MXPA98002409A - Detergent composition comprising zeolite and enzyme proteolit - Google Patents

Abstract

A detergent composition is provided which contains a zeolite builder having a particle size, d 50, of less than 1.0 micron, and a proteolytic enzyme having an isoelectric point of less than 10.0, Alcalase is illustrated, the composition contains less of 7% by weight of the carbonate builder composition, preferably, the composition lacks a proteolytic enzyme having an isoelectric point above 10.

Description

DETERGENT COMPOSITION COMPRISING ZEOLITE AND PROTEOLITIC ENZYME DESCRIPTIVE MEMORY The present invention relates to a detergent composition comprising zeolite as a sequestering agent for the hardness of water and an enzyme. Detergent compositions for washing fabrics conventionally contain builders that decrease the concentration of water hardness ions of calcium and magnesium in the wash liquor and thus provide an acceptable detergency effect in both hard and soft water . Conventionally, inorganic phosphates, such as sodium tripolyphosphate, have been used as builders for laundry detergents. More recently, alkali metal aluminosilicate ion exchangers, particularly crystalline sodium aluminosilicate zeolite A, have been proposed as replacements for 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 384070A (Unilever) describes specific zeolite P materials that they have an especially low silicon to aluminum ratio of no more than 1.33 (hereinafter referred to as zeolite MAP) and describe their use as a detergency builder, optionally with detergent builders. Detergent compositions containing proteases are well known in the art. By using a protease in a detergent it is possible to hydrolyze the proteins present in clothing stains and dirt, to such an extent that they become easily soluble in water. Applicants have now surprisingly discovered that a problem can occur when a water-insoluble zeolite having a small particle size is used as a builder in a fabric washing detergent composition containing certain protease enzymes and relatively high levels of alcohol. -carbonate detergency improver. It has been found that the problem is particularly pronounced when the zeolite builder is zeolite MAP. The choice of a small particle size for a zeolite MAP component, i.e., particles having a particle size, measured as a dso value, up to 1.0 microns has been previously thought to be preferred in the art as represented by example, by EP 384070. The problem relates to the aforementioned detergent compositions which have a marked incompatibility with printed cotton fabrics. In particular, it has been found that the use of detergent compositions containing small particle size zeolite tend to lead to the removal of printed pigment from a surface of printed cotton cloth. It has been found that the presence of certain proteolytic enzymes, in particular those having a high isoelectric point, and relatively high levels of carbonate builder enhances this effect. The Applicant has surprisingly discovered that this problem can be mitigated by using in the detergent composition of proteolytic enzyme having an isoelectric point below 10.0, and limiting the level of any co-builder, The present invention is based, so both, in the unexpected discovery that the care profile of a printed cotton fabric of a detergent composition comprising zeolite of a small particle size, low carbonate builder levels and containing a protease having an isoelectric point below 10.0, it is superior to that of comparable compositions containing other proteases that have an isoelectric point of more than 10.0. Examples of suitable proteases according to this invention having an isoelectric point below 10.0 include Alcalase (trademark), Maxatase (trademark), Optimase (trademark) and Primase (trademark) commercial). Examples of proteases having an isoelectric point of more than 10.0 and which have been found not to produce said superior profile of care of printed cotton cloth are Savinase (trademark), which is described in EP 384070a (Unilever), Opticlean ( trademark), Maxacal (trademark), Purafect (trademark) and Esperase (trademark). This discovery allows the formulation of detergent compositions that provide both excellent cleansing and excellent care properties of fabrics printed on cotton fabrics. Although the prior art, represented for example by patent applications EP 384070 A, EP 448297 A, EP 522726 A, EP 533392 A, EP 544492 A, EP 552053 A, and EP 552054 A has envisioned the use of enzymes in combination with zeolite in laundry detergent compositions, none of these prior art documents specifically disclose the use of a proteolytic enzyme having an isoelectric point of more than 10.0 with a zeolite component of a small particle size. Moreover, none of these prior art documents provides any teaching that addresses the problem of care of printed cotton fabrics encompassed by the present invention, nor any solution that includes the selection of a particular proteolytic enzyme. In this way, the present invention provides a detergent composition containing (a) a zeolite builder having a particle size, dso, less than 1.0 miera; and (b) a proteolytic enzyme having an isoelectric point of less than 10.0 wherein said composition contains less than 7% by weight of the carbonate builder composition. In a preferred embodiment of the invention, the zeolite builder comprises zeolite P having a ratio of silicon to aluminum of not more than 1.33 (zeolite MAP). In another preferred embodiment of the invention, the detergent composition is free of any proteolytic enzyme having an isoelectric point of more than 10.0. In a further preferred embodiment, the detergent composition according to the invention is formulated to be especially useful in the washing of colored fabrics and is preferably free of bleach. According to another aspect of the invention, the composition is substantially free of an optical brightener.

Zeolite detergency builder The first essential component of the present invention is a builder of aluminosilicate zeolite, optionally in conjunction with one or more co-builders. The zeolite builder is present typically at a level of from 1% to 80%, most preferably from 15% to 40% by weight of the compositions. Suitable aluminosilicate zeolites have the unit cell formula Nai [(AIO2) r (SIO2) y]. XH2O, where z and y are at least 6; the molar ratio of zay is from 1.0 to 0.5 and x is at least 5, preferably from 7.5 to 276, most preferably from 10 to 264. The aluminosilicate material is in hydrated form and is preferably crystalline, containing from 10% to 28% , most preferably from 18% to 22% water in bound form. The aluminosilicate zeolites may be materials that occur naturally, but are preferably derived in synthetic form. Synthetic crystalline aluminosilicate ion exchange materials are available under the designations Zeolite A, Zeolite B, Zeolite P, Zeolite X, Zeolite MAP, Zeolite HS and mixtures thereof. Zeolite A has the formula: Nai2 CAIO2) l2 (SiO2) 12] XH2O where x is from 20 to 30, especially 27. Zeolite X has the formula Nass [(AIO2) ße (SÍO2)? Oe] .276H2O . Zeolite MAP is described in EP 384070A (Unilever). It is defined as an alkali metal aluminosilicate type zeolite P having a ratio of silicon to aluminum not greater than 1.33, preferably within the range of 0.9 to 1.33 and most preferably within the range of from 0.9 to 1.2.

Of particular interest is zeolite MAP which has a silicon to aluminum ratio not higher than 1.15 and very particularly, 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 a sodium aluminate having a molar ratio Na2 ?: A? ? 3 within the range of 1.4 to 2.0 and a sodium silicate having a molar ratio Si? 2: Na2? within the range of 0.8 to 3.4 with vigorous stirring at a temperature within the range of 25 ° C to the boiling point, usually 95 ° C, to give a gel having the following composition; AI2O3: (1.75-3.5) Si02: (2.3-7.5) Na20: P (80-450) H2 ?; (ii) aging the gel composition for 0.5 to 10 hours, preferably 2 to 5 hours, at a temperature within the range of from 70 ° C to the boiling point, usually at 95 ° C, with sufficient stirring to maintain any solid present in the suspension; (iii) separating the crystalline sodium aluminosilicate in this formed manner, washing at a pH within the scale of to 12.5 and drying, preferably at a temperature not exceeding 150 ° C, to a moisture content of not less than 5% by weight. The drying methods that are preferred are spray drying and spray drying. It seems that drying with an oven at a very high temperature could affect adversely the calcium binding capacity of the product under certain circumstances. The sodium metasilicate commercial pentahydrate dissolved in water and the commercial sodium silicate solution (aterglass) are both silica sources suitable 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) both create 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 aging step, appear to be essential for the formation of pure P zeolite. In the absence of agitation, several mixtures of crystalline and amorphous materials can be obtained. Zeolite MAP generally has a calcium binding capacity of at least 150 mg CaO per g of anhydrous aluminosilicate, as measured by the normal method described in GB 1473201 (Henkel). The capacity for calcium binding is normally 160 mg CaO / g and can be as high as 170 mg CaO / g. Although zeolite MAP like other zeolites contains water of hydration, for the purposes of the present invention the amounts and percentages of zeolite are expressed in terms of the notional anhydrous material.

The amount of water present in the hydrated MAP zeolite at room temperature and humidity is generally about 20% by weight. The zeolite builder used in the present invention has a particle size dso of less than 1.0 miera, preferably 0.05 to 0.9 micrometer, most preferably 0.2 to 0.7 micrometer. The dso value indicates that 50% by weight of the particles have a diameter smaller than that of that figure. The particle size can be determined by conventional analytical techniques such as, for example, microscopic determination using a scanning electron microscope or by means of a laser granulometer. The zeolite builder having the necessary particle size according to the present invention can be prepared, for example, by conventional techniques as described above, while adopting one or more of the following steps: a) reduce the time of crystallization; b) reducing the size of the seed crystals used to produce the zeolite; c) sieving the zeolite product to remove coarse material. An article by D. Vucelic, published in Progr Colloid Polymer Science, 1994, Volume 95, p. 14-38 describes methods for the synthesis of zeolite particles, and in particular how to influence the size characteristics of particle of the zeolites by modifying the steps of the synthesis procedure.

Rotease Enzyme The detergent composition according to the present invention essentially comprises a proteolytic enzyme of an isoelectric point below 10.0, preferably below 9.0, most preferably below 7.0. Suitable proteases include the proteases represented by the genus Subtilisin Carlsberg, producible by Bacillus licheniformis. Other suitable proteases include proteases represented by the genus Subtilisin BPN ', producible by Bacillus amyloliquefaciens.

Other suitable proteases are proteases that show a positive unological cross-reaction with the protease antibody as described hereinabove. The proteases that are most preferred are the proteases that are commercially sold under the trade names Alcalase (trademark), Maxatase (commercial maraca), Optimase (trademark), Primase (trademark) or mixtures thereof. The proteases according to the present invention are preferably present in an amount of from 0.001% to 2%, preferably from 0.001% to 1%, most preferably from 0. 002% to 0.5%, active enzyme by weight of the detergent composition.

Detergent co-builder In addition to zeolite, the detergent compositions may contain an organic or inorganic co-builder. Suitable organic builder co-builders may be monomeric or polymeric carboxylates such as citrates or polymers of acrylic, methacrylic and / or maleic acid in neutralized form. Suitable inorganic builder co-builders include crystalline and amorphous layered carbonates and silicates. Suitable crystalline layered silicates have the composition: NaMSix02x + 1. yH2? wherein 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. Nos. 4664839; 4728443 and 482039 (Hoechst AG). Especially preferred are those compounds in which x = 2 and y = 0. The synthetic material is commercially available from Hoechst AG as d-Na2 Si2? S (SKS6) and is described in the US patent. No. 4664830. The total amount of builder in the granular composition typically ranges from 10 to 80% by weight, preferably from 15 to 60% by weight and most preferably from 10 to 45% by weight. In one essential aspect, the level of carbonate builder, that is, the inorganic compound capable of releasing carbonate ions in a washing solution is less than 7% by weight, preferably less than 4% by weight of the detergent composition. Most preferably, the detergent composition is free of a carbonate builder.

Additional detergent components The detergent composition according to the invention may contain other detergent components such as surfactants, bleaching agents, fluorescers, antiredeposition agents, inorganic salts such as sodium sulfate, other enzymes, foam control agents, fabric softening agents, pigments, colored spots and perfumes.

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

Anionic Sulfate Surfactant The suitable anionic sulfate surfactants for use herein include the linear and branched primary alkyl sulfates, alkyl ethoxy sulfates, oleyl glycerol sulfates, ethylene oxide ether sulfates of alkylphenol, the acyl-N- (C? -G;) and - N- (Ci-C2 hydroxyalkyl) C5-C17 glucamin sulfates and alkylpolysaccharide sulfates such as alkylpolyglucoside sulfates (the non-sulphonated nonionic compounds are described herein). The alkyl ethoxy sulfate surfactants are preferably selected from the group consisting of Cs-Cis alkyl sulphates which have been ethoxylated with an amount of 0.5 to 20 moles of ethylene oxide per molecule. Most preferably, the alkyl ethoxy sulfate surfactant is C 1 - i β alkyl sulfate which has been ethoxylated with an amount of 0.5 to 20, preferably 0.5 to 5 moles of ethylene oxide per molecule.

Anionic Sulfonate Surfactant The anionic sulphonate surfactants to be used herein include the salts of linear alkylbenzene sulphonates of CS-C20, alkyl ester sulphonates, primary or secondary C6-C22 alkan sulfonates, C6-C24 olefinsulfonates, polycarboxylic acids sulphonates, alkyl glycerol sulfonates, fatty acyl glycerol sulfonates, fatty oleyl glycerol sulfonates and mixtures thereof.

Nonionic Surfactant The nonionic surfactant is preferably a hydrophobic nonionic surfactant, particularly an alkoxylated nonionic surfactant having a hydrophilic-lipophilic equilibrium (ehl) value of < 9.5, very preferably < 10.5. Examples of suitable hydrophobic alkoxylated nonionic 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. Preferred alkylene oxide adducts of fatty alcohols useful in the present invention can be chosen suitably from those of the general formula: R-0- (CnH2nO) and H wherein R is an alkyl or alkenyl group having at least 10 carbon atoms, most preferably 10 to 22 carbon atoms, and 0.5 to 3.5 and n is 2 or 3. Preferred nonionic surfactants include aliphatic alcohols of Cu - Primary condensed with an average of not more than five 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 15 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 of Empilan KB3 (ex Marchon), which is lauric alcohol 3E0. Another class of nonionic surfactants comprises alkylpolyglucoside compounds of the general formula wherein Z is a portion derived from glucose; 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% fatty alcohol without react and less than 50% short chain alkyl polyglucosides. Compounds of this type and their use in detergent compositions are described in EP-B 0070074, 0070077, 0075996 and 0094118.

Bleach The detergent compositions according to the invention may also contain a bleach system. Where present, it preferably comprises one or more peroxy bleach compounds, for example, inorganic persalts or organic peroxyacids, which may be used in conjunction with bleach precursors to improve the bleaching action at low temperatures. The bleach system preferably comprises a peroxy bleach compound, preferably an inorganic persalt, optionally together with a peroxyacid bleach precursor. Suitable persalts include sodium perborate monohydrate and tetrahydrate and sodium percarbonate, with sodium percarbonate being more preferred. Preferred bleach precursors are precursors of peracetic acid, such as tetraacetylethylene dia (TAED); precursors of perbenzoic acid. In a preferred aspect, the detergent compositions lack bleach and are particularly useful in washing loads containing brightly colored fabrics.

PH / Low Alkalinity Detergent Compositions The preferred detergent compositions according to the invention are characterized by having a pH measured as a 1% solution of the detergent composition in distilled water at 25 ° C of < 10.5, preferably < 10.4, very preferably < 10.3. It has been found that compositions having a low level of reserve alkalinity are advantageous since they have a reduced tendency to produce the removal of printed pigment from printed cotton fabrics. The inverse alkalinity is expressed as g of NaOH per 100 grams of composition as determined by acid titration of a sample, as a 1% solution in distilled water at a pH of 9.5. Preferred values of reverse alkalinity are < 8.0 g, preferably < 5.0 g, very preferably < 3.0 g of NaOH per 100 grams of the composition.

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.

Manufacturing process 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 processes based on a spray-drying tower, a base powder is again prepared by spray-drying a suspension, and then other components not suitable for processing through the suspension can be sprayed or mixed (post-dosed). The zeolite builder is suitable for inclusion in the suspension, although it may be advantageous for processing reasons that a part of the zeolite builder is then incorporated into the tower. Where employed, the crystalline layered silicate is also incorporated through a non-tower process and is preferably post-dosed. Alternatively, particulate detergent compositions according to the invention can be prepared by methods that are not tower at all 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, most preferably at least 700 g / 1 and, with particular reference, at least 800 g / 1. The benefits of the present invention are particularly evident in powders of high volumetric density, for example, 700 g / 1 or more. Such powders can be prepared either by densification after the spray-dried powder tower, or by non-tower methods at all such as dry mixing and granulation; in both cases, a high speed mixer / granulator can be advantageously used. Processes using high speed mixer / granulators are described, for example, in EP340 013A, EP 367 339A, EP 390 251A, 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 paste-like viscous formulations such as gels. The liquid detergent composition usually has a pH of 6.5 to 10.5. The total amount of 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, the abbreviated component identifications have the following meanings: 24AS: Sodium alkyl sulfate surfactant agent containing predominantly C12 and CIA alkyl chains TAS: Alkyl Sulfate Surfactant of sodium containing predominantly Cie-Cis alkyl chains derived from wood oil. 24AE3S: C 12 -C 14 alkylcytosulfate containing an average of three ethoxy groups per mole. 35E3: Primary alcohol of C13-15 condensed with an average of three moles of ethylene oxide. 25E3: A primary alcohol of C12-C1S condensed with an average of 3 mols of ethylene oxide. Carbonate: Anhydrous sodium carbonate. Perborate: Sodium perborate tetrahydrate. TAED: Tetraacetylethylenediamine Silicate: Amorphous sodium silicate (ratio of SiO 2: Na 2? Normally comes) SKS6: Crystallized layered silicate available from Hoechst AG as SKS6 (trade name) Zeolite MAP: Zeolite MAP of hydrated sodium aluminosilicate having a ratio of silicon to 1.07 aluminum that has a particle size, expressed as a value of dso, of 3.0 microns. Zeolite A: Hydrated sodium aluminosilicate zeolite A having a particle size, expressed as a dso value, of 3.0 microns. MA / AA: Copolymer of maleic / acrylic acid 1: 4, average molecular weight of approximately 80,000. Alcalase: Proteolytic enzyme sold under the trade name alcalase by Novo Industries A / S (enzymatic activity of approximately 1% by weight). BSA: amylolytic enzyme sold under the trade name LE17 by Novo Industries A / S (enzymatic activity of approximately 1%).

EXAMPLE 1 The following granular laundry detergent compositions (parts by weight) were prepared according to the invention.

Water and minor components (including foam suppressant, sodium sulfate, perfume) make up the rest. Detergent compositions according to the invention, comprising larger particle size zeolite builder and Alcalase, show good results in stain removal and damage to lower printed cotton fabrics compared to a composition comprising a zeolite of small particle size and Savinase.

Claims (11)

NOVELTY OF THE INVENTION CLAIMS

1. - A detergent composition containing: a) a zeolite builder having a particle size dso of less than 1.0 miera; and b) a proteolytic enzyme having an isoelectric point less than 10.0, wherein said composition contains less than 7% by weight of the carbonate builder composition.

2. A detergent composition according to claim 1, further characterized in that the zeolite builder has a particle size dso of 0.05 to 0.9 microns.

3. A detergent composition according to claim 1, further characterized in that the zeolite builder comprises zeolite P having a ratio of silicon to aluminum not greater than 1.33 (zeolite MAP).

4. A detergent composition according to claim 3, further characterized in that zeolite MAP has a silicon to aluminum ratio not greater than 1.1

5. 5. A detergent composition according to claim 1, comprising from 1 to 80% by weight of a zeolite builder.

6. A detergent composition according to claim 1, comprising the proteolytic enzyme in a amount to provide from 0.001% to 2% by weight of active enzyme of the detergent composition.

7. A detergent composition according to claim 1, which does not contain isoelectric point proteolytic enzyme greater than 10.0.

8. A detergent composition according to claim 1, further characterized in that the proteolytic enzyme is represented by subtilisin protease BP i.

9. A detergent composition according to claim 1, further characterized in that the proteolytic enzyme is represented by subtilisin protease Carlsberg.

10. A detergent composition according to claim 1, further characterized in that the composition has an inverse alkalinity (expressed as g of NaOH per 100 g of composition as determined by titration with acid from a sample as a 1% solution in distilled water at a pH of 9.5) of less than 8.0 g.

11. A detergent composition according to claim 1, further characterized in that it lacks optical brightener or brightener.