MXPA97010167A - Compositions that include cobalt catalysts for automatival - Google Patents

Abstract

Automatic dishwashing detergent compositions comprising certain cobalt catalysts are provided, more specifically, the invention relates to automatic dishwashing detergents which provides improved cleaning / bleaching benefits (especially tea stain removal) by the selection of a bleach catalyst of cobalt having the formula: [Co (NH3) n (B) b] Ty, where the cobalt is in the oxidation state +3, n is 4 or 5 (preferably 5), M is one or more ligands coordinated with the cobalt at one site, m is 0, 1 or 2 (preferably 1), B is a ligand coordinated with the cobalt at two sites, b is 0 or 1 (preferably 0), and when b = 0, then m + n = 6, and when b = 1, then m = 0 and n = 4, and T is one or more appropriately selected counter-anions present in a number y, where y is an integer to obtain a balanced salt in charge (preferably and is from 1 to 3, most preferably 2 when T is an anion charged with -1); said catalyst has a base hydrolysis rate constant of less than 0.023 M-1 s 1 (25 ° C), the preferred automatic dishwashing compositions comprise anilase and / or protease enzymes, including methods for washing dishes in domestic automatic dishwashers using the cobal catalysts

Description

COMPOSITIONS THAT COMPRISE COBALT CATALYSTS PflRñ AUTOMATIC LAVAPLATOS TECHNICAL FIELD [. Preserve invention is in the field of detergent compositions that contain bleach, specifically detergents for iavapLats < In particular, bleach comprises detergents for commercial dishwashers (liquids, solids and such as tablets and especially granules), which comprise selected cobalt / ammonia catalysts. Preferred methods for dishwashing are included.

BACKGROUND OF THE INVENTION The washing of automatic crockery, part i cu 1 ai ment in domestic appliances, is a very di ffi cult technique for washing fabrics. The washing of household towels is normally done on ¿Machines built that * IPGI? a .oction i ve 1 ved i a. These are very different from the »? Ara» os domest i < , or < dishwashing to omático, \ o ,,; c? ,, n »lo aspo rs i n - la ~ < < or ion of aspoision on the last *? in < | < - a piovocaí ospu acion. the foam may flood the windpipe, and the windpipe of the windmill will be flooded, and the I GI D do aopoi < ll. . | UO to < -.u VP. ? »- (iu < (-? T? C < iti cleaned! I)»?? », T, in the domestic dishwashing machine field, the use is normally resumed of detergent surfactants for common lathering laundry detergents These aspects are only a brief illustration of the unique formulation constraints in the domestic washing of garbage field.The washing of automatic crockery with chemical plating agents is different from bleaching In the washing of automatic dishes, the use of bleaching chemicals involves the promotion of removal of dirt from dishes, although dirt bleaching may also occur, in addition, the effects of anti-redeposition and anti-aging would be desirable. dirtying of bleaching chemicals Some chemical bleaching agents (such as a source of hydrogen peroxide, alone or in combination with tetraacid-ethylenediandryanine (TAED)) can, in certain circumstances, be useful for cleaning dishes, but are The technology gives very satisfactory results in a dishwashing context: for example, the ability to remove tea stains is limited, especially in hot water, and requires fairly large amounts of bleach. Other bleach activators developed for use in laundry can still have negative effects, such as creating non-visible deposits, when they are in an automatic dishwashing product, especially when they have solubility and baa. Other bleaching systems can give unique items for dishwashing, such as silver items, aluminum cookware1 or certain plastic items. Glassware, tableware and consumer cutlery, especially decorative pieces, such as washing in household automatic dishwashers, are often susceptible to damage and may be costs to replace. Typically, consumers dislike having to separate the most-needed parts and they would refer the convenience and simplicity of being able to combine all of their items for cooking and cooking utensils into a single LCO autornat washing operation. However, doing this as a matter of routine has not been possible. Due to the above technical constraints as well as the needs and demands of the consumer, the automatic dishwashing detergent compositions (ADD) are undergoing continuous change and improvement. In addition, environmental factors such as the restriction of time, the desire to provide even better cleaning results with less product, provide less thermal energy, and less water to aid the washing process, have driven the need for improved ADD compositions. . A recognized need in ODD compositions is to have present one or more ingredients that improve the removal of hot beverage stains (e.g., tea, coffee, chocolate, etc.) of consumer goods. Strong alkalis such as sodium hydroxide, bleaches such as hypochlorite, detergents such as phosphate and the like can help to vary the grades but they can all be harmful, or leave a film on glassware, crockery or silverware. - therefore, softer ADD compositions have been developed. Kst s make use of a source of hydrogen peroxide, optionally with a bleach activator such as TAED, as noted. In addition, enzymes such as commercial aminolithic enzymes can be added (for example, TERMAMYLR available from Novo Nordisk S / A). The alpha-hardened component provides at least some benefit in the properties (removal of starchy dirt from ADD.) ADDs containing arnides can typically go a wash pH of some moderate degree in use and can remove dirt. starch to the ism time avoiding to supply large amounts of sodium hLodroxide on a per gram basis of product.It would therefore be highly desirable to ensure improved bleach activators specifically designed to be compatible in ADD formulations, especially with such enzymes as Likewise, there is a need to ensure better action of arnilasa in the presence of bleach activators.Some machine-washer compositions containing manganese catalyst are described in US Patent 5,246,612, issued September 21, 1993, to Van. Dijl-- and others The compositions are said to be free-machine dishwashing compositions chlorine bleach comprising arnilasa and a manganese catalyst (in the +3 or +4 oxidation state), as defined by the structure given herein. The preferred manganese catalyst herein is a dmuclear manganese, which contains a metabolic ligand that is MnIV2 (U-O3 (1, 4, 7-t prnetyl -1,4,7-tpazac? Clononane ) 2 (PFß) 2. D ossome catalyst materials containing these more complicated ligands will typically require several steps of synthesis for production, thus increasing the cost of the catalysts and making them less expensive to use. there being a need for widely available, simple catalysts that are effective in automatic dishwashing compositions and methods.The simple cobalt catchers useful herein have been described for use in laundry compositions containing bleach to wash soiled fabrics, as taught in U.S. Patent No. 4,810,410 par-a Diakun et al., issued March 7, 1989. For example, table 8 therein provides the results of man-made removal. for a series of stains on fabrics washed with laundry compositions with and without the cobalt catalyst CCo (NH3) sCl] Cl2. The elimination of tea stains from the fabrics, as it is reported in the same, at least, seems marginal in comparison with the other medium stains. The comparative inferiority of said cobalt catalysts for laundry applications, for example to remove tea stains, is reinforced by the teachings contained in the last filed European Patent Application No. 400,131, published on January 16, 1991 by U ilever NV . Example IV herein is said to be a comparison of the cobalt-cobal complexes or that is observed as the invention of the application against the "[Co (NH3) s C1" C12 of the art "(referring to the publication previous of the European equivalent of the Diakun patent and others noted above), registers value-is for the removal of tea stains as follows: Co-Co (26: 3); CCo (NH3) 5CllCl2 (20.6), which is less than that observed for a simple Mn + 2 catalyst as reported in Example El (having a tear removal value of 21.4). Similar results for manganese catalysts against cobalt catalysts are recorded for laundry uses to remove tea stains from cotton fabrics in the U.S. Patent. 5,244,594, to Favre et al., Issued September 14, 1993. Herein, example T provides data showing a Co-Co catalyst in accordance with EP 408,131 which is lower than manganese catalysts. In addition, the TV example also records less stain removal at 20 ° C for a Co-Co catalyst of EP 408,131 and the CCo (NH 3) sCl] Cl 2 catalyst of the Diakun patent against a manganese-catalyst. Although such inferior results are observed for the removal of tea stains from fabrics during laundry procedures, when used in automatic dishwashing compositions in accordance with the present invention, these catalysts provide a surprisingly effective removal of the Tea stains from the dishes. This effectiveness could not be expected from the prior art. It is an object of the present invention to provide automatic dishwashing compositions, especially of the granular, phosphate-free and chlorine free bleach type, which incorporate an improved selection of bleach ingredients containing cobalt catalyst. A further object is to provide fully formulated ADD compositions, with or without arylase enzymes, but especially the former, in which specific bleach systems containing cobalt catalyst are combined with additional selected ingredients including conventional arnis or stable arnides. in bleach, so that they provide superior tea cleaning results and at the same time excellent care of the tableware and tableware of the consumer.

TECHNICAL BACKGROUND In addition to the Patent of E.U.A. 4,810,410 noted above, to Diakun et al., Issued March 7, 1989; the Patent of E.U.A. 5,246,612, to Van Dijl-- et al., Issued September 21, 1993; the Patent of E.U.A. 5,244,594, to Favre et al., Issued September 14, 1993; and European Patent Application No., 400,131, published on January 16, 1991 by Unilever MV, see also: US Patent. A. 5,114,611, to Van Kralingen and others, issued on May 19, 199? (transition metal complex of a transition metal, such as cobalt, and a non-chemical ligand); Patent of E.U.A. 4,430,243, to Uragg, issued February 1, 1984 (laundry bleaching compositions comprising heavy catalytic metal cations, including cobalt); German Patent Specification 2,054,019, published on October 7, 1971 by U ilever NV (cobalt chelator catalyst); and European Patent Application Publication No. 549,271, published on June 30, 1993 by Uniiever PLC (organic ligands in cellulose compositions).

BRIEF DESCRIPTION OF THE INVENTION It has now been discovered that a specific group of cobalt-containing catalysts coordinated with NH3 provide superior mobility and stability in detergent compositions containing bleach. These properties make these catalysts especially useful for improved cleaning performance of automatic dishwashing detergents ("ADD"), and have other benefits such as enzyme compatibili, good characteristics regarding mottling / film formation and no deposit in the machines. This performance is exemplified with the removal of tea stains, but is not in accordance with the general way, the present invention encompasses automatic dishwashing detergents comprising: a) a catalytically effective amount of a cobalt bleach catalyst having the formula: wherein the cobalt is in the +3 oxidation state; n is 4 or 5 (preferably 5); M is one or more l gandos coordinated with the cobalt in one place; m is 0, 1 or 2 (preferably 1); B is a 1 igando coordinated with cobalt in two sites; b is 0 or 1 (preferably 0); and when b = 0, then m * n = 6 and when b = l, then rn = ü and n = 4; and T is one or more contra-anions present in a number y, where y is an integer to obtain a balanced salt in charge (preferably y is 3, very preferably 2 when T is an anion charged with -l); and further said catalyst has a base hydrolysis rate constant of less than 0.23 -i 8-i (25 ° C). (b) an effective amount of a source of hydrogen peroxide; and (c) adjunct materials, preferably automatic dishwashing detergent or adjuncts for laundry. Preferred detergent compositions herein also comprise an arylase enzyme. Although conventional amylases such as TERMAMYL can be used with excellent results, the preferred HDD compositions can use amino acids with improved oxidative stability.That amylase is available from NOVO.In it, oxidative stability improves upon substitution using tremone of the residue of etiomna located at position 197 of B.Licheni forrni or the variation of homologous position of an arnilasa similar origin.The present ADDs have numerous advantages, for example, they are economical, compact, less harmful to articles for the table of what would be expected on the basis of its potent whitening action, do not depend on chlorine compounds, and can be formulated to avoid the unwanted use of very high levels of caustic ingredients In certain preferred embodiments, they are substantially free of charge. boron, chlorine bleach and / or phosphate In the modalities of ADD composition, materials may be present Additional bleach improvers. Preferably, these are selected from bleach activator materials, such as tetraacetyle j lendiamine ("TAED"). The present invention encompasses fully formulated ADDs in a granulated form, preferably free of phosphate buffer and chlorine bleach, wherein additional ingredients, including other enzymes (especially proteases and / or amylases), are formulated. The present invention also encompasses cleaning methods; very similarly, a method of dishwashing in a domestic automatic dishwasher, comprising treating the dirty dishes in an automatic dishwashing machine with an alkaline aqueous bath which comprises a catalyst which has cobalt having the formula provided. above and a hydrogen pere bridge. The present invention also relates to automatic dishwashing rinsing compositions comprising a catalyst-containing cobalt as described in the foregoing, and methods for treating table-to-table articles in an apparition. Domestic automatic dishwashing during a rinse cycle with these cobalt-containing catalysts. As already noted, the invention has advantages, including the excellent combination of stain removal, good care of dishes, and good overall cleaning helped by a greater flexibility to formulate enzymes, especially amylases. All parts, percentages and ratios used herein are expressed as weight percent unless otherwise specified. All the documents cited, in relevant part, are incorporated herein by reference.

DETAILED DESCRIPTION OF THE INVENTION Bl nting compositions. The automatic dishwashing compositions of the present invention comprise a source of hydrogen peroxide and a particularly selected cobalt catalyst. The source of hydrogen peroxide is any salt that releases hydrogen peroxide, such as sodium perborate, sodium percarbonate, and mixtures of the same. Also available are sources of available oxygen such as per-sulfate bleach (e.g., OXONE, manufactured by DuPont). In the preferred embodiments, additional ingredients are present such as water-soluble silicates (useful for providing alkalinity and helping to control corrosion), low foaming nonionic surfactants (especially useful in automatic dishwashing to control the formation of stain / film), dispersing polymers (which modify and inhibit the crystal growth of calcium and / or magnesium salts), chelators (which control transition metals), detergency builders such as citrate (which help control calcium and / or magnesium and can help to re-egulate the action), alkalis (to adjust the pH), and detersive enzymes (to help- with cleaning hard foods, especially starchy soils and proteins). Additional bleach modifying materials such as conventional bleach activators may be added to the 1 ED as long as said bleach modifying materials are supplied in such a manner as to be compatible with the purposes of the present invention. Furthermore, detergent compositions can comprise one or more processing aids, fillers, perfumes, conventional enzyme particle making materials including "unparalleled" enzyme cores, such as pigments, and the like. In general, the materials used for the production of ADD compositions herein are preferably checked for compatibility with stain / film formation in glassware. The test methods for spot / film formation are generally described in the automatic dishwashing detergent literature, including DEN test methods. Certain oily materials, especially in long chain lengths, and insoluble materials such as clays, as well as long-chain fatty acids or soaps that form soap impurity layer are thus preferably limited or excluded from those present. compositions. The amounts of the essential ingredients may vary within broad ranges, however the preferred automatic dishwashing detergent compositions (which have pH IX of aqueous solution of from about 7 to about 12, more preferably from about 9 to about 11.5, and most preferred less than about 11, especially from about-9 to about 11) are those where it is present: from about-from OL% to about? il%, preferably from about 0.5% to about 30. % of a source of hydrogen peroxide; from about 0.01% to about 1%, preferably from about 0.08% to about 0.36% of the cobalt-catalyst; from about 0.1% to about 40%, preferably from about- 0.1% to about 20% of a water-soluble silicate (ratio two); and from about 0.1% to about 20%, preferably from about 0.1% to about 10% of a low foaming nonionic surfactant. Such fully formulated modalities typically also comprise from about 0.1% to about 15% of a polymerase dispersant, from about 0.01% to about 10% of a chelator, and from about 0.00001% to about 10% of a detersive enzyme although other additional ingredients or adjuncts may be present. The detergent compositions herein in granular form typically limit the water content, for example to less than about 7% free 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 form does not deliberately add a chlorine-containing bleach additive, such as chloro socianurat, or the preferred ADD composition. However, it is recognized that by-factors outside the control of the form, such as chlorination of the water supply, some non-zero amount of the chlorine bleach may be present in the wash liquor. "Substantially free" can be construed in a similar manner with reference to the preferred limitation of other ingredients, such as a phosphate detergent builder, by "effective amount" herein is meant an amount that is sufficient, under any condition The term "catalytically effective amount" refers to an amount of cobalt catalyst that is sufficient under any comparative test condition employed to improve the performance of a compacted test. Cleaning the dirty surface In the washing of automatic dishes, the dirty surface can be - for example, a porcelain cup with tea stains, dirty dishes with starch s simple or more complex food soils, a plastic spatula stained with tornado soup. The test conditions will vary, depending on the type of washing apparatus used and the habits of the user. Some machines have considerable wash cycles longer than others. Some users choose to use hot water without much heating inside the appliance; others use warm or even cold water, followed by heating through an integrated electric coil. Of course, the operation of the bleaches and enzymes will be affected by said considerations, and the levels used in fully formulated detergent and cleaning compositions can be adjusted appropriately. Cobalt catalysts The compositions and methods of the present invention use cobalt bleach catalysts (TIT) having the formula: CCo (NH3) n (M) m (B) b 3Ty where the cobalt is in the oxidation state +3; n is 4 or 5 (preferably 5); M is one or more ligands coordinated with the cobalt in one place; m is 0, 1 or 2 (preferably 1); B is a ligand coordinated with cobalt in two sites; b is 0 or 1 (preferably 0), and when b = 0, then rrp n - 6, and when b = l, then rn = 0 and n = 4; and T is one or more contours appropriately selected, present in a number and, where y is an integer to obtain a balanced salt in charge (preferably y is 1 to 3, rnuy preferably 2 when T is an anion loaded with -1 ); and further said catalysts have a base hydrolytic rate constant of less than 0.23 M-1, -i (25 ° C). Preferred T's are selected from the group consisting of chloride, nitrate, nitrite, sulfate, citrate, acetate, carbonate, bromide, PFé ", BF" -, phosphate, tosylate, methane fonate, and combinations thereof.

Entities M include, but are not limited to, for example, F-, SO4"" 2, NCS-, S2O3"2, NH3, and carboxylates (which preferably are monocarbo-ilates, but may be present in the entity more of a carboxy lato, as long as the binding to cobalt is only by a carboxylate per entity), The preferred entities of M are substituted and unsubstituted C 1 -C 30 carboxylic acids having the formulas: RC (0) 0 ~ in wherein R is preferably selected from the group consisting of hydrogen and unsubstituted and substituted C 1 -C 30 alkyl (preferably Ci-Ciß), unsubstituted and substituted C 6 -C 30 aryl (preferably Cß-Ciß), and unsubstituted and substituted heterocycle of C3-C30 (preferably C5-C30), wherein the substituents are selected from the group consisting of -MR'3, -NR'A +, -C (0) 0R ', - OR ', -C (0) NR'2, wherein R' is selected from the group consisting of hydrogen and portions of Ci-Cß.Therefore, said substituted R includes the portions - (CH2) n0H and (CH2) nNR '' +, wherein n is an integer from 1 to about 16, preferably from about 2 to about 10, and most preferred from about 2 to about 5. The Preferred are carboxylic acids having the above formula wherein R is selected from the group consisting of hydrogen, methyl, ethyl, propyl, straight or branched chain C4-C12 alkyl, and benzyl. Preferably, R is methyl. The M entities of carboxylic acid f > References include formic, benzoic, octanoic, nonanoic, decanoic, dodecanoic, and acetic acids. Entities include carbona or, dicarboxylates and higher carboxylates (for example oxalate, malonate, malic acid, succmate, maleate), picolimic acid, and alpha- and beta-amino acids (for example glycine, animal, beta-alamine, phenylalanine) . The cobalt bleach catalysts useful herein are known; for example, they are described along with their base hydrolysis rates, in M. L. Tobe, "Base Hydrolysis of T ransit ion-Metal Cornplexes", A and, Ino g. Biomorg, Mech. , (1983), 2, pages 1-94. For example, in table 1 on page 17, base hydrolysis rates (designated in the same way as koH) are given for cobalt pentaamma catalysts in complex with oxalate U-OH = 2.5 x L0- * Ml ß- l (25 ° C)), format (I? H - 5.8 x 10 ~ 4 Ml, -l (25"C)), and acetate U-OH = 9.6 x 10- | * | -?, - * (25 C)). The useful cobalt catalyst herein has the formula L "Co (NH3 JsO cJ Ty, where OAc r-epr'esenta an acetate entity and especially cobalt pentaamineacetate chloride, CCo (NH3) sOAc Cl2 ("PAC", in the present.) These cobalt catalysts are readily prepared by known methods, as taught for example in the Tobe article, mentioned above and the references cited in the ism, in the US Patent. 4,810,410, to Diakun et al., Issued March 7, 1989, 3.

Chem. Ed. (19B9), 66_ (12), 1043-45; The Synthes s and Charactenzat ion of Inorganic Compounds, U. L. olly (Prentice-Hall; 19)), pp. 461-3; Inorg. Che.,! _, 1497-1502 (1979); Ln rg. Chein., 21, 2881-2885 (1902); Inor-g. Ohem., J_B, 2023-2026 (1979); Tnorg. Synthesis, 173-176 (1960); and ournal or Physical Chernist Ry, 56, 22-25 (1952); as well as the synthesis examples p rov i t o s ma a de l n te. These cobalt catalysts can be coprocessed with adjuncts to reduce the color impact - if desired for the aesthetics of the product, or the composition can be manufactured to contain "stains" of the coater. As a practical matter, and not by way of limitation, the ADD compositions and methods of the present may be adjusted to provide in the order of at least one part per ten million cobalt catalyst species in the aqueous wash medium. , and preferably provide from about 0.1 ppm to about 50 pprn, most preferably from about 1 pprn to about 25 pprn and most preferably from about 2 pprn to about 10 ppm, of the cobalt catalyst species in the solution of washed. To obtain such levels in the wash solution, typical ADD compositions herein will comprise from about 0.04% to about 1%, most preferably from about 0.08% to about 0.36% by weight of the ADD compositions.

Source of Hydrogen Peroxide Sources of hydrogen per-oxide are described in detail in the previously incorporated Kirl-- üthrner's Encyclopedia of Chemical Technology, 4th Fd (1992, John Uiley ft Sons), Vol. 271-300"Bleachmg Agents (Survey)", and include the various forms of sodium perborate and sodium percarbonate, including various coated and modified forms. An "effective amount" of a source of hydrogen peroxide is any amount capable of significantly improving the removal of stains (especially from tea stains) from soiled dishes as compared to a composition without a source of hydrogen peroxide when the dirty tableware is washed by the consumer in a household automatic dishwashing machine in the presence of lcali. Very generally, a source of hydrogen peroxide herein is any convenient compound or mixture that under conditions of use by the consumer provides an effective amount of hydrogen peroxide. The levels can vary widely and are generally on the scale of about 0.1% to about 70%, very typically from about 0.5% to about 30% of the ADD compositions herein. The preferred source of hydrogen peroxide used herein can be any convenient source, including the hydrogen peroxide itself. For example, perborate, e.g., sodium perborate (any hydrate but preferably 71). mono or tet ahydrate), sodium carbonate peroxyhydrate or percarbonat salts or equivalents, sodium pyrophosphate but hydrochloride, urea peroxyhydrate or sodium peroxide can be used herein. Also useful are available oxygen sources such as persulfate-whitener (v.gr-., OXONE, manufactured by DuPont). Sodium perborate monohydrate and sodium percarbonate are particularly preferred. Mixtures of any convenient hydrogen peroxide sources can also be used. A preferred percarbonate bleach comprises dry particles having an average particle size in the range of about 500 microns to about 1,000 microns, no more than about 10% by weight of said particles being less than 200 microns and not more than about 10 microns. % by weight of said particles being greater than about 1,250 microns. Optionally, the percarbonate can be coated with a silicate, borate or water-soluble surfactants. Percarbonate is available from several commercial sources such as FMC, Solvay and Tokai Den. Although the effective bleaching compositions herein may comprise only the identified cobalt catalysts and a source of hydrogen peroxide, fully formulated ADD compositions will typically comprise other automatic dishwashing detergent auxiliary materials to improve or modify the 0 0 0 For this purpose, the materials are selected as appropriate by the required properties of a composition for automatic dishwashing. For example, if low staining and film removal is desired - the preferred compositions have stain removal and film formation rates of 3 or less, substantially less than 2, and most preferably less than 1. , as determined by the normal test of The American Society for Testing and Materials (The American Society for Testing and Materials, for its acronym in English "ASTM") D3556-85 (Approved again 1989) "Standard Test Method for üeposition on Glassware During Mechanical Di hwashing ". Also, for example, if sputtering is desired - preferred compositions produce less than 5.08 crn, most preferably less than 2.54 crn, of spreaders at the bottom of the dishwashing machine during normal use conditions (as determined using methods known to those such as, for example, those described in U.S. Patent 5,294,365 to Uelch et al., issued March 15, 1994). Auxiliary Materials Detersive or auxiliary agents optionally included in the present compositions may include one or more materials to help increase the cleaning performance, treatment of the substrate to be cleaned or may be designed to improve the aesthetics of the compositions . In addition they are selected based on the composition form, 73 I will tell you, if the composition is going to be sold as a liquid form, in paste (sernisolide) or solid (including tablets and the preferred granular forms for the compositions herein). Auxiliaries which may also be included in compositions of the present invention, at levels established in the conventional art to be used (generally auxiliary materials comprise in total of from about 30% to about 99.9%, preferably from about 70% to about 95%, by weight of the compositions), include other active ingredients such as dispersing polymers (eg, from BASF Corp. or Rohm ft Haas), colored specks, silver cleaning, anti-rust and / or anti-corrosion, colorants, fillers, germicides, alkalinity sources, hydrotropes, anti-oxidizers, enzyme stabilizing agents, perfumes, solubilizing agents, vehicles, processing aids, pigments and, for liquid formulations, solvents such as describe in more detail later on. 1. Detergent Surfactants a) Low foaming nonionic surfactant - Surfactants are useful in automatic dishwashing to help cleaning, help to remove foams from food dirt, especially protein, and ayu «. control the staining / forming of film and desirably include in the present detergent compositions at levels of from about 0.1% to about 20% of the composition. In general, surfactants J K are preferred stable to bleaching. The HDD (automatic dishwashing detergent) compositions of the present invention preferably comprise foaming nonionic surfactants (LFNTs). LFNT may be present in amounts of from 0 to about 10% by weight, preferably from about 0.25% to about 4%. The LFNIs are most typically used in ADDs considering the improved water film action (especially in glass) that can confer to the ADD product. It also encompasses polymeneous materials that are not phosphate or silicon with future illusions that are known to remove foams from food stains found in automatic dishwashing. Preferred LFNIs include nonionic alkoxylated surfactants, especially ethoxylates derived from primary alcohols, and mixtures thereof with sophisticated lymphocyte agents, such as polypropylene or polyol reversal blocking polymers. et? ieno / pol loxipropi-leno (P0 / EO / P0). It is well known that surfactants of the PO / EO / PO polymer type have foam suppressor or puffer action, especially in relation to known food dirt ingredients such as egg. The invention encompasses preferred embodiments wherein LFNI is present, and wherein this component is solid at about 35 ° C, and preferably solid at about 25 ° C. For ease of manufacture, a preferred LFNI has a melting point between about 25 ° C and about 60 ° C, most preferably between about 26.6 ° C and about 43.3 ° C. In a preferred embodiment, the LFNT is an ethoxylated surfactant derived from the reaction of monohydric alcohol or alkyl phenol. It contains from about 8 to about 20 carbon atoms, with about 6 to approximately L5. minols of ethylene oxide per mole of alcohol or alkyl phenol on an average basis. A particularly pronounced LFNI is derived from a straight chain fatty alcohol containing from about 16 to about 20 carbon atoms (C20 -C20 alcohol), preferably a C2 alcohol, condensed with an average of about. Reader from 6 to about 15 rulers, preferably around? to about 12 moieties, and preferably about 7 to about 9 mole of ethylene oxide per mole of alcohol. Preferably, the ethoxylated nonionic surfactant thus derived has a narrow ethoxylate distribution in relation to the average. The LFNT may optionally contain propylene oxide in a high amount of about 15% by weight. Preferred LFNI surfactants can be prepared by the methods described in the U.S. Patent. No. 4,223,163, issued September 16, 1980, Builloty, incorporated herein by reference. Highly preferred ADDs in which LFNI is present use ethoxylated monohydroxy alcohol or alkyl phenol and also comprise a polyoxyethylated, polyoxypropylene-containing polyvinylpropyl block compound.; the ethoxylated rnonohydroxyl alcohol or phenol alcohol fraction of the LFN1 comprising from about 20% to about 100%, preferably from about 30% to about 70%, of the total LFNI. Suitable polyoxyethylene-polyoxypropylene block polyoxyethylene compounds satisfying the requirements described above include those based on ethylene glycol, propylene glycol, glycerol, tprneti Lolpropane and etiiendiarnine as a reactive hydrogen-initiator compound. Polymeric compounds made from sequential ethoxylation and propoxylation of initiator compounds with an individual reactive hydrogen atom, such as C12-18 aliphatic alcohols, generally do not provide control of sati factor foams in ADDs herein. Some of the polyarnene block surfactant compounds designated PLURONIC * and TETRONIC * by BASF Uyandotte Corp., Uyandotte, Michigan, are suitable in ADD compositions of the invention. A particularly preferred LFNI contains from about 40% to about 70% of a mixture of? Ol? Ox? Propylene / polyoxyethylene / 10x1-propylene polymer comprising about 75% by weight of the mixture, of a polyox letiieno and polyoxypropylene inverse block copolymer containing 17 moles of ethylene oxide and 44 moles of propylene oxide; and about 25% by weight of the mixture, of a copolymer or block of polyethylene and poly 10x1 p-pylene initiated with a protopolyol and containing 99 moles of propylene oxide and 24 moles of oleic acid oxide. t rimeti lol ropano. Suitable for use as LFNI in ADD compositions are those LFN1 which have relatively low turbidity points and hydrophilic equilibrium L! ICO (HLB) elevated. Turbidity points of 1% solutions in water are typically less than about 32 ° C and preferably lower, v.gr-,., 0 ° C, optimum counter-part of suppression of foams at full scale full of water temperatures. LFNIs that may also be used include pointoxylated alcohol, which has a degree of ethoxylation of about 8, commercially available from SLF 18 of Olm Corp., and any biodegradable LFNI having the melting point properties described above. (b) Anionic Surfactant Coagent - The automatic dishwashing detergent compositions herein are preferably substantially free of ammonium surfactant coagents. It has been found that some ammonium surfactant coagents, particularly carboxylated fatty acids, can produce films on the dishes. In addition, many ammonium surfactants are highly foaming. If present, the ammonium surfactant coagent is typically of a type having good ubiquitous sunlight in the presence of calcium. Said ammonium coagents are also illustrated by sulfates, the polyol isulphates (FS), alkylpolyme oxycarboxylates, and their short chain. 5 2. Detersive Enzymes "Detersive Enzyme", as used herein, means any enzi to < It has a cleansing effect, smudge replenishment or other beneficial effect in an ADD composition. Preferred detersive enzymes are hydrolases such as LC) proteases, arnilases and lipases. Highly preferred for automatic washing of va llla are arnilases and / or proteases, including current commercially available types and improved types which, although more compatible with bleach, have a remaining degree of susceptibility to deactivation of the bleach.

In general, as indicated, the preferred ADD compositions herein comprise one or more detersive enzymes. If only one enzyme is used, an arylolithic enzyme is preferred when the composition is for automatic dishwashing use. Highly referencing for washing Automatic tableware is a mixture of proteolytic enzymes and amyolitic enzymes. Very generally, the enzymes that are going to be incorporated are Luyen proteases, arnilases, lipases, cellulases and peroxidases, as well as mixtures thereof. You can also include other types of enzymes. It can be of any suitable origin such as vegetable, animal, bacterial, fungi and yeasts. However, your choice is regulated by several factors such as pH activity and / or optimal stability, thermostativity, stability versus active detergents, detergency enhancers, etc. In this regard, bacterial or fungal enzymes are preferred, such as bacterial Lasias and proteases and cellulose. Enzymes are normally incorporated in the present detergent compositions at levels sufficient to provide an "effective amount of cleaning". The term "effective cleaning amount" refers to which "amount" capable of producing cleaning, stain removal or dirt removing effect on substrates such as fabrics, tableware and the like. Since enzymes are catalytic materials, these amounts can be very small. In practical terms for current commercial preparations, typical amounts are up to 5 mg in weight, very typically from about 0.01 mg to about 3 mg, of active enzyme per gram of the composition. Stated otherwise, the compositions herein will typically comprise from about 0.001% to about 6%, preferably from 0.01% to 1% by weight of the commercial enzyme preparation. Protease enzymes are generally present in such commercial compositions at levels sufficient to provide 0.005 to 0.1. Anson Units (UA) «per gram composition activity. For automatic dishwashing purposes, it may be desirable to increase the active enzyme content of the commercial preparations to minimize the total amount of the as-catalytically active materials assorted and chicken as well as to improve. The res ‡ lated «The elimination of fi nances / film. Suitable examples of proteases are the sympthyses that are obtained from particular strains of B.subtiii and B. licheni forrns. Another suitable protease is obtained from a strain of Bacillus, having a rnaxirna activity on the entire pH scale of 8 to 12, developed and sold by Novo Industries A / S under the trademark name ESPERASE. "The preparation of this enzyme and analogous enzymes are disclosed in British Patent Specification No. 1,243,784"Je Novo." The appropriate proteolytic enzymes for removing proetham-based stains that are commercially available include those sold under the brand names ALCALASETM and SAVINASETM μor Novo Industries A / S (Denmark) and MAXATASETM by International Bio-Synthetics, Inc. (The Netherlands), Other proteases include Protease A (see European patent application 130,756, published January 9, 1985) and Protease B (see application for European Patent No. "Je series 87303761.8, filed on April 28, 1987, and European patent application 130,756, Bott et al., published January 9, 1985.) A specially prepared protease. ferida, known as "protease D" is a carbomyl hydrolase variant that has an amino acid sequence that is not found in nature, which is derived from a precursor carbyl hydrolase substituting a plurality of amino acid residues for an amino acid. or different at a position in said carbonyl hydrolase equivalent to the +76 position, preferably also in combination with one or more amino acid residue positions equivalent to a <;? those selected from the group consisting of +99, +101, +103, 04, «-107, +123, +27, +105, +109,« -L26, +128, +135, H56, +165 , + 195, +197, +204, +206, +210, +216, +217, +218, +222, +260, +265, and / or +274 according to the subtilisin numbering of Bacillus arnylol iquefaciens , as described in the patent applications of A. Baeck et al., entitled "Protease-Cont aimng Cleaning Cornposi lons" that the USA has Sene No. 08 / 322,676, and C. Ghosh et al., "Bleachmg Coinpositions Cornppsing Protease Enzymes" which has E.U.A. Series No. 08 / 322,677, both filed on October 13, 1994. Suitable arnides include, for example, α-amylases described in the specification of British Patent No. 1,296, 839 (Novo), RAPIDASE ", International Bio-Synthetics, Inc. and TERMAMYI.R, Novo Industries Enzyme management is known by genetic engineering (eg, arnilasa of increased stability) for improved stability, v.gr-., Oxidative stability. for example, 3. Biological Chern., Vol. 260, No. 11, June 1985, pp. 6518-6521"Reference RNA" refers to a conventional arnilase within the scope of the armlassa component of this invention. Arnilases of increased stability, also within the scope of the invention, are typically co-processed with these "ani Lasses of faith." The present invention, at certain preferred incidences, can use the Arni Lashas that have improved stability in detergents, especially oxy stability dativa rnejora «Ja. A convenient absolute stability reference point against which the amyl sas used in these preferred embodiments of the present invention represent a better-yet "stable is TERMAMYL stability" in commercial use in 1993 and available from Novo Nordi k A / S This THREADED arnid TERMAMYL "is a" reference arní lasa ", and is by itself well suited for use in the ADD (automatic dishwashing detergent) detergent compositions of the invention. The even more preferred arniases in the present share the characteristic "They are amylases of" increased stability ", characterized, at a minimum, by a measurable improvement in one or more of: oxyzative stability, e.g., to hydrogen peroxide. / tetraacetylendiarnine in solution regulated in its pH at a pH of 9-10; thermal stability, e.g., at common wash temperatures such as about 60 ° C; or alkaline stability, e.g., at a pH of about 8 to about 11, all measured against the aforementioned reference arylase. The preferred amylases in the present may demonstrate further improvement versus reference amylases of greater challenge, the ultimate reference amylases being illustrated by any of the precursor arnides of which the preferred arnides are present. Go before. Said precursor armras by themselves may be natural or may be the product of genetic engineering. The stability can be determined using any of the technical tests described in the art. See references written in UO 94/02597, and documents thereof incorporated herein by reference. In general, the arnilases of increased stability with respect to the preferred embodiments of the invention can be obtained from Novo Nordisk A / S, or from Genencor Tnternat? Onal. Preferred amino acids of the present have the common aspect of being derived using site-directed rnutagenesis from one or more of the Bacillus arylases, especially Bacillus alpha-amylases, regardless of whether one, two or multiple strains of arnilasa are the intermediate precursors. As indicated, the "increased oxydative stability" tools are preferred for use in the present in spite of the fact that the invention makes them "optional but useful". what essentials These are not necessarily illustrated for the following reasons: a) an amylase in accordance with the previously incorporated UO / 94/02597, Novo Nordisk-A / S, published on 3 February 1994, as illustrated by a mutant in 1 which is a substitution, using alan or treomna (preferably threonine) of the residue of ethionine located at position 197 of the fa-arm lasa of B. licheniformis, known as TERMAMYL ", or the variation of homologous position <Je an arní lasa pro ge ni tora, such as. arny 1 or 11 that facien, B. subtili s, or B. stearotherrnophil us; b) Arní lasas "Je stabil i« Jad increased as described in Genencor International in a document entitled "Oxidatively Resistant to pha-Arnylases" presented at the 207th American Chemical Society National Meeting, March 13-17 1994, by C. Mitchi nson, in which it was noted that the bleaches in automatic dishwashing detergents inactivate the alpha-amylas but the oxidatively enhanced stability arnilases were made by Genencor from B. lichemforrnis NCIB8061. The rnetiomna (Met) was identified as the residue most likely to be modified.Rnethionine was replaced, one at a time, in positions 8, 15, 197, 256, 304, 366 and 438 leading to specific mutants, M197L and M197T being particularly important with the M197T variant in the most stable expressed variant. Stability was reduced CASCADE "AND SUNLIGHTR; c) Particularly preferred here are the arnilasa variants which have additional modification in the immediate parent available from Novo Nordisk A / S. These arnilases do not have a commercial name yet but are those known to the supplier as 0L37 + M197T. 3 b It can be used as any other oxidatively stable stability arylase, for example, as it is derived by mutants, irrespective of whether they are in the form of progenitor or non-essential forms, hybrid. or simple knowledge of available ainilasas. Useful cellulases, but not preferred, in the present invention include both bacterial cellulase and fungal cellulase. Typically, they must have an optimum pH of between 5 and 9.5. Suitable cellulases are described in U.S. Pat. 4,435,307, Babesgoard et al., Issued March 6, 1984 describing fungal cellulase produced by Hurnicola msolens and DMS 1800 strain of Húmicola or a cellulase-producing fungus 212 for the genus Aerornonas, and cellulase extracted from the hepatopancreas of a marine mollusk ( Dolabella auricle Solander). Suitable cellulases are also described in GB-A-075.028; GB-A-2,095,275 and DE-OS-2,247,832. CAREZYMER (Novo) is especially useful. Lipase enzymes suitable for use in detergents include those produced by microorganisms of the Pseudornonas group, such as Psem Jomonas stutzen ATCC 19,154, as described in British Patent No. 1,372,034. See also lipases in Japanese Patent Application No. 53-20487, open for public inspection on February 24, 1978. This lipase is available from Amano Pharmaceutical Co. Ltd., Nagoya, Japan, under the brand name Lipase P "Amano", hereinafter referred to as "Arnano-P". Other commercial lipases include Arnano-CES, Lipases from ex Chrornobacter i co urn, v.gr. Chromobacter vi cosum var. Lipolytic urn NRRLB 3673, commerce. Available from Toyo Jozo Co., Tagata, Japan; and also the Chromobacter vi scosum Lipases from U.S. Boichernical Corp., E.U..A. and Disoynth Co., The Netherlands, and lipases from ex Pseudomonas gladioli. The enzyme LIPOLASE "derived from Hurnicola lanugmosa and which is commercially available from Novo (see also EPO 341,947) is a preferred lipase to be used herein.Another preferred lipase enzyme is the D96L variant of the native lipase from Hurnicola lanuginosa, as is described in UO 92/05249 and Research Description No. 35944, March 10, 1994, both published by- Novo., lipolytic enzymes are less preferred than arnides and / or proteases for automatic dishwashing embodiments of the present invention. The peroxidase enzymes are used in combination oxygen supplies, e.g., percarbonate, pei borate, persulfate, hydrogen peroxide, etc. They are typically used for "bleaching solutions", that is, to avoid transfer of dyes or pigments removed from the substrates during washing operations to other substrates in the washing solution. Peroxidase enzymes are known in the art and include, for example, horseradish peroxidase, ligase and haloperoxidase such as chlorine, erox, jasa and brornoperoxidase. Detergent compositions containing peroxidase are described, for example, in International Application PCT UO 89/099813, published on October 19, 1989, by 0. Kirl '. assigned to Novo Tndudtpes A / S. The present invention includes composition modalities for automatic dishwashing without porox dasa. A wide variety of enzyme materials and media are described for their incorporation into synthetic detergent compositions in the U.S. Patent. 3,553,139, issued on January 5, 1971 to McCarty et al. In addition, enzymes are written in the U.S. Patent. 4,101,457, from Place et al., Issued July 18, 1978 and in the U.S. Patent. 4,507,219, Hughes, issued March 26, 1985. Enzymes for use in detergents can be stabilized by various techniques. Enzyme stabilization techniques are described and illustrated in the U.S. Patent. 3,600,319, issued August 17, 1971 to Gedge et al. And in European Patent Application No. O 199 405, published on October 29, 1986, by Venegas. Enzyme stabilization systems are also described, for example, in the U.S. Patent. 3,519,570. a) Enzyme stabilizing system - Enzyme-containing compositions, especially liquid compositions, herein can comprise from about 0.001% to about 10%, preferably from about 0.005% to about 8%, most preferably about 0.01% to about 6% by weight of an enzyme stabilizer system. The enzyme stabilizer system can be any stabilizing system that is compatible with the detersive enzyme. Said stabilizing systems may comprise calcium, boric acid, propylene glycol, short chain carboxylic acid, boronic acid and mixtures thereof. The stabilizer system of the ADDs herein may comprise "jars from 0 to about 10%, preferably from about" 0.01% to about 10% by weight, from chlorine bleach scrubber, additives to prevent the chlorine bleaching species present in many water supplies from attacking and inactivating enzymes, especially under alkaline conditions. Although the chlorine levels in the water may be small typically in the range of about 0.5 pprn to about 1.75 pprn, the available chlorine in the total volume of water that comes in contact with the enzyme during dishwashing is relatively large; therefore, enzyme stability during use can be problematic. Suitable chlorine scavenging anions are widely known and readily available, and are illustrated by salts containing arnine cations with sulfite, disulfite, thiosulfite, thiosulfate, iodide, and the like. Antioxidants such as carbamate, ascorbate, etc., organic amines such as ethylenediaryn-tetraacetic acid (EDTA) or the alkaline metal salt < The same, monoethanol amine (MEA) and mixtures of the same. Other conventional scrubber such as hisuLfate, nitrate, chloride, sources of hydrogen peroxide such as tetrahydrated sodium perborate, nitrogen peroxide and percarbonate, sodium, as well as phosphate, condensed phosphate, acetate, benzoate, citrate, formate, lactate, maleate, tartrate, silicilate, etc., and mixtures thereof may be used if desired. In general, since the purifying function of chlorine can be carried out by various ingredients listed separately in better recognized functions (for example, other components of the invention such as sodium perbor-ato), there is no need to add a separate chlorine scrubber unless a compound that performs that function to the desired degree is absent from the embodiment of the invention containing the enzyme; even in this case, it is added to the debugger only to achieve optimal results. In addition, the forrnulator will exercise the normal skill of a chemist by avoiding the use of any debugger that is fundamentally incompatible with other ingredients, if used. In relation to the use of salts and ammonium, such salts can be simply mixed with the detergent composition but are prone to absorb water and / or release ammonia during storage. According to the above, such materials, if present, are desirably protected in a particle such as that described and the U.S. Pat. 4,652,392, Bagmsl-'i and others. 3. Optional Whitening Additives (a) Bleaching activators - Whitening activating components are optional materials for the inventive compositions. Such activators are typified by the TAED (t etraacet i lendianina). Numerous conventional activators are known. See for example the U.S. Patent. 4,915,854, published on April 10, 1990 to Mao et al. And the U.S. Patent. 4,412,934. Activators of nonanoyloxybenzene sulfonate (NOBS) or acylactaine can be shown and mixtures thereof can also be used with TAED. See also the U.S. Patent. 4,634,551 with respect to other conventional conventional bleach activators. Also known are the activators bleach-is derived from arnido «Je formulas: Rl N (R *) C (0) R2C (0) L or Rl C (0) N (R5) R2C (0) L where R is an alkyl group containing from about 6 to about 12 carbon atoms, Rl2 is an alkylene which contains about 6 carbon atoms, RS is H or alkyl, aryl or alkaline containing from about 1 to about 10 atoms of carbon. carbon, and L is a suitable output group different from a lactam to the a-rnodifi ed. Another illustration of the bleach activators of the above formulas include (6-octane-do-caproyl) -oxabenzenesulfonate, (6-nonanenediol), oxobenzenesulfonate, (6-decane-dodene) caproyl) oxobenzenesulfonate, and mixtures thereof as described in the US Patent 4,634,551. Another class of bleaching activators comprises activators of the benzoxacin type described by Hodge et al. In U.S. Pat. No. 4,966,723, published on October 30, 1990. Another class of bleaching activators include acyl-lactam activators such as octanol lcaprolactarin, 3,5,5-tprnethylhexanoi Icaprolact arna, nonanoylcaprolactarna, decanoyl-caprolactarna, undecenoyl-caprolactarna, Octanol Ivalerolactarna, decanoyl valerolactan, undecenoylvalerolactarna, nonanoyl-valerolactarna, 3,5,5-tr? rnet? hexane? l valerolactane and mixtures thereof. The present compositions may contain, for example, acylbenzoates, such as phenylbenzoate. (b) Organic peroxides, especially diacyl peroxides - These are illustrated extensively in Kirl-- Othrner, Encyclopedia of Chemical Technology, Vol. 17, John Uiley and Sons, 1982 on pages 27-90 and especially on pages 63-72 , all incorporated herein by reference. If "Jiacylperoxide" is used, it will preferably be one that exerts minimal adverse impact on the formation of spots / films. 4. pH and Variation of pH Regulation Many detergent compositions herein will be regulated in their pH, that is, they are relatively resistant to the pH decrease in the presence of acidic dirt. However, other compositions herein may have exceptionally high pH-regulating capacity or may be substantially unregulated in their pH. Techniques for controlling or varying the pH at recommended levels include more generally the use not only of pH regulators, but also of additional alkalis, acids, rapid pH raising systems, double-dose recipients. , etc., and are well known to experts in the art. Preferred ADD compositions herein comprise a pH adjusting component, selected from the water-soluble inorganic alkaline salts and the water-soluble organic and inorganic detergoncy builders. The pH-adjusting components are selected from When the ADD is dissolved in water at a concentration of 1,000-5,000 pprn, the pH remains in the range of about 8, preferably from about 9.5 to about 11. The preferred component for adjusting phosphate-free pH of the invention is selected from the group consisting of: (i) carbonate or sesquicarbonat? of sodium; (n) sodium silicate, preferably the hydrous sodium silicate having a S 2: Na 2? from about 1: 1 to about 2: 1, and mixtures thereof with limited amounts of sodium rnetasilicate; (ni) sodium citrate; dv) citric acid; (v) sodium bicarbonate; (vi) sodium borate, preferably borax; (vn) sodium hydroxide; and (viii) mixtures "Je incisos (?) - (v ??). Preferred embodiments contain low silicate levels (i.e. from about 3% to about 10% SI02). Illustrative of the highly preferred systems of pH-adjusting components are the binary mixtures of granular sodium citrate with anhydrous sodium carbonate and the three-component mixtures of granular sodium tetraptate, citric acid nonohydrate and sodium carbonate. anhydrous. The amount of component to adjust 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 component for using the pH is present in the ADD composition in an amount of from about 5% to about 40%, preferably from about 10% to about 30% by weight. For the compositions herein having a pH of about 9.5 and about ll of the initial wash solution, the particularly preferred embodiments of ADD comprise, by weight of ADD from about 5% to about 40%, preferably from about 10% to about 30%, most preferably from about 15% to about 20%, of sodium citrate with from about 5% to about 30%, preferably from about 7% to about 25%, most preferably from about 8% to about 20% sodium carbonate. The essential system for adjusting the pH can be complemented (it is said for the improved sequestration in water «Jura) by other optional salts as inejorators of < ergency, selected from among the "Je detergencia < They do not contain phosphate known in the art, which include the various water-soluble borates, hydroxysulphonates, polyacetates and polyalkali metal carboxylates, ammonium or substituted ammonium. Alkali metal salts, especially sodium salts, of such materials are preferred. They can be used inejectors of «Jetergencia organic, that do not contain phosphorus, soluble in water, alternative for their sequestering properties. Some examples of better builders of poly acetate and polycarboxylate are the sodium, potassium, lithium, ammonium and substituted ammonium salts of the eti lendiarnin-tet racetico acid; salts of mtrilotpacetic acid, acid tart time-rnonosuccimco, acid tart while-di succi co, carboxymethoxy acid, rnelitic acid and sodium benzene carboxylate. (a) Water-Soluble Silicates - The present detergent compositions for automatic dishwashers may also contain water-soluble silicates. The water soluble silicones herein are any silicates that are soluble to the extent that they do not adversely affect the spotting / film forming characteristics of the ADD composition.

Some examples of silicates are rnetasilicate < The sodium and, more generally, the alkali metal silicates, particularly those having a S 2: N 2 O ratio in the range of 1.6: 1 to 3.2: 1; and stratified silicates, such as the layered sodium silicates described in U.S. Pat. 4,664,839 published May 12, 1987 in favor of HP Rieck NaSKS-6"is a crystalline layered silicate distributed by Hoechst (commonly abbreviated herein as" SKS-6"). zeolite, Na SKS-6 and other water-soluble silicates useful herein do not contain aluminum NaSKS-6 is the form of 6 ~ Na2 0 0s of stratified silicate and can be prepared by methods such as those described in US Pat. German patents DE-A-3, 417, 649 and DE-A-3, 742, 043. SKS-6 is a preferred layered silicate for use herein, other similar layered silicates, such as those having the general formula NaMSi * 02x +? and H2? wherein M is sodium or hydrogen, X is a number from 1.9 to 4, preferably 2, and is a number from 0 to 20, preferably 0. Other various layered silicates from Hoechst include NaSKS-5, NaSKS-7 and NaSKS-ll, such as the alpha, beta and gamma forms. Other silicates may also be useful, such as for example magnesium silicate, which can serve as a tightening agent in granular formulations, as a stabilizing agent for oxygen bleaches and as a component of systems for the control of jets.

Particular particulate silicates in applications for automatic debris washing (ADD) include 2-granular hydrous silicates such as BRTTESILR H2O from PQ Corp. and BRTTFSILR H24 ob + commonly but classes can be used liquids of silicate vanes when the composition of ADD has liqunJa form. Within safe limits, the sodium metasilicate or sodium hydroxide alone or in combination with other silicates can be used in an ADD context to enhance the wash pH to a lessened level. 5. Enhancement of Detergents Detectants of different types of silicates may optionally be included in the compositions herein to help control mineral hardness. Inorganic detergents as well as organic can be used. Detergency builders are typically used in compositions for automatic dishwashing or for washing fabrics, for example to assist in the removal of particulate dirt. The level of an emergency enhancer can vary widely depending on the final use of the composition and its desired physical form. When present, the compositions will typically contain at least about 1% of antergency enhancer. High performance compositions typically contain from about 10% to about 10%, more typically from about 15% to about 50% by weight of the builder. However, the lowest or highest levels of the ergometer improver are not excluded. Potential inorganic or phosphorus-containing detergents include, but are not limited to, the alkali metal, ammonium or alkanolammon salts of polysulfates (exemplified by the polyphosphates, polyphosphatic phosphates and metaphosphates), phosphonates, phytic acid , silicates, carbonates (including bicarbonates and sesquicarbonates), sulfates and alurninosi 1 icates. However, they are required in some "Jetergency" locations that do not contain phosphate. In the compositions herein they function simply well even in the presence of "weak" detergency builders (as compared to phosphates) such as citra or the so-called "buzzing" situation may occur with the zeolite or with the energetic builders of silicate stratified. See U.S. Pat. 4, 605,509 par-a examples of alurninosi Licatos? Refer? Jos. Some examples of carbonate detergency builders are the alkaline earth metal and alkali metal carbonates as described in German Patent Application No. 2,321,011, published November 15, 1973. Various kinds and types of sodium carbonate and sesquicarbonate can be used. sodium, some of which are particularly useful as carriers for other ingredients, /? H surfactants, especially detersive agents. Aluminum detergent builders can be used in the present compositions although they are not [referred to by detergents for automatic dishwashing. The formation of detergencies of the urm nosi i cat o are of great importance in the granular detergent compositions ar ar intensive service, very commonly distributed, and can be also a significant detergent forming ingredient in detergent formulations. liquids The aluminosil icato detergency builders include those with the empirical formula: 2O "L2O3 - SIOz -yH2" where z and e are integers of at least 6, the molar ratio of the la and is in the range of 1.0 to about 0.5, and x is an integer from about 15 to about 264. Useful materials from the unique exchange of aluminosilicate are commercially obtainable.They may be crystalline or amorphous in structure and may be the urninosilicates that are available. The present invention is in nature or synthetically derived.A method for producing aluinmosilicate ion exchange materials is described in US Pat. No. 3,985,669, Krurnrnel et al. published on October 12, 1976. Alkalmosilicate ion exchange materials, Preferred crystalline, synthetic, useful in the present are obtainable with the designations Zeolite A, Zeolite P (B), Zeolite MAP and Zeolite X. In another mod ality, the exchange material /, 9 ionic, crystalline alumina has The formula: N? 12 (AIO2) i2 (S1O2) i21- H2O where x is approximately 70 to approx. 30, specifically and approximately 27. This material is known as Zeolite A Dehydrated zeolites (x-0-10) can also be used in the present. Preferably, the alumina has a particle size of about 0.1-10 microns in diameter. The mibridors particles may desirably be smaller than 0.1 microns to further assist the exchange kinetics by maximizing the surface area. The large surface area also increases the usefulness of the inosilicates as adsorbents for surfactants, especially in granular compositions. Aggregates of silicate particles or alurninosi licato are useful, having a single aggregate «specified junctions to minimize segregation in the granular-is compo- sitions, while the aggregate particle remains dispersible to individual particles. subrnicrornet icas during washing. As with other forms of detergency such as carbonates, it may be desirable to use zeolites in any physical or morphological form adapted to promote the carrier function of the surfactants and the appropriate particle sizes can be selected freely by the formulator. Organic detergent formers suitable for the purposes of the present invention include, but are not restricted to, a large vape "Jad". He composed "Je pol i car-box i lato. As used herein, "policarboxylate" refers to compounds having a multitude of carboxyl groups, preferably at least 3 carboxyl groups. Polycarboxylate builder builders can generally be added to the composition in the acrylic form, but can also be added in the form of the neutralized salt "overbased". When used in the form of salt, those of alkali metals, such as the sodium, potassium and lithium or alkanolar salts, are preferred. Including among the polycarboxylate detergent builders is the variety of categories of useful materials. An important category of poly carboxylate detergents encompasses polyether ether carboxylates, including oxydisuccinate, as described in Berg, U.S. Patent 3,128,287, published April 7, 1964, and Lamber i et al., U.S. Pat. 3,635,830, published January 18, 1972. See also the "TMS / TDS" detergency builders of the U.S. Patent. No. 4,663,071, issued to Bush et al. On May 5, 1987. Suitable ether carboxylates also include cyclic compounds, particularly alicyclic compounds, such as those described in the "Je E.U.A. 3, 923, 679; 3, 835, 163; 4,158,635; 4,120,874 and 4,102,903. Other useful builders include ether hydroxypolycarboxylates, copolymers, maleic anhydride with ethylene vinyl ether, acid 1,3,5-t phi drox ibencen- 7.4, 6-t psulonic and Carboxymethyl and Loxi-succinic acid, the various alkali metal, ammonium and substituted ammonium salts of polyacetic acids such as diethylene diacetic racerate acid and methyl triatot acid, as well as polycarboxylates such as methyl acid, succinic acid, acid oxidisuccinic acid, polyrnaleic acid, benzene-1,3,5-tricarboxylic acid, carboxymethoxysuccinic acid and soluble salts thereof. Citrate detergent builders, for example, citric acid and soluble salts thereof (particularly sodium salt), are polycarboxylate detergent builders of particular importance * for intensive service detergent formulations for laundry and automatic laundry. tackle due to its availability from renewable resources and its biodegradability. Citrates in combination with zeolite, the aforementioned types of BRITESIL and / or sacrificial silicate builders can also be used. Oxidiscetics are also useful in such compositions and combinations. Also suitable in the detergent compositions of the present invention are 3, 3-d? Carbox? -4 -oxa-1, 6-hexanedionates and related compounds, described in the U.S. Patent. 4,566,8984, Bush, published January 28, 1986. The succimic acid detergency builders include the succinic C5-C20 alkyl and alkenyl acids and salts thereof. A particularly preferred compound < This is the reason why I do not know how to do it. Some specific examples of succinate detergent binders include: 1 still lsuccinate, rni p stilsuccinate, born pa itilsucci, 2-dodecenylsucdan (preferred), 2-pentadecemlsuccinate and the like. Lauplsuccinates are the preferred detergency formers of this group and are described in European Patent Application No. 36200690.5 / 0,200,263, published on November 5, 1986. Other suitable polycarboxylates are described in US Pat.

Patent of E.U.A. 4,144,226, CrutchfLeld and others published on March 13, 1979 in the patent "le E.U.A. 3,308,067, Diehl, published on March 7, 1967. See also The U.S. Patent. 3,723,322. Fatty acids, for example C12-C18 monocarboxylic acids, can also be incorporated into the compositions alone or in combination with the above-mentioned detergency builders, especially citrate detergent builders and / or succime builders, to provide additional detergent builder activity. , but they are not generally desired. Such use of fatty acids will generally result in a decrease in the formation of suds in the laundry compositions, which needs to be taken into account by the fornulator. The fatty acids and their salts are undesirable in the modalities for the automatic washing of tackles (ADD) in situations in which creams of soap can be formed and deposited in the tackle. In cases where phosphorus-based builders can be used, various alkali metal phosphates such as the well-known sodium polyphosphate, sodium pyrophosphate and sodium ortho-phosphate can be used. Phosphonate builders such as ethane-1-hydrox i -1, 1-d can also be used. phosphonate and other known phosphonates (see, for example, U.S. Patents 3,159,581, 3,213,030, 3,422,021, 3,400,148 and 3,472,137) although such materials are more commonly used in a low level mode as chelators or stabilizers. 6 Chelating Agents The compositions herein may also optionally contain one or more selective sequestrants of transition metals, "chelators" or "chelating agents", for example, iron and / or copper and / or manganese chelating agents. Chelating agents suitable for use herein may be selected from the group consisting of aninocarboxylates, phosphonates (especially the arninos phosphonates), polyfunctionally substituted aromatic chelating agents and mixtures thereof. Without pretending to be limited by theory, it is believed that the benefit of these materials is due in part to their exceptional ability to control iron, copper and manganese in washing solutions; Other benefits include the prevention of inorganic films and the inhibition "Je escarnas. Commercial chelating agents for use in the present include in the DEQUESTR series and creators of Monsanto, DuPont, and Nalco, Tnc. Useful arninocarboxylates as optional chelating agents are illustrated to a greater extent by ethyl niami net racemates, N-hi rox letileti lendiammetmacetatos, or tp lot pacetato, ethylenediamma tetraproprionates, tpetilen-tetraami nhexacetates, diethylene paminapentaacet at and ethanol-digly acids, alkali metal salts, ammonium and substituted ammonium thereof. In general, chelator mixtures can be used for a combination of functions, such as the multiple control of transition metals, the stabilization of long-term products and / or the control of metal oxides and / or hydroxides. of transition, precipitates. Poly-functionally substituted aromatic chelating agents are also useful in the compositions herein. See Patent of U.S.A. 3,812,044 published May 21, 1974, to Connor et al. Preferred compounds of this type in acid form are the dihydroxydisulfobenzenes, such as 1,2-d? H? Drox? -3,5-disulfobenzene. A highly preferred biodegradable chelator for use herein is ethylenediamine disuccinate, "EDDS") especially (but not limited to) in CS, Slisornero as described in the U.S. Patent. 4,704,233, published on November 3, 1987, to Hartrnan and Perkin. The salt of hate is preferred although other forms, such as magnesium salts, may also be useful. Arnides not phosphonates can also be useful for their use as chelating agents in the compositions of the invention when at least more total phosphorus levels are acceptable in the detergent compositions include the ethylene-aminote raqui (methylene phosphonate) and the diethylene-tparninopentaxes ( methylene phosphonate) pre fei-1b 1, these arninophosphonates do not contain alkyl groups or quen the groups of approximately 6 carbon atoms. If used, chelating agents or selective sequestrants of transition mats will preferably constitute from about 0.001% to about 10%, most preferably from about 0.05% to about 1% by weight of the compositions herein. . 7. Dispersant Polymer Preferred ADD compositions herein may additionally contain a dispersant polymer. When present, a dispersing polymer in the present ADD compositions is typically at levels in the range of 0 to about 25%, preferably of approximate "from 0.5% to about 20%, preferably preferably from about 1% to about 8% by weight of the ADD composition. Dispersing polymers are useful for the improved ability to form films of the present ADD compositions, especially higher pH moieties, such as those in which the wash pH exceeds approximately 9.5. Particularly preferred are polymers that inhibit the deposition of calcium carbonate or the magnesium salt in the tackle. Suitable dispersant polymers for use herein are illustrated to a greater degree by the film forming polymers described in the U.S. Patent. No. 4,379,080 (Mur-phy), published April 5, 1983. Suitable polymers are preferably at least partially neutralized salts or of alkali metals, ammonium or substituted ammonium (for example, mono-, di- or tpetanolarnome) of polycarboxylic acids. Alkali metal salts, especially sodium, are very preferred. Although the molecular weight of the polymer can vary over a wide range, it is preferably from about 1,000 to about 500,000, it is most preferably from about 1,000 to about 250,000 and is most preferably still, especially if the ADD is par-to its use in US automatic dishwashing machines, from approximately L, 000 to approximately 5,000. Other suitable dispersing polymers include those described in the U.S. Patent. No. 3,308,067, published on March 7, 1967 to Diehl. Unsaturated monomeric acids which can be polymerized to form suitable dispersing polymers include acrylic acid, acrylic acid (or maleic anhydride), fumaric acid, itacomco acid, aconitic acid, inesaconic acid, raconic acid and metidolanum Lomeo acid. . The presence of mono-metal segments that do not contain carboxylate radicals such as ether-ivinate, est-rene, et full, etc. is suitable as long as such segments do not constitute more than about 50% by weight of the dispersant polymer. Acid copolymers of acyl lime and acplate having a molecular weight of from about 3,000 to about 10,000, preferably from about 4,000 to about 20,000, and an acplarnide content of less than about 50%, preferably less than about 20% by weight of the "Jispersant" polymer. Most preferably still, such a dispersant polymer has a molecular weight of from about 4,000 to about 20,000 and an aclarnide content of from about 0% to about 15% by weight of the polymer. Particularly preferred dispersing polymers are copolymers of modified molecular weight polycarbonate. Such a flake! The articles contain as monomer units: a) from about 90% to about 10%, preferably from about 80% to about 20% by weight of the acrylic acid or its salts and b) from about 10% to about 90%, preferably «Approximately 20% approx.« About 80% by weight of a substituted acrylic resin or its salt and have the general formula: (C (P2) C () (C (0) 0R3) 1 in the which apparently uncovered valences are occupied in affection by hydrogen and at least one of the substituents R, R2 or R3, preferably R or R, is an alkyl or hydroxyalkyl group of 1 to 4 carbons; or R 2 can be a hydrogen and R 3 can be a hydrogen or an alkaline metal salt Very preferred is the substituted acrylic monomer in which R is methyl, R 2 is hydrogen and 3 is sodium F.1 suitable dispersing polymer of poly ac The low molecular weight layer preferably has a molecular weight of less than about 15,000, preferably from about 500 to about 10,000, most preferably from about 1,000 to about 5,000. The polyacrylate copolymer formerly intended for use herein has a molecular weight of about 3,500 and is the fully neutralized form of the polymer which contains about 70% by weight of acrylic acid and about 30% by weight of methane acid. . Other suitable modified polyacrylate derivatives include the copolymers of ba or molecular weight of unsaturated aliphatic carboxylic acids described in the "Je E.U.A. 4,530,766 and 5,084,535. The agglomerated forms of the present ADD compositions employ aqueous solutions of polymer dispersants as liquid binders to make the agglomerate "Jo (particularly when the composition consists of a mixture of sodium chloride and sodium carbonate). Especially preferred are the lattice polymers with an average molecular weight of from about 1,000 to about 10,000 and the acrylic / maleate or acnlate / fumarate copolymers with an average molecular weight of from about 7,000 to about 80,000. and a ratio of the segments from acp lato to maleate or fumarate from about 30: 1 to about 1: 2. Some examples of such copolymers based on a mixture of unsaturated mono- and dicarboxylate monomers are described in European Patent Application No. 66,915, published on December 15, 1982. Other dispersion polymers useful herein include polyethylene glycols and propylene glycols having a molecular weight of about 950 to about 30,000 obtainable through the Dow Chemical Company of Midland, Michigan. Such compounds, for example, having a melting point in the range of about 30 ° C to about 100 ° C, can be obtained with molecular weights of 1,450.3,400, 4,500, 6,000, 7,400, 9,500 and 20,000. Such compounds are formed by the polymerization of ethylene glycol or propylene glycol with the required number of moles of propylene or propylene oxide to provide the desired molecular weight and melting point of the respective polyethylene glycol and polypropylene glycol. Polyethylene, polypropylene and mixed glycols are referred to using the formula: HO (CH 2 CH 20) m (CH CH (CH 3) 0) "(CH (CH 3) CH 20) 0 OH in < Jon «Je rn, n and o are integers that satisfy the molecular weight and temperature requirements given above. Other dispersant polymers most useful herein include cellulose sulfate esters such as cellulose acetate sulfate., cellulose sulfate, hydroxyethylcellulose sulfate, rilethylcellulose sulfate and hydroxypropyl cellulose sulfate. Sodium sulfate-cellulose is the most preferred polymer of this group. Other suitable dispersing polymers are the carboxylated polysaccharides, particularly starches, celluloses and alginates, described in the U.S. Pat. No. 3,723,322, Diehl published on March 27, 1973; the esters of dextpna and polycarboxylic acids described in the U.S. Patent. No. 3,929,107, Thompson, published November 11, 1975; the hydroxyalkylnrnidon ethers, starch esters, oxidized starches, dext fights and starch hydrolyzates described in the U.S. Pat. No. 3,803,285, Densen, published on April 9, 1974; the car-boxylated starches described in the U.S. Pat. No. 3,629,121, Eldib, published December 21, 1971; and the dextrinones described in the U.S. Patent. 4,141,841, McDonald, published on February 27, 1979. Preferred dispersing polymers of cellulose are carboxymethylene glycol. Another group of acceptable dispersants are organic dispersant polymers, such as polyspartate.8. Caring Materials Agents The present compositions of FDD may contain one or more material agents "Je cu? Da" Jo que s "> They are effective as corrosion inhibitors and / or as auxiliary materials for anti-rhemorites. Such materials are preferred components of machine-washing compositions, especially in certain European countries where the use of galvanized silver-nickel and pure silver is still comparatively common in domestic vases, or when the protection of aluminum It is a concern and the composition is low in silicate. Generally, such care materials include rnetasil icate, silicate, bismuth salts, manganese salts, paraffin, tnazoles,? Reasons, thiols, rnercaptanes, salts of fatty acids of aluminum 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 ina pair oil, typically a predominantly branched fatico hydrocarbon having a number of carbon atoms in the range of about 20 to about 50; the preferred paraffin oil is selected from predominantly branched C25-45 species with a ratio < Cyclic hydrocarbons with respect to non-cyclic hydrocarbons of about 32:68. A paraffin oil that 6? satisfies these characteristics it is marketed by Uintershall, Salzbergen, Germany, under the corner name UINOG 70. Addition Also, it is also preferable to add low levels of bismuth nitrate (ie-, H? (N? 3 3. Other corrosion-inhibiting compounds include benzot riazole and comparable compounds, mercaptans or thiols include thionophthol and thioantr-anol, and finely divided alumina fatty acids, such as aluminum stearate, are formulated! that maternal sayings are generally used judiciously and in limited quantities in order to avoid any tendency to produce stains or films on the glassware or to compromise the bleaching action of the compositions.For this reason, ercaptan antiherrurnbres are preferably avoided. They are fairly common carboxylic fatty acids and remarkably reactive with bleach that in particular are precipitated with calcium 9. Ester Foam Suppressors of Phosphate and Silicone The ADD's of the invention may optionally contain an alkyl phosphate ester suppressant, a suppressant of ilicon foams, or combinations thereof. The levels are in general from 0% to approximately 10%, preferably from around -0.001% to approximately «5%. Typical levels tend to be low, for example, from about 0.01% to about 3% when a silicone foam suppressant is used. Preferred non-phosphate compositions completely omit the phosphate ester component. The technology of ilicon foam suppressors and other defoaming agents useful in the present invention is documented extensively in "Defoaming, Theor-y and Industrial Applications", Ed., P "R. Garrett, Mareel Dekker, N.Y., 1973, ISBN 0-8247-8770-6, incorporated herein by reference. See especially the chapters entitled "Foarn control m Detergent Products" (Ferch et al.) And "Surfactant Antifoams" (Blease et al.). See also the Patents of E.U.A. 3,933,672 and 4,136,045. Highly preterred silicone foam suppressors are the mixed types known to be used in detergents < Such laundry as heavy duty granules, although the types hitherto used only in heavy duty liquid detergents can also be incorporated in the present compositions. For example, polydimethylsiloxanes having trirnethylsilyl or terminal blockers alternately as the ilicon can be used. These may be combined with silica and / or with non-silicone surfactant components, as shown by a foam suppressor comprising 12% silica / silica, 18% stearyl alcohol and 70% starch in granular form. An adequate commercial source of the active silicone compounds is Dow Corning Corp. The levels of the foam suppressant depend to a certain extent on the foaming tendency of the composition.; for example, an ADD even used at 7000 pprn comprising 7% oxide "Je octadeci 1 dimet ílarnina may not require the presence of a suppressor of foams. Furthermore, it is an advantage of the present invention effective amine selectives which inherently show a much lower tendency to form foams than typical cocoamine oxides. In contrast, formulations in which the amine oxide is combined with an ammonium co-surfactant of high foam formation, eg, alcyuil ethoxysulfate, benefit greatly from the presence of the foam suppressant. It has also been claimed that phosphate esters provide some surface protection < Je utensils of silver and covered with silver; however, the compositions of the present invention can have excellent care of the silver although they lack a phosphate ester component. Without being limited by theory, it is thought that low pH formulations, for example, those having a pH of 9.5 and lower, plus the presence of low level amine oxide, contribute to the improved care of the silver. However, if it is desired to use a phosphate ester, suitable compounds are described in the U.S. Patent. 3,314,891, filed April 18, 1967 by Schrnolka et al., Incorporated herein by reference. Preferred alkyl ester phosphates contain from 16 to 20 carbon atoms. Highly preferred alkyl phosphate esters are monostearyl acid phosphate or rnonooleyl acid phosphate, or salts thereof, particularly alkali metal salts, or mixtures of the same. It has been found preferable to avoid the use of simple soaps of calcium precipitants as an antifoam before in the present compositions, since they tend to be deposited on the tableware. In addition, the phosphate esters are not totally free of such problems, so the formulator will generally choose to minimize the content of antisplants presently deposited in the present compositions. 10. Other Optional Adjuvants Depending on whether a greater or lesser degree of density is required, filler materials may also be present in the present ADDs. These include sucrose, sucrose esters, sodium sulfate, potassium sulfate, etc., in amounts up to about 70%, preferably < Je 0% to next «Hap 40%« He composition of ADD. The preferred filler is sodium sulfate, especially in good grades that have at least low levels of traces of impurities. The sodium sulfate used in the present invention preferably has a sufficient purity to ensure that it does not react with the bleach; it can also be treated with low levels of sequestration «Jores, such as phosphonates or EDDS in the form of magnesium salt. Note that the preferences, in terms of purity sufficient to avoid the decomposition of the bleach, are also applied to reliable pH adjusting ingredients, specifically including any silicate used in the present invention. Although optionally present in the present compositions, the present invention encompasses embodiments that are substantially free of sodium chloride or potassium chloride. Hydrotropic materials such as sodium benzenesulfonate, sodium toluene fonate, sodium curnensulphonate, etc. may be present, for example, for better dispersing surfactant. Perfumes stable to bleaching (stable to release aroma) and color-formerly stable to bleaching, such as those described in U.S. Pat. 4,714,562 by Roselle et al., Filed December 22, 1987, may also be added to the present compositions in appropriate amounts. Other common detergent ingredients that are consistent with the spirit and scope of the present invention are not excluded. Since the ADD compositions of the present invention may contain water-sensitive ingredients or ingredients that can belt-up when combined in an aqueous environment, it is convenient to keep the moisture-free content of the ADDs at a minimum, for example, 7% or more. less, preferably 4% or less of the ADI); and provide a package that is substantially impermeable to water and carbon dioxide. Coating measures have been described in the present invention to illustrate how to protect the ingredients from each other and from the ai r-e and moisture. Plastic bottles, including refillable or recyclable types, as well as cartons or conventional barrier boxes, are another useful way to ensure maximum storage stability. As it has been observed, when the ingredients are not highly compatible, it may also be convenient to coat at least one of said ingredients with a low foaming nonionic surfactant for protection purposes. There are numerous waxy materials that can be easily used to form suitable coated particles of any of said otherwise incompatible components; however, the forrnulador prefers those materials that do not have a marked tendency to deposit or form films on plates, including those of plastic construction. Some preferred granular compositions substantially free of chlorine bleach for the automatic dishwashing of the present invention are the following: a substantially free chlorine bleach-free automatic dishwashing composition comprising (i.e. TERMAMYL "and / or a bleach-stable arnillase and a bleaching system" [comprising a source of hydrogen peroxide selected from sodium erratate and sodium percarbonate and a cobalt catalyst as defined in This invention is also contemplated as a free-flowing, free-flowing chlorine bleach composition for automatic dishwashing comprising an oxidative arnilasa of increased stability and a bleaching system comprising a source of? er * ox? Hydrogen selected from sodium per-borate and sodium percarbonate, a cobalt catalyst and TAED or NOBS.

Cleaning Method; The present invention also encompasses a method for cleaning soiled dishes which involves contacting said tableware with an aqueous medium comprising a cobalt catalyst, preferably at a concentration of about 2 pprn to about 10. ppm, as described above in the present invention. The preferred aqueous medium has an initial pH in a wash solution of about 8, more preferably about 9.5 to about 12, and most preferably about 9.5 to about LO.5. This invention also encompasses a method of dishwashing in a household appliance that relies on automatic dishwashing, which involves treating the dirty dishware in an automatic dishwashing machine with an aqueous alkaline bath comprising amylase and a cobalt catalyst.

Compositions and Methods for Facilitating Rinsing: The present invention also relates to compositions useful in the "flushing" cycle of the procedure for automatic dishwashing, said compositions being commonly referred to as "rinsing aids". Although the compositions described above may also be formulated for use as auxiliary rinsing compositions, no use purposes are required as a rinsing aid having a source of hydrogen peroxide present in said compositions (even a source of peroxide is not required). of hydrogen, at least at low levels to complement at least the drag). 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 the residual detergent composition is brought to the next stage of the wash cycle to the rinse cycle. Thus, when an ADD composition containing a source of hydrogen peroxide is used, the source of hydrogen peroxide for the rinsing cycle is taken to the next stage from the wash cycle. The catalytic activity provided by the cobalt catalyst is thus effective with this remnant of the Wash cycle. Thus, the present invention further encompasses automatic dishwashing rinse aid compositions comprising: (a) a catalytically effective amount of a cobalt catalyst as described in the present invention, and (b) detergent adjuvant materials. for automatic dishwashing. Preferred compositions comprise a low foaming nonionic surfactant. These compositions are also preferably in liquid or solid form. The present invention also encompasses methods for dishwashing in a household appliance for automatic dishwashing, said method comprising treating the dishware dur-ante with a washing cycle of an automatic dishwashing machine with a alkaline aqueous bath comprising a source of hydrogen peroxide, followed by treating the ware in a subsequent rinse cycle with an aqueous bath comprising a cobalt catalyst as described in the present invention.

Synthesis Methods of Cobalt Catalysts: Cobalt bleach catalysts having carboxylate ligands can be further obtained by the following synthesis methods described for the preferred catalyst CCo (NH3) sOAc] Cl2.

Synthesis of CCo (NH3) sQAc] Cl2 NH4? H (with) CC? (NH3) sCl] Cl2 > + AC20 PAC Add "Co (NH3) sCpci2 (26.4 g, 0.10 mol) to water destilled for (800 rnL)." NH4OH (23.4 mL, 0.600 mol) is added slowly with stirring. then at 75 ° C and the solid is dissolved with stirring.The solution is cooled to room temperature.Anhydr-L-acetic acid (30.6 g, 0.30 mole) is added slowly with stirring.The solution is stirred for 1 hour at ambient temperature At this point, the reaction solution can be lyophilized to a pink powder or the solution can be rotavapped and the resulting solid can be pumped overnight at 0.05 nm to remove residual water and NH4OAC. Ammonium chloride and ammonium chloride can also be removed by washing the solution with ethanol., 78.1% by spectroscopy of absorption measurements in UV light and visible light. CLAR C in accordance with the method of D.A. Buc ingharn and others, Inorg. Chem. 2_8, 4567-4574 (1989)] shows that all cobalt is present as CCo (NH3) sOAc JCI2 - NH * 0H (with) 30% H2 02 [Co (H20) 6 lCl2 > - > + Ac20 - > PAC NH4CI NH4Cl (25.0 g) is dissolved in NH "OH (150 rnL). Add [Co (H2?) ß] Cl2 (26.4 g, 0.10 moles) to this solution to form a suspension. H2O2 (30%, 40.0 rnL) is slowly dripped into the solution with stirring. It is added slowly with anhydrous acetic stirring (30.6 g, 0.30 mol). The solution is stirred for 1 hour at room temperature. At this point, the reaction solution can be filtered to a pink powder or the solution can be rotavapped and the resulting solid pumped overnight at 0.05 mm to remove residual water and NH4OA0. The excess salts of ammonium acetate and ammonium chloride can also be removed by washing the solid with ethanol. Yield of 35 g, 78.1% by spectroscopy of absorption measurements in UV light and vLSible light. CLAR T e compliance with the method of D.A. Buck Ingharn and others, Tnorg. Chem. 28, 4567-4574 (1989)] shows that all cobalt is present as "Co (NH3) sOAc] Cl2." The following non-limiting examples further illustrate the ADD compositions of the present invention.

EXAMPLES 1 fl 3 The following detergents were prepared in solid form fully formulated for automatic dishwashing: % Act? Vo% Act? Vo% Act? Vo Sodium citrate 15.0 15.0 15.0 Sodium carbonate 17.5 20.0 20.0 Dispersant polymer (see note 1) 6.0 6.0 6.0 I l l l e th e r (Phosphonate (HEDP; acid) 1.0 0.5 0.71 Agent and non-ionic operation (SLF18, 01 Corf or Plur-afac) 2.0 2.0 2.0 Sodium perborate rnonohydrate (see note 3) 1.5 1.5 1.5 TAED 2.5 DTPMP (see note 4) 0.13 Cobalt catalyst 0.2 0.07 0.4 (see note 2) Savinase 6.0T (protease) 2.0 2.0 Savinase 12T (protease) 2.2 Tennarnyl 60T (amylase) 1.5 1.0 1.0 BRITFSIL H20, PO Corp. (as S102) 8.0 8.0 8.0 Metasil icato (anhydrous) 1.25 For fine 0.5 Benzotnazol 0.3 Sulfate, water, minor components Balance to Balance to 100% Balance 100% 100% Note 1: Dispersing polymer: one or more of Socolan PA30, BASF Corp., Accusol 480N, Rohrn R Haas. Note 2: [Co (NH3) 5? Ac Cl2, prepared in accordance with the synthesis examples above. Note 3: These sources of hydrogen peroxide are expressed on a weight percent basis of available oxygen. To convert to a percentage basis of the total composition, divide by approximately 0.15. 7k Note 4: Diet i lent p armnapentak i s (Acido metí Lenfosfomco) EXAMPLE 4 15 70 GO 40 45 Note l: Dispersing polymer: one or more of Socolan PA30, BASF Corp., Accusol? 80N, Rohm »Haas. Note 2: rCo (NH3) 5? c] Cl2, prepared in accordance with the above synthesis examples. Note 3: These sources of hydrogen peroxide are expressed on a weight percent basis of available oxygen.

To convert to a percentage basis of the total composition, divide- between approximately 0.15.

EXAMPLE 5 The following fully formulated solid form detergents were prepared for the automatic washing of vajil Las: 7B Note 1: Dispersing polymer: one or more of Soolan PA30, BASF Corp., Accusol 480N, Roh Haas. Note 2: CCo (NH3) 5? AcJCl2, prepared in accordance with the synthesis examples above. Note 3: These sources of hydrogen peroxide are expressed on a weight percent basis of available oxygen. To convert to a percentage basis of the total composition, divide by approximately 0.15.

EXAMPLE 6 The following detergents were prepared in a solKja form, fully formulated for automatic dishwashing: Note 1: Dispersing polymer: one or more "Je Sokolan PA30, BASF Corp., Accusol 480N, Rohrn? I. Haas. Note 2: rCo (NH3) 5? Ac] Cl2, prepared in accordance with the above synthesis examples. Note 3: These sources of peroxide are expressed on a weight percent basis of available oxygen.

To convert to a percentage basis of the total composition, divide by approximately 0.15.

EXAMPLE 7 Note 1: Dispersing polymer: one or more Sokolan PA30, BASF Corp., Accusol 480N, Rohm S Haas. Note 2: CCo (NH3) sO c Cl2, prepared according to the synthesis examples above. Note 3: These sources of hydrogen peroxide are expressed on a basis of percent by weight of available oxygen. To convert to a percentage basis of the total composition, divide in re approximately 0.15. no EXAMPLE 8 L5 twenty 40 45 50 Note I: Dispersing polymer: one or more of Sokolan PA30, BASF Corp., Accusol 480N, Rohm 8 ¿Haas. Note 2: L "Co (NH3) sO c Cl2, prepared in accordance with the synthesis examples above Note 3: These sources of hydrogen peroxide are expressed on a weight percent basis of available oxygen. convert to a percentage basis of the total composition, divide approximately between 0.15 ADD's of the above examples of dishwashing detergent composition are used to wash tea-stained copings, soiled dishes of noodles and contaminated with starch, cups contaminated with milk, covered with starch, cheese, egg or food for babies, and plastic spatulas stained with tarn, loading the dirty dishes in a domestic appartment for the automatic washing of dishes and washing by using cold wash cycles at a maximum level of 60 ° C, or uniformly from 45 to 50 ° C with a product concentration of the exemplary compositions of around 1,000 to about 5,000 pprn, with Excellent results.

Claims (17)

f! 2 NOVELTY OF THE INVENTION CLAIMS

1. - A detergent composition for automatic dishwashers comprising: a) a catalytically effective amount of a cobalt catalyst-bleach having the formula: fCo (NH3) n (M) m (B) ~ iTy, wherein the cobalt is in the oxidation state +3; n is 4 or 5; M is one or more ligands coordinated with the cobalt in one site; rn is 0, 1 or 2; B is a ligand coordinated with cobalt in two sites; b is 0 or 1 and when b = 0, then rn + n = 6, and when b = l, then rn = 0 and n-4; and T is one or more countermasses present in a number and, where y is an integer to obtain a balanced salt in charge; and further said catalyst- has a base hydrolysis rate constant of less than 0.23 ~? s ~? (25 ° C); b) an effective amount of a source of hydrogen peroxide; and c) auxiliary materials for LCOS autornat dishwasher detergent.

2. A detergent composition for automatic dishwashers comprising: a) a catalytically effective amount of a cobalt catalyst having the formula: [Co (NH3) 5? Ac] Ty, wherein T is one or more contra-acids present in a number and, in «Jonde and is 1 or 2; b) an effective amount of hydrogen peroxide selected from the group consisting of perborate, percarbonate, and mixtures thereof; and c) Auxiliary materials for automatic dishwashing detergents, selected from the group consisting of one or more low foaming nonionic surfactants, proteases, arnilases, water soluble silicates, activators, bleaching agents and mixtures thereof. same.

3. A detergent composition automatic dishwasher according to any of claims 1 or 2 comprising as part or all «He1 auxiliary material of automatic dishwashing one or more low-foaming nonionic surfactants. .

4. A automatic dishwashing detergent composition according to any of claims 1-3, further characterized in that it comprises as a whole or part of the automatic dishwashing auxiliary material one or more agents "care of materi l.

5. A detergent composition for the automatic dishwasher according to any of claims 1-4, further characterized by the fact that it comprises, as part or all of the automatic dishwashing auxiliary material *, one or more water-soluble silicates.

6. An automatic dishwashing detergent composition according to any of claims 1-5, further characterized in that it comprises as part or all of the automatic dishwashing auxiliary material one or more bleach activators, preferably TAED. 04 i7.- A detergent composition for automatic dishwashers according to any of claims 1-6, further characterized in that it comprises a cobalt catalyst of the formula: L "Co (NH3) s lTy. 8.- A detergent composition for automatic dishwashers in accordance with any of the rei indications 1-7, further characterized because it comprises automatic dishwashing auxiliary material selected so that the composition produces less than 5 crn of foam under normal conditions of use 9.- A detergent composition for automatic dishwashers according to any of claims 1-8, further characterized in that a 1% aqueous solution has a pH of less than 11.5 10.- A dishwashing method in a domestic automatic washing machine, said method comprises treat dirty crockery in an automatic dishwasher with an alkaline aqueous barium comprising an automatic dishwashing detergent composition nity with any of claims 1-9. 11. A dishwashing method in a domestic automatic dishwashing appliance, said method comprising treating the dirty dishware in an automatic dishwashing machine with an alkaline aqueous bath comprising a source of hydrogen peroxide and a cobalt bleaching catalyst having the formula: CCo (NH3) n (M) m (B) b] fy, where the cobalt is in the oxidation state +3; n is 4 or 5; M is one or more ligands coordinated with the cobalt in one place; is 0, 1 or 2; B is a Ligand coordinated with the cobalt in two places; b is 0 or l and when b = f), then m + n = 6, and when b-1, then rn = 0 and n = 4; and T is one or more contraons present in a number and, where y is an integer to obtain a balanced salt in charge; and further said catalyst has a base hydrolysis rate constant of less than 0.23 M-i ~ i (25 ° C). 12. A method according to claim 11, further characterized in that the cobalt catalyst has the formula: CCo (NH3) sMl Ty. 13. The method according to claim 11 or 12, further characterized in that the pH of the bath is below 11.5. 14. A method for removing tea and / or coffee stains from the tableware, said method comprises treating the tea articles stained with tea with an alkaline aqueous bath comprising a source of hydrogen peroxide and the bleaching catalyst of cobalt of the formula CCo (NH3 IsOAclT ^, where T is one or more contraAMONS present in a number y, where y is 1 or 2. 15.- An auxiliary rinsing composition for automatic dishwashers that comprises: a) an amount catalytically effective of a cobalt bleach catalyst having the formula: CCo (NH3) n (M) m (B) b lTy, wherein the cobalt is in the oxidation state +3; n is 4 or 5; M is one or more ligands coordinated with the cobalt in one place; rn is 0, 1 or 7; B is a ligand coordinated with cobalt in two sites; b is 0 or 1 and when h-fl, in oces in + n - 6, and how (Jo b-1, then m = 0 and n = 4; and T is one or several contientes firesentes in a number and, in where y is an integer to obtain a balanced salt in charge, and further said catalyst has a base hydrolysis rate constant of less than 0.23 M-1 if (25 ° C), and b) auxiliary materials for dishwashing detergent automatic. 16. An auxiliary rinsing composition for automatic dishwashing "Je with opni" Jad with claim 15, further characterized by the addition of one or more non-ionic surfactants. 1

7. A method for washing dishes in a domestic automatic dishwashing appliance, said method comprising storing the dirty dishes during a washing cycle in an automatic dishwashing machine with an alkaline aqueous bath comprising a source of hydrogen peroxide, followed by - treatment of the dishes during the subsequent rinse cycle with an aqueous bath comprising a cobalt bleach catalyst having the formula: CCo (NH3) n (M) B (B)? > 1TY, where the cobalt is in the oxidation state +3; n is 4 or 5; M is one or more ligands coordinated with cobalt in one site; rn is 0, 1 or 2; B is a ligand coordinated with cobalt in two sites; b is 0 or 1 and when b = 0, then rn + n = 6, and when «Jo b = l, then rn = 0 and n = 4; and T is one or more counter-anions present in a number and, in < Jon "Je and is an integer to obtain a balanced salt in charge;and furthermore said catalyst- has a base hydrolysis rate constant of less than 0.23 M-s-1 (25 ° C) "