WO1997019155A1

WO1997019155A1 - Laundry detergent compositions containing lipolytic enzyme and selected quaternary ammonium compounds

Info

Publication number: WO1997019155A1
Application number: PCT/US1996/017430
Authority: WO
Inventors: Ayako Asahara; Mitsuyo Okamoto; Borra Sudarsana
Original assignee: The Procter & Gamble Company
Priority date: 1995-11-17
Filing date: 1996-10-31
Publication date: 1997-05-29
Also published as: AU7528196A; CN1207759A; MA24008A1; JPH11500180A; BR9611602A; TR199800872T2; MX9803935A; EP0876452A1; IL124520A0; CZ136098A3; EG21152A; AR004594A1

Abstract

The present invention relates to laundry detergent compositions containing a lipolytic enzyme (lipase) and selected quaternary ammonium surfactants. The compositions provide enhanced cleaning of grease/oil soils and stains.

Description

LAUNDRY DETERGENT COMPOSITIONS CONTAINING LIPOLYTIC ENZYME AND SELECTED QUATERNARY AMMONIUM COMPOUNDS

FIELD OF THE INVENTION

The present invention relates to laundry detergent compositions containing a lipolytic enzyme (lipase) and selected quaternary ammomium surfactants. The compositions provide enhanced cleaning of grease/oil soils and stains.

BACKGROUND OF THE INVENTION

The inclusion of lipase in detergent compositions for improved cleaning performance is known, e.g. enhancement of removal of triglycerides containing soils and stains from fabrics. Examples are US Patent 4,769,173; US Patent 5,069,809; PCT application WO94/03578. In USP 4,769,173 is disclosed a certain class of lipases consisting of fungal

Upases ex Humicola lanuginosa together with strong bleaching agents in detergent compositions. An example of a fungal lipase in this patent is the lipase ex Humicola lanuginosa, available from Amano under the tradename Amano-CE. In USP 5,069,809 is disclosed the combination of strong bleaching agents with a lipase enzyme produced by cloning the gene encoding the lipase produced by Humicola lanuginosa and expressing the gene in Aspergillus oryzae as host for use in detergent compositions. In WO 94/03578 is disclosed an enzymatic detergent composition containing 10 to 20 000 LU (Lipolytic units) per gram of detergent composition of a lipase showing a substantial lipolytic activity during the main cycle of a wash process. This lipase is selected in particular on its inactivation behaviour with Diisopropyl Fluoro Phosphate (DFP).

Of the lipase enzymes, only the lipase derived from Humicola lanuginosa and produced in Aspergillus oryzae as host has so far found wide-spread application as additive for fabric washing products. It is available under the tradename Lipolase,, from Novo Nordisk.

In order to optimize the stain removal performance of Lipolase, Novo Nordisk have made a number of variants. WO 92/05249 describes the D96L variant of the native Humicola lanuginosa lipase improves the lard stain removal efficiency by a factor 4.4 over the wild-type lipase (enzymes compared in an amount ranging from 0.075 to 2.5 mg protein per liter).

The ability of lipase to clean soils and stains from fabrics present in the typical load of laundry is of high importance in the evaluation of detergent performance. Unfortunately, the relative ability of lipase to meet various performance criteria is among other depending on the presence of cosurfactants.

There is thus a standing desire for performance and flexibility reasons to make available a surfactant system capable of providing optimum detergency performance of the lipase. The above objective has been met by a surfactant system comprising a cosurfactant selected from the group of selected quaternary ammomium compounds.

It has been suφrisingly found that the inclusion of specially selected quaternary ammonium compounds into liquid detergent compositions containing a lipolytic enzyme (lipase) substantially enhances their ability to rapidly lower the interfacial tension of aqueous washing liquors containing greasy and oily soils. This substantial reduction of interfacial tension of greasy and oily soils improves their removal from soiled surfaces and inhibits the redeposition ofthe soils onto substrates.

LIPOLYTIC ENZYME An essential ingredient in the present laundry detergent compositions is a performance-enhancing amount, preferably from about 0.0001 to 1.0%, more preferably from about 0.05 to about 0.5%, on an active basis, of a detergent- compatible lipase (lipolytic enzyme). By "detergent-compatible" is meant compatibility with the other ingredients of the composition, particularly detergent surfactants and any detergency builders. Liquid detergent compositions, particularly heavy duty liquids, are preferred herein.

Any lipase suitable for use in a laundry detergent composition can be used herein. Suitable lipases for use herein include those of bacterial and fiingal origin. Lipase from chemically or genetically modified mutants are included herein. Suitable bacterial lipases include those produced by Pseudomonas. such as

Pseudomonas stutzeri ATCC 19.154, as disclosed in British Patent 1,372,034, incoφorated herein by reference. Suitable lipases include those which show a positive immunological cross-reaction with the antibody ofthe lipase produced by the microorganism Pseudomonas fluorescens IAM 1057. This lipase and a method for its purification have been described in Japanese Patent Application 53-20487, laid open on February 24, 1978. which is incoφorated herein by reference. This lipase is available under the trade name Lipase P "Amano," hereinafter referred to as "Amano- P." Such lipases should show a positive immunological cross reaction with Amano-P antibody, using the standard and well-known im unodiffusion procedure according to Ouchterlony (Acta. Med. Scan., 133, pages 76-79 (1950)). These lipases, and a method for their immunological cross-reaction with Amano-P. are also described in U.S. Patent 4,707,291 , Thom et al, issued November 17, 1987. incoφorated herein by reference. Typical examples thereof are the Amano-P lipase, the lipase ex Pseudomonas fragi FERM P 1339 (available under the trade name Amano-B), lipase ex Pseudomonas nitroreducens var. lipolyticum FERM P 1338 (available under the trade name Amano-CES), lipases ex Chromobacter viscosum. e.g., Chromobacter viscosum var. lipolyticum NRRLB 3673. and further Chromobacter viscosum lipases, and lipases ex Pseudomonas gladioli. Other lipases of interest are Amano AKG and Bacillis Sp lipase.

Suitable fungal lipases include those producible by Humicola lanuginosa and Thermomvces lanuginosus. Most preferred is lipases obtained by cloning the gene from Humicola lanuginosa and expressing the gene in Aspergillus oryzae as described in European Patent Application 0 258 068, incoφorated herein by reference, commercially available under the trade name Lipolase'.

Highly preferred lipases are the D96L lipolytic enzyme variant of the native lipase derived from Humicola lanuginosa as described in US Serial No. 08/341,826. Preferably the Humicola lanuginosa strain DSM 4106 is used. This enzyme is incoφorated into the composition in accordance with the invention at a level of from 50LU to 8500LU per liter wash solution. Preferably the variant D96L is present at a level of from 100LU to 7500LU per liter of wash solution. More preferably at a level of from 150 LU to 5000 LU per liter of wash solution. By D96L lipolytic enzyme variant is meant the lipase variant as described in patent application WO 92/05249 viz. wherein the native lipase ex Humicola lanuginosa aspartic acid (D) residue at position 96 is changed to Leucine (L). According to the nomenclature said substitution of aspartic acid to Leucine in position 96 is shown as : D96L. It has been found that D96L lipolytic enzyme variant is particularly preferred because ofthe good odor characteristics associated with the combined use of amines.

From about 2 to about 20,000, preferably about 10 to about 6,000, most preferably from about 200 to about 2000, lipase units per gram (LU/g) of lipase can be used in these compositions. A lipase unit is that amount of lipase which produces 1 μmol 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. THE QUATERNARY AMMONIUM COMPOUNDS

The compositions herein also contain from about 1 % to about 10%. preferably from about 2% to about 7%, by weight of a quaternary ammonium surfactant ofthe formula:

wherein R\ and Ro are individually selected from the group consisting of C_j- C4 alkyl, C1-C4 hydroxy alkyl, benzyl, and -(C2H4θ)_xH where x has a value from about 2 to about 5; X is an anion; and (1) R3 and R4 are each a C6-C14 alkyl or (2) R3 is a Cg-Cj alkyl. and R4 is selected from the group consisting of C1 -C 10 alkyl, C \ -C \ Q hydroxyalkyl, benzyl, and -(C2H4θ)_xH where x has a value from 2 to 5.

Preferred quaternary ammonium surfactants are the chloride, bromide, and methylsulfate salts. Examples of preferred mono-long chain alkyl quaternary ammonium surfactants are those wherein R] , R2, and R4 are each methyl and R3 is a Cg-Cjg alkyl; or wherein R3 is Cg.i alkyl and Rj , R2, and R4 are selected from methyl and hydroxyalkyl moieties. Lauryl trimethyl ammonium chloride, myristyl trimethyl ammonium chloride, palmityl trimethyl ammonium chloride, coconut trimethylammonium chloride, coconut trimethylammonium methylsulfate, coconut dimethyl-monohydroxy- ethylamrnonium chloride, coconut dimethyl-monohydroxyethylammonium methylsulfate, steryl dimethyl-monohydroxy-ethylammonium chloride, steryl dimethyl-monohydroxyethylammonium methylsulfate, di- C12-C14 alkyl dimethyl ammonium chloride, and mixtures thereof are particularly preferred. ADOGEN 412', a lauryl trimethyl ammonium chloride commercially available from Witco, is also preferred. Even more highly preferred are the lauryl trimethyl ammonium chloride and myristyl trimethyl ammonium chloride.

Inventions herein comprise the detergent composition wherein the weight ratio of anionic surfactant component to quaternary ammonium surfactant is from about 1.5:1 to about 5: 1 , preferably from about 1.5: 1 to about 4.5:1, more preferably from about 2: 1 to about 4: 1 , even more preferably from about 2:1 to about 3.5:1.

FABRIC LAUNDERING AND PRETREATMENT PROCESS The present invention also provides a process for laundering fabrics soiled with greasy/oily stains or soil. Such a process employs contacting these fabrics with an aqueous washing solution formed from an effective amount of the detergent compositions hereinbefore described. Contacting of fabrics with washing solution will generally occur under conditions of agitation.

Agitation is preferably provided in a washing machine for good cleaning. Washing is preferably followed by drying the wet fabric in a conventional clothes dryer. An effective amount of the liquid or granular detergent composition in the aqueous wash solution in the washing machine is preferably from about 500 to about 7000 ppm. more preferably from about 1000 to 3000 ppm

Detergent ingredients

In another embodiment of the present invention, the liquid detergent composition may comprise one or more of a surfactant selected from a wide range of surfactants.

A typical listing of anionic, nonionic, ampholytic and zwitterionic classes, and species of these surfactants, is given in US Patent 3,664,961 issued to Norris on May 23, 1972.

Preferred anionic surfactants include the alkyl sulfate surfactants hereof are water soluble salts or acids of the formula ROSO3M wherein R preferably is a C 1 _Q- C24 hydrocarbyl, preferably an alkyl or hydroxyalkyl having a Ci g-Cj alkyl component, more preferably a Ci 2-C1 5 alkyl or hydroxyalkyl, and M is H or a cation, e.g., an alkali metal cation (e.g. sodium, potassium, lithium), or ammonium or substituted ammonium (e.g. methyl-, dimethyl-, and trimethyl ammonium cations and quaternary ammonium cations such as tetramethyl-ammonium and dimethyl piperdinium cations and quaternary ammonium cations derived from alkylamines such as ethylamine, diethylamine, triethylamine, and mixtures thereof, and the like).

Highly preferred anionic surfactants include alkyl alkoxylated sulfate surfactants hereof are water soluble salts or acids ofthe formula RO(A)_mSO3M wherein R is an unsubstituted C j Q- 24 alkyl or hydroxyalkyl group having a C 1 Q- C24 alkyl component, preferably a C^-C j alkyl or hydroxyalkyl, more preferably C12-C15 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. Alk^l ethoxylated sulfates as well as alkyl propoxylated sulfates are contemplated herein. Specific examples of substituted ammonium cations include methyl-, dimethyl, trimethyl-ammonium cations and quaternary ammonium cations such as tetramethyl-ammonium and dimethyl piperdinium cations and those derived from alkylamines such as ethylamine, diethylamine, triethylamine, mixtures thereof, and the like. Exemplary surfactants are C12-C15 alkyl polyethoxylate (1.0) sulfate (Cι₂-C ι ₅E(1.0)M), C 12-C15 alkyl polyethoxylate (2.25) sulfate (C₁₂-

Cι ₅E(2.25)M), C12-C15 alkyl polyethoxylate (3.0) sulfate (Cι₂-Ci 5E(3.0)M). and ^c12"^c15 ^al polyethoxylate (4.0) sulfate (Ci2-Ci 5E(4.0)M), wherein M is conveniently selected from sodium and potassium.

Other suitable anionic surfactants to be used are alkyl ester sulfonate surfactants including linear esters of C -C2Q carboxylic acids (i.e.. fatty acids) which are sulfonated with gaseous SO3 according to "The Journal of the American Oil Chemists Society", 52 (1975), pp. 323-329. Suitable starting materials would include natural fatty substances as derived from tallow, palm oil, etc.

The preferred alkyl ester sulfonate surfactant, especially for laundry applications, comprise alkyl ester sulfonate surfactants ofthe structural formula :

O

II R³ - CH - C - OR⁴

SO3M

wherein R³ is a C -C20 hydrocarbyl, preferably an alkyl, or combination thereof, R⁴ is a C j -Cg hydrocarbyl, preferably an alkyl, or combination thereof, and M is a cation which forms a water soluble salt with the alkyl ester sulfonate. Suitable salt-forming cations include metals such as sodium, potassium, and lithium, and substituted or unsubstituted ammonium cations, such as monoethanolamine, diethanolamine, and triethanolamine. Preferably, R³ is \Q-C I(, alkyl, and R⁴ is methyl, ethyl or isopropyl. Especially preferred are the methyl ester sulfonates wherein R³ is Cj_Q-C i g alkyl. Other anionic surfactants useful for detersive purposes can also be included in the laundry detergent compositions of the present invention. These can include salts (including, for example, sodium, potassium, ammonium, and substituted ammonium salts such as mono-, di- and triethanolamine salts) of soap, C9-C20 linear alkylbenzenesulfonates, C -C22 primary of secondary alkanesulfonates, C -C24 olefinsulfonates, sulfonated polycarboxylic acids prepared by sulfonation ofthe pyrolyzed product of alkaline earth metal citrates, e.g., as described in British patent specification No. 1,082,179, C -C24 alkylpolyglycolethersulfates (containing up to 7

10 moles of ethylene oxide); alkyl glycerol sulfonates, fatty acyl glycerol sulfonates, fatty oleyl glycerol sulfates, alkyl phenol ethylene oxide ether sulfates. paraffin sulfonates, alkyl phosphates, isethionates such as the acyl isethionates, N-acyl taurates, alkyl succinamates and sulfosuccinates, monoesters of sulfosuccinates (especially saturated and unsaturated C \ 2-C i g monoesters) and diesters of sulfosuccinates (especially saturated and unsaturated -C 2 diesters), sulfates of alkylpolysaccharides such as the sulfates of alkylpolyglucoside (the nonionic nonsulfated compounds being described below), and alkyl polyethoxy carboxylates such as those of the formula RO(CH2CH2θ)] -CH2COO-M+ wherein R is a Cg-C22 alkyl, k is an integer from 0 to 1 Ω, and M is a soluble salt-forming cation. 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 described 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 incoφorated by reference).

When included therein, the laundry detergent compositions of the present invention typically comprise from about 1% to about 40%, preferably from about 5% to about 25% by weight of such anionic surfactants. One class of nonionic surfactants useful in the present invention are condensates of ethylene oxide with a hydrophobic moiety to provide a surfactant having an average hydrophilic-lipophilic balance (HLB) in the range from 8 to 17, preferably from 9.5 to 14, more preferably from 12 to 14. The hydrophobic (lipophilic) moiety may be aliphatic or aromatic in nature and the length of the polyoxyethylene group which is condensed with any particular hydrophobic group can be readily adjusted to yield a water-soluble compound having the desired degree of balance between hydrophilic and hydrophobic elements.

Especially preferred nonionic surfactants of this type are the C9-C 15 primary alcohol ethoxylates containing 3-12 moles of ethylene oxide per mole of alcohol, particularly the C12-C15 primary alcohols containing 5-8 moles of ethylene oxide per mole of alcohol.

Another class of nonionic surfactants comprises alkyl polyglucoside compounds of general formula

RO (C_nH_2nO)_tZ_x wherein Z is a moiety derived from glucose; R is a saturated hydrophobic alkyl group that contains from 12 to 18 carbon atoms; t is from 0 to 10 and n is 2 or 3; x is from 1.3 to 4, the compounds including less than 10% unreacted fatty alcohol and less than 50% short chain alkyl polyglucosides. Compounds of this type and their use in detergent are disclosed in EP-B 0 070 077, 0 075 996 and 0 094 1 18.

Also suitable as nonionic surfactants are poly hydroxy fatty acid amide surfactants ofthe formula

R2 - C - N - Z,

O Rl

wherein R¹ is H, or R* is Cj_4 hydrocarbyl, 2-hydroxy ethyl, 2-hydroxy propyl or a mixture thereof, R2 is C5.3 ] hydrocarbyl, and Z is a polyhydroxyhydrocarbyl having a linear hydrocarbyl chain with at least 3 hydroxyls directly connected to the chain, or an alkoxylated derivative thereof. Preferably, Rl is methyl, R2 is a straight C_{] j}.i 5 alkyl or alkenyl chain such as coconut alkyl or mixtures thereof, and Z is derived from a reducing sugar such as glucose, fructose, maltose, lactose, in a reductive amination reaction. Highly preferred nonionics are amine oxide surfactants. The compositions of the present invention may comprise amine oxide in accordance with the general formula I:

R (EO) (PO) (BO) N(O)(CH R') .qH O (I) x y z 2 2 2

In general, it can be seen that the structure (I) provides one long-chain moiety

R (EO) (PO) (BO) and two short chain moieties, CH R'. R' is preferably selected x y z ₁ 2 from hydrogen, methyl and -CH2OH. In general R¹ is a primary or branched hydrocarbyl moiety which can be saturated or unsaturated, preferably, R is a primary alkyl moiety. When x+y+z = 0, R is a hydrocarbyl moiety having chainlength of from about 8 to about 18. When x+y+z is different from 0, R may be somewhat longer, having a chainlength in the range C12-C24. The general formula also encompasses amine oxides wherein x+y+z = 0, Ri = Cg-Cjg, R' = H and q = 0-2, preferably 2. These amine oxides are illustrated by C 12- 14 alkyldimethyl amine oxide,hexadecyl dimethylamine oxide, octadecylamine oxide and their hydrates, especially the dihydrates as disclosed in U.S. Patents 5,075,501 and 5,071,594, incoφorated herein by reference. The invention also encompasses amine oxides wherein x+y+z is different from zero, specifically x+y+z is from about 1 to about 10, R is a primary alkyl group containing 8 to about 24 carbons, preferably from about 12 to about 16 carbon atoms; in these embodiments y + z is preferably 0 and x is preferably from about 1 to about 6, more preferably from about 2 to about 4; EO represents ethyleneoxy; PO represents propyleneoxy; and BO represents butyleneoxy. Such amine oxides can be prepared by conventional synthetic methods, e.g., by the reaction of alkylethoxysulfates with dimethylamine followed by oxidation of the ethoxylated amine with hydrogen peroxide. Highly preferred amine oxides herein are solids at ambient temperature, more preferably they have melting-points in the range 30_C to 90_C. Amine oxides suitable for use herein are made commercially by a number of suppliers, including Akzo Chemie, Ethyl Coφ., and Procter & Gamble. See McCutcheon's compilation and Kirk-Othmer review article for alternate amine oxide manufacturers. Preferred commercially available amine oxides are the solid, dihydrate ADMOX 16 and ADMOX 18, ADMOX 12 and especially ADMOX 14 from Ethyl Coφ.

Preferred embodiments include hexadecyldimethylamine oxide dihydrate, dodecyldimethylamine oxide dihydrate, octadecyldimethylamine oxide dihydrate, hexadecyltris (ethyleneoxy )dimethyl-amine oxide, and tetradecyidimethyl-amine oxide dihydrate.

Whereas in certain ofthe preferred embodiments R' = H, there is some latitude with respect to having R' slightly larger than H. Specifically, the invention further encompasses embodiments wherein R' = CH OH, such as hexadecylbis(2- hydroxyethyl)amine oxide, tallowbis(2-hydroxyethyl)amine oxide, stearylbis(2- hydroxyethyl)amine oxide and oleylbis(2- hydroxyethyl)amine oxide, dodecyldimethylamine oxide dihydrate.

When included therein, the laundry detergent compositions ofthe present invention typically comprise nonionic surfactants in the weight ratio of anionic surfactant to nonionic surfactant from 6:1 to 1 :3, preferably from 5:1 to 2: 1. The compositions according to the present invention may further comprise a builder system. Any conventional builder system is suitable for use herein including aluminosilicate materials, silicates, polycarboxylates and fatty acids, materials such as ethylenediamine tetraacetate, metal ion sequestrants such as aminopolyphosphonates, particularly ethylenediamine tetramethylene phosphonic acid and diethylene triamine pentamethylenephosphonic acid. Though less preferred for obvious environmental reasons, phosphate builders can also be used herein. Suitable polycarboxylates builders for use herein include citric acid, preferably in the form of a water-soluble salt, derivatives of succinic acid of the formula R-CH(COOH)CH2(COOH) wherein R is C 10-20 alkyl or alkenyl, preferably C12-16, or wherein R can be substituted with hydroxyl, sulfo sulfoxyl or sulfone substituents. Specific examples include lauryl succinate , myristyl succinate, palmityl succinate 2-dodecenyisuccinate, 2-tetradecenyl succinate. Succinate builders are preferably used in the form of their water-soluble salts, including sodium, potassium, ammonium and alkanolammonium salts.

Other suitable polycarboxylates are oxodisuccinates and mixtures of tartrate monosuccinic and tartrate disuccinic acid such as described in US 4.663,071.

Especially for the liquid execution herein, suitable fatty acid builders for use herein are saturated or unsaturated CIO- 18 fatty acids, as well as the corresponding soaps. Preferred saturated species have from 12 to 16 carbon atoms in the alkyl chain. The preferred unsaturated fatty acid is oleic acid. Other preferred builder system for liquid compositions is based on dodecenyl succinic acid and citric acid.

Detergency builder salts are normally included in amounts of from 3% to 50% by weight ofthe composition preferably from 5% to 30% and most usually from 5% to 25%o by weight.

Optional detergent ingredients

Preferred detergent compositions of the present invention may further comprise one or more enzymes which provide cleaning performance and/or fabric care benefits. Said enzymes include enzymes selected from cellulases. hemicellulases, peroxidases, proteases, gluco-amylases, amylases, lipases, cutinases, pectinases, xylanases, reductases, oxidases, phenoloxidases, lipoxygenases, ligninases, pullulanases, tannases, pentosanases, malanases, β-glucanases, arabinosidases or mixtures thereof.

A preferred combination is a detergent composition having a cocktail of conventional applicable enzymes like protease, amylase, lipase, cutinase and/or cellulase in conjunction with the lipolytic enzyme variant D96L at a level of from 50

LU to 8500 LU per liter wash solution.

The cellulases usable in the present invention include both bacterial or fungal cellulase. Preferably, they will have a pH optimum of between 5 and 9.5. Suitable cellulases are disclosed in U.S. Patent 4,435,307, Barbesgoard et al, 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-OS-2.247.832. Examples of such cellulases are cellulases produced by a strain of Humicola insolens (Humicola grisea var. thermoidea), particularly the Humicola strain DSM 1800.

Other suitable cellulases are cellulases originated from Humicola insolens having a molecular weight of about 50KDa, an isoelectric point of 5.5 and containing 415 amino acids. Especially suitable cellulases are the cellulases having color care benefits. Examples of such cellulases are cellulases described in European patent application No. 91202879.2, filed November 6, 1991 (Novo).

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 WO 89/099813 and in European Patent application EP No. 91202882.6, filed on November 6, 1991.

Said cellulases and/or peroxidases are normally incoφorated in the detergent composition at levels from 0.0001% to 2% of active enzyme by weight ofthe detergent composition.

Preferred commercially available protease enzymes include those sold under the tradenames Alcalase, Savinase, Primase, Durazym, and Esperase by Novo Nordisk A/S (Denmark), those sold under the tradename Maxatase, Maxacal and Maxapem by Gist-Brocades, those sold by Genencor International, and those sold under the tradename Opticlean and Optimase by Solvay Enzymes. Also proteases described in our co-pending application USSN 08/136,797 can be included in the detergent composition of the invention. Protease enzyme may be incoφorated into the compositions in accordance with the invention at a level of from 0.0001% to 2% active enzyme by weight ofthe composition. A preferred protease herein referred to as "Protease D" is a carbonyl hydrolase variant having an amino acid sequence not found in nature, which is derived from a precursor carbonyl hydrolase by substituting a different amino acid for the amino acid residue at a position in said carbonyl hydrolase equivalent to position +76, preferably also in combination with one or more amino acid residue positions equivalent to those selected from the group consisting of +99, +101, +103, +104, +107, +123, +27, +105, +109, +126, +128, +135, +156, +166, +195, +197, +204, +206, +210, +216, +217, +218, +222, +260, +265, and/or +274 according to the numbering of Bacillus amyloliquefaciens subtilisin, as described in the concurrently filed patent application of A. Baeck et al. entitled "Protease-Containing Cleaning Compositions" having U.S.

Serial No. 08/322,676. fiied October 13, 1994, which is incoφorated herein by reference in its entirety. Also suitable are cutinases [EC 3.1.1.50] which can be considered as a special kind of lipase, namely lipases which do not require interfacial activation. Addition of cutinases to detergent compositions have been described in e.g. WO-A-88/09367

(Genencor).

The lipases and/or cutinases are normally incoφorated in the detergent composition at levels from 0.0001% to 2% of active enzyme by weight of the detergent composition.

Amylases (& and/or ^β) can be included for removal of carbohydrate-based stains. Suitable amylases are TermamylP- (Novo Nordisk), Fungamyl^ and BAN

(Novo Nordisk). The above-mentioned enzymes may be of any suitable origin, such as vegetable, animal, bacterial, fungal and yeast origin.

Said enzymes are normally incoφorated in the detergent composition at levels from 0.0001% to 2% of active enzyme by weight of the detergent composition.

Other suitable detergent ingredients that can be added are enzyme oxidation scavengers which are described in Copending European Patent application

92870018.6 filed on January 31, 1992. Examples of such enzyme oxidation scavengers are ethoxylated tetraethylene polyamines.

A preferred component to be used in the detergent compositions of the present invention comprise soil-release agents. Soil release agents useful in compositions ofthe present invention are conventionally copolymers or teφolymers of terephthalic acid with ethylene glycol and/or propylene glycol units in various arrangements. Examples of such polymers are disclosed in the commonly assigned US Patent Nos. 41 16885 and 471 1730 and

European Published Patent Application No. 0 272 033. A particular preferred polymer in accordance with EP-A-0 272 033 has the formula

(CH3(PEG)43)o.75(POH)o.25[T-PO)2.8(T-PEG)o.₄]T(PO- H)o.25((PEG)43CH₃)o.75

where PEG is -(OC H )0-,PO is (OC3H₆0) and T is (pcOCg^CO). Also very useful are modified polyesters as random copolymers of dimethyl terephtalate, dimethyl sulfoisophtalate, ethylene glycol and 1-2 propane diol, the end groups consisting primarily of sulphobenzoate and secondarily of mono esters of ethylene glycol and/or propane-diol. The target is to obtain a polymer capped at both end by sulphobenzoate groups, "primarily", in the present context most of said copolymers herein will be end-capped by sulphobenzoate groups. However, some copolymers will be less than fully capped, and therefore their end groups may consist of monoester of ethylene glycol and/or propane 1-2 diol, thereof consist "secondarily" of such species. The selected polyesters herein contain about '16% by weight of dimethyl terephtalic acid, about 16% by weight of propane -1.2 diol, about 10% by weight ethylene glycol about 13% by weight of dimethyl sulfobenzoid acid and about 15% by weight of sulfoisophtalic acid, and have a molecular weight of about 3.000. The polyesters and their method of preparation are described in detail in EPA 31 1 342. Particularly suitable soil-release polymers include oligomeric esters such as described in US Patent Application No. 08/355 938 filed December 14, 1994. Said esters comprise :

( 1 ) a backbone comprising

(a) at least one unit selected from the group consisting of dihydroxy or polyhydroxy sulfonate, a unit which is at least trifunctional whereby ester linkages are formed resulting in a branched oligomer backbone, and combinations thereof;

(b) at least one unit which is a terephthaloyl moiety; and

(c) at least one unsulfonated unit which is a 1 ,2-oxyalkleneoxy moiety; (2) one or more (nonionic and/or anionic) capping units.

Other components used in detergent compositions may be employed, such as soil-suspending agents, abrasives, bactericides, tarnish inhibitors, coloring agents, foam control agents, corrosion inhibitors and perfumes. Preferably, the liquid compositions according to the present invention are in

"concentrated form"; in such case, the liquid detergent compositions according to the present invention will contain a lower amount of water, compared to conventional liquid detergents. The level of water is less than 50%, preferably less than 30% by weight ofthe detergent compositons. Said concentrated products provide advantages to the consumer, who has a product which can be used in lower amounts and to the producer, who has lower shipping costs. The liquid compositions are especially effective when applied directly to soils and stains in a pretreatment step.

The detergent compositions of the present invention can also be used as detergent additive products. Such additive products are intended to supplement or boost the performance of conventional detergent compositions.

The detergent compositions according to the present invention include compositions which are to be used for cleaning of substrates, such as fabrics,fibers, hard surfaces, skin etc., for example hard surface cleaning compositions(with or without abrasives), laundry detergent compositions, automatic and non-automatic dishwashing compositions.

The following examples are meant to exemplify compositions ofthe present inventions, but are not necessarily meant to limit the scope ofthe invention.

EXAMPLE

The following liquid detergent composition is made :

% by weight of the detergent composition

COMPONENT Wt

(%)

C12-C15 Alkyl ethoxylated sulfate 14.50

C12-C15 Alkyl sulfate 9.00

C12-C14 N-methyl glucamide 3.00

C12-C14 fatty alcohol ethoxylate 1.00

C12-14 Alkyl dimethyl hydroethyl ammonium 2.50 chloride

C12-C14 Fatty acid 4.50

Citric 3.00

Acid

Sodium hydroxide 0.73

Monoethanolamine 6.93

Propanediol 8.53

Ethanol 5.50

Boric 3.50 acid

Sodium xylene sulfonate 1.90 Tetraethylenepentamine ethoxylated ( 15-18) 3.00

Terephthalate-based polymer 0.30

Protease (34g/l) 1.50

Lipase D96 L (lOOKNU/g) 0.12

Carezyme (5000 CEVU/g) 0.084

Diethanol amine (stilbene) 0.100

2-Hexyl Decanol 2.00

Water & Minors Up to 100%

The above liquid detergent composition was found to be very efficient in the removal of greasy/oily soils under various usage conditions.

Claims

WHAT IS CLAIMED IS:

1. A detergent composition comprising

(a) a lipolytic enzyme, and

(b) from about 1% to about 10% of a quaternary ammonium surfactant having the formula

«

\ / ^R1

N β

wherein Rj and R2 are individually selected from the group consisting of C1 -C4 alkyl, C1 -C4 hydroxy alkyl, benzyl, and -(C2H4θ)_xH where x has a value from about 2 to about 5; X is an anion; and (1) R3 and R4 are each a C6-C14 alkyl or (2) R3 is a C6-Cj alkyl, and R4 is selected from the group consisting of C \ -C \ Q alkyl, C \ -C \ hydroxy alkyl, benzyl, and -(C2H4θ)_xH where x has a value from 2 to 5.

2. The composition of Claim 1 comprising from about 2% to about 7% of the quaternary ammonium surfactant.

3. The composition of Claim 2 wherein the quaternary ammonium surfactant is selected from the group consisting of lauryl trimethyl ammonium chloride, myristyl trimethyl ammonium chloride, palmityl trimethyl ammonium chloride, coconut trimethyl ammonium chloride, coconut trimethyl ammonium methylsulfate, coconut dimethyl-mσno- hydroxyethylammonium chloride, coconut dimethyl-monohydroxy- ethylarnmonium methylsulfate, steryl dimethyl-monohydroxyethyl- ammonium chloride, steryl dimethyl-monohydroxyethylammonium methylsulfate, di- C12-C14 alkyl dimethyl ammonium chloride, and mixtures thereof.

4. The composition of Claim 3 wherein the lipolytic enzyme is D96L lipolytic enzyme.

5. The composition of Claim 4 comprising from about 0.05% to about 0.5% ofthe lipolytic enzyme.

6. The composition of Claim 1 wherein the weight ratio of anionic surfactant component to quaternary ammonium surfactant is from about 2: 1 to about 3.5: 1.

7. The composition of Claim 1 further comprising from about 1% to about 20% of a non-citrate, non-fatty acid detergent builder material.

8. A detergent composition according to Claim 1 which is in a liquid form.