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EP0399752B1 - Mildes, flüssiges oder gelförmiges Spülwaschmittel, enthaltend ein Alkyl-ethoxy-carboxylat als oberflächenaktiven Stoff - Google Patents

Mildes, flüssiges oder gelförmiges Spülwaschmittel, enthaltend ein Alkyl-ethoxy-carboxylat als oberflächenaktiven Stoff Download PDF

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Publication number
EP0399752B1
EP0399752B1 EP90305469A EP90305469A EP0399752B1 EP 0399752 B1 EP0399752 B1 EP 0399752B1 EP 90305469 A EP90305469 A EP 90305469A EP 90305469 A EP90305469 A EP 90305469A EP 0399752 B1 EP0399752 B1 EP 0399752B1
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alkyl
composition
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compositions
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French (fr)
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EP0399752A2 (de
EP0399752A3 (de
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Rodney Mahlon Wise
Thomas Anthony Cripe
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Procter and Gamble Co
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Procter and Gamble Co
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Classifications

    • D—TEXTILES; PAPER
    • D21—PAPER-MAKING; PRODUCTION OF CELLULOSE
    • D21D—TREATMENT OF THE MATERIALS BEFORE PASSING TO THE PAPER-MAKING MACHINE
    • D21D1/00—Methods of beating or refining; Beaters of the Hollander type
    • 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
    • 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
    • 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
    • C11D1/66—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 the washing of dishes with a 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 carb
  • the present invention relates to a process of washing dishes with a light-duty liquid or gel, preferably liquid, dishwashing detergent composition comprising from about 5% to 70% of a surfactant mixture comprising:
  • the light-duty liquid or gel, preferably liquid, dishwashing detergent compositions used in the process 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.
  • a surfactant mixture comprising a major amount of an alkyl ethoxy carboxylate surfactant and little or no alcohol ethoxylate and soap by-product contaminants.
  • the liquid compositions used in the process 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 contain from about 20% to about 70%, preferably from about 25% to about 45%, most preferably from about 28% 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 about 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 about 10, and the ethoxylate distribution is such that, on a weight basis, the amount of material where x is 0 is less than about 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 about 25%, preferably less than about 15%, most preferably less than about 10%, the average x is from about 2 to 4 when the average R is C 13 or less, and the average x is from about 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-
  • Suitable alcohol precursors of the alkyl ethoxy carboxylates 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.
  • 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 used in the compositions in the process of the present invention also contains from 0% to about 10%, preferably less than about 8%, most preferably less than about 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 about 10 and the average x is less than 6.
  • the surfactant mixture also contains 0% to about 10%, preferably less than about 8%, most preferably less than about 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 the process of 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.
  • a hindered base such as potassium tert-butoxide can replace the sodium hydroxide in the above cited patents, thus yielding high purity alkyl ethoxy carboxylates with less stringent temperature and pressure requirements.
  • a hindered base of the formula RO - M + constituting generally an alkyl group, a reactive oxygen center, and a cation is used.
  • the structure of this hindered base is secondary or tertiary and contains a non-linear alkyl group with at least one site of branching within 3 carbon atoms of the reactive center, the oxygen atom, and an alkali metal or alkaline earth metal cation.
  • 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 1 to 760 mm Hg.
  • compositions used in the process of this invention have a pH from about 7 to 11, preferably determined as the pH of a 10% by weight aqueous solution with a pH meter.
  • the preferred detergent compositions have a pH from about 8 to 10.5 and most preferably from about 8.5 to 10.
  • liquid dishwashing compositions have a pH of about 7. It has been found for detergent compositions used in the process of this invention that a more alkaline pH of about 9 greatly improves the grease cleaning as compared to a product with a pH of 7. This cleaning benefit appears to be unique to compositions containing the present alkyl ethoxy carboxylates. Surprisingly, the compositions used in the process of this invention are also more mild to hands at this alkaline pH than at a pH of 7.
  • a composition with a pH greater than 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).
  • Dishwashing compositions used in the process of the invention will be subjected to acidic stresses created by food soils when put to use, i.e., diluted and applied to soiled dishes.
  • a buffering agent having a pKa value about 0.5 to 1.0 pH units below the desired pH value should be present therein. Under these conditions the buffering agent most effectively controls the pH while using the least amount thereof.
  • 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.
  • Preferred buffering agents for compositions used in the process of this invention are nitrogen-containing materials. Some examples are glycine or other amino acids or lower alcohol amines like mono-, di-, and tri-ethanolamine. Other preferred nitrogen-containing buffering agents are 2-amino-2-ethyl-1,3-propanediol, tris-(hydroxymethyl)aminomethane, and disodium glutamate. Boric acid is also preferred. These buffering agents are typically present at a level of from about 0.1% to 10% by weight, preferably from about 1% to 7%, most preferably from about 1.5% to 5%.
  • 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 used in the process of the invention are ammonium, sodium, and potassium.
  • ammonium is most preferred, but at pH levels above about 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 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.
  • the divalent ions are added as a chloride or sulfate 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.
  • the level of divalent ion in the composition is from 0% to about 1.5%, preferably from about 0.2% to 1%, most preferably from about 0.3% to 0.8%, by weight.
  • Particularly preferred divalent ions are magnesium ions.
  • the divalent ion is magnesium, present in the composition at a level of from about 0.1% to 1%, most preferably from about 0.3% to 0.8%, by weight, while the pH is preferably from about 8 to 9.5 and most preferably from about 8.5 to 9.5.
  • Compositions that contain higher levels of magnesium and have a pH much above about 9.5 are not preferred due to a tendency to form precipitates.
  • the amount of magnesium ions present will be dependent upon the amount of total anionic surfactant present therein, including the amount of alkyl ethoxy carboxylates.
  • the molar ratio of magnesium ions to total anionic surfactant is from about 0.25:1 to about 0.5:1.
  • compositions used in the process 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.
  • the co-surfactants for the compositions can also contain mixtures of anionic surfactants with alkyl polyglucosides.
  • 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 (suds booster) at 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.
  • the composition 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 atom
  • 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, all of which are incorporated herein by reference.
  • 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.
  • ethylene oxide condensates suitable as suds stabilizers are the condensation products of aliphatic alcohols with ethylene oxide.
  • the alkyl chain of the aliphatic alcohol can either be straight or branched and generally contains from about 8 to about 18, preferably from about 8 to about 14, carbon atoms for best performance as suds stabilizers, the ethylene oxide being present in amounts of from about 8 moles to about 30, preferably from about 8 to about 14 moles of ethylene oxide per mole of alcohol.
  • 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 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
  • 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 compositons 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), incorporated herein by reference.
  • detergency builders either of the organic or inorganic type.
  • water-soluble inorganic builders which can be used, alone or in admixture with themselves or with organic alkaline sequestrant builder salts, are alkali metal carbonates, phosphates, polyphosphates, and silicates.
  • alkali metal carbonates phosphates, polyphosphates, and silicates.
  • Specific examples of such salts are sodium tripolyphosphate, sodium carbonate, potassium carbonate, sodium pyrophosphate, potassium pyrophosphate, potassium tripolyphosphate, and sodium hexametaphosphate.
  • alkali metal polycarboxylates e.g., water-soluble citrates such as sodium and potassium citrate, sodium and potassium tartrate, sodium and potassium ethylenediaminetetraacetate, sodium and potassium N-(2-hydroxyethyl)-ethylene diamine triacetates, sodium and potassium nitrilo triacetates (NTA), sodium and potassium N-(2-hydroxyethyl)-nitrilo diacetates, sodium and potassium oxydisuccinates, and sodium and potassium tartrate mono- and di-succinates, such as described in U.S. Pat. No.
  • alkali metal polycarboxylates e.g., water-soluble citrates such as sodium and potassium citrate, sodium and potassium tartrate, sodium and potassium ethylenediaminetetraacetate, sodium and potassium N-(2-hydroxyethyl)-ethylene diamine triacetates, sodium and potassium nitrilo triacetates (NTA), sodium and potassium N-(2-hydroxyethy
  • detergency builders such as water-soluble phosphonates can find use in the compositions of the invention.
  • detergency builders have limited value in dishwashing detergent compositions, and use at levels above about 10% can restrict formulation flexibility in the liquid or gel compositions herein because of solubility and phase stability considerations.
  • Alcohols such as ethyl alcohol and propylene glycol
  • hydrotropes such as sodium and potassium toluene sulfonate, sodium and potassium xylene sulfonate, trisodium sulfosuccinate, and related compounds (as disclosed in U.S. Pat. No. 3,915,903, incorporated herein by reference), and urea, 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%, potassium or sodium toluene, xylene, or cumene sulfonate at a level of from 0% to about 10%, urea at a level of from 0% to about 10%, and trisodium sulfosuccinate at a level of from 0% to about 15% are particularly useful in liquid compositions.
  • Gel compositions normally would not contain alcohols. These gel compositions may contain higher levels of potassium or sodium toluene, xylene, or cumene sulfonate, and urea at higher levels, i.e., from about 10% to about 30%, as gelling agents (see U.S. Patent No. 4,615,819 and GB 2,179,054A).
  • compositions herein will typically contain up to about 80%, preferably from about 30% to about 70%, most preferably from about 40% to about 65%, of water.
  • Formulation A is made by adding ethanol, sodium chloride, and sodium xylene sulfonate to the alkyl ethoxy carboxylate-containing surfactant mixture.. The remaining surfactants are then added and mixed in. Glycine is then added and the pH is adjusted to about 10 with sodium hydroxide. Finally, the magnesium chloride is added, which reduces the pH to about 9.5. Final viscosity and pH adjustments can be made at this time, followed by the addition of perfume and dye. The balance is water.
  • Formulation B is made by adding ethanol, sodium chloride, and sodium xylene sulfonate to the sodium alkyl ethoxy carboxylate. The remaining formula components are added in the order given in the table.
  • Formulation C is made by adding ethanol, sodium chloride, and sodium xylene sulfonate to the sodium salt of alkyl ethoxy carboxylate.
  • the alkyl glucoside is mixed in and the temperature of the mixture raised to about 40°C.
  • the coconut monoethanolamine amide is warmed to about 65°C and mixed in. Minor pH and viscosity adjustments are made at this time, followed by the addition of dye and perfume and water to bring the formulation to 100%.
  • the surfactant portion of the above mixture contains about 93.9% 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 2.8% and the amount of material where x is greater than 7 is less than about 2% by weight of the alkyl ethoxy carboxylates.
  • the average x in the distribution is 2.8.
  • the surfactant mixture contains 0% soap materials.
  • Example I The liquid formulations in Example I can also be successfully made by replacing the alkyl ethoxy carboxylate-containing surfactant mixture with a surfactant mixture (described below) prepared via an oxidation process wherein alcohol ethoxylates are reacted with oxygen in the presence of a noble metal catalyst as is disclosed generally in U.S. Pat. Nos. 4,223,460; 4,214,101; and 4,348,509; and German Pat. No. 3,446,561; and Japanese Patent Application No. 62,198,641.
  • a noble metal catalyst as is disclosed generally in U.S. Pat. Nos. 4,223,460; 4,214,101; and 4,348,509; and German Pat. No. 3,446,561; and Japanese Patent Application No. 62,198,641.
  • the surfactant mixture comprises 92.4% alkyl ethoxy carboxylates of the formula RO(CH 2 CH 2 O) x CH 2 COO - Na + wherein R is a C 12-14 alkyl averaging 12.7 with x ranging from 0 to about 12.
  • R is a C 12-14 alkyl averaging 12.7 with x ranging from 0 to about 12.
  • the average x in the distribution is 2.5.
  • the surfactant mixture also contains about 6.4% of alcohol ethoxylates of the formula RO(CH 2 CH 2 O) x H with R being a C 12-14 alkyl averaging 12.7 and the average x is about 3.7.
  • the surfactant mixture contains about 1.2% by weight of soaps of the formula RCOO - Na + wherein R is C 11-13 averaging C 11.7 .
  • This formulation would contain 15% by weight of the alkyl ethoxy carboxylates, 1.04% by weight of alcohol ethoxylates, and 0.20% by weight of soaps.
  • the other components in the formulations are identical. Minor modifications in the ethanol and the sodium xylene sulfonate levels may be made to adjust the viscosity and stability of the formulation to match the formulations of Example I.
  • a gel composition suitable by use in the process of the present invention can be prepared using the general method described in U.S. Patent No. 4,615,819.
  • the composition contains 35.0% by weight sodium C 12-14 alkyl ethoxy (3.0 ave.) carboxylate and 2.3% by weight C 12-14 alkyl ethoxy (3.0 ave.) alcohol.
  • urea is used as the gelling "additive"
  • the pH of a 10% by weight aqueous solution should be kept below about 8.0 in order to prevent ammonia smell in the composition, which results from decomposition of the urea.
  • This gel composition has good grease cutting ability and excellent hand mildness properties as compared to current available gel compositions (e.g., U.S. Patent No. 4,615,819).
  • Ethanol is added to the acid-form of the alkyl ethoxy carboxylate mixture. Then a slight excess over the stoichiometric amount of sodium hydroxide needed to neutralize the acid is added and mixed in. Following neutralization, alkyl sulfate, cumene sulfonate, trisodium sulfosuccinate, betaine, and amine oxide are added if called for.
  • the appropriate buffering agents glycine and/or tris(hydroxymethyl)aminomethane
  • glycine and/or tris(hydroxymethyl)aminomethane are then added as an aqueous solution at or, in the cases of Formulations X and Y, slightly above the target pH of the composition.
  • magnesium chloride is added at this time to the mixture having a pH of between 9.5 and 10. If the magnesium is added to a mixture having a pH greater than about 10, precipitation of the magnesium can occur. Finally, perfume and dye are added, the viscosity is adjusted using ethanol, and water is added to complete the formula.

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Claims (7)

  1. Verfahren zum Geschirrspülen mit einer milden, flüssigen oder gelförmigen Geschirrspülmittelzusammensetzung, die auf Gewichtsbasis 5 bis 70 % einer Tensidmischung umfaßt, dadurch gekennzeichnet, daß die Tensidmischung auf Gewichtsbasis:
    (a) 80 bis 100 %, vorzugsweise 90 bis 95%, Alkylethoxycarboxylate der Formel:

            RO(CH2CH2O)xCH2COO-M+

    worin R eine C12-C16-, vorzugsweise eine C12-C14-Alkylgruppe ist, x im Bereich von 0 bis 10 liegt, und die Ethoxylatverteilung der Art ist, daß auf Gewichtsbasis die Menge an Material, worin x 0 ist, weniger als 20 % beträgt und die Menge an Material, worin x größer als 7 ist, weniger als 25 % beträgt, wobei im Durchschnitt x 2 bis 4 ist, wenn R im Durchschnitt C13 oder weniger ist, und x im Durchschnitt 3 bis 6 ist, wenn R im Durchschnitt größer als C13 ist, und M ein Kation ist;
    (b) 0 bis 10 %, vorzugsweise weniger als 5 % Alkoholethoxylate der Formel:

            RO(CH2CH2O)xH

    worin R eine C12-C16-Alkylgruppe ist und x im Bereich von 0 bis 10 liegt, und x im Durchschnitt weniger als 6 ist: und
    (c) 0 bis 10 %, vorzugsweise weniger als 5 % Seifen der Formel:

            RCOO-M+

    worin R eine C11-C15-Alkylgruppe ist und M ein Kation ist; umfaßt, wobei eine 10 gew.-%-ige wäßrige Lösung der Zusammensetzung einen pH von 7 bis 11 aufweist.
  2. Verfahren nach Anspruch 1, wobei die Zusammensetzung eine Flüssigkeit ist und 12 bis 30 % der Tensidmischung umfaßt.
  3. Verfahren nach Anspruch 1, wobei die Zusammensetzung ein Gel ist und 28 bis 35 % der Tensidmischung umfaßt.
  4. Verfahren nach mindestens einem der vorangehenden Ansprüche, wobei die Zusammensetzung einen pH von 8,5 bis 10 aufweist.
  5. Verfahren nach mindestens einem der vorangehenden Ansprüche, wobei die Zusammensetzung 0,3 bis 0.8 % Magnesiumionen umfaßt.
  6. Verfahren nach mindestens einem der vorangehenden Ansprüche, wobei die Zusammensetzung weiterhin ein Co-Tensid umfaßt, gewählt aus Alkylbenzolsulfonaten, Alkylsulfaten, Paraffinsulfonaten, Olefinsulfonaten, Alkylethersulfaten, Fettsäureestersulfonaten, Alkylpolyglukosiden und Mischungen hiervon.
  7. Verfahren nach mindestens einem der vorangehenden Ansprüche, wobei die Zusammensetzung weiterhin einen Schaumverbesserer umfaßt, gewählt aus Betainen, Ethylenoxidkondensaten, Fettsäureamiden, semipolaren nichtionogenen Aminoxid-Verbindungen, kationischen Tensiden und Mischungen hiervon.
EP90305469A 1989-05-22 1990-05-21 Mildes, flüssiges oder gelförmiges Spülwaschmittel, enthaltend ein Alkyl-ethoxy-carboxylat als oberflächenaktiven Stoff Expired - Lifetime EP0399752B1 (de)

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KR101998346B1 (ko) 2013-04-30 2019-07-09 애경산업(주) 우수한 상 안정성을 가지는 구조화된 액체 세제 조성물

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KR20180016467A (ko) * 2018-02-06 2018-02-14 애경산업(주) 보관 안정성이 우수한 액체세제 조성물

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EP0399752A2 (de) 1990-11-28
NZ233747A (en) 1993-04-28
AU4622193A (en) 1993-12-02
BR9002406A (pt) 1991-08-06
CN1048059A (zh) 1990-12-26
MA21850A1 (fr) 1990-12-31
JPH0331398A (ja) 1991-02-12
DE69031193D1 (de) 1997-09-11
AU5575090A (en) 1990-11-22
FI902495A0 (fi) 1990-05-21
DE69031193T2 (de) 1998-03-12
ATE156514T1 (de) 1997-08-15
EP0399752A3 (de) 1991-05-08
JP2798481B2 (ja) 1998-09-17
ES2106729T3 (es) 1997-11-16

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