MXPA97005327A - Detergent composition comprising zeolite and enzyme amil - Google Patents

Abstract

A detergent composition containing an amylase enzyme, and a detergency builder comprising zeolite having a particle size, expressed as a d50 value, of less than 1.0 micrometer is described, granular and liquid detergent compositions are preferred and methods are described to make such composition

Description

COMPOSITION DETERGENT COMPRISING ZEOLIT AND ENZYME FHILAS BACKGROUND OF THE INVENTION The present invention relates to a detergent composition comprising an arnilasa enzyme and a small particle size component as a sequestering agent for water hardness. Conventionally, water-soluble inorganic phosphates, such as sodium polyphosphate, have been used as detergents for laundry detergents. More recently, alkaline metal alkali metal halides have been proposed, in particular, sodium alkylsilicate insoluble in crystalline water, as replacements for inorganic phosphates. For example, EP 21 91R (Procter S Gamble) discloses detergent compositions containing a detergency builder system that includes zeolite P, X or P (B) or a mixture thereof. EP 3840700 (Umlever) discloses specific zeolite P materials having an especially low ratio of silicon to aluminum no greater than 1.33 (hereinafter referred to as zeolite tnP) and describes their use as detergency builders. It has been surprisingly discovered that a problem can occur when water-soluble zeolite having a small particle size is used as a detergency builder in a composition formulated for use in fabric laundry. The problem has been found to be pronounced in particular when the zeolite is tlAP zeolite. The choice of a small particle size for any MRP zeolite component, that is, for particles that have a particle size, measured as a * / alor deo, up to 1.0 micrornetres, is preferred in the art, as represented, for example, by EP 384070 R. The problem refers to the formation of white residues, which adhere to the fabrics and remain in them 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 Vela where there are spots, which interfere with and prevent the complete removal of the stain. As a result of the visible contrast between the white debris and the stained cloth, the stained area where white deposits have formed may be more noticeable than the ophthalmological stain. S has established that when an arnilasa enzyme is employed in compositions containing MRP zeolite in the form of small particle size the pro lem of the white residue formation in the fabrics is reduced. It has also been established that the choice of a zeol ta having a larger particle size than that preferred by the art, in particular EP 384070 fl, may further reduce the tendency for white deposit formation to occur. Since the prior art, as represented, for example, by European Patent Applications, EP 384070 fl, EP 448297 fl, EP 52272BA, EP 533392 fl, EP 544492 fl, EP 552053, and EP 552054 fl, has contemplated the use of enzymes in combination with MflP zeolite in laundry detergent compositions; none of these prior art documents specifically describes the use of arnilasa enzyme with a zeolite to riflP 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. In accordance with the present invention a detergent composition is provided which contains (a) a zeolite detergent builder having a particle size, expressed as a d or a dso value, of less than 1.0 micro particles; (b) an amylase enzyme; In a preferred aspect the zeolite detergent builder comprises zeolite P having a silicon to aluminum ratio which is not greater than 1.33 (MflP zeolite).

DETAILED DESCRIPTION OF THE INVENTION BETTER ZEOLITE DETERIORATION The first essential component of the present invention is a detergent builder of aluninosilicate zeolite, optionally in conjunction with one or more supplementary detergency builders. The zeolite detergent builder is typically present at a level of 1% to 80%, most preferred 15% to 40% by weight of the compositions. In one essential aspect, the zeolite detergent builder has a particle size, expressed as a dso value of less than 1.0 millimeters, more preferably 0.05 to 0.9"aerometers, very preferred from 0.2 to 0.7 micrometers. 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 granulometer. Alurninosilicate zeolites have the unit cell formula Naz (AÍO2) z (SÍO2) and] - XH2O where z and y are at least 67 the molar ratio of z to y is from 1.0 to 0.5 and ?! =; x is at least 5, preferably from 7.5 to 276, most preferred from 10 to 264. The inosilicate alu material is in hydrated form and is preferably crystalline, containing from 10% to 28%, most preferred from 18% to 22% water in the form of ce. Alurnmosilicate zeolites can be naturally occurring materials, but are preferably derived synthetically. The ion exchange materials of the synthetic crystalline nosylate upu are available under the designations Zeolite fl, Zeolite B, Zeolite P, Zeolite X, 7eol? MflP, Zeolit HS and mixtures of the most. Zeolite fl has the formula ai2tfll? 2) i2 (S1O2) i21 H2O where x is from 20 to 30, especially 27. Zeolite X has the formula N ßß í (AIO2> 86 (1O2)? Or 1 276 H2O. MflP is described in EP 384070A (Umlever) It is defined as an alkali metal alkalinosilicate of the zeolite P type having a silicon to aluminum ratio which is not greater than 1.33, preferably within the 0.9 scale. 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: (1) mix together an alu mosil icato sodium having a molar ratio of N 2 ?: l2? 3 within the scale from 1.4 to 2.0 and a sodium silicate having a mol ratio of ?? 2 -Na2? within the scale of 0. 8 to 3. 4 with vigorous agitation at a temperature within the range of 25 ° C to the boiling point ueualmente 95 ° C, to give a gel having the following composition; AI2 O3: (1. 75-3.5) S1O2: (2.3-7.5) Na2? : P (80-450) H2 O; (11) aging the gel composition for 0.5 to 1 (3 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 maintain Any solid suspension should be separated (???) to separate the crystalline sodium alummosilicate thus formed, wash at a pH within the range of 10 to 12.5, and dry, preferably at a temperature not exceeding 150 ° C, at a moisture content which is not less than 5% by weight.The preferred drying methods are spray drying and flash drying.It seems that oven drying at a very high temperature can adversely affect the calcium binding capacity of the product under certain circumstances: commercial sodium mercantile pentahydrate 1 dissolved in water and 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 the slow addition at high 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 the subsequent passage of yearning be essential for the formation of pure P zeolite. In the absence of agitation, several mixtures of cri taline and amorphous materials can be obtained. Zeolite MAP generally has a calcium binding capacity of at least 150 rnG CaO per g of anhydrous aluminosilicate, as determined by the standard method described in GB 1473201 (Henkel). The calcium binding capacity is normally 160 rnG CaO / g and can be as high as 170 rng CaO / g. Although the zeolite MAP as other zeolites contains water of hydration, for the purposes of the present invention the amounts and percentages of zeolites are expressed in terms of the notional material. The amount of water present in the MAP zeolite hydrated at room temperature and the humidity is generally about 20% by weight.

OMILOSO The second essential component of the compositions is an arnilasa enzyme, that is to say, for example, an enzyme having arylolithic 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 / Grarno Units (KNU / g)" are well-known means for defining the activity of amylolitic enzyme and are described in GB-1, 269,839 A (Novo). In more detail, 1 KNU is the amount of enzyme that divides 5.25 grams of starch (Merck, Amylum Solubile Erg. B.6, Batch 9947275) per hour in the method described in 6B-.1, 26, 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 37 ° C pH 5.6 The enzyme amylase can be fungal or bacterial in origin. Amylases obtained by chemical or genetic manipulation of fungal or bacterial derived chains are also useful herein. The α -lase enzyme is preferably an a-arnilasse. Preferred harnesses include, for example, a ~ arm obtained from a special chain of B. licheniforrnis, described in more detail in GB-1,269,839 A. Deposit numbers registered for B. lichemformis chains capable of producing "- Amylases include NCTB 8061, NCIB 8059, ATCC 6634, ATCC 6598, flTCC 11945, ATCC 8480 and ATCC 9945a. Preferred commercially available preferred wams include, for example, those sold under the trademark Rapidase and Maxamyi by Gist-Brocades; those sold under the trademark Taka-Therm L-340 by Miles Laboratories, Elkhart, Indiana; those sold under 1 ^ trademark Rohalase AT by Rohm and Haas, lest Philadelphia, PA; and those sold under the trademarks Terrnarnyl 60T and 120T, Fungamyi and BAN by Novo Industries A / S. In a preferred aspect, 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 medium using any of the technical tests known in the art including those referred to in UO 94/02597 A. The improved stability amylases are commercially available from Novo Industries R / S or from Genencor International. Highly preferred arnilases with improved oxidative stability are derived using site-specific utagenesis from one or more of the Bacillus amylases, especially the Bacillus amylases, regardless of whether one, two or multiple amylase chains are the intermediary precursors. The reported arylases of this type are described in UO 94/02597 fl, and they comprise a mutant wherein the substitution is made, using alanine or threonine, preferably threonine, from the residue of etiomne located at position 197 of the ot-arninase. B. li chem forrnis, sold under the trademark Terrnarnyl, or the variation of the homologous position of a similar original arnilasa, such as B. amyloliquefaciens, B. subt ilis, or B. stea ro th rnoph 11 us. Other preferred Ilases having improved oxidative stability, derived from B. lichenifor is NCIB806, are described by Genencor International in a document entitled "Oxidatively Resistant a-flrnylases" which was presented at the 207th American Chemical Sodety National Meetmg, from March 17, 1994, by C. Mitchinson. Rnetiomna (Met) was identified as the residue with a greater probability of being modified. Met was substituted, one at a time, in positions 8, 15, 197, 256, 304, 366 and 438 leading to mut is specific, in particular being important M197L and M197T with the variant M197T 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 O (Novo). Any other arnilases of improved oxidative stability can be used, for example as derived by site-directed mutagenesis from original, chimeric, hybrid or simple, known forms of available amylases. Other enzyme modifications are acceptable including those described in WO 95/09909 fl (Novo). It will be appreciated that enzymes for incorporation in solid detergent compositions are generally sold as enzyme pellets containing active enzyme supported on a variety of inert host materials, which, for example, may include alkali metal sulphate, carbonate © 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. 20 COMPONENTS ADDITIONAL DETERGENTS The detergent composition according to the invention can contain other detergent components such ? < co or surfactants, detergent co-detergents, bleaches, fluorescents, anti-redeposition agents, 1? inorganic salts such as sodium sulfate, other enzymes, foam control agents, fabric softening agents, pigments, stained spots and perfumes. TENSION AGENT r5 The detergent composition according to the invention preferably includes a surfactant selected from ammonium, nonionic, zwitterionic, ampholytic and cationic. The surfactant is preferably present in the detergent compositions at a level of from 1% to 50%, preferably from 3% to 30%, and preferably 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 TT by Sch? Artz, Perry and Berch). Examples of additional ammonium surfactants include sulfates to ionics, olefin sulphonates, Alkylxylenesulphates, dialkyl sulfosuccinates, and sulphates of fatty acid ester. Sodium salts are generally preferred. oc ANIONIC SULPHATE SURGICAL AGENT Ammonium sulfate surfactants suitable for use herein include the linear and branched primary alkyl sulphates, alkyl ethoxy sulfates, fatty oleolyl glycerol sulfates, alkyl phenol ethylene oxide ether sulfate, C5-C17 sulphate acyl-N- (C1 alkyl) -C4) and -N- (Ci-C2 hydroxyalkyl) < J ucainin, and alkylaryl sulfates Ipol i ac akars such as the alkali sulphites Ipoliglucoside (the non-sulphonated nonionic compounds are described herein). The alkoxy-sulfate surfactant agent (s) are preferably selected from the group consisting of Cs-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 -Cis alkyl sulphate which has been ethoxylated with from 0.5 to 20, preferably from 0.5 to 5, moles of ethylene oxide per molecule.

ANIONIC SULPHONATE TENSIOACTIVE AGENT The agent (s) of suitable sulfonate surfactants suitable for use herein include the salts of alkylbenzenesulfonates of CS-C20, the ester (s) -carbonate sulfonate, primary or secondary C6-C22-alkano-sulphonate, C6-C24-olefin sulfonates, acid. © polycarboxylics © ulfon dos, lky lic olsul fonatos, acil licerolsulfonato © fatty, oleil gli cerolsul fatty fonatos, and any mixture thereof.

NON-IONIC TENSITIVE AGENT The nonionic surfactant is preferably a nonionic, non-ionic surfactant, particularly an alkoxylated nonionic surfactant, having a hydrophilic-lipophilic equilibrium (HLB) value of <; 9.5, much better than < 10.5. Example de de nonionic surfactant hid hydrophobic alco alkoxylated surfactants incluyen include alkoxylated adducts de of fatty alcohols containing an average of less than 5 © alkylene oxide group per molecule. The alkylene oxide residuo residues, for example, can be recycled from ethylene oxide or mixtures thereof, with residue de of propylene oxide. The preferred urea adducts of fatty alcohols ions useful in the present invention can be chosen from those of the general formula: R-0- (C "H2nO) and H wherein R e is an alkyl or alkenyl group it has 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 aliphatic Cu -is aliphatics. primary condensed with a prornedLO < no more than 5 groups of ethylene oxide per mole of alcohol, which have a content of filled oxide 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 atom 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 Synperomc A3 (ex ICI), which is a C13-C15 alcohol with about three ethylene oxide groups per molecule, and E pilan KB3 (ex Marc on), which is alcohol laupco 3EO. Another class of non-ionic surfactant agents comprises the alkoxycarboxylic acid glycoside compound of the general formula wherein Z is a glucose derivative; R is a saturated hydrophobic alkyl group containing from 12 to 18 carbon atoms; t e © from 0 to 10 and n is 2 or 3; x is from 1.1 to 4, which compounds include less than 10% unreacted fatty alcohol and less than 50% alkyl polygly short chain coss. What is © © © © © of this type and its use in cornposicione © detergents © e of © cr? Ben in EP-B 0070074, 0070077, 0075996 and 0094118.

CO-ME30R DETERGENT In addition to the MAP zeolite, the detergency builder system may contain a detergent builder or non-organic co-regulator. Suitable organic builder cores may be monomeric or polyrheric carboxylates such as chlorine. Treatments or polymers of acrylic, rnetacrylic and / or rnaleic acids in neutralized form. Suitable inorganic builder co-builders © include carbonate © and © icat © © hate, lamellar, amorphous and crystalline. The appropriate laminar silicate © have the composition: NaMSl? 02? + L and H2? where M is hate or hydrogen, I preferi © hate; X e © a number from 1.9 to 4; and Y is a number from 0 to 20. Said 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 6 N 2 i2? 5 (SKS6) and is described in US Pat. No. 4664830. The total amount of detergency agent in the granular composition typically ranges from 10 to 80% by weight, most preferably from 15 to 60% by weight and very preferably from 10 to 45% by weight.

BLEACH The detergent compositions according to the invention can also suitably contain a bleaching system. This preferably comprises one or more peroxy bleach compounds, for example, inorganic persalts or organic peroxyacids, which may be used. together with bleach precursors to improve the bleaching action at low temperatures. The bleaching system preferably comprises a peroxy bleach compound preferably a Persian! inorganic, optionally together with a precursor. The persale © Suitable L5s include sodium perborate onhydrated, and rattan tedrai and sodium carbonate, with the preferred form being the uerbonate of hate. Preferred bleach precursors are precursors of peracetic acid; ta Les as tetracetiletilen- 20 diarnma (TflEO); precursors of peroxybenzoic acid.

PHYSICAL FORM The detergent composition in accordance with The invention can be of any physical type, for example, powders, liquid © and gels. However, © ía granulated © and liquid © compositions.

TRAINING PROCEDURE The detergents of the invention can be prepared by any suitable method. The detergent compositions in particle © are suitably prepared by any tower (spray-drying) or non-tower process. In the process, based on a spray-drying tower, a base powder is first prepared by spray-drying a suspension and then another component that is not suitable for processing through the suspension can be sprayed or mixed (post-dosing). two) . The zeolite detergent builder is suitable for inclusion in the suspension, although it may be advantageous by reason of processing for a part of the zeolite builder to be incorporated after the tower. The layered silicate, where it is used, is also incorporated by a non-tower process and is preferably post dosed. Alternatively, the detergent compositions © in accordance with the invention can be prepared by completely non-tower processes such as ranching. 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 800 g / 1. The benefits of the present invention are particularly evident in volurnet rich high density powders, for example 700 g / 1 or © uperiore ©. Said powder © can already be prepared by densification after the powder spray tower, or by a completely towerless method such as dry mixing and granulation; in both cases a high density mixer / granulator can advantageously be used. Processes using high density mixers / granules © e describe, for example, in EP340 013A, EP 367 339A, EP 390 251 and EP 420 317A (Umlever). 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 gel is. The liquid detergent composition generally has a pH of 6.5 to 10.5. The total amount of detergent improver in the liquid composition is preferably from 5 to 70% of the total liquid composition. The illustrative compositions according to the present invention are presented in the following examples. In the detergent compositions, the identifications of abbreviated components have the following meanings: linear C11-C13 Alkylbenzene sulphonates 45AS Branched sodium alkylsulphate surfactant containing Cu alkyl chains, Cis-246AS alkyl sulphate surfactant sodium containing a weight distribution of alkyl chain length of 15% of C12 alkyl chains 45% of C? ¿alkyl chains, 35% of C cadenas alquilo alkyl chains, 5% of chains TAS alkyl ester Surfactant agent which is predominantly a chain of cis-Ciß alkyl derivative derived from tallow oil. 24AE3S: C E-C sodium ethoxysulfate ?? which contains an average of groups of ethoxy groups per 'mol. 35E3: A primary alcohol of C13-15 condensed with an average of 3 moles of ethylene oxide. 25E3: A primary alcohol of C12-15 condensed with an average of 3 mol of ethylene oxide. 24EY A linear primary alcohol of C12-14 condensed with an average of Y moles of ethylene oxide Carbonate: Anhydrous sodium carbonate.

P rborate: Sodium perborate tet rahydrate Percar- bon or Perc bonate of © hate TAED Tetraacetilet i lendiarni to Sil i cato Silicato of amorphous hatred (the ratio of io2 »normally proceeds) CMC carbox? Met? Icelulo © to Your pe Spumas 25% wax p > arafma, melting point of 50 ° C 17% hydrophobic silica, 58% paraffin oil Zeollt MAP: fllummo ©? l? cato of hydrated hatred of MflP formula having a silicon to aluminum ratio of 1.07. Zeol i a fl Zeollta fl hydrated sodium alurninosil icato having a particle size, expressed as a dso value, of 0.6 rni crornet ros. Mfl / Ofl: Coppermer of maleic / acrylic acid 1: 4, average molecular weight of approximately 80,000. Flrm l sa Enzyme to ilasa sold under the trademark Tepnarnyl 60T by Novo Industrie © A / S (60KNU / gram of enzyme activity) BSfl Apulolytic enzyme - variant M197T, which has an improved oxidant tab (60KNU / gram of enzymatic activity) P rote sa Proteolytic enzyme sold by Novo Industrie © A / S under the trademark Savmase of 2? Activity of 4.0 KNPU / grarno Lipase Lipolytic enzyme sold by Novo Industries A / S ba or Lipolase registered trademark of 100,000 I.U / gram activity EXAMPLE 1 The following granular laundry detergent compositions (parts by weight) were prepared according to the invention. All levels of the enzyme arnilasa refer to active enzyme levels, expressed on an activity basis of 60 KNU / g.

Water and various component © (including superoxide foam, 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 the levels of enzyme to Ilase refer to active enzyme levels, expressed on an activity basis of 60 KNU / g. fifteen '• > ? 4 45 ligua and component © miscellaneous (including foam suppressors, sulfate cream, perfume) for the rest.

Claims (13)

NOVELTY OF THE INVENTION CLAIMS

1. - A detergent composition containing (a) a zeolite detergent builder having a particle size, expressed as a dso value, of less than 1.0 nichrometers; (b) an arnilasa enzyme.

A detergent composition in accordance with the rei indication 1, further characterized in that said zeollta detergency builder has a particle size, exp as a dso value of 0.05 to 0.9 millimeters.

3. A detergent composition according to any of claims 1 or 2, further characterized in that said zeolite detergent builder comprises zeoLLta P having a silicon to aluminum ratio which is not greater than 1.33 (zeollta MflP).

4. A detergent composition according to claim 1, further characterized in that said zeollta detergent detergent is present at a level of 1% to 80% by weight of the composition.

5.- A detergent composition > In accordance with the rei indication l, characterized further because said enzyme cancels e © an a-ainilasa.

6. A detergent composition according to claim 1, further characterized in that said armillase enzyme has been modified to improve oxidant stability. ? . - A detergent composition in accordance with claim 1, further characterized in that said enzyme Lina ar il asa is present at a level of 0.01% to 5%, of active enzyme by weight of the composition, in a activity base of

60 KNU / g.

8. A detergent composition according to claim 7, further characterized in that said enzyme is present at a level of 0.2% to 2% active enzyme by weight of the composition in an activity base of 60 KNU / g.

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. A detergent composition according to claim 1, further characterized in that it contains an organic or inorganic detergency builder.

11. A detergent composition according to claim 10, further characterized in that said detergent builder is a silicate laminated cp s l mo.

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. - A detergent composition according to claim 12, further characterized in that said peroxy bleach compound is sodium percarbonate.