EP0639222A1

EP0639222A1 - Granular detergent compositions with lipase

Info

Publication number: EP0639222A1
Application number: EP93911031A
Authority: EP
Inventors: Ann Margaret Wolff; Michael Stanford Showell
Original assignee: Procter and Gamble Co
Current assignee: Procter and Gamble Co
Priority date: 1992-05-08
Filing date: 1993-05-04
Publication date: 1995-02-22
Also published as: CZ270494A3; RU94046042A; JPH07506618A; WO1993023516A1; CN1080952A; AU4231493A; MA22891A1; SK133194A3; HUT70073A; TW243469B; CA2134978A1; HU9403201D0

Abstract

This relates to a granular detergent composition containing (a) from about 0,00025 to about 0.015 grams of active enzyme per 100 grams of composition, of certain lipases, (b) from about 0.5 to about 10 wt.% of alkyl alkoxy sulfate or polyhydroxy fatty acid amide, and (c) from about 2 to about 30 wt.% of additional anionic or nonionic surfactant, wherein (a)/(b) is between about 0.09 and about 0.28, for improved performance after the first wash cycle. A method for cleaning fabrics is also provided.

Description

GRANULAR DETERGENT COMPOSITIONS WITH LIPASE

FIELD OF THE INVENTION

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 Pseudoπtonas Dseudoalcaliqenes or Pseudomonas fluorescens. A method of cleaning fabrics using such a composition is also included.

BACKGROUND OF THE INVENTION The inclusion of 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, Cornelissen et al issued September 6, 1988, 4,861,509, Cornelissen 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.

Unfortunately, although cleaning benefits from using granular laundry detergent compositions on stained or soiled laundry are clear after multiple laundry cycles, it has heretofore been difficult to see those benefits (particularly on grease and oil stains such as bacon grease and spaghetti sauce) after only one cycle in the washing machine and clothes drier. In fact, washing in granular detergents containing lipase at the conventional higher levels (in commercial products) often brings about a first cycle cleaning loss although there is a multi-cycle cleaning benefit. It has been found that, for the lipases shown below, keeping the amount of lipase low (i.e. at the level shown below), and including certain anionic or nonionic surfactants in a specified weight ratio in the granular detergent composition, will result in improvement in the removal of triglyceride-based stains or soils, such as greasy food stains and body soils, from fabrics even after the first laundry cycle. SUMMARY OF THE INVENTION The present invention relates to a granular detergent composition comprising, by weight:

(a) 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 pseudoalcalioenes or Pseudomonas fluorescens.:

(b) from about 0.5 to about 10% of aikyl alkoxy sulfate and/or polyhydroxy fatty acid amide; and

(c) from about 2 to about 30% of additional anionic or nonionic surfactant; wherein (a)/(b) is between about 0.09 and about 0.28.

DETAILED DESCRIPTION OF THE INVENTION

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%). Preferably, 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.

A. Lipase 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 (LU) 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

NaCl in phosphate buffer.

B. Surfactant 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)_mS03M 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. 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. 2. Polyhydroxy Fatty Acid Amide 5 Polyhydroxy fatty acid amide surfactant comprises compounds of the structural formula: 0 Rl

(I) R2 - C - N - Z 0 wherein: R¹ 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 R² is a C5-C31 hydrocarbyl, preferably straight chain C7-C19 aikyl or alkenyl, more preferably straight chain C9-C17

₁₅ aikyl or alkenyl, most preferably straight chain C11-C15 aikyl 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

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 -CH₂-(CH0H)_n-CH₂0H, -CH(CH₂0H)-(CH0H)_n.₁-CH₂0H,

_:5 -CH₂-(CHOH)2(CHOR')(CHOH)-CH2θH, and alkoxylated derivatives thereof, where n is an integer from 3- to 5, inclusive, and R' is H or a cyclic or aliphatic onosaccharide. Most preferred are glycityls wherein n is 4, particularly -CH2-(CHOH)4-CH2θH.

The polyhydroxy fatty acid amide preferred herein is glucose

30 amide, preferably C12-I8 N-acetyl glucamide. 3. Additional Anionic Surfactant

Anionic surfactants useful for detersive purposes are included in the compositions hereof. These can include salts (including, for example, sodium, potassium, ammonium, and

3 substituted ammonium salts such as mono-, di- and triethanolamine salts) of 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. 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 CH2θ)|ζCH2COO-M+ wherein R is a C8-C 2 aikyl, 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 Column 29, line 23 (herein incorporated by reference).

Aikyl sulfate surfactants are a type of anionic surfactant preferred for use herein. In addition to providing excellent overall cleaning ability when used in combination with polyhydroxy fatty acid amides (see below), including good grease/oil cleaning over a wide range of temperatures, wash concentrations, and wash times, 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 ammonium and quaternary ammonium cations, e.g., tetramethyl-ammonium and dimethyl piperdinium, and cations derived from alkanolamines such as ethanolamine, diethanola ine, triethanolamine, and mixtures thereof, and the like. Typically, 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). 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. Preferably the 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 Cιo-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.

1. The polyethylene, polypropylene, and polybutylene oxide condensates of aikyl phenols. In general, the polyethylene oxide condensates 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).

2. The condensation products of aliphatic alcohols with from about 1 to about 25 moles of ethylene oxide. The aikyl 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 "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.

3. The condensation products of ethylene oxide with a hydrophobic base formed by the condensation of propylene oxide

5 with propylene glycol.

4. The condensation products of ethylene oxide with the product resulting from the reaction of propylene oxide and ethylenediamine.

5. 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

20 the group consisting of aikyl and hydroxyalkyl moieties of from about 1 to about 3 carbon atoms.

6. Aikylpolysaccharides disclosed in U.S. Patent 4,565,647, Llenado, issued January 21, 1986, having a hydrophobic group containing from about 6 to about 30 carbon atoms, preferably from

-- about 10 to about 16 carbon atoms and a polysaccharide, e.g., a polyglycoside, hydrophilic group containing from about 1.3 to about 10, preferably from about 1.3 to about 3, most preferably from about 1.3 to about 2.7 saccharide units.

7. Fatty acid amide surfactants having the formula:

30

- wherein R⁶ 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 -(C2H4θ)_xH where x varies from about 1 to about 3.

C. Deterqencv Builder From 1 to about 80, preferably about 20 to about 70, weight %

₅ 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 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 builders, as well as builders containing

₁₅ borate-forming materials that can produce borate under detergent storage or wash conditions (hereinafter, collectively "borate builders"), can also be used. Preferably, 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.

20 Examples of silicate builders are the alkali metal silicates, particularly those having a Siθ2:Na2θ 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. However, other silicates τ₅ 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.

Examples of carbonate builders are the alkaline earth and

30 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.

₃₅ 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:

M_z(zAlθ2-ySiθ2) wherein M is sodium, potassium, ammonium or substituted ammonium, z is from about 0.5 to about 2; .and y is 1; this material having a magnesium ion exchange capacity of at least about 50 milligram equivalents of CaC03 hardness per gram of anhydrous aluminosilicate. Preferred aluminosilicates are zeolite builders which have the formula:

Na_z[(A10₂)z (Si0₂)_y]-xH₂0 wherein 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. Useful 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.

Specific examples of 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. Examples of 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. the trisodium and tripotassium salts and the water-soluble salts of substituted methylene diphosphonic acids, such as the trisodium and tripotassium ethylidene, isopyropylidene benzylmethylidene and halo methylidene 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. As used herein, "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. When utilized in salt form, alkali metals, such as sodium, potassium, and lithium, or alkanolammonium salts are preferred.

Included among the polycarboxylate builders are 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:

CH(A)(C00X)-CH(C00X)-0-CH(C00X)-CH(C00X)(B) wherein A is H or OH; B is H or -0-CH(C00X)-CH2(C00X) ; and X is H or a salt-forming cation. For example, if in the above general formula 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 -0-CH(C00X)-CH2(C00X), then the compound is tartrate disuccinic acid (TDS) and its water-soluble salts. 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.

These builders are disclosed in U.S. Patent 4,663,071, issued to Bush et al., on May 5, 1987.

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.

Other useful detergency builders include the ether hydroxypolycarboxylates represented by the structure:

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.

Also included are 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"^c16 ^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.

Specific examples of 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.

Examples of 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.

Other suitable polycarboxylates are the 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.

Polycarboxylate builders are also disclosed in U.S. Patent

3,308,067, Diehl, issued March 7, 1967, incorporated herein by reference. 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.

Other organic builders known in the art can also be used. For example, 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. Preferably 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.

D. Second Enzyme Optional, and preferred, ingredients include second enzymes, which include protease (most preferred), amylase, peroxidase, cellulase, and mixtures thereof. By "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.

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,

Barbesgaard et al., issued March 6, 1984, incorporated herein by reference, which discloses fungal cellulase produced from Humicola insolens. Suitable cellulases are also disclosed in GB-A-2.075.028, GB-A-2.095.275 and DE-0S-2.247.832.

Examples of such cellulases are 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).

Any amylase suitable for use in a detergent composition can be used in these compositions. A ylases include, for example, α-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 Termamyl™.

From about 0.0001% to 1.0, preferably 0.0005 to 0.5, weight % on an active enzyme basis of amylase can be used. 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.

From about 0.0001 to about 1.0, preferably about 0.0005 to about 0.5, most preferably about 0.002 to about 0.1, weight % on an active basis of detergent-compatible protease is preferred for use herein. Mixtures of protease enzymes are also included. The protease 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, then, 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

Other 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:

(a) from about 0.0000025 to about 0.006 grams of active enzyme per gram of composition, of lipase produced by a lipase producing strain of Humicola sp. or Ther omvces sp. or Pseudomonas pseudoalcaliqenes or Pseudomonas fluorescens;

(b) from about 0.5 to about 10 wt.% of aikyl alkoxy sulfate or polyhydroxy fatty acid amide; and

(c) from about 2 to about 30 wt.% of additional anionic or nonionic surfactant; wherein (a)/(b) is between about 0.09 and about 0.28.

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 following examples illustrate the compositions of the present invention, but are not necessarily meant to limit or otherwise define the scope of the invention. All parts, percentages and ratios used herein are by weight unless otherwise specified.

EXAMPLE I The following wash tests were done to observe the effects on cleaning when a lower amount of lipase is used, and a more robust detergent is evaluated with and without lipase.

METHOD

Both polycotton and cotton fabrics were stained with greasy foods using either a bacon grease composite (4 drops) or a spaghetti sauce composite (brushed on). These stains were washed in duplicate in three washing machines for each product evaluated (see Detergents A and B below); thus, comparisons were based on six different stained swatches for each bacon grease or spaghetti stain. After a 12 minute wash cycle and a 35 minute dry cycle, the stains were "graded", or compared for overall stain removal by three graders (blind test), with results listed below.

CONCLUSION

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.%). 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. Surprisingly, 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.

RESULTS

Table A

Scale used: 0 = stain after detergent treatment; +1 to +4 shows degrees of improved removal over detergent alone; -1 to -4 shows degrees of decreased removal over detergent alone.

* = significant difference, at 95% Confidence Interval (LSD). Note: 500 LU/1 is 0.012g/100g or 0.48 wt.% and 1500 LU/1 is 0.036g/100g or 1.44 wt.% in the composition.

Table B

Stain bacon grease/polycotton bacon grease/cotton spaghetti/polycotton spaghetti/cotton

Scale used: same as in Table A

* = significant difference, at 95% Confidence Interval (LSD)

Detergent A (without ai kyl al koxy sul fate or pol yhydroxy fatty acid amide)

Component Weight %

Sodium 12.3 l inear ai kyl benzene sul fonate 18.41

Sodium C14-15 ai kyl sul fate 5.95

Sodium carbonate 21.33 Sodium al uminosil icate 26.30

Sil icate sol ids (2. Or) 2.29

Polyethylene glycol (MW 8000) 1.74 ^c12-13 Alcohol polyethoxyl ate (E6.5) 0.50

Brightener 0.30 Perfume 0.10

Water 10.06

Citric acid 3.50

Admi x : Sodium carbonate 8.39

Sodium perborate 0.35

Perfume 0.26

Savinase^® protease 0.52

Detergent B (with pol yhydroxy fatty acid amide)

Component Weight %

Sodium 12.3 l inear ai kyl benzene sul fonate 22.39

effectiveness of lipolytic enzyme in a comparative detergent formulation, are estimated as follows:

(a) Triolein-soiled polyester materials are washed in a miniwasher under uniform conditions using two detergent formulations as given below.

(b) Gravimetric analysis of the residue remaining on the fabric is carried out to show an index quantity of oil remaining per standard test cloth. Additionally, gas chromatographic readings of the thereafter extracted residues were carried out to show the relative efficiency of the lipolytic enzyme under each condition.

The detergent formulas are as follows:

Sodium linear aikylbenzene sulfonate/ sodium aikyl sulfate (70/30) Cχ2-13 Alcohol polyethoxylate (6.5) Aikylethoxy (El) sulfate Glucose amide Sodium carbonate 23 21 Citric acid 3 3 Savinase^® protease 1 1

Lipase (Lipolase^®) is used in each case in an equal amount. Wash temperature is 40'C.

After washing with formulation (a) the test shows the presence of O.lβg 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.

It is apparent that 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%). Conclusion: 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).

EXAMPLE III

Sodium i4_i5 aikyl sulfate 6.36 i6-18 N-acetyl glucamide 3.82

Alkylethoxy (E2.25) sulfate 1.27

Ci2-13 Alcohol polyethoxylate (6.5) 3.44

Sodium aluminosilicate 14.00

Water and miscellaneous Balance

* from Pseudomonas oseudoalcaligenes (100,000 LU/g) Lipolase^® from Humicola lanuginosa can be substituted herein.

Claims

WHAT IS CLAIMED IS:

1. A granular detergent composition comprising:

(a) from 0.00025 to 0.015 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;

(b) from 0.5 to 10 weight % of alkyl alkoxy sulfate or polyhydroxy fatty acid amide; and

(c) from 2 to 30 weight % of additional anionic or nonionic surfactant;

wherein (a)/(b) is between 0.09 and 0.28.

2. A granular detergent composition according to Claim 1 wherein the anionic surfactant is sodium C₁₂-C₂₀ alkyl sulfate and sodium C₉-C₂₀ linear alkylbenzene sulfonate, and the nonionic surfactant is the condensation product of C₁₀-C₂₀ alcohol and between 2 and 20 moles of ethylene oxide per mole of alcohol; and the composition further comprising from 1 to 80 weight % of detergency builder.

3. A granular detergent composition according to Claim 1 or 2 comprising from 0.0025 to 0.010 grams of active enzyme per 100 grams of composition, of lipase produced by a lipase producing strain of Humicola lanuginosa or Pseudomonas pseudoalcaligenes.

4. A granular detergent composition according to any of the preceding claims comprising from 0.5 to 5 weight % of alkyl sulfate which has been ethoxylated with from 0.5 to 10 moles of ethylene oxide per mole of alkyl sulfate.

5. A granular detergent composition according to any of the preceding claims wherein the amount of lipase divided by the amount of alkyl al koxy sulfate or polyhydroxy fatty acid amide is between 0.10 and 0.20.

6. A granular detergent composition according to any of the preceding claims further comprising from 20 to 70 weight % of detergency builder selected from the group consisting of the salts of carbonate, silicate, sulfate, phosphate, aluminosilicate, and citric acid and mixtures thereof.

7. A granular detergent composition according to any of the preceding claims further comprising from 0.0001 to 1.0 weight % on an active basis of second enzyme.

8. A granular detergent composition according to any of the preceding claims comprising from 0.0005 to 0.5 weight % on an active basis of detergent-compatible protease.

9. A granular detergent composition according to any of the preceding claims comprising from 0.0001 to 0.6 weight %, on a 100,000 LU/g active basis, of lipase produced by cloning the gene from Humicola lanuginosa and expressing the gene in Aspergillus oryzae.

10. A method for cleaning fabrics in the wash by contacting the fabrics with effective amounts of a granular detergent composition comprising:

(a) from 0.00025 to 0.015, preferably 0.0025 to 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:

(b) from 0.5 to 10 weight % of alkyl alkoxy sulfate and/or polyhydroxy fatty acid amide; and

(c) from 2 to 30 weight % of additional anionic or nonionic surfactant; wherein (a)/(b) is between 0.09 and 0.28.