MXPA00000359A - Detergent compositions comprising a specific oxygenase - Google Patents

Abstract

The present invention relates to detergent compositions, including laundry, fabric care, dishwashing and hard surface cleaner compositions, comprising an oxygenase directed to body soils, which provide effective and efficient cleaning of everyday body stains and/or soils and provide sanitisation of the treated surfaces. Furthermore, the detergent compositions of the present invention provide substantive fabric realistic items cleaning and whitening performance when formulated as a laundry detergent composition.

Description

DETERGENT COMPOSITIONS THAT COMPRISE A SPECIFIC OXYGENASE FIELD OF THE INVENTION The present invention relates to detergent compositions, including laundry, dishwashing and hard surface cleaning compositions, which comprise an oxygenase targeted to body soils.

BACKGROUND OF THE INVENTION The performance of a cleaning product, for use in a washing or cleaning method, is judged by numerous factors, including the possibility of removing dirt and the ability to prevent redeposition of dirt or decomposition products. the dirt, on the items that are being washed. The complex nature of daily "body" soils typically found in pillow cases, t-shirts, collars and socks, provides a continuous challenge for detergents during cleaning. These soils are difficult to remove completely and often the residues accumulate on the fabric, which causes it to be percieved and yellow. Body dirt is a complex mixture of organic and inorganic components, excreted by the human body. They contain unsaturated, hydrophobic organic compounds, difficult to remove with normal detergents. For example, the epidermal secretion of humans can contain up to 35% of these hydrophobic unsaturated compounds, such as long chain paraffinic hydrocarbons (up to 3%), squalene (up to 12%), wax esters of 26 to 42 carbon atoms. carbon (up to 16%) and heterocyclic and polycyclic organic compounds, such as cholesterol and its derivatives (up to 6% in total). These hydrophobic organic compounds tend to accumulate on the fabric, causing yellowing and perc, and increase the ability of the fabric to get dirty. Diary body dirt has also been found on sanitary and kitchen surfaces, such as bath tubs, toilet bowls and dishes. The articles can be fabrics, hard surfaces, crockery, for example, plastic, glass or porcelain tableware. Traditionally, enzymes, surfactants, detergency builders and / or high levels of bleaching compounds, optionally with bleach precursors and / or bleach enhancers, are incorporated in detergent compositions. Bleaching agents are compounds that are precursors of hydrogen peroxide, which is formed in the course of the washing process. Perborates and percarbonates are the most important examples of said hydrogen peroxide precursors. In view of the foregoing, there remains clearly a need to provide detergent compositions having excellent detergency performance. Accordingly, it is an object of the present invention to provide a cleaning composition that provides effective and efficient cleaning of body soiling. It is another objective to provide a cleaning composition that provides for real cleaning and bleaching of fabric articles. The previous objective has been satisfied when formulating compositions detergents comprising an oxygenase directed to body soils. It has been surprisingly discovered that an enzyme whitening system, based on an oxygenase targeted to body soiling, provides similar detergent-like benefits in a detergent composition. a bleach, on an unexpectedly wide scale of functional areas, such as dirt cleaning, maintaining whiteness and removing stains. It has also been found that the detergent compositions of the present invention impart sanitization to the treated surfaces. It has been further discovered that the operation of the detergent compositions of the present invention is improved by the addition of another enzyme whitening system, a bleaching system. ** »» ** ^^ activated, conventional, a whitening system based on metal catalyst and / or another detergent enzyme. In a preferred embodiment, the present invention relates to a laundry composition comprising an oxygenase directed to body soiling, which additionally provides real cleaning and whiteness to fabric articles. In a second embodiment, the present invention relates to dishwashing or household cleaning compositions, which comprise an oxygenase directed to body soiling. The use of an oxygenase directed at the soils of the body, in a detergent composition, for the substantive elimination of daily body soils, and for sanitization, had never been previously recognized. The actual cleaning and bleaching performance of cloth articles, substantive, when using oxygen directed to body dirt, with a laundry detergent composition, was also not recognized.BRIEF DESCRIPTION OF THE INVENTION The present invention relates to detergent compositions, which include compositions for laundry, dishwashing and for cleaning hard surfaces, which comprise an oxygenase directed to body soiling, which give effective and efficient cleaning of body stains. every day, and / or dirt, and that impart the sanitation of the treated surfaces. Additionally, the detergent compositions of the present invention give real cleaning and bleaching performance to cloth articles, noun, when formulated as a laundry detergent composition.

DETAILED DESCRIPTION OF THE INVENTION The essential component of the detergent compositions of the present invention is an oxygenase directed to body soils. It is preferred that said enzyme be additionally characterized as being an iron-sulfur or iron heme-oxygenase and / or a heavy metal-dependent oxygenase. All the oxygenases of the present invention will pass the following test on stain removal, obtained on common test fabrics, and which is compared to a reference without oxygenase, under the same conditions. The small scale test is carried out on a Washtec ROACHES laundry meter, equipped with 500 ml stainless steel containers. The small scale test is carried out at 30-40 ° C, with a total washing time of 30 minutes. The tests are carried out in a 1% detergent solution, using the detergent described in Example 10, 1% detergent, using the detergent described in Example 10, composition 5. The detergent is dissolved in 400 ml. of water with a total hardness between 2.0 and 3.0 mmol of Ca2 + / L. The pH of the detergent solution is adjusted to 1% with an acid (citric acid) or with an alkali (NaOH) at pH 8-9. Each container also contains 15 steel spheres for better agitation. The stained test cloths, common and current, are supplied by wfk-Testgewebe GmbH (Chrustenfeld, 10-Brueggen, Germany). At least two duplicates are made for each test. The size of the spots is 3 cm x 4 cm. The common test cloth that has the wfk 10D (cotton stained with dirt / sebum). The level of enzyme in this small-scale test is 1 mg of enzyme protein / L. The levels of the cofactor (s), when necessary, are calculated according to the ratio of enzyme to cofactor (s), known in the literature. For the reference treatment, no enzyme or cofactor is added to the solution. In the test treatment, enzyme and cofactor, previously weighed, are added to the solution; and in a second test treatment only the cofactor is added to the solution. After this it is placed in the test recipients. The wash meter is set at the required temperature. The wash meter is preheated to the correct temperature before starting the test, so that the test is run at a constant temperature. The containers are closed and placed in the previously heated washing meter. The washing cycle is established and the test is started.

After 30 minutes the test is stopped, the containers are removed from the equipment and opened. The ordinary test cloths are removed and rinsed three times in ordinary cold water (hardness 2-3 mmol Ca2 + / L). After rinsing, the followers are dried in a mixer in a normal domestic dryer, until they are completely dry. The stain elimination operation of the enzyme is analyzed, visually qualifying by means of a panel of experts, or preferably, measuring with an instrument the elimination of the stain, for example, with the Datacolor Spectraflash 500 apparatus. The Spectraflash 500 settings used for this test are: speculate excluded; small aperture and UV filter FL40 (= filter with UV cut at 400 nm), and the calibration is carried out against a standard white and black. The result, expressed in the color difference (Cielab) dE, is calculated between the test treatment and the reference treatment. Test 1 comprises the oxygenase of the present invention; Test 2 comprises a monophenolic monooxygenase of EC 1.14.18.1. The enzymes of the invention (test 1) have a deE of 1 or more, against monophenolic monooxygenase (test 2) tested under the same conditions. It has been found that the cleaning compositions of the present invention give effective and efficient removal of everyday body soils, and in particular, cleaning and bleaching is obtained • i-saa ^ a ^ a-f-ft-A real in cloth items when formulated as a laundry detergent composition. Without wishing to be bound by theory, it is believed that the oxygenases of the present invention increase the removal of body dirt by degrading hydrophobic organic compounds based on steroidal structures and on aliphatic, heterocyclic and polycyclic structures, with partial or total unsaturation. of the structural skeleton. It is believed that this enzyme de-cyclizes and fragments the hydrophobic compound or hydroxylates its substrate, making it more hydrophilic and, therefore, easier to remove from the surfaces, in an aqueous solution. Said oxygenases directed to body dirt catalyze the direct insertion of molecular oxygen into the hydrophobic components of the body's dirt. Additionally, the cleaning compositions of the present invention provide sanitization of the treated surfaces. Sanitation includes all the positive effects obtained by the inhibition or reduction of microbial activity in fabrics and other surfaces, such as the prevention of the development of bad odors and bacterial / fungal development. For example, it imparts prevention of the development of bad odor in stored and used fabrics, in stored tableware, especially plastic kitchen items, and in toilets. In particular, the composition of the invention will inhibit or at least reduce the bacterial and / or fungal growth in wet fabric, which is expected to be further processed in the laundry, and thus prevents malodour formation. Additionally, bacterial and / or fungal development on hard surfaces, such as silicone mosaics and sealants, sanitary facilities, etc., will be prevented. The sanitizing potential of the cleaning compositions of the present invention can be enhanced by the addition of chemical sanitizers, such as Triclosan and / or hexemidine. Parums Cosmétiques Actualités, No. 125, November 1995, 51-4, describes suitable chemical sanitizers. The sanitizing benefits of the cleaning compositions of the present invention can be evaluated by the minimum inhibitory concentration (MIC), as described in Tuber. Lung.

Dis., August 1994; 75 (4): 286-90; J. Clin. Microbiol., May 1994; 32 (5): 1261 -7 and J. Clin. Microbiol, October 1992 30 (10): 2692-7 The following is a list of suitable oxygenases targeted to body soiling, for the purposes of the present invention: EC No. Recommended Name 1.13.11.21 ß-carotene- 15,15 '-. Dioxygenase 1.13.11.25 3,4-dihydroxy-9,10-secoandrosta-1, 3,5 (10) -triene-9,17-dione-4,5-dioxygenase 1.14.13.15 cholestanotriol- 26-monooxygenase 1.14.13.43 leukotriene-E4-20-monooxygenase 1.14.15.3 alkane-1 -monooxygenase 1.14-15.5 corticosterone-18-monooxygenase 1.14.99.3 heme-oxygenase 1.14.99.4 progesterone-monooxygenase 1.14.99.7 escueleno-monooxygenase 1.14.99.9 steroid-17a-monooxygenase 1.14.99.10 steroid 21 -monooxygenase 1.14.99.11 estradiol-6b-monooxygenase 1.14.99.12 4-androstene-3,17-dione-monooxygenase 1.14.99.14 progesterone-11 a-monooxygenase 1.14.99.15 methylsterol-monooxygenase 1.14 .99.24 steroid-9a-monooxygenase Some of the oxygenases targeted to the body soiling of the present invention require of the presence of a cofactor. In this case, the cleaning compositions of the present invention will additionally comprise a cofactor, such as ascorbate, oxoglutarate, flavin mononucleotide (FMN), flavin-adenine dinucleotide (FAD), nicotinamide adenine dinucleotide (phosphate (NAD (P)). H) When included, the cofactor will be at a weight ratio of pure oxygen to cofactor which is generally between 10: 1 and 1: 10, preferably between 5: 1 and 1: 8, most preferably between 1: 2 and 1: 5 The enzyme oxygenase directed to body soiling in the detergent compositions according to the invention is incorporated., preferably at a level of 0.0001% to 2%, more preferably, from 0.001% to 0.5%, very preferably, from 0.002% to 0.1% pure enzyme, by weight of the composition. Preferred oxygenases, targeted to body soiling, for specific applications, are alkaline oxygenases targeted to body soiling, ie, enzymes having an enzymatic activity of at least 10%, preferably at least 25% , more preferably at least 40% of maximum activity at a pH ranging from 7 to 12. The most preferred oxygenases, directed to the body soils, are the enzymes that have their maximum activity at a pH ranging from 7 to 12. Homologs of the oxygenase enzymes directed to the body soils of the present invention are also contemplated. The term "homologous" is intended to indicate a polypeptide encoded by DNA that hybridizes to the same probe as the DNA encoding the protein substrate-based oxygenase enzyme, with this amino acid sequence, under certain specific conditions (such as pre-soaking in 5xSSC and pre-hybridization for one hour at ~ 40 ° C in a solution of 20% formamide, 5x Denhardt's solution, 50 mM sodium phosphate, pH 6.8, and 50 μg of denatured and sonically treated calf thymus DNA, followed by hybridization in the same solution, supplemented with 100 μM of ATP for 18 hours at about 40 ° C). The term is intended to include derivatives of the polyphenol / heterocyclic substrate oxygenase sequence, obtained by the addition of one or more amino acid residues, either to the C terminal and the N terminus of the natural sequence, or to any of those terminals; the substitution of one or more amino acid residues at one or more sites of the natural sequence; the omission of one or more amino acid residues at either end of the natural amino acid sequence, or at both ends, or at one or more sites within the natural sequence; or the insertion of one or more amino acid residues at one or more sites of the natural sequence. The enzymes mentioned above may be of any suitable origin, such as of vegetable, animal, bacterial, fungal, or yeast origin. The origin can be additionally mesophilic or extremophilic (psychrophilic, psychrotrophic, thermophilic, barophilic, alkalophilic, acidophilic, halogenophilic, etc.). Purified and unpurified forms of these enzymes can be used. At present it is common practice to modify the wild-type enzymes by protein / genetic engineering techniques, in order to optimally carry out their functional efficiency in the cleaning compositions of the invention. For example, variants can be designed in such a way that they increase the compatibility of the enzyme with the ingredients usually found in these compositions. Alternatively, the variant can be designed so that the optimal pH, the bleach or chelator stability, the catalytic activity and the like of the enzyme are tailored to suit the particular cleaning application. In particular, attention should be focused on amino acids sensitive to oxidation, in the case of bleach stability, and on surface charges, for compatibility with the surfactant. HE can modify the isoelectric point of these enzymes, substituting some amino acids with charge, for example, an increase in the isoelectric point can help improve compatibility with anionic surfactants. The stability of the enzymes can be further increased by creating, for example, additional salt bridges, and forcing the calcium binding sites to increase the stability to the chelator.

THE DETERGENT COMPONENTS The detergent compositions of the present invention may also contain additional detergent components. The precise nature of these additional components, and the levels of their incorporation, will depend on the physical form of the composition and the nature of the cleaning operation for which they are to be used. The detergent compositions preferably additionally comprise another enzymatic bleach system, an activated, conventional bleach system, a bleach system based on metallo catalyst, and / or another detergent enzyme. In a preferred embodiment, the present invention relates to a composition for laundry and / or fabric care, comprising an oxygenase based on a protein substrate (examples 1-18). In a second embodiment, the present invention relates to compositions for wash household crockery and cleaners, which include sanitizing compositions (examples 19-28). The detergent compositions according to the present invention may be liquid, in the form of paste, gel, stick, tablet, spray, foam, powder, or granular form. The granulated compositions can also be in "compact" form; while the liquid compositions may also be in a form "concentrated." The compositions of the invention, for example, can be formulated as dishwashing compositions by hand and in the washing machine; laundry detergent compositions by hand and in the washing machine, including laundry additive compositions and compositions suitable for use in soaking and / or pretreatment of soiled fabrics, such as fabric softening compositions, added during rinsing, and as compositions for use them in general domestic hard surface cleaning operations. When formulated as compositions for use in manual dishwashing methods, the compositions of the present invention preferably contain a surfactant and, preferably, other detergent compounds selected from organic polymeric compounds, foaming agents, group II metal ions. , solvents, hydrotropes and additional enzymes.

When formulated as suitable compositions for use in a washing machine washing method, the compositions of the invention preferably contain both a surfactant and a builder compound and, additionally, one or more detergent components, preferably selected of organic polymeric compounds, bleaching agents, additional enzymes, suds suppressors, dispersants, lime soap dispersants, agents for suspending and preventing redeposition of dirt, and corrosion inhibitors. The laundry compositions also contain softening agents, as additional detergent components. Said compositions containing said oxygenase can provide fabric cleaning, stain removal, maintenance of whiteness, softening, color appearance, inhibition of dye transfer and sanitation, when formulated as laundry detergent compositions. The compositions of the invention can also be used as additive products for detergent. Said additive products are intended to supplement or reinforce the operation of conventional detergent compositions. If necessary, the density of the detergent compositions for laundry, here, varies between 400 and 1200 g / liter, preferably between 600 and 950 g / liter of composition, measured at 20 ° C.

The "compact" form of the compositions herein is best reflected by density and, in terms of composition, by the amount of inorganic filler salt. Inorganic filler salts are conventional ingredients in detergent compositions in powder form; In conventional detergent compositions, the filler salts are present in substantial amounts, typically from 17 to 35% by weight of the total composition. In compact compositions, the filler salt is present in amounts not exceeding 15% of the total composition, preferably not exceeding 10%, most preferably, not greater than 5% by weight of the composition. The inorganic filler salts, as it is meant in the compositions herein, are selected from the alkali metal and alkaline earth metal salts of sulfates and chlorides. A preferred filler salt is sodium sulfate. The liquid detergent compositions according to the present invention may also be in "concentrated form". In such a case, the liquid detergent compositions according to the present invention will contain a smaller amount of water, as compared to conventional liquid detergents. It is typically preferred that the water content of the concentrated liquid detergent be less than 40%, more preferably, less than 30%, most preferably less than 20% by weight of the detergent composition.

THE CONVENTIONAL DETERGENT ENZYMES The cleaning compositions of the present invention, in addition to the oxygenase enzyme directed to body soiling, additionally comprise one or more enzymes that provide cleaning, care and / or sanitizing performance benefits of the fabric. It has been found that the combination of said specific oxygenase with the detergent enzyme gives improved cleaning of the polyphenol / heterocyclic stains and / or soils, and stains and / or body soils of daily use, and when formulated as a composition for laundry, obtains cleaning and bleaching improved, real, in cloth items. Said enzymes include selected enzymes of: cellulases, hemicellulases, peroxidases, proteases, glucoamylases, amylases, xylanases, lipases, phospholipases, esterases, cutinases, petinases, keratanases, reductases, oxidases, phenoloxidases, lipoxygenases, ligninases, pullulanases, tannases, pentosanases, malanases, beta-glutanas, arabinosidases, hyaluronidase, chondroitinase, laccase, or mixtures thereof. A preferred combination is a cleaning composition having a combination of conventional applicable enzymes, such as protease, amylase, lipase, cutinase and / or cellulase, together with one or more plant cell wall degrading enzymes. Suitable proteases are subtilisins that are obtained from particular strains of B. subtilis and β. licheniformis (subtilisin BPN and BPN ').

A suitable protease is obtained from a Bacillus strain having maximum activity across the pH range of 8-12, developed and sold as ESPERASE® by Novo Industries A / S of Denmark, hereinafter referred to as "Novo". The preparation of this enzyme and analogous enzymes is described in GB 1, 243,784, by Novo. Other suitable proteases include: ALCALASE ®, DURAZYM ®, and SAVINASE ® by Novo, and MAXATASE ®, MAXACAL ®, PROPERASE ® and MAXAPEM ® (Maxacal engineered with protein) from Gist - Brocades. Proteolytic enzymes also comprise modified bacterial serine proteases, such as those written in European Patent Application Serial No. 87 303761.8, filed on April 28, 1987 (in particular pages 17, 24 and 98), and referred to herein as "Protease B", and in European patent application 199,404, Venegas, published October 29, 1986, which relates to a modified bacterial serine proteolytic enzyme, which is referred to as "protease A" in the present. The one called "Protease C" is suitable, which is a variant of a Bacillus alkaline serine protease, in which lysine replaced arginine in position 27, tyrosine replaced valine in position 104, serine replaced asparagine in position 123, and alanine replaced threonine at position 274. Protease C is described in EP 90915958.4, which corresponds to WO 91/06637, published May 16, 1991. Also included are genetically modified variants, particularly C-protease.

A preferred protease, termed "protease D" is a variant of carbonylhydrolase having an amino acid sequence that is not found in nature, which is derived to a precursor carbonylhydrolase by substituting a plurality of amino acid residues at a position with a different amino acid, in said carbonylhydrolase, equivalent to the +76 position, preferably also in combination with one or more amino acid residue positions, equivalent to those selected from the group consisting of +99, +101, +103, +104, +107, +123, +27, +105, +109, +126, +128, +135, +156, +166, +194, +197, +204, +206, +210, +216, +217, +218 , +222, +260, +265, and / or +274, according to the numeration of the subtilisin of Bacillus amyloliquefaciens, as described in WO 95/10591, and in the patent application of C. Ghosh and co-authors, "Bleaching compositions comprising protease enzymes", which has the serial number of the United States 08 / 322,677, filed on October 13, 1994. The proteases described in patent applications EP 251 446 and WO 91/06637, the BLAP ® protease described in WO 91/02792 and its variants described in WO 95/23221 are also suitable for the present invention. See also a high pH protease of Bacillus sp NCIMB 40338, described in WO 93/18149 A of Novo. Enzymatic detergents comprising protease, one or more other enzymes and a reversible protease inhibitor are described in WO 92/03529 A by Novo. When desired, a protease having decreased adsorption and increased hydrolysis is available, as described in WO 95/07791 áate ^^^^ Procter & Gamble. A recombinant trypsin-like protease for detergents, suitable herein, is described in WO 94/25583 by Novo. Other suitable proteases are described in EP 516 200 by Unilever. Proteolytic enzymes are incorporated in the detergent compositions of the present invention at a level of from 0.0001% to 2%, preferably from 0.001% to 0.2%, more preferably, from 0.005% to 0.1% pure enzyme by weight of the composition. The cellulases usable in the present invention include both bacterial and fungal cellulases. It is preferred that they have an optimum pH of between 5 and 12, and an activity greater than 50 UVCE (Cellulose Viscosity Unit). Suitable cellulases are described in U.S. Patent 4,435,307, Barbesgoard and co-inventors, J61078384 and WO 96/02653, which describes the fungal cellulase produced, respectively, from Humicola insolens, Trichoderma, Thielavia and Sporotrichum. EP 739 982 describes isolated cellulases of the Bacillus species. Suitable cellulases are also described in GB-A-2,075,028, GB-A-2,095,275, DE-OS-2,247,832 and WO 95/26398. Examples of these cellulases are those produced by a strain of Humicola insolens. { Humicola grisea var. Thermoidea), particularly the DSM 1800 strain of Humicola. Other suitable cellulases are those originated from Humicola insolens which have a molecular weight of approximately 50 KDa, an isoelectric point of 5.5 and which contain 415 amino acids; and a -43 kD endoglucanase, derived from Humicola insolens, DSM 1800, exhibiting cellulase activity; a preferred endoglucanase component has the amino acid sequence described in the patent application of TCP No. WO 91/17243. Also suitable cellulases are the EGIII cellulases of Trichoderma longibrachiatum, described in WO 94/21801, Genencor, published September 29, 1994. Cellulases having color care benefits are especially suitable. Examples of these cellulases are those described in European patent application No. 91202879.2, filed on November 6, 1991 (Novo). Carezyme and Celluzyme (Novo Nordisk A / S) are especially useful. See also WO 91/17244 and WO 91/21801. Other cellulases suitable for their fabric care and / or cleaning properties are described in WO 96/34092, WO 96/17994 and WO 95/24471. Said cellulases are normally incorporated in the detergent composition at levels of 0.0001% to 2% active enzyme by weight of the detergent composition. Other preferred enzymes that can be included in the detergent compositions of the present invention include the lipases. Lipase enzymes suitable for use in detergents include those produced by microorganisms of the Pseudomonas group, as Pseudomonas stutzeri ATCC 19,154, which was described in the British patent 1, 372,034. Suitable lipases include those which show a positive immunological cross-reaction with the lipase antibody, produced by the microorganism Pseudomonas fluorescens IAM 1057. This lipase is available from Amano Pharmaceutical Co. Ltd., Nagoya, Japan, under the brand name Lipase P "Amano", hereinafter referred to as "Amano-P". Other suitable commercial lipases include the Amano-CES lipases from Chromobacter viscosum, for example, from Chromobacter viscosum var. Lipolyticum NRRLB 3673 from Toyo Jozo Co., Tagata, Japan; lipases from Chromobacter viscosum, from U. S. Biochemical Corp., E. U. A., and from Disoynth Co., The Netherlands; and lipases from Pseudomonas gladiolii. Lipases such as M1 Lipase ® and Lipomax ® (Gist Brocades) and Lipolase ® and Lipolase Ultra ® (Novo, which have have been found to be very effective when used in combination with the compositions of the present invention. Also suitable are the lipolytic enzymes described in EP 258 068, WO 92/05249 and WO 95/22615, of Novo Nordisk, and in WO 94/03578, WO 95/35381 and WO 96/00292, from Unilever. Cutinases are also suitable [EC 3.1.1.50], which may to be considered as a special class of lipase, that is, lipases that do not require interfacial activation. The addition of cutinases to the detergent compositions had been described, for example, in WO-A-88/09367 (Genencor); WO 90/09446 (Plant Genetic System) and WO 94/15963 and WO 94/14964 (Unilever). Normally lipases and / or cutinases are incorporated in the detergent composition at levels of 0.0001% to 2% active enzyme, by weight of the detergent composition.

J ^ aJhBi ^^^^ i ^, "^^ .. ^ a ^ a ^ a ^ Amylases (alpha and / or beta) can be included to remove carbohydrate-based stains. WO 94/02597, from Novo Nordisk A / S, published on February 3, 1994, describes cleaning compositions that incorporate mutant amylases. See also WO 95/106303, from Novo Nordisk A / S, published on April 20, 1994. Other amylases known for use in cleaning compositions include both alpha- and beta-amylases. Alpha-amylases are known in the art, and include those described in U.S. Patent No. 5,003, 257; EP 252,666; WO 91/00353; FR 2,676,456; EP 285,123, EP 525,610, EP 368,341, and in British patent specification No. 1, 296,839 (de Novo). Other suitable amylases are amylases with enhanced stability, described in WO 94/18314, published August 18, 1994, and WO 96/05295, Genencor, published February 22, 1996; and the amylase variants having further modification in the immediate predecessor, obtainable from Novo Nordisk A / S, described in WO 95/10603, published in April 1995. Also suitable are the amylases described in EP 277 216; WO 95/26397 and WO 96/23873 (all from Novo Nordisk). Examples of commercial alpha-amylases products are: Purafect Ox Am ® from Genencor, and Termamyl ®, Ban ®, Fungamyl ® and Duramyl ®, all available from Novo Nordisk A / S, Denmark. WO 95/26 397 describes other suitable amylases: alpha-amylases, characterized in that they have a specific activity at least 25% higher than the specific activity of Termamyl ®, at a temperature range of 25 ° C to 55 ° C, and a pH value on the scale of 8 to 10, measured by the analysis of ^^ fe ^ -a- iiftt? & Sh *.

Alpha-amylase activity of Phadebas ®. The variants of the above enzymes, described in WO 96/23873 (Novo Nordisk), are suitable. Other amylolytic enzymes with improved properties, with respect to the level of activity and the combination of thermostability, and a higher level of activity, are described in WO 95/35382. The amylolytic enzymes are incorporated in the detergent compositions of the present invention at a level of from 0.0001% to 2%, preferably from 0.00018% to 0.06%, more preferably, from 0.00024 $ to 0.048% pure enzyme, by weight of the composition . The enzymes mentioned above can be of any suitable origin, such as of vegetable, animal, bacterial, fungal and yeast origin. The origin can be additionally mesophilic or extremophile (psychrophilic, psychrotrophic, thermophilic, barophilic, alkalophilic, acidophilic, halogenophilic, etc.). Purified or unpurified forms of these enzymes can be used. Mutants of natural enzymes are also included, by definition. Mutants can be obtained, for example, by protein and / or genetic engineering, chemical and / or physical modifications of natural enzymes. It is also common practice the expression of the enzyme by means of host organisms, in which the genetic material, responsible for the production of the enzyme, has been cloned. Said enzymes are normally incorporated in the detergent composition at approximate levels of 0.0001% to 2% active enzyme by weight of the detergent composition. You can add the enzymes ea ám **? as separate individual ingredients (clods, granulates, stabilized liquids, etc., containing an enzyme) or as mixtures of two or more enzymes (for example, cogranulates). Other suitable detergent ingredients that can be additions are the enzyme oxidation scavengers, which are described in co-pending European Patent Application No. 92870018.6, filed on January 31, 1992. Examples of such enzyme oxidation scavengers are the ethoxylated tetraethylenepolyamines. A variety of enzyme materials are also described, and means for their incorporation into synthetic detergent compositions, in WO 9307263 A and in WO 9307260 A, from Genencor International; WO 8908694 A de Novo and US Pat. No. 3,553,139, January 5, 1971, by McCarty and coauthors. Enzymes are further described in U.S. Patent 4,101,457, to Place et coinventores, of 18 July 15, 1978, and in U.S. Patent 4,507,219, Hughes, March 26, 1985. Enzyme materials useful for liquid detergent formulations, and their incorporation into such formulations, are described in US Pat. No. 4,261, 868, of Hora and co-inventors, dated April 14, 1981. Enzymes for use in detergents may be stabilized by means of various techniques. Enzyme stabilization techniques are described and exemplified in US Pat. No. 3,600,319, August 17, 1971, by Gedge and co-inventors; EP 199,405 and EP 200,586, of October 29, 1986, of Venegas. They are also described enzyme stabilization systems, for example, in U.S. Patent 3,519,570. A useful Bacillus, sp AC 13, which gives proteases, xylanases and cellulases, is described in WO 9401532 A, by Novo.

THE WHITENING AGENT Additional preferred optional detergent ingredients, including conventional bleaching systems, activated, other enzymatic catalysts and / or metallo catalyst catalysts may be included in the cleaning compositions of the present invention. It has been found that the combination of said specific oxygenase with another bleach system provides improved cleaning of spots and / or protein-based dirt, such as stains and / or food stains containing proteins and body dirt, of daily use, and when is formulated as a laundry composition, obtains improved real bleaching and cleaning of fabric articles, while providing color security. The bleaching agent component, for use herein, can be any of the bleaching agents useful for cleaning compositions, including oxygenated bleach, as well as others known in the art. The bleaching agent suitable for the present invention may be an activated or non-activated bleaching agent. Bleaching agents are such as hydrogen peroxide, PB1, PB4 and percarbonate, with a particle size of 400 to 800 microns. These bleaching agent components can include one or more oxygenated bleaching agents and, depending on the bleaching agent selected, one or more bleach activators. When present, the oxygenated bleaching compounds will typically be at approximate levels of 1% to 25%. Hydrogen peroxide releasing agents can be used in combination with the bleach activators, such as tetraacetylethylenediamine (TADE), nonanoyloxybenzenesulfonate (NOBS, described in US 4,412,934), 3,5-trimethylhexanooyloxybenzenesulfonate (ISONOBS, 0 described in EP 120,591), or pentaacetylglucose (PAG) or N-nonanoyl-6-aminocaproic acid phenolsulfonate ester (NACA-OBS, described in WO 94/28106), which are perhydrolyzed to form a peracid as an active bleaching species, leading to an improved bleaching effect . Suitable activators are also acylated citrate esters, such as those described in co-pending European Patent Application No. 91870207.7, and the asymmetric acyclic amide bleach activator, of the formula below, as described in US Pat. pending patent applications of Procter & Gamble Serial No. 60 / 022,786 (filed July 30, 1996), and No. 60 / 028,122 (filed October 15, 2006) m ^ m ^^^^^^^^ in which Ri is a straight or branched chain alkyl group, saturated or unsaturated, of 7 to 13 carbon atoms; R2 is a straight or branched chain alkyl group, saturated or unsaturated, of 1 to 8 carbon atoms; and R3 is a straight or branched chain alkyl group, saturated or unsaturated, of 1 to 4 carbon atoms. A category of oxygenated bleaching agent that can be used comprises the percarboxylic acid bleaching agents and their salts. Suitable examples of this class of agents include: magnesium monoperoxyphthalate hexahydrate, the magnesium salt of meta-chloroperbenzoic acid, 4-nonylamino-4-oxoperoxybutyric acid and diperoxydecanedioic acid. Such bleaching agents are described in U.S. Patent 4,483,781, in U.S. Patent Application Serial No. 740,446; in the European patent application 0,133,354 and in the US patent 4,412,934. Highly preferred bleaching agents also include 6-nonyllamino-6-oxoperoxycaproic acid, which is described in U.S. Patent 4,634,551. Another category of bleaching agents that can be used comprises halogenated bleaching agents. Examples of hypohalogenite whiteners are, for example, trichloroisocyanuric acid and sodium and potassium dichloroisocyanurates, N-chloro- and N-bromoalkanesulfonamides. Said materials are normally added to 0.5-10% by weight of the final product, preferably from 1 to 5% by weight. m & é? "- * - *" - Useful bleaching agents, including peroxyacids and bleaching systems, comprise bleach activators and peroxygen bleach compounds for use in detergent compositions according to the invention, are described in patent applications in process, US Pat. No. 08 / 136,626, PCT / US95 / 07823, WO 95/27772, WO 95/27773, WO 95/27774 and WO 95/27775 The peroxide may also be present. hydrogen by adding an enzyme system (i.e., an enzyme and a substrate therefor), which is capable of generating hydrogen peroxide at the beginning of, or during the washing and / or rinsing process.These enzyme systems are described in the application European Patent EP 91202655.6, filed October 9, 1991. The enzymes peroxidase in combination with oxygen, sources of hydrogen peroxide, for example, percarbonate, perborate, persulfate, peroxide, are used. hydrogen, etc., and a bleach increaser. They are used for "bleaching in solution", that is, to prevent the transfer of dyes or pigments removed from substrates during washing operations, to other substrates present in the washing solution. Peroxidase enzymes are known in the art and include, for example, horseradish peroxidase, ligninase and halogenoperoxidase, such as chloro- and bromo-peroxidase. Peroxidase-containing detergent compositions are described, for example, in the international applications of TCP WO 89/099813, WO 89/09813 and in European patent applications EP No. 91202882.6, filed on November 6, 1991, and EP No 96870013.8, filed February 20, 1996. The lacease enzyme is also suitable. 5 Increters are usually included at a level of 0. 1% to 5% by weight of the total composition. Preferred enhancers are phenothiazine and substituted phenoxazine, 10-phenothiazinepropionic acid (PPT), 10-ethylphenothiazine-4-carboxylic acid (EPC), 10-phenoxazinpropionic acid (POP) and 10-methylphenoxazine (described in WO 94/12621) and the syringatos substituted (substituted alkyl syringates, 3 to 5 carbon atoms) and phenols. Percarbonate or sodium perborate are the preferred sources of hydrogen peroxide. Said peroxidases are usually incorporated in the detergent composition at levels of 0.0001% to 2% of active enzyme, by weight of the detergent composition. Metal-containing catalysts for use in bleaching compositions include cobalt-containing catalysts, such as pentaamine-cobalt acetate (III) salts and manganese-containing catalysts, such as those described in EPA 549 271; EPA 549 272, EPA 458 397, US 5,246,621, EPA 458 398, EPA 458 397, US 5,194,416 and US 5,114,611. The bleaching composition comprising a peroxy compound, a manganese-containing bleach catalyst and a chelating agent, is described in patent application No. 94870206.3. «3a 6 ^ fa» fc- | Preferred metal-containing catalysts for the purposes of the present invention are a transition metal complex of a rigid macropolyclic ligand. The phrase "rigid macropolicíclico ligand" is abbreviated in some cases "MRL" in the following discussion. The amount used is a catalytically effective amount, suitably about 1 part per 1, 000 million parts or more, for example, up to about 99.9%, more typically, about 0.001 ppm or more, preferably about 0.05 ppm at 500 ppm (where one billion parts are by weight, and "ppm" denotes parts per million, by weight). Suitable transition metals, for example, Mn, are illustrated below. "Macropolicíclico" means that an MRL is at the same time and macrocycle and a polycyclic. "Polycyclic" means at least bicyclic. The term "rigid", as used herein, includes "having a superstructure" and "with a cross bridge". "Rigid" has been defined as the strict opposite of flexibility; see D. H. Busch, Chemical Reviews, (1993), 93, 847-860, incorporated herein by this reference. More particularly, "rigid", as used herein, means that the MRL must be determinably stiffer than a macrocycle ("macrocycle ancestor") that is otherwise identical (having the same ring size and the same type and same). number of atoms in the main ring), but lacking a superstructure (especially the linker portions or, preferably, the cross bridge portions) found in the MRLs. In determining the comparative stiffness of macrocycles with and without superstructures, the practitioner will use the free form (not the metal-bonded form) of the macrocycles. It is well known that rigidity is useful when comparing macrocycles; The appropriate tools to determine, measure or compare stiffness include computational methods (see, for example, Zimmer, Chemical Reviews, (1995), 94 (38), 2629-2648 or Hancock and co-authors, Inorganic Chimica Acta, (1989) , 164, 73-84 Often a determination can be made as to whether a macrocycle is more rigid than another simply by making a molecular model, so it is not essential in general to know the configuration energies in absolute terms, nor to compute them accurately. Excellent comparative determinations of the stiffness of one macrocycle versus another can be made using computational tools based on a low-cost personal computer, such as ALCHEMY III, commercially available from Tripos Associates.Tripos also has more expensive application programs available, that not only allow comparative determinations, but also absolute, alternatively, SHAPES can be used (see Zimmer, ci One observation that is important in the context of the present invention is that there is an optimum for the purposes of the present, when the original macrocycle is clearly flexible, as compared to the cross-bridge shape. Thus, unexpectedly, it is preferred to use predecessor macrocycles containing at least four donor atoms, such as the cyclam derivatives, and bypass them, instead of starting with a more rigid predecessor macrocycle. Another observation is that macrocycles with a cross bridge are significantly preferred over macrocycles that are bridged in other ways. Preferred MRLs herein are a special type of ultra-rigid ligand, which has cross-links. A "cross bridge" is illustrated non-limitingly in 1.11 below. In 1.11, the transverse bridge is a portion -CH2CH2-. Join N1 and N8 in the illustrative structure. By comparing, a bridge "on the same side", for example, if it were to be introduced through N1 and N12 in 1.11, would not be enough to constitute a "cross bridge" and, consequently, would not be preferred. Suitable metals in the rigid ligand complexes include: Mn (ll), Mn (lll), Mn (IV), Mn (V), Fe (ll), Fe (lll), Fe (IV), Co (l), Co (ll), Co (lll), Ni (l), Ni (ll), Ni (lll), Cu (l), Cu (ll), Cu (lll), Cr (ll), Cr (lll), Cr (IV), Cr (V), Cr (VI), V (lll), V (IV), V (V), Mo (IV), Mo (V), Mo (VI), W (IV), W (V), W (VI), Pd (ll), Ru (ll), Ru (lll) and Ru (IV). Preferred transition metals in the transition metal bleach catalyst of the present include: manganese, iron and chromium. Preferred oxidation states include the oxidation states (II) and (III). Manganese (II) is included in both the low-spin configuration and the high-spin complex. It should be noted that complexes, such as Mn (ll) complexes of low "spin" are rather rare throughout the coordination chemistry. The designation (II) or (III) denotes a coordinated transition metal that has the required oxidation state; The coordinated metal atom is not a free atom or one that has only water as a ligand. In general, as used herein, a "ligand" is any portion capable of directing the covalent bond to a metal ion. The ligands can be charged or neutral, and can vary widely, including simple monovalent donors, such as chloride, or simple amines that form a single coordinated bond and a single point of attachment to a metal, to oxygen or ethylene, which can form a ring of three members with a metal and, in this way, can be said to have two potential points of fixation, to larger portions, such as ethylenediamine or aza macrocycles, which form up to the maximum number of simple ligatures to one or more metals which are allowed by the available sites in the metal and the number of single pairs or alternative binding sites of the free ligand. Numerous ligands can form different ligatures to simple donor ligations, and can have multiple attachment points. The ligands useful herein may fall into several groups: the MRL, preferably a cross-linked macropolicicy (preferably there will be an MRL in a useful transition metal complex, but more, for example, two may be present; not in preferred mononuclear transition metal complexes); other optional ligands, which are generally different from the MRL (generally there will be from 0 to 4, preferably from 1 to 3 of said ligands) and ligands transiently associated with the metal as part of the catalytic cycle; the latter are typically ^^ & M ^^ S ^^^ éit > i? ^ íí ^ related to water, hydroxide, oxygen or peroxides. The ligands of the third group are not essential to define the metal bleach catalyst, which is a stable, isolable chemical compound, which can be fully characterized. Ligands that bind to metals through donor atoms, each of which has at least a single lone pair of electrons available for donation to a metal, have a donor capacity, or a potential denticity, at least equal to the number of donor atoms. In general, that donor capacity can be exercised totally or only partially. In general, the MRLs herein may be viewed as the result of imposing additional structural rigidity on the "predecessor macrocycles" specifically selected. More generally, the MRLs (and the corresponding transition metal catalysts) herein, suitably comprise: (a) at least one macrocycle main ring, comprising four or more heteroatoms; and (b) a non-metallic superstructure, covalently connected, capable of increasing the stiffness of the macrocycle, preferably selected from: (i) a bridge superstructure, such as a linker portion; (ii) a transverse bridge superstructure, such as a linker portion that forms a transverse bridge; and (iii) combinations of them.

The term "superstructure" is used here as defined in the literature, by Busch and coauthors; see, for example, Busch's articles in Chemical Reviews. The preferred superstructures herein not only increase the rigidity of the predecessor macrocycle, but also favor the folding of the macrocycle, so that a metal is coordinated in a crack. The right superstructures can be notoriously simple; for example, a linker portion may be used, such as those illustrated in 1.9 and 1.10 below: wherein n is an integer, for example, from 2 to 8, preferably less than 6, typically 2 or 4; or 1. Where m and n are integers of about 1 to 8, more preferable, of 1 to 3; Z is N or CH; and T is a compatible substituent, for example, H, alkyl, The complex aromatic ring in 1.10 may be replaced by a saturated ring, in which the Z atom, which connects to the ring, may contain N, O. , S or C. Without pretending to be limited by any theory, it is believed that the preorganization constituted in the MRLs of the present, which leads to the extra kinetic and / or thermodynamic stability of its metal complexes, arises from either or both of the topological restrictions and the increased stiffness (loss of flexibility) compared to the free predecessor macrocycle, which has no superstructure, MRLs, as defined here, and their preferred cross-bridge sub-family, which can be said to be "ultra-rigid". "combine two sources of fixed preorganization In the preferred MRLs of the present, the linking portions and the preceding macrocyclic rings are combined to form ligands that have a significant degree of" folding ", typically greater than in many known superstructure ligands, in which a superstructure is attached to a largely flat, often unsaturated macrocycle. See, for example, D. H. Busch, Chemical Reviews (1993), 93, 847-880. Additionally, preferred MRLs herein have numerous properties, including: (1) they are characterized by very high protonic affinities, as in so-called "proton sponges"; (2) tend to react slowly with multivalent transition metals, which when combined with (1) above, make it difficult to synthesize their complexes with certain metal ions hydrolysable in hydroxyl solvents; (3) when coordinated to transition metal atoms, as identified here, MRLs result in complexes that have exceptional kinetic stability, so that metal ions only dissociate extremely slowly, under conditions that would destroy the complexes with ordinary ligands; and (4) these complexes have exceptional thermodynamic stability; however, the unusual kinetics of the MRL dissociation of the transition metal may challenge conventional equilibrium measures that could quantify this property. In one aspect of the present invention, MRLs include those comprising: (i) an organic macrocyclic ring containing four or more donor atoms (preferably at least three, more preferably at least four, of these donor atoms are N) ) separated from each other by covalent ligatures of at least one, preferably two or three, non-donor atoms; two to five (preferably three to four, more preferably four) of these donor atoms are coordinated to the same transition metal in the complex; and (ii) a linker portion, preferably a cross-bridge chain, which covalently connects at least two donor atoms (preferably non-adjacent) of the organic macrocyclic ring; said covalently connected (preferably non-adjacent) donor atoms are donor heads with bridgeheads, which are coordinated to the same transition metal in the • ^ - ^^ ß ^^^^^ complex; and wherein the linker portion (preferably a cross-bridge chain) comprises from 2 to about 10 atoms (preferably, the cross-bridge chain is selected from two, three or four non-donor atoms and from four to six non-donor atoms with an additional donor atom). Suitable MRLs are further illustrated, non-limitingly, by the following compound: 1. eleven This is an MRL according to the invention, which is a methyl-substituted cyclam derivative (all nitrogen atoms are tertiary), with highly preferred cross-bridge. Formally, this ligand is called 5,12-dimethyl-1, 5,8,12-tetraazabicyclo [6.6.2] hexadecane, using the von Baeyer extended system. See A Guide to IUPAC Nomenclature of Organic Compounds: Recommendations 1993, R. Panic, W. H. Powell and J-C Richer (Eds.), Blackwell Scientific Publications, Boston, 1993; see especially section R-2.4.2.1. According to conventional terminology, N1 and N8 are "bridgehead" atoms; as defined herein, more particularly, "bridgehead donor atoms", since they have single pairs, capable of donating to a metal. N1 is connected to two non-bridgehead donor atoms, N5 and N12, by distinct saturated carbon chains, 2, 3, 4 and 14, 13, and to the N8 donor bridgehead by means of a "linker portion" to , b, that here is a carbon chain saturated with two carbon atoms. N8 is connected to two non-bridgehead donor atoms, N5 and N12, by different chains 6, 7 and 9, 10, 11. Chain a, b is a "linker portion" as defined herein, and is of special type , preferred, called a "cross-bridge" portion. The "macrocyclic ring" of the ligand appearing above, or "main ring" (IUPAC) includes the four donor atoms and the chains 2, 3, 4; 6, 7; 9, 10, 11;: and 13, 14; but not a, b. This ligand is conventionally bicyclic. The short bridge or "linker portion" a, b, is a "transverse bridge", as defined herein, bisecting a, b the macrocyclic ring. The MRLs of the present, of course, are not limited to being synthesized from some preformed macrocycle, plus a preformed element, "rigidity imparter" or "conformation modifier"; Rather, a wide variety of synthetic media are useful, such as in template or model synthesis. See, for example, Busch and coauthors, which is summarized in Heterocyclic compounds: Aza-crown macrocycles ", J. S. Bradshaw and coauthors.Transition metal bleach catalysts useful in the compositions of the invention may generally include compounds ^ ah? 3ttte ^ rfS ^ A. known in which they are adapted to the definition of the present as well as, more preferably, any of a large number of novel compounds, expressly designed for the laundry and cleaning uses herein, and are non-limitingly illustrated by any of the following: dichloro-5,12-dimethyl-1, 5,8,12-tetraazabicyclo [6.6.2] hexadecane-manganese (II), dichloro-4,10-dimethyl-1, 4,7,10-tetraazabicyclo [5.5.2] tetradecane-manganese (ll), diacuo-5,12-dimethyl-1, 5,8,12-tetraazabicyclo [6.6.2] hexadecano-manganese (II) hexafluorophosphate, aqueous-hydroxy hexafluorophosphate -5,12-dimethyl-1, 5,8,12-tetraazabicyclo [6.6.2] hexadecane-manganese (11), diacuo-4,10-dimethyl-1,4J, 10-tetraazabicyclohexafluoro [5.5.2 ] tetra-decane-manganese (II), diacuo-4,10-dimethyl-1, 4,7,10-tetraazabicyclo [5.5.2] tetra-decane-manganese tetrafluoroborate (II). tetrafluoroborate of diaquo-4,10-dimethyl-1, 4,7,10-tetraazabicyclo [5.5.2) hexa-decane-manganese (ll), dichloro-5,12-dimethyl-1,5,6 hexafluorophosphate -tetraazabicyclo [6.6.2) hexadecano-manganese (lll), dichloro-5,12-di-n-butyl-1, 5,8,12-tetraazabicyclo [6.6.2] hexadecane-manganese (II), dichloro-5,12-dibenzyl-1, 5,8,12-tetraazabicyclo [6.6.2] hexadecane-manganese (II), dichloro-5-n-butyl-12-methyl-1, 5,8,12-tetraazabicyclo [6.6.2] hexadecane-manganese (II), dichloro-5-n-octyl-12-methyl-1, 5, 8,12-tetraazabicyclo [6.6.2] hexadecane-manganese (II), dichloro-5-n-butyl-12-methyl-1, 5,8,12-tetraazabicyclo [6.6.2] hexadecane-manganese (II) dichloro -5,12-dimethyl-1, 5,8,12-tetraazabicyclo [6.6.2] hexadecane-iron (II), dichloro-4,10-dimethyl-1, 4,7,10-tetraazabicyclo [5.5.2] tetradecane-iron (ll), dichloro-5,12-dimethyl-1, 5,8,12-tetraazabicyclo [6.6.2] hexadecane-copper (ll), dichloro-4,10-dimethyl-1, 4,7, 10-tetraazabicyclo [5.5.2] tetradecane-copper (II), dichloro-5,12-dimethyl-1, 5,8,12-tetraazabicyclo [6.6.2] hexadecane-cobalt (II), dichloro-4,10- dimethyl-1, 4J, 10-tetraazabicyclo [5.5.2] tetradecane-cobalt (ll), dichloro-5,12-dimethyl-4-phenyl-1, 5,8,12-tetraazabicyclo [6.6.2 ] hexadecane-manganese (II), dichloro-4,10-dimethyl-3-phenyl-1, 4,7,10-tetraazabicyclo [5.5.2] tetradecane-manganese (II), dichloro-5,12-dimethyl-4 , 9-diphenyl-1, 5,8,12-tetraazabicyclo [6.6.2] hexadecane-manganese (II), dicl Gold-4,10-dimethyl-3,8-diphenyl-1,4,7,10-tetraazabicyclo [5.5.2] tetradecane-manganese (II), dichloro-5,12-dimethyl-2,11-diphenyl -1, 5,8,12-tetraazabicyclo [6.6.2] hexadecane-manganese (II), a ^ gg ^ l dichloro-4,10-dimethyl-4,9-diphenyl-1, 4,7,10-tetraazabicyclo [5.5.2] tetradecane-manganese (II), dichloro-2,4,5,9, 11, 12-hexamethyl-1, 5,8,12-tetraazabicyclo [6.6.2] hexadecane-manganese (II), dichloro-2,3,5,9,10,12-hexamethyl-1, 5,8,12 -tetraazabicyclo [6.6.2] hexadecane-manganese (II), dichloro-2,2,4,5,9,9,11,1-octamethyl-1, 5,8,12-tetraazabicyclo [6.6.23] hexadecane- manganese (ll), dichloro-2,2,4,5,9,11,11, 12-octamethyl-1, 5,8, 12-tetraazabicyclo [6.6.2] hexadecane-manganese (II), dichloro-3, 3, 5,10,10,12-hexamethyl-1, 5,8,12-tetraazabicyclo [6.6.2] hexadecane-manganese (II), dichloro-3,5,10,12-tetramethyl-1, 5,8 , 12-tetraazabicyclo [6.6.2] hexadecane-manganese (II), dichloro-3-butyl-5,10,12-trimethyl-1, 5,8,12-tetraazabicyclo [6.6.2] hexadecane-manganese (II) , dichloro-1, 5,8,12-tetraazabicyclo [6.6.2] hexadecane-manganese (II), dichloro-1, 4J, 10-tetraazabicyclo [5.5.2] tetradecane-manganese (II), dichloro-1, 5 , 8,12-tetraazabicyclo [6.6.2] hexadecane-iron (II), dichloro-1, 4J, 10-tetraazabicyclo [5.5.2] tetradecane-hydro (II), aqueous-chloro-2- (2-hydroxyphenyl) -5,12-dimethyl-1, 5,8,12-tetraazabicyclo [6.6.2] -hexadecane-manganese (I I), • ^^^^ AttiáiÉi acuo-chloro-10- (2-hydroxybenzyl) -4,10-dimethyl-1, 4,7,10-tetraazabicyclo [5.5.2] - tetradecano-manganese (ll), chloro-2- (2-hydroxybenzyl) -5-methyl-1, 5,8,12-tetraazabicyclo [6.6.2] hexadecane-manganese (II), 5-chloro-10- (2-hydroxybenzyl) -4-methyl-1,4, 7,10-tetraazabicyclo [5.5.2] tetradecane-manganese (II), chloro-5-methyl-12- (2-picolyl) -1,5,8,12-tetraazabicyclo [6.6.2] - hexadecane- manganese (ll), chloro-4-methyl-10- (2-picolyl) -1,4,7,10-tetraazabicyclo [5.5.2] tetra-10-decane-manganese chloride (ll), dichloro-5- ( 2-sulfate) dodecyl-12-methyl-1, 5,8,12-tetraazabicyclo [6.6.2] hexadecane -manganese (III), aqueous-chloro-5- (2-sulfate) dodecyl-12-methyl-1, 5,8,12-tetraazabicyclo [6.6.2] hexadecane-manganese (II), chloro-5- (3-sulfopropyl) -12-methyl-1, 5,8,12-tetraazabicyclo [6.6.2] hexadecane-manganese (ll), dichloro-5- (trimethylammoniopropyl) -dodecyl-12 chloride -methyl-1, 5,8,12-tetra-azabicyclo [6.6.2] hexadecane-manganese (III), dichloro-5,12-dimethyl-1, 4,7,10,13-pentaazabicyclo [8.5.2] heptadecane-20 manganese (ll), dichloro-M ^ O-dimethyl-1 .O.U ^ O-tetraazatriciclotd.e.? ldodosa-SjJ ^ .e-triene-manganese (ll), ^^^^ ^^ dichloro-4,11-dimethyl-1, 4,7,11-tetraazabicyclo [6.5.2] pentadecane-manganese (II). dichloro-5,12-dimethyl-1, 5,8,12-tetraazabicyclo [7.6.2] heptadecane-manganese (II). dichloro-5,13-dimethyl-1, 5,9,13-tetraazabicyclo [7J.2] heptadecane-manganese (II), dichloro-3,10-bis (butylcarboxy) -5,12-dimethyl-1, 5, 8,12-tetraazabicyclo [6.6.2] hexa-decane-manganese (ll), diacuo-3,10-dicarboxy-5,12-dimethyl-1, 5,8,12-tetraazabicyclo [6.6.2] hexadecane-manganese (ll), chloro-20-methyl-1, 9,20,24,25-pentaaza-tetracycle hexafluorophosphate [7JJ.13,7. 111'15] pentacosa-3,5J (24), 11, 13,15 (25) -hexane-manganese (ll), trifluoromethanesulfonate of trifluoromethanesulfone-20-methyl-1, 9,29,24,25-pentaaza-tetracycle [7JJ.13'7.111'15.] Pentacosa-3,5,7 (24), 11, 13,15 (25) -hexane-manganese (ll), trifluoromethanesulfonate of trifluoromethanesulfone-20-methyl-1, 9,20 , 24,25-pentaaza-tetracycle [7JJ.13 .111 '15.] Pentacosa-3,5,7 (24), 11, 13,15 (25) -hexane-iron (ll), chloro-5-hexafluorophosphate , 12,17-trimethyl-1, 5,8,12,17-pentaazabicyclo [6.6.5] -nonadecane-manganese (II), chloro hexafluorophosphate, 1-cistrimethyl-1YIO.Id-pentaazabiciclotd. dd] heptadecane-manganese (ll), chloro-d chloride, 12,17-trimethyl-1, d, 8,12,17-pentaazabicyclo [6.6.d] nonadecane -manganese (II) chloro-4 chloride, 10.1 d-trimethyl-1, 4,7,10,1 d-pentaazabicyclo [d.d.d] heptadecane-manganese (II). Practitioners can benefit additionally if certain terms receive additional definition and illustration. As used herein, "macrocyclic rings" are covalently linked rings, formed of four or more donor atoms (i.e., heteroatoms, such as nitrogen or oxygen) with carbon chains connecting them, and any macrocyclic ring, as defined here, it must contain a total of at least ten, preferably at least twelve, atoms in the macrocyclic 0 ring. An MRL herein may contain more than one ring of any kind per ligand; but at least one macrocyclic ring must be identifiable. Additionally, in the preferred embodiments, there are no directly connected heteroatoms. Preferred transition metal bleach catalysts are those in which the MRL comprises an organic macrocyclic ring (main ring) containing at least 10 to 20 atoms, preferably 12 to 18 atoms, more preferably approximately 12 to 20 atoms; very preferable, from 12 to 16 atoms. "Donor atoms", herein, are heteroatoms such as nitrogen, oxygen, phosphorus or sulfur, which when incorporated into a ligand, still have at least a single pair of electrons available to form a donor-receptor ligation with a metal. The preferred transition metal bleach catalysts are those in which the donor atoms in the organic macrocyclic ring of the bridged MRL crossed or transverse, are selected from the group consisting of N, O, S and P, preferably N and O, and most preferably, all N. It is also preferred that all MRLs with crossed or transverse bridges comprise 4 or donor atoms, all of which are coordinated to the same transition metal, d The most preferred transition metal bleach catalysts are those in which the MRL with transverse bridge comprises four nitrogen donors, all coordinated to the same transition metal , and those in which the MRL with transverse bridge, comprises five nitrogen atoms, all coordinated to the same transition metal. 0"Non-donor atoms" of the MRL, herein, are the carbon atoms most commonly, although various types of atoms may be included, especially in optional exocyclic substituents (such as the "dependent" portions, illustrated below) of the macrocyclics, which are not donor atoms, for the essential purposes of forming metal catalysts, nor are they carbon atoms. Thus, in the broadest sense, the term "non-donor atoms" may refer to any non-essential atom to form donor bonds with the catalyst metal. Examples of such atoms would include heteroatoms such as sulfur, when incorporated in a non-coordinating sulfonate group; 0 phosphorus, when incorporated in a portion of phosphonium salt; phosphorus, when it is incorporated in a P (V) oxide; a non-transition metal, or similar. In certain preferred embodiments, all non-donor atoms are carbon atoms.

The transition metal complexes of the MRLs can be prepared in any convenient manner. Two of these preparations are illustrated as follows: SYNTHESIS OF rMn (Bc¡clam) C l (a) .- Method I "Bciclam" (d, 12-dimethyl-1, d, 8,12-tetraaza-bicyclo [6.6.2] hexadecane) is prepared by a synthetic method described by G. R. Weisman and co-authors J. Amer. Chem. Soc, (1990), 112, 8604. 1.00 g (3.93 mmol) of Bciclam is dissolved in 3d ml of acetonitrile (distilled from CaH2). The solution is then brought to a vacuum of 1d mm, until acetonitrile begins to boil. The flask is then brought to atmospheric pressure with argon. The degassing process is repeated four times. Under argon, 1.12 g (3.93 mmol) of Mn (pyridine) 2Cl2, synthesized according to the literature procedure, is added from H.T. Witteveen and coauthors, J. Inorg. Nucí Chem., (1974) 36, 1d3d. The cloudy reaction solution begins to darken slowly. After stirring overnight at room temperature, the reaction solution becomes dark brown with fine suspended particles. The reaction solution is filtered with a 0.2 μm filter. The filtrate is light tan. This filtrate is evaporated to dryness, using a rotary evaporator. After drying overnight at O.Od mm at ambient temperature, 1.3 d g of solid product, matt white, is collected in 90% yield. Elemental analysis:% of Mn, 14.4d; % of C, 44.22; % of H, 7. 94; theoretical for [Mn (Bciclam) CI2]: MnC? 4H30N CI2: molecular weight: 380.26.

Found:% Mn, 14.98; % of C, 44.48; % of H, 7.86. The 0 ion spray mass spectroscopy: shows a peak greater than 3d4 mu, which corresponds to [Mn (Bciclam) (formate)] +. (b) .- Method II Dissolve 25.00 g (0.0984 mol) of freshly distilled Bciclam, which was prepared by the same method as above, in 900 ml of acetonitrile (distilled from CaH2). The solution is then placed under vacuum at 15 mm, until the acetonitrile begins to boil. The flask is then brought to atmospheric pressure with Ar. This degassing procedure is repeated four times. 11.25 g (0.0894 mol) of MnCl2 is added, under argon. Immediately darken the cloudy reaction solution. After stirring for four hours at reflux, the reaction solution becomes dark brown, with fine particles suspended. Filter the reaction solution to S & amp; aje £ tí &£ s¡? & through a 0.2 μm filter, under dry conditions. The filtrate is light tan. This filtrate is evaporated to dryness using a rotary evaporator. The resulting cinnamon solid is dried overnight at O.Od mm at room temperature. The solid is suspended in 100 ml of toluene and heated to reflux. The toluene is removed by decanting and the procedure is repeated with another 100 ml of toluene. The remaining toluene is removed using a rotary evaporator. After drying overnight at O.d mm, at room temperature, 31 Jd g of light blue solid product is collected. Yield: 93. d%. 0 Elemental analysis:% of Mn, 14.4d; % of C, 44.22; % of H, 7. 9d; % of N, 14.73; % of Cl, 18.6d; theoretical for [Mn (Bciclam) CI2], MnC H30 N4Cl2, molecular weight = 380.26. Found:% Mn, 14.60; % of C, 44.69; % of H, 7.99; % of N, 14.78; % of Cl, 18.90 (Karl Fischer water, 0.68%). The ion spray mass spectroscopy shows a main peak at d 3d4 mu, corresponding to [Mn (Bciclam) (formate) +. Bleaching agents other than oxygenated bleaching agents are also known in the art, and may be used herein. One type of non-oxygenated bleaching agent, of particular interest, includes photoactivated bleaching agents, such as zinc and / or aluminum phthalocyanines. These materials can be deposited on the substrate during the washing process. By irradiation with light, in the presence of oxygen, such as by hanging the garments on the outside to dry, in the light of day, the sulphonated zinc phthalocyanine is activated and, consequently, the substrate is bleached. The preferred zinc phthalocyanine and the photoactivated bleaching process are described in U.S. Patent No. 4,033,718. Typically, the detergent compositions will contain about 0.02d% to 1.2d% by weight of sulfonated zinc phthalocyanine.

THE SURGICAL SYSTEM The cleaning compositions according to the present invention generally comprise a surfactant system in which the surfactant can be selected from nonionic and / or anionic and / or cationic and / or ampholytic and / or hybrid surfactants and / / or semi-polar. Typically, the surfactant is present at a level of 0.1% to 60% by weight. The most preferred levels of incorporation are 1% to 3d% by weight, most preferably from 1% to 30% by weight of the cleaning compositions according to the invention. Preferably, the surfactant is formulated to be compatible with the enzyme components present in the composition. In liquid or gel compositions, the surfactant is most preferably formulated so as to promote, or at least not degrade, the stability of any enzyme present in the compositions.

T? AYes? .i.a? I ,.

Preferred surfactant systems for use in accordance with the present invention comprise, as a surfactant, one or more of the nonionic and / or anionic surfactants described herein, d. They are suitable for use as a nonionic surfactant of surfactant systems. of the present invention, the condensates of alkylphenols with polyethylene oxide, polypropylene oxide and polybutylene oxide; the condensates being preferred with polyethylene oxide. These compounds include the condensation products of alkylphenols that have an alkyl group containing about 6 to 14 carbon atoms, preferably about 8 to 14 carbon atoms, either in straight chain or branched chain configuration, with the alkylene oxide. In a preferred embodiment, the ethylene oxide is present in an amount equal to about 2 to 25 moles, more preferably, about 3 to 15 moles, of ethylene oxide per mole of alkylphenol. Commercially available nonionic surfactants, of this type, include: lgepal ™ CO-630, sold by GAF Corporation; and Triton ™ X-45, X-114, X-100 and X-102, all sold by Rohm & Haas Company. These surfactants are commonly known as alkylphenol alkoxylates (for example, alkylphenol ethoxylates). The condensation products of primary and secondary aliphatic alcohols with from about 1 to about 2 moles of ethylene oxide, are suitable for use as the non-ionic surfactant of the flfliíftlÉffÑff'tl nonionic surfactant systems of the present invention. The alkyl chain of the aliphatic alcohol may be straight or branched, primary or secondary, and generally contains about 8 to 22 carbon atoms. Preferred are the condensation products of alcohols having an alkyl group containing about 8 to 20 carbon atoms, more preferably about 10 to 18 carbon atoms, with about 2 to about 10 moles of ethylene oxide per mol of alcohol. About 2 to 7 moles of ethylene oxide and, most preferably, 2 to 1 moles of ethylene oxide per mole of alcohol are present in the aforesaid condensation products. Examples of commercially available nonionic surfactants of this type include: Tergitol ™ Ld-S-9 (the linear alcohol condensation product of 11 to 15 carbon atoms with 9 moles of ethylene oxide), Tergitol ™ 24-L-6 NMW (the condensation product of primary alcohol of 12 to 14 carbon atoms with 6 moles of ethylene oxide, and having a narrow molecular weight distribution), both sold by Union Carbide Corporation; NeodolMR 45-9 (the condensation product of linear alcohol of 14-15 carbon atoms with 9 moles of ethylene oxide), NeodolMR 23-3 (the linear alcohol condensation product of 12 to 13 carbon atoms with 3.0 moles ethylene oxide); NeodolMR 4d-7 (the condensation product of linear alcohol of 14 and 1d carbon atoms with 7 moles of ethylene oxide), NeodolMR 4d-d (the condensation product of linear alcohol of 14 to 15 carbon atoms, with d moles of ethylene oxide) sold by Shell Chemical Company; Kyro R EOB (the condensation product of alcohol of 13 to 1d carbon atoms with 9 moles of ethylene oxide), sold by The Procter & Gamble Company; and Genapol LA 030 or OdO (the condensation product of alcohol of 12 to 14 carbon atoms with 3 or d moles of d ethylene oxide), sold by Hoechst. The preferred scale of hydrophilic / lipophilic balance (EHL) in these products is from 8 to 11, and most preferably, from 8 to 10. Also useful as the nonionic surfactant of the surfactant systems of the present invention are the alkylpolysaccharides or those described in US Pat. US Patent 4, d6d, 647, to Llenado, issued January 21, 1986, having a hydrophobic group containing about 6 to 30 carbon atoms, preferably about 10 to 16 carbon atoms, and a polysaccharide , for example, a polyglycoside; a hydrophilic group containing about 1.3 to 10, preferably about 1.3 to 3, most preferably about 1.3 to 2J saccharide units. Any reducing saccharide containing 6 carbon atoms can be used, for example: the glucose, galactose and galactosyl moieties can substitute the glucosyl moieties (optionally, the hydrophobic moiety is fixed at positions 2, 3, 0 4, etc., thus giving a glucose or galactose, as opposed to a glucoside or galactoside). Intersaccharide ligatures may be, for example, between position one of the additional saccharide units and positions 2, 3, 4, and / or 6 of the preceding saccharide units. - ^^ * ata * »« * "« ft »*» s ^? * «i Preferred alkyl polyglycosides have the formula: R20 (CnH2nO) t (glycosyl) x d wherein R2 is selected from the group consisting of alkyl, alkylphenyl, hydroxyalkyl, hydroxyalkylphenyl, and mixtures thereof, wherein the alkyl groups contain about 10 to 18 carbon atoms, preferably about 12 to 14 carbon atoms; n is 2 or 3, preferably 2; t is from 0 to about 10, preferably 0; and x is 0 about 1.3 to 10, preferably about 1.3 to 3, most preferably about 1.3 to 2J. The glycosyl is preferably derived from glucose. To prepare these compounds the alcohol or alkylpolyethoxy alcohol is first formed, and then reacted with glucose, or with a glucose source, to form the glucoside d (fixation at position 1). The additional glycosyl units can then be fixed between their position 1 and positions 2, 3, 4 and / or 6 of the preceding glycosyl units, preferably, predominantly in position 2. The condensation products of ethylene oxide with 0 Hydrophobic base, formed by the condensation of propylene oxide with propylene glycol, are also suitable for use as additional nonionic surfactant systems of the present invention. The hydrophobic portion of these compounds will preferably have a molecular weight of about 1600 to 1800, and will exhibit insolubility in water. The addition of polyoxyethylene portions to this hydrophobic portion tends to increase the water solubility of the molecule as a whole, and the liquid nature of the product is retained to the point where the polyoxyethylene content is about d% of the total weight of the product. condensation product, which corresponds to condensation with up to about 40 moles of ethylene oxide. Examples of compounds of this type include some of the commercially available Plurafac ™ LF404 and Pluronic® surfactants sold by BASF. Also suitable for use as the nonionic surfactant of the nonionic surfactant system of the present invention are the condensation products of ethylene oxide with the product resulting from the reaction of propylene oxide and ethylene diamine. The hydrophobic portion of these products consists of the reaction product of ethylenediamine and an excess of propylene oxide, and in general has a molecular weight of approximately 2d00 to 3000. This hydrophobic portion is condensed with ethylene oxide to the extent that the product of condensation contains about 40% to 80% by weight of polyoxyethylene and has an approximate molecular weight of from d, 000 to 11,000. Examples of this type of non-ionic surfactant include some of the commercially available Tetronic ™ compounds sold by BASF.

It is preferred for use as a nonionic surfactant of the surfactant systems of the present invention the condensates with polyethylene oxide of alkylphenols, condensation products of primary and secondary aliphatic alcohols with approximately 2d moles of ethylene oxide, alkylpolysaccharides and mixtures thereof: alkylphenol ethoxylates of 8 to 14 carbon atoms, having 3 to 1 d ethoxy groups, and alcohol ethoxylates of 8 to 18 carbon atoms (preferably 10 carbon atoms on average) having from 2 to 10 ethoxy groups, and mixtures thereof The most preferred nonionic surfactants are the polyhydroxy fatty acid amide surfactants of the formula: R2-C-N - ZO R1 wherein R1 is H or R1 is a hydrocarbyl of 1 to 4 carbon atoms, 2-hydroxyethyl, 2-hydroxypropyl or a mixture thereof; R2 is hydrocarbyl of from d to 31 carbon atoms and Z is a polyhydroxyhydrocarbyl having a linear hydrocarbyl chain with at least three hydroxyls directly connected to the chain, or an alkoxylated derivative thereof. It is preferred that R1 is methyl, R2 is an alkyl of 11 to 1 d carbon atoms, straight, or an alkyl or alkenyl chain of 16 to 18 carbon atoms, such as cocoalkyl or mixtures thereof; and Z is derived from a reducing sugar, such as glucose, fructose, maltose, lactose, in a reductive amination reaction. - i? tKW ^ t ^ < & b ^ Se ^ B6Í ^ í ¡¡& ká Suitable anionic surfactants, to be used, are the alkylbenzenesulfonate, alkyl ester sulphonate surfactants, which include the linear esters of carboxylic acids of the alkyl ester. to 20 carbon atoms (that is, fatty acids) that are sulfonated with gaseous SO3, according to Journal of the American Oil Chemists Society, 52 (1975), pages 323-329. The right starting materials they would include the natural fatty substances that are derived from tallow, palm oil, etc. The preferred alkyl ester sulphonate surfactant, especially for laundry applications, comprises the alkyl ester sulphonate surfactants of the structural formula: O R 3 - CH - C - OR 4 | SO3M wherein R3 is a hydrocarbyl of 8 to 20 carbon atoms, preferably an alkyl, or a combination thereof; R4 is a hydrocarbyl of 1 to 6 carbon atoms, preferably an alkyl, or a combination thereof; and M is a cation that forms a water soluble salt with the alkyl ester sulfonate.

Salt-forming cations include metals, such as sodium, potassium and lithium; and substituted or unsubstituted ammonium cations, such as monoethanolamine, diethanolamine and triethanolamine. It is preferred that R3 is alkyl of 10 to 16 carbon atoms and R4 is methyl, ethyl or isopropyl. Especially preferred are methyl ester sulfonates, wherein R3 is alkyl of 10 to 16 carbon atoms. Other suitable anionic surfactants include the alkyl sulfate surfactants, which are water soluble salts or water soluble acids of the formula ROS03M, wherein R is preferably a hydrocarbyl of 10 to 24 carbon atoms, preferably a alkyl or hydroxyalkyl having an alkyl component of 10 to 20 carbon atoms, more preferably, an alkyl or hydroxyalkyl of 12 to 18 carbon atoms; and M is H or a cation, for example, an alkali metal cation (eg, sodium, potassium, lithium) or an ammonium or substituted ammonium (eg, methylammonium, dimethylammonium and trimethylammonium cations, and quaternary ammonium cations, such such as tetramethylammonium and dimethylpiperidinium cations and quaternary ammonium cations derived from alkylamines such as ethylamine, diethylamine, triethylamine and mixtures thereof, and the like). Alkyl chains d of 12 to 16 carbon atoms are typically preferred for lower wash temperatures (eg, less than about d0 ° C) and alkyl chains of 16 to 18 carbon atoms are preferred for higher wash temperatures ( for example, more than around d0 ° C). Other anionic surfactants, useful for detergent purposes, may also be included in the cleaning compositions or compositions of the present invention. These may include salts (including, for example, sodium, potassium, ammonium and substituted ammonium salts, such as the monoethanolamine, diethanolamine and triethanolamine salts) of O ^^^^ p ^ feMS ^^^ soap, primary or secondary alcansulfonates of 8 to 22 carbon atoms, olefinsulfonates of 8 to 24 carbon atoms, sulfonated polycarboxylic acids, prepared by sulfonation of the pyrolyzed product of alkali metal citrates- earth, for example, those described in the memory of British patent No. 1, 082,179; polyglycol ether alkyl sulfates of 8 to 24 carbon atoms (containing up to 10 moles of ethylene oxide); alkyl glycerol sulphonates, fatty acyl glycerol sulphonates, fatty oleyl glycerol sulfates, alkylphenol ether sulfates and ethylene oxide, paraffin sulfonates, alkyl phosphates, isethionates, or acyl isethionates; N-acyltaurates, alkylsuccinamates and sufosuccinates, monoesters of sulfosuccinates (especially saturated and unsaturated monoesters of 12 to 18 carbon atoms) and diesters of sulfosuccinates (especially saturated and unsaturated diesters of 6 to 12 carbon atoms); alkyl sarcocinates, alkylpolysaccharide d sulfates, such as alkylpolyglucoside sulfates (the non-sulphonated nonionic compounds described below); the branched primary alkyl sulfates, and the alkyl polyethoxycarboxylates, such as those having the formula RO (CH2CH20) k-CH2COO-M +; wherein R is an alkyl of 8 to 22 carbon atoms; k is an integer from 1 to 10 and M is a 0 cation that forms a soluble salt. Also suitable are resin acids and hydrogenated resin acids, such as rosin, hydrogenated rosin and resin acids and hydrogenated resin acids present in, or derived from, second distillation oil.

Other examples are described in Surface Active Agents and Detergents (volumes I and II, by Schwartz, Perry and Berch). A variety of such surfactants are generally included in US Patent 3,929,678, issued December 30, 197d to Laughlin and co-inventors, in column 23, row 68, to column 29, row 23 (incorporated herein by this reference). When included herein, the laundry detergent compositions of the present invention typically comprise about 1% to 40%, preferably about 3% to 20% by weight. weight of said anionic surfactants. The highly preferred anionic surfactants include the alkoxylated alkyl sulfate surfactants herein, which are water soluble salts or water soluble acids having the formula RO (A) mS03M, wherein R is an alkyl group or 1d hydroxyalkyl of 10 to 24 carbon atoms, having an alkyl component of 10 to 24 carbon atoms, preferably an alkyl or hydroxyalkyl of 12 to 20 carbon atoms, more preferably, alkyl or hydroxyalkyl of 12 to 18 carbon atoms; A is an ethoxy or propoxy unit; m is greater than zero, typically between about O.d and about 6, more preferable, between about O.d and about 3; and M is H or a cation which may be, for example, a metal cation (eg, sodium, potassium, lithium, calcium, magnesium, etc.), an ammonium cation or a substituted ammonium cation. Ethoxylated alkyl sulfates, as well as propoxylated alkyl sulphates are flBMteaa. contemplated here. Specific examples of substituted ammonium cations include cations: methyl-, dimethyl-, trimethyl-ammonium and quaternary ammonium cations, such as tetramethylammonium and dimethylpyridinium cations, and alkylamines derivatives, such as ethylamine, diethylamine, triethylamine, mixtures thereof and the like. Examples of surfactants are: polyethoxylate (1.0) alkyl sulphate of 12 to 18 carbon atoms (C-? 2-18E (1.0) M), polyethoxylate sulfate (2.2d) of alkyl of 12 to 18 carbon atoms carbon (C? 2 -? 8E (2.2d) M); polyethoxylate sulfate (3.0) of alkyl of 12 to 18 carbon atoms (C-? 2- 18E (3.0) M); and polyethoxylate sulfate (4.0) of alkyl of 12 to 18 carbon atoms (C-? 2-i8E (4.0) M), where M is conveniently selected from sodium and potassium. The detergent compositions of the present invention may also contain ampholytic, zwitterionic and semi-polar surfactants, as well as other nonionic and / or anionic surfactants, different from those already described herein. The cationic detergent surfactants suitable for use in the cleaning compositions of the present invention are those having a long chain hydrocarbyl group. Examples of cationic surfactants of this type include ammonium surfactants, such as alkyltrimethylammonium halides, and surfactants having the formula: [R ^ OR-3) and] [R ORJ) and] 2R 5 ° NM ++ XV- where R 2 is an alkyl or alkylbenzyl group having about 8 to 18 carbon atoms in the alkyl chain; each R3 is selected from the group consisting of -CH2CH2-, -CH2CH (CH3) -, -CH2CH (CH2OH) -, -CH2CH2CH2-, and mixtures thereof; each R4 is selected from the group consisting of alkyl of 1 to 4 carbon atoms, hydroxyalkyl of 1 to 4 carbon atoms, benzyl ring structures, formed by joining the two groups R4; -CH2CHOH-CHOHCOR6CHOHCH2OH, where R6 is any hexose or hexose polymer having a molecular weight of less than about 1000; and hydrogen, when y is not 0; R5 is equal to R4 or is an alkyl chain in which the total number of carbon atoms of R2 plus R5 is not greater than about 18; each "y" is from 0 to around 10 and the sum of the values "y" is from 0 to about 1d; and X is any compatible anion. The quaternary ammonium surfactant, suitable for the present invention, has the formula (I): Formula I wherein Ri is an alkyl of short chain length; or an alkylamidoalkyl of 6 to 10 carbon atoms of the formula (II): Formula . ^^ ¿T ^ TflflflrtMaflattdft ^ aMfcÉidfciii "y" is 2-4, preferably 3; whereby R2 is preferably H or an alkyl of 1 to 3 carbon atoms; whereby R3, R and R5 are the same or different and can be a short chain alkyl (of 1 to 3 carbon atoms) or alkoxylated alkyl of the formula whereby X "is an opposite ion, preferably a halide, for example, a chloride or methylisulfate.

Formula ilt R6 is 1 to 4 carbon atoms and z is 1 or 2. Preferred quaternary ammonium surfactants are those defined in formula I, wherein: Ri is 8 carbon atoms, 10 carbon atoms or mixtures of them; x = 0; R3, R4 = CH3 and R5 = CH2CH2OH. The most preferred cationic surfactants are the water-soluble quaternary ammonium compounds, useful in the composition herein, having the formula: R1R2R3R4N + X "(i) in which Ri is alkyl of 8 to 16 carbon atoms, each of R2, R3 and R is independently alkyl of 1 to 4 carbon atoms, hydroxyalkyl of 1 to 4 carbon atoms, benzyl and - (C2H40)? H, where H has a value of 2 ad, and X is an anion.Not more than one of R2, R3 or R4 must be benzyl.d The preferred length of the alkyl chain for Ri is 12 a 1 d carbon atoms, in particular when the alkyl group is a mixture of chain lengths derived from coconut fat or palm kernel is synthetically derived from olefin, constituted or by synthesis of OXO alcohols. The preferred groups for R2R3 and R are methyl and hydroxyethyl groups and the X anion can be selected from halide, methosulfate, acetate and phosphate ions. Examples of suitable quaternary ammonium compounds of the formulas (i) for use herein are: cocotrimethylammonium chloride or bromide, cocomethyldihydroxyethylammonium chloride or bromide, decyltriethylammonium bromide, decildimethylhydroxyethylammonium chloride or bromide, chloride or bromide. dimethylhydroxyethylammonium of 12 to 1 carbon atoms, cocodimethylhydroxyethylammonium bromide chloride, myristyltrimethylammonium methylisulfate, lauryl dimethylbenzylammonium bromide, lauryldimethyl bromide (ethenoxy) 4ammonium chloride, choline ester (compounds of the formula i) in which Ri is dialkylimidazolines [compounds of the formula (i)], d Other cationic surfactants, useful herein are also described in U.S. Patent 4,228,044, Cambre, issued October 14, 1980, and in European Patent Application EP 000,224 Fabric softening components, cationic, typical, 0 include the water softening active ingredients of quaternary ammonium fabrics, or their corresponding amine precursor; the most commonly used being long-chain dialkyl ammonium chloride or methylisulfate. Preferred cationic softeners include the following d: 1) ditallowdimethylammonium chloride (DTDMAC); 2) hydrogenated dichloromethane-dimethylammonium chloride, 3) hydrogenated dichloromethane-dimethylammonium methylisulfate 4) distearyldimethylammonium chloride, 0 d) dioleyl-dimethylammonium chloride 6) dipalmityl-hydroxyethyl-methylammonium chloride, 7) stearylbenzyldimethylammonium chloride, 8) chloride sebotrimethylammonium 9) hydrogenated tallow-trimethylammonium chloride, 10) alkyl chloride of 12 to 14 carbon atoms-hydroxyethyl-dimethylammonium 11) alkyl chloride of 12-18 carbon atoms-dihydroxyethyldimethylammonium, 12) di (stearoyloxyethyl) chloride dimethylammonium (DSOEDMAC), 13) di (tallowoxyethyl) dimethylammonium chloride, 14) diseboimidazolinium methylisulfate, 1d) 1- (2-tallowamemidoethyl) -2-tallowyl imidazolinium methylisulfate. The biodegradable quaternary ammonium compounds have been presented as an alternative for long-chain ammonium dialkyl chlorides and diallyl methylsulfates used transitions. Said quaternary ammonium compounds contain long chain alkyl (en) yl groups, interrupted by functional groups, such as carboxy groups. Such materials and fabric softening compositions containing them are described in numerous publications, such as EP-A-0,040, d62 and EP-A-0,239,910. The quaternary ammonium compounds and the amine precursors herein have the formula (I) or the formula (II) which follow: (I) (H) where Q is selected from -O-C (O) -, -O-C (0) -0-, -NR4-C (0) -, -C (0) -NR4-; R1 is (CH2) n-Q-T2 or T3; R2 is (CH2) m-Q-T4 or T5 OR R3; d R3 is alkyl of 1 to 4 carbon atoms or hydroxyalkyl of 1 to 4 carbon atoms, or H; R 4 is H or alkyl of 1 to 4 carbon atoms or hydroxyalkyl of 1 to 4 carbon atoms; T1, R2, T3, T4 and T5 are independently alkyl or alkenyl of 11 to 22 0 carbon atoms; n and m are integers from 1 to 4; and X "is an anion compatible with the softener.Non-limiting examples of anions compatible with the softener include chloride or methylisulfate d The alkyl or alkenyl chains of T1, T2, T3, T4, T5 must contain at least 11 carbon atoms, preferably at least 16 carbon atoms The chain can be straight or branched Sebum is a convenient and inexpensive source of long chain alkyl and alkenyl material Compounds where T1, T2, T3, T4, 0 T5 represent the mixture of long chain materials for sebum, they are particularly preferred.

Specific examples of quaternary ammonium compounds, suitable for use in aqueous fabric softener compositions, • present, include: 1) N, N-di () tallowyl-oxy-ethyl) -N, N-dimethylammonium chloride, d 2) N, N-di (tallowyloxyethyl) -N- methylisulfate methyl, N- (2-hydroxyethyl) ammonium, 3) N, N-di (2-tallowyl-oxy-2-oxo-ethyl) -N, N-dimethylammonium chloride, 4) N, N-di (2- tallowyl-oxy-ethylcarbonyl-oxy-ethyl) -N, N-dimethylammonium, 5) N- (2-tallowyl-oxy-2-ethyl) -N- (2-tallowyl-oxy-2-oxo-ethyl) chloride) -N, N-dimethylammonium, 10 6) N, N, N-tri (tallowyl-oxy-ethyl) -N-methylammonium chloride, 7) N- (2-tallowyloxy-2-oxo-ethyl) chloride -N- (tallowyl-N, N-dimethylammonium, and 8) 1,2-diisoboxy-3-trimethylammoniopropane chloride; and mixtures of any of the above materials. When included herein, the detergent compositions 1d of the present invention typically comprise from 0.2% to 2d%, preferably from about 1% to 8% by weight of said cationic surfactants. The ampholytic surfactants are also suitable for use in the detergent compositions of the present invention. These surfactants can be broadly described as aliphatic derivatives of secondary or tertiary amines, or aliphatic derivatives of heterocyclic secondary and tertiary amines, in which the aliphatic radical can be straight chain or branched chain. One of the aliphatic substituents x ^ - * contains at least about 8 carbon atoms, typically about 8 to 18 carbon atoms, and at least one contains an anionic water-solubilizing group, eg, carboxy, sulfonate, sulfate. See U.S. Patent No. 3,929,678, Laughlin and co-inventors, issued December 30, 1976, in column 19, lines 18-36, for examples of ampholytic surfactants. When included herein, the detergent compositions of the present invention typically comprise from 0.2% to about 1d%, preferably from about 1% to 10% by weight of said ampholytic agents or surfactants. Hybrid ion surfactants are also suitable for use in detergent compositions. These surfactants can be broadly described as derivatives of secondary and tertiary amines, derivatives of heterocyclic secondary and tertiary amines, or d derived from quaternary ammonium, quaternary phosphonium or tertiary sulfonium compounds. See U.S. Patent No. 3,929,678, Laughlin and co-inventors, issued December 30, 1976, in column 19, line 38, to column 22, line 48, for examples of hybrid surfactants. When included herein, the cleaning compositions of the present invention typically comprise from 0.2% to about 1d%, preferably from about 1% to about 10% by weight of said hybrid surfactants.

The nonionic, semi-polar surfactants are a special category of nonionic surfactants which include water-soluble amine oxides containing an alkyl portion of from about 10 to about 18 carbon atoms and two portions selected from the group consisting of alkyl groups and hydroxyalkyl groups containing about 1 to 3 carbon atoms; water-soluble phosphine oxides, containing an alkyl portion of from about 10 to about 18 carbon atoms, and two portions selected from the group consisting of alkyl groups and hydroxyalkyl groups containing about 1 to 3 carbon atoms; and water-soluble sulfoxides containing an alkyl portion of from about 10 to about 18 carbon atoms, and a portion selected from the group consisting of alkyl and hydroxyalkyl portions of about 1 to 3 carbon atoms. The non-ionic, semi-polar detergent surfactants include the amine oxide surfactants having the formula: O 3 4 T 5 R 3 (OR 4) x N (R 5) 2 wherein R3 is an alkyl, hydroxyalkyl or alkylphenyl group, or mixtures thereof, containing about 8 to 22 carbon atoms; R4 is an alkylene or hydroxyalkylene group containing about 2 to 3 carbon atoms, or mixtures thereof; x is from 0 to about 3; and each R 5 is an alkyl or hydroxyalkyl group containing about 1 to 3 carbon atoms, or a polyethylene oxide group containing about 1 to 3 ethylene oxide groups. The R5 groups may be attached to each other, for example, by means of an oxygen or nitrogen atom, to form an annular structure. These amine oxide surfactants, in particular, include the alkyldimethylamine oxides, of 10 to 18 carbon atoms in the alkyl, and the alkoxyethyldihydroxyethylamine oxides, of 8 to 12 carbon atoms in the alkoxy. When included herein, the detergent compositions of the present invention typically comprise from 0.2% to about 15%, preferably about 1% to 10% by weight of said semi-polar nonionic surfactants. The cleaning composition of the present invention may additionally comprise a surfactant coagent selected from the group of primary or tertiary amines. Primary amines suitable for use herein include the amines according to the formula R- | NH2) wherein Ri is an alkyl chain of 6 to 12 carbon atoms, preferably 6 to 10 carbon atoms, or R4X (CH2) n; X is -O-, -C (O) NH- or -NH-; R 4 is an alkyl chain of 6 to 12 carbon atoms; n is between 1 and 5, preferably 3. The alkyl chains Ri can be straight or branched and can be interrupted with up to 12, preferably less than d, ethylene oxide moieties. Preferred amines according to the formula given here above are the n-alkylamines. Amines suitable for use herein may be selected from 1-hexylamine, 1-octylamine, 1-decylamine and laurylamine. Other preferred primary amines include: oxypropylamine of 8 to 10 carbon atoms, octyloxypropylamine, 2-ethylhexyloxypropylamine, laurylamidopropylamine and amidopropylamine. d Tertiary amines suitable for use herein include tertiary amines having the formula R.sub.2 R.sub.3 N, where Ri and R.sub.2 are alkyl chains of 1 to 8 carbon atoms or R5 10 - (CH2 - CH - 0) x H R3 is an alkyl chain of 6 to 12 carbon atoms, preferably of 6 to 10 carbon atoms, or R3 is R4X (CH2) n, whereby X is -O-, -C (O) NH-, or -NH-; R4 is from 4 to 12 carbon atoms; n is between 1 and d, of 16 preferably between 2 and 3. R5 is H alkyl of 1 or 2 carbon atoms and x is between 1 and 6; R3 and R can be linear or branched; the alkyl chains of R3 may be interrupted with up to 12, preferably less than d, ethylene oxide portions. The tertiary amines are R? R2R3N, where Ri is an alkyl chain of 6 to 12 carbon atoms, R2 and R3 are alkyl of 1 to 3 carbon atoms, or R5 - (CH2 - CH - 0) x H where R5 is H or CH3 and x = 12. Amidoamines of the formula are also preferred: OR I I R - C - NH - (CH2) n - N - (R2) 2 Wherein Ri is alkyl of 6 to 12 carbon atoms; n is 2-4; preferably, n is 3; R2 and R3 are from 1 to 4 carbon atoms. Highly preferred amines of the present invention include: 1-octylamine, 1-hexylamine, 1-decylamine, 1-dodecylamine, oxy-propylamine of 8 to 10 carbon atoms, N-coclo-1,3-diam-niopropane, cocoalkyldimethylamine , 1-lauryldimethylamine, laurylbis (hydroxyethyl) amine, coco-bis (hydroxyethyl) amine, lauryl-amine propoxylated with 2 moles, propoxylated octylamine with 2 moles, laurylamidopropyldimethylamine, amidopropyldimethylamine of 8 to 10 carbon atoms, and amidopropyldimethylamine of 10 carbon atoms. The most preferred amines of all for use in the compositions herein are: 1-hexylamine, 1-octylamine, 1-decylamine, 1-dodecylamine. Especially convenient: n-dodecyldimethylamine and ethoxylated bishydroxyethylcocoalkylamine and oleylamine 7 times; laurylamidopropylamine and cocoamidopropylamine. a- ^ a ~ • * - ~ - * - - *** fc * - * - BENEFITS OF COLOR CARE AND CARE OF THE FABRICS You can also include technologies that provide a type of color care benefit. The examples of these technologies are the metallo catalysts for color maintenance. Said metallo catalysts are described in the pending European patent application No. 92870181.2. Dye fixing agents, polyolefin dispersion for anti-wrinkle effects and improved water absorbency, perfume and amino-functional polymer for color care treatment, and perfume substantivity, are additional examples of technologies for care of color / fabric care, and are described in co-pending patent application No. 96870140.9, filed on November 7, 1996. Fabric softening agents may also be incorporated in the cleaning compositions according to the present invention. These agents may be of inorganic or organic type. The inorganic softening agents are exemplified by the smectite clays described in GB-A-1 400 898 and in US 5,019,292. Organic fabric softening agents include water-insoluble tertiary amines, which are described in GB-A1 514 276 and in EP-B0 011 340, and their combination with monoquaternary ammonium salts of 12 to 14 carbon atoms is described in US Pat. EPB026 527 and EP-B-0 026528; and the long double-chain amides are described in EP-B-0 242 919. Other organic ingredients useful in fabric softener systems include the oxide materials of «^ - .t.t« ^. A .. ,, at «. . , High molecular weight polyethylene, which are described in EP-A-0 299 676 and 0 313 146. Smectite clay levels are usually in the range of 2% to 20%, more preferably, 5% to 16% by weight, with the material added as a dry, mixed component to the remainder of the formulation. Organic fabric softening agents, such as water-insoluble tertiary amines or long double-chain amide materials, are incorporated at levels of 0.6% to 6% by weight, usually from 1% to 3% by weight, while High molecular weight polyethylene oxide materials and water soluble cationic materials are added at levels of 0.1% to 2%, usually from 0.15% to 1.5% by weight. These materials are usually added to the spray-dried portion of the composition, although, in some cases, it may be more convenient to add them as a mixed, dry particulate material, or spray them as a molten liquid over other solid components of the composition.

THE DETERGENT IMPROVEMENT SYSTEM The compositions according to the present invention may additionally comprise a builder system.

Any conventional builder system is suitable for use herein, including aluminosilicate materials, silicates, polycarboxylates, alkyl- or alkenyl-succinic acid and fatty acids; materials Jg ^ jaMKafe ^^^ ßj '^ as ethylenediamine tetraacetate, diethylenetriamine pentamethylene-acetate, metal ion sequestrants, such as aminopolyphosphonates, particularly ethylenediamine-tetramethylene-phosphonic acid and diethylenetriamine-pentamethylene-phosphonic acid. Phosphate builders can also be used herein. The detergency builders may be an inorganic ion exchange material, commonly an hydrous, inorganic aluminosilicate material, more in particular, a hydrated synthetic zeolite, such as a hydrated zeolite A, X, B, HS or MAP. Another suitable inorganic builder material is a layered silicate, for example, SKS-6 (Hoechst). SKS-6 is a crystalline layered silicate consisting of sodium silicate (Na2Si2O5). Suitable polycarboxylates containing a carboxy group include: lactic acid, glycolic acid and its ether derivatives, which are described in Belgian patents No. 831, 368, 821, 369 and 821, 370. Polycarboxylates containing two carboxy groups include the water-soluble salts of succinic acid, malonic acid (ethylenedioxy) diacetic acid, maleic acid, diglycolic acid, tartaric acid, tartronic acid and fumaric acid, as well as the ether carboxylates described in the publications German 2,446,686 and 2,446,687, and in U.S. Patent No. 3,935,267, and the sulfinyl carboxylates described in Belgian Patent No. 840,623. Polycarboxylates containing three carboxy groups include, in particular, the water-soluble citrates, aconitrates and citraconates, as well as the succinate derivatives, such as the carboxymethyloxysuccinates described in British Patent No. 1, 379,241; the lactoxysuccinates described in the Netherlands application 7205873; and oxypolycarboxylate materials, such as the tricarboxylates of 2-oxa-1,1,3-propane, described in British Patent No. 1, 387,447. Polycarboxylates containing four carboxy groups include the oxydisuccinates described in British Patent No. 1, 261, 829, 1,1, 2,2-ethane tetracarboxylates, 1,1-tetracarboxylate, 3,3-propane and tetracarboxylate 1 , 1, 2,3-propane. Polycarboxylates containing sulfo substituents include the sulfosuccinate derivatives described in British Patents No. 1, 398,421 and 1, 398,422, and in US Patent No. 3,936,448, and the sulfonated pyrolysed citrates described in British Patent No. 1,082,179. , while polycarboxylates containing phosphon substituents are described in British Patent No. 1, 439,000. Alicyclic and heterocyclic polycarboxylates include cis, cis, cyclopentane cis-tetracarboxylates, cyclopentadienide pentacarboxylates, cis -cis.cis-tetracarboxylates of 2,3,4,5-tetrahydrofuran, 2,5-tetrahydrofuran cis-discarboxylates, tetracarboxylates of 2,2,5,6-tetrahydrofuran, hexacarboxylates of 1, 2,3,4, 5,6-hexane and carboxymethyl derivatives of polyhydric alcohols, such as sorbitol, mannitol and xylitol. Aromatic polycarboxylates include: mellitic acid, pyromellitic acid and the phthalic acid derivatives described in British Patent No. 1, 425, 433.

• SMAafeaA - ^ i Of the above, the preferred polycarboxylates are hydroxycarboxylates containing up to three carboxy groups per molecule, plus • in particular, citrates. Preferred builder systems for use in the compositions herein include a mixture of water-insoluble aluminosilicate builder, such as zeolite A or a layered silicate (SKS-6) and a soluble carboxylate chelating agent. in water, like citric acid. Preferred builder systems include a mixture of a water-insoluble aluminosilicate builder, such as zeolite A, and a water-soluble carboxylate chelating agent, such as citric acid. Preferred builder systems for use in the liquid detergent compositions of the present invention are soaps and polycarboxylates. Other builder materials that can form part of the builder system for use in granular compositions include inorganic materials, such as carbonates, bicarbonates, alkali metal silicates, and organic materials such as organic phosphonates, aminopolyalkylene phosphonates and amino polycarboxylates. Other suitable water-soluble organic salts are homopolymeric or copolymeric acids or their salts, in which the polycarboxylic acid comprises at least two separate carboxyl radicals each other by no more than two carbon atoms. Polymers of this type are described in GB-A-1, 596,756. Examples of such salts are polyacrylates with molecular weight of 2,000 to 5,000 and their copolymers with maleic anhydride; said copolymers having a molecular weight of 20,000 to 70,000, especially about 40,000. The detergent builder salts are usually included in amounts of 5% to 80% by weight of the composition, preferably 10% to 70% and, most commonly, 30% to 60% by weight.

THE CHELATING AGENTS The detergent compositions herein may also optionally contain one or more iron and / or manganese chelating agents. Such chelating agents may be selected from the group consisting of aminocarboxylates, aminophosphonates, polyfunctionally substituted aromatic chelating agents and mixtures thereof; everything as defined here below. Without attempting to adhere to any theory, it is believed that the benefit of these materials is due, in part, to their exceptional ability to remove iron and manganese from washing solutions, through the formation of soluble chelates. Aminocarboxylates useful as optional chelating agents include: ethylenediaminetetraacetates, N-hydroxyethylenediaminetriacetates, nitrilotriacetates, ethylenediaminetetrapropionates, triethylenetetramine- hexaacetates, diethylenetriaminepentaacetates and ethanoldiglicins; its alkali metal, ammonium and substituted ammonium salts, and mixtures thereof. The aminophosphonates are also suitable for use as chelating agents in the compositions of the invention, when at least low levels of total phosphorus are allowed in the detergent compositions, and include ethylenediaminetetracis (methylenephosphonates), such as DEQUEST. It is preferred that these aminophosphonates contain no alkyl or alkenyl groups with more than about 6 carbon atoms. The polyfunctionally substituted aromatic chelating agents are also useful in the compositions herein. See US Patent 3,812,044, issued May 21, 1974, to Connor and co-inventors. Preferred compounds of this type, in acid form, are the dihydroxydisulfobenzenes, such as 1,2-dihydroxy-3,5-disulfobenzene. A preferred biodegradable chelator for use herein is ethylenediamine disuccinate ("EDDS"), especially the [S, S] isomer, which is described in U.S. Patent 4,704,233, November 3, 1987 to Hartman and Perkins. The compositions herein may also contain salts of water-soluble glycolindiacetic acid (MGDA) (or the acid form) as a chelator or co-builder, useful, for example, with insoluble builders, such as zeolites, stratified silicates and the like.

If used, these chelating agents will generally constitute from about 0.1% to 15% by weight of the detergent compositions herein. It is more preferred that, if used, the chelating agents constitute approximately 0.1% to 3.0% by weight of such compositions.

THE FOAM SUPPRESSOR Another optional ingredient is a foam suppressant, exemplified by silicones, and silica-silicone blends. Silicones can generally be represented by alkylated polysiloxane materials, while silica is normally used in finely divided forms, exemplified by silica aerogels and xerogels, and hydrophobic silicas of various types. These materials can be incorporated as particles, in which the foam suppressor is advantageously advantageously incorporated in a carrier impermeable to the detergent, which is not substantially surfactant., soluble in water or dispersible in water. Alternatively, the foam suppressant can be dissolved or dispersed in a liquid carrier and applied by spraying on one or more of the other components. A preferred silicone foam controlling agent is described in Bartollota and co-inventors, US Pat. No. 3,933,672. Other particularly useful foam suppressors are self-emulsifying silicone foam suppressors, described in the German patent application DTOS 2 646 126, published April 28, 1977. An example of such a compound is DC-644, commercially available from Dow Corning, which is a siloxane-glycol copolymer. Especially preferred foam controlling agents are the suds suppressor systems comprising a mixture of silicone oils and 2-alkyl alkanols. Suitable 2-alkyl-alkanols are: 2-butyloctanol, which can be obtained commercially under the brand name Isofol 12 R. This foam suppressor system is described in the co-pending European patent application No. 92870174J, filed on 10 November 1992. Especially preferred silicone foam controlling agents are described in co-pending European Patent Application No. 92291649.8 Said compositions may comprise a silicone / silica blend, in combination with non-porous smoked silica, such as Aerosil®. The foam suppressors described above are usually employed at levels from 0.001% to 2% by weight of the composition, preferably from 0.01% to 1% by weight.

OTHERS Other components used in detergent compositions can be used, such as soil suspending agents, agents I ^ sggag? | ^ | afe¿ ^ ». dirt release agents, optical brighteners, abrasives, bactericides, discoloration inhibitors, coloring agents and / or encapsulated or non-encapsulated perfumes. Particularly suitable encapsulating materials are water-soluble capsules consisting of a matrix of polysaccharide compounds and polyhydroxy compounds, such as that described in British Patent 1, 464,616. Other suitable water-soluble encapsulating materials comprise the dextrins derived from non-gelatinized starch acid / substituted dicarboxylic acid esters, as described in US 3,456,838. These acid-ester dextrins are preferably prepared from starches such as waxy maize starch, waxy sorghum, sago, tapioca and potato starch. Suitable examples of encapsulating materials include N-Lok, manufactured by National Starch. The N-Lok encapsulating material consists of a modified corn starch and glucose. The starch is modified by adding monofunctional substituted groups, such as octenylsuccinic acid anhydride. The anti-redeposition and dirt suspending agents, suitable herein, include cellulose derivatives, such as methylcellulose, carboxymethylcellulose and hydroxyethylcellulose; and the homopolymeric or copolymeric polycarboxylic acids, or their salts. Polymers of this type include polyacrylates and maleic anhydride-acrylic acid copolymers, previously mentioned as builders, as well as copolymers of maleic anhydride with ethylene, methyl vinyl ether or methacrylic acid; the maleic anhydride constituting at least 20 mole percent of the copolymer. These materials are normally used at approximate levels of 0.5% to 10% by weight, more preferably, from 0.75% to 8%, most preferably, from 1% to 6% by weight of the composition. Preferred optical brighteners are anionic in nature; and examples are: 4,4'-bis- (2-diethanolamino-4-anilino-s-triazin-6-ylamino) -stilben-2,2'-disulfonate of disodium, 4,4'-bis- ( 2-morpholino-4-anilino-s-triazin-6-ylamino-stilbene-2,2'-disulfonate, 4,4'-bis- (2,4-dianilino-s-triazin-6-ylamino) disodium stilben-2,2'-disulfonate, 4 ', 4"-bis (2,4-dianilino-s-triazin-6-ylamino) stilbene-2-sulfonate monosodium, 4,4'-bis- ( 2-anilino-4- (N-methyl-N-2-hydroxyethylamino) -s-triazin-6-amyl) -neben-2,2'-disulfonate of disodium, 4,4'-bis (2 -anilino-4- (1-methyl-2-hydroxyethylamino) -s-triazin-6-ylamino) stilbene-2,2'-disulfonate, disodium, 2- (stilbe-4"- (naphtho-1 ', 2 ', 4,5) -1, 2,3-triazole-2"sodium sulfonate and 4,4'-bis (2-sulphotryl) biphenyl The highly preferred brighteners are the specific brighteners of the European patent application No 95201943.8 Other useful polymeric materials are polyethylene glycols, in particular those having molecular weights of 1,000 to 10,000, more in particular, 2,000 to 8,000. 0 and, very preferable, around 4,000. These are used at levels of 0.20% to 5%, more preferably, from 0.2d% to 2.6% by weight. These polymers and the above-mentioned homopolymer or copolymeric polycarboxylate salts are valuable for improving the maintenance of whiteness, the deposition of ash in the fabric and the cleaning performance in clay, proteinaceous and oxidizable soils, in the presence of transition metal impurities. The soil release agents useful in the compositions of the present invention are conventionally copolymers or terpolymers of terephthalic acid with ethylene glycol and / or propylene glycol units in various arrangements. Examples of such polymers are those described in United States patents assigned to the same successor as the present one, No. 4 116 885 and 4 711 730, and in published European patent application No. 0 272 033. A preferred polymer in particular, according to EP-A-0 272 033, it has the formula: (CH3 (PEG) 43) 075 (POH) or 5 [T-PO) 2 8 (T-PEG) 04] T (PO-H) 025 ((PEG) 43CH3) or 75 where PEG is - (OC2H4) O-, PO is (OC3H6O) and T is (pcOC6H4CO). Modified polyesters are also very useful as random copolymers of dimethyl terephthalate, dimethyl sulfoisophthalate, ethylene glycol and 1,2-propanediol; the end groups consisting primarily of sulfobenzoate and secondarily of monoesters of ethylene glycol and / or propanediol. The goal is to obtain a polymer capped at both ends by sulfobenzoate groups, "primarily" in the present context, most of the copolymers herein will be capped at the end by sulfobenzoate groups. However, some copolymers will be less than fully crowned and, accordingly, their end groups may consist of monoester of ethylene glycol and / or propane-1,2-diol, which consist "secondarily" of said species. The polyesters selected herein contain about 46% by weight of dimethylterephthalic acid, about 16% by weight of propane-1,2-diol, about 10% by weight of ethylene glycol, about 13% by weight of dimethyl sulfobenzoic acid and about 15% by weight of sulfoisophthalic acid, and have a molecular weight of approximately 3,000. The polyesters and their method of preparation are described in detail in EPA 311 342. It is well known in the art that free chlorine in tap water rapidly deactivates the enzymes that are included in the detergent compositions. Accordingly, the use of a chlorine scavenger, such as perborate, ammonium sulfate, sodium sulfite or polyethyleneimine, at a level greater than 0.1% by weight of the total composition, in the formulas, will provide improved stability of the detergent enzymes during washing. Compositions comprising the chlorine scrubber are described in European patent application 92870018.6, filed on January 31, 1992. Alkoxylated polycarboxylates, such as those prepared from polyacrylates, are useful herein to give the additional elimination operation of fat. These materials are described in WO 91/08281 and in PCT 90/01815, on page 4 et seq., Incorporated herein by this reference. Chemically, these materials comprise polyacrylates having an ethoxy side chain for every 7 to 8 acrylate units. The side chains have the formula - (CH2CH20) m (CH2) nCH3, where m is 2-3 and n is 6- 12. The side chains are linked with ester to the polyacrylate "backbone", to provide a polymer structure of the type "hair comb". The molecular weight can vary, but typically it is within the approximate range of 2,000 to 50,000. Said alkoxylated polycarboxylates may constitute from about 0.05% to 10% by weight of the composition herein.

THE DISPERSANTS The cleaning compositions of the present invention may also contain dispersants. Suitable organic water-soluble salts are the homopolymeric and copolymeric acids or their salts, where the polycarboxylic acid comprises at least two carboxyl radicals separated from each other by not more than two carbon atoms. Polymers of this type are described in GB-A-1, 596,756. Examples of such salts are polyacrylates of molecular weight 2,000 to 5,000 and their copolymers with maleic anhydride; said copolymers having a molecular weight of 1,000 to 100,000. Especially, acrylate-methacrylate copolymer, such as 480N, having a molecular weight of 4,000, at a level of 0.5 to 20% by weight of the composition can be added to the cleaning compositions of the present invention. '-' ~ --- > The compositions of the invention may contain a lime soap peptizer compound, which preferably has a lime soap dispersing power (LSDP, acronym for its name). designation in English: Lime Soap Dispersing Power), as defined below, of not more than 8, preferably not more than 7, most preferably, not more than 6. The lime soap peptizing compound is preferably present at a level of 0% to 20% by weight. A numerical measure of the effectiveness of a lime soap peptizer is given by the lye soap dispersing power (LSDP) that is determined using the soap dispersant test of that described in an article by HC Borghetty and CA Bergman , J. Am. Oil. Chem. Soc, volume 27, pages 88-90 (1960). This method of testing the lime soap dispersion is widely used by practitioners in this field of the art and is mentioned, for example, in the following summary articles W. N: Linfield, Surfactant Science Series, tome 7, page 3; W. N: Linfield, Tenside Surf. Del, volume 27, pages 169-163 (1990); and M. K. Nagarajan, W. F. Masler, Cosmetics and Toiletries, volume 104, pages 71-73 (1989). The LSDP is the percentage by weight ratio of dispersing agent to sodium oleate, necessary to disperse lime soap deposits formed by 0.025 g of sodium oleate in 30 ml of water with 333 ppm of CaCO3 (Ca: Mg = 3.2 ) of equivalent hardness.

"-« »*» * »^« - B- ™ ^ ~ "" - "« »i« > > tj A? L.

Surfactants having good lime soap peptising ability will include certain amine oxides, betaines, sulfobetaines, alkyl ethoxysulfates and ethoxylated alcohols. Exemplary surfactants, having an LSDP of not greater than 8, for use in accordance with the present invention, include dimethylamine oxide of 16 to 18 carbon atoms, alkyl ethoxy sulfates of 12 to 18 carbon atoms, with a average degree of ethoxylation of 1 ad, in particular the alkyl ethoxy sulfate surfactant of 12 to 1d carbon atoms, with an ethoxylation degree of about 3 (LSDP = 4), and the ethoxylated alcohols of 14 to 15 carbon atoms carbon, with an average degree of ethoxylation of 12 (LSDP = 6) or 30, sold under the brands Lutensol A012 and Lutensol A030, respectively, by BASF GmbH. Polymeric lime soap peptizers, suitable for use herein, are described in an article by M. K. Nagarajan, W. F. Masier, found in Cosmetics and Toiletries, volume 104, pages 71-73 (1989). Hydrophobic bleaches, such as 4- [N-octanoyl-6-aminohexanoyl] benzenesulfonate, 4- [N-nonanoyl-6-aminohexanoyl] benzenesulfonate, 4- [N-decanoyl-6-aminohexanoyl] benzenesulfonate and mixtures thereof, and Nonanoyloxybenzenesulfonate, together with hydrophilic / hydrophobic whitening formulations, can also be used as lime soap peptiser compounds.

THE INHIBITION OF DYE TRANSFER The detergent compositions of the present invention may also include compounds for inhibiting dye transfer from one fabric to another, from solubilized and suspended dyes encountered during fabric washing operations, involving colored fabrics.

POLYMERIC AGENTS INHIBITORS OF TRANSFER OF DYE The cleaning compositions according to the present invention also comprise from 0.001% to 10%, preferably from 0.01% to 2%, more preferably from 0.05% to 1% by weight, of polymeric agents inhibitors of dye transfer. Said dye transfer inhibiting polymeric agents are normally incorporated in the cleaning compositions in order to inhibit the transfer of the dyes of colored fabrics onto the fabrics washed therewith. These polymers have the ability to complex with, or adsorb, the fugitive dyes, removed by washing the dyed fabrics, before the dyes have an opportunity to be fixed to other articles present in the wash. Especially suitable dye transfer inhibiting polymeric agents are polymers of polyamine N-oxide, copolymers of N-vinylpyrrolidone and N-vinylimidazole, polymers of polyvinylpyrrolidone, polyvinyloxazolidones and polyvinylimidazoles, or mixtures thereof. The addition of such polymers also enhances the functioning of the enzymes according to the invention. fa) .- THE POLYMERS OF POLYAMINE N-OXIDE The polyamine N-oxide polymers, suitable for use herein, contain units having the following structural formula: P (I) Ax R wherein P is a polymerizable unit, to which the group R-N-O may be attached, or where the group R-N-O forms part of the polymerizable unit, or a combination of both conditions; O O O A is NC, CO, C, -O-, -S-, -N-; x is O or l; The Rs are aliphatic, aliphatic, ethoxylated, aromatic, heterocyclic or alicyclic groups, or any combination thereof, to which the N-O group may be attached, or where the nitrogen of the N-0 group is part of those groups.

The N-O group can be represented by the following general structures: O (R1) x - N - (R2) y =? N - (R1) X (R3); wherein Ri, R2 and R3 are aliphatic, aromatic, heterocyclic or alicyclic groups, or combinations thereof; x o / y "y" o / y z is 0 or 1 and where the nitrogen of the N-O group can be fixed, or where the nitrogen of the N-O group is part of these groups. The N-O group can be part of the polymerizable unit (P) or it can be attached to the polymer backbone, or a combination of both conditions. Suitable polyamine N-oxides, in which the N-O group forms part of the polymerizable unit, comprise the polyamine N-oxides in which R is selected from aliphatic, aromatic, alicyclic or heterocyclic groups. A class of polyamine N-oxides comprises the group of polyamine N-oxides in which the nitrogen of the group NO is part of the group R. The preferred N-oxides of polyamine are those in which R is a heterocyclic group, pyrridine, pyrrole, imidazole, pyrrolidine, piperidine, quinoline, acridine and its derivatives. ^ .a ..... ^^ .. jfiflmiífmrtrfT- '\? p *** ^ - ~ -z ~ * & ~ * Another class of polyamine N-oxides comprises the group of N-polyamine oxides in which the nitrogen of the NO group is attached to the R group. Other suitable N-oxides of polyamine are the 5-polyamine oxides to which it is set the NO group to the polymerizable unit. The preferred class of these polyamine N-oxides are the polyamine N-oxides having the general formula (I); wherein R is an aromatic, heterocyclic or alicyclic group; where the nitrogen of the functional group N-O is part of said group R. 0 Examples of these classes are the polyamine oxides, wherein R is a heterocyclic compound, such as pyrridine, pyrrole, imidazole and their derivatives. Another preferred class of polyamine N-oxides are polyamine oxides having the general formula (I), in which the R are the aromatic, heterocyclic or alicyclic d groups in which the N-O functional group is attached to said groups. Examples of these classes are polyamine oxides in which the R groups can be aromatic, such as phenyl. Any polymeric backbone can be used, provided that the amine oxide polymer formed is water soluble and has properties that inhibit dye transfer. Examples of suitable polymeric backbones are polyvinyls, polyalkylenes, polyesters, polyethers, polyamides, polyimides, polyacrylates, and mixtures thereof. *** ^ m ** »*. - llllllllllllllllllllllllllllllllllllllllllllllllllllllllllllllllllllllllllllllllllllllllllllllllllllllllllllllllllllllllllllllllllllllllllllllllllllllllllllllllllllllllllllllllllll The amine N-oxide polymers of the present invention typically have a ratio of amine to amine N-oxide from 10: 1 to 1: 1,000,000. However, the amount of amine oxide groups present in the polyamine oxide polymer may vary by appropriate copolymerization or by the appropriate degree of N-oxidation. Preferably, the ratio of amine to amine oxide is from 2: 3 to 1: 1,000,000. More preferable, from 1: 4 to 1: 1, 000,000, and most preferred, from 1: 7 to 1: 1, 000,000. The polymers of the present invention actually comprise random or block copolymers in which one type of monomer is an N-0 amine oxide and the other type of monomer is an amine N-oxide or not. The amine oxide unit of the polyamine N-oxides has a pKa < 10, preferably pKa < 7, more preferable, pKa < 6. Polyamine oxides can be obtained in almost any degree of polymerization. The degree of polymerization is not critical, provided that the material has the desired water solubility and the desired dye suspension power. Typically, the average molecular weight is in the range of 500 to 1,000,000, preferably 1,000,000 to 50,000, more preferably 2,000,000 to 30,000, most preferably 3,000 to 20,000. 0 (b) .- THE COPOLYMERS OF N-VINILPIRROLIDONE AND N-VINYLIMIDAZOLE The polymers of N-vinylimidazole and N-vinylpyrrolidone, used in the present invention, have an average molecular weight scale of from 6,000 to 1,000,000, preferably from 6,000 to 200,000. Highly preferred polymers for use in detergent compositions according to the present invention comprise a polymer selected from copolymers of N-vinylimidazole and N-vinylpyrrolidone, wherein said polymer has an average molecular weight scale of 6,000 to 60,000, more preferable, from 8,000 to 30,000, very preferable, from 10,000 to 20,000. The average molecular weight scale was determined by light diffraction, as described by Barth H. G. and Mays J. W., Chemical Analysis, volume 113 Modern Methods of Polymer Characterization. d The highly preferred copolymers of N-vinylimidazole and N-vinylpyrrolidone have a scale of average molecular weight of 6,000 to 60,000, more preferable, from 8,000 to 30,000, very preferable, from 10,000 to ,000. The copolymers of N-vinylimidazole and N-vinylpyrrolidone, characterized in that they have said average molecular weight scale, give excellent dye transfer inhibition properties, while at the same time not adversely affecting the cleaning performance of the detergent compositions formulated therewith .

The copolymer of N-vinylimidazole and N-vinylpyrrolidone of the present invention has a molar ratio of N-vinylimidazole to N- • vinylpyrrolidone from 1 to 0.2, more preferably from 0.8 to 0.3, most preferably from 0.6 to 0.4. 5 c) .- The polyvinyl pyrrolidone The detergent compositions of the present invention may also use polyvinylpyrrolidone ("PVP"), which has average molecular weight Approximately 2,600 to 400,000, preferably about 5,000 to 200,000, more preferably, about 5,000 to 50,000 and, most preferably, about 5,000 to 15,000. Suitable polyvinylpyrrolidones can be obtained commercially from ISP Corporation, New York, NY, USA and Montreal, Canada, under the product names PVP K-16 1 d (average molecular weight of 10,000), PVP K-30 (molecular weight average of 40,000), PVP K-60 () average molecular weight of 160,000) and PVP K-90 (average molecular weight of 360,000). Other suitable polyvinyl pyrrolidones which can be obtained commercially from BASF Corporation include: Sokalan HP 165 Sokalan HP 12; the polyvinylpyrrolidones known to experts in the field of detergents (see, for example, EP-A-262,897 and EP-A-256,696). ± ñ jjlfi? Itm d .- POLYVINYLOXAZOLIDONE The detergent compositions of the present invention may also use polyvinyloxazolidone as a polymeric dye transfer inhibiting agent. Said polyvinyloxazolidones have an average molecular weight of about 2,600 to 400,000, preferably about 6,000 to 200,000, more preferably about 5,000 to 50,000 and, most preferably, about 6,000 to 16,000. the.- POLIVINYLIMIDAZOLE The detergent compositions of the present invention may also use polyvinylimidazole as a polymeric dye transfer inhibiting agent. Said polyvinylimidazoles have an average molecular weight 1d of about 2,600 to 400,000, preferably about 5,000 to 200,000, more preferably about 5,000 to 60,000, and most preferably about 5,000 to 15,000. fi.- THE INTERLACED POLYMERS 20 The entangled polymers are polymers whose skeleton is interconnected to a certain degree; these links can be of nature chemical or physical, possibly with active groups in the skeleton or ramifications; crosslinked polymers have been described in Journal of Polymer Science, volume 22, pages 1035-1039. In one embodiment, the entangled polymers are made in such a way as to form a rigid three-dimensional structure, which can trap the dyes in the pores formed by the three-dimensional structure. In another embodiment, the entangled polymers trap the dyes by swelling. Said entangled polymers are described in the pending patent application 94870213.9.

THE WASHING METHOD The compositions of the invention can be used essentially in any washing or cleaning method, including soaking methods, pretreatment methods and methods with rinse steps, for which a separate rinse aid composition can be added. The process described herein comprises contacting the fabrics with a wash solution in the usual manner, and as exemplified below. The process of the invention is conveniently carried out in the course of the cleaning process. The cleaning method is carried out preferably at 5 ° C to 95 ° C, especially between 10 ° C and 60 ° C. The pH of the treatment solution is preferably from 7 to 12. A preferred method for washing dishes in a washing machine comprises treating the soiled articles with an aqueous liquid in which an effective amount of the composition for washing or rinsing is dissolved or dispersed. tableware in washing machine. An effective amount of the dishwashing composition in the washing machine means from 8 to 60 g of product dissolved or dispersed in a washing volume of 3 to 10 liters. According to a method for washing dishes by hand, the dirty articles are contacted with an effective amount of the dishwashing composition, typically from 0.5 to 20 g (for 25 items being treated). Preferred methods for washing dishes by hand include the application of a concentrated solution to the surfaces of the articles or soaking in a large volume of diluted solution of the detergent composition. The following examples are intended to illustrate the compositions of the present invention; but it does not necessarily mean that they limit or otherwise define the scope of the invention. In the cleaning compositions, the levels of enzyme by pure enzyme, by weight of the total composition and, unless otherwise specified, the detergent ingredients are expressed by weight of the total compositions. The abbreviated identifications of components, in the present, have the following meanings ^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^ ^^^^^ ^^^ S Linear sodium alkylbenzenesulfonate, 11 to 13 carbon atoms. TAS Sodium tallow alkyl sulfate CxyAS sodium alkyl sulphate of 1x to 1 and carbon atoms CxySAS Secondary sodium alkylsulfate (2,3) from 1x to 1y carbon atoms. CxyEz Primary predominantly linear alcohol, from 1x to 1y carbon atoms, condensed with an average of z moles of ethylene oxide. CxyEzS Sodium alkylsulphate of 1x to 1y carbon atoms, condensed with an average of z moles of ethylene oxide. QAS R2.N + (CH3) 2 (C2H4OH), with R2 = 12 to 14 carbon atoms. QAS 1 R2.N + (CH 3) 2 (C 2 H 4 OH), with R 2 = 8 to 11 carbon atoms. APA Amidopropyldimethylamine of 8 to 10 carbon atoms. Soap: Sodium linear alkylcarboxylate, derived from an 80/20 mixture of tallow and coconut fatty acids. Non-ionic Mixed ethoxylated / propoxylated fatty alcohol, of 13 to 15 carbon atoms, with an average degree of ethoxylation of 3.8 and an average degree of propoxylation of 4.5.

Neodol 45-13 Linear primary alcohol ethoxylate, 14 to 15 carbon atoms, sold by Shell Chemical Co. STS Sodium toluene sulfonate CFAA Alkyl-N-methylglucamide of 12 to 14 carbon atoms in the alkyl. TFAA Alkyl-N-methylglucamide of 16 to 18 carbon atoms in the alkyl. TPKFA Fatty acids of whole cut, with extracted upper portion, of 12 to 14 carbon atoms. 10 DEQA Di (tallowoxyethyl) dimethylammonium chloride. DEQA (2) Di- (tallowyl-oxyethyl) hydroxyethylmethyl ammonium methylisulfate. DTDMAMS Disodbodimethylammonium methylisulfate. SDASA Reason 1: 2 of stearyldimethylamine: triple stearic acid pressed. Silicate Amorphous sodium silicate (Si02 ratio: Na2O = 1.6-3.2) Metasilicate Sodium metasilicate (ratio S02: Na20 = 1.0). Zeolite A Hydrated sodium aluminosilicate having the formula Na-? 2 (AI02S02)? 2.27H20, which has a size of primary particle within the scale of 0.1 to 10 microns (weight expressed on an anhydrous basis). Na-SKS-6 Crystalline stratified silicate having the formula d- Na2Si2O5.

Citrate Trisodium citrate dihydrate, with activity of 86.4%, with particle size distribution between 425 and 850 microns. Citrus Anhydrous citric acid. 5 Sodium borate sodium carbonate Anhydrous carbonate with a particle size between 200 and 900 microns. Bicarbonate Anhydrous sodium bicarbonate, with particle size distribution between 400 and 1200 microns. 10 Sulfate Anhydrous sodium sulfate. Magnesium sulfate Anhydrous magnesium sulfate. STPP Tripol sodium phosphate. TSPP Tetrasodium pyrophosphate MA / AA 4: 1 random copolymer of acrylate / maleate, average molecular weight approximately 70,000-80,000. MA / AA 1 Acrylate / maleate 6: 4 random copolymer, average molecular weight approximately 10,000. AA Sodium polyacrylate polymer, with an average molecular weight of 4,500. 20 PA30 Polyacrylic acid with average molecular weight between about 4,500 and 8,000. 480N Acrylate / methacrylate 7: 3 random copolymer, average molecular weight around 3,500 Poligel / carbopol Interlaced polyacrylates of high molecular weight. PB1 Anhydrous sodium perborate monohydrate, of nominal formula NaB02.H202. PB4 Sodium perborate tetrahydrate, of nominal formula NaB023H2O.H202 Percarbonate Anhydrous sodium percarbonate, of nominal formula 2Na2C03.3H202. NaDCC Sodium dichloroisocyanurate TAED Tetraacetylethylenediamine 10 NOBS Nonanoyloxybenzenesulfonate, in the form of the sodium salt. NACA-OBS (6-nonamidocapropyl) oxybenzenesulfonate DTPA Diethylenetriaminepentaacetic acid HEDP 1,1-Hydroxy-diethyphosphonic acid. DETPMP Penta (methylene) phosphonate of diethylenetriamine, sold by Monsanto under the trademark Dequest 2060. EDDS Isomer (S, S) of ethylenediamine-N.N'-disuccinic acid, in the form of its sodium salt. MnTACN 1, 4J-trimemethyl-1,4-triazacyclononane-manganese. 20 Zinc sulfonated foFtalocyanine bleach, encapsulated in dextrin-soluble activated polymer. Bleach 1 fo sulfonated phthalocyanine, encapsulated in dexalated soluble activated polymer. »^^^^^^ - ^. * ~ ** í ****? * ~. £ || j PAAC Cobalt salt (lll) of pentaamine acetate Paraffin Paraffin oil, sold under the Winog 70 brand by Wintershall. NaBz Benzoate sodium BzP Benzoyl peroxide Oxygenase β-carotene-15,15'-dioxygenase (EC 1.13.11.21), obtained as described in Biochem. Biophys. Acta, 370, 49 (1974) and / or squalene-monooxygenase (EC 1.14.99J), obtained as described in J. Biol. Chem., 245. 1670 (1970) and its cofactor FAD in a weight ratio of pure enzyme / cofactor between 1: 2 and 1: 5. Protease Proteolytic enzyme sold under the trademark Savinase, Alcalase, Durazym, by Novo Nordisk A / S; Maxacal, Maxapem, sold by Gist-Brocades, and proteases described in patents WO 91/06637 and / or WO 95/10591 and / or EP 251 446. Amylase Amylolytic enzyme sold under the trademark Purafact Ox Am ®, described in WO 94/18314, WO 96/05295, sold by Genencor; Termamyl ®, Fungamyl ® and Duramyl ®, all obtainable from Novo Nordisk A / S, and those described in WO 95/26397. 3tím? £ ieSj ^^^^^^^^^^ Lipase Lipolytic enzyme sold under the Lipolase brand, Lipolase Ultra, by Novo Nordisk A S and Lipomax by Gist-Brocades. Cellulase: Cellulite enzyme sold under the trademark Carezyme, Celluzyme and / or Endolase by Novo Nordisk A / S. CMC Carboxymethylcellulose sodium PVP Polyvinyl polymer with average molecular weight of 60,000. PVNO N-oxide polyvinylpyridine, with average molecular weight of 50,000. PVPVI Copolymer of vinylimidazole and vinylpyrrolidone, with average molecular weight of 20,000 Brightener 1 4,4'-bis (2-sulphotrisbiphenyl disodium) Brightener 2 4,4'-bs (4-anilino-6-morpholino-1,3, Disodium 5-triazin-2-yl) stilben-2,2'-disulfonate Defoamer of Polydimethylsiloxane foam controller, with siloxane-oxyalkylene lime copo-silicone as a dispersing agent, with a ratio of foam controller to dispersing agent of 10: 1 to 100: 1 Suppressor 12% silicone / silica, 18% stearyl alcohol, 70% starch foam in granulated form.

Opacrator Mix of water-based monostyrene latex, sold by BASF Aktiengesellschaft, under the brand name Lytron 621. SRP1 Amosically crowned polyesters at the end SRP2 Short block polymer of poly (1, 2-propylene) diethoxylated terephthalate. QEA bis ((C2H50) (C2H40) n) (CH3-N + .C6H12-N +. (CH3) bis ((C2H50). (C2H40)) n where n = from 20 to 30. PEI polyethylenimine, with average molecular weight of 1800 and an average degree of ethoxylation of 7 ethyleneoxy residues per nitrogen SCS Sodium Cumensulfonate HMWPEO High molecular weight polyethylene oxide PEGx Polyethylene glycol, with molecular weight x PEO Polyethylene oxide, with average molecular weight of 5,000 TEPAE Ethoxylate tetraethylene pentaamin BTA benzotriazole pH Measured as a 1% solution in distilled water at 20 ° C.

EXAMPLE 1 The following high density laundry detergent compositions were prepared according to the present invention: EXAMPLE 2 The following laundry detergent compositions were prepared, granulated, of particular utility under the European washing conditions in washing machine, in accordance with the present invention: O- "^ * is ^ ^^ ..? J ^ &^^^ ^ "^, ^" Á ^^^^^^^ ¿"^ ^^^^^ fe ^ 0 EXAMPLE 3 The following detergent compositions of particular utility were prepared under washing conditions in a European washing machine, in accordance with the present invention: EXAMPLE 4 The following granular detergent compositions were prepared according to the present invention: jügg ^^^^ il ^^^^^^^^ ^ á? ? ^ t ^^^^^^ -i ...... «gÉiiiiÉB ^^ 10 fifteen twenty EXAMPLE 5 The following detergent compositions containing no bleach, for particular use in washing colored fabrics, were prepared in accordance with the present invention: EXAMPLE 6 The following detergent compositions were prepared, in accordance with the present invention: fifteen 10 EXAMPLE 7 The following granular detergent compositions were prepared according to the present invention: fifteen twenty *? AÍá * ^ 3 * tofc < * A, ^ 1, > '* tfiüttatt? EXAMPLE 8 The following detergent compositions were prepared according to the present invention. fifteen twenty EXAMPLE 9 The following detergent compositions were prepared in accordance with the present invention: •? & ^^^^^ b ^ &^^ i. ^^^ M ^ ¿? Iau? Imb »*» », **, ^ - > ? ** »~. * ..- S ^ Í *? I EXAMPLE 10 The following liquid detergent formulations were prepared according to the present invention (the levels are given in parts by weight, and the enzymes are expressed in pure enzyme): ¡^^ & g &xx gg ^^ Miscellaneous and water EXAMPLE 11 The following liquid detergent formulations were prepared according to the present invention (the levels are given in parts by weight, the enzymes are expressed in pure enzyme): Miscellaneous and water EXAMPLE 12 The following liquid detergent compositions were prepared in accordance with the present invention (the levels are given in parts by weight, the enzymes are expressed in pure enzyme): fifteen twenty Miscellaneous and water EXAMPLE 13 The following liquid detergent compositions were prepared in accordance with the present invention (the levels are given in parts by weight, and the enzymes are expressed in pure enzyme): 15 twenty ? ^^^ - ^^^ t? atíU? **** - * ^ Miscellaneous and water EXAMPLE 14 The following granular, fabric detergent compositions were prepared according to the present invention, which give "softness during washing": EXAMPLE 15 The following fabric softening composition, added during the rinsing, was prepared in accordance with the present invention: EXAMPLE 16 The following fabric softening compositions were prepared and fabric conditioners, added in the dryer, in accordance with the present invention: 20 EXAMPLE 17 The following laundry detergent compositions were prepared according to the present invention (the levels are given in parts by weight, the enzymes are expressed in pure enzyme): ro n n ^ 1 r o Ol n oo EXAMPLE 18 The following detergent additive compositions were prepared in accordance with the present invention: 15 EXAMPLE 19 The following, high density (0.96 kg / L), compact dishwashing detergent compositions were prepared in accordance with the present invention: -Ji ^^ s ^ iti? Iíi ^ ÁSí a ^ áM ^^^^ S ^ i ^^^^? TM or cn cn cn 4k O K3 O cn cn ro or n EXAMPLE 20 or n The following granular dishwashing detergent compositions, with a volumetric density of 1.02 kg / L, were prepared in accordance with the present invention: ro fO or n n EXAMPLE 21 The following detergent compositions were prepared in tablet, according to the present invention, by compression of a granular dishwashing detergent composition, at a pressure of 13 KN / cm2, using a common rotary press, of 12 heads: fifteen twenty atrfaM Lafa ^ fcJSSfca * EXAMPLE 22 The following liquid dishwashing detergent compositions, with a density of 1.40 kg / L, were prepared in accordance with the present invention: fifteen EXAMPLE 23 The following liquid rinse aid compositions were prepared in accordance with the present invention: EXAMPLE 24 The following liquid dishwashing compositions were prepared in accordance with the present invention: twenty fifteen twenty ^ a ^^ fe ^^^^^ j ^ S ^^^ sSteéj ^^ i ^^^^^^^^^^^^^^^^ jSÍ EXAMPLE 25 The following hard, liquid surface cleaning compositions were prepared in accordance with the present invention: fifteen twenty ^^^^ fer ^^^^^^ T ^ fe ^ i ^^ a ^^^^^^^^^^^, * Ethylenediamine diacetic acid of Na ** Diethylene glycol monohexyl ether *** All formulas were adjusted to pH 7-12.

EXAMPLE 26 The following spray composition was prepared to clean hard surfaces and remove domestic mold, in accordance with the present invention: Oxygenase 0.05 Amylase 0.01 Protease 0.01 Octylsulphate Na 2.0 Dodecyl sulfate Na 4.0 Na hydroxide 0.8 Silicate 0.04 Butylcarbitol * 4.0 Perfume 0.35 Water / minors up to 100% "diethylene glycol monobutyl ether EXAMPLE 27 The following lavatory cleaning block compositions were prepared in accordance with the present invention. 0 EXAMPLE 28 The following cleaning composition for toilet bowl was prepared, in accordance with the present invention:

Claims (20)

NOVELTY OF THE INVENTION CLAIMS

1. - A detergent composition, characterized in that it comprises an oxygenase directed to body dirt.

2. A detergent composition according to claim 1, further characterized in that the oxygen directed to the soils of the body is also characterized by being a sulfur or iron heme-oxygenase and / or an oxygenase that depends on metal 10 heavy.

3. A detergent composition according to claims 1 and 2, further characterized in that the oxygen directed to the soils of the body is present at a level of 0.0001% to 2%, preferably 0.001% to 0.5%, more preferably, from 0.002% to 0.1% enzyme 15 pure by weight of the total composition.

4. A detergent composition according to any of the preceding claims, further characterized in that the oxygenase directed to body dirt is alkaline.

5. A detergent composition according to any of the preceding claims, further characterized in that it additionally comprises a cofactor. g ^^^^^^^ ^ g? jg¡ ^^^^^^^^^^^^^^^^^^^^^^^^ __ ^^^^^

6. - A detergent composition according to claim 5, further characterized in that the cofactor is included at a weight ratio of pure oxygenase directed to body soils with respect to the cofactor, between 10: 1 and 1:10, preferably 5: 1 to 1: 8, more preferable, between 1: 2 and 1: 5.

7. A detergent composition according to any of the preceding claims, further characterized in that it additionally comprises a detergent enzyme, preferably selected from: cellulase, lipase, protease, amylase, and / or mixtures thereof.

8. A detergent composition according to any of the preceding claims, further characterized in that it additionally comprises another bleaching system.

9. A detergent composition according to claim 8, further characterized in that the bleaching system is an activated, conventional bleaching system.

10. A detergent composition according to claim 9, further characterized in that the bleaching agent is selected from perborate and / or percarbonate, and the activator is selected from tetraacetylethylenediamine, nonanoyloxybenzenesulfonate and / or 3,5-trimethylhexanoyloxybenzenesulfonate.

11. A detergent composition according to claim 8, further characterized in that the bleaching system is another enzymatic bleaching system. '..saA ßa

12. - A detergent composition according to claim 8, further characterized in that the bleaching system is a bleaching system based on a metal catalyst.

13. A detergent composition according to claim 12, further characterized in that the metallo catalyst is a transition metal complex of a rigid macropolycyclic ligand.

14. A detergent composition according to claims 12 and 13, further characterized in that the metal catalyst is manganese.

15. A detergent composition according to any of the preceding claims, further characterized in that it is in the form of an additive.

16. A fabric softening composition, characterized in that it comprises oxygenase directed to the soils of the body, and a cationic surfactant agent comprising two long chain stretches.

17. The use of an oxygenase directed to body soiling in a detergent and / or a softening composition for cleaning fabrics and / or removing fabric stains and / or maintaining the whiteness of fabrics and / or softening fabrics and / or the appearance of color of fabrics and / or the inhibition of 20 Transfer of dye on fabrics.

18. The use of an oxygenase directed to the soils of the body in a detergent composition for cleaning hard surfaces, such as floors, walls, tiles and the like.

19. - The use of an oxygenase directed to body dirt in a dishwashing detergent composition by hand and machine.

20. The use of an oxygenase directed to soils of the body in a detergent and / or softening composition, to sanitize the treated surfaces.