater detail as follows: Optional organic additives The detergent compositions may contain an organic additive. An organic additive that is preferred is hydrogenated castor oil and its derivatives. Hydrogenated castor oil is a commercially available product sold, for example, in various grades under the CASTO RWAX.RTM brand. by NL Industries, Inc., Highstown, New Jersey. Other suitable hydrogenated castor oil derivatives are Thixcin R, Thixcin E, Thixatrol ST, Perchem R and Perchem ST. The hydrogenated castor oil that is especially preferred is Thixatrol ST. Castor oil can be added as a mixture with, for example, stearamide. ^^ = * jjÉgj ^^^^ The organic additive will partially dissolve in the non-aqueous liquid diluent. To form the structured liquid phase which is required for adequate phase stability and acceptable rheology, the organic additive is generally present to the extent of from about 0.05% to 20% by weight of the liquid phase. Most preferably, the organic additive comprises about 0.1% to 10% by weight of the non-aqueous liquid phase of the compositions herein.

Optional inorganic detergency builders The compositions herein may also optionally contain one or more types of inorganic builders other than those listed here above, which also function as alkalinity sources. Such optional inorganic builders may include, for example, aluminosilicates such as zeolites. The aluminosilicate zeolites and their use as detergency builders are described in more detail in Corkill et al., U.S. Pat. No. 4,605,509; issued on August 12, 1986, the description of which is hereby incorporated by reference. Also suitable for use in the detergent compositions herein are the layered crystalline silicates such as those described in this' 509 patent of E.U.A. If used, optional inorganic builders may comprise about 2% to 15% by weight of the compositions herein.

M * "* ^ - ^ - - - - ^^ Optional enzymes The detergent compositions herein may also optionally contain one or more types of detergent enzymes, which enzymes may include proteases, amylases, cellulases and lipases. they are known in the art and are also commercially available.Non-aqueous liquid detergents herein can be incorporated in the form of suspensions, "disks" or "pellets." Another suitable type of enzyme comprises those in the form of enzyme suspensions. In nonionic surfactants, the enzymes in this form have been marketed, for example, by Novo Nordisk under the tradename "LDP." It is especially preferred here to use enzymes that are added to the compositions herein in the form of pellets. of conventional enzymes, said pellets will generally vary in size from approximately 100 to 1,000 microns, most preferably around 200 to 800 microns and will be their suspended along the non-aqueous liquid phase of the composition. It has been found that pellets in the compositions of the present invention, in comparison with other forms of enzyme, exhibit an enzyme stability especially desirable in terms of retention of enzymatic activity with the passage of time. Thus, compositions using enzyme pellets do not need to contain a conventional enzyme stabilization such as is most often used when the enzymes are incorporated in aqueous liquid detergents.

If employed, the excipients will normally be incorporated into the non-aqueous liquid compositions herein at levels sufficient to provide up to about 10 mg by weight, very typically about 0.01 mg to about 5 mg, of active enzyme per gram of the composition. In other words, the non-aqueous liquid detergent compositions herein will typically comprise about 0.001% to 5%, preferably about 0.01% to 1% by weight, of a commercial enzyme preparation. Protease enzymes, for example, are normally present in such commercial preparations at levels sufficient to provide 0.005 to 0.1 Anson units (AU) of activity per gram of the composition.

Optional guelatary agents The detergent compositions herein may also optionally contain a chelating agent that serves to chelate metal ions, eg, iron and / or manganese, in the non-aqueous detergent compositions herein. Said chelating agents then serve to form complexes with metal impurities in the composition that would otherwise tend to deactivate components of the composition such as the peroxygen bleaching agent. Useful chelating agents can include aminocarboxylates, phosphonates, aminophosphonates, polyfunctionally substituted aromatic chelating agents and mixtures thereof.

The aminocarboxylates useful as optional chelating agents include ethylenediaminetetraacetates, N-hydroxyethyl-ethylene-diaminotriacetates, nitrotriacetates, ethylenediaminetetrapropionates, triethylenetetraminohexacetates, diethylenetriaminepentaacetates, ethylenediamine disuccinates and ethanoldiglicines. The alkali metal salts of these materials are preferred. Also suitable are amino phosphonates for use as chelating agents in the compositions of this invention, when at least low levels of total phosphorus are allowed in the detergent compositions., and include ethylene diamine tetrakis (methylene phosphonates) as DEQUEST. Preferably, these aminophosphonates do not contain alkyl or alkenyl groups with more than about 6 carbon atoms. Preferred chelating agents include hydroxyethyl diphosphonic acid (HEDP), diethylenetriaminepentaacetic acid (DTPA), ethylenediamine disuccinic acid (EDDS) and dipicolinic acid (DPA) and salts thereof. The chelating agent can, of course, also act as a builder during the use of the compositions herein for washing / bleaching fabrics. The chelating agent, if employed, may comprise about 0.1% to 4% by weight of the compositions herein. Most preferably, the chelating agent will comprise from about 0.2% to 2% by weight of the detergent compositions herein.

Optional thickening, viscosity control and / or dispersing agents The detergent compositions herein may also optionally contain a polymeric material which serves to improve the ability of the composition to maintain its components in solid particles in suspension. Said materials can then act as thickeners, viscosity control agents and / or dispersing agents. Such materials are often polymeric polycarboxylates, but may include other polymeric materials such as polyvinylpyrrolidone (PVP) and polymeric amine derivatives such as ethoxylated and quaternized hexamethylenediamines. The polymeric polycarboxylate materials can be prepared by polymerizing or copolymerizing suitable unsaturated monomers, preferably in their acid form. The unsaturated monomeric acids which can be polymerized to form suitable polymeric polycarboxylates include acrylic acid, maleic acid (or maleic anhydride), fumaric acid, itaconic acid, aconitic acid, mesaconic acid, citraconic acid and methylenemalonic acid. The presence of monomeric segments in the polymeric polycarboxylates of the present which do not contain carboxylate radicals such as vinyl methyl ether, styrene, ethylene, etc., is adequate, as long as said segments do not constitute more than about 40% by weight of the polymer. Particularly suitable polymeric polycarboxylates can be derived from acrylic acid. Said acrylic acid-based polymers which are useful herein are the water-soluble salts of polymerized acrylic acid. He The average molecular weight of said polymers in acid form varies from about 2,000 to 10,000, most preferably from about 4,000 to 7,000, and more preferably from about 4,000 to 5,000.The water-soluble salts of said acrylic acid polymers they may include, for example, the alkali metal salts.Soluble polymers of this type are known materials.The use of polyacrylates of this type in detergent compositions has been described, for example, in Diehl, US Patent No. 3,308,067 issued on March 7, 1967. Such materials also perform a detergency builder function.If used, the optional thickening, viscosity control and / or dispersing agents should be present in the compositions herein to the extent of about 0.1%. to 4 by weight Most preferably, said materials may comprise from about 0.5% to 2% by weight of the detergent compositions herein.

Polishes, foam suppressors and / or optional perfumes The detergent compositions herein may also optionally contain brighteners, suds suppressors, silicone oils, bleach catalysts and / or conventional perfume materials. Such brighteners, suds suppressors, silicone oils, bleach catalysts and perfumes must, of course, be compatible and non-reactive with the other components of the composition in a non-aqueous environment. If they are present, the brighteners, suds suppressors and / or perfumes ftl? xtti ?. will typically comprise about 0.01% to 2% by weight of the compositions herein. Suitable bleach catalysts include the manganese-based complexes described in US 5,246,621, US 5,244,594, US 5,114,606 and US 5,114,611. Especially preferred catalysts are the metallo-catalysts as described in the patent applications of E.U.A. Copending Serial No. 60 / 040,629, Serial No. 60 / 039,915, Serial No. 60 / 040,222, Serial No. 60 / 040,156, Serial No. 60 / 040,115, Serial No. 60 / 038,714 and No of series 60/039, 920, filed on March 7, 1997. The catalyst can be protected by dissolving the catalyst in a biopolymer. Suitable biopolymers are described in EP 672 104. A preferred biopolymer is starch.

FORM OF COMPOSITION The liquid detergent compositions containing particles of this invention have a substantially non-aqueous (or anhydrous) character. Although very small amounts of water may be incorporated into said compositions as an impurity in the essential or optional components, the amount of water should not by any means exceed about 5% by weight of the compositions herein. Most preferably, the water content of the non-aqueous detergent compositions herein will comprise less than about 1% by weight. ^ mu ^, ^^^^^? Í m ^ t ^ M ^? The non-aqueous detergent compositions containing particles herein will be in the form of a liquid.

Preparation and use of the composition The non-aqueous liquid detergent compositions herein can be prepared by mixing a non-aqueous liquid phase and subsequently adding to this phase additional particulate components in any convenient order and mixing, for example, by stirring, the combination of components resulting to form the stable phase compositions of the present. In a typical procedure for preparing said compositions, certain essential and preferred optional components will be combined in a particular order and under certain conditions. In a first step of a preferred preparation process, the liquid phase containing anionic surfactant is prepared. This preparation step includes the formation of an aqueous suspension containing about 30 to 60% of one or more alkali metal salts of linear C 10 -C 16 alkylbenzenesulfonic acid and about 2-15% of one or more non-surfactant diluent salts. In a subsequent step, this suspension is dried to the extent necessary to form a solid material containing less than about 4% by weight of waste water. After the preparation of this solid material containing anionic surfactant, this material can be combined with one or more of the non-aqueous organic diluents to form the liquid phase containing This is a surfactant of the detergent compositions herein. This is done by reducing the anionic surfactant-containing material formed in the pre-preparation step described above in powder form and combining said powder material with a stirred liquid medium comprising one or more of the non-aqueous organic diluents, either surfactant or non-surfactant, or both, as described hereinabove. This combination is carried out under stirring conditions which are sufficient to form a completely mixed dispersion of particles of the insoluble fraction of the LAS / co-dried salt material along a non-aqueous organic liquid diluent. Subsequently, the particulate material to be used in the detergent compositions herein can be added. Such components, which can be added under high shear agitation, include any optional surfactant particles, particles of substantially all of an organic builder, for example, citrate and / or fatty acid and / or source of alkalinity, for example, Sodium carbonate can be added by continuing to maintain this mixture of composition components under agitation by shear stress. The agitation of the mixture is continued, and if necessary, it can be increased at this point to form a uniform dispersion of insoluble solid phase particulate materials in the liquid phase. The non-aqueous liquid dispersion prepared in this way can be subjected to pulverization or shear agitation. Spraying conditions will generally include maintaining a temperature between about 10 and 90 ° C, preferably between 20 ° C and 60 ° C. The equipment suitable for this purpose includes agitated ball mills, two-ball mills (Fryma), colloid mills, high pressure homogenizers, high shear mixers and the like. The colloid mill and high shear mixers are preferred for their high output speed and low maintenance costs. The small particles produced in said equipment will generally vary in size from 0.4-150 microns. Agitation is then continued, and if necessary, it can be increased at this point to form a uniform dispersion of solid phase particles insoluble in the liquid phase. In a second processing step, the particles of the bleach precursor are mixed with the suspension of the first mixing step in a second mixing step. This mixture is then subjected to wet pulverization in such a way that the average particle size of the bleach precursor is less than 600 microns, preferably between 50 and 500 microns, most preferably between 100 and 400 microns. After some or all of the above solid materials have been added to this stirred mixture, the highly preferred peroxygen bleach particles can be added to the composition, again while the mixture is maintained under shear agitation. In a third processing step, the activation of the organic additive is obtained. The organic additives are subjected to wetting and dispersing forces to reach a dispersed state. It is inside the The ability of an organic expert to activate the organic additive is capable of being realized by a person skilled in the art. The activation can be done according to the one described by Rheox, in the Rheology Handbook, A practical guide to rheological additives. There are basically three different stages. The first step is to add the agglomerated powder to the solvent. This combination is carried out under conditions of agitation (shear, heat, stage 2) which are sufficient to lead to complete de-agglomeration. With continuous agitation and heat development over a period of time, the solvent-swollen particles of the organic additive are reduced to their active state in step 3. By adding solid components to the non-aqueous liquids according to the above procedure, it is advantageous to keep the moisture content unbound and free of these solid materials below certain limits. The moisture in said solid materials is frequently present at levels of 0.8% or more (see the method described below). By reducing the free moisture content, for example, by fluidized-bed drying, of solid particulate materials at a free moisture level of 0.5% or less prior to their incorporation into the detergent composition matrix, stability advantages can be obtained. significant for the resulting composition.

Free and total water determinations For the purposes of this patent application, and without wishing to be bound by theory, reference is made to "free water" as the amount of water that can be detected after the removal of the solid components and not dissolved from the product, while "total water" refers to the amount of water that is present in the product as a whole, whether it is bound to solids (for example, water of hydration), dissolved in the liquid phase or in any other way One method of determining water that is preferred is the so-called "Karl Fischer titration" method. Other Karl Fischer titration methods, for example, NMR, microwave or IR spectrometry may also be suitable for the determination of water in the liquid part of the product and in the complete product as described below. The "free water" of a formulation is determined in the following manner. At least one day after the preparation of the formula (to allow equilibration), a sample is subjected to centrifugation until a transparent layer is obtained visually and free of solid components. This transparent layer is separated from the solids, and a heavy sample is introduced directly into a vessel for coulometric Karl Fischer titration. The water level determined in this way (mg of water / kg of transparent layer) is known as "free water" (in ppm). The "total water" is determined by first extracting a heavy amount of the finished product with a polar and anhydrous extraction liquid. The extraction liquid is selected in such a way that interferences of undissolved solids are minimized. In many cases, dry methanol is a preferred extraction liquid. Normally, the extraction procedure reaches a balance within a few hours - this requires validation for different formulations - and can be accelerated by sonification (bathing ^ - ^ -. feaü ^^. , ^ fl ^ - ultrasonic). After that time, a sample of the extract is centrifuged or filtered to remove the solids, and a known aliquot is then introduced into the Karl Fischer titration cell (coulometric or volumetric). The value found in this way (mg of water / kg of product) is referred to as the "total water" of the formulation. Preferably, the non-aqueous liquid detergent compositions of the present invention comprise less than 5%, preferably less than 3%, most preferably less than 1% free water.

Viscosity and Relaxation Measurements The non-aqueous liquid detergent compositions containing particles herein will be relatively viscous and phase stable under conditions of commercialization and use of said compositions. Frequently, the viscosity of the compositions herein will vary from about 300 to 10,000 cps, most preferably about 500 to 3000 cps. The physical stability of these formulations can also be determined by relaxation measurements. Frequently, relaxation of the compositions herein will vary from about 1 to 20 Pa, most preferably around 1.5 to 10 Pa. For the purpose of this invention, viscosity and relaxation are measured with a Carri-Med CSL2100 rheometer according to the invention. method described below. The rheological properties were determined by means of a constant voltage rheometer (Carri-Med CSL2100) at 25 ° C. A parallel plate configuration with a disc radius of 40 mm and a layer thickness of 2 mm was used. The shear stress varied between 0.1 Pa and 125 Pa. The reported viscosity was the value measured at a shear rate of approximately 20 s "1. The effort to relax was defined as the previous effort whose disc movement was detected. This implies that the shear rate was below 3 x 10"4 s" 1. The compositions of this invention, prepared as described hereinabove, can be used to form aqueous wash solutions for use in washing and bleaching. In general, an effective amount of said compositions is added to water, preferably in a conventional automatic laundry washing machine, to form said aqueous washing / bleaching solutions.The aqueous wash / bleach solution formed in this way is placed in contact then, preferably under agitation, with the fabrics to be washed and bleached therewith.An effective amount of the compositions Liquid gels of the present added to water to form the aqueous wash / bleach solutions may comprise sufficient amounts to form about 500 to 8,000 ppm of the composition in aqueous solution. Most preferably, about 800 to 5,000 ppm of the detergent compositions herein will be provided in the aqueous wash / bleach solution. The following examples illustrate the preparation and performance advantages of the non-aqueous liquid detergent compositions herein invention. However, said examples do not necessarily attempt to limit or otherwise define the scope of the present invention.

EXAMPLE I Preparation of the bleach precursor composition The following bleach precursor particles were made: NACA-OBS: (6-Nonanamidocaproil) oxibencenesulfonate TAED: Tetraacetylethylenediamine LAS: Linear C12 sodium alkylbenzene sulfonate AE3: A predominantly linear primary C? 2.? 5 alcohol condensed with an average of 3 moles of ethylene oxide. C12-C1 AE3S: C12-14 sodium alkylsulfate condensed with an average of 3 moles of ethylene oxide per mole. AMM: Copolymers of acrylic acid / maleic acid.

In each of examples A to D, the bleach activator (i.e., NACA-OBS or TAED) was premixed with sodium citrate (when present), LAS or AS and an aqueous solution (40% active) of the polymer AAM in a Loedige® FM mixer. The premix was then fed to a dome extruder (Fuji Paudal model DGL-1) having a die with 0.7 mm holes and extruded at a pressof about 20 bar. The resulting extruded material was then fed to a spinning disk spheronizer (Fuji Paudal QJ-400) where they were broken into short lengths and shaped into substantially spherical particles. The particles were then dried in a Niro vibratory fluid bed dryer, resulting in free flowing and crisp dust-free particles with a particle size of 0.25 mm to 2.00 mm.

EXAMPLE II Preparation of a non-aqueous liquid detergent composition 1) Part of the butoxy-propoxy-propanol (BPP) and a non-ionic ethoxylated alcohol surfactant CnEO (5) (Genapol 24/50) are mixed for a short time (1-5 minutes) using a paddle impeller in a mixing tank in a single phase. 2) LAS is added to the BPP / NI mixtafter heating the BPP / NI mixtto 45 ° C. 3) If required, the liquid base (LAS / BPP / NI) is pumped into drums. Molecular sieves (type 3A, 4-8 meshes) are added to each drum at 10% of the net weight of the liquid base. The molecular sieves are mixed in the liquid base using individual paddle turbine mixers and drum spinning techniques. The mixing is carried out under a cover of nitrogen to prevent the collection of moistfrom the air. The total mixing time is 2 hours, after which 0.1-0.4% of the moistin the liquid base is removed. The molecular sieves are removed by passing the liquid base through a 20-30 mesh screen. The liquid base is returned to the mixing tank. 4) The additional solid ingredients are prepared for addition to the composition. Such solid ingredients include the following: Sodium carbonate (particle size 100 microns) Sodium citrate dihydrate Maleic acrylic copolymer (BASF Sokalan) Brightener (Tinopal PLC) Tetrasodic hydroethylidene diphosphonic acid salt (HEDP) Sodium diethylenetriaminepentamethylenephosphonate Ethylenediamine disuccinic acid (EDDS) These solid materials, which are all sprayable, are added to the mixing tank and mixed with the liquid base until uniform. This takes about 1 hour after the addition of the last powder. The tank is covered with nitrogen after the addition of the powders. A particular order of addition for these powders is not critical.

H ^ 5) The batch is pumped once through a Fryma colloid mill, which has a simple rotor-stator configuration in which a high-speed rotor rotates within a stator that creates a zone of high shear stress. This reduces the particle size of all solids. This leads to an increase in the performance value (ie, struct. The batch is then reloaded into the mixing tank after cooling. 6) The bleach precursor particles are mixed with the spray suspension of the first mixing step in a second mixing step. This mixtis then subjected to wet pulverization in such a way that the average particle size of the bleach precursor is less than 600 microns., preferably between 50 to 500 microns, most preferably between 100 and 400 microns. 7) Other solid materials may be added after the first processing step. These include the following: Sodium percarbonate (400-600 microns) Protease enzyme, cellulase and amylase pellets (400-800 microns, specific density less than 1.7 g / mL) Titanium dioxide particles (5 microns) Catalyst These materials Non-sprayable solids are then added to the mixing tank followed by the liquid ingredients (perfume and suds suppressor based on silicone, fatty acid / silicone). The batch is then mixed for one hour (under a nitrogen blanket).

The resulting composition has the formula described in Table 1. The catalyst is prepared by adding starch modified with octenylsuccinate, to water in the approximate ratio of 1: 2. The catalyst is then added to the solution and mixed until dissolved. The composition of the solution is: catalyst 5% starch 32% (starch includes 4-6% bound water) water 63% The solution is then spray-dried using a Niro Atomizer laboratory spray dryer. The inlet of the spray dryer is set at 200 ° C, and the atomization air is about 4 bar. The drop in air pressure in the procedure is 30-35 mm of water. The feed rate of the solution is set to obtain an exit temperature of 100 ° C. The powder material is collected at the base of the spray dryer. The composition is: Catalyst 15% starch (and bound water) 85% The particle size is 15 to 100 μm leaving the dryer.

TABLE 1 Non-aqueous liquid detergent composition with bleach Component% by weight of% by weight of active active salt Sodium salt of LAS 16 15 Alcohol ethoxylate C11 EO = = 5 21 20 BPP 19 19 Sodium citrate 4 5 Sodium salt of [4- [N-nonanoyl-6- 6 7 aminohexanoyloxybenzenesulfonate] Hexamethylenediamine chloride salt 1,2 1 polyethoxylated quatemized with methyl Ethylenediamine disuccinic acid 1 1 Sodium carbonate 7 7 Maleic acrylic copolymer 3 3 Protease pellets 0.40 0.4 Amylase pellets 0.8 0.8 Cellulase pellets 0.50 0.5 Sodium percarbonate 16 - Sodium Perborate - 15 Foam suppressor 1.5 1.5 Perfume 0.5 0.5 Titanium dioxide 0.5 0.5 Brightener 0.14 0.2 Thixatrol ST 0.1 0.1 Catalyst 0.03 0.03 Speck 0.4 0.4 Miscellaneous ingredients up to 100% The resulting table 1 composition is a structured, stable, pourable and anhydrous heavy-duty laundry detergent liquid that provides excellent stain and dirt removal performance when used in normal fabric washing operations. The chemical decomposition of the bleach precursor was negligible even after 6 weeks of storage at room temperature. ^ gHj i

Claims (11)

NOVELTY OF THE INVENTION CLAIMS

1. - A non-aqueous liquid detergent composition comprising a bleach precursor composition containing: a) a bleach precursor; b) a surfactant system and c) salt of an organic acid.

2. The non-aqueous liquid detergent composition according to claim 1, further characterized in that said surfactant system comprises a nonionic and an anionic surfactant.

3. A non-aqueous liquid detergent composition comprising a bleach precursor composition containing: a) a bleach precursor; b) a surfactant system comprising a non-ethoxylated anionic surfactant and / or a nonionic surfactant; c) salt of an organic acid, wherein said surfactant system, the precursor and the organic acid are in the form of an agglomerate, granule or extruded material in which said precursor, said surfactant system and the organic acid salt are optionally coated in an intimate mix.

4. The non-aqueous liquid detergent composition according to claim 1, further characterized in that said surfactant system is present in an amount of 0.1% to 50% by weight of the precursor composition.

5. - A non-aqueous liquid detergent composition according to any of claims 1-4, further characterized in that said precursor is present in an amount of 10% to 99% by weight of the precursor composition.

6. A non-aqueous liquid detergent composition according to any of claims 2-5, further characterized in that said anionic surfactant is selected from sulfate surfactants, sulfonate surfactants, carboxylate surfactants, sarcosinate surfactants. and mixtures thereof.

7. A non-aqueous liquid detergent composition according to claim 6, further characterized in that said anionic surfactant is the linear C5-C2o alkylbenzenesulfonate salt.

8. A non-aqueous liquid detergent composition according to any of claims 1-7, further characterized in that said The bleach precursor is selected from (6-octanamido-caproyl) oxybenzenesulfonate, (6-nonanamidocaproyl) oxybenzenesulfonate, (6- decanamido-caproyl) oxybenzenesulfonate, and mixtures thereof.

9. A non-aqueous liquid detergent composition according to claims 1-10, further characterized in that the organic salt is present at 1-20% by weight of the bleach precursor composition.

10. A non-aqueous liquid detergent composition according to any of claims 1-9, characterized in that said composition further comprises a polymeric film composite. ^^ ¡^^^^ ¡^^^^^^^^ j ^^^^^^ X ^ gjí = ^^^^^^^^^^^^^^^^^^ ^ & ^^ & jg

11. - A non-aqueous liquid detergent composition according to any of claims 1-10, further characterized in that said composition is in the form of an agglomerate or an extruded material in spheres.