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WO1998005742A1 - Compositions nettoyantes liquides contenant des esters dianioniques - Google Patents

Compositions nettoyantes liquides contenant des esters dianioniques Download PDF

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Publication number
WO1998005742A1
WO1998005742A1 PCT/US1997/013746 US9713746W WO9805742A1 WO 1998005742 A1 WO1998005742 A1 WO 1998005742A1 US 9713746 W US9713746 W US 9713746W WO 9805742 A1 WO9805742 A1 WO 9805742A1
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alkyl
surfactants
weight
linear
dianionic
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PCT/US1997/013746
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English (en)
Inventor
Peter Robert Foley
Stephen Wayne Heinzman
Eugene Paul Gosselink
Jeffrey John Scheibel
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The Procter & Gamble Company
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Publication of WO1998005742A1 publication Critical patent/WO1998005742A1/fr

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    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
    • A61K8/00—Cosmetics or similar toiletry preparations
    • A61K8/18—Cosmetics or similar toiletry preparations characterised by the composition
    • A61K8/30—Cosmetics or similar toiletry preparations characterised by the composition containing organic compounds
    • A61K8/46—Cosmetics or similar toiletry preparations characterised by the composition containing organic compounds containing sulfur
    • A61K8/466—Cosmetics or similar toiletry preparations characterised by the composition containing organic compounds containing sulfur containing sulfonic acid derivatives; Salts
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
    • A61K8/00—Cosmetics or similar toiletry preparations
    • A61K8/18—Cosmetics or similar toiletry preparations characterised by the composition
    • A61K8/30—Cosmetics or similar toiletry preparations characterised by the composition containing organic compounds
    • A61K8/40—Cosmetics or similar toiletry preparations characterised by the composition containing organic compounds containing nitrogen
    • A61K8/44—Aminocarboxylic acids or derivatives thereof, e.g. aminocarboxylic acids containing sulfur; Salts; Esters or N-acylated derivatives thereof
    • A61K8/442—Aminocarboxylic acids or derivatives thereof, e.g. aminocarboxylic acids containing sulfur; Salts; Esters or N-acylated derivatives thereof substituted by amido group(s)
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61Q—SPECIFIC USE OF COSMETICS OR SIMILAR TOILETRY PREPARATIONS
    • A61Q5/00—Preparations for care of the hair
    • A61Q5/006—Antidandruff preparations
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61Q—SPECIFIC USE OF COSMETICS OR SIMILAR TOILETRY PREPARATIONS
    • A61Q5/00—Preparations for care of the hair
    • A61Q5/02—Preparations for cleaning the hair
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C309/00—Sulfonic acids; Halides, esters, or anhydrides thereof
    • C07C309/01—Sulfonic acids
    • C07C309/02—Sulfonic acids having sulfo groups bound to acyclic carbon atoms
    • C07C309/03—Sulfonic acids having sulfo groups bound to acyclic carbon atoms of an acyclic saturated carbon skeleton
    • C07C309/17—Sulfonic acids having sulfo groups bound to acyclic carbon atoms of an acyclic saturated carbon skeleton containing carboxyl groups bound to the carbon skeleton
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D1/00—Detergent compositions based essentially on surface-active compounds; Use of these compounds as a detergent
    • C11D1/02—Anionic compounds
    • C11D1/12—Sulfonic acids or sulfuric acid esters; Salts thereof
    • C11D1/126—Acylisethionates
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D1/00—Detergent compositions based essentially on surface-active compounds; Use of these compounds as a detergent
    • C11D1/02—Anionic compounds
    • C11D1/12—Sulfonic acids or sulfuric acid esters; Salts thereof
    • C11D1/28—Sulfonation products derived from fatty acids or their derivatives, e.g. esters, amides
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
    • A61K2800/00—Properties of cosmetic compositions or active ingredients thereof or formulation aids used therein and process related aspects
    • A61K2800/40—Chemical, physico-chemical or functional or structural properties of particular ingredients
    • A61K2800/59—Mixtures
    • A61K2800/596—Mixtures of surface active compounds
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61Q—SPECIFIC USE OF COSMETICS OR SIMILAR TOILETRY PREPARATIONS
    • A61Q5/00—Preparations for care of the hair
    • A61Q5/12—Preparations containing hair conditioners

Definitions

  • the present invention relates to liquid cleaning compositions (e.g.. heavy duty liquid laundry detergents; hair shampoo compositions; dishwashing compositions) containing surfactants selected from dianionic or alkoxylated dianionic ester cleaning agents and co-surfactants. More particularly, the invention is directed to liquid cleaning compositions containing a surfactant system comprising a dianionic or alkoxylated dianionic ester cleaning agent selected from substituted or unsubstituted, saturated or unsaturated, branched or linear chain, alpha-sulfonated esters of C2 - Cg alcohol sulfonates, optionally alkoxylated, in combination with one or more other co- surfactants.
  • a surfactant system comprising a dianionic or alkoxylated dianionic ester cleaning agent selected from substituted or unsubstituted, saturated or unsaturated, branched or linear chain, alpha-sulfonated esters of C2 - Cg alcohol s
  • Most conventional detergent compositions contain mixtures of various detersive surfactant components.
  • Commonly encountered surfactant components include various anionic surfactants, especially the alkyl benzene sulfonates, alkyl sulfates. alkyl alkoxy sulfates and various nonionic surfactants, such as alkyl ethoxylates and alkylphenol ethoxylates.
  • Surfactants have found use as detergent components capable of the removal of a wide variety of soils and stains. A consistent effort however is made by detergent manufacturers to improve detersive properties of detergent compositions by providing new and improved surfactants.
  • anionic surfactants are their apparent sensitivity to free multivalent cations in solution. It is believed that an increase in the number of such ions in solution generally results in reduced surfactant performance.
  • hardness ions calcium or magnesium ion
  • the dianionic or alkoxylated dianionic ester cleaning agents utilized herein provide improved cleaning performance in the presence of relatively high levels of hardness ions.
  • they when used in combination with other surfactants in a surfactant system, they provide liquid cleaning compositions having superior cleaning properties. They are especially effective when used in laundry cleaning processes.
  • liquid cleaning compositions are particularly useful for personal cleansing uses, as formulated for use as hair shampoos and body washes.
  • An advantage of the present invention is the improved cleaning performance of liquid detergent compositions formulated containing the described dianionic or alkoxylated dianionic surfactant component as a part of the total surfactant system.
  • the present invention relates to liquid cleaning compositions
  • liquid cleaning compositions comprising: a) as part of the surfactant system, from about 0.1% to about 40% by weight of a dianionic or alkoxylated dianionic ester cleaning agent selected from substituted or unsubstituted, saturated or unsaturated, branched or linear chain, alpha-sulfonated esters of C2 - (preferably C2 - C4) alcohol sulfonates, optionally alkoxylated; b) as the other part of the surfactant system, from about 0.1% to about 50% by weight of one or more co-surfactants; c) from about 1% to about 99.7% by weight of solvent; and d) from about 0.1% to about 75% by weight of liquid cleaning composition adjunct ingredients.
  • a dianionic or alkoxylated dianionic ester cleaning agent selected from substituted or unsubstituted, saturated or unsaturated, branched or linear chain, alpha-sulfonated esters of
  • the dianionic or alkoxylated dianionic ester cleaning agent is used in the present invention liquid detergent compositions as a component of a surfactant system (i.e., the surfactant system comprises the dianionic or alkoxylated dianionic ester cleaning agent and one or more co-surfactants) wherein the dianionic ester cleaning agent is present at levels of from about 0.1 % to about 50%, preferably from about 1% to about 40%, most preferably from about 2% to about 30% by weight of the surfactant system.
  • the surfactant system comprises the dianionic or alkoxylated dianionic ester cleaning agent and one or more co-surfactants
  • the dianionic ester cleaning agent is present at levels of from about 0.1 % to about 50%, preferably from about 1% to about 40%, most preferably from about 2% to about 30% by weight of the surfactant system.
  • the alkoxylated dianionic ester cleaning agent is present at levels of from about 0.1 % to about 50%, preferably from about 1% to about 40%, most preferably from about 2% to about 30% by weight of the surfactant system. It is to be noted however that higher levels of dianionic or alkoxylated dianionic ester cleaning agent are within the present invention.
  • these liquid compositions comprise a surfactant system further comprising one or more co-surfactants selected from: anionic surfactants, preferably selected from the group of alkyl alkoxylated sulfates, alkyl sulfates, and/or linear alkyl benzenesulfonate surfactants; cationic surfactants, preferably selected from quaternary ammonium surfactants; nonionic surfactants, preferably alkyl ethoxylates, alkyl polyglucosides, and/or amine (e.g., amidopropylamines) or amine oxide surfactants; amphoteric surfactants, preferably selected from betaines and or polycarboxylates (for example polyglycinates); and zwiterionic surfactants.
  • anionic surfactants preferably selected from the group of alkyl alkoxylated sulfates, alkyl sulfates, and/or linear alkyl benzenesulfonate
  • Preferred liquid cleaning composition adjunct ingredients include builders, preferably water soluble builders, for example citrate/fatty acid builder systems, and detersive enzymes.
  • the present invention is also directed to hair shampoo compositions comprising: a) as part of the surfactant system, from about 0.1 % to about 40% by weight of a dianionic or alkoxylated dianionic ester cleaning agent selected from substituted or unsubstituted, saturated or unsaturated, branched or linear chain, alpha-sulfonated esters of C2 - (preferably C2 - C4) alcohol sulfonates, optionally alkoxylated; b) as the other part of the surfactant system, from about 0.1% to about 50% by weight of one or more co-surfactants; c) from about 1% to about 99.7% by weight of solvent; and d) from about 0.05% to about 10% by weight of one or more silicone hair conditioning agents; and e) from about 0.1% to about 75% by weight of shampoo composition adjunct ingredients.
  • a dianionic or alkoxylated dianionic ester cleaning agent selected from substituted or unsubstituted, saturated or unsaturated
  • An essential component of the liquid cleaning compositions of the present invention may be a dianionic ester cleaning agent.
  • the dianionic ester cleaning agent is selected from substituted (e.g., halogen substituents) or unsubstituted, saturated or unsaturated, branched or linear chain, alpha-sulfonated esters of C2 - Cg (preferably C2 - C4) alcohol sulfonates.
  • the acid portion of the ester preferably comprises from 5 to 32, preferably 7 to 28, most preferably 12 to 24 carbon atoms, which may be straight or branched chains.
  • the alcohol sulfonate portion of the ester may be straight or branched chains; preferred are the ethyl and propyl chains.
  • a preferred dianionic ester cleaning agent has the formula
  • R' and R" are independently selected from substituted or unsubstituted, branched or unbranched alkyl, alkenyl, aryl, or alkaryl groups of chain length C5 to C24, preferably Cg to C22 > rnost preferably CJ Q to C22 > or hydrogen, and R' and R" in total contain from 5 to 24 carbon atoms; each R"' is independently selected from substituted (e.g., -SO3 " M + , -SO2 " M + )or unsubstituted C ⁇ to Cg alkyl, phenyl, - SO3 " M + , -SO2 " M + , and hydrogen (preferred R'" are selected from: all hydrogen; one methyl and all other hydrogen; -CH2-SO3 " M + attached to the carbon alpha to the sulphonate and all other hydrogen; -SO2 " M + attached to the carbon beta to the sulfonate and all other hydrogen); n is an integer from 2 to 6 (p
  • the more preferred dianionic ester cleaning agent has the formula as above where R' is an unsubstituted, linear or branched alkyl group of chain length from Cg to C22 ⁇ R" and R'" are hydrogen, n is an integer from 2 to 4, and M is a potassium, ammonium, sodium, magnesium, or calcium ion.
  • the most preferred dianionic ester cleaning agent has the above formula wherein R' is selected from Cj linear alkyl, Cjg linear alkyl, C14 linear alkyl, C ⁇ 2 linear alkyl, C J O linear alkyl, Cg linear alkyl, Cg linear alkyl, Cjg linear alkenyl, Cj linear alkenyl, C14 linear alkenyl, 2-ethyl hexyl, and 2-propyl heptyl. Many of these esters are readily prepared from naturally occuring materials such as tallow fatty acids, oleic acid, palm oil, coconut oil, palm kernel oil, and rapeseed oil.
  • Particularly preferred dianionic ester cleaning agents useful herein therefore include: the isethionate ester of alpha sulfo palmitic acid, the isethionate ester of alpha sulfo steric acid, the isethionate ester of alpha sulfo lauric acid, the isethionate ester of alpha sulfo myristic acid, the isethionate ester of alpha sulfo behenic acid, the isethionate ester of alpha sulfo octanoic acid, the isethionate ester of alpha sulfo decanoic acid, the ester of 3-hydroxy propyl sulfonate and alpha sulfo palmitic acid, the ester of 3-hydroxy propyl sulfonate and alpha sulfo steric acid, the ester of 3- hydroxy propyl sulfonate and alpha sulfo lauric acid,
  • the dianionic ester cleaning agent is typically present at levels of incorporation of from about 0.1% to about 40%, preferably from about 0.1% to about 35%, most preferably from about 0.5% to about 15% by weight of the liquid detergent composition, although higher levels may be used if cost is not a consideration.
  • Preferred dianionic ester cleaning agents herein include:
  • R' is a straight or branched chain alkyl or alkenyl group of chain length from about CJO to about C22;
  • R' is a straight or branched chain alkyl or alkenyl group of chain length from about Ci ⁇ to about C22;
  • R * — C— C— O— CH 2 CHCH 2 SO 3 M SO 3 " M + SO 2 " M + wherein R' is a straight or branched chain alkyl or alkenyl group of chain length from about C]o to about C22 (these sulfinate-sulfonate compounds are not typically preferred for bleach-containing compositions due to in-product oxidation of these compounds by the bleaching agent).
  • An essential component of the liquid cleaning compositions of the present invention may be an alkoxylated dianionic ester cleaning agent.
  • the alkoxylated dianionic ester cleaning agent is selected from substituted (e.g., halogen substituents) or unsubstituted, saturated or unsaturated, branched or linear chain, alpha-sulfonated esters of alkoxylated C2 - Cg (preferably C2 - C4) alcohol sulfonates.
  • Preferred alkoxy moieties are ethoxy, propoxy, and combinations thereof.
  • the acid portion of the ester preferably comprises from 5 to 32, preferably 7 to 28, most preferably 12 to 24 carbon atoms, which may be straight or branched chains.
  • the alkoxylated alcohol sulfonate portion of the ester may be straight or branched chains; preferred are the ethoxy and/or propoxy moieties linked to sulfoethyl or sulfopropyl groups.
  • a preferred alkoxylated dianionic ester cleaning agent has the formula
  • R' and R" are independently selected from substituted or unsubstituted, branched or unbranched alkyl, alkenyl, aryl, or alkaryl groups of chain length C5 to C24, preferably C to C22, most preferably CJO to C22 > or hydrogen, and R' and R" in total contain from 5 to 24 carbon atoms; each R'" is independently selected from substituted (e.g., -SO3 - M + , -SO2 " M + )or unsubstituted C ⁇ to Cg alkyl, phenyl, - SO3 " M + , -SO2 " M + , and hydrogen (preferred R'" are selected from: all hydrogen; one methyl and all other hydrogen; -CH2-SO3 ** M + attached to the carbon alpha to the sulphonate and all other hydrogen; -SO2 " M + attached to the carbon beta to the sulfonate and all other hydrogen); n is an integer from 2 to 6 (preferred from 2 to
  • the (EO PO) m moiety may be either a distribution with average degree of ethoxylation and or propoxylation corresponding to m, or it may be a single specific chain with ethoxylation and/or propoxylation of exactly the number of units corresponding to m.
  • the more preferred alkoxylated dianionic ester cleaning agent has the formula as above where R' is an unsubstituted, linear or branched alkyl group of chain length from Cg to C22 > R" and R" 1 are hydrogen, n is an integer from 2 to 4, m is within the range of from about 0.5 to about 2, and M is a potassium, ammonium, sodium, magnesium, or calcium ion.
  • the most preferred alkoxylated dianionic ester cleaning agent has the above formula wherein R' is selected from Cj linear alkyl, Cj g linear alkyl, C14 linear alkyl, Cj2 linear alkyl, C J O linear alkyl, Cg linear alkyl. Cg linear alkyl, Cjg linear alkenyl, Cjg linear alkenyl, C14 linear alkenyl, 2-ethyl hexyl. and 2-propyl heptyl. Many of these esters are readily prepared from naturally occuring materials such as tallow fatty acids, oleic acid, palm oil, coconut oil, palm kernel oil, and rapeseed oil.
  • Particularly preferred alkoxylated dianionic ester cleaning agents useful herein therefore include: the one time ethoxylated isethionate ester of alpha sulfo palmitic acid, the one time ethoxylated isethionate ester of alpha sulfo steric acid, the one time ethoxylated isethionate ester of alpha sulfo lauric acid, the one time ethoxylated isethionate ester of alpha sulfo myristic acid, the one time ethoxylated isethionate ester of alpha sulfo behenic acid, the one time ethoxylated isethionate ester of alpha sulfo octanoic acid, the one time ethoxylated isethionate ester of alpha sulfo decanoic acid, the ester of one time ethoxylated 3-hydroxy propane sulfonate and alpha
  • the alkoxylated dianionic ester cleaning agent is typically present at levels of incorporation of from about 0.1% to about 40%, preferably from about 0.1% to about 35%, most preferably from about 0.5% to about 15% by weight of the liquid detergent composition, although higher levels may be used if cost is not a consideration.
  • Preferred alkoxylated dianionic ester cleaning agents herein include:
  • R' is a straight or branched chain alkyl or alkenyl group of chain length from about C10 to about C22;
  • the present invention compositions may also comprise some amount of alpha-sulfonated carboxylic acids and/or alpha-sulfonated carboxylic acid esters of non-sulfonated alcohols, wihch may be alkoxylated (e.g., the methyl ester of an alpha- sulfonated carboxylic acid) which may comprise (to differing degrees depending on the reaction conditions used) a portion of the dianionic or alkoxylated dianionic ester cleaning agent raw material used to manufacture the present invention compositions.
  • Such carboxylic acids and esters are typically compatible with the present invention compositions and may be present as long as the requisite amount of dianionic or alkoxylated dianionic ester cleaning agent is present in the final composition.
  • dianionic ester cleaning agents Synthesis of these dianionic ester cleaning agents are known, having been described for example in U.S. Patent 2,806,044, issued September 10, 1957 to Weil et al, and Weil et al., "Synthetic Detergents from Animal Fat. V. Esters from Alpha- Sulfonated Fatty Acids and Sodium Isethionate", JAOCS. 32, pp. 370-2 (1955).
  • the dianionic esters may be prepared from the alpha-sulfo acid (as described hereinafter) or from the corresponding ester (e.g., the methyl ester) or mixtures of the acid and ester.
  • the reaction between the acid and/or ester and isethionate can be catalytic or non-catalytic.
  • catalysts include, but are not limited to, tetraalkyl titanates (e.g., tetraisopropyl titanate) and tin oxides (e.g.,
  • the alkoxylated dianionic esters while novel compounds, may be prepared from the alpha-sulfo acid (as described hereinafter) or from the corresponding ester (e.g., the methyl ester) or mixtures of the acid and ester.
  • the reaction between the acid and or ester and alkoxylated isethionate can be catalytic or non-catalytic.
  • catalysts include, but are not limited to, tetraalkyl titanates (e.g., tetraisopropyl titanate) and tin oxides (e.g., hydrated butyl tin oxide).
  • Patent 5,519,154 issued May 21, 1996 to Naylor, by using the alpha-sulfo fatty acid as the starting material, and the chemistry taught in Scheibel et al., US 4,968,451.
  • a typical synthesis of these compounds is provided in the following Synthesis Example.
  • the resulting solid is dissolved in 125 ml hot water, allowed to cool to room temperature and the resulting solution filtered through Whatman No.l paper (a trace of insoluble material is collected on paper). 1000 ml ethanol is added to the solution and immediately a precipitate forms. This is allowed to stand overnight and the solid is filtered off using vacuum filtration and No.54 paper. The collected solid on the pad is then washed with 200 ml of 90:10 ethanol: water and then with 100ml ethanol and then dried to constant weight in vacuum desiccator over sodium hydroxide pellets to provide the desired product.
  • the alpha-sulfonated laurate ester of ethoxylated (2 times) isethionate is prepared similar to the synthesis method described in Synthesis Example 1 but using sodium 2-[2-(2-hydroxyethoxy)ethoxy]ethanesulfonate in place of the sodium salt of 2-(2-sulfoethoxy)ethanol.
  • This starting material is prepared as follows.
  • NMR(DMSO-dg) shows that the reaction is complete by the disappearance of the isethionate peaks at ⁇ 53.5ppm and ⁇ 57.4ppm.
  • the solution is cooled to room temperature and neutralized to pH 7 with 57.4g of a 16.4% solution of p- toluenesulfonic acid monohydrate in diethylene glycol. (Alternatively, methanesulfonic acid may be used.)
  • the ⁇ C-NMR spectrum of the product shows resonances at ⁇ 51ppm (-CH2SO3Na) , ⁇ 60ppm (-CH2OH), and at ⁇ 69ppm, ⁇ 72ppm, and ⁇ 77ppm for the remaining four methyienes.
  • the alpha-sulfonated laurate ester of ethoxylated (3 times) isethionate is prepared similar to the synthesis method described in Synthesis Example 1 but using sodium 2- ⁇ 2-[2-(2-hydroxyethoxy)ethoxy]ethoxy ⁇ ethanesulfonate in place of the sodium salt of 2-(2-sulfoethoxy)ethanol.
  • This starting material is prepared as follows.
  • Sodium hydroxide pellets (MCB, 5.5g, 0.138 mol) are added, followed by triethylene glycol (Aldrich, 448.7g, 3.0 mol).
  • the triethylene glycol can be purified by heating with strong base such as NaOH until color stabilizes and then distilling off the purified glycol for use in the synthesis. The solution is heated at 190C° under argon overnight as water distills from the reaction mixture.
  • a ⁇ C-NMR(DMSO-dg) shows that the reaction is complete by the disappearance of the isethionate peaks at ⁇ 53.5ppm and ⁇ 57.4ppm, and the emergence of product peaks at ⁇ 51ppm (-CH2SO3Na) , ⁇ 60ppm (-CH2OH), and at ⁇ 67ppm, ⁇ 69ppnvand ⁇ 72ppm for the remaining methyienes.
  • the solution is cooled to room temperature and neutralized to pH 7 with methanesulfonic acid (Aldrich).
  • the reaction affords 650g of a 59.5% solution of sodium 2- ⁇ 2-[2-(2- hydroxyethoxy)ethoxy]ethoxy ⁇ ethanesulfonate in triethylene glycol.
  • the excess triethylene glycol is removed by adding 0.8 mol% of monobasic potassium phosphate (Aldrich) as a buffer and heating on a Kugelrohr apparatus (Aldrich) at 180C° for - 5.5 hrs. at -lrnmHg to give the desired material as a brown solid.
  • a more soluble buffer can be more effective in controlling pH during the stripping of excess triethylene glycol.
  • a more soluble buffer is the salt of N- methylmorpholine with methanesulfonic acid.
  • the pH can be controlled by frequent or continuous addition of acid such as methanesulfonic acid to maintain a pH near neutral during the stripping of excess glycol.
  • the material is believed to contain a low level of the disulfonate arising from reaction of both ends of the triethylene glycol with isethionate. However, the crude material is used without further purification.
  • the sodium salt of allyl alphasulfopalmitate is reacted with 1.0 molar equivalent of sodium metabisulfite at a pH of 3-4 in water using a redox initiator system as in the above example.
  • the resulting sulfinate-sulfonate is oxidized with hydrogen peroxide and the pH adjusted with sodium hydroxide to give the desired trisodium 2,3-disulfopropyl alpha-sulfopalmitate.
  • the procedure is also substantially the same as described in Scheibel et al., US 4,968,451 (to free radical disulfonation of allyl end capped oligomeric esters at low pH).
  • the alpha-sulfonated laurate ester of ethoxylated (average 2.5 times) isethionate is prepared similar to the synthesis method described in Synthesis Example 1 but using an equimolar mixture of sodium 2-[2-(2- hydroxyethoxy)ethoxy]ethanesulfonate and sodium 2-[2-(2- ⁇ 2- hydroxy ethoxy ⁇ ethoxy )ethoxy]ethanesulfonate in place of the sodium salt of 2-(2- sulfoemoxy)ethanol.
  • This starting material is prepared as follows.
  • the neat material is obtained by adding 2 mol% of potassium phosphate, monobasic (predissolved in water) and heating on a Kugelrohr apparatus (Aldrich) at 150°C for - 4 hrs. at -ImmHg to afford 90g of brown solid. Analysis indicates that a 0.96:1 molar ratio of diethoxylated:triethoxylated starting material has been achieved.
  • the surfactant system of the liquid detergent compositions according to the present invention further comprise additional surfactants, herein also referred to as co- surfactants, preferably selected from: anionic surfactants, preferably selected from the group of alkyl alkoxylated sulfates, alkyl sulfates, alkyl disulfates, and/or linear alkyl benzenesulfonate surfactants; cationic surfactants, preferably selected from quaternary ammonium surfactants; nonionic surfactants, preferably alkyl ethoxylates, alkyl polyglucosides, polyhydroxy fatty acid amides, and/or amine or amine oxide surfactants; amphoteric surfactants, preferably selected from betaines and/or polycarboxylates (for example polyglycinates); and zwiterionic surfactants.
  • anionic surfactants preferably selected from the group of alkyl alkoxylated sulfates, alkyl s
  • a wide range of these co-surfactants can be used in the cleaning compositions of the present invention.
  • a typical listing of anionic, nonionic, ampholytic and zwitterionic classes, and species of these co-surfactants, is given in US Patent 3,664,961 issued to Norris on May 23, 1972.
  • Amphoteric surfactants are also described in detail in "Amphoteric Surfactants, Second Edition", E.G. Lomax, Editor (published 1996, by Marcel Dekker, Inc.)
  • the laundry detergent compositions of the present invention typically comprise from about 0.1% to about 35%, preferably from about 0.5% to about 15%, by weight of co-surfactants.
  • Selected co-surfactants are further identified as follows.
  • Nonlimiting examples of anionic co-surfactants useful herein typically at levels from about 0.1% to about 50%, by weight, include the conventional Cj j-Cjg alkyl benzene sulfonates ("LAS") and primary, branched-chain and random C10-C20 alkyl sulfates ("AS"), the Ci ⁇ -Ci g secondary (2,3) alkyl sulfates of the formula CH 3 (CH 2 ) x (CHOSO3 " M + ) CH3 and CH3 (CH 2 )y(CHOSO 3 " M + ) CH 2 CH 3 where x and (y + 1 ) are integers of at least about 7, preferably at least about 9, and M is a water-solubilizing cation, especially sodium, unsaturated sulfates such as oleyl sulfate.
  • LAS Cj j-Cjg alkyl benzene sulfonates
  • AS primary, branched-chain and random C10-C20 alkyl
  • the C j 2-C ⁇ betaines and sulfobetaines ("sultaines”), Ci ⁇ -Cig amine oxides, and the like, can also be included in the overall compositions.
  • C10-C20 conventional soaps may also be used. If high sudsing is desired, the branched-chain Ci Q-Cjg soaps may be used.
  • Other conventional useful anionic co-surfactants are listed in standard texts.
  • alkyl alkoxylated sulfate surfactants useful herein are preferably water soluble salts or acids of the formula RO(A) m SO3M wherein R is an unsubstituted C] ⁇ -C24 alkyl or hydroxyalkyl group having a Cj -C24 alkyl component, preferably a Ci 2-C ⁇ alkyl or hydroxyalkyl, more preferably Ci 2-Cj5 alkyl or hydroxyalkyl, A is an ethoxy or propoxy unit, m is greater than zero, typically between about 0.5 and about 6, more preferably between about 0.5 and about 3, and M is H or a cation which can be, for example, a metal cation (e.g., sodium, potassium, lithium, calcium, magnesium, etc.), ammonium or substituted-ammonium cation.
  • R is an unsubstituted C] ⁇ -C24 alkyl or hydroxyalkyl group having a Cj -C24 alkyl component, preferably
  • Alkyl ethoxylated sulfates as well as alkyl propoxylated sulfates are contemplated herein.
  • Specific examples of substituted ammonium cations include ethanol-, triethanol-, methyl-, dimethyl, trimethyl-ammonium cations and quaternary ammonium cations such as tetramethyl -ammonium and dimethyl piperidinium cations and those derived from alkylamines such as ethylamine, diethylamine, tri ethylamine, mixtures thereof, and the like.
  • Exemplary surfactants are C12-C15 alkyl polyethoxylate (1.0) sulfate (C12- C 15 E(1.0)M), Ci2-C 15 alkyl polyethoxylate (2.25) sulfate (C 1 -C ⁇ 5 E(2.25)M), C 12 - C15 alkyl polyethoxylate (3.0) sulfate (Ci2-C ⁇ sE(3.0)M), and C12-C15 alkyl polyethoxylate (4.0) sulfate (Cj2-Ci5E(4.0)M), wherein M is conveniently selected from sodium and potassium.
  • alkyl sulfate surfactants useful herein are preferably water soluble salts or acids of the formula ROSO3M wherein R preferably is a C10-C24 hydrocarbyl, preferably an alkyl or hydroxyalkyl having a Ci -Cj alkyl component, more preferably a C12-C15 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.
  • R preferably is a C10-C24 hydrocarbyl, preferably an alkyl or hydroxyalkyl having a Ci -Cj alkyl component, more preferably a C12-C15 alkyl or hydroxyalkyl
  • M is H or a cation, e.g., an alkali metal cation (e.g. sodium, potassium, lithium), or ammonium or substituted ammonium
  • methyl-, dimethyl-, and trimethyl ammonium cations and quaternary ammonium cations such as tetramethyl-ammomum and dimethyl piperidinium cations and quaternary ammonium cations derived from alkylamines such as ethylamine, diethylamine, triethylamine, and mixtures thereof, and the like).
  • alkyl ester sulfonate surfactants including linear esters of Cg-C20 carboxylic acids (i.e., fatty acids) which are sulfonated with gaseous SO3 according to "The Journal of the American Oil Chemists Society", 52 (1975), pp. 323-329.
  • Suitable starting materials would include natural fatty substances as derived from tallow, palm oil, etc.
  • alkyl ester sulfonate surfactant especially for laundry applications, comprise alkyl ester sulfonate surfactants of the structural formula :
  • R 3 - CH(SO 3 M) - C(O) - OR 4 wherein R 3 is a C -C20 hydrocarbyl, preferably an alkyl, or combination thereof, R 4 is a C j -Cg hydrocarbyl, preferably an alkyl, or combination thereof, and M is a cation which forms a water soluble salt with the alkyl ester sulfonate.
  • Suitable salt-forming cations include metals such as sodium, potassium, and lithium, and substituted or unsubstituted ammonium cations, such as monoethanolamine, diethanolamine, and triethanolamine.
  • R 3 is Cjj ⁇ -Ci g alkyl
  • R 4 is methyl, ethyl or isopropyl.
  • methyl ester sulfonates wherein R 3 is Cj ⁇ -Cjg alkyl.
  • anionic co-surfactants useful for detersive purposes can also be included in the laundry detergent compositions of the present invention.
  • These can include salts (including, for example, sodium, potassium, ammonium, and substituted ammonium salts such as mono-, di- and triethanolamine salts) of soap, Cg-C22 primary of secondary alkanesulfonates, C -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.
  • alkylpolyglycolethersulfates (containing up to 10 moles of ethylene oxide); alkyl glycerol sulfonates, fatty acyl glycerol sulfonates, fatty oleoyl glycerol sulfates, alkyl phenol ethylene oxide ether sulfates, paraffin sulfonates, alkyl phosphates, isethionates such as the acyl isethionates, N-acyl taurates, alkyl succinamates and sulfosuccinates, monoesters of sulfosuccinates (especially saturated and unsaturated l2"Cl8 monoesters) and diesters of sulfosuccinates (especially saturated and unsaturated Cg-Ci2 diesters), sulfates of alkylpolysaccharides such as the sulfates of alkylpolyglu
  • Resin acids and hydrogenated resin acids are also suitable, such as rosin, hydrogenated rosin, and resin acids and hydrogenated resin acids present in or derived from tall oil.- Further examples are described in "Surface Active Agents and Detergents" (Vol. I and II by Schwartz, Perry and Berch). A variety of such surfactants are also generally disclosed in U.S. Patent 3,929,678, issued December 30, 1975 to Laughlin, et al. at Column 23. line 58 through Column 29, line 23 (herein incorporated by reference).
  • a preferred disulfate surfactant has the formula
  • R is an alkyl, substituted alkyl, alkenyl, aryl, alkaryl, ether, ester, amine or amide group of chain length C ⁇ to C2g, preferably C3 to C24. most preferably Cg to C20, or hydrogen;
  • a and B are independently selected from alkyl, substituted alkyl, and alkenyl groups of chain length C ⁇ to C2g, preferably C] to C5, most preferably C] or C2, or a covalent bond, and A and B in total contain at least 2 atoms;
  • A, B, and R in total contain from 4 to about 31 carbon atoms;
  • X and Y are anionic groups selected from the group consisting of sulfate and sulfonate, provided that at least one of X or Y is a sulfate group; and
  • M is a cationic moiety, preferably a substituted or unsubstituted ammonium ion, or an alkali or alkaline
  • the most preferred disulfate surfactant has the formula as above where R is an alkyl group of chain length from Ci ⁇ to Cjg, A and B are independently C] or C2, both X and Y are sulfate groups, and M is a potassium, ammonium, or a sodium ion.
  • the disulfate surfactant is typically present at levels of incorporation of from about 0.1% to about 50%, preferably from about 0.1% to about 35%, most preferably from about 0.5% to about 15% by weight of the detergent composition.
  • Preferred disulfate surfactant herein include:
  • 1,3 disulfate compounds preferably 1,3 C7-C23 (i.e., the total number of carbons in the molecule) straight or branched chain alkyl or alkenyl disulfates, more preferably having the formula:
  • R is a straight or branched chain alkyl or alkenyl group of chain length from about C4 to about C ⁇ g;
  • R is a straight or branched chain alkyl or alkenyl group of chain length from about C4 to about C] g; preferred R are selected from octanyl, nonanyl, decyl, dodecyl, tetradecyl, hexadecyl, octadecyl, and mixtures thereof; and
  • R is a straight or branched chain alkyl or alkenyl group of chain length from about C4 to about C ⁇ g.
  • US-A-3, 959,334 and US-A-4,000,081 describe 2-hydrocarbyl-l,4-butanediol disulfates also prepared using a method involving the reduction of alkenyl succinic anhydrides with lithium aluminium hydride to produce either alkenyl or alkyl diols which are then sulfated.
  • These compounds may also be made by a method involving synthesis of the disulfate surfactant from a substituted cyclic anhydride having one or more carbon chain substituents having in total at least 5 carbon atoms comprising the following steps:
  • the laundry detergent compositions of the present invention typically comprise from about 0.1% to about 50%, preferably from about 1% to about 40% by weight of an anionic surfactant.
  • Nonlimiting examples of nonionic co-surfactants useful herein typically at levels from about 0.1% to about 50%, by weight include the alkoxylated alcohols (AE's) and alkyl phenols, polyhydroxy fatty acid amides (PFAA's), alkyl polyglycosides (APG's), Cj ⁇ -Cig glycerol ethers, and the like.
  • AE alkoxylated alcohol
  • PFAA's polyhydroxy fatty acid amides
  • APG's alkyl polyglycosides
  • Cj ⁇ -Cig glycerol ethers Cj ⁇ -Cig glycerol ethers
  • condensation products of primary and secondary aliphatic alcohols with from about 1 to about 25 moles of ethylene oxide (AE) are suitable for use as the nonionic surfactant in the present invention.
  • the alkyl chain of the aliphatic alcohol can either be straight or branched, primary or secondary, and generally contains from about 8 to about 22 carbon atoms.
  • Especially preferred nonionic surfactants of this type are the C9-C15 primary alcohol ethoxylates containing 3-12 moles of ethylene oxide per mole of alcohol, particularly the C12-C15 primary alcohols containing 5-10 moles of ethylene oxide per mole of alcohol.
  • nonionic surfactants of this type include: TergitolTM 15-S-9 (the condensation product of C ⁇ ⁇ -C ⁇ linear alcohol with 9 moles ethylene oxide) and Tergitol ⁇ M 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 23-3 (the condensation product of C12-C13 linear alcohol with 3 moles of ethylene oxide), Neodol ⁇ M 45.7 (the condensation product of C14-C15 linear alcohol with 7 moles of ethylene oxide) and NeodolTM 45.5 (the condensation product of C ] 4-Cj5 linear alcohol with 5 moles of ethylene oxide) marketed by Shell Chemical Company; Kyro ⁇ M EOB (the condensation product of C13-C15 alcohol with 9 moles ethylene oxide), marketed by The Procter
  • Another class of preferred nonionic co-surfactants for use herein are the polyhydroxy fatty acid amide surfactants of the formula.
  • R* is H, or C]_4 hydrocarbyl, 2-hydroxy ethyl. 2-hydroxy propyl or a mixture thereof
  • R ⁇ is C5.31 hydrocarbyl
  • Z is a polyhydroxyhydrocarbyl having a linear hydrocarbyl chain with at least 3 hydroxyls directly connected to the chain, or an alkoxylated derivative thereof.
  • R is methyl
  • R ⁇ is a straight Cu.15 alkyl or C 15.
  • ⁇ alkyl or alkenyl chain such as coconut alkyl or mixtures thereof
  • Z is derived from a reducing sugar such as glucose, fructose, maltose, lactose, in a reductive amination reaction.
  • Typical examples include the C ⁇ -Cjg and C12-C14 N-methylglucamides. See U.S. 5,194,639 and 5,298,636. N-alkoxy polyhydroxy fatty acid amides can also be used; see U.S. 5,489,393.
  • alkylpolysaccharides such as those disclosed in U.S. Patent 4,565,647, Llenado, issued January 21, 1986, having a hydrophobic group containing from about 6 to about 30 carbon atoms, preferably from about 10 to about 16 carbon atoms, and a polysaccharide, e.g. a polyglycoside, hydrophilic group containing 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 saccharide units.
  • Any reducing saccharide containing 5 or 6 carbon atoms can be used, e.g., glucose, galactose and galactosyl moieties can be substituted for the glucosyl moieties (optionally the hydrophobic group is attached at the 2-, 3-, 4-, etc. positions thus giving a glucose or galactose as opposed to a glucoside 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.
  • Preferred alkylpolyglycosides have the formula
  • R ⁇ is selected from the group consisting of alkyl, alkylphenyl, 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. To prepare these compounds, 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- ⁇ osition, preferably predominately the 2-position.
  • Compounds of this type and their use in detergent are disclosed in EP-B 0 070 077, 0 075 996 and 0 094 118.
  • Polyethylene, polypropylene, and polybutylene oxide condensates of alkyl phenols are also suitable for use as the nonionic surfactant of the surfactant systems of the present invention, with the polyethylene oxide condensates being preferred.
  • These compounds include the condensation products of alkyl phenols having an alkyl group containing from about 6 to about 14 carbon atoms, preferably from about 8 to about 14 carbon atoms, in either a straight-chain or branched-chain configuration with the alkylene oxide.
  • the ethylene oxide is present in an amount equal to from about 2 to about 25 moles, more preferably from about 3 to about 15 moles, of ethylene oxide per mole of alkyl phenol.
  • nonionic surfactants of this type include Igepal ⁇ M CO-630, marketed by the GAF Corporation; and TritonTM X-45, X-114, X-100 and X-102, all marketed by the Rohm & Haas Company. These surfactants are commonly referred to as alkylphenol alkoxylates (e.g., alkyl phenol ethoxylates).
  • the condensation products of ethylene oxide with a hydrophobic base formed by the condensation of propylene oxide with propylene glycol are also suitable for use as the additional nonionic surfactant in the present invention.
  • the hydrophobic portion of these compounds will preferably have a molecular weight of from about 1500 to about 1800 and will exhibit 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 product, 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.
  • nonionic surfactant of the nonionic surfactant system of the present invention are the condensation products of ethylene oxide with the product resulting from the reaction of propylene oxide and ethylenediamine.
  • the hydrophobic moiety of these products consists 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 1 1,000.
  • this type of nonionic surfactant include certain of the commercially available TetronicTM compounds, marketed by BASF.
  • compositions of the present invention may comprise amine oxide in accordance with the general formula I:
  • the structure (I) provides one long-chain moiety Rl(EO) x (PO)y(BO) z and two short chain moieties, CH2R'- R' is preferably selected from hydrogen, methyl and -CH2OH.
  • R* is a primary or branched hydrocarbyl moiety which can be saturated or unsaturated, preferably, R' is a primary alkyl moiety.
  • R ⁇ is a hydrocarbyl moiety having chainlength of from about 8 to about 18.
  • R ⁇ may be somewhat longer, having a chainlength in the range C12-C24.
  • amine oxides are illustrated by C12-14 alkyldimethyl amine oxide, hexadecyl dimethylamine oxide, octadecylamine oxide and their hydrates, especially the dihydrates as disclosed in U.S. Patents 5,075,501 and 5,071,594, incorporated herein by reference.
  • the invention also encompasses amine oxides wherein x+y+z is different from zero, specifically x+y+z is from about 1 to about 10, R is a primary alkyl group containing 8 to about 24 carbons, preferably from about 12 to about 16 carbon atoms; in these embodiments y + z is preferably 0 and x is preferably from about 1 to about 6, more preferably from about 2 to about 4; EO represents ethyleneoxy; PO represents propyleneoxy; and BO represents butyleneoxy.
  • amine oxides can be prepared by conventional synthetic methods, e.g., by the reaction of alkylethoxysulfates with dimethylamine followed by oxidation of the ethoxylated amine with hydrogen peroxide.
  • amine oxides herein are solutions at ambient temperature.
  • Amine oxides suitable for use herein are made commercially by a number of suppliers, including Akzo Chemie, Ethyl Corp., and Procter & Gamble. See McCutcheon's compilation and Kirk-Othmer review article for alternate amine oxide manufacturers.
  • R' is H
  • R' is CH2OH, such as hexadecylbis(2- hydroxyethyl)amine oxide, tallowbis(2-hydroxyethyl)amine oxide, stearylbis(2- hydroxyethyl)amine oxide and oleylbis(2-hydroxyethyl)amine oxide, dodecyldimethylamine oxide dihydrate.
  • Preferred amines for use herein include amines according to the formula:
  • Rj is a Cg-Cj2 a 'kyl group
  • n is from about 2 to about 4
  • X is a bridging group which is selected from NH, CONH, COO, or O or X can be absent; and R3 and R4 are individually selected from H, C1-C4 alkyl, or (CH2-CH2-O(R5)) wherein R5 is H or methyl.
  • R1 is a C -Ci2 lkyl group and R5 is H or CH3.
  • the amine is described by the formula: R 1 -C(O)-NH-(CH 2 )3-N(CH 3 ) 2 wherein R] is Cg-Cj2 alkyl.
  • Particularly preferred amines include those selected from the group consisting of octyl amine, hexyl amine, decyl amine, dodecyl amine, C -Ci2 bis(hydroxyethyl)amine, Cg-C]2 bis(hydroxyisopropyl)amine. and C -Ci2 amido- propyl dimethyl amine, and mixtures.
  • Nonlimiting examples of cationic co-surfactants useful herein typically at levels from about 0.1% to about 50%, by weight include the choline ester-type quats and alkoxylated quaternary ammonium (AQA) surfactant compounds, and the like.
  • AQA alkoxylated quaternary ammonium
  • Most preferred for aqueous liquid compositions herein are soluble cationic co- surfactants which do not readily hydrolyze in the product.
  • Cationic co-surfactants useful as a component of the surfactant system is a cationic choline ester-type quat surfactant which are preferably water dispersible compounds having surfactant properties and comprise at least one ester (i.e. -COO-) linkage and at least one cationically charged group.
  • Suitable cationic ester surfactants, including choline ester surfactants have for example been disclosed in U.S. Patents Nos. 4,228,042, 4,239,660 and 4,260,529.
  • Cationic ester surfactants include those having the formula:
  • Rj is a C5-C31 linear or branched alkyl, alkenyl or alkaryl chain or M" .N + (R R7Rg)(CH2) s ;
  • X and Y independently, are selected from the group consisting of COO, OCO, O, CO, OCOO, CONH, NHCO, OCONH and NHCOO wherein at least one of X or Y is a COO, OCO, OCOO, OCONH or NHCOO group;
  • R 2 , R3, R4, Rg, R7 and Rg are independently selected from the group consisting of alkyl, alkenyl, hydroxyalkyl, hydroxyalkenyl and alkaryl groups having from 1 to 4 carbon atoms; and
  • R5 is independently H or a C-.
  • R2 and R4 are independently selected from CH3 and - CH 2 CH 2 OH.
  • M is selected from the group consisting of halide, mediyl sulfate, sulfate, and nitrate, more preferably methyl sulfate, chloride, bromide or iodide.
  • Preferred water dispersible cationic ester surfactants are the choline esters having the formula:
  • R ⁇ is a C ⁇ 1-C19 linear or branched alkyl chain.
  • the particularly preferred choline esters may be prepared by the direct esterification of a fatty acid of die desired chain length with dirnethylaminoethanol, in the presence of an acid catalyst.
  • the reaction product is then quaternized with a methyl halide, preferably in the presence of a solvent such as ethanol, propylene glycol or preferably a fatty alcohol ethoxylate such as Cj ⁇ -Ci fatty alcohol ethoxylate having a degree of ethoxylation of from 3 to 50 ethoxy groups per mole forming the desired cationic material.
  • a solvent such as ethanol, propylene glycol or preferably a fatty alcohol ethoxylate such as Cj ⁇ -Ci fatty alcohol ethoxylate having a degree of ethoxylation of from 3 to 50 ethoxy groups per mole forming the desired cationic material.
  • They may also be prepared by the direct esterification of a long chain fatty acid of the desired chain length together with 2-haloethanol
  • Suitable cationic ester surfactants have the structural formulas below, wherein d may be from 0 to 20.
  • cationic ester surfactant are hydrolysable under the conditions of a laundry wash method.
  • Cationic co-surfactants useful herein also include alkoxylated quaternary ammonium (AQA) surfactant compounds (referred to hereinafter as "AQA compounds") having the formula:
  • R! is an alkyl or alkenyl moiety containing from about 8 to about 18 carbon atoms, preferably 10 to about 16 carbon atoms, most preferably from about 10 to about 14 carbon atoms;
  • R* is an alkyl group containing from one to three carbon atoms, preferably methyl;
  • R 3 and R 4 can vary independently and are selected from hydrogen (preferred), methyl and ethyl;
  • X" is an anion such as chloride, bromide, methylsulfate, sulfate, or the like, sufficient to provide electrical neutrality.
  • a and A' can vary independently and are each selected from C1-C4 alkoxy, especially ethoxy (i.e., -CH2CH2O-), propoxy, butoxy and mixed ethoxy/propoxy; p is from 1 to about 30, preferably 1 to about 4 and q is from 1 to about 30, preferably 1 to about 4, and most preferably to about 4; preferably both p and q are 1. See also: EP 2,084, published May 30, 1979, by The Procter & Gamble Company, which describes cationic co-surfactants of this type which are also useful herein..
  • the levels of the AQA surfactants used to prepare finished laundry detergent compositions typically range from about 0.1% to about 5%, preferably from about 0.45% to about 2.5%, by weight.
  • AQA surfactants used herein. It is to be understood that the degree of alkoxylation noted herein for the AQA surfactants is reported as an average, following common practice for conventional ethoxylated nonionic surfactants. This is because the ethoxylation reactions typically yield mixtures of materials with differing degrees of ethoxylation. Thus, it is not uncommon to report total EO values other than as whole numbers, e.g., "EO2.5", “EO3.5”, and the like.
  • the preferred bis-ethoxylated cationic surfactants herein are available under the trade name ETHOQUAD from Akzo Nobel Chemicals Company.
  • R! is Cj ⁇ -Ci g hydrocarbyl and mixtures thereof, preferably Ci ⁇ , C]2, C14 alkyl and mixtures thereof, and X is any convenient anion to provide charge balance, preferably chloride.
  • R* is derived from coconut (C12-C - 4 alkyl) fraction fatty acids
  • R2 is methyl and ApR ⁇ and A'qR * "* are each monoethoxy. This preferred type of compound is referred to herein as "CocoMeEO2" or "AQA-1 " in the above list.
  • R ⁇ is Cj ⁇ -Ci g hydrocarbyl, preferably C10-C14 alkyl, independently p is 1 to about 3 and q is 1 to about 3, R ⁇ is C1-C3 alkyl, preferably methyl, and X is an anion, especially chloride.
  • Liquid cleaning compositions further comprise water and/or other solvents. Low molecular weight primary or secondary alcohols exemplified by methanol, ethanol, propanol, and isopropanol are suitable.
  • Monohydric alcohols are preferred for solubilizing surfactant, but polyols such as those containing from 2 to about 6 carbon atoms and from 2 to about 6 hydroxy groups (e.g., 1 ,3-propanediol, ethylene glycol, glycerine, and 1 ,2-propanediol) can also be used.
  • the compositions may contain from about 1% to about 99.7%, preferably from about 5% to about 90%, and most typically from about 10% to about 50% of solvents.
  • Heavy duty liquid detergent compositions herein, especially those designed for fabric laundering, may also comprise a non-aqueous carrier medium as described in more detail hereinafter.
  • the heavy duty liquid detergent compositions according to the present invention preferably further comprise a builder system.
  • a builder system or mixed builder system is suitable for use herein including aluminosilicate materials, silicates, polycarboxylates and fatty acids, materials such as ethylenediamine tetra-acetate, metal ion sequestrants such as aminopoly- phosphonates, particularly ethylenediamine tetramethylene phosphonic acid and diethylene triamine pentamethylene phosphonic acid.
  • phosphate builders can also be used herein.
  • Most preferred laundry detergent compositions according to the present invention comprise citrate/fatty acid mixed builder systems.
  • Suitable polycarboxylates builders for use herein include citric acid, preferably in the form of a water-soluble salt, derivatives of succinic acid of the formula R- CH(COOH)CH2(COOH) wherein R is Cio_20 alkyl or alkenyl, preferably C- ⁇ -i ⁇ or wherein R can be substituted with hydroxyl, sulfo sulfoxyl or sulfone substituents.
  • Specific examples include lauryl succinate, myristyl succinate, palmityl succinate 2- dodecenylsuccinate, 2-tetradecenyl succinate.
  • Succinate builders are preferably used in the form of their water-soluble salts, including sodium, potassium, ammonium and alkanolammonium salts.
  • polycarboxylates are oxodisuccinates and mixtures of tartrate monosuccinic and tartrate disuccinic acid such as described in US 4,663,071, as well as maleates.
  • suitable fatty acid builders for use herein are saturated or unsaturated C ⁇ Q. ⁇ g fatty acids, as well as the corresponding soaps.
  • Preferred saturated species have from 12 to 16 carbon atoms in the alkyl chain.
  • the preferred unsaturated fatty acid is oleic acid.
  • Other preferred builder system for liquid compositions is based on dodecenyl succinic acid and citric acid.
  • Detergency builders are normally included in amounts of from 0.5% to 50% by weight of the composition preferably from 3% to 30% and most usually from 5% to 15% by weight.
  • Preferred detergent compositions of the present invention may further comprise one or more enzymes which provide cleaning performance and/or fabric care benefits.
  • Said enzymes include enzymes selected from cellulases, hemicellulases, peroxidases, proteases, gluco-amylases, amyiases, upases, cutinases, pectinases, xylanases, reductases, oxidases, phenoloxidases, lipoxygenases, ligninases, pullulanases, tannases, pentosanases, malanases, ⁇ -glucanases, arabinosidases or mixtures thereof.
  • a preferred combination is a detergent composition having a cocktail of conventional applicable enzymes like protease, amylase, lipase, cutinase and or cellulase in conjunction with the lipolytic enzyme variant D96L at a level of from 50 LU to 8500 LU per liter wash solution.
  • the cellulases usable in the present invention include both bacterial or fungal cellulase. Preferably, they will have a pH optimum of between 5 and 9.5. Suitable cellulases are disclosed in U.S. Patent 4,435,307 ⁇ Barbesgoard et al, which discloses fungal cellulase produced from Humicola insolens. Suitable cellulases are also disclosed in GB-A-2.075.028; GB-A-2.095.275 and DE-OS-2.247.832.
  • cellulases examples include cellulases produced by a strain of Humicola insolens (Humicola grisea var. thermoidea), particularly the Humicola strain DSM 1800.
  • suitable cellulases are cellulases originated from Humicola insolens having a molecular weight of about 50KDa, an isoelectric point of 5.5 and containing 415 amino acids. Especially suitable cellulases are the cellulases having color care benefits. Examples of such cellulases are cellulases described in European patent application No. 91202879.2, filed November 6, 1991 (Novo).
  • Peroxidase enzymes are used in combination with oxygen sources, e.g. percarbonate, perborate, persulfate, hydrogen peroxide, etc. They are used for "solution bleaching", i.e. to prevent transfer of dyes or pigments removed from substrates during wash operations to other substrates in the wash solution.
  • Peroxidase enzymes are known in the art, and include, for example, horseradish peroxidase, ligninase, and haloperoxidase such as chloro- and bromo-peroxidase.
  • Peroxidase- containing detergent compositions are disclosed, for example, in PCT International Application WO 89/099813 and in European Patent application EP No. 91202882.6, filed on November 6, 1991. Said cellulases and or peroxidases are normally incorporated in the detergent composition at levels from 0.0001% to 2% of active enzyme by weight of the detergent composition.
  • protease enzymes include those sold under the tradenames Alcalase, Savinase, Primase, Durazym, and Esperase by Novo Nordisk A/S (Denmark), those sold under the tradename Maxatase, Maxacal and Maxapem by Gist-Brocades, those sold by Genencor International, and those sold under the tradename Opticlean and Optimase by Solvay Enzymes. Also proteases described in our co-pending application USSN 08/136,797 can be included in the detergent composition of the invention. Protease enzyme may be incorporated into the compositions in accordance with the invention at a level of from 0.0001% to 2% active enzyme by weight of the composition.
  • a preferred protease herein referred to as "Protease D” is a carbonyl hydrolase variant having an amino acid sequence not found in nature, which is derived from a precursor carbonyl hydrolase by substituting a different amino acid for the amino acid residue at a position in said carbonyl hydrolase equivalent to position +76, preferably also in combination with one or more amino acid residue positions equivalent to those selected from the group consisting of +99, +101, +103, +104, +107, +123, +27, +105, +109, +126, +128, +135, +156, +166, +195, +197, +204, +206, +210, +216, +217, +218, +222, +260, +265, and/or +274 according to the numbering of Bacillus amyloliquefaciens subtilisin, as described in WO 95/10615 published April 20, 1995 by Genencor International.
  • proteases are also described in PCT publications: WO 95/30010 published Novenber 9, 1995 by The Procter & Gamble Company; WO 95/3001 1 published Novenber 9, 1995 by The Procter & Gamble Company; WO 95/29979 published Novenber 9, 1995 by The Procter & Gamble Company.
  • Highly preferred enzymes that can be included in the detergent compositions of the present invention include Upases. It has been found that the cleaning performance on greasy soils is synergistically improved by using lipases.
  • Suitable lipase enzymes include those produced by microorganisms of the Pseudomonas group, such as Pseudomonas stutzeri ATCC 19.154, as disclosed in British Patent 1,372,034.
  • Suitable lipases include those which show a positive immunological cross-reaction with the antibody of the lipase, produced by the microorganism Pseudomonas fluorescens IAM 1057. This lipase is available from Amano Pharmaceutical Co.
  • Lipase P (Amano,” hereinafter referred to as "Amano-P".
  • lipases such as Ml Lipase® and Lipomax® (Gist-Brocades).
  • Highly preferred lipases are the D96L lipolytic enzyme variant of the native lipase derived from Humicola lanuginosa as described in US Serial No. 08/341,826.
  • the Humicola lanuginosa strain DSM 4106 is used.
  • This enzyme is incorporated into the composition in accordance with the invention at a level of from 50 LU to 8500 LU per liter wash solution.
  • the variant D96L is present at a level of from 100 LU to 7500 LU per liter of wash solution. More preferably at a level of from 150 LU to 5000 LU per liter of wash solution.
  • D96L lipolytic enzyme variant is meant the lipase variant as described in patent application WO 92/05249 viz. wherein the native lipase ex Humicola lanuginosa aspartic acid (D) residue at position 96 is changed to Leucine (L). According to this nomenclature said substitution of aspartic acid to Leucine in position 96 is shown as : D96L.
  • cutinases [EC 3.1.1.50] which can be considered as a special kind of lipase, namely lipases which do not require interfacial activation. Addition of cutinases to detergent compositions have been described in e.g. WO-A-88/09367 (Genencor).
  • the lipases and/or cutinases are normally incorporated in the detergent composition at levels from 0.0001% to 2% of active enzyme by weight of the detergent composition.
  • Amylases (& and or ⁇ ) can be included for removal of carbohydrate-based stains. Suitable amylases are TermamylR (Novo Nordisk), FungamylR and BANR (Novo Nordisk).
  • Certain preferred embodiments of the present compositions can make use of amylases having improved stability in detergents, especially improved oxidative stability as measured against a reference-point of TERMAMYL® in commercial use in 1993.
  • These preferred amylases herein share the characteristic of being "stability- enhanced" amylases, characterized, at a minimum, by a measurable improvement in one or more of: oxidative stability, e.g., to hydrogen peroxide/tetraacetylethylenediamine in buffered solution at pH 9-10; thermal stability, e.g., at common wash temperatures such as about 60°C; or alkaline stability, e.g., at a pH from about 8 to about 1 1, measured versus the above-identified reference-point amylase.
  • oxidative stability e.g., to hydrogen peroxide/tetraacetylethylenediamine in buffered solution at pH 9-10
  • thermal stability e.g., at common wash temperatures such as about 60°C
  • Stability-enhanced amylases can be obtained from Novo or from Genencor International.
  • One class of highly preferred amylases herein have the commonality of being derived using site-directed mutagenesis from one or more of the Bacillus amylases, especially the Bacillus ⁇ - amylases, regardless of whether one, two or multiple amylase strains are the immediate precursors.
  • Oxidative stability-enhanced amylases vs. the above-identified reference amylase are preferred for use, especially in bleaching, more preferably oxygen bleaching, as distinct from chlorine bleaching, detergent compositions herein.
  • Such preferred amylases include (a) an amylase according to the hereinbefore incorporated WO 9402597, Novo, Feb. 3, 1994, as further illustrated by a mutant in which substitution is made, using alanine or threonine, preferably threonine, of the methionine residue located in position 197 of the B. licheniformis alpha-amylase, known as TERMAMYL®, or the homologous position variation of a similar parent amylase, such as B. amyloliquefaciens, B. subtilis, or B.
  • Met was substituted, one at a time, in positions 8, 15, 197, 256, 304, 366 and 438 leading to specific mutants, particularly important being M197L and M197T with the M197T variant being the most stable expressed variant. Stability was measured in CASCADE® and SUNLIGHT®; (c) particularly preferred amylases herein include amylase variants having additional modification in the immediate parent as described in WO 9510603 A and are available from the assignee, Novo, as DURAMYL®. Other particularly preferred oxidative stability enhanced amylase include those described in WO 9418314 to Genencor International and WO 9402597 to Novo.
  • Any other oxidative stability-enhanced amylase can be used, for example as derived by site-directed mutagenesis from known chimeric, hybrid or simple mutant parent forms of available amylases. Other preferred enzyme modifications are accessible. See WO 9509909 A to Novo.
  • the above-mentioned enzymes may be of any suitable origin, such as vegetable, animal, bacterial, fungal and yeast origin.
  • Said enzymes are normally incorporated in the detergent composition at levels from 0.0001% to 2% of active enzyme by weight of the detergent composition.
  • Other suitable detergent ingredients that can be added are enzyme oxidation scavengers which are described in Copending European Patent application 92870018.6 filed on January 31, 1992. Examples of such enzyme oxidation scavengers are ethoxylated tetraethylene polyamines.
  • liquid compositions according to the present invention are in "concentrated form"; in such case, the liquid detergent compositions according to the present invention will contain a lower amount of water, compared to conventional liquid detergents.
  • the level of water is less than 50%, preferably less than 30% by weight of the detergent compositons.
  • Said concentrated products provide advantages to the consumer, who has a product which can be used in lower amounts and to the producer, who has lower shipping costs.
  • the liquid compositions are especially effective when applied directly to soils and stains in a pretreatment step before washing the fabrics.
  • the detergent compositions of the present invention can also be used as detergent additive products. Such additive products are intended to supplement or boost the performance of conventional detergent compositions.
  • the detergent compositions according to the present invention include compositions which are to be used for cleaning of substrates, such as fabrics, fibers, hard surfaces, skin etc., for example hard surface cleaning compositions (with or without abrasives), laundry detergent compositions, automatic and non-automatic dishwashing compositions.
  • substrates such as fabrics, fibers, hard surfaces, skin etc.
  • hard surface cleaning compositions with or without abrasives
  • laundry detergent compositions automatic and non-automatic dishwashing compositions.
  • compositions can contain various paniculate detersive ingredients (including the bleaching agents, as disclosed hereinabove) stably suspended therein.
  • Such non-aqueous compositions thus comprise a LIQUID PHASE and, optionally but preferably, a SOLID PHASE, all as described in more detail hereinafter and in the cited references.
  • the dianionic ester cleaning agent is incorporated in the compositions at the levels and in the manner described hereinabove for the manufacture of other laundry detergent compositions.
  • the liquid phase will generally comprise from about 35% to 99% by weight of the detergent compositions herein. More preferably, the liquid phase will comprise from about 50% to 95% by weight of the compositions. Most preferably, the liquid phase will comprise from about 45% to 75% by weight of the compositions herein.
  • the liquid phase of the detergent compositions herein essentially contains relatively high concentrations of a certain type anionic surfactant combined with a certain type of nonaqueous, liquid diluent.
  • the anionic surfactant essentially utilized as an essential component of the nonaqueous liquid phase is one selected from the alkali metal salts of alkylbenzene sulfonic acids in which the alkyl group contains from about 10 to 16 carbon atoms, in straight chain or branched chain configuration.
  • alkylbenzene sulfonic acids in which the alkyl group contains from about 10 to 16 carbon atoms, in straight chain or branched chain configuration.
  • LAS sodium and potassium linear straight chain alkylbenzene sulfonates
  • Sodum C ⁇ 1-C14 LAS is especially preferred.
  • the alkylbenzene sulfonate anionic surfactant will be dissolved in the nonaqueous liquid diluent which makes up the second essential component of the nonaqueous phase.
  • the alkylbenzene sulfonate anionic surfactant is generally present to the extent of from about 30% to 65% by weight of the liquid phase. More preferably, the alkylbenzene sulfonate anionic surfactant will comprise from about 35% to 50% by weight of the nonaqueous liquid phase of the compositions herein. Utilization of this anionic surfactant in these concentrations corresponds to an anionic surfactant concentration in the total composition of from about 15% to 60% by weight, more preferably from about 20% to 40% by weight, of the composition.
  • the hereinbefore described alkylbenzene sulfonate anionic surfactant is combined with a nonaqueous liquid diluent which contains two essential components. These two components are a liquid alcohol alkoxylate material and a nonaqueous, low-polarity organic solvent. i) Alcohol Alkoxylates
  • Such materials are themselves also nonionic surfactants.
  • Such materials correspond to the general formula:
  • R 1 (C m H 2m O) n OH wherein R* is a Cg - Cjg alkyl group, m is from 2 to 4, and n ranges from about 2 to 12.
  • R! is an alkyl group, which may be primary or secondary, that contains from about 9 to 15 carbon atoms, more preferably from about 10 to 14 carbon atoms.
  • the alkoxylated fatty alcohols will be ethoxylated materials that contain from about 2 to 12 ethylene oxide moieties per molecule, more preferably from about 3 to 10 ethylene oxide moieties per molecule.
  • the alkoxylated fatty alcohol component of the liquid diluent will frequently have a hydrophilic-lipophilic balance (HLB) which ranges from about 3 to 17. More preferably, the HLB of this material will range from about 6 to 15, most preferably from about 8 to 15.
  • HLB hydrophilic-lipophilic balance
  • fatty alcohol alkoxylates useful as one of the essential components of the nonaqueous liquid diluent in the compositions herein will include those which are made from alcohols of 12 to 15 carbon atoms and which contain about 7 moles of ethylene oxide. Such materials have been commercially marketed under the trade names Neodol 25-7 and Neodol 23-6.5 by Shell Chemical Company.
  • Neodols include Neodol 1-5, an ethoxylated fatty alcohol averaging 11 carbon atoms in its alkyl chain with about 5 moles of ethylene oxide; Neodol 23-9, an ethoxylated primary Cj2 - C13 alcohol having about 9 moles of ethylene oxide and Neodol 91-10, an ethoxylated C9 - Ci j primary alcohol having about 10 moles of ethylene oxide. Alcohol ethoxylates of this type have also been marketed by Shell Chemical Company under the Dobanol tradename.
  • Dobanol 91-5 is an ethoxylated C9-C1 1 fatty alcohol with an average of 5 moles ethylene oxide and Dobanol 25-7 is an ethoxylated C12-C15 fatty alcohol with an average of 7 moles of ethylene oxide per mole of fatty alcohol.
  • Suitable ethoxylated alcohols include Tergitol 15-S-7 and Tergitol 15-S-9 both of which are linear secondary alcohol ethoxylates that have been commercially marketed by Union Carbide Corporation.
  • the former is a mixed ethoxylation product of Cj ⁇ to C15 linear secondary alkanol with 7 moles of ethylene oxide and the latter is a similar product but with 9 moles of ethylene oxide being reacted.
  • Neodol 45-1 1 are similar ethylene oxide condensation products of higher fatty alcohols, with the higher fatty alcohol being of 14-15 carbon atoms and the number of ethylene oxide groups per mole being about 11. Such products have also been commercially marketed by Shell Chemical Company.
  • the alcohol alkoxylate component which is essentially utilized as part of the liquid diluent in the nonaqueous compositions herein will generally be present to the extent of from about 1 % to 60% of the liquid phase composition. More preferably, the alcohol alkoxylate component will comprise about 5% to 40% of the liquid phase. Most preferably, the essentially utilized alcohol alkoxylate component will comprise from about 5% to 30% of the detergent composition liquid phase. Utilization of alcohol alkoxylate in these concentrations in the liquid phase corresponds to an alcohol alkoxylate concentration in the total composition of from about 1% to 60% by weight, more preferably from about 2% to 40% by weight, and most preferably from about 5% to 25% by weight, of the composition. ii) Nonaqueous Low-Polarity Organic Solvent
  • a second essential component of the liquid diluent which forms part of the liquid phase of the detergent compositions herein comprises nonaqueous, low-polarity organic solvent(s).
  • solvent is used herein to connote the non-surface active carrier or diluent portion of the liquid phase of the composition. While some of the essential and/or optional components of the compositions herein may actually dissolve in the "solvenf'-containing liquid phase, other components will be present as paniculate material dispersed within the "solvenf-containing liquid phase. Thus the term “solvent” is not meant to require that the solvent material be capable of actually dissolving all of the detergent composition components added thereto.
  • nonaqueous organic materials which are employed as solvents herein are those which are liquids of low polarity.
  • low-polarity liquids are those which have little, if any, tendency to dissolve one of the preferred types of particulate material used in the compositions herein, i.e., the peroxygen bleaching agents, sodium perborate or sodium percarbonate.
  • relatively polar solvents such as ethanol should not be utilized.
  • Suitable types of low-polarity solvents useful in the nonaqueous liquid detergent compositions herein do include non-vicinal C4 ⁇ Cg alkylene glycols, alkylene glycol mono lower alkyl ethers, lower molecular weight polyethylene glycols, lower molecular weight methyl esters and amides, and the like.
  • a preferred type of nonaqueous, low-polarity solvent for use in the compositions herein comprises the non- vicinal C4-Cg branched or straight chain alkylene glycols.
  • Materials of this type include hexylene glycol (4-methyl-2,4- pentanediol), 1 ,6-hexanediol, 1,3-butylene glycol and 1,4-butylene glycol. Hexylene glycol is the most preferred.
  • nonaqueous, low-polarity solvent for use herein comprises the mono-, di-, tri-, or tetra- C2-C3 alkylene glycol mono C2-Cg alkyl • ethers.
  • the specific examples of such compounds include diethylene glycol monobutyl ether, tetraethylene glycol monobutyl ether, dipropylene glycol monoethyl ether, and dipropylene glycol monobutyl ether.
  • Diethylene glycol monobutyl ether and dipropylene glycol monobutyl ether are especially preferred.
  • Compounds of the type have been commercially marketed under the tradenames Dowanol, Carbitol. and Cellosolve.
  • nonaqueous, low-polarity organic solvent useful herein comprises the lower molecular weight polyethylene glycols (PEGs).
  • PEGs polyethylene glycols
  • Such materials are those having molecular weights of at least about 150.
  • PEGs of molecular weight ranging from about 200 to 600 are most preferred.
  • non-polar, nonaqueous solvent comprises lower molecular weight methyl esters.
  • methyl esters Such materials are those of the general formula: Rl- C(O)-OCH3 wherein R! ranges from 1 to about 18.
  • suitable lower molecular weight methyl esters include methyl acetate, methyl propionate, methyl octanoate, and methyl dodecanoate.
  • the nonaqueous, low-polarity organic solvent(s) employed should, of course, be compatible and non-reactive with other composition components, e.g., bleach and/or activators, used in the liquid detergent compositions herein.
  • a solvent component will generally be utilized in an amount of from about 1% to 70% by weight of the liquid phase.
  • the nonaqueous, low-polarity organic solvent will comprise from about 10% to 60% by weight of the liquid phase, most preferably from about 20% to 50% by weight, of the liquid phase of the composition.
  • Utilization of this organic solvent in these concentrations in the liquid phase corresponds to a solvent concentration in the total composition of from about 1 % to 50% by weight, more preferably from about 5% to 40% by weight, and most preferably from about 10% to 30% by weight, of the composition.
  • the ratio of alcohol alkoxylate to organic solvent within the liquid diluent can be used to vary the rheological properties of the detergent compositions eventually formed.
  • the weight ratio of alcohol alkoxylate to organic solvent will range from about 50:1 to 1 :50. More preferably, this ratio will range from about 3:1 to 1 :3.
  • the amount of total liquid diluent in the nonaqueous liquid phase herein will be determined by the type and amounts of other composition components and by the desired composition properties.
  • the liquid diluent will comprise from about 35% to 70% of the nonaqueous liquid phase of the compositions herein. More preferably, the liquid diluent will comprise from about 50% to 65% of the nonaqueous liquid phase. This corresponds to a nonaqueous liquid diluent concentration in the total composition of from about 15% to 70% by weight, more preferably from about 20% to 50% by weight, of the composition.
  • the nonaqueous detergent compositions herein also essentially comprise from about 1% to 65% by weight, more preferably from about 5% to 50% by weight, of a solid phase of particulate material which is dispersed and suspended within the liquid phase.
  • a solid phase of particulate material which is dispersed and suspended within the liquid phase.
  • particulate material will range in size from about 0.1 to 1500 microns. More preferably such material will range in size from about 5 to 200 microns.
  • the particulate material utilized herein can comprise one or more types of detergent composition components which in particulate form are substantially insoluble in the nonaqueous liquid phase of the composition.
  • the types of particulate materials which can be utilized are described in detail as follows:
  • nonaqueous liquid detergent compositions herein can be prepared by combining the essential and optional components thereof in any convenient order and by mixing, e.g., agitating, the resulting component combination to form the phase stable compositions herein.
  • essential and certain preferred optional components will be combined in a particular order and under certain conditions.
  • an admixture of the alkylbenzene sulfonate anionic surfactant and the two essential components of the nonaqueous diluent is formed by heating a combination of these materials to a temperature from about 30°C to 100°C.
  • a second process step the heated admixture formed as hereinbefore described is maintained under shear agitation at a temperature from about 40°C to 100°C for a period of from about 2 minutes to 20 hours.
  • a vacuum can be applied to the admixture at this point.
  • This second process step serves to completely dissolve the anionic surfactant in the nonaqueous liquid phase.
  • this liquid phase combination of materials is cooled to a temperature of from about 0°C to 35°C.
  • This cooling step serves to form a structured, surfactant-containing liquid base into which the particulate material of the detergent compositions herein can be added and dispersed.
  • Particulate material is added in a fourth process step by combining the particulate material with the liquid base which is maintained under conditions of shear agitation.
  • the liquid base which is maintained under conditions of shear agitation.
  • any optional surfactants in solid particulate form can be added in the form of particles ranging in size from about 0.2 to 1 ,000 microns.
  • particles of substantially all of an organic builder e.g., citrate and/or fatty acid, and/or an alkalinity source, e.g., sodium carbonate
  • an organic builder e.g., citrate and/or fatty acid
  • an alkalinity source e.g., sodium carbonate
  • Other solid form optional ingredients can then be added to the composition at this point. Agitation of the mixture is continued, and if necessary, can be increased at this point to form a uniform dispersion of insoluble solid phase particulates within the liquid phase.
  • particles of bleaching agent can be added to the composition, again while the mixture is maintained under shear agitation.
  • the bleaching agents used herein can be any of the bleaching agents useful for detergent compositions in textile cleaning. These include oxygen bleaches as well as other bleaching agents such as percarboxylic acid bleaching agents and salts thereof. Suitable examples of this latter class of agents include magnesium monoperoxyphthalate hexahydrate, the magnesium salt of metachloro perbenzoic acid, 4-nonylamino-4-oxoperoxybutyric acid and diperoxydodecanedioic acid. Such bleaching agents are disclosed in U.S. Patent 4,483,781 , Hartman, issued November 20, 1984, U.S.
  • Highly preferred bleaching agents also include 6-nonylamino-6-oxoperoxycaproic acid as described in U.S. Patent 4,634,551, issued January 6, 1987 to Burns et al.
  • peroxygen bleaching agents which include sodium carbonate peroxyhydrate and equivalent "percarbonate” bleaches, perborate bleaches, sodium pyrophosphate peroxyhydrate, urea peroxyhydrate, sodium peroxide, and persulfate bleach (e.g., OXONE, manufactured commercially by DuPont).
  • enzyme prills are incorporated, they are preferably added to the nonaqueous liquid matrix last.
  • composition preparation procedure As a final process step, after addition of all of the particulate material, agitation of the mixture is continued for a period of time sufficient to form compositions having the requisite viscosity and phase stability characteristics. Frequently this will involve agitation for a period of from about 1 to 30 minutes.
  • one or more of the solid components may be added to the agitated mixture as a slurry of particles premixed with a minor portion of one or more of the liquid components.
  • a premix of a small fraction of the alcohol alkoxylate and/or nonaqueous, low-polarity solvent with particles of the organic builder material and/or the particles of the inorganic alkalinity source and/or particles of a bleach activator may be separately formed and added as a slurry to the agitated mixture of composition components. Addition of such slurry premixes should precede addition of bleaching agent and/or enzyme particles which may themselves be part of a premix slurry formed in analogous fashion.
  • compositions of this invention can be used to form aqueous washing solutions for use in the laundering and bleaching of fabrics.
  • an effective amount of such compositions is added to water, preferably in a conventional fabric laundering automatic washing machine, to form such aqueous laundering solutions.
  • the aqueous washing solution so formed is then contacted, preferably under agitation, with the fabrics to be laundered therewith.
  • An effective amount of the liquid detergent compositions herein added to water to form aqueous laundering solutions can comprise amounts sufficient to form from about 500 to 7,000 ppm of composition in aqueous solution. More preferably, from about 800 to 3,000 ppm of the detergent compositions herein will be provided in aqueous washing solution.
  • CxyEzS Sodium C ⁇ x -C] v branched alkyl sulfate condensed with z moles of ethylene oxide
  • CxyFA C ⁇ x -C ⁇ y fatty acid
  • Citric acid Anhydrous citric acid Carbonate Anhydrous sodium carbonate with a particle size between 200 ⁇ m and 900 ⁇ m Citrate Tri-sodium citrate dihydrate of activity 86.4% with a particle size distribution between 425 ⁇ m and 850 ⁇ m
  • NOBS Nonanoyloxybenzene sulfonate in the form of the sodium salt.
  • Brightener 1 Disodium 4,4'-bis(2-sulphostyryl)biphenyl
  • Brightener 2 Disodium 4,4'-bis(4-anilino-6-morpholino- 1.3.5-triazin-2-yl)amino) stilbene-2:2'-disulfonate.
  • EXAMPLE 1 A non-limiting example of bleach-containing nonaqueous liquid laundry- detergent is prepared having the composition as set forth in Table I.
  • Dianionic is the isethionate ester or ethoxylated isethionate ester of alpha- sulfonated Cjg/Cig fatty acid.
  • the resulting composition is an anhydrous heavy duty liquid laundry detergent which provides excellent stain and soil removal performance when used in normal fabric laundering operations.
  • Example further illustrates the invention herein with respect to a hand dishwashing liquid.
  • Liquid detergent compositions are made according to the following.
  • *SESA is the isethionate ester of alpha-sulfonated Ci /Ci fatty acid.
  • SEASA is the ethoxylated isethionate ester of alpha-sulfonated Cjg/Cig fatty acid.
  • liquid detergent compositions (A-D) are found to be very efficient in the removal of a wide range of stains and soils from fabrics under various usage conditions.
  • EXAMPLES 4-9 The following are heavy duty liquid laundry detergent compositions according to the present invention.
  • the shampoo compositions of the present invention typically can comprise the following ingredients, components, or limitations described herein.
  • water soluble refers to any material that is sufficiently soluble in water to form a substantially clear solution to the naked eye at a concentration of 0.1% in water, i.e. distilled or equivalent, at 25°C.
  • the shampoo compositions of the present invention will comprise, in addition to the dianionic or alkoxylated dianionic ester cleaning agent, one or more detersive co-surfactants selected from the group consisting of anionic surfactant, nonionic surfactant, cationic surfactant, amphoteric surfactant, zwitterionic surfactants, and mixtures thereof.
  • the shampoo compositions preferably comprise an anionic co- surfactant.
  • Surfactant mixture i.e., the dianionic ester cleaning agent plus the co- surfactant concentrations range from about 5% to about 50%, preferably from about 8% to about 30%, more preferably from about 10% to about 25%, by weight of the compositions.
  • Anionic surfactant i.e., the dianionic ester cleaning agent plus the co- surfactant
  • the shampoo compositions preferably comprise an anionic co-surfactant, and preferably at concentrations of from about 5% to about 30%, more preferably from about 7% to about 25%, even more preferably from about 7% to about 20%, and most preferably from about 9% to about 18%, by weight of the composition.
  • Anionic surfactants for use in the shampoo compositions include alkyl and alkyl ether sulfates. These materials have the respective formulae ROSO3M and RO(C2H4O) x SO3M, wherein R is alkyl or alkenyl of from about 8 to about 30 carbon atoms, x is 1 to 10, and M is a cation such as ammonium, alkanolamines, such as triethanolamine, monovalent metals, such as sodium and potassium, and polyvalent metal cations, such as magnesium, and calcium.
  • the cation M, of the anionic surfactant should be chosen such that the anionic surfactant component is water soluble. Solubility will depend upon the particular anionic surfactants and cations chosen.
  • R has from about 12 to about 18 carbon atoms in both the alkyl and alkyl ether sulfates.
  • the alkyl ether sulfates are typically made as condensation products of ethylene oxide and monohydric alcohols having from about 8 to about 24 carbon atoms.
  • the alcohols can be derived from fats, e.g., coconut oil or tallow, or can be synthetic. Lauryl alcohol and straight chain alcohols derived from coconut oil are preferred herein. Such alcohols are reacted with between about 0 and about 10, and especially about 3, molar proportions of ethylene oxide and the resulting mixture of molecular species having, for example, an average of 3 moles of ethylene oxide per mole of alcohol, is sulfated and neutralized.
  • alkyl ether sulfates which may be used in the shampoo compositions of the present invention are sodium and ammonium salts of coconut alkyl triethylene glycol ether sulfate; tallow alkyl triethylene glycol ether sulfate. and tallow alkyl hexaoxyethylene sulfate.
  • Highly preferred alkyl ether sulfates are those comprising a mixture of individual compounds, said mixture having an average alkyl chain length of from about 10 to about 16 carbon atoms and an average degree of ethoxylation of from about 1 to about 4 moles of ethylene oxide.
  • Suitable anionic surfactants are the water-soluble salts of organic, sulfuric acid reaction products of the general formula [ R1-SO3-M ] where Rj is selected from the group consisting of a straight or branched chain, saturated aliphatic hydrocarbon radical having from about 8 to about 24, preferably about 10 to about 18, carbon atoms; and M is a cation, as previously described, subject to the same limitations regarding polyvalent metal cations as previously discussed.
  • Rj is selected from the group consisting of a straight or branched chain, saturated aliphatic hydrocarbon radical having from about 8 to about 24, preferably about 10 to about 18, carbon atoms; and M is a cation, as previously described, subject to the same limitations regarding polyvalent metal cations as previously discussed.
  • Examples of such surfactants are the salts of an organic sulfuric acid reaction product of a hydrocarbon of the methane series, including iso-, neo-.
  • n-paraffms having about 8 to about 24 carbon atoms, preferably about 12 to about 18 carbon atoms and a sulfonating agent, e.g., SO3, H2SO4, obtained according to known sulfonation methods, including bleaching and hydrolysis.
  • a sulfonating agent e.g., SO3, H2SO4
  • SO3, H2SO4 a sulfonating agent
  • anionic surfactants are the reaction products of fatty acids esterified with isethionic acid and neutralized with sodium hydroxide where, for example, the fatty acids are derived from coconut oil; sodium or potassium salts of fatty acid amides of methyl tauride in which the fatty acids, for example, are derived from coconut oil.
  • Other similar anionic surfactants are described in U.S. Patents 2,486,921; 2,486,922; and 2.396,278.
  • anionic surfactants suitable for use in the shampoo compositions are the succinnates, examples of which include disodium N-octadecylsulfosuccinnate; disodium lauryl sulfosuccinate; diammonium lauryl sulfosuccinate; tetrasodium N-(l,2-dicarboxyethyl)-N-octadecylsulfosuccinnate; diamyl ester of sodium sulfosuccinic acid; dihexyl ester of sodium sulfosuccinic acid; dioctyl esters of sodium sulfosuccinic acid.
  • succinnates examples of which include disodium N-octadecylsulfosuccinnate; disodium lauryl sulfosuccinate; diammonium lauryl sulfosuccinate; tetrasodium N-(l,2-dicarboxy
  • Suitable anionic surfactants include olefin sulfonates having about 10 to about 24 carbon atoms.
  • olefin sulfonates is used herein to mean compounds which can be produced by the sulfonation of alpha-olefins by means of uncomplexed sulfur trioxide, followed by neutralization of the acid reaction mixture in conditions such that any sulfones which have been formed in the reaction are hydrolyzed to give the corresponding hydroxy-alkanesulfonates.
  • the sulfur trioxide can be liquid or gaseous, and is usually, but not necessarily, diluted by inert diluents, for example by liquid SO2, chlorinated hydrocarbons, etc., when used in the liquid form, or by air, nitrogen, gaseous SO2, etc., when used in the gaseous form.
  • inert diluents for example by liquid SO2, chlorinated hydrocarbons, etc., when used in the liquid form, or by air, nitrogen, gaseous SO2, etc., when used in the gaseous form.
  • the alpha-olefins from which the olefin sulfonates are derived are mono-olefins having about 12 to about 24 carbon atoms, preferably about 14 to about 16 carbon atoms. Preferably, they are straight chain olefins.
  • the olefin sulfonates can contain minor amounts of other materials, such as alkene disulfonates depending upon the reaction conditions, proportion of reactants, the nature of the starting olefins and impurities in the olefin stock and side reactions during the sulfonation process.
  • Another class of anionic surfactants suitable for use in the shampoo compositions are the beta-alkyloxy alkane sulfonates. These compounds have the following formula:
  • R ⁇ is a straight chain alkyl group having from about 6 to about 20 carbon atoms
  • R2 is a lower alkyl group having from about 1 (preferred) to about 3 carbon atoms
  • M is a water-soluble cation as hereinbefore described.
  • Preferred anionic surfactants for use in the shampoo compositions include ammonium lauryl sulfate, ammonium laureth sulfate, triethylamine lauryl sulfate, tri- ethylamine laureth sulfate, triethanolamine lauryl sulfate, triethanolamine laureth sulfate, monoethanolamine lauryl sulfate, monoethanolamine laureth sulfate, diethanolamine lauryl sulfate, diethanola ine laureth sulfate, lauric monoglyceride sodium sulfate, sodium lauryl sulfate, sodium laureth sulfate, potassium lauryl sulfate, potassium laureth sulfate, sodium lauryl sarcosinate, sodium lauroyl sarcosinate, lauryl sarcosine, cocoyl sarcosine, ammonium cocoyl sulfate
  • the detersive surfactant of the shampoo compositions may comprise an amphoteric and/or zwitterionic surfactant. Concentrations of such surfactants will generally range from about 0.5% to about 20%, preferably from about 1% to about 10%, by weight of the shampoo compositions.
  • Amphoteric surfactants for use in the shampoo compositions include the derivatives of aliphatic secondary and tertiary amines in which the aliphatic radical is straight or branched and one of the aliphatic substituents contains from about 8 to about 18 carbon atoms and one contains an anionic water solubilizing group, e.g., carboxy, sulfonate, sulfate, phosphate, or phosphonate.
  • an anionic water solubilizing group e.g., carboxy, sulfonate, sulfate, phosphate, or phosphonate.
  • Zwitterionic surfactants for use in the shampoo compositions include the derivatives of aliphatic quaternary ammonium, phosphonium, and sulfonium compounds, in which the aliphatic radicals are straight or branched, and wherein one of the aliphatic substituents contains from about 8 to about 18 carbon atoms and one contains an anionic group, e.g., carboxy, sulfonate, sulfate, phosphate, or phosphonate.
  • a general formula 1 A general formula
  • R contains an alkyl, alkenyl, or hydroxy alkyl radical of from about 8 to about 18 carbon atoms, from 0 to about 10 ethylene oxide moieties and from 0 to about 1 glyceryl moiety;
  • Y is selected from the group consisting of nitrogen, phosphorus, and sulfur atoms;
  • R is an alkyl or monohydroxyalkyl group containing about 1 to about 3 carbon atoms;
  • X is 1 when Y is a sulfur atom, and 2
  • R is an alkylene or hydroxyalkylene of from about 1 to about 4 carbon atoms and Z is a radical selected from the group consisting of carboxylate, sulfonate, sulfate, phosphonate, and phosphate groups.
  • amphoteric and zwitterionic surfactants also include sultaines and amidosultaines. Sultaines and amidosultaines can be used as foam enhancing surfactants that are mild to the eye in partial replacement of anionic surfactants.
  • Sultaines including amidosultaines, include for example, cocodimethylpropylsultaine, stearyldimethylpropylsultaine, lauryl-bis-(2-hydroxyethyl) propylsultaine and the like; and the amidosultaines such as cocoamidodimethylpropylsultaine, stearylamidododimethylpropylsultaine, laurylamidobis-(2-hydroxyethyl) propylsultaine, and the like.
  • amidohydroxysultaines such as the Ci2-C ⁇ hydrocarbyl amidopropyl hydroxy- sultaines, especially C12-C14 hydrocarbyl amido propyl hydroxysultaines, e.g., laurylamidopropyl hydroxysultaine and cocamidopropyl hydroxysultaine.
  • Other sultaines are described in U.S. Patent 3,950,417, which descriptions are incorporated herein by reference.
  • amphoteric surfactants are the aminoalkanoates of the formula R-NH(CH2 n COOM, the iminodialkanoates of the formula R-N[(CH 2 ) m COOM] 2 and mixtures thereof; wherein n and m are numbers from 1 to 4, R is Cg - C22 alkyl or alkenyl, and M is hydrogen, alkali metal, alkaline earth metal, ammonium or alkanolammonium.
  • suitable aminoalkanoates include n-alkylamino-propionates and n-alkyliminodipropionates, specific examples of which include N-lauryl- -beta-amino propionic acid or salts thereof, and N-lauryl-beta-imino-dipropionic acid or salts thereof, and mixtures thereof.
  • amphoteric surfactants include d ose represented by the formula :
  • R* is Cg - C22 alkyl or alkenyl, preferably C ⁇ -Cjg
  • R-2 is hydrogen or CH 2 CO 2 M
  • R3 is CH CH 2 OH or CH2CH2OCH2CH2COOM
  • R 4 is hydrogen, CH 2 CH 2 OH, or CH2CH2OCH2CH2COOM
  • Z is CO 2 M or CH 2 CO 2 M
  • n is 2 or 3, preferably 2
  • M is hydrogen or a cation, such as alkali metal (e.g., lithium, sodium, potassium), alkaline earth metal (beryllium, magnesium, calcium, strontium, barium), or ammonium.
  • This type of surfactant is sometimes classified as an imidazoline-type amphoteric surfactant, although it should be recognized that it does not necessarily have to be derived, directly or indirectly, through an imidazoline intermediate.
  • Suitable materials of this type are marketed under the trade name MIRANOL and are understood to comprise a complex mixture of species, and can exist in protonated and non-protonated species depending upon pH with respect to species that can have a hydrogen at R ⁇ . All such variations and species are meant to be encompassed by the above formula.
  • surfactants of the above formula are monocarboxylates and dicarboxylates. Examples of these materials include cocoamphocarboxypropionate, cocoamphocarboxypropionic acid, cocoamphocarboxyglycinate (alternately referred to as cocoamphodiacetate), and cocoamphoacetate.
  • Commercial amphoteric surfactants include those sold under the trade names MIRANOL C2M CONC. N.P., MIRANOL C2M CONC.
  • MIRANOL C2M SF MIRANOL CM SPECIAL (Miranol, Inc.); ALKATERIC 2CIB (Alkaril Chemicals); AMPHOTERGE W-2 (Lonza, Inc.); MONATERIC CDX-38, MONATERIC CSH-32 (Mona Industries); REWOTERIC AM-2C (Rewo Chemical Group); and SCHERCOTERIC MS-2 (Scher Chemicals).
  • Betaine surfactants (zwitterionic) suitable for use in the shampoo compositions are those represented by the formula:
  • R is a member selected from the group consisting of
  • R2 is lower alkyl or hydroxyalkyl
  • R3 is lower alkyl or hydroxyalkyl
  • R4 is a member selected from the group consisting of hydrogen and lower alkyl
  • R5 is higher alkyl or alkenyl
  • Y is lower alkyl, preferably methyl; m is an integer from 2 to 7, preferably from 2 to 3; n is the integer 1 or 0;
  • M is hydrogen or a cation, as previously described, such as an alkali metal, alkaline earth metal, or ammonium.
  • lower alkyl or "hydroxyalkyl” means straight or branch chained, saturated, aliphatic hydrocarbon radicals and substituted hydrocarbon radicals having from one to about three carbon atoms such as, for example, methyl, ethyl, propyl, isopropyl, hydroxypropyl, hydroxyethyl, and the like.
  • higher alkyl or alkenyl means straight or branch chained saturated (i.e., “higher alkyl") and unsaturated (i.e., “higher alkenyl”) aliphatic hydrocarbon radicals having from about eight to about 20 carbon atoms such as, for example, lauryl, cetyl, stearyl, oleyl, and the like. It should be understood that the term “higher alkyl or alkenyl” includes mixtures of radicals which may contain one or more intermediate linkages such as ether or polyether linkages or non-functional substitutents such as hydroxyl or halogen radicals wherein the radical remains of hydrophobic character.
  • surfactant betaines of the- above formula wherein n is zero which are useful herein include the alkylbetaines such as cocodimethylcarboxymethylbetaine, lauryldimethylcarboxymethylbetaine, lauryl dimethyl-alpha-carboxyethylbetaine, cetyldimethylcarboxymethylbetaine, lauryl-bis-(2-hydroxyethyl)carboxymethylbetaine, stearyl-bis-(2-hy- droxypropyl)carboxymethylbetaine, oleyldimethyl-gamma-carboxypropylbetaine, lauryl-bix-(2-hydroxypropyl)alpha-carboxyethylbetaine, etc.
  • alkylbetaines such as cocodimethylcarboxymethylbetaine, lauryldimethylcarboxymethylbetaine, lauryl dimethyl-alpha-carboxyethylbetaine, cetyldimethylcarboxymethylbetaine, lau
  • the sulfobetaines may be represented by cocodimethylsulfopropylbetaine, stearyldimethylsulfo- propylbetaine, lauryl-bis-(2-hydroxyethyl)sulfopropylbetaine, and the like.
  • amido betaines and amidosulfo betaines useful in the shampoo compositions include the amidocarboxybetaines, such as cocoamidodimethylcarboxymethylbetaine, lauxylamidodi- methylcarboxymethylbetaine, cetylamidodimethylcarboxymethylbetaine, laurylamido-bis-(2-hydroxyethyl)-carboxymethylbetaine, cocoamido-bis-(2-hydroxyethyl)-carboxymethylbetaine, etc.
  • amidocarboxybetaines such as cocoamidodimethylcarboxymethylbetaine, lauxylamidodi- methylcarboxymethylbetaine, cetylamidodimethylcarboxymethylbetaine, laurylamido-bis-(2-hydroxyethyl)-carboxymethylbetaine, cocoamido-bis-(2-hydroxyethyl)-carboxymethylbetaine, etc.
  • amido sulfobetaines may be represented by cocoamidodimethylsulfopropylbetaine, stearylamidodimethylsulfopropylbetaine, lauryl- amido-bis-(2-hydroxyethyl)-sulfopropylbetaine, and the like.
  • Nonionic surfactant may be represented by cocoamidodimethylsulfopropylbetaine, stearylamidodimethylsulfopropylbetaine, lauryl- amido-bis-(2-hydroxyethyl)-sulfopropylbetaine, and the like.
  • the shampoo compositions of the present invention may comprise a nonionic surfactant as the detersive surfactant component therein.
  • Nonionic surfactants include those compounds produced by condensation of alkylene oxide groups (hydrophilic in nature) with an organic hydrophobic compound, which may be aliphatic or alkyl aromatic in nature.
  • Preferred nonionic surfactants for use in the shampoo compositions include the following:
  • polyethylene oxide condensates of alkyl phenols e.g., the condensation products of alkyl phenols having an alkyl group containing from about 6 to about 20 carbon atoms in either a straight chain or branched chain configuration, with ethylene oxide, the said ethylene oxide being present in amounts equal to from about 10 to about 60 moles of ethylene oxide per mole of alkyl phenol;
  • ethylene oxide e.g., a coconut alcohol ethylene oxide condensate having from about 10 to about 30 moles of ethylene oxide per mole of coconut alcohol, the coconut alcohol fraction having from about 10 to about 14 carbon atoms
  • R! contains an alkyl, alkenyl or monohydroxy alkyl radical of from about 8 to about 18 carbon atoms, from 0 to about 10 ethylene oxide moieties, and from 0 to about 1 glyceryl moiety, and R 2 and R ⁇ contain from about 1 to about 3 carbon atoms and from 0 to about 1 hydroxy group, e.g., methyl, ethyl, propyl, hydroxyethyl, or hydroxypropyl radicals;
  • R contains an alkyl, alkenyl or monohydroxyalkyl radical ranging from about 8 to about 18 carbon atoms in chain length, from 0 to about 10 ethylene oxide moieties and from 0 to about 1 glyceryl moiety and R' and R" are each alkyl or monohydroxyalkyl groups containing from about 1 to about 3 carbon atoms;
  • long chain dialkyl sulfoxides containing one short chain alkyl or hydroxy alkyl radical of from about 1 to about 3 carbon atoms (usually methyl) and one long hydrophobic chain which include alkyl, alkenyl, hydroxy alkyl, or keto alkyl radicals containing from about 8 to about 20 carbon atoms, from 0 to about 10 ethylene oxide moieties and from 0 to about 1 glyceryl moiety;
  • alkyl polysaccharide (APS) surfactants e.g. alkyl polyglycosides
  • alkyl polysaccharide (APS) surfactants e.g. alkyl polyglycosides
  • alkyl polysaccharide (APS) surfactants having a hydrophobic group with about 6 to about 30 carbon atoms and polysaccharide (e.g., polyglycoside) as the hydrophilic group; optionally, there can be a polyalkylene-oxide group joining the hydrophobic and hydrophilic moieties; and the alkyl group (i.e., the hydrophobic moiety) can be saturated or unsaturated, branched or unbranched, and unsubstituted or substituted (e.g., with hydroxy or cyclic rings); and
  • polyethylene glycol (PEG) glyceryl fatty esters such as those of the formula R(O)OCH 2 CH(OH)CH 2 (OCH 2 CH 2 ) n OH wherein n is from about 5 to about 200, preferably from about 20 to about 100, and R is an aliphatic hydrocarbyl having from about 8 to about 20 carbon atoms.
  • Optional cationic surfactants for use as hair conditioning agents in the shampoo compositions will typically contain quaternary nitrogen moieties.
  • suitable cationic surfactants are described in following documents, all of which are incorporated by reference herein in their entirety: M.C. Publishing Co., McCutcheon's, Detergents & Emulsifiers, (North American edition 1979); Schwartz, et al., Surface Active Agents, Their Chemistry and Technology, New York: Interscience Publishers, 1949; U.S. Patent 3,155,591; U. S. Patent 3,929,678; U. S. Patent 3,959,461 and U. S. Patent 4,387,090.
  • Suitable cationic surfactants are those corresponding to the general formula:
  • R ⁇ , R2, R3, and R4 are independently selected from an aliphatic group of from 1 to about 22 carbon atoms or an aromatic, alkoxy, polyoxyalkylene, alkylamido, hydroxyalkyl, aryl or alkylaryl group having up to about 22 carbon atoms; and X is a salt-forming anion such as those selected from halogen, (e.g. chloride, bromide), acetate, citrate, lactate, glycolate, phosphate nitrate, sulfate, and alkylsulfate radicals.
  • the aliphatic groups can contain, in addition to carbon and hydrogen atoms, ether linkages, and other groups such as amino groups.
  • the longer chain aliphatic groups e.g., those of about 12 carbons, or higher, can be saturated or unsaturated.
  • R ⁇ , R2, R3, and R4 are independently selected from Cl to about C22 alkyl.
  • cationic materials containing two long alkyl chains and two short alkyl chains or those containing one long alkyl chain and three short alkyl chains.
  • the long alkyl chains in the compounds described in the previous sentence have from about 12 to about 22 carbon atoms, preferably from about 16 to about 22 carbon atoms, and the short alkyl chains in the compounds described in the previous sentence have from 1 to about 3 carbon atoms, preferably from 1 to about 2 carbon atoms.
  • the shampoo compositions of the present invention preferably also comprise a silicone hair conditioning agent at concentrations effective to provide hair conditioning benefits. Such concentrations range from about .05% to about 10%, preferably from about 0.1% to about 8%, more preferably from about 0.1% to about 5%, most preferably from about 0.2% to about 3%, by weight of the shampoo compositions.
  • the silicone hair conditioning agents for use in the shampoo compositions are insoluble in the shampoo compositions, and are preferably nonvolatile. Typically it will be intermixed in the shampoo composition so as to be in the form of a separate, discontinuous phase of dispersed, insoluble particles, also referred to as droplets. These droplets are suspended witii a suspending agent described hereinafter.
  • the silicone hair conditioning agent phase will comprise a silicone fluid hair conditioning agent such as a silicone fluid and can also comprise other ingredients, such as a silicone resin to enhance silicone fluid deposition efficiency or enhance glossiness of the hair (especially when high refractive index (e.g. above about 1.46) silicone conditioning agents are used (e.g. highly phenylated silicones).
  • nonvolatile refers to silicone material with little or no significant vapor pressure under ambient conditions, as is understood by those in the art. Boiling point under one atmosphere (atm) will preferably be at least about 250°C, more preferably at least about 275°C, most preferably at least about 300°C. Vapor pressure is preferably about 0.2mm HG at 25°C or less, preferably about 0.1mm HG at 25°C or less.
  • the silicone hair conditioning agent phase may comprise volatile silicone, nonvolatile silicone, or mixtures thereof. Typically, if volatile silicones are present, it will be incidental to their use as a solvent or carrier for commercially available forms of nonvolatile silicone materials ingredients, such as silicone gums and resins.
  • the silicone hair conditioning agents for use in the shampoo compositions preferably have a viscosity of from about 20 to about 2,000.000 centistokes, more preferably from about 1,000 to about 1,800,000 centistokes, even more preferably from about 50,000 to about 1,500,000 centistokes, most preferably from about 100,000 to about 1,500,000 centistokes, at 25°C.
  • the viscosity can be measured by means of a glass capillary viscometer as set forth in Dow Corning Corporate Test Method CTM0004, July 20, 1970.
  • Silicone fluid for use in the shampoo compositions includes silicone oil which are flowable silicone materials with a viscosity of less than 1,000,000 centistokes, preferably between about 5 and 1,000,000 centistokes, more preferably between about 10 and about 100,000 centistokes, at 25°C.
  • Suitable silicone oils include polyalkyl siloxanes, polyaryl siloxanes, polyalkylaryl siloxanes, polyether siloxane copolymers, and mixtures thereof.
  • Other insoluble, nonvolatile silicone fluids having hair conditioning properties can also be used.
  • Silicone oils for use in the composition include polyalkyl or polyaryl siloxanes of the following structure (I)
  • R is aliphatic, preferably alkyl or alkenyl, or aryl
  • R can be substituted or unsubstituted
  • x is an integer from 1 to about 8,000.
  • Suitable unsubstituted R groups include alkoxy, aryloxy, alkaryl, arylalkyl, arylalkenyl, alkamino, and ether- substituted, hydroxyl-substituted, and halogen-substituted aliphatic and aryl groups.
  • Suitable R groups also include cationic amines and quaternary ammonium groups.
  • the aliphatic or aryl groups substituted on the siloxane chain may have any structure as long as the resulting silicones remain fluid at room temperature, are hydrophobic, are neither irritating, toxic nor otherwise harmful when applied to the hair, are compatible with the other components of the shampoo compositions, are chemically stable under normal use and storage conditions, are insoluble in the shampoo compositions, and are capable of being deposited on and, of conditioning, the hair.
  • the two R groups on the silicon atom of each monomeric silicone unit may represent the same group or different groups.
  • the two R groups represent the same group.
  • Preferred alkyl and alkenyl substituents are C1-C5 alkyls and alkenyls, more preferably from C1-C4, most preferably from C1-C2.
  • the aliphatic portions of other alkyl-, alkenyl-, or alkynyl-containing groups can be straight or branched chains and preferably have from one to five carbon atoms, more preferably from one to four carbon atoms, even more preferably from one to three carbon atoms, most preferably from one to two carbon atoms.
  • the R substituents hereof can also contain amino functionalities, e.g.
  • alkamino groups which can be primary, secondary or tertiary amines or quaternary ammonium. These include mono-, di- and tri- alkylamino and alkoxyamino groups wherein the aliphatic portion chain length is preferably as described above.
  • the R substituents can also be substituted with other groups, such as halogens (e.g. chloride, fluoride, and bromide), halogenated aliphatic or aryl groups, and hydroxy (e.g. hydroxy substituted aliphatic groups).
  • Suitable halogenated R groups could include, for example, tri- halogenated (preferably fluoro) alkyl groups such as -Rl-C(F)3, wherein R is C1-C3 alkyl.
  • tri- halogenated (preferably fluoro) alkyl groups such as -Rl-C(F)3, wherein R is C1-C3 alkyl.
  • polysiloxanes include polymethyl -3,3,3 trifluoropropylsiloxane.
  • Suitable R groups include methyl, ethyl, propyl, phenyl, methylphenyl and phenylmethyl.
  • the preferred silicones are polydimethyl siloxane, polydiethylsilox- ane, and polymethylphenylsiloxane. Polydimethylsiloxane is especially preferred.
  • R groups include methyl, methoxy, ethoxy, propoxy, and aryloxy.
  • the three R groups on the end caps of the silicone may also represent the same or different groups.
  • the nonvolatile polyalkylsiloxane fluids that may be used include, for example, polydimethylsiloxanes. These siloxanes are available, for example, from the General Electric Company in their Viscasil R and SF 96 series, and from Dow Corning in their Dow Corning 200 series.
  • polyalkylaryl siloxane fluids that may be used, also include, for example, polymethylphenylsiloxanes. These siloxanes are available, for example, from the General Electric Company as SF 1075 methyl phenyl fluid or from Dow Corning as 556 Cosmetic Grade Fluid.
  • the polyether siloxane copolymers that may be used include, for example, a polypropylene oxide modified polydimethylsiloxane (e.g., Dow Corning DC-1248) although ethylene oxide or mixtures of ethylene oxide and propylene oxide may also be used.
  • a polypropylene oxide modified polydimethylsiloxane e.g., Dow Corning DC-1248
  • ethylene oxide or mixtures of ethylene oxide and propylene oxide may also be used.
  • the ethylene oxide and polypropylene oxide level must be sufficiently low to prevent solubility in water and the composition hereof.
  • Suitable alkylamino substituted silicones include those represented by the following structure (II)
  • x and y are integers which depend on the molecular weight, the average molecular weight being approximately between 5,000 and 10,000.
  • This polymer is also known as "amodimethicone".
  • Suitable cationic silicone fluids include those represented by the formula (III):
  • Ri is a monovalent radical of formula CqH2qL in which q is an integer from 2 to 8 and L is chosen from the groups
  • R2 is chosen from the group consisting of hydrogen, phenyl, benzyl, a saturated hydrocarbon radical, preferably an alkyl radical containing from 1 to 20 carbon atoms, and A " denotes a halide ion.
  • silicone cationic polymers which can be used in the shampoo compositions are represented by the formula (V):
  • R ⁇ denotes a monovalent hydrocarbon radical having from 1 to 18 carbon atoms, preferably an alkyl or alkenyl radical such as methyl
  • R4 denotes a hydrocarbon radical, preferably a Ci-Cjg alkylene radical or a C -C ⁇ g, and more preferably Cj-Cg, alkyleneoxy radical
  • Q " is a halide ion, preferably chloride
  • r denotes an average statistical value from 2 to 20, preferably from 2 to 8
  • s denotes an average statistical value from 20 to 200, and preferably from 20 to 50.
  • a preferred polymer of this class is available from Union Carbide under the name "UCAR SILICONE ALE 56.”
  • silicone fluids for use in the silicone conditioning agents are insoluble silicone gums. These gums are polyorganosiloxane materials having a viscosity at 25°C of greater than or equal to 1,000,000 centistokes. Silicone gums are described in U.S. Patent 4,152,416; Noll and Walter, Chemistry and Technology of Silicones. New York: Academic Press 1968; and in General Electric Silicone Rubber Product Data Sheets SE 30, SE 33, SE 54 and SE 76, all of which are incorporated herein by reference.
  • the silicone gums will typically have a mass molecular weight in excess of about 200,000, generally between about 200,000 and about 1,000,000, specific examples of which include polydimethylsiloxane, (polydimethylsiloxane) (methylvinylsiloxane) copolymer, poly(dimethylsiloxane) (diphenyl siloxane)(methyl- vinylsiloxane) copolymer and mixtures thereof.
  • the silicone hair conditioning agent preferably comprises a mixture of polydimethylsiloxane gum (viscosity greater than about 1,000,000 centistokes) and polydimethylsiloxane oil (viscosity from about 10 to about 100,000 centistokes), wherein the ratio of gum to fluid is from about 30:70 to about 70:30, preferably from about 40:60 to about 60:40.
  • nonvolatile, insoluble silicone fluid conditioning agents are high refractive index silicones, having a refractive index of at least about 1.46, preferably at least about 1.48, more preferably at least about 1.52, most preferably at least about 1.55. Although not intended to necessarily be limiting, the refractive index of the polysiloxane fluid will generally be less than about 1.70, typically less than about 1.60.
  • Polysiloxane "fluid" includes oils as well as gums.
  • the high refractive index polysiloxane fluid suitable for purposes hereof includes those represented by general Formula (I) above, as well as cyclic polysiloxanes such as those represented by Formula (VI) below:
  • n is from about 3 to about 7, preferably from 3 to 5.
  • the high refractive index polysiloxane fluids contain a sufficient amount of aryl-containing R substituents to increase the refractive index to the desired level, which is described above.
  • R and n must be selected so that the material is nonvolatile, as defined above.
  • Aryl-containing substituents contain alicyclic and heterocyclic five and six membered aryl rings, and substituents containing fused five or six membered rings.
  • the aryl rings themselves can be substituted or unsubstituted.
  • Substituents include aliphatic substituents, and can also include alkoxy substituents, acyl substituents, ketones, halogens (e.g., Cl and Br), amines, etc.
  • aryl-containing groups include substituted and unsubstituted arenes, such as phenyl, and phenyl derivatives such as phenyls with C, -C ⁇ - alkyl or alkenyl substituents, e.g., allylphenyl, methyl phenyl and ediyl phenyl, vinyl phenyls such as styrenyl, and phenyl alkynes (e.g. phenyl C 2 -C 4 alkynes).
  • Heterocyclic aryl groups include substituents derived from furan, imidazole, pyrrole, pyridine, etc.
  • Fused aryl ring substituents include, for example, napthalene, coumarin, and purine.
  • the high refractive index polysiloxane fluids will have a degree of aryl-containing substituents of at least about 15%, preferably at least about 20%, more preferably at least about 25%, even more preferably at least about 35%, most preferably at least about 50%.
  • the degree of aryl substitution will be less than about 90%, more generally less than about 85%, preferably from about 55% to about 80%.
  • the polysiloxane fluids are also characterized by relatively high surface tensions as a result of their aryl substitution.
  • the polysiloxane fluids are also characterized by relatively high surface tensions as a result of their aryl substitution.
  • the polysiloxane fluids are also characterized by relatively high surface tensions as a result of their aryl substitution.
  • the polysiloxane fluids are also characterized by relatively high surface tensions as a result of their aryl substitution.
  • Preferred high refractive index polysiloxane fluids have a combination of phenyl or phenyl derivative substituents (preferably phenyl), with alkyl substituents, preferably C1-C4 alkyl (most preferably methyl), hydroxy, C1-C4 alkylamino (especially -R'NHR NH2 where each R and R independently is a C, -C, alkyl, alkenyl, and/or alkoxy.
  • High refractive index polysiloxanes are available from Dow Corning Corporation (Midland, Michigan, U.S.A.) Huls America (Piscataway, New Jersey, U.S.A.), and General Electric Silicones (Waterford, New York, U.S.A.).
  • the spreading agent will preferably reduce the surface tension by at least about 2 dynes/cm 2 , preferably at least about 3 dynes/cm 2 , even more preferably at least about 4 dynes/cm 2 , most preferably at least about 5 dynes/cm 2.
  • the surface tension of the mixture of d e polysiloxane fluid and the spreading agent, at the proportions present in the final product, is preferably 30 dynes/cm" or less, more preferably about 28 dynes/cm 2 or less most preferably about 25 dynes/cm 2 or less. Typically the surface tension will be in the range of from about 15 to about
  • the weight ratio of the highly arylated polysiloxane fluid to the spreading agent will, in general, be between about 1000:1 and about 1 :1, preferably between about 100:1 and about 2:1, more preferably between about 50:1 and about 2:1, most preferably from about 25:1 to about 2:1.
  • fluorinated surfactants particularly high polysiloxane: spreading agent ratios may be effective due to the efficiency of these surfactants.
  • mat ratios significantly above 1000:1 may be used.
  • Silicone resins can be included in the silicone conditioning agent. These resins are highly crosslinked polymeric siloxane systems. The crosslinking is introduced through the incorporation of trifunctional and tetrafunctional silanes with monofunctional or difunctional, or both, silanes during manufacture of the silicone resin. As is well understood in the art, the degree of crosslinking that is required in order to result in a silicone resin will vary according to the specific silane units incorporated into the silicone resin. In general, silicone materials which have a sufficient level of trifunctional and tetrafunctional siloxane monomer units (and hence, a sufficient level of crosslinking) such that they dry down to a rigid, or hard, film are considered to be silicone resins.
  • the ratio of oxygen atoms to silicon atoms is indicative of the level of crosslinking in a particular silicone material.
  • Silicone materials which have at least about 1.1 oxygen atoms per silicon atom will generally be silicone resins herein.
  • the ratio of oxygen:silicon atoms is at least about 1.2:1.0.
  • Silanes used in the manufacture of silicone resins include monomethyl-, dimethyl-, trimethyl-, monophenyl-, diphenyl-, methylphenyl-, monovinyl-, and methylvinyl-chlorosilanes, and tetrachlorosilane, with the methyl-substituted silanes being most commonly utilized.
  • Preferred resins are offered by General Electric as GE SS4230 and SS4267.
  • Commercially available silicone resins will generally be supplied in a dissolved form in a low viscosity volatile or nonvolatile silicone fluid.
  • the silicone resins for use herein should be supplied and incorporated into the present compositions in such dissolved form, as will be readily apparent to those skilled in the art.
  • Silicone materials and silicone resins in particular can conveniently be identified according to a shorthand nomenclature system well known to those skilled in the art as "MDTQ" nomenclature. Under this system, the silicone is described according to presence of various siloxane monomer units which make up the silicone. Briefly, the symbol M denotes the monofunctional unit (CH3>3SiO 5; D denotes the difunctional unit (CH3)2SiO; T denotes the trifunctional unit (CH3)SiO ⁇ 5; and Q denotes the quadri- or tetra-functional unit Si ⁇ 2- Primes of the unit symbols, e.g., M', D', T', and Q' denote substituents other than methyl, and must be specifically defined for each occurrence.
  • Typical alternate substituents include groups such as vinyl, phenyls, amines, hydroxyls, etc.
  • the molar ratios of the various units, eid er in terms of subscripts to the symbols indicating the total number of each type of unit in the silicone (or an average thereof) or as specifically indicated ratios in combination with molecular weight complete the description of the silicone material under the MDTQ system.
  • Higher relative molar amounts of T, Q, T' and/or Q' to D, D', M and/or M' in a silicone resin is indicative of higher levels of crosslinking.
  • the overall level of crosslinking can also be indicated by the oxygen to silicon ratio.
  • the silicone resins for use herein which are preferred are MQ, MT, MTQ, MDT and MDTQ resins.
  • the preferred silicone substituent is methyl.
  • MQ resins wherein the M:Q ratio is from about 0.5:1.0 to about 1.5:1.0 and the average molecular weight of the resin is from about 1000 to about 10,000.
  • the weight ratio of the nonvolatile silicone fluid, having refractive index below 1.46, to the silicone resin component, when used, is preferably from about 4:1 to about 400: 1, preferably this ratio is from about 9:1 to about 200:1, more preferably from about 19:1 to about 100:1, particularly when the silicone fluid component is a polydimethylsiloxane fluid or a mixture of polydimethylsiloxane fluid and polydimethylsiloxane-gum as described above.
  • the silicone resin forms a part of the same phase in the compositions hereof as the silicone fluid, i.e. the conditioning active, the sum of the fluid and resin should be included in determining the level of silicone conditioning agent in the composition.
  • the shampoo compositions of the present invention may further comprise selected polyalkylene glycols in amounts effective to enhance lather performance and enhance spreadability of the shampoo compositions on hair. Effective concentrations of the selected polyed ylene glycols range from about 0.025% to about 1.5%, preferably from about 0.05% to about 1%, more preferably from about 0.1% to about 0.5%, by weight of the shampoo compositions.
  • polyalkylene glycols suitable for use in the shampoo compositions are characterized by the general formula:
  • R is hydrogen, methyl or mixtures thereof, preferably hydrogen, and n is an integer having an average value of from about 1,500 to about 25.000, preferably from about 2,500 to about 20,000, and more preferably from about 3.500 to about 15,000.
  • R is hydrogen
  • these materials are polymers of ethylene oxide, which are also known as polyethylene oxides, polyoxyethylenes, and polyethylene glycols.
  • R is methyl
  • these materials are polymers of propylene oxide, which are also known as polypropylene oxides, polyoxypropylenes, and polypropylene glycols.
  • R is methyl, it is also understood that various positional isomers of the resulting polymers can exist.
  • suitable polyethylene glycol polymers include PEG-2M wherein R equals hydrogen and n has an average value of about 2,000 (PEG 2-M is also known as Polyox WSR® N-10, which is available from Union Carbide and as PEG-2,000); PEG-5M wherein R is hydrogen and n has an average value of about 5,000 (PEG 5-M is also known as Polyox WSR® N-35 and Polyox WSR® N-80, both available from Union Carbide and as PEG-5,000 and Polyethylene Glycol 300,000); PEG-7M wherein R is hydrogen and n has an average value of about 7,000 (PEG 7-M is also known as Polyox WSR® N-750 available from Union Carbide); PEG-9M wherein R is hydrogen and n has an average value of about 9,000 (PEG 9-M is also known as Polyox WSR® N-3333 available from Union Carbide); and PEG-14 M wherein R is hydrogen and n has an average value of about 14,000 (PEG 14-M where
  • the shampoo compositions of the present invention may further comprise a suspending agent at concentrations effective for suspending the silicone hair conditioning agent in dispersed form in the shampoo compositions. Such concentrations range from about 0.1% to about 10%, preferably from about 0.3% to about 5.0%, by weight of the shampoo compositions.
  • Suitable suspending agents include acyl derivatives, long chain amine oxides, and mixtures thereof, concentrations of which range from about 0.1% to about 5.0%, preferably from about 0.5% to about 3.0%, by weight of the shampoo compositions. When used in the shampoo compositions, these suspending agents are present in crystalline form. These suspending agents are described in U.S. Patent 4,741,855, which description is incorporated herein by reference. These preferred suspending agents include ethylene glycol esters of fatty acids preferably having from about 16 to about 22 carbon atoms. More preferred are the ethylene glycol stearates, both mono and distearate, but particularly the distearate containing less than about 7% of the mono stearate.
  • suspending agents include alkanol amides of fatty acids, preferably having from about 16 to about 22 carbon atoms, more preferably about 16 to 18 carbon atoms, preferred examples of which include stearic monoethanolamide, stearic diedianolamide, stearic monoisopropanolamide and stearic monoethanolamide stearate.
  • long chain acyl derivatives include long chain esters of long chain fatty acids (e.g., stearyl stearate, cetyl palmitate, etc.); glyceryl esters (e.g., glyceryl distearate) and long chain esters of long chain alkanol amides (e.g., stearamide diethanolamide distearate, stearamide monoethanolamide stearate).
  • Long chain acyl derivatives, ethylene glycol esters of long chain carboxylic acids, long chain amine oxides, and alkanol amides of long chain carboxylic acids in addition to the preferred materials listed above may be used as suspending agents.
  • suspending agents with long chain hydrocarbyls having Cg-C22 chains may be used.
  • acyl derivatives suitable for use as suspending agents include N,N-dihydrocarbyl amido benzoic acid and soluble salts thereof (e.g., Na and K salts), particularly N,N-di(hydrogenated) Cig, Cig and tallow amido benzoic acid species of this family, which are commercially available from Stepan Company (Northfield, Illinois, USA).
  • suitable long chain amine oxides for use as suspending agents include alkyl (C ⁇ g-C22) dimethyl amine oxides, e.g., stearyl dimethyl amine oxide
  • suitable suspending agents include xanthan gum at concentrations ranging from about 0.3% to about 3%, preferably from about 0.4% to about 1.2%, by weight of the shampoo compositions.
  • xanthan gum as a suspending agent in silicone containing shampoo compositions is described, for example, in U.S. Patent 4,788,006, which description is incorporated herein by reference.
  • Combinations of long chain acyl derivatives and xanthan gum may also be used as a suspending agent in the shampoo compositions. Such combinations are described in U.S. Patent 4,704,272, which description is incorporated herein by reference.
  • suspending agents include carboxy vinyl polymers. Preferred among these polymers are the copolymers of acrylic acid crosslinked with polyallylsucrose as described in U.S. Patent 2,798,053, which description is incorporated herein by reference. Examples of these polymers include Carbopol 934, 940, 941, and 956, available from B. F. Goodrich Company .
  • 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 monoolefmic monomeric materials may be present in the monomeric mixture if desired, even in predominant proportion.
  • Carboxyvinyl polymers are substantially insoluble in liquid, volatile organic hydrocarbons and are dimensionally stable on exposure to air.
  • Preferred polyhydric alcohols used to produce carboxyvinyl polymers include polyols selected from the class consisting of oligosaccharides, reduced derivatives thereof in which the carbonyl group is converted to an alcohol group, and pentaerythritol; more preferred are oligosaccharides, most preferred is sucrose. It is preferred that the hydroxyl groups of the polyol which are modified be etherified with allyl groups, the polyol having at least two allyl ether groups per polyol molecule. When the polyol is sucrose, it is preferred that the sucrose have at least about five allyl ether groups per sucrose molecule. It is preferred that the polyether of the polyol comprise from about 0.1% to about 4% of the total monomers, more preferably from about 0.2% to about 2.5%.
  • Preferred monomeric olefinically unsaturated carboxylic acids for use in producing carboxyvinyl polymers used herein include monomeric, polymerizable, alpha-beta monoolefmically unsaturated lower aliphatic carboxylic acids; more preferred are monomeric of the structure
  • R is a substituent selected from the group consisting of hydrogen and lower alkyl groups; most preferred is acrylic acid.
  • Preferred carboxyvinyl polymers have a molecular weight of at least about 750,000; more preferred are carboxyvinyl polymers having a molecular weight of at least about 1,250,000; most preferred are carboxyvinyl polymers having a molecular weight of at least about 3,000,000.
  • suspending agents include nonionic suspending agents.
  • suspending agents include primary amines having a fatty alkyl moiety having at least about 16 carbon atoms, examples of which include palmitamine or stearamine, and secondary amines having two fatty alkyl moieties each having at least about 12 carbon atoms, examples of which include dipalmitoylamine or di(hydrogenated tallow)amine. Still other suitable suspending agents include di(hydrogenated tallow)phthalic acid amide, and crosslinked maleic anhydride-methyl vinyl edier copolymer.
  • suspending agents may be used in the shampoo compositions, including those that can impart a gel-like viscosity to the composition, such as water soluble or colloidally water soluble polymers like cellulose ethers (e.g., methylcellulose, hydroxybutyl methylcellulose, hyroxypropylcellulose, hydroxypropyl methylcellulose, hydroxyethyl ethylcellulose and hydorxethylcellulose), guar gum, polyvinyl alcohol, polyvinyl pyrrolidone, hydroxypropyl guar gum, starch and starch derivatives, and other thickeners, viscosity modifiers, gelling agents, etc. Mixtures of these materials can also be used.
  • water soluble or colloidally water soluble polymers like cellulose ethers (e.g., methylcellulose, hydroxybutyl methylcellulose, hyroxypropylcellulose, hydroxypropyl methylcellulose, hydroxyethyl ethylcellulose and
  • the shampoo compositions of the present invention comprise from about 20% to about 94.8%, preferably from about 50% to about 94.8%, more preferably from about 60% to about 85%, by weight of water.
  • the shampoo compostions of d e present invention may f rther comprise water soluble cationic polymeric conditioning agents, hydrocarbon conditioning agents, and mixtures thereof.
  • Optional cationic polymers for use as hair conditioning agents are ose having a weight average molecular weight of from about 5,000 to about 10 million, and will generally have cationic nitrogen-containing moieties such as quaternary ammonium or cationic amino moieties, and mixtures d ereof.
  • Cationic charge density should be at least about 0.1 meq/gram, preferably less than about 3.0 meq/gram, which can be determined according to the well known Kjeldahl Method. Those skilled in the art will recognize that the charge density of amino-containing polymers can vary depending upon pH and the isoelectric point of the amino groups. The charge density should be within the above limits at the pH of intended use. Any anionic counterions can be utilized for the cationic polymers so long as the water solubility criteria is met.
  • the cationic nitrogen-containing moiety will be present generally as a substituent, on a fraction of the total monomer units of the cationic hair conditioning polymers.
  • the cationic polymer can comprise copolymers, terpolymers, etc. of quaternary ammonium or cationic amine-substituted monomer units and other non-cationic units referred to herein as spacer monomer units.
  • Such polymers are known in the art, and a variety can be found in International Cosmetic Ingredient Dicitonary, Fifth Edition, 1993, which is incorporated by reference herein in its entirety.
  • Suitable optional cationic polymers include, for example, copolymers of vinyl monomers having cationic amine or quaternary ammonium functionalities with water soluble spacer monomers such as acrylamide, methacrylamide, alkyl and dialkyl acrylamides, alkyl and dialkyl methacrylamides, alkyl acrylate. alkyl methacrylate, vinyl caprolactone, and vinyl pyrrolidone.
  • the alkyl and dialkyl substituted monomers preferably have C1-C7 alkyl groups, more preferably C1-C3 alkyl groups.
  • Other suitable spacer monomers include vinyl esters, vinyl alcohol (made by hydrolysis of polyvinyl acetate), maleic anhydride, propylene glycol, and ethylene glycol.
  • the cationic amines can be primary, secondary, or tertiary amines, depending upon the particular species and the pH of the composition. In general, secondary and tertiary amines, especially tertiary amines, are preferred.
  • the cationic polymers can comprise mixtures of monomer units derived from amine- and/or quaternary ammonium-substituted monomer and/or compatible spacer monomers.
  • Otiier cationic polymers that can be used include polysaccharide polymers, such as cationic cellulose derivatives, cationic starch derivative, and cationic guar gum derivatives.
  • Other materials include quaternary nitrogen-containing cellulose ethers as described in U.S. Patent 3,962,418, and copolymers of etherified cellulose and starch as described in U.S. Patent 3,958,581, which descriptions are incorporated herein by reference.
  • the shampoo compositions of the present invention may comprise one or more optional ingredients to improve or otherwise modify a variety of product characteristics, including aesthetics, stability and use benefits.
  • optional ingredients are known in the art and may be used in the shampoo compositions herein, provided mat such ingredients are compatible with me essential ingredients described herein, or do not otherwise unduly impair cleansing or conditioning performance of the shampoo compositions.
  • the shampoo compositions of the present invention are intended for application to the hair and scalp, and will typically be applied using the hands and fingers.
  • the shampoo compositions must therefore be safe and suitable for frequent (e.g. daily) use. Ingredients unsuitable for such frequent application should not be used at levels which would be unacceptable for frequent use, or which could cause undue irritation or damage to the hair or skin.
  • the shampoo compositions of the present invention are therefore essentially free of such materials.
  • Optional materials include foam boosters, preservatives, mickeners, cosurfactants, dyes, perfumes, solvents, styling polymers, anti-static agents, anti- dandruff aids, and pediculocides.
  • Preferred optional materials include foam boosters, especially fatty ester (e.g. C8-C22) mono- and di (C1-C5, especially C1-C3) alkanol amides, specific examples of which include coconut monoethanolamide and coconut diethanolamide.
  • foam boosters especially fatty ester (e.g. C8-C22) mono- and di (C1-C5, especially C1-C3) alkanol amides, specific examples of which include coconut monoethanolamide and coconut diethanolamide.
  • Suitable optional materials include preservatives such as benzyl alcohol, methyl paraben, propyl paraben and imidazolidinyl urea; fatty alcohols; block polymers of ethylene oxide and propylene oxide such as Pluronic F88 offered by BASF Wyandotte; sodium chloride, sodium sulfate; ammonium xylene sulfonate; propylene glycol; polyvinyl alcohol; ethyl alcohol; pH adjusting agents such as citric acid, succinic acid, phosphoric acid, sodium hydroxide, sodium carbonate, etc.; perfumes; and dyes.
  • preservatives such as benzyl alcohol, methyl paraben, propyl paraben and imidazolidinyl urea
  • fatty alcohols block polymers of ethylene oxide and propylene oxide such as Pluronic F88 offered by BASF Wyandotte
  • Optional anti-static agents such as water-insoluble cationic surfactants may also be used, but should not unduly interfere with the in-use performance and end- benefits of the shampoo composition; particularly, the anti-static agent should not interfere with the anionic detersive surfactant.
  • Suitable anti-static agents include tricetyl methyl ammonium chloride. Concentrations of such agents can range from about 0.1% to about 5% by weight of the shampoo compositions.
  • Optional antidandruff agents include particulate antidandruff agents such as pyridinethione salts, selenium compounds such as selenium disulfide, and soluble antidandruff agents. Concentrations of optional antidandruff agents range from about 0.1% to about 4%, preferably about 0.2% to about 2%, by weight of the shampoo compositions.
  • compositions illustrated in Examples 10-14 illustrate specific embodiments of the shampoo compositions of the present invention, but are not intended to be limiting ⁇ ereof. Otiier modifications can be undertaken by the skilled artisan wimout departing from the spirit and scope of this invention.
  • the compositions illustrated in Examples 10-14 may be prepared in the following manner (all percentages are based on weight unless otherwise specified).
  • a silicone premix is prepared by adding 70% dimethicone, 29% ammonium laureth-2 sulfate (solution basis, 26% active) and 1% sodium chloride, all by weight of the silicone premix, to a high shear mixing vessel and mixing for about 30 minutes or until the desired silicone particle size is achieved (typically a number average particle size of from about 5 microns to about 25 microns).
  • a conventional silicon emulsion may also be used.
  • dianionic ester cleaning agent surfactant For each of me compositions illustrated in Examples 10-14, about one-third to all of the total dianionic ester cleaning agent surfactant is added to a jacketed mix tank and heated to about 74°C with slow agitation to form a surfactant solution.
  • Cocamide monoethanolamide and fatty alcohol, as applicable, are added to the tank and allowed to disperse.
  • Ethylene glycol distearate (EGDS) is then added to the mixing vessel, and melted. After the EGDS is well dispersed (usually after about 5 to 20 minutes) optional preservative are added and mixed into the surfactant solution. This mixture is passed through a heat exchanger where it is cooled to about 35°C and collected in a finishing tank.
  • the ethylene glycol distearate crystallizes to form a crystalline network in the product.
  • the remainder of the ammonium laureth sulfate, lauryl sulfate and other ingredients including the silicone premix are added to the finishing tank with ample agitation to insure a homogeneous mixture. A sufficient amount of the silicone premix is added to provide the desired level of dimethicone in the final product.
  • Polyethylene glycol and optional Polyquaternium 10 are dispersed in water as a 1% to 10% solution before addition to the final mix.
  • ammonium xylene sulfonate or additional sodium chloride can be added to the mixture to thin or thicken respectively to achieve a desired product viscosity.
  • Preferred viscosities range from about 3500 to about 9000 centistokes at 25°C (as measured by a Wells-Brookfield cone and plate viscometer at 2/s at 3 minutes).
  • compositions illustrated in Examples 10-14 all of which are embodiments of the present invention, provide excellent cleansing and conditioning of hair.
  • Dime icone is a 40(gum)/60(fluid) weight ratio blend of SE-76 dimethicone gum available from General Electric Silicones Division and a dimethicone fluid having a viscosity of 350 centistokes.
  • Dianionic is the isethionate ester or the alkoxylated isetfiionate ester of alpha- sulfonated C 2/C14 fatty acid.

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Abstract

L'invention concerne une composition nettoyante liquide comprenant un système tensioactif qui contient un agent nettoyant constitué d'un ester dianionique ou dianionique alcoxylé, choisi entre les esters alpha-sulfonés substitués ou non substitués, saturés ou insaturés, ramifiés ou linéaires, d'alcools sulfonates C2-C6 (de préférence C2-C4), éventuellement alcoxylés.
PCT/US1997/013746 1996-08-07 1997-08-05 Compositions nettoyantes liquides contenant des esters dianioniques WO1998005742A1 (fr)

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Cited By (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20130333204A1 (en) * 2012-06-15 2013-12-19 Samsung Electro-Mechanics Japan Advanced Technology Co., Ltd. Method of manufacturing hard disk drive device and hard disk drive device
US8921295B2 (en) 2010-07-23 2014-12-30 American Sterilizer Company Biodegradable concentrated neutral detergent composition
US9745543B2 (en) 2012-09-10 2017-08-29 Ecolab Usa Inc. Stable liquid manual dishwashing compositions containing enzymes
US10626350B2 (en) 2015-12-08 2020-04-21 Ecolab Usa Inc. Pressed manual dish detergent
DE102018127180A1 (de) * 2018-10-31 2020-04-30 Henkel Ag & Co. Kgaa Wirkstoffzusammensetzung zur Pflege von Humanhaaren

Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2806044A (en) * 1955-01-14 1957-09-10 James K Weil Esters of hydroxyalkanesulfonates with alpha-sulfonated long-chain fatty acids
US5519154A (en) * 1994-01-10 1996-05-21 Huntsman Corporation Ethoxylated ester surfactants and a process therefor

Patent Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2806044A (en) * 1955-01-14 1957-09-10 James K Weil Esters of hydroxyalkanesulfonates with alpha-sulfonated long-chain fatty acids
US5519154A (en) * 1994-01-10 1996-05-21 Huntsman Corporation Ethoxylated ester surfactants and a process therefor

Cited By (9)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US8921295B2 (en) 2010-07-23 2014-12-30 American Sterilizer Company Biodegradable concentrated neutral detergent composition
US20130333204A1 (en) * 2012-06-15 2013-12-19 Samsung Electro-Mechanics Japan Advanced Technology Co., Ltd. Method of manufacturing hard disk drive device and hard disk drive device
US9745543B2 (en) 2012-09-10 2017-08-29 Ecolab Usa Inc. Stable liquid manual dishwashing compositions containing enzymes
US10723974B2 (en) 2012-09-10 2020-07-28 Ecolab Usa Inc. Stable liquid manual dishwashing compositions containing enzymes
US10626350B2 (en) 2015-12-08 2020-04-21 Ecolab Usa Inc. Pressed manual dish detergent
US11268045B2 (en) 2015-12-08 2022-03-08 Ecolab Usa Inc. Pressed manual dish detergent
US11746304B2 (en) 2015-12-08 2023-09-05 Ecolab Usa Inc. Pressed manual dish detergent
US12227717B2 (en) 2015-12-08 2025-02-18 Ecolab Usa Inc. Pressed manual dish detergent
DE102018127180A1 (de) * 2018-10-31 2020-04-30 Henkel Ag & Co. Kgaa Wirkstoffzusammensetzung zur Pflege von Humanhaaren

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