SK133194A3 - Pelletized detergent compositions and method of matters cleaning by these compositions - Google Patents

Abstract

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

Description

(57) Annotation:

A granular detergent composition comprising a lipase produced by Humicola sp.

Thermomyces sp., Pseudomonas pseudoalcaligenes or Pseudomonas fluorescens in an amount of 0.00025 to

0.015 g of active enzyme per 100 g of preparation, from 0.5 to 10 wt. and from 2 to 30% by weight of another anionic or non-ionic surfactant, wherein the ratio of lipase to alkyl alkoxy sulphate and / or polyhydroxy fatty acid amide is between 0.09 and 0.28. Also described is a method for purifying substances using this composition.

9512

Granular detergent compositions and method of cleaning therewith

Qblast techniques

The present invention relates to a granular detergent composition. which comprises a lipase produced by a strain selected from Humicola sp. or Thermoinyces sp. or of Pseudomonas Pseudomonascigenes or Pseudomonas fluorescens, and a method for purifying substances therefrom.

It is known that iipase is added to the detergent compositions as non-cleaning agents. By way of examples, Patent Application 0 368 589, published 16. U.S. Pat. No. 4,707,291 to Thoma et al., Issued 1987. 4,769,173 to Cornelissen et al., Issued

861,509 to Cornelissen et al., Issued

No. 069,809 to Lagerwaard et al., Japanese Publication No. 01161-096.

1988th

1989, and 1991, 1987 published for the improved European May 1990. 18 November 6 September 29 August 3 December 17 December

However, although the cleaning results using granular detergent detergents when washing laundry with stains or soiled laundry after multiple wash cycles are clear, this effect is hardly noticeable after a single wash cycle in a washer and dryer (especially for oily and oily stains such as ointment and spaghetti sauce stains). In fact, washing in granular detergent compositions. which contain lipase in conventional high amounts (in commercial products) often causes a loss of purification in the first wash cycle, although there is an improvement in multi-cycle wash. It has been found for the lipases listed below. that a small amount of lipase (i.e., the amount given below) and the inclusion of some anionic and nonionic po 2

The 9512 surfactants to the granular detergent composition at a specific weight ratio results in improved stain or dirt removal from triglycerides, such as greasy food stains or body soils, from the fabric even in the first wash cycle.

SUMMARY OF THE INVENTION

The present invention relates to a granular detergent composition. which contains;

a) lipase. produced by Ilumicoia sp., Thennoinyces sp., Pseudomonas pseudoalcalIgenes or Pseudomonas fluorescens in an amount of from 0.00025 to 0.0.15. preferably from 0.0025 to 0.010 g active enzyme per 100 g preparation,

b) from 0.5 to 10% by weight. alkyl alkoxy sulphate and / or polyhydroxy fatty acid amide; and

c) from 2 to 30% by weight. a further anionic or nonionic surfactant, wherein the ratio of component a) to component b) is between 0.09 and 0.28.

The granular detergent compositions of the present invention comprise a lipase, an alkyl alkoxysulfate or a polyhydroxy fatty acid amide and a further anionic or nonionic surfactant. The weight ratio of lipase to alkyl and 1-oxysulphuric acid or the mixture (9 wt%) and 0.20 (28 to the amount of alkyl alkoxy or fatty polyhydroxyamide of the two compounds) is between 0.09 wt%.). Preferably, the amount of sulfate lipase or polyhydroxy fatty acid amide is between 0.10 and 0.20. The compositions of the invention preferably further comprise a detergent component, second enzymes, and other conventional detergent components.

The granular detergent compositions of the invention remove triglyceride-based dirt (e.g., spaghetti sauce and bacon fat) after the first wash cycle (i.e.

9512 (washed for the first time) better than granulated preparations with a higher lipase content. Without being bound by theory, it is believed that this is the case. as the composition of the formulation disclosed herein allows the hydrolytic products to remain after washing of the triglyceride-based dirt by the action of lipase in the wash water. so they are removed more efficiently than in the case of formulations outside the present invention. It is assumed that the fact that there is a good wash already in the first wash cycle. is due to the optimized ratio of lipase to alkyl alkoxy sulphate or polyhydroxy fatty acid amide of the present invention in combination with low amounts of lipase. used according to the invention.

A. Lipase.

An essential component of the granular detergent composition of the present invention is a lipase produced by Humicola sp. Thermomyces sp., Pseudomonas pseudoalcaligenes or Pseudomonas fluorescens, which is present in the composition in an amount of from 0.0025 to 0.015, preferably from 0.0025 to 0.010 active. enzyme per 100 g preparation.

Lipase from chemically or genetically modified mutants of these strains is also within the scope of the invention. Lipase mixtures from different strains are also included, although these mixtures are not preferred.

A preferred lipase is derived from Pseudomonas pseudoalcaligenes, which is described in U.S. Patent 4,933,287 to Farina et al., Issued July 12, 1990. This patent is incorporated by reference.

The most preferred lipase of the invention is obtained by cloning a gene from Humicola lanuginosa and expressing the gene in Aspergillus oryzae according to European patent application 0 258 068, which is incorporated herein by reference, which is commercially available.

9512 available lipase from Novo Industri A / S. Bagsvaerd, Denmark, under the trade name Lipolase ^(R) . This lipase is also described in U.S. Patent 4,810,414 to Huge-Jensen et al., Issued Mar. 7, 1989, which is incorporated herein by reference. Preferably, from 0.001 to 0.6, preferably from 0.1 to 0.4% by weight is used in the composition of the invention. Lipolase ^{IR (&gt}; 100,000 IU / g).

The lipases of the invention are preferably compatible with anionic (and nonionic) surfactants and have high activity at alkaline pH. Preferably, they are compatible with the compositions of the present invention, are stable therein, and if present in the compositions of the present invention, improve washing.

Suitable lipases include those lipases. which exhibit a positive immunological cross-reaction with a lipase antibody produced by Pseudomonas fluorescens. This lipase is disclosed in Japanese Patent Application 53-20487, which was set forth on February 24, 1978 and is incorporated herein by reference. It is available under the tradename Lipase P Amano. A method for testing an immunological cross-reaction with an Amano P antibody is described in U.S. Patent 4,707,291 to Thoin et al., Issued November 17, 1987. which is incorporated herein by reference.

The lipase unit C (abbreviated as LU) is defined as the amount of lipase that produces lpmol of titratable butyric acid per minute in pHstat at pH 7.0 at 30 ° C, the substrate being an emulsion of tributyrin and acacia in the presence of calcium ions and chloride sodium phosphate buffer.

EJ. Surface - active agent

The granular detergent compositions of the present invention also contain from 0.5 to 10% by weight, preferably from 0.5 to 5% by weight. . most preferably from 1 to 2% by weight of an alkyl alkoxy sulphate, preferably an alkyl sulphate which is alkoxylated from 0.5 to

9512

10. preferably 0.5 to 2 moles of ethylene oxide per mole of alkyl sulfate, and / or polyhydroxy fatty acid amide. The present invention encompasses mixtures of the two surfactants. The formulations further comprise from 2 to 30% by weight, preferably from 10 to 20% by weight. another anionic or nonionic surfactant.

1. Alky1alkoxy with u

Alkyl alkoxy sulfate surfactants are salts or acids that are water-soluble, typically of the formula ROCA11SCbM. wherein R is unsubstituted C 10 -C 24 alkyl or C 10 -C 24 hydroxyalkyl, more preferably C 12 -C 18, A is ethoxy or propoxy / unit, m is greater than 0. typically between 0.5 and 6, more preferably between 0.5 and 3. and M represents a hydrogen atom or a cation, which may be, for example, a metal cation (e.g. sodium, potassium, lithium, calcium, magnesium, etc.), ammonium or substituted ammonium cation. Alkyl ethoxy sulfates and alkyl propoxysulfates are considered suitable. Specific examples of substituted ammonium cations include methyl-, dimethyl-. trimetes of 1-ammonium and quaternary ammonium cations such as tetramethylammonium and dimethylpiperidinium cations, and cations derived from alcauciamines, for example methanolairiin, diethanolamine and triethanolamine and mixtures thereof. Examples of surfactants are alkyl (12 to 18 carbon atoms), polyethoxylated (1.0) sulfate, alkyl (12 to 18 carbon atoms), polyethoxylated (2.25) sulfate, alkyl (12 to 18 carbon atoms), polyethoxylated (3, 18, 0) sulfate. and alkyl (12 to 18 carbon atoms) polyethoxylated (4.0) sulfate. wherein M is preferably selected from the group consisting of sodium and potassium.

2. Polyhydroxy fatty acid amide

95.12

Surfactants of the polyhydroxy fatty acid amides type are compounds of formula (I)

R ¹

^R2 - C - N - Z

wherein R ¹ is hydrogen, C 1 -C 4 hydrocarbyl, 2-hydroxyethyl.

A 2-hydroxypropyl group or a mixture thereof. preferably an alkyl group having 1 to 4 carbon atoms, more preferably an alkyl group having 1 or 2 carbon atoms, most preferably an alkyl group having 1 carbon atom (ie a methyl group). R ² is a hydrocarbon group of 5-31 carbon atoms, preferably alkyl or alkenyl group having 7 to 19 carbon atoms, a straight-chain, preferably an alkyl or alkenyl group having 9 to 17 carbon atoms, a straight-chain, preferably an alkyl or alkenyl 1.1 and Z is a linear hydrocarbon chain polyhydroxy hydrocarbon group having at least 3 hydroxyl groups directly attached to the chain or an alkoxylated derivative thereof (preferably ethoxylated or propoxylated). Z is preferably derived from a reducing sugar in a reductive amination reaction, more preferably Z is a glycityl group. Suitable reducing sugars include glucose, fructose, maltose, lactose, galactose, mannose, and xylose. Z represents a group which is preferably selected from the group consisting of the groups of the formulas -CH ₂ - (CHOH), h- Father 11, -CH (CH ₂ OH) - (C 1-10 OH) -CH ₂ OH and -CH ₂ (CHOH) ₂ (CHOR ') (CHOH) -Cl 2 OH and their alkoxylated derivatives. wherein n represents a number from 3 to 5 inclusive and R 'represents a hydrogen atom or a cyclic or aliphatic monosaccharide d. Most preferred are glycityls wherein n is 4, especially -CH ₂ - (CHOH) 4 -CH ₂ OH.

Fatty acid polyhydroxyamide is preferably glucamide, preferably N-acetyl-gliicamide having from 1.2 to 18 carbon atoms.

953.2 ka.

3. Other anionic surfactant

Anionic surfactants useful for cleaning purposes are included in the compositions of the invention. These include salts (including, for example, sodium, potassium, ammonium and substituted ammonium salts such as mono-, di-, and triethanolamine salts) of soaps, linear C 9 -C 20 alkyibenzenesulfonates, C 0 -C 22 primary or secondary alkanesulfonates carbon, olefin sulfonates of 8 to 24 carbon atoms, sultonated polycarboxylic acids prepared by sulfonating the pyrolyzed alkaline earth metal citrate product, e.g. as described in British Pat. 1,082 3.79. alkyl glycerol sulfonates.

fatty acylglycerol sulfonates. oleyglycerol fatty sulfates, alkylphenolethylene oxide ether sulfates.

nu. alkyl phosphates. izoetionáty. such as

N-acyl taurates, fatty acid amides of methyl tauride, alkyl succinamates and sulfosuccinates. sulfo-succinate monoesters (especially saturated and unsaturated monoesters having 3.2 to 3.8 carbon atoms), sulfosuccinate diesters (especially saturated and unsaturated 6 to 14 carbon atoms).

N-acyl sarcosinates, alkyl polysaccharide sulfates, such as alkyl polyglucoside sulfates (nonionic unsulfated compounds described below), branched primary alkyl sulfates. alkyl polyethoxy carboxylates such as those of the formula R 0 (0 CH2CIl2) ^kCH2C0Cľ'M> ·. wherein R is an alkyl group of 8 to 22 carbon atoms, and M is a cation consisting of selines esterified with isoethionic acid and neutralized with sodium hydroxide. Resin acids present or derived from body oil are also suitable. Further examples are provided in Surfactants and Detergents. parts I and II by Schwari.za. Perry and Berch. Various surfactants are also described in U.S. Patent No. 3,929; u 1 Phthalates of phthalic isoisolates.

means a number from 0 to 10 soluble salt. and fatty acids

9512

678, Laughlin et al., Issued December 30, at column 23, line 58, to column 29, line 23 (incorporated herein by reference).

A preferred type of anionic surfactants for use herein are alkyl sulfate surfactants. In addition to achieving excellent overall cleaning performance when used in combination with polyhydroxy fatty acid amides (see below), including good grease / oil cleansing over a wide range of temperatures, the concentration of laundry detergents and wash time achieves the dissolution of alkyl sulfates and also improves the ability to form liquid detergents. These formulations are water-soluble salts or acids of the general formula ROSO3M. wherein R is preferably a C 10 -C 24 hydrocarbon group, preferably an C 10 -C 20 alkyl or hydroxyalkyl group, more preferably a C 12 -C 18 alkyl or hydroxyalkyl group, and M is hydrogen or a cation, e.g. an alkali metal cation (e.g., sodium, potassium, lithium), substituted or unsubstituted ammonium cations such as methyl, dimethyl, and trimethyl ammonium, and quaternary ammonium cations, e.g. tetramethylammonium and dimethylpiperidinium cations, and cations derived from alkanolamines. such as ethanolamine. diethanolamine. triethanolamine and mixtures thereof, and the like - Typically, alkyl chains of 12 to 16 carbon atoms are preferred for low temperature wash (e.g., below 50 ° C) and alkyl chains of 16 to 18 carbon atoms for higher temperature wash (e.g., above 50 ° C).

Preferred for use herein is a C 12 -C 20 alkyl sulfate (AS) α / or a C 9 -C 20 linear alkylbenzene sulfonate (preferably sodium salt). Preferably, from 2 to 10% by weight is used. AS with 12 to 20 carbon atoms and from 10 to 15 wt%. LAS with 9 to 20 carbon atoms. A preferred nonionic surfactant is

9512 a C10-C20-C20 alcohol condensation product with 2 to 20 moles of ethylene oxide per mole of alcohol (E2-20 ethoxylated C10-C20 alcohol ').

4. Another nonionic surfactant.

Suitable nonionic surfactants are described in U.S. Pat. No. 3,929,678 (Laughlin et al., Issued December 30, 1975) at column 13, line 14, to column 16, line 14.

6. which is incorporated herein by reference. Examples of non-limiting surfactant groups are given below.

Polyethylene polypropylene- and polybutylene oxide condensates of alkylphenols. condensates. Between

In general, preferred polyethylene oxide compounds include the condensation products of alkylphenols and an alkyl group of 6 to 12 carbon atoms in either a straight or branched chain with alkylene oxide. These compounds are commonly referred to as alkylphenolalkoxilate (e.g., alkylienoethoxylates).

2. Condensation products of aliphatic alcohols with 1 to 25 moles of ethylene oxide. The alkyl chain of the aliphatic alcohol may be either straight or branched, primary or secondary, usually having 0 to 22 carbon atoms. This category of rionic surfactants is commonly referred to as alkyl ethoxylates. Preferred are aliphatic alcohols having 12 to 16, preferably 12 to 13 carbon atoms, ethoxylated with 3 to 10 moles of ethylene oxide per mole of alcohol.

3. Hydrophobic base ethylene oxide condensation products formed by condensation of polyene oxide with propylene glycol.

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

5. The semi-polar nonionic surfactants are

95.1.2. A special category of surfactants, including water-soluble amine oxides containing an alkyl group of 10 to 18 carbon atoms, and 2 groups selected from the group consisting of alkyl groups and hydroxyalkyl groups of 1 to 3 carbon atoms, water-soluble phosphine oxides containing one alkyl group of 10 to 18 carbon atoms and 2 groups selected from the group consisting of alkyl and hydroxyalkyl groups of 1 to 3 carbon atoms, and water-soluble sulfoxides containing one alkyl group of 10 to 18 carbon atoms And a group selected from the group consisting of alkyl and hydroxy groups having 1 to 3 carbon atoms.

6-Alkylpolysaccharides described in I.JSA patent 4,556,547 Llenada, issued January 21, 1986, having a hydrophobic group of 6 to 30 carbon atoms, preferably 10 to 16 carbon atoms, and a polysaccharide. e.g. polyglucosides. the hydrophilic group comprises an axis of from 1.3 to 10, preferably from 1.3 to 3, most preferably from 1 to 10

1.3 to 2.7 carbohydrate units.

7. Fatty acid amide surfactants of the general formula

II

^R6 - C - NCRylz.

wherein R is a C 7 -C 21 alkyl group preferably having 9 to 17 carbon atoms and a group consisting of C 1 to 4 carbon atoms, carbon atoms, and wherein x is a number from

C. Detergent

R ² are independently selected from hydrogen, an alkyl group of the hydroxyalkyl group having 1 to the formula - (CII 84O) χII, to 3.

The compositions according to the invention may optionally contain 1.

9512 is preferably present and is comprised of from 1 to 80%, preferably from 20 to 70% by weight. detergent component. Both inorganic and organic components can be used.

Inorganic detergent builders include, but are not limited to, ammonium, alkanolammonium, and alkali metal salts of polyphosphates (e.g., tripolyphosphates, diphosphates, and glass polymeric metaphosphates). phosphonates. phytic acid. silicates, carbonates (including bicarbonates), sulphates and alcohols. Borate ingredients and ingredients containing borate forming materials under detergent storage or washing conditions (collectively referred to herein as borate ingredients) may also be used, non-borate ingredients are preferably used in the compositions of the invention when intended for use in laundry compositions. temperatures below 50 ° C, in particular below 40 ° C.

Examples of silicate components are alkali metal silicates, especially those in which the silica to sodium ratio is 1.6 = 1 to 3.2 = 1, and layered silicates, such as layered sodium silicates, described in US Pat. No. 4,664,839 H.P.Ri Greek. issued May 12, 1987, which is incorporated herein by reference. Other silicates may also be used, for example magnesium silicate, which serves as a fabric softener, as a stabilizing agent for oxygen bleaching agents, and as a component of suds control systems.

Examples of carbonate components are alkali metal and alkaline earth carbonates, including sodium carbonate, bicarbonate and mixtures thereof with ultrafine calcium carbonate, as described in German Patent Application 2,321,001, published November 15, 1973, which is incorporated herein by reference.

Aluminosilicate are useful for the present invention

9512 Ingredients - Hl Initiatives Rope components are very important in the most commonly marketed high performance detergent compositions. They may also be an important builder in liquid detergent compositions. The compounds or compounds of the general formula are included

Mz (from A1C) ₂ . y S i 0 ?. ).

wherein M is a sodium, potassium, ammonium or substituted ammonium ion, z is from 0.5 to 2 and y is 1. This material has a magnesium ion exchanger capacity of at least 50 µg equivalents of CaCO 3 hardness per gram of anhydrous aluminosilicate. Preferred zeolites are zeolite components of the general formula

Nazli (allose) z yCSiOz) y] xH ₂ 0th

wherein z and y are at least a number, the molar ratio of z to y ranges from 1.0 to 0.5 and x is a number from 15 to 264.

Useful aluminosilicates Rope ion exchange materials are commercially available. These hydrotreaters can be crystalline or amorphous, can occur in nature or can go. o synthetic aluminosilicates. A method for producing lilino-silicone rope ion exchange materials is described in U.S. Pat. No. 3,985,669 to Krummel et al., Issued Oct. 12, 1976, which is incorporated herein by reference. Preferred synthetic crystalline aluminosilicates. Rope ion exchange materials useful in the present invention are available under the designation Zeolite A. Zeolite P (B) and Zeolite X.

Specific examples of polyphosphates are the alkali salts of tripolyphosphates, sodium, potassium and ammonium pyrophosphate. sodium and potassium orthophosphate, sodium polymetaphosphate in which the degree of polymerization ranges from 6 to 21, and the phytic acid salt (phosphoric acid).

Examples of components of the phosphate salt types are the water-soluble salts of ethane-1-hydroxy-1. 1-diphosphonate, in particular

9512 sodium and potassium salts, water-soluble salts of methylenediphospharic acid. e.g. trisodium and tripotassium salt. and water-soluble salts of substituted methylenedio-phosphoric acids such as ethylidene, isopropylidene, benzylmethylidene and halomethylidenephosphonate trisodium and trisodium. Components of the above types of phosphonate salts are described in U.S. Pat. 3,159,581 and 3,231,030 Diehl. issued December 1, 1964 and October 19, 1965, U.S. Patent 3,422,021 to Roya. issued January 14, 1969; and U.S. Patents 3,400,140 and 3,424. 137 of Quimby, issued September 3, 1960 and January 14, 1969.

Organic detergent builders useful for the purposes of this invention include various polycarboxylate compounds. The term polycarboxylate thus. as used herein, refers to compounds with multiple carboxylate groups, preferably at least 3 carboxylate groups.

The polycarboxylate component may generally be added to the formulation in acid form, but may also be added in the form of a crystallized salt. When used in salt form, alkali metal salts such as sodium are preferred. potassium and lithium or alkanolammonium salts.

Polycarboxylate components include various categories of useful materials. One important category of polycarboxylate components includes ether polycarboxylates. The use of several ether polycarboxylates as detergent ingredients has been described. Examples of useful ether polycarboxylates include the oxydisuccinates described by Berg in U.S. Patent 3,128,207, issued April 7, 1964, and Lamberti et al. U.S. Patent 3,635,030, issued Jan. 18, 1972. Both are incorporated herein by reference.

Among specific types of ether polycarboxylates. which are useful as components of the present invention include polycarboxylates of the general formula

9512

CH (A) (COOX) -CH (COOX) -O-CH (COOX) -CH (COOX) (B). in which A represents a hydrogen atom or a hydroxyl group, B represents a hydrogen atom or a group of the formula -O-CH (COOX) -CIte - (COOX) and X represents a hydrogen atom or a salt-forming cation. Thus, B represents a hydrogen atom, then the compound is oxydisuccinic acid and its water-soluble salts. When A is a hydroxyl group and B is a hydrogen atom, the compound is monosuccinic acid tartrate (TDS) and its water-soluble salts. When A is hydrogen and B is -O-CH (COOX) -Cite - (COOX), then the compound is succinic acid tartrate (C1DS) and its water-soluble salts. of these components. Particularly preferred are mixtures of IMS and TDS in a weight ratio of TMS to TDS of from 97-3 to 20 ^: 80. These components are described in U.S. Patent 4,663,071 Bush et al., Issued May 5, 1987.

Suitable ether polycarboxylates also include cyclic compounds, especially alicyclic compounds such as those described in U.S. Patents 3,923,679, 3,835

163, 4,158,635. 4,120,874 and 4,110,903. All of these patents are incorporated herein by reference.

Other useful detergent builders are the ether polyhydroxypolycarboxylates of formula

HO - [C (R) (COOM) - C (R) (COOM) - 01 n - I I. in which M represents a hydrogen atom or a cation, the resulting salt being soluble in water. preferably an alkali metal cation salt. an ammonium cation or a substituted ammonium cation, n is from 2 to 15 (preferably n is from 2 to 10, more preferably n is an average of 2 to 4) and the substituents R are independently hydrogen, C1-C4alkyl or a substituted alkyl group having 1 to 4 carbon atoms (preferably R is hydrogen).

9512

Other ether polycarboxylates include copolymers of maleic anhydride with ethylene or vinyl ether, 1,3,5-trihydroxybenzene-2,4,6-trisulfonic acid, and carboxymethyloxysuccinic acid.

Organic polycarboxylate components include various alkali metal salts. ammonium salts or substituted ammonium salts of polyacetic acids. Examples include sodium. potassium, lithium. ammonium and substituted ammonium salts of ethylenediaminoetetraacetic acid and n-tritriacetic acid.

Polycarboxylates also include succinic acid, succinic oxydisuccinic acid and polyaminoic acid. benzene-1,3,5-tricarboxylic acid, carboxymethyloxy succinic acid and soluble salts thereof.

Citrate ingredients, e.g. citric acid and its soluble salts (especially the sodium salt) are polycarboxylate components which can also be used in granular formulations.

Other carboxylate components include the carboxylated carbohydrates described in U.S. Patent 3,723,322 Diehl, issued March 28, 1973, which is incorporated herein by reference.

Also suitable for use in the detergent compositions of the present invention are the 3,3-dicarboxy-4-oxalines described in U.S. Pat. of the type Alkyl, the antioxidants are of the formula R-CH (COOH). CH 2 (COOII).

, 6 - h ex and other patents:

and the like:

566 984 Busha out of 1 is reported here for 11 pounds and cat. Mejantaric include alkyl (5 to 5 acids and salts thereof. Especially in which R is a hydrocarbon group, e.g., an alkyl or alkenyl group, both having from 10 to 20 carbon atoms and dodecenyl antarboxylic acid.

typically compounds of general interest

i succinic acid derivatives16

95.12 ka, preferably having 12 to 16 carbon atoms, or wherein R may be substituted with hydroxyl, sulfonyl. a sulfoxyl or sulfone substituent, all as described in the aforementioned patents.

Succinate components are preferably used in the form of their soluble alkali salts, including sodium, potassium, ammonium and alkaloammonium salts.

Specific examples of the succinate components include: lauryl succinate, myristyl succinate, paucyl succinate. 2-dodecenyl succinate (preferred), 2-pentadecenyl succinate and the like. Lauryl succinates are preferred components of this group and are described in European Patent Application 86200690.5 / 0.200,263, published November 5, 1986.

Examples of useful ingredients also include carboxymethyloxymalonates. sodium and potassium carboxymethyl succinates, cis-cyclohexane-hexycarboxylates and sodium and potassium cis-cyclopentane tetracarboxylates, water-soluble polyacrylates (these polyacrylates have a molecular weight up to 2000 and can also be effectively used as dispersants) and copolymers of maleic anhydride .

Other suitable polycarboxylates are polyacetal carboxylates. See U.S. Patent 4,144,226 Crutchi et al., issued March 13, 1979, which is incorporated herein by reference. These polyacetal carboxylates can be prepared by contacting a glyoxylic acid ester with a polymerization initiator under polymerization conditions. The resulting polyacetal carboxylate ester is then attached to chemically stable end groups to stabilize the polyacetal carboxylate against rapid depolymerization, even in an alkaline solution, converted to the corresponding salt, and added to the surfactant.

95.12

Polycarboxylate components are also disclosed in U.S. Patent 3,308,067 Diehl, issued March 7, 1967, which is incorporated herein by reference. These materials also include the water-soluble salts of homo- and copolymers of aliphatic carboxylic acids, such as maleic acid, itaconic acid, mesaconic acid, fumaric acid, aconitic acid, citraconic acid, and methylene malonic acid.

Other inorganic components known to those skilled in the art may also be used, for example, monocarboxylic acids and their soluble long chain hydrocarbon salts. These include materials commonly referred to as soaps. Typical chain lengths are 10 to 20 carbon atoms. The hydrocarbons may be saturated or unsaturated.

According to the invention, the detergent component is preferably selected from the group consisting of salts, preferably carbonate, silicate, sulfate, phosphate and sodium nitro-silicate, citric acid and mixtures thereof.

D. Second enzyme

Optional and preferred components include second enzymes which include protein C in the most preferred e), amylase, peroxase, cellulase, and mixtures thereof. By the second enzyme is meant the enzymes that are. in addition to lipase, they include second enzymes from chemically or genetically modified mutants and enzymes derived from bacteria or fungi.

The amount of second enzyme to be used in the formulation depends on the type of enzyme and the intended use. In general, from 0.000.1 to 1.0, more preferably from 0.001 to 0.5% by weight are preferably used. of these second enzymes (relative to the active enzyme). Mixtures of enzymes of the same class (e.g. proteinase) or two or more may also be used;) classes (e.g.

9512 (eg cellulase and proteinase).

Any cellulase may be used in the detergent composition. which is suitable for use in such formulations. From 0.0001 to 1.0, preferably from 0.001, can be used. up to 0% by weight. cellulases (relative to the active enzyme).

Suitable cellulases are described in U.S. Patent 4,435,307 to Barbesgaard et al., Issued March 6, 1984, which is incorporated herein by reference and which discloses fungal cellulase produced by Humicola insolens. Suitable cellulases are also described in British patent applications A 2 075 028 and A 2 095 275 and in German patent publication no. 2,247,832.

Examples of such cellulases are cellulases produced by Humicola insolens (Humicola grisea var. Thermoidea), in particular Humicola strain DSM 1800, cellulases produced by Bacillus N or by Aeromonas. which produces cellulase 212, and cellulase extracted from the marine shellfish hepatopakrea (Dolabe.Ua Auricula Solander).

Any amylase suitable for use in a detergent composition may be used in these compositions. Amylases include, for example, N-amylases obtained from a special strain of Bicheninforms, described in more detail in British Pat. Amylolytic proteins include, for example, Rapidasa ™, Maxamyl ™ and Termamyl ™.

From 0.0001 to 1.0, preferably 0.0005 to 0.5% by weight are used. active enzyme based amylases.

Peroxidase enzymes are used in combination with oxygen sources, e.g. peruhl ichi tanoin. perborate, persulfate, hydrogen peroxide, etc. They are used to bleach solution, i. to prevent it. that the dyes or pigments which are removed from the substrates during washing are transferred to

9512 other substrates in wash solution. Peroxidase enzymes are known to those skilled in the art. These include, for example, horseradish peroxidase. ligninase and haloperoxidase. such as chlorine bromo-peroxidase-Detergent-containing peroxidase-containing agents are described, for example, in International PCT Application WO 89/099813. published October 19, 1989 by Kirk (Novo Industries A / S), which is incorporated herein by reference.

An amount of from 0.0001 to 1.0, preferably 0.0005 to 0.5, most preferably 0.002 to 0.1% by weight is preferred for use in the invention. with a detergent-compatible proteinase (relative to the active enzyme). Also included are mixtures of proteinase enzymes. The proteinase can be of animal, vegetable or microorganism origin (preferably). More preferred is a serial proteinase enzyme of bacterial origin. They may also use purified or unpurified forms of this enzyme. By definition, proteinases produced by chemically or genetically modified inutants are included because they are close structural variants of enzymes. Particularly preferred is a bacterial serial proteinase enzyme derived from Bacillus subtilis and / or Paclitus icheninformis.

Suitable commercially available proteinase Inazô floor and Alcalase ^<R>, Esperase ^(R>. Savinase ^<R) (preferred), Naxatase ^(B), Maxacal ^<BJ (preferred), and Maxapem 15 ^<R) (made protein Maxacal ^(B) and subtilisin BPN and BPN '(preferred). Preferred proteinases are also modified bacterial serine proteinases, such as those described in European patent application no. No. 87 303761.8, filed April 28, 1987 (particularly pages 17, 24 and 98), herein referred to as proteinase B, and European Patent Application 199,404 Veriegasa, published October 29, 1986, referred to herein as a modified bacterial serial proteolytic enzyme. which is referred to herein as proteiriase A. Preferred proteolytic enzymes are selected from the group consisting of

Savinase ^(R) , Maxacal ^(R) , BPN ', B and mixtures thereof. Most preferred is Proteinase A, Proteinase B.

for inase

E. Other ingredients

Other ingredients suitable for use in the compositions of the invention include water. perfume, brightener, conditioners such as silica powder, polyethylene glycol. dyes and peroxyacids. Preferred components are preferably from 0.5 to 5% by weight. polyethylene glycol (preferably having a molecular weight between 5000 and 1,000,000, most preferably 0000), from 0.01 to 0.7% by weight. % fluorescent whitening and / or brightening agents and from 0.01 to 1.0% by weight. perfume u.

Bleaching agents, including preformed peracids, activated perborates and activated percarbonates, may also be present in the granular compositions, although such agents are not preferred. The amounts proposed are from 0.5 to 5% by weight. peracids, from 5 to 25 wt%. percarbonate or perborate and from 0.1 to 10% by weight. an activator. A preferred activator for use with a lipase is tertaacetylethylenediainin. Preferred are bleach-free compositions with the exception of 0.5 to 1.0% by weight. sodium perborate.

The granular detergent composition is generally added to the wash water in an amount of 1/4 to 1 measuring cup.

The present invention further provides a method of purifying substances in the wash water thereby. by contacting these substances with effective amounts of a granular detergent composition. which contains:

(a) a lipase produced by Humicola sp., Thermomyces sp., Pseudomonas pseudoalcaligenes or Pseudomonas fluorescens in an amount of from 0.0000025 to 0.006 g active enzyme per 100 g of preparation.

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b) from 0.5 to 10% by weight of alkyl laxysulfate and / or polyoxydroxy fatty acid amide; and

(c) from 2 to 30% lunts. a further au-tin or non-ionic surfactant, wherein the ratio of component a) to component b) is between 0.09 and 0.28.

For good cleaning, stirring is preferably carried out in the washing machine. Stirring is preferably followed by drying the wet fabric in a conventional laundry dryer. The effective amount of the granular detergent composition is preferably from 500 to 7000 ppm, more preferably from 1000 to 3000 ppm.

The following examples illustrate the invention, but do not necessarily mean limiting or otherwise defining the scope of the invention.

All proportions, percentages and ratios used herein are by weight. unless otherwise specified.

DETAILED DESCRIPTION OF THE INVENTION

Example 1

The following wash tests were carried out to determine the effects of purification when using less lipase. A more potent defergent formulation with and without lipase was evaluated.

S posotí

He was on both cotton and cotton fabrics. I made stains from fatty foods either with bacon fat (4 drops) or spaghetti sauce (coated). These stains were washed twice in three washing machines for each product (see detergents A and B below). The evaluation was therefore based

9512 on six different pieces of fabric with stains for both bacon fat stains and spaghetti sauce stains. For a 12-minute wash cycle and a 35-minute drying cycle, stains were scored ”or compared to total stain removal in three stages (blank test) with the results below.

conclusion

Detergent A samples do not contain an alkyl or alkoxy fatty acid or polyhydroxy fatty acid amide. Detergent A samples contain lipase in three different amounts: 0, 0.012 grams of active enzyme per 100 grams of the formulation (500 LU / L, 0.48% by weight) and 0.036 g / 100g (1500LU / L, 1.44% by weight). . As shown in Table A, in the first wash cycle, detergent A with lipase (both samples) was worse than. lipase-free detergent A.

Table B relates to detergent composition 0. Surprisingly, it has been found that detergent B containing polyhydroxy fatty acid amide (N-acetyl fatty acid amide) and 0.012 g / 100ci lipase (500 LU / L) is significantly superior to detergent B with triple lipase (0.036 g / 100g, 1500 LU / L) and lipase-free detergent B (Table B). Detergent EI with 0.012g / 100g lipase is within the scope of the invention. The other two detergents are not within the scope of the invention23

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Result

Table A

spots deterg.A very deterg.A 500 LU / L 1 ipázy deterg- A 1500 LU / L 1 i pasy Bacon / Cotton fat 0.0 -0.68 -1,34.x grease with linen / cotton 0.0 -0.03 -0.76 Spaghetti / polybav1na 0.0 -1.05 -1.53 * Spaghetti / bav1na 0.0 -1. .1.6 * -1.07 *

Scale used: 0 means stain after standard detergent treatment, +1 to +4 means degree of improvement of removal after use of detergent alone, -1 to -4 means degree of deterioration of removal after use of detergent alone x means significant difference at 95¾ confidence interval (LSD)

Note: 500 LU / 1 means 0.012 g / 100 g or 0.40% by weight. and 1500 LU / L means 0.036g / 100g or 1.44% by weight.

in preparationTable B

spots de terg- B very deterg.B 500 LU / L 11pázy deterg.B 1500 LU / L 1 i pasy Fat salty ny / pojy bav1n a 0.0 00:12 0. .1.8 saline fat / cotton 0.0 .1,34 * 0,1.8 * Spaghetti / po1ybav1na 0.0 1.24 * 00:30 Spaghetti / bav1na 0.0 1,27 x 00:33

Scale used: same as in table Λ: χ means significant difference at 95¾ confidence interval (LSD)

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Detergent Ä (without alkyl alkoxy sulphate or polyhydroxy fatty acid amide component% by weight12.3 1 1-alkyl alkylbenzenesulfonate 18,41 sodium alkyl of 14 to 15 carbon atoms 5.95 sodium carbonate 21.33

A sodium aluminosilicate 26.30 solid creams 2.29 polyethylene glycol (molar mass 8000) 1.74 alcohols (C 12 -C 13) polyethoxylate (E6.5) 0.50 brightening agent 0.30 perfume 0.10 water 10.06 acid or throne 3.50 primes. sodium carbonate 8.39 sodium perborate 0.35, perfume 0.26 proteinase Savi nase ⁽¹¹ * 0.52

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Detergent B (with polyhydroxy fatty acid) component% by weight.

12.3 linear sodium alkylbenzene sulphonate 22.39 alkyl sulphate. sodium carbonate of 14 to 15 carbon atoms 9.50 sodium carbonate 26.60 polyethylene glycol (mol. wt. 8000) 2.04 N-acetyl fatty acid glucaine 1.94 brightener 0.30 perfume 0.10 water .1.0.06 citric acid 11.29 layered silicate 6.40 impurity sodium carbonate 0.39 sodium perborate 0.35 perfume 0.26 proteinase Savinase ^(RJ 0.52

Example 2

The efficacy of the lipotic enzyme in the detergent composition of the type described and the comparative efficacy of the lipotic enzyme in the comparative detergent composition are evaluated as follows:

(a) Trioine soiled polyester materials are washed in a mini washing machine under individual conditions using the two detergent preparations listed below.

(b) A gravimetric analysis of the residue remaining on the substance is performed to obtain an index of the amount of oil remaining on the standard test substance. Gas chromatography of the extracted residues is carried out. in order to obtain the relative potency of the lipolytic enzyme under the given conditions.

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The following detergent compositions were used (Ca) (b)% limot -% wt linear sodium alkylbenzene sulphate / sodium alkyl sulphate ¢ 70/30) 19 21 alcohol C 12 to 13 carbon atoms) polyethoxylate (6.5) 0 3 alkyl ethoxy (E1) sulfate 0 1 glucosamide 0 3 sodium carbonate 23 21 citric acid 3 3 proteinase Savinase ^(R) 1 1

In both cases the same amount of lipase (L1polase ^<R> ) is used. The water temperature is 40 ° C.

For washing with formulation (a), the test shows the presence of 0.18 g oil and 40 wt. triglyceride remaining in the extracted material.

Obviously, formulation (b) allows the removal of more free fatty acids (ΓΓΑ) from the material (removed by 0.7 g more), while the lipolytic enzyme releases the same percentage ΡΓΆ (40 and 50% w / w) in both cases.

Conclusion: An improved surfactant formulation (e.g., detergent b with glucosamide and alkyl ethoxy sulfate; according to the present invention) allows more efficient removal of hydrolytic lipase products than a formulation with a weaker surfactant (e.g., detergentite a, which is not according to the invention).

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At the dump 3

The composition of the invention has the following benefits; Ingredients:

% limott component

12.3 linear sodium alkylbenzene sulphonate 14.31 sodium alkyl sulphate of 1.4 to 15 carbon atoms 4.09 solid phosphates 43.85 sodium carbonate 0.32 sodium silicate 6.47 polyethylene glycol (mw 8000) 0.80 alkylethoxy (E1) sulfate 2.00 alcohol (with 12 to 12) 15 carbon atoms) polyethoxylate (E9) 0.50 brightener 0.28 perfume 0.10 water 6.13 * causes:

sodium carbonate 8.39 _r sodium perborate 0.35 perfume 0.21

Lipolase ^<R> 0.29 proteinase B 0.52 si 1 icon flakes 0.20

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Example 4

The composition of the invention has the following composition:

component % wt. 12.3 sodium linear alkylbenzenesulfonate 13.16 sodium alkyl sulfate of 14 to 15 carbon atoms 3.70 sodium carbonate 9:46 sodium aluminosilicate 26.30 solid silicates 2.29 sodium polyacrylate 3:39 sodium sulfate 10.36 alky1etoxy (El) sulfate 1.94 (C12 -C13 alkoxy) polyl- ethoxylate (E9) 00:50 brightener 00:30 Water 9, t 1 admixture ^: sodium carbonate 14.70 sodium perbortate 1.00 perfume 0.35 Lipolase ^ťR * 0.29 proteinase B 0.26 silicon dioxide 00:45

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Example 5

The composition of the invention has the following composition:

component touch. sodium alkyl sulfate of 14 to 15 carbon atoms 6.36 N-acetylglucamide of 16 to 18 carbon atoms 3.82 alkyl ethoxy <E2.25) sulfate 1.27 alcohol (C12-C13) poly- ethoxylate C6.5) 3.44 sodium aluminosilicate 14,00 acidic to thionic acid 3.82 layered silicate 14:00 tet. racetyl ethylenediamine; 6.36 sodium percarbonate 20.36 d i 0.48 magnesium sulfate 0.51 Savinase proteinase 1.78 1ipázax 00:46 cellulase 0.32 sodium carbonate 7.64 a soil release polymer 0.64 acrylic / maleic acid copolymer 3.82 brightener 0.31 f taokyan i ns u1f onate i n night 0.29 perfume 0.41 foam suppressor 2.4 water and minor components to add

χ from Pseudomonas pseudoalcaligenes <100000 LU / g)

May be replaced by Lipolase _of Humicola lanuginosa.

Claims (9)

I &apos;, 3 < 9/9512 Granular characterized by a) lipase Therinomyces sp. , a detergent composition, e.g. comprising: a strain of Humicola sp., Pseudomonas pseudoalcaligenes; or Pseudomonas fluorescens in an amount of from 0.00025 to 0.015 g of active enzyme per 100 g of preparation, b) from 0.5 to 10% by weight. alkyl alkoxy sulphate or polyhydroxy fatty acid amide; and c) from 2 to 30% by weight of an additional anionic or nonionic surfactant, wherein the ratio of component a) to component b) is between 0.09 and 0.28. t ' 2. A granular detergent composition according to claim 1, wherein the anionic surfactant is sodium alkyl sulfate of 12 to 20 carbon atoms and linear alkylbenzene sodium sulfate of 9 to 20 carbon atoms, and the nonionic surfactant is a condensation product of an alcohol with 10 to 20 carbon atoms with 2 to 20 moles of ethylene oxide per mole of alcohol, the composition further comprising from 1 to 80% by weight. detergent component. 3. A granular detergent composition according to claim 1 or 2. The composition comprises a lipase produced by Humicola Lanuginosa or Pseudomonas pseudoalcal i geries in an amount of from 0.0025 to 0.010 g of active enzyme per 100 g of formulation. 4. A granular detergent composition according to any one of claims 1 to 3. It comprises from 0.5 to 5% by weight. alkyl sulfate which is ethoxylated with 0.5 to 10 moles of ethylene oxide πει mole of alkyl 9512 sulfate. A granular detergent composition according to any one of claims 1 to 4, characterized by t. wherein the amount of lipase divided by the amount of alkylalkoxysuifate or polyhydroxy fatty acid amide is between 0.10 and 0.20. A granular detergent composition according to any one of claims 1 to 5, further comprising from 20 to 70% by weight. a detergent component selected from the group consisting of salts of carbonate, silicate, sulfate, phosphate, hemi-silicate, citric acid, and mixtures thereof. A granular detergent composition according to any one of claims 1 to 6, further comprising from 0.0001 to 1.0% by weight. of an active second enzyme. A granular detergent composition according to any one of claims 1 to 7, further comprising from 0.0005 to 0.5% by weight. of an active proteinase compatible with a detergent. A granular detergent composition according to any one of claims 1 to 8, further comprising from 0.0001 to 0.6% by weight. lipase (having activity of 100,000 LU / g), which is produced by cloning the gene from Humlcola lanuglnosa and expressing the gene in Aspergillus oryzae. The method of purification is that in riymi amounts comprising: The compositions are contacted with an effective granular detergent composition. 9512 (a) the lipase produced by Huinicola sp. Thermomyces sp. Pseudomonas pseudoalcaligenes or F'seudomonas fluorescens in an amount of from 0.00025 to 0.015. preferably from 0.0025 to 0.010 g of active enzyme per 100 g of preparation, b) from 0.5 to 10% by weight. alkyl alkoxy sulphate and / or polyhydroxy fatty acid amide; and c) from 2 to 30% by weight. a further anionic or nonionic surfactant, wherein the ratio of component a) to component b) is between 0.09 and 0.28.