MXPA96004781A - Detergents containing an enzyme and a retard releasing peroxiacide sistemablanqueador - Google Patents

Abstract

A detergent composition containing a) an enzyme is provided, and b) an organic peroxyacid bleach system wherein means are provided to retard the release to a wash solution of said peroxyacid bleach in connection with the release of said enzyme.

Description

'-DETERGENT PUF CONTAINS AN ENZYME AND A PEROXIflCTDO BLQNOUEßDOR SYSTEM. RELEASE RETPRDPDft This invention relates to detergent compositions containing an enzyme, preferably an arnilasse enzyme, and an organic peroxyacid bleach system; wherein a means is provided for retarding the release of organic peroxy acid bleach to the wash solution, with respect to the release of the enzyme. Successful removal of naturally occurring color stains / spots, such as blood, egg, chocolate, gravy, from soiled / soiled substrates, is a particular challenge for the formulator of a detergent composition for use in a washing method, such as a method of washing fabrics or a method of washing dishes in a machine. Traditionally, the removal of such stains / stains of color has been facilitated by the use of bleaching components, such as oxygen bleaches, which include hydrogen peroxide and organic peroxyacids, and also by enzyme components. Organic peroxyacids are frequently obtained by the perhydrolysis reaction, carried out in aitu. between the hydrogen peroxide and an organic peroxyacid bleach precursor. A problem encountered with the use of certain organic peroxyacid bleaches, in washing methods, is the tendency of these organic peroxyacid bleaches to affect the color stability of the products that are being used. The types of damage to fabrics can include the opacity of the fabric's color dyes, or localized areas of color bleaching in the form of "patches." A problem encountered with the use of enzymes as detergent components , is that the enzymatic activity in the washing can be affected by the presence of the detergent components present in the washing solution.The degradation of the enzymes by the bleaching components has been found to be a particular problem. found that the degradation of the enzyme substrates by the bleach reduces the activity of the enzyme, particularly the amylase. The challenge of formulating a product that maximizes the removal of dirt / stains, but minimizes the occurrence of any degradation of the enzymes, undesirable, or effects on the color stability of the fabrics, by the bleach. The inventors of the present have found that the occurrence of any undesirable effect on the color stability of the fabric or any degradation effect of the enzyme, which is due to the use of organic peroxyacid bleach in a washing method, can be relate to the égirnen or release rate of the peroxyacid bleach to the wash solution, and also to the absolute level of peroxyacid that is present in the wash solution. A rapid rate or rate of release of the peroxyacid bleach to the wash solution tends to highlight the likelihood of undesirable effects occurring on the color stability of the fabrics, and degradation effects of the enzyme, as well as a high absolute level of the bleach in the washing solution. While reducing the release rate of the peroxyacid bleach or the absolute level of the bleach employed in the washing tends to improve these problems, this may be accompanied by a negative effect on the ability to remove bleaching stains / grime. The inventors, however, have found that when a composition containing both an organic enzyme is employed a source of peroxyacid bleach, and wherein a means is provided to retard the release of the peroxyacid bleach to a washing solution, with With respect to the release of the enzyme, an improved removal of stains / grime can be obtained, particularly of naturally occurring spots / blots of color. The invention is particularly useful for compositions containing proteases, lipases and, particularly, amylases, cellulases and peroxidases.

In addition, when the composition is used in a method for washing fabrics, a reduction in the propensity to observe negative effects on the color stability of the fabrics is also obtained.Therefore, it is an object of the present invention providing compositions suitable for use in machine washing and dishwashing methods, which have increased stain removal, It is also an object of the present invention to Aroveer compositions for use in a fabric washing method wherein compositions show less propensity to cause negative effects on the color stability of the fabrics.

BRIEF DESCRIPTION OF THE INVENTION In accordance with one aspect of the present invention, ^ 3 provides a detergent composition containing: a) an enzyme; and b) an organic peroxyacid bleach system; wherein a means is provided for retarding the release of said organic peroxyacid to a wash solution, with respect to the release of the enzyme; such that in the T50 test method, described herein, the time to obtain a concentration that is 50% of the final concentration of the enzyme is less than 120 seconds; and the time to obtain a concentration of 50% of the final concentration of the organic peroxyacid is greater than 180 seconds. According to another aspect of the present invention, a detergent composition is provided which contains: (a) an enzyme; and (b) an organic peroxyacid bleach system; wherein a means is provided for retarding the release of said organic peroxyacid to a wash solution, with respect to the release of the enzyme, so that, in the T50 test method described herein, the time to obtain a concentration q? e is 50% of the final concentration of the enzyme is at least 100 seconds, preferably at least 120 seconds, better still, at least 150 seconds, less than the time to obtain a concentration that is 50% of the final concentration of organic peroxyacid. The organic peroxyacid bleach system preferably comprises, in combination: i) a source of hydrogen peroxide; and (ii) an organic peroxyacid bleach precursor compound.

The enzyme An essential component of the detergent compositions is an enzyme. Suitable enzymes include lipases, arnilases, neutral and alkaline lipases, cellulases, pectinases, lactases and peroxidases obtainable commercially, ie enzymes having lipolytic, amylolytic, proteolytic, cellulolytic, pectolytic, lactolytic activity. and peroxydolitics, respectively, conventionally incorporated into detergent compositions Suitable enzymes are discussed in US Patents 3,519,570 and 3,533,139 Protease enzymes are the especially preferred enzyme component Commercially available protease enzymes include those sold under the trade names Alcalase, Savinase, Primase, Durazym and Esperase by Novo Industries A / S (Denmark), those sold under the trade name Maxatase, Maxacal and Maxapem by Gist-Brocades, the sales by Genencor International and those sold under the trade names Opticlean and Optirnase by Solvay Enzymes.

The protease enzyme can be incorporated in the compositions z according to the invention at a level of 0.0001 to 4% of active enzyme, by weight of the composition. Preferred amylases include, for example, α-amylases, obtained from a special strain of B. licheniformis, described in greater detail in GB-1,269,839 (Novo). Preferred amylases, obtainable commercially, include, for example, those sold under the tradename Rapidase by G.ist ~ Brocades and those sold under the trade name Termamyl and BAN by Novo Industries A / S. The enzyme amylase can be incorporated into the composition according to the invention at a level of 0.0001% up to 2% of active enzyme, by weight, with respect to the composition. The lipolytic enzyme (lipase) can be present at levels of active lipolytic enzyme from 0.0001% to 2% by weight, preferably from 0.001% to 1% by weight, most preferably from 0.001% to 0.5% by weight, based on weight of the composition. The lipase can be of fungal or bacterial origin, obtaining, for example, a pair + from a lipase producing strain of Humi ola sp. , Th rmomv? GS sp. Or Pseudomonas sp., Including Pseudoditomas DSBudoalkalioflnBR or Pseudomonas fluorescens. Lipase from mutants of these strains, chemically or genetically modified, are also useful here. A preferred lipase is derived from Pse? Domonas Dse? Doalcaligenes. which is described in the European patent granted EP-B-0,218, 272. Another preferred lipase herein is obtained ~ aligning the gene of Humicola lanuqinosa and expressing the gene in Asperaillus orvzae. as host, as described in European patent application EP-A-0,258,068, which is commercially available from Novo Industri A / S, Bagsvaerd, Denmark, under the name Lipolase. This lipase is also described in U.S. Patent 4,810,414, Huge-Jensen and co-inventors, issued March 7, 1989. ~ > C1 organic peroxyacid bleach system An essential aspect of the invention is an organic peroxyacid bleach system. In a preferred embodiment, the bleaching sis + erna contains a source of hydrogen peroxide and an organic peroxyacid bleach precursor compound. The production of the organic peroxyacid occurs by an in situ reaction of the precursor with a source of hydrogen peroxide. Preferred sources of hydrogen peroxide include inorganic perhydrate bleaches. In an alternative preferred embodiment, a preformed organic peroxyacid is incorporated directly into the composition. Compositions containing mixtures of a source of hydrogen peroxide and organic peroxyacid precursor, in combination with a preformed organic peroxyacid, are also contemplated. __os inorganic hydrocarbon bleaches The inorganic perhydrate salts are usually incorporated in the form of the sodium salt, at a level of 1% to 40% by weight, better still, from 2% to 30% by weight and, most preferred, of 5% to 25% by weight of the compositions. Examples of the inorganic perhydrate salts include the perborate, percarbonate, petent, persulfate and persilicate salts, and any mixtures thereof.

The inorganic perhydrate salts are usually the alkaline metal salts. The inorganic perhydrate salt may be included as the crystalline solid, without additional protection. However, for certain perhydrate salts, the preferred embodiments of said granulated compositions utilize a coating coated with the material, which provides better storage stability for the perhydrate salt in the granulated product. Sodium perborate may be in the form of the monohydrate of the nominal formula: NaBOa-HaOs », or the tetrahydrate aBOsíHszOz 3HaO. The alkali metal percarbonates, particularly sodium percarbonate, are the preferred perhydrates to be included in the compositions according to the invention. It has been found that compositions containing percarbonate have a reduced tendency to form undesirable gels in the presence of surfactants and water, than similar compositions containing perborate. It is believed that this is because typically, the percarbonate has a smaller surface area and smaller porosity than the perborate monohydrate. This low surface area and low porosity act to prevent cogelling with the fine particles of the agglomerates of surfactant and, therefore, are not harmful when dispensed. Sodium percarbonate, which is the preferred perhydrate to be included in the compositions according to the present invention, is an addition compound having a formula corresponding to 2Na = .C03 IH ^ O ^, and is available commercially as? n crystalline solid. The percarbonate, most preferably, is incorporated into the compositions in a coated form, which gives stability to the product. A suitable coating material which gives product stability comprises the mixed salt of a sulphate and an alkaline metal carbonate, soluble in water. Said coatings, together with the coating processes, have been previously described in GB-1, 466, 799, granted to Interox on March 9, 1977. The weight ratio of the mixed salt coating material to the percarbonate lies in the scale from 1: 200 to 1: 4, better yet, from 1:99 to 1: 9 and, most preferably, from 1:49 to 1:19. Preferably, the mixed salt is sodium sulfate and sodium carbonate, which has the general formula: NaaS0 • n.Na2C0a, wherein n is from 0.1 to 3, preferably, n is from 0.3 to 1.0 and, most preferably, n is from 0.2 to 0.5. Other coatings containing silicate (alone or with borate salts or boric or other inorganic acids), waxes, oils, fatty soaps, may also be advantageously used within the present invention. Potassium peroximonopersulfate is another inorganic perhydrate salt for use in the detergent compositions herein. 51 precursor «Je blangueatior g peroxiácigo Peroxyacid bleach precursors are compounds that react with hydrogen peroxide in a perhydrolysis reaction to produce a peroxyacid.

Generally peroxyacid bleach precursors can be represented as: 0 X C - L wherein L is a substitutable group, such that, when subjected to perhydrolysis, the structure of the produced peroxyacid is: 0 Said peroxy acid bleach precursor compounds are preferably incorporated at a level of from 0.5% to 20% by weight, better still, from 1% to 15% by weight, especially from 1.5% to 10% by weight of the compositions. Suitable peroxyacid bleach precursor compounds typically contain one or more N- or O-acyl groups, and said precursors may be selected from a wide range of classes. Suitable classes include the -anhydrides, esters, umides, lactams, and acylated derivatives of nidazoles and oxiranes. Examples of useful materials within those classes are described in GB-A-1, 586,789. Suitable esters are described in GB-A-836,988, 864,798, 1,147,871, 2,143,231 in EP-A-0, 170,386. The inventors of the present have found that "patching" damage can be particularly associated with the peroxyacid bleach precursor compounds which, when subjected to perhydrolysis, provide a peroxyacid which is: (i) a perbenzoic acid or a non-derivative substituted cationic of the same; or (ii) a cationic peroxyacid. It has also been found that benzoxazine precursors are particularly susceptible to the aforementioned problem.

SUSTAINABLE GROUPS The substitutable group, hereinafter referred to as the group L, must be sufficiently reactive for the perhydrolysis reaction to occur within the optimum time frame (eg, within a wash cycle). However, if L is too reactive, this activator can hardly be stabilized to be used in a composition of * 1 lanq? Eo. The preferred L groups are selected from the group consisting of: R4 its mixtures; wherein R3- is an alkyl, aryl or alkaryl group containing from 1 to 14 carbon atoms; R3 is an alkyl chain containing from 1 to 8 carbon atoms; R * is H or R3; and Y is H or a solbilizing group. Any of R, R3 and R * may be substantially substituted with any functional group including, for example, alkyl, hydroxy, alkoxy, halogen, amine, nitrosyl, amide and ammonium or alkylenonium groups. Preferred solubilizing groups are: -SOa ~ M "', -COa-M *, -N * (R3 X- and 0 <--N (Ra) a, and most preferably, -S0a ~ ri" * "and -COa ~ M "A wherein R3 is an alkyl chain containing 1 to 4 carbon atoms, M is a cation which gives solubility to the bleach activator and X is an anion that provides solubility to the bleach activator. Preferably, M is an alkali metal, ammonium or substituted ammonium cation, with sodium and potassium being more preferred, and X is a halide, hydroxide, methylisulfate or acetate anion.

The precursor of oerbenzoic acid The perbenzoic acid precursor compounds give perbenzoic acid by hydrolysis. Suitable 0-acylated perbenzoic acid precursor compounds include the substituted and unsubstituted benzoyl oxybenzenesulfonates, including, for example, benzoyl oxybenzenesulfonate: * * • Also suitable are benzolization products of sorbitol, glucose and all saccharides, with benzoylating agents, including, for example: Ac = C0CHa; Bz = benzoyl. The perbenzoic acid precursor compounds of the imide type include: N-benzoylsuccinirnide, tetrabenzoyl-ethylenediamine and the ureas substituted with N-benzoyl. Suitable perbenzoic acid precursors, of the imidazole type, include: N-benzoylimidazole and N-benzoylbenzimidazole and other perbenzoic acid precursors containing the N-acyl group, useful, include: N-benzoylpyrrolidone, dibenzoyltaurine and benzoylpyrugltrarnic acid. Other precursors of perbenzoic acid include the benzoyl A-aliacylperoxides, the benzoyl tetraacylperoxides and the compound q ee having the formula: Phthalic anhydride is another suitable perbenzoic acid precursor compound, herein: Suitable N-acylated lactam perbenzoic acid precursors have the formula: -9n where n is from 0 to about 8, preferably from 0 to 2; and R * is the benzoyl group.

Precursors of perbenzoic acid derivative Suitable perbenzoic acid derivative precursors give substituted, non-cationic perbenzoic acids by perhydrolysis. Suitable substituted perbenzoic acid derivative precursors include any of the perbenzoic precursors described herein, in which the benzoyl group is substantially substituted with any functional group not positively charged (ie, non-cationic), including, for example, alkyl, hydroxy, alkoxy, halogen, amine, nitrosyl and amide. A preferred class of substituted perbenzoic acid precursor compounds are the amide substituted compounds of the following general formulas: "1-C-N_R2_C-L Rl-N-C-R2-c-L or? ¿? O »o; R ° O II O II wherein R is an aryl or alkaryl group having from 1 to 14 carbon atoms; Ra is an arylene or alkarylene group containing from 1 to 14 carbon atoms, and Ra is H or a group - Alkyl, aryl or alkaryl containing from 1 to 10 carbon atoms and L can be essentially any substitutable group. R3- preferably contains from 6 to 12 carbon atoms. Ra preferably contains from 4 to 8 carbon atoms. R3- can be aryl, substituted aryl or alkylaryl containing branching, substitution or both, and can be derived from synthetic sources or from natural sources, including, for example, serous fat. Analogous structural variations for Ra are permissible. The substitution may include alkyl, aryl, halogen, nitrogen, sulfur and other typical substituent groups or typical organic compounds. Rs preferably is H or methyl. R and Rs must not contain more than 18 carbon atoms in total. The amide-substituted bleach activator compounds of this type are described. in EP-A-0, 170, 386.

Cationic peroxyacid precursors The cationic peroxyacid precursor compounds produce cationic peroxyacids, by perhydrolysis. Typically, the cationic peroxyacid precursors are formed by substituting the peroxyacid portion of a peroxyacid precursor compound with a charged functional group, such as an ammonium or alkylammonium group, preferably an ethyl- or ethylammonium group. Cationic peroxyacid precursors are typically present in detergent compositions which smell a salt with a suitable anion, such as a halide ion.The peroxyacid precursor compound to be cationically substituted in that manner may be a compound per-benzoic acid precursor or a substituted derivative of the same, as described above.Alternatively, the peroxyacid precursor compound may be a precursor alkyl fatty peroxyacid compound or a precursor of alkyl substituted peroxyacid with amide, such as which are described below. Cationic peroxyacid precursors are described in U.S. Patents 4,904,406, 4,751,015, 4,988,451, 4,397,757, 5,269,962, 5,127,852, 5,093,022, ,106,528; UK 1,382,594; EP 475,512, 458,396 and 284,292; and in 3P 87-318,332. Examples of preferred cationic peroxyacid precursors are described in the United Kingdom patent application.

-Jnido No. 9,407,944.9 and in the US patent applications No. 08 / 298,903, 08 / 298,650, 08 / 298,904 and 08 / 298,906. Suitable cationic peroxyacid precursors include any of the alkyl or benzoyl oxybenzenesulphonates, substituted with ammonium or with alkynylononium, N-acylated caprolactams and rnonobenzoyl-tetraacetylglucosebenzoyl peroxides. A cationically benzoyl oxybenzene fonate < • Astitute, preferred, is the 4- (trimethylammonium) rnetium derivative of benzoyl oxybenzenes: A preferred cationically substituted alkyl oxybenzene sulfate has the formula: Preferred cationic peroxyacid precursors of the N-acylated caprolactam class include the trialkylammonium methylenebenzoylcaprolactams, particularly the trimethylaronium methylenebenzoylcaprolactane: Another preferred class of cationic peroxyacid precursor includes the trialkylammonium n-alkyl caprolactams: wherein n is from 0 to 12. Another preferred cationic peroxyacid precursor is 2- (N, N, N-trimethylarononium) ethysodonium 4-sulfophenylcarbonate chloride.

The precursors of alkylcarbonyl alcohol bleach The alkylpercarboxylic acid bleach precursors form, by perhydrolysis, two percarboxylic acids. Preferred precursors of this type - roveen, by perhydrolysis, peracetic acid. Preferred alkylcarboxylic acid precursor compounds, of the imide type, include the N, N, NAN'-tetraacetylated alkylenearnines, wherein the alkylene group contains from 1 to 6 carbon atoms, particularly those compounds in which the alkylene group contains 1 to 6 carbon atoms. , 2 and 6 carbon atoms. Tetraacetylethylenediamine (TAED) is particularly preferred. Other preferred alkylpercarboxylic acid precursors include sodium 3,5,5-trimethylhexanoyloxybenzenesulfonate (iso-NOBS), nonanoyloxybenzene sodium fonate (NOBS), sodium acetoxybenzenesulfonate (ABS) and pentaacetylglucose.

The amino acid-substituted alauylperoxy acid precursors The alkylperoxyacid precursor compounds substituted with amide are also suitable, including those having the following general formulas: • ^ m where R3- is an alkyl group of 1 to 14 carbon atoms; R3 is an alkyl group containing 1 to 14 carbon atoms and RB is H or an alkyl group containing 1 to 10 carbon atoms and L can be essentially any substitutable group. R preferably contains from 6 to 12 carbon atoms. R2 preferably contains from 4 to 8 carbon atoms. R3- can be straight or branched chain alkyl which contains branching, substitution or both, and can be derived from synthetic sources or from natural sources, including, for example, tallow grease. Analogous structural variations for Ra are permissible. The substitution may include alkyl, halogen, nitrogen, sulfur and other typical substituent groups or typical organic compounds. Ra preferably is H or methyl. R3- and Rs must not contain more than 18 carbon atoms in total. Amide-substituted bleach activator compounds of this type are described in EP-A-0 170 086.

The organic peroxyacid precursors of henzoxayine Also suitable are benzoxazine type precursor compounds, such as those discussed, for example, in EP-A-332,294 and EP-A-482, 807, particularly those having the formula: including the substituted benzoxazines of the type: wherein R is H, alkyl, alkaryl, aryl, arylalkyl; and where Ra, Ra, R + and r? they can be the same or different substituents, selected from H, and the halogen, alkyl, alkenyl, aryl, hydroxyalkyl, alkoxy, amino, alkylamino, COOR functions? (wherein R * is H or an alkyl group) and carbonyl. An especially preferred precursor of the benzoxazine type is: 6 ?? - • »'1 preformed organic peroxyacid The organic peroxyacid bleach system may contain, in addition to, or as an alternative to, a precursor organic peroxyacid bleach compound, a preformed organic peroxyacid, typically at a level of 1% a % by weight, better still, from 1% to 10% by weight of the composition. A preferred class of organic peroxyacid compounds are the amide substituted compounds of the following general formulas: R1 - wherein R3- is an alkyl, aryl or alkaryl group having 1 to 14 carbon atoms; Ra is an alkylene, arylene and alkarylene group containing 1 to 14 carbon atoms; and Ra is H or an alkyl, aryl or alkaryl group containing from 1 to 10 carbon atoms. R3- preferably contains from 6 to 12 carbon atoms. Ra preferably contains from 4 to 8 carbon atoms. R3- may be straight or branched chain alkyl, substituted aryl or alkylaryl which contains branching, -'-Substitution or both, and may be derived from synthetic sources or from natural sources, including, for example, tallow grease. Analogous structural variations for Ra are permissible. The substitution may include alkyl, aryl, halogen, nitrogen, sulfur and other substituent groups or typical organic compounds. R is preferably H or methyl. R3- and Rs must not contain more than 18 carbon atoms in total. Organic amide-substituted peroxyacid compounds of this type are described in EP-A-0, 170,386. Other organic peroxyacids include the diacyl- and tetraacylperoxides, especially diperoxydodecanedioic acid, diperoxytetradecanedioic acid and diperoxyhexadecanedioic acid. The mono- and diperazelaic acids and the rnono- and di-perbranilic acids as well as the N-phthaloylarninoperoxycaproic acid are also suitable for use herein. t chlorine bleach The compositions herein are preferably free of chlorine bleach.

The bleach catalyst The invention also includes compositions containing a catalytically effective amount of a bleach catalyst, such as a water soluble manganese salt. The bleach catalyst is used in a catalytically effective amount in the compositions of the present. By "catalytically effective amount" is meant an amount which is sufficient, under any comparative test condition employed, to increase the bleaching and removal of the stain or spots of interest from the target substrate. Thus, in a fabric washing operation, the target substrate will typically be a stained fabric, for example, with various food stains. For automatic dishwashing, the target substrate may be, for example, a porcelain cup or dish, with tea stains, or a polyethylene dish stained with tomato soup. The test conditions will vary, depending on the type of washing device used and the user's habits.

Thus, laundry washing machines, which are charged by the * Rente, of the type used in Europe, generally use less water and higher concentrations of detergent than top-loading machines that are styled in the United States. Some washing machines have wash cycles that are considerably longer than others. Some users choose to use very hot water; others use warm water or even cold water in fabric washing operations. Of course, the. catalytic performance of the bleach catalyst will be affected by those considerations, and the levels of bleach catalyst used in the fully formulated bleach and detergent compositions can be adjusted appropriately. As a practical matter, and not to establish a limitation, the compositions and methods herein can be adjusted to provide active bleach catalyst species, in the order of at least one part per ten million such species, in the liquor of aqueous wash; and preferably provide about 1 pprn to 200 pprn of the catalyst species, in the laundry wash liquor. To further illustrate this point, an amount of manganese catalyst of the order of 3 micronols at 40 ° C, pH 10, is effective under European conditions, using perborate and a bleach precursor (for example benzoyl-caprolactane). An increase of 3 to 5 times ba or US conditions may be necessary to obtain the same results. Conversely, the use of a bleach precursor and the manganese catalyst with perborate may allow the formulator to obtain equivalent bleaching at lower levels of use of perborate than the products without the manganese catalyst. The bleach catalyst material herein may comprise the free acid or may be in the form of any suitable salts. One type of bleach catalyst is a catalyst system comprising a heavy metal cation with defined bleach catalytic activity, such as copper, iron or manganese; an auxiliary metallic cation, having little or no catalytic bleaching activity, such as zinc or aluminum cations; and a scavenger having defined stability constants for the catalytic and auxiliary metal cations, particularly ethylenediaminetetraacetic acid, rilethylenephosphonic ethylenediaminetetraacetate) and their water soluble salts. Said catalysts are described in U.S. Patent No. 4,430,243. Other types of bleach catalysts include manganese-based complexes, described in U.S. Patent No. 5,246,621 and U.S. Patent No. 5,244,594. Preferred examples of these catalysts include HnIV2 (u-0) to (1,4, 7-trimethyl-1,, -triazacyclononane) a- (PFβ) 2; nnI?: c2 (u-0) 3. (u-0Ac) 3 (1, 7-trimethyl-1, 4, 7-triaza-cyclononane) a - (C10A) a; MnIV (u-0)? (1, 4, 7-triazacyclononane) - < C10_ a, rmII: tivJnIV «(u-0) a. (? - 0Ac) as-l / 4, 7-trimethyl-l, 4,7-riazacyclononane) s_ (C10«.) A and their mixtures. Others are described in European patent application publication No. 549, 272. Other ligands suitable for use herein include: l ^^ - trimethyl-l / d ^ -triazacyclododecane, 2-metii-i, 4,7-triazacyclononane, 2-methyl-l, 4,7-triazacyclononane, 1, 2,4,7-tetramethyl-7, 7-triazacyclononane and mixtures thereof. For examples of suitable bleach catalysts see U.S. Patent No. 4,246,612 and U.S. Patent No. 5,227,084. See also U.S. Patent 5,194,416, which teaches rnonon? Clear (IV) manganese complexes, such as rtn (1,4,4-trimethyl-1,4,4-triazacyclononane) (0CH3) a- (PFß). Yet another type of bleach catalyst, which is described in US Patent 5,114,606, is a water-soluble complex of manganese (II), (III) and / or (IV) with a ligand that is a polyhydroxy compound that does not contain carboxylate , which has at least three consecutive C-OH groups. Preferred ligands include: sorbitol, iditol, dulsitol, mannitol, xylitol, arabitol ,. adonitol, meso-erythritol, meso-inositol, lactose and mixtures thereof. U.S. Patent No. 5,114,611 teaches a bleach catalyst comprising a complex of transition metals, including Mn, Co, Fe or Cu, with a non (macro) -cyclic ligand. These ligands have the formula: R2 R3 R1-N = C-B-C = N-R4 wherein each of R3-, Ra, Ra and R * can be selected from H, substituted alkyl and aryl groups, such that each R3-- N = C-Ra and Ra-C = NR * form a Five or six member ring. Said ring may be additionally substituted. B is a linking group selected from O, S, CRaRa, NRV and C = 0, ~ "* n where each naN of Ra, R * and R7 can be H, alkyl or aryl groups, including the substituted or The preferred ligands include pyridine, pyridazine, pyrimidine, pyrazine, imidazole, pyrazole and triazole rings, optionally said rings may be substituted with substituents such as alkyl, aryl, alkoxy, halide and nitro. 2'-bispyridylamine Preferred bleach catalysts include the complexes of Co, Cu, Un, Fe, -bispyridylrnetane and -bispyridylamine.The highly preferred catalysts include: Co (2,2'-bispyridyla unaJCla, di (isothiocyanato) -bis) ? iridylamine-cobalt (II), trisdipyridylarnine-cobalt (II) perchlorate, Co (2,2-bispyridylamine) 5_0aC10. ", bis- (2,2'-bispyridylamine) copper (II) perchlorate, tps perchlorate (di-2-pyridylamine) iron (II) and mixtures thereof Other examples include gluconate end, rin (CFaSOa) a, Co (NHa) aC.ly and the binuclear end formed to complex with ligands of tetra-N-dentate and bi-N-dentate, including N MnIXI (u-0) aMnI N *) - and rBipyannIII ( u-0) 2l1n:?: vbipyS?] - (C10 *) 3. Bleach catalysts may also be prepared by combining a water soluble ligand with a water soluble manganese salt, in aqueous media and concentrating the resulting mixture by evaporation. Any suitable water-soluble manganese salt can be used herein. Manganese (II), (III), (IV) and / or (V) is available commercially available. In some cases, sufficient manganese may be present in the wash liquor but, in general, it is preferred to add end cations in the compositions to ensure their presence in catalytically effective amounts. Thus, the sodium salt of the ligand and a member selected from the group consisting of HnSO *, rin (C10A) a or (InCl-a (preferred moieties) at molar proportions of ligand: salt of tln on the scale are dissolved in water. from about 1: 4 to 4: 1, at a neutral or slightly alkaline pH, the water is first deoxygenated by boiling and cooled by bubbling with nitrogen, the solution is evaporated (under nitrogen, if desired) and solids are used. resulting in the bleach and detergent compositions herein, without further purification In an alternative mode, the source of water-soluble manganese, such as InesSO, is added to the bleaching / cleaning composition or to the aqueous bleaching / cleaning bath, It is understood that some type of complex is formed in situ, and the improved operation of the bleach is ensured In said in situ procedure it is convenient to use a considerable molar excess of the ligand with respect to the manganese, and the Ligand sources: Mn are typically in the order of 3: 1 to 15: 1. The additional ligand also serves to purify the vaping metal ions, such as iron and copper; thus protecting the bleach against its decomposition. One such system, possible, is described in the publication of the European patent application No. 9,271. While the structures of some of the manganese complexes that catalyze the bleach have not been fully elucidated, it can be speculated that they comprise chelates or other hydrated coordination complexes, which are the result of the interaction of the carboxyl and the nitrogen atoms of the ligand with the manganese cation. Similarly, the oxidation state of the manganese cation during the catalytic process is not known with certainty; and it can be the state of valence (+11) (+ III), (+ IV) or (+ V). Due to the possible six binding points of the ligand to the manganese cation, it can be reasonably speculated that there may be multi-nuclear species and / or "cage" structures in the aqueous bleaching media. Whatever the form in which the active Mn-ligand species actually exists, it functions in a seemingly catalytic manner to provide improved bleaching operations on difficult spots, such as teas, ketchup, coffee, blood and the like. Other ethanic bleach catalysts described, for example, in European Patent Application No. 408,131 (complex cobalt catalysts), in European patent applications Publication No. 384,503 and 306,089 (etalo-porphyrin catalysts); in U.S. Patent No. 4,728,455 (manganese ligand / multidentate catalyst), U.S. Patent 4,711,748 and European Patent Application Publication No. 24,952, (manganese catalyst absorbed on aluminosilicate); in U.S. Patent 4,601,845 (aluminosilicate support with manganese and zinc or magnesium salt), U.S. Patent 4,626,373 (manganese / ligand catalyst) U.S. Patent 4,119,557 (ferric complex catalyst), German Patent Specification 2,054,019 (cobalt chelator catalyst ), Canadian patent 866,191 (salts containing transition metal), US patent 4,430,243 (chelators with manganese cations and non-catalytic metal cations) and in US patent 4,728,455 (manganese gluconate catalysts).

Relative release kinetics In an essential aspect of the invention, means are provided for retarding the release of the organic peroxyacid bleach to a wash solution, with respect to the release of the enzyme. Said medium may comprise a means for delaying the release of the organic peroxyacid bleach to the washing solution. Alternatively, said medium may comprise a means for increasing the rate of release of the enzyme to the solution. A very preferred way is to retard the release of the peroxyacid bleach as the release of the Hs-Oa.

Delayed release rate - means.

The media can provide the delayed release of the organic peroxyacid bleach source itself to the wash solution. Alternatively, when the peroxyacid source is an organic peroxyacid precursor compound, the delayed release means may comprise a means to inhibit or prevent the in situ perhydrolysis reaction which releases the organic peroxyacid to the solution. Such means, for example, include controlling the release of the hydrogen peroxide source to the wash solution, for example, by controlling the release of any inorganic perhydrate salt, which acts as a source of hydrogen peroxide, into the solution of washing. The delayed release media may include coating any suitable component with a coating or a mixture of coatings designed to provide the delayed release. Accordingly, the coating, for example, may comprise a sparingly water-soluble material, or be a coating of sufficient thickness so that the dissolution kinetics of the coarse coating provides the rate of delayed release. The coating material can be applied • using various methods. Any coating material is typically present at a weight ratio of coating material to bleach-from 1:99 to 1: 2, preferably from 1:49 to 1: 9. Suitable coating materials include triglycerides, mono- or diglycerides of hydrogenated vegetable oil (eg, partially hydrogenated), soybean oil, cottonseed oil), microcrystalline waxes, gelatin, cellulose, acids fatty and any mixtures of them. Other suitable coating materials may include the alkali metal and alkaline earth metal sulphates, silicates and carbonates, including calcium carbonate and the silicas. The preferred coating material is sodium silicate, with a Si02: Na20 ratio of 1.6: 1 to 3.4: 1, preferably 2.2: 1 to 2.8: 1, applied as an aqueous solution to give a level of 2. % to 10% (preferably 3% to 5%) of silicate solids by weight of the percarbonate. Magnesium silicate can also be included in the coating. Any inorganic salt coating materials may be combined with organic agglutinating materials to give inorganic salt / organic binder mixed coatings. Suitable binders include the alcohol ethoxylates of 10 to 20 carbon atoms containing from 5 to 100 moles of ethylene oxide per milliliter of alcohol, and, furthermore, the primary alcohol ethoxylates of 15 to 20 carbon atoms. carbon containing 20 to 100 moles of ethylene oxide per mole of alcohol. Other preferred binders include certain polymeric materials. Polyvinylpyrrolidones, with an average molecular weight of 12,000 to 700,000, and polyethylene glycols (PEG) with an average molecular weight of 600 to 5 x 10 *, preferably 1,000 to 400,000, preferably from 1,000 to 10,000, are examples of said polymeric materials. Copolymers of maleic anhydride with ethylene, methylvinyl ether or methacrylic acid, wherein the anionic acid constitutes at least 20 mole percent of the polymer, are other examples of polymeric materials useful as binders. These polymeric materials can be used as such or in combination with solvents such as water, propylene glycol and the alcohol ethoxylates of 10 to 20 carbon atornoe mentioned above, containing from 5 to 100 moles of ethylene oxide per mole of alcohol. Other examples of agglutinators include the mono- and diglycerol ethers of 10 to 20 carbon atoms, and also the fatty acids of 10 to 20 carbon atoms. The cellulose derivatives, such as methylcellulose, carboxymethylcellulose, ethylhydroxyethylcellulose and hydroxyethylcellulose, and the copolymeric or copolymeric polycarboxylic acids or their salts, are other examples of suitable binders to be used herein.

A method for applying the coating material involves agglomeration. Preferred agglomeration processes include the use of any of the organic binder materials described above. Any conventional agglomerator / mixer can be used, including, but not limited to, tray mixer, rotary drum and vertical mixer types. Molten coating compositions can also be applied, either by pouring them on or atomizing them on a moving bed of bleaching agent. Other means to provide the controlled release required include mechanical means to alter the physical characteristics of the bleach in order to control its solubility and release rate. Sule protocols would include compaction, mechanical injection, manual injection and adjustment of the solubility of the bleaching compound, selecting the particle size of any particulate Component. While the selection of the particle size will depend both on the composition of the particulate component and the desire to satisfy the desired controlled release kinetics, it is desirable that the particle size is not more than 500 micrometers, preferably having a diameter average particle size from 800 to 1,200 micrometers. Additional protocols for providing the controlled release means include the proper selection of any other components in the detergent composition matrix, such that, when the composition is introduced into the wash solution, the ion concentration environment provided in it, allows the required controlled release kinetics to be obtained.

Increased release regime - means All sule means are contemplated to increase the rate or rate of release of the heavy metal ion sequestrant in the solution. The increased release means may include the coating of any sule component with a coating designed to provide increased release. Therefore, the coating may comprise, for example, a material highly soluble in water, or even effervescent. Other means for providing the required delayed release include mechanical means for altering the physical characteristics of the heavy metal ion sequestrant, in order to increase its solubility and rate of release. A sule protocol could include the deliberate selection of the particle size of any component that contains the heavy metal ion sequestrant. The selection of the particle size will depend both on the composition of the particulate component, and the desire to satisfy the desired increased release. It is desirable that the particle size be less than 1200 micrometers, preferably having an average particle diameter of 1,100 to 500 micrometers. Other protocols for giving the delayed release means include the proper selection of any other components of the detergent composition matrix, or of any particulate component that contains the heavy metal ion sequestrant, so that " If the composition is introduced to the washing solution, the ionic concentration environment provided there allows the increased release kinetics to be obtained.

Delayed release - kinetic parameters The release of the organic peroxyacid bleach component from the bleach-peroxy acid system with respect to that of the enzyme component is such that in the T50 test method described herein, the time to obtain a concentration that is 50% of the concentration end of the enzyme is less than 120 seconds, preferably less than 90 seconds, still better, less than 60 seconds; and the time necessary to obtain a concentration that is 50% of the final concentration of the peroxyacid bleach is greater than 180 seconds, preferably 180 to 480 seconds, better still, 240 to 360 seconds. In another 4.1 In this regard, the T50 for the enzyme component is at least 100 seconds less than the T50 for the peroxyacid bleach In a highly preferred aspect of the invention, the bleach release is of such a nature that, in the T40 test method described here, the time to obtain a total available oxygen level (ODT) that is 50% of the final level, is greater than 180 seconds, preferably 180 to 480 seconds, better still, 240 to 360 seconds A method for determining ODT levels is described in European Patent Application No. 93870004.4 In another preferred aspect of the invention, when the source of peroxyacid bleach is a precursor of peroxyacid bleach, used in combination with a source of hydrogen peroxide, the kinetics of release of hydrogen peroxide to the washing solution, relative to that of the enzyme component is such, that in the T40 test method described herein, the time to obtain a concentration that is 50% of the final concentration of said enzyme is less than 120 seconds, preferably less than 90 seconds, still better, less than 60 seconds; and the time to obtain a concentration which is 50% of the final concentration of the hydrogen peroxide and the peroxyacid bleach precursor is greater than 180 seconds, preferably 180 to 480 seconds, even better, from 240 to 360 seconds When the enzyme is a protease, the final amount in a typical wash solution is 0.1 to 100 KNPU, but preferably 0.5 to 50 KNPU, even better, 3 to 30 KNPU and, even better, 6 to 30 KNPU. When the enzyme is arní lasa, the final amount in a typical wash solution is 1 to 200 KNU, but preferably 10 to 100 KNU, better still, 40 to 80 KNU. When the enzyme is a lipase, the final amount in a typical wash solution is from 1 to 300 KLU, but preferably from 10 to 200 KLU, preferably even 10 to 100 KLU. When the enzyme is a cellulase, the final amount in the wash is typically from 10 to 1200 CEVU, but preferably from 50 to 100 CEVU, even better, from 80 to 500 CEVU. The final concentration in the lava < The amount of any inorganic perhydrate bleach is typically from 0.005% to 0.25% by weight, but preferably by more than 0.05%, better still, by more than 0.075%. The final concentration in the wash "of any peroxyacid precursor is typically" 0.001% to 0.08% by weight, but preferably 0.005% to 0.05%, even better, 0.015% to 0.05%.

Delayed release - pruftba method The delayed release kinetics is "here compared to" a TA test method "which measures the time to obtain AZ of the concentration (vfinal level of that component, when a composition containing the component is dissolved, In accordance with the standard conditions that are now given, the standard conditions involve a 1-liter glass beaker filled with 1,000 ml of distilled water at 20 ° C, to which 10 g of composition is added. The content of the beaker using a magnetic stirrer set at 100 rpm The magnetic stirrer is of the pea / egg form, which has a maximum dimension of 1.5 cm and a minimum dimension of 0.5 cm.The concentration / final level is taken As the concentration / level reached 10 minutes after the addition of the composition to the beaker filled with water, the appropriate analytical methods are selected to allow a reliable determination of the concentrations incidental and final in the solution, of the < } This is after the addition of the composition to the water in the beaker. Such analytical methods may include those involving continuous monitoring of the concentration level of the component, including, for example, photo-electric and conductometric methods. Alternatively, methods may be employed that involve removing the titers from the solution at fixed time intervals "two, "Stopping the dissolution process by an appropriate means, such as rapidly reducing the temperature of the titre, and then determining the concentration of the component in the titre, by any means, such as by chemical title methods. Appropriate graphical methods, including curve fitting methods, can be used, where appropriate, to allow calculation of the TA value from the raw analytical results. The particular analytical method selected to determine the concentration of the component will depend on the nature of that component and the nature of the composition contained in that component.

The additional detergent components The detergent compositions of the invention may also contain other detergent components. The precise nature of the additional components cited, and the levels "Of their incorporation, they will depend" on the physical form of the composition and on the nature "of the cleaning operation for which they are to be used. The compositions of the invention, for example, can be formulated as laundry detergent compositions by hand and machine, including additive compositions for laundry and composition suitable for use in the pretreatment of soiled fabrics and in dishwashing compositions in machine. When formulated as a suitable co-position for use in a machine washing method, for example, the methods for washing clothes in machine and for washing dishes in the machine, the compositions of the invention preferably contain one or more components "additional detergents, selected from surfactants, water-insoluble builders, organic polyrneric compounds, additional enzymes, foam euphorres, lime soap diers, agents for sludge suspension and to prevent redeposition, and corrosion inhibitors. The laundry compositions may also contain, as additional detergent components, softening agents.

The surfactant The detergent compositions of the invention may contain as an additional detergent component a surfactant agent selected from the anionic, cationic, nonionic, ampholytic, amphoteric and zwitter ionic surfactants, as well as their mixtures. Typically, the surfactant is present at a level of 0.1% to 60% by weight. The most preferred levels of incorporation of the surfactant are from 1% to 35% in peeo, better still, from 1% to 20% in peeo. Preferably the surfactant is formulated to be compatible with any "enzyme" components present in the composition. In the In liquid or gel compositions, the surfactant is most preferably formulated in such a way that it promotes, or at least does not degrade, the stability of any enzyme present in the compositions A typical listing of the anionic, non-ionic classes , Zwitterionic and ampholytic, and of the species "of these surfactants, is given in the U.S. Pat. 3,929,678, "by Laughlin and Heuring, issued on December 30, 1975. Other exercises are given in Surfaca Active Agents and Eteraents (volumes I and II by Schwartz, Perry and Berch). A list of suitable cationic surfactants is given in U.S. Patent No. 4,259,217, issued to Nurphy on March 31, 1981. When present, the ampholytic, amphoteric and zwitterionic surfactants are generally used in combination with one or more ionic and / or nonionic surfactants.

The anionic surfactant Essentially any nonionic surfactant useful for detersive purposes can be included in the compositions. They may include salts (eg, sodium, potassium, ammonium and substituted ammonium salts, such as the mono-, di- and triethanolamine salts) of anionic surfactants, sulfate, sulfonate, carboxylate and other sarcosinate Other anionic surfactants include the isethionates, such as acyl isethionates, the N-acyltaurates, the fatty acid amides of rnetiltauride, the alkylsuccinates and the sulfosuccinates, the elasto-succinate mononucleotides (especially the nucleotide esters). at 18 carbon atoms, saturated and unsaturated), the diesters of sulfosuccinate (especially the diesters of 6 to 14 carbon atoms, saturated and unsaturated), and the sarcosinatoe of N-acyl, the resin acids and the resin acids Hydrogenated hydrocarbons are also suitable, such as rosin, hydrogenated rosin and the resin acids and hydrogenated resin acids that are present in, or derived from, oil. eboThe anionic sulfate surfactant The anionic sulfate surfactants, for use herein, include the primary, linear and branched alkyl sulphates, the alkyl ethoxysulfates, the oleyl glycerol fatty sulphates, the alkyl phenol alkyl sulphates of ethylene oxide, the acyl sulfates of Cs-aT-N-talkyl of C _ *) and -N- (hydroxyalkyl of Cx-s.) glucamine, and the sulfatoe of alkylpolysaccharides, such as the sulphates of alkyl polyglucosides (the non-sulfated compounds do not are described here). The alkyl ethoxy sulfate surfactants are preferably selected from the group consisting of alkyl sulfates of 6 to 18 carbon atoms, which have been ethoxylated with about 0.5 to 20 moles of ethylene oxide per molecule. Still better, the surface-active agent of alkyl ethoxysulfate is an alkyl sulphate of 6 to 18 carbon atoms which has been on the side of about 0.5 to 20, preferably 0.5 to 5, moles of zinc. ethylene per molecule.

The anionic sulfonate surfactant The ammonium sulfonate surfactants, suitable for use herein, include the linear alkylbenzene sulphonate salts of 5 to 20 carbon atoms; The ester sulphates of alkyl, the primary alkanesulphonates ) secondaries of 6 to 22 carbon atoms, olefin sulfonates of 6 to 24 carbon atoms, sulfonated polycarboxylic acids, alkyl glycerol sulphonates, fatty acyl glycerol sulphonates, fatty oleic acid glycerolsulphates and any mixtures from them.

The anionic carboxylate surfactant The ammonium carboxylate surfactants, ~~ - > For use herein, include the alkyl ethoxycarboxylates, the alkyl polyethoxypolycarboxylate surfactants and the soaps ("alkylcarboxyls"), especially certain secondary soaps described herein. Preferred alkyl ethoxycarboxylates, for use herein, include those having the following formula: RO (CHszCHzO) XCHSYCOO-M * wherein R is an alkyl group of 6 to 18 carbon atoms; x varies from 0 to 10 and the ethoxylate distribution is such that, on a weight basis, the amount of material where x is 0, is less than about 20%; and the amount of material where x is greater than 7, is less than 25%; the average of x is 2 to 4 when the average "of R is 13 carbon atoms or less, and the average of x is 3 to 10 when the average of R is" of more than 13 carbon atoms; and M is a cation, preferably selected from the alkali metal, alkaline earth metal, ammonium, mono-, di- and triethanolammonium cations and, most preferably, sodium, potassium, ammonium and mixtures thereof, with magnesium ions. Preferred alkyl ethoxycarboxylates are those in which R is an alkyl group of 12 to 18 carbon atoms. The alkyl polyethoxypolycarboxylate surfactants, suitable for use herein, include those having the formula: RO- (CHR-CHRa-0) -R3 *? where R is an alkyl group of 6 to 18 carbon atoms, x is 1 to 25, R_. and Ra are selected from the group consisting of hydrogen, the methyl acid radical, the succinic acid radical, the hydroxysuccinic acid radical and mixtures thereof; wherein at least one of R and R_ > is a succinic acid radical or a hydroxyacyclic acid radical; and Ra is selected from the group consisting of hydrogen, a substituted or unsubstituted hydrocarbon having from 1 to 8 carbon atoms, and mixtures thereof.

The anionic secondary soap surfactant The preferred soap surfactants are secondary soap surfactant agents containing a carboxyl unit connected to a secondary carbon. The secondary carbon may be in an annular structure, for example, as in the case of the p-octylbenzoic acid, or as in the alkyl substituted carboxylic acid carboxylates. The secondary soap surfactants preferably do not "contain ether ligatures, ester ligatures or hydroxyl groups. Preferably there should not be "nitrogen atoms in the leader group (amphiphilic portion). The secondary soap surfactants ordinarily contain "from 11 to 15 carbon atoms in total., although it can be tolerated slightly more (for example, up to 16), for example, p-octylbenzoic acid. The following general structures illustrate ^ "In addition some of the preferred secondary soap surfactants: A. A highly referred class of secondary soaps comprises the secondary carboxyl materials of the formula RaCH (R *) COOM, wherein R3 is CHaíCH ^) *. and R * is CHaíCHs,) ^, where y can be 0 or an integer from 1 to 4; x is an integer from 4 to 10 and the sum of (x + y) is from 6 to 10, "preferably from 7 to 9, most preferably, 8. B. Another preferred class of secondary soaps comprises those carboxyl compounds in wherein the carboxyl substituent is on a ring hydrocarbyl unit, ie, the secondary soaps of the formula Ra-R < s-C00p, wherein Ra is alkyl or alkenyl of 7 to 10 carbon atoms, preferably 8 to 9 carbon atoms, and R * is an annular structure, such as benzene, cyclopentane and cyclohexane. (NOTE: Ra may be in the ortho, meta or para position with respect to the carboxyl of the ring). C. Another preferred class of secondary soaps comprises the secondary carboxyl compounds "of the formula CHa (CHR)? - (CH2) m- (CHR) N-CH (CO? P) (CHR) o- (CHa) r > - (CHR) < , -CHa, wherein each R is alkyl of 1 to 4 carbon atoms, where k, n, mo, q, are integers on the scale from 0 to 8, provided "that the total number of carbon atoms (including the carboxylate) eeté on the scale of 10 to 18. In each of the above formulas, A, B and C, the species fl can be any suitable counter ion, and especially solubilizes < dor in water. The secondary soap surfactants, especially preferred for use herein, are the water-soluble members selected from the group consisting of the water-soluble salts of 2-methyl-1-undecanoic acid, 2-ethyl-1-acid. -decanoic, 2-propyl-l-nonanoic acid, 2-butyl-1-octanoic acid and 2-pentu-i-heptanoic acid.

The alkaline metal sarcosinate surfactant Other suitable anionic surfactants are the alkali metal sarcosinates of the formula R-C0N (R) CHa COOM, wherein R is a linear or branched alkyl or alkenyl group, R3- is an alkyl group of 1 to 4 carbon atoms and fl is an alkali metal ion. Preferred examples are the myristyl- and oleyl-methyl sarcoeinates in the form of their sodium salts.

The nonionic surfactant Any nonionic surfactant for detergency purposes can be included in the compositions herein. The exemplary, non-limiting, clauses of the non-ionic, useful surfactants appear below.

~ The acid amide surfactant agent. ionic ion The polyhydroxy fatty acid amides, suitable for use herein, are those which have the structural formula RaCONRxZ, where "R3- is H, hydrocarbyl of 1 to 4 carbon atoms, 2-hydroxyethyl, 2-hydroxypropyl or? a mixture thereof, preferably alkyl of 1 to 4 carbon atoms, better still, alkyl of 1 or 2 carbon atoms, especially alkyl of 1 carbon atom (i.e., methyl) and Ra is hydrocarbyl from 5 to 31 carbon atoms, preferably alkyl or alkenyl of 5 to 19 carbon atoms, straight chain, better still, alkyl or alkenyl of 9 to 17 carbon atoms, straight chain, and especially alkyl or alkenyl of 11 to 17 carbon atoms, straight chain, or mixtures thereof; and Z is a polyhydroxyhydrocarbyl having a linear hydrocarbyl chain, with at least 3 hydroxyls directly connected to the chain, or an alkoxylated derivative (preferably ethoxylated or propoxylated) thereof. Z preferably will be derived from a reducing sugar, in a reductive amination reaction; Better yet, Z is a glycityl.

The non-ionic condensates of algae phenols The condensates of alkylphenols with polyethylene, polypropylene and polybutylene oxides are suitable for use herein. In general, polyethylene oxide condensates are preferred. These compounds include the condensation products of alkylphenol. Which have an alkyl group containing from 6 to 18 carbon atoms, in straight chain or branched chain configuration with the alkylene oxide.

The non-ionic ethoxylated alcohol surfactant The condensation products with alkyl ethoxylate, of the aliphatic alcohols with about 1 to 25 moles "of ethylene oxide, are suitable for use herein. The alkyl chain of the aliphatic alcohol can be straight or branched, primary or secondary and, in general, contains from 6 to 22 carbon atoms. Particularly preferred are the condensation products of alcohols having an alkyl group containing from 8 to 20 carbon atoms, with from about 2 to 10 moles of ethylene oxide per mole of alcohol.

The surfactant of ethoxylated / propoxylated nonionic fatty alcohol.

Fatty alcohols of 6 to 18 carbon atoms, ethoxylate < two, and the fatty alcohol ethoxylated /? roxylates "two mixed alcohols, of 6 to 18 carbon atoms, are suitable surfactants for use herein, particularly when they are soluble in water. Preferably the ethoxylated fatty alcohols are the ethoxylated fatty alcohols of 10 to 18 carbon atoms, with a degree of ethoxylation of 3 to 50, even better, are ethoxylated fatty alcohols of 12 to 18 carbon atoms, with a degree of ethoxylation from 3 to 40. Preferably, the mixed ethoxylated / propolated fatty alcohols have an alkyl chain length of 10 to 18 carbon atoms; a degree of ethoxylation of 3 to 30 and a degree of propoxylation «of 1 to 10.

OE / OP condensates with propylene glycol. non-ionic The condensation products of ethylene oxide with a hydrophobic base, formed by the condensation of propylene oxide with propylene glycol, are suitable for use here. The hydrophobic portion of these compounds preferably has a molecular weight of about 1,500 to 1,800 and exhibits insolubility in water. Examples of compounds of this type include certain commercially available Pluronic ™ surfactants sold by BASF.

The condensation products of QE with adducts d xi or d ethylene / ethylenediamine. not ionic The condensation products of ethylene oxide with the product resulting from the reaction of β-propylene oxide and β-thianediamine, are suitable to be used here. The hydrophobic portion of these products consists of the reaction product of ethylenediamine and an excess of propylene oxide, and in general has a molecular weight of about 2,500 to 3,000. Examples of this type of nonionic surfactant include some of the commercially available Tetronic ™ compounds sold by BASF.

The alkylpolysaccharide surfactant. non-ionic Suitable alkyl polysaccharides to be used herein are "described in U.S. Patent 4,565,647. of Filling, issued January 21, 1986, having a hydrophobic group containing from 6 to 30 carbon atoms, approximately, preferably from 10 to 16 carbon atoms, approximately, and a polysaccharide, for example, a polyglycoside, the hydrophilic group containing "from 1.3 to 10," preferably from 1.3 to 3, better still, from 1.3 to 2.7 saccharide units. Any reducing saccharide containing 5 or 6 carbon atoms can be used; for example, the glucose, galactose and galactosyl portions can be used instead of the glucosyl moieties. (Optionally, the hydrophobic group is attached at positions 2, 3, 4, etc., thus giving a glucose or a galactose as opposed to a glucoside or a galactoside). The intersaccharide junctions may be, for example, between position 1 of the additional saccary units, and positions 2, 3, 4 and / or 6 of the sacchari or preceding units. Preferred alkyl polyglycosides have the formula: Ra0 (Cr? H? 2r? 0) t (glycosyl), < where Ra is selected from the group consisting of alkyl, alkylphenyl, hydroxyalkyl, hydroxyalkylphenyl, and mixtures of the moieties, wherein the alkyl groups contain from 10 to 18 carbon atoms, preferably from 12 to 14 carbon atoms. carbon; n is 2 or 3; t is 0 to 10, "preferably 0; and x is from 1.3 to 8, preferably from 1.3 to 3, better still, from 1.3 to 2.7. The glycoeil is preferably derived from glucose.

The non-ionic fatty acid amide surfactant.

The fatty acid amide surfactants, suitable for use in the preend, are those having the formula: R * C0N (R'7) Si, where "R * is an alkyl group containing from 7 to 21 atoms of carbon, preferably of 9 to 17 carbon atoms, and each R7 is selected from the group consisting of hydrogen, alkyl of 1 to 4 carbon atoms, hydroxyalkyl of 1 to 4 carbon atoms and - (CaH ^ O ^ H, where x is on the scale of 1 to 3. ^ 1 amphoteric surfactant.

Suitable amphoteric surfactants to be used herein include amine oxide surfactants and alkylamphocarboxylic acids. A suitable example of an alkylamphocarboxylic acid to be used herein is fliranol (MR) C2M Conc., Manufactured by Miranol, Inc., Dayton, NJ.

Amine oxide surfactant Amine oxides useful herein include those compounds having the formula Ra (0R '* -) > < Na (Ra) a, wherein Ra is selected from an alkyl, hydroxyalkyl, acylamidopropyl and alkylphenyl group, or mixtures thereof, containing from 8 to 26 carbon atoms, < preferably from 8 to 18 carbon atoms; R * is an alkylene or hydroxyalkylene group "Thu contains from 2 to 3 carbon atoms, preferably 2 carbon atoms or their mixtures; x is from 0 to 5, preferably from 0 to 3; and each Ra is an alkyl or hydroxyalkyl group containing 1 to 3, preferably 1 or 2 carbon atoms, or a polyethylene oxide group, containing 1 to 3, preferably 1 ethylene oxide group. . The groups Ra can be linked together, for example, by means of an oxygen or nitrogen atom to form a ring structure. Ammonium oxide surfactants, in particular, include the oxides of alkyldimethylamine of 10 to 18 carbon atoms in the alkyl and alcoxiet.-dihydroxyethylazole of 8 to 18 carbon atoms in the alkoxy. Examples of such materials include: dimethyloctylamine oxide, diethyldecylamine oxide, bis- (2-hydroxyethydodecylamine oxide, dimethydecylamine oxide, dipropyltetradecylamine oxide, methylethylhexadecylamine oxide, dodecylamidopropyldimethylamine oxide, cetyldinetiiarnine oxide, of stearyldirnethylamine, sebodirnethylamine oxide and dimethyl-2-hydroxyoctadecylamine oxide. Alkyldimethylamine oxide having 10 to 18 carbon atoms in the alkyl and acylamidoalkyl-dimethyl amine oxide having 10 to 18 carbon atoms in the alkyl is preferred.

Z itter ionic surfactant Zwitterionic surfactants may also be incorporated into the detergent compositions herein. These surfactants can be "broadly described as" derivatives of secondary and tertiary amines, derivatives of heterocyclic secondary and tertiary amines or derivative of quaternary ammonium, quaternary phosphonium or tertiary sulfonium compounds. Betaine and Stalin surfactants have exemplary Zwitterionic ionic surfactants for use herein. ^ l betaine surfactant The betaines useful herein are those compounds having the formula R (R ') aN * RaC00 ~, wherein R is a hydrocarbyl group of 6 to 18 carbon atoms, preferably an alkyl group of 10 to 16 carbon atoms or an acylarnidoalkyl group of 10 to 16 carbon atoms; each R3- is typically alkyl of 1 to 3 carbon atoms, preferably methyl; and Ra is a hydrocarbyl group of 1 to 5 carbon atoms, preferably an alkylene group of 1 to 3 carbon atoms, more preferably an alkylene group of 1 to 2 carbon atoms. Examples of suitable betaines include cocoacylamidopropyldimethylbetaine, hexadecyldimethylbetaine, acylamidopropylbetaine of 12 to 14 carbon atoms, acylamidohexydiethylbetaine of 8 to 14 carbon atoms, 4-Cacylmethyl amido-diethylammonium of 14 to 16 carbon atoms] -l-carboxybutane, acylarnidodirnetiibetaine of 16 to 18 arbono atoms, acylamido "dopentanodiethylbetaine" of 12 to 16 carbon atoms, Cacilmethylamine "dodimethyl of 12 to 16 carbon atoms] -betaine. Preferred betaines are dimethylammonium hexanoate of 12 to 18 carbon atoms and acylamidopropan- (or ethan-) dimethyl- (or diethyl betaine) The betaine complex surfactants are also suitable to be used here. ^ 1 Sultaine Surfactant The sultaines useful herein are those compounds having the formula (R (R3-) aN) R * ZS0a ~, where R is a hydrocarbyl group of 6 to 18 carbon atoms, preferably an alkyl group of 10 to 16 carbon atoms, better still, an alkyl group of 12 to 13 carbon atoms, each R 3 - typically is alkyl of 1 to 3 carbon atoms, preferably methyl and Ra is a hydrocarbyl group of 1 to 6 carbon atoms carbon, preferably an alkylene group of 1 to 3 carbon atoms or, preferably, a hydroxyalkylene group.

The ampholytic surfactant Ampholytic surfactants may be incorporated in the detergent compositions herein. These surfactants can be broadly described as "secondary or tertiary amine derivatives" or "aliphatic derivatives of heterocyclic secondary and tertiary amines, wherein the aliphatic radical can be straight or branched chain.

Cationic surfactants Cationic surfactants can also be used in the detergent compositions herein.

Suitable cationic surfactants include the quaternary ammonium surfactants selected from the alkyl nitrogen or alkenyl surface-active agents, preferably N-alkyl or alkenyl-C-a. -ammonium; wherein the remaining N positions are substituted by methyl, hydroxyethyl or hydroxypropyl groups.

The water soluble detergent composition compound The detergent compositions of the present invention contain, as a preferred optional component, a water-soluble builder compound, typically present at a level of 1% to 80% by weight, preferably 10% to 70% by weight, better still, from 20% to 60% by weight of the composition. The "water-soluble" detergency builder compounds include the water-soluble monomeric polycarboxylates or their acid forms, the homopolymeric or copolymeric polycarboxylic acids or their salts, wherein the polycarboxylic acid comprises at least two carboxylic radicals separated from each other by no more than two carbon atoms; carbonates, bicarbonates, borates, phosphates, erylates and mixtures of any of the foregoing. The carboxylate or polycarboxylate builder may be of the monomeric or oligomeric type, if - ^ > In general, polycarboxylates are preferred in terms of cost and operation. Suitable carboxylates containing a carboxy group include the water-soluble saltse "of lactic acid, glycolic acid and their ether derivatives. Polycarboxylates containing two carboxy groups include the water-soluble salts of succinic acid, rhenal acid, acid (ethylenedioxy) diacetic acid, maleic acid, diglycolic acid, tartaric acid, tartronic acid and fumaric acid, as well as the ether carboxylates. and the sulfinyl carboxylates. Polycarboxylates containing three carboxy groups include, in particular, the citrates, aconitrates and citraconates soluble in water, as well as the succinate derivatives, such as the carboxymethyloxyauccinatees described in British Patent No. 1,379,241, the lactoxysuccinates described in British Patent No. 1,389,732 and the aminosuccinates "described in the application of the Netherlands 7205873, and oxypolycarboxylate materials, such as tricarboxylates of 2-oxa-l, l, 3-propane as described in British Patent No. 1,387,447. The polycarboxylates containing four carboxy groups include the oxydisuccinate described in British Patent No. 1,261,829, 1,1,2,2-ethane tetracarboxylates, 1,1,3,3-propane tetracarboxylates and 1,1-tetracarboxylates. , 2,3-propane. Polycarboxylate containing sulfo substituents include the sulfosuccinate derivatives disclosed in British Patent Nos. 1,398,421 and 1,398,422, as in US Pat. No. 3,936,448, and the sulfonated, polymerized citrates described in British Patent No. 1,439,000 The alicyclic and heterocyclic polycarboxylates include the cis, cie, cyclopentane tetracarboxylate, pentacarboxylate, cyclopentadienide, cis, cis, 2,3,4,5-tetrahydrofuran cistetracarboxylate, cis-dicarboxylates, and the like. -tetrahydrofuran, tetracarboxylates from 2,2,5,5-tetrahydrofuran, 1,2,3,4,5,6-hexane hexacarboxylates and carboxymethyl derivatives of polyhydric alcohols, such as sorbitol, mannitol and xylitor. Aromatic polycarboxylates include mellitic acid, pyromellitic acid and "phthalic acid derivatives" described in British Patent No. 1,425,343. Of the above, hydroxycarboxylates are the preferred polycarboxylates when they contain three groups _ carboxy per molecule, more particularly citrates. The original acids of the monomeric or oligomeric polycarboxylate chelating agents, or their mixtures with their saltse, for example, citric acid or citrate / citric acid mixture, are contemplated as useful builders components. Borate builders, as well as detergency builders containing borate-forming mate- rials, which can produce borate under the storage or washing conditions of the detergent, can still be used, but are not preferred. washing conditions lower than around 50 ° C, especially at less than around 0 ° C. Examples of carbonate detergent builders are alkali metal and alkaline earth metal carbonates, including carbonate and sodium sesquicarbonate and mixtures thereof with ultrafine calcium carbonate, as described in the German patent application. No. 2,321,001 ,. published on November 15, 1973. Specific examples of detergent buffers < Water-soluble phosphate materials are alkali metal tripoli phosphates, sodium, potassium and ammonium pyrophosphate, sodium and potassium and ammonium pyrophosphate, sodium and potassium orthophosphate, polymeta / phosphate "Sodium in which the degree of polymerization varies from 6 to 21, and salts of phytic acid. Suitable silicates include water-soluble sodium silicas, with a SiOa: NaOa ratio of 1.0 to 2.8, with proportions of 1.6 to 2.4 being preferred, and 2.0 being the most preferred. The silicate can come in the form of the anhydrous salt or a hydrated salt. The most preferred silicate is sodium silicate which has a SiOa: Na02 ratio of 2.0. The silicate are preferably present in the detergent compositions according to the invention at a level of from 5% to 50% by weight of the composition, better still from 10% to 40% by weight.

The insoluble partially soluble SQlUPle Q detergency compound.

The detergent compositions of the present invention may contain a partially soluble or insoluble detergency builder compound, typically present at a level of from 1% to 80% by weight, preferably from 10% to 70% by weight, most preferably, « from 20% to 60% by weight of the composition. Examples of partially water soluble builders include crystalline layered silicate. The examples of the improvement < Water-insoluble detergency builders include sodium aluminosilicates. The layered, crystalline sodium silicates have the general formula: where M is sodium or hydrogen, x is a number from 1.9 to 4 e and is a number from 0 to 20. The crystalline sodium silicates, dß this type, are "described in EP-A-0,164,514 and methods for their preparation are described in DE-A-3,417,649 and DE-A-3, 742, 043. For the purposes" of the present invention, x in the formula above general- has a value of 2, 3 or 4 and, preferably, is 2. The most preferred material is d-NaaSiaOa, obtainable from Hoechst AG as NaSKS- The crystalline, layered sodium silicate material, preferably it is present in granular detergent compositions as particles in intimate admixture with a water soluble, solid ionizable material. The solid ionizable material, soluble in water, is selected from the organic acids, the salts "of organic and inorganic acid and their mixtures. The aluminosilicate zeolites have the formula of unit cell: where z and y are at least 6.; the molar ratio of zay is from 1.0 to 0.5 and x is at least 5, preferably from 7.5 to 276, even better, from 10 to 264. The material of alurninosilicate is in hydrated form and "preferably is crietalino, containing 10% to 28%, better still, «from 18% to 22%, of water in a united form. The exchange materials of aluminosilicate can be materials that occur in nature, but are preferably derived in a synthetic way. Synthetic crystalline aluminosilicate ion exchange materials are available under the designations Zeolite A, Zeolite B, Zeolite P, Zeolite X, Zeolite MAP, Zeolite HS, and mixtures thereof. Zeolite A has the formula: a aC lOaJ aiSiOJ a; xHa0? where x is «from 20 to 30, especially 27. Zeolite X has the formula: NaßA [(A1052) ß? (SÍ0a)? O« _ 276Ha0 The heavy metal ion sequestrant.

The detergent compositions of the present invention may contain, as an optional component, a heavy metal ion ion sequestrant. By heavy metal ion sequestrant is meant here the components that act to sequester (chelate) heavy metal ions. These components may also have the ability to chelate calcium and magnesium, but preferably show selectivity for binding heavy metal ions, such as manganese and copper ions. The sequestrants of metal ion are generally present at a level of 0.005% to 20%, preferably from 0.1% to 10%, better still, from 0.25% to 7.5% and, still better, 0.5. % to 5% by weight of the compositions. The heavy metal ion sequestrants, which are acidic in nature, having, for example, functional phosphonic acid or carboxylic acid functionalities, can be present either in their acid form or as a complex / salt with an opposite or opposite cation suitable, such as an alkali or an alkali metal ion, an ammonium or substituted ammonium ion, or any mixtures thereof. Preferably the salt / water complex is soluble in water. The molar ratio of the opposite cation to the sequestrant of heavy metal ion preferably is at least 1: 1. Suitable heavy metal ion sequestrants, for use herein include organic phosphonates, such as the? Ol? (Alkanoyl alkylene glyphonphosphonates, alkali metal ethan-1-hydroxydiphosphonates and nitplotri ethylene phosphonates. Among the above species, the penta (diethylenetriammenethylenetriammanethylenephosphonate, ethylenediaminetrimethylenephosphonate, hexanethylene diamine tetramethylenephosphonate, and letty hydroxyl 1,1-phosphonate are preferred.) Other heavy metal ion sequestrants suitable for use in the present include: nitrilotpacét co acid and polycarboxylic acids, such as ethylenediaminetetraacetic acid, ethylentpa inopentaacetic acid, _ "Ethylendia modisuccinic acid, ethylene-diaryninigiglutanic acid, 2-hydroxy acid, or any of these substances. Especially preferred are ethylenediarn-N, N'-d-succinic acid (EDDS) or its alkali metal, "alkaline earth metal," ammonium or substituted ammonium salts, or mixtures thereof. The preferred EDDS compounds are the free acid form and the sodium or magnesium salt or its complex. Examples of said preferred sodium salts of EDDS include NaaEDDS and NaaEDD5. Examples of said preferred EDDS - • - with magnesium complexes include MgEDDS and MgaEDDS. Other "heavy metal ion" sequestrants to be used herein are the iminodiacetic acid derivatives, such as 2-hydroxyethyl ethyl acid or glyceryl iminodiacetic acid, described in EP-A-317,542 and in EP-A- 399.133. The sequestrants of iminodiacetic acid-acid N-2-hydroxypropylsulonic acid and aspartic acid-N-carboxymethyl-N-2-hydroxyl propyl-3-sylphonic acid, "described in EP ~ A-516.102 They are also suitable here. Sequestrants of b-alamine-N, N'-diacetic acid, aspartic acid-N, N'-diacetic acid, aspartic acid-N-rnonoacetic acid and iminodi succinic acid, described in EP-A-509,382, are also suitable. EP-A-476,257"describes sequestrants at low temperature, suitable. EP-A-510,331 describes suitable sequestrant, der? Va "two d? Collagen, q? Eratin or casein. EP-A-528,859"discloses an appropriate alkyliminodiacetic acid sequestrant. Also suitable are dipicolinic acid and 2-phosphonobutane-1, 2,4-tricarboxylic acid. Glycinamido-N, N'-disuccinic acid (GADS) is also suitable.

The enzyme stabilizer system Preferred compositions containing enzyme in the present may comprise "from 0.001% to 10%, approximately, preferably from 0.005% to 8%, better still, from 0.01% to 6%, * ~ approximately, by weight of an enzyme stabilizer system. The enzyme stabilizer system can be any stabilizing system that is compatible with the detergent enzyme. Said sieternae stabilizers may comprise calcium ion, boric acid, propylene glycol, short chain carboxylic acid, boronic acid and mixtures thereof. Said stabilizing systems may also comprise reversible enzyme inhibitors, such as reversible protease inhibitors. The compositions herein may optionally comprise from about 0 to 10%, preferably from 0.01% to 6% by weight, of chlorine "bleach" scrubbers, added to prevent chlorine bleach species, present in many chlorine bleach supplies. water, attack and inactivate lae enzymes, especially under alkaline conditions. Although chlorine levels in water can be small, typically in the range of 0.5 ppm to 1.75 ppm, chlorine is available in the total volume of water that remains in contact with the enzyme during washing, usually large.; consequently, the stability of the enzyme during use may be problematic. Said suitable chlorine scavenging anions are widely available and are illustrated by the salts containing ammonium or sulphite cations, bisulfite, thiosulfite, thiosulfate, iodide, etc. Similarly, antioxidants, such as carbamate, ascorbate, etc., can be used, organic amines, such as ethylenediaminetetraacetic acid (EDTA) or an alkali metal salt thereof; monoethanol (MEA) and its mixtures. Other conventional scrubbers, such as bisulfate, nitrate, chloride, sources of hydrogen peroxide, such as sodium perborate rahydrate, sodium perborate and sodium per-carbonate, as well as phosphate, condensed phosphate, acetate , benzoate, citrate, forrniate, lactate, malate, tartrate, salicylate, etc., and their mixtures, can also be used, if desired.

The organic polymeric compound Organic polymeric compounds are particularly preferred components of the detergent compositions according to the invention. By organic polymeric compound is meant essentially any commonly polyrnecopically-organic compound, such as dispersants and polymers. soil-suspending agents and those that prevent their redeposition, in detergent compositions. The organic polymeric compound is typically incorporated into the detergent compositions of the invention at a level of 0.1% to 30%, "preferably from 0.5% to 15%, better still, from 1% to 10% by weight, based on the The compositions. Examples of organic polymeric compounds include the homopolymeric or copolymeric organic polycarboxylic acids, soluble in water, or their salts, where the polycarboxylic acid comprises at least two carboxyl radicals, separated from each other by not more than two atoms. of carbon. Polymers of the latter type are described in GB-A-1, 596, 756. Examples of such salts are polyacrylate with molecular weight from 2,000 to 5,000 and their copolymers with maleic anhydride; said copolymers having a molecular weight of from 20,000 to 100,000, especially from 40,000 to 80,000. Other suitable organic polymeric compounds include the acrylamide and acrylate polymers, which have a molecular weight of 3,000 to 100,000 and the acrylate / fumarate copolymers having a molecular weight of 2,000 to 80,000. The polyamino compounds are useful herein, including those derived from aspartic acid, such as those described in EP-A-305, 252, EP-A-305,283 and EP-A-351, 629. Terpolymers containing selected onomeric units of maleic acid, acid < Acrylic, polyaspartic acid and vinyl alcohol, particularly those with an average molecular weight of 5,000 to 10,000 are also suitable herein. Other organic polymeric compounds suitable for incorporation into detergent compositions herein include cellulose derivatives, such as methyl cellulose, carboxymethyl cellulose and hydroxyethyl cellulose. Other useful organic polymeric compounds are polyethylene glycols, particularly the < of molecular weight 1,000 to 10,000, better still, of 2,000 to 8,000 and, what is most preferred, of around 4,000.

The lime soap dispersant compound The compositions of the invention may contain a dispersing compound of lime soap, which has a lime soap dispersing power (PDJC) as defined below, of no more than 8, preferably no more. of 7, still better, no more than 6. The lime soap dispersing compound is preferably present at a level of 0.1% to 40% by weight, better still, of 1% to 20% by weight, still better, of 25 to 10% by weight of the compositions. A dispersant "of lime soap is a material that prevents the precipitation of alkali metal salts, from . Ammonium or amine of fatty acids, by calcium or magnesium ions. A numerical measure "of the effectiveness of a lime soap dispersant is given by the lime soap dispersing power (PDJC) which is determined using the lime soap dispersion test, as described in an article by HC Boghetty and CA Bergrnan, J. Am. Oil. Chem. Soc, volume 27, pages 88-90 (1950). This test method of the "effusion" of lime soap is widely used by those having practice in this technical field referred to, for example, in the following articles < from 'magazine: U. N. Linfield, Surfactant Science Series. lathe 7, page 3; U. N. Linfield, Tensi «of Surf. Det .. lathe 27, pages 159-161 (1990); and M. K. Nagarajan, U. F. Masler-, Cosmetics and Toiletries. volume 104, pages 71-72 (1989). The PDJC is the ratio, in percent by weight, of dispersing agent to sodium oleate required to disperse lime soap deposits formed by 0.025 g of sodium oleate in 30 ml of water with a hardness equivalent to 333 ppm <of CaCO3 (Ca: Mg = 3: 2). Surfactants having good lime soap diebility will include certain amine oxide, betaines, sulfobetaines, alkyl ethoxysulfates and ethoxylated alcohols. Exemplary surfactants, having a PDJC of not more than 8, for use in accordance with the invention, include direthylamine oxide of 16 to 18 carbon atoms, alkyl ethoxysulfate of 12 to 18 carbon atoms, with a "ethoxylation average of 1-5, particularly the alkyl ethoxy sulfate surfactant" of 12 to 15 carbon atoms, with a degree of ethoxylation of about 3 (PDJC = 4) and ethoxylated alcohols of 13 to 15 carbon atoms, with an average degree of ethoxylation of 12 (PDJC = 6) or 30, sold under the trade names Lutensol A012 and Lutensol A030, respectively, by BASF GmbH. Polymeric lime soap dispersants, suitable for use here, are described in an article by M. K. Nagarajan and U. F. Masler, which is found in 'Cosmetics and Toilet ries. volume 104, pages 71-73 (1989). Examples of such polymeric lime soap dispersants include certain water-soluble salts of acrylic acid, methacrylic acid or mixtures thereof, and a substituted acrylamide or acrylamide, wherein said polymers typically have a molecular weight of from 5,000 to 20,000.

The foam suppressor system The detergent compositions of the invention, when formulated for use in machine wash compositions, preferably comprise a suppressant system of eepurn, present at a level of 0.01% to 15%, "preferably from 0.05% to 10%, rnuy preferably from 0.1% to 5% in weight, relative to the weight of the composition. Suitable foam suppressor systems, to be used here, can essentially comprise any known antifoam compound, including, for example, silicone anti-foaming compounds, 2-alkylene antifoaming compounds and alkanol. Here, any compound or mixture of compounds that act to depress foam or foam formation produced by the dissolution of a detergent composition, particularly in the presence of agitation of the solution, particularly preferred antifoaming compounds, to be used here. , are silicone antispilling compounds, defined herein with any antifoam compound that includes a silicone component.These silicone antispray compounds also typically contain a silica component.The term "silicone", as used here and, in general, throughout the industry, covers a variety of "polymers" of relatively high molecular weight, containing siloxane units and hydrocarbyl groups of various types. The preferred illicone antispilling compounds are the siloxanes, particularly the polydimethylsiloxane and the end-block, trimethylsilyl units. Other suitable defoaming compounds include the monocarboxylic fatty acids and their soluble salts. These materials are described in US Patent 2,954,347, issued September 27, 1960 to Uayne St. John. The monocarboxylic fatty acids and their salts, for use as foam suppressors, typically have hydrocarbyl chains of from about 10 to about 24 carbon atoms, preferably from 12 to 18 carbon atoms. Suitable salts include the alkali metal salts, such as the sodium, potassium and lithium salts, and the ammonium and alkanolammonium salts. Other suitable antiperspirant compounds include, for example, the high molecular weight fatty esters (for example, the triglycerides of fatty acid), the fatty-free t esters of monovalent alcohols, the aliphatic ketones of 18 to 40 carbon atoms. (eg, stearone), N-alkylated arninotriazines, talents such as tri- to hexaalkylmelainam or di- to tetraalkyldiarninochlorotriazines, formed as cyanuric chloride products with two or three moles of a primary or secondary amine containing from 1 to 24 carbon atoms; propylene oxide, bis-steape acid amide and phosphates and alkali monostearyl-dirnetal phosphate esters (eg, sodium, potassium, lithium). The copolymers of ethylene oxide and propylene oxide, in particular the ethoxylated / propoxylated fatty alcohols with an alkyl chain length of 10 to 16 carbon atoms, with an ethoxylation degree of 3 to 30 and with a degree of propoxylation of 1 to 10, are also antifoaming compounds suitable for use here. The defoaming compounds of 2-alkylalkanols suitable for use herein have been described in DE 40 21 265. The 2-alkylalkanols suitable for use here consist of an alkyl chain of 6 to 16 carbon atoms, which carries a hydroxy group ends; and said alkyl chain is substituted in the alpha position by an alkyl chain of 1 to 10 carbon atoms. Mixtures of 2-alkylalkanolee can be used in the compositions according to the present invention. A preferred foam suppressor system comprises: (a) antifoam compound, preferably "silicone-based" composition, most preferably a silicone antifoam compound, which comprises, in combination: (i) polydimethylsiloxane, at a level of 50% to 99%, preferably from 75% to 95% by weight of silicone antifoam compound; and (ii) silica, at a level of "from 1% to 50%, preferably" from 5% to 25% by weight relative to the weight "of the antispilling agent of silicone / silica; wherein said silica / silicone antifoam compound is incorporated at a level of 5% to 50%, preferably 10% to 40% by weight; (b) a fluxing compound, most preferably comprising a silicone and glycol grid copolymer, with a polyoxyalkylene content of 72-78% and a ratio of ethylene oxide to propylene oxide of 1: 0.9 to 1: 1.1, at a level of 0.5% to 10%, preferably "from 1% to 10% by weight; A particularly preferred silicone and glycol grid copolymer of this type, eß DC0544, commercially available from Dow Corning under the trademark DC0544; (c) an inert carrier fluid compound, most preferably comprising an ethoxylated alcohol with an ethoxylation degree of from 5 to 50, preferably from 8 to 15, at a level of from 5% to 80%, preferably from 10% to 70% by weight. A preferred particulate foam suppressor system useful herein comprises a mixture of an alkylated siloxane, of the type described above, and solid silica.

- / The solid silica can be a silica ah? Ma «da, precipitated silica or a silica made by the technique and gel formation. Suitable silica particles have an average particle size of 0.1 to 50 microns, preferably 1 to 20 microns, and a surface area of at least 50 nm / g. These silica particles can be rendered hydrophobic by treating them with dialkylsilyl groups and / or with t-palleylethyl groups, either directly attached to the silica or by means of a silicone resin. It is preferred to employ a silica whose particles have become hydrophobic with di-ethyl- and / or trimethyl-silyl groups. A particulate antifoam composition, preferred, for inclusion in the detergent compositions according to the invention suitably contains an amount of silica such that the weight ratio of silica to silicone is on the scale "from 1: 100 to 3". : 10, preferably from 1:50 to 1: 7. Another suitable particulate foam suppressor system is represented by a hydrophobic silanated silica (most preferably trimethylsilane) having a particle size in the range of 10 nanometers to 20 nanometers, and a specific surface area "of more than of 50 ma / g, intimately mixed with dirnetyl silicon fluid having a molecular weight on the scale of about 500 to 200,000, at a ratio of silicone to silica silanada about 1: 1 to 1: 2. A preferred particulate foam suppressor system is "described in EP-A-0, 21.0, 731 and comprises a silicone antifoam compound and an organic carrier material having a melting point on the scale of 50. ° C at 85 ° C, wherein the organic carrier material comprises a glycerol rnonoester and a fatty acid which has a carbon chain containing from 12 to 20 carbon atoms. EP-A-0,210,721"discloses other preferred particulate foam suppressant systems, wherein the organic carrier material is a fatty acid or a fatty alcohol having a carbon chain containing 12 to 20 carbon atoms, or a mixture of them, with a point of fire of 45 to 80 ° C. Other highly preferred particulate foam suppressant systems are described in the co-pending European Application No. 91870007.1, in the name of The Procter and Gamble Company, which comprise a silicone antifoam compound, a carrier material, a material of organic coating and glycerol, at a weight ratio of glycerol: antifoam «silicone compound from 1: 2 to 3: 1. The pending European application 91201342.0 also "discloses highly preferred particulate foam suppressant systems, which comprise a silicone antifoam compound, a carrier material, a material of" organic coating and crystalline or amorphous aluminosilicate, at a weight ratio " of aluminosilicate: silicone antifoam compound "from 1: 3 to 3: 1. The preferred carrier material in both granular foam controllers, highly preferred, above described, is starch.A exemplary particulate foam suppressor system for use herein, is a particulate agglomerated component, by an agglomeration process which comprises, in combination: (i) from 5% to 30%, preferably from 8% to 15% by weight, of the component of the anti-spiking compound of eylicon, preferably comprising in combination, polydirnethylsiloxane and silica; (n) from 50% to 90%, preferably from 60% to 80% by weight «of the component, of carrier material, preferably, starch, (ni)« of 5% by weight 30%, preferably 10% to 20% by weight of the component, of agglomerated agglutinating compound, wherein said compound can be any compound, or its mixtures, typically used as agglomerators for agglomerates, preferably preferably, said agglomerating agglomerating compound comprises an alcohol et oxylate of 16 to 18 carbon atoms, with an ethoxylation degree of 50 to 100; and (iv) from 2% to 15%, preferably from 3% to 10% by weight, of hydrogenated fatty acid, from 12 to 22 carbon atoms.

Polymeric dye transfer inhibiting agents The detergent compositions herein may also comprise from 0.01% to 10%, preferably 0.05% a 0. 5% by weight of inhibitors dye transfer "~ >. Or file rich Loe agentee inhibitdoree dye transfer polirnérico copolirneros N-pyrrolidone and N- lpi vini are preferably selected" N-oxide polymers of polyamine, vinylimidazole, polymere «de polivini.ipi rroli« dona or combinations thereof. a) Polyamine N-oxide polymers The polyamine N-oxide polymers, suitable for use herein, contain bonds that have the following structural formula: P | Ax (I) wherein P is a polimerizable unit, to which the group R-N-0 can be joined, or where the group R-N-0 forms part of the polymerizable unit or a combination of both; A is 0 0 0 NC, C 0, C, -0-, -S-, -N-; x is 0 or 1; R is g? Poe aliphatic, ethoxylated aliphatic, aromáticoe, heterocíclicoe or alicyclic groups or any combination thereof, to which can bind the nitrogen of the N-0, or wherein the nitrogen of the N-0 is part of these groups The group N-0 can be represented by the following general structures: O (ity x -N-fl and < R3) z! ^ Í? J wherein R3-, Ra and R3 are aliphatic, aromatic, heterocyclic or alicyclic groups or combinations thereof; x and / or y and / or z are 0 or 1, and wherein the nitrogen of the group N-0 may be attached or wherein the nitrogen of the group N-0 is part of those groups > oe The group N-0 can be part of the polyrneable unit (P) or can be attached to the structure, polymeric, or a combination of both aspects. The N-oxides < Suitable polyamine, wherein the N-0 group of the uni forrna "dad comprise polymerizable N-óxidoe" polyamine wherein R is selected from aliphatic, aromatic, alicyclic or heterocyclic groups. One class of the polyamine N-oxides comprises the polyamine N-oxide group, wherein the nitrogen of the group N-0 is part of the group R. The preferred polyamine N-oxides are those in which R is a heterocyclic group such as pyrridine, pyrrole, imidazole, pyrrolidine, piperidine, "íumolina, acridine and" der? is "two. Another class of said N-oxides and ina polia comprises the group of N-oxides and polia to in The nitrogen of the N-0 group is linked to the group R. Other suitable polyarynide N-oxides are the polyamine oxides, to which the N-0 group is attached to the polyepable unit. -polyamine oxides are the polyamine N-oxides having the general formula (I), wherein R is an aromatic, heterocyclic or alicyclic group, wherein the nitrogen of the functional group N-0 is part of the R group. Examples of these classes are the polyamine oxides "doe" in which R is a heterocyclic compound, such as py Ridin, pyrrole, imidazole and its derivatives. Another class of N-oxides EETA poliamma consisting loe óxidoe of polyAM to have the general formula (I), loe cualee R is aromatic, heterocyclic or alicyclic groups wherein the nitrogen "of the N-0 functional is joined to the groups R. The examples of these classes are the polyamine oxides in which the R groups can be aromatic, such as phenyl. Any polymeric structure can be used as long as the amine oxide polymer formed is soluble in water and has dye transfer inhibiting properties. Examples of suitable polymer structures are polyvinyl, polyalkylene, polyesters, polyesters, polyamides, polynides, 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 may vary, either by appropriate copolymerization or by the appropriate degree.of N-oxidation. Preferably, the ratio of amine to amine N-oxide is from 2: 3 to 1: 1,000,000. Better still, from 1: 4 to 1: 1,000,000, most preferably from 1: 7 to 1: 1,000,000. The polymers of the present invention actually encompass random or block copolymers, wherein one type of monomer is an amine N-oxide and the other type of monomer is an amine N-oxide or not. The amine oxide unit of the polyamine N-oxides has a pKa < 10, preferably pKa < 7, better yet, pKa < 6. The polyamine oxides can be obtained in almost any degree of polymerization. The degree of polymerization is not critical, provided that the material has the desired water solubility and the dye-suspending potency. Typically, the average molecular weight is within the range of 500 to 1,000,000; preferably from 1,000 to 50,000, better still, from 2,000 to 30,000, even better, from 3,000 to 20,000.

^ The copolymers of N-vinylpyrrolidone and N-vinylimidazole Preferred polymers for use herein may comprise a polymer selected from the copolymers of N-vinylnitridazole, N-vimlpyrrolidone, wherein the polymer has an average molecular weight scale of from 5,000 to 50,000 better, from 8,000 to 30,000, especially from 10,000 to 20,000. Preferred copolymers of N-vinylimidazole-N-vmvpyrrolidone have a molar ratio of N-vinylniridazole to N-vimlpyrrolidone from l to 0.2, better still, from 0.8 to 0.3, still better, from 0.6 to 0.4. cJ pLivinilPyrrplidone The detergent compositions herein also use polyvinyl pyrrolidone ("PVP"), which has an average molecular weight of 2,500 to 400,000, preferably "from 5,000 to 200,000, better still, from 5,000 to 50,000; and especially "from 5,000 to 15,000. Suitable polyvinylpyrrolidones are commercially available "from ISP Corporation, New York, NY USA and Montreal, Canada, under the names" of product PVP K-15 (average molecular weight 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). PVP K-15 is also available from ISP Corporation. Other suitable polyvinylpyrrolidones, obtainable from BASF Corporation, include: Sokalan HP 165 and Sokalan HP 12. The polyvinylpyrrolidone can be incorporated in the detergent compositions herein at a level of from 0.01% to 5% by weight of the detergent. , preferably from 0.05% to 3% by weight, better still, from 0.1% to 2% by weight. The amount of polyvinylpyrrolidone supplied in the wash solution is preferably 0.5 ppm to 250 ppm, preferably 2.5 pprn to 150 ppm, better still, "5 ppm to 100 pprn. sil The polyvinyl Qxazplidone The detergent compositions herein can also utilize polyvinyloxazolidones as a polynuclear dye traneffective agent. Said polyvinyloxazolidones have an average molecular weight of 2,500 to 400,000, "preferably 5,000 to 200,000, better still," of 5,000 to 50,000, and most preferably "of 5,000 to 15,000. The amount of polyvinyloxazolidone incorporated in the detergent compositions can be from 0.01% to 5% by weight, preferably from 0.05% to 3% by weight, and more preferably from 0.1% to 2% by weight. The amount of polyvinyloxazolidone delivered in the wash solution is typically from 0.5 ppm to 250 ppm, preferably from 2.5 ppm to 150 ppm, even better, from 5 ppm to 100 ppm.

*) Polyvinylimidazole The detergent compositions herein can also use polyvinylimidazole as a polymeric dye transfer inhibiting agent. Said polyvinylimidazoles preferably have an average molecular weight of 2,500 to 400,000, better still, "from 5,000 to 50,000, and even better," from 5,000 to 15,000. The amount of polyvinylimidazole incorporated in the detergent compositions can be from 0.01% to 5% by weight, preferably from 0.05% to 3% by weight and, still better still, from 0.1% to 2% by weight. The amount of polyvinylimidazole in the wash solution is from 0.5 ppm to 250 ppm, preferably from 2.5 ppm to 150 ppm, even better, from 5 ppm to 100 pprn.

Optical brightener The detergent compositions herein may also optionally contain from 0.005% to 5% by weight of certain types of hydrophilic optical brighteners that also provide an inhibitory action of dye transfer. If used, the compositions of the preferentially will preferably comprise from 0.01% to 1% by weight of said optical brighteners. The hydrophilic optical brighteners, useful in the present invention, are those having the formula A "A; wherein R ee selects from anilino, N-2-bis-hydroxyethyl and NH-2-hydroxyethyl; Ra is selected from N-2-bis-hydroxyethyl, N-2-hydroxyethyl-N-methylamino, morpholino, chloro and amino; and M ee a salt-forming cation, such as sodium or potassium. When, in the above formula, R is anilino, Ra is N-2-bie-hydroxyethyl and M ee a cation such as sodium, the brightener is 4,4'-bisC (4-anilino-6- (N-2) acid. -bis-hydroxyeti1) -e-triazin-2-yl) amino] -2, .2'-stilbenedisulfonic acid and the disodium salt. This particular kind of brightener, is sold commercially under the trade name Tinopal- UNPA-GX, by Ciba-Geigy Corporation. Tinopal-UNPA-GX is the preferred hydrophilic optical brightener, useful in the detergent compositions herein. When, in the above formula, R is anilino, Ra ee N-2-hydroxyethyl-N-2-methylamino and M is a cation, such as sodium, the brightener is the sodium salt of the acid 4,4'- bieC (4-anilino-6- (N-2-hydroxyethyl-N-methylamino) -e-triazin-2-** l) arn? no] -2, 2'-styrylisonic acid. This particular polishing species is sold commercially under the trade name Tinopal 5BM-GX by Ciba-Geigy Corporation. When, in the above formula, Rx is anilino, R2 is rnorfolino and M is a cation such as sodium, the brightener- is the sodium salt of 4,4'-bisC (4-anilino-6-morpholino- s-triazin-2-yl) aminol-2,2'-eethylbenzene sulfonic acid. Eeta particular polish is sold commercially by Ciba-Geigy Corporation under the trade name Tinopal AMS-GX. Specific species of optical brightener selected for use in the present invention, give performance benefits especially effective in the inhibition of dye transfer, when used in combination with the selected, polymeric, dye transfer inhibiting agents described above. . The combination of said selected polymeric materials (by Example, PVNO and / or PVPVI) with said selected optical brighteners (for example, Tinopal UNPA-GX, Tinopal 5BM-GX and / or Tinopal AMS-GX), give significantly better inhibition of dye transfer in aqueous wash solutions, than any of these two components of detergent composition, when left alone. Without adhering to any theory, it is believed that such brighteners work "in this way because they have great affinity for the fabrics that are in the wash solution and, therefore, deposit relatively quickly on these fabrics. The length to which the optical brighteners are deposited on the fabrics present in the solution < 1e washing can be defined by means of a parameter called "the exhaustion coefficient". The coefficient of depletion, in general, is the proportion of a) the polishing material "deposited on the cloth, with respect to b) the initial concentration of polish in the wash liquor. Brighteners with relatively high exhaustion coefficients are the most suitable for inhibiting dye transfer in the context of the present invention.

Softening agents Fabric softening agents may also be incorporated into fabric laundry detergent compositions, "in accordance with the present invention. Esoe agents They can be of inorganic or organic type. The softening agents inorganic are exemplified by the smectite clays described in GB-1, 400, 898. Organic fabric softening agents include tertiary amines insoluble in water, which are described in GB-Al, 514, 276 and in EP-B-0,011,340. Smectite clay levels are normally in the range of 5% to 15%, better still, 8% to 12% by weight, adding the material as a dry-mixed component to the rest of the formulation. The softening agents of organic fabrics, such as tertiary amines and water-insoluble or long double-chain amide materials are incorporated at levels of 0.5% to 5% by weight, usually from 1% to 3% by weight, while that high molecular weight polyethylene oxide materials and water soluble cationic materials are added at levels of 0.1% to 2%, usually from 0.15% to 1.5% by weight.

Other optional ingredients Other optional ingredients, suitable for being included in the compositions of the invention, include perfumes, colors and filler salts, sodium sulfate being preferred as the filler salt.

The form of the compositions The detergent compositions of the invention can be formulated in any desirable form, such as powders, granules, pastes, liquids and gels.

The livid compositions The detergent compositions of the present invention can be formulated as liquid detergent compositions. Said liquid detergent compositions comprise from 94% to 35% by weight, "preferably" from 90% to 40% by weight, and preferably from 80% to 50% by weight, of a liquid carrier, for example, water, preferably a mixture of water and organic solvent.

The compositions in oel Lae composition detergente of this . invention can also be in the form of gels. Said compositions are typically formulated with polyalkenyl polyether, which has a molecular weight of about 750,000 to 4,000,000.

The solid compositions The detergent compositions of the present invention preferably are in the form of solids, taladides, and granules. The particle size of the components of the granulated compositions, according to the invention, should preferably be such that no more than "5%" of the particles is greater than 1.4 mm in diameter, and no more than 5% of the particles. particles are less than 0.15 mm in diameter. The volumetric density of the granular detergent compositions according to the present invention, typically it will be "of at least 450 g / liter, more ^ abitually at least 600 g / liter and, even better, from 650 g / liter to 1,200 y / 1. The "volumetric density is measured by means of a simple embedding device and cup, which consists of a conical funnel, rigidly molded on a base, and provided with a butterfly valve at its lower end, to allow The contents of the funnel are emptied into an axially aligned cylindrical cup disposed below the funnel. The funnel is 130 mm and 40 nm, at its upper and lower ends, respectively. It is mounted so that the lower end is 140 rnm above the upper surface of the base. The cup has a total height of 90 mrn, an internal height of 87 mm and an inner diameter of 84 mm. Its nominal volume is 500 rnl. To make a measurement the funnel is filled with powder, pouring it by hand; the butterfly valve opens and . Let the dust fill the cup. The full cup "of the 'frame and remove excess powder' from the cup by passing an implement with a straight edge, eg a knife, through its top edge. Then weigh the full cup and double the value obtained for the weight of the powder to give the volumetric density in g / liter. If required, duplicate the measurements.

Preparation procedure - the granulated compositions In general, granular detergent compositions can be formed in accordance with the present invention, by means of a variety of other methods, including dry mixing, spray drying, agglomeration and granulation.

The washing methods The compositions of the invention can be used essentially in any washing or cleaning method, / including the methods of washing clothes and washing "of dishes in machine.

The method of washing dishes in machine A preferred method for washing dishes in machine comprises treating the dirty items selected from pots, glassware, cookware and cutlery, and mixtures thereof, with an aqueous liquid having dissolved or supplied therein, an effective amount of a washing composition. tableware in machine, according to the invention. By an effective amount of the machine dishwashing composition, it is typically meant from 8 g to 60 g of product, dissolved or diered in a lava solution with a volume of 3 to 10 liters, as the dosage of the product. and the volume of typical washing solution, commonly used in conventional machine dishwashing methods.

The methods to wash clothes in machine The "methods" for washing clothes in a machine here include trimming the laundry with an aqueous washing solution in a washing machine, which has an effective amount of a washing detergent composition available therein or dispensed therein. , according to the invention. The detergent can be added to the washing solution either by means of a dispenser drawer of the washing machine or by means of a supplying device. By an effective amount of the detergent composition is typically meant from 40 g to 300 g of the product, dissolved or dispersed in a washing solution with a volume "of 5 to 65 liters, which are the product dosage and the volume of solution of typical washing, commonly used in conventional methods for washing clothes in a machine. In a preferred method of washing in the present, a dispensing device is introduced which contains an effective amount of "detergent" product inside the tub of a washing machine, preferably one that is charged from the front, before beginning the lava cycle «Jo . The dispensing device is a container for the product "detergent used to directly supply the product in the tub of the washing machine, its volumetric capacity must be such that it is capable of containing sufficient detergent product, such as would normally be used in the washing machine. The washing method Once the washing machine has been loaded with clothes, the dispensing device containing the detergent product is placed inside the tub At the beginning of the washing cycle, the washing machine introduces water into the tub and periodically rotates the tub.The design of the dispensing device must be such that it allows the containment of the dry detergent product, but then allows the release of that product during the washing cycle, in response to its agitation, as it rotates the tub, and also as a result of "immersion in the lava water" do.To allow the release of the detergent product during washing, the device may possess vari as openings "Through which the product can pass.

Alternatively, the device can be made of a material that is permeable to liquid, but impermeable to the solid product, which will allow the release of the dissolved product. Preferably the product «detergent will be released quickly at the beginning of the washing cycle, thereby providing high, localized, transient concentrations of the components, such as water soluble detergent builder components and heavy metal ion sequestrant, in the washing machine tub, at that stage of the cycle, The preferred dispensing devices are reusable and are designed in such a way that the integrity of the container is maintained both in the dry state and during the washing cycle. The dispensing devices are especially preferred.Two for use in accordance with the invention have been described in the following patents: GB-B-2,147,717, GB-B-2,147,718, EP-A-0201376, EP-A-0288345 and EP-A-0288346. An article by J. Bland, published in Man? F cturina Che i ^ t. in November 1989, pages 41-46, also discloses especially preferred dispensing devices, to be used with granular laundry products, which are "of the type commonly referred to as" grand? letee ". Especially preferred dispensing devices are described in European Patent Publication Nos. 0343069 and 0343070. This latter application describes a device comprising a flexible sheath, in the shape of a bag, extending from a support ring defining a hole; the hole being adapted to admit sufficient product into the bag for a washing cycle in a washing process. A portion of the washing medium flows through the orifice into the bag, dissolves the product and the solution then exits through the hole towards the washing medium. A device is masked on the eroporter ring to prevent the "leakage" of wet, undissolved product; this arrangement typically comprises walls which extend adialy, which project from a central protuberance, in the configuration of wheel and spokes, or a similar structure, where the walls have a helical shape. In the detergent compositions, the abbreviated identifications of the components have the following meanings: XYAS: Alkyl (C? _? V) sodium sulfate 24EY: A predominantly linear primary alcohol of 12 to 15 carbon atoms, condensed with an average of Y moles of oxide «Je ethylene.

XYEZ: A predominantly linear primary alcohol of lx to l carbon atoms, condemned with an average of Z moles "of oxide" of ethylene.

XYEZS: an alkylene alkyl ester of IX to I atoms of carbon, condensed with an average of Z moles of ethylene oxide per mole. ? TFAA: N-metiigi? Alkyl phase of 16 to 18 carbon atoms. Silicate: Amorphous sodium silicate (proportion of Si02: Naa0 = 2.0). NaSKS-6: Crystal layered silicate, which has the formula d-NaaSiaOa. Carbonate: Anhydrous sodium carbonate. Polycarboxylate: Copolymer of 1: 4"of aleic / acrylic acids, average molecular weight approximately 80,000.

Zeolite A Hydrated sodium metasilicate of the formula (A10a? 02) 2 • 27HaO that has a primary particle size on the scale < 1 to 1 to 10 starters. Citrate Trisodium citrate dihydrate. Percarbonate bleach of sodium percarbonate anhi (dro particle, of empirical formula 2NaaC03- 3Ha0, reveals rapid release with a mixed salt of the formula ^ O * ask) -n.Naa.C0a. where n is 0.29 and in which the proportion by weight of per-carbonate to mixed salt is 39: 1. Percarbonate Percarbonate bleach from sodium anhydride (a particle coated with a sodium-silicate leaching solution (ratio SiaO: Naa.O = 2: 1) at a higher ratio of per-carbonate to silicate. sodium of 39: 1. TAED Tetraacetiletilendiarni na. TAED (Particle formed by agglomerating TAED with citric acid release and polyethylene glycol (PEG) "of slow Mw = 4,000), with a proportion by weight of components" of TAEDacid citric acid: PEG "of 75:10:15 coated with an outer coating of citric acid to a weight ratio of agglomerate: citric acid coating of 95: 5. Benzoylcapro- Particle formed by agglomerating benzoylcapro-lactam (partílactam (BzCl) with citric acid and liberalenglycol polyethylene (PEG) of Mw = 4,000, with a slow portion) by weight portion of BzCl components: citric acid: PEG of 63: 21:16, coated with an external coating of citric acid, at a weight ratio of agglomerate: citric acid coating of 95: 5. TAED (particle formed by agglomerating TAED with that of partially neutralized, fast neutralizing liberapolycarboxylate) at a ratio of TAED: polycarboxylate of 93: 7, coated with an outer coating of polycarboxylate at a weight ratio of "agglomerate: coating of 96: 4.

EDDS (Particulate particle formed by EDDS sprinkling that is liberated with MgSO *, at a weight ratio of 26:74 fast) Protease Proteolytic enzyme, sold under the trade name Savinase by Novo Induetriee A / S, with an activity of 13 KNPU / g. Amylase Amylolytic enzyme, sold under the trade name Termamyl 60T, by Novo Ind? Etriee A / S, with an activity of 300 KNU / g. Cellulase Cellulose enzyme sold by Novo Induetries A / S, with an activity "of 1,000 CEVU / g. Lipase Lipolytic enzyme sold under the trade name Lipolase by Novo Industries A / S, with an activity of 165 KLU / g. CMC Carboxirneti1celulosa eódic. HEDP Aci «do 1, 1 -hydrox ietandi phosphoric. EDDS etiiendiarnino-N, N'-dieuccinic acid, isomer [S, S], in the form of the sodium salt.

PVNO N-oxide of poly (4-vinylpyridine), copolymer of vinylnidazole and vinylpyrrolidone, which has an average molecular weight of 10,000.

Suppressor of 12% silicone / silica, 18% stea alcohol-granuryl foam, 70% starch, in granulated form. side. Non-ionic Ethoxylated / propoxylated, mixed fatty alcohol with 13 to 15 carbon atoms, with an average ethoxylation value of 3.8 and an average degree of propoxylation of 4.5, sold under the trade name Plurafac LF404, by BASF GmbH (low foam). Sodium metasilicate metasilicate (SiO ratio: Na20 = 1.0) Sodium Tripoli phosphate 480N Copper random copolymer of 3: 7 acrylic / methacrylic acid, average molecular weight around "3,500. PB1 Anhydrous sodium perborate monohydrate in the form of compacted particles to retard the release of hydrogen peroxide. Lactam was isolated from C3-carylactane monoethylene alkyl, from tialkynyl onium with tosylate, precursor of cationic peroxy acid bleach.

DETPMP Dietilentriani a-penta (methylene phosphonic acid), sold by Monsanto under the trade name Dequest 2060. Nitrate salt bismuth nitrate. bismuth. Paraffin Oil for finnish sold under the brand Sinog 70 by Uintershall. BSA Amylolytic enzyme sold under the trade name LE17 by Novo Industries A / S (enzyme activity around 1%). Sulfate Anhydrous sodium sulfate. PH Measured as a 1% solution in distilled water at 20 ° C.

EXAMPLE 1 The following detergent compositions were prepared for washing fabrics, the values being expressed as percentages by weight of the compositions. Composition A is a comparative composition, compositions B to E are according to the invention.

A B C D E Per-carbonate (particu- 22.5 22.5 fast release) Percarbonate (particle 22.5 22.5 slow release) PB1 16.0 DETPMP 0.5 0.8 EDDS (particle of li0.3 0.75 0.5 rapid beration) Protease 0.55 1.27 0.55 1.27 1.3 Lipase 0.15 0.15 0.15 0.15 0.2 Cellulase 0.28 0.28 0.28 0.28 0.3 Amilaea 0.27 0.27 0.27 0.27 0.3 Polycarboxylate 5.1 5.1 5.1 5.1 5.1 CMC 0.4 0.4 0.4 0.4 0.4 PVNO 0.03 0.03 0.03 0 .03 0.0 3 Supreeor dß eepuma 1.5 1.5 1.5 1.5 1.5 granulated Ingredientse menoree / miscellaneous up to 100% The following TSO values (in seconds) were obtained for each of the products A to D: T50 A B C D Protease < 60 < 60 < 60 < 60 Peroxyacid 130 190 2.05 240 AVO 95 225 230 115 CQIPflRnATIVES TEST METHOD - ELIMINATION OF STAIN Preication of the sample Three white cotton sheets were previously washed in a "non-biological, free" heavy-duty "whitening" detergent ". A series of six 6 x 6 cm fabric samples was cut from each sheet. Stains were painted uniformly on each series of samples. Additionally, previously prepared samples obtained from the EMPA Institute were also used. In summary, the following series of "fabric strands" was used: Enzymatic spots: Grass. Blanqueadles spots; Sangr-e EMPA Blood, milk and ink EMPA Greasy spots Coffee with milk. Lipstick The series of fabric samples were subjected to a washing cycle in an automatic washing machine. Then the elimination of the spots of the samples was determined, by means of a panel of experts, using a Schaffe scale of four points. The results by averaged, combined pairs of each of the series of comparisons are as given below, with composition A "of the prior art being used as the common reference. In more detail, automatic washing machine was used Miele 698 U and the "short cycle at 40 ° C" program was selected.

Water was used with d? Germán race of 12 ° (Ca: Mg = 3: 1). 75 g d of detergent was used, diepensed from a device with a granular head, placed in the middle of the canga. A fabric cloth of each type was washed together with a "ballast" can of 2.7 kg of lightly soiled sheets (one week "for domestic use).

"Comparative test - stain removal The above method of stain removal was followed to compare the efficiency of composition B with composition A of the prior art, to distinguish different types of stains. The results were the following.

Type of stain Benefit of stain removal (PSU) blood L? PM + .B * Blood, milk and ink EMPA + 1.6 * Paste +1.0 Coffee with milk + 1.1 * Lipstick +0.8 - «• Signi fi cant to the limit of 95% EXAMPLE 2 The following machine dishwashing compositions were prepared, containing bleach (parts by weight) according to the invention.

A D G TAED (slow-release particle) 2.2 2.2 2.2 3.5 1 o Calcium lactase 3.3 Paraffin 0.5 0.5 0.5 0.5 0.5 0.5 0.5 Bismuth nitrate 0.2 0.2 0.2 0.3 0.4 0.2 Protease 2.0 2.0 2.0 2.0 2.0 2.0 2.0 Amylase 1.5 1.5 1.5 1.5 1.5 1.5 BSA 1.5 DETPMP 0.13 0.13 0.13 0.13 0.13 0.13 HEDP 1.0 1.0 1.0 1.0 1.0 1.0 Non-ionic 2.0 2.0 2.0 2.0 2.0 2.0 1.5 Sul fato 23.0 22.8 22.4 22.7 22.2 21.5 0.3 Mieceláneos, including humidity, haeta the rest pH (1% solution) 10.7 10.7 10.7 10.7 10.7 10.7 11.0

Claims (15)

NOVELTY OF THE INVENTION CLAIMS

1. - A detergent composition, characterized in that it contains: (a) an enzyme; and (b) an organic peroxyacid bleach system; wherein a means is provided for retarding the release of the organic peroxyacid to a wash solution, with respect to the release of the enzyme, such that, in the T50 test method described herein, the time to obtain a concentration that is 50% of the final concentration of the enzyme is less than 120 seconds; and the time to achieve a concentration that is 50% of the final concentration of the organic peroxyacid is greater than 180 seconds.

2. A detergent composition according to claim 1, further characterized in that the time to obtain a concentration that is 50% of the final concentration of the organic peroxyacid is 180 to 480 seconds.

3. A detergent composition, characterized in that it contains: (a) an enzyme; and (b) an organic peroxyacid bleach seventh; wherein a means is provided for retarding the release of the organic peroxyacid to a wash solution, with respect to the release of the enzyme; so that, in the TSO test method described here, the time to obtain a concentration that is 50% of the final concentration of the enzyme is at least 100 seconds less than the time to obtain a concentration. that is 50% of the final concentration of organic peroxyacid.

4. A detergent composition according to claim 1 or claim 3, further characterized in that the organic peroxyacid bleach system comprises, in combination: (i) a source of hydrogen peroxide; and (n) an organic peroxyacid bleach precursor compound.

5. A detergent composition according to claim 4, further characterized in that the peroxyacid bleach precursor compound is selected from a peroxyacid bleach precursor compound which, by perhydrolysis, provides a peroxyacid which is: (i) a perbenzoic acid or a non-cationic substituted derivative thereof; or (n) a cationic peroxyade.

6. A detergent composition according to claim 5, further characterized in that the peroxyacid bleach precursor compound is selected from the group consisting of: a) an amine-substituted bleach precursor of the general formula: R1-C-N-R2-C-L, R1-N-C-R2-C-L R5 R5 wherein R is an aryl or alkaryl group containing 1 to 14 carbon atoms; Rp is an arylene or alkarylene group containing 1 to 14 carbon atoms; Rs is H or an alkyl, aryl or alkaryl group containing "from 1 to 10 carbon atoms; and L is a substitutable group; or b) a N-acylated lactam bleach precursor of the formula: in «where n is from 0 to 8, preferably from 0 to 2; and R * is an aryl, alkoxyaryl or alkaryl group containing from 1 to 12 carbon atoms, or a substituted phenyl group containing from 6 to 18 carbon atoms; and mixtures of a) and b).

7. A detergent composition according to claim 4, further characterized in that the peroxyacid bleach precursor compound is: wherein R ee H, alkyl, alkaryl, aryl, arylalkyl; and where R_. , R-R * and R "can eer loe miemoe or differnetee euetituyentee, eeleccionadoe of halogen, alkyl, alkenyl, aryl, hydroxyl, alkoxyl, amino, alkylamino, -C00R« a., Where R * is H or an alkyl group; and carbonyl functions.

8. A composition "detergent according to claim 4, further characterized in that the peroxyacid bleach precursor compared is tetracetyl-ethylenediarnine.

9. A detergent co-product according to claim 4, further characterized in that the source of hydrogen peroxide is an inorganic perhydrate salt.

10. A detergent composition according to claim 9, further characterized in that the inorganic perhydrate salt is an alkali metal percarbonate.

11. A detergent composition according to claim 1 or claim 3, further characterized in that it additionally contains a bleach catalyst.

12. A detergent composition according to claim 11, further characterized in that the bleach catalyst of the group consisting of MnIV2 (u-0) s (1,4,7-trimethyl-1,4,7) is selected. -triazacyclononane) 2- (PFA) 2; r \ r > xxx _. (u-0)? (u-0Ac) 2 (1,4, 7-trimethyl-1,4,7-triaza-cyclononane) 2- (C104.) a; Mnlv «(u-0) ß (l, 4,7-triazacyclononane - (C10 __»)! Z, MnITIMnIV «(u- O)? (U-OAc) 2- (1,4, 7-trimethyl-l, 4, 7-triazacyclo-nonane) 2 (C10) a. Mn (1,4,4-trimethyl-1,4,7-triazacyclononane (0CH) a- (PF?); Co (2,2, -bibepyridyl-arnine) Cl.sub.2; di- (isothiocyanate) bis-pyridyl-a ina-cobalt (II), trisdipyridylanine-cobalt (II) perchlorate, Co (2,2-bispyridylamine) a-OaC10_ * perchlorate, bis- (2,2'-bispyridylarnine) perchlorate-copper (II) , perchlorate "Of tris (di-2-pyridyl-amine) iron (II), gluconate of Mn, Mn (CFaS0a) s > Co (NHa) aCl, binuclear Mn, complexed with ligand of tßtra-N-dentate and bi-N- "dentate, including ^ Mn ^^ u-Oa n ^ N *) * and ÜBipyzMn111 (u-0) aMnIvbi ? ya] - (C10) ay their mixtures.

13. A detergent composition according to any one of claim 1 or claim 3, characterized in that it is free of chlorine bleach.

14. A detergent composition according to claim 1 or claim 3, further characterized in that it is in a different form to tablet.

15. The use of a detergent composition according to claim 1 or claim 3, in a method for washing fabrics, characterized in that the detergent composition is supplied to the washing solution by means of a dispeneator introduced into the fabric. tub of a washing machine, before starting the wash.