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
  • C11D3/0094—High foaming 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
  • 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
  • C11D1/86—Mixtures of anionic, cationic, and 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
  • 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
  • C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
  • C11D3/02—Inorganic compounds ; Elemental compounds
  • C11D3/04—Water-soluble compounds
  • C11D3/046—Salts
• • 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
  • C11D1/38—Cationic compounds
  • C11D1/52—Carboxylic amides, alkylolamides or imides or their condensation products with alkylene oxides
  • C11D1/521—Carboxylic amides (R1-CO-NR2R3), where R1, R2 and R3 are alkyl or alkenyl groups
• • 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
  • C11D1/38—Cationic compounds
  • C11D1/52—Carboxylic amides, alkylolamides or imides or their condensation products with alkylene oxides
  • C11D1/525—Carboxylic amides (R1-CO-NR2R3), where R1, R2 or R3 contain two or more hydroxy groups per alkyl group, e.g. R3 being a reducing sugar rest
• • 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
  • C11D1/662—Carbohydrates or derivatives
• • 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
  • C11D1/722—Ethers of polyoxyalkylene glycols having mixed oxyalkylene groups; Polyalkoxylated fatty alcohols or polyalkoxylated alkylaryl alcohols with mixed oxyalkylele groups
• • 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

Definitions

• the present invention relates to liquid dishwashing detergent compositions suitable for use in manual dishwashing operations. These compositions contain certain detergent surfactants, suds boosters and other adjuvants which in combination serve to impart desirable low temperature stability as well as consumer preferred greasy soil cleaning and sudsing characteristics to such dishwashing detergent products.
• LDL Light-duty liquid
• 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 solubilization and removal of food soils, especially greasy soils, from dishware being cleaned with, or in aqueous solutions formed from, such products.
• LDL compositions will also desirably possess other attributes that enhance the aesthetics or consumer perception of the effectiveness of the manual dishwashing operation.
• useful hand dishwashing liquids should also employ materials that enhance the sudsing characteristics of the wash solutions formed from such products. Sudsing performance entails both the production of a suitable amount of suds in the wash water initially, as well as the formation of suds which last well into the dishwashing process.
• LDL compositions in the form of consumer dishwashing products must exhibit sufficient physical stability to withstand conditions that such products may encounter during the course of commercial trade.
• such products should maintain their physical integrity during shipping and storing, which can include exposure of the products to extremes of heat and cold (including subfreezing temperatures) as well as to prolonged periods of shipping and storage before such products are used.
• the present invention relates to especially stable, aqueous light-duty liquid detergent compositions having especially desirable greasy soil removal and sudsing performance when such compositions are used to clean soiled dishware.
• Such compositions comprise A) from about 34% to 40% of a specific type of a anionic surfactant component; B) from about 0.3% to 4.5% of a certain type of nonionic surfactant component; C) from about 4.5% to 9% of a suds booster/stabilizer; and D) from about 40% to 60% of an aqueous liquid carrier.
• the anionic surfactant component essentially comprises lightly ethoxylated alkyl ether sulfates containing from about 8 to 18 carbon atoms in the alkyl group. These lightly ethoxylated alkyl ether sulfates also contain from about 0.4 to 1.6 moles of ethylene oxide per molecule.
• the nonionic surfactant component can be selected from Cg.js polyhydroxy fatty acid amides, C$_ ⁇ alcohol ethoxylates having from about 1 to 15 moles of ethylene oxide, ethylene oxide-propylene oxide block co-polymer surfactants and combinations of these nonionic co-surfactants.
• the suds boosters/stabilizers utilized in the compositions herein are selected from betaine surfactants, hydroxy-free fatty acid amides, amine oxide semipolar nonionic surfactants, Cs_22 alkylpolyglycosides and combinations of these suds boosters/stabilizers.
• the total concentration of the Component B nonionic surfactant and the Component C suds booster/stabilizer must be at least about 7%.
• compositions of the present invention which exhibit especially desirable low temperature stability are those which also contain a source (from about 0.2% to 2%) of both Mg "1-1" and Ca “1" ions and at least 4% of a hydrotrope selected from alkali metal and calcium xylene and toluene sulfonates.
• Light-duty liquid detergent compositions of especially desirable low temperature stability also have a pH (10% solution) of 7.5 or less.
• ethoxylated alcohol nonionic surfactants will comprise no more than about 1% of the composition.
• the light-duty liquid dishwashing detergent compositions of the present invention contain four essential components. These components are:
• compositions herein A wide variety of optional ingredients can also be added to compliment the performance, aesthetics and/or stability characteristics of the compositions herein.
• compositions of the present invention refers to those compositions which are employed in manual (i.e. hand) dishwashing. Such compositions are generally high sudsing or foaming in nature.
• concentrations and ratios are on a weight basis unless otherwise specified.
• compositions herein essentially contain relatively large amounts, i.e., from about 34% to 40%, of an anionic surfactant component. More preferably the anionic surfactant component comprises from about 35% to 38% of the compositions herein.
• the anionic surfactant component essentially comprises lightly ethoxylated alkyl ether sulfates.
• Alkyl ether sulfates are also known as alkyl polyethoxylate sulfates. These lightly ethoxylated alkyl sulfates are those which correspond to the formula:
• R' is a Cg-C ⁇ g alkyl group, n is from about 0.4 to 1.6, and M is a salt- forming cation.
• R' is CIQ-16 alkyl, n is from about 0.5 to 1.4, and M is sodium, potassium, ammonium, alkylammonium, or alkanolammonium.
• R' is C12-C16, n is from about 0.6 to 1.1 and M is sodium.
• compositions herein also essentially contain from about 0.3% to 4.5% of a certain type of nonionic surfactant component. More preferably, the nonionic surfactant component will comprise from about 0.4% to 4% of the compositions herein.
• nonionic surfactant which can be present in the nonionic surfactant component of the compositions herein comprises the Cg. ⁇ g, preferably CjQ-16' polyhydroxy fatty acid amides. These materials are more fully described in Pan/Gosselink; U.S Patent 5,332,528; Issued July 26, 1994, which is incorporated herein by reference. These polyhydroxy fatty acid amides have a general structure of the formula:
• R2_ C _ N __ Z wherein R! is H, C1-C4 hydrocarbyl, 2-hydroxyethyl, 2-hydroxypropyl, or a mixture thereof; R ⁇ is Cg-Cj hydrocarbyl; and Z is a polyhydroxylhydrocarbyl having a linear hydrocarbyl chain with at least 3 hydroxyls directly connected to the chain, or an alkoxylated derivative thereof.
• surfactants include the Cjo-Ci N-methyl, or N-hydroxypropyl, glucamides.
• the N-propyl through N-hexyl C12- C ⁇ glucamides can be used for lower sudsing performance.
• Polyhydroxy fatty acid amides will preferably comprise from about 1% to 5% of the compositions herein.
• the nonionic surfactant component of the compositions herein may also comprise ethoxylated alcohols.
• Ethoxylated alcohol surfactant materials useful in the nonionic surfactant component herein are those which correspond to the general formula:
• R ⁇ is a Cg-C ⁇ g alkyl group and n ranges from about 1 to 15.
• R ⁇ is an alkyl group, which may be primary or secondary, that contains from about 11 to 14 carbon atoms, more preferably from about 10 to 13 carbon atoms.
• the ethoxylated fatty alcohols will contain from about 2 to 12 ethylene oxide moieties per molecule, more preferably from about 6 to 12 ethylene oxide moieties per molecule.
• the ethoxylated fatty alcohol nonionic co-surfactant will frequently have a hydrophilic-lipophilic balance (HLB) which ranges from about 6 to 15, most preferably from about 10 to 15.
• HLB hydrophilic-lipophilic balance
• fatty alcohol ethoxylates useful as the nonionic co-surfactant component of the compositions herein will include those which are made from alcohols of 12 to 15 carbon atoms and which contain about 7 moles of ethylene oxide. Such materials have been commercially marketed under the tradenames Neodol 25-7 and Neodol 23-6.5 by Shell Chemical Company.
• Neodols include Neodol 1-5, ethoxylated fatty alcohol averaging 11 carbon atoms in its alkyl chain with about 5 moles of ethylene oxide; Neodol 23-9, an ethoxylated primary C12- 13 alcohol having about 9 moles of ethylene oxide and Neodol 91-10, an ethoxylated C9-C1 j primary alcohol having about 10 moles of ethylene oxide. Alcohol ethoxylates of this type have also been marketed by Shell Chemical Company under the Dobanol tradename.
• Dobanol 91-5 is an ethoxylated C9-C1 ⁇ fatty alcohol with an average of 5 moles ethylene oxide and Dobanol 25-7 is an ethoxylated C12- C ⁇ fatty alcohol with an average of 7 moles of ethylene oxide per mole of fatty alcohol.
• suitable ethoxylated alcohol nonionic surfactants include Tergitol 15-S-7 and Tergitol 15-S-9, both of which are secondary alcohol ethoxylates that have been commercially marketed by Union Carbide Corporation.
• the former is a mixed ethoxylation product of C ⁇ ⁇ to C15 linear secondary alkanol with 7 moles of ethylene oxide and the latter is a similar product but with 9 moles of ethylene oxide being reacted.
• Alcohol ethoxylate nonionics useful in the present compositions are higher molecular weight nonionics, such as Neodol 45-11, which are similar ethylene oxide condensation products of higher fatty alcohols, with the higher fatty alcohol being of 14-15 carbon atoms and the number of ethylene oxide groups per mole being about 11. Such products have also been commercially marketed by Shell Chemical Company.
• Ethoxylated alcohol nonionics can help impart useful cleaning attributes to the compositions herein. Such materials, however, can adversely affect low temperature stability of the products. If used, therefore, ethoxylated alcohol nonionics will preferably comprise no more than about 1%, e.g., from about 0.5% to 1%, by weight of the compositions herein.
• nonionic surfactant suitable for use in the nonionic surfactant component herein comprises the ethylene oxide-propylene oxide block co-polymers that function as polymeric surfactants.
• block co-polymers comprise one or more groups which are hydrophobic and which contain mostly ethylene oxide moieties and one or more hydrophobic groups which contain mostly propylene oxide moieties.
• groups are attached to the residue of a compound that contained one or more hydroxy groups or amine groups.
• Such polymeric surfactants have a molecular weight ranging from about 400 to 60,000.
• Preferred ethylene oxide-propylene oxide polymeric surfactants are those in which propylene oxide is condensed with an amine, especially a diamine, to provide a base that is then condensed with ethylene oxide. Materials of this type are marketed under the tradename Tetronic®. Similar structures wherein the ethylene diamine is replaced with a polyol such as propylene glycol are marketed under the tradename "Pluronic®”. Preferred ethylene oxide-propylene oxide (EO-PO) polymeric surfactants have an HLB which ranges from about 4 to 30, more preferably about 10 to 20.
• ethylene oxide-propylene oxide block co-polymers used herein are described in greater detail in Pancheri/Mao; U.S. Patent 5,167,872; Issued December 2, 1992. This patent is incorporated herein by reference. Ethylene oxide-propylene oxide block co-polymers will frequently be present to the extent of from about 0.1% to 1% of the compositions herein. More preferably, these polymeric surfactant materials will comprise from about 0.2%) to 0.8% of the compositions herein.
• compositions herein further include from about 4.5% to 9%, preferably from about 5% to 8%, of a suds booster or stabilizer component such as betaine surfactants, hydroxy-free fatty acid amides, amine oxide semi-polar nonionic surfactants, and Cg_22 alkyl polyglycosides. Combinations of these suds boosters/stablizers can also be used.
• a suds booster or stabilizer component such as betaine surfactants, hydroxy-free fatty acid amides, amine oxide semi-polar nonionic surfactants, and Cg_22 alkyl polyglycosides.
• Betaine surfactants useful as suds boosters herein have the general formula:
• R is a hydrophobic group selected from alkyl groups containing from about 10 to about 22 carbon atoms, preferably from about 12 to about 18 carbon atoms, alkyl aryl and aryl alkyl groups containing a similar number of carbon atoms with a benzene ring being treated as equivalent to about 2 carbon atoms, and similar structures interrupted by amido or ether linkages; each R is an alkyl group containing from 1 to about 3 carbon atoms; and R is an alkylene group containing from 1 to about 6 carbon atoms.
• betaines dodecyl dimethyl betaine, cetyl dimethyl betaine, dodecyl amidopropyldimethyl betaine, tetradecyldimethyl betaine, tetradecylamidopropyldimethyl betaine, and dodecyldimethylammonium hexanoate.
• Other suitable amidoalkylbetaines are disclosed in U.S. Patent Nos. 3,950,417; 4,137,191; and 4,375,421; and British Patent GB No. 2,103,236, all of which are incorporated herein by reference.
• Hydroxy-free amide surfactants useful as suds boosters herein include the ammonia, monoethanol, and diethanol amides of fatty acids having an acyl moiety containing from about 8 to about 18 carbon atoms. Such materials are characterized herein as "hydroxy-free” in order to distinguish them from the polyhydroxy fatty acid amides essentially used in the nonionic surfactant component hereinbefore described. Accordingly, "hydroxy-free" amides, for purposes of this invention, are those wherein the acyl moiety contains no hydroxy substituents. These materials are represented by the formula: R - CO - N(H) (R OH)
• R j is a saturated or unsaturated, hydroxy-free aliphatic hydrocarbon group having from about 7 to 21, preferably from about 11 to 17 carbon atoms; R represents a methylene or ethylene group; and m is 1, 2, or 3, preferably 1.
• Specific examples of such amides are monoethanol amine coconut fatty acid amide and diethanolamine dodecyl fatty acid amide. These acyl moieties may be derived from naturally occurring glycerides, e.g., coconut oil, palm oil, soybean oil, and tallow, but can be derived synthetically, e.g., by the oxidation of petroleum or by hydrogenation of carbon monoxide by the Fischer-Tropsch process. The monoethanolamides and diethanolamides of C fatty acids are preferred.
• Amine oxide semi-polar nonionic surfactants useful as suds boosters/stabilizers comprise compounds and mixtures of compounds having 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 and R are each methyl, ethyl, propyl, isopropyl, 2-hydroxyethyl, 2-hydroxypropyl, or 3-hydroxypropyl, and n is from 0 to about 10.
• Particularly preferred are amine oxides of the formula:
• R is a C alkyl and R and R are methyl or ethyl.
• surfactants suitable for use as suds boosters/stabilizers in the compositions herein are the nonionic fatty alkylpolyglycosides. Such materials have the formula:
• Z is derived from glucose
• R is a hydrophobic group selected from alkyl, alkylphenyl, hydroxyalkylphenyl, and mixtures thereof in which said alkyl groups contain from 8 to 22, preferably from 12 to 14 carbon atoms; n is 2 or 3 preferably 2, y is from 0 to 10, preferably 0; and x is from 1.5 to 8, preferably from 1.5 to 4, most preferably from 1.6 to 2.7.
• the suds booster/stabilizer component hereinbefore described must be present in the compositions herein in certain amounts relative to the nonionic surfactant component which has also been hereinbefore described.
• the total concentration of the nonionic surfactant component plus the suds booster/stabilizer component should be at least about 7%, preferably at least about 7%, of the compositions herein.
• Aqueous Liquid Carrier Aqueous Liquid Carrier
• the light duty dishwashing detergent compositions herein further contain from about 40%) to 60%) of an aqueous liquid carrier in which the other essential and optional compositions components are dissolved, dispersed or suspended. More preferably the aqueous liquid carrier will comprise from about 45% to 55% of the compositions herein.
• the aqueous liquid carrier may contain other materials which are liquid, or which dissolve in the liquid carrier, at room temperature and which may also serve some other function besides that of a simple filler.
• Such materials can include, for example, hydrotropes and solvents.
• the aqueous liquid carrier may and preferably will comprise one or more materials which are hydrotropes.
• Hydrotropes suitable for use in the compositions herein include the C1-C3 alkyl aryl sulfonates, Cg-C ⁇ alkanols, Cj-Cg carboxylic sulfates and sulfonates, urea, Cj-Cg hydrocarboxylates, C1-C4 carboxylates, C2-C4 organic diacids and mixtures of these hydrotrope materials.
• Suitable C1-C3 alkyl aryl sulfonates include sodium, potassium, calcium and ammonium xylene sulfonates; sodium, potassium, calcium and ammonium toluene sulfonates; sodium, potassium, calcium and ammonium cumene sulfonates; and sodium, potassium, calcium and ammonium substituted or unsubstituted naphthalene sulfonates and mixtures thereof.
• Suitable Cj-Cg carboxylic sulfate or sulfonate salts are any water soluble salts or organic compounds comprising 1 to 8 carbon atoms (exclusive of substituent groups), which are substituted with sulfate or sulfonate and have at least one carboxylic group.
• the substituted organic compound may be cyclic, acylic or aromatic, i.e. benzene derivatives.
• Preferred alkyl compounds have from 1 to 4 carbon atoms substituted with sulfate or sulfonate and have from 1 to 2 carboxylic groups.
• hydrotrope examples include sulfosuccinate salts, sulfophthalic salts, sulfoacetic salts, m-sulfobenzoic acid salts and diester sulfosuccinates, preferably the sodium or potassium salts as disclosed in U.S. 3,915,903.
• Suitable C1-C4 hydrocarboxylates and C1-C4 carboxylates for use herein include acetates and propionates and citrates.
• Suitable C2-C4 diacids for use herein include succinic, glutaric and adipic acids.
• hydrotrope examples include C6-C12 alkanols and urea.
• Preferred hydrotropes for use herein are sodium, potassium, calcium and ammonium cumene sulfonate; sodium, potassium, calcium and ammonium xylene sulfonate; sodium, potassium, calcium and ammonium toluene sulfonate and mixtures thereof. Most preferred are sodium cumene sulfonate and calcium xylene sulfonate and mixtures thereof.
• These preferred hydrotrope materials can be present in the composition to the extent of from about 3% to 8% by weight. Hydrotrope concentrations of about 4%-5% may be especially useful in imparting beneficial low temperature stability to the compositions herein.
• water-mi scible liquids such as lower alkanols, diols, other polyols, ethers, amines, and the like may be used as part of the aqueous liquid carrier. Particularly preferred are the Cj_4 alkanols. Such solvents can be present in the compositions herein to the extent of from about 3% to 8%.
• Optional Ingredients such as lower alkanols, diols, other polyols, ethers, amines, and the like may be used as part of the aqueous liquid carrier.
• Particularly preferred are the Cj_4 alkanols.
• solvents can be present in the compositions herein to the extent of from about 3% to 8%.
• Preferred optional ingredients in the dishwashing compositions herein include ancillary surfactants, calcium and/or magnesium ions, enzymes such as protease, and a stabilizing system for the enzymes. These and other optional ingredients are described as follows:
• compositions herein may contain a wide variety of ancillary surfactants in addition to the essentially utilized surfactants hereinbefore described.
• ancillary surfactants for example, can include C _22 alkyl sulfates; 09.15 a ' benzene sulfonates; C _22 olefin sulfonates; Cg.22 paraffin sulfonates; Cg.22 alkyl glyceryl ether sulfonates; fatty acid ester sulfonates; secondary alcohol sulfates; C12-I6 alkyl ethoxy carboxylates; ⁇ ⁇ . ⁇ secondary soaps; ampholytic detergent surfactants; and zwitterionic detergent surfactants.
• compositions containing alkyl ethoxy sulfates and/or polyhydroxy fatty acid amides can improve the cleaning of greasy soils for various compositions, i.e., compositions containing alkyl ethoxy sulfates and/or polyhydroxy fatty acid amides. 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 interfacial tension and improving grease cleaning.
• Addition of both calcium and magnesium ions can also improve the low temperature stability of the compositions herein.
• This ion combination will thus preferably be present in the compositions herein at an active level of from about 0.2% to 2%, more preferably from about 0.3% to 1.5%, by weight.
• the magnesium ions are added as a hydroxide or as a chloride, sulfate, acetate, formate, oxide or nitrate salt to the compositions of the present invention.
• Inorganic salts such as chloride and sulfate are preferred and may provide an extra low temperature stability benefit.
• Such magnesium salts may comprise from about 2% to 6% of the compositions herein.
• Magnesium ions may also be added as the counterion to anionic surfactants that are employed Calcium ions are preferably added to the compositions herein as salts of a hydrotrope.
• compositions of the invention will be dependent upon the amount of total surfactant present therein.
• the molar ratio of calcium and magnesium ions to total anionic surfactant should be from about 0.25:1 to about 2:1.
• 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.
• the stability of these compositions becomes poor due to the formation of hydroxide precipitates. Therefore, chelating agents discussed hereinafter may also be necessary.
• compositions of this invention can also optionally contain from about 0.001% to about 5%, more preferably from about 0.003% to about 4%, most preferably from about 0.005% to about 3%, by weight, of active protease, i.e., proteolytic, enzyme.
• Protease activity may be expressed in Anson units (AU.) per kilogram of detergent composition.
• Levels of from 0.01 to about 150, preferably from about 0.05 to about 80, most preferably from about 0.1 to about 40 AU. per kilogram have been found to be acceptable in compositions of the present invention.
• proteolytic enzymes can be of animal, vegetable or microorganism (preferred) origin. More preferred is serine proteolytic enzyme of bacterial origin. Purified or nonpurified forms of this enzyme may be used. Proteolytic enzymes produced by chemically or genetically modified mutants are included by definition, as are close structural enzyme variants. Particularly preferred is bacterial serine proteolytic enzyme obtained from Bacillus subtilis and/or Bacillus licheniformis.
• Suitable proteolytic enzymes include Novo Industri A/S Alcalase® (preferred), Esperase® , Savinase® (Copenhagen, Denmark), Gist-brocades' Maxatase®, Maxacal® and Maxapem 15® (protein engineered Maxacal®) (Delft, Netherlands), and subtilisin BPN and BPN'(preferred), which are commercially available.
• Preferred proteolytic enzymes are also modified bacterial serine proteases, such as those made by Genencor International, Inc. (San Francisco, California) which are described in European Patent EP-B-251,446, granted December 28, 1994 and published January 7, 1988 (particularly pages 17, 24 and 98) and which are also called herein "Protease B".
• Protease A a modified bacterial serine proteolytic enzyme
• BPN' modified bacterial serine proteolytic enzyme
• Preferred proteolytic enzymes are selected from the group consisting of Alcalase ® (Novo Industri A/S), BPN', Protease A and Protease B (Genencor), and mixtures thereof. Protease B is most preferred.
• protease D is a carbonyl hydrolase variant having an amino acid sequence not found in nature, which is derived from a precursor carbonyl hydrolase by substituting a different amino acid for a plurality of amino acid residues at a position in said carbonyl hydrolase equivalent to position +76, preferably also in combination with one or more amino acid residue positions equivalent to those selected from the group consisting of +99, +101, +103, +104, +107, +123, +27, +105, +109, +126, +128, +135, +156, +166, +195, +197, +204, +206, +210, +216, +217, +218, +222, +260, +265, and/or +274 according to the numbering of Bacillus amyloliquefaciens subtilisin, as described in WO 95/10615 published April 20, 1995 by Genencor International.
• proteases are also described in PCT publications: WO 95/30010 published November 9, 1995 by The Procter & Gamble Company; WO 95/30011 published November 9, 1995 by The Procter & Gamble Company; WO 95/29979 published November 9, 1995 by The Procter & Gamble Company.
• compositions herein may additionally comprise from about 0.001%) to about 10%, preferably from about 0.005% to about 8%, most preferably from about 0.01% to about 6%, by weight of an enzyme stabilizing system.
• the enzyme stabilizing system can be any stabilizing system which is compatible with the protease or other enzymes used in the compositions herein.
• Such stabilizing systems can comprise calcium ion, boric acid, propylene glycol, short chain carboxylic acid, boronic acid, polyhydroxyl compounds and mixtures thereof such as are described in U.S.
• chlorine bleach or oxygen bleach scavengers can be added to compositions of the present invention to prevent chlorine bleach species present in many water supplies from attacking and inactivating the enzymes, especially under alkaline conditions. While chlorine levels in water may be small, typically in the range from about 0.5 ppm to about 1.75 ppm, the available chlorine in the total volume of water that comes in contact with the enzyme during dishwashing is usually large; accordingly, enzyme stability in-use can be problematic.
• Suitable chlorine scavenger anions are salts containing ammonium cations. These can be selected from the group consisting of reducing materials like sulfite, bisulfite, thiosulfite, thiosulfate, iodide, etc., antioxidants like carbonate, ascorbate, etc., organic amines such as ethylenediaminetetracetic acid (EDTA) or alkali metal salt thereof and monoethanolamine (MEA), and mixtures thereof.
• reducing materials like sulfite, bisulfite, thiosulfite, thiosulfate, iodide, etc.
• antioxidants like carbonate, ascorbate, etc.
• organic amines such as ethylenediaminetetracetic acid (EDTA) or alkali metal salt thereof and monoethanolamine (MEA), and mixtures thereof.
• EDTA ethylenediaminetetracetic acid
• MEA monoethanolamine
• detergency builders can also be present in the compositions herein in amounts of from 0% to about 50%, preferably from about 2% to about 30%, most preferably from about 5% to about 15%. It is typical in light-duty liquid or gel dishwashing detergent compositions to have no detergent builder present.
• compositions containing magnesium or calcium ions may require the additional presence of low levels of, preferably from 0 to about 10%, more preferably from about 0.5% to about 3% ⁇ , chelating agents selected from the group consisting of bicine/bis(2- ethanol)blycine), citrate N-(2-hydroxylethyl) iminodiacetic acid (HID A), N-(2,3- dihydroxy- propyl) diethanolamine, l,2-diamino-2-propanol N,N'-tetramethyl-l,3- diamino-2-propanol, N,N-bis(2-hydroxyethyl)glycine (a.k.a. bicine), and N-tris (hydroxymethyl)methyl glycine (a.k.a. tricine) are also preferred. Mixtures of any of the above are acceptable.
• Liquid dishwashing detergent compositions of this invention which are relatively thick, i.e., which have higher viscosity, can be prepared without the use of polymeric thickeners by selecting specific types and amounts of the components hereinbefore described.
• relatively thickened products can be realized by:
• liquid detergent compositions of the instant invention that are thickened will have a Brookfield viscosity of from about 500 to 3,500 cps at 25°C. More preferably, such thickened products will have a viscosity of from about 800 to 2,000 cps at 25°C. For purposes of this invention, viscosity is measured with a Brookfield LNTDN-11 viscometer apparatus using an RV#2 spindle at 1.0 rpm.
• the dishwashing compositions of the present invention will generally provide a 10% aqueous solution pH of from about 6 to 8. More preferably, the compositions herein will be alkaline in nature with a 10% aqueous solution pH of from about 7 to 7.8. Compositions of especially desirable low temperature stability may be realized by keeping the 10% aqueous solution pH of the products herein below about 7.5.
• 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 should contain a buffering agent capable of providing a generally more alkaline pH in the composition and in dilute solutions, i.e., about 0.1% to 0.4% by weight aqueous solution, of the composition.
• 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 buffering agent should be from about 7 to about 9.5. 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 in this composition solely for maintaining an alkaline pH.
• Preferred buffering agents for compositions of this invention are nitrogen-containing materials. Some examples are amino acids or lower alcohol amines like mono-, di-, and tri-ethanolamine.
• Useful inorganic buffers/alkalinity sources include the alkali metal carbonates, e.g., sodium carbonate.
• the buffering agent if used, is present in the compositions of the invention herein at a level of from about 0.1% to 15%, preferably from about 1% to 10%, most preferably from about 2% to 8%, by weight of the composition.
• liquid or gel dishwashing detergent compositions herein may be prepared by combining the essential and optional ingredients together in any convenient order using suitable agitation to form a homogeneous product.
• Preferred methods for making detergent compositions of the type disclosed herein, and for preparing various components of such compositions, are described in greater detail in Ofosu- Asante; U.S. 5,474,710; Issued December 12, 1995, incorporated herein by reference.
• the liquid dishwashing detergent products of the present invention exhibit desirable phase stability when subjected to prolonged low temperature and freeze/thaw testing
• the compositions of the present invention are generally stable for not less than 4 days.
• the temperature at which they recover from phase instability caused by freezing should be 60°F (16°C) or lower.
• Soiled dishes can be contacted with an effective amount, typically from about 0.5 ml. to about 20 ml. (per 25 dishes being treated), preferably from about 3 ml. to about 10 ml., of the detergent composition of the present invention.
• the actual amount of liquid detergent composition used will be based on the judgment of user, and will typically depend upon factors such as the particular product formulation of the composition, including the concentration of active ingredient in the composition, the number of soiled dishes to be cleaned, the degree of soiling on the dishes, and the like.
• the particular product formulation in turn, will depend upon a number of factors, such as the intended market (i.e., U.S., Europe, Japan, etc.) for the composition product.
• a liquid detergent composition in a typical U.S. application, from about 3 ml. to about 15 ml., preferably from about 5 ml. to about 10 ml. of a liquid detergent composition is combined with from about 1,000 ml. to about 10,000 ml., more typically from about 3,000 ml. to about 5,000 ml. of water in a sink having a volumetric capacity in the range of from about 5,000 ml. to about 20,000 ml., more typically from about 10,000 ml. to about 15,000 ml.
• the detergent composition has a surfactant mixture concentration of from about 21%) to about 44% by weight, preferably from about 25% to about 40% by weight.
• the soiled dishes are immersed in the sink containing the detergent composition and water, where they are cleaned by contacting the soiled surface of the dish with a cloth, sponge, or similar article.
• the cloth, sponge, or similar article may be immersed in the detergent composition and water mixture prior to being contacted with the dish surface, and is typically contacted with the dish surface for a period of time ranging from about 1 to about 10 seconds, although the actual time will vary with each application and user.
• the contacting of the cloth, sponge, or similar article to the dish surface is preferably accompanied by a concurrent scrubbing of the dish surface.
• a liquid detergent composition in a typical European market application, from about 3 ml. to about 15 ml., preferably from about 3 ml. to about 10 ml. of a liquid detergent composition is combined with from about 1,000 ml. to about 10,000 ml., more typically from about 3,000 ml. to about 5,000 ml. of water in a sink having a volumetric capacity in the range of from about 5,000 ml. to about 20,000 ml., more typically from about 10,000 ml. to about 15,000 ml.
• the detergent composition has a surfactant mixture concentration of from about 20% to about 50% by weight, preferably from about 30% to about 40%, by weight.
• the soiled dishes are immersed in the sink containing the detergent composition and water, where they are cleaned by contacting the soiled surface of the dish with a cloth, sponge, or similar article.
• the cloth, sponge, or similar article may be immersed in the detergent composition and water mixture prior to being contacted with the dish surface, and is typically contacted with the dish surface for a period of time ranging from about 1 to about 10 seconds, although the actual time will vary with each application and user.
• the contacting of the cloth, sponge, or similar article to the dish surface is preferably accompanied by a concurrent scrubbing of the dish surface.
• a detergent composition in a typical Latin American market application, from about 1 ml. to about 50 ml., preferably from about 2 ml. to about 10 ml. of a detergent composition is combined with from about 50 ml. to about 2,000 ml., more typically from about 100 ml. to about 1,000 ml. of water in a bowl having a volumetric capacity in the range of from about 500 ml. to about 5,000 ml., more typically from about 500 ml. to about 2,000 ml.
• the detergent composition has a surfactant mixture concentration of from about 5% to about 40% by weight, preferably from about 10% to about 30% by weight.
• the soiled dishes are cleaned by contacting the soiled surface of the dish with a cloth, sponge, or similar article.
• the cloth, sponge, or similar article may be immersed in the detergent composition and water mixture prior to being contacted with the dish surface, and is typically contacted with the dish surface for a period of time ranging from about 1 to about 10 seconds, although the actual time will vary with each application and user.
• the contacting of the cloth, sponge, or similar article to the dish surface is preferably accompanied by a concurrent scrubbing of the dish surface.
• Another dishwashing method used worldwide involves direct application of the detergent compositions herein, either neat or diluted in a dispenser bottle, onto the soiled dishes to be cleaned. This can be accomplished by using a device for absorbing liquid dishwashing detergent, such as a sponge or dishrag, which is placed directly into a separate quantity of undiluted or somewhat diluted liquid dishwashing composition for a period of time typically ranging from about 1 to about 5 seconds.
• the absorbing device, and consequently the undiluted or somewhat diluted liquid dishwashing composition can then be contacted individually with the surface of each of the soiled dishes to remove food soil.
• the absorbing device is typically contacted with each dish surface for a period of time ranging from about 1 to about 10 seconds, although the actual time of application will be dependent upon factors such as the degree of soiling of the dish.
• the contacting of the absorbing device with the dish surface is preferably accompanied by concurrent scrubbing. Prior to contact and scrubbing, this method may involve immersing the soiled dishes into a water bath without any liquid dishwashing detergent. After scrubbing, the dish can be rinsed under running water.
• Light-duty liquid dishwashing detergent products having the following compositions are prepared:
• liquid dishwashing detergent products all provide excellent greasy soil removal from dishes and excellent sudsing when they are used in aqueous dishwashing solution to clean dirty dishware. These products also have especially desirable low temperature stability as evidenced, for example, by their performance under 40°F (4.4°C) Constant Temperature conditions and their clarity recovery from 0°F (-18°C) freeze/thaw testing.
• a thickened, light-duty liquid dishwashing detergent product of relatively high viscosity is prepared having the following formula: This product is free of polyhydroxy fatty acid amides and polymeric thickeners.

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• 1998
  • 1998-06-08 JP JP50303299A patent/JP2002504168A/ja not_active Ceased
  • 1998-06-08 CN CN 98808143 patent/CN1267323A/zh active Pending
  • 1998-06-08 EP EP98926414A patent/EP0988359A1/en not_active Withdrawn
  • 1998-06-08 WO PCT/US1998/011813 patent/WO1998056884A1/en not_active Application Discontinuation
  • 1998-06-08 BR BR9810747-0A patent/BR9810747A/pt not_active IP Right Cessation
  • 1998-06-08 AU AU78258/98A patent/AU7825898A/en not_active Abandoned
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