CA2423920A1 - 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

wo 96ns86o ~cTmsqbioi ms r 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 1NVEA~TIOI~~
Automatic dishwashing, particularly in domestic appliances, is an art very different from fabric laundering. Domestic fabric laundering is normally done in purpose-built machines having a tumbling action. These are very different from spray-action domestic automatic dishwashing appliances.
The spray action in the tatter tends to cause foam. Foam can easily overflow the low sills of domestic dishwashers and slow down the spray action, which in tum reduces the cleaning action. Thus in the distinct field of domestic machine dishwashing, 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 dishwashing 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 atso 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 f;~r from satisfactory results in a dishwashing context: for example, ability to remove tough tea stains is limited, especially in hard water, and requires rather large amounts of Wo 96123860 PCTItJS96t01198 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 (ADDS
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 hypochiorite, 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, enrymes such as commercial amylolytic enzymes (e.g., TERMAMY!~ available from Novo Nordisk SIAM can be added. The aipha-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 CVO 96123860 PCTlUS9610I198 secure improved bleach activators specifically designed to be compatible in AD~ 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 described in U.S. Patent 5,246,612, issued September 21, 1993, to Van ~ijk et 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 dinuclear manganese, macrocyclic figand-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. 6,244,594, to Favre et al., issued September 14, 1993.
Therein, Example I provides data slowing a Co-Co catalyst according to European Patent Application, Publication iVo. 408,131, published January 16, 1991 by Unilever hIV, 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 compasitions, especially compact granular, phosphate-free types, incorporating an improved selection of cobalt catalyst-containing bleaching ingredients. A further object is to provide fully-formulated A~D
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.
SACKGR~UIVD ART
In addition to the hereinbefore-noted U.S. Patent 4,810,410, to Diakun et a1, issued March 7,19!39; U.S. 5,246,612, to Van Dijk et al., issued WO 96!23860 PCT11JS9610119$

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 Uniiever NV, see also: U.S. Patent 5,114,611, to Van Kraiingen 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 ~ragg, issued February 7, 1984 (laundry bleaching compositions comprising catalytic heavy metal rations, 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 iIVVENl'ION
The present invention encompasses automatic dishwashing detergents comprising:
(a) a eatalytieally effective amount of a cobalt ehelated catalyst having the formula:
CConLmXplz 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 5y; 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°, 18,'OH, 022', 02°, HOO', H2~, SH, CN', OCN°, S42-, NH3, NRg, RCOO°, RO°;
~ ~.
i1 r~cccHCC~
RSOe' and RSO4 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 i'VO 96123860 PCTNS9610 l l 98 S
molecule containing more than one heteroatom (preferably 2 to 5; more preferably 2 to 4) selected from N, P, O, and S which coordinate via at least two heteroatoms (preferably via two nitrogen atoms);
(b) an effective 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 TERMAMYL~ 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.Licheniformis 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 andlor 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-farm, fully-formulated ADD's, preferably phosphate builder-free and chlorine bleach-free, in which additional ingredients, including other enzymes (especially proteases andlor amylases) are formu8ated.
The instant invention also encompasses methods; more particularly, a method of washing tableware in a domesvtic automatic dishwashing appliance, comprising treating the soiled tableware in an automatic dishwasher with an aqueous alkaline bath comprising a cobalt-containing catalyst having the formula as provided hereinbefor~e and a source of hydrogen peroxide, WO 96123860 3'C'YYtIS96101198 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. All documents cited are, in relevant part, incorporated herein by reference, DETAILED ~ESCRIPTION OF THE INVENTION
Automatic Dishwashing Compositions:
Automatic dishwashing compositions of the present invention preferably comprise a source of hydrogen peroxide and a particularly selected cobalk catalyst. The source of hydrogen peroxide is any common hydrogen-peroxide releasing salt, such as sodium perborate or sodium percarbonate. In the preferred embodiments, additional 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 spottinglfilming), 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 TAE~ 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 9b/238b0 PCTIUS9bI01198 In general, materials used for the production of ADD compositions herein are preferably checked for compatibility with spottinglfilming on glassware. Test methods for spottinglfiiming 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 0.1 % to about 20% , preferably from about 0.1 % to about 10% of a low-foaming nonionic surfactant. such fully-formulated embodiments typically further comprise from about 0.1 % to about 15% of a polymeric dispersant, from about 0.01 °l° to about 10% of a chelant, and from about 0.00001 % to about 1 D% 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 composition.
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-iW0 96I~3860 PC'&YUS9G101198 Sy '°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 maohines 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.
C',obalt Catalr, sr ts:
The present invention compositions and methods utilize cobalt (III) catalysts having the formula:
~ConLmXPJz Yz wherein n is an integer from 1 to 4; m is an integer from 1 to 12; p is an integer from ~ 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, 02~', O2', HOO', H2~, SH, CN-, OCN', S~2', NH3, NR3, RCOO', RO';
O O-II

RSO3' 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 WO 9b!23860 PC'I'/US9b101198 molecule containing more than one heteroatam (preferably 2 to 5; more preferably 2 to 4} selected from N, P, O, and S which coordinate via at least two heteroatoms (preferably via two nitrogen atoms).
Preferred L are selected from the following grou~rs, (a) Macrocyclic organic molecules of the formula:
D--(CR&RZ}~-f-D-(CR'~2}~-l~~
L
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, O 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 will be unsaturated, giving rise 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:
-(~~E~2~._".~~I3°°°(CRyR2}t'-]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 N, NR, PR, O 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 iigands are those in which D or D' is NH or NR; t and t' are 2 or 3, s=2, and R1=R2=H, more preferably, wherein D or D' is NCHg and t, t'=2.
Other preferred ligands are those whereic~ D or D° is NCH3; t, t'=2, s=2; and R1 and RZ can each be H or alkyl.
Examples of these ligands are:
9) 1,4, 7-triazacycfononane;

Wo 96123860 PCTJ(7s961U1198 1,4,7-triazacyclodecane;
1,4,7-trimethyl-1,4,7-triazacyclononane;
1,4,7-trimethyl-I-4,7-triazacyclodecane;
1,4,8-trimethyl-1,4,8-triazacycloundecane;
1, 5,9-trimethyl-1,5,9-triatriazacyciododecane;
1,4-dimethyl-7-ethyl-1,4,7-triazacyclononane.
ii) Tris(pyridin-2-yl}methane;
Tris(pyrazol-I-yl)methane;
Tris(imidazol-2-yl)methane Tris(triazol-1-yl)methane;
iii) Tris(pyridin-2-yl)borate;
Tris(triazol)-i-yl)borate;
Tris(imidazol-2-yl)phosphine;
Tris( imidazol-2-yl)borate.
iv) cis-cis-1,3,5-trisamino-cyclohexane;
1,1,1-tris(methylamino)ethane.
v) Bis(pyridin-2-yl-methyl)amine;
Bis(pyrazol-I-yl-methyl}amine;
Bis(triazol-I-yl-methyl)amine;
Bis(imidazol-2-yl-methyl}amine;
They may be substituted on amine nitrogen atoms andlor CH2 carbon atoms and/or aromatic rings.
Such iigands 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 Kerschner et al., issued ~ecember 28, 1993, both incorporated herein by reference in their entirety.
(b) SALEN-type and SALP~-type ligands of the general formulae:

WO 96123860 PCT/US96lU1198 ~2 and ~1 O_ ,1V
(CRS
I
T
(CRl O N
,R
Rz)m R2)m b RW.-J
~- N
( ~ R 1R2)tga (CRS R2)in T T
(CRS Rz)m b CCR~ R2 )m N. O_ N b R.
wherein m is 2-~, preferably 2-3; R~ , R~ can each be a substituent selected from H, substituted and unsubstituted alkyl, substituted and unsubstituted aryl; Q~ and Q~ can each be a substituent selected from H, optionally substituted alkyl or aryl, N02, NR2, NR3~', O-alkyl, O-aryl, WO 96/2386(i PCT/EIS96101198 halogen, SO2-, alkyl SO3' and aryl S03-, T is either NR, O, 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, the disclosures of which are incorporated herein by reference in their entirety.
(c) Non-macro-cyclic iigands of the formula:

.r R
s~ CaaN
FCC N ~
in which R1, R~, 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 Rg-C=N-R~ form a five- or six-membered, optionally substituted, nitrogen-containing heterocyclic ring system; and B is a bridging group selected from O, S, CR5R6, NR7 and C=O, wherein R5 R5 and R7 can each be H, alkyl or aryl groups which may optionally be substituted. Examples of optional substituents are halogen, OH, N02 NH2, Sgt , 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, far 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 ace 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, 192, the disclosures of which are incorporated herein by reference in their entirety.
(d) Porphyrin-type ligands of the formula:

WO 96123860 PCTILIS9blp1198 Ar as described in European Patent Applications Publication No.
306,089, published March 8, 1989 and Publication No. 384,503, published August 29, 1990, both incorporated herein by reference in their entirety.
Methods for making these cobalt cheiated 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, both incorporated herein by reference in their entirety.
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 minion of the active cobalt c;ataiyst 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 0.47°J° to about 0.4°/~, by weight of the ADD
compositions.
H,ydroaen Peroxide Source Hydrogen peroxide sources are described in detail in the hereinabove incorporated Kirk ~thmer°s Encyclopedia of Chemical Technology, 4th Ed (1992, John Wiley & Sons), Vol. 4, pp. 271-300 "Bleaching Agents (Survey}", and include the various forms of sodium perborate and sodium percarbonate, including 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°/0, mare 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 fram about 500 micrometers to about 1,000 mirxometers, 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 hydragen 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 far the properties required of WO 96123860 PCT/~JS96101198 an automatic dishwashing 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") D3~56->35 (Reapproved 1939) '°Standard Test Method for Deposition on Glassware During Mechanical Dishwashing". Also far 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, far example, that described in U.S. Patent 5,294,365, to Weich et a1_, issued March 15, 1994}.
Adiunct 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 an the form of the composition, i.e., whether the composition is to be said as a liquid, paste semi-solid}, or solid form (including tablets and the preferred granular forms 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 andlor anti-corrosion agents, dyes, fillers, germicides, alkalinity sources, hydrotropes, anti-oxidants, enzyme stabilizing agents, pertumes, solubilizing agents, carriers, processing aids, pigments, and, for liquid formulations, solvents, as described in detail hereinafter.
1. Detercrent Surfactants:
~,a) tow-Foaming Nonionic Surfactant - Surfactants are useful in Automatic Dishwashing to assist cleaning, help defoam food soil foams, especially from proteins, and to help control spottinglfilming and are desirably included in the present detergent compositions at levels of from WO 96!23860 PCTlIJS96101198 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 prefereabiy 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 water-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 t_FNIs include nonionic alkoxylated surfactants, especially ethoxylates derived from primary alcohols, and blends thereof with more sophisticated surfactants, such as the polyoxypropyienelpoiyoxyethylenelpoiyoxypropylene (POIEOlPO) reverse block polymers. The POIEOI~'O 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 95oF (35oC)> more preferably solid at about 77oF (25oC). For ease of manufacture, a preferred LFNI has a melting paint between about 77oF (25oC) and about 140oF (60oC), more preferably between about 80oF {26.6oC) and 110oF
{43.3oC).
!n a preferred embodiment, the LFNi is an ethoxyfated 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 mote 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 (C f 6-C20 alcohol), preferably a C1g alcohol, condensed with an average of from about 6 to about 15 moles, preferably from about '~ to about 12 moles, and most preferably from about 7 to about 0 moles of ethylene oxide per mole of W4 96123860 PCTltJS96101198 alcohol. Preferably the ethoxylated nonionic surfactant so derived has a narrow ethoxyiate distribution relative to the average.
The LFN1 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 18, 1980, Builloty, incorporated herein by reference, Highly preferred ADDS herein wherein the LFNI is present make use of ethoxylated monohydroxy alcohol or alkyl phenol and additionally comprise a polyoxyethylene, polyoxypropylene block polymeric compound;
the ethoxylated monohydroxy alcohol or alkyl phenol fraction of the LFNI
comprising from about 20°/~ to about 9 a0°/a, 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, trimethylotpropane 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 C~ 2.~ g aliphatic alcohots, do not generally provide satisfactory suds control in the instant ADDS. Certain of the block polymer surfactant compounds designated PLURONIC~ and TEl'RONIC~ by the BASF-Wyandotte Corp., 111Fyandotte, Allichigan, are suitable in ADD compositions of the invention.
A particularly preferred LFN1 contains from about 40% to about r 0% of a polyoxypropylenelpolyoxyethylenelpolyoxypropylene block polymer blend comprising about 75°~, by weight of the blend, of a reverse block co-polymer of polyoxyethylene and polyoxypropylene containing 17 moles of ethylene oxide and ~44 moles of propylene oxide; and about 25°~6, by weight of the blend, of a block co-polymer of polyoxyethytene and polyoxypropylene initiated with trimethylolpropane and containing 99 moles of propylene oxide and 24 moles of ethylene oxide per mole of trimethytolpropane.
Suitable for use as LFNI in the ADD compositions are those LFNI
having relatively low cloud points and high hydrophilic-fipophilic balance !8 (HLB). Cloud points of 9 % 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 poiyethoxylate, having a degree of ethoxylation of about 8, commercially available as SLF18 from Olin Carp., and any biodegradable LFldi 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. tt 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-surtaetant is typically of a type having good solubility in the presence of calcium. Such anionic co-surfactants are further illustrated by sulfobetaines, alkyi(poiyethoxy)sulfates (AES), alkyl (polyethoxy)carboxylates, and short chained Cg-Cep 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 and/or 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 ADO compositions herein comprise one or more detersive enzymes. if only one enzyme is used, it is preferably an amyoiytic enzyme when the composition is for automatic dishwashing use. Highly preferred for automatic dishwashing is a mixture of proteoiytic enzymes and amyloytic enzymes. More generally, the enzymes to be incorporated include proteases, amylases, lipases, celluiases, and peroxidases, as well as mixtures thereof. Other types of enzymes rnay 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 WO 96123860 PCTlUS96101198 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. 8n 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 % to about 8°~, preferably 0.01 %-1 % 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/filming results.
Suitable examples of proteases are the subtiiisins which are obtained from particular strains of 8. subtilis and B. licheniformis. Another suitable protease is obtained from a strain of Bacil9us, having maximum activity throughout the pH range of 8-12, developed and said by Novo Industries AIS as ESPEI~ASE~. 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 SAV1NASE~ by Novo Industries AIS (Denmark) and MAXATASE~ by International Bio-Synthetics, Inc, (The Netherlands).
ether proteases include Protease A (see European Patent Application 130,756, published January 9, 1985) and Protease B (see European Patent WO 96I2~860 PCTJUS96lOI 198 Application Serial No. 873087fi1.8, filed April 28, 1987, and European Patent Application 130,756, Bott et al, published January 9, 1985).
An especially preferred protease, referred to as "Protease 0" 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, +1fifi, +195, +197, +204, +206, +210, +216, +217, +218, +222, +260, +265, andlor +274 according to the numbering of Bacillus arr~yloliquefaciens subtiiisin, as described in the patent applications of A. Baeck, et al, entitled "Protease-Containing Cleaning Compositions" having U.S. Serial No, x81322,676, and C. Ghosh, et al, '°Bleaching Compositions Comprising Protease Enzymes'°
having U.S.
Serial No. 081322,677, both filed ~ctober 13, 1994.
Amylases suitable herein include, for example, a-amylases described in British Patent Specification No. 1,29fi,839 (Novo), RAPIDASE~, International Bio-Synthetics, Inc. and TERMAMYL~, Novo Industries.
Engineering of enzymes (e.g., stability-enhanced amylase) for improved stability, e.g., oxidative stability is known. See, for example J.Bioiogical 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 TERMAMYL~ 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}

compositions of the invention. Evero 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 peroxideltetraacetyiethylenediamine in buffered solution at phl 9-1 U; thermal stability, e.g., at Gammon wash temperatures such as about 60oC; or alkaline stability, e.g., at a pH from about 9 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 94102597, itself and documents therein referred to being incorporated by reference.
In general, stability-enhanced amylases respecting the preferred embodiments of the invention can be obtained from Novo Nordisk AIS, 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-limitingly illustrated by the following:
(a) An amylase according to the hereinbefore incorporated WGl94!(12597, Novo Nordisk AIS, published Feb. 3, 1994, as further illustrated by a mutant in which substitution is made, using alanine or threonine (preferably threonine), of the methionine residue located in position 197 of the B.licherriformis alpha-amylase, known as TERMAMYL~, or the homalagous position variation of a similar parent amylase, such as B.
amylohquefaclens, B.subtlhs, or B.stearofhermophiJus;

WO 96I238so PC'fIUS96101198 (b) Stability-enhanced amylases as described by Genencor International in a paper entitled "Oxidativefy 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.licher~iformis NCIB80fi1. Methionine (Met) was identified as the most likely residua 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 Ml9iT 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 AlS. 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 celiuiases. 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 Numicola strain DSM1800 or a cellulase 212-producing fungus belonging to the genus Aeromonas, and celluiase extracted from the hepatopancreas of a marine mollusk (Dola6ella Auricula Solander). Suitable cellulases are also disclosed in GB-A-2.075.028; GB-A-2.095.275 and DE-C1S-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 stufzeri ATCC 19.154, as disclosed in British Patent 1,372,034. See also iipases in Japanese Patent Application 53,20487" laid open to public inspection on February 24, 1978. This lipase is available from Amano Pharmaceutical WO 96123860 PGTlIJS9G/01198 Co. Ltd., Nagoya, Japan, under the trade name Lipase P "Arnano,"
hereinafter referred to as "Amano-P." Other commercial lipases include Amano-CES, lipases ex Chromobacrer viscosum, e.g, Chromobacter viscosum var. lipalyticum NRRLi3 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 LIPOLASE~ enzyme derived from Numicola larruginosa 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 V1lO 92105249 and Research Disclosure No. 35944, March 10, 1994, both published by Novo. fn general, lipolytic 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 salution. 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, far example, in PCT
International Application WO 891099813, published October 19, 1989, by O.
Kirk, assigned to Novo tndustries A/S. The present invention encompasses peroxidase free automatic dishwashing composition embodiments.
A wide range of enzyme materials and means for their incorporation into synthetic detergent compositions ate 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 at, issued July 18, 1978, and in U.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 ai, and European Patent Application Publicatian No. 0 199 405, Application No. 86200586.5, published October WO 96!23860 PCTIUS961o1198 29, 1986, Venegas. Enzyme stabilization systems are also described, for example, in !!.S. Patent 3,519,570.
ja) ~nzvme 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%, mast preferably from about 0.01 % to about fi°~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°l°, preferably from about 0.01 % to about 6% by weight, of chlorine bleach scavengers, added to prevent chorine 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 tats! 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 rations with sulfite, bisulfite, thiosulfite, thiosulfate, iodide, etc. Antioxidants such as carbamate, ascorbate, etc., organic amines such as ethyfenediaminetetracetic 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 percarbanate, as well as phosphate, condensed phosphate, acetate, benzoate, citrate, farmate, lactate, malate, tartrate, salicylate, etc., and mixtures thereof can be used if desired. In general, since the chlorine scavenger function can be pertormed 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 enzyrne-containing embodiment of the invention; even then, the scavenger is added only for optimum results. Moreover, the formulator will exercise a chemist's norrnai 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. Ot~tional Bleach Adjuncts Via) Bleach Activators - Hleach 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.S. Patent 4,915,954, issued April 10, 1990 to Mao et al, and U.S. Patent 4,412,934. Nonanoyioxybenzene sulfonate (HOBS) 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:
R1N(R5)C(O)R2C(O)L or R1C{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 factam. Further illustration of bleach activators of the above formulae include (6-octanamido-caproyl)oxybenzenesulfonate, (6-nonanamidocaproyl)axybenzenesulfonate, (6-decanamido-capr~y!)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, issued October 30, 1990. Still another class of bleach activators includes acyl lactam activators such as octanoyi caprolactam, 3,5,5-trimethylhexanoyl caprolactam, nonanoyl caprolactam, decanoyl caprolactam, undecenoyl caprolactam, octanoyl valerolactam, decanoyl valerolactam, undecenoyl valerolactam, nonanoyl valerolactam, 3,5,5-trimethylhexanoyl valerolactam and mixtures thereof. The present WU 9bl238b0 PC'1'It7S96101198 compositions can optionally comprise acyl benzoates, such as phenyl benzoate.
(b) Or4anic Peroxides. es ep ciallv Diacyl Peroxides - These are extensively illustrated in Kirk Othmer, Encyclopedia of Chemical Technology, Vol. 17, John 111liiey and Sons, 1982 at pages 2790 and especially at pages 63-72, all incorporated herein by reference. If a diacyl peroxide is used, it will preferably be one which exerts minimal adverse impact on spottinglfilming, 4. saH and Bufferin4 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 additions! 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 - 5,0~0 ppm, the pH remains in the range of above about 8, preferably from about 9.5 to about 11. The preferred nonphosphate pH-adjusting carnponent 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% SiO2).

wo 9s~asssa pc°rnrs~srol i9a Illustrative of highly preferred pH-adjusting camponent systems are binary mixtures of granular sadium citrate with anhydrous sodium carbonate, and three-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°~6 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 fram 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 ammanium berates, hydroxysulfonates, polyacetates, and polycarboxylates. Preferred are the alkali metal, especially sodium, salts of such materials. Alternate water-soluble, nan-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-saluble silicates herein are any silicates which are soluble to the extent that they do not adveresely affect spottinglfilming 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 zeoiite builders, Na SKS-f 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 ~yH2o wherein M is sodium or hydrogen, x is a number from 1.9 to 4, preferably 2, and y is a number from 0 to 20, preferably 0 can be used. lfarious other layered silicates from Hoechst include NaSKS-5, NaSKS-7 and NaSKS-11, as the a.-, ~- 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 s;~~cates 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 typicalPy comprise at least about 1% builder, High performance compositions typically comprise from about 10% to about 80%, WO 9bI23860 P~T/US96t01198 za 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 mete-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 has 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.
Aluminosilicate 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 buifders 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 2fi4.
Useful aluminosi irate 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 Zeoiite A, Zeolite P (B), Zeolite MAP and Zeolite X. In an embadiment, the crystalline aluminosilicate ion exchange material has the formula:
Nal2t~A102)12~Sa~2)12I'xH2~ wherein x is from about 20 to about 30, especially about 27. This material is known as Zeoiite A. Dehydrated zeolites (x - 0 - 10) may also be used herein. Preferably, the aiuminosilicate has a particle size of about U.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 aluminosiiicates as adsorbents for surfactants, especially in granular compositions. Aggregates of silicate or aiuminosiiicate 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 farm adapted to promote surfactant carrier function, and appropriate particle sizes may be freely selected by the formulator.
Organic detergent builders suitable for the purposes of the present invention include, but are not restricted t~, a wide variety of polycarboxylate compounds. As used herein, "pofycarboxylate" 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 alkanoiammonium 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 polycarboxytates, including oxydisuccinate, as disclosed in Berg, U.S. Patent 3,128,281, issued Apri! 7, 1864, and Lamberti et al, U.S. Patent 3,635,830, issued January 18, 197'2. See also 'TMSfTDS" builders of U.S. Patent 4,663,071, issued to Bush et al, on May 5, 1987. Suitable ether polycarboxyiates also include cyclic compounds, particularly alicyclic compounds, such as those described in U.S. Patents 3,923,679; 3,835,163; 4,158,835; 4,120,874 and 4,102,903.

WU 96123860 PCTIUS9b101198 Other useful detergency builders include the ether hydroxypolycarboxyBates, copolymers of malefic anhydride with ethylene or vinyl methyl ether, 1, 3, 5-trihydroxy benzene-2, 4, E~-trisulphonic acid, and carboxymethyloxysuccinic acid, the various alkali metal, ammonium and substituted ammonium salts of polyacetic 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, carboxymethyloxysuecinic acid, and soluble salts thereof.
Citrate builders, e.g., citric acid and soluble salts thereof 4particularly 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 BRITESDL
types, andlor layered silicate builders. Oxydisuccinates 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 di closed in U.S. Patent 4,566,984., Bush, issued January 28, 1986. Useful succinic acid builders include the C5-C20 alkyl and alkenyl 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 Pike. Laurylsuccinates are the preferred builders of this group, and are described in European Patent Application 86200690.5!0,20(7,263, published November 5, 1986.
Other suitable polycarboxy3ates are disclosed in U.S. Patent 4,144,226, Crutchfield et a!, 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-C1g monocarboxylic acids, may also be incorporated into the compositions atone, or in combination with the aforesaid builders, especially citrate andlor 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 WO 96!23860 PCTIUS96101198 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 ace more commonly used in a low-level mode as chelants or stabilizers.
6. Ghelatinct A4ents The compositions herein may also optionally contain one or more transition-metal selective sequestrants, "chelants" or "chelating agents", e.g., iron andlor 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 cheiating 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-hydroxyethyiethylenediaminetriacetates, nitrilo-triacetates, ethylenediamine tetraproprionates, triethylenetetraaminehexacetates, diethylenetriamine-pentaacetates, and ethanoldigiycines, alkali metal, ammonium, and substituted ammonium salts thereof. (n general, chelant mixtures may be used for a combination of functions, such as multiple transition-metal control, long-term product stabilization, andlor control of precipitated transition metal oxides andlor hydroxides.

W~ 96123860 p~TIUS96101198 Polyfunctionally-substituted aromatic chelating agents are also useful in the compositions herein. See U_S. Patent 3,812,044, issued May 21, 1974, to Connor et 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 Iota!
phosphorus are acceptable in detergent compositions, and include the ethylenediaminetetrakis (methylenephosphonates} and the diethylenetriaminepentakis (methylene phosphonates}. Preferably, these aminophosphonates do not contain alkyl or alkenyl groups with more than about 5 carbon atoms.
If utilized, chelating agents or transition-metal-selective sequestrants 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. Disaersant Polymer - Preferred ADD compositions herein may additionally contain a dispersant polymer. When present, a dispersant polymer in the instant ADD compositions is typically at levels in the range from 0 to about 25°~, preferably from about 0.5°~6 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 deposifiion of calcium carbonate or magnesium silicate on dishware.
Dispersant polymers suitable for usa herein are further illustrated by the film forming polymers described in U.S. Pat. No. 4,379,080 (Murphy), issued Apr. 5, 1983.
Suitable polymers are preferably at least partially neutralized or alkali metal, ammonium or substituted ammonium (e.g., mono-, dl- or triethanolammonium) salts of polycarboxyiic acids. The alkali metal, especially sodium salts are most preferred. IPVhile 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 25(1,000, 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,Ofi7 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°l°, 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)OR3)j wherein the apparently unfilled valencies are in fact occupied by hydrogen and at least one of the substituents R1, R2, or R~, preferably R1 or R2, is a 1 to 4 carbon alkyl or hydroxyalkyl group; R1 or R2 can be a hydrogen and R3 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.

WO 96/23860 PCTIUS961~119~
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 3,5D0 and is the fully neutralized form of the polymer comprising about 70°!~ by weight acrylic acid and about 30% by weight methacrylic acid.
~ther suitable modified polyacryfate copolymers include the low molecular weight copolymers of unsaturated aliphatic carboxylic acids disclosed in U.S. Patents 4,530,766, and 5,084,535.
Agglomerated forms of the present ADD compositions may employ aqueous solutions of polymer dispersants as liquid binders for snaking 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 acrylatelmaleate or acrylatelfiumarate copolymers with an average molecular weight of from about 2,000 to about r30,000 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 hawing 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 10DpC, can be obtained at molecular weights of 1,450, 3,400, 4,500, 6,000, T,400, 9,500, and 20,000. Such compounds are formed by the polymerization of ethylene glycol or propylene glycol with the requisite number of motes of ethylene or propylene oxide to provide the desired molecular weight and melting paint of the respective polyethylene glycol and polypropylene glycol. The polyethylene, polypropylene and mixed glycols are referred to using the formula:

W~ 96123860 PCTIUS96IU1198 HO(CH2CH2O)m(CH2CH(CH3)O)n(CH(CH3)CH2O)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, methylcellufose 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, ~iehl, issued Mar. 27, 1973; the dextrin esters of polycarboxylic acids disclosed in U.S. Pat. No. 3,929,1Q7, Thompson, issued Nov. 11, 1975; the hydroxyaikyl starch ethers, starch esters, oxidized starches, dextrins and starch hydrolysates described in U.S. Pat No. 3,8D3,285, 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 ~,~ents - The present A~D compositians may contain one or more material care agents which are effective as corrosion inhibitors andlor 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 salver 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 metasificate, silicate, bismuth salts, manganese salts, paraffin, triazoles, pyrazoles, thio(s, mercaptans, aluminium fatty acid salts, and mixtures thereof.
When present, such protecting materials are preferably incorporated at low levels, e.g., from about ~.01°I° to about 5% of the A~~
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 025..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
70. Additionally, the addition of low levels of bismuth nitrate (i.e., Bi(NO3)3) is afro 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 avaid any tendency to produce spots or films on glassware or to compromise the bleaching action of the campositions. For this reason, mercaptan anti-tarnishes 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 Suaaressors - The ADD's of the invention can optionally contain an alkyl phosphate ester 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. C~arrett, Marce! Dekker, N.Y., 1973, ISBN
0-8247-8770-6, incorporated herein by reference. See especially the chapters entitled "Foam control in Detergent Products" {Ferch et al) and "Surtactant Antifoams" (Blease et al). See alto IJ.S. Patents 3,933,fi72 and 4,136,045. Highly preferred silicone suds suppressers 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, WO 96!23860 PCT/US96101198 polydimethylsiloxanes having trimethylsilyl or alternate endblocking units may be used as the silicone. These may be compounded with silica and/or with surtace-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 campounds is Dow Corning 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% octadecyldimethylamine oxide may not require the presence of a suds suppresser. 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 coco 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 suppresser.
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 aster component. Vllithout 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 tJ.S. Patent 3,314,891, issued April 18, 1967, to Schmolka et al, incorporated herein by reference. Preferred alkyl phosphate esters contain from 16-20 carbon atoms. Highly preferred alkyl phosphate esters are monostearyl acid phosphate or monooleyl acid phosphate, or salts thereof, particularly alkali metal salts, or mixtures thereof.
It has been found preferable to avoid the use of simple calcium-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.

6V~ 9612386a P~T143S96101198 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.
(Vote that preferences, in terms of purity suffiicient to avoid decomposing bleach, applies also to pH-adjusting component ingredients, specifically including any silicates used herein.
Although aptionally 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.
Teach-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, 1987 can also be added to the present compositions in appropriate amounts. Other common detergent ingredients consistent with the spirit and scope 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 WO 96123860 PCTII~JS96101198 with a low-foaming nonionic surtactant 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.
Some preferred substantially chlorine bleach free granular automatic dishwashing compositions of the invention are as fellows; a substantially chlorine-bleach free automatic dishwashing composition comprising amylase (e.g., TERMAMYL~) andlor a bleach stable amylase and a bleach system comprising a source of hydrogen peroxide selected from sodium perborate and sodium percarbanate 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 IV~BS.
Method for Cleaninct:
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 Compositions 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'°. Vllhile the hereinbefore described compositions may also be formutated to be used as rinse aid compositions, it is not required for purposes of use as a rinse aid to have a source of WO 96123860 1~CTIUS96J01198 hydrogen peroxide present in such compositions (although a source of hydrogen peroxide is preferred, at least at low levels to at least supplement the cant'-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 cataiytically effective amount of a cobalt catalyst as described herein, and (b) automatic dishwashing detergent adjunct materials. Preferred compositions comprise a low foaming nonionic surfactant. These compositions also preferably are in liquid or solid form.
The present invention also encompasses methods for washing tableware in a domestic 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.
Examales 1-3 The following fully-formulated solid-form automatic dishwashing detergents aye prepared:

°/~ Active % Actiye % Active Sodium Citrate 15.0 15.0 15.0 Sodium Carbonate 17.5 20.0 20.0 WO 96123860 PCTNS96f01198 Dispersant Polymer (See 6.0 6.0 6.0 Note 1) Hydroxyethyldiphosphonate1.0 0.5 0.71 {HEDP; acid) Nonionic Surfactant (SLF18,2.0 ~.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 0.2 0.07 0.4 Note 2) Savinase G.OT {protease)-- 2.0 2.0 Savinase 12T (protease} 2.2 -- --Termamyl 60T {amylase) 1.5 1.0 1.0 BRITESIL H20, PQ Corp. i3.0 8.0 8.0 (as Si02) Meta Silicate (anhydrous)1.25 - --Paraffin ~ 0.5 -- --Benzotriazole 0.3 - --Sulphate, water, monors Balance Saiance to Balance to to 100% 100% 100l0 Note 1: Dispersant Polymer: One or more of: Sokolan PA30, BASF Corp.,Accusol 480N, Rohm ~ Haas.
Note 2: N,N'-Bis(salicylidene)ethyienediaminocobalt ((l} (hereinafter °'Cobalt SALEN"), supplied by Aidrich.
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, Note 4: djethylenetriaminepentakis (methylene phosphonic acid}
Examr~le 4 INGREDIENT wt l wt /o 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 rotein2.5 ' 0 WO 96!23860 P'CTIUS9610119~

Protease 2 (Protease D, as 4/_ active rotein0 2.5 Trisodium Citrate Dih drate anh drous basis15 15 Sodium Carbonate, anh drous 20 20 BRfTESIL H20, PQ Gor . as SiC3 ~ 8 Dieth fenetriamine entaacetic Acid, Sodium 0 0-1 Sait Eth ienediamine Disuccinate, Trisodium Salt0.13 0 H drox eth ldi hos honate t-IEDP , Sodium 0.5 0-5 Salt Dis ersant Pol mer See Note 1 8 8 Nonionic Surfactant SLF18, Olin Cor , or 2 2 LF40~, BASF

Sodium Sulfate, water, minors Balance Balance to 100! to 100!~

Note 1: Dispersant Polymer: One or more of: Sofcolan 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, dirride by about 0.15.
Example 5 The following fully formulated solid-form automatic dishwashing ,.i..,~~,r..,or,i~ urn nranarssei~

_.
ucam v. m.m. A J'B

INGREDIENT W

Cobalt Catal st See Note 2 O.U7 0.4 Sodium Perborate Monoh drate See Note ~ 0.1 Sodium Percarbonate See Note 3 1.5 1.2 Am lass ~ QL37 + M197T as 3% active rotein,1.5 1.5 NOVO

Protease 1 SAVINASE 12 T, 3.fi! aetive 2.s 0 rotein Protease 2 Protease D, as 4/o active rotein0 2~5 Trisodium Citrate Dih drate anh drous 15 15 basis Sodium Carbonate anh drous 20 20 BRITESIL H20, PQ Ca as SiQ s Dieth lenetriamine entaacetic Acid, Sodiumo 0.1 Salt Eth lenediamine Disuccinate, Trisodium 0.13 f 0 I
Salt WD 96!23860 PCT/LIS96/01198 H drox eth ldipho,s~rhonate H( EDP), 0.5 0.5 -,Sodium Salt Dis ersant Pol mar See Note 1 8 g Nonionic Surfactant SLF18, Olin Co . 2 2 or LF404. BASF) Sodium Sulfate, water, minors Balance Salance to 100% to 100%

Note 1: Dispersant Polymer: Cane or more of: SakoPan PA30, BASF Corp.,Accusol 480N, Rohm 8~ Haas.
Note 2: Cobalt SALEM, 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 6 The following fully-formulated solid-form automatic dishwashing deter ants are re ared:

INGREDIENT wt % wt /a Cobalt Catal st See Note 2 0.2 0.07 Sodium Perborate Monoh drate See Note 3 1.5 1.5 Am case QL37 + I~A197T as 3/o active rotein,1.5 1.5 Protease 1 SAVINASE 12 T, 3.6% active rotein2.5 0 Protease 2 Protease D, as 4% active rotein0 2.5 Trisodium Citrate Dih drate anh drous basis15 15 Sodium Carbonate, anh drous 20 20 BRITESIL H20, Pfd Cor . as Si~ 9 8 Sodium Metasilicate Pentah drate, as Si0 0 3 Dietfi lenetriamine entaacetic Acid, Sodium0 0.1 Salt Eth ienediamine Disuccinate, Trisodium 0.13 0 Sait H dro eth ldi hos honate HEDP , Sodium 0.5 0.5 Salt Dis ersant Poi mar See Note 1 8 8 Nonionic Surfactant SLF18, Olin Go . or 2 2 LF4~04, BASF

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

WO 96123860 PCTlUS96101198 4$
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 °/o available oxygen basis. To convert to a basis of percentage of the total composition, divide by about 0.15.
Exam !e 7 INGREDIENT wt % wt % wt Cobalt Catal st See Note 2 0.7 0.2 0.3 Sodium Perborate Monoh drate See 1.5 0 0.5 Note 3 Sodium Percarbonate See Note 3 0 1.0 1.2 Amylase 2 1.5 1 C~L37 + M197T as 3% active rotein, NOVA

Dibenzo I Peroxide 0.8 0.8 3.0 Bleach Activator AED or NOBS 0 0 0.5 Protease 1 (SAV1NASE 12 T, 3.fi% 2.5 0 0 active rotein Protease 2 Protease D, as 4% active0 1 1 rotein 15 15 15 Trisodiurn Citrate Dih drate anh drous basis Sodium Carbonate, anh drous 20 20 20 gRITESIL H20, PQ Co as SiO 7 7 ~ 17 Sodium Metasilicate Pentah drate, 3 0 0 as Sid Dieth lenetriamine entaacetic Acid,0 0.1 0 Sodium Salt Diethylenetriaminepenta(methylenephosphonic0.1 0 0.1 acrd , Sodium Sait H dro eth Idi hos honate HEDP , 0.5 0 0.5 Sodium Salt 6 5 6 Dis ersant Pol er See Note 1 Nonionic Surfactant (SLF18, Olin 2 2 3 Corp. or LF404, BASF

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

W U 961238b0 PCTIU S96I01198 =l6 Note l:Dispersant Polymer: One or more of: Sokolan PA30, BASF Carp.,Accusol 480N, Rohm 8 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 /o wt Cobalt Catal st See Note 2 0.2 0.07 0.4 Sodium Perborate Monoh drate See 1 2 1 Note 3 Sodium Percarbonate See Nate 3 0 0 0 Amylase 2 1.5 t?
(1'ermamyl~
from NOVO

Dibenzo I Peroxide 0 0.1 1 Bleach Activator AED or NABS 0 0 2 Protease 1 SAVINASE 12 T, 3.6~o active2.~ 0 0 rotein Protease 2 Protease D, as 4% active 0 1 rotein Trisodium Citrate Dih drate anh drous15 30 15 basis Sodium Carbonate, anh drous 20 0 20 BRITESIL H20, PQ Co as SiO 7 10 8 Sodium Metasilicate Pentah drate, 3 0 1 as Si0 Dieth lenetriamine entaacetic Acid, 0 0.1 0 Sodium Salt Diethylenetriaminepenta(methylenephasphonic0.'1 0 0.1 acid , ~So~ium Salt H dra eth Idi hos honate HEDP , Sodium0.1 0 0,1 Salt Dis ersant Pol mer Sae Note 1 8 5 6 Nonionic Surfactant (SLF18, Olin 1.5 2 3 Corp. or LF404, BAS

Sodium Sulfate, water, minors Balance BalanceBalance to 1009 to 9009~o to 100%

Note l:Dispersant Polymer One or more of: Sokofan PA30, BASF Corp.,Act;usoi 480N, Rohm 8~ Haas.

W~ 96!23860 PCTIUS9f>101198 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 compasition examples are used to wash tea-stained cups, starch-soiled and spaghetti-soiled dishes, milk-soiled glasses, starch, cheese, egg or babyfood- sailed 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-~OoC wash cycles with a product concentration of the exemplary compositions of from about 1,000 to about 5,000 ppm, with excellent results.

Claims (13)

1. ~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 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 selected from N, P, O, and S which coordinate via at least two heteroatoms;
(b) an effective amount of a source of hydrogen peroxide; and (c) automatic dishwashing detergent adjunct materials.

2. ~An automatic dishwashing detergent composition according to Claim 1 comprising automatic dishwashing adjunct material selected such that the composition produces less than 2 inches of suds under normal use conditions.

3. ~An automatic dishwashing detergent composition according to either of Claims 1 or 2 comprising as part or all of the automatic dishwashing adjunct maternal one or more low foaming nonionic surfactants.

4. An automatic dishwashing detergent composition according to any of Claims 1-3 comprising as part or all of the automatic dishwashing adjunct material one or more material care agents.

5. An automatic dishwashing detergent composition according to any of Claims 1-4 comprising as part or all of the automatic dishwashing adjunct material one or more water soluble silicates.

6. An automatic dishwashing detergent composition according to any of Claims 1-5 comprising as part or all of the automatic dishwashing adjunct material one or more bleach activators, preferably TAED.

7. An automatic dishwashing detergent composition according to any of Claims 1-6 having a 1% aqueous solution pH of less than 11.

8. A method of washing tableware in a domestic automatic dishwashing appliance, said method comprising treating the soiled tableware in an 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 an the charge z of the complex; X is a coordinating species selected from the group consisting of Cl-, Br, l-, F-, NCS-, l3,-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 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 selected from N, P, O, and S which coordinate via at least two heteroatoms.

9. A method according to Claim 8 wherein the pH of the bath is below 11.

10. A method of washing tableware in a domestic automatic dishwashing appliance, said method comprising treating the soiled tableware in an automatic dishwasher with an aqueous alkaline bath comprising an automatic dishwashing detergent composition according to any of Claims 1-7.

11. 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 an automatic dishwasher with an aqueous alkaline bath comprising a source of hydrogen peroxide and the 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-, l-, F-, NCS-, l3,-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 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 selected from N, P, O, and S which coordinate via at least two heteroatoms.

12. An automatic dishwashing rinse aid composition comprising:
(a) a catalytically effective amount of 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, l-, F-, NCS-, l3,-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 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 selected from N, P, 0, and S which coordinate via at least two heteroatoms; and (b) automatic dishwashing detergent adjunct materials, preferably comprising one or more low foaming nonionic surfactants.

13. A method for washing tableware in a domestic automatic dishwashing appliance, said method comprising creating 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 during the subsequent rinse cycle with an aqueous bath comprising a cobalt 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 an the charge z of the complex; X is a coordinating species selected from the group consisting of Cl-, Br-, l-, F-, NCS-, l3,-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 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 selected from N, P, O, and S which coordinate via at least two heteroatoms.