HUT78084A - Laundry detergent compositions containing lipolytic enzyme and amines - Google Patents

Description

The present invention relates to laundry detergent compositions comprising a lipolytic (lipase) enzyme and specially selected primary and / or tertiary amines. The compositions provide better cleaning of grease / oil contaminants and stains, especially when applied to greasy / oily contaminated stains in a pre-treatment washing process.

It is known to incorporate lipase into detergent compositions to improve cleaning performance, for example, to remove triglyceride-containing impurities and stains from fabrics. Examples are U.S.P. 4,769,173; U. U.S. Patent 5,069,809; International Patent Publication No. WO94 / 03578.

U.S.P. U.S. Patent No. 4,769,173 discloses certain lipase groups consisting of fungal lipases derived from Humicola lanuginosa together with strong bleaching agents in detergent compositions. In this patent, for example, a fungal lipase is available from Amano under the trademark Amano-CE, obtained from Humicola lanuginosa.

U.S.P. U.S. Patent 5,069,809 discloses a combination of strong bleaching agents for use in the preparation of detergents by cloning a gene encoding a lipase produced by Humicola lanuginosa and for use in a lipase enzyme expressed in Aspergillus oryzae as a host. WO 94/03578 discloses an enzymatic detergent composition comprising 10 to 20000 LU (lipolytic units) / g of detergent composition having a significant lipolytic activity during the main cycle of the washing process. This lipase was typically selected for its inactivation properties with diisopropyl fluorophosphate (DFP).

Of the lipase enzymes, only lipase derived from Humicola lanuginosa and expressed in Aspergillus oryzae as host has so far been widely used. It is available under the trade name Lipolase® from Novo Nordisk.

To optimize Lipolase's stain removal performance, Novo Nordisk has produced several variants. WO

International Patent Publication No. 92/05249 discloses that the D96L variant of native Humicola lanuginosa lipase enhances the removal efficiency of wild-type lipase-type pig fat (4.4 enzymes in the range of 0.075-2.5 mg protein / liter).

For the evaluation of the cleaning performance, the contamination and stain removal ability of the lipase from the fabrics present in the typical washing dose is of great importance. Unfortunately, the relative ability of lipase to meet different performance criteria depends, among other things, on the presence of co-surfactants.

Thus, for performance and flexibility reasons, we require a surfactant system capable of providing optimal lipase purification performance.

The above requirement is met by a surfactant system comprising a co-surfactant selected from the group consisting of primary and tertiary amines.

It has been surprisingly found that by incorporating specially selected primary or tertiary amines in a liquid detergent composition containing a lipolytic enzyme (lipase), their ability to rapidly reduce the interfacial tension of aqueous washing solutions containing fatty and oily impurities is significantly improved. This substantial reduction in the interfacial tension of greasy and oily contaminants improves their removal from contaminated surfaces and prevents the re-deposition of contaminants on the substrates.

Surprisingly, it has also been found that liquid detergent compositions containing a lipolytic enzyme and a specifically selected predominantly tertiary amine show synergistic removal of greasy / oily soils, particularly when the laundry composition is applied to greasy / oily stains on fabrics, prior to normal washing of fabrics. in connection therewith, it is used in a pretreatment.

LIPOLITIC ENZYME - The laundry detergent compositions of the present invention preferably contain from about 0.0001% to about 1.0% detergent-compatible lipase (lipolytic enzyme) per effective amount of active ingredient. "Compatible with a detergent is intended to be compatible with the other ingredients of the formulation, in particular with detergent surfactants and with any detergent builders. Liquid detergent compositions, particularly high performance liquids, are preferred in the present invention.

A lipase suitable for use in any laundry detergent composition may be used herein. Lipases suitable for use in the present invention are bacterial and fungal. The invention encompasses lipase from chemically or genetically modified mutants.

Suitable bacterial lipases are those produced by Pseudomonas, such as Pseudomonas stutzerí ATCC 19,154, as disclosed in British Patent No. 1,372,034, which is incorporated herein by reference. Suitable lipases include those which exhibit a positive immunological cross-reaction with the lipase antibody produced by Pseudomonas fluorescens IAM 1057. This lipase and purification process are disclosed in Japanese Patent Publication No. 53-20487, published February 24, 1978, which is incorporated herein by reference. This lipase is available under the trademark Lipase P, "Amano-P, hereinafter referred to as" Amano-P. " Such lipases may exhibit a positive immunological cross-reaction with the Amano-P antibody according to Ouchterlony, Acta. Med. Scan., 133, 76-79. (1950)] using a standard and well known immuno-diffusion procedure. These lipases and the method for their cross-reactivity with Amano-P are described in U.S.P. No. 4,707,291 to Tóm et al., Also incorporated herein by reference. Typical examples of these are Amano-P lipase, a

Lipase from Pseudomonas fragi FERM P 1339 (available under the trade name Amano-B); Lipase from Pseudomonas nitroreducens var lipoliticum FERM P 1338 (available under the trade name Amano-CES) from Chromobacter viscosum, e.g. Chromobacter viscosum var. lipoliticum NRRLB 3673; and other Chromobacter viscosum lipases and Pseudomonas gladioli. Other interesting lipases are Amano AKG and Bacillus Sp.

Suitable fungal lipases are those produced by Humicola lanuginosa and Thermomyces lanuginosus. Most preferred lipases are obtained by cloning a gene from Hu · · · micola lanuginosa and expressing the gene in Aspergillus oryzae, as disclosed in European Patent 0 258 068, which is commercially available under the trade name Lipolase ™.

Highly preferred lipases are variants of the D96L lipolytic enzyme native lipases from Humicola lanuginosa as disclosed in U.S. Patent Application Serial No. 08 / 341,826. Preferably, Humicola lanuginosa strain DSM 4106 is used. This enzyme is added to the composition of the present invention in an amount of 50 LU to 8500 LU / liter of wash solution. The D96L variant is preferably present in an amount of 100LU-7500LU / liter of wash solution. More preferably, it is present in an amount of 150LU-5000LU / liter of wash solution.

By D96L lipolytic enzyme variant is meant the lipase variant disclosed in WO 92/05249 in which the aspartic acid moiety (D) of the native lipase from Humicola lanuginosa is replaced at position 96 by leucine (L). According to the nomenclature, the substitution of aspartic acid at position 96 with leucine is designated as D96L.

The D96L lipolytic enzyme variant has been found to be particularly advantageous due to the good odor characteristics associated with its use in combination with amines.

These compositions may contain from about 2 to 20000, preferably from about 10 to 6000, most preferably from about 200 to 2000, units of lipase g (LU / g). One lipase unit is the amount of lipase that produces 1 pmol of titratable butyric acid per minute at pH 7.0, the temperature 30 ° C and the substrate in a phosphate buffer in the presence of calcium ion and sodium chloride, and gum arabic emulsion.

Amines - For the purposes of the present invention, amines correspond to primary or tertiary amines which are said to form a mixed micelle with the anionic surfactant and in which the alkyl group has a carbon chain length of 6 or more carbon atoms.

Suitable primary amines for use in the present invention are those of the formula R3NH2

R 1 is C 6 -C 12 alkyl, preferably C 6 -C 10 alkyl, or R ₄ X (CH ₂ ) _n ;

X is -O-, C (O) NH- or -NH-;

R ₄ is a C 6 -C 12 alkyl chain;

n is from 1 to 5, preferably 3 (R _x alkyl chains are straight or branched and may be interrupted by less than 12, preferably less than 5 ethylene oxide groups.) - amines.

Preferred amines of the formula given above are alkyl amines. Suitable amines for use in the present invention can be selected from 1-hexylamine, 1-octylamine, 1-decylamine and laurylamine. Other preferred primary amines include (C 8 -C 10) alkyloxy-propylamine, (octyloxy) -propylamine, 2-ethylhexyloxypropylamine, laurylamidopropylamine and amido. propylamine.

Suitable tertiary amines for use in the present invention are those amines of the formula R _X R ₂ R ₃ N wherein

R _x and R ₂ are C 1 -C 8 alkyl chains or * 5

I

- (CH ₂ -CH-O) _X H;

R ₃ is either a C 6 -C 12 alkyl, preferably C 6 -C 10 alkyl chain, or R ₃ is a R ₄ X (CH ₂ ) _n - group in which

X is -O-, - (O) NH- or -NH-;

R ₄ is a C 4 -C 12 alkyl chain; and n is 1-5, preferably 2-3;

R ₅ is hydrogen or C 1-2 alkyl; and x is a number from 1 to 6.

R ₃ and R ₄ may be straight or branched; alkyl groups R ₃ may be interrupted by up to 12 ethylene oxide groups, more preferably up to 5 ethylene oxide groups.

Preferred tertiary amines are those of the formula R ₁ R ₂ R ₃ N in which

R 1 is a C 6 -C 12 alkyl chain;

R ₂ and R ₃ are C 1-3 alkyl or * 5

I

- (CH ₂ -CH-O) _X H wherein R ₅ is hydrogen or methyl and x = 1-2.

Also preferred are

R _{x is} -C (O) -NH- (CH ₂ ) _n -N- (R ₂ ) ₂ - wherein

R 1 is C 6 -C 12 alkyl; n is from 2 to 4, preferably 3;

R ₂ and R ₃ are C 1-3 amidoamines.

The most preferred amines of the invention are 1-hexylamine,

1-octylamine, 1-decylamine, 1-dodecylamine, (C 8 -C 10 alkyloxy) propylamine, N-coconut-1,3-diaminopropane, coconut alkyl dimethyl- amine, lauryldimethylamine, laurylbis (hydroxyethyl) amine, coconut bis (hydroxyethyl) amine, 2 molar propoxylated laurylamine, 2 molar propoxylated octylamine, laurylamidopropyl- dimethylamine, C8-C10 alkylamido-propyldimethylamine and C10-alkylamido-propyldimethylamine. The most preferred amines for use in the compositions of the present invention are 1-hexylamine, 1-octylamine, 1-decylamine, 1-dodecylamine. Particularly preferred are dodecyldimethylamine and bis (hydroxyethyl) coconut alkylamine and seven-ethoxylated oleylamine, laurylamidopropylamine and coconut amidopropylamine.

TEXTILE WASHING AND PRE - TREATMENT PROCEDURE

The present invention also relates to a process for washing fabrics contaminated with greasy / oily stains or impurities. Such a process involves contacting these fabrics with an effective amount of the above-mentioned detergent compositions in contact with a formulated aqueous solution. The fabrics are usually contacted with the washing solution under stirring conditions.

For good cleaning, mixing is preferably provided in a washing machine. The washing is preferably followed by drying the wet cloth in a conventional clothes dryer. The effective amount of the liquid or particulate detergent composition in the washing machine, the aqueous washing solution, is preferably about 7000 ppm, more preferably about 1000-3000 ppm.

The detergent compositions of the present invention may also be used to pre-treat fabrics contaminated with greasy / oily stains or impurities prior to washing such fabrics using conventional aqueous washing solutions. Such pretreatment involves the direct application of the highly concentrated forms of detergent compositions of the present invention to greasy or oily stains or impurities present on the fabric to be cleaned. In the liquid form compositions of the present invention, this generally means direct application of the composition to the patch / dirt on the fabric in its original form.

Grease / oil stains or soils are generally pretreated for about 30 seconds to 24 hours before washing the pretreated soiled / stained substrate in a conventional manner. More preferably, the pretreatment times range from about 1 to about 180 minutes.

Detergent Ingredients - In another embodiment of the invention, the liquid detergent composition may comprise one or more surfactants selected from a wide variety of surfactants.

A representative list of anionic, nonionic, ampholite and 1kerionic groups and species of these surfactants is disclosed in U.S. Pat. 3,664,961 (Norris).

'· · ··· ·· · ··· · · · · · · · · · ·

Preferred anionic surfactants include alkyl sulfate surfactants of the general formula ROSO3M

R is preferably an alkyl or hydroxyalkyl group having from 10 to 24 carbon atoms, preferably having from 10 to 18 carbon atoms, more preferably from 12 to 15 carbon atoms or hydroxyalkyl; and

M is hydrogen or a cation such as an alkali metal cation (e.g. sodium, potassium, lithium) or ammonium or substituted ammonium (e.g. methyl, dimethyl and trimethylammonium cations and quaternary ammonium cations such as tetramethylammonium and dimethylpiperidine and quaternary ammonium cations derived from alkylamines such as ethylamine, diethylamine, triethylamine and mixtures thereof) and water-soluble salts or acids.

Very preferred anionic surfactants include, among the alkoxylated alkyl sulfate surfactants, RO (A) _m SO ₃ M, wherein

R is an unsubstituted C 10 -C 24 alkyl component or C 10 -C 24 alkyl, preferably C 12 -C 18 alkyl or hydroxyalkyl, more preferably C 12 -C 15 alkyl or hydroxyalkyl group;

A is an ethoxy or propoxy unit;

m is greater than zero, typically about 0.5-6, more preferably about 0.5-3; and

M represents a hydrogen atom or a cation which may be exemplified by a metal cation (e.g., sodium, potassium, lithium, calcium, magnesium, etc.), ammonium or substituted ammonium cation water soluble salts or acids. The present invention includes ethoxylated alkyl sulfates and propoxylated alkyl sulfates. Representative examples of substituted ammonium cations are methyl, dimethyl, trimethylammonium cations and quaternary ammonium cations such as tetramethylammonium and dimethylpiperidium cations, and alkylamine derivatives such as ethylamine, diethylamine, triethyl amines, mixtures thereof, and the like. Examples of surfactants include C 12 -C 15 alkyl polyethoxylate (1.0) sulfate [C 12 -C 15 1.0 (1.0) M], C 12 -C 15 alkyl polyethoxylate (2,25) sulfate [C 12 -C 15 E ( 2.25) M], C4-alkyl polyethoxylate (3.0) sulfate [C12-C15 E (3.0) M] and C12-C15 alkyl polyethoxylate (4.0) sulfate [C12-C15 E] (4.0) ) Μ], wherein M ion is obviously selected from sodium and potassium.

Other suitable anionic surfactants include alkyl ester sulfonate surfactants, including linear esters of C8-C20 carboxylic acids (i.e., fatty acids) which are sulfonated with sulfur trioxide gas according to The Journal of the American Oil Chemists Society, 52, 323329 (1975). . Suitable starting materials include natural fats such as tallow, palm oil and the like. from materials.

Preferred alkyl ester sulfonate surfactants are particularly useful for laundry applications

R ^{3 is} -CH (SO ₃ M) -C (O) -OR ⁴ having the formula:

R ³ is a C 8-20 hydrocarbon, preferably an alkyl group, or a combination thereof;

R ⁴ is a C 1 -C 6 hydrocarbon group, preferably an alkyl group or a combination thereof; and

M is a cation which forms a water-soluble salt with 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 .);

R ³ is preferably C 10 -C 16 alkyl; and

R ⁴ is methyl, ethyl or isopropyl group (particularly / 3 preferred are the methyl ester sulfonates wherein R is

(C 10 -C 16 alkyl) alkyl ester sulfonate surfactants.

Other anionic surfactants useful for cleaning purposes may also be included in the laundry detergent compositions of the present invention. These include soap salts (including, for example, mono-, di-, and triethanolamine salts), C 8 -C 22 primary alkanesulfonates, C 8 -C 24 olefin sulfonates, sulfonated polycarboxylic acids 17 produced by sulfonation of pyrrolized products of alkaline earth metal citrates, e.g. British Polyglycol ether sulfonates having from 8 to 24 carbon atoms (containing up to 10 moles of ethylene oxide); alkyl glycerol sulfonates, fatty acyl glycerol sulfonates, fatty oleoyl glycerol sulfonates, (alkylphenol) ethylene oxide ether sulfates, paraffin sulfonates, α-acyl phosphates, isethionates, e.g. acyl isethionates monoesters of sulfosuccinates and sulfosuccinates, monoesters of sulfosuccinates (especially C12-C18 saturated and unsaturated monoesters) and di-esters of sulfosuccinates (especially C12-C18 saturated and unsaturated diesters), alkyl- polysaccharide sulfates, such as alkyl polyglucoside sulfates (the nonionic non-sulfated compounds will be disclosed later) and alkyl polyethoxycarboxylates such as RO (CH ₂ CH ₂ O) _k -CH ₂ COO M ⁺ , wherein R is an 8- C 22 alkyl, 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 resin acids and hydrogenated resin acids in or derived from tall oil. Further examples are given by Schwartz, Perry and Berch; In Surface Active Agents and Detergents (Volumes I and II). A series of such surfactants are also generally disclosed in USP 3,929,678 (Laughlin et al.), Column 23, line 58 to column 29, line 23 (which is incorporated herein by reference).

The laundry detergent compositions of the present invention typically contain from about 1% to about 40%, preferably from about 5% to about 25%, by weight of such anionic surfactants.

Condensates of a group of nonionic surfactants useful in the present invention with a hydrophobic group to provide a surfactant having an average hydrophilic lipophilic balance (HLB) in the range of 8-17, preferably 9.5-14, more preferably 12-14. form. The hydrophobic (lipophilic) group may be aliphatic or aromatic, and the length of the polyoxyethylene group fused to any typical hydrophobic group may be readily adjusted to obtain a water-soluble compound having the desired degree of balance between the hydrophilic and hydrophobic elements.

Particularly preferred compounds of this type are C9-C15 primary alcohol ethoxylates containing from 3 to 12 moles of ethylene oxide per mole of alcohol, especially C12-C15 primary alcohol ethoxylates containing from 5 to 8 moles of ethylene oxide per mole of alcohol.

Another class of nonionic surfactants is

RO (C 1 H _2n O) _t Z _x -

Z is a group derived from glucose;

R is a C12-C18 saturated hydrophobic alkyl group;

t is from 0 to 10;

n is 2 or 3; and x is from 1.3 to 4 alkyl polyglucosides, less than 10% unreacted fatty alcohol and less than 50% lower alkyl polyglucosides. Such compounds and their use in detergents are disclosed in EP-B 0 070 077,

U.S. Patent Nos. 075,996 and 0,094,118.

Nonionic surfactants include

R ^{2 is} -C (O) -NR ¹ ) -z

R ¹ is hydrogen, or R ¹ is C 1 -C 4 hydrocarbon, 2-hydroxyethyl, 2-hydroxypropyl, or a mixture thereof;

R ² is C 5 -C 31 hydrocarbon; and

Z is a linear polyhydroxy hydrocarbon radical having at least 3 hydroxyl groups directly attached to the chain or an alkoxylated derivative thereof. Preferably R is methyl, R is straight,

C 11 -C 15 alkyl or alkenyl chains such as coconut alkyl or mixtures thereof and Z is a group derived from a reducing sugar such as glucose, fructose, maltose, lactose, a reductive amination reaction - polyhydroxy fatty acid amide surfactants are also very suitable .

Very preferred nonionic materials are amine oxide surfactants. Compositions of the invention

R ¹ (EO) _x (PO) _y (BO) _{Z may contain} N-O (CH ₂ R ') ₂ .qH ₂ O (I).

In general, it can be seen that structure (I) provides a long chain R ¹ (EO) _x (PO) _y (BO) ₂ and two short chain CH ₂ R 'groups. Preferably R 'is selected from the group consisting of hydrogen, methyl, and -CH ₂ OH. ^R1 is usually a primary or branched hydrocarbyl moiety which can be saturated or unsaturated, R ¹ is a primary alkyl group. When x + y + z = 0, R ¹ is a hydrocarbon group having a chain length of about 8 to about 18 carbon atoms. If x + y + z is different from 0, then R ¹ is a little bit of β · · · · · · · · · · · · · · · · · · · · · · · · · · · · · · · · · · · · · · may be longer in the chain length range of 12 to 24 carbon atoms. The general formula also includes amine oxides wherein x + y + z = 0, R ^{1 = C} 8-18, R '= hydrogen, and q = 0-2, preferably 2. These amine oxides are C 12 -C 14 alkyldimethylamine oxide, hexadecyldimethylamine oxide, octadecylamine oxide and their hydrates, in particular dihydrates, as disclosed in U.S. Patent Nos. 5,075,501 and 5,071,594, which are incorporated herein by reference. documents.

The invention also includes amines wherein x + y + z is different from O, more particularly x + y + z is from about 1 to about 10, R ¹ is from 8 to about 24 carbon atoms, preferably from about 12 to 16 carbon atoms; in these embodiments, y + z is preferably from 0 to x, preferably from about 1 to about 6, more preferably from about 2 to about 4; EO ethyleneoxy; PO represents propyleneoxy and BO represents butyleneoxy. Such amine oxides may be prepared by conventional synthetic methods, for example by reaction of alkyl ethoxysulfates with dimethylamine followed by oxidation of the ethoxylated amine with hydrogen peroxide.

Very preferred amine oxides in the present invention are solids at room temperature, and more preferably have a melting point in the range of 30 ° C to 90 ° C. Amine oxides suitable for use in the present invention are commercially manufactured by many companies, including

Akzo Chemie, Ethyl Corp. and Procter & Gamble. For the various amine oxide manufacturers, see the McCutcheon assembly and the comprehensive article by Kirk-Othmer. The commercially available preferred amine · · «« · · a * «4 * 4 4 4« 4 <

»·« ·> · · «« «• · 4 4 4 4

IQ »« · 44 «· ·· 44

SHE

oxides available from Ethyl Corp. are ADMOX 16 and ADMOX 18, ADMOX 12 and especially ADMOX 14, solids, dihydrates.

Preferred embodiments are hexadecyldimethylamine oxide water (1/2), dodecyldimethylamine oxide water (1/2), octadecyl dimethylamine oxide water (1 / 2), hexadecyl tris (ethyleneoxy) dimethylamine oxide and tetradecyl dimethylamine oxide-water (1/2).

Although, in certain preferred embodiments, R '= hydrogen, there is some room for maneuver with respect to a slightly larger R' group than hydrogen. The invention further typically includes embodiments wherein R '= CH ₂ OH, for example in hexadecylbis (2-hydroxyethyl) amine oxide, tallow bis (2-hydroxyethyl) amine oxide, stearyl-. dodecyldimethylamine oxide-water (1/2) -bis in bis (2-hydroxyethyl) amine oxide and oleyl bis (2-hydroxyethyl) amine oxide.

When added to the detergent compositions of the invention, the nonionic surfactants are present in a weight ratio of from 6: 1 to 1: 3, preferably from 5: 1 to 2: 1, based on the anionic surfactants.

Suitable cationic detergent surfactants for use in the laundry detergent compositions of the present invention have a long chain hydrocarbon group. Such cationic surfactants are, for example, ammonium surfactants, such as alkyldimethylammonium halides, and surfactants of the formula [R ² (OR ³ ) y] [R ⁴ (OR ³ ) y] ₂ R ⁵ N ⁺ X. - of which

R ² is alkyl or alkylbenzyl of about 8 to 18 carbon atoms;

· «• · · 4 4 4 4 4 4 4 az ⁴ az az az az az az az az az az az az az az az az az az az az az az az az az az az az az az az az az az az az az az az az az az az az az az az az az az az az az az az az az az az az az az -CH ₂ CH ₂ -, -CH ₂ CH (CH ₃ ) -, -CH ₂ CH (CH ₂ OH) -, -CH ₂ CH ₂ CH ₂ - and mixtures thereof;

each R ^{4 is} selected from C 1 -C 4 alkyl, C 1 -C 4 hydroxyalkyl, benzyl ring structures formed by the attachment of two R ⁴ groups, -CH ² CHOH-CHOHCOR ⁶ CHOHCH ² OH, wherein R ⁶ is any hexose or about A hexose polymer and hydrogen having a molecular weight of less than 1000, when y is other than 0;

R is the same as R or an alkyl chain in which the total number of carbon atoms R ² plus R ^{3 is} not greater than about 18;

each y value is from 0 to about 10 and the sum of y values is from 0 to about 15; and

X is any compatible anion.

Preferred cationic surfactants for use in the compositions of the invention include

R 1 is RaRXx of formula (i) - wherein

R 1 is C 8 -C 16 alkyl;

each of R ₂ , R ₃ and R _{4 is} independently C 1-4 alkyl, C 1-4 hydroxyalkyl, benzyl, and - (C ₂ H ₄ O) _X H wherein x is 1- And X is an anion, and at most one of R ₂ , R ₃ and R ₄ may be benzyl - water-soluble quaternary ammonium compounds.

For Rj, C12-C15 is the preferred alkyl chain length, especially if the alkyl group is made from coconut or palm grease. It is obtained by a mixed chain length or synthetically derived from olefinic structures or synthesis of oxo-alcohols. Preferred groups for R ₂ , R ₃ and R ₄ are methyl and hydroxyethyl groups, and anion X can be selected from halides, methosulfate, acetate and phosphate ions.

Suitable compounds of formula (I) for use in the present invention include:

coconut trimethylammonium chloride or bromide; coconut methyl (dihydroxyethyl) ammonium chloride or bromide;

deci1 triethyl ammonium chloride;

decyldimethylhydroxyethylammonium chloride or bromide;

Or C12-C15 dimethylhydroxyethylammonium chloride;

bromide;

coconut dimethyl (dihydroxyethyl) ammonium chloride or bromide;

myristyl (trimethyl ammonium) methyl sulfate;

lauryldimethylbenzylammonium chloride or bromide; lauryl dimethyl (ethoxy) _4- ammonium chloride or bromide; choline esters (compounds of formula (I) wherein R _x is -CH ₂ -OC (O) - (C 12 -C 14 alkyl); and R ₂ , R ₃ , R ₄ are methyl.]

Other cationic surfactants useful in the present invention are described in U.S.P. No. 4,228,044 to Cambre.

The laundry detergent compositions of the present invention will typically contain from about 0.5% to about 5%, preferably from about 1% to about 3%, by weight of such cationic surfactants.

The compositions of the present invention may further comprise a builder system. Any conventional builder system is suitable for use in the present invention, including aluminum silicate materials, silicates, polycarboxylates and fatty acids such as ethylene diamine tetraacetate materials, metal ion complexing agents such as aminopiphosphonates, in particular ethylene diamine tetramethylene acid and pentamethylene acid. Phosphate builders may also be used in the present invention, although less obvious for obvious environmental reasons.

Suitable polycarboxylate builders for use in the present invention include citric acid, preferably a water-soluble salt, of the formula R-CH (COOH) CH ₂ (COOH) - wherein R is C 10-20 alkyl, preferably C 12-16 alkyl or alkenyl. , or R may be substituted with hydroxy, sulfo, sulfoxy or sulfone substituents - succinic acid derivatives. Typical examples are lauryl succinate, myristyl succinate, palmityl succinate, 2-dodecenyl succinate, 2-tetradecenyl succinate. Succinate builder is preferably used in the form of its water-soluble salts, including sodium, potassium, ammonium salts.

Other suitable polycarboxylates are mixtures of oxodisuccinate and tartrate monobasic and tartrate dibasic, e.g. 4,663,071.

Suitable fatty acid builders for use in the invention, particularly for the liquid embodiments disclosed herein, are saturated or unsaturated fatty acids having from 10 to 18 carbon atoms, and suitable soaps. Preferred saturated builders in the alkyl chain are from 12 to 16 carbon atoms. The preferred unsaturated fatty acid is oleic acid. Another preferred builder system for liquid formulations is based on dodecenyl succinic acid and citric acid.

The detergent builder salts are usually added to the composition in an amount of from 3 to 50% by weight, preferably from 5 to 30% by weight, and most typically from 5 to 25% by weight.

Optional detergent ingredients:

Preferred detergent compositions of the present invention further comprise one or more enzymes for providing cleaning performance and / or fabric care benefits. These enzymes include cellulases, hemicellulases, peroxidases, proteases, glucoamylases, amylases, lipases, cutinases, pectases, xylanases, reductases, oxidases, phenol oxybases, lipoxygenases, lipoxygenases, lipoxygenases, lipoxygenases, lipoxygenases, lipoxygenases, lipoxygenases, may contain enzymes selected from arabiposidases or mixtures thereof.

A preferred combination is a detergent composition of conventionally used enzymes, such as protease, amylase, lipase, cutinase and / or cellulase, in a cocktail of ptjgL lipolytic enzyme variant in a volume of 50-8500 U / L wash solution.

In the present invention, both bacterial and fungal cellulases are useful cellulases. Their optimum pH is preferably 5-9.5. Suitable cellulases are disclosed in U.S.P. U.S. Patent No. 4,435,307 to Barbesgoard et al., Which discloses fungal cellulases produced from Humicola insolens. Suitable cellulases are disclosed in GB-A-2,075,028; GB-A-2,095,275 and DE-OS-2,247,832.

Such cellulases are, for example, a strain of Humicola insolens (Humicola grisea var. Thermoidea), especially those produced by Humicola DSM 1800.

Other suitable cellulases from Humicola insolens,

Cellulases with a molecular weight of about 50KDa, an isoelectric point of 5.55 and 415 amino acids. Examples of such cellulases are those disclosed in European Patent Application No. 91202879.2 (Novo), filed November 6, 1991.

Peroxidase enzymes with oxygen sources such as percarbonate, perborate, persulphate, hydrogen peroxide, etc. used in combination. They are used for "solution bleaching", i.e. to prevent the transfer of dyes or pigments removed from substrates during washing increments to other substrates in the washing solution. Peroxidase enzymes are known in the art, and include, for example, horseradish peroxidase such per _p, ligninase, and haloperoxidase such as chloro- and _bromo-p per xidéz. Examples of detergent formulations containing peroxidase are given! WO 89/0998133 international publication of PCT international patent application mainly consists _sz herein and in 1991 announced on November 6, gp. European Patent Publication No. 91202882.6.

The respective cellulases and / or peroxidases are usually added to the detergent composition in an amount of 0.0001 to 2% active enzyme by weight of the detergent.

Preferred commercially available protease enzymes are sold by Novo Nordisk A / S (Denmark) under the trade names Alcalase, Savinase, Primate, Durazym and Esperase and sold by Gist-Brocades under the trade names Maxatase, Maxacal and Maxapem, sold by Genencor International and Solvay Enzymes sold under the trade names Opticlean and Optimase. The detergent composition of the present invention may include the proteases disclosed in USSN 08 / 136,797, which is pending. The compositions of the present invention may contain from 0.0001% to 2% by weight of the protease enzyme of the active enzyme.

The preferred protease, referred to herein as "Protease D," is a variant of a non-naturally occurring amino acid sequence] <arbonyl hydrolase, which is a subtilis subunit of the amino acid residue at position +76 of a carbonyl hydrolase precursor, preferably Bacillus amyloliquefaciens. +99, +101, +103, +104, +107, +123, +27, + 105, +109, +126, +128, +135, +156, +166, +195, +197 , +204, +206, +210, +216, +217, +222, +260, +265 and / or +274, also obtained by substitution with one or more amino acid residues at a selected location, as "Protease-containing cleaning compositions IMU 08 _c / serial No. 322.676, reported on 13 October 1994 patent leírásásukban simultaneously A. Baeck et al has reported, in common, which is incorporated herein in its entirety for hivat25 herein.

Also suitable are cutinases (EC 33.1.1.50) which can be considered as a special type of lipase, namely lipases which do not require interfacial activation. The administration of cutinases to detergent compositions is described, for example, in WO-A88 / 09367 (Genencor).

The lipases and / or cutinases are usually added to the detergent composition in amounts of 0.0001 to 2% active enzyme by weight of the detergent.

Amylases (a and / or β) may be used to remove carbohydrate-based stains. Suitable amylases include Termamyl ^R (Novo Nordisk), Fungamyl ^R and BAN ^R (Novo Nordisk).

The above-mentioned enzymes can be of any suitable origin, such as plant, animal, bacterial, fungal and yeast.

Normally 0.0001 to 2% by weight of the active enzyme is added to the detergent composition in the detergent composition.

Other suitable detergent ingredients that may be added are the enzyme oxidation cleaners disclosed in European Patent Application Serial No. 92870018.6, filed January 31, 1992. Examples of such enzyme oxidation purifiers are ethoxylated tetraethylene polyamines.

A detergent used in the compositions of the present invention preferably component, soil release agents content & ^z

Suitable soil release agents for use in the compositions of the present invention are usually copolymers or terpolymers of terephthalic acid with ethylene glycol and / or propylene glycol units in various configurations. Such polymers are disclosed, for example, in U.S. Patent Nos. 4,116,885 and 4,711,730 and European Patent Publication No. 0 272 033. A particularly preferred polymer according to EP-A-0 272 033 is [CH ₃ (EEG) _c ] ₀ , ₇₅ (EOH) _0/25 [(T-EO) ₂₈ (T-PEG) "] T (PO). -H) ', ₂₅ [(EEG) ₄₃ CH ₃ ] _0-75 , wherein

PEG is - (OC ₂ H ₄ ) O-;

PO is - (OCH ₃ H ₆ O) -; and

T is - (pCOC ₆ H ₄ CO) -.

Modified polyesters, such as random copolymers of dimethyl terephthalate, dimethylsulfoisophthalate, ethylene glycol and 1-2-propaldiol, are also very suitable, with the end groups being primarily sulfobenzoate and secondary ethylene glycol and / or propanediol mono. The aim is to obtain a polymer sealed at both ends with sulfobenzoate groups. However, some copolymers are not completely sealed and therefore their end groups may consist of "secondary end groups, ethylene glycol and / or propane-1,2-diol monoester".

The polyesters selected herein contain about 46% by weight of dimethyl terephthalic acid, about 16% by weight of propane-1,2-diol, about 10% by weight of ethylene glycol, about 13% by weight of dimethylsulfobenzoic acid and about 15% by weight of sulfoisophthalic acid, and about 3000 molecular weights. The polyesters and their preparation process are described in detail in EPA 311 342.

Particularly suitable soil release polymers are oligomeric esters such as those disclosed in U.S. Patent Application Serial No. 08 / 355,838, filed December 14, 1994. The esters disclosed (1) are a backbone which is (a) a unit selected from the group consisting of dihydroxy or polyhydroxysulfonate, a unit having at least three functionalities, whereby ester linkages are formed to form a branched oligomeric backbone and combinations thereof;

(b) at least one unit which is a terephthaloyl group; and (c) at least one non-sulfonated moiety which is a 1,2-oxyalkyleneoxy group; containing (2) one or more (nonionic and / or anionic) closure units.

Preferred ester molecules are represented by the structural formula [A] wherein R = hydrogen, a methyl group at a ratio of 1.7: 1, which is an example of an oligomer with three SE3 blocking units, one SEG unit and one glycerol unit in the oligomeric structure.

Other ingredients may also be included in the detergent compositions, such as soil suspending agents, abrasives, bactericides, coatings, colorants, antifoams, corrosion inhibitors, and perfumes.

The liquid compositions of the invention are preferably in a "concentrated form; in this case, the liquid detergent compositions of the invention contain less water than conventional liquid detergents. The amount of water in the detergent composition is less than 50%, preferably less than 30%, more preferably less than 20%.

These concentrated products are beneficial to the consumer who has a product from which he can use smaller quantities and benefits the manufacturer, who has lower shipping costs.

Liquid formulations are particularly effective when applied directly to dirt and stains in a pre-treatment step.

The detergent compositions of the present invention may also be used as a detergent supplement. Such supplemental products are intended to supplement or enhance the performance of conventional detergent formulations.

The detergent compositions of the present invention include compositions which are applied to materials such as fabrics, fibers, hard surfaces, leather, and the like. intended for use in cleaning, such as hard surface cleaning compositions (with or without abrasives), laundry detergent compositions, and machine and hand dishwashing detergents.

The compositions of the present invention are illustrated by the following examples, which are not, however, to be construed as limiting the scope of the invention.

Example 1:

The following detergent compositions were prepared:

weight% of detergent compositions

THE B C D E Linear alkyl benzene sulfonate 18 - - - - C12-C15 ethoxylated alkyl- -sulfate - 2 8 11 5 C 12 -C 14 alkyldimethylamine- -oxide - - - - 2 C12-C15 alkyl sulfate - 17 12 7 8 C12-C14 N-methylglucamide - 5 4 4 3 C12-C14 fatty alcohol ethoxylate 12 6 1 1 1 C12-C18 fatty acids 11 11 4 4 3 Citric acid, anhydrous 5 1 3 3 2

Diethylenetriamine pentamethylene

-phosphonicacid 1 1 1 1 0, 5 Monoethanolamine 11 8 5 5 2 Sodium hydroxide 1 1 2, 5 1 1.5 propanediol 12.7 14.5 13, i: 10.0 8 Ethyl alcohol 1.8 1.8 4.7 5.4 1 Amylase (300KNU / g) 0.1 0.1 0.1 0, 1 0.1 Lipase D96 / L (100OOU / g) 0.15 0.15 0.15 0.15 0.15 Protease (34g / L) 0.5 0.5 0.5 0, 5 0.5 Endo-A (5000 CEVU / g) 0, 05 0.05 0, 05 0, 05 0.5 Carezyme (5000 CEVU / g) 0.09 0.09 0.09 0, 09 0.9 Polymer based on terephthalate 0, 15 0.15 - - Oligomeric ester (Preparation A) - - 0.07 0, 07 0.07

· · ·

Boric acid

Sodium xylene sulfonate

DC 3225C

2-butyl-octanol

Branched silicone

Water and other minor ingredients

2.4 2.4 2.8 2.8 2.4

0.03 0.04 0.04 0.03 0.03

11111

0, 3 0.3 0, 3 0, 3 0.3 Supplement to 100%.

component THE crowd% B crowd% C crowd% C12-C15 alkyl polyethoxylate (2.5) sulfate 13, 50 13.70 9.40 C12-C15 alkyl sulfate 4.50 4.00 3.10 Ethyl alcohol 3.50 2.64 2.18 Monoethanolate amine 1.00 0.75 1.00

amidopropyldimethyl-carbon

amine 1.30 1.30 1.30 propanediol 7.5 7.5 3.2 C12-13 alkyl polyethoxylate (9) 2.00 0, 63 1.00 C12 -C14 alkyl glucosamide 4.50 3, 35 2.00 C12 -C14 fatty acid 2.00 3.50 1, 00 lipolase 0, 18 0, 18 0, 18 Sodium toluene sulfonate 2.5 2.25 2.25 Citric acid 3.00 2.65 1, 80 Borax 3.50 3.50 - Sodium hydroxide (PH 8.0) 2.95 2, 10 2, 07 pH 8.0 pH 7.6 to pH 8,

Tetraethylene pentamine 1.18 1.18 1.00

Water, Perfume, Enzymes, Soil Release Polymers, Antifoam & Other

where appropriate -parts creative To 100% To 100% To 100% Example 3: component THE B C D crowd% crowd% crowd% crowd% C 12 -C 15 alkyl polyethoxylate (3) sulfate 13.70 13.70 13.70 13, 70 C 12 -C 15 alkyl -sulfate 4.00 4.00 4.00 4.00 Ethyl alcohol 2, 64 2.64 2.64 2.64 Monoethanolate amine 0.75 0, 75 0, 75 0.75 C 12 amidopropyl dimethylamine 1.30 C 10 amidopropyl dimethylamine __ 1.30 12 carbon bis (hydroxy) -ethyl) -amine __ 1, 30 1.30 Octylamine - - - - propanediol 7, 5 7.5 7.5 7.5 C 12 -C 13 alkyl -Polyethoxylate (9) 0, 63 0, 63 0, 63 0, 63 C 12 -C 14 alkyl- -glucose amide 3, 35 3, 35 3, 35 3, 35

C12-16 fatty acids 3.50 3.50 3.50 3.50 lipolase 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 2.10 2.1 2.1 You traethylene pen, pH 8.0 pH 8.0 pH 8.0 pH 8.0 ethoxylated (15-18) 1.18 1.18 1.18 1, 18

Water, perfume, enzymes, soil release polymers, antifoam and other optional ingredients 100% to 100% to 100% to 100%.

The liquid detergent compositions of Examples 1, 2 and 3 above have been found to be very effective in removing greasy / oily soils under various conditions of use, especially in a pretreatment process.

Claims (9)

PATENT CLAIMS CLAIMS 1. A detergent composition comprising a lipolytic enzyme, wherein said detergent composition is further a) a compound of the formula R ₁ -NH _{2 in} which R _x is a C 6 -C 12 alkyl, preferably C 6 -C 10 alkyl chain, or R ₄ X (CH ₂ ) _n - X is -O-, -C (O) NH- or -NH-, R ₄ is a C 6 -C 12 alkyl chain, n is 1 to 5 of primary amines; (b) tertiary amines which: i) R ₁ R ₂ R ₃ N wherein R _x and R ₂ are C 1 -C 8 alkyl chains or r ₅ I - (CH ₂ -CH-O) _x H, R ₃ is either a C 6 -C 12 alkyl chain or R ₃ is R ₄ X (CH ₂ ) _n - in which X is -O-, - (O) NH- or -NH-, R ₄ is 4-12 is alkyl chains, n is 1-5, R _s is hydrogen or C1-2alkyl, and x is a number from 1 to 6 - ii) R _x R ₂ R ₃ N of formula: - wherein R _x is 6-12 alkyl chain with carbon, R ₂ and R ₃ are C 1-3 alkyl chains or r ₅ - (CH ₂ -CH-O) _x H - _R5 is hydrogen or methyl, and x = 1-2; iii) R 1 -C (O) -NH- (CH ₂ ) _n -N- (R ₂ ) ₂ - R! is C 6 -C 12 alkyl, n is 2 to 4, preferably 3, R ₂ and R ₃ are C 1-3; c) it contains an amine selected from mixtures of the disclosed primary and tertiary amines. Liquid detergent composition according to claim 1, characterized in that said primary amine is selected from alkyl amines, (C 8 -C 10 alkyloxy) propylamine, (octyloxy) propylamine, 2-ethyl selected from the group consisting of -hexyloxypropylamine, laurylamidopropylamine and amidopropylamine. Liquid detergent composition according to claim 2, characterized in that said alkylamine is 1-octylamine. Liquid detergent composition according to Claim 1, characterized in that the amine is selected from a tertiary amine of formula (i) wherein R ₃ is a C 6 -C 10 alkyl chain and n is 2 or 3. Liquid detergent composition according to claim 1, characterized in that the amine is a tertiary amine of formula iii) wherein n is 3. 6. A detergent composition according to any one of claims 1 to 5, characterized in that the lipolytic enzyme disclosed is D96L lipolytic enzyme. A detergent composition according to any one of claims 1 to 6, further comprising other surfactants, laundry detergents, enzymes and other conventional detergent ingredients. A detergent composition according to any one of claims 1 to 7 in liquid form. Use of a detergent composition according to claim 8 for the pretreatment of fabrics.