MXPA97002728A - Detergent compositions for laundry quecontain lipolitic enzyme and ami - Google Patents

Abstract

The present invention relates to a liquid washing detergent composition, characterized in that it comprises: A) an enzyme lipase at a level of 2 to 20,000 LU / g, B) 1% to 40% of a surfactant, and C) a mine tertiary having the formula R1R2R3N wherein R1 and R2 are C1-C8 alkyl chains or wherein R5 is H or C1-C2 alkyl and x is an integer between 1 and 6; R3 is R4X (CH2) n where x is -NH-, R4 is C4-C12 alkyl, and n is 2 or

Description

COMPOSITIONS DETERGENT PORO flVflNDERIñ THAT CONTAIN ENZIMA LIPOLITICñ AND FLMINñ CHAMBER OF L INVENTION The present invention relates to laundry detergent compositions containing ipolytic enzyme (lipase) and specially selected unary and / or tertiary amines. The compositions provide improved cleanliness of soils and grease / oil stains, particularly when used in a pretreatment laundry cleaning procedure for grease / oil stains.

BACKGROUND OF THE INVENTION The inclusion of lipase in detergent compositions for improved cleaning performance is known, for example, by increasing the removal of dirt and stains with two on the two fabrics. Examples are the Patent of EUR 4,769,173; Patent of EUR 5,069,009; Solici +? D of PCT UO94 / 0357R. No. 4,769,173 discloses a certain class of lipases which consist of fungal lipases from ex Hurnicola lanuginosa together with heavy blotting agents in detergent compositions. An example of a fungal lipase in this patent is the l pass of ex Humicola lanugmosa, available from Hmano ba or the trade name Amano-CE. No. 5,069,809 describes the combination of strong cleaning agents with a lipase enzyme produced by cloning the gene encoding the lipase produced by Humicola lanugmosa and expressing the gene in fispergillus oryzae as a host for use in detergent compositions. No. 94/03578 discloses an enziotic detergent composition containing 10 to 20,000 LU (lipolytic units) per unit of a 11-pass detergent composition that exhibits substantial Jipolitic activity during the main cycle of a washing process. this lipase is selected particularly for its inactivation behavior with diisopropyl fluorophosphate (DFP). Of the lipase enzymes, only the lipase derived from Húmicola lanuginosa and produced in Ospergillus oryzae as a host has found wide application as an additive for fabric washing products, is available under the trade name Lipolase *, from Novo No dis. ñ In order to optimize the stain removal performance of Lipo ase, Nevo Nordis has made a number of variants. 92/05249 describes the vanant D96I of the native lipase of Humicola lanuginosa that improves the efficiency of butter spot regeneration by a factor of 4.4 over the wild-type lipase (enzymes compared in an amount varying from 0.075 to 2.5 rn protein per liter). The ability of the lipase to clean dirt and stains from fabrics present in the typical laundry load is of utmost importance in the evaluation of detergent yield. Unfortunately, the relative ability of the unit to meet various performance criteria among other things depends on the presence of surfactant co-agents. Therefore, for reasons of performance and flexibility, it is desired to make available a surfactant system capable of providing buoyant performance of detergent. The above objective has been met by a surfactant system comprising a co-surfactant selected from the group of primary or tertiary amines. Surprisingly it has been found that the inclusion of specially selected primary or tertiary amines in liquid detergent compositions containing lipolytic enzyme (lipase) substantially increases their ability to rapidly reduce the surface tension of aqueous washing solutions than with oil and grease. Substantial reduction in the interfacial tension of oily and oily soils improves their removal from soiled surfaces and inhibits the redeposition of soils onto substrates. It has also surprisingly been found that liquid detergent compositions containing a lipolytic enzyme and a specially selected primary or tertiary amine show smerge removal of greasy / oily soils particularly when the detergent composition is used in a pretreatment application for stains or oily / oily soils on the fabrics before and together with the washing procedure nor ai of the tolas.

ENZIMA LIPOLITICfl An essential ingredient in the present laundry detergent compositions is a yield increasing amount, preferably from about 0.0001 to 1.0% on an active basis, of a lipase comparable with detergent (lipolytic enzyme). By "detergent compatible" is meant compability with the other ingredients of the composition, particularly detergent surfactants and detergency builders. Liquid detergent compositions, particularly heavy duty liquids, are preferred herein. Any suitable lipase for use in a laundry detergent composition can be used herein. Lipases suitable for use herein include those of bacterial and icotic origin. The lipase of chemically or genetically modified utants is included in the present invention. Suitable bacterial lipases include those produced by pseudomonas, such as Pseudomonas stutzeri OTCC 19. 154, as described in British Patent 1,372,034, incorporated herein by reference. Suitable li rases include those that show a positive immunological cross-reaction with the lipase antibody produced by the microorganism Pseudomonas luorescens IAM 1057. this lipase and a method for its purification has been described in Lapland Patent Application 53-2 (1407 , open to the public on February 4, 70, which is incorporated herein by reference.This lipase is available under the trade name Lipase P "Amano", hereinafter referred to as "flrnano-P". a positive cross-immunological reaction with Omno-P antibody, using the normal and well known mmunodi fusion method in accordance with Ouchterlony (chart, Med. Sean., 133, pages 76-79 (1950)). and a method for its immunological cross-reaction, with Oinano-P, is also described in USPatent 4,707,291, Tho et al, issued November 17, 1987, incorporated herein by reference. but they are the Ornano lipase ~ P, the lipase ex Pseudomonas fra í FERM P 1339 (available under the tradename flrnano-B), the lipase ex Pseudornonas nitroreducens v r. 1 ipolyticum FERM P 1338 (available under the trade name FLmano-OFS), lipases ex Chromobacter vi cosum, v.gr-, Chromobacter viscosum var. lipoly i curn NRRLB 3673, and also li raisins Chrornobact er vi scosurn and lipasas ex Pseudomonas gladioli. Other lipases of interest are the lipases Amano AKG and Bacillis Sp. Suitable fungal lipases include those that are produced by Humicola lanuginosa and Ther omyces lanugmosus. The most preferred is the lipase obtained by cloning the Hu icola lanuginosa gene and expressing the gene in Aspergillus oryzae as described e > In the Request for European Patent 0 258 068, incorporated herein by reference, commercially available under the trade name I. ípola eTM "The highly preferred lipases are the lipolytic enzyme variant D96L from the native lipase derived from Hum ícela lanuginosa as described in EUR Series No. 08 / 341,826. Preferably, strain DSM 4106 from Humic la Lanuginosa is used. this enzyme is incorporated in the composition according to the invention at a level of 50LU to 8500LU per liter of solution d elavate. Preferably, the D96L variant is present at a level of 100LU to 7500LU per liter of wash solution. Nuy preferably at a level of 150 LU to 5000 LU per liter of wash solution. By lipolytic enzyme variant D96I. is understood the vanant of lipase co or is described in the patent application UO 92/05249 viz. wherein the residue of aspartate acid (D) of native lipase ex H? icola lanugmosa in position 96 is changed to Leucina (L). According to the nomenclature, said substitution of aspartic acid to Leucine in position 96 is shown as; D96L. It has been found that the lipolytic enzyme variant D96L is particularly preferred due to the characteristics of t >odor associated with the combined use of amines. From about 2 to approximately 20,000, preferably from 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 unit of lipase is that amount of lPaza that produces 1 jj of butyric acid titrable per minute at a set pH value, where the pH is 7.0, the temperature is 30 ° C and the substrate is an emulsion of tpbutipna, and gum arabic, in the presence of Ca ++ and NaCl in the phosphate pH regulator.

LO OMINO The amides as they are used herein refer to primary or tertiary amines which are believed to form a complex ion with the ammonium surfactant agent and where the length of the carbon chain of the group at is equal to or greater than 0 & . Primary amines suitable for use herein include amines of "Jad" conformation with the formula R1NH2 wherein Ri is C6-C12, preferably an alkyl chain of Ce-Cio or R "X (CH2) n, X is -0-, - C (0) NH- or -NH-, R "is a C6-C12 alkyl chain, n is between 1 to 5, preferably 3. The alkyl chains of Ri can be straight or branched and can be interrupted until with 12, preferably less than 5 portions of packed oxide. Preferred amines according to the formula of the present invention are n-alkylammers. Suitable amines to be used herein can be selected from l-hexylamin, 1-octilamin, 1 -decylalanine and lauplarnine. Other preferred primary products include oxypropyl sheet of Cß-Cio, C i lox i ropí la a, 2-et? Lhex? the ipropilama na, lauplami do propí lamina and ami opropí lamina. Tertiary amines suitable for use herein include tertiary amines having the formula R1R2R3N wherein R1 and R2 Ci-C alkyl chains or Rs - (CH2-CH-0) R3 H is either an alkyl chain of C6-C12, preferably Ce -Cio vo R3 is R «XfCH2) n, whereby X is -0-, -C (0) NH- or -NH-, R¿ is C4-C12, n is in + re 1 and 5, preferably 2-3. R 5 is II or C 1 -C 2 alkyl and x is between 1 and 6. R 3 and R < 4 can be linear or branched, the alkyl chains of R3 can be interrupted with up to 12, preferably less than 5, portions of ethylene oxide. Preferred tertiary amines are R 1 R 2 R 3 N wherein R 1 is an alkyl chain of 6-C 12, R 2 and R 3 are C 1 -C 3 alkyl or Rs - (CH 2 - 0H- -0) "H wherein Rs is H or CH 3 and x - 1-2. Also preferred are amidoamines of the formula: R1 - C - NH - (CH2> n - N - IR2> 2 where Ri is Cg - Ci2 alkyl; n is 2-4, preferably n is 3; R2 and R3 is C-C, The most preferred amines of the present invention include l-oc ila aa, 1-hex? lamina, 1- deci Lamina, 1-dodecylarnma, oxiprOpi-a C8-C10, N-coco-1- 3d? Am? No? Clothing, cocoal? Ildirnetilarn? Na, lauryldimethylamine, ur? Lb? (Water Darní na, cocob? S (hydroxyethyl) amine, lauryl amine? 2 propoxylated moles, octyl ma 2 propoxylated moles, laurilarní dopropildi eti laiiu na, arm dopropí Idirnetilarní of C8-10 and ami dopropí Id irnet 1 sheet of C O. most of the preferred amines to be used in the compositions herein are 1 -he 1 sheet, 1 -o alamin, 1 -decal ana, 1- dodecalama A. Especially desirable are n-dodecildainet ílarnma and bihidroxiet ícocoalquilarní and eleila ma 7 times otoxalada, lauplarnidopropa lamina and cocoarnidopropílami na.

PROCEDURE OF LOVODO AND PRETROT MIENT OF FABRICS The present invention also provides a method for washing fabrics soiled with stains or oily / oily dirt. 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 generally occurs under conditions of agitation. The agitation is preferably provided in a washing machine for good cleaning. The washing is preferably followed by drying the wet cloth in a conventional 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, most preferably from about 1000 to 3000 ppin. The detergent compositions herein can also be used to re-tie fabrics containing greasy / oily soils or stains before washing said fabrics using conventional aqueous wash solutions. Said pretreatment involves the application of highly concentrated forms of the detergent compositions herein directly on greasy or oily stains or dirt on the fabric to be cleaned. For the compositions of the present in liquid form, this usually involves the direct application of the composition as it is for the stain / dirt on the fabric. Pretreatment of oily / oily stains or soils will generally occur for a period of about 30 seconds to 24 hours before washing a pretreated soiled / stained substrate in a conventional manner. Most preferably, the pretreatment times will vary from about 1 to 180 minutes.

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 list of ammonia, non-ionic, follicle and suitepome classes, and species of these surfactants is given in US Patent 3,664,961 issued to Norris on May 23, 1972. Preferred ammonium surfactants include the alkyl sulfate surfactants of the same and are water soluble salts or acids of the formula ROSO3M wherein R is preferably a Cι-C24 hydrocarbyl, preferably an alkyl or hydroxyalkyl having an alkyl component of Cι-Ciß, most preferably a C 12 -C 15 alkyl or hydroxyalkyl, and M is H or a cation, e.g., an alkali metal cation (e.g., sodium, potassium, lithium), or substituted ammonium or ammonium (v. g., Rethyl-, di-ethyl-, and trimethyl-a-cations or quaternary ammonium cations such as tetrarnetillarylonium cations and dirnetri Ipipep dinium and quaternary ammonium cations derived from alkylamines such as ethylamine, diethylamine, tetylamine and mixtures thereof And yes illary). Highly preferred ammonium surfactants include alkoxylated alkylsultoxylated surfactants thereof are water soluble or acidic salts of the formula R0 (R) mS031 wherein R is an unsubstituted C10-24 alkyl or hydroxyl group which it has a C10-C24 alkyl component, preferably an alkyl or hydroxyl which is C12-O18, preferably C12-C15 alkyl or hydroxyalkyl, A is an ethoxy or propoxy unit, rn is greater than zero, typically between about 0.5 and about 6, most preferably between about 0.5 and about 3, and M is H or a cation which may be, for example, a metal cation (e.g., sodium, potassium, lithium, calcium, magnesium, etc.), ammonium or substituted ammonium cation. Ethoxylated alkylsuiphates as well as propoxylated alkylsulphonates are also contemplated here. Specific examples of substituted ammonium cations include rnetii-, di-, di-, tri- and ammonium cations and quaternary ammonium cations such as ar- daryl anmonium and dirnethyl piperidinium cations and those derived from alkylanes such as ethylamine, diethylamine, t petilarnin, mixtures thereof, and the like. Exemplary surfactants are polyethoxylated C12-C1S alkylsulfate (1.0) (C12 -C15 E (1.0) M), C12-C15 alkyl ethoxylate (2.25) (C12 -CisEi 2.25) M), alkylsui C12-C15 polyethoxylated fate (3.0) (C12-C? sE (.0) M) and polyethoxylated Ci2-C? alkyl sulfate (4.0) (Ci2-C? sE (4.0) M), where M is selected conveniently sodium and potassium. Other ammonium surfactants suitable for use herein are alkyl ether sulfonate surfactants including linear esters of C8-C20 carboxylic acids, ie, fatty acids) which are sulfonated with gaseous SO3 according to "The 'j'nal of the American Oil Che ists Socaety ", 52 (1975), pp. 323-329. Suitable starting materials include natural fatty substances such as are derived from tallow, palm oil, etc. The preferred alkyl ether sulphonate surfactant, especially for laundry applications, comprises alkyl ether sulphonate surfactants of the structural formula of: wherein R 3 is C 1 -C 20 hydrocarbyl and preferably an alkyl, or coation thereof R * is Ci-Cd hydrocarbyl, preferably an alkyl, or coation thereof, and M is a cation forming a water-soluble al with the alkyl ether sulfonate. Suitable salt-forming cations include metals such as sodium, potassium and lithium, and substituted or unsubstituted ammonium cations, such as ammonium methanol, diethanolamine and triethanolamine.

Preferably, R3 is a C10-C16 alkyl, and R * is methyl, ethyl or isopropyl. Especially preferred are the rnethyl ester sulfates wherein R3 is C10-C16 alkyl. Other ionic surfactants useful for detersive purposes can also be included in the laundry detergent compositions of the present invention. These may include salts (including, for example, salts of sodium, potassium, ammonium and substituted ammonium, such as salts of mono, di and tpetanolane) soap linear C9-Q20 alkylbenzenesulphonates, primary or secondary aralnes of C8-C22 olef sulphonates of C8-C 4, sulphonated polycarboxylic acids prepared by sulfonation of the pyrolyzed product of alkaline earth metal citrates, as described in British Patent Specification No. 1,082,179, to the C8-C24 methyl polyglycol ether sulphates (containing up to 10 moles of ethylone oxide); llk li-rol sulfonates, acylgl ice rol fatty ulfonates, oleyl 1 fatty alcohols, ethersulfates of alkyl phenolethylene oxide, paraf sulphonates, the phosphates, isethionates such as acyl bisonates, N-acetic acid, alkyl succinates and sulfosuccmatoe, rnonoesters of sulfosuccinates (especially saturated and unsaturated C 12 -C 18 monomers) and sulosuccinate diesters (especially saturated and saturated C 6 -C 12 -adiesters), alkylpolysaccharide sulfates such as the compounds described below), and alkylpolyethoxycarboxylates such as those of the formula RO (CH2CH2?) -CH2COO-M + wherein R is an alkyl of Ce-C22, k is an integer from 0 to 10 and M is a soluble salt caponator cation. Resin acids and hydrogenated ream acids are also suitable, such as collodromic acids, hydrogenated rosin acids and ream acids and hydrogenated rsin acids present in or derived from wood oil. Additional examples are described in "Surface-Active Agent and Detergents" (Vol. I and TT by Sch? Artz, Perry and Berch). A variety of such surfactant agents are also described generically in U.S. Pat. 3,929,678, issued December 30, 1975 to Laughlin, and others in Column 23, line 58 to Column 29, line 23 (which is incorporated herein by reference). When included herein, 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 said ammonium surfactants. One class of nonionic surfactants used in the present invention are condensates of ethane oxide with a hydrophobic portion to provide a surfactant having an average hydrophilic-lipophilic balance (EHL) in the range of 8 to 17, preferably from 9.5 to 14, most preferably from 12 to 14. The hydrophobic (lipophilic) portion may be aliphatic or aromatic in nature and the length of the polyoxyethylene group that is condensed with any particular hydrophobic group may be easily adjusted to produce a compound soluble in water having the degree of equilibrium between the hydrophilic and hydrophilic elements. Especially preferred nonionic surfactants of this type are ethoxylated C9-C15 primary alcohols containing 3-12 moles of ethylene oxide per mole of alcohol, particularly primary C12-C15 alcohols containing 5-6 moles. 8 moles of ethylene oxide per mole of alcohol. Another class of non-linear surfactants comprises alky1-poly-glucoside compounds of the general formula wherein Z is a portion derived from glucose; R is a saturated hydrophobic piquilo group containing 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 glucosides. Compounds of this type and their use in detergents are described in EP-B 0 070 077, 0 075 996 and 0 094 118. Also suitable as non-ionic surfactants are the polyurethane fatty acid amide surfactants of the forrn. The R2 - C N - Z, or II Il where Ri is H, or R1 is C1-4 hydrocarbyl, 2 - hydroxyethyl, 2 - hydroxyl? propyl or a mixture thereof, R2 is C5-31 hydrocarbyl, and Z is a polyhydroxycarboxylane < It has a linear hydrocarbyl chain with at least 3 hydroxyls directly connected to the chain, or an alkoxylated derivative of the mimes. Preferably, R1 is methyl, 2 is a straight alkyl or alkenyl chain of C? -? S such co cocoalkyl or mixtures thereof, and Z is derived from a reducing sugar such as glucose, fructose, maltose, lactose, in a reaction of reductive animation. The highly preferred nonionics are amine oxide surfactants. The compositions of the present invention may comprise amine oxide according to the general formula T: Rl (F0) x (P0) and (B0) x (0) (CH2R ') 2-qH20 (I) In general, it can be seen that structure (I) provides a long chain portion R * (EO) (PO) (BO) and two short chain portions CH2R '. R 'is preferably selected from hydrogen, methyl and -CH2OH. In general, R1 is a primary or branched hydrocarbyl portion which may be saturated or unsaturated, preferably, R1 is a primary alkyl portion. When x + y + z - 0, R 1 is a hydrocarbyl portion having a chain length of about 8 to about 18. When x + y + z is different from 0, R 1 can be a little longer, having a length of chain on the scale of C12-C24. The general formula also encompasses amine oxides wherein x + y + z-0, Rl-Cβ-Ciß, R'-H and q-0-2, preferably 2. These amine oxides are illustrated by alkyldi ethylamide C12-C14, hexadecyldirnetilarynin oxide, octadeca oxide lamina and its hydrates, especially hydrates as described in the FUA Patents 5,075,501 and 5,071,594, incorporated herein by reference. The motion also comprises arc oxides wherein x + y + z is different from zero, especially x + y + z is from 1 to approximately 10, R 1 is a primary alkyl group containing from 8 to 24 carbon atoms, 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, most preferably from about 3e 2 to about 4; EO represents ethyleneoxy; PO represents propyleneoxy, - and BO represents butyleneoxy. Said amine oxides can be prepared by conventional synthetic methods, eg, by the reaction of alkyl ethoxysulfates with dirnet 1 followed by oxidation of the ethoxylated amine with hydrogen peroxide. The highly preferred amine oxides herein are solids at room temperature, very preferably have melting points on the scale of 30 ° C to 90 ° C. The amine oxides suitable for use herein are commercially made by a number of suppliers, including Al'zo, Ohernie, Ethyl Corp-. V Procter to Gamble. See the McCu cheon 's compilation and the Ki r * -Oth er review article for alternate amine oxide manufacturers. The most preferably available amine oxides available are ADMOX 16 and ADRIOX 18 dlhydrate solid, RDMOX 12 and especially ADflOX 14 from Ethyl Corp. Preferred embodiments include hexadecyl dimethyl oxide dihydrate, dodecyldirnethylaminine dihydrate oxide, octadecyldirnet amine dihydrate oxide, hexadecyltra s (et? lenox?) d? rnet? larna oxide and tet radecyl dimethiamine dihydrate oxide. Although in some of the preferred modalities R '~ H, there is a certain latitude with respect to having R 'slightly greater than H. Specifically, the invention also encompasses embodiments wherein R' = CH2OH, such as hexadecylbis (2-ludroxyethyl) amine oxide, sebob's oxide ( 2-hydroxyethanol), stearic acid (2-hydroxyethyl) arnine oxide and oleic acid oxide (2-hydroxyethyl) amine, dodecyldimidiamamine dihydrate oxide. When included herein, the laundry detergent compositions of the present invention typically comprise nonionic surfactants in the weight ratio of ammonium surfactant to nonionic surfactant of from 6: 1 to 1: 3, preferably 5%. : 1 to 2: 1. Suitable cationic detersive surfactants for use in the laundry detergent compositions of the present invention are those having a long chain hydrocarbyl group. Examples of such cationic surfactants include the ammonium surfactants such as alkyldimethyl arnide halide, and those surfactants which have the formula: wherein R2 in an alkyl or alkylbenzyl group having from about 8 to about 18 carbon atoms in the alkyl chain, each R3 is selected from the group which? consists of -CH2CH2-, -CH2CH (CH3) -, ~ CH2CH (CH2OH) ~, -CH2CH2CH2-, and mixtures of the rings; each R * is selected from the group consisting of C1-C4 alkyl, C1-C4 hydroxyalkyl, benzyl ring structures formed by the two group R4, -CH2CH0H-CH0HC0R6CH0HCH20H wherein R6 is any hexose or hexose polymer which it has a molecular weight less than about 1000, and hydrogen when yy is not 0; R5 is the same as R * or is an alkyl chain wherein the total number of carbon atoms of R2 plus RS is not greater than about 18; each y is from 0 to approximately 10 and the sum of the values y is from 0 to approximately 15; and X is any comparable amount. The preferred cationic surfactants are the water-soluble quaternary ammonium compounds useful in the present composition having the formula: wherein Ri is Cs-Ci6 alkyl, each of R2, R3 and R4 is independently C1-C4 alkyl, Ci-C¿ hydroxyalkyl, benzyl and - (C2HAO) XH wherein x has the value of 1 to 5 , and x is an ani. No more than R2, R3, or 4 must be benzyl. The preferred alkyl chain length for Ri is C 12 -C 15 particularly where the alkyl group is a mixture of alkyl lengths derived from coconut or palm kernel fat or is synthetically derived by accumulation of olefin or synthesis of OXO alcohols . Preferred groups for R2R3 and R4 are methyl and hydroxyethyl groups and the anion x can be selected from halide, rnetosulfate, acetate and fos oions. Examples of quaternary ammonium compounds of the formula (1) to be used herein are: cocot chloride or bromide prnet 1 larna or; cobalt chloride or bromide iodide hydroxylamine; decile chloride riet 1 larna or; decildimethylhydroxyethyl ammonium chloride or bromide; chloride or dimethylhy droxietiia onium bromide of Ci2 ~ Cis; cocodimet hydrochloride 11-hydroxyethylammonium chloride or bromide; rni-ristyl ristyl sulfate, rirnet to ammonium, laupldimethylbenzilainonium chloride or bromide; lauryl-di-methyl-ketoxy-ammonium chloride or bromide; colma esters (compounds of the formula (i) wherein Ri is CH2-0 ~ C (0) -alkyl of C12-14 R2R3R4 are methyl). Other cationic surfactants useful herein are also described in the U.S. Patent. 4,228,044, Carnbre, issued October 14, 1980. When included herein, the laundry detergent compositions of the present invention typically comprise from 0.5% to about 5%, preferably from about 1% to about 3% by weight of said cationic surfactants. The compositions according to the present invention may further comprise a detergent reduction system. Any conventional detergent improving system is suitable for use here including aluminosilicate materials, silicates, polycarboxylates and fatty acids, materials such as ethylenediamine tetraacetate, metal ion sequestrants such as ammopoliphosphonates, particularly ethylenediaminetetranethane phosphonic acid and dietetic acid not -pentamethylene phosphom. Although less preferred for obvious environmental reasons, phosphate detergent builders can also be used here. Polycarboxy builder detergents or suitable for use herein include citric acid, preferably in the form of a water soluble salt, succinic acid derivatives of the formula R-CH (C0OH) CH2 (C0OH) wherein R is alkyl or alkene of C10-C20, preferably C12-16, or when R can be substituted with hydroxyl, sulfo sulphoxy or sulphone substituents. Specific examples include lauplsuccmate, my risti Lsuccmato, pal itiisuccinate, 2-dodecenylsuccinate, 2-tetradecemlsucc? born. Succ ato builders are preferably used in the form of their water soluble salts, including salts of sodium, potassium, ammonium and alkanol irnonio. Other suitable polycarboxylates are the oxodisuccinates and mixtures of onosucci co tartrate and tartrate disuccide as described in US 4,663,071. Especially for the liquid form herein, the fatty acid detergents which are used herein are saturated or saturated CIO-18 fatty acids, as well as the corresponding soaps. The 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 dodecetic acid and citric acid. The detergency builder salts are usually included in amounts of 3% to 50% by weight of the composition, preferably 5% to 30% and very generally 5% to 25% by weight.

OPTIONAL DETERGENT INGREDIENTS The preferred detergent compositions of the present invention may further comprise one or more enzains that provide cleaning performance and / or fabric care benefits. Said enzymes include enzymes selected from cellulases, hernical cellulases, peroxidase, proteases, glucoalases, amylases, Lipaeas, cutmases, pectmases, xylanases, reductases, oxidases, phenoloxidases, lipoxygenases, lignmases, pullulanases, tanases, pentosanas, rnalanases, β-glucanases , Arab osidases or mixtures thereof. A preferred combination is a detergent composition having a combination of conventional applicable enzymes such as protease, anilase, lipase, cut-off and / or cellulase together with vanatin lipolytic enzyme D96L at a level of 50 LU to 8500 LU per liter of solution of washing. Cellulases useful in the present invention include bacterial or fungal cellulases. Preferably, they have an optimum pH between 5 and 9.5. Suitable cellulases are described in the U.S. Patent. 4,435,307, Barbesgoard et al., Which describes cellulases of fungi produced from Humicola insolens. Suitable cellulases are also described in GB-A-2,075,028; GB-A-2,095,275 and DE-OS-2,247,832. Examples of said cellulases are cellulases produced by a strain of Hu icola insolens (Hurnicola grísea v w therrnoidea), particularly the strain Humicola DSM 1800.

Other suitable cellulases are cellulases originated from Hurnicola msolens having a molecular weight of approximately 50KDa, an isoelectric point of 5.5 and containing 415 amino acids. Particularly suitable cellulases are cellulases that have color care benefits. Examples of said cellulases are cellulases described in European Patent Application No. 91202879.2, filed on November 6, 1991 (Novo). The peroxidase enzymes are used in combination with oxygen sources, e.g., percarbonate, perborate, persulfate, hydrogen peroxide, etc. They are used for "bleaching in solution", ie to avoid the transfer of dye or pigments removed from substrates during washing operations to other substrates in the washing solution. Peroxidase enzymes are known in the art, and include, for example, horseradish peroxidase, ligmnase and halogenoperoxidase such as chlorine and brom peroxidase. Peroxidase-containing detergent compositions are described, for example, in the PCT International Application UO 89/099813 and in European Patent Application EP No. 91202882.6, filed on November 6, 1991. Said cellulases and / or peroxidases are usually they incorporate in the detergent composition at levels of 0.0001% to 2% of active enzyme by weight of the detergent composition. Preferred commercially available protease enzymes include those sold under the names t. Alcaner, Sav ase, Primase, Durazy and Esperase by Novo Nordis A / S (Denmarl), those sold under the Maxatase, Maxacal and Maxapem norms by Gist -Brocades, those sold by Genencor International and those sold under the trade name Opticlean and Optirnase by Solvay Enzy is. Also, the proteases described in the copending application of the inventors of the present USSN 08/136, 797 may be included in the detergent composition of the invention. 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 of the present invention referred to as a "Protease D" is a variant of carbonylhydrolase having an amino acid sequence not found in nature, which is derived from a carbonylhydro sa precursor by substituting the amino acid residue for a different amino acid in a position in said carbonylhydrolase equivalent to the position +76, preferably also in combination with one or more positions of amino acid residues equivalent to those selected from the group consisting of +99, +101, +103, +104, +107, +123, +27, +105, + L09, +126, +128, +135, +156, +166, +195, +197, +204, + 206, +210, +216, ^ 217, +218, +222, «-260, +265, and / or +274 according to the subtilisma number of Bac llus arnyloliquefaciens, as described in the Patent Application concurrently filed by A. Baec et al. entitled "Protease-Contaimng Cleamng Co positions" which has an EUA Series No. 08 / 322,676, filed on October 13, 1994, which is hereby incorporated by reference in its entirety. TarnbLen adndas are ls cut handles CEC 3.1.1.50] that can be considered as a special type of lipase, namely li raisins that do not require interfacial activation. The addition of cut masses for detergent compositions have been described in v.gr1., IO-A-88/09367 (Genencor). The iipases and / or cut masses are usually incorporated in the detergent composition at levels of 0.0001% to 2% active enzyme by weight of the detergent composition. Arm lasas (R and / or ß) can be included to remove carbohydrate-based stains. Suitable alasics are Terrnarnyi® (Novo NordislO, Fungamyl® and BanR (novo Nordisk) .The aforementioned enzymes can be of any suitable origin, such as vegetable, animal, bacterial, fungal and yeast, said enzymes are normally incorporated into the composition detergent at levels of 0.0001% to 2% active enzyme by weight of the detergent composition.Other suitable detergent ingredients that can be added are enzyme oxidation scavengers which are described in co-pending European Patent Application 92 0018 filed 31 January 1992. Examples of said enzyme oxidation scavengers are etexilated tetraethylene pollamines.

A preferred component to be used 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 conventionally copolymers or terpolymers of terephthalic acid with ethylene glycol and / or propylene glycol units in various arrangements. Examples of said polymers are described in the Pa + ents of E.U.A. Commonly assigned Nos. 4116885 and 4711730 and in European Published Patent Application No. 0 272 033. A particular preferred polymer in accordance with EP-A-0 272 033 has the formul (CH3 (PEG) A3)? 7S (P0H ) 0.2SCT-P0) 2.8 (T ~ PEG) 0.4] T (P0- H) O.2S ((PEOÍ3CH3)? 75 where PEG is - (OC2H4) 0-, PO is (OC3H6O) and T is ( They are also very useful on polyesters such as random copolymers of di-ethyl terephthalate, dimethyl-sulphonophthalate, ethylene glycol and 1-2-propanediol, the end groups consisting mainly of sulfobenzoate and secondarily of onosters of ethylene glycol and / or propanediol. is to obtain a polymer blocked at both ends by sulfobenzoate groups, "primarily", in the present context most of said copolymers will be blocked at the ends by sulfobenzoate groups, however, some copolymers will be less completely blocked, and therefore its extreme groups may consist of mono esters of ethylene glycol and / or propanol-2-diol, of the same consists "secondarily" of said species. The polyesters selected herein contain about 46% by weight of dimethylterephthalic acid, about 16% by weight of propane-1,2-diol, about 10% by weight of ethylene glycol, about 13% by weight of dirnemisulfobenzoic acid and about 15% by weight of acid sulfoisophthalic, 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 soil release polymers include oligomeric esters such as described in the co-pending US Patent Application. No. 08/355/938 filed on December 14, 1994. Said esters comprise: (1) a base structure copying (a) at least one unit selected from the group consisting of dihydroxy or polyhydroxy sulfonate, a unit which it is at least tri functional by which the ester linkages are formed resulting in a branched oligorne base structure, and combinations thereof; (b) at least one unit that is a terefta1oi 1o portion; (c) at least one unsubstituted unit which is a 1,2-oxyalkenyloxy portion; (2) one or more blocking units (non-ionic and / or ammonia).

The preferred ester molecules have the following structure (For-rnu i a A): where R = H, CH3 in relation of 1.7: 1, which is a plo axis of an oligomer having three SE3 blocking units, a SEG unit, and a glycerin unit incorporated in the structure of the oligomer. Other components used in detergent compositions may be employed, such as soil suspending agents, abrasives, bactericides, rinse 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 a case, the liquid detergent compositions in accordance with the present invention will contain a lower amount of water, compared to 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 to the consumer, who has a product that can be used in lower quantities and to the producer, who has lower shipping costs. 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. Said additive products complement or increase the performance of conventional detergent compositions. The detergent compositions according to the present invention include compositions to be used for cleaning substrates., such as fabrics, fibers, hard surfaces, skin, etc., for example surface cleaning compositions last (with or without abrasives), laundry detergent compositions, automatic and non-automatic dishwashing compositions. The following examples illustrate compositions of the present invention, but do not necessarily limit the scope of the invention.

EXAMPLES EXAMPLE 1 The following liquid detergent compositions are made:% by weight of the detergent compositions A B C D E Linear alkylbenzene-1-alkyl sulfate or C12-C1S-2 complex Amidopropyla of Cß ~ C? O 2 2 2 2 1 Alkyldi ethylamide oxide of C12-C14 - - 2 C12-C15 alkylsulfate ~ 17 12 7 8 N-rnetilgl ucanide of C12-C1; 5 4 4 3 Fatty alcohol of C12-O14 bundled ethoxy 12 6 1 1 1 Fatty acid of C12-C18 11 11 4 4 3 Layered citric anhydrous 5 1 3 3 2 Acid diet lentpaminopenta-rnetilenfosfómco 1 1 1 1 0.5 Monoethanolamine 11 8 5 5 2 Sodium hydroxide 1 1 2.5 1 1.5 Pr-opanediol 12.7 14.5 13.1 10.0 8 Ethanol 1.8 1.8 4.7 5.4 l flrnilasa (300 KNU / g) 0.1 0.1 0.1 0.1 0.1 Lipase D96 / L (lOOKNU / g) 0.15 0.15 0.15 0.15 0.15 Protease (34g / l) 0.5 0.5 0.5 0.5 0.5 Ende- A (5000 CEVU / g) 0.05 0.05 0.05 0.05 0.05 Carezy e (5000 CEVU / g) 0.09 0.09 0.09 0.09 0.09 Polymer based on terephthalate 0.15 0.15 - - -Ester olí gornepco (Formula A) - - 0.17 0.07 0.07 Boric laughing 2.4 2.4 2.8 2.8 2.4 Xyl n sodium sulfonate - - 3 - - DC 32250 0.03 0.04 0.04 0.03 0.03 2-but? L-octanol 1 1 1 1 1 Branched Silicon 0.3 0.3 0.3 0.3 0.3 Water and minor components up to 100% EXAMPLE 2 Ingredient R B C% in% in% in weight w or weight C12-15 alkyl ethoxylated alkyl sulfate (2.5) 13.50 13.70 9.40 C12-15 alkyl sulfate 4.50 4.00 3.10 Ethanol 3.50 2.64 2.18 Monoethanol ina 1.00 0.75 1.00 Amidopropyl 1 di-ethylene diamine from CÍO 1.30 1.30 1.30 Propanediol 7.50 7.50 3.20 Alkyl C1 - 1 pol i ethox 11 ado (9) 2.00 0.63 1.00 Amide of alkyl lucosa of C12-14 4.50 3.35 2.00 Fatty acid of C12-14 2.00 3.50 1.00 Lipotasa 0.18 0.18 0.10 Sodium toluene sulfonate 2.50 2.25 2. 5 Citric acid 3.00 2.65 1.80 Borax 3.50 3.50 --- Sodium hydroxide (at a pH of 8.0) 2.95 to 2.10 to 2.07? pH = B., 0 pH = 7. , 6 pH = 8., 0 Tetr-aet iienpenta ina ettoxia (15-18) 1.18 1.18 1.00 Water, perfume, enzymes, polymers to stop dirt, 100% 100% 100% suppressant and other optional ingredients EXAMPLE 3 Ingredient A B C D% in% in% in% by weight weight in weight C12-15 Alkyl Sulphate Potato (3) 13.70 13.70 13.70 13.70 C12-15 Alkyl Sulfate 4.00 4.00 4.00 4.00 Et ol 2.64 2.64 2.64 2.64 Mono-ethanol 0.75 0.75 0.75 0.75 Amidopropa 1 dimethylane of C12 1.30 1.30 1.30 1.30 Arnidopropildirnetiiarní na of CIO - 1.30 B? S (hydroxy? L sheet of C12 - - 1.3 1.3 Octilarin Propanodiol 7.50 7.50 7.50 7.50 C12-13 alkyl polyethoxylated (9) 0.63 0.63 0.63 0.63 Alkylamine glucose C12-14 3.35 3.35 3.35 3.35 Fatty acid C12--16 3.50 3.50 3.50 3.50 Lipol sa 0.12 0.12 0.12 0.12 Sodium toluene sulfonate 2.25 2.25 2.25 2.25 Citric acid 2.65 2.65 2.65 2.65 Borax 3.50 3.50 3.50 3.50 Sodium hydroxide 2.1 to 2.1 a 2.1 a 2.1 a pH = 7.B pH = 7.6 pH = 7.6 pH = 7.6 Ethoxylated ethoxylated ethoxylate (15-18) 1.18 1.18 1.18 1.18 Water, perfume, enzymes, for para-pair 100% releasing polymers 100% 100% 100% dirt, foam suppressant and other optional ingredients The above liquid detergent compositions of the Examples 1, 2 and 3 were found to be very efficient for the removal of greasy / oily soils under vain conditions of use, particularly when used in a "pull" procedure.

Claims (9)

3 b NOVEDRD OF THE INVENTION CLAIMS

1. A detergent composition comprising a lipolytic enzyme, characterized in that said detergent composition further comprises an amine selected from a) primary amines according to the formula R1NH2 wherein Ri is a C6-C12 alkyl chain, preferably Cs-Cio R4X ( CH2) n ', X is -0 -, - C (0) NH- or -NH-, R "is an alkyl chain of Ce -C12, r > it is between 1 and 5; b) tertiary amines having the formula a) R 1 R 2 R 3 N wherein Ri and R 2 are Ci -e chains or Ci -e or Rs I - (CH 2 - 0H- -0) XH R 3 is either C 6 -C 12 or R 3 is R "X (CH2) n ', whereby X is -0-, -C (0) NH_ or -NH-, R4 is C4 -C12, n is between 1 and 5, Rs is H or C1-alkyl C2 and x is between 1 and 6; li) R1R2R3N wherein Ri is an alkyl chain of O6-C12, R2 and are Ci-C3 alkyl or Rs - (CH2 -CH-0) "H wherein Rs is H or CH3 and x = 1- 2; 111) 0 R 1 -C-NH- (CH 2) n -N- (R 2> wherein Ri is C 6 -C 12 alkyl, r 2 is 2-4, preferably n is 3, R 2 and R 3 is C1-O4; c) mixtures of said primary and tertiary amines.

2. A liquid detergent composition according to claim 1, further characterized in that said primary amine is selected from n-alkylamines, Cs-CiO oxytopylaryl / octyloxypropyl larnin, 2-ethylhexyl- or propyl-larone, iauplamidopropylamine and amidopropyla ina.

3. A liquid detergent composition according to claim 2, further characterized in that said n-alkylarynin is l-octylamine.

4. A liquid detergent composition according to claim 1, further characterized in that the amine is selected from the tertiary amine of formula i) whereby R3 is an alkyl chain of Ce-Cio and so n is 2 or 3. A detergent composition according to claim 1, further characterized in that the arn is a tertiary amine of the formula ni) wherein n is 3. 6. A detergent composition according to claim 1-5, further characterized in that the political enzyme is lipolytic enzyme T) 96L 7. A liquid detergent composition according to claim 1-6, further characterized in that it comprises other conventional surfactants, builders, enzymes and other detergent ingredients. 8. A detergent composition according to claim 1-7, further characterized in that it is in liquid form. 9. The use of a liquid detergent composition according to claim 8 for fabric treatment. O P96 / 383F