EP0551410B1 - Detergent compositions containing anionic surfactants, polyhydroxy fatty acid amides and magnesium - Google Patents

Detergent compositions containing anionic surfactants, polyhydroxy fatty acid amides and magnesium Download PDF

Info

Publication number
EP0551410B1
EP0551410B1 EP91918975A EP91918975A EP0551410B1 EP 0551410 B1 EP0551410 B1 EP 0551410B1 EP 91918975 A EP91918975 A EP 91918975A EP 91918975 A EP91918975 A EP 91918975A EP 0551410 B1 EP0551410 B1 EP 0551410B1
Authority
EP
European Patent Office
Prior art keywords
fatty acid
alkyl
sulfonate
polyhydroxy fatty
weight
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Expired - Lifetime
Application number
EP91918975A
Other languages
German (de)
English (en)
French (fr)
Other versions
EP0551410A1 (en
Inventor
Thomas Richard Rolfes
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Procter and Gamble Co
Original Assignee
Procter and Gamble Co
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Procter and Gamble Co filed Critical Procter and Gamble Co
Publication of EP0551410A1 publication Critical patent/EP0551410A1/en
Application granted granted Critical
Publication of EP0551410B1 publication Critical patent/EP0551410B1/en
Anticipated expiration legal-status Critical
Expired - Lifetime legal-status Critical Current

Links

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
    • 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
    • C11D1/38—Cationic compounds
    • C11D1/65—Mixtures of anionic with cationic compounds
    • C11D1/652—Mixtures of anionic compounds with carboxylic amides or alkylol amides
    • 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
    • C11D1/86—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
    • C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
    • C11D3/16—Organic compounds
    • C11D3/26—Organic compounds containing nitrogen
    • C11D3/32—Amides; Substituted amides
    • 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
    • C11D1/14—Sulfonic acids or sulfuric acid esters; Salts thereof derived from aliphatic hydrocarbons or mono-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
    • 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
    • C11D1/18—Sulfonic acids or sulfuric acid esters; Salts thereof derived from amino alcohols
    • C11D1/20—Fatty acid condensates
    • 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
    • C11D1/22—Sulfonic acids or sulfuric acid esters; Salts thereof derived from aromatic 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
    • C11D1/02—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
    • C11D1/42—Amino alcohols or amino ethers
    • C11D1/44—Ethers of polyoxyalkylenes with amino alcohols; Condensation products of epoxyalkanes with 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
    • 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
    • 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

Definitions

  • the present invention relates to detergent compositions comprising one or more anionic sulfate or sulfonate surfactants, one or more polyhydroxy fatty acid amides and magnesium.
  • it relates to detergent compositions which possess desirable cleaning and sudsing properties, are mild to the hand, and are especially suitable for use in dishwashing applications.
  • anionic sulfated or sulfonated surfactants in detergent compositions is known. However, it would be desirable to incorporate such surfactants into detergent compositions which exhibit improved cleaning and sudsing performance.
  • detergent compositions containing one or more anionic sulfated or sulfonated detergent surfactants, one or more polyhydroxy fatty acid amides and magnesium exhibit sudsing and cleaning performance which is unexpectedly superior to the performance of anionic sulfated or sulfonated surfactants alone.
  • compositions when compared to anionic sulfated or sulfonated surfactants, milder to the hand, have improved rinsability, are not as slippery to the touch, and are easier to formulate due to a reduced need for process additives such as solvents and hydrotropes.
  • the polyhydroxy fatty acid amide component contained in the composition of the present invention is also known in the art, as are several of its uses.
  • N-acyl, N-methyl glucamides for example, are disclosed by J. W. Goodby, M. A. Marcus, E. Chin, and P. L. Finn in "The Thermotropic Liquid-Crystalline Properties of Some Straight Chain Carbohydrate Amphiphiles," Liquid Crystals, 1988, Volume 3, No. 11, pp. 1569-1581, and by A. Muller-Fahrnow, V. Zabel, M. Steifa, and R. Hilgenfeld in "Molecular and Crystal Structure of a Nonionic Detergent: Nonanoyl-N-methylglucamide," J. Chem. Soc. Chem. Commun., 1986, pp. 1573-1574.
  • N-alkyl polyhydroxyamide surfactants have been of substantial interest recently for use in biochemistry, for example in the dissociation of biological membranes. See, for example, the journal article "N-D-Gluco-N-methyl-alkanamide Compounds, a New Class of Non-Ionic Detergents For Membrane Biochemistry," Biochem. J. (1982), Vol. 207, pp. 363-366, by J. E. K. Hildreth.
  • N-alkyl glucamides in detergent compositions has also been discussed.
  • U.S. Patent 2,965,576, issued December 20, 1960 to E. R. Wilson, and U.K. Patent Specification 809,060, already referred to herein, relate to detergent compositions containing anionic surfactants and certain amide surfactants, which can include N-methyl glucamide, added as a low temperature suds enhancing agent.
  • These compounds include an N-acyl radical of a higher straight-chain fatty acid having 10-14 carbon atoms.
  • These compositions may also contain auxiliary materials such as alkali metal phosphates, alkali metal silicates, sulfates, and carbonates.
  • FR 1 580 491 relates to detergent compositions comprising certain amides acting as high temperature suds inhibitors and low temperature suds enhancers
  • U.S. Patent 2,703,798, issued March 8, 1955 to A. M. Schwartz relates to aqueous detergent compositions containing the condensation reaction product of N-alkyl glucamine and an aliphatic ester of a fatty acid. The product of this reaction is said to be useable in aqueous detergent compositions without further purification. It is also known to prepare a sulfuric ester of acylated glucamine as disclosed in U.S. Patent 2,717,894, issued September 13, 1955, to A. M. Schwartz.
  • PCT International Application WO 83/04412, published December 22, 1983, by J. Hildreth relates to amphiphilic compounds containing polyhydroxyl aliphatic groups said to be useful for a variety of purposes including use as surfactants in cosmetics, drugs, shampoos, lotions, and eye ointments, as emulsifiers and dispensing agents for medicines, and in biochemistry for solubilizing membranes, whole cells, or other tissue samples, and for preparing liposomes.
  • R'CON(R)CH2R'' and R''CON(R)R' wherein R is hydrogen or an organic grouping, R' is an aliphatic hydrocarbon group of at least three carbon atoms, and R'' is the residue of an aldose.
  • European Patent 0 285 768 published October 12, 1988, H. Kelkenberg, et al., relates to the use of N-polyhydroxy alkyl fatty acid amides as thickening agents in aqueous detergent systems. Included are amides of the formula R1C(O)N(X)R2 wherein R1 is a C1-C17 (preferably C7-C17) alkyl, R2 is hydrogen, a C1-C18 (preferably C1-C6) alkyl, or an alkylene oxide, and X is a polyhydroxy alkyl having four to seven carbon atoms, e.g., N-methyl, coconut fatty acid glucamide.
  • the thickening properties of the amides are indicated as being of particular use in liquid surfactant systems containing paraffin sulfonate, although the aqueous surfactant systems can contain other anionic surfactants, such as alkylaryl sulfonates, olefin sulfonate, sulfosuccinic acid half ester salts, and fatty alcohol ether sulfonates, and nonionic surfactants such as fatty alcohol polyglycol ether, alkylphenol polyglycol ether, fatty acid polyglycol ester, polypropylene oxide-polyethylene oxide mixed polymers, etc.
  • anionic surfactants such as alkylaryl sulfonates, olefin sulfonate, sulfosuccinic acid half ester salts, and fatty alcohol ether sulfonates
  • nonionic surfactants such as fatty alcohol polyglycol ether, alkylphenol polyglycol ether,
  • Paraffin sulfonate/N-methyl coconut fatty acid glucamide/nonionic surfactant shampoo formulations are exemplified.
  • the N-polyhydroxy alkyl fatty acid amides are said to have superior skin tolerance attributes.
  • U.S. Patent 2,982,737 issued May 2, 1961, to Boettner, et al., relates to detergent bars containing urea, sodium lauryl sulfate anionic surfactant, and an N-alkylglucamide nonionic surfactant which is selected from N-methyl,N-sorbityl lauramide and N-methyl, N-sorbityl myristamide.
  • glucamide surfactants are disclosed, for example, in DT 2,226,872, published December 20, 1973, H. W. Eckert, et al., which relates to washing compositions comprising one or more surfactants and builder salts selected from polymeric phosphates, sequestering agents, and washing alkalis, improved by the addition of an N-acylpolyhydroxyalkylamine of the formula R1C(O)N(R2)CH2(CHOH) n CH2OH, wherein R1 is a C1-C3 alkyl, R2 is a C10-C22 alkyl, and n is 3 or 4.
  • the N-acylpolyhydroxyalkyl-amine is added as a soil suspending agent.
  • U.S. Patent 3,654,166, issued April 4, 1972, to H. W. Eckert, et al. relates to detergent compositions comprising at least one surfactant selected from the group of anionic, zwitterionic, and nonionic surfactants and, as a textile softener, an N-acyl, N-alkyl polyhydroxyalkyl compound of the formula R1N(Z)C(O)R2 wherein R1 is a C10-C22 alkyl, R2 is a C7-C21 alkyl, R1 and R2 total from 23 to 39 carbon atoms, and Z is a polyhydroxyalkyl which can be -CH2(CHOH) m CH2OH where m is 3 or 4.
  • U.S. Patent 4,021,539 issued May 3, 1977, to H. Möller, et al., relates to skin treating cosmetic compositions containing N-polyhydroxyalkyl-amines which include compounds of the formula R1N(R)CH(CHOH) m R2 wherein R1 is H, lower alkyl, hydroxy-lower alkyl, or aminoalkyl, as well as heterocyclic aminoalkyl, R is the same as R1 but both cannot be H, and R2 is CH2OH or COOH.
  • French Patent 1,360,018, April 26, 1963, assigned to Commercial Solvents Corporation, relates to solutions of formaldehyde stabilized against polymerization with the addition of amides of the formula RC(O)N(R1)G wherein R is a carboxylic acid functionality having at least seven carbon atoms, R1 is hydrogen or a lower alkyl group, and G is a glycitol radical with at least 5 carbon atoms.
  • German Patent 1,261,861, February 29, 1968, A. Heins relates to glucamine derivatives useful as wetting and dispersing agents of the formula N(R)(R1)(R2) wherein R is a sugar residue of glucamine, R1 is a C10-C20 alkyl radical, and R2 is a C1-C5 acyl radical.
  • G.B. Patent 745,036, published February 15, 1956, assigned to Atlas Powder Company, relates to heterocyclic amides and carboxylic esters thereof that are said to be useful as chemical intermediates, emulsifiers, wetting and dispersing agents, detergents, textile softeners, etc.
  • the compounds are expressed by the formula N(R)(R1)C(O)R2 wherein R is the residue of an anhydrized hexane pentol or a carboxylic acid ester thereof, R1 is a monovalent hydrocarbon radical, and -C(O)R2 is the acyl radical of a carboxylic acid having from 2 to 25 carbon atoms.
  • U.S. Patent 3,312,627 discloses solid toilet bars that are substantially free of anionic detergents and alkaline builder materials, and which contain lithium soap of certain fatty acids, a nonionic surfactant selected from certain propylene oxide-ethylenediamine-ethylene oxide condensates, propylene oxide-propylene glycol-ethylene oxide condensates, and polymerized ethylene glycol, and also contain a nonionic lathering component which can include polyhydroxyamide of the formula RC(O)NR1(R2) wherein RC(O) contains from about 10 to about 14 carbon atoms, and R1 and R2 each are H or C1-C6 alkyl groups, said alkyl groups containing a total number of carbon atoms of from 2 to about 7 and a total number of substituent hydroxyl groups of from 2 to about 6.
  • a substantially similar disclosure is found in U.S. Patent 3,312,626, also issued April 4, 1967 to D. T. Hooker.
  • the present invention is directed to detergent compositions comprising from about 5% to about 65% by weight of a surfactant mixture comprising:
  • the present invention is also directed toward a method for cleaning soiled dishes, said method comprising treating said dishes with the detergent compositions claimed herein.
  • the detergent compositions of the present invention comprise from about 5% to about 65% by weight, preferably from about 10% to about 50% by weight, most preferably from about 20% to about 40% by weight of a surfactant mixture comprising one or more anionic sulfated or sulfonated surfactants and one or more polyhydroxy fatty acid amides.
  • These compositions additionally contain magnesium in a molar amount corresponding to 0.1X-2.0X, preferably 0.2X-1.7X, more preferably 0.3X-1.5X, wherein X is the number of moles of anionic sulfate or sulfonate surfactant present in said composition.
  • the detergent compositions of the present invention are preferably in the form of either a liquid or a gel, more preferably light-duty liquid detergent compositions, most preferably light-duty liquid dishwashing detergent compositions.
  • the surfactant mixture of the present invention comprises from about 5% to about 95%, preferably from about 20% to about 80%, more preferably from about 40% to about 60% by weight of one or more anionic sulfate or sulfonate surfactants.
  • the anionic sulfate or sulfonate surfactants may be any organic sulfate or sulfonate surfactant, but is preferably selected from C11-C15 alkyl benzene sulfonates, C10-C16 alkyl sulfates and their ethoxy analogues containing up to twelve moles of ethylene oxide per mole of alkyl ethoxy sulfates, C13-C18 paraffin sulfonates and secondary alkane sulfonates, C10-C16 olefin sulfonates, C10-C20 alkyl glyceryl ether sulfonates, C9-C17 acyl-N-(
  • Alkyl benzene sulfonates useful in compositions of the present invention are those in which the alkyl group, which is substantially linear, contains 10-16 carbon atoms, preferably 10-13 carbon atoms, a material with an average carbon chain length of 11.2 being most preferred.
  • the phenyl isomer distribution i.e., the point of attachment of the alkyl chain to the benzene nucleus, is not critical, but alkyl benzenes having a high 2-phenyl isomer content are preferred.
  • Suitable alkyl sulfates are primary alkyl sulfates in which the alkyl group contains 10-16 carbon atoms, more preferably an average of 12-14 carbon atoms preferably in a linear chain.
  • C10-C16 alcohols derived from natural fats, or Ziegler olefin build-up, or OXO synthesis, form suitable sources for the alkyl group.
  • Examples of synthetically derived materials include Dobanol 23 (RTM) sold by Shell Chemicals (UK) Ltd., Ethyl 24 sold by the Ethyl Corporation, a blend of C13-C15 alcohols in the ratio 67% C13, 33% C15 sold under the trade name Lutensol by BASF GmbH and Synperonic (RTM) by ICI Ltd., and Lial 125 sold by Liquichimica Italiana.
  • Examples of naturally occurring materials from which the alcohols can be derived are coconut oil and palm kernel oil and the corresponding fatty acids.
  • Alkyl ethoxy sulfate surfactants comprise a primary alkyl ethoxy sulfate derived from the condensation product of a C10-C16 alcohol with an average of up to 7 ethylene oxide groups.
  • the C10-C16 alcohol itself can be obtained from any of the sources previously described for the alkyl sulfate component.
  • C12-C13 alkyl ethoxy sulfates are preferred.
  • Blends can be made of material having different degrees of ethoxylation and/or different ethoxylate distributions arising from the specific ethoxylation techniques employed and subsequent processing steps such as distillation.
  • Secondary alkane sulfonates useful in the present invention have from 13 to 18 carbon atoms per molecule, more desirably 13 to 16 carbon atoms per molecule. These sulfonates are preferably prepared by subjecting a cut or paraffin, corresponding to the chain lengths specified above, to the action of sulfur dioxide and oxygen in accordance with the well-known sulfoxidation process. The product of this reaction is a secondary sulfonic acid which is then neutralized with a suitable base to provide a water-soluble secondary alkyl sulfonate.
  • Similar secondary alkyl sulfonates may be obtained by other methods, e.g., by the sulfochlorination method in which chlorine and sulfur dioxide are reacted with paraffins in the presence of actinic light, the resulting sulfonyl chlorides being hydrolyzed and neutralized to form the secondary alkyl sulfonates.
  • the proportions of disulfonate or higher sulfonated material will be minimized, although some may be present.
  • the monosulfonate may be terminally sulfonated or the sulfonate group may be joined on the 2-carbon or other carbon of the linear chain.
  • any accompanying disulfonate usually produced when an excess of sulfonating agent is present, may have the sulfonate groups distributed over different carbon atoms of the paraffin base, and mixtures of the monosulfonates and disulfonates may be present.
  • Olefin sulfonates useful in the present invention are mixtures of alkene-1-sulfonates, alkene hydroxysulfonates, alkene disulfonates and hydroxydisulfonates, and are described in the commonly assigned U.S. Patent 3,332,880, issued to P. F. Pflauner and A. Kessler on July 25, 1967.
  • Suitable alkyl glyceryl ether sulfonates are those derived from ethers of coconut oil and tallow.
  • sulfate surfactants include the C9-C17 acyl-N-(C1-C4 alkyl) or -N-(C1-C2 hydroxyalkyl) glucamine sulfates, preferably those in which the C9-C17 acyl group is derived from coconut or palm kernel oil. These materials can be prepared by the method disclosed in U.S. Patent 2,717,894, issued September 13, 1955 to Schwartz.
  • the counterion for the anionic surfactant component is preferably selected from sodium, potassium, magnesium, ammonium or alkanol-ammonium, and mixtures thereof, with magnesium being preferred.
  • the surfactant mixture of the present invention comprises from about 5% to about 95%, preferably from about 20% to about 80%, more preferably from about 40% to about 60% by weight of one or more polyhydroxy fatty acid amides having the structural formula: wherein: R1 is H, C1-C4 hydrocarbyl, 2-hydroxy ethyl, 2-hydroxy propyl, or a mixture thereof, preferably C1-C4 alkyl, more preferably C1 or C2 alkyl, most preferably C1 alkyl (i.e., methyl); and R2 is a C5-C31 hydrocarbyl, preferably straight-chain C7-C19 alkyl or alkenyl, more preferably straight-chain C9-C17 alkyl or alkenyl, most preferably straight-chain C11-C17 alkyl or alkenyl, or mixture thereof; and Z is a polyhydroxyhydrocarbyl having a linear hydrocarbyl chain with at least 3 hydroxyls directly connected to the chain, or an alkoxy
  • Z preferably will be derived from a reducing sugar in a reductive amination reaction; more preferably Z is a glycityl.
  • Suitable reducing sugars include glucose, fructose, maltose, lactose, galactose, mannose, and xylose.
  • high dextrose corn syrup, high fructose corn syrup, and high maltose corn syrup can be utilized as well as the individual sugars listed above. These corn syrups may yield a mix of sugar components for Z. It should be understood that it is by no means intended to exclude other suitable raw materials.
  • Z preferably will be selected from the group consisting of -CH2-(CHOH) n -CH2OH, -CH(CH2OH)-(CHOH) n-1 -CH2OH, -CH2-(CHOH)2(CHOR')(CHOH)-CH2OH, where n is an integer from 3 to 5, inclusive, and R' is H or a cyclic or aliphatic monosaccharide, and alkoxylated derivatives thereof. Most preferred are glycityls wherein n is 4, particularly -CH2-(CHOH)4-CH2OH.
  • R1 can be, for example, N-methyl, N-ethyl, N-propyl, N-isopropyl, N-butyl, N-2-hydroxy ethyl, or N-2-hydroxy propyl.
  • R2-CO-N ⁇ can be, for example, cocamide, stearamide, oleamide, lauramide, myristamide, capricamide, palmitamide, tallowamide, etc.
  • Z can be 1-deoxyglucityl, 2-deoxyfructityl, 1-deoxymaltityl, 1-deoxylactityl, 1-deoxygalactityl, 1-deoxymannityl, 1-deoxymaltotriotityl, etc.
  • the most preferred polyhydroxy fatty acid amide has the general formula wherein R2 is a C11-C17 straight-chain alkyl or alkenyl group.
  • polyhydroxy fatty acid amides are known in the art. In general, they can be made by reacting an alkyl amine with a reducing sugar in a reductive amination reaction to form a corresponding N-alkyl polyhydroxyamine, and then reacting the N-alkyl polyhydroxyamine with a fatty aliphatic ester or triglyceride in a condensation/amidation step to form the N-alkyl, N-polyhydroxy fatty acid amide product.
  • Processes for making compositions containing polyhydroxy fatty acid amides are disclosed, for example, in G.B. Patent Specification 809,060, published February 18, 1959, by Thomas Hedley & Co., Ltd., U.S.
  • N-deoxyglycityl fatty acid amides wherein the glycityl component is derived from glucose and the N-alkyl or N-hydroxy- alkyl functionality is N-methyl, N-ethyl, N-propyl, N-butyl, N-hydroxyethyl, or N-hydroxypropyl
  • the product is made by reacting N-alkyl- or N-hydroxyalkyl-glucamine with a fatty ester selected from fatty methyl esters, fatty ethyl esters, and fatty triglycerides in the presence of a catalyst selected from the group consisting of trilithium phosphate, trisodium phosphate, tripotassium phosphate, tetrasodium pyrophosphate, pentapotassium tripolyphosphate, lithium hydroxide, sodium hydroxide, potassium hydroxide, calcium hydroxide, lithium carbonate, sodium carbonate, potassium carbonate
  • the amount of catalyst is preferably from about 0.5 mole % to about 50 mole %, more preferably from about 2.0 mole % to about 10 mole %, on an N-alkyl or N-hydroxyalkyl-glucamine molar basis.
  • the reaction is preferably carried out at from about 138°C to about 170°C for typically from about 20 to about 90 minutes.
  • the reaction is also preferably carried out using from about 1 to about 10 weight % of a phase transfer agent, calculated on a weight percent basis of total reaction mixture, selected from saturated fatty alcohol polyethoxylates, alkylpolyglucosides, linear glucamide surfactant, and mixtures thereof.
  • this process is carried out as follows:
  • N-linear glucosyl fatty acid amide product is added to the reaction mixture, by weight of the reactants, as the phase transfer agent if the fatty ester is a triglyceride. This seeds the reaction, thereby increasing reaction rate.
  • a detailed experimental procedure is provided below in the section entitled Experimental.
  • polyhydroxy "fatty acid” amide materials used herein also offer the advantages to the detergent formulator that they can be prepared wholly or primarily from natural, renewable, non-petro-chemical feedstocks and are degradable. They also exhibit low toxicity to aquatic life.
  • the processes used to produce them will also typically produce quantities of nonvolatile by-product such as esteramides and cyclic polyhydroxy fatty acid amide.
  • the level of these by-products will vary depending upon the particular reactants and process conditions.
  • the polyhydroxy fatty acid amide incorporated into the detergent compositions hereof will be provided in a form such that the polyhydroxy fatty acid amide-containing composition added to the detergent contains less than about 10%, preferably less than about 4%, of cyclic polyhydroxy fatty acid amide.
  • the preferred processes described above are advantageous in that they can yield rather low levels of by-products, including such cyclic amide by-product.
  • the detergent compositions of the present invention contain magnesium in a molar amount corresponding to 0.1X-2.0X, preferably from 0.2X-1.7X, more preferably from 0.3X-1.5X, wherein X is the number of moles of anionic sulfate or sulfonate surfactant present in such detergent compositions.
  • individual anionic surfactants can be made as aqueous solutions of alkali metal or ammonium salts which are then mixed together with a hydrotrope, after which the magnesium can be introduced as a water soluble salt, such as the chloride or sulfate.
  • a water soluble salt such as the chloride or sulfate.
  • Optional minor ingredients may then be added before pH and viscosity are adjusted.
  • This method has the advantage of utilizing conventional techniques and equipment but does result in the introduction of additional chloride or sulfate ions which can increase the chill point temperature (the temperature at which inorganic salts precipitate as crystals in the liquid).
  • the magnesium can be added by neutralization of the acid with a magnesium oxide or magnesium hydroxide slurry in water. This technique avoids the addition of chloride and sulfate ions. The neutralized surfactant salts and the hydrotrope are then added to the final mixing tank and any optional ingredients are added before adjusting the pH.
  • a third technique is to add the anionic sulfate or sulfonate surfactant as a magnesium sulfate salt.
  • any magnesium desired in molar excess of anionic surfactant can be added in one of the other methods identified herein, or by methods known to those skilled in the art.
  • the detergent compositions of the present invention are liquid detergent compositions.
  • These preferred liquid detergent compositions comprise from about 95% to about 35% by weight, preferably from about 90% to about 50% by weight, most preferably from about 80% to about 60% by weight of a liquid carrier, e.g., water, preferably a mixture of water and a C1-C4 monohydric alcohol (e.g., ethanol, propanol, isopropanol, butanol, and mixtures thereof), with ethanol being the preferred alcohol.
  • a liquid carrier e.g., water, preferably a mixture of water and a C1-C4 monohydric alcohol (e.g., ethanol, propanol, isopropanol, butanol, and mixtures thereof), with ethanol being the preferred alcohol.
  • a liquid carrier e.g., water, preferably a mixture of water and a C1-C4 monohydric alcohol (e.g., ethanol, propanol, isopropanol
  • liquid detergent compositions hereof will preferably be formulated such that during use in aqueous cleaning operations the wash water will have a pH of between about 5.5 and about 9.5, more preferably between about 6.5 and about 8.0.
  • Liquid product formulations preferably have a pH in the range of from about 5.0 to about 10.5, preferably from about 6.0 to about 9.0, most preferably from about 6.5 to about 7.5.
  • Techniques for controlling pH at recommended usage levels include the use of buffers, alkali, acids, etc., and are well known to those skilled in the art.
  • the detergent compositions of the present invention may also be in the form of a gel.
  • Such compositions are typically formulated in the same manner as liquid detergent compositions, except they contain an additional thickening agent.
  • any material or materials which can be admixed with the aqueous liquid to provide shear-thinning compositions having sufficient yield values can be used in the compositions of this invention.
  • Materials such as colloidal silica, particulate polymers, such as polystyrene and oxidized polystyrene, combinations of certain surfactants, and water-soluble polymers such as polyacrylate are known to provide yield values.
  • a preferred thickening agent useful in the compositions of the present invention is a high molecular weight polycarboxylate polymer thickener.
  • high molecular weight it is meant from about 500,000 to about 5,000,000, preferably from about 750,000 to about 4,000,000.
  • the polycarboxylate polymer may be a carboxyvinyl polymer.
  • carboxyvinyl polymer Such compounds are disclosed in U.S. Patent 2,798,053, which is incorporated herein by reference. Methods for making carboxyvinyl polymers are also disclosed in Brown, and are also incorporated herein by reference.
  • a carboxyvinyl polymer is an interpolymer of a monomeric mixture comprising a monomeric olefinically unsaturated carboxylic acid, and from about 0.1% to about 10% by weight of the total monomers of a polyether of a polyhydric alcohol, which polyhydric alcohol contains at least four carbon atoms to which are attached at least three hydroxyl groups, the polyether containing more than one alkenyl group per molecule.
  • Other monoolefinic monomeric materials may be present in the monomeric mixture if desired, even in predominant proportion.
  • Carboxyvinyl polymers are substantially insoluble in liquid, volatile organic hydrocarbons and are dimensionally stable on exposure to air.
  • Preferred polyhydric alcohols used to produce carboxyvinyl polymers include polyols selected from the class consisting of oligosaccharides, reduced derivatives thereof in which the carbonyl group is converted to an alcohol group, and pentaerythritol; more preferred are oligosaccharides, most preferred is sucrose. It is preferred that the hydroxyl groups of the polyol which are modified be etherified with allyl groups, the polyol having at least two allyl ether groups per polyol molecule. When the polyol is sucrose, it is preferred that the sucrose have at least about five allyl ether groups per sucrose molecule. It is preferred that the polyether of the polyol comprise from about 0.1% to about 4% of the total monomers, more preferably from about 0.2% to about 2.5%.
  • Preferred monomeric olefinically unsaturated carboxylic acids for use in producing carboxyvinyl polymers used herein include monomeric, polymerizable, alpha-beta monoolefinically unsaturated lower aliphatic carboxylic acids; more preferred are monomeric monoolefinic acrylic acids of the structure herein R is a substituent selected from the group consisting of hydrogen and lower alkyl groups; most preferred is acrylic acid.
  • Carboxyvinyl polymers useful in formulations of the present invention have a molecular weight of at least about 750,000. Preferred are highly cross-linked carboxyvinyl polymers having a molecular weight of at least about 1,250,000. Also preferred are carboxyvinyl polymers having a molecular weight of at least about 3,000,000, which may be less highly cross-linked.
  • Carboxyvinyl polymers useful in formulations of the present invention include Carbopol 910 having a molecular weight of about 750,000; preferred is Carbopol 941 having a molecular weight of about 1,250,000, and more preferred are Carbopols 934 and 940 having molecular weights of about 3,000,000 and 4,000,000, respectively.
  • Carbopol 934 is a very slightly cross-linked carboxyvinyl polymer having a molecular weight of about 3,000,000. It has been described as a high molecular weight polyacrylic acid cross-linked with about 1% of polyallyl sucrose having an average of about 5.8 allyl groups for each molecule of sucrose.
  • Additional polycarboxylate polymers useful in the present invention are Sokolan PHC-25 R , a polyacrylic acid available from BASF Corp., and Gantrez R a poly(methyl vinyl ether/maleic acid) interpolymer available from GAF Corp.
  • Preferred polycarboxylate polymers of the present invention are non-linear, water-dispersible, polyacrylic acid cross-linked with a polyalkenyl polyether and having a molecular weight of from about 750,000 to about 4,000,000.
  • polycarboxylate polymer thickeners are the Carbopol 600 series resins available from B. F. Goodrich. Especially preferred are Carbopol 616 and 617. It is believed that these resins are more highly cross-linked than the 900 series resins and have molecular weights between about 1,000,000 and 4,000,000. Mixtures of polycarboxylate polymers as herein described may also be used in the present invention. Particularly preferred is a mixture of Carbopol 616 and 617 series resins.
  • the polycarboxylate polymer thickener is utilized preferably with essentially no clay thickening agents. In fact, it has been found that if the polycarboxylate polymers of the present invention are utilized with clay in the composition of the present invention, a less desirable product, in terms of phase instability, results. In other words, the polycarboxylate polymer is preferably used instead of clay as a thickening/stabilizing agent in the present compositions.
  • the polycarboxylate polymer also provides a reduction in what is commonly called “bottle hang-up". This term refers to the inability to dispense all of the dishwashing detergent product from its container. Without intending to be bound by theory, it is believed that the thickened compositions of the present invention provide this benefit because the force of cohesion of the composition is greater than the force of adhesion to the container wall. With clay thickener systems, which most commercially available products contain, bottle hang-up can be a significant problem under certain conditions.
  • the long chain molecules of the polycarboxylate polymer thickener help suspend solids in the thickened detergent compositions of the present invention and help keep the matrix expanded.
  • the polymeric material is also less sensitive than clay thickeners to destruction due to repeated shearing, such as occurs when the composition is vigorously mixed.
  • the polycarboxylate polymer is used as a thickening agent in the compositions of the present invention, it is typically present at a level of from about 0.1% to about 10%, preferably from about 0.2% to about 2% by weight.
  • the thickening agents are used to provide a yield value of from about 50 to about 350 and most preferably from about 75 to about 250.
  • the yield value is an indication of the shear stress at which the gel strength is exceeded and flow is initiated. It is measured herein with a Brookfield RVT model viscometer with a T-bar B spindle at 25°C utilizing a Helipath drive upward during associated readings. The system is set to 0.5 rpm and a reading is taken for the composition to be tested after 30 seconds or after the system is stable. The system is stopped and the rpm is reset to 1.0 rpm. A reading is taken for the same composition after 30 seconds or after the system is stable. Stress at zero shear is equal to two times the 0.5 rpm reading minus the reading at 1.0 rpm. The yield value is calculated as the stress at zero shear times 18.8 (conversion factor).
  • anionic surfactants useful for detersive purposes can also be included in the compositions hereof.
  • exemplary, non-limiting useful anionics include salts (e.g., sodium, potassium, ammonium, and substituted ammonium salts such as mono-, di- and triethanolamine salts) of soap, sulfonated polycarboxylic acids prepared by sulfonation of the pyrolyzed product of alkaline earth metal citrates, e.g., as described in British patent specification No.
  • alkyl glycerol sulfonates 1,082,179, C8-C22 alkylsulfates, C8-C24 alkylpolyglycolethersulfates (containing up to 10 moles of ethylene oxide); alkyl glycerol sulfonates, fatty acyl glycerol sulfonates, fatty acyl glycerol sulfates, alkyl phenol ethylene oxide ether sulfates, alkyl phosphates, isethionates such as the acyl isethionates, acyl taurates, fatty acid amides, alkyl succinates and sulfosuccinates, acyl sarcosinates, sulfates of alkylpolysaccharides such as the sulfates of alkylpolyglucoside (the nonionic nonsulfated compounds having already been described herein), alkyl ether carbonates, al
  • Suitable nonionic detergent surfactants are generally disclosed in U.S. Patent 3,929,678, Laughlin et al., issued December 30, 1975, at column 13, line 14 through column 16, line 6, incorporated herein by reference. Exemplary, non-limiting classes of useful nonionic surfactants are listed below.
  • Ampholytic surfactants may also be incorporated into the detergent compositions hereof. These surfactants can be broadly described as aliphatic derivatives of secondary or tertiary amines, or aliphatic derivatives of heterocyclic secondary and tertiary amines in which the aliphatic radical can be straight-branched chains.
  • One of the aliphatic substituents contains at least 8 carbon atoms, typically from 8 to 18 carbon atoms, and at least one contains an anionic water-solubilizing group, e.g., carboxy, sulfonate, sulfate. See U.S. Patent No. 3,929,678 to Laughlin et al., issued December 30, 1975, at column 19, lines 18-35 (herein incorporated by reference) for examples of useful ampholytic surfactants.
  • Zwitterionic surfactants may also be incorporated into the detergent compositions hereof. These surfactants can be broadly described as derivatives of secondary and tertiary amines, derivatives of heterocyclic secondary and tertiary amines, or derivatives of quaternary ammonium, quaternary phosphonium or tertiary sulfonium compounds. See U.S. Patent No. 3,929,678 to Laughlin et al., issued December 30, 1975, at column 19, line 38 through column 22, line 48 (herein incorporated by reference) for examples of useful zwitterionic surfactants.
  • ampholytic and zwitterionic surfactants are generally used in combination with one or more anionic and/or nonionic surfactants.
  • Betaine and sulfobetaine (“sultaine”) surfactants, and mixtures thereof, are especially preferred for use herein.
  • Preferred additional surfactants are anionic and nonionic surfactants.
  • Preferred nonionic surfactants include polyethylene, polypropylene and polybutylene oxide condensates of alkyl phenols; the alkyl ethoxylate condensation products of aliphatic alcohols with ethylene oxide; the condensation products of ethylene oxide with a hydrophobic base formed by the condensation of propylene oxide with propylene glycol; the condensation product of ethylene oxide with the product resulting from the reaction of propylene oxide and ethylenediamine; alkylpolysaccharides, more preferably alkylpolysaccharides having a hydrophobic group containing from about 6 to about 30 carbon atoms and a polysaccharide group containing from about 1.3 to about 10 saccharide units; fatty acid amides; and mixtures thereof.
  • these optional additional surfactants are typically present at a concentration of from about 1.0% to about 15%, preferably from about 2% to about 10% by weight.
  • detergency builders either of the organic or inorganic type, although such builders in general are not preferred for use in the composition of the present invention.
  • water-soluble inorganic builders which can be used, either alone or in admixture with themselves or with organic alkaline sequestrant builder salts, are glycine, alkyl and alkenyl succinates, alkali metal carbonates, phosphates, polyphosphates, and silicates.
  • Specific examples of such salts are sodium tripolyphosphate, sodium carbonate, potassium carbonate, sodium pyrophosphate, potassium pyrophosphate, potassium tripolyphosphate, and sodium hexametaphosphate.
  • alkali metal polycarboxylates examples of which include, but are not limited to, water-soluble citrates such as sodium and potassium citrate, sodium and potassium tartrate, sodium and potassium ethylenediaminetetraacetate, sodium and potassium N-(2-hydroxyethyl)-ethylene diamine triacetates, sodium and potassium nitrilo triacetates, sodium and potassium N-(2-hydroxyethyl)-nitrilo diacetates, sodium and potassium oxydisuccinates, and sodium and potassium tartrate mono- and di-succinates, such as those described in U.S.
  • water-soluble citrates such as sodium and potassium citrate, sodium and potassium tartrate, sodium and potassium ethylenediaminetetraacetate, sodium and potassium N-(2-hydroxyethyl)-ethylene diamine triacetates, sodium and potassium nitrilo triacetates, sodium and potassium N-(2-hydroxyethyl)-nitrilo diacetates, sodium and potassium oxydis
  • Patent 4,663,071 (Bush et al., issued May 5, 1987), the disclosure of which is incorporated herein.
  • Other organic detergency builders such as water-soluble phosphonates, can be used in the compositions of the present invention.
  • detergency builders in general have limited value when the compositions of the present invention are in the form of light-duty liquid dishwashing detergent compositions. If included in the compositions of the present invention, these optional builders are typically present at a concentration of from about 1.0% to about 10%, preferably from about 2% to about 5% by weight.
  • Diluents can be inorganic salts, such as sodium and potassium sulfate, ammonium chloride, sodium and potassium chloride, sodium bicarbonate, etc.
  • Diluents useful in the compositions of the present invention are typically present at levels of from about 1% to about 10%, preferably from about 2% to about 5% by weight.
  • Solvents useful herein include water and lower molecular weight alcohols, such as ethyl alcohol, isopropyl alcohol, etc. Solvents useful in the compositions of the present invention are typically present at levels of from about 1% to about 60%, preferably from about 5% to about 50% by weight.
  • Hydrotropes such as sodium and potassium toluene sulfonate, sodium and potassium xylene sulfonate, sodium and potassium cumene sulfonate, trisodium and tripotassium sulfosuccinate, and related compounds (as disclosed in U.S. Patent 3,915,903, the disclosure of which is incorporated herein) can be utilized in the interests of achieving a desired product phase stability and viscosity. It has been found that the hydrotropes can have a positive effect on the suds benefit of the present invention. While not intending to be bound by theory, it is believed that this benefit is due to the viscosity characteristics of such hydrotropes. Hydrotropes useful in the compositions of the present invention are typically present at levels of from about 1% to about 10%, preferably from about 2% to about 7% by weight.
  • Optional ingredients useful when the compositions of the present invention are used in liquid dishwashing detergent applications include drainage promoting ethoxylated nonionic surfactants of the type disclosed in U.S. Patent 4,316,824, issued to Pancheri on February 23, 1982, the disclosure of which is incorporated herein.
  • compositions of the present invention are beneficial in that they provide unexpected improved sudsing and grease cleaning performance and clean dishes without imparting a "greasy" feel to the cleaned dish, which is especially important in consumer markets where the cleanliness of a dish is judged by the lack of such a "greasy” feel.
  • additional benefits of the compositions of the present invention are their ease of rinsing and that they reduce the slippery feel associated with typical liquid detergent compositions. This is important in consumer markets where such a "slippery" feel is not favored and is viewed as resulting from incomplete rinsing of surfactants from the dish surface.
  • soiled dishes are 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 composition of the present invention.
  • the actual amount of liquid detergent composition used will be based on the judgement 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 21% to about 44% by weight, preferably from about 25% to about 35% 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 and Japanese 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 method of use will comprise immersing the soiled dishes into a water bath which is absent any liquid dishwashing detergent.
  • a device for absorbing liquid dishwashing detergent such as a sponge, is placed directly into a separate quantity of undiluted liquid dishwashing composition for a period of time typically ranging from about 1 to about 5 seconds.
  • the absorbing device, and consequently the undiluted liquid dishwashing composition is then contacted individually to the surface of each of the soiled dishes to remove said soiling.
  • the absorbing device is typically contacted with each dish surface for a period of time range 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 to the dish surface is preferably accompanied by concurrent scrubbing.
  • one suitable apparatus for use herein comprises a three-liter four-necked flask fitted with a motor-driven paddle stirrer and a thermometer of length sufficient to contact the reaction medium.
  • the other two necks of the flask are fitted with a nitrogen sweep and a wide-bore side-arm (caution: a wide-bore side-arm is important in case of very rapid methanol evolution) to which is connected an efficient collecting condenser and vacuum outlet.
  • the latter is connected to a nitrogen bleed and vacuum gauge, then to an aspirator and a trap.
  • a 500 watt heating mantle with a variable transformer temperature controller (“Variac”) used to heat the reaction is so placed on a lab-jack that it may be readily raised or lowered to further control temperature of the reaction.
  • Variac variable transformer temperature controller
  • N-methylglucamine (195 g., 1.0 mole, Aldrich, M4700-0) and methyl laurate (Procter & Gamble CE 1270, 220.9 g., 1.0 mole) are placed in a flask.
  • the solid/liquid mixture is heated with stirring under a nitrogen sweep to form a melt (approximately 25 minutes).
  • catalyst anhydrous powdered sodium carbonate, 10.5 g., 0.1 mole, J. T. Baker
  • the nitrogen sweep is shut off and the aspirator and nitrogen bleed are adjusted to give 16934 Pa (5 inches (5/31 atm.)) Hg. vacuum. From this point on, the reaction temperature is held at 150° C by adjusting the Variac and/or by raising or lowering the mantle.
  • a surfactant paste is initially formed by combining any desired surfactants with water and alcohol.
  • the surfactants contained in this surfactant paste include the polyhydroxy fatty acid amides of the present invention.
  • the surfactant paste should be pumpable at room or elevated temperatures.
  • three-quarters of the water of the formulated product, one-half of the alcohol of the formulated product, and any required hydrotropes are combined with mixing to give a clear solution.
  • Magnesium is added next, followed by the surfactant paste, to form a mixture.
  • the magnesium may be added directly to the mixing vessel as magnesium chloride, magnesium sulfate, or as magnesium oxide or hydroxide powder.
  • the magnesium oxide or hydroxide powder is added to the acid form of the surfactant salts (e.g, alkyl benzene sulfonates, alkyl sulfates, alkyl ethoxylated sulfates, methyl ester sulfonates, etc.) in the surfactant paste.
  • the surfactant salts e.g, alkyl benzene sulfonates, alkyl sulfates, alkyl ethoxylated sulfates, methyl ester sulfonates, etc.
  • the pH of the magnesium-containing surfactant paste is then adjusted by using NaOH or KOH solutions.
  • the mixture is mixed until a homogenous, clear solution product is obtained. Additional water, alcohol, and any desired additional hydrotropes (added as a solution) may then be added to trim the solution product viscosity to the desired level, ideally between 50 and 1 x 10 ⁇ 3 Pa (1000 cps), as measured by a Brookfield viscometer at 38.9°C (70°F).
  • the pH of the solution product is then adjusted with either HCl or NaOH to a level of 7.0 ⁇ 0.7 for formulas containing ammonium ions, and 8.5 ⁇ 1.5 for formulas which do not contain ammonium ions.
  • Perfume, dye and other ingredients are added as the last step.
  • Lytron can be added directly as a dispersion with mixing.
  • Ethylene glycol distearate must be added in a molten state with rapid mixing to form the desired pearlescent crystals.
  • compositions are formulated on a weight percent basis. These compositions are prepared in same manner as the compositions of Example I.
  • Component A B C D E C12 ⁇ 14 alkyl N-methyl glucamide 5.0 5.0 10.0 10.0 6.0 Sodium C 11.2 linear alkyl benzene sulfonate 10.0 - - - - Ammonium coconut alcohol ethoxylate (1.0 ave.) sulfate - 25.0 - - 8.0 Ammonium coconut alcohol sulfate 10.0 5.0 - - 8.0 Sodium salt of coconut acid methyl ester sulfonate - - 15.0 - - MgCl2 0.5 1.5 0.8 0.6 1.8 Sodium C14 ⁇ 16 alpha olefin sulfonate - - - 20.0 - Coconut polyglycoside (1.6 ave.
  • compositions are formulated on a weight percent basis. These compositions are prepared in same manner as the compositions of Example I.
  • Coconut polyglycoside (1.6 ave.
  • compositions are formulated on a weight percent basis. These compositions are prepared in the same manner as the compositions of Example I.
  • COMPONENT A B C D E Ammonium C 11.2 linear alkyl benzene sulfonate - 10.0 8.0 13.5 13.5 C12 ⁇ 14 fatty acid N-methyl glucamide 16.5 12.5 10.0 12.5 10.0 Ammonium C12-C14 alkyl (EO) 0.8 sulfate 12.5 11.0 10.0 - 6.0 Cocoamide propyl betaine 1.5 4.0 3.0 2.0 2.0 Hexadecyl dimethyl betaine 2.0 3.5 3.0 3.0 2.5 Coconut monoethanolamide 3.8 3.8 3.8 2.0 - C12-C14 alkyl dimethyl amine oxide - - 4.0 2.0 3.0 Sodium cumene sulfonate 1.0 1.0 1.0 1.0 2.0 Ethanol 4.5 5.0 4.0 4.0 Urea 0.5 - - - 0.7 Magnesium hydroxide 1.6 1.5 1.5 1.5 1.5 Water & Mis
  • compositions are formulated on a weight percent basis. These compositions are prepared in the same manner as the compositions of Example I. COMPONENT A B C D E F C14 ⁇ 16 alpha olefin sulfonate - - 5.0 - - Magnesium C14 ⁇ 16 alpha olefin sulfonate 5.0 10.0 10.0 5.0 - - Dodecyl benzene sulfonate - - - - 5.0 - C12 ⁇ 14 fatty acid N-methyl glucamide 12.0 12.0 5.0 10.0 10.0 12.0 Magnesium C12 ⁇ 14 alkyl ethoxy (0.8 ave.) sulfate 12.0 12.0 - - - 15.0 Magnesium C12 ⁇ 13 alkyl ethoxy (1.0 ave.) sulfate - - 5.0 5.0 - C10 primary alcohol ethoxylate (8.0 ave.) - - - -
  • compositions are formulated on a weight percent basis. These compositions are prepared in the same manner as the compositions of Example I. COMPONENT A B C D E F C12 ⁇ 14 fatty acid N-methyl glucamide 5.0 10.0 14.0 8.0 10.0 10.0 Magnesium C12 ⁇ 14 alkyl ethoxy (0.8 ave.) sulfate 5.0 - - - - - Magnesium C12 ⁇ 13 alkyl ethoxy (1.0 ave.) sulfate 5.0 10.0 13.0 - - 10.0 Magnesium C12 ⁇ 13 alkyl ethoxy (6.5 ave.) sulfate 5.0 - - 13.0 - - Magnesium C14 ⁇ 16 paraffin sulfonate - 5.0 - 5.0 10.0 - Magnesium C12 ⁇ 14 methyl ester sulfonate - - - 5.0 10.0 - C12 ⁇ 14 polyglycoside 5.0 5.0 5.0
  • compositions A, C, E and G do not exemplify the present invention COMPONENT A B C D E F G Sodium C14 ⁇ 15 paraffin sulfonate 26.0 - - - 15.0 - - Magnesium C14 ⁇ 16 paraffin sulfonate - 26.0 - - - - - Sodium salt of a sulfated coconut alcohol ethoxylated with 3 moles of ethoxylated oxide - - 14.0 - - 15.0 10.0 Magnesium salt of a sulfated coconut alcohol ethoxylated with 3 moles of ethylene oxide - - - 34.0 - - - Sodium coconut glyceryl ether sulfonate - - - - 5.0 - - Magnesium coconut glyceryl ether sulfonate - - - - 5.0 - - Magnesium coconut glyceryl ether sulfon
  • An alternate method for preparing the polyhydroxy fatty acid amides used herein is as follows.
  • a reaction mixture consisting of 84.87g. fatty acid methyl ester (source: Procter & Gamble methyl ester CE1270), 75g. N-methyl-D-glucamine (source: Aldrich Chemical Company M4700-0), 1.04g. sodium methoxide (source: Aldrich Chemical Company 16,499-2), and 68.51g. methyl alcohol is used.
  • the reaction vessel comprises a standard reflux set-up fitted with a drying tube, condenser and stir bar. In this procedure, the N-methyl glucamine is combined with methanol with stirring under argon and heating is begun with good mixing (stir bar; reflux).
  • the ester and sodium methoxide catalyst are added. Samples are taken periodically to monitor the course of the reaction, but it is noted that the solution is completely clear by 63.5 minutes. It is judged that the reaction is, in fact, nearly complete at that point.
  • the reaction mixture is maintained at reflux for 4 hours. After removal of the methanol, the recovered crude product weighs 156.16 grams. After vacuum drying and purification, an overall yield of 106.92 grams purified product is recovered. However, percentage yields are not calculated on this basis, inasmuch as regular sampling throughout the course of the reaction makes an overall percentage yield value meaningless.
  • the reaction can be carried out at 80% and 90% reactant concentrations for periods up to 6 hours to yield products with extremely small by-product formation.
  • polyhydroxy fatty acid amides are, by virtue of their amide bond, subject to some instability under highly basic or highly acidic conditions. While some decomposition can be tolerated, it is preferred that these materials not be subjected to pH's above about 11, preferably 10, nor below about 3 for unduly extended periods. Final product pH (liquids) is typically 7.0-9.0.
  • the detergent formulator will recognize that it is a simple and convenient matter to use an acid which provides an anion that is otherwise useful and desirable in the finished detergent composition.
  • citric acid can be used for purposes of neutralization and the resulting citrate ion ( ca . 1%) be allowed to remain with a ca . 40% polyhydroxy fatty acid amide slurry and be pumped into the later manufacturing stages of the overall detergent-manufacturing process.
  • the acid forms of materials such as oxydisuccinate, nitrilotriacetate, ethylenediaminetetraacetate, tartrate/succinate, and the like, can be used similarly.
  • the polyhydroxy fatty acid amides derived from coconut alkyl fatty acids are more soluble than their tallow alkyl (predominantly C16-C18) counterparts. Accordingly, the C12-C14 materials are somewhat easier to formulate in liquid compositions, and are more soluble in cool-water laundering baths. However, the C16-C18 materials are also quite useful, especially under circumstances where warm-to-hot wash water is used. Indeed, the C16-C18 materials may be better detersive surfactants than their C12-C14 counterparts. Accordingly, the formulator may wish to balance ease-of-manufacture vs . performance when selecting a particular polyhydroxy fatty acid amide for use in a given formulation.
  • solubility of the polyhydroxy fatty acid amides can be increased by having points of unsaturation and/or chain branching in the fatty acid moiety.
  • materials such as the polyhydroxy fatty acid amides derived from oleic acid and iso-stearic acid are more soluble than their n-alkyl counterparts.
  • polyhydroxy fatty acid amides prepared from disaccharides, trisaccharides, etc. will ordinarily be greater than the solubility of their monosaccharide-derived counterpart materials. This higher solubility can be of particular assistance when formulating liquid compositions.
  • polyhydroxy fatty acid amides wherein the polyhydroxy group is derived from maltose appear to function especially well as detergents when used in combination with conventional alkylbenzene sulfonate ("LAS") surfactants.
  • LAS alkylbenzene sulfonate
  • the polyhydroxy fatty acid amides can be manufactured not only from the purified sugars, but also from hydrolyzed starches, e.g., corn starch, potato starch, or any other convenient plant-derived starch which contains the mono-, di-, etc. saccharide desired by the formulator. This is of particular importance from the economic standpoint. Thus, "high glucose” corn syrup, "high maltose” corn syrup, etc. can conveniently aid economically be used. De-lignified, hydrolyzed cellulose pulp can also provide a raw material source for the polyhydroxy fatty acid amides.
  • polyhydroxy fatty acid amides derived from the higher saccharides such as maltose, lactose, etc.
  • the more soluble polyhydroxy fatty acid amides can help solubilize their less soluble counterparts, to varying degrees.
  • the formulator may elect to use a raw material comprising a high glucose corn syrup, for example, but to select a syrup which contains a modicum of maltose (e.g., 1% or more).
  • the resulting mixture of polyhydroxy fatty acids will, in general, exhibit more preferred solubility properties over a broader range of temperatures and concentrations than would a "pure" glucose-derived polyhydroxy fatty acid amide.
  • the polyhydroxy fatty acid amides prepared from mixed sugars can offer very substantial advantages with respect to performance and/or ease-of-formulation.
  • some loss of grease removal performance may be noted at fatty acid maltamide levels above about 25% and some loss in sudsing above about 33% (said percentages being the percentage of maltamide-derived polyhydroxy fatty acid amide vs . glucose-derived polyhydroxy fatty acid amide in the mixture). This can vary somewhat, depending on the chain length of the fatty acid moiety.
  • the formulator electing to use such mixtures may find it advantageous to select polyhydroxy fatty acid amide mixtures which contain ratios of monosaccharides (e.g., glucose) to di- and higher saccharides (e.g., maltose) from about 4:1 to about 99:1.
  • monosaccharides e.g., glucose
  • di- and higher saccharides e.g., maltose
  • the formulator of, for example, solid, typically granular, detergent compositions may find it convenient to run the process at 30°C-90°C in solvents which comprise ethoxylated alcohols, such as the ethoxylated (EO 3-8) C12-C14 alcohols, such as those available as NEODOL 23 EO6.5 (Shell).
  • ethoxylated alcohols such as the ethoxylated (EO 3-8) C12-C14 alcohols, such as those available as NEODOL 23 EO6.5 (Shell).
  • the industrial scale reaction sequence for preparing the preferred acyclic polyhydroxy fatty acid amides will comprise: Step 1 - preparing the N-alkyl polyhydroxy amine derivative from the desired sugar or sugar mixture by formation of an adduct of the N-alkyl amine and the sugar, followed by reaction with hydrogen in the presence of a catalyst; followed by Step 2 - reacting the aforesaid polyhydroxy amine with, preferably, a fatty ester to form an amide bond.
  • Step 2 of the reaction sequence can be prepared by various art-disclosed processes, the following process is convenient and makes use of economical sugar syrup as the raw material. It is to be understood that, for best results when using such syrup raw materials, the manufacturer should select syrups that are quite light in color or, preferably, nearly colorless ("water-white").
  • Adduct Formation The following is a standard process in which about 420 g of about 55% glucose solution (corn syrup - about 231 g glucose - about 1.28 moles) having a Gardner Color of less than 1 is reacted with about 119 g of about 50% aqueous methylamine (59.5 g of methylamine - 1.92 moles) solution.
  • the methylamine (MMA) solution is purged and shielded with N2 and cooled to about 10°C, or less.
  • the corn syrup is purged and shielded with N2 at a temperature of about 10°-20°C.
  • the corn syrup is added slowly to the MMA solution at the indicated reaction temperature as shown.
  • the Gardner Color is measured at the indicated approximate times in minutes.
  • the time to reach substantial equilibrium concentration of the adduct is shortened by the use of higher ratios of amine to sugar.
  • equilibrium is reached in about two hours at a reaction temperature of about 30°C.
  • the time is at least about three hours.
  • the combination of amine:sugar ratio; reaction temperature; and reaction time is selected to achieve substantially equilibrium conversion, e.g., more than about 90%, preferably more than about 95%, even more preferably more than about 99%, based upon the sugar, and a color that is less than about 7, preferably less than about 4, more preferably less than about 1, for the adduct.
  • substantially equilibrium conversion e.g., more than about 90%, preferably more than about 95%, even more preferably more than about 99%, based upon the sugar, and a color that is less than about 7, preferably less than about 4, more preferably less than about 1, for the adduct.
  • the product after removal of water and MMA by evaporation, is about 95% N-methyl glucamine, a white powder.
  • the above procedure is repeated with about 23.1 g of Raney Ni catalyst with the following changes.
  • the catalyst is washed three times and the reactor, with the catalyst in the reactor, is purged twice with 13.8 x 105 Pa (200 psig H2) and the reactor is pressurized with H2 at 1600 psig for two hours, the pressure is released at one hour and the reactor is repressurized to 110.3 x 105 Pa (1600 psig).
  • the adduct is then pumped into the reactor which is at 13.8 x 105 Pa (200 psig) and 20°C, and the reactor is purged with 13.8 x 105 Pa (200 psig) H2, etc., as above.
  • the resulting product in each case is greater than about 95% N-methyl glucamine; has less than about 10 ppm Ni based upon the glucamine; and has a solution color of less than about Gardner 2.
  • the crude N-methyl glucamine is color stable to about 140°C for a short exposure time. It is important to have good adduct that has low sugar content (less than about 5%, preferably less than about 1%) and a good color (less than about 7, preferably less than about 4 Gardner, more preferably less than about 1).
  • adduct is prepared starting with about 159 g of about 50% methylamine in water, which is purged and shielded with N2 at about 10-20°C. About 330 g of about 70% corn syrup (near water-white) is degassed with N2 at about 50°C and is added slowly to the methylamine solution at a temperature of less than about 20°C. The solution is mixed for about 30 minutes to give about 95% adduct that is a very light yellow solution. About 190 g of adduct in water and about 9 g of United Catalyst G49B Ni catalyst are added to a 200 ml autoclave and purged three times with H2 at about 20°C.
  • the H2 pressure is raised to about 13.8 x 105 Pa (200 psi) and the temperature is raised to about 50°C.
  • the pressure is raised 17.25 x 105 Pa to (250 psi) and the temperature is held at about 50-55°C for about three hours.
  • the product, which is about 95% hydrogenated at this point, is then raised to a temperature of about 85°C for about 30 minutes and the product, after removal of water and evaporation, is about 95% N-methyl glucamine, a white powder. It is also important to minimize contact between adduct and catalyst when the H2 pressure is less than about 68.9 x 105 Pa (1000 psig) to minimize Ni content in the glucamine.
  • the nickel content in the N-methyl glucamine in this reaction is about 100 ppm as compared to the less than 10 ppm in the previous reaction.
  • the following reactions with H2 are run for direct comparison of reaction temperature effects.
  • a 200 ml autoclave reactor is used following typical procedures similar to those set forth above to make adduct and to run the hydrogen reaction at various temperatures.
  • Adduct for use in making glucamine is prepared by combining about 420 g of about 55% glucose (corn syrup) solution (231 g glucose; 1.28 moles) (the solution is made using 99DE corn syrup from CarGill, the solution having a color less than Gardner 1) and about 119 g of 50% methylamine (59.5 g MMA; 1.92 moles) (from Air Products).
  • the reaction procedure is as follows:
  • the preparation of the tallow (hardened) fatty acid amide of N-methyl maltamine for use in detergent compositions according to this invention is as follows.
  • the surfactants comprise various alkyl ethoxy sulfate surfactants which, using standard terminology, are abbreviated to indicate their average degree of ethoxylation; thus C12 ⁇ 13EO(0.8) sulfate indicates a sulfated mixed C12-C13 alcohol fraction having an average degree of ethoxylation of 0.8.
  • C12 ⁇ 13 amine oxide is a mixed C12 ⁇ 13 (average) dimethyl amine oxide.
  • the C12 ⁇ 14 AP betaine is C 12/14 H 25/29 CONH(CH2)3N+(CH3)2CH2CO2H.
  • the C12 ⁇ 14 AP sultaine is C12/C14H 25/29 CONH(CH2)3N+(CH3)2CH2CH(OH)CH2SO3H.
  • the C12 ⁇ 14 DM betaine is C 12/14 H 25/29 N+(CH3)2CH2CO2H.
  • the ethoxylated nonionic surfactant designated C9 ⁇ 1EO(8) refers to C9-C11 alcohols ethoxylated with an average of 8 moles of ethylene oxide, respectively.
  • the Ca++ and Mg++ cations are conveniently introduced into the compositions as CaCl2 and MgCl2.
  • compositions comprises water and citrate/propylene glycol present in the glucamide surfactant (1-5%) and 1-3% cumene sulfonate or xylene sulfonate hydrotrope.
  • the pH is typically 6.8-7.4 (NH4+ salts) or 7-8.2 (Na+ salts) .
  • Compositions C and D do not exemplify the present invention.
  • a granular laundry detergent composition suitable for use at the relatively high concentrations common to front-loading automatic washing machines, especially in Europe, and over a wide range of temperatures is as follows.
  • Ingredient Wt. % SOKALAN CP5 (100% active as Na salt)1 3.52 DEQUEST 2066 (100% as acid)2 0.45 TINOPAL DMS3 0.28 MgSO4 0.49 Zeolite A (anhydrous) 17.92 CMC (100% active)4 0.47 Na2CO3 9.44 Citric acid 3.5
  • SAVINASE (4.0 KNPU)6 1.65
  • the procedure for preparing the granules comprises various tower-drying, agglomerating, dry-additions, etc., as follows. The percentages are based on the finished composition.
  • the C16-C18 glucose amide nonionic material is synthesized with DOBANOL C12 ⁇ 15EO(3) present during the reaction of methyl ester and N-methyl glucamine.
  • the C12 ⁇ 15EO(3) acts as a melting point depressor which allows the reaction to be run without forming cyclic glucose amides which are undesirable.
  • a surfactant mixture of 20% DOBANOL C12 ⁇ 15 EO(3) and 80% C16-C18 N-methyl glucose amide is obtained and coagglomerated with 10% sodium carbonate.
  • the above particle is then coagglomerated with a high active paste (70%) of a sodium salt of C14-C15 alkyl sulfate and C12 ⁇ 15 EO(3) sulfate and Zeolite A and extra sodium carbonate.
  • This particle evidences a good dispersibility in cold water of the C16-C18 N-methyl glucose amide.
  • the overall formulation of this particle (contribution to the detergent formulation after the drying of the agglomerate) is: C16-C18 N-methyl glucose amide 4.1% DOBANOL C12 ⁇ 15 EO(3) 0.94% Sodium carbonate 4.94% Zeolite A 5.3% Na C14-C15 alkyl sulfate 3.5% Na C12 ⁇ 15 EO(3) sulfate 0.59%
  • the silicone suds suppressor X2-3419 (95-97% high molecular weight linear silicone; 3%-5% hydrophobic silica) ex Dow Corning is coagglomerated with Zeolite A (2-5 ⁇ size), starch and stearyl alcohol binder.
  • This particle has the following formulation: Zeolite A 0.22% Starch 1.08% X2-3419 0.22% Stearyl alcohol 0.35%
  • the detergent preparation exhibits excellent solubility, superior performance and excellent suds control when used in European washing machine, e.g., using 85 g detergent in a AEG-brand washing machine in 30°C, 40°C, 60°C and 90°C cycles.
  • the fatty acid glucamide surfactant can be replaced by an equivalent amount of the maltamide surfactant, or mixtures of glucamide/maltamide surfactants derived from plant sugar sources.
  • the use of ethanolamides appears to help cold temperature stability of the finished formulations.
  • the use of sulfobetaine and/or amine oxide surfactants provides superior sudsing.
  • compositions A and B do not exemplify the present invention
  • compositions where especially high sudsing is desired e.g., dishwashing
  • the formulator of high sudsing compositions will desirably avoid the introduction of suds-suppressing amounts of such fatty acids into high sudsing compositions with the polyhydroxy fatty acid amide, and/or avoid the formation of C14 and higher fatty acids on storage of the finished compositions.
  • One simple means is to use C12 ester reactants to prepare the polyhydroxy fatty acid amides herein. Fortunately, the use of amine oxide or sulfobetaine surfactants can overcome some of the negative sudsing effects caused by the fatty acids.
  • anionic optical brighteners to liquid detergents containing relatively high concentrations (e.g., 10% and greater) of anionic or polyanionic substituents such as the polycarboxylate builders may find it useful to pre-mix the brightener with water and the polyhydroxy fatty acid amide, and then to add the pre-mix to the final composition.

Landscapes

  • Chemical & Material Sciences (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Oil, Petroleum & Natural Gas (AREA)
  • Wood Science & Technology (AREA)
  • Organic Chemistry (AREA)
  • Health & Medical Sciences (AREA)
  • Molecular Biology (AREA)
  • Detergent Compositions (AREA)
EP91918975A 1990-09-28 1991-09-25 Detergent compositions containing anionic surfactants, polyhydroxy fatty acid amides and magnesium Expired - Lifetime EP0551410B1 (en)

Applications Claiming Priority (5)

Application Number Priority Date Filing Date Title
US59061790A 1990-09-28 1990-09-28
US590617 1990-09-28
US75590591A 1991-09-06 1991-09-06
US755905 1991-09-06
PCT/US1991/006982 WO1992006156A1 (en) 1990-09-28 1991-09-25 Detergent compositions containing anionic surfactants, polyhydroxy fatty acid amides and magnesium

Publications (2)

Publication Number Publication Date
EP0551410A1 EP0551410A1 (en) 1993-07-21
EP0551410B1 true EP0551410B1 (en) 1995-09-13

Family

ID=27080893

Family Applications (1)

Application Number Title Priority Date Filing Date
EP91918975A Expired - Lifetime EP0551410B1 (en) 1990-09-28 1991-09-25 Detergent compositions containing anionic surfactants, polyhydroxy fatty acid amides and magnesium

Country Status (24)

Country Link
EP (1) EP0551410B1 (hu)
JP (1) JPH06505032A (hu)
CN (1) CN1029010C (hu)
AU (1) AU8768891A (hu)
BR (1) BR9106933A (hu)
CA (1) CA2092184C (hu)
CZ (1) CZ281623B6 (hu)
DE (1) DE69113057T2 (hu)
DK (1) DK0551410T3 (hu)
EG (1) EG19743A (hu)
ES (1) ES2077250T3 (hu)
FI (1) FI931368A (hu)
GR (1) GR3018284T3 (hu)
HU (1) HU214048B (hu)
IE (1) IE913418A1 (hu)
MA (1) MA22304A1 (hu)
MX (1) MX9101364A (hu)
MY (1) MY131214A (hu)
NO (1) NO931021L (hu)
NZ (1) NZ240040A (hu)
PT (1) PT99101B (hu)
SK (1) SK21893A3 (hu)
TR (1) TR26011A (hu)
WO (1) WO1992006156A1 (hu)

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2023122542A1 (en) * 2021-12-22 2023-06-29 Integrity Bio-Chemicals, Llc Compositions comprising reaction products of saccharide polymers and fatty acids or fatty esters formulated with an amide-based neutral surfactant

Families Citing this family (50)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0602179B1 (en) * 1991-09-06 1999-06-30 The Procter & Gamble Company Detergent compositions containing calcium and polyhydroxy fatty acid amide
EP0656046A4 (en) * 1992-08-21 1995-09-20 Procter & Gamble CONCENTRATED LIQUID DETERGENT COMPOSITION COMPRISING ALKYL ETHER SULFATE AND PROCESS FOR PREPARING THE SAME.
US5545354A (en) * 1992-09-01 1996-08-13 The Procter & Gamble Company Liquid or gel dishwashing detergent containing a polyhydroxy fatty acid amide, calcium ions and an alkylpolyethoxypolycarboxylate
EP0658188A4 (en) * 1992-09-01 1995-08-09 Procter & Gamble LIQUID OR GEL DETERGENT COMPOSITIONS CONTAINING CALCIUM AND STABILIZING SAME.
US5580849A (en) * 1992-09-01 1996-12-03 The Procter & Gamble Company Liquid or gel detergent compositions containing calcium and stabilizing agent thereof
CA2143328A1 (en) * 1992-09-01 1994-03-17 Kofi Ofosu-Asante Liquid or gel dishwashing detergent containing alkyl ethoxy carboxylate, divalent ions and alkylpolyethoxypolycarboxylate
DE4229442A1 (de) * 1992-09-03 1994-03-10 Henkel Kgaa Dispergiermittel
WO1994010273A1 (en) * 1992-11-04 1994-05-11 The Procter & Gamble Company Detergent gels
JPH08503986A (ja) * 1992-11-30 1996-04-30 ザ、プロクター、エンド、ギャンブル、カンパニー 低起泡性混合ポリヒドロキシ脂肪酸アミド非イオン界面活性剤／陰イオン界面活性剤によるクリーニング
US5318728A (en) * 1992-11-30 1994-06-07 The Procter & Gamble Company Low sudsing polyhydroxy fatty acid amide detergents
DE69313298T2 (de) * 1992-11-30 1998-03-26 Procter & Gamble Hochschäumende waschmittelzusammensetzungen mit speziell ausgewählten seifen
EP0670886A1 (en) * 1992-11-30 1995-09-13 The Procter & Gamble Company Detergent compositions containing polyhydroxy fatty acid amide, sulfated polyhydroxy fatty acid amide and soap
EP0693113A1 (en) * 1993-04-08 1996-01-24 The Procter & Gamble Company Secondary (2,3) alkyl sulfate surfactants in detergent compositions with polyhydroxy fatty acid amides
DE4323253C1 (de) * 1993-07-12 1995-01-05 Henkel Kgaa Verwendung von Fettsäure-N-alkylpolyhydroxyalkylamiden als Klarspülmittel für die maschinelle Reinigung harter Oberflächen
DE4331297A1 (de) * 1993-09-15 1995-03-16 Henkel Kgaa Stückseifen
DE69434635D1 (en) 1993-10-08 2006-04-27 Novo Nordisk As Amylasevarianten
JP2710468B2 (ja) * 1993-10-12 1998-02-10 ステパン カンパニー アルファ−スルホン化脂肪酸メチルエステル及びアニオン性界面活性剤を有する液体合成洗剤組成物
DE4400632C1 (de) * 1994-01-12 1995-03-23 Henkel Kgaa Tensidgemische und diese enthaltende Mittel
DE4409321A1 (de) * 1994-03-18 1995-09-21 Henkel Kgaa Detergensgemische
MX9605418A (es) * 1994-05-06 1997-12-31 Procter & Gamble Detergente liquido que contiene amida de acido graso polihidroxilico y sal de toluensulfonato.
GB2292155A (en) * 1994-08-11 1996-02-14 Procter & Gamble Handwash laundry detergent composition comprising three surfactants
DE19533539A1 (de) 1995-09-11 1997-03-13 Henkel Kgaa O/W-Emulgatoren
WO1997012022A1 (en) * 1995-09-29 1997-04-03 The Procter & Gamble Company Stable aqueous laundry detergent compositions comprising quaternary surfactants and amine oxides and having improved suspension properties
DE19544422A1 (de) * 1995-11-29 1997-06-05 Hoechst Ag Sulfonsuccinate von Polyhydroxyamiden
DE19544710C2 (de) 1995-11-30 1998-11-26 Henkel Kgaa Verdickungsmittel
DE19548068C1 (de) 1995-12-21 1997-06-19 Henkel Kgaa Verfahren zur Herstellung hellfarbiger, niedrigviskoser Tensidkonzentrate
US5932535A (en) * 1995-12-21 1999-08-03 Henkel Kommanditgesellschaft Auf Aktien Process for the production of light-colored, low-viscosity surfactant concentrates
US5965508A (en) 1997-10-21 1999-10-12 Stepan Company Soap bar compositions comprising alpha sulfonated fatty acid alkyl esters and long chain fatty acids
JP2000073085A (ja) * 1998-08-31 2000-03-07 Lion Corp 洗浄剤組成物
DE19840342A1 (de) * 1998-09-04 2000-03-09 Clariant Gmbh Feste Tensidmischungen enthaltend Fettsäurepolyhydroxyamide
US6387870B1 (en) 1999-03-29 2002-05-14 Ecolab Inc. Solid pot and pan detergent
DE10018812A1 (de) 2000-04-15 2001-10-25 Cognis Deutschland Gmbh Verfahren zur Herstellung von nichtionischen Tensidgranulaten
DE102004017112B4 (de) * 2004-04-07 2007-06-28 Henkel Kgaa Verwendung von Pudermittel
DE102005025933B3 (de) 2005-06-06 2006-07-13 Centrotherm Photovoltaics Gmbh + Co. Kg Dotiergermisch für die Dotierung von Halbleitern
JP4795298B2 (ja) * 2007-04-12 2011-10-19 花王株式会社 液体洗浄剤組成物
BR112012010823B1 (pt) * 2009-10-21 2020-10-06 Stepan Company Composições de limpeza líquidas viscosas compreendendo ácidos graxos sulfonados, ésteres ou sais dos mesmos e betaínas ou sultaínas e processo de fabricação das mesmas
KR101218398B1 (ko) * 2010-12-02 2013-01-03 애경산업(주) 액체 세정제용 조성물
EP2652107B1 (en) 2010-12-13 2019-03-27 Colgate-Palmolive Company Dilutable concentrated cleaning composition
BR112014029752A2 (pt) * 2012-05-30 2017-06-27 Clariant Finance Bvi Ltd uso de n-metil-n-acilglucaminas como estabilizadores de frio em soluções de tensoativos
CN103860398A (zh) * 2012-12-17 2014-06-18 江苏华艺服饰有限公司 一种去染料洗手液
JP6659705B2 (ja) * 2015-01-15 2020-03-04 エコラボ ユーエスエー インコーポレイティド 長時間残る洗浄泡
JP6688613B2 (ja) * 2016-01-15 2020-04-28 株式会社ニイタカ 液体洗浄剤組成物
JP6646512B2 (ja) * 2016-04-15 2020-02-14 花王株式会社 食器用液体洗浄剤組成物
DE102019207891A1 (de) * 2019-05-29 2020-12-03 Henkel Ag & Co. Kgaa Schaumstabilisierung durch spezifisches Tensidgemisch
DE102019207890A1 (de) * 2019-05-29 2020-12-03 Henkel Ag & Co. Kgaa Schaumstabilisierung durch spezifisches Tensidgemisch
US20230018865A1 (en) 2021-07-16 2023-01-19 The Procter & Gamble Company Liquid hand dishwashing cleaning composition
US20230034095A1 (en) 2021-07-16 2023-02-02 The Procter & Gamble Company Liquid hand dishwashing cleaning composition
US20230029458A1 (en) 2021-07-16 2023-02-02 The Procter & Gamble Company Liquid hand dishwashing cleaning composition
EP4194533B1 (en) * 2021-12-08 2024-06-05 The Procter & Gamble Company Liquid hand dishwashing detergent composition
CN115678690A (zh) * 2022-12-14 2023-02-03 山东宙雨消防科技股份有限公司 一种氢氧化镁清洁剂及其制备方法

Family Cites Families (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
BE557103A (hu) * 1956-05-14
DK130418A (hu) * 1967-07-19
JPS5950200B2 (ja) * 1978-02-17 1984-12-06 ライオン株式会社 改良された液体洗浄剤組成物
GB2058823B (en) * 1979-09-17 1983-06-22 Unilever Ltd Dishwashing compositions
DE3370164D1 (en) * 1982-10-28 1987-04-16 Procter & Gamble Liquid detergent compositions
ES8708009A1 (es) * 1984-11-07 1987-09-01 Procter & Gamble Un metodo para preparar una composicion detergente liquida
DE3538451A1 (de) * 1985-10-29 1987-05-07 Sueddeutsche Zucker Ag Fettsaeureamide von aminopolyolen als nichtionogene tenside
DE3711776A1 (de) * 1987-04-08 1988-10-27 Huels Chemische Werke Ag Verwendung von n-polyhydroxyalkylfettsaeureamiden als verdickungsmittel fuer fluessige waessrige tensidsysteme

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2023122542A1 (en) * 2021-12-22 2023-06-29 Integrity Bio-Chemicals, Llc Compositions comprising reaction products of saccharide polymers and fatty acids or fatty esters formulated with an amide-based neutral surfactant

Also Published As

Publication number Publication date
HUT64378A (en) 1993-12-28
CA2092184C (en) 1998-06-30
DE69113057T2 (de) 1996-05-30
HU214048B (en) 1997-12-29
FI931368A (fi) 1993-04-26
CA2092184A1 (en) 1992-03-29
NZ240040A (en) 1995-05-26
IE913418A1 (en) 1992-04-08
GR3018284T3 (en) 1996-03-31
MA22304A1 (fr) 1992-04-01
CZ281623B6 (cs) 1996-11-13
TR26011A (tr) 1993-11-01
HU9300765D0 (en) 1993-07-28
MY131214A (en) 2007-07-31
DK0551410T3 (da) 1996-02-05
NO931021D0 (no) 1993-03-22
AU8768891A (en) 1992-04-28
CN1061036A (zh) 1992-05-13
SK21893A3 (en) 1993-07-07
ES2077250T3 (es) 1995-11-16
WO1992006156A1 (en) 1992-04-16
BR9106933A (pt) 1993-08-17
MX9101364A (es) 1992-05-04
NO931021L (no) 1993-05-12
CZ32393A3 (en) 1994-03-16
EG19743A (en) 1996-01-31
PT99101B (pt) 1999-02-26
EP0551410A1 (en) 1993-07-21
JPH06505032A (ja) 1994-06-09
PT99101A (pt) 1992-08-31
FI931368A0 (fi) 1993-03-26
DE69113057D1 (de) 1995-10-19
CN1029010C (zh) 1995-06-21

Similar Documents

Publication Publication Date Title
EP0551410B1 (en) Detergent compositions containing anionic surfactants, polyhydroxy fatty acid amides and magnesium
EP0550653B1 (en) Detergent compositions containing polyhydroxy fatty acid amides and suds enhancing agent
EP0550652B1 (en) Detergent compositions containing alkyl ethoxy carbozylates and polyhydroxy fatty acid amides
EP0550606B1 (en) Nonionic surfactant systems containing polyhydroxy fatty acid amides and one or more additional nonionic surfactants
EP0550690B1 (en) Polyhydroxy fatty acid amide surfactants in bleach-containing detergent compositions
EP0551396B1 (en) Detergent compositions containing polyhydroxy fatty acid amide and alkyl ester sulfonate surfactants
EP0550557B1 (en) Detergent containing alkyl sulfate and polyhydroxy fatty acid amide surfactants
EP0551375B2 (en) Polyhydroxy fatty acid amides in zeolite/layered silicate built detergents
EP0550644B1 (en) Detergent compositions containing polyhydroxy fatty acid amide and alkyl alkoxylated sulfate
EP0602179B1 (en) Detergent compositions containing calcium and polyhydroxy fatty acid amide
EP0551413B1 (en) Detergent compositions containing polyhydroxy fatty acid amide and alkyl benzene sulfonate
EP0658188A1 (en) Liquid or gel detergent compositions containing calcium and stabilizing agent thereof
IE913419A1 (en) Detergent compositions containing anionic surfactants, polyhydroxy fatty acid amides and a critically selected suds enhancing agent
CZ284004B6 (cs) Čistící prostředek obsahující polyhydroxyamidy mastné kyseliny a prostředek podporující pěnění

Legal Events

Date Code Title Description
PUAI Public reference made under article 153(3) epc to a published international application that has entered the european phase

Free format text: ORIGINAL CODE: 0009012

17P Request for examination filed

Effective date: 19930315

AK Designated contracting states

Kind code of ref document: A1

Designated state(s): AT BE CH DE DK ES FR GB GR IT LI LU NL SE

17Q First examination report despatched

Effective date: 19930908

GRAA (expected) grant

Free format text: ORIGINAL CODE: 0009210

RBV Designated contracting states (corrected)

Designated state(s): BE CH DE DK ES FR GB GR IT LI NL SE

AK Designated contracting states

Kind code of ref document: B1

Designated state(s): BE CH DE DK ES FR GB GR IT LI NL SE

REF Corresponds to:

Ref document number: 69113057

Country of ref document: DE

Date of ref document: 19951019

ET Fr: translation filed
REG Reference to a national code

Ref country code: ES

Ref legal event code: FG2A

Ref document number: 2077250

Country of ref document: ES

Kind code of ref document: T3

ITF It: translation for a ep patent filed
REG Reference to a national code

Ref country code: DK

Ref legal event code: T3

REG Reference to a national code

Ref country code: GR

Ref legal event code: FG4A

Free format text: 3018284

PLBE No opposition filed within time limit

Free format text: ORIGINAL CODE: 0009261

STAA Information on the status of an ep patent application or granted ep patent

Free format text: STATUS: NO OPPOSITION FILED WITHIN TIME LIMIT

26N No opposition filed
PGFP Annual fee paid to national office [announced via postgrant information from national office to epo]

Ref country code: DK

Payment date: 20000614

Year of fee payment: 10

PGFP Annual fee paid to national office [announced via postgrant information from national office to epo]

Ref country code: NL

Payment date: 20000620

Year of fee payment: 10

PGFP Annual fee paid to national office [announced via postgrant information from national office to epo]

Ref country code: GR

Payment date: 20000726

Year of fee payment: 10

PGFP Annual fee paid to national office [announced via postgrant information from national office to epo]

Ref country code: GB

Payment date: 20000807

Year of fee payment: 10

PGFP Annual fee paid to national office [announced via postgrant information from national office to epo]

Ref country code: SE

Payment date: 20000901

Year of fee payment: 10

PGFP Annual fee paid to national office [announced via postgrant information from national office to epo]

Ref country code: FR

Payment date: 20000905

Year of fee payment: 10

PGFP Annual fee paid to national office [announced via postgrant information from national office to epo]

Ref country code: ES

Payment date: 20000926

Year of fee payment: 10

PGFP Annual fee paid to national office [announced via postgrant information from national office to epo]

Ref country code: DE

Payment date: 20000928

Year of fee payment: 10

PGFP Annual fee paid to national office [announced via postgrant information from national office to epo]

Ref country code: BE

Payment date: 20001010

Year of fee payment: 10

PGFP Annual fee paid to national office [announced via postgrant information from national office to epo]

Ref country code: CH

Payment date: 20001013

Year of fee payment: 10

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: GB

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20010925

Ref country code: DK

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20010925

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: SE

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20010926

Ref country code: ES

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20010926

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: LI

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20010930

Ref country code: GR

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20010930

Ref country code: CH

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20010930

Ref country code: BE

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20010930

REG Reference to a national code

Ref country code: GB

Ref legal event code: IF02

BERE Be: lapsed

Owner name: THE PROCTER & GAMBLE CY

Effective date: 20010930

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: NL

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20020401

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: DE

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20020501

EUG Se: european patent has lapsed

Ref document number: 91918975.3

GBPC Gb: european patent ceased through non-payment of renewal fee

Effective date: 20010925

REG Reference to a national code

Ref country code: CH

Ref legal event code: PL

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: FR

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20020531

NLV4 Nl: lapsed or anulled due to non-payment of the annual fee

Effective date: 20020401

REG Reference to a national code

Ref country code: DK

Ref legal event code: EBP

REG Reference to a national code

Ref country code: FR

Ref legal event code: ST

NLV4 Nl: lapsed or anulled due to non-payment of the annual fee

Effective date: 20020401

REG Reference to a national code

Ref country code: ES

Ref legal event code: FD2A

Effective date: 20021011

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: IT

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES;WARNING: LAPSES OF ITALIAN PATENTS WITH EFFECTIVE DATE BEFORE 2007 MAY HAVE OCCURRED AT ANY TIME BEFORE 2007. THE CORRECT EFFECTIVE DATE MAY BE DIFFERENT FROM THE ONE RECORDED.

Effective date: 20050925