MXPA99001405A - Detergent compositions comprising alkaline polygalacturonase - Google Patents

Abstract

The present invention relates to detergent compositions, including dishwashing, hard surface cleaning and laundry compositions containing an alkaline polygalacturonase enzyme for improved overall cleaning performance and enhanced stain/soil removal benefits and in particular improved removal of plant, dried-on fruit and vegetables juice soils/stains.

Description

DETERGENT COMPOSITIONS COMPRISING ALKALINE POLYGALACTURQNASE TECHNICAL FIELD This invention relates to detergent compositions that include compositions for household cleaning, dishwashing and laundry washing, containing alkaline polygalacturonase enzyme substantially free of other pectic enzymes.

BACKGROUND OF THE INVENTION The overall performance of a detergent product, to be used in a washing or cleaning method, such as a laundry or dishwashing method, is judged by many factors, including the ability to remove dirt, and the ability to avoid the redeposition of the dirt, or the degradation products of the dirt on the articles in the wash. The removal of stains that come from plants, wood, dirt based on clay mud and fruits is one of the most difficult cleaning tasks at present; in particular with tendencies to change at low wash temperatures. These stains typically contain complex mixtures of fibrous material based primarily on carbohydrates and their derivatives: fibers and cell wall components. Soils of vegetable origin are also accompanied by amylose, sugars and their derivatives. Food stains are often difficult to remove effectively from a dirty substrate. Highly stained or "dried" soils derived from fruit and / or vegetable juices are particularly difficult to remove. Specific examples of such dirt would include soils of orange juice, tomato juice, banana, mango or broccoli. The substrates can be fabrics, crockery or hard surfaces. The pectic substances are found, for example, in fruit juices. The pectic substances act to keep dispersed particles in suspension in said fruit juices, which will tend to be viscous and opaque in nature.

Pectic enzymes are commonly used in the fruit / vegetable juice processing industry in the clarification of juices by degradation of pectic substances in them (depectinization). The German patent specification 3,635,427, published on April 23 by Lion Corporation, is directed to phosphate-free detergents for cleaning fabrics containing enzymes with pectinase activity, which are said to include enzymes such as polygalacturonase, pectin lyase and / or pectin esterase. However, in addition to the general teachings in the same related to mixtures of these pectinase enzymes for removal of the inorganic dirt of fabrics, the only specific teaching related to an individual pectinase enzyme is found in example 3, where the enzyme (designated as "Enzyme D") is characterized as an enzyme that contains a large amount of pectin lyase. Table III provides the results of the evaluation of this enzyme D in a detergent formulation, indicating that this mixture of high pectin lyase content has the highest percentage of pectinase activity (10%) and one of the highest detergency values. (83%) in combination with water-soluble high molecular weight compounds compared to compounds with other enzyme compositions reported. The benefits for the specific use of polygalacturonase enzyme which is substantially free of other pectic enzymes in detergent formulations, particularly those designed for use in laundry, dishwashing and household cleaning operations have been recognized in the patent application of E.U.A. Copendent US08 / 529816. It is an object of the present invention to provide laundry detergent, dishwashing or household cleaning compositions that provide improved soil / stain removal benefits when used in washing and cleaning operations. In accordance with the present invention, it has now surprisingly been found that the polygalacturonase enzyme having at least 10%, preferably 25%, most preferably 40% of its optimum activity, at a pH ranging from 7 to 11 and in particular with an optimum activity at a pH ranging from 7 to 11 significantly improves the removal of a wide range of spots based in plants and fruits and increases the actual cleaning profile of the detergent compositions. In fact, the inclusion of the alkaline polygalacturonase enzyme provides in particular improved removal of dirt and stains from dried fruit and vegetable juices. In addition, it has been found that the alkaline polygalacturonase enzyme substantially free of other pectic enzymes exhibits improved compatibility and increased activity in the wash solution thus providing improved removal of soils and body fluid stains, dried fruit and vegetable juices, especially when they come from heavy-duty laundry and ware washing compositions. It has also been found that the alkaline polygalacturonase enzyme substantially free of other pectic enzymes demonstrates better compatibility with detergent matrix, for example, during processing and shelf-life of the product. Furthermore, it has also been surprisingly found that the inclusion of dispersants, particularly organic polymeric dispersants, is of great value in detergent compositions containing alkaline polygalacturonase enzymes.

The dispersants help to the dispersion of the degradation products of the enzymatic degradation of the dirt, thus preventing its redeposition in articles that are in the washing water. The improved cleaning performance has also been observed when the alkaline polygalacturonase enzymes are combined with other detergent enzymes. The bleaching system or conventional activated bleaching system together with alkaline polygalacturonase enzymes provides increased performance benefits over a wide range of blemishes. In addition, polymers that provide inhibition of dye transfer combined with alkaline polygalacturonase enzymes result in improved properties of maintenance of whiteness and / or release of dirt.

BRIEF DESCRIPTION OF THE INVENTION The present invention relates to detergent compositions, including dishwashing compositions, hard surface cleaning and laundry washing containing an alkaline polygalacturonase enzyme substantially free of other pectic enzymes for improved overall cleaning performance and stain removal / dirt removal benefits. increased and in particular improved removal of dirt and stains from fruit and vegetable juices.

DETAILED DESCRIPTION OF THE INVENTION Alkaline polygalacturonase enzyme An essential component of the detergent compositions of the invention is an alkaline polygalacturonase enzyme. The term "alkaline" is intended to cover polygalacturonase enzyme having an enzymatic activity of at least 10%, preferably 25%, most preferably 40% of its optimal activity, at a pH ranging from 7 to 11 and to cover polygalacturonase enzyme having its optimal activity at a pH ranging from 7 to 11. Enzymatic activity can be measured according to "Assay of APGase" described by K. Horikoshi in Agr. Biol. Chem. Vol. 36 (2), 286. As used herein, "substantially free of other pectic enzymes" means compositions containing polygalactinase enzyme containing less than 50% pectic enzymes that are not polygalactanase alkaline enzymes, preferably less about 25%, most preferably less than about 10%, and most preferably still about 5%. Said pectic enzymes include, for example, the pectin methylesterases that hydrolyze the pectin methyl ester bonds, and the pectin transeliminases or lyases that act on the pectic acids to produce non-hydrolytic cleavage of alpha-1-4 glycosidic bonds to form unsaturated derivatives of galacturonic acid. The polygalactinase alkaline enzyme is preferably incorporated in the compositions according to the invention at a level of from 0.0001% to 2%, preferably from 0.0005% to 0.5%, most preferably from 0.001% to 0.1% pure enzyme by weight of the total composition . By alkaline polygalactinase enzyme is meant any enzyme that acts to break down substances by cleaving the bonds between molecules of galacturonic acid. Pectic substances can be found in vegetable teas, and are common constituents of fruit juices such as orange, tomato and grape juices. The pectic substances contain galacturonic acids and / or their derivatives. Pectic substances include pectins and pectic acids. Pectins are, in general, polymers made of chains of galacturonic acids linked by alpha-1,4-glycosidic bonds. Typically, in natural pectins approximately two-thirds of the carboxylic acid groups are esterified with methanol. The partial hydrolysis of these methyl esters gives pectins with low methoxyl content, which tend to form gels with calcium ions. Complete hydrolysis with methyl ester gives pectic acids. The alkaline polygalacturonase enzymes herein include natural alkaline polygalacturonase enzymes and any variants obtained, for example, by genetic engineering techniques. The alkaline polygalacturonase enzymes are produced by alkalophilic microorganisms, for example, bacteria, fungi and yeasts such as Bacillus species. Preferred microorganisms are Bacillus firmus, Bacillus circulans and Bacillus subtilis as described in JP 56131376 and JP 56068393. Said enzymes can also be produced by Eria species. E are preferred. chrysanthemi, E. carotovora, E. amylovora, E. herbicola, E. dissolvens as described in EP 59066588, JP 63042988 and in World J. Microbiol. Microbiotechnol. (8, 2, 115-120) 1992. Alkaline pectin degrading enzymes can also be produced by Bacuillus species as described in JP 73006557 and Agr. Bioí. Chem. (1972), 36 (2) 285-93. Pectin-degrading enzymes are produced by alkaloflucos microorganisms, for example, bacteria, fungi and yeasts such as Bacillus species. Preferred microorganisms are Bacillus firmus, Bacillus circulans and Bacillus subtilis as described in JP 56131376 and JP 56068393. Pectin decomposing enzymes include galacuran-1, 4-alpha-galcturonase (EC 3.2.1.67), polygalacturonase activities (EC 3.2.1.15) pectin esterase (EC 3.1.1.11), pectate lyase (EC 4.2.2.2) and its isoenzymes and can be produced by Erwinia species. E. chrysanthemi, E. carotovora, E are preferred. amylovora, E. herbicola, E. dissolvens as described in EP 59066588, JP 63042988 and in World J. Microbiol. Microbiotechnol. (8, 2, 115-120) 1992. Said pectin enzymes can also be produced by Bacuillus species as described in JP 73006557 and Agr. Biol. Chem. (1972), 36 (2) 285-93. Said enzymes can be used after purification to isolate polygalacturonase enzymes substantially free of another pectic enzyme. Pectic enzyme compositions consisting essentially of polygalactinase enzymes are preferred. At present, it is common practice to modify wild-type enzymes through protein / genetic engineering techniques to optimize their efficiency of performance in the cleaning compositions of the invention. For example, variants can be designed in such a way that the compatibility of the enzyme to commonly found ingredients of said compositions is increased. Alternatively, the variant can be designed in such a way that the optimum pH, bleach stability, catalytic activity and the like, of the enzyme variant is adjusted to suit the particular cleaning application. In particular, attention must be focused on amino acids sensitive to oxidation in the case of bleaching stability and surface charges for the compatibility of surfactant. The isoelectric point of said enzymes can be modified by the substitution of some charged amino acids, for example, an increase in the isoelectric point can help improve compatibility with surfactants. The stability of the enzymes can be further increased by creating, for example, additional salt bridges and promoting calcium binding sites to increase chelator stability.

Dispersants It has surprisingly been found that the inclusion of dispersants, particularly organic polymer dispersants, is of great value in detergent compositions containing polygalactinase enzymes. alkaline The dispersants help the dispersion of the degradation products of the enzymatic degradation of soils, thus preventing their redeposition in articles in the wash. Suitable organic water-soluble salts are homo- or copolymeric acids or their salts, in which the polycarboxylic acid comprises at least two carboxyl radicals separated from one another by not more than two carbon atoms. Polymers of this type are described in GB-A-1596, 756. Examples of these salts are polyacrylates with MW of 2000-5000 and copolymers with maleic anhydride, such copolymers having a molecular weight of 1,000 to 100,000. Especially, in the detergent compositions of the present invention, acrylate and methacrylate copolymers such as 480N having a molecular weight of 4000, at a level of 0.5 to 20% by weight of the composition can be added. The compositions of the invention may contain a lime soap peptising compound, having a lime soap dispersing power (LSDP), as hereinafter defined to be no more than 8 preferably no more than 7, more preferably no more of 6. The lime soap peptizer compound is preferably present at a level of 0% to 20% by weight. A numerical measure of the effectiveness of the lime soap peptizer is given by the dispersing power of lime soap (LSDP) which is determined using the lime soap dispersant test, as described in an H.C. Borghetty and C.A. Bergman, J. Am. Oil. Chem. Soc., Volume 27, pages 88-90, (1950). This method of testing the dispersion of lime soap is used extensively by spatialists in this field of art who are referred to, for example, in the following articles of specialized journals: W.N. Linfield, Surfactant science Series, Volume 7, page 3: W.N. Linfield, Tenside surf. det. , volume 27, pages 159-163, (1990); and M.K. Nagarajan, W.F. Masler, Cosmetics and Toiletries, volume 104, pages 71-73, (1989). The LSDP is the ratio of percent by weight of the dispersing agent to the sodium oleate required to disperse the lime soap deposits formed by 0.025 g of sodium oleate in 30 ml of water with equivalent hardness of 333 ppm of CaC 3 (Ca). : Mg = 3: 2). Surfactants having good lime soap peptising ability will include certain amine oxides, betaines, sulfobetaines, alkyl ethoxysulfate and ethoxylated alcohols. Exemplary surfactants having an LSDP of not more than 8 for use in accordance with the present invention include dimethylamine oxide of C ^ gC ^ g] -2 ~ C] _3 alkylcytoisulfates with an average degree of ethoxylation of 1 to 5, in particular C12-C15 ethoxysulfate surfactant with an ethoxylation degree of about 3 (LSDP = 4) and ethoxylated alcohols of C14-C] _5 with an average degree of ethoxylation of either 12 (LSDP = 6) or 30, sold under the factory names of Lutensol A012 and Lutensol A030 respectively, by BASF GmbH. Polymeric lime soap peptizers suitable for use herein are described in the article by Nagarajan, W.F. Masier, which is in Cosmetics and Toiletries, volume 104, pages 71-73, (1989). Lime soap peptizers, hydrocarbon bleaches such as 4- [N-octanoyl-6-aminohexanoyl] benzenesulfate, 4- [N-nonanoyl-6-aminohexanoyl] benzenesulfonate, 4- [N-decanoyl-] can also be used as lime soap peptiser compounds. 6-aminohexa-noyl] benzenesulfonate and mixtures thereof; and nonanoyloxybenzenesulfonate together with hydrophilic / hydrophobic bleach formulations.

Detergent enzymes The improved removal of a wide range of stains based on body fluids, fruit juices and vegetables is achieved with a combination of polygalactinase alkaline enzymes with other detergent enzymes.

Synergistic effects of detergent compositions containing a polygalactinase enzyme and a cellulase, xylanase and / or protease are observed. Cellulases useful in the present invention include bacterial or fungal celluloses. Preferably, they have an optimum pH of between 5 and 9.5. Suitable cellulases are described in the U.S. Patent. 4,435,307, Barbegoard et al., Which describes a fungal cellulase produced by Hu icola insolens. Suitable cellulases are also described in GB-A-2,075,028; GB-A- 2,095,275; and DE-OS-2,247,832. Examples of said cellulases are cellulases produced by a strain of Humicola insolens (Humicola grísea var. Thermoidea), particularly the strain Humicola DSM 1800. Other suitable cellulases are the cellulases originated from the Humicola insolens which has a molecular weight of approximately 50KDa, a point isoelectric of 5.5 and containing 415 amino acids.

Especially suitable cellulases are cellulases that have color care benefits. Examples of said cellulases are the cellulases described in the European patent application No. 91202879.2, filed on November 6, 1991 (Novo).

Caresyme and Celluzyme (Novo Nordisk A / S) are especially useful. See also WO 91/17243. Xylanase enzymes include the commercially available xylanases such as Pulpzyme HB and SP431 from Novo Nordisk), Lyxasan by Gist-Brocades, Optipulp and Xylanase (Solvay). Suitable proteases are the subtilisins that are obtained from particular strains of B. subtilis and B. licheniformis (subtilisins BPN and BPN '). A suitable protease is obtained from a strain of Bacillus, which has maximum activity along the pH scale of 8 to 12, developed and marketed as ESPERASER 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 ALCALAS? R, DURAZYMR and SAVINASER de Novo, and MAXATASER, MAXACALR, PROPERASER and MAXAPEMR (Maxacal treated by genetic engineering techniques of proteins) of International Bio-Synthetics, Inc., The Netherlands; as well as Protease A, as described in EP 130,756 A, of January 9, 1985, and Protease B as described in EP 303,761 A, of April 28, 1987 and EP 130,756 A, of January 9, 1985. See also a high pH protease of Bacillus sp., NCIMB 40338, described in WO 93/18140 A by Novo. Enzymatic detergents comprising protease, one or more other enzymes, and a reversible protease inhibitor are described in WO 92/03529 A by Novo. Other preferred proteases include those of WO 95/10591 A by Procter & Gamble. When desired, a protease having reduced adsorption and increased hydrolysis is available as described in WO 95/07791 by Procter & Gamble. A recombinant protease similar to trypsin for detergents suitable herein is described in WO 94/25583 by Novo. In more detail, the protease referred to as "Protease D" is a carbonyl hydrolase variant having an amino acid sequence not found in nature, and which is derived from a carbonyl hydrolase 'precursor by substituting a different amino acid for a plurality of residues of amino acids at a position in said carbonyl hydrolase 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, +195, +197, +204, +206, +210, +216, +217 , +218, +222, +260, +265 and / or +274 in accordance with the Bacillus amyloliguefaciens subtilisin numbering, as described in WO 95/10591 and in the patent application of C. Ghosh et al. , "Bleaching Compositions Comprising Protease Enzymes", with US serial number No. 08 / 322,677, filed October 13, 1994. Also suitable for the present invention are proteases described in patent applications EP 251 446 and WO 91/06637 and the BLAPR protease described in WO91 / 02792. Improved removal of dirt and bodily fluid stains, fruit and vegetable juices are observed with detergent compositions of the present invention further comprising starch degrading enzymes, sugar and its derivatives, such as amylase, glucoamylase, dextranase, pullulanase, invertase, laccase, insulinase. Suitable amylases (alpha and / or beta) to be included in the detergent compositions of the present invention are those of: WO / 94/02597, Novo Nordisk A / S, published on February 3, 1994, describes cleaning compositions that incorporate mutant amylases . See also WO / 94/18314, Genencor, published August 18, 1994 and WO / 95/10603 Novo Nordisk A / S, published April 20, 1995. Other amylases known for use in cleaning compositions include alpha and beta amylases Alpha amylases are known in the art, and include those described in the 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 British Patent Specification No. 1,296,839 (Novo). Other suitable amylases are amylases of improved stability including Purafact Ox Arrr described in WO 94/18314, published on August 18, 1994, and amylase variants having further modification in the immediate parent molecule, available from Novo Nordisk A / S, described in WO 95/10603, published in April 1995. Examples of commercial products of alpha amylases are Termamyl, Ban, Fungamyl® and Duramyl®, all available from Novo Nordisk A / S, Denmark. W095 / 26397 describes other suitable amylases: alpha amylases characterized by having 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 in the scale from 8 to 10, measured by the alpha amylase activity test • Phadebas. Other amylolitic enzymes with improved properties with respect to the activity level and the combination of thermostability and higher level of activity are described in W095 / 35382. Other carbohydrases combined with polygalactinase alkaline enzymes show synergistic performance benefits, such as beta-glucanase (lichenase, laminase) and exo-glucanase (lignase, tannase, pentosanase), malanase and hemicellulase). Finally, combinations of enzymes that hydrolyze fat and waxes such as lipases, cutinases and wax esterases, and polygalactinase enzymes provide improved synergistic removal of dirt and fluid stains from fruit and vegetable juices. Lipase enzymes suitable for use in detergents include those produced by microorganisms of the Pseudomonas group, such as Pseudomonas stutzeri, ATCC 19,154, as described in British Patent 1,372,034. Suitable lipases include those that show a positive immunological cross-reaction with the lipase antibody, produced by the microorganism Pseudomonas fluorescent, IAM 1057. This lipase is available from Amano Pharmaceutical Co. Ltd., Nagoya, Japan, under the trade name Lipase P "Amano", referred to later as "Amano-P". Other suitable commercial lipases include Amano-CES, lipases, for example, from Chromobacter viscosum, for example Chromobacter viscosum var. lipolyticum, NRRLB 3673, from Toyo Jozo Co., Tagata, Japan; Chromobacter viscosum lipases from U.S. Biochemical Corp., E.U.A. and Disoynth Co., The Netherlands, and lipases, for example, from Pseudomonas gladioli. Especially suitable lipases are lipases such as Ml Lipase and Lipomax (Gist-Brocades), and Lipolase® and Lipolase Ultra® (Novo), which have been found to be very effective when used in combination with the compositions of the present invention. Also suitable are cutinases [EC 3.1.1.50], which may be considered as a special type of lipase, namely, lipases that do not require interfacial activation. The addition of cutinases to detergent compositions has been described, for example, in WO-A-88/09367 (Genencor). The lipases and / or cutinases are normally incorporated in the detergent composition at levels of 0.0001% to 2% active enzyme by weight of the detergent composition. The aforementioned enzymes can be of any suitable origin, such as of vegetable, animal, bacterial, fungal and yeast origin. Said enzymes are normally incorporated in the detergent composition at levels of 0.0001% to 2% active enzyme by weight of the detergent composition. Enzymes can be added as separate individual ingredients (pellets, granules containing an enzyme), or as mixtures of two or more enzymes (eg, cogranulates). Other suitable detergent ingredients that can be added are enzyme oxidation scavengers, which are described in co-pending European patent application 92870018.6, filed on January 31, 1992. Examples of said enzyme oxidation scavengers are ethoxylated tetraethylenepolyamines. A range of enzyme materials and means for their incorporation into synthetic detergent compositions is also disclosed in WO 9307263 A and WO 9307260 A by Genencor International, WO 8908694 A by Novo, and U.S. 3,553,139, January 5, 1971, by McCarty et al. The enzymes are further described in U.S. 4,101,457, Place et al., Of July 18, 1978, and in U.S. 4,507,219, Hughes, March 26, 1985. Useful enzyme materials for liquid detergent formulations, and their incorporation into such formulations, are described in U.S. 4,261,868, Hora et al., April 14, 1981. Enzymes for use in detergents can be stabilized by various techniques. Enzyme stabilization techniques are described and exemplified in U.S. 3,600,319, of August 17, 1971, Gedge et al., EP 199,405 and EP 200,586, of October 29, 1986, Venegas. Enzyme stabilization systems are also described, for example, in U.S. 3,519,570. A useful Bacillus, the AC13 species, which produces proteases, xylanases and cellulases, is described in WO 9401632 A, by Novo.

Bleaching agent It has been found that a wide range of removal of soils and stains from body fluids, fruit and vegetable juices is achieved with detergent compositions containing an enzymatic bleaching system or a conventional activated bleaching system in addition to the polygalactinase alkaline enzyme. Bleaching agents such as hydrogen peroxide, PB1, PB4 and percarbonate with a particle size of 400-800 microns. These bleaching agent components can include one or more oxygen bleaching agents and, depending on the bleaching agent chosen, one or more bleach activators. When present, oxygen bleach compounds will typically be present at levels of about 1% to about 25%. The bleaching agent component for use herein may be any of the bleaching agents useful for detergent compositions including oxygen bleaching 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. A category of oxygen bleaching agent that can be used encompasses percarboxylic acid bleaching agents and salts thereof. Suitable examples of this class of agents include in magnesium monoperoxyphthalate hexahydrate, the magnesium salt of meta-chloroperbenzoic acid, 4-nonylamino-4-oxoperoxybutyric acid and diperoxydecanedioic acid. Such bleaching examples are set forth in the US patent. 4,483,781, the patent application of E.U.A. 740,446, European patent application 0,133,354 and US patent 4,412,934. Highly preferred bleaching agents include 6-nonylamino-6-oxoperoxycaproic acid as described in the US patent. 4,634,551. Another category of bleaching agents that can be used includes halogen bleaching agents. Examples of hypohalogenite bleaching agents, for example, include isocyanuric acid and dichloroisocyanurates and sodium and potassium N-chloro- and N-bromo-alkan-sulphonamides. Such materials are usually added to 0.5-10% by weight of the finished product, preferably, 1-5% by weight. The hydrogen peroxide releasing agents can be used in combination with the bleach activators such as tetraacetylethylenediamine (TAED), nonanoyloxybenzenesulfonate (NOBS, described in US 4,412,934), 3,5, -trimethylhexanoloxybenzenesulfonate (ISONOBS, described in EP 120,591). ) or pentaacetylglucose (PAG) or phenol-sulfonate-ether of N-nonanoyl-6-aminocaproic acid (NACA-OBS, described in WO94 / 28106), which are perhydrolyzed to form a peracid as the active bleaching species, producing an improved bleaching effect. Suitable acylate citrate esters are also suitable activators as disclosed in co-pending European Patent Application No. 91870207.7 Useful bleaching agents are disclosed, including peroxyacids comprising bleach activators and peroxygen bleach compounds for use in detergent compositions in accordance with US Pat. the invention, in our pending applications USSN 08 / 136,626, PCT / US95 / 07823, W095 / 27772, W095 / 27773, W095 / 27774 and W096 / 27775. The hydrogen peroxide may also be present by adding an enzyme system (ie, an enzyme and therefore a substrate) which is capable of generating hydrogen peroxide at the beginning and where the washing and / or rinsing process is carried out. Such enzyme systems are disclosed in patent application EP 91202655.6 filed on October 9, 1991. Peroxidase enzymes are used in combination with oxygen sources, for example, percarbonate, perborate, persulfate, hydrogen peroxide, etc. They are used for "bleaching in solution", that is, to prevent the transfer of dyes or pigments removed from substrates, during the washing operations, to other substrates in the washing solution. Peroxidase enzymes are known in the art and include, for example, horseradish peroxidase, ligninase, laccase and haloperoxidase, such as chloro- and bromo-peroxidase. Detergent compositions containing peroxidase are described, for example. in the PCT International Application WO 89/099813, WO 89/09813, and in the European Patent Application EP No. 91202882.6, filed on November 6, 1991, and in EP No. 96870013.8, filed on February 20 1996. Laccase is also suitable. Preferred builders are substituted phenoxyzine and phenoxazine, 10-phenothiazinopropionic acid (PPT), 10-ethylphenothiazine-4-carboxylic acid (EPC), 10-phenothiazinopropionic acid (POP) and 10-methylphenoxazine (described in WO 94/12621), and substituted syringes (substituted C3-C5 alkylsalicylates) and phenols. Sodium percarbonate or perborate are preferred sources of hydrogen peroxide. Said peroxidases are normally 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 catalysts including cobalt such as pentamine-acetate cobalt (III) salts and manganese-containing catalysts such as described in EPA 549 271; EPA 549 272; EPA 458 397; US 5,246,621; EPA 458 398; US 5,194,416 and US 5,114,644. A bleaching composition comprising a peroxy compound, a manganese-containing bleach catalyst and a chelating agent is described in patent application No. 94870206.3. Bleaching agents other than oxygen bleaching agents are also known in the art and can be used herein. One type of oxygen free bleaching agent of particular interest includes photoactivated bleaching agents such as zinc phthalocycins and / or sulfonated aluminum. These materials can be deposited on the substrate during the washing process. By irradiation with light, in the presence of oxygen, for example by hanging clothes outside to dry in daylight, the suftenated zinc phthalocyanine is activated and, consequently, the substrate is bleached. The preferred zinc phthalocyanine and a photoactivated bleaching process are described in the U.S.A. 4,033,718. Typically, the detergent compositions will contain from about 0.025% about 1.25%, by weight, of the sulfonated zinc phthalocyanine.

Inhibition of dye transfer Maintenance of whiteness and / or increased soil release properties have been observed when the detergent compositions of the present invention include compounds to inhibit the transfer of dye from one fabric to another, of solubilized and suspended dyes which They are found during operations for washing fabrics that involve colored fabrics.

Polymeric dye transfer inhibiting agents The detergent 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 transfer inhibiting polymeric agents of dyes. Such polymeric dye transfer inhibiting agents are normally incorporated into the detergent compositions in order to inhibit the transfer of dyes from colored fabrics onto fabrics washed therewith. These polymers have the ability to form complexes or absorb the fugitive centers released in the washing of the dyed fabrics before the dyes have the opportunity to be fixed to other articles 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 performance of the enzymes according to the invention.

Polyamine N-oxide polymers Polyamine N-oxide polymers suitable for use contain units having the following structure formula: P I (1) Ax R wherein P is a polymerizable unit, to which the group R-N-0 may be linked or where the group R-N-0 forms part of the polymerizable unit or a combination of both. 0 0 0 II II II A is NC, CO, C, -O-, -S-, -N-; x is 0 or 1; R are aliphatic, aliphatic, ethoxylated, aromatic, heterocyclic or alicyclic groups or any combination thereof to which the nitrogen of the N-O group may be linked or in which the nitrogen of the N-O group is part of these groups. The N-O group can be represented by the following structures: (Rl) - (Rl) x wherein R1, R2, and R3 are aliphatic, aromatic, heterocyclic or alicyclic groups or combination thereof, x or / e Y o / y z is 0 or 1 and wherein the nitrogen of the N-O group can be linked or where the nitrogen of the N-O group forms part of these groups. The N-O group can be part of the polymerizable unit (P) or it can be linked to the polymeric base structure or a combination of both. The N-O suitable polyamine oxides wherein the N-O group forms part of the polymerizable unit comprises N-oxide polyamines in which R is selected from aliphatic, aromatic, alicyclic or heterocyclic groups. A class of said polyamine N-oxides comprises the group of polyamine N-oxides in which the nitrogen of the NO forms part of the group R. The preferred polyamine N-oxides are those in which R is a heterocyclic group such as pyridine, pyrrole, imidazole, pyrrolidine, piperidine, quinoline, acridine and derivatives thereof. Another class of said polyamine N-oxides comprises the group of polyamine N-oxides in which the nitrogen of the NO group is linked to the R group. Other suitable polyamine N-oxides are the polyamine acids in which the NO group it is linked to the polymerizable unit. Preferred classes of these polyamine N-oxides are the polyamine N-oxides having the general formula (I) wherein R are aromatic, heterocyclic or alicyclic groups in which the nitrogen of the functional group NO is part of said group R Examples of these classes are polyamine oxides in which R is a heterocyclic compound such as pyridine, pyrrole, imidazole and derivatives thereof. Another preferred class of N-polyamine oxides are the polyamine oxides having the general formula (I) wherein R are aromatic, heterocyclic or alicyclic groups in which the nitrogen of the functional group is NOT linked to said R groups. of these classes are the polyamine oxides in which the R groups can be aromatic such as phenyl. Any polymer base structure can be used as long as the amine oxide polymer formed is water soluble and has dye transfer inhibiting properties. Examples of polymeric base structures are polyvinyls, polyalkylenes, polyesters, polyethers, polyamides, polyimides, polyacrylates and mixtures thereof. 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 can be varied by appropriate copolymerization or by an appropriate degree of N-oxidation. Preferably, in the ratio of the amine to the amine N-oxide is from 2: 3 to 1: 1,000,000, more preferably from 1: 4 to 1, 1,000,000, more preferably from 1: 7 to 1: 1,000,000. The polymers of the present invention actually encompass random or block copolymers in which one type of monomer is an amine N-oxide of another type of monomer or is an amine N-oxide or not. The amine oxide unit of the polyamine N-oxides has a PKa < 10, preferably PKa < 7, more preferably PKa < 6. Polyamine oxides can be obtained in almost any degree of polymerization. The degree of polymerization is not critical as long as the material has the water solubility and the suspension potency in desired dyes. Typically, the average molecular weight is within the range of from 500 to 1,000,000, preferably from 1,000 to 50,000, more preferably from 2,000 to 30,000, more preferably even from 3,000 to 20,000. b) Copolymers of N-vinylpyrrolidone and N-vinylimidazole The polymers of N-vinylimidazole and N-vinylpyrrolidone used in the present invention have a range of average molecular weights of 5000-1,000,000, preferably 5000-200,000. 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 in which said polymer has a range of average molecular weights of from 5,000 to 50,000, more preferably from 8,000 to 30,000, more preferably even from 10,000 to 20,000. The range of average molecular weights per light diffusion was determined as described by Barth H.G. and Mays J.W. , Chemical Analysis Vol 113, "Modern Methods of Polymer Characterization". The highly preferred N-vinylimidazole and N-vinylpyrrolidone copolymers have a range of average molecular weights of from 5,000 to 50,000; more preferably from 8,000 to 30,000; more preferably from 10,000 to 20,000. The copolymers of N-vinylimidazole and N-vinylpyrrolidone characterized in that they have said range of average molecular weights provide excellent dye transfer inhibition properties while not adversely affecting the cleaning performance of the detergent compositions formulated therewith. The copolymer of N-vinylimidazole and N-vinylpyrrolidone of the present invention have a molar ratio of N-vinylimidazole to N-vinylpyrrolidone from 1 to 0.2, more preferably from 0.8 to 0.3, more preferably from 0.6 to 0.4. c) Polyvinylpyrrolidone The detergent compositions of the present invention may also use polyvinylpyrrolidone ("PVP") having an average molecular weight of from about 2,500 to about 400,000, preferably from about 5,000 to about 200,000, more preferably from about 5,000 to about 50,000 and more preferably still from about 5000 to about 15,000. Suitable polyvinyl pyrrolidones are commercially available from ISP Corporation, New York, NY and Montreal, Canada under the product names PVP K-15 (molecular weight with viscosity of 10,000), PVP K-30 (average molecular weight 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 are commercially obtainable from BASF Cooperation include Sokalan HP 165 and Sokalan HP 12; polyvinylpyrrolidones known to those skilled in the detergent field (see for example EP-A-262,897 and EP-A-256,696). d) Polyvinyloxazolidone The detergent compositions of the present invention can also use polyvinyloxazolidone as the polymeric agent of the dye transfer division. Said polyvinyloxazolidones have an average molecular weight of from about 2,500 to about 40,000, preferably from about 5,000 to about 200,000, more preferably from about 5,000 to about 50,000 and more preferably even from about 5,000 to about 15,000. e) Polyvinylimidazole The detergent compositions of the present invention can also use polyvinylimidazole as a polymeric agent for inhibition of dye transfer.

Said polyvinylimidazoles averaged from about 2,500 to about 400,000, preferably from about 5,000 to 200,000, more preferably from about 5,000 to about 50,000 and more preferably even from about 5,000 to about 15,000.

£) Interlaced polymers Interlaced polymers are polymers whose base structure is interconnected to a certain degree; these links can be of a chemical or physical nature, possibly with an active group n in the base structure or on the branches; the entangled 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 that they form a rigid three-dimensional structure, which can trap dyes in the pores formed by the three-dimensional structure. In another embodiment, the entangled polymers trap the dyes by swelling. Such entangled polymers are described in co-pending patent application 94870213.9.

Detergent Components The detergent compositions of the invention may also contain additional detergent components. The precise nature of said additional components, and levels of incorporation thereof 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 according to the invention may be in liquid, paste, gel, stick, tablet, powder and granule form. Granulated compositions can also be found in the "compact" form, liquid compositions can also be found in a form "concentrated." The compositions of the invention can, for example, be formulated as dishwashing compositions by hand and machine, laundry detergent compositions by hand and machine including additive laundry compositions and compositions suitable for use in the rinsing and / or pretreatment of stained fabrics, rinsing of fabric softener compositions added, for use in general hard surface cleaning operations. Compositions of this type containing an alkaline polygalactinase enzyme can provide fabric cleaning, stain removal, maintenance of whiteness, softening, color appearance and inhibition of colloidal transfer when formulated as laundry detergent compositions. When formulated as a composition for use in the manual dishwashing methods, the compositions of the invention preferably contain a surfactant and preferably other detergent compounds selected from the organic polymeric compounds, foam impellers, metal ions of the Group II, solvents, hydrotropes and additional enzymes. When formulated as compositions suitable for use in the laundry machine washing method, the compositions of the invention preferably contain a surfactant and a builder compound and additionally one or more detergent components preferably selected from the polymeric compounds. organic, bleaching agents, additional enzymes, foam suppressors, dispersants, lemon dispersants, soap, dirt suspension and antiredeposition agents and corrosion inhibitors. The laundry compositions may also contain softening agents as additional detergent components. The compositions of the invention can also be used as detergent additive products. Said additive products are intended to complement or increase the performance of conventional detergent compositions. If required, the density in the granular laundry detergent compositions herein ranges from 400 to 1200 g / 1, preferably 600 to 950 g / 1 of the composition measured at 20 ° C. The "compact" form of the laundry detergent compositions herein is best reflected by the density and, in terms of composition, by the amount of inorganic filler salt; the inorganic filler salts are conventional ingredients of detergent compositions in powder form; In conventional detergent compositions, the filler salts are present in substantial amounts, typically 17-35% 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 exceeding 5% by weight of the composition. The inorganic filler salts, as referred to in the present compositions, are selected from the alkali and alkali metal salts of sulfates and chlorides. A preferred filler salt is sodium sulfate. The liquid detergent compositions according to the present invention can also be found in a "concentrated form", in which case, the liquid detergent compositions according to the present invention contain a lower amount of water, compared to conventional liquid detergents. Typically, the water content of the concentrated liquid detergent is preferably less than 40%, most preferably less than 30%, most preferably less than 20% by weight of the detergent composition.

Surfactant System The detergent compositions according to the present invention comprise a surfactant system wherein the surfactant can be selected from nonionic and / or anionic and / or cationic and / or ampholytic and / or zwitterionic surfactants and / or semi-polar. The surfactant is typically present at a level of 0.1% to 60% by weight. Very preferred levels of incorporation are 1% to 35% by weight, most preferably 1% to 30% by weight of the detergent compositions according to the invention. The surfactant is preferably formulated to be compatible with the enzyme components present in the composition. In liquid or gel compositions, the surfactant is most preferably formulated to promote, or at least not degrade, the stability of any enzyme in said compositions. Preferred surfactant systems to be used in accordance with the present invention comprise as the surfactant one or more nonionic and / or anionic surfactants described herein. The polyethylene oxide, polypropylene and polybutylene oxide condensates of alkylphenols are suitable for use as the nonionic surfactant of the surfactant systems of the present invention, with particular preference being given to polyethylene oxide condensates. These compounds include the condensation products of alkylphenols having an alkyl group containing from about 6 to about 14 carbon atoms, preferably from about 8 to about 14 carbon atoms, either in a straight chain or chain configuration branched with the alkylene oxide. In a preferred embodiment, the ethylene oxide is present in an amount equal to from about 2 to about 25 moles, most preferably from about 3 to about 15 moles, of ethylene oxide per mole of alkylphenol. Commercially available nonionic surfactants of this type include Igepal ™ CO-630, marketed 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 (alkylphenol ethoxylates). The condensation products of primary and secondary aliphatic alcohols containing from about 1 to about 25 moles of ethylene oxide are suitable for use as the nonionic surfactant in the present invention. The alkyl chain of the aliphatic alcohol may be straight or branched, primary or secondary, and generally contains from about 8 to about 22 carbon atoms. Preferred are condensation products of alcohols having an alkyl group containing from about 8 to about 20 carbon atoms, most preferably from about 10 to about 18 carbon atoms, with from about 1 to about 10 moles, preferably 2 to 7, most preferably 2 to 5 ethylene oxide per mole of alcohol. Examples of commercially available nonionic surfactants of this type include Tergitol ^ M 15-S-9 (the linear alcohol condensation product of C] _3_-C_5 with 9 moles of ethylene oxide), Tergitol-pM 24- L-6 NMW (the primary alcohol condensation product of C ^ -C ^ with 6 moles of ethylene oxide of narrow molecular weight distribution), both marketed by the Union Carbide Corporation; Neodoltj [45-9 (the condensation product of linear alcohol with 9 moles of ethylene oxide), Neodol ^ M 23-3 (the linear alcohol condensation product of Ci2_cl3 with 3.0 moles of ethylene oxide), Neodol ^ 45-7 (the linear alcohol condensation product of C ^ ^ - ^ s with 7 moles of ethylene oxide) Neodol ^ M 45-5 (the condensation product of linear C14-C15 alcohol with 5 moles of ethylene), marketed by the Shell Chemical Company, KyrotM E0B (the linear alcohol condensation product of c13 ~ c15 with 9 moles of ethylene oxide), marketed by Procter & Gamble Company and Genapol LA 030 or 050 (the linear alcohol condensation product of C] _2 ~ C15 with 3 or 5 moles of ethylene oxide) marketed by Hoechst. The preferred scale of HLB in these products is 8-11 and most preferably 8-10.

Also useful as a nonionic surfactant coagent in the present invention are the alkyl polysaccharides such as those described in the U.S.A. No. 4,565,647, Filling, issued January 21, 1986, having a hydrophobic group containing from 6 to 30 carbon atoms, preferably from about 10 to about 16 carbon atoms, and a polysaccharide, e.g., a polyglycoside hydrophilic group containing from about 1.3 to about 1, preferably from about 1.3 to about 3, more preferably from about 1.3 to about 2.7 units of saccharide. Any reducing saccharide containing 5 or 6 carbon atoms can be used, eg, the glucose, galactose and galactosyl portions can be substituted for the glucosyl portions (optionally the hydrophilic group is attached in the 2-, 3- positions , 4-, etc., thus giving a glucose or galactose as opposed to a glycoside or galactoside). The linkages between saccharides can be eg between position one of the additional saccharide units and positions 2, 3, 4 and / or 6 in the preceding saccharide units. Preferred alkyl polyglycosides have the formula R20 (CnH2nO) t (glucosyl) x wherein R is selected from the group consisting of alkyl, alkylphenyl, hydroxyalkyl, hydroxyalkylphenyl, and mixtures thereof, wherein the alkyl groups contain from about 10 to about 18, preferably from about 12 to about 14 carbon atoms; n is 2 or 3, preferably 2; t is from 0 to about 10, preferably 0; and x is from about 1.3 to about 10, preferably about 1.3 to about 3, most preferably from about 1.3 to about 2.7. The glucosyl is preferably derived from glucose. To prepare these compounds, the alkylpolyethoxylated alcohol or alcohol is first formed, and then reacted with glucose or a source of glucose to form the glucoside (attachment at position 1). The additional glucosyl units can then be fixed between their position '1 and the preceding glucosyl units in the 2-, 3-, 4- and 4- position, preferably predominantly in the 2-position. The oxide condensation products of ethylene with a hydrophobic base formed by the condensation of propylene oxide with propylene glycol are also suitable for use as the additional nonionic surfactant system of the present invention. The hydrophobic portion of these compounds will preferably have a molecular weight of from about 1500 to about 1800, and will exhibit insolubility in water. The addition of polyoxethylene portions to this hydrophobic portion tends to increase the water solubility of the molecule as a whole, and the liquid character of the product is retained to the point where the polyoxethylene content is about 50% of the total weight of the condensation product, which corresponds to the condensation with up to about 40 moles of ethylene oxide. Examples of compounds of this type include certain 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 ethylenediamine. The hydrophobic portion of these products consists of the reaction product of ethylenediamine and excess propylene oxide, and generally has a molecular weight of from about 2500 to about 3000. This hydrophobic portion is condensed with ethylene oxide to the extent that the product of The condensation contains from about 40% to about 80% by weight of polyoxyethylene and has a molecular weight of from about 5000 to about 11000. Examples of this type of nonionic surfactant include certain of the commercially available Tetron? c TxMX compounds marketed by BASF . Preferred for use as the surfactant of the surfactant systems of the present invention are the polyethylene oxide condensates of alkylphenols., condensation products of primary and secondary aliphatic alcohols with about 1 to 25 moles of ethylene oxide, alkylpolysaccharides and mixtures thereof. Most preferred are Cg-C ^ alkylphenol ethoxylates having from 3 to 15 ethoxy ethoxylated ethanol groups of Cg-Cig (preferably C] _Q on average) having from 2 to 10 ethoxy groups, and mixtures thereof. same. The highly preferred surfactants are the polyhydroxy fatty acid amide surfactants of the formula.

R2 - C N - Z, I O R1 wherein R is H, or R1- is C1-C4 hydrocarbyl, 2-hydroxyethyl, 2-hydroxypropyl or a mixture thereof, R is C5-31 hydrocarbyl and Z is polyhydroxyhydrocarbyl having a linear hydrocarbyl chain with at least 3 hydroxyls directly connected to the chain, or an alkoxylated derivative thereof. Preferably, R is methyl, R is a C11-C15 alkyl chain, or an alkyl or alkenyl chain of C ^ gC ^ g such as coconut alkyl or mixtures thereof, and z is derived from a reducing sugar such as glucose, fructose, maltose and lactose, in a reductive amination reaction. Suitable anionic surfactants to be used are linear alkylbenzene sulphonate, alkyl ester sulphonate surfactants including linear esters of C8-C20 carboxylic acids (v. G, fatty acids) which are sulfonated with gaseous SO3 in accordance with "The Journal of the American Oil Chemists Society ", 52 (1975), pp. 323-329. Suitable starting materials may include natural fatty substances such as those derived from tallow, palm oil, etc. The preferred alkyl ester sulphonate surfactant, especially for laundry applications, comprises alkyl ester sulfonate surfactants of the structural formula.

OR II CH C OR- SO3M wherein R3 is a Cg-C2c hydrocarbyl, preferably an alkyl, or combination thereof, R is a hydrocarbyl of C] _-Cg, preferably an alkyl or combination thereof, and M is a salt forming cation which forms a salt soluble in water with the alkyl ester sulfonate. Suitable salt-forming cations include metals such as sodium, potassium and lithium, and substituted or unsubstituted ammonium cations, such as monoethanolamine, diethanolamine and triethanolamine. Preferably, R3 is CiQ-Cig alkyl.

Other suitable anionic surfactants include alkylsulfate surfactants which are water soluble salts or acids of the ROSO3M formule wherein R is preferably a hydrocarbyl of 10-C24, preferably an alkyl or hydroxyalkyl having an alkyl component of Ci0". c20 'most preferably an alkyl or hydroxyalkyl of 0 ^ 2"cg, and M is H or a cation, ie, an alkali metal cation (ie, sodium, potassium, lithium), or substituted ammonium or ammonium ( that is, methyl-, dimethyl-, and trimethyl ammonium cations and quaternary ammonium cations such as tetramethylammonium and dimethyl piperdinium cations and quaternary ammonium cations derived from alkylamines such as ethylamine, diethylamine, triethylamine and mixtures thereof, and the like). Typically, the alkyl chains of C] _2 ~ ci6 are preferred for the lower wash temperatures (ie, below about 50 ° C) and the alkyl chains of C [_ _? g prefer for higher wash temperatures (eg. , above approximately 50 ° C). Other anionic surfactant coagents useful for detersive purposes can also be included in the lavender detergent compositions of the present invention. These may include salts (including, for example, sodium, potassium, ammonium and substituted ammonium salts, such as mono-, di and triethanolamine salts) of soap, C3-C22 primary or secondary alkanesulfonates / Cg-C24 olefinsulfonates, sulfonated polycarboxylic acids prepared by sulfonation of the pyrolyzed product of alkaline earth metal citrates v.gr, as described in the British Patent Specification No. 1,082,179, alkyl polyglycol ether esters of c8-c24 (fJ-e contain up to 10 moles of ethylene); alkyl glyceryl sulfonates, fatty acyl glyceryl sulphonates, fatty oleyl glyceryl sulphonates, alkylphenol ethylene oxide ether sulphates, paraffinsulfonates, alkyl phosphates, isethionates such as acyl isethionates, N-acyl aurates, alkylsuccinamates and sulfosuccinates, monoesters of sulfosuccinates (especially saturated and unsaturated C mono-C ^ g monoesters) ) and diesters of sulfosuccinates (especially saturated and unsaturated Cg-C? 2 diesters), acyl sarcosinates, alkyl polyaccharide sulfates such as alkyl polyglycoside sulphates (the non-sulphonated nonionic compounds described below) and alkyl polyethoxycarboxylates such as those of the formula RO (CH2CH2O) j-CH2COO "M + wherein R is a Cg-C22 alkyl ' k is an integer from 0 to 10, and M is a soluble salt-forming cation Resin acids and hydrogenated resin acids are also suitable, such as colophonic acids, hydrogenated rosin acids and resin acids and hydrogenated resin acids present in or wood oil derivatives Additional examples are described in "Suface Active Agents and Detergents" (Vol.I and II of Schwartz, Perry and Berch.) A variety of such surfactants are also generally described in US Patent 3,929,678, issued on December 30, 1975 Laughlin and others in column 23, line 58, to column 29, row 13 (incorporated herein by reference). included herein, the laundry detergent compositions of the present invention typically comprise from about 1% to about 40%, preferably from about 3% to about 20% by weight of the anionic surfactants. The highly preferred anionic surfactants which include alkoxylated sulfate surfactants herein are the water soluble salts or acids of the formula RO (A) mS? 3M wherein R is an alkyl or hydrocarbyl group of C? _C24 not substituted having an alkyl component of C] _g ~ C24, preferably an alkyl or hydroxyalkyl of Ci2-Cl8 'most preferably an alkyl or hydroxyalkyl of c12"c15' A is an ethoxy or propoxy unit, m is greater than zero, typically between around 0.5 and about 6; most preferably between about 0.5 and about 3, and M is H or a cation which can be, for example, a metal cation (e.g., sodium, potassium, lithium, calcium, magnesium, etc.), a Ammonium or substituted ammonium cation. Ethoxylated alkyl sulfates as well as propoxylated alkyl sulphates are contemplated herein. Specific examples of substituted ammonium cations include methyl-, dimethyl-, trimethylammonium cations and quaternary ammonium cations such as terdamethylammonium and dimethylpiperidinium cations and those derivatives of alkylamines such as ethylamine, diethylamine, triethylamine, mixtures thereof and the like . Exemplary surfactants are polyethoxylated alkyl sulfate (1.0) of Ci2 ~ 18 (C12-C18E (1.0) M), polyethoxylated alkyl sulfate (2.25) of C1-C18 (C12"18E (2 -25) M), polyethoxylated alkyl sulfate (3.0) of C1-C? (C1 -C15E (3.0) M) and polyethoxylated alkyl sulfate (4.0) of C1-C18 (Ci2-C? GE (4.0) M), wherein M is conveniently selected from sodium and potassium. The detergent compositions of the present invention may also contain cationic, ampholytic, zwitterionic and semi-polar surfactants, as well as nonionic and / or anionic surfactants other than those described herein. The cationic detersive surfactants suitable for use in the detergent compositions of the present invention are those which have a long chain hydrocarbyl group. Examples of such cationic surfactants include ammonium surfactants such as alkyltrimethylammonium halides, and those surfactants having the formula: [R2 (OR3) and] [R4 (OR3) and] 2R5N + X- wherein R2 is an alkyl or alkylbenzyl group having from about 8 to about 18 carbon atoms in the alkyl chain, each R3 is selected from the group consists of -CH2CH2-, -CH2CH (CH3) -, -CH2CH (CH2OH) -, -CH2CH2CH2-, mixtures thereof; each R4 is selected from the group consisting of C1-C4 alkyl, C1-C4 hydroxyalkyl, benzyl ring structures formed by joining the two groups R4, CH2CHOH-CHOHCORgCHOHCH2OH wherein Rg is any hexose or hexose polymer having a molecular weight less than about 1000, and hydrogen when and is not 0; R5 is the same as R4 or is an alkyl chain wherein the total number of carbon atoms of R2 plus R5 is not more than about 18; each y is from 0 to approximately 10 and the sum of the values y is from 0 to approximately 15; and X is any compatible anion. The quaternary ammonium surfactant for the present invention has the formula (I): Formula I wherein R 1 is a short chain (C 6 -C 10) alkyl or alkylamidoalkyl alkyl of the formula (II): C Ct ^ Jl tc Formula II and is 2-4, preferably 3. wherein R2 is H or a C1-C3 alkyl, wherein 2 is 0-4, preferably 0-2, most preferably 0, wherein R, R and R5 are the same or different which may be a short chain alkyl (C1-C3) or alkoxylated alkyl of formula III, wherein X "is a counterion, preferably a halide, i.e., chloride or methylsulfate 78 Formula III R6 is C] _- C4 and z is 1 or 2 Preferred quaternary ammonium surfactants are those as defined in formula I wherein: R] _ is C, C] _Q ° mixtures thereof, x = 0, R3, R4 = CH3 and R5 = CH2CH2OH. The highly preferred cationic surfactants are the water-soluble quaternary ammonium compounds useful in the present composition having the formula: R1R2R3R4N + X ~ (i) wherein R ^ is Cg-C ^ alkyl, each R2, R3 and R4 are independently C1-C4 alkyls, C1-C4 hydroxyalkyl, benzyl, and - (C2H4Q) XH wherein x has a value of 2 to 5 , X is an anion. No more than one R, R3 or R4 must be benzyl. The preferred alkyl chain length for R] _ is C 12 -C 15 particularly where the alkyl group is a mixture of chain lengths derived from coconut or palm kernel fat or its synthetic derivatives by olefin accumulation or 0X0 alcohol synthesis . Preferred groups for R2R3 and R3 are methyl and hydroxyethyl groups and the anion X can be selected from halide, methosulfate, acetate and phosphate ions. Examples of the suitable quaternary ammonium compound of the formulas (i) for use herein are: cocotrimethylammonium chloride or bromide; cocomethyldihydroxyethyl chloride or bromide; decyltriethylammonium chloride; decyl dimethylhydroxyethyl onium chloride or bromide; C12-15 dimethylhydroxyethylammonium chloride or bromide; cocodimethylhydroxyethylammonium chloride or bromide; I am sulfur of myristyltrimethylammonium; Lauryl-ethyl-ethyl-benzylammonium chloride or bromide; lauryl dimethyl (etonoxi) 4 ammonium chloride or bromide; choline esters (compound of the formula (i) wherein Ri is CH2-CH2-OC-C12-14 alkyl? R2R3 are methyl or di-alkylimidazoline [compound of formula (i)]. Other cationic surfactants useful in the present are also disclosed in US Patent 4,228,044, Cambre, issued October 14, 1980 and European Patent Application EP 000,224 Typical cationic fabric softening components include the water-insoluble quaternary ammonium fabric softening actives or its precursor of corresponding amine, the most commonly used being di-long chain alkylammonium chloride or methylsulfate.The cationic softeners that are preferred among these include the following: ditallowdimethylammonium chloride (DTDMAC); dihydrogenated sebodimethylammonium chloride; sebodimethylammonium methylsulfamate; dihydrogenated; distearyldimethylammonium chloride; dioleyldimethylammonium chloride; dipamitylhydroxyethylmethyl ammonium chloride; stearylbenzyldimethylammonium, sebotrimethylammonium chloride; hydrogenated sebotrimethylammonium chloride; 10) alkylhydroxyethyldimethylammonium chloride of i2-14; 11) alkyldihydroxyethyldimethylammonium chloride of c12-18 '"12) di (stearoyloxyethyl) dimethylammonium chloride (DSOEDMAC); 13) di (tallowoxyethyl) dimethylammonium chloride; 14) diseboimidazolinium methylsulfate; 15) 1- (2-tallowamemidoethyl) -2-tallowylimidazolinium methylsulfate. Biodegradable quaternary ammonium compounds have been presented as alternatives for traditionally used di-long chain alkyl chlorides and methylsulfates. Said quaternary ammonium compounds contain long chain alkyl (en) yl groups interrupted by functional groups such as carboxyl groups. Such materials and fabric softening compositions containing them are described in numerous publications such as EP-A-0,040,562 and EP-A-0, 239, 910. The quaternary ammonium compounds and amine precursors of the present have the formula ( I) or (II), below: (I) (II) where Q is selected from -0-C (0) -, -C (0) -0-, -0-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; R is C-C4 alkyl or C 1 -C 4 hydroxyalkyl or H; R 4 is H or C 1 -C 4 alkyl or hydroxy alkyl of C 2 -C 4; T1, T2, T3, T4 and T5 are independently C11-C22 alkyl or alkenyl; n and m are integers from 1 to 4; and X- is an anion compatible with softener. Non-limiting examples of anions compatible with softener include chloride or methyl sulfate. The alkyl or alkenyl chain T1, T2, T3, T4 and 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. Particularly preferred are compounds in which T1, T, T3, T4 and T5 represent the mixture of long chain materials typical of tallow. Specific examples of quaternary ammonium compounds for use in the aqueous fabric softening compositions herein include: 1) N, N-di (tallowyloxyethyl) -N, N-dimethylammonium chloride; 2) N, N-di (tallowyloxyethyl) -N-methyl, N- (2-hydroxyethyl) ammonium ethylsulfate; 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 chloride 5) N- (2-tallowyloxy-2-ethyl) -N- (2-seboyl) -oxi-2-oxo-ethyl) -N, N-dimethylammonium; 6) N, N, N-tri (tallowyloxyethyl) -N-methylammonium chloride; 7) N- (2-tallowyl-oxy-2-oxo-ethyl) -N- (tallowyl-N, N-dimethylammonium chloride and 8) 1,2-disodium-oxy-3-trimethylammonium-propane chloride and mixtures of any of the above materials. When included herein, the detergent compositions of the present invention typically comprise from 0.2% to about 25%, preferably from about 1% to about 8%, of said cationic surfactants. The ampholytic surfactants are also suitable for use in the detergent compositions of the present invention. Such 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 or branched chain. One of the aliphatic substituents contains at least about 8 carbon atoms, typically from about 8 to about 18 carbon atoms, and at least one contains an anionic group solubilizable in water, ie, carboxy, sulfonate, sulfate. See patent of E.U.A. 3,929,678 to Laughlin et al., Issued December 30, 1975 in column 19, lines 18-35, for examples of ampholytic surfactants. When included herein, the detergent compositions of the present invention typically comprise from 0.2% to about 15%, preferably from about 1% to about 10%, by weight of said ampholytic surfactants. Zuteinionic surfactants are also suitable for use in detergent compositions. Such surfactants can be broadly described as derivatives of secondary and tertiary amines, derivatives of heterocyclic secondary and tertiary amines, or derivatives of quaternary ammonium, quaternary phosphonium or tertiary sulfonium compound. See patent of E.U.A. DO NOT. 3,929,678 to Laughlin et al., Issued December 30, 1975 in column 19, line 38 to column 22, line 48, for examples of zwitterionic surfactants. When included herein, the detergent compositions of the present invention typically comprise from 0.2% to about 15%, preferably from about 1% to about 10% by weight of said zwitterionic surfactants. Semi-polar nonionic surfactants are a special category of nonionic surfactants that include water-soluble amine oxides containing an alkyl portion of about 10 to about 18 carbon atoms and two portions selected from the group consisting of alkyl group and groups hydroxyalkyl containing from about 1 to about 3 carbon atoms; water-soluble phosphine oxide containing an alkyl portion of about 10 to about 18 carbon atoms and two portions selected from the group consisting of alkyl groups and hydroxyalkyl groups containing from about 1 to about 3 carbon atoms; and water-soluble sulfoxides containing an alkyl portion of about 10 to about 18 carbon atoms and a portion selected from the group that connects X of alkyl and hydroxyalkyl portions of about 1 to about 3 carbon atoms. The semipolar nonionic detergent surfactants include the amine oxide surfactants having the formula 0R3 (OR4) xN (R5) 2 wherein R3 is an alkyl, hydroxyalkyl or alkylphenyl group or mixtures thereof containing from about 8 to about 22 carbon atoms; R is an alkylene or hydrsyalkylene group containing from about 2 to about 3 carbon atoms or mixtures thereof; x is from 0 to about 3; each R is an alkyl or hydroxyalkyl group containing from about 1 to about 3 carbon atoms or a polyethylene oxide group containing from about 1 to about 3 ethylene oxide groups. The R- * can be linked together, that is, by an oxygen or nitrogen atom, to form a ring structure. These amine oxide surfactants in particular include dimethylacyl amine oxide of CiQ-Cig and ammonium oxide of Cg-Ci2 alkoxyethyldihydroxyethyl. When included herein, the detergent compositions of the present invention typically comprise 0.2% a about 15%, preferably about 1 to about 10% by weight of said semi-polar nonionic surfactants. The detergent composition of the present invention may further comprise an adjunct surfactant selected from the group of primary or tertiary amines. Primary amines suitable for use herein include amine according to the formula R1NN-2 wherein Ri is an alkyl chain of C -Ci2 'd preferably C -C? R4 (CE-2) n, X is -0-, - C (0) NH- or -NH-, R4 is an alkyl chain of Cg-c12- n is between 1 to 5, preferably 3. The alkyl chains Ri can be straight or branched and they can interrupt with up to 12, preferably less than 5 portions of ethylene oxide. Preferred families according to the formula herein are N-alkyl amines. Amines suitable for use herein may be selected from 1-hexylamine, 1-octylamine, 1-dicylamine and laurylamine. Other preferred primary amines include C6-C6-oxypropylamine, octioxypropylamine, 2-ethylhexyl-oxypropylamine, laurylamido-propylamine and amidopropylamine. Tertiary amines suitable for use herein include tertiary amines having the formula R 1 R 2 3 N wherein R 1 and R 2 are alkyl chains of C 2 -Cg or R5 - (CH2- CH- 0) xH R3 is any alkyl chain of C-C2, &eq; preferably Cg-10 '° R3 is R4X (CH2) n, wherein X is -O-, -C (0) NH- or -NH-, R4 is C4-C12, n is between 1 to 5, preferably 2-3. R5 is H or C2-C2 alkyl and x is between 1 to 6. R3 and R4 can be linear or branched; alkyl chains of R3 can be interrupted with up to 12, preferably 5, portions of ethylene oxide. The preferred tertiary amines are R 2 3N where R1 is an alkyl chain of C -C2, 2 and R3 is C1-C3 alkyl or - (CH2-CH-0) xH where R5 is CH3 and x = 1-2. Amidoamines of the formula are also preferred: O R1-C II-NH- (CH2) n-N- (R2) 2 wherein R] _ is C -C2 alkyl / n is 2-4, preferably n is 3; R_2 and R3 are C1-C4. Most preferred amines of the present invention include 1-octylamine, 1-hexalamine, 1-decylamine, 1-dodecylamine, C8-10 oxypropylamine, N-coco-1-3-diaminopropane, coco-alkyldimethylamine, lauryldimethylamine, laurylbis (hydroxyethyl) ) amine, coco-bis (hydroxyethyl) amine, lauryl amine propoxylated with 2 moles, popoxylated actylamine with 2 moles, laurylamidopropyl dimethylamine, amidopropyldimethylamine of C8-10 and amidopropyldimethylamine of CIO. The most preferred amines for use in the compositions herein are l-octylamine, l-decylamine, 1- odecylamine. Especially desirable are n-dodecyldimethylamine and bishydroxyethylcocoalkylamine and 7-fold ethoxylated oleylamine, laurylamidopropylamine and cocoamidopropylamine.

Benefits for color care Technologies that provide a type of benefit for color care can also be included. Examples of these technologies are metallocatalysts for color maintenance. Metallocatalysts are also described in European Patent Application No. 92870181.2.

Builder System The compositions of the present invention may further comprise a builder system. Any conventional builder system is suitable for use herein including aluminosilicate materials, silicates, polycarboxilicates, alkylalkenyl succinic acid and fatty acids, materials such as ethylenediaminetetraacetate, diethylenetriaminpentamethylenacetate, metal ion sequestrants such as aminophosphonates, particularly ethylenediaminetetramethylenephosphonic acid and acid. inpentamethylene phosphonic diethylenetria. Phosphate builders can also be used herein. Suitable builders may be an inorganic ion exchange material, commonly an inorganic hydrated aluminosilicate material, more particularly a hydrated synthetic zeolite such as zeolite A, X, B, HS or hydrated MAP. Another suitable inorganic builder material is layered silicate, for example SKS-6 (Hoechst). SK-6 is a crystalline statified silicate consisting of sodium silicate (Na2Si2? _5). Suitable polycarboxylates containing a carboxy group include lactic acid, glycolic acid and ether derivatives thereof as set forth in the Belgian patents Nos. 831,368, 821,369 and 821,370. Carboxylates containing two carboxy groups include the water-soluble salts of succinic acid, malonic acid, ethylenedioxydiacetic acid, maleic acid, diglycolic acid, tartaric acid, tartronic acid and fumaric acid, as well as other ether carboxylates described in German patents 2,446,686 , and 2,446,687 and the US patent No. 3,935,257, and the sulfonyl caboxylates described in Belgian Patent No. 3,935,257. The carboxylates containing three carboxy groups include, in particular, water-soluble citrates, aconitrates and citraconates as well as succinate derivatives such as the carboxymethyloxysuccinates described in British Patent No. 1,379,241, the lactoxysuccinates described in Dutch Application 7205873 and the oxypolycarboxylate such as 2-oxa-l, 1,3-polypanicricarboxylates 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-ethanetenetecorboxylates. 1, 1,3,3-propanotetraorboxylates and 1, 2, 1, 3-propanotetracarboxylatos. Polycarboxylates containing sulfo substituents including sulfosuccinate derivatives described in British Patent Nos. 1,398,421 and 1,398,422 and in the US patent. No. 3,936,448, and the sulfonated pyrolysed sulfonates described in British Patent No. 1,082,179, while exposing the caboxylates containing phosphone substituents of British Patent No. 1,439,000. Alicyclic and heterocyclic polycarboxylates include cyclopentane-cis, cis, cis-tetracarboxylates, cyclo-pentadienidopentacarboxylates, 2,3,4,5-tetrahydro-furan-cis, cis, cis-tetracarboxylates, 2,5-tetrahydra-furan-cis- dicarboxylates, 2, 2, 5, 5-tetrahydrofuran-tetracarboxylates, 1,2,3,4,5,6-hexanohexacarboxylates and carboxymethyl derivatives of polyhydric alcohols such as sorbitol, mannitol and xylitol. Aromatic polycarboxylates include the melitic acid, pyromellitic acid and phthalic acid derivatives set forth in British Patent No. 1,425,343. Of the above, the preferred polycarboxylates are hydroxycarboxylates containing up to three carboxy groups per molecule, more particularly citrates. Preferred builder systems for use in the present compositions include a mixture of a water insoluble aluminosilicate builder such as zeolite A or a layered silicate (SKS-6) and a water soluble carboxylate chelating agent such as citric acid. Preferred builders systems for use in liquid detergent compositions of the present invention are soaps and polycarboxylates.

A suitable chelator for inclusion in the detergent compositions according to the invention is ethylenediamine-N, N'-disuccinic acid or alkali metal salts, alkaline earth metals, ammonium or substituted ammonium thereof or mixtures thereof. The preferred EDDS compounds are the free acid form and the sodium or magnesium salt thereof. Examples of such preferred sodium salts of EDDS include Na2EDDS and Na4EDDS. Examples of such preferred magnesium salts of EDDS include MgEDDS and g2EDDS. Magnesium salts are most preferred for inclusion in the compositions according to the invention. 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. The builders systems to be used in liquid detergent compositions of the present invention are soaps and polycarboxylates. Other detergency builder materials that can form part of the builder system for use in granular compositions include inorganic materials such as carbonates, bicarbonates, silicates and organic materials such as phosphonates, aminopolyalkylene phosphonates and organic aminopolycarboxylates of alkali metals. Other suitable water-soluble organic salts are homo- or copolymeric acids or their salts, in which the polycarboxylic acid comprises at least two carboxyl radicals separated from one another by not more than two carbon atoms. The polymer of this type is exposed in GB-A-1, 596, 756. Examples of such salts are polyacrylates with MW of 2000-5000 and their copolymers with maleic anhydride, such as copolymers having a molecular weight of 20,000 to 70,000, especially about 40,000. Builder salts are usually included in amounts of 5% to 80% by weight of the composition, preferably 10% to 70% and most usually 30% to 60% by weight.

Spudna Suppressor Another optional ingredient is a suds suppressor, exemplified by silicones and silica / silicone blends. The silicones can be represented generally by alkylated polysiloxane materials while the silicas are normally used in finely divided forms exemplified by silica aerogels and xerogels and hydrophobic silicas of various types. These materials can be incorporated as particulate materials in which the foam suppressor is advantageously incorporated in a water-soluble detergent water-soluble or water-dispersible vehicle, substantially non-surfactant. Alternatively, the foam suppressant can be dissolved or dispersed in a liquid vehicle and applied by spraying on one or more of the other components. A preferred silicone foam controlling agent is described, in Bartollota et al., U.S. 3 933 672. Other particularly useful suds 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-544, commercially available from Dow Corning, which is a siloxane-glycol copolymer. The especially preferred foam controlling agent is the foam suppressor system comprising a mixture of silicone oil and 2-alkylalkanols.

The suitable 2-alkylalcanol is 2-butyloctanol which is commercially available under the factory name of Isofol 12 R. Such a foam suppressor system is described in the European patent application N 92870174.7, in progress, filed on November 10, 1992 Particularly preferred silicone foam controlling agents are described in European patent application No. 92201649.8, in progress. Such compositions may comprise a mixture of silicone / silica in combination with fumed non-porous silica such as Aerosil.RTM. The foam suppressors described above are normally employed at levels from 0.001% to 2% by weight of the composition, preferably from 0.01% to 1% by weight.

Other components Other components used in the detergent compositions may be employed, such as soil suspending agents, soil release agents, optical brighteners, abrasives, bactericides, bleaching inhibitors, coloring agents and / or encapsulated or unencapsulated perfumes. Especially suitable encapsulating materials are water soluble capsules consisting of a matrix of polysaccharide and polyhydroxy compounds such as described in GB 1,464,616. Other suitable water-soluble encapsulating materials comprise dextrins derived from ungelatinized starch acid-esters of substituted dicarboxylic acids such as are described in US 3,455,838. These acid-ester dextrins are prepared, preferably, from starches such as waxy maize, waxy sorghum, sago, tapioca and potato. Suitable examples of such 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 polyfunctional substituted groups such as octenylsuccinic acid anhydride. Suitable antiredeposition and soil suspending agents herein include cellulose derivatives such as methylcellulose, carboxymethylcellulose and hydroxyethylcellulose, and homo- or copolymeric polycarboxylic acids or salts thereof. Polymers of this type include the polyacrylates and the maleic anhydride-acrylic acid copolymers previously mentioned as detergency builders, as well as copolymers of maleic anhydride with ethylene, methyl vinyl ether or methacrylic acid, constituting maleic anhydride at least 20% by weight. mol of the copolymer. These materials are normally used at levels of 0.5% to 10% by weight, more preferably 0.75% to 8%, more preferably still 1% to 6% by weight of the composition. Preferred optical brighteners are of anionic character, examples of which are 4,4'-bis- (2-diethanolamino-4-anilino-s-triazin-6-ylamino) stilbene-2,2'-disodium disulfonate, , 4'-bis- (2-mofolino-4-anilino-s-triazin-6-ylamino-stilbene-2, 2'-disodium disodium 4,4'-bis- (2,4-dianilino-s-triazin -6-ylamino) stilbene-2, 2'-monosodium disulfonate, 4 ', 4"-bis- (2,4-dianilino-s-tri-azin-6-ylamino) stilbene-2-sulfonate disodium, 4,4'-bis- (2-anilino-4- (N-methyl-N-2-hydroxyethylamino) -s-triazin-6-ylamino) -stilbene-2, 2'-disodium disulfsnate, 4, 4 ' -bis- (4-phenyl-2, 1, 3-triazol-2-yl) -stilbene-2, 2'-disodium disulfonate, 4,4'bis (2-anilino-4- (1-methyl-2) -hydroxyethylamino) -s-triazin-6-ylamino) -stilbene-2, 2 'disodium disulfonate, 2 (stilbil-4"- (naphtho-1', 2 ': 4, 5) -1.2, 3 -triazole-2"-sodium sulphonate and 4,4'-bis (2-sulfostyril) biphenyl The highly preferred brighteners are the specific brighteners of the application European Patent No. 95201943.8.

Other useful polymeric materials are polyethylene glycols, particularly those with a molecular weight of 1,000-10,000, more particularly from 2,000 to 8,000, and most preferably about 4,000. These are used at levels of 0.20% to 5%, more preferably 0.25% to 2.5% by weight. These polymers and the homo- or copolymeric polycarboxylate salts mentioned above are valuable for improving the maintenance of whiteness, the deposition of ash in the fabric and the cleaning performance on clay, protein and oxidisable soils in the presence of metal impurities of transition. 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 distributions. Examples of such polymers are set forth in the U.S.A. Nos. 4116885 and 4711730, commonly assigned, and published European patent application No. 0 272 033. A particular preferred polymer according to EP-A-0 272 033 has the formula (CH3 (PEG) 43) 0.75 (POH) 0.25 t (T-PO) 2.8 (T-PEG) -0.4 T (P0- H) or.25 ((PEG) 43CH-3) 0.75 where PEG is - (OC2H4) 0-PO is (OC3H60) and T is (pcOC6H CO). Also highly useful are polyester polyesters such as random copolymers of dimethylterephthalate, dimethylsulfoisophthalate, ethylene glycol and 1,2-propanediol, the terminal groups consisting primarily of sulfonbenzoate and secondarily of * monoesters of ethylene glycol and / or propanediol. The objective is to obtain a polymer blocked at both ends by sulfobenzoate groups; "Primordially", in the present context most of said copolymers herein will be blocked at the ends by the sulfobenzoate groups. However, some copolymers will be less than completely blocked and therefore the end groups may consist of monoesters of ethylene glycol and / or popane-1,2-diol, of which they consist "secondarily" in such 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 methylsulfobenzoic acid and about 15% by weight of sulfoisophthalic acid, and has a molecular weight of about 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 from the tap water rapidly deactivates the enzymes comprised in the detergent compositions. Therefore, using chlorine scavenger such as perborate, ammonium sulfate, sodium sulfite or polyethyleneimine with a level greater than 0.1% by weight of the total composition, in the formulas, will provide improvement through the washing stability of the detergent enzymes. The compositions comprising chlorine scavenger are described in European patent application 92870018.6 filed on January 31, 1992. Alkoxylated polycarboxylates, such as those prepared from polyacrylate, are useful herein to provide additional yield in the elimination of fat. Such materials are described in WO 91/08281 and PCT 90/07815 on page 4 and the following, incorporated herein by reference. Chemically, these materials comprise polyacrylates that have a side chain of ethoxy for every 7 and 8 acrylate units. The side chains are of the formula - (CH2-H2?) M (CH2) 11 H3 where m is 2-3 and n is 6-12. The side chains are linked with esters to the polyacrylate "base structure" to provide a "comb" polymer type structure. The molecular weight may vary, but is typically in the range of about 2,000 to about 50,000. Such annealed polycarboxylates may comprise from about 0.05% to about 10%, by weight, of the compositions herein.

SOFTENING AGENTS Fabric softening agents can be incorporated into laundry detergent compositions according to the present invention. These agents may be of inorganic or organic type. Inorganic softening agents are exemplified with the smectite arecillas exposed in GB-A-1 400 898 and USP 5,019,292. Organic fabric softening agents include the water insoluble tertiary amines which are exposed in GBA-A1 514 276 and EP-BO 011 340 and their combination with quaternary ammonium momosales of Ci2 ~ ci4 are disclosed in EP-B-0 026 527 and EP-B-0 026 528 and the dilarga chain amides are exposed in EP-B-0 242 919. Other useful organic ingredients of fabric softening systems include high molecular weight polyethylene oxide materials as set forth in EP. -A-0 299 575 and 0 313 146. The smectite clay levels are usually in the range of 2% to 20%, more preferably 5% to 15% by weight, the material being added as a dry mixed component to the remainder of the composition. the formulation. Other organic fabric softening agents such as water insoluble tertiary amines or dilarga chain amide materials are incorporated at levels of 0.5% to 5% by weight, usually from 1% to 3% by weight while adding high molecular weight polyethylene oxide materials and water soluble cationic materials at levels of 0.1% to 2%, usually 0.15% to 1.15% 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 dry mixed material in the form of particles or sprinkle them as molten liquid over the other solid components of the composition.

Washing Method The compositions of the invention can be used essentially in any washing or cleaning methods, including soaking methods, pretreatment methods and methods with rinsing steps for which a separate auxiliary rinsing composition can be added. The process described herein comprises contacting the fabrics with a washing solution in the usual manner and exemplified herein. The method of the invention is conveniently carried out during the course of the cleaning process. The cleaning method is preferably carried out at 5 ° C and up to 95 ° C, especially between 10 ° C and 60 ° C. The pH of the treatment solution is preferably from 7 to 11. A preferred method for washing dishes by machine comprises treating the soiled articles with an aqueous solution in the dishwashing or machine rinse composition. A conventional effective amount for the machine dishwashing composition means from 8 to 60 g of the product dissolved or dispersed in a wash volume of 3 to 10 liters. According to a manual method for dishwashing, dirty dishes are contacted with an effective amount of the dishwashing composition, typically 0.5 to 20 g (for 25 dishes that are being treated). Manual methods for dishwashing that are preferred include the application of a concentrated solution to the surface of the dishes or soaking in a large volume of diluted solution of the detergent composition. The following examples are intended to exemplify compositions of the present invention, but are not necessarily intended to limit or otherwise define the scope of the invention. In the detergent compositions, the level of enzymes is expressed in pure enzyme by weight of the total composition and the identifications of the abbreviated components have the following meanings: LAS: Sodium C12 linear alkylbenzene sulfonate TAS: sodium tallow alkyl sulfate CXYAS: C-alkyl sulphate? of C? Sodium 25EY: A predominantly linear primary alcohol of C12-C15 condensed with an average of Y moles of ethylene oxide CXYEZ: A predominantly linear primary alcohol of C ?? -C? condensed with an average of Z moles of ethylene oxide XYEZS Alkylsulfate of C -C? of condensed sodium with an average of Z moles of ethylene oxide per mole QAS R2. + (CH3) 2 (C2H 0H) with R2 = C12-C Linear solid sodium alkylcarboxylate soap derived from a mixture of 80/20 oils sebum and coconut Surfactant Ethoxylated / propoxylated mixed non-ionic fatty acid of C 3-C15 with an average degree of ethoxylation of 3.8 and an average degree of propoxylation of 4.5 sold under the trade name Plurafac LF404 by BASF GmbH. CFAA Alkyl-N-methylglucamide of C? 2-Ci4-TFAA Alkyl-N-methylglucamide of C g-Cig. TPKFA C12-C14 full-cut, crowned fatty acids.

DEQA Di- (tallowoxyethyl) dimethylammonium chloride. SDASA 1: 2 ratio of steryl dimethyl amine: triple-compressed stearic acid. Neodol 45-13 Ethoxylated C14-C15 linear primary alcohol, sold by Shell Chemical CO. Silicato amorphous sodium silicate (ratio Si? 2: a2? = 2.0). NaSKS-6 Crystallized statified silicate of the formula delta-Na2SÍ2? 5. Carbonate Anhydrous sodium carbonate with a particle size between 200μm and 900μm. Bicarbonate Anhydrous sodium bicarbonate with a particle size between 400μm and 1200μm. STPP Anhydrous sodium tripolyphosphate. MA / AA Copolymer of maleic / acrylic acid at 1: 4, an average molecular weight of approximately 80,000. PA30 Polyacrylic acid with average molecule weight of approximately 8,000. Terpolymer terpolymer with average molecular weight of about 7,000, comprising acrylic acid: maleic: ethylacrylic acid monomer units with a weight ratio of 60:20:20. 480N Acrylic / methacrylic random copolymer at 3: 7, average molecular weight of about 3,500. Polyacrylate Polyacrylate homopolymer with an average molecular weight of 8,000, sold under the factory name PA30 by BASF GmbH. Zeolite A Hydrated sodium aluminosilicate of the formula Nai2 (IO2SÍO2) 12.27H2O having a primary particle size in the range of 0.1 to 10 micrometers. Citrate trisodium citrate dihydrate with activity of 86.4%, with a particle size distribution between 425.μm and 850 μm. * Citrus anhydrous citric acid. PB1 Anhydrous sodium perborate bleach monohydrate, empirical formula NaB? 2.H2? 2- PB4 Sodium perborate anhydrous tetrahydrate Percarbonate Anhydrous sodium percarbonate bleach of the empirical formula 2Na2C? 3.3H2? 2. TAED Tetraacetylethylenediamine. NOBS Nonanoiloxybenzenesulfonate in the form of sodium salt.

Photoactivated bleach: Sulfonated zinc phthalocyanine encapsulated in dextrin-soluble polymer. PAAC: Cobalt salt (III) of pentamine acetate. Paraffin: Paraffin oil sold under the factory name Winog 70 by Wintershall. BzP: Benzoyl peroxide. Polygalacturonase: Alkaline polygalacturonase as described in Agr. Biol. Chem. (1972) 285-93. Protease: Proteolytic enzyme sold under the trade names Savinasa, Alcalasa, Durazim by Novo Nordisk A / S, Maxacal, Maxapem, Properasa sold by Gist-Brocades and the proteases described in patents WO91 / 06637 and / or WO95 / 10591 and / or EP 251 446. Amylase: Aminolytic enzyme sold with the factory name Ox AmR described in WO 94/18314, WO96 / 05295 sold by Genencor; TermamilR, FungamilR and DuramilR, all obtainable from Novo Nordisk A / S and those described in W095 / 26397. Lipase: Lipolytic enzyme sold under the factory name Lipolasa, Lipolasa Ultra by Novo Nordisk A / S. Cellulase: Cellulite enzyme sold under the factory name Carezime, Celluzime and / or Endolasa by Novo Nordisk A / S.

CMC: Sodium carboxymethylcellulose. HEDP: 1, 1-hydroxyethanediphosphonic acid DETPMP: Diethylenetriaminpenta (methylene phosphoric acid), sold by Monsanto under the factory name Dequest 2060.

PVNO: Poly (4-vinylpyridine) -N-oxide. PVPVI: Poly (4-vinylpyridine) -N-oxide / copolymer of vinylimidazole and vinylpyrrolidone. Brightener 1: Disodium-4,4'-bis (2-sulfostyril) -biphenyl. Brightener 2: Disodium-4,4'-bis (4-anilino-6-morpholino-1,3,5-triazin-2-yl) stilbene-2: 2'-disulfonate. Silicone antifoam: Controller of polydime-ilsiloxane foam with siloxane-oxyalkylene copolymer as a dispersing agent with a ratio of said foam controller to said dispersing agent from 10: 1 to 100: 1. Spupresores: 12% of silicone / silica, 18% of foam granulated stearyl alcohol, 70% of starch in granular form. SRP 1: blocked esters at the sulfobenzoyl ends with an oxyethyleneoxytephthaloyl base structure. SRP 2: Short block polymer of poly (1, 2-propyleneteraphthalate) diethoxylate. Sulfate: Anhydrous sodium sulfate. HMWPEO: High molecular weight polyethylene oxide. PEG: Polyethylene glycol. BTA: Benzotriazole Bismuth nitrate: Bismuth nitrate salt. NaDCC: Sodium dichloroisocyanurate. Encapsulated particle: Technology for the supply of fragrance insoluble fragrance Zeolite 13x perfume and a binder agglomerating detrusor / glycerin is used.

KOH: Active solution of 100% potassium hydroxide. pH: Measured as a 1% solution in distilled water at 20 ° C.

EXAMPLE 1 The following detergent compositions for washing clothes according to the invention were prepared: I II III IV V VI LAS 8.0 8.0 8.0 8.0 8.0 8.0 C25E3 3.4 3.4 3.4 3.4 3.4 3.4 QAS - 0.8 0.8 - 0.8 0.4 Zeolite A 18.1 18.1 18.1 18.1 18.1 18.1 Carbonate 13.0 13.0 13.0 27.0 27.0 27.0 Silicate 1.4 1.4 1.4 3.0 3.0 3.0 Sulfate 26.1 26.1 26.1 26.1 26.1 26.1 PB4 9.0 9.0 9.0 9.0 9.0 9.0 TAED 1.5 1.5 1.5 1.5 1.5 1.5 DETPMP 0.25 0.25 0.25 0.25 0.25 0.25 HEDP 0.3 0.3 0.3 0.3 0.3 0.3 Poligalactu0.005 0.01 0.05 0.01 0.02 0.08 Protease ronasa 0.0026 0.0026 0.0026 0.0026 0.0026 0.0026 Amylase 0.0009 0.0009 0.0009 0.0009 0.0009 0.0009 MA / AA 0.3 0.3 0.3 0.3 0.3 0.3 CMC 0.2 0.2 0.2 0.2 0.2 0.2 Bleach 15 15 15 15 15 15 photoactivated (ppm) Brightener! 0.09 0.09 0.09 0.09 0.09 0.09 Perfume 0.3 0.3 0.3 0.3 0.3 0.3 Anti-foam 0.5 0.5 0.5 0.5 0.5 0.5 silicone Various / secondary ingredients for 100% Density 850 850 850 850 850 850 g / liter EXAMPLE 2 The following granular laundry detergent compositions with a bulk density of 750 g / liter were prepared according to the invention: I II III LAS 5.25 5.61 4.76 TAS 1.25 1.88 1.57 C 5AS - 2.24 3.89 C25AE3S - 0.76 1.18 C45E7 3.25 - 5.0 C25E3 - 5.5 - QAS 0.8 2.0 2.0 STPP 19.7 - - Zeolite A - 19.5 19.5 NaSKS-6 / citric acid (79:: 21) _ 10.6 10.6 Carbonate 6.1 21.4 21.4 Bicarbonate - 2.0 2.0 Silicate 6.8 - - Sodium sulfate 39.8 - 14.3 PB4 5.0 12.7 -TAED 0.5 3.1 -DETPMP 0.25 0.2 0.2 HEDP - 0.3 0.3 Polygalacturonase 0.001 0.02 0.005 Protease 0.0026 0 .0085 0.045 Lipase 0.003 0.003 0.003 Cellulase 0.0006 0 .0006 0.0006 Amylase 0.0009 0.0009 0.0009 MA / AA 0.8 0.6 0.6 CMC 0.2 0.4 0.4 Activated bleach (ppm) 15 ppm 15 ppm 15 ppm Rinse aid i 0.08 0.19 0.19 Rinse aid 2 - 0.04 0.04 Perfume particles 0.3 0.3 0.3 Silicone antifoam 0.5 2.4 2.4 Secondary ingredients / various components for 100% EXAMPLE 3 The following detergent formulations were prepared, in accordance with the present invention, wherein I is a phosphorus-containing detergent composition, II is a detergent composition containing zeolite and III is a compact detergent composition: II III Blown powder STPP 24.0 - 24.0 Zeolite A - 24.0 - C45 S 9.0 6.0 13.0 MA / AA 2.0 4.0 2.0 LAS 6.0 8.0 11.0 TAS 2.0 - - Silicate 7.0 3.0 3.0 CMC 1.0 1.0 0.5 Brightener 2 0.2 0.2 0.2 Soap 1.0 1.0 1.0 DETPMP 0.4 0.4 0.2 Application by sprinkling C45E7 2.5 2.5 2.0 C25E3 2.5 2.5 2.0 Silicone antifoam 0.3 0.3 0.3 Perfume 0.3 0.3 0.3 Dry additives Carbonate 6.0 13.0 15.0 PB4 18.0 18.0 10.0 PB1 4.0 4.0 0 TAED 3.0 3.0 1.0 Photoactivated bleach 0.02 0.02 0.02 Polygalacturonase 0.5 0.05 0.01 Protease 0.01 0.01 0.01 Lipase 0.009 0.009 0.009 Amylase 0.002 0.003 0.001 Sodium sulphate mixed 3.0 3.0 5.0 Dry rest (humidity e 100.0 100.0 100.0 various ingredients) Density (g / liter) 630 670 670 EXAMPLE 4 The following detergent formulations that do not contain bleach of particular use were prepared in the laundry of color laundry, in accordance with the present invention: I II III Blown Powder Zeolite A 15.0 15.0 Sodium Sulfate 0.0 5.0 LAS 3.0 3.0 DETPMP 0.4 0.5 CMC 0.4 0.4 MA / AA 4.0 4.0 Agglomerates C45AS - - 11.0 LAS 6.0 5.0 - TAS 3.0 2.0 - Silicate 4.0 4.0 - Zeolite A 10.0 15.0 13.0 CMC - - 0.5 MA / AA - - 2.0 Carbonate 9.0 7.0 7.0 Application by sprinkling Perfume 0.3 0.3 0.5 C45E7 4.0 4.0 4.0 C25E3 2.0 2.0 2.0 Dry additives MA / AA - - 3.0 NaSKS-6 - - 12.0 Citrate 10.0 - 8.0 Bicarbonate 7.0 3.0 5.0 Carbonate 8.0 5.0 7.0 PVPVI / PVNO 0.5 0.5 0.5 Polygalacturonase 0.05 0 .005 0.02 Protease 0.026 0 .016 0.047 Lipase 0.009 0.009 0.009 Amylase 0.005 0.005 0.005 Cellulase 0.006 0.006 0.006 Silicone antifoam 5.0 5.0 5.0 dry ions Sodium sulphate 0.0 9.0 0.0 Other (humidity e 100.0 100.0 100.0 miscellaneous ingredients) Density (g / liter) 700 700 700 EXAMPLE 5 The following detergent formulations were prepared, in accordance with the present invention: I II III IV LAS 20.0 14.0 24.0 22.0 QAS 0.7 1.0 - 0.7 TFAA - 1.0 - - C25E5 / C45E7 - 2.0 - 0.5 C45E3S - 2.5 - - STPP 30.0 18.0 30.0 22.0 Silicate 9.0 5.0 10.0 8.0 Carbonate 13.0 7.5 - 5.0 Bicarbonate - 7.5 - - DETPMP 0.7 1.0 - - SRP 1 0.3 0.2 - 0.1 MA / AA 2.0 1.5 2.0 1.0 CMC 0.8 0.4 0.4 0.2 Polygalacturonase 0.08 0.04 0.02 0.01 Protease 0.08 0.01 0.026 0.026 Amylase 0.007 0.004 0.002 Lipasa 0 .004 0.002 0.004 0.002 Cellulase 0.? 0004 0.0001 Bleach 70 ppm 45 ppm 10 ppm photoactivated (ppm) Brightener 1 0.2 0.2 0.08 0.2 PB1 6.0 2.0 NOBS 2.0 1.0 Rest (humidity e 100 100 100 100 diverse ingredients) EXAMPLE 6 The following detergent formulations were prepared, in accordance with the present invention: I II III IV Zeolite A 30.0 22.0 6.0 6.7 Na SKS-6 - - - 3.3 Polycarboxylate - - - 7.1 Sodium Sulfate 19.0 5.0 7.0 - MA / AA 3.0 3.0 6.0 - LAS 14.0 12.0 22.0 21.5 C 5AS 8.0 7.0 7.0 5.5 Surfactant - _ _ 1.0 Cationic Silicate - 1.0 5.0 11.4 Soap - - 2.0 - Brightener 1 0.2 0.2 0.2 - Carbonate 8.0 16.0 20.0 10.0 DETPMP - 0.4 0.4 - Spray ligation C45E7 1.0 1.0 1.0 3.2 dry additives PVPVI / PVNO 0.5 0.5 0.5 - Polygalacturonase 0.005 0.01 0.01 0.005 Protease 0.05 0.01 0.005 0.01 Lipase 0.009 0.009 0.009 0.009 Amilase 0.0008 0.0008 0.0008 0.0008 Cellulase 0.0002 0.0002 0.0002 0.0002 NOBS - 6.1 4.5 3.2 PB1 1.0 5.0 6.0 3.9 Sodium Sulfate - 6.0 - for the rest Rest (humidity 100 100 100 100 different ingredients) EXAMPLE 7 The following high density and bleach-containing detergent formulations were prepared according to the present invention: I II III Zeolite Blowing Powder A 15.0 15.0 15.0 Sodium Sulfate 0.0 5.0 0.0 LAS 3.0 3.0 3.0 QAS - 1.5 1.5 DETPMP 0.4 0.4 0.4 CMC 0.4 0.4 0.4 MA / AA 4.0 2.0 2.0 Agglomerates LAS 5.0 5.0 5.0 TAS 2.0 2.0 1.0 Silicate 3.0 3.0 4.0 Zeolite A 8.0 8.0 8.0 Carbonate 8.0 8.0 4.0 Application by spray Perfume 0.3 0.3 0.3 C45E7 2.0 2.0 2.0 C25E3 2.0 _ _ Dry additives Citrate 5.0 - 2.0 Bicarbonate - 3.0 - Carbonate 8.0 15.0 10.0 TAED 6.0 2.0 5.0 PB1 14.0 7.0 10.0 Polyethylene oxide with - - 0.2 MW of 5,000,000 Bentonite clay - - 10.0 Polygalacturonase 0.005 0.011 0.08 Protease 0.01 0.01 0.01 Lipase 0.009 0.009 0.009 Amylase 0.005 0.005 0.005 Cellulase 0.002 0.002 0.002 Silicone antifoam 5.0 5.0 5.0 Dry additives Sodium sulfate 0.0 3.0 0.0 Rest (moisture and miscellaneous ingredients) 100.0 100.0 100.0 Density (g / liter) 850 850 850 EXAMPLE 8 The following high density detergent formulations were prepared according to the present invention: II Agglomerate C45 S 11.0 14.0 Zeolite A 15.0 6.0 Carbonate 4.0 8.0 MA / AA 4.0 2.0 CMC 0.5 0.5 DETPMP 0.4 0.4 Spray application C25E5 5.0 5.0 Perfume 0.5 0.5 Dry additives HEDP 0.5 0.3 SKS 6 13.0 10.0 Citrate 3.0 1.0 TAED 5.0 7.0 Percarbonate 20.0 20.0 SRP 1 0.3 0.3 Polygalacturonase 0.02 0.02 Protease 0.04 0.04 Lipase 0.009 0.009 Cellulase 0.004 0.004 Amylase 0.005 0.005 Silicone antifoam 5.0 5.0 Brightener 1 0.2 0.2 Brightener 2 0.2 -Rest (moisture and ingredients 100 100 various) Density (g / liter) 850 850 EXAMPLE 9 The following granular detergent formulations were prepared according to the present invention: I II III IV V LAS 21.0 25.0 18.0 18.0 - COCO- (AS de C12-14) - - - - 21.9 AE3S - - 1.5 1.5 2.3 Decildimethylhydroxyethyl - 0.4 0.7 0.7 0.8 NH4 + C1 Surfactant 1.2 - 0.9 0.5 - non-ionic Coco- (fatty alcohol - - - - 1.0 C12-14) STPP 44.0 25.0 22.5 22.5 22.5 Zeolite A 7.0 10.0 - - 8.0 MA / AA - - 0.9 0.9 - SRP1 0.3 0.15 0.2 0.1 0.2 CMC 0.3 2.0 0.75 0.4 1.0 Carbonate 17.5 29.3 5.0 13.0 15.0 Silicate 2.0 - 7.6 7.9 - Polygalacturonase 0.005 0.01 0.007 0.01 0.007 Protease 0.007 0.007 0.007 0.007 0.007 Amylase - 0.004 0.004 0.004 0.004 Lipasa 0.003 0.003 0.003 - - Celulasa - 0.001 0.001 0.001 0.001 NOBS - - - 1.2 1.0 PB1 _ _ _ 2.4 1.2 Diethylenetriamine-0.7 1.0 pentaacetic acid Diethylenetriamine-0.6 pentamethylphosphonic acid uae ao? V? G ua Photoactivated bleach 45 50 15 45 42 ppm ppm ppm ppm ppm Polisher 1 0.05 - 0.04 0.04 0.04 Polisher 2 0.1 0.3 0.05 0.13 0.13 Water and minor ingredients up to 100% EXAMPLE 10 The following liquid detergent formulations were prepared according to the present invention: I II III IV V VI VII VIII LAS 10.0 L3.0 9.0 - 25.0 _ _ - C25AS 4.0 1.0 2.0 10.0 - 13.0 18.0 15.0 C C2255EE33SS 1 1..00 - - 3.0 - 2.0 2.0 4.0 C25E7 6.0 8.0 13.0 2.5 - - 4.0 4.0 TFAA - 4.5 - 6.0 8.0 8.0 QAS - 3.0 1.0 TPKFA 2.0 13.0 2.0 - 15.0 7.0 7.0 cciiddooss ggrraassooss - - - 5.0 - - 4.0 4.0 Rapeseed seed Citric acid 2.0 3.0 1.0 1.5 1.0 1.0 1.0 1.0 Acid 12.0 10.0 - - 15.0 dodecetyltetra-decenylsuccinic Oleic acid 4.0 2.0 1.0 - 1.0 Ethanol 4.0 4.0 7.0 2.0 7.0 2.0 3.0 2.0 1,2-Propanediol 4.0 4.0 2.0 7.0 6.0 8.0 10.0 13.0 Monoethanol Amina - - - 5.0 - - 9.0 9.0 Triethanolamine Amina - _ 8 - - - - - NaOH (pH) 8.0 8.0 7.6 7.7 8.0 7.5 8.0 8.2 Tetraethylene 0.5 - 0.5 0.2 - - 0.4 0.3 Ethoxylated pentamine DETPMP 1.0 1.0 0.5 1.0 2.0 1.2 1.0 SRP-2 0.3 - 0.3 0.1 - - 0.2 0.1 PVNO - - - - - - - 0.10 Polygalacturo- .005 .005 .005 .005 0.05 0.07 0.02 0.01 nasa Protease .005 .005 .004 .003 .008 .005 .003 .006 Lipase - .002 - .002 - - .003 .003 Amylase .002 .002 - - .002 - .005 .005 Cellulase - .0001 - - .0002 .0001 peroxide Boric acid 0.1 0.2 - 2.0 1.0 1.5 2.5 2.5 Na Formate - - 1.0 Ca Chloride - 0.015 - 0.01 - Clay - - - - 4.0 4.0 Bentonite Clay in - - - - 0.6 0.3 SD3 The rest 100 100 100 100 100 100 100 100 (moisture and miscellaneous ingredients): EXAMPLE eleven Granular fabric cleaning compositions were prepared which provide "wash-softening" capability, according to the present invention: I II 45AS - 10.0 LAS 7.6 - 68AS 1.3 - 45E7 4.0 - 25E3 - 5.0 COCO Chloride - alkyl- 1.4 1.0 dimethylhydroxyethylammonium Citrate 5.0 3.0 Na-SKS-6 - 11.0 Zeolite A 15.0 15.0 MA / AA 4.0 4.0 DETPMP 0.4 0.4 PB1 15.0 - Percarbonate - 15.0 TAED 5.0 5.0 Smectite clay 10.0 10.0 HMWPEO - 0.1 Polygalacturonase 0.01 0.01 Protease 0.02 0.01 Lipase 0.02 0.01 Amylase 0.03 0.005 Cellulase 0.001 - Silicate 3.0 5.0 Carbonate 10.0 10.0 Granular foam suppressor 1.0 4.0 CMC 0.2 0.1 Water / minor ingredients up to 100: O, EXAMPLE 12 The following fabric softener composition with added rinse was prepared according to the present invention: Softening active 20.0 Polygalacturonase 0.01 Amylase 0.001 Cellulase 0.001 HCL 0.03 Antifoam agent 0.01 Blue dye 25 ppm CaCl2 0.20 Perfume 0.90 Water / minor ingredients up to 100% EXAMPLE 13 The following fabric softening composition was prepared, in accordance with the present invention: I II III DEQA 2.60 19.00 SDASA - - 70.0 Stearic acid with VY = 0 0.30 - Neodol 45-13 - - 13.0 Hydrochloric acid 0.02 0.02 Ethanol - - 1.0 PEG - 0 0..6600 - Poligalacturonase 0 0..000055 0 0..0055 0.01 Perfume 1 1..0000 1 1.000 0.75 Digeranyl succinate - - 0.38 Silicone antifoam 0 0..0011 0 0..001 - Electrolyte - 6 60000pp; pm - Colorant llOOOOppppmm 5 500ppppmm 0.01 Water and ingredients menore 1 10000 %% 1 1000% _ EXAMPLE 14 The Syndet bar cloth cleaning compositions were prepared according to the present invention: I II III IV C26 AS 20.00 20.00 20.00 20.00 CFAA 5.0 5.0 5.0 5.0 LAS (Cll-13) 10.0 10.0 10.0 10.0 Sodium carbonate 25.0 25.0 25.0 25.0 Sodium pyrophosphate 7.0 7.0 7.0 7.0 STPP 7.0 7.0 7.0 7.0 Zeolite A 5.0 5.0 5.0 5.0 CMC 0.2 0.2 0.2 0.2 Polyacrylate (MW 1400) 0.2 0.2 0.2 0.2 Coconut Monetanolamide 5.0 5.0 5.0 5.0 Polyigalcturonase 0.1 0.1 0.15 0.2 Amylase 0.01 0.02 - - Protease 0.3 - 0.5 0.05 Brightener, perfume 0.2 0.2 0.2 0.2 CaS04 1.0 1.0 1.0 1.0 MgS04 1.0 1.0 1.0 1.0 Water 4.0 4.0 4.0 4.0 Filler *: rest for 100% Suitable materials may be selected, such as CaCO3, talc, clay (kaolinite, smectite), silicates and the like.

EXAMPLE 15 The following compact, high-density dishwashing detergent compositions (0.96 Kg / 1) were prepared in accordance with the present invention: I II III IV V VI STPP - - 49.0 38.0 - - Citrate 33.0 17.5 - - 54.0 25.4 Carbonate - 17.5 - 20.0 14.0 25.4 Silicate 33.0 14.8 20.4 14.8 14.8 - Metasilicate - 2.5 2.5 - - - PB1 1.9 9.7 7.8 14.3 7.8 - PB4 8.6 - - - - - Percarbonate - - - - - 6.7 Agent tensioac1.5 2.0 1.5 1.5 1.5 2.6 non-ionic agent TAED 4.8 2.4 2.4 - 2.4 4.0 HEDP 0.8 1.0 0.5 - - - DETPMP 0.6 0.6 - - - - PAAC - - - 0.2 - - BzP - - - 4.4 - - Paraffin 0.5 0.5 0.5 0.5 0.5 0.2 Polygalacturonase 0.07 0.05 0.1 0.001 0.08 0.01 Protease 0.075 0.05 0.10 0.10 0.08 0.01 Lipase - 0.001 - 0.005 - - Amylase 0.01 0.005 0.015 0.015 0.01 0.0025 BTA 0.3 0.3 0.3 0.3 0.3 - Nitrate of - 0.3 - - - - * bismuth PA30 4.0 - - - - - Terpolymer - - - 4.0 - - 480N - 6.0 2.8 - - - Sulphate 7.1 20.8 8.4 - 0.5 1.0 pH (solution 10.8 11.0 10.9 10.8 10.9 9.6 to 1%) EXAMPLE 16 The following granular dishwashing detergent compositions were prepared, examples I to IV, with a density of 1.02 kg / 1, according to the present invention: I II III IV V VI STPP 30.0 30.0 30.0 27.9 34.5 26.7 Carbonate 30.5 30.5 30.5 23.0 -30.5 2.80 Silicate 7.4 7.4 7.4 12.0 8.0 20.3 PB1 4.4 4.4 4.4 _ 4.4 _ NaDCC - - - 2.0 - 1.5 Agent tensioac0.75 0.75 0.75 1.9 1.2 0.5 non-ionic TAED 1.0 1.0 - - 1.0 PAAC - - 0.004 - - BzP - 1.4 - - - Paraffin 0.25 0.25 0.25 - - Polygalacturonase 0.01 0.01 0.01 0.05 0.01 0.05 Protease 0.05 0.05 0.05 - 0.1 Lipase 0.05 - 0.001 - - Amylase - - 0.01 0.02 0.01 BTA 0.15 - 0.15 - - Sulfate 23.9 23.9 23.9 31.4 17.4 pH (solution 10.8 10.8 10.8 10.7 10.7 12.3 to 1%) EXAMPLE 17 The following detergent composition tablets of 25 g in weight, according to the present invention, were prepared by compressing a granular dishwashing detergent composition at a pressure of 13 KN / cm using a regular rotary press of 12 heads: I II III STPP - 48.8 47.5 Citrate 26.4 Carbonate - 5.0 - Silicate 26.4 14.8 25.0 Polygalacturonase 0.007 0.01 0.05 Protease 0.03 0.075 0.01 Lipase 0.01 - - Amylase 0.01 - 0.00 PB1 1.6 7.8 - PB4 6.9 - 11.4 Surfactant 1.2 2.0 1.1 non-ionic TAED 4.3 2.4 0.8 HEDP 0.7 - - DETPMP 0.65 - - Paraffin 0.4 0.5 - BTA 0.2 0.3 - PA30 3.2 - - Sulfate 25.0 14.7 3.2 pH (1% solution 10.6 10.6 11.0 EXAMPLE 18 The following liquid dishwashing detergent compositions were prepared, according to the present invention I to II, with a density of 1.40 kg / 1: I II STPP 33.3 20.0 Carbonate 2.7 2.0 Silicate - 4.4 NaDCC 1.1 1.15 Surfactant 2.5 1.0 nonionic Paraffin 2.2 - Polygalacturonase 0.005 0.05 Protease 0.03 0.02 Amylase 0.005 - 480N 0.50 4.00 KOH - 6.00 Sulfate 1.6 -pH (1% solution) 9.1 10.0 EXAMPLE 19 The following hard surface cleaning compositions were prepared according to the present invention: I II III IV V VI Polygalacti- 0.005 0.01 0.02 0.02 0.005 0.005 rusty Amylase - - 0.005 0.02 - 0.005 Protease 0.05 0.01 0.02 0.03 0.005 0.005 EDTA * - - 2.90 2.90 Citrate - - - - 2.90 2.90 LAS 1.95 - 1.95 - 1.95 - AS of C12 - 2.20 2.20 - 2.20 Sulphate of - 2.20 2.20 _ 2.20 C12 of Na (ethoxy) Oxide of - 0.50 - 0.50 - 0.50 dimeti1amine of C12 SCS 1.30 - 1.30 - 1.30 Hexilcarbitol ** 6.30 6.30 6.30 6.30 6.30 6.30 Water The rest for 100% * Ethylenediamine diacetic acid of Na4 ** Diethylene glycol monohexyl ether *** All formulas adjusted to pH 7 EXAMPLE 20 The following spray composition will be prepared for cleaning hard surfaces and removing fungus in the home, in accordance with the present invention: I Polygalacturonase 0.01 Amylase 0.01 Protease 0.01 Sodium Octyl Sulfate 2.00 Sodium dodecylisulfate 4.00 Sodium hydroxide 0.80 Silicate (Na) 0.04 Perfume 0.35 Water / minor ingredients up to 100%

Claims (15)

NOVELTY OF THE INVENTION CLAIMS

1. - A detergent composition comprising a substantially free poligalacturanasa enzyme other pectic enzymes having an enzymatic activity of at least 10%, preferably 25%, most preferably 40% of its optimum activity, at a pH ranging from 7 to 11.

2. a detergent composition according to claim 1 further characterized in that said poligalacturanasa enzyme has an optimal activity at a pH ranging from 7 to 11.

3. - a detergent composition according to claims 1-2, characterized further because said polygalactinase enzyme is present at a level of from 0.0001% to 2%, preferably from 0.0005% to 0.5%, most preferably from 0.001% to 0.1% pure enzyme by weight of the total composition.

4. - A detergent composition according to claims 1-3, comprising less than 25%, preferably less than 10%, most preferably less than 5% by weight of the enzyme polygalactinase, of other pectic enzymes.

5. A detergent composition according to any of the preceding claims, further characterized in that it comprises a dispersant.

6. - A detergent composition according to any of the preceding claims, further characterized in that it comprises another detergent enzyme.

7. A detergent composition according to claim 6, further characterized in that said detergent enzyme is selected from cellulase, protease, lipase, amylase and / or mixture thereof.

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

9. A detergent composition according to any of the preceding claims, further characterized in that it comprises a conventional activated bleaching system with a bleaching catalyst based on Mn.

10. - A detergent composition according to any of the preceding claims, further characterized in that it comprises a dye transfer inhibiting polymer.

11. A detergent composition according to any of the preceding claims, further characterized in that said composition is in liquid, paste, gel, bar, tablet, powder or granulated form.

12. A detergent additive comprising a polygalactinase enzyme substantially free of other pectic enzymes having an enzyme activity of at least 10%, preferably 25%, most preferably 40% of its optimum activity, at a pH ranging from 7 to 11.

13. The use of a detergent composition according to any of the preceding claims for fabric cleaning and / or removal of fabric stains and / or maintenance of whiteness of fabrics and / or fabric softening and / or appearance of fabric color and / or inhibition of dye transfer in fabrics.

14. The use of a detergent composition according to claims 1-12 for cleaning hard surfaces such as floors, walls, bathroom mosaic and the like.

15. The use of a detergent composition according to claims 1-12 for manual and machine dishwashing.