MXPA01008526A

MXPA01008526A - Automatic dishwashing compositions comprising selected nonionic surfactants.

Info

Publication number: MXPA01008526A
Application number: MXPA01008526A
Authority: MX
Inventors: Jeffrey Painter Donald
Original assignee: Procter & Gamble
Priority date: 1999-02-22
Filing date: 2000-02-10
Publication date: 2002-06-04
Also published as: WO2000050551A1; CA2369120A1; ATE324426T1; EP1155105B1; EP1155105A1; AU2990000A; JP2002537484A; DE60027549T2; DE60027549D1

Abstract

Automatic dishwashing detergent compositions comprising: a) 5 % to 90 % by weight of builder; b) 0.1 % to 15 % by weight of: I) a surfactant of the formula R1(EO)a(PO)b(BO)c, wherein R1 is a linear or branched C6 to C20 alkyl; a is from 2 to 30; b is from 0 to 30; c is from 1 to 30; and said surfactant has an X/Y number less than 1.90; and or ii) a surfactant of the formula R1OoCH2CH(R3)O!e?R2, wherein R1 is a hydrocarbon radical having from 1 to 30 carbon atoms; R2 is a hydrocarbon radical having 1 to 30 carbon atoms; R3 is H, or a linear aliphatic hydrocarbon radical having from 1 to 4 carbon atoms; e is an integer having an average value from 1 to 40; c) optionally, from 0.1 % to 40 % by weight of a bleaching agent and d) adjunct materials, such as enzymes, surfactants other than (b), or chelating agents.

Description

COMPOSITIONS FOR THE AUTOMATIC WASHING OF DISHES COMPRISING SELECTED NON-IONIC SURGERY 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.

BACKGROUND TECHNIQUE 10 Patent of E.U.A. 4,272,394, WO 94/22800 and WO 93/04153.

BRIEF DESCRIPTION OF THE INVENTION It has now been readily discovered that automatic dishwashing detergent compositions ("ADD") comprising detergency builder and butoxy-blocked nonionic surfactant system, preferably further comprising a bleaching agent and / or enzymes, provide Higher stain reduction benefits.

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 from 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 from about 0.1% to about 15% by weight of the composition of a nonionic surfactant, wherein the nonionic surfactant is selected from the group which consists of: (i) a nonionic surfactant of the formula R 1 (EO) to (PO) b (BO) c Where R 1 is a straight or branched chain alkyl of C 2 to C 2; a is from about 2 to about 30; b is from 0 to about 30; c is from about 1 to about 30; and the nonionic surfactant has an X / Y number of less than 1.90; (ii) a nonionic surfactant of the formula: R 1 O [CH 2 CH (R 3) 0] e R 2 Where R 1 is a straight or branched, saturated or unsaturated, aliphatic or aromatic hydrocarbon radical having from 1 to 30 atoms of carbon, R 2 is a straight or branched chain hydrocarbon radical, saturated or unsaturated, aliphatic or aromatic having from 1 to 30 carbon atoms, optionally containing from 1 to 5 hydroxy groups; and further 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 fe has an average value of 1 to 40, wherein R2 can optionally be alkoxylated wherein the alkoxy is selected from ethoxy, propoxy, butyloxy and mixtures thereof; and (iii) their mixtures; c) 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 d) auxiliary materials, preferably automatic dishwashing detergent auxiliary materials selected from the group consisting of enzymes, surfactants other than chelating agents (b) and mixtures thereof. The present invention comprises (but is not limited to) fully formulated ADD compositions, in granulated form, 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, most particularly a dishwashing method in an automatic household dishwashing appliance, which involves 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 the excellent removal of greasy dirt, good care of dishes and good general cleaning. 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. 10 DETAILED DESCRIPTION OF THE INVENTION Automatic Dishwashing Compositions: The automatic dishwashing compositions of the present invention comprise a detergent builder and a non-ionic surfactant system blocked by butoxy, and preferably also include a bleaching agent (such as a bleach). chlorine 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. Also useful are sources of available oxygen such as a persulfate bleach (e.g., OXONE, manufactured by DuPont). In the preferred embodiments, ingredients are present M MÉ &ÍÍÍÍÍÍIMIM * mJ - * - l * ^ -, ^. ai,. »*. - r. ",,, M-. • a. . .. ... to , -"--. m * ~ * 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 about 5% a 10 about 75%, of 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, of about 0.01% at 15 approximately 10% of a chelator, and from about 0.00001% to about 10% of a detersive enzyme, although additional or auxiliary ingredients may be present. The detergent compositions herein in granular form typically limit the water content, for example, to less than about 7% free water, for better stability to the water. 20 storage. Although the compositions of the present invention can be formulated using chlorine-containing bleach additive, the preferred ADD compositions of this invention (especially those comprising enzymes detersives) 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 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 low enough. 15 any conditions of comparative test that are used, to increase the cleanliness of the dirty surface. In the automatic dishwashing, the dirty surface may be, for example, a porcelain cup with a tea stain, a porcelain cup with lipstick stain, dishes soiled with simple tears or more complex food stains, or 20 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 mucgo 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.

Selected nonionic surfactant The basic nonionic surfactants of the present invention should have an X / Y number of less than 1.90, preferably of less than 1.85, most preferably less than 1.75. The determination of this X / Y number is described below. The surfactants of the present invention are selected from the group consisting of: (i) a surfactant of the formula R 1 (EO) to (PO) b (BO) c wherein R 1 is a linear C 6 to C 20 alkyl or branched, preferably straight or branched C8 to C18 alkyl, most preferably straight 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 20 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 30, preferably from 1 to 15, most preferably from 1 to 10, most preferably still from 1 to 6. (i) a nonionic surfactant of the formula: R1O [CH2CH (R3) 0] eR2 wherein R1 is a saturated aliphatic or aromatic hydrocarbon radical or unsaturated, linear or branched having from 1 to 30 carbon atoms; R2 is a saturated or unsaturated aliphatic or aromatic hydrocarbon radical, linear or branched having 1 to 30 carbon atoms, which optionally contains 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 from 1 to 40, wherein R2 can optionally be alkoxylated, wherein said alkoxy is selected from ethoxy, propoxy, butyloxy and mixtures thereof. Suitable surfactants include, but are not limited to; Surfactant Value of X / Y C9.11 PO3EO13BO6 1.41 C9.11 PO3EO13BO3 1.70 C9.11 EO13B06 1.49 C9.11 EO13B03 1.88 15 C9,11BO1 E013B03 1.72 C9.11 EO8BO3 1.29 C12.15EO7B02 1.03 C9.11 EO8BO2 1.41 C9.11 EO8BO1 1.58 C12,13EO6.5T * BO1 1.10 Oenota the highest, or narrow selection of EO distribution. twenty IiiiinfWiMilrfptir- MilliMIl Calculation of X / Y The LFNI surfactants of the present invention must all have a hydrophobic to hydrophilic ratio, or "X / Y" 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, A typical example is shown below. For C-? 3EO-? 2C? 3, 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 "Y" 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 systems of nonionic surfactants wherein foaming (when absent) are preferred.

^ St ^ tHaüt any silicone foaming agent) is less than 5.08 cm, preferably less than 2.54 cm, determined by the method described in the US patent. 5,294,365.

Optional Surfactant Coagents The composition of the present invention may also contain optional surfactant coagents. These optional surfactants will preferably be stable to the bleach. Preferred optional surfactant coagents are low cloud point nonionic surfactants, non-ionic high-cloud point surfactants, anionic surfactants and mixtures thereof. Nonionic surfactant coagents 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% of the composition . In general, surfactant coagents 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 is can observe is referred to as the "turbidity point" (see Kirk Othmer, pp. 360-362, previously mentioned). As used herein, a non-ionic co-surfactant of "low cloud point 5" 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 surfactant coagents include nonionic alkoxylated surfactants, especially primary ethoxylated alcohol ethoxylates, and polyoxypropylene / polyoxyethylene / polyoxypropylene (PO / EO / PO) reverse block polymers. Also, such low cloud point nonionic surfactant coagents include, for example, ethoxylated-propoxylated alcohol (e.g., Poly-Tergent® SLF18 from Olin Corporation) and poly (oxyalkylated) alcohols blocked with epoxy (eg.

For example, Olin Corporation Poly-Tergent® SLF18B series of nonionics, as described for example in WO 94/22800, published October 13, 1994 by Olin Corporation). The nonionic surfactant coagents may optionally contain propylene oxide in an amount of up to 15% by weight. Others Preferred nonionic surfactant coagents 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 surfactant coagents further comprise a polymeric polyoxyethylene-polyoxypropylene block composite. The polymeric polyoxyethylene-polyoxypropylene block compounds include those based on ethylene glycol, propylene glycol, glycerol, trimethylolpropane and ethylene diamine as 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 10 REVERSED PLURONIC® 25R2 and TETRONIC® 702. Such surfactant coagents are typically used herein as low cloud point nonionic surfactants. As used herein, a "high cloud point" nonionic surfactant coagent is defined herein as an agent system ingredient.

A nonionic surfactant having a cloud point greater than 40 ° C, preferably greater than about 50 ° C, and most preferably greater than about 60 ° C. Preferably, the nonionic surfactant coagent system comprises an ethoxylated surfactant derived from the reaction of a monohydric alcohol or alkylphenol containing from about 8 to 20 about 20 carbon atoms, with an amount of about 6 to about 15 moles of ethylene oxide per mole of alcohol or alkylphenol on an average basis. Such high cloud point nonionic surfactant coagents include, for example, Tergitol 15S9 (provided by Union ? tp? nffiiü * i * w? i * '' '* 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 surfactant coagent further has a hydrophilic-lipophilic balance value ("HLB", see Kirk Othmer below) within the range of about 9 to about 15, preferably 1 1 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 point nonionic surfactant coagent is derived from a straight chain or preferably branched or secondary fatty alcohol containing from about 6 to about 20 carbon atoms (C6-C20 alcohol). including secondary alcohols and branched chain primary alcohols. Preferably, high cloud point nonionic surfactant coagents 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 20 moles of ethylene oxide per mole of alcohol. Preferably the ethoxylated nonionic surfactant coagent derived in this manner has a narrow ethoxylate distribution relative to the average.

*** S¡ * K »»? + ** m -,. , .TO . «». * .- ... . . ... ^^ When the optional surfactant coagents are a mixture of low cloud point and high cloud point nonionic surfactants, it is preferred that the mixture be combined in a weight ratio preferably within the range of about 10: 1 to approximately 5 1: 10. The anionic surfactant coagent can be selected from alkyl ethoxycarboxylates, alkyl ethoxy sulfates, with the degree of ethoxylation greater than 3 (preferably from 4 to 10, most preferably from 6 to 8), and the length of the chain in the range from C8 to C16, preferably 11-15. In addition, it has It has been found that the branched alkylcarboxylates are useful in ADW compositions when the branching occurs at half the chain and the total chain length is from 10 to 18, preferably from 12 to 16 with the side branch from 2 to 4 carbon atoms in length. An example is 2-butyloctanoic acid. The anionic surfactant coagent is typically of a type that has good 15 solubility in the presence of calcium. Said anionic surfactant coagents are further illustrated by alkyl (polyethoxy) sulfates (AES), alkyl (polyethoxy) carboxylates (AEC) and short chain Cs-C-io alkyl sulfates and alkylsulphonates. It has been shown that straight chain fatty acids are ineffective due to their sensitivity to calcium. 20 Detergency Meters Detergent builders other than silicates may optionally be included in the compositions of the present invention for help control the hardness of minerals. Inorganic and organic builders can be used. Detergency builders are used in automatic dishwashing to help remove particulate dirt. The level of the detergency 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. Without 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, 15 zeolite or stratified 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 20 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., 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, copolymers of maleic anhydride with ethylene or vinyl methyl ether, I .SS-trihydroxybenzene-A-trisulphonic acid, and carboxymethyloxysuccinic acid, various alkali metal, ammonium and substituted ammonium salts of polyacetic acids such as acid. ethylenediaminetetraacetic and nitrilotriacetic acid, as well as polycarboxylates such as melific 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. The citrates can also be used in combination with zeolite, the aforementioned BRITESIL types, and / or layered 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: laurylsuccinate, myristylsuccinate, palmitylsuccinate, 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 on November 5, 1986. Other suitable polycarboxylates are described in the U.S. patent. 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 can also be incorporated into the compositions alone or in combination with the aforementioned builders, especially citrate and / or succinate builders, to provide enhancing activity of additional detergency but 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-diphosphonate 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) are also available.

Tlim iil! i 11 j \ 1 1 ni í 1 1 lll 1 1 1. -? liMil? f ?? «MMM'¿t | they can be used although such materials are most commonly used in a low level mode as chelators or stabilizers. Phosphate builders for use in ADD compositions are well known. They include, but are not limited to, alkali metal, ammonium and alkanolammonium salts of polyphosphates (polished by the 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 Wiikinson, 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. 15 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, 20 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 peroxide source. of hydrogen 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 herein 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 non-ionic surfactant system and builder, the fully formulated ADD compositions will typically also comprise other detergent auxiliary materials for automatic dishwashing 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, preferred compositions have stain and film removal rates of 3 or less, preferably less than 2, and most preferably less than 1, as measured by the standard test of the American Society for Testing and Materials ("ASTM") 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 assist 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; 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. 1. 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 enzymes selected from cellulases, hemicellulases, proteases, glucoamylases, amylases, lipases, cutinases, pectinases, xylanases, reductases, oxidases, phenoloxidases, lipoxygenases, ligninases, pullulanases, tanases, pentosanas, malanases, β-glucanases, arabinosidases or mixtures from the same. 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, - «a» - * '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 β. Subtilis and B. Licheniformis. Suitable proteolytic enzymes include Alcalase® (preferred), Esperase® and Savinase® from Novo Industri A / S (Copenhagen, Denmark), Gist-brocades' and Maxatase®, Maxaeal® and Maxapem 15® (Maxaeal® 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 description, 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. - > . . -. . . -t ^ mWWt Of particular interest for use herein are the proteases described in the U.S.A. No. 5,470,733. Also, the proteases described in copending application U08 / 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 95/10615 published April 20, 1995 by Genecor International (A. Baeck et al. Titled "Protease-Containing Cleaning Compositions" which has the serial number of USA 08 / 322,676, filed on October 13, 1994). Useful proteases are also described in the PCT publications: WO 95/30010 published November 9, 1995 by The Procter & Gamble Company; WO 95/30011 published November 9, 1995 by The Procter & Gamble Company; WO 95/29979 published November 9, 1995 by The Procter & Gamble Company. »- * ^ - > ^ "A * -" 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. 5 2. Amylases Amylases (alpha and / or beta) can be included for the removal of carbohydrate-based stains. The suitable amylases are Termamyl® (Novo Nordisk), Fungamyl® and BAN® (Novo Nordisk). The enzymes may be of any suitable origin, such as of vegetable, animal, bacterial, 10 fungi and yeast. 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 approximately 0.05% of 15 active enzyme by weight of the detergent compositions. Amylase enzymes also include those described in W095 / 26397 and in the co-pending application by Novo Nordisk PCT / DK96 / 00056. A suitable amylase enzyme is NATALASE® available from Novo 20 Nordisk.

Other amylases suitable herein include, for example, the α-amylases described in GB 1, 296, 839 to Novo; RAPIDASE®, International Bio- A ^ », **» * - **. »* - Synthetics, Inc. AND TERMAMYL®, Novo. FUNGAMYL® by Novo is especially useful. Particularly preferred amylases herein include the amylase variants having further modification in the immediate parent as those 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, the one derived by site-directed mutagenesis. 10 mutant 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. Said enzymes include Endoglucosidase, type II endoglycosidase and glucosidase are described in Nos. 5,041, 236, 5,395,541, 5,238,834 and 5,356,803, the disclosures of which are incorporated herein by reference. Of course, other enzymes having antimicrobial activity including peroxidases can also be used, 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. ^! lltrW i ^^ l > ut6Mm? M 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 wash solution. Peroxidase enzymes are known in the art and include, for example, horseradish peroxidase, ligninase, and haloperoxidase such as chloro- and bromo-peroxidase. Peroxidase-containing detergent compositions are described, for example, in the PCT International Application WO 89/099813, published 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 U.S. 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.

Mi * on October 29, 1986, Venegas. Enzyme stabilization systems are also described, for example, in the U.S. patent. 3,519,570. 3. Optional whitening aids (a) Blanoator activators Preferably, the peroxygen bleaching component in the composition is formulated with an activator (peracid precursor). The activator is present at levels of from about 0.01% to about 15%, preferably from about 0.5% 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 tetraacetylethylene diamine (TAED), benzoylcaprolactam (BzCL), 4-nitrobenzoylcaprolactam, 3-chlorobenzoylcaprolactam, 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 about 8 to about 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. Hartshorn, 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 (such as AvO) to bleach activator in the present invention generally ranges from at least 1: 1, preferably from about 20: 1 to about 1: 1, most preferably about 10: 1 to 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 herein by reference. Yes ??? ha ^ ^^^ t ?? diacylperoxide is used, preferably it will 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 U.S. Patents. 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 Patents Nos. 408,131, 549,271, 384,503, 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 0 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 how much charge, and preferred is selected from the group consisting 5 of chloride, iodide, I3", formate, nitrate, nitrite, sulfate, sulfite, citrate, acetate, carbonate, bromide, PFQ-, BF4-, B (Ph) 4", phosphate, phosphite, silicate, tosylate, methane sulfonate and combinations thereof [optionally, and can be protonated if there is more than one anionic group in Y, by example HPO-42-. HCO3-, H2PO4-, etc., and in addition, Y can be selected from the group consisting of 10 non-traditional inorganic anions such as anionic surfactants (eg linear alkylbenzene sulphonate (LAS), alkyl sulfates (AS), alkyl ethoxy sulfonates (AES), etc.) and / or anionic polymers (eg, polyacrylates, polymethacrylates, etc.); and wherein at least one of the coordination sites bound to the cobalt is labile under conditions of washing use 15 automatic crockery 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 about 0.4 volts (preferably less than about 0.2 volts) versus a normal hydrogen electrode. Cobalt catalysts having the formula are preferred: [Co (NH3) n (M ') m] Yy * ^ ~ < * - < e * '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; 5 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 is 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) b] Ty 15 where the cobalt is in the state of oxidation +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 = 1, then m = 0 and n = 4; and T is one or more appropriately selected counterions present in a number and, 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 where said - • t - t < Wiiittf? ? r? Tfrt m *? * - * ~ * B 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, in 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] (S04); [Co (NH3) 5? Ac] (BF4) 2; and [Co (NH3) 5? ac] (N03) 2. As practical, and not by way of limitation, the compositions The cleaning and cleaning procedures 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 aqueous washing medium, and preferably will provide about 0.01 ppm. at about 25 ppm, most preferably from about 0.05 ppm to about 10 ppm, and 15 very preferably still around 0.1 ppm to about 5 ppm, of the bleach catalyst species in the wash solution. In order to obtain such levels in the solutions of an automatic dishwashing process, the automatic dishwashing compositions of the present will comprise from about 0.0005% to about 0.2%, very 20 preferably from about 0.004% to about 0.08% of the bleach catalyst of the cleaning compositions.

HÜliariHi ^ MÜkriÉ ^ É Aüiw 4. pH and variation of pH regulation Many detergent compositions of the present invention will be regulated in terms of their pH, ie 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 leap 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 11. The phosphate-free pH adjusting component of the invention is selected from the group consisting of: 1 sodium carbonate or sesquicarbonate; (ii) sodium silicate, preferably sodium hydrosilicate having a ratio of Si? 2: Na2? from about 1: 1 to about 2: 1, and mixtures thereof with limited amounts of sodium metasilicate; ? TO . - 1 sodium citrate; 1 citric acid; 1 sodium bicarbonate; (vi) sodium borate, preferably borax; (vii) sodium hydroxide; and (viii) mixtures of (i) - (vii). Preferred embodiments contain low levels of silicate (ie, from about 3% to about 10% SiO2.) Modes of highly preferred 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 the 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, the modalities of particularly preferred ADD compositions comprise, by weight of ADD, from about 5% to about 40%, preferably from about 10% to about 30%, most preferably from about 15% to ^? * i? j? l * ^ approximately 20%, of sodium citrate with an amount of from about 5% to about 30%, preferably from about 7% to about 25%, most preferably from about 8% to approximately 20%, of 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 10 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 acid 15 ethylenediaminetetraacetic; nitriloacetic acid, tartrate monosuccinic acid, tartrate disuccinic acid, oxydisuccinic acid, carboxymethylsuccinic acid, mellitic acid and sodium benzenepolycarboxylate salts. 5. Water Soluble Silicates The automatic dishwashing detergent compositions of the present invention may also comprise water soluble silicates. The water soluble silicates of the present are any silicates which 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 the U.S.A. 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 zee builders, NaSKS-6 and other water-soluble silicates useful herein do 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. 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® H20 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. Guelatary 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. The agents BHMUriÉfate commercial chelators for use in the present include the series DEQUEST®, and chelators of Monsanto, DuPont and Nalco, Inc. The aminocarboxylates useful as optional chelating agents are further polished by ethylenediaminetetracetates, N-5-hydroxyethylenediaminetriacetates, nitrilotriacetates, ethylenediamonotetraproprio- nates, triethylenetetraaminohexacetates, diethylenetriaminepentaacetates and ethanoldiglicines, alkali metal salts. , ammonium and substituted ammonium thereof. In general, mixtures of chelating agents can be used for a combination of functions, such as control of multiple transition metals, long-term product stabilization, and / or control of precipitated metal oxides and / or hydroxides of transition. Polyfunctionally substituted aromatic chelating agents are also useful in the compositions herein. See the patent of E.U.A. 3,812,044 issued on May 21, 1974 to Connor and others The 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 (more limited to) the [S, S,] isomer as described in the U.S.A. 4,704,233 issued 20 on 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 They can allow low levels of total phosphorus in detergent compositions and include ethylene diamine tetrakis (methylene phosphonates) and 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. Dispersing polymer The preferred ADD compositions of the present invention. they may also contain a dispersing 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 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. ja a-aan > -Mrftatortr n * ¡m **. t t, s .. - - -! . The dispersant polymers suitable for use herein are illustrated by the film polymeric polymers described in E, U, A, No. 4,379,080 (Murphy), issued April 5, 1983. Suitable polymers are preferably at least partially neutralized salts or alkali metal, ammonium or substituted ammonium salts (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 used in North American automatic dishwashers, is from about 1,000 to about 5,000. Other suitable dispersing polymers include those 15 described in the patents of E.U.A. Nos. 3,308, 067, issued on March 7, 1967 to Diehl. 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 20 monomeric segments that do not contain carboxylate radicals such as methylvinyl ether, styrene, ethylene, etc., are suitably provided so that these segments do not constitute more than 50% by weight of the dispersant 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 about 20%, can also be used. by weight of the dispersant polymer. Most preferably, this dispersant polymer has a molecular weight of about 4,000 to about 20,000 and an acrylamide content of 0% to about 15% by weight of the polymer. Particularly preferred dispersant polymers are low molecular weight modified polyacrylate copolymers. These copolymers contain as monomer units: a) from about 90% to about 10%, preferably from 80% to about 20% by weight of acrylic acid or its salts and b) from about 10% to about 90%, preferably from 20% to about 80% by weight of a substituted acrylic monomer or its salt and has the general formula: [(C (R2) C (R1) (C (0) OR3)] in which the valences apparently not occupied they are in fact occupied by hydrogen and at least one of the R1, R2 or R3, preferably R1 or R2 substituents, is an alkyl or hydroxyalkyl group of 1 to 4 carbon atoms, R1 or R2 can be a hydrogen and R3 can be a hydrogen or an alkali metal salt A substituted acrylic monomer in which R1 is methyl, R2 is hydrogen and R3 is sodium is the most preferred The suitable low molecular weight polyacrylate dispersing polymer preferably has a molecular weight of less than around 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 5 comprising about 70% by weight of acrylic acid and about 30% by weight of methacrylic acid. Other suitable modified polyacrylate copolymers include the low molecular weight copolymers of unsaturated aliphatic carboxylic acids which are described in the U.S. Patents. 4,530,766 and 5,048,535. The agglomerated forms of the ADD compositions of the present invention can use aqueous solutions of dispersing polymers as liquid binders to make the agglomerate (particularly when the composition consists of a mixture of sodium citrate and sodium carbonate). Especially preferred are polyacrylates with an average molecular weight of 15 about 1, 000 to about 10,000 and acrylate / maleate or acrylate / fumarate copolymers with average molecular weight of about 2,000 to about 80,000 and a ratio of the acrylate to maleate or fumarate segments of about 30: 1 to about of 12. Some examples of these copolymers based on a mixture of unsaturated mono-20 and dicarboxylate monomers are described in European Patent Application No. 66,915, published on December 15, 1982. Other dispersion polymers useful herein include polyethylene glycols and polypropylene glycols that have a molecular weight around * i tmA "tl i ** i? m? from 950 to about 30,000 obtainable from the Dow Chemical Company of Midland, Michigan. For example, these compounds having a melting point within the range of about 30 ° C to about 100 ° C, can be obtained at molecular weights of 1, 450, 3,400, 4,500, 6,000, 7,400, 5,900 and 20,000. These compounds are formed by the polymerization of ethylene glycol or propylene glycol with the required number of moles of the ethylene oxide or propylene oxide to provide the desired molecular weight and melting point of the respective polyethylene glycol and polypropylene glycol. Polyethylene glycol, polypropylene glycol and mixed glycols are mentioned using the formula: HO (CH2CH20) m (CH2CH (CH3) 0) n (CH (CH3) CH2?) Or OH in which m, nyo are integers that satisfy the molecular weight and temperature required before dice. Other dispersant polymers useful herein include cellulose sulfate esters such as cellulose acetate sulfate, sulfate 15 of cellulose, hydroxyethylcellulose sulfate, methylcellulose sulfate and hydroxypropylcellulose sulfate. Sodium cellulose sulfate is the most preferred polymer of this group. Other suitable dispersing polymers are carboxylated polysaccharides, particularly starches, celluloses and alginates, described in 20 patent of E.U.A. No. 3,723,322, to Diehl, issued March 27, 1973; the dextrin esters of polycarboxylic acids described in the U.S.A. No. 3,929,107, to Thompson, issued November 11, 1975; starchy hydroxyalkyl ethers, starch esters, oxidized starches, dextrins and starch hydrolysates described in the U.S.A. No. 3,803,285 to Jensen, issued April 9, 1974; the carboxylated starches described in the U.S.A. No. 3,629,121, to Eldib, issued December 21, 1971; and dextrin starches described in the US patent. No. 4,141, 841, to McDonald, issued February 27, 1979. Preferred cellulose-derived dispersant polymers are carboxymethyl celluloses. Yet another group of acceptable dispersants are organic dispersant polymers such as polyaspartate. 8. Material 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 suppressor of * - ^^, .... "... * j, ^. . . . . . _. ,. . »Silicone foams or combinations thereof. Levels in general are from about 0% to about 10%, preferably from about 0.001% to about 5%. However, generally (for considerations of cost and / or deposition) the preferred compositions of the present invention 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 10 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. Suppressors of silicone foams Highly preferred 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 end blocking units 20 alternatives can be used like silicone. These can be combined with silica and / or active surface components that do not contain silicone, 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 5 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 antifoaming 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 antifoams potentially depositable in the compositions of the present invention. 10. 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. This includes sucrose, sucrose esters, sodium sulfate, potassium sulfate, etc., in amounts up to about 70%, preferably from 0% to about 40% of the m sil composition ADD. 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 be co-hardened 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. 5 Coating measures have been described herein to illustrate a way to protect the ingredients from one another 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 0 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 granular tableware wash compositions 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 stable amylase to the bleach and a bleaching system comprising a source of hydrogen peroxide selected from perborate < jaaaMMit «i > - .. . .. .... ... . . ,. ,, *** ^ ** Ammonium sodium 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 non-ionic surfactant of C / EOß BO3 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, pressure equalizer drip funnel, reflux condenser, internal thermometer and inlet for argon, and dried under vacuum at 75 ° C. After releasing the vacuum with argon, sodium metal (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 the 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 C9 / 1 EOgC H yC ^ Ch ^ Neodol 91-8 (30.00 g, 58.7 mmol) is placed in a 250 ml three-necked round bottom flask equipped with a blanket of The second heating, magnetic stirrer, internal thermometer and inlet for argon, and drying 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, 5-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 EO8ÍCH2I4CH3 15 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, equalizer drip funnel of 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 to 20 drops for 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 ,? UámÍ? L? Mtm? .A..A? * A ^ A * ... *, * - ** * ** r ..........., ... . . "- - * A ** Concentrated HCl, diluted with 500 ml of diethyl ether and then extracted once with saturated NaHC 3 and once with brine. The ether layer dries under magnesium sulfate and concentrated under rotary evaporation. This mixture it is purified by flash chromatography (5:95 MeOH: CH 2 Cl 2) to give a 5 liquid of golden color. The NMR is consistent with the desired compound.

The following non-limiting examples further illustrate compositions suitable for use in methods of the present invention.

EXAMPLE 4 10 Compositions for automatic dishwashing Ingredients% by weight AB Sodium tripolyphosphate (STPP) 24.0 45.0 Sodium carbonate 20.0 13.5 Silicated2R hydrated 15.0 13.5 5 Nonionic surfactant1 3.0 3.0 Non-ionic surfactant Poly-tergent® 1 1..00 1.0 SLF 18B4 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 14.5 14.5 Cobalt catalyst4 0.008 - Dibenzoyl peroxide (18% active) 4.4 4.4 Water, sodium sulfate, comp. The remainder The remainder 20 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%. 5 Pentaaminoacetatecobalt Nitrate (III) prepared as described above; it can be replaced by MnTacN. 5 Poly (oxyalkylated) alcohol blocked by epoxy of Example III of WO 94/22800 wherein 1,2-epoxydodecane is replaced by 1,2-epoxydecane. The following examples illustrate the 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. fifteen EXAMPLES 5-6 Ingredients% by weight 5 6 STPP 30.0 32.0 5 Na2C03 30.5 20.5 Silicate 2R SÍO2) 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 - Dibenzoyl peroxide 0.2 0.15 Paraffin 0.5 0.5 Benzotriazole 0.10 0.3 10 Non-ionic surfactant Tergitol 15S9 ° 00..55 0.5 Nonionic surfactant3 2.0 2.0 Sodium sulphate, moisture Pl r octn 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. Ethoxylated secondary alcohol supplied by Union Carbide (cloud point = 60 ° C). In the compositions of examples 6 and 7, respectively, the The catalyst and the enzymes are introduced into the compositions as mixed particles of 200-2400 microns which are prepared by spray coating, fluidized bed granulation, marumerization, pill formation or flaking / crushing. If desired, the Protease and amylase enzymes can be formed as their mixed particles of catalyst / enzyme, for stability reasons, and these Separate compositions can be added to the compositions. The following example best illustrates the granular compositions ADD with chlorine bleach suitable for use in the methods of the present invention.

EXAMPLES 7-8 10 Ingredients% by weight 7 8 STPP 25 31 Na2C03 23.0 15.0 Silicate 2R (S02) 17.5 25.0 Hypochlorite 1.0 3.0 Polymer1 2.0 - Dibenzoyl peroxide - 0.15 Paraffin 1.0 1.0 Nonionic surfactant2 2.0 3.0 15 Sodium sulphate, moisture -The rest- 1 Polyacrylate or Acusol 480N or polyacrylate / polymethacrylate copolymers 3 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.

MHÜMMUÉi EXAMPLES 9-10 Ingredients% by weight 9 10 STPP 32.0 25.0 Na2C03 0.7 2.0 Silicate 2R (Si02) 0.3 1.0 Savinase ™ 12T 2.0 1.0 Termamyl ™ 1.4 0.5 Perborate (AvO) 3.5 - Nonionic surfactant SLF 184 0.8 0.8 Nonionic surfactant1 3.5 3.5 Sulfate sodium, humidity The rest 1 Nonionic surfactant according to example 3. 2 Supplied by Olin Corporation (turbidity point = 18 ° C). The following examples illustrate ADD compositions to be added during rinsing suitable for use in the methods of the present invention.

EXAMPLES 11-12 Ingredients% by weight 11 12 Citric acid 10.0 15.0 Ethanol 5.0 10.0 Acid HEDP1 1.0 0.7 Sodium cumenesulfonate 15.0 10.0 Polymer2 - 1.0 Nonionic surfactant3 15.0 8.0 Humidity The rest ^ 1 1-Hydroxyethylidene-1,1-diphosphonic acid. 2 Polyacrylate or Acusol 480N or polyacrylate / polymethacrylate copolymers 3 Nonionic surfactant according to example 2.

The following examples illustrate ADD compositions in the form of tablets suitable for use in the methods of the present invention.

EXAMPLES 13-14 10 Ingredients% by weight 13 14 STPP 48.0 30 Na2C03 15.0 25.0 Silicate 2R Si02) 4.0 8.0 Catalyst 0.008 0.004 Savinase ™ 12T - 1.0 Termamyl ™ 0.6 0.5 15 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 Nonionic surfactant Tergitol 15S9 1.0 1.0 Nonionic surfactant 3.0 3.0 3.0. 20 Pentaaminoacetatecobalt nitrate (III) can be replaced by MnTacN. a * e »« ^ t? BiM? t? ítrit 2 Polyacrylate or Acusol 480N or polyacrylate / polymethacrylate copolymers 3 Nonionic surfactant according to example 1. 4 Ethoxylated secondary alcohol supplied by Union Carbide 5 (turbidity point) = 60 ° C). ? ^ a | j ^^ ^ ¡¡¡¡

Claims

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 a nonionic surfactant, said nonionic surfactant being selected from the group consisting of: (i) a nonionic surfactant of the formula R1 (EO) a ( PO) b (BO) c in which R1 is a straight or branched chain alkyl of Ce to C20; a is from about 2 to about 30; b is from 0 to about 30; c is from about 1 to about 30; and the nonionic surfactant has an X / Y number of less than 1.90; (ii) a nonionic surfactant of the formula: R10 [CH2CH (R3) 0] eR2 wherein R1 is a straight or branched, saturated or unsaturated, aliphatic or aromatic hydrocarbon radical having from 1 to 30 atoms of carbon, R 2 is a straight or branched chain hydrocarbon radical, saturated or unsaturated, aliphatic or aromatic having from 1 to 30 carbon atoms, optionally containing from 1 to 5 hydroxy groups; and further 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 from 1 to 40, wherein R2 can optionally be alkoxylated wherein the alkoxy is selected from ethoxy, propoxy, butyloxy and mixtures thereof; and (iii) their mixtures; c) optionally, from about 0.1% to about 40% by weight of the composition of a bleaching agent; and d) auxiliary materials.

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

3. The detergent composition for automatic dishwashing according to any of claims 1 to 3, further characterized in that it comprises a coagent surfactant selected from the group consisting of non-ionic surfactants of low turbidity point, nonionic surfactants of high turbidity point, anionic surfactants and mixtures thereof.

4. The detergent composition for automatic dishwashing according to any of claims 1 to 3, further characterized in that it comprises a bleach activating material, preferably tetraacetylethylenediamine, cationic bleach activators and mixtures thereof.

5. The detergent composition for automatic dishwashing according to any of claims 1 to 4, further characterized in that it is in the form of granules, tablets or liquid gels.

6. The detergent composition for automatic dishwashing according to any of claims 1 to 5, further characterized in that it comprises less than 0.1% of active foam suppressing agent. ¡^ ^^^ áuiiij.

7. The detergent composition for automatic dishwashing according to any of claims 1 to 6, further characterized in that said nonionic surfactant is selected from the group consisting of C9.11 P03E013P015; C9.11 P03E013B06; C9.11 P03E013B03 C9.11 E013B06; C9.11E013B03; C9.11 B01 E013B03; C9.11 EO8B03 C12.E5E7B02; C9.11 E08B02; C9.11 E08B01; C12.13E06.5TB01 C9.11 E08 (CH3) 2CH2CH3; C11 / 15E015P06C12 / 14; C 9, 11 E08 (CH 2) 4 CH 3; 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 detersive enzyme selected from the group consisting of proteases, lipases, cellulases, amylases and mixtures thereof.

9. The detergent composition for automatic dishwashing according to any of claims 1 to 8, further characterized in that the bleaching agent is dibenzoyl peroxide.

10. 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 washing of dishes. Tableware according to claims 1 to 9. _ ^ _ ^^ u_