EP0199403B1 - Stabile flüssige Reinigungsmittel - Google Patents

Stabile flüssige Reinigungsmittel Download PDF

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Publication number
EP0199403B1
EP0199403B1 EP86200584A EP86200584A EP0199403B1 EP 0199403 B1 EP0199403 B1 EP 0199403B1 EP 86200584 A EP86200584 A EP 86200584A EP 86200584 A EP86200584 A EP 86200584A EP 0199403 B1 EP0199403 B1 EP 0199403B1
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Prior art keywords
alkyl
composition
group
carbon atoms
formula
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EP86200584A
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English (en)
French (fr)
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EP0199403A2 (de
EP0199403A3 (en
Inventor
Eugene Paul Gosselink
Larry James Hughes
Antoinette Louise Larrabee
Robert Mermelstein
Nodie Monroe Washington
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Procter and Gamble Co
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Procter and Gamble Co
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Priority to AT86200584T priority Critical patent/ATE98674T1/de
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Publication of EP0199403A3 publication Critical patent/EP0199403A3/en
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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
    • C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
    • C11D3/16—Organic compounds
    • C11D3/37—Polymers
    • C11D3/3703—Macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
    • C11D3/3715—Polyesters or polycarbonates
    • 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
    • C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
    • C11D3/0005—Other compounding ingredients characterised by their effect
    • C11D3/0036—Soil deposition preventing compositions; Antiredeposition agents
    • 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
    • C11D1/42—Amino alcohols or amino ethers
    • C11D1/44—Ethers of polyoxyalkylenes with amino alcohols; Condensation products of epoxyalkanes with amines
    • 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
    • C11D1/38—Cationic compounds
    • C11D1/62—Quaternary ammonium 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
    • C11D1/72—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

Definitions

  • the present invention relates to heavy-duty liquid detergent compositions containing a soil release agent; anionic surfactant (preferably comprising a sulfonate surfactant and alcohol ethoxylate sulfate surfactant); ethoxylated nonionic surfactant; an optional quaternary ammonium, amine, amide, or amine oxide surfactant; preferably, saturated fatty acid and polycarboxylate builders; a neutralization system preferably comprising sodium, potassium and/or low levels of alkanolamines; and a solvent system preferably comprising ethanol, polyol and water.
  • the compositions are isotropic liquids which provide a high level of detergency performance.
  • liquid detergents capable of providing superior cleaning under a wide variety of laundering conditions.
  • Such compositions generally require a number of ingredients which tend to separate into discrete phases.
  • Isotropic liquid detergents are desired for both consistency of performance and aesthetic reasons.
  • the compositions should remain isotropic during shipping and storage, where temperatures of 55°F (12.8°C) or lower are often encountered. They preferably are also formulated to recover, after freezing and thawing, to an isotropic phase prior to consumer use.
  • Liquid detergents desirably contain a soil release agent to enhance performance.
  • soil release agents are difficult to incorporate in liquid detergents.
  • an isotropic liquid detergent with a soil release agent capable of providing superior cleaning, bleach compatibility and product stability.
  • US 4 125 370 discloses random ethylene terephtalate polyethylene oxide terephtalate polymers useful as soil release agents.
  • European Patent Application 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 compositions have a pH of from about 6.0 to about 7.5.
  • EP-A-185 427 discloses liquid detergent compositions of the presently claimed type comprising block polyester soil release agents belonging to the same class as the present soil release agents.
  • the present invention encompasses heavy-duty liquid detergent compositions comprising, by weight:
  • compositions preferably contain from 20% to 40% of (a), (b), (c) and (d); said components being selected to provide an isotropic liquid at 55°F (12.8°C) having an initial pH of from 7.5 to 9, preferably from 8.4 to 8.8, at a concentration of 10% by weight in water at 68°F (20°C).
  • the liquid detergents of the present invention contain anionic surfactant, preferably a mixture of sulfonate and alcohol ethoxylate sulfate anionic surfactants; ethoxylated nonionic surfactant; optional quaternary ammonium, amine, amide, and/or amine oxide surfactants; builders, preferably saturated fatty acid and/or, polycarboxylate builders; a neutralization system, preferably comprising sodium, potassium and preferably low levels of alkanolamines; and a solvent system said system not consisting of water only, said system preferably comprising ethanol, polyol and water.
  • anionic surfactant preferably a mixture of sulfonate and alcohol ethoxylate sulfate anionic surfactants
  • ethoxylated nonionic surfactant optional quaternary ammonium, amine, amide, and/or amine oxide surfactants
  • builders preferably saturated fatty acid and/or, polycarboxylate builders
  • compositions herein are formulated to provide a high level of detergency performance under a wide variety of laundering conditions.
  • Preferred compositions herein are isotropic liquids at 50°F (10°C). They preferably also recover, after freezing and thawing, to an isotropic form by 55°F (12.8°C), more preferably by 50°F (10°C).
  • compositions preferably comprise a neutralization system comprising mixed potassium and sodium ions.
  • Complete sodium neutralization tends to cause crystallization of the polycarboxylate builder and poor incorporation of the soil release polymer, whereas all potassium neutralization results in an unacceptably high gel point.
  • the total level of organic and inorganic bases should also be selected to provide a sufficiently high product pH to minimize the level of poorly-soluble free fatty acids, without being so high that pH sensitive stain removal, enzyme stability, soil release polymer stability, and greasy/oily soil removal are compromised.
  • compositions also preferably have a solvent system comprising water and a mixture of ethanol and polyol.
  • Polyols such as propylene glycol are especially good at solubilizing the soil release polymer. Crystallization occurs without the polyol and unacceptably high gel points tend to occur without the ethanol.
  • the amount of ethanol and polyol must also be sufficient to prevent organic phase separation (i.e., keep free fatty acids and poorly soluble surfactants in solution), and yet not be so high as to cause lye phase separation and/or crystallization by limiting the amount of water available.
  • the soil release component has the generic formula in which X is selected from the group consisting of H, alkyl groups having from 1 to 4 carbon atoms, preferably 1 to 2 carbon atoms, or acyl groups containing from 2 to 4 carbon atoms preferably alkyl groups.
  • n is selected for water solubility and is a range of values which averages from 10 to 50, preferably from 10 to 25.
  • the selection of u is critical to formulation in a liquid detergent having a relatively high ionic strength. There should be very little material, i.e. less than 10 mol %, preferably less than 5 mol %, more preferably less than 1 mol %, in which u is greater than 5. Furthermore there should be at least 20 mol %, preferably at least 40 mol %, of material in which u ranges from 3 to 5. The average value for u is from 3 to 5.
  • the R1 moieties are 1,4-phenylene moieties.
  • suitable moieties include ethylene or 1,2-propylene, and mixtures thereof. Although inclusion of a greater percentage of ethylene moieties tends to improve the soil release activity of the compounds, the percentage included is limited by water solubility. Surprisingly, inclusion of a greater percentage of 1,2-propylene moieties tends to improve the water solubility of the compounds and consequently the ability to formulate isotropic aqueous detergent compositions without significantly harming soil release activity.
  • 1,2-propylene moieties is extremely important for maximizing incorporation of a substantial percentage of the soil release component in the heavy duty liquid detergent compositions.
  • soil release components which are soluble in cool (15°C) ethanol are also useful in compositions of the invention.
  • the value for n averages at least 10, but a distribution of n values is present.
  • the value for each n usually ranges from 10 to 50.
  • the value for each n averages in the range of from 10 to 25.
  • a preferred process for making the soil release component comprises the step of extracting a polymer having a typical distribution in which a substantial portion comprises a material in which u is greater than 5 with essentially anhydrous ethanol at low temperatures, e.g. from 10°C to 15°C, preferably less than 13°C.
  • the ethanol soluble fraction is substantially free of the longer polymers and is much easier to incorporate into isotropic heavy duty liquids, especially those with higher builder levels.
  • the polymers wherein u is less than 3 are essentially of no value in providing soil release effects, they can be more easily incorporated than higher u values.
  • a more preferred process for making the soil release component is by direct synthesis.
  • the anionic surfactant herein can comprise any of the synthetic anionic surfactants conventionally used in heavy duty laundry detergents including alkyl benzene sulfonates, alkyl sulfates, alkyl polyethoxylate sulfates, olefin sulfonates, paraffin sulfonates, etc. Mixtures can also be used. Suitable synthetic anionic surfactants are disclosed in detail in U.S. Patent 3,929,678, Laughlin et al, issued December 30, 1975.
  • Preferred synthetic anionic surfactants include the sulfonates, the alkyl sulfates, and alkylpolyethoxylate ether sulfates discussed more specifically below.
  • the detergent compositions herein preferably contain from 5% to 15%, more preferably from 6% to 12%, by weight (on an acid basis) of an anionic sulfonate surfactant containing a C10-C16 alkyl or alkenyl group.
  • Anionic sulfonate surfactants useful herein are disclosed in U.S. Patent 4,285,841, Barrat et al, issued August 25, 1981, and in U.S. Patent 3,919,678, Laughlin et al, issued December 30, 1975.
  • Preferred sulfonate surfactants are the water-soluble salts, particularly the alkali metal, and alkanolammonium (e.g., monoethanolammonium or triethanolammonium) salts of alkylbenzene sulfonates in which the alkyl group contains from 10 to 15 carbon atoms, in straight chain or branched chain configuration, e.g., those of the type described in U.S. Patents 2,220,099 and 2,477,383.
  • Especially valuable are linear straight chain alkylbenzene sulfonates in which the average number of carbon atoms in the alkyl group is from 11 to 13.
  • compositions also preferably contain an alcohol polyethoxylate ether sulfate surfactant of the formula RO(C2H4O) m SO3M, wherein R is a C10-C16 alkyl (preferred) or hydroxyalkyl group, m is from 0.5 to 4, and M is a compatible cation.
  • This surfactant preferably represents from 5% to 18%, more preferably from 9% to 14%, by weight (on an acid basis) of the composition.
  • Preferred alcohol ethoxylate sulfate surfactants of the above formula are those wherein the R substituent is a C12 ⁇ 15 alkyl group and m is from 1.5 to 3.
  • examples of such materials are C12 ⁇ 15 alkyl polyethoxylate (2.25) sulfate (C12 ⁇ 15 E 2.25 S); C14 ⁇ 15E 2.25 S; C12 ⁇ 13E 1.5 S; C14 ⁇ 15E3S; and mixtures thereof.
  • the sodium, potassium, monoethanolammonium, and triethanolammonium salts of the above are preferred.
  • compositions also preferably contain from 2% to 15%, more preferably from 4% to 12%, by weight of an ethoxylated nonionic surfactant of the formula R1(OC2H4) n OH, wherein R1 is a C10-C16 alkyl group or a C8-C12 alkyl phenyl group, n is from 3 to 9, and said nonionic surfactant has an HLB (hydrophile-lipophile balance) of from 10 to 13.
  • HLB hydrophile-lipophile balance
  • Particularly preferred are condensation products of C12-C14 alcohols with from 3 to 8 moles of ethylene oxide per mole of alcohol, e.g., C12-C13 alcohol condensed with about 6.5 moles of ethylene oxide per mole of alcohol.
  • the ethoxylated nonionic surfactants herein have an HLB (hydrophilic-lipophilic balance) of from 5 to 17, preferably from 6 to 13.
  • HLB hydrophilic-lipophilic balance
  • Suitable ethoxylated nonionic surfactants herein are as follows:
  • compositions herein can also contain from 0% to 15%, preferably from 0.5% to 3%, by weight of a cosurfactant selected from certain quaternary ammonium, amine, amide and/or amine oxide surfactants.
  • a cosurfactant selected from certain quaternary ammonium, amine, amide and/or amine oxide surfactants.
  • the quaternary ammonium and amide surfactants are particularly preferred.
  • the quaternary ammonium surfactants useful herein are of the formula: [R2(OR3) y ][R4(OR3) y ]2R5N+X ⁇ wherein R2 is an alkyl or alkyl benzyl group having from 6 to 16 carbon atoms in the alkyl chain; each R3 is selected from the group consisting of -CH2CH2-, -CH2CH(CH3)-, -CH2CH(CH2OH)-, -CH2CH2CH2-, and mixtures thereof; each R4 is selected from the group consisting of C1-C4 alkyl, C1-C4 hydroxyalkyl, benzyl, and hydrogen when y is not 0; R5 is the same as R4 or is an alkyl chain wherein the total number of carbon atoms of R2 plus R5 is from 8 to 16; each y is from 0 to 10 and the sum of the y values is from 0 to 15; and X is any compatible anion.
  • alkyl quaternary ammonium surfactants especially the mono-long chain alkyl surfactants described in the above formula when R5 is selected from the same groups as R4.
  • the most preferred quaternary ammonium surfactants are the chloride, bromide and methylsulfate C8 ⁇ 16 alkyl trimethylammonium salts, C8 ⁇ 16 alkyl di(hydroxyethyl)methylammonium salts, the C8 ⁇ 16 alkyl hydroxyethyldimethylammonium salts, C8 ⁇ 16 alkyloxypropyl trimethylammonium salts, and the C8 ⁇ 16 alkyloxypropyl dihydroxyethylmethylammonium salts.
  • the C10-C14 alkyl trimethylammonium salts are preferred, e.g., decyl trimethylammonium methylsulfate, lauryl trimethylammonium chloride, myristyl trimethylammonium bromide and coconut trimethylammonium chloride and methylsulfate.
  • the C8 ⁇ 10 alkyl trimethylammonium surfactants are particularly preferred since they have lower Kraft boundaries and crystallization temperatures than the longer chain quaternary ammonium surfactants.
  • Amine surfactants useful herein are of the formula: [R2(OR3) y ][R4(OR3) y ]R5N wherein the R2, R3, R4, R5 and y substituents are as defined above for the quaternary ammonium surfactants. Particularly preferred are the C12 ⁇ 16 alkyl dimethyl amines.
  • Amine oxide surfactants useful herein are of the formula: [R2(OR3) y ][R4(OR3) y ]R5N ⁇ 0 wherein the R2, R3, R4, R5 and y substituents are also as defined above for the quaternary ammonium surfactants. Particularly preferred are the C12 ⁇ 16 alkyl dimethyl amine oxides.
  • Amine and amine oxide surfactants are preferably used at higher levels than the quaternary ammonium surfactants since they are only partially protonated in the present systems.
  • preferred compositions herein can contain from 0.5% to 1.5% of the quaternary ammonium surfactant, or from 1% to 3% of the amine or amine oxide surfactants.
  • Amide surfactants herein are of the formula wherein R6 is an alkyl, hydroxyalkyl or alkenyl radical containing from 8 to 20 carbon atoms, and R7 and R8 are selected from the group consisting of hydrogen, methyl, ethyl, propyl, isopropyl, 2-hydroxyethyl, 2-hydroxypropyl, 3-hydroxypropyl, and said radicals additionally containing up to 5 ethylene oxide units, provided at least one of R7 and R8 contains a hydroxyl group.
  • Preferred amides are the C8-C20 fatty acid alkylol amides in which each alkylol group contains from 1 to 3 carbon atoms, and additionally can contain up to 2 ethylene oxide units. Particularly preferred are the C12-C16 fatty acid monoethanol and diethanol amides.
  • compositions of the present invention preferably contain from 0% to 20%, more preferably from 8% to 18%, most preferably from 10% to 16%, by weight of a saturated fatty acid containing from 10 to 14 carbon atoms.
  • weight ratio of C10-C12 fatty acid to C14 fatty acid is preferably at least 1, more preferably at least 1.5.
  • Suitable saturated fatty acids can be obtained from natural sources such as plant or animal esters (e.g., palm kernel 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 kernel fatty acid.
  • Preferred are saturated coconut fatty acids, from 5:1 to 1:1 (preferably about 3:1) weight ratio mixtures of lauric and myristic acid, mixtures of the above with minor amounts (e.g., 10%-50% of total fatty acid) of oleic acid; and palm kernel fatty acid.
  • compositions herein also preferably contain from 3% to 20%, more preferably from 3% to 6%, more preferably from 3.5% to 5% by weight on an acid basis, of a water-soluble polycarboxylate detergent builder material.
  • Polycarboxylate builders are described in U.S. Patent 4,284,532, Leikhim et al, issued August 18, 1981.
  • 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; the polycarboxylate materials described in U.S. Patent 3,364,103; and the water-soluble salts of polycarboxylate polymers and copolymers described in U.S. Patent 3,308,067, Diehl, issued March 7, 1967.
  • 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 350 calculated as to the acid form; (b) an equivalent weight of 50 to 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, carboxymethyloxysuccinic 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, carboxymethyloxysuccinic acid, carboxymethyloxymalonic acid, cis-cyclohexanehexacarboxylic acid, cis-cyclopentanetetracarboxylic acid and oxydisuccinic acid.
  • 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 4,146,495, issued March 27, 1979 to Crutchfield et al.
  • Citric acid is a highly preferred polycarboxylate builder.
  • the present compositions can contain from 0 to 0.04 moles, preferably from 0.01 to 0.035 moles, more preferably from 0.015 to 0.03 moles, per 100 grams of composition of an alkanolamine selected from the group consisting of monoethanolamine, diethanolamine, triethanolamine, and mixtures thereof. Low levels or none of the alkanolamines, particularly monoethanolamine, are preferred to enhance product stability, detergency performance, and odor. The amount of alkanolamine should be minimized for best chlorine bleach compatibility and stability of the soil release component. While the present compositions can contain mixtures of the alkanolamines, best color stability is obtained using single alkanolamines.
  • the solvent system for the compositions is preferably comprised of ethanol, a polyol, e.g., propanediol, and water.
  • Ethanol is preferably present at a level of from 2% to 10%, more preferably from 5% to 9%, by weight of the composition.
  • Any polyol containing from 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, propanediol, propylene glycol and glycerine. Propylene glycol is particularly preferred.
  • the polyol preferably represents from 2% to 15%, more preferably from 3% to 10%, by weight of the composition.
  • compositions also preferably contain from 25% to 40%, more preferably from 28% to 37%, by weight of water.
  • the ethanol and polyol together preferably represent from 8% to 20%, more preferably 11% to 16%, by weight of the composition.
  • the ethanol, polyol and water preferably total from 35% to 55%, more preferably 40% to 50%, by weight of the composition.
  • compositions of the present invention preferably have the following limits, in which all percentages and ratios are calculated on an acid basis where anionic materials are involved.
  • the fatty acid and polycarboxylate builder together preferably represent from 5% to 30%, more preferably from 10% to 25%, by weight of the composition.
  • the fatty acid, polycarboxylate builder and above surfactants preferably represent a total of from 33% to 50%, more preferably from 36% to 48%, by weight of the composition.
  • all of the above components are selected to provide an isotropic liquid detergent at 55°F (12.8°C), preferably at 50°F (10°C).
  • the components are also selected to provide an initial pH of from 7.5 to 9.0, preferably from 7.8 to 8.8, at a concentration of 10% by weight in water at 68°F (20°C).
  • Optional components for use in the liquid detergents herein include enzymes, enzyme stabilizing agents, polyacids, soil removal agents, antiredeposition agents suds regulants, hydrotropes, opacifiers, antioxidants, bactericides, dyes, perfumes, and brighteners described in the U.S. Patent 4,285,841, Barrat et al, issued August 25, 1981.
  • Such optional components generally represent less than 15%, preferably from 2% to about 10%, by weight of the composition.
  • Enzymes are highly preferred optional ingredients and are incorporated in an amount of from 0.025% to 2%, preferably from 0.05% to 1.5%.
  • Preferred proteolytic enzymes should provide a proteolytic activity of at least 5 Anson units (about 1,000,000 Delft units) per liter, preferably from 15 to 70 Anson units per liter, most preferably from 20 to 40 Anson units per liter.
  • a proteolytic activity of from 0.01 to 0.05 Anson units per gram of product is desirable.
  • Other enzymes, including amylolytic enzymes are also desirably included in the present compositions.
  • Suitable proteolytic enzymes include the many species known to be adapted for use in detergent compositions. Commercial enzyme preparations such as “Alcalase®” sold by Novo Industries, and “Maxatase®” sold by Gist-Brocades, Delft, The Netherlands, are suitable. Other preferred enzyme compositions include those commercially available under the tradenames SP-72' (“Esperase”®) manufactured and sold by Novo Industries, A/S, Copenhagen, Denmark and "AZ-Protease®” manufactured and sold by Gist-Brocades, Delft, The Netherlands.
  • Suitable amylases include “Rapidase®” sold by Gist-Brocades and “Termamyl®” sold by Novo Industries.
  • enzymes When enzymes are incorporated in the detergent compositions of this invention, they are desirably stabilized by using a mixture of a short chain carboxylic acid salt and calcium ion, such as disclosed in U.S. Patent 4,318,818, Letton et al, issued March 9, 1982.
  • the short chain carboxylic acid salt is preferably water-soluble, and most preferably is a formate, e.g., sodium formate.
  • the short chain carboxylic acid salt is used at a level from about 0.25% to about 10%, preferably from 0.3% to 3%, more preferably from 0.5% to 1.5%.
  • Any water-soluble calcium salt can be used as a source of calcium ion, including calcium acetate, calcium formate and calcium propionate.
  • the composition should contain from 0.1 to 30 millimoles of calcium ion per liter, preferably from 0.5 to 15 millimoles of calcium ion per liter. When materials are present which complex calcium ion, it is necessary to use high levels of calcium ion so that there is always some minimum level available for the enzyme.
  • Enzymes are preferably stabilized in the present compositions by the addition of from 0.25% to 10%, preferably from 0.5% to 5%, more preferably from 0.75% to 3%, by weight of boric acid or a compound capable of forming boric acid in the composition (calculated on the basis of the boric acid).
  • Boric acid is preferred, although other compounds such as boric oxide, borax and other alkali metal borates (e.g., sodium ortho-, meta- and pyroborate, and sodium pentaborate) are suitable.
  • Substituted boric acids e.g., phenylboronic acid, butane boronic acid, and p-bromo phenylboronic acid
  • boric acid and formate provides improved protease stability, although amylase stability appears to be slightly less than that obtained using boric acid alone.
  • Preferred compositions also contain from 0.01% to 1% of a polyacid or salt thereof, to enhance pretreatment performance.
  • Preferred polyacids for use herein are ethylenediamine tetramethylenephosphonic acid, diethylene triamine pentamethylenephosphonic acid, and diethylenetriamine pentaacetic acid, or the salts thereof. These polyacids/salts are preferably used in an amount from 0.1% to 0.8%.
  • compositions herein further contain from 0.5% to 3%, preferably from 1% to 2%, by weight of a highly ethoxylated polyethyleneamine or polyethyleneimine soil removal and antiredeposition agent.
  • a particularly preferred species of the like soil removal and anti-redeposition agent is tetraethylenepentamine ethoxylated with about 15-18 moles of ethylene oxide at each hydrogen site.
  • a liquid detergent composition of the present invention is as follows: A compound having a range of copolymers of the formula: CH3 ( ⁇ OCH2CH2) ⁇ 16 in which about 20% by weight of the material has a value of u higher than 5 is dissolved at about 15% level in anhydrous ethanol; cooled to about 10°C; the insoluble portion ( ⁇ 20%) is filtered; enough ethanol is distilled to reduce the ethanol level to within the level in the following formula; and the compound is added to the formula.
  • a liquid detergent composition of the present invention is as follows: A compound having a range of copolymers of the formula: CH3 - ( ⁇ OCH2CH2) ⁇ 16 in which about 20% by weight of the material has a value of u higher than 5 is dissolved at about 15% level in anhydrous ethanol; cooled to about 10°C; the insoluble portion ( ⁇ 20%) is filtered; enough ethanol is distilled to reduce the ethanol level to within the level in the following formula; and the compound is added to the formula.

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Claims (18)

  1. Flüssige Vollwaschmittelzusammensetzung, umfassend, bezogen auf das Gewicht:
    (a) 10 % bis 35 % eines anionischen grenzflächenaktiven Mittels auf einer Säurebasis;
    (b) 0 % bis 15 % eines ethoxylierten nichtionischen grenzflächenaktiven Mittels der Formel R¹(OC₂H₄)nOH, worin R¹ eine C₁₀-C₁₆-Alkylgruppe oder eine C₈-C₁₂-Alkylphenylgruppe darstellt, n durchschnittlich von 3 bis 9 beträgt, und die genannte nichtionische grenzflächenaktive Verbindung einen HLB-Wert von 10 bis 13 besitzt;
    (c) 0 % bis 15 % eines co-grenzflächenaktiven Mittels, welches von der Gruppe ausgewählt ist, die aus:
    (i) quaternären Ammonium-grenzflächenaktiven Mitteln der Formel:



            [R²(OR³)y][R⁴(OR³)y)₂R⁵N⁺X⁻ ,



    worin R² eine Alkyl- oder Alkylbenzylgruppe mit 6 bis 16 Kohlenstoffatomen in der Alkylkette darstellt; jeder Rest R³ von der Gruppe, welche aus -CH₂CH₂-, -CH₂CH(CH₃)-, -CH₂CH(CH₂OH)-, -CH₂CH₂CH₂- besteht und aus Gemischen hievon ausgewählt ist; jeder Rest R⁴ von der Gruppe, welche aus C₁-C₄-Alkyl, C₁-C₄-Hydroxyalkyl, Benzyl ausgewählt ist und Wasserstoff bedeutet, wenn y nicht 0 ist; R⁵ die gleiche Bedeutung wie R⁴ besitzt oder eine Alkylkette darstellt, wobei die Gesamtzahl der Kohlenstoffatome von R² plus R⁵ von 8 bis 16 beträgt; jedes y durchschnittlich 0 bis 10 ist und die Summe der y-Werte von 0 bis 15 beträgt; und X für jedes beliebige verträgliche Anion steht;
    ii) Amin-grenzflächenaktiven Mitteln der Formel:



            [R²(OR³)y][R⁴(OR³)y]R⁵N ,



    worin R², R³, R⁴ , R⁵ und y wie vorstehend definiert sind;
    iii) Aminoxid-grenzflächenaktiven Mitteln der Formel:



            [R²(OR³)y][R⁴(OR³)y]R⁵N → 0



    worin R², R³, R⁴, R⁵ und y wie vorstehend definiert sind;
    (iv) einem Amid-grenzflächenaktiven Mittel der Formel:
    Figure imgb0011
     worin R⁶ einen Alkyl-, Hydroxyalkyl- oder Alkenylrest mit 8 bis 20 Kohlenstoffatomen darstellt und R⁷ und R⁸ jeweils von der Gruppe ausgewählt sind, welche aus Wasserstoff, Methyl, Ethyl, Propyl, Isopropyl, 2-Hydroxyethyl, 2-Hydroxypropyl, 3-Hydroxypropyl besteht und worin die genannten Reste zusätzlich bis zu 5 Ethylenoxideinheiten enthalten; und
    (v) Gemischen hievon besteht;
    (d) 5 % bis 30 % an Detergensgerüststoff;
    (e) ein Neutralisationssystem;
    (f) ein wäßriges Lösungsmittelsystem, wobei das genannte System nicht ausschließlich aus Wasser besteht;
    (g) 0,25 % bis 4 % einer Schmutzlösekomponente, welche eine Verbindung der Formel:
    Figure imgb0012
     ist, worin jeder Rest R¹ ein 1,4-Phenylenrest ist, jeder Rest R² einen Ethylen- oder einen 1,2-Propylenrest darstellt; jedes n durchschnittlich 10 bis 50 beträgt; jedes X für H, einen Alkylrest mit 1 bis 4 Kohlenstoffatomen oder einen Acylrest mit 2 bis 4 Kohlenstoffatomen steht; wobei in weniger als 10 Mol-% der genannten Schmutzlöseverbindung u mehr als 5 beträgt, in mindestens 20 Mol-% der genannten Schmutzlöseverbindung u im Bereich von 3 bis 5 liegt und worin der durchschnittliche Wert von u von 3 bis 5 ist.
  2. Zusammensetzung nach Anspruch 1, worin in der Komponente (g) n von 10 bis 25 beträgt und 90 % bis 100 % der Reste R²-1,2-Propylenreste sind.
  3. Zusammensetzung nach Anspruch 2, worin X einen Alkylrest mit 1 bis 2 Kohlenstoffatomen darstellt.
  4. Zusammensetzung nach Anspruch 2, worin die Komponente (g) eine in absolutem Ethanol bei einer Temperatur von 10°C bis 15°C lösliche Polymerenfraktion ist.
  5. Zusammensetzung nach Anspruch 1, worin die Komponente (g) eine in absolutem Ethanol bei einer Temperatur von 10°C bis 15°C lösliche Polymerenfraktion ist.
  6. Zusammensetzung nach Anspruch 5, worin die Detergenszusammensetzung, bezogen auf das Gewicht:
    (a) 5 % bis 15 %, auf einer Säurebasis, an einem Sulfonat-grenzflächenaktiven Mittel mit einer C₁₀-C₁₆-Alkyl- oder -Alkenylgruppe;
    (b) 8 % bis 18 %, auf einer Säurebasis, an einem Alkoholethoxylat-Sulfat-grenzflächenaktiven Mittel der Formel RO(C₂H₄O)mSO₃M, worin R eine C₁₀-C₁₆-Alkyl- oder -Hydroxyalkylgruppe darstellt, m von 0,5 bis 4 beträgt und M ein verträgliches Kation ist; und
    (c) 2 % bis 15 % eines ethoxylierten nichtionischen grenzflächenaktiven Mittels der Formel R¹(OC₂H₄)nOH umfaßt, worin R¹ eine C₁₀-C₁₆-Alkylgruppe oder eine C₈-C₁₂-Alkylphenylgruppe ist, n von 3 bis 9 beträgt und das genannte nichtionische grenzflächenaktive Mittel einen HLB-Wert von 10 bis 13 besitzt.
  7. Zusammensetzung nach Anspruch 5, worin die Detergenszusammensetzung, bezogen auf das Gewicht,
    (a) 5 % bis 15 %, auf einer Säurebasis, an einem Sulfonat-grenzflächenaktiven Mittel mit einer C₁₀-C₁₆-Alkyl oder -Alkenylgruppe;
    (b) 1 % bis 4 %, auf einer Säurebasis, an einem C₁₀-C₁₆-Alkylsulfat; und
    (c) 2 % bis 15 % eines ethoxylierten nichtionischen grenzflächenaktiven Mittels der Formel R¹(OC₂H₄)nOH umfaßt, worin R¹ eine C₁₀-C₁₆-Alkylgruppe oder eine C₈-C₁₂-Alkylphenylgruppe darstellt, n von 3 bis 9 beträgt und das genannte nichtionische grenzflächenaktive Mittel einen HLB-Wert von 10 bis 13 aufweist.
  8. Zusammensetzung nach Anspruch 6, worin das Sulfonat-grenzflächenaktive Mittel ein lineares C₁₁-C₁₃-Alkylbenzolsulfonat ist; worin im Alkoholethoxylat-Sulfat-grenzflächenaktiven Mittel R für eine C₁₂-C₁₅-Alkylgruppe steht und m von 1,5 bis 3 beträgt, und worin im ethoxylierten nichtionischen grenzflächenaktiven Mittel R für eine C₁₂-C₁₄-Alkylgruppe steht und n von 3 bis 7 beträgt.
  9. Zusammensetzung nach Anspruch 8, umfassend 0,5 Gew.-% bis 3 Gew.-% des co-grenzflächenaktiven Mittels, welches ein C₁₀-C₁₄-Alkyltrimethylammoniumchlorid, -bromid oder -methylsulfat ist.
  10. Zusammensetzung nach Anspruch 8, worin der Gerüststoff einen Polycarboxylatgerüststoff umfaßt.
  11. Zusammensetzung nach Anspruch 8, umfassend, bezogen auf das Gewicht, 6 % bis 10 % des Sulfonat-grenzflächenaktiven Mittels, 9 % bis 14 % des Alkoholethoxylat-Sulfat-grenzflächenaktiven Mittels, 4 % bis 10 % des ethoxylierten nichtionischen grenzflächenaktiven Mittels und 0,5 % bis 1,5 % des co-grenzflächenaktiven Mittels, welches ein C₁₀-C₁₄-Alkyltrimethylammoniumchlorid, -bromid oder -methylsulfat ist.
  12. Zusammensetzung nach Anspruch 11, worin der Gerüststoff, bezogen auf das Gewicht der Zusammensetzung, 10 % bis 16 % an gesättigter Fettsäure und 3 % bis 6 % an Zitronensäure umfaßt.
  13. Zusammensetzung nach Anspruch 12, umfassend 0 bis 0,035 Mol je 100 g an Zusammensetzung von einem Alkanolamin, welches Monoethanolamin ist.
  14. Zusammensetzung nach Anspruch 13, umfassend, bezogen auf das Gewicht, 5 % bis 9 % Ethanol, 3 % bis 10 % eines Polyols, welcher Propylenglykol ist, und 28 % bis 37 % Wasser.
  15. Zusammensetzung nach Anspruch 14, mit einem Anfangs-pH-Wert von 7,8 bis 9,0 bei einer Konzentration von 10 Gew.-% in Wasser bei 68°F (20°C).
  16. Verfahren zur Herstellung einer Schmutzlösekomponente der Formel:
    Figure imgb0013
     worin jeder Rest R¹ einen 1,4-Phenylenrest darstellt, jeder Rest R² einen Ethylen- oder einen 1,2-Propylenrest bedeutet; jeder Rest X von der aus Wasserstoff, Alkylgruppen mit 1 bis 4 Kohlenstoffatomen und Acylgruppen mit 2 bis 4 Kohlenstoffatomen bestehenden Gruppe ausgewählt ist; n durchschnittlich von 10 bis 50 beträgt; worin in weniger als 10 Mol-% der genannten Schmutzlösekomponente u mehr als 5 beträgt, in mindestens 20 Mol-% der genannten Schmutzlösekomponente u im Bereich von 3 bis 5 liegt, und worin der mittlere Wert von u von 3 bis 5 ist; umfassend den Schritt des Auflösens einer Schmutzlösekomponente, welche das gewünschte Material und eine wesentliche Menge an Material, worin u mehr als 5 beträgt, in absolutem Alkohol bei einer Temperatur von 10°C bis 15°C und das Abtrennen des ausfallenden Materials.
  17. Ethanol-lösliche Schmutzlösekomponente der Formel
    Figure imgb0014
     worin jeder Rest R¹ ein 1,4-Phenylenrest ist, jeder Rest R² einen Ethylen- oder einen 1,2-Propylenrest darstellt; jedes n durchschnittlich von 10 bis 50 beträgt; jeder Rest X für H, einen Alkylrest mit 1 bis 4 Kohlenstoffatomen oder einen Acylrest mit 2 bis 4 Kohlenstoffatomen steht, worin 90 % bis 100 % der Reste R²- 1,2-Propylenreste sind und worin in weniger als 10 Mol-% der genannten Schmutzlöseverbindung u mehr als 5 beträgt, in mindestens 20 Mol-% der genannten Schmutzlöseverbindung u im Bereich von 3 bis 5 beträgt, und worin der durchschnittliche Wert von u von 3 bis 5 ist; erhältlich durch das Verfahren nach Anspruch 16.
  18. Komponente nach Anspruch 17, worin jeder Rest X eine Alkylgruppe mit 1 bis 2 Kohlenstoffatomen ist.
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Publication number Publication date
EP0199403A2 (de) 1986-10-29
DE3689385D1 (de) 1994-01-27
ATE98674T1 (de) 1994-01-15
AU601679B2 (en) 1990-09-20
AU5612086A (en) 1986-10-23
EP0199403A3 (en) 1989-07-05
DE3689385T2 (de) 1994-05-19

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