WO2000041522A2

WO2000041522A2 - Cleaning compositions containing a multi-function component and method for using

Info

Publication number: WO2000041522A2
Application number: PCT/US2000/000437
Authority: WO
Inventors: Jean-Luc Philippe Bettiol; Yong Zhu; Eric Christopher Wells; Michael Stanford Showell; Andre Christian Convents; Christiaan Arthur Jacques Kamiel Thoen; Glenn Steven Ward; Lynda Anne Speed
Original assignee: The Procter & Gamble Company
Priority date: 1999-01-11
Filing date: 2000-01-07
Publication date: 2000-07-20
Also published as: WO2000041522A3; AU2495900A

Abstract

The present invention relates to cleaning compositions comprising a multi-function component that is capable of hydrolyzing 1,3-β-glucans, 1,4-β-glucans and combinations of both physically and chemically linked 1,3-β-glucans and 1,4-β-glucans, and one or more cleaning adjunct materials selected from the group consisting of low foaming nonionic surfactants, hydrotropes and mixtures thereof, and methods for using the cleaning compositions for cleaning, especially tough food cleaning, or otherwise removing and/or reducing soils, especially carbohydrate soils, and/or removing or reducing spotting and films, from dishware, cookware and other hard surface substrates.

Description

CLEANING COMPOSITIONS CONTAINING A MULTI-FUNCTION COMPONENT AND METHOD FOR USING

TECHNICAL FIELD

The present invention relates to cleaning compositions comprising a multifunction component capable of hydrolyzmg 1,3-β-glucans, 1,4-β-glucans and combinations of both physically and chemically linked 1,3-β-glucans and 1,4-β-glucans, and methods for cleaning hard surface substrates, especially dishware, cookware, tableware, etc., by applying such cleaning compositions to the substrates. More specifically, the present invention relates to cleaning compositions that provide tough food cleaning, or otherwise removing and/or reducing soils, especially carbohydrate soils, and/or removing and/or reducing spotting and/or films, from hard surface substrates, especially dishware, cookware, tableware, etc. The cleaning compositions of the present invention and methods of using same, provide enhanced cleaning and improved tough food cleaning and/or removal and/or reduction of spotting and/or films from hard surface substrates relative to amylase-containmg detergent compositions without such a multifunction component.

BACKGROUND OF THE INVENTION

Detergents used for washing tableware (i.e., glassware, china, silverware, plastic, etc.), dishware, cookware or kitchenware m the home or institution have long been known. Dishwashing m the seventies is reviewed by Mizuno in Vol. 5, Part EH of the Surfactant Science Seπes, Ed. W.G. Cutler and R.C. Davis, Marcel Dekker, N.Y., 1973, incorporated by reference The particular requirements of cleansing tableware and leaving it m a sanitary, essentially stainless, residue-free state has indeed resulted in so many particular compositions that the body of art pertaining thereto is now recognized as quite distinct from other cleansing product art. Various types of enzymes have long been used in laundry detergents to assist in the removal of certain stams from fabπcs. Each class of enzyme (amylase, protease, etc ) generally catalyzes a different chemical reaction For example, protease enzymes are known for their ability to hydrolyze (break down a compound into two or more simpler compounds) other proteins. This ability has been taken advantage of through the incorporation of naturally occurring or engineered protease enzymes to laundry detergent compositions.

In recent years the use of enzymes has also been investigated for use in automatic dishwashing compositions.

However, consumers continue to expeπence problems with stain, soil and tough food removal on vaπous substrates, including typical kitchenware surfaces. In particular, formulators have expeπenced difficulties m formulating detergents which remove carbohydrate soils such as cereal and gram soils, for example, oatmeal, barley, rye, wheat, and πce. Typically, for carbohydrate soil removal, formulators have turned to amylase and hemicellulase enzymes. However, consumers continue to expeπence problems m removing carbohydrate soils.

WO 95/35382 to Gist-Brocades discloses the use of hemicellulases, such as xylanases, in dishwashing compositions.

Additionally, consumers interest in automatic dishwashing compositions which deliver tough food cleaning is increasing. Cooked-on, baked-on, dπed-on and/or bumed-on cereals and grains have long been difficult to effectively remove via automatic dishwashing. In addition, consumers now desire less handwashmg or pre-washmg of dishes and more cleaning ability delivered via the automatic dishwasher.

The pπor art fails to teach or suggest the cleaning compositions of the present invention comprising the multi-function component of the present invention.

Accordingly, there is still a need for compositions that provide enhanced and improved tough food cleaning, especially of carbohydrate soils; that provide enhanced and improved tough food cleaning under automatic dishwashing conditions; that provide tough food cleaning via cellulase enzymes designed to deliver such benefits; and that provide removal/reduction of spotting and films from hard surfaces.

SUMMARY OF THE INVENTION

The present invention meets the needs discussed above The present invention provides cleaning compositions that contain a multi-function component capable of hydrolyzing 1,3-β- glucans, 1 ,4-β-glucans and combinations of both physically and chemically linked 1,3-β-glucans and 1,4-β-glucans, and methods for cleaning hard surface substrates, especially dishware, cookware, tableware, etc.. by applying such cleaning compositions to the substrates.

By the present invention, it has now been surpnsingly found that cleaning compositions containing the multi-function component of the present invention, when applied directly to a surface m need of cleaning, such as a carbohydrate soiled surface, provide significantly better cleaning of the surface relative to amylase-contaming detergent compositions without such a multi-function component.

The cleaning compositions descnbed herein provide supeπor removal and/or reduction of soils, especially carbohydrate soils, such as oatmeal, barley, rye, wheat and πce, and/or spotting and films objected to by the consumer from stainless steel and other metals, plastic, ceramic, dishware, cookware, glass, wood, baby bottles, and many other known hard surface substrates, both porous and non-porous.

By "multi-function component" it is meant a component that exhibits or performs more than one function. In the case of the present invention, the multi-function component is capable of hydrolyzing 1,3-β-glucans, 1 ,4-β-glucans and combinations of both physically and chemically linked 1,3-β-glucans and 1,4-β-glucans. With respect to the combinations, by "physically linked" it is meant that distinct, discrete 1,3-β-glucans and 1 ,4-β-glucans are mixed with each other; by "chemically linked", it is meant that 1,3-β-glucans and 1 ,4-β-glucans are present in a single molecule (i.e. branched 1,3/1,4-β-glucans, and mixed 1,3/1,4-β-glucans). By "effective amount" or "soil removal-improving amount" it is meant an enzyme m any amount capable of measurably improving soil removal (especially carbohydrate soils) from the surface, i.e., soiled dishware, cookware, countertop, etc., when it is washed by the consumer, either manually or by an automatic washing machine (laundry or dishwashing). In general, this amount may vary quite widely. By "tough food cleaning" it is meant the ability to clean cooked-on, burned-on, baked-on or dπed-on foods. Examples include burned-on, baked-on and dπed-on oatmeal.

By "surface m need of cleaning" it is meant a surface such as tableware, dishware, cookware and other hard surface substrates including but not limited to vaπeties of stainless steel and other metals, glass, ceramic, baby bottles, wood and plastic that is soiled by any type of soil, preferably a carbohydrate soil, and/or has spots or films.

In accordance with one aspect of the present invention, a cleaning composition, preferably a detergent composition, compπsmg the multi-function component of the present invention and one or more cleaning adjunct matenals selected from the group consisting of low foaming nonionic surfactants, hydrotropes and mixtures thereof is provided. In accordance with another aspect of the present invention, a cleaning composition, preferably a detergent composition, compnsmg the multi-function component of the present invention, an amylase and one or more cleaning adjunct mateπals selected from the group consisting of low foaming nonionic surfactants, hydrotropes and mixtures thereof is provided.

In accordance with yet another aspect of the present invention, a fabπc cleaning composition compπsing the multi-function component of the present invention, at least about 5% surfactant and at least about 5% builder, at least one other cleaning adjunct mateπal selected from the group consisting of low foaming nonionic surfactants, hydrotropes and mixtures thereof, and optionally, a bleaching agent and/or amylase is provided

In accordance with yet another aspect of the present invention, a dishwashing detergent composition compnsmg: (a) from about 0.0001% to about 10% by weight of the composition of the multifunction component of the present invention;

(b) from about 0.1% to about 10% by weight of the composition of a low foaming nonionic surfactant; and

(c) optionally, from about 0.5% to abotu 20% by weight of the composition of a bleaching agent; and

(d) optionally, from about 0.0001 % to about 2% by weight of an amylase is provided.

In accordance with still yet another aspect of the present invention, an automatic dishwashing composition compnsmg: (a) a tablet body including one or more cleaning adjunct mateπals; and

(b) a dimple portion including the multi-function component of the present invention; wherein said dimple portion is attached to said tablet body such that said multi-function component is capable of activation in a wash solution pπor to activation of said one or more cleaning adjunct matenals of said tablet body is provided. In accordance with yet another aspect of the present invention, a method for cleaning a surface in need of cleaning is provided. The method compnses contacting the surface m need of cleaning with an effective amount of a cleaning composition containing the multi-function component of the present invention, and optionally an amylase and/or optionally one or more cleaning adjuncts, such that the cleaning composition cleans (e g., cleans a wide range of soils) the surface.

In accordance with yet another aspect of the present invention, a method for cleaning a dish m need of cleaning compnsmg contacting the dish with a dishwashing cleaning composition descnbed herein is provided.

In accordance with still yet another aspect of the present invention, a surface cleaned by the methods of the present invention is provided. Yet another aspect of the present invention is a product comprising a cleaning composition containing the multi-function component of the present invention and a cleaning adjunct matenal selected from the group consisting of low foammmg nonionic surfactants, the product further including instructions for using the cleaning composition to clean surfaces in need of cleaning.

Still yet another aspect of the present invention is a product compnsmg a cleaning composition containing the multi-function component of the present invention and an amylase and at least one cleaning adjunct mateπal selected from the group consisting of low foaming nonionic surfactants, hydrotropes and mixtures thereof, the product further including instructions for using the cleaning composition to clean surfaces need of cleaning.

Accordingly, the present invention provides: cleaning compositions that are effective and efficient in cleaning surfaces in need of cleaning; methods of using the cleaning composition to clean such surfaces; surfaces cleaned with the cleaning compositions; and products compnsmg the cleaning compositions. All percentages and proportion herein are by weight, and all references cited herein are hereby incorporated by reference, unless otherwise specifically indicated.

DETAILED DESCRIPTION OF THE INVENTION

Multi-function component - Suitable multi-function components for use in the cleaning compositions of the present invention include multi-function components that hydrolyze 1,3-β- glucans, 1 ,4-β-glucans and combinations of both physically and chemically linked 1,3-β-glucans and 1 ,4-β-glucans. Preferred multi-funcnon components in accordance with the present invention are enzymes. More preferred multi-function components in accordance with the present invention are cellulases. Most preferred multi-function components in accordance with the present invention are endoglucanases (EC 3.2.1.4).

One of the top consumer relevant tough soils based on cleaning failure and frequency is oatmeal cereal which contains significant amounts of glucan substrates. Glucan substrates present in the cell wall of cereal meals are very sticky and difficult to remove. The also glue and prevent other soils from being removed. It has been found that the endoglucanase of the present invention can digest glucan polymers that are not degradable by amylases, and further release other soil multi-function components, leading to improved cleaning benefits.

Suitable endoglucanases are descnbed m WO 94/14953 as "Endoglucanase Type IV (otherwise known as Endoglucanase IV or EG IV) and are. (1) encoded at least partially by DNA sequences disclosed m WO 94/14953, which is incorporated herein by reference, m the appended SEQ ED No 8 and/or SEQ ID No. 19 or a sequence homologous thereto encoding a polypeptide ("a homologue") with 1,3 and 1,4-β-D-glucans activity; and/or (2) enzymes that are lmmunologically reactive with an antibody raised against a highly punfied endoglucanase encoded by the DNA sequence SEQ ID No. 19 and deπved from Aspergi I lus aculeatus, CBS 101 43. Endoglucanase IV exhibits a surpnsmgly high specificity and specific activity towards β- glucan. Endoglucanase IV is descnbed in WO 94/14953 as being capable of degrading cellulose and cellulose deπvatives like carboxymethylcellulose and hydroxyethylcellulose, and mixed β- 1,3-1,4 glucans like cereal β-glucans.

Other endoglucanases for use in the cleaning compositions of the present invention is an endoglucanase (EC 3.2.1.4), which surpnsingly catalyzes hydrolysis of internal 1,3-β-D- glycosidic linkages in hemicellulose β-D-glucans, and 1,4-β-D-glycosιdιc linkages in cellulose, chenin, and cereal β-D-glucans. The endoglucansase (EC 3.2.1.4) exhibits significant activity on both the 1,3 and 1,4-β-D glycosidic linkages, and does not show substantially greater activity for one over the other. Suitable endoglucanases (EC 3.2.1.4) include, but are not limited to, the endoglucanases (EC 3.2.1.4) descnbed in WO 94/14953 to Novo Nordisk A/S, which is incorporated herein by reference.

Other specific cellulases suitable for the present invention have been descnbed in W091/17244 wherein single-multi-function component enzymes selected for high specific activity are descnbed and wherein an enzyme capable of degrading cellulose or hemicellulose is disclosed.

Also suitable are the cellulolytic enzymes covered in W095/02675 which descnbes a detergent composition compnsmg two cellulase multi-function components : a first cellulase multi-function component having a retainmg-type activity and being capable of particulate soil removal and a second cellulase multi-function component having multiple domains compπsing at least one non-catalytic domain attached to a catalytic domain and being capable of color claπfication wherein at least one of the cellulase multi-function components is a single multifunction component. Said enzymatic detergent composition is capable of providing both sufficient colour claπfication and particulate soil removal which, after a limited number of washing cycles, neither damage nor partly degrade the cellulose-containing fabnc. A preferred endoglucanase is an endoglucanase which is immunoreactive with an antibody raised against a highly punfied ~50kD endoglucanase deπved from Humicola insolens, DSM 1800, or which is a homologue or deπvative of the ~50kD endoglucanase exhibiting cellulase activity; a preferred endoglucanase has the ammo acid sequence disclosed in PCT Patent Application No. W091/17244, or an endoglucanase which is immunoreactive with an antibody raised against a highly punfied ~50kD (apparent molecular weight, the am o acid composition corresponds to 45kD with 2n glycosylation sites) endoglucanase deπved from Fusanum oxysporum, DSM 2672, or which is a homologue or deπvative of the ~50kD endoglucanase exhibiting cellulase activity; another preferred endoglucanase has the ammo acid sequence disclosed in PCT Patent Application No. W091/17244.

A preferred multi-function component is a cellulase, more preferably the endoglucanase having the ammo acid sequence disclosed WO95/02675 in the appended SEQ ED N0:3 or in

W091/17244, Fig. 13, or a vaπant of said endoglucanase having an amino acid sequence being at least 60%, preferably at least 70%, more preferably 75%, more preferably at least 80%, more preferably 85%, especially at least 90% homologous with said sequence. The endoglucanase is produced by Aspergillus oryzae after transformation with a plasmid containing the DNA sequence corresponding to the ammo acid sequence of the SEQ ID NO: 3 descnbed in

WO95/02675 and using a Taka promotor and AMG terminator. This endoglucanase may be punfied to homogeneity using cationic chromatography and has a pl>9. The calculated pi is based on the amino acid composition using the PHKa values from Adv. Protein Chem. 17, p. 69- 165 (1962) C. Tanford. the molar extinction coefficient is calculated to be 58180. More preferred is the cellulase deπved from Humicola tnsolens, DSM 1800, having an approximate molecular weight of about 50 kDa, an iso-electπc point of about 5.5 and containing 415 ammo acids, such as descnbed m WO95/02675 which is an endoglucanase and has the ammo acid sequence disclosed therein in the appended SEQ ED NO:2 or in W091/17244, Fig. 14A-E, or a vaπant of said endoglucanase having an ammo acid sequence being at least 60%, preferably at least 70%, more preferably 75%, more preferably at least 80%, more preferably 85%, especially at least 90% homologous with said sequence.

Other suitable multi-function components include the cellulases that exhibit endo- 1,3(4)- β-glucanase activity as descnbed in PCT Patent Application No. WO 95/31533.

Other suitable specific cellulases are the EGiπ cellulases from Tnchoderma longibrachiatum descnbed m W094/21801, Genencor, published September 29, 1994.

The endoglucanase may be deπved or isolated and punfied from microorganisms which are known to be capable of producing cellulolytic enzymes, e.g. species of Humicola, Bacillus, Trichederma, Fusanum, Myceliophtora, Phanerochaete, Schizophyllum, Pemcillium, Aspergillus and Geotricum. The deπved multi-function components may be either homologous or heterologous multi-function components. Preferably, the multi-function components are homologous. However, a heterologous multi-function component which is immunoreactive with an antibody raised against a highly punfied cellulase multi-function component possessing the desired property or properties and which heterologous multi-function component is deπved from a specific microorganism is also preferred. Other suitable cellulases are the EG Lfrom Trichoderma longώrachiatum descnbed m WO94/21801, Genencor, published September 29, 1994, and the cellulases that exhibit endo- l,3(4)-β-glucanase activity descnbed in W097/44361.

In the present context, the term "homologue" is intended to indicate a polypeptide encoded by DNA which hybπdizes to the same probe as the DNA coding for the endoglucanase enzyme with this ammo acid sequence under certain specified conditions (such as presoakmg in 5xSSC and prehybπdizmg for 1 h at about 40°C in a solution of 20% formamide, 5xDenhardt's solution, 50mM sodium phosphate, pH 6.8, and 50 μg of denatured sonicated calf thymus DNA, followed by hybπdization in the same solution supplemented with 100 μM ATP for 18 h at about 40°C). The term is intended to include denvatives of the aforementioned sequence obtained by addition of one or more amino acid residues to either or both the C- and N-terminal of the native sequence, substitution of one or more am o acid residues at one ore more sites in the native sequence, deletion of one or more ammo acid residues at either or both ends of the native am o acid sequence or at one or more sites within the native sequence, or insertion of one or more ammo acid residues at one or more sites in the native sequence.

For industrial production of the cellulase preparation herein, however, it is preferred to employ recombmant DNA techniques or other techniques involving adjustments of fermentations or mutation of the micro-organisms involved to ensure overproduction of the desired enzymatic activities. Such methods and techniques are known in the art and may readily be earned out by persons skilled in the art.

The above-mentioned enzymes may be of any suitable oπgin, such as vegetable, animal, bactenal, fungal and yeast origin. Oπgin can further be mesophi c or extremophi c (psychrophihc, psychrotrophic, thermophihc, barophi c, alkalophihc, acidophihc, halophi c, etc.) Punfied or non-puπfied forms of these enzymes may be used. Nowadays, it is common practice to modify wild-type enzymes via protein / genetic eng eeπng techniques m order to optimize their performance efficiency in the cleaning compositions of the invention. For example, the vanants may be designed such that the compatibility of the enzyme to commonly encountered ingredients of such compositions is increased. Alternatively, the vaπant may be designed such that the optimal pH, bleach or chelant stability, catalytic activity and the like, of the enzyme vaπant is tailored to suit the particular cleaning application.

In particular, attention should be focused on ammo acids sensitive to oxidation in the case of bleach stability and on surface charges for the surfactant compatibility. The isoelectπc point of such enzymes may be modified by the substitution of some charged ammo acids, e.g. an increase in isoelectπc point may help to improve compatibility with anionic surfactants. The stability of the enzymes may be further enhanced by the creation of e.g. additional salt bπdges and enforcing calcium binding sites to increase chelant stability. Amylase - In preferred embodiments of the cleaning compositions of the present invention, an amylase, in addition to the multi-function components descnbed above, is incorporated into the cleaning compositions. A preferred amylase is an α-amylase. The α- amylase is an endoglucosidase (EC 3.2.1.1) which catalyzes the hydrolysis of internal α- glucosidic linkages in starches.

It has been surpnsmgly found that a cleaning composition containing the endoglucanase (3.2.1.4) of the present invention and an amylase delivers synergistic performance benefits in dish applications. In other words, a cleaning composition containing the endoglucanase (3.2.1.4) of the present invention and the amylase performs significantly better than each single enzyme alone at equal total enzyme levels. Therefore, the combination performs better than the cumulative performance of the enzymes used alone.

The endoglucanase (EC 3.2.1.4) of the invention exhibits different substrate specificity from amylase. α-amylases used in detergent systems is an endoglucosidase (EC 3.2.1.1), which catalyzes hydrolysis of internal α-glucosidic linkages m starches. As discussed above, it has been found that a combination of the endoglucanase (EC 3.2.1.4) of the invention with an amylase, such as the α-amylases descnbed herein, maximizes and optimizes the specific functions of each enzyme m the wash and delivers synergistic benefits in cleaning performance that normally can not be achieved by each single enzyme. With such combinations of the two enzymes at different ratios and levels, a wide range of substrate specificity against different consumer soils and high flexibility toward vanety of wash conditions and cost-effectiveness can be achieved that leads to performance robustness in global applications.

Amylases useful in the present invention include, but are not limited to, the amylases descnbed in WO 95/26397 and WO 96/23873 (Novo). These enzymes are incorporated into cleaning compositions at a level of from about 0.0001%, preferably from about 0.00018%, more preferably from about 0.00024%, most preferably from about 0.05% to about 0.1%, preferably to about 0.060%), more preferably to about 0.048% by weight of the cleaning compositions of pure enzyme.

The amylases for use in the present invention are preferably selected from the group consisting of α-amylase vanants. Suitable α-amylase vanants for use m the present invention include, but are not limited to the following α-amylases:

(_l) α-amylase charactenzed by having a specific activity at least 25% higher than the specific activity of Termamyl® at a temperature range of 25°C to 55°C and at a pH value in the range of 8 to 10, measured by Phadebas® α-amylase activity assay and/or; (n) α-amylase according to (1) compπsing the amino acid sequence shown m SEQ ID No. 1 or an α-amylase being at least 80% homologous with the ammo acid sequence shown in SEQ ID No 2 and/or;

(in) α-amylase according to (I) compπsing the ammo acid sequence shown m SEQ ED No. 2 or an α-amylase being at least 80% homologous with the ammo acid sequence shown SEQ ID No. 3 and/or;

(iv) α-amylase according to (l) compnsmg the following ammo acid sequence N- terminal: Hιs-Hιs-Asn-Gly-Thr-Asn-Gly-Thr-Met-Met-Gln-Tyr-Phe-Glu-T -Tyr-Leu-Pro-Asn- Asp (SEQ ID No. 4) or an α-amylase being at least 80% homologous with the ammo acid sequence shown (SEQ ID No. 4) m the N-termmal and/or;

(v) α-amylase according to (ι-ιv) wherein the α-amylase is obtainable from an alkalophi c Bacillus species and/or;

(vi) α-amylase according to (v) wherein the amylase is obtainable from any of the strains NCIB 12289, NCTB 12512, NCB 12513 and DSM 935 and/or; (vn) α-amylase showing positive immunological cross-reactivity with antibodies raised against an α-amylase having an ammo acid sequence corresponding respectively to SEQ ID No. 2, ID No. 3, or ID No. 4 and/or;

(vm) vaπant of a parent α-amylase, wherein the parent α-amylase (1) has one of the ammo acid sequences shown m SEQ ID No. 2, ED No. 3, or ED No. 4, respectively, or (2) displays at least 80% homology with one or more of said ammo acid sequences, and/or displays immunological cross-reactivity with an antibody raised against an α-amylase having one of said amino acid sequences, and/or is encoded by a DNA sequence which hybπdizes with the same probe as a DNA sequence encodmg an α-amylase having one of said amino acid sequences, in which vanants: (A) at least one ammo acid residue of said parent α-amylase has been deleted; and/or (B) at least one ammo acid residue of said parent α-amylase has been replaced by a different ammo acid residue; and/or (C) at least one ammo acid residue has been inserted relative to said parent α-amylase; said vanant having an α-amylase activity and exhibiting at least one of the following properties relative to said parent α-amylase: increased thermostabihty; increased stability towards oxidation; reduced Ca ion dependency; increased stability and/or α-amylolytic activity at neutral to relatively high pH values; increased α-amylolytic activity at relatively high temperature: and increase or decrease of the isoelectπc point (pi) so as to better match the pi value for α-amylase vaπant to the pH of the medium.

A polypeptide is considered to be X% homologous to the parent amylase if a compaπson of the respective ammo acid sequences, performed via algonthms, such as the one descnbed by Lipman and Pearson in Science 227, 1985, p. 1435, reveals an identity of X%. In the context of the present invention, the term "obtainable from" is intended not only to indicate an amylase produced by a Bacillus strain but also an amylase encoded by a DNA sequence isolated from such a Bacillus strain and produced m a host organism transformed with the DNA sequence. Multi-function component/ Amylase Combination - In the cleaning compositions of the present invention, when the multi-function component and amylase are present, the multifunction component and amylase may be present m the cleaning compositions in any ratio. Preferably, the multi-function component and amylase are present in a ppm ratio of multifunction component to amylase of from about 1.20, more preferably from about 1: 10, most preferably from about 1 : 5 to about 20: 1, more preferably to about 10: 1, most preferably from about 5: 1 It is highly desirable that the multi-function component and amylase are present in a ppm ratio of multi-function component to amylase of from about 1 :3 to about 3: 1.

Further, the multi-function component and amylase, when present, are preferably present m the cleaning compositions of the present invention at a total enzyme level of from about 0.01 ppm, more preferably from about 0.2 ppm, most preferably from about 0.6 ppm to about 50 ppm, more preferably 10 ppm, even more preferably 7 ppm, most preferably 4 ppm. It is highly desirable that the multi-function component and amylase, when present, are present m the cleaning compositions of the present invention at a total enzyme level of from about 0.6 ppm to about 3.0 ppm. CLEANING COMPOSITIONS

The cleaning compositions of the present invention compnse an effective amount of a multi-function component that is capable of hydrolyzing 1,3-β-glucans, 1 ,4-β-glucans and combinations of both physically and chemically linked 1,3-β-glucans and 1,4-β-glucans. Preferably, the cleaning compositions further include one or more of the following cleaning ad_junct mateπals selected from the group consisting of: surfactants, solvents, clay, polycarboxylate thickeners, builders, dispersants, other enzymes, bleaches, bleach activators, bleach catalysts, baking soda, carbonates, phosphates, hydrobenzoic acid, dicarboxyhc acid, siloxanes, perfumes, water and mixtures thereof. More preferably, the cleaning compositions further include an amylase, preferably an α-amylase, as discussed herein. It has been found that the cleaning compositions of the present invention provide supeπor tough food cleaning benefits, especially on carbohydrate soils, than cleaning compositions that contain amylase, a leading carbohydrate soil enzyme, without a multi-function component that is capable of hydrolyzing 1,3-β-glucans, 1,4-β-glucans and combinations of both physically and chemically linked 1,3-β-glucans and 1,4-β-glucans. Preferred cleaning compositions in accordance with the present invention compnse from about 0.0001%, more preferably from about 0.001%, most preferably from about 0.02% to about 10%, more preferably 1%, most preferably 0.2% by weight of the compositions of a pure multifunction component (m other words, when the multi-component is an enzyme, the cleaning composition compπses from about 0.0001% by weight of the composition of the pure enzyme) that is capable of hydrolyzing 1,3-β-glucans, 1 ,4-β-glucans and combinations of both physically and chemically linked 1,3-β-glucans and 1,4-β-glucans.

Further, it is desirable that the multi-function component of the present invention is present m the cleaning compositions of the present invention in an amount sufficient to provide from about 0.001 ppm, more preferably 0.01 ppm to about 10 ppm, more preferably 6 ppm, of multi-function component m the wash liquor. The cleaning compositions can be in a vanety of forms including, but not limited to, a liquid, a gel, a foam, a spray, a powder, a particulate, a bar, a granule or a tablet, especially a dimple tablet or multi-layer detergent tablet having both compressed and non-compressed portions.

A more preferred multi-layer detergent tablet compπses: 1) a compressed solid body portion having therein at least one mould the compressed solid body portion; and 2) at least one non-compressed, non-encapsulating portion mounted in the at least one mould of the compressed solid body portion, having an area of B, the at least one non-compressed, non- encapsulatmg portion compnsmg at least one detergent active; wherein the surface area of the detergent tablet, excluding areas of the at least one mould, is A; and preferably, wherein the ratio ofB to A is from about l:50 to 4: l, by area.

Most preferred cleaning compositions of the present invention compnse the multifunction component of the present invention, an amylase, and one or more cleaning adjunct mateπals selected from the group consisting of low foaming nonionic surfactants.

In addition to the multi-function component of the present invention, one or more cleaning adjunct mateπals selected from the group consisting of low foammmg nonionic surfactants, and optionally an amylase, the cleaning compositions of the present invention may include an enzyme cocktail deπved from two or more other enzymes, such as other carbohydrases including but not limited to other cellulases, other amylases, hemicellulases, cell-degrading enzymes, and pectm-degrading enzymes, and also proteases, hpases, bleaching enzymes and phosphohpid/phosphoprotein degrading enzymes. The term "cleaning adjunct mateπals". as used herein, means any liquid, solid or gaseous mateπal selected for the particular type of cleaning composition desired and the form of the product (e.g., liquid; granule; powder; bar; paste; spray; tablet; gel, foam composition), which mateπals are also preferably compatible with the protease enzyme used m the composition Granular compositions can also be in "compact" form and the liquid compositions can also be m a "concentrated" form.

The specific selection of cleaning adjunct mateπals are readily made by consideπng the surface, item or fabπc to be cleaned, and the desired form of the composition for the cleaning conditions duπng use (e.g., through the wash detergent use). The term "compatible", as used herein, means the cleaning composition matenals do not reduce the proteolytic activity of the protease enzyme to such an extent that the protease is not effective as desired during normal use situations. Examples of suitable cleaning adjunct mateπals include, but are not limited to, surfactants, builders, bleaches, bleach activators, bleach catalysts, other enzymes, enzyme stabilizing systems, chelants, optical bπghteners, soil release polymers, dye transfer agents, dispersants, suds suppressors, dyes, perfumes, colorants, filler salts, hydrotropes, photoactivators, fluorescers, fabnc conditioners, hydrolyzable surfactants, perservatives, anti-oxidants, anti- shπnkage agents, anti-wπnkle agents, germicides, fungicides, color speckles, silvercare, anti- tarnish and or anti-corrosion agents, alkalinity sources, solubilizing agents, earners, processing aids, pigments and pH control agents as descnbed m U.S. Patent Nos. 5,705,464, 5,710,115, 5,698,504, 5,695,679, 5,686,014 and 5,646,101. Specific cleaning composition mateπals are exemplified m detail hereinafter.

If the cleaning adjunct mateπals are not compatible with the protease vaπant(s) in the cleaning compositions, then suitable methods of keeping the cleaning adjunct mateπals and the protease vaπant(s) separate (not m contact with each other) until combination of the two components is appropnate can be used. Suitable methods can be any method known in the art, such as gelcaps, encapulation, tablets, physical separation, etc.

Preferably an effective amount of one or more protease vanants descnbed above are included in compositions useful for cleaning a vanety of surfaces in need of prote aceous stam removal. Such cleaning compositions include detergent compositions for cleaning hard surfaces, unlimited in form (e.g., liquid and granular); detergent compositions for cleaning fabncs, unlimited m form (e.g., granular, liquid and bar formulations); dishwashing compositions (unlimited m form and including both granular and liquid automatic dishwashing); oral cleaning compositions, unlimited m form (e.g., dentifrice, toothpaste and mouthwash formulations); and denture cleaning compositions, unlimited m form (e.g , liquid, tablet). As used herein, "effective amount of protease vaπant" refers to the quantity of protease vaπant descnbed hereinbefore necessary to achieve the enzymatic activity necessary in the

SUBST-TUTE SHEET (RULE 26) specific cleaning composition. Such effective amounts are readily ascertained by one of ordinary skill in the art and is based on many factors, such as the particular vaπant used, the cleaning application, the specific composition of the cleaning composition, and whether a liquid or dry (e.g., granular, bar) composition is required, and the like. Preferably the cleaning compositions compnse from about 0.0001%, preferably from about 0.001%, more preferably from about 0.01% by weight of the cleaning compositions of one or more protease vanants of the present invention, to about 10%, preferably to about 1%, more preferably to about 0.1%. Also preferably the protease vanant of the present invention is present m the compositions an amount sufficient to provide a ratio of mg of active protease per 100 grams of composition to ppm theoretical Available O2 ("Avθ2") from any peroxyacid in the wash liquor, referred to herein as the Enzyme to Bleach ratio (E/B ratio), ranging from about 1.1 to about 20: 1. Several examples of vaπous cleaning compositions wherein the protease vanants of the present invention may be employed are discussed in further detail below. Also, the cleaning compositions may include from about 1% to about 99.9% by weight of the composition of the cleaning adjunct matenals.

As used herein, "cleaning compositions" include hard surface cleaning compositions, dishwashing detergent compositions, oral cleaning compositions, denture cleaning compositions and personal cleansing compositions.

The compositions of the present invention can also be used as detergent additive products in solid or liquid form. Such additive products are intended to supplement or boost the performance of conventional detergent compositions and can be added at any stage of the cleaning process.

When formulated as compositions for use in manual dishwashing methods the compositions of the invention preferably contain a surfactant and preferably other cleaning adjunct matenals selected from organic polymenc compounds, suds enhancing agents, group II metal ions, solvents, hydrotropes and additional enzymes.

If needed the density of the laundry detergent compositions herein ranges from 400 to 1200 g/litre, preferably 500 to 950 g/htre of composition measured at 20°C.

The "compact" form of the cleaning compositions herein is best reflected by density and, m terms of composition, by the amount of inorganic filler salt; inorganic filler salts are conventional ingredients of detergent compositions m powder form; m conventional detergent compositions, the filler salts are present in substantial amounts, typically 17-35% by weight of the total composition. In the compact compositions, the filler salt is present in amounts not exceeding 15% of the total composition, preferably not exceeding 10%, most preferably not exceeding 5% by weight of the composition. The inorganic filler salts, such as meant m the present compositions are selected from the alkali and alkaline-earth-metal salts of sulfates and chlorides. A prefeπed filler salt is sodium sulfate.

Liquid cleaning compositions according to the present invention can also be in a

"concentrated form", m such case, the liquid cleaning compositions according the present invention will contain a lower amount of water, compared to conventional liquid detergents.

Typically the water content of the concentrated liquid cleaning composition is preferably less than 40%, more preferably less than 30%, most preferably less than 20% by weight of the cleaning composition.

Preferably, the cleaning compositions, especially the dishwashing compositions, compnse phosphate builders and/or bleaching agents.

Cleaning Adiunct Matenals

Surfactant System - Detersive surfactants included in the fully-formulated cleaning compositions afforded by the present invention compnse at least about 0.01%, preferably at least about 0.1%, more preferably at least about 1% to preferably about 60%, more preferably to about 35%, most preferably to 30% by weight of cleaning composition depending upon the particular surfactants used and the desired effects.

The detersive surfactant can be nonionic, anionic, ampholytic, zwitteno c, cationic, semi-polar nonionic, and mixtures thereof, nonhmitmg examples of which are disclosed m U.S.

Patent Nos. 5,707,950 and 5,576,282. Preferred cleaning compositions compnse anionic deter- sive surfactants or mixtures of anionic surfactants with other surfactants, especially nonionic surfactants.

Nonhmitmg examples of surfactants useful herein include the conventional C\ 1 -Ci g alkyl benzene suifonates and pπmary, secondary and random alkyl sulfates, the Ci Q-Cig alkyl alkoxy sulfates, the Ci _Q-Ci g alkyl polyglycosides and their corresponding sulfated polyglyco- sides, C^-C^g alpha-sulfonated fatty acid esters, C12-C1 g alkyl and alkyl phenol alkoxylates

(especially ethoxylates and mixed ethoxy/propoxy), C^-Cj betaines and sulfobetames ("sul- tames"), C JQ-C ι amine oxides, and the like. Other conventional useful surfactants are listed in standard texts.

The surfactant is preferably formulated to be compatible with enzyme components present in the composition. In liquid or gel compositions the surfactant is most preferably formulated such that it promotes, or at least does not degrade, the stability of any enzyme in these compositions.

Examples of suitable nonionic, anionic, cationic, ampholytic, zwittenomc and semi-polar nonionic surfactants are disclosed in U.S. Patent Nos. 5,707,950 and 5,576,282. Nonionic Surfactants - Particularly preferred surfactants in the preferred automatic dishwashing compositions (ADD) of the present invention are low foaming nonionic surfactants (LFNI) LFNI may be present in amounts from 0.01% to about 10% by weight, preferably from about 0.1% to about 10%, and most preferably from about 0.25% to about 4%. LFNIs are most typically used in ADDs on account of the improved water-sheeting action (especially from glass) which they confer to the ADD product. They also encompass non-si cone, nonphosphate polymenc mateπals further illustrated hereinafter which are known to defoam food soils encountered in automatic dishwashing.

Preferred LFNIs include nonionic alkoxylated surfactants, especially ethoxylates deπved from pπmary alcohols, and blends thereof with more sophisticated surfactants, such as the polyoxypropylene/polyoxyethylene/polyoxypropylene (PO/EO/PO) reverse block polymers as descnbed U.S. Patent Nos. 5,705,464 and 5,710,115. The PO/EO/PO polymer-type surfactants are well-known to have foam suppressing or defoammg action, especially in relation to common food soil ingredients such as egg.

Highly preferred ADDs herein wherein the LFNI is present make use of ethoxylated monohydroxy alcohol or alkyl phenol and additionally compnse a polyoxyethylene, polyoxypropylene block polymenc compound as descnbed m U.S. Patent Nos. 5,705,464 and 5,710,115.

The invention encompasses preferred embodiments wherein LFNI is present, and wherein this component is solid at about 95°F (35°C), more preferably solid at about 77°F (25°C). For ease of manufacture, a preferred LFNI has a meltmg point between about 77°F (25°C) and about 140°F (60°C), more preferably between about 80°F (26.6°C) and 110°F (43.3°C).

In a preferred embodiment, the LFNI is an ethoxylated surfactant denved from the reaction of a monohydroxy alcohol or alkylphenol containing from about 8 to about 20 carbon atoms, with from about 6 to about 15 moles of ethylene oxide per mole of alcohol or alkyl phenol on an average basis.

A particularly preferred LFNI is deπved from a straight chain fatty alcohol containing from about 16 to about 20 carbon atoms (C 16-^20 alcohol), preferably a Ci g alcohol, condensed with an average of from about 6 to about 15 moles, preferably from about 7 to about 12 moles, and most preferably from about 7 to about 9 moles of ethylene oxide per mole of alcohol. Preferably the ethoxylated nonionic surfactant so deπved has a narrow ethoxylate distnbution relative to the average.

The LFNI can optionally contain propylene oxide m an amount up to about 15% by weight. Other preferred LFNI surfactants can be prepared by the processes descnbed in U.S.

Patent 4,223,163, issued September 16, 1980, Builloty, incorporated herein by reference. Highly preferred ADDs herein wherein the LFNI is present make use of ethoxylated monohydroxy alcohol or alkyl phenol and additionally compnse a polyoxyethylene, polyoxypropylene block polymenc compound: the ethoxylated monohydroxy alcohol or alkyl phenol fraction of the LFNI compnsmg from about 20% to about 100%, preferably from about

30% to about 70%, of the total LFNI.

Suitable block polyoxyethylene-polyoxypropylene polymenc compounds that meet the requirements descnbed hereinbefore include those based on ethylene glycol, propylene glycol, glycerol, tπmethylolpropane and ethylenediamme as initiator reactive hydrogen compound.

Polymenc compounds made from a sequential ethoxylation and propoxylation of initiator compounds with a single reactive hydrogen atom, such as C12-1 g aliphatic alcohols, do not generally provide satisfactory suds control in the instant ADDs. Certain of the block polymer surfactant compounds designated PLURONIC® and TETRONIC® by the BASF-Wyandotte Corp., Wyandotte, Michigan, are suitable in ADD compositions of the invention.

A particularly preferred LFNI contains from about 40% to about 70% of a polyoxypropylene/polyoxyethylene/polyoxypropylene block polymer blend compnsmg about 75%, by weight of the blend, of a reverse block co-polymer of polyoxyethylene and polyoxypropylene containing 17 moles of ethylene oxide and 44 moles of propylene oxide; and about 25%, by weight of the blend, of a block co-polymer of polyoxyethylene and polyoxypropylene initiated with tπmethylolpropane and containing 99 moles of propylene oxide and 24 moles of ethylene oxide per mole of tnmethylolpropane.

Suitable for use as LFNI in the ADD compositions are those LFNI having relatively low cloud points and high hydrophilic-hpophilic balance (HLB). Cloud points of 1% solutions in water are typically below about 32°C and preferably lower, e.g., 10°C, for optimum control of sudsmg throughout a full range of water temperatures.

LFNIs which may also be used include those POLY-TERGENT® SLF-18 nonionic surfactants from Olm Corp., and any biodegradable LFNI having the melting point properties discussed hereinabove.

These and other nonionic surfactants are well known m the art, being descnbed in more detail in Kirk Othmer's Encyclopedia of Chemical Technology, 3rd Ed., Vol. 22, pp. 360-379, "Surfactants and Detersive Systems", incorporated by reference herein.

Preferred are ADD compositions compnsmg mixed surfactants wherein the sudsmg (absent any silicone suds controlling agent) is less than 2 inches, preferably less than 1 inch, as determined by the disclosure below.

The equipment useful for these measurements are: a Whirlpool Dishwasher (model 900) equipped with clear plexiglass door, IBM computer data collection with Labview and Excel Software, proximity sensor (Newark Corp - model 95F5203) using SCXI interface, and a plastic ruler. The data is collected as follows. The proximity sensor is affixed to the bottom dishwasher rack on a metal bracket. The sensor faces downward toward the rotating dishwasher arm on the bottom of the machine (distance approximately 2 cm. from the rotating arm). Each pass of the rotating arm is measured by the proximity sensor and recorded. The pulses recorded by the computer are converted to rotations per mmute (RPM) of the bottom arm by counting pulses over a 30 second interval. The rate of the arm rotation is directly proportional to the amount of suds in the machine and in the dishwasher pump (i.e., the more suds produced, the slower the arm rotation).

The plastic ruler is clipped to the bottom rack of the dishwasher and extends to the floor of the machine. At the end of the wash cycle, the height of the suds is measured using the plastic ruler (viewed through the clear door) and recorded as suds height.

The following procedure is followed for evaluating ADD compositions for suds production as well as for evaluating nonionic surfactants for utility. (For separate evaluation of nonionic surfactant, a base ADD formula, such as Cascade powder, is used along with the nonionic surfactants which are added separately m glass vials to the dishwashing machine.) First, the machine is filled with water (adjust water for appropnate temperature and hardness) and proceed through a nnse cycle. The RPM is monitored throughout the cycle (approximately 2 mm.) without any ADD product (or surfactants) being added (a quality control check to ensure the machine is functioning properly). As the machine begins to fill for the wash cycle, the water is again adjusted for temperature and hardness, and then the ADD product is added to the bottom of the machine (in the case of separately evaluated surfactants, the ADD base formula is first added to the bottom of the machine then the surfactants are added by placing the surfactant-contammg glass vials inverted on the top rack of the machine). The RPM is then monitored throughout the wash cycle. At the end of the wash cycle, the suds height is recorded using the plastic ruler. The machine is again filled with water (adjust water for appropnate temperature and hardness) and runs through another nnse cycle. The RPM is monitored throughout this cycle.

An average RPM is calculated for the 1st nnse, mam wash, and final nnse. The % RPM efficiency is then calculated by dividing the average RPM for the test surfactants into the average RPM for the control system (base ADD formulation without the nonionic surfactant). The RPM efficiency and suds height measurements are used to dimension the overall suds profile of the surfactant.

Nonionic ethoxylated alcohol surfactant - The alkyl ethoxylate condensation products of aliphatic alcohols with from 1 to 25 moles of ethylene oxide are suitable for use herein. The alkyl chain of the aliphatic alcohol can either be straight or branched, pnmary or secondary, and generally contains from 6 to 22 carbon atoms. Particularly preferred are the condensation products of alcohols having an alkyl group containing from 8 to 20 carbon atoms with from 2 to 10 moles of ethylene oxide per mole of alcohol

End-capped alkyl alkoxylate surfactant - A suitable endcapped alkyl alkoxylate surfactant is the epoxy-capped poly(oxyalkylated) alcohols represented by the formula.

R₁0[CH₂CH(CH3)0]_x[CH₂CH2θ]_y[CH2CH(OH)R2] (I)

wherein Ri is a linear or branched, aliphatic hydrocarbon radical having from 4 to 18 carbon atoms; R2 is a linear or branched aliphatic hydrocarbon radical having from 2 to 26 carbon atoms; x is an integer having an average value of from 0 5 to 1.5, more preferably 1 ; and y is an integer having a value of at least 15, more preferably at least 20.

Preferably, the surfactant of formula I, at least 10 carbon atoms in the terminal epoxide unit [CH2CH(OH)R2]. Suitable surfactants of formula I, according to the present invention, are

Ohn Corporation's POLY-TERGENT® SLF-18B nonionic surfactants, as descnbed, for example, in WO 94/22800, published October 13, 1994 by Ohn Corporation.

Ether-capped ρoly(oxyalkylated) alcohols - Preferred surfactants for use herein include ether- capped poly(oxyalkylated) alcohols having the formula:

R¹0[CH₂CH(R³)0]_x[CH₂]kCH(OH)[CH2]_JOR²

wherein R¹ and R² are lmear or branched, saturated or unsaturated, aliphatic or aromatic hydrocarbon radicals having from 1 to 30 carbon atoms; R³ is H, or a linear aliphatic hydrocarbon radical having from 1 to 4 carbon atoms, x is an mteger having an average value from 1 to 30, wherein when x is 2 or greater R³ may be the same or different and k and j are integers having an average value of from 1 to 12, and more preferably 1 to 5.

R¹ and R² are preferably linear or branched, saturated or unsaturated, aliphatic or aromatic hydrocarbon radicals having from 6 to 22 carbon atoms with 8 to 18 carbon atoms being most preferred. H or a linear aliphatic hydrocarbon radical having from 1 to 2 carbon atoms is most preferred for R³ Preferably, x is an integer having an average value of from 1 to 20, more preferably from 6 to 15.

As descnbed above, when, in the preferred embodiments, and x is greater than 2, R³ may be the same or different That is, R³ may vary between any of the alklyeneoxy units as descnbed above For instance, if x is 3, R³may be selected to form ethlyeneoxy(EO) or propyleneoxy(PO) and may vary in order of (EO)(PO)(EO), (EO)(EO)(PO), (EO)(EO)(EO), (PO)(EO)(PO), (PO)(PO)(EO) and (PO)(PO)(PO) Of course, the integer three is chosen for example only and the variation may be much larger with a higher integer value for x and include, for example, multiple (EO) units and a much small number of (PO) units.

Particularly preferred surfactants as descnbed above include those that have a low cloud point of less than 20°C. These low cloud point surfactants may then be employed in con_junction with a high cloud point surfactant as descnbed in detail below for supenor grease cleaning benefits.

Most preferred ether-capped poly(oxyalkylated) alcohol surfactants are those wherein k is 1 andj is 1 so that the surfactants have the formula:

R¹0[CH₂CH(R )0]_xCH₂CH(OH)CH₂OR²

where Rs R² and R³ are defined as above and x is an integer with an average value of from 1 to 30, preferably from 1 to 20, and even more preferably from 6 to 18 Most preferred are surfactants wherein R^ and R² range from 9 to 14, R³ is H forming ethyleneoxy and x ranges

The ether-capped poly(oxyalkylated) alcohol surfactants compnse three general components, namely a linear or branched alcohol, an alkylene oxide and an alkyl ether end cap. The alkyl ether end cap and the alcohol serve as a hydrophobic, oil-soluble portion of the molecule while the alkylene oxide group forms the hydrophilic, water-soluble portion of the molecule.

These surfactants exhibit significant improvements m spotting and filming charactenstics and removal of greasy soils, when used conjunction with high cloud point surfactants, relative to conventional surfactants.

Generally speaking, the ether-capped poly(oxyalkylene) alcohol surfactants of the present invention may be produced by reacting an aliphatic alcohol with an epoxide to form an ether which is then reacted with a base to form a second epoxide. The second epoxide is then reacted with an alkoxylated alcohol to form the novel compounds of the present invention. Examples of methods of prepaπng the ether-capped poly(oxyalkylated) alcohol surfactants are descnbed below:

A Cp/ii fatty alcohol (100.00 g, 0.515 mol.) and tm

(IV) chlonde (0.58 g, 2.23 mmol, available from Aldπch) are combined m a 500 mL three-necked round-bottomed flask fitted with a condenser, argon inlet, addition funnel, magnetic stirrer and internal temperature probe. The mixture is heated to 60 °C. Epichlorhydπn (47 70 g, 0.515 mol, available from Aldπch) is added dropwise so as to keep the temperature between 60-65 °C After stimng an additional hour at 60 °C, the mixture is cooled to room temperature. The mixture is treated with a 50% solution of sodium hydroxide (61.80 g, 0.773 mol, 50%) while being stirred mechanically. After addition is completed, the mixture is heated to 90 °C for 1.5 h, cooled, and filtered with the aid of ethanol. The filtrate is separated and the organic phase is washed with water (100 mL), dπed over MgSO filtered, and concentrated. Distillation of the oil at 100-120

°C (0.1 mm Hg) providing the glycidyl ether as an oil Pre^paration of Ci 2/14 alleyl-Coyi i ether capped alcohol surfactant - Neodol® 91 -8 (20.60 g,

0.0393 mol ethoxylated alcohol available from the Shell chemical Co.) and tin (IV) chloπde (0 58 g, 2.23 mmol) are combined in a 250 mL three-necked round-bottomed flask fitted with a condenser, argon mlet, addition funnel, magnetic stirrer and internal temperature probe. The mixture is heated to 60 °C at which point C12/14 alkyl glycidyl ether (11.00 g, 0.0393 mol) is added dropwise over 15 min. After stimng for 18 h at 60 °C, the mixture is cooled to room temperature and dissolved m an equal portion of dichloromethane. The solution is passed through a 1 inch pad of silica gel while elutmg with dichloromethane. The filtrate is concentrated by rotary evaporation and then stπpped in a kugelrohr oven (100 °C, 0.5 mm Hg) to yield the surfactant as an oil. For more details on these and other suitable nonionic surfactants see U.S. Patent Seπal

Nos. 60/054,702 (Docket No. 6781P), 60/054,688 (Docket No. 6779P) and 60/057,025 (Docket

No. 6780P) all of which are incorporated herem by reference.

Nonionic ethoxylated propoxylated fatty alcohol surfactant - The ethoxylated C5-C1 g fatty alcohols and Cg-C_j mixed ethoxylated/propoxylated fatty alcohols are suitable surfactants for use herein, particularly where water soluble. Preferably the ethoxylated fatty alcohols are the C JQ-CI g ethoxylated fatty alcohols with a degree of ethoxylation of from 3 to 50, most preferably these are the C^-C_jg ethoxylated fatty alcohols with a degree of ethoxylation from 3 to 40 Preferably the mixed ethoxylated/propoxylated fatty alcohols have an alkyl chain length of from 10 to 18 carbon atoms, a degree of ethoxylation of from 3 to 30 and a degree of propoxylation of from 1 to 10.

Nonionic EO/PO condensates with propylene glycol - The condensation products of ethylene oxide with a hydrophobic base formed by the condensation of propylene oxide with propylene glycol are suitable for use herein. The hydrophobic portion of these compounds preferably has a molecular weight of from 1500 to 1800 and exhibits water insolubility. Examples of compounds of this type include certain of the commercially-available PluronicTM surfactants, marketed by BASF.

Nonionic EO condensation products with propylene oxide/ethylene diam e adducts - The condensation products of ethylene oxide with the product resulting from the reaction of propylene oxide and ethylenediamme are suitable for use herein. The hydrophobic moiety of these products consists of the reaction product of ethylenediamme and excess propylene oxide, and generally has a molecular weight of from 2500 to 3000. Examples of this type of nonionic surfactant include certain of the commercially available Tetromc™ compounds, marketed by BASF.

Mixed Nonionic Surfactant System - In a preferred embodiment of the present invention the detergent tablet compnses a mixed nonionic surfactant system compnsmg at least one low cloud point nonionic surfactant and at least one high cloud point nonionic surfactant.

"Cloud point", as used herein, is a well known property of nonionic surfactants which is the result of the surfactant becoming less soluble with increasing temperature, the temperature at which the appearance of a second phase is observable is referred to as the "cloud point" (See Kirk Oth er's Encyclopedia of Chemical Technology, 3 Ed. Vol. 22, pp. 360-379). As used herein, a "low cloud point" nonionic surfactant is defined as a nonionic surfactant system ingredient having a cloud point of less than 30°C, preferably less than 20°C, and most preferably less than 10°C. Typical low cloud point nonionic surfactants include nonionic alkoxylated surfactants, especially ethoxylates denved from pnmary alcohol, and polyoxypropylene/polyoxyethylene/polyoxypropylene (PO/EO/PO) reverse block polymers. Also, such low cloud point nonionic surfactants mclude, for example, ethoxylated-propoxylated alcohol (e.g., Ohn Corporation's Poly-Tergent® SLF18), epoxy-capped poly(oxyalkylated) alcohols (e.g., O n Corporation's Poly-Tergent® SLF18B senes of noniomcs, as descnbed, for example, in WO 94/22800, published October 13, 1994 by Olin Corporatιon)and the ether- capped poly(oxyalkylated) alcohol surfactants. Nonionic surfactants can optionally contain propylene oxide in an amount up to 15% by weight. Other preferred nonionic surfactants can be prepared by the processes descnbed m U.S. Patent 4,223,163, issued September 16, 1980, Builloty, incorporated herein by reference.

Low cloud point nonionic surfactants additionally compnse a polyoxyethylene, polyoxypropylene block polymenc compound. Block polyoxyethylene-polyoxypropylene polymenc compounds mclude those based on ethylene glycol, propylene glycol, glycerol, tnmethylolpropane and ethylenediamme as initiator reactive hydrogen compound. Certain of the block polymer surfactant compounds designated PLURONIC®, REVERSED PLURONIC®, and TETRONIC® by the BASF-Wyandotte Corp., Wyandotte, Michigan, are suitable m ADD compositions of the invention. Preferred examples include REVERSED PLURONIC® 25R2 and TETRONIC® 702, Such surfactants are typically useful herein as low cloud point nonionic surfactants.

As used herein, a "high cloud point" nonionic surfactant is defined as a nonionic surfactant system ingredient having a cloud point of greater than 40°C, preferably greater than 50°C, and more preferably greater than 60°C Preferably the nonionic surfactant system compπses an ethoxylated surfactant deπved from the reaction of a monohydroxy alcohol or alkylphenol containing from 8 to 20 carbon atoms, with from 6 to 15 moles of ethylene oxide per mole of alcohol or alkyl phenol on an average basis. Such high cloud point nonionic surfactants include, for example, Tergitol 15S9 (supplied by Union Carbide), Rhodasurf TMD

8.5 (supplied by Rhone Poulenc), and Neodol 91-8 (supplied by Shell).

It is also preferred for purposes of the present invention that the high cloud point nonionic surfactant further have a hydrophile- pophile balance ("HLB", see Kirk Othmer hereinbefore) value withm the range of from 9 to 15, preferably 11 to 15. Such mateπals include, for example, Tergitol 15S9 (supplied by Union Carbide), Rhodasurf TMD 8.5 (supplied by Rhone Poulenc), and Neodol 91-8 (supplied by Shell).

Another preferred high cloud point nonionic surfactant is deπved from a straight or preferably branched chain or secondary fatty alcohol containing from 6 to 20 carbon atoms (Cg-

C20 alcohol), including secondary alcohols and branched chain pnmary alcohols. Preferably, high cloud point nonionic surfactants are branched or secondary alcohol ethoxylates, more preferably mixed C9/11 or CI 1/15 branched alcohol ethoxylates, condensed with an average of from 6 to 15 moles, preferably from 6 to 12 moles, and most preferably from 6 to 9 moles of ethylene oxide per mole of alcohol. Preferably the ethoxylated nonionic surfactant so denved has a narrow ethoxylate distπbution relative to the average.

In a preferred embodiment the detergent tablet compnsmg such a mixed surfactant system also compπses an amount of water-soluble salt to provide conductivity m deiomsed water measured at 25°C greater than 3 mil Siemens/cm, preferably greater than 4 milh Siemens/cm, most preferably greater than 4.5 milh Siemens/cm as descnbed in co-pending GB Patent

Application (attorney docket number CM 1573F).

In another preferred embodiment the mixed surfactant system dissolves m water having a hardness of 1.246mmol L m any suitable cold-fill automatic dishwasher to provide a solution

2 with a surface tension of less than 4 Dynes/cm at less than 45°C, preferably less than 40°C, most preferably less than 35°C as descnbed in co-pending U.S. Patent Application (attorney docket number 6252).

In another preferred embodiment the high cloud point and low cloud point surfactants of the mixed surfactant system are separated such that one of either the high cloud point or low cloud point surfactants is present in a first matrix and the other is present in a second matnx as descnbed in co-pending U.S Patent Application (attorney docket number 6252). For the purposes of the present invention, the first matnx may be a first particulate and the second matrix may be a second particulate. A surfactant may be applied to a particulate by any suitable known method, preferably the surfactant is sprayed onto the particulate. In a preferred aspect the first matnx is the compressed portion and the second matnx is the non-compressed portion of the detergent tablet of the present invention. Preferably the low cloud point surfactant is present in the compressed portion and the high cloud point surfactant is present m the non-compressed portion of the detergent tablet of the present invention.

Branched alkyl alkoxylate surfactants - Also suitable are the branched nonionic surfactants disclosed in co-pending U.S. patent application senal number 60/031,917 (Docket No. 6404) all of which is incorporated herein by reference. These branched nonionic surfactants show, some in applications, improved spotting and filming benefits over conventional linear surfactants. Other Nonionic Surfactants - Polyethylene, polypropylene, and polybutylene oxide condensates of alkyl phenols are suitable for use as the nonionic surfactant of the surfactant systems of the present invention, with the polyethylene oxide condensates being preferred. Commercially available nonionic surfactants of this type mclude Igepal™ CO-630, marketed by the GAF

Corporation; and Tnton™ X-45, X-l 14, X-100 and X-102, all marketed by the Rohm & Haas Company. These surfactants are commonly referred to as alkylphenol alkoxylates (e.g., alkyl phenol ethoxylates).

The condensation products of pnmary and secondary aliphatic alcohols with from about 1 to about 25 moles of ethylene oxide are suitable for use as the nonionic surfactant of the nonionic surfactant systems of the present invention. Examples of commercially available nonionic surfactants of this type include Tergitol™ 15-S-9 (the condensation product of Ci 1 - Ci 5 linear alcohol with 9 moles ethylene oxide), Tergitol™ 24-L-6 NMW (the condensation product of C₁2-C₁4 pnmary alcohol with 6 moles ethylene oxide with a narrow molecular weight dis_tribution), both marketed by Union Carbide Corporation; Neodol™ 45-9 (the condensation product of C₁4-C15 linear alcohol with 9 moles of ethylene oxide), Neodol™ 23-3 (the condensation product of C12-C13 linear alcohol with 3.0 moles of ethylene oxide), Neodol™ 45-7 (the condensation product of C14-C15 linear alcohol with 7 moles of ethylene oxide), Neodol™ 45-5 (the condensation product of C14-C15 linear alcohol with 5 moles of ethylene oxide) marketed by Shell Chemical Company, Kyro™ EOB (the condensation product of C13- C₁5 alcohol with 9 moles ethylene oxide), marketed by The Procter & Gamble Company, and Genapol LA 030 or 050 (the condensation product of C12-C14 alcohol with 3 or 5 moles of ethylene oxide) marketed by Hoechst.

Also useful as the nonionic surfactant of the surfactant systems of the present invention are the alkylpolysacchandes, especially alkylpolyglycosides, disclosed m U.S. Patent 4,565,647, Llenado, issued January 21, 1986, having a hydrophobic group containing from about 6 to about 30 carbon atoms, preferably from about 10 to about 16 carbon atoms and a polysacchande

The preferred alkylpolyglycosides have the formula

R2θ(C_nH_2nO)_t(glycosyl)_x wherein R² is selected from the group consisting of alkyl, alkylphenyl, hydroxyalkyl, hydroxyalkylphenyl, and mixtures thereof in which the alkyl groups contain from about 10 to about 18. preferably from about 12 to about 14, carbon atoms; n is 2 or 3, preferably 2, t is from 0 to about 10, preferably 0; and x is from about 1.3 to about 10, preferably from about 1.3 to about 3, most preferably from about 1.3 to about 2.1. The glycosyl is preferably denved from glucose. To prepare these compounds, the alcohol or alkylpolyethoxy alcohol is formed first and then reacted with glucose, or a source of glucose, to form the glucoside (attachment at the 1 -position) The additional glycosyl units can then be attached between their 1 -position and the preceding glycosyl units 2-, 3-, 4- and/or 6-posιtιon, preferably predominately the 2-posιtιon. The condensation products of ethylene oxide with a hydrophobic base formed by the condensation of propylene oxide with propylene glycol are also suitable for use as the additional nonionic surfactant systems of the present invention. Examples of compounds of this type include certain of the commercially-available PlurafacT LF404 and PluronicTM surfactants, marketed by BASF. Also suitable for use as the nonionic surfactant of the nonionic surfactant system of the present invention, are the condensation products of ethylene oxide with the product resulting from the reaction of propylene oxide and ethylenediamme. Examples of this type of nonionic surfactant include certain of the commercially available TetronicTM compounds, marketed by BASF. Polyethylene oxide condensates of alkyl phenols, condensation products of pnmary and secondary aliphatic alcohols with from about 1 to about 25 moles of ethylene oxide, alkylpolysacchandes, and mixtures thereof.

Polyhydroxy fatty acid amide surfactants of the formula: R² - C(0) - N(R¹) - Z, wherein R¹ is H, or R¹ is C1-4 hydrocarbyl, 2-hydroxy ethyl, 2-hydroxy propyl or a mixture thereof, R² is C5.31 hydrocarbyl, and Z is a polyhydroxyhydrocarbyl having a linear hydrocarbyl chain with at least 3 hydroxyls directly connected to the chain, or an alkoxylated deπvative thereof can also be used in the present invention. Preferably, R¹ is methyl, R² is a straight C\ \. 15 alkyl or C _\ alkyl or alkenyl chain such as coconut alkyl or mixtures thereof, and Z is denved from a reducing sugar such as glucose, fructose, maltose, lactose, in a reductive animation reaction.

Anionic Surfactants - Suitable anionic surfactants to be used are linear alkyl benzene sulfonate, alkyl ester sulfonate surfactants including linear esters of Cg-C20 carboxylic acids (i.e., fatty acids) which are sulfonated with gaseous SO3 according to "The Journal of the Amencan Oil Chemists Society", 52 (1975), pp. 323-329. Suitable starting mateπals would include natural fatty substances as deπved from tallow, palm oil, etc. Other suitable anionic surfactants include the alkyl sulfate surfactants which are water soluble salts or acids of the formula ROSO3M wherein R preferably is a C10-C24 hydrocarbyl, preferably an alkyl or hydroxyalkyl having a Ci 0-C20 ^alkyl component, more preferably a C_j2- Cjg alkyl or hydroxyalkyl, and M is H or a cation, e.g., an alkali metal cation (e.g. sodium, potassium, lithium), or ammonium or substituted ammonium (e.g. methyl-, dimethyl-, and tnmethyl ammonium cations and quaternary ammonium cations such as tetramethyl-ammomum and dimethyl piperdmium cations and quaternary ammonium cations denved from alkylamines such as ethylamme, diethylamme, triethylamine, and mixtures thereof, and the like). Typically, alkyl chains of C12-C1 g are preferred for lower wash temperatures (e.g. below about 50°C) and Ci6_ι g alkyl chains are preferred for higher wash temperatures (e.g. above about 50°C).

Other anionic surfactants useful for detersive purposes can also be included in the cleaning compositions of the present invention. These can include salts (including, for example, sodium, potassium, ammonium, and substituted ammonium salts such as mono-, di- and tπethanolamme salts) of soap, Cg-C22 pnmary of secondary alkanesulfonates, Cg-C24 olefinsulfonates, sulfonated polycarboxyhc acids prepared by sulfonation of the pyrolyzed product of alkaline earth metal citrates, e.g., as descnbed in Bπtish patent specification No. 1,082,179, Cg-C24 alkylpolyglycolethersulfates (containing up to 10 moles ofethylene oxide); alkyl glycerol suifonates, fatty acyl glycerol suifonates, fatty oleyl glycerol sulfates, alkyl phenol ethylene oxide ether sulfates, paraffin suifonates, alkyl phosphates, isethionates such as the acyl isethionates, N-acyl taurates, alkyl succma ates and sulfosuccinates, monoesters of sulfosuccinates (especially saturated and unsaturated C12-C1 g monoesters) and diesters of sulfosuccinates (especially saturated and unsaturated Cg-Ci2 diesters), acyl sarcosinates, sulfates of alkylpolysacchaπdes such as the sulfates of alkylpolyglucoside (the nonionic nonsulfated compounds being descnbed below), branched pnmary alkyl sulfates, and alkyl polyethoxy carboxylates such as those of the formula RO^^C^O^-C^COO-M wherein R is a Cg- C22 alkyl, k is an mteger from 1 to 10, and M is a soluble salt-forming cation. Res acids and hydrogenated resin acids are also suitable, such as rosin, hydrogenated rosm, and resm acids and hydrogenated resm acids present in or deπved from tall oil.

Further examples are descnbed in "Surface Active Agents and Detergents" (Vol. I and EJ by Schwartz, Perry and Berch). A vanety of such surfactants are also generally disclosed in U.S. Patent 3,929,678, issued December 30, 1975 to Laughlm, et al. at Column 23, line 58 through Column 29, line 23 (herein incorporated by reference).

When included therein, the cleaning compositions of the present invention typically compnse from about 1%, preferably from about 3% to about 40%, preferably about 20% by weight of such anionic surfactants. Highly preferred anionic surfactants include alkyl alkoxylated sulfate surfactants hereof are water soluble salts or acids of the formula RO(A)_mS03M wherein R is an unsubstituted C \Q- C24 alkyl or hydroxyalkyl group having a C10-C24 alkyl component, preferably a C12-C20 alkyl or hydroxyalkyl, more preferably C12- 1 g alkyl or hydroxyalkyl, A is an ethoxy or propoxy unit, m is greater than zero, typically between about 0.5 and about 6, more preferably between about 0.5 and about 3, and M is H or a cation which can be, for example, a metal cation (e.g., sodium, potassium, lithium, calcium, magnesium, etc.), ammonium or substituted-ammomum cation Alkyl ethoxylated sulfates as well as alkyl propoxylated sulfates are contemplated herein. Specific examples of substituted ammonium cations include methyl-, dimethyl, tπmethyl- ammonium cations and quaternary ammonium cations such as tetramethyl-ammonium and dimethyl p perdinium cations and those deπved from alkylamines such as ethylamme, diethylamine, tπethylamme, mixtures thereof, and the like. Exemplary surfactants are C12-C1 g alkyl polyethoxylate (1 0) sulfate (C₁₂-Cι E(1.0)M), C^-Ci alkyl polyethoxylate (2.25) sulfate (Cι ₂-Cι gE(2.25)M), C^-C_jg alkyl polyethoxylate (3.0) sulfate (Cι₂- E(3.0)M), and C 12-C 1 g alkyl polyethoxylate (4 0) sulfate (C 12-C 1 gE(4.0)M), wherein M is conveniently selected from sodium and potassium.

Other Surfactants - The cleaning compositions of the present invention may also contain cationic, ampholytic, zwittenomc, and semi-polar surfactants, as well as the nonionic and or anionic surfactants other than those already descnbed herein. Cationic detersive surfactants suitable for use m the cleaning compositions of the present invention are those having one long-chain hydrocarbyl group. Examples of such cationic surfactants include the ammonium surfactants such as alkyltnmethylammonium halogenides, and those surfactants having the formula ^•

[R²(OR³)_y][R⁴(OR³)_y]₂R⁵N+X-

wherem R² is an alkyl or alkyl benzyl group having from about 8 to about 18 carbon atoms in the alkyl chain, each R³ is selected from the group consisting of -CH2CH2-, -CH2CH(CH3)-, - CH2CH(CH2θH)-, -CH2CH2CH2-, and mixtures thereof; each R⁴ is selected from the group consisting of C ₁ -C4 alkyl, C 1 -C4 hydroxyalkyl, benzyl nng structures formed by j ommg the two R⁴ groups, -CH2CHOH-CHOHCOR°CHOHCH2θH wherein R⁶ is any hexose or hexose polymer having a molecular weight less than about 1000, and hydrogen when y is not 0, R⁵ is the same as R⁴ or is an alkyl chain wherein the total number of carbon atoms of R² plus R⁵ is not more than about 18; each y is from 0 to about 10 and the sum of the y values is from 0 to about 15; and X is any compatible anion.

Quaternary ammonium surfactant suitable for the present invention has the formula (I)

SUBSTΓΓUTE SHEET (RULE 26)

Formula I wherein RI is a short chamlength alkyl (C6-C 10) or alkylarmdoalkyl of the formula (II)

Formula II

y is 2-4, preferably 3; wherein R2 is H or a C1-C3 alkyl, wherein x is 0-4, preferably 0-2, most preferably 0, wherein R3, R4 and R5 are either the same or different and can be either a short chain alkyl (C1-C3) or alkoxylated alkyl of the formula III,

Formula JH R6 is C1 -C4 and z is 1 or 2; wherein X" is a countenon, preferably a halide, e.g. chlonde or methylsulfate.

Preferred quat ammonium surfactants are those as defined in formula I whereby R\ is Cg, Ci 0 or mixtures thereof, x=o, R3, R4 = CH3 and R5 = CH2CH2OH.

Highly preferred cationic surfactants are the water-soluble quaternary ammonium compounds useful in the present composition having the formula (1):

R₁R₂R3R N⁺X- (i)

wherein Ri is Cg-Ci g alkyl, each of R , R3 and R4 is independently C \ -C4 alkyl, C1-C4 hydroxy alkyl, benzyl, and -(C2H4Q)_XH where x has a value from 2 to 5, and X is an anion. Not more than one of R2, R3 or R4 should be benzyl. The preferred alkyl chain length for Rj is C12- Ci 5 particularly where the alkyl group is a mixture of chain lengths deπved from coconut or palm kernel fat or is denved synthetically by olefin build up or OXO alcohols synthesis. Preferred groups for R2R3 and R4 are methyl and hydroxyethyl groups and the anion X may be selected from hahde, methosulfate, acetate and phosphate. Other cationic surfactants useful herein are also descnbed m U S. Patent 4,228,044, Cambre, issued October 14, 1980 and m European Patent Application EP 000,224.

When included therein, the cleaning compositions of the present invention typically comprise from about 0.2%, preferably from about 1% to about 25%, preferably to about 8% by weight of such cationic surfactants.

Ampholytic surfactants are also suitable for use m the cleaning compositions of the present invention. These surfactants can be broadly descnbed as aliphatic denvatives of secondary or tertiary amines, or aliphatic denvatives of heterocychc secondary and tertiary amines in which the aliphatic radical can be straight- or branched-cham. One of the aliphatic substituents contains at least about 8 carbon atoms, typically from about 8 to about 18 carbon atoms, and at least one contains an anionic water-solubi zmg group, e.g. carboxy, sulfonate, sulfate. See U.S. Patent No. 3,929,678 to Laughlm et al., issued December 30, 1975 at column 19, lines 18-35, for examples of ampholytic surfactants.

When included therein, the cleaning compositions of the present invention typically compnse from about 0.2%, preferably from about 1% to about 15%, preferably to about 10% by weight of such ampholytic surfactants.

Zwittenomc surfactants are also suitable for use in cleaning compositions. These surfactants can be broadly descnbed as denvatives of secondary and tertiary amines, denvatives of heterocychc secondary and tertiary amines, or denvatives of quaternary ammonium, quaternary phosphomum or tertiary sulfomum compounds. See U.S. Patent No. 3,929,678 to

Laughlm et al., issued December 30, 1975 at column 19, line 38 through column 22, line 48, for examples of zwittenomc surfactants.

When included therein, the cleaning compositions of the present invention typically compnse from about 0.2%, preferably from about 1% to about 15%, preferably to about 10% by weight of such zwittenomc surfactants.

Semi-polar nonionic surfactants are a special category of nonionic surfactants which include water-soluble amme oxides containing one alkyl moiety of from about 10 to about 18 carbon atoms and 2 moieties selected from the group consisting of alkyl groups and hydroxyalkyl groups containing from about 1 to about 3 carbon atoms; water-soluble phosphine oxides containing one alkyl moiety of from about 10 to about 18 carbon atoms and 2 moieties selected from the group consisting of alkyl groups and hydroxyalkyl groups containing from about 1 to about 3 carbon atoms; and water-soluble sulfoxides containing one alkyl moiety of from about 10 to about 18 carbon atoms and a moiety selected from the group consisting of alkyl and hydroxyalkyl moieties of from about 1 to about 3 carbon atoms. Semi-polar nonionic detergent surfactants mclude the am e oxide surfactants having the formula O

R³(OR⁴) N(R⁵)₂ wherein R³ is an alkyl, hydroxyalkyl, or alkyl phenyl group or mixtures therof containing from about 8 to about 22 carbon atoms; R⁴ is an alkylene or hydroxyalkylene group containing from about 2 to about 3 carbon atoms or mixtures thereof; x is from 0 to about 3; and each R^ is an alkyl or hydroxyalkyl group containing from about 1 to about 3 carbon atoms or a polyethylene oxide group containing from about 1 to about 3 ethylene oxide groups. The R^ groups can be attached to each other, e.g., through an oxygen or nitrogen atom, to form a nng structure. These amme oxide surfactants in particular include C 1 Q-C I g alkyl dimethyl amme oxides and C -Ci2 alkoxy ethyl dihydroxy ethyl amme oxides.

When included therein, the cleaning compositions of the present invention typically compnse from about 0.2%, preferably from about 1% to about 15%, preferably to about 10% by weight of such semi-polar nonionic surfactants. The cleaning compositions of the present invention may further compnse a cosurfactant selected from the group of pnmary or tertiary amines. Suitable pnmary ammes for use herein include amines according to the formula R2-NH2 wherein Rj is a Cg-C^, preferably Cg-Cjo alkyl chain or R4X(CH2)_n, X is -0-,-C(0)NH- or -NH-_> R4 is a Cg-C^ alkyl chain n is between 1 to 5, preferably 3. R\ alkyl chains may be straight or branched and may be interrupted with up to 12, preferably less than 5 ethylene oxide moieties.

Preferred am es according to the formula herein above are n-alkyl amines. Suitable ammes for use herein may be selected from 1 -hexylam e, 1-octylamme, 1-decylamιne and laurylam e. Other preferred pnmary amines include C8-C10 oxypropylamine, octyloxypropylamme, 2-ethylhexyl-oxypropylamme, lauryl amido propylamine and amido propylamine.

Suitable tertiary ammes for use herein include tertiary amines having the formula R1R2R3N wherein RI and R2 are -Cg alky -chains or

— ( CH₂— CH θ )χH

R3 is either a C^-C^ preferably Cg-Cjo alkyl chain, or R3 is 4X(CH2)_n, whereby X is -0-, - C(0)NH- or -NH- R4 is a C4-C12, ^{n 1S} between 1 to 5, preferably 2-3. R5 is H or Cι-C₂ alkyl and x is between 1 to 6 .

R3 and R4 may be linear or branched , R3 alkyl chains may be interrupted with up to 12, preferably less than 5, ethylene oxide moieties.

Preferred tertiary ammes are Ri R2R3N where RI is a C6-C12 alkyl chain, R2 and R3 are C1-C3 alkyl or R₅

— ( cH₂— CH θ )χ_;H where R5 is H or CH3 and x = 1-2.

Also preferred are the amidoamines of the formula:

wherein R is Cg-C^ alkyl; n is 2-4, preferably n is 3; R2 and R3 is Ci -C4.

Most preferred ammes of the present invention include 1-octylamme, 1 -hexylamme, 1- decylamine, l-dodecylamme,C8-10oxypropylamιne, N coco l-3dιammopropane, coconutalkyldimethylamme, lauryldimethylamine, lauryl bιs(hydroxyethyl)amme, coco bis(hydroxyehtyl)amme, lauryl amme 2 moles propoxylated, octyl amine 2 moles propoxylated, lauryl amidopropyi-dimethylamine, C8-10 amidopropyldimethylamme and CIO amidopropyl- dimethylam e.

The most preferred ammes for use m the compositions herein are 1 -hexylamme, 1 - octylamme, 1-decylamme, 1-dodecylamιne. Especially desirable are n-dodecyldimethylamine and bishydroxyethylcoconutalkylamme and oleylamme 7 times ethoxylated, lauryl amido propylamine and cocoamido propylamine.

Bleaching System - The cleaning compositions of the present invention preferably compnse a bleaching system. Bleaching systems typically compnse a "bleaching agent" (source of hydrogen peroxide) and an "initiator" or "catalyst". When present, bleaching agents will typically be at levels of from about 1%, preferably from about 5% to about 30%, preferably to about 20% by weight of the composition. If present, the amount of bleach activator will typically be from about 0.1%, preferably from about 0.5% to about 60%, preferably to about 40% by weight, of the bleaching composition compnsmg the bleaching agent-plus-bleach activator. Bleaching System - The cleaning compositions of the present invention preferably compnse a bleaching system. Bleaching systems typically compnse a "bleachmg agent" (source of hydrogen peroxide) and an "initiator" or "catalyst". When present, bleaching agents will typically be at levels of from about 1%, preferably from about 5% to about 30%, preferably to about 20% by weight of the composition. If present, the amount of bleach activator will typically be from about 0.1%), preferably from about 0.5% to about 60%, preferably to about 40% by weight, of the bleaching composition compnsmg the bleaching agent-plus-bleach activator.

Bleaching Agents - Hydrogen peroxide sources are descnbed in detail m the herein incorporated Kirk Othmer's Encyclopedia of Chemical Technology, 4th Ed (1992, John Wiley & Sons), Vol. 4, pp. 271-300 "Bleaching Agents (Survey)", and include the various forms of sodium perborate and sodium percarbonate, including vaπous coated and modified forms.

The preferred source of hydrogen peroxide used herein can be any convenient source, including hydrogen peroxide itself. For example, perborate, e.g., sodium perborate (any hydrate but preferably the mono- or tetra-hydrate), sodium carbonate peroxyhydrate or equivalent percarbonate salts, sodium pyrophosphate peroxyhydrate, urea peroxyhydrate, or sodium peroxide can be used herein. Also useful are sources of available oxygen such as persulfate bleach (e.g., OXONE, manufactured by DuPont). Sodium perborate monohydrate and sodium percarbonate are particularly preferred. Mixtures of any convenient hydrogen peroxide sources can also be used.

A preferred percarbonate bleach compnses dry particles having an average particle size in the range from about 500 micrometers to about 1,000 micrometers, not more than about 10% by weight of said particles being smaller than about 200 micrometers and not more than about 10% by weight of said particles being larger than about 1,250 micrometers. Optionally, the percarbonate can be coated with a silicate, borate or water-soluble surfactants. Percarbonate is available from vaπous commercial sources such as FMC, Solvay and Tokai Denka.

Compositions of the present invention may also compnse as the bleaching agent a chloπne-type bleaching mateπal. Such agents are well known in the art, and include for example sodium dichloroisocyanurate ("NaDCC"). However, chlonne-type bleaches are less preferred for compositions which compnse enzymes.

(a) Bleach Activators - Preferably, the peroxygen bleach component m the composition is formulated with an activator (peracid precursor). The activator is present at levels of from about 0.01%, preferably from about 0.5%, more preferably from about 1% to about 15%, preferably to about 10%, more preferably to about 8%, by weight of the composition. Preferred activators are selected from the group consisting of tetraacetyl ethylene diamme (TAED), benzoylcaprolactam (BzCL), 4-nιtrobenzoylcaprolactam, 3-chlorobenzoylcaprolactam, benzoyloxybenzenesulphonate (BOBS), nonanoyloxybenzenesulphonate (NOBS), phenyl benzoate (PhBz), decanoyloxybenzenesulphonate (C IQ-OBS), benzoylvalerolactam (BZVL), octanoyloxybenzenesulphonate (Cg-OBS), perhydrolyzable esters and mixtures thereof, most preferably benzoylcaprolactam and benzoylvalerolactam. Particularly preferred bleach activators in the pH range from about 8 to about 9.5 are those selected having an OBS or VL leaving group Preferred hydrophobic bleach activators include, but are not limited to, nonanoyloxybenzenesulphonate (NOBS), 4-[N-(nonaoyl) ammo hexanoyloxy] -benzene sulfonate sodium salt (NACA-OBS) an example of which is descnbed m U.S. Patent No. 5,523,434, dodecanoyloxybenzenesulphonate (LOBS or C12-OBS), 10-undecenoyloxybenzenesulfonate (UDOBS or Ci j-OBS with unsaturation in the 10 position), and decanoyloxybenzoic acid (DOBA).

Preferred bleach activators are those descnbed in U S. 5,698,504 Christie et al , issued December 16, 1997; U.S. 5,695,679 Chπstie et al. issued December 9, 1997; U.S. 5,686,401 Willey et al., issued November 1 1, 1997; U.S. 5,686,014 Hartshorn et al., issued November 1 1, 1997; U.S. 5,405,412 Willey et al., issued Apπl 11, 1995, U.S. 5,405,413 Willey et al., issued Apnl 1 1, 1995; U.S. 5,130,045 Mitchel et al., issued July 14, 1992; and U.S. 4,412,934 Chung et al, issued November 1, 1983, and copendmg patent applications U. S. Seπal Nos. 08/709,072, 08/064,564, all of which are incorporated herein by reference. The mole ratio of peroxygen bleaching compound (as AvO) to bleach activator in the present invention generally ranges from at least 1 :1, preferably from about 20: 1, more preferably from about 10.1 to about 1: 1, preferably to about 3:1.

Quaternary substituted bleach activators may also be included. The present cleaning compositions preferably compnse a quaternary substituted bleach activator (QSBA) or a quaternary substituted peracid (QSP); more preferably, the former. Preferred QSBA structures are further descnbed in U.S. 5,686,015 Willey et al., issued November 11, 1997; U.S. 5,654,421 Taylor et al., issued August 5, 1997; U.S. 5,460,747 Gosselmk et al., issued October 24, 1995; U.S. 5,584,888 Miracle et al., issued December 17, 1996; and U.S. 5,578,136 Taylor et al., issued November 26, 1996; all of which are incorporated herein by reference. Highly preferred bleach activators useful herein are amide-substituted as descnbed m

U.S. 5,698,504, U.S. 5,695,679, and U.S. 5,686,014 each of which are cited herein above. Preferred examples of such bleach activators include: (6-octanamιdocaproyl) oxybenzenesulfonate, (6-nonanamιdocaproyl)oxybenzenesulfonate, (6-decanamιdocaproyl)oxybenzenesulfonate and mixtures thereof. Other useful activators, disclosed in U.S. 5,698,504, U.S. 5,695,679, U.S. 5,686,014 each of which is cited herein above and U.S. 4,966,723Hodge et al., issued October 30, 1990, include benzoxazm-type activators, such as a CeH-t nng to which is fused in the 1,2-posιtιons a moiety -C(0)OC(R^I)=N-.

Depending on the activator and precise application, good bleaching results can be obtained from bleaching systems having with m-use pH of from about 6 to about 13, preferably from about 9.0 to about 10.5. Typically, for example, activators with electron- withdrawing moieties are used for near-neutral or sub-neutral pH ranges. Alkalis and buffenng agents can be used to secure such pH.

Acyl lactam activators, as descnbed in U.S. 5,698,504, U.S. 5,695,679 and U S. 5,686,014, each of which is cited herein above, are very useful herein, especially the acyl caprolactams (see for example WO 94-28102 A) and acyl valerolactams (see U.S. 5,503,639 Willey et al., issued Apnl 2, 1996 incorporated herein by reference).

(b) Organic Peroxides, especially Diacyl Peroxides - These are extensively illustrated m Kirk Othmer, Encyclopedia of Chemical Technology, Vol. 17, John Wiley and Sons, 1982 at pages 27-90 and especially at pages 63-72, all incorporated herein by reference. If a diacyl peroxide is used, it will preferably be one which exerts minimal adverse impact on spotting/filming.

(c Metal-contammg Bleach Catalysts - The present invention compositions and methods may utilize metal-containing bleach catalysts that are effective for use in bleaching compositions. Preferred are manganese and cobalt-containing bleach catalysts.

One type of metal-contammg bleach catalyst is a catalyst system compnsmg a transition metal cation of defined bleach catalytic activity, such as copper, iron, titanium, ruthenium tungsten, molybdenum, or manganese cations, an auxiliary metal cation having little or no bleach catalytic activity, such as zmc or aluminum cations, and a sequestrate having defined stability constants for the catalytic and auxiliary metal cations, particularly ethylenediaminetetraacetic acid, ethylenediammetetra (methylenephosphonic acid) and water-soluble salts thereof. Such catalysts are disclosed U.S. 4,430,243 Bragg, issued February 2, 1982.

Manganese Metal Complexes - If desired, the compositions herein can be catalyzed by means of a manganese compound. Such compounds and levels of use are well known m the art and include, for example, the manganese-based catalysts disclosed m U.S. Patent Nos. 5,576,282; 5,246,621; 5,244,594; 5,194,416; and 5,114,606; and European Pat. App. Pub. Nos. 549,271 Al, 549,272 Al, 544,440 A2, and 544,490 Al; Preferred examples of these catalysts include Mn^rv (^u-°)3( ^l A7-tnmethyl- 1 ,4,7-tnazacyclononane)₂(PF₆)2, Mn^m ₂(u-0) 1 (u-OAc)₂( 1 ,4,7- tπmethyl- 1 ,4,7-tπazacyclononane)2(Clθ4)2, Mn^r 4(u-0)6( 1 ,4,7-tnazacyclononane)4(Clθ4)4, Mn Mn^IV4(u-0) ι (u-0 Ac)₂.( 1 ,4,7-tπmethyl- 1 ,4,7-tnazacyclononane)₂(C10₄)₃ , Mn^w( 1 ,4,1- tπmethyl-l,4,7-tπazacyclononane)- (OC^^PFg), and mixtures thereof. Other metal-based bleach catalysts include those disclosed in U.S. Patent Nos. 4,430,243 and U.S. 5,114,611. The use of manganese with vaπous complex ligands to enhance bleach g is also reported in the following: U.S. Patent Nos. 4,728,455; 5,284,944; 5,246,612, 5,256,779; 5,280,117; 5,274,147; 5,153,161; and 5,227,084.

Cobalt Metal Complexes - Cobalt bleach catalysts useful herein are known, and are descnbed, for example, in U.S. Patent Nos. 5,597,936, 5,595,967; and 5,703,030; and M. L. Tobe, "Base Hydrolysis of Transition-Metal Complexes", Adv Inorg. Bioinorg Mech., (1983), 2, pages 1-94. The most preferred cobalt catalyst useful herein are cobalt pentaamme acetate salts having the formula [Co(NH₃)₅OAc] T_y, wherein "OAc" represents an acetate moiety and "T_y" is an anion, and especially cobalt pentaamme acetate chlonde, [Co(NH3)5θAc]Cl2; as well as [Co(NH₃)₅OAc](OAc)₂, [Co(NH₃)₅OAc](PF₆)₂, [Co(NH₃)₅OAc](S0₄), [Co- (NH₃)5θAc](BF₄)2, and [Co(NΗ3)₅OAc](N0₃)2 (herein "PAC").

These cobalt catalysts are readily prepared by known procedures, such as taught for example m U.S. Patent Nos. 5,597,936; 5,595,967; and 5,703,030; in the Tobe article and the references cited therein; and m U.S. Patent 4,810,410, J. Chem Ed. (1989), 66 (12), 1043-45, The Synthesis and Characteπzation of Inorganic Compounds, W.L. Jolly (Prentice-Hall, 1970), pp. 461-3, Inorg. Chem.. 18, 1497-1502 (1979); Inorg Chem.. 21, 2881-2885 (1982); Inorg. Chem.. 18, 2023-2025 (1979); Inorg. Synthesis, 173-176 (1960); and Journal of Physical Chemistry. 56, 22-25 (1952). Transition Metal Complexes of Macropolycychc Rigid Ligands - Compositions herein may also suitably include as bleach catalyst a transition metal complex of a macropolycychc ngid ligand. The phrase "macropolycychc πgid ligand" is sometimes abbreviated as "MRL" in discussion below. The amount used is a catalytically effective amount, suitably about 1 ppb or more, for example up to about 99.9%, more typically about 0.001 ppm or more, preferably from about 0.05 ppm to about 500 ppm (wherein "ppb" denotes parts per billion by weight and "ppm" denotes parts per million by weight).

Suitable transition metals e.g., Mn are illustrated hereinafter. "Macropolycychc" means a MRL is both a macrocycle and is polycyc c. "Polycyc c" means at least bicychc. The term "πgid" as used herein herein includes "having a superstructure" and "cross-bndged". "Rigid" has been defined as the constrained converse of flexibility: see D.H. Busch., Chemical Reviews.. (1993), 93, 847-860, incorporated by reference. More particularly, "ngid" as used herein means that the MRL must be determinably more ngid than a macrocycle ("parent macrocycle") which is otherwise identical (having the same nng size and type and number of atoms in the mam nng) but lacking a superstructure (especially linking moieties or, preferably cross-bπdgmg moieties) found m the MRL's. In determining the comparative πgidity of macrocycles with and without superstructures, the practitioner will use the free form (not the metal-bound form) of the macrocycles. Rigidity is well-known to be useful in companng macrocycles; suitable tools for determining, measuπng or companng πgidity include computational methods (see, for example, Zimmer, Chemical Reviews, (1995), 95(38), 2629-2648 or Hancock et al., Inorgamca Chimica Acta, (1989), 164, 73-84.

Preferred MRL's herein are a special type of ultra-ngid ligand which is cross-bndged. A "cross-bπdge" is nonhmitmgly illustrated m 1.11 here below. In 1.11, the cross-bndge is a -

CH2CH2- moiety. It bπdges N and N m the illustrative structure. By compaπson, a "same-

1 12 side" bndge, for example if one were to be introduced across N and N in 1.1 1 , would not be sufficient to constitute a "cross-bndge" and accordingly would not be preferred. Suitable metals in the ngid ligand complexes include Mn(EI), Mn(IH), Mn(IV), Mn(V), Fe(II), Fe(m), Fe(IV), Co(I), Co(II), Co( ), Nι(I), Nι(II), Nι(m), Cu(I), Cu(II), Cu(m), Cr(II), Cr(ffl), Cr(IV), Cr(V), Cr(VI), V(m), V(IV), V(V), Mo(IV), Mo(V), Mo(VI), W(IV), W(V), W(VI), Pd(II), Ru(π), RU(IH), and Ru(rV). Preferred transition-metals the instant transition- metal bleach catalyst include manganese, iron and chromium.

More generally, the MRL's (and the corresponding transition-metal catalysts) herein suitably compnse:

(a) at least one macrocycle ma nng compnsmg four or more heteroatoms; and

(b) a covalently connected non-metal superstructure capable of increasing the ngidity of the macrocycle, preferably selected from

(l) a bndgmg superstructure, such as a linking moiety;

(n) a cross-bndgmg superstructure, such as a cross-bπdgmg linking moiety; and

(m) combinations thereof.

The term "superstructure" is used herem as defined in the literature by Busch et al., see, for example, articles by Busch in "Chemical Reviews".

Preferred superstructures herem not only enhance the πgidity of the parent macrocycle, but also favor folding of the macrocycle so that it co-ordmates to a metal m a cleft. Suitable superstructures can be remarkably simple, for example a linking moiety such as any of those illustrated in Fig. 1 and Fig. 2 below, can be used.

CH^n F Fiigg.. 11 wherein n is an mteger, for example from 2 to 8, preferably less than 6, typically 2 to 4, or

wherein m and n are integers from about 1 to 8, more preferably from 1 to 3; Z is N or CH; and T is a compatible substituent, for example H, alkyl, tnalkylammonium, halogen, mtro, sulfonate, or the like The aromatic nng in 1.10 can be replaced by a saturated nng, m which the atom in Z connecting into the nng can contain N, O, S or C.

Suitable MRL's are further nonhmitmgly illustrated by the following compound:

This is a MRL m accordance with the invention which is a highly preferred, cross- bndged, methyl-substituted (all nitrogen atoms tertiary) denvative of cyclam. Formally, this ligand is named 5,12-dιmethyl-l,5,8,12-tetraazabιcyclo[6.6.2]hexadecane using the extended von Baeyer system. See "A Guide to IUPAC Nomenclature of Organic Compounds Recommendations 1993", R. Pamco, W.H. Powell and J-C Richer (Eds ), Blackwell Scientific Publications, Boston, 1993; see especially section R-2.4.2.1

Transition-metal bleach catalysts of Macrocyc c Rigid Ligands which are suitable for use m the invention compositions can in general mclude known compounds where they conform with the definition herein, as well as, more preferably, any of a large number of novel compounds expressly designed for the present laundry or cleaning uses, and non-hmitingly illustrated by any of the following:

Dιchloro-5,12-dιmethyl-l,5,8,12-tetraazabιcyclo[6 6.2]hexadecane Manganese(EI) Dιaquo-5,12-dιmethyl-l,5,8,12-tetraazabιcyclo[6.6.2]hexadecane Manganese(Ef) Hexafluorophosphate Aquo-hydroxy-5, 12-dιmethyl- 1 ,5,8, 12-tetraazabιcyclo[6.6.2]hexadecane Manganese(IH)

Hexafluorophosphate Diaquo-5, 12-dimethyl- 1,5,8,12-tetraazabιcyclo[6.6.2]hexadecane Manganese(II) Tetrafluoroborate Dichloro-5,12-dimethyl-l,5,8,12-tetraazabicyclo[6.6.2]hexadecane Manganese(HI) Hexafluorophosphate Dιchloro-5,12-dι-n-butyl-l,5,8,12-tetraaza bιcyclo[6.6 2]hexadecane Manganese(II) Dιchloro-5, 12-dιbenzyl-l ,5,8, 12-tetraazabιcyclo[6.6.2]hexadecane Manganese(II) Dιchloro-5-n-butyl-12-methyl-l,5,8,12-tetraaza- bιcyclo[6.6.2]hexadecane Manganese(H) Dιchloro-5-n-octyl-12-methyl-l,5,8,22-tetraaza- bιcyclo[6.6.2]hexadecane Manganese(II) Dιchloro-5-n-butyl-12-methyl-l,5,8,12-tetraaza- bιcyclo[6.6.2]hexadecane Manganese(EI). As a practical matter, and not by way of limitation, the compositions and cleaning processes herein can be adjusted to provide on the order of at least one part per hundred million of the active bleach catalyst species m the aqueous washing medium, and will preferably provide from about 0.01 ppm to about 25 ppm, more preferably from about 0 05 ppm to about 10 ppm, and most preferably from about 0.1 ppm to about 5 ppm, of the bleach catalyst species in the wash liquor. In order to obtain such levels m the wash liquor of an automatic washing process, typical compositions herein will compnse from about 0.0005% to about 0.2%, more preferably from about 0.004% to about 0.08%, of bleach catalyst, especially manganese or cobalt catalysts, by weight of the bleaching compositions.

(d) Other Bleach Catalysts - The compositions herein may compnse one or more other bleach catalysts. Preferred bleach catalysts are zwittenomc bleach catalysts, which are descnbed in U.S. Patent No. 5,576,282 (especially 3-(3,4-dιhydroιsoqumolmιum) propane sulfonate. Other bleach catalysts include cationic bleach catalysts are descnbed in U.S. Patent Nos. 5,360,569, 5,442,066, 5,478,357, 5,370,826, 5,482,515, 5,550,256, and WO 95/13351, WO 95/13352, and WO 95/13353.

Also suitable as bleaching agents are preformed peracids, such as phtha mido-peroxy- caproic acid ("PAP"). See for example U.S. Patent Nos. 5,487,818, 5,310,934, 5,246,620, 5,279,757 and 5,132,431. Controlled rate of release

The detergent tablet may be provided with a way for controlling the rate of release of bleaching agent, particularly oxygen bleach to the wash solution.

The controlling of the rate of release of the bleach may provide for controlled release of peroxide species to the wash solution. This could, for example, include controlling the release of any inorganic perhydrate salt, acting as a hydrogen peroxide source, to the wash solution.

Suitable ways of controlled release of the bleaching agent can include confining the bleach to either the compressed or non-compressed, non-encapsulating portions. Where more than one non-compressed, non-encapsulating portions are present, the bleach may be confined to the first and or second and/or optional subsequent non-compressed, non-encapsulating portions. Another way for controlling the rate of release of bleach may be by coating the bleach with a coating designed to provide the controlled release. The coating may therefore, for example, compnse a poorly water soluble matenal, or be a coating of sufficient thickness that the kinetics of dissolution of the thick coating provide the controlled rate of release.

The coating mateπal may be applied using vanous methods. Any coating matenal is typically present at a weight ratio of coating mateπal to bleach of from 1 :99 to 1 :2, preferably from 1:49 to 1:9.

Suitable coating mateπals include tπglycendes (e.g. partially) hydrogenated vegetable oil, soy bean oil, cotton seed oil) mono or diglyceπdes, microcrystalline waxes, gelatin, cellulose, fatty acids and any mixtures thereof. Other suitable coating mateπals can compnse the alkali and alkaline earth metal sulphates, silicates and carbonates, including calcium carbonate and silicas. A preferred coating matenal, particularly for an inorganic perhydrate salt bleach source, compnses sodium silicate of S1O2 . Na2θ ratio from 1.8 : 1 to 3.0 1, preferably 1.8:1 to 2.4: 1, and/or sodium metasi cate, preferably applied at a level of from 2% to 10%, (normally from 3% to 5%) of S1O2 by weight of the inorganic perhydrate salt. Magnesium silicate can also be included in the coating.

Any inorganic salt coating matenals may be combined with organic binder matenals to provide composite inorganic salt/organic binder coatings. Suitable binders include the Ci 0- 20 alcohol ethoxylates containing from 5 - 100 moles of ethylene oxide per mole of alcohol and more preferably the C15-C20 pnmary alcohol ethoxylates containing from 20 - 100 moles of ethylene oxide per mole of alcohol.

Other preferred binders include certain polymenc matenals. Polyvmylpyrrohdones with an average molecular weight of from 12,000 to 700,000 and polyethylene glycols (PEG) with an average molecular weight of from 600 to 5 x 10^ preferably 1000 to 400,000 most preferably 1000 to 10,000 are examples of such polymenc matenals. Copolymers of maleic anhydnde with ethylene, methylvinyl ether or methacryhc acid, the maleic anhydnde constituting at least 20 mole percent of the polymer are further examples of polymenc matenals useful as binder agents.

These polymenc mateπals may be used as such or in combination with solvents such as water, propylene glycol and the above mentioned C10-C20 alcohol ethoxylates containing from 5 - 100 moles of ethylene oxide per mole. Further examples of binders include the C1Q-C20 mono- and diglycerol ethers and also the C10-C20 fatty acids.

Cellulose denvatives such as methylcellulose, carboxymethylcellulose and hydroxyethylcellulose, and homo- or co-polymeπc polycarboxyhc acids or their salts are other examples of binders suitable for use herein.

One method for applying the coating mateπal involves agglomeration. Preferred agglomeration processes include the use of any of the organic binder mateπals descnbed heremabove. Any conventional agglomerator/mixer may be used including, but not limited to pan, rotary drum and vertical blender types. Molten coating compositions may also be applied either by being poured onto, or spray atomized onto a moving bed of bleaching agent.

Other ways of providing the required controlled release include alteπng the physical charactenstics of the bleach to control its solubility and rate of release. Suitable ways could include compression, mechanical injection, manual injection, and adjustment of the solubility of the bleach compound by selection of particle size of any particulate component.

Whilst the choice of particle size will depend both on the composition of the particulate component, and the desire to meet the desired controlled release kinetics, it is desirable that the particle size should be more than 500 micrometers, preferably having an average particle diameter of from 800 to 1200 micrometers. Additional ways for providing controlled release include the suitable choice of any other components of the detergent composition matnx such that when the composition is introduced to the wash solution the ionic strength environment therein provided enables the required controlled release kinetics to be achieved Optional Detersive Enzymes - The detergent and cleaning compositions herein may also optionally contain one or more types of detergent enzymes. Such enzymes can include other proteases, amylases, cellulases and hpases. Such matenals are known in the art and are commercially available under such trademarks as . They may be incorporated into the non- aqueous liquid detergent compositions herein in the form of suspensions, "marumes" or "pnlls". Another suitable type of enzyme compπses those m the form of slumes of enzymes m nonionic surfactants, e.g., the enzymes marketed by Novo Nordisk under the tradename "SL" or the microencapsulated enzymes marketed by Novo Nordisk under the tradename "LDP " Suitable enzymes and levels of use are descnbed in U.S. Pat. No 5,576,282, 5,705,464 and 5,710,115.

Enzymes added to the compositions herein m the form of conventional enzyme pnlls are especially preferred for use herein. Such pnlls will generally range m size from about 100 to

1,000 microns, more preferably from about 200 to 800 microns and will be suspended throughout the non-aqueous liquid phase of the composition. Pnlls in the compositions of the present invention have been found, in companson with other enzyme forms, to exhibit especially desirable enzyme stability m terms of retention of enzymatic activity over time. Thus, compositions which utilize enzyme pnlls need not contain conventional enzyme stabilizing such as must frequently be used when enzymes are incorporated into aqueous liquid detergents.

However, enzymes added to the compositions herein may be m the form of granulates, preferably T-granulates.

"Detersive enzyme", as used herein, means any enzyme having a cleaning, stain removing or otherwise beneficial effect in a laundry, hard surface cleaning or personal care detergent composition. Preferred detersive enzymes are hydrolases such as proteases, amylases and hpases. Preferred enzymes for laundry purposes include, but are not limited to, proteases, cellulases, hpases and peroxidases. Highly preferred for automatic dishwashing are amylases and/or proteases, including both current commercially available types and improved types which, though more and more bleach compatible though successive improvements, have a remaining degree of bleach deactivation susceptibility.

Examples of suitable enzymes include, but are not limited to, hemicellulases, peroxidases, proteases, cellulases, xylanases, hpases, phosphohpases, esterases, cutinases, pectmases, keratanases, reductases, oxidases, phenoloxidases, hpoxygenases, gninases, pullulanases, tannases, pentosanases, malanases, β-glucanases, arabmosidases, hyaluromdase, chondroitmase. laccase, and known amylases. or mixtures thereof. Examples of such suitable enzymes are disclosed in U.S. Patent Nos. 5,705,464, 5,710,115, 5,576,282. 5.728,671 and 5,707,950

The cellulases useful m the present invention include both bactenal or fungal cellulases. Preferably, they will have a pH optimum of between 5 and 12 and a specific activity above 50 CEVU/mg (Cellulose Viscosity Unit). Suitable cellulases are disclosed in U.S. Patent 4,435,307, J61078384 and WO96/02653 which discloses fungal cellulase produced respectively from Humicola msolens, Tnchoderma, Thielavia and Sporotnchum. EP 739 982 descπbes cellulases isolated from novel Bacillus species. Suitable cellulases are also disclosed m GB-A-2.075.028; GB-A-2.095.275; DE-OS-2.247.832 and W095/26398. Examples of such cellulases are cellulases produced by a strain of Humicola insolens

(Humicola gπsea var. thermoidea), particularly the Humicola strain DSM 1800. Other suitable cellulases are cellulases ongmated from Humicola msolens having a molecular weight of about 50KDa, an isoelectπc point of 5.5 and containing 415 ammo acids; and a ~43kD endoglucanase deπved from Humicola msolens, DSM 1800, exhibiting cellulase activity; a preferred endoglucanase component has the ammo acid sequence disclosed in WO 91/17243. Also suitable cellulases are the EG-H cellulases from Tnchoderma longibrachiatum descnbed m WO94/21801 to Genencor. Especially suitable cellulases are the cellulases having color care benefits. Examples of such cellulases are cellulases descnbed m European patent application No. 91202879.2, filed November 6, 1991 (Novo). Carezyme and Celluzyme (Novo Nordisk A/S) are especially useful. See also W091/17244 and W091/21801. Other suitable cellulases for fabπc care and or cleanmg properties are descnbed in WO96/34092, W096/17994 and W095/24471

Cellulases, when present, are normally incorporated m the cleaning composition at levels from 0.0001%) to 2% of pure enzyme by weight of the cleaning composition.

Peroxidase enzymes are used m combination with oxygen sources, e.g percarbonate, perborate, persulfate, hydrogen peroxide, etc and with a phenolic substrate as bleach enhancing molecule. They are used for "solution bleaching", i.e. to prevent transfer of dyes or pigments removed from substrates dunng wash operations to other substrates in the wash solution. Peroxidase enzymes are known in the art, and include, for example, horseradish peroxidase, hgninase and haloperoxidase such as chloro- and bromo-peroxidase. Suitable peroxidases and peroxidase-contammg detergent compositions are disclosed, for example, m U.S. Patent Nos. 5,705,464, 5,710,115, 5,576,282, 5,728,671 and 5,707,950, PCT International Application WO 89/099813, WO89/09813 and m European Patent application EP No. 91202882.6, filed on November 6, 1991 and EP No 96870013.8, filed February 20, 1996. Also suitable is the laccase enzyme. Enhancers are generally compnsed at a level of from 0.1% to 5% by weight of total composition. Preferred enhancers are substitued phenthiazme and phenoxasme 10-

SUBSTΓΓUTE SHEET (RULE 26) Phenothiazmepropionicacid (PPT), 10-ethylphenothιazme-4-carboxylιc acid (EPC), 10- phenoxazmepropionic acid (POP) and 10-methylphenoxazme (descnbed in WO 94/12621) and substitued syπngates (C3-C5 substitued alkyl syπngates) and phenols. Sodium percarbonate or perborate are preferred sources of hydrogen peroxide. Said peroxidases are normally incorporated m the cleaning composition at levels from 0.0001% to 2% of pure enzyme by weight of the cleaning composition.

Enzymatic systems may be used as bleaching agents. The hydrogen peroxide may also be present by adding an enzymatic system (i.e. an enzyme and a substrate therefore) which is capable of generating hydrogen peroxide at the beginning or duπng the washing and/or nnsmg process. Such enzymatic systems are disclosed m EP Patent Application 91202655.6 filed October 9, 1991.

Other preferred enzymes that can be included the cleaning compositions of the present invention include hpases. Suitable lipase enzymes for detergent usage include those produced by microorganisms of the Pseudomonas group, such as Pseudomonas stutzeπ ATCC 19.154, as disclosed in Bπtish Patent 1,372,034. Suitable hpases mclude those which show a positive immunological cross-reaction with the antibody of the lipase, produced by the microorganism Pseudomonas fluorescent JAM 1057. This lipase is available from Amano Pharmaceutical Co. Ltd., Nagoya, Japan, under the trade name Lipase P "Amano," hereinafter referred to as "Amano- P". Other suitable commercial hpases include Amano-CES, hpases ex Chromobacter viscosum. e.g. Chromobacter viscosum var lipolyticum NRRLB 3673 from Toyo Jozo Co., Tagata, Japan; Chromobacter viscosum hpases from U.S. Biochemical Corp., U S.A. and Disoynth Co., The Netherlands, and hpases ex Pseudomonas gladioli. Especially suitable hpases are hpases such as Ml

which have found to be very effective when used in combination with the compositions of the present invention. Also suitable are the hpolytic enzymes descnbed in EP 258 068, WO 92/05249 and WO 95/22615 by Novo Nordisk and in WO 94/03578, WO 95/35381 and WO 96/00292 by Unilever.

Also suitable are cutmases [EC 3.1.1.50] which can be considered as a special kind of lipase, namely hpases which do not require interfacial activation. Addition of cutmases to cleaning compositions have been descnbed in e.g WO-A-88/09367 (Genencor); WO 90/09446 (Plant Genetic System) and WO 94/14963 and WO 94/14964 (Unilever).

Lipases and/or cutmases, when present, are normally incorporated m the cleaning composition at levels from 0.0001% to 2% of pure enzyme by weight of the cleaning composition. In addition to the above referenced lipases, phosphohpases may be incorporated into the cleaning compositions of the present invention. Nonhmitmg examples of suitable phosphohpases included: EC 3.1.1.32 Phosphohpase Al; EC 3.1.1.4 Phosphohpase A2: EC 3.1.1.5 Lysophohpase; EC 3.1.4.3 Phosphohpase C, EC 3.1.4.4. Phospohpase D. Commercially available phosphohpases include LECITASE® from Novo Nordisk A/S of Denmark and Phosphohpase A2 from Sigma. When phospo pases are included in the compositions of the present invention, it is preferred that amylases are also included. Without desmng to be bound by theory, it is believed that the combined action of the phosphohpase and amylase provide substantive stain removal, especially on greasy/oily, starchy and highly colored stains and soils. Preferably, the phosphohpase and amylase, when present, are incorporated into the compositions of the present invention at a pure enzyme weight ratio between 4500:1 and 1:5, more preferably between 50:1 and 1:1.

Suitable proteases are the subti sins which are obtained from particular strains of -9. subtilis and B. licheniformis (subtihsm BPN and BPN') One suitable protease is obtained from a strain of Bacillus, having maximum activity throughout the pH range of 8-12, developed and sold as ESPERASE® by Novo Industries A/S of Denmark, hereinafter "Novo". The preparation of this enzyme and analogous enzymes is descnbed m GB 1,243,784 to Novo. Proteolytic enzymes also encompass modified bactenal seπne proteases, such as those descnbed in European Patent Application Serial Number 87 303761.8, filed Apπl 28, 1987 (particularly pages 17, 24 and 98), and which is called herein "Protease B", and in European Patent Application 199,404, Venegas, published October 29, 1986, which refers to a modified bactenal senne protealytic enzyme which is called "Protease A" herein. Suitable is the protease called herein "Protease C", which is a vaπant of an alkaline seπne protease from Bacillus in which Lysme replaced argimne at position 27, tyrosine replaced valme at position 104, seπne replaced asparagme at position 123, and alanine replaced threonme at position 274. Protease C is descnbed EP 90915958:4, corresponding to WO 91/06637, Published May 16, 1991. Genetically modified vanants, particularly of Protease C, are also included herein.

A preferred protease referred to as "Protease D" is a carbonyl hydrolase as descnbed m U.S. Patent No. 5,677,272, and WO95/10591. Also suitable is a carbonyl hydrolase vanant of the protease descnbed in WO95/1059 I, having an ammo acid sequence derived by replacement of a plurality of ammo acid residues replaced m the precursor enzyme corresponding to position +210 in combination with one or more of the following residues : +33, +62, +67, +76, +100, +101, +103, +104, +107, +128, +129, +130, +132, +135, +156, +158, +164, +166, +167, +170, +209, +215, +217, +218, and +222, where the numbered position corresponds to naturally- occurnng subtihsm from Bacillus amyloliquefaciens or to equivalent ammo acid residues m other carbonyl hydrolases or subtihsins, such as Bacillus lentus subtihsm (co-pending patent application US Serial No. 60/048,550, filed June 04, 1997 and PCT International Application Senal No. PCT/IB98/00853).

SUBSTITUTE SHEET (RULE 25) Also suitable for the present invention are proteases descnbed m patent applications EP 251 446 and WO 91/06637, protease BLAP® descnbed in W091/02792 and their vanants descnbed in WO 95/23221.

See also a high pH protease from Bacillus sp. NCIMB 40338 descnbed in WO 93/18140 A to Novo. Enzymatic detergents compnsmg protease, one or more other enzymes, and a reversible protease inhibitor are descnbed m WO 92/03529 A to Novo. When desired, a protease having decreased adsorption and increased hydrolysis is available as descnbed m WO 95/07791 to Procter & Gamble. A recombinant trypsin-hke protease for detergents suitable herein is descnbed WO 94/25583 to Novo. Other suitable proteases are descnbed in EP 516 200 by Unilever.

Particularly useful proteases are descnbed in PCT publications: WO 95/30010; WO 95/30011; and WO 95/29979. Suitable proteases are commercially available as ESPERASE®, ALCALASE®, DURAZYM®, SAVINASE®, EVERLASE® and KANNASE® all from Novo Nordisk A/S of Denmark, and as MAXATASE®, MAXACAL®, PROPERASE® and MAXAPEM® all from Genencor International (formerly Gist-Brocades of The Netherlands). Such proteolytic enzymes, when present, are incorporated in the cleaning compositions of the present invention a level of from 0.0001% to 2%, preferably from 0.001% to 0.2%, more preferably from 0.005% to 0.1% pure enzyme by weight of the composition.

Amylases (α and or β) can be included for removal of carbohydrate-based stains. WO94/02597 descnbes cleaning compositions which incorporate mutant amylases. See also W095/ 10603. Other amylases known for use in cleaning compositions include both α- and β- amylases. α-Amylases are known m the art and include those disclosed in US Pat. no. 5,003,257; EP 252,666; WO/91/00353; FR 2,676,456; EP 285,123; EP 525,610; EP 368,341; and Bntish Patent specification no. 1,296,839 (Novo). Other suitable amylases are stability-enhanced amylases descnbed m W094/18314 and WO96/05295, Genencor, and amylase vanants having additional modification in the immediate parent available from Novo Nordisk A S, disclosed in WO 95/10603. Also suitable are amylases descnbed in EP 277 216.

Examples of commercial α-amylases products are Purafect Ox Am® from Genencor and Termamyl®, Ban® ,Fungamyl® and Duramyl®, all available from Novo Nordisk A S Denmark. W095/26397 descnbes other suitable amylases : α-amylases charactensed by having a specific activity at least 25% higher than the specific activity of Termamyl® at a temperature range of 25° C to 55°C and at a pH value in the range of 8 to 10, measured by the Phadebas® α-amylase activity assay. Suitable are vanants of the above enzymes, descnbed in W096/23873 (Novo Nordisk). Other amylolytic enzymes with improved properties with respect to the activity level and the combination of thermostability and a higher activity level are descnbed m W095/35382. Such amylolytic enzymes, when present, are incorporated in the cleaning compositions of the present invention a level of from 0.0001% to 2%, preferably from 0.00018% to 0.06%, more preferably from 0.00024% to 0.048% pure enzyme by weight of the composition.

The above-mentioned enzymes may be of any suitable oπgm, such as vegetable, animal, bactenal, fungal and yeast ongin. Oπgm can further be mesophihc or extremophihc

(psychrophi c, psychrotrophic, thermophilic, barophi c, alkalophihc, acidophi c, halophihc, etc.). Punfied or non-punfied forms of these enzymes may be used. Nowadays, it is common practice to modify wild-type enzymes via protein / genetic engmeeπng techniques m order to optimize their performance efficiency m the laundry detergent and or fabnc care compositions of the invention. For example, the vanants may be designed such that the compatibility of the enzyme to commonly encountered ingredients of such compositions is increased. Alternatively, the vanant may be designed such that the optimal pH, bleach or chelant stability, catalytic activity and the like, of the enzyme vaπant is tailored to suit the particular cleaning application. In particular, attention should be focused on ammo acids sensitive to oxidation in the case of bleach stability and on surface charges for the surfactant compatibility. The isoelectπc point of such enzymes may be modified by the substitution of some charged ammo acids, e.g. an increase m isoelectnc point may help to improve compatibility with anionic surfactants. The stability of the enzymes may be further enhanced by the creation of e.g. additional salt bndges and enforcing calcium binding sites to increase chelant stability. These optional detersive enzymes, when present, are normally incorporated m the cleaning composition at levels from 0.0001% to 2% of pure enzyme by weight of the cleaning composition. The enzymes can be added as separate single ingredients (pnlls, granulates, stabilized liquids, etc... containing one enzyme ) or as mixtures of two or more enzymes ( e.g. cogranulates ). Other suitable detergent ingredients that can be added are enzyme oxidation scavengers.

Examples of such enzyme oxidation scavengers are ethoxylated tetraethylene polyamines.

A range of enzyme matenals and means for their incorporation into synthetic detergent compositions is also disclosed in WO 9307263 and WO 9307260 to Genencor International, WO 8908694, and U.S. 3,553,139, January 5, 1971 to McCarty et al. Enzymes are further disclosed in U.S. 4,101,457, and in U.S. 4,507,219. Enzyme mateπals useful for liquid detergent formulations, and their incorporation into such formulations, are disclosed m U.S. 4,261,868. Enzyme Stabilizers - Enzymes for use in detergents can be stabilized by vaπous techniques. Enzyme stabilization techniques are disclosed and exemplified in U.S. 3,600,319, EP 199,405 and EP 200,586. Enzyme stabilization systems are also descnbed, for example, in U.S. 3,519,570. A useful Bacillus, sp. AC 13 giving proteases, xylanases and cellulases, is descnbed in WO 9401532. The enzymes employed herein can be stabilized by the presence of water-soluble sources of calcium and or magnesium ions m the finished compositions which provide such ions to the enzymes. Suitable enzyme stabilizers and levels of use are descnbed m U.S. Pat. Nos. 5,705,464, 5,710,115 and 5,576,282. Disrupting Agents As it was stated above, the detergent tablet of the present invention may further compnse a disrupting agent. Disrupting agents are typically included m the tablet at levels of from about 5% to about 60%, and more preferably from about 20% to about 50%, by weight. The disrupting agent may be a disintegrating or effervescing agent. Suitable disintegrating agents include agents that swell on contact with water or facilitated water influx and/or efflux by forming channels in compressed and/or non-compressed portions. Any known disintegrating or effervescing agent suitable for use in laundry or dishwashing applications is envisaged for use herein. Suitable disintegrating agent include starch, starch denvatives, alg ates, carboxymethylcellulose (CMC), cellulosic-based polymers, sodium acetate, aluminium oxide. Suitable effervescing agents are those that produce a gas on contact with water. Suitable effervescing agents may be oxygen, nitrogen dioxide or carbon dioxide evolving species. Examples of preferred effervescing agents may be selected from the group consisting of perborate, percarbonate, carbonate, bicarbonate and carboxylic acids such as citnc or maleic acid.

Builders - When present, the compositions will typically compnse at least about 1% builder, preferably from about 5%, more preferably from about 10% to about 80%, preferably to about 50%), more preferably to about 30% by weight, of detergent builder. Lower or higher levels of builder, however, are not meant to be excluded.

Preferred builders for use m the detergent and cleaning compositions, particularly dishwashing compositions, especially automatic dishwashing compositions or detergents ("ADD" or "ADW") descnbed herein include, but are not limited to, water-soluble builder compounds, (for example polycarboxylates) as descnbed in U.S. Patent Nos. 5,695,679,

5,705,464 and 5,710,115. Other suitable polycarboxylates are disclosed in U.S. Patent

Nos. 4,144,226, 3,308,067 and 3,723,322. Preferred polycarboxylates are hydroxycarboxylates containing up to three carboxy groups per molecule, more particularly titrates.

Inorganic or P-contammg detergent builders include, but are not limited to, the alkali metal, ammonium and alkanolammomum salts of polyphosphates (exemplified by the tπpolyphosphates, pyrophosphates, and glassy polymenc meta-phosphates), phosphonates (see, for example, U.S. Patent Nos. 3,159,581; 3,213,030; 3,422,021, 3,400,148 and 3,422,137), phytic acid, silicates, carbonates (including bicarbonates and sesquicarbonates), sulphates, and alummosihcates. However, non-phosphate builders are required some locales. Importantly, the compositions herein function surpnsmgly well even in the presence of the so-called "weak" builders (as compared with phosphates) such as citrate, or in the so-called "underbuilt" situation that may occur with zeolite or layered silicate builders.

Preferably, the silicates are water-soluble silicates, more preferably they are any silicates which are soluble to the extent that they do not adversely affect spotting' filming charactenstics of the ADD composition.

Suitable silicates include the water-soluble sodium silicates with an Sι0 .Na₂0 ratio of from about 1.0 to 2.8, with ratios of from about 1.6 to 2.4 being preferred, and about 2.0 ratio being most preferred. The silicates may be m the form of either the anhydrous salt or a hydrated salt. Sodium silicate with an Sι0₂.'Na₂0 ratio of 2.0 is the most preferred. Silicates, when present, are preferably present m the detergent and cleaning compositions descnbed herein at a level of from about 5% to about 50% by weight of the composition, more preferably from about 10% to about 40% by weight.

Partially soluble or insoluble builder compounds, which are suitable for use the detergent and cleaning compositions, particularly granular detergent compositions, include, but are not limited to, crystalline layered silicates, preferably crystalline layered sodium silicates

(partially water-soluble) as descnbed in U.S. Patent No. 4,664,839, and sodium alummosihcates (water-msoluble). When present in detergent and cleaning compositions, these builders are typically present at a level of from about 1% to 80% by weight, preferably from about 10% to 70% by weight, most preferably from about 20% to 60% by weight of the composition. Crystalline layered sodium silicates having the general formula NaMSι_xθ2_x+ι Y^O wherein M is sodium or hydrogen, x is a number from about 1.9 to about 4, preferably from about 2 to about 4, most preferably 2, and y is a number from about 0 to about 20, preferably 0 can be used m the compositions descnbed herein. Crystalline layered sodium silicates of this type are disclosed in EP-A-0164514 and methods for their preparation are disclosed in DE-A- 3417649 and DE-A-3742043. The most preferred matenal is delta-Na2Sιθ5, available from

Hoechst AG as NaSKS-6 (commonly abbreviated herein as "SKS-6"). Unlike zeolite builders, the Na SKS-6 silicate builder does not contain aluminum. NaSKS-6 has the delta-Na2Sιθ5 morphology form of layered silicate. SKS-6 is a highly preferred layered silicate for use m the compositions descnbed herein herein, but other such layered silicates, such as those having the general formula NaMSι_xθ2_x+i y^O wherein M is sodium or hydrogen, x is a number from 1.9 to 4, preferably 2, and y is a number from 0 to 20, preferably 0 can be used m the compositions descnbed herein. Vanous other layered silicates from Hoechst include NaSKS-5, NaSKS-7 and NaSKS-11, as the alpha, beta and gamma forms. As noted above, the delta-Na2Sιθ5 (NaSKS-6 form) is most preferred for use herein. Other silicates may also be useful such as for example magnesium silicate, which can serve as a cπspenmg agent in granular formulations, as a stabilizing agent for oxygen bleaches, and as a component of suds control systems. Silicates particularly useful in automatic dishwashing (ADD) applications include granular hydrous 2-ratιo silicates such as BR--TESIL® H20 from PQ Corp , and the commonly sourced BRITESIL® H24 though liquid grades of vanous silicates can be used when the ADD composition has liquid form. Within safe limits, sodium metasihcate or sodium hydroxide alone or in combination with other silicates may be used in an ADD context to boost wash pH to a desired level.

The crystalline layered sodium silicate mateπal is preferably present m granular detergent compositions as a particulate in intimate admixture with a solid, water-soluble lomzable mateπal. The solid, water-soluble lomzable matenal is preferably selected from organic acids, organic and inorganic acid salts and mixtures thereof.

Also suitable in the detergent compositions descnbed herein are the 3,3-dιcarboxy-4-oxa- 1,6-hexanedιoates and the related compounds disclosed m U.S. 4,566,984 Useful succi c acid builders include the C5-C20 alkyl and alkenyl succimc acids and salts thereof. A particularly preferred compound of this type is dodecenylsuccmic acid. Specific examples of succmate builders include: laurylsuccmate, myπstylsuccmate, palmitylsuccmate, 2-dodecenylsuccιnate

(preferred), 2-pentadecenylsuccmate, and the like. Laurylsuccinates are the preferred builders of this group, and are descnbed m European Patent Application 86200690.5/0,200,263, published

November 5, 1986.

Fatty acids, e.g., C^- monocarboxyhc acids, can also be incorporated into the compositions alone, or in combination with the aforesaid builders, especially citrate and/or the succmate builders, to provide additional builder activity. Such use of fatty acids will generally result in a diminution of sudsmg, which should be taken into account by the formulator. Dispersants - One or more suitable polyalkyleneimine dispersants may be incorporated into the cleaning compositions of the present invention. Examples of such suitable dispersants can be found m European Patent Application Nos. 111,965, 111,984, and 112,592; U.S. Patent Nos. 4,597,898, 4,548,744, and 5,565,145. However, any suitable clay/soil dispersent or anti- redepostion agent can be used in the laundry compositions of the present invention.

In addition, polymenc dispersing agents which mclude polymenc polycarboxylates and polyethylene glycols, are suitable for use in the present invention. Unsaturated monomeπc acids that can be polymenzed to form suitable polymenc polycarboxylates include acrylic acid, maleic acid (or maleic anhydride), fumanc acid, itacomc acid, aconitic acid, mesacomc acid, citraconic acid and methylenemalomc acid. Particularly suitable polymenc polycarboxylates can be denved from acrylic acid. Such acrylic acid-based polymers which are useful herein are the water- soluble salts of polymenzed acrylic acid. The average molecular weight of such polymers in the acid form 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. Soluble polymers of this type are known matenals. Use of polyacrylates of this type in detergent compositions has been disclosed, for example, in U.S. 3,308,067.

Acrylic/maleic-based copolymers may also be used as a preferred component of the dispersmg/anti-redeposition agent. Such mateπals include the water-soluble salts of copolymers of acrylic acid and maleic acid. The average molecular weight of such copolymers m the acid form 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 in such copolymers will generally range from about 30: 1 to about 1:1, more preferably from about 10:1 to 2: 1. Water-soluble salts of such acrylic acid/maleic acid copolymers can include, for example, the alkali metal, ammonium and substituted ammonium salts. Soluble acrylate/maleate copolymers of this type are known matenals which are descnbed in European Patent Application No. 66915, published December 15, 1982, as well as in EP 193,360, published September 3, 1986, which also descnbes such polymers compnsmg hydroxypropylacrylate. Still other useful dispersing agents include the maleic/acryhc/vmyl alcohol terpolymers. Such matenals are also disclosed in EP 193,360, including, for example, the 45/45/10 terpolymer of acryhc/maleic/vmyl alcohol.

Another polymenc mateπal 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, especially in conjunction with zeolite builders. Dispersing agents such as polyaspartate preferably have a molecular weight (avg.) of about 10,000.

Chelating Agents - The compositions of the present invention herein may also optionally contain a chelating agent which serves to chelate metal ions and metal impuπties which would otherwise tend to deactivate the bleaching agent(s). Useful chelating agents can include ammo carboxylates, phosphonates, amino phosphonates, polyfunctionally-substituted aromatic chelating agents and mixtures thereof. Further examples of suitable chelating agents and levels of use are descnbed in U.S. Pat. Nos. 5,705,464, 5,710,115, 5,728,671 and 5,576,282.

The compositions herein may also contain water-soluble methyl glycine diacetic acid (MGDA) salts (or acid form) as a chelant or co-builder useful with, for example, insoluble builders such as zeolites, layered silicates and the like. If utilized, these chelating agents will generally compnse from about 0.1% to about 15%, more preferably from about 0 1% to about 3.0% by weight of the detergent compositions herein. Corrosion inhibitor compound - The detergent tablets of the present invention suitable for use in dishwashing methods may contain corrosion inhibitors preferably selected from organic silver coating agents, particularly paraffin, nitrogen-contammg corrosion inhibitor compounds and Mn(H) compounds, particularly Mn(H) salts of organic ligands. Organic silver coating agents are descnbed in PCT Publication No. WO94/16047 and copending European application No. EP-A-690122. Nitrogen-containing corrosion inhibitor compounds are disclosed m copending European Application no. EP-A-634,478. Mn(H) compounds for use in corrosion inhibition are descnbed in copending European Application No. EP-A-672 749. Organic silver coating agent, when present, may be incorporated at a level of preferably from about 0.05% to about 10%o, more preferably from about 0.1% to about 5% by weight of the total composition.

The functional role of the silver coating agent is to form 'in use' a protective coating layer on any silverware components of the washload to which the compositions of the invention are being applied. The silver coating agent should hence have a high affinity for attachment to solid silver surfaces, particularly when present in as a component of an aqueous washing and bleaching solution with which the solid silver surfaces are being treated.

Suitable organic silver coating agents herein include, but are not limited to, fatty esters of mono- or polyhydnc alcohols having from about 1 to about 40 carbon atoms m the hydrocarbon chain.

The fatty acid portion of the fatty ester can be obtained from mono- or poly-carboxyhc acids having from about 1 to about 40 carbon atoms the hydrocarbon chain. Suitable examples of monocarboxyhc fatty acids include behenic acid, steaπc acid, oleic acid, palmitic acid, mynstic acid, launc acid, acetic acid, propiomc acid, butync acid, isobutyπc acid, Valeπe acid, lactic acid, glycohc acid and β,β'- dihydroxyisobutyπc acid. Examples of suitable polycarboxyhc acids include: n-butyl-malomc acid, isocitπc acid, citπc acid, maleic acid, malic acid and succimc acid.

The fatty alcohol radical m the fatty ester can be represented by mono- or polyhydnc alcohols having from about 1 to about 40 carbon atoms in the hydrocarbon chain. Examples of suitable fatty alcohols include; behenyl, arachidyl, cocoyl, oleyl and lauryl alcohol, ethylene glycol, glycerol, ethanol, isopropanol, vmyl alcohol, diglycerol, xy tol, sucrose, erythπtol, pentaerythπtol, sorbitol or sorbitan.

Preferably, the fatty acid and/or fatty alcohol group of the fatty ester adjunct matenal have from about 1 to about 24 carbon atoms in the alkyl chain. Preferred fatty esters herein are ethylene glycol, glycerol and sorbitan esters wherein the fatty acid portion of the ester normally compπses a species selected from behenic acid, steaπc acid, oleic acid, palmitic acid or mynstic acid.

The glycerol esters are also highly preferred. These are the mono-, di- or tπ-esters of glycerol and the fatty acids as defined above.

Specific examples of fatty alcohol esters for use herein include: stearyl acetate, palmityl di-lactate, cocoyl isobutyrate, oleyl maleate, oleyl dimaleate , and tallowyl propπonate. Some fatty acid esters useful herein include: xyhtol monopalmitate, pentaerythntol monostearate, sucrose monostearate, glycerol monostearate, ethylene glycol monostearate, sorbitan esters. Suitable sorbitan esters include sorbitan monostearate, sorbitan palmitate, sorbitan monolaurate, sorbitan monomynstate, sorbitan monobehenate, sorbitan mono-oleate, sorbitan dilaurate, sorbitan distearate, sorbitan dibehenate, sorbitan dioleate, and also mixed tallowalkyl sorbitan mono- and di-esters.

Glycerol monostearate, glycerol mono-oleate, glycerol monopalmitate, glycerol monobehenate, and glycerol distearate are preferred glycerol esters herem.

Suitable organic silver coating agents include tπglycendes, mono or diglyceπdes, and wholly or partially hydrogenated denvatives thereof, and any mixtures thereof. Suitable sources of fatty acid esters include vegetable and fish oils and animal fats. Suitable vegetable oils include soy bean oil, cotton seed oil, castor oil, olive oil, peanut oil, safflower oil, sunflower oil, rapeseed oil, grapeseed oil, palm oil and corn oil.

Waxes, including microcrystalline waxes are suitable organic silver coating agents herein. Preferred waxes have a melting point in the range from about 35°C to about 1 10°C and compnse generally from about 12 to about 70 carbon atoms. Preferred are petroleum waxes of the paraffin and microcrystalline type which are composed of long-cham saturated hydrocarbon compounds.

Alginates and gelatin are suitable organic silver coating agents which can be used in the compositions herem.

Dialkyl amme oxides such as about C\2 to about C20 methylamine oxide, and dialkyl quaternary ammonium compounds and salts, such as the about C[2 ^t0 about C20 methylammo um ha des are also suitable.

Other suitable organic silver coating agents include certain polymenc matenals. Polyvmylpyrrohdones with an average molecular weight of from about 12,000 to about 700,000, polyethylene glycols (PEG) with an average molecular weight of from about 600 to about 10,000, polyamme N-oxide polymers, copolymers of N-vmylpyrrohdone and N-vinyhmidazole, and cellulose denvatives such as methylcellulose, carboxymethylcellulose and hydroxyethylcellulose are examples of such polymenc matenals. Certain perfume mateπals, particularly those demonstrating a high substantivity for metallic surfaces, are also useful as the organic silver coating agents herein.

Polymenc soil release agents can also be used as an organic silver coating agent.

A preferred organic silver coating agent is a paraffin oil, typically a predominantly branched aliphatic hydrocarbon having a number of carbon atoms in the range of from about 20 to about 50; preferred paraffin oil selected from predominantly branched C25- 5 species with a ratio of cyclic to noncychc hydrocarbons of from about 1.10 to about 2: 1, preferably from about 1 :5 to about 1 : 1. A paraffin oil meeting these charactenstics, having a ratio of cyclic to noncychc hydrocarbons of about 32:68, is sold by Wmtershall, Salzbergen, Germany, under the trade name WINOG 70.

Suitable nitrogen-containing corrosion inhibitor compounds include imidazole and denvatives thereof such as benzimidazole, 2-heptadecyl imidazole and those imidazole denvatives descnbed in Czech Patent No 139, 279 and Bntish Patent GB-A-1,137,741, which also discloses a method for making imidazole compounds. Also suitable as nitrogen-containing corrosion inhibitor compounds are pyrazole compounds and their denvatives, particularly those where the pyrazole is substituted in any of the 1, 3, 4 or 5 positions by substituents Rj, R3, R4 and R5 where Rj is any of H, CH2OH, CONH3, or COCH3, R3 and R5 are any of Cj-C20 alkyl or hydroxyl, and R4 is any of H, NH2 or NO2. Other suitable nitrogen-containing corrosion inhibitor compounds include benzotriazole, 2-mercaptobenzothιazole, l-phenyl-5-mercapto-l,2,3,4-tetrazole, thionahde, morphohne, melamme, distearylamme, stearoyl stearamide, cyanunc acid, ammotπazole, ammotetrazole and indazole.

Nitrogen-containing compounds such as ammes, especially distearylamme and ammonium compounds such as ammonium chlonde, ammonium bromide, ammonium sulphate or diammomum hydrogen citrate are also suitable.

The detergent tablets may contain an Mn(U) corrosion inhibitor compound. The Mn(Et) compound is preferably incorporated at a level of from about 0.005% to about 5% by weight, more preferably from about 0.01% to about 1%, most preferably from about 0.02% to about 0 4% by weight of the compositions. Preferably, the Mn(II) compound is incorporated at a level to provide from about 0.1 ppm to about 250 ppm, more preferably from about 0.5 ppm to about 50 ppm, even more preferably from about 1 ppm to about 20 ppm by weight of Mn(JI) ions in any bleaching solution.

The Mn (ET) compound may be an inorganic salt m anhydrous, or any hydrated forms. Suitable salts include manganese sulphate, manganese carbonate, manganese phosphate, manganese nitrate, manganese acetate and manganese chlonde. The Mn(EI) compound may be a salt or complex of an organic fatty acid such as manganese acetate or manganese stearate. The Mn(II) compound may be a salt or complex of an organic ligand. In one preferred aspect the organic ligand is a heavy metal ion sequestrant. In another preferred aspect the organic ligand is a crystal growth inhibitor.

Other suitable additional corrosion inhibitor compounds include, mercaptans and diols, especially mercaptans with about 4 to about 20 carbon atoms including lauryl mercaptan, thiophenol, thionapthol, thionahde and thioanthranol. Also suitable are saturated or unsaturated C10-C20 fatty acids, or their salts, especially aluminium tnstearate. The C12- 20 hydroxy fatty acids, or their salts, are also suitable. Phosphonated octa-decane and other anti-oxidants such as betahydroxytoluene (BHT) are also suitable. Copolymers of butadiene and maleic acid, particularly those supplied under the trade reference no. 07787 by Polysciences Inc. have been found to be of particular utility as corrosion inhibitor compounds.

Another preferred detergent active component for use in the present invention is a hydrocarbon oil, typically a predominantly long chain, aliphatic hydrocarbons having a number of carbon atoms in the range of from about 20 to about 50; preferred hydrocarbons are saturated and/or branched; preferred hydrocarbon oil selected from predominantly branched C25--45 species with a ratio of cyclic to noncychc hydrocarbons of from about 1: 10 to about 2:1, preferably from about 1 :5 to about 1 : 1. A preferred hydrocarbon oil is paraffin. A paraffin oil meeting the characteπstics as outlined above, having a ratio of cyclic to noncychc hydrocarbons of about 32:68, is sold by Wmtershall, Salzbergen, Germany, under the trade name WINOG 70. The detergent tablets of the present invention suitable for use in dishwashing methods may contain a water-soluble bismuth compound, preferably present at a level of from about 0.005% to about 20%, more preferably from about 0.01% to about 5%, even more preferably from about 0.1 % to about 1% by weight of the compositions. The water-soluble bismuth compound may be essentially any salt or complex of bismuth with essentially any inorganic or organic counter anion. Preferred inorganic bismuth salts are selected from the bismuth tnhahdes, bismuth nitrate and bismuth phosphate. Bismuth acetate and citrate are preferred salts with an organic counter anion. Colorant - The term 'colorant', as used herein, means any substance that absorbs specific wavelengths of light from the visible light spectrum. Such colorants when added to a detergent composition have the effect of changing the visible color and thus the appearance of the detergent composition. Colorants may be for example either dyes or pigments. Preferably the colorants are stable m composition in which they are to be incorporated. Thus in a composition of high pH the colorant is preferably alkali stable and m a composition of low pH the colorant is preferably acid stable. The compressed and/or non-compressed, non-encapsulating portions may contain a colorant, a mixture of colorants, colored particles or mixture of colored particles such that the compressed portion and the non-compressed, non-encapsulating portion have different visual appearances. Preferably one of either the compressed portion or the non-compressed, non- encapsulating portion a colorant. The compressed and/or non-compressed, non-encapsulating portions may also be of one color and contain particles or speckles, of another color. For example the compressed portion could be white with blue speckles, while the non- compressed, non-encapsulating portion is blue.

Where the non-compressed, non-encapsulating portion compπses two or more compositions of detergent active components, preferably at least one of either the first and second and/or subsequent compositions compπses a colorant. Where both the first and second and/or subsequent compositions compnse a colorant it is preferred that the colorants have a different visual appearance.

Where present the coating layer preferably compnses a colorant. Where the compressed portion and the coating layer compnse a colorant, it is preferred that the colorants provide a different visual effect.

Examples of suitable dyes include reactive dyes, direct dyes, azo dyes. Preferred dyes include phthalocyanine dyes, anthraqu one dye, quinohne dyes, monoazo, disazo and polyazo. More preferred dyes include anthraqumone, quinohne and monoazo dyes. Preferred dyes mclude SANDOLAN E-HRL 180% (tradename), SANDOLAN MILLING BLUE (tradename),

TURQUOISE ACID BLUE (tradename) and SANDOLAN BRILLIANT GREEN (tradename) all available from Claπant UK, HEXACOL QUINOLINE YELLOW (tradename) and HEXACOL BRILLIANT BLUE (tradename) both available from Pointings, UK, ULTRA MARINE BLUE (tradename) available from Holliday or LEVAFD TURQUISE BLUE EBA (tradename) available from Bayer, USA.

Furthermore, it is preferred that the colorant does not cause visible staining to plastic, such as an automatic dishwasher or plastic tableware, after a plurality of cycles, more preferably between 1 and 50 cycles.

The colorant may be incorporated into the compressed and/or non-compressed, non- encapsulating portion by any suitable method. Suitable methods include mixing all or selected detergent active components with a colorant in a drum or spraying all or selected detergent active components with the colorant in a rotating drum. Alternatively, the colorants color may be improved by predisolving the colorant in a compatible solvent pnor to addition of the colorant to the composition. Colorant when present as a component of the compressed portion is present at a level of from about 0.001% to about 1.5%, preferably from about 0.01% to about 1.0%, most preferably from about 0.1 % to about 0.3% When present as a component of the non-compressed, non- encapsulating portion , colorant is generally present at a level of from about 0.001% to about 0.1%, more preferably from about 0.005% to about 0.05%, most preferably from about 0 007% to about 0.02%. When present as a component of the coating layer, colorant is present at a level of from about 0.01% to about 0.5%, more preferably from about 0 02% to about 0 1%, most preferably from about 0.03% to about 0.06%.

Silicone and Phosphate Ester Suds Suppressors - The compositions of the invention can optionally contain an alkyl phosphate ester suds suppressor, a silicone suds suppressor, or combinations thereof. Preferably, the suds suppressors, when present, are silicone and/or si ca- silicone mixtures, as disclosed in U.S. Patent Nos. 5,707,950 and 5,728,671. Levels in general are from 0% to about 10%, preferably, from about 0.001% to about 5%, more preferably from about 0.001%) to 2%, most preferably from about 0.01% to 1% by weight of the cleaning composition. However, generally (for cost considerations and/or deposition) preferred compositions herein do not compnse suds suppressors or compnse suds suppressors only at low levels, e.g., less than about 0.1% of active suds suppressing agent.

Silicone suds suppressor technology and other defoaming agents useful herein are extensively documented in "Defoaming, Theory and Industnal Applications", Ed., P.R. Garrett, Marcel Dekker, N.Y., 1973, ISBN 0-8247-8770-6, incorporated herem by reference. See especially the chapters entitled "Foam control m Detergent Products" (Ferch et al) and "Surfactant Antifoams" (Blease et al). See also U.S. Patents 3,933,672 and 4,136,045. Highly preferred silicone suds suppressors are the compounded types known for use laundry detergents such as heavy-duty granules, although types hitherto used only m heavy-duty liquid detergents may also be incorporated m the instant compositions. For example, polydimethylsiloxanes having tπmethylsilyl or alternate endblockmg units may be used as the silicone. These may be compounded with silica and or with surface-active nonsihcon components, as illustrated by a suds suppressor compnsmg 12% sihcone/sihca, 18% stearyl alcohol and 70% starch m granular form. A suitable commercial source of the silicone active compounds is Dow Corning Corp.

If it is desired to use a phosphate ester, suitable compounds are disclosed in U.S. Patent 3,314,891, issued Apnl 18, 1967, to Schmolka et al, incorporated herein by reference. Preferred alkyl phosphate esters contain from 16-20 carbon atoms. Highly preferred alkyl phosphate esters are monostearyl acid phosphate or monooleyl acid phosphate, or salts thereof, particularly alkali metal salts, or mixtures thereof.

It has been found preferable to avoid the use of simple calcium-precipitatmg soaps as antifoams in the present compositions as they tend to deposit on the dishware. Indeed, phosphate esters are not entirely free of such problems and the formulator will generally choose to minimize the content of potentially depositing antifoams in the instant compositions. pH and Buffenng Vanation

The detergent compositions herein can be buffered, i.e., they are relatively resistant to pH drop in the presence of acidic soils. However, other compositions herein may have exceptionally low buffenng capacity, or may be substantially unbuffered. Techniques for controlling or varying pH at recommended usage levels more generally include the use of not only buffers, but also additional alkalis, acids, pH-jump systems, dual compartment containers, etc., and are well known to those skilled in the art. The preferred compositions herein compnse a pH -adjusting component selected from water-soluble alkaline inorganic salts and water-soluble organic or inorganic builders. The pH- ad_justmg components are selected so that when the composition is dissolved in water at a concentration of 1,000 - 10,000 ppm, the pH remains m the range of above about 8, preferably from about 9.5 to about 11. The preferred nonphosphate pH-adjusting component of the invention is selected from the group consisting of: (l) sodium carbonate or sesquicarbonate; (n) sodium silicate, preferably hydrous sodium silicate having Sιθ2:Na2θ ratio of from about 1 : 1 to about 2: 1, and mixtures thereof with limited quantities of sodium metasi cate;

(iii) sodium citrate; (iv) citπc acid;

(v) sodium bicarbonate;

(vi) sodium borate, preferably borax;

(vn) sodium hydroxide; and

(vin) mixtures of (ι)-(vιi). Preferred embodiments contain low levels of silicate (i.e. from about 3% to about 10%

Sι0₂).

The amount of the pH ad_justing component in the instant composition is preferably from about 1%) to about 50%), by weight of the composition. In a preferred embodiment, the pH- ad_justmg component is present in the composition an amount from about 5% to about 40%, preferably from about 10% to about 30%, by weight.

The preferred ADD compositions herein compnse a pH-adjusting component selected from water-soluble alkaline inorganic salts and water-soluble organic or inorganic builders as descnbed m U.S. Patent Nos. 5,705,464 and 5,710,115.

Matenal Care Agents - The preferred ADD compositions may contain one or more matenal care agents which are effective as anti-tarnish aids as descnbed in U S. Patent Nos. 5,705,464,

5,710,1 15 and 5,646,101.

SUBSTrrUTE SHEET (RULE 26) When present, such protecting matenals are preferably incorporated at low levels, e.g., from about 0.01% to about 5% of the ADD composition.

Other Matenals - Detersive ingredients or adjuncts optionally included the instant compositions can include one or more matenals for assisting or enhancing cleaning performance, treatment of the substrate to be cleaned, or designed to improve the aesthetics of the compositions. Adjuncts which can also be included in compositions of the present invention, at their conventional art-established levels for use (generally, adjunct matenals compnse, in total, from about 30% to about 99.9%, preferably from about 70% to about 95%, by weight of the compositions), include other active ingredients such as dyes, fillers, germicides, alkalinity sources, hydrotropes, anti-oxidants, perfumes, solubilizing agents, earners, processing aids, and pigments as descnbed in U.S. Patent Nos. 5,705,464, 5,710,115, 5,698,504, 5,695,679, 5,686,014 and 5,646,101. Tablet Form

As mentioned above, the composition of the present invention can be in a tablet form, especially a dimple tablet, which is preferred for use m automatic dishwashing machines.

A prefeiTed dimple tablet of the composition of the present invention and means for producing such a dimple tablet follows.

The preferred dimple tablet compnses (A) at least one compressed solid body portion (the tablet body) and (B) at least one non-compressed, non-encapsulating portion (the dimple portion). The use of the non-compressed, non-encapsulating portιon(s) and compressed portιon(s) provides a supeπor delivery mechanism for detergent active agents into the domestic wash process. Either of the non-compressed, non-encapsulating portιon(s) or the compressed portιon(s) can rapidly dissolve or disperse thereby providing for the earliest possible delivery of detergent active agents into the domestic wash process. The detergent tablet must have a ratio of B to A from about 1 :50 to about 4; 1 , preferably from about 1 :20 to about 1: 1, more preferably about 1 : 10 to about 1 : 1 , by area. Area A is the area of the detergent tablet, but excluding the area of the mould. Area B is the area of the non- compressed, non-encapsulating portion s.

The ratio of B to A gives optimal dissolution kinetics to the dimple. Additionally, the non-compressed, non-encapsulating portion s have improved visual noticibihty.

The detergent tablet, the mould(s) and non-compressed, non-encapsulating portιon(s) can be of any conceivable size and shape as long as the ratio of B to A remains from about 1:50 to about 4: 1. Preferably, when the detergent tablet is to be used in a dispensing device, such as those found in automatic dishwashers, the detergent tablet will be of a size suitable to be dispensed from the dispenser. Accordingly, by using this preferred dimple tablet, the detergent active components of a detergent tablet previously adversely affected by the compression pressure used to form the tablets may now be included in a detergent tablet. Examples of these components include bleaching agents and enzymes, such as the endolase enzyme of the present invention. In addition, these detergent active components may be separated from one another by having one or more compatible components contained in the compressed portion and one or more compatible components contained in the non-compressed, non-encapsulating portιon(s) of the tablet Examples of components that may interact and may therefore require separation include bleaching agents, bleach activators or catalyst and enzymes; bleaching agents and bleach catalysts or activators; bleaching agents and surfactants; alkalinity sources and enzymes. It may be advantageous to provide the compressed and the non-compressed, non- encapsulating portιon(s) such that they dissolve in the wash water with different dissolution rates. By controlling the rate of dissolution of each portion relative to one another, and by selection of the detergent active components in the respective portions, their order of release into the wash water can be controlled and the cleaning performance of the detergent tablet may be improved. For example it is often preferred that enzymes are delivered to the wash pπor to bleaching agent and/or bleach activator. It may also be preferred that a source of alkalinity is released into the wash water more rapidly than other components of the detergent tablet. It is also envisaged that it may be advantageous to prepare a detergent tablet accordmg to the present invention wherein the release of certain components of the tablet is delayed relative to other components.

The tablet may also compnse a plurality of moulds in the compressed solid body portion. These plurality of moulds may be overlapping or be distinctly separate.

The tablet may also compnse a plurality non-compressed, non-encapsulating portions. Such a plurality of non-compressed, non-encapsulating portions may be advantageous, enabling a tablet to be produced which has for example, a first and second and optional subsequent portions so that they have different rates of dissolution. Such performance benefits are achieved by selectively dehvenng detergent active components into the wash water at different times.

It is preferred that the detergent tablets, of the present invention be free from foul or noxious odors. If present such odors may be masked or removed. This includes the addition of masking agents, perfumes, odor absorbers, such as cyclodextnns, etc.

The detergent tablet can be transparent, opaque or any possible shade m between these two extremes. The compressed solid body and the at least one non-compressed, non- encapsulating portion can have the same or different degree of transparency, i.e. ranging from totally transparent to opaque. However, it is preferred that they be different. When there are more than one non-compressed, non-encapsulating portion present m the detergent tablet it is possible for each of the non-compressed, non-encapsulating portion to have the same or different degree of transparency, i.e. ranging from totally transparent to opaque However, it is preferred that they be different.

Furthermore, it is preferred that greater than 90%, more preferably 95%, even more preferably 98%, of the at least one non-compressed, non-encapsulating portion be free from visible cracks after one week of storage at ambient conditions Additionally, it is preferred that any gaps between the compressed solid body and the at least one non-compressed, non- encapsulating portion be less than 1 mm, more preferably 0 75 mm, even more preferably 0.5 mm, after one week of storage at ambient conditions.

The detergent tablets descnbed herein are preferably between 15g and lOOg in weight, more preferably between 18g and 80g in weight, even more preferably between 20g and 60g weight. The detergent tablet descnbed herein that are suitable for use m automatic dishwashing methods are most preferably between 20g and 40g in weight Detergent tablets suitable for use in fabπc laundenng methods are most preferably between 40g and lOOg, more preferably between 40g and 80g, most preferably between 40g and 65g m weight. The weight ratio of compressed portion to non-compressed, gel portion is generally greater than 0.5: 1, preferably greater than 1: 1, more preferably greater than 2:1, even more preferably greater than 3: 1 or even 4: 1, most preferably at least 5:1.

The compressed portions of the detergent tablets descnbed herein have Child Bite Strength (CBS) which is generally greater than lOKg, preferably greater than 12Kg, most preferably greater than 14Kg. CBS is measured as per the U.S. Consumer Product Safety Commission Test Specification

The dissolution rate of the at least one non-compressed, non-encapsulating portion can be greater than the dissolution rate of the compressed portion determined using the SOT AX dissolution test method. Alternatively, the dissolution rate of the compressed portion can be greater than the dissolution rate of the at least one non-compressed, non-encapsulating portion determined using the SOT AX dissolution test method.

Dissolution rate is measured using the SOT AX dissolution test method. For the purposes of the present invention dissolution of detergent tablets is achieved using a SOT AX (tradename) machine; model number AT7 available from SOT AX. SOTAX Dissolution Test Method: The SOTAX machine consists of a temperature controlled waterbath with lid. 7 pots are suspended in the water bath. 7 electric stimng rods are suspended from the underside of the hd, in positions corresponding to the position of the pots in the waterbath. The lid of the waterbath also serves as a lid on the pots.

The SOTAX waterbath is filled with water and the temperature gauge set to 50°C Each pot is then filled with 1 litre of deionised water and the stirrer set to revolve at 250rpm The lid of the waterbath is closed, allowing the temperature of the deionised water the pots to equilibrate with the water in the waterbath for 1 hour

The compressed portion and non-compressed, non-encapsulating portιon(s) are weighed and one tablet is placed in each pot, the hd is then closed. The compressed portion and non- compressed, non-encapsulating portion/s is visually monitored until it completely dissolves. The time is noted when the compressed portion and non-compressed, non-encapsulating portιon(s) has completely dissolved. The dissolution rate of the compressed portion and non-compressed, non-encapsulating portιon(s) is calculated as the average weight (g) of tablet dissolved in deionized water per minute. a Compressed portion

The compressed portion of the detergent tablet compπses at least one detergent active component descnbed herein but may compnse a mixture of more than one detergent active components, which are compressed. Any detergent tablet component conventionally used in known detergent tablets is suitable for incorporation into the compressed portion of the detergent tablets of this invention.

Detergent active component(s) present in the compressed layer may optionally be prepared in combination with a earner and/or a binder for example polymer (e g. PEG), liquid silicate. The detergent active components are preferably prepared in particulate form (i.e. powder or granular form) and may be prepared by any known method, for example conventional spray drying, granulation or agglomeration. The particulate detergent active component(s) are then compressed using any suitable equipment suitable for forming compressed tablets, blocks, bncks or bπquettes; descnbed in more detail hereafter.

The compressed solid body portion preferably has at least one mould on a surface of the compressed solid body portion. The non-compressed, non-encapsulating portιon(s) are mounted m to the moulds.

The compressed solid body portion may also be provided with a coating of a water- soluble matenal to protect the body portion. The coating layer preferably compnses a matenal that becomes solid on contacting the compressed and or the non-compressed portions within preferably less than 15 minutes, more preferably less than 10 minutes, even more preferably less than 5 minutes, most preferably less than 60 seconds. Preferably the coating layer is water- soluble. Preferred coating layers compnse matenals selected from the group consisting of fatty acids, alcohols, diols, esters and ethers, adipic acid, carboxylic acid, dicarboxylic acid, polyvinyl acetate (PVA), polyvinyl pyrro done (PVP), polyacetic acid, polyethylene glycol (PEG) and mixtures thereof. Preferred carboxylic or dicarboxylic acids preferably compnse an even number of carbon atoms. Preferably carboxylic or dicarboxylic acids compnse at least 4, more preferably at least 6, even more preferably at least 8 carbon atoms, most preferably between 8 and 13 carbon atoms. Preferred dicarboxylic acids mclude adipic acid, subenc acid, azelaic acid, subacic acid, undecanedioic acid, dodecanedioic acid, tndecanedioic and mixtures thereof. Preferred fatty acids are those having a carbon chain length of from C12 to C22, most preferably from C18 to C22. The coating layer may also preferably compnse a disrupting agent. Where present the coating layer generally present at a level of at least 0.05%, preferably at least 0.1%, more preferably at least 1%, most preferably at least 2% or even at least 5% of the detergent tablet. However, when the detergent tablet is an automatic dishwashing composition, it is preferred that when the compressed portion is coated that the coating not be a fatty acid, b. Non-Compressed. Non-Encapsulating Portion The non-compressed, non-encapsulating portion compnses deteregent active components, preferably the multi-function component of the present invention, and optionally, compnses other detergent active components, preferably other enzymes, more preferably an amylase.

The detergent active component(s) may be m any form for example particulate (i.e. powder or granular), gel or liquid form. The non-compressed, non-encapsulating portion in addition to compnsmg an detergent active component, may also optionally compnse a earner component. The detergent active component may be present m the form of a solid, gel or liquid, pπor to combination with a earner component.

The non-compressed, non-encapsulating portion is formulated such that the detergent active ingredient is essentially completely delivered a short penod of time. Typically, the gel portion is formulated so that at least about 80% of the detergent active is delivered to the wash of a domestic washing process withm the first 5 minutes, more preferably at least about 90% the first 3 minutes and even more preferably 95% withm the first 2 minutes.

The non-compressed, non-encapsulating portion of the detergent tablet may be in solid, gel, liquid or powder form.

The detergent tablet of the present invention requires that the non-compressed, non- encapsulating portion be delivered to the compressed portion such that the compressed portion and non-compressed, non-encapsulating portion contact each other. The non-compressed, non- encapsulating portion may be delivered to the compressed portion m solid or flowable form. Where the non-compressed, non-encapsulating portion is in solid form, it is pre-prepared, optionally shaped and then delivered to the compressed portion. The non-compressed, non- encapsulating portion is then affixed to a pre-formed compressed portion, for example by adhesion or by insertion of the non-compressed, non-encapsulating portion to a co-operating surface of the compressed portion. The compressed portion compnses at least one mould into which the non-compressed, non-encapsulating portion/s is/are delivered.

SUBSTΓΓUTE SHEET (RULE 26) The non-compressed, non-encapsulating portion is preferably delivered to the compressed portion m flowable form. The non-compressed, non-encapsulating portion is then affixed to the compressed portion for example by adhesion, by forming a coating over the non- compressed, non-encapsulating layer to secure it to the compressed portion, or by hardening, for example (I) by cooling to below the melting point where the flowable composition becomes a solidified melt; (n) by evaporation of a solvent; (in) by crystallization, (iv) by polymeπzation of a polymenc component of the flowable non-compressed, non-encapsulating portion, (v) through pseudo-plastic properties where the flowable non-compressed, non-encapsulating portion compnses a polymer and shear forces are applied to the non-compressed, non-encapsulating portion; (vi) combining a binding agent with the flowable non-compressed, non-encapsulating portion. In an alternative embodiment the flowable non-compressed, non-encapsulating portion may be an extrudate that is affixed to the compressed portion by for example any of the mechanism descnbed above or by expansion of the extrudate to the parameters of a mould provided by the compressed portion. The compressed portion compπses at least one mould into which the non-compressed non-encapsulated portιon(s) is/are delivered. In an alternative embodiment the surface of the compressed portion compπses more than one mould into which the non-compressed, non- encapsulating portion may be delivered. The mould(s) preferably at least partially accommodates one or more non-compressed, non-encapsulating portions. The non-compressed, non- encapsulating portιon(s) is then delivered into the mould(s) and affixed to the compressed portion as descnbed above. Alternatively, the detergent tablet contains one mould m which there are two non-compressed, non-encapsulating portions. The first non-compressed, non-encapsulating portion could be added as a liquid, which is allowed to set or harden, or as a pre formed gel. These two different non-compressed, non-encapsulatmg portion could have different rates of dissolution.

The non-compressed, non-encapsulatmg portion may compnse particulates, such as powders or granules. The particulates may be prepared by any known method, for example conventional spray drying, granulation, encapsulation or agglomeration. Particulates may be affixed to the compressed portion by incorporating a binding agent or by forming a coating layer over the non-compressed, non-encapsulating portion.

Where the detergent tablet compπses more than one non-compressed, non-encapsulatmg portion, the first and second and optional subsequent non-compressed, non-encapsulating portion may compnse particulates having substantially different average particle size. By substantially different average particle size we mean that the difference between the average particle size of the first and second and/or subsequent compositions is greater than 5%, preferably greater than 10%), more preferably greater than 15% or even 20% of the smaller average particle size. The average particle size of the particulate detergent active components used herein is calculated using a seπes of Tyler sieves. The senes consists of a number of sieves each having a different aperture size. Samples of a composition of detergent active components are sieved through the senes of sieves (typically 5 sieves). The weight of a sample of composition retained in the sieve is plotted against the aperture size of the sieve. The average particle size of the composition is defined as the aperture size through which 50% by weight of the sample of composition would pass.

Alternatively, compositions containing more than one detergent active components can have substantially different density. For example, the difference between the density of the first and second and/or subsequent compositions can be greater than about 5%, more preferably greater than about 10%, even more preferably greater than about 15% or even about 20% of the smaller density. Density of the particulate composition of detergent active components can be measured by any known method suitable for measuring density of particulate matenal.

Preferably, the density of the composition of detergent active components is measured usmg a simple funnel and cup device consisting of a conical funnel moulded ngidly on a base and provided with a flap valve at its lower extremity to allow the contents of the funnel to be emptied into an axially aligned cylmdncal cup disposed below the funnel. The funnel is 130 mm high and has internal diameters of 130 mm and 40 mm at its respective upper and lower extremities. It is mounted so that the lower extremity is 140 mm above the upper surface of the base. The cup has an overall height of 90 mm, an internal height of 87 mm and an internal diameter of 84 mm. Its nominal volume is 500 ml.

A density measurement is taken by hand pouring the composition into the funnel. Once the funnel is filled, the flap valve is opened and powder allowed to run through the funnel, overfilling the cup. The filled cup is removed from the frame and excess powder removed from the cup by passmg a straight edged implement e.g. a knife, across its upper edge The filled cup is then weighed and the value obtained for the weight of powder doubled to provide a bulk density m grams/litre. Replicate measurements are made as required.

Tablets m which one or more of the non-compressed, non-encapsulating portion compnse particulates and the average particle size and/or density of the first and the subsequent non-compressed, non-encapsulatmg portions are substantially different are preferred where the first and second and optionally subsequent non-compressed, non-encapsulatmg portions are required to have different rates of dissolution.

Where the non-compressed, non-encapsulatmg portion compnses a solidified melt, the melt is prepared by heating a composition compπsing a detergent active component and optional earner component(s) to above its melting point to form a flowable melt. The flowable melt is then poured into a mould in the surface of the compressed portion and allowed to cool. As the melt cools it becomes solid, taking the shape of the mould at ambient temperature Where the composition compπses one or more earner components, the earner component(s) may be heated to above their melting point, and then an detergent active component may be added. Carner components suitable for prepanng a solidified melt are typically non-active components that can be heated to above melting pomt to form a liquid and cooled to form an mtermolecular matnx that can effectively trap detergent active components. A preferred non-active carher component is an organic polymer that is solid at ambient temperature Preferably the non-active detergent component is polyethylene glycol (PEG) The compressed portion of the detergent tablet provides at least one mould to accommodate the melt. The flowable non-compressed, non-encapsulatmg portion may be in a form compnsmg a dissolved or suspended detergent active component. The flowable non-compressed, non- encapsulat g portion may harden over time to form a solid, semi-solid or highly viscous liquid non-compressed, non-encapsulatmg portion by any of the methods descnbed above. In particular, the flowable non-compressed, non-encapsulatmg portion may harden by evaporation of a solvent. Solvents suitable for use herein may include any known solvent in which a binding agent is soluble. Preferred solvents may be polar or non-polar and may include water, alcohol, (for example ethanol, acetone) and alcohol denvatives. In an alternative embodiment more than one solvent may be used.

The flowable non-compressed, non-encapsulat g portion may compnse one or more binding agents. Any binding agent that has the effect of causing the composition to become solid, semi-solid or highly viscous over time is envisaged for use herein. Although not wishing to be bound by theory, it is believed that mechanisms by which the binding agent causes a non-solid composition to become solid, semi-solid or highly viscous include, chemical reaction (such as chemical cross linking), or interaction between two or more components of the flowable compositions either; chemical or physical interaction of the binding agent with a component of the composition. Preferred binding agents mclude a sugar/gelatme combination, starch, glycerol and organic polymers. The sugar may be any monosacchaπde ( e.g. glucose), disacchande (e.g sucrose or maltose) or polysacchaπde. The most preferred sugar is commonly available sucrose For the purposes of the present invention type A or B gelatine may be used, available from for example Sigma. Type A gelatine is preferred since it has greater stability m alkaline conditions m compaπson to type B Preferred gelatine also has a bloom strength of between 65 and 300, most preferably between 75 and 100 Preferred organic polymers include polyethylene glycol (PEG) of molecular weight from 500 to 10,000, preferably from 750 to 8000, most preferably from 1000 to 6000 available from for example from Hoechst. Where the non-compressed, non-encapsulat g portion is an extrudate, the extrudate is prepared by premixing the detergent active components with optional carner components to form

TE SHEET RULE 26 a viscous paste. The viscous paste is then extruded using any suitable commonly available extrusion equipment such as for example a single or twin screw extruder available from for example APV Baker, Peterborough. U.K. The extrudate is then cut to size either after delivery to the compressed portion, or pπor to delivery to the compressed portion of the detergent tablet. The compressed portion of the tablet compπses at least one mould into which the extruded non- compressed, non-encapsulatmg portion is be delivered.

In a preferred embodiment the non-compressed, non-encapsulatmg portion is coated with a coating layer. The coating may be used to affix a non-compressed, non-encapsulat g portion to the compressed portion. This may be particularly advantageous where the non-compressed, non-encapsulatmg portion compπses flowable particulates, gels or liquids.

The coating layer preferably compπses a matenal that becomes solid on contacting the compressed and or the non-compressed, non-encapsulatmg portions withm preferably less than 15 minutes, more preferably less than 10 minutes, even more preferably less than 5 minutes, most preferably less than 60 seconds. Preferably the coating layer is water-soluble. Preferred coating layers compnse matenals selected from the group consisting of fatty acids, alcohols, diols, esters and ethers, adipic acid, carboxylic acid, dicarboxylic acid, polyvinyl acetate (PVA), polyvinyl pyrro done (PVP), polyacetic acid, polyethylene glycol (PEG) and mixtures thereof. Preferred carboxylic or dicarboxylic acids preferably compnse an even number of carbon atoms. Preferably carboxylic or dicarboxylic acids compnse at least 4, more preferably at least 6, even more preferably at least 8 carbon atoms, most preferably between 8 and 13 carbon atoms. Preferred dicarboxylic acids include adipic acid, subeπc acid, azelaic acid, subacic acid, undecanedioic acid, dodecandioic acid, tπdecanedioic and mixtures thereof. Preferred fatty acids are those having a carbon chain length of from C 12 to C22, most preferably from C18 to C22. The coating layer may also preferably compnse a disrupting agent. Where present the coating layer generally present at a level of preferably at least about 0.05%, more preferably at least about 0.1%, even more preferably at least about 1%, even more preferably still at least about 2% or even at least about 5% of the detergent tablet. However, when the detergent tablet is an automatic dishwashing composition, it is preferred that the coating not be a fatty acid.

As an alternative embodiment the coating layer may encapsulate the detergent tablet. In this embodiment the coating layer is present at a level of at least about 4%, more preferably at least about 5%, most preferably at least about 10% of the detergent tablet.

In a preferred embodiment the compressed and or non-compressed, non-encapsulatmg portions and/or coating layer additionally compnse a disrupting agent. The disrupting agent may be a disintegrating or effervescing agent. Suitable disintegrating agents include agents that swell on contact with water or facilitated water influx and/or efflux by forming channels m compressed and/or non-compressed, non-encapsulating portions . Any known disintegrating or effervescing agent suitable for use m laundry or dishwashing applications is envisaged for use herein. Suitable disintegrating agent include starch, starch denvatives, alg ates, carboxymethylcellulose (CMC), cellulosic-based polymers, sodium acetate, aluminium oxide. Suitable effervescing agents are those that produce a gas on contact with water. Suitable effervescing agents may be oxygen, nitrogen dioxide or carbon dioxide evolving species. Examples of preferred effervescing agents may be selected from the group consisting of perborate, percarbonate, carbonate, bicarbonate and carboxylic acids such as citnc or maleic acid.

An advantage of including a disrupting agent m the detergent tablet of the present invention is the transport, storage and handling benefits that can be achieved by increasing the hardness of the detergent tablet without adversely affecting the cleaning performance.

The non-compressed, non-encapsulatmg portion may additionally contain a drying agent. Any, conventional drying agent can be used. See Vogels Text book of Practical Organic

Chemistry, 5 Edition (1989) Longman Scientific & Technical, pp. 165-168, incorporated herein by reference. For example, suitable drying agents are anhydrous CaSθ4, anhydrous Na2Sθ4, calcium chlonde, sodium sulfite and MgSθ4. The selection of suitable drying agents may depend on the end use of the tablet. A drying agent for a detergent tablet for an automatic dishwashing composition for low temperatures preferably is sodium sulfite or calcium chlonde, but anhydrous CaSθ4, may be used for higher use temperatures. When present, drying agents are included in an amount of about 0.1% to about 15%, more preferably from about 0.1% to about 10%, even more preferably from about 0.5% to about 7%, by weight.

When the non-compressed, non-encapsulatmg portion is a gel mounted or formed onto the compressed solid body portion of the detergent tablet into a mould formed on the compressed solid body portion, the non-compressed, non-encapsulatmg portion may additionally contain a thickening system m addition to the at least one detergent active agent. When the non-compressed, non-encapsulatmg portion is a gel it may include solid ingredients which are dispersed or suspended within the gel. The solid ingredients aid m the control of the viscosity of the gel formulation in conjunction with the thickening system. When included, the non-compressed, non-encapsulatmg portion typically compnses at least about 15% solid ingredients, more preferably at least about 30% solid ingredients and most preferably at least about 40% solid ingredients. However, due to pumpabihty and other processing concerns, the non-compressed, non-encapsulatmg portion of the present invention typically do not include more than about 90% solid ingredients, when in the form of a gel. Thickening System As noted earlier, the detergent tablet of the present invention compnses thickening system in the non-compressed, non-encapsulatmg portion when it is a gel, to provide the proper viscosity or thickness of the gel portion The thickening system typically compnses a non- aqueous liquid diluent and an organic or polymenc gelling additive a) Liquid Diluent

The term "diluent" is used herein to connote the liquid portion of the thickening system. While some of the essential and/or optional components of the compositions herein may actually dissolve in the "diluenf-contammg phase, other components will be present as particulate mateπal dispersed withm the "dιluent"-contamιng phase. Thus the term "diluent" is not meant to require that the solvent matenal be capable of actually dissolving all of the detergent composition components added thereto. Suitable types of diluent useful in the non-aqueous thickening systems herein include alkylene glycol mono lower alkyl ethers, propylene glycols, ethoxylated or propoxylated ethylene or propylene, glycerol esters, glycerol triacetate, lower molecular weight polyethylene glycols, lower molecular weight methyl esters and amides, and the like

A preferred type of non-aqueous diluent for use herem compnses the mono-, di-, tn-, or tetra- C2-C3 alkylene glycol mono C2-Cg alkyl ethers. The specific examples of such compounds include diethylene glycol monobutyl ether, tetraethylene glycol monobutyl ether, dipropylene glycol monoethyl ether, and dipropylene glycol monobutyl ether. Diethylene glycol monobutyl ether and dipropylene glycol monobutyl ether are especially preferred. Compounds of the type have been commercially marketed under the tradenames Dowanol, Carbitol, and Cellosolve.

Another preferred type of non-aqueous diluent useful herein compnses the lower molecular weight polyethylene glycols (PEGs). Such matenals are those having molecular weights of at least about 150. PEGs of molecular weight ranging from about 200 to 600 are most preferred.

Yet another preferred type of non-aqueous diluent compπses lower molecular weight methyl esters. Such matenals are those of the general formula: Rl-C(0)-OCH3 wherein R^ ranges from 1 to about 18. Examples of suitable lower molecular weight methyl esters include methyl acetate, methyl propionate, methyl octanoate, and methyl dodecanoate.

The non-aqueous organic dιluent(s) employed should, of course, be compatible and non- reactive with other composition components, e.g., enzymes, used in the detergent tablets herein. Such a diluent component will generally be utilized in an amount of from about 10% to about 60% by weight of the composition. More preferably, the non-aqueous, low-polanty organic diluent will compnse from about 20% to about 50% by weight of the composition, most preferably from about 30% to about 50% by weight of the composition, b) Gelling Additive

As noted earlier, a gelling agent or additive is added to the non aqueous diluent of the present invention to complete the thickening system To form the gel required for suitable phase stability and acceptable rheology of the non-compressed, non-encapsulating portion, the organic gelling agent is generally present to the extent of a ratio of diluent to gelling agent in thickening system typically ranging from about 99: 1 to about 1 : 1 More preferably, the ratios range from about 19- 1 to about 4: 1.

The preferred gelling agents of the present invention are selected from castor oil denvatives, propylene glycol, polyethylene glycol, sorbitols and related organic thixatropes, organoclays, cellulose and cellulose denvatives, pluronics, stearates and stearate denvatives, sugar/gelatin combination, starches, glycerol, organic acid amides such as N-lauryl-L-glutamic acid di-n-butyl amide and mixtures thereof.

The preferred gelling agents are castor oil denvatives. Castor oil is a naturally occumng tπglyceπde obtained from the seeds of Ricmus Commums, a plant which grows m most tropical or subtropical areas. The pnmary fatty acid moiety m the castor oil tnglyceπde is ncmoleic acid (12-hydroxy oleic acid). It accounts for about 90% of the fatty acid moieties. The balance consists of dihydroxysteanc, palmitic, steanc, oleic, hnoleic, hnolenic and eicosanoic moieties. Hydrogenation of the oil (e.g., by hydrogen under pressure) converts the double bonds m the fatty acid moieties to single bonds, thus "hardening" the oil. The hydroxyl groups are unaffected by this reaction.

The resulting hydrogenated castor oil, therefore, has an average of about three hydroxyl groups per molecule. It is believed that the presence of these hydroxyl groups accounts in large part for the outstanding structunng properties which are imparted to the non-compressed, non- encapsulating portion compared to similar liquid detergent compositions which do not contain castor oil with hydroxyl groups in their fatty acid chains. For use in the compositions of the present invention the castor oil should be hydrogenated to an iodine value of less than about 20, and preferably less than about 10. Iodme value is a measure of the degree of unsaturation of the oil and is measured by the "Wijis Method," which is well-known in the art. Unhydrogenated castor oil has an iodine value of from about 80 to 90.

Hydrogenated castor oil is a commercially available commodity being sold, for example, in vanous grades under the trademark CASTORWAX.RTM. by NL Industπes, Inc., Highstown, New Jersey. Other Suitable hydrogenated castor oil denvatives are Thixcm R, Thixcin E, Thixatrol ST, Perchem R and Perchem ST, made by Rheox, Laporte. Especially preferred is Thixatrol ST.

Polyethylene glycols when employed as gelling agents, rather than solvents, have a molecular weight range of from about 2000 to about 30000, preferably about 4000 to about 12000, more preferably about 6000 to about 10000.

Cellulose and cellulose denvatives when employed m the present invention preferably include: I) Cellulose acetate and Cellulose acetate phthalate (CAP); n) Hydroxypropyl Methyl Cellulose (HPMC); ιπ)Carboxymethylcellulose (CMC); and mixtures thereof. The hydroxypropyl methylcellulose polymer preferably has a number average molecular weight of about 50,000 to 125,000 and a viscosity of a 2 wt. % aqueous solution at 25°C (ADTMD2363) of about 50,000 to about 100,000 cps. An especially preferred hydroxypropyl cellulose polymer is Methocel® J75MS-N wherein a 2.0 wt % aqueous solution at 25°C has a viscosity of about 75,000 cps.

The sugar may be any monosacchaπde ( e.g. glucose), disacchande (e.g. sucrose or maltose) or polysacchande. The most preferred sugar is commonly available sucrose. For the purposes of the present invention type A or B gelatin may be used, available from for example Sigma. Type A gelatin is preferred since it has greater stability in alkaline conditions in compaπson to type B. Preferred gelatin also has a bloom strength of between 65 and 300, most preferably between 75 and 100.

The non-compressed, non-encapsulatmg portion of the present invention may include a vanety of other ingredients in addition to the thickening agent as herein before descnbed and the detergent active disclosed in more detail below. Ingredients such as perfumes and dyes may be included as well as swelling/adsorbing agents such as carboxymethylcelluloses and starches to aid in adsorption of excess diluent or aid in the dissolution or breakup of the non-compressed, non-encapsulatmg portion m the wash. In addition, hardness modifying agents may incorporated into the thickening system to adjust the hardness of the gel if desired. These hardness control agents are typically selected from vanous polymers and polyethylene glycol's and when included are typically employed in levels of less than about 20% and more preferably less than about 10% by weight of the solvent m the thickening system. For example, hardening agents, such as high molecular weight PEG, preferably of a molecular weight from 10,000 to 20,000 or possibly even higher molecular weight, can be added to decrease the hardening time of the non-compressed, non-encapsulatmg portion. Alternatively, water soluble polymenc mateπals such as of low molecular weight polyethylene glycols may be added to the mould to form an intermediate barner layer pπor to addition of the non-compressed, non-encapsulatmg portion when it is a gel. This speeds coolmg and hardening of the gel by the melting/mixing of the water soluble polymenc matenal when the gel is added to the at least one mould. In addition, the intermediate layer may act as a bamer to prevent ingredients from the gel mixing or bleeding into the compressed portion.

Addition of an alkaline mateπal, such as sodium or potassium hydroxide can also speed in hardening of the non-compressed, non-encapsulating portion when it is a gel. Preferably, these alkaline matenals would be added to the mould before the addition of the gel. However, in alternative systems, the alkaline matenal may be added to the gel composition These alkaline matenals also have the advantage of acting as an additional alkalinity source that is discrete and would be slower dissolving and hence have a minimal impact on any effervescence system present m the non-compressed, non-encapsulatmg portion yet provide an alkalinity boost in the wash.

When it is a gel the non-compressed, non-encapsulatmg portion of the present invention is formulated so that the gel is a pumpable, flowable gel at slightly elevated temperatures of around 30°C or greater to allow increased flexibility in producing the detergent tablet, but becomes highly viscous or hardens at ambient temperatures so that the gel in maintained in position m the at least one mould in the compressed solid body portion of the detergent tablet through shipping and handling of the detergent tablet. Such hardening of the non-compressed, non-encapsulatmg portion may achieved, for example, by (l) by cooling to below the flowable temperature of the gel; (n) by evaporation of the diluent; or by (in) by polymenzation of the gelling agent. Preferably, the gel portion is formulated such that the gel hardens to sufficiently so that the maximum force needed to push a probe into the dimple preferably ranges from about 0.5N to about 40N. This force may be characteπzed by measunng the maximum force needed to push a probe, fitted with a strain gauge, a set distance into the gel. The set distance may be between 40 and 80% of the total gel depth. This force can be measured on a QTS 25 tester, usmg a probe of 5mm diameter. Typical forces measured are in the range of IN to 25N.

Additionally, it is preferred that when a 48 hour old tablet is inverted, at ambient conditions, for 10 minutes, more preferably 30 minutes, even more preferably 2 hours, the non- compressed, non-encapsulatmg portion does not dπp or separate from the compressed solid body. Lime soap dispersant compound - The compositions of detergent active components may contain a lime soap dispersant compound, preferably present at a level of from about 0.1% to about 40% by weight, more preferably about 1% to about 20%> by weight, most preferably from about 2% to about 10%) by weight of the compositions.

A lime soap dispersant is a mateπal that prevents the precipitation of alkali metal, ammonium or amme salts of fatty acids by calcium or magnesium ions. Preferred lime soap dispersant compounds are disclosed in PCT Application No. WO93/08877. Matenal Care Agents - The preferred ADD compositions may contain one or more matenal care agents which are effective as corrosion inhibitors and/or anti-tarmsh aids as descnbed m U.S. Patent Nos. 5,705,464, 5,710,115 and 5,646,101. When present, such protecting matenals are preferably incorporated at low levels, e.g., from about 0.01% to about 5% of the ADD composition.

Other Matenals - Detersive ingredients or adjuncts optionally included in the instant compositions can include one or more matenals for assisting or enhancing cleaning performance, treatment of the substrate to be cleaned, or designed to improve the aesthetics of the compositions. Ad_juncts which can also be included in compositions of the present invention, at their conventional art-established levels for use (generally, adjunct mateπals compnse, in total, from about 30% to about 99 9%, preferably from about 70% to about 95%, by weight of the compositions), include other active ingredients such as non-phosphate builders, chelants, enzymes, suds suppressors, dispersant polymers (e.g., from BASF Corp. or Rohm & Haas), color speckles, silvercare, anti-tarmsh and or anti-corrosion agents, dyes, fillers, germicides, alkalinity sources, hydrotropes, anti-oxidants, enzyme stabilizing agents, perfumes, solubilizing agents, earners, processing aids, pigments, and pH control agents as descnbed m U.S. Patent Nos. 5,705,464, 5,710,115, 5,698,504, 5,695,679, 5,686,014 and 5,646,101.

Since ADD compositions herein can contain water-sensitive ingredients or ingredients which can co-react when brought together m an aqueous environment, it is desirable to keep the free moisture content of the ADDs at a minimum, e.g., 7% or less, preferably 5% or less of the ADD; and to provide packaging which is substantially impermeable to water and carbon dioxide. Coating measures have been descnbed herein to illustrate a way to protect the ingredients from each other and from air and moisture. Plastic bottles, including refillable or recyclable types, as well as conventional bamer cartons or boxes are another helpful means of assunng maximum shelf-storage stability. As noted, when ingredients are not highly compatible, it may further be desirable to coat at least one such ingredient with a low-foammg nonionic surfactant for protection. There are numerous waxy mateπals which can readily be used to form suitable coated particles of any such otherwise incompatible multi-function components; however, the formulator prefers those mateπals which do not have a marked tendency to deposit or form films on dishes including those of plastic construction.

Product/Instructions - This invention also encompasses the inclusion of instructions on the use of the cleaning compositions descnbed herem with the packages containing the cleaning compositions or with other forms of advertising associated with the sale or use of the cleaning compositions. The instructions may be included in any manner typically used by consumer product manufactunng or supply companies. Examples include providing instructions on a label attached to the container holding the composition; on a sheet either attached to the container or accompanying it when purchased; or in advertisements, demonstrations, and or other wπtten or oral instructions which may be connected to the purchase or use of the cleaning compositions. Specifically the instructions will include a descnption of the use of the cleaning composition. The instructions, for instance, may additionally include information relating to the recommended amount of cleaning composition to apply to the surface, if soaking or rubbing is appropnate to the surface; the recommended amount of water, if any, to apply to the surface before and after treatment; other recommended treatment. ,

A product compnsmg a cleaning composition containing a multi-function component capable of hydrolyzing ,3-β-glucans, 1,4-β-glucans and combinations, both physically and chemically, of 1,3-β-glucans and 1 ,4-β-glucans, as more fully descnbed above, and optionally containing an amylase, the product further including instructions for using the cleaning composition to clean a surface (fabπc, dish, or other hard surface) in need of cleaning, the instructions including the step of contacting a surface with an effective amount of the cleaning composition such that said cleaning composition cleans said surface Process for Making Tablet

The detergent tablets of the present invention are prepared by separately prepanng the composition of detergent active components forming the respective compressed portion and the non-compressed, non-encapsulat g portion/s, forming the compressed soild body portion and dehveπng or adhenng the non-compressed, non-encapsulatmg portion s to the mould/s in the compressed portion.

The compressed portion is prepared by obtaining at least one detergent active component and optionally premixing with earner components. Any pre-mixmg will be earned out in a suitable mixer; for example a pan mixer, rotary drum, vertical blender or high shear mixer. Preferably dry particulate components are admixed in a mixer, as descnbed above, and liquid components are applied to the dry particulate components, for example by spraying the liquid components directly onto the dry particulate components. The resulting composition is then formed into a compressed portion in a compression step using any known suitable equipment. Preferably the composition is formed into a compressed portion using a tablet press, wherein the tablet is prepared by compression of the composition between an upper and a lower punch. In a preferred embodiment of the present invention the composition is delivered into a punch cavity of a tablet press and compressed to form a compressed portion using a pressure of preferably greater

2 2 than 6.3KN/cm , more preferably greater than 9KN/cm , most preferably greater than

2

14.4KN/cm^'

In order to form a tablet of the invention, wherein the compressed portion provides at least one mould to receive the non-compressed, non-encapsulat g portion/s, the compressed portion is prepared using a modified tablet press compnsmg modified upper and or lower punches. The upper and lower punches of the modified tablet press are modified such that the compressed portion provides one or more indentations which form the mould(s) to which the one non-compressed, non-encapsulating portion/s is delivered. The compressed portion can be cooled or even frozen before the non-compressed, non- encapsulatmg portion/s are added to the at least one mould. This cooling or freezing is particularly beneficial when the non-compressed, non-encapsulatmg portion is a gel.

As descnbed m detail herein before, the non-compressed, non-encapsulatmg portion/s compnses at least one detergent active component. The detergent active component and any other ingredients m the non-compressed, non-encapsulatmg portion s are pre-mixed using any known suitable mixing equipment. The non-compressed, non-encapsulatmg portion compπses at least one detergent active component. Where the non-compressed, non-encapsulatmg portion compnses more than one detergent active component the components are pre-mixed using any known suitable mixing equipment. In addition the non-compressed, non-encapsulatmg portion may optionally compnse a earner with which the detergent active components are combined. The non-compressed, non- encapsulatmg portion may be prepared in solid or flowable form. Once prepared the composition is delivered to the compressed portion. The non-compressed, non-encapsulatmg portion may be delivered to the compressed portion by manual delivery or using a nozzle feeder extruder or by any other suitable means. As the compressed portion compπses a mould, the non-compressed, non-encapsulatmg portion is preferably delivered to the mould using accurate delivery equipment, for example a nozzle feeder, such as a loss in weight screw feeder available from Optima, Germany or an extruder.

Where the flowable non-compressed, non-encapsulatmg portion is m particulate form the process compπses dehveπng a flowable non-compressed, non-encapsulatmg portion to the compressed portion in a delivery step and then coating at least a portion of the non-compressed, non-encapsulatmg portion with a coating layer such that the coating layer has the effect of substantially adhenng the non-compressed portion to the compressed portion.

Where the flowable non-compressed, non-encapsulatmg portion is affixed to the compressed portion by hardening, the process compnses a delivery step in which the flowable non-compressed, non-encapsulatmg portion is delivered to the compressed portion and a subsequent conditioning step, wherein the non-compressed, non-encapsulatmg portion hardens. Such a conditioning step may compnse drying, cooling, binding, polymeπzation etc. of the non- compressed, non-encapsulating portion , duπng which the non-compressed, non-encapsulatmg portion becomes solid, semi-solid or highly viscous. Heat may be used in a drying step. Heat, or exposure to radiation may be used to effect polymeπzation in a polymeπzation step.

It is also envisaged that the compressed portion may be prepared having a plurality of moulds. The plurality of moulds are then filled with a non-compressed, non-encapsulatmg portion. It is also envisaged that each mould can be filled with a different non-compressed, non- encapsulatmg portion or alternatively, each mould can be filled with a plurality of different non- compressed, non-encapsulating portion.

The detergent tablets may be employed m any conventional domestic washing process wherein detergent tablets are commonly employed, including but not limited to automatic dishwashing and fabπc laundeπng. Methods of Cleaning The surface in need of treatment is preferably selected from the group consisting of stainless steel and other metals, ceramic, plastic, metal, dishware, cookware, baby bottles, wood, glass and mixtures thereof. Such surfaces can be either non-porous or porous.

The method herein when employed to remove or reduce soils or stains is highly effective on cooked-on, burned-on, dπed-on and baked-on food soils. Additionally, it is highly effective on starch soils such as oatmeal and macaroni soils.

The cleaning compositions of the present invention are effective immediately upon contacting the soils and/or stains. However, the cleaning compositions are preferably in contact with the soils and/or stains for a penod of about 1 to about 120 minutes, more preferably, about 5 to about 60 minutes, most preferably, about 10 to about 30 minutes (the typical wash cycle time for automatic dishwashmg machines).

The cleaning compositions of the present invention are suitable for use at any temperature at which the multi-function components that are capable of hydrolyzing both 1-3-β- D-glucans and 1-4-β-D-glucans are effective. Preferably, the cleaning compositions are used at temperatures below about 70°C, more preferably, below about 60°C, most preferably, below about 50°C.

Preferred multi-function components that are capable of hydrolyzing both 1-3-β-D- glucans and 1-4-β-D-glucans include, but are not limited to, enzymes, more preferably cellulases.

The dishwashing methods of the present invention compnse contacting a surface m need of treatment with an effective amount of a cleaning composition containing a multi-function component that is capable of hydrolyzing both 1-3 -β-D-glucans and 1 -4-β-D-glucans such that the cleanmg composition treats the surface. Preferably, the cleaning compositions of the present invention are used in automatic dishwashers. However, m the case of manual dishwashing, any friction between the surface and the cleanmg composition, such as by scrubbing, etc., will facilitate removal and/or reduction of the soils. Although the methods and cleaning compositions of the present invention can be employed to assist in cleaning, especially tough food cleaning and/or removing and/or reducing spotting and or films, surfaces m need of treatment for any desired purpose, examples of likely uses include one or more of the following: soil removal, soil reduction, spot and or film removal and/or reduction, gnt removal, filter cleaning, stam removal and stam reduction. Preferably, the soils are carbohydrate soils, such as cellulose, gluon and xylon substrates deπved from cereal and gram soils. More preferably, the soils are oatmeal, barley, rye, wheat, nee and mixtures thereof.

Any suitable methods for machine washing or cleaning soiled tableware are envisaged. A preferred machine dishwashing method compnses treating soiled articles selected from crockery, glassware, silverware, metallic items, cutlery and mixtures thereof, with an aqueous liquid having dissolved or dispensed therein an effective amount of a detergent tablet in accord

UBSTΓΓUTE SHEET RULE 26 with the invention. By an effective amount of the detergent tablet it is meant from 8g to 60g of product dissolved or dispersed in a wash solution of volume from 3 to 10 litres, as are typical product dosages and wash solution volumes commonly employed in conventional machine dishwashing methods. Preferably the detergent tablets are from 15g to 40g m weight, more preferably from 20g to 35g in weight.

The following examples are meant to exemplify compositions of the present invention, but are not necessanly meant to limit or otherwise define the scope of the invention. Cleaning Compositions for Hard Surfaces and Dishes Examples

The abbreviations and terms used in the Examples are known to those of ordinary skill m the art and/or are defined herein.

Hard surface cleaning compositions

As used herein "hard surface cleaning composition" refers to liquid and granular detergent compositions for cleaning hard surfaces such as floors, walls, bathroom tile, and the like. Hard surface cleaning compositions of the present invention compnse an effective amount of one or more protease enzymes, preferably from about 0.0001%) to about 10%, more preferably from about 0.001% to about 5%, more preferably still from about 0.001% to about 1% by weight of active protease enzyme of the composition. In addition to compnsmg one or more protease enzymes, such hard surface cleanmg compositions typically compnse a surfactant and a water- soluble sequestering builder. In certain specialized products such as spray window cleaners, however, the surfactants are sometimes not used since they may produce a filmy/streaky residue on the glass surface. (See U.S. Patent No. 5,679,630 Examples).

The surfactant component, when present, may compnse as little as 0.1% of the compositions herein, but typically the compositions will contain from about 0.25% to about 10%, more preferably from about 1% to about 5% of surfactant. Typically the compositions will contain from about 0.5% to about 50% of a detergency builder, preferably from about 1% to about 10%. Preferably the pH should be m the range of about 8 to 12. Conventional pH adjustment agents such as sodium hydroxide, sodium carbonate or hydrochlonc acid can be used if adjustment is necessary.

Solvents may be included m the compositions. Useful solvents include, but are not limited to, glycol ethers such as diethyleneglycol monohexyl ether, diethyleneglycol monobutyl ether, ethyleneglycol monobutyl ether, ethyleneglycol monohexyl ether, propyleneglycol monobutyl ether, dipropyleneglycol monobutyl ether, and diols such as 2,2,4-tnmethyl-l,3- pentanediol and 2-ethyl-l,3-hexanedιol. When used, such solvents are typically present at levels of from about 0.5% to about 15%, preferably from about 3% to about 11%. Additionally, highly volatile solvents such as isopropanol or ethanol can be used in the present compositions to facilitate faster evaporation of the composition from surfaces when the surface is not nnsed after "full strength" application of the composition to the surface. When used, volatile solvents are typically present at levels of from about 2% to about 12% in the compositions.

The hard surface cleaning composition embodiment of the present invention is illustrated by the following nonhmitmg examples.

Examples 1-7 Liquid Hard Surface Cleaning Compositions

Example No.

Component 1 2 3 4 5 6 7

Endoglucanase¹ (pure) 0.05 0.05 0.20 0.02 0.03 0.10 0.03

Amylase² 0.36 - - 0.42 - 0.36 -

Chelant** - - - 2.90 2.90 - -

Citrate - - - - - 2.90 2.90

LAS - 1.95 - 1.95 - 1.95 -

AS 2.00 - 2.20 - 2.20 - 2.20

AES 2.00 - 2.20 - 2.20 - 2.20

Amine Oxide 0.40 - 0.50 - 0.50 - 0.50

Hydrotrope - 1.30 - 1.30 - 1.30 -

Solvent*** - 6.30 6.30 6.30 6.30 6.30 6.30

Water and Minors balance to 100%

¹ Endoglucanase having the amino acid sequence SEQ ID No. 1.

² Amylase as descnbed m WO 95/26397 and WO 96/23873. **Na4 ethylenediamme diacetic acid

***Dιethyleneglycol monohexyl ether

**** All formulas adjusted to pH 7

Dishwashing Compositions

EXAMPLE 8 A detergent tablet according to the present invention may be prepared as follows A detergent composition as m Example 2, formulation A is prepared and passed into a conventional rotary press. The press includes one punch shaped so that a mould is formed into one of the tablet surfaces. A gel matnx formulation as disclosed m Example 2, formulation A is then prepared. The proper amount of non-aqueous solvent is provided to a mixer and shear is applied to the solvent at a moderate rate (2,500-5,000 rpm) The proper amount of gelling agent is gradually added to the solvent under shear conditions until the mixture is homogeneous. The shear rate of the mixture is gradually increased to high shear condition of around 10,000 rpm. The temperature of the mixture is increased to between 55°C and 60°C. The shear is then stopped and the mixture is allowed to cool to temperatures between 35°C and 45°C. Using a low shear mixer, the remaining ingredients are then added to the mixture as solids. The final mixture is then metered into the mould on the compressed tablet body and allowed to stand until the gel hardens or is no longer flowable.

EXAMPLE 9 Automatic dimple tablet dishwashing detergent formulations in accordance with the present invention are prepared as follows:

Endoglucanase having the ammo acid sequence SEQ ED No. 1.

² Amylase as descnbed in WO 95/26397 and WO 96/23873.

³ Protease as disclosed in U.S. Patent No. 5,677,272.

⁴ Termamyl® 2xPCA commercially available from Novo Nordisk A S.

⁵ Termamyl® lxPCA commercially available from Novo Nordisk A/S.

⁶ White Termamyl® commercially available from Novo Nordisk A S.

Savinase® commerically available from Novo Nordisk A/S.

Plurafac C₁3-C15 mixed ethoxylated propoxylated fatty alcohol with an average degree of ethoxylation of 3.8 and an average degree of propoxylation of 4.5, sold under the tradename Plurafac by BASF. Alkyl-capped nonionic surfactant.

EXAMPLE 10 Automatic dimple tablet dishwashing detergent formulations in accordance with the present invention are prepared as follows:

Endoglucanase having the amino acid sequence SEQ ED No. 1. Amylase as described in WO 95/26397 and WO 96/23873. Protease as disclosed in U.S. Patent No. 5,677,272. Termamyl® 2xPCA commercially available from Novo Nordisk A/S. ⁶ White Termamyl® commercially available from Novo Nordisk A S.

⁷ Savinase® commerically available from Novo Nordisk A/S.

Plurafac C 13-^5 mixed ethoxylated/propoxylated fatty alcohol with an average degree of ethoxylation of 3.8 and an average degree of propoxylation of 4.5, sold under the tradename Plurafac by BASF.

Example 11 The following formulations are examples of compositions in accordance with the invention, which may be in the form of granules or in the form of a tablet.

¹ Endoglucanase having the amino acid sequence SEQ ID No. 1.

² Amylase as described in WO 95/26397 and WO 96/23873.

³ Protease as disclosed in U.S. Patent No. 5,677,272.

While particular embodiments of the subject invention have been described, it will be obvious to those skilled in the art that various changes and modifications of the subject invention can be made without departing from the spirit and scope of the invention. It is intended to cover, in the appended claims, all such modifications that are within the scope of the invention.

Having described the invention in detail with reference to preferred embodiments and the examples, it will be clear to those skilled in the art that various changes and modifications may be made without departing from the scope of the invention and the invention is not to be considered limited to what is described in the specification.

Claims

WHAT IS CLAIMED IS :

1. A cleaning composition compnsmg a) a multi-function component that is capable of hydrolyzing 1,3-β-glucans, 1,4-β- glucans and combinations of both physically and chemically linked 1,3-β-glucans and 1,4-β- glucans; and b) one or more cleaning adjunct matenals selected from the group consisting of: low foaming nonionic surfactants, hydrotropes and mixtures thereof.

2. The cleaning composition according to Claim 1 wherem said multi-function component is a cellulase enzyme, preferably an endoglucanase (EC 3.2.1.4), more preferably an endoglucanase (EC 3.2.1.4) which exhibits the following properties: (a) denved from Humicola insolens, DSM 1800; (b) approximate molecular weight of 50 kDa;

(c) iso-electnc point of 5.5; and

(d) containing 415 ammo acids; or an endoglucanase (EC 3.2.1.4) that has the amino acid sequence SEQ ID No. 1.

3. The cleaning composition according to Claim 1 wherein said cleaning composition further compnses an amylase, preferably an α-amylase vanant selected from the group consisting of:

(I) α-amylase charactenzed by having a specific activity at least 25% higher than the specific activity of Termamyl® at a temperature range of 25°C to 55°C and at a pH value in the range of 8 to 10, measured by Phadebas® α-amylase activity assay and/or;

(ii) α-amylase according to (l) compnsmg the ammo acid sequence shown m SEQ ID No. 2 or an α-amylase being at least 80% homologous with the amino acid sequence shown m SEQ DD No. 2 and/or;

(in) α-amylase according to (I) compnsmg the ammo acid sequence shown m SEQ ID No. 3 or an α-amylase being at least 80% homologous with the ammo acid sequence shown in SEQ ID No. 3 and/or;

(iv) α-amylase according to (l) compnsmg the following amino acid sequence N- termmal: Hιs-Hιs-Asn-Gly-Thr-Asn-Gly-Thr-Met-Met-Gln-Tyr-Phe-Glu-Tφ-Tyr-Leu-Pro-Asn- Asp (SEQ ID No. 4) or an α-amylase being at least 80% homologous with the ammo acid sequence shown (SEQ ID No 4) in the N-termmal and/or; (v) α-amylase according to (ι-ιv) wherein the α-amylase is obtainable from an alkalophi c Bacillus species and/or;

(vi) α-amylase according to (v) wherein the α-amylase is obtainable from any of the strains NCIB 12289, NCEB 12512, NCIB 12513 and DSM 935 and/or; (vn) α-amylase showing positive immunological cross-reactivity with antibodies raised against an α-amylase having an ammo acid sequence corresponding respectively to SEQ ID No 2, ED No. 3, or ED No 4 and/or;

(vni) vaπant of a parent α-amylase, wherein the parent α-amylase (1) has one of the amino acid sequences shown in SEQ ID No. 2, ED No. 3, or ED No 4, respectively, or (2) displays at least 80% homology with one or more of said ammo acid sequences, and/or displays immunological cross-reactivity with an antibody raised against an α-amylase having one of said ammo acid sequences, and/or is encoded by a DNA sequence which hybπdizes with the same probe as a DNA sequence encoding an α-amylase having one of said ammo acid sequences, m which vanants: (A) at least one ammo acid residue of said parent α-amylase has been deleted; and or (B) at least one amino acid residue of said parent α-amylase has been replaced by a different ammo acid residue; and or (C) at least one ammo acid residue has been inserted relative to said parent α-amylase; said vaπant having an α-amylase activity and exhibiting at least one of the following properties relative to said parent α-amylase: increased thermostability; increased stability towards oxidation; reduced Ca ion dependency; increased stability and/or α-amylolytic activity at neutral to relatively high pH values, increased α-amylolytic activity at relatively high temperature; and increase or decrease of the isoelectπc point (pi) so as to better match the pi value for α-amylase vaπant to the pH of the medium

4. The cleaning composition according to Claim 3 wherein said multi-function component and amylase are present m said cleaning composition m a range of ratios by ppm from 20: 1 to

1:20, preferably from 10:1 to 1:10, more preferably from 3:1 to 1:3.

5. The cleanmg composition according to any of the preceding Claims wherein said cleaning adjunct matenals further compnse one or more other surfactants, solvents, buffers, other enzymes, soil release agents, clay soil removal agents, thickeners, builders, dispersing agents, bleaching agents, baking soda, carbonates, phosphates, suds suppressors, fabnc softening agents, chelants, dyes, hydrobenzoic acid, dicarboxylic acid, siloxanes, perfumes, water and mixtures thereof, preferably wherein said cleaning adjunct mateπals further compnse a branched surfactant.

6. The cleaning composition according to Claim 5 wherein said cleaning adjunct matenals further compnse at least 0.1% surfactant by weight of the composition, said surfactant compnsmg mateπals selected from the group consisting of alkyl benzene suifonates, pnmary alkyl sulfates, secondary alkyl sulfates, alkyl alkoxy sulfates, alkyl alkoxy carboxylates, alkyl polyglycosides and their corresponding sulfated polyglycosides, α-sulfonated fatty acid esters, alkyl and alkyl phenol alkoxylates, betames and sulfobetaines amme oxides, N-methyl glucamides, nonionic pnmary alcohol ethoxylates, nonionic pnmary alcohol mixed ethoxy/propoxy, and mixtures thereof, preferably further compnsmg at least 5% builder selected from the group consisting of zeolites, polycarboxylates, layered silicates, phosphates, and mixtures thereof.

7. The cleaning composition according to Claim 5 wherein said cleanmg adjunct mateπals further compnse at least one bleaching agent selected from the group consisting of percarbonates, perborate, and mixtures thereof, preferably further compnsmg at least one bleach activator selected from the group consisting of tetraacetyl ethylene diamme (TAED), benzoylcaprolactam (BzCL), 4-mtrobenzoylcaprolactam, 3-chlorobenzoylcaprolactam, benzoyloxybenzenesulphonate (BOBS), nonanoyloxybenzenesulphonate (NOBS), phenyl benzoate (PhBz), decanoyloxybenzenesulphonate (C^Q-OBS), benzoylvalerolactam (BZVL), octanoyloxybenzenesulphonate (Cg-OBS), perhydrolyzable esters, 4-[N-(nonaoyl) ammo hexanoyloxyj-benzene sulfonate sodium salt (NACA-OBS), lauryloxybenzenesulphonate (LOBS or C12-OBS), 10-undecenoyIoxybenzenesulfonate (UDOBS or Cj j-OBS with unsaturation in the 10 position), and decanoyloxybenzoic acid (DOB A) and mixtures thereof.

8. The cleaning composition accordmg to Claim 5 wherein said cleaning adjunct mateπals further compnse at least one other detersive enzyme selected from the group consisting of other cellulases, lipases, other amylases, phosphohpases, proteases, peroxidases and mixtures thereof.

9. The cleanmg composition according to Claim 1 wherein said cleaning composition is in the form of a liquid, granule or bar.

10. The cleaning composition according to any of Claims 1-8 wherein said cleaning composition is a dishwashing detergent composition compnsmg:

(a) from 0.0001 % to 10% by weight of the composition of said multi-function component; and (b) from 0.1 % to 10% by weight of the composition of said low foaming nonionic surfactant; and (c) optionally, from 0.5% to 20% by weight of the composition of a bleaching agent.

11. The cleaning composition according to Claim 10 wherein said dishwashing detergent composition is in the form of a liquid, granule, powder or tablet.

12. An automatic dishwashing composition comprising:

(a) a tablet body including one or more cleaning adjunct materials; and

(b) a dimple portion including a multi-function component capable of hydrolyzing 1,3-β- glucans, 1,4-β-glucans and combinations, both physically and chemically, of 1,3-β-glucans and 1 ,4-β-glucans; wherein said dimple portion is attached to said tablet body such that said multi-function component is capable of activation prior to activation of said one or more cleaning adjunct materials of said tablet body.

13. A method for cleaning a surface in need of cleaning comprising contacting said surface with the dishwashing detergent composition according to Claim 10.

14. A method according to Claim 13 wherein said surface is selected from the group consisting of stainless steel, other metal substrates, ceramic, plastic, dishware, cookware, baby bottles, wood, glass, and mixtures thereof.

15. The method according to Claim 13 wherein said surface is treated for soil removal and/or soil reduction, preferably wherein the soil is a carbohydrate soil.

16. The method according to Claim 13 wherein said cleaning composition is formulated for activation of said multi-function component prior to activation of said one or more cleaning adjunct materials.

17. The method according to Claim 13 wherein said cleaning composition is an automatic dishwashing composition.

18. Use of the cleaning composition according to any of Claims 1-11 to clean a surface in need of cleaning.

19. A surface cleaned by the method according to Claim 13.

20 A dishwashing product compπsing a cleaning composition containing a multi-function component capable of hydrolyzing 1,3-β-glucans, 1 ,4-β-glucans and combinations of both physically and chemically linked 1,3-β-glucans and 1 ,4-β-glucans, and one or more cleaning adjunct mateπals selected from the group consisting of low foaming nonionic surfactants, said product further including instructions for using said cleaning composition, the instructions including the step of contacting a surface in need of cleaning with an effective amount of said cleaning composition such that said cleaning composition cleans said surface.

21. The product of Claim 20 wherein said multi-function component is an endoglucanase (EC 3.2.1.4), preferably an endoglucanase (EC 3.2.1.4) which exhibits the following properties:

(a) deπved from Humicola msolens, DSM 1800;

(b) approximate molecular weight of 50 kDa;

(c) iso-electπc point of 5.5; and (d) containing 415 ammo acids or an endoglucanase (EC 3.2.1.4) having the amino acid sequence SEQ. ID No. 1.

22. The product of Claim 20 wherein said cleaning composition further includes an amylase.