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
  • C11D3/43—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
  • 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
  • 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 or gel dishwashing detergent compositions suitable for use in manual dishwashing operations.
• These compositions contain amphote ⁇ c and anionic surfactants, organic diammes, and solvents selected from the group consisting of diols and polymeric glycols and mixtures thereof as well as other detergent adjuvants
• These components serve to impart preferred food soil cleaning, handling and sudsmg characteristics to such dishwashing detergent products.
• Light-duty liquid (LDL) or 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 characte ⁇ stics.
• 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 greasy soils, from dishware being cleaned with, or m aqueous solutions formed from such products.
• formulators of liquid dishwashing compositions to incorporate additional components into LDL detergents to provide consumers with improved cleaning benefits.
• liquid dishwashing products must be formulated to be physically stable and free of adverse heterogeneity.
• “Physical stability” in this sense refers to the tendency of a liquid composition to remain as a homogeneous solution rather than having one or more components precipitate (if the discontinuous phase is a solid) or separate (if the discontinuous phase is a liquid) out of the liquid.
• a useful detergent composition is one that is free of inhomogeneties and is stable under a variety of different service conditions and storage temperatures— previous formulators have found cold temperature stability particularly difficult to obtam Physical stability not only enhances the appearance and hence the consumer perception of the product, but is also essential to providing effective cleaning performance.
• liquid dishwashing products should be formulated to have a viscosity that makes the use of the product convenient and practicable
• a liquid dishwashing composition should not be so thick that it cannot be easily poured out of its container and at the same time not so thin that it is difficult to concentrate onto the surface of a sponge or kitchen article.
• Liquid dishwashing compositions should also have a favorable "dilution profile", meaning that as the liquid dishwashing product is further diluted with water, the composition decreases in viscosity.
• Dissolution is another important attribute of liquid dishwashing products.
• dissolution is meant the rate at which the liquid dishwashing product mixes with water.
• a detergent product mix quickly with water so that its detersive benefits are immediately available to the consumer, thus minimizing the amount of time he or she must devote to cleaning tasks.
• liquid dishwashing products which include enzymes so that the enzymes are not degraded or decomposed by their interaction with other detergent ingredients.
• Enzymes are important components of dishwashing compositions because they offer improved cleaning benefits on protein-based soils and have also been shown to provide consumers with a mildness or skin feel/appearance advantage over other similar detergent compositions which do not contain enzymes.
• 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.
• enzymes are active in the presence of water and because most liquid dishwashing compositions are aqueous, care must be taken that the enzymes are not activated du ⁇ ng storage and thus depleted by the time the LDL composition is ready for use.
• diols prepared according to the present invention and desc ⁇ bed in greater detail below have been shown to improve the physical stability of liquid dishwashing compositions even at high pHs (above 10.0) and low temperatures where typically it is likely that certain components will separate out from the composition solution and form inhomogeneities. These diols have also been shown to improve enzymatic stability even in compositions with high water levels.
• these diols like other solvents, provide stabilizing benefits to dishwashing compositions, but unlike other solvents (e.g. ethanol), do not thm the dishwashing compositions in which they are included. This allows a formulator to stabilize dishwashing compositions over a greater range of viscosities, because the diols provide formula stability benefits without the corresponding cost of decreasing formula viscosity.
• solvents e.g. ethanol
• the detergent compositions according to the first aspect of the present invention comprise: (a) a low molecular weight organic diamme having a pKl and a pK2, wherein the pKl and the pK2 of said diamme are both in the range of from about 8.0 to about 11.5; (b) an anionic surfactant; (c) an amphote ⁇ c 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:
• PO propylene oxide group
• EO represents an ethylene oxide group
• x+y is from about 17 to 68
• x/(x+y) is from about 0.25 to 1.0
• the pH (as measured as 10% aqueous solution) is from about 5.0 to about 12.5 and the mole ratio of said anionic surfactant to said amphote ⁇ c surfactant to said diamme is from about 100:40: 1 to about 9:0.5: 1
• a detergent composition suitable for use in hand dishwashing said composition comp ⁇ sing: (a) from about 0.1% to about 5%, by weight of a diamme having a molecular weight less than or 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 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 polyme ⁇ c glycols being those described above in the paragraph on the first aspect of the invention.
• the detergent composition also includes: (f) from about 0.01% to about 5%, by weight, of a polyme ⁇ c suds stabilizer selected from the group consisting of: l) homopolymers of (N,N-d ⁇ alkylam ⁇ no)alkyl acrylate esters having the formula:
• each R is independently hydrogen, Cj-Cg alkyl, and mixtures thereof, R' is hydrogen, C ⁇ -C alkyl, and mixtures thereof, n is from 2 to about 6; n) copolymers of (l) and
• R 1 is hydrogen, C1-C6 alkyl, and mixtures thereof; provided that the ratio of (n) to (l) is from about 2 to 1 to about 1 to 2; and wherein said polyme ⁇ c suds stabilizer has a molecular weight of from about 1,000 to about 2,000,000 daltons; and
• the pH (as measured as 10% aqueous solution) is from about 5.0 to about 12.5 and wherein mole ratio of said anionic surfactant to said amphote ⁇ c surfactant to said diamme is from about 27:8.1 to about 11 :3: 1.
• a detergent composition suitable for use m hand dishwashing comprising: (a) from about 0.1% to about 5%, by weight, of an organic diamme having a molecular weight less than or 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 amphote ⁇ c surfactant; (d) from about 0.1 % to about 10.0 %, by weight, of a buffering agent; (e) from about 0.1 % to about 1.5 %, by weight, of an alkali metal inorganic salt; and (f) from about 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 polyme ⁇ c glycols being those described above.
• the pH (as measured as 10% aqueous solution) is from about 10 to about 12 and the mole ratio of said anionic surfactant to said amphote ⁇ c surfactant to said diamme is from about 27.8: 1 to about 1 1 :3: 1. All parts, percentages and ratios used herein are expressed as percent weight unless otherwise specified. All documents cited are, in relevant part, incorporated herein by reference. DETAILED DESCRIPTION OF THE INVENTION Definitions - The present detergent compositions comprise an "effective amount” or a "grease removal-improving amount" of individual components defined herein.
• an “effective amount” of the diammes herein and adjunct ingredients herein is meant an amount which is sufficient to improve, either directionally or significantly at the 90% confidence level, the performance of the cleaning composition against at least some of the target soils and stains.
• an “effective amount” of the diammes herein and adjunct ingredients herein is meant an amount which is sufficient to improve, either directionally or significantly at the 90% confidence level, the performance of the cleaning composition against at least some of the target soils and stains.
• the formulator will use sufficient diamme to at least directionally improve cleaning performance against such stains.
• ethylene oxide group it is meant the following structure:
• LDL light-duty liquid
• a detergent composition which is employed in manual (i.e. hand) dishwashing.
• the present liquid detergent compositions contain either diols or polyme ⁇ c glycols or a mixture of both diols and polyme ⁇ c glycols.
• Diols suitable for use in the present invention have the following formula.
• Preferred diols include propylene glycol, 1,2 hexanediol, 2-ethyl-l,3-hexaned ⁇ ol and 2,2,4-trimethyl-l,3-pentanediol.
• the present compositions will comprise at least about 0 5 %, more preferably at least about 1%, even more preferably still, at least about 3% by weight of the composition of diols.
• 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 6% by weight of the composition of diols.
• Polyme ⁇ c 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 moieties to the ends of polypropylene glycol chains.
• Polyme ⁇ c gycols suitable for use in the present invention are of the following formula:
• a preferred polymeric glycol is a polyproylene glycol (corresponding to when y « 0) having an average molecular weight of between about 1000 to about 5000, more preferably between about 2000 to about 4000, most preferably about 2000 to about 3000.
• the present liquid detergent compositions will contain at least about 0.25 %, more preferably at least about 0.5 %, even more preferably still, at least about 0.75 % by weight of the composition of polyme ⁇ c glycols.
• the composition will also preferably contain no more than about 5 %, more preferably no more than about 3 %, even more preferably, no more than about 2 % by weight of the composition.
• a diol and/or an alkali metal inorganic salt such as sodium chlo ⁇ de.
• Suitable amounts of diols to provide physical stability are in the amounts in the ranges found above, while a suitable amount of an alkali metal lnorga c salt is at least about 0 1 % and less than about 1.5 %, preferably less than about 0.8 % by weight of the composition.
• diols can improve the physical and enzymatic stability of a liquid dishwashing composition.
• diols provide important stabilizing benefits to certain polymer suds stabilizers and enzymes. Both polymer suds stabilizers and enzymes can provide important benefits by their incorporation.
• diols provide enzyme stabilizing benefits by limiting the activity of enzymes in the liquid dishwashing composition du ⁇ ng storage. Enzymes require water for optimal performance, thus deactivation is accomplished by reducing the amount of free water interacting with the enzyme by displacing a portion of the water with the diols described above which are completely miscible with water. Upon use, the liquid dishwashing composition is significantly diluted with water, thus providing the enzyme with a water environment conducive to optimal activity and performance.
• the present invention includes a carrier/solvent system which may consist of one or more of the following ingredients: diols and polymeric glycols as desc ⁇ bed above, water, alkali metal inorganic salts and one or more of the conventional solvents disclosed below.
• 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.
• solvents may be used in conjunction with an aqueous liquid earner, such as water, or they may be used without any aqueous liquid earner being present.
• Solvents are broadly defined as compounds that are liquid at temperatures of 20°C-25°C and which are not considered to be surfactants. One of the distinguishing features is that solvents tend to exist as discrete entities rather than as broad mixtures of compounds. Examples of suitable solvents for the present invention include ethanol, propanol, isopropanol, 2-methyl pyrro dinone, benzyl alcohol and morphohne n-oxide. Preferred among these solvents are ethanol and isopropanol.
• Suitable solvents for use herein include ethers and diethers having from 4 to 14 carbon atoms, preferably from 6 to 12 carbon atoms, and more preferably from 8 to 10 carbon atoms.
• suitable solvents are glycols or alkoxylated glycols, alkoxylated aromatic alcohols, aromatic alcohols, aliphatic branched alcohols, alkoxylated aliphatic branched alcohols, alkoxylated linear C1-C5 alcohols, linear C1-C5 alcohols, C8-C14 alkyl and cycloalkyl hydrocarbons and halohydrocarbons, C6-C16 glycol ethers and mixtures thereof.
• glycols according to the formula: HO-CR1R2-OH wherein Rl and R2 are independently H or a C2-C10 saturated or unsarurated aliphatic hydrocarbon chain and/or cyclic are suitable and can be used herein.
• Rl and R2 are independently H or a C2-C10 saturated or unsarurated aliphatic hydrocarbon chain and/or cyclic are suitable and can be used herein.
• One such suitable glycol is dodecaneglycol.
• Suitable alkoxylated glycols which can be used herein are according to the formula
• R — (A) n -R -OH wherein R is H, OH, a linear saturated or unsarurated alkyl of from 1 to 20 carbon atoms, preferably from 2 to 15 and more preferably from 2 to 10, wherein R 1 is H or a linear saturated or unsarurated alkyl of from 1 to 20 carbon atoms, preferably from 2 to 15 and more preferably from 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.
• Suitable alkoxylated glycols to be used herein are methoxy octadecanol and or ethoxyethoxyethanol.
• Suitable aromatic alcohols which can be used herein are according to the formula R-OH wherein R is an alkyl substituted or non-alkyl substituted aryl group of from 1 to 20 carbon atoms, preferably from 1 to 15 and more preferably from 1 to 10.
• R is an alkyl substituted or non-alkyl substituted aryl group of from 1 to 20 carbon atoms, preferably from 1 to 15 and more preferably from 1 to 10.
• a suitable aromatic alcohol to be used herein is benzyl alcohol.
• Suitable aliphatic branched alcohols which can be used herein are according to the formula R-OH wherein R is a branched saturated or unsarurated alkyl group of from 1 to 20 carbon atoms, preferably from 2 to 15 and more preferably from 5 to 12.
• Particularly suitable aliphatic branched alcohols to be used 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 branched saturated or unsarurated alkyl group of from 1 to 20 carbon atoms, preferably from 2 to 15 and more preferably from 5 to 12, wherein A is an alkoxy group preferably butoxy, propoxy and/or ethoxy, and n is an integer of from 1 to 5, preferably 1 to 2.
• Suitable alkoxylated aliphatic branched alcohols include 1- methylpropoxyethanol and/or 2-methylbutoxyethanol.
• Suitable linear C1-C5 alcohols which can be used herein are according to the formula R- OH wherein R is a linear saturated or unsarurated alkyl group of from 1 to 5 carbon atoms, preferably from 2 to 4.
• Suitable linear d-C 5 alcohols are methanol, ethanol, propanol or mixtures thereof.
• Suitable solvents include, but are not limited to, butyl diglycol ether (BDGE), butylt ⁇ glycol ether, ter amilic alcohol and the like. Particularly preferred solvents which can be used herein are butoxy propoxy propanol, butyl diglycol ether, benzyl alcohol, butoxypropanol, ethanol, methanol, isopropanol and mixtures thereof.
• BDGE butyl diglycol ether
• benzyl alcohol butoxypropanol
• ethanol ethanol
• methanol isopropanol and mixtures thereof.
• Suitable solvents for use herein include propylene glycol de ⁇ vatives such as n- butoxypropanol or n- butoxypropoxypropanol, water-soluble CARBITOL R solvents or water- soluble CELLOSOLVE R solvents; water-soluble CARBITOL R solvents are compounds of the 2-(2-alkoxyethoxy)ethanol class wherein the alkoxy group is de ⁇ ved from ethyl, propyl or butyl; a preferred water-soluble carbitol is 2-(2-butoxyethoxy)ethanol also known as butyl carbitol.
• Water-soluble CELLOSOLVE R solvents are compounds of the 2-alkoxyethoxy ethanol class, with 2-butoxyethoxyethanol being preferred.
• Suitable solvents include benzyl alcohol, and diols such as 2-ethyl-l, 3-hexaned ⁇ ol and 2,2,4-t ⁇ methyl-l,3-pentaned ⁇ ol 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 comp ⁇ sing ether derivatives of mono-, di- and tn-ethylene glycol, butylene glycol ethers, and mixtures thereof.
• the molecular weights of these solvents are preferably less than 350, more preferably between 100 and 300, even more preferably between 115 and 250.
• preferred solvents include, for example, mono-ethylene glycol n-hexyl ether, mono-propylene glycol n-butyl ether, and t ⁇ -propylene glycol methyl ether.
• Ethylene glycol and propylene glycol ethers are commercially available from the Dow Chemical Company under the tradename "Dowanol” and from the Arco Chemical Company under the tradename "Arcosolv”.
• Other preferred solvents including mono- and di-ethylene glycol n-hexyl ether are available from the Union Carbide company.
• Diamines used herein in detergent compositions in combination with detersive surfactants at levels which are effective for achieving at least a directional improvement in cleaning performance.
• usage levels can vary depending not only on the type and severity 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.
• 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 diamme.
• the 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 diamme.
• 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 diam es' proclivity as a buffe ⁇ ng agent to increase the alkalinity of the dishwashing composition.
• the supe ⁇ or rate of dissolution achieved by divalent ion elimination even allows the formulator to make hand dishwashing detergents, especially compact formulations, at even significantly higher viscosities (e.g., 1,000 centipoise or higher) than conventional formulations while maintaining excellent dissolution and cleaning performance.
• compact or “Ultra” is meant detergent formulations with reduced levels of water compared to conventional liquid detergents.
• the level of water is less than 50%, preferably less than 30% by weight of the liquid dishwashing detergent compositions.
• Said concentrated products provide advantages to the consumer, who has a product which can be used in lower amounts and to the producer, who has lower shipping costs.
• a suitable water level is less than about 85 %, more preferably less than about 70 % by weight of the liquid dishwashing detergent compositions.
• the diammes used m the present invention are substantially free from impu ⁇ ties. That is, by “substantially free” it is meant that the diam es are over 95% pure, i.e., preferably 97%, more preferably 99%, still more preferably 99.5%, free of impu ⁇ ties.
• impu ⁇ ties which may be present m commercially supplied diamines include 2-Methyl-l,3- diaminobutane and alkylhydropy ⁇ midine. Further, it is believed that the diamines 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 in diamine containing compositions. Having the diamine act as an enzyme stabilizer also prevents the diamine from providing the benefits to the composition for which it was originally put in to perform, namely, grease cleaning, sudsing, dissolution and low temperature stability.
• the amount of hydrogen peroxide present as an impurity in 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 diamme can act malodorous compounds and the reduction in the amount of diamine available present to perform its p ⁇ mary role.
• Preferred organic diammes are those in which pKl 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 more preferably from about 8.6 to about 10.75.
• mate ⁇ als are the p ⁇ mary/p ⁇ mary diammes with alkylene spacers ranging from C4 to C8. In general, it is believed that p ⁇ mary diammes are preferred over secondary and tertiary diamines.
• pKal and pKa2 are quantities of a type collectively known to those skilled in the art as “pKa” pKa is used herein in 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: Volume 2, Amines” by Smith and Martel, Plenum Press, NY and London, 1975. Additional information on pKa's can be obtained from relevant company literature, such as information supplied by Dupont, a supplier of diamines.
• the pKa of the diammes is specified in an all-aqueous solution at 25°C and for an ionic strength between 0.1 to 0.5 M.
• the pKa is an equilib ⁇ um constant which can change with temperature and ionic strength; thus, values reported m the literature are sometimes not in agreement depending on the measurement method and conditions.
• the relevant conditions and/or references used for pKa's of this invention are as defined herein or m "Critical Stability Constants: Volume 2, Ammes”.
• 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
• 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.
• Examples of preferred diamines can be found m the copendmg provisional patent application of Phillip Kyle Vinson et al., entitled “Dishwashing Detergent Compositions Containing Organic Diammes for Improved Grease Cleaning, Sudsing, Low Temperature Stability and Dissolution", having P & G Case No. 7167P, application se ⁇ al no. 60/087,693, and filed on June 2, 1998, which is hereby incorporated by reference.
• 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, tau ⁇ nates, and mixtures thereof.
• anionic detersive surfactant 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 copending provisional patent application of Chand ⁇ ka Kastu ⁇ et al, entitled “Liquid Detergent Compositions Comprising 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 II by Schwartz, Perry and Berch).
• a va ⁇ ety of such surfactants are also generally disclosed in U.S. Patent 3,929,678, issued December 30, 1975 to Laughlm, et al. at Column 23, line 58 through Column 29, line 23.
• Suitable anionic surfactants may further be found m U.S. Pat. No. 5,415,814 issued 16 May 1995, to Ofosu-Asante et al, all of which are hereby incorporated by reference.
• Amphotenc surfactants - The amphoteric surfactants useful in the present invention are preferably selected from amine oxide surfactants.
• Amine oxides are semi -polar nonionic surfactants and include water-soluble amine 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 nonionic detergent surfactants include the amme oxide surfactants having the formula
• R ⁇ is an alkyl, hydroxyalkyl, or alkyl phenyl group or mixtures thereof containing from about 8 to about 22 carbon atoms;
• R ⁇ is an alkylene or hydroxyalkylene group containing from about 2 to about 3 carbon atoms or mixtures thereof;
• x is from 0 to about 3; and each R-> is an alkyl or hydroxyalkyl group containing from about 1 to about 3 carbon atoms or a polyethylene oxide group containing from about 1 to about 3 ethylene oxide groups.
• the R-> groups can be attached to each other, e.g., through an oxygen or nitrogen atom, to form a ⁇ ng structure.
• These amine oxide surfactants in particular include C I Q-C I ⁇ alkyl dimethyl amine oxides and Cg-Cj2 alkoxy ethyl dihydroxy ethyl amine oxides
• amine oxides such as propyl amine oxides, represented by the formula-
• Rj 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.
• a further suitable species of amine oxide semi-polar surface active agents comprise compounds and mixtures of compounds having the formula:
• Rj 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.
• R 3 wherein Rj is a C 10 .i 4 alkyl and R 2 and R 3 are methyl or ethyl. Because they are low-foaming it may also be desirable to use long chain amme oxide surfactants which are more fully described in U.S. Pat. Nos.
• amphote ⁇ c detergent surfactants that are useful in the present invention include amido propyl betaines and derivatives of aliphatic or heterocyc c secondary and ternary amines in which the aliphatic moiety can be straight chain or branched and wherein one of the aliphatic substituents contains from about 8 to about 24 carbon atoms and at least one aliphatic substituent contains an anionic water-solubilizing group.
• amphoteric surfactants are given in "Surface Active Agents and Detergents" (Vol. I and II by Schwartz, Perry and Berch), hereby incorporated by reference.
• the amphoteric sufactant 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.
• Secondary Surfactants - Secondary detersive surfactant can be selected from the group consisting of no onics, catiomcs, ampholytics, zwitte ⁇ omcs, and mixtures thereof.
• the present detergent compositions can be formulated to be used m the context of laundry cleaning or m 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 desc ⁇ bed in detail in the copending provisional patent application of Chand ⁇ ka Kastu ⁇ et al., entitled “Liquid Detergent Compositions Comprising Polyme ⁇ c Suds Enhancers", having P & G Case No. 6938P, application se ⁇ al no. 60/066,344, incorporated above. Ratio of anionic to amphoteric to diamme
• the ratio of the anionic surfactant: amphote ⁇ c- diamme is from about 100:40:1 to about 9:0.5: 1, by mole, preferably the ratio of the anionic surfactant: amphote ⁇ c: diamine is from about 27:8: 1 to about 11 :3: 1, by mole. It has been found that detergent compositions containing anionic surfactant, amphote ⁇ c surfactant and diamme m this specific ratio range provide improved low temperature stability, deliver better grease removal and tough food cleaning benefits at pH less than 12.5, and improved hard water cleaning.
• the mole ratio of anionic surfactant to diamine of greater than 9: 1 , preferably greater than 20: 1 has been found to give improved low temperature stability, deliver better grease removal and tough food cleaning benefits and improved hard water cleaning.
• compositions of the present invention may optionally contain a polyme ⁇ c suds stabilizer. These polyme ⁇ c suds stabilizers provide extended suds volume and suds duration without sacrificing the grease cutting ability of the liquid detergent compositions These polyme ⁇ c suds stabilizers are selected from.
• each R is independently hydrogen, Ci -Cg alkyl, and mixtures thereof, R 1 is hydrogen, Ci -Cg alkyl, and mixtures thereof, n is from 2 to about 6; and n) copolymers of (l) and
• R 1 IS hydrogen, C1-C6 alkyl, and mixtures thereof, provided that the ratio of (n) to (l) is from about 2 to 1 to about 1 to 2;
• the molecular weight of the polyme ⁇ c suds boosters, determined via conventional gel permeation chromatography, is from about 1,000 to about 2,000,000, preferably from about 5,000 to about 1,000,000, more preferably from about 10,000 to about 750,000, more preferably from about 20,000 to about 500,000, even more preferably from about 35,000 to about 200,000.
• the polyme ⁇ c suds stabilizer can optionally be present in the form of a salt, either an inorganic or organic salt, for example the citrate, sulfate, or nitrate salt of (N,N-d ⁇ methylam ⁇ no)alkyl acrylate ester.
• One preferred polyme ⁇ c suds stabilizer is (N,N-d ⁇ methylam ⁇ no)alkyl acrylate esters, namely
• the polymeric suds booster may be present in the composition from about 0.01% to about 15%, preferably from about 0.05% to about 10%, more preferably from about 0.1% to about 5%, by weight.
• Builder - The compositions according to the present invention may further comp ⁇ se a builder system Because builders such as citric acid and citrates impair the stability of enzymes in LDL compositions, it is desirable to include reduce the amounts or completely remove the builder salts normally utilized in LDL compositions incorporating propylene glycol as a builder. When a detergent composition includes propylene glycol solvent as a part or a whole of the detergent's earner, enzymes are more stable and smaller amounts or no builder salts are needed.
• any conventional builder system is suitable for use herein including alummosilicate mate ⁇ als, silicates, polycarboxylates and fatty acids, matenals such as ethylene-diamine tetraacetate, metal ion sequestrants such as ammopolyphosphonates, particularly ethylenediamme tetramethylene phosphonic acid and diethylene tnam e pentamethylene-phosphonic acid.
• phosphate builders can also be used herein.
• Suitable polycarboxylates builders for use herein include citric acid, preferably in the form of a water-soluble salt, derivatives of succmic acid of the formula R-CH(COOH)CH 2 (COOH) wherein R is C 10 . 2 o alkyl or alkenyl, preferably C I2 . 16 , or wherein R can be substituted with hydroxyl, sulfo sulfoxyl or sulfone substituents.
• Specific examples include lauryl succmate, mynstyl succmate, palmityl succinate 2-dodecenylsuccmate, 2- tetradecenyl succinate.
• Succinate builders are preferably used in the form of their water-soluble salts, including sodium, potassium, ammonium and alkanolammonium salts.
• Other suitable polycarboxylates are oxodisuccinates and mixtures of tartrate monosuccimc and tartrate disuccmic acid such as descnbed m US 4,663,071.
• suitable fatty acid builders for use herein are saturated or unsarurated C JO - IS fatty acids, as well as the corresponding soaps.
• Preferred saturated species have from 12 to 16 carbon atoms in the alkyl chain.
• the preferred unsarurated fatty acid is oleic acid.
• Other preferred builder system for liquid compositions is based on dodecenyl succmic acid and cit ⁇ c acid.
• 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.
• Enzymes - Detergent compositions of the present invention may further comp ⁇ se one or more enzymes which provide cleaning performance benefits.
• Said enzymes include enzymes selected from cellulases, hemicellulases, peroxidases, proteases, gluco-amylases, amylases, Upases, cutmases, pectinases, xylanases, reductases, oxidases, phenoloxidases, hpoxygenases, hgninases, pullulanases, tannases, pentosanases, malanases, ⁇ -glucanases, arabmosidases or mixtures thereof.
• a preferred combination is a detergent composition having a cocktail of conventional applicable enzymes like protease, amylase, lipase, 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
• 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 Preferred amylase enzymes include TERMAMYL®.
• DURAMYL® and the amylase enzymes those described in WO 9418314 to Genencor International and WO 9402597 to Novo Further non-hmitmg examples of suitable and preferred enzymes are disclosed m the copending application "Dishwashing Detergent Compositions Containing Organic Diammes for Improved Grease Cleaning, Suds g, Low temperature stability and Dissolution", having P & G Case No. 7167P and application serial no 60/087,693, which is hereby incorporated by reference
• divalent ions be omitted from LDL compositions prepared according to the present invention
• alternate embodiments of the present invention may include magnesium ions.
• magnesium ions offer several benefits.
• the inclusion of such divalent ions improves the cleaning of greasy soils for va ⁇ ous LDL compositions, in particular compositions containing alkyl ethoxy carboxylates and/or polyhydroxy fatty acid amide. This is especially true when the compositions are used m softened water that contains few divalent ions.
• these benefits can be obtained without the inclusion of divalent ions.
• improved grease cleaning can be achieved without divalent ions by the inclusion of organic diamines in combination with amphote ⁇ c and anionic surfactants in the specific ratios discussed above while enzymes have been shown to improve the skin mildness performance of the present LDL compositions.
• the magnesium ions are present at an active level of from about 0.01 % to 1 %, preferably from about 0.015 % to 0.5 %, more preferably from about 0.025 % to 0.1 %, by weight.
• the amount of magnesium ions present m compositions of the invention will be also dependent upon the amount of total surfactant present therein, including the amount of alkyl ethoxy carboxylates and polyhydroxy fatty acid amide.
• the magnesium ions are added as a hydroxide, chlo ⁇ de, acetate, sulfate, formate, oxide or nitrate salt to the compositions of the present invention. Because du ⁇ ng storage, the stability of these compositions becomes poor due to the formation of hydroxide precipitates in the presence of compositions containing moderate concentrations of hydroxide ions, it may be necessary to add certain chelating agents. Suitable chelatmg agents are discussed further below and in U.S. Pat. No. 5,739,092, issued Ap ⁇ l 14, 1998, to Ofosu-asante, incorporated herein by reference.
• Non-hmitmg examples of perfume ingredients useful herein can be found m the copendmg provisional patent application: "Dishwashing Detergent Compositions Containing Organic Diammes for Improved Grease Cleaning, Sudsing, Low temperature stability and
• the detergent compositions herein may also optionally contain one or more iron and or manganese chelating agents.
• chelating agents can be selected from the group consisting of ammo carboxylates, ammo phosphonates, polyfunctionally-substituted aromatic chelating agents and mixtures therein, all as hereinafter defined. Without intending to be bound by theory, it is believed that the benefit of these materials is due in part to their exceptional ability to remove iron and manganese ions from washing solutions by formation of soluble chelates.
• Ammo carboxylates useful as optional chelating agents include ethylenediaminetetrace- tates, N-hydroxyethylethylenediammet ⁇ acetates, nit ⁇ lo-t ⁇ -acetates, ethylenediamme tetrapro- p ⁇ onates, t ⁇ ethylenetetraaminehexacetates, diethylenet ⁇ aminepentaacetates, and ethanoldi- glycines, alkali metal, ammonium, and substituted ammonium salts therein and mixtures therein Ammo phosphonates are also suitable for use as chelating agents m the compositions of the invention when at lease low levels of total phosphorus are permitted in detergent compositions, and include ethylenediaminetetrakis (methylenephosphonates) as DEQUEST.
• these ammo phosphonates to not contain alkyl or alkenyl groups with more than about 6 carbon atoms.
• Polyfunctionally-substituted aromatic chelating agents are also useful m the compositions herein. See U.S. Patent 3,812,044, issued May 21, 1974, to Connor et al.
• Preferred compounds of this type in acid form are dihydroxydisulfobenzenes such as l,2-d ⁇ hydroxy-3,5-d ⁇ sulfobenzene
• EDDS ethylenediamme disuccmate
• compositions herein may also contain water-soluble methyl glycme diacetic acid (MGDA) salts (or acid form) as a chelant or co-builder.
• MGDA water-soluble methyl glycme diacetic acid
• so called "weak” builders such as citrate can also be used as chelating agents.
• these chelating agents will generally comp ⁇ se from about 0.1% to about 15% by weight of the detergent compositions herein. More preferably, if utilized, the chelating agents will comp ⁇ se from about 0.1% to about 3.0% by weight of such compositions.
• Dishwashing compositions of the invention will be subjected to acidic stresses created by food soils when put to use, i.e., diluted and applied to soiled dishes. If a composition with a pH greater than 7 is to be more effective, it preferably should contain a buffe ⁇ ng agent capable of providing a generally more alkaline pH m 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 (determined as described above
• the pKa of the buffe ⁇ ng agent should be from about 7 to about 12. Under these conditions the buffering agent most effectively controls the pH while using the least amount thereof.
• Preferred inorganic buffers/alkalmity sources include the alkali metal carbonates, alkali metal hydroxides and alkali metal phosphates, e.g., sodium carbonate, sodium hydroxide, sodium polyphosphate.
• the buffe ⁇ ng agent may be an active detergent in its own ⁇ ght, or it may be a low molecular weight, organic or inorganic matenal that is used in this composition solely for maintaining an alkaline pH.
• Preferred buffe ⁇ ng agents for compositions of this invention are nitrogen-containing materials. Some examples are ammo acids such as lysine or lower alcohol amines like mono-, di-, and t ⁇ -ethanolamme.
• the diamines desc ⁇ bed m detail above, also act as buffering agents and are preferred buffe ⁇ ng agents.
• Preferred buffering system for use in the present detergent compositions include a combination of 0.5 % diamine and 2.5 % citrate and a combination of 0.5 % diamme, 0.75 % potassium carbonate and 1.75 % sodium carbonate.
• the detergent compositions will further preferably comp ⁇ se one or more detersive adjuncts selected from the following: soil release polymers, polyme ⁇ c dispersants, polysaccha ⁇ des, abrasives, bacte ⁇ cides and other antimicrobials, tarnish inhibitors, builders, enzymes, dyes, buffers, antifungal or mildew control agents, insect repellents, perfumes, hydro ropes, thickeners, processing aids, suds boosters, b ⁇ ghteners, anti-corrosive aids, stabilizers antioxidants and chelants.
• soil release polymers polyme ⁇ c dispersants
• polysaccha ⁇ des polysaccha ⁇ des
• abrasives bacte ⁇ cides and other antimicrobials
• tarnish inhibitors builders, enzymes, dyes, buffers, antifungal or mildew control agents, insect repellents, perfumes, hydro ropes, thickeners, processing aids, suds boosters, b ⁇ ghteners, anti
• compositions herein 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 pi ments, solvents for liquid formulations, solid fillers for bar compositions, etc.
• suds boosters such as the C I Q-C I 6 alkanolamides can be incorporated into the compositions, typically at 1%-10% levels.
• the C10-C14 monoethanol and diethanol amides illustrate a typical class of such suds boosters.
• Use of such suds boosters with high sudsing adjunct surfactants such as the amine oxides, betames and sultames noted above is also advantageous.
• An antioxidant can be optionally added to the detergent compositions of the present invention.
• antioxidants used in detergent compositions, such as 2,6- d ⁇ -tert-butyl-4-methylphenol (BHT), carbamate, ascorbate, thiosulfate, monoefhanolam ⁇ ne(MEA), diefhanolamine, t ⁇ ethanolamine, etc. It is preferred that the antioxidant, when present, be present m the composition from about 0.001% to about 5% by weight.
• BHT 2,6- d ⁇ -tert-butyl-4-methylphenol
• MEA monoefhanolam ⁇ ne
• t ⁇ ethanolamine t ⁇ ethanolamine
• detersive ingredients employed in the present compositions optionally can be further stabilized by absorbing said ingredients onto a porous hydrophobic substrate, then coating said substrate with a hydrophobic coating.
• the detersive ingredient is admixed with a surfactant before being absorbed into the porous substrate.
• the detersive ingredient is released from the substrate into the aqueous washing liquor, where it performs its intended detersive function.
• a porous hydrophobic silica (trademark SIPERNAT D10, DeGussa) is admixed with a proteolytic enzyme solution containing 3%-5% of C13-15 ethoxylated alcohol (EO 7) nonionic surfactant.
• the enzyme/surfactant solution is 2.5 X the weight of silica.
• the resulting powder is dispersed with stir ⁇ ng in silicone oil (va ⁇ ous silicone oil viscosities in the range of 500-12,500 can be used).
• the resulting silicone oil dispersion is emulsified or otherwise added to the final detergent mat ⁇ x.
• ingredients such as the aforementioned enzymes, bleaches, bleach activators, bleach catalysts, photoactivators, dyes, fluorescers, fabnc conditioners and hydrolyzable surfactants can be "protected” for use in detergents, including liquid laundry detergent compositions.
• these hand dishwashing detergent embodiments preferably further comp ⁇ ses a hydrotrope.
• Suitable hydrotropes include sodium, potassium, ammonium or water-soluble substituted ammonium salts of toluene sulfonic acid, naphthalene sulfomc acid, cumene sulfonic acid, xylene sulfonic acid.
• liquid detergent compositions which comprise a non-aqueous earner medium can be prepared according to the disclosures of U.S. 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-A-2, 195,649; U.S. 4,988,462; U.S. 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); U.S.
• compositions can contain va ⁇ ous particulate detersive ingredients stably suspended therein.
• Such non-aqueous compositions thus compnse a LIQUID PHASE and, optionally but preferably, a SOLID PHASE, all as desc ⁇ bed in more detail hereinafter and in the cited references.
• compositions of this invention can be used to form aqueous washing solutions for use hand dishwashing.
• 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 comprise amounts sufficient to form from about 500 to 20,000 ppm of composition m aqueous solution. More preferably, from about 800 to 5,000 ppm of the detergent compositions herein will be provided m aqueous cleaning liquor.
• the following examples are illustrative of the present invention, but are not meant to limit or otherwise define its scope. All parts, percentages and ratios used herein are expressed as percent weight unless otherwise specified.
• Liqht Duty Liquid dishwashing detergents of the present invention are as follows:
• Nonionic may be either Cl 1 Alkyl ethoxylated surfactant containing 9 ethoxy groups or CIO
• Alkyl ethoxylated surfactant containing 8 ethoxy groups. Alkyl ethoxylated surfactant containing 8 ethoxy groups.
• Liqht Duty Liquid dishwashing detergents of the present invention are as follows:
• Diamme 5 0.5 0.5 0.5 0.25 0.5
• Nonionic may be either Cl 1 Alkyl ethoxylated surfactant containing 9 ethoxy groups or or CIO
• Alkyl ethoxylated surfactant containing 8 ethoxy groups 4: Polymer is (N,N-d ⁇ methylam ⁇ no)ethyl methacrylate homopolymer 5: 1,3 b ⁇ s(methylam ⁇ ne)-cyclohexane. 6: The protease is selected from- Savinase®; Maxatase®; Maxacal®; Maxapem 15®; subtihsin
• BPN and BPN' Protease B; Protease A; Protease D; Pnmase®; Durazym®; Opt ⁇ clean®;and
• Table ffl Liqht Duty Liquid dishwashing detergents of the present invention are as follows:
• Viscosity (cps @ 353 640 635 848 70F) pH @ 10% 10.8 10.8 10.80 10.8
• Nonionic may be either CIO Alkyl ethoxylated surfactant containing 8 ethoxy groups or CIO Alkyl ethoxylated surfactant containing 8 ethoxy groups.
• 5 1,3 bis(methylam ⁇ ne)-cyclohexane

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