Background of the Invention Oral care, water softening and detergent compositions containing phosphates and polyphosphates are well known. In particular, detergent compositions have employed phosphates and polyphosphates as builders for many years and oral care compositions have employed polyphosphates to prevent tartar build-up on teeth.

Detergency is a complex phenomenon believed to involve many factors such as cleaning ability, i. e. the ability to remove soils from substrates such as fabrics and whiteness maintenance, the ability of the detergent to prevent suspended soils from redepositing on the surface. In built detergent systems, builders are thought to have a beneficial influence on many factors such as stabilization of suspended solid soils, emulsification of soils, the surface activity of the detergent solution, the solubility of water-soluble materials in addition to perhaps there most important role of the sequestration of mineral and heavy metal constituents in the washing solution.

Various inorganic salts such as alkali metal carbonates, bicarbonates, borates, phosphates, and silicates are known to display builder properties. The best of these inorganic builders are the water soluble polyphosphates and in particularly the pyrophosphates and tripolyphosphates. Of these, tripolyphosphate (STPP) is the builder most generally used in solid detergent compositions. However, STPP reverts or hydrolyzes to pyro and orthophosphates during the crutching and spray drying processing steps typical in detergent making. Pyro and orthophosphates are less efficient builders.

Particulate soil redeposition also increases in the presence of mixtures of pyro and orthophosphates brought about from reversion. This increase in particulate redeposition leads to a decrease in whiteness maintenance performance and consumer dissatisfaction.

Accordingly, the need remains for phosphates which display improved performance characteristics such as detergency building and reversion resistance.

Summary of the Invention This need is met by the present invention wherein phosphate is polymerized with polyhydroxyl containing moieties to provide polyhydroxyl/phosphate poiymers. Specifically, the present invention provides a polyhyroxyl/phosphate polymer comprising a polyhydroxy moiety and a phosphorous moiety. This polymer comprises the general structure: wherein : each Z is independently selected from the group consisting of H, each Q is independently selected from the group consisting of each X is independently selected from the group consisting of M, and

each M is independently selected from the group consisting of H, Na, K,-OCH2CH2SO3Na, -OCH2CH2N (CH3) 3C1 and Oh4+ ; each R is independently selected from the group consisting of C2 to C22 alkyl alcool. Moreover, at least about 10%, by weight of the polyhydroxyl/phosphate polymer is phosphorous, at least about 1%, by weight of the polyhydroxyl/phosphate polymer is carbon, and wherein the polyhydroxyl/phosphate polymer has an average molecular weight of at least about 600.

In one aspect of the present invention, the ratio, by weight of carbon to phosphorous in the polyhyroxyl/phosphate polymer is from about 0.01 to about 3.0, preferably from about 0.16 to about 2. Preferably, the polyhydroxyl moiety is selected from the group consisting of ethylene glycol, propylene glycol, glycerin, sorbitol, glucose, maltose, starch, polyvinyl alcohol, and mixtures thereof.

In yet another aspect of this invention, there is provided a process for preparing the polyhydroxyl/phosphate polymers of this invention comprising the steps of: a) providing polyphosphoric acid; b) adding at least one polyhydroxyl moiety to the polyphosphoric acid and initiating esterification to form a polyphosphoric acid ester; c) neutralizing said polyphosphoric acid ester to form the polyhydroxyl/phosphate polymer described above. In a preferred aspect of this process, the polyphosphoric acid is formed from the activation of P205 with phosphoric acid.

Further there is provided a built detergent composition comprising:

a) a detergency builder system comprising at least in part, a polyhyroxyl/phosphate polymer defined above; and b) detergent adjunct ingredients, which are preferably selected from the group consisting of surfactants, enzymes, oxygen bleach promoting agents, fabric care promoting agents, and mixtures thereof.

These polyhydroxyl/phosphate polymers provide improved detergency builder capabilities over traditional phosphate builders such as STPP, improved dispersant properties over conventional polyacrylate dispersants at a fraction of the cost, and improved detergency capabilities to conventional aluminosilicate builders at a fraction of the cost. They also provide superior whiteness maintenance, reversion resistance and clay dispersion benefits to traditional phosphate builders and dispersants such as STPP and Glass-H.

Accordingly, it is an object of the present invention to provide polyhydroxyl/phosphate polymers. It is another object of the present invention to provide detergent and oral care compositions containing the polymers of the present. These, and other, objects features and advantages of the present invention will become readily apparent to one of ordinary skill in the art from the following detailed description and the appended claims.

All percentages, ratios and proportions herein are by weight, unless otherwise specified. All temperatures are in degrees Celsius (0 C) unless otherwise specified. All documents cited are in relevant part, incorporated herein by reference.

Brief Description of the Drawinqs While this specification concludes with claims that distinctly define the present invention, it is believed that these claims can be better understood by reference to the Detailed Description Of The Invention and the drawings, wherein: Figure 1 is the Ion Chromatography (IC) spectrum of Sample 1, Example 1; and Figure 2 is the C 13 NMR spectrum of Sample 1, Example 1.

Detailed Description of the Invention The present invention provides improved polymeric phosphate materials which display improved characteristics for detergency building, water softening and oral care compositions. In particutar, the materials are preferred as detergency builders for laundry compositions. As discussed above, phosphate materials provide detergent builder benefits and are relatively low in cost in comparasion to other builder materials, such as zeolites. The detergent builders provide a key role to the overall performance of a fully formulated laundry composition. In addition to other benefits, stabilization of suspended solid soils and sequestration of mineral and heavy metal constituents (i. e. binding capacity) are performed by builders. The polymeric phosphates of the present invention provide superior performance in both of these critical areas of builder activity as measured by calcium binding capacity and clay dispersion rates. In addition, fully formulated detergent composition including the polymeric phosphates of the present invention, display outstanding performance profiles such as in whiteness maintenance profiles and stain removal as well as superior processing advantages.

POLYHYROXYL/PHOSPHATE POLYMERS The present invention lies in the discovery of a novel class of polyhydroxyl containing phosphate polymers. The novel polymers of the present invention comprise phosphate polymers having the general formula: A polyhyroxyl/phosphate polymer comprising a polyhydroxy moiety and a phosphorous moiety, which polymer comprises the general structure: wherein: each Z is independently selected from the group consisting of H, each Q is independently selected from the group consisting of- each X is independently selected from the group consisting of M, and each M is independently selected from the group consisting of H, Na, K,-OCH2CH2SO3Na, -OCH2CH2N (CH3) 3CI and NH4 ; each R is independently selected from the group consisting of C2 to C22 alkyl alcohol; and wherein at least about 10%, by weight of the polyhydroxyl/phosphate polymer is phosphorous, at least about 1%, by weight of the polyhydroxyl/phosphate polymer is carbon, and wherein the polyhydroxyl/phosphate polymer has an average molecular weight of at least about 600.

As stated previously, the phosphate polymers of the present invention display outstanding clay dispersing rates and calcium binding capacities.

Calcium binding capacity (CBC) is a measure of the ability of a detergency builder material to perform one of its most vital roles in a fully formulated laundry detergent composition, sequestration of mineral constituents. CBC is typically measured as mg of CaC03 taken up per gram of the builder compound at room temperature.

To characterize the polyhydroxyl/phosphate polymers of the present invention in accordance with their proposed utility as water softeners or detergent builders, the following method is used to measure the CBC of the materials of the present invention. 0.1 g of test compound is dispersed in 1000 ml of an aqueous solution containing 41 ppm of Ca2+, and where necessary, adjusted to a pH of 10 with dilute NaOH. The solution is stirred at 20°C for 15 minutes, tested for free Ca2+ using a calcium-selective electrode with the results reported in mg CaCO3 per gram test material. The phosphate polymers of the present invention have a calcium binding capacity in the range of from 300 to about 750 mg CaCO3/g, and more preferably 400 to 750 mg CaC03/g.

Clay dispersing rate (CDR) is a measure of the ability of a detergent builder/dispersant material to suspend soils in solution, thereby reducing the amount of re-deposition of the suspended soils. It is typically measured in 100 a. u./min at 520nm in UV-vis spectroscopy. 20 mg of Clay is added into an aqueous solution containing 20ppm phosphate polymer of the present invention.

After stirring for 15 minutes, The turbidity of the suspension is measured in UV- vis Spectroscopy at 520nm in ABS, The results are reported in 100a. u./min. The phosphate polymers of the present invention display clay dispersing rate in the range of from about 4.0 to 7.0 100a. u./min, more preferably about 4.2 to about 6.8 100a. u./min.

In general, the phosphate polymers of the present invention are formed from the reaction of polyphosphoric acid and the polyhydroxy containing moiety to form a polyphosphoric acid ester followed by neutralization of the ester to form the polyhydroxyl/phosphate polymer. The polyphosphoric acid is preferably formed from the activation of P20, with phosphoric acid (H3PO4) and the neutralization is carried out by an alkaline material such as sodium carbonate.

The method of making the phosphate polymers of the present invention may be further illustrated by the Examples given below.

Detergent Compositions

Detergent compositions of the invention comprising a builder system of which at least a portion of the system is the phosphate polymers described herein, may suitably comprise, in more detail, a detergent adjunct ingredient such as: (a) one or more detersive surfactants, (b) a builder system comprising a phosphate polymer as defined above, and optionally at least one of (c) a bleach system (typically a perborate salt or percarbonate salt, preferably with a bleach activator, organic bleach catalyst or transition-metal containing bleach catalyst) and (d) an enzyme system and (e) optionally other detergent ingredients. The compositions preferably include at least three relatively low-level additives other than a conventional brightener, for example an enzyme, a bleach activator and/or catalyst, and at least one polymer, such as those described in more detail hereinafter.

Preferred detergent compositions according to the invention may contain: (a) from 2 to 60 wt. % of one or more detergent surfactants, (b) from 10 to 80 wt. % of one or more detergency builders, including the polyhydroxyl/phosphate polymers, (c) from 5 to 40 wt. % of a bleach system, (d) from 0.05 to 10% of enzyme or mixtures thererof, and (e) optionally other detergent ingredients to 100 wt. %. Bleach-free embodiments are, of course, also contemplated. The compositions may be in granular, bar, liquid or tablet forms as are generally known in the art. The compositions may be packaged in conventional detergent packaging such as bottles with self draining caps for liquids, boxes and bags for granular detergents, etc.

Detergent surfactants The detergent compositions of the invention typically will contain one or more detergent-active compounds (detersive surfactants) which may be chosen from soap and non-soap anionic, cationic, nonionic, amphoteric and zwitterionic detergent-active compounds, and mixtures thereof. Many suitable detergent- active compounds are available and are described in the literature, for example, in"Surface-Active Agents and Detergents", Volumes I and 11, by Schwartz, Perry

and Berch. Preferred detergent-active include synthetic non-soap anionic and nonionic compounds though soaps can also be used, especially in bars.

Anionic surfactants are well-known and include alkylbenzene sulphonates, e. g.,"linear"types having an alkyl chain length of C8-C15; primary and secondary alkyl sulphates, particularly C12-C15 primary alkyl sulphates; alkyl ether sulphates; olefin sulphonates ; alkyl xylene sulphonates; dialkyl sulphosuccinates ; and fatty acid ester sulphonates. Sodium salts are generally preferred.

Nonionic surfactants that may be used include primary and secondary alcohol ethoxylates, especially C8-C20 primary and secondary aliphatic alcools ethoxylated with from 1 to 20 moles of ethylene oxide per mole of alcool, and more especially C9-C15 primary aliphatic alcools ethoxylated with an average of from 1 to 10 moles of ethylene oxide per mole of alcohol.

Also of interest are non-ethoxytated nonionic surfactants, for example, alkylpolyglycosides; O-alkanoyl glucosides, and polyhydroxyamides including the glucose amides. The choice of detergent-active compound (surfactant), and the amount, will depend on the intended use of the composition: different surfactant systems may be chosen for handwashing products and for products intended for use in different types of washing machine.

Preferred anionic surfactants useful herein also include mid-chain branched primary alkyl alkoxylated sulphate (s) of W097/39087 A1 published 10/23/97 and mid-chain branched primary alkyl alkoxylated sulphate (s) of W097/39088 A1 published 10/23/97. The phosphate polymers can be incorporated into bleaching detergent compositions comprising bleaching agent, mid-chain branched surfactant and adjunct ingredients as described in W097/39090 A1, published 10/23/97. Also the longer alkyl chain, mid-chain branched surfactant compounds, especially the mid-chain branched alkyl sulfates as described in W097/39091 A1 10/23/97 are useful herein, as are any surfactants derived from branched chain alpha-olefins such as those derived by reacting a mixture of carbon monoxide and hydrogen with a catalyst and

separating the olefin (s) from the mixture as described in W097/38956 A1 of 10/23/97. See also the methods for producing longer chain alkyl sulphate surfactant and alkyl alkoxylated sulphate surfactant compositions using mid- chain branched alcohol or polyoxyalkylene alcohol in the sulphation reaction as described in W097/38972 A1 published 10/23/97; all of said publications being incorporated herein by reference.

The surfactant system can optionally be complemented by one or more cationic surfactants, such as fatty alkyl trimethylammonium salts or any variants thereof, for example those in which one or more substituents attached to the nitrogen atom contain oxygen, as for example in hydroxyethyl. Additionally, special-purpose surfactants, for example the fatty alkyldimethylamine-N-oxides may be added for grease cleaning. Cationic or amine oxide surfactants, when present, are typically used at levels below about 5%, more generally at levels in the range from about 0.1 % to about 2%.

The total amount of surfactant system present will also depend on the intended end use, but suitably ranges from about 2% to about 60 wt. %, preferably from 5% to 40 wt. %.

Detergent compositions suitable for use in most automatic fabric washing machines generally contain anionic non-soap surfactant, or nonionic surfactant, or combinations of the two in any ratio, optionally together with soap. While detergent compositions suitable for use in automatic dishwashing compositions contain nonionic surfactants.

The Detergency Builder System As noted, the detergent compositions of the invention contain as an essential component the polyhydroxyl/phosphate polymers as described herein as a detergency builder. This material may be complemented by one or more known detergency builders. The total amount of detergency builder in the compositions, including the phosphate polymers and other builders, if present, will suitably range from 10 to 85 wt. %.

A suitable complementary builder is selected from zeolite A, zeolite P, zeolite X, zeolite AX (or any other co-crystallized zeolite having equivalent effect), maximum aluminum zeolite P, and mixtures thereof. The amount of zeolite present may suitably range from 5 to 60 wt. %, more preferably from 15 to 40 wt. %, calculated on an anhydrous basis (equivalent to from 6 to 75 wt. %, preferably from 19 to 50 wt. %, calculated on a hydrated basis).

The zeolite may, if desired, be used in conjunction with other inorganic or organic builders. Inorganic builders that may be present include sodium carbonate, if desired in combination with a crystallization seed for calcium carbonate, see GB 1 437 950. Organic builders that may be present include polycarboxylate polymers such as polyacrylates, acrylic/maleic copolymers, and acrylic phosphinates; monomeric polycarboxylates such as citrates, gluconates, oxydisuccinates, glycerol mono-, di-and trisuccinates, carboxymethyloxysuccinates, carboxymethyloxymalonates, dipicolinates, hydroxyethyliminodiacetates, alkyl-and alkenylmalonates and succinates; and sulphonated fatty acid salts though this list is not intended to be exhaustive.

Supplementary builders for use in the present invention also include include citric acid salts, more especially sodium citrate, suitably used in amounts of from 3 to 20 wt. %, more preferably from 5 to 15 wt. %. Other preferred supplementary builders are the water-soluble or partly water-soluble silicates, whether crystalline or amorphous. These include the so-called layer silicates such as SKS-6 from Hoechst/Clariant and/or common 2-ratio or 3-ratio soluble silicates. Such materials, when present, are typically used at levels in the range from about 0.1% to about 20% of the composition; more commonly, the level is below about 10%.

In more detail, suitable silicate builders include water-soluble and hydrous solid types and including those having chain-, layer-, or three-dimensional- structure as well as amorphous-solid silicates or other types. Preferred are alkali metal silicates, particularly those liquids and solids having a SiO2 : Na2O ratio in the range 1.6: 1 to 3.2: 1, including solid hydrous 2-ratio silicates marketed by PQ

Corp. under the tradename BRITESILO, e. g., BRITESIL H20; and layered silicates, e. g., those described in U. S. 4,664,839, May 12,1987, H. P. Rieck.

NaSKS-6 or"SKS-6", is a crystalline layered aluminum-free 6-Na2SiOs silicate marketed by Hoechst and is preferred especially in granular laundry compositions. See DE-A-3,417,649 and DE-A-3,742,043. Other layered silicates, such as those having the general formula NaMSiXO2X+,. yH2O 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 also or alternately be used herein.

Layered silicates from Hoechst also include NaSKS-5, NaSKS-7 and NaSKS-11, as the a, P and y layer-silicate forms. Other silicates may also be useful, e. g. magnesium silicate, for example for bleach stabilizing or process aid purposes.

Also suitable herein are crystalline ion exchange materials or hydrates having chain structure and a composition represented by: xM20 ySiO2. zM'O as anhydride wherein M is Na and/or K, M'is Ca and/or Mg; y/x is 0.5 to 2.0 and z/x is 0.005 to 1.0 as taught in U. S. 5,427,711.

Aluminosilicate builders or zeolites can be useful in certain embodiments. These include materials having formula: [Mz (AIO2) z (SiO2) v] xH2O wherein z and v are integers of at least 6, the molar ratio of z to v is in the range from 1.0 to 0.5, and x is an integer from 15 to 264. Aluminosilicates can be crystalline or amorphous, naturally-occurring or synthetically derived. An aluminosilicate production method is in U. S. 3,985,669, Kummel, et al, October 12,1976. Preferred synthetic crystalline aluminosilicate ion exchange materials are available as Zeolite A, Zeolite P (B), Zeolite X and, to whatever extent this differs from Zeolite P, the so- called Zeolite MAP. Natural types, including clinoptilolite, may be used. Zeolite A has the formula: Na, 2 [(AIO2), 2 (SiO2), 2]. xH2O wherein x is from 20 to 30, especially 27. Dehydrated zeolites (x = 0-10) may also be used. Preferably, the aluminosilicate has a particle size of 0.1-10 microns in diameter.

Suitable carbonate builders include alkaline earth and alkali metal carbonates as disclosed in German Patent Application No. 2,321,001 published on November 15,1973, although sodium bicarbonate, sodium carbonate, sodium

sesquicarbonate, and other carbonate mineras such as trona. Other useful carbonate builders are those of U. S. 5,658,867 issued August 19,1997, to Pancheri et al incorporated herein by reference or any convenient multiple salts of sodium carbonate and calcium carbonate such as those having the composition 2Na2CO3. CaCO3 when anhydrous, and even calcium carbonates including calcite, aragonite and vaterite, especially forms having high surface areas relative to compact calcite may be useful, for example as seeds or for use in synthetic detergent bars.

Also preferred to complement the builder in certain embodiments are polycarboxylate polymers, more especially acrylic/maleic copolymers, suitably used in amounts of from 0.5 to 15 wt. %, especially from 1 to 10 wt. %, of the detergent composition. The invention however includes embodiments from which such conventional polycarboxylate polymers are substantially absent. The term "substantially absent"means that no amount is deliberately added though adventitious amounts may be present, for example as a result of presence in a preformulated additive, such as a particulate enzyme additive.

The Bleach System Preferred detergent compositions of the invention include those containing a bleach system. The bleach system may generally comprise a peroxy bleach compound, for example, an inorganic or organic persalt, optionally but preferably in conjunction with a bleach activator (bleach precursor) to improve bleaching action at low wash temperatures; or an inorganic or organic peroxyacid. A bleach stabilizer (heavy metal sequestrant) may also be present. According to preferred embodiments of the invention, one or more transition-metal-containing, for example Manganese containing, bleach catalysts based on any rigid macropolycyclic ligands may also be present. Likewise organic bleach catalysts such as sulfonimines can be used. Preferred inorganic persalts are sodium perborate monohydrate and sodium percarbonate. In detergent compositions herein, sodium percarbonate or other persalts may be present in an amount of

from 5 to 30 wt. %, preferably from 10 to 25 wt. %. Bleach activators are suitably used in amounts of from 1 to 8 wt. %, preferably from 2 to 5 wt. %. Organic or inorganic peroxyacids can also be used. These are normally in an amount within the range of from 2 to 10 wt. %, preferably from 4 to 8 wt. %. The amount of the bleach catalyst when present in the detergent compositions of the invention is suitably from 0.0001% to 1 wt. %, more typically from 0.001% to about 0.1%. A particuiarly useful transition-metal bleach catalyst is [Mn (Bcyclam) CI2]: "Bcyclam" (5,12-dimethyl-1, 5,8,12-tetraaza-bicyclo [6.6.2] hexadecane) is prepared according to J. Amer. Chem. Soc., (1990), 112,8604. Bcyclam (1.00 g., 3.93 mmol) is dissolved in dry CH3CN (35 mL, distille from CaH2). The solution is evacuated at 15 mm until the CH3CN begins to boil. The flask is then brought to atmospheric pressure with Ar. This degassing procedure is repeated 4 times.

Mn (pyridine) 2CI2 (1.12 g., 3.93 mmol), synthesized according to the literature procedure of J. Inorg. Nucl. Chem., (1974), 36,1535, is added under Ar and the mixture is stirred overnight at room temperature. The reaction solution is filtered with a 0.2p filter. The filtrate is evaporated. 1.35 g. of product is collecte, 90% yield. Organic bleach catalysts can also be used. These include the compounds themselves and/or their precursors, for example any suitable ketone for production of dioxiranes and/or any of the hetero-atom containing analogs of dioxirane precursors or dioxiranes, such as sulfonimines and/or the imines described in U. S. 5,576,282 and references described therein. Levels can be, for example, from about 0.01 % to about 5%.

Monoperoxycarboxylic acids suitable herein can be hydrophilic, such as peracetic acid, or can be relatively hydrophobic. The hydrophobic types include those containing a chain of six or more carbon atoms, preferred hydrophobic types having a linear aliphatic C8-C14 chain optionally substituted by one or

more ether oxygen atoms and/or one or more aromatic moieties positioned such that the peracid is an aliphatic peracid. More generally, such optional substitution by ether oxygen atoms and/or aromatic moieties can be applied to any of the peracids or bleach activators herein. Branched-chain peracid types and aromatic peracids having one or more C3-C 16 linear or branched long-chain substituents can also be useful. The peracids can be used in the acid form or as any suitable salt with a bleach-stable cation. Very useful herein are the organic percarboxylic acids of formula: or mixtures thereof wherein R1 is alkyl, aryl, or alkaryl containing from about 1 to about 14 carbon atoms, R2 is alkylene, arytene or alkarylene containing from about 1 to about 14 carbon atoms, and R5 is H or alkyl, aryl, or alkaryl containing from about 1 to about 10 carbon atoms. When these peracids have a sum of carbon atoms in R1 and R2 together of about 6 or higher, preferably from about 8 to about 14, they are particularly suitable as hydrophobic peracids for bleaching a variety of relatively hydrophobic or"lipophilic"stains, including so-called"dingy" types. Calcium, magnesium, or substituted ammonium salts may also be useful.

With respect to any of these peracids, a bleach activator which yields the corresponding peracid under perhydrolysis conditions can desirably be used.

The bleach activator will generally have a leaving group having any suitable pKa for perhydrolysis in-use. The pKa of the conjugate acid of the leaving group is a measure of suitability, and is typically from about 4 to about 16, or higher, preferably from about 6 to about 12, more preferably from about 8 to about 11.

Common leaving groups include oxybenzenesulfonate. Most commonly, when peracetic acid is the desired peracid, the bleach activator or precursor is an acethylated diamine, such as tetracetylethylenediamine (TAED).

More particularly, preferred hydrophobic bleach activators include sodium nonanoyloxybenzene sulfonate (NOBS or SNOBS), substituted amide types, and

activators related to certain imidoperacid bleaches, for example as described in U. S. 5,061,807. Also useful are the acyl lactam activators especially the acyl caprolactams (e. g. WO 94-28102 A) and acyl valerolactams (e. g. U. S.

5,503,639).

Detersive Enzymes Enzymes can be included in the instant detergent compositions for any of their known purposes. Recent enzyme disclosures in detergents useful herein include bleach/amylase/protease combinations (EP 755,999 A; EP 756,001 A; EP 756,000 A); chondriotinase (EP 747,469 A); protease variants (WO 96/28566 A; WO 96/28557 A; WO 96/28556 A; WO 96/25489 A); xylanase (EP 709,452 A); keratinase (EP 747,470 A); lipase (GB 2,297,979 A; WO 96/16153 A; WO 96/12004 A ; EP 698,659 A; WO 96/16154 A); cellulase (GB 2,294,269 A; WO 96/27649 A; GB 2,303,147 A); thermitase (WO 96/28558 A). More generally, suitable enzymes include proteases, amylases, lipases, cellulases, peroxidases, xylanases, keratinases, chondriotinases; thermitases, cutinases and mixtures thereof of any suitable origin, such as vegetable, animal, bacterial, fungal and yeast origin. Preferred selections are influence by factors such as pH-activity and/or stability optima, thermostability, and stability to active detergents, builders and the like. In this respect bacterial or fungal enzymes are preferred, such as bacterial amylases and proteases, and fungal cellulases.

Clay Soil Removal/Anti-redeposition Agents The compositions of the present invention can also optionally contain water-soluble ethoxylated or acylated amines or polyamines having clay soil removal and antiredeposition properties. Granular detergent compositions which contain these compounds typically contain from about 0.01% to about 10.0% by weight of the water-soluble ethoxylated amines; liquid detergent compositions typically contain about 0.01 % to about 5%.

A preferred soil release and anti-redeposition agent is ethoxylated tetraethylene pentamine. See U. S. 4,597,898. See also European Patent Application 111,965, published June 27,1984. Other clay soil removal/antiredeposition agents which can be used include the ethoxylated amine polymers disclosed in European Patent Application 111,984, published June 27,1984; the zwitterionic polymers disclosed in European Patent Appli- cation 112,592, published July 4,1984; and the amine oxides disclosed in U. S.

4,548,744. Other clay soil removal and/or anti redeposition agents are disclosed in U. S. and WO 95/32272, published November 30,1995. Another type of preferred antiredeposition agent includes the known cellulosic materials such as carboxy methyl cellulose (CMC).

Polymeric Dispersing Agents In addition to the polymers of the present invention, polymeric dispersing agents can be used herein at levels from about 0.1% to about 7%, by weight, especially in the presence of magnesiosilicate, zeolite and/or layered silicate builders. Additional polymeric dispersing agents are disclosed in co-pending US patent application 09/, entitled NITROGEN/PHOSPHATE COPOLYMERS AND COMPOSITIONS CONTAINING THE SAME, filed June-, 1999, in the name of Robert Pan and Derek Liu. The entire disclosure of the 09/ application is incorporated herein by reference. Such agents include polymeric polycarboxylates and polyethylene glycols. Polymeric dispersing agents are believed to enhance detergent builder performance, by mechanisms such as crystal growth inhibition, particulate soil release, peptization, or anti-redeposition.

Polymeric polycarboxylate materials can be prepared by polymerizing or copolymerizing suitable unsaturated monomers, preferably in their acid form.

Unsaturated monomeric acids that 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 in the polymeric polycarboxylates herein

or monomeric segments, containing no carboxylate radicals such as vinylmethyl ether, styrene, ethylene, etc. is suitable provided that such segments do not constitute more than about 40% by weight.

Particularly suitable polymeric polycarboxylates can be derived from acrylic acid, as in water-soluble salts of polymerized acrylic acid. The average molecular weight of such polymers preferably ranges from about 2,000 to 10,000, more preferably from about 4,000 to 7,000 and most preferably from about 4,000 to 5,000. Water-soluble salts of such acrylic acid polymers can include, for example, the alkali metal, ammonium and substituted ammonium salts. See U. S.

3,308,067.

Acrylic/maleic-based copolymers may also be used. Such materials include the water-soluble salts of copolymers of acrylic acid and maleic acid.

The average molecular weight of such copolymers preferably ranges from about 2,000 to 100,000, more preferably from about 5,000 to 75,000, most preferably from about 7,000 to 65,000. The ratio of acrylate to maleate segments will generally range from about 30: 1 to about 1: 1, more preferably from about 10: 1 to 2: 1. Alkali metal, ammonium and substituted ammonium salts of the polymers can be used. See European Patent Application No. 66915, published December 15,1982, as well as in EP 193,360, published September 3,1986, which also describes such polymers comprising hydroxypropylacrylate. Still other useful dispersing agents include the maleic/acrylic/vinyl alcohol terpolymers. Such materials are also disclosed in EP 193,360, including, for example, the 45/45/10 terpolymer of acrylic/maleic/vinyl alcohol.

Another polymeric material which can be included is polyethylene glycol (PEG). PEG can exhibit dispersing agent performance as well as act as a clay soil removal-antiredeposition agent. Typical molecular weight ranges for these purposes range from about 500 to about 100,000, preferably from about 1,000 to about 50,000, more preferably from about 1,500 to about 10,000.

Polyaspartate and polyglutamate dispersing agents may also be used. A preferred average molecular weight is about 10,000.

Other polymer types which may be used include various terpolymers and hydrophobically modified copolymers, including those marketed by Rohm & Haas, BASF Corp., Nippon Shokubai and others for all manner of water- treatment, textile treatment, or detergent applications.

Brightener Any optical brighteners or other brightening or whitening agents known in the art can be incorporated at levels typically from about 0.01% to about 1.2%, by weight, into the detergent compositions herein. Suitable brighteners include those identified in U. S. 4,790,856. These include PHORWHITE brighteners from Verona. Other brighteners disclosed in'856 include: Tinopal UNPA, Tinopal CBS and Tinopal 5BM; available from Ciba-Geigy; Arctic White CC and Arctic White CWD, the 2- (4-styryl-phenyl)-2H-naptho [1,2-d] triazoles; 4,4'-bis- (1.2,3-triazol-2- yl)-stilbenes; 4,4'-bis (styryl) bisphenyls; and the aminocoumarins. Specific examples of these brighteners include 4-methyl-7-diethyl-amino coumarin; 1,2- bis (benzimidazol-2-yl) ethylene; 2,5-bis (benzoxazol-2- yl) thiophene; 2-styryl-naptho and 2- (stilben-4-yl)-2H-naphtho [1,2- d] triazole. See also U. S 3,646,015.

Dye Transfer Inhibiting Agents The compositions of 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, and certain materials accounted for in the bleach system such as zinc, manganese, aluminum and silicon phthalocyanines, peroxidases, and mixtures thereof. If used, these agents typically comprise from about 0.01% to about 10% by weight of the composition, preferably from about 0.01 % to about 5%, and more preferably from about 0.05% to about 2%.

Chelatina Agents Detergent compositions herein may also optionally contain one or more chelating agents for metals such as iron and/or manganese in water-soluble, colloidal or particulate form or associated as oxides or hydroxides, or found in association with soils such as humic substances.. Preferred chelants effectively control such transition metals, especially limiting deposition of such transition- metals or their compounds on fabrics and/or controlling undesired redox reactions in the wash medium and/or at fabric or hard surface interfaces. Such chelating agents include those having low molecular weights as well as polymeric types, typically having at least one, preferably two or more donor heteroatoms such as O or N, capable of co-ordination to a transition-metal, Common chelating agents can be selected from the group consisting of aminocarboxylates, aminophosphonates, polyfunctionally-substituted aromatic chelating agents and mixtures thereof. Preferred chelating agents (chelants) include EDTA, S, S'-EDDS, DTPA, phosphonate types such as HEDP and mixtures thereof.

If utilized, chelating agents will generally comprise from about 0.001% to about 15% by weight of detergent composition. More preferably, chelating agents will comprise from about 0.01 % to about 3.0% by weight of the composition.

Suds Suppressors See, for example, Kirk Othmer Encyclopedia of Chemical Technology, 3rd.

Ed., Vol. 7, pp 430-447 (Wiley, 1979). Compositions herein will generally comprise from 0% to about 10% of suds suppressor. When used as suds suppressors, monocarboxylic fatty acids, or salts thereof, will be present typically in amounts up to about 5%, preferably 0.5%-3% by weight, of the detergent composition. although higher amounts may be used. Preferably, from about 0.01% to about 1% of silicone suds suppressor is used, more preferably from

about 0.25% to about 0.5% including any silica that may be utilized in combination with polyorganosiloxane, as well as any suds suppressor adjunct materials that may be utilized. Hydrocarbon suds suppressors are typically utilized in amounts ranging from about 0.01% to about 5.0%, although higher levels can be used. The alcohol suds suppressors can be used at 0.2%-3% by weight of detergent composition.

Other ingredients A wide variety of other ingredients useful in detergent compositions can be included in the compositions herein, including perfumes, enzyme stabilizers, chlorine scavengers, such as ammonium sulfate; other active ingredients, carriers, hydrotropes, processing aids, dyes or pigments, filles, especially for bar compositions, etc. If desired, magnesium and/or calcium salts such as MgCl2, MgSO4, Cal2, CaSO4, magnesium silicates and the like, can be added, for example as fillers for bar forms of the compositions.

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.

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 about 6.5 and about 11, preferably between about 7.0 and 10.5, more preferably between about 7.0 to about 9.5. 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.

Form of the Compositions

Compositions herein can vary in physical form, as nonlimitingly illustrated by granular, tablet, bar, and pouch forms. The compositions include the so-called concentrated granular detergent compositions adapted to be added to a washing machine by means of a dispensing device placed in the machine drum with the soiled fabric load.

The mean particle size of the components of granular detergent compositions herein is preferably be such that no more that 5% of particles are greater than 1.7mm in diameter and not more than 5% of particles are less than 0.15mm in diameter.

"Mean particle size"herein can be determined by sieving a sample of material to be sized into a number of fractions (typically 5) on a series of Tyler sieves. Weights of fractions are plotted against the aperture size of the sieves.

The mean particle size is the aperture size through which 50% by weight of the sample would pass.

Certain preferred granular detergent compositions in accordance herein are high-density types, now common in the marketplace; typically these have a bulk density of at least 600 g/litre, more preferably from 650 g/litre to 1200 g/litre.

Although, lower densities in the neighborhood of 450-550 g/litre are also contemplated herein.

Laundry Washinq Method Machine laundry methods herein typically comprise treating soiled laundry with an aqueous wash solution in a washing machine having dissolved or dispensed therein an effective amount of a detergent composition of the invention. By an"effective amount"is here meant from 40g to 300g of product dissolved or dispersed in a wash solution of volume from 5 to 65 litres.

In the context of fabric laundering, product"usage levels"can vary widely, depending not only on the type and severity of soils and stains, but also on wash water temperatures and volumes and type of washing machine.

In a preferred use aspect a dispensing device is employed in the washing method. The dispensing device is charged with the detergent product, and is used to introduce the product directly into the drum of the washing machine before the start of the wash cycle. Its capacity should be such as to be able to contain sufficient detergent product as would normally be used in the washing method.

Once the washing machine has been loaded with laundry, the dispensing device containing the detergent product is placed inside the drum. At the commencement of the wash cycle of the washing machine, water is introduced into the drum and the drum periodically rotates. The design of the dispensing device should be such that it permits containment of the dry detergent product but then allows release of this product during the wash cycle in response to its agitation as the drum rotates and also as a result of its contact with the wash water.

Alternatively, the dispensing device may be a flexible container, such as a bag or pouch. The bag may be of fibrous construction coated with a water impermeable protective material so as to retain the contents, such as is disclosed in European published Patent Application No. 0018678. Alternatively it may be formed of a water-insoluble synthetic polymeric material provided with an edge seal or closure designed to rupture in aqueous media as disclosed in European published Patent Application Nos. 0011500,0011501,0011502, and 0011968.

A convenient form of water-frangible closure comprises a water soluble adhesive disposed along and sealing one edge of a pouch formed of a water impermeable polymeric film such as polyethylene or polypropylene.

High Density Detergent Composition Processes Spray-drying towers can be used to make granular laundry detergents or base powders. These often have a density less than about 500 g/l. Typically, an aqueous slurry of ingredients is passed through a spray-drying tower at temperatures of about 175°C to about 225°C.

Additional process steps must be used to obtain high density, low dosage detergents."High density"means greater than about 550, typically greater than about 650, grams/liter or"g/l"). Thus spray-dried granules can be densified by loading a liquid, often a nonionic surfactant, into the pores of the granules and/or passing them through one or more high speed mixer/densifiers such as a device sold as a"Lödige CB 30"or"Lodige CB 30 Recycler". This comprises a static cylindrical mixing drum having a central rotating shaft on which are mounted mixing/cutting blades. Ingredients for the detergent composition are introduced into the drum and the shafVblade assembly is rotated at speeds in the range of 100-2500 rpm to provide thorough mixing/densification. See U. S. 5,149,455 and Other suitable commercial apparatus includes the"Shugi Granulator" and the"Drais K-TTP 80.

Spray-dried granules can also be densified by treating them in a moderate speed mixer/densifier so as to obtain particles, for which the"Lödige KM" (Series 300 or 600) or"Lödige Ploughshare"mixer/densifiers are suitable and are typically operated at 40-160 rpm. Other useful equipment includes the"Drais K-T 160". This process step using a moderate speed mixer/densifier (e. g. Lödige KM) can be used alone or sequentially with the aforementioned high speed mixer/densifier (e. g. Lödige CB) to achieve the desired density. Other types of granules manufacturing apparatus useful herein include the apparatus disclosed in U. S. Patent 2,306,898, to G. L. Heller, December 29,1942.

While it may be more suitable to use the high speed mixer/densifier followed by the low speed mixer/densifier, the reverse sequential mixer/densifier configuration can also be used. One or a combination of various parameters including residence times in the mixer/densifiers, operating temperatures of the equipment, temperature and/or composition of the granules, the use of adjunct ingredients such as liquid binders and flow aids, can be used to optimize densification of the spray-dried granules. By way of example, see the processes in U. S. 5,133,924; U. S. 4,637,891, (granulating spray-dried granules with a liquid binder and aluminosilicate); U. S. 4,726,908, (granulating spray-dried granules

with a liquid binder and aluminosilicate); and U. S. 5,160,657, (coating densified granules with aluminosilicate).

Heat sensitive or highly volatile detergent ingredients are preferably incorporated into the detergent composition without resorting to spray drying, for example, by feeding thermally sensitive or volatile ingredients continuously or batchwise into mixing/densifying equipment. One preferred embodiment involves charging a surfactant paste and an anhydrous material into a high speed mixer/densifier (e. g. Lödige CB) followed by a moderate speed mixer/densifier (e. g. Lödige KM) to form high density agglomerates. See U. S. 5,366,652 and U. S. 5,486,303. The liquid/solids ratio of ingredients can be selected to obtain high density agglomerates that are more free flowing and crisp. See U. S.

Optionally, the process may include one or more streams of undersized particles. These can be recycled to the mixer/densifiers for further agglomeration or build-up. Oversized particles can be sent to grinding apparatus, the product of which is fed back to the mixing/densifying equipment. Such recycles facilitate overall particle size control giving in finished compositions which having a relatively uniform distribution of particle size (400-700 microns) and density (> 550 g/I). See U. S. 5,516,448 and U. S. 5,489,392. Other suitable processes which do not call for spray-drying are described in U. S. 4,828,721, U. S. 5,108,646 and U. S. 5,178,798.

In yet another embodiment, the high density detergent compositions can be produced using a fluidized bed mixer in which the ingredients are combined as an aqueous slurry (typically 80% solids content) and sprayed into a fluidized bed to provide finished granules. Optionally prior to fluid bed mixing the slurry can be treated using the aforementioned Lödige CB mixer/densifier or a"Flexomix 160" mixer/densifier, available from Shugi. Fluidized bed or moving beds of the type available under the tradename"Escher Wyss"can also be used.

Another alternate process involves feeding a liquid acid precursor of an anionic surfactant, an alkaline inorganic material (e. g. sodium carbonate) and

optionally other detergent ingredients into a high speed mixer/densifier (residence time 5-30 seconds) so as to form particles containing a partially or totally neutralized anionic surfactant salt and the other starting detergent ingredients. Optionally, the contents in the high speed mixer/densifier can be sent to a moderate speed mixer/densifier (e. g. Lödige KM) for further mixing resulting in the finished high density detergent composition. See U. S. 5,164,108.

Optionally, high density detergent compositions can be produced by blending conventional spray-dried detergent granules with detergent agglomerates in various proportions (e. g. a 60: 40 weight ratio of granules to agglomerates) produced by one or a combination of the processes discussed herein. Additional adjunct ingredients such as enzymes, perfumes, brighteners and the like can be sprayed or admixed with the agglomerates, granules or mixtures thereof produced by the processes discussed herein. For example, see US 5,569,645.

EXAMPLES The following Examples are intended to illustrate the present invention, but they are not intended to limit the invention.

Abbreviations used in Examples LAS Sodium C 1-13 alkyl benzene sulfonate (linear, branched or mixed) Alkyl Sulfate CxyAS: Alkyl sulfate, typically sodium salt form, derived from fatty alcohol containing from x to y carbon atoms.

Examples include sodium tallow alkyl sulfate (TAS) and primary, guerbet, and mid-chain branched (WO 97/39088) alkyl sulfates containing from 10 to 20 carbon atoms (more typically from 14 to 16 or from 16 to 18) or mixtures thereof.

Alkyl Alkoxy Sulfate Sodium salt of linear or branched (WO 97/39087) fatty alcohol condensed with one or more moles of ethylene oxide, propylene oxide, esp. sodium Cix-Cly alkyl sulfate condensed with z moles of ethylene oxide, e. g., C15E1S.

Nonionic linear or branched (WO 97/39091) nonionic surfactant, typically CxyEz, derived from fatty alcohol with chainlength of from x to y condensed with an average of z moles of ethylene oxide Suitable examples include C25E3, C24E5, C45E7.

Glucamide C12-C14 (coco) alkyl N-methyl glucamide or C16-Cl8 alkyl N-methyl glucamide Amine Oxide linear or branched (WO 97/39091) C12-C18 Alkyldimethylamine N-Oxide QAS Quaternary ammonium surfactant, e. g., dodecyltrimethylammonium chloride or R2. N+ (CH3) 2 (C2H40H) X-with R2 = C12-C14 and X- Cl Fatty Acid Sodium linear alkyl carboxylate derived from an 80/20 mixture of tallow and coconut fatty acids (longer-chain soaps may be dual-functional and contribute to suds suppression); C12 C14 topped whole cut fatty acids; mixtures Phosphate polymer Material as disclosed in the present invention and in particular Examples 1-2 Zeolite system: one or more of :- Zeolite A Hydrated sodium aluminosilicate of formula Na12 (A102Si02) 12. 27H20 having a primary particle size in the range from 0.1 to 10 micrometers (weight expressed on an anhydrous basis) Zeolite P Zeolite P (may be maximum aluminum type) Zeolite X Zeolite X Zeolite AX Zeolites A, X co-crystallized (Condea, EP 816291 A1) Silicate system 2r or 3r sodium silicate; crystalline layered silicate of formula â-Na2Si2Os; (Hoechst/Clariant) Amorphous sodium silicate (Si02: Na20 = 2.0: 1); mixtures thereof (hydration of any zeolite may vary) Phosphates:-one or more of STPP Anhydrous sodium tripolyphosphate TSPP Tetrasodium pyrophosphate non-polymer type polycarboxylate:<BR> one or more of :- Citrate Anhydrous citric acid; tri-sodium citrate dihydrate of activity 86.4% with a particle size distribution between 425um and 850um; mixtures thereof TMS/TDS Tartrate Monosuccinate/Tartrate Disuccinate, Sodium Salts ODS 2,2'-oxydisuccinate, Sodium Salts CMOS Carboxymethyloxysuccinate, Sodium Salts NTA Nitrilotriacetic Acid, Sodium Salts Carbonate Anhydrous sodium or potassium carbonate, e. g., with particle size between 200pm and 900pm for admix; or lower, e. g., below 100um, if to be further agglomerated. polymer-type any polycarboxylate of m. w. above about 1,000, polycarboxylate especially sodium salt of copolymer of 1: 4 maieic/acrylic acid, average molecular weight about 70,000, sodium salt; Sodium polyacrylate of average molecular weight 4,500; mixtures thereof; or mixtures of said polymers with any PEG. A preferred polymer-type polycarboxylate has polyglyoxylate structural units (see, for example, US US 4,140,676; EP 803,521 A) Carbohydrate Sodium carboxymethyl cellulose; methyl cellulose ether antiredeposition with a degree of polymerization of 650 available from agent Shin Etsu Chemicals; starch-derived, sugar-derived, sorbitol-derived or any other carbohydrate-derived antiredeposition agent or ash buildup prevention agent, or mixtures thereof.

Enzyme system: one or more of :- Protease Proteolytic enzyme of activity 4KNPU/g sold by NOVO Industries A/S under the tradename Savinase Alcalase Proteolytic enzyme of activity 3AU/g sold by NOVO Industries A/S Cellulase Cellulolytic enzyme of activity 1000 CEVU/g sold by NOVO Industries A/S under the tradename Carezyme Amylase Amylolytic enzyme of activity 120KNU/g sold by NOVO Industries A/S under the tradename Termamyl 120T Lipase Lipolytic enzyme of activity 100KLU/g sold by NOVO Industries A/S under the tradename Lipolase Endolase Endoglucanase enzyme of activity 3000 CEVU/g sold by NOVO Industries A/S Primary Oxygen Sodium perborate tetrahydrate of nominal formula Bleach NaB02.3H20. H202 (abbrev. PB4); anhydrous sodium perborate bleach of nominal formula NaBO2. H202 (abbrev. PB1); sodium percarbonate of nominal formula 2Na2CO3.3H202 (abbrev. PC); any of these in coated or uncoated forms; or mixtures thereof Hydrophilic Bleach any water-soluble acylated di-or lower poly-amine, esp.

Activator tetraacetylethylenediamine Hydrophobic Bleach NOBS, i. e., nonanoyloxybenzene sulfonate in the form of Activator the sodium salt; NAC-OBS, i. e., (6-nonamidocaproyl) oxybenzene sulfonate; mixtures; or similar Hydrophobic e. g., EP 778342 A1 preformed peroxyacid Organic Bleach e. g., omega- (3, 4-dihydroisoquinolinium alkane Booster sulfonate (s) of U. S. 5,576,282 Transition-metal e. g., as described in WO 97/00937, WO 96/06155, EP Bleach Catalyst 718,398 A Photobleach Sulfonated zinc phthlocyanine encapsulated in bleach dextrin soluble polymer; or low-hue photobleach-see, for example, Si phthalocyanine derivatives of WO 97/05202 Chelant System: one or more of: DTPA Diethylene triamine pentaacetic acid DTPMP Diethylene triamine penta (methylene phosphonate), marketed by Monsanto under the Tradename Dequest 2060 EDDS Ethylenediamine-N, N'-disuccinic acid, (S, S) isomer in the form of its sodium salt.

HEDP 1,1-hydroxyethane diphosphonic acid Brightener Disodium 4,4'-bis (2-sulphostyryl) biphenyl; Disodium 4,4'- bis (4-anilino-6-morpholino-1.3.5-triazin-2-yl) amino) stilbene-2: 2'-disulfonate; mixtures Soil Release Agent: one or more of: SRP 1 Sulfobenzoyl and capped esters with oxyethylene oxy and terephthaloyl backbone or SRP of US 5,415,807 SRP 2 Diethoxylated poly (1,2 propylene terephthalate) short block polymer Cotton Soil Release e. g., as described in WO 97/42285 Agent Additional low-level benefit agent: for example, for dye transfer inhibition, fabric care, etc.

TEPAE Tetraethylenepentaamine ethoxylate PVP Polyvinylpyrrolidine polymer, with an average molecular weight of 60,000 PVNO Polyvinylpyridone N-oxide polymer, with an average molecular weight of 50,000 PVPVI Copolymer of polyvinylpyrolidone and vinylimidazole, with an average molecular weight of 20,000 Antifoam System: e. g., polydimethylsiloxane foam controller with siloxane- oxyalkylene copolymer as dispersing agent with a ratio of said foam controller to said dispersing agent of 10: 1 to 100: 1; may be complemented by fatty acid (s).

Other materials Bicarbonate Anhydrous sodium bicarbonate with a particle size distribution between 400ium and 12001Jm Sulfate Anhydrous sodium sulfate Stabilizers, process aids, other minors e. g., one or more of:

Borate Sodium borate Wax Paraffin wax PEGx Polyethylene glycol, with a molecular weight of x PEO Polyethylene oxide, with an average molecular weight of 50,000 Perfume Any perfume or pro-perfume, see, for example,"blooming perfume"in WO 97/34987 In the following examples all levels are quoted as % by weight of the composition: EXAMPLE 1 Samples. 1 1.0 gH3PO4 (85%) is mixed with 10 g P205 to generate polyphosphoric acid paste. Then 1.5 g Glycerol is added into the polyphosphoric acid. Keep the product at 90C for about 2 hours to form polyphosphoric acid ester. After the product cools to room temperature, put 9.5 g sodium carbonate and 20g water into the product to neutralize the polyphosphoric acid ester, and produce the sample 1. The Ca binding capacity of sample 1 is 665 mg CaC03/g. The Clay dispersing rate of this sample is 5.8 (100a. u./min). Ion Chromatography (IC) spectrum of Sample 1 is shows in Fig 1. Fig 2 is the C13 NMR spectrum of Sample 1.

Samples 2 through 7 Samples 2 through 7 are obtained in the same manner as in Sample1 except that the amount of H3PO4 (85%) and Glycerol added is changed to provide the composition shown in Table 1. These samples are excellent in both CBC and CDR in the same manner as in example 1. All samples show similar IC spectra and C13 NMR spectra to that of Sample 1.

Sample 8

10 g P205 powder is mixed with 1.5 g H3PO4 containing 25% Isethonic acid sodium. Then put 1.85 g Glycerol into the reactant to obtain polyphosphoric acid ester. Keep the product at 90C for 2 hours, then cool the product to room temperature. Finally 9.5 g sodium carbonate and 20 g water are used to neutralize the reactant to generate Sample 8. The Ca binding capacity of Sample 8 is 586 mg CaC03/g. The Clay dispersing rate of this sample is 6.3 (100a. u./min).

Samoles 9 through 12 Samples 9 through 12 are obtained in the same manner as in Sample 8 except that the amount of solution of Isethionic acid sodium in H3PO4 (85%) and Glycerol added is changed to provide the composition shown in Table 2. These samples are excellent in both CBC and CDR in the same manner as in Sample 8. All samples have similar IC and C13 NMR spectra to that of Sample 8.

TABLE 1A Sample No. 1 2 3 4 5 6 7 H3PO4/P2O5 0. 10 0.10 0.10 0.15 0.15 0.15 0.20 Glycerol/P205 0.15 0.2 0.25 0.15 0.2 0.25 0.2 CBC (mgCaC03/g 665 564 521 730 720 715 703 ) CDR (100a.u./min) 5.95.86.46.16.25.7 TABLE 1B Sample No. 10111289 Isethionate solution/P205 0.2 0. 2 Glycerol/P205 0. 18 0.18 0.18 0.15 0. 2 CBC (mg CaC03/g) 586 673 733 568 629 CDR6.86.05.65.86.3 EXAMPLE 2 Granular laundry detergents for use in domestic appliances or

handwashing of laundry at from 100 to 10,000 ppm, depending on appliance and/or water and/or conditions, are prepared in accordance with the invention: Ingredient (Range, % unless A B C D E F noted) LAS -102030354 Alkyl Sulfate (0-20) 10 3 1- Alkyl Alkoxy Sulfate (0-5)--0. 5-5 Nonionic(0-15) 5 10 2 0. 5 1 Glucamide (0-5) 3 1 - - - Amine Oxide (0-2) 0. 5-2-- QAS(0-2)----1. 8 2 Phosphate polymer, Sample 1 1 5 3 10 3 5 Zeolite system (0-30)-20-- Carbonate (0-30) 10 10 5 15-20 Phosphates (0-30) 10 5 15 10-20 Silicate system (0-20) 5 1 3-2 10 Non-polymer type--5-5- polycarboxylate (0-20) Polymer-type polycarboxylate (0-1 5 - 10 4 - 20) Carbohydrateantiredeposition 0. 1 0. 2 5 0. 3 0. 2 agent (0-10) Primary Oxygen Bleach (0-20) 20 15 10 5 3 - Hydrophilic Bleach Activator (0--2--4 2 10) Hydrophobic Bleach Activator (0- - 2 1 - 5 10) Organic Bleach Booster (0-5) 2 Transition-metal bleach catalyst 10 100 1000-50 1000 (- 10,000 ppm) 0 Photobleach (0-1000 -10-5-- Chelant System 10.53102 Enzyme System (0-8) 8-3 4 6 1 Brightener (0-2) 0. 1 0. 1 0. 1 0. 2 0. 3 1 Soil Release Agent (0-5)-0. 1 1 2-0. 3 Additional low-level benefit agent--1-1- (0-5) Perfume (0-5) 0.01 0. 1-3 2 1 Antifoam system (0-5) 0. 05 0.1 0.2 0.5 0.7 - Sulfate, stabilizers, process aids, 100 100 100 100 100 100 minors to % % % % % % Density in g/litre (range) 200-200-200-200-200-200- 900 900 900 900 900 900

EXAMPLE 3 Granular laundry detergents for use in domestic appliances or handwashing of laundry at from 100 to 10,000 ppm, depending on appliance and/or water and/or conditions, are prepared in accordance with the invention: Ingredient (Range, % unless A B C D E F noted) LAS (0.5-25) 15 15 20 25 5 10 Alkyl Sulfate(0.5-15)-15 2-10 5 AlkylAlkoxy Sulfate (0-5)-3 5 5 2 Nonionic(0.5-10) 5 1 2 0. 5 1 0. 5 ----21Glucamide(0-5) QAS (0-2) 1 1 1. 8 0. 5 Phosphate Polymer, Sample 2 1 5 25 10 30 5 Zeolite system (0-20)-20---- Carbonate (0-30) 10 10 5 15-20 Silicate system (0-15) 5 1 3-2 10 Non-polymer type--3-2- polycarboxylate (0-5) Polymer-type polycarboxylate (0-1 5 - 9 4 - 9) Carbohydrate antiredeposition 0. 1 0. 2 1 0. 3 0. 2 agent (0-2) Primary Oxygen Bleach (0-20) 20 15 10 5 3 Hydrophilic Bleach Activator (0-5)-2--4 2 Hydrophobic Bleach Activator (0--2 1 - 5 - 8) Photobleach (0-1000 ppm)--10-5- Chelant System (0-2) 2 1 0. 5 2 1 0 Enzyme System (0-3) 3-3 3 3 1 Brightener(0-2) 0. 1 0. 1 0. 1 0. 2 0. 3 1 Soil Release Agent (0-3)-0. 1 1 2-0. 3 Additional low-level benefit agent (0-2) Perfume (0-3) 0. 01 0.1 - 3 2 1 Antifoam system (0-3) 0. 05 0.1 0.2 0.5 0.7 - Sulfate, stabilizers, process aids, 100 100 100 100 100 100 minors to % % % % % % Density in g/litre (range) 200-200-200-200-200-200- 900 900 900 900 900 900 EXAMPLE 4 Laundry Bar compositions are prepared according to the present invention. A B C D E F Tallow Soap 38.00 28.80 0.00 0. 00 0. 00 0.00 Coconut Soap 9. 50 7. 20 0. 00 0. 00 0. 00 0.00 Alkyl Glycerate Ether 0.00 0. 00 0. 00 0.00 Sulphonate Coco (C12-C14) Aikyl 0.00 0.00 15.05 15.05 0. 00 0. 00 Sulfate C12-C14 Amine Oxide 0.00 0.00 0. 00 2. 50- 0. 00 2.50- 4.00 4.50 LAS 2. 50 2.00 19.0%- 16.50 22% Coco Fatty Alcohol 0. 00 0.00 1. 5 0. 00 0. 00 0.00 Coconut 0. 00 0.00 1.00 0. 00 0. 00 0.00- Monethanolamide 0.00 Sodium Carbonate 0. 00- 0. 00- 0. 00- 0. 00- 0. 00- 0.00- 6.00 6.00 15.00 12.00 12.00 15.00 STPP 5. 00 5.00 10.00 15.00 20. 00 0.00 Zeolite A 0. 00 0.00 1.00 1. 00 1. 00 1.00 Carboxymethyl 0.5- 0. 5- 0. 40 0. 50 0. 00 0.50 Cellulose 1.5 1.5 Polymers 0. 00 0.00 0.64 0. 40 1. 20 1.20 DTPA 0. 60 0.60 0.90 0. 00 0. 80 0.80 Phosphate polymer, 1.00 5. 00 2. 00 3. 00 2. 00 20.00 Sample 1 Calcium Carbonate 0.00 21.5 25.00 Talc 0.00- 25. 00 0. 00 0. 00 0. 00- 0.00- 10.00 SodiumPerborate 0. 0- 0. 0 4. 50 0. 00- 4. 50 4.50 4.5 4.50 Amylase 0. 00 0. 00 0. 05 0. 00 0. 00 0.00 Cellulase 0. 00 0. 00 0. 00 0. 08 0. 00 0.02 Protease 0. 00- 0. 00 0. 10 0. 00- 0. 12 0.10 0.12 0.12 Brightener 0. 20 0. 20 0. 20 0. 20 0. 22 0.32 Photobleach 0. 005 0. 005 0. 005 0. 005 0.005 0.005 PEG 0. 00 0. 00 0. 00 0. 00 1. 00 1.00 SodiumBorate 0. 00 0. 00 0. 00 0. 00 1. 50 1.00 CaO 0. 00 0. 00 0. 00 1. 80 1. 80 1.80 SodiumSilicate 0. 00 0. 00 0. 00 3. 3 2. 70 2.70 SodiumSulfate 0. 0 0. 00 9. 00 0. 00 0. 00 0.00 MgS04 2. 00 1. 85 0. 00 0. 00 3. 00 0.00 Water 17. 00 17. 00 3. 00 2. 00- 4. 70 5. 0 3.00 Balance to 100. 00% balan balan balanc balanc balanc balance ce ce e e e

EXAMPLE 5 Several detergent compositions made in accordance with the invention and specifically for top-loading washing machines are exemplified below. The base granule is prepared by a conventional spray drying process in which the starting ingredients are formed into a slurry and passed though a spray drying tower having a countercurrent stream of hot air (200-300°C) resulting in the

formation of porous granules. The admixed agglomerates are formed from two feed streams of detergent ingredients which are continuously fed, at a rate of 1400 kg/hr, into a Lödige CB-30 mixer/densifier, one of which comprises a surfactant paste containing surfactant and water and the other stream containing starting dry detergent material containing sodium carbonate and insoluble inorganic builder such as magnesiosilicate or combinations thereof with zeolite.

The rotational speed of the shaft in the Lödige CB-30 mixer/densifier is about 1400. The contents from the Lödige CB-30 mixer/densifier are continuously fed into a Lödige KM-600 mixer/densifier for further build-up agglomeration. The resulting detergent agglomerates are then fed to a fluid bed dryer and to a fluid bed cooler before being admixed with the spray dried granules. The remaining adjunct detergent ingredients are sprayed on or dry added to the blend of agglomerates and granules. Alternately the magnesiosilicate can be dry-added, in whole or in part, to the composition.

A B C Base Granule Aluminosilicate 18.0 0 0 Sodium sulfate 10.0 8.0 19.0 STPP 0 0 17.0 Sodium polyacrylate polymer 3.0 3.0 2.0 PolyethyleneGlycol (MW=4000) 2.0 2.0 1.0 C12-13 linear alkylbenzene 6.0 6.0 7.0 sulfonate, Na C14-16 secondary alkyl sulfate, Na 3.0 3.0 3.0 C14-15 alkyl ethoxylated sulfate, Na 3.0 3.0 9.0 Sodium silicate 1.0 1.0 2.0 Brightener 246 0. 3 0.3 0.3 Sodium carbonate 7.0 7.0 25.7 DTPA 1 0.5 0.5 Phosphate polymer, Sample 1 1.0 2.0 3.0

AdmixedAaalomerates C14-15 alkyl sulfate, Na 5.0 5.0 C12-13 linear alkylbenzene 2.0 2.0 sulfonate, Na Sodium Carbonate 4.0 11.0 PolyethyleneGlycol (MW=4000) 1.0 1.0 Admix C12-15 alkyl ethoxylate (EO = 7) 2.0 2.0 0.5 Perfume 0.3 0.3 1.0 Polyvinylpyrrilidone 0.5 0.5 Polyvinylpyridine N-oxide 0.5 0.5 Polyvinylpyrrolidone-poiyvinylimidazole 0.5 0.5 Distearylamine & Cumene sulfonic acid 2.0 2.0 Soil Release Polymer 2 0.5 0.5 Lipolase Lipase (100.000 LU/I) 4 0.5 0.5 Termamyl amylase (60 KNU/g) 5 0.3 0.3 CAREZYME cellulase (1000 CEVU/g) 4 0.3 0.3- Protease (40mg/g) 5 0.5 0.5 0. 5 NOBS 3 5.0 5.0 Sodium Percarbonate 12.0 12.0 Polydimethylsiloxane 0.3 0. 3 Miscellaneous (water, etc.) balance balance balance Total 100 100 100 1 Diethylene Triamine Pentaacetic Acid 2Made according to U. S. Patent 5,415,807, issued May 16,1995 to Gosselink et al 3 Nonanoyloxybenzenesulfonate 4 Purchased from Novo Nordisk A/S 5 Purchased from Genencor 6 Purchased from Ciba-Geigy Aluminosilicate = 1-10 A Zeolite A