EP0342177B1 - Heavy duty liquid laundry detergents containing anionic and nonionic surfactant, builder and proteolytic enzyme - Google Patents

Heavy duty liquid laundry detergents containing anionic and nonionic surfactant, builder and proteolytic enzyme Download PDF

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Publication number
EP0342177B1
EP0342177B1 EP89870064A EP89870064A EP0342177B1 EP 0342177 B1 EP0342177 B1 EP 0342177B1 EP 89870064 A EP89870064 A EP 89870064A EP 89870064 A EP89870064 A EP 89870064A EP 0342177 B1 EP0342177 B1 EP 0342177B1
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weight
heavy duty
duty liquid
liquid laundry
acid
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German (de)
English (en)
French (fr)
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EP0342177A2 (en
EP0342177A3 (en
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Michael Stanford Showell
William Conrad Wertz
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Procter and Gamble Co
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Procter and Gamble Co
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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
    • C11D1/00—Detergent compositions based essentially on surface-active compounds; Use of these compounds as a detergent
    • 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
    • C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
    • C11D3/16—Organic compounds
    • C11D3/38—Products with no well-defined composition, e.g. natural products
    • C11D3/386—Preparations containing enzymes, e.g. protease or amylase
    • C11D3/38618—Protease or amylase in liquid compositions only
    • 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
    • C11D1/29—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
    • C11D1/66—Non-ionic compounds
    • C11D1/72—Ethers of polyoxyalkylene glycols

Definitions

  • the present invention relates to heavy duty liquid laundry detergent compositions containing synthetic anionic and ethoxylated nonionic surfactant, detergency builder, specific proteolytic enzyme, an enzyme stabilization system, and water.
  • the compositions have a pH in a 10% by weight solution in water at 20°C of between 7.0 and 9.0, a Critical Micelle Concentration of less than or equal to 200 ppm, and an air/water Interfacial Tension above the Critical Micelle Concentration of less than or equal to 32 dynes/cm at 35°C in distilled water.
  • the compositions are preferably clear, homogeneous, and stable and provide good cleaning performance, particularly through-the-wash on enzyme-sensitive stains.
  • Laundry detergents containing high levels of anionic surfactant and builder, and capable of providing superior cleaning performance, are currently on the market. Some of these compositions contain enzymes to enhance removal of enzyme-sensitive stains. The stabilization of enzymes is particularly difficult in these compositions because anionic surfactants, especially alkyl sulfates, tend to denature enzymes and render them inactive. Detergency builders can also sequester the calcium ion needed for enzyme activity and/or stability.
  • the enzymes of this reference are said to be useful in laundry detergents, both liquid and granular. They can be combined with surfactants (including anionics), builders, bleach and/or fluorescent whitening agents.
  • the compositions provide improved cleaning performance, particularly through-the-wash, of enzyme-sensitive stains such as grass, blood, gravy and chocolate pudding.
  • European Patent Application Serial No. 199,405 discloses liquid detergent compositions containing synthetic surfactant, the same Protease A, boric acid or a boron compound capable of forming boric acid in the composition, and calcium ion.
  • the compositions exhibit improved enzyme stability because the boric acid stabilizes the Protease A to a greater degree than it does other proteolytic enzymes.
  • Preferred laundry detergent compositions containing anionic surfactant and detergency builder also provide improved cleaning performance, particularly through-the-wash, on enzyme-sensitive stains.
  • Protease B An improved proteolytic enzyme referred to herein as "Protease B" is described in European Patent Application EP-A-251 446, filed April 28, 1987, on pages 17, 24 and 98.
  • Protease B differs from the above cited Protease A in that it has a leucine substituted for the tyrosine in position 217 on the protein backbone.
  • U.S. Patent 4,507,219, Hughes, issued March 26, 1985 discloses heavy duty liquid laundry detergents which may contain proteolytic enzyme along with anionic surfactant, optional quaternary ammonium, amine or amine oxide surfactants, saturated fatty acid, polycarboxylate builder, a neutralization system, and a solvent system.
  • the compositions are isotropic liquids.
  • the present invention relates to a heavy duty liquid laundry detergent composition
  • a heavy duty liquid laundry detergent composition comprising, by weight:
  • compositions contain six essential ingredients which are: (1) synthetic anionic surfactant, (2) ethoxylated nonionic surfactant, (3) detergency builder, (4) a specific proteolytic enzyme, (5) an enzyme stabilization system, and (6) water.
  • the weight ratio of synthetic anionic surfactant to ethoxylated nonionic surfactant is from 1:1 to 5:1.
  • the compositions have a pH in a 10% by weight solution in water at 20°C of from 7.0 to 9.0, a Critical Micelle Concentration of less than or equal to 200 ppm, and an air/water Interfacial Tension at the Critical Micelle Concentration of less than or equal to 32 dynes/cm at 35°C in distilled water.
  • the compositions are preferably clear, homogeneous and phase stable, and have good cleaning performance and enzyme stability.
  • compositions of the present invention contain from 10% to 50%, preferably from 15% to 50%, more preferably from 20% to 40%, and most preferably from 20% to 30%, by weight of a synthetic anionic surfactant.
  • Suitable synthetic anionic surfactants are disclosed in U.S. Patent 4,285,841, Barrat et al., issued August 25, 1981, and in U.S. Patent 3,929,678, Laughlin et al., issued December 30, 1975.
  • Useful anionic surfactants include the water-soluble salts, particularly the alkali metal, ammonium and alkylolammonium (e.g., monoethanolammonium or triethanolammonium) salts, of organic sulfuric reaction products having in their molecular structure an alkyl group containing from 10 to 20 carbon atoms and a sulfonic acid or sulfuric acid ester group.
  • water-soluble salts particularly the alkali metal, ammonium and alkylolammonium (e.g., monoethanolammonium or triethanolammonium) salts, of organic sulfuric reaction products having in their molecular structure an alkyl group containing from 10 to 20 carbon atoms and a sulfonic acid or sulfuric acid ester group.
  • alkyl is the alkyl portion of aryl groups.
  • alkyl sulfates especially those obtained by sulfating the higher alcohols (C8-C18 carbon atoms) such as those produced by reducing the glycerides of tallow or coconut oil; and the alkylbenzene sulfonates in which the alkyl group contains from 9 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 14.
  • anionic surfactants herein are the water-soluble salts of: paraffin sulfonates containing from 8 to 24 (preferably 12 to 18) carbon atoms; alkyl glyceryl ether sulfonates, especially those ethers of C8 ⁇ 18 alcohols (e.g., those derived from tallow and coconut oil); alkyl phenol ethylene oxide ether sulfates containing from 1 to 4 units of ethylene oxide per molecule and from 8 to 12 carbon atoms in the alkyl group; and alkyl ethylene oxide ether sulfates containing 1 to 4 units of ethylene oxide per molecule and from 10 to 20 carbon atoms in the alkyl group.
  • Other useful anionic surfactants include the water-soluble salts of esters of alpha-sulfonated fatty acids containing from 6 to 20 carbon atoms in the fatty acid group and from 1 to 10 carbon atoms in the ester group; water-soluble salts of 2-acyloxy- alkane-l-sulfonic acids containing from 2 to 9 carbon atoms in the acyl group and from 9 to 23 carbon atoms in the alkane moiety; water-soluble salts of olefin sulfonates containing from 12 to 24 carbon atoms; and beta-alkyloxy alkane sulfonates containing from 1 to 3 carbon atoms in the alkyl group and from 8 to 20 carbon atoms in the alkane moiety.
  • Preferred anionic surfactants are the C10-C18 alkyl sulfates and alkyl ethoxy sulfates containing an average of up to 4 ethylene oxide units per mole of alkyl sulfate, C11-C13 linear alkylbenzene sulfonates, and mixtures thereof.
  • a second essential ingredient is from 2% to 14%, preferably from 2% to 8%, most preferably from 3% to 5% by weight, of an ethoxylated nonionic surfactant.
  • the weight ratio of synthetic anionic surfactant (on an acid basis) to nonionic surfactant is from 1:1 to 5:1, preferably from 2:1 to 5:1, most preferably from 3:1 to 4:1. This is to ensure the formation and adsorption of sufficient hardness surfactants at the air/water interface to provide good greasy/oily soil removal.
  • the ethoxylated nonionic surfactant is 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 (Hydrophilic-Lipophilic Balance) of from 6 to 14, preferably from 10 to 13.
  • HLB Hydrophilic-Lipophilic Balance
  • Particularly preferred are condensation products of C12-C15 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.
  • Optional cosurfactants for use with the above ethoxylated nonionic surfactants include amides of the formula wherein R1 is an alkyl, hydroxyalkyl or alkenyl radical containing from 8 to 20 carbon atoms, and R2 and R3 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 R2 and R3 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.
  • amides are preferably present at a level such that the above ethoxylated nonionic surfactant and amide surfactant is in a weight ratio of from 4:1 to 1:4, preferably from 3:1 to 1:3.
  • Preferred and optional cosurfactants used at a level of from 0.15% to 1%, are the quaternary ammonium, amine and amine oxide surfactants described in U.S. Patent 4,507,219, Hughes, issued March 26, 1985.
  • 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. From 0.2% to 0.8% of monoalkyl trimethylammonium chloride is preferred.
  • compositions herein contain from 5% to 20%, preferably from 10% to 15%, by weight of a detergency builder which can be a fatty acid containing from 10 to 18 carbon atoms and/or a polycarboxylate, polyphosphonate and/or polyphosphate builder.
  • a detergency builder which can be a fatty acid containing from 10 to 18 carbon atoms and/or a polycarboxylate, polyphosphonate and/or polyphosphate builder.
  • Preferred are from 0 to 10% (more preferably from 3% to 10%) by weight of saturated fatty acids containing from 12 to 14 carbon atoms, along with from 0 to 10%, more preferably from 2% to 8%, most preferably from 2% to 5%, by weight of a polycarboxylate builder, most preferably citric acid, in a weight ratio of from 1:1 to 3:1.
  • the compositions preferably contain sufficient builder to sequester from 2 to 10, preferably from 3 to 8, grains per gallon of hardness.
  • 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., 1%-30% of total fatty acid) of oleic acid; and palm kernel fatty acid.
  • compositions herein preferably also contain the polycarboxylate, polyphosphonate and polyphosphate builders described in U.S. Patent 4,284,532, Leikhim et al., issued August 18, 1981.
  • Water-soluble polycarboxylate builders, particularly citrates, are preferred of this group.
  • Suitable polycarboxylate builders include the various aminopolycarboxylates, cycloalkane polycarboxylates, ether polycarboxylates, alkyl polycarboxylates, epoxy polycarboxylates, tetrahydrofuran polycarboxylates, benzene polycarboxylates, and polyacetal polycarboxylates.
  • 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.
  • Other useful detergency builders 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 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 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..
  • detergency builders include the aluminosilicate ion exchange material described in U.S. Patent 4,405,483, Kuzel et al., issued September 20, 1983.
  • succinate builders are those of the general formula R-CH(COOH)CH2(COOH), i.e. derivatives of succinic acid, wherein R is C10-C20 alkyl or alkenyl, preferably C12-C16, or wherein R may be substituted with hydroxyl, sulfo, sulfoxy or sulfone substituents.
  • succinate builders are preferably used in the form of their water soluble salts, including the sodium, potassium and alkanolammonium salts.
  • Specific examples of succinate builders include: lauryl succinate, myristyl succinate, palmityl succinate, 2-dodecenyl succinate, and the like.
  • compositions herein preferably contain from 0 to 10%, preferably from 0 to 6%, by weight on an acid basis, of a tartrate succinate builder material selected from the group consisting of:
  • compositions can also optionally 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.
  • an alkanolamine selected from the group consisting of monoethanolamine, diethanolamine, triethanolamine, and mixtures thereof.
  • 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.
  • compositions contain sodium ions, and preferably potassium ions, at a level sufficient to neutralize the anionic species and provide the desired product pH.
  • compositions of the present invention contain from 0.01% to 5%, preferably from 0.1% to 2%, by weight of the proteolytic enzyme referred to herein as Protease B.
  • the described proteolytic enzyme is preferably included in an amount sufficient to provide an activity of from 0.05 to 1.0, more preferably from 0.1 to 0.75, most preferably from 0.125 to 0.5, mg of active enzyme per gram of composition.
  • An enzyme stabilization system comprising calcium ion, boric acid, propylene glycol and/or short chain carboxylic acids, is the fifth essential element of the instant heavy duty liquid detergent composition.
  • the enzyme stabilization system comprises from 0.5% to 15% by weight of the composition.
  • the composition preferably contains from 0.01 to 50, preferably from 0.1 to 30, more preferably from 1 to 20, millimoles of calcium ion per liter.
  • the level of calcium ion should be selected so that there is always some minimum level available for the enzyme, after allowing for complexation with builders in the composition.
  • Any water-soluble calcium salt can be used as the source of calcium ion, including calcium chloride, calcium formate, and calcium acetate.
  • a small amount of calcium ion generally from 0.05 to 0.4 millimoles per liter, is often also present in the composition due to calcium in the enzyme slurry and formula water. From 0.03% to 0.6% of calcium formate is preferred.
  • a second preferred enzyme stabilizer is polyols containing only carbon, hydrogen and oxygen atoms. They preferably contain from 2 to 6 carbon atoms and from 2 to 6 hydroxy groups. Examples include propylene glycol (especially 1,2 propanediol, which is preferred), ethylene glycol, glycerol, sorbitol, mannitol, and glucose.
  • the polyol generally represents from 0.5% to 15%, preferably from 1.5% to 8%, by weight of the composition.
  • the weight ratio of polyol to any boric acid added is at least 1, more preferably at least 1.3.
  • compositions preferably also contain the water-soluble, short chain carboxylates described in U.S. Patent 4,318,818, Letton et al., issued March 9, 1982.
  • the formates are preferred and can be used at levels of from 0.05% to 5%, preferably from 0.2% to 2%, most preferably from 0.4% to 1.5%, by weight of the composition.
  • Sodium formate is preferred.
  • the compositions herein also optionally contain from 0.25% to 5%, most preferably from 0.5% to 3%, by weight of boric acid.
  • the boric acid may be, but is preferably not, formed by a compound capable of forming boric acid in the composition. 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
  • compositions herein contain from 30% to 80%, preferably from 35% to 60%, by weight of water.
  • Another optional component for use in the liquid detergents herein is from 0 to 1.5%, preferably from 0.5% to 1.0%, by weight of silicone based suds suppressor agent.
  • Silicones are widely known and taught for use as highly effective suds controlling agents.
  • U.S. Patent 3,455,839 relates to compositions and processes for defoaming aqueous solutions by incorporating therein small amounts of polydimethylsiloxane fluids.
  • Useful suds controlling silicones are mixtures of silicone and silanated silica as described, for instance, in German Patent Application DOS 2,124,526.
  • Silicone defoamers and suds controlling agents have been successfully incorporated into granular detergent compositions by protecting them from detergent surfactants as in U.S. Patent 3,933,672, Bartolotta et al., and in U.S. Patent 4,652,392, Baginski et al., issued March 24, 1987.
  • a preferred silicone based suds suppressor for use herein is a suds suppressing amount of a suds controlling agent consisting essentially of:
  • optional components for use in the liquid detergents herein include soil removal agents, soil release polymers, antire-deposition agents such as tetraethylene pentamine ethoxylate (from 0.5% to 3%, preferably from 1% to 3%, by weight), suds regulants, hydrotropes such as sodium cumene sulfonate, opacifiers, antioxidants, bactericides, dyes, perfumes, and brighteners known in the art.
  • Such optional components generally represent less than 15%, preferably from 0.5% to 10%, more preferably from 1% to 10%, by weight of the composition.
  • compositions may contain from 0% to 8%, preferably from 0% to 5%, by weight of a C12-C14 alkenyl succinic acid or salt thereof.
  • These materials are of the general formual R-CH(COOX)CH2(COOX), wherein R is a C12-C14 alkenyl group and each X is H or a suitable cation, such as sodium, potassium, ammonium or alkanolammonium (e.g., mono-, di-, or tri-ethanolammonium).
  • suitable cation such as sodium, potassium, ammonium or alkanolammonium (e.g., mono-, di-, or tri-ethanolammonium).
  • 2-dodecenyl succinate preferred
  • 2-tetradecenyl succinate 2-tetradecenyl succinate.
  • compositions herein optionally contain from 0.1% to 1%, preferably from 0.2% to 0.6%, by weight of water-soluble salts of ethylenediamine tetramethylenephosphonic acid, diethylenetriamine pentamethylenephosphonic acid, ethylenediamine tetraacetic acid (preferred), or diethylenetriamine pentaacetic acid (most preferred) to enhance cleaning performance when pretreating fabrics.
  • compositions herein preferably contain up to 10% of ethanol.
  • the instant composition has a pH, in a 10% by weight solution in water at 20°C, of from 7.0 to 9.0, preferably from 8.0 to 8.5.
  • compositions also have a Critical Micelle Concentration (CMC) of less than or equal to 200 parts per million (ppm), and an air/water Interfacial Tension above the CMC of less than or equal to 32, preferably less than or equal to 30, dynes per centimeter at 35°C in distilled water.
  • CMC Critical Micelle Concentration
  • ppm parts per million
  • Enzyme activity can be measured using the PNA assay, according to reaction with the soluble substrate succinyl-alanine-alanine-proline-phenylalanine-para-nitrophenol, which is described in the Journal of American Oil Chemists Society, Rothgeb, T.M., Goodlander, B.D., Garrison, P.H., and Smith, L.A., in press (1988).
  • a heavy duty liquid laundry detergent composition of the prevent invention is as follows: Component Active Weight % C13 linear alkylbenzene sulfonic acid 8.00 C14 ⁇ 15 alkyl polyethoxylate (2.25) sulfonic acid 12.00 1,2 Propanediol 3.50 Sodium diethylenetriamine pentaacetate 0.30 Monoethanolamine 2.00 C12 ⁇ 13 alcohol polyethoxylate (6.5)* 5.00 Ethanol 8.50 Sodium hydroxide 3.85 Potassium hydroxide 1.80 C12 ⁇ 14 fatty acid 10.00 Citric acid 4.00 Calcium formate 0.12 Sodium formate 0.86 C12 alkyltrimethylammonium chloride 0.50 Tetraethylene pentamine ethoxylate (15-18) 2.00 Water 37.14 Dye 0.08 Perfume 0.25 Protease B** 0.099 *Alcohol and monoethoxylated alcohol removed. **mg active enzyme/g (@27 mg active enzyme/g stock)
  • the ingredients listed above are added to a mixing tank with a single agitator in the order in which they appear below.
  • the pH of the mix is adjusted so that a 10% by weight solution in water at 20°C has a pH of about 8.5.
  • This formula is clear, homogeneous, and stable, and has a Critical Micelle Concentration of about 220 ppm and an air/water Interfacial Tension above this CMC of about 25 dynes/cm at 35°C in distilled water.
  • the composition with Protease B provides superior cleaning of enzyme-sensitive stains, even when compared to Protease A (described above) at 0.25 mg active enzyme/g product in a 60°F (15.6°C) wash at 85.59 parts per million (ppm) [5 grains per gallon (gpg)] hardness (3:1 Ca/Mg).
  • Protease B also shows superior enzyme stability in the composition of Example I versus other proteolytic enzymes such as Protease A and Alcalase B (Novo Industries, Copenhagen, Denmark): Enzyme Activity* (after 1 week storage at 37.8°C) % Activity Half Life (days) Protease B 58.4 9.1 Protease A 33.6 4.5 Alcalase B 13.7 2.5 *PNA assay
  • a heavy duty liquid composition of the present invention is as follows: Component Active Weight % C13 linear alkylbenzene sulfonic acid 3.80 C 11.8 linear alkylbenzene sulfonic acid 3.80 C14 ⁇ 15 alkyl polyethoxylate (2.25) sulfonic acid 11.41 C12 ⁇ 13 alkyl polyethoxylate (6.5)* 3.80 C12 alkyl trimethyl ammonium chloride 0.28 Sodium cumene sulfonate 2.38 Ethanol 2.61 1,2 Propanediol 2.85 Brightener 0.12 Monoethanolamine 1.66 Potassium hydroxide 0.19 Sodium hydroxide 3.85 C12 ⁇ 14 fatty acid 3.33 Citric acid 3.80 Tartrate succinate 3.80 Sodium formate 0.92 Calcium formate 0.04 Tetraethylene pentamine ethoxylate (15-18) 1.66 Water 48.04 Soil release polymer 1.10 Dye 0.08 Perfume 0.30 Protease B** 0.175 *Alcohol and monoethoxylated alcohol
  • the ingredients listed above are added to a mixing tank with a single agitator in the order which they appear below.
  • the pH of the mixture is adjusted such that a 10% by weight solution in water has a pH of about 8.5.
  • the above formula is clear, stable, and homogeneous, and has a Critical Micelle Concentration of about 100 ppm and an air/water Interfacial Tension above the CMC of about 30 dynes/cm at 35°C in distilled water.
  • the composition with Protease B provides protease-sensitive stain removal equal to that achieved with the same formula using 0.35 mg active enzyme/g product of Protease A (described above).
  • Protease B also shows superior enzyme stability in the composition of Example II versus other proteolytic enzymes such as Protease A and Alcalase B (Novo Industries, Copenhagen, Denmark). Enzyme Activity* (After 4 weeks storage at 37.8°C) % Activity Half Life (days) Protease B 16.2 10.7 Protease A 4.2 6 Alcalase B 0.00 - *PNA assay
  • a heavy duty liquid laundry detergent composition of the present invention is as follows: Component Active Weight % C13 linear alkylbenzene sulfonic acid 13.00 C13 ⁇ 14 alkyl sulfuric acid 13.00 C12 ⁇ 13 alcohol polyethoxylate (6.5)* 6.00 Sodium cumene sulfonate 6.30 Ethanol (92%) 2.50 1,2 Propanediol 7.50 Brightener 0.12 Monoethanolamine 2.00 Potassium hydroxide 0.15 Sodium hydroxide 4.29 C12 ⁇ 14 fatty acid 1.0 Tartrate succinate 10.0 Citric acid 4.0 Calcium formate 0.04 Sodium formate 0.86 C12 alkyltrimethylammonium chloride 0.50 Tetraethylene pentamine ethoxylate (15-18) 1.65 Water 25.36 Soil release polymer 1.00 Dye 0.08 Perfume 0.25 Protease B** 0.397 *Alcohol and monoethoxylated alcohol removed. **mg active enzyme/g (@ 27 mg active enzyme/g stock)
  • composition is prepared as in Example II.
  • a heavy duty liquid laundry detergent composition of the present invention is as follows: Component Active Weight % C13 linear alkylbenzene sulfonic acid 4.23 C 11.8 alkylbenzene sulfonic acid 4.23 C14 ⁇ 15 alkyl polyethoxylate (2.25) sulfonic acid 8.46 C12 ⁇ 13 alkyl polyethoxylate (6.5)* 3.39 Sodium cumene sulfonate 5.45 Ethanol (92%) 1.18 Propanediol 2.89 Brightener 0.11 Monoethanolamine 1.57 Tartrate succinate 9.62 Calcium formate 0.102 Formic acid 0.51 C12 Trimethylammonium chloride 0.51 Tetraethylene pentamine ethoxylate (15-18) 0.96 Water 55.57 Soil release polymer 0.90 Silicone suds suppressor 0.10 Protease B** 0.221 *Alcohol and monoethoxylated alcohol removed. **mg active enzyme/g (@ 27 mg active enzyme/g stock)
  • composition is prepared as in Example II.
  • the above formula is clear, stable, and homogeneous, and has a Critical Micelle Concentration of about 100 ppm and an air/water Interfacial Tension above that CMC of about 30 dynes/cm at 35°C in distilled water.
  • the composition with Protease B provides protease-sensitive stain removal equal to that achieved with the same formula using 0.35 mg active enzyme/g product of Protease A (described above).
  • Protease B also shows superior enzyme stability in the composition of Example IV versus other proteolytic enzymes such as Protease A and Alcalase B (Novo Industries, Copenhagen, Denmark). Enzyme Activity* (After 2 weeks storage at 37.8°C) % Activity Half Life (days) Protease B 64.0 20.7 Protease A 50.0 13.8 Alcalase B --- 3.3 *PNA assay
  • a heavy duty liquid laundry detergent composition of the present invention is as follows: Component Active Weight % C10 ⁇ 15 Linear alkylbenzene sulfonic acid 12.86 Sodium C12 ⁇ 14 alkyl sulfate 2.00 1,2 Propanediol 2.00 Diethylenetriamine pentamethylene phosphonic acid 0.70 C14 ⁇ 15 alcohol polyethoxylate (E07) 7.77 Ethanol 4.60 Sodium hydroxide 7.00 Soil release polymer 0.46 C12 ⁇ 14 alkenyl succinic acid 11.44 Brightener 0.163 Oleic acid 1.80 Citric acid (monohydrate) 2.90 Calcium chloride 0.014 Boric acid 1.00 Silane 0.03 Water & miscellaneous Balance Protease B* 0.28 *41 g active enzyme/liter of enzyme
  • composition with Protease B provides 61% retained protease activity after three weeks storage at 35°C.
  • a heavy duty liquid laundry detergent composition of the present invention is as follows: Component Active Weight % C10 ⁇ 15Linear alkylbenzene sulfonic acid 10.25 Triethanolamine C12 ⁇ 14 alkyl sulfate 3.88 1,2 Propanediol 1.50 Diethylenetriamine pentamethylene phosphonic acid 0.765 Triethanolamine (free) 4.335 C14 ⁇ 15 alcohol polyethoxylate (E07) 11.620 Ethanol 5.510 Sodium hydroxide 3.400 C8 ⁇ 18 fatty acid 10.68 Oleic acid 3.88 Citric acid (anhydrous) 0.83 Calcium chloride 0.0167 Sodium formate 0.972 Tetraethylene pentamine ethoxylate (15-18) 0.30 Dye 0.0032 Opacifier 0.224 Perfume 0.30 Soil release polymer 0.50 N-(ethylene diaminoethyl) aminopropyltrimethoxy silane 0.030 Silicone suds suppressor 0.0025 Brightener 0.148 Water & miscellaneous Balance Protease B* 0.28
  • the ingredients listed above are added to a mixing tank with a single agitator.
  • the pH of the mix is adjusted so that it is between about 8.0 and 8.5.

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  • Chemical & Material Sciences (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Oil, Petroleum & Natural Gas (AREA)
  • Wood Science & Technology (AREA)
  • Organic Chemistry (AREA)
  • Detergent Compositions (AREA)
EP89870064A 1988-05-12 1989-05-10 Heavy duty liquid laundry detergents containing anionic and nonionic surfactant, builder and proteolytic enzyme Expired - Lifetime EP0342177B1 (en)

Applications Claiming Priority (6)

Application Number Priority Date Filing Date Title
US19332088A 1988-05-12 1988-05-12
US193320 1988-05-12
US28873888A 1988-12-22 1988-12-22
US288738 1988-12-22
US34191889A 1989-04-26 1989-04-26
US341918 1989-04-26

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EP0342177A2 EP0342177A2 (en) 1989-11-15
EP0342177A3 EP0342177A3 (en) 1990-10-10
EP0342177B1 true EP0342177B1 (en) 1995-07-12

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EP (1) EP0342177B1 (ja)
JP (1) JP2716522B2 (ja)
KR (1) KR960012272B1 (ja)
AU (1) AU631793B2 (ja)
BR (1) BR8902223A (ja)
CA (1) CA1336895C (ja)
DE (1) DE68923398T2 (ja)
DK (1) DK232889A (ja)
IE (1) IE891559L (ja)
MX (1) MX170133B (ja)
NZ (1) NZ229079A (ja)
PT (1) PT90535B (ja)

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US6365785B1 (en) * 1997-08-02 2002-04-02 Therprocter & Gamble Company Process for preparing ether-capped poly(oxyalkylated) alcohol surfactants
EP2213714A1 (en) 2009-02-02 2010-08-04 The Procter & Gamble Company Liquid hand dishwashing detergent composition
EP2213713A1 (en) 2009-02-02 2010-08-04 The Procter & Gamble Company Liquid hand dishwashing detergent composition
EP2213715A1 (en) 2009-02-02 2010-08-04 The Procter & Gamble Company Liquid hand dishwashing detergent composition
WO2010088161A1 (en) 2009-02-02 2010-08-05 The Procter & Gamble Company Liquid hand dishwashing detergent composition
WO2010088164A1 (en) 2009-02-02 2010-08-05 The Procter & Gamble Company Liquid hand dishwashing detergent composition
WO2010088163A1 (en) 2009-02-02 2010-08-05 The Procter & Gamble Company Liquid hand dishwashing detergent composition
WO2013016031A1 (en) 2011-07-27 2013-01-31 The Procter & Gamble Company Multiphase liquid detergent composition
US8685171B2 (en) 2010-07-29 2014-04-01 The Procter & Gamble Company Liquid detergent composition
US9109189B2 (en) 2010-07-29 2015-08-18 The Procter & Gamble Company Liquid detergent composition
US9951298B2 (en) 2014-01-20 2018-04-24 The Procter & Gamble Company Fluorescent brightener premix
EP3202880B1 (en) 2016-02-05 2019-06-12 The Procter and Gamble Company Water-soluble unit dose article

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US5308530A (en) * 1990-11-21 1994-05-03 Lever Brothers Company, Division Of Conopco, Inc. Detergent compositions containing polycarboxylates and calcium-sensitive enzymes
CA2088230A1 (en) * 1992-02-03 1993-08-04 James Gordon Detergent composition
MX9302819A (es) * 1992-05-13 1994-07-29 Procter & Gamble Composicion detergente liquida para trabajo pesado.
JPH07152135A (ja) * 1993-08-11 1995-06-16 Eastman Kodak Co ハロゲン化銀写真要素をリンスするための水溶液及びハロゲン化銀写真要素の処理方法
USH1478H (en) * 1993-09-30 1995-09-05 Shell Oil Company Secondary alkyl sulfate-containing liquid laundry detergent compositions
USH1467H (en) * 1993-11-16 1995-08-01 Shell Oil Company Detergent formulations containing a surface active composition containing a nonionic surfactant component and a secondary alkyl sulfate anionic surfactant component
US5565135A (en) * 1995-01-24 1996-10-15 The Procter & Gamble Company Highly aqueous, cost effective liquid detergent compositions
ES2201281T3 (es) * 1996-03-26 2004-03-16 Basf Aktiengesellschaft Agentes de lavado y lavavajillas mejorados.
EP1124880A1 (en) 1998-11-05 2001-08-22 The Procter & Gamble Company Process for preparing ether-capped poly(oxyalkylated) alcohol surfactants
CA2348081A1 (en) 1998-11-05 2000-05-18 Deborah Jean Back Process for preparing ether-capped poly(oxyalkylated) alcohol surfactants
AU749498B2 (en) * 1998-12-16 2002-06-27 Unilever Plc Transparent/translucent liquid enzyme compositions in clear bottles comprising antioxidants
US10590368B2 (en) * 2007-03-27 2020-03-17 Novozymes A/S Stable enzyme solutions and method of manufacturing
KR20110095260A (ko) * 2008-11-11 2011-08-24 다니스코 유에스 인크. 하나 이상의 조합가능 돌연변이를 포함하는 바실러스 서브틸리신
EP2647692A3 (en) 2008-11-11 2014-01-22 The Procter and Gamble Company Compositions and methods comprising serine protease variants
DE102010029348A1 (de) 2010-05-27 2011-12-08 Henkel Ag & Co. Kgaa Maschinelles Geschirrspülmittel
EP3257377A1 (en) * 2016-06-13 2017-12-20 Universitat Autonoma de Barcelona Process for removing the fouling deposited in a milk processor unit and a cleaning solution used therein

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US4318818A (en) * 1979-11-09 1982-03-09 The Procter & Gamble Company Stabilized aqueous enzyme composition
IL78178A0 (en) * 1985-03-27 1986-07-31 Phinney Robin Production of potassium sulphate
US4670179A (en) * 1986-05-29 1987-06-02 Colgate Palmolive Company Stabilized built single phase liquid detergent composition containing enzymes
GB2194956A (en) * 1986-09-12 1988-03-23 Procter & Gamble Stable liquid detergent compositions

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US6365785B1 (en) * 1997-08-02 2002-04-02 Therprocter & Gamble Company Process for preparing ether-capped poly(oxyalkylated) alcohol surfactants
EP2216390A1 (en) 2009-02-02 2010-08-11 The Procter & Gamble Company Liquid hand dishwashing detergent composition
EP2213715A1 (en) 2009-02-02 2010-08-04 The Procter & Gamble Company Liquid hand dishwashing detergent composition
EP2216392A1 (en) 2009-02-02 2010-08-11 The Procter & Gamble Company Liquid hand dishwashing detergent composition
WO2010088158A1 (en) 2009-02-02 2010-08-05 The Procter & Gamble Company Liquid hand dishwashing detergent composition
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WO2010088161A1 (en) 2009-02-02 2010-08-05 The Procter & Gamble Company Liquid hand dishwashing detergent composition
WO2010088159A1 (en) 2009-02-02 2010-08-05 The Procter & Gamble Company Liquid hand dishwashing detergent composition
WO2010088164A1 (en) 2009-02-02 2010-08-05 The Procter & Gamble Company Liquid hand dishwashing detergent composition
EP2216391A1 (en) 2009-02-02 2010-08-11 The Procter & Gamble Company Liquid hand dishwashing detergent composition
EP2213714A1 (en) 2009-02-02 2010-08-04 The Procter & Gamble Company Liquid hand dishwashing detergent composition
EP3023483A1 (en) 2009-02-02 2016-05-25 The Procter and Gamble Company Liquid hand diswashing detergent composition
EP2213713A1 (en) 2009-02-02 2010-08-04 The Procter & Gamble Company Liquid hand dishwashing detergent composition
WO2010088163A1 (en) 2009-02-02 2010-08-05 The Procter & Gamble Company Liquid hand dishwashing detergent composition
US8575083B2 (en) 2009-02-02 2013-11-05 The Procter & Gamble Company Liquid hand diswashing detergent composition
US8685171B2 (en) 2010-07-29 2014-04-01 The Procter & Gamble Company Liquid detergent composition
US9109189B2 (en) 2010-07-29 2015-08-18 The Procter & Gamble Company Liquid detergent composition
WO2013016030A1 (en) 2011-07-27 2013-01-31 The Procter & Gamble Company Multiphase liquid detergent composition
WO2013016031A1 (en) 2011-07-27 2013-01-31 The Procter & Gamble Company Multiphase liquid detergent composition
US9951298B2 (en) 2014-01-20 2018-04-24 The Procter & Gamble Company Fluorescent brightener premix
EP3202879B2 (en) † 2016-02-05 2022-07-27 The Procter & Gamble Company Water-soluble unit dose article
EP3202880B1 (en) 2016-02-05 2019-06-12 The Procter and Gamble Company Water-soluble unit dose article
EP3202879B1 (en) 2016-02-05 2019-06-19 The Procter and Gamble Company Water-soluble unit dose article

Also Published As

Publication number Publication date
AU631793B2 (en) 1992-12-10
IE891559L (en) 1989-11-12
EP0342177A2 (en) 1989-11-15
EP0342177A3 (en) 1990-10-10
PT90535A (pt) 1989-11-30
DE68923398T2 (de) 1996-01-25
JPH0251596A (ja) 1990-02-21
KR900018349A (ko) 1990-12-21
CA1336895C (en) 1995-09-05
BR8902223A (pt) 1990-01-02
DK232889D0 (da) 1989-05-12
DK232889A (da) 1989-11-13
KR960012272B1 (ko) 1996-09-18
PT90535B (pt) 1994-11-30
MX170133B (es) 1993-08-09
JP2716522B2 (ja) 1998-02-18
NZ229079A (en) 1992-04-28
DE68923398D1 (de) 1995-08-17
AU3473289A (en) 1989-11-16

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