Classifications

• • C—CHEMISTRY; METALLURGY
  • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
  • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
  • C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
  • C11D3/0005—Other compounding ingredients characterised by their effect
  • C11D3/0084—Antioxidants; Free-radical scavengers
• • C—CHEMISTRY; METALLURGY
  • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
  • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
  • C11D1/00—Detergent compositions based essentially on surface-active compounds; Use of these compounds as a detergent
  • C11D1/66—Non-ionic compounds
  • C11D1/83—Mixtures of non-ionic with anionic compounds
• • C—CHEMISTRY; METALLURGY
  • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
  • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
  • C11D1/00—Detergent compositions based essentially on surface-active compounds; Use of these compounds as a detergent
  • C11D1/88—Ampholytes; Electroneutral compounds
  • C11D1/94—Mixtures with anionic, cationic or non-ionic compounds
• • C—CHEMISTRY; METALLURGY
  • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
  • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
  • C11D11/00—Special methods for preparing compositions containing mixtures of detergents
  • C11D11/0094—Process for making liquid detergent compositions, e.g. slurries, pastes or gels
• • C—CHEMISTRY; METALLURGY
  • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
  • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
  • C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
  • C11D3/0005—Other compounding ingredients characterised by their effect
  • C11D3/0047—Other compounding ingredients characterised by their effect pH regulated compositions
• • C—CHEMISTRY; METALLURGY
  • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
  • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
  • C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
  • C11D3/16—Organic compounds
  • C11D3/20—Organic compounds containing oxygen
  • C11D3/2003—Alcohols; Phenols
  • C11D3/2041—Dihydric alcohols
• • C—CHEMISTRY; METALLURGY
  • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
  • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
  • C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
  • C11D3/16—Organic compounds
  • C11D3/20—Organic compounds containing oxygen
  • C11D3/2003—Alcohols; Phenols
  • C11D3/2041—Dihydric alcohols
  • C11D3/2044—Dihydric alcohols linear
• • C—CHEMISTRY; METALLURGY
  • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
  • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
  • C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
  • C11D3/16—Organic compounds
  • C11D3/20—Organic compounds containing oxygen
  • C11D3/2003—Alcohols; Phenols
  • C11D3/2041—Dihydric alcohols
  • C11D3/2048—Dihydric alcohols branched
• • C—CHEMISTRY; METALLURGY
  • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
  • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
  • C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
  • C11D3/16—Organic compounds
  • C11D3/26—Organic compounds containing nitrogen
  • C11D3/30—Amines; Substituted amines ; Quaternized amines
• • C—CHEMISTRY; METALLURGY
  • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
  • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
  • C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
  • C11D3/16—Organic compounds
  • C11D3/37—Polymers
  • C11D3/3703—Macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
  • C11D3/3707—Polyethers, e.g. polyalkyleneoxides
• • C—CHEMISTRY; METALLURGY
  • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
  • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
  • C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
  • C11D3/16—Organic compounds
  • C11D3/38—Products with no well-defined composition, e.g. natural products
  • C11D3/386—Preparations containing enzymes, e.g. protease or amylase
  • C11D3/38618—Protease or amylase in liquid compositions only
• • C—CHEMISTRY; METALLURGY
  • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
  • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
  • C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
  • C11D3/43—Solvents
• • C—CHEMISTRY; METALLURGY
  • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
  • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
  • C11D1/00—Detergent compositions based essentially on surface-active compounds; Use of these compounds as a detergent
  • C11D1/02—Anionic compounds
  • C11D1/12—Sulfonic acids or sulfuric acid esters; Salts thereof
  • C11D1/29—Sulfates of polyoxyalkylene ethers
• • C—CHEMISTRY; METALLURGY
  • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
  • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
  • C11D1/00—Detergent compositions based essentially on surface-active compounds; Use of these compounds as a detergent
  • C11D1/66—Non-ionic compounds
  • C11D1/72—Ethers of polyoxyalkylene glycols
• • C—CHEMISTRY; METALLURGY
  • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
  • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
  • C11D1/00—Detergent compositions based essentially on surface-active compounds; Use of these compounds as a detergent
  • C11D1/66—Non-ionic compounds
  • C11D1/75—Amino oxides
• • C—CHEMISTRY; METALLURGY
  • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
  • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
  • C11D1/00—Detergent compositions based essentially on surface-active compounds; Use of these compounds as a detergent
  • C11D1/88—Ampholytes; Electroneutral compounds
  • C11D1/90—Betaines
• • C—CHEMISTRY; METALLURGY
  • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
  • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
  • C11D2111/00—Cleaning compositions characterised by the objects to be cleaned; Cleaning compositions characterised by non-standard cleaning or washing processes
  • C11D2111/10—Objects to be cleaned
  • C11D2111/14—Hard surfaces

Definitions

• the present invention relates to liquid dishwashing detergent compositions containing amylase enzymes and which exhibit excellent greasy soil removal performance and having a high pH of greater than about 8.
• LDL Light-duty liquid
• gel detergent compositions useful for manual dishwashing are well known in the art. Such products are generally formulated to provide a number of widely diverse performance and aesthetics properties and characteristics.
• liquid or gel dishwashing products must be formulated with types and amounts of surfactants and other cleaning adjuvants that will provide acceptable solubihzation and removal of food soils, especially grease, fat and other hydrophobic soils, from dishware being cleaned with aqueous solutions of these dishwashing products.
• Heavily soiled dishware can present special problems du ⁇ ng manual dishwashing operations.
• Kitchen articles such as plates, utensils, pots, pans, crockery and the like may be heavily soiled m the sense that relatively large amounts of food soils and residues, particularly polymerized and burnt-on greasy soils, may still be found on the dishware at the time such soiled dishware is to be manually washed.
• Such soil residues may be tenaciously adhered or stuck to the surfaces of the dishware to be cleaned as the result of the food soils present, the nature of the dishware surfaces involved or even the type of cooking operations to which the soiled dishware had been subjected.
• Starch-based soils are particularly prone to become tenaciously adhered to the side of kitchenware
• formulators of liquid dishwashing compositions to incorporate additional components into LDL detergents to provide consumers with improved cleaning benefits, particularly on the difficult, baked and burnt-on soils which make cleaning kitchenware labo ⁇ ous.
• One such component which can improve cleaning performance on tenacious soils is amylase enzymes.
• amylase enzymes can be extremely effective at removing starch-based soils and residues adhered to kitchen articles such as cookware and dishware.
• amylase enzymes provide excellent cleaning benefits
• it has been difficult to successfully incorporate amylases into a liquid dish ashing detergent formulation because the enzymes tend to be unstable and rapidly degrade, leaving the formulation's amylase enzyme constant at levels far too low to provide adequate cleaning benefits
• the formulation's starch-cleanmg performance will gradually deteriorate as the amylase enzymes degrade to levels insufficient to provide starch-cleaning benefits
• the present invention relates to a liquid dishwashing detergent composition
• a liquid dishwashing detergent composition comprising: (a) from about 0.0001% to about 5%, of an amylase enzyme; and (b) at least about 0.5% of a suds booster; wherein the composition has a pH of greater than about 8, preferably greater than about 9 and the detergent composition has especially desirable greasy soil removal performance when used to clean heavily soiled kitchen articles.
• LDL light duty liquid detergent composition
• ENZYMES Detergent compositions of the present invention comprise at least one amylase enzyme and (if desirable) other enzymes which provide cleaning performance benefits.
• Amylase - Amylases ( ⁇ and/or ⁇ ) can be included for removal of carbohydrate-based stains.
• Suitable amylases are Termamyl® (Novo Nordisk), Fungamyl® and BAN® (Novo Nordisk).
• the enzymes may be of any suitable origin, such as vegetable, animal, bacterial, fungal and yeast origin.
• Amylase enzymes are normally incorporated in the detergent composition at levels from about 0.0001% to about 2%, preferably from about 0 0001% to about 0.5%, more preferably from about 0.0005% to about 0.1%.
• amylase enzymes are used at very low levels- from about 0 0001 % to about 0.05%, preferably from about 0 0002% to about 0.02% Based on experience with other enzyme species, it would seem that the use of such small amounts of amylase enzymes would not enhance cleaning efficacy; but it has been determined m the present invention that appreciable cleaning benefits are obtained even at these low levels.
• liquid dishwashing composition When enzymes are used m a liquid dishwashing composition, at very low levels, m order to prevent such small amounts of enzyme from becoming quickly destabilized and destroyed it is preferable that certain enzyme destabilizing ingredients (discussed m greater detail below) are excluded from the liquid dishwashing composition.
• Amylase enzymes also include those described in W095/26397 and m co-pending application by Novo Nordisk PCT/DK96/00056.
• Other specific amylase enzymes for use m the detergent compositions of the present invention therefore include :
• ⁇ -amylases characte ⁇ sed by having a specific activity at least 25% higher than the specific activity of Termamyl® at a temperature range of 25°C to 55°C and at a pH value in the range of 8 to 10, measured by the Phadebas® ⁇ -amylase activity assay.
• Phadebas® ⁇ -amylase activity assay is desc ⁇ bed at pages 9-10, W095/26397.
• ⁇ -amylases according (a) comprising the ammo sequence shown m the SEQ ID listings m the above cited reference, or an ⁇ -amylase being at least 80% homologous with the ammo acid sequence shown in the SEQ ID listing.
• a polypeptide is considered to be X% homologous to the parent amylase if a comparison of the respective ammo acid sequences, performed via algorithms, such as the one desc ⁇ bed by
• the term "obtainable from” is intended not only to indicate an amylase produced by a Bacillus strain but also an amylase encoded by a DNA sequence isolated from such a Bacillus strain and produced in an host organism transformed w ith said DNA sequence.
• Variants of the following parent ⁇ -amylases which (I) have one of the ammo acid sequences shown in corresponding respectively to those ⁇ -amylases in (a-e), or ( ⁇ ) displays at least 80% homology with one or more of said amino acid sequences, and/or displays lmmunological cross- reactivity with an antibody raised against an ⁇ -amylase having one of said amino acid sequences, and/or is encoded by a DNA sequence which hybridizes with the same probe as a DNA sequence encoding an ⁇ -amylase having one of said amino acid sequence; in which va ⁇ ants :
• At least one ammo acid residue of said parent ⁇ -amylase has been replaced by a different ammo acid residue; and/or 3. at least one ammo acid residue has been inserted relative to said parent ⁇ -amylase; said variant having an ⁇ -amylase activity and exhibiting at least one of the following properties relative to said parent ⁇ -amylase : increased thermostabihty, increased stability towards oxidation, reduced Ca ion dependency, increased stability and/or ⁇ - amylolytic activity at neutral to relatively high pH values, increased ⁇ -amylolytic activity at relatively high temperature and increase or decrease of the isoelectric point (pi) so as to better match the pi value for ⁇ -amylase variant to the pH of the medium.
• Said va ⁇ ants are desc ⁇ bed in the patent application PCT/DK96/00056.
• amylases suitable herein include, for example, ⁇ -amylases desc ⁇ bed in GB 1,296,839 to Novo; RAPID ASE®, International Bio-Synthetics, Inc. and TERMAMYL®. Novo FUNGAMYL® from Novo is especially useful.
• Engineering of enzymes for improved stability e.g., oxidative stability, is known. See, for example J. Biological Chem., Vol. 260, No. 11, June 1985, pp. 6518-6521.
• Certain preferred embodiments of the present compositions can make use of amylases having improved stability m detergents such as automatic dishwashing types.
• oxidative stability as measured against a reference-point of TERMAMYL® m commercial use in 1993
• preferred amylases herein share the characteristic of being "stability-enhanced" amylases, characterized, at a minimum, by a measurable improvement in one or more of oxidative stability, e g , to hydrogen peroxide/tetraacetylethylenediamine in buffered solution at pH 9-10, thermal stability, e.g , at common wash temperatures such as about 60°C, or alkaline stability, e.g., at a pH from about 8 to about 1 1, measured versus the above-identified reference-point amylase.
• Stability-enhanced amylases can be obtained from Novo or from Genencor International
• One class of highly preferred amylases herein have the commonality of being derived using site-directed mutagenesis from one or more of the Bacillus amylases, especially the Bacillus ⁇ -amylases, regardless of whether one, two or multiple amylase strains are the immediate precursors Oxidative stability-enhanced amylases vs. the above-identified reference amylase are preferred for use, especially in bleaching, more preferably oxygen bleaching, as distinct from chlorine bleaching, detergent compositions herein.
• Such preferred amylases include (a) an amylase according to the hereinbefore incorporated WO 9402597, Novo, Feb. 3, 1994, as further illustrated by a mutant in which substitution is made, using alamne or threonme, preferably threonine, of the methiomne residue located in position 197 of the B. licheniformis alpha-amylase, known as TERMAMYL®, or the homologous position variation of a similar parent amylase, such as B. amylohquefaciens, B. subtihs, or B.
• Met was substituted, one at a time, in positions 8, 15, 197, 256, 304, 366 and 438 leading to specific mutants, particularly important being M197L and M197T with the M197T variant being the most stable expressed variant. Stability was measured in CASCADE® and SUNLIGHT®; (c) particularly preferred amylases herein include amylase va ⁇ ants having additional modification in the immediate parent as desc ⁇ bed in WO 9510603 A and are available from the assignee, Novo, as DURAMYL®.
• oxidative stability enhanced amylase include those described in WO 9418314 to Genencor International and WO 9402597 to Novo Any other oxidative stability-enhanced amylase can be used, for example as de ⁇ ved by site-directed mutagenesis from known chime ⁇ c, hybrid or simple mutant parent forms of available amylases. Other preferred enzyme modifications are accessible See WO 9509909 A to Novo.
• amylase enzymes provide excellent cleaning benefits when included in a detergent composition, it is preferred that they be used as one part of a cocktail of conventional applicable enzymes like protease, amylase, hpase, cutinase and/or cellulase.
• Enzymes when present in the compositions at from about 0 0001% to about 5% of active enzyme by weight of the detergent composition
• Other enzymes suitable for use in the present invention include cellulases, hemicellulases, peroxidases, proteases, hpases, cutinases, pectinases, xylanases, reductases, oxidases, phenoloxidases.
• Preferred proteolytic enzymes are selected from the group consisting of Alcalase ® (Novo Indust ⁇ A/S), BPN', Protease A and Protease B (Genencor), and mixtures thereof Protease B is most preferred.
• the compositions of the present invention will have a pH of at least about 8, preferably at least about 9, more preferably at least about 9.5.
• the pH of the present detergent compositions will be less than about 12, more preferably less than about 1 1.
• Amylase enzymes are especially effective as part of a high pH detergent composition. Without intending to be limited by theory it is believed that the increased efficacy of amylases at high pH is because amylase enzymes are effective only against hydrated soils and the increased alkalinity of the detergent composition increases the hydration of the tenacious, baked-on starch soils thereby increasing the catalysis of starch hydrolysis.
• high pH detergent compositions improves overall dish cleaning performance, regardless of the presence of amylase enzymes, because the higher pH environment increases elimination of soil mate ⁇ als by hydrolysis Those hydrolyzed soils which are not completely eliminated are typically loosened and softened to such a degree that amylase enzymes, as well as other cleaning adjuvants, can more readily work to eliminate them.
• dishwashing compositions of the invention will be subjected to acidic stresses created by food soils when put to use, 1 e , diluted and applied to soiled dishes, so if a composition with a pH greater than 8 or 9 is to be more effective, it preferably should contain a buffe ⁇ ng agent capable of providing a generally more alkaline pH in the composition and in dilute solutions.
• Dishwashing compositions of the present invention will thus contain from about 0.1% to 15%, preferably from about 1% to 10%, most preferably from about 2% to 8%, by weight, of a buffering agent.
• the pKa value of this buffering agent should be about 0.5 to 1 0 pH units below the desired pH value of the composition ( with the pKa value determined as described above) Under these conditions the buffering agent most effectively controls the pH while using the least amount thereof.
• the buffering agent may be an active detergent in its own right, or it may be a low molecular weight, organic or inorganic material that is used m this composition solely for maintaining an alkaline pH.
• Preferred buffe ⁇ ng agents for compositions of this invention are nitrogen-containing mate ⁇ als. Some examples are amino acids such as lysme or lower alcohol amines like mono-, di-, and t ⁇ -ethanolamine.
• the diammes, described m detail above, also act as buffe ⁇ ng agents and are preferred buffering agents
• Preferred inorganic buffers/alkalinity sources include the alkali metal carbonates, alkali metal hydroxides and alkali metal phosphates, e.g., sodium carbonate, sodium hydroxide, sodium polyphosphate.
• Preferred buffe ⁇ ng system for use in the present detergent compositions include a combination of 0.5 % diamme and 2.5 % citrate and a combination of 0.5 % diamine, 0.75 % potassium carbonate and 1 75 % sodium carbonate.
• Other preferred nitrogen-containing buffe ⁇ ng agents are T ⁇ (hydroxymethyl)am ⁇ no methane (HOCH 2 ) 3 CNH 3 (TRIS), 2-ammo-2 -ethyl- 1,3- propanediol, 2-am ⁇ no-2-methyl-propanol, 2-ammo-2-methyl-l,3-propanol, disodium glutamate, N-methyl diethanolamide, 1,3-d ⁇ ammo-propanol N,N'-tetra-methyl-l,3-d ⁇ am ⁇ no-2-propanol, N,N- b ⁇ s(2-hydroxyethyl)glycme (bicme) and N-t ⁇ s (hydroxymethyl)methyl glycme (t ⁇ cine).
• compositions of this invention comprise from about 5 % to about 90 %, more preferably from about 25 % to about 70 % by weight surfactant.
• anionic surfactants useful in the present invention are preferably selected from the group consisting of linear alkylbenzene sulfonate, alpha olefin sulfonate, paraffin sulfonates, alkyl ester sulfonates, alkyl sulfates, alkyl alkoxy sulfate. alkyl sulfonates, alkyl alkoxy carboxylate, alkyl alkoxylated sulfates, sarcosinates, taunnates, and mixtures thereof.
• An effective amount typically from about 0.5% to about 90%, preferably about 5% to about 50%, more preferably from about 10 to about 30%, by weight of anionic detersive surfactant can be used in the present invention.
• anionic surfactants may be found in copendmg provisional patent application of Chand ⁇ ka Kastu ⁇ et al., entitled “Liquid Detergent Compositions Comp ⁇ sing Polymeric Suds Enhancers", having P & G Case No. 6938P, serial no. 60/066,344 and filed on November 21, 1997, which is hereby incorporated by reference. Further examples of suitable anionic surfactants are given in "Surface Active Agents and Detergents" (Vol. I and LI by
• Amine oxides are semi-polar nomonic surfactants and include water-soluble amme oxides containing one alkyl moiety of from about 10 to about 18 carbon atoms and 2 moieties 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 one alkyl moiety of from about 10 to about 18 carbon atoms and 2 moieties 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 one alkyl moiety of from about 10 to about 18 carbon atoms and a moiety selected from the group consisting of alkyl and hydroxyalkyl moieties of from about 1 to about 3 carbon atoms.
• Semi-polar amphote ⁇ c detergent surfactants including amine oxide surfactants are discussed in greater detail in U.S. Pat. No. 5,167,872, issued December 1, 1992, to Panche ⁇ et al. These amme oxide surfactants in particular include Ci o-Cjg alkyl dimethyl amine oxides and
• amine oxides such as propyl amme oxides, represented by the formula.
• R is an alkyl. 2 -hydroxyalkyl, 3-hydroxyalkyl, or 3-alkoxy-2-hydroxypropyl radical in which the alkyl and alkoxy, respectively, contain from about 8 to about 18 carbon atoms, R 2 and R 3 are each methyl, ethyl, propyl, isopropyl, 2-hydroxyethyl, 2-hydroxypropyl, or 3- hydroxypropyl and n is from 0 to about 10.
• amphote ⁇ c surfactants are given in "Surface Active Agents and Detergents" (Vol. I and II by Schwartz, Perry and Berch), hereby incorporated by reference.
• the amphote ⁇ c surfactant is present in the composition in an effective amount, more preferably from about 0.1% to about 20%, even more preferably about 0.1% to about 15%, even more preferably still from about 0.5% to about 10%,by weight.
• Noniomc Surfactants Examples of nomonic detergent surfactants that are useful in the present invention are generally disclosed in U.S. Pat. No. 3,929,678, Laugh n et al., issued Dec 30, 1975, at column 13, line 14 through column 16, line 6, incorporated herein by reference. These include: (I) the polyethylene, polypropylene, and polybutylene oxide condensates of alkyl phenols.;
• (n) alcohol ethoxylates which are the condensation products of aliphatic alcohols with from about 1 to about 25 moles of ethylene oxide. They are represented by the general formula: R(OCH 2 CH 2 ) n OH .
• Secondary Surfactants - Secondary detersive surfactant can be selected from the group consisting of cationics, ampholytics, zwitterionics, and mixtures thereof
• the present detergent compositions can be formulated to be used in the context of laundry cleaning or in other different cleaning applications, particularly including dishwashing.
• the particular surfactants used can therefore vary widely depending upon the particular end-use envisioned.
• Suitable secondary surfactants are described in detail in the copending provisional patent application of Chand ⁇ ka Kastu ⁇ et al., entitled “Liquid Detergent Compositions Comp ⁇ smg Polymeric Suds Enhancers", having P & G Case No. 6938P, application se ⁇ al no. 60/066,344, incorporated above.
• Diam es - Diamines used herein in detergent compositions in combination with detersive surfactants at levels and ratios which are effective for achieving at least a directional improvement in cleaning performance.
• usage levels can vary depending not only on the type and seventy of the soils and stains, but also on the wash water temperature, the volume of wash water and the length of time the dishware is contacted with the wash water. Since the habits and practices of the users of detergent compositions show considerable variation, the composition will preferably contain at least about 0.1%, more preferably at least about 0.2%, even more preferably, at least about 0.25%, even more preferably still, at least about 0.5% by weight of said composition of diamine.
• composition will also preferably contain no more than about 15%, more preferably no more than about 10%, even more preferably, no more than about 6%, even more preferably, no more than about 5%, even more preferably still, no more than about 1.5% by weight of said composition of diamine.
• this invention provides a means for enhancing the removal of greasy/oily soils by combining the specific diammes of this invention with surfactants.
• Greasy/oily "everyday" soils are a mixture of t ⁇ glyce ⁇ des, hpids, complex polysaccha ⁇ des, fatty acids, inorganic salts and protemaceous matter.
• diamines in combination with amphote ⁇ c and anionic surfactants in the specific ratios discussed below, offer the benefit of improved grease and tough food cleaning which allows the elimination or reduction in the amount of divalent ions in the preferred embodiments of the present formula.
• This improved cleaning is a result of diamines' proclivity as a buffering agent to increase the alkalinity of the dishwashing composition.
• the diamines used in the present invention are substantially free from impurities. That is, by “substantially free” it is meant that the diamines are over 95% pure, i.e., preferably 97%, more preferably 99%, still more preferably 99 5%, free of impu ⁇ ties.
• impurities which may be present in commercially supplied diamines include 2 -Methyl- 1,3- diaminobutane and alkylhydropy ⁇ midine. Further, it is believed that the diammes should be free of oxidation reactants to avoid diamine degradation and ammonia formation.
• 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 draw back of this stabilization of the enzymes by the diamine is that the nitrogen compounds produced are believed to cause the malodors which can be present m diamine containing compositions. Having the diamme act as an enzyme stabilizer also prevents the diamme from providing the benefits to the composition for which it was o ⁇ ginally put m to perform, namely, grease cleaning, sudsing, dissolution and low temperature stability.
• the inventive compositions either by using components which are substantially free of as an enzyme stabilizer, because of the possible generation of hydrogen peroxide and/or by using non-diamme antioxidants even though the diamine can act malodorous compounds and the reduction m the amount of diamine available present to perform its primary role.
• Preferred organic diammes are those in which pKl and pK2 are in the range of about 8.0 to about 11.5, preferably m the range of about 8.4 to about 11, even more preferably from about 8.6 to about 10.75.
• Other preferred mate ⁇ als are the primary/primary diammes with alkylene spacers ranging from C4 to C8. In general, it is believed that primary diam
• pKal and pKa2 are quantities of a type collectively known to those skilled m the art as “pKa” pKa is used herein m the same manner as is commonly known to people skilled in the art of chemistry. Values referenced herein can be obtained from literature, such as from "Critical Stability Constants.
• R 3 S R 5 wherein R2.5 are independently selected from H, methyl, -CH3CH2, and ethylene oxides; C x and C v are independently selected from methylene groups or branched alkyl groups where x+y is from about 3 to about 6; and A is optionally present and is selected from electron donating or withdrawing moieties chosen to adjust the diamme pKa's to the desired range. If A is present, then x and y must both be 1 or greater.
• the LDL compositions contain anionic surfactant, amphote ⁇ c surfactants, and diamme m a ratio of anionic: amphotenc: diamme from about 100 40: 1 to about 9:0.5: 1, by mole. preferably the ratio of the anionic: amphotenc diamine is from about 27:8- 1 to about 11 :3: 1, by mole. It has been found that detergent compositions containing anionic surfactant, amphotenc surfactant and diamme in this specific ratio range provide improved low temperature stability, deliver better grease removal and tough food cleaning benefits as well as improved hard water cleaning.
• compositions containing alkyl ethoxy carboxylates and/or polyhydroxy fatty acid amide improves the cleaning of greasy soils for various compositions, i.e. compositions containing alkyl ethoxy carboxylates and/or polyhydroxy fatty acid amide. This is especially true when the compositions are used in softened water that contains few divalent ions. It is believed that calcium and/or magnesium ions increase the packing of the surfactants at the oil/water interface, thereby reducing mterfacial tension and improving grease cleaning.
• compositions of the invention hereof containing magnesium and/or calcium ions exhibit good grease removal, manifest mildness to the skin, and provide good storage stability.
• the magnesium or calcium ions are added as a hydroxide, chloride, acetate, formate, oxide or nitrate salt to the compositions of the present invention.
• the amount of calcium or magnesium ions present in compositions of the invention will be dependent upon the amount of total surfactant present therein, including the amount of alkyl ethoxy carboxylates and polyhydroxy fatty acid amide.
• the molar ratio of calcium ions to total anionic surfactant is from about 0.25: 1 to about 2:1 for compositions of the invention.
• Formulating such divalent ion-containing compositions in alkaline pH matrices may be difficult due to the incompatibility of the divalent ions, particularly magnesium, with hydroxide ions.
• divalent ions and alkaline pH are combined with the surfactant mixture of this invention, grease cleaning is achieved that is superior to that obtained by either alkaline pH or divalent ions alone.
• du ⁇ ng storage the stability of these compositions becomes poor due to the formation of hydroxide precipitates. Therefore, chelatmg agents discussed herein below may also be necessary.
• the ions are present in the compositions hereof at an active level of from about 0.1% to 4%, preferably from about 0.3% to 3.5%, more preferably from about 0.5% to 1%, by weight.
• an active level of from about 0.1% to 4%, preferably from about 0.3% to 3.5%, more preferably from about 0.5% to 1%, by weight.
• either species of divalent ion provides benefits when included in a detergent composition, preferably the detergent compositions of the present invention contain no calcium ions.
• Solvents - contain either diols or polymenc glycols or a mixture of both diols and polymenc glycols (polymenc glycols are composed of ethylene oxide (EO) and propylene oxide (PO) groups). In addition to diols and polymenc glycols, a variety of other water-miscible liquids such as lower alkanols, diols.
• polymenc glycols are composed of ethylene oxide (EO) and propylene oxide (PO) groups.
• EO ethylene oxide
• PO propylene oxide
• diols and polymenc glycols a variety of other water-miscible liquids such as lower alkanols, diols.
• the composition will preferably contain at least about 0.01%, more preferably at least about 0.5%, even more preferably still, at least about 1% by weight of the composition of solvent.
• the composition will also preferably contain no more than about 20%, more preferably no more than about 10%, even more preferably, no more than about 8% by weight of the composition of solvent.
• Suds Booster Another component which may be included in the composition of this invention is a suds stabilizing surfactant (suds booster) at a level of at least about 0.5%, preferably at least about 2%, more preferably at least about 5%.
• the composition will also contain no more than about 20%, preferably no more than about 15%, more preferably, no more than about 10% of said suds booster.
• Suds stabilizing surfactants operable in the instant composition are: sultanas, complex betames, betames, ethylene oxide condensates, fatty acid amides, amme oxide semi-polar noniomcs, and catiomc surfactants.
• suds boosters are the polymeric suds stabilizers disclosed in the provisional application of Clarke et al., entitled “Diols and Polymenc Glycols for Improved Dishwashing Detergent Compositions", having P & G Case No. 7408 provisional se ⁇ al no. 60/119,044, filed on February 8, 1999, which is hereby incorporated by reference.
• Builder Cosmetic (Chelants) -
• the compositions according to the present invention may further compnse builders.
• a general desc ⁇ ption of builder materials is contained m U. S. Pat. No. 5,990,065, to Vinson et al., issued Nov. 23, 1999, which is hereby incorporated by reference. If detergency builder salts are included, they will be included in amounts of from 0.5 % to 50 % by weight of the composition preferably from 5% to 30% and most usually from 5% to 25% by weight.
• the detergent compositions will further preferably compnse one or more detersive adjuncts selected from the following: soil release polymers, polymenc dispersants, polysaccha ⁇ des, abrasives, bactencides and other antimicrobials, tarnish inhibitors, builders, enzymes, dyes, buffers, antifungal or mildew control agents, insect repellents, perfumes, hydrotropes, thickeners, processing aids, b ⁇ ghteners, anti-corrosive aids, stabilizers antioxidants and chelants
• a wide variety of other ingredients useful 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 sudsmg is desired, suds boosters such as the C I Q-C I 6 alkanolamides can be incorporated into the compositions, typically at 1%-10% levels The C J Q-
• the present liquid dishwashing detergent compositions may optionally be in the form of either a microemulsion or a bicontmuous microemulsion.
• microemulsion or “conventional microemulsion” it is meant a thermodynamically stable mixture of oil and water in which a discontinuous domain is suspended in a continuous domain.
• the discontmous domain is in the form of spherical droplets having radii of between 100 and 1000 A.
• the discontinuous domain is oil and the continuous domain is water, it is an oil- m-water microemulsion.
• the discontinuous domain is water and the continuous domain is oil, it is a water-m-oil microemulsion.
• bicontmuous microemulsion it is meant a thermodynamically stable mixture of oil and water wherein two continuous, interconnecting and separate domains, separated by a surfactant interface, are present rather than there being both a continuous and a discontinuous domain.
• a bicontmuous microemulsion is classified as a Wmsor Type III microemulsion. P. A Wmsor, Chem. Rev 68, p. 3-6 (1968); Surfactant Science Series, Volume 6 Emulsions and Emulsion Technology Part 1 (edited by Kenneth J. Lissant), p. 191-92 Marcel Dekker, New York (1997).
• compositions of this invention can be used to form aqueous washing solutions for use hand dishwashing. Generally, an effective amount of such compositions is added to water to form such aqueous cleaning or soaking solutions. The aqueous solution so formed is then contacted with the dishware, tableware, and cooking utensils.
• An effective amount of the detergent compositions herein added to water to form aqueous cleaning solutions can compnse amounts sufficient to form from about 500 to 20,000 ppm of composition in aqueous solution. More preferably, from about 800 to 5,000 ppm of the detergent compositions herein will be provided in aqueous cleaning liquor.
• a light-duty liquid dishwashing detergent formula having the following composition is prepared:
• Example 1 Example 2 Example 3 Example 4 Example 5
• Noniomc 3 2.4 3.0 2.0 3.5 3.0
• Noniomc may be either C ⁇ Alkyl ethoxylated surfactant containing 9 ethoxy groups or Cio Alkyl ethoxylated surfactant containing 8 ethoxy groups.

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