EP0639222A1 - Granular detergent compositions with lipase - Google Patents

Granular detergent compositions with lipase

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Publication number
EP0639222A1
EP0639222A1 EP93911031A EP93911031A EP0639222A1 EP 0639222 A1 EP0639222 A1 EP 0639222A1 EP 93911031 A EP93911031 A EP 93911031A EP 93911031 A EP93911031 A EP 93911031A EP 0639222 A1 EP0639222 A1 EP 0639222A1
Authority
EP
European Patent Office
Prior art keywords
lipase
weight
granular detergent
detergent composition
aikyl
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Withdrawn
Application number
EP93911031A
Other languages
German (de)
English (en)
French (fr)
Inventor
Ann Margaret Wolff
Michael Stanford Showell
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Procter and Gamble Co
Original Assignee
Procter and Gamble Co
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Procter and Gamble Co filed Critical Procter and Gamble Co
Publication of EP0639222A1 publication Critical patent/EP0639222A1/en
Withdrawn legal-status Critical Current

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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 Ther omvces sp., or the bacteria Pseudo ⁇ tonas Dseudoalcaliqenes or Pseudomonas fluorescens.
  • a method of cleaning fabrics using such a composition is also included.
  • the present invention relates to a granular detergent composition comprising, by weight:
  • the granular detergent compositions herein comprise lipase, aikyl alkoxy sulfate or polyhydroxy fatty acid amide and additional anionic or nonionic surfactant.
  • the weight ratio of lipase to aikyl 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 aikyl 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:aikyl 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 Thermomvces sp. or Pseudomonas oseudoalcalioenes or Pseudomonas Huorescens. 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 orvzae 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 Huorescens. 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 30 * C, 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 aikyl alkoxy sulfate, preferably aikyl 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 aikyl 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
  • Aikyl alkoxy!ated sulfate surfactants are water soluble salts or acids typically of the formula R0(A) m S03M wherein R is an unsubstituted C10-C 4 aikyl or hydroxyalkyl group having a C10-C24 aikyl component, preferably a C12-C20 aikyl or hydroxyalkyl, more preferably C12-C18 aikyl 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 C10-C 4 aikyl or hydroxyalkyl group having a C10-C24 a
  • Aikyl ethoxylated sulfates as well as aikyl 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 alkanolamines, e.g. monoethanolamine, diethanolamine, and triethanolamine, and mixtures thereof.
  • Exemplary surfactants are C12-C18 aikyl polyethoxylate (1.0) sulfate, C12-C18 aikyl polyethoxylate (2.25) sulfate, C12-C18 aikyl polyethoxylate (3.0) sulfate, and C12-C18 aikyl polyethoxylate (4.0) sulfate wherein M is conveniently selected from sodium and potassium.
  • Polyhydroxy Fatty Acid Amide 5 Polyhydroxy fatty acid amide surfactant comprises compounds of the structural formula: 0 Rl
  • R2 - C - N - Z 0 wherein: R 1 is H, C1-C4 hydrocarbyl, 2-hydroxy ethyl, 2-hydroxy propyl, or a mixture thereof, preferably C1-C4 aikyl, more preferably Ci or C2 aikyl, most preferably Ci aikyl (i.e., methyl); and R 2 is a C5-C31 hydrocarbyl, preferably straight chain C7-C19 aikyl or alkenyl, more preferably straight chain C9-C17
  • 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
  • Z 20 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 -(CH0H) n -CH 2 0H, -CH(CH 2 0H)-(CH0H) n . 1 -CH 2 0H,
  • n is an integer from 3- to 5, inclusive
  • R' is H or a cyclic or aliphatic onosaccharide.
  • glycityls wherein n is 4, particularly -CH2-(CHOH)4-CH2 ⁇ H.
  • the polyhydroxy fatty acid amide preferred herein is glucose
  • 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
  • soap C9-C20 linear aikylbenzenesulphonates, C8-C22 primary or secondary al anesulphonates, C8-C24 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.
  • aikyl glycerol sulfonates 1,082,179, aikyl glycerol sulfonates, fatty acyl glycerol sulfonates, fatty oleyl glycerol sulfates, aikyl phenol ethylene oxide ether sulfates, paraffin sulfonates, aikyl 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 C12-C18 monoesters) diesters of sulfosuccinate (especially saturated and unsaturated C6-C14 diesters), N-acyT sarcosinates, sulfates of aikylpolysaccharides such as the sulfates of aikylpolyglucoside (the nonionic nonsulfated compounds being described below), branched primary aikyl sulfates, aikyl polyethoxy carboxylates such as those of the formula RO(CH CH2 ⁇ )
  • 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 Column 29, line 23 (herein incorporated by reference).
  • Aikyl sulfate surfactants are a type of anionic surfactant preferred for use herein.
  • dissolution of aikyl sulfates can be obtained, as well as improved formulability in liquid detergent formulations are water soluble salts or acids of the formula ROSO3M wherein R preferably is a C10-C24 hydrocarbyl, preferably an aikyl or hydroxyalkyl having a C10-C 0 aikyl component, more preferably a C12-C18 aikyl 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
  • R preferably is a C10-C24 hydrocarbyl, preferably an aikyl or hydroxyalkyl having a C10-C 0 aiky
  • aikyl chains of C12-I6 are preferred for lower wash temperatures (e.g., below about 50'C) and Cj6-18 aikyl chains are preferred for higher wash temperatures (e.g., above about 50 * C).
  • Preferred for use herein are C12-C 0 aikyl sulfate ("AS"), and/or C9-C20 linear aikylbenzene sulfonate (preferably sodium salts).
  • AS C12-C 0 aikyl sulfate
  • C9-C20 linear aikylbenzene sulfonate preferably sodium salts.
  • Preferred are from about 2 to about 10 wt.% of the Cj2-20 AS and from about 10 to about 15 wt.% of the Cg_2o LAS.
  • nonionic surfactant is the condensation product of C10-C20 alcohol and between about 2 and about 20 moles of ethylene oxide per mole of alcohol ("E2-20 ethoxylated C ⁇ o-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 aikyl phenols are preferred.
  • These compounds include the condensation products of aikyl phenols having an aikyl 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 aikyl phenol alkoxylates, (e.g., aikyl phenol ethoxylates).
  • the condensation products of aliphatic alcohols with from about 1 to about 25 moles of ethylene oxide can either be straight or branched, primary or secondary, and generally contains from about 8 to about 22 carbon atoms.
  • This category of nonionic surfactant is referred to generally as "aikyl ethoxylates.”
  • Preferred are C12-16, 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 10 o nonionic surfactants which include water-soluble amine oxides containing one aikyl moiety of from about 10 to about 18 carbon atoms and 2 moieties selected from the group consisting of aikyl groups and hydroxyalkyl groups containing from about 1 to about 3 carbon atoms; water-soluble phosphine oxides containing one aikyl 15 moiety of from about 10 to about 18 carbon atoms and 2 moieties selected from the group consisting of aikyl groups and hydroxyalkyl groups containing from about 1 to about 3 carbon atoms; and water-soluble sulfoxides containing one aikyl moiety of from about 10 to about 18 carbon atoms and a moiety selected from
  • R 6 is an aikyl group containing from about 7 to about 21 (preferably from about 9 to about 17) carbon atoms and each R? is selected from the group consisting of hydrogen, C1-C4 aikyl, C1-C hydroxyalkyl , and -(C2H4 ⁇ ) x H where x varies from about 1 to about 3.
  • Deterqencv Builder From 1 to about 80, preferably about 20 to about 70, weight %
  • 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 alkanolammonium salts of 0 polyphosphates (exemplified by the tripolyphosphates, pyrophosphates, and glassy polymeric meta-phosphates), phosphonates, phytic acid, silicates, carbonates (including bicarbonates and sesquicarbonates), sulphates, and aluminosili- cates.
  • borate-forming materials that can produce borate under detergent storage or wash conditions can also be used.
  • non-borate builders are used in the compositions of the invention intended for use at wash conditions less than about 50 * C, especially less than about 40"C.
  • silicate builders are the alkali metal silicates, particularly those having a Si ⁇ 2:Na2 ⁇ 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 ⁇ 5 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:
  • Preferred aluminosilicates are zeolite builders which have the formula:
  • aluminosilicate ion exchange materials are commercially available. These aluminosilicates can be crystalline or amorphous in structure and can be naturally-occurring aluminosil cates 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-l, 1-diphosphonate particularly the sodium and potassium salts, the water-soluble salts of methylene diphosphonic acid e.g.
  • 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 alkanolammonium 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.
  • a specific type of ether polycarboxylates useful as builders in the present invention also include those having the general formula:
  • TDS tartrate disuccinic acid
  • the compound is tartrate disuccinic acid (TMS) and its water-soluble salts.
  • TMS 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-J 4,120,874 and 4,102,903, all of which are incorporated herein by reference.
  • ether hydroxypolycarboxylates represented by the structure:
  • n H0-[C(R)(C00M)-C(R)(C00M)-0] n -H wherein 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, C1-4 aikyl or C1-4 substituted aikyl (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 ellitic acid, succinic acid, oxydisuccinic acid, polymaleic acid, benzene 1,3,5-tricarboxyl c 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.
  • Other 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-l,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 C5-C20 aikyl succinic acids and salts thereof.
  • a particularly preferred compound, of this type is dodecenylsuccinic acid.
  • Aikyl succinic acids typically are of the general formula R-CH(C00H)CH2(C00H) i.e., derivatives of succinic acid, wherein R is hydrocarbon, e.g., C10-C20 aikyl or alkenyl, preferably Cj2" 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 alkanolammonium salts.
  • succinate builders include: laurylsuc- cinate, myristylsuccinate, palmitylsuccinate, 2-dodecenylsuccinate (preferred), 2-pentadecenylsuccinate, and the like. Laurylsuc- cinates 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, carboxy ethyloxysuccinate, cis-cyclo- hexane-hexacarboxylate, cis-cyclopentane-tetracarboxylate, water- soluble 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 car- boxylates 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.
  • monocarboxylic acids, and soluble salts thereof, having long chain hydrocarbyls can be utilized. These would include materials generally referred to as "soaps.” Chain lengths of C10-C20 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.
  • Second Enzyme Optional, and preferred, 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 qrisea 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).
  • amylase suitable for use in a detergent composition can be used in these compositions.
  • a ylases 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, Rapidase , 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 bro o-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 Maxape 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. E. Other Ingredients
  • 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 dia ine.
  • 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.
  • This invention further provides a method for cleaning fabrics in the wash by contacting the fabrics with effective amounts of a granular detergent composition comprising:
  • 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 aikyl 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/lOOg (1500 LU/1; 1.44 wt.%).
  • 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/lOOg; 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 ai kyl al koxy sul fate or pol yhydroxy fatty acid amide)
  • Detergent B (with pol yhydroxy fatty acid amide)
  • the detergent formulas are as follows:
  • Lipase (Lipolase ® ) is used in each case in an equal amount. Wash temperature is 40'C.
  • test shows the presence of O.l ⁇ g oil and 48% triglyceride remaining in the extracted material. After washing with formulation (b) the test shows the presence of O.llg 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
  • allows hydrolytic products of lipase to be removed more efficiently than the weaker surfactant formulation e.g. Detergent a, which is outside the present invention.
  • Lipolase ® from Humicola lanuginosa can be substituted herein.

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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)
EP93911031A 1992-05-08 1993-05-04 Granular detergent compositions with lipase Withdrawn EP0639222A1 (en)

Applications Claiming Priority (3)

Application Number Priority Date Filing Date Title
US88039292A 1992-05-08 1992-05-08
US880392 1992-05-08
PCT/US1993/004192 WO1993023516A1 (en) 1992-05-08 1993-05-04 Granular detergent compositions with lipase

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EP0639222A1 true EP0639222A1 (en) 1995-02-22

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EP (1) EP0639222A1 (enrdf_load_stackoverflow)
JP (1) JPH07506618A (enrdf_load_stackoverflow)
CN (1) CN1080952A (enrdf_load_stackoverflow)
AU (1) AU4231493A (enrdf_load_stackoverflow)
CA (1) CA2134978A1 (enrdf_load_stackoverflow)
CZ (1) CZ270494A3 (enrdf_load_stackoverflow)
HU (1) HUT70073A (enrdf_load_stackoverflow)
MA (1) MA22891A1 (enrdf_load_stackoverflow)
RU (1) RU94046042A (enrdf_load_stackoverflow)
SK (1) SK133194A3 (enrdf_load_stackoverflow)
TW (1) TW243469B (enrdf_load_stackoverflow)
WO (1) WO1993023516A1 (enrdf_load_stackoverflow)

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JPH08511826A (ja) * 1993-06-25 1996-12-10 ザ、プロクター、エンド、ギャンブル、カンパニー リパーゼとノナノイルオキシベンゼンスルホン酸ナトリウムとを含有する粒状洗濯洗剤組成物
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
DE4411349A1 (de) * 1994-03-31 1995-10-05 Henkel Kgaa Lipasehaltiges Textilwaschmittel
USH1513H (en) * 1994-06-01 1996-01-02 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
MX9703716A (es) * 1994-11-18 1997-08-30 Procter & Gamble Composiciones detergentes que contienen enzimas lipoliticas especificas.
ATE191497T1 (de) * 1994-11-18 2000-04-15 Procter & Gamble Lipase- und proteasehaltige waschmittelzusammensetzungen
BE1009312A3 (fr) * 1995-05-05 1997-02-04 Solvay Compositions detergentes.
EP0912681A1 (en) * 1996-05-15 1999-05-06 The Procter & Gamble Company Detergent compositions comprising specific lipolytic enzyme and lime soap dispersant
WO1997043375A1 (en) * 1996-05-15 1997-11-20 The Procter & Gamble Company Detergent compositions comprising specific lipolytic enzyme and a specific surfactant system
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
BR112021004507A2 (pt) * 2018-09-17 2021-06-08 Unilever Ip Holdings B.V. composição detergente, método de tratamento de um substrato com uma composição detergente e uso de uma enzima lipase bacteriana

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WO1993023516A1 (en) 1993-11-25
SK133194A3 (en) 1995-04-12
AU4231493A (en) 1993-12-13
MA22891A1 (fr) 1993-12-31
TW243469B (enrdf_load_stackoverflow) 1995-03-21
CZ270494A3 (en) 1995-03-15
JPH07506618A (ja) 1995-07-20
CN1080952A (zh) 1994-01-19
HUT70073A (en) 1995-09-28
RU94046042A (ru) 1996-09-27
CA2134978A1 (en) 1993-11-25
HU9403201D0 (en) 1995-02-28

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