MXPA00001141A - Compositions including ether-capped poly(oxyalkylated) alcohol surfactants - Google Patents

Abstract

Compositions including ether-capped poly(oxyalkylated) alcohol surfactants having superior grease cleaning abilities and improved spotting/filming benefits are provided . The alcohol surfactants have the formula:R1O[CH2CH(R3)O]x[CH2]kCH(OH)[CH2]jOR2 wherein R1 and R2 are linear or branched, saturated or unsaturated, aliphatic or aromatic hydrocarbon radicals having from 1 to 30 carbon atoms;R3 is H, or a linear aliphatic hydrocarbon radical having from 1 to 4 carbon atoms;x is an integer having an average value from 1 to 40, wherein when x is 2 or greater R3 may be the same or different and k and j are integers having an average value of from 1 to 12;further wherein when x is 15 or greater and R3 is H and methyl, at least four of R3 are methyl, further wherein when x 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, further wherein R2 can optionally be alkoxylated, wherein said alkoxy is selected from ethoxy, propoxy, butyloxy and mixtures thereof. Various other detergent adjunct ingredients may also be included.

Description

COMPOSITIONS THAT INCLUDE POLYOXY RIDING ALCOHOL SURGICAL AGENTS OF BLOCKED EXTREMES WITH ETHER TECHNICAL FIELD The present invention relates to detergent compositions having low foaming nonionic surfactants, and more particularly to dishwashing compositions or hard surfaces having polyoxyalkylated alcohol surfactants of ether-blocked end-ends having benefits Superior stain and film reduction in dishwashing and hard surface cleaning applications, as well as foam suppression in detergent compositions.

BACKGROUND OF THE INVENTION Dishwashing and cleaning hard surfaces, in particular automatic dishwashing in domestic applications, is a very different technique from that of fabric washing. Domestic fabric washing is usually done on purposely made machines that have a rotating action. These are very different from domestic applications for automatic dishwashing by means of sprinkling action. The spray action in the latter tends to foam. The foam can easily flood the lower soles of domestic dishwashers and slow down the spray action, which in turn reduces the cleaning action. Thus, in the different field of automatic domestic dishwashing, the use of laundry detergent surfactants that produce foam is usually restricted. These aspects are but a brief illustration of the unique formulation constraints in the fields of automatic household dishwashing and cleaning of hard surfaces. One solution to this problem of foaming has been to include a foam suppressant, typically a silicone foam suppressant. However, this solution, although it works to a certain degree in compositions for washing fabrics, fails in automatic domestic dishwashers. The high shear forces involved in domestic dishwashers degrade the silicone foam suppressors, so any foam suppressant present at the start of washing disappears before completion. Silicone foam suppressors are not strong enough to survive in the environment of a domestic dish washer. Even in laundry applications, although less shear than in a domestic dish washing machine, there is still a decrease in foam suppression towards the end of the wash cycle, due to the degradation of the silicone foam suppressant. An alternative would be to increase the amount of the silicone foam suppressant present; however, the cost of silicone foam suppressors and the fact that they have a tendency to redeposite on hydrophobic surfaces such as plastic makes this an undesirable solution. The need remains today for a viable and cost-effective alternative to a silicone foam suppressant suitable for use in automatic dishwashers as well as in clothes washers. Due to the previous technical restrictions, as well as the needs and demands of consumers, these compositions undergo continuous changes and improvements. In addition, environmental factors such as phosphate restriction, the desire to provide even better cleaning results with less product, provide less thermal energy and use less water to facilitate the washing process, have led to the need for improved compositions. However, many compositions proposed so far for washing dishes and hard surfaces have had aesthetic and technical disadvantages, one being the presence of undesirable spots and films on the cleaned surfaces. These undesirable spots and films can be caused by redeposition of soils and cleaning agents such as surfactants having low water solubility. As an alternative, the composition can provide desirable results with respect to undesirable spots films, provide excellent cleaning, but be totally inadequate due to the high foam it produces. In addition, there continues to be a need for better cleaning, especially regarding the reduction of stain film formation the removal of greasy soils. Accordingly, there remains a need for compositions that can provide improved stain film removal benefits, as well as removal of greasy soils, while providing improved stain film reduction benefits, as well as providing foam suppression that is strong enough to survive in the wash environment in which it develops.

BACKGROUND OF THE INVENTION Patent of E.U.A. No. 4,272,394, issued June 9, 1981; patent of E.U.A. No. 5,294,365; issued on March 15, 1994; patent of E.U.A. No. 4,248,729, issued February 3, 1981; patent of E.U.A. No. 4,284,532, issued August 18, 1981; patent of E.U.A. No. 4,627,927, issued December 9, 1986; patent of E.U.A. No. 4,790,856, issued December 13, 1988; patent of E.U.A. No. 4,804,492, issued February 14, 1989; patent of E.U.A. No. 4,770,815, issued September 13, 1989; patent of E.U.A. No. 5,035,814, issued July 30, 1991; patent of E.U.A. No. 5,047,165, issued September 10, 1991; patent of E.U.A. No. 5,419,853, issued May 30, 1995; patent of E.U.A. No. 5,294,365, issued March 15, 1994; GB application No. 2,144,763, published March 13, 1985; GB application No. 2,154,599, published September 9, 1985; WO application No. 9,296,150, published April 16, 1992; WO application No. 94/22800, published October 13, 1994; application WO 93/04153, published March 4, 1993; WO application No. 97/22651, published June 26, 1997; EP Application No. 342,177, published November 15, 1989 and "Glyceril Bisether Sulfates.1: Improved Synthesis", Brian D. Condón; Journal of the American Chemical Society, Vol. 71, No. 7 (July 1994).

BRIEF DESCRIPTION OF THE INVENTION This need is met by the present invention, in which detergent compositions are provided, and in particular, a dishwashing or hard surface cleaning composition having a non-ionic low foaming surfactant. The compositions employ the novel surfactants of the present invention, either alone or in combination with other surfactants, to provide improved performance of stain and film reduction, as well as improved cleaning performance on greasy soils and foam suppression. Although not intended to be limited by theory, it is believed that the alcohol surfactants of the present invention provide superior stain and film reduction benefits through improved spreading action. As to the improved cleaning performance in greasy soils, said benefits are shown when the alcohol surfactants of the present invention are used in conjunction with a high-point cloudiness nonionic surfactant as described in detail herein. Finally, the alcohol surfactants of the present invention also act to reduce foam or foaming associated with food stains or various other cleaning agents, and allow the use of soluble surfactants, which are highly volatile. foam, such as amine oxides. In accordance with a first aspect of the present invention, a detergent composition is provided. The composition comprises from about 0.1% to about 15% by weight of the composition, of a polyoxyalkylated alcohol surfactant of ether-blocked end ends. The alcohol has the formula: R 1 O [CH 2 CH (R 3) O] x [CH 2] kCH (OH) [CH 2] jOR 2 wherein R 1 and R 2 are aliphatic or aromatic hydrocarbon radicals, linear or branched, saturated or unsaturated, having around from 1 to about 30 carbon atoms; R3 is H or a linear aliphatic hydrocarbon radical having from about 1 to about 4 carbon atoms; x is an integer having an average value of 1 to about 40, wherein when x is 2 or more, R3 may be identical or different, and y and y are integers having an average value of about 1 to about 12, and more preferably from 1 to about 5, and also where when x is 15 or more and R3 is H and methyl, at least four of R3 are methyl, where when x is 15 or more and R3 includes H and from 1 to 3 groups methyl, then at least one R3 is ethyl, propyl or butyl, and wherein R2 can also be optionally alkoxylated, wherein said alkoxy is selected from ethoxy, propoxy, butyloxy, and mixtures thereof; and from about 0.1% to about 99% by weight of the composition of auxiliary detergent ingredients. R1 and R2 are preferably linear or branched, saturated or unsaturated, aliphatic or aromatic hydrocarbon radicals, having from about 6 to about 22 carbon atoms, with more than about 8 to about 18 carbon atoms being preferred. R2 may optionally be alkoxylated, wherein the alkoxy is selected from ethoxy, propoxy, butyloxy, and mixtures thereof. It is more preferable for R3 H or a linear aliphatic hydrocarbon radical having from about 1 to about 2 carbon atoms. Preferably, x is an integer having an average value of from about 1 to about 20, more preferably from about 6 to about 15. Also, preferred in the present invention are the alcohol surfactants as described above, wherein the cloud point of the surfactant is less than about 20 ° C. In accordance with a second aspect of the present invention, a method of foam suppression is provided. The method comprises the step of adding an effective amount of a foam-suppressing composition to an aqueous cleaning solution, the composition comprising from about 0.1% to about 15% by weight of the composition, of a poly-oxyalkylated alcohol end-face surfactant. blocked with ether. The alcohol has the formula: R1O [CH2CH (R3) O] x [CH2] kCH (OH) [CH2], OR2 wherein R1, R2, R3, x, k and j are as defined above, and of about 0.1% to about 99% by weight of the composition, of detergent adjunct ingredients. Preferably, the aqueous cleaning solution is for use in a washing apparatus, such as an automatic dishwashing machine. An effective amount of the foam suppressant composition is added to an aqueous cleaning solution, preferably from about 0.1% to about 15%, more preferably from about 0.1% to about 10%, even more preferably about 0.5% to about 5% by weight. The composition can take the granulated, tablet or liquid forms, including gels - liquids and gels. In addition, the compositions may include auxiliary ingredients including builders, surfactants, enzymes, bleaching agents and anti-rust agents. As already mentioned, the invention has advantages including superior stain and film reduction benefits, as well as good excellent grease removal performance, good dish care performance, good foam suppression performance and general cleaning. good Accordingly, it is an aspect of the present invention to provide a composition that includes a low foaming nonionic surfactant that has superior stain and film reduction benefits as well as good excellent removal performance of greasy soils. , good tableware care performance, good foam suppression performance and good general cleaning. Another aspect of the present invention is to provide a composition having a polyoxyalkylated alcohol surfactant of ether-blocked ends. Yet another aspect of the present invention is to provide a composition that suppresses or reduces the foam associated with food soils, for example, egg soils, or various other cleaning agents, for example, surfactants. These and other aspects, features and advantages will be apparent from the following description and the appended claims. All parts, percentages and ratios used herein are expressed as percent by weight, unless otherwise specified. All the cited documents are incorporated, in a relevant part, in the present as reference.

BRIEF DESCRIPTION OF THE DRAWINGS Figure 1 is a graph of arm rotation versus time, showing the foam suppression effect that the novel alcohol surfactants of the present invention have on the high foaming surfactants. Figure 2 is a graph of arm rotation versus time, showing the effect of foam suppression that the novel alcohol surfactants of the present invention have in the presence of high foaming soils.

DETAILED DESCRIPTION OF THE PREFERRED MODALITIES Once again, the present invention is directed to a low foaming nonionic surfactant for use in detergent compositions. Although tableware and other hard surface cleaning compositions are the preferred utility for the surfactants of the present invention, the described compounds can also be used in laundry and skin care compositions. The compositions of the present invention comprise the novel alcohol surfactants as described in detail herein, and may optionally include various other detergent auxiliary ingredients including, but not limited to, detersive enzymes (to facilitate firm cleaning of food, especially of starch and proteinaceous soils), detergency builder and a bleaching agent (such as a chlorine bleach or a source of hydrogen peroxide). Bleaching agents useful herein include oxygen-chlorine bleach (e.g., hypochlorite; without NaDCC) and sources of hydrogen peroxide, including any common hydrogen peroxide-releasing salt, such as sodium perborate, sodium percarbonate, and mixtures thereof. Also useful are sources of available oxygen, such as persulfate bleaches (e.g., OXONE, manufactured by DuPont). In the preferred embodiments, other ingredients are present such as water-soluble silicates (useful to provide alkalinity and facilitate corrosion control), dispersing polymers (which modify and inhibit the growth of calcium and / or magnesium salts crystals), chelators (which control transition metals), and agents for pH control. Other bleach modifying materials, such as conventional bleach activators, for example TAED and / or bleach catalysts, may be added, provided that any of said bleach modifying materials is supplied in such a way as to be compatible with the purposes of the present invention. . The present detergent compositions may further comprise one or more processing aids, fillers, perfumes, conventional enzyme particle-forming materials, including enzyme cores or "spheres of active agent", as well as pigments, and the like.

In general, the materials that are used for the production of the compositions herein are preferably checked for compatibility with spotting / film formation on surfaces such as glassware. Test methods for stain formation / film formation are generally described in the literature on automatic dishwashing detergents, including DIN and ASTM test methods. Some oily materials, especially long chain, and insoluble materials such as clays, as well as fatty acids or long chain soaps that form soap cream, are therefore limited or preferably excluded from the present compositions. The quantities of the essential ingredients can vary within wide scales; however, the preferred compositions herein (which typically have a pH in aqueous solution at 1% of more than about 8, more preferably from about 9.5 to about 12, most preferably from about 9.5 to about 11), are those where it is present: from about 5% to about 90%, preferably from about 5% to about 75%, of detergency builder; from about 0.1% to about 40%, preferably from about 0.5% to about 30%, of bleaching agent; from about 1% to about 15%, preferably from about 0.2% to about 10%, of the nonionic alcohol surfactant; from about 0.0001% to about 1%, preferably from about 0.001% to about 0.05%, of a metal-containing bleach catalyst (the most preferred cobalt catalysts useful herein are present from about 0.001% to about 0.01%); and from about 0.1% to about 40%, preferably from about 0.1% to about 20% of a water-soluble silicate (ratio of two). Said fully formulated embodiments also typically comprise from about 0.1% to about 15% of a polymeric dispersant, from about 0.01% to about 10% of a chelating agent, and from about 0.00001% to about 10% of a detersive enzyme, although other additional or auxiliary ingredients may be present. The detergent compositions herein in granular or tablet form typically limit the water content, for example, to not less than about 7% free water, for better storage stability. In fact, the compositions may also be in liquid or gel form. Although the compositions of the present invention can be formulated using bleach-containing bleach additives, the preferred compositions of this invention (especially those comprising detersive enzymes) are substantially free of chlorine bleach. By "substantially free" chlorine bleach it is understood that the formulator does not deliberately add a bleach-containing bleach additive, such as a dichloroisocyanurate, to the preferred composition. However, it is recognized that due to factors that are outside the control of the formulator, such as the chlorination of the water supply, some amount of non-zero chlorine may be present in the wash solution. The term "substantially free" can be constructed in the same way in relation to the preferred limitation of other ingredients. By "effective amount" is meant herein an amount that is sufficient, under the comparative test conditions used, to improve the cleanliness of a soiled surface. Likewise, the term "catalytically effective amount" refers to an amount of metal-containing bleach catalyst that is sufficient under the comparative test conditions that are used to improve the cleanliness of the soiled surface. In automatic dishwashing, the soiled surface may be, for example, a porcelain cup with tea stain, a porcelain cup with lipstick stain, dishes contaminated with simple starches or more complex food stains, or a spatula of plastic stained with tomato soup. The test conditions will vary, depending on the type of washing apparatus used and the habits of the user. Some machines have significantly longer wash cycles than others. Some users choose to use hot water without a high level of heating inside the appliance; others use hot or even cold water, followed by heating by using an integrated electric coil. In fact, the performance of bleaches and enzymes will be affected by such considerations, so that the levels used in cleaning compositions and fully formulated detergents can be adjusted appropriately.

Surfactants The surfactant useful in the compositions of the present invention is desirably included at levels of from about 0.1% to about 15% of the composition. The surfactant used in the compositions of the present invention includes a nonionic surfactant or mixtures of various nonionic surfactants. Although a wide range of nonionic surfactants can be selected for the purposes of the mixed nonionic surfactants useful in the compositions of the present invention, it is necessary that the nonionic surfactant comprise to a minimum a surfactant selected from the alcohols. ether-blocked polyoxyalkylates having the formula: R 1 O [CH 2 CH (R 3) O] x [CH 2] kCH (OH) [CH 2] jOR 2 wherein R 1 and R 2 are aliphatic or aromatic hydrocarbon radicals, linear or branched, saturated or unsaturated , which have from about 1 to about 30 carbon atoms; and R3 is H, or a linear aliphatic hydrocarbon radical having from about 1 to about 4 carbon atoms; x is an integer having an average value of 1 to about 40, where when x is 2 or more, R3 can be the same or different, and y and y are integers having an average value of about 1 to about 12, and more preferably from 1 to about 5, wherein when x is 15 or more and R3 is H and methyl, at least four of R3 are methyl, wherein when x is 15 or more and R3 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. R1 and R2 are preferably aliphatic or aromatic hydrocarbon radicals, linear or branched, saturated or unsaturated, having from about 6 to about 22 carbon atoms, with more than about 8 to about 18 carbon atoms being preferred. In addition, R2 can be selected from hydrocarbon radicals that are ethoxylated or propoxylated. It is more preferable for R 3 H or a linear aliphatic hydrocarbon radical having from about 1 to about 2 carbon atoms. Preferably, x is an integer having an average value of from about 1 to about 20, more preferably from about 6 to about 15. As described above when, in the preferred embodiments and x is greater than 2, R3 may be the same or different That is, R3 can vary between any of the alkyleneoxy units as described above: For example, if x is 3, R3 can be selected to form ethyleneoxy (EO) or propyleneoxy (PO), and can vary in order of (EO) (PO) (EO), (EO) (EO) (PO); (EO) (EO) (EO); (PO) (EO) (PO); (PO) (PO) (EO) and (PO) (PO) (PO). In fact, the integer 3 is chosen only as an example, and the variation can be much larger as a larger integer value for x and includes, for example, multiple units (EO) and a very small number of units (PO). However, when x is 15 or more and R3 is H and methyl, at least four of R3 are methyl, where when x is 15 or more, and R3 includes H and from 1 to 3 methyl groups, then at least an R3 is ethyl, propyl or butyl. Particularly preferred surfactants as described above, include those having a low cloud point of less than about 20 ° C. These low-cloud point surfactants can then be used in conjunction with a high-point cloud surfactant as described in detail below for superior fat cleaning benefits. More preferred in accordance with the present invention are surfactants wherein k is 1 and j is 1, so that the surfactants have the formula: R 1 O [CH 2 CH (R 3) O] x CH 2 CH (OH) CH 2 OR 2 wherein R 1, R 2 and R3 are as defined above, and x is an integer with an average value of from about 1 to about 30, preferably from about 1 to about 20, and even more preferably from about 6 to about 18. More preferred are the agents surfactants wherein R1 and R2 vary from about 9 to about 14, R3 is ethyleneoxy H-forming, and x ranges from about 6 to about 15.

Basically, the alcohol surfactants of the present invention comprise three general components, namely linear or branched alcohol, an alkylene oxide and ends blocked with alkyl ether. The ends blocked with alkyl ether and the alcohol function as the hydrophobic, fat-soluble portion of the molecule, while the alkylene oxide group forms the water-soluble hydrophilic portion of the molecule. It has surprisingly been found in accordance with the present invention, that significant improvements in the characteristics of reduction of film formation and staining and, when used in conjunction with high-cloud point surfactants, in the removal of greasy soils With respect to conventional surfactants, they are provided by the polyoxyalkylene alcohol surfactants of ether-blocked ends of the present invention. It has surprisingly been found that the ether-blocked polyoxyalkylene alcohol surfactants of the present invention, in addition to providing superior cleaning benefits, also provide good foam control. This foam control can be clearly seen in the presence of high foaming surfactants, such as amine oxides or in the presence of high foaming soils, such as egg or proteinaceous soils. Broadly speaking, the ether-blocked polyoxyalkylene alcohol surfactants of the present invention can be produced by reacting an aliphatic alcohol with an epoxide to form an ether, which is reacted with a base to form a second epoxide. . The second epoxide is then reacted with an alkoxylated alcohol to form the novel compounds of the present invention. The process comprises the first step of providing a glycidyl ether having the formula: where R is as defined above. Various glycidyl ethers are available from a number of commercial sources including the Aldrich Chemical Company. Alternatively, the glycidyl ether can be formed from the reaction of a linear or branched aromatic or aliphatic alcohol of the formula R2OH, where R2 is as defined above, and an epoxide of the formula: where X in a suitable leaving group. Although a number of leaving groups can be used in the present invention, X is preferably selected from the group consisting of halides including chloride, bromide and iodide, tosylate, mesylate and brosylate, with chloride and bromide being even more preferred, and most preferred chloride (for example, epichlorohydrin). The linear or branched alcohol and the epoxide are preferably reacted at ratios ranging from about 0.5 equivalents of alcohol to 2 equivalents of epoxide with 0.95 equivalents of alcohol per 1.05 equivalents of epoxide, being more typical under acidic conditions for catalysis purposes. Acids which can be used as a catalyst include mineral acids including, but not limited to, H2SO and H3PO, and Lewis acids including, but not limited to, TiCl, Ti (O'Pr), ZnCl, SnCl, AICI3 and BF3- OEt2. Preferred catalysts include Lewis acids, with SnCl and BF3-OEt2 being more preferred. The catalysts are preferably used in amounts of from about 0.1 mol% to about 2.0 mol%, with 0.2 mol% being more typical at about 1.0 mol%. Although the reaction can be carried out in the presence of a suitable solvent such as benzene, toluene, dichloromethane, tetrahydrofuran, diethyl ether, tert-butyl methyl ether or the like, the reaction is preferably carried out in pure form or in the presence of solvent . Finally, the reaction is carried out at temperatures ranging preferably from about 40 ° C to about 90 ° C, more preferably from about 50 ° C to about 80 ° C, and most preferably from about 55 ° C to Approximately 65 ° C.

After concluding the reaction, the mixture treats with a basic material to form the glycidyl ether. The basic material is preferably a strong base such as a hydroxide. Preferred hydroxides include alkali metal hydroxides, with sodium being the typical choice. However, the person skilled in the art will recognize that other basic materials can also be used. The basic material is preferably added at levels of from about 0.5 equivalents to about 2.5 equivalents, 0.95 equivalents being equivalent to 2.0 equivalents, and 1.0 to 1.5 equivalents being most preferred. The product, glycidyl ether, can then be collected after optional filtration, drying and distillation, in accordance with methods well known in the art. To form the surfactant, an ethoxylated alcohol having the formula: wherein R1 and x are as defined above in an amount of from about 0.80 to about 1.5 equivalents, is combined with a catalyst as described above, and heated to a temperature ranging from about 50 ° C to about 95 ° C , and more preferably from about 60 ° C to about 80 ° C. The glycidyl ether is then added to the mixture, and reacted for about 0.5 hours to about 30 hours, and more preferably about 1 hour to about 24 hours. The ether-blocked polyoxyalkylated alcohol surfactant product is then collected by common means in the art, such as filtration. If so desired, the surfactant can be further treated by separation, distillation or various other means before use. The surfactants obtained by the process described herein may contain related impurities, which will not adversely affect the yield. A representative synthesis route is demonstrated by the following examples.

EXAMPLE 1 Preparation of Cry2 alkyl aryl ether Neodol® 23 (100.00 g, 0.515 moles, available from The Shell Chemical Co.) and tin (IV) chloride (0.58 g, 2.23 mmoles, available from Aldrich) are combined in a 500 ml three-necked flask and bottom round adapted with a condenser, argon inlet, addition funnel, magnetic stirrer and internal temperature probe. The mixture is heated to 60 ° C. Epichlorohydrin (47.70 g, 0.515 moles, available from Aldrich) is added dropwise to maintain the temperature between 60-65 ° C. After stirring for another hour at 60 ° C, the mixture is cooled to room temperature. The mixture is treated with a 50% solution of sodium hydroxide (61.80 g, 0.773 mol, 50%), while stirring mechanically. After the addition is complete, the mixture is heated at 90 ° C for 1.5 h, cooled and filtered with the aid of ethanol. The filtrate is separated and the organic phase is washed with water (100 ml), dried over MgSO 4, filtered and concentrated. Distillation of the product mixture at 100-120 ° C (0.1 mm Hg) provides the glycidyl ether as an oil.

EXAMPLE 2 Preparation of Cg / n alkyl glycidyl ether Neodol® 91 (100.00 g, 0.632 moles, available from The Shell Chemical Co.) and tin (IV) chloride (0.82 g, 3.20 mmol, available from Aldrich) are combined in a 500 ml three-necked flask and bottom round adapted with a condenser, argon inlet, addition funnel, magnetic stirrer and internal temperature probe. The mixture is heated to 65 ° C. Epichlorohydrin (58.46 g, 0.632 moles, available from Aldrich) is added dropwise to maintain the temperature between 60-65 ° C. After stirring for another hour at 60 ° C, the mixture is cooled to room temperature and treated with a 50% solution of sodium hydroxide (61.80 g, 0.773 mol, 50%). After the addition is complete, the mixture is heated at 90 ° C for 3.0 h, cooled and treated with water to dissolve all white solids. The organic phase is dried over MgSO 4, filtered and concentrated. Distillation of the product mixture at 100 ° C (0.1 mm Hg) provides the glycidyl ether as an oil.

EXAMPLE 3 Preparation of C12 / 14 alkyl glycidyl ether The proce of Example 1 is repeated, with the replacement of Neodol® 23 by fatty alcohol of C-? 2? 4.

EXAMPLE 4 Preparation of C14 / 15 alkyl aryl ether The proce of Example 1 is repeated, with the replacement of Neodol® 23 by Neodol® 45.

EXAMPLE 5 Preparation of C14 / 15 alkyl aryl ether The proce of Example 1 is repeated, with the replacement of Neodol® 23 by Tergitol® 15-S-15.

EXAMPLE 6 Preparation of alcohol surfactant with blocked ends with ethoxylated alkyl ether of C? /? -alkyl Cg / n Neodol® 91-8 (16.60 g, 0.0325 moles, from The Shell is placed Chemical Co.) in a 250 ml three-necked round bottom flask fitted with a condenser, argon inlet, addition funnel, magnetic stirrer and internal temperature probe. The contents of the flask are dried under vacuum at 75 ° C for 15 minutes after establishing an argon atmosphere. Tin (IV) chloride (0.25 ml, 2.1 mmol Aldrich) is added to the flask by syringe. The mixture is heated to 60 ° C, at which point glycidyl C 12/14 alkyl glycidyl ether (10.00 g, 0.039 mol) is added dropwise over 15 minutes, while maintaining the temperature at 75 to 80 ° C, then of stirring for 18 hours at 60 ° C. The mixture is stirred for another hour at 75 ° C, until the glycidyl ether is consumed, as determined by TLC. 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, 7x12 diameter), while eluting with 5% dichloromethane-methanol (40 ml). The filtrate is concentrated by rotary evaporation, and then separated in a Kugeirohr oven (70 ° C, 0.1 mm Hg for 30 minutes) to give the product as an oil.

EXAMPLE 7 Preparation of end-capped alcohol surfactant blocked with ethoxylated alkyl ether of Ci2 / i4-alkyl-Cn /? S It melts Tergitol® 15-S-15 (2820.0 g, 3.275 moles, Union Carbide) in a three-necked round-bottomed 12-liter flask fitted with a condenser, argon inlet, addition funnel, mechanical stirrer and internal thermometer. The contents of the flask are dried at 75 ° C for 30 minutes under vacuum. An argon atmosphere is established. Tin (IV) chloride (25 ml, 0.214 mmol, Aldrich) is added to the flask by syringe. The mixture is heated to 85 ° C. C.sub.2-14 alkyl glycidyl ether (1679.48 g, 6.549 mol) is added dropwise over 1 hour while maintaining the reaction temperature. After stirring for another 15 minutes at 75 ° C, the reaction is quenched with the addition of water (75 ml). The reaction is diluted with 500 ml of 5% dichloromethane-methanol. The mixture is cooled to room temperature, and then separated in a Kugeirohr oven (70 ° C, 0.1 mm Hg for 30 minutes) to produce the surfactant as an oil. In effect, the person skilled in the art will recognize that the surfactant as described above can be used in combination with other commercially available nonionic surfactants, in particular non-ionic low foaming surfactants (LFNIs) to form the surfactant. of the present invention.

Low foaming nonionic surfactant The LFNI may be present in amounts of from 0 to about 15% by weight, preferably from about 0.1% to about 10%, and more preferably from about 0.25% to about 4% . LFNIs are more typically used in automatic dishwashing compositions or ADDs because of the enhanced water extendable action (especially on glass) that they give to the product. The LNFIs also include polymeric materials without silicon and without phosphate, better illustrated later on, which is known to defoam the food dirt found in automatic dishwashing. Preferred LFNIs include nonionic alkoxylated surfactants, especially ethoxylates derived from primary alcohols, and mixtures thereof, with more sophisticated surfactants, such as the polyoxypropylene / polyoxyethylene / polyoxypropylene (PO / EO / PO) reverse block polymers. Surfactants of the PO / EO / PO polymer type are well known to have defoaming or foam suppressant action, especially in relation to common ingredients of food soils, such as egg. The invention encompasses preferred embodiments wherein the LFNI is present, and wherein this component is solid at about ° C, more preferably solid at about 25 ° C. For ease of manufacture, a preferred LFNI has a melting point between about 25 ° C and about 60 ° C, more preferably between about 26.6 ° C and 43.3 ° C. In a preferred embodiment, the LFNI is an ethoxylated surfactant derived from the reaction of a monohydric alcohol or alkylphenol containing from about 8 to about 20 carbon atoms, with from about 6 to about 15 moles of ethylene oxide per mole. of alcohol or alkylphenol on an average basis. A particularly preferred LFNI is derived from a straight chain fatty alcohol containing from about 16 to about 20 carbon atoms (Ci6-C2o alcohol), preferably a C-ie alcohol, condensed with an average of about 6. to about 15 moles, preferably from about 7 to about 12 moles, and more preferably from about 7 to about 9 moles of ethylene oxide per mole of alcohol. Preferably, the ethoxylated nonionic surfactant derived in this way has a narrow ethoxylate distribution with respect to the average. The LFNI may optionally contain propylene oxide in an amount of up to about 15% by weight. Other preferred LFNI surfactants can be prepared by the methods described in the U.S.A. 4,223,163, issued September 16, 1980, Builloty, incorporated herein by reference. Highly preferred compositions herein, wherein LFNI is present, make use of alkylphenol or ethoxylated monohydric alcohol, and additionally comprise a polymeric polyoxyethylene-polyoxypropylene block compound; the fraction of alkylphenol or ethoxylated monohydric alcohol of the LFNI ranging from about 20% to about 100%, preferably from about 30% to about 70%, of the total LFNI. Suitable polyoxyethylene-polyoxypropylene block polymer compounds that satisfy the requirements described above include those based on ethylene glycol, propylene glycol, glycerol, trimethylolpropane and ethylene diamine as a reactive hydrogen reactant compound. Polymeric compounds made from a sequential ethoxylation and propoxylation of initiator compounds with a single reactive hydrogen atom, such as the aliphatic alcohols of C-? 2 -? 8, do not generally provide satisfactory foam control in the ADDs herein. Some of the block polymer surfactants designated as PLURONIC® and TETRONIC® by BASF-Wyandotte Corp., Wyandotte, Michigan, are suitable in the ADD compositions of the invention. A particularly preferred LFNI contains from about 40% to about 70% of a polyoxypropylene / polyoxyethylene / polyoxypropylene block polymer blend, comprising about 75% by weight, of the blend, of a polyoxyethylene and polyoxypropylene inverted block copolymer which it contains 17 moles of ethylene oxide and 44 moles of propylene oxide; and about 25%, by weight of the mixture, of a polyoxyethylene and polyoxypropylene block copolymer initiated with trimethylolpropane and containing 99 moles of propylene oxide and 24 moles of ethylene oxide per mole of trimethylolpropane. Suitable for use as LFNI in compositions, are LFNIs that have relatively low turbidity points, and high hydrophilic-lipophilic balance (HLB). Turbidity points of 1% solutions in water are typically below about 32 ° C and preferably at a lower value, for example, 20 ° C, for optimum control of foam formation over a full scale of water temperatures. These and other nonionic surfactants are well known in the art, being described in more detail in Kirk Othmer's Encyclopedia of Chemical Technology, 3a. ed., Vol. 22, pp. 360-379, "Surfactants and Detersive Systems", citation incorporated herein by reference. Particularly preferred in the present invention are the mixed nonionic surfactants. Although a wide range of nonionic surfactants can be selected for the purposes of the mixed nonionic surfactant systems useful in the compositions of the present invention, it is preferred that the nonionic surfactants comprise a low haze point surfactant. represented by the ether-blocked poly (oxyalkylated alcohol) surfactant, and high-cloud point nonionic surfactants as described below. The "cloud point", as used herein, is a well-known property of nonionic surfactants, where the surfactant becomes less soluble as the temperature increases, and the temperature at which the appearance is observed from a second phase, it is referred to as the "turbidity point" (see Kirk Othmer, pp. 360-362, cited above). As used herein, a non-ionic "low cloud point" surfactant is defined as an ingredient of the nonionic surfactant system having a cloud point of less than 30 ° C, preferably less than about 20 ° C. ° C, and more preferably less than about 10 ° C, and is represented by the ether-blocked poly (oxyalkylated) alcohols as described herein. In fact, other low-cloud point surfactants can be included in conjunction with ether-blocked poly (oxyalkylated) surfactants. Such optional low cloud point surfactants include nonionic alkoxylated surfactants, especially primary alcohol derived ethoxylates, 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., Poly-Tergent® SLF18 from Olin Corporation) and poly (oxyalkylated) alcohols end-blocked with epoxy (e.g. series of non-ionic surfactants Poly-Tergent® SLF18B from Olin Corporation), as described, for example, in WO 94/22800, published on October 13, 1994 by Olin Corporation). These nonionic surfactants may optionally contain propylene oxide in an amount up to about 15% by weight. Other preferred nonionic surfactants can be prepared by the methods described in the U.S.A. 4,223,163, issued September 16, 1980, Builloty, incorporated herein by reference. Optional low cloud point nonionic surfactants additionally comprise a polymeric polyoxyethylene-polyoxypropylene block compound. The polyoxyethylene-polyoxypropylene block polymer compounds include those based on ethylene glycol, propylene glycol, glycerol, trimethylolpropane and ethylene diamine as a reactive hydrogen reactant compound. Some of the block polymer surfactants designated as PLURONIC®, REVERSED PLURONIC® and TETRONIC® by BASF-Wyandotte Corp., Wyandotte, Michigan, are suitable in the ADD compositions of the invention. Preferred examples include REVERSED PLURONIC® 25R2 and TETRONIC® 702. Such surfactants are typically useful herein as low cloud point nonionic surfactants. As used herein, a non-ionic surfactant of "high cloud point" is defined as a nonionic surfactant system having a cloud point greater than 40 ° C, preferably greater than about 50 ° C, and more preferably greater than about 60 ° C. Preferably, the nonionic surfactant system comprises an ethoxylated surfactant derived from the reaction of an alkylphenol or monohydric alcohol containing from about 8 to about 20 carbon atoms, having from about 6 to about 15 moles of sodium oxide. ethylene per mole of alcohol or alkylphenol on an average basis. Such high cloud point nonionic surfactants include, for example, Tergitol 15S9 (supplied by Union Carbide), Rhodasurf TMD 8.5 (supplied by Rhone Poulenc) and Neodol 91-8 (supplied by Shell). It is also preferred for the purposes of the present invention that the high-cloud point nonionic surfactant further has a hydrophilic-lipophilic balance ("HLB", see Kirk Othmer, cited above) within the range of about 9 to about 15, preferably 11 to 15. Such materials include, for example, Tergitol 15S9 (supplied by Union Carbide), Rhodasurf TMD 8.5 (supplied by Rhone Poulenc) and Neodol 91-8 (supplied by Shell). Another preferred high cloud point nonionic surfactant is derived from a straight chain or preferably branched or secondary fatty alcohol containing from about 6 to about 20 carbon atoms (C 2 -C 2) alcohol, including secondary alcohols and branched chain primary alcohols. Preferably, high cloud point nonionic surfactants are branched or secondary alcohol ethoxylates, more preferably branched alcohol C9 / 11 or C11 / 15 branched ethoxylates, 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 surfactant derived in this way has a narrow ethoxylate distribution with respect to the average. Preferred nonionic surfactant systems useful herein, are mixed high-cloud point, low-cloud point non-ionic surfactants combined in a weight ratio preferably in the range of about 10: 1 to about 1:10. Compositions comprising such mixed nonionic surfactant systems are preferred, wherein foaming (absent any silicone foam control agent) is less than 5.08 cm, preferably less than 2.54 cm, determined as follows : Measuring the efficiency, in RPM, of the dishwashing machine arm and the height of the washing foam The useful equipment for these measurements is: a Whirlpool dishwashing machine (model 900) or a Miele dishwashing machine (model G7750) equipped with clear Plexiglas door, data collection on IBM computer with Labview and Excel programs, proximity sensor (Newark Corp. -model 95F5203) using SCXI interface, and a plastic ruler.

The data is collected in the following manner. The proximity sensor is attached to the bottom shelf of the tableware washer on a metal support. The sensor faces downwards towards the rotating arm of the dishwasher, on the lower part of the machine (approximately 2 cm distance from the rotating arm). Each step of the rotating arm is measured by the proximity sensor, and is recorded. The pulses recorded by the computer are converted to rotations per minute (RPM) of the lower arm, counting the pulses during a 30-second interval. The rotation speed of the arm is directly proportional to the amount of foam in the machine and in the dishwasher of the dishwasher (ie, the more foam is produced, the slower the rotation of the arm). The plastic rule is attached to the bottom shelf of the dishwasher and extends to the floor of the machine. At the end of the wash cycle, the height of the foam is measured using the plastic ruler (seen through the clear door), and recorded as the height of the foam. The following procedure is followed to evaluate ADD compositions for foam production, as well as to evaluate the utility of nonionic surfactants (to separately evaluate the nonionic surfactant, an ADD base formula, such as Cascade powder. , it is used together with the nonionic surfactants which are added separately in glass containers to the dishwashing machine).

First, the machine is filled with water (the water is adjusted for appropriate temperature and hardness), and a rinse cycle is carried out. The RPM is monitored throughout the cycle, (approximately 2 minutes), without the addition of any ADD product (or surfactants) (quality control is applied to ensure the machine is working properly). As the machine begins to fill for the wash cycle, the water is adjusted again for temperature and hardness, and then the ADD product is added to the bottom of the machine (in the case of surfactants evaluated separately, the base formula ADD is first added to the bottom of the machine and then the surfactants are added by placing the glass containers containing the inverted surfactant on the top shelf of the machine). The RPM is then monitored throughout the wash cycle. At the end of the wash cycle, the height of the foam is recorded using the plastic ruler. The machine is refilled with water (the water is adjusted for appropriate temperature and hardness), and it is operated through another rinse cycle. The RPM is monitored throughout this cycle. The average RPM for the first rinse, main wash and final rinse are calculated. The percentage of efficiency of the RPM is then calculated by dividing the average RPM for the surfactants of the test between the average RPM between the control system (base formulation of ADD without the nonionic surfactant). RPM efficiency and foam height measurements are used to calculate the general foam profile of the surfactant. To demonstrate the control of foam supplied by the nonionic surfactants of the present invention, the following experiment is carried out. In a Miele G7750 dishwasher, at a hardness of 1.20 g / l, no dirt, 48 ° C water temperature at filling and a wash temperature of 65 ° C, arm rotation is measured during the main wash cycle (from time = 0 minutes at time = 27 minutes) and both rinses (rinsing 1 from time = 28 minutes at time = 33 minutes, and rinsing 2 from time = 34 minutes at the end), for the following compositions: A. Base granule + 0.5% by weight of an amine oxide of the formula: O CH3 (CH2) 15N (CH3) 2 B. Base granule + 0.5% by weight of an amine oxide used at point A and 2% of the nonionic surfactant of example 7.

See Figure 1 for a graph of this information as arm rotation against time.

In order to demonstrate the control of foam supplied by the nonionic surfactants of the present invention in the presence of dirt, and to compare them and to know the non-ionic low foaming surfactants, the following experiment is carried out. In a Miele G7750 dishwasher, at a hardness of 0 grams per liter, 20 g of egg dirt, 48 ° C of water temperature at filling and wash temperature of 65 ° C, arm rotation was measured during the main wash cycle (from time = 0 minutes to time = 27 minutes) and both rinses (rinse 1 from time = 28 minutes at time = 33 minutes, and rinse 2 from time = 34 minutes at the end), for the following compositions: C. Base granule + 2% by weight of the low foaming nonionic surfactant available from BASF under the tradename PLURAFAC LF404®. D. Base granule + 2% of the nonionic surfactant of example 7. E. Base granule + 0.5% by weight of an amine oxide used in point A above, and 2% of the nonionic surfactant of example 7.

See Figure 2 for a graph of this information as arm rotation versus time.

The base granule in all compositions comprises (by weight): 53.75% STPP, 14% sodium carbonate, 12% sodium silicate 2R, 12.26% sodium perborate, 0.30% BTA, 0.5% paraffin oil (Winog 70), 1.5% granule of Termamil nitrate / pentaaminoacetocobalt (lll) and 1.27% of stable protease to bleach. It can be clearly seen from the above examples, that not only the non-ionic surfactants of the present invention suppress the foam associated with food soils, in this case egg soiling, but also remove the soils associated with several other soils. cleaning agents, in this case the foam caused by an amine oxide surfactant. In addition, as shown above, the nonionic surfactants of the present invention provide better foaming control than conventional low foaming nonionic surfactants.

Optional surfactants In fact, optional detersive surfactants may be included in conjunction with the nonionic surfactants of the present invention. The optional surfactants included in the fully formulated detergent compositions produced by the present invention comprise at least 0.01%, preferably from about 0.5% to about 50% by weight of the detergent composition, depending on the surfactants used and the surfactants used. desired effects in particular. In a highly preferred embodiment, the detersive surfactant comprises from about 0.5% to about 20% by weight of the composition. The present invention may also include a nonionic surfactant coagent. However, the automatic dishwashing detergent compositions herein are preferably substantially free of anionic surfactant coagents. It has been discovered that certain anionic surfactant coagents, in particular fatty carboxylic acids, can produce unpleasant looking films on the dishes. When included, the anionic surfactant coagent is typically of a type that has good solubility in the presence of calcium. Said anionic surfactant coagents are best illustrated by sulfobetaines, alkyl (polyethoxy) sulfates (AES), alkyl (polyethoxy) carboxylates, and short chain C6-C? Alkyl sulfates. However, no restriction is necessary when the compositions are different from the automatic dishwashing compositions. The detersive surfactant may be anionic as described above, or ampholytic, zwitterionic or cationic. Mixtures of these surfactants can also be used. Non-limiting examples of surfactants useful herein include the conventional Cn-Ciß alkylbenzene sulphonates and primary, secondary and random alkyl sulphates, the C10-C18 alkyl alkoxy sulphates, the alkyl polyglycosides of C-IO-C-IS and their polyglucosides. corresponding sulfates, suifonated alpha fatty acid esters of C? 2-C? 8, betaines and sulfobetaines ("sultaines") of C12-C-? 8, amine oxides of C10-C18, and the like. Other conventional useful surfactants are cited in standard texts.

Detergency builders The present invention may include an optional builder in the composition of the product. The level of salt / builder can vary widely depending on the final use of the composition and its desired physical form. When present, the compositions will typically comprise at least about 1% builder, and very typically from about 10% to about 80%, even very typically from about 15% to about 50% by weight, of the detergency builder However, no attempt is made to exclude higher or lower levels. Inorganic or phosphate-containing builders include, but are not limited to, alkali metal, ammonium and alkanolammonium salts of polyphosphates (illustrated by tripolyphosphates, pyrophosphates and vitreous polymeric metaphosphates), phosphonates, phytic acid, silicates, carbonates (including bicarbonates and sesquicarbonates), sulfates and aluminosilicates. However, non-phosphate builders are required in certain places. Importantly, the compositions herein work surprisingly well even in the presence of so-called "weak" builders (as compared to phosphate builders) such as citrate, or in the so-called "lower builder" situation which can occur with zeolite builders or stratified silicate. Examples of silicate builders are alkali metal silicates, particularly those having a ratio of Yes? 2: Na2? in the scale 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 marketed 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 delta-Na2Si? 5 layered silicate. It can be prepared by methods such as those described in the 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? +? and H 2 ?, 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, can 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 delta-Na2Si? 5 form (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. Examples of carbonate salts as builders are alkali metal and alkaline earth metal carbonates such as those described in German Patent Application No. 2,321,001, published November 15, 1973. Aluminosilicate builders are useful I presented it as a detergent salt. Aluminosilicate builders are of great importance in most heavy duty granular detergent compositions currently marketed. The aluminosilicate builders include those that have the empirical formula: Mz (zAIO2) and] xH2O where z and y are integers of at least 6, the molar ratio of z: y is on the scale of about 1.0 to about 0.5 , and x is an integer from about 15 to about 264. Useful aluminosilicate ion exchange materials are commercially available. These aluminosilicates may be of crystalline or amorphous structure, and may be naturally occurring or synthetically derived aluminosilicates. A method for producing aluminosilicate ion exchange materials is described in the U.S.A. No. 3,985,669, Krummel et al., Issued October 12, 1976. Preferred synthetic crystalline aluminosilicate ion exchange materials useful herein, are available under the designations Zeolite A, Zeolite P (B), Zeolite MAP and Zeolite X In an especially preferred embodiment, the crystalline aluminosilicate ion exchange material has the formula: Nai 2_ (AI02) 12 (Si 2)? 2] xH2? wherein x is from about 20 to about 30, especially about 27. The material is known as Zeolite A. Dehydrated zeolites (x = 0-10) can also be used herein. Preferably, the aluminosilicate has a particle size of about 0.1-10 microns in diameter. 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, "polycarboxylates" refers to compounds having a plurality of carboxylate groups, preferably at least 3 carboxylates. Polycarboxylate builders can generally be added to the composition in acid form, but can also be added in the form of a neutralized salt. When used in the form of salt, alkali metal salts, such as sodium, potassium and lithium salts, or alkanolammonium salts are preferred. Included among the polycarboxylate builders are a variety of useful material categories. A Also suitable in the detergent compositions of the present invention are the 3,3-dicarboxy-4-oxa-1,6-hexanedioates and the related compounds described in the US patent. 4,566,984, Bush, issued January 28, 1986. Useful succinic acid builders include the C5-C20 alkyl and alkenyl succinic acids. and you come out of them. A particularly preferred compound of this type is dodecenylsulinic 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 US Pat. 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 Diehl, patent of E.U.A. 3,723,322. Fatty acids, for example, monocarboxylic acids of C- | 2-Ci8 >; they can also be incorporated into the compositions alone, or in combination with the aforementioned builders, especially the citrate and / or succinate builders, to provide additional builder activity. Such use of fatty acids will generally result in decreased foaming, which would be considered by the formulator.

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 (Article)", citation incorporated herein by reference, and include 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 hydrogen peroxide source-free composition when the tableware be washed by the consumer in a domestic automatic dishwasher in the presence of alkali. More generally, a source of hydrogen peroxide herein is any convenient compound or mixture which, under the 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%, more I typically from about 0.5% to about 30%, by weight of the compositions herein. The preferred source of hydrogen peroxide used herein may be any convenient source, including the hydrogen peroxide itself. For example, perborates can be used, for example, sodium perborate (any hydrate but preferably mono- or tetrahydrate), sodium carbonate peroxyhydrate or equivalent percabonate salts, sodium pyrophosphate peroxyhydrate, urea peroxyhydrate or sodium peroxide. Also available are available oxygen sources such as persulfate-based bleach (e.g., OXONE, manufactured by DuPont). Particularly preferred are sodium perborate monohydrate and sodium percarbonate. Mixtures of any of the suitable hydrogen peroxide sources can also be used. A preferred bleach based on percarbonate contains dry particles having an average particle size in the range of about 500 microns to about 1000 microns, with no more than about 10% by weight of said particles less than 200 microns and being no more of 10% by weight of said particles greater than about 1,250 microns. Optionally, the percarbonate can be coated with a silicate, borate or with water-soluble surfactants. Percarbonate can be obtained from various commercial sources such as FMC, Solvay and Tokai Denka. Although not preferred for the compositions of the present invention which contain detersive enzymes, the compositions of the present invention may also contain as the bleaching agent a chlorine bleaching material. Such agents are well known in the art, and include for example sodium dichloroisocyanurate ("NADCC"). (a) Blanking activator Preferably, the peroxygen bleaching component in the composition is formulated with an activator (peracid precursor). The activator is present at levels from about 0.01% to about 15%, preferably from about 0.5% to about 10%, most preferred from about 1% to 8%, by weight of the composition. Preferred activators are selected from the group consisting of tetraacetylethylenediamine (TAED), benzoylcaprolactam (BzCL), 4-nitrobenzoylcaprolactam, 3-chlorobenzoylcaprolactam, benzoyloxy-benzenesulfonate (BOBS), nonanoyloxybenzenesulfonate (NOBS), phenylbenzoate (PhBz), decanoyloxybenzenesulfonate (C) -to-OBS), benzoylvalerolactam (BZVL), octanoyloxybenzenesulfonate (C8-OBS); perhydrolyzable esters and mixtures thereof, preferably benzoylcaprolactam and benzoylvalerolactam. Particularly preferred bleach activators in the pH range of about 8 to 9.5 are those selected having an OBS or VL leaving group. Preferred bleach activators are those described in the patent E.U.A. 5, 130,045, Mitchell et al, and 4,412,934, Chung et al, and co-pending patent applications E.U.A. serial numbers 08 / 064,624, 08 / 064,623, 08 / 064,621, 08 / 064,562, 08 / 064,564, 08/082, 270 and the copending application for M. Burns, A. D. Willey, R. T. Hartshorn, C.K. Ghosh, entitled "Bleaching Compounds Comprising Peroxyacid Activators Used With Enzymes" and having the serial number E.U.A. 08 / 113,691 (P & G Case 4890R), of which all are incorporated herein for reference. The molar ratio of peroxygen-based bleaching 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, more preferred from about 10: 1 to about 3: 1. Activators of substituted quaternary bleach can also be included. The detergent compositions herein preferably contain a substituted quaternary bleach activator (QSBA) or a substituted quaternary peracid (QSP), the former being more preferred. Preferred QSBA structures are further described in the U.S.A. Copending Nos. 5,460,747, 5,584,888 and 5,578,136, incorporated herein by reference. (b) Organic peroxides, especially diacyl peroxides 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. If a diacyl peroxide is used, it will preferably be one that exerts a minimal adverse impact on the formation of spots / films. The preferred is dibenzoyl peroxide. (c) Metal-containing blanching catalysts The compositions and methods of the present invention utilize metal-containing bleach catalysts which are effective for use in ADD compositions. Preferred are bleach catalysts containing manganese and cobalt. One type of metal-containing bleach catalyst is a catalyst system containing a transition metal cation with defined bleach catalytic activity, such as copper, iron, titanium, ruthenium, tungsten, molybdenum, manganese, an auxiliary metal cation. which has little or no catalytic bleaching activity, such as zinc or aluminum cations, and a sequestrant having defined stability constants for catalytic and auxiliary metal cations, particularly ethylenediaminetetraacetic acid, ethylenediaminetetra (methylene phosphonic acid) and water-soluble salts thereof. Such catalysts are described in the patent E.U.A. 4,430,243. Other types of bleach catalysts include the manganese-based complexes described in the U.S.A. 5,246,621 and the patent E.U.A. 5,244,594. Preferred examples of these catalysts include Mnlv2 (uO) 3 ((1, 4,7-trimethyl-1, 4,7-triazacyclononane) 2- (PF6) 2 ("MnTACN"), Mnlll2 (u-0)? (U -OAc) 2 (1, 4,7-trimethyl-1, 4,7-triazacyclononane) 2- (CIO4) 2, Mn? V4 (uO) 6 (1, 4,7-triazacyclononane) 4- (CIO4) 2 , Mn "'Mnlv4 (uO)? (U-OAc) 2 (1, 4,7-trimethyl-1, 4,7-triazacyclononane) 2- (CIO) 3? And mixtures thereof See also the publication of European Patent Application No. 549,272 Other suitable ligands for use herein include 1, 5,9-trimethyl-1, 5,9-triazacyclododecane, 2-methyl-1, 4,7-triazacyclononane, 2-methyl -1,7,7-triazacyclononane and mixtures thereof Bleach catalysts useful in automatic dishwashing compositions and powder concentrated detergent compositions can also be selected as being suitable for the present invention. of suitable bleaching see US patent 4,246,612 and US patent 5,227,084. bleaching are described for example in the European patent application, publication no. 408,131 (catalyst based on cobalt complex), European patent applications, publication number 384,503 and 306,089 (metallo-porphyrin-based catalysts), patent E.U.A. 4, .728,455 (manganese catalyst / multidentate ligand), patent E.U.A. 4,711, 748 and the European patent application publication number, 224,952 (manganese absorbed in aluminosilicate-based catalyst), patent E.U.A. 4,601, 845 (aluminosilicate support with manganese and zinc or magnesium salt), patent E.U.A. 4,626,373 (manganese / ligand catalyst), patent E.U.A. 4,119,557 (catalyst based on ferric complex), German patent specification 2,054,019 (cobalt chelator catalyst) Canadian document 866,191 (salts containing transition metal), patent E.U.A. 4,430,243 (chelators with manganese cations and non-catalytic metal cations), and patent E.U.A. 4,728,455 (manganese gluconate catalysts).

Cobalt-based catalysts having the formula: [Co (NH3) n (M ') m] Yy wherein n is an integer from 3 to 5 (preferably 4 or 5, most preferred 5) are preferred; 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 preferred 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 from 2 to 3, most preferred 2 when Y is an anion with load -1), to obtain a balanced salt in As for charges. The preferred cobalt-based catalyst of this type useful herein are cobalt pentaamincloride salts having the formula [Co (NH3) 5CI] Yy, and especially [Co (NH3) CI] CI2. Most preferred are the compositions of the present invention which use cobalt-based bleach catalysts (III) having the formula: [Co (NH3) n (M) m (B) 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 with the 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 1 or more appropriately selected counterions present in a number y, where y is an integer to obtain a balanced salt in terms of charges (preferably y is 1 to 3, more preferred 2 when T is an anion with charge - 1 ); and wherein further said catalyst has a hydrolysis rate constant in basic medium of less than 0.23 M "1 s" 1 (25 ° C). The preferred T is selected from the group consisting of chloride, iodide, l3", formate, nitrate, nitrite, sulfate, sulfite, citrate, acetate, carbonate, bromide, PF6", BF ", B (Ph) 4", phosphate, phosphite, silicate, tosylate methanesulfonate and combinations thereof. Optionally T may be protonated if there is more than one anionic group in T, for example, HP0 2", HC03", H2PO4", etc. In addition T may be selected from the group consisting of non-traditional inorganic anions such as surfactants anionics (for example linear alkylbenzenesulfonates (LAS), alkyl sulfates (AS), alkyl ethoxysulfonates (AES), etc.) and / or anionic polymers (eg, polyacrylates, polymethacrylates, etc.) The M-portions include, but are not limited to a, for example, F ", S04" 2, NCS ", SCN", S2O3"2, NH3, PO43", and carboxylates (which are preferably monocarboxylates, but more than one carboxylate may be present in the portion in both that the cobalt binding is made only by one carboxylate per portion, in which case the other carboxylate in the M-portion may be protonated or in salt form.) M may optionally be protonated if there is more than one anionic group in-M (for example, HPO42", HCO3", H2PO4", HOC (O) CH2C (O) O ", etc.). Preferred M-portions are substituted and unsubstituted C-α-C3o carboxylic acids having the formulas: RC (O) O- wherein R is preferably selected from the group consisting of hydrogen and C - ?C3o alkyl ( preferably CC? 8) unsubstituted and substituted, unsubstituted and substituted C 1 -C 3 aryl (preferably C 6 -C 8) and substituted and unsubstituted and substituted C 3 -C 3 heteroaryl (preferably C -C 8), in wherein the substituents are selected from the group consisting of -NR'3, -NR'4 +, -C (O) OR ', -OR', -C (O) NR'2, wherein R 'is selected from the group consisting of hydrogen and portions of CrC6. Such substituted R thus includes the portions - (CH2) nOH and - (CH2) nNR'4 +, wherein n is an integer of 1 about 16, preferably from about 2 to about 10 and more preferred from about 2 to aproximadamented. The most preferred M are carboxylic acids having the above formula wherein R is selected from the group consisting of hydrogen, methyl, ethyl, propyl, straight or branched C4-C-? 2 alkyl, and benzyl. The most preferred R is methyl. Preferred M-moieties of carboxylic acid include formic, benzoic, octanoic, nonanoic, decanoic, dodecanoic, malonic, maleic, succinic, adipic, phthalic, 2-ethylhexanoic, naphthenoic, oleic, palmitic, triflate, tartrate, stearic, butyric, citric, acrylic, aspartic fumaric, lauric, linoleic, lactic, malic and especially acetic acid. Portions B include carbonate, dicarboxylates, and higher carboxylates (e.g., oxalate, malonate, malic, succinate, maleate), picolinic acid, and alpha and beta amino acids (eg, glycine, alanine, beta-alanine, phenylalanine). The cobalt-based bleach catalysts useful herein are known, being described for example together with their rates of hydrolysis in basic medium, in M. L. Tobe, "Hydrolysis-Base Metal Complexes", Adv. Inorg. Bioinorg. Mech., (1983), 2, pages 1-94. For example, Table 1 on page 17, provides hydrolysis rates in basic medium (designated in that reference as k0hi) for pentamincobalt-based catalysts complexed with oxalate (koH = 2.5 x 10'4 M_1 s "1 (25 ° C)), NCS- (kO = 5.0 x 10"4 M'1 s" 1 (25 ° C), formate (kOH = 5.8 x 10"4 M" 1 s "1 (25 ° C)), and acetate (kO = 9.6 x 10"4 M'1 s" 1 (25 ° C).) The most preferred cobalt-based catalysts useful herein are the cobalt pentamine acetate salts having the formula [Co (NH3) 5OAc] Ty, wherein OAc represents an acetate portion, and especially cobalt pentamine acetate chloride, [Co (NH3) 5OAc] CI2; 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) 5? Ac] (N03) 2. The cobalt-based catalysts according to the present invention can be produced in accordance with the synthetic routes described in US Pat. do not. 5,559,261, 5,581, 005 and 5,597,936, the descriptions of which are incorporated herein by reference. These catalysts can be coprocessed with auxiliary materials if it is desired to reduce the impact on the color for the aesthetic appearance of the product, or they can be included in particles containing enzyme as hereinafter exemplified, or the compositions can be manufactured so that contain "specks" of catalyst. As a practical aspect, and not by way of limitation, the cleaning compositions and cleaning methods herein can be adjusted to provide in the order of at least one part per one hundred million active reactive catalyst species in the aqueous washing medium, and preferably will provide from 0.01 ppm to about 25 ppm, more preferred from 0.05 ppm to about 10 ppm and more preferably even from about 0.1 ppm to about 5 ppm, of the bleach catalyst species in the liquor of washed. In order to obtain such levels in the washing solution of an automatic dishwashing process, the typical automatic dishwashing compositions herein will consist of from about 0.0005% to about 0.2%, more preferred from about 0.004% to about 0.08% bleach catalyst by weight of the cleaning compositions ..

Detersive Enzymes The compositions of the present invention can also include the presence of at least one detersive enzyme. "Detersive enzyme", as used herein, means any enzyme that has a cleaning effect, stain removal or some other beneficial effect in a composition. Preferred detersive enzymes are hydrolases such as proteases, amylases and lipases. They are highly preferred for automatic dishwashing amylases and / or proteases, including both currently commercially available types and improved types which, although more compatible with the bleach, have a remaining degree of susceptibility to bleach degradation, such as lipases , cellulases, peroxidases and mixtures thereof of any In general, as indicated, the preferred compositions herein contain one or more detersive enzymes. If only one enzyme is used, it is preferably an amylolytic enzyme when the composition is for use in automatic dishwashing. A mixture of proteolytic enzymes and amylolytic enzymes is highly preferred for automatic dishwashing. More generally, the enzymes to be incorporated include proteases, amylases, lipases, cellulases and peroxidases as well as mixtures thereof. Other types of enzymes can also be included. These can be of suitable origin, such as vegetable, animal, bacterial, mycotic and yeast. However, its selection is governed by several factors such as optimal levels of Ph-activity and / or stability, thermostability, stability versus active detergents, detergency builders, etc. In this sense bacterial or fungal enzymes are preferred, such as bacterial amylases and proteases and fungal cellulases. Enzymes are normally incorporated in the detergent compositions herein at levels sufficient to provide an "effective amount of cleaning". The term "effective cleaning amount" refers to any amount capable of producing a cleaning effect, removing stains or removing dirt on substrates such as fabrics, tableware and the like. Since enzymes are catalytic materials, such amounts can be very small. In practical terms for current commercial preparations, typical amounts are up to about 5 mg by weight, more typically about 0.01 mg to about 3 mg of active enzyme per gram of composition. Stated otherwise, the compositions herein will typically consist of from about 0.001% to about 6%, preferably 0.01% -1% by weight of a commercial enzyme preparation. Generally, protease enzymes are present in such commercial preparations at levels sufficient to provide from 0.005 to 0.1 Anson units (AU) of activity per gram of composition. For the purposes of automatic dishwashing, it may be desirable to increase the active enzyme content of commercial preparations in order to minimize the total amount of non-catalytically active materials supplied and thereby improve staining results. films. Suitable examples of proteases are the subtilisins that are obtained from particular strains of B.subtilis and β. licheniformis. Other suitable proteases are obtained from a Bacillus strain, having a maximum activity throughout the pH range of 8 to 12, developed and sold as ESPERASE® by Novo Industries A S. The preparation of this enzyme and analogues is described in British patent specification 1, 243,784, by Novo. Suitable proteolytic enzymes for removing commercially available protein-based spots include those sold under the trade names ALCALASE® and SAVINASE® from Novo Industries A / S (Denmark) and MAXATASE® from International Bio-Synthetics, Inc. (Countries) Low). Other proteases include Protease A (see European patent application 130, 756, published January 9, 1985) and Protease B (see European patent application Serial No. 87303761.8, filed April 28, 19875 and European Patent Application 130,756, Bott et al., Published on September 9, 1985). January 1985). An especially preferred protease, called "protease D" is a carbonyl hydrolase variant having an amino acid sequence that is not found in nature, which is derived from a precursor carbonyl hydrolase by substituting a different amino acid for a plurality of amino acid residues. at a position in said carbonyl hydrolase equivalent to the +76 position, preferably also in combination with one or more amino acid residue 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 according to the numeration of the subtilisin of Bacillus amyloliquefaciens, as described in WO 95/10615, published on April 20, 1995 by Genencor International.

Another preferred protease enzyme includes protease enzymes that are a variant of carbonyl hydrolase having an amino acid sequence that is not found in nature, which is derived by substituting a plurality of amino acid residues of a precursor carbonyl hydrolase with different amino acids, in wherein said plurality of amino acid residues replaced in the precursor enzyme corresponds to position +210 in combination with one or more of the following residues: +33, +62, +67, +76, +100, +101, +103 , +104, +107, +128, +129, +130, +132, +135, +156, +158, +164, +166, +167, +170, +209, +215, +217, + 218 and +222, wherein the numbered positions correspond to a subtilisin present in nature from Bacillus amyloliquefaciens or to equivalent amino acid residues in other carbonyl hydrolases or subtilisins (such as Bacillus lentus subtilisin). Preferred compliance enzymes include those that have changes at positions +210, +76, +103, +104, +156 and +166. Useful proteases are also described in 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 and WO 95/29979, published November 9, 1995 by The Procter & Gamble Company. Amylases suitable herein include, for example, α-amylases described in British Patent Specification No. 1, 296,839 (Novo), RAPIDASE®, International Bio-Synthetics, Inc. and TERMAMYL®, Novo. Industries. Preferred amylases herein have the common characteristic of being derived using the site-directed mutagenesis of one or more of the Bacillus amylases, especially the Bacillus alpha-amylases, regardless of whether one, two or multiple strains of amylases are the same. immediate precursors. As indicated, it is preferred to use amylases in the present "improved in terms of their oxidative stability" despite the fact that the invention converts them into "optional but preferred" materials instead of essential materials. Such amylases are illustrated in a non-limiting manner by the following: a) an amylase according to WO / 94/02597, Novo Nordisk A / S, published on February 3, 1994 previously incorporated, as further illustrated by a mutant in which the substitution is made, using alanine or threonine, (preferably threonine), of the methionine residue located at position 197 of the alpha-amylase of B.lichemiformis, known as TERMAMYL®, or the variation of the homologous position of a similar progenitor amylase, such as B. amyloliquefaciens, B. subtilis or B. stearothermophilus; b) improved stability amylases as described by Genencor International in a document entitled "Oxidatively Resistant alpha-Amylases", presented at the 207 American Chemical Society National Meeting, March 13-17, 1944, by C. Mitchinson. It is mentioned that the bleaches in automatic dishwashing detergents inactivate alpha-amylases, but that oxidant amylases of improved stability have been made by Genencor from B. licheniformis NCIB8061. Methionine (Met) was identified as the residue most likely to be modified. The Met was substituted, one at a time, in positions 8, 15, 197, 256, 304, 366 and 438 carrying specific mutants, being particularly important the variants MI97L and MI97T, with the variant M197T being the most stable expressed variant. The stability was measured in CASCADE® and SUNLIGHT®; (c) variants of amylases which have additional modification in the immediate parent from Novo Nordisk A / S and are those named by the supplier as QL37 + M197T are particularly preferred herein. Cellulases that can be used herein, but are not preferred, include both bacterial and fungal cellulases. Typically, these will have an optimum pH between 5 and 9.5. the appropriate cellulases are described in the patent E.U.A. 4,435,307, Barbesgoard et al., Issued March 6, 1984, which describes fungal cellulase produced from Humicola insolens and from Humicola strain DSM 1800, or a cellulase-producing fungus 212 belonging to the genus Aeromonas, and the cellulase extracted from the hepatopancreas of a marine mollusk (Dolabella Auricle Solander). Suitable cellulases are also described in GB-A-2,075,028; GB-A-2,095,275 and DE-OS-2,247,832. CAREZYME® (Novo) is especially useful.

Lipase enzymes suitable for detergent use include those produced by microorganisms of the Pseudomonas group, such as Pseudomonas stutzeri ATCC 19,154 as described in British Patent 1, 372,034. Also see lipases in Japanese Patent Application 53,20487, open to public inspection on February 24, 1978. This lipase is available from Amano Pharmaceutical Co. Ltd., Nagoya, Japan, under the tradename Lipase P "Amano," hereinafter referred to as "Amano-P." Other suitable commercial lipases include Amano-CES, lipases ex Chromobacter viscosum, e.g. Chromobacter viscosum var. lipoliticum NRRLB 3673, from Toyo Jozo Co., Tagata, Japan; Chromobacter viscosum lipases from U.S. Biochemical Corp, E.U.A. and Disoynth Co., Holland. The lipase ex Pseudomonas gladioli. The LIPOLASE® enzyme derived from Humicola lanuginosa and commercially available from Novo (see also EPO 341, 947) is a preferred lipase for use herein. Another preferred lipase enzyme is the D96L variant of the native lipase of Humicola lanuginosa, as described in WO 92/05249 and Research Pamphlet No. 35944, of March 10, 1994, both published by Novo. In general, lipolytic enzymes are less preferred than amylases and / or proteases for automatic dishwashing modalities of the present invention. The peroxidase enzymes can be used in combination with oxygen sources, e.g., percarbonate, perborate, persulfate, hydrogen peroxide, etc. Typically, these are used for "bleaching in solution", ie to avoid the transfer of dyes or pigments removed from the substrates during the washing operations to other substrates in the washing solution. Known peroxidase enzymes include horseradish peroxidase, ligninase and haloperoperoxidase such as chloroperoxidase and bromoperoxidase. Peroxidase-containing detergent compositions are described, for example, in PCT International Application WO 89/099813 published October 19, 1989 by O. Kirk, assigned to Novo Industries A / S. The present invention encompasses modalities of peroxidase-free automatic dishwashing compositions. A wide variety of enzyme materials and means for their incorporation into synthetic detergent compositions are described in US Pat. 3,553,139, issued January 5, 1971 to McCarty et al. The enzymes are further described in the patent E.U.A. 4,101, 457, Place et al, issued July 18, 1978 and in the patent E.U.A. 4,507,219, Hughes, issued March 26, 1985. Enzymes for detergents can be stabilized by various techniques. Enzyme stabilization techniques are described and illustrated in the US patent. 3,600,319, issued August 17, 1971 to Gedge et al., And in the 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 patent E.U.A. 3,519,570.

Variation and regulation of the pH Many detergent compositions herein will be regulated, ie they will be relatively resistant to pH drop in the presence of acid-type soils. However, other compositions herein may also have exceptionally low regulatory capacity, or may be substantially unregulated. The techniques to control or vary the pH to recommended levels of use generally include the use not only of regulatory solutions, but also of alkalis, acids, pH jump systems, containers with additional double compartment, etc. and are known to those skilled in the art. Preferred compositions herein comprise a pH adjusting component selected from water soluble alkaline inorganic salts and water soluble organic or inorganic builders. The components for adjusting the pH are selected so that when the composition is dissolved in water at a concentration of 1,000 - 10,000 ppm, the pH remains above the range of about 8, preferably from 9.5 to about 11. Preferred non-phosphatized pH adjuster of the invention is selected from the group consisting of: (i) sodium carbonate or sesquicarbonate; (i) sodium silicate, preferably hydrated sodium silicate having an SiO2: Na20 ratio of about 1: 1 to about 2: 1, and mixtures thereof with limited amounts of sodium metasilicate; (iii) sodium citrate; (iv) citric acid; (v) sodium bicarbonate; (vi) sodium borate, preferably borax; (vii) sodium hydroxide; and (viii) mixtures of (i) - (vii). Preferred embodiments contain low levels of silicate (i.e. from about 3% to about 10% SiO2). The amount of the pH adjusting component in the present composition 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 composition in an amount of from about 5 to about 40%, preferably from about 10% to about 30%, by weight.

Water-soluble silicates The compositions herein may also contain water-soluble silicates. The water soluble silicates herein are any silicate that is soluble to the extent that these do not adversely affect the spotting / film forming characteristics of the ADD composition.

Examples of silicates are sodium metasilicate and, more generally, alkali metal silicates, particularly those having a ratio of SiO2: Na20 in the range of 1.6: 1 to 3.2: 1; and the layered silicates, such as the layered sodium silicates described in US Pat. 4,664,839, issued May 12, 1987 for H.P. Rieck NaSKS-6® is a crystalline layered silicate sold by Hoechst (commonly abbreviated herein as "SKS-6"). Unlike zeolite-based builders, NaSKS-6 and other water-soluble silicates useful herein do not contain aluminum. NaSKS-6 is the d-Na2S05 form of the layered silicate and can be prepared by methods such as those described in German DE-A-3,417,649 and DE-A-3,742,043. SKS-6 is a preferred layered silicate to be used herein, but other such layered silicates, such as those having the general formula NaMSix02X + 1 and H20 where M is sodium or hydrogen, x is a number from 1.9 to 4 , preferably 2, e and is a number from 0 to 20, preferably 0 can be used. Some other stratified silicates from Hoeschst include NaSKS-5, NaSKS-7 and NaSKS-11, as the a-, ß- and? - forms. Other silicates may also be useful, such as for example magnesium silicate, which may serve as a crisp agent in granulated formulations, as a stabilizing agent for oxygen-based bleaches, and as a component of foam control systems.

Silicates particularly useful in automatic dishwashing (ADD) applications include 2-ratio hydrated granular silicates such as BRITESIL® H20 from PQ Corp., and the commonly used BRITESIL® H24 although liquid grades of various silicates can be used when ADD compositions have liquid form. Within safe limits, the sodium metasilicate or sodium hydroxide by itself or in combination with other silicates can be used in an ADD context to boost the pH of the wash to a desired level.

Guelatary Agents The compositions herein may optionally also contain one or more selective transition metal sequestrants, "chelants" or "chelating agents", for example, iron and / or copper and / or manganese chelating agents. Chelating agents suitable for use herein may be selected from the group consisting of aminocarboxylates, phosphonates (especially aminophosphonates), polyfunctionally substituted aromatic chelating agents, and mixtures thereof. Without being limited to 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 from which hydrogen peroxide and / or activators are known to decompose. bleaching; Other benefits include the prevention of inorganic film or the inhibition of incrustation. Commercial chelating agents to be used herein include the DEQUEST® series, and the chelators of Monsanto, DuPont, and Nalco, Inc. The aminocarboxylates useful as optional chelating agents are further illustrated by the ethylenediaminetetraacetates, N-hydroxyethylenediaminetriacetates, nitrilotriacetates, ethylenediaminetetra -propionates, triethylenetetraminehexaacetates, diethylenetriaminpentaacetates and ethanoldiglicines, alkali metal salts, ammonium and substituted ammonium thereof. In general, chelator agent mixtures can be used for a combination of functions, such as multiple transition metal control, 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 patent E.U.A. 3,812,044, issued May 21, 1974 for 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 chelating agent to be used herein is ethylene diamine disuccinate ("EDDS"), especially (but not limited to) the [S, S] isomer as described in US Pat. 4,704,233, November 3, 1987, for Hartman and Perkins. Trisodium salt is preferred although other forms, such as magnesium salts, may also be useful.

Aminophosphonates are also suitable for use as chelating agents in the compositions of the invention when at least low levels of total phosphorus are acceptable in detergent compositions, and include ethylene diamine tetrakis (methylene phosphonate) and diethylenetriaminpentakis (methylene phosphonate). Preferably, these aminophosphonates do not contain alkyl or alkenyl groups with more than about 6 carbon atoms. If used, chelating agents or selective transition metal sequestrants will preferably constitute from about 0.001% to about 10%, more preferably from about 0.05% to about 1% by weight of the compositions herein.

Dispersing polymer Preferred compositions herein may additionally contain a dispersing polymer. When present, a dispersant polymer in the compositions herein is typically at levels in the range of from 0 to about 25%, preferably from about 0.5% to about 20%, more preferred from about 1% to about 8% by weight of the composition. Dispersing polymers are useful for the improved film-forming performance of the compositions herein, especially in embodiments with higher pH, such as those in which the wash pH is above about 9.5. Particularly preferred are polymers which inhibit the deposition of calcium carbonate or magnesium silicate in the ware. Dispersing polymers suitable for use herein are further illustrated by the film-forming polymers described in the U.S.A. No. 4,379,080 (Murphy), issued April 5, 1983. Suitable polymers are preferably at least partially neutralized or are alkali metal, ammonium or substituted ammonium salts (eg, mono-, di- or triethanolammonium) of polycarboxylic acids. Alkali metal salts, especially sodium salts, are most preferred. Although the molecular weight of the polymer can vary over a wide range, it is preferably from about 1,000 to about 500,000, more preferred from about 1,000 to about 250,000, and even more preferred, especially if the composition is will be used in washing machines for automatic washing of North American dishes, preferably from 1,000 to 5,000. Other suitable dispersing polymers include those described in U.S. Patent No. 3,308,067 issued 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 monomeric segments which do not contain carboxylate radicals such as methyl vinyl ether, styrene, ethylene, etc., are suitable provided that such segments do not constitute more than about 50% by weight of the dispersing polymer. The 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%, by weight of the dispersing polymer They can also be used. Preferably, such dispersion polymers have a molecular weight of about 4,000 to about 20,000 and an acrylamide content of at least about 0% to about 15%, by weight of the polymer. Particularly preferred dispersant polymers are low molecular weight modified polyacrylate copolymers. Such copolymers contain monomer units: a) from about 90% to about 10%, preferably from about 80% to about 20% by weight of acrylic acid or its salts and b) from about 10% to about 90%, preferably from about 20% to about 80% by weight of a substituted acrylic monomer or its salt and have the general formula - [(C (R2) C (R1) (C (0) OR3] wherein the apparently non-full valencies are in fact occupied by hydrogen and at least one of the substituents R1, R2 or R3, preferably R1 or R2 is an alkyl or hydroxyalkyl group of 1 to 4 carbon atoms; R1 or R2 may be a hydrogen and R3 may be a hydrogen or an alkali metal salt. The most preferred is a substituted acrylic monomer in which R1 is methyl, R2 is hydrogen and R3 is sodium. The suitable low molecular weight polyacrylate dispersing polymer preferably has a molecular weight of less than about 15,000, preferably from about 500 to about 10,000, more preferred from about 1,000 to about 5,000. The most preferred polyacrylate-based copolymer to be used herein has a molecular weight of about 3,500 and is the completely neutral form of the polymer consisting of about 70% by weight of acrylic acid and about 30% by weight of methacrylic acid. Other suitable modified polyacrylate-based copolymers include the low molecular weight copolymers of unsaturated aliphatic carboxylic acids described in U.S. Patents 4,5330,766 and 5,084,535. The agglomerated forms of the compositions herein may employ aqueous solutions of polymer dispersants 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 about 1,000 to about 10,000 and acrylate / maleate or acrylate / fumarate copolymers with a molecular weight of about 2,000 to 80,000 and an acrylate to maleate or fumarate segments from about 30: 1 to about 1: 2. Examples of such copolymers which are based on a mixture of unsaturated mono- and dicarboxylate monomers are described in European Patent Application No. 66,915, published on December 15, 1982. Other dispersion polymers useful herein include polyethylene glycols and propylene glycols having a molecular weight of about 950 to about 30,000 which can be obtained from the Dow Chemical Company of Midland, Michigan. Such compounds, for example, having a melting point in the range of about 30 ° C to about 100 ° C, can be obtained with molecular weights of 1, 450, 3,400, 4,500, 6,000, 7,400, 9,500 and 20,000. Such compounds are formed by polymerization of ethylene glycol or propylene glycol with the required number of moles of ethylene or propylene oxide to provide the desired molecular weight and melting point of the respective polyethylene glycol and propylene glycol. Polyethylene, polypropylene and the mixed glycols are referred to to use the formula: HO (CH2CH2O) m (CH2CH (CH3) CH2O) 0OH in which m, n and o are integers satisfying the molecular weight and temperature requirements given above. Even other dispersing polymers useful herein include the cellulose sulfate esters such as cellulose acetate sulfate, cellulose sulfate, hydroxyethyl cellulose sulfate, methyl cellulose sulfate and hydroxypropyl cellulose sulfate. Sodium cellulose sulfate is the most preferred polymer of this group. Other suitable dispersing polymers are carboxylated polysaccharides, particularly starches, celluloses and alginates, described in U.S. Patent No. 3,723,322, Diehl, issued March 27, 1973; the dextrin esters of polycarboxylic acids described in U.S. Patent No. 3,929, 107, Thompson, issued November 11, 1975; the hydroxyalkyl starch ethers, starch esters; oxidized starches, dextrins and starch hydrolysates described in U.S. Patent No. 3,803,285, Jensen, issued April 9, 1974; the carboxylated starches described in the patent E.U.A. do not. 3,629,121, Eldib, issued December 21, 1971; and the dextrin starches described in the patent E.U.A. do not. 4,141, 841, McDonald, issued February 27, 1979. The preferred cellulose dispersant polymers obtained are carboxymethyl celluloses. Even another group of acceptable dispersants are organic dispersant polymers such as polyaspartate.

Material Care Agents The compositions herein may contain one or more agents for care of the material that are effective as corrosion inhibitors and / or anti-rust auxiliaries. Such materials are preferred components of compositions for dishwashing machines, especially in certain European countries where the use of silver and nickel electrodeposited and sterling silver is still comparatively common in household dishes, or when protection to aluminum is a concern and the composition is low in silicate. Generally, such care agents for the material include metasilicate, silicate, bismuth salts, manganese salts, paraffin, triazoles, pyrazoles, thiols, mercaptans, fatty acid and aluminum salts and mixtures thereof. When present, such protective materials are preferably incorporated at low levels, for example from about 0.01% to about 5% of the ADD composition. Suitable corrosion inhibitors include paraffin oil, typically a predominantly branched 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 C25.45 species with a cyclic to non-cyclic hydrocarbon ratio of about 32:68. A paraffin oil that fulfills these characteristics is sold by Wintershall, Salzbergen, Germany, under the trade name WINOG 70. Additionally, 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 thiophthol and thioanthranol; and finely divided fatty acid and aluminum salts, such as aluminum tristearate. The formulator will recognize that such materials will generally be used judiciously and in limited quantities so as to avoid any tendency to produce stains or films on the dishes or to jeopardize the bleaching action of the compositions. For this reason, preferably anti-rust agents based on mercaptan are avoided, which react strongly with bleach and common carboxylic fatty acids which precipitate with calcium.

Phosphate ester and silicone ester-based foam suppressants The compositions of the invention may optionally contain a foam suppressant based on alkyl phosphate ester, a silicone-based foam suppressant or combinations thereof. In general, the levels are from 0% to approximately 10%, preferably from approximately 0.001% to approximately 5%. However, the generally preferred compositions (based on cost and / or deposition considerations) do not contain foam suppressors, ie they are completely free of them, or contain foam suppressors only at low levels, for example less than about 0.1% of active foam suppressant agent. The silicone-based foam suppressor technology and other defoaming 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 E.U.A. 3,933,672 and 4,136,045. Highly preferred silicone-based foam suppressors are the known mixed types used in laundry detergents such as heavy-duty granules, although the types currently used only in heavy-duty liquid detergents may also be incorporated into the compositions of the present. For example, polydimethylsiloxanes having trimethylsilyl units or alternating block terminating units can be used as the silicone. These can be mixed with silica and / or with surface-active non-siliceous components, as illustrated by a foam suppressant containing 12% silicone / silica, 18% stearyl alcohol and 70% starch in granulated form. An appropriate commercial source of the silicone-based active 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 phosphate esters contain from 16-20 carbon atoms. Highly preferred alkyl phosphate esters are monostearyl acid phosphate or monooleyl acid phosphate, or salts thereof, particularly alkali metal salts or mixtures thereof.

It has been found to be preferable to avoid the use of simple soaps that precipitate calcium as defoamers in the compositions herein since these tend to be deposited on the dishes. Indeed, the phosphate esters are not completely free of such problems and the formulator will generally choose to minimize the antifoam content potentially deposited in the compositions herein.

Auxiliary Materials The detersive or auxiliary ingredients optionally included in the compositions herein may include one or more materials to assist or increase the cleaning performance, the treatment of the substrate to be cleaned, or it may be designed to improve the aesthetic appearance of the substrate. The compositions. Auxiliaries that can be included in the compositions of the present invention, at the conventional levels established by the art to be used, (generally, the auxiliary materials constitute, in total, from about 30% to about 99.9%, preferably from about 70% up to about 95% by weight of the compositions) include other active ingredients such as non-phosphate builders, chelators, enzymes, dispersing polymers (eg from BASF Corp. or Rohm &Haas), color spots, agents for care of silver, anti-rust and / or anti-corrosion agents, silicates, dyes, fillers, germicides, alkalinity sources, hydrotropes, antioxidants, enzyme stabilizing agents, perfumes, solubilizing agents, vehicles, processing aids, pigments and agents for pH control. Depending on whether a greater or lesser degree of compaction is required, filler materials may also be present in the compositions herein. These include sucrose, sucrose esters, sodium sulfate, potassium sulfate, etc., in amounts up to about 70%, preferably from 0% to about 40% of the composition. The preferred filler material is sodium sulfate, especially in suitable grades that have when more low levels of trace impurities. The sodium sulfate used herein is preferably of sufficient purity to ensure that it does not react with the bleach; it can also be treated with low levels of sequestrant, such as phosphonates or EDDS in the form of magnesium salt. Note that the preferences, in terms of sufficient purity to avoid bleach decomposition, also apply to the ingredients of the component to adjust the pH, specifically including any silicate used herein. Hydrotropic materials such as sodium benzenesulfonate, sodium toluenesulfonate, sodium cumenesulfonate, etc., may be present, for example, to more uniformly disperse the surfactant.

Perfumes stable to bleach (stable in terms of aroma); and bleach-stable dyes such as those described in US Pat. 4,714,562, Roselle et al, issued December 22, 1987 may also be added to the compositions herein in appropriate amounts. Since the compositions herein may contain water-sensitive ingredients or ingredients that can co-react when put together in an aqueous medium, it is desired to keep the free moisture content to a minimum, for example 7% or less, preferably 5% or less of the compositions; and providing the package that is substantially impermeable to water and carbon dioxide. The 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 re-circulatable types, as well as conventional cartons or barrier boxes are other useful means of ensuring maximum shelf-storage stability. As indicated, when the ingredients are not highly compatible, it would also be desirable to coat at least one such ingredient with a low foaming nonionic surfactant to protect it. There are numerous waxy materials that can easily be used to form appropriate coated particles from any of the other, otherwise incompatible, components.; however, the formulator prefers those materials that do not have a marked tendency to deposit or to form films on the plates including those of construction based on plastic material. The following non-limiting examples further illustrate the present invention.

EXAMPLE 8 An automatic dishwashing detergent composition is prepared as follows: Ingredients% by weight BA Sodium tripolyphosphate (STPP) 24.0 45 Sodium carbonate 20.0 13.5 Hydrated 2R silicate 15 13.5 Nonionic surfactants1 2.0 2.0 Nonionic surfactant Tergitol 15S92 1.0 1.0 Polymer3 4.0 - Protease (4% active) .83 .83 Amylase (0.8% active) 0.5 0.5 Perborate monohydrate (AvO 15.5% active) 4 1 144..55 14.5 Catalyst based on cobalt5 0.008 Water, sodium sulfate and several others Polyol (oxyalkylated) alcohol end blocked with ether of example 6 2 Ethoxylated secondary alcohol supplied by Union Carbide (cloud point = 60 ° C). 3 Terpolymer selected from either 60% acrylic acid / 20% maleic acid / 20% ethyl acrylate or 70% acrylic acid / 10% maleic acid / 20% ethyl acrylate. 4The AvO level of the previous formula is 2.2%. 5 Pentaaminacetatecobalt nitrate (III).

The ADDs of the foregoing dishwashing detergent composition examples can be used to wash plastic and ceramic stained with lipstick, cups stained with tea, dishes soiled with starch and spaghetti, glasses soiled with milk, flat dishes soiled with starch, cheese , egg or baby food, and plastic spatulas stained with tomato loading the dirty dishes in a domestic appliance for automatic dishwashing and washing them using either cold fill washing cycles, maximum 60 ° C peak, or washing cycles between 45-50 ° C uniformly with a product concentration of the example compositions of about 1,000 to 10,000 ppm, with excellent results. The following examples further illustrate accumulated phosphate ADD compositions containing a bleach / enzyme particle, but are not intended to be limiting thereof. All the indicated percentages are by weight of the finished composition, different from the component perborate (monohydrate), which is listed as AvO.

EXAMPLES 9 - 10 9 10 Catalyst1 0.008 0.004 Savinase ™ 12T - 1.1 Protease D 0.9 ~ Duramyl ™ 1.5 0.75 STPP 31.0 30.0 Na2CO3 20.0 30.5 Polymer2 4.0 - Perborate (AvO) 2.2 0.7 Dibenzoyl peroxide 0.2 0.15 Silicate 2 R (Si02) 8.0 3.5 Paraffin 0.5 0.5 Benzotriazole 0.3 0.15 Ag. Non-ionic surfactant 1.0 1.0 Sodium sulfate, humidity d the rest the rest In the compositions of Examples 9 and 10, respectively, the catalyst and the enzymes are introduced into the compositions as particles of mixed material of 200-2400 microns which are prepared by spraying, fluidized bed granulation, disk formation operations. , of pills or flake / grinding. If desired, the protease and amylase enzymes can be formed separately into their respective catalyst material / enzyme particles, for stability reasons, and these separate mixed materials are added to the compositions.

EXAMPLES 11 AND 12 Granulated dishwashing detergents are as follows: 11 12 Mixed material particle 1.5 0.75 Savinase ™ 12T 2.2 __ Protease D STPP 34.5 30.0 Na2CO3 20.0 30.5 Acusol 480N 4.0 - Perborate (AvO) 2.2 0.7 Silicate 2R (Si02) 8.0 3.5 Paraffin - * _ 0.5 11 12 Benzotriazole - 0.15 Surfactant nonionic1 1.0 1.0 LF4042 1.0 1.75 Sodium sulfate, moisture the rest the rest 1 Prepared according to example 6. 2 A mixture of ethoxylated / propoxylated nonionic surfactants available from BASF.

EXAMPLE 13 The liquid detergent formulas for dishwashing for light work are prepared as follows: Composition Ingredient A B C *% by weight Surfactant1 1.00 2.00 1.50 AES 32.00 33.00 29.00 Surfactant based on 5.00 oxide 4.50 6.00 amine Composition Ingredient A B % in weigh Surfactant 3.00 5.00 1.75 based on betaine Perfume 0.18 0.18 0.18 Water and minors rest Prepared in accordance with example 6.

EXAMPLE 14 A detergent tablet for automatic dishwashing is prepared from the composition as follows: Ingredients% by weight Sodium Tripolyphosphate (STPP) 50.0 47.0 Sodium Carbonate 14.0 15 Hydrated 2-R Silicate 8.0 5.0 Non-ionic Surfactant1 0.4 2.0 Non-ionic Surfactant 1.0 1.0 Tergitol 15S92 Polymer3 4.0 i co Protease (4% active) 2.0 1.50 Amylase (0.8% active ) 0.5 Perborate monohydrate (AvO 1.5 1.5 15.5% active) 4 Catalyst based on cobalt5 0.008 TAED 2.2 Benzotriazole 0.3 Paraffin oil 6 0.5 Water, sodium sulfate, and several others the rest 1 Poly (oxyalkylated) alcohol with ether-blocked ends of Example 6. 2 Ethoxylated secondary alcohol supplied by Unión Carbide (cloud point = 60 ° C). 3 Polyacrylate-based polymer mixed with HEDP. 4The AvO level of the previous formula is 2.2%. 5 Pentaaminacetatecobalt nitrate (III). ^? / inog 70 available from Wintershall, Salzbergen, Germany. The ADDs of the above detergent ware washing composition examples can be used to wash plastic and ceramic materials stained with lipstick, cups stained with teas, dishes stained with starch and spaghetti, glasses soiled with milk, flat dishes soiled with starch, cheese, egg or baby food, and plastic spatulas stained with tomato loading the dishes soiled in a domestic automatic dishwashing machine and washing using washing cycles either with cold filling, 60 ° C peak, or 45-50 ° C uniformly with a product concentration of the example compositions of about 1,000 to 10,000 ppm with excellent results.

EXAMPLE 15 A hard surface cleaning composition of the present invention is illustrated as follows:% by weight Ingredients 18 19 20 21 22 23 Surfactant Agent1 0.25 3.5 5.5 6.5 6.1 9.5 Sodium hypochlorite 0.9 1.4 1.4 - - - Calcium hypochlorite - ~ ~ 0.5 - - Dichlorocyanurate of - - - - 1.2 2.0 Sodium Pyrophosphate 6.0 - - ~ 13.0 - tetrapotassium Tripotassium Phosphate 2.0 ~ - - 12.0 ~ Sodium tripolyphosphate - - ~ 1.6 ~ - Calcium carbonate - - - ~ 39.0 1.1 Calcium oxide 2.8 Abrasive based on 6.5 ~ ~ - 22.5 0.5 perlite Sodium hydroxide 0.8 1.6 1.8 0.8 1.1 1.0 Potassium hydroxide ~ ~ ~ 0.85 - - Colorants 0.75 0.28 0.28 0.28 - ~ Lanolin - - - - ~ 2.1 Carboxymethylcellulose - - - - - 2.6 Water / several the rest the rest the rest the rest the rest the rest the rest EXAMPLE 16 The liquid, gel-type automatic dishwashing detergent compositions according to the present invention are prepared as follows: Detergent builder based on STPP 17.5 16 Potassium carbonate 8 Sodium carbonate - 1.5 Potassium hydroxide 2 2.0 Potassium silicate 4 1.5 Sodium silicate 2 3 Thickener 1 1 Nitric acid 0.02 0.02 Aluminum tristearate 0.1 Polymer dispersant2 0.5 Sodium benzoate 0.8 0.5 Surfactant 1.0 1.0 2.0 Perborate 2.2 Sodium hypochlorite 1.5 Water and minors rest the rest Poly (oxyalkylated) alcohol end blocked with ether of Example 6. Sodium polyacrylate of molecular weight 4,500.

Claims (14)

NOVELTY OF THE INVENTION CLAIMS

1. A composition for cleaning hard surfaces comprising: a) from 0.1% to 15% by weight of the composition, of a surfactant, characterized in that said surfactant comprises a poly (oxyalkylated) alcohol surfactant with ether-blocked ends having the formula: R 1 O [CH 2 CH (R 3) O] x [CH 2] kCH (OH) [CH 2] jOR 2 wherein R 1 and R 2 are aliphatic or aromatic hydrocarbon radicals, linear or branched, saturated or unsaturated, having from 1 to 30 carbon atoms; R3 is H or a linear aliphatic hydrocarbon radical having 1 to 4 carbon atoms; x is an integer that has an average value of 1 to 40, where when x is 2 or more, R3 can be identical or different, and k and j are integers that have an average value of 1 to 12; wherein in addition when x is 15 or more and R3 is H and methyl, at least four of R3 are methyl, wherein when x is 15 or more and R3 includes H and from 1 to 3 methyl groups, then at least one R3 is ethyl, propyl or butyl, and wherein R2 can also be optionally alkoxylated, wherein said alkoxy is selected from ethoxy, propoxy, butyloxy, and mixtures thereof; b) from 0.1% to 99% by weight of the composition of auxiliary detergent ingredients.

2. - A detergent composition comprising: a) 0.1% a 15% by weight of the composition, of a surfactant, characterized in that said surfactant comprises an ether-blocked poly (oxyalkylated alcohol) surfactant having the formula: R1O [CH2CH (R3) 0] x [CH2] kCH (OH) [CH2] jOR2 wherein R1 and R2 are aliphatic or aromatic hydrocarbon radicals, linear or branched, saturated or unsaturated, having from 1 to 30 carbon atoms; R3 is H or a linear aliphatic hydrocarbon radical having 1 to 4 carbon atoms; x is an integer that has an average value of 1 to 40, where when x is 2 or more, R3 can be identical or different, and k and j are integers that have an average value of 1 to 12; wherein in addition when x is 15 or more and R3 is H and methyl, at least four of R3 are methyl, wherein when x is 15 or more and R3 includes H and from 1 to 3 methyl groups, then at least one R3 is ethyl, propyl or butyl, and wherein R2 can also be optionally alkoxylated, wherein said alkoxy is selected from ethoxy, propoxy, butyloxy, and mixtures thereof; b) from 0.1% to 99% by weight of the composition of auxiliary detergent ingredients. 3. A composition for automatic dishwashing comprising: a) from 0.1% to 15% by weight of the composition, of a surfactant, characterized in that said surfactant comprises a poly (oxyalkylated) alcohol surfactant of blocked ends with ether that has the formula:

R10 [CH2CH (R3) 0] x [CH2] kCH (OH) [CH2] JOR2 wherein R1 and R2 are aliphatic or aromatic hydrocarbon radicals, linear or branched, saturated or unsaturated, having from 1 to 30 carbon atoms; R3 is H or a linear aliphatic hydrocarbon radical having 1 to 4 carbon atoms; x is an integer that has an average value of 1 to 40, where when x is 2 or more, R3 can be identical or different, and k and j are integers that have an average value of 1 to 12; wherein in addition when x is 15 or more and R3 is H and methyl, at least four of R3 are methyl, wherein when x is 15 or more and R3 includes H and from 1 to 3 methyl groups, then at least one R3 is ethyl, propyl or butyl, and wherein R2 can also be optionally alkoxylated, wherein said alkoxy is selected from ethoxy, propoxy, butyloxy, and mixtures thereof; b) from 0.1% to 99% by weight of the composition of auxiliary detergent ingredients.

4. A composition for automatic dishwashing that is added in the rinse comprising: a) from 0.1% to 15% by weight of the composition, of a surfactant, characterized in that said surfactant comprises an alcohol poly surfactant (oxyalkylated) of ends blocked with ether having the formula: R10 [CH2CH (R3) 0] x [CH2] kCH (OH) [CH2] jOR2 wherein R1 and R2 are aliphatic or aromatic hydrocarbon radicals, linear or branched, saturated or unsaturated, which have from 1 to 30 carbon atoms; R3 is H or a linear aliphatic hydrocarbon radical having 1 to 4 carbon atoms; x is an integer that has an average value of 1 to 40, where when x is 2 or more, R3 can be identical or different, and k and j are integers that have an average value of 1 to 12; wherein in addition when x is 15 or more and R3 is H and methyl, at least four of R3 are methyl, wherein when x is 15 or more and R3 includes H and from 1 to 3 methyl groups, then at least one R3 is ethyl, propyl or butyl, and wherein R2 can also be optionally alkoxylated, wherein said alkoxy is selected from ethoxy, propoxy, butyloxy, and mixtures thereof; b) from 0.1% to 99% by weight of the composition of auxiliary detergent ingredients.

5. The composition according to any of claims 1 to 4, further characterized in that R1 and R2 are aliphatic or aromatic hydrocarbon radicals, linear or branched, saturated or unsaturated, having from 6 to 22 carbon atoms.

6. The composition according to any of claims 1 to 5, further characterized in that said auxiliary detergent ingredients are selected from the group consisting of builders, surfactants, bleaching agents, enzymes and mixtures thereof.

7. The composition according to any of claims 1 to 6, further characterized in that said composition includes an enzyme that is selected from the group consisting of protease enzymes, amylase enzymes and mixtures thereof.

8. The composition according to any of claims 1 to 7, further characterized in that said composition includes a bleaching system and said bleaching system comprises a source of hydrogen peroxide and an additional ingredient selected from bleach activators, catalysts from bleaching and mixtures thereof.

9. The composition according to claim 8, further characterized in that said bleaching system comprises a source of hydrogen peroxide and a bleaching catalyst having the formula: [Co (NH3) n (M) m (B) b ] Ty where the cobalt is in the +3 oxidation state; n is 4 or 5; M is one or more ligands coordinated with the cobalt by a site; m is 0, 1 or 2; B is a ligand coordinated to cobalt by two sites; b is 0 or 1; and when b = 0, then m + n = 6, and when b = 1, then m = 0 and n = 4; and T is 1 or more appropriately selected counter-anions present in a number and, where y is an integer to obtain a balanced salt in terms of charges; and wherein further said catalyst has a hydrolysis rate constant in basic medium of less than 0.23 M "1 s" 1 (25 ° C).

10. The composition according to any of claims 1 to 9, further characterized in that said composition includes an amine oxide.

11. The composition according to any of claims 1 to 10, further characterized in that said composition is free of foam suppressors based on phosphate ester and silicon.

12. - A method for washing dishes in a household automatic dishwashing appliance, said method comprising treating the dirty tableware in an automatic dishwashing machine with an alkaline aqueous bath containing a composition for automatic dishwashing according to any of the claims 3 to 10.

13. A method for suppressing foam, said method comprising the step of adding an effective amount of a foam suppressing composition to an aqueous cleaning solution, said composition comprising: a) from about 0.1% to about 15% by weight of the composition, of a surfactant, characterized in that said surfactant comprises an ether-blocked poly (oxyalkylated alcohol) surfactant having the formula: R10 [CH2CH (R3) 0] x [CH2] kCH ( OH) [CH2] jOR2 wherein R1 and R2 are aliphatic or aromatic hydrocarbon radicals, linear or branched, saturated or unsaturated, having n of 1 to 30 carbon atoms; R3 is H or a linear aliphatic hydrocarbon radical having 1 to 4 carbon atoms; x is an integer that has an average value of 1 to 40, where when x is 2 or more, R3 can be identical or different, and k and j are integers that have an average value of 1 to 12; wherein in addition when x is 15 or more and R3 is H and methyl, at least four of R3 are methyl, wherein when x is 15 or more and R3 includes H and from 1 to 3 methyl groups, then at least one R3 is ethyl, propyl or butyl, and wherein R2 can also be optionally alkoxylated, wherein said alkoxy is selected from ethoxy, propoxy, butyloxy, and mixtures thereof and b) from about 0.1% to about 99% by weight of the composition of detergent auxiliary ingredients.

14. A method for suppressing foam according to claim 13, further characterized in that said aqueous cleaning solution is in an automatic dishwashing machine.