PEROXYACID BLEACH PRECURSOR COMPOSITIONS

Abstract: There is provided a peroxyacid bleach precursor composition comprising: a) a peroxyacid bleach precursor, b) a water-insoluble inorganic compound of surface area 2m<2>/g to 4m<2>/g; wherein said precursor and said inorganic compound are in close physical proximity. Also provided herein are detergent compositions containing said peroxyacid acid compositions. The peroxyacid compositions of the invention show improved free flowing properties.

Description: PEROXYACID BLEACH PRECURSOR COMPOSITIONS Technical field This invention relates to peroxyacid precursor particles and to detergent compositions containing them. More particularly the invention relates to peroxyacid precursor particles incorporating a water-insoluble inorganic compound of specific surface area as co-agglomerating agent of the peroxyacid precursor to provide free flowing peroxyacid precursor particles. Background of the invention The incorporation of a peroxyacid precursor as a discrete particulate component of a fabric washing composition is well known in the art. The particulate may comprise the precursor as a crystalline material of the desired particle size as disclosed in GB-A-846798, but a more preferred form comprises an agglomerate of relatively finely divided precursor particles bound together by a binder or agglomerating agent. Examples of this type of precursor particle are discussed in EP-A- 0070474, EP-A-0375241, W092/13798 and EP-A-0356700. The last named Application discloses the use of water-soluble organic compounds, of which citric acid is a preferred example, as co- agglomerating agents of the precursor. Agglomeration with citric acid is asserted according to EP-A-0356700 to enhance the dispersibility, solubility and storage stability of the precursor particulates. Another suitable compound for co-agglomeration with the precursor is a water-insoluble compound. The prior art contains numerous examples of precursor co-agglomerated with water-insoluble inorganic compounds so as to increase the dispersibility of the resulting particle. EP 240 057 discloses the use of a peroxyacid bleach precursor composition comprising a peroxyacid bleach precursor, a polymeric material and 0.5% to 15% of a water-insoluble inorganic material such as smectite or zeolite. Specifically disclosed is a granule composition comprising 84.9% TAED, 2.2% kaolin clay, 1.1% copolymer of maleic anhydride-methyl vinyl ether with the balance being water and Na2SO.j. EP 028432 discloses the use of a peroxyacid precursor particle containing granular laundry composition comprising from 15% to 60% of a water-insoluble inorganic material having a surface area of at least 5m2/g together with a peroxyacid bleach precursor and an alkoxylated nonionic surfactant; wherein said particle shows enhanced storage stability. Specifically disclosed are granule compositions comprising either 32%TAED, 48% clay and 20% surfactant, or 20% alkyl oxybenzene sulfonate, 50% clay and 30% surfactant. Notwithstanding the advance in the art represented by the above disclosures, difficulties have still been encountered in providing peroxyacid precursor particles having satisfactory particle flow and solubility characteristics without adversely reducing the effectiveness of the resultant peroxycarboxyhc acid bleach. The Applicants have now found that these problems can be overcome by the provision of a peroxyacid precursor particle comprising, in close physical proximity to the precursor, a water-insoluble inorganic compound having a surface area lying within a defined range. All documents cited in the present description are, in relevant part, incorporated herein by reference. Summary of the Invention According to the present invention, there is provided a peroxyacid bleach precursor composition comprising: a- a peroxyacid bleach precursor b- a water-insoluble inorganic compound of surface area 2m^/g to 4m2/g; wherein said precursor and said inorganic compound are in close physical proximity. For the purpose of the present invention, the term close physical proximity means one of the following: i) an agglomerate or extrudate in which said precursor and said inorganic compound are in intimate admixture; ii) a bleach precursor particulate coated with one or more layers wherein at least one layer contains the inorganic compound; iii) an inorganic compound coated with one or more layers wherein at least one layer contains the bleach activator. It also has to be understood by close physical proximity that the precursor and the inorganic compound are not two separate discrete particles in the detergent composition. In a yet further aspect of the present invention a detergent composition is provided comprising a surfactant material, a source of alkaline hydrogen peroxide and Tperoxyacid bleach precursor composition as hereinbefore defined. Detailed description of the invention Peroxyacid bleach precursor Peroxyacid bleach precursors are compounds which react with hydrogen peroxide in a perhydrolysis reaction to produce a peroxyacid. Generally peroxyacid bleach precursors may be represented as O II X-C-L where L is a leaving group and X is essentially any functionality, such that on perhydrolysis the structure of the peroxyacid produced is O X-C-OOH Peroxyacid bleach precursor compounds are preferably incorporated at a level of from 50% to 95% by weight, more preferably at least 55% by weight, most preferably at least 60% by weight of the precursor composition. Leaving groups The leaving group, hereinafter L group, must be sufficiently reactive for the perhydrolysis reaction to occur within the optimum time frame (e.g., a wash cycle). However, if L is too reactive, this activator will be difficult to stabilize for use in a bleaching composition. Preferred L groups are selected from the group consisting of: R 3 -0-CH=C-CH=CH2 -O-C H=C-C H=C Hfc and mixtures thereof, wherein R is an alkyl, aryl, or alkaryl group containing from 1 to 14 carbon atoms, R is an alkyl chain containing from 1 to 8 carbon atoms, R is H or R , and Y is H or a solubilizing group. Any of R , R and R may be substituted by essentially any functional group including, for example alkyl, hydroxy, alkoxy, halogen, amine, nitrosyl, amide and ammonium or alkyl ammmonium groups The preferred solubilizing groups are -Sθ3 ~ M + , -CO^Tvl "1" , -SO^M , -N + (R 3 ) X ' and 0<--N(R 3 ) 3 and most preferably -S0 3 ~ M + and -Cθ2 ~ M wherein R is an alkyl chain containing from 1 to 4 carbon atoms, M is a cation which provides solubility to the bleach activator and X is an anion which 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 is a halide, hydroxide, methylsulfate or acetate anion. Suitable peroxyacid bleach precursor materials are compounds containing one or more N- or O-acyl groups. These can be selected from a wide range of classes that include anhydrides, esters, lmides, lactams and acylated derivatives of imidazoles and oximes. Examples of useful materials within these classes are disclosed in GB-A-1586789. Suitable esters are disclosed in GB-A-836988, 864798, 1147871, 2143231 and EP-A-0170386. Peroxyacid precursor compositions containing mixtures of any of the precursors hereinafter disclosed are also contemplated by the present invention. Perbenzoic acid precursor Perbenzoic acid precursor compounds provide perbenzoic acid on perhydrolysis. Suitable O-acylated perbenzoic acid precursor compounds include the substituted and unsubstituted benzoyl oxybenzene sulfonates, including for example benzoyl oxybenzene sulfonate: Also suitable are the benzoylation products of sorbitol, glucose, and all saccharides with benzoylating agents, including for example: Ac = COCH3; Bz = Benzoyl Perbenzoic acid precursor compounds of the imide type include N- benzoyl succinimide, tetrabenzoyl ethylene diamine and the N-benzoyl substituted ureas. Suitable imidazole type perbenzoic acid precursors include N-benzoyl imidazole and N-benzoyl benzimidazole and other useful N-acyl group-containing perbenzoic acid precursors include N- benzoyl pyrrolidone, dibenzoyl taurine and benzoyl pyroglutamic acid. Other perbenzoic acid precursors include the benzoyl diacyl peroxides, the benzoyl tetraacyl peroxides, and the compound having the formula. Phthalic anhydride is another suitable perbenzoic acid precursor compound herein: @ $ o Suitable N-acylated precursor compounds of the lactam class are disclosed generally in GB-A-855735. Whilst the broadest aspect of the invention contemplates the use of any lactam useful as a peroxyacid precursor, preferred materials comprise the caprolactams and valerolactams. Suitable caprolactam bleach precursors are of the formula: CH. CH. CH, N CH. CH. wherein R*> 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 valero lactams have the formula: CH. CH. N CH 2 CH 2 wherein R" 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 most preferred materials are those which are normally solid at < 30°C, particularly the phenyl derivatives, ie. benzoyl valerolactam, benzoyl caprolactam and their substituted benzoyl analogues such as chloro, amino alkyl, alkyl, aryl and alkyloxy derivatives. Caprolactam and valerolactam precursor materials wherein the R*> moiety contains at least 6, preferably from 6 to about 12, carbon atoms provide peroxyacids on perhydrolysis of a hydrophobic character which afford nucleophilic and body soil clean-up. Precursor compounds wherein R6 comprises from 1 to 6 carbon atoms provide hydrophilic bleaching species which are particularly efficient for bleaching beverage stains. Mixtures of 'hydrophobic' and 'hydrophilic' caprolactams and valero lactams, typically at weight ratios of 1:5 to 5:1 , preferably 1:1 , can be used herein for mixed stain removal benefits. Perbenzoic acid derivative precursors Perbenzoic acid derivative precursors provide substituted perbenzoic acids on perhydrolysis. Suitable substituted perbenzoic acid derivative precursors include any of the herein disclosed perbenzoic precursors in which the benzoyl group is substituted by essentially any non-positively charged (ie; non-cationic) functional group including, for example alkyl, hydroxy, alkoxy, halogen, amine, nitrosyl and amide groups. A preferred class of substituted perbenzoic acid precursor compounds are the amide substituted compounds of the following general formulae: R -C — N — -R 2 — C — L R 1 — N — -C — R 2 — C — I! ! II i ς n I! 0 R 5 0 or R 5 0 0 wherein Rl is an aryl or alkaryl group with from 1 to 14 carbon atoms, R 2 is an arylene, or alkarylene group containing from 1 to 14 carbon atoms, and R^ is H or an alkyl, aryl, or alkaryl group containing 1 to 10 carbon atoms and L can be essentially any leaving group. Rl preferably contains from 6 to 12 carbon atoms. R 2 preferably contains from 4 to 8 carbon atoms. R Ϊ may be aryl, substituted aryl or alkylaryl containing branching, substitution, or both and may be sourced from either synthetic sources or natural sources including for example, tallow fat. Analogous structural variations are permissible for R 2 . The substitution can include alkyl, aryl, halogen, nitrogen, sulphur and other typical substituent groups or organic compounds. R^ is preferably H or methyl. R and R^ should not contain more than 18 carbon atoms in total. Amide substituted bleach activator compounds of this type are described in EP-A-0170386. Cationic peroxyacid precursors Cationic peroxyacid precursor compounds produce cationic peroxyacids on perhydrolysis. Typically, cationic peroxyacid precursors are formed by substituting the peroxyacid part of a suitable peroxyacid precursor compound with a positively charged functional group, such as an ammonium or alkyl ammmonium group, preferably an ethyl or methyl ammonium group. Cationic peroxyacid precursors are typically present in the solid detergent compositions as a salt with a suitable anion, such as a halide ion. The peroxyacid precursor compound to be so cationically substituted may be a perbenzoic acid, or substituted derivative thereof, precursor compound as described hereinbefore. Alternatively, the peroxyacid precursor compound may be an alkyl percarboxylic acid precursor compound or an amide substituted alkyl peroxyacid precursor as described hereinafter Cationic peroxyacid precursors are described in U.S. Patents 4,904,406; 4,751,015; 4,988,451; 4,397,757; 5,269,962; 5,127,852; 5,093,022; 5,106,528; U.K. 1,382,594; EP 475,512, 458,396 and 284,292; and in JP 87-318,332. Examples of preferred cationic peroxyacid precursors are described in UK Patent Application No. 9407944.9 and US Patent Application Nos. 08/298903, 08/298650, 08/298904 and 08/298906. Suitable cationic peroxyacid precursors include any of the ammonium or alkyl ammonium substituted alkyl or benzoyl oxybenzene sulfonates, N- acylated caprolactams, and monobenzoyltetraacetyl glucose benzoyl peroxides. A preferred cationically substituted benzoyl oxybenzene sulfonate is the 4-(trimethyl ammonium) methyl derivative of benzoyl oxybenzene sulfonate: A preferred cationically substituted alkyl oxybenzene sulfonate has the formula: Preferred cationic peroxyacid precursors of the N-acylated caprolactam class include the trialkyl ammonium methylene benzoyl caprolactams, particularly trimethyl ammonium methylene benzoyl caprolactam: Other preferred cationic peroxyacid precursors of the N-acylated caprolactam class include the trialkyl ammonium methylene alkyl caprolactams: where n is from 0 to 12. Another preferred cationic peroxyacid precursor is 2-(N,N,N-trimethyl ammonium) ethyl sodium 4-sulphophenyl carbonate chloride. Alkyl percarboxylic acid bleach precursors Alkyl percarboxylic acid bleach precursors form percarboxyhc acids on perhydrolysis. Preferred precursors of this type provide peracetic acid on perhydrolysis. Preferred alkyl percarboxyhc precursor compounds of the imide type include the N-,N,N1N1 tetra acetylated alkylene diamines wherein the alkylene group contains from 1 to 6 carbon atoms, particularly those compounds in which the alkylene group contains 1, 2 and 6 carbon atoms. Tetraacetyl ethylene diamine (TAED) is particularly preferred. Other preferred alkyl percarboxyhc acid precursors include sodium 3,5,5- tri-methyl hexanoyloxybenzene sulfonate (ISONOBS), sodium nonanoyloxybenzene sulfonate (NOBS), sodium acetoxybenzene sulfonate (ABS) and pentaacetyl glucose. Amide substituted alkyl peroxyacid precursors Amide substituted alkyl peroxyacid precursor compounds are also suitable, including those of the following general formulae: R 1 — C — N — R 2 — C — L R 1 — N — C — R 2 C I I I I c II i c i i II O R 5 0 or R 5 O O wherein R^ is an alkyl group with from 1 to 14 carbon atoms, R 2 is an alkylene group containing from 1 to 14 carbon atoms, and R^ is H or an alkyl group containing 1 to 10 carbon atoms and L can be essentially any leaving group. Rl preferably contains from 6 to 12 carbon atoms. R 2 preferably contains from 4 to 8 carbon atoms. Rl may be straight chain or branched alkyl containing branching, substitution, or both and may be sourced from either synthetic sources or natural sources including for example, tallow fat. Analogous structural variations are permissible for R 2 . The substitution can include alkyl, halogen, nitrogen, sulphur and other typical substituent groups or organic compounds. R^ is preferably H or methyl. R and R^ should not contain more than 18 carbon atoms in total. Amide substituted bleach activator compounds of this type are described in EP-A-0170386. Benzoxazin organic peroxyacid precursors Also suitable are precursor compounds of the benzoxazin-type, as disclosed for example in EP-A-332,294 and EP-A-482,807, particularly those having the formula: including the substituted benzoxazins of the type wherein R j is H, alkyl, alkaryl, aryl, arylalkyl, and wherein R2, R3, R4, and R5 may be the same or different substituents selected from H, halogen, alkyl, alkenyl, aryl, hydroxyl, alkoxyl, amino, alkyl amino, COOR^ (wherein R^ is H or an alkyl group) and carbonyl functions. An especially preferred precursor of the benzoxazin-type is: Water-insoluble inorganic compound The composition of the invention also contains one or more water- insoluble inorganic compounds of specific surface area 2m 2 /g to 4m 2 /g, preferably 2.5m 2 /g to 3.5m 2 /g. Specific area is measured, for the purposes of the present invention, by the following technique. The specific surface area, of peroxyacid precursor particulate, is measured using Physisorption equipment comprising of a Micromeritics Gemini 2360 analyser, a Flow prep 060 sample handler and printer. This equipment is manufactured by Micromeritics Instrument Corporation, One Micromeritics Drive, Norcross GA 30093-1877, USA. For this analysis a Flow prep sample container is filled, up to the marked line, with a known weight (to 4 dp (decimal places)) of particulate material. This is then placed in the heating station of the equipment, which is preset to the highest temperature at which the particulate is thermodynamically stable. A gas delivery tube is inserted in the sample tube and held in position with a bung. The sample is then left for two hours to degas. While the test sample is degassing, the saturation pressure (Po) in mm of Hg is determined and stored in the Gemini analyser, using a Balance tube and filler rod in the left (reference) port and an empty tube in the right (sample) port, of the Gemini. After degassing, the sample tube is reweighed to determine the final weight of particulate material. It is then filled with a filler rod and placed in the sample port of the analyser. The sample is then analysed at five points over a range of relative pressures between 0.05 to 0.30 P/Po where P is the sample pressure. The analyser provides a direct reading of the specific surface area of the particle in m /g. The water-insoluble inorganic compounds of such specific surface area are present in amount of from 1 to 15% by weight of the precursor composition, preferably from 2% to 10% by weight thereof. Preferred water-insoluble inorganic compounds of surface area 2m 2 /g to 4m 2 /g, and most preferably 2.5m 2 /g to 3.5m 2 /g, include crystalline layered silicates, aluminosilicates of the synthetic zeolites class such as Zeolite A, X, P (B) and MAP, and natural aluminosihcates such as Montmorillonite, hectorite and saponite of the smectite class of clay minerals. Crystalline layered silicates Preferred crystalline layered silicates for use herein have the general formula NaMSi x θ2χ+ι .yH2θ wherein M is sodium or hydrogen, x is a number from 1.9 to 4 and y is a number from 0 to 20. Crystalline layered sodium silicates of this type are disclosed in EP-A-0164514 and methods for their preparation are disclosed in DE-A-3417649 and DE-A-3742043. Herein, x in the general formula above preferably has a value of 2, 3 or 4 and is preferably 2. The most preferred material is δ-Na2Si2θ5, available from Hoechst AG as NaSKS-6. Crystalline layered silicates are incorporated either as dry mixed solids, or as solid components of agglomerates with other components. Aluminosilicates of the synthetic zeolite class Whilst a range of aluminosilicate ion exchange materials can be used, preferred sodium aluminosilicate zeolites have the unit cell formula Na z [(AIO2 ) z (Si0 2 ) y ] xH 2 0 wherein z and y are at least 6; the molar ratio of z to y is from 1.0 to 0.5 and x is at least 5, preferably from 7.5 to 276, more preferably from 10 to 264. The aluminosilicate materials are in hydrated form and are preferably crystalline, containing from 10% to 28% , more preferably from 18% to 22% water in bound form. The above aluminosilicate ion exchange materials are further characterised by a particle size diameter of from 0.1 to 10 micrometers, preferably from 0.2 to 4 micrometers. The term "particle size diameter" herein represents the average particle size diameter of a given ion exchange material as determined by conventional analytical techniques such as, for example, microscopic determination utilizing a scanning electron microscope or by means of a laser granulometer. The aluminosilicate ion exchange materials are further characterised by their calcium ion exchange capacity, which is at least 200 mg equivalent of CaCθ3 water hardness/g of aluminosilicate, calculated on an anhydrous basis, and which generally is in the range of from 300 mg eq./g to 352 mg eq./g. The aluminosilicate ion exchange materials herein are still further characterised by their calcium ion exchange rate which is at least 130 mg equivalent of CaCθ3/litre/minute/(g/litre) [2 grains Ca+ + / gallon/minute/gram/gallon)] of aluminosilicate (anhydrous basis), and which generally lies within the range of from 130 mg equivalent of CaCθ3/litre/minute/(gram/litre) [2 grains/gallon/minute/ (gram/gallon)] to 390 mg equivalent of CaC03/litre/minute/ (gram/litre) [6 grains/gallon/minute/(gram/gallon)], based on calcium ion hardness. Optimum aluminosilicates for builder purposes exhibit a calcium ion exchange rate of at least 260 mg equivalent of CaCθ3/litre/ minute/ (gram/litre) [4 grains/gallon/minute/(gram/gallon)]. Aluminosilicate ion exchange materials useful in the practice of this invention are commercially available and can be naturally occurring materials, but are preferably synthetically derived. A method for producing aluminosilicate ion exchange materials is discussed in US Patent No. 3,985,669. Preferred synthetic crystalline aluminosilicate ion exchange materials useful herein are available under the designations Zeolite A, Zeolite B, Zeolite MAP (as disclosed in EP-A- 0384070), Zeolite X, Zeolite HS and mixtures thereof. In an especially preferred embodiment, the crystalline aluminosilicate ion exchange material is Zeolite A and has the formula Na 12 [(Alθ2 ) 12 (Siθ2)l2 L *H 2 O wherein x is from 20 to 30, especially 27. Zeolite X of formula Na86 [(Alθ2)86(Siθ2)l06]« 7 6 H2O is also suitable, as well as Zeolite HS of formula Na6 [(Alθ2)6(Siθ2)6l 7.5 H2 O). Natural aluminosilicates By clay mineral compound (or in abbreviation, "clay") it is meant herein a hydrous phyllosilicate, typically having a two or three layer crystal structure. Further description of clays may be found in Kirk-Othmer, Encyclopaedia of Chemical Technology, 4th edition, Volume 6, page 381, as published by John Wiley and Sons. The clay mineral compound is preferably a smectite clay compound. Smectite clays are disclosed in the US Patents No.s 3,862,058, 3,948,790, 3,954,632 and 4,062,647 and European Patents No.s EP-A- 299,575 and EP-A-313,146 all in the name of the Procter and Gamble Company. The term smectite clays herein includes both the clays in which aluminium oxide is present in a silicate lattice and the clays in which magnesium oxide is present in a silicate lattice. Typical smectite clay compounds include the compounds having the general formula Al2(Si2θ5)2(OH)2.nH2θ and the compounds having the general formula Mg3(Si2θ5)2(OH)2.nH2θ. Smectite clays tend to adopt an expandable three layer structure. Specific examples of suitable smectite clays include those selected from the classes of the montmorillonites, hectorites, volchonskoites, nontronites, saponites and sauconites, particularly those having an alkali or alkaline earth metal ion within the crystal lattice structure. Sodium or calcium montmorillonite are particularly preferred. Suitable smectite clays, particularly montmorillonites, are sold by various suppliers including English China Clays, Laviosa, Fordamin, Georgia Kaolin and Colin Stewart Minerals. Preferred smectite clays are sold under the tradename of White Bentonite STP by Fordamin and Detercal P7 by Laviosa Chemical Mineria SPA. Substitution of small cations, such as protons, sodium ions, potassium ions, magnesium ions and calcium ions, and of certain organic molecules including those having positively charged functional groups can typically take place within the crystal lattice structure of the smectite clays. The crystal lattice structure of the clay mineral compounds may have, in a preferred execution, a cationic fabric softening agent substituted therein. Such substituted clays have been termed hydrophobically activated' clays. The cationic fabric softening agents are typically present at a weight ratio, cationic fabric softening agent to clay, of from 1:200 to 1:10, preferably from 1:100 to 1:20. Suitable cationic fabric softening agents include the water insoluble tertiary amines or dilong chain amide materials as disclosed in GB-A-1 514 276 and EP-B-0 011 340. A preferred commercially available "hydrophobically activated" clay is a bentonite clay containing approximately 40% by weight of a dimethyl ditallow quaternary ammonium salt sold under the tradename Claytone EM by English China Clays International. Another preferred but optional embodiment of the invention are clays which have been subjected to an acid washing treatment with any suitable mineral or organic acid. Such clays give rise to an acid pH on dissolution in distilled water. A commercially available "acid clay" of this type is sold under the tradename Tonsil P by Sud Chemie AG. The bleach precursor and said water-insoluble inorganic compound are combined so as to form a particulate material. One preferred method of combining the peroxyacid precursor and the inorganic compound is by agglomeration. Suitable binders for both solid and liquid peroxyacid precursors materials include C12-C ]g fatty acids, C12-C18 aliphatic alcohols condensed with from 10 to 80 moles of ethylene oxide per mole of alcohol, polyethylene glycols of MWt 4000 - 10000 and polymeric materials such as polyvinyl pyrrolidone. The binders agents are preferably present in amounts from 1% to 35% by weight of the particulate and most preferably from 5% to 20% by weight thereof. The agglomeration of the peroxyacid precursor and the water-insoluble inorganic compound can be carried out in a number of ways using equipment known in the art and the process may take place in batch wise or continuous fashion. In a batch process to make the preferred agglomerate embodiments of the invention, an Eirich or Lodige FM agglomeration is used whilst the continuous process can utilise a Shugi Mixer or a Lodige CB or KM Mixer. A combination of the Lodige CB and KM Mixers is preferred. A typical agglomerate formulation comprises: Bleach Activator 50 to 95% Water-insoluble Inorganic Agglomerating Agent 1 % to 15% Binder 3 to 35% The materials, viz. the bleach activator and the water-insoluble inorganic agglomerating agent of specific surface area are fed to the agglomerator at a temperature between 20°C and 30°C. The binder, which is preferably a Tallow alcohol condensed with from 11 to 50 moles of ethylene oxide per mole, or a Polyethylene glycol of MWt 1000 to 8000, is then fed to the agglomerator as a molten material at approximately 55 °C. The binder is added over a period of from 30 to 60 seconds and the mass is then mixed for a further 1 to 2 minutes, the temperature of the mixture being approximately 30 to 35 °C. The mixing is then stopped and the agglomerate product removed from the mixer and further cooled in a fluid bed cooler. The product is then sieved and materials that are greater than 1180 micrometers and smaller than 250 micrometers are removed. More preferably the particle size should be in the range of from 400 micrometers to 750 micrometers and most preferably from 550 micrometers to 650 micrometers. Additionally, the particulate can also include other components that are conventional in detergent compositions, provided that these are not incompatible per se. Examples of such components include chelants, surfactants, soil suspending agents, enzymes and water-soluble organic acid. Specific embodiments of such additional components and their levels of incorporation are described hereinafter but the total level of these components normally lies in the range of from 4% to 49% by weight of the peroxyacid precursor composition. The peroxyacid precursor(s) should form the major component of the precursor composition, i.e from 50% to 95% by weight of the agglomerate, preferably at least 55% by weight and most preferably at least 60% by weight thereof, together with a water-insoluble inorganic compound present in amount of from 1 % to 15%, preferably 2% to 10 % by weight thereof. A preferred additional component in the agglomerated embodiments of the precursor composition is a water-soluble organic acid compound present in an amount of from 3% to 35% by weight of the composition more preferably in an amount of from 5% to 30% and most preferably from 10% to 25% by weight. For the purposes of the invention an acid compound is defined as a compound that, in a 1 % solution in distilled water at 20°C, has a pH of 6.5 or less. Also for the purposes of the invention, 'a solid' is defined as material that is a solid at ambient temperatures, and so organic acid compounds must have a Melting Point of at least 30°C and preferably of at least 40°C. Preferred organic acid compounds will have a Melting Point in excess of 50°C. The acid compound must also be highly soluble in water at ambient temperatures, highly soluble being defined for the purposes of the present invention as at least 5g of the acid dissolving in lOOg of distilled water at 20°C. Preferably the acid compound has a solubility of at least 20g/100g of water at 20°C and most preferably the acid compound will dissolve in its own weight of water at 20°C. Organic acid compounds suitable for incorporation in the agglomerated embodiments of the invention include citric acid and the acid citrate salts, glycolic acid, polyacrylic acid of MWt 500 - 20,000 and acid copolymers of maleic anhydride and acrylic acid of MWt 500 - 100,000. A preferred but optional component of the precursor compositions of the invention is one or more dusting agent used at a level of from 1 % to 5 % by weight, particularly for those precursors in agglomerated form. This dusting component improves the flow of the precursor compositions. A suitable dusting agent is a water-insoluble inorganic compound of specific surface area as herein before described. Examples of such compounds include the synthetic zeolites and hydrophobic silicas. The detergent composition aspect of the invention comprises the incorporation of the hereinbefore described precursor compositions together with a surfactant material, a source of alkaline hydrogen peroxide, and optionally other detergent ingredients, in a detergent product. Detergent compositions incorporating the peroxy acid bleach precursor particulates will normally contain from 0.5% to 12% of the precursor, more frequently from 1 % to 10% and most preferably from 2% to 9%, on a composition weight basis. Such detergent compositions will, of course, contain a source of alkaline hydrogen peroxide necessary to form a peroxyacid bleaching species in the wash solution and preferably will also contain other components conventional in detergent compositions. The precise nature of these additional components and levels of incorporation thereof will depend on the physical form of the composition, and the nature of the cleaning operation for which it is to be used. The compositions of the invention may, for example, be formulated as hand and machine laundry detergent compositions, including laundry additive compositions and compositions suitable for use in the pretreatment of stained fabrics and machine dishwashing compositions. When incorporated in compositions suitable for use in a machine washing method, eg: machine laundry and machine dishwashing methods, the compositions of the invention preferably contain one or more additional detersive components. Thus preferred detergent compositions will incorporate one of more of surfactants, organic and inorganic builders, soil suspending and anti- redeposition agents, suds suppressors, enzymes, fluorescent whitening agents photo activated bleaches, perfumes and colours. Alkaline hydrogen peroxide source Detergent compositions incorporating the peroxyacid precursor particulates of the present invention will include an inorganic perhydrate bleach, normally 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, more preferably from 5% to 35% by weight and most preferably from 8% to 30% by weight of the composition. The perhydrate may be any of the alkali metal inorganic salts such as perborate monohydrate or tetrahydrate, percarbonate, perphosphate and persilicate salts, but is conventionally an alkali metal perborate or percarbonate. Sodium percarbonate, which is the preferred perhydrate, is an addition compound having a formula corresponding to 2Na2Cθ3.3H2θ2, and is available commercially as a crystalline solid. Most 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-phosphonate, that is incorporated during the manufacturing process. For the purposes of the detergent composition aspect of the present invention, the percarbonate can be incorporated into detergent compositions without additional protection, but preferred executions of such compositions utilise a coated form of the material. A variety of coatings can be used including borosilicate borate, boric acid and citrate or sodium silicate of Siθ2:N 2θ ratio 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%, (normally from 3% to 5%) of silicate solids by weight of the percarbonate. However the most preferred coating is a mixture of sodium carbonate and sulphate or sodium chloride. The particle size range of the crystalline percarbonate is from 350 micrometers to 1500 micrometers with a mean of approximately 500- 1000 micrometers. Surfactant A wide range of surfactants can be used in the detergent compositions. A typical listing of anionic, nonionic, ampholytic and zwitterionic classes, and 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 USP 4,259,217 issued to Murphy on March 31 , 1981. Nonlimiting examples of surfactants useful herein typically at levels from 1% to 55%, by weight, include the conventional C l-C s alkyl benzene sulfonates ("LAS") and primary, branched-chain and random C10-C20 alkyl sulfates ("AS"), the C10-C18 secondary (2,3) alkyl sulfates of the formula CH3(CH2)χ(CHOSθ3 " M + ) CH3 and CH3 (CH2) y (CHOSθ3 " M "1" ) CH2CH3 where x and (y + 1) are integers of at least 7, preferably at least 9, and M is a water-solubilizing cation, especially sodium, unsaturated sulfates such as oleyl sulfate, the C10-C18 a lkyl alkoxy sulfates ("AE X S"; especially EO 1-7 ethoxy sulfates), C10-C18 alkyl alkoxy carboxylates (especially the EO 1-5 ethoxycarboxylates), the CiO-18 glycerol ethers, the C10-C1 alkyl polyglycosides and their corresponding sulfated polyglycosides, and C12-C 8 alpha-sulfonated fatty acid esters. If desired, the conventional nonionic and amphoteric surfactants such as the C12-C 8 alkyl ethoxylates ("AE") including the so-called narrow peaked alkyl ethoxylates and C6-C12 alkyl phenol alkoxylates (especially ethoxylates and mixed ethoxy/propoxy), Ci2-Cj8 betaines and sulfobetaines ("sultaines"), Cιo-C]8 amine oxides, and the like, can also be included in the overall compositions. The Cιo-Cj N-alkyl polyhydroxy fatty acid amides can also be used. Typical examples include the C 2-C1 N- methylglucamides. See WO 9,206,154. Other sugar-derived surfactants include the N-alkoxy polyhydroxy fatty acid amides, such as C 0-C18 N (3-methoxypropyl) glucamide. The N-propyl through N-hexyl C12-C18 glucamides can be used for low sudsing. C10-C20 conventional soaps may also be used. If high sudsing is desired, the branched-chain CJO- Ci6 soaps may be used. Mixtures of anionic and nonionic surfactants are especially useful. Other conventional useful surfactants are listed in standard texts. Builders - Detergent builders can optionally be included in the compositions herein to assist in controlling mineral hardness. Inorganic as well as organic builders can be used. Builders are typically used in fabric laundering compositions to assist in the removal of particulate soils. The level of builder can vary widely depending upon the end use of the composition and its desired physical form. When present, the compositions will typically comprise at least 1% builder. Liquid formulations typically comprise from 5% to 50%, more typically 5% to 30%, by weight, of detergent builder. Granular formulations typically comprise from 10% to 80%, more typically from 15% to 50% by weight, of the detergent builder. Lower or higher levels of builder, however, are not meant to be excluded. Inorganic or phosphate-containing detergent builders include, but are not limited to, the alkali metal, ammonium and alkanolammonium salts of polyphosphates (exemplified by the tripolyphosphates, pyrophosphates, and glassy polymeric meta-phosphates). Non-phosphate builders may also be used. These can include, but are not restricted to phytic acid, silicates, alkali metal carbonates (including bicarbonates and sesquicarbonates), sulphates, aluminosilicates, monomeric polycarboxylates, homo or copolymeric polycarboxylic acids or their salts in which the polycarboxylic acid comprises at least two carboxylic radicals separated from each other by not more than two carbon atoms, organic phosphonates and aminoalkylene poly (alkylene phosphonates). Importantly, the compositions herein function surprisingly well even in the presence of the so-called "weak" builders (as compared with phosphates) such as citrate, or in the so-called "underbuilt" situation that may occur with zeolite or layered silicate builders. Examples of silicate builders are the so called 'amorphous' alkali metal silicates, particularly those having a Siθ2:Na2θ ratio in the range 1.6: 1 to 3.2:1 and crystalline layered silicates, such as the layered sodium silicates described in U.S. Patent 4,664,839. NaSKS-6 is the trademark for a crystalline layered silicate marketed by Hoechst (commonly abbreviated herein as "SKS-6"). Unlike zeolite builders, the Na SKS-6 silicate builder does not contain aluminium. NaSKS-6 has the delta- Na2Si2θ5 morphology form of layered silicate. It can be prepared by methods such as those described in German DE-A-3 ,417,649 and DE-A- 3,742,043. SKS-6 is a highly preferred layered silicate for use herein, but other such layered silicates, such as those having the general formula NaMSiχθ2χ+ι yH2θ 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. Various other layered silicates from Hoechst include NaSKS-5, NaSKS-7 and NaSKS-11, as the alpha, beta and gamma forms. As noted above, the delta-Na2Si2θ5 (NaSKS-6 form) is most preferred for use herein. Other silicates may also be useful such as for example magnesium silicate, which can serve as a crispening agent in granular formulations, as a stabilising agent for oxygen bleaches, and as a component of suds control systems. Examples of carbonate builders are the alkaline earth and alkali metal carbonates as disclosed in German Patent Application No. 2,321,001 published on November 15, 1973. Aluminosilicate builders are useful in the present invention. Aluminosilicate builders are of great importance in most currently marketed heavy duty granular detergent compositions, and can also be a significant builder ingredient in liquid detergent formulations. Aluminosilicate builders include those having the empirical formula: Na z [(A10 2 )z(Si0 2 )y]χH2θ wherein z and y are integers of at least 6, the molar ratio of z to y is in the range from 1.0 to 0.5, and x is an integer from 15 to 264. Useful aluminosilicate ion exchange materials are commercially available. These aluminosilicates can be crystalline or amorphous in structure and can be naturally-occurring aluminosilicates or synthetically derived. A method for producing aluminosilicate ion exchange materials is disclosed in U.S. Patent 3,985,669. Preferred synthetic crystalline aluminosilicate ion exchange materials useful herein are available under the designations Zeolite A, Zeolite P (B), Zeolite MAP and Zeolite X. In an especially preferred embodiment, the crystalline aluminosilicate ion exchange material has the formula: Nai2[(Alθ2)i2(Siθ2)l2l-xH2θ wherein x is from 20 to 30, especially 27. This material is known as Zeolite A. Dehydrated zeolites (x = 0 - 10) may also be used herein. Preferably, the aluminosilicate has a particle size of 0.1-10 microns in diameter. Organic detergent builders suitable for the purposes of the present invention include, but are not restricted to, a wide variety of polycarboxylate compounds. As used herein, "polycarboxylate" refers to compounds having a plurality of carboxylate groups, preferably at least 3 carboxylates. Polycarboxylate builder can generally be added to the composition in acid form, but can also be added in the form of a neutralised salt. When utilized in salt form, alkali metals, such as sodium, potassium, and lithium, or alkanolammonium salts are preferred. Included among the polycarboxylate builders are a variety of categories of useful materials. One important category of polycarboxylate builders encompasses the ether polycarboxylates, including oxydisuccinate, as disclosed in U.S. Patent 3,128,287 and U.S. Patent 3,635,830. See also "TMS/TDS" builders of U.S. Patent 4,663,071. Suitable ether polycarboxylates also include cyclic compounds, particularly alicyclic compounds, such as those described in U.S. Patents 3,923,679; 3,835,163; 4,158,635; 4,120,874 and 4,102,903. Other useful detergency builders include the ether hydroxypolycarboxylates, copolymers of maleic anhydride with ethylene or vinyl methyl ether, or acrylic acid, 1, 3, 5-trihydroxy benzene-2, 4, 6- trisulphonic acid, and carboxymethyloxysuccinic acid, the various alkali metal, ammonium and substituted ammonium salts of polyacetic acids such as ethylenediamine tetraacetic acid and nitrilotriacetic acid, as well as polycarboxylates such as mellitic acid, succinic acid, oxydisuccinic acid, polymaleic acid, benzene 1,3,5-tricarboxylic acid, carboxymethyloxysuccinic acid, and soluble salts thereof. Citrate builders, e.g., citric acid and soluble salts thereof (particularly sodium salt), are polycarboxylate builders of particular importance for heavy duty liquid detergent formulations due to their availability from renewable resources and their biodegradability. Citrates can also be used in granular compositions, especially in combination with zeolite and/or layered silicate builders. Oxydisuccinates are also especially useful in such compositions and combinations. Also suitable in the compositions containing the present invention are the 3,3-dicarboxy-4-oxa-l,6-hexanedioates and the related compounds disclosed in U.S. Patent 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 do- decenylsuccinic acid. Specific examples of succinate builders include: laurylsuccinate, myristylsuccinate, palmitylsuccinate, 2- dodecenylsuccinate (preferred), 2-pentadecenylsuccinate, and the like. Laurylsuccinates are the preferred builders of this group, and are described in EP 0,200,263. Other suitable polycarboxylates are disclosed in U.S. Patent 4,144,226 and in U.S. Patent 3,308,067. See also U.S. Pat. 3,723,322. Fatty acids, e.g., C 2-C18 monocarboxylic acids, can also be incorporated into the compositions alone, or in combination with the aforesaid builders, especially citrate and/or the succinate builders, to provide additional builder activity. Such use of fatty acids will generally result in a diminution of sudsing, which should be taken into account by the formulator. In situations where phosphorus-based builders can be used, and especially in the formulation of bars used for hand-laundering operations, the various alkali metal phosphates such as the well-known sodium tripolyphosphates, sodium pyrophosphate and sodium orthophosphate can be used. Phosphonate builders such as ethane- 1 -hydroxy- 1,1- diphosphonate and other known phosphonates (see, for example, U.S. Patents 3,159,581; 3,213,030; 3,422,021; 3,400,148 and 3,422,137) can also be used. 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 amino carboxylates, amino phosphonates, polyfunctionally-substituted aromatic chelating agents and mixtures therein, all as hereinafter defined. Without intending to be bound by theory, it is believed that the benefit of these materials is due in part to their exceptional ability to remove iron and manganese ions from washing solutions by formation of soluble chelates. Amino carboxylates useful as optional chelating agents include ethylenediaminetetracetates, N-hydroxyethylethylenediaminetriacetates, nitrilotriacetates, ethylenediamine tetraproprionates, triethylenetetra- aminehexacetates, diethylenetriaminepentaacetates, and ethanoldi- glycines, alkali metal, ammonium, and substituted ammonium salts therein and mixtures therein. Amino phosphonates are also suitable for use as chelating agents in the compositions of the invention when at least low levels of total phosphorus are permitted in detergent compositions, and include ethylenediaminetetrakis (methylenephosphonates) available under the trademark DEQUEST from Monsanto. Preferably, these amino phosphonates do not contain alkyl or alkenyl groups with more than 6 carbon atoms. Polyfunctionally-substituted aromatic chelating agents are also useful in the compositions herein. See U.S. Patent 3,812,044. Preferred compounds of this type in acid form are dihydroxydisulfobenzenes such as l,2-dihydroxy-3,5-disulfobenzene. Preferred biodegradable non-phosphorus chelants for use herein are ethylenediamine disuccinate ("EDDS"), especially the [S,S] isomer as described in U.S. Patent 4,704,233, ethylenediamine-N,N'-diglutamate (EDDG) and 2-hydroxypropylene-diamine-N,N'-disuccinate (HPDDS) compounds. If utilized, these chelating agents will generally comprise from 0.1% to 10% by weight of the detergent compositions herein. More preferably, if utilized, the chelating agents will comprise from 0.1% to 3.0% by weight of such compositions. Clav Soil Removal/Anti-redeposition Agents - The compositions according to the present invention can also optionally contain water- soluble ethoxylated amines having clay soil removal and antiredeposition properties. Granular detergent compositions which contain these compounds typically contain from 0.01% to 10.0% by weight of the water-soluble ethoxylates amines; liquid detergent compositions typically contain 0.01% to 5%. The most preferred soil release and anti-redeposition agent is ethoxylated tetraethylenepentamine. Exemplary ethoxylated amines are further described in U.S. Patent 4,597,898, VanderMeer, issued July 1, 1986. Another group of preferred clay soil removal-antiredeposition agents are the cationic compounds disclosed in EP 111,965. Other clay soil removal/antiredeposition agents which can be used include the ethoxylated amine polymers disclosed in EP 111,984; the zwitterionic polymers disclosed in EP 112,592; and the amine oxides disclosed in U.S. Patent 4,548,744. Other clay soil removal and or anti redeposition agents known in the art can also be utilized in the compositions herein. Another type of preferred antiredeposition agent includes the carboxy methyl cellulose (CMC) materials. These materials are well known in the art. Polymeric Soil Release Agent - Any polymeric soil release agent known to those skilled in the art can optionally be employed in the compositions and processes of this invention. Polymeric soil release agents are characterised by having both hydrophilic segments, to hydrophilize the surface of hydrophobic fibers, such as polyester and nylon, and hydrophobic segments, to deposit upon hydrophobic fibers and remain adhered thereto through completion of washing and rinsing cycles and, thus, serve as an anchor for the hydrophilic segments. This can enable stains occurring subsequent to treatment with the soil release agent to be more easily cleaned in later washing procedures. Soil release agents characterised by poly( vinyl ester) hydrophobe segments include graft copolymers of poly(vinyl ester), e.g., C]-C6 vinyl esters, preferably poly(vinyl acetate) grafted onto polyalkylene oxide backbones, such as polyethylene oxide backbones (see EP 0 219 048). Commercially available soil release agents of this kind include the SOKALAN type of material, e.g., SOKALAN HP-22, available from BASF (West Germany). One type of preferred soil release agent is a copolymer having random blocks of ethylene terephthalate and polyethylene oxide (PEO) terephthalate. The molecular weight of this polymeric soil release agent is in the range of from 25,000 to 55,000. See U.S. Patent 3,959,230 to Hays and U.S. Patent 3,893,929. Another preferred polymeric soil release agent is a polyester with repeat units of ethylene terephthalate units contains 10-15% by weight of ethylene terephthalate units together with 90-80% by weight of polyoxyethylene terephthalate units, derived from a polyoxyethylene glycol of average molecular weight 300-5,000. Examples of this polymer include the commercially available material ZELCON 5126 (from Dupont) and MILEASE T (from ICI). See also U.S. Patent 4,702,857. Another preferred polymeric soil release agent is a sulfonated product of a substantially linear ester oligomer comprised of an oligomeric ester backbone of terephthaloyl and oxyalkyleneoxy repeat units and terminal moieties covalently attached to the backbone. These soil release agents are described fully in U.S. Patent 4,968,451. Other suitable polymeric soil release agents include the terephthalate polyesters of U.S. Patent 4,711,730, the anionic end-capped oligomeric esters of U.S. Patent 4,721,580 and the block polyester oligomeric compounds of U.S. Patent 4,702,857. Preferred polymeric soil release agents also include the soil release agents of U.S. Patent 4,877,896, which discloses anionic, especially sul- foarolyl, end-capped terephthalate esters. If utilized, soil release agents will generally comprise from 0.01% to 10.0%, by weight, of the detergent compositions herein, typically from 0.1% to 5%, preferably from 0.2% to 3.0%. Still another preferred soil release agent is an oligomer with repeat units of terephthaloyl units, sulfoisoterephthaloyl units, oxyethyleneoxy and oxy-1 ,2-propylene units. The repeat units form the backbone of the oligomer and are preferably terminated with modified isethionate end- caps. A particularly preferred soil release agent of this type comprises one sulfoisophthaloyl unit, 5 terephthaloyl units, oxyethyleneoxy and oxy-1 ,2-propyleneoxy units in a ratio of from 1.7 to 1.8, and two end-cap units of sodium 2-(2-hydroxyethoxy)-ethanesulfonate. Said soil release agent also comprises from 0.5% to 20%, by weight of the oligomer, of a crystalline-reducing stabilizer, preferably selected from xylene sulfonate, cumene sulfonate, toluene sulfonate, and mixtures thereof. Dve Transfer Inhibiting Agents The compositions according to the present invention may also include one or more materials effective for inhibiting the transfer of dyes from one fabric to another during the cleaning process. Generally, such dye transfer inhibiting agents include polyvinyl pyrrolidone polymers, polyamine N-oxide polymers, copolymers of N-vinylpyrrolidone and N- vinylimidazole, manganese phthalocyanine, peroxidases, and mixtures thereof. If used, these agents typically comprise from 0.01% to 10% by weight of the composition, preferably from 0.01% to 5%, and more preferably from 0.05% to 2%. More specifically, the polyamine N-oxide polymers preferred for use herein contain units having the following structural formula: R-A x -P; wherein P is a polymerizable unit to which an N-O group can be attached or the N-O group can form part of the polymerizable unit or the N-O group can be attached to both units; A is one of the following structures: - NC(O)-, -C(0)0-, -S-, -0-, -N=; x is 0 or 1; and R is aliphatic, ethoxylated aliphatics, aromatics, heterocyclic or alicyclic groups or any combination thereof to which the nitrogen of the N-O group can be attached or the N-O group is part of these groups. Preferred polyamine N-oxides are those wherein R is a heterocyclic group such as pyridine, pyrrole, imidazole, pyrrolidine, piperidine and derivatives thereof. The N-O group can be represented by the following general structures: O O I I (Rι)χ-N— (R 2 )y; =N— (R,)χ (R 3 )z 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 N-O group can be attached or form part of any of the aforementioned groups. The amine oxide unit of the polyamine N-oxides has a pKa <10, preferably pKa <7, more preferred pKa <6. Any polymer backbone can be used as long as the amine oxide polymer formed is water-soluble and has dye transfer inhibiting properties. Examples of suitable polymeric backbones are polyvinyls, polyalkylenes, polyesters, polyethers, polyamide, polyimides, polyacrylates and mixtures thereof. These polymers include random or block copolymers where one monomer type is an amine N-oxide and the other monomer type is an N-oxide. The amine N-oxide polymers typically have a ratio of amine to the amine N-oxide 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. The 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; more preferred 1,000 to 500,000; most preferred 5,000 to 100,000. This preferred class of materials can be referred to as "PVNO". The most preferred polyamine N-oxide useful in the detergent compositions herein is poly(4-vinylpyridine-N-oxide) which as an average molecular weight of 50,000 and an amine to amine N-oxide ratio of 1 :4. Copolymers of N-vinylpyrrolidone and N-vinylimidazole polymers (referred to as a class as "PVP VI") are also preferred for use herein. Preferably the PVP VI has an average molecular weight range from 5,000 to 1,000,000, more preferably from 5,000 to 200,000, and most preferably from 10,000 to 20,000. (The average molecular weight range is determined by light scattering as described in Barth, et al., Chemical Analysis. Vol 113. "Modern Methods of Polymer Characterization".) The PVPVI copolymers typically have a molar ratio of N-vinylimidazole to N-vinylpyrrolidone from 1 :1 to 0.2:1, more preferably from 0.8:1 to 0.3:1, most preferably from 0.6:1 to 0.4:1. These copolymers can be either linear or branched. The present invention compositions also may employ a polyvinyl- pyrrolidone ("PVP") having an average molecular weight of from 5,000 to 400,000, preferably from 5,000 to 200,000, and more preferably from 5,000 to 50,000. PVP's are known to persons skilled in the detergent field; see, for example, EP-A-262,897 and EP-A-256,696. Compositions containing PVP can also contain polyethylene glycol ("PEG") having an average molecular weight from 500 to 100,000, preferably from 1,000 to 10,000. Preferably, the ratio of PEG to PVP on a ppm basis delivered in wash solutions is from 2:1 to 50:1, and more preferably from 3:1 to 10:1. The detergent compositions herein may also optionally contain from 0.005% to 5% by weight of certain types of hydrophilic optical brighteners which also provide a dye transfer inhibition action. If used, the compositions herein will preferably comprise from 0.01% to 1% by weight of such optical brighteners. The hydrophilic optical brighteners useful in the present invention are those having the structural formula: wherein R] is selected from anilino, N-2-bis-hydroxyethyI and NH-2- hydroxyethyl; R is selected from N-2-bis-hydroxyethyl, N-2- hydroxyethyl-N-methylamino, moφhilino, chloro and amino; and M is a salt-forming cation such as sodium or potassium. When in the above formula, R\ is anilino, R2 is N-2-bis- hydroxyethyl and M is a cation such as sodium, the brightener is 4,4',- bis[(4-anilmo-6-(N-2-bis-hydroxyethyl)-s-triazine-2-yl)amino]-2,2'- stilbenedisulfonic acid and disodium salt. This particular brightener species is commercially marketed under the tradename Tinopal-UNPA- GX by Ciba-Geigy Coφoration. Tinopal-UNPA-GX is the preferred hydrophilic optical brightener useful in the detergent compositions herein. When in the above formula, R is anilino, R2 is N-2-hydroxyethyl- N-2-methylamino and M is a cation such as sodium, the brightener is 4,4'- bis[(4-anilino-6-(N-2-hydroxyethyl-N-memylamino)-s-triazine-2- yl)amino]2,2'-stilbenedisulfonic acid disodium salt. This particular brightener species is commercially marketed under the tradename Tinopal 5BM-GX by Ciba-Geigy Coφoration. When in the above formula, Ri is anilino, R2 is moφhilino and M is a cation such as sodium, the brightener is 4,4'-bis[(4-anilino-6- moφMlino-s-triazine-2-yl)amino]2,2'-stilbenedisulfonic acid, sodium salt. This particular brightener species is commercially marketed under the tradename Tinopal AMS-GX by Ciba Geigy Coφoration. Other specific optical brightener species which may be used in the present invention provide especially effective dye transfer inhibition performance benefits when used in combination with the selected polymeric dye transfer inhibiting agents hereinbefore described. The combination of such selected polymeric materials (e.g., PVNO and/or PVPVI) with such selected optical brighteners (e.g., Tinopal UNPA-GX, Tinopal 5BM-GX and/or Tinopal AMS-GX) provides significantly better dye transfer inhibition in aqueous wash solutions than does either of these two detergent composition components when used alone. Without being bound by theory, it is believed that such brighteners work this way because they have high affinity for fabrics in the wash solution and therefore deposit relatively quick on these fabrics. The extent to which brighteners deposit on fabrics in the wash solution can be defined by a parameter called the "exhaustion coefficient". The exhaustion coefficient is in general as the ratio of a) the brightener material deposited on fabric to b) the initial brightener concentration in the wash liquor. Brighteners with relatively high exhaustion coefficients are the most suitable for inhibiting dye transfer in the context of the present invention. Of course, it will be appreciated that other, conventional optical brightener types of compounds can optionally be used in the present compositions to provide conventional fabric "brightness" benefits, rather than a true dye transfer inhibiting effect. Such usage is conventional and well-known to detergent formulations. Conventional optical brighteners or other brightening or whitening agents known in the art can be incoφorated at levels typically from 0.05% to 1.2%, by weight, into the detergent compositions herein. Commercial optical brighteners which may be useful in the present invention can be classified into subgroups, which include, but are not necessarily limited to, derivatives of stilbene, pyrazoline, coumarin, carboxylic acid, methinecyanines, dibenzothiphene-5,5-dioxide, azoles, 5- and 6-membered-ring heterocycles, and other miscellaneous agents. Examples of such brighteners are disclosed in "The Production and Application of Fluorescent Brightening Agents", M. Zahradnik, Published by John Wiley & Sons, New York (1982). Specific examples of optical brighteners which are useful in the present compositions are those identified in U.S. Patent 4,790,856. These brighteners include the PHOR WHITE series of brighteners from Verona. Other brighteners disclosed in this reference include: Tinopal UNPA, Tinopal CBS and Tinopal 5BM; available from Ciba-Geigy; Artie White CC and Artie White CWD, available from Hilton-Davis, located in Italy; the 2-(4-stιyl-phenyl)-2H-napthol[l,2-d]triazoles; 4,4'- bis- (l,2,3-triazol-2-yl)-stil- benes; 4,4'-bis(stryl)bisphenyls; and the aminocoumarins. Specific examples of these brighteners include 4- methyl-7-diethyl- amino coumarin; l,2-bis(-venzimidazol-2-yl)ethylene; 1,3-diphenyl-phrazolines; 2,5-bis(benzoxazol-2-yl)thiophene; 2-stryl- napth-[l,2-d]oxazole; and 2-(stilbene-4-yl)-2H-naphtho- [l,2-d]triazole. See also U.S. Patent 3,646,015. Anionic brighteners are preferred herein. Suds Suppressors - Compounds for reducing or suppressing the formation of suds can be incoφorated into the compositions of the present invention. Suds suppression can be of particular importance in the so- called "high concentration cleaning process" and in front-loading European-style washing machines. A wide variety of materials may be used as suds suppressors, and suds suppressors are well known to those skilled in the art. See, for example, Kirk Othmer Encyclopedia of Chemical Technology, Third Edition, Volume 7, pages 430-447 (John Wiley & Sons, Inc., 1979). One category of suds suppressor of particular interest encompasses monocarboxyhc fatty acid and soluble salts therein. See U.S. Patent 2,954,347. The monocarboxyhc fatty acids and salts thereof used as suds suppressor typically have hydrocarbyl chains of 10 to 24 carbon atoms, preferably 12 to 18 carbon atoms. Suitable salts include the alkali metal salts such as sodium, potassium, and lithium salts, and ammonium and al anol ammonium salts. The detergent compositions herein may also contain non-surfactant suds suppressors. 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 Ci8- C40 ketones (e.g., stearone), etc. Other suds inhibitors include N- alkylated amino triazines such as tri- to hexa-alkylmelamines or di- to tetra-alkyldiamine chlortriazines formed as products of cyanuric chloride with two or three moles of a primary or secondary amine containing 1 to 24 carbon atoms, propylene oxide, and monostearyl phosphates such as monostearyl alcohol phosphate ester and monostearyl di-alkali metal (e.g., K, Na, and Li) phosphates and phosphate esters. The hydrocarbons such as paraffin and haloparaffin can be utilized in liquid form. The liquid hydrocarbons will be liquid at room temperature and atmospheric pressure, and will have a pour point in the range of -40°C and 50°C, and a minimum boiling point not less than 110°C (atmospheric pressure). It is also known to utilise waxy hydrocarbons, preferably having a melting point below 100°C. The hydrocarbons constitute a preferred category of suds suppressor for detergent compositions. Hydrocarbon suds suppressors are described, for example, in U.S. Patent 4,265,779. The hydrocarbons, thus, include aliphatic, alicyclic, aromatic, and heterocyclic saturated or unsaturated hydrocarbons having from 12 to 70 carbon atoms. The term "paraffin," as used in this suds suppressor discussion, is intended to include mixtures of true paraffins and cyclic hydrocarbons. Another preferred category of non-surfactant suds suppressors comprises silicone suds suppressors. This category includes the use of polyorganosiloxane oils, such as polydimethylsiloxane, dispersions or emulsions of polyorganosiloxane oils or resins, and combinations of polyorganosiloxane with silica particles wherein the polyorganosiloxane is chemisorbed or fused onto the silica. Silicone suds suppressors are well known in the art and are, for example, disclosed in U.S. Patent 4,265,779 and EP 354016. Other silicone suds suppressors are disclosed in U.S. Patent 3,455,839 which relates to compositions and processes for defoaming aqueous solutions by incoφorating therein small amounts of polydimethylsiloxane fluids. Mixtures of silicone and silanated silica are described, for instance, in German Patent Application DOS 2,124,526. Silicone defoamers and suds controlling agents in granular detergent compositions are disclosed in U.S. Patent 3,933,672 and in U.S. Patent 4,652,392. An exemplary silicone based suds suppressor for use herein is a suds suppressing amount of a suds controlling agent consisting essentially of: (i) polydimethylsiloxane fluid having a viscosity of from 20 cs. to 1,500 cs. at 25°C; (ii) from 5 to 50 parts per 100 parts by weight of (i) of siloxane resin composed of (CH3)3SiOι/2 units of Siθ2 units in a ratio of from (CH3)3 SiOι/2 units and to Siθ2 units of from 0.6:1 to 1.2:1; and (iii) from 1 to 20 parts per 100 parts by weight of (i) of a solid silica gel. In the preferred silicone suds suppressor used herein, the solvent for a continuous phase is made up of certain polyethylene glycols or polyethylene-polypropylene glycol copolymers or mixtures thereof (preferred), or polypropylene glycol. The primary silicone suds suppressor is branched crosslinked and preferably not linear. To illustrate this point further, typical liquid laundry detergent compositions with controlled suds will optionally comprise from 0.001 to 1, preferably from 0.01 to 0.7, most preferably from 0.05 to 0.5, weight % of said silicone suds suppressor, which comprises (1) a nonaqueous emulsion of a primary antifoam agent which is a mixture of (a) a polyorganosiloxane, (b) a resinous siloxane 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) at least one nonionic silicone surfactant; and (3) polyethylene glycol or a copolymer of polyethylene-polypropylene glycol having a solubility in water at room temperature of more than 2 weight %; and without polypropylene glycol. Similar amounts can be used in granular compositions, gels, etc. See also U.S. Patents 4,978,471 and 4,983,316; 5,288,431 and U.S. Patents 4,639,489 and 4,749,740, Aizawa et al at column 1, line 46 through column 4, line 35. The silicone suds suppressor herein preferably comprises polyethylene glycol and a copolymer of polyethylene glycol polypropylene glycol, all having an average molecular weight of less than 1,000, preferably between 100 and 800. The polyethylene glycol and polyethylene/polypropylene copolymers herein have a solubility in water at room temperature of more than 2 weight %, preferably more than 5 weight %. The preferred solvent herein is polyethylene glycol having an average molecular weight of less than 1,000, more preferably between 100 and 800, most preferably between 200 and 400, and a copolymer of polyethylene glycol/polypropylene glycol, preferably PPG 200/PEG 300. Preferred is a weight ratio of between 1:1 and 1:10, most preferably between 1 :3 and 1 :6, of polyethylene glycol: copolymer of polyethylene- polypropylene glycol. The preferred silicone suds suppressors used herein do not contain polypropylene glycol, particularly of 4,000 molecular weight. They also preferably do not contain block copolymers of ethylene oxide and propylene oxide, like PLURONIC L101. Other suds suppressors useful herein comprise the secondary alcohols (e.g., 2-alkyl alkanols) and mixtures of such alcohols with silicone oils, such as the silicones disclosed in U.S. 4,798,679, 4,075,118 and EP 150,872. The secondary alcohols include the C6-C 6 alkyl alcohols having a Cj-Ciό chain. A preferred alcohol is 2-butyl octanol, which is available from Condea under the trademark ISOFOL 12. Mixtures of secondary alcohols are available under the trademark ISALCHEM 123 from Enichem. Mixed suds suppressors typically comprise mixtures of alcohol + silicone at a weight ratio of 1 :5 to 5: 1. For any detergent compositions to be used in automatic laundry washing machines, suds should not form to the extent that they overflow the washing machine. Suds suppressors, when utilized, are preferably present in a "suds suppressing amount. By "suds suppressing amount" is meant that the formulator of the composition can select an amount of this suds controlling agent that will sufficiently control the suds to result in a low-sudsing laundry detergent for use in automatic laundry washing machines. The compositions herein will generally comprise from 0% to 5% of suds suppressor. When utilized as suds suppressors, monocarboxyhc fatty acids, and salts therein, will be present typically in amounts up to 5%, by weight, of the detergent composition. Preferably, from 0.5% to 3% of fatty monocarboxylate suds suppressor is utilized. Silicone suds suppressors are typically utilized in amounts up to 2.0%, by weight, of the detergent composition, although higher amounts may be used. This upper limit is practical in nature, due primarily to concern with keeping costs minimized and effectiveness of lower amounts for effectively controlling sudsing. Preferably from 0.01% to 1% of silicone suds suppressor is used, more preferably from 0.25% to 0.5%. As used herein, these weight percentage values include any silica that may be utilized in combination with polyorganosiloxane, as well as any adjunct materials that may be utilized. Monostearyl phosphate suds suppressors are generally utilized in amounts ranging from 0.1% to 2%, by weight, of the composition. Hydrocarbon suds suppressors are typically utilized in amounts ranging from 0.01% to 5.0%, although higher levels can be used. The alcohol suds 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 commercially available amylases, neutral and alkaline proteases, upases, peroxidases, esterases and cellulases conventionally incoφorated into detergent compositions. Suitable proteolytic enzymes are described in GB-A- 1243784, EP-A-0130756 and USP 5185250 and 5204015. Suitable amylases are disclosed in GB-A- 1296839 while cellulases are disclosed in USP 4435307, GB-A-2075028 and 2095275. Lipases for use in detergent compositions are disclosed in GB-A- 1372034 and EP-A- 0341947. A suitable peroxidase is disclosed by WO89/099813. A wide range of enzyme materials and means for their incoφoration into synthetic detergent granules is also discussed in US Patents 3,519,570 and 3,533,139. Fabric Softeners - Various through-the-wash fabric softeners, especially the impalpable smectite clays of U.S. Patent 4,062,647, as well as other softener clays known in the art, can optionally be used typically at levels of from 0.5% to 10% by weight in the present compositions to provide fabric softener benefits concurrently with fabric cleaning. Clay softeners can be used in combination with amine and cationic softeners as disclosed, for example, in U.S. Patent 4,375,416 and U.S. Patent 4,291,071. Other Ingredients - A wide variety of other functional ingredients useful 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 bar compositions, etc. If high sudsing is desired, suds boosters such as the ClO~Cl6 alkanolamides can be incoφorated into the compositions, typically at 1%-10% levels. The C10-C14 monoethanol and diethanol amides illustrate a typical class of such suds boosters. Use of such suds boosters with high sudsing adjunct surfactants such as the amine oxides, betaines and sultaines noted above is also advantageous. If desired, soluble magnesium salts such as MgCl2, MgS04, and the like, can be added at levels of, typically, 0.1%-2%, to provide additional suds and to enhance grease removal performance. Various detersive ingredients employed in the present compositions optionally can be further stabilized by absorbing said ingredients onto a porous hydrophobic substrate, then coating said substrate with a hydrophobic coating. Preferably, the detersive ingredient is admixed with a surfactant before being absorbed into the porous substrate. In use, the detersive ingredient is released from the substrate into the aqueous washing liquor, where it performs its intended detersive function. To illustrate this technique in more detail, a porous hydrophobic silica (trademark SIPERNAT D10, DeGussa) is admixed with a proteolytic enzyme solution containing 3%-5% of C13.15 ethoxylated alcohol (EO 7) nonionic surfactant. Typically, the enzyme/surfactant solution is 2.5 X the weight of silica. The resulting powder is dispersed with stirring in silicone oil (various silicone oil viscosities in the range of 500-12,500 can be used). The resulting silicone oil dispersion is emulsified or otherwise added to the final detergent matrix. By this means, ingredients such as the aforementioned enzymes, bleaches, bleach activators, bleach catalysts, photoactivators, dyes, fluorescers, fabric conditioners and hydrolyzable surfactants can be "protected" for use in detergents, including liquid laundry detergent compositions. Liquid detergent compositions can contain water and other solvents as carriers. Low molecular weight primary or secondary alcohols exemplified by methanol, ethanol, propanol, and isopropanol are suitable. Monohydric alcohols are preferred for solubilizing surfactant, but polyols such as those containing from 2 to 6 carbon atoms and from 2 to 6 hydroxy groups (e.g., 1,3-propanediol, ethylene glycol, glycerine, and 1,2-propanediol) can also be used. The compositions may contain from 5% to 90%, typically 10% to 50% of such carriers. The detergent compositions herein will preferably be formulated such that, during use in aqueous cleaning operations, the wash water will have a pH of between 6.5 and 11, preferably between 7.5 and 10.5. Liquid dishwashing product formulations preferably have a pH between 6.8 and 9.0. Laundry products are typically at pH 9-11. Techniques for controlling pH at recommended usage levels include the use of buffers, alkalis, acids, etc., and are well known to those skilled in the art. The bulk density of granular detergent compositions is typically at least 450 g/litre, more usually at least 600 g/litre and more preferably from 650 g/litre to 1000 g/litre. The invention is illustrated in the following non limiting examples, in which all percentages are on a weight basis unless otherwise stated. In the detergent compositions, the abbreviated component identifications have the following meanings: C12LAS Sodium linear C12 alkyl benzene sulphonate CnAS Sodium coconut alkyl sulphate TAS Sodium tallow alcohol sulphate C45AS Sodium C12-C15 linear alkyl sulphate C25E3S Sodium C12-C15 branched alkyl sulphate condensed with three moles of ethylene oxide Soap Sodium linear alkyl carboxylate derived from an 80/20 mixture of tallow and a coconut oils. C45E7 A C 14-15 predominantly linear primary alcohol condensed with an average of 7 moles of ethylene oxide C25 E3 A C 12-15 branched primary alcohol condensed with an average of 3 moles of ethylene oxide 25E5 A C 12- 15 branched primary alcohol condensed with an average of 5 moles of ethylene oxide Glucamide C 12"C 14 methyl glucamide Polyethylene Homopolymer of ethylene glycol of MWt 4000 Glycol Silicate Amoφhous Sodium Silicate (Siθ2".Na2θ ratio normally follows) NaSKS-6 Crystalline layered silicate of formula δ -Na2Si2θ5 Carbonate Anhydrous sodium carbonate Bicarbonate Anhydrous sodium bicarbonate MgSθ4 Anhydrous magnesium sulphate Sulphate Anhydrous sodium sulphate Zeolite A Hydrated Sodium Aluminosilicate of formula Nai2(A102SiO )l2. 7H 2 0 having a primary particle size in the range from 1 to 10 micrometers STPP Anhydrous sodium tripolyphosphate Citrate Tri-sodium citrate dihydrate Citric Acid Anhydrous citric acid Polyacrylate Homopolymer of acrylic acid of MWt 4000 MA/AA Copolymer of 1 :4 maleic/acrylic acid, average molecular weight about 60,000. Perborate Sodium perborate tetrahydrate of nominal formula NaBO2.3H2O.H2O2 Perborate Anhydrous sodium perborate bleach of Monohydrate nominal formula NaBθ2-H2θ2 Percarbonate Sodium Percarbonate of nominal formula 2Na2Cθ3.3H2θ2 CMC Sodium carboxymethyl cellulose Fluorescer Disodium 4,4'-bis(4-anilino-6~moφholino- 1.3.5-triazin-2-yl)amino) stilbene-2:2'- disulphonate. DETPMP Diethylene triamine penta (Methylene phosphonic acid), marketed by Monsanto under the Trade name Dequest 2060 EDDS : S,S ethylene diamine disuccinate Mixed Suds 25% paraffin wax Mpt 50°C, 17% Suppressor hydrophobic silica, 58% paraffin oil. Savinase proteolytic enzyme activity 4KNPU/g Alcalase 3T proteolytic enzyme activity 3AU/g Cellulase IT cellulytic enzyme activity 1000 SCEVU/g Termamyl 60T Amyloytic enzyme activity 60KNU/g Lipalase Lipolytic enzyme activity lOOkLU/g all sold by NOVO Industries AS PVP polyvinylpyrrolidone of MWt 13000 PVNP poly (4-vinyl pyridine)-N-oxide copolymer of vinyl imidazole and vinylpyrrolidone Granular Suds 12% Silicone/silica, 18% stearyl alcohol,70% Suppressor starch in granular form Example 1 Agglomerates having the following formulations, expressed in %, were made in a Kenwood food mixer: * supplied as Sokolan 45 ex BASF Formulations 1 and 2 were made as follows: The benzoyl caprolactam, citric acid, zeolite A of surface area 2.5m /g to 3.5m 2 /g, and Sokolan CP45 were added to the Kenwood food mixer and pre-mixed. The temperature of the powders was 25 °C. The molten nonionic binder, which was at a temperature of 55 °C, was added to the powder mix over a period of 35 seconds. The resulting preparation was mixed for a further 90 seconds. The temperature of the agglomerated particles was 31 °C and this temperature was maintained while the further Sokolan CP45 was added over a period of 20 seconds to provide a powder coating of the agglomerate. The mixing was then stopped and the coated agglomerate product removed from the Kenwood food mixer and cooled to ambient temperature (15-20°C). This product was then sieved and materials that were greater than 1180 micrometers and smaller than 250 micrometers were removed. Formulations 3 and 4 were made in the same way as Formulation 1 and 2 with the exception of the step of coating with Sokolan CP45 being replaced with a step of dusting the resulting particle with Zeolite A of surface area 2.5m 2 /g to 3.5m /g. Formulation 5 was made in the same way as Formulations 3 and 4 with the exception of the agglomerate containing no zeolite as co- agglomerating agent. Formulation 6 and 7 were made as follows: The benzoyl caprolactam, anhydrous citric acid and zeolite A of surface area 2.5m /g to 3.5m 2 /g were added to the Kenwood food mixer and pre-mixed. The temperature of the powders was 25 °C. The molten nonionic binder (Poly ethylene glycol 4000), which was at a temperature of 55 °C, was added to the powder mix over a period of 35 seconds. The resulting preparation was mixed for a further 90 seconds. The temperature of the agglomerated particles was 31 °C and this temperature was maintained while the further anhydrous Citric acid was added over a period of 20 seconds to provide a powder coating of the agglomerate. The mixing was then stopped and the coated agglomerate product removed from the Kenwood food mixer and cooled to ambient temperature (15-20°C). This product was then sieved and materials that were greater than 1180 micrometers and smaller than 250 micrometers were removed. Formulation 8 was made in the same way as Formulations 6 and 7 with the exception of the agglomerate containing no zeolite as co- agglomerating agent and the step of coating with citric acid being replaced with a step of dusting the resulting particle with Zeolite A of surface area 2.5m 2 /g to 3.5m 2 /g. Formulations 9 and 10 were made in the same way as Formulations 6 and 7 with the exception of the step of coating with citric acid being replaced with a step of dusting the resulting particle with Zeolite A of surface area 2.5m 2 /g to 3.5m /g. Formulation 11 was made in the same way as Formulations 6 and 7 with the exception of the agglomerate containing no zeolite as co- agglomerating agent. Formulation 12 was made in the same way as Formulations 1 and 2 with the exception of the agglomerate containing no zeolite as co- agglomerating agent. The formulations 1 to 12 were then evaluated using the indicated tests: Absolute flow test: A Rotational Split Level Shear Tester RO-200 Automatic was used to determine the absolute flowability factor. The sample was pre- consolidated and then a rotational shear force was applied to the consolidated sample. This resulted in certain shear forces being measured to calculate the particle/particle flow characteristics. Flow grade of at least 3 are acceptable. Cake strength test: The compressed, unsupported cylinder of granules created by the compression test is fractured by applying a weight to the top until the cylinder fractures. The weight in kilograms (kg) required to fracture the cylinder is the cake grade. Cake grade less than or equal to 2 are acceptable. Results Formuliti 1 2 3 4 5 6 7 8 9 10 11 12 ons Absolute 3.79 3.08 3.77 4.25 4.15 4.37 3.09 4.05 3.80 3.92 2.53 2.68 flow Cake - 0.9 1.5 0 1.4 1.6 2 1.8 0 1.5 - - strength It can be seen that the presence of a water-insoluble inorganic compound of specific area such as Zeolite A of surface area 2.5m 2 /g to 3.5m 2 /g as a co-agglomerating agent of the precursor and /or as a dusting agent of the particle greatly enhance the flow properties of the peroxyacid precursor particle. Example 2 The following detergent compositions are in accordance with the invention. A B C D C12LAS 6.5 6.5 7.6 6.9 TAS 3.0 3.0 1.3 2.0 C25E3S 0.15 0.15 0.15 0.15 C45E7 4.0 5.0 1.3 4.0 Zeolite 18.0 17.0 17.0 20 Citrate - - 1.5 5.5 Citric Acid 2.3 1.8 2.6 - NaSKS-6 8.7 6.5 9.5 - Carbonate 16.0 15.5 7.0 15.4 Silicate (2.0 ratio) 0.5 0.5 0.5 3.0 Bicarbonate 4.5 7.5 1.5 - MA/AA Copolyme r: 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 Cellulase IT 0.15 0.15 - 0.1 Alcalase 3T - 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 MgSθ4 0.4 0.4 0.4 0.4 Fluorescer 0.19 0.19 0.15 0.19 Suds Suppressor 0.8 0.8 0.8 0.8 Perfume 0.35 0.4 0.35 0.4 Peroxyacid precursor composition 4.5(D 2.5(1) 3.4( 2 ) 5.0(D Sulphate Minors etc. to 100 100 100 100 * (1) as in Example 4 (2) as in Example 10 A separate spray dried granular component is produced that incoφorated a small quantity (0.3%) of the TAS, the MA/AA polymer, CMC, fluorescer chelant, magnesium sulphate and soil zeolite. Compositions A-D are made in several stages. Firstly an anionic surfactant agglomerate is produced by combining the LAS, C25E3S, and most of the TAS together with the carbonate and most of the zeolite in an in-line mixer and this component, together with the particulate copolymer, is mixed with the surfactant agglomerate. The nonionic surfactant and suds suppressor components are sprayed on to this mixture and the remaining components are then added viz enzymes as granules, citrate, bicarbonate and citric acid-SKS-6 agglomerate (where present), inorganic perhydrate bleach and bleach precursor particles of the invention. Finally perfume is sprayed on. These products have a bulk density of at least 700g/litre. Example 3 The following detergent compositions are in accordance with the invention The Compositions are made as follows: Composition M is made in the same way as Compositions A-D of Example 2 and has a similar density. For Composition E, all of the anionic surfactants together with some zeolite and carbonate are agglomerated in an inline mixer to form one component and the nonionic surfactant components are similarly agglomerated in a separate in line mixer. A 'minors' granule is formed of chelant, fluorescer, CMC and magnesium sulphate and the remaining components are added as dry mix materials or sprayed on as for compositions A-D in Example 2. This product has higher bulk density than that of Compositions A-D being at least 750 g/litre. In Compositions F-L the anionic surfactants, Zeolite A, CMC, MA/AA polymer, chelant, carbonate, fluorescer and, where present, PVP and silicate, are incoφorated in a spray dried granular component to which the remaining materials are dry mixed or sprayed on as appropriate. These spray dried granules can be further processed to achieve a predetermined product bulk density by e.g. communication or compaction by techniques and apparatus well known to those skilled in the art.

Claims: Claims 1 - A peroxyacid bleach precursor composition comprising: a- a peroxyacid bleach precursor b- a water-insoluble inorganic compound of surface area 2m 2 /g to 4m /g; wherein said precursor and said inorganic compound are in close physical proximity. 2- A peroxyacid bleach precursor composition according to Claim 1, wherein said inorganic compound is selected from crystalline layered silicates, synthetic aluminosilicates and natural aluminosilicates and mixtures thereof. 3-A peroxyacid bleach precursor composition according to either one of Claims 1 or 2, wherein said inorganic compound is a synthetic aluminosilicate of the zeolite class. 4-A peroxyacid bleach precursor composition according to either one of Claims 1 or 2, wherein said inorganic compound is a natural aluminosilicate from the clay mineral compounds. 5- A peroxyacid bleach precursor composition according to Claim 4, wherein said clay mineral compounds are selected from the montmorillonites, hectorites, volchonskoites, nontronites, saponites and sauconites of the smectite clay type. 6-A peroxyacid bleach precursor composition according to any one of Claims 1-5, wherein said inorganic compound is in amount from 1% to 15%, preferably from 2 to 10% by weight of the bleach precursor composition. 7- A peroxyacid bleach precursor composition according to any one of Claims 1-6, wherein said peroxyacid bleach precursor is selected from those containing one or more N-or O-acyl groups. 8- A peroxyacid bleach precursor composition according to Claim 7, wherein said peroxyacid bleach precursor is benzoyl caprolactam. 9-A peroxyacid bleach precursor composition according to any one of Claims 1-8, wherein said said bleach precursor composition is an agglomerate which comprises from 50% to 95% of the peroxyacid bleach precursor, from 1% to 15% of the water-insoluble inorganic compound of surface area 2m 2 /g to 4m 2 /g and from 4% to 49% of one or more components selected from binders, chelants, surfactants, soil suspending agents, enzymes and water-soluble organic acid. 10-A peroxyacid bleach precursor composition according to Claim 9, wherein said water-soluble organic acid is a monomeric or oligomeric carboxylate, more preferably a monomeric aliphatic polycarboxylate acid or an acid salt thereof, present in an amount of from 3 to 35 % by weight of the agglomerate. 11-A peroxyacid bleach precursor composition according to either one of Claim 1-10, wherein said agglomerate further comprises a dusting agent selected from synthetic aluminosilicates and natural aluminosilicates and mixtures thereof, present in an amount of from 0.2 to 5% by weight of the agglomerate. 12-A detergent composition comprising a surfactant material, a source of alkaline hydrogen peroxide and a peroxyacid bleach precursor composition as claimed in any one of Claims 1-11. 13-A detergent composition according to Claim 12, wherein the source of alkaline hydrogen peroxide is an inorganic perhydrate salt, preferably sodium perborate or sodium percarbonate.

Inventors: DORSET ANDREW, SHERRINGTON PAUL RICHARD, DORSET, ANDREW, SHERRINGTON, PAUL, RICHARD
Applicants: PROCTER & GAMBLE, THE PROCTER & GAMBLE COMPANY
Application year: 1995
Main classification: C09K3
IPC codes: C11D3, C11D17