EP0699228B1 - High foaming nonionic surfactant based liquid detergent - Google Patents

High foaming nonionic surfactant based liquid detergent Download PDF

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Publication number
EP0699228B1
EP0699228B1 EP94915886A EP94915886A EP0699228B1 EP 0699228 B1 EP0699228 B1 EP 0699228B1 EP 94915886 A EP94915886 A EP 94915886A EP 94915886 A EP94915886 A EP 94915886A EP 0699228 B1 EP0699228 B1 EP 0699228B1
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alkyl
liquid detergent
weight
amide
surfactant
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German (de)
French (fr)
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EP0699228A1 (en
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Rita Erilli
Stephen T. Repinec, Jr.
Gilbert S. Gomes
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Colgate Palmolive Co
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Colgate Palmolive Co
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    • CCHEMISTRY; METALLURGY
    • C11ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11DDETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D3/00Other compounding ingredients of detergent compositions covered in group C11D1/00
    • C11D3/0005Other compounding ingredients characterised by their effect
    • C11D3/0094High foaming compositions
    • CCHEMISTRY; METALLURGY
    • C11ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11DDETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D1/00Detergent compositions based essentially on surface-active compounds; Use of these compounds as a detergent
    • C11D1/88Ampholytes; Electroneutral compounds
    • C11D1/94Mixtures with anionic, cationic or non-ionic compounds
    • CCHEMISTRY; METALLURGY
    • C11ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11DDETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D1/00Detergent compositions based essentially on surface-active compounds; Use of these compounds as a detergent
    • C11D1/02Anionic compounds
    • C11D1/12Sulfonic acids or sulfuric acid esters; Salts thereof
    • C11D1/123Sulfonic acids or sulfuric acid esters; Salts thereof derived from carboxylic acids, e.g. sulfosuccinates
    • CCHEMISTRY; METALLURGY
    • C11ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11DDETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D1/00Detergent compositions based essentially on surface-active compounds; Use of these compounds as a detergent
    • C11D1/02Anionic compounds
    • C11D1/12Sulfonic acids or sulfuric acid esters; Salts thereof
    • C11D1/126Acylisethionates
    • CCHEMISTRY; METALLURGY
    • C11ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11DDETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D1/00Detergent compositions based essentially on surface-active compounds; Use of these compounds as a detergent
    • C11D1/02Anionic compounds
    • C11D1/12Sulfonic acids or sulfuric acid esters; Salts thereof
    • C11D1/14Sulfonic acids or sulfuric acid esters; Salts thereof derived from aliphatic hydrocarbons or mono-alcohols
    • CCHEMISTRY; METALLURGY
    • C11ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11DDETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D1/00Detergent compositions based essentially on surface-active compounds; Use of these compounds as a detergent
    • C11D1/02Anionic compounds
    • C11D1/12Sulfonic acids or sulfuric acid esters; Salts thereof
    • C11D1/22Sulfonic acids or sulfuric acid esters; Salts thereof derived from aromatic compounds
    • CCHEMISTRY; METALLURGY
    • C11ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11DDETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D1/00Detergent compositions based essentially on surface-active compounds; Use of these compounds as a detergent
    • C11D1/02Anionic compounds
    • C11D1/12Sulfonic acids or sulfuric acid esters; Salts thereof
    • C11D1/28Sulfonation products derived from fatty acids or their derivatives, e.g. esters, amides
    • CCHEMISTRY; METALLURGY
    • C11ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11DDETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D1/00Detergent compositions based essentially on surface-active compounds; Use of these compounds as a detergent
    • C11D1/38Cationic compounds
    • C11D1/52Carboxylic amides, alkylolamides or imides or their condensation products with alkylene oxides
    • C11D1/523Carboxylic alkylolamides, or dialkylolamides, or hydroxycarboxylic amides (R1-CO-NR2R3), where R1, R2 or R3 contain one hydroxy group per alkyl group
    • CCHEMISTRY; METALLURGY
    • C11ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11DDETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D1/00Detergent compositions based essentially on surface-active compounds; Use of these compounds as a detergent
    • C11D1/66Non-ionic compounds
    • C11D1/662Carbohydrates or derivatives
    • CCHEMISTRY; METALLURGY
    • C11ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11DDETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D1/00Detergent compositions based essentially on surface-active compounds; Use of these compounds as a detergent
    • C11D1/66Non-ionic compounds
    • C11D1/667Neutral esters, e.g. sorbitan esters
    • CCHEMISTRY; METALLURGY
    • C11ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11DDETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D1/00Detergent compositions based essentially on surface-active compounds; Use of these compounds as a detergent
    • C11D1/66Non-ionic compounds
    • C11D1/72Ethers of polyoxyalkylene glycols
    • CCHEMISTRY; METALLURGY
    • C11ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11DDETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D1/00Detergent compositions based essentially on surface-active compounds; Use of these compounds as a detergent
    • C11D1/66Non-ionic compounds
    • C11D1/722Ethers of polyoxyalkylene glycols having mixed oxyalkylene groups; Polyalkoxylated fatty alcohols or polyalkoxylated alkylaryl alcohols with mixed oxyalkylele groups
    • CCHEMISTRY; METALLURGY
    • C11ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11DDETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D1/00Detergent compositions based essentially on surface-active compounds; Use of these compounds as a detergent
    • C11D1/66Non-ionic compounds
    • C11D1/75Amino oxides
    • CCHEMISTRY; METALLURGY
    • C11ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11DDETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D1/00Detergent compositions based essentially on surface-active compounds; Use of these compounds as a detergent
    • C11D1/88Ampholytes; Electroneutral compounds
    • C11D1/90Betaines

Definitions

  • the present invention relates to novel light duty liquid detergent compositions with high foaming properties. containing a nonionic surfactant as the major active ingredient supplemented with lesser amounts of a specific group of anionic surfactants and even smaller amounts of a Zwitterionic betaine surfactant and an amine oxide in an aqueous medium.
  • Nonionic surfactants are in general chemically inert and stable toward pH change and are therefore well suited for mixing and formulation with other materials. The superior performance of nonionic surfactants on the removal of oily soil is well recognized. Nonionic surfactants are also known to be mild to human skin. However. as a class, nonionic surfactants are known to be low or moderate foamers. Consequently, for detergents which require copious and stable foam, the application of nonionic surfactants is limited. There have been substantial interest and efforts to develop a high foaming detergent with nonionic surfactants as the major ingredient. Yet, little has been achieved.
  • 4,329,335 also discloses a shampoo containing a betaine surfactant as the major ingredient and minor amounts of a nonionic surfactant and of a fatty acid mono- or di-ethanolamide.
  • U.S. Patent No. 4,259,204 discloses a shampoo comprising 0.8-20% by weight of an anionic phosphoric acid ester and one additional surfactant which may be either anionic, amphoteric, or nonionic.
  • U.S. Patent No. 4.329.334 discloses an anionic-amphoteric based shampoo containing a major amount of anionic surfactant and lesser amounts of a betaine and nonionic surfactants.
  • U.S. Patent No. 3.935.129 discloses a liquid cleaning composition based on the alkali metal silicate content and containing five basic ingredients, namely, urea, glycerin. triethanolamine. an anionic detergent and a nonionic detergent.
  • the silicate content determines the amount of anionic and/or nonionic detergent in the liquid cleaning composition.
  • the foaming property of these detergent compositions is not discussed therein.
  • U.S. Patent No. 4.129.515 discloses a heavy duty liquid detergent for laundering fabrics comprising a mixture of substantially equal amounts of anionic and nonionic surfactants alkanolamines and magnesium salts. and. optionally, zwitterionic surfactants as suds modifiers.
  • U.S. Patent No. 4,224,195 discloses an aqueous detergent composition for laundering socks or stockings comprising a specific group of nonionic detergents. namely. an ethylene oxide of a secondary alcohol, a specific group of anionic detergents, namely, a sulfuric ester salt of an ethylene oxide adduct of a secondary alcohol, and an amphoteric surfactant which may be a betaine. wherein either the anionic or nonionic surfactant may be the major ingredient.
  • the specific class of anionics utilized in this patent is the very same group of anionic detergents expressly excluded in present invention in order to eliminate the alkanol ethoxylate sulfation process and the potential dioxane toxicity problem. Furthermore. this patent finds heavily foaming detergents undesirable for the purpose of washing socks.
  • the prior art also discloses detergent compositions containing all nonionic surfactants as shown in U.S. Patent Nos. 4.154.706 and 4.329.336 wherein the shampoo compositions contain a plurality of particular nonionic surfactants in order to effect desirable foaming and detersive properties despite the fact that nonionic surfactants are usually deficient in such properties.
  • U.S. Patent No. 4.013.787 discloses a piperazine based polymer in conditioning and shampoo compositions which may contain all nonionic surfactant or all anionic surfactant.
  • U.S. Patent No. 4,450,091 discloses high viscosity shampoo compositions containing a blend of an amphoteric betaine surfactant, a polyoxybutylenepolyoxyethylene nonionic detergent. an anionic surfactant. a fatty acid alkanolamide and a polyoxyalkylene glycol fatty ester. But. none of the exemplified compositions contains an active ingredient mixture wherein the nonionic detergent is present in major proportion. probably due to the low foaming properties of the polyoxybutylene polyoxyethylene nonionic detergent.
  • U.S. Patent No. 4.595,526 describes a composition comprising a nonionic surfactant, a betaine surfactant. an anionic surfactant and a C 12 -C 14 fatty acid monethanolamide foam stabilizer.
  • a high foaming, nonionic based. liquid detergent composition containing a nonionic surfactant as a major active ingredient and minor amounts of a supplementary high foaming anionic sulfate or sulfonate surfactant excluding ethoxylated alcohol ether sulfates.
  • a supplementary foaming zwitterionic surfactant selected from betaine type surfactants, an amine oxide. an alkyl monoalkanol amide. an alkyl dialkanol amide and wherein the nonionic ingredient constitutes more than 50% of the total surfactant content.
  • a high foaming liquid detergent can be formulated with a nonionic surfactant as the major active ingredient which has desirable cleaning properties, mildness to the human skin and avoids the dioxane toxicity problem associated with the sulfation process of manufacturing anionic ethoxylated alcohol ether sulfates.
  • one object of the invention is to provide novel, high foaming, nonionic based. light duty liquid detergent compositions containing a nonionic surfactant at a concentration of at least 50% of the total surfactant content.
  • Another object of this invention is to provide novel, nonionic based. liquid detergent compositions containing a major amount of nonionic surfactant supplemented with lesser amounts of an anionic surfactant, a zwitterionic betaine surfactant. an alkyl monoalkanol amide. an alkyl dialkanol amide, and an amine oxide.
  • Still another object of this invention is to provide a novel. nonionic based. liquid detergent with desirable high foaming and cleaning properties which is mild to the human skin.
  • a further object of this invention is to provide a novel, nonionic based liquid detergent containing a supplemental anionic surfactant excluding the ethoxylated alkyl ether sulfates which eliminates the alkanol ethoxylate sulfation process and the potential dioxane toxicity problem.
  • high foaming, nonionic based. light duty liquid detergent of this invention comprises an alkyl monoalkanol amide and an alkyl dialkanol amide in combination with four essential surfactants a water soluble.
  • ethoxylated, nonionic surfactant as the major active ingredient in an amount exceeding 50% by weight of the total surfactant content: a supplemental amount of a foaming anionic surfactant selected from the group consisting of water soluble organic sulfates and organic sulfonates, excluding the ethoxylated alkyl ether sulfates; a lesser amount of a foaming water soluble, zwitterionic surfactant selected from the class of betaines dissolved in an aqueous vehicle and an amine oxide, wherein the composition does not contain any polyoxyalkylene glycol fatty ester.
  • a foaming anionic surfactant selected from the group consisting of water soluble organic sulfates and organic sulfonates, excluding the ethoxylated alkyl ether sulfates
  • a lesser amount of a foaming water soluble, zwitterionic surfactant selected from the class of betaines dissolved in an aqueous vehicle and an
  • the present invention relates to a high foaming, nonionic based, liquid detergent containing more than 50% by weight of the total surfactant content of a nonionic surfactant selected from the group consisting of water soluble primary aliphatic alcohol ethoxylates secondary aliphatic alcohol ethoxylates, alkyl phenol ethoxylates and alcohol ethylene oxide propylene oxide condensates; and supplementary amounts of an anionic surfactant selected from the group consisting of water soluble salts of C 8 -C 18 alkyl sulfates, C 8 -C 16 alkyl benzene sulfonates, C 10 -C 20 paraffin sulfonates, alpha C 10 -C 24 olefin sulfonates, C 8 -C 18 alkyl sulfoacetates, C 8 -C 18 alkyl sulfosuccinate esters, C 8 -C 18 acyl isethionates and C
  • percent of the total surfactant content is critical to the high foaming and desirable cleansing properties of present liquid detergent and the retention of the mildness to the skin property.
  • the total amount of surfactants may constitute 17.5%-51%. preferably 20%-40%, most preferably 25%-35%, by weight of the liquid composition.
  • Excluded from the instant compounds are polyoxyalkylene glycol fatty esters, abrasives, polymeric thickeners, clay thickeners, silica, abrasive, clays, alkali metal carbonates or more than 3 wt. % of a fatty acid or its salt thereof.
  • the nonionic surfactant which constitutes the major ingredient in present liquid detergent is present in amounts of 10%-30%. preferably 13%-25%. most preferably 16%-22%, by weight of the composition and provides superior performance in the removal of oily soil and mildness to human skin.
  • the water soluble nonionic surfactants utilized in this invention are commercially well known and include the primary aliphatic alcohol ethoxylates. Secondary aliphatic alcohol ethoxylates, alkylphenol ethoxylates and ethylene-oxide-propylene oxide condensates on primary alkanols. such a Plurafacs (BASF) and condensates of ethylene oxide with sorbitan fatty acid esters such as the Tweens (ICI).
  • the nonionic synthetic organic detergents generally are the condensation products of an organic aliphatic or alkyl aromatic hydrophobic compound and hydrophilic ethylene oxide groups.
  • any hydrophobic compound having a carboxy, hydroxy, amido, or amino group with a free hydrogen attached to the nitrogen can be condensed with ethylene oxide or with the polyhydration product thereof, polyethylene glycol, to form a water-soluble nonionic detergent. Further, the length of the polyethenoxy chain can be adjusted to achieve the desired balance between the hydrophobic and hydrophilic elements.
  • the nonionic detergent class includes the condensation products of a higher alcohol (e.g., an alkanol containing 8 to 18 carbon atoms in a straight or branched chain configuration) condensed with 5 to 30 moles of ethylene oxide, for example, lauryl or myristyl alcohol condensed with 16 moles of ethylene oxide (EO), tridecanol condensed with 6 to moles of EO, myristyl alcohol condensed with about 10 moles of EO per mole of myristyl alcohol, the condensation product of EO with a cut of coconut fatty alcohol containing a mixture of fatty alcohols with alkyl chains varying from 10 to 14 carbon atoms in length and wherein the condensate contains either 6 moles of EO per mole of total alcohol or 9 moles of EO per mole of alcohol and tallow alcohol ethoxylates containing 6 EO to 11 EO per mole of alcohol.
  • a higher alcohol e.g., an alkanol containing 8
  • Neodol ethoxylates which are higher aliphatic, primary alcohols containing about 9-15 carbon atoms, such as C 9 -C 11 alkanol condensed with 8 moles of ethylene oxide (Neodol 91-8), C 12-13 alkanol condensed with 6.5 moles ethylene oxide (Neodol 23-6.5), C 12-15 alkanol condensed with 12 moles ethylene oxide (Neodol 25-12) and C 14-15 alkanol condensed with 13 moles ethylene oxide (Neodol 45-13).
  • Neodol ethoxylates such as C 9 -C 11 alkanol condensed with 8 moles of ethylene oxide (Neodol 91-8), C 12-13 alkanol condensed with 6.5 moles ethylene oxide (Neodol 23-6.5), C 12-15 alkanol condensed with 12 moles ethylene oxide (Neodol 25-12) and C 14
  • Such ethoxamers have an HLB (hydrophobic lipophilic balance) value of 8-15 and give good/W emulsification, whereas ethoxamers with HLB values below 8 contain less than 5 ethyleneoxy groups and tend to be poor emulsifiers and poor detergents.
  • HLB hydrophobic lipophilic balance
  • Additional satisfactory water soluble alcohol ethylene oxide condensates are the condensation products of a secondary aliphatic alcohol containing 8 to 18 carbon atoms in a straight or branched chain configuration condensed with 5 to 30 moles of ethylene oxide.
  • Examples of commercially available nonionic detergents of the foregoing type are C 11 -C 15 secondary alkanol condensed with either 9 EO (Tergitol 15-S-9) or 12 EO (Tergitol 15-S-12) marketed by Union Carbide.
  • nonionic detergents include the polyethylene oxide condensates of one mole of alkyl phenol containing from 8 to 18 carbon atoms in a straight- or branched chain alkyl group with 5 to 30 moles of ethylene oxide.
  • alkyl phenol ethoxylates include nonyl condensed with 9.5 moles of EO per mole of nonyl phenol, dinonyl phenol condensed with 12 moles of EO per mole of phenol, dinonyl phenol condensed with 15 moles of EO per mole of phenol and diisoctylphenol condensed with 15 moles of EO per mole of phenol.
  • nonionic surfactants of this type include Igepal CO-630 (nonyl phenol ethoxylate) marketed by GAF Corporation.
  • nonionic detergents are the water-soluble condensation products of a C 8 -C 20 alkanol with a heteric mixture of ethylene oxide and propylene oxide wherein the weight ratio of ethylene oxide to propylene oxide is from 2.5:1 to 4:1, preferably 2.8:1-3.3:1, with the total of the ethylene oxide and propylene oxide (including the terminal ethanol or propanol group) being from 60-85%, preferably 70-80%, by weight.
  • Such detergents are commercially available from BASF-Wyandotte and a particularly preferred detergent is a C 10 -C 16 alkanol condensate with ethylene oxide and propylene oxide, the weight ratio of ethylene oxide to propylene oxide being 3:1 and the total alkoxy content being 75% by weight.
  • Suitable water-soluble nonionic detergents which are less preferred are marketed under the trade name "Pluronics.”
  • the compounds are formed by condensing ethylene oxide with a hydrophobic base formed by the condensation of propylene oxide with propylene glycol.
  • the molecular weight of the hydrophobic portion of the molecule is of the order of 950 to 4000 and preferably 200 to 2,500.
  • the addition of polyoxyethylene radicals to the hydrophobic portion tends to increase the solubility of the molecule as a whole so as to make the surfactant water-soluble.
  • the molecular weight of the block polymers varies from 1,000 to 15,000 and the polyethylene oxide content may comprise 20% to 80% by weight.
  • these surfactants will be in liquid form and satisfactory surfactants are available as grades L62 and L64.
  • the anionic surfactant which is an essential ingredient of present liquid detergent composition, constitutes 1% to 10%, preferably 2%-9%, most preferably 3%-8%, by weight thereof and provides good foaming properties. However, preferably reduced amounts are utilized in order to enhance the mildness of the skin property desired in the inventive compositions, and thus, the weight ratio of nonionic detergent to anionic should exceed about 3:1.
  • the particular group of anionic surfactants utilized excludes the C 8 -C 18 alkyl polyethenoxy ether sulfate surfactants in order to avoid the dioxane toxicity associated with the process of sulfation of ethoxylated alcohols. Thus, the ethoxylated alcohol ether sulfates are expressly excluded from the specific group of anionic surfactants utilized.
  • the anionic surfactants which may be used in the nonionic based liquid detergent of this invention are water soluble such as triethanolamine and include the sodium, potassium, ammonium and ethanolammonium salts of C 8 -C 18 alkyl sulfates such as lauryl sulfate and myristyl sulfates; linear C 8 -C 16 alkyl benzene sulfonates; C 10 -C 20 paraffin sulfonates; alpha olefin sulfonates containing about 10-24 carbon atoms; C 8 -C 18 alkyl sulfoacetates; C 8 -C 18 alkyl sulfosuccinate esters; C 8 -C 18 acyl isethionates; and C 8 -C 18 acyl taurates.
  • C 8 -C 18 alkyl sulfates such as lauryl sulfate and myristyl sulfates
  • Preferred anionic surfactants are the water soluble C 12 -C 16 alkyl sulfates, the C 10 -C 15 alkylbenzene sulfonates, the C 13 -C 17 paraffin sulfonates and the alpha C 12 -C 18 olefin sulfonates.
  • the water-soluble zwitterionic surfactant which is also an essential ingredient of present liquid detergent composition, constitutes 0.5-10%, preferably 2%-9%. most preferably 7%-8%, by weight and provides good foaming properties and mildness to the present nonionic based liquid detergent.
  • the zwitterionic surfactant is a water soluble betaine having the general formula: wherein R 1 is an alkyl group having 10 to 20 carbon atoms, preferably 12 to 16 carbon atoms, or the amido radical: wherein R is an alkyl group having 9 to 19 carbon atoms and a is the integer 1 to 4; R 2 and R 3 are each alkyl groups having 1 to 3 carbons and preferably 1 carbon; R 4 is an alkylene or hydroxyalkylene group having from 1 to 4 carbon atoms and, optionally, one hydroxyl group.
  • Typical alkyldimethyl betaines include decyl dimethyl betaine or 2-(N-decyl-N, N-dimethyl-ammonia) acetate, coco dimethyl betaine or 2-(N-coco N. N-dimethylammonio) acetate, myristyl dimethyl betaine, palmityl dimethyl betaine, lauryl diemethyl betaine, cetyl dimethyl betaine and stearyl dimethyl betaine.
  • the amidobetaines similarly include cocoamidoethylbetaine and cocoamidopropyl betaine.
  • a preferred betaine is coco (C 8 -C 18 ) amidopropyl dimethyl betaine.
  • Amine oxide semi-polar nonionic surfactants comprise compounds and mixtures of compounds having the formula wherein R 1 is an alkyl. 2-hydroxyalkyl, 3-hydroxyalkyl, or 3-alkoxy-2-hydroxypropyl radical in which the alkyl and alkoxy, respectively, contain from 8 to 18 carbon atoms.
  • R 2 and R 3 are each methyl, ethyl, propyl, isopropyl, 2-hydroxyethyl, 2-hydroxypropyl, or 3-hydroxypropyl, and n is from 0 to 10.
  • Particularly preferred are amine oxides of the formula: wherein R 1 is a C 12-16 alkyl and R 2 and R 3 are methyl or ethyl.
  • the concentration of the amine oxide in the instant compositions is 1.0 to 5 wt. %, more preferably 2 to 4 wt. % and most preferably 2.5 to 3.5 wt. %.
  • the instant composition contains a mixture of a C 12-14 alkyl monoalkanol amide such as lauryl monoalkanol amide and a C 12-14 alkyl dialkanol amide such as lauryl diethanol amide or coco diethanol amide, wherein the concentration of the monoalkanol amide is 1 to 3 wt. % and the concentration of the dialkanol amide is 1 to 3 wt. %.
  • a C 12-14 alkyl monoalkanol amide such as lauryl monoalkanol amide
  • a C 12-14 alkyl dialkanol amide such as lauryl diethanol amide or coco diethanol amide
  • This particular combination of C 12-14 alkyl monoalkanol amide, C 12-14 alkyl dialkanol amide, anionic surfactant, amine oxide and betaine surfactant provides a detergent system which coacts with the nonionic surfactant to product a liquid detergent composition with desirable foaming, foam stability, detersive properties and mildness to human skin.
  • the resultant homogeneous liquid detergent exhibits the same or better foam performance, both as to initial foam volume and stability of foam in the presence of soils, and cleaning efficacy as an anionic based light duty liquid detergent (LDLD) as shown in the following Examples.
  • LDLD light duty liquid detergent
  • the nonionic surfactant, the anionic surfactant, the betaine surfactant, the C 12-14 alkyl monoalkanol amide, the C 12-14 alkyl dialkanol amide and the amine oxide are solubilized in the water.
  • water soluble hydrotropic salts include sodium, potassium, ammonium and mono-, di- and triethanolammonium salts.
  • the aqueous medium is primarily water, preferably said solubilizing agents are included in order to control the viscosity of the liquid composition and to control low temperature cloud clear properties. Usually, it is desirable to maintain clarity to a temperature in the range of 5°C to 10°C.
  • the proportion of solubilizer generally will be from 1%-15%, preferably 2%-12%, most preferably 2%-8%, by weight of the detergent composition with the proportion of ethanol, when present, being 5% of weight or less in order to provide a composition having a flash point above 46°C.
  • the solubilizing ingredient will be a mixture of ethanol and either sodium xylene sulfonate or sodium cumene sulfonate or a mixture of said sulfonates or ethanol and urea.
  • Inorganic salts such as sodium sulfate, magnesium sulfate, sodium chloride and sodium citrate can be added at concentrations of 0.5 to 4.0 wt.
  • solubilizing agents such as perfumes, sodium bisulfite, ETDA, isoethanoeic acid and proteins such as lexine protein.
  • solubilizing ingredients also facilitate the manufacture of the inventive compositions because they tend to inhibit gel formation.
  • various coloring agents and perfumes such as the Uvinuls, which are products of GAF Corporation; sequestering agents such as ethylene diamine tetraacetates; magnesium sulfate heptahydrate; pearlescing agents and opacifiers; pH modifiers; etc.
  • the proportion of such adjuvant materials. in total will normally not exceed 15% of weight of the detergent composition, and the percentages of most of such individual components will be a maximum of 5% by weight and preferably less than 2% by weight.
  • Sodium formate can be included in the formula as a perservative at a concentration of 0.1 to 4.0%.
  • Sodium bisulfite can be used as a color stabilizer at a concentration of 0.01 to 0.2 wt. %
  • nonionic based light duty liquid detergents such as dishwashing liquids are readily made by simple mixing methods from readily available components which, on storage, do not adversely affect the entire composition.
  • the nonionic surfactant be mixed with the solubilizing ingredients, e.g., ethanol and. if present. prior to the addition of the water to prevent possible gelation.
  • the nonionic based surfactant system is prepared by sequentially adding with agitation the anionic surfactant, the betaine surfactant, the amine oxide, the C 12-14 alkyl monoalkanol amide and the C 12-14 alkyl dialkanol amide to the aqueous solution of the non-ionic surfactant which has been previously mixed with a solubilizing agent such as ethyl alcohol and/or sodium xylene sulfonate to assist in solubilizing said surfactants, and then adding with agitation the formula amount of water to form an aqueous solution of the nonionic based surfactant system.
  • a solubilizing agent such as ethyl alcohol and/or sodium xylene sulfonate
  • the viscosities are adjustable by changing the total percentage of active ingredients. Usually, no thickening agent is added, but thickeners may be added if higher viscosity liquids are desired. In all such cases the product made will be pourable from a relatively narrow mouth bottle (1.5 cm. diameter) or opening, and the viscosity of the detergent formulation will not be so low as to be like water.
  • the viscosity of the detergent desirably will be at least 100 centipoises (cps) at room temperature, but may be up to 1,000 centipoises as measured with a Brookfield Viscometer using a number 3 spindle rotating at 12 rpm. Its viscosity may approximate those of commercially acceptable detergents now on the market.
  • the detergent viscosity and the detergent itself remain stable on storage for lengthy periods of time, without color changes or settling out of any insoluble materials.
  • the pH of this formation is substantially neutral to skin, e.g., 4.5 to 8 and preferably 5.0 to 5.0.
  • the foam quality and detersive property is equal to or better than standard light duty liquid detergents while using a nonionic surfactant as the primary surfactant and minimal amounts of anionic surfactant, thereby achieving a mild, non-irritating liquid detergent.
  • Example 1 of U. S. Patent 4,495,526 (designated L) and Formula A of Example 1 of this application were compared in a Hand Dish Wash Test.
  • the test was run with Olive Oil, Beef Tallow and Butter in a ratio of equal amounts.
  • the results show that Formula A of Example 1 gave better results than the standard Formula L (Example 1 of U.S. Patent 4.495.526).
  • the test was run blind with each trial consisting of two runs of each product and the test was done in hard water (300 ppm).

Abstract

A high foaming, nonionic surfactant based, light duty, liquid detergent with desirable cleansing properties and mildness to the human skin comprising: a water soluble nonionic surfactant as the major active ingredient, in an amount in excess of 50 % by weight of the total surfactant content; a supplemental amount of a water soluble, foaming, anionic surfactant excluding the ethoxylated alkyl ether sulfates; and a lesser amount of a water soluble, foaming zwitterionic betaine surfactant, a C12-14 alkyl monoalkanol amide, a C12-14 alkyl dialkanol amide, and an amine oxide.

Description

    Related Application
  • This application is a continuation in part application of U.S. Serial No. 8/056,086, filed May 3, 1993.
  • Background of the Invention
  • The present invention relates to novel light duty liquid detergent compositions with high foaming properties. containing a nonionic surfactant as the major active ingredient supplemented with lesser amounts of a specific group of anionic surfactants and even smaller amounts of a Zwitterionic betaine surfactant and an amine oxide in an aqueous medium.
  • Nonionic surfactants are in general chemically inert and stable toward pH change and are therefore well suited for mixing and formulation with other materials. The superior performance of nonionic surfactants on the removal of oily soil is well recognized. Nonionic surfactants are also known to be mild to human skin. However. as a class, nonionic surfactants are known to be low or moderate foamers. Consequently, for detergents which require copious and stable foam, the application of nonionic surfactants is limited. There have been substantial interest and efforts to develop a high foaming detergent with nonionic surfactants as the major ingredient. Yet, little has been achieved.
  • The prior art is replete with light duty liquid detergent compositions containing nonionic surfactants in combination with anionic and/or betaine surfactants wherein the nonionic detergent is not the major active surfactant, as shown in U.S. Patent No. 3.658,985 wherein an anionic based shampoo contains a minor amount of a fatty acid alkanolamide. U.S. Patent No. 3,769,398 discloses a betaine-based shampoo containing minor amounts of nonionic surfactants. This patent states that the low foaming properties of nonionic detergents renders its use in shampoo compositions non-preferred. U.S. Patent No. 4,329,335 also discloses a shampoo containing a betaine surfactant as the major ingredient and minor amounts of a nonionic surfactant and of a fatty acid mono- or di-ethanolamide. U.S. Patent No. 4,259,204 discloses a shampoo comprising 0.8-20% by weight of an anionic phosphoric acid ester and one additional surfactant which may be either anionic, amphoteric, or nonionic. U.S. Patent No. 4.329.334 discloses an anionic-amphoteric based shampoo containing a major amount of anionic surfactant and lesser amounts of a betaine and nonionic surfactants.
  • U.S. Patent No. 3.935.129 discloses a liquid cleaning composition based on the alkali metal silicate content and containing five basic ingredients, namely, urea, glycerin. triethanolamine. an anionic detergent and a nonionic detergent. The silicate content determines the amount of anionic and/or nonionic detergent in the liquid cleaning composition. However. the foaming property of these detergent compositions is not discussed therein.
  • U.S. Patent No. 4.129.515 discloses a heavy duty liquid detergent for laundering fabrics comprising a mixture of substantially equal amounts of anionic and nonionic surfactants alkanolamines and magnesium salts. and. optionally, zwitterionic surfactants as suds modifiers.
  • U.S. Patent No. 4,224,195 discloses an aqueous detergent composition for laundering socks or stockings comprising a specific group of nonionic detergents. namely. an ethylene oxide of a secondary alcohol, a specific group of anionic detergents, namely, a sulfuric ester salt of an ethylene oxide adduct of a secondary alcohol, and an amphoteric surfactant which may be a betaine. wherein either the anionic or nonionic surfactant may be the major ingredient. The specific class of anionics utilized in this patent is the very same group of anionic detergents expressly excluded in present invention in order to eliminate the alkanol ethoxylate sulfation process and the potential dioxane toxicity problem. Furthermore. this patent finds heavily foaming detergents undesirable for the purpose of washing socks.
  • The prior art also discloses detergent compositions containing all nonionic surfactants as shown in U.S. Patent Nos. 4.154.706 and 4.329.336 wherein the shampoo compositions contain a plurality of particular nonionic surfactants in order to effect desirable foaming and detersive properties despite the fact that nonionic surfactants are usually deficient in such properties.
  • U.S. Patent No. 4.013.787 discloses a piperazine based polymer in conditioning and shampoo compositions which may contain all nonionic surfactant or all anionic surfactant.
  • U.S. Patent No. 4,450,091 discloses high viscosity shampoo compositions containing a blend of an amphoteric betaine surfactant, a polyoxybutylenepolyoxyethylene nonionic detergent. an anionic surfactant. a fatty acid alkanolamide and a polyoxyalkylene glycol fatty ester. But. none of the exemplified compositions contains an active ingredient mixture wherein the nonionic detergent is present in major proportion. probably due to the low foaming properties of the polyoxybutylene polyoxyethylene nonionic detergent.
  • U.S. Patent No. 4.595,526 describes a composition comprising a nonionic surfactant, a betaine surfactant. an anionic surfactant and a C12-C14 fatty acid monethanolamide foam stabilizer.
  • However, none of the above-cited patents discloses a high foaming, nonionic based. liquid detergent composition containing a nonionic surfactant as a major active ingredient and minor amounts of a supplementary high foaming anionic sulfate or sulfonate surfactant excluding ethoxylated alcohol ether sulfates. a supplementary foaming zwitterionic surfactant selected from betaine type surfactants, an amine oxide. an alkyl monoalkanol amide. an alkyl dialkanol amide and wherein the nonionic ingredient constitutes more than 50% of the total surfactant content.
  • Summary of the Invention
  • It has now been found that a high foaming liquid detergent can be formulated with a nonionic surfactant as the major active ingredient which has desirable cleaning properties, mildness to the human skin and avoids the dioxane toxicity problem associated with the sulfation process of manufacturing anionic ethoxylated alcohol ether sulfates.
  • Accordingly, one object of the invention is to provide novel, high foaming, nonionic based. light duty liquid detergent compositions containing a nonionic surfactant at a concentration of at least 50% of the total surfactant content.
  • Another object of this invention is to provide novel, nonionic based. liquid detergent compositions containing a major amount of nonionic surfactant supplemented with lesser amounts of an anionic surfactant, a zwitterionic betaine surfactant. an alkyl monoalkanol amide. an alkyl dialkanol amide, and an amine oxide.
  • Still another object of this invention is to provide a novel. nonionic based. liquid detergent with desirable high foaming and cleaning properties which is mild to the human skin.
  • A further object of this invention is to provide a novel, nonionic based liquid detergent containing a supplemental anionic surfactant excluding the ethoxylated alkyl ether sulfates which eliminates the alkanol ethoxylate sulfation process and the potential dioxane toxicity problem.
  • Additional objects. advantages and novel features of the invention will be set forth in part in the description which follows, and in part will become apparent to those skilled in the art upon examination of the following or may be learned by practice of the invention. The objects and advantages of the invention may be realized and attained by means of the instrumentalities and combinations particularly pointed out in the appended claims.
  • To achieve the foregoing and other objects and in accordance with the purpose of the present invention. as embodied and broadly described herein the novel. high foaming, nonionic based. light duty liquid detergent of this invention comprises an alkyl monoalkanol amide and an alkyl dialkanol amide in combination with four essential surfactants a water soluble. ethoxylated, nonionic surfactant as the major active ingredient in an amount exceeding 50% by weight of the total surfactant content: a supplemental amount of a foaming anionic surfactant selected from the group consisting of water soluble organic sulfates and organic sulfonates, excluding the ethoxylated alkyl ether sulfates; a lesser amount of a foaming water soluble, zwitterionic surfactant selected from the class of betaines dissolved in an aqueous vehicle and an amine oxide, wherein the composition does not contain any polyoxyalkylene glycol fatty ester.
  • More specifically, the present invention relates to a high foaming, nonionic based, liquid detergent containing more than 50% by weight of the total surfactant content of a nonionic surfactant selected from the group consisting of water soluble primary aliphatic alcohol ethoxylates secondary aliphatic alcohol ethoxylates, alkyl phenol ethoxylates and alcohol ethylene oxide propylene oxide condensates; and supplementary amounts of an anionic surfactant selected from the group consisting of water soluble salts of C8-C18 alkyl sulfates, C8-C16 alkyl benzene sulfonates, C10-C20 paraffin sulfonates, alpha C10-C24 olefin sulfonates, C8-C18 alkyl sulfoacetates, C8-C18 alkyl sulfosuccinate esters, C8-C18 acyl isethionates and C8-C18 acyl taurates; a C12-C14 alkyl monoethanol amide; a C12-C14 alkyl diethanol amide; a water soluble zwitterionic betaine surfactant and an amine oxide; the total content of said amine oxide, said anionic surfactant, said alkyl monoethanol amide, said alkyl diethanol amide and said betaine surfactant, constituting less that 50% by weight of the total surfactant content, dissolved in an aqueous vehicle.
  • This particular combination of ingredients in the proportions. by weight, of 10 to 30% of a nonionic surfactant, 1 to 10% by weight of anionic surfactant, 0.5 to 10% by weight of a betaine surfactant, 1.0 to 5% of an amine oxide 1 to 3 wt. % of a C12-C14 alkyl monoalkanol amide such as a C12-C14 alkyl monoethanolamide; 1 to 3 wt. % of a C12-C14 alkyl dialkanol amide such as a C12-C14 alkyl diethanol amide and the balance being water, wherein the nonionic constitutes at least 50 wt. percent of the total surfactant content is critical to the high foaming and desirable cleansing properties of present liquid detergent and the retention of the mildness to the skin property. The total amount of surfactants may constitute 17.5%-51%. preferably 20%-40%, most preferably 25%-35%, by weight of the liquid composition. Excluded from the instant compounds are polyoxyalkylene glycol fatty esters, abrasives, polymeric thickeners, clay thickeners, silica, abrasive, clays, alkali metal carbonates or more than 3 wt. % of a fatty acid or its salt thereof.
  • Detailed Description of the Invention
  • The nonionic surfactant which constitutes the major ingredient in present liquid detergent is present in amounts of 10%-30%. preferably 13%-25%. most preferably 16%-22%, by weight of the composition and provides superior performance in the removal of oily soil and mildness to human skin.
  • The water soluble nonionic surfactants utilized in this invention are commercially well known and include the primary aliphatic alcohol ethoxylates. secondary aliphatic alcohol ethoxylates, alkylphenol ethoxylates and ethylene-oxide-propylene oxide condensates on primary alkanols. such a Plurafacs (BASF) and condensates of ethylene oxide with sorbitan fatty acid esters such as the Tweens (ICI). The nonionic synthetic organic detergents generally are the condensation products of an organic aliphatic or alkyl aromatic hydrophobic compound and hydrophilic ethylene oxide groups. Practically any hydrophobic compound having a carboxy, hydroxy, amido, or amino group with a free hydrogen attached to the nitrogen can be condensed with ethylene oxide or with the polyhydration product thereof, polyethylene glycol, to form a water-soluble nonionic detergent. Further, the length of the polyethenoxy chain can be adjusted to achieve the desired balance between the hydrophobic and hydrophilic elements.
  • The nonionic detergent class includes the condensation products of a higher alcohol (e.g., an alkanol containing 8 to 18 carbon atoms in a straight or branched chain configuration) condensed with 5 to 30 moles of ethylene oxide, for example, lauryl or myristyl alcohol condensed with 16 moles of ethylene oxide (EO), tridecanol condensed with 6 to moles of EO, myristyl alcohol condensed with about 10 moles of EO per mole of myristyl alcohol, the condensation product of EO with a cut of coconut fatty alcohol containing a mixture of fatty alcohols with alkyl chains varying from 10 to 14 carbon atoms in length and wherein the condensate contains either 6 moles of EO per mole of total alcohol or 9 moles of EO per mole of alcohol and tallow alcohol ethoxylates containing 6 EO to 11 EO per mole of alcohol.
  • A preferred group of the foregoing nonionic surfactants are the Neodol ethoxylates (Shell Co.), which are higher aliphatic, primary alcohols containing about 9-15 carbon atoms, such as C9-C11 alkanol condensed with 8 moles of ethylene oxide (Neodol 91-8), C12-13 alkanol condensed with 6.5 moles ethylene oxide (Neodol 23-6.5), C12-15 alkanol condensed with 12 moles ethylene oxide (Neodol 25-12) and C14-15 alkanol condensed with 13 moles ethylene oxide (Neodol 45-13). Such ethoxamers have an HLB (hydrophobic lipophilic balance) value of 8-15 and give good/W emulsification, whereas ethoxamers with HLB values below 8 contain less than 5 ethyleneoxy groups and tend to be poor emulsifiers and poor detergents.
  • Additional satisfactory water soluble alcohol ethylene oxide condensates are the condensation products of a secondary aliphatic alcohol containing 8 to 18 carbon atoms in a straight or branched chain configuration condensed with 5 to 30 moles of ethylene oxide. Examples of commercially available nonionic detergents of the foregoing type are C11-C15 secondary alkanol condensed with either 9 EO (Tergitol 15-S-9) or 12 EO (Tergitol 15-S-12) marketed by Union Carbide.
  • Other suitable nonionic detergents include the polyethylene oxide condensates of one mole of alkyl phenol containing from 8 to 18 carbon atoms in a straight- or branched chain alkyl group with 5 to 30 moles of ethylene oxide. Specific examples of alkyl phenol ethoxylates include nonyl condensed with 9.5 moles of EO per mole of nonyl phenol, dinonyl phenol condensed with 12 moles of EO per mole of phenol, dinonyl phenol condensed with 15 moles of EO per mole of phenol and diisoctylphenol condensed with 15 moles of EO per mole of phenol. Commercially available nonionic surfactants of this type include Igepal CO-630 (nonyl phenol ethoxylate) marketed by GAF Corporation.
  • Also among the satisfactory nonionic detergents are the water-soluble condensation products of a C8-C20 alkanol with a heteric mixture of ethylene oxide and propylene oxide wherein the weight ratio of ethylene oxide to propylene oxide is from 2.5:1 to 4:1, preferably 2.8:1-3.3:1, with the total of the ethylene oxide and propylene oxide (including the terminal ethanol or propanol group) being from 60-85%, preferably 70-80%, by weight. Such detergents are commercially available from BASF-Wyandotte and a particularly preferred detergent is a C10-C16 alkanol condensate with ethylene oxide and propylene oxide, the weight ratio of ethylene oxide to propylene oxide being 3:1 and the total alkoxy content being 75% by weight.
  • Other suitable water-soluble nonionic detergents which are less preferred are marketed under the trade name "Pluronics." The compounds are formed by condensing ethylene oxide with a hydrophobic base formed by the condensation of propylene oxide with propylene glycol. The molecular weight of the hydrophobic portion of the molecule is of the order of 950 to 4000 and preferably 200 to 2,500. The addition of polyoxyethylene radicals to the hydrophobic portion tends to increase the solubility of the molecule as a whole so as to make the surfactant water-soluble. The molecular weight of the block polymers varies from 1,000 to 15,000 and the polyethylene oxide content may comprise 20% to 80% by weight. Preferably, these surfactants will be in liquid form and satisfactory surfactants are available as grades L62 and L64.
  • The anionic surfactant, which is an essential ingredient of present liquid detergent composition, constitutes 1% to 10%, preferably 2%-9%, most preferably 3%-8%, by weight thereof and provides good foaming properties. However, preferably reduced amounts are utilized in order to enhance the mildness of the skin property desired in the inventive compositions, and thus, the weight ratio of nonionic detergent to anionic should exceed about 3:1. In addition, the particular group of anionic surfactants utilized excludes the C8-C18 alkyl polyethenoxy ether sulfate surfactants in order to avoid the dioxane toxicity associated with the process of sulfation of ethoxylated alcohols. Thus, the ethoxylated alcohol ether sulfates are expressly excluded from the specific group of anionic surfactants utilized.
  • The anionic surfactants which may be used in the nonionic based liquid detergent of this invention are water soluble such as triethanolamine and include the sodium, potassium, ammonium and ethanolammonium salts of C8-C18 alkyl sulfates such as lauryl sulfate and myristyl sulfates; linear C8-C16 alkyl benzene sulfonates; C10-C20 paraffin sulfonates; alpha olefin sulfonates containing about 10-24 carbon atoms; C8-C18 alkyl sulfoacetates; C8-C18 alkyl sulfosuccinate esters; C8-C18 acyl isethionates; and C8-C18 acyl taurates. Preferred anionic surfactants are the water soluble C12-C16 alkyl sulfates, the C10-C15 alkylbenzene sulfonates, the C13-C17 paraffin sulfonates and the alpha C12-C18 olefin sulfonates.
  • The water-soluble zwitterionic surfactant, which is also an essential ingredient of present liquid detergent composition, constitutes 0.5-10%, preferably 2%-9%. most preferably 7%-8%, by weight and provides good foaming properties and mildness to the present nonionic based liquid detergent. The zwitterionic surfactant is a water soluble betaine having the general formula:
    Figure imgb0001
    wherein R1 is an alkyl group having 10 to 20 carbon atoms, preferably 12 to 16 carbon atoms, or the amido radical:
    Figure imgb0002
    wherein R is an alkyl group having 9 to 19 carbon atoms and a is the integer 1 to 4; R2 and R3 are each alkyl groups having 1 to 3 carbons and preferably 1 carbon; R4 is an alkylene or hydroxyalkylene group having from 1 to 4 carbon atoms and, optionally, one hydroxyl group. Typical alkyldimethyl betaines include decyl dimethyl betaine or 2-(N-decyl-N, N-dimethyl-ammonia) acetate, coco dimethyl betaine or 2-(N-coco N. N-dimethylammonio) acetate, myristyl dimethyl betaine, palmityl dimethyl betaine, lauryl diemethyl betaine, cetyl dimethyl betaine and stearyl dimethyl betaine. The amidobetaines similarly include cocoamidoethylbetaine and cocoamidopropyl betaine. A preferred betaine is coco (C8-C18) amidopropyl dimethyl betaine.
  • Amine oxide semi-polar nonionic surfactants comprise compounds and mixtures of compounds having the formula
    Figure imgb0003
    wherein R1 is an alkyl. 2-hydroxyalkyl, 3-hydroxyalkyl, or 3-alkoxy-2-hydroxypropyl radical in which the alkyl and alkoxy, respectively, contain from 8 to 18 carbon atoms. R2 and R3 are each methyl, ethyl, propyl, isopropyl, 2-hydroxyethyl, 2-hydroxypropyl, or 3-hydroxypropyl, and n is from 0 to 10. Particularly preferred are amine oxides of the formula:
    Figure imgb0004
    wherein R1 is a C12-16 alkyl and R2 and R3 are methyl or ethyl. The above ethylene oxide condensates, amides, and amine oxides are more fully described in U.S. Pat. No. 4,316,824 which is hereby incorporated herein by reference.
  • The concentration of the amine oxide in the instant compositions is 1.0 to 5 wt. %, more preferably 2 to 4 wt. % and most preferably 2.5 to 3.5 wt. %.
  • The instant composition contains a mixture of a C12-14 alkyl monoalkanol amide such as lauryl monoalkanol amide and a C12-14 alkyl dialkanol amide such as lauryl diethanol amide or coco diethanol amide, wherein the concentration of the monoalkanol amide is 1 to 3 wt. % and the concentration of the dialkanol amide is 1 to 3 wt. %.
  • All of the aforesaid ingredients in this light duty liquid detergent are water soluble or water dispersible and remain so during storage.
  • This particular combination of C12-14 alkyl monoalkanol amide, C12-14 alkyl dialkanol amide, anionic surfactant, amine oxide and betaine surfactant, provides a detergent system which coacts with the nonionic surfactant to product a liquid detergent composition with desirable foaming, foam stability, detersive properties and mildness to human skin. Surprisingly, the resultant homogeneous liquid detergent exhibits the same or better foam performance, both as to initial foam volume and stability of foam in the presence of soils, and cleaning efficacy as an anionic based light duty liquid detergent (LDLD) as shown in the following Examples.
  • The nonionic surfactant, the anionic surfactant, the betaine surfactant, the C12-14 alkyl monoalkanol amide, the C12-14 alkyl dialkanol amide and the amine oxide are solubilized in the water. To the composition can also be added water soluble hydrotropic salts include sodium, potassium, ammonium and mono-, di- and triethanolammonium salts. While the aqueous medium is primarily water, preferably said solubilizing agents are included in order to control the viscosity of the liquid composition and to control low temperature cloud clear properties. Usually, it is desirable to maintain clarity to a temperature in the range of 5°C to 10°C. Therefore, the proportion of solubilizer generally will be from 1%-15%, preferably 2%-12%, most preferably 2%-8%, by weight of the detergent composition with the proportion of ethanol, when present, being 5% of weight or less in order to provide a composition having a flash point above 46°C. Preferably the solubilizing ingredient will be a mixture of ethanol and either sodium xylene sulfonate or sodium cumene sulfonate or a mixture of said sulfonates or ethanol and urea. Inorganic salts such as sodium sulfate, magnesium sulfate, sodium chloride and sodium citrate can be added at concentrations of 0.5 to 4.0 wt. % to modify the cloud point of the nonionic surfactant and thereby control the haze of the resultant solution. Various other ingredients such as urea at a concentration of 0.5 to 4.0 wt. % or urea at the same concentration in combination with ethanol at a concentration of 0.5 to 4.0 wt. % can be used as solubilizing agents. Other ingredients which have been added to the compositions at concentrations of 0.1 to 4.0 wt. percent are perfumes, sodium bisulfite, ETDA, isoethanoeic acid and proteins such as lexine protein. The foregoing solubilizing ingredients also facilitate the manufacture of the inventive compositions because they tend to inhibit gel formation.
  • In addition to the previously mentioned essential and optional constituents of the light duty liquid detergent, one may also employ normal and conventional adjuvants, provided they do not adversely affect the properties of the detergent. Thus. there may be used various coloring agents and perfumes; ultraviolet light absorbers such as the Uvinuls, which are products of GAF Corporation; sequestering agents such as ethylene diamine tetraacetates; magnesium sulfate heptahydrate; pearlescing agents and opacifiers; pH modifiers; etc. The proportion of such adjuvant materials. in total will normally not exceed 15% of weight of the detergent composition, and the percentages of most of such individual components will be a maximum of 5% by weight and preferably less than 2% by weight. Sodium formate can be included in the formula as a perservative at a concentration of 0.1 to 4.0%. Sodium bisulfite can be used as a color stabilizer at a concentration of 0.01 to 0.2 wt. %
  • The present nonionic based light duty liquid detergents such as dishwashing liquids are readily made by simple mixing methods from readily available components which, on storage, do not adversely affect the entire composition. However, it is preferred that the nonionic surfactant be mixed with the solubilizing ingredients, e.g., ethanol and. if present. prior to the addition of the water to prevent possible gelation. The nonionic based surfactant system is prepared by sequentially adding with agitation the anionic surfactant, the betaine surfactant, the amine oxide, the C12-14 alkyl monoalkanol amide and the C12-14 alkyl dialkanol amide to the aqueous solution of the non-ionic surfactant which has been previously mixed with a solubilizing agent such as ethyl alcohol and/or sodium xylene sulfonate to assist in solubilizing said surfactants, and then adding with agitation the formula amount of water to form an aqueous solution of the nonionic based surfactant system. The use of mild heating (up to 100°C.) assists in the solubilization of the surfactants. The viscosities are adjustable by changing the total percentage of active ingredients. Usually, no thickening agent is added, but thickeners may be added if higher viscosity liquids are desired. In all such cases the product made will be pourable from a relatively narrow mouth bottle (1.5 cm. diameter) or opening, and the viscosity of the detergent formulation will not be so low as to be like water. The viscosity of the detergent desirably will be at least 100 centipoises (cps) at room temperature, but may be up to 1,000 centipoises as measured with a Brookfield Viscometer using a number 3 spindle rotating at 12 rpm. Its viscosity may approximate those of commercially acceptable detergents now on the market. The detergent viscosity and the detergent itself remain stable on storage for lengthy periods of time, without color changes or settling out of any insoluble materials. The pH of this formation is substantially neutral to skin, e.g., 4.5 to 8 and preferably 5.0 to 5.0.
  • These products have unexpectedly desirably properties. For example, the foam quality and detersive property is equal to or better than standard light duty liquid detergents while using a nonionic surfactant as the primary surfactant and minimal amounts of anionic surfactant, thereby achieving a mild, non-irritating liquid detergent.
  • The following examples are merely illustrative of the invention and are not to be construed as limiting thereof.
  • Description of the Preferred Embodiments EXAMPLE 1
  • The following formulas were prepared at room temperature by simple liquid mixing procedures as previously described
    A B C D
    Nonionic Neodol 11-9 19 19 19 19
    Ammonium Lauryl sulfate 6 6 8 -
    Sodium lauryl sulfate - - - 9.5
    Paraffin Na sulfonate - - - -
    Cocoamido propyl betaine 2.5 2.5 2.5 2.5
    Dioctyl sulfosuccinate - - - -
    Lauric myristic monoethanol amide (LMMEA) 2.0 4.0 - -
    Lauric diethanol amide (LDEA) 2.0 - - -
    Amine Oxide 2.5 2.5 4.5 3.0
    Water Balance Balance Balance Balance
    Product Appearance Okay need solubilizer need solubilizer need solubilizer
    Foam Volume Test Start (ml) 50 - 10 -
    Foam Volume Test end (ml) 100 - 50 -
    Miniplate Test (1) (number of miniplates) - 48 - -
    (1) I.R.M. Anstell et al, The Journal of the American Oil Chemist Society, Vol 43, page 576-580(1966)
  • EXAMPLE 1 (Continued)
  • E F G H I
    Skin Sensitive Palmolive
    Nonionic Neodol 11-9 19 19 19 20.5
    Ammonium lauryl sulfate 9.5 - - -
    Sodium lauryl sulfate 9.5 - - -
    Paraffin Na sulfonate - 6.0 7.1 8.0
    Cocoamido propylbetaine 2.5 2.5 2.5 2.5
    Dioctyl sulfosuccinate - - - -
    Lauric myristic monoethanol amide (LMMEA) - 2.0 - -
    Lauric diethanol amide (LDEA) - 2.0 - -
    Amine Oxide 3.0 2.5 3.0 3.0
    Water Bal Bal Bal Bal
    Product Appearance need solubilizer Okay need solubilizer need solubilizer Okay
    Foam Volume Test Start (ml) 50 - - 50 5
    Foam Volume Test end (ml) 150 - - 100 100
    Miniplate Test (number of miniplates) N/A 29 27 - -
    Formulas B, C, D, E, G, H and I are comparative Examples.
  • EXAMPLE 2
  • Example 1 of U. S. Patent 4,495,526 (designated L) and Formula A of Example 1 of this application were compared in a Hand Dish Wash Test. The test was run with Olive Oil, Beef Tallow and Butter in a ratio of equal amounts. The results show that Formula A of Example 1 gave better results than the standard Formula L (Example 1 of U.S. Patent 4.495.526). The test was run blind with each trial consisting of two runs of each product and the test was done in hard water (300 ppm).
  • Results of Formula A Versus L
    Trial Sample #Plates (300 ppm)
    1 A 8
    L 6
    2 A 8
    L 6
    Average A 8
    L 6

Claims (9)

  1. A high foaming, nonionic surfactant based, light duty, liquid detergent comprising approximately, by weight,
    (a) 10% to 30% of a water soluble nonionic surfactant selected from the group consisting of primary and secondary C8-C18 alkanol condensates with 5 to 30 moles of ethylene oxide, condensates of C8-C18 alkylphenol with 5 to 30 moles of ethylene oxide, condensates of C8-C20 alkanol with a heteric mixture of ethylene oxide and propylene oxide having a weight ratio of ethylene oxide to propylene oxide from 2.5:1 to 4:1 and a total alkylene oxide content of 60% to 85% by weight and condensates of 2 to 30 moles of ethylene oxide with sorbitan mono and tri- C10-C20 alkanoic acid esters having an HLB of 8 to 15;
    (b) 1% to 10% of a water-soluble anionic detergent selected from the group consisting of C8-C18 alkyl sulfates, C8-C16 alkylbenzene sulfonates, C10-C20 paraffin sulfonates, C10-C24 alpha olefin sulfonates and C8-C18 alkyl sulfosuccinate esters, C8-C18 acyl isethionates and C8-C18 acyl taurates; and
    (c) 0.5% to 10% of a water-soluble betaine;
    (d) 1 to 3 wt.% of a C12-14 alkyl monoalkanol amide:
    (e) 1 to 3 wt.% of a C12-14 alkyl dialkanol amide;
    (f) 1% to 5% of a water soluble amine oxide; and
    (g) the balance being water as an aqueous medium in which said nonionic surfactant. said anionic detergent, said betaine said C12-14 alkyl monoalkanol amide, said C12-14 alkyl dialkanol amide and said amine oxide are solubilized in said water, wherein the sum of B, C, D, E and F being from 15% to 48% by weight of the composition, said nonionic surfactant being in excess of 50% by weight of the total surfactant content.
  2. A liquid detergent composition according to claim 1 which includes, in addition. 1% to 15% by weight of a solubilizing agent which is a water soluble salts of C1-C3 substituted benzene sulfonate hydrotropes and mixtures thereof.
  3. A liquid detergent composition according to claim 2 wherein said nonionic surfactant is a condensate of a primary C8-C18 alkanol with 5-30 moles of ethylene oxide.
  4. A liquid detergent composition according to claim 3 wherein said anionic detergent is selected from the group consisting of C12-C16 alkyl sulfates, C10-C15 alkylbenzene sulfonates. C13-C17 paraffin sulfonates and C12-C18 alpha olefin sulfonates.
  5. A liquid detergent composition according to claim 1 wherein said nonionic surfactant is present in an amount of 16% to 22% by weight. said anionic detergent is present in an amount of 2% to 9% by weight and said betaine is present in an amount of 2% to 9% by weight.
  6. A liquid detergent composition according to claim 5 wherein said anionic detergent is a C12-C16 alkyl sulfate.
  7. A liquid detergent composition according to Claim 1 further including a perservative.
  8. A liquid detergent composition according to Claim 1 further including a color stabilizer.
  9. A liquid detergent composition according to Claim 1, wherein C12-14 alkyl monoalkanol amide is a C12-14 alkyi monoethanol amide and said C12-14 alkyl dialkanol amide is a C12-14 alkyl diethanol amide.
EP94915886A 1993-05-03 1994-05-03 High foaming nonionic surfactant based liquid detergent Expired - Lifetime EP0699228B1 (en)

Applications Claiming Priority (5)

Application Number Priority Date Filing Date Title
US5608693A 1993-05-03 1993-05-03
US56086 1993-05-03
US19392994A 1994-02-09 1994-02-09
US193929 1994-02-09
PCT/US1994/004551 WO1994025554A1 (en) 1993-05-03 1994-05-03 High foaming nonionic surfactant based liquid detergent

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EP0699228A1 EP0699228A1 (en) 1996-03-06
EP0699228B1 true EP0699228B1 (en) 1996-12-04

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EP94915886A Expired - Lifetime EP0699228B1 (en) 1993-05-03 1994-05-03 High foaming nonionic surfactant based liquid detergent

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EP (1) EP0699228B1 (en)
AT (1) ATE145934T1 (en)
AU (1) AU6774094A (en)
DE (1) DE69401066T2 (en)
DK (1) DK0699228T3 (en)
WO (1) WO1994025554A1 (en)

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* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
GB2303637B (en) * 1995-07-21 1999-04-21 Cussons Int Ltd Personal cleaning composition
MX341184B (en) 2010-10-25 2016-08-09 Stepan Co Light-duty liquid detergents based on compositions derived from natural oil metathesis.
US9347111B2 (en) * 2012-11-06 2016-05-24 Lixivia, Inc. Making mineral salts from various sources

Family Cites Families (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4329334A (en) * 1980-11-10 1982-05-11 Colgate-Palmolive Company Anionic-amphoteric based antimicrobial shampoo
US4450091A (en) * 1983-03-31 1984-05-22 Basf Wyandotte Corporation High foaming liquid shampoo composition
GB8411110D0 (en) * 1984-05-01 1984-06-06 Beecham Group Plc Detergent formulations
US4595526A (en) * 1984-09-28 1986-06-17 Colgate-Palmolive Company High foaming nonionic surfacant based liquid detergent
JPH01292098A (en) * 1988-05-19 1989-11-24 Kao Corp Liquid detergent composition
CA2002095C (en) * 1988-11-03 1998-06-02 Ralph S. Itoku High viscosity detergent gel composition and method of making same
NZ247673A (en) * 1992-06-03 1994-10-26 Colgate Palmolive Co High foaming aqueous liquid detergent containing non-ionic surfactant supplemented by anionic and betaine surfactants

Also Published As

Publication number Publication date
EP0699228A1 (en) 1996-03-06
DK0699228T3 (en) 1997-06-02
WO1994025554A1 (en) 1994-11-10
DE69401066D1 (en) 1997-01-16
ATE145934T1 (en) 1996-12-15
AU6774094A (en) 1994-11-21
DE69401066T2 (en) 1997-07-03

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