MXPA98003551A - Blanq catalyst particles - Google Patents

Abstract

The present invention relates to mixed particles containing bleach catalyst suitable for incorporation into granular detergent compositions, said mixed particles comprising: from about 1% to about 60% bleach catalyst, preferably a cobalt catalyst, and from about 40% to about 99% of carrier material that is melted within the range of about 38øC to about 77øC, preferably selected from the group consisting of polyethylene glycols, paraffin waxes, and mixtures thereof, and to procedures for obtaining this particle These particles are particularly useful components of detergent compositions, such as laundry detergent compositions, hard surface cleaners and especially detergent compositions for automatic washing of vajil

Description

WHITENING CATALYTIC PARTICLES TECHNICAL FIELD The present invention relates to particles containing bleach catalyst and to the preparation of these bleach catalyst-containing particles. These particles are particularly useful components of detergent compositions such as laundry detergent compositions, hard surface cleaners and especially automatic dishwashing detergent compositions.

BACKGROUND OF THE INVENTION Automatic dishwashing, particularly in household appliances, is a very different technique than washing fabrics. Household cloth washing is usually done on specific machines that have a rotating action. These are very different from the domestic and automatic appliances for the washing of dishes of spray action. The spray action is the latter tends to cause foam. The foam can easily overfill in the lower screeds of domestic dishwashers and decrease the spray action, which in turn reduces the cleaning action. Thus, in the field other than dishwashing in domestic machine, the use of common foam-producing laundry detergent surfactants is normally restricted. These aspects are a brief illustration of the only limitations of the formulation in the field of household dishwashing. Automatic dishwashing with bleaching chemicals is different from the bleaching of fabrics. In the automatic dishwashing, the use of bleaching chemicals includes the promotion of the removal of dirt from dishes, although the bleaching of soils can also occur. In addition, the antiredeposition effects of dirt and stain removals of the bleaching chemicals would be desirable. Some bleaching chemicals (such as a source of hydrogen peroxide, alone or together with tetraacetylethylenediamine, TAED) can, under certain circumstances, be useful for cleaning dishes, but this technology gives more than satisfactory results in the context of dishwashing: for example, the ability to remove difficult stains from tea is limited, especially in hard water, and requires greater amounts of bleach. Other bleach activators developed for laundry use can even give negative effects, such as the creation of unpleasant deposits when placed in a product for automatic dishwashing, especially have a very low solubility. Other bleaching systems can damage unique items in dishwashing, such as silverware, aluminum items or certain plastics.

Consumer glasses, tableware and accessories, especially decorative pieces, when washed in automatic dishwashers, are commonly susceptible to damage and can be costly to replace. Typically, consumers do not want to have to separate finer pieces and would prefer the convenience and simplicity of being able to combine all their items and kitchen utensils in a single automatic washing operation. However, doing this as a routine matter has not yet been achieved. Due to the above technical problems, as well as to the needs and demands of the consumers, the detergent compositions for automatic dishwashing (ADD) undergo continuous changes and improvements. Moreover, environmental factors such as phosphate restriction, the desire to provide even better cleaning results with less product, providing less thermal energy and less water to aid the washing process, have all led to the need for improved ADD compositions. . A recognized need in ADD compositions is to have present one or more ingredients that improve the removal of hot beverage stains (e.g., tea, coffee, cocoa, etc.) from consumer articles. Strong alkalis such as sodium hydroxideBleaches such as hypochlorite, builders such as phosphates and the like can help in varying degrees, but all can be harmful as well, or leave a film on glasses, dinnerware or silverware. Consequently, softer ADD compositions have been developed. These make use of a source of hydrogen peroxide, optionally with a bleach activator such as TAED, as already mentioned. In addition, enzymes such as commercial amylolytic enzymes (e.g., TERMAMYL * available from Novo Nordisk S / A) can be added. The alpha-amylase component provides at least some benefit in the starch removal properties of ADD. ADD's containing amylases can typically provide a wash pH in a somewhat more moderate manner during use and can remove starch soils while avoiding to provide large weight equivalents of sodium hydroxide on a per gram basis of product. Therefore, it would be highly desirable to ensure improved bleach activators specifically designed to be compatible in ADD formulations, especially with enzymes such as amylases. Likewise, there is a need to ensure a better action of the amylase in the presence of bleach activators. Enzymes such as commercial protease enzymes (e.g., SAVINASER, available from Novo Nordisk S / A) can also be added. Certain machine dishwashing compositions containing manganese catalyst are described in U.S. Patent No. 5,246,612, issued September 21, 1993, to Van Dijk et al. These compositions are said to be chlorine-free bleach-free machine dishwashing compositions comprising amylase and a manganese catalyst (in the oxidation state +3 or +4), as defined by the structure given herein. The manganese catalyst that is preferred there is a molecule containing dinuclear macrocyclic manganese ligand which is lniv2 (u-0) 3 (l, 4,7-trimethyl-l, 4,7-triazacyclononane) 2 (PF & amp;; ) 2 - It has been more recently discovered that bleach catalysts containing cobalt are particularly effective for use in bleaching compositions such as automatic dishwashing compositions. However, direct incorporation of the small particles of bleach catalyst at typically very low levels in a particulate detergent composition can present problems. Said granular compositions should typically be composed of particles with average particle sizes similar to each other, to avoid segregation of the components in the composition. Such compositions commonly comprise particles having average particle sizes on a defined scale of from about 400 to about 2400 microns, most commonly from about 500 to about 2000 microns, to achieve a good flow and absence of dusty properties. Any fine particle or size exceeded outside these limits should be removed generally by sieving to avoid a problem of particle segregation. The addition of fine particle bleach catalysts in conventional granular detergent products thus potentially presents a problem of component separation. The fine particles of bleach catalyst in a detergent composition may also have chemical stability problems caused by a tendency of the fine particles to interact with other components of the detergent composition, such as the other components of the bleach system. In light of all this, the formulator may wish to incorporate small particles of bleach catalyst, which are preferred for their stain removal performance, in a detergent matrix containing other components having a larger overall average particle size distribution. However, in doing so, the formulator must avoid the problems of segregation and chemical stability associated with the use of small particles of bleach catalyst in this context. The formulator must also maximize consumer acceptance of the aesthetics of the compositions. Given the foregoing considerations, it is an object of the present invention to provide mixed particles containing bleach catalyst and which are useful for incorporating bleach catalysts into granular detergent products, preferably detergent products for automatic dishwashing, in a form that maximizes Stain removal performance, chemical stability and acceptance by the consumer, but minimizing its problems of particle segregation. It is a further object of the present invention to incorporate said mixed particles containing bleaching catalyst in the form of flakes, micro-tablets or extruded materials which, although having a size distribution comparable to that of the other components of the granular detergent composition, allow the supply of bleach catalyst particles in the wash solution. Said objects can be obtained by preparing and using mixed particles containing bleach catalyst according to the present invention.

TECHNICAL BACKGROUND Patent of E.U.A. 4,810,410, to Diakun et al., Issued March 7, 1989; E.U.A. 5,246,612, to Van Dijk et al., Issued September 21, 1993; E.U.A. 5,244,594 to Favre et al., Issued September 14, 1993; and European Patent Application Publication No. 408,131, published January 16, 1991 by Unilever NV. See also: patent of E.U.A. No. 5,114,611 to Van Kralingen et al., Issued May 19, 1992 (transition metal complex, such as cobalt, and a non-acro-cyclic ligand); patent of E.U.A. No. 4,430,243 to Bragg, issued February 7, 1984 (laundry bleaching compositions comprising heavy metals metal cations, including cobalt); German patent specification 2,054,019, published October 7, 1971 by Unilever N.V. (cobalt chelant catalyst); and European Patent Application Publication No. 549,271, published June 30, 1993 by Unilever PLC (macrocyclic organic ligands in cleaning compositions).

BRIEF DESCRIPTION OF THE INVENTION The present invention relates to mixed particles containing bleach catalyst suitable for incorporation into granular detergent compositions, said mixed particles comprising: (a) from about 1% to about 60% bleach catalyst; and (b) from about 40% to about 99% of a melting vehicle material within the range of from about 38 ° C to about 77 ° C, preferably selected from the group consisting of polyethylene glycols, paraffin waxes and mixtures thereof; and wherein further, said mixed particles have an average particle size of from about 200 to about 2400 microns. The particles that are preferred have a free water content of less than about 10% by weight. The particles may also optionally contain extender materials.

The process of the present invention includes the preparation of mixed particles containing bleach catalyst suitable for incorporation into granular detergent compositions such as those described hereinabove, especially granular detergent products for automatic dishwashing. Said process comprises the steps of: (a) combining the bleach catalyst particles with a melted carrier material that melts within the range of from about 38 ° C to 77 ° C, while stirring the particle-particle combination resulting vehicle to form a substantially uniform combination of the particles and the carrier material; (b) cooling the vehicle-particle combination of step (a) to form a solidified mixture of particles and carrier material; and (c) further work the particle-solidified vehicle material mixture formed in step (b) if necessary to form the desired mixed particles. The present invention also relates to mixed particles containing bleach catalyst such as those prepared by the present process and to detergent compositions, especially detergent products for automatic dishwashing, using these mixed particles containing bleach catalyst. The mixed particles of this invention comprise both discrete bleach catalyst particles of a relatively small particle size and a carrier material, the mixed particles having an average particle size which is comparable to that of the other conventional component particles used in the granular detergent compositions. Said particles then allow the supply in a wash solution of small particles of bleach catalyst when the carrier material in the mixed particles is dissolved in the aqueous wash solution, thereby releasing the bleach catalyst particles. Although other forms of particles are possible, the mixed particles of this invention are preferably in the form of flakes or icropastillas. It has been found that particles (e.g., flakes and micropaints) exhibit increased storage stability in the presence of a detergent matrix. In addition, the mixed particles are not segregated from other particles in the granular detergent compositions in which they are incorporated. Finally, compositions containing such mixed particles provide a mottled appearance more acceptable to the consumer than compositions having individual bleach catalyst particles.

DETAILED DESCRIPTION OF THE INVENTION The particles according to the present invention comprise discrete particles of bleach catalyst and of a carrier material. These particles may optionally contain other components, such as stabilization additives and / or diluents. Each of these materials, the steps in the mixed particle preparation process, the mixed particles thus prepared and the granular detergents (e.g., for automatic dishwashing) containing these particles, are described in detail as follows : Bleach Catalyst The mixed particles according to the present invention comprise from about 1% to about 60% by weight, most preferably from about 2% to about 20% by weight, more preferably from about 3% to about 10% by weight of the mixture of discrete particles and bleach catalyst. These typical bleach catalyst particles and preferably have an average particle size of less than about 300 microns, preferably less than about 200 microns, most preferably from about 1 to about 150, more preferably from about 10 to about 100 microns. The bleach catalyst material may comprise the free acid form, the salts and the like. One type of bleach catalyst is a catalyst system comprising a transition metal cation of defined bleach catalytic activity such as copper, iron, titanium, ruthenium, tungsten, molybdenum or manganese cations, an auxiliary metal cation having very little or no catalytic bleaching activity such as zinc or zinc or aluminum cations and a sequestrant having defined stability constants for the catalytic and auxiliary metal cations, particularly ethylenediaetetraacetic acid, ethylenediaminetetramethylenephosphonic acid and water soluble salts thereof . Said catalysts are described in the patent of E.U.A. No. 4,430,243. Other types of bleach catalysts include the manganese-based complexes described in the U.S.A. No. 5,246,621 and in the patent of E.U.A. No. 5,244,594. Preferred examples of these catalysts include MnIV2 (u-0) 3 (1, 4,7-trimethyl-1, 4,7-triazacyclononane) 2- (PF6) 2, Mn1 XI2 (u-0)? (u-0Ac) 2 (1, 4,7-trimethyl-1, 4,7-triazacyclononane) 2- (C10) 2, MnIV4 (u-0) 6 (1, 4,7-triazacyclononane)? - ( C10 / i) 2, MnIIIlinIV4 (u-0)? (u-0Ac) 2 (1, 4,7-trimethyl-1, 4,7-triazacyclononane) - (Cl) 3, and mixtures thereof. Others are described in the publication of European patent application No. 549,272. Other ligands suitable for use herein include 1, 5,9-trimethyl-1, 5,9-triazacyclododecane, 2-methyl-1, 4,7-triazacyclononane, 2-methyl-1,4,7-triazacyclononane and mixtures thereof. same. Bleach catalysts useful in automatic dishwashing compositions and concentrated powder detergent compositions may also be selected as appropriate for the present invention. For examples of suitable bleach catalysts see U.S. No. 4,246,612 and US patent. No. 5,227,084. See also patent of E.U.A. No. 5,194,416, which teaches mononuclear (IV) manganese complexes such as Mn (1, 4,7-trimethyl-1, 4,7-triazacyclononane (0CH 3) 3 ~ (PFs) - One more type of bleaching catalyst as described in U.S. Patent No. 5,114,606 is a water-soluble complex of manganese (II), (III) and / or (IV) with a ligand that is a polyhydroxy compound that is non-carboxylate and has at least three groups Consecutive C-OH Preferred ligands include sorbitol, iditol, dulsitol, mannitol, xylitol, arabitol, adonitol, meso-erythritol, meso-inositol, lactose and mixtures thereof U.S. Patent No. 5,114,611 teaches a catalyst bleaching comprising a transition metal complex, including Mn, Co, Fe, or Cu, with a non-macrocyclic ligand.These ligands have the formula: R3 Ri-N = C-B-C = - * in the that R1, R2, R3 and R * can each be selected from H, substituted alkyl and aryl groups so that each Ra-N = C-R2 and R3-C = N-R4 forms a five or six member ring. Said ring can also be replaced. B is a bridging group selected from 0, S. CR5R6, NR7 and C = 0, where R5, R6 and R? they can each be H, alkyl or aryl groups including substituted or unsubstituted groups. Preferred ligands include pyridine, pyridazine, pyrimidine, pyrazine, imidazole, pyrazole and triazole rings. Optionally, said rings can be substituted with substituents such as alkyl, aryl, alkoxy, halide and nitro. Particularly preferred is the 2,2'-bispyridylamine ligand. Preferred bleach catalysts include Co, Cu, Mn, Fe, -bispyridylmethane and -bispyridylamine complexes. Highly preferred catalysts include Co (2,2'-bispyridylamine) Cl, Di (isothiocyanato) bispyridylamine-cobalt (II), trisdipyridylamine-cobalt (II) perchlorate, Co (2,2-bispi-ridylamine) 202C104, Bischri- perchlorate (2, 2'-bispyridylamine) copper (II), tris (di-2-pyridylamine) iron (II) perchlorate and mixtures thereof. Other examples include Mn gluconate, Mn (CF3S03) 2, Co (NH3) sCl, and the binuclear Mn complexed with tetra-N-dentate and bi-N-dentate ligands, including N ^ Mn111 (u-0) 2Mn * VN¿) + and [Bipy2Mnin (u-0) 2Mniybipy2] - (C10Ü) 3. Bleach catalysts can also be prepared by combining a water soluble ligand with a water soluble manganese salt in an aqueous medium and concentrating the resulting mixture by evaporation. Any suitable water-soluble manganese salt can be used here. Manganese (II), (III), (IV) and / or (V) is readily available on a commercial scale. In some cases, sufficient manganese may be present in the wash liquid, but, in general, Mn cations are preferred in the compositions to ensure their presence in catalytically effective amounts. In this manner, the sodium salt of the ligand and a member selected from the group consisting of MnSOi, Mn (C10 *) 2 or MnCl2 (less preferred) are dissolved in water at molar ratios of ligand: salt of Mn on the scale of approximately 1: 4 to 4: 1 at neutral or slightly alkaline pH. Water can be deoxygenated first by boiling it, and it can be cooled by spraying it with nitrogen. The resulting solution is evaporated (under N2 if desired) and the resulting solids are used in the bleaching compositions and detergents herein without further purification. In an alternative embodiment, the source of water soluble manganese such as MnSO ^, is added to the bleaching / cleaning composition or to the aqueous bleaching / cleaning bath comprising the ligand. A certain type of complex is formed apparently in situ, and an improved bleaching performance is ensured. In said in situ procedure, it is convenient to use a considerable molar excess of the ligand over manganese, and molar ratios of ligand: Mn typically from 3: 1 to 15: 1. The additional ligand also serves to sweep vapid metal ions such as iron and copper, thus protecting the bleach from decomposition. Such a system is described in European Patent Application Publication No. 549,271. Although the structures of the manganese catalyst bleaching complexes of the present invention have not been elucidated, it can be speculated that they comprise chelates or other hydrated coordination complexes resulting from the interaction of the nitrogen and carboxy atoms of the ligand with the manganese cation. Likewise, the oxidation state of the manganese cation during the catalytic process is not known with certainty, and it can be the valence state (+11), (+ III), (+ IV) or (+ V). Due to the six possible fixation points to the manganese cation of the ligands, it can be reasonably speculated that the multinuclear species and / or "cage" structures may exist in the aqueous bleach medium. Whatever the form of the active Mn-ligand species that currently exist, they function in a seemingly catalytic way to provide improved bleaching performance in difficult spots such as tea, ketchup, coffee, wine, juice and the like. Other bleach catalysts are described, for example, in European Patent Application Publication No. 108,131 (Cobalt Complex Catalysts), publications of European Patent Applications Nos. 384,503 and 306,089 (metallo-porphyrin catalysts), USA 4,728,455 (manganese / multidentate ligand catalyst), E.U. 4,711,748 and European patent application publication No. 224,952 (manganese absorbed on aluminosilicate catalyst), E.U. 4,601,845 (aluminosilicate support with manganese and zinc or magnesium salt), E.U. 4,626,373 (manganese / ligand catalyst), E.U. 4,119,557 (ferric complex catalyst), German patent specification 2,054,019 (cobalt chelator catalyst), Canadian 866,191 (salts containing transition metal), E.U. 4,430,243 (chelators with manganese cations and non-catalytic metal cations) and E.U. 4,728,455 (manganese gluconate catalysts). Cobalt (III) catalysts having the formula: C [(NH3) nM'mB'bT'tQqPp] Yy in which the cobalt is in the +3 oxidation state are preferred; n is an integer from 0 to 5 (preferably 4 or 5, most preferably 5); M 'represents a monodentate ligand; m is an integer from 0 to 5 (preferably 1 or 2, most preferably 1); B 'represents a bidentate ligand; b is an integer from 0 to 2; T 'represents a tridentate ligand; t is 0 or 1; 0 is a tetradentate ligand; q is 0 or 1; P is a pentadentate ligand; p is 0 or l; and n + m + 2b + 3t + 4q + 5p = 6; Y is one or more suitably selected counterions present in a number y, where y is an integer from 1 to 3 (preferably 2 to 3, most preferably 2 when Y is a charged anion -1), to obtain a balanced charge salt; The Y referred to are selected from the group consisting of chloride, nitrate, nitrite, sulfate, citrate, acetate, carbonate and combinations thereof; and where in addition at least one of the coordination sites fixed to cobalt is unstable under the conditions of use of automatic dishwashing and the rest of the coordination sites stabilize the cobalt under conditions of automatic dishwashing for a potential of reduction for cobalt (III) to cobalt (II) under alkaline conditions is less than about 0.4 volts (preferably less than about 0.2 volts) against a normal hydrogen electrode. Preferred cobalt catalysts of this type have the formula: CCo (NH3) n (M ') m] Yy wherein n is an integer from 3 to 5 (preferably 4 or 5, most preferably 5); M 'is an unstable coordinating moiety, preferably selected from the group consisting of chlorine, bromine, hydroxide, water and (when m is greater than 1) combinations thereof; m is an integer from 1 to 3 (preferably 1 or 2, most preferably 1); m + n = 6; and Y is a suitably selected counterion present in a number y, which is an integer of 1 to 3 (preferably 2 or 3, most preferably 2 when Y is a charged anion -1), to obtain a balanced charge salt. The preferred cobalt catalyst of this type useful herein are the cobalt pentaamine chloride salts having the formula [Co (NH3) sCl] Yy. , and especially [Co (NH3) sCl] Cl2. The particles and compositions of the present invention which use cobalt (III) bleach catalysts having the formula: [C (NH3) n (M) m (B) b] Ty in which the cobalt is the oxidation state +3; n is 4 or 5 (preferably 5); M is one or more ligands coordinated to cobalt by a site; m is 0, 1 or 2 (preferably 1); B is a ligand coordinated to cobalt by two sites; b is 0 or 1 (preferably 0) and when b = 0, then m + n = 6, and when b = l, then m = 0 and n = 4; and T is one or more suitably selected counterions present in a number and, where y is an integer to obtain a balanced charge salt (preferably y is 1 to 3, most preferably 2 when T is a charged anion -1); and wherein further said catalyst has a base hydrolysis rate of less than 0.23 M-1 s-1 (25 ° C). Preferred T are selected from the group consisting of chloride, iodide, I3-, formate, nitrate, nitrite, sulfate, sulfite, citrate, acetate, carbonate, bromide, PFe-, BF «-, B (Ph) -, phosphate , phosphite, silicate, tosylate, methanesulfonate and combinations thereof. Optionally, T can be protonated if there is more than one anionic group in T, e.g., HPOA2", HCO3-, H2PO4-, etc. In addition, T can be selected from the group consisting of non-traditional inorganic anions such as agents anionic surfactants (e.g., linear alkylbenzenesulfonates (LAS), alkyl sulphates (AS), alkyl ethoxy sulfonates (AES), etc.) and / or anionic polymers (e.g., polyacrylates, polymethacrylates, etc.). include, but are not limited to, for example, F ", SO *" 2, NCS ", SCN-, S2O3-2, NH3, O43-, and carboxylates (which preferably are onocarboxylates, but more than one carboxylate may be present in the portion as long as the link to cobalt is by only one carboxylate per serving, in which case the other carboxylate in the M portion may be protonated or in its salt form). Optionally, M can be protonated if there is more than one anionic group in M (e.g., HPO? 2-, HCO3-, H2 0? -, H0C (0) CH2C (0) 0-, etc.). Preferred M portions are substituted and unsubstituted C 1 -C 30 carboxylic acids having the formula: RC (0) 0 - wherein R is preferably selected from the group consisting of hydrogen and C 1 -C 30 alkyl (preferably C 1 -C 30) Cie) unsubstituted and substituted, C6-C30 aryl (preferably Cß-Cis) unsubstituted and substituted, and C3-C30 heteroaryl (preferably Cs-C s) unsubstituted and substituted, wherein the substituents are selected from the group consisting of - NR'3, -NR'4 +, -C (0) 0R ', -C (0) NR'2, wherein R' is selected from the group consisting of hydrogen and portions of Ci -Ce. Said substituted R includes therefore the portions - (CH2) n0H and - (CH2) n NR'¿ +, wherein n is an integer from 1 to about 16, preferably from about 2 to about 10 and most preferably from about 2. to about 5. Most preferred M's are carboxylic acids having the above formula wherein R is selected from the group consisting of hydrogen, methyl, ethyl, propyl, straight or branched C4-C12 alkyl, and benzyl. The R that is most preferred is methyl. The most preferred M-moieties of the carboxylic acid include formic, benzoic, octanoic, nonanoic, decanoic, dodecanoic, malonic, maleic, succinic, adipic, phthalic, 2-ethylhexanoic, naphthenoic, oleic, palmitic, triflate, tartrate, stearic, butyric, citric, acrylic, aspartic, fumaric, lauric, linoleic, lactic, malic and especially acetic acid. Portions B include carbonate, higher di- and carboxylates (e.g., oxalate, malonate, malic, succinate, maleate), picolinic acid, and alpha and beta amino acids (eg, glycine, alanine, beta-alanine, phenylalanine). Cobalt bleach catalysts useful herein are known, and are described for example together with their base hydrolysis rates, in M.L. Tobe, "Base Hydrolysis of Transition-Metal Complexes", Adv. Inorg. Bioinorg. Mech., (1983), 2, pgs. 1-94. For example, Table 1 on page 17, provides the base hydrolysis rates (designated here koh) for oxallate complexed cobalt pentaamine catalysts (k0H = 2.5 x 10"« M "is" i (25 °)), NCS "(koH = 5.0 x 10- * Ml if (25 ° C)), formate (koH = 5.8 x 10- * M ~? S ~ (25 ° C)), and acetate (koH = 9.6 x 10" * M_1 s_1 (25 ° C)) The cobalt catalyst that is most preferred and useful herein are the cobalt pentaamine acetate salts having the formula [Co (NH3) s0Ac] Ty, where OAc represents a portion acetate, and especially cobalt pentaamine acetate chloride [C0 (NH3) s0Ac] Cl2; as well as [C0 (NH3) s0Ac] (0Ac) 2; [C0 (NH3) s0Ac] (PF6) 2; CC0 (NH3) ) 50 AC] (S0) A; [C0 (NH3) 50Ac] (BF 2; and [C0 (NH3) 50Ac] (N03) 2 (here "PAC"). These cobalt catalysts are easily prepared by known procedures such as those taught for example in Tobe's article hereinabove and in the references cited herein, in the US patent A No. 4,810,410 to Diakun et al., Issued March 7, 1989, J. Chem. Ed. (1989), 66_ (12), 1043-45; The Synthesis and Characterization of Inorganic Compounds, .L. Jolly (Prentice-Hall, 1970), pp. 461-3; Inorg. Chem., 18, 1497-7502 (1979); Inorg. Chem. 21, 2881-2885 (1982); Inoro; Chem., 18, 2023-2025 (1979); Inorg. Synthesis, 173-176 (1960); and Journal of Physical Chemistry, 26, 22-25 (1952); as well as in the synthesis examples provided hereinafter. As a practical matter and not by way of limitation, the cleaning compositions and cleaning methods herein can be adjusted to provide in the order of hands one part per ten million active catalytic bleaching species in the medium of aqueous washing, and will preferably provide from about 0.1 ppm to about 50 ppm, most preferably from about 1 ppm to about 25 ppm, and more preferably from about 2 ppm to about 10 ppm; of the bleach catalyst species in the washing liquid. To obtain such levels in the washing liquid of an automatic dishwashing process, the typical automatic dishwashing compositions of the present invention will comprise from about 0.01% to about 1%, most preferably from about 0.01% to about 0.36, of bleach catalyst by weight of the cleaning compositions.

Synthesis of pentaap-inaacetatocobalt (III) nitrate Ammonium acetate (67.83 g, 0.880 mol) and ammonium hydroxide (256.62, 2.050 mol, 28%) are combined in a 1000 ml three-necked round bottom flask equipped with a condenser, magnetic stirrer and internal thermometer. Cobalt (II) acetate tetrahydrate (110.00 g, 0.400 mol) is added to the clear solution which turns black-brown after the addition of the metal salt is complete. The mixture is briefly heated to 40 ° C. Hydrogen peroxide (27.21 g, 0.400 mol, 50%) is added dropwise over 20 minutes. The reaction is heated to 60-65 ° C and becomes red when the peroxide is added to the reaction mixture. After stirring for an additional 20 min, the red mixture is treated with a solution of sodium nitrate (74.86 g, 0.880 mol) dissolved in 50 ml of water. When the mixture is at room temperature, red crystals form. The solid is collected by filtration and washed with cold water and isopropanol to give 6.38 g (4.9%) of the complex as a red solid. The combined filtrates are concentrated by rotary evaporation (50-55 ° C, 15 mm Hg (vacuum water aspirator)) to form a suspension. The suspension is filtered and the remaining red solid is washed with cold water and isopropanol to give 89.38 g (68.3%) of the complex. Total yield: 95.76 g (73.1%). The analysis by means of CLAR, UV-Vis and combustion are consistent with the proposed structure. Anal. cale, for C2H 8C0N7O8: C, 7.34; H, 5.55; N, 29.97; Co, 18.01. Found: C, 7.31; H, 5.72; N, 30.28; Co, 18.65.

Vehicle material Mixed particles containing bleach catalyst comprise from about 40% to about 99% by weight, preferably from about 50% to about 98% by weight, most preferably from about 60% to about 97% by weight of the particle Mixed of a vehicle material. The carrier material melts in the range of from about 38 ° C to about 77 ° C, preferably from about 43 ° C to about 71 ° C, most preferably from about 46 ° C to 66 ° C. The carrier material must be inert to the reaction with the particle whitening catalyst component under processing conditions and after solidification. Moreover, the carrier material is preferably soluble in water. In addition, the carrier material should preferably be substantially free of moisture present as unbound water. It has been found that polyethylene glycols, particularly those of a molecular weight of from about 2000 to about 12000, very particularly from about 3000 to about 10000 and most preferably from about 4000 (PEG 4000) to about 8000 (PEG 8000), are water soluble carriers especially suitable herein. Said polyethylene glycols provide the advantages that, when present in the wash solution, they exhibit dirt dispersion properties and show little or no tendency to deposit as stains or films on the articles in the wash. Also suitable as vehicle materials are paraffin waxes which must melt on the scale of from about 38 ° C to about 43 ° C and C16-C20 fatty acids and C16-C20 alcohols ethoxylated. Vehicles comprising mixtures of suitable vehicle materials are also glimpsed.

Water content of the particle The mixed particles should have a low free water content to favor the stability of the product and minimize the stickiness of the mixed particles. The mixed particles should then preferably have a water content of less than about 10%, preferably less than about 6%, most preferably less than about 3% and still most preferably less than 1%.

Preparation procedure for the mixed particle The mixed particles are made by a process comprising the following basic steps: (i) combining the bleach catalyst particles with the carrier material as described hereinabove, while the carrier material it is in a molten state and stirring this combination to form a substantially uniform mixture; (ii) rapidly cooling the resulting mixture to solidify it: and then (iii) further work the resulting solidified mixture if necessary, to form the desired mixed particles. (i) Blending / Mixing Step The purpose of the blending / mixing step is to ensure dispersion of the discrete bleaching catalyst particles in the melted carrier material. In more detail, the combined / mixed step can be carried out using any suitable liquid / solid mixing equipment such as that described in Perry's Chemical Enginer's Handbook under "Phase Contacting and Liquid / Solid Processing." For example, the combination and Subsequent blending can be done in an intermittent mode using a simple agitated intermittent tank containing the melted vehicle.The discrete bleaching catalyst particles can be added to the melted vehicle and dispersed with an impeller.This is preferable for small lots that can solidify. Quickly (for reasons hereinafter stated) Alternatively, the combined / mixed step can be done continuously For example, a feeder can be used to dose the bleach catalyst in the flowing melted vehicle (e.g., through a dust eductor). The mixture may optionally be further dispersed using any suitable continuous liquid / solid mixing device such as an in-line mixer (such as those described in chapter 19 of James Y. Oldshue, Fluid Mixing Technology, McGraw Hill Publishing Co., 1983) or a static or non-moving mixer (e.g., from Kenics Corporation) in which stationary elements successively divide and recombine portions of the fluid stream. The cutting speed can be varied both to optimize the dispersion and to determine the particle size of eventual whitening catalyst that is obtained. In some applications, a further reduction in the size of the bleach catalyst particle can be achieved by the use of a colloid mill as the continuous liquid / solid mixing device. In a preferred embodiment, the combined / mixed step acts to disintegrate any aggregate that may have formed in the bleaching catalyst mass. It is acceptable that the mixing step leads to a slight reduction in the overall average particle size of the bleach catalyst particles.

Cii) Cooling / solidification and particle formation steps The combined / mixed step is followed by one or more subsequent steps including cooling and subsequent solidification of the resulting mixture from the combined / mixed step. Subsequent steps may also include forming the mixed particles. These steps encompass executions in which the solidification and particle formation aspects occur coincidentally, or alternatively, where these steps are carried out sequentially in any order of occurrence. In embodiments where the solidification of the overall mixture occurs, the particle is formed from the solidified mixture by the use of any suitable fragmentation process, such as milling procedures. Cooling and solidification can be carried out using any conventional equipment such as that described in Perry's Chemical Enginer's Handbook under 'Heat Exchangers for Solids'. In a preferred embodiment that includes the manufacture of flake-like mixed particles, solidification occurs by introducing the mixture into a cooling roll or cooling band, thereby forming a layer of solid material on the roll or band. This is followed by a step which comprises removing the layer of solid material from the roller or band and subsequently grinding the solid material removed. This can be achieved, for example, by cutting the solid layer into smaller pieces, followed by reducing these parts to an acceptable size using conventional size reduction equipment (eg Quadro Co-mil or a cage mill). . The ground solidified material may also be worked as needed by sifting the ground material to provide particles of average particle size and size distribution desired. In another preferred embodiment that includes making mixed particles in the form of a micro-chip, aspects of cooling, solidification and particle formation occur in an integral process that includes supplying droplets of bleach catalyst / vehicle material through the mixture. of a feeding hole on a cooling band. The feeding orifice is preferably chosen to promote the formation of micro-tablets having an average particle size of from about 200 to about 2400 microns, preferably from about 500 to about 2000 microns and most preferably from about 600 to about 1400 microns. In said process, additional work of the solidified mixture is not necessary to achieve mixed particles of the desired size. In a further preferred embodiment which includes making extruded mixed particles, the formation of the particle takes place in an extrusion process in which the mixture of bleach catalyst particle / carrier material is extruded through a die plate in a cooling device (e.g., a cooling drum, fluidized bed cooler, etc.). The holes in the die plate are preferably chosen to favor a formation of extruded materials with a diameter of between about 400-1000 microns, preferably 500-900 microns, most preferably 600-700 microns and having an average particle size (per screening) of from about 200 about 2,400 microns, preferably from about 500 microns to about 2,000 microns and most preferably from about 600 to about 1,400 microns. The solidified extruded materials are then screened to obtain mixed particles of the desired size fraction.

Ciii) Optional additional steps An additional step that is preferred, particularly when the formation of flakes or extruded materials is included, comprises the step of sifting the particles to obtain mixed particles having an average particle size of from about 200 about 2400 microns, preferably about 500 about 2000 microns, most preferably about 600 to about 1400 microns. Any particle of larger size can be subjected to a size reduction step and any particle of smaller size can be reintroduced into the melted mixture of the combined / mixed step.

DETERGENT COMPOSITIONS The mixed particles herein are useful components of detergent compositions, particularly those designed for use in automatic dishwashing methods. The detergent compositions may additionally contain any known detergent component, particularly those selected from pH adjusting and detergency improving components, other bleach, bleach activators, silicates, dispersing polymers, low-foaming nonionic surfactants, -anionic surfactants, enzymes, enzyme stabilizers, foam suppressors, corrosion inhibitors, fillers, hydrotropes and perfumes. A preferred granular or powder detergent composition contains by weight: a) from about 0.1% to about 10% of the mixed particles containing the bleach catalyst as described hereinabove; b) a bleaching component containing from about 0.01% to about 8% as available oxygen from a peroxygen bleach; c) from about 0.1% to about 60% of a pH adjusting component consisting of water-soluble salt or salt / builder mixture selected from sodium carbonate, sodium sesquicarbonate, sodium citrate, citric acid, sodium bicarbonate sodium, sodium hydroxide and mixtures thereof; d) from about 3% to about 10% silicate such as Si 2; e) from 0 to about 3% to 10% of a low foaming nonionic surfactant other than amine oxide; f) from 0 to about 10% of a suds suppressor; g) from 0% to about 5% of an active active enzyme; and h) from 0% to about 25% of a dispersant polymer. Such a composition provides a pH of the wash solution from about 9.5 to about 11.5 pH adjusting control components / detergency builders The detergent compositions herein will preferably provide wash solutions having a pH of at least seven; the compositions may therefore contain a builder and pH adjuster component selected from water soluble alkaline inorganic salts and water soluble inorganic and organic builders. A pH in the wash solution is convenient from 7 to about 13, preferably from about 8 to about 12, most preferably from about 8 to about 11.0. The pH adjusting component is selected so that when the detergent composition is dissolved in water at a concentration of 2000-6000 ppm, the pH remains in the ranges considered above. The pH-free phosphate-adjusting component of the preferred embodiments of the invention is selected from the group consisting of: i) sodium / potassium carbonate or sesquicarbonate ii) sodium / potassium citrate iii) citric acid iv) sodium / potassium bicarbonate v) sodium / potassium borate, preferably borax vi) sodium / potassium hydroxide vii) sodium / potassium silicate and viii) mixtures of clauses (l) - (vii). Illustrative of the highly preferred pH adjusting component systems are the binary mixtures of granulated sodium citrate dehydrated with anhydrous sodium carbonate and the three component mixtures of sodium citrate granulated dihydrate, sodium carbonate and sodium disilicate. The amount of the pH adjusting component included in the detergent compositions is generally from about 0.9% to about 99%, preferably from about 5% to about 70%, most preferably from about 20% to about 60% by weight of the composition. Any pH adjuster system (i.e. for improved sequestration in hard water) can be supplemented by other optional builder salts selected from phosphate or non-phosphate builders known in the art., which include the various water-soluble hydroxy sulphonates, polyacetates and polycarboxylates of alkali metals, ammonium or substituted ammonium. Salts of such alkali metal materials, especially sodium, are preferred. It is possible to use non-phosphorous, water-soluble organic builders for their sequestration properties. Some examples of polyacetate builders and polycarboxylate builders are the sodium, potassium, lithium, ammonium and substituted ammonium salts of ethylenediamine tetraacetic acid, ethylene diamine disuccinic acid (especially the S, S- form); nitrilotriacetic acid, tartrate monosuccinic acid, tartrate disuccinic acid, oxydiacetic acid, oxydisuccinic acid, carboxymethyloxysuccinic acid, mellitic acid and sodium benzene polycarboxylate salts. Builders may be any of the detergency builders known in the art, including the various water-soluble phosphates, polyphosphates, phosphonates, polyphosphonates, carbonates, borates, polyhydrosulfonates, polyacetates, carboxylates (eg, citrates), aluminocilicates, and polycarboxylates. of alkali metals, ammonium or substituted ammonium. Preference is given to the above alkali metal salts, especially sodium, and mixtures thereof. Some specific examples of inorganic phosphate builders are tripolyphosphate, pyrophosphate, sodium and potassium polymeric metaphosphate having a degree of polymerization of about 6 to 21, and orthophosphate. Some examples of polyphosphonate builders are the sodium and potassium salts of ethylene diphosphonic acid, the sodium and potassium salts of ethan-1-hydroxy-1- diphosphonic acid and the sodium and potassium salts of Ethan-1, 2-triphosphonic acid. Other phosphorous builder compounds are disclosed in the U.S.A. Nos. 3,159,581; 3,213,030; 3,422,021; 3,422,137, 3,400,176 and 3,400,148, incorporated herein by reference.

The phosphate-free builders include, but are not limited to, the various water-soluble hydroxy sulphonates, polyacetates and polycarboxylates of alkali metals, ammonium or substituted ammonium. Salts of such alkali metal materials, especially sodium, are preferred. It is possible to use non-phosphorous, water-soluble organic builders for their sequestration properties. Some examples of polyacetate builders and polycarboxylate builders are the sodium, potassium, lithium, ammonium and substituted ammonium salts of ethylenediaminetetraacetic acid, ethylenediamine disuccinic acid (especially the S, S- form); nitrilotriacetic acid, tartrate monosuccinic acid, tartrate disuccinic acid, oxydiacetic acid, oxydisuccinic acid, carboxymethyloxy-succinic acid, mellitic acid and sodium benzenedicarboxylate salts. In general, the pH values of the detergent compositions may vary during the course of washing as a result of the water and dirt present. The best method to determine without any given composition has the pH values indicated herein is as if: prepare a solution and aqueous dispersion of all the ingredients of the composition by mixing them in finely divided form with the required amount of water to have a concentration of 3000 ppm. Measure the pH using a conventional glass electrode at room temperature, approximately 2 minutes after the solution or dispersion has been formed. To be more precise, this method refers to the pH measurement and should not be interpreted in any way as limiting the detergent compositions; for example, it is clearly seen that the fully formulated embodiments of the present detergent compositions can comprise a variety of ingredients applied as coatings to other ingredients.

Bleachers The detergent compositions contain an oxygen bleach source. The oxygen bleach is employed in an amount sufficient to provide from 0.01% to about 8% preferably from about 0.1% to about 5.0%, most preferably from about 0.3% to about 4.0%, most preferably even from about 0.8% to about 3% available oxygen (AvO) by weight of the detergent composition. The available oxygen of a detergent composition or a bleaching component is the equivalent bleaching oxygen content thereof expressed as% oxygen. For example, commercially available sodium perborate monohydrate typically has an oxygen content for bleaching use of approximately 15% (the theory predicts a maximum of about 16%). The methods for determining the available oxygen of a formula after its manufacture share similar chemical principles, but depend on whether the oxygen bleach incorporated herein is a simple source of hydrogen peroxide, such as perborate or sodium precarbonate, is a type activated (for example, perborate with tetra-acetyl ethylenediamine) or comprises a realized peracid, such as monoperphthalic acid. Analysis of peroxygen compounds is well known in the art: see, for example, Swern's publications, such as "Organic Peroxides", Vol. I, D. H. Swern, Editor; Wiley, New York, 1970, LC # 72-84965, incorporated by reference. See for example the calculation of "percentage of active oxygen" on page 499. This term is equivalent to the terms "available oxygen" or "percent of available oxygen" as used herein. The peroxygen bleach systems useful herein are those capable of producing hydrogen peroxide in aqueous bath. These compounds include, but are not limited to, alkali metal peroxides, organic peroxide bleaching compounds, such as urea peroxide and inorganic persal bleach compounds., such as alkali metal perborates, percarbonates, perfosphates and the like. Mixtures of 2 or more such bleaching compounds can also be used. Preferred peroxygen bleach compounds include sodium perborate, commercially available in mono-, tri- and tetra-hydrated form, sodium pyrophosphate peroxyhydrate, urea peroxyhydrate, sodium percarbonate and sodium peroxide. Particularly preferred are sodium perborate tetrahydrate, sodium perborate monohydrate and sodium percarbonate. Percarbonate is especially preferred. The oxygen type bleaches suitable in the U.S.A. patent are described in more detail. No. 4,412,934 (Chung et al.), Published on lo. November 1983, and the peroxyacid bleaches described in European Patent Application 033,259, Sagel et al., published September 13, 1989, both incorporated herein by reference, may be used. The highly preferred precarbonate may be in uncoated or coated form. The average particle size of the uncoated precarbonate ranges from about 400 to about 1200 microns, most preferably from about 400 to about 600 microns. If coated precarbonate is used, the preferred coating materials include carbonate, sulfate, silicate, borosilicate, fatty carboxylic acids and mixtures thereof. Preferably, the peroxygen bleach component was formed in the composition with an activator (peracid precursor). The activator is present at levels from about 0.01% to about 15%, preferably from about 1% to about 10%, most preferably from about 1% to about 8%, by weight of the composition. Preferred activators are selected from the group consisting of trtraacetiletylendia ina (TAED), benzoylcaprolactam (BzCL), 4-nitrobenzoyIcaprolactam, 3-chlorobenzoycaprolactam, benzoyloxybenzene sulfonate (AOBS), nonanoloxybenzene sulfonate (NOBS), phenyl benzoate (PhBz), decanoyloxybenzene sulfonate (CIO), OBS), benzolivalerolactam (BZVL), octanoyloxybenzensulfonate (Cß-OBS), perhydrolyzable esters and mixtures thereof, most preferably, benzoylcaprolactam and benzoylvalerolactam. Particularly preferred bleach activators in the pH range from about 8 to about 9.5 are those selected having an OBS or VL output group. Preferred bleach activators are those described in US Patents. 5,130,045, Mitchell et al., And 4,412,934, Chung et al., And the pending U.S. Patent Applications. Nos. 08 / 064,624, 08 / 064,623, 08 / 064,621, 08 / 064,562, 08 / 064,564, 08 / 082,270 and the pending application by M. Burns, Willey AD, RT Hartshorn, CK Ghosin, entitled "Bleaching Compounds Comprising Peroxiacid Activators Used With Enzymes "and having a US serial number 08 / 133,691 (P & G Case 4890R), all of which are incorporated herein by reference. The molar ratio of the peroxygen bleach compound (as AvO) to the bleach activator in the present invention generally ranges from at least 1: 1, preferably from about 20: 1 to about 1: 1, most preferably from about 10: 1 to about 3: 1 Whitening activators substituted with quaternary ammonium may also be included. The present detergent compositions comprise a bleach activator substituted with quaternary ammonium (QSBA) or a peracid substituted with quaternary ammonium (QSP); most preferably, the first. The preferred QSBA structures are described in more detail in the copending U.S. Patent. Nos. 08 / 298,903, 08 / 298,650, 08 / 298,906 and 08 / 298,904, published August 31, 1994, incorporated herein by reference.

Diacyl Peroxide bleaching species. The mixed particles according to the present invention may also comprise from about 1% to about 50% by weight, most preferably from about 5% to about 40% by weight, most preferably still from about 10% to about 35% by weight of the mixed group of continuous particles of diacyl peroxide insoluble in water. The individual acyl peroxide particles in the mixed body have an average particle size of less than about 300 microns, preferably less than about 200 microns, most preferably from about 1 to about 50 microns, most preferably still from about 10 to about 100 micras The acyl peroxide is preferably water-insoluble diacyl peroxide of the general formula: RC (0) 00 (0) CRi wherein R and R1 may be the same or different, and each comprises a hydrocarbyl group containing more than 10 atoms of carbon. Preferably, at least one of these groups has an aromatic core. Some examples of suitable diacyl peroxides are those selected from the group consisting of dibenzoyl peroxide, benzoyl glutaryl peroxide, benzoyl succinyl peroxide, di- (2-methibenzoyl) peroxide, diftaloyl peroxide and mixtures thereof, very preferably dibenzoyl peroxide, diftaloyl peroxides and mixtures thereof. The preferred diazyl peroxide is dibenzoyl peroxide. The diacyl peroxide is thermally decomposed under washing conditions (ie typically about 38 ° C to about 71 ° C) to form free radicals. This occurs even when the diacyl peroxide particles are dissolvable in water. Surprisingly, particle size can play an important role in the performance of diacyl peroxide, not only in the prevention of waste deposition problems, but also in the enhancement of stain removal, particularly from stained plastic articles. . The average particle size of the diacyl peroxide particles produced in wash solution after dissolution of the mixed particulate carrier material, as measured by a laser particle size analyzer (eg, Malvern) on a stirred mixture with Diacyl peroxide water is less than about 300 microns, preferably less than about 200 microns. Although insolubility in water is an essential feature of the diacyl peroxide used in the present invention, the size of the particles containing it is also important to control the formation of residue in the wash and maximize the performance of spot removal. Preferred are also the preferred diacyl peroxides used in the present compositions, forming a carrier material that melts within the range of about 38 ° C to about 77 ° C, preferably selected from the group consisting of polyethylene glycols, paraffin waxes and mixtures of them, as stated in the US patent application in process, serial number 08 / 424,132, published on April 17, 1995.

SILICATES Compositions of the type described herein optionally contain, but preferably, alkali metal silicates and / or silicates. The alkali metal silicates described hereinafter provide the ability to adjust pH (as described above) protection against corrosion of metals and against attack on tableware, inhibition of corrosion to glassware and porcelain articles. The level of SIO2 is from about 0.5% to about 20%, preferably from about 1% to about 15%, most preferably from about 2% to about 12%, most preferably still from about 3% to about 10%, based on the weight of the detergent composition. The ratio of SIO2 to alkali metal oxide (M2O), wherein M = alkali metal) is typically from about 3.2 to about 3.2, preferably from about 1 to about 3, most preferably from about 1 to about 2.4. Preferably, the alkali metal silicate is aqueous, having from about 15% to about 25% water, more preferably, from about 17% to about 20%. The anhydrous forms of alkali metal silicate with a ratio of Si? 2: M2? of 2.0 or more are less preferred because they tend to be more significantly less lumens than aqueous alkali metal silicates having the same ratio. Sodium and potassium silicates, and especially sodium, are preferred. A particularly preferred alkali metal silicate is a granular aqueous sodium silicate having an Si? 2: Na2? Ratio. from 2.0 to 2.4 available through PQ Corporation, called Britesil H20 and Britesil H24. A granular aqueous sodium silicate having an Si? 2 Na2 ratio is highly preferred. of 2.0. While typical forms, ie powders and granules, of aqueous silicate particles are suitable, the prevented silicate particles have an average particle size of between about 300 and about 900 microns with less than 40% smaller than 150 microns. and less than 5% larger than 1,700 microns. Particularly preferred is a silicate particle with an average particle size of between about 400 and about 700 microns with less than 20% smaller than 150 microns and less than 1% larger than 1,700 microns. Other suitable silicates include the crystalline layered sodium silicates having the general formula: NaMS? ? x + l * and H2 O where M is sodium or hydrogen, x is a number from 1.9 to 4 e and is a number from 0 to 20. Silo-ratified sodium silicates are decanted. in EP-A-0164514 and methods for their repair are disclosed in DE-A-3417649 and DE-A-3742043. For the purpose of the present invention, x in the above general formula has a value of 2, 3 or 4. The most preferred material is d-Na2Si2? E, available through Hoechst AG as NaSKS-6. The crystalline layered sodium silicate material is preferably present in granular detergent compositions as an intimate mix particle with a water soluble, solid ionizable material. The solid ionizable material, soluble in water, is selected from organic acids, salts of organic and inorganic acids and mixtures thereof.

Dispersing Polymers When present, a dispersing polymer in the present detergent compositions is typically present in the range of 0 to about 25%, preferably from about 0.5% to about 20%, most preferably from about 1% to about 7% by weight of the detergent composition. Dispersing polymers are also useful for the improved effectiveness of film formation of the present detergent compositions, especially the higher pH modes, such as those in which the wash pH exceeds about 9.5. Particularly preferred are polymers which inhibit the deposition of calcium carbonate or magnesium silicate on the tableware.

Dispersing polymers suitable for use herein are illustrated by the film-forming polymers described in the U.S. Patent. No. 4,379,080 (Murphy), published on April 5, 1983, incorporated herein by reference. Suitable polymers are preferably at least partially neutralized salts or of alkali metals, ammonium or substituted ammonium (for example, mono-, di- or triethanolamine) see carboxylic acids. The alkali metals, especially the sodium salts are most preferred. While the molecular weight of the polymer can vary over a wide range, it is preferably from 1,000 to about 500,000, most preferably from about 1,000 to about 250,000, and most preferably still, especially if the detergent composition is for use in washing apparatuses of American automatic devices, is from about 1,000 to about 5,000. Other suitable dispersant polymers include those described in the U.S. Patent. No. 3,308,067, published on March 07, 1967, by Diehl, incorporated herein by reference. The unsaturated monomeric acids which can be polymerized to form suitable dispersing polymers include acrylic acid, maleic acid (or maleic anhydride), fumaric acid, itaconic acid, aconitic acid, mesaconic acid, citraconic acid, and methylenemalonic acid.

The presence of monomeric segments which do not contain carboxylate radicals, such as ethyl vinyl ether, styrene, ethylene, etc., is suitable provided that such segments do not constitute more than about 50% by weight of the dispersible polymer. Acrylamide and acrylate copolymers having a molecular weight of from about 3,000 to about 100,000, preferably from about 4,000 to about 20,000, and an acrylamide content of less than about 50%, preferably less than 20%, can also be used in weight of the dispersant polymer. Most preferably still such a dispersant polymer has a molecular weight of about 4,000 to about 20,000 and an acrylamide content of about 0% to about 15%, the weight of the polymer. Particularly preferred dispersant polymers are low molecular weight modified polyacrylate copolymers. Such copolymers contain monomer conveniences: a) from about 90% to about 10%, preferably from about 80% to about 20% by weight of acrylic acid plus its salts and b) from about 10% to about 90%, preferably from about 20% to about 80% by weight of a substituted acrylic monomer or its salt and having the general formula - [(C (R2) C (R) CC (0) 0R3)] - wherein the valences incomplete within the brackets are hydrogen and at least one of the substituents Ri, R2 or R3, preferably R or R2, is an alkyl or hydroxyalkyl group of 1 to 4 carbons, Ri or R2 may be a hydrogen and R3 may be a hydrogen or alkali metal salts. The most preferred is a substituted acrylic monomer wherein R is methyl, R2 is hydrogen and R3 is sodium. The low molecular weight polyacrylate dispersing polymer has a molecular weight of less than about 15, 000, preferably from about 500 to about 10,000, most preferably from about 1000 to about 5000. The most preferred polyacrylate copolymer for use herein has a molecular weight of 3500 and is the fully localized form of the polymer comprising approximately 70% by weight of acrylic acid and approximately 30% by weight of methacrylic acid. Other suitable modified polyacrylate copolymers include the low molecular weight copolymers of unsaturated aliphatic carboxylic acids described in the U.S. Patents. 4,530,766 and 5,084,535, both incorporated herein by reference. Other dispersant polymers useful herein include polyethylene glycols and polypropylene glycols having a molecular weight of about 950 to about 30,000 obtainable through the Dow Chemical Company of Midland, Michigan. Such compounds, which have for example a melting point in the range of about 30 ° to about 100 ° C can be obtained with the molecular weights of 1450, 3400, 4500, 6000, 7400, 9500, and 20,000. Such compounds are formed by polymerization of ethylene glycol or propylene glycol with the required number of moles of ethylene or propylene oxide to provide the desired molecular weight and melting point of the respective polyethylene glycol and polypropylene glycol. Reference is made to polyethylene glycol, polypropylene glycol and mixed glycols, using the formula H0 (CH2CH20) m (CH2CH (CH3) 0) n (CH (CH3) CH20) 0H where m, n, I are integers that meet the requirements of molecular weight and temperature given above. Still other dispersing polymers useful herein include the cellulose sulfate esters, such as cellulose acetate sulfate, cellulose sulfate, hydroxyethyl cellulose sulfate, methyl cellulose 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 March 28, 1973; the dextrin esters of polycarboxylic acids described in the U.S.A. No. 3,929,107, Thompson, published November 11, 1975; the hydroxyalkyl starch ethers, starch esters, oxidized starches, dextrins and starch hydrolysates described in the U.S.A. No. 3,803,285, Jensen, published April 9, 1974; the carboxylated starches described in the U.S.A. No. 3,629,121, Eldib, published December 21, 1971; and dextrin starches described in the US patent. No. 4,541,841, McDanald, published February 27, 1979; all incorporated herein by reference. Preferred cellulose-derived dispersing polymers are carboxymethylcelluloses. Yet another group of acceptable dispersants are organic dispersant polymers, such as polyaspartate.

Low foaming nonionic surfactant The detergent compositions of the present invention may comprise low foaming nonionic surfactants (LFNIs). The LFNI can be present in amounts of 0 to about 10% by weight, preferably from about 1% to about 8%, most preferably from about 0.25% to about 4%. LFNIs are typically used in detergent compositions because of their improved action of layering on water (especially glass) that confer the product of the detergent composition. They also include non-silicone, non-phosphate polymeric materials, illustrated in detail hereinafter, which are known to defoam the food soils found in automatic dishwashing. Preferred LFNIs include nonionic alkoxylated surfactants, especially ethoxylates derived from primary alcohols and mixtures thereof with more sophisticated surfactants, such as polyoxypropylene / polyoxyethylene / poly-oxypropylene reverse block polymers. Surfactants of the polymer type PO / EO / PO are well known to have foam suppressing or defoaming action, especially in relation to the common ingredients of the food society, such as egg. The invention includes preferred embodiments in which LFNI is present and in which this component is solid at temperatures below about 37.7 ° C, most preferably below about 48.8 ° C. In a preferred embodiment, the LFNI is an ethoxylated surfactant derived from the reaction of a monohydroxy alcohol or alkylphenol containing from about 8 to about 20 carbon atoms, excluding the cyclic carbon atoms, from about 6 to about 15 mmole of oxide of ethylene per mole of alcohol or alkylphenol on an average basis. A particularly preferred LFNI is derived from a straight chain fatty alcohol containing from about 16 to about 20 carbon atoms (C 16 -C 20 alcohol), preferably a Cys alcohol, condensed with an average of from 6 to about 15 mmoles, preferably from about 7 to about 12 mmoles and most preferably from about 7 to about 9 mmoles of ethylene oxide per mole of alcohol. Preferably, the ethoxylated nonionic surfactant thus derived has a narrow distribution of ethoxylate relative to the average. The LFNI may optionally contain propylene oxide in an amount of up to about 15% by weight. Other preferred LFNI surfactants can be prepared by the methods described in the U.S.A. 4,223,163, published September 16, 1980, Builloty, incorporated herein by reference. The highly preferred detergent compositions herein in which the LFNI is present make use of ethoxylated monohydroxy alcohol or alkylphenol and additionally comprise a polyoxyethylene and polyoxypropylene block polymer compound; the attraction of alkylphenol ethoxylated monohydroxy alcohol of the LFNI comprising from about 20% to about 80%, preferably from about 30% to about 70%, of the total LFNI. Suitable polyoxyethylene-polyoxypropylene block polymeric compounds that meet the requirements described hereinbefore include those based on ethylene glycol, propylene glycol, glycerol, trimethylolpropane, and ethylenediamine as a reactive hydrogen reactant compound. Polymeric compounds made from sequential ethoxylation and propoxylation of the initiator compounds with a single reactive hydrogen atom, such as C12-18 aliphatic alcohols, do not generally provide satisfactory soap control in the present detergent compositions. Some of the block polymer surfactant compounds designated PLURONIC * and TET ONIC * by BASF-Wyandotte Corp., Wyandotte, Michigan, are suitable in the detergent compositions herein. A particularly preferred LFNI contains from about 40% to about 79% of a polyoxypropylene / polyoxyethylene / polyoxypropylene block polymer mixture comprising about 75%, by weight of the blend, of a polyoxyethylene and polyoxypropylene reverse block copolymer which contains 17 mmoles of ethylene oxide and 44 mmoles of propylene oxide; and about 25%, by weight of the mixture, of a polyoxyethylene and polyoxypropylene block copolymer initiated with trimethylolpropane and contains 99 mmole of propylene oxide and 24 mmole of ethylene oxide per mole of trimethylolpropane. Suitable for use as LFNI in detergent compositions are those LFNIs which have relatively low turbidity points and high hydrophilic-lipophilic balance (HLB). The turbidity points of the 1% solutions in water are typically less than about 32 ° C and preferably lower, for example 0 ° C, for the optimum control of suds formation over a whole range of temperatures of Water. The LFNIs that can be used also include a polyethoxylated alcohol dec, having an ethoxylation degree of about 8, commercially available as SLF18 through Olin Corp. and any biodegradable LFNI having the melting point properties considered herein. previously.

Anionic Surfactant Coagent The automatic dishwashing detergent compositions herein may additionally contain an anionic surfactant coagent. When present, the anionic surfactant coagent is typically in an amount of from 0 to about 10%, preferably from about 0.1% to about 8%, most preferably from about 0.5% to about 5%, by weight of the detergent composition. Suitable anionic surfactant coagents include branched or linear alkyl sulfates and sulfonates. These may contain from about 8 to about 20 carbon atoms. Other anionic surfactant coagents include alkylbenzene sulfonates containing from about 6 to about 13 carbon atoms in the alkyl group, and mono- and / or di-disulfonates of mono- and / or dialkylphenyl oxide wherein the alkyl groups contain about 6 carbon atoms. to approximately 16 carbon atoms. All of these anionic surfactant coagents are used as stable salts, preferably sodium and / or potassium. Preferred anionic surfactant coagents include sulfobetaines, betaines, alkyl (polyethoxy) sulfates (AES) and alkyl (polyethoxy) carboxylates which are generally high sudsing. The optional anionic surfactant coagents are illustrated in more detail in published British patent application No. 2,116,199A; the patent of E.U.A. No. 4,005,027, Hartman; the patent of E.U.A. No. 4,116,851, Rupe et al .; and the patent of E.U.A. No. 4,116,849, Leikhim, all of which is incorporated herein by reference. The alkyl (polyethoxy) sulfate surfactants comprise a primary alkylethoxy sulfate derived from the condensation product of a Cß-C alcohol alcohol with an average of from about 0.5 to about 20, preferably from about 0.5 to about 5, oxide groups. ethylene. The Cß-Ciß alcohol itself is preferably commercially available. C12-C15-acylsulfate which has been ethoxylated with about 1 to about 5 mmoles of ethylene oxide per molecule is preferred. When the compositions of the invention are formulated to have a pH between 6.5 and 9.3, preferably between 8.0 and 9, wherein the pH is defined herein as being the pH of a 1% solution of the composition measured at 20. ° C, removal of surprisingly vigorous dirt, particularly removal of protiolytic dirt, is obtained when the cyclo-Ciß alkylcytosulfate surfactant with an average degree of ethoxylation of 0.5 to 5 is incorporated into the composition in combination with a protiolytic enzyme, such as neutral or alkaline proteases at an active enzyme level of 0.005% to 2%. The alkyl (polyethoxysulfate) surfactants for inclusion in the present invention are C12-C1S alkylethylsulfate surfactants with a medium ethoxylation grade of 1 to 5, preferably 2 to 4, most preferably 3. Conventional ethoxylation procedures with catalysis at the base to produce an average degree of ethoxylation of 12 result in a distribution of individual ethoxylates ranging from 1 to 15 ethoxy groups per mole of alcohol, so that the desired average can be obtained in a variety of ways. it can make mixtures of material having different degrees of ethoxylation and / or different ethoxylate distributions originating from the specific ethoxylation techniques employed and the subsequent treatment steps, such as distillation. Suitable alkyl (polyethoxy) carboxylates for use herein include those with the formula RO (CH2CH2?)? CH2C00-M + wherein R is an alkyl group of Ce to C25, x ranges from 0 to 10, preferably selected from alkali metal, alkaline earth metal, mono-, di-, and triethanolammonium ammonium, most preferably sodium, potassium, ammonium, and mixtures thereof with magnesium ions the preferred alkyl (polyethoxy) carboxylates are those in which R is an alkyl group of C12 to Cie. The highly preferred anionic surfactant coagents herein are the sodium or potassium salt forms for which the corresponding calcium salt form has a low Kraft temperature., for example 30 ° C or less or, even better, 20 ° C or lower. Some examples of such highly preferred anionic surfactant coagents are the alkyl (polyethoxy) sulfates.

Degreasing Enzymes (including Enzyme Aids) Enzymes may be included in the present detergent compositions for a variety of purposes, including the removal of protein-based, carbohydrate-based or triglyceride-based stains from surfaces such as textiles or clutter, for the prevention of the migratory dye transfer, for example in the washing of clothes and for the restoration of the fabric. Suitable enzymes include proteases, amylases, lipases, cellulases, peroxidases and mixtures thereof of any suitable origin, for example of vegetable, animal, bacterial, fungino and yeast origin. Preferred selections are influenced by factors such as pH activity and / or stability optima, thermostability and stability to active detergents, builders and the like.

In this regard, bacterial or fungal enzymes are preferred, such as bacterial amylases and proteases and fungal cellulases. "Detersive Enzyme", as used herein, means any enzyme that has a cleansing, stain remover or otherwise beneficial effect in a detergent composition for laundry, hard surface cleaning or personal care. Preferred detersive enzymes are hydrolases, such as proteases, amylases and lipases. Preferred enzymes for laundry purposes include, but are not limited to, proteases, cellulases, lipases and peroxidases. The amylases and / or the proteases are highly preferred for automatic gum washing, including both common commercially available types and improved types which, although increasingly compatible with the bleach through successive improvements, have a remaining degree of susceptibility to deactivation of bleach. Enzymes are normally incorporated into the detergent or additive detergent compositions at levels sufficient to provide an "effective amount of cleaning". The term "effective cleaning amount" refers to any amount capable of producing a cleaning, stain remover, soil remover, whitening, deodorizing or freshness enhancing effect on substrates, such as fabrics, binders and the like. In practical terms for common commercial preparations, typical amounts are up to about 5 mg by weight, more typically 0.01 mg to 3 mg, of the active enzyme per gram of the detergent composition expressed otherwise, the compositions herein will comprise typically from 0.01% to 5%, preferably from 0.01% -1% by weight of a commercial enzyme apreparation. Protease enzymes are usually present in such commercial preparations at sufficient levels to provide 0.005 to 0.1 Anson units (AU) of program activity of the composition. For certain detergents, for example in automatic dishwashing, it may be desirable to increase the active enzyme content of the commercial preparation in order to reduce the total amount of non-catalytically active materials to amino and thereby improve staining / filming or other final results. Higher active levels in highly concentrated detergent formulations may also be desirable. Some suitable examples of proteases are the subtilisins that are obtained from particular strains of B subtilis and B. bicenifor is. An adequate protease is obtained from a Basalt ceoa. which has a maximum activity throughout the entire pH range of 8-12, developed and sold as ESPERASE "by Novo Industries A / S of Denmark, hereinafter referred to as" Novo. "The preparation of this enzyme is described. and analogous enzymes in GB 1,243,784, by Novo Other suitable proteases include LACALASER and SAVINASER from Novo and MAXATASE "from International Bio-Synthetics, Inc., The Netherlands; as well as protease A as described in EP 130,756A, of January 9, 1985, and protease B as described in EP 303,761 A, of April 28, 1987, and EP 130,7546 A, of January 9, 1985 See also a protease of high pH of basillus sp. NCIMB 40338 described in WO 9318140 A de Novo. Enzymatic detergents comprising protease one or more additional enzymes, and an irreversible protease inhibitor are described in WO 9203529 A by Novo. Other preferred proteases include those of WO 9510591 A of Procter &; Gamble. When desired, a protease having decreased adsorption and increased hydrolysis is available as described in WO 9507791 of Procter & Gamble. A recombinant protease similar to trypsin for detergents, suitable herein is described in WO 9425583 by Novo. In more detail, an especially preferred protease, referred to as "Protease D" is a carbonyl hydrolase variant having an amino acid sequence not found in nature that is derived from a precursor carbonyl hydrolase by substituting a different amino acid for a multitude of amino acid residues at a position in said carbonyl hydrolase equivalent to the +76 position, preferably also in combination with one or more amino acid residue compositions equivalent to those selected from the group consisting of +99, +101, +103 , +104, +107, +123, +27, +105, +109, +126, +128, +135, +156, +166, +195, +197, +204, +206, +210, + 216, +217, +218, +222, +260, +265 and / or +274, according to the numbering of the subtilisin of Bacillus amyloloquefacies, as described in the patent applications of A. Baeck et al., Entitled "Protease-Containing Cleaning Compositions" that have the US serial number 08 / 322,676, and C. Ghosh et al., "BLeaching Compositions Comprising Protease Enzymes" which has the serial number of E.U.A. 08 / 322,677, both filed on October 13, 1994. Suitable amylases herein, especially for, but not limited to, tack-washing purposes, include, for example, a-amylases described in GB 1,296,839 of Novo.; RAPIDASE ", International Bio-Synhetics, Inc. and TERMAMIYR Novo, FUNGAMYLR from Novo is especially useful Engineering of enzymes for improved stability, for example oxidative stability, is known, see, for example, J. Biological Chem., Vol. 260, No. 11, June 1985, pp 6518-6521 Certain preferred embodiments of the present compositions can make use of amylases having improved stability in detergents, as measured against a reference point of TERMAMYLR in commercial use in 1993. These preferred amylases of the present share the characteristic of being "enhanced in stability" amylases, characterized, at least, by a measurable improvement in one or more of: oxidative stability, for example to hydrogen peroxide / tetracetylenediamine in solution regulated in its pH at 9-10, thermal stability, for example at common wash temperatures, such as about 60 ° C, or alkaline stability, for example at an approximate pH 8 to approximately 11, measured with respect to the amylase of the previously identified reference point. The stability can be mediated using any of the technical tests described in the art. See, for example, the references described in WO 9402597. The amilsas enhanced in their stability can be obtained through Novo or Genencor International. A class of highly preferred amylases herein have the common feature of being derived using site-directed mutagenesis of one or more of the Bacillus ilases, especially the Bacillus α-amylases, regardless of whether one, two or multiple amylase strains. they are the immediate precursors. Oxidative amylases enhanced in their stability with respect to the above-identified reference amylase are preferred for use, especially in bleaching, most preferably oxygen bleaching detergent compositions, so different from chlorine bleaching, of the present. Preferred amylases include (a) an amylases according to WO 9402597, Novo, of February 3, 1994, previously ineffective herein, as illustrated in more detail by a mutant in which substitution is made, using alanine or trionine, preferably trionine of the methionine residue located at position 197 of the α-amylase of B. licheniformis. known as TERMAMYLR, or the position variance of an original or similar amylase, such as B. amyloliquefaciens, B. subtilis or B. stearithermophilus; (b) the amylases enhanced in their stability described by Genencord International in a document entitled "Oxidatively Resistant alpha-Amylases" presented at the 207 National Meeting of the American Chemical Society, from March 13 to 17, 1994 by C. Mitchison. There, it was observed that the bleaches and detergents for automatic dishwashing inactivate alpha-amylases, but that amylases of improved oxidative stability have been obtained by Genencor from NCIB8061 of B. licheniformis. Methionine (Met) was identified as the most likely residue to be modified. Methionine was substituted, 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 variant M197T being the variant expressed in a more stable form . The stability was measured in CASCADER and SUNLIGHTR; (c) Particularly preferred amylases of the present invention include amylase variants having further modification in the immediate parent molecule as described in WO 9510603 A and are available from the parent, Novo, as DURAMYLR. Other particularly preferred amylases of improved oxidative stability include those described in WO 9418314 by Genencor International and W0 9402597 by Novo. Any other amylase of improved oxidative stability can be used, for example, those which are derived by site-directed mutagenesis from original hybrid or simple chimeric mutant forms of available amylases. Other preferred enzyme modifications are accessible. See WO 9509909 A, by Novo. The cellulases usable in the present invention include types derived from fungi and bacteria, preferably having an optimum pH between 5 and 9.5. US 4,435,307 by Barbesgoard et al., March 6, 1984, describes suitable cellulases of fungi of the species Humicola insolens or of strain DSM1800 of Humicola, or of a fungus producing cellulase 212 belonging to the genus Aeromonas, and the cellulase extracted from the hepatopancreas of a marine mollusk, Dolabella auricula solander. Suitable cellulases are also described in GB-A-2,075,028; GB-A-2,095,275 and DE-0S-2,247,832. CAREZYMER (Novo) is especially useful. See also WO 9117243, by Novo. Lipases suitable for use in detergents include those produced by microorganisms of the Pseudomonas group, such as ATCC 19,154 of Pseudomonas stutzeri, as described in GB 1,372,034. See also lipases in Japanese Patent Application 53,20487, filed on February 24, 1978. This lipase is available from Amano Pharmaceutical Co. Ltd., Nagoya, Japan, under the tradename of Lipase P "Amano, "or" Amano-P ". Other commercially suitable lipases include A ano-CES, Chromobacter viscosum lipases, for example, NRRLB 3673 from Chromobacter viscosum var. lipolyticum from Toyo Jozo Co., Tagata, Japan; Chromobacter viscosum lipases from E.U.A .. Biochemical Corp., E.U.A .. and Disoynth Co., Holland, and lipases from Pseudomonas gladioli. The LIPLASER enzyme derived from Humicola lanuginosa and commercially available from Novo, see also EP 341,947, is a preferred lipase for use in the present invention. Stabilized lipase and amylase variants against peroxidases are described in WO 9414951 A, by Novo. See also WO 9205249 and RD 94359044. Cutynase enzymes suitable for use in the present invention are described in WO 8809367 A, by Genencor. Peroxidase enzymes may be used in combination with oxygen sources, for example, percarbonate, perborate, hydrogen peroxide, etc., for "solution bleaching" or prevention of transfer of dyes or pigment removed from substrates during washing to other substrates present in the the washing solution. Known peroxidases include horseradish peroxidase, ligninase and haloperoxidases, such as chloro- or bromo-peroxidase. Peroxidase-containing detergent compositions are described in WO 89099813 A, of October 19, 1989 by Novo and WO 8909813 A, by Novo. A range of enzyme materials and means for their incorporation into synthetic detergent compositions is also described in WO 9307263 A, and in WO 9307260 A by Genencor International, WO 8908694 A by Novo, and E.U.A. 3,553,139, dated January 5, 1971 by McCarty and others. Other enzymes are described in US Pat. No. 4,101,457, Place et al., July 18, 1978, and in US Pat. No. 4,507,219, Hughes, March 26, 1985. Useful enzyme materials for liquid detergent formulations, and their incorporation in said formulations are described in US 4,261,868, by Hora et al., April 14, 1981. Enzymes used in detergents can be stabilized by various techniques. Enzyme stabilization techniques are described and exemplified in document E.U.A .. 3,600,319, of August 17, 1971, by Gedge et al., EP 199,405 and EP 200,586, of October 29, 1986, by Venegas. Enzyme stabilization systems are also described, for example, in document E.U.A. 3,519,570. A useful bacillus, the AC13 species, which produces proteases, xylanases and cellulases, is described in WO 9401532 A, by Novo.

Enzyme Stabilizer System - Enzyme stabilizer systems of the present invention that contain enzymes and that include, but are not limited to, liquid compositions, may comprise from about 0.001% to about 10%, preferably from about 0.005% to about 8%, more preferably from about 0.01% to about 6%, by weight of an enzyme stabilizer system. The enzyme stabilizing system can be any stabilizing system that is compatible with the detersive enzyme. Said system can be provided inherently by other active agents of the formulation, or it can be added separately, for example, by the for ulator or by the manufacturer of detergents containing enzyme. Said stabilizer systems may comprise, for example, calcium ion, boric acid, propylene glycol, short chain carboxylic acids, boronic acids, and mixtures thereof, and are designed to highlight different stabilization problems, depending on the type and physical form of the stabilizer. the detergent composition. A stabilizing system is the use of water-soluble sources of calcium and / or magnesium ions in the finished compositions that provide said ions to the enzymes. Calcium ions are generally more effective than magnesium ions, and are preferred in the present invention if only one type of cation is being used. Typical detergent compositions, especially liquid, will comprise from about 1 to about 30, preferably from about 2 to about 20, more preferably from about 8 to about 12 millimoles of calcium ion per liter of finished detergent composition, although certain variations depending on factors that include the multiplicity, type and levels of enzymes incorporated. Water-soluble calcium or magnesium salts are preferably used, including for example calcium chloride, calcium hydroxide, calcium formate, calcium alato, calcium maleate, calcium hydroxide and calcium acetate; Generally, magnesium salts or calcium sulfate corresponding to the calcium salts exemplified can be used. In fact, more increased levels of calcium and / or magnesium may be useful, for example to promote the short action of certain types of surfactant. Another eetatema etabilizer is the use of borate species. See Severson, E.U.A .. 4,537,706. Borate stabilizers, when used, may be at levels of up to 10% or more of the composition, although more typically, levels of up to about 3% by weight of boric acid or other compounds of borate talee such as borax or orthoborate eon Suitable for use in liquid detergents. Boric acids subetituidoe talee such as phenylboronic acid, butanoboronic acid, p-bromophenylboronic acid, and eimilares, can be used in place of boric acid, and reduced levels of total boron in the detergent compositions can be made possible by the use of said sub-boron boron derivative. The stabilizer seeds of certain cleaning compositions, for example, automatic dishwashing compositions, may further comprise from 0 to about 10%, preferably from about 0.01% to about 100% by weight, of chlorine bleach scavengers, added to prevent chlorine bleach species present in many water supplies from attacking and inactivating enzymes, especially under alkaline conditions. Even though the chlorine levels in the water may be small, typically in the range of about 0.5 ppm to about 1.75 ppm, the available chlorine in the total volume of water that comes in contact with the enzyme, for example during the washing of fabrics or tableware, can be relatively large; consequently, the stability of the enzyme to chlorine is problematic. Since perborate or percarbonate, which have the ability to react with chlorine bleach, may be present in some of the compositions in amounts determined separately by the stabilizer system, the addition of ethanol stabilizer against chlorine may Generally, it is not essential, although a better result can be obtained. The appropriate chlorine scavenging anions are widely known and readily available and, they are used, they can be made up of ammonium cations with sulfite, bisulfite, thiosulphite, thioeulfate, iodide, etc. In the same way, antioxidants can be used as carbamate. , aecorbate, etc., organic amines such as ethylenediamine tetraacetic acid (EDTA) or alkali metal salts of the ismoe, monoethanolamine (MEA), and mix thereof. In the same way, special enzyme inhibition systems can be incorporated, so that different enzymes have maximum compatibility. If desired, another conventional barrier can be used, such as bisulfate, nitrate, chloride, hydrogen peroxide source such as sodium perborate tetrahydrate, sodium perborate monohydrate and sodium percarbonate, as well as phosphate, concomitant phosphate, acetate, benzoate, citrate, formate, lactate, malate, tartrate, ealicylate, etc., and mixtures thereof. In general, since the chlorine scavenging function can be performed per ingredient included per part under better recognized functions, (eg, hydrogen peroxide sources), there is no absolute requirement to add a separate chlorine scavenger, unless that a compound that performs that function to the desired degree is absent from an embodiment of the invention that contains enzyme; Even so, the sweeper is added only for optimal results. In addition, the formulator will exercise the normal dexterity of a chemical to avoid the use of any enzyme scavenger or stabilizer that is primarily incompatible, as formulated, with other reactive ingredients, if used. In relation to the use of ammonium saltse, said salts can be simply mixed with the detergent composition, but are subject to absorbing water and / or releasing ammonia during storage. Accordingly, said materials, if present, are conveniently protected in a particle such as that which is described in US 4,62,392, by Bagineki et al.

Phosphate and silicone ether foam suppressors The detergent compositions optionally contain an alkyl phosphate ester foams suppressant, a silicone foams suppressor, or combinations thereof. The levels in general are from 0% to about 10%, preferably from about 0.001% to about 5%. Typical levels tend to be low, for example from about 0.1% to about 3% when using a foaming suppressor of eylicon. Preferred compositions that do not contain foethate completely omit the ether component of foethate. The technology of silicone euphoric euphorors and other defoaming agents useful in the present invention are documented extensively in "Defoaming, Theory and Industrial Applications," Ed., PR Garrett, Marcel Dekker, NY, 1973, ISBN 0-8247-8770 -6, incorporated in the present invention as reference. See especially the chapters entitled "Foam Control in Detergent Products" (Ferch et al.) And "Surfactant Antifoams" (Blease et otroe). See also Lae Patentee of E.U.A. 3,933,672 and 4,136,045. The highly preferred silicone foam suppressants are the known mixed types which are used in laundry detergents as high performance granules, although the types hitherto used only in high performance liquid detergents can also be incorporated in the present compositions. For example, they can be used as a polydimethyleryloxane eilicon having an alternating terminal blocking unit or t? ethyleryl. They can be mixed with silicone and / or surfactant components that do not contain silicone, as exemplified by a foam supplier comprising 12% silicone / silica, 18% stearyl alcohol and 70% starch in granular form. A suitable commercial source of silicone active compounds is Dow Corning Cof. The levels of the foam supplier depend, to some degree, on the eupreerate tendency of foams in the composition; for example, a detergent composition for use at 2000 ppm comprising 2% octadecyldimethylamine oxide may not require the presence of a foam eupherer. Furthermore, an advantage of the present invention is that it allows to select amine oxides for effective cleaning which exhibit an inherently much less tendency in the formation of foams than the typical amine coconut oxides. In contrast, the formulations in which the amine oxide is combined with a high foaming anionic surfactant coagent, for example, alkyl ethoxy-sulfate, are greatly benefited by the prerequisite of foam suppressor. It has also been claimed that the nature of foetura provide some protection to the surface of silver uteneilium and coated with silver; However, the present compositions can provide excellent care for silverware without 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 an essential amine oxide, contribute to an improved care of silver utensils. If it is not desired to use a phosphate ester, suitable compounds are described in the patent of US Pat. 3,34,891. filed on April 18, 1967, by Shmolka et al., incorporated herein by reference. Preferred alkyl phosphate ethers contain 16 to 20 carbon atoms. Highly preferred alkyl phosphate esters are monostearyl foethac acid or monooleyl foethac acid, or ealloe of the mers, particularly alkali metal salts, or mixtures thereof. It has been found preferable to avoid the use of soap and precipitate calcium precipitate as anti-foam in the present compositions, since they tend to deposit on the ware. In addition, the ethers of phosphate are not totally free of such problems, so the formulator will generally choose to minimize the antifoam content potentially depoeted in the present compositions.

Corroeion inhibitor Lae detergent compositions may contain a corrosion inhibitor. Said corrosion inhibitor is a preferred component of automatic dishwashing compositions according to the invention, and will preferably be incubated at a level of from about 0.05% to 10%, preferably from 0.1% to 5% by weight of the total composition. Suitable corrogonion inhibitors include paraffin oil, typically a predominantly branched aliphatic hydrocarbon having a number of carbon atoms on the scale of 20 to 50: preferred paraffin oil selected from predominantly branched C S-45, with a ratio of of cyclic hydrocafides: non-cyclic of about 32:68; a paraffin oil which satieface eetae is marketed by Winterehall, Salzbergen, Germany, under the trade name of WINOG 70. Another suitable inhibiting component of corrode and include benzotriazole and any derivative of the mieme, ercaptanoe and diolee, especially mercaptan with 4 to 20 atoms. of coffee, including lauryl mercaptan. thiophenol, tione tol, tionalide and thioanthranol. Also suitable are C 12 -C 20 fatty acids or salts, especially aluminum tristearate. Hydroxy acids of C12-C20, or eue ealee, are also suitable. The foefonated octadecane and other antioxidants such as betahydroxytoluene (HT) are also suitable.

Other optional adjuvant Depending on whether more or less compaction is required, fillers may also be present in the detergent compositions of the present invention. These include sucrose, sucrose starch, eodium chloride, sodium sulfate, potassium chloride, potassium sulfate, etc., in amounts up to about 70%, preferably from 0% to about 40% of the detergent composition. A preferred filler is sodium sulfate, especially in good grades which have at very low levels of impurities. The sodium sulfate used in the present invention preferably has a high purity to assure that it is not reactive with the bleach; It can also be treated with low levels of sequestrants, talee as foefonatoe in the form of magneal eal. Note that the preferences, in terms of sufficient purity to avoid bleach decomposition, also apply to builders. Hydrophilic materials such as eodium benzene sulfonate, sodium toluene sulphonate, emethylene cumene sulphonate, etc., can be prepared in small quantities. Perfume is available to the bleach (eetablee to have aroma); and coloring to the bleach (such as those described in U.S. Patent 4,714,562, by Roselle et al., filed December 22, 1987), may also be added to the present compositions in appropriate amounts. Other common ingredients of the detergent composition are not excluded. Since certain detergent compositions of the present invention may contain water-sensitive ingredients, for example, in embodiments comprising anhydrous amine oxide or anhydrous citric acid, it is desirable to keep the free moisture content of the detergent compositions at a minimum, for example. 7% or less, preferably 4% or less, of the detergent composition; and provide a package that is subetancialmente impervious to water and carbon dioxide. Plastic bottles, including recirculatable or refillable types, as well as conventional packaging or barrier boxes, generally suitable. When the ingredients are not highly compatible, for example, mixtures of silicate and citric acid, it may be convenient to also coat at least one of said ingredients with a low-surfactant surfactant for protection. There are numerous waxy materials that can be easily used to form coated particles suitable for any of said otherwise incompatible component.Cleaning method The detergent compositions of the present invention can be used in cleaning dirty dishes. A preferred method comprises contacting the dishes with an aqueous washing medium having a pH of at least 8. The aqueous medium comprises at least about 0.1 ppm of oxygen-bleached bleach catalyst from a peroxygen bleach. The bleach catalyst is added in the form of the particles described in the present invention. A preferred method for cleaning dirty dishes comprises using the particles containing bleach catalyst, enzyme, low foam forming surfactant, and builder. The aqueous medium is formed by dissolving a detergent in a solid form for the automatic washing of dishes in a machine for the automatic washing of dishes. A particularly preferred method also includes low eylicate level, preferably from about 3% to about 10% SiO 2.

EXAMPLES The following examples are illustrative of the present invention. These examples are not intended to limit or otherwise define the scope of the invention. All parts, percentages and ratios used in the present invention are expressed as percent by weight, unless otherwise specified.

EXAMPLE I Flakes containing defined particles of cobalt catalyst (for example, pentaaminoacetatecobalt (III) nitrate, referred to herein as "PAC", preparer as described above) and PEG 8000 as carrier, are obtained as eigue, in accordance with the present invention: 960 gram of polyethylene glycol of molecular pee 8000 (PEG 8000, marketed by BASF as Pluracol E-8000) are placed in a 1,895-liter plastic barrel, and heated in a microwave over a high setting for 7 minutes to melt the PEG 8000. The PEG is agitated to ensure consistency. uniform and complete fusion. The final temperature of the molten PEG 8000 is 61 ° C. 40 grams of cobalt catalyst [pentaaminoacetatecobalt (III) nitrate, prepared as described above] are slowly added to molten PEG 8000. This mixture is stirred with a spatula for 3 minutes to evenly dispel the powder in the molten PEG. Immediately, the entire mixture is poured into the grip of a twin cylinder cooling roller. The following is valued on the cooling roller in the following: space: .015 mm speed: 50 fm water temperature 13 ° C (cold water of the tap) the leaflets formed on the cooling roller and are wiped off by the use of a bieturí in a tray, and collected. The flakes are then reduced in size by the use of a Quadro Co-mil mill, which is a cone mill form, with a sieve having an aperture of 1 mm. Lae small-sized flakes are then sieved in 200-gram slices using a Tyler 28 sieve, a Tyler 65 sieve and a pan on a Rotap. The portion that passes through the Tyler 28 sieve, but is retained in the Tyler 65 sieve, is collected as an acceptable leaflet. The composition of the resulting leaflet ee: PEG 8000 96% cobalt catalyst 4% A similar procedure can be used starting with PEG 4000 instead of PEG 8000 to obtain particles of PEG 4000 / cobalt catalyst (96% / 4%). A similar procedure using 800 grams of PEG 8000, 120 grams of sodium sulfate and 80 grams of cobalt catalyst, produces a flake particle that has: PEG 8000 80% cobalt catalyst 8% sodium sulfate 12% EXAMPLE II The granular detergent compositions for automatic dishwashing according to the invention, on as follows: TABLE I% in peeo Ingredients A B Sodium citrate (as anhydrous ingredient) 29.00 15.00 15.00 Acusol 480N1 (as an active ingredient) 6.00 6.00 6.00 Cafonato de eodio - 17.50 20.00 Briteeil H20 (as SÍO2) 17.00 8.00 8. 00 1-hydroxyethylidene-1,1-diphephonic acid 0.50 1.00 0. .50 Nonionic non-ionic agent2 - - Nonionic non-ionic agent3 1.50 2.00 1.50 Savinaee 12T 2.20 2.20 2.20 Termamyl 60T 1.50 - 0. 75 Duramyl - 1.50 PeForato monohydrate (as AvO) 0.30 2.20 2.20 Pe Fo rato tet rahid ratado (as AvO) 0.90 Pa plate of catalyzed r * 2.00 2.00 2.00 TAED 3.00 Diethylenetriamine pentamethylene phosphonic acid 0.13 0.13 Pa rafina 0.50 0.50 0.50 Benzotriazole 0.30 - 0.30 Sulfate, water, etc. balance Dispersant of Rohm and Haas 2 Surfactant Poly Tergent SLF-18 of Olin Coforation 3 Surfactant Plurafac LF404 from BASF. * The cobalt catalyst of Example I, which has 96% PEG 8000 and 4% cobalt PAC catalyst.

EXAMPLE III The detergent compositions are granulated for automatic dishwashing in accordance with the present invention, and are included as shown in Table 2: TABLE 2% in peeo Ingredients D Sodium time (as anhydrous reagent) 15.00 15.00 15.00 Acueol 480N1 (as active active network) 6.00 6.00 6.00 Eodium carbonate 20.00 20.00 20.00 Briteeil H20 (as Si? 2) 8.00 8.00 8.00 1-Hydroxyethylene-1,1-diphosphonic acid 1.00 1.00 1.00 Nonionic surfactant2 2.00 2.00 2.00 Savinaee 6T 2.00 2.00 2.00 2.00 2.00 2.00 2.00 Savinaee 6T 2.00 2.00 2.00 Termamyl 60T 1.00 1.00 Duramyl * - - 1.00 Dibenzoyl peroxide (active) 0 0.8800 - 0.80 PeForate monohydrate (as AvO) 2 2..2200 2 2..2200 1.50 Catalyst particle3 22..0000 22..0000 1.00 Sulphate, water, etc. balance i Dispersant from Rohm and Haas 2 Surfactant Poly Tergent SLF-18 from Olin Coforation 3 The cobalt catalyst of Example I, which has 96% PEG 8000 and 4% cobalt PAC catalyst. * Amylase provided by Novo Nordisk; can be replaced by OXAmylase provided by Genencor International.

EXAMPLE IV The detergent compositions granulate for the automatic dishwashing, in accordance with the present invention, are included as shown in Table 3: TABLE 3 % peeo Ingredients (a H I Sodium citrate (as anhydrous redient) 10.00 15.00 20.00 Acusol 480N1 (as active active ingredient) 6 6.0000 6 6..0000 6.00 Ca Sodium Fonate 1155..0000 1100..0000 5.00 T ripol ifoefato de eodio 1100..0000 1100..0000 10.00 Bri teei l H20 (as SiO-2) 8.00 8.00 8.00 1-hydroxyethylene-1,1-diphosphonic acid 1.00 1.00 1.00 Non-ionic surface active agent2 2 2..0000 2 2..0000 2.00 Savinaee 12T 2 2..0000 2 2..0000 2.00 Termamyl 60T 1 1..0000 1 1..0000 1.00 Dibenzoyl peroxide (active) 0 0.8888 0 0.8800 0.80 PeForate Monohydrate (as AvO) 11..5500 11..5500 1.50 Catalyst particle3 11.0000 11.0000 1.00 TAED - 2.20 Sulphate, water, etc. Dielectric balance of Rohm and Haas 2 Surfactant Poly Tergent SLF-18 from Olin Coforation 3 The cobalt catalyst of Example I, which has 96% PEG 8000 and 4% cobalt PAC catalyst.

Claims (20)

NOVELTY OF THE INVENTION CLAIMS

1. - A mixed particle containing bleach catalyst suitable for incorporating it into granular detergent compositions, said mixed particle comprising: (a) from about 1% to about 60% bleach catalyst; and (b) from about 40% to about 99% of carrier material that melts within the range of about 38 ° C to about 77 ° C.

2. Lae particles mixtae containing bleach catalyst according to claim 1, characterized in that the carrier material is selected from the group consisting of polyethylene glycol, paraffin waxes, and mixtures thereof; and further characterized in that said mixed particles have an average particle size of from about 200 to about 2400 micra.

3. Lae mixed particles containing bleach catalyst according to claim 2, characterized in that the carrier material is selected from the group consisting of polyethylene glycols having a molecular weight of about 2000 to about 12000. 4.- Lae particle mixtae containing bleach catalyst according to claim 1, characterized in that the bleach catalyst is selected from the group that you connected with cobalt bleach catalysts. 5. The mixed particles containing bleach catalyst according to claim 4, characterized in that the bleach catalyst is selected from the group consisting of cobalt (III) bleach catalysts having the formula: [C? (NH3) n (M) m (B) b] Typed because the cobalt is in the +3 oxidation state; n ee 4 or 5; I have one or more ligands coordinated with the cobalt by one site; is 0, 1 or 2; B is a ligand coordinated with cobalt at two sites; b is 0 or 1, and when b = 0, then m + n = 6, and when b = l, then m = 0 and n = 4; and T is one or more counterions appropriately selected preeentee in a number y, where y ee an integer to obtain a salt balanced in loads; and further characterized in that said catalyst has a low water velocity hydrolytic conectant of 0.23 M ~ 1 s-1 (25 ° C). 6. Lae particle mixee containing bleach catalyst according to claim 4, wherein the bleach catalyst is selected from the group consisting of cobalt pentaamine chloride salt, cobalt pentaamine acetate ealee, and mixed of the same. 7. A mixed particle containing bleaching catalyst suitable for incubating it in granular detergent compositions, said mixed particle comprising: (a) from about 1% to about 60% of a bleaching catalyst having the formula [Co (NH3) s0Ac] Ty, characterized in that OAc repre- sents a portion of acetate, and that one or more of the appropriate counterparts are present in a number and, where y is an integer to obtain a balanced equilibrium in charge; and (b) from about 40% to about 99% polyethylene glycol carrier material that melts within the range of about 38 ° C to about 77 ° C; and further characterized in that said mixed particles have an average particle size of about 200 to about 2400 microns. 8. The mixed particles containing bleach catalyst according to claim 7, characterized in that the carrier material is selected from the group consisting of polyethylene glycols having a molecular weight of about 2000 to about 12000. 9.- Lae particle mixtae containing bleach catalyst according to claim 7, characterized in that the bleach catalyst is selected from the group consisting of [Co (NH 3) sOAc 3 Cl 2; CCo (NH3) 50Ac] (0Ac) 2; [Co (NH3) s0Ac] (PFβ) 2; [Co (NH3) s0Ac] (SO4); [Co (NH3) sOAc] (BF?) 2; [Co (NH3) s0Ac] (N03) 2; and mix of them. 10. A process for the preparation of mixed particles containing bleaching catalyst suitable for incubating them in granular detergent compositions, said method comprising the steps of (a) combining a bleach catalyst particle with a molten carrier material that is melted within the range of about 38 ° C to 77 ° C, while stirring the resulting combination of particle- vehicle to form a substantially uniform mixture of the particles and the vehicle material; (b) cooling the particle-carrier mixture of the pae (a) to form a solidified mixture of particle and carrier material; and (c) working in addition to the mixture of solidified particle-vehicle material formed in step (b), as necessary to form the desired mixed particles. 11. A process according to claim 10, characterized in that the mixed particles that are formed comprise from about 1% to 60% by weight of the bleach catalyst particles selected from cobalt bleach catalysts and from about 40% by weight. % to 99% by weight of the vehicle material. 12. A process according to claim 11, characterized in that: the bleach catalyst is selected from the group consisting of cobalt (III) bleach catalysts having the formula: characterized in that the cobalt is present in the oxidation state + 3; n ee 4 or 5; I am one or more ligand coordinated with cobalt for one year; ee 0, 1 or 2; B is a ligand coordinated with cobalt at two sites; b is 0 or 1, and when b = 0, then m + n = 6, and when b = l, then m = 0 and n = 4; and T one or more counterions appropriately selected preeentee in a number y, where y is an integer to obtain a balanced salt in charges; and further characterized in that said catalyst has a base hydrolysis rate constant of less than 0.23 M ~ 1 s-1 (25 ° C). 13. A process according to claim 12, characterized in that the bleach catalyst is selected from the group consisting of [Co (NH3) sOAc] Cl2; [Co (NH3) d0Ac] (0Ac) 2; [Co (NH3) sOAc] (PF6) 2; [Co (NH3) 5? Ac] (S? 4); [Co (NH3) s0Ac] (BF?) 2; [Co (NH3) eOAc] (N03) 2; and mix of the same; and further characterized in that the carrier material is selected from the group consisting of polyethylene glycols having a molecular weight of from about 2000 to about 12,000. 1

4. A process according to claim 10, characterized in that the pae (b) of The solidification / solidification comprises introducing the mixture of step (a) onto a cooling roller or cooling band to thereby form a layer of solid material on the roller or band. 1

5. A process according to claim 14, characterized in that the solid material on the cooling roller or the cooling band is removed and further worked by grinding to form a mixtae particle in the form of leaflets having the average size of desired particle. 1

6. The mixed particles containing bleach catalyst prepared by a process according to claim 10. 1

7. The mixed particles containing bleach catalyst prepared by a process according to claim 13. 18.- A detergent composition granular, especially suitable for use in automatic dishwashing machines, whose composition comprises by weight: (a) from about 0.1% to about 10% of the lae particle and mixtae containing bleach catalyst, according to claim 1; (b) a bleach component comprising from about 0.01% to about 8% as the oxygen available from a peroxygen bleach; (c) from about 0.1% to about 60% of a pH adjusting component consisting of water-soluble salt or salt / builder mixture selected from sodium capropate, sodium hydroxide, sodium citrate, citric acid , sodium bicarbonate, sodium hydroxide, and mixtures thereof; (d) from about 3% to about 10% eilicate as SIO2; (e) from 0 to about 10% of a nonionic nonionic surfactant with low foam formation different from amine oxide; (f) from 0 to about 10% of a suds suppressor; (g) from 0% to about 5% of an active detective enzyme; and (h) from 0% to about 25% of a dietary polymer. 19. A granular detergent composition especially suitable for use in automatic machine for dishwashing, whose composition comprises by weight: (a) from about 0.1% to about 10% of the mixtae particles containing bleach catalyst, in accordance with claim 1; (b) a bleach component comprising from about 0.01% to about 8% as the oxygen available from a peroxygen bleach; (c) from about 0.1% to about 60% of a pH adjusting component consisting of water-soluble salt or salt / detergent builder mixture selected from sodium caFonate, sodium seeker sodium, sodium citrate, citric acid , sodium bicarbonate, sodium hydroxide, and mixtures thereof; (d) from about 3% to about 10% eilicate as SIO2; (e) from 0 to about 10% of a nonionic nonionic surfactant with low foam formation different from amine oxide; (f) from 0 to about 10% of an eupressor of eepumas; (g) from 0% to about 5% of an active detersive enzyme; and (h) from 0% to about 25% of a dispersant polymer; characterized in that said composition provides a pH of wash solution of from about 9.5 to about 11.5. 20. A granular detergent composition especially suitable for use in automatic dishwashing machines, whose composition comprises by weight: (a) from about 0.1% to about 10% of the mixed particles containing bleaching catalyst, in accordance with with claim 1; (b) a bleach component comprising from about 0.01% to about 8% as available oxygen from a peroxygen bleach; (c) from about 0.1% to about 60% of a pH adjusting component consisting of water-soluble salt or salt / detergent builder mixture selected from sodium caFonate, sodium seeker sodium, sodium citrate, citric acid , sodium bicarbonate, eodium hydroxide, and mixtures thereof; (d) from about 3% to about 10% eilicate as SIO2; (e) from 0 to about 10% of a nonionic nonionic surfactant with low foam formation other than amine oxide; (f) from 0 to about 10% of a suds suppressor; (g) from 0% to about 5% of an active detective enzyme; and (h) from 0% to about 25% of a dieperatant polymer; characterized in that said composition provides a pH of wash solution of from about 9.5 to about 11.5.