CA2211864C - Automatic dishwashing compositions comprising cobalt chelated catalysts - Google Patents

Abstract

Automatic dishwashing detergent compositions comprising certain cobalt catalysts are provided. More specifically, the invention relates to automatic dishwashing detergents which provide enhanced cleaning/bleaching benefits (especially tea stain removal) through the selection of cobalt chelated catalysts having the formula: [Co n L m X p]z Y
z. Preferred automatic dishwashing compositions comprise amylase and/or protease enzymes. Included are methods for washing tableware in domestic automatic dishwashing appliances using the cobalt catalysts.

Description

AUTOMATIC DISHWASHING COMPOSITIONS
COMPRISING COBALT CHELATED CATALYSTS
TECHNICAL FIELD
The present invention is in the field of automatic dishwashing detergents comprising bleach. More specifically, the invention encompasses automatic dishwashing detergents (liquids, pastes, and solids such as tablets and especially granules) comprising selected cobalt chelated catalysts. Preferred methods for washing tableware are included.
BACKGROUND OF THE INVENTION
Automatic dishwashing, particularly in domestic appliances, is an art very different from fabric laundering. Domestic fabric laundering is normally done in purpose-bui-It machines having a tumbling action. These are very different from spray-action domestic automatic dishwashing appliances.
The spray action in the latter tends to cause foam. Foam can easily overtlow the low sills of domestic dishwashers and slow down fihe spray action, which in turn reduces the cleaning action. Thus in the distinct field of domestic machine dcshwashing, the use of common foam-producing laundry detergent surfactants is normally restricted. These aspects are but a brief illustration of the unique formulation constraints in the domestic dishwashing field.
Automatic di;>hwashing with bleaching chemicals is different from fabric bleaching. In automatic dishwashing, use of bleaching chemicals involves promotion of soil removal from dishes, though soil bleaching may also occur. Additionally, soil antiredeposition and anti-spotting effects from bleaching chemicals would be desirable. Some bleaching chemicals, (such as a hydrogen peroxide source, alone or together with tetraacetylethylenediamine, TAED) can, in certain circumstances, be helpful for cleaning dishware, but this technology gives far from satisfactory results in a dishwashing context: for example, ability to remove tough tea stains is limited, especially en hard water, and requires rather large amounts of WO 96/23860 1'CT/US96/01198

2 bleach. Other bleach activators developed for laundry use can even give negative effects, such as creating unsightly deposits, when put into an automatic dishwashing product, especially when they have overly low solubility. Other bleach systems can damage items unique to dishwashing, such as silverware, aluminium cookware or certain plastics.
Consumer glasses, dishware and flatware, especially decorative pieces, as washed in domestic automatic dishwashing appliances, are often susceptible to damage and can be expensive to replace. Typically, consumers dislike having to separate finer pieces and would prefer the convenience and simplicity of being able to combine all their tableware and cooking utensils into a single, automatic washing operation. Yet doing this as a matter of routine has not yet been achieved.
On account of the foregoing technical constraints as well as consumer needs and demands, automatic dishwashing detergent (ADD) compositions are undergoing continual change and improvement. Moreover environmental factors such as the restriction of phosphate, the desirability of providing ever-better cleaning results with less product, providing less thermal energy, and less water to assist the washing process, have all driven the need for improved ADD compositions.
A recognized need in ADD compositions is to have present one or more ingredients which improve the removal of hot beverage stains (e.g., tea, coffee, cocoa, etc.) from consumer articles. Strong alkalis like sodium hydroxide, bleaches such as hypochlorite, builders such as phosphates and the like can help in varying degrees but all can also be damaging to, or leave a film upon, glasses, dishware or silverware. Accordingly, milder ADD
compositions have been developed. These make use of a source of hydrogen peroxide, optionally with a bleach activator such as TAED, as noted. Further, enzymes such as commercial amylolytic enzymes (e.g., TERMAMYL~ available from Novo Nordisk S/A) can be added. The alpha-amylase component provides at least some benefit in the starchy soil removal properties of the ADD. ADD's containing amylases typically can deliver a somewhat more moderate wash pH in use and can remove starchy soils while avoiding delivering large weight equivalents of sodium hydroxide on a per-gram-of-product basis. It would therefore be highly desirable to

3 secure improved bleach activators specifically designed to be compatible in ADD formulations, especially with enzymes such as amylases. A need likewise exists to :secure better amylase action in the presence of bleach activators.
Certain manganese catalyst-containing machine dishwashing compositions are d~°scribed in U.S. Patent 5,246,612, issued September 21, 1993, to Van Dijk Eat al. The compositions are said to be chlorine bleach-free machine dishwashing compositions comprising amylase and a manganese catalyst (in the +3 or +4 oxidation state), as defined by the structure given therein. Preferred manganese catalyst therein is a Binuclear manganese, macrocyclic ligand-containing molecule said to be MnIV2(u-O)3(1,4,7-trimethyl~-1,4,7-triazacyclononane)2(PFg)2. There continues to be, however, a need for catalysts that are effective in automatic dishwashing compositions and methods.
The comparative inferiority of the cobalt catalysts herein versus manganese catalysts is reported for laundry uses to remove tea stains from cotton fabrics in U.;S. 5,244,594, to Favre et al., issued September 14, 1993.
Therein, Example I provides data slowing a Co-Co catalyst according to European Patent Application, Publication No. 408,131, published January 16, 1991 by Unilever NV, is inferior to the manganese catalysts. Further, Example IV also reports lower stain removal at 20°C for a Co-Co catalyst of EP 408,131 versus a manganese catalyst.
It is an object of the instant invention to provide automatic dishwashing compositions, especially compact granular, phosphate-free types, incorporating an improved selection of cobalt catalyst-containing bleaching ingredients. A further object is to provide fully-formulated ADD
compositions with or without amylase enzymes, but especially the former, wherein specific cobalt catalyst-containing bleach systems are combined with additional selected ingredients including conventional amylases or bleach-stable amylases, so as to deliver superior tea cleaning results and at the same time excellent care for consumer tableware and flatware.
BACKGROUND ART
In addition to the hereinbefore-noted U.S. Patent 4,810,410, to Diakun et al, issued March 7,1989; U.S. 5,246,612, to Van Dijk et al., issued

4 September 21, 1993; U.S. 5,244,594, to Favre et al., issued September 14, 1993; and European Patent Application, Publication No. 408,131, published January 16, 1991 by Unilever NV, see also: U.S. Patent 5,114,611, to Van Kralingen et al, issued May 19, 1992 (transition metal complex of a transition metal, such as cobalt, and a non-macro-cyclic ligand); U.S. Pat.
4,430,243, to Bragg, issued February 7, 1984 (laundry bleaching compositions comprising catalytic heavy metal cations, including cobalt), German Patent Specification 2,054,019, published October 7, 1971 by Unilever N.V. (cobalt chelant catalyst); and European Patent Application Publication No. 549,271, published June 30, 1993 by Unilever PLC
(macrocyclic organic ligands in cleaning compositions).
SUMMARY OF THE INVENTION
The present invention encompasses automatic dishwashing detergents comprising:
(a) a catalytically effective amount of a cobalt chelated catalyst having the formula:
~ConLmXP~z Yz wherein n is an integer from 1 to 4 (preferably 1 or 2); m is an integer from 1 to 12 (preferably from 1 to 5); p is an integer from 0 to 8 (preferably from 0 to 4); Y is a counterion selected dependent on the charge z of the complex; X is a coordinating species selected from the group consisting of CI-, Br, I-, F-, NCS-, 13,-0H, 022-, 02-, HOO-, H20, SH, CN-, OCN-, S42-, NH3, NR3, RCOO-, RO-;
O O

RS03- and RS04 in which R is selected from hydrogen, substituted and unsubstituted alkyl, substituted and unsubstituted aryl, and R'COO- where R' is selected from substituted and unsubstituted alkyl and substituted and unsubstituted aryl, and mixtures thereof; and L is an organic ligand molecule containinl~ more than one heteroatom (preferably 2 to 5; more preferably 2 to 4) sE:lected from N, P, O, and S which coordinate via at least two heteroatoms (preferably via two nitrogen atoms);
(b) an effectiv~a amount of a source of hydrogen peroxide; and (c) automatic dishwashing detergent adjunct materials.
The preferred automatic dishwashing detergent compositions herein further comprise an amylase enzyme. Whereas conventional amylases such as TERMAMh'L~ may be used with excellent results, preferred ADD
compositions can use oxidative stability-enhanced amylases. Such an amylase is available from NOVO. In it, oxidative stability is enhanced from substitution using threonine of the methionine residue located in position 197 of B.Lichenifc~rmis or the homologous position variation of a similar parent amylase.
The instant ADD's have numerous advantages, for example they are economical, compact, less damaging to consumer tableware than might be expected on the basis of their potent bleaching action, they are not reliant on chlorinated compounds, and they may be formulated to avoid the undesirable use of overly high levels of caustic ingredients. In certain preferred embodiments, they are substantially free of boron and/or phosphate.
In the ADD composition embodiments, additional bleach-improving materials can be present. Preferably, these are selected from bleach activator materials, such as tetraacetylethylenediamine ("TAED").
The present invention encompasses granular-form, fully-formulated ADD's, preferably phosphate builder-free and chlorine bleach-free, in which additional ingredients, including other enzymes (especially proteases and/or amylases) are formulated.
The instant invention also encompasses methods; more particularly, a method of washing tableware in a domestic automatic dishwashing appliance, comprising treating the soiled tableware in an automatic dishwasher with an aqueous alkaline bath comprising a cobalt-containing catalyst having th~~ formula as provided hereinbefore and a source of hydrogen peroxide.

The present invention also relates to automatic dishwashing rinse aid compositions comprising a cobalt-containing catalyst as described herein, and methods for treating tableware in a domestic automatic dishwashing appliance during a rinse cycle with these cobalt-containing catalysts.
As already noted, the invention has advantages, including the excellent combination of tea stain removal, good dishcare, and good overall cleaning aided by a greater flexibility to formulate enzymes, especially amylases.
All parts, percentages and ratios used herein are expressed as percent weight unless otherwise specified.
DETAII~D DESCRIPTION, OF THE INVENTION
Automatic Dishwashing Compositions:
Automatic dishwashing compositions of the present invention preferably comprise a source of hydrogen peroxide and a particularly selected cobalt catalyst. The source of hydrogen peroxide is any common hydrogen-peroxide releasing salt, such as sodium perborate or sodium percarbonate. In the preferred embodiments, additions) ingredients such as water-soluble silicates (useful to provide alkalinity and assist in controlling corrosion), low-foaming nonionic surfactants (especially useful in automatic dishwashing to control spotting~lming), dispersant polymers (which modify and inhibit crystal growth of calcium andlor magnesium salts), chelants (which control transition metals), builders such as citrate (which help control calcium andlor magnesium and may assist buffering action), alkalis (to adjust pH), and detersive enzymes (to assist with tough food cleaning, especially of starchy and proteinaceous soils), are present. Additional bleach-modifying materials such as conventional bleach activators such as TAED may be added, provided that any such bleach-modifying materials are delivered in such a manner as to be compatible with the purposes of the present invention. The present detergent compositions may, moreover, comprise one or more processing aids, fillers, perfumes, conventional enzyme particle-making materials including enzyme cores or "nonpareils", as well as pigments, and the like.

WO 96123860 PCT/US96l01198 In general, materials used for the production of ADD compositions herein are preferably checked for compatibility with spottinglfilming on glassware. Test methods for spotting/filming are generally described in the automatic dishwashing detergent literature, including DIN test methods.
Certain oily materials, especially at longer chain lengths, and insoluble materials such as clays, as well as long-chain fatty acids or soaps which form soap scum are: therefore preferably limited or excluded from the instant compositions.
Amounts of the essential ingredients can vary within wide ranges, however preferred automatic dishwashing detergent compositions herein (which have a 1 % .aqueous solution pH of from about 7 to about 12, more preferably from about 9 to about 12, and most preferably less than about 11, especially from about 9 to about 11 ) are those wherein there is present:
from about 0.1 % to about 70%, preferably from about 0.5% to about 30% of a source of hydrogen peroxide; from about 0.01 % to about 2%, preferably from about 0.05% to about 1 % of the cobalt catalyst; from about 0.1 % to about 40%, preferably from about 0.1 % to about 20% of a water-soluble silicate; and from about 0.'I % to about 20% , preferably from about 0.1 % to about 10% of a low-foaming nonionic surtactant. Such fully-formulated embodiments typically further comprise from about 0.1 % to about 15% of a polymeric dispersant, from about 0.01 % to about 10% of a chelant, and from about 0.00001 % 1:o about 10% of a detersive enzyme though further additional or adjunct ingredients may be present. Detergent compositions herein in granular form typically limit water content, for example to less than about 7% free water, for best storage stability.
Further, preferred ADD compositions of this invention are substantially free of chlorine bleach. By "substantially free" of chlorine bleach is meant that the formulator does not deliberately add a chlorine-containing bleach additive, such as a chloroisocyanurate, to the preferred ADD camposition.
However, it is recognized 'that because of factors outside the control of the formulator, such as. chlorination of the water supply, some non-zero amount of chlorine bleach may be present in the wash liquor. The term "substantially free" can be similarly constructed with reference to preferred limitation of other ingredients, such as phosphate builder.

WO 96/23860 PCT/LTS96l01198 By "effective amount" herein is meant an amount which is sufficient, under whatever comparative test conditions are employed, to enhance cleaning of a soiled surface. Likewise, the term "catalytically effective amount" refers to an amount of cobalt catalyst which is sufficient under whatever comparative test conditions are employed, to enhance cleaning of the soiled surface. In automatic dishwashing, the soiled surface may be, for example, a porcelain cup with tea stain, dishes soiled with simple starches or more complex food soils, or a plastic spatula stained with tomato soup.
The test conditions will vary, depending on the type of washing appliance used and the habits of the user. Some machines have considerably longer wash cycles than others. Some users elect to use warm water without a great deal of heating inside the appliance; others use warm or even cold water fill, followed by a warm-up through a built-in electrical coil. Of course, the performance of bleaches and enzymes will be affected by such considerations, and the levels used in fully-formulated detergent and cleaning compositions can be appropriately adjusted.
Cobalt Catalysts:
The present invention compositions and methods utilize cobalt (III) catalysts having the formula:
IConLmXplz Yz wherein n is an integer from 1 to 4; m is an integer from 1 to 12; p is an integer from 0 to 8; Y is a counterion selected dependent on the charge z of the complex; X is a coordinating species selected from the group consisting of CI-, Br, I-, F-, NCS-, Ig,-OH, 022-, 02-, HOO-, H20, SH, CN-, OCN-, S42-, NHg, NRg, RCOO-, RO-;

RS03- and RS04 in which R is selected from hydrogen, substituted and unsubstituted alkyl, substituted and unsubstituted aryl, and R'COO- where R' is selected from substituted and unsubstituted alkyl and substituted and unsubstituted aryl, and mixtures thereof; and L is an organic ligand molecule containing more than one heteroatom (preferably 2 to 5; more preferably 2 to 4) selected from N, P, 0, and S which coordinate via at least two heteroatoms (preferably via two nitrogen atoms).
Preferred L are selected from the following groups.
(a) Macrocyclic organic molecules of the formula:
D-(CR~R~~-[-D-(CRS R'~-]s wherein R~ and R2 can each be zero, H, substituted and unsubstituted alkyl, substituted and unsubstituted aryl, each D can be independently N, NR, PR, 0 or S, wherein R is H, substituted or unsubstituted alkyl, and substituted or unsubstituted aryl. If D=N, one of the hetero-carbon bonds attached thereto~vill be unsaturated, giving ris~ to a -N=CRS- fragment, t and t' are each independently 2 or 3, and s=2, 3, 4 or 5.
This ligand L is preferably a macrocyclic organic molecule of the following general formula:
D-(CRtR2~-I-D--(CR~R2~'-'~s wherein R~ and R2 can each be zero, H, substituted and unsubstituted alkyl, or substituted and unsubstituted aryl; D and D' are each independently NR, PR, 0 or S, wherein R is H, substituted and unsubstituted alkyl or substituted and unsubstituted aryl; t and t' are each independently integers from 2-3: and s is an integer from 2-4. Preferably, n=m=2.
Preferred ligands are those in which D or D' is NH or NR; t and t' are 2 or 3, s=2, and R~ =RZ=H, more preferably, wherein D or D' is NCH3 and t, t'=2.
Other preferred ligands are those wherein D or D' is NCH; t, t'=2, s=2; and R~ and R2 can each be H or alkyl.
Examples of these ligands are:

1,4, 7-triazacyclononane;

1,4,7-triazacyciodecane;
1,4, 7-trimethyl-1, 4, 7-triazacyclononane;
1,4,7-trimethyl-I-4,7-triazacycfodecane;
1,4,8-trimethyl-1,4,8-triazacycloundecane;
1, 5, 9-trimethyl-1, 5,9-triatriazacyclododecane;
1,4-dimethyl-7-ethyl-1,4, 7-triazacyclonanane.
ii) Tris(pyridin-2-yl)methane;
Tris(pyrazol-!-yl)methane;
Tris(imidazol-2-yl)methane Tris(triazol-I-yl)methane;
iii) Tris(pyridin-2-yl)borate;
Tris(triazol)-!-yl)borate;
Tris(imidazol-2-yl)phosphine;
Tris(imidazol-2-yl)borate.
iv) cis-cis-1, 3, 5-trisamino-cyciohexane;
1,1,1-tris(methylamino)~thane.
v) Bis(pyridin-2-yl-methyi)amine;
Bis(Pyrazol-1-yl-methyi)amir~s;
Bis(triazol-I-yl-methyl)amine;
B is( imidazol-2-yl-methyl )amine;
They may be substituted on amine nitrogen atoms andlor CH2 carbon atoms and/or aromatic rings.
Such ligands are known and are described in U.S. Patent 5,246,621, to Favre et al, issued September 21, 1993, and in U.S. Patent 5,274,147, to Kerschnsr et al., issued December 28, 1993.
(b) SALEN-type and SALPD-type ligands of the general formulae:

_ ., O N
~CRIR2)m t R2) m b ~2 and QI
I~ JI
O N
(CR 1R2)m (CR1 R2)m T T
(CRi R2)m b (CRl R2 )m "T .. _ _ b wherein m is 2-6, preferably 2-3; R~ , R2 can each be a substituent selected from H, substituted and unsubstituted alkyl, substituted and unsubstituted aryl; Q~ and Q2 can each be a substituent selected from H, optionally substituted alkyl or aryl, N02, NR2, NR3+, O-alkyl, O-aryl, halogen, S02-, alkyl S03- and aryl S03-, T is either NR, 0, PR or S, wherein R=R1 or R2 and b is 0-1.
Preferred ligands are those wherein T=NR, m=3 and R, R1 and R2 are H; more preferably wherein b=0.
Such ligands are known and are described in European Patent Application Publication No. 408,131, published January 16, 1991.
(c) Non-macro-cyclic ligands of the formula:
' 3 R~ ~B~ ,R
R~ N C C~~N_R°
in which R1, R2, R3 and R4 can each be selected from H, optionally substituted alkyl and aryl groups, and such substituents in which each R1-N=C-R2 and R3-C=N-R4 form a five- or six-membered, optionally substituted, nitrogen-containing heterocyclic ring system; and B is a bridging group selected from 0, S, CR5R6, NR7 and C=0, wherein R5 R6 and R7 can each be H, alkyl or aryl groups which may optionally be substituted. Examples of optional substituents are halogen, OH, N02 NH2, S03-, OCH3, N+(CH3)3.
The ligands as contemplated herein are thus non(macro) cyclic compounds.
Typical five- or six-membered ring systems forming the ligand are, for example, pyridine, pyridazine, pyrimidine, pyrazine, imidazole, pyrazole and triazole rings which can optionally contain the usual types of substituents, such as alkyl, aryl, alkoxy, halide and vitro. The two rings may be identical or different, preferably identical.
Especially preferred ligands are those in which both rings are pyridine, preferably having NH as the bridging group B.
Such ligands are known and are described in U.S. Patent 5,114,611, to Van Kralingen et al., issued May 19, 1992.
(d) Porphyrin-type ligands of the formula:

Ar Ar as described in European Patent Applications Publication No.
306,089, published March 8, 1989 and Publication No. 384,503, published August 29, 1990.
Methods for making these cobalt chelated catalysts are known, having been described, for example, in U. S. Patent 5,114,611, to Van Kralingen et al., issued May 19, 1992 and European Patent Application Publication No. 408,131, published January 16, 1991.
These cobalt catalysts may be coprocessed with adjunct materials so as to reduce the color impact if desired for the aesthetics of the product, or the composition may be manufactured to contain catalyst "speckles".
As a practical matter, and not by way of limitation, the ADD
compositions and processes herein can be adjusted to provide on the order of at least one part per ten million of the active cobalt catalyst species in the aqueous washing medium, and will preferably provide from about 0.1 ppm to about 50 ppm, more preferably from about 1 ppm to about 25 ppm, and most preferably from about 2 ppm to about 10 ppm, of the cobalt catalyst species in the wash liquor. In order to obtain such levels in the wash liquor, typical ADD compositions herein will comprise from about 0.04°~ to about 1 °~, more preferably from about 0.07°~ to about 0.4°r6, by weight of the ADD
compositions.
Hvdroaen Peroxide Source Hydrogen peroxide sources are described in Kirk Othmer's Encyclopedia of Chemical WO 96/23860 PCTlUS96/01198 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 various coated and modified forms. An "effective amount" of a source of hydrogen peroxide is any amount capable of measurably improving stain removal (especially of tea stains) from soiled dishware compared to a hydrogen peroxide source-free composition when the soiled dishware is washed by the consumer in a domestic automatic dishwasher in the presence of alkali.
More generally a source of hydrogen peroxide herein is any convenient compound or mixture which under consumer use conditions provides an effective amount of hydrogen peroxide. Levels may vary widely and are usually in the range from about 0.1 % to about 70%, more typically from about 0.5% to about 30%, by weight of the ADD compositions herein.
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. Sodium perborate monohydrate and sodium percarbonate are particularly preferred. Mixtures of any convenient hydrogen peroxide sources can also be used.
A preferred percarbonate bleach comprises 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 various commercial sources such as FMC, Solvay and Tokai Denka.
While effective bleaching compositions herein may comprise only the identified cobalt catalysts and a source of hydrogen peroxide, fully-formulated ADD compositions typically will also comprise other automatic dishwashing detergent adjunct materials to improve or modify performance.
These materials are selected as appropriate for the properties required of an automatic dishvvashing composition. For example, low spotting and filming is desired -- preferred compositions have spotting and filming grades of 3 or less, preferably less than 2, and most preferably less than 1, as measured by the standard test of The American Society for Testing and Materials ("ASTM") D3556-85 (Reapproved 1989) "Standard Test Method for Deposition on i~lassware During Mechanical Dishwashing". Also for example, low sudsing is desired -- preferred compositions produce less than 2 inches, more preferably less than 1 inch, of suds in the bottom of the dishwashing machine during normal use conditions (as determined using known methods such as, for example, that described in U.S. Patent

5,294,365, to Welch et al., issued March 15, 1994).
Adjunct Materials:
Detersive ingredients or adjuncts optionally included in the instant compositions can include one or more materials for assisting or enhancing cleaning performance, treatment of the substrate to be cleaned, or designed to improve the aesthetics of the compositions. They are further selected based on the form of the composition, i.e., whether the composition is to be sold as a liquid, paste (semi-solid), or solid form (including tablets and the preferred granular norms for the present compositions). Adjuncts which can also be included in compositions of the present invention, at their conventional art-established levels for use (generally, adjunct materials comprise, 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 dispersant polymers (e.g., from BASF Corp. or Rohm &
Haas), color speckles, silvercare, anti-tarnish and/or anti-corrosion agents, dyes, fillers, germicides, alkalinity sources, hydrotropes, anti-oxidants, enzyme stabilizinl~ agents, perfumes, solubilizing agents, carriers, processing aids, pigments, and, for liquid formulations, solvents, as described in detail inereinafter.
1. Detergent Suifiactants:
(a) Low-Foamin4 Nonionic Surtactant - Surfactants are useful in Automatic Dishwa:ching to assist cleaning, help defoam food soil foams, especially from proteins, and to help control spotting/filming and are desirably included in the present detergent compositions at levels of from about 0.1 % to about 20% of the composition. In general, bleach-stable surfactants are preferred. ADD (Automatic Dishwashing Detergent) compositions of the present invention prefereably comprise low foaming nonionic surfactants (LFNIs). LFNI can be present in amounts from 0 to about 10% by weight, preferably from about 0.25% to about 4%. LFNIs are most typically used in ADDs on account of the improved wafer-sheeting action (especially from glass) which they confer to the ADD product. They also encompass non-silicone, nonphosphate polymeric materials further illustrated hereinafter which are known to defoam food soils encountered in automatic dishwashing.
Preferred LFNIs include nonionic alkoxylated surfactants, especially ethoxylates derived from primary alcohols, and blends thereof with more sophisticated surfactants, such as the polyoxypropylene/polyoxyethylene/polyoxypropylene (PO/EO/PO) reverse block polymers. The PO/EO/PO polymer-type surfactants are well-known to have foam suppressing or defoaming action, especially in relation to common food soil ingredients such as egg.
The invention encompasses preferred embodiments wherein LFNI is present, and wherein this component is solid at about 95°F (35oC), more preferably solid at about 77°F (25oC). For ease of manufacture, a preferred LFNI has a melting point between about 77°F (25°C) and about 140oF (60oC), more preferably between about 80oF (26.6oC) and 110°F
(43.3oC).
In a preferred embodiment, the LFNI is an ethoxylated surfactant derived 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 derived from a straight chain fatty alcohol containing from about 16 to about 20 carbon atoms (C16-C20 alcohol), preferably a C1g 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 ethoxyiated nonionic surfactant so derived has a narrow ethoxylate distribution relative to the average.
The LFNI can optionally contain propylene oxide in an amount up to about 15% by weight. Other preferred LFNI surfactants can be prepared by the processes described in U.S. Patent 4,223,163, issued September 16, 1980, Builloty.
Highly preferred ADDS herein wherein the LFNI is present make use of ethoxylated monohydroxy alcohol or alkyl phenol and additionally comprise a polyoxyethylene, polyoxypropylene block polymeric compound;
the ethoxylated monohydroxy alcohol or alkyl phenol fraction of the LFNI
comprising from about 20°~ to about 100°~, preferably from about 30% to about 70°~, of the total LFNI. .
Suitable block polyoxyethylene-polyoxypropylene polymeric compounds that meet the requirements described hereinbefore include those based on ethylene glycol, propylene glycol, glycerol, trimethylolpropane and ethylenediamine as initiator reactive hydrogen compound. Polymeric compounds made from a sequential ethoxylation and propoxylation of initiator compounds with a single reactive hydrogen atom, such as C12-18 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/polyoxyethylenelpolyoxypropylene block polymer blend comprising about 75°~, by weight of the blend, of a reverse block co-polymer of polyoxyethyiene 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 trimethylolpropane and containing 99 moles of propylene oxide and 24 moles of ethylene oxide per mole of trimethylolpropane.
Suitable for use as LFNI in the ADD compositions are those LFNI
having relatively low cloud points and high hydrophilic-lipophilic balance (HLB). Cloud points of 1 % solutions in water are typically below about 32°C and preferably lower, e.g., OoC, for optimum control of sudsing throughout a full range of water temperatures.
LFNIs which may also be used include a C1g alcohol polyethoxylate, having a degree of ethoxylation of about 8, commercially available as SLF18 from Olin Corp., and any biodegradable LFNI having the melting point properties discussed hereinabove.
(b) Anionic Co-surfactant - The automatic dishwashing detergent compositions herein are preferably substantially free from anionic co-surfactants. It has been discovered that certain anionic co-surfactants, particularly fatty carboxylic acids, can cause unsightly films on dishware.
Moreover, may anionic surFactants are high foaming. If present, the anionic co-surfactant is typically of a type having good solubility in the presence of calcium. Such anionic co-surtactants are further illustrated by sulfobetaines, alkyl(polyethoxy)sulfates (AES), alkyl (polyethoxy)carboxylates, and short chained Cg-C1 p alkyl sulfates.
2. Detersive Enzymes "Detersive enzyme", as used herein, means any enzyme having a cleaning, stain removing or otherwise beneficial effect in an ADD
composition. Preferred detersive enzymes are hydrolases such as proteases, amylases and lipases. Highly preferred for automatic dishwashing are amylases andlor proteases, including both current commercially available types and improved types which, though more bleach compatible, have a remaining degree of bleach deactivation susceptibility.
In general, as noted, preferred ADD compositions herein comprise one or more detersive enzymes. If only one enzyme is used, it is preferably an amyolytic enzyme when the composition is for automatic dishwashing use. Highly preferred for automatic dishwashing is a mixture of proteolytic enzymes and amyloytic enzymes. More generally, the enzymes to be incorporated include proteases, amylases, lipases, cellulases, and peroxidases, as well as mixtures thereof. Other types of enzymes may also be included. They may be of any suitable origin, such as vegetable, animal, bacterial, fungal and yeast origin. However, their choice is governed by several factors such as pH-activity andlor stability optima, thermostability, stability versus active detergents, builders, etc. In this respect bacterial or fungal enzymes are preferred, such as bacterial amylases and proteases, and fungal cellulases.
Enzymes are normally incorporated in the instant detergent compositions at levels sufficient to provide a "cleaning-effective amount".
The term "cleaning-effective amount" refers to any amount capable of producing a cleaning, stain removal or soil removal effect on substrates such as fabrics, dishware and the like. Since enzymes are catalytic materials, such amounts may be very small. In practical terms for current commercial preparations, typical amounts are up to about 5 mg by weight, more typically about 0.01 mg to about 3 mg, of active enzyme per gram of the composition. Stated otherwise, the compositions herein will typically comprise from about 0.001 °7O to about 6°~, preferably 0.01 °~-1 °r6 by weight of a commercial enzyme preparation. Protease enzymes are usually present in such commercial preparations at levels sufficient to provide from 0.005 to 0.1 Anson units (AU) of activity per gram of composition. For automatic dishwashing purposes, it may be desirable to increase the active enzyme content of the commercial preparations, in order to minimize the total amount of non-catalytically active materials delivered and thereby improve spotting~lming results.
Suitable examples of proteases are the subtilisins which are obtained from particular strains of B. subriiis and 8. iicheniformis. Another suitable protease is obtained from a strain of Bacillus, having maximum activity throughout the pH range of 8-12, developed and sold by Novo Industries AIS as ESPERASE~. The preparation of this enzyme and analogous enzymes is described in British Patent Specification No. 1,243,784 of Novo.
Proteolytic enzymes suitable for removing protein-based stains that are commercially available include those sold under the tradenames ALCALASE~ and SAVINASE~ by Novo Industries AIS (Denmark) and MAXATASE~ by International Bio-Synthetics, Inc. (The Netherlands).
Other proteases include Protease A (see European Patent Application 130,756, published January 9, 1985) An especially preferred protease, referred to as "Protease D" is a carbonyl hydroiase variant having an amino acid sequence not found in nature, which is derived from a precursor carbonyl hydrolase by substituting a different amino acid for a plurality of amino acid residues at a position in said carbonyl hydrolase equivalent to position +76, preferably also in combination with one or more amino acid residue positions equivalent to those selected from the group consisting of +99, +101, +103, +104, +107, +123, +27, +105, +109, +126, +128, +135, +156, +16fi, +195, +197, +204, +206, +210, +216, +217, +218, +222, +260, +265, and/or +274 according to the numbering of Bacillus amyloliquefaaens subtilisin.
Amylases suitable herein include, for example, a-amylases described in British Patent Specification No. 1,296,839 (Novo), RAPIDASE~, International Bio-Synthetics, Inc. and TERAAAMYL~, Novo Industries.
Engineering of enrymes (e.g., stability-enhanced amylase) for -- improved stability, e.g., oxidative stability is known. See, for example J. Biological Chem., Vol. 260, No. 11, June 1985, pp 6518-6521.
"Reference amylase" refers to a conventional amylase inside the scope of the amylase component of this invention. Further, stability-enhanced amylases, also within the invention, are typically compared to these "reference amylases".
The present invention, in certain preferred embodiments, can makes use of amylases having improved stability in detergents, especially improved oxidative stability. A convenient absolute stability reference-point against which amylases used in these preferred embodiments of the instant invention represent a measurable improvement is the stability of TERMAMYLm in commercial use in 1993 and available from Novo Nordisk AIS. This TERMAMYL~ amylase is a "reference amylase", and is itself well-suited for use in the ADD (Automatic Dishwashing Detergent) ~1 compositions of the invention. Even more preferred amylases herein share the characteristic of being "stability-enhanced" amylases, characterized, at a minimum, by a measurable improvement in one or more of: oxidative stability, e.g., to hydrogen peroxideltetraacetylethylenediamine in buffered solution at pH 9-10; thermal stability, e.g., at common wash temperatures such as about 60oC; or alkaline stability, e.g., at a pH from about 8 to about 11, all measured versus the above-identified reference-amylase. Preferred amylases herein can demonstrate further improvement versus more challenging reference amylases, the latter reference amylases being illustrated by any of the precursor amylases of which preferred amylases within the invention are variants. Such precursor amylases may themselves be natural or be the product of genetic engineering. Stability can be measured using any of the art-disclosed technical tests. See references disclosed in WO 94/02597.
In general, stability-enhanced amylases respecting the preferred embodiments of the invention can be obtained from Novo Nordisk AlS, or from Genencor International.
Preferred amylases herein have the commonality of being derived using site-directed mutagenesis from one or more of the Baccillus amylases, especialy the Bacillus alpha-amylases, regardless of whether one, two or multiple amylase strains are the immediate precursors.
As noted, "oxidative stability-enhanced" amylases are preferred for use herein despite the fact that the invention makes them "optional but preferred" materials rather than essential. Such amylases are non-iimitingly illustrated by the following:
(a) An amylase acxording to WO/94102597, Novo Nordisk AIS, published Feb. 3, 1994, as further illustrated by a mutant in which substitution is made, using alanine or ttireonine (preferably threonine), of the methionine residue located in position 197 of the H.licheniformis alpha-amylase, known as TERMAMYL~, or the homologous position variation of a similar parent amylase, such as B.
amyloliquefeciens, B.subtilis, or 8.stearothermophilus;

(b) Stability-enhanced amylases as described by Genencor International in a paper entitled "Oxidatively Resistant alpha-Amylases"
presented at the 207th American Chemical Society National Meeting, March 13-17 1994, by C. Mitchinson. Therein it was noted that bleaches in automatic dishwashing detergents inactivate alpha-amylases but that improved oxidative stability amylases have been made by Genencor from B.licheniformis NCIB8061. Methionine (Met) was identified as the most likely residue to be modified. Met was substituted, one at a time, in positions 8,15,197,256,304,366 and 438 leading to specific mutants, particularly important being M197L and M197T with the M197T variant being the most stable expressed variant. Stability was measured in CASCADE~ and SUNLIGHT~;
(c) Particularly preferred herein are amylase variants having additional modification in the immediate parent available from Novo Nordisk A/S. These amylases do not yet have a tradename but are those referred to by the supplier as QL37+M197T.
Any other oxidative stability-enhanced amylase can be used, for example as derived by site-directed mutagenesis from known chimeric, hybrid or simple mutant parent forms of available amylases.
Cellulases usable in, but not preferred, for the present invention include both bacterial or fungal cellulases. Typically, they will have a pH
optimum of between 5 and 9.5. Suitable cellulases are disclosed in U.S.
Patent 4,435,307, Barbesgoard et al, issued March 6, 1984, which discloses fungal cellulase produced from Humicola insolens and Humicola strain DSM1800 or a cellulase 212-producing fungus belonging to the genus Aeromonas, and cellulase extracted from the hepatopancreas of a marine mollusk (Dolabella Auricula Solander). Suitable cellulases are also disclosed in GB-A-2.075.028; GB-A-2.095.275 and DE-OS-2.247.832.
CAREZYME~ (Novo) is especially useful.
Suitable lipase enzymes for detergent use include those produced by microorganisms of the Pseudomonas group, such as Pseudomonas stutzeri ATCC 19.154, as disclosed in British Patent 1,372,034. See also lipases in Japanese Patent Application 53,20487, laid open to public inspection on February 24, 1978. This lipase is available from Amano Pharmaceutical Co. Ltd., Nagoya, Japan, under the trade name Lipase P "AmanoT"","
hereinafter referred to as "Amano-P " Other commercial lipases include Amano-CES, lipases ex Chromobacter viscosum, e.g. Chromobacter viscosum var. lipolyticum NRRLB 3673, commercially available from Toyo Jozo Co., Tagata, Japan; and further Chromobacter viscosum lipases from U.S. Biochemical Corp., U.S.A. and Disoynth Co., The Netherlands, and lipases ex Pseudomonas gladioli. The LIPO~ASE~ enzyme derived from i4umicola lanuginosa and commercially available from Novo (see also EPO
341,947 is a preferred lipase for use herein. Another preferred lipase enzyme is the D96L variant of the native Humicola lanuginosa lipase, as described in WO 92105249 and Research Disclosure No. 35944, March 10, 1994, both published by Novo. In general, iipoiytic enzymes are less preferred than amylases andlor proteases for automatic dishwashing embodiments of the present invention.
Peroxidase enzymes can be used in combination with oxygen sources, e.g., percarbonate, perborate, persulfate, hydrogen peroxide, etc.
They are typically used for "solution bleaching," i.e. to prevent transfer of dyes or pigments removed from substrates during wash operations to other substrates in the wash solution. Peroxidase enzymes are known in the art, and include, for example, horseradish peroxidase, ligninase, and haloperoxidase such as chloro- and bromo-peroxidase. Peroxidase-containing detergent compositions are disclosed, for example, in PCT
International Application WO 89/099813, published October 19, 1989, by 0.
Kirk, assigned to Novo Industries AJS. The present invention encompasses peroxidase-free automatic dishwashing composition ~mbodiments.
A wide range of enzyme materials and means for their incorporation into synthetic detergent compositions are also disclosed in U.S. Patent 3,553,139, issued January 5, 1971 to McCarty et al. Enzymes are further disclosed in U.S. Patent 4,101,457, Place et al, issued July 18, 1978, and in fiJ.S. Patent 4,507,219, Hughes, issued March 26, 1985. Enzymes for use in detergents can be stabilized by various techniques. Enzyme stabilization techniques are disclosed and exemplified in U.S. Patent 3,600,319, issued August 17, 1971 to Gedge, et al, and European Patent Application Publication No. 0 199 405, published October 29, 1986, Venegas. Enzyme stabilization systems are also described, for example, in U.S. Patent 3,519,570.
(a) Enzyme Stabilizing System - The enzyme-containing compositions, especially liquid compositions, herein may comprise from about 0.001 % to about 10%, preferably from about 0.005% to about 8%, most preferably from about 0.01 % to about 6%, by weight of an enzyme stabilizing system.
The enzyme stabilizing system can be any stabilizing system which is compatible with the detersive enzyme. Such stabilizing systems can comprise calcium ion, boric acid, propylene glycol, short chain carboxylic acid, boronic acid, and mixtures thereof.
The stabilizing system of the ADDs herein may further comprise from 0 to about 10%, preferably from about 0.01 % to about 6% by weight, of chlorine bleach scavengers, added to prevent chlorine bleach species present in many water supplies from attacking and inactivating the enzymes, especially under alkaline conditions. While chlorine levels in water may be small, typically in the range from about 0.5 ppm to about 1.75 ppm, the available chlorine in the total volume of water that comes in contact with the enzyme during dishwashing is relatively large; accordingly, enzyme stability in-use can be problematic.
Suitable chlorine scavenger anions are widely known and readily available, and are illustrated by salts containing ammonium cations with sulfite, bisulfite, thiosulfite, thiosulfate, iodide, etc. Antioxidants such as carbamate, ascorbate, etc., organic amines such as ethylenediaminetetracetic acid (EDTA) or alkali metal salt thereof, monoethanolamine (MEA), and mixtures thereof can likewise be used.
Other conventional scavengers such as bisulfate, nitrate, chloride, sources of hydrogen peroxide such as sodium perborate tetrahydrate, sodium perborate monohydrate and sodium percarbonate, as well as phosphate, condensed phosphate, acetate, benzoate, citrate, formate, lactate, malate, tartrate, salicylate, etc., and mixtures thereof can be used if desired. In general, since the chlorine scavenger function can be performed by several of the ingredients separately listed under better recognized functions, (e.g., other components of the invention such as sodium perborate), there is no requirement to add a separate chlorine scavenger unless a compound pertorming that function to the desired extent is absent from an enzyme-containing embodiment of the invention; even then, the scavenger is added only for optimum re~;ults. Moreover, the formulator will exercise a chemist's normal skill in avoiding the use of any scavenger which is majorly incompatible with other ingredients, if used. In relation to the use of ammonium salts, such salts can be simply admixed with the detergent composition but are prone to adsorb water andlor liberate ammonia during storage. Accordingly, such materials, if present, are desirably protected in a particle such as that described in U.S. Patent 4,652,392, Baginski et al.
3. Optional Bleach Adjuncts Via) Bleach Activators - Bleach activator components are optional materials for the inventive compositions. Such activators are typified by TAED
(tetraacetylethylenediamine). Numerous conventional activators are known.
See for example U.:i. Patent 4,915,854, issued April 10, 1990 to Mao et al, and U.S. Patent 4,4'12,934. Nonanoyloxybenzene sulfonate (NOBS) or acyl lactam activators may be used, and mixtures thereof with TAED can also be used. See also U.S. 4,634,551 for other typical conventional bleach activators. Also known are amido-derived bleach activators of the formulae:
R1 N(R5)C(O)R2C(CI)L or R1 C(O)N(R5)R2C(O)L wherein R1 is an alkyl group containing from about 6 to about 12 carbon atoms, R2 is an alkylene containing from 1 to about 6 carbon atoms, R5 is H or alkyl, aryl, or alkaryl containing from about 1 to about 10 carbon atoms, and L is any suitable leaving group other than an alpha-modified lactam. Further illustration of bleach activators of the above formulae include (6-octanamido-caproyl)oxybenzenesulfonate, (6-nonanamidocaproyi)oxybenzenesulfonate, (6-decanamido-caproyl)oxybenzenesulfonate, and mixtures thereof as described in U.S. Patent 4,634,551. Another class of bleach activators comprises the benzoxazin-type activators disclosed by Hodge et al in U.S.
Patent 4,966,723, i:~sued October 30, 1990. Still another class of bleach activators includes acyl lactam activators such as octanoyl caprolactam, 3,5,5-trimethylhexanoyl caprolactam, nonanoyl caprolactam, decanoyl caprolactam, undec;enoyl caprolactam, octanoyl valerolactam, decanoyl valerolactam, undecenoyl valerolactam, nonanoyl valerolactam, 3,5,5-trimethylhexanoyl valerolactam and mixtures thereof. The present compositions can optionally comprise acyl benzoates, such as phenyl benzoate.
(b) Organic Peroxides, especially Diacvl Peroxides - These are extensively illustrated in Kirk Othmer, Encyclopedia of Chemical Technology, Vol. 17, John Wiley and Sons, 1982 at pages 27-90 and especially at pages 63-72, If a diacyl peroxide is used, it will preferably be one which exerts minimal adverse impact on spottinglfilming.
4. pH and Buffering Variation Many detergent compositions herein will 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 buffering 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 ADD compositions herein comprise a pH-adjusting component selected from water-soluble alkaline inorganic salts and water-soluble organic or inorganic builders. The pH-adjusting components are selected so that when the ADD is dissolved in water at a concentration of 1,000 - 5,000 ppm, the pH remains in 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:
(i) sodium carbonate or sesquicarbonate;
(ii) sodium silicate, preferably hydrous sodium silicate having Si02:Na20 ratio of from about 1:1 to about 2:1, and mixtures thereof with limited quantites of sodium metasilicate;
(iii) sodium citrate;
(iv) citric acid;
(v) sodium bicarbonate;
(vi) sodium borate, preferably borax;
(vii) sodium hydroxide; and (viii) mixtures of (i)-(vii).
Preferred embodiments contain low levels of silicate (i.e. from about 3% to about 10°r6 Si02).

Illustrative of highly preferred pH-adjusting component systems are binary mixtures of granular sodium citrate with anhydrous sodium carbonate, and i:hree-component mixtures of granular sodium citrate trihydrate, citric acid monohydrate and anhydrous sodium carbonate.
The amount of the pH adjusting component in the instant ADD
compositions is preferably from about 1 % to about 50%, by weight of the composition. In a preferred embodiment, the pH-adjusting component is present in the ADD composition in an amount from about 5% to about 40%, preferably from about 10% to about 30%, by weight.
For compositions herein having a pH between about 9.5 and about 11 of the initial wash solution, particularly preferred ADD embodiments comprise, by weight of ADD, from about 5% to about 40%, preferably from about 10% to about 30%, most preferably from about 15% to about 20%, of sodium citrate with from about 5% to about 30%, preferably from about 7%
to 25%, most preferably from about 8% to about 20% sodium carbonate.
The essential pH-adjusting system can be complemented (i.e. for improved sequestration in hard water) by other optional detergency builder salts selected from nonphosphate detergency builders known in the art, which include the various water-soluble, alkali metal, ammonium or substituted ammonium borates, hydroxysulfonates, polyacetates, and polycarboxylates. Preferred are the alkali metal, especially sodium, salts of such materials. Alternate water-soluble, non-phosphorus organic builders can be used for their sequestering properties. Examples of polyacetate and polycarboxylate builders are the sodium, potassium, lithium, ammonium and substituted ammonium salts of ethylenediamine tetraacetic acid;
nitrilotriacetic acid, tartrate monosuccinic acid, tartrate disuccinic acid, oxydisuccinic acid, carboxymethoxysuccinic acid, mellitic acid, and sodium benzene polycarboxylate salts.
(a) Water-Soluble: Silicates The present automatic dishwashing detergent compositions may further comprise water-soluble silicates. Water-soluble silicates herein are any silicates which are soluble to the extent that they do not adveresely affect spotting/filming characteristics of the ADD composition.

Examples of silicates are sodium metasilicate and, more generally, the alkali metal silicates, particularly those having a Si02:Na20 ratio in the range 1.6:1 to 3.2:1; and layered silicates, such as the layered sodium silicates described in U.S. Patent 4,664,839, issued May 12, 1987 to H. P.
Rieck. NaSKS-6~ is a crystalline layered silicate marketed by Hoechst (commonly abbreviated herein as "SKS-6"). Unlike zeolite builders, Na SKS-6 and other water-soluble silicates usefule herein do not contain aluminum. NaSKS-6 is the 8-Na2Si05 form of layered silicate and can be prepared by methods such as those described in German DE-A-3,417,649 and DE-A-3,742,043. SKS-6 is a preferred layered silicate for use herein, but other such layered silicates, such as those having the general formula NaMSix02x+1 ~yH20 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. Various other layered silicates from Hoechst include NaSKS-5, NaSKS-7 and NaSKS-11, as the oc-, (3- and y- forms. Other silicates may also be useful, such as for example magnesium silicate, which can serve as a crispening 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-ratio silicates such as BRITESIL~
H20 from PQ Corp., and the commonly sourced BRITESIL~ H24 though liquid grades of various silicates can be used when the ADD composition has liquid form. Within safe limits, sodium metasilicate 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.
5. Builders - Detergent builders other than silicates can optionally be included in the compositions herein to assist in controlling mineral hardness. Inorganic as well as organic builders can be used. Builders are typically used in automatic dishwashing and fabric laundering compositions, for example to assist in the removal of particulate soils.
The level of builder can vary widely depending upon the end use of the composition and its desired physical form. When present, the compositions will typically comprise at least about 1 % builder. High performance compositions typically comprise from about 10% to about 80%, WO 96/23860 PCTlLTS96/01198 more typically from about 15% to about 50% by weight, of the detergent builder. Lower or higher levels of builder, however, are not excluded.
Inorganic or P-containing detergent builders include, but are not limited to, the alkali metal, ammonium and alkanolammonium salts of polyphosphates (exemplified by the tripolyphosphates, pyrophosphates, and glassy polymeric meta-phosphates), phosphonates, phytic acid, silicates, carbonates (including bicarbonates and sesquicarbonates), sulfates, and aluminosilicates. However, non-phosphate builders are required in some locales. Compositions herein function surprisingly well even in the presence of "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. See U.S. Pat. 4,605,509 for examples of preferred aluminosilicates.
Examples of carbonate builders are the alkaline earth and alkali metal carbonates as disclosed in German Patent Application No. 2,321,001 published on November 15, 1973. Various grades and types of sodium carbonate and sodium sesquicarbonate may be used, certain of which are particularly useful as carriers for other ingredients, especially detersive surfactants.
Aluminosificate builders may be used in the present compositions though are not preferred for automatic dishwashing detergents.
Aluminosilicate builders are of great importance in most currently marketed heavy duty granular detergent compositions, and can also be a significant builder ingredient. in liquid detergent formulations. Aluminosilicate builders include those having the empirical formula: NA20~AL203~xSiOz~yH20 wherein z and y are integers of at least 6, the molar ratio of z to y is in the range from 1.0 to about 0.5, and x is an integer from about 15 to about 264.
Useful aluminosilicate ion exchange materials are commercially available. These aluminosilicates can be crystalline or amorphous in structure and can be naturally-occurring aluminosilicates or synthetically derived. A method for producing aluminosilicate ion exchange materials is disclosed in U.S. Patent 3,985,669, Krummel, et al, issued October 12, 1976. Preferred :synthetic crystalline aluminosilicate ion exchange materials useful herein are available under the designations Zeolite A, Zeolite P (B), Zeolite MAP and Zeolite X. In an embodiment, the crystalline aluminosilicate ion exchange material has the formula:
Nal2[(A102)12(Si02)121'xH20 wherein x is from about 20 to about 30, especially about 27. This material is known as Zeolite A. Dehydrated zeolites (x - 0 - 10) may also be used herein. Preferably, the aluminosilicate has a particle size of about 0.1-10 microns in diameter.
Individual particles can desirably be even smaller than 0.1 micron to further assist kinetics of exchange through maximization of surface area. High surface area also increases utility of aluminosilicates as adsorbents for surfactants, especially in granular compositions. Aggregates of silicate or aluminosilicate particles may be useful, a single aggregate having dimensions tailored to minimize segregation in granular compositions, while the aggregate particle remains dispersible to submicron individual particles during the wash. As with other builders such as carbonates, it may be desirable to use zeolites in any physical or morphological form adapted to promote surfactant carrier function, and appropriate particle sizes may be freely selected by the formulator.
Organic detergent builders suitable for the purpases of the present invention include, but are not restricted to, a wide variety of polycarboxylate compounds. As used herein, "polycarboxylate" refers to compounds having a plurality of carboxylate groups, preferably at least 3 carboxylates.
Polycarboxylate builder can generally be added to the composition in acid form, but can also be added in the form of a neutralized salt or "overbased".
When utilized in salt form, alkali metals, such as sodium, potassium, and lithium, or alkanolammonium salts are preferred.
Included among the polycarboxylate builders are a variety of categories of useful materials. One important category of polycarboxylate builders encompasses the ether polycarboxylates, including oxydisuccinate, as disclosed in Berg, U.S. Patent 3,128,287, issued April 7, 1964, and Lamberti et al, U.S. Patent 3,635,830, issued January 18, 1972. See also "TMSITDS" builders of U.S. Patent 4,663,071, issued to Bush et al, on May 5, 1987. Suitable ether polycarboxylates also include cyclic compounds, particularly alicyclic compounds, such as those described in U.S. Patents 3,923,679; 3,835,163; 4,158,635; 4,120,874 and 4,102,903.

Other useful detergency builders include the ether hydroxypolycarboxylates, copolymers of malefic anhydride with ethylene or vinyl methyl ether, 1, 3, 5-trihydroxy benzene-2, 4, 6-trisulphonic acid, and carboxymethyloxysuccinic acid, the various alkali metal, ammonium and substituted ammonium salts of poiyacetic acids such as ethylenediaminetetraacetic acid and nitrilotriacetic acid, as well as polycarboxylates such as mellitic acid, succinic acid, oxydisuccinic acid, polymaleic acid, benzene 1,3,5-tricarboxylic acid, carboxymethyfoxysuccinic acid, and soluble salts thereof.
Citrate builders, e.g., citric acid and soluble salts thereof (particularly -- sodium salt), are polycarboxylate builders of particular importance for heavy duty laundry detergent and automatic dishwashing formulations due to their availability from renewable resources and their biodegradability. Citrates can also be used in combination with zeolite, the aforementioned BRITESIt types, and/or layered silicate builders. Oxydisuocinates are also useful in such compositions and combinations.
Also suitable in the detergent compositions of the present invention are the 3,3-dicarboxy-4-oxa-1,6-hexanedionates and the related compounds disclosed in U.S. Patent 4,566,984, Bush, issued January 28, 1986. Useful succinic acid builders include the C5-C20 alkyl and aikenyi succinic acids and salts thereof. A particularly preferred compound of this type is dodecenylsuccinic acid. Specific examples of succinate builders include:
laurylsuccinate, myristylsuccinate, palmitylsuccinate, 2-dodecenylsuccinate (preferred), 2-pentadecenylsuccinate, and the like. Laurylsuccinates are the preferred builders of this group, and are described in European Patent 0,200,263, published November 5, 1986.
Other suitable polycarboxylates are disclosed in U.S. Patent 4,144,226, Crutchfield et al, issued March 13, 1979 and in U.S. Patent 3,308,067, Diehl, issued March 7, 1967. See also U.S. Patent 3,723,322.
Fatty acids, e.g., C12-C18 monocarboxyiic acids, may also be incorporated into the compositions alone, or in combination with the aforesaid builders, especially citrate and/or the succinate builders, to provide additional builder activity but are generally not desired. Such use of fatty acids will generally result in a diminution of sudsing in laundry compositions, which may need to be be taken into account by the formulator. Fatty acids or their salts are undesirable in Automatic Dishwashing (ADD) embodiments in situations wherein soap scums can , form and be deposited on dishware.
Where phosphorus-based builders can be used, the various alkali metal phosphates such as the well-known sodium tripolyphosphates, sodium pyrophosphate and sodium orthophosphate can be used.
Phosphonate builders such as ethane-1-hydroxy-1,1-diphosphonate and other known phosphonates (see, for example, U.S. Patents 3,159,581;
3,213,030; 3,422,021; 3,400,148 and 3,422,137) can also be used though such materials are more commonly used in a low-level mode as chelants or stabilizers.

6. Chelatinc~ Agents The compositions herein may also optionally contain one or more transition-metal selective sequestrants, "chelants" or "chelating agents", e.g., iron and/or copper and/or manganese chelating agents. Chelating agents suitable for use herein can be selected from the group consisting of aminocarboxylates, phosphonates (especially the aminophosphonates), polyfunctionally-substituted aromatic chelating agents, and mixtures thereof.
Without intending to be bound by theory, it is believed that the benefit of these materials is due in part to their exceptional ability to control iron, copper and manganese in washing solutions; other benefits include inorganic film prevention or scale inhibition. Commercial chelating agents for use herein include the DEQUEST~ series, and chelants from Monsanto, DuPont, and Nalco, Inc.
Aminocarboxylates useful as optional chelating agents are further illustrated by ethylenediaminetetracetates, N-hydroxyethylethylenediaminetriacetates, nitrilo-triacetates, ethylenediamine tetraproprionates, triethylenetetraaminehexacetates, diethylenetriamine-pentaacetates, and ethanoldiglycines, alkali metal, ammonium, and substituted ammonium salts thereof. In general, chelant mixtures may be used for a combination of functions, such as multiple -transition-metal control, long-term product stabilization, and/or control of precipitated transition metal oxides and/or hydroxides.

Polyfunctionally-substituted aromatic chelating agents are also useful in the composition, herein. See U.S. Patent 3,812,044, issued May 21, 1974, to Connor e1: al. Preferred compounds of this type in acid form are dihydroxydisulfobenzenes such as 1,2-dihydroxy-3,5-disulfobenzene.
A highly preferred biodegradable chelator for use herein is ethylenediamine disuccinate ("EDDS"), especially (but not limited to) the [S,S] isomer as described in U.S. Patent 4,704,233, November 3, 1987, to Hartman and Perkins. The trisodium salt is preferred though other forms, such as magnesium salts, may also be useful.
Aminophosphonates are also suitable for use as chelating agents in the compositions of the invention when at least low levels of total phosphorus are acceptable in detergent compositions, and include the ethylenediaminetetrakis (methylenephosphonates) and the diethylenetriaminep~entakis (methylene phosphonates). Preferably, these aminophosphonate;s do not contain alkyl or alkenyl groups with more than about 6 carbon atoms.
If utilized, chelating agents or transition-metal-selective seguestrants will preferably comprise from about 0.001 % to about 10%, more preferably from about 0.05% to about 1 % by weight of the compositions herein.

7. Dispersant F'olymer - Preferred ADD compositions herein may additionally contain a dispersant polymer. When present, a dispersant polymer in the inst<ant ADD compositions is typically at levels in the range from 0 to about 25%, preferably from about 0.5% to about 20%, more preferably from about 1 % to about 8% by weight of the ADD composition.
Dispersant polymers are useful for improved filming performance of the present ADD compositions, especially in higher pH embodiments, such as those in which wash pH exceeds about 9.5. Particularly preferred are polymers which inhibit the deposition of calcium carbonate or magnesium silicate on dishwars~.
Dispersant polymers suitable for use herein are further illustrated by the film-forming pollymers described in U.S. Pat. No. 4,379,080 (Murphy), issued Apr. 5, 1983.
Suitable polyrners are preferably at least partially neutralized or alkali metal, ammonium or substituted ammonium (e.g., mono-, di- or triethanolammonium) salts of polycarboxylic acids. The alkali metal, especially sodium salts care most preferred. While the molecular weight of the polymer can vary over a wide range, it preferably is from about 1,000 to about 500,000, more preferably is from about 1,000 to about 250,000, and most preferably, especially if the ADD is for use in North American automatic dishwashing appliances, is from about 1,000 to about 5,000.
Other suitable dispersant polymers include those disclosed in U.S.
Patent No. 3,308,067 issued March 7, 1967, to Diehl. Unsaturated monomeric acids that can be polymerized to form suitable dispersant polymers include acrylic acid, malefic acid (or malefic anhydride), fumaric acid, itaconic acid, aconitic acid, mesaconic acid, citraconic acid and methylenemalonic acid. The presence of monomeric segments containing no carboxylate radicals such as methyl vinyl ether, styrene, ethylene, etc. is suitable provided that such segments do not constitute more than about 50% by weight of the dispersant polymer.
Copolymers of acrylamide and acrylate having a molecular weight of from about 3,000 to about 100,000, preferably from about 4,000 to about 20,000, and an acrylamide content of less than about 50%, preferably less than about 20%, by weight of the dispersant polymer can also be used.
Most preferably, such dispersant polymer has a molecular weight of from about 4,000 to about 20,000 and an acrylamide content of from about 0% to about 15%, by weight of the polymer.
Particularly preferred dispersant polymers are low molecular weight modified polyacrylate copolymers. Such copolymers contain as monomer units: a) from about 90% to about 10%, preferably from about 80% to about 20% by weight acrylic acid or its salts and b) from about 10% to about 90%, preferably from about 20% to about 80% by weight of a substituted acrylic monomer or its salt and have the general formula: -[(C(R2)C(R1 )(C(O)ORS)] wherein the apparently unfilled valencies are in fact occupied by hydrogen and at least one of the substituents R1, R2, or RS, preferably R1 or R2, is a 1 to 4 carbon alkyl or hydroxyalkyl group; R1 or R2 can be a hydrogen and RS can be a hydrogen or alkali metal salt.
Most preferred is a substituted acrylic monomer wherein R1 is methyl, R2 is hydrogen, and R3 is sodium.

Suitable low molecular weight polyacrylate dispersant polymer preferably has a molecular weight of less than about 15,000, preferably from about 500 to about 10,000, most preferably from about 1,000 to about 5,000. The most preferred polyacrylate copolymer for use herein has a molecular weight of about 3,500 and is the fully neutralized form of the polymer comprising about 70% by weight acrylic acid and about 30% by weight methacrylic .acid.
Other suitable modified polyacrylate copolymers include the low molecular weight copolymers of unsaturated aliphatic carboxylic acids disclosed in U.S. P;atents 4,530,766, and 5,084,535.
Agglomeratecl forms of the present ADD compositions may employ aqueous solutions of polymer dispersants as liquid binders for making the agglomerate (particularly when the composition consists of a mixture of sodium citrate and sodium carbonate). Especially preferred are polyacrylates with an average molecular weight of from about 1,000 to about 10,000, and acrylate/maleate or acrylate/fumarate copolymers with an average molecular weight of from about 2,000 to about 80,000 and a ratio of acrylate to maleate~ or fumarate segments of from about 30:1 to about 1:2.
Examples of such copolymers based on a mixture of unsaturated mono- and dicarboxylate monomers are disclosed in European Patent Application No.
66,915, published December 15, 1982.
Other dispersant polymers useful herein include the polyethylene glycols and polypropylene glycols having a molecular weight of from about 950 to about 30,000 which can be obtained from the Dow Chemical Company of Midland, Michigan. Such compounds for example, having a melting point within the range of from about 30oC to about 100°C, can be obtained at molecular weights of 1,450, 3,400, 4,500, 6,000, 7,400, 9,500, and 20,000. Such compounds are formed by the polymerization of ethylene glycol or propylene glycol with the requisite number of moles of ethylene or propylene oxide to provide the desired molecular weight and melting point of the respective polyethylene glycol and polypropylene glycol. The polyethylene, polypropylene and mixed glycols are referred to using the formula:

WO 96/23860 PCTlLTS96/01198 HO(CH2CH20)m(CH2CH(CH3)O)n(CH(CH3)CH20)oOH wherein m, n, and o are integers satisfying the molecular weight and temperature requirements given above. , Yet other dispersant polymers useful herein include the cellulose sulfate esters such as cellulose acetate sulfate, cellulose sulfate, hydroxyethyl cellulose sulfate, methylcellulose sulfate, and hydroxypropylcellulose sulfate. Sodium cellulose sulfate is the most preferred polymer of this group.
Other suitable dispersant polymers are the carboxylated polysaccharides, particularly starches, celluloses and alginates, described in U.S. Pat. No. 3,723,322, Diehl, issued Mar. 27, 1973; the dextrin esters of polycarboxylic acids disclosed in U.S. Pat. No. 3,929,107, Thompson, issued Nov. 11, 1975; the hydroxyalkyl starch ethers, starch esters, oxidized starches, dextrins and starch hydrolysates described in U.S. Pat No. 3,803,285, Jensen, issued Apr. 9, 1974; the carboxylated starches described in U.S. Pat. No. 3,629,121, Eldib, issued Dec. 21, 1971; and the dextrin starches described in U.S. Pat. No. 4,141,841, McDonald, issued Feb. 27, 1979. Preferred cellulose-derived dispersant polymers are the carboxymethyl celluloses.
Yet another group of acceptable dispersants are the organic dispersant polymers, such as polyaspartate.

8. Material Care A4ents - The present ADD compositions may contain one or more material care agents which are effective as corrosion inhibitors and/or anti-tarnish aids. Such materials are preferred components of machine dishwashing compositions especially in certain European countries where the use of electroplated nickel silver and sterling silver is still comparatively common in domestic flatware, or when aluminium protection is a concern and the composition is low in silicate. Generally, such material care agents include metasilicate, silicate, bismuth salts, manganese salts, paraffin, triazoles, pyrazoles, thiols, mercaptans, aluminium fatty acid salts, and mixtures thereof.
When present, such protecting materials are preferably incorporated at low levels, e.g., from about 0.01 % to about 5% of the ADD composition.
Suitable corrosion inhibitors include 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 is selected from predominantly branched C25..45 species with a ratio of cyclic to noncyclic hydrocarbons of about 32:68. A paraffin oil meeting those characteristics is sold by Wintershall, Salzbergen, Germany, under the trade name WINOG~M
70. Additionally, the addition of low levels of bismuth nitrate (i.e., 8i(N03)3) is also preferred.
Other corrosion inhibitor compounds include benzotriazole and comparable compounds; mercaptans or thiols including thionaphtol and thioanthranol; and finely divided Aluminium fatty acid salts, such as aluminium tristearate. The formulator will recognize that such materials will generally be used judiciously and in limited quantities so as to avoid any tendency to produce spots or films on glassware or to compromise the bleaching action of the compositions. For this reason, mercaptan anti-tamishes which are quite strongly bleach-reactive and common fatty carboxylic acids which precipitate with calcium in particular are preferably avoided.

9 Silicone and Phosphate Ester Suds Suooressors - The ADD's of the invention can optionally contain an alkyl phosphate aster suds suppressor, a silicone suds suppressor, or combinations thereof. Levels in general are from 0°~ to about 10%, preferably, from about 0.001 °~ to about 5%. Typical levels tend to be low, e.g., from about 0.01 % to about 3% when a silicone suds suppressor is used. Preferred non-phosphate compositions omit the phosphate ester component entirely.
Silicone suds suppressor technology and other defoaming agents useful herein are extensively documented in "Defoaming, Theory and Industrial Applications", Ed., P.R. Garrett, Marcel Dekker, N.Y., 1973, ISBN
0-8247-8770-6. See especially the chapters entitled "Foam control in 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 in laundry detergents such as heavy-duty granules, although types hitherto used only in heavy-duty liquid detergents may also be incorporated in the instant compositions. For example, polydimethylsiloxanes having trimethylsilyl or alternate endblocking units may be used as the silicone. These may be compounded with silica andlor with surface-active nonsilicon components, as illustrated by a suds suppressor comprising 12% siliconelsilica, 18% stearyl alcohol and 70%
starch in granular form. A suitable commercial source of the silicone active compounds is Dow Coming Corp.
Levels of the suds suppressor depend to some extent on the sudsing tendency of the composition, for example, an ADD for use at 2000 ppm comprising 2°r6 octadecyldimethylamine oxide may not require the presence of a suds suppressor. Indeed, it is an advantage of the present invention to select cleaning-effective amine oxides which are inherently much lower in foam-forming tendencies than the typical corn amine oxides. In contrast, formulations in which amine oxide is combined with a high-foaming anionic cosurfactant, e.g., alkyl ethoxy sulfate, benefit greatly from the presence of suds suppressor.
Phosphate esters have also been asserted to provide some protection of silver and silver-plated utensil surfaces; however, the instant compositions can have excellent silvercare without a phosphate ester component. Without being limited by theory, it is believed that lower pH
formulations, e.g., those having pH of 9.5 and below, plus the presence of the low level amine oxide, both contribute to improved silver care.
If it is desired nonetheless to use a phosphate ester, suitable compounds are disclosed in U.S. Patent 3,314,891, issued April 18, 1967, to Schmolka et al. 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-precipitating 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.

10. Other Optional Adjuncts - Depending on whether a greater or lesser degree of compactness is required, filler materials can also be present in the instant ADDs. These include sucrose, sucrose esters, sodium sulfate, potassium sulfate, etc., in amounts up to about 70%, preferably from 0% to about 40% of the ADD composition. Preferred filler is sodium sulfate, especially in good grades having at most low levels of trace impurities.
Sodium sulfate used herein preferably has a purity sufficient to ensure it is non-reactive with bleach; it may also be treated with low levels of sequestrants, such: as phosphonates or EDDS in magnesium-salt form.
Note that preferences, in terms of purity sufficient to avoid decomposing bleach, applies al~;o to pH-adjusting component ingredients, specifically including any silicai:es used herein.
Although optionally present in the instant compositions, the present invention encompasses embodiments which are substantially free from sodium chloride or potassium chloride.
Hydrotrope materials such as sodium benzene sulfonate, sodium toluene sulfonate, sodium cumene sulfonate, etc., can be present, e.g., for better dispersing surfactant.
Bleach-stable perfumes (stable as to odor); and bleach-stable dyes such as those disclosed in U.S. Patent 4,714,562, Roselle et al, issued December 22, 19E~7 can also be added to the present compositions in appropriate amounts. Other common detergent ingredients consistent with the spirit and scopes of the present invention are not excluded.
Since ADD compositions herein can contain water-sensitive ingredients or ingredients which can co-react when brought together in an aqueous environment, it is desirable to keep the free moisture content of the ADDs at a minimum, e.g., 7% or less, preferably 4% or less of the ADD; and to provide packaging which is substantially impermeable to water and carbon dioxide. Coating measures have been described 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 barrier cartons or boxes are another helpful means of assuring 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-foaming nonionic surfactant for protection. There are numerous waxy materials which can readily be used to form suitable coated particles of any such otherwise incompatible components; however, the formulator .
prefers those materials which do not have a marked tendency to deposit or form films on dishes including those of plastic construction. t Some preferred substantially chlorine bleach-free granular automatic dishwashing compositions of the invention are as follows: a substantially chlorine-bleach free automatic dishwashing composition comprising amylase (e.g., TERMAMYL~) and/or a bleach stable amylase and a bleach system comprising a source of hydrogen peroxide selected from sodium perborate and sodium percarbonate and a cobalt catalyst as defined herein.
There is also contemplated a substantially chlorine-bleach free automatic dishwashing composition comprising an oxidative stability-enhanced amylase and a bleach system comprising a source of hydrogen peroxide selected from sodium perborate and sodium percarbonate, a cobalt catalyst, and TAED or NOES.
Method for Cleanin4:
The present invention also encompasses a method for cleaning soiled tableware comprising contacting said tableware with an aqueous medium comprising a cobalt catalyst, preferably at a concentration of from about 2 ppm to about 10 ppm, as described herein before. Preferred aqueous medium have an initial pH in a wash solution of above about 8, more preferably from about 9.5 to about 12, most preferably from about 9.5 to about 10.5.
This invention also encompasses a method of washing tableware in a domestic automatic dishwashing appliance, comprising treating the soiled tableware in an automatic dishwasher with an aqueous alkaline bath comprising amylase and a cobalt catalyst.
Rinse Aid Comaositions and Methods:
The present invention also relates to compositions useful in the rinse cycle of an automatic dishwashing process, such compositions being commonly referred to as "rinse aids". While the hereinbefore described compositions may also be formulated to be used as rinse aid compositions, it is not required for purposes of use as a rinse aid to have a source of ' hydrogen peroxide; present in such compositions (although a source of hydrogen peroxide is preferred, at least at low levels to at least supplement the carry-over).
The optional inclusion of a source of hydrogen peroxide in a rinse aid composition is possible in view of the fact that a significant level of residual detergent composition is carried over from the wash cycle to the rinse cycle.
Thus, when an ADD composition containing a hydrogen peroxide source is used, the source of hydrogen peroxide for the rinse cycle is carry-over from the wash cycle. Catalytic activity provided by the cobalt catalyst is thus effective with this carry-over from the wash cycle.
Thus, the present invention further encompasses automatic dishwashing rinse aid compositions comprising: (a) a catalytically effective amount of a cobalt catalyst as described herein, and (b) automatic dishwashing detergent adjunct materials. Preferred compositions comprise a low foaming nonionic surtactant. These compositions also preferably are in liquid or solid form.
The present invention also encompasses methods for washing tableware in a de~mestic automatic dishwashing appliance, said method comprising treating the soiled tableware during a wash cycle of an automatic dishwasher with an aqueous alkaline bath comprising a source of hydrogen peroxide, followed by treating the tableware in the subsequent rinse cycle with an aqueous bath comprising a cobalt catalyst as described herein.
The following nonlimiting examples further illustrate ADD compositions of the present invention.
Examples 1-3 The following fully-formulated solid-form automatic dishwashing detergents are prepared:

Active % Active % Active Sodium Citrate 15.0 15.0 15.0 Sodium Carbonate 17.5 20.0 20.0 Dispersant Polymer (See 6.0 6.0 6.0 Note 1) Hydroxyethyldiphosphonate1.0 0.5 0.71 (HEDP; acid) Nonionic Surfactant (SLF18,2.0 2.0 2.0 Olin Corp. or Plurafac) Sodium Perborate Monohydrate1.5 1.5 1.5 (See Note 3) TAED 2.5 -- -DTPMP (See Note 4) 0.13 - --Cobalt Catalyst (See Note0.2 0.07 0.4 2) Savinase 6.0T (protease) - 2.0 2.0 Savinase 12T (protease) 2.2 - -Tennamyl 60T (amylase) 1.5 1.0 1.0 BRITESIL H20, PQ Corp. 8.0 8.0 8.0 (as Si02) Meta Silicate (anhydrous)1.25 - -Paraffin 0.5 - -Benzotriazole 0.3 -Sulphate, water, monors Balance Balance to Balance to to 100% 100% 100%

Note 1: Dispersant Polymer. One or moro of: Sokolan~A30, BASF Corp.,Accusol M
480N, Rohm 8 Haas.
Note 2: N,N'-Bis(salicylidene)ethylenediaminocobalt (II) (hereinafter "Cobalt SALENT"""), supplied by Aldrich.
Note 3: These hydrogen peroxide sources are expressed on a weight ~o available oxygen basis. To convert to a basis of percentage of the total composition, divide by about 0.15.
Note 4: c(iethylenetriaminepentakis (methylene phosphoric acid) Examcle 4 _ 4A 4B

INGREDIENT

Cobalt Catal st See Note 2 0.2 0.4 Sodium Perborate Monoh drate See Note 3 1.5 1.5 Am lase Termam I~ 60T, Novo 1 0 Protease 1 SAVINASE 12 T, 3.6~ active rotein 2.5 0 -~ i Protease 2 (Protease D, as 4% active rotein 0 2.5 Trisodium Citrate Dih drate anh drous basis 15 ~ 15 Sodium Carbonate. anh drous 20 I 20 BRITESIL H20, PQ Cor . as Si0 9 I 8 Dieth lenetriamine entaacetic Acid, Sodium 0 0.1 Salt Eth lenediamine Disuccinate, Trisodium Salt 0.13 0 H drox eth Idi hos honate HEDP , Sodium Salt 0.5 0.5 Dis ersant Pol mer See Note 1 8 8 Nonionic Surfactant SLF18, Olin Cor . or LF404,2 2 BASF

.. Sodium Sulfate, water, minors Balance Balance to 100r6to 100r6 TM

Note 1: Dispersant Polymer. One or more of: Sokolar~'~A30, BASF Corp.,Accusol 480N, Rohm 8~ Haas.
Note 2: Cobalt SALEN, supplied by Aldrich.
Note 3: These hydrogen peroxide sources are expressed on a weight % available oxygen basis. To convert to a basis of percentage of the total composition, divide by about 0.15.
Exa The following fully-formulated solid-form automatic dishwashing d is are repared~
eter en p INGREDIENT ~ ~ ~ %

Cobalt Catal st See Note 2 0.07 0.4 Sodium Perborate Manoh drate See Note 3 0 0.1 Sodium Percarbonate Sae Note 3 1.5 1.2 Am ase G1L37 + M197T as 3% active rotein, 1.5 1.5 NOVO

Protease 1 SAVINASE 12 T, 3.69~o active 2.5 0 rotein Protease 2 Protease D, as 496 alive rotein 0 2.5 Trisodium Citrate Dih drate anh drous basis15 15 Sodium Carbonate anh drous 20 20 BRITESIL H20, PD Co as Si0 Dieth lenetrtamine ntascstic Acid, Sodium 0 0.1 Salt Ethylenediamine Disuccinate, Trisodium Salt~ 0.13 ~ 0 J

H drox eth Idiohos honate HEDP . Sodium 0.5 0.5 Salt Dis ersant Pol mer See Note 1 8 8 Nonionic Surfactant SLF18, Olin Co . or 2 2 LF404. BASF

Sodium Sulfate, water, minors Balance Balance LO 100% t0100%

Note 1: Dispersant Polymer: One or more of: Sokolar~~A30, BASF Corp.,AccusoITM
480N, Rohm 8 Haas.
Note 2: Cobalt SALEN, supplied by Aldrich.
Note 3: These hydrogen peroxide sources are expressed on a weight % available oxygen basis. To convert to a basis of percentage of the total composition, divide by about 0.15.
Examcle 6 The following fully-formulated solid-form automatic dishwashing detergents are prepared:

INGREDIENT wt ~6 wt r6 Cobalt Catal st See Note 2 0.2 0.07 Sodium Perborate Monoh drate See Note 3 1.5 1.5 Am (ase QL37 + M197T as 3% active rotein, 1.5 1.5 NOVO

Protease 1 SAVINASE 12 T, 3.fi~ alive rotein 2.5 0 Protease 2 Protease D, as 4~ active rotein 0 2.5 Trisodium Citrate Dih drate anh drous basis 15 15 Sodium Carbonate, anh drous 20 20 BRITESIL H20, PQ Co as Si0 9 8 Sodium Metasilicate Pentah drate, as Si0 0 3 Dietti lenetriamine ntaacetic Acid, Sodium 0 0.1 Salt Eth lenediamine Disuccinate, Trisodium Salt 0.13 0 H ro eth Idi hos honate HEDP , Sodium Salt 0.5 0.5 Dis ~rsant Pol er See Note 1 8 8 Nonionic Surfactant SLF18, Olin Co . or LF404,2 2 BASF

Sodium Sulfate, water, minors Balance Balance t0100~fo10100%

Note 1: Dispersant Polymer: One or more of: Sokolan PA30, BASF Corp.,Accusol 480N, Rohm & Haas.
Note 2: Cobalt SALEN, supplied by Aldrich.
Note 3: These hydrogen peroxide sources are expressed on a weight % available oxygen basis. To convert to a basis of percentage of the total composition, divide by about 0.15.
Example 7 INGREDIENT wt % wt % wt Cobalt Catal st See Note 2 0.7 0.2 0.8 Sodium Perborate Monoh ~drate See 1.5 0 0.5 Note 3 Sodium Percarbonate Sera Note 3 0 1.0 1.2 Amylase 2 1.5 1 QL37 + M197T as 3% active rotein, NOVO

Dibenzo I Peroxide 0.8 0.8 3.0 Bleach Activator AED or NOBS 0 0 0.5 Protease 1 (SAVINASE 12 T, 3.6% active2.5 0 0 rotein Protease 2 Protease D, as 4% active 0 1 1 rotein Trisodium Citrate Dih drate anh drous15 15 15 basis Sodium Carbonate, anh drous 20 20 20 BRITESIL H20, PQ Co as Si0 7 7 17 Sodium Metasilicate Pentahydrate, 3 0 0 as Si0 Dieth lenetriamine entaac:etic Acid,0 0.1 0 Sodium Salt Diethylenetriaminepenta(methylenephosphonic0.1 0 0.1 acid , Sodium Salt H dro eth Idi hos honate HEDP , Sodium0.5 0 0.5 Salt Dis ersant Pol mer See Note 1 6 5 6 Nonionic Surfactant (SLF'IB, Olin 2 2 3 Corp. or LF404, BASF

Sodium Sulfate, water, mi~~nors BalanceBalance Balance to 100%to 100% to 100%

Note 1:Dispersant Polymer: One or more of: Sokolan PA30, BASF Corp.,Accusol 480N, Rohm & Haas.
Note 2: Cobalt SALEN, supplied by Aldrich.
Note 3: These Hydrogen Peroxide Sources are expressed on an available oxygen basis. To convert to a basis of percentage of the total composition, divide by 0.15 Example 8 INGREDIENT wt % wt % wt Cobalt Catal st See Note 2 0.2 0.07 0.4 Sodium Perborate Monoh drate See Note1 2 1 Sodium Percarbonate See Note 3 0 0 0 Amylase 2 1.5 0 (Termamyl~
from NOVO

Dibenzo I Peroxide 0 0.1 1 Bleach Activator AED or NOBS 0 0 2 Protease 1 SAVINASE 12 T, 3.6% active2.5 0 0 rotein Protease 2 Protease D, as 4% active 0 1 1 rotein Trisodium Citrate Dih drate anh drous15 30 15 basis Sodium Carbonate, anh drous 20 0 20 BRITESIL H20, PQ Co as Si0 7 10 8 Sodium Metasilicate Pentah drate, 3 0 1 as Si0 Dieth lenetriamine entaacetic Acid, 0 0.1 0 Sodium Salt Diethylenetriaminepenta(methylenephosphonic0.1 0 0.1 acid , -Sodium Salt H dro eth Idi hos honate HEDP , Sodium0.1 0 0.1 Salt Dis ersant Pol mer See Note 1 8 5 6 Nonionic Surfactant (SLF18, Olin Corp.1.5 2 3 or LF404, BASF

Sodium Sulfate, water, minors Balance Balance Balance to 100% to 100% to 100%

Note 1:Dispersant Polymer: One or more of: Sokolan PA30, BASF Corp.,Accusol 480N, Rohm & Haas.

Note 2: Cobalt SALEN, supplied by Aldrich.
Note 3: These Hydrogen Peroxide Sources are expressed on an available oxygen basis. To convert to a basis of percentage of the total composition, divide by 0.15 The ADD's of the above dishwashing detergent composition examples are used to wash tea-stained cups, starch-soiled and spaghetti-soiled dishes, milk-soiled glasses, starch, cheese, egg or babyfood- soiled flatware, and tomato-stained plastic spatulas by loading the soiled dishes in a domestic automatic dishwashing appliance and washing using either cold fill, 60oC peak, or uniformly 45-50oC wash cycles with a product concentration of the exemplary compositions of from about 1,000 to about 5,000 ppm, with excellent results.

Claims (24)

What is claimed is:

1. A method of washing tableware in a domestic automatic dishwashing appliance, said method comprising treating the soiled tableware in the automatic dishwasher with an aqueous alkaline bath comprising a source of hydrogen peroxide and a cobalt catalyst having the formula:
[Co n L m X p]z Y z wherein n is an integer from 1 to 4; m is an integer from 1 to 12; p is an integer from 0 to 8; Y is a counterion selected dependent on the charge z of the complex; X is a coordinating species selected from the group consisting of Cl-, Br-, I-, F-, NCS-, I3, -OH, O2 2-, O2-, HOO-, H2O, SH-, CN-, OCN-, S4 2-, NH3, NR3, RCOO-, RO-, ,RSO3- and RSO4- in which R is selected from hydrogen, substituted alkyl, unsubstituted alkyl, substituted aryl, unsubstituted aryl, and R'COO- where R' is selected from substituted alkyl, unsubstituted alkyl and substituted aryl, unsubstituted aryl, and mixtures thereof; and L is an organic ligand molecule having the general formula wherein R1 and R2 can each be absent, H, substituted and unsubstituted alkyl, substituted and unsubstituted aryl; each D can be independently NR, PR, O, S, wherein R is H, substituted or unsubstituted alkyl, and substituted or unsubstituted aryl; t and t' are each independently 2 or 3, and s=2, 3, 4, or 5.

2. A method according to claim 1 wherein the pH of the bath is below 11.

3. A method of washing tableware in a domestic automatic dishwashing appliance, said method comprising treating the soiled tableware in the automatic dishwasher with an aqueous alkaline bath comprising an automatic dishwashing detergent composition comprising:
(a) a catalytically effective amount of a cobalt chelated catalyst having the formula:
[Co n L m X p]z Y z wherein n is an integer from 1 to 4; m is an integer from 1 to 12; p is an integer from 0 to 8; Y is a counterion selected dependent on the charge z of the complex; X is a coordinating species selected from the group consisting of Cl-, Br-, I-, F-, NCS-, I3, -OH, O2 2-, O2-, HOO-, H2O, SH-, CN-, OCN-, S4 2-, NH3, NR3, RCOO-, RO-, ,RSO3- and RSO4 in which R is selected from hydrogen, substituted alkyl, unsubstituted alkyl, substituted aryl, unsubstituted aryl, and R'COO- where R' is selected from substituted alkyl, unsubstituted alkyl, substituted aryl, unsubstituted aryl, and mixtures thereof; and L
is an organic ligand molecule having the general formula wherein R' and R2 can each be absent, H, substituted and unsubstituted alkyl, substituted and unsubstituted aryl; each D can be independently NR, PR, O, S, wherein R is H, substituted or unsubstituted alkyl, and substituted or unsubstituted aryl; t and t' are each independently 2 or 3, and s=2, 3, 4, or 5;
(b) a stain removing effective amount of a source of hydrogen peroxide;
and (c) automatic dishwashing detergent adjunct materials.

4. A method for removing tea and/or coffee stains from tableware in a domestic automatic dishwashing appliance, said method comprising treating tea-stained tableware in the automatic dishwasher with an aqueous alkaline bath comprising a source of hydrogen peroxide and a cobalt catalyst of the formula:
[Co n L m X p]z Y z wherein n is an integer from 1 to 4; m is an integer from 1 to 12; p is an integer from 0 to 8; Y is a counterion selected dependent on the charge z of the complex; X is a coordinating species selected from the group consisting of Cl-, Br-, I-, F-, NCS-, I3, -OH, O2 2-, O2-, HOO-, H2O, SH-, CN-, OCN-, S4 2-, NH3, NR3, RCOO-, RO-, ,RSO3- and RSO4 in which R is selected from hydrogen, substituted alkyl, unsubstituted alkyl, substituted aryl, unsubstituted aryl, and R'COO- where R' is selected from substituted alkyl, unsubstituted alkyl, substituted aryl, unsubstituted aryl, and mixtures thereof; and L is an organic ligand molecule having the general formula wherein R1 and R2 can each be absent, H, substituted and unsubstituted alkyl, substituted and unsubstituted aryl; each D can be independently NR, PR, O, S, wherein R is H, substituted or unsubstituted alkyl, and substituted or unsubstituted aryl; t and t' are each independently 2 or 3, and s=2, 3, 4, or 5.

5. A method for washing tableware in a domestic automatic dishwashing appliance, said method comprising treating the soiled tableware during a wash cycle of the automatic dishwasher with an aqueous alkaline bath comprising a source of hydrogen peroxide, followed by treating the tableware during the subsequent rinse cycle with an aqueous bath comprising a cobalt catalyst having the formula:
[Co n L m X p]z Y z wherein n is an integer from 1 to 4; m is an integer from 1 to 12; p is an integer from 0 to 8; Y is a counterion selected dependent on the charge z of the complex; X is a coordinating species selected from the group consisting of Cl-, Br-, I-, F-, NCS-, I3, -OH, O2 2-, O2-, HOO-, H2O, SH-, CN, OCN-, S4 2-, NH3, NR3, RCOO-, RO-, ,RSO3- and RSO4- in which R is selected from hydrogen, substituted alkyl, unsubstituted alkyl, substituted aryl, unsubstituted aryl, and R'COO- where R' is selected from substituted alkyl, unsubstituted alkyl, substituted aryl, unsubstituted aryl, and mixtures thereof; and L is an organic ligand molecule having the general formula 52~

wherein R1 and R2 can each be absent, H, substituted and unsubstituted alkyl, substituted and unsubstituted aryl; each D can be independently NR, PR, O, S, wherein R is H, substituted or unsubstituted alkyl, and substituted or unsubstituted aryl; t and t' are each independently 2 or 3, and s=2, 3, 4, or 5.

6. A method according to claim 3 wherein the automatic dishwashing adjunct material includes at least one of an alkyl phosphate suds suppressor, a silicone suds suppressor and mixtures thereof whereby the composition produces less than 5 centimetres of suds under normal use conditions.

7. A method according to claim 3 comprising as part or all of the automatic dishwashing adjunct material one or more low foaming nonionic surfactants.

8. A method according to claim 3 comprising as part or all of the automatic dishwashing adjunct material one or more material care agents.

9. A method according to claim 3 comprising as part or all of the automatic dishwashing adjunct material one or more water soluble silicates.

10. A method according to claim 3 comprising as part or all of the automatic dishwashing adjunct material one or more bleach activators.

11. A method according to claim 10 wherein the bleach activator is TAED.

12. A method according to claim 3 having a 1 % aqueous solution pH of less than 11.

13. An automatic dishwashing detergent composition comprising:
(a) from 0.01% to 2% by weight of the composition of a cobalt chelated catalyst having the formula:
[Co n L m X p]z Y z wherein n is an integer from 1 to 4; m is an integer from 1 to 12; p is an integer from 0 to 8; Y is a counterion selected dependent on the charge z of the complex; X is a coordinating species selected from the group consisting of Cl-, Br-, I-, F-, NCS-, I3, -OH, O2 2-, O2-, HOO-, H2O, SH-, CN, OCN-, S4 2-, NH3, NR3, RCOO-, RO-, ,RSO3- and RSO4- in which R is selected from hydrogen, substituted alkyl, unsubstituted alkyl, substituted aryl, unsubstituted aryl, and R'COO- where R' is selected from substituted alkyl, unsubstituted alkyl, substituted aryl, unsubstituted aryl, and mixtures thereof; L is an organic ligand molecule containing more than one heteroatom selected from N, P, O and S which coordinate via at least two heteroatoms;
wherein L does not include a non-(macro)-cyclic ligand;
(b) from 0.1% to 69.89% by weight, of a source of hydrogen peroxide;
(c) from 30% to 99.79%, by weight, of one or more automatic dishwashing adjunct materials; and (d) from 0.1% to 10% by weight of the composition of a low-foaming nonionic surfactant, wherein said nonionic surfactant has a cloud point of less than 32°C.

14. An automatic dishwashing detergent composition according to Claim 13 wherein the automatic dishwashing adjunct material includes at least one of an alkyl phosphate suds suppressor, a silicone suds suppressor and mixtures thereof whereby the composition produces less than 5 centimetres of suds under normal use conditions.

15. An automatic dishwashing detergent composition according to Claim 13 comprising as part or all of the automatic dishwashing adjunct material one or more material care agents.

16. An automatic dishwashing detergent composition according to Claim 13 comprising as part or all of the automatic dishwashing adjunct material one or more water soluble silicates.

17. An automatic dishwashing detergent composition according to Claim 13 comprising as part or all of the automatic dishwashing adjunct material one or more bleach activators.

18. An automatic dishwashing detergent composition according to Claim 17 wherein the bleach activator is TAED.

19. An automatic dishwashing detergent composition according to Claim 13 having a 1% aqueous solution pH of less than 11.

20. An automatic dishwashing rinse aid composition comprising:
(a) from 0.01% to 2% by weight of the composition of a cobalt chelated catalyst having the formula:
[Co n L m X p]z Y z wherein n is an integer from 1 to 4; m is an integer from 1 to 12; p is an integer from 0 to 8; Y is a counterion selected dependent on the charge z of the complex; X is a coordinating species selected from the group consisting of Cl-, Br-, I-, F-, NCS-, I3, -OH, O2 2-, O2-, HOO-, H2O, SH-, CN-, OCN, S4 2-, NH3, NR3, RCOO-, RO-, ,RSO3- and RSO4 in which R is selected from hydrogen, substituted alkyl, unsubstituted alkyl, substituted aryl, unsubstituted aryl, and R'COO- where R' is selected from substituted alkyl, unsubstituted alkyl, substituted aryl, unsubstituted aryl, and mixtures thereof; L is an organic ligand molecule containing more than one heteroatom selected from N, P, O and S which coordinate via at least two heteroatoms;

(b) from 30% to about 99.89% of automatic dishwashing adjunct materials;
from 0.1% to 10% by weight of the composition of a low-foaming nonionic surfactant, wherein said nonionic surfactant has a cloud point of less than 32°C.

21. An automatic dishwashing detergent composition comprising:
(a) from 0.01% to 2% by weight of the composition of a cobalt chelated catalyst having the formula:
[Co n L m X p]z Y z wherein n is an integer from 1 to 4; m is an integer from 1 to 12; p is an integer from 0 to 8; Y is a counterion selected dependent on the charge z of the complex; X is a coordinating species selected from the group consisting of Cl-, Br-, I-, F-, NCS-, I3, -OH, O2 2-, O2-, HOO-, H2O, SH-, CN-, OCN-, S4 2-, NH3, NR3, RCOO-, RO-, ,RSO3- and RSO4- in which R is selected from hydrogen, substituted alkyl, unsubstituted alkyl, substituted aryl, unsubstituted aryl, and R'COO- where R' is selected from substituted alkyl, unsubstituted alkyl, substituted aryl, unsubstituted aryl, and mixtures thereof; L is an organic ligand molecule containing more than one heteroatom selected from N, P, O and S which coordinate via at least two heteroatoms;
wherein L does not include a non-(macro)-cyclic ligand;
(b) from 0.1% to 70% by weight, of a source of hydrogen peroxide;

(c) from 0.1% to 10% by weight of the composition of a low-foaming nonionic surfactant, wherein said nonionic surfactant has a cloud point of less than 32°C; and, (d) from 0.001% to 5% by weight of the composition of a sud suppresser.

22. An automatic dishwashing detergent composition according to claim 21 wherein said sud suppresser is selected from the group consisting of alkyl phosphate sud suppressors, silicone sud suppressors and combinations thereof.

23. An automatic dishwashing detergent composition according to claim 21 wherein said sud suppresser is present in an amount of from about 0.01% to about 3% by weight of the composition and said low-foaming nonionic surfactant is present in an amount of from about 0.25% to about 4% by weight of the composition.

24. An automatic dishwashing detergent composition according to claim 23 wherein said composition further includes a nonphosphate, water soluble detergency builder.