MXPA01008036A - Diols and polymeric glycols in dishwashing detergent compositions - Google Patents

Abstract

Disclosed are detergent compositions comprising organic diamines, anionic surfactants and amphoteric surfactants including amine oxide for hand dishwashing which, by incorporating certain organic solvents, results in a liquid dishwashing detergent composition that is not only a more effective cleaning agent, but also offers improved physical and enzymatic stability and more convenient rheology and handling characteristics than typical liquid dishwashing compositions.

Description

POLYMERIC DIOLES AND GLYCOLS IN DETERGENT COMPOSITIONS FOR WASHING DISHES TECHNICAL FIELD The present invention relates to liquid or dishwashing detergent compositions suitable for use in manual dishwashing operations. These compositions contain amphoteric and anionic surfactants, organic diamines and solvents selected from the group consisting of diols and polymeric glycols and mixtures thereof, as well as other detergent adjuvants. These components, in the combinations described herein, serve to impart preferred foaming, handling and cleaning of food soils to such dishwashing detergent products.

BACKGROUND OF THE INVENTION Light duty gel or liquid detergent compositions (LDL) useful for manual dishwashing are known in the art. Such products are generally formulated to provide a number of widely varying properties and aesthetic and performance characteristics. First, gel or liquid dishwashing products should be formulated with types and amounts of surfactants and other cleaning adjuvants that will provide solubilization and acceptable removal of food soils, especially grease, dishware, or in solutions aqueous formed from such products. In this way, there is a continuing effort on the part of formulators of liquid dishwashing compositions to incorporate additional components in LDL detergents to provide consumers with improved cleaning benefits. Second, liquid dishwashing products should be formulated to be physically stable and free from adverse heterogeneity. "Physical stability" in this sense, refers to the tendency of a liquid composition to remain as a homogeneous solution instead of having one or more precipitated components (if the discontinuous phase is a solid) or separated (if the discontinuous phase is a liquid) in the liquid. In this way, a useful detergent composition is one that is free from irregularities and that is stable under a variety of different service conditions and storage temperatures - previous formulators have found that cold temperature stability is particularly difficult to obtain. Physical stability not only improves the appearance and therefore the consumer's perception of the product, but it is also essential to provide effective cleaning performance. Third, liquid dishwashing products must be formulated to have a viscosity that makes the use of the product convenient and feasible. In this way, a liquid dishwashing composition should not be so thick that it can not be easily poured out of its contents and at the same time, not so thin that it is difficult to concentrate on the surface of a sponge or kitchenware. The liquid dishwashing compositions should also have a favorable "dilution profile", which means that as the liquid dishwashing product is subsequently diluted with water, the composition decreases in viscosity. This is in contrast to the manner in which many typical liquid dishwashing compositions perform, in which the compositions with the first aqueous dilution become more viscous, thus making them not only more difficult to use, but also harming their dilution. The "dissolution" is another important attribute of liquid products for dishwashing. By dissolution it refers to the speed at which the liquid dishwashing product is mixed with water. Generally, it is preferable that a detergent product mix quickly, so that its detersive benefits are immediately available to the consumer, thus minimizing the amount of time that must be devoted to cleaning tasks. In fourth place, special care must be taken to formulate liquid dishwashing products which include enzymes, so that the enzymes do not degrade or decompose after their interaction with other detergent ingredients. Enzymes are important components of dishwashing compositions, because they offer improved cleaning benefits in protein-based soils and have also been shown to provide consumers with a softness or appearance / skin feel advantage over other detergent compositions. similar ones which do not contain enzymes. However, it can be difficult to incorporate enzymes into liquid dishwashing compositions because they are unstable in the presence of many standard LDL ingredients, such as citric acid. In addition, because the enzymes are active in the presence of water since most liquid dishwashing compositions are aqueous, care must be taken that the enzymes are not activated during storage and thus run out for the time being. in which the LDL composition is ready to be used. Given the above, there is a continuing need to formulate handwash liquids that provide excellent cleaning benefits, have stable formulations over a wide range of temperatures, and have a viscosity and consistency so that they are useful and convenient for a manual dishwashing operation. Accordingly, it is a benefit of the present invention to provide light duty liquid dishwashing compositions which not only provide improved cleaning benefits, but are also of a suitable consistency and viscosity, that are colorless and odorless, that are stable. and serving under a broad range of service temperatures and having improved enzyme stability over existing liquid dishwashing formulations.

BRIEF DESCRIPTION OF THE INVENTION It has now been determined that the use of a solvent selected from the group consisting of certain diols, certain polymeric glycols and mixtures thereof, as described in detail below in combination with amphoteric surfactants, anionic surfactants and organic diamines in a specific relationship, provides superior cleaning, fat cutting, physical stability, dissolution and rheological behavior on typical liquid dishwashing compositions. In particular, it has been found that the addition of diols can improve the physical and enzymatic stability of a liquid dishwashing composition. Diols prepared according to the present invention and described in detail below have been shown to improve the physical stability of liquid dishwashing compositions even at high pH (more than 10.0) and low temperatures where it is typically likely that certain components will will separate from the composition solution and will form irregularities. These diols have also been shown to improve enzyme stability even in compositions with high water levels. In addition, these diols, like other solvents, provide stabilizing benefits for dishwashing compositions, but unlike other solvents (e.g., ethanol), they do not thin the dishwashing compositions in which they are included. This allows a formulator to stabilize dishwashing compositions on a larger scale of viscosities, because the diols provide stability benefits of formula without the corresponding cost of decreasing the viscosity of the formula. In addition, it has been found that the addition of certain polymeric glycols, particularly in combination with sodium chloride or other inorganic alkali metal salts, can improve the dilution profile and low temperature stability of an LDL detergent composition. The detergent compositions according to the first aspect of the present invention comprises: (a) a low molecular weight organic diamine having a pK1 and a pK2, wherein the pK1 and the pK2 of said diamine are on the scale of about 8.0 to approximately 11.5; (b) an anionic surfactant; (c) an amphoteric surfactant; and (d) a solvent selected from the group consisting of diols, polymeric glycols and mixtures thereof; wherein said diol is selected from the group consisting of: wherein n = 0-3, R7 = H, methyl or ethyl; and R8 = H, methyl, ethyl, propyl, isopropyl, butyl and isobutyl; and wherein the polymeric glycol is selected from the group consisting of: (PO)? (EO)? H wherein PO represents a group of propylene oxide and EO represents a group of ethylene oxide and x + y is from about 17 to 68, and x / (x + y) is from about 0.25 to 1.0. The pH (measured according to 10% aqueous solution) is from about 5.0 to about 12.5 and the molar ratio of said anionic surfactant to said amphoteric surfactant to said amine is from about 100: 40: 1 to about 9: 0.5: 1. . According to a second aspect of the present invention, a detergent composition suitable for use in hand dishwashing, said composition comprises: (a) from about 0.1% to about 5% by weight of a diamine having a molecular weight less than or equal to equal to 400 g / mol; (b) from about 5% to about 50% by weight of an anionic surfactant; (c) from about 0.5% to about 10% by weight of an amphoteric surfactant; (d) from about 0.0001% to about 5%, by weight of an enzyme; (e) from about 0.75% to about 25.0%, by weight of a solvent selected from the group consisting of diol, polymeric glycol and mixtures thereof; the diols and polymeric glycols are those described above in the paragraph on the first aspect of the invention. The detergent composition further includes: (f) from about 0.01% to about 5% by weight of a polymeric foam stabilizer selected from the group consisting of: i) (N, N-dialkylamino) alkylacrylate ester homopolymers having the formula : wherein each R is independently hydrogen, alkyl d-Cs and mixtures thereof; R1 is hydrogen, dCS alkyl and mixtures thereof; n is from 2 to about 6; ii) copolymers of (i) and wherein R1 is hydrogen, CrC6 alkyl and mixtures thereof; provided that the ratio of (i) to (i) is from about 2 to 1 to about 1 to 2; and wherein said polymeric foam stabilizer has a molecular weight of from about 1,000 to about 2,000,000 daltons; and ii) and mixtures thereof. The pH (measured according to 10% aqueous solution) is from about 5.0 to about 12.5 and wherein the molar ratio of said anionic surfactant to said amphoteric surfactant to said diamine is from about 27: 8: 1 to about 11: 3. :1. According to a third aspect of the present invention, a detergent composition suitable for use in hand dishwashing, the composition comprises: (a) from about 0.1% to about 5% by weight of an organic diamine having a lower molecular weight ao equal to 400 g / mol; (b) from about 5% to about 50% by weight of an anionic surfactant; (c) from about 0.5% to about 10% by weight of an amphoteric surfactant; (d) from about 0.1% to about 10.0%, by weight of a pH regulating agent; (e) from about 0.1% to about 1.5%, by weight of an inorganic alkali metal salt; and (f) from about 0.75% to about 25.0%, by weight of a solvent selected from the group consisting of diol, polymeric glycol and mixtures thereof; the diols and polymeric glycols are those described above. The pH (measured according to 10% aqueous solution) is from about 10 to about 12 and the molar ratio of said anionic surfactant to said amphoteric surfactant to said diamine is from about 27: 8: 1 to about 11: 3: 1. . All parts, percentages and relationships used herein are expressed as percentages by weight unless otherwise specified. All of the cited documents are largely incorporated herein by reference.

DETAILED DESCRIPTION OF THE INVENTION Definitions The detergent compositions herein comprise an "effective amount" or an "amount to improve the removal of fat" of individual components described herein. By an "effective amount" of the diamines herein and adjunct ingredients refers to an amount which is sufficient to improve, either directionally or significantly at 90% confidence level, the performance of the cleaning composition against minus some of the target spots and dirt. Thus, in a composition whose objectives include certain grease stains, the formulator will use sufficient diamine to at least directionally improve the cleaning performance against said stains. By "ethylene oxide group" refers to the following structure: By "propylene oxide group" refers to the following structure: By "liquid detergent composition for light work (LDL)" refers to a detergent composition which is used in manual dishwashing. The liquid detergent compositions herein contain either diols or polymeric glycols or a mixture of both. Diols suitable for use in the present invention have the following formula: wherein n = 0-3, R7 = H, methyl or ethyl; and R8 = H, methyl, ethyl, propyl, isopropyl, butyl and isobutyl. Preferred diols include propylene glycol, 1,2-hexanediol, 2-ethyl-1,3-hexanediol and 2,2,4-trimethyl-1,3-pentanediol. When the diols are present, these compositions will comprise at least about 0.5%, preferably at least about 1%, even preferably at least about 3% by weight of the diol composition. further, the composition preferably will not contain more than about 20%, preferably not more than 10%, even preferably not more than about 6% by weight of the composition of diols. Polymeric glycols, which comprise ethylene oxide (EO) and propylene oxide (PO) groups may also be included in the present invention. These materials are formed by adding blocks of ethylene oxide portions to the ends of polypropylene glycol chains. The polymeric glycols suitable for use in the present invention are of the following formula: (PO) x (EO) yH where x + y is approximately 17 to 68, and x / (x + y) is approximately 0.25 to 1.0. A preferred polymeric glycol is a polypropylene glycol (corresponding when "0") having an average molecular weight of from about 1000 to about 5000, preferably from about 2000 to about 4000, preferably about 2000 to about 3000. When polymeric glycols are present, the liquid detergent compositions herein will contain at least about 0.25%, preferably at least about 0.5%, even preferably at least about 0.75% by weight of the polymeric glycol composition. The composition also preferably will contain no more than about 5%, preferably no more than about 3%, even preferably no more than about 2% by weight of the composition. To ensure satisfactory physical stability, as long as polymeric glycols are added to a liquid dishwashing composition, it may also be necessary to include either a diol and / or an inorganic alkali metal salt, such as sodium chloride. Suitable amounts of diols to provide physical stability are in the amounts and scales mentioned above, while a suitable amount of an inorganic alkali metal salt is at least about 0.1% and less than about 1.5%, preferably less than about 0.8% by weight of the composition. As discussed above, the addition of diols can improve the physical and enzymatic stability of a liquid dishwashing composition. It is of particular importance for the present invention that the diols provide significant stabilization benefits to certain polymeric foam stabilizers and enzymes. Both polymeric foam stabilizers and enzymes can provide important benefits by their incorporation.

Without being limited to the theory, diols are considered to provide benefits of enzyme stabilization by limiting the enzyme activity in the liquid dishwashing composition during storage. Enzymes require water for optimal performance, thus deactivation is performed by reducing the amount of free water that interacts with the enzyme by displacing a portion of the water with the diols described above which are completely miscible with water. With use, the liquid dishwashing composition is significantly diluted with water, thus providing the enzyme with an environment of water conducive to optimal activity and performance. It is also considered, again without being limited to theory, that the physical stability benefits of diols and polymeric glycols come from their ability to act as a hydrotrope. By maintaining the phase stability of the composition, even at low temperatures, certain components, particularly certain polymers, are prevented from precipitating out of the composition and forming a multiple phase LDL composition. Thus, the present invention includes a vehicle / solvent system which may consist of one or more of the following ingredients: diols and polymeric glycols as described above, water, inorganic alkali metal salts and one or more of the solvents conventional methods described below.

Conventional solvents In addition to propylene glycol and polypropylene glycol, a variety of other water miscible liquids such as lower alkanoyl, diols, other polyols, ethers, amines and the like can be used in the present invention. The C1-C4 alkanols are particularly preferred. When present, the composition preferably will contain at least about 0.01%, preferably at least about 0.5%, even preferably at least about 1% by weight of the solvent composition. The composition will also contain no more than about 20%, preferably no more than about 10%, even preferably not more than about 8% of the solvent composition. These solvents can be used in conjunction with an aqueous liquid vehicle, such as water, or they can be used without any aqueous liquid vehicle that is present. Solvents are broadly defined as compounds that are liquid at temperatures of 20 ° C-25 ° C and which are not considered as surfactants. One of the distinguishing features is that solvents tend to exist as separate entities and not as large mixtures of compounds. Examples of suitable solvents for the present invention include ethanol, propanol, isopropanol, 2-methylpyrrolidinone, benzyl alcohol and morpholine n-oxide. Among these solvents, ethanol and isopropanol are preferred. Suitable solvents for use herein include ethers and diethers having from 4 to 14 carbon atoms, preferably from 6 to 12 carbon atoms, and preferably from 8 to 10 carbon atoms. In addition, other suitable solvents are alkoxylated glycols or glycols, alkoxylated aromatic alcohols, aromatic alcohols, aliphatic branched alcohols, alkoxylated aliphatic branched alcohols, alkoxylated C1-C5 linear alcohols, C1-C5 linear alcohols, halohydrocarbons and cycloalkyl hydrocarbons and C8-C14 alkyl , C6-C16 glycol ethers and mixtures thereof. In addition to propylene glycol, polypropylene glycol and the diols illustrated above, other glycols according to the formula: HO-CR 1 R 2 -OH where R 1 and R 2 are independently H or a cyclic and / or R 2 chain are suitable and can be used herein. unsaturated or saturated aliphatic hydrocarbon C2- C10. A suitable glycol is dodecane glycol. Suitable alkoxylated glycols that can be used herein are according to the formula R- (A) n-R 1 -OH wherein R is H, OH, a saturated or unsaturated linear alkyl of 1 to 20 carbon atoms, preferably from 2 to 15 and preferably from 2 to 10, wherein R1 is H or a saturated or unsaturated linear alkyl of 1 to 20 carbon atoms, preferably 2 to 15 and preferably 2 to 10, and A is an alkoxy group preferably ethoxy, methoxy, and / or propoxy and n is from 1 to 5, preferably 1 to 2. The alkoxylated glycols suitable for use herein are methoxyoctadecanol and / or ethoxyethoxyethanol. Suitable aromatic alcohols that can be used herein are according to the formula R-OH wherein R is an aryl group substituted with non-alkyl or substituted with alkyl of 1 to 20 carbon atoms preferably 1 to 15 and preferably from 1 to 10. For example, an aromatic alcohol suitable for use herein is benzyl alcohol. Suitable aliphatic branched alcohols which can be used herein are according to the formula R-OH wherein R is a saturated or unsaturated branched alkyl group of 1 to 20 carbon atoms, preferably 2 to 15 and preferably 5 to 12. Branched aliphatic alcohols particularly suitable for use herein include 2-ethylbutanol and / or 2-methylbutanol. Suitable alkoxylated aliphatic branched alcohols which can be used herein are according to the formula R (A) n-OH wherein R is a saturated or unsaturated branched alkyl group of 1 to 20 carbon atoms, preferably 2 carbon atoms. to 15 and preferably from 5 to 12, wherein A is an alkoxy group preferably butoxy, propoxy and / or ethoxy, and n is an integer from 1 to 5, preferably 1 to 2. Suitable alkoxylated aliphatic branched alcohols include 1 - methyl propoxyethanol and / or 2-methylbutoxyethanol. Suitable C1-C5 linear alcohols which can be used herein are according to the formula R-OH wherein R is a saturated or unsaturated linear alkyl group of 1 to 5 carbon atoms, preferably 2 to 4. Suitable linear C1-C5 alcohols are methanol, ethanol, propanol or mixtures thereof. Other suitable solvents include without limit, butyl diglycol ether (BDGE), butyltriglycolic ester, teramyl alcohol and the like. Particularly preferred solvents which may be used herein are butoxypropoxypropanol, butyldiglycol ether, benzyl alcohol, butoxypropanol, ethanol, methanol, sodium propane and mixtures thereof. Other solvents suitable for use herein include propylene glycol derivatives such as n-butoxypropanol or n-butoxyproxypropanol, water soluble CARBITOL R solvents or water soluble CELLOSOLVE R solvents.; the water-soluble CARBITOL R solvents are compounds of the 2- (2-alkoxyethoxy) ethanol class wherein the alkoxy group is derived from ethyl, propyl or butyl; a preferred water-soluble carbitol is 2 (2-butoxyethoxy) ethanol also known as butylcarbitol. The water-soluble CELLOSOLVE R solvents are compounds of class 2-alkoxyethoxyethanol, with 2-butoxyethoxyethanol being preferred. Other suitable solvents include benzyl alcohol and diols such as 2-ethyl-1,3-hexanediol and 2,2,4-trimetryl-1,3-pentanediol and mixtures thereof. Some preferred solvents for use herein are n-butoxypropoxypropanol, BUTYL CARBITOL ® and mixtures thereof. The solvents can also be selected from the group of compounds comprising mono-, di- and tri-ethylene glycol ether derivatives, butylene glycol ethers and mixtures thereof. The molecular weights of these solvents are preferably less than 350, preferably between 100 and 300, even preferably between 115 and 250. Examples of preferred solvents include, for example, mono-ethylene glycol n-hexyl ether, mono-propylene glycol ether n- butyl and methyl tri-propylene glycol ether. The ethylene glycol and propylene glycol ethers are commercially available from the Dow Chemical Company under the tradename "Dowanol" and from Arco Chemical Company under the tradename "Arcosolv". Other preferred solvents including n-hexylic mono- and di-ethylene glycol ether are available from Union Carbide.

Diamines As mentioned above, diamines are used herein in detergent compositions in combination with detersive surfactants at levels which are effective to achieve at least a directional improvement in cleaning performance. In the context of a composition for manual dishwashing, such "levels of use" may vary depending not only on the type and severity of the soils and stains, but also on the temperature of the washing water, the volume of washing water and the duration in which the dishes are in contact with the washing water. Because the habits and practices of the users of detergent compositions show considerable variation, the composition preferably will contain at least about 0.1%, preferably at least about 0.2%, even preferably at least about 0.25%, and even preferably at least about 0.5% by weight of said diamine composition. In addition, the composition preferably will contain not more than about 15%, preferably not more than about 10%, even more preferably not more than about 6% and even preferably not more than 5%, preferably not more than about 1.5% in weight of said diamine composition. In one of its different aspects, this invention provides a means to increase the removal of greasy / oily soils by combining the specific diamines of this invention with surfactants. The "daily" greasy / oily soils are a mixture of triglycerides, lipids, complex polysaccharides, fatty acids, inorganic salts and protein matter. In this way, the diamines, in combination with amphoteric and anionic surfactants in the specific relationships discussed below, offer the benefit of improved cleaning of fat and difficult foods which allows the elimination or reduction in the amount of divalent ions in the modes Preferred of the present formula. This improved cleaning is a result of the propensity of diamines as a pH regulating agent to increase the alkalinity of the dishwashing composition. The higher rate of dissolution achieved by a divalent ion elimination even allows the formulator to perform hand dishwashing detergents, especially compact formulations, at even significantly higher viscosities (eg, 1,000 centipoise or more) than conventional formulations, while maintaining excellent cleaning and dissolving performance. This has important potential advantages for making compact products with a higher viscosity while maintaining an acceptable solution. By "compact" or "Ultra" it refers to detergent formulations with reduced levels of water compared to conventional liquid detergents. For "compact" or "Ultra" formulations, the water level is less than 50%, preferably less than 30% by weight of the liquid dishwashing detergent compositions. These concentrated products provide advantages to the consumer, who has a product which can be used in lower quantities and for the producer, who has less shipping costs. For compositions that do not intend to be concentrated, an adequate level of water is less than about 85%, preferably less than about 70% by weight of the liquid dishwashing detergent compositions. It is preferred that the diamines used in the present invention be substantially free of impurities. That is, by "substantially free" it is meant that the diamines are more than 95% pure, ie, preferably 97%, preferably 99%, even preferably 99.5% free of impurities. Examples of impurities that may be present in commercially provided diamines include 2-methyl-1,3-diaminobutane and alkylhydropyrimidine. In addition, it is considered that the diamines should be free of oxidation reagents to prevent the degradation of diamines and formation of ammonia. As discussed in detail laterIt is important to make the compositions free of hydrogen peroxide when the compositions contain an enzyme. Even small amounts of hydrogen peroxide can cause problems with formulations containing enzymes. However, the diamine can react with any peroxide present and act as an enzyme stabilizer and prevent the hydrogen peroxide from reacting with the enzyme. The only disadvantage of this stabilization of the enzymes by the diamine is that it is considered that the nitrogen compounds produced cause bad odors that may be present in compositions containing diamine. By making the diamine act as an enzyme stabilizer, diamine is also prevented from providing the benefits to the composition in which it was originally placed to perform, namely, fat cleaning, foaming, dissolution and low temperature stability. . Therefore, it is preferred to minimize the amount of hydrogen peroxide present as an impurity in the compositions of the invention, either by using components that are substantially free as an enzyme stabilizer, due to the possible generation of hydrogen peroxide and / or by using antioxidants that are not diamine even though the diamine can act in bad odor compounds and reducing the amount of available diamine present to perform its main function. 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 about 8.4 to about 11, even preferably from about 8.6 to about 10.75. Preferred materials for performance and delivery considerations are 1, 3-bis (methylamine) -cyclohexane (pKa = 10 to 10.5), 1, 3-propanediamine (pK1 = 10.5; pK2 = 8.8), 1.6 hexane diamine (pK1 = 11, pK2 = 10), 1.3 pentane diamine (Dytek EP) (pK1 = 10.5, pK2 = 8.9), 2-methyl 1,5-pentane diamine (Dytek A) (pK = 11.2; pK2 = 10.0).

Other preferred materials are primary diamines with alkylene spacers ranging from C4 to Ce. In general, it is considered that primary diamines are preferred over secondary and tertiary diamines.

Definition of pK1 and pK2 As used herein, "pKal" and "pKa2" are amounts of a type known collectively by those skilled in the art as "pKa". pKa is used in the present in the same way as it is commonly known to those skilled in the chemistry art. The values referred to herein can be obtained from the literature, such as from "Critical Stability Constants: Volume 2, Amines" by Smith and Martel, Plenumm Press, NY and London, 1975. Additional information on pKa can be obtained from relevant corporate literature, such as information provided by Dupont, a supplier of diaminas. As a working definition in the present, the pKa of the diamines is specified in an all aqueous solution at 25 ° C and for an ionic resistance between 0.1 to 0.5 M. The pKa is an equilibrium constant which can change with temperature and ionic resistance; in this way, the values reported in the literature sometimes do not agree depending on the measurement method and conditions. To eliminate ambiguity, the conditions and / or relevant references used for pKa of this invention are as defined herein or in "Critical Stability Constants: Volume 2, Amines". A typical method of measurement is the potentiometric titration of acid with sodium hydroxide and determination of pKa by suitable methods as described and referenced in Shugar and Dean's "The Chemist's Ready Reference Handbook", McGraw Hill, NY, 1990 It has been determined that substituents and structural modifications that decrease pK1 and pK2 to less than about 8.0 are undesirable and can cause performance losses. This may include substitutions leading to ethoxylated diamines, hydroxyethyl substituted diamines, oxygen diamines in the beta (and less range) position for nitrogen in the spacer group (e.g., Jeffamine EDR 148). In addition, materials based on ethylenediamine are not suitable. The diamines useful herein can be defined by the following structure: wherein R2.5 are independently selected from H, methyl, -CH3-CH2, and ethylene oxide; 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 present and selected from portions that withdraw or donate selected electrons to adjust the diamine pKa to the desired scale. If A is present, then x and y must be both 1 or more.

Examples of preferred diamines can be found in the co-pending provisional patent application of Phillip Kyle Vinson et al., Entitled "Dishwashing Detergent Compositions Containing Organic Diamines for Imporved Grease Cleaning, Sudsing, Low Temperature Stability and Dissolution", which has the No. Case of P & G 7176 P, application with no. series 60 / 087,693, and filed June 2, 1998, which is incorporated herein by reference.

Anionic Surfactants The anionic surfactants useful in the present invention are preferably selected from the group consisting of linear alkylbenzenesulfonate, alphaolephinsulfonate, paraffin sulphonates, alkyl ester sulfonates, alkyl sulfates, alkylalkoxysulfate, alkylsulfonates, alkylalkoxycarboxylate, alkoxylated alkylsulfates, sarcosinates, taurinates and mixtures of the same. An effective amount, typically from about 0.5% to about 90%, preferably about 5% to about 50%, preferably from about 10 to about 30%, by weight of anionic detersive surfactant can be used in the present invention. Suitable examples of anionic surfactants can be found in the co-pending provisional patent application of Chandrika Kasturi et al., Entitled "Liquid Detergent Compositions Comprising Polymeric Suds Enhancers", which has the P &; G. 6938P, series number 60 / 066,344 and filed November 21, 1997, which is incorporated herein by reference. Additional examples of suitable anionic surfactants are given in "Surface Active Agents and Detergents" (Vol. I and II of Schwartz, Perry and Berch). A variety of such surfactants are also generally described in U.S. Patent 3,929,678, issued December 30, 1975 to Laughlin, et al. in column 23, line 58 to column 29, line 23. In addition, suitable anionic surfactants can be found in U.S. Patent No. 5,415,814 issued May 16, 1995, to Ofosu-Asante et al., which are incorporated in the present as a reference.

Amphoteric Surfactants The amphoteric surfactants useful in the present invention are preferably selected from amine oxide surfactants. The amine oxides are semi-polar nonionic surfactants and include water-soluble amine 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; 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 about 10 to about 18 carbon atoms and a portion selected from the group consisting of alkyl and hydroxyalkyl portions of about 1 to about 3 carbon atoms. The semi-polar nonionic detergent surfactants include the amine oxide surfactants having the formula wherein R3 is an alkyl, hydroxyalkyl, or alkylphenyl group or mixtures thereof containing from about 8 to about 22 carbon atoms; R4 is an alkylene or hydroxyalkylene group containing from about 2 to about 3 carbon atoms or mixtures thereof; x is from 0 to about 3; each R 5 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 R5 groups can be linked together, for example, through an oxygen or nitrogen atom, to form a ring structure. These amine oxide surfactants in particular include dimethylamine oxides of C-io-C-iß alkyl and oxides of alkoxyethyldihydroxyethyl amine Cß-C 2. Also suitable are amine oxides such as propylamine oxides, represented by the formula: wherein Ri is an alkyl, 2-hydroxyalkyl, 3-hydroxyalkyl, or 3-alkoxy-2-hydroxypropyl radical wherein alkyl and alkoxy, respectively, contain from about 8 to about 18 carbon atoms, R2 and R3 are each methyl, ethyl, propyl, isopropyl, 2-hydroxyethyl, 2-hydroxypropyl, or 3-hydroxypropyl and n is from 0 to about 10. Another suitable species of active agents of semipolar surfaces of amine oxide comprise compounds and mixtures of compounds that They have the formula: wherein Ri is an alkyl, 2-hydroxyalkyl, 3-hydroxyalkyl, or 3-alkoxy-2-hydroxypropyl radical, wherein the alkyl and alkoxy, respectively, contain from about 8 to about 18 carbon atoms, R2 and R3 are each methyl, ethyl, propyl, isopropyl, 2-hydroxyethyl, 2-hydroxypropyl, or 3-hydroxypropyl and n is from 0 to about 10. Particularly preferred are amine oxides of the formula: wherein Ri is an alkyl C-io- and R2 and R3 are methyl or ethyl. Because they are low in foam, it may also be convenient to use long chain amine oxide surfactants which are more fully described in the U.S. Patents. Nos. 4,316,824 (Pancheri), 5,075,501 and 5,071, 594, incorporated herein by reference. Other suitable non-limiting examples of amphoteric detergent surfactants which are useful in the present invention include amidopropyl betaines and derivatives of secondary and tertiary aliphatic or heterocyclic amines in which the aliphatic portion can be straight or branched chain and wherein one of the Aliphatic substituents contain from about 8 to about 24 carbon atoms and at least one aliphatic substituent contains an anionic water solubilizing group. Additional examples of suitable amphoteric surfactants are given in "Surface Active Agents and Detergents" (Vol. I and II of Schwartz, Perry and Berch), which is incorporated herein by reference.

Preferably, the amphoteric surfactant is present in the composition in an effective amount, preferably from about 0.1% to about 20%, preferably about 0.1% to about %, and even preferably from about 0.5% to about 10%, by weight.

Secondary surfactants The secondary detersive surfactant can be selected from the group consisting of non-ionic, cationic, ampholytic, zwitterionic and mixtures thereof. In selecting the type and amount of detersive surfactant, together with other auxiliary ingredients described herein, the detergent compositions can be formulated to be used in the context of laundry cleaning or in other different cleaning applications, particularly including dishwashing. . Therefore, the particular surfactants used can vary widely depending on the particular designed end use. Suitable secondary surfactants are described in detail in the co-pending provisional patent application of Chandrika Kasturi et al., Entitled "Liquid Detergent Compositions Comprising Polymeric Suds Enhancers", which has the Case No. of P & G 6938P, application with serial number 60 / 066,344, incorporated above.

Ratio of anionic to amphoteric to diamine In the compositions of the present invention, the ratio of the anionic: amphoteric surfactant: diamine is from about 100: 40: 1 to about 9: 0.5: 1, in moles, preferably the ratio of the agent anionic surfactant: amphoteric: diamine is from about 27: 8: 1 to about 11: 3: 1, in moles. It has been found that detergent compositions containing anionic surfactant, amphoteric surfactant and diamine in this specific ratio scale, provide improved low temperature stability, provide better fat removal and cleaning benefits of difficult foods at pH less than 12.5, and improved hard water cleaning. In another aspect of the invention, the molar ratio of the anionic surfactant to diamine of more than 9: 1, preferably greater than 20: 1, has been found to give improved stability at low temperature, provides better fat removal and benefits of cleaning of difficult foods and improved cleaning of hard water.

Optional Detergent Ingredients Polymeric Foam Stabilizer The compositions of the present invention may optionally contain a polymeric foam stabilizer. These polymeric foam stabilizers provide extended foam volume and foam duration without sacrificing the fat-cutting ability of liquid detergent compositions. These polymeric stabilizers are selected from: i) (N, N-dialkylamino) alkyl acrylate ester homopolymers having the formula: wherein each R is independently hydrogen, C 1 -C 2 alkyl, and mixtures thereof, R 1 is hydrogen, C 1 -C 6 alkyl and mixtures thereof, n is from 2 to about 6; and i) copolymers of (i) and wherein R 1 is hydrogen, C 1 -C 2 alkyl and mixtures thereof, provided that the ratio of (ii) to (i) is from about 2 to 1 to about 1 to 2; The molecular weight of polymeric foaming promoters, determined through conventional gel permeation chromatography, is from about 1,000 to about 2,000,000, preferably from about 5,000 to about 1,000,000, preferably from about 10,000 to about 750,000. , preferably from 20,000 to about 500,000, even more preferably from 35,000 to about 200,000. The polymeric foam stabilizer may optionally be present in the form of a salt, either an inorganic or organic salt, for example the (N, N-dialkylamino) alkyl acrylate citrate, sulfate or nitrate salt. A preferred polymeric foam stabilizer is (N, N-dialkylamino) alkyl acrylate ester, namely When present in the compositions, the polymeric foam booster may be present in the composition of about 0. 01% to about 15%, preferably from about 0.05% to about 10%, preferably from about 0.1% to about 5%, by weight.

Detergency Meter The compositions according to the present invention may further comprise a builder system. Because detergency builders such as citric acid and citrate impair the stability of enzymes in LDL compositions, it is convenient to include and reduce the amounts or completely remove the builder salts normally used in LDL compositions that incorporate propylene glycol as a builder. . When a detergent composition includes propylene glycol solvent as a part or as a whole of the detergent vehicle, the enzymes are more stable and smaller amounts or no detergency builder salts are necessary. If it is convenient to use a builder, then any conventional builder system is suitable for use herein including aluminosilicate materials, silicates, polycarboxylates and fatty acids, materials such as ethylenediamine tetraacetate, metal ion sequestrants such as aminopolyphosphonates, particularly ethylenediaminetetramethylenephosphonic acid and diethylenetriaminepentamethylenephosphonic acid. Although less preferred for obvious environmental reasons, phosphate builders also can be used herein. Polycarboxylate builders suitable for use herein include citric acid, preferably in the form of a water soluble salt, succinic acid derivatives of the formula R-CH (COOH) CH2 (COOH) wherein R is alkenyl or C 0-2 alkyl. preferably C 12-16, or where R can be substituted with hydroxyl, sulfosulfoxyl or sulfone substituents. Specific examples include lauryl succinate, myristylsuccinate, palmitylsuccinate; 2-dodecinylsuccinate; 2-tetradecenylsuccinate. The succinate builders are preferably used in the form of water-soluble salts, including sodium, potassium, ammonium, and alkanolammonium salts. Other suitable polycarboxylates are oxodisuccinates and mixtures of monosuccinic and disuccinic tartrate acid as described in US 4,663,071. Especially for the liquid execution of the present, the fatty acid builders suitable for use herein are saturated or unsaturated C-io-iß fatty acids, as well as the corresponding soaps. Preferred saturated species have from 12 to 16 carbon atoms in the alkyl chain. The preferred unsaturated fatty acid is oleic acid. Another preferred builder system for liquid compositions is based on dodecenylsuccinic acid and citric acid. If builder salts are included, they will be included in amounts of 0.5% to 50% by weight of the composition, preferably 5% to 30% and usually 5% to 25% by weight.

Enzymes The detergent compositions of the present invention may further comprise one or more enzymes which provide cleaning performance benefits. Such enzymes include enzymes selected from cellulases, hemicellulases, peroxidases, proteases, gluco-amylases, amylases, lipases, cutinases, pectinases, xylanases, reductases, oxidases, phenoloxidases, lipoxygenases, ligninases, pullulanases, tanases, pentosanas, malanases, β-glucanases, arabinosidases or mixtures thereof. A preferred combination is a detergent composition having a variety of conventional applicable enzymes such as protease, amylase, lipase, cutinase and / or cellulase. When the enzymes are present in the compositions, they are from about 0.0001% to about 5% active enzyme by weight of the detergent composition. The preferred proteolytic enzymes, are then selected from the group consisting of Alcalase ® (Novo Industri A / S), BPN ', Protease A and Protease B (Genecor), and mixtures thereof. Protease B is the most preferred. Preferred amylase enzymes include TERMAMYIL®, DURAMYIL® and the amylase enzymes described in WO 9418314 for Genencor International and WO 9402597 for Novo. Other non-limiting examples of suitable and preferred enzymes are described in the co-pending application: "Dishwashing Detergent Compositions Containing Organic Diamines for Improved Grease Cleaning, Sudsing, Low Temperature Stability and Dissolution", which has the P &; G 7167P and application serial number 60 / 087,693, which is incorporated herein by reference. Because hydrogen peroxide and detergency builders such as citric acid and citrates impair the stability of enzymes in LDL compositions, it is convenient to reduce or eliminate the levels of these compounds in compositions containing enzymes. Frequently, hydrogen peroxide is found as an impurity in surfactants and pastes of surfactants. As such, the preferred level of hydrogen peroxide in the amine oxide or amine oxide surfactant paste is 0-40 ppm, preferably 0-15 ppm. Amine impurities in amine oxide and betaine, if present, should be minimized at the aforementioned levels for hydrogen peroxide.

Magnesium Ions Although it is preferred to omit the divalent ions of LDL compositions prepared according to the present invention, the alternate embodiments of the present invention may include magnesium ions. It is advisable to exclude all divalent ions from the LDL compositions herein, because such ions can lead to decrease dissolution properties, as well as poor rinse and poor low temperature stability. In addition, the formulation of such compositions containing divalent ions in matrices of alkaline pH can be difficult due to the incompatibility of the divalent ions, particularly magnesium, with hydroxide ions. However, the presence of magnesium ions offers different benefits. Notably, the inclusion of such divalent ions improves the cleaning of greasy soils for different LDL compositions, in particular, compositions containing alkyl ethoxycarboxylates and / or polyhydroxy fatty acid. This is especially true when the compositions are used in softened water containing few divalent ions.

But in the present invention, these benefits can be obtained without the inclusion of divalent ions. In particular, improved fat cleaning can be achieved without divalent ions by the inclusion of organic diamines in combination with amphoteric and anionic surfactants in the specific ratios discussed above, while the enzymes have been shown to improve the performance of softness to the skin. the LDL compositions of the present. If they are to be included in an alternate embodiment of the LDL compositions herein, then the magnesium ions are present at an active level of from about 0.01% to 1%, preferably from about 0.015% to 0.5%, preferably from about 0.025% to 0.1% by weight. The amount of magnesium ions present in compositions of the invention will also depend on the amount of total surfactant present therein, including the amount of alkyl ethoxycarboxylates and polyhydroxy fatty acid amide. Preferably, the magnesium ions are added as a salt of hydroxide, chloride, acetate, sulfate, formate, oxide or nitrate to the compositions of the present invention. Because during storage the stability of these compositions becomes poor due to the formulation of hydroxide precipitates in the presence of compositions containing moderate concentrations of hydroxide ions, it may be necessary to add certain chelating agents. Suitable chelating agents are discussed below and in the U.S. patent. No. 5,739,092, issued April 14, 1998, to Ofosu-asante, incorporated herein by reference.

Perfumes Perfumes and perfumery ingredients useful in the compositions and methods herein that comprise a wide variety of natural and synthetic chemical ingredients, include without limit, aldehydes, ketones, esters and the like. Also included are different extracts or natural 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 the like . The finished perfumes may comprise extremely complex mixtures of such ingredients. The finished perfumes typically comprise from about 0.01% to about 2% 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. Non-limiting examples of perfume ingredients useful herein can be found in the co-pending provisional patent application: "Dishwashing Detergent Compositions Containing Organic Diamines for Improved Grease Cleaning, Sudsing, Low Temperature Stability and Dissolution" which has the Case No. of P & G 7167P, application with serial number 60 / 087,893, previously incorporated.Guelaator Agents The detergent compositions herein may also optionally contain one or more magnesium and / or iron chelating agents. Such chelating agents can be selected from the group consisting of amino polycarboxylates, aminophosphonates, polyfunctionally substituted aromatic chelating agents and mixtures thereof, all defined below. Without intending to be limited to theory, it is considered that the benefits of these materials is due in part to their exceptional ability to remove manganese ions and iron from wash solutions by the formation of soluble chelates. Aminocarboxylates useful as optional chelating agents include ethylenediaminetetracetates, N-hydroxyethylenediaminetriacetates, nitrile tri-acetates, ethylenediaminetetraproprionates, triethylenetetraminehexacetates, diethylenetriaminepentaacetates, and ethanoldi glycines, alkali metal, ammonium and substituted ammonium salts, and mixtures thereof. The aminophosphonates are also suitable for use as chelating agents in the compositions of the invention when at least low levels of total phosphorus are permitted in detergent compositions, and include ethylene diamine tetrakis (methylene phosphonates) as DEQUEST. Preferably, these aminophosphonates do not contain alkyl or alkenyl groups with more than about 6 carbon atoms.

Polyfunctionally substituted aromatic chelating agents are also useful in the compositions herein. See patent of 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 preferred biodegradable chelator for use herein is ethylene diamine disuccinate ("EDDS"), especially the [S, S] isomer as described in U.S. Patent 4,704,233, November 3, 1987, to Hartman and Perkins. The compositions herein may also contain salts of water soluble methyl glycine diacetic acid (MGDA) (or acid form) as a chelator or builder. Similarly, so-called "weak" detergency builders such as citrate can also be used as chelating agents. If used, these chelating agents will generally comprise from about 0.1% to about 15% by weight of the detergent compositions herein. Preferably, if used, the chelating agents will comprise from about 0.1% to about 3.0% by weight of such compositions.

Composition pH The dishwashing compositions of the invention will be subjected to acidic stresses created by food soils when put into use, that is, diluted and applied to dirty dishes. If a composition with a pH greater than 7 is more effective, it should preferably contain a pH regulating agent capable of providing a generally more alkaline pH in the composition and in diluted solutions. The dishwashing compositions of the present invention will contain from about 0.1% to 15%, preferably from about 1% to 10%, preferably from about 2% to 8% by weight of a pH regulating agent. The pKa value of this pH regulating agent should be from about 0.5 to 1.0 pH units below the desired pH value of the composition (determined as described above). Preferably, the pKa of the pH regulating agent should be about 7 about 12. Under these conditions, the pH regulating agent must effectively control the pH while using the minimum amount thereof. Preferred inorganic pH / alkalinity sources include alkali metal carbonates, alkali metal hydroxides and alkali metal phosphates, eg, sodium carbonate, sodium hydroxide, sodium polyphosphate. The pH regulating agent can be an active detergent in its own right, or it can be an inorganic or organic material of low molecular weight that is used in this composition exclusively to maintain an alkaline pH. Preferred pH regulating agents for compositions of this invention are nitrogen-containing materials. Some examples are amino acids such as lysine or low alcohol amines such as mono-, di-, and tri-ethanolamine. The diamines, described in detail above, also act as pH regulating agents and are preferred pH regulating agents. The preferred pH regulator system for use in the detergent compositions herein includes a combination of 0.5% diamine and 2.5% citrate and a combination of 0.5% diamino, 0.75% potassium carbonate and 1.75% sodium carbonate. Other preferred nitrogen-containing pH regulating agents are Tri (hydroxymethyl) amino methane (HOCH2) 3CNH3 (TRIS), 2-amino-2-ethyl-1,3-propanediol, 2-amino-2-methyl-propanol, 2-amino-2-methyl-1,3-propanol, disodium glutamate, N-methyldiethanolamide, 1,3-diamino-propanol N, N'-tetra-methyl-1,3-diamino-2-propanol, N, N -bis (2-hydroxyethyl) glycine (bicine) and N-tris (hydroxymethyl) methylglycine (tricine). Mixtures of any of the foregoing are also acceptable. For additional pH regulators, see McCutcheon's EMULSIFIERS AND DETERGENTS, North American Edition, 1997, McCutcheon Division, MC Publishing Company Kirk and WO 95/07971, both incorporated herein by reference.

Other ingredients Detergent compositions will preferably comprise one or more detersive auxiliaries selected from the following: soil release polymers, polymeric dispersants, polysaccharides, abrasives, bactericides and other antimicrobials, rust inhibitors, builders, enzymes, dyes, regulators pH, antifungal and mold control agents, insect repellents, perfumes, hydrotropes, thickeners, processing aids, foamers, brighteners, anti-corrosive auxiliaries, antioxidants stabilizers and chelators. A wide variety of other useful ingredients in detergent compositions can be included in the compositions herein, including other active ingredients, carriers, hydrotropes, antioxidants, processing aids, dyes or pigments, solvents for liquid formulations, solid fillers for bar compositions , etc. If high foaming is desired, foaming compositions such as C10-16 alkanolamides can be incorporated into the foam compositions. normally at levels of 1% -10%. C-IO-CH monoethanol and diethanolamides illustrate a typical class of such foam boosters. It is also advantageous to use such foam boosters with high foaming auxiliary surfactants such as the amine oxides, betaines and sultaines mentioned above. An antioxidant may optionally be added to the detergent compositions of the present invention. It can be any conventional antioxidant used in detergent compositions, such as 2,6-di-tebutyl-4-methylphenol (BHT), carbamate; ascorbate; - thiosulfate, monoethanolamine (MEA), diethanolamine, triethanolamine, etc. It is preferred that the antioxidant, when present in the composition, be made from about 0.001% to about 5% by weight.

Different detersive ingredients optionally employed in the compositions herein can be stabilized by absorbing said ingredients in a porous hydrophobic substrate, then covering said substrate with a hydrophobic coating. Preferably, the detersive ingredient is mixed with a surfactant before being absorbed into the porous substrate. In use, the detersive ingredient is released from the substrate in the aqueous wash solution, where it performs its detersive function. To illustrate this technique in more detail, a porous hydrophobic silica (trademark SIPERNAT D10, DeGussa) is mixed with a proteolytic enzyme solution containing 3% -5% nonionic surfactant of C? 3-? Ethoxylated alcohol. s (E07). Normally, the enzyme / surfactant solution is 2.5X the weight of silica. The resulting powder is dispersed with agitation in silicone oils (different viscosities of silicone oil can be used in the range of 500-12,500). The resulting silicone oil dispersion is emulsified or otherwise added to the final detergent matrix. By this means, ingredients such as the aforementioned enzymes, bleaches, bleach activators, bleach catalysts, photoactivators, dyes, fluorescers, fabric conditioners and hydrolysable surfactants can be "protected" for use in detergents, including detergent compositions liquid for washing. In addition, these detergent modalities for manual dishwashing preferably also comprise a hydrotrope. Suitable hydrotropes include sodium, potassium, ammonium or water-soluble substituted ammonium salts of toluenesulfonic acid, naphthalenesulfonic acid, cumenesulfonic acid, xylene sulfonic acid.

NON-AQUEOUS LIQUID DETERGENTS The manufacture of liquid detergent compositions comprising a nonaqueous vehicle medium can be prepared according to the descriptions of the US patents. 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-A2, 195,649; E.U.A. 4,988,462; E.U.A. 5,266,233; 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); E.U.A. 4,615,820; EP- A-565,017 (10/13/93); EP-A-030,096 (10/6/81), incorporated herein by reference. Such compositions may contain different detersive ingredients of particulate material stably suspended therein. Such non-aqueous compositions comprise a liquid phase and optionally, but preferably, a solid phase, all as described below in more detail and in the cited references. The compositions of this invention can be used to form aqueous wash solutions for use in manual dishwashing.

Generally, an effective amount of such compositions in water is added to form aqueous soaking or cleaning solutions. The aqueous solution formed is put in contact with the dishes, tableware and kitchen utensils.

An effective amount of the detergent compositions herein added in water to form aqueous cleaning solutions may comprise sufficient amounts to form about 500 to 20,000 ppm of composition in aqueous solution. Preferably, from about 800 to 5,000 ppm of the detergent compositions herein will be provided in an aqueous cleaning solution. The following examples are illustrative of the present invention, but are not intended to limit, or otherwise define, its scope. All parts, percentages and relationships used herein are expressed as percentages by weight, unless otherwise specified.

EXAMPLES PICTURE \ The light duty liquid dishwashing detergents of the present invention are the following: Example 1 AE0.6S1 26.1 Amine oxide2 6.5 Citric acid 2.6 Foaming polymer3 0.2 Sodium methersulfate 3.50 Propylene glycol 9.8 Nonionic4 3.0 Diamine5 0.50 Water Rest Total active 36% Viscosity (cps @ 20 ° C) 780 PH @ 10% 9.0 1: C12-13 alkyl ethoxysulfonate containing an average of 0.6 ethoxy groups. 2: Amine oxide C-? 2-C-? . 3: The polymer is homopolymer of (N, N-dimethylamino) ethyl methacrylate 4: Non-ionic can be either ethoxylated C 11 alkyl surfactant containing 9 ethoxy groups or ethoxylated C 10 alkyl surfactant containing 8 ethoxy groups. 5: 1, 3-bis (methylamino) -cyclohexane TABLE II The light duty liquid dishwashing detergents of the present invention are the following: Example 2 Example 3 Example 4 Example 5 Example 6 AE0.6S1 26.1 26.1 26.1 13.05 26.1 Amine oxide2 6.5 6.5 6.5 3.25 5.5 Nonionic3 3 3 3 1.53 Foaming polymer 0.2 0.2 0.2 0.1 0.2 of foam4 Diamine5 0.5 0.5 0.5 0.25 0.5 Sodium metomulfate 3.5 3.5 3.5 1.75 2.0 Sodium chloride - 0.5 0.5 0.25 0.6 Propylene glycol 9.8 10.0 5.0 - Polypropylene glycol - 1.0 1.0 0.5 1.0 Citrate 2.6 Mg2 + ~ 0.04 Protease6 - 0.015 0.0075 Ethanol - 7.0 0.0 0.0 7.0 Anion molar ratio: 23: 8: 1 oxide 23: 8: 1 23: 8: 1 23: 8: 1 23: 8: 1 amine: diamine pH @ 10% 9 * 1: C12-13 alkyl ethoxysulfonate containing an average of 0.6 ethoxy groups. 2: Amine oxide C? 2-C? . 3: Non-ionic can be either C11 alkyl ethoxylate surfactant containing 9 ethoxy groups or C10 alkyl ethoxylated surfactant containing 8 ethoxy groups. 4: The polymer is homopolymer of (N, N-dimethylamino) ethyl methacrylate : 1, 3 bis (methylamino) -cyclohexane. 6: The protease is selected from: Savinase®; Maxatase®; Maxacal®; Maxapem 15®; subtilisin BPN and BPN '; Protease B; Protease A; Protease D; Primase®; Durazym®; Opticlean®; and Optimase®; and Alcalase ®.

TABLE III The light duty liquid dishwashing detergents of the present invention are the following: Example 7 Example 8 Example 9 Example 10 AE0.6S1 26.09 26.09 26.09 28.80 Oxide of amine2 6.50 6.5 8.0 8.0 Polymer fomentator of 0.20 0.20 0.20 0.20 foam3 Cumensulfonate of 3.50 3.50 3.50 3.90 sodium Not ionic4 3.00 3.00 3.00 3.00 Diamine5 0.50 0.50 0.50 0.50 0.55 Sodium chloride 1.5 1.5 1.5 1.5 NaOH 0.35 0.35 0.35 0.35 Na2CO3 1.75 1.75 1.75 1.75 K2CO3 0.75 0.75 0.75 0.75 Propylene glycol 4.0 4.0 4.0 4.0 Polypropylene glycol 1.0 1.0 1.0 1.0 Ethanol 3.0 0.7 0.7 - Water and Mise. REST REST REST REST Viscosity (cps @ 70F) 353 640 635 848 pH @ 10% 10.8 10.8 10.80 10.8 1: C12-13 alkyl ethoxysulfonate containing an average of 0.6 ethoxy groups. 2: Amine oxide C? 2-C. 3: The polymer is homopolymer of (N, N-dimethylamino) ethyl methacrylate 4: Non-ionic can be either C10 alkyl ethoxylate surfactant containing 8 ethoxy groups or ethoxylated C10 alkyl surfactant containing 8 ethoxy groups. 5: 1, 3-bis (methylamino) -cyclohexane

Claims (10)

NOVELTY OF THE INVENTION CLAIMS

1. A liquid dishwashing detergent composition suitable for use in manual dishwashing, said composition characterized by: a) an organic low molecular weight diamine having a pK1 and a pK2, wherein the pK1 and the pK2 of said diamine they are on the scale of approximately 8.0 to 11.5; b) an anionic surfactant; c) an amphoteric surfactant; and d) a solvent selected from the group consisting of a diol, polymeric glycol and mixtures thereof; wherein said diol is selected from the group consisting of: wherein n = 0-3, R = H, methyl or ethyl; and R8 = H, methyl, ethyl, propyl, isopropyl, butyl and isobutyl; and wherein the polymeric glycol is selected from the group consisting of: (PO) x (EO)? H where PO represents a group of propylene oxide and EO represents a group of ethylene oxide and x + y is 17 to 68, and x / (x + y) is from 0.25 to 1.0; and wherein the pH (measured according to 10% aqueous solution) is from 5.0 to 12.5 and the molar ratio of said anionic surfactant to said amphoteric surfactant to said amine is from 100: 40: 1 to 9: 0.5: 1.

2. The liquid dishwashing detergent composition according to claim 1, further characterized by a pH regulating agent and wherein the composition has a pH of 10 to 11.5.

3. The liquid dishwashing detergent composition according to any of claims 1-2, further characterized in that the diol is selected from the group consisting of propylene glycol, 1,2-hexanediol, 2-ethyl-1,3-hexanediol and 2,2,4-trimethyl-1,3-pentanediol.

4. The liquid dishwashing detergent composition according to any of claims 1-3, further characterized in that the polymeric glycol is polypropylene glycol having a molecular weight of 1000 to 5000. 5.- The liquid detergent composition for washing Tableware according to any of claims 1-4, further characterized in that said diamine is selected from the group consisting of: wherein R2-5 are independently selected from H, methyl, -CH3-CH2, and ethylene oxide; 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 present and selected from portions that withdraw or donate selected electrons to adjust the diamine pKa to the desired scale; where if A is present, then x and y must be 2 or more. 6. The liquid dishwashing detergent composition according to any of claims 1-5, further characterized in that the polymeric glycol is polypropylene glycol having a molecular weight of 2000 to 4000 and is present on a scale of 0.25% to 5.0 % by weight of the composition. 7. The liquid dishwashing detergent composition according to any of claims 1-6, further characterized by a polymeric foam stabilizer selected from the group consisting of: i) (N, N-dialkylamino) ester homopolymers alkyl acrylate having the formula: wherein each R is independently hydrogen, C? -C8 alkyl, and mixtures thereof, R1 is hydrogen, C-pC? alkyl and mixtures thereof, n is from 2 to about 6; and ii) copolymers of (i) and wherein R 1 is hydrogen, C 1 -C 2 alkyl and mixtures thereof, provided that the ratio of (ii) to (i) is from 2 to 1 to 1 to 2; and wherein said polymeric foam stabilizer has a molecular weight of 1, 000 to 2,000,000 daltons. 8. The liquid dishwashing detergent composition according to any of claims 1-7, further characterized by an α-amylase having a specific activity at least 25% greater than the specific activity of Termamyl® on a scale of temperature from 25 ° C to 55 ° C and at a pH value in the range of 8 to 10, measured by the Phadebas® α-amylase activity test. 9. A method for cleaning a substrate in a manual dishwashing operation characterized by the steps of: (a) contacting the substrate with a liquid dishwashing detergent composition prepared in accordance with claim 1; and (b) allowing the detergent composition to remain in contact with the substrate for a sufficient time to provide effective cleaning benefits to the substrate. 10. The method according to any of claims 1-9, further characterized in that the liquid detergent composition for dishwashing is applied to the substrate with no more than 90% dilution with water.