MXPA00000791A - Method for sanitization of substrates with detergent compositions - Google Patents

Abstract

A method for sanitizing a substrate by contacting a microbe containing substrate with a detergent composition for a sufficient time to substantially reduce the amount of microbes on the substrate. Metals, coated metals, plastics, rubber, dishware, countertops, fabric, wood surfaces, and other substrates can be sanitized by applying a light duty detergent composition, preferably a liquid, cream, paste, or gel detergent composition, which comprises an antimicrobial agent such as a surfactant.

Description

METHOD FOR SANITATION OF SUBSTRATES WITH DETERGENT COMPOSITIONS RELATED REQUESTS This application claims priority under 36 U.S.C. 119 (e) to the provisional request of E.U.A. No. 60 / 053,322, published July 21, 1997, and to the application of E.U.A. Copending No. 08/961, 622, published on October 31, 1997.

TECHNICAL FIELD The present invention relates to detergent compositions, preferably liquid or gel detergents. Specifically, the invention relates to a method for removing dirt and sanitizing (significantly reducing populations of microorganisms) plastics, crockery, cabinets, cloth, wood surfaces and other substrates by applying a light duty detergent composition, preferably a composition in the form of a liquid. , cream, paste or gel, which preferably comprises non-quaternary surfactants. This method provides improved cleaning along with sanitizing, disinfecting or antibacterial action on the treated surfaces.

BACKGROUND OF THE INVENTION Detergents that are used to wash dishes at a domestic or institutional level (ie, glassware, china, silver, plastic, etc.) or kitchen utensils (ie cooking utensils, cutting boards, cabinets) have been known for some time. , etc). Dishwashing in the seventies is described by Mizuno in Vol. 5, Part III of the Surfactant Science Series, Ed. W.G. Cutler and R.C. Davis, Marcel Dekker, NY, 1973. The particular requirements for cleaning dishes and leaving them in a hygienic state, essentially free of dirt and debris has resulted in particular compositions that the field of technology to which they belong now is recognized as a field different to other fields of cleaning products. In addition, consumers continue to worry about the sanitary conditions in their homes. The above is perceived as a real problem with germs in the home, particularly on tableware, food preparation areas, and on equipment used with children or sick people. Consumers continue to experience problems in obtaining adequate antibacterial action on various substrates, including typical kitchen surfaces and tableware. The formulators have experienced difficulties in formulating detergents that can remove dirt and reduce the amount of microorganisms on the surface. Normally to achieve both jobs, consumers have resorted to the addition of chlorine in the wash water or to the action of rinsing the already cleaned surface with a solution containing bleach to add antibacterial action. Although chlorine bleach is effective in fighting dirt and for antibacterial action, it is not compatible with a variety of detergent ingredients and does very little to really remove dirt from the substrate. In addition, the bleach is strong for many surfaces and for the consumer's hands and has an unpleasant odor. As a consequence of the above problem, a considerable amount of research has been carried out to develop detersive systems that are stable with a variety of ingredients and achieve both removal and sanitation. Also, an important point in the development of effective products for the consumer, both in the removal and in the elimination of dirt and germs, are the additional costs associated with the use of multiple additives. In this way, it is of considerable interest to the manufacturers of detergent products, to find a less expensive component that can perform both jobs.

BRIEF DESCRIPTION OF THE INVENTION By the present invention, it has been discovered that certain surfactants are stable, perform good soil removal and sanitation when the surfactant is applied without additional water (or with a minimum amount of additional water) to a substrate and remain in contact for a period of time. time frame. Likewise, the present invention solves the need for an economical cleaning system that acts efficiently and effectively under dirt loading conditions and which provides very good antimicrobial action. This, in turn, can lead to family members being healthier, which results in fewer sick days, less opportunity for disease transmission, and fewer appointments with a person who provides health care. The present invention is a method for sanitizing a substrate containing microbes comprising the steps of: a) contacting the substrate with a detergent composition comprising an effective amount of an antimicrobial agent; b) allowing the detergent composition to remain in contact with the substrate for a sufficient time to significantly reduce the amount of microbes on the substrate. In a preferred embodiment of the invention, step b) can be carried out in a conventional microwave oven to activate the antimicrobial action of the detergent composition. Without trying to limit the types of substrates that can be treated, examples of substrates that can be treated by this method include fabrics, ceramics, porcelain, plastic, scourers, cutting boards, surgical / medical equipment, baby bottles, tableware, dentures / dentures, wood, surfaces for the preparation of food, sponges, glass, rubber, metal, coated metal (for example, pans coated with Teflon®) and mixtures thereof. The method of application can vary significantly. For example, the product can be applied directly to the substrate, sprayed onto the substrate or dispersed by an implement (sponge, roller, paper towel, cleaning cloth, etc.) on the surface to be treated. The method herein may be employed to eliminate or reduce the viable level of microbes that may include any microorganism, such as bacteria (gram + or -), viruses (covered or uncovered), parasites, fungi / spores, and other household germs typical commonly found on surfaces in the kitchen. All proportions and percentages herein are by weight, and all references cited are incorporated herein by reference, unless otherwise specified.

DETAILED DESCRIPTION OF THE INVENTION Definitions The detergent compositions herein comprise an "effective amount" or a "sanitizing or soiling amount" of a particularly defined antimicrobial agent that is preferably a surfactant. An "effective amount" or "amount of sanitation" of an antimicrobial agent is any amount capable of improving both the removal of dirt and the cleaning of the substrate, i.e. dirty dishes, when washed by the consumer. In general, this amount can vary widely. As used herein, the terms "disinfection", "disinfection", "antibacterial", "germ removal", and "sanitation" refer to eliminating microbes commonly found in kitchens and domestic places. Examples of various microbes include: germs, bacteria, viruses, parasites and fungi / spores. Preferably the detergent compositions herein are contacted with the substrate for a time sufficient to significantly reduce the amount of microbes on the substrate. By "significant reduction" is meant that at least 50% of the microbes on the substrate are removed or otherwise become inactive, preferably the amount of microbes on the substrate is reduced by at least about 90%, and most preferably the amount of microbes on the substrate is reduced by at least about 99.9%. Examples of surfactants that are useful antimicrobial agents for use herein include anionic, cationic, nonionic and amphoteric surfactants. Preferred examples are: alkylalkoxy sulfates, including alkyl ethoxy sulfates, linear alkylbenzene sulphonates, amine oxide, polyhydroxy fatty acid amides, ethoxylated alcohols, diamines, amides, alkyl polyglycosides, betaines and mixtures thereof. When the antimicrobial agent is a cationic surfactant it is preferred that the cationic surfactant is not a quaternary ammonium surfactant. The detergent compositions of the present invention comprise surfactants at from about 1% to about 80%, preferably from about 10% to about 70%, most preferably from about 20% to about 60%, and still most preferably from about 30% to about 50%, by weight of the total composition. Usually the "sufficient time" in step b) is at least about 10 seconds, preferably about 15 seconds to about 2 minutes and most preferably about 30 seconds to about 1 minute. Of course, longer times are more effective. Surprisingly it has been found that by placing the substrate, while still in contact with the detergent composition, in a conventional microwave oven and operating the oven for a sufficient time, the antimicrobial action of a detergent composition can be improved. Without wishing to delve into the theory, it is believed that the energy imparted to the detergent composition by microwave radiation in the furnace serves to activate and improve the antimicrobial action of the detergent composition. Microwave ovens suitable for use in the present invention are manufactured by companies such as Litton®, Amana®, Sharp®, General Electric®, and others, and have become ubiquitous in kitchens throughout the global industry. Microwave ovens can be purchased at any department store, appliance stores and a variety of large stores, such as K-Mart® and Wal-Mart®. By "operating" the microwave oven means that enough time is selected and the microwave oven is turned on for the selected length of time; In this regard, manufacturers suggest operating instructions and safety precautions that should be followed. Depending on the length of time selected for the microwave oven, the substrate may be hot and require care when removed from the oven. A cooling period for the substrate is also desirable. To achieve maximum sanitation action, the detergent compositions are preferably applied directly to the substrate with a minimum of water, even very preferably free of water. In addition, the substrate should remain in contact with the detergent for a sufficient time before adding water or before the detergent is rinsed. However, the surface to be treated can be pre-rinsed or moistened before the application of the detergent composition herein provided there is no water left. In other words, the surface can be wet but not submerged in water. It is believed that detergent compositions with the level of surfactant level percentage set forth herein have concentrations of ingredients high enough to allow dissolution during use. Of course this depends on the concentration of the active ingredients in the product. Preferably, the detergent composition is diluted with less than about 10% water, most preferably less than about 30% water and still most preferably less than about 50% water. In contrast and for comparison purposes, in a typical domestic kitchen, a sink filled with water and dishes and dosed by an average amount of detergent product for liquid dishwashing (4 to 7g, with approximately 10-45% surfactant) will have a total product concentration level of less than about 1% in the wash water, that is, diluted 99% with water. If the washing is done in a rubber tube or in a large container placed in the sink, the concentration of the total product is only about 5%, ie 95% dissolution. Even a sponge that has been soaked in water, with detergent applied to the surface of the sponge will have a detergent product concentration of only about 10%, ie 90% dissolution.

Product / Instructions The invention also comprises the inclusion of instructions in the use of the detergent composition with the package containing the detergent compositions herein or with other forms of advertising associated with the sale or use of the detergent compositions. The instructions may be included in any manner typically used by the product manufacturer or supplier companies. Examples include providing instructions on a label attached to the container containing the composition; on a sheet attached to the container or accompanying it when it is purchased; or in advertisements, demonstrations and / or other written or oral instructions that may be connected with the purchase or use of the detergent compositions. Specifically the instructions include a description of use of the detergent composition containing surfactant in connection with allowing the detergent to remain in contact with the substrate before the addition of a substantial volume of water or before rinsing. The instructions, for example, may additionally include information that refers to the length of contact time; the recommended dose or amount of treatment composition to apply to the substrate, if soaking or rubbing is appropriate; the recommended amount of water, if any, to be applied to the substrate before or after treatment; Another recommended treatment to accompany the application of the detergent. Also, the present invention comprises a product consisting of a detergent composition comprising an effective amount of an antimicrobial agent and instructions for using the detergent composition, the instructions include the steps of: a) Contacting a substrate containing microbes with the detergent composition; and b) allowing the detergent composition to remain in contact with the substrate for a sufficient time to significantly reduce the amount of microbes on the substrate.

Other Ingredients The detersive or adjunct ingredients optionally included in the compositions herein may include one or more materials to aid or improve cleaning performance, substrate treatment that will be cleaned, or designed to improve aesthetics, maintain chemical and physical stability , or facilitate the manufacture of the compositions. Other adjunct materials that may also be included in the compositions of the invention at their levels established in the conventional art, generally from 0 to about 20% of the composition, preferably from about 0.1% to about 10%, include one or more auxiliaries of processing, polymer thickeners, dyes, fillers, enzymes, alkalinity sources, hydrotropes, stabilizers, perfumes, solvents, vehicles, sodium bicarbonate, carbonates, hydrobenzoic acid, dicarboxylic acid, bleach, divalent ions, dispersing polymers, chelators, improvers detergency such as citrate and pH regulators. The composition preferably has a pH of about 3 to about 11.5, preferably about 6 to about 11. The divalent ions, when present, are preferably selected from inorganic cations, organic cations and mixtures thereof and very preferably are selected from Mg2 +, Ca2 + and mixtures thereof. Other non-surfactant germicides may be included for further antimicrobial action if they do not interfere adversely with the surfactants used herein. Examples of antimicrobials include triclosan, trichlorocarbon, hydrogen peroxide, other oxygen bleaches, for chloro-meta-xylenol, iodine / iodophors, selected alcohols, chlorhexidine, phenols, phospholipids, thymol, eugenol, geraniol, lemon leaf oil, and Limonene Certain quaternary surfactants may also show antimicrobial action and may be included as a secondary germ killing agent.

Anionic Surfactants The anionic surfactants useful in the present invention are preferably selected from the group consisting of branched alkylethylsulfates, linear Ce-Cia alkylbenzenesulfonate, alphaolephinsulfonate, paraffin sulphonates, methyl estersulfonates, branched-chain primary random C 1 -s-alkylsulfonates ( "AS"), the secondary alkyl sulfates (2,3) of Ce-Cie of the formula CH 3 (CH 2)? (CHOSO 3 -M +) CH 3 and CH 3 (CH 2) and (CHOS 3-M +) CH 2 CH 3 where xy (y + 1) are integers of at least 7, preferably at least 9, and M is a cation that is solubilized in water, especially sodium, unsaturated sulfates such as oleyl sulfate, C 8 -C 18 alkyl ethoxy sulfates ("AEXS"; especially EO 0.5-7 ethoxysulfates), alkylalkoxycarboxylates of C8-C- | 8 (especially EO 0.5-5 ethoxycarboxylates), glycerol ethers of C8-C8, alkyl polyglycosides of C8-C8) and their corresponding polyphosphonates, aliphatic sulphonates, sarcosinates, taurinates, acid esters alpha-sulfonated fatty acids of C8-C, 8 and mixtures thereof. One type of anionic surfactant that can be used comprises the alkyl ester sulfonates. These are desirable since they can be made from renewable non-oil resources. The preparation of the alkyl ester sulfonate surfactant component can be carried out according to known methods described in the technical literature. For example, the linear esters of C8-C20 carboxylic acids can be suifonated with gaseous SO3 according to "The Journal of the American Oil Chemists Society, "52 (1975), p 323-329. Suitable starting materials should include natural fatty substances such as those derived from tallow, palm and coconut oils, etc. The preferred alkyl sulfonate ester surfactant comprises alkyl sulfonate ester surfactants of the structural formula: OR R3-CH-C-OR4 SO3M wherein R3 is a C8-C20 hydrocarbyl. preferably an alkyl, or combination thereof, R ^ is a hydrocarbyl of C- \ -CQ, preferably an alkyl or combination thereof, and M is a salt-forming cation. Suitable salts include metal salts such as sodium, potassium and lithium, and substituted or unsubstituted ammonium salts, such as methyl-, dimethyl-, trimethyl- and suitable salt-forming cations include metals such as sodium, potassium and lithium. , and substituted or unsubstituted ammonium catrones, such as monoethanolamine, diethanolamine and triethanolamine. Preferably, R3 is C- | Q-Ci6 alkyl and is methyl, or isopropyl. Especially preferred are the methyl estersulfonates wherein R3 is C14-C16 alkyl. Alkyl sulfate surfactants are another type of surfactant useful herein. Examples of alkyl sulfates are water-soluble salts or acids of the formula ROSO3M, wherein R is preferably a C-10-C24 hydrocarbyl. preferably an alkyl or hydroxyalkyl having an alkyl component of C- | rj-C20 > most preferably an alkyl or hydroxyalkyl of C-12-C18. and M is H or a cation, for example, an alkali or alkali metal cation (Group IA or Group HA) (eg, sodium, potassium, lithium, magnesium, calcium), or substituted ammonium or ammonium such as cations of methyl-, dimethyl-, and trimethylammonium and quaternary ammonium cations such as tetramethylammonium and dimethylpiperidinium cations and cations derived from alkanolamines such as ethanolamine, diethanolamine, triethanolamine and mixtures thereof, and the like. Typically, alkyl chains of C-12-C- | e are preferred for lower wash temperatures (e.g., below about 50 ° C) and alkyl chains of C-J6-18 are preferred for higher wash temperatures. (for example, about 50 ° C). The alkoxylated alkyl sulfate surfactants are another category of suitable anionic agent. These surfactants are salts or water soluble acids that normally have the formula RO (A) mSO3M, wherein R is an unsubstituted C 0 -C 24 alkyl or hydroxyalkyl group having an C 0 -C 2 alkyl component, preferably an C 1 -C 20 alkyl or hydroxyalkyl, most preferably C 2 alkyl or hydroxyalkyl. -C.8, A is an ethoxy or propoxy unit, m is greater than zero, typically between 0.5 and about 6, most preferably between about 0.5 and about 3, and M is H or a cation which may be, for example , a metal cation (eg, sodium, potassium, lithium, magnesium, calcium, etc.), an ammonium or substituted ammonium cation. The ethoxylated alkyl sulfates as well as the propoxylated alkyl sulphates are understood herein. Exemplary surfactants are polyethoxylated alkyl sulfate (1.0) of C 2 -C 8, polyethoxylated alkyl sulfate (2.25) of C 12 -C 18, polyethoxylated alkyl sulfate (3.0) of C 2 -C 8 and polyethoxylated alkyl sulphate (4.0) of C? 2-C? 8, wherein M is conveniently selected from sodium and potassium. The surfactants which are used herein may be made from natural or synthetic alcohol supply materials. The chain lengths represent the average hydrocarbon distributions, including branching. Other anionic surfactants useful for detersive or sanitizing purposes may also be included in the detergent compositions of the present invention. These may include salts (including, for example, sodium, potassium, ammonium and substituted ammonium salts such as mono-, di- and triethanolamine salts) of soap, linear C9-C2o alkylbenzenesulfonates, primary or secondary C8-alkanesulfonates. C22 'C8-C24 olefinsulfonates, suifonated polycarboxylic acids prepared by the sulfonation of the pyrolyzed product of alkaline earth metal citrates, for example, as described in the description of British Patent No. 1, 082,179, alkyl glycerol sulfonates, fatty acyl glycerol sulfonates , fatty oleylglycerol sulfonates, alkylphenol ethylene oxide sulphates, paraffin sulfonates, alkyl phosphates, isothionates, such as acyl isothionates, N-acyl taurates, fatty acid amides of methyltauride, alkyl succinamates and sulfosuccinates, sulfosuccinate monoesters (especially saturated and unsaturated C-12-C18 monoesters) and sulfosuccinate diesters (especially saturated and unsaturated CQ-C-14 diesters), N-acyl sarcosinates, alkylpolysaccharide sulfates such as the alkyl polyglycoside sulphates (the non-sulphonated nonionic compounds being described below), branched primary alkyl sulphates and alkyl polyethoxycarboxylates such as those of the formula RO (CH2CH2?) KCH2COO-M + in which R is a C8-C22 alkyl, k is an integer from 0 to 10 and M is a soluble salt-forming cation, and fatty acids esterified with isethionic acid and neutralized with hydroxide of sodium. Resin acids and hydrogenated resin acids are also suitable, such as rosin, hydrogenated rosin and rosin acids, as well as hydrogenated rosin acids present in or derived from tallow oil. Additional examples are described in "Surface Active Agents and Detergents" (Vol. I and II by Schwartz, Perry and Berch). A variety of such surfactants are generally also described in the U.S.A. No. 3,929,678, issued December 30, 1975 to Laughiin, and others, in Column 23, line 58 to Column 29, line 23.

Nonionic detergent surfactants Suitable nonionic surfactants are generally described in US Pat. 3,929,678, Laughiin et al, issued December 30, 1975, in column 13, line 14 to column 16, line 6, incorporated herein by reference. Exemplary and non-limiting classes of useful nonionic surfactants include: C 8 -C 8 alkyl ethoxylates ("AE"), with EO of about 1-22, including so-called narrow peak alkyl ethoxylates and C 6 -C 12 alkoxylated alkylphenols (especially ethoxylates and mixed ethoxy / propoxy), alkyldialkylamine oxide, alkanoyl glucosamide and mixtures thereof. Other nonionic surfactants that can be used herein include: The condensates of polyethylene oxide, polypropylene and polybutylene of alkylphenols. In general, polyethylene oxide condensates are preferred. These compounds include the condensation products of alkylphenols having an alkyl group containing from about 6 to about 12 carbon atoms, either in a straight chain or branched chain configuration with the alkylene oxide. In a preferred embodiment, the ethylene oxide is present in an amount equal to about 5 to about 25 moles, of ethylene oxide per mole of alkylphenol. Commercially available nonionic surfactants of this type include Igepal® CO-630, marketed by GAF Corporation; and Triton® X-45, X-114, X-100 and X-102, all sold by Rohm & Haas Company. These compounds are commonly known as alkylphenol alkoxylates (eg, alkylphenol ethoxylates). The condensation products of primary and secondary aliphatic alcohols with from about 1 to about 25 moles of ethylene oxide. The alkyl chain of the aliphatic alcohol may be either straight or branched, primary or secondary, and generally contains from about 8 to about 22 carbon atoms. Preferred are the condensation products of alcohols having an alkyl group containing from about 10 to about 20 carbon atoms, with from about 2 to about 18 moles of ethylene oxide per mole of alcohol. Examples of commercially available nonionic surfactants of this type include Tergitol® 15-S-9 (the linear alcohol condensation product of C- | 1-C15 with 9 moles of ethylene oxide), Tergitol® 24-L-6 NMW (the primary alcohol condensation product of C-12-C14 with 6 moles of ethylene oxide with a limited molecular weight distribution), both marketed by Union Carbide Corporation; Neodol® 45-9 (the linear condensation product of C14-C15 with 9 moles of oxide of ethylene), Neodol® 23-6.5 (the linear condensation product of C-12-C13 with 6.5 moles of ethylene oxide), Neodol® 45-7 (the linear condensation product of C14-C- 15 with 7 moles of ethylene oxide), Neodol® 45-4 (the linear alcohol condensation product of C14-C15 with 4 moles of ethylene oxide) marketed by Shell Chemical Company, and Kyro® EOB (the condensation product of C-13-C15 alcohol with moles of ethylene oxide), marketed by The Procter & Gamble Company. Other nonionic surfactants include Donabol 91-8® marketed by Shell Chemical Co. and Genapol UD-080® marketed by Hoechst. This category of nonionic surfactant is generally referred to as "alkyl ethoxylates". The condensation products of ethylene oxide with a hydrophobic base formed by the condensation of propylene oxide with propylene glycol. The hydrophobic portion of these compounds will preferably have a molecular weight of from about 1500 to about 1800, and will exhibit insolubility in water. The addition of polyoxethylene portions to this hydrophobic portion tends to increase the water solubility of the molecule as a whole, and the liquid character of the product is retained to the point where the polyoxethylene content is fj) of about 50% of the total weight of the condensation product, corresponds to the condensation with up to about 40 moles of ethylene oxide. Examples of compounds of this type include certain Pluronic® surfactants commercially available as Pluronic®, marketed by BASF. The condensation products of ethylene oxide with the product resulting from the reaction of propylene oxide and ethylenediamine. The hydrophobic portion of these products consists of the reaction product of ethylenediamine and excess propylene oxide, and generally has a molecular weight of from about 2500 to about 3000. This hydrophobic portion is condensed with sodium oxide.

Ethylene to the extent that the condensation product contains from about 40% to about 80% by weight of polyoxyethylene and has a molecular weight of from about 5,000 to about 11,000. Examples of this type of nonionic surfactant include certain of the commercially available Tetronic® compounds, marketed by BASF. Semi-polar nonionic surfactants are a special category of nonionic surfactants that include water-soluble amine oxides containing an alkyl portion of from about 10 to about 18 carbon atoms and 2 portions selected from the group consisting of alkyl groups and hydroxyalkyl groups containing from about 1 to about 3 carbon atoms; water-soluble phosphine oxides containing an alkyl portion of about 10 to about 18 carbon atoms and two portions selected from the group consisting of alkyl groups and hydroxyalkyl groups containing from about 1 to about 3 carbon atoms; and water soluble sulfoxides containing an alkyl portion of from about 10 to about 18 carbon atoms and a portion selected from the group consisting of alkyl and hydroxyalkyl portions of from about 1 to about 3 carbon atoms. The semipolar nonionic detergent surfactants include the amine oxide surfactants having the formula: wherein R 3 is an alkyl, hydroxyalkyl or alkylphenyl group or mixtures thereof, containing from about 8 to about 22 carbon atoms; R ^ is an alkylene or hydroxyalkylene group containing from about 2 to about 3 carbon atoms, or mixtures thereof; x is from 0 to about 3; and each R ^ is an alkyl or hydroxyalkyl group containing from about 1 to about 3 carbon atoms, or a polyethylene oxide group containing from about 1 to about 3 ethylene oxide groups. The R ^ groups may be attached to each other, for example, through an oxygen or nitrogen atom to form a ring structure. These amine oxide surfactants include, in particular, alkyldimethylamine oxides of C < | rj-C- | 8 and C8-C- 2- alkoxyethyldihydroxyethylamine oxides The alkylpolysaccharides described in the U.S.A. No. 4,565,647, Filling, issued January 21, 1986, having a hydrophobic group containing from about 6 to about 30 carbon atoms, preferably about 10 to about 16 carbon atoms, and a polysaccharide, for example, a polyglycoside, a hydrophilic group containing from about 1.3 to about 10, preferably from about 1.3 to about 3, most preferably from about 1.3 to about 2.7 units of saccharide. Any reducing saccharide containing 5 or 6 carbon atoms can be used, eg, glucose, galactose and galactosyl portions can be replaced by glucosyl moieties. (Optionally, the hydrophobic group is fixed at positions 2-, 3-, 4-, etc., thus giving a glucose or galactose as opposed to a glycoside or galactoside). The links between saccharides can be, for example, between position one of the additional saccharide units and positions 2-, 3-, 4- and / or 6- of the above saccharide units. Optionally, but less desirable, there may be a polyalkylene oxide chain linking the hydrophobic portion and the polysaccharide portion. The preferred alkylene oxide is ethylene oxide. Typical hydrophobic groups include alkyl groups, whether saturated or unsaturated, branched or unbranched containing from about 8 to about 18, preferably about 10 to about 16, carbon atoms. Preferably, the alkyl group is a saturated straight-chain alkyl group. The alkyl group can contain up to about 3 hydroxy groups and / or the polyalkylene oxide chain can contain up to about 10, preferably less than 5, alkylene oxide portions. Suitable alkylpolysaccharides are octyl, nonyl, decyl, undecyldecyl, tridecyl, tetradecyl, pentadecyl, hexadecyl, heptadecyl and octadecyl, di-, tri-, tetra-, penta- and hexaglucosides, galactosides, lactosides, glucoses, fructosides, fructose and / or Galactoses Suitable mixtures include cocoalkyldi, tri-, tetra- and pentalglucosides and tallowalkyltetra-, penta- and hexaglucosides. Preferred alkyl polyglycosides have the formula R2? (CnH2nO) t (glucosyl) x wherein R2 is selected from the group consisting of alkyl, alkylphenyl, hydroxyalkyl, hydroxyalkylphenyl groups and mixtures thereof, in which the alkyl groups contain from about 10 to about 18, preferably from about 12 to about 14 carbon atoms; n is 2 or 3, preferably 2; t is from 0 to about 10, preferably 0; and x is from about 1.3 to about 10, preferably about 1.3 to about 3, most preferably from about 1.3 to about 2.7. The glucosyl is preferably derived from glucose. For preparing these compounds, the alcohol or alkylpolyethoxylated alcohol is formed first, and then reacted with glucose or a source of glucose to form the glucoside (fixation at position 1). The additional glucosyl units can then be fixed between their position 1 and the preceding glucosyl units in the 2-, 3-, 4- and / or 6- position, preferably and predominantly in the 2-position. Fatty acid amide surfactants have the formula: O R6-C-N (R7) 2 wherein R6 is an alkyl group containing from about 7 to about 21 (preferably about 9 to about 17) carbon atoms and each R7 is selected from the group that it consists of hydrogen, C? -C alkyl, hydroxyalkyl of C? -C and - (C2H4O) xH wherein x ranges from about 1 to about 3. The amides that are preferred are C8-C20 ammonia amides, monoethanolamides , diethanolamides and isopropanolamides.

Cationic / amphoteric surfactant Non-quaternary cationic detersive surfactants may also be included in the detergent compositions of the present invention. Cationic surfactants useful herein are described in the U.S.A. 4,228,044, Cambre, issued October 14, 1980. Ampholytic surfactants can be incorporated into the detergent compositions herein. These surfactants can be broadly described as aliphatic derivatives of secondary or tertiary amines, or aliphatic derivatives of heterocyclic secondary and tertiary amines in which the aliphatic radical can be straight or branched chain. One of the aliphatic substituents contains at least about 8 carbon atoms, typically about 8 to about 18 carbon atoms, and at least one contains an anionic water solubilizing group, for example, carboxy, sulfonate, sulfate. See patent of E.U.A. No. 3,929,678 to Laughiin et al, issued December 30, 1975 in column 19, lines 18-35 for examples of ampholytic surfactants. Preferred amphoteric surfactants include C 2 -C 8 alkylethoxylates ("AE") including the so-called narrow-alkylethoxylated and the C 6 -d 2 alkoxylated alkylphenols (especially ethoxylated and mixed ethoxy / propoxy), betaines and sulfobetaines of Ci2-C? 8 ("sultaines"), amine oxides of C? oC? 8 and mixtures thereof.

Polyhydroxy fatty acid amide surfactant The compositions herein may also contain a polyhydroxy fatty acid amide surfactant. The polyhydroxy fatty acid amide surfactant component comprises compounds of the structural formula: OR R1 R2 - C - N - Z wherein R 1 is H, C C, 2-hydroxyethyl, 2-hydroxypropyl hydrocarbyl or a mixture thereof, preferably C 1 -C 4 alkyl, most preferably C 1 or C 2 alkyl, more preferably C 1 alkyl (ie methyl); and R2 is a C5-C3 hydrocarbyl, preferably straight-chain C7-C9 alkyl or alkenyl, most preferably straight-chain C9-C7 alkyl or alkenyl, more preferably C11-C15 alkyl or alkenyl of Straight chain or mixtures thereof; and Z is a polyhydroxyhydrocarbyl having a linear hydrocarbyl chain with at least 3 hydroxyls directly connected to the chain, or an alkoxylated derivative (preferably ethoxylated or propoxylated) thereof. Z will preferably be derived from a reducing sugar in a reductive amination reaction; most preferably Z will be a glycityl. Suitable reducing sugars include glucose, fructose, maltose, lactose, galactose, mannose and xylose. As raw material, high dextrose corn syrups, high fructose corn syrup and high maltose corn syrup, as well as the individual sugars listed above can be used. These corn syrups can produce a mixture of sugar components for Z. It should be understood that for no reason is it intended to exclude other suitable materials. Z will preferably be selected from the group consisting of -CH2- (CHOH) n -CH2OH, -CH (CH2OH) - (CHOH) n -? - CH2OH, -CH2- (CHOH) 2 (CHOR ') (CHOH) -CH2OH , and alkoxylated derivatives thereof, wherein n is an integer from 3 to 5, inclusive, and R 'is H or a cyclic or aliphatic monosaccharide. Most preferred are glycityls wherein n is 4, particularly -CH2- (CHOH) 4-CH2OH. R 'can be, for example, N-methyl, N-ethyl, N-propyl, N-isopropyl, N-butyl, N-hydroxyethyl or N-2-hydroxypropyl. R2-CO-N < it can be, for example, cocamide, stearamide, oleamide, lauramide, myristamide, capricamide, palmitamide, seboamide, etc. Z may be 1-deoxyglucityl, 2-deoxyfuctilityl, 1-deoxymaltytyl, 1-deoxylactityl, 1-deoxygalactityl, 1-deoxyanityl, 1-deoxymalototriotityl, etc. Methods for making polyhydroxy fatty acid amides are known in the art. In general, they can be made by reacting an alkylamine with a reducing sugar in a reductive amination reaction to form a corresponding N-alkyl polyhydroxyamine and then reacting the N-alkyl polyhydroxyamine with a fatty aliphatic ester or triglyceride in a condensation / amidation step to form the N-alkyl, N-polyhydroxylic acid amide product. The processes for making compositions containing polyhydroxy fatty acid amides are described, for example, in the description of British patent 809,060, published on February 18, 1959 by Thomas Hedley & Co., Ltd., patent of E.U.A. 2,965,576, issued on December 20, 1960 to E.R. Wilson and patent of E.U.A. No. 2,703,798, Anthony M. Schwartz, issued March 8, 1955 and patent of E.U.A. 1, 985,424, issued on December 25, 1934 to Piggott, each of which is hereby incorporated by reference.

Diamines Preferred organic diamines are those in which pK1 and pK2 are in the range of about 8.0 to about 11.5, preferably in the range of 8.4 to about 11, even very preferably from about 8.6 to about 10.75. The preferred materials in terms of supply and yield are 1,3-propanediamine (pK1 = 10.5, pK2 = 8.8), 1.6 hexandiamine (pK1 = 11, pK2 = 10), 1.3 pentanediamine (Dytek EP) (pK1 = 10.5, pK2 = 8.9), 2-methyl 1,5-pentanediamine (Dytek A) (pK1 = 11.2, pK2 = 10.0). Other preferred materials are the primary diamines with alkylene spacers on the C4 to C8 scale.

Definition of pK1 and pK2 As used herein, "pKal" and pKa2"are amounts of a type commonly known to those skilled in the art as" pKa. "PKa is used herein in the same manner as is commonly known by the experts in the field of chemistry The values of the present can be obtained from the literature, such as "Critical Stability" Constants: Volume 2, Amine "by Smith and Martel, Plenum Press, NY and London 1975. Information Additional information on pKa's can be obtained from relevant literature, such as the information provided by Dupont, a diamine supplier. As a working definition of the present, pKa of the diamines is specified in a completely aqueous solution at 25 ° C and for an ionic resistance between 0.1 and 0.5 M. The pKa is an equilibrium constant that can vary with temperature and ionic strength, therefore, the values reported in the literature sometimes do not coincide depending on the measurement of methods and conditions. To eliminate ambiguity, the conditions and / or relevant references used for pKa's are as defined herein or in "Critical Stability Constants: Volume 2, Amines". A typical method of measurement is the potentiometric trituration of the acid with sodium hydroxide and the determination of pKa by suitable methods as described and presented in "The Chemist's Ready Reference Handbook" by Shugar and Dean, McGraw Hill, NY, 1990. has determined that substituents and structural modifications that decrease pK1 and pK2 to less than about 8.0 are undesirable and cause yield losses. They may include substitutions that lead to ethoxylated diamines, hydroxyethyl substituted diamines, oxygen diamines in the beta position (and therefore range) to the nitrogen in the spacer group (e.g., Jeffamine EDR 148). In addition, ethylenediamine-based materials are inadequate. The diamines useful herein can be defined by the following structure: wherein R? - are independently selected from H, methyl, -CH3CH2 and ethylene oxides; Cx and Cy are independently selected from methylene groups or branched alkyl groups wherein x + y is from about 3 to about 6; and A is optionally presented and selected from selected donor or electron withdrawing portions to adjust the pKa's of the diamine to the desired scale. If A is presented, then x and y must be both 1 or more. Examples of preferred diamines include the following: Dimethylaminopropila 1, 6-Hexanodiamine: 1, 3 propane diamine - H f ^^ NH ^ 2-methyl 1,5-pentanediamine 1, 3-pentanediamine, available 1 - . 1-methyl-diaminopropane- Jeffamine EDR 148- and mixtures thereof.

Secondary surfactants Secondary detersive surfactants can be selected from quaternary ammonium surfactants as long as the quaternary surfactant does not adversely affect the primary surfactant of the invention. In general, the quaternary secondary surfactant can be added for further antimicrobial action in the detergent compositions herein. Quaternary surfactants include ammonium surfactants such as alkyldimethylammonium halides, and those surfactants having the formula: [R2 (OR3) and] [R4 (OR3) and] 2R5N +? - wherein R2 is an alkyl or alkylbenzyl group which has about 8 to about 18 carbon atoms in the alkyl chain, each R3 is selected from the group consisting of -CH2CH2-CH2CH (CH3) -, -CH2CH (CH2OH) -, -CH2CH2CH2-, and mixtures thereof, each R4 is selected from the group consisting of C1-C4 alkyl hydroxyalkyl of C1-C4, benzyl, ring structures formed by the joining of the two groups R4, -CH2CHOHCHOHCOR6CHOH-CH2OH, wherein R6 is a hexose or hexose polymer having a molecular weight of less than about 1000, and hydrogen when and is not O; R5 is the same as R4 or is an alkyl chain wherein the total number of carbon atoms of R2 plus R5 is not more than about 18; each y is from about 0 to about 10 and the sum of the y values is from about 0 to about 10 and the sum of the y values is from about 0 to about 15; and X is any compatible anion.

Detergency builders Builders may optionally be included in the compositions herein to help control mineral hardness. Inorganic builders as well as organic builders can be used. The level of builder can vary widely depending on the final use of the composition and its desired physical form. The liquid formulations may comprise from about 1% to about 50%, usually from about 2% to about 30%, by weight, of builder. Examples of carbonate 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. Organic builders suitable for purposes of the present invention include, but are restricted to, a wide variety of polycarboxylate compounds. As used herein, "polycarboxylate" refers to compounds having a plurality of carboxylate groups, preferably at least 3 carboxylates. The polycarboxylate builder can generally be added to the composition in acid form, but also added in the form of a neutralized salt. When used in the salt form, alkali metals, such as sodium, potassium and lithium or alkanolammonium salts are preferred. Polycarboxylate builders include a variety of categories of useful materials. An important category of polycarboxylate builders is described in Berg, U.S. Patent. 3,128,287, issued April 7, 1964, and Lamberti et al, patent of E.U.A. do not. 3,635,830, issued January 18, 1972. See also "TMS / TDS" improvers of the U.S.A. No. 4,663,071, issued to Bush et al, May 5, 1987. Ether polycarboxylates also include cyclic compounds, particularly alicyclic compounds, such as those described in U.S. Pat. numbers 3,923,679; 3,835,163; 4,158,635; 4,120,874 and 4,102,903. Citrate improvers, for example citric acid and soluble salts thereof (particularly sodium salt), are important polycarboxylate builders for liquid detergent formulations due to their availability from renewable sources and their biodegradability. Oxydisuccinates are especially useful in said compositions and combinations.

Also useful in the compositions of the present invention are the 3,3-dicarboxy-4-oxa-1,6-hexanedioates and their related compounds described in the US patent. No. 4,566,894, Bush, issued January 28, 1986. Lauryl succinates are the preferred builders of this group, and are described in European patent application 86200690.5 / 0,200,263, published November 5, 1986. Other suitable polycarboxylates are describe in the US patent No. 4,144,226, Crutchfield et al, issued March 13, 1979 and in the U.S. patent. No. 3,308,067, Diehl, issued March 7, 1967. See also Diehl patent of E.U.A. no. 3,723,322. Fatty acids, for example C 2 -C 8 monocarboxylic acids, can also be incorporated into the compositions alone, or in combination with the aforementioned improvers, especially citrate and / or succinate builders, to provide additional enhancing activity. . Inorganic or P-containing detergent builders include, but are not limited to, alkali metal, ammonium and alkanolammonium salts of polyphosphates (exemplified by polymeric tripolyphosphates, pyrophosphates and metaphosphates), phosphonates, phytic acid, silicates, carbonates (including bicarbonates and sesquicarbonates), sulfates and aluminosilicates. Phosphonate builders such as ethan-1-hydroxy-1,1-diphosphonate and other known phosphonates (see, for example, U.S. Patent Nos. 3,159,581; 3,213,030; 3,422,021; 3,400,148 and 3,422,137) can also be used. Examples of silicate builders are the alkali metal silicates, such as the layered sodium silicates described in US Pat. No. 4,664,839, issued May 12, 1987 to H.P. Rieck NaSKS-6 is the trade name for a crystalline layered silicate sold by Hoechst (commonly abbreviated herein as "SKS-6"). NaSKS-6 can be prepared by methods such as those described in DE-A-3,417,649 and DE-A-3,742,043 of Germany. Other stratified silicates from Hoechst include NaSKS-5, NaSKS-7, and NaSKS-11, such as the alpha, beta and gamma forms. Useful aluminosilicate ion exchange materials are commercially available. A method for producing aluminosilicate ion exchange materials is described in the U.S.A. 3,985,669, Kel et al, issued October 12, 1976.

Enzymes Suitable enzymes include proteases, amylases, lipases, cellulases, peroxidases and mixtures thereof of any suitable origin, such as vegetable, animal, bacterial, fungal and yeast. The selections that are preferred are influenced by factors such as activity by pH and / or optimum stability, thermostability and stability in active bleach, detergents, builders and the like. In this regard, bacterial or mycotic enzymes, such as bacterial amylases and proteases and fungal cellulases, are preferred. Enzymes are normally incorporated in detergent compositions or detergent additives at levels sufficient to provide an "effective cleaning amount". The term "effective cleaning amount" refers to any amount capable of producing an improving cleaning, stain removal, dirt removal, whiteness, deodorization or freshness effect on substrates such as tableware and the like. In practical terms for current commercial preparations, the compositions herein may comprise from about 0.001% to 5%, preferably 0.01% -1% by weight of the commercial enzyme preparation. Protease enzymes are normally present in such commercial preparations at levels sufficient to provide 0.005 to 0.1 Anson units (AU) of activity per gram of composition. The preparation of enzyme protease and analogous enzymes is described in GB 1, 243,784 to Novo. Other suitable proteases include ALCALASE® and SAVINASE® from Novo and MAXATASE® from International Bio-Synthetics, Inc., The Netherlands; as well as protease A as described in EP 130,756 A, January 9, 1985 and protease B as described in EP 303,761 A, April 28, 1987 and EP 130, 756 A, January 9, 1985. See also a high pH protease. of Bacillus sp. NCIMB 40338 described in WO 9318140 A to Novo. Enzymatic detergents comprising protease, one or more other enzymes, and a reversible protease inhibitor are described in WO 9203529 A de Novo. Other proteases that are preferred include those of WO 9510591 A of Procter & Gamble. When desired, a protease having decreased adsorption and increased hydrolysis is available as described in WO 9507791 to Procter & Gamble. A recombinant trypsin-like protease for detergents suitable herein is described in WO 9425583 to Novo. Suitable amylases herein, especially for, but not limited to, automatic dish washing, include, for example, α-amylases described in GB 1, 296, 839 to Novo; RAPIDASE®, International Bio-Synthetics, Inc. and TERMAMYL®, Novo. FUNGAMYL® by Novo is especially useful. The genetic manipulation of enzymes is known for improved stability, for example, oxidative stability. See, for example J. Biological Chem., Vol. 260, No. 11, June 1985, pp. 6518-6521. Preferred amylases include (a) an amylase according to WO 9402597, Novo, Feb. 3 1994. Other amylases include variants that have a further modification in the immediate parent as in those described in WO 9510603 A and are available from the assignee, Novo, as DURAMYL®. Another amylase of improved oxidative stability that is particularly preferred includes those described in WO 9418314 to Genencor International and WO 9402597 to Novo. Suitable cellulases of the present invention include those described in US Pat. No. 4,435,307, Barbesgoard et al., March 6, 1984. 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. see also WO 9117243 to Novo. Lipase enzymes suitable for use in detergents include those produced by microorganisms of the Pseudomonas group, such as Pseudomonas stutzeri ATCC 19,154, as described in GB 1, 372, 034. See also lipases in Japanese Patent Application 53,20487, open to the public on February 24, 1978. Other suitable commercial lipases include Amano-CES, lipases ex Chromobacter viscosum, e.g., Chromobacetr viscosum var. lipolyticum NRRLB 3673 from Toyo Jozo Co., Tagata, Japan; Chromobacter viscosum lipases from U.S. Biochemical Corp., E.U.A. and Disoynth Co., The Netherlands, and lipases ex Pseudomonas gladioli. The LIPOLASE® enzyme derived from Humicola lanuginosa and commercially available from Novo, see also EP 341, 947, is a lipase which is preferred to be used herein. Variants of lipase and amylase stabilized against peroxidase enzymes are described in WO 9414951 A to Novo. See also WO 9205249 and RD 94359044. Cutinase enzymes suitable for use herein are described in WO 8809367 A of Genencor. The peroxidase enzymes can be used in combination with oxygen sources, for example, percarbonate, perborate, hydrogen peroxide, etc., for "bleaching in solution" or for the prevention of the transfer of dyes or pigments removed from substrates during washing to other substrates present in the wash solution. Known peroxidases include horseradish peroxidase, ligninase, and haloperoxidases such as chloro- or bromoperoxidase. Detergent compositions containing peroxidases are described in WO 89099813 A, October 19, 1989 to Novo and WO 8909813 A to Novo. A range of enzyme materials and means for their incorporation into synthetic detergent compositions are also disclosed in WO 9307263 and WO 9307260 A to Genencor International, WO 8908694 A to Novo, and US Pat. No. 3,553,139, January 5, 1971 to McCarty et al. Enzymes are also described in E.U.A. 4,101, 457, Place et al, July 18, 1978, and in E.U.A. 4,507,219, Hughes, March 26, 1985. Enzyme materials useful for liquid detergent formulations and their incorporation into such formulations are described in E.U.A. 4,261, 868, Hora et al, April 14, 1981. Enzymes for use in detergents can be stabilized by various techniques. Enzyme stabilization techniques are described and exemplified in E.U.A. 3,600,319, August 17, 1971, Gedge et al, EP 199,405 and EP 200,586, October 29, 1986, Venegas. Enzyme stabilization systems are also described, for example, in E.U.A. 3,519,570. A Bacillus, sp. Useful AC13 which gives proteases, xylanases and cellulases is described in WO 9401532 A to Novo.

Enzyme stabilization system Enzyme-containing compositions, including but not limited to liquid compositions, herein can comprise from about 0.001% to about 10%, preferably about 0.005% to about 8%, most preferably about 0.01% a about 6% by weight, of an enzyme stabilization system. Said stabilization systems may, for example, comprise calcium ions, boric acid, propylene glycol, short chain carboxylic acids, boronic acids and mixtures thereof, and are designed to solve different stabilization problems depending on the type and physical form of the detergent composition. See Severson, patent of E.U.A. No. 4,537,706 for a review of borate stabilizers. Suitable chlorine scavenging anions are widely known and readily available, and, if used, may be salts containing ammonium cations with sulfite, bisulfite, thiosulfite, thiosulfate, iodide, etc. Antioxidants such as carbamate, ascorbiate, etc., organic amines such as ethylenediaminetetraacetic acid (EDTA) or an alkali metal salt thereof, monoethanolamine (MEA), and mixtures thereof may also be used. Other conventional scrubbers such as bisulfate, nitrate, chloride, sources of hydrogen peroxide such as sodium perborate tetrahydrate, sodium perborate monohydrate and sodium percarborate, as well as phosphate, condensed phosphate, acetate, benzoate, citrate, formate, lactate, malate , tartrate, salicylate, etc., and mixtures thereof may be used if desired.

Bleaching agents Suitable bleaching agents for use herein are listed below: Diacyl peroxide bleaching species The composition of the present invention may comprise diacyl peroxide of the general formula: RC (O) OO (O) CR1 wherein R and R1 may be the same or different and are hydrocarbyls, preferably not more than one is a hydrocarbyl chain of ten carbon atoms length, most preferably at least one has an aromatic nucleus. Examples of suitable diacyl peroxides are selected from the group consisting of dibenzoyl peroxide, dianisoyl peroxide, benzoylglyryl peroxide, benzoylsuccinyl peroxide, di- (2-methibenzoyl) peroxide, diptaloyl peroxide, dynaphthoyl peroxide, dynaphthoyl peroxide. substituted, and mixtures thereof, most preferably dibenzoyl peroxide, dicumyl peroxide, diftaloyl peroxides, and mixtures thereof. A particularly preferred diacyl peroxide is dibenzoyl peroxide.

Hydrogen peroxide source The compositions of the present invention may comprise a source of oxygen bleach, preferably a source of hydrogen peroxide with or without a selected bleach activator. The source of hydrogen peroxide is commonly any hydrogen peroxide release salt, such as sodium perborate or sodium percarbonate. Sources of hydrogen peroxide include various forms of sodium perborate and sodium percarbonate 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 and tomato stains) from the soiled substrate as compared to a hydrogen peroxide source-free composition when the dirty substrate is washed by the consumer. The preferred source of hydrogen peroxide used herein may be any convenient source, including hydrogen peroxide itself. For example, perborate, such as sodium perborate (any hydrate but preferably mono or tetrahydrate), sodium carbonate peroxyhydrate or equivalent percarbonate salts, sodium pyrophosphate peroxyhydrate, urea peroxyhydrate, or sodium peroxide may be used herein . Sodium perborate monohydrate and sodium percarbonate are particularly preferred. Mixtures of any source of hydrogen peroxide can also be used. Another source of hydrogen peroxide are enzymes. Examples include lipoxidase, glucose oxidase, peroxidase, alcohol oxidases and mixtures thereof.

Bleach Activators Numerous conventional bleach activators are known. See, for example, triggers mentioned above, as well as the Patent of E.U.A. 4,9151, 854 issued April 10, 1990 to Mao et al., And in the U.S. Patent. 4,412,934. It is possible to use activators of nonanoyloxy-benzenesulfonate (NOBS) or acylactam and mixtures thereof with TAED can also be used. See also E.U.A. 4,634,551 for other typical bleach activators. Also known are amido-derived bleach activators of the formulas: R 1 N (R 5) C (O) R 2 C (O) L or R 1 C (O) N (R 5) R 2 C (O) L wherein R 1 is an alkyl group which contains from about 6 to about 12 carbon atoms, R 2 is an alkylene containing from 1 to about 6 carbon atoms, R 5 is H or alkyl, aryl or alkaryl containing from about 1 to about 10 carbon atoms and L is any suitable residual group. Preferred examples of bleach activators of the above formulas include (6-octanamidocaproyl) oxybenzenesulfonate, (6-nonanamidocaproyl) oxybenzenesulfonate, (6-decanamidocaproyl) oxybenzenesulfonate and mixtures thereof as described in the patent of E.U.A. 4,634,551. Another class of bleach activators includes activators of the benzoxazine type described by Hodge et al. In the U.S. Patent. 4,966,723 issued October 30, 1990. Another class of bleach activators includes acylactam activators such as octanoylcaprolactam, 3,5,5-trimethylhexanoylcaprolactam, nonanoylcaprolactam, decanoylcaprolactam, undecenoylcaprolactam, octanoylvalerolactam, decanoylvalerolactam, undecenoylvalerolactam, nonanoylvalerolactam, 3,5, 5-trimethylhexanoylvalerolactam, t-butylbenzoylcaprolactam, t-butylbenzoylvalerolactam and mixtures thereof. The compositions herein may optionally comprise aryl benzoates, such as phenyl benzoate and acetitriethyl citrate.

Substituted quaternary bleach activators The present compositions may also comprise substituted quaternary bleach activators (QSBA). The QSBAs in the present typically have the formula E- [Z] nC (O) -L, where group E is referred to as "head", group Z is referred to as the "spacer" (n is 0 or 1, that is, this group may be present or absent, although its presence is generally preferred) and L is referred to as "leaving group". These compounds generally contain at least a portion of substituted quaternary nitrogen, which may be comprised in E, Z or L. Most preferably, a simple quaternary nitrogen is present and is located in the E or Z group. In general, L is a leaving group, the pKa of the corresponding carbon acid (HL) of which may be on the general scale of about 5 to about 30, most preferably about 10 to about 20, depending on the hydrophilicity of the QSBA. The outgoing group pKa's are further defined in the US patent.

No. 4,283,301. The leaving groups and solubilizing tendencies of quaternary portions that may be present in the QSBAs are also illustrated in the patent of E.U.A. No. 4,539,130, September 3, 1985, incorporated by reference. The British patent 1, 382,594, published on February 5, 1975, describes a class of QSBA suitable for use herein. The patent of E.U.A. No. 4,818,426 issued April 4, 1989 describes another class of QSBA suitable for use. See, for example, US patent. No. 5,093,022 issued March 3, 1992 and patent of E.U.A. No. 4,904,406, issued February 27, 1990. Additionally, the QSBA's are described in EP 552,812 A1, published July 28, 1993 and EP 540,090 A2, published May 5, 1993.

Chlorine bleach Any chlorine bleach typically known in the art is suitable for use herein. Preferred chlorine bleaches for use herein include sodium hypochlorite, lithium hypochlorite, calcium hypochlorite, chlorinated trisodium phosphates, and mixtures thereof. For more information about chlorine bleaches see Surfactant Science Series, Vol. 5, Part II, pages 520-26.

Bleach Catalysts If desired, the detergent compositions herein may additionally incorporate a catalyst or accelerator to further improve stain removal or bleaching. Any suitable bleach catalyst can be used. The compositions will comprise about 0.0001% to about 0.1% by weight of the bleach catalyst. Typical bleach catalysts are those described in the US patent. No. 4,810,410 to Diakun et al, issued March 7, 1989. The active species thereof are believed to be. { Co (NH3) 5 (OOH)} 2+ and are described in J. Chem. Soc. Faraday Trans., 1994, Vol. 90, 1105-1114. Other catalysts include manganese-based catalysts described in the U.S.A. No. 5,246.62, E.U.A. 5,244,594; E.U.A. 5,194,419; E.U.A. 5,114,606; and EP Nos. 549,271 A1, 549,272 A1, 544,440 A2, and 544,490 A1. Other metal-based bleach catalysts include those described in the U.S.A. No. 4,430,243 and patent of E.U.A. No. 5,114,611. The use of manganese with several complex ligands to improve bleaching is also shown in the following U.S. Patents: 4,728,455; 5,284,944; 5,246,612; 5,256,779; 5,280,117: 5,274,147, 5,153,161; and 5,227,084. The transition metals can be precomplexed or complexed in-situ with suitable donor ligands selected based on their metal selection, oxidation state and denticity. Other complexes that may be included herein are those set forth in U.S. Patent Application No. 08 / 210,186, filed on March 17, 1994.

Perfumes Perfume and perfumery ingredients useful in the present compositions and methods comprise a wide variety of natural and synthetic chemical ingredients, including, but not limited to, aldehydes, ketones, esters and the like. Also included are different natural extracts and essences which may comprise complex mixtures of ingredients, such as orange oil, lemon oil, rose extract, lavender, musk, patchouli, balsamic essence, sandalwood oil, pine oil, cedar and similar. The finished perfumes can comprise extremely complex mixtures of said ingredients. The finished perfumes typically comprise from about 0.01% to about 4%, by weight, of the detergent compositions herein, and the individual perfumery ingredients may comprise from about 0.0001% to about 90% of a finished perfume composition.

Material Care Agents The present compositions may optionally contain as corrosion inhibitors and / or anti-rust auxiliaries, one or more agents for the care of materials, such as silicate. Agents for the care of materials include bismuth salts, transition metal salts such as those of manganese, certain types of paraffin, triazoles, pyrazoles, thiols, mercaptans, aluminum fatty acid salts and mixtures thereof, and they preferably incorporate at low levels, for example, from about 0.01% to about 5% of the composition. A preferred paraffin oil is a predominantly branched aliphatic hydrocarbon comprising about 20 to about 50 carbon atoms with a cyclic to non-cyclic hydrocarbon ratio of about 32 to 68 sold by Wintershall, Salzbergen, Germany as WINOG 70®. Bi (N03) 3 can be added. Other corrosion inhibitors are illustrated by benzotriazole, thiols including thiophthol and thioanthranol, and finely divided aluminum fatty acid salts. All these materials will generally be used judiciously to avoid producing stains or films on glass articles or compromising the bleaching action of the compositions. For this reason, the formulation without mercaptan anti-rust which are quite reactive in bleach or common fatty carboxylic acids which precipitate with calcium may be preferred.

Chelating Agents The detergent compositions herein may also optionally contain one or more iron and / or manganese chelating agents. Such chelating agents can be selected from the group consisting of amino carboxylates, amino phosphonates, polyfunctionally substituted aromatic chelating agents and mixtures thereof, all as described hereinabove. If desired to be limited by theory, it is believed that the benefit of these materials is due in part to their exceptional ability to remove iron and manganese ions from wash solutions through the formation of soluble chelates. Aminocarboxylates useful as optional chelating agents include: ethylenediaminetetraacetates, N-hydroxyethylenediaminetriacetates, nitrilotriacetates, ethylenediaminetetrapropionates, triethylenetetraaminohexacetates, diethylenetriaminepentaacetates and ethanoldiglicines, alkali metal, ammonium and substituted ammonium salts thereof and mixtures thereof. Polyfunctionally substituted aromatic chelating agents are also useful in the compositions herein. See the patent of E.U.A. No. 3,812,044 issued May 21, 1974 to Connor et al. Compounds of this type that are preferred in acid form are dihydroxydisulfobenzenes such as 1,2-dihydroxy-3,5-disulfobenzene. A biodegradable chelator that is preferred to be used herein is ethylene diamine disuccinate ("EDDS"), especially the [S, S] isomer as described in the U.S.A. 4,704,233, November 3, 1987 to Hartman and Perkins. If used, these chelating agents will generally comprise from about 0.1% to about 10% by weight of the detergent compositions herein. Most preferably, if used, the chelating agents will comprise from about 0.1% to about 3.0% by weight of said compositions.

Polymeric dispersion agents Polymeric dispersion agents can be advantageously used at levels of from about 0.1% to about 7%, by weight, in the compositions herein, especially in the presence of zeolite and / or zeolite and / or silicate builders. stratified Suitable polymeric dispersing agents include polymeric polycarboxylates and polyethylene glycols, although others known in the art may also be used. It is believed, although not intended to be limited by theory, that polymer dispersion agents increase the overall performance of the detergency builder when used in combination with other detergency builders (including low molecular weight polycarboxylates) by inhibiting the growth of crystals. , the peptidization of particle fouling and antiredeposition release. The polymeric polycarboxylate materials can be prepared by the polymerization or copolymerization of suitable unsaturated monomers, preferably in their acid form. Unsaturated monomeric acids which can be polymerized to form suitable polymeric polycarboxylates include acrylic acid, maleic acid (or maieic anhydride), itaconic fumaric acid, aconitic acid, mesaconic acid, citraconic acid and methylenemalonic acid. The presence in the polymeric polycarboxylates of the present of monomeric segments which do not contain carboxylate radicals such as vinyl methyl ether, styrene, ethylene etc. is adequate, as long as said segments do not constitute more than about 40% by weight. Particularly suitable polymeric polycarboxylates can be derived from acrylic acid. Said acrylic acid-based polymers which are useful herein are the water-soluble salts of polymerized acrylic acid. The average molecular weight of said polymers in acid form preferably ranges from about 2,000 to 10,000, most preferably about 4,000 to 7,000 and more preferably about 4,000 to 5,000. The water-soluble salts of said acrylic acid polymers may include, for example, the alkali metal, ammonium and substituted ammonium salts. Soluble polymers of this type are known materials. The use of polyacrylates of this type in detergent compositions has been described, for example, in Diehl, U.S. Pat. No. 3,308,067, issued March 7, 1967. Copolymers based on acrylic / maleic acid may also be used as a preferred component of the dispersing / anti-redeposition agent. Such materials include water-soluble salts of copolymers of acrylic acid and maleic acid. The average molecular weight of said copolymers in acid form preferably ranges from about 2,000 to 100,000, most preferably about 5,000 to 75,000, most preferably about 7,000 to 65,000. The ratio of acrylate to maleate segments in said copolymers will generally vary from about 30: 1 to about 1: 1, most preferably about 10: 1 to 2: 1. The water-soluble salts of said acrylic acid / maleic acid copolymers can include, for example, the alkali metal, ammonium and substituted ammonium salts. Soluble acrylate / maleate copolymers of this type are known materials which are described in European Patent Application No. 66915, published on December 15, 1982, as well as in EP 193,360, published on September 3, 1986, which also describes polymers comprising hydroxypropylacrylate. Other useful dispersing agents include the terpolymers of maleic acid / acrylic / vinyl alcohol. Said materials are also described in EP 193,360, including, for example, the terpolymer 45/45/10 acrylic acid / maleic / vinyl alcohol. Other polymeric materials that may be included are polypropylene glycol (PPG), propylene glycol (PG) and polyethylene glycol (PEG). PEG can exhibit dispersing agent performance, as well as act as a removal / antiredeposition agent of clay soils. The typical molecular weight varies for these purposes in the range of about 500 to about 100,000, preferably about 1,000 to about 50,000, most preferably about 1,500 to about 10,000. Dispersants of polyaspartate and polyglutamate, especially in conjunction with zeolite builders, can also be used. Dispersing agents such as polyaspartate preferably have a molecular weight (average) of about 10,000. Alkoxylated polycarboxylates such as those prepared from polyacrylates are useful herein to provide an additional fat removal performance. Such materials are described in WO 91/08281 and PCT 90/01815, on page 4 and onwards. Chemically, these materials comprise polyacrylates having an ethoxy side chain for every 7-8 acrylate units. The side chains have the formula - (CH2CH20) m (CH2) nCH3 where m is 2-3 and n is 6-12. The side chains are linked by ester to the "base structure" of polyacrylate to provide a "comb" type polymer structure. The molecular weight may vary, but is typically in the range of about 2,000 to about 50,000. Said alkoxylated polycarboxylates may comprise from about 0.05% to about 10%, by weight of the compositions herein. Another polymeric dispersant for use herein includes polyethoxylated polyamine (PPP) polymers. The polyethoxylated polyamines which are preferred and are useful herein are generally polyalkyleneamines (PAA's), polyalkyleneimines (PAI's), preferably polyethyleneamine (PEA's), polyethyleneimines (PEI's). A common polyalkyleneamine (PAA) is tetrabutylenepentamine. PEA's are obtained by reactions that include ammonia and ethylene dichloride, followed by fractional distillation. The common PEA's obtained are triethylenetetramine (TETA) and tetraethylenepentamine (TEPA). On the pentamines, that is, the hexamines, heptamines, octamines and possibly nonamines, the cogenically derived mixture does not appear to be separated by distillation and may include other materials such as cyclic amines, particularly piperazines. Cyclic amines with side chains in which nitrogen atoms appear may also be present. See the patent of E.U.A. No. 2,792,372, Dickinson, issued May 14, 1957, which describes the preparation of PEA's. The polyamines can be prepared, for example, by polymerizing ethyleneimine in the presence of a catalyst such as carbon dioxide, sodium bisulfite, sulfuric acid, hydrogen peroxide, hydrochloric acid, acetic acid, etc. The specific methods for preparing these polyamine base structures are described in the U.S. patent. 2,182,306, Ulrich et al, issued December 5, 1939; patent of E.U.A. 3,033,746, Mayle et al, issued May 8, 1962; patent of E.U.A. 2,208,095, Esselmann et al, issued July 16, 1940; patent of E.U.A. 2,806,839, Crowther, issued September 17, 1957 and patent of E.U.A. 2,553,696, Wilson, issued May 21, 1951; all incorporated herein by reference. Additionally, certain alkoxylated (especially ethoxylated) quaternary polyamine dispersants are used herein as dispersants. The alkoxylated quaternary polyamine dispersants useful for this invention are those of the general formula: wherein R is selected from C2-C2 alkylene, C3-C2 hydroxyalkylene, C4-C2 dihydroxyalkylene, linear or branched C8-d2 dialkylarylene, [(CH2CH20) qCH2CH2] - and -CH2CH ( OH) CH20- (CH2CH20) qCH2CH (OH) CH2] -, wherein q is from about 1 to about 100. Each Ri is independently selected from C1-C4 alkyl, C7-C2 alkylaryl or A. Ri it may be absent in some nitrogens; however, at least three nitrogens must be quaternized. A has the formula: (CH-CH2-0) nB R3 wherein R3 is selected from H or CrC3 alkyl, n is from about 5 to about 100 and B is selected from H, C?-C4 alkyl, acetyl or benzoyl; m is from about 0 to about 4, and X is a water soluble anion. In preferred embodiments, R is selected from C4 to C8 alkylene, Ri is selected from CrC2 alkyl or C2-C3 hydroxyalkyl, and A is: (CH-CH2-0) nH R wherein R3 is selected from H or methyl, and n is from about 10 to about 50; and m is 1. In another preferred embodiment R is linear or branched C6, Ri is methyl, R3 is H and n is from about 20 to about 50, and m is 1. The levels of these dispersants used can vary from about 0.1% to about 10%, typically about 0.4% to about 5%, by weight. These dispersants can be synthesized following the methods mentioned in the U.S. patent. No. 4,664,848, or other forms known to those skilled in the art.

Hydrotropes Suitable hydrotropes for use in the compositions herein include C1-C3 alkylaryl sulfonates, C6-C12 alkanoies, C1-C6 carboxylic sulfates and sulfonates, urea, hydrocarboxylates, C1-C4 carboxylates, organic diacids, and mixtures of the same. Suitable C 1 -C 3 alkylaryl sulfonates include sodium, potassium, calcium and ammonium xylene sulfonate, toluenesulfonates, cumenesulfonates and naphthalenesulfonates.

Divalent Ions The compositions of the invention herein optionally contain, but preferably, calcium and / or magnesium ions to aid in the removal of fat and improved storage stability.

These ions may be present in the compositions herein at an active level of from about 0.1% to about 4%, by weight.

Thickeners Thickeners for use herein may be selected from clay, polycarboxylate, such as Polygel®, gums, carboxymethylcellulose, polyacrylates, polyvinylpyrrolidones, polyamide resins, titanium dioxide, fumed silica, and mixtures thereof. One type of clay preferred herein has a double layer structure. The clay can be natural, for example bentonite, or synthetic, for example Laponite ®, Laponite ® which is supplied by Southern Clay Products, Inc. See The Chemistry and Physics of Clays Grimshaw, 4th ed., 1971, pages 138-155, Wiley-lnterscience. Another preferred thickener for use in the present invention is hydroxypropylmethylcellulose. The unsaturated monomeric acids which can be polymerized to form suitable polymeric polycarboxylates include acrylic acid, maleic acid, maleic anhydride, fumaric acid, itaconic, aconitic acid, mesaconic acid, citraconic acid and methylenemalonic acid. Particularly suitable polymeric polycarboxylates can be derived from acrylic acid. See for example, Diehl, patent of E.U.A. No. 3,308,067, March 7, 1967. The liquid detergent compositions may comprise water and other solvents as carriers. The primary or secondary low molecular weight alcohols exemplified by methanol, ethanol, propanol and isopropanol are suitable. Monohydric alcohols are preferred to solubilize the surfactant, but polyols such as those containing from 2 to about 6 carbon atoms and from 2 to about 6 hydroxy groups (for example 1,3-propanediol, ethylene glycol, glycerin) can also be used. , and 1,2-propanediol). The compositions may comprise from about 5% to about 90%, typically from 10% to 50% of said vehicles.

Non-Aqueous Liquid Detergents The manufacture of liquid detergent compositions comprising a non-aqueous vehicle medium can be prepared according to the descriptions of the US patents. Nos. 4,753,570, 4,767,558; 4,772,413, 4,889,652; 4,892,673, GB-A-2,158,838, GB-A-2,195,125; GB-A-2,195,649; US 4,988,462; US 5,266,673; EP-A-225,654 (6/16/87); EP-A-510,762 (10/28/92); EP-A-540,089 (5/5/93); EP-A-540,090 (5/5/93), U.S. 4,615,820; EP-A-565,017 (10/13/93); EP-A-030,096 (6/10/81), incorporated herein by reference. Said compositions may comprise various particulate detersive ingredients (for example, bleaching agents, such as those described above) stably suspended herein. Said non-aqueous compositions therefore comprise a liquid phase and, optionally but preferably, a solid phase, such as those described in greater detail hereinafter and in the cited references. In addition to the sanitation discussed above, the compositions of the invention can be used to form aqueous wash solutions for use in manual dishwashing. Generally, an effective amount of said compositions is added to water to form said aqueous cleaning or soaking solutions. The aqueous solution formed in this way is put in contact with the kitchen utensils, crockery and cutlery. An effective amount of the detergent compositions herein, added to water to form aqueous cleaning solutions, may comprise sufficient amounts to form about 500 to 20,000 ppm of the composition in aqueous solution. Most preferably, from about 500 to 5,000 ppm of the detergent compositions herein will be provided in aqueous cleaning solution. The following examples illustrate the present invention, but do not attempt to limit or otherwise define its scope. All parts, percentages and relationships used herein are expressed as weight percent unless otherwise specified. In the following examples all levels are presented as percent by weight of the composition.

EXAMPLE 1 DTPA is ethylene diamine tetraacetate. The hydrotropes can be selected from calcium xylenesulfonate, sulfate or sodium and toluenesulfonate. • Thickeners include Tetronic ™ and Accusol ™. The formulas provide significant germ removal (Escherichia coli and Staphococcus aureus) when applied to a surface and allowed to remain in contact with the surface for at least 15 seconds before rinsing. •

Claims (10)

NOVELTY OF THE INVENTION CLAIMS

1. - A method for cleaning a substrate containing microbes characterized by the steps of: a) contacting the substrate with a detergent composition characterized by an effective amount of an antimicrobial agent; and b) allowing the detergent composition to remain in contact with the substrate for a sufficient time to significantly reduce the amount of microbes on the substrate.

2. A method according to claim 1, further characterized in that the antimicrobial agent is a surfactant selected from the group consisting of anionic, nonionic, cationic, amphoteric surfactants and mixtures thereof.

3. A method according to claim 2, further characterized in that the surfactant comprises from about 1% to about 80% by weight of the detergent composition.

4. A method according to claim 1, further characterized in that the substrate is constructed of a material selected from the group consisting of metal, coated metal, ceramic, porcelain, plastic, rubber, sponge, cloth, wood, glass and mixtures thereof.

5. A method according to claim 1, further characterized in that the detergent compositions additionally comprise one or more detergent adjuvants selected from the group consisting of processing aids, polymer thickeners, colorants, fillers, enzymes, alkalinity sources, hydrotropes , stabilizers, perfumes, solvents, vehicles, sodium bicarbonate, carbonates, hydrobenzoic acid, dicarboxylic acid, bleach, bivalent ions, dispersing polymers, chelating agents, detergency builders, pH regulators and mixtures thereof.

6. An antimicrobial product characterized by: a detergent composition comprising an effective amount of an antimicrobial agent; and instructions for using the detergent composition; wherein the instructions include the steps of: a) contacting a substrate containing microbes with the detergent composition; and b) allowing the detergent composition to remain in contact with the substrate for a sufficient time to significantly reduce the amount of microbes on the substrate.

7. A method according to claim 1, further characterized in that the detergent composition is applied with no more than 50% dilution with water.

8. A method according to claim 1, further characterized in that the substrate is selected from the group consisting of tableware, washing cloths, cutting boards, sponges, dentifrices / dentures, surfaces for preparing food, surgical / medical equipment, baby bottles and mixtures thereof.

9. A method for cleaning a substrate containing microbes characterized by the steps of: a) contacting the substrate with a detergent composition comprising an effective amount of an antimicrobial agent; b) while the detergent composition and the substrate are in contact, place the substrate in a microwave oven; c) Operating the microwave oven for a sufficient time to significantly reduce the amount of microbes on the substrate.

10. A product according to claim 6, further characterized in that step b) further comprises the following instructions: the substrate can optionally be placed in a microwave oven, and the microwave oven operated for a sufficient time.