WO1993023516A1 - Granular detergent compositions with lipase - Google Patents

Granular detergent compositions with lipase Download PDF

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Publication number
WO1993023516A1
WO1993023516A1 PCT/US1993/004192 US9304192W WO9323516A1 WO 1993023516 A1 WO1993023516 A1 WO 1993023516A1 US 9304192 W US9304192 W US 9304192W WO 9323516 A1 WO9323516 A1 WO 9323516A1
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WIPO (PCT)
Prior art keywords
lipase
alkyl
weight
granular detergent
detergent composition
Prior art date
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PCT/US1993/004192
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English (en)
French (fr)
Inventor
Ann Margaret Wolff
Michael Stanford Showell
Original Assignee
The Procter & Gamble Company
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Filing date
Publication date
Application filed by The Procter & Gamble Company filed Critical The Procter & Gamble Company
Priority to EP93911031A priority Critical patent/EP0639222A1/en
Priority to SK1331-94A priority patent/SK133194A3/sk
Priority to JP5520289A priority patent/JPH07506618A/ja
Publication of WO1993023516A1 publication Critical patent/WO1993023516A1/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
    • C11D3/38—Products with no well-defined composition, e.g. natural products
    • C11D3/386—Preparations containing enzymes, e.g. protease or amylase
    • C11D3/38627—Preparations containing enzymes, e.g. protease or amylase containing lipase
    • 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
    • C11D1/37—Mixtures of compounds all of which are anionic
    • 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
    • C11D1/65—Mixtures of anionic with cationic compounds
    • C11D1/652—Mixtures of anionic compounds with carboxylic amides or alkylol amides
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D1/00—Detergent compositions based essentially on surface-active compounds; Use of these compounds as a detergent
    • C11D1/66—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
    • C11D1/00—Detergent compositions based essentially on surface-active compounds; Use of these compounds as a detergent
    • C11D1/66—Non-ionic compounds
    • C11D1/835—Mixtures of non-ionic with cationic compounds
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D1/00—Detergent compositions based essentially on surface-active compounds; Use of these compounds as a detergent
    • C11D1/02—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
    • C11D1/525—Carboxylic amides (R1-CO-NR2R3), where R1, R2 or R3 contain two or more hydroxy groups per alkyl group, e.g. R3 being a reducing sugar rest
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D1/00—Detergent compositions based essentially on surface-active compounds; Use of these compounds as a detergent
    • C11D1/66—Non-ionic compounds
    • C11D1/72—Ethers of polyoxyalkylene glycols

Definitions

  • This invention relates to a granular detergent composition containing lipase produced by a lipase producing strain from the fungi Humicola sp. or Thermomyces sp., or the bacteria Pseudomonas pseudoalcaligenes or Pseudomonas fluorescens. A method of cleaning fabrics using such a composition is also included.
  • lipase in detergent compositions for improved cleaning performance is known.
  • Examples are European Patent Application 0368 589, published May 16, 1990; U.S. Patents 4,707,291, Thorn et al, issued November 18, 1987, 4,769,173, Cornel issen et al issued September 6, 1988, 4,861,509, Cornel issen et al, issued August 29, 1989, 5,069,809, Lagerwaard et al, issued December 3,1991; and Japanese Publication 01161-096, published December 17, 1987.
  • the present invention relates to a granular detergent composition
  • a granular detergent composition comprising, by weight:
  • the granular detergent compositions herein comprise lipase, alkyl alkoxy sulfate or polyhydroxy fatty acid amide and additional anionic or nonionic surfactant.
  • the weight ratio of lipase to alkyl alkoxy sulfate or polyhydroxy fatty acid amide (or mixtures of the two) is between about 0.09 (9%) and about 0.28 (28%).
  • the amount of lipase divided by the amount of alkyl alkoxy sulfate or polyhydroxy fatty acid amide is between about 0.10 and about 0.20.
  • the present compositions preferably additionally comprise detergency builder, second enzymes, and other conventional detergent ingredients.
  • the present granular detergent compositions remove triglyceride-based soils (eg spaghetti sauce and bacon grease) after the first laundry cycle (ie the first time the fabric is washed after it is soiled) better than granular compositions with higher levels of lipase do. Without meaning to be bound by theory, it is believed that this is because the present formulas allow the hydrolytic products remaining after breakdown of the triglyceride-based soil by the lipase in the wash to be removed more efficiently than do formulas outside this invention.
  • the present optimized weight ratio of lipase: alkyl alkoxy sulfate or polyhydroxy fatty acid amide in combination with the low lipase levels employed herein are believed to bring about this first cycle benefit.
  • An essential ingredient of the present granular detergent composition is from about 0.00025 to about 0.015, preferably about 0.0025 to about 0.010, grams of active enzyme per 100 grams of composition, of lipase produced by a lipase producing strain of Humicola sp. or Thermomyces sp. or Pseudomonas pseudoalcaligenes or Pseudomonas fluorescens.
  • Lipase from chemically or genetically modified mutants of these strains are also included herein. Mixtures of lipase from various strains are included herein, though not preferred.
  • a preferred lipase is derived from Pseudomonas pseudoalcaligenes, which is described in U.S. Patent 4,933,287, Farin et al, issued June 12, 1990, incorporated herein by reference.
  • the most preferred lipase herein is obtained by cloning the gene from Humicola lanuginosa and expressing the gene in Aspergillus oryzae as described in European Patent Application 0 258 068, incorporated herein by reference, which is commercially available from Novo Industri A/S, Bagsvaerd, Denmark, under the trade name Lipolase ® .
  • This lipase is also described in U.S. Patent 4,810,414, Huge-Jensen et al, issued March 7, 1989, incorporated herein by reference.
  • Preferably, from about 0.001 to about 0.6, preferably about 0.1 to about 0.4, wt.% of Lipolase ® (100,000 LU/g) is employed in the present composition.
  • Lipases herein are preferably compatible with anionic (and nonionic) surfactants and have high activity at alkaline pH. They are preferably compatible with and stable in the present compositions and improve cleaning when they are included in the present compositions.
  • Suitable lipases include those which show a positive immunological cross-reaction with the antibody of the lipase produced by Pseudomonas fluorescens. This lipase is described in Japanese Patent Application 53-20487, laid open February 24, 1978, which is incorporated herein by reference. It is available under the trade name Lipase P Amano. A method for testing immunological cross-reaction with Amano P antibody is described in U.S. Patent 4,707,291, Thom et al, issued November 17, 1987, incorporated herein by reference.
  • a lipase unit is defined as the amount of lipase which produces 1 umol of titratable butyric acid per minute in a pH stat, where pH is 7.0, temperature is 30oC, and substrate is an emulsion of tributyrin and gum arabic in the presence of Ca++ and
  • the granular detergent compositions herein also comprise from about 0.5 to about 10 wt.%, preferably from about 0.5 to about 5 wt.%, most preferably from about 1 to about 2 wt. %, of alkyl alkoxy sulfate, preferably alkyl sulfate which has been ethoxylated with from about 0.5 to about 10, preferably from about 0.5 to about 2, moles of ethylene oxide per mole of alkyl sulfate, and/or polyhydroxy fatty acid amide. Mixtures of the two surfactants are included herein.
  • the compositions further comprise from about 2 to about 30 wt.%, preferably from about 10 to about 20 wt.%, of additional anionic or nonionic surfactant. 1. Alkyl Alkoxy Sulfate
  • Alkyl alkoxy!ated sulfate surfactants are water soluble salts or acids typically of the formula RO(A) m SO 3 M wherein R is an unsubstituted C 10 -C 24 alkyl or hydroxyalkyl group having a C 10 -C 24 alkyl component, preferably a C 12 -C 20 alkyl or hydroxyalkyl, more preferably C 12 -C 18 alkyl or hydroxyalkyl, A is an ethoxy or propoxy unit, m is greater than zero, typically between about 0.5 and about 6, more preferably between about 0.5 and about 3, and M is H or a cation which can be, for example, a metal cation (e.g., sodium, potassium, lithium, calcium, magnesium, etc.), ammonium or substituted-ammonium cation.
  • R is an unsubstituted C 10 -C 24 alkyl or hydroxyalkyl group having a C 10 -C 24 alkyl component, preferably
  • Alkyl ethoxylated sulfates as well as alkyl propoxylated sulfates are contemplated herein.
  • Specific examples of substituted ammonium cations include methyl-, dimethyl-, trimethyl-ammonium and quaternary ammonium cations, such as tetramethyl-ammonium, dimethyl piperydinium and cations derived from alkanol amines, e.g. monoethanolamine, diethanolamine, and triethanolamine, and mixtures thereof.
  • Exemplary surfactants are C 12 -C 18 alkyl polyethoxylate (1.0) sulfate, C 12 -C 18 alkyl polyethoxylate (2.25) sulfate, C 12 -C 18 alkyl polyethoxylate (3.0) sulfate, and C 12 -C 18 alkyl polyethoxylate (4.0) sulfate wherein M is conveniently selected from sodium and potassium.
  • Polyhydroxy fatty acid amide surfactant comprises compounds of the structural formula:
  • R 1 is H, C 1 -C 4 hydrocarbyl, 2-hydroxy ethyl, 2-hydroxy propyl, or a mixture thereof, preferably C 1 -C 4 alkyl, more preferably C 1 or C 2 alkyl, most preferably C 1 alkyl (i.e., methyl); and R 2 is a C 5 -C 31 hydrocarbyl, preferably straight chain C 7 -C 19 alkyl or alkenyl, more preferably straight chain C 9 -C 17 alkyl or alkenyl, most preferably straight chain C 11 -C 15 alkyl or alkenyl, or mixtures thereof; and Z is a polyhydroxyhydrocarbyl having a linear hydrocarbyl chain with at least 3 hydroxyls directly connected to the chain, or an alkoxylated derivative (preferably ethoxylated or propoxylated) thereof.
  • Z preferably will be derived from a reducing sugar in a reductive amination reaction; more preferably Z will be a glycityl.
  • Suitable reducing sugars include glucose, fructose, maltose, lactose, galactose, mannose, and xylose.
  • Z preferably will be selected from the group consisting of -CH 2 -(CHOH) n -CH 2 OH, -CH(CH 2 OH)-(CHOH) n-1 -CH 2 OH, -CH 2 -(CHOH) 2 (CHOR')(CHOH)-CH 2 OH, and alkoxylated derivatives thereof, where n is an integer from 3 to 5, inclusive, and R' is H or a cyclic or aliphatic monosaccharide. Most preferred are glycityl s wherein n is 4, particularly -CH 2 -(CHOH) 4 -CH 2 OH.
  • the polyhydroxy fatty acid amide preferred herein is glucose amide, preferably C 12-18 N-acetyl glucamide.
  • Anionic surfactants useful for detersive purposes are included in the compositions hereof. These can include salts (including, for example, sodium, potassium, ammonium, and substituted ammonium salts such as mono-, di- and triethanolamine salts) of soap, C 9 -C 20 linear alkyl benzenesulphonates, C 8 -C 22 primary or secondary alkanesulphonates, C 8 -C 24 olefinsulphonates, sulphonated polycarboxylic acids prepared by sulphonation of the pyrolyzed product of alkaline earth metal citrates, e.g., as described in British Patent Specification No.
  • salts including, for example, sodium, potassium, ammonium, and substituted ammonium salts such as mono-, di- and triethanolamine salts
  • C 9 -C 20 linear alkyl benzenesulphonates C 8 -C 22 primary or secondary alkanesulphonates
  • alkyl glycerol sulfonates 1,082,179, alkyl glycerol sulfonates, fatty acyl glycerol sulfonates, fatty oleyl glycerol sulfates, alkyl phenol ethylene oxide ether sulfates, paraffin sulfonates, alkyl phosphates, isothionates such as the acyl isothionates, N-acyl taurates, fatty acid amides of methyl tauride, alky!
  • succinamates and sulfosuccinates monoesters of sulfosuccinate (especially saturated and unsaturated C 12 -C 18 monoesters) diesters of sulfosuccinate (especially saturated and unsaturated C 6 -C 14 diesters), N-acyl sarcosinates, sulfates of aikylpolysaccharides such as the sulfates of alkylpolyglucoside (the nonionic nonsulfated compounds being described below), branched primary alkyl sulfates, alkyl polyethoxy carboxylates such as those of the formula RO(CH 2 CH 2 O) k CH 2 COO-M + wherein R is a C 8 -C 22 alkyl, k is an integer from 0 to 10, and M is a soluble salt-forming cation, and fatty acids esterified with isothionic acid and neutralized with sodium hydroxide.
  • Resin acids and hydrogenated resin acids are also suitable, such as rosin, hydrogenated rosin, and resin acids and hydrogenated resin acids present in or derived from tall oil. Further examples are given in "Surface Active Agents and Detergents" (Vol. I and II by Schwartz, Perry and Berch). A variety of such surfactants are also generally disclosed in U.S. Patent 3,929,678, issued December 30, 1975 to Laughlin, et al. at Column 23, line 58 through Col umn 29, line 23 (herein incorporated by reference).
  • Alkyl sulfate surfactants are a type of anionic surfactant preferred for use herein.
  • dissolution of alkyl sulfates can be obtained, as well as improved formul ability in liquid detergent formulations are water soluble salts or acids of the formula ROSO 3 M wherein R preferably is a C 10 -C 24 hydrocarbyl, preferably an alkyl or hydroxyalkyl having a C 10 -C 20 alkyl component, more preferably a C 12 -C 18 alkyl or hydroxyalkyl, and M is H or a cation, e.g., an alkali metal cation (e.g., sodium, potassium, lithium), substituted or unsubstituted ammonium cations such as methyl-, dimethyl-, and trimethyl ammonium and quatern
  • C 12 -C 20 alkyl sulfate (“AS"), and/or C 9 -C 20 linear alkylbenzene sulfonate (preferably sodium salts). Preferred are from about 2 to about 10 wt.% of the C 12-20 AS and from about 10 to about 15 wt.% of the C 9-20 LAS.
  • the nonionic surfactant is the condensation product of C 10 -C 20 alcohol and between about 2 and about 20 moles of ethylene oxide per mole of alcohol (“E2-20 ethoxylated C 10-20 alcohol”). 4. Additional Nonionic Surfactant
  • Suitable nonionic detergent surfactants are generally disclosed in U.S. Patent 3,929,678, Laughlin et al., issued December 30, 1975, at column 13, line 14 through column 16, line 6, incorporated herein by reference. Exemplary, non-limiting classes of useful nonionic surfactants are listed below.
  • the polyethylene, polypropylene, and polybutylene oxide condensates of alkyl phenols are preferred. These compounds include the condensation products of alkyl phenols having an alkyl group containing from about 6 to about 12 carbon atoms in either a straight chain or branched chain configuration with the alkylene oxide. These compounds are commonly referred to as alkyl phenol alkoxylates, (e.g., alkyl phenol ethoxylates).
  • alkyl chain of the aliphatic alcohol can either be straight or branched, primary or secondary, and generally contains from about 8 to about 22 carbon atoms.
  • This category of nonionic surfactant is referred to generally as "alkyl ethoxylates.”
  • alkyl ethoxylates Preferred are C 12-16 , preferably C12-13, aliphatic alcohols ethoxylated with from about 3 to about 10 moles of ethylene oxide per mole of alcohol.
  • Semi-polar nonionic surfactants are a special category of nonionic surfactants which include water-soluble amine oxides containing one alkyl moiety of from about 10 to about 18 carbon atoms and 2 moieties selected from the group consisting of alkyl groups and hydroxyalkyl groups containing from about 1 to about 3 carbon atoms; water-soluble phosphine oxides containing one alkyl moiety of from about 10 to about 18 carbon atoms and 2 moieties selected from the group consisting of alkyl groups and hydroxyalkyl groups containing from about 1 to about 3 carbon atoms; and water-soluble sulfoxides containing one alkyl moiety of from about 10 to about 18 carbon atoms and a moiety selected from the group consisting of alkyl and hydroxyalkyl moieties of from about 1 to about 3 carbon atoms.
  • R 6 is an alkyl group containing from about 7 to about 21 (preferably from about 9 to about 17) carbon atoms and each R 7 is selected from the group consisting of hydrogen, C 1 -C 4 alkyl, C 1 -C 4 hydroxyalkyl, and -(C 2 H 4 O) x H where x varies from about 1 to about 3.
  • weight % of detergency builder can optionally be, and preferably is, included herein.
  • Inorganic as well as organic builders can be used.
  • Inorganic detergency builders include, but are not limited to, the alkali metal, ammonium and alkanol ammonium salts of polyphosphates (exemplified by the tripolyphosphates, pyrophosphates, and glassy polymeric meta-phosphates), phosphonates, phytic acid, silicates, carbonates (including bicarbonates and sesquicarbonates), sulphates, and aluminosilicates.
  • Borate builders, as well as builders containing borate-forming materials that can produce borate under detergent storage or wash conditions hereinafter, collectively “borate builders"
  • non-borate builders are used in the compositions of the invention intended for use at wash conditions less than about 50oC, especially less than about 40oC.
  • silicate builders are the alkali metal silicates, particularly those having a SiO 2 :Na 2 O ratio in the range 1.6:1 to 3.2:1 and layered silicates, such as the layered sodium silicates described in U.S. Patent 4,664,839, issued May 12, 1987 to H. P. Rieck, incorporated herein by reference.
  • layered silicates such as the layered sodium silicates described in U.S. Patent 4,664,839, issued May 12, 1987 to H. P. Rieck, incorporated herein by reference.
  • other silicates may also be useful such as for example magnesium silicate, which can serve as a crispening agent- in granular formulations, as a stabilizing agent for oxygen bleaches, and as a component of suds control systems.
  • carbonate builders are the alkaline earth and alkali metal carbonates, including sodium carbonate and sesquicarbonate and mixtures thereof with ultra-fine calcium carbonate as disclosed in German Patent Application No. 2,321,001 published on November 15, 1973, the disclosure of which is incorporated herein by reference.
  • Aluminosilicate builders are useful in the present invention. Aluminosilicate builders are of great importance in most currently marketed heavy duty granular detergent compositions, and can also be a significant builder ingredient in liquid detergent formulations. Aluminosilicate builders include those having the empirical formula:
  • aluminosilicates are zeolite builders which have the formula:
  • z and y are integers of at least 6, the molar ratio of z to y is in the range from 1.0 to about 0.5, and x is an integer from about 15 to about 264.
  • aluminosilicate ion exchange materials are commercially available. These aluminosilicates can be crystalline or amorphous in structure and can be naturally-occurring aluminosilicates or synthetically derived. A method for producing aluminosilicate ion exchange materials is disclosed in U.S. Patent 3,985,669, Krummel, et al., issued October 12, 1976, incorporated herein by reference. Preferred synthetic crystalline aluminosilicate ion exchange materials useful herein are available under the designations Zeolite A, Zeolite P (B), and Zeolite X.
  • polyphosphates are the alkali metal tripolyphosphates, sodium, potassium and ammonium pyrophosphate, sodium and potassium and ammonium pyrophosphate, sodium and potassium orthophosphate, sodium polymeta phosphate in which the degree of polymerization ranges from about 6 to about 21, and salts of phytic acid.
  • phosphonate builder salts are the water-soluble salts of ethane 1-hydroxy-1, 1-diphosphonate particularly the sodium and potassium salts, the water-soluble salts of methylene diphosphonic acid e.g. the trisodium and tripotassium salts and the water-soluble salts of substituted methylene diphosphonic acids, such as the trisodium and tripotassium ethyl idene, isopyropylidene benzylmethyl idene and halo methyl idene phosphonates.
  • Phosphonate builder salts of the aforementioned types are disclosed in U.S.
  • Patents 3,159,581 and 3,213,030 issued December 1, 1964 and October 19, 1965, to Diehl; U.S. Patent 3,422,021 issued January 14, 1969, to Roy; and U.S. Patents 3,400,148 and 3,422,137 issued September 3, 1968, and January 14, 1969 to Quimby.
  • Organic detergent builders preferred for the. purposes of the present invention include a wide variety of polycarboxylate compounds.
  • polycarboxylate refers to compounds having a plurality of carboxylate groups, preferably at least 3 carboxylates.
  • Polycarboxylate builder can generally be added to the composition in acid form, but can also be added in the form of a neutralized salt.
  • alkali metals such as sodium, potassium, and lithium, or alkanol ammonium salts are preferred.
  • polycarboxylate builders include a variety of categories of useful materials.
  • One important category of polycarboxylate builders encompasses the ether polycarboxylates.
  • a number of ether polycarboxylates have been disclosed for use as detergent builders.
  • Examples of useful ether polycarboxylates include oxydisuccinate, as disclosed in Berg, U.S. Patent 3,128,287, issued April 7, 1964, and Lamberti et al., U.S. Patent 3,635,830, issued January 18, 1972, both of which are incorporated herein by reference.
  • ether polycarboxylates useful as builders in the present invention also include those having the general formula:
  • A is H or OH; B is H or -O-CH(COOX)-CH 2 (COOX); and X is H or a salt-forming cation.
  • a and B are both H, then the compound is oxydissuccinic acid and its water-soluble salts. If A is OH and B is H, then the compound is tartrate monosuccinic acid (TMS) and its water-soluble salts. If A is H and B is -O-CH(COOX)-CH 2 (COOX), then the compound is tartrate disuccinic acid (TDS) and its water-soluble salts.
  • TMS monosuccinic acid
  • TDS tartrate disuccinic acid
  • TDS tartrate disuccinic acid
  • Mixtures of these builders are especially preferred for use herein. Particularly preferred are mixtures of TMS and TDS in a weight ratio of TMS to TDS of from about 97:3 to about 20:80.
  • Suitable ether polycarboxylates also include cyclic compounds, particularly alicyclic compounds, such as those described in U.S. Patents 3,923,679; 3,835,163; 4, 158, 635 ;4,120,874 and 4,102,903, all of which are incorporated herein by reference.
  • ether hydroxypolycarboxylates represented by the structure:
  • M is hydrogen or a cation wherein the resultant salt is water-soluble, preferably an alkali metal, ammonium or substituted ammonium cation, n is from about 2 to about 15 (preferably n is from about 2 to about 10, more preferably n averages from about 2 to about 4) and each R is the same or different and selected from hydrogen, C 1-4 alkyl or C 1-4 substituted alkyl (preferably R is hydrogen).
  • Still other ether polycarboxylates include copolymers of maleic anhydride with ethylene or vinyl methyl ether, 1, 3, 5-trihydroxy benzene-2, 4, 6-trisulphonic acid, and carboxymethyloxysuccinic acid.
  • Organic polycarboxylate builders also include the various alkali metal, ammonium and substituted ammonium salts of polyacetic acids. Examples include the sodium, potassium, lithium, ammonium and substituted ammonium salts of ethylenediamine tetraacetic acid, and nitrilotriacetic acid.
  • polycarboxylates such as mellitic acid, succinic acid, oxydisuccinic acid, polymaleic acid, benzene 1,3,5-tricarboxylic acid, and carboxymethyloxysuccinic acid, and soluble salts thereof.
  • Citrate builders e.g., citric acid and soluble salts thereof (particularly sodium salt), are polycarboxylate builders which can also be used in granular compositions.
  • carboxylate builders include the carboxylated carbohydrates disclosed in U.S. Patent 3,723,322, Diehl, issued March 28, 1973, incorporated herein by reference. Also suitable in the detergent compositions of the present invention are the 3,3-dicarboxy-4-oxa-1,6-hexanedioates and the related compounds disclosed in U.S. Patent 4,566,984, Bush, issued January 28, 1986, incorporated herein by reference.
  • Useful succinic acid builders include the C 5 -C 20 alkyl succinic acids and salts thereof. A particularly preferred compound, of this type is dodecenylsuccinic acid.
  • Alkyl succinic acids typically are of the general formula R-CH(COOH)CH 2 (COOH) i.e., derivatives of succinic acid, wherein R is hydrocarbon, e.g., C 10 -C 20 alkyl or alkenyl, preferably C 12 -C 16 or wherein R may be substituted with hydroxyl, sulfo, sulfoxy or sulfone substituents, all as described in the above-mentioned patents.
  • R is hydrocarbon, e.g., C 10 -C 20 alkyl or alkenyl, preferably C 12 -C 16 or wherein R may be substituted with hydroxyl, sulfo, sulfoxy or sulfone substituents, all as described in the above-mentioned patents.
  • the succinate builders are preferably used in the form of their water-soluble salts, including the sodium, potassium, ammonium and alkanol ammonium salts.
  • succinate builders include: laurylsuccinate, myristylsuccinate, palmitylsuccinate, 2-dodecenyl succinate (preferred), 2-pentadecenyl succinate, and the like. Laurylsuccinates are the preferred builders of this group, and are described in European Patent Application 86200690.5/0,200,263, published November 5, 1986.
  • useful builders also include sodium and potassium carboxymethyloxymalonate, carboxymethyloxysuccinate, cis-cyclohexane-hexacarboxylate, cis-cyclopentane-tetracarboxylate, watersoluble polyacrylates (these polyacrylates having molecular weights to above about 2,000 can also be effecitvly utilized as dispersants), and the copolymers of maleic anhydride with vinyl methyl ether or ethylene.
  • polyacetal carboxylates are the polyacetal carboxylates disclosed in U.S. Patent 4,144,226, Crutchfield et al., issued March 13, 1979, incorporated herein by reference. These polyacetal carboxylates can be prepared by bringing together, under polymerization conditions, an ester of glyoxylic acid and a polymerization initiator. The resulting polyacetal carboxylate ester is then attached to chemically stable end groups to stabilize the polyacetal carboxylate against rapid depolymerization in alkaline solution, converted to the corresponding salt, and added to a surfactant.
  • Such materials include the water-soluble salts of homo- and copolymers of aliphatic carboxylic acids such as maleic acid, itaconic acid, mesaconic acid, fumaric acid, aconitic acid, citraconic acid and methylenemalonic acid.
  • organic builders known in the art can also be used.
  • monocarboxyl ic acids, and soluble salts thereof, having long chain hydrocarbyl s can be utilized. These would include materials generally referred to as "soaps.” Chain lengths of C 10 -C 20 are typically utilized.
  • the hydrocarbyls can be saturated or unsaturated.
  • the detergency builder herein is selected from the group consisting of the salts, preferably the sodium salt, of carbonate, silicate, sulfate, phosphate, aluminosilicate, and citric acid and mixtures thereof.
  • ingredients include second enzymes, which include protease (most preferred), amylase, peroxidase, cellulase, and mixtures thereof.
  • second enzyme is meant enzymes in addition to lipase which are also added to the composition. Second enzymes from chemically or genetically modified mutants, and from bacterial or fungal origin, are included herein.
  • the amount of second enzyme used in the composition varies according to the type of enzyme and the use intended. In general, from about 0.0001 to about 1.0, more preferably about 0.001 to about 0.5, weight % on an active basis of these second enzymes are preferably used. Mixtures of enzymes from the same class (e.g. protease) or two or more classes (e.g. cellulase and protease) may be used.
  • same class e.g. protease
  • two or more classes e.g. cellulase and protease
  • Any cellulase suitable for use in a detergent composition can be used in these compositions. From about 0.0001 to 1.0, preferably 0.001 to 0.5, weight % on an active enzyme basis of cellulase can be used. Suitable cellulases are disclosed in U.S. Patent 4,435,307,
  • cellulases examples include cellulases produced by a strain of Humicola insolens (Humicola grisea var. thermoidea). particularly the Humicola strain DSM 1800, and cellulases produced by a fungus of Bacillus N or a cellulase 212-producing fungus belonging to the genus Aeromonas, and cellulase extracted from the hepatopancreas of a marine mollusc (Dolabella Auricula Solander).
  • Amylases include, for example, ⁇ -amylases obtained from a special strain of B.Iicheniforms. described in more detail in British Patent Specification No. 1,296,839.
  • Amylolytic proteins include, for example, RapidaseTM, MaxamylTM and TermamylTM.
  • Peroxidase enzymes are used in combination with oxygen sources, e.g., percarbonate, perborate, persulfate, hydrogen peroxide, etc. They are used for "solution bleaching," i.e. to prevent transfer of dyes or pigments removed from substrates during wash operations to other substrates in the wash solution.
  • Peroxidase enzymes are known in the art, and include, for example, horseradish peroxidase, ligninase, and haloperoxidase such as chloro-and bromo-peroxidase.
  • Peroxidase-containing detergent compositions are disclosed, for example, in PCT International Application W0 89/099813, published October 19, 1989, by 0. Kirk, assigned to Novo Industries A/S, incorporated herein by reference.
  • protease enzymes can be of animal, vegetable or microorganism (preferred) origin. More preferred is serine protease enzyme of bacterial origin. Purified or nonpurified forms of this enzyme may be used. Proteases produced by chemically or genetically modified mutants are included by definition, as are close structural enzyme variants. Particularly preferred is bacterial serine protease enzyme obtained from Bacillus subtilis and/or Bacillus licheniformis.
  • Suitable proteases include Alcalase ® , Esperase ® , Savinase ® (preferred); Maxatase ® , Maxacal ® (preferred), and Maxapem 15 ® (protein engineered Maxacal ® ); and subtilisin BPN and BPN' (preferred); which are commercially available.
  • Preferred proteases are also modified bacterial serine proteases, such as those described in European Patent Application Serial Number 87 303761.8, filed April 28, 1987 (particularly pages 17, 24 and 98), and which is called herein "Protease B", and in European Patent Application 199,404, Venegas, published October 29, 1986, which refers to a modified bacterial serine proteolytic enzyme which is called "Protease A” herein.
  • Preferred proteolytic enzymes are selected from the group consisting of Savinase ® , Maxacal ® , BPN', Protease A, Protease B, and mixtures thereof. Protease B is most preferred.
  • ingredients suitable for use in the present compositions such as water, perfume, brightener, conditioners such as fumed silica, polyethylene glycol, dyes and colorants, and peroxyacids, can be included.
  • Preferred ingredients are from about 0.5 to about 5 wt.% of polyethylene glycol (preferably with molecular weight between 5,000 and 10,000, most preferably 8,000), from about 0.01 to about 0.7 wt.% of fluorescent whitening and/or brightening agents, and from about 0.01 to about 1.0 wt.% of perfume.
  • Bleaching agents including preformed peroxyacids, activated perborate, and activated percarbonate may also be present in the granular compositions, though they are not preferred. Suggested levels are from about 0.5 to about 5 wt% of peroxyacid, from 5 to about 25 wt.% of percarbonate or perborate and from about 0.1 to about 10 wt% of activator.
  • a preferred activator for use with lipase is tetra acetyl ethylene diamine. Preferred are formulas without bleaching agent except for from about 0.5 to about 1.0 wt.% of sodium perborate.
  • the granular detergent composition is added to the wash, usually at levels of 1/4 to 1 cup.
  • Agitation is preferably provided in the washing machine for good cleaning. Washing is preferably followed by drying the wet fabric in a conventional clothes dryer.
  • An effective amount of the granular detergent composition is preferably from about 500 to about 7000 ppm, more preferably from about 1000 to about 3000 ppm.
  • the Detergent A samples do not contain alkyl alkoxy sulfate or polyhydroxy fatty acid amide.
  • the Detergent A samples do contain lipase at three levels: 0; 0.012 grams of active enzyme per 100 grams of composition (500 LU/1; 0.48 wt.%); and 0.036 g/100g (1500 LU/1; 1.44 wt.%). As shown in Table A, Detergent A with lipase (both samples) performed worse than Detergent A without lipase after the first wash cycle.
  • Table B concerns Detergent B.
  • Detergent B containing polyhydroxy fatty acid amide (N-acetyl fatty acid glucamide) and 0.012g/100g lipase (500 LU/1) performs significantly better than both Detergent B with three times as much lipase (0.036 g/100g; 1500 LU/1), and Detergent B without lipase (Table B).
  • Detergent B with 0.012g/100g lipase is within the present invention. The other two Detergent B samples are not.
  • Detergent A (without al kyl al koxy sul fate or pol yhydroxy fatty acid amide)
  • Polyethylene glycol (MW 8000) 1.74
  • lipolytic enzyme in a detergent composition of the type described, and the comparative effectiveness of lipolytic enzyme in a comparative detergent formulation, are estimated as follows:
  • the detergent formulas are as follows:
  • Savinase ® protease 1 1 Lipase (Lipolase ® ) is used in each case in an equal amount. Wash temperature is 40oC.
  • test shows the presence of 0.18g oil and 48% triglyceride remaining in the extracted material. After washing with formulation (b) the test shows the presence of 0.11g oil and 50% triglyceride remaining.
  • formulation (b) enables the removal of more free fatty acids (FFA) from the material (0.7g more removed) while the lipolytic enzyme functions to release the same percentage of FFA from both treatments (48% vs. 50%).
  • Improved surfactant formulation e.g. Detergent b with glucose amide and alkylethoxy sulfate; within the present invention
  • the weaker surfactant formulation e.g. Detergent a, which is outside the present invention
  • composition of the present iinvention is as follows:
  • Polyethylene glycol (MW 8000) 0.80
  • composition of the present invention is as follows:
  • composition of the present invention is as follows:
  • Lipolase ® from Humicola lanuginosa can be substituted herein.

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  • Engineering & Computer Science (AREA)
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PCT/US1993/004192 1992-05-08 1993-05-04 Granular detergent compositions with lipase WO1993023516A1 (en)

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EP93911031A EP0639222A1 (en) 1992-05-08 1993-05-04 Granular detergent compositions with lipase
SK1331-94A SK133194A3 (en) 1992-05-08 1993-05-04 Pelletized detergent compositions and method of matters cleaning by these compositions
JP5520289A JPH07506618A (ja) 1992-05-08 1993-05-04 リパーゼを含有する粒状洗剤組成物

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Cited By (10)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO1995000625A1 (en) * 1993-06-25 1995-01-05 The Procter & Gamble Company Granular laundry detergent compositions containing lipase and sodium nonanoyloxybenzene sulfonate
WO1995027029A1 (de) * 1994-03-31 1995-10-12 Henkel Kommanditgesellschaft Auf Aktien Lipasehaltiges textilwaschmittel
WO1995033034A1 (en) * 1994-06-01 1995-12-07 The Procter & Gamble Company Oleoyl sarcosinate with polyhydroxy fatty acid amides in cleaning products
EP0698659A1 (en) * 1994-08-23 1996-02-28 The Procter & Gamble Company Detergent compositions comprising lipolytic enzymes
WO1996034936A1 (fr) * 1995-05-05 1996-11-07 Genencor International, Inc. Compositions detergentes
WO1997043375A1 (en) * 1996-05-15 1997-11-20 The Procter & Gamble Company Detergent compositions comprising specific lipolytic enzyme and a specific surfactant system
US5707950A (en) * 1994-11-18 1998-01-13 The Procter & Gamble Company Detergent compositions containing lipase and protease
US5837010A (en) * 1994-11-18 1998-11-17 Procter & Gamble Company Detergent compositions containing a lipase variant at low levels
EP0912681A1 (en) * 1996-05-15 1999-05-06 The Procter & Gamble Company Detergent compositions comprising specific lipolytic enzyme and lime soap dispersant
WO2020058024A1 (en) * 2018-09-17 2020-03-26 Unilever Plc Detergent composition

Families Citing this family (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2859520B2 (ja) * 1993-08-30 1999-02-17 ノボ ノルディスク アクティーゼルスカブ リパーゼ及びそれを生産する微生物及びリパーゼ製造方法及びリパーゼ含有洗剤組成物
CN101688152B (zh) * 2007-06-22 2012-06-27 荷兰联合利华有限公司 粒状加酶洗涤剂组合物
US7618801B2 (en) * 2007-10-30 2009-11-17 Danison US Inc. Streptomyces protease
CN102286557A (zh) * 2011-07-01 2011-12-21 江南大学 一种提高脂肪酶底物转化效率的非热加工方法

Citations (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE1767413A1 (de) * 1967-08-14 1971-09-09 Henkel & Cie Gmbh Als Textilwaschmittel brauchbare Tensidkombinationen sowie diese enthaltende Wasch- oder Waschhilfsmittel
EP0179533A2 (en) * 1984-10-26 1986-04-30 The Procter & Gamble Company Spray dried granular detergent compositions and process for their manufacture
EP0206390A2 (en) * 1985-06-11 1986-12-30 Unilever N.V. Enzymatic detergent composition
WO1989004361A1 (en) * 1987-11-02 1989-05-18 Novo-Nordisk A/S Enzymatic detergent composition
WO1989010955A1 (en) * 1988-05-09 1989-11-16 Unilever Plc Enzymatic detergent and bleaching composition
WO1989010954A1 (en) * 1988-05-10 1989-11-16 Unilever Plc Enzymatic detergent composition
EP0368589A2 (en) * 1988-11-08 1990-05-16 Unilever Plc Enzyme-containing detergent compositions
WO1992006154A1 (en) * 1990-09-28 1992-04-16 The Procter & Gamble Company Polyhydroxy fatty acid amide surfactants to enhance enzyme performance

Patent Citations (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE1767413A1 (de) * 1967-08-14 1971-09-09 Henkel & Cie Gmbh Als Textilwaschmittel brauchbare Tensidkombinationen sowie diese enthaltende Wasch- oder Waschhilfsmittel
EP0179533A2 (en) * 1984-10-26 1986-04-30 The Procter & Gamble Company Spray dried granular detergent compositions and process for their manufacture
EP0206390A2 (en) * 1985-06-11 1986-12-30 Unilever N.V. Enzymatic detergent composition
WO1989004361A1 (en) * 1987-11-02 1989-05-18 Novo-Nordisk A/S Enzymatic detergent composition
WO1989010955A1 (en) * 1988-05-09 1989-11-16 Unilever Plc Enzymatic detergent and bleaching composition
WO1989010954A1 (en) * 1988-05-10 1989-11-16 Unilever Plc Enzymatic detergent composition
EP0368589A2 (en) * 1988-11-08 1990-05-16 Unilever Plc Enzyme-containing detergent compositions
WO1992006154A1 (en) * 1990-09-28 1992-04-16 The Procter & Gamble Company Polyhydroxy fatty acid amide surfactants to enhance enzyme performance

Non-Patent Citations (3)

* Cited by examiner, † Cited by third party
Title
DATABASE WPI Section Ch, Derwent Publications Ltd., London, GB; Class A97, AN 89-224557[31] *
RESEARCH DISCLOSURE no. 290, June 1988, NEW YORK,NY,USA page 397 , ANONYMOUS 'Use of Lipase' *
THE INSTITUTE OF PAPER CHEMISTRY-LIBRARY. APPLETON.; 1 January 1988 (1988-01-01), BORDEI M., PREDA M. A., HAZU S., ET AL.: "LEATHER SUBSTITUTES BASED ON CELLULOSE PULP AND RUBBER.", XP000029056 *

Cited By (13)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO1995000625A1 (en) * 1993-06-25 1995-01-05 The Procter & Gamble Company Granular laundry detergent compositions containing lipase and sodium nonanoyloxybenzene sulfonate
WO1995027029A1 (de) * 1994-03-31 1995-10-12 Henkel Kommanditgesellschaft Auf Aktien Lipasehaltiges textilwaschmittel
WO1995033034A1 (en) * 1994-06-01 1995-12-07 The Procter & Gamble Company Oleoyl sarcosinate with polyhydroxy fatty acid amides in cleaning products
EP0698659A1 (en) * 1994-08-23 1996-02-28 The Procter & Gamble Company Detergent compositions comprising lipolytic enzymes
US6133220A (en) * 1994-11-18 2000-10-17 The Procter & Gamble Company Detergent compositions containing a lipase variant at low levels
US5707950A (en) * 1994-11-18 1998-01-13 The Procter & Gamble Company Detergent compositions containing lipase and protease
US5837010A (en) * 1994-11-18 1998-11-17 Procter & Gamble Company Detergent compositions containing a lipase variant at low levels
WO1996034936A1 (fr) * 1995-05-05 1996-11-07 Genencor International, Inc. Compositions detergentes
BE1009312A3 (fr) * 1995-05-05 1997-02-04 Solvay Compositions detergentes.
WO1997043375A1 (en) * 1996-05-15 1997-11-20 The Procter & Gamble Company Detergent compositions comprising specific lipolytic enzyme and a specific surfactant system
EP0912681A1 (en) * 1996-05-15 1999-05-06 The Procter & Gamble Company Detergent compositions comprising specific lipolytic enzyme and lime soap dispersant
WO2020058024A1 (en) * 2018-09-17 2020-03-26 Unilever Plc Detergent composition
CN112703246A (zh) * 2018-09-17 2021-04-23 联合利华知识产权控股有限公司 洗涤剂组合物

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CA2134978A1 (en) 1993-11-25
CZ270494A3 (en) 1995-03-15
MA22891A1 (fr) 1993-12-31
RU94046042A (ru) 1996-09-27
CN1080952A (zh) 1994-01-19
HU9403201D0 (en) 1995-02-28
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SK133194A3 (en) 1995-04-12
AU4231493A (en) 1993-12-13

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