MXPA01008463A - Automatic dishwashing compositions comprising mixed surfactants systems - Google Patents

Abstract

Automatic dishwashing detergent compositions comprising a mixed surfactant system comprising a low foaming nonionic surfactant with an X/Y number of greater than 1.00 and an oxide surfactant.

Description

COMPOSITIONS FOR AUTOMATIC WASHING OF DISHES COMPRISING SYSTEMS OF MIXED SURFACTANT AGENTS TECHNICAL FIELD The present invention pertains to the field of automatic dishwashing detergents comprising surfactants and preferably bleach.

BACKGROUND OF THE INVENTION Automatic dishwashing, particularly in household appliances, is a very different technique from laundry. Household laundry is usually done in machines built with multiple purposes that have revolving action. These are very different from the domestic automatic dishwashing appliances for spray action. The spray action in the latter tends to produce foam. The foam can easily overflow the edges of domestic dishwashers and slow down the spray action, which in turn reduces the cleaning action. Thus, in the singular household dishwashing dish washing field, the use of common laundry detergent surfactants which produce foam is normally restricted. These aspects are just a brief illustration of the unique formulation constraints in the domestic dishwashing field. Automatic dishwashing with bleaching chemicals is different from the bleaching of fabrics. In the automatic dishwashing, the use of bleaching chemicals involves the promotion of removal of dirt from the dishes, although bleaching of dirt may also occur. In addition, the effects of antiredeposition of dirt and antiforming of spots are convenient. Some bleaching substances (such as a source of hydrogen peroxide, alone or together with tetraacetylethylenediamine, also known as "TAED"), under certain circumstances, can be helpful in cleaning dishes. Considering the previous technical restrictions as well as the needs and demands of the customer, the automatic dishwashing compositions (ADD) are undergoing continuous changes and improvements. Moreover, environmental factors such as the restriction of phosphate, the desire to provide better and better results in the elimination of stains and films with less product, provide less thermal energy and less water to aid the washing process, all have the need for compositions ADD improved. Despite such continuous changes in the formulation of ADD compositions, there remains a need for better cleaning ADD compositions, especially for the removal of stains and films. Typically, in other types of cleaning compositions such as laundry detergent compositions, cleaning improvements are continually being made by changing and improving the surfactants used. However, as noted above, the ADD compositions have the unique limitation of requiring very low foaming compositions which is not compatible with most of the surfactant systems and ingredients typically used in other cleaning compositions. In this way, the need for ADD compositions that provide stain reduction benefits without unacceptably high foaming persists.

TECHNICAL BACKGROUND Patent of E.U.A. 4,272,394, WO 94/22800 and WO 93/04153.

BRIEF DESCRIPTION OF THE INVENTION It has now surprisingly been found that automatic dishwashing detergent compositions ("ADD") comprising detergency builder and a select nonionic surfactant system, preferably further comprising a bleaching agent and / or enzymes, provide reduction benefits. of upper spots. Therefore, the present invention encompasses automatic dishwashing detergent compositions comprising: a) from about 5% to about 90% (preferably from about 5% to about 75%, most preferably from about 10% to about 50%) by weight of the composition of a builder (preferably phosphate or non-phosphate builder systems containing citrate and carbonate). b) from about 0.1% to about 15% (preferably from about 0.2% to about 10%, most preferably from about 0.5% to about 5%) by weight of the composition of an oxide surfactant, said oxide surfactant being selected from the group consisting of amine oxides, phosphine oxides, silfoxides and mixtures thereof. themselves, preferably amine oxides; c) from about 0.1% to about 15% (preferably from about 0.2% to about 10%, most preferably from about 0.5% to about 5%) by weight of the composition of a low foaming nonionic surfactant with an X / Y number greater than or equal to 1.00, preferably greater than 1.10, most preferably greater than 1.30; and when said low foaming nonionic surfactant contains a glyceryl ether group, the block in said low foaming nonionic surfactant is a linear or branched alkyl group containing at least 4 carbon atoms and the number XY is calculated in the absence of dimers and trimers; d) optionally, from about 0.1% to about 40% by weight of the composition of a bleaching agent (preferably a hypochlorite, e.g., sodium dichloroisocyanurate, "NaDCC", or source of hydrogen peroxide bleach system, e.g., perborate or percarbonate), preferably also containing a cobalt bleach catalyst and / or manganese bleach catalyst; and e) auxiliary materials; wherein the weight ratio of the low foaming nonionic surfactant to the oxide surfactant is from about 2: 1 to about 30: 1. An alternative embodiment of the present invention are automatic dishwashing detergent compositions comprising: a) from about 5% to about 90% by weight of the composition of a builder; b) from about 0.1% to about 15% by weight of the composition of an oxide surfactant, said oxide surfactant being selected from the group consisting of amine oxides, phosphine oxides, silfoxides and mixtures thereof, preferably amine oxides; c) from about 0.1% to about 15% by weight of the composition of a low foaming nonionic surfactant wherein said low foaming nonionic surfactant has an interfacial tension of less than 8 dynes / cm; d) optionally, from about 0.1% to about 40% by weight of the composition of a bleaching agent; and e) auxiliary materials; wherein the weight ratio of the low foaming nonionic surfactant to the oxide surfactant is from about 2: 1 to about 30: 1. The present invention comprises (but is not limited to) fully formulated ADD compositions, granulated, in which additional ingredients, including other enzymes (especially proteases and / or amylases) are formulated together with other forms of ADD products such as liquids, gels and tablets. The present invention also encompasses cleaning methods, very particularly a dishwashing method in an automatic household dishwashing appliance, which consists of treating the dirty dishware in the automatic dishwashing machine with an aqueous alkaline solution comprising an ADD composition as previously provided. As already indicated, the invention has advantages, including excellent removal of greasy dirt, good care of dishes and good cleaning in general. All parts, percentages and relationships are expressed in percent by weight, unless otherwise specified. All the documents cited, in part important, are incorporated here by reference.

DETAILED DESCRIPTION OF THE INVENTION Automatic Dishwashing Compositions: The automatic dishwashing compositions of the present invention comprise a detergency builder and a select nonionic surfactant system, and preferably also include a bleaching agent (such as a chlorine bleach or a source). of hydrogen peroxide), and / or detersive enzymes. Bleaching agents useful herein include oxygen and chlorine bleach / v.gr., Hypochlorite or NaDCC) and sources of hydrogen peroxide, including any common hydrogen peroxide-liberating salt, such as sodium perborate, sodium percarbonate and mixtures thereof. the same. Also useful are sources of available oxygen such as a persulfate bleach (e.g., OXONE, manufactured by DuPont). In the preferred embodiments, additional ingredients such as water-soluble silicates (useful to provide alkalinity and assist in the control of corrosion), dispersing polymers (which modify and inhibit the growth of calcium and / or magnesium salts crystals) are present. , chelators (that control transition metals), alkalis (to adjust pH) and detersive enzymes (to help with cleaning dirty foods difficult to remove, especially from starchy and proteinaceous soils). Additional conventional bleach modifying materials (e.g., TAED and / or bleach catalysts) may be added, provided that any bleach modifying materials are supplied in a manner that is compatible with the purposes of the present invention. Moreover, the detergent compositions of the present invention comprise one or more processing aids, fillers, perfumes, materials for making conventional enzyme particles including enzyme centers or "nonpareils", as well as pigments, and the like. In general, the materials used for the production of ADD compositions herein are preferably verified for compatibility with stain removal / film on glassware. The test methods for stain / film removal are generally described in the literature on automatic dishwashing detergents, including DIN and ASTM test methods. Certain oily materials, especially at longer chain lengths, and insoluble materials such as clays, as well as long-chain fatty acids or soap-forming soaps are therefore preferably limited or excluded from the present compositions. Quantities of the essential ingredients may vary within broad scales; however, the automatic dishwashing detergent compositions preferred herein (which typically have a pH of 1% aqueous solution of about 8, preferably from about 9.5 to about 12, most preferably from about 9.5 to about 10.5) are those where it is present: from about 5% to about 90%, preferably from about 5% to about 75%, of detergent builder; from about 0.1% to about 15%, preferably from about 0.2% to about 10%, of the nonionic surfactant. Such fully formulated modalities typically comprise from about 0.1% to about 15% of a polymeric dispersant, from about 0.01% to about 10% of a chelator, and from about 0.00001% to about 10% of a detersive enzyme, although they can Additional or auxiliary ingredients are present. The detergent compositions herein in granular form typically limit the water content, for example, to less than about 7% free water, for better storage stability. Although the compositions of the present invention can be formulated using bleach-containing bleach additive, the preferred ADD compositions of this invention (especially those comprising detersive enzymes) are substantially free of chlorine bleach. By "substantially free" chlorine bleach is meant that the formulator does not deliberately add a chlorine-containing bleach additive, such as a dichloroisocyanurate, to the preferred ADD composition. However, it is recognized that due to factors beyond the control of the formulator, such as the chlorination of the water supply, a non-zero amount of chlorine binder may be present in the wash solution. The term "substantially free" may be similarly considered with reference to the preferred limitation of other ingredients.

By "effective amount" herein is meant an amount that is sufficient, under whatever comparative test conditions are employed, to increase the cleanliness of a soiled surface. Also, the term "catalytically effective amount" refers to an amount of metal-containing bleach catalyst, which is sufficient under whatever comparative test conditions are employed, to increase the cleanliness of the soiled surface. In the automatic washing of dishes, the dirty surface may be, for example, a porcelain cup with a tea stain, a porcelain cup with a lipstick stain, dishes soiled with simple tears or more complex food stains, or a plastic spatula stained with tomato soup. The test conditions will vary depending on the type of washing device used and the habits of the user. Some machines have significantly longer wash cycles than others. Some users choose to use warm water without any heating inside the appliance; others use warm or even cold water, followed by heating through an integrated electrical resistance. Of course, the performance of the bleaches and enzymes will be affected by such considerations, and the levels used in fully formulated detergents and cleaning compositions can be adjusted appropriately.

Low foaming nonionic surfactant (LFNI) The low foaming nonionic surfactants of the present invention should have an X / Y number of more than 1.00, preferably more than 1.10, most preferably more than 1.30. The determination of this number X Y is described below. It has surprisingly been found that surfactants with an X / Y number of more than 1.00 demonstrate superior cleaning to nonionic surfactants with an X / Y number of 1.00 or less. When the LFNIs contain a glyceryl ether group, then the X / Y number is calculated exclusive of any possible dimers and trimers, ie, any dimers and trimers present are not used to calculate the X / Y value for any LFNI containing a group glyceryl ether. In addition, these surfactants provide foam control and in combination with the oxide surfactant provide a level of foams that is suitable for use in an ADW composition. In addition, the surfactants and LFNI of the present invention have minimal negative interaction with the cleaning of the oxide surfactant. Surfactants include ether-blocked poly (oxyalkylated alcohol) surfactant containing ethoxy and propoxy, poly (oxyalkylated) alcohol surfactant blocked with ether containing ethoxy and butoxy, alkylalkoxylates containing ethoxy and butoxy, and alkylalkoxylates containing ethoxy , propoxy and butoxy. However, when the LFNI surfactant contains a glyceryl ether group, then it is preferred that the amount of any possible dimer or trimer present be reduced to a minimum. The amount of dimer and trimer is minimized to such levels that these have minimal negative interaction with the cleaning of the oxide surfactant. The amount of dimer and trimer present in the glyceryl ether-containing surfactant depends on the process used to produce the surfactant. The preferred method for minimizing or eliminating dimer and trimer formation can be controlled by stoichiometry of the reagents or by typical purification methods (e.g., chromatography, crystallization, separation, etc.). A preferred LFNI of the present invention has the formula: R1 (EO) a (PO) b (BO) c wherein R1 is a linear or branched C6 to C20 alkyl, preferably straight or branched C8 to C18 alkyl, most preferably linear or branched C9 to C16 alkyl; a is an integer from 2 to 30, preferably from 4 to 25, most preferably from 5 to 20, most preferably still from 5 to 18; b is an integer from 0 to 30, preferably from 0 to 25, most preferably from 0 to 20, most preferably still from 0 to 10; c is an integer from 1 to 10, preferably from 1 to 9, most preferably from 1 to 7, most preferably still from 1 to 6. Another preferred LFNI of the present invention has the formula: R1? [CH2CH (R3) O] m [CH2] kCH (OH) [CH2] jOR2 wherein R ^ and R ^ are saturated or unsaturated, linear or branched aliphatic or aromatic hydrocarbon radicals having from 1 to 30 carbon atoms; R3 is H, or a linear aliphatic hydrocarbon radical having 1 to 4 carbon atoms; m is an integer that has an average value of 1 to 40, where when m is 2 or greater R3 can be the same or different and k and j are integers that have an average value of 1 to 12; wherein when m is 15 or greater and R3 is H and methyl, at least four of R ^ are methyl, wherein when m is 15 or greater and R includes H and from 1 to 3 methyl groups, then at least one R3 is ethyl, propyl or butyl, wherein R2 can be optionally alkoxylated, wherein said alkoxy is selected from ethoxy, propoxy, butyloxy and mixtures thereof; wherein said surfactant has less than 30%, preferably less than 15% and most preferably less than 5% of dimers and trimers of said nonionic surfactant. Another preferred LFNI of the present invention has the formula: R O [CH2CH (R3) O] eR2 wherein R1 is a saturated or unsaturated, linear or branched aliphatic or aromatic hydrocarbon radical having from 1 to 30 carbon atoms; R2 is a saturated or unsaturated, linear or branched aliphatic or aromatic hydrocarbon radical having from 1 to 30 carbon atoms, optionally containing from 1 to 5 hydroxy groups; and optionally substituted with an ether group; R ^ is H, or a linear aliphatic hydrocarbon radical having from 1 to 4 carbon atoms; e is an integer having an average value of 1 to 40, wherein R2 can optionally be alkoxylated, wherein said alkoxy is selected from ethoxy, propoxy, butoxy and mixtures thereof. Suitable surfactants include, but are not limited to; Surfactant X / Y value C9.11PO3EO13BO6 1.41 C9.11PO3EO13BO3 1.70 C9.11EO13BO6 1.49 C9.11EO13BO3 1.88 C9,11BO1EO13BO3 1.72 C9.11E08B03 1.29 C12.15EO7B02 1.03 C9.11EO8BO2 1.41 C9.11E08B01 1.58 C12,13EO6.5T * BO1 1.10 Oenota the highest, or narrow selection of EO distribution.

Calculation of X / Y The LFNI surfactants of the present invention must all have a hydrophobic to hydrophilic ratio, or "XY" number greater than or equal to 1.00. The calculation of "X / Y" is as follows. For a given alkoxylated nonionic surfactant structure, "X" is defined as the sum of protons attached to carbon atoms that are adjacent to oxygen. "Y" is defined as the sum of protons added to carbon atoms within said molecule that are not adjacent to oxygen. That is to say, -X x I A typical example is shown below. For C-? 3EO? 2Ci3, X = 52 and Y = 50. Therefore, X / Y = 52/50 = 1.04. X / Y can also be measured experimentally from the integration of the 1 H NMR spectrum. Protons "X" are represented as the maximum area defined by the spectrum region of d 3.0 to 4.0 ppm. The "protons" are represented as the maximum defined area from d 0.5 to 2.0 ppm. X / Y is then calculated by dividing the maximum area from 3.0 to 4.0 ppm by the area of 0.5 to 2.0. ADD compositions comprising surfactant systems are preferred wherein the foaming (when any silicone foaming agent is absent) is less than 5.08 cm, preferably less than 2.54 cm, determined by the method described in the US patent. ,294,365.

Oxide Surfactant - The oxide surfactant is selected from the group consisting of amine oxides, phosphine oxides, sulfoxides and mixtures thereof, with amine oxide being preferred. Preferred amine oxides have the formula O R3 (OR) XN (R5) 2 wherein R3 is an alkyl, hydroxyalkyl or alkylphenyl group or mixtures thereof containing from about 8 to about 22 carbon atoms; R4 is an alkylene or hydroxyalkylene group containing from about 2 to about 3 carbon atoms or mixtures thereof; x is from 0 to about 3; and each of R ^ is an alkyl or hydroxyalkyl group containing from about 1 to about 3 carbon atoms or a polyethylene oxide group containing from about 1 to about 3 ethylene oxide groups. Preferred phosphine oxides have the formula O I R3 (OR4) xP (R5) 2 wherein Rβ, R4, X and R5 are as defined above. The preferred sulfoxides have the formula O I R3 (OR4) xS (R5) 2 where R3, R4, X and R5 SOn as defined above.

Co-surfactants - The composition of the present invention may also contain optional co-surfactants. These optional surfactants will preferably be stable to the bleach. Preferred optional co-surfactants are low cloud point nonionic surfactants, high cloud point nonionic surfactants, anionic surfactants and mixtures thereof. The nonionic co-surfactants useful in the automatic dishwashing compositions of the present invention, when present, are conveniently included in the detergent compositions of the present invention at levels of from about 0.1% to about 15%. the composition . In general, co-surfactants stable to the bleach are preferred. Nonionic surfactants are generally well known in the art, described in more detail in Kirk Othmer's Encyclopedia of Chemical Technology, 3a. Ed., Vol. 22, pp. 360-379, "Surfactants and Detersive Systems", incorporated herein by reference. "Turbidity point" as used herein, is a well-known property of nonionic surfactants which is the result of the surfactant which becomes less soluble with increasing temperature, the temperature at which the appearance of a second phase it can be observed is referred to as the "turbidity point" (see Kirk Othmer, pp. 360-362, previously mentioned). As used herein, a "low cloud point" nonionic surfactant is defined as a nonionic surfactant system ingredient having a cloud point of less than 30 ° C, preferably less than about 20 ° C. and most preferably less than about 10 ° C. Typical low cloud point co-surfactants include nonionic alkoxylated surfactants, especially ethoxylates derived from primary alcohol, and polyoxypropylene / polyoxyethylene / polyoxypropylene (PO / EO / PO) reverse block polymers. Also, such low cloud point nonionic surfactants include, for example, ethoxylated-propoxylated alcohol (e.g., IPoly-Tergent® SLF18 from Olin Corporation) and poly (oxyalkylated) alcohols blocked with epoxy (e.g. Tergent® SLF18B from Olin Corporation of non-ionics, as described for example in WO 94/22800, published October 13, 1994 by Olin Corporation). The nonionic co-surfactants may optionally contain propylene oxide in an amount of up to 15% by weight. Other preferred nonionic surfactants can be prepared by the methods described in the U.S. Patent. 4,223,163, issued September 16, 1980, Builloty, incorporated herein by reference. The low cloud point nonionic co-surfactants further comprise a polymeric polyoxyethylenepolyoxypropylene block compound. The polyoxyethylene-polyoxypropylene block polymer compounds include those based on ethylene glycol, propylene glycol, glycerol, trimethylolpropane and ethylene diamine as the reactive hydrogen compound of initiator. Some of the block polymer surfactant compounds designated as PLURONIC®, REVERSED PLURONIC® and TETRONIC® by BASF-Wyandotte Corp., Wyandotte, Michigan, are suitable in ADD compositions of the invention. Preferred examples include REVERSED PLURONIC® 25R2 and TETRONIC® 702. Said surfactant co-agents are typically used herein as non-low-point cloudiness surfactants. As used here, a "high cloud point" nonionic co-surfactant is defined herein as a nonionic surfactant system ingredient having a cloud point greater than 40 ° C, preferably greater than about 50 ° C, and preferably greater than about 60 ° C. Preferably, the nonionic co-surfactant co-surfactant system comprises an ethoxylated surfactant derived from the reaction of a monohydric alcohol or alkylphenol containing from about 8 to about 20 carbon atoms, with an amount of from about 6 to about 15 moles. of ethylene oxide per mole of alcohol or alkylphenol on an average basis. Such high cloud point nonionic co-surfactants include, for example, Tergitol 15S9 (provided by Union Carbide), Rhodasurf TMD 8.5 (provided by Rhone Poulenc), and Neodol 91-8 (provided by Shell). It is also preferred for purposes of the present invention that the high cloud point nonionic co-surfactant also has a balance of hydrophilic-lipophilic equilibrium ("HLB"); see Kirk Othmer below) within the range of about 9 to about 15, preferably 11 to 15. Such materials include, for example, Tergitol 15S9 (provided by Union Carbide), Rhodasurf TMD 8.5 (provided by Rhone Poulenc), and Neodol 91-8 (provided by Shell). Another preferred high-cloud non-ionic co-surfactant is derived from a straight chain or preferably branched or secondary fatty alcohol containing from about 6 to about 20 carbon atoms (C5-C20 alcohol). including secondary alcohols and branched chain primary alcohols. Preferably, the high cloud point nonionic co-surfactants are branched or secondary ethoxylated alcohols, most preferably branched ethoxylated alcohols of mixed C9 / 11 or Cj 1/15, condensed with an average of about 6 to about 15 moles, preferably from about 6 to about 12 moles, and most preferably from about 6 to about 9 moles of ethylene oxide per mole of alcohol. Preferably the ethoxylated nonionic co-surfactant derived in this manner has a narrow ethoxylate distribution in relation to the average. When the optional surfactant co-agents are a mixture of low cloud point and high cloud point nonionic surfactants, it is preferred that the blend be combined in a weight ratio preferably within the range of about 10: 1 to approximately 1: 10. The anionic co-surfactant may be selected from alkylethyloxycarboxylates, alkyl ethoxy sulfates, with the degree of ethoxylation greater than 3 (preferably from 4 to 10, most preferably from 6 to 8), and the chain length in the range from C8 to C16 , preferably 11-15. In addition, it has been found that the branched alkylcarboxylates are useful in ADW compositions when the branching occurs in the middle of the chain and the total chain length is 10 to 18, preferably 12 to 16 with the side branch of 2 to 4 atoms carbon length. An example is 2-butyloctanoic acid. The anionic surfactant coagent is typically of a type which has good solubility in the presence of calcium. Said anionic co-surfactants are further polished by alkyl (polyethoxy) sulfates (AES), alkyl (polyethoxy) carboxylates (AEC) and C6-C- or short chain alkyl sulfates and alkylsulfonates. It has been shown that straight chain fatty acids are ineffective due to their sensitivity to calcium.

Detergency builders Detergent builders other than silicates may optionally be included in the compositions of the present invention to help control the hardness of the minerals. Inorganic and organic builders can be used. Detergency builders are used in automatic dishwashing to help remove particulate dirt. The level of the builder may vary depending on the final use of the composition and its desired physical form. The compositions will typically comprise at least about 1% builder. High performance compositions will typically comprise from about 5% to about 90%, very typically from about 5% to about 75% by weight of the builder. However, lower or higher levels of detergency builder are not excluded. Inorganic or non-phosphate builders include, but are not limited to, phosphonates, phytic acid, silicates, carbonates (including bicarbonates and sesquicarbonates), sulfates, citrate, zeolite or layered silicate, and aluminosilicates.

Examples of carbonate builders are the alkali metal and alkaline earth metal carbonates such as those described in German Patent Application No. 2,321,001 published November 15, 1973. Various grades and types of carbonates can be used. sodium carbonate and sodium sesquicarbonate, some of which are particularly useful as vehicles for other ingredients, especially detersive surfactants. Organic builders suitable for the purposes of the present invention include, but are not limited to, a wide variety of polycarboxylate compounds. As used herein, "polycarboxylate" refers to compounds having a plurality of carboxylate groups, preferably at least 3 carboxylates. Polycarboxylate builders can be added to the composition in acid form, but can also be added in the form of a neutralized or "overbased" salt. When they are in salt form, alkali metals such as sodium, potassium and lithium, or alkanolammonium salts are preferred. Polycarboxylate builders include a variety of categories of useful materials. An important category of detergency builders includes ether polycarboxylates, including oxydisuccinates, such as those described in Berg, U.S. Pat. 3,128,287, issued April 7, 1964, and Lamberti et al., Patent of E.U.A. 3,635,830, issued January 18, 1972. See also detergency builders of "TMS / TDS" of the U.S. patent. No. 4,663,071, issued to Bush et al., On May 5, 1987. Suitable ether polycarboxylates also include cyclic, particularly alicyclic, compounds, such as those described in U.S. Pat. 3,923,679; 3,835,163; 4,158,635; 4,120,874 and 4,102,903. Other useful builders include ether hydroxypolycarboxylates, maleic anhydride copolymers with ethylene or vinyl methyl ether, 1,3-trihydroxybenzene-2,4,6-trisulfonic acid, and carboxymethyloxysuccinic acid, various alkali metal, ammonium, and substituted ammonium salts of polyacetic acids such as ethylenediaminetetraacetic acid and nitrilotriacetic acid, as well as polycarboxylates such as mellitic acid, succinic acid, oxydisuccinic acid polymaleic acid, benzene-1, 3,5-tricarboxylic acid, carboxymethyloxysuccinic acid and soluble salts thereof. Citrate builders, eg, citric acid and soluble salts thereof (particularly sodium salt), are polycarboxylate builders of particular importance for heavy-duty laundry detergent formulations and for automatic dishwashing due to its availability from renewable resources and its biodegradability. Citrates can also be used in combination with zeolite, the aforementioned BRITESIL types, and / or stratified silicate builders. Oxydisuccinates are also useful in said compositions and combinations. Also suitable in the detergent compositions of the present invention are the 3,3-dicarboxy-4-oxa-1,6-hexanedioneates and the related compounds described in E.U.A. No. 4,566,984, Bush, issued January 28, 1986. Useful succinic acid builders include alkyl and C5-C20 alkenyl succinic acids and salts thereof.

A particularly preferred compound of this type is dodecenylsuccinic acid. Specific examples of succinate builders include: lauryl succinate, myristiisuccinate, palmityl succinate, 2-dodecenylsuccinate (preferred), 2-pentadecenylsuccinate, and the like. Lauryl succinates are the preferred builders of this group and are described in European patent application 86200690.5 / 0,200,263, published November 5, 1986. Other suitable polycarboxylates are described in the US Pat.

E.U.A. 4,144,226, Crutchfield et al., Issued March 13, 1979 and in the U.S. patent. 3,308,067, Diehl, issued March 7, 1967. See also the patent of E.U.A. 3,723,322. The fatty acids, e.g., C12-C18 monocarboxylic acids. they may also be incorporated into the compositions alone or in combination with the aforementioned builders, especially citrate and / or succinate builders, to provide additional builder activity but are generally not desired. Such use of fatty acids will generally result in a decrease in foaming in laundry compositions, which may need to be considered by the formulator. Fatty acids or their salts are not desirable in automatic dishwashing (ADD) modalities in situations in which soap soiling can be formed and deposited on the dishes.

Where it is possible to use phosphorus-based builders, the various alkali metal phosphates such as the well-known sodium tripolyphosphates, sodium pyrophosphate and sodium orthophosphate can be used. Phosphonate builders such as ethan-1-hydroxy-1,1-d-phosphonate and other known phosphonates (see, for example, US Patents 3,159,581, 3,213,030, 3,422,021, 3,400,148 and 3,422,137) can also be used although Such materials are most commonly used in a low level mode as chelators or stabilizers. Builders for use in ADD compositions are well known. They include, but are not limited to, alkali metal, ammonium and alkanolammonium salts of polyphosphates (illustrated by tripolyphosphates, pyrophosphates and vitreous polymeric metaphosphates). The sources of builder are described in detail in Kirk Othmer, 3a. Edition, Vol. 17, pp 426-472 and in "Advanced Inorganic Chemistry" by Cotton and Wilkinson, pp. 394-400 (John Wiley &Sons, Inc., 1972). Preferred levels of phosphate builders of the present are from about 10% to about 75%, preferably from about 15% to about 50%, of phosphate builder.

Bleaching agents Sources of hydrogen peroxide are described in detail in Kirk Othmer's Encyclopedia of Chemical Technology, 4a. Ed. (1992, John Wiley &Sons), Vol. 4, pp. 271-300"Bleaching Agents (Survey)", which is incorporated herein, and includes the different forms of sodium perborate and sodium percarbonate, including various coated and modified forms. An "effective amount" of a source of hydrogen peroxide is any amount capable of measurably improving the removal of stains (especially tea stains) from soiled dishes compared to a composition that lacks a source of hydrogen peroxide when the dishes are washed by the consumer in an automatic household dish washing machine in the presence of alkaline material. Very generally, a source of hydrogen peroxide herein is any convenient compound or mixture that under conditions of consumer use provides an effective amount of hydrogen peroxide. The levels can vary widely and are generally in the range of from about 0.1% to about 70%, very typically from about 0.5% to about 30%, by weight of the ADD compositions herein. The preferred source of hydrogen peroxide used here can be any convenient source, including the hydrogen peroxide itself. For example, perborate, e.g., sodium perborate (any hydrate but preferably mono or tetrahydrate), sodium carbonate peroxyhydrate or equivalent percarbonate salts, sodium pyrophosphate peroxyhydrate, urea peroxyhydrate or sodium peroxide may be used here. Also useful are available oxygen sources such as a persulfate bleach (e.g., OXONE, manufactured by DuPont). Sodium perborate monohydrate and sodium percarbonate are particularly preferred. Mixtures of any suitable hydrogen peroxide sources can also be used. A preferred percarbonate bleach comprises dry particles having an average particle size in the range of about 500 microns to about 1,000 microns, no more than about 10% by weight of said particles being less than about 200 microns and no more of about 10% by weight of said particles being greater than about 1.250 microns. Optionally, the percarbonate can be coated with a silicate, borate or water soluble surfactants. Percarbonate is available from various commercial sources such as FMC, Solvay and Tokai Denka. Although not preferred for the ADD compositions of the present invention which comprise detersive enzymes, the compositions of the present invention may also comprise as the bleaching agent a chlorine bleach material. Such agents are well known in the art and include for example sodium dichloroisocyanurate ("NaDCC"). Although the effective ADD compositions herein may comprise only the nonionic surfactant system and builder, the fully formulated ADD compositions will typically also comprise other automatic dishwashing detergent auxiliary materials in order to improve or modify the performance. These materials are selected as appropriate for the properties of an automatic dishwashing compositions. For example, if low stain and film removal is desired, the preferred compositions have stain and film removal rates less than 1, as measured by the American Society for Testing and Materials ("ASTM") standard test D3556- 85 (reapproved in 1989), "Standard Test Method for Deposition on Glassware During Mechanical Dishwashing".

Auxiliary Materials The detersive or auxiliary ingredients optionally included in the compositions of the present invention include one or more materials to aid or increase cleaning performance, treatment of the substrate to be cleaned, or designed to improve the aesthetics of the compositions. They are selected based on the form of the composition, that is, whether the composition is to be sold as a liquid, paste (semi-solid) or solid (including tablets and the preferred granular forms for the compositions of the present invention). Auxiliaries may also be included in compositions of the present invention, at their conventional levels established in the art to be used (generally, auxiliary materials comprise, in total, from about 30% to about 99.9%, preferably of about 70% to about 95%, by weight of the compositions), include other active ingredients such as non-phosphate builders, chelators, enzymes, foam suppressors, dispersant polymers (e.g., from BASF Corp. O Rohm & amp;; Haas), color spots, silver care agent, anti-rust and / or anti-corrosion agents, dyes, fillers, germicides, alkalinity sources, hydrotropes, antioxidants, enzyme stabilizing agents, perfumes, solubilizing agents, vehicles, processing aids , pigments, pH control agents and, for liquid formulations, solvents, as described in detail below.

Detersive Enzymes The detergent compositions of the present invention may further comprise one or more enzymes that provide cleaning performance benefits. "Detersive enzyme" as used herein, means any enzyme that has a beneficial effect of cleaning, stain removal or other beneficial effect in ADD compositions. Said detersive enzymes include selected enzymes of cellulases, hemicellulases, proteases, glucoamylases, amylases, lipases, cutinases, pectinases, xylanases, reductases, oxidases, phenoloxidases, lipoxygenases, ligninases, pullulanases, tanases, pentosanas, malanases, β-glucanases, arabinosidases or mixtures thereof. A preferred combination is a detergent composition having a mixture of conventional applicable enzymes such as protease, amylase, lipase, cutinase and / or cellulase. When present in the compositions, the enzymes are from about 0.0001% to about 5% active enzyme by weight of the detergent composition. Highly preferred for automatic dishwashing are amylases and / or proteases, including current commercially available types and improved types which, although more compatible with the bleach, have a residual degree of susceptibility to deactivation of bleach.

Proteolytic enzyme - The proteolytic enzyme can be of animal, vegetable or microorganism origin (preferred). Proteases for use in the detergent compositions herein include (but are not limited to) trypsin, subtilisin, chymotrypsin, and elastase-type proteases. Preferred to be used herein are proteolytic enzymes of the subtilisin type. Particularly preferred is a bacterial serine proteolytic enzyme obtained from B. subtilis and β. licheniformis. Suitable proteolytic enzymes include Alcalase® (preferred), Esperase® and Savinase® from Novo Industri A / S (Copenhagen, Denmark), Gist-brocades' and Maxatase®, Maxacal® and Maxapem 15® (Maxacal® treated by genetic engineering techniques). of proteins) (Delft, Holland), and subtilisins BPN and BPN '(preferred), which are commercially available. Preferred proteolytic enzymes are also modified bacterial serine proteases, such as those made by Genecor International, Inc. (San Francisco, California) which are described in European Patent No. 251,446B, issued December 28, 1994 (particularly pages 17, 24 and 98) and which is called here "Protease B", and in the patent of E.U.A. 5,503,378, Venegas, issued July 9, 1991, which refers to a modified bacterial serine proteolytic enzyme which is referred to herein as "Protease A". (the same as BPN '). In particular, see columns 2 and 3 of the US patent. 5,030,378 for a complete descron, including amino acid sequence, of protease A and its variants. Other proteases are sold under the trade names: Primase, Durazym, Opticlean and Optimase. The preferred proteolytic enzymes are selected from the group consisting of Alcalase® (Novo Industri A / S), Protease A and Protease B (Genecor), and mixtures thereof, Protease B is the most preferred. Of particular interest for use herein are the proteases described in the U.S. patent. No. 5,470,733. Also, the proteases described in the co-pending USSN application 8 / 136,797 can be included in the detergent composition of the invention. Another preferred protease, referred to as "Protease D" is a carbonyl hydrolase variant having an amino acid sequence not found in nature, which is derived from a precursor carbonyl hydrolase by substituting a different amino acid with a plurality of amino acid residues in a position in said carbonyl hydrolase equivalent to the +76 position, preferably also in combination with one or more amino acid residue positions equivalent to 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 in accordance with the subtilisin numbering of Bacillus amyloliquefaciens, as described in WO 95/10591 published on April 20, 1995 by Genecor International (A. Baeck et al. Entitled "Protease-Containing Cleaning Compositions" which has the serial number of USA 08 / 322,676 , presented on October 13, 1994). Useful proteases are also described in PCT publications: WO 95/30010 published November 9, 1992 by The Procter & Gamble Company; WO 95/30011 published November 9, 1992 by The Procter & Gamble Company; WO 95/29979 published November 9, 1992 by The Procter & Gamble Company. Protease enzymes can be incorporated according to the present invention at a level of 0.0001% to 2% active enzyme by weight of the composition. Amylase - Amylases (alpha and / or beta) can be included for the removal of carbohydrate-based stains. The appropriate amylases are TermamylR (Novo Nordisk), Fungamyl ^ and BAN ^ (Novo Nordisk). The enzymes can be of any suitable origin, such as of vegetable, animal, bacterial, fungal and yeast origin. Amylase enzymes are normally incorporated into the detergent composition at levels of from about 0.0001% to about 2%, preferably from about 0.0001% to about 0.5%, most preferably from about 0.0005% to about 0.1%, most preferably still around from 0.001% to about 0.05% active enzyme by weight of the detergent compositions. Amylase enzymes also include those described in WO95 / 26397 and in the co-pending application by Novo Nordis PCT / DK96 / 00056. A suitable amylase enzyme is NATALASE® available from Novo Nordisk.

Other amylases suitable herein include, for example, the α-amylases described in GB 1, 296, 839 to Novo; RAPIDASE®, International Bio-Synthetics, Inc. and TERMAMYL®, Novo. FUNGAMYL® by Novo is especially useful. Particly preferred amylases herein include the amylase variants having further modification in the immediate parent as described in WO 9510603 A and are available from the assignee Novo, as DURAMYL®. Another oxidizing amylase of improved stability that is preferred includes that described in WO 9418314 to Genencor International and WO 9402597 to Novo. Any other oxidative amylase of improved stability can be used, for example that derived by site-directed mutagenesis of chimeric, hybrid or simple known mutant progenitor forms of available amylases. Other preferred enzyme modifications are accessible. See WO 9509909 to Novo. Several carbohydrase enzymes that impart antimicrobial activity may also be included in the present invention. Such enzymes include endoglycosidase, endoglycosidase type II and glucosidase are described in the patents Nos. 5,041, 236, 5,395,541, 5,238,834 and 5,356,803, the descriptions of which are incorporated herein by reference. Of course, other enzymes having antimicrobial activity can also be employed. peroxidases, oxidases and some other enzymes.

It is also possible to include an enzyme stabilization system in the compositions of the present invention when any enzyme is present in the composition. Peroxidase enzymes are used in combination with oxygen sources, that is, precarbonate, perborate, persulfate, hydrogen peroxide, etc. They are used for "solution bleaching", that is, to prevent the transfer of dyes or pigments removed from the substrates during washing operations to other substrates in the washing solution.The peroxidase enzymes are known in the art and include, example, horseradish peroxidase, ligninase, and haloperoxidase such as chlorine and bromoperoxidase, peroxidase-containing detergent compositions are described, for example, in the PCT International Application WO 89/099813, published on October 19, 1989, by O. Kirk, assigned to Novo Industries A / S. The present invention comprises peroxidase-free automatic dishwashing composition embodiments. A variety of enzyme materials and means for their incorporation into synthetic detergent compositions are also described in the US patent. 3,553,139, issued January 5, 1971 to McCarty et al. Enzymes are further described in the U.S. patent. 4,101, 457, Place et al., Issued July 18, 1978, and in U.S. Patent 4,507,219, Hughes, issued March 26, 1985. Enzymes for use in detergents can be stabilized by various techniques. Enzyme stabilization materials are described and exemplified in US Patent 3,600,319, issued August 17, 1971, Gedge et al., And European Patent Application Publication No. 0 199 405, Application No. 86200586.5, published. on October 29, 1986, Venegas. Enzyme stabilization systems are also described, for example, in the U.S. patent. 3,519,570.

Optional bleaching aids a) Bleach activators Preferably, the peroxygen bleaching component in the composition is formulated with an activator (peracid precursor). The activator is present at levels of about 0.01%, preferably about 0.5%, most preferably about 1% to about 15%, preferably about 10%, most preferably about 8%, by weight of the composition. Preferred activators are selected from the group consisting of tetraacetylethylenediamine (TAED), benzoylcaprolactam (BzCL), 4-nitrobenzoylcaprolactam, 3-chlorobenzoyl-caprolactam, benzoyloxybenzenesulfonate (BOBS), nonanoyloxybenzenesulfonate (NOBS), phenylbenzoate (PhBz), decanoyloxybenzenesulfonate (CI Q- OBS), benzoylvalerolactam (BZVL), octanoyloxybenzene sulfonate (Cß-OBS), perhydrolyzable esters and mixtures thereof, most preferably benzoylcaprolactam and benzoylvalerolactam. Particularly preferred bleach activators in the pH range of from about 8 to about v 9.5 are those selected having a residual group OBS or VL.

Preferred bleach activators are those described in the U.S.A. 5,130,045, Mitchell et al., And 4,412,934, Chung et al. "And the co-pending patent applications of E.U.A. Nos. 08 / 064,624, 08 / 064,623, 08 / 064,621, 08 / 064,562, 08 / 064,564, 08 / 082,270 and the co-pending application of M. Burns, A.D. Willey, R.T. Hartshom, C.K. Ghosh, entitled "Bleaching Compounds Comprising Peroxyacid Activators Used With Enzymes" and which has the serial number of E.U.A. 08 / 133,691 (Case 4890R of P &G), all of which are incorporated herein by reference. The molar ratio of peroxygen bleach compound (as AvO) to bleach activator in the present invention generally ranges from at least 1: 1, preferably from about 20: 1, most preferably from about 10: 1 to about 1: 1, preferably at about 3: 1. The substituted quaternary bleach activators can also be included. The present cleaning compositions preferably contain a substituted quaternary bleach activator (QSBA) or a substituted quaternary peracid (QSP); most preferably, the first. The preferred QSBA structures are further described in the U.S.A. copending series No. 08 / 298,903, 08 / 298,650, 08 / 298,906 and 08 / 298,904, filed on August 31, 1994, incorporated herein by reference. b) Organic peroxides, especially diacylperoxides - These are illustrated extensively in Kirk Othmer, Encyclopedia of Chemical Technology, Vol. 17, John Wiley and Sons, 1982, on pages 27-90 and especially on pages 63-72, all incorporated here by reference. If diacylperoxide is used, it will preferably be one that exerts minimal adverse impact on stain removal / film removal. (c) Metal-containing bleach catalysts - The compositions of the present invention and the methods of the present invention can utilize metal-containing bleach catalysts that are effective for use in ADD compositions. Bleach catalysts containing manganese and cobalt are preferred. For examples of suitable catalysts, see the patents of E.U.A. Nos. 4, 246,612, 5,804,542, 5,798,326, 5,246,621, 4,430,243, 5,244,594, 5,597,936, 5,705,464, 4,810,410, 4,601, 845, 5,194,416, 5,703,030, 4,728,455, 4,711, 748, 4,626,373. 4,119,557, 5,114,606, 5,599,781, 5,703,034, 5,114,611, 4,430,243, 4,728,455 and 5,227,084; European Patent Nos. 408,131, 549,271, 384m503, 549,272, 224,952 and 306,089; German Patent No. 2,054,019; Canadian Patent No. 866,191. Cobalt catalysts (III) are preferred having the formula: Co [(NH3) n (M ') m] B'bT'tQqPp] Yy where the cobalt is in the oxidation state +3; 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; Q is a tetradentate ligand; q is O or 1; P is a pentadentate ligand; p is 0 or 1; and n + m + 2b + 3t + 4q + 5p = 6; Y is one or more appropriately selected counterions present in a number y, where y is an integer of 1 to 3 (preferably 2 to 3, most preferably 2 when Y is an anion with charge -1), to obtain a salt balanced in as charged, and preferred is selected from the group consisting of chloride, iodide, I3", formate, nitrate, nitrite, sulfate, sulfite, citrate, acetate, carbonate, bromide, PFß ", BF4", B (Ph) 4", phosphate, phosphite, silicate, tosylate, methanesulfonate and combinations thereof [optionally, Y can be protonated if there is more than one anionic group in Y, for example HPO-42", HCO3-, H2PO4-, etc., and in addition, Y may be selected from the group consisting of non-traditional inorganic anions such as anionic surfactants (eg, linear alkylbenzene sulphonate (LAS), alkyl sulfates (AS), alkyl ether sulfonates (AES), etc.) and / or anionic polymers (for example, polyacrylates, polymethacrylates, etc.), and wherein at least one of the coordination sites bound to cobalt is labile under conditions of use of automatic washing Tableware and the remaining coordination sites stabilize the cobalt under automatic dishwashing conditions such as the reduction potential for cobalt (III) to cobalt (II) under alkaline conditions is less than approximately 0.4 volts (preferably lower than max 0.2 volts) versus a normal hydrogen electrode. Cobalt catalysts are preferred having the formula: [Co (NH3) n (M ') m] Yy wherein n is an integer from 3 to 5 (preferably 4 or 5, most preferably 5); M 'is a labile 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 an appropriately selected counter ion present in a number y, which is an integer from 1 to 3 (preferably 2 to 3, most preferably 2 when Y is an anion charged with -1), to obtain a balanced salt in charge . The preferred cobalt catalyst of this type useful herein are the cobalt-pentamine chloride salts having the formula [Co (NH3) 5CI] Yy and especially [Co (NH3) 5CI] Cl2. Very preferred are the compositions of the present invention which use cobalt bleach catalysts (III) having the formula: [Co (NH3) n (M) m (B)] Ty wherein the cobalt is in 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 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 = 1, then m = 0 and n = 4; and T is one or more appropriately selected counterions present in number y, where y is an integer to obtain a salt balanced in charge (preferably y is 1 to 3, most preferably 2 when T is an anion charged with -1); and wherein said catalyst has a base hydrolysis constant of less than 0.23 M ~ 1 s ~ 1 (25 ° C). The most preferred cobalt catalyst useful herein are salts of cobalt pentaminoacetate having the formula [Co (NH3) 5? Ac] Ty, wherein OAc represents an acetate portion and especially cobalt pentaminoacetate chloride, Co (NH3) 5? Ac] Cl2; as well as [Co (NH3) 5OAc] (OAc) 2; [Co (NH3) 5OAc] (PF6) 2; [Co (NH3) 5OAc] (SO4); [Co (NH3) 5OAc] (BF4) 2; and [Co (NH3) 5OAc] (NO3) 2. As a practical matter, and not by way of limitation, the cleaning compositions and cleaning methods herein can be adjusted to provide the order of at least one part per one hundred million of the active bleach catalyst species in the medium of aqueous wash, and preferably will provide from about 0.01 ppm to about 25 ppm, most preferably from about 0.05 ppm to about 10 ppm, and most preferably still from about 0.1 ppm to about 5 ppm, of the catalyst species of bleaching in the washing solution. In order to obtain such levels in the automatic dishwashing compositions of the present invention will comprise from about 0.0005% to about 0.2%, most preferably from about 0.004% to about 0.08% of the bleach catalyst of the cleaning compositions. 4. pH and variation of pH regulation Many detergent compositions of the present invention will be regulated as to their pH, that is, they are relatively resistant to pH drop in the presence of acid soils. However, other compositions herein may have exceptionally low pH regulation capacity, or they may not be regulated in terms of their pH. Techniques for controlling or varying the pH to recommended levels of use in general include the use not only of pH regulators but also alkalis, acids, pH jump systems, additional double-compartment vessels, etc., and well known by those skilled in the art. Preferred ADD compositions herein comprise a pH adjusting component selected from inorganic alkaline salts and water soluble organic or inorganic builders. The pH adjusting components are selected such that when the ADD compositions are dissolved in water at a concentration of 1,000 to 10,000 ppm, the pH remains in the range above about 8, preferably from about 9.5 to about 1. 1. The phosphate-free pH adjusting component of the invention is selected from the group consisting of: (i) sodium carbonate or sesquicarbonate; (ii) sodium silicate, preferably sodium hydrosilicate having a ratio of Si 2: Na 2? from about 1: 1 to about 2: 1, and mixtures thereof with limited amounts of metasilicate; (iii) sodium citrate; (iv) citric acid; (v) sodium bicarbonate; (vi) sodium borate, preferably borax; (vii) sodium hydroxide; and (viii) mixtures of (i) - (vii). The most preferred embodiments of pH adjusting component systems are binary mixtures of granulated sodium citrate with anhydrous sodium carbonate, and mixtures of three components of granulated sodium citrate trihydrate, citric acid monohydrate and anhydrous sodium carbonate. The amount of pH adjusting component in the ADD compositions is preferably from about 1% to about 50%, by weight of the composition. In a preferred embodiment, the pH adjusting component is present in the ADD compositions in an amount of from about 5% to about 40%, preferably from about 10% to about 30% by weight. For compositions of the present invention having a pH between 9.5 and 11 of the initial wash solution, embodiments of particularly preferred ADD compositions comprise, by weight of ADD composition, from about 5% to about 40%, preferably from about 10% to about 30%, most preferably from about 15% to about 20%, of sodium citrate with an amount of from about 5% to about 30%, preferably from about 7% to about 25%, very preferably from about 8% to about 20%, sodium carbonate. The pH adjustment system can be complemented (i.e., for improved sequestration in hard water) by other optional builder salts selected from phosphate-free builders known in the art, including the various borates, hydroxysulfonates, polyacetates and polycarboxylates of alkali metal, ammonium or substituted ammonium soluble in water. Alkali metal salts are preferred, especially sodium salts of said materials. Alternative, water-soluble organic phosphorus-free builders, can be used for their sequestering properties. Examples of polyacetate and polycarboxylate builders are the sodium, lithium, ammonium and substituted ammonium salts of ethylenediaminetetraacetic acid; nitriloacetic acid, tartrate monosuccinic acid, tartrate disuccinic acid, oxydisuccinic acid, carboxymethylsuccinic acid, mellitic acid and sodium benzene polycarboxylate salts.

. Water soluble silicate The automatic dishwashing detergent compositions of the present invention may also comprise water soluble silicates. The water soluble silicates herein are any silicates that are soluble to the extent that they do not adversely affect the stain removal / film removal characteristics of the ADD composition.

Examples of silicate are sodium metasilicate and, in general, alkali metal silicates, particularly those having a ratio of Si 2: Na 2? in the range of 1.6: 1 to 3.2: 1 and layered silicates, such as the layered sodium silicates described in U.S. Patent 4,664,839, issued May 12, 1987 to H. P. Rieck. NaSKS-6® is the trade name for a crystalline layered silicate sold by Hoechst (commonly abbreviated as "SKS-6"). Unlike zeolite builders, the NaSKS-6 silicate builder does not contain aluminum. NaSKS-6 has the morphological form of stratified silicate d-Na2Si? 5. It can be prepared by methods such as those described in German Application DE-A-3,417,649 and DE-A-3,742,043. SKS-6 is a highly preferred stratified silicate for use herein, but other layered silicates, such as those having the general formula NaMSix? 2? +? yH2? wherein M is sodium or hydrogen, x is a number from 1.9 to 4, preferably 2, and y is a number from 0 to 20, preferably 0 may be used herein. Some other stratified silicates from Hoechst include NaSKS-5, NaSKS-7 and NaSKS-11 as the alpha, beta and gamma forms. As indicated above, the d-Na2S¡Os (NaSKS-6) form is most preferred for use herein. Other silicates can also be used such as for example magnesium silicate, which can serve as a tightening agent in granulated formulations, as a stabilizing agent for oxygen bleaches, and as a component of foam control systems.

Silicates particularly useful in automatic dishwashing (ADD) applications include granular water-ratio silicates such as BRITESIL® H2O from PQ Corp., and BRITESIL® H24 from a common source, although liquid grades of various silicates can be used when the composition ADD has liquid form. Within safety limits, the sodium metasilicate or sodium hydroxide alone or in combination with other silicates can be used in an ADD context to increase the wash pH to a desired level. 6. Chelating Agents The compositions herein also optionally contain one or more selective transition metal sequestrants, "chelators" or "chelating agents", eg, iron and / or copper and / or manganese chelating agents. Chelating agents suitable for use herein may be selected from the group consisting of aminocarboxylates, phosphonates (especially aminophosphonates), polyfunctionally substituted aromatic chelating agents, and mixtures thereof. Without pretending to be limited by theory, it is believed that the benefit of these materials is due in part to their exceptional ability to control iron, copper and manganese in washing solutions known to decompose hydrogen peroxide and / or activators. bleach; Other benefits include inorganic film prevention or inhibition of scale. Commercial chelating agents to be used in the present include the series DEQUEST®, and chelators of Monsanto, DuPont and Nalco, Inc. The aminocarboxylates useful as optional chelating agents are further reported by the ethylenediaminetetracetates, N-hydroxyethylenediaminetriacetates, nitrilotriacetates, ethylenediamonotetraproprio-ines, triethylenetetraaminohexacetates, diethylenetriaminepentaacetates and ethanoldiglicines, alkali metal salts, ammonium. and substituted ammonium thereof. In general, chelator mixtures can be used for a combination of functions, such as control of multiple transition metals, long-term product stabilization, and / or control of oxides and / or precipitated transition metal hydroxides. Polyfunctionally substituted aromatic chelating agents are also useful in the compositions herein. See the patent of E.U.A. 3,812,044 issued May 21, 1974 to Connor et al. Preferred compounds of this type in acid form are dihydroxydisulfobenzenes such as 1,2-dihydroxy-3,5-disulfobenzene. A highly preferred biodegradable chelator for use herein is ethylenediamine disuccinate ("EDDS"), especially the [S, S,] isomer as described in the U.S.A. 4,704,223 issued November 3, 1987 to Hartman and Perkins. The trisodium salt is preferred although other forms, such as magnesium salts, may also be useful. The aminophosphonates are also useful for use as chelating agents in the compositions of the invention when at least low levels of total phosphorus are allowed in the detergent compositions and include ethylene diamine tetrakis (methylene phosphonates) and the diethylene diamine tetrakis (methylene phosphonates). Preferably, these aminophosphonates do not contain alkyl or alkenyl groups with more than 6 carbon atoms. If used, these chelating agents or selective sequestrants in terms of transition metal will preferably comprise from about 0.001% to about 10%, most preferably from about 0.05% to about 1% by weight of the compositions herein. 7. Dispersant polymer The preferred ADD compositions of the present invention may further contain a dispersant polymer. When present, a dispersing polymer in the ADD compositions of the present invention is typically at levels in the range of from about 0 to about 25%, preferably from about 0.5% to about 20%, most preferably from about 1% to about 8% by weight of the ADD composition. The dispersing polymers are useful for improved film removal performance of the ADD compositions of the present invention, especially in higher pH embodiments, such as those in which the wash pH exceeds about 9.5. Particularly preferred are polymers that inhibit the deposition of calcium carbonate or magnesium silicate in the ware.

Dispersant polymers suitable for use herein are illustrated by the film-forming polymers described in E, U, A, No. 4,379,080 (Murphy), issued April 5, 1983. Suitable polymers are preferably salts by at least partially neutralized or of alkali metal, ammonium or substituted ammonium (e.g., mono-, di- or triethanolammonium) of polycarboxylic acids. Alkali metal salts, especially sodium, are most preferred. Although the molecular weight of the polymer can vary over a broad spectrum, it is preferably from about 1,000 to about 500,000, most preferably from about 1,000 to about 250,000, and most preferably, especially if the ADD composition is to be Use in American automatic dishwashing equipment, is from about 1,000 to about 5,000. Other suitable dispersing polymers include those described in the U.S.A. Nos. 3,308, 067, 4,530,766, 3,723,322, 3,929,107, 3,803,285, 3,629,121, 4,141,841 and 5,084,535; European Patent No. 66,915. 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 about 20%, can also be used. by weight of the dispersant polymer.

Particularly preferred dispersant polymers are low molecular weight modified polyacrylate copolymers. The suitable low molecular weight polyacrylate dispersing polymer preferably has a molecular weight of less than about 15,000, preferably from about 500 to about 10,000, most preferably from about 1,000 to about 5,000. The most preferred polyacrylate copolymer for use herein has a molecular weight of about 3,500 and is the fully neutralized form of the polymer comprising about 70% by weight of acrylic acid and about 30% by weight of methacrylic acid. Other dispersant polymers useful herein include polyethylene glycols and polypropylene glycols having a molecular weight of about 950 to about 30,000 which can be obtained from the Dow Chemical Company of Midland, Michigan. Other dispersant polymers useful herein include cellulose sulfate esters such as cellulose acetate sulfate, cellulose sulfate, hydroxyethyl cellulose sulfate, methyl cellulose sulfate, and hydroxypropyl cellulose sulfate. Sodium cellulose sulfate is the most preferred polymer of this group. Yet another group of acceptable dispersants are organic dispersant polymers such as polyaspartate. 8. Materials Care Agents The ADD compositions of the present invention may contain one or more agents for the care of materials that are effective as corrosion inhibitors and / or anti-rust auxiliaries. Said materials are preferred components of automatic dishwashing compositions, especially in some European countries where the use of electrodeposited silver and nickel and fine silver is still comparatively common in domestic ware, or when aluminum protection is a concern and the composition is low in silicate. Generally, such materials care agents include metasilicate, silicate, bismuth salts, manganese salts, paraffin, triazoles, pyrazoles, thiols, mercaptans, aluminum fatty acid salts and mixtures thereof. When present, said protective materials are preferably incorporated at low levels, for example, from about 0.01% to about 5% of the ADD compositions. Suitable corrosion inhibitors include paraffin oil, typically a predominantly branched aliphatic hydrocarbon having a number of carbon atoms in the range of from about 20 to about 50; the preferred paraffin oil is selected from predominantly branched C 25-45 species with a cyclic to non-cyclic hydrocarbon ratio of about 32:68. A paraffin oil which satisfies these characteristics is sold by Wintershall, Salzbergen, Germany, under the trade name WINOG 70. Furthermore, the addition of low levels of bismuth nitrate (ie Bi (N03) 3) is also preferred.

Other corrosion inhibiting compounds include benzotriazole and comparable compounds; mercaptans or thiols including thionephthol and thioanthranol; and finely divided aluminum fatty acid salts, such as aluminum tristearate. The formulator will recognize that such materials will generally be used judiciously and in limited amounts to avoid any tendency to produce stains or films on the glassware or to compromise the bleaching action of the compositions. For this reason, mercaptan anti-rust agents that are strongly reactive to the bleach and common fatty carboxylic acids that precipitate with calcium in particular are preferably avoided. 9. Silicone Foam and Phosphate Adsorbers The ADD compositions of the invention may optionally contain an alkyl ester phosphate suppressant, a silicone foam suppressant or combinations thereof. The levels in general are from about 0% to about 10%, preferably around 0. 001% to approximately 5%. However, generally (for considerations of cost and / or deposition) the preferred compositions herein do not comprise foam suppressors or comprise foam suppressors only at low levels, less than about 0.1% active foam suppressing agent. The technology of silicone foam suppressors and other foam removing agents useful herein are extensively documented in "Defoaming, Theory and Industrial Applications," Ed., P.R. Garrett, Marcel Dekker, N.Y., 1973, ISBN 0-8247-8770-6, incorporated herein by reference. See especially the chapters entitled "Foam control in Detergent Products" (Ferch et al) and "Surfactant Antifoams" (Blease et al). See also U.S.A. 3,933,672 and 4,136,045. Highly preferred silicone foam suppressors are the combined types known for use in laundry detergents such as heavy duty granules, although the types hitherto used only in heavy duty liquid detergents can also be incorporated into the present compositions. For example, polydimethylsiloxanes having trimethylsilyl or alternative end blocking units can be used as the silicone. These can be combined with silica and / or non-silicone-containing active surface components, as illustrated by a foam suppressor comprising 12% silicone / silica, 18% stearyl alcohol and 70% starch in granulated form. A suitable commercial source of the active silicone compounds is Dow Corning Corp. If it is desired to use a phosphate ester, suitable compounds are described in US Pat. 3,314,891, issued April 18, 1967 to Schmolka et al, incorporated herein by reference. Preferred alkyl ester phosphates contain from 16 to 20 carbon atoms. Highly preferred alkyl ester phosphates are monostearyl acid phosphate or monoleic acid phosphate, or salts thereof, particularly alkali metal salts or mixtures thereof.

It has been found preferable to avoid the use of simple calcium precipitating soaps as antifoam agents in the present compositions as they tend to be deposited on the dishes. In fact, the ester phosphates are not completely free of these problems and the formulator will generally choose to minimize the content of potentially depositable antifoams in the compositions of the present invention.

. Other optional auxiliaries Depending on whether a greater or lesser degree of compaction is required, the filler materials may also be present in the ADD compositions of the present invention. These include sucrose, sucrose esters, sodium sulfate, potassium sulfate, etc., in amounts up to about 70%, preferably from 0% to about 40% of the ADD composition. The preferred filler is sodium sulfate, especially in good grades that have when very low levels of trace impurities. The sodium sulfate used herein is preferably of sufficient purity to ensure that it is not reactive with the bleach; It can be treated with low levels of sequestrants, such as phosphonates or EDDS in the form of magnesium salt. It should be noted that the preferences, in terms of sufficient purity to avoid bleach decomposition, also apply to ingredients of pH adjusting components, specifically including any silicates used therein.

Although optionally present in the compositions of the present invention, this includes embodiments that are substantially free of sodium chloride or potassium chloride. Hydrotrope materials such as sodium benzenesulfonate, sodium toluenesulfonate, sodium cumenesulfonate, etc., may be present, for example, for a better dispersing surfactant. Perfumes stable to bleach (stable as to smell); and bleach stable dyes such as those described in the U.S.A. 4,714,562, Roselle et al., Issued December 22, 1987 can also be added to the present compositions in appropriate amounts. Other common detergent ingredients consistent with the spirit and scope of the present invention are not excluded. Since the ADD compositions herein may contain water-sensitive ingredients or ingredients that can co-react when put together in an aqueous environment, it is desirable to keep the free moisture content of the ADD compositions to a minimum, for example, 7% or less. , preferably 4% or less of the ADD composition; and providing a package that is substantially impermeable to water and carbon dioxide. Coating measures have been described herein to illustrate a way to protect the ingredients from each other and from air and moisture. Plastic bottles, including refillable or recyclable types, as well as conventional boxes or barrier containers are other useful means to help maximum shelf storage stability. As indicated, when the ingredients are not highly compatible, it may be convenient to coat at least one of these ingredients with a low foaming nonionic surfactant for protection. There are numerous waxy materials that can be easily used to form suitable coated particles of any otherwise incompatible components; however, the formulator prefers those materials that do not have a marked tendency to deposit or to form films on tableware including those of plastic construction. Some automatic dishwashing compositions granulated substantially free of chlorine bleach of the invention are the following: an automatic dishwashing composition substantially free of chlorine bleach comprising amylase (e.g.

TERMAMYL®) and / or a bleach-stable amylase and a bleaching system comprising a source of hydrogen peroxide selected from sodium perborate and sodium percarbonate and a cobalt catalyst as defined herein. An automatic dishwashing composition substantially free of chlorine bleach comprising an amylase increased in oxidative stability and a bleaching system comprising a source of hydrogen peroxide selected from sodium perborate and sodium percarbonate, is also contemplated. cobalt catalyst and TAED or NOBS.

Cleaning Methods The present invention also comprises a method for cleaning dirty tableware consisting of contacting the tableware with an aqueous medium comprising a cobalt catalyst, preferably at a concentration of about 2 ppm to about 10 ppm. , as described above. The preferred aqueous medium has an initial pH in a wash solution above about 8, most preferably from about 9.5 to about 12, most preferably from about 9.5 to about 10.5. This invention also comprises a method for washing tableware in an automatic household dishwashing appliance, which consists in treating the soiled tableware in an automatic dishwashing machine with an aqueous alkaline solution comprising the ADW compositions of the present invention. . The following non-limiting examples further illustrate ADD compositions of the present invention.

EXAMPLE 1 Preparation of Co / I nonionic surfactant EOpBO ^ Neodol 91-8 (30.00 g 58.7 mmoles) is placed in a 250 ml three-necked round bottom flask equipped with a heating mantle, magnetic stirrer, pressure equalizing drip funnel, reflux condenser, internal thermometer and entry for argon, and dried under vacuum at 75 ° C. After releasing the vacuum with argon, metallic sodium (0.03 g, 1.2 mmol) is placed in the flask and the mixture is heated and stirred at 140 ° C until all the sodium has been consumed. Then 1,2-epoxybutane (12.71 g, 176.2 mmol) is added dropwise at a rate to maintain the reaction temperature at > 120 ° C with a target of 140 ° C. All 1, 2-epoxybutane is added and when the reflux has ceased, the mixture is stirred and heated for a further 3 hours at 140 ° C. The mixture at 140 ° C is then placed under vacuum for 15 minutes to remove any traces of 1,2-epoxybutane. A light brown liquid is isolated. The NMR is consistent with the desired compound.

EXAMPLE 2 Preparation of nonionic surfactant of Cg / i 1 EOpCfCH ^ yChbCH Neodol 91-8 (30.00 g, 58.7 mmol) is placed in a 250 ml three-necked round bottom flask equipped with a heating mantle, magnetic stirrer, internal thermometer and inlet for argon, and dried under vacuum at 75 ° C. After cooling to room temperature and releasing the vacuum with argon, methylene chloride (12 ml) and 2-methyl-1-butane (4.53 g, 64.6 mmol) are added. Then, boron trifluoride diethyl ether (0.83 g, 5.9 mmol) is added all at once. This mixture is stirred for 5 days at room temperature. After adding 200 ml of diethyl ether the mixture is washed once with saturated sodium bicarbonate and once with brine. The ether layer is dried under magnesium sulfate and concentrated by rotary evaporation to leave a yellow liquid. The NMR is consistent with the desired compound.

EXAMPLE 3 Preparation of nonionic surfactant of CQ / I 1 EO8Í H2I4 H3 Anhydrous tetrahydrofuran (250 ml) and 60% 60% sodium hydride (8.22 g, 205.6 mmol) are placed in a 500 ml three-necked round bottom flask equipped with a magnetic stirrer, drip funnel, equalizer pressure, internal thermometer and inlet for argon. After cooling the mixture to 0 ° C, Neodol 91-8 (35.00 g, 68.5 mmol) is added dropwise over 10 minutes. After warming to room temperature, the mixture is stirred for 2 hours. 1-Iodopentane (33.93 g, 171.3 mmol) is added dropwise over 10 minutes. After stirring at room temperature for 4 days, the mixture is quenched with alcohol, neutralized with concentrated HCl, diluted with 500 ml of diethyl ether and then extracted once with saturated NaHCO 3 and once with brine. The ether layer is dried under magnesium sulfate and concentrated under rotary evaporation. This mixture is purified by flash chromatography (5:95 MeOH: CH 2 Cl 2) to give a golden colored liquid. The NMR is consistent with the desired compound.

EXAMPLE 4 Preparation of ether-blocked alcohol surfactant Place Neodol® 91-8 (16.60 g, 0.0325 mol Shell Chemical Co.) in a 250 ml three-necked round bottom flask equipped with a condenser, argon inlet, addition funnel, magnetic stirrer and probe internal temperature. The contents of the flask are dried under vacuum at 75 ° C for 15 minutes after establishing an atmosphere of argon, tin (IV) chloride (0.25 ml, 2.1 mmol Aldrich) is added to the flask by means of a syringe. The mixture is heated to 60 ° C, at which point C 12/14 alkyl glycidyl ether (10.00 g, 0.039 mol) is added dropwise over 15 minutes while maintaining a temperature of 75-80 ° C. After stirring for 18 hours at 60 ° C the mixture is stirred for an additional hour at 75 ° C until the glycidyl ether is consumed, as determined by thin layer chromatography. The mixture is cooled to room temperature and diluted with 1 ml of water. The solution is passed through 170 g of silica gel (Aldrich 227196, diameter 7x12) while eluting with 5% methanol (40 ml) dichloromethane. The filtrate is concentrated by rotary evaporation and separated in a Kugeirohr oven (70 ° C, 0.1 mm Hg for 30 minutes) to give a product as an oil. The following non-limiting examples illustrate compositions suitable for use in methods of the present invention.

EXAMPLE 5 Compositions for automatic dishwashing Ingredients% by weight AB Sodium Tripolyphosphate (STPP) 24.0 45.0 Sodium Carbonate 20.0 13.5 Silicate 2R hydrated 15.0 13.5 Nonionic Surfactant1 3.0 3.0 Amine Oxide of C-iß 1.0 1.0 Polymer2 4.0 - Protease (4% active) 0.83 0.83 Amylase ( 0.8% active) 0.5 0.5 Perborate monohydrate (15.5% active AvO) 3 0.5 0.5 Cobalt catalyst4 0.008 - Dibenzoyl oxide (18% active) 4.4 4.4 Water, sodium sulphate, comp. various The rest The rest 1 Nonionic surfactant according to example 1. 2 Terpolymer selected from either 60% acrylic acid / 20% maleic acid / 20% ethyl acrylate, or 70% acrylic acid / 10% maleic acid / 20% ethyl acrylate. 3 The AvO level of the previous formula is 2.2%. 4 Pentaaminoacetatecobalt Nitrate (III) prepared as described above; it can be replaced by MnTacN. The following examples illustrate ADD compositions with phosphate builder that contain a bleach / enzyme particle, but are not intended to limit them. These compositions are suitable for use in the methods of the present invention. All the percentages indicated are by weight of the finished compositions, other than the perborate component (monohydrate), which are listed as AvO.

EXAMPLES 6-7 Ingredients% by weight 6 7 STPP 30.0 32.0 Na2CO3 30.5 20.5 Silicate 2R SiO2) 8.0 4.0 Catalyst 0.008 0.004 Savinase ™ 12T - 1.1 Protease D 0.9 - Perborate (AvO) 5.0 0.7 Polymer2 4.0 0.7 Dibenzoyl peroxide 0.2 0.15 Paraffin 0.5 0.5 Benzotriazole 0.10 0.3 Amine oxide of C-iß 0.5 0.5 Nonionic surfactant3 2.0 2.0 Sodium sulfate, moisture The rest- 1 Pentaaminoacetatecobalt Nitrate (III) prepared as described above; it can be replaced by MnTacN. 2 Polyacrylate or Acusol 480N or polyacrylate copolymers / polymethacrylate 3 Nonionic surfactant according to example 2. In the compositions of examples 6 and 7, respectively, the catalyst and the enzymes are introduced into the compositions as mixed particles of 200-2400 microns which are prepared by coating operations by spraying, fluidized bed granulation, marumerization, pill formation or flaking / crushing. If desired, the protease and amylase enzymes, for reasons of stability, and these separate compositions can be added to the compositions.

EXAMPLES 8-9 Ingredients% by weight 8 9 STPP 25 31 Na2C03 23.0 15.0 Silicate 2R (SiO2) 17.5 25.0 Hypochlorite 1.0 3.0 Polymer1 2.0 - Dibenzoyl peroxide - 0.15 Paraffin 1.0 1.0 Ci6 amine oxide 0.5 1.0 Nonionic surfactant2 2.0 3.0 Sodium sulfate, humidity -The rest- 1 Polyacrylate or Acusol 480N or polyacrylate / polymethacrylate copolymers 2 Nonionic surfactant according to example 3. The following examples illustrate ADD compositions in gel-liquid form suitable for use in the methods of the present invention.

EXAMPLES 10-11 Ingredients% by weight 10 11 STPP 32.0 25.0 Na2C03 0.7 2.0 Silicate 2R (SiO2) 0.3 1.0 Savinase ™ 12T 2.0 1.0 Termamyl ™ 1.4 0.5 Perborate (AvO) 3.5 - Amine oxide of C-? 6 0.8 0.8 Nonionic surfactant1 3.5 3.5 Sodium sulfate, humidity The rest 1 Nonionic surfactant according to example 4. The following examples illustrate ADD compositions to be added during rinsing suitable for use in the methods of the present invention.

EXAMPLES 12-13 Ingredients% by weight 12 13 Citric Acid 10.0 15.0 Ethanol 5.0 10.0 Acid HEDP1 1.0 0.7 Sodium Cumensulfonate 15.0 10.0 Polymer > 2 - 1.0 C16 amine oxide 2.0 0.5 Nonionic surfactant3 15.0 8.0 HnmoHarl Fl roctn 1 1-hydroxyethylidene-1,1-diphosphonic acid. 2 Polyacrylate or Acusol 480N or polyacrylate copolymers / polymethacrylate 3 Nonionic surfactant according to example 2. The following examples illustrate ADD compositions in the form of suitable tablets for use in the methods of the present invention.

EXAMPLES 14-15 Ingredients% by weight 14 15 STPP 48.0 30 Na2CO3 15.0 25.0 Silicate 2R (SiO2) 4.0 8.0 Catalyst 0.008 0.004 Savinase ™ 12T - 1.0 Termamyl ™ 0.6 0.5 Perborate (AvO) 10.0 15.0 Polymer 2.0 2.0 2.0 Dibenzoyl peroxide 0.2 0.15 Paraffin 1.0 1.0 Benzotriazole 0.5 0.5 Amine oxide of C-? 6 1.0 1.0 Nonionic surfactant3 3.0 3.0. ^ Ilfatn Ho cnHin hnmc-HaH The pentaaminoacetatecobalt nitrate (III) can be replaced by MnTacN. 2 Polyacrylate or Acusol 480N or polyacrylate / polymethacrylate copolymers 3 Nonionic surfactant according to example 2.

Claims (13)

NOVELTY OF THE INVENTION CLAIMS

1. - A detergent composition for automatic dishwashing comprising: a) from 5% to 90% by weight of the composition of a builder; b) from 0.1% to 15% by weight of the composition of an oxide surfactant, said oxide surfactant being selected from the group consisting of amine oxides, phosphine oxides, silfoxides and mixtures thereof; c) from 0.1% to 15% by weight of the composition of a low foaming nonionic surfactant with an X / Y number greater than or equal to 1.00 and when said low foaming nonionic surfactant contains a glyceryl ether group , the block in said low foaming nonionic surfactant is a linear or branched alkyl group containing at least 4 carbon atoms and the number X / Y is calculated in the absence of dimers and trimers; d) optionally, from 0.1% to 40% by weight of the composition of a bleaching agent; and e) auxiliary materials; wherein the weight ratio of the low foaming nonionic surfactant to the oxide surfactant is from 2: 1 to about 30: 1.

2. A detergent composition for automatic dishwashing comprising: a) from 5% to 90% by weight of the composition of a builder; b) from 0.1% to 15% by weight of the composition of an oxide surfactant, said oxide surfactant being selected from the group consisting of amine oxides, phosphine oxides, silfoxides and mixtures thereof; c) from 0.1% to 15% by weight of the composition of a low foaming nonionic surfactant wherein said low foaming nonionic surfactant has an interfacial tension of less than 8 dynes / cm; d) optionally, from 0.1% to 40% by weight of the composition of a bleaching agent; and e) auxiliary materials; wherein the weight ratio of the low foaming nonionic surfactant to the oxide surfactant is from 2: 1 to about 30: 1.

3. The detergent composition for automatic dishwashing according to any of claims 1 or 2, further characterized in that said low foaming nonionic surfactant has the formula: R1 (EO) a (PO) b (BO) c wherein R1 is a linear or branched C6 to C20 alkyl, a is an integer from 2 to 30, b is an integer from 0 to 30; c is an integer from 1 to 10.

4. The detergent composition for automatic dishwashing according to any of claims 1 or 2, further characterized in that said low foaming nonionic surfactant has the formula: R10 [CH2CH ( R3) 0] m [CH2] kCH (OH) [CH2] jOR2 wherein R1 and R2 are saturated or unsaturated, linear or branched aliphatic or aromatic hydrocarbon radicals having from 1 to 30 carbon atoms; R3 is H, or a linear aliphatic hydrocarbon radical having 1 to 4 carbon atoms; m is an integer that has an average value of 1 to 40, where when m is 2 or greater R3 can be the same or different and k and j are integers that have an average value of 1 to 12; wherein when m is 15 or greater and R3 is H and methyl, at least four of R3 are methyl, wherein when m is 15 or greater and R3 includes H and from 1 to 3 methyl groups, then at least one R3 is ethyl, propyl or butyl, wherein R2 may be optionally alkoxylated, wherein said alkoxy is selected from ethoxy, propoxy, butyloxy and mixtures thereof; wherein said surfactant has less than 30%, preferably less than 15% and most preferably less than 5% of dimers and trimers of said nonionic surfactant.

5. The detergent composition for automatic dishwashing according to any of claims 1 or 2, further characterized in that said low foaming nonionic surfactant has the formula: R 0 [CH 2 CH (R 3) 0] e R 2 wherein R ^ is a saturated aliphatic or aromatic hydrocarbon radical or Unsaturated, linear or branched having from 1 to 30 carbon atoms; R 2 is a saturated or unsaturated, linear or branched aliphatic or aromatic hydrocarbon radical having from 1 to 30 carbon atoms, optionally containing from 1 to 5 hydroxy groups; and optionally substituted with an ether group; R3 is H, or a linear aliphatic hydrocarbon radical having 1 to 4 carbon atoms; e is an integer having an average value of 1 to 40, wherein R2 can optionally be alkoxylated, wherein said alkoxy is selected from ethoxy, propoxy, butoxy and mixtures thereof.

6. - The detergent composition for automatic dishwashing according to any of claims 1 to 5, further characterized in that it comprises a detersive enzyme.

7. The detergent composition for automatic dishwashing according to any of claims 1 to 6, further characterized in that it comprises a metal-containing bleach catalyst selected from bleach catalysts containing manganese, bleach catalysts containing cobalt and mixtures thereof.

8. The detergent composition for automatic dishwashing according to any of claims 1 to 7, further characterized in that it comprises a co-surfactant selected from the group consisting of non-ionic surfactants of low turbidity point, surfactants non-ionic high-cloud point, anionic surfactants and mixtures thereof.

9. The detergent composition for automatic dishwashing according to any of claims 1 to 8, further characterized in that it comprises less than 0.1% of active foam suppressing agent.

10. The detergent composition for automatic dishwashing according to any of claims 1 to 9, further characterized in that said oxide surfactant is an amine oxide surfactant having the formula: O R3 (OR4) xN ( R5) 2 wherein R is an alkyl, hydroxyalkyl or alkylphenyl group or mixtures thereof containing from about 8 to about 22 carbon atoms; R4 is an alkylene or hydroxyalkylene group containing from about 2 to about 3 carbon atoms or mixtures thereof; x is from 0 to about 3; and each of R ^ is an alkyl or hydroxyalkyl group containing from about 1 to about 3 carbon atoms or a polyethylene oxide group containing from about 1 to about 3 ethylene oxide groups.

11. The detergent composition for automatic dishwashing according to any of claims 1 to 10, further characterized in that said amine oxide having the formula: wherein R5 is as defined above.

12. The detergent composition for automatic dishwashing according to any of claims 1 to 11, further characterized in that said low foaming nonionic surfactant is selected from the group consisting of C9.11 P03E013P015; C9.11 P03E013B06; C9.11 P03E013B03; C9.11 E013B06; C9.11 E013B03; C9.11 B01 E013B03; C9.11EO8BO3; C12.15EO7B02; C9.11EO8BO2; C 9, 11 EO 8 BO 1; C12.13E06.5TB01; C9.11 EO8 (CH3) 2CH2CH3; C11 / 15E015P06C12 / 14; C9.11 E08 (CH2) 4CH3; and mixtures thereof.

13. - A method of washing tableware in an appliance for automatic washing of domestic dishes, said method consisting of treating the dirty tableware in an automatic dishwashing machine with an aqueous alkaline solution comprising a composition for automatic dishwashing of according to claims 1 to 12.