WO1999050382A1

WO1999050382A1 - Detergent compositions

Info

Publication number: WO1999050382A1
Application number: PCT/IB1999/000475
Authority: WO
Inventors: Robert Henry Rohrbaugh; Eugene Joseph Pancheri; Robert Ya-Lin Pan; Scott William Capeci; James Charles Theophile Roger Burckett-St. Laurent
Original assignee: The Procter & Gamble Company
Priority date: 1998-03-30
Filing date: 1999-03-22
Publication date: 1999-10-07

Abstract

Detergent compositions, especially laundry detergent granules, comprising certain siliceous builders, preferably certain magnesiosilicate builders.

Description

DETERGENT COMPOSITIONS

TECHNICAL FIELD

This invention relates to built detergent compositions, especially having granular or syndet bar form. The compositions contain particular siliceous builders, preferably magnesiosilicates, combined with valuable surfactants, and preferably, certain classes of polymers and/or bleaches, especially hydrophobically modified bleach activators and/or bleach catalysts. Other adjuncts, e.g., enzymes, can also be present.

BACKGROUND OF THE INVENTION

Fuller's earth and other minerals have been used from ancient times for textile washing. Clays, especially white montmorillonites (smectites, bentonites) and other types, such as hectorites, have more recently been used for simultaneous washing and softening of textiles. Soluble and insoluble silicates have been widely used in detergents as alkalis, crispening agents. Other insoluble minerals, including magnesium-containing, aluminium-free types, such as talc, have been used as fillers, for example in laundry bars. Synthetic aluminosilicate materials such as zeolites A, P, the so-called "maximum aluminum" zeolite P, zeolite X and combinations thereof are well-known in laundry detergents, both as builders and as absorbents for surfactants. Regrettably, none of such materials have been found to have anywhere near an ideal combination of low cost, ease of manufacture, high equilibrium binding of both Ca and Mg, rapid kinetics of binding for Ca and Mg, and ability to hold large amounts of surfactant. Moreover, some materials of these kinds, when added to laundry detergents, can interact adversely with laundry detergent adjuncts, e.g. bleaches, bleach catalysts, enzymes, brighteners and other additives, and/or produce unacceptable harshness and/or give other major problems, such as redeposition onto textiles. Another technical problem is the strong tendency for low-level adjuncts or differently charged additives such as cationic surfactants, catalysts or enzymes to adsorb onto the relatively large, anionically charged surface of insoluble inorganic builders. Accordingly, heavy research and experimentation are needed to integrate any new synthetic inorganic builder material with other detergent ingredients so as to benefit from its properties and at the same time avoid negating or reducing the desirable effect(s) of the adjuncts with which it is formulated. Such experimentation often results in failure.

BACKGROUND ART

WO 97/10179, Australian National University, published March 20, 1997, provides assertedly novel magnesiosilicate compounds for use in detergents and water softeners. Also provided are some simple detergent formulations using the magnesiosilicates.

EP 384070 describes certain types of zeolite P in detergent compositions with common additives.

More typical of known silicates used in detergents is a crystalline layered sodium silicate, SKS-6 (Na2Si2O5), which is used commercially. It has been developed by Hoechst AG and is described in US 4,664,839; 4,820,439; 4,950,310 and 5,308,596.

Numerous patents and texts describe detergent builders, both of silicate- containing and non-siliceous types.

All proportions herein are percentages by weight of the detergent composition unless otherwise noted. All references cited are incorporated by reference in their entirety. Proportions are by weight unless otherwise noted.

SUMMARY OF THE INVENTION

It has now been discovered that certain siliceous builders, preferably a very particular type of magnesiosilicates, can be advantageously combined with specifically identified detergent ingredients to provide superior laundry detergent compositions. The invention encompasses a detergent composition comprising: (a) from about 0.1% to about 99% of a particulate inorganic ion-exchanging siliceous builder, said siliceous builder being characterizable by X-ray diffraction, and said siliceous builder having a measurable improvement in the sum of Calcium binding and Magnesium binding as compared to Zeolite A; and (b) from about 0.1% to about 99% of at least one detersive adjunct selected from the group consisting of: (i) detersive surfactants having at least one branched, preferably mid-chain branched hydrophobe (see, for example, WO97/39088, WO97/39087, WO 97/39091) (ii) organic polymeric materials selected from polyacetal carboxylates, for example polymers and copolymers having polyglyoxylate structural units (see, for example, US 4,146,495; US 4,140,676; EP 803,521 A; such materials are available from Monsanto, Nippon Shokubai, BASF and others), hydrophobically modified polyacrylates (see, for example, EP 812,905 A2, EP 786,516 A2; such materials are available from Rohm & Haas, National Starch and others), terpolymers comprising acrylate or maleate (see, for example, US 4,647,396, US 4,698,174, EP 608,845; such materials are available from Rohm & Haas and others), polymeric soil release agents (see, for example, US 5,415,807, WO96/18715 A2, WO97/23542 Al and many other patents to Gosselink et al - such materials include end-capped polyester oligomers and are available from Hoechst / Clariant, though many non-end capped versions can also be used), polymeric dye transfer inhibitors (for example PVPNO, see for example EP-704523 Al or WO96/20996 Al or polymers of DEI 9621509 Al or WO96/37598 Al available from BASF or peroxidase, see US 5,605,832 A and other types illustrated hereinafter ), polyamines (see, for example WO97/00936 Al, WO97/23546 Al, WO97/28207 Al, WO97/42285 Al and WO 97/35950 Al), polyimine derivatives such as ethoxylated/propoxylated polyalkyleneamine polymers (see for example US 5,565,145) or functionalized backbone polyamines (see WO97/42286 Al) polymeric rheology modifiers (see, for example modified polysaccharides, known "deflocculating polymers" - see for example US 5,147,576, and mixtures thereof); (iii) oxygen bleach promoting materials selected from hydrophobic bleach activators, for example NOBS and its analogs and homologs; organic bleach boosters, for example omega-(3,4-dihydroisoquinolinium alkane sulfonates as in US 5,576,282; transition- metal bleach catalysts (for example those more specifically illustrated hereinafter - see also WO 97/00937, WO 96/06155, EP 718398 A, US 5,720,897 and WO 97/48787); photobleaches and mixtures thereof (such as Si-phthalocyanines in WO 97/05202 though sulfonated zinc phthalocyanines can also desirably be used); (iv) fabric care promoting agents other than said organic polymeric materials (for example complexes or ion pairs of anionic and cationic surfactants, softening clays such as smectites and hectorites, and organosilicon compounds); and (v) mixtures of (i) - (iv).

The compositions suitably comprise from about 0.1% to about 80%, preferably from about 0.5% to about 30%, by weight, of the particularly defined siliceous builder, preferably magnesiosilicate in accordance with the synthetic magnesiosilicate materials of WO 97/10179, herein incorporated by reference in its entirety. More generally, any equivalent material may be used provided that it has a measurable improvement in the sum of Calcium binding and Magnesium binding as compared to Zeolite A; highly preferred siliceous builders herein have a measurable improvement in the sum of Calcium binding and Magnesium binding as compared to Zeolite A, delta-layer silicates (e.g., SKS-6 from Hoechst Clariant) and mixtures thereof.

A highly preferred illustrative magnesiosilicate compound for use as the essential siliceous builder component herein is one having a calcium binding capacity (CBC) of at least 10 mg CaO per gram at room temperature, a magnesium binding capacity (MBC) of at least 10 mg MgO per gram at room temperature, and a calcium binding rate (CBR) of no more than 300 seconds at room temperature, being the time taken to remove half of the Ca2+ from a ~ 100 ppm Ca2+ solution at a loading of 3g per litre, and having either a stuffed silica polymorph-related structure or a layered structure with a characteristic broad X-ray powder diffraction peak occurring at a d-spacing of between 11 and 17 A.

These stuffed silica polymorph-related magnesiosilicates, particularly those that are imperfectly crystallized and possess substantial disordering of the framework cations, and magnesiosilicates having a layered structure with a characteristic broad X-ray powder diffraction peak occurring al a d-spacing of between 11 and 17 A, preferably between 12 and 16 A, can have a significant calcium binding capacity (CBC), magnesium binding capacity (MBC) and a relatively high calcium binding rate (CBR) in aqueous solution.

For the purposes of the present invention, CBC is expressed in units of mg CaO per gram of anhydrous magnesiosilicate and MBC is expressed in units of mg MgO per gram of anhydrous magnesiosilicate, both at room temperature. Advantageously, the selected magnesiosilicates may have a CBC of at least 20, preferably at least 50 and in many embodiments at least 100. Advantageously, the magnesiosilicates may have an MBC of at least 15, preferably at least 40 and in many embodiments at least 90. When well-prepared, these compounds may have a CBC of at least 150 and/or an MBC of at least 140. For the purposes of the present invention, CBR is expressed in terms of the time taken to remove half of the Ca²⁺ from a -100 ppm Ca²⁺ solution at room temperature at a loading of 3 g per litre. Advantageously, compounds of the invention may have a CBR of no more than 200 seconds, preferably no more than 100 seconds, more preferably no more than 50 seconds, even more preferably no more than 20 seconds, and most preferably no more than 10 seconds.

The preferred magnesiosilicates advantageously also have an oil absorption (OA) of at least 50g oil per lOOg of anhydrous material, preferably at least 70g oil, more preferably at least lOOg oil per lOOg of anhydrous material. Methods for determining CBC, MBC, CBR and OA are described hereinafter.

The magnesiosilicates selected for use herein may be characterized in terms of their composition, which may, in anhydrous form of the compounds, be given by M_aMg_bAl_cSi_Hb+c)O_d, where M = alkali, optionally partially substituted by H or NH₄, where 0.0 < a < 2.0, 0.0 < b < 0.7, 0.0 Φ c Φ 0.3, and 1.15 < d < 3.0; where c < b, where there may be partial substitution of the atoms (Mg + Al + Si) by one or more other elements T selected from the group B, Be, Zn, Ga, Fe, Ge, As and P such that T/(Mg + Al + Si) < 0.1 and Mg is > 0; where there may be partial substitution of the interstitial atoms M by one or more other elements A selected from the group alkaline earth, transition metal and rare earth elements such that A/M < 0.2; and where impurity minerals or compounds which are not integrated into the structure are not accounted for in the composition. Such impurity minerals or compounds may include, for example, TiO2 - anatase and SiO2 - quartz.

Preferably, 0.4 < a < 1.4, 0.2 < b < 0.6, 0.0 Φ c Φ 0.2, and 1.5 < d < 2.5; and T/(Mg + Al + Si ) < 0.05. More preferably 0.6 < a <1.3, 0.35 < b <0.6, 0.0 Φ c Φ 0.1, and 1.65 < d < 2.25, and T(Mg + Al + Si) < 0.02. Advantageously, Mg/Ca Φ 100 and Si/(Mg+Ca) < 1.4.

As is clear from the composition above, the interstitial cations may be K⁺ or Na⁺, as in the compounds Na₂MgSiO₄, Na₄Mg₂Si₃O₁₀, K₂MgSiO₄, and KMg_{0 5}Si, ₅O₄, or it may be another alkali cation, such as Li⁺, Rb⁺ or Cs⁺. The alkali cations may be partially substituted by one or more other monovalent cations, such as NH₄ ⁺ or H⁺. These materials may also be prepared such that a small proportion of the monovalent interstitial cations is substituted by polyvalent cations, such as alkaline earth, transition metal and rare earth cations. The interstitial sites may be occupied by a mixture of any two or more of the aforementioned cations. However, alkali metal cations are the preferred cations, in particular Na^* or K⁺ .

It is believed that unreacted reagent anions which may be used in the synthesis of magnesiosilicate compounds in accordance with the invention, for example bicarbonate, carbonate, carboxylate, nitrate and hydroxide, are not integrated into the structures, and it is for this reason they are not included in the empirical composition above.

Preferred compositions herein are powders, tablets or granules, though other forms such as pouches, nonaqueous liquids and the like are also envisaged.

The present invention has numerous advantages, for example excellent cleaning and/or bleaching and at the same a low tendency to damage fabrics.

DETAILED DESCRIPTION OF THE INVENTION

The present detergent compositions require a particular siliceous builder component as defined in the summary. Preferred in this role is a particular magnesiosilicate component to be present as substantially the entire builder or as at least one component of a builder system. Suitable levels are from about 0.1% to about 80%, preferably from about 0.5% to about 30%, by weight, of the particularly defined magnesiosilicate when it is used alone. A "builder system" as defined herein comprises one or more detergent builders, (in the formula accounting, any organic polymeric additives, which are sometimes used to complement the builder, are counted separately from the builder system). Suitable levels of a builder system in the present detergent compositions are from about 0.1% to about 85%, preferably from about 1% to about 40%, by weight. All percentages and proportions are for the complete detergent composition, unless otherwise noted. Builders other than the magnesiosilicate are conventional and can. for example, be selected from water-soluble organic builders such as 2,2'-oxydisuccinate sodium salts, citric acid sodium salts, carboxymethyloxysuccinate sodium salts, nitrilotriacetic acid sodium salts and the like; water-insoluble organic builders such as zeolites A, P, X, or any of their modifications, water-soluble inorganic builders such as various cellulosic polymers, and water-soluble inorganic builders such as sodium carbonate sodium phosphates, sodium tripolyphosphates and the like, encompassing a wide range of calcium and/or magnesium binding capability and rate. The builder system can be complemented by one or more materials known as chelants, (chelants like, organic polymers, being added up separately in the formula accounting and being materials which generally have the capability to strongly bind transition metal ions or colloidal transition metal precipitates in aqueous alkaline media). Chelants suitable for use herein include ethylenediamine disuccinate sodium salts, EDTA, HEDP, DTPA and mixtures thereof; typical levels are in the range of from about 1 ppm to about 2% by weight of the detergent composition.

Magnesiosilicate Component

The essential siliceous builder, preferably magnesiosilicates, useful herein can include those having a stuffed silica polymorph-related structure or, less preferably, can include those having a layer structure subject to the defining characteristics given hereinafter. To be clear, no such structure can be mistaken for the common "layer silicates" such as delta- type layer silicate, based on the X-ray diffraction pattern.

Magnesiosilicate compounds having a stuffed silica polymorph-related structure can be characterized in terms of their structure and composition.

The structures of the various magnesiosilicate compounds having a stuffed silica polymorph-related structure are characterized most definitively by X-ray powder diffraction. When well -prepared, these compounds give X-ray powder diffraction profiles which display diffraction peaks characteristic of the stuffed silica polymorphs. Characteristic diffraction profiles for the various magnesiosilicates having a stuffed silica polymorph related structure can be seen in Figures 3 to 5 of WO 97/10179, incorporated by reference, for compounds a-k of Examples 1 to 11 of WO 97/10179 respectively. The corresponding tabulated information is given in Table 1 of WO 97/10179.

Cristobalite-related sodium magnesiosilicates are characterized by the presence of dominant X-ray powder diffraction peaks or groups of peaks occurring simultaneously at a d-spacing of 4.30 ± 0.15 A and at a d-spacing of 2.64 + 0.22 A. These peaks or groups of peaks are related to the 111 and 220 X-ray powder diffraction peaks, respectively, of high cristobalite. 8

Cristobalite-related potassium magnesiosilicates are characterized by the presence of a dominant X-ray powder diffraction peak or group of peaks occurring at a d-spacing of 2.73 ± 0.15 A and a weaker peak or group of peaks at a d-spacing of 4 44 ± 0.10 A. These peaks or groups of peaks are related to the 220 and 111 X-ray powder diffraction peaks, respectively, of high cristobalite.

Tridymite-related potassium magnesiosilicates are characterized by the presence of a dominant X-ray powder diffraction peak occurring at a d-spacing of 3. 11+ 0.20 A. This peak is related so the 202 X-ray powder diffraction peaks of high tridymite.

The XRD profiles observed for magnesiosilicates having a stuffed silica polymorph related structure are dependent on the choice of starting reagents and reaction conditions. They are also sometimes complicated by the presence of unreacted starting materials, reaction byproducts such as MgO or Na₂SiO₃ or impurity minerals, such as quartz, calcite, dolomite and feldspar, when naturally-occurring components are used.

Both these magnesiosilicate compounds and the magnesiosilicate compounds in accordance with the invention and having a layered structure described below can be further characterized by their composition.

In the broadest embodiment the subject magnesiosilicates have a composition range in anhydrous form given by M_aMg_bAl_cSi_Hb+c)O_d, (M = alkali, optionally partially substituted by H or NH₄), where 0.0 < a <2.0, 0.0 < b < 0.7, 0.0 Φ c Φ 0.3, and 1.15 < d < 3.0. Also c<b.

This general formula does not account for partial substitution of the tetrahedral atoms (Mg + A1+ Si) by other elements T (where T - B, Be, Zn, Ga, Fe, Ge, As or P) which can occupy such positions in a tetrahedral framework structure. In the broadest embodiment T/(Mg + Al + Si) < 0.1 and Mg > 0 . Neither does this general formula account for partial substitution of the interstitial atoms M by other elements A (where A = alkaline earth, transition metal or rare earth elements) which can occupy such interstitial sites in the structures. In the broadest embodiment A M < 0.2. Neither does the general formula account for impurity minerals or compounds which are not integrated into the structure, e g TiO2-anatase, SiO2-quartz. In a more preferred embodiment, the subject magnesiosilicates have a composition range in anhydrous form given by M_aMg_bAl_cSi,._(b+c)O_d, where 0.4 < a < 1.4, 0.2 < b < 0 6, 0.0 Φ c Φ 0.2, 1.5 < d < 2.5, and c < b. In this more preferred embodiment T/(Mg + Al + Si) < 0 05, A/M < 0.2 and Mg > 0. Again, the general formula does not account for impurity minerals or compounds which are not integrated into the structure, e.g. TiO,-anatase, SiO₂-quartz.

In the most preferred embodiment, the subject magnesiosilicates have a composition range in anhydrous form given by M_aMg_bAl_cSi,._(b+c)O_d, where 0.6 < a < 1.3, 0.35 < b < 0 6, 0.0 Φ c Φ 0.1, 1.65 < d < 2.25, and c < b. In this most preferred embodiment, T/(Mg + Al + Si) < 0 02, A M < 0.2 and Mg > 0. Again, the general formula does not account for impurity minerals or compounds which are not integrated into the structure, e.g. TiO₂-anatase, SiO₂-quartz.

It is believed that unreacted reagent anions which may be used in the synthesis of magnesiosilicate cation exchange compounds, for example, carbonate, bicarbonate, nitrate, are also not integrated into the structures, and it is for this reason that they are not included in the empirical composition.

Composition analyses and derived formulae for magnesiosilicate compounds having silica polymorph-related structures and prepared according to Examples 1-11 of WO 97/10179, incorporated by reference, can be found in Table 2 of said patent publication.

Magnesiosilicates useful herein and having the stuffed silica polymorph-related structure can be prepared according to any of Examples 1-11 of WO 97/10179. Magnesiosilicates useful herein and having the layered structure can be prepared according to any of Examples 12-14 of WO 97/10179.

For the purposes of the present invention two different methods can be used to determine calcium binding capacity (CBC) Calcium binding capacity is measured as milligrams of CaO taken up per gram of the magnesiosilicate compound at room temperature.

CBC: Method A. 10

To characterize the magnesiosilicate compounds in accordance with their proposed utility as water softeners or detergent builders, a method similar to that described in GB 1 473 201 (Henkel) and EP 0 384 070 A2 (Unilever) can be used. In this test, 0.1 g of test compound is dispersed in 100 ml of an aqueous solution containing 202 ppm of Ca²⁺, and where necessary, adjusted to a pH of 10 with dilute NaOH. The suspension is stirred at 20°C for 15 minutes, then centrifuged to remove the solid. The aqueous solution is then tested for residual Ca²⁺ using a calcium-selective electrode.

Various examples of the subject magnesiosilicate compounds and, for comparison, other commercially produced detergent builders can be tested in this manner. The results of such are given in Table 3 of WO 97/10179. All of the magnesiosilicate compounds of Examples 1 to 14 of WO 97/10179 and found useful herein have a CBC of greater than 10 mg CaO at room temperature.

CBC: Method B

Calcium binding capacities can also be compared in the presence of background 0.01 M Na⁺ in a manner similar to the method described in EP 0 384 070 A2 (Unilever) for the purpose of more closely simulating a wash liquor environment. In this test 0.1 g of compound is dispersed in 100 ml of an 0.01 M NaCl solution containing 202 ppm of Ca²⁺, and where necessary, adjusted to a pH of 10 with dilute NaOH. The suspension is stirred at 20°C for 15 minutes then centrifuged to remove the solid. The aqueous solution is then tested for residual Ca2 using a calcium-selective electrode.

Various examples of the subject magnesiosilicate compounds and, for comparison, other commercially produced detergent builders can be tested in this manner. Results are given in Table 4 of WO 97/10179, incorporated by reference.

Magnesium Binding Capacity (MBC)

Magnesium binding capacity is measured as milligrams of MgO taken up per gram of the magnesiosilicate compound at room temperature.

MBC: Method C.

To characterize the magnesiosilicate compounds further in accordance with their proposed utility as water softeners or detergent builders, a method C similar to Method A described above is used to measure magnesium binding capacity (MBC). In this test 0.1 11

g of test compound is dispersed in 100 ml of an aqueous solution containing 200 ppm of Mg²⁺ and, where necessary, adjusted to a pH of 10 with dilute NaOH. The suspension is stirred at 20°C for 15 minutes, then centrifuged to remove the solid. The aqueous solution is then tested for residual Mg²⁺ using atomic absorption spectroscopy.

Various examples of the subject magnesiosilicate compounds and, for comparison, other commercially produced detergent builders can be tested in this way. The results of such tests are given in Table 5 of WO 97/10179, incorporated by reference. All of the magnesiosilicate compounds of Examples 1 to 14 of WO 97/10179 and useful herein have an MCB of greater than 10 mg MgO at room temperature.

Calcium Binding Rate (CBR)

Calcium binding rate is measured as the time taken to remove half of the Ca^2* from approximately a 100 ppm Ca²⁺ solution at room temperature at a loading of 3 g of the magnesiosilicate compound per litre.

CBR: Method D

The subject magnesiosilicate compounds are further characterized in terms of their calcium binding rate (CBR) in accordance with their utility as water softeners or detergent builders. To quantify the rate at which Ca²⁺ is removed from solution, using method D, 0 15 g of test compound is dispersed in about 1 ml of water which is then injected into 50 ml of stirred solution containing 0.01 M NaCl, 0.1 M KC1 and -100 ppm of Ca²⁺ concentration of the stirred solution is measured as a function of time using a calcium selective electrode.

Various examples of the subject magnesiosilicate compounds and, for comparison, other commercially produced detergent builders can be tested in this way. The results of such tests are given in Table 6 of WO97/10179, incorporated by reference. All of the magnesiosilicate compounds of Examples 1 to 13 of WO97/10179 have a CBR of less than 300 seconds at room temperature.

Oil Absorption (OA)

Oil absorption herein can be determined by the ASTM spatula rub-out method D281 as also used in EP 0 565 364 Al. This test is based on the principle of mixing linseed oil with the particulate material by rubbing with a spatula on a smooth surface 12

until a stiff putty-like paste is formed which will not break or separate^' when it is cut with a spatula. The Oil Absorption (OA) is expressed in grams of oil per 100 g of dry material.

Various examples of the subject magnesiosilicate compounds and, for comparison, other commercially produced detergent builders can be tested in this way. The results of such tests are given in Table 7 of WO97/10179, incorporated by reference. Useful OA's for the subject magnesiosilicates include those in the range 60-154.

Detergent compositions

Detergent compositions of the invention comprising the siliceous builder, preferably the herein-identified magnesiosilicates, may suitably comprise, in more detail, the following ingredients: (a) one or more detersive surfactants, (b) a builder system comprising a magnesiosilicate as defined above, 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 said magnesiosilicate, (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.

Highly preferred detergent compositions herein comprise, in addition to (a) the essential siliceous builder, (b) from about 0.1 % to about 99% of at least one detersive adjunct selected from the group consisting of: (i) detersive surfactants having at least one branched, preferably mid-chain branched hydrophobe; (ii) organic polymeric materials selected from polyacetal carboxylates, hydrophobically modified polyacrylates, terpolymers comprising acrylate or maleate, polymeric soil release agents, polymeric dye 13

transfer inhibitors, polyamines, polyimines, polymeric rheology modifiers, and mixtures thereof; (iii) oxygen bleach promoting materials selected from hydrophobic bleach activators; organic bleach boosters; transition-metal bleach catalysts; photobleaches and mixtures thereof; (iv) fabric care promoting agents other than said organic polymeric materials; and (v) mixtures of (i) - (iv). Sources and examples of such materials have been given in the summary hereinabove.

Detergent surfactants

The detergent compositions of the invention will contain, as essential ingredients, 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 II, 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 alcohols ethoxylated with from 1 to 20 moles of ethylene oxide per mole of alcohol, and more especially C9- C15 primary aliphatic alcohols ethoxylated with an average of from 1 to 10 moles of ethylene oxide per mole of alcohol.

Also of interest are non-ethoxylated 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 14

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 WO97/39087 Al published 10/23/97 and mid- chain branched primary alkyl alkoxylated sulphate(s) of WO97/39088 Al published 10/23/97. The magnesiosilicates can be incorporated into bleaching detergent compositions comprising bleaching agent, mid-chain branched surfactant and adjunct ingredients as described in WO97/39090 Al, published 10/23/97. Also the longer alkyl chain, mid-chain branched surfactant compounds, especially the mid-chain branched alkyl sulfates as described in WO97/39091 Al 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 WO97/38956 Al 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 WO97/38972 Al 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. 15

The detergency builder system

As noted, the detergent compositions of the invention contain as an essential component a magnesiosilicate 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 magnesiosilicate 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 poly carboxy late 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.

Preferred supplementary builders for use in conjunction with the magnesiosilicate 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%. 16

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 BRITESIL®, e.g., BRITESIL H2O; 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 δ- Na₂SiO₅ 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 NaMSi_xO_2x+1.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-1 1, as the α, β and γ 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: xM₂O-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: [M_z(AlO2)_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, Krummel, 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[(AlO₂)₁₂(SiO₂)₁₂].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. 17

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 minerals 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.

18

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 particularly useful transition-metal bleach catalyst is [Mn(Bcyclam)C12]:

N-

Ck .-NrV N- ^N

"Bcyclam" (5,12-dimethyl-l,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, distilled 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)2Cl2 (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 19

overnight at room temperature. The reaction solution is filtered with a 0.2μ filter. The filtrate is evaporated. 1.35 g. of product is collected, 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-C16 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:

O O O O

II II II II

R1-C— N— R2-C-OOH R1— N— C— R2-C-OOH

I I

R5 R5 or mixtures thereof wherein Rl is alkyl, aryl, or alkaryl containing from about 1 to about 14 carbon atoms, R2 is alkylene, arylene 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 Rl 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 20

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, upases, 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 influenced 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. 21

Polymeric Soil Release Agent

Polymeric soil release agents, hereinafter "SRA" or "SRP's", can be used herein. Levels include from 0.01% to 10.0%, typically from 0.1% to 5%, preferably from 0.2% to 3.0%. Preferred SRA's can have hydrophilic segments and hydrophobic segments and can include charged, e.g., anionic or even cationic (see U.S. 4,956,447), as well as noncharged monomer units. Structures may be linear, branched or even star-shaped. SRA's may include capping moieties. Preferred SRA's include oligomeric terephthalate esters, e.g., made by transesterification/oligomerization with a suitable catalyst. Such esters may incorporate additional monomers binding through one, two, three, four or more positions, generally without heavy crosslinking. Suitable SRA's can have an oligomeric ester backbone of terephthaloyl and oxyalkyleneoxy repeat units and allyl- derived sulfonated terminal moieties covalently attached to the backbone as described in U.S. 4,968,451; nonionic end-capped 1 ,2-propylene/polyoxyethylene terephthalate polyesters as in U.S. 4,711,730; partly- and fully- anionic-end-capped oligomeric esters of U.S. 4,721,580; the nonionic-capped block polyester oligomeric compounds of U.S. 4,702,857; and the anionic, especially sulfoaroyl, end-capped terephthalate esters of U.S. 4,877,896, the latter being typical of SRA's useful in both laundry and fabric conditioning products, an example being an ester composition made from m- sulfobenzoic acid monosodium salt, PG and DMT optionally but preferably further comprising added PEG, e.g., PEG 3400.

SRA's also include those with segments of ethylene terephthalate or propylene terephthalate with ethylene oxide or propylene oxide, see U.S. 3,959,230 and U.S. 3,893,929; cellulosic derivatives such as the hydroxyether cellulosic polymers available as METHOCEL from Dow; and the C1-C4 alkylcelluloses and C4 hydroxyalkyl celluloses; see U.S. 4,000,093. Suitable SRA's characterized by poly(vinyl ester) hydrophobe segments include graft copolymers of poly(vinyl ester), e.g., Cj-Cg vinyl esters, preferably poly(vinyl acetate), grafted onto polyalkylene oxide backbones. See European Patent Application 0 219 048, published April 22, 1987 by Kud, et al. Commercially available SRA's include SOKALAN SRA's such as SOKALAN HP-22, available from BASF, Germany. Other SRA's are polyesters with repeat units containing 22

10-15% by weight of ethylene terephthalate together with 90-80% by weight of polyoxyethylene terephthalate, derived from a polyoxyethylene glycol of average molecular weight 300-5,000. Commercial examples include ZELCON 5126 from duPont and MILEASE T from ICI.

Another preferred SRA is an oligomer having empirical formula (CAP)2(EG/PG)5(T)5(SIP)1 which comprises terephthaloyl (T), sulfoisophthaloyl (SIP), oxyethyleneoxy and oxy-l,2-propylene (EG/PG) units and which is preferably terminated with end-caps (CAP), preferably modified isethionates, as taught in U.S. 5,415,807.

Yet another group of preferred SRA's are oligomeric esters of empirical formula: {(CAP)x(EG/PG)y'(DEG)y"(PEG)y'"(T)z(SIP)z'(SEG)q(B)m} Preferred SEG and CAP monomers for these esters include Na-2-(2-,3- dihydroxypropoxy)ethanesulfonate ("SEG"), Na-2-{2-(2-hydroxyethoxy) ethoxy} ethanesulfonate ("SE3") and its homologues and mixtures thereof and the products of ethoxylating and sulfonating allyl alcohol. Preferred SRA esters in this class include the product of transesterifying and oligomerizing sodium 2-{2-(2- hydroxyethoxy)ethoxy}ethanesulfonate and/or sodium 2-[2-{2-(2-hydroxyethoxy)- ethoxy}ethoxy]ethanesulfonate, DMT, sodium 2-(2,3-dihydroxypropoxy) ethane sulfonate, EG, and PG using an appropriate Ti(IV) catalyst and can be designated as (CAP)2(T)5(EG/PG)1.4(SEG)2.5(B)0.13 wherein CAP is (Na+ -O3S[CH2CH2O]3.5)- and B is a unit from glycerin and the mole ratio EG/PG is about 1.7:1 as measured by conventional gas chromatography after complete hydrolysis.

Additional classes of SRA's include (I) nonionic terephthalates using diisocyanate coupling agents to link up polymeric ester structures, see U.S. 4,201,824 and U.S. 4,240,918; (II) SRA's with carboxylate terminal groups made by adding trimellitic anhydride to known SRA's to convert terminal hydroxyl groups to trimellitate esters. See also U.S. 4,525,524; (III) anionic terephthalate-based SRA's of the urethane-linked variety, see U.S. 4,201,824; (IV) poly(vinyl caprolactam) and related co-polymers with monomers such as vinyl pyrrolidone and/or dimethylaminoethyl methacrylate, including both nonionic and cationic polymers, see U.S. 4,579,681; (V) graft copolymers, in 23

addition to the SOKALAN types from BASF made, by grafting acrylic monomers on to sulfonated polyesters; these SRA's assertedly have soil release and anti-redeposition activity similar to known cellulose ethers: see EP 279,134 A, 1988; (VI) grafts of vinyl monomers such as acrylic acid and vinyl acetate on to proteins such as caseins, see EP 457,205 A, 1991 ; (VII) polyester-polyamide SRA's prepared by condensing adipic acid, caprolactam, and polyethylene glycol, especially for treating polyamide fabrics, see DE 2,335,044 1974. Other useful SRA's are described in U.S. 4,240,918, 4,787,989, 4,525,524 and 4,877,896.

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 Application 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. 4,891,160, 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

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. Such agents include polymeric polycarboxylates and polyethylene glycols. Polymeric dispersing agents are believed to enhance detergent 24

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- 25

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[l ,2-d]triazoles; 4,4'-bis-(l ,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; l,2-bis(benzimidazol-2-yl)ethylene; 1,3-diphenyl-pyrazolines; 2,5-bis(benzoxazol-2-yl)thiophene; 2-styryl-naptho[l,2-d]oxazole; and 2-(stilben-4-yl)- 2H-naphtho[l,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 26

weight of the composition, preferably from about 0.01% to about 5%, and more preferably from about 0.05% to about 2%.

Chelating 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. 27

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, fillers, especially for bar compositions, etc. If desired, magnesium and/or calcium salts such as MgCl₂, MgSO₄, CaCl₂, 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. 28

"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.

Laundry washing 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 29

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 001 1968. 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.

30

Abbreviations used in Examples

LAS Sodium Cn_i2 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 Cj_x-Ciy 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 l2*- i4 (coco) alkyl N-methyl glucamide or l6" i8 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(C2H₄OH) X^" with R₂ = C_U - C_M and X^" = d^"

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 31

Magnesiosilicate Material of any of Examples 1-14, WO 97/10179

Zeolite system: one or more of :- Zeolite A Hydrated sodium aluminosilicate of formula

Nai2(A102 iθ2)l2-27H2θ 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 Al) Silicate system 2r or 3r sodium silicate; crystalline layered silicate of formula δ

- Na2Si2θ5 -(Hoechst/Clariant) Amorphous sodium silicate

(SiO₂:Na₂O = 2.0:1); _mi_xtUres thereof

(hydration of any zeolite may vary) Phosphates: - one or more of STPP Anhydrous sodium tripolyphosphate

TSPP Tetrasodium pyrophosphate non-polymer type polycarboxylate: one or more of :- Citrate Anhydrous citric acid; tri-sodium citrate dihydrate of activity

86.4% with a particle size distribution between 425 μm and

850μm; mixtures thereof

TMS/TDS Tartrate Monosuccinate / Tartrate Disuccinate, Sodium Salts ODS 2,2'-oxydisuccinate, Sodium Salts 32

CMOS Carboxymethyloxysuccinate, Sodium Salts

NTA Nitrilotriacetic Acid, Sodium Salts Carbonate Anhydrous sodium or potassium carbonate, e.g., with particle size between 200μm and 900μm for admix; or lower, e.g., below lOOμm, if to be further agglomerated. polymer-type any polycarboxylate of m.w. above about 1,000, especially polycarboxylate sodium salt of copolymer of 1 :4 maleic/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 4,146,495; US 4,140,676;

EP 803,521 A)

Carbohydrate Sodium carboxymethyl cellulose; methyl cellulose ether with a antiredeposition agent degree of polymerization of 650 available from 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 3 AU/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 1 OOKLU/g sold by NOVO

Industries A/S under the tradename Lipolase 33

Endolase Endoglucanase enzyme of activity 3000 CEVU/g sold by

NOVO Industries A/S

Primary Oxygen Sodium perborate tetrahydrate of nominal formula Bleach NaBO2.3H2O.H2O2 (abbrev. PB4); anhydrous sodium perborate bleach of nominal formula NaBθ2-H2θ2 (abbrev.

PB1); sodium percarbonate of nominal formula

2Na2Cθ3-3H2θ2 (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 the Activator sodium salt; NAC-OBS, i.e., (6-nonamidocaproyl) oxybenzene sulfonate; mixtures; or similar

Hydrophobic e.g., EP 778342 Al preformed peroxyacid Organic Bleach e.g., omega-(3,4-dihydroisoquinolinium alkane sulfonate(s) of Booster U.S. 5,576,282

Transition-metal e.g., as described in WO 97/00937, WO 96/06155, EP 718,398 Bleach Catalyst 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. 34

HEDP 1,1-hydroxy ethane diphosphonic acid Brightener Disodium 4,4'-bis(2-sulphostyryl)biphenyl; Disodium 4,4'- bis(4-anilino-6-morpholino-l .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 35

between 400μm and 1200μm 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

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 noted) A B c D E F

LAS (0-35) 4 - 10 20 30 35

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

Magnesiosilicate (0.1-40) 1 5 25 10 30 5

Zeolite system (0-30) - 20 - - - -

Carbonate (0-30) 10 10 5 15 - 20

Phosphates (0-30) - - - - - 20

Silicate system (0-20) 5 1 3 - 2 10

Non-polymer type polycarboxylate (0-20) - - 5 - 5 -

36

Polymer-type polycarboxylate (0-20) 1 5 - 10 4 -

Carbohydrate antiredeposition agent (0-10) 0.1 0.2 5 0.3 0.2 -

Primary Oxygen Bleach (0-20) 20 15 10 5 3 -

Hydrophilic Bleach Activator (0-10) - 2 - - 4 2

Hydrophobic Bleach Activator (0-10) - 2 1 - 5 -

Organic Bleach Booster (0-5) - - - 2 - -

Transition-metal bleach catalyst (0 - 10.000 ppm) 10 100 1000 - 50 10000

Photobleach (0-1000 ppm) - - 10 - 5 -

Chelant System (0-3) 2 1 0.5 3 1 0

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 (0-5) - - 1 - 1 -

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, minors to 100% 100% 100% 100% 100% 100%

Density in g/litre (range) 200-900 200-900 200-900 200-900 200-900 200-900

Example 2

Ingredient (Range, % unless noted) A B c D E F

LAS (0.5 - 25) 15 15 20 25 5 10

Alkyl Sulfate (0.5-15) - 15 2 - 10 5

Alkyl Alkoxy Sulfate (0-5) - - 3 5 5 2

Nonionic (0.5-10) 5 1 2 0.5 1 0.5

Glucamide (0-5) - - - - 2 1

QAS (0-2) 1 1 - 1.8 - 0.5

Magnesiosilicate (1-40) 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

37

Non-polymer type polycarboxylate (0-5) - - 3 - 2 -

Polymer-type polycarboxylate (0-9) 1 5 - 9 4 -

Carbohydrate antiredeposition agent (0-2) 0.1 0.2 1 0.3 0.2 -

Primary Oxygen Bleach (0-20) 20 15 10 5 3 -

Hydrophilic Bleach Activator (0-5) - 2 - - 4 2

Hydrophobic Bleach Activator (0-8) - 2 1 - 5 -

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) - - 1 - 1 -

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, minors to 100% 100% 100% 100% 100% 100%

Density in g/litre (range) 200-900 200-900 200-900 200-900 200-900 200-900

Example 3

Laundry Bar compositions are prepared according to the present invention.

I II III IV V VI

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 4.00 0.00 0.00 0.00 0.00 Sulphonate

Coco (C12-C 14) Alkyl 0.00 0.00 15.05 15.05 0.00 0.00 Sulfate

C12-C14 Amine Oxide 0.00 0.00 0.00 2.50-4.00 0.00 2.50-4.50

LAS 2.50 2.50 6.45 15.00- 22.00 19.0%-22% 16.50

Coco Fatty Alcohol 0.00 0.00 1.5 0.00 0.00 0.00

Coconut Monethanolamide 0.00 0.00 1.00 0.00 0.00 0.00-0.00

Sodium Carbonate 0.00- 0.00- 0.00- 0.00- 0.00- 0.00-15.00 6.00 6.00 15.00 12.00 12.00

38

STPP 5.00 5.00 0.00 0.00 0.00 0.00

Zeolite A 0.00 0.00 1.00 1.00 1.00 1.00

Carboxymethyl Cellulose 0.5-1.5 0.5-1.5 0.40 0.50 0.00 0.50

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

Magnesiosilicate (0.1-40) 1.00 5.00 18.00 18.00 20.00 20.00

Calcium Carbonate 0.00 0.00 0.00- 0.00- 0.00 0.00 21.5 25.00

Talc 0.00- 25.00 0.00 0.00 0.00- 0.00-10.00 25.00 10.00

Sodium Perborate 0.0-4.5 0.0 4.50 0.00-4.50 4.50 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 0.12 0.10 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

Sodium Borate 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

Sodium Silicate 0.00 0.00 0.00 3.3 2.70 2.70

Sodium Sulfate 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 2.00-3.00 4.70 5.0

Balance to 100.00% balance balance balance balance balance balance

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/1. 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/1"). Thus spray-dried granules can be densified by loading a liquid, 39

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 "Lδdige CB 30" or "Lδdige 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 shaft/blade assembly is rotated at speeds in the range of 100-2500 rpm to provide thorough mixing/densification. See U.S. 5,149,455 and 5,565,422. 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 "Lδdige KM" (Series 300 or 600) or "Lόdige 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. Lδdige KM) can be used alone or sequentially with the aforementioned high speed mixer/densifier (e.g. Lόdige 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 40

paste and an anhydrous material into a high speed mixer/densifier (e.g. Lόdige CB) followed by a moderate speed mixer/densifier (e.g. Lδdige 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. 5,565,137.

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/1). 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 Lδdige 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. Lόdige 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 41

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 4-6

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 Lόdige 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 Lόdige CB-30 mixer/densifier is about 1400. The contents from the Lόdige CB-30 mixer/densifier are continuously fed into a Lόdige 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 magnseiosilicate can be dry-added, in whole or in part, to the composition.

4 5 6

Base Granule

Aluminosilicate 18.0 0 17.0

Sodium sulfate 10.0 8.0 19.0

Sodium polyacrylate polymer 3.0 3.0 2.0

PolyethyleneGlycol (MW=4000) 2 2..00 2.0 1.0 l2-13 linear alkylbenzene

6.0 6.0 7.0 42

sulfonate, Na

Cl4-16 secondary alkyl sulfate, Na 3.0 3.0 3.0 14- 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

Admixed Agglomerates ^c 14- 15 ^al y! sulfate, Na 5.0 5.0

C 12- 13 linear alkylbenzene 2.0 2.0 sulfonate, Na

Sodium Carbonate 4.0 11.0

PolyethyleneGlycol (MW=4000) 1.0 1.0

Admix

Magnesiosilicate 20.0 5.0 12- 15 ^alky! 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-polyvinylimidazole 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)^ 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 43

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

Preferred Preparations of Siliceous Builder and Incorporation into Detergent

In accordance with this invention, a preferred process embodiment involves blending water insoluble starting materials including those for forming the essential siliceous builder (preferably said magnesiosilicates), silicas, and the like with water soluble starting materials such as magnesium oxide, alkali oxide(s) and the like with water to form a blended mixture. The composition of this blended mixture should be in accordance to the ranges of these materials as described in WO 97/10179. The blended mixture is then dehydrated via a spray dryer with an inlet temperature of greater than about 200°C or preferentially is agglomerated, prilled, tableted, etc. and dehydrated in such a manner to produce a high density, low moisture solid. Non-heat sensitive detergent adjuncts may be present, especially when the practitioner selects an agglomeration process.

The dehydrated mixture is heated until the siliceous builder material is formed. In the typical heating step, the temperature is from about 350°C to about 1000°C and occurs for at least 0.5 hours, preferably for at least 4 hours, and preferably in a CO2-free atmosphere. Preferably the heating step uses a rotating or stirred reactor or kiln, preferably with a low chromium content reactor vessel, which reduces greatly the heating or reaction time to obtain the desired builder material. In that regard, either direct fired or indirect fired kilns can be used, although direct fired kilns are preferred. The actual time, temperature and other conditions of the heating step will vary depending upon the particular starting materials. It will be appreciated by those skilled in 44

the art that lower and higher temperatures for the aforedescribed methods are possible provided longer heating times are available for the lower temperatures. The builder material is preferably cooled after heating.

Optionally, after the heating is complete, the resulting material undergoes sufficient grinding and/or crushing operations, either manually or using conventional apparatus, such that the siliceous builder material is suitably sized for incorporation into the cleaning composition. The optimum particle size of the magnesium silicate builder itself is surprisingly small relative to the average particle size of detergent granules. This preferred particle size range is 0.1 to 20 microns, more preferably 0.3 to 15 microns, and most preferably 0.5 to 10 microns.

A combination of two or more of the processes described herein can be used to achieve a builder material suitable for use in the compositions described herein. Another variation of the processes described herein contemplates blending and heating an excess of one of the starting ingredients (e.g. Na2CO3) such that the balance of the starting ingredient can be used as an active ingredient in the cleaning composition in which the builder material is contained. Additionally, seed crystals of the builder material may be used to enhance the time it takes to form the builder material from the starting components (e.g. use of crystalline Na2MgSiO4). Furthermore, slow addition of any of the reactants to the reaction mixture has also been found to be unexpectedly beneficial. Also, preheating the starting materials prior to input into the kiln enhances the speed of conversion to the siliceous builder material.

Claims

45What is claimed is:

1. A detergent composition comprising:

(a) from 0.1% to 99% of a particulate inorganic ion-exchanging siliceous builder, said siliceous builder being characterizable by X-ray diffraction, and said siliceous builder having a measurable improvement in the sum of Calcium binding and Magnesium binding as compared to Zeolite A; and

(b) from 0.1% to 99% of at least one detersive adjunct selected from the group consisting of:

(i) detersive surfactants having at least one branched, preferably mid-chain branched hydrophobe;

(ii) organic polymeric materials selected from polyacetal carboxylates, hydrophobically modified polyacrylates, terpolymers comprising acrylate or maleate, polymeric soil release agents, polymeric dye transfer inhibitors, polyamines, polyimines, polymeric rheology modifiers, and mixtures thereof;

(iii) oxygen bleach promoting materials selected from hydrophobic bleach activators; organic bleach boosters; transition-metal bleach catalysts; photobleaches and mixtures thereof;

(iv) fabric care promoting agents other than said organic polymeric materials; and

(v) mixtures of (i) - (iv).

2. he detergent composition according Claim 2 wherein said detersive surfactant is selected from mid-chain branched alkyl sulfates and mid-chain branched ethoxylated alkyl sulfates; and wherein said detersive surfactant is present at a level of from 0.1% to 30% by weight of said detergent composition.

3. The detergent composition according to any of Claims 1-2 comprising from 0.1% to 5% by weight of the detergent composition of a material selected from the group 46

consisting of hydrophobically modified polyacrylate, a terpolymer comprising acrylate or maleate, a polymeric soil release agent, a polymeric dye transfer inhibitor, and a polyamine, polyimine or derivative thereof.

4. The detergent composition according to any of Claims 1-3, comprising from 1 ppb to 10% of one or more hydrophobic bleach activators; organic bleach boosters; transition-metal bleach catalysts; photobleaches, or mixtures thereof.

5. The detergent composition according to any of Claims 1-4 wherein said siliceous builder is a magnesiosilicate.

6. The detergent composition according to any of Claims 1-5 wherein said siliceous builder has a stuffed silica polymorph-related structure.

7. The detergent composition according to any of Claims 1-6 wherein said siliceous builder has a measurable improvement in the sum of Calcium binding and Magnesium binding as compared to Zeolite A, delta-layer silicates and mixtures thereof.

8. The detergent composition according to any of Claims 1-7 wherein said siliceous builder is characterizable by X-ray diffraction as being different from any of: Zeolites A, P, X.

9. The detergent composition according to any of Claims 1-8 wherein said siliceous builder is combined into an agglomerate with at least one of said polymers, b(ii), without resorting to spray-drying said polymer.

10. The detergent composition according to any of Claims 1-9 wherein said siliceous builder is formed by a process comprising a step of blending and heating an excess of one of the starting ingredients (preferably sodium carbonate) such that the balance of said 47

starting ingredient is copresent with said siliceous builder as an active ingredient in the final detergent composition.