WO1992006157A1 - 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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Publication number
WO1992006157A1
WO1992006157A1 PCT/US1991/006983 US9106983W WO9206157A1 WO 1992006157 A1 WO1992006157 A1 WO 1992006157A1 US 9106983 W US9106983 W US 9106983W WO 9206157 A1 WO9206157 A1 WO 9206157A1
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Prior art keywords
alkyl
fatty acid
weight
polyhydroxy fatty
mixtures
Prior art date
Application number
PCT/US1991/006983
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English (en)
Inventor
Yi-Chang Fu
Jeffrey John Scheibel
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The Procter & Gamble Company
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Publication date
Priority to BR919106896A priority Critical patent/BR9106896A/pt
Priority to PL91298221A priority patent/PL169553B1/pl
Priority to JP3517002A priority patent/JPH06501730A/ja
Priority to AU87425/91A priority patent/AU663855B2/en
Priority to DE69101928T priority patent/DE69101928T2/de
Priority to SK25793A priority patent/SK25793A3/sk
Priority to RU93005200A priority patent/RU2105790C1/ru
Priority to AT9191918309T priority patent/ATE105332T1/de
Application filed by The Procter & Gamble Company filed Critical The Procter & Gamble Company
Priority to EP91918309A priority patent/EP0550652B1/fr
Priority to CS93405A priority patent/CZ282518B6/cs
Publication of WO1992006157A1 publication Critical patent/WO1992006157A1/fr
Priority to NO931022A priority patent/NO301283B1/no
Priority to FI931363A priority patent/FI931363A0/fi
Priority to HK98105323A priority patent/HK1006180A1/xx

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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 com ⁇ prising 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.
  • compositions claimed in the present invention provide this desired effect.
  • 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 Thermo- tropic 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. Che . Soc. Che . 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 Com ⁇ pounds, a New Class of Non-Ionic Detergents For Membrane Biochemis- try," 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 constit ⁇ uents 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 condensa ⁇ tion 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.
  • amphiphilic compounds contain ⁇ ing 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'C0N(R)CH2R" and R"C0N(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.
  • N-polyhydroxy alkyl fatty acid amides as thickening agents in aqueous detergent systems. Included are amides of the formula R ⁇ C(0)N(X)R2 wherein R is a C1-C17 (preferably C7-C17) alkyl, R2 is hydrogen, a Ci-Cis (prefer ⁇ ably Ci-C ⁇ ) 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.
  • 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-acyl ⁇ polyhydroxyalkyl-amine of the formula R ⁇ C(0)N(R2)CH2(CHOH) n CH2 ⁇ H, wherein Ri 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 R ⁇ N(Z)C(0)R2 wherein Ri is a C10-C22 alkyl, R2 is a C7-C21 alkyl, Ri and R2 total from 23 to 39 carbon atoms, and Z is a polyhydroxyalkyl which can be -CH2(CH0H) m - CH2OH where is 3 or 4.
  • U.S. Patent 4,021,539 issued May 3, 1977, to H. M ⁇ ller, et al., relates to skin treating cosmetic compositions containing N-polyhydrox alkyl-amines which include compounds of the formula RlN(R)CH(CH0H) m R2 wherein Ri is H, lower alkyl, hydroxy-lower alkyl, or a inoalkyl, as well as heterocyclic aminoalkyl, R is the same as Rl but both cannot be H, and R2 is CH OH or COOH.
  • French Patent 1,360,018, April 26, 1963, assigned to Commercial Solvents Corporation, relates to solutions of formaldehyde stabi ⁇ lized against polymerization with the addition of amides of the formula RC(0)N(R ⁇ )G wherein R is a carboxylic. acid functionality having at least seven carbon atoms, Ri 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)(R ⁇ )(R2) wherein R is a sugar residue of glucamine, Rl 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)(R ⁇ )C(0)R2 wherein R is the residue of an anhydrized hexane pentol or a carboxylic acid ester thereof, Rj is a monovalent hydrocarbon radical, and -C(0)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 polyhydrox amide of the formula RC(0)NR 1 (R 2 ) wherein RC(0) contains from about 10 to about 14 carbon atoms, and R 1 and R 2 each are H or Ci-C ⁇ 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.
  • RC(0)NR 1 (R 2 ) wherein RC(0) contains from about 10 to about 14 carbon atoms, and R 1 and R 2 each are H or Ci-C ⁇ alkyl
  • 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:
  • R is H, a C1-C4 hydrocarbyl , 2-hydroxy ethyl, 2-hydroxy propyl, or mixtures thereof
  • R 2 is a C5-C31 hydrocarbyl
  • Z is a polyhydroxyhydrocarbyl having a linear hydrocarbyl chain with at least 3 hydroxyl groups directly connected to the chain, or an alkoxylated deriva ⁇ tive thereof.
  • 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 prefer ⁇ ably liquid or gel detergent compositions, more preferably light- duty liquid detergent compositions, most preferably light-duty liquid dishwashing detergent compositions.
  • These detergent composi ⁇ tions 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.
  • a surfactant mixture comprising one or more alkyl ethoxy carboxylates and one or more polyhydroxy fatty acid amides.
  • 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
  • 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
  • M is a cation, preferably an alkali metal, alkaline earth metal, ammonium, lower alkanol ammonium, and mono-, di-, and tri- ethanolammonium, more preferably sodium, potassium and ammonium, most preferably sodium and potassium, and mixtures thereof with magnesium and calcium ions.
  • 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 C1 -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 incorpor ⁇ ated 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 car ⁇ boxylates
  • desired distribution of carboxylates may be derived by reacting a corresponding distribution of ethoxylated alcohol precursors. It has been found that the presence of divalent cations with the alkyl ethoxy carboxylates in the compositions of the present invention greatly improves the cleansing of greasy soils. This is especially true when the composition is used in softened water that contains few divalent ions.
  • divalent ions increase the packing of the alkyl ethoxy carboxylates at the oil/water interface, thereby producing reduced interfacial tension and improved grease cleaning.
  • liquid detergent composi ⁇ tions used in dishwashing applications which contain alkyl ethoxy carboxylates and which do not conform to the narrow definition of this invention will benefit less from the addition of divalent ions and, in many cases, will actually exhibit reduced cleaning perfor ⁇ mance upon the addition of divalent cations.
  • the divalent ions are preferably added as a chloride, sulfate salt, or a hydroxide, most preferably the chloride salt, to compositions con ⁇ taining alkali metal or ammonium salts of the alkyl ethoxy carboxyl- ates, most preferably sodium or potassium salts, after the composi ⁇ tion 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' ⁇ (CH 2 CH2 ⁇ ) w H (II) wherein R' is a Ci2" i6 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 composi ⁇ tions contain no more than about 5.0% by weight of the alcohol ethoxylates from which the alkyl ethoxy carboxylates are derived.
  • alkyl ethoxy carboxylates contain 10% or more of alcohol ethoxylates
  • 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. 4,098,818 (Example I), or by recrystallization of the alkyl ethoxy carboxylate, British Pat. No. 1,027,481 (Example I).
  • Other routes to the desired carboxylates are the reaction of sodium hydroxide or sodium metal and monochloracetic acid, or its salt, with alcohol ethoxylates under special pressure and temperature conditions, as described in U.S. Pat. Nos.
  • the surfactant mixture of the present invention further com ⁇ prises 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 0 Rl
  • Rl is H, C1-C4 hydrocarbyl, 2-hydroxy ethyl, 2-hydroxy propyl , or a mixture thereof, preferably C1-C4 alkyl, more prefer ⁇ ably Ci or C2 alkyl, most preferably Ci alkyl (i.e., methyl); and R 2 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 hydro ⁇ carbyl chain with at least 3 hydroxyls directly connected to the chain, or an anhydro derivative derived by dehydration of such polyhydroxyhydrocarbyl, or an alkoxylated derivative (preferably ethoxylated or propoxylated) thereof.
  • 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 prefer ⁇ ably will be selected from the group consisting of -CH 2 -(CHOH) n - CH 2 0H, -CH(CH 2 0H)-(CH0H) n . 1 -CH 2 0H, -CH 2 -(CHOH)2(CHOR")(CHOH)-CH2 ⁇ H, 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.
  • R can be, for example, N-methyl, N-ethyl , N-propyl, N-isopropyl, N-butyl, N-2-hydroxy ethyl, or N-2-hydroxy propyl .
  • R 2 -C0-N ⁇ can be, for example, coca ide, stearamide, oleamide, lauramide, myristamide, capricamide, palmitamide, tallowa ide, etc.
  • Z can be 1-deoxyglucityl , 2-deoxyfructityl, 1-deoxymaltityl, 1-deoxylactityl , 1-deoxygalactityl , 1-deoxymannityl , 1-deoxymalto- triotityl, etc.
  • the most preferred polyhydroxy fatty acid amide has the general formula
  • R 2 is a straight-chain C ⁇ -Cij 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 triglycer- ide in a condensation/amidation step to form the N-alkyl, N- polyhydroxy fatty acid amide product.
  • Processes for making composi ⁇ tions 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
  • 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:
  • 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-con ⁇ taining 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 advanta ⁇ geous 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 pre ⁇ ferred 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,
  • 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 formula- tions 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 compo ⁇ sitions have a pH of about 7.
  • compositions of the present inven ⁇ tion 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.
  • the compositions of this invention are still very mild to the hand at this alkaline pH. It is desirable to include a buffering agent in order to prepare liquid detergent compositions having enhanced pH stability.
  • buffering agents include, but are not neces ⁇ sarily limited to, glycine (preferred), N,N-bis(2-hydroxyethyl)gly- cine (preferred), tris(hydroxymethyl)aminomethane, triethanolamine, monoethanolamine, 2-amino-2-ethyl-l,3-propanediol, 2-amino-2-methyl- 1,3-propanediol, N-methyl diethanol a ine, l,3-diamino-2-hydroxy- propane, 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.
  • compositions of this invention 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.
  • a preferred thickening agent useful in the compositions of the present invention is a high molecular weight polycarboxylate polymer thickener. By “high molecular weight” it is meant from about
  • the polycarboxylate polymer may be a carboxyvinyl polymer.
  • 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 predomi- nant 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 ally! groups, the polyol having at least two ally! ether groups per polyol molecule. When the polyol is sucrose, it is preferred that the sucrose have at least about five ally! ether groups per sucrose molecule.
  • the poly ⁇ ether 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 R
  • CH2 C - COOH 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. Pre ⁇ ferred 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. Various carboxyvinyl polymers are commercially available from B. F. Goodrich Company, New York, N.Y., under the trade name Carbopol.
  • 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 composi ⁇ tion 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 thick ⁇ ener 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. Yield Value Analysis
  • 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 read- ings. 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 Other surfactants, such as anionic, nonionic, ampholytic and zwitterionic surfactants may also be incorporated into the detergent compositions of the present invention.
  • Anionic Surfactants such as anionic, nonionic, ampholytic and zwitterionic surfactants may also be incorporated into the detergent compositions of the present invention.
  • Alkyl ester sulfonate surfactants hereof include linear esters of C8-C 0 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 de ived from tallow, palm oil, etc.
  • alkyl ester sulfonate surfactant especially for laundry applications, comprise alkyl ester sulfonate surfactants of the structural formula:
  • R 3 is a C8-C20 hydrocarbyl, preferably an alkyl, or combina ⁇ tion thereof
  • R4 is a Ci-C ⁇ hydrocarbyl, preferably an alkyl, or combination thereof
  • 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 monoethanol- amine, diethanolamine, and triethanolamine.
  • R 3 is C14-C16 alkyl, and R is methyl, ethyl or isopropyl. Especially preferred are the methyl ester sulfonates wherein R 3 is C14-C16 alkyl. Alkyl Sulfate Surfactant
  • 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 tri ethyl ammonium cations and quaternary ammonium cations such as tetramethylammonium and dimethyl piper- dinium cations and quaternary ammonium cations derived from alkyla- mines such as ethylamine, diethylamine, triethylamine, and mixtures thereof, and the like).
  • alkyl chains
  • Alkyl alkoxylated sulfate surfactants hereof are water soluble salts or acids of the formula R0(A) m S03M wherein R is an unsubsti- tuted C10-C24 alkyl or hydroxyalkyl group having a C10-C24 alkyl component, preferably a C12-C 0 alkyl or hydroxyalkyl , more prefer ⁇ ably 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 unsubsti- tuted C10-C24 alkyl or hydroxyalkyl group having a C10-C24 alkyl component,
  • Alkyl ethoxylated sulfates as well as alkyl propoxy!ated 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, triethyl ⁇ amine, mixtures thereof, and the like.
  • Exemplary surfactants are C12-C18 alkyl polyethoxylate (1.0) sulfate (Ci2-C ⁇ sE(1.0)M), C12-C18 alkyl polyethoxylate (2.25) sulfate (Ci2-C ⁇ sE(2.25)M), C12-C18 alkyl polyethoxylate (3.0) sulfate (Ci2-C ⁇ sE(3.0)M), and C12-C1 . 8 alkyl polyethoxylate (4.0) sulfate (Ci2-C ⁇ sE(4.0)M), wherein M is con ⁇ veniently selected from sodium and potassium.
  • Other Anionic Surfactants are C12-C18 alkyl polyethoxylate (1.0) sulfate (Ci2-C ⁇ sE(1.0)M), C12-C18 alkyl polyethoxylate (2.25) sulfate (Ci2-C ⁇ sE(2.25)M), C12-C18 alkyl polyethoxy
  • 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
  • alkylpolyglycol- ethersulfates (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 sulfosuccin- ates (especially saturated and unsaturated C12-C18 monoesters), diesters of sulfosuccinates (especially saturated and unsaturated C5-C12 diesters), acyl sarcosinates, sulfates of alkyl
  • Resin acids and hydro- genated 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 incor ⁇ porated by reference).
  • Nonionic Detergent Surfactants Suitable nonionic detergent surfactants are generally disclosed in U.S.
  • Exemplary, non-limiting classes of useful nonionic surfactants are listed below. 1.
  • the ethylene oxide is present in an amount equal to from about 5 to about 25 moles of ethylene oxide per mole of alkyl phenol.
  • nonionic surfactants of this type include IgepalTM C0-630, marketed by the GAF Corporation; and TritonTM ⁇ .45, ⁇ -114, X-100, and X-102, all marketed by the Rohm & Haas Company.
  • the condensation products of aliphatic alcohols with from about 1 to about 25 moles of ethylene oxide can either be straight or branched, primary or secondary, and generally contains from about 8 to about 22 carbon atoms. Particularly preferred are the condensation products of alcohols having an alkyl group containing from about 10 to about 20 carbon atoms with from about 2 to about 10 moles of ethylene oxide per mole of alcohol.
  • nonionic surfactants of this type include TergitolTM 15-S-9 (the condensation product of C11-C15 linear alcohol with 9 moles ethylene oxide), TergitolTM 24-L-6 NMW (the condensation product of C12-C14 primary alcohol with 6 moles ethylene oxide with a narrow molecular weight distribution), both marketed by Union Carbide Corporation; NeodolTM 45-9 (the condensation product of C14-C15 linear alcohol with 9 moles of ethylene oxide), NeodolTM 23-6.5 (the condensation product of C12-C13 linear alcohol with 6.5 moles of ethylene oxide), NeodolTM 45-7 (the condensation product of C14-C15 linear, alcohol with 7 moles of ethylene oxide), NeodolTM 45-4 (the condensation product of C1 -C15 linear alcohol with 4 moles of ethylene oxide), marketed by Shell Chemical Company, and KyroTM E0B (the condensation product of C13-C15 alcohol with 9 moles ethylene oxide), marketed by The Procter & Gamble Company
  • the hydrophobic portion of these compounds preferably has a molecular weight of from about 1500 to about 1800 and exhibits water insolubility.
  • the addition of polyoxyethylene moieties to this hydrophobic portion tends to increase the water solubility of the molecule as a whole, and the liquid character of the product is retained up to the point where the polyoxyethylene content is about 50% of the total weight of the condensation prod- uct, which corresponds to condensation with up to about 40 moles of ethylene oxide.
  • Examples of compounds of this type include certain of the commercially-available PluronicTM surfactants, marketed by BASF.
  • the condensation products of ethylene oxide with the product resulting from the reaction of propylene oxide and ethylene- diamine consist of the reaction product of ethylenediamine and excess propylene oxide, and generally has a molecular weight of from about 2500 to about 3000.
  • This hydrophobic moiety is condensed with ethylene oxide to the extent that the condensation product contains from about 40% to about 80% by weight of polyoxyethylene and has a molecular weight of from about 5,000 to about 11,000.
  • this type of nonionic surfactant include certain of the comrnercially available TetronicTM compounds, marketed by BASF.
  • Semi-polar nonionic surfactants are a special category of nonionic surfactants which include water-soluble amine oxides containing one alkyl moiety of from about 10 to about 18 carbon atoms and 2 moieties selected from the group consisting of alkyl groups and hydroxyalkyl groups containing from about 1 to about 3 carbon atoms; water-soluble phosphine oxides containing one alkyl moiety of from about 10 to about 18 carbon atoms and 2 moieties selected from the group consisting of alkyl groups and hydroxyalkyl groups containing from about 1 to about 3 carbon atoms; and water- soluble sulfoxides containing one alkyl moiety of from about 10 to about 18 carbon atoms and a moiety selected from the group consist ⁇ ing of alkyl and hydroxyalkyl moieties of from about 1 to about 3 carbon atoms.
  • Semi-polar nonionic detergent surfactants include the amine oxide surfactants having the formula
  • R 3 is an alkyl, hydroxyalkyl , or alkyl phenyl group or mixtures thereof containing from about 8 to about 22 carbon atoms
  • R4 is an alkylene or hydroxyalkylene group containing from about 2 to about 3 carbon atoms or mixtures thereof
  • x is from 0 to about 3
  • each R 5 is an alkyl or hydroxyalk l group containing from about 1 to about 3 carbon atoms or a polyethylene oxide group containing from about 1 to about 3 ethylene oxide groups.
  • the R 5 gr ⁇ ps can be attached to each other, e.g., through an oxygen or nitrogen atom, to form a ring structure.
  • amine oxide surfactants in particular include Cio-Cis alkyl dimethyl amine oxides and C8-C12 alkoxy ethyl dihydroxy ethyl amine oxides.
  • Any reducing saccharide containing 5 or 6 carbon atoms can be used, e.g., glucose, galactose and galacto- syl moieties can be substituted for the glucosyl moieties.
  • the hydrophobic group is attached at the 2-, 3-, 4-, etc. positions thus giving a glucose or galactose as opposed to a gluco- side or galactoside.
  • the intersaccharide bonds can be, e.g., between the one position of the additional saccharide units and the 2-, 3-, 4-, and/or 6- positions on the preceding saccharide units.
  • the preferred alkyleneoxide is ethylene oxide.
  • Typical hydrophobic groups include alkyl groups, either saturated or unsatu ⁇ rated, branched or unbranched containing from about 8 to about 18, preferably from about 10 to about 16, carbon atoms.
  • the alkyl group is a straight chain saturated alkyl group.
  • the alkyl group can contain up to about 3 hydroxy groups and/or the polyalkyl- eneoxide chain can contain up to about 10, preferably less than 5, alkyleneoxide moieties.
  • Suitable alkyl polysaccharides are octyl , nonyldecyl, undecyldodecyl, tridecyl, tetradecyl, pentadecyl, hexadecyl, heptadecyl , and octadecyl, di-, tri-, tetra-, penta-, and hexaglucosides, galactosides, lactosides, glucoses, fructosides, fructoses and/or galactoses.
  • Suitable mixtures include coconut alkyl, di-, tri-, tetra-, and pentaglucosides and tallow alkyl tetra-, penta-, and hexaglucosides.
  • the preferred alkylpolyglycosides have the formula
  • R 0(CnH 2n 0)t(glycosyl) ⁇ wherein R 2 is selected from the group consisting of alkyl, alkyl- phenyl, hydroxyalkyl , hydroxyalkylphenyl , and mixtures thereof in which the alkyl groups contain from about 10 to about 18, preferably from about 12 to about 14, carbon atoms; n is 2 or 3, preferably 2; t is from 0 to about 10, preferably 0; and x is from about 1.3 to about 10, preferably from about 1.3 to about 3, most preferably from about 1.3 to about 2.7.
  • the glycosyl is preferably derived from glucose.
  • the alcohol or alkylpolyethoxy alcohol is formed first and then reacted with glucose, or a source of glucose, to form the glucoside (attachment at the 1-position).
  • the additional glycosyl units can then be attached between their 1-position and the preceding glycosyl units 2-, 3-, 4- and/or 6-position, preferably predominately the 2-position.
  • Fatty acid amide surfactants having the formula:
  • R> is an alkyl group containing from about 7 to about 21 (preferably from about 9 to about 17) carbon atoms and each R 7 is selected from the group consisting of hydrogen, C1-C4 alkyl, C1-C4 hydroxyalkyl , and -(C2H4 ⁇ ) x H where x varies from about 1 to about 3.
  • Preferred amides are C8-C20 ammonia amides, monoethanolamides, diethanolamides, and isopropanolamides.
  • Amoholytic Surfactants Ampholytic surfactants can be incorporated into the detergent compositions hereof.
  • 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
  • Zwitterionic surfactants can also be incorporated into the detergent compositions hereof. These surfactants can be broadly described as derivatives of secondary and tertiary amines, deriva- tives 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 C ⁇ -27 alkyl ester sulfonates, Cs-22 primary and secondary alkane sulfonates, C ⁇ o-18 alkyl dimethyl amine oxides, alkylpolysaccharides, and mixtures thereof being most preferred. If included in the compositions of the present invention, these optional additional surfactants are typically present at a concen ⁇ tration of from about 1.0% to about 10%, preferably from about 2% to about 5% by weight.
  • Optional Ingredients include 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 inven ⁇ tion.
  • 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 inven ⁇ tion.
  • 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 tripolyphos- phate, 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 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-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 inven ⁇ tion.
  • 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 benefi ⁇ cial 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 inven ⁇ tion 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 associ- ated 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 con ⁇ tacted 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.
  • 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.
  • composition prod- uct 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 prod- uct.
  • a liquid deter ⁇ gent 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 deter ⁇ gent 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 deter ⁇ gent 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 deter ⁇ gent 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-methyl gl ucamine (195 g . , 1.0 mol e, Al dri ch , M4700-0) and methyl l aurate (Procter & Gambl e CE 1270, 220.9 g . , 1.0 mol e) are pl aced in a fl ask.
  • the sol id/l i quid mixture i s heated with sti rring 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 C1 -1 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 viscos ⁇ ity 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 deter- gent/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 deter- gent/polyhydroxy fatty acid amide mixture of the type prepared in Formulation A.
  • C ⁇ 2-14 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 mixture containing sodium alkyl ethoxy car ⁇ boxylate is prepared according to the process outlined below: 1.
  • a Ci2-13 alkyl ethoxy (3.0 ave.) alcohol is reacted with potassium t-butoxide and sodium chloroacetate in the ratio of 1:1.1:1.1 by first mixing the alkyl ethoxy!ate with the potas ⁇ sium t-butoxide at about 60°C and about 20 mm Hg pressure for about 1 hour. Thereafter, t-butanol is continuously removed from the reaction mixture by distillation. The vacuum is then broken and sodium chloroacetate is added with mixing.
  • the pressure is reestablished at about 18-20 mm Hg, and the reac ⁇ tion is allowed to continue for about 3 hours. Afterwards, the reaction pressure is brought to atmospheric level with nitro ⁇ gen, and the steam heating coils are turned off. The reaction mixture is left in this state overnight. The next, day the reaction mixture temperature is increased and the pressure reduced to remove more t-butanol from the system. The reaction mixture is then added to an aqueous solution of hydrochloric acid containing 105% of the theoretical amount needed to neutralize the potassium t-butoxide initially added. The acid aqueous reaction product is heated to force phase separation of the organic and aqueous materials. The organic phase is collected.
  • Step 1 above is repeated using a C12-13 alkyl ethoxy (2.7 ave.) alcohol and a ratio of this ethoxy alcohol to potassium t- butoxide and sodium chloroacetate of 1:1.3:1.3.
  • the potassium t-butoxide is added to the alkyl ethoxylate, which is at a temperature of about 32.2°C, and the reaction mixture is then increased to about 76.7°C.
  • the vacuum pump is then turned on to achieve reduced pressure.
  • the reaction temperature is increased to about 104. °C, and the t-butanol is pulled off and collected over about a 30 minute period.
  • the sodium chloro ⁇ acetate is then added to the reaction mixture, which has been cooled slightly to about 66°C.
  • the reac t ion is mixed for about 1.5 hours, cooled, and added to an aqueous solution of suffi- cient hydrochloric acid to achieve a pH of 3.4. Water is added to increase the volume of the reaction mixture by about 50%, and the mixture is then heated to about 49°C. The top organic layer is collected, and the washing process is repeated. 3.
  • the surfactant mixtures produced in Steps 1 and 2 above are mixed at a ratio of 40.4 to 59.6. A portion of this larger combined surfactant mixture is neutralized with 50% sodium hydroxide to a pH of about 8 and diluted by about 50% with a 25/75 by volume mixture of water and ethanol. The resulting solution is continuously extracted at room temperature with hexanes for about four days. The lower aqueous phase is collected, and some ethanol and water is removed by heating to yield a paste containing the alkyl ethoxy carboxylate contain- ing surfactant mixture described below.
  • the surfactant portion contains about 93.9% alkyl ethoxy carboxylates of the formula RO(CH2CH2 ⁇ ) ⁇ CH2COO " Na+, wherein R is a C12-13 alkyl averaging 12.5, x ranges from 0 to about 10, and the ethoxy!ate 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).
  • 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 C 16 -C 18 ) counterparts. Accordingly, the C 12 -C 14 materials are somewhat easier to formulate in liquid compo ⁇ sitions, and are more soluble in cool-water laundering baths. However, the C 16 -C 18 materials are also quite useful, especially under circumstances where warm-to-hot wash water is used. Indeed, the C 16 -C 18 materials may be better detersive surfactants than their C 12 -C 14 counterparts. Accordingly, the formulator may wish to balance ease-of-manufacture vs.
  • the solubility of the poly- hydroxy 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.
  • the solubility of 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 deter ⁇ gents when used in combination with conventional alkylbenzene sulfonate ("LAS") surfactants. While not intending to be limited by theory, it appears that the combination of LAS with the polyhydroxy fatty acid amides derived from the higher saccharides such as maltose causes a substantial and unexpected lowering of interfacial tension in aqueous media, thereby enhancing net detergency perfor ⁇ mance.
  • LAS alkylbenzene sulfonate
  • the manufacture of a polyhydroxy fatty acid amide derived from maltose is described hereinafter.
  • 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 manufacture of preferred uncyclized polyhydroxy fatty acid amides from fatty esters and N-alkyl polyols can be carried out in alcohol solvents at temperatures from about 30 ⁇ C to 90 ⁇ C, preferably about 50 ⁇ C-80 ⁇ C. It has now been determined that it may be conve ⁇ nient for the formulator of, for example, liquid detergents to conduct such processes in 1,2-propylene glycol solvent, since the glycol solvent need not be completely removed from the reaction product prior to use in the finished detergent formulation.
  • 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) C 12 -C 1 alcohols, such as those available as NEODOL 23 E06.5 (Shell).
  • ethoxylated alcohols such as the ethoxylated (EO 3-8) C 12 -C 1 alcohols, such as those available as NEODOL 23 E06.5 (Shell).
  • EO 3-8 ethoxylated (EO 3-8) C 12 -C 1 alcohols, such as those available as NEODOL 23 E06.5 (Shell).
  • EO 3-8 ethoxylated (EO 3-8) C 12 -C 1 alcohols, such as those available as NEODOL 23 E06.5 (Shell).
  • T designation.
  • methods for making polyhydroxy fatty acid amides per se form no part of the invention herein, the formulat
  • 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. While a variety of N-alkyl polyhydroxy amines useful in 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.
  • MMA methyla ine
  • 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.
  • 1.5:1 mole ratio of amine to sugar noted, equil brium 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.
  • Adduct 3 4/5 7/8 7/8 1 2 1 Adduct 3 4/5 7/8 7/8 1 2 1
  • the starting sugar material must be very near colorless in order to consistently have adduct that is acceptable.
  • 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 200 psig H 2 and the reactor is pressurized with H 2 at 1600 psig for two hours, the pressure is released at one hour and the reactor is repressurized to 1600 psig.
  • the adduct is then pumped into the reactor which is at 200 psig and 20 * C, and the reactor is purged with 200 psig H 2 , 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 N 2 at about 10-20'C.
  • About 330 g of about 70% corn syrup (near water-white) is degassed with N 2 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 H 2 at about 20 ⁇ C.
  • the H 2 pressure is raised to about 200 psi and the temperature is raised to about 50 * C.
  • the pressure is raised 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.
  • 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 glucamine adduct hydrogen reactions are as follows:
  • Step 1 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 (3X500 psig) and hydrogen (2X500 psig) and rocked under H 2 at room temperature over a weekend at temperatures 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.
  • 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.).
  • 20.36 g of the tallow methyl ester is heated to its melting point (water bath) and loaded into a 250 ml 3-neck round-bottom flask with mechanical stirring. The flask is heated to ca . 70 * C to prevent the ester from solidifying.
  • the product is allowed to remain in the reaction flask at 110'C (external temperature) for 60 minutes.
  • the product is scraped from the flask and triturated in ethyl ether over a weekend.
  • Ether is removed on a rotary evaporator and the product is stored in an oven overnight, and ground to a powder. Any remaining N-methyl maltamine is removed from the product using silica gel.
  • 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 tallow ' alkyl 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.
  • the 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.
  • EXAMPLE V In any of the foregoing examples of detergent compositions, the fatty acid glucamide surfactant can be replaced by an equivalent amount of the maltamide surfactant, or mixtures of glucamide/ alt- amide surfactants derived from plant sugar sources. In the composi ⁇ tions the use of ethanolamides appears to help cold temperature stability of the finished formulations. Moreover, the use of sulfobetaine (aka "sultaine”) surfactants provides superior sudsing. CaCl 2 can be used (ca . 1%) in the formulations to enhance greasy soil removal from dishes. MgCl 2 enhances sudsing.
  • the present invention provides especially high sudsing compositions, it is preferred that less than about 5%, more prefer ⁇ ably less than about 2%, most preferably substantially no C 14 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 C 14 and higher fatty acids on storage of the finished compositions.
  • One simple means is to use C 12 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 bright- ener with water and the polyhydroxy fatty acid amide, and then to add the pre-mix to the final composition.

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Abstract

On décrit des compositions détersives comprenant un constituant de carboxylate d'éthoxy d'alkyle et un constituant d'amide d'acide gras de polyhydroxy. Les compositions détersives de la présente invention possèdent des caractéristiques nettoyantes et moussantes améliorées et une douceur accrue pour la peau. On décrit aussi un procédé de nettoyage de vaisselle sale qui consiste à traiter ladite vasselle au moyen des compositions détersives décrites ci-dessus.
PCT/US1991/006983 1990-09-28 1991-09-25 Compositions detersives contenant des elements carboxylates d'ethoxy d'alkyle et des amides d'acide gras de polyhydroxy WO1992006157A1 (fr)

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RU93005200A RU2105790C1 (ru) 1990-09-28 1991-09-25 Детергентная композиция и способ очистки посуды
JP3517002A JPH06501730A (ja) 1990-09-28 1991-09-25 アルキルエトキシカルボキシレートと多価脂肪酸アミドを含有する洗剤組成物
AU87425/91A AU663855B2 (en) 1990-09-28 1991-09-25 Detergent compositions containing alkyl ethoxy carbozylates and polyhydroxy fatty acid amides
DE69101928T DE69101928T2 (de) 1990-09-28 1991-09-25 Alkylethoxycarboxylate und polyhydroxyfettsäureamide enthaltende waschmittelzusammensetzungen.
SK25793A SK25793A3 (en) 1990-09-28 1991-09-25 Detergent composition containing alkylethoxy carbozylates and polyhydroxy fatty acid amides
BR919106896A BR9106896A (pt) 1990-09-28 1991-09-25 Composicoes detergentes que contem carboxilatos de alquil etoxi e amidas de acido graxo poliidroxil
AT9191918309T ATE105332T1 (de) 1990-09-28 1991-09-25 Alkylethoxycarboxylate und polyhydroxyfettsaeureamide enthaltende waschmittelzusammensetzungen.
PL91298221A PL169553B1 (pl) 1990-09-28 1991-09-25 Alkoksykarboksylanowa kompozycja detergentowa zawierająca alkiloetoksykarboksylany i polihydroksyamidy kwasów tłuszczowych
EP91918309A EP0550652B1 (fr) 1990-09-28 1991-09-25 Compositions detersives contenant des elements carboxylates d'ethoxy d'alkyle et des amides d'acide gras de polyhydroxy
CS93405A CZ282518B6 (cs) 1990-09-28 1991-09-25 Čistící prostředek obsahující alkylethoxykarboxyláty a polyhydroxyamidy mastné kyseliny
NO931022A NO301283B1 (no) 1990-09-28 1993-03-22 Alkoksykarboksylatdetergentblanding og anvendelse derav
FI931363A FI931363A0 (fi) 1990-09-28 1993-03-26 Tvaettmedelskompositioner innehaollande alkyletoxikarboxylater och polyhydroxyfettsyraamider
HK98105323A HK1006180A1 (en) 1990-09-28 1998-06-15 Detergent compositions containing alkyl ethoxy carbozylates and polyhydroxy fatty acid amides

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EP0780464A2 (fr) 1995-12-21 1997-06-25 Henkel Kommanditgesellschaft auf Aktien Procédé pour la préparation des concentrés d'agents tensio-actifs de couleur claire à basse viscosité
US5691300A (en) * 1993-07-12 1997-11-25 Henkel Kommanditgesellschaft Auf Aktien Rinse aids for the machine washing of hard surfaces
US5691291A (en) * 1994-10-28 1997-11-25 The Procter & Gamble Company Hard surface cleaning compositions comprising protonated amines and amine oxide surfactants
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US5789372A (en) * 1994-01-12 1998-08-04 Henkel Kommanditgesellschaft Auf Aktien Surfactant mixtures having improved surface-active properties
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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
US5990064A (en) * 1994-10-28 1999-11-23 The Procter & Gamble Company Compositions and methods for cleaning hard surfaces using protonated amines and amine oxide surfactants
US6165972A (en) * 1998-09-04 2000-12-26 Clariant Gmbh Solid surfactant mixtures comprising fatty acid polyhydroxyamides
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US6846796B2 (en) 2000-04-15 2005-01-25 Cognis Deutschland Gmbh & Co. Kg Method for producing non-ionic tenside granulates
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WO2011049945A2 (fr) 2009-10-23 2011-04-28 Danisco Us Inc. Procédés destinés à réduire le saccharide donnant une couleur bleue
EP2428572A2 (fr) 2007-03-09 2012-03-14 Danisco US, Inc., Genencor Division Variants de l'alpha-amylase d'une espèce de Bacillus alcaliphile, compositions comprenant des variants de l'alpha-amylase, et procédés d'utilisation
US8323945B2 (en) 2008-06-06 2012-12-04 Danisco Us Inc. Variant alpha-amylases from Bacillus subtilis and methods of uses, thereof
US9040279B2 (en) 2008-06-06 2015-05-26 Danisco Us Inc. Saccharification enzyme composition and method of saccharification thereof
US9040278B2 (en) 2008-06-06 2015-05-26 Danisco Us Inc. Production of glucose from starch using alpha-amylases from Bacillus subtilis
US10550355B2 (en) 2015-01-15 2020-02-04 Ecolab Usa Inc. Long lasting cleaning foam
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WO2011049932A1 (fr) * 2009-10-21 2011-04-28 Stepan Company Compositions nettoyantes liquides visqueuses comprenant des acides gras sulfonés, des esters ou des sels de ceux-ci et des bétaïnes ou des sultaïnes
CN101830944A (zh) * 2010-05-25 2010-09-15 中国林业科学研究院林产化学工业研究所 氢化油酸单乙醇酰胺环氧丙烷聚醚醇丁基葡萄糖苷制备和用途
US9222059B2 (en) * 2011-09-20 2015-12-29 The Sun Products Corporation Cleaning formulations with improved surfactant solubility and methods of production and use thereof
CN114867820A (zh) * 2019-11-06 2022-08-05 先进湿润技术私人有限公司 新型润湿组合物

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EP0560570A2 (fr) * 1992-03-09 1993-09-15 Amway Corporation Composition détergente liquide pour la vaisselle
EP0560570A3 (fr) * 1992-03-09 1995-05-10 Amway Corp
US5736503A (en) * 1992-11-30 1998-04-07 The Procter & Gamble Company High sudsing detergent compositions with specially selected soaps
US5691300A (en) * 1993-07-12 1997-11-25 Henkel Kommanditgesellschaft Auf Aktien Rinse aids for the machine washing of hard surfaces
WO1995007337A1 (fr) * 1993-09-09 1995-03-16 The Procter & Gamble Company Detergent extremement savonnant comprenant un amide d'acide gras n-alkoxy polyhydroxy et des tensioactifs de carboxylate secondaire
WO1995007334A1 (fr) * 1993-09-09 1995-03-16 The Procter & Gamble Company Compositions detergentes comportant un melange d'amides d'acides gras n-alkoxy ou n-aryloxy polyhydroxy et d'un tensioactif de carboxylate alkoxyle
US5489393A (en) * 1993-09-09 1996-02-06 The Procter & Gamble Company High sudsing detergent with n-alkoxy polyhydroxy fatty acid amide and secondary carboxylate surfactants
US5712235A (en) * 1993-09-15 1998-01-27 Henkel Kommanditgesellschaft Auf Aktien Bar soaps
EP2199386A1 (fr) 1993-10-08 2010-06-23 Novozymes A/S Variants d'amylase
US5616781A (en) * 1993-10-12 1997-04-01 Stepan Company Liquid detergent compositions comprising salts of alpha sulfonated fatty acid esters and anionic surfactants
EP0723576B1 (fr) * 1993-10-12 2000-03-01 Stepan Company Compositions detergentes liquides comprenant des sels d'esters methyliques ou ethyliques alpha sulfones d'acide gras et des agents tensio-actifs anioniques
US5789372A (en) * 1994-01-12 1998-08-04 Henkel Kommanditgesellschaft Auf Aktien Surfactant mixtures having improved surface-active properties
US5500155A (en) * 1994-03-18 1996-03-19 Henkel Kommanditgesellschaft Auf Aktien Detergent mixtures of fatty acid isethionate salts and fatty alcohols
US5990064A (en) * 1994-10-28 1999-11-23 The Procter & Gamble Company Compositions and methods for cleaning hard surfaces using protonated amines and amine oxide surfactants
US5691291A (en) * 1994-10-28 1997-11-25 The Procter & Gamble Company Hard surface cleaning compositions comprising protonated amines and amine oxide surfactants
US5562865A (en) * 1995-05-18 1996-10-08 Lever Brothers Company, Division Of Conopco, Inc. Oxazolidine and tetrahydrooxazine amide surfactants
US5560872A (en) * 1995-05-18 1996-10-01 Lever Brothers Company Compositions comprising oxazolidine and tetrahydrooxazine amide surfactants
US6264961B1 (en) 1995-09-11 2001-07-24 Henkel Kommanditgesellschaft Auf Aktien Oil-water emulsifiers
EP0776653A1 (fr) 1995-11-30 1997-06-04 Henkel Kommanditgesellschaft auf Aktien Compositions cosmétiques et/ou pharmaceutiques contenant des amides d'acides gras polyhydroxyle
EP0780464A2 (fr) 1995-12-21 1997-06-25 Henkel Kommanditgesellschaft auf Aktien Procédé pour la préparation des concentrés d'agents tensio-actifs de couleur claire à basse viscosité
US5932535A (en) * 1995-12-21 1999-08-03 Henkel Kommanditgesellschaft Auf Aktien Process for the production of light-colored, low-viscosity surfactant concentrates
US6172026B1 (en) 1997-10-21 2001-01-09 Stepan Company Soap bar compositions comprising alpha sulfonated fatty acid alkyl esters and long chain fatty acids
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
WO1999024535A1 (fr) * 1997-11-10 1999-05-20 Henkel Kommanditgesellschaft Auf Aktien Detergents non agressifs pour laver la vaisselle a la main
US6165972A (en) * 1998-09-04 2000-12-26 Clariant Gmbh Solid surfactant mixtures comprising fatty acid polyhydroxyamides
US6387870B1 (en) 1999-03-29 2002-05-14 Ecolab Inc. Solid pot and pan detergent
US6608023B2 (en) 1999-03-29 2003-08-19 Ecolab Inc. Solid pot and pan detergent
US6846796B2 (en) 2000-04-15 2005-01-25 Cognis Deutschland Gmbh & Co. Kg Method for producing non-ionic tenside granulates
US8043946B2 (en) 2005-06-06 2011-10-25 Centrotherm Photovoltaics Ag Mixture for doping semiconductors
DE102005025933B3 (de) * 2005-06-06 2006-07-13 Centrotherm Photovoltaics Gmbh + Co. Kg Dotiergermisch für die Dotierung von Halbleitern
EP2428572A2 (fr) 2007-03-09 2012-03-14 Danisco US, Inc., Genencor Division Variants de l'alpha-amylase d'une espèce de Bacillus alcaliphile, compositions comprenant des variants de l'alpha-amylase, et procédés d'utilisation
US8323945B2 (en) 2008-06-06 2012-12-04 Danisco Us Inc. Variant alpha-amylases from Bacillus subtilis and methods of uses, thereof
US8975056B2 (en) 2008-06-06 2015-03-10 Danisco Us Inc. Variant alpha-amylases from Bacillus subtilis and methods of uses, thereof
US9040279B2 (en) 2008-06-06 2015-05-26 Danisco Us Inc. Saccharification enzyme composition and method of saccharification thereof
US9040278B2 (en) 2008-06-06 2015-05-26 Danisco Us Inc. Production of glucose from starch using alpha-amylases from Bacillus subtilis
US9090887B2 (en) 2008-06-06 2015-07-28 Danisco Us Inc. Variant alpha-amylases from Bacillus subtilis and methods of use, thereof
WO2011049945A2 (fr) 2009-10-23 2011-04-28 Danisco Us Inc. Procédés destinés à réduire le saccharide donnant une couleur bleue
US10550355B2 (en) 2015-01-15 2020-02-04 Ecolab Usa Inc. Long lasting cleaning foam
US11208613B2 (en) 2015-01-15 2021-12-28 Ecolab Usa Inc. Long lasting cleaning foam
US11370997B2 (en) 2016-08-25 2022-06-28 Ecolab Usa Inc. Cleaning compositions and methods of use

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PT99085A (pt) 1992-08-31
DE69101928D1 (de) 1994-06-09
MA22305A1 (fr) 1992-04-01
TW223114B (fr) 1994-05-01
HUT64381A (en) 1993-12-28
HU213735B (en) 1997-09-29
MY109694A (en) 1997-04-30
CN1028878C (zh) 1995-06-14
DK0550652T3 (da) 1994-10-10
SK25793A3 (en) 1993-07-07
FI931363A (fi) 1993-03-26
HU9300895D0 (en) 1993-07-28
AU663855B2 (en) 1995-10-26
CN1061795A (zh) 1992-06-10
CZ282518B6 (cs) 1997-07-16
EG19520A (en) 1995-06-29
HK1006180A1 (en) 1999-02-12
RU2105790C1 (ru) 1998-02-27
CA2092185A1 (fr) 1992-03-29
NO301283B1 (no) 1997-10-06
EP0550652A1 (fr) 1993-07-14
NO931022D0 (no) 1993-03-22
EP0550652B1 (fr) 1994-05-04
ATE105332T1 (de) 1994-05-15
TR25928A (tr) 1993-11-01
NZ240039A (en) 1995-04-27
JPH06501730A (ja) 1994-02-24
PT99085B (pt) 1999-02-26
IE913417A1 (en) 1992-04-08
BR9106896A (pt) 1993-07-20
FI931363A0 (fi) 1993-03-26
ES2052392T3 (es) 1994-07-01
AU8742591A (en) 1992-04-28
IE64631B1 (en) 1995-08-23
MX9101362A (es) 1992-05-04
CA2092185C (fr) 1997-11-04
DE69101928T2 (de) 1994-10-13
CZ40593A3 (en) 1994-04-13
NO931022L (no) 1993-05-25

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