MXPA98003935A - Detergent compositions for laundry containing lipolitic enzyme and quaternary ammonium compounds select - Google Patents

Abstract

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

Description

COMPOSITIONS DETERGENTS FOR LAUNDRY CONTAINING LIPOLITIC ENZYME AND SELECTED QUATERNARY AMMONIUM COMPOUNDS FIELD OF THE INVENTION The present invention relates to compositions containing a lipolytic enzyme (lipase) and selected quaternary ammonium surfactants. The compositions provide increased cleaning of soils and grease / oil stains.

BACKGROUND OF THE INVENTION The inclusion of lipase in detergent compositions for improved cleaning performance is known, for example, for the increased removal of triglyceride-containing blotches and stains from fabrics. Examples of this are US Pat. No. 4,769,173 »US Pat. No. 5,069, B09, the application of TCP WO 94/0357B. US Pat. No. 4,769,173 discloses a certain class of lipases consisting of fungal lipases from Humicola lanuginosa, together with strong bleaching agents in detergent compositions. An example of a funga lipase! in this patent is the lipase of Humicola lanuginosa obtainable from Amano under the brand Amano-CE. In USP 5,069,809, 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 lysyzae as a host for use in detergent compositions is described. / 0357B an enzymatic detergent composition containing from 10 to 20,000 UL (lipolytic units) per gram of detergent composition of a lipase exhibiting substantial lipolytic activity during the main cycle of a washing process. Particularly, based on its inactivation behavior with d isopropyl fluorophosphate (DFP) .. Of the lipase enzymes »only the lipase derived from Humicola lanuginosa and produced in Aspergillus oryzae as a host, has so far found wide application as an additive for products for wash fabrics is available under the Lipolase brand of Novo NordisK. to optimize the elimination operation of the Lipolase »Novo NordisK has made several variants. WO 92/05249 discloses the D96L variant of the Humicola lanuginosa natural lipase »which improves the efficiency of elimination of butter stains by a factor of 4.4 with respect to the wild-type lipase (enzymes compared in an amount ranging from 0.075 to 2.5 mg of protein per liter). The capacity of the lipase to clean grime and fabric stains »present in the typical laundry load» is of great importance to evaluate the performance of the detergent. Unfortunately, the relative capacity of lipase to satisfy various functional criteria depends, inter alia, on the presence of surfactant coagents. Thus, there remains the desire "for functional and lexi-ty reasons" to provide a surfactant system capable of providing the optimal detergent performance of the lipase. The above objective has been met by a system of surfactants comprising a surfactant coagent selected from the group of selected quaternary ammonium compounds. It has surprisingly been found that the inclusion of quaternary ammonium compounds selected especially in liquid detergent compositions containing a lipolytic enzyme (lipase) substantially improves their ability to rapidly decrease the interfacial tension of aqueous wash liquors containing oily and oily mules. This substantial reduction in the interfacial tension of oily and oily grimes improves their removal from soiled surfaces and inhibits the redeposition of grubs on substrates.

THE LIPOLITIC ENZYME An essential ingredient in the laundry detergent compositions herein is an "operation enhancing amount" preferably of about 0.0001 to 1o, or better still about 0.05 to 0.5%. on an active base »of a lipase compatible with the detergent (lipolytic enzyme). By "compatible with the detergent" is meant the compatibility with the other ingredients of the composition, particularly the detergent surfactants and any builders. Liquid detergent compositions, particularly heavy-duty liquids »are preferred herein. Any suitable lipase can be used here for use in a laundry detergent composition. Lipases suitable for use herein include those of bacterial and fungal origin. Lipases from chemically or genetically modified mutants are included here. Suitable bacterial lipases include those produced by Pseudomonas »such as Pseudomonas stutzeri ATCC 19.154» which is described in British Patent 1,372,034, which is incorporated herein by reference. Suitable lipases include those which show a positive unological cross-reaction with the lipase antibody produced by the microorganism Pseudomonas fluorescens IAM 1057. This lipase and a method for its purification have been described in Japanese Patent Application 53-204B7 »which It was opened to public inspection on February 24, 197B, which is incorporated herein by this reference. This lipase is available under the brand name Lipase P "Amano", hereinafter referred to as "Amano-P". Said lipases must show a positive immunological cross-reaction with the Amano-P antibody. using the common and current immunodiffusion procedure and well known »according to Ouchterlony (Acta. Med. Sean., 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. of Thom and coi ventores »issued on November 17, 197» incorporated herein by this reference. Typical examples are the Amano-P lipase, the Pseudomonas fragi lipase FERM P 1339 (obtainable under the Amano-B brand), the 1-ipase from Pseudomonas nitroreducens, var. lipolyticu FERM P 133B (obtainable under the trademark Amano-CES), Chromobacter viscoso lipases, for example »Chromobacter viscosu var. lipolyticum NRRLB 3673, and other lipases from Chromobacter viscosum and the lipases from Pseudomonas glad oli. Other 1 compounds of interest are Amano AKG and the lipase from Bac lis Sp. Suitable f lipases include those that are producible by Humicola lanuginosa and Thermomyces lanuginosus. Most preferred are the lipases obtained by cloning the Humicola lanuginosa gene and expressing the gene in Aspergillus oryzae "as described in European patent application 0 258068. incorporated herein by this reference" obtainable commercially under the trademark Lipolase1">; . Most preferred are lipases which are a lipolytic enzyme D96L, variant of the natural lipase derived from Humicola lanuginosa »as described in the US application Serial No. 0B / 341, B26. Preferably the strain DSM 4106 of Humicola lanuginosa is used. This enzyme is incorporated into the composition according to the invention at a level of 50 UL to B500 UL per liter of wash solution. Preferably, the D96L variant is present at a level of 100 UL to 7500 UL per liter of wash solution. It is further preferred that it be at a level of 150 UL to 5000 UL per liter of the washing solution. By variant of lipolytic enzyme D96L is meant the lipase variant which is described in the patent application WO 92/05249"that is" where the natural lipase "from Humicola lanuginosa" has the aspartic acid residue (D) of the 96 position changed to leucine (L). According to the nomenclature »said replacement of aspartic acid by leucine in position 96 is shown as D96L. It has been found that the D96L lipolytic enzyme variant is particularly preferred due to the good odor characteristics associated with the combined use of enzymes. In these compositions, about 2 to 20,000, preferably about 10 to 6,000, may be used. Most preferably, about 200 to 2,000, lipase units per gram (UL / g) of lipase. One unit of lipase is that amount of lipase that produces 1 μmol of titratable butyric acid per minute at a stable pH, where the pH is 7.0, the temperature is 30 ° C and the substrate is an emulsion of tributyrin and gum arabic, in presence of Ca ** and IMaCl in phosphate buffer.

THE COMPOUNDS OF QUATERNARY AMMONIUM The compositions herein also contain about 1% to 10%, preferably about 2 *? to 7% by weight of quaternary ammonium surfactant, of the formula \ / N X * / R. R. wherein Rt and R2 are selected from the group consisting of alkyl of 1 to 4 carbon atoms, hydroxyalkyl of 1 to 4 carbon atoms, benzyl and - (CarH ^ 0)), < H where x has a value of 2 to 5 »approximately» X is an anion and (1) each of R3 and R ^ is an alkyl of 6 to 14 carbon atoms or (2) R ..]: it is a alkyl of 6 to 18 carbon atoms and R ^ is selected from the group consisting of alkyl of 1 to 10 carbon atoms »hydroxyalkyl of the 10 carbon atoms» benzyl and - (C ^ H ^ O ^ H. where x it has a value of 2 to 5. Preferred quaternary ammonium surfactants are the chloride, bromide and methyl isulfate salts, examples of long-chain monoalkyl quaternary ammonium surfactants are those in which each of R x R - and R ^ is methyl and R3 is an alkyl of 8 to 16 carbon atoms, or where R3 is alkyl of 8 to 18 carbon atoms and Rx, Re and. * are selected from methyl and hydroxyalkyl portions. Particularly lauryl chloride 1 trimethylammonium chloride, iristi chloride 1 trimethylammonium chloride »palmium chloride 1 trimethylammonium» cocotrimeti chloride 1-ammonium , cocotimetilammonium methylsulfate »coconut-dimethyl-1-monohydroxy-ammonium chloride» cocodimethyl-hydroxymethyl-sulphonium hydroxide »ammonium chloride" Idimeti 1-monohydroxy-ethylammonium »ester methylsulfate Idimeti 1-monohydroxy-1-a onium» dialkyl chloride of Cia_jL ^ -dimet 1 ammonium and its mixtures. Also preferred is ADOSEN 412 < R > . a chloride of lauri l trimeti lamonio »obtainable in the Witco trade. Still more preferred is lauryl chloride 1 trimethylammonium chloride and myristium chloride 1 trimethylammonium chloride. The inventions herein comprise the detergent composition wherein the weight ratio of anionic surfactant component to quaternary ammonium surfactant is about 1.5: 1 to 5: 1, preferably about 1.5: 1 to 4.5: 1. better yet »around 2: 1 to 4: 1» even better »around 2: 1 to 3.5: 1.

THE PROCESS OF WASHING AND PRE-TREATMENT OF FABRICS The present invention also provides a process for washing fabrics soiled with greasy / oily stains or grime. Said method employs contacting these fabrics with an aqueous washing solution »formed from an effective amount of the detergent compositions described above. The contact of the fabrics with the washing solution will generally occur under agitating conditions. Preferably agitation is provided in a washing machine for good cleaning. Preferably washing is followed by drying the wet cloth, in a conventional fabric dryer. An effective amount of the liquid or granular detergent composition in the aqueous wash solution in the washing machine is preferably about 500 to 7000 ppm, better still, about 1000 to 3000 ppm.

THE 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 variety of surfactants. A typical list of the anionic »nonionic» ampholytic and zwitterionic classes and the species of these surfactants is given in US Pat. No. 3,665,961 issued to Norris on May 23, 1972. Surfactants Preferred anionic agents include the alkyl sulfate surfactants herein which are salts or water-soluble acids of the formula R0S03M "wherein R is preferably a hydrocarbyl of 10 to 24 carbon atoms" preferably an alkyl or hydroxyalkyl which has an alkyl component of 10 to 18 carbon atoms, better still, an alkyl or hydroxyalkyl of 12 to 15 carbon atoms, and M is H or a cation »for example» an alkali metal cation (for example »sodium, potassium» lithium) »or ammonium or substituted ammonium (for example» methyl- »dimethyl- and trimethylammonium cations and ammonium cations quaternary »such as the cations of tetra eti 1 ammonium and dimethylpiperidinium» and the quaternary ammonium cations derived from alkylamines »such as etila» dieti lamina »triethylamine and their mixtures» and sires). Highly preferred anionic surfactants include the alkoxylated alkyl sulfate surfactants herein, which are salts or water-soluble acids of the formula R0 (A) mS0 M "wherein R is an unsubstituted alkyl group of 10. to 24 carbon atoms, or hydroxyalkyl having an alkyl component of 10 to 24 carbon atoms, preferably an alkyl or hydroxyalkyl of 12 to IB carbon atoms, better still alkyl or hydroxyalkyl of 12 to 15 carbon atoms; A is an ethoxy or propoxy unit »m is greater than zero» typically between 0.5 and 6 »approximately» better still »between 0.5 and approximately 3, and M is H or a cation that, for example, can be a metal cation (for example, sodium, potassium, lithium »calcium, magnesium, etc.); an ammonium or substituted ammonium cation. The alkyl ethoxylated sulfates, as well as the propoxylated alkyl sulphates are contemplated herein. Specific examples of substituted ammonium cations include the methyl- »dimethyl-» trimethyl-ammonium cations and the quaternary ammonium cations »such as tetramethyl-ammonium and the dimethylpiperidine cations and the alkylamines derivatives such as ethyl acetate. ina »dieti lamina» triethylamine and mixtures thereof, and the like. Exemplary surfactants are polyethoxylate (IO) alkyl sulfate of 12 to 15 carbon atoms (C, -, L, E (1.0) M). the polyethoxylate sulfate (2.25 alkyl of 12 to 15 carbon atoms (C? ai_JLBE (2.25) M), the polyethoxylate sulfate (3. O) of alkyl of 12 to 15 carbon atoms (C13t_a. ß> E (3.0) M) »and polyethoxylate sulfate (4.0) of alkyl of 12 to 15 carbon atoms (Ca.2_xßE (4.0) M)» where M is conveniently selected from sodium and potassium Other suitable anionic surfactants to be used are the surfactants of this alkyl sulfonate which include the linear esters of carboxylic acids of B to 20 carbon atoms (ie the fatty acids), which are sulphonated with gaseous S03. According to The Journal of the American Oil Chemistry Society, 52 (1975), pages 323- 329. Suitable starting materials would include natural fatty substances »which are derived from tallow, palm oil, etc. The surfactant Preferred alkyl ester sulfonate, especially for laundry applications , comprises the alkyl ester sulfonate surfactants of the structural formula: OR II Rß - CH - C - 0R- »! SO3M where R3 is a hydrocarbyl of? at 20 carbon atoms, preferably an alkyl or a combination thereof; R * 4 is a hydrocarbyl of 1 to 6 carbon atoms, preferably an alkyl or a combination thereof, and M is a cation that forms a water soluble salt with the alkyl ester sulfonate. Suitable salt-forming cations include the metals »such as sodium» potassium and lithium and the substituted or unsubstituted ammonium cations such as monoethanolamine, diethanolamine and triethanolamine. Preferably R3 is alkyl of 10 to 16 carbon atoms and R-4 is methyl or etho isopropyl. Methyl ester sulfonates are particularly preferred, where R 3 is alkyl of 10 to 16 carbon atoms. Other anionic surfactants for detergent purposes may also be included in the laundry detergent compositions of the present invention. These may include salts (including, for example, the "potassium sodium" ammonium and substituted ammonium salts, such as the mono-, di- and tr-ethanolamine salts) of soap linear alkylbenzenesulfonates of 9 to 20 carbon atoms. carbon, primary or secondary alkanesulphonates of 8 to 22 carbon atoms »olefinsulfonates of 8 to 24 carbon atoms, sulphonated polycarboxylic acids» prepared by sulfonation of the pyro product! of alkaline-earth metal treatments, for example, those described in British Patent Application No. 1, 082,179, the alkyl ether sulfates, Ipol igl, from B to 24 carbon atoms (containing up to 10 moles of sodium oxide). ethylene); sulphonates of alkylene glycol, fatty acyl sulphonates, glycerol, sulphonates of oily fatty acid, sulphonates of alkylphenol and ethylene oxide, paraffin sulfonates, alkyl phosphates, isethionates, such as acyl isethionates, taurates of N-ac lo. succina alkyl acids and alkyl sulfosuccinates; monoesters of sulfosuccinates (especially saturated and unsaturated monoesters of 12 to 18 carbon atoms) and diesters of sulfosuccinates (especially saturated and unsaturated diesters of 6 to 12 carbon atoms). alkane sulfates Ipol isaccharides »such as the alkyl polyglucoside sulfates (the nonionic, unsulfated compounds are described below) and the alkyl polyethoxycarboxylates, such as those of the formula: RO (CH, H,) lt-CH_COO-M + wherein R is an alkyl of B to 22 carbon atoms »K is an integer from 0 to 10 and M is a soluble salt-forming cation. Resin acids and hydrogenated resin acids are also suitable, such as rosin, hydrogenated rosin and the resin acids and hydrogenated resin acids present in or derived from first distillation oil. Other examples are described in Surface-Acti ve Agents and Detergents (volumes I and II, by Schwartz, Perry and Berch). A variety of such surfactants is also generally described in U.S. Patent 3,929,678 B issued December 30, 1975 by Laughlin and co-inventors in column 23, row 58 through column 29, line 23 (incorporated herein by reference). this reference). When included herein, the laundry detergent compositions of the present invention typically comprise about 1% to 40%, preferably about 5% to 25% by weight of said ionic surfactants. A class of nonionic surfactants useful in the present invention are the condensates of ethylene oxide with a hydrophobic portion to give a surfactant having a hydrophilic equilibrium (EHL) on the scale of 8 to 17 »preferably from 9.5 to 14» better still »from 12 to 14. The hydrophobic portion (1 iphophyl) may be aliphatic or aromatic in nature» and the length of the polyoxyethylene group that is condensed with any particular hydrophobic group may be be easily adjusted to produce a water-soluble compound, which has the desired degree of balance between the hydrophilic and hydrophobic elements. Especially preferred surfactants of this type are the primary alcohol ethoxylates of 9 to 15 carbon atoms containing from 3 to 12 moles of ethylene oxide per mole of alcohol, in particular the primary alcohols of 12 to 15 atoms of carbon containing from 5 to B moles of ethylene oxide per mole of alcohol. Another class of nonionic surfactants comprises the alkyl glycolide compounds of the general formula: RO (C "HanO) ^ Z, wherein Z is a portion derived from glucose; R is a saturated hydrophobic alkyl group containing from 12 to IB 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 iglucoside alkyl. Compounds of this type and their use in detergents are described in EP-B 0 070 077 »0 075 996 and 0 094 11B. Also suitable as nonionic surfactants are the hydroxy fatty acid amide surfactants of the formula: R2 - C - N - Z I! I 0 R ^ - wherein A is H or RA is hydrocarbyl of 1 to 4 carbon atoms. 2-hydroxyethyl 1 or, 2-hydroxypropyl or a mixture thereof; Rz is hydrocarbyl of 5 to 31 carbon atoms and Z is a polyhydroxyhydrocarbon which has a linear chain of hydrocarbyl with at least 3 hydroxy directly connected to the chain or an alkoxylated derivative thereof. Preferably R is methyl, R * is a straight alkyl or alkenyl chain of 11 to 15 carbon atoms "such as cocoalkyl" or mixtures thereof "and Z is derived to a reducing sugar" such as glucose, fructose »maltose» latose »In a reductive reaction. The highly preferred nonionics are the amine oxide surfactants. The compositions of the present invention may comprise amine oxide according to general formula i: Ri (OE) > < (OP) (OB) I.N (0) (CHj-R ') 2FqH20 (I) In general, it can be seen that structure (I) provides a portion of long chain RA (OE) > < (0P) > , 0B) x and two short chain portions »CH.?»R '», preferably hydrogen "R" being selected methyl and -CH-.OH In general, RA is a primary or branched hydrocarbyl portion which may be saturated or unsaturated »Preferably» RA is a primary alkyl portion When x + y + z is different from 0 »RA it can be somewhat longer» with a chain length on the scale of 12 to 24 carbon atoms The general formula also it comprises the amine oxides in which x + y + z = 0, Rx = 8 to IB carbon atoms, Rt = H and q = 0-2, preferably 2. These amine oxides are illustrated by oxide of qui Idimeti 1 amine of 12 to 14 carbon atoms in the alkyl, hexadecyl oxide Idimeti sheet »octadecylamine oxide and its hydrates» especially the dihydrates which are described in US Patents 5,075, 501 and 5,071,994, incorporated herein by This reference also includes amine oxides in which x + y + z is different from zero, specifically x + y + z is from 1 to 10, approximately; R3- is a primary alkyl group containing from 8 to 24 carbon atoms, preferably from about 12 to 16 carbon atoms; in these modalities »y + z is preferably O and x is preferably around 1 to 6, better still» around 2 to 4; OE represents oxyethylene; OP represents oxipropylene and OB represents oxybutyl. Said amine oxides can be prepared by conventional synthesis methods, for example by reaction of alkyl ethoxysulfates with dimethylamine, followed by oxidation of the amine ethoxide with hydrogen peroxide. The highly preferred amine oxides herein are solids at room temperature; it is more preferred that they have melting points on the scale of 30 ° C to 90 ° C. The amine oxides suitable for use herein are commercially made by numerous suppliers »including AKzo Chemie» Ethyl Corp. and Procter & Gamble. The compilation of McCutcheon's and the KirK-Othmer abstract article for other amine oxide manufacturers. The preferred amine oxides commercially obtainable are the ADMOX 16 and ADMOX 18 »ADMOX 12 dihydrate solids and, especially» ADMOX 14, from Ethyl Corp. Preferred embodiments include the hexadecyl dihydrate Idimeti Lamina »the dihydrate of oxide of dodecy Idimet lamina »the dihydrate of oxide of octadeci Idimet lamina» the oxide of hexadeci 1 tris (eti lenox) -dimetilamina and the dihidrato of oxide of tetradecildi eti lamina. While in some of the preferred embodiments R '= H »there is a certain latitude with respect to R' being slightly greater than H. Specifically» the invention additionally comprises modality, wherein R '= CH.ÍOH »such as hexadec lbis (2-hydroxyeti 1) amine oxide» tallowbis- (2-hydroxyeti 1) amine oxide »stearylbis (2-hydroxyeti 1) amine oxide and olebis lbis (2-hydroxyeti 1) amine oxide »dodecyl dihydrate Idimeti lamina.

When they are included in this. The laundry detergent compositions of the present invention typically comprise nonionic surfactants in a weight ratio of anionic surfactant to nonionic surfactant of from 6: 1 to 1: 3, preferably from 5: 1 to 2: 1. The compositions according to the present invention may additionally comprise a builder system. Any conventional builder system is suitable for use herein including aluminosilicate materials, polycarboxylates and fatty acids, materials such as ethylenediamine tetraacetate, metal ion sequestrants such as intophosphonates, particularly eti lendia, inotetramethylphosphosphonic acid. and diethi lentriaminopentameti lenphosphonic acid. Although less preferred for obvious environmental reasons, phosphate builders can also be used here. Polycarboxylate builders suitable for use herein include citric acid "preferably in the form of a water soluble salt" succinic acid derivatives of the formula R-CH (COOH) CHse (COOH), in where R is alkyl or alkenyl of 10 to 20 carbon atoms, preferably of 12 to 16 carbon atoms, or where R can be substituted with hydroxyl, sulfo, sulfoxyl or sulfone substituents. Specific examples include: lauryl succinate »mistyl succinate» palmityl succinate »2-dodecem succinate and succinate and 2-tetradecemyl. The succinate builders are preferably used in the form of their water-soluble salts, which include the sodium potassium salts of ammonium and alkanolammonium salts. Other suitable polycarboxylates are the oxodisuccinates and the mixtures of tartratomonosuccinic acid and tartrate diuccinate which are described in US 4,663,071. Especially for the liquid execution of the present »fatty acid improvers suitable for use herein are the saturated or unsaturated fatty acids of 10 to 18 carbon atoms, 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. Another preferred builder system for liquid compositions is based on dodeceni lsuccinico acid and citric acid. Builder salts are usually included in amounts of 3% to 50% by weight of the composition, preferably 5% to 30% and very usually 5% to 25% by weight.

THE OPTIONAL DETERGENT INGREDIENTS The preferred detergent compositions of the present invention may additionally comprise one or more enzymes that provide cleansing performance and / or fabric care benefits. Said enzymes include the enzymes selected from cellulases. semicelul handles. peroxidases »proteases» glucoa and lasas »amylases» lipases »cutinases» pectinases »xylanases» reductases »oxidases. phenoloxidases, 1 ipoxygenases, ligninases, pullulanases, tannases, pentosanas, malanases, beta-glucanases »arabinosidases or their mixtures. A preferred combination is a detergent composition having a combination of applicable conventional enzymes such as "protease" amylase, lipase, cutinases and / or cellulase "together with the enzyme variant 1 ipollicic D96L" at a level of 50 UL to 8500 UL per liter of washing solution. The cellulases usable in the present invention include bacterial or fungal cellulase. Preferably they will have an optimum pH between 5 and 9.5. Suitable cellulases are described in US Pat. No. 4,435,307 of Barbesgoard and co-inventors, which describes cellulase funga! produced from Humicola insolens Suitable cellulases are also described in GB-A-2.075 »028; GB-A-2,095 »275 and DE-OS-2,247. B32 Examples of said cellulases are cellulases produced by a strain of Humicola insolene. { Humicola grisea var. thermoidea) »in particular the strain DSM 1800 Humicola. Other suitable cellulases are the cellulases originated from Humicola insolens which have a molecular weight of about 50 KDa »an isoelectric point of 5.5 and which contain 415 amino acids. Especially suitable cellulases are those that have color care benefits. Examples of such cellulases are those described in European patent application No. 91202879.2, presented on November 6, 1991 (Novo). Peroxidase enzymes are used with "oxygen sources" eg "percarbonate" perborate "persulfate" hydrogen peroxide "etc. They are used for" bleaching in solution ", ie to prevent the transfer of dyes or pigments removed from the substrates during washing operations to other substrates present in the wash solution The peroxidase enzymes are known in the art and include, for example, horseradish peroxidase »ligninase and halogenoperoxidase» such as chloro- and bromo-peroxidases. detergents containing peroxidase are described, for example, in the international application of! TCP WO 89/099813 and European patent application EP No. 91202882.6, filed on November 6, 1991. The cellulases and / or peroxidases mentioned are usually incorporated in the detergent composition at levels of 0.0001% to 2% of active enzyme »by weight of the detergent composition.The preferred protease enzymes» obtain Trademarks include those sold under the brands Alcalase »Savinase» Primase »Durazym and Esperase by Novo NordisK A / S» (Denmark); those sold under the Maxatase brands »Maxacal and Maxapem. by Gist-Brocades; those sold by Genencor International, and those sold under the Opticlean and Optirnase brands by Solvay Enzymes. The proteases described in the US application of the same inventors may also be included in the detergent composition of the invention. Serial No. 08 / 136,797. The protease enzyme can be incorporated in the compositions according to the invention at a level of 0.0001% to 2% active enzyme, by weight of the composition. A preferred protease, which is referred to herein as "Protease D" is a variant of carboni Ihydrolase having an amino acid sequence that is not found in nature "which is derived from a precursor Ihydrol asa carbonyl" by substituting the amino acid residue that it is in a position of the hydroxylahydrolase equivalent to the position +76 »by a different amino acid; preferably also in combination with one or more amino acid residue positions equivalent to those selected from the group consisting of +99 »+101» +104 »+107, +123, +27, +105, +109, +126, + 12B, +135, +136, +166 »+195» +197, +204, +206, +210, +216. +217, + 21B. +222, +260, +265 and / or +274, according to the numeration of the subti lysine of Bacillus amy1 ol ique aciens, which is described in the concurrently filed patent application of A. Baeck and co-inventors, entitled " Cleaning compositions containing protease ", which has e! Serial No. of the United States No. 0B / 322,676, filed on October 13, 1995, which is hereby incorporated in its entirety by this reference. Also suitable are CEC cutinases 3.1.1.503 which can be considered as a special class of lipase, ie, lipases that do not require interfacial activation. The addition of cutinases to the detergent compositions has been described, for example, in W0-A-88/09367 (Genencor). Lipases and / or cutinases are usually incorporated into the detergent composition at levels of 0.0001% to 2% active enzyme by weight of the detergent composition. The amyl asas (alpha and / or beta) can be included for elimination of carbohydrate-based stains. The suitable ami lasas are Termamyl "(Novo Nordisk), Fur \ gamyl and BAN" (Novo NordisK). The enzymes mentioned above can be of any suitable origin, such as vegetable, animal, bacterial, fungal and yeast origin. Said enzymes are normally incorporated in the detergent composition at levels of 0.001% to 2% active enzyme by weight of the detergent composition. Other suitable detergent ingredients that can be added are the enzyme oxidation scavengers, which are described in the European patent application of the same inventors No. 92870018.6. filed on January 31, 1992. Examples of such enzyme oxidation scavengers are ethylated tetraethylene-polyamines. A preferred component for use in the detergent compositions of the present invention comprises soil release agents.

The soil release agents useful in the compositions of the present invention are usually copolymers or terpenes of terephthalic acid with ethylene glycol and / or propylene glycol units in various arrangements. Examples of such polymers are described in United States patents assigned to the same successor as the present one, Nos. 4,116,885 and 4,711,730, as well as in European Patent Application Publication No. 0 272033. A particularly preferred polymer, in accordance with US Pat. EP-A-0 272033, has the formula: (CH3 (PEG) ^ 3) or .-. ß (P0H) os, ßC (T-P0) 2.β (T-PEG) or. ^ 1 (P0- H) 0. = fß (< PEG) ^ 3 H3) 0, -re where PEG is - < OCa! H,) 0-, PO is (OC3HßO) and T is (pcOCß-H ^ CO). Polyesters modified as random copolymers of dimethyl terephthalate »dimethyl sulfoisophthalate» ethylene glycol and 1,2-propanediol are also very useful, the end groups consisting primarily of sulfobenzoate and secondarily of monoesters of ethylene glycol and / or propanediol. The objective is to obtain a polymer crowned at both ends by sulfobenzoate groups "" primarily "in the present context means that most of the codend! The present will be crowned in e! end with sulfobenzoate groups. However, some copiers will be less than fully crowned and. consequently, their end groups may consist of ethylene glycol monoester and / or propane-2-diol, which consist "secondarily" of said species. The polyesters selected here contain about 46% by weight of dimethyl-1-terephthalic acid, about 16% by weight of propane-1,2-diol, about 10% by weight of ethylene glycol, about 13% by weight of acid. dimethylsulfo-benzoic acid and about 15% by weight of sulphuric acid, and have a molecular weight of about 3,000. The polyesters and their method of preparation are described in detail in EPA 311 342. Particularly suitable grit-blocking polymers include the oléric esters, such as those described in U.S. Patent Application No. 08 / 355,938, filed December 14, 1994. Said esters comprise: a) a fundamental structure comprising: (a) at least one unit selected from the group consisting of dihydroxy- or polyhydroxysulfonate, a unit that is at least trifunctional, so that ligatures are formed ester that result in a fundamental structure! bran oligomeric, and combinations thereof; (b) at least one unit that is a tereftaloi portion; Y (c) at least one non-sulfonated unit, which is a 1,2-oxyalkanoxynoxy moiety; (2) one or more coronary units (non-ionic and / or anionic).

Other components used in the detergent compositions may be employed, such as grime suspending agents, abrasive agents, bactericides, mist inhibitors, dyes, foam control agents, corrosion inhibitors and perfumes. Preferably the liquid compositions according to the present invention are in "concentrated form", in which case, the liquid detergent compositions according to the present invention will contain a smaller amount of water »in comparison with conventional liquid detergents. The water level is less than 50%, preferably less than 30% by weight of the detergent compositions. Such concentrated products provide advantages for the consumer »who has a product that can be used in smaller quantities» and for the producer, who has lower shipping costs. Liquid compositions are especially effective when applied directly to soils and stains in a pre-treatment step. The detergent compositions of the present invention can also be used as additive products for detergent. Said additive products are intended to supplement or enhance the operation of conventional detergent compositions. Detergent compositions according to the present invention include compositions that are to be used for the removal of substrates such as fabrics, fibers, hard surfaces, skin, etc., for example., hard surface cleaning compositions (with or without abrasives), laundry detergent compositions. compositions for automatic and non-automatic dishwashers. The following examples are intended to exemplify the compositions of the present invention, but are not necessarily intended to limit the scope of the invention.

EXAMPLE The following liquid detergent composition is prepared. % by weight of the detergent composition FORMULATION A: Component% by weight Alkyl ethoxylated sulfate of CX2_iB 14.50 C12_1B alkyl sulphate 9.00 N-methyl glycol of Z_: L ^ 3.00 Ct2_14 fatty alcohol ethoxylate 1.00 Alkyldramethylhydroxyethylammonium chloride of Ca.at.a. ^ in alkyl 2.50 Fatty acid of Ci2_AJ »4.50 Citrus acid 3.00 Sodium hydroxide 0.73 Monoetano1 amine 6.93 Propanod ol 8.53 Ethanol 5.50 Boric acid 3.50 Sodium xylenesulphate 1.90 Ethoxylated tetraeti lenpentamine (15-1B) 3.00 Terephthalate-based polymer 0.30 Protease (34 g / 1 ) 1.50 L pass D96 / L (100 KUN / g> 0.12 Carezyme (5000 UCEV / g) 0.0B4 Di ethanolamine (sty ene) 0.100 2-he i Idecanol 2.00 Water and minor ingredients Up to 100% It was found that the above liquid detergent composition was very efficient in removing greasy / oily soils, under various conditions of use.

Claims (8)

NOVELTY OF THE INVENTION CLAIMS

1. - A detergent composition »characterized in that it comprises: (a) a lipolytic enzyme and (b) about 1% to 10% of a quaternary ammonium surfactant having the formula:

\ / N / \ R. R. wherein R x and R 2 are individually selected from the group consisting of alkyl of 1 to 4 carbon atoms, hydroxyalkyl of 1 to 4 carbon atoms, benzyl and - (C ^ H ^ O ^ H where x has a value of 2 to about 5. X is an anion and (1) each of R3 and R ^ is an alkyl of 6 to 14 carbon atoms or (2) R.I is an alkyl of 6 to 18 carbon atoms and R ^ is selected from the group consisting of alkyl of 1 to 10 carbon atoms, hydroalkyl of 10 carbon atoms, benzyl and - (C ^ H ^ CD ^ H, where x has a value of 2 to 5. 2 .- The composition according to claim 1 »further characterized in that it comprises about 2% to 7% of the quaternary ammonium surfactant.

3. - The composition according to claim 2 »further characterized in that the surfactant is selected from the group consisting of lauryl chloride 1 trimethylammonium chloride, 1-trimethylammonium chloride, palmiyl chloride, 1-trimethylammonium chloride, cocotrimeti 1-ammonium, cocotrimetilammonium methylsulfate. coconut chloride-dimeti 1-monohydroxyethylammonium. coconut-dimethyl 1-monohydroxy eti 1 ammonium methylsulfate. 1-dimethyl-1-monohydroxy-ethylammonium ester chloride, 1-dimethyl-1-monohydroxy-1-ammonium ester-sulfate, dialkyl-2-dimethyl-ammonium chloride, and mixtures thereof.

4. The composition according to claim 3 »further characterized in that the lipolytic enzyme is a 1-enzyme D96L enzyme.

5. The composition according to the rei indication 4, also characterized because it comprises about 0.05% to 0.5% of the lipolytic enzyme.

6. The composition according to claim 1, further characterized in that the weight ratio of anionic surfactant component to quaternary ammonium surfactant is about 2: 1 to 3.5: 1.

7. The composition according to claim 1 »further characterized in that it additionally comprises about 1% to 20% of a builder material that does not contain citrate or fatty acid.

8. - A detergent composition according to claim 1 »further characterized in that it is in the form! iquida.