EP0550652B1 - Compositions detersives contenant des elements carboxylates d'ethoxy d'alkyle et des amides d'acide gras de polyhydroxy - Google Patents

Compositions detersives contenant des elements carboxylates d'ethoxy d'alkyle et des amides d'acide gras de polyhydroxy Download PDF

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EP0550652B1
EP0550652B1 EP91918309A EP91918309A EP0550652B1 EP 0550652 B1 EP0550652 B1 EP 0550652B1 EP 91918309 A EP91918309 A EP 91918309A EP 91918309 A EP91918309 A EP 91918309A EP 0550652 B1 EP0550652 B1 EP 0550652B1
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Prior art keywords
alkyl
weight
fatty acid
polyhydroxy fatty
mixtures
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EP0550652A1 (fr
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Yi-Chang Fu
Jeffrey John Scheibel
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Procter and Gamble Co
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Procter and Gamble Co
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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
    • C11D1/66—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
    • C11D1/02—Anionic compounds
    • C11D1/04—Carboxylic acids or salts thereof
    • C11D1/06—Ether- or thioether carboxylic acids
    • 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
    • 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

Definitions

  • the present invention relates to detergent compositions comprising alkyl ethoxy carboxylates and polyhydroxy fatty acid amides.
  • it relates to detergent compositions which possess desirable cleaning and sudsing properties, and are especially suitable for use in dishwashing applications.
  • the polyhydroxy fatty acid amide component contained in the composition of the present invention is 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 G.B. Patent 809,060, published February 18, 1959, assigned to Thomas Hedley & Co., Ltd. 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. It is also generally indicated that additional constituents to impart desirable properties to the composition can also be included in the compositions, such as fluorescent dyes, bleaching agents, perfumes, etc.
  • 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.
  • 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 is hydrogen or an organic grouping
  • R' is an aliphatic hydrocarbon group of at least three carbon atoms
  • 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-acylpolyhydroxyalkyl-amine 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. Moller, 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 1%, preferably 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 are preferably liquid or gel detergent compositions, more preferably light-duty liquid detergent compositions, most preferably light-duty liquid dishwashing detergent compositions. These detergent compositions 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 alkyl ethoxy carboxylates and one or more polyhydroxy fatty acid amides. These and other optional ingredients typically found in detergent compositions are set forth below.
  • the surfactant mixture of the present invention comprises from about 5% to about 95% by weight, preferably from about 20% to about 80% by weight, more preferably from about 40% to about 60% by weight of one or more alkyl ethoxy carboxylates having the general formula RO(CH2CH2O) k CH2COO ⁇ M+ (I) wherein R is a C8-C22 alkyl group, preferably a C12-C14 alkyl group, k is an integer ranging from 0 to 10, preferably from 1 to 5, and M is a cation, preferably an alkali metal, alkaline earth metal, ammonium, lower alkanol ammonium, and mono-, di-, and triethanolammonium, more preferably sodium, potassium and ammonium, most preferably sodium and potassium, and mixtures thereof with magnesium and calcium ions.
  • R is a C8-C22 alkyl group, preferably a C12-C14 alkyl group
  • k is an integer ranging from 0 to 10,
  • the number of carbon atoms on the R group and the value of the integer k are interrelated in that if the number of carbon atoms on the R group is increased, then it is preferable that the value of the integer k be correspondingly increased to preserve the solubility of the detergent compound.
  • k will be in the range of from about 1 to about 4
  • R is a C12-C18 alkyl group
  • k will be in the range of from about 1 to about 6
  • R is a C8-C12 alkyl group
  • k will be in the range of from 0 to about 3.
  • the alkyl ethoxy carboxylate component of the present invention may be prepared by methods known in the art. One preferred method is disclosed in U.S. Patent Application Serial No. 354,968, entitled “Process for Making Alkyl Ethoxy Carboxylates,” filed May 22, 1989 on behalf of Thomas A. Cripe, the disclosure of which is incorporated herein.
  • the alkyl ethoxy carboxylate component of the present invention may comprise a distribution of alkyl ethoxy carboxylates.
  • the ethoxylate distribution will be such that, on a weight basis, the amount of material where k is 0 is less than about 20%, preferably less than about 15%, most preferably less than about 10%, and the amount of material where k is greater than 7 is less than about 25%, preferably less than about 15%, most preferably less than about 10%.
  • the average k will fall in the range of from 1 to 4 when the average R is C13 or less, and the average k will fall in the range of from 2 to 6 when the average R is greater than C13.
  • compositions of the present invention are comprised of a distribution of ethoxy carboxylates
  • desired distribution of carboxylates may be derived by reacting a corresponding distribution of ethoxylated alcohol precursors.
  • the divalent ions are preferably added as a chloride, sulfate salt, or a hydroxide, most preferably the chloride salt, to compositions containing alkali metal or ammonium salts of the alkyl ethoxy carboxylates, most preferably sodium or potassium salts, after the composition has been neutralized with a strong base.
  • concentration of divalent ion is typically in the range of from 0% to about 1.5%, preferably from about 0.2% to about 1%, most preferably from about 0.3% to about 0.8% by weight.
  • Magnesium and calcium ions are particularly preferred divalent ions.
  • compositions of the present invention may also contain from 0% to about 5.0%, preferably less than 4.0%, more preferably less than 2.5% by weight of alcohol ethoxylates of the formula R'O(CH2CH2O) w H (II) wherein R' is a C12-C16 alkyl group and w is in the range of from 0 to about 10, with the average w being less than 6.
  • the uncarboxylated alcohol ethoxylates of structure (II) are a detriment to the alkyl ethoxy carboxylate-containing compositions of the present invention. Therefore, it is critical that such compositions contain no more than about 5.0% by weight of the alcohol ethoxylates from which the alkyl ethoxy carboxylates are derived.
  • commercially available alkyl ethoxy carboxylates contain 10% or more of alcohol ethoxylates, there are known routes to obtain the desired high purity alkyl ethoxy carboxylates. For example, unreacted alcohol ethoxylates can be removed by steam distillation, U.S. Pat. No.
  • the surfactant mixture of the present invention further comprises from about 5% to about 95% by weight, preferably from about 20% to about 80% by weight, more preferably from about 20% to about 60% by weight of one or more polyhydroxy fatty acid amides having the 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 anhydro
  • 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.
  • 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 straight-chain C11-C17 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-hydroxyalkyl functionality is N-methyl, N-ethyl, N-propyl, N-butyl, N-hydroxyethyl, or N-hydroxy-propyl
  • 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-petrochemical 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 2%, preferably less than about 0.5%, 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 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 8 and about 10, more preferably between about 8.5 and about 9.5.
  • Liquid product formulations of the present invention are prepared at a pH in the range of from about 7.0 to about 11.0, preferably from about 8.5 to about 10.5, more preferably from about 8.8 to about 10.0.
  • the liquid detergent compositions may be adjusted to these pH levels using methods known to those skilled in the art, for example by adding a base to the compositions.
  • liquid dishwashing compositions have a pH of about 7.
  • compositions of the present invention exhibit greatly improved grease cleaning if formulated at an alkaline pH, as compared to a pH of below 7. This cleaning benefit appears to be unique to liquid detergent compositions containing the present alkyl ethoxy carboxylate component. Surprisingly, the compositions of this invention are still very mild to the hand at this alkaline pH.
  • buffering agent in order to prepare liquid detergent compositions having enhanced pH stability.
  • buffering agents include, but are not necessarily limited to, glycine (preferred), N,N-bis(2-hydroxyethyl)glycine (preferred), tris(hydroxymethyl)aminomethane, triethanolamine, monoethanolamine, 2-amino-2-ethyl-1,3-propanediol, 2-amino-2-methyl-1,3-propanediol, N-methyl diethanol amine, 1,3-diamino-2-hydroxypropane, and mixtures thereof.
  • such buffering agents are typically present at a level of from about 0.1% to about 15% by weight, preferably from about 1% to about 7% by weight, most preferably from about 1.5% to about 5% by weight.
  • 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 wherein 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).
  • surfactants such as anionic, nonionic, ampholytic and zwitterionic surfactants may also be incorporated into the detergent compositions of the present invention.
  • alkyl ester sulfonates One type of anionic surfactant which can be utilized encompasses alkyl ester sulfonates.
  • Alkyl ester sulfonate surfactants hereof include linear esters of C8-C20 carboxylic acids (i.e., fatty acids) which are sulfonated with gaseous SO3 according to "The Journal of the American Oil Chemists Society," 52 (1975), pp. 323-329.
  • Suitable starting materials would include natural fatty substances as derived from tallow, palm oil, etc.
  • the preferred alkyl ester sulfonate surfactant especially for laundry applications, comprise alkyl ester sulfonate surfactants of the structural formula: wherein R3 is a C8-C20 hydrocarbyl, preferably an alkyl, or combination thereof, R4 is a C1-C6 hydrocarbyl, preferably an alkyl, or combination thereof, and M is a cation which forms a water soluble salt with the alkyl ester sulfonate.
  • Suitable salt-forming cations include metals such as sodium, potassium, and lithium, and substituted or unsubstituted ammonium cations, such as monoethanolamine, diethanolamine, and triethanolamine.
  • R3 is C14-C16 alkyl
  • R4 is methyl, ethyl or isopropyl.
  • methyl ester sulfonates wherein R3 is C14-C16 alkyl.
  • Alkyl sulfate surfactants hereof are water soluble salts or acids of the formula ROSO3M wherein R preferably is a C10-C24 hydrocarbyl, preferably an alkyl or hydroxyalkyl having a C10-C20 alkyl component, more preferably a C12-C18 alkyl or hydroxyalkyl, and M is H or a cation, e.g., an alkali metal cation (e.g., sodium, potassium, lithium), or ammonium or substituted ammonium (e.g., methyl-, dimethyl-, and trimethyl ammonium cations and quaternary ammonium cations such as tetramethylammonium and dimethyl piperdinium cations and quaternary ammonium cations derived from alkylamines such as ethylamine, diethylamine, triethylamine, and mixtures thereof, and the like).
  • alkyl chains of C12 ⁇ 16 are
  • Alkyl alkoxylated sulfate surfactants hereof are water soluble salts or acids of the formula RO(A) m SO3M wherein R is an unsubstituted C10-C24 alkyl or hydroxyalkyl group having a C10-C24 alkyl component, preferably a C12-C20 alkyl or hydroxyalkyl, more preferably C12-C18 alkyl or hydroxyalkyl, A is an ethoxy or propoxy unit, m is greater than zero, typically between about 0.5 and about 6, more preferably between about 0.5 and about 3, and M is H or a cation which can be, for example, a metal cation (e.g., sodium, potassium, lithium, calcium, magnesium, etc.), ammonium or substituted-ammonium cation.
  • R is an unsubstituted C10-C24 alkyl or hydroxyalkyl group having a C10-C24 alkyl component, preferably a C12-C
  • Alkyl ethoxylated sulfates as well as alkyl propoxylated sulfates are contemplated herein.
  • Specific examples of substituted ammonium cations include methyl-, dimethyl-, trimethyl-ammonium cations and quaternary ammonium cations such as tetramethyl-ammonium and dimethyl piperdinium cations and those derived from alkylamines such as ethylamine, diethylamine, triethylamine, mixtures thereof, and the like.
  • Exemplary surfactants are C12-C18 alkyl polyethoxylate (1.0) sulfate (C12-C18E(1.0)M), C12-C18 alkyl polyethoxylate (2.25) sulfate (C12-C18E(2.25)M), C12-C18 alkyl polyethoxylate (3.0) sulfate (C12-C18E(3.0)M), and C12-C18 alkyl polyethoxylate (4.0) sulfate (C12-C18E(4.0)M), wherein M is conveniently selected from sodium and potassium.
  • anionic surfactants useful for detersive purposes can also be included in the compositions hereof. These can include salts (including, for example, sodium, potassium, ammonium, and substituted ammonium salts such as mono-, di- and triethanolamine salts) of soap, C9-C20 linear alkylbenzenesulfonates, C8-C22 primary or secondary alkanesulfonates, C8-C24 olefinsulfonates, sulfonated polycarboxylic acids prepared by sulfonation of the pyrolyzed product of alkaline earth metal citrates, e.g., as described in British patent specification No.
  • salts including, for example, sodium, potassium, ammonium, and substituted ammonium salts such as mono-, di- and triethanolamine salts
  • C9-C20 linear alkylbenzenesulfonates C8-C22 primary or secondary alkanesulfonates
  • alkylpolyglycolethersulfates (containing up to 10 moles of ethylene oxide); alkyl glycerol sulfonates, fatty acyl glycerol sulfonates, fatty oleyl glycerol sulfates, alkyl phenol ethylene oxide ether sulfates, paraffin sulfonates, alkyl phosphates, isethionates such as the acyl isethionates, acyl taurates, fatty acid amides of methyl tauride, alkyl succinamates and sulfosuccinates, monoesters of sulfosuccinates (especially saturated and unsaturated C12-C18 monoesters), diesters of sulfosuccinates (especially saturated and unsaturated C6-C12 diesters), acyl sarcosinates, sulfates of alkylpolysacc
  • Resin acids and hydrogenated resin acids are also suitable, such as rosin, hydrogenated rosin, and resin acids and hydrogenated resin acids present in or derived from tall oil. Further examples are described in "Surface Active Agents and Detergents" (Vol. I and II by Schwartz, Perry and Berch). A variety of such surfactants are also generally disclosed in U.S. Patent 3,929,678, issued December 30, 1975 to Laughlin, et al. at Column 23, line 58 through Column 29, line 23 (herein incorporated by reference).
  • 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.
  • Preferred amides are C8-C20 ammonia amides, monoethanolamides, diethanolamides, and isopropanolamides.
  • Ampholytic surfactants can 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 chain or branched.
  • 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 ampholytic surfactants.
  • Zwitterionic surfactants can 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 zwitterionic surfactants.
  • Ampholytic and zwitterionic surfactants are generally used in combination with one or more anionic and/or nonionic surfactants.
  • Preferred additional surfactants are anionic and nonionic surfactants, with C11 ⁇ 27 alkyl ester sulfonates, C8 ⁇ 22 primary and secondary alkane sulfonates, C10 ⁇ 18 alkyl dimethyl amine oxides, alkylpolysaccharides, and mixtures thereof being most preferred.
  • these optional additional surfactants are typically present at a concentration of from about 1.0% to about 10%, preferably from about 2% to about 5% 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-hydroxy- ethyl)-nitrilo diacetates , sodium and potassium oxydisuccinates, and sodium and potassium tartrate mono- and disuccinates, 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-hydroxy- ethyl)-nitrilo diacetates , sodium and potassium
  • 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 a level of from about 1% to about 10% by weight, preferably from about 2% to about 5% by weight.
  • compositions of the present invention are beneficial in that they provide unexpected improved sudsing performance when the particular polyhydroxy fatty acid amide is combined with the alkyl ethoxy carboxylate. While not intending to be bound by theory, it is believed that the compositions of the present invention offer the additional benefits of improved cleaning performance and are mild to the skin, even when formulated as a liquid and having a high alkaline pH. Again, while not intending to be bound by theory, it is further believed that an additional benefit of the compositions of the present invention is that they clean dishes without imparting a "greasy" feel to the finish product. This is especially important in consumer markets where the cleanliness of a dish is judged by the lack of such a "greasy" feel.
  • compositions of the present invention offer the further benefit of a reduced "slippery" feel typically associated with detergent compositions. This is especially important in consumer markets where such a feeling is not favored and is viewed as 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., preferably 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.
  • from about 1 ml. to about 50 ml., preferably from about 2 ml. to about 10 ml. of a 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 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.
  • Formulation A is made by initially combining an alkyl ethoxy carboxylate detergent mixture with a C12 ⁇ 14 fatty acid N-methyl glucamide to form a mixture. Ethanol, sodium chloride and sodium xylene sulfonate are then added to this mixture. Any desired remaining surfactants are then added. Glycine is added and the pH is adjusted to about 9.0 with sodium hydroxide. Finally, magnesium chloride is added, which reduces the pH accordingly. Final viscosity and pH adjustments can be made at this time, followed by the addition of perfume and dye. The balance is water.
  • Formulation B is made by adding ethanol, sodium chloride and sodium xylene sulfonate to an alkyl ethoxy carboxylate detergent/polyhydroxy fatty acid amide mixture of the type prepared in Formulation A.
  • the remaining formula components are added in the order given in the table below.
  • Formulation C is made by adding ethanol, sodium chloride and sodium xylene sulfonate to an alkyl ethoxy carboxylate detergent/polyhydroxy fatty acid amide mixture of the type prepared in Formulation A.
  • C12 ⁇ 14 monoethanol amide is warmed to about 65°C and is then added to the mixture. Minor pH and viscosity adjustments are made at this time, followed by the addition of dye, perfume and water to bring the formulation to 100%.
  • the surfactant portion contains about 93.9% alkyl ethoxy carboxylates of the formula RO(CH2CH2O) x CH2COO ⁇ Na+, wherein R is a C12 ⁇ 13 alkyl averaging 12.5, x ranges from 0 to about 10, and the ethoxylate distribution is such that the amount of material where x is 0 is about 2.8% and the amount of material where x is greater than 7 is less than about 2% by weight of the alkyl ethoxy carboxylates.
  • the average x in the distribution is 2.8.
  • the surfactant mixture contains 0% soap materials.
  • 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).
  • 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 and 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 malt-amide 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 Gardner Color for the adduct is much worse as the temperature is raised above about 30°C and at about 50°C, the time that the adduct has a Gardner Color below 7 is only about 30 minutes.
  • the temperature should be less than about 20°C.
  • the Gardner Color should be less than about 7, and preferably less than about 4 for good color glucamine.
  • 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.
  • the MMA adduct color (after substantial equilibrium is reached in at least about two hours) is as indicated.
  • the starting sugar material must be very near colorless in order to consistently have adduct that is acceptable.
  • the sugar has a Gardner Color of about 1, the adduct is sometimes acceptable and sometimes not acceptable.
  • the Gardner Color is above 1 the resulting adduct is unacceptable. The better the initial color of the sugar, the better is the color of the adduct.
  • 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 14.06 bar (200 psig) H2 and the reactor is pressurized with H2 at 112.52 bar (1600 psig) for two hours, the pressure is released at one hour and the reactor is repressurized to 112.52 bar (1600 psig).
  • the adduct is then pumped into the reactor which is at 14.06 bar (200 psig) and 20°C, and the reactor is purged with 14.06 bar (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.
  • 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 14.06 bar (200 psi) and the temperature is raised to about 50°C.
  • the pressure is raised to 17.58 bar (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.
  • Ni content in the glucamine is about 100 ppm as compared to the less than 10 ppm in the previous reaction.
  • 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 adduct is used for the hydrogen reaction right after making, or is stored at low temperature to prevent further degradation.
  • the glucamine adduct hydrogen reactions are 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.
  • Step 1 - Reactants Maltose monohydrate (Aldrich, lot 01318KW); methylamine (40 wt% in water) (Aldrich, lot 03325TM); Raney nickel, 50% slurry (UAD 52-73D, Aldrich, lot 12921LW).
  • the reactants are added to glass liner (250 g maltose, 428 g methylamine solution, 100 g catalyst slurry - 50 g Raney Ni) and placed in 3 L rocking autoclave, which is purged with nitrogen [3x35.16 bar (3X500 psig)] and hydrogen [2x35.16 bar (2X500 psig)] and rocked under H2 at room temperature over a weekend at temperature ranging from 28°C to 50°C.
  • the crude reaction mixture is vacuum filtered 2X through a glass microfiber filter with a silica gel plug. The filtrate is concentrated to a viscous material.
  • the final traces of water are azetroped off by dissolving the material in methanol and then removing the methanol/water on a rotary evaporator. Final drying is done under high vacuum.
  • the crude product is dissolved in refluxing methanol, filtered, cooled to recrystallize, filtered and the filter cake is dried under vacuum at 35°C. This is cut #1.
  • the filtrate is concentrated until a precipitate begins to form and is stored in a refrigerator overnight.
  • the solid is filtered and dried under vacuum. This is cut #2.
  • the filtrate is again concentrated to half its volume and a recrystallization is performed. Very little precipitate forms.
  • a small quantity of ethanol is added and the solution is left in the freezer over a weekend.
  • the solid material is filtered and dried under vacuum.
  • the combined solids comprise N-methyl maltamine which is used in Step 2 of the overall synthesis.
  • Step 2 Reactants: N-methyl maltamine (from Step 1); hardened tallow methyl esters; sodium methoxide (25% in methanol); absolute methanol (solvent); mole ratio 1:1 amine:ester; initial catalyst level 10 mole % (w/r maltamine), raised to 20 mole %; solvent level 50% (wt.).
  • a silica gel slurry in 100% methanol is loaded into a funnel and washed several times with 100% methanol.
  • a concentrated sample of the product (20 g in 100 ml of 100% methanol) is loaded onto the silica gel and eluted several times using vacuum and several methanol washes.
  • the collected eluant is evaporated to dryness (rotary evaporator). Any remaining tallow ester is removed by trituration in ethyl acetate overnight, followed by filtration. The filter cake is vacuum dried overnight.
  • the product is the tallowalkyl N-methyl maltamide.
  • Step 1 of the foregoing reaction sequence can be conducted using commercial corn syrup comprising glucose or mixtures of glucose and, typically, 5%, or higher, maltose.
  • the resulting polyhydroxy fatty acid amides and mixtures can be used in any of the detergent compositions herein.
  • Step 2 of the foregoing reaction sequence can be carried out in 1,2-propylene glycol or NEODOL.
  • the propylene glycol or NEODOL need not be removed from the reaction product prior to its use to formulate detergent compositions.
  • the methoxide catalyst can be neutralized by citric acid to provide sodium citrate, which can remain in the polyhydroxy fatty acid amide.
  • compositions herein can contain more or less of various suds control agents. Typically, for dishwashing high sudsing is desirable so no suds control agent will be used.
  • the fatty acid glucamide surfactant can be replaced by an equivalent amount of the maltamide surfactant, or mixtures of glucamide/malt-amide surfactants derived from plant sugar sources.
  • the use of ethanolamides appears to help cold temperature stability of the finished formulations.
  • the use of sulfobetaine (aka "sultaine") surfactants provides superior sudsing.
  • CaCl2 can be used ( ca . 1%) in the formulations to enhance greasy soil removal from dishes. MgCl2 enhances sudsing.
  • the present invention provides especially high sudsing compositions, it is preferred that less than about 5%, more preferably less than about 2%, most preferably substantially no C14 or higher fatty acids be present, since these can suppress sudsing. Accordingly, 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 amides, 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.
  • amine oxide or sulfobetaine surfactants such as cocoamidopropyl hydroxysultaine and betaines such as cocoamidopropyl betaine 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.

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Claims (12)

  1. Composition détergente à base d'un alcoxycarboxylate, caractérisée en ce qu'elle comprend de 1 à 65 % en poids d'un mélange de tensioactifs comprenant :
    (a) de 5 à 95 % en poids d'un ou plusieurs alkyléthoxycarboxylates ayant la formule générale

            RO(CH₂CH₂O)kCH₂COO⁻M⁺

    dans laquelle R est un groupe alkyle en C₈-C₂₂, k est un entier de 0 à 10 et M est un cation ; et
    (b) de 5 à 95 % en poids d'un ou plusieurs amides d'acides gras polyhydroxylés ayant la formule générale
    Figure imgb0021
     dans laquelle R¹ est H, un radical hydrocarboné en C₁-C₄, 2-hydroxyéthyle, 2-hydroxypropyle ou leurs mélanges, R² est un radical hydrocarboné en C₅-C₃₁ et Z est un radical hydrocarboné polyhydroxylé comportant une chaîne hydrocarbonée linéaire ayant au moins 3 groupes hydroxy directement liés à la chaîne, ou un de leurs dérivés alcoxylés.
  2. Composition selon la revendication 1, dans laquelle le composant alkylalcoxycarboxylate (a) est distribué de façon que la quantité de matière soit inférieure à 20 % quand k = 0 et que la quantité de matière soit inférieure à 25 % quand k est supérieur à 7, la valeur moyenne de k est comprise entre 1 et 4 quand le radical moyen R est en C₁₃ ou moins, et la valeur moyenne de k est comprise entre 2 et 6 quand le radical moyen R est supérieur à C₁₃.
  3. Composition selon la revendication 1, dans laquelle la composition détergente est un liquide, de préférence l'eau ou un mélange d'eau et d'un alcool en C₁-C₄, et comprend de 10 à 50 % en poids du mélange de tensioactifs et de 90 à 50 % en poids d'un support liquide.
  4. Composition selon la revendication 3, dans laquelle le mélange de tensioactifs comprend de 20 à 80 % en poids du composant alkylalcoxycarboxylate et de 20 à 80 % en poids du composant amide d'acide gras polyhydroxylé.
  5. Composition selon la revendication 4, dans laquelle le cation M de l'alkyléthoxycarboxylate (a) est choisi parmi l'ensemble comprenant les cations de métal alcalin, de métal alcalino-terreux, d'ammonium, d'(alcanol inférieur)-ammonium, et de mono-, di- et triéthanolammonium, et leurs mélanges avec des ions magnésium et calcium.
  6. Composition selon la revendication 5, dans laquelle le pH est compris entre 7,0 et 11,0, et qui de préférence contient en outre de 0,1 à 15 % en poids d'un agent tampon et aussi, de préférence, contient en outre de 2 à 5 % en poids d'un hydrotrope.
  7. Composition selon la revendication 6, dans laquelle le détergent liquide contient un ou plusieurs tensioactifs anioniques ou non-ioniques supplémentaires choisis parmi l'ensemble comprenant les alkylestersulfonates en C₁₂-C₂₇, les alcanesulfonates primaires et secondaires en C₈-C₂₂, les oxydes de (alkyle en C₁₀-C₁₈)-diméthylamine, les alkylpolysaccharides et leurs mélanges.
  8. Composition selon la revendication 7, dans laquelle le mélange de tensioactifs comprend de 40 à 60 % en poids du composant alkyléthoxycarboxylate et de 20 à 60 % en poids du composant amide d'acide gras polyhydroxylé, le support liquide comprenant de l'eau ou un mélange d'eau et d'éthanol.
  9. Composition selon la revendication 8, dans laquelle le cation M du composant alkyléthoxycarboxylate (a) est choisi parmi les cations sodium, potassium et ammonium et leurs mélanges avec des ions magnésium et calcium, et dans laquelle l'amide d'acide gras polyhydroxylé (b) a la formule
    Figure imgb0022
     dans laquelle R² est un groupe alkyle ou alcényle en C₁₁-C₁₇ à chaîne droite, Z dérivant du glucose, du maltose ou de leurs mélanges.
  10. Procédé pour nettoyer de la vaisselle salie, caractérisé en ce qu'il consiste à mettre en contact la vaisselle avec une quantité efficace d'une composition détergente comprenant de 5 à 65 % en poids d'un mélange de tensioactifs comprenant :
    (a) de 5 à 95 % en poids d'un ou plusieurs alkyléthoxycarboxylates ayant la formule générale

            RO(CH₂CH₂O)kCH₂COO⁻M⁺

    dans laquelle R est un groupe alkyle en C₈-C₂₂, k est un entier de 1 à 4 et M est un cation ; et
    (b) de 5 à 95 % en poids d'un ou plusieurs amides d'acides gras polyhydroxylés ayant la formule générale
    Figure imgb0023
     dans laquelle R¹ est H, un radical hydrocarboné en C₁-C₄, 2-hydroxyéthyle, 2-hydroxypropyle ou leurs mélanges, R² est un radical hydrocarboné en C₅-C₃₁ et Z est un radical hydrocarboné polyhydroxylé comportant une chaîne hydrocarbonée linéaire ayant au moins 3 groupes hydroxy directement liés à la chaîne, de préférence un N-méthylglucamide en C₁₁-C₁₇, un N-méthylmaltamide en C₁₁-C₁₇ ou des mélanges de ce glucamide et de maltamide, ou un de leurs dérivés alcoxylés, et éventuellement
    (c) un ou plusieurs tensioactifs anioniques autres que des carboxylates.
  11. Procédé selon la revendication 10, dans lequel le fragment Z de l'amide d'acide gras polyhydroxylé dérive de mélanges de monosaccharides, de disaccharides et de polysaccharides d'origine végétale.
  12. Procédé selon la revendication 10, dans lequel le fragment R² de l'amide d'acide gras polyhydroxylé est un radical alkyle ou alcényle en C₁₅-C₁₇ ou un de leurs mélanges.
EP91918309A 1990-09-28 1991-09-25 Compositions detersives contenant des elements carboxylates d'ethoxy d'alkyle et des amides d'acide gras de polyhydroxy Expired - Lifetime EP0550652B1 (fr)

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