MXPA97005326A - Detergent composition that comprises zeolite map and amil enzymes - Google Patents

Abstract

A detergent composition containing an amylase enzyme, and a detergency builder comprising zeolite P having a silicon to aluminum ratio that is not greater than 1.33 (zeolite MAP), preferred are granular and liquid detergent compositions and methods are described. to make such composition

Description

DETERGENT COMPOSITION COMPRISING ZEOLITE MAP AND AMILASA ENZYMES BACKGROUND OF THE INVENTION The present invention relates to a detergent composition comprising an amylase enzyme and a zeolite component as a sequestering agent for water hardness. Conventionally, water-soluble inorganic phosphates, such as sodium tripolyphosphate, have been used as detergency builders for laundry detergents. More recently, alkali metal aluminosilicate ion intercarriers have been proposed, in particular sodium aluminosilicate zeolites insoluble in crystalline water, as replacements for the inorganic phosphates. For example, EP 21 491A (Procter »Gamble) discloses detergent compositions containing a builder system including zeolite A, X or P (B) or a mixture thereof. EP 384Q70A (Unilever) discloses specific zeolite P materials having an especially low ratio of silicon to aluminum no greater than 1.33 (hereinafter referred to as zeolite MAP) and describes their use as builders. It has been surprisingly discovered that a problem can occur when zeolite MAP insoluble in water, in particular when it is present as particles having a small particle size, is used as a detergency meaner in a composition containing no amylase enzyme formulated to be used in the laundry of fabrics. The choice of a size of p > small particle for any component of zeolite MAP, ie for example particles having a particle size, measured as a deo value, up to 1.0 millimeter, is preferred in the art, as co-represented by, for example, EP 384070 A. The problem relates to the formation of white residues, which adhere to the fabrics and remain there at the end of a washing procedure for laundry. The degree of residue formation can vary. In dyed fabrics, the appearance of white debris tends to be more evident visually than in white fabrics. White debris is often formed in areas of cloth where there are stains, which interfere with and prevent the complete removal of the stain. As a result of the visible contrast between the white residues and the stained cloth, the stained area where white deposits have formed may be more noticeable than the original stain. It has been established that when an amylase enzyme is employed in compositions containing zeolite MAP, even when it is in the form of small particle size, the problem of white residue formation in fabrics is reduced. It has also been established that the choice of a zeolite having a larger particle size than that preferred by the art, in particular EP 384070 A, can further reduce the tendency for white deposit formation to occur. As the prior art, as represented, for example, by European Patent Applications, EP 384070 A, EP 448297 A, EP 522726A, EP 533392 A, EP 544492 A, EP 552053, and EP 552054 A, has contemplated the Use of enzymes in combination with zeolite MAP in laundry detergent compositions, none of these prior art documents specifically describe the use of amylase enzyme with a zeolite MAP component. Furthermore, none of these prior art documents provides any teaching that addresses the problem of white residue deposition addressed by the present invention, nor a solution thereto that involves the selection of a particular enzyme. According to the present invention there is provided a detergent composition containing (a) a zeolite detergent builder comprising zeolite P having a silicon to aluminum ratio which is not greater than 1.33 (zeolite MAP) (b) an amylase enzyme; DETAILED DESCRIPTION OF THE INVENTION IMPROVING THE DETERGENT OF ZEOLITfl MflP The first essential component of the present invention is a builder of zeolite MAP, optionally in conjunction with one or more supplementary detergency builders. Zeolite MAP is typically present at a level of 1% to 80%, most preferred of 15% to 40% by weight of the compositions. Zeolite MAP is described in EP 384070A (Unilever). It is defined as an alkali metal aluminosilicate of the zeolite P type having a silicon to aluminum ratio which is not greater than 1.33, preferably within the range of 0.9 to 1. 33 and very preferred within the scale of 0.9 to 1.2. Of particular interest is zeolite MAP which has a silicon to aluminum ratio which is not greater than 1.15 and, more particularly, is not greater than 1.07. Zeolite P having a Si: Al ratio of 1.33 or less can be prepared by the following steps: (i) mixing together a sodium aluminosilicate having a molar ratio of Na2? : Al2? 3 within the scale of .1. 4 to 2 0 and a sodium silicate having a molar ratio of Si? 2: a2? within the scale of 0. 8 to 3. 4 with stirring vi gorosa at a temperature within the range of 25 ° C to boiling point usually 95 ° C, to give a gel having the following composition; AI2O3: (1.75-3.5) Si02: (2.3-7.5) N 2? : P (80-450) H20; (ii) aging the gel composition for 0.5 to 10 hours, preferably 2 to 5 hours, at a temperature within the range of 70 ° C to boiling point, usually at 95 ° C with sufficient stirring to keep any solid in suspension I presented; (iii) separating the crystalline sodium aluminosilicate so formed, washing at a pH within the range of 10 to 12.5, and drying, preferably at a temperature not exceeding 150 ° C, at a moisture content not less than 5% by weight. The preferred drying methods are spray drying and flash drying. It appears that oven drying at a very high temperature can adversely affect the calcium binding capacity of the product under certain circumstances. The commercial sodium eosilicate pentahydrate dissolved in water and the commercial sodium silicate solution (liquid glass) are suitable silica sources for the production of zeolite P according to the invention. The reagents can be added together in any order either quickly or slowly. Rapid addition at room temperature, and slow addition at elevated temperature (90-95 ° C) give the desired product. However, the vigorous agitation of the gel during the addition of the reagents, and at least the moderate agitation during p > Subsequent aging appear to be essential for the formation of pure P zeolite. In the absence of agitation, various mixtures of crystalline and amorphous materials can be obtained. The zeolite MAP generally has a calcium binding capacity of at least 150 g CaO per g of anhydrous aluminosilicate, as measured by the standard method described in GB 1473201 (Hen el). The calcium binding capacity is normally 160 mg CaO / g and can be as high as 170 mg CaO / g. Although zeolite MAP co or other zeolites contain water for the purposes of the present invention the amounts and percentages of zeolites are expressed in terms of the notional anhydrous material. The amount of water present in the MAP zeolite hydrated at room temperature and the humidity is generally about 20% by weight. In a preferred aspect, the zeolite MAP builder has a particle size, expressed as a dso value of 1.0 to 10.0 microns, more preferably 2.0 to 7.0 microns, most preferred 2.5 to 5.0 microns. 324 The dso value indicates that 50% by weight of the particles have a smaller diameter than that figure. The particle size can, in particular, be determined by conventional analytical techniques such as microscopic determination using a scanning electron microscope or by means of a laser granulometer. Other methods for establishing dso values in EP 384070A are described. flMILflSfl The second essential component of the compositions is an amylase enzyme, i.e., for example, an enzyme having aryl-lolithic activity. The amylase enzyme is typically incorporated in the compositions according to the invention at a level from 0.01% to 5%, preferably from 0.1% to 3%, more preferably from 0.2% to 2%, most preferred from 0.3% to 1.5% of Active enzyme by weight of the composition, on an activity basis of 60 KNU / g (Kilo Novo / Gram units). Units of "Kilo Novo / Gram Units (KNU / g)" are well-known means for defining the activity of amylolytic enzyme and are described in GB-1,259,839 A (Novo). In more detail, 1 KNU is the amount of enzyme that divides 5.25 grams of starch (Merck, Amylu Solubile Erg. B.6, Batch 9947275) per hour in the method described in 6B-1,269,839 A, which has the following normal conditions: Substrate Soluble Starch Content of calcium in solvent 0.0043 M Reaction time 7-20 minutes Temperature 7 ° C pH 5.6 The enzyme arnilasa can be fungal or bacterial in origin. Ilases obtained by chemical or genetic manipulation of fungal or bacterial derived chains are also useful herein. The amylase enzyme is preferably an α-amylase. Preferred amylases include, for example, α-alases obtained from a special chain of B. licheniformis, described in more detail in GB-1,269,839 A. Registered deposit numbers for B. licheniformis chains capable of producing α-amylases include NCIB 8061, NCIB 8059, ATCC 6634, ATCC 6598, ATCC 11945, ATCC 8480 and ATCC 9945a. Preferred commercially available α-amylases include, for example, those sold under the tradename Rapidase and Maxamyl by Gist-Brocades; those sold under the trademark Taka-Therm L-340 by Miles Laboratories, Elkhart, Indiana; those sold under the trademark Rohalase AT by Rohm and Haas, Uest Philadelphia, PA; and those sold under the trademarks Terrnamyl 60T and 120T, Fungamyl and BAN by Novo Industries A / S.

In a preferred aspect, the amylases have been designed to have improved stability, in particular having improved stability for oxidation, for example in a bleaching environment, and improved thermal stability. The stability can be average using any of the technical tests known in the art including those referred to in UO 94/02597 0. The arnilases of improved stability are + commercially available from Novo Industries A / S or from Genencor 'Internal * íonai. Preferred alkali metals with improved oxidative stability are derived using si-mutagenesis directed from one or more of the Baccillus arylases, especially the Baccillus α-amylases, regardless of whether one, two or multiple amylase chains are the precursors. intermediaries. Preferred amylases of this type are described in UlO 94/02597 A, and comprise a utante in which the substitution is made, using alanine or threonine, preferably threonine, of the ethionine residue located at position 197 of α-amylase B licheniformis, sold under the trademark Terrna yl, or the variation of the homologous position of a similar original amylase, such as B. amyloliquefaciens, B. subtilis, or B. stearothermophilus. Other preferred amino acids having improved oxidative stability, derived from B. licheniformis NCIB806, are described by Genencor International in a document entitled "Oxidatively Resistant a-Amylases" which was presented at the 207th meeting of the American Chemical Society National Meeting, from 13 to 17 March 1994, by C. Mitchinson. Inethionine (Met) was identified as the residue most likely to be modified. Met, one at a time, was substituted at positions 8, 15, 197, 256, 304, 366 and 438 leading to specific utants, in particular M.197L and M197T being impotant with the M197T variant being the variant expressed more stable. Other preferred amylases having improved oxidative activity include those described in UO 94/18314 A (Genencor International) and UO 94/02597 A (Novo). Any other amylase of improved oxidative stability can be used, for example as derived by means of site mutagenesis directed from chimeric, hybrid or simple, known, original forms of available amylases. Other enzyme modifications are acceptable including those described in UO 95/09909 A (Novo). It will be appreciated that enzymes for incorporation into solid detergent compositions are generally sold commercially with enzyme pellets containing active enzyme supported on a variety of inert host materials, which, for example, may include alkali metal sulfates, carbonates and silicates. Optionally, organic binder materials can also be incorporated. In a preferred aspect, the calcium content of these enzyme pellets is minimized to ensure storage stability in good product of the enzyme.

ADDITIONAL DETERGENT COMPONENTS The detergent composition according to the invention may contain other detergent components such as surfactants, detergent co-builders, bleaches, fluorescers, anti-redeposition agents, inorganic salts such as sodium sulfate, other enzymes, foam control agents. , fabric softening agents, pigments, stained spots and perfumes.

TENSIOflCTIVE AGENT The detergent composition according to the invention preferably includes a surfactant selected from anionic, nonionic, zwitterionic, ampholytic and cationic agents. The surfactant is preferably present in the detergent compositions at a level of from 1% to 50%, preferably from 3% to 30%, most preferred from 5% to 20% by weight of the compositions. Many suitable active detergent compounds are available and are fully described in the literature (for example "Surface Active Agents and Detergents" volumes I and II by Schwartz, Perry and Berch). Examples of additional anionic surfactants include anionic sulfates, olefin sulphonates, alkylxylene sulphonates, dialkylsulfosuccinates, and fatty acid ester sulfonates. Sodium salts are generally preferred.

TENSITIZING AGENT OF FUNNIC SULFATE Suitable anionic sulfate surfactants for use herein include the linear and branched alkali metal salts, alkyl ethoxy sulfates, fatty oleolyl glycerol sulfates, alkyl phenol ethylene oxide ether sulphates, sulfates of Cs-Ci? acyl-N- (Ci-C * alkyl) and -N- (Ci-C2 hxyalkyl) gl? walks, and alkylpolysaccharide sulfates such as the alkyl polyglucoside sulfates (the non-sulphonated non-ionic compounds are described herein) . The alkyl ethoxy sulfate surfactants are preferably selected from the group consisting of Cß-Ciß alkyl sulphonates which have been ethoxylated with 0.5 to 20 moles of ethylene oxide per molecule. More preferably, the alkyl ethoxy sulfate surfactant is a C 1 -Cys alkylsulfate which has been ethoxylated with from 0.5 to 20, preferably from 0.5 to 5, moles of ethylene oxide per molecule.

ANIONIC SULPHONATE SURGICAL AGENT Suitable anionic sulfonate surfactants for use herein include salts of C5-C20 alkylbenzene sulphonates, ester alkylsulfonates, C6-C22 primary or secondary alkanesulfonates, C6-C24 olefinsulfonates, sulfonated polycarboxylic acids, alkyl glycerol sulfonates, fatty acyl glycerol sulfonates, fatty oleyl glycerol sulfonates, and any mixture thereof.

NON-IONIC TENSITIZING AGENT The nonionic surfactant is preferably a non-ionic hphobic surfactant, particularly an alkoxylated nonionic surfactant, having a hphilic-lipophilic equilibrium (HLB) value of < 9.5, most preferably from < 10.5. Examples of non-ionic alkoxylated hphobic surfactants include alkoxylated adducts of fatty alcohols containing an average of less than 5 alkylene oxide groups per molecule. The alkylene oxide residues, for example, may be residues of ethylene oxide or mixtures thereof with residues of propylene oxide. The preferred alkylene oxide adducts of fatty alcohols useful in the present invention can be suitably chosen from those of the general formula: R-0- (C "H2nO) and H wherein R is an alkyl or alkenyl group having at least 10 carbon atoms, most preferably 10 to 22 carbon atoms, and is 0.5 to 3.5 and n is 2 or 3. Preferred nonionic surfactants include condensed primary Cn-Cis aliphatic alcohols with an average of no more than 5 ethylene oxide groups per mole of alcohol, having an ethylene oxide content of less than 50% by weight, preferably from 25% to less than 50% by weight. A particularly preferred ethoxylated aliphatic alcohol is a primary alcohol having an average of 12 to carbon atoms in the alkyl chain condensed with an average of three ethoxy groups per mole of alcohol. Specific examples of suitable alkoxylated adducts of fatty alcohols are Synperonic A3 (ex ICI), which is a C13-C15 alcohol with about three ethylene oxide groups per molecule, and E pilan KB3 (ex Marchon), which is lauric alcohol 3E0. Another class of nonionic surfactants comprises alkylpolyglucoside compounds of the general formula wherein Z is a glucose-derived portion; R is a saturated hydrophobic alkyl group containing from 12 to 18 carbon atoms; t is from 0 to 10 and n is 2 or 3; x is from 1.1 to 4, the compounds including less than 10% unreacted fatty alcohol and less than 50% short chain alkyl polyglycosides. Compounds of this type and their use in detergent compositions are described in EP-B 0070074, 0070077, 0075996 and 0094118.

C0-DETERGENCY ME3QRAD0RES In addition to zeolite MAP, the builder system may contain an organic or inorganic co-builder. Suitable organic detergent builders may be onerous or polymeric carboxylates such as citrates or polymers of acrylic, methacrylic and / or metal acids in neutralized form. Suitable inorganic co-builders include sodium, lamellar, amorphous and crystalline carbonates and silicates. Suitable layered silicates have the composition: NaMSÍH? 2? + L and H20 where M is sodium or hydrogen, preferably sodium; X is a number from 1.9 to 4; and Y is a number from 0 to 20. Such materials are described in the patents of E.U.A. No. 4664839: No. 4728443 and No. 4820439 (Hoechst AG). Especially preferred are compounds in which x = 2 y = O. The synthetic material is commercially available from Hoechst SG as or Na2S.i.2? 5 (SKS6) and the patent of E.U.A. No. 4664830. The total amount of builder in the granular composition typically ranges from 10 to 80% by weight, most preferably from 15 to 60% by weight and most preferably from 10 to 45% by weight.

BLEACH The detergent compositions according to the invention may also suitably contain a bleaching system. This preferably comprises one or more peroxy bleach compounds. , for example, inorganic persalts or organic peroxyacids, which can be used together with bleach precursors to improve the bleaching action at low temperatures. The bleach system preferably comprises a bleach compound of p > preferably an inorganic persalt, optionally together with a precursor. Suitable persalts include sodium perborate monohydrate, and tedraidrate and sodium percabonate, with sodium percabonate being most preferred. Preferred bleach precursors are peracetic acid precursors; such as tetracetyethylene diamine (TAED); peroxybenzoic acid precursors.

PHYSICAL FORM The detergent composition according to the invention can be of any physical type, for example, powders, liquids and gels. However, granular and liquid compositions are preferred.

TRAINING PROCEDURE The detergent compositions of the invention can be prepared by any suitable method. The particulate detergent compositions are suitably prepared by any tower (spray-drying) or non-tower process. In methods based on a spray-drying tower, a base powder is first prepared by spray-drying a suspension and then other components not suitable for processing through the suspension can be sprayed or mixed (post-dosed). Zeolite MAP is suitable for inclusion in the suspension, although it may be advantageous for processing reasons for part of the zeolite MAP to be incorporated after the tower. The layered silicate, where employed, is also incorporated by a non-tower process and is preferably post-dosed. Alternatively, the particulate detergent compositions according to the invention can be prepared by completely towerless processes such as granulation. The granular detergent compositions of the invention can be prepared at any suitable bulk density. The compositions preferably have a bulk density of at least 400 g / 1, preferably at least 550 g / 1 and particularly preferably at least 800 g / 1. The benefits of the present invention are particularly evident in powders of high bulk density, for example 700 g / 1 or more. Said p >olvos can be prepared either by densification after the spray dried tower, or by completely non-tower methods such as dry mixing and granulation; in both cases, a high density nezclador / granulator can be advantageously used. Proes using high density mixers / granulators are described, for example, in EP340 013A, EP 367 339A, EP 390 251 and EP 420 317A (Unilever). The detergent composition of the invention can be formulated as a liquid detergent composition which can be aqueous or anhydrous. The term "liquid" used herein includes viscous, pasty formulations, such as gels. The liquid detergent composition generally has a pH of 6.5 to 10.5.

The total amount of detergency builder in the liquid composition is preferably from 5 to 70% of the total liquid composition. Illustrative compositions in accordance with the present invention are presented in the following examples. In detergent compositions, abbreviated component identifications have the following meanings: C11-C13 linear alkyl acylbenzenesulfonate 45AS Branched sodium alkylsulphate surfactant containing Cm-C15 alkyl chains 246AS Sodium alkylsulfate surfactant containing a weight distribution of alkyl chain length of 15% C12 alkyl chains 45% Cu alkyl chains, 35% Cyan alkyl chains, 5% Cyan alkyl chains TAS Surfactant sodium alkylsulfate containing predominantly Ciß-Ciß alkyl chains derived from tallow oil. 24AE3S: C E-C sodium ethoxysulfate ?? which contains an average of three ethoxy groups per mole. 35E3: A primary alcohol of C13-IS condensed with an average of 3 moles of ethylene oxide. 25E3: A primary alcohol C12-15 condensed with an average of 3 moles of ethylene oxide. 24EY A linear primary alcohol of C12-1-; condensed with an average of Y moles of ethylene oxide Carbonate: Anhydrous sodium carbonate. Perborate: Sodium Perborate Tetrahydrate Perca Bonate Sodium Percarbonate TAED Tetraacetiletilendiarni to Silicato Amorphous sodium silicate (the ratio of S lo2 = 2 Noapnamente proceeds) CMC carboxymethylcellulose Suppressor of Foams 25% paraffin wax, 50 ° C melting point 17% of hydrophobic silica, 58% of parafi oil to Zeolíta MAP: hydrated sodium alkylno-silicate of formula MAP having a silicon to aluminum ratio of 1.07. MA / AA: Rnaleic acid / acrylic copolymer 1: 4, average molecular weight of approximately 80,000.

Amylase Enzyme amylase sold under the trademark Termarnyl 60T by Novo Industries A / S (60KNU / gram of enzyme activity) BSA Enzyme to ilolytic - variant M197T, which has improved oxidative stability (60KNU / gram of enzymatic activity) Protease Proteolytic enzyme sold by Novo Industries A / S under trademark Savinase activity of 4.0 KNPU / gram Lipase Lipolytic enzyme sold by Novo Industries A / S under registered trademark Lipelase activity of 100,000 LU / gram 00 EXAMPLE 1 The following granular laundry detergent compositions (parts by weight) were prepared according to the invention. All amylase enzyme levels refer to active enzyme levels, expressed on an activity basis of 60 KNU / g.

Water and various components (including foam suppressors, sodium sulfate, perfume) for the rest.

EXAMPLE 2 The following granular laundry detergent compositions of 850 grams / liter (parts by weight) were prepared according to the invention. All amylase enzyme levels refer to active enzyme levels, expressed on an activity basis of 60 KNU / g.

Water and various components (including foam suppressors, sodium sulfate, perfume) for the rest.

Claims (13)

1. NOVELTY OF THE INVENTION CLAIMS l. ~ A detergent composition containing (a) a zeolite detergent builder which complies rende zeolite P having a ratio of silicon to aluminum which is not greater than 1.33 (zeolite MAP) (b) an amylase enzyme.
2. 2. A detergent composition according to claim 1, further characterized in that said detergent builder of zeolite MAP has a particle size, expressed co or a dso value of 1.0 to 10.0 micrometers.
3. 3. A detergent composition according to claim 2, further characterized in that said zeolite MAP builder has a particle size, expressed as a dso value of 2.0 to 7.0 micron.
4. 4. A detergent composition according to claim 1, further characterized in that said zeolite detergent builder is present at a level of 1% to 80% by weight of the composition.
5. 5. A detergent composition according to claim 1, further characterized in that said enzyme amylaea is an a-arnilasse.
6. 6. A detergent composition according to claim 1, further characterized in that said amylase enzyme has been modified in order to improve its oxidative stability.
7. 7. A detergent composition according to claim 1, further characterized in that said amylase enzyme is present at a level of 0.01% to 5%, of active enzyme by weight of the composition, on a base of activity of 60 KNU / g. B.
8. A detergent composition according to claim 1, further characterized in that said amylase enzyme is present at a level of 0.2% to 2% active enzyme by weight of the composition on an activity basis of 60 KNU / g.
9. 9. A detergent composition according to claim 1, further characterized in that it contains a surfactant at a level of 1% to 50% by weight of the composition.
10. 10. A detergent composition according to claim 1, further characterized in that it contains an organic or inorganic detergency builder.
11. 11. A detergent composition according to claim 10, further characterized in that said co-builder is a crystalline layered silicate.
12. 12. A detergent composition according to claim 1, further characterized in that it contains a bleaching system comprising a peroxy bleach compound and a peroxy acid whitening precursor.
13. 13. A detergent composition according to claim 12, further characterized in that said peroxy bleach is sodium percarbonate.