MXPA97005991A - Compositions of automatic washing machine quecomprenden catalysts of cobalt (i - Google Patents

Abstract

Detergent automatic dishwashing compositions comprising certain cobalt catalysts are provided, more specifically, the invention relates to automatic dishwashing detergents that provide improved cleaning / bleaching benefits (especially in the removal of tea stains) through of the selection of cobalt (III) catalysts having the formula [Co (NH3) mMmBbTtQqPp] Yy, the preferred automatic dishwashing compositions comprise amylase and / or protease enzymes, including methods for washing utensils for service of table in appliances for automatic dishwashing using cobal catalysts

Description

AUTOMATIC WASHING COMPOSITIONS COMPRISING COBALT CATALYSTS (III) FIELD OF THE INVENTION The present invention is found in the field of detergents for automatic dishwashing that I understand bleach. More specifically, the invention encompasses the ete ge t s trusted automatic washing of boxes (liquids, pastes, and solids such as the ball and especially the granulates) comprising catalysts that are bound cobalt selected. The most preferred methods for washing-cutlery are included.

BACKGROUND OF THE INVENTION IT automatic dishwashing, particularly in household appliances, is a very different technique of industrial washing procedure. Industrial washing is usually done in machines built exprofeso that have cleaning action. These are very different from appliances for automatic dishwashing that has a spray action. The spray action in the last tends to cause foam. The foam can easily exceed the limits of the domestic dishwashers and decrease the spray action, which in turn reduces the cleaning action. In this way, the use of detergent surfactants for washing that produce foam is normally restricted in the field other than domestic dishwashing machines. These aspects are not just a brief illustration of the formulation restrictions in the domestic dishwashing field. Automatic dishwashing with bleaching chemicals is different from that of industrial bleach. In the automatic dishwashing, the use of bleaching chemicals involves the promotion of removal of dirt from the dishes, it can also happen that bleaching difficult dirt. In addition, the redeposition of dirt and the effects of annealing of the bleaching chemicals would be desirable. Some whitening chemicals, (such as a source of hydrogen peroxide, alone or together with tet raacet iletilenodiarnine, TAFD) may, in certain circumstances, be useful for washing kitchen utensils, but this technology has more than satisfactory results. In a context of dishwashing: for example, the ability to remove difficult stains is limited, especially in hard water, and requires greater amounts of bleach.Another activators developed for use in washing can even have negative effects, such as create unpleasant deposits, when placed in a product for automatic dishwashing, especially when they have diminished too much or the solubility.Other bleaching systems can damage unique pieces to wash, such as silverware, kitchen utensils or certain plastics. tableware and cutlery for consumption, especially decorative pieces, when washed in household dishwashing machines, po Generally, they are susceptible to damage and can be expensive to replace. Typically, consumers do not like having to separate the finest pieces and would prefer the convenience and simplicity of being able to combine all of their table and kitchen utensils into a single automatic washing operation. Although the above is done as a routine, it has not yet been achieved. Regarding the restrictions of previous techniques as well as the needs and demands of the consumer, detergent compositions for automatic dishwashing (ADD) are undergoing roads and continuous improvements. In addition, environmental factors such as phosphate restriction, desire to provide better results, cleaning with less product, providing less thermal energy, and less water to aid in the washing process, have led to the need for ADD compositions. Improved .. A recognized need in HDD compositions is to have one or more ingredients that improve the removal of hot beverage stains (e.g., tea, coffee, chocolate, etc.) from consumer items. The alkaline as the sodium drug, bleaches such as potion, builders such as phosphates and the like can help to vary the degree but all can also damage, or leave a film, glassware, crockery or cutlery. Accordingly, softer ADD compositions have been developed. These use a source of hydrogen peroxide, optionally with a bleach activator as TflED, as indicated. In addition, enzymes such as commercially available enzymes (eg, T RMP, MYLR available from Novo Nordi k / A) can be added. The component to the a-ama lasa provides at least some benefit in the properties of the ADD for removal of stiff dirt. ADD's that contain arnilases can typically provide a slightly more moderate pH wash in use and can remove stubborn dirt while avoiding large weight equivalents of sodium hydroxide on a per gram basis of product. Therefore, it would be very convenient to ensure improved bleach activators specifically designed to be compatible with the flDD formulations, especially with enzymes such as arnides. There is also a. need to ensure better action of ailase in the presence of bleach activators. Certain machine dishwashing compositions containing manganese as a catalyst are described in the U.S.A. 5,246,612, filed on September 21, 1993, by Van Dijl-- et al. The compositions are said to be machine dishwashing compositions free of bleach with chlorine comprising arnilasa and manganese catalyst (in the oxidation state +3 or +4), as defined by the structure given therein. The manganese catalyst that is preferred therein is a dinuclear manganese, the molecule containing the inacrocyclic ligand is said to be Plniv2 (u-0) 3 C l, 4, 7-t prnet 11 - .4, 7 -t riazací clononano) 2 (PFe) 2 »Such catalytic materials that contain these more complicated liquids will typically require many synthetic steps to produce, thus increasing the cost of the catalysts and making them less likely to be found. easily available for use. Thus, a need continues to exist for widely available simple catalysts that are effective in the compositions and methods for automatic dishwashing. Simple cobalt catalysts useful in the present have been described for use on washing compositions containing bleach for washing stained fabrics as discussed in the U.S. Patent. 4,810,410, for Dial-un v '-'t, filed March 7, 1989. For example, table 8 thereof provides the results of stain removal for a series of washes on washed fabrics with washing compositions with and without the cobalt-catalyst CCo (NH3) sClICI2 - The removal of tea stains on fabrics as reported therein seems marginal when compared to other measured stains. The comparative inferiority of cobalt catalysts herein for laundry applications for removing tea stains is reinforced by what is shown in the European patent application filed later, publication No. 408,131, published on January 15, 1991 by Uní lever NV. The TV example in it, which claims to be a comparison of the cobalt-cobalt complexes that are perceived as the invention of that application against the "CCo (NH3) sCl] Cl2 technique" (referring to the first publication of the European latent equivalent mentioned above by Diakun and others), reports values for tea stain removal as follows: Co-Co (25.3); [Co (NH3) s C11C12 (20.5), which is lower than that observed for a simple catalyst Mn + 2 co or was reported in the TI example (which have a stain removal value of 1.4). Similar results are reported for manganese catalysts with cobalt catalysts, and uses of washing to remove tea stains from cotton fabrics in E.U.A. 5,244,594, for Favre et al., Filed on September 4, 1993. In the same, example T provides information that the reduction of a Co-Co catalyst in accordance with EP 408,131 is lower than that of the manganese catalyst. In addition, Example V also reports stain removal of less than 20 ° C for a Co-Co catalyst of EP 408,131 and the rCo (NH 3) sCl] Cl 2 catalyst of the Diakun patent against a manganese catalyst. While such inferior results are perceived for the removal of tea stains on fabrics during washing procedures, when used in automatic dishwashing compositions according to the present invention, these catalysts provide surprisingly effective e-spot spotting. for tableware .. Such effectiveness would not be expected from the prior art. It is an object of the present invention to provide compositions for autogenous washing of vat 111, especially compact granular, phosphate-free types, which incorporate an improved selection of bleach ingredients containing cobalt catalyst. A further object is to provide fully formulated ODD compositions with or without arylase enzymes, but especially the former, wherein the specific bleach systems containing cobalt catalyst are combined with additional ingredients selected including conventional arnilases or stable bleaching arnilases, so They provide superior tea stain cleaning results and provide excellent care for tableware and eating utensils.

ANTECEDENTS OF THE TECHNIQUE In addition to the aforementioned herein, US patents. 4,810,410 for a day and a year presented on March 7, 1989; E.U.A. 5,246,512, for Van üijk and others filed on September 21, 1993; E.U.A. 5,244,594, trust Favre et al., Presented on September 14, 1993; and European Patent Application No. 408,131, published on January 16, 1991 by Uní lever NV, also see; the patent of F.U.A. 5,114,511, Van Kralingen et al., Submitted on August 19, 1992 (transition metal complex of a transition metal, such as cobalt, and a non-microbial ligand), U.S. Patent No. 5,114,511. 4,430,243, Bragg fiafer, filed on February 7, 1984 (laundry bleach compositions comprising heavy metal catalytic cations, including cobalt), German patent specification 2,054,019, published on October 7, 1971 by Unilever NV ( cobalt chelator catalyst); and European patent application publication No. 549,271, published June 30, 1993 by Unilever PLO (macrocyclic organic ligands in cleaning compositions).

BRIEF DESCRIPTION OF THE INVENTION Now it has been discovered that a specific group of Coordinated NH3, cobalt-containing catalysts provide an unexpected superior cleaning performance for automatic dishwashing ("ADD"). Such performance is illustrated by the removal of tea stains, but is not limited to it. Viewed loosely, the present invention encompasses automatic dishwashing detergents comprising: (a) a catalytically effective amount of a cobalt catalyst having the formula: R (NH3)? Mii'Bb U qPp "lYy in where the cobalt is in the oxidation state +3; n an integer from 0 to 5 (preferably 4 or 5; very proferi or 5); M represents a monodentate ligand, is an integer from 0 to 5 (preferably 2) very preferred 1); I) represents a ligand of bidentate, b is an integer of 0 to, T represents a ligand of tridentate, t is 0 or 1, • 0 is a ligand of teradentate, q is 0 or 1; P is a ligand of peni adent ato; p is 0 or 1; and n 'rn + 2b' + 4q + 5p - 5; and one or more selected contions appropriately present in a number y, where y is an integer of 1 to 3 (preferably 2 to 3, most preferred 2 when Y is a charged anion of 1), to obtain a balanced charge salt, the preferred Y are selected from the group consisting of oruro, nitrate, nitrite, sulfate, citrate, acetate, carbonate, and combinations thereof; wherein in addition at least one of the cobalt fixed coordination sites labil ba or automatic dishwashing use conditions and the remaining coordination sites stabilize the cobalt under automatic dishwashing conditions so that the reduction potential for cobalt (Til) to cobalt (II) under alkaline conditions (eg, pH = 10) is less than about 0.4 volts (preferably less than about 0.2 volts) against an electrogen of normal hydrogen; (b) an effective amount of a source of hydrogen peroxide; and (<;) adjunct materials, detergents, and self-cleaning washing dishes. The detergent compositions for automatic dishwashing herein further comprise an amylase enzyme. Since conventional rings such as TERMAMYLR can be used with excellent results, preferred ADD compositions can use adhesives with improved oxidative stability. Such arnilasa is available from NOVO. In this, oxidative stability is improved by substitution using threonine of the rnetonine residue located at position 197 of B.Licheni forrnis or the homologous variation of position of an amylase of similar origin. The ADD's present have numerous advantages, for example, they are economical, compact and less harmful than what can be expected- for tableware for consumption based on its powerful bleaching action, are not safe or chlorinated compounds, and can be formulated to avoid the inconvenient use of too high levels of caustic ingredients. In certain preferred embodiments, they are substantially free of boron / or phosphate. In the modalities of ADD composition, there may be additional materials that improve bleaching. Preferably, these are selected from bleach activating materials, such as tet raacetilet ilenediarnma ("TAED"). The present invention encompasses granular form, fully formulated ADD's, preferably phosphate-free detergency builder and chlorine bleach 1, in which the additional ingredients are formulated, including other enzymes (especially proteases and / or or amylases). The present invention also encompasses methods; more particularly, a method for washing tableware in an automatic dishwashing machine, which comprises treating the dirty utensils in an automatic dishwasher with an aqueous alkaline bath comprising catalyst- containing cobalt having the formula as provided. above and a source of hydrogen peroxide The present invention also relates to compositions that assist the automatic dishwashing rinse process comprising a cobalt-containing catalyst as described herein, and methods for treating utensils in an automatic dishwashing machine for domestic use during a rinse cycle with these cobalt-containing catalysts. As already mentioned, the invention has advantages, including the excellent combination of tea stain removal, good care of the dishes, and good overall cleaning helped by a greater flexibility to formulate enzymes, especially amino acids. All parts, percentages and ratios used herein are expressed as weight percent unless otherwise specified. All the cited documents, in relevant parts, are incorporated herein by reference.

DETAILED DESCRIPTION OF THE INVENTION Automatic Dishwashing Compositions The automatic dishwashing compositions of the present invention preferably comprise a source of hydrogen peroxide and a selected cobalt couplet catalyst. The source of hydrogen peroxide is any hydrogen peroxide that liberates salt, such as sodium perborate or sodium percarbonate. In preferred embodiments, additional ingredients are present such as water-soluble silicates (useful for providing alkalinity and to help control corrosion), low foaming nonionic surfactants (especially useful in automatic dishwashing, reliable control of refrigeration). / the film, dispersant polymers (which modify and inhibit the growth of calcium crystals and / or magnesium salts, chelated is (which control the transition metals), detergency builders such as oitrate (which help control calcium and / or magnesium and can help to improve the action), alkalis (to adjust the pH) and detersive enzymes (to help with the difficult cleaning of food stains, especially of rigid and protective soils). bleached bleach such as conventional bleach activators such as TAFB, as long as any of the materials that modif The bleaching is carried out in such a manner as to be compatible with the purposes of the present invention. The detergent compositions present may, in addition, comprise one or more adjuncts for processing, fillers, pe? Fumes, enzymatic materials that make particles including enzyme cores as well as pigments, and the like. In general, the materials used for the production of ADD-containing compositions are preferably reviewed for compatibility with width / width in glassware. Stain / film test methods are generally described in the literature on automatic dishwashing detergents, including DIN test methods. Certain greasy materials, especially in longer chain lengths, and insoluble materials such as clays, like long chain fatty acids or tartar forming soaps are, therefore, preferably limited or excluded from the present compositions. The amounts of the essential ingredients may vary within wide ranges, however in the present automatic dishwashing detergent compositions (having a pH of 1% aqueous solution of about 7 to about 12, more preferably about 9 to about 11) are those that are present from about n.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% 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 surfactant non-ionic low foam. Such fully formulated embodiments further comprise from about 0.1% to about 15% of a polymerase dispersant, from about 0.01% to about 1% of a chelator and from about 0.00001% to about 10% of a detersive enzyme although they may be present. attached or additional ingredients. The detergent compositions herein are in granular form typically of limiting water content, for example less than about 7% free of water, for better storage stability. In addition, the preferred ADD compositions of this invention are substantially free of chlorine bleach. By "substantially free" chlorine bleach it is meant that the formula does not deliberately add a chlorine-containing bleach additive., such as a chloroisocyanurate, to the preferred ADD composition. However, it is recognized that due to factors external to the contol of the processor, such as chlorination of the water supply, a non-zero amount of chlorine bleach may be present in the water liquor. The term "substantial free agent" can be similarly improved - with reference to the preferred limitation of other ingredients, such as phosphate improver. By "effective amount" herein is meant an amount that is sufficient, ba or any comparative test condition employed, to improve the cleanliness of a soiled surface. Thus, the term "effective catalytic amount" refers to an amount of cobalt catalyst that is sufficient under any comparative test condition employed to improve the cleanliness of the soiled surface. In an automatic dishwasher, the dirty surface can be - for example, a porcelain cup with a tea stain, dirty dishes with simple residues or more complex food stains, or a plastic spatula stained with tomato puree. The test conditions will vary, depending on the type of washing appliance used and the user's habits. Some machines have wash cycles considerably longer than others. Some users choose to use hot water regardless of internal heating of the electrode.; others use hot or even cold water to fill, followed by heating through an integrated coil. Of course, such considerations will affect the performance of the bleaches and enzymes, and the levels used in the fully formulated detergent and the cleaning compositions can be adjusted appropriately.

Cobalt catalysts: The compositiand methods of the present invention utilize cobalt (III) catalysts having the formula; rCO (NH3) n Mm Bb Tt Oq PP 3Yy where the cobalt is in the oxidation state +3; n is an integer from 0 to 5 (preferably 4 or 5, very preferred 5); M represents a rnonodentate ligand; m is an integer from 0 to 5 (preferably 1 or 2; very preferred 1); B represents a bidentate ligand; b is an integer from 0 to; r represents a tridentate ligand; t is 0 or 1; it is a tetradentate ligand; q is 0 or l; P is a pentadentate ligand; p is 0 or 1; and n «• rn + 2b * • 3t + 4q + 5p-6; And it is one or more appropriately selected counteripresent in a number and, where y is an integer of 3 (preferably 2 to 3, very preferred 2 when Y is an anion charged of 1), to obtain a cation salt. balanced, the preferred Y's are selected from the group csting of chloride, nitrate, nitrite, sulfate, citrate, acetate, carbonate, and combinatithereof; wherein in addition at least one of the cobalt fixed coordination sites is labile under automatic dishwashing conditiand the remaining coordination sites stabilize the cobalt under automatic dishwashing conditiso that the reduction potential cobalt (III) to cobalt (II) under alkaline conditi(eg,? H ~ 10) is less than about 0.4 volts (preferably less than about 0.2 volts) i 7 against a standard hydrogen electrode. Preferred cobalt catalysts have the formula: wherein n is an integer from 3 to 5 (preferably 4 or ; very preferred 5); More a labile coordination portion, preferably selected from the group csting of chloride, bromide, hydroxide, water, and (when m is greater than 1) combinatiof the same; rn is an integer of 1 a '! (preferably 1 or 2; rnuy preterido 1); m + n - 6; and Y is selected with an appropriately selected present number, which is an integer of 1 to 3 (preferably 2 to 3, most preferred 2 when Y is a charge anion L), to obtain a salt of balanced load. The most preferred cobalt catalyst or il in the present has the formula CCo (NH3) sCl] Yy, and in particular Be know ligands M, B, T, Q and P suitable for use herein, such as those ligands described in the FUA Patent 4,810,410, to Dia un et al., Issued March 7, 1989. In addition, examples of M include ?? ri dina and SCN; examples of B include eti 1 end i amine, bipyridine, acetate, phentrinine, binidazole, and tropolone; and drugs of T include terpriridm, salicylaldehyde acylhy- drates, and dietary ileum; Examples of 0 include tpetilent et rarnina, N (CH CH2 H2> 3, Schi bases ff (for 13 example, H0CH2CH2C = CH2CH2 ~ CCH CH20H); and examples of P include polyamidazoles and H0CH H C- ^ NCH2 H-2MH-CH2 H2N = CCH2 H20H. The most preferred cobalt catalyst useful herein is The formula L "Co (NH3 IsCllTy, and especially CCo (NH3) sClDCl2 - These cobalt catalysts are easily prepared by known methods, such as those shown for example in the US patent. 4,810,410, for Dialun and others, filed March 7, 1989, and J. Chein. Ed. (1989), 56 (12), 1043-45; The Synthesis and Characterizat ion of Tnorganic Compounds, U.L. 3olly (Prenti ce-Hall, 1970), pp. 461-3. These cobalt catalysts can be coprocessed with attached materials to reduce the color impact desired, the aesthetics of the product is trusted, or the composition can be manufactured to contain "sparks" cat to the hoists. As a practical matter, and not by way of limitation, the compositiADl) and methods herein may be adjusted to provide in the order of at least one part per ten million species of active cobalt catalysts in the washing medium. watery, and will preferably provide from about 0.1 pprn to about 50 pprn, more preferably from about 1 pprn to about 25 pprn, and more 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, the DW compositions in the present will comprise approximately 0.04% to about 1%, more preferably from about 0.07% to about 0.4% by weight of the ADD compositions.

SOURCE OF HYDROGEN PEROXIDE The sources of hydrogen peroxide are distilled in detail in the previously incorporated Kirk Othmer's Encyclopedia, Chemical Technology, 4 Ed. (1992, John Wiley R Sons), Vol. 4, p. 271-300"BLeachmg Agents (Survey)", and includes the different forms of sodium perborate and sodium percarbonate, including different covered and odified forms »An" effective amount "of a source of hydrogen peroxide is any amount capable of improving in measurable manner Removal of stains (especially from tea stains) from stained dishes compared to a hydrogen peroxide source-free composition when stained dishes are washed by the consumer in an automatic domestic dishwashing machine in the presence of alkali. Most often a source of hydrogen peroxide in the present is any convenient compound or mixture that provides an effective amount of hydrogen peroxide or consumer use conditions. The levels can range widely and are generally in the range of approximately 0.1% to about 70%, more typically from about 0.5% to about 30%, by weight of the ADD compositions herein. The preferred hydrogen peroxide source herein can be any convenient source, including the hydrogen peroxide itself. For example, perborate eg, sodium perborate (any hydrate but preferably the mono or tet rehydrate), sodium carbonate peroxide or equivalent percarbonate salts, peroxy sodium hydrate peroxide, urea peroxyhydrate can be used. or sodium peroxide. Sodium perborate monohydrate and sodium percarbonate are particularly preferred. Mixtures of any suitable sources of hydrogen peroxide can also be used. A percarbonate bleach comprises dry particles having an average particle size in the range of about 500 microns to about 1,000 microns, not more than about 10% by weight of said particles being smaller than about 200 microns and no more of about 10% by weight of said particles being greater than about 1,250 millimeters. Optionally, the percarbonate can be coated with a borate silicate or water soluble surfactants. Fl percarbonate is available from vain commercial sources such as FrC, Solvay and Tokai Den a. Although the bleaching compositions effective in the present may comprise only the identified cobalt catalysts and a source of hydrogen peroxide, the fully formulated AD1) compositions will typically also comprise other adjunct detergent materials for dishwashing to improve or modify the performance. These materials are selected in an appropriate manner for the required properties of a composition for automatic dishwashing. For example, it is desirable to have low stain and film - preferred compositions have stain and film grades of 3 or less, preferably less than 2, and most preferably less than 1, as measured by The American regular test. Society for Testing and Materials ("ASTM") D3556-85 (Reapproved on 1989) "Standards Test Method for- Deposition on Glassware During Mechanical Dishwashing" .. Also as an example, it is desirable that there be foam ba - the preferred compositions produces less than 5.08 cm. , preferably less than 1 inch, of foam on the bottom of the dishwashing machine under conditions of use (as determined using known methods such as, for example, those described in U.S. Patent 5,294,365, Uelch et al., filed on March 15, 1994).

ATTACHED MATERIALS Detersive ingredients or attachments included > 2 Optionally in the compositions herein may include one or more materials that will help or increase cleaning performance., treatment of the subtraction to be cleaned, or designed to improve the aesthetics of the compositions. They are also selected based on the form of the composition, decn-, if the composition is to be sold in liquid form, paste (solid), or solid (including tablets and granular forms preferred for the present compositions) . Auxiliaries that may also be included in the compositions of the present invention, at their levels established by the conventional technique for use (generally, the adjunct materials comprise, in total, from about 30C% to about 99.9%, preferably about 70 % to about 95%, by weight axis compositions), include other active ingredients such as dispersant polymers (e.g., from BASF Corp. or Rohm & amp;; Hass), sparks of color, silver cracking, anti-oxidation and / or corrosion agents, intes, fillers, germicides, alkalinity sources, hydrotropes, antioxidants, enzyme stabilizing agents, perfumes, sunscreens, vehicles, processing aids, pigments and, for liquid formulations, solvents as described in detail below. 1. DETERGENT TENSIOACTIVE AGENTS: (a) Low Foaming Non-ionic Surfactant Surfactants are useful in automatic dishwashing to help clean, help defoam foams from food stains, especially proteins, and to help control staining / adhesion and are conveniently included in the present compositions. detergents at levels from about 0.1% to about 20% of the composition. In general, stable bleach surfactants are preferred. The ADD (Automatic dishwashing detergent) compositions of the present invention preferably comprise low foaming nonionic surfactants (LFNTs). The LFNI may be present in amounts of from 0 to about 10% by weight, preferably from about 0.25% to about 4%. LFNTs are typically used in ADDs because of the enhanced water-extending action (especially glass) that they give to the ADD product. They also include, without silicon, polyme- pic materials without phosphate, better illus- trated below, which is known to defoam food dirt found in automatic dishwashing. Preferred LFNTs include nonionic alkoxylated surfactants, especially ethoxylates derived from primary alcohols, and mixtures thereof with more sophisticated surfactants, such as polyoxypropylene / polyoxyethylene / polypropylene (PO / EO / PO) polymers. of reverse block. The polymeric surfactants PO / F0 / P0 are well known to have foam-suppressing or de-purifying action. especially in relation to common food dirt ingredients such as egg. The invention encompasses preferred embodiments in which LFNI is present, and wherein this component is -oli or at about 35 ° C, more preferably solid at about 25 ° C. For ease of manufacture, a preferred I.F I has a melting point between about 25 ° C and about 60 ° C, more preferably between about 26.6 ° C and 43.3 ° C. In a preferred embodiment, the LFNI is an ethoxylated surfactant derived from the reaction of a rnononohydroxy or aliphenol alcohol having from about B to about 20 carbon atoms, with from about 6 to about 15 moles of ethylene oxide. per mole of alcohol or alkyl phenol on an average basis. A particularly preferred I.FMT is derived from a straight-chain fatty alcohol containing from about 16 to about 20 carbon atoms (C16-C20 alcohol), preferably a C6 alcohol, condensed with an average of about 6 to about 15 moles, I preferred from about 7 to about 12 moles, and preferably from about 7 to about 9 moles of ethylene oxide per mole of alcohol. Preferably the ethoxylated nonionic surfactant thus derived has a narrow ethoxylated distribution in relation to the average FL I. FNT may optionally contain propylene oxide in a quantity of up to about 15% by weight. Other preferred LFN1 surfactants can be prepared by the process described in the U.S.A. 4,223,163, filed September 16, 1980, Builloty, incorporated herein by reference. Highly preferred ADDs in the present in which the LFNF is present make use of monohydric or othoxylated alcohol or alkyl phenol and furthermore comprise polyexyethylene, polymecopyl compound of Lyoxypropyl cell block; monohydroxy ethoxylated alcohol or alkyl phenol fraction of the LFNI comprising from about 20% to about 100%, preferably from about 30% to about 70% of the total I.FNI. Polyoxyl and i-leno-pol IOX Lpropyl-block polyene compounds that coincide with the requirements described above include those based on ethanol., propylene glycol, glycerol, tprnethylpropane and ot ilenodiamine as a reactive hydrogen initiator compound. Polyrnepic compounds made from an ethoxylation and sequence propoxilation of initiator compounds with only a reactive hydrogen atom, such as Ci2 ~ 8 alcohols, generally do not provide satisfactory foam control in the present ADDs. Some of the block polymer surfactant compounds designated PLURONTCR and TFTRONICR by BASF-Uyandot te Corp., Uyandotte, Michigan, are suitable in the ADD compositions of the invention. A particularly suitable LFMT contains from about 40% to about 70% of a polymer mixture of polypropylene oxide / polyoxyethylene / hydroxypropyl alcohol comprising approximately 755 by weight of the mixture, of a block copolymer inverse of poloxethanol and polypropylene that contains L7 moles of ethylene oxide and 44 moles of propylene oxide; and approximately 25% by weight of the mixture, of a polyoxyethylene and polyoxypropylene block copolymer initiated with tprneti Lolpropane and containing 99 mol of propylene oxide and 24 mol of ethylene oxide per mole of methanol 11o1 propane. Those LFMr that have relatively low dark spots and high hydrophilic ico-1-phylophilic balance (HLB) are suitable for use with LFNT in ADD compositions. The dark spots of 1% of the solutions in water are typically below about 32 ° C and preferably lower, e.g., 0 ° C, for optimum control of the spheres through a full scale of temperatures of the water. LFNEs that can also be used include an alcohol polyethoxylate having an ethoxylation degree of about 8, commercially available as SLF18 from Olin Corp. , and any biodegradable I.FNI that has the melting point properties that are unraveled beforehand. b) Co-anionic surfactant - The detergent compositions for automatic dishwashing in the present preferably are substantially free < he co-ammonium surfactants. It has been found that certain ammonium surfactant co-agents, particularly carboxylic fatty acids, can cause imperceptible films in the dishes. In addition, ammonium surfactants are of high espionage. If present the ammonium surfactant co-agent is generally of a good type which has good solubility in the presence of calcium. Such surfactant co-agents are further illustrated by means of sulfobetaines, the uyl (polyethoxy) sulphates (AES), alkyl (polyoxy) carboxy sides, and short chain alkyl sulfates Ce -Cio »2. Detersive Enzymes In the First, "detersive enzyme" is used as any enzyme that has a cleansing, stain remover or < In another beneficial manner in an ADD composition, the preferred detersive enzymes are hydrolases such as proteases, ilases and lipases. Highly preferred for automatic dishwashing are amylases and / or proteases, including both currently commercially available types and improved types which, being more compatible with strong bleach, have a remaining degree of susceptibility to deactivation of the bleach.

In general, as mentioned, preferred ADD compositions herein comprise one or more detersive enzymes. If only one enzyme is used, it is preferably an amiolyl enzyme when the composition is for use in automatic dishwashing. What is most preferred for automatic dishwashing is a mixture of proteolytic enzymes and enzymes to ioliticae. More generally, the enzymes to be incorporated include proteases, arnilases, lipases, celluLases and peroxidases, as well as mixtures thereof. Other types of enzymes may also be included. These should be of any suitable origin, such as vegetable, animal, bacterial, fungal and foam. However, its choice is governed by many factors such as pH activity and / or optimal stability, tepnoestability, stability against active detergents, deturgency enhancers, etc. In this regard, bacterial or fungal enzymes, such as bacteria and bacterial proteases and fungal cellulases, are preferred. Enzymes are normally incorporated into the present detergent compositions at levels sufficient to provide an "effective cleaning amount". The term "effective cleaning amount" refers to any amount capable of producing a cleaning effect, axis removal of stains or dirt on substrates such as fabrics, tableware and the like. Already the enzymes are catalytic materials, such quantities can be very small. In practical terms for current commercial preparations, typical amounts are up to about 5 grams by weight, more typically from about 0.01 grams to about 3 grams, the enzyme, .c. + Grams per gram of < -om? os? cion. Stated another way, compositions herein will typically comprise from 0.001% to about 6%, preferably f) .01% -l% by weight of a commercial enzyme preparation. Protease enzymes are usually found in commercial preparations at levels sufficient to provide 0.-005 to 0.1 nson units (AU) of activity per gram of composition. For purposes of automatic dishwashing, it is desirable to increase the active enzyme content of the non-calatically active assorted materials and thereby improve the staining / film results. Suitable examples of proteases are the subtils that are obtained from particular strains of B. s? Bt i li s and B. licheni ormis. Another suitable protease is obtained from a strain of accillus, which has a maximum activity through the scale of pH 8-12, developed and sold by Novo Industries A / S as ESPERASE. "The preparation of this enzyme and similar enzymes was discloses in British Patent Specification No. 1,243,784 ele Novo.The suitable commercially available protein-soluble protein removal enzymes include those sold under the trademarks ALCAI.ASER and SAVTNASE "by Novo Industries A / S (Denmark) and MAXTASE "by International Ba- yntheti cs, Inc. (Holland) Other proteases include Protease A (see European patent application 130,756, published January 9, 1985) and Protease B (see the application for European patent Mo. ele sene 87303751.8, filed on April 28, 1987, and European patent application 130,756, Bott et al., published on January 9 <Je 1985.) A particularly preferred protease, designated as "Prot easa D "is a variant of carbomlo hydrolase having an amino acid sequence that is not found in nature, which is derived from a carbonyl hydrolase precursor by substituting a different amino acid for a plurality of amino acid residues. It is also present in a position in said hydrolase-carbonyl equivalent for the +76 position, 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, M23, +27, +105, +109. +126, «-128, +135, + L55, +166, +195, +197, +204, +206, * 210, * 215, +217, -« 218, +222, +260, +265 and / or +274 in accordance with the numbering of s? Btiiisma Rasi llus ama loli quefaciens, as described in the patent applications of A. Baeck, et al., Entitled "Prot ease-Contai ni ng Cleamng Compositions" which has the serial number in United States 08 / 322,676 and C. Ghosh et al., "Bleaching Coinpositions Com- pping Protease Enzymes", which has the United States number 08 / 322,677, both filed on October 13, 1994. In this case, adequate armrests include , for example, cr-arní lasas described in the specification of the axis British patent No. 1,296,839 (Novo), RAPTDASFR, International Bio-Synthetics, Tnc. and TERMAMYLR, Novo Indust laugh Axial enzyme engineering (eg, amylase of increased stability) is known to improve stability, e.g., oxidative stability. See, for example, I). Biologí cal Chem., Vol. 260, No. 11, jumo axis 1985, pp 6518-6521. "Reference amylase" refers to a conventional arylase within the scope of the arnilasa component of this invention. In addition, the stability axes, also an example of the invention, are typically compared to these "reference axis axes". The present invention, in certain preferred embodiments, can make use of rings having improved stability in detergents, especially improved oxidation stability. A convenient dark point of absolute stability against which the amylases used are these embodiments of the present invention represent an edible improvement is the stability of TERMAMYI.R in commercial use in 1993 and available from Novo Nordisk A / S. This amylase TERMAMYL.R is an "arnilasa reference axis", and is well suited for use in the ADD (Automatic Dishwashing Detergent) compositions of the invention. Even the arnilasas most proffered in the present share the characteristic of being ami Jasas "Improved stability" characterizes, at a minimum, a measurable improvement in one or more axis: oxidant stability, eg, for peroxide / tetraacetic acid and hydrogen lendiary in pH-corrected solutions at a pH from 9-10; thermal stability, e.g., at common wash temperature as about 60 ° C; or alkaline stability, e.g., at a pH of approximately 8 to about 11, all measured against the reference aryllase identified above. The preferred arnides herein can demonstrate further improvement over the challenge of the anus, the reference antiphasic lesions are illustrated by any precursor proteins of which the preferred amylases are vanishing within the invention. Such precursor molecules can be natural in themselves or be the genetic engineering axis. The stability can be measured using any of the technical tests of the described technique. See the references given in UO 94/02597, same and documents of the same epinas as i ncorporaelas by reference. In general, the increased amylases in relation to the preferred embodiments of the invention can be obtained from Novo Nordisk A / S, or from Genencor International. Present-day arnides in the present have in common that they are derived by using site-directed agnosis directed to one or more Bacillus amides, especially Baccillus alpha-amylas. regardless of whether one, two or more amylase strains are immediate precursors. As mentioned, "increased oxidative stability" slabs are preferred for use herein although the fact of the invention makes them "optional but preferred" materials rather than essential. Such examples are illustrated as non-limiting by means of the following: (a) An amylase in accordance with the previously incorporated UO / 94/02597, Novo Nordisk A / S, published on February 3, 1994, co. better illustrated by means of a mulant in which substitution is made, using alamna or treomna (preferably treomna), from the residue of rnet tonina located at position 197 of the alpha-arrn lasa B. licheni forrni, cornocieja as TERMAMYLR, or the homologous variation of position of an arnilasa of similar origin, such as B. ama loliguefaciens, B. s? bt j lis, or B. s tea ro t he rpoph 11? s; (b) The improved arnilases in est a da < J are described by Genencor International in a tit? Laelo document "OxieJatavely Resist ant pha-Amy lases" presented at the 207th American Chemical Society National Meeting (207th National Meeting of American Chemistry), March 13-17, 1994, by- C. Matchinson. In this it was emphasized that the bleaches in the detergents for automatic dishwashing inactivates the alpha-amylases but that Genencor has made amylas of improved oxidative stability of B. licheniformis NCIB8061. The rnetaonine (Met) is identified as the most likely residue to be modified. Met was replaced, one at a time, in positions 8, 15, 197, 256, 304, 366, and 438 conferring to specific mutants, particularly important are M197L and M197T with the variant M197T being the vanant expressed more stable. The statute was measured in CASCflDER and UNI.IGHT *. (c) Particularly preferred herein are the arnilasse variants which have additional modification in the immediate origin of Novo Nordisk A / S. These friends still do not have a commercial name but are those referred to as the supplier * such as QL37 »M197T .. Anyone with improved oxidative stability can be used, for example, as a derivative by site-directed utagénesis of forms of origin imitating chemical, hybrid or simple of the available materials. The cellulases usable in, but not preferred for, the present invention include bacterial or fungal cells. Typically, they will have an optimum pH of between 5 and 9.5. Cellulases are described in the axis patent E.U.A. 4,435,307, Barbesgoard et al., Filed March 6, 1984, which discovers the cel? Lasa funga1 produced from strains H? i co The msolens and Humicola DSM1800 or a fungus jue produces 212 cellulase that belongs to the genus of Aeromoñas, and cellulase extracted from the hepatopancreas of marine mollusk (Dolabella Auricular Solander). Suitable cellulases are also described in GB-A-2-075-028; GB-A-2,095,275 and DE-0S2. 47,832. it is especially useful for the detergent use include those produced by the medium of the microorganisms of the Pseudonomas stutzen ATCC 19,154 group, as described in the British patent 1,372,034. See also lipases in Japanese Patent Application 53,20487, open to public inspection on February 24, 1978. This lipase is available to Amano Phar acetic acid Co. Ltd., Nagoya, Japan, under the trade name P " By hand." hereinafter < nicknamed "Amano P." Other commercial lipases include Amano-CES, lipases ex Chrornobacter viscosum, v. gr. li polyticurn NRRLB 3673, available from Toyo, ozo Co., T gata, 3a pon; and in addition, you pass Chromobacter viscosuin from U.S. Biochernical Corp., E.U.A. and Disoynth Co. The Dutch, and lipases ex Pseudomonas gladioli. The enzyme LIPOLASE "derived from the lanuginous and commercially available 1-lamp of Novo (see also EPO 341,947) is a preferred lipase for use in the present.Other enzyme 11 passes preferably is the variant D96L of the lipase Hu icola lanuginosa native, as described in UO 92/05249 and the investigation case No. 35944, March 10, 1994, both published by Novo. In general, lipolytic enzymes are less preferred than amylases and / or proteases for automatic dishwashing modalities of the present invention. • Peroxidase enzymes can be used in combination with oxygen axis sources, eg, percarbonate, perborate, per-sulfate, hydrogen peroxide, etc. They are typically used to "bleach solution," that is, to prevent the transfer of dyes or pigments removed from the substrates during the operations of the washing axis to other substrates in the washing solution. Enzymes but idase are known in the art, and include, for example, spicy bath perox idasa, ligninase and haloperoxidase such as chlorine and bromo peroxidase. The peroxidase containing detergent compositions is described, for example, in the international application PCT UO 89/099813, published on 19 October axis, 1989, by =. Kir! -, cedtßla to Novo Tnel? Stpes A / S. The present invention encompasses the modal axles composition for automatic dishwashing 11 bers of peroxidase "A wide range of materials and enzyme media for their incorporation into the synthetic detergent compositions are also described in the patent of E.U.A. 3,553,139, present on the 5th January axis < 1971 for McCarty and others. Enzymes are described further in the patent E.U.A. 4,101,457, Place et al., Filed July 18, 1978, and in the U.S. patent. 4,507,219, Hughes, filed March 26, 1985. Enzymes for use in detergents can be stabilized by various techniques. Techniques for the stabilization of enzymes are described and exemplified in the patent of E.U.A. 3,600,319, filed on August 17, 1971 for Gedge et al. And European patent application publication No. 0 199 405, application No. 86200586.5, published on October 29, 1986, Venegas. Enzyme stabilization systems are also described, for example, in the US patent. 3,519,570. (a) Enzyme Stabilization System - Enzyme-containing compositions, especially liquid compositions, may contain from about 0.001% to about 10%, preferably from about 0.005% to about 8%, highly preferred. from about 0.01% to about 6%, by weight of the axis system is enzyme stabilization. The enzyme stabilization system may be any stabilization system that is compatible with the detersive enzyme. Said stabilization systems may comprise calcium-axis ions, boric acid, glycol propane, short-chain carboxylic acid, and mixtures of the same. The axle stabilization system of the ADDs herein may further comprise from 0 to about 10%, preferably from about 0.01% to about 6% by weight sweeping axis of chlorine bleaching, aggregates to prevent species from bleaching. of chlorine present in many water supplies attack or inacti on enzymes, especially under alkaline conditions. While the chlorine level in water may be small, typically on the scale of about 0.5 pprn to about 1.75 ppm, the chlorine available in the total volume of water contacting the enzyme is relatively large. dishwashing; therefore, the stability of the enzyme in use may be a problem. Suitable chlorine scavenging anions are well known and available, and are illustrated by salts containing ammonium cations with sulfite, bisulfite, sodium sulphite, sodium sulphite, sulfur, thiosulphite, thiosulfate, iodine, etc. Antioxidants such as carbamate, ascorbate, etc., may also be used, organic amines such as tetracyclic tetrahedral acid (FDTA) or alkali metal salt thereof, rnonoet anolamana (MEA), and mixtures thereof. While other conventional barrators such as bisulfate, nitrate, chloride, hydrogen peroxide sources such as sodium perborate, tetherhydrate, monohydrated sodium perborate and sodium per-carbonate, as well as phosphate, can be used. phosphate coneJensaejo, acetate, benzoate, citrate, formate, lactate, rnalato, tartrate, saltcilato, etc., and mixtures axis isms. In general, since the function of the chlorine scavenger can be carried out by several of the ingredients listed separately under the functions best recognized, (for example, other components of the invention such as sodium perborate), it is not required to add-? A separate chlorine scavenger unless the compound performing such function to the degree of the absence is an enzyme-containing mode of the invention; even then the sweeper is added only for results optarnos. In addition, if desired, the forrnulador will perform the normal task of the chemist avoiding the use of any sweeper that is very incompatible with other ingredients. In relation to the use of ammonium salts, said salts can be simply mixed with the detergent composition but are prone to adsorb water and / or release arnonia during storage. Accordingly, said materials, if present, are desirably protected in a particle as described in the U.S. Patent. 4,652,392, Eaginsl'i et ot., 3. Optional Bleach Attachments (a) Bleach Activators - Blanejueo activator shaft components are optional materials for the compositions of the invention. These activaejores are typical for TAED (te raacetti et i lendi amina). Numerous conventional activators are known. See, for example, Patent of U.S.A. 4,915,854, issued the LO of April 1990 to Mao et al., And US Pat. 4,412,934. Activators of nonanotloxabenzenesulfonate (NOBS) or acyl lactase can be used, and mixtures thereof can also be used with TAED. See also document E.U.A. 4,634,551 will rely on other typical conventional bleach activators. Known binding-derived bleach activators are those of the formulas: RiN (R5) C (0) R2C (0) L or RC (0) N (R5) R2c (0) l where R1 is? N gr-upo alkyl containing from about 6 to about 12 carbon atoms, R2 is an alkylene containing from about 1 to about 6 carbon atoms, R5 is H or alkyl, aplo, or alkaryl containing from about 1 to approximately 10 carbon atoms, and L is any suitable leaving group. An additional illustration of conventional and optional bleach activators of the above formulas include 6-octanapodocant oxtbenzenesulfonate? it, 6-nonanam? -doxycarbon oxibenzene sulfonate, 6-decanamide dopamine oxybenzenesulfonate, and mixtures thereof, as defined in the patents of E.U.A. 4,634,551. Another class of conventional bleach activators comprises the benzoxazine-type activators described by Hodge et al. In the U.S. Patent. No. 4,966,723, issued October 30, 1990. Yet another class of bleach activators includes active ingredient and acyl lactate such as octanoyl caprolactam, caprolactam 3,5, 5-tprnet? L hexanoyl, caprolactate a nonanoyl, caprolactam decanoyl axis, iodecenoyl caprolactan, octanol valerolactarna Lo, decanoyl valerolactarna, undecenoyl valerolactane, nonanoyl axis valerolactam, 3,5,5-trimethylhexanoyl valerolactam, and mixtures thereof. The present compositions may optionally comprise aryl benzoates, such as phenyl benzoate. (c) Organic peroxides, especially peroxides of Diacillo - These are illustrated extensively in Kirl 'Othiner, Encyclopaedia of Chemical Technology, Vol. 17, John Uiloy and Sons, 1982, on pages 27-90 and especially on pages 63-72, all incorporated herein by reference. If a diacyl peroxide is used, it will preferably be one that exerts minimal adverse impact on the spot / film formation. 4. pH and Regulatory Variation - Many detergent compositions herein will be regulated, i.e., are relatively resistant to falling <; je pH on presence of acid soils. However, other compositions herein may have exceptionally low regulatory capacity, or may be substantially unregulated. The techniques used to control or vary the pH at recommended levels of use include more generally the use not only of regulators, but also additional alkalis, acids, pH boost systems, 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 inorganic alkaline salts and water-soluble organic or inorganic detergency builders, the components' adj adjust the pH are selected so that when the ADÜ is dissolved in water at a concentration of 1,000 ,000 ppm, the pH remains at the scale of about 8, preferably about 9.5 to about 11. The component that adjusts the phosphate-free pH of the invention is selected by the group consisting of: (i) ) carbonate or sodium sesquicarbonate; (n) sodium silicate, preferably sodium hydrous sodium silicate having a ratio of ?? 2: Na2? from about 1: 1 to about 2: 1, and mixtures thereof with limited amounts of sodium axis metasilicate; (nor) sodium time; (iv) citric acid; (v) sodium bicarbonate; (vi) borate je soelio, preferably borax; (vn) sodium hydroxide; and (viii) mixtures ele (?) - (v ??). Preferred embodiments contain low silicate levels (ie, from about 3% to about 10% S i O 2) - binary mixtures of granulated sodium citrate with anhydrous sodium carbonate, and mixtures of the various components of Sodium citrate granulated hydrolyzed, citric acid onohi drained and anhydrous sodium carbonate are illustrative of the systems of the component that adjusts the pH highly pre fep two. The amount of the component that adjusts the pH in the present 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 compositions in an amount of from about 5% to about 40%, preferably from about 10% to about 30%, by weight. For the compositions herein having an in-pH of about 9.5 and about 11, of the initial Wash solution, the preferred ADD modalities in particular comprise, by weight ADD, from about 5% to about 40% , preferably from about 10% to about 30%, most preferably from about 15% to about 20% axis, of sodium citrate with from about 5% to about 30%, preferably from about 7% to 25%, very about 8% to about 20% sodium carbonate. The essential sasterna that adjusts the pH may be supplemented (elecar, for improved sequestration in hard water) by other optional detergent salts selected from "phosgene buffers" known in the art, < These include the different water-soluble borates of alkali metal, ammonium or substituted ammonium, hyaloxy sulphonates, polyacetates, and polycarboxylates. Salts of said alkali metal materials, especially sodium, are preferred. Non-phosphorus, non-phosphorus, organic water-soluble shaft enhancers, alternating with their sequestering properties, can be used. Examples of polyacetate and polycarboxylate detergent builders are the sodium, potassium, lithium, ammonium and substituted ammonium salts of acid eta lendiami ntetraaceti co; mt ploetico acid, tartrate monosucci ruco acid, tartrate disuccimic acid axis, disuccinic and oxidic acid, carboxy- mer oxa succina acid, meiic acid, and sodium benzene polcarboxylate salts. (a) Water-Soluble Silicates - The present automatic dishwashing detergent compositions may further comprise water-soluble silicates. The water-soluble silicates of the present invention are any silicate that is soluble to the extent that it does not adversely affect the stain / film formation characteristics of the ADD composition. Examples of silicates are sodium metasilicate and, in general, alkali metal syllables, particularly those that have a ratio of ?? : Na2? in the scale from 1.6: 1 to 3.2: 1 and stratified silicates, such as the stratified sodium silicates described in La patent patente F.U.A 4,664,839, issued on May 12, 1987 to H.

P. Riec. NaSKS-6 is the trade name for a crystalline layered silicate sold by Hoechst (commonly abbreviated as "SKS-6" herein). Unlike zeolite detergents improvers, NaSKS-6 and other water-soluble silicates useful herein do not contain aluminum. NaSKS-6 is the morphological form of d-Ma2? 0s of layered silicate and can be prepared by methods such as those described in German Application DE-A-3,417,649 and DE-A-3, 742, 043. SKS- 6 is a highly preferred layered silicate for use herein, but other layered silicates, such as those having the general formula NaMSi 2x +? H2? 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 may be used in the present. Some other Hoechst stratified silicates include NaSKS-5, NaSK-7 and NaSKS-ll as the a-, β- and t ~ forms. Other silicates can also be used, such as for example magnesium silicate, which can serve as a tightening agent in granulated formulations, as a stabilizing agent for oxygen bleaches and as a component of foam control systems. 4!.

The silicates useful in the "Automatic washing" of the tableware (ADÜ) applications include granular silicates that are "free", such as the BRITESTLR II20 from PO Corp., and the commonly obtained BRITFSILR H24 although the liquid grades of vanes. Silicates can be used when the ADD composition is in liquid form. Within the Safety Limits, sodium asylate or sodium hydroxide alone or in combination with other silicates can be used in an Aüü context to increase the wash pH to the lesion level. 5. Detergent Enhancers - The best detergent agents other than Silicates can optionally be included in the components of the present to help control the hardness of minerals. Inorganic and organic builders can be used. The detergent builders are tapped into compositions for the automatic washing of cloths to wash fabrics to help remove their particles. The level of builder * ele detergency can vary widely depending on the final use of the composition and its physical form. When present, the compositions typically comprise at least about 1% and detergency builder. High throughput shaft formulations typically comprise about 10% to about 80% axis, and typically about 15% to about 50% by weight of the builder. However, lower or higher detergency builder levels are not excluded. The builders for detergents for inorganic detergents, and contain P mcLuy, but are not limited to the alkali metal, ammonium and alkanolarnone salts of poly phosphates (exemplified by glassy polyphosphatic ripoli, pyrophosphates and metaphosphates). , phosphonates, phytic acid, silicates, carbonates (including bicarbonates and ses "carbonates), sulfates and aluminosilicates. However, phosphate-free builders are required in some scenarios. Importantly, the compositions herein work surprisingly well even in the presence of Los Llarna < The weak "eletergencia" (compared with the phosphates) as the time, or in the so-called situation of "underconstuction" that could occur * with stratified detergents or zeolite detergents. See-patent of E.U.A. No. 4,605,509 for preferred examples of al-rninosilicates. Examples of carbonate detergent builders are alkali metal and alkali metal carbonates as described in German Patent Application No. 2,321,001 published November 15, 1973. Vanos grades and types of sodium carbonate and sesqui carbonate sodium they can be used, certain of which are particularly useful as vehicles for other ingredients, especially detersive surfactants.

The "aluminosilicate Jetergency" improvers are useful in the present invention. The detergent builders of aluminosilicate are of great importance in the majority of the heavy duty granular detergent compositions currently marketed, and they can also be an important detergency builder ingredient in liquid detergent formulations. The detergents for the detergency of alurninosil icato include those that have the empirical formula: NA2O AL2O3 xSiOz H = O where z and y are integers of at least 6, the molar ratio of zay is on the scale around LO to about 0.5, and x is an integer from about 15 to about 264. Useful aluninosi licato ion exchange materials are commercially available. These alurnanosilacatos can be crystalline or amorphous structure axis and they can be aluminosilicatos «jue happen naturally or synthetically derived. A method for producing materials and exchange of aluminosilicate ions is described in US Pat. No. 3,985,669, Kru mel et al. Issued October 12, 1976. Preferred synthetic crystalline alummonium ion exchange materials useful herein are available under the designations Zeolite A, Zeolitea P (B), Zeolite MAP and Zeolite X. In a particularly preferred embodiment, the crystalline aluninosil icato ion ion exchange material has the formula: Nai2 L "(AIO2) i2 (S1O2) i2 IxH2O at doneje x is the right axis from 20 to about 30, especially the material 27. The material is known as Zeolite A. The dehydrated zeolite (x = 0-10) is also can be used in the present Preferably, the alu i nosilicate has a particle size of approximately 0.1-10 microns in diameter.The individual particles may desirably be still smaller than 0.1 miera to help-in addition to the exchange kinetics. Through the maximum surface area increase, the high surface area also increases the usefulness of aluminosilicates as adsorbents for surfactants, especially in granular compositions.Aluninosilicate silicate aggregates or particles may be useful. , an individual aggregate that has tailor-made dimensions to minimize segregation in granular compositions, while "the aggregate particle remains dispersed even to the individual sub-icra particles during washing. As with other detergency builders such as carbonates, it may be desirable to use zeolites in any physical or morphological form adapted to promote the vehicle function of the surfactant, and the appropriate particle sizes can be freely selected by the formulator . The organic detergent builders suitable for the purposes of the present invention include, but are not limited to, a wide variety of polycarboxylate compounds. As used herein, "polycarboxylates" refers to compounds having a carboxylate group, preferably at least 3 carboxylates. The phycocarthoxy Lato builders can generally be added to the composition in acid form, but can also be added in the form of a neutralized or "overbased" salt. When used in -forma «He salt, alkali metals such as sodium, potassium and lithium, or salts are preferred. Included among the buffers are the poly earboxes are a variety of useful material categories. An important category of polycarboxylate detectors encompasses polycarboxylates of ether, including oxygen, as described in Berg, Patent "Je E.U.A. 3,128,287, issued April 7, 1964, and Lamber and others, Patent < .1e E.U.A. 3,635,830, former February 18, 1972. See also breeders d €) ejetergencia de "TMS / TDS" of the U.S. Patent. 4,663,071, issued to B? Sh and others. May 5, 1987. Suitable polycarboxylates of smell also include cyclic compounds, particularly alicyclic compounds, such as those described in U.S. Pat. 3,923,679; 3,835,163; 4, 158, 635; 4,120,874 and 4, 102,903. Other useful builders include the hydroxypolycarboxylates of ether, copolymers of rhenal anhydride with ether * of ethylene or viml methyl, acid 1,3,5-tphydroxybenzen-2, 4,6-tpsulfom, and carboxyrneti acid 1-oxtosucciruco, the vain metal salts of alkali, ammonium and substituted ammonium of polyacetic acids such as the acid et ilendia and notet raacetic acid and ploacetic acid, as well as polycarboxylates such as acid elite, succinic acid, oxy acid and succinic acid. , polyrnaleic acid, benzene 1,3,5-tr * acid? carboxy 1, carboxymethyloxysuccinic acid, and soluble salts thereof. The builders of citrate, for example, citric acid and soluble salts thereof (particularly sodium salt), are polycarboxylate builders of particular importance to laundry detergents when placed on the job because of their ready availability. of renewable resources and their biodegradability. The treatments can also be used in combination with zeolite builders and / or layered silicate and / or silicate builders. Oxydisuccinates are also especially useful in such compositions and combinations. Also suitable in the detergent compositions of the present invention are the 3, 3-d? Carbox.? 4-oxa-l, 6-hexanedioates and the related compounds described in the patent "e E.U.A. No. 4,566,984, Bush, issued January 28, 1986. Useful builders of succinic acid builder include the succinic alkyl and C5-C20 alkene acids and salts thereof. A particularly preferred compound of this type is dodeceni ls? Ccic acid. Specific examples of succinate detergency enhancers include: lauryl Isccinate, Isuccinate rnipsti, pal itil- M succmato, 2-doeJecemlsucc? nato (preferred), 2-? enta-deceni lsuccmato and the like, the lupus is the most preferred letergency metrics in this group, and are described in European patent application 86200690.5 / 0,200,263, published on 5 axis November axis 1986. Other suitable polycarboxylates are described in the US Patent 4,144,726, Crutchfield et al., Issued on March 13, 1979 and in the patent "Je E.U.A. 3,308,067, Diehl, issued March 7, 1967. See also Patent of U.S.A. Diehl, 3,723,322. The fatty acids, for example, rnononocarboxylic acids of O12-C18, can also be incorporated into the compositions alone, or in combination with the aforementioned builders, especially citrate and / or succime builders, to provide activity Improver additional detergency shaft. Such use of fatty acids will generally result in the decrease in the foam formation, which should be taken into account by the former. Fatty acids or their salts are not desirable in the "soap lava" or "automatic table" (ADD) mode in situations where soap scum can form and settle in the dishes. In situations where phosphorus-based builders can be used, various alkali metal phosphates such as the well-known sodium polyphosphates, sodium pyrophosphate, and sodium orthophosphate can be used. They can "• .2 also use the phosphonate builders as etan-1-h? drox? -1,1-osphonate and other known phosphonates (see, for example, Patents EU.A. 3,159,581; 3,213,030; 3,422,021; 3,400,148 and 3,422,137), although such materials are more commonly used in a low level chelating mode. or stabilizers. 6. Chelating Agents - The compositions herein may also optionally contain one or more selective transition metal sequestrants, "chelators" or "chelating agents", for example, iron and / or copper and / or manganese chelating agents. Suitable chelating agents for use herein may be selected from the group consisting of arninocarboxylates, phosphonates (especially the amiophosphonates), optionally substituted amino-substituted aromatic chelating agents, and mixtures thereof. Without intending to be limited to theory, it is believed that the benefit of these materials is due in part to their exceptional ability to remove iron, copper and manganese ions from washing solutions; Other benefits include the prevention of inorganic film or scale inhibition. Commercial chelating agents suitable for use herein include the DEQUESTR seneum and "Monsanto, DuPont and Nalco, Inc." chelators. Useful ammocarboxylates as optional chelating agents include ethylendia inotet raacetates, N-hydroxyeti lendiami notpacetates, mt ri lot ri acetates , and iiendiaminotet r * a? r * o ?? onatos, t petotlonothaminohexacet, dieti lenotr-iarninopent aacet ats and otanoldigli cmas, alkali metal salts, ammonium and substituted ammonium thereof. In general, chelator mixtures can be used for a combination of functions, such as multiple transition metal control, long filament product stabilization, and / or control of oxides and / or precipitated metal hydroxides. The substituted aromatic chelating agents, polymers, and the like are also useful in the compositions herein. See patent of E.U.A. 3,812,044, issued May 21, 1974 to Connor and others. Preferred compounds of this type, in the form of an acid, are the dihydroxydisulfobenzenes such as 1,2-d? H? Drox? -3, 5-dtsol fobenzene. A preferred biodegradable chelator will be used in the present is ethylene dianate disuccinate (EDDS), especially (but not limited to) the l-S isomer, Sl described in U.S. Pat. 4,704,233, the 3rd November 1987 axis, to Hartman and Perkms. The thapsodic salt is preferred, although other forms, such as magnesium salts, may also be useful. The non-phosphonic arnides are also suitable for use as "whitening agents" in the compositions of the invention when at least low levels of total phosphorus are allowed in detergent compositions, and include etiiendiarm nt raqui s (methylenephosphonates) and dietiientpamintetraquis (meth iienophosphonates). It is preferred <That these amophosphonates do not contain alkyl or alkaline groups with more than about six carbon atoms. If used, the agents of the transition will preferably comprise about 0.001% to about 10%, and preferably about 0.05% to about 1% by weight of the agents. compositions of the present. 7. Dispersant Polymer - Preferred ADÜ compositions herein may also contain a dispersant polymer. When present, a dispersing polymer in the present ADD compositions is typically at levels in the range of from 0 to approximately 25%, preferably from about 0.5% to approximately 20%, very much lower than about 1. % to about 8% by weight of the ADD composition. The dispersing polymers are useful for improving the performance of the present ADD compositions, especially in the higher pH modes, such as those in which the wash pH exceeds about 9.5. Particular preference is given to polymers which inhibit the deposition of calcium carbonate or magnesium silicate in the ware. Dispersing polymers suitable for use herein are further illustrated by the film forming polymers described in U.S. Patent 4,379,080 (Murphy), issued April 5, 1983. r i; cb Suitable polymers are preferably at least partially neutralized salts or alkali metal, ammonium or substituted ammonium (eg, mono-, di- or triethanolamome) of carboxylic acids. Alkali metal salts, especially sodium, are highly preferred. While the molecular weight of the polymer can vary on a wide scale, it is preferably from about 1,000 to about 500,000, preferably it is from about 1,000 to about 250,000, and very preferred, especially if the ADD is used. in American automatic dishwashing machines, it is around 1,000 to about 5,000. Other suitable dispersing polymers include those described in the "Je E.U.A. No. 3,308,067, issued March 7, 1967, to Diehl. The unsaturated inonomeic acids which can be polymerized to form suitable dispersing polymers include acipic acid, malic acid (or aleic anhydride), fumaric acid, itaconic acid, aconitic acid, esacmene acid, citraconic acid and methylene-tronic acid. The presence of carboxylate-free radicals containing monomeric segments such as methyl vinyl ether, styrene, ethylene, etc., is suitable provided that said segments do not constitute more than about 50% by weight of the polymer. . Acrylate copolymers nJa and acplate having an axle molecular weight of from about 3,000 to about 100,000, preferably from about 4,000 to about 20,000, and an acrylamide content less than about 50%, preferably less than axle, can also be used. about 20%, by weight of the dispersant polymer. Most preferred, said dispersant polymer has a molecular weight of from about 4,000 to about 20,000 and an acrylamide content of from about 0% to about 15%, by weight of the polymer. The preferred dispersant polymers in particular are modified low molecular weight copolymers of lac p Lato pol. Said copolymers contain monomer units: a) from about 90% to about 10%, preferably from about 80% to about 20% by weight of 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 (C (R2) C (R) C (0) 0R3)] wherein the valences not filled are in fact indeed occupied by hydrogen and at least one of the substituents R, R2 or R3, preferably R1 or R2, is an alkyl or hydroxyl group of about 1 to 4 carbon atoms; Rl or R2 can be hydrogen and R3 can be a hydrogen or alkali metal salt. Most preferred is a substituted acrylic monomer wherein R 1 is methyl, R 2 is hydrogen, and R 3 is sodium. The suitable low molecular weight polyacrylate dispersing polymer preferably has a molecular weight of less than about 15,000, preferably from about 500 to about 10,000, most preferably from 1,000 to about 5,000. The highly preferred polyacrylate copolymer will be used in the present invention to have a molecular weight of about 3,500 and is the fully neutralized form, eg the polymer comprising about 70% by weight of acrylic acid and approximately 30% by weight of the metacrylic acid. . Other suitable modified pollock copolymers include copolymers of molecular weight ba or carboxylic acids to the unsaturated ifatides described in the Patents "Je E.U.A. 4,530,766 and 5,084,535. The agglomerated forms of the present ADD compositions can employ aqueous solutions of polymer dispersants as liquid binders to make the agglomerate. (in particular 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 copolymers of acrylate / acrylate or acrylate / fumarate with an average molecular weight of about 2,000 to about 30,000 and a r * the ation of segments of acplato a maLeato or smokes axis time around 30: 1 to approximately 1: 2. Examples of such copolymers based on a mixture of unsaturated mono- and dicarboxylate monomers are written in the Application European Patent No. 66,915, published December 15, 1982. Other dispersing polymers useful herein include polyethylene glycols and polypropylene glycols having a molecular weight of about 950 to about 30,000 which can be obtained from Dow Chemical Company of Midland, Michigan. Such compounds, for example, which have a melting point within the range of about 30 ° C to 100 ° C approximately, can be obtained at molecular weights of 1,450, 3,400, 4,500, 6,000, 7,400, 9,500 and 20,000. . Said compounds are formed by the polymerization of ethylene glycol or propylene glycol with the required number of moles of ethylene oxide or full prop to provide the desired molecular weight and point to the fusion of the polyethylene glycol and the respective polypropylene glycol. The polyethylene, polypropylene glycols and the mixed ones are referred to to use the rmul: HO (CH2CH2?) M (CH2CH (CH3) 0) n (CI-KCH3) CH2?) 0OH where m, nyo are integers «j? E satisfy the molecular weight requirements and temperatures given above. Still other dispersing polymers useful in the present include cellulosic sulfate esters such as cellulose acetate sulfate, cellulose sulfate, cellulose hydroxyethyl sulfate, rilel cellulose sulfate, and hydroxypropyl cellulose sulfate. The preferred polymer of this group is sodium cellulose sulfate. Other suitable dispersing polymers are the carboxylated polysaccharides, in particular starches, celluloses and alginates, described in the U.S. Pat. No. 3,723,322, Dieh, issued March 27"Je 1973; the esters < The dextr a of polycarboxylic acids described in the patent of E.U.A. No. 3,929,107, Thompson, issued November 11, 1075; the ethers of hydroxyl starch, starch esters, oxygenated starches, dextrins and starch hydrolysates, described in US Pat. No. 3,803,285, 3ensen, issued April 9, 1974; the carboxylated starches described in the U.S. Patent. No. 3,920,121, Eldib, issued December 21, 1971; and the dextpna starches described in the U.S. Patent. No. 4,141,841, McDonald, issued February 27, 1979. Preferred cellulose-derived dispersant polymers are carboxymethyl celluloses. Still another group of acceptable dispersants are organic dispersant polymers, such as polyaspartate. 8. Material Care Agents - as present ADD compositions may contain one or more material care agents that are effective as corrosion inhibitors and / or ancillary rust aids. Said materials are preferred components of machine-to-machine washing compositions especially in certain European countries where the use of electrically deposited nickel plating in plates and fine silver is still comparatively common in silverware, or when the Aluminum protection is a concern and the composition is low in silicate. Generally, such materials care agents include metasilicate, silicate, bismuth salts, manganese salts, par-refines, tpazoles, pi rads, triols, mercaptans, aluminum fatty acid salts, and mixtures thereof. When present, said protective materials are preferably incorporated at low levels, for example, from about 0.01% to about 5% of the ADD composition. Suitable corrosion inhibitors include paraffin oil, typically a predominantly branched alkylamino hydrocarbon having a number of carbon atoms on the scale of about 20 to about 50; the preferred paraffin oil is selected from the predominantly branched C25-45 species with a ratio of cyclic to non-cyclic hydrocarbons of about 32:68. A fine-grained oil that meets these characteristics is sold by Uintershall, Salzbergen, Germany, under the trademark UTNOG 7. In addition, the addition of low levels of bismuth nitrate (ie, B? (N? 3) 3) is also preferred. Other corrosion inhibiting compounds include benzotpazole and comparable compounds; ercaptans or thiols that include thionephthol and thioanthranol; and aluminum fatty acid salts finely divided, such as aluminum stearate. The consultant will be aware that such materials will generally be used judiciously and in limited quantities to avoid any tendency to produce stains or v-films. He would "jeopardize the bleaching action" of the compositions. For this reason, preference is given in particular to anti-mercaptan rusts which are reactive to strong bleaching and carboxy acids which precipitate with calcium. 9. Suppressors of Silicone Foams and Phosphate Esters - The ADDs of the invention which may contain optionally foam suppressant, alkyl ester, phosphate, suppressor of stlicon foams, or combinations thereof. . The levels in general are from 0% to approximately 10%, preferably, from about 0.001% to about 5%. Typical levels tend to be low, for example, about 0.01% to about 3% amount will be used suppressor of silicone foams. Preferred phosphate-free compositions omit the phosphate ester component per complete. The technology of the silicone foam suppressant with and other defoaming agents useful herein are documented extensively in "Defoarning, Theory an" J Industrial Applications, "Ed., PR Garrett, Marcel Dek er, NY, 1973, TSBN 0 -8247-8770-6, incorporated herein by reference. See in particular the chapters entitled "Foam control ín üetorgent Products" (Ferch et al.) And "Surfactant Antifoarns" (Blease et al.). See also the Patents of E.U.A. 3,933,672 and 4,136,045. Preferred Silicon foam suppressors are the types of compounds known for use in laundry detergents such as heavy duty granules, although the types used herein only in heavy duty liquid detergents may be incorporated into the detergents. - present compositions. For example, the f > The idyrene and isyloxanes having t prnet or silyl blocked units at the alternate ends can < 1in use as silicon. These may be composed of silicon and / or silicon-free components of the surfactant, as illustrated by * a foam suppressor comprising 12% Si 1 icon / yes Lice, 18% steappyl alcohol and 70% starch in granulated shape. A suitable commercial source of the active compounds of the invention is Dow Corni g Corp. The levels of the foam suppressant depend to some extent on the tendency of sputtering of the composition, for example, an AÜD to be used at 2000 ppm comprising 2. % octaderate oxide Idimet ilarnine does not require the presence of a foam suppressant. In fact, it is an advantage of the present invention to select the effective amine oxides in the cleaning which are inherently lower in tendencies to foam than the typical coconut amine oxides. In contrast, the surfactant coagent, for example, alkyletosis fa, is greatly beneficial in the presence of foam suppressant. The phosphate esters have also been given to provide some protection of surfaces of silver and fine silver; however, the present compositions can have excellent silver axis care without a phosphate ester component. Without being limited by the theory, it is believed that formulations that have a lower pH, for example, those that have a pH of 9.5 or less, plus the presence of low-level amine oxide, will contribute to the silver axis care. Improvement If it is desired to use a phosphate ester, suitable compounds are described in the U.S.A. Patent. 3,314,891, issued on April 18, 1967, to SchmoH-a et al., Incorporated herein by reference. Preferred alkyl phosphate esters contain from 16 to 20 carbon atoms. The highly preferred alkyl phosphate esters are nonoesteapyl acid phosphate or nonoleilic acid phosphate., or salts thereof, in particular alkali metal salts, or mixtures thereof. It has been found that it is preferable to avoid the use of soaps that precipitate simple calcium as anti-foaming agents in the present compositions since they tend to be deposited on the dishes. In fact, the phosphate esters are not completely free of such problems and the formulator usually chooses to minimize the content of potentially depositing antigens in the present compositions. 10. Other Optional Attachments - Depend on enejo if a larger or smaller degree of compacibility is required, the filler materials may be * also present in the present ADDs. These include sucrose, sucrose esters, sodium sulfate, potassium sulfate, etc., in amounts of up to about 70%, preferably from 0% to about 40%, with the composition ADÜ. The preferred filler is sodium sulfate, especially in good grades, and they have at low levels of trace impurities. The sodium sulfate used herein preferably has a sufficient purity to ensure that it is not reactive with ol bleaching.; it can also be treated with low levels of sequestrants, such as phosphonates or EDDS in the form of a magnesium salt. Note that such preferences, in terms of sufficient purity to avoid bleaching decomposition, also involve component ingredients that adjust the pH, specifically including any silicate used in the present. Although optionally present in the present compositions, the present invention encompasses modalities which are substantially free of sodium chloride or potassium chloride. Hydrotropic materials, such as benzene sulfonate, sodium, sodium toluens, sodium cinnamon, etc., may be present, for example, for better dispersion of the surfactant. Perfumes stable in bleaching (stalls as for smell); and stable dyes in the bleaching such as those described in the Patent of F.U.A. 4,714,562, Roselle et al., Issued December 22, 1987, may also be added to the present compositions in appropriate amounts. Other ingredients are not excluded «common letergents consistent with the spirit and scope« I foresaw it? tnvenei on. Since the ADD compositions herein may contain water-sensitive ingredients or ingredients that do not interact when carried together in an aqueous environment, it is desired to keep the free moisture content of the AODs to a minimum, for example, 7% or less, preferably 4% or less of the ADD; and provide * packaging that is impermeable substantially to the water and carbon dioxide. The coating measures have been described herein to illustrate a way to protect the ingredients of each and of the air and moisture. Plastic bottles, including types that can be filled and recirculated, as well as conventional carbons or barrier boxes are other useful means to ensure maximum storage stability. As noted, when the ingredients are not highly comparable, it may be desired to reverse at least one of said ingredients with a nonionic low-foaming agent for protection. There are numerous wax materials that can be readily used to form suitable coated particles of any otherwise compatible component; however, the fornulator prefers that those materials do not have a marked tendency to be deposited or to form film in dishes including those of plastic construction. Some automatic dishwashing compositions granulated in the foreground chlorine bleaching books of the invention are the following: a composition of free-flowing automatic dishwashing liquid of chlorine bleach comprising amylase (eg, TERMAMYLR) and / or arní lasa stable in bleaching and a bleaching system comprising a source of hydrogen peroxide selected from sodium perborate and sodium percarbonate and a cobalt catalyst as defined herein. Also contemplated is a substantially free chlorine bleach washing composition comprising an amylase with improved oxidative stability and a bleaching system comprising a source of hydrogen peroxide selected from sodium perborate and percarbonate or sodium axis. , a cobalt catalyst, and TAEü or MOBS. Cleaning method. The present invention also encompasses a method for cleaning dirty dishes since it comprises that said dishes make contact with an aqueous medium comprising a cobalt-axis catalyst, preferably at a concentration of about 2 pprn to about 10 ppin, as described above in the I presented. The preferred aqueous medium has an initial pH in a wash solution of more than about 8, more preferably about 9.5 to about 12, most preferred about 9.5 to about 10.5.

This invention also encompasses a dishwashing method in an automatic dishwashing appliance, which comprises treating the dirty dish in an automatic dishwashing machine with an aqueous alkaline bath comprising amiiase and a cobalt catalyst. Compositions and Auxiliary Methods of Rinsing: The present invention also relates to compositions useful in the rinse cycle of an automatic dishwashing process, said compositions being commonly referred to as "rinse aids". While the compositions described hereinabove may also be formulated for use as auxiliary rinse compositions, no use purposes are required as a rinse aid having a source of hydrogen peroxide present in said compositions (although a source is preferred). of hydrogen peroxide, at least at low levels to be at least the transfer supplement). The optional inclusion of a source of hydrogen peroxide in an auxiliary rinsing composition is possible in view of the fact that a significant level of residual detergent composition is carried from the wash cycle to the rinse cycle. In this way, when an ADD composition containing a source of hydrogen peroxide is used, the source of hydrogen peroxide for the rinse cycle is taken from the wash cycle. In this way, the catalytic activity provided by the cobalt catalyst is effective with this transfer of the "washed" cycle. Thus, the present invention also encompasses automatic dishwashing rinse aid compositions comprising: (a) a catalytically effective amount of a cobalt catalyst as described herein, and (b) dishwashing detergent adjunct materials. automatic. Preferred compositions comprised a low sputtering non-lime surfactant. These compositions are also preferably in liquid or solitary form. The present invention also encompasses methods for washing dishes in a domestic automatic dishwashing appliance, said method comprising treating the dirty dish during a washing cycle of an automatic dishwashing machine with an aqueous alkaline bath comprising a source of peroxide hydrogen, followed by the treatment in the course of the cycle and subsequent rinsing with an aqueous bath comprising a cobalt catalyst as described herein. The following non-limiting examples further illustrate the ADD compositions of the present invention.

EXAMPLES 1 TO 3 The following detergents were prepared for washing the automatic dish in solid form completely formulated: Active% Active% Active Sodium citrate 15.0 15.0 15.0 Carbonate «Je sodium 17.5 20.0 20.0 Dispersant polymer (see not L) 6.0 6.0 6.0 H i d rox i et 11 d i os f onat o (HEDP; aciejo) 1.0 1.0 1.0 Nonionic surfactant (SLF 18, 01 in Corp. or Plurafac) 2.0 2.0 Sodium perborate rnonoha dratado (see note 3) 1.5 1.5 1.5 TAED 2.0 - DTPMP (See note 4) 0.13 - Cobalt catalyst (see * note 2) 0.2 0.07 0.4 Savinase 6.0T (protease) - 2.0 2.0 Savinase 12T (protease) 2.2 Terrnarnyl 60T (amylase) 1.5 1.0 1.0 BRITESTL H20, PQ Corp. (as i?) 8.0 8.0 ao Metasilicato (anhydrous) 1.25 - - Paraf i na 0.5 - - Benzot pazol 0.3 Sulfate, water, minors Rest Rest Rest at 100% to 100% to 100 % Note 1: Poly "J? Sper * sant e, one or more of: Sokolan PA30, BASF Corp., Accusol 480N, Rohm 8¡ Haas. Note 2: CCo (NH3) sCpci2 provided by Dixon Fine Chemicals. Note 3: These sources of hydrogen peroxide are expressed in an available oxygen base of% by weight. In order to convert to a percentage of the total composition, divide between a and x i rna dame nt e 0..15. Note 4: dietilent r'iaminpentaquis (ethylene phosphorus acid).

EXAMPLE 4 Note 1: Dispersing polymer, one or more of: So olan PA30, BASF Corp., Accusol 480N, Rohrn & Haas.

Note 2: CCo (NH3) sCl] Cl2 provided by Dixon Fine Chemicals. Note 3: These sources of hydrogen peroxide are expressed in a base of available oxygen of% by weight. To convert to a percentage basis of the total composition, divide by approximately 0.15.

EXAMPLE 5 The following automatic dishwashing detergents in solid form were completely formulated: Note 1: Polymer «1? spersant e, one or more of: Socolan PA30, BASF Corp., Accusol 480N, Rohrn S Haas. Note 2: CCo (NH3) sCl3Cl provided by Dixon Fine Chemicals. Note 3: These sources of hydrogen peroxide are expressed in a base of available oxygen of% by weight. To convert to a base percentage of the total composition, divide by approx. Imadamen to n .15.

EXAMPLE 6 It f > repaired the following detergents of automatic table washing in solid form completely formulated: Note 1: Dispersing polymer, one or more of: Socolan PA30, BASF Corf), Accusol 480N, Rohrn 3¡ Haas. Note 2: CCo (NH3) 5Cpci provided f > or Dixon Fine Chemicals. Note 3: These hydrogen peroxide sources are expressed in an available oxygen base of% by weight. To convert to a percentage basis of the total composition, divide by approximately 0.15.

EXAMPLE 7 Note l: Polymer «Jispersante, one or more of: So olan PA30, BASF Corp., Accusol 480N, Rohm a Haas. Note 2: CCo (NH3) 5CllCl2 provided by Dixon Fine Chemicals. Note 3: These hydrogen peroxide sources are expressed in an oxygen base available in% by weight. To convert to a base percentage of the total composition, divide by approximately 0.1.

EXAMPLE 8 0 0 ! =? 0 0 0 00 Note 1: Dispersing polymer, one or more of: Socolan PA30, BASF Corp., Accusol 480N, Rohm S Haas. Note 2: CCo (NH3) sCpci2 provided by Dixon Fine Chemicals. Note 3: These sources of hydrogen peroxide are expressed in an available oxygen base of% by weight. To convert to a percentage basis of the total composition, divide by approximately 0.1 percent. The ADDs of the above examples of the dishwashing detergent composition are used for washing tea-stained cups, dishes stained with starch and spaghetti, milk-stained glasses, dishes stained with starch, "jueso, egg or baby food, and spatulas. of tomato-stained plastic by loading the dirty dishes into an automatic dishwashing appliance and washing using cold fill, 60 ° C peak, or uniform washing cycles of 45 ° -0 ° C with a product concentration of the compositions of example of about 1,000 to about 5,000 ppm with excellent results.

Claims (15)

1. NOVELTY OF THE INVENTION
2. CLAIMS i.- A detergent composition for automatic dishwashing detergent comprising: (a) a catalytically effective amount of a cobalt catalyst having the formula: rCo (NH3) n Mm Bh Tt Oq Pp JYy where the cobalt is in the state oxidation 3; n is an integer from 0 to 5; M represents a monodentate ligand; m is an integer from 0 to 5; B represents a bidentate axis ligand; b is an integer from 0 to 2; T represents a tdentate ligand; t is 0 or l; 0 is a tetradentate ligand; q is 0 or 1; P is a ligand of pentadent ato; p is 0 or 1; and n + * • 2b + 3t + 4q * 5? - 6; And it is one or more selected antions presently present in a number and, in which "ey is an integer from 1 to 3 to obtain a balanced charge salt, the Y fe fe are selected from the group" jue consist of chloride, nitrate, nitrite, sulfate, citrate, acetate, carbonate, and combinations thereof; In addition, at least one of the cobalt fixed coordination sites is liable under conditions of automatic dishwashing and the remaining coordination sites stabilize the cobalt under automatic dishwashing conditions so that the reduction potential for cobalt (III) to cobalt (II) under alkaline conditions (for example,? H = 10) is less "approximate" 0.4 87 vol ios against an electrode and normal hydrogen; (b) an effective amount of a hydrogen peroxide source; and (c) materia The adjuncts detergents for automatic washing of vají lias. 2.- A detergent composition for automatic washing
3. "Tableware" according to claim 1, further characterized in that it comprises auxiliary material * for automatic dishwashing selected in that the composition produces less than 5.08 crn "of foam under normal conditions of use. 3. A detergent composition for automatic dishwashing in accordance with claim 1, further characterized in that it comprises as a part or all of the attached material for automatic dishwashing one or more low foaming surfactants.
4. 4. A detergent composition automatic dishwashing ware according to claim 1, further characterized in that it comprises as part or all the materials for automatic dishwashing equipment one or more agents for care of material.
5. 5. A detergent composition for automatic dishwashing machine shaft with ormidad with the claim 1, characterized in addition because they compose as part or all the materials attached to automatic dishwashing one or more water-soluble silicates.
6. 6. A detergent composition for automatic dishwashing in accordance with claim 1, characterized in that it comprises one or more bleach activators as part or all of the adjuncts for automatic dishwashing.
7. 7. A detergent composition for automatic dishwashing in accordance with claim 5, further characterized by the bleach activator is TAED.
8. 8. A detergent composition for automatic dishwashing according to claim 1, further characterized in that it has a pH "le 1% of aqueous solution of less than 11.
9. 9.- A method" Jo for washing utensils for service of table in an ico appliance for automatic dishwashing, said method comprises treating the dirty tableware in an automatic dishwasher with an aqueous alkaline barium comprising a source of hydrogen peroxide and a cobalt catalyst which has the formula: CC? (NH3) n m Bb Tt 0 Pp] Yy in «where the cobalt is in the state of ox?« Jac? Ón * 3; n is an integer from 0 to 5; M represents a monodentate ligand; in is an integer from 0 to 5; B represents a ligand «je bidentate; b is an integer from 0 to 2; T represents a tdentate ligand; t is 0 or l; 0 is a tetradentate ligand; q is 0 or 1; It is a pentadentate lysis; p is 0 or 1; and n + rn * • 2b + 3t «- * 5? - 6; And it is one or more selected counterions appropriately present in a number and, where y is an integer axis 1 to 3 to obtain a balanced charge salt, the preferred Y's are selected from the group consisting of chloride, nitrate, nitrite, sulfate, citrate, acetate, carbonate, and combinations thereof; wherein in addition at least one of the cobalt fixed coordination sites is labile or automatic ware washing conditions and the remaining coordination sites stabilize the cobalt under automatic dishwashing conditions so that the potential for reduction for cobalt (III) to cobalt (II) under condition n.1; alkaline is less than about 0.4 volts against a normal hydrogen electrode.
10. 10 ..- A method «Je conformity to the claim 9, further characterized in that the pH of the bath is less than 11.
11. 11.- A method of washing utensils for table service in household appliance for automatic dishwashing, said method comprises treating utensils for dirty table service in a Automatic water washer with an alkaline water bath "comprising a detergent composition for automatic washing" in accordance with claim 1.
12. 12.- A method for removing stains from tea and / or utensils for table service in an ico appliance for automatic dishwashing, said method comprises treating them for tableware stained with tea in an automatic dishwasher with an aqueous alkaline bath which comprises a source of hydrogen peroxide and a cobalt catalyst of the formula re (NH3) n Mm Bb Tt Q PP lYy where the cobalt is in the oxidation state +3; n is an integer from 0 to 5; M represents a monodentate ligand, - m is an integer from 0 to 5; B represents a bidentate ligand; b is an integer < 0 to 2; T represents a tdentate ligand; t is 0 or 1; 0 is a ligand of tet radentate; q is 0 or 1; P is a pentadentate ligand; p is 0 or 1; and n + + 2b + 3t + 4q * 5? = 6; And it is one or more with appropriately selected mice present in a number and, where y is an integer from 1 to 3 to obtain a balanced charge salt, the preferred Y are selected from the group consisting of chloride, nitrate, nitrite, sulfate , citrate, acetate, carbonate, and combinations thereof; where in addition at least one of the sites for fixed cobalt coordination is labile under automatic dishwashing conditions and the remaining co-ordinating sites statute cobalt under the condition of automatic dishwashing, so that the reduction potential for cobalt (III) to cobalt (II) under alkaline conditions at least about 0.4 volts against an electrode «Normal hydrogen.
13. 13.- A composition that helps to rinse in the automatic dishwashing «jue comprises: (a) a catalytically effective amount of a cobalt catalyst that has the formula: rCo (NH3) n Mm Bb Tt 0q PP] Yy 06 where the cobalt is in the oxidation state +3; n is an integer from 0 to 5; M represents a ligand of rnonodeni ate; an integer from 0 to; B represents a bidentate ligand; b is an integer «Je 0 to 2; T represents a tdentate ligand; t is 0 or 1; 0 is a tetradentate ligand; q is 0 or 1; P is a ligand of pentadont to; p is 0 or 1; and n + m + 2b + 3t + 4q * 5? - 6; And it is one or more appropriately selected counterions present in a number and, where y is an integer from 1 to 3 to obtain a balanced charge salt, the Y 's are selected from the group consisting of chloride, nitrate, nitrite, sulfate, citrate, acetate, carbonate, and combinations thereof; wherein in addition at least one of the cobalt-fixed coordination sites is labile under automatic dishwashing conditions and the remaining coordination sites stabilize the cobalt under automatic dishwashing conditions "so that the potential of reduction for cobalt (III) to cobalt (II) under alkaline conditions is less than about 0.4 volts against a normal hydrogen elect; (b) adjunct automatic dishwashing detergent materials, preferably comprising one or more nonionic surfactants at low sputum.
14. 14. An automatic dishwashing auxiliary rinsing composition according to claim 13, further characterized in that it comprises one or more low foaming nonionic surfactants. R?
15. 15. - A method for washing utensils for table service in an appliance for automatic dishwashing, said method comprises treating dirty tableware during a cycle "washing an automatic dishwasher with an aqueous alkaline bath"? It comprises a source of hydrogen peroxide, followed by treating the utensils for table service during the subsequent rinse cycle with a water bath comprising a cobalt having the formula: rCo (NH3) nMmBbTtQqPp] Yy where the cobalt is in the oxidation state +3; n is an integer from 0 to 5; M represents a monodentate ligand; rn is an integer from 0 to 5; B represents a bidentate axis ligand; ti is an integer «e 0 to 2; T represents a ligand «je tpdentato; t is 0 or 1; 0 is a tetradentate ligand; q is 0 or L; P is a pentadentate liying; p is 0 or 1, - and n + + 2b + 3t + 4q * • 5p = 6; And it is one or several contions selected appropriately present in a number and, where y is an integer from 1 to 3 to obtain a balanced charge salt, the preferred Y are selected from the group «} which consists of chloride, nitrate, nitrite, sulfate, citrate, acetate, carbonate, and combinations thereof; where in addition at least one of the cobalt fixed co-ordination sites is L bil under conditions of automatic dishwashing use and the remaining coordination sites stabilize the cobalt under automatic dishwashing conditions so that the potential of The reduction for cobalt (III) to cobalt (TI) under alkaline conditions is less than approximately 0.4 volts against a standard of normal hydrogen.