Classifications

• • C—CHEMISTRY; METALLURGY
  • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
  • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
  • C11D1/00—Detergent compositions based essentially on surface-active compounds; Use of these compounds as a detergent
  • C11D1/86—Mixtures of anionic, cationic, and 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
  • C11D1/02—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
• • 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
  • C11D1/29—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
  • 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
  • C11D1/523—Carboxylic alkylolamides, or dialkylolamides, or hydroxycarboxylic amides (R1-CO-NR2R3), where R1, R2 or R3 contain one hydroxy group per alkyl group
• • 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

Definitions

• the present invention relates heavy-duty liquid laundry detergent compositions containing anionic synthetic surfactant, ethoxylated nonionic surfactant. amide surfactant, and a calcium-selective detergent builder. This combination of ingredients provides superior cleaning on greasy and oily soils and overall outstanding detergency performance under a wide variety of laundering conditions, including washing in cool and cold water.
• U.S. Patent 4,153,570, Hennemann et al discloses low-foaming liquid detergents containing a specific mixture of anionic surfactants, ethoxylated nonionic surfactants, amide surfactant, fatty acid soap, hydrotrope and solvent.
• the compositions have a low ratio of anionic to nonionic surfactant. They can contain up to 6% of the soap, and up to 2% of a heavy metal complexing agent.
• U.S. Patent 3,707,503, Kenny, issued December 26, 1972 discloses stable, controlled sudsing heavy-duty liquid detergents containing anionic surfactants, fatty acid and alkanolamide in a weight ratio of fatty acid to amide of 1:2 to 1:11.
• European Patent Application No. 0 095 205 discloses detergent compositions containing anionic surfactants, quaternary ammonium, amine or amine oxide surfactants, and fatty acids, and formulated to provide a near-neutral wash pH.
• the compositions are preferably liquid detergents which additionally contain ethoxylated nonionic surfactants and polycarboxylate builders.
• the present invention encompasses a heavy-duty liquid laundry detergent composition comprising, by weight:
• the liquid detergents of the present invention contain anionic synthetic surfactant, ethoxylated nonionic surfactant, amide surfactant, and a calcium selective builder.
• anionic synthetic surfactant ethoxylated nonionic surfactant
• amide surfactant ethoxylated nonionic surfactant
• calcium-selective builder means any detergent builder that preferentially controls calcium ion in the wash solution, rather than magnesium or other hardness ions. This includes all manner of detergent builders except for polyphosphates, such as the tripolyphosphates, pyrophosphates, orthophosphates and glassy polymeric metaphosphates.
• the calcium-selective builder should be used at a level sufficient to sequester of at least about 2.0, preferably at least about 2.5, more preferably at least about 3.0, grains per gallon of calcium carbonate, while leaving at least about 0.5, preferably at least about 1.0, more preferably at least about 1.5, and up to a maximum of about 4, grains per gallon of unsequestered hardness, preferably in the form of magnesium.
• the calcium-selective builder generally represents from about 5% to about 30%, preferably from about 8% to about 25%, more preferably from about 10% to about 20%, by weight of the composition.
• the calcium-selective builder adequately controls wash water hardness, preventing excessive interactions with anionic surfactants and with soils. while allowing sufficient free hardness to complex some of the anionic surfactant to produce a hardness-surfactant (such as magnesium linear alkylbenzene sulfonate) that is highly effective at removing greasy and oily soils.
• a hardness-surfactant such as magnesium linear alkylbenzene sulfonate
• Such hardness--surfactants pack at the oil/water interface where they lower interfacial tension and enhance removal of greasy/oily soils.
• the ethoxylated nonionic surfactants herein suspend hardness-surfactants in the wash water solution.
• the amide surfactants further reduce oil/water interfacial tension, by hydrogen bonding with anionic surfactants, to improve greasy/oily soil removal. It will be appreciated that the level and type of surfactants and builders herein can thus be selected to optimize greasy/oily soil removal while providing overall outstanding detergency performance.
• the detergent compositions herein contain from about 10% to about 50%. preferably from about 15% to about 4 0%, more preferably from about 18% to about 30%, by weight, on an acid basis, of an anionic synthetic surfactant.
• Anionic synthetic surfactants are disclosed in U.S. Patent 4 ,285,8 41 , Barrat et al, issued August 25, 1981, and in U.S. Patent 3,919.678, Laughlin et al, issued December 30, 1975, both incorporated herein by reference.
• Useful anionic surfactants include the water-soluble salts, particularly the alkali metal, ammonium and alkylolam- monium (e.g., monoethanolammonium or triethanol--ammonium) salts, of organic sulfuric reaction products hav- mg in their molecular structure an alkyl group containing from about 8 to about 20 carbon atoms and a sulfonic acid or sulfuric acid ester group.
• alkyl is the alkyl portion of aryl groups.
• Examples of this group of synthetic surfactants are the alkyl sulfates, especially those obtained by sulfating the higher alcohols (C.-C,.
• alkylbenzene sulfonates in which the alkyl group contains from about 9 to about 15 carbon atoms, in straight chain or branched chain configuration, e.g., those of the type described in United States Patents 2,220,099 and 2,477,383.
• anionic surfactants herein are the water-soluble salts of: paraffin sulfonates containing from about 8 to about 2 4 (preferably about 12 to 18) carbon atoms; alkyl glyceryl ether sulfonates, especially those ethers of C 8-18 alcohols - (e.g., those derived from tallow and coconut oil); alkyl phenol ethylene oxide ether sulfates containing from about 1 to about 4 units of ethylene oxide per molecule and from about 8 to about 12 carbon atoms in the alkyl group; and alkyl ethylene oxide ether sulfates containing about 1 to about 4 units of ethylene oxide per molecule and from about 1 0 to about 20 carbon atoms in the alkyl group.
• Other useful anionic surfactants herein include the water-soluble salts of esters of alpha-sulfonated fatty acids containing from about 6 to about 20 carbon atoms in the fatty acid group and from about 1 to 10 carbon atoms in the ester group; water-soluble salts of 2-acyloxy-alkane-1--sulfonic acids containing from about 2 to 9 carbon atoms in the acyl group and from about 9 to about 23 carbon atoms in the alkane moiety; water-soluble salts of olefin sulfonates containing from about 12 to 24 carbon atoms; and beta--alkyloxy alkane sulfonates containing from about 1 to 3 carbon atoms in the alkyl group and from about 8 to 20 carbon atoms in the alkane moiety.
• Preferred anionic surfactants herein are the alkyl sulfates of the formula wherein R is an alkyl chain having from about 12 to about 18 carbon atoms, saturated or unsaturated, M is a cation which makes the compound water-soluble, especially an alkali metal, ammonium or substituted ammonium cation, and x is from 0 to about 4.
• R is a C,rC,6 alkyl or hydroxyalkyl group, especially a C"-C,5 alkyl, and m is from about 0 to about 3.
• anionic surfactants are the linear straight chain alkylbenzene sulfonates in which the average number of carbon atoms in the alkyl group is from about 1 2 to about 13, and the C 12 . 15 alcohol sulfates containing from 0 to about 3 ethylene oxide units, as described above. Also preferred are mixtures of these surfactants in a weight ratio of from about 3:1 to about 1:3, preferably from about 2:1 to about 1:2. These anionics form hardness, preferably magnesium, surfactants that are particularly effective at lowering interfacial tension and removing greasy/oily soils.
• Compositions of the present invention also contain from about 5% to about 20%, preferably from about 6% to about 15%, more preferably from about 7% to about 12%, by weight of a mixture of an ethoxylated nonionic surfactant and an amide surfactant in a weight ratio of from about 4:1 to 1:4, preferably from about 3:1 to about 1:3, more preferably from about 2:1 to about 1:2.
• the weight ratio of anionic synthetic surfactant (on an acid basis) to the total nonionic surfactant (both the ethoxylated nonionic and the amide) should be from about 2:1 to about 4:1, preferably from about 2.5:1 to about 3.5:1, to ensure the formation and adsorption of sufficient hardness surfactants at the oil/water interface to provide good greasyloily soil removal.
• the ethoxylated nonionic surfactants herein have an HLB (hydrophilic-lipophilic balance) of from about 5 to about 17, preferably from about 6 to about 13.
• HLB hydrophilic-lipophilic balance
• Suitable ethoxylated nonionic surfactants herein are as follows: (1) The polyethylene oxide condensates of alkyl phenols.
• These compounds include the condensation products of alkyl phenols having an alkyl group containing from about 6 to 12 carbpn atoms in either a straight chain or branched chain configuration with ethylene oxide, said ethylene oxide being present in an amount equal to 3 to 25 moles of ethylene oxide per mole of alkyl phenol.
• Examples of compounds of this type include nonyl phenol condensed with about 9.5 moles of ethylene oxide per mole of nonyl phenol; dodecylphenol condensed with about 12 moles of ethylene oxide per mole of phenol; dinonyl phenol condensed with about 15 moles of ethylene oxide per mole of phenol; and diisooctyl phenol condensed with about 15 moles of ethylene oxide per mole of phenol.
• Commercially available nonionic surfactants of this type include Igepal CO-630, marketed by the GAF Corporation, and Triton X-45, X-114, X-100, and X-102, all marketed by the Rohm & Haas Company.
• the condensation products of aliphatic alcohols with from about 1 to about 25 moles of ethylene oxide can either be straight or branched, primary or secondary, and generally contains from about 8 to about 22 carbon atoms.
• Examples of such ethoxylated alcohols include the condensation product of myristyl alcohol condensed with about 10 moles of ethylene oxide per mole of alcohol; and the condensation product of about 9 moles of ethylene oxide with coconut alcohol (a mixture of fatty alcohols with alkyl chains varying in length from 10 to 14 carbon atoms).
• nonionic surfactants in this type include Tergitol 1 5-S-9, marketed by union Carbide Corporation, Neodol 45-9, Neodol 23-6.5, Neodol 45-7, and Neodol 45-4, marketed by Shell Chemical Company, and Kyro EOB, marketed by The Procter & Gamble Company.
• the condensation products of ethylene oxide with the product resulting from the reaction of propylene oxide and ethylenediamine consist of the reaction product of ethylenediamine and excess propylene oxide, said moiety having a molecular weight of from about 2500 to about 3000.
• This hydrophobic moiety is condensed with ethylene oxide to the extent that the condensation product contains form about 40% to about 80% by weight of polyoxyethylene and has a molecular weight of from about 5,000 to about 11,000.
• Examples of this type of nonionic surfactant include certain of the commercially available Tetronic compounds, marketed by Wyandotte Chemical Corporation.
• Preferred ethoxylated nonionic surfactants are of the formula R' (OC 2 H 4 ) n OH, wherein R' is a C, o -C, 6 alkyl group or a C,-C" alkyl phenyl group, n is from about 3 to about 9, and said nonionic surfactants has an HLB (hydrophile--lipophile balance) of from about 9 to about 13, preferably from about 1 0 to about 13.
• HLB hydrophile--lipophile balance
• Amide surfactants herein are of the formula wherein R' is an alkyl, hydroxyalkyl or alkenyl radical containing from about 8 to about 20 carbon atoms, and R 2 and R' are selected from the group consisting of hydrogen, methyl, ethyt, propyl, isopropyl, 2-hydroxyethyl, 2--hydroxypropyl, 3-hydroxypropyl, and said radicals additionally containing up to about 5 ethylene oxide units, provided at least one of R' and R 3 contains a hydroxyl group.
• Preferred amides are the C,-C, ° fatty acid alkylol amides in which each alkylol group contains from 1 to 3 carbon atoms, and additionally can contain up to about 2 ethylene oxide units. Particularly preferred are the C 12 -C 16 fatty acid monoethanol and diethanol amides.
• compositions of the present invention comprise from about 5% to about 30%, preferably from about 8% to about 25%, more preferably from about 10% to about 20%, by weight of a calcium-selective builder.
• Preferred builders herein are fatty acids containing from about 12 to about 22 carbon atoms.
• Preferred are saturated fatty acids containing from about 12 to about 18 carbon atoms.
• Suitable saturated fatty acids can be obtained from natural sources such as plant or animal esters (e.g., palm kemel oil, palm oil and coconut oil) or synthetically prepared (e.g., via the oxidation of petroleum or by hydrogenation of carbon monoxide via the Fisher-Tropsch process).
• suitable saturated fatty acids for use in the compositions of this invention include capric, lauric, myristic, coconut and palm kemel fatty acid.
• aminopolycarboxylates cycloalkane polycarboxylates, ether polycarboxylates, alkyl polycarboxylates, epoxy polycarboxylates, tetrahydrofuran polycarboxylates, benzene polycarboxylates, and polyacetal polycarboxylates are suitable for use herein.
• polycarboxylate builders are sodium and potassium ethylenediaminetetraacetate; sodium and potassium nitrilotriacetate; the water-soluble salts of phytic acid, e.g., sodium and potassium phytates, disclosed in U.S. Patent 1,739,942, Eckey, issued March 27, 1956, incorporated herein by reference; the polycarboxylate materials described in U.S. Patent 3,364,103, incorporated herein by reference; and the water-soluble salts of polycarboxylate polymers and copolymers described in U.S. Patent 3,308,067, Diehl, issued March 7, 1967, incorporated herein by reference.
• Useful detergent builders also include the water-soluble salts of polymeric aliphatic polycarboxylic acids having the following structural and physical characteristics: (a) a minimum molecular weight of about 350 calculated as to the acid form; (b) an equivalent weight of about 50 to about 80 calculated as to acid form; (3) at least 45 mole percent of the monomeric species having at least two carboxyl radicals separated from each other by not more than two carbon atoms: (d) the site of attachment of the polymer chain of any carboxyl-containing radical being separated by not more than three carbon atoms along the polymer chain from the site of attachment of the next carboxyl-containing radical.
• Specific examples of such builders are the polymers and copolymers of itaconic acid, aconitic acid, maleic acid, mesaconic acid, fumaric acid, methylene malonic acid, and citraconic acid.
• Suitable polycarboxylate builders include the water-soluble salts, especially the sodium and potassium salts, of mellitic acid, citric acid, pyromellitic acid, benzene pentacarboxylic acid, oxydiacetic acid, carboxymethylox- ysuccinic acid, carboxymethyloxymalonic acid, cis--cyclohexanehexacarboxylic acid, cis--cyclopentanetetracarboxylic acid and oxydisuccinic acid.
• water-soluble salts especially the sodium and potassium salts, of mellitic acid, citric acid, pyromellitic acid, benzene pentacarboxylic acid, oxydiacetic acid, carboxymethylox- ysuccinic acid, carboxymethyloxymalonic acid, cis--cyclohexanehexacarboxylic acid, cis--cyclopentanetetracarboxylic acid and oxydisuccin
• polycarboxylates for use herein are the polyacetal carboxylates described in U.S. Patent 4,144,226, issued March 13, 1979 to Crutchfield et al, and U.S. Patent 4 , 14 6,495, issued March 27, 1979 to Crutchfield et al, both incorporated herein by reference.
• calcium-selective detergent builders useful herein include the alummosilicate ion exchange material described in U.S. Patent 4,405,483, Kuzel et al, issued September 20, 1983, incorporated herein by reference. Crystalline aluminosilicates are of the formula wherein z and y are at least about 6, the molar ratio of z to y is from about 1.0 to about 0.5 and x is from about 10 to about 264.
• Amorphous hydrated aluminosilicate material useful herein has the empirical formula wherein M is sodium, potassium, ammonium, or substituted ammonium, z is from about 0.5 to about 2, y is 1 and said material has a magnesium ion exchange capacity of at least about 50 milligram equivalents of CaCO, hardness per gram of anhydrous aluminosilicate.
• Preferred synthetic crystalline aluminosilicate ion exchange materials useful herein are available under the designations Zeolite A, Zeolite B, and Zeolite X.
• the crystalline aluminosilicate ion exchange material has the formula wherein x is from about 20 to about 30, especially about 27.
• compositions also contain from about 20% to about 75%, preferably from about 25% to about 65%, more preferably from about 30% to about 55%, of water.
• Optional components for use in the liquid detergents herein include neutralizing agents, buffering agents. , phase regulants, solvents, hydrotropes, enzymes, enzyme stabiiiz- ing agents, polyacids, suds regulants, opacifiers, antioxidants, bacteriacides, dyes, perfumes, and brighteners described in U.S. Patent 4,285,84 1 , Barrat et al, issued August 25, 198 1 , incorporated herein by reference.
• compositions herein are preferably formulated to provide an initial pH of from about 7.0 to about 9.0, preferably from about 7.0 to about 8.5, more preferably from about 7.2 to about 8.0, at a concentration of from about 0.1% to about 1 % by weight in water at 20°C.
• Such near-neutral wash pH's are preferred for best overall detergency performance, including on greasy and oily soils.
• a preferred neutralization system contains from about 0 to about 0.04 moles, preferably from about 0.01 to about 0.035 moles, more preferably from about 0.015 to about 0.03 moles, per 100 grams of composition of an alkanolamine selected from the group consisting of monoethanolamine, diethanolamine, triethanolamine, and mixtures therof.
• Low levels of the alkanolamines, particularly monoethanolamine, are preferred to enhance product stability, detergency performance, and odor. However, the amount of alkanolamine should be minimized for best chlorine bleach compatibility. While the present compositions can contain mixtures of the alkanolamines, best color stability is obtained using single alkanolamines.
• compositions herein contain potassium and sodium ions in a potassium to sodium molar ratio of from about 0.1 to about 1.3, preferably from about 0.6 to about 1, for best phase stability.
• a preferred solvent system is comprised of ethanol, a polyol and water.
• Ethanol is preferably present at a level of from about 2% to about 1 0%, more preferably from about 5% to about 9%, by weight of the composition.
• Any polyol containing 2 to 6 carbon atoms and from 2 to 6 hydroxy groups can be used in the present compositions.
• examples of such polyols are ethylene glycol, propylene glycol and glycerine. Propylene glycol is particularly preferred.
• the polyol preferably represents from about 2% to about 1 5%, more preferably from about 3% to about 10%, by weight of the composition.
• compositions herein further contain from about 0.5% to about 5%, preferably from about 1% to about 3%, by weight of a highly ethoxylated polyethyleneamine or polyethyleneimine soil removal and antiredeposition agent, such as those described in European Patent Application No. 112,593, Vander Meer, published July 4, 1984, incorporated herein by reference.
• a particularly preferred material is tetraethylene pentaimine ethoxylated with about 15-18 moles of ethylene oxide at each hydrogen site.
• Heavy-duty liquid laundry detergents of the present invention are as follows.
• Composition A is preferably prepared by adding the components, with continuous mixing, in the following order: paste premix of alkylbenzene sulfonic acid, sodium hydroxide, propylene glycol and ethanol; paste premix of alkyl polyethoxylate sulfuric acid, sodium hydroxide and ethanol; premix of water, brighteners, alkanolamine, and alcohol polyethoxylate; alcohol polyethoxylate; ethanol; sodium and potassium hydroxide; fatty acid; citric acid; premix of formate, amide and TEPA-E 15-18 ; adjust pH to about 8.1; and balance of components.
• compositions B and C can be prepared in a similar manner.
• Composition A provided better overall cleaning, particularly on greasy/oil soils at warm (95°F) wash water temperatures, than similar compositions containing 8% of the alcohol polyethoxylate and none of the amide, and 8% of the amide and none of the alcohol polyethoxylate.

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• 1986
  • 1986-01-13 EP EP86200049A patent/EP0189225A2/de not_active Withdrawn
  • 1986-01-21 GB GB08601381A patent/GB2169916B/en not_active Expired
  • 1986-01-21 GR GR860171A patent/GR860171B/el unknown
  • 1986-01-21 AU AU52583/86A patent/AU5258386A/en not_active Abandoned
  • 1986-01-22 JP JP61011825A patent/JPS61252300A/ja active Pending
• 1987
  • 1987-09-30 MY MYPI87002619A patent/MY102707A/en unknown

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