MXPA97002939A - Deterge composition - Google Patents

Abstract

A detergent composition comprising a surface active agent selected from anionic, nonionic, amphoteric and zwitterionic detergent active compounds and mixtures thereof, a builder comprising zeolite P having a silicon to aluminum ratio not greater than 1.33 (zeolite MAP); and a cellulitic enzyme. Preferably the zeolite MAP has a particle size of (deo) of < 1.0 micrommet

Description

DETERGENT COMPOSITION The present invention relates to a detergent composition and, in particular - / with improvements in the performance of the detergent effect of laundry detergent compositions comprising zeolites as a water hardness sequestering agent. Detergent compositions for washing heavily soiled fabrics conventionally contain detergent effect enhancers that decrease the concentration of hardness ions of calcium and magnesium water in the liquor wash, thereby providing a good detergent effect in both hard water and water. soft. Conventionally, inorganic phosphates, such as sodium tripolyphosphates, have been used as speakers for laundry detergents. Recently, alkalinosilicate ion exchangers of alkaline metal, particularly zeolite, of crystalline sodium alosilicate, have been proposed as replacements for inorganic phosphates. For example, EP 21 491R (Proter a Gable) discloses detergent compositions containing a builder system including zeolite fi, X or P (B) or a mixture thereof. EP 384070A (Unibarra) discloses specific zeolite P materials having an especially low silicon to aluminum ratio of no greater than 1.33 (hereinafter referred to as MfiP zeolite) and describes their use as a detergency builder. However, to date, zeoli + a P is the most preferred aluminum rne oder in the commercially available products. It is also known in the art that detergent formulations containing small zeolite particles may have advantages over other zeolites in the process of the active agents due to the increase in the absorption surface area. For example r.Pfl 0521b35 (Unil ver) I discover a free-flowing particle detergent composition that includes NRP zeolite which preferably has a dsa particle size (defined below) within the range of 0.4 to 2.0 microns and greater preference of 0.4 to 1.0 millimeters. The amount "dao" indicates that 50wt% of the particles have a smaller diameter-than that amount. EPfl 0522726, EPA 0552053 and ETfl 00552054 (Umlever) all also show a preference for the HflP zeolite having an average particle size and illustrates detergent compositions in which the MftP zeolite has a particle size (dso) of 0.8. However, we have found that formulations containing small zeolite particles (dMO) < 1.0 rnicrorne ros) show a significant increase in scale on the fabric after several washings as compared to the coarse zeolites (d_ »0> 1.0 micro eters). Surprisingly we have found that superior detergent effects can be achieved by incorporating a cellulitic enzyme into the detergent composition. Detergent compositions containing cellulases are known in the art. By using said enzymes in a detergent, it is possible to hydrolyze the cellulases present in stains and dirt of the fabric, to such a degree that they become readily soluble in water. The use of a cellulite enzyme has benefited the washing process, in particular with the removal of lint and clays and achieving a whiter appearance. We have found that the use of MflP zeolite with a cellulite enzyme leads to significant performance benefits especially in incrustations in washing by boiling. According to a particular aspect of this invention we find that particular advantages arise using a cellulitic enzyme in a detergent composition comprising small particles of zeolite MOP such as zeolite I1RP having a particle size dao of < 1.0 icrómetroe. In particular the problem of embedding in fabrics after several washings was reduced or eliminated by means of the present invention. In this way, the present invention provides a detergent composition comprising: a). A surfactant of anionic, nonionic, cationic, amphoteric and zwitterionic active compounds and mixtures thereof; b) A detergency improver comprising zeolite having a SLlicon in relation to aluminum no greater than 1.33 (zoolite MftP); and c) A cellulose enzyme. The cellulitic enzymes usable in the present invention generally have a molecular weight scale of 20 KD to 70 KD and include both bacterial and fungal cellulitic enzymes. Preferably, these will have an optimum pH of between 5 and 9.5. Suitable cellulases are disclosed in the EU patent 4,435,307, Barbesgoard et al., Published on March 5, 1984, which discovers that the fungal cellulase produced from Hurnicola insolens and Hurnicola type OSI11800 or a cellulase 212-which produces fungi that belong to the genus flernonas, and ceiulasas extracted from the hepatopancreas of a marine mollusk (Dolabella Auricular Solander) .The appropriate celuiases are also discovered in GN-fl-2, 075, 028, GB-fl.2, 095, 275 and DE -O-2, 247, 832. The enzyme can be incorporated into the granular composition in an amount for example, from 0.01 to 4% by weight, preferably 0.05 to 2% by weight, more preferably from 0.1 to 0.2% by weight in an activity of 1000 cevu / g, to provide respectively from 10 to 4000, from 50 to 2000 and from 100 to 200 cev for 100 g of composition Examples of commercially available catalytic enzymes suitable and specific for use in the present invention include Carezi ay Endolasa.

Endolase A, for example, can be incorporated in the granular detergent composition in an amount of 0..1 to 3% by weight, preferably 0.5 to 2% by weight in an activity of 1250 cevu / g. In liquid detergent formulations, typical examples of suitable amounts for cellulitic enzymes are 0.09% cellulase at 3000 cevu / g and 8.08% Endolase A at 5000 cevu / g. The detergent composition according to the invention contains, as an essential ingredient, one or more surfactants chosen from the anionic, nonionic, cationic, amphoteric and zweterionic detergent active compounds and mixtures thereof. Such surfactants are well known and are described in the literature, for example, in "Surface Active Agents and Detergents", Volumes I and II written by Sch artz, Perry and Berch. Examples of suitable anionic surfactants include alkylbenzene sulfonates, particularly linear sodium alkyl benzene sulphonates having an alkyl chain length of C 1 -C 6 S; C? 2-C? 3 primary alkyl sulfates; olefin sulfanatoe; alkyl, ileum sulfonates; uilo dial sulfosuccinates; and fatty acid ester sulfonates. Sodium salts are generally preferred. Examples of a suitable nonionic surfactant include alkoxylated adducts that approximate fatty alcohols containing an average ranging from 3 to 10 alkylene oxide groups per molecule. Preferred alkoxylated adducts of fatty alcohols containing an average of less than 5 alkylene oxide groups per molecule, for example less than 4 groups of Alkyl oxide per molecule, for example 3.5 and use 3 alkylene oxide groups per molecule or less and advantageously - also greater than 0.5, or 1, or 2 alkylene oxide groups per molecule. A particularly preferred aliphatic alcohol ethoxylate is a primary alcohol having an average of 12 to 15 carbon atoms in the condensed alkyl chain with an average of 3 ethoxy groups per molecule of alcohol. Specific examples of alkoxylated adducts of suitable fatty alcohols with Sirnperonic A3 (ex ICI), which is an alcohol C aC? .s with about three groups of ethylene oxide per molecule and in Ernpilane KB3 (ex Narchon), which is a lacup alcohol 3E0. Another class of nonionic surfactant comprises polyalkyl alkyl compounds of the general formula wherein Z is a glucose-derived portion; R is a 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 polyglucoedes. Compounds of this type and their use in detergent compositions are disclosed in EP-B 0070074, 0070077, 0075996 and 0094118. The surfactant will generally be included in the detergent composition in an amount of 5 to 60% by weight, preferably 5 to 40% by weight and more preferably 10 to 25% by weight of the composition. According to the present invention, the better detergency system is based on the zeolite MAP, optionally in conjunction with 1 or more supplementary reagents. The amount of zeolite MAP used can fluctuate, for example, from 5 to 60 wt%, more preferably from 15 to 40 wt%. Zeolite MAP is described EP384070A (Unilever). it is defined as an aluminum silicate alkali metal of the P type zeolite having a silicon to aluminum ratio not greater than 1.33, preferably within the range from 0.9 to 1.33 and more preferably within the scale from 0.9 to 1.2. Of particular interest is zeolite MAP which has a silicone to aluminum ratio not greater than 1.15 and, more particularly, not greater than 1.07. The zeolite P having a Si: Al ratio of 1.33 or less can be prepared by means of the following steps: (i) Mix together a sodium aluminate having a gram molecule ratio of NA / g.0: Als_0a within the scale from 1.4 to 2.0 and a sodium silicate that has a gram molecule ratio of SiO2: Na20 within the range from 0.8 to 3.4 with vigorous stirring at a temperature in the range of 25 ° C to the boiling point generally 95 ° C, to give a gel having the following composition; (n) Attach the gel composition for 0.5 to 10 hours, preferably 2 to 5, at a temperature within the range of 70 ° C to boiling point. Usually 95 ° C, with sufficient stirring to keep any solid present in suspension; (m) 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 not less than 5 wt%. Preferred drying methods are spray drying and intermittent drying. It appears that oven drying at too high a temperature can adversely affect the calcium binding capacity of the product under certain circumstances. Commercial sodium metasilacate pentahydrate dissolved in water and the commercial sodium silacate 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 the subsequent aging step, 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 tAP zeolite has a calcium binding capacity of at least 150 mg CaO per g of anhydrous aluminosilacate, as measured by the standard method described in GB 1473201 (Henkel). The calcium binding capacity is normally 160 mg CaO / g and can be as high as 170 rng CaO / g. Although zeolite I1AP co or other zeolites contain water of hydration, 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 IAP zeolite hydrated at room temperature and the humidity is generally around 20? TS. A particularly preferred tAP zeolite for use in accordance with the present invention has an aa of < 1.0 micrometers, for example from 0.4 to 1.0 micrometers. The size of the particle is determined by conventional analytical techniques such as, for example, microscopic determination using a scanning electron microscope or by means of a granulometer. Zeolite MAP having the small particle size required according to one aspect of the present invention can be prepared by the conventional techniques as described above while adopting one or more of the following steps: a) Increase the crystallization temperature and reduce the time of crystallization. b) Increase the size of the grain crystals used to produce the zeolite; c) Feeding the aluroinosilicate gels towards the crystallization stage immediately after forming (that is to say, eliminating the aging of the gels); d) Sift the zeolite product to remove the fine material. According to one embodiment of the invention, the zeolite HAP builder is in powder form. For convenience of handling, however, the material can be granulated by conventional techniques such as abstention drying or a non-tower method to form larger particles. In the granular detergent compositions according to the invention, the builder may be zeolite MAP alone or a combination of zeolite MAP with organic or inorganic builder. Suitable organic detergency builders may be monomeric or polydrug carboxylates such as citrates or acyl polymers, racrylic and / or maleic acid in neutralized form. Suitable inorganic builders include carbonates, and amorphous and crystalline layered sodium silicates. Suitable crystalline layered silicates have the composition: Where f 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 U.S. Patent No. 4,648,489; No. 4728443 and No. 820439 (Hoechst AG). Especially preferred are compounds in which x = 2 and y = 0. Synthetic material is available commercially from Hoechst AG as S-Na2 20a (SKS6) and described in US patent 4664830. The total amount of enhancer Detergency in granular composition scales ranges from 10 to 80 wt%, most preferably from 10 to 45 wt%. The detergent compositions according to the invention may also contain a bleaching system. This 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 bleaching system preferably comprises a peroxy bleach compound, preferably an inorganic salt, optionally together with a precursor. Suitable per-salts include tetrahydrate sodium perborate hydrochloride and sodium percabonate in which the most preferred is sodium percabonate. Preferred bleach precursors are peracetic acid precursors, such as full tetracycline diaryn (TAED); and peroxybenzoic acid precursors, such as benzoyloxybenzenate of sodium (SBOB). Other materials that may be present in the detergent compositions of the present invention include, for example, florescence agents, anti-sediment agents, inorganic salts such as sodium sulfate, other enzymes, foam controlling agents, fabric softening agents. , pigments, color granules and perfumes. The detergent compositions of the invention can be prepared by any suitable method. The particle detergent compositions are suitably prepared by any process of tor-re (spray drying) or without tower. In the processes based around a spray-drying tower, a base powder is first prepared by spray-drying a slurry and then other components unsuitable for processing by means of the slurry. The slurry can be sprayed or added (post-dose). Generally the enzyme will be post-dosed. The zeolite MAP is suitable for inclusion in the slurry, although it could be advantageous for processing reasons for part of the zeol ta flAP to be incorporated by tower. The layered silicate, where it is used, is also post-dosed. Alternatively, the particulate detergent compositions according to the invention can be prepared by completely non-tower 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, more preferably at least 700 g / 1, and particularly preferably at least 800 g / 1. The benefits of the present invention are especially evident in powders of high bulk density, for example, 700 g / 1 or greater. Said powders can be prepared either by post-tower densification of spray dried powder, or by totally non-tower methods with dry mix or granulation; in both cases a high speed mixer / granulator can be advantageously used. Processes using high speed mixer / granulator are described, for example, in EP340 013A, EP367 339A, EP 390 251D and EP 420 317A (Unibarra). According to a later aspect of the invention a liquid detergent composition is provided, preferably a heavy duty liquid detergent composition comprising a surfactant people as previously described, a detergency builder comprising zeolite MAP and a cellulitic enzyme. According to this embodiment, the liquid detergent composition may be of any convenient physical form which may be aqueous or anhydrous. The term "liquid" used herein includes paste-like viscous formulations such as gels. The liquid detergent system comprises, as the detergent builder zeolite MAP optionally in combination with other builders such as fatty acids, citric acids or zeolite A. A preferred builder-detergent is a layered sodium silicate such as SKS-6 which is particularly useful in formulations pasty viscous co or gels or liquid or aqueous detergents such as those described in UO92 / 16608 (Henkel). The liquid detergent composition generally has a pH ranging from 6.5 to 10.5. The total amount of builder in the liquid composition is preferable to be from 5 to 70% of the total liquid composition.

The invention is illustrated by the following example in which the abbreviations have a meaning that is defined below. AS: Sodium alkyl sulfate E05: Cx -C? Aliphatic alcohol ethoxylate which has an average of 5 ethoxy groups per molecule of alcohol. Soap: Tallow soap. TAED: Di mino ethylene tetracetyl. DETPMP: Penta reamine of diethylene (ethylene phosphonic acid), marketed by Monsanto under the trade name Dequest 2060. MA / AA: Copolymer of 1: 4 rnaleic / acrylic acid (Mw 80,000). Citrate: Trisodium citrate dihydrate. Antispurna granules: Silanated silica mixture: silicone in a ratio of 1: 1.5 (M U 100,000).

AXIS PLQS The particle components and compositions were prepared as follows: 1 2 3 Anionic surfactant AS (C12-15) 9 AS (C12-14) - 9 9 Nonionic surfactant E05 7 7 9 Soap - - 3 Zeolite MAP (anhydrous) 20 20 30 Sodium carbonate 13 6 13 Baking soda 0 0 5 Amorphous sodium silicate 3 0 3 Crystalline sodium silicate 0 10 0 Citrate 2 0 5 Sodium percarbonate 18 24 0 Granules DTAE 10 4 0 DETPMP 0.5 0.3 0.4 MA / AA 3 4 5 Anti-foam granules 2 2 2 Enzyme granules 2 Carezi a (1000 cevu / g) 0.15 0.20 0.10 Endolasa (5000 cevu / g) 0.20 0.30 Moisture / Miscellaneous balance sheet balance (Soil release agents, fabric bleaching agents, perfumes, water) 100 100 100 The following examples and reference examples demonstrate the reduced fouling in the fabrics after a cycle of several washes of the composition of detergent according to the invention.

Claims (10)

IB NQVEPRD PE L INVENTION CLAIMS

1. - A detergent composition comprising: (a) a surfactant chosen from ammonium ammonium active compounds, acycotics, amphoteric and switerioids and mixtures thereof; (b) a detergency builder comprising zeol ta P quo Wene a Silicon to aluminum ratio not greater than 1.33 (zeolite MAP); and (c) a Ceiulitic enzyme.

2. A detergent composition according to claim 1, further characterized in that the zeolite MAP has a particle size (dso) of < 1.0 micro et os.

3. A detergent composition according to claim 2, further characterized in that the zeolite MAP has a particle size (dso) of 0.4 to 1.0 m centimeter.

4. A detergent composition according to claim 1, further characterized in that the zeolite MAP has a silicone to aluminum ratio not greater than 1.1

5. 5. A detergent composition according to claim 4, further characterized in that zeolite MAP has a silicon to aluminum ratio not greater than 1.07.

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

7. A detergent composition according to claim 1, comprising the cellulite enzyme in a consti- tude to provide from 10 to 4000 cevu per 100 g of composition.

8. A granular detergent composition according to claim 1, comprising from 5 to 60 wt% of component (a); from 10 to 80 wt% of component (b) and a cellulite enzyme (c) in an amount to provide 50 to 2000 cevu per 100 g of composition.

9. ~ A detergent composition according to claim 1, comprising from 5 to 60 wt% component (to); from 5 to 40 wt% of component (b); and a cellulitic enzyme (c) in an amount that provides 100 to 200 cevu per 100 g of composition.

10. A detergent composition according to claim 1, comprising the cellulitic enzyme in an amount that provides 100 to 4000 cevu per 100 g of composition.