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EP0557426B1 - Composition detergente douce pour vaisselle contenant un tensioactif d'ethoxycarboxylate d'alkyle et des ions de calcium ou de magnesium - Google Patents

Composition detergente douce pour vaisselle contenant un tensioactif d'ethoxycarboxylate d'alkyle et des ions de calcium ou de magnesium Download PDF

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Publication number
EP0557426B1
EP0557426B1 EP92900582A EP92900582A EP0557426B1 EP 0557426 B1 EP0557426 B1 EP 0557426B1 EP 92900582 A EP92900582 A EP 92900582A EP 92900582 A EP92900582 A EP 92900582A EP 0557426 B1 EP0557426 B1 EP 0557426B1
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Prior art keywords
alkyl
calcium
compositions
composition
composition according
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EP92900582A
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German (de)
English (en)
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EP0557426A1 (fr
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Thomas Anthony Cripe
Kofi Ofosu-Asante
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Procter and Gamble Co
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Procter and Gamble Co
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    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D1/00—Detergent compositions based essentially on surface-active compounds; Use of these compounds as a detergent
    • C11D1/02—Anionic compounds
    • C11D1/04—Carboxylic acids or salts thereof
    • C11D1/06—Ether- or thioether carboxylic acids
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D1/00—Detergent compositions based essentially on surface-active compounds; Use of these compounds as a detergent
    • C11D1/66—Non-ionic compounds
    • C11D1/83—Mixtures of non-ionic with anionic compounds
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D10/00—Compositions of detergents, not provided for by one single preceding group
    • C11D10/04—Compositions of detergents, not provided for by one single preceding group based on mixtures of surface-active non-soap compounds and soap
    • 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
    • C11D10/00—Compositions of detergents, not provided for by one single preceding group
    • C11D10/04—Compositions of detergents, not provided for by one single preceding group based on mixtures of surface-active non-soap compounds and soap
    • C11D10/042—Compositions of detergents, not provided for by one single preceding group based on mixtures of surface-active non-soap compounds and soap based on anionic surface-active compounds and soap
    • 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
    • C11D17/00—Detergent materials or soaps characterised by their shape or physical properties
    • C11D17/0008—Detergent materials or soaps characterised by their shape or physical properties aqueous liquid non soap compositions
    • C11D17/003—Colloidal solutions, e.g. gels; Thixotropic solutions or pastes
    • 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
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D1/00—Detergent compositions based essentially on surface-active compounds; Use of these compounds as a detergent
    • C11D1/02—Anionic compounds
    • C11D1/12—Sulfonic acids or sulfuric acid esters; Salts thereof
    • C11D1/14—Sulfonic acids or sulfuric acid esters; Salts thereof derived from aliphatic hydrocarbons or mono-alcohols
    • C11D1/143—Sulfonic acid esters
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D1/00—Detergent compositions based essentially on surface-active compounds; Use of these compounds as a detergent
    • C11D1/02—Anionic compounds
    • C11D1/12—Sulfonic acids or sulfuric acid esters; Salts thereof
    • C11D1/14—Sulfonic acids or sulfuric acid esters; Salts thereof derived from aliphatic hydrocarbons or mono-alcohols
    • C11D1/146—Sulfuric acid esters
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D1/00—Detergent compositions based essentially on surface-active compounds; Use of these compounds as a detergent
    • C11D1/02—Anionic compounds
    • C11D1/12—Sulfonic acids or sulfuric acid esters; Salts thereof
    • C11D1/22—Sulfonic acids or sulfuric acid esters; Salts thereof derived from aromatic compounds
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D1/00—Detergent compositions based essentially on surface-active compounds; Use of these compounds as a detergent
    • C11D1/02—Anionic compounds
    • C11D1/12—Sulfonic acids or sulfuric acid esters; Salts thereof
    • C11D1/28—Sulfonation products derived from fatty acids or their derivatives, e.g. esters, amides
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D1/00—Detergent compositions based essentially on surface-active compounds; Use of these compounds as a detergent
    • C11D1/02—Anionic compounds
    • C11D1/12—Sulfonic acids or sulfuric acid esters; Salts thereof
    • C11D1/29—Sulfates of polyoxyalkylene ethers
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D1/00—Detergent compositions based essentially on surface-active compounds; Use of these compounds as a detergent
    • C11D1/38—Cationic compounds
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D1/00—Detergent compositions based essentially on surface-active compounds; Use of these compounds as a detergent
    • C11D1/38—Cationic compounds
    • C11D1/52—Carboxylic amides, alkylolamides or imides or their condensation products with alkylene oxides
    • C11D1/521—Carboxylic amides (R1-CO-NR2R3), where R1, R2 and R3 are alkyl or alkenyl groups
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D1/00—Detergent compositions based essentially on surface-active compounds; Use of these compounds as a detergent
    • C11D1/38—Cationic compounds
    • C11D1/52—Carboxylic amides, alkylolamides or imides or their condensation products with alkylene oxides
    • C11D1/525—Carboxylic amides (R1-CO-NR2R3), where R1, R2 or R3 contain two or more hydroxy groups per alkyl group, e.g. R3 being a reducing sugar rest
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D1/00—Detergent compositions based essentially on surface-active compounds; Use of these compounds as a detergent
    • C11D1/66—Non-ionic compounds
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D1/00—Detergent compositions based essentially on surface-active compounds; Use of these compounds as a detergent
    • C11D1/66—Non-ionic compounds
    • C11D1/662—Carbohydrates or derivatives
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D1/00—Detergent compositions based essentially on surface-active compounds; Use of these compounds as a detergent
    • C11D1/66—Non-ionic compounds
    • C11D1/72—Ethers of polyoxyalkylene glycols
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D1/00—Detergent compositions based essentially on surface-active compounds; Use of these compounds as a detergent
    • C11D1/66—Non-ionic compounds
    • C11D1/75—Amino oxides
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D1/00—Detergent compositions based essentially on surface-active compounds; Use of these compounds as a detergent
    • C11D1/88—Ampholytes; Electroneutral compounds
    • C11D1/90—Betaines

Definitions

  • the present invention relates to light-duty liquid or gel dishwashing detergent compositions containing alkyl ethoxy carboxylate surfactants (alternatively labeled alkyl polyethoxy carboxy methylates, alkyl polyethoxy acetates, alkyl polyether carboxylates, etc.) of the type disclosed in U.S. Pat. Nos. 2,183,853; 2,653,972; 3,003,954; 3,038,862; 3,741,911; and 3,941,710; British Pat. Nos. 456,517 and 1,169,496; Canadian Pat. No. 912,395; French Pat. Nos. 2,014,084 and 2,042,793; Netherland Patent Application Nos. 7,201,735-Q and 7,406,336; and Japanese Patent Application Nos. 96,579/71 and 99,331/71.
  • alkyl ethoxy carboxylate surfactants alternatively labeled alkyl polyethoxy carboxy methylates, alky
  • the present invention relates to a light-duty liquid or gel, preferably liquid, dishwashing detergent composition
  • a light-duty liquid or gel, preferably liquid, dishwashing detergent composition comprising:
  • the light-duty liquid or gel, preferably liquid, dishwashing detergent compositions of the present invention contain a surfactant mixture comprising a major amount of an alkyl ethoxy carboxylate surfactant and little or no alcohol ethoxylate and soap by-product contaminants, and a source of calcium or magnesium ions.
  • a surfactant mixture comprising a major amount of an alkyl ethoxy carboxylate surfactant and little or no alcohol ethoxylate and soap by-product contaminants
  • a source of calcium or magnesium ions In compositions hereof containing magnesium ions, magnesium chelating agent and an alkalinity buffering agent are also required.
  • the compositions hereof containing calcium ions may also require a calcium chelating agent.
  • the liquid compositions of this invention contain from about 5% to 50% by weight, preferably from about 10% to 40%, most preferably from about 12% to 30%, of a surfactant mixture restricted in the levels of contaminants.
  • Gel compositions of this invention contain from about 5% to about 70%, preferably from about 10% to about 45%, most preferably from about 12% to about 35%, of the surfactant mixture.
  • the surfactant mixture contains from about 80% to 100%, preferably from about 85% to 95%, most preferably from 90% to 95%, of alkyl ethoxy carboxylates of the generic formula RO(CH 2 CH 2 O) x CH 2 COO - M + wherein R is a C 12 to C 16 alkyl group, x ranges from 0 to 10, and the ethoxylate distribution is such that, on a weight basis, the amount of material where x is 0 is less than 20%, preferably less than about 15%, most preferably less than about 10%, and the amount of material where x is greater than 7 is less than 25%, preferably less than about 15%, most preferably less than about 10%, the average x is from 2 to 4 when the average R is C 13 or less, and the average x is from 3 to 6 when the average R is greater than C 13 , and M is a cation, preferably chosen from alkali metal, alkaline earth metal, ammonium, mono-, di-, and tri-ethanol-ammonium,
  • Suitable alcohol precursors of the alkyl ethoxy carboxylates of this invention are primary aliphatic alcohols containing from about 12 to about 16 carbon atoms.
  • Other suitable primary aliphatic alcohols are the linear primary alcohols obtained from the hydrogenation of vegetable or animal fatty acids such as coconut, palm kernel, and tallow fatty acids or by ethylene build up reactions and subsequent hydrolysis as in the Ziegler type processes.
  • Preferred alcohols are n-octyl, n-nonyl, n-decyl, n-undecyl, n-dodecyl, n-tridecyl, n-tetradecyl, n-pentadecyl, and n-hexadecyl.
  • Other suitable alcohol precursors include primary alcohols having a proportion of branching on the beta or 2-carbon atoms wherein the alkyl branch contains from 1 to 4 carbon atoms. In such alcohols at least 30% of the alcohol of each specific chain length is desirably linear and the branching preferably comprises about 50% of methyl groups with smaller amounts of ethyl, propyl and butyl groups.
  • These alcohols are conveniently produced by reaction of linear olefins having from about 11 to 17 carbon atoms with carbon monoxide and hydrogen. Both linear and branched chain alcohols are formed by these processes and the mixtures can either be used as such or can be separated into individual components and then recombined to give the desired blend.
  • the equivalent secondary alcohols can also be used. It will be apparent that by using a single chain length olefin as starting material, a corresponding single chain length alcohol will result, but it is generally more economical to utilize mixtures of olefins having a spread of carbon chain length around the desired mean. This will, of course, provide a mixture of alcohols having the same distribution of chain lengths around the mean.
  • the desired average ethoxy chain length on the alcohol ethoxylate can be obtained by using a catalyzed ethoxylation process, wherein the molar amount of ethylene oxide reacted with each equivalent of fatty alcohol will correspond to the average number of ethoxy groups on the alcohol ethoxylated.
  • the addition of ethylene oxide to alkanols is known to be promoted by a catalyst, most conventionally a catalyst of either strongly acidic or strongly basic character.
  • Suitable basic catalysts are the basic salts of the alkali metals of Group I of the Periodic Table, e.g., sodium, potassium, rubidium, and cesium, and the basic salts of certain of the alkaline earth metals of Group II of the Periodic Table, e.g., calcium, strontium, barium, and in some cases magnesium.
  • Suitable acidic catalysts include, broadly, the Lewis acid of Friedel-Crafts catalysts. Specific examples of these catalysts are the fluorides, chlorides, and bromides of boron, antimony, tungsten, iron, nickel, zinc, tin, aluminum, titanium, and molybdenum.
  • the surfactant mixture also contains from 0% to 10%, preferably less than about 8%, most preferably less than 5%, of alcohol ethoxylates of the formula RO(CH 2 CH 2 O) x H wherein R is a C 12 to C 16 alkyl group and x ranges from 0 to 10 and the average x is less than 6.
  • the surfactant mixture also contains 0% to 10%, preferably less than about 8%, most preferably less than 5%, of soaps of the formula RCOO - M + wherein R is a C 11 to C 15 alkyl group and M is a cation as described above.
  • the uncarboxylated alcohol ethoxylates noted above are a detriment to the alkyl ethoxy carboxylate surfactant mixture, especially with respect to the performance benefits provided therefrom. Therefore, it is critical that the alkyl ethoxy carboxylate-containing surfactant mixture used in this invention contain less than about 10% by weight of the alcohol ethoxylates they are derived from.
  • commercially available alkyl ethoxy carboxylates contain 10% or more of alcohol ethoxylates, there are known routes to obtain the desired high purity alkyl ethoxy carboxylates. For example, unreacted alcohol ethoxylates can be removed by steam distillation, U.S. Pat. No.
  • the process comprises reacting the alcohol ethoxylates with the hindered base described -above and either anhydrous chloroacetic acid, at a molar ratio of the hindered base to the anhydrous chloroacetic acid of 2:1, or an alkali metal salt or alkaline earth metal salt of anhydrous chloroacetic acid, at a molar ratio of the hindered base to the alkali metal salt or alkaline earth metal salt of chloroacetic acid of 1:1, wherein the molar ratio of the ethoxylated fatty alcohol to the anhydrous chloroacetic acid or the alkali metal salt or alkaline earth metal salt thereof is from about 1:0.7 to about 1:1.25, the temperature is from about 20 to 140°C, and the pressure is from about 0.133 to 101 kPa (1 to 760 mm Hg).
  • the cations for the alkyl ethoxy carboxylates herein can be alkali metals, alkaline earth metals, ammonium, and lower alkanol ammonium ions.
  • the source of cations for the alkyl ethoxy carboxylates come from neutralization of the alkyl ethoxy carboxylic acid and from additional ingredients, e.g., performance enhancing divalent ion-containing salts.
  • compositions of the invention are ammonium, sodium, and potassium.
  • ammonium is most preferred, but at pH levels above 8, it is undesirable due to the release of small amounts of ammonia gas resulting from deprotonation of the ammonium ions in the composition.
  • potassium is preferred over sodium since it makes the compositions of the invention more resistant to precipitate formation at low temperatures and provides improved solubility to the composition.
  • sodium is preferred over potassium since it makes it easier to gel a composition. Mixtures of the cations may be present in any of the compositions of the invention.
  • a composition with a pH greater than about 7 should contain a buffering agent capable of maintaining the alkaline pH in the composition and in dilute solutions, i.e., about 0.1% to 0.2% by weight aqueous solution, of the composition.
  • the pKa value of this buffering agent should be about 0.5 to 1.0 pH units below the desired pH value of the composition (determined as described above).
  • the buffering agent may be an active detergent in its own right, or it may be a low molecular weight, organic or inorganic material that is used in this composition solely for maintaining an alkaline pH.
  • Suitable buffering agents for compositions of this invention are nitrogen-containing materials. Some examples are other amino acids than glycine or lower alcohol amines like mono-, di-, and tri-ethanolamine.
  • the preferred nitrogen-containing buffering agents are 2-amino-2-ethyl-1,3-propanediol, 2-amino-2-methylpropanol, 2-amino-2-methyl-1,3-propanediol, and tris-(methanol) aminomethane, (a.k.a.
  • N-methyldiethanolamine 1,3-diamino-2-propanol, N,N-tetramethyl -1,3-diamino-2-propanol, bis(2-ethanol)glycine (a.k.a. bicine) imidazole, N-tris-(methanol)methylglycine (a.k.a. tricine) are also preferred.
  • buffering agents are typically present at a level of from about 0.1% to 15% by weight, preferably from about 1% to 10%, most preferably from about 1.5% to 8%.
  • composition containing the present alkyl ethoxy carboxylates that the presence of divalent cations greatly improves the cleaning of greasy soils. This is especially true when the compositions are used in softened water that contains few divalent ions. Dishwashing liquid compositions that contain alkyl ethoxy carboxylates that do not conform to the narrow definition of this invention will be less benefited by the addition of divalent ions and, in many cases, will actually exhibit reduced cleaning performance upon the addition of divalent cations. It is believed that divalent ions increase the packing of the present alkyl ethoxy carboxylates at the oil/water interface, thereby reducing interfacial tension and improving grease cleaning.
  • compositions of the invention hereof containing calcium or magnesium ions exhibit good grease removal, manifest mildness to the skin, and provide good storage stability.
  • Calcium ions are present in the compositions hereof at a level of from about 0.1% to 4% preferably from about 0.5% to 3.5% by weight.
  • the incorporation of a magnesium chelating agent (described below) into the compositions herein prevents the formation of magnesium hydroxide precipitates and makes it possible to incorporate larger doses of magnesium ions, at higher pH levels, required in soft water areas where the divalent ion concentration is low. Therefore, the level of magnesium ions in the composition is from about 0.1% to 3%, preferably from about 0.3% to 2%, most preferably from about 0.5 to 1%, by weight.
  • the calcium or magnesium ions are added as a chloride, acetate, or nitrate salt to compositions containing an alkali metal or ammonium salt of the alkyl ethoxy carboxylate, most preferably the sodium salt, after the composition has been neutralized with a strong base.
  • compositions containing calcium or magnesium ions exhibit superior grease cleaning benefits. Without being held to theory, it is believed that calcium or magnesium binds the alkyl ethoxy carboxylate molecules tighter allowing for tighter packing at the water/oil interface. Lower inter-facial tension (IFT) measurements are exhibited by composition containing calcium ions as compared to compositions containing other divalent ions. Furthermore, at these pH levels, compositions of the invention hereof provide better storage stability over other compositions as described above.
  • IFT inter-facial tension
  • compositions containing calcium ions is easier than that for compositions containing magnesium ions since the pH level of such compositions can be readily adjusted without inducing precipitate formation, whereas in formulating the magnesium compositions once hydroxide precipitates are formed they cannot be readily dissolved.
  • Alkaline compositions hereof can tolerate a higher level of calcium ions at higher pH levels without forming undesirable precipitates, provided some amount of a chelating agent is used.
  • the amount of calcium or magnesium ions present in compositions of the invention will be dependent upon the amount of total anionic surfactant present therein, including the amount of alkyl ethoxy carboxylates.
  • the molar ratio of divalent ions to total anionic surfactant is from about 0.25:1 to about 2:1 for compositions of the invention containing calcium and from about 0.25:1 to about 1:1 for compositions of the invention containing magnesium.
  • composition of the invention hereof may contain a calcium or magnesium chelating agent to sequester calcium or magnesium ions present in the liquid phase of the composition thereby inhibiting the interaction between the calcium or magnesium ions and hydroxide ions which would result in the formation of CaCO 3 or Mg(OH) 2 precipitates, particularly at pH levels between 9 and 11.
  • the calcium or magnesium chelating complex agent forms must be soluble. If an insoluble calcium or magnesium-chelant complex is formed, it will cause unsightly product turbidity, and if the complex settles to the bottom of the product there may be insufficient levels of calcium or magnesium ion delivered to the wash solution upon normal dispensing of the product.
  • the chelating agent must associate with the calcium or magnesium ions only moderately, i.e. only strong enough to prevent interaction between the calcium and carbonate ions or magnesium and hydroxide ions, but not too much so as to significantly reduce the amount of calcium or magnesium ions available in dilute solution. Therefore, the log of formation constant, log K f , for the chelating agent is between 0.5 and 5.
  • the amount of chelating agent present in the composition of the invention hereof is that amount sufficient to prevent the formation of CaCO 3 or Mg(OH) 2 precipitates in the composition. This amount is dependent upon three factors: the desired pH of the composition, the level of calcium or magnesium ions in the composition and the strength of the chelating agent, i.e. its log K f .
  • compositions containing magnesium ions As for compositions containing magnesium ions, higher desired pH levels of a composition in dilute solution results in higher concentrations of hydroxide ions in the composition. This in turn results in more hydroxide ions in the composition available to interact with magnesium ions in the composition and a higher tendency to form Mg(OH) 2 precipitates therein. This requires a higher level of chelating agent incorporated into the composition provided the same chelating agent is used. The use of a stronger chelating, i.e. higher log K f could replace the use of more of a weaker chelating agent.
  • the log of formation constant, log K f must be considered in determining the amount of chelating agent to use in a composition.
  • the log K f of the chelating agent is between 0.5 and 5, preferably between 1 and 3.5. The higher the log K f , the tighter the hold on calcium ions, and the less required for the prevention of CaCO 3 precipitate formation in the composition.
  • the amount of chelating agent in the compositions hereof is set forth in Table I, below.
  • the formulator In determining the amount of chelating agent to use in compositions of the invention hereof, the formulator must determine the log K f of the chelating agent. A method for determining the formation constants of these chelating agents is described in Determination and Use of Stability Constants; A.E.
  • Table I log K f % (by weight) 0.5 to 1.5 ⁇ 10 1.5 to 3 ⁇ 8 3 to 5 ⁇ 3
  • suitable chelating agents bicine (bis(2-ethanol) glycine), N-(2-hydroxyethyl)iminodiacetic acid (HIDA), N-(2,3-dihydroxypropyl)iminodiacetic acid (GIDA), and their alkali metal salts but exclude glycine and citrate. Mixtures of the above are acceptable.
  • the preferred chelating agent is bicine.
  • Primary amines are not preferred as chelating agents of compositions of the invention hereof containing magnesium because they tend to cause discoloration of the composition upon storage. Therefore, preferred compositions of the invention hereof are substantially free of chelating agents that are primary amines.
  • compositions of the invention hereof containing magnesium work well together in compositions of the invention hereof containing magnesium.
  • alkanol amines including 2-amino-2-ethyl-1,3-propanediol, 2-amino-2-methyl-1,3 propanedial, and 2-amino-2-methylpropanol
  • bicine with tris bicine with N-methyldiethanolamine
  • bicine with diethanolamine bicine with 1,3-diamino-2-propanol
  • bicine with triethanolamine bicine with triethanolamine.
  • compositions of this invention preferably contain certain co-surfactants to aid in the foaming, detergency, and/or mildness.
  • anionic surfactants commonly used in liquid or gel dishwashing detergents.
  • the cations associated with these anionic surfactants can be the same as the cations described previously for the alkyl ethoxy carboxylates.
  • anionic co-surfactants that are useful in the present invention are the following classes:
  • nonionic fatty alkylpolyglucosides are the nonionic fatty alkylpolyglucosides. These surfactants contain straight chain or branched chain C 8 to C 15 , preferably from about C 12 to C 14 , alkyl groups and have an average of from about 1 to 5 glucose units, with an average of 1 to 2 glucose units being most preferred.
  • U.S. Pat. Nos. 4,393,203 and 4,732,704 describe these surfactants.
  • compositions hereof may also contain a polyhydroxy fatty acid amide surfactant of the structural formula: wherein: R 1 is H, C 1 -C 4 hydrocarbyl, 2-hydroxy ethyl, 2-hydroxy propyl, or a mixture thereof, preferably C 1 -C 4 alkyl, more preferably C 1 or C2 alkyl, most preferably C 1 alkyl (i.e., methyl); and R 2 is a C 5 -C 31 hydrocarbyl, preferably straight chain C 7 -C 19 alkyl or alkenyl, more preferably straight chain C 9 -C 17 alkyl or alkenyl, most preferably straight chain C 11 -C 17 alkyl or alkenyl, or mixtures thereof; and Z is a polyhydroxyhydrocarbyl having a linear hydrocarbyl chain with at least 3 hydroxyls directly connected to the chain, or an alkoxylated derivative (preferably ethoxylated or propoxylated) thereof.
  • R 1 is H, C 1
  • Z preferably will be derived from a reducing sugar in a reductive amination reaction; more preferably Z is a glycityl.
  • Suitable reducing sugars include glucose, fructose, maltose, lactose, galactose, mannose, and xylose.
  • high dextrose corn syrup, high fructose corn syrup, and high maltose corn syrup can be utilized as well as the individual sugars listed above. These corn syrups may yield a mix of sugar components for Z. It should be understood that it is by no means intended to exclude other suitable raw materials.
  • Z preferably will be selected from the group consisting of -CH 2 -(CHOH) n -CH 2 OH, -CH(CH 2 OH)-(CHOH) n-1 -CH 2 OH, -CH 2 -(CHOH) 2 (CHOR')(CHOH)-CH 2 OH, where n is an integer from 3 to 5, inclusive, and R' is H or a cyclic or aliphatic monosaccharide, and alkoxylated derivatives thereof. Most preferred are glycityls wherein n is 4, particularly -CH 2 -(CHOH) 4 -CH 2 OH.
  • R 1 can be, for example, N-methyl, N-ethyl, N-propyl, N-isopropyl, N-butyl, N-2-hydroxy ethyl, or N-2-hydroxy propyl.
  • Z can be 1-deoxyglucityl, 2-deoxyfructityl, 1-deoxymaltityl, 1-deoxylactityl, 1-deoxygalactityl, 1-deoxymannityl and 1-deoxymaltotriotityl.
  • polyhydroxy fatty acid amides are known in the art. In general, they can be made by reacting an alkyl amine with a reducing sugar in a reductive amination reaction to form a corresponding N-alkyl polyhydroxyamine, and then reacting the N-alkyl polyhydroxyamine with a fatty aliphatic ester or triglyceride in a condensation/amidation step to form the N-alkyl, N-polyhydroxy fatty acid amide product.
  • Processes for making compositions containing polyhydroxy fatty acid amides are disclosed, for example, in G.B. Patent Specification 809,060, published February 18, 1959, by Thomas Hedley & Co., Ltd., U.S. Patent 2,965,576, issued December 20, 1960 to E. R. Wilson, and U.S. Patent 2,703,798, Anthony M. Schwartz, issued March 8, 1955, and U.S. Patent 1,985,424, issued December 25, 1934 to Piggott.
  • the product is made by reacting N-alkyl- or N-hydroxyalkyl-glucamine with a fatty ester selected from fatty methyl esters, fatty ethyl esters, and fatty triglycerides in the presence of a catalyst selected from the group consisting of trilithium phosphate, trisodium phosphate, tripotassium phosphate, tetrasodium pyrophosphate, pentapotassium tripolyphosphate, lithium hydroxide, sodium hydroxide, potassium hydroxide, calcium hydroxide, lithium carbonate, sodium carbonate, potassium
  • this process is carried out as follows:
  • N-linear glucosyl fatty acid amide product is added to the reaction mixture, by weight of the reactants, as the phase transfer agent if the fatty ester is a triglyceride. This seeds the reaction, thereby increasing reaction rate.
  • polyhydroxy "fatty acid” amide materials also offer the advantages to the detergent formulator that they can be prepared wholly or primarily from natural, renewable, non-petrochemical feedstocks and are degradable. They also exhibit low toxicity to aquatic life.
  • the processes used to produce them will also typically produce quantities of nonvolatile by-product such as esteramides and cyclic polyhydroxy fatty acid amide.
  • the level of these by-products will vary depending upon the particular reactants and process conditions.
  • the polyhydroxy fatty acid amide incorporated into the detergent compositions hereof will be provided in a form such that the polyhydroxy fatty acid amide-containing composition added to the detergent contains less than about 10%, preferably less than about 4%, of cyclic polyhydroxy fatty acid amide.
  • the preferred processes described above are advantageous in that they can yield rather low levels of by-products, including such cyclic amide by-product.
  • the co-surfactants for the compositions of this invention can also contain mixtures of anionic surfactants with alkyl polyglucosides or polyhdroxy fatty acid amides.
  • the co-surfactants are present in the composition at a level of from 0% to about 35% by weight, preferably from about 5% to 25%, and most preferably from about 7% to 20%.
  • suds stabilizing surfactant is a level of less than about 15%, preferably from about 0.5% to 12%, more preferably from about 1% to 10%.
  • Optional suds stabilizing surfactants operable in the instant composition are of five basic types -- betaines, ethylene oxide condensates, fatty acid amides, amine oxide semi-polar nonionics, and cationic surfactants.
  • composition of this invention can contain betaine detergent surfactants having the general formula: wherein R is a hydrophobic group selected from the group consisting of alkyl groups containing from about 10 to about 22 carbon atoms, preferably from about 12 to about 18 carbon atoms, alkyl aryl and aryl alkyl groups containing a similar number of carbon atoms with a benzene ring being treated as equivalent to about 2 carbon atoms, and similar structures interrupted by amido or ether linkages; each R 1 is an alkyl group containing from 1 to about 3 carbon atoms; and R 2 is an alkylene group containing from 1 to about 6 carbon atoms.
  • R is a hydrophobic group selected from the group consisting of alkyl groups containing from about 10 to about 22 carbon atoms, preferably from about 12 to about 18 carbon atoms, alkyl aryl and aryl alkyl groups containing a similar number of carbon atoms with a benzene ring being treated as equivalent to about 2 carbon
  • betaines dodecyl dimethyl betaine, cetyl dimethyl betaine, dodecyl amidopropyldimethyl betaine, tetradecyldimethyl betaine, tetradecylamidopropyldimethyl betaine, and dodecyldimethylammonium hexanoate.
  • amidoalkylbetaines are disclosed in U.S. Pat. Nos. 3,950,417; 4,137,191; and 4,375,421; and British Patent GB No. 2,103,236.
  • alkyl (and acyl) groups for the above betaine surfactants can be derived from either natural or synthetic sources, e.g., they can be derived from naturally occurring fatty acids; olefins such as those prepared by Ziegler, or Oxo processes; or from olefins separated from petroleum either with or without "cracking".
  • the ethylene oxide condensates are broadly defined as compounds produced by the condensation of ethylene oxide groups (hydrophilic in nature) with an organic hydrophobic compound, which can be aliphatic or alkyl aromatic in nature.
  • the length of the hydrophilic or polyoxyalkylene radical which is condensed with any particular hydrophobic group can be readily adjusted to yield a water-soluble compound having the desired balance between hydrophilic and hydrophobic elements.
  • amide surfactants useful herein include the ammonia, monoethanol, and diethanol amides of fatty acids having an acyl moiety containing from about 8 to about 18 carbon atoms and represented by the general formula: R 1 - CO - N(H) m - 1 (R 2 OH) 3 - m wherein R is a saturated or unsaturated, aliphatic hydrocarbon radical having from about 7 to 21, preferably from about 11 to 17 carbon atoms; R 2 represents a methylene or ethylene group; and m is 1, 2, or 3, preferably 1.
  • Specific examples of said amides are mono-ethanol amine coconut fatty acid amide and diethanol amine dodecyl fatty acid amide.
  • acyl moieties may be derived from naturally occurring glycerides, e.g., coconut oil, palm oil, soybean oil, and tallow, but can be derived synthetically, e.g., by the oxidation of petroleum or by hydrogenation of carbon monoxide by the Fischer-Tropsch process.
  • the monoethanol amides and diethanolamides of C 12-14 fatty acids are preferred.
  • Amine oxide semi-polar nonionic surfactants comprise compounds and mixtures of compounds having the formula wherein R 1 is an alkyl, 2-hydroxyalkyl, 3-hydroxyalkyl, or 3-alkoxy-2-hydroxypropyl radical in which the alkyl and alkoxy, respectively, contain from about 8 to about 18 carbon atoms, R 2 and R 3 are each methyl, ethyl, propyl, isopropyl, 2-hydroxyethyl, 2-hydroxypropyl, or 3-hydroxypropyl, and n is from 0 to about 10.
  • Particularly preferred are amine oxides of the formula: wherein R 1 is a C 12-16 alkyl and R 2 and R 3 are methyl or ethyl.
  • composition of this invention can also contain certain cationic quarternary ammonium surfactants of the formula: [R 1 (OR 2 ) y ][R 3 (OR 2 ) y ] 2 R 4 N + X - or amine surfactants of the formula: [R 1 (OR 2 ) y ][R 3 (OR 2 ) y ]R 4 N wherein R 1 is an alkyl or alkyl benzyl group having from about 6 to about 16 carbon atoms in the alkyl chain; each R 2 is selected from the group consisting of -CH 2 CH 2 -, -CH 2 CH(CH 3 )-, -CH 2 CH(CH 2 OH)-, -CH 2 CH 2 CH 2 -, and mixtures thereof; each R 3 is selected from the group consisting of C 1 -C 4 alkyl, C 1 -C 4 hydroxyalkyl, benzyl, and hydrogen when y is not 0; R 4 is the same as R 3 or is an alkyl chain
  • alkyl quaternary ammonium surfactants especially the mono-long chain alkyl surfactants described in the above formula when R 4 is selected from the same groups as R 3 .
  • the most preferred quaternary ammonium surfactants are the chloride, bromide, and methylsulfate C 8-16 alkyl trimethylammonium salts, C 8-16 alkyl di(hydroxyethyl)methylammonium salts, the C 8-16 alkyl hydroxyethyldimethylammonium salts, C 8-16 alkyloxypropyl trimethylammonium salts, and the C 8-16 alkyloxypropyl dihydroxyethylmethylammonium salts.
  • the C 10-14 alkyl trimethylammonium salts are preferred, e.g., decyl trimethylammonium methylsulfate, lauryl trimethylammonium chloride, myristyl trimethylammonium bromide and coconut trimethylammonium chloride, and methylsulfate.
  • the suds boosters used in the compositions of this invention can contain any one or mixture of the suds boosters listed above.
  • compositions can contain other conventional ingredients suitable for use in liquid or gel dishwashing compositions.
  • Optional ingredients include drainage promoting ethoxylated nonionic surfactants of the type disclosed in U.S. Pat. No. 4,316,824, Pancheri (February 23, 1982).
  • Alcohols such as ethyl alcohol and propylene glycol, can be utilized in the interests of achieving a desired product phase stability and viscosity. Alcohols such as ethyl alcohol and propylene glycol at a level of from 0% to about 15%, are particularly useful in the liquid compositions of the invention.
  • the following liquid composition which does not exemplify the present invention is prepared according to the descriptions set forth below.
  • the alkyl ethoxy carboxylate and the appropriate co-surfactant the booster, ethanol, sodium chloride, and the buffer are blended.
  • the pH of the mixture is adjusted with ammonium hydorixed to about 8.
  • the calcium ions (added as calcium chloride dihydrate) are added and the final pH adjusted, if necessary, to about 7.2.
  • Final viscosity and minor pH adjustments can be made at this time, followed by the addition of perfume and dye.
  • the balance is water.
  • the above formulation give excellent combinations of grease cleaning and mildness and are stable to storage at elevated temperatures (up to 66.7°C (120°F).
  • the cleaning provided by this composition at pH of about 7.2-7.5 is better than that provided by a similar composition containing an equivalent (molar basis) amount of magnesium ions.
  • These formulations also provide superior stability during storage especially when compared to similar compositions containing magnesium ions.
  • This formulation of the present invention provides both good dilute solution grease cleaning and formulation storage stability at elevated temperatures of 66.7°C (120°F) especially, when compared to equivalent magnesium ion-containing compositions.
  • the above formulation of the present invention provides both good dilute solution grease cleaning and formulation storage stability at elevated temperatures of 66.7°C (120°F) especially, when compared to equivalent magnesium ion-containing compositions. This formulation is particularly useful for dishwashing habits where high product concentration in solution is used.
  • the formulations are made by adding ethanol to the alkyl ethoxy carboxylate-containing surfactant mixture. The remaining surfactants are then added and mixed in. The buffering and chelating agents are then added and the pH is adjusted to about 0.5 pH units above the target for the formula with sodium hydroxide. Finally, the magnesium chloride is added, which reduces the pH to the target. Final viscosity and minor pH adjustments can be made at this time, followed by the addition of perfume and dye. The balance is water.
  • the surfactant mixture contains about 94.2% alkyl ethoxy carboxylates of the formula RO(CH 2 CH 2 O) x CH 2 COO - Na + where R is a C 12-13 alkyl averaging 12.5; x ranges from 0 to about 10, and the ethoxylate distribution is such that the amount of material where x is 0 is about 1.0 and the amount of material where x is greater than 7 is less than about 2% by weight of the alkyl ethoxy carboxylates.
  • the average x in the distribution is 3.5.
  • the surfactant mixture contains 0% soap materials.
  • the above formulations give excellent combinations of grease cleaning and mildness and do not exhibit precipitation when stored at elevated temperatures (up to 66.7°C 120°F).
  • the grease cleaning ability of these products is directly related to their ability to maintain dilute solution alkaline wash pH.
  • the rank order of these products in terms of their ability to maintain a high wash pH is A>B>C>D.
  • the hand mildness of these products are directly related to their levels of alkyl ethoxy carboxylate-containing surfactant mixture and inversely related to their levels of alkyl sulfate and alkyl ethoxy sulfate surfactants. For these reasons the rank order of hand mildness of these products is C>A,B>D.
  • These formulations also provide superior stability during storage especially when compared to similar compositions without a buffering and/or chelating agent.
  • Formulation D contains glycine and does exhibit discoloration of the composition upon storage.
  • Formulation B which does not exemplify of the present invention provides both good dilute solution grease cleaning and formulation storage stability at elevated temperatures of 66.7°C (120°F). This is in contrast to Formulations A, C and D which are not within the scope of the present invention.
  • Formulation A provides good dilute solution grease cleaning, even in soft water, because of its combination of alkylethoxy carboxylate containing surfactant mixture, magnesium ions and its alkaline pH in a dishwashing solution due to 2-Amino-2-ethyl-1,3-propanediol. However, Formulation A is not stable to storage and precipitates of Mg(OH) 2 are formed.
  • Formulation C provides good product storage stability by virtue of the citrates ability to prevent Mg(OH) 2 precipitation but does not provide sufficient grease cleaning ability in dilute solution. This is because the level of citrate is too high and reduces the available Mg ++ in dilute solution needed for good cleaning.
  • Formulation D provides good storage stability but poorer grease cleaning than Formulations A and B.

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Abstract

Composition détergente douce pour la vaisselle, sous forme de liquide ou de gel, contenant un mélange tensioactif d'éthoxycarboxylate d'alkyle et des ions de calcium ou de magnésium. Les compositions contenant du magnésium nécessitent un agent chélatant le magnésium et un agent de tamponnage destiné à maintenir le pH de la composition entre 8 et 10 environ. Les compositions contenant des ions de calcium peuvent nécessiter un agent chélatant le calcium, en particulier à des niveaux de pH supérieurs à 9, de manière à empêcher la formation de précipités de CaCO3 pendant le stockage. Lesdites compositions ont une bonne action dégraissante, tout en étant douces pour la peau. Elles possèdent également une bonne stabilité au stockage. Les compositions détergentes pour la vaisselle sous forme liquide constituent un type préféré. Le pH élevé et les ions de calcium ou de magnésium desdites compositions augmentent leurs propriétés dégraissantes, tout en conservant leur douceur.

Claims (12)

  1. Composition détergente liquide ou en gel pour le lavage délicat de la vaisselle, caractérisé. en ce qu'elle comprend, en poids:
    (a) de 5% à 70% d'un mélange de tensioactifs comprenant, en poids:
    (i) de 80% à 100% d'alkyléthoxycarboxylates de formule:

            RO(CH2CH2O)xCH2COO-M+

    dans laquelle R est un groupe alkyle en C12 à C16, x s'échelonne de 0 à 10 et la distribution des éthoxylats est telle que, sur une base pondérale, la quantité de substance où x est nul soit inférieure à 20% et la quantité de substance où x est supérieur à 7 soit inférieure à 25%, la valeur moyenne de x est de 2 à 4 lorsque la longueur moyenne de R est de C13 ou moins, et la valeur moyenne de x est de 3 à 6 lorsque la longueur moyenne de R est supérieure à C13, et M est un cation;
    (ii) de 0% à 10% d'éthoxylates d'alcool de formule:

            RO(CH2CH2O)xH

    dans laquelle R est un groupe alkyle en C12 à C16 et x s'échelonne de 0 à 10 et la valeur moyenne de x est inférieure à 6; et
    (iii) de 0% à 10% de savons de formule:

            RCOO-M+

    dans laquelle R est un groupe alkyle en C11 à C15 et M est un cation;
    (b) de 0,1% à 4% d'ions calcium ou magnésium;
    (c) un agent chélatant les ions calcium ou magnésium, qui forme un complexe soluble de calcium ou de magnésium présentant un log de la constante de formation, log Kf, compris entre 0,5 et 5, à l'exclusion de la glycine et du citrate, en quantité suffisante pour empêcher la formation de précipité de carbonate de calcium ou d'hydroxyde de magnésium dans la composition;
    dans laquelle une solution aqueuse à 10% en poids de ladite composition possède un pH de 7 à 11.
  2. Composition selon la revendication 1, dans laquelle le mélange de tensioactifs comprend de 90% à 95% d'alkyléthoxycarboxylates.
  3. Composition selon la revendication 1 ou 2, dans laquelle le pH est de 8 à 10.
  4. Composition selon l'une quelconque des revendications précédentes, dans laquelle le mélange de tensioactifs comprend moins de 5% des éthoxylates d'alcool.
  5. Composition selon l'une quelconque des revendications précédentes, dans laquelle le mélange de tensioactifs comprend moins de 5% des savons.
  6. Composition liquide selon l'une quelconque des revendications précédentes, comprenant de 12% à 30% du mélange de tensioactifs.
  7. Composition de gel selon l'une quelconque des revendications 1 à 5, comprenant de 10% à 45% du mélange de tensioactifs.
  8. Composition selon l'une quelconque des revendications précédentes, comprenant par ailleurs un cotensioactif choisi dans l'ensemble constitué par les alkylbenzènesulfonates, les alkylsulfates, les paraffinesulfonates, les oléfinesulfonates, les alkyléthersulfates, les estersulfonates d'acides gras, les alkylpolyglucosides et les polyhydroxylamides d'acides gras, et leurs mélanges.
  9. Composition selon l'une quelconque des revendications précédentes, comprenant par ailleurs un renforçateur de moussage choisi dans l'ensemble constitué par les bétaïnes, les condensats d'oxyde d'éthylène, les amides d'acides gras, les non ioniques semipolaires de type oxyde d'amine, les tensioactifs cationiques, et leurs mélanges.
  10. Composition selon l'une quelconque des revendications précédentes, comprenant par ailleurs une quantité suffisante d'agent tampon pour l'alcalinité pour maintenir le pH de la composition entre 8 et 10.
  11. Composition selon l'une quelconque des revendications précédentes, dans laquelle l'agent chélatant les ions calcium ou magnésium est choisi dans l'ensemble constitué par la sarcosine, la bicine, l'acide N-(2-hydroxyéthyl)iminodiacétique, l'acide N-(2,3-dihydroxypropyl)iminodiacétique, et leurs sels de métaux alcalins, et leurs mélanges.
  12. Composition selon la revendication 10, dans laquelle l'agent tampon est choisi dans l'ensemble constitué par la N-méthyldiéthanolamine, le 1,3-diamino-2-propanol, la bicine, le N,N'-tétraméthyl-1,3-diamino-2-propanol.
EP92900582A 1990-11-16 1991-11-08 Composition detergente douce pour vaisselle contenant un tensioactif d'ethoxycarboxylate d'alkyle et des ions de calcium ou de magnesium Expired - Lifetime EP0557426B1 (fr)

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Families Citing this family (36)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CA2116955C (fr) * 1991-09-06 1998-06-23 Kofi Ofosu-Asante Compositions detergentes renfermant du calcium et un amide d'acide gras polyhydroxyle
US5298195A (en) * 1992-03-09 1994-03-29 Amway Corporation Liquid dishwashing detergent
NL9201339A (nl) * 1992-07-24 1994-02-16 Chem Y Gmbh Vloeibare geconcentreerde oplossingen van alkylethercarbonzuurzouten in water.
US5545354A (en) * 1992-09-01 1996-08-13 The Procter & Gamble Company Liquid or gel dishwashing detergent containing a polyhydroxy fatty acid amide, calcium ions and an alkylpolyethoxypolycarboxylate
US5269974A (en) * 1992-09-01 1993-12-14 The Procter & Gamble Company Liquid or gel dishwashing detergent composition containing alkyl amphocarboxylic acid and magnesium or calcium ions
WO1994005758A1 (fr) * 1992-09-01 1994-03-17 The Procter & Gamble Company Compositions detergentes liquides ou en gel contenant du calcium et stabilisant de celles-ci
EP0658191A1 (fr) * 1992-09-01 1995-06-21 The Procter & Gamble Company Detergent liquide ou en gel pour lave-vaisselle, contenant du carboxylate d'ethoxy d'alkyle, des ions bivalents et de l'alkylpolyethoxypolycarboxylate
EP0670884A1 (fr) * 1992-11-30 1995-09-13 The Procter & Gamble Company Compositions detergentes comprenant un melange d'ions de calcium et de tensioactifs/savons non ioniques/anioniques selectionnes contenant des amides d'acide gras polyhydroxy
US5415801A (en) * 1993-08-27 1995-05-16 The Procter & Gamble Company Concentrated light duty liquid or gel dishwashing detergent compositions containing sugar
US5415814A (en) * 1993-08-27 1995-05-16 The Procter & Gamble Company Concentrated liquid or gel light duty dishwashing detergent composition containing calcium xylene sulfonate
US5417893A (en) * 1993-08-27 1995-05-23 The Procter & Gamble Company Concentrated liquid or gel light duty dishwashing detergent compositions containing calcium ions and disulfonate surfactants
US5474710A (en) * 1993-08-27 1995-12-12 Ofosu-Asanta; Kofi Process for preparing concentrated surfactant mixtures containing magnesium
RU2142981C1 (ru) * 1993-09-14 1999-12-20 Дзе Проктер Энд Гэмбл Компани Удобная в эксплуатации жидкая или гелевая моющая композиция для мытья посуды и удобная в эксплуатации жидкая моющая композиция для мытья посуды
ATE318304T1 (de) 1993-10-08 2006-03-15 Novozymes As Amylasevarianten
DE19581539B4 (de) 1994-02-23 2009-09-17 Ecolab Inc., St. Paul Alkalische Reiniger auf der Basis von Alkohol-Ethoxy-Carboxylaten
CA2147674C (fr) * 1994-05-16 1999-03-30 David Robert Zint Detergent semi-solide ou solide pour lave-vaisselle
ZA955295B (en) * 1994-06-27 1996-02-13 Diversey Corp Non-silicated soft metal safe product
US7404967B2 (en) 1994-12-21 2008-07-29 Cosmederm, Inc. Topical product formulations containing strontium for reducing skin irritation
US5958436A (en) * 1995-12-21 1999-09-28 Cosmederm Technologies Formulations and methods for reducing skin irritation
US6172021B1 (en) 1996-12-20 2001-01-09 The Procter & Gamble Company Dishwashing detergent compositions containing alkanolamine
AR017745A1 (es) * 1999-02-08 2001-09-12 Procter & Gamble Composiciones detergentes para lavar vajilla, que contienen diaminas organicas y magnesio, para una mejor limpieza con aguas blandas.
JP4509292B2 (ja) * 2000-04-04 2010-07-21 ライオン株式会社 界面活性剤組成物
US20080293607A1 (en) 2007-03-09 2008-11-27 Jones Brian E Alkaliphilic Bacillus Species alpha-Amylase Variants, Compositions Comprising alpha-Amylase Variants, And Methods of Use
BRPI0913378A2 (pt) 2008-06-06 2015-09-01 Danisco Us Inc Produção de glicose a partir do amido usando alfa-amilase do bacillus subtilis
EP2297312B1 (fr) 2008-06-06 2013-09-04 Danisco US Inc. Alpha amylases variantes de bacillus subtilis et leurs procédés d utilisation
JP5599113B2 (ja) 2008-06-06 2014-10-01 ダニスコ・ユーエス・インク 糖化酵素組成物及びその糖化方法
ES2412707T5 (es) * 2009-06-19 2023-06-12 Procter & Gamble Composición detergente líquida para lavado de vajillas a mano
EP2264136B1 (fr) 2009-06-19 2013-03-13 The Procter & Gamble Company Composition de détergent liquide pour lavage de la vaisselle à la main
CA2778471A1 (fr) 2009-10-23 2011-04-28 Danisco Us Inc. Procedes destines a reduire le saccharide donnant une couleur bleue
SE1250261A1 (sv) * 2011-10-31 2013-05-01 Billerudkorsnaes Gaevle Froevi Ab Bestrykningskomposition, ett förfarande för bestrykning av ett substrat, ettbestruket substrat, ett förpackningsmaterial och vätskeförpackning
US9096818B2 (en) * 2011-12-09 2015-08-04 Clariant International Ltd. Automatic dishwashing detergent compositions comprising ethercarboxylic acids or their salts and nonionic surfactants with a high cloud point
AU2012396242B2 (en) * 2012-12-07 2015-08-13 Colgate-Palmolive Company Cleaning composition
MY194073A (en) * 2014-11-18 2022-11-10 Basf Se Method of mineral oil production
AU2015376928B2 (en) 2015-01-15 2019-12-05 Ecolab Inc. Long lasting cleaning foam
CN109126622A (zh) * 2017-06-27 2019-01-04 华南师范大学 一种阴离子表面活性剂、洗涤剂和洗涤剂组合物
JP2020090606A (ja) * 2018-12-05 2020-06-11 株式会社コープクリーン 洗浄剤組成物

Family Cites Families (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
GB1225218A (fr) * 1968-07-31 1971-03-17
US4098818A (en) * 1976-12-10 1978-07-04 The Procter & Gamble Company Process for making carboxyalkylated alkyl polyether surfactants with narrow polyethoxy chain distribution
DE2754210A1 (de) * 1976-12-10 1978-06-15 Procter & Gamble Oberflaechenaktives mittel auf basis von carboxyalkylierten alkylpolyethern
DE3370164D1 (en) * 1982-10-28 1987-04-16 Procter & Gamble Liquid detergent compositions
DE3905938A1 (de) * 1989-02-25 1990-08-30 Huels Chemische Werke Ag Detergentienzusammensetzungen mit erhoehter viskositaet
EP0399752B1 (fr) * 1989-05-22 1997-08-06 The Procter & Gamble Company Détergent doux, liquide ou sous forme de gel pour laver la vaisselle et contenant comme agent tensio-actif un alkyl-éthoxy carboxylate

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HU9301418D0 (en) 1993-09-28
PT99527A (pt) 1992-09-30
MX9102078A (es) 1992-06-01
PT99530A (pt) 1992-09-30
DE69125022T2 (de) 1997-09-25
ATE149561T1 (de) 1997-03-15
BR9106983A (pt) 1993-08-24
MA22342A1 (fr) 1992-07-01
MY131210A (en) 2007-07-31
NO931738D0 (no) 1993-05-13
NO931738L (no) 1993-07-15
HUT64782A (en) 1994-02-28
GR3023502T3 (en) 1997-08-29
FI932199A (fi) 1993-05-14
WO1992008777A1 (fr) 1992-05-29
CZ87393A3 (en) 1994-07-13
DK0557426T3 (da) 1997-09-01
JPH06502884A (ja) 1994-03-31
CN1062371A (zh) 1992-07-01
FI932199A0 (fi) 1993-05-14
EP0557426A1 (fr) 1993-09-01
AU9063991A (en) 1992-06-11
SK48093A3 (en) 1994-01-12
JP3009464B2 (ja) 2000-02-14
DE69125022D1 (de) 1997-04-10
AR244795A1 (es) 1993-11-30
TR26532A (tr) 1995-03-15
ES2101078T3 (es) 1997-07-01

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