MXPA96004828A - Detergents with reduced levels of peroxigenate whitener containing a chelator and enzi - Google Patents

Abstract

An Index of Biological Whiteners ("BBI") is provided whereby detergent compositions containing bleach are defined, which contain lower levels of bleach and bleach activator along with particular levels of chelating agents and enzymes. The detergent compositions of the invention have a Biological Bleach Index greater than 65 as defined by a particular formula. In another aspect of the present invention, bleach-containing detergent compositions are provided, which contain lower levels of bleach and bleach activator and higher levels of chelator and preferably higher levels of enzymes. Particularly, the level of bleach / activator reduction is represented by the equation [X] f = a [X] or where "a" is less than 1, the amount of chelator increment is represented by the equation [Y] f > 2 / a [Y] o, and the amount of enzyme increase is represented by the equation [Z] f < 1 / a [Z

Description

FRGFNTES WITH REDUCED LEVELS OF PEROXTGFNQDO WHITENER CONTAINING A QUELflTRPQR AND ENZII1RS CR? PQ TECHNICAL 5 The present invention relates to detergent compositions containing bleach. In particular, the invention relates to detergent compositions that give effective bleaching performance using higher levels. '' of bleach and bleach activator ..

BACKGROUND OF THE INVENTION The addition of bleach to detergents It is often convenient due to the functional benefits that bleach can provide. For example, • laundry detergents, which contain bleaching! -, provide improved stain removal, cleaning and maintenance of whiteness percudidas. (1) Unfortunately, under certain circumstances, high levels of bleach in laundry detergents will dull the color of the fabrics.The elevated bleach levels in dishwashing detergents, under certain circumstances, may result in ; > 5 problems of tartarity in silver articles. Traditionally, high levels of bleach and bleach levels increase the costs of detergents for consumers. On the other hand, low levels of bleach can lead to defi cient performance. Accordingly, there is a need for detergents which give improved bleach performance, but which contain a low level of bleach. It is an object of the present invention to provide such detergents containing bleach, in a manner described in detail in what follows.

BRIEF DESCRIPTION OF THE INVENTION One aspect of the present invention is the establishment of a biological bleach index (IBB), by which bleach-containing detergent compositions are provided including those formulated for use in -methods for washing clothes and automatic washing c.e tableware, which contain lower levels of bleach and bleach activator with particular levels of chelating agent and enzymes. The detergent compositions of the invention have a biological bleach index (IBB) of nm of 65, when defined by the formula: I BELIEVED [RBIGBPT EBB - 4CC] + 26TE] -. + where: TC] - Chelator level (% by weight) x (number of chelator groups in the chelator)] / (molecular weight of the chelator) x i, 0UÜ; TE] - percentage by weight of enzymes selected from the group consisting of proteases, ilases, raisins, cellulases and their mixtures, in the detergent composition; assuming normal activities of protease J3 KNPU, arnilasa 300 KNU, l pass L65 'u and cellulase 2000 Cevu; CAB] = C (% by weight of bleach activator-) x (a factor of 6 par-a BOBS), a factor of 6 for catimotor activators, a factor of 550 for manganese dinuclear complex activators, and a factor of 4 for all other bleach activators)] / (bleach activator molecular weight) ) x 1,000; and XBP] = (% by weight of peroxygenated bleach) x (% of oxygen available from bleach peroxed) / J00. In another aspect of the present invention, bleach-containing detergent compositions are provided, which contain lower levels of bleach and bleach activator, and higher levels of chelator and, preferably, higher levels of enzymes. In particular, the level of the bleach / activator reduction is represented by the equation: λX = aCX] OJ where "a" is less than 1; the amount of chelator increase is represented by the effect [?] f 2.2 / aCYl "; and the quantity Ldad of enzyme increase is represented by the equation CZ! l / aCZ] 0. This is described in more detail later.

DESCRIPTION DETRLLRDR PE LR INVENTION It has now been discovered, surprisingly, that the higher levels of chelator and enzymes can compensate for lower levels of bleach in a composition.

A tergent. In other words, you can get benefits a. Cleaners for improved stain removal, percussive cleaning and maintenance of whiteness, provided by a predetermined level of bleach, at lower levels of bleach if higher levels of chelator and enzymes are used. i) The iolo bleach induction More particularly, one aspect of the present invention relates to the establishment of a biological bleach index ("IBB") that defines a formula that relates to lower levels of perborate bleach and bleach activator with particular required levels of chelator and of enzymes. According to this aspect of the present invention there is provided a detergent composition containing bleach, which comprises from 5% to 95% by weight of surfactant + detergent; from 0% to 80% by weight of improvement or detergency; from 0.5% to 40% by weight of peroxygen bleach; from 0.01% to 10% by weight of bleach activator; from 0.1% to 10% by weight of chelator; and from 0.05% to 5% by weight of selected enzymes of the group q? e consists of proteases, amylases, lipases, cellulases and their mixtures; wherein the detergent composition has a biological-bleach index ("IBB" of more than 65, as defined by the formula: LAB] CRB1CBP1 IBB 4CC] + 26CE] 320 12 where: CC] - [chelator level (% by weight) x (number of chelator groups in the chelator-)] / (molecular weight of the chelator) x 1,000; LE] = percentage by weight of enzymes selected from the group consisting of pro-teases, to lases, li raisins, cellulases and their mixtures, in the detergent composition; Assuming normal activities of protease 13 KNPU, amylase 300 KNU, lipase 165 KLU and cellulase 2000 Cevu; [AB] = [(% by weight of bleach activator) x (a factor- of 6 pair-to BOBS), a factor of 6 for cationic activators, a factor of 550 for complex dinucleate activators of manganese, and a factor of 4 for all activating bf activators)] / (molecular weight of bleach activator) x 1,000; and [BP] - (% by weight of peroxygenated bleach) x (% of oxygen available from the peroxygen bleach) / 100. The biological bleach index defines a particular relationship between the level of the chelator, the level of the enzymes, the level of peroxygen bleach and level of bleach activator. By following the relationships defined in the formula, compositions can be provided. Airborne agents that contain lower levels of peroxygen bleach and bleach activator, but still give benefits of laundry detergents containing bleach. The detergent compositions according to the invention have a biological bleach index of more than 65, preferably more than 75, and still better than R 0. As seen in the formula, fC] is defined by Ou the chelator- (% by weight) x (number of chelating groups in the chelator)] / (molecular weight- of the chelator-) x 1,000. The number of chelator groups in the chelator is factored into the formula, as a way to factopzar the chelator efficiency of the chelator (ie, it is believed that the chelator efficiency is influenced by the number of those chelating groups). "heady" "chelating groups" is meant, herein, functional groups that have a chelating ability, including, for example, the phosphonate and carboxylate groups. It is to be noted. {; said chelating groups frequently comprise, in solution, oxygen charged above. By way of example, the etiiend aminotetraacetic acid (EDTA) has four chelating groups (carboxylate). Again when seen in the formula, [E] is defined as the percentage by weight of the total enzymes present in the detergent composition, assuming normal activities of 13 KNPU protease, 300 KNU amylase, 165 KLU lipase and 2,000 Cevu cellulase. If the actual activities of these agents in the detergent compositions are different from their normal activities, the CE factor is adjusted accordingly.

For example, protease having an activity of 26 is used.

KNPU instead of the normal 13 KNPU, multiply the factor [E] by 2 to compensate for the extra activity of the enzyme. The same applies to arn lasas, lipases and cellulases. KNPU means kiloNovo units of protease; KNU are units , -i-? loNovo to measure amylase activity; KLU are Normal units defined by Novo to measure lipase activity; CEVU are normal units to measure cellulase activity. Those units of normal activity of the enzymes are well understood by persons skilled in the art. The detergent compositions of the present invention may also include other types of enzymes (e.g., peroxidases or lignases). The factor [AB] in the formula defines the level of bleach activator as adjusted by-a factor-that limits its per-activity. A factor of 6 is assigned for BOBS and for cationic activators; a factor of 550, for the complex activators of manganese di nuclear; and a factor of 4 is assigned to all other bleach activators. Again in the formula, with [BP] the level of peroxygen bleach is adjusted by the percentage by weight of oxygen available from the peroxygen bleach. The percentage by weight of "available oxygen" or percentage of "active oxygen" of the bleaching compounds p roxige os, _. well understood by experts in the field. For example, percarbonates have an available oxygen percentage of 13.5%, perborate rnonohydrides have an available oxygen percentage of 13.5%, perborate monohydrates have an available oxygen percentage of 5.5%, and perborate tetrahydrates Have an available percentage of oxygen of 10.5%. "« ~ In summary [C] is the chelator parameters / 100 g -the detergent, corrected for the number of chelating groups, CE] is the total enzyme level, corrected for the activity level of the enzymes; [AB] is the my bleach activator limolles / 100 g of detergent, corrected for the activity; and [BP] is the percentage by weight of oxygen available from the peroxy bleach.

') Detergent compositions having a reduced biana disinfectant and increased enzymes / enzymes In accordance with another aspect of the present invention, detergent compositions containing bleach are provided, which are defined by a reduction in the level of bleaching agent and an increase in the level of chelating agents and / or enzymes. In particular, a detergent composition containing bleach is provided, comprising from 5% to 95% by weight of rinsing detergent surfactant; from 0% to 80% by weight of detergency builder, bleaching and chelating agent and / or enzymes, wherein the ingredient levels are defined as follows. It has been found that the cleaner benefits are provided for a given amount of CX] 0 of bleach can also be obtained at reduced levels of bleach iX], if -A5® increases the levels of chelating agent TY] and / or is increased The enzyme levels [Z], according to the following cor-relations: CY] * 1 2 / a [?] 0 rz] _L 1 / aCXlo increase of the chelator and co enzyme levels, will result the improved removal of certain stains with respect to the product with high bleach content. In the above formulas, "f" means "final"; that is to say-, L > amounts in the final claimed detergent composition of the present invention, while "o" means "original", ie, the amounts that were present before the reductions / increases according to the present invention. Here [X] is the sum of bleaching agents, by percentage levels in weight in the product, considering 100 percent activity for bleaching agents. The bleaching agents are a hydrogen peroxide bleach or a bleach activator, an organic peroxyacid or mixtures of them. For example, the reduction of bleach can be derived from the decrease in the level of per-oxygenated bleach and / or in the bleach activator, in the detergen-e. TY] is the sum of one or more chelators, in percentage by weight, in the product. The increases in the level and the level can be from the increase in the level of the chelator type present in the product with a high level of bleach (if there is one) or by adding another one (s) of chelator (s) product or both. If the product with high level of bleach, that is,? 0 does not contain any chelator, then it is preferred that Y] * _ >; (CX] 0 - [?] *) / 3. CZ] is the sum of the total of enzymes, in% by weight in the product, assuming enzymatic activities as: Pr-oteases: 13 KNPU Arnilases: 300 KNU (^ Lipolases: 165 KLU Cellulases: 2,000 Cevu. in percentage by weight they can be corrected for other enzymatic activities, such as% by weight of protease (13 KNPU) =% by weight of protease ("P" KNPU) x (P713);% by weight of alase (300 KNU) =% by weight of amylase ("A" KNU) x A / 300); and sirní larrnente for lipolasas and cellulases. Other types of enzymes (eg, peroxidases or lignases), when present, are used for normal activities. Increases in enzyme levels may come from increases in all or some of the enzymes in the high-bleach formula, or by adding different enzymes, or both. In the above formulas, "a" is less than 1 !; CX] 0 is between 3% and 80%; TY] 0 is between 0% and 10% and CZ] 0 is between -n.01% and 10%. Preferably, 0.2 < _ a < l; better- yet, 0.5 j. a < 1; preferably, CY] 0 is between 0% and 3%, and preferably [Z] o is between 0.05% and 5%.

Examples of formulations: Ingredients = l to 0.75 a = 0.50 = 0 50 (1) (2) (2) (2) PB1 + 4.0 3.0 2.0 2.0 CX] 7.2 5.4 3.6 3.6 [Y] DTPA 0.4 1.2 1.6 1.6 Ingredients a = l a = 0. 75 a = 0.50 a - 0.50 (1) (2) (2) (2) A Savinase «- 0.18 0.24 0.36 0.18 BAN» - 0.23 0.31 0.45 0.23 Lipolasae 0.07 0.09 0.14 0.07 Cellulase * - - _ - _ GZ] 0.48 0.65 0.96 0.48 (1) High bleach content (2) Low bleach content With a low-bleach content product, [X] f, with increases in cellulase enzyme levels, the detergent should preferably have a robust anti-deposition system. (3) The bleaching agent An essential aspect of the invention is an oxygenated bleaching system. In a preferred embodiment, the bleaching system contains a peroxide compound and an Amino compound, bleach activator. The production of the organic peroxyacid occurs by an in situ reaction of the activator with the hydrogen peroxide, which is provided by the peroxygenated compound. Preferred peroxygen compounds include inorganic perhydrate bleaches. Compositions containing mixtures of a peroxygen compound and a bleach activator, in combination with a preformed organic peroxyacid, are also contemplated. r Peroxyacid compounds The inorganic perhydrate salts are the per-oxygenated bleaching compounds preferred herein. These salts are normally incorporated in the form of the salt of an alkali metal, preferably the sodium salt, at a level of 0.5% to 40% by weight, better still, of 1% to 30% by weight and, still - better still, from 1% to 7% by weight of the compositions. The examples of perhi salts < l? The inorganic salts include the perborate salts, particularly the perborate monoohydrate and the perborate te ahydrate, the per-carbonate, perphosphate, persulfate and persilicate salts. The inorganic per-hydrated salts are usually the alkali metal salts. The inorganic in-hydrated salt may be included as the crystalline solid, without additional protection. However, for certain perhydrated salts, the preferred embodiments of said granulated compositions utilize an iron-coated material that provides better storage stability for the perhydrated salt, in the granulated product. Sodium perborate may be in the form of the monohydrate of the nominal formula aBOaU ^ Os- or the tetrahydrate, NaB0aHa0a.3Ha0. Alkali metal percarbonates, particularly sodium percarbonate, are preferred perhydrates for inclusion in the compositions according to the invention. It has been found that compositions containing percarbonate have a tendency to undesirable formals in the presence of surfactants and water, less than compositions containing perborate. It is believed that this is typically due to the fact that the percarbonate has a smaller surface area and lower porosity than the perborate rnonohydrate.

This surface area and porosity act to promote the co-gel with fine particles of agglomerates. < the surfactant agent and, therefore, do not harm the sumi nor stro. Sodium percarbonate is an addition compound that has a formula corresponding to 2NasC03.3H; 2 ?, and can be obtained- in commerce as a crystalline solid. The percarbonate is most preferably incorporated into said compositions in a coated form, which gives stability to the product. A suitable coating material, which gives a product tability, combines the mixed salt of a sulphate and an alkali metal carbonate, soluble in water. Said coatings, together with the coating processes, have been described in GB-1,466, 99, issued by Tnterox on March 9, 1977. The weight ratio of the mixed salt coating material to the per-carbonate remains in the scale from 1: 200 to 1: 4, better still, from 1:99 to 1: 9 and, even better, from 1:49 to 1:19. Preferably, the mixed salt is sodium sulfate and sodium carbonate, having the general formula "aa O ^ .n-NaaCOs, wherein n is from 0.1 to 3, preferably n is from 0.3 to 1.0 and, better still , is from 0.2 to 0.5. Other coatings containing silicate, (alone or with borate salts or boric acids or other inorganic substances), waxes, oils, fatty soaps, may also be advantageously used with the present invention. The potassium peroxyphenol potassium peroxide is another inorganic salt that is used in the detergent compositions herein.

The bleach activator Bleach activators are compounds that react with hydrogen peroxide in a perhydrolysis reaction to produce a peroxyacid. In general, the bleach activators can be represented- OR wherein L is a substitutable group and X is essentially any functionality, such that, by perhydrolysis, the structure of the peroxyac produced is: Preferably the bleach activator compounds are incorporated at a level of from 0.01% to 10% by weight, better still, from 0.2% to 7% by weight, still better, from 0.5% to 4% by weight of the detergent compositions . The bleach activator compounds typically contain one or more N- or 0-acyl groups, and said activators can be selected from a wide variety of classes. Suitable classes include anhydrides, esters, linked, lactams and the acylated derivatives of irnidazoles and oxiranes. Examples of useful materials within these classes are described in GB-A-1686789. Suitable esters are described in GB-A-836988, 865798, m 1147871, 2143231 and EP-A-0170386. The bleach activator is preferably selected from the group consisting of tetraacetic acid ("TAED"), sodium nonanoi loxybenzenesulphonate ("NOBS"), sodium benzoyloxybenzenesulfonate ("BOBS"), benzoyl-? , 'rolactam, 6-nonanarn sulfonate? docaproil) ox? benzene ("NACA-OBS"), bleaches activators substituted with quaternary ammonium and fos omo, cationic mtryls, complexes with manganese (III) or (TV) dinuclear, and mixtures thereof. What is most preferred is tetraacetylethylene i a.

The substituent groups y and the substitutable group, hereinafter the group L, must be sufficiently reactive for the perhydrolysis reaction to occur within the optimum time frame (for example, during a wash cycle). However, if L is too reactive, that activator will be difficult to stabilize to be used in a bleaching composition. In a preferred aspect of the invention, L is a substituted group. ble in which the acid -Conju the anion formed in L has a pKa of 4 to 13. The preferred L groups are selected from the group consisting of: R4 -0-CH-C f-CH-CH2 -O-CH- and C-CH-CHz its mixtures; wherein R is an alkyl, aplo or alkaline group containing from 1 to 14 carbon atoms; R3 is a string of yz. alkyl containing from 1 to 8 carbon atoms; RA is H or R3 and Y is H or a solubilizing group. Any of R, R3 or R may be essentially substituted by any functional group including, for example, alkyl, hydroxyl, alkoxy, halogen, amine, nitrosyl, knot and ammonium or alkyne groups. Preferred solubilizer groups are: - Os / IA, "-A0 * -? T, -NAR3 X ~ and 0 < - and, most preferably, - OaTT and -CO2TTA wherein R3 is an alkyl chain containing from 1 to 4 carbon atoms; M os a cation that gives solubility to the bleach activator and X is an anion that gives solubility to the bleach activator. Preferably II is an alkali metal, ammonium or substituted ammonium caton, with sodium and potassium being most preferred, and X being an anion halide, hydroxide, rnetylsulfate or acetal.

The perbenzoic acid activator The perbenzoic acid activating compounds provide perbenzoic acid for perhydroly. Suitable per-benzoic acid activating compounds, 0-acylates, include benzoyl oxybenzenesulfonates, substituted or unsubstituted, including, for example, benzoyl ox benzenesulfoncyte: The benzolization products of sorbitol, glucose and all saccharides are also suitable, with benzoylating agents, including, for example: rA * = C0CHa; Bz - benzo io. The perbenzoic acid activating compounds, of the amide type, include: N-benzo Isucci ni ida, tetrabenzoi 1-ethylendiamma and the N-benzoyl-substituted ureas. Suitable perbenzoic acid activators of the ylidazole type include N-benzoylimidazole and N-benzo-1-benzylnidazole; and other useful N-acyl group-containing perbenzoic acid activators include N-benzoylpyrrolidone, dibenzoyltaupna and benzoyl acid Ipiroglutani or. Other perbenzoic acid activators include benzoyldiacyl peroxides, benzoyl tet aacyl peroxides and the compound having the formula: Phthalic anhydride is another per-benzoic acid activating compound, suitable, in the present: @ $ Suitable N-ac-lactate N-per-benzoic acid activators have the formula: / where n is from 0 to 8, preferably from 0 to 2, and R? It is a benzollo group.

Activators derived from acid oerhen? Oirn Activators derived from per-benzoic acid provide per-benzo substituted acids, when subjected to perhydrolysis. Suitable substituted perbenzoic acid derivative activators include any of the benzoic activators described herein, wherein the benzoyl group is substituted by essentially any functional group not positively charged (ie, not cationic). ), including, for example, alkyl, hydroxy, alkoxy, halogen, amine, nitrosyl and amide groups. A preferred class of susA-tuted perbenzoic acid activating compounds are the amide-substituted compounds of the following general formulas: 1 -C-N-R2-C-L R1 -N-C-R2-C-L p 1? "II R O R5 O O y-? X where R is an aplo or alkaryl group with 1 to 14 carbon atoms; R5 * is an aphenol or alkarylene group containing from 1 to 14 carbon atoms; and Ra is H or an alkyl, aplo or alkapol group having 1 to 10 carbon atoms; and L may be essentially any substitutable group. Rx preferably contains from 6 to 12 carbon atoms. Ra preferably contains from 4 to 8 carbon atoms. R * - may be aryl, substituted aryl or alkyl containing branching, substitution or both, and may be derived from any synthetic source or any natural source, including, for example, A, a tallow . Analogous structural variations are permissible even. The substrate may include substituent groups alkyl, halo, halogen, nitrogen, sulfur and other typical substituents or organic compounds. Rs preferably is H or methyl. R 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-0170386.

Cationic bleach activators The cath-ion bleach activating compounds produce cationic peroxyacids when subjected to peri-drolysis. Typically, cationic bleach activators are formed by substituting the peroxyacid portion of an appropriate bleach activator, with a positively charged functional group, such as an ammonium or alkylammonium group, preferably an 11- or 4-meriary group. Cationic bleach activators are typically present in solid detergent compositions as a salt with a suitable anion, such as a halide ion. The bleach activator compound which is to be substituted in this manner cationically, may be a perbenzoic acid or a substituted derivative thereof, an activating compound as described hereinabove.

Natively, the bleach activator compound can be any alkylcarboxylic acid activator compound or amide substituted alkylic bleach activator, as described below. Cationic bleach activators 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 475,512,458,896 and 284,292; and in JP 87-318,332. And - In UK patent application No. 9407944.9 and in US patent applications No. 08/298903, 08/298650, 08/298904 and 08/298906, examples of preferred cationic bleach activators are disclosed. Suitable cationic bleach activators include any of the alkyl- or benzoyloxybenzene sulfonates substituted with ammonium or with alkylammonium; ^ - * N-acylated caprolactans and benzoylperoxides of rnonobenzoi 1 ~ tet r-aacet? l lucosa. A preferred preferred substituted benzyllocarbon oxibencensulonat is the 4 - (t-n-methylalenonium) -nethyl derivative of benzoyl oxybenzenesulphonate: An oxybenzene fonate of alkyl cat iom substituted meat, preferred, has the formula: and s Preferred cos cation bleach activators of the N-acylated caprolactam class include the trialkylamino rnetylene benzoyl caprolactans, particularly methyld-benzoyl caprolactam of -rirnetium ammonium: Other preferred cationic bleach activators of the N-acylated caprolactam class include the trialkylamino r-thialkyl caprolactans: wherein n is from 0 to 12. Another preferred cationic bleach activator is 2- (N, N, N- -Ar-irnet-urnonium) ethyl-sodium or-4-sulphophenylcarbonate.

Activators of alkylpercarboxylic acid bleach Acid bleach activators to the ketopercarboxylic acid form percarb and lye acids when subjected to perhydrolytic acid. The preferred activators of this -How they give peraceic acid when they are subjected to peri drol i si s. Preferred carboxylic acid activating compounds of the iride class include the N, N, N ', N' -tetraacetylated alkylenders, in which the alkylene group contains from 1 to 6 carbon atoms, particularly those compounds in which the alkylene group contains 1, 2 and 6 carbon atoms. Particular preference is given to tetraacet-Iletiiendiarnine (TAED). Other preferred alkoxycarboxylic acid activators include: 3,5,5-t-phenethiohexanoyloxybenzene-1-fonate < sodium (iso-NOBS), nonanoi loxibencensul sodium fonate (NOBS), sodium acetoxybenzenesulfonate (ABS) and pentaacet l-glucose.

The activators of aikiroperoxy acid bleach. substituted with amide.

The amide-substituted alkylperoxy acid bleach activating compounds are also suitable, occluding those having the following general formulas: R-C-N-R52-C-L or Rx-N-C-R52-C-L II I II I II M I I 0 Ra 0 Rß 0 0 wherein R is an alkyl group having from 1 to 14 carbon atoms; R2 is an alkaline group that con-t lene from 1 to 14 car-bono atoms; and Ra is 1-l or an alkyl group containing from 1 to 10 carbon atoms and L can be essentially any substitutable group. R preferably con-t lene from 6 to 12 carbon atoms. R2 preferably contains 8 carbon atoms. R may be straight or branched chain alkyl containing branching, substitution or both, and may be from any synthetic source or any natural source, including, for example, tallow fat. Analogous structural variations for RA are permissible Substitution may include alkyl, halogen, nitrogen, sulfur and other typical constituents or organic compounds .. Rs is preferably H or methyl Rx and Rs must not contain more than 18 total carbon atoms The amide-substituted bleach activator compounds of this type are described in EP-A-0170386.

The organic peroxyacid activators of ben7? Xa? Ina Also suitable are benzoxazole ipo compounds, such as those described, for example, in EP-A-332,294 and EP-A-48, 07, particularly those having the formula: which include benzoxazines of the type: N where R is H, alkyl, alcaplo, aplo, aplaxyl; and where Ra. Ra. R * and R "may be the same or different substituents, selected from H, halogen, alkyl, alkenyl, aplo, hydroxy, alkoxy, arnino, alkylam, COOR * (where Res, is H or an alkyl group) and functions ilo coal. An especially preferred activator of the ben "? Oxazine type is: Y Nuclear manganese complex activators Other preferred bleach activators are a complex of manganese (III) dinuclear or manganese (IV) di nuclear, such as those described, for example, in US Patent Applications Nos. 5,246,621 and 5,244,594. Preferred activators of this class are those referred to by 'having the following formulas: 1) CrinIva (? N-0) 3IMe-7ftCN) a] (PF?) A 2) CMnIVa (rn-0) « (Ne / rie-TACN) s.] (PF?): A. i CMnttt: 2 (rn-0) (rn -OAc) -, (Me-TACN) a3 (PF *) __- *, Cnntt?: .. (? n-0) (m-OAc) =! (re / lvle-TACN) ^] (PF < s) Or where Me -TACN is 1, 4, 7 -t pmet 11 -i, 4, 7-tr? azac? clononane and Me / Me-TACN is 1, 2,4, 7-tet rarneti ll, 4, 7-tpazac clononane.

Preformed organic peroxyacid The bleach system may contain a preformed organic peroxyacid, typically at a level of from 0.1% to 20% by weight, still better, from 0.2% to 10% by%, or, even better, from 0. 3% to 5% by weight of the composition. A preferred class of organic peroxyacid compounds are the amide substituted compounds of the following general formulas: R - C ~ N - Ra ~ C - OOH or R1 - N - C - R2 - C - OOH II I II I II II I I 0 Ra 0 R59 0 0 wherein Rx is an alkyl, aplo or aralkyl group having from 1 to 14 carbon atoms; Ra is an alkali, arylene or alean group containing 1 to 14 carbon atoms; and RM is H or an alkyl, aplo or alkaryl group containing from 1 to 10 carbon atoms. R may be straight or branched chain alkyl, aplo or substituted alkyl, which contain, substitution or both, and may be from synthetic or natural sources, including, for example, tallow grease.

' On? more? Structural analogue variations for Ra. The substitution may include alkyl, halogen, nitrogen, sulfur and other typical substituent groups or organic compounds. R "* is preferably H or methyl R and Rs should not contain more than 18 carbon atoms in total The amide-substituted bleach activator compounds of this type are described in EP-A-0170386. Other organic peroxyacids They include diacyl- and tert-acylperoxides, especially diperoxy dodecanedioic acid, diperoxtradecanedioic acid and diperoxyhexadecanedioic acid, and also mono- and di-zelactic acid, mono- and diperbranic acid and N-phthalolanyl acid are suitable here. noperox? capro? co. (4) The chelator • Suitable chelators have the ability to sequester heavy metal ions (such as Mn "*" * -, Fe - * "* and Cu + ") in solution Such chelators include amine carboxylates, aryl phosphonates, and polyfunctionally substituted aromatic chelators.The amino carboxylates useful as chelating agents in the compositions of the present invention may have a more, preferably at least two units of the structure: CHa \ N - (CHa) > < ~ COOH / wherein M is hydrogen, alkali metal, ammonium or substituted ammonium (eg, ethanolam ma) and x is from 1 to 3, preferably 1. Preferably these arnino carboxylates do not contain alkyl groups of more than 6 carbon atoms. The carboxylates of apu or operable include: * T ilendiarninotetr-aacetatos, N-hydrox? Eti letiiendiaininotriacetatos, or tplotpacetat os, et Llendiammodisuccmatos, et? Lend? Arn? No ~ N, N '-diglutamatos, 2- H? drox? pr'o ?? lend? arn? no-N, N '- disuccinates, and ilendiarninotetrapropionates, triet-Ilentetra-ammohexaacetates, dietary lenthia nopentaacetatos and ethanol-diglyces, their alkali metal, ammonium salts and substituted ammonium, and mixtures thereof. The monophosphonates are also useful for using "" "DI? Or chelating agents in the compositions of the invention, when at least low levels of total phosphorus are allowed in the detergent compositions." Compounds with one or more, preferably two units of the substructure: CHa \ 1 1 N CHa); P0"Ma / where M is hydrogen, alkali metal, ammonium or ammonium or substituted and x is 3, preferentially 1, are occluding: tet rarnetilenephosphonates of ilendiapu, tetraethylenephosphonates of hexane, and phosphonates de ami notet ranetlleno, nitride threonine phosphonates and penta ethylene phosphonates of diethientriami a. Preferably those phosphonates of a or do not contain alkyl or alkenyl groups of more than 6 carbon atoms. Alkylene groups can be shared by the best structures. Aromatic chelating agents, substituted with polyfunctionality, are also useful in the compositions herein. These materials can comprise compounds that have the generic formula: wherein at least one R comprises chelating groups S03H or -COOH or their soluble salts and mixtures thereof. US Pat. No. 3,812,044, issued May 21, 1974 to Connor 'and co-inventors, incorporated herein by reference, discloses chelating agents and sequestrant-is aromatic, poly-unanally substituted. Preferred compounds of this type, in acid form, are dihydroxydisulfobenzenes, such as 1,2-d? H? Drox? -3, 5 -disulfobenzene. The compositions ? Alkali metals may contain these materials in the form of alkali metal, ammonium or substituted ammonium salts (for example, rnonono- or t-bentanolamine salts). Other suitable chelators include hydroxyl-1, 1-ethylidenediphosphonic acid and its derivatives; ethylenediamine succinate, sodium t-disodium salt of S, S-ethylend a ma, indole diacetic acid, N-2-hydroxypr-opylsulphonic acid (see EP 516,102 of Dow Chemicals); the beta-alam acid, non-N, Nd? acetic acid, asparic acid, acid?, Nd? acetic acid, aspart co-N-? nonoacetic acid and indole dihydric acid (see FP 509,382 of Gi). Ace Co.); alkynyl dianacetic acid (see EP 526,959, Grace Co.); the iso-serindiacetic acid (BASF); 2-phosphobutan-l, 2,4-tricarboxylic acid (Bayer); acid dipi coll meo, the protein derived from collagen, keratin or casein (see EP 510,331, by Huís); amino acid-based chelators (see -K-P 476,257 by Huís) and chelators having the following structure (see DE 4024552 of Henl-el): Preferred chelators according to the present invention are selected from the group consisting of diethylene triamine pentamethylene phosphonates, ethylene diamine tetramethylene phosphonates, diethylammonium pentaacetates, ethylene diamine disuccinates, ethylene amine tetraacetates, and mixtures thereof. The amount of chelator-used in the present detergent compositions is typically from 0.1% to 10% by weight, preferably from 0.2% to 7%, better still, from 0.4% to 3% and, even better, from 1% to 1.8% (5) Enzymes Enzymes suitable for use in the present invention are proteases, alases, lipases, cellulases or their mixtures and, optionally, other types of enzyme. Proteases and amylases are preferred. - * - Suitable examples of proteases are subtypes, which are obtained from particular strains of B. subtilis. B. lent.us and B. licheni forrnis. Another suitable protease is a bacterial septa protease enzyme, modified, obtained from Bad lUS SufrtlllS or from Bac llus licharu for-iin s. which has maximum activity across the pH range of 8 to 12, developed and sold by Novo Industries A / S (Denmark) under the trademark ESPERASE. The preparation of that enzyme and analogous enzymes is described in British Patent Specification No. 1,243,784 of Novo. The enzymes V > Theories, suitable for removing protein-based stains, which can be obtained commercially, include those sold under the commercial designations ALCALASE and SAVINASE by- Novo Industries A / S and MAXATASE by International Bio-Synthetics, Inc. ( Netherlands). Other proteases include protease A (see European patent application 130,746, published January 9, 1985) and Protease B (see European patent application Serial No. 87303761.8, filed on April 28, 1987, and the application European patent 130,756, by Bott and co-inventors, published January 9, 1985). What is most preferred is what is called "Pr-oteasa C", which is a vanant of an alkaline serine protease, from Bacillus / particularly Bacillus lentus. where the arg mina replaces the lisma in position 27, the tyrosma replaces the val in position 104, senna replaces asparagine at position 123, and "^ a alanine replaces threonine at position 274. Protease C is described in EP 90915958: 4, US patent 5,185,250 and US patent 5,204,015, which are incorporated herein by reference.The gene variants are also included herein. modified, in particular, from protease C. Arnilases include, for example, α-amylases, described in British Pat. No. 1,296,039 (Novo), RAPIDASF, International Bio-Synthe-t i cs, Inc. and TERMAMYL and BAN (bacterial α-amylase), from Novo Industries.

The cellulases usable in the present invention include both bacterial cellulose and fungal cellulose. Preferably they will have an optimum pH between 5 and 9.5. Suitable cellulases are described in U.S. Patent 4,435,307, Barbesgoard and co-inventors, issued March 6, 1984, which describes fungal cellulase, produced from Hurnicola insolens and the Humicola DEM 1800 strain, or a cellulase-producing fungus 212 , which belongs to the genus Aero onas and La cellulasa extracted from the hepatopancreas of a marine mollusk (Dolabella auricula solander). Suitable cellulases are also described in GB-A-2, 075, 028, GB-A-2,095,275 and DE-O -2, 247, 832. Lipase enzymes suitable for use in detergents include those produced by microorganisms of the Pseudomonas group. such as Pseudornonas stut, -ep ATCC 19,154, as described in British Patent 1,372,034. See also ??? raisings in the Japanese patent application 53-20487, open to public inspection on February 28, 1978. The lipase is available from Amana Phar aceutical Co., Ltd., Nagoya, Japan, under the trade name Lipase P. "Amano" , hereinafter referred to as "Amano-P". Other commercial lipases include: Arnano-CES, Chromobacter viscosur lipases. for example, Chrornobacter viscosum ya, llLOlVtJLCUffl NRRLB 3673, commercially available from Toyo Jozo Co., Tagata, Japan; and other lipases from Chrornobac r vi scosurn. from U. S. Biochepu cal Corp. E. U. A. and Disoynth Co., The Netherlands; and li raisins from U. S. Eiochemical, rp., E.U.A ,. and Disoynth Co., The Netherlands, and lipases from Pseudomonas gladioli. The LIPOLASE enzyme, derived from the fungus HumiCQla lanuqinQSa and expressed in Asoerg llus orvzae. as a guest and commercially available from Novo (see also EP 341,947) is a preferred lipase for use herein. Other enzymes, such as peroxidases and / or lignases, may also be used in the detergent compositions herein. The peroxidase enzymes are known in the art and include, for example, horseradish peroxidase, ! "xigninase and haloperoxidase, such as chloro- and bromo-peroxidase." The detergent compositions containing perox idasa are described, for example, in the international application of the TCP WO 89/099813, published on October 19, 1989 by 0. Kirk , as a transfer agent to Novo Industries A / S. The detergent compositions of the invention preferably have from 0.05% to 5% by weight of enzymes, / - better yet, from 0.1% to 3%, still better still, of 0.2. % to 2% and, what is more preferred, from 0.5% to 1.5%. (6) The detergent surfactant The detergent surfactants, useful herein, are mentioned in U.S. Pat. 3,664,961, of Norps, issued May 23, 1972, and 3,919,678, of Laughlm and co-inventors, issued on December 30, 1975, both incorporated herein by reference.

The following are representative examples of detergent surfactants useful in the compositions herein. Water-soluble salts of higher fatty acids, ie, "soaps", are useful ammonium surfactants in the compositions herein. This includes alkali metal soaps, such as the sodium, potassium, ammonium and alkylbenzoic salts of higher fatty acids having from R to 24 carbon atoms and, preferably, from 12 to 18. carbon atoms. It can be formed by soaps by direct saponification of fats and oils, or by the freezing of free fatty acids. Particularly useful are the sodium and potassium salts of the fatty acid mixtures derived from coconut oil and tallow, ie sodium and potassium tallow and coconut soaps. Useful ammonium surfactants include Also, the water-soluble salts, preferably the alkali metal, ammonium, and onion salts, of the organic reaction products-sulphonates having their molecular structure-are an alkyl group containing 10 to 20 carbon atoms and a sulphonic acid or sulphonic acid ester group (the alkyl portion of the acyl groups is included in the term "alkyl") Examples of this group of synthetic surfactants are: sodium and potassium alkylsulfates, especially those obtained by sulfation of higher alcohols (8 to 18 carbon atoms), such as 1 j's produced by reducing the glycerides of sebum or coconut oil; and the alkali metal and potassium carbonates, in which the alkyl group contains from 9 to 15 carbon atoms, in straight chain or branched chain configuration; for example, those of the type described in US Patents 2,220,099 and 2,477,383. Linear straight chain alkylbenzene sulphonates are particularly preferred, wherein the average number of carbon atoms in the alkyl group is from 11 to 13; the primary and secondary alkylsulphates of 12 to 25 carbon atoms, and the methyl ester sulphonates. Other anionic surfactants herein are the sodium alkoxyglyceryl ether sulfonates, especially the ethers of higher alcohols derived from tallow and coconut oil; the sulphonates and sulphonates of monoglyceride of sodium acid coconut coconut oil; the sodium or potassium salts of alkylphenol ether sulfates, which contain 1 to 10 units of wood oxide per molecule; and wherein the alkyl groups contain from 8 to 12 carbon atoms; and the sodium or potassium salts of alkyl ether sulfates and ethylene oxide, containing from 1 to 10 ethylen oxide units per molecule, and wherein the alkyl group contains from 10 to 20 carbon atoms. Other ammonium surfactants useful herein include the water-soluble salts of alpha-sulfonated fatty acid esters, which contain from 6 to 20 carbon atoms in the fatty acid group and from 1 to 10 carbon atoms in the the ester group; the water-soluble salts of 2-ac? lox? alk-1-phonic acids containing from 2 to 9 carbon atoms in the acyl group and from 9 to 23 carbon atoms in the alkane portion; the water-soluble salts of olefam and fine sulfonates containing from 12 to 20 carbon atoms; and the beta-alkyloxyalkanesulonates containing from 1 to 3 carbon atoms in the alkyl group and from 8 to 20 carbon atoms in the alkane portion. Water-soluble nonionic surfactants are also useful in the compositions of the invention. Such nonionic materials include compounds produced by the condensation of alkylene oxide groups (hydrophilic in nature) with an organic hydrophobic compound, which may be aliphatic or aromatic alkyl. The length of the polyoxyalkylene group that is condensed with any particular hydrophobic group can be adjusted to a specific pair.

-Produce a water-soluble compound that has the desired degree of balance between the hydrophilic and hydrophobic elements. A particular class of additional nonionic detergents, especially useful herein, comprises the amides of acidic hydroxyl hydroxide of the formula: wherein R is H, hydrocarbyl of 1 to 8 carbon atoms. carbon, 2-hydroxyethyl, 2-h? drox? prop? it or a mixture of them; of alkyl difference of 1 to 4 carbon atoms, better still, alkyl of 1 or 2 carbon atoms, still better still, alkyl of 1 carbon atom (ie, methyl); and Ra is a hydrocarbyl portion of 5 to 32 carbon atoms, preferably straight chain alkyl or alkene, of 7 to 19 carbon atoms, better still, straight chain alkyl or alkene, of 9 to 17 carbon atoms, still still better, straight chain alkyl or alkem, from 11 to 19 carbon atoms, or mixtures thereof; and Z is a portion po) ih droxi hi drocarbilo, which has a linear hydrocarbon chain with at least 2 (in the case of giiceraldehyde) or at least 3 hydroxyl (in the case of other reducing sugars), directly connected to the chain; or an alcoholic derivative (preferably ethoxylated or propoxylated) thereof. Z, preferably, will be derived from a reducing sugar in a reductive ammation reaction; Even better, Z is a glycityl moiety. Reducing sugars Suitable include: glucose, fructose, maltose, lactose, galactose, mannose, and slabs, as well as dextrose glyceral, and high-dextrose corn syrup, high-fructose corn syrup, and syrup may be used as raw materials. of maize with a high maltose content, as well as the individual sugars mentioned above.These corn syrups can produce a mixture of sugar components for Z. It should be understood that in no way is it intended to exclude other suitable prunes. Z, preferably, will be selected from the group consisting of: -CH2- r M-10H) N-CHaOH, -CH (CHaOH) - (CHOH) rl_j.-CHaOH and CHa (CHOH) 2 (CHOR ') ( CHOH) -CHaOH, wherein n is an integer from 1 to 5, inclusive, and R 'is H or a cyclic mono- or poly-saccharide, and its alkoxylated derivatives. Glycidyl, in which n is 4, is most preferred. in particular ~ CHa- (CHOH) * CHaOH In the formula (I), R can be, for example, N-methyl, N-ethyl, N ~ pr-opyl, Ni sopropyl, N-butiio, N ~? sobut? io, N-2-hydrox? et? lo or N-2-h? Roxypropyl. For maximum foaming, R is preferably methyl or hydro Lalqui lo. If little foam production is desired, R is preferably alkyl of 2 to 8 carbon atoms, especially n-propyl, isopropyl, n-butyl, isobutyl, pentyl, hexyl and 2-ethylhexyl. Ra-C0-N < it can be, for example, cocarnida, est ram ida, olearnida, laureruda, iristarnida, cappca ida, palmitamida, seboarnida, etc. Other suitable nonionic surfactants They include the condensates of alkylphenols with full polyether oxide, for example, the condensation products of alkyl phenols having an alkyl group containing from 6 to 15 carbon atoms, either in the r-chain configuration ecta or branched chain, with 3 to 12 moles of ethylene oxide per mole of alkyl phenol. Preferred nonionics are condensation products, water-soluble or water-dispersible, of aliphatic alcohols containing from 8 to 22 carbon lathes, in straight chain or branched chain configuration, with 3 > . 12 moles of ethylene oxide per mole of alcohol. Particularly preferred are the condensation products of alcohols having an alkyl group containing from 9 to 15 carbon atoms, with 4 to 8 moles of ethylene oxide per level of alcohol. The non-ionic, zwitterionic surfactants include the water-soluble amine oxides, which contain an alkyl portion of 10 to 18 carbon atoms and two portions selected from the group of alkyl and hydroxyalkyl groups of 1 to 3 carbon atoms; water-soluble phosphine oxides, containing an alkyl portion of 10 to 18 carbon atoms, and two portions selected from the group consisting of alkyl groups and hydroxyalkyl groups containing from 1 to 3 carbon atoms; and water-soluble sulfoxides containing an alkyl portion of 10 to 18 carbon atoms and a portion selected from the group consisting of - "Alkyl and hydroxyalkyl joreiones of 1 to 3 carbon atoms The ampholytic surfactants include the aliphatic derivatives of secondary amines and alicyclic or heterocyclic amines, wherein the aliphatic portion can be straight chain or branched, and wherein one of the aliphatic substituents may be straight or branched chain, and wherein one of the aliphatic substituents contains from 8 to 18 carbon atoms and at least one aliphatic substituent contains an ammonium-water-soluble ammonium group .

Zwitter ionic surfactants include those derived from aliphatic ammonium, phospho- and sulfo or quaternary compounds, wherein one of the aliphatic substituents contains from 8 to 18 carbon atoms. The detergent compositions of the present invention contain from 5 to 95% by weight of detergent surfactant, preferably from 5% to 50% and, most preferably, from 10% to 30%. Y. The detergent surfactants used in the detergent compositions herein are preferably a mixture of ammonium and nonionic surfactants. (6) The optional detergency builder The optional ingredients of the detergent, in the present invention, are inorganic detergent builders. - "" - 'and / or organic. Inorganic builders include, but are not limited to, alkali metal, ammonium and alkanolarnome salts, polyphosphate salts (exemplified by tripol phosphates, pyrophosphates and vitreous polymetic metaphosphates), phosphonates, phytic acid , silicates, carbonates (including bicarbonates and sesquicarbonates), sulphates and alu-musilicates. However, in some cases, it is required that the detergency agents do not have phosphate. Examples of builders of builder are alkali metal silicates, in particular those having a S Oa O a to O ratio in the range of 1.6: 1 to 3.2: 1, and layered silicates, such as layered sodium silicates, described in US Pat. No. 4,665,839, issued May 12, 1987 to HP Riecl-, obtainable from Hoechst under the tradename "SKS"; SKS-6 is a layered silicate detergent builder, especially preferred. Carbonate improvers, especially a finely ground calcium carbonate with a surface area of more than 10 rn ^ / g, are preferred builders that can be used in granular compositions. The density of said detergents with alkali metal carbonate improver may be in the range of 450-850 g / 1, with a moisture content preferably less than 4%. Examples of carbonate enhancers are carbonates of "~ *) of the alkaline metal and alkali metal which are described in the German patent application No. 2,321,001, published on November 15, 1973. Alurinosilicat detergency builders are especially useful in the present invention. The polyunsaturated alkenes are zeolite detergent builders having the formula: Na? C (fllOa) _r (SlOa) v] -xHaO where z and y are integers of at least 6; The molar ratio of z to y is on the scale of 1.0 to 0.5 and x is an integer 4? riw1 14 to 264. Useful alurninosilicate ion exchange matepals are commercially available. These alurninosil icates can be crystalline or amorphous in structure and can be alu mosi licates that occur in nature or synthetically derived. Methods for producing alummosilicate ion exchange materials are described in US Pat. No. 3,985,669, to Corkill and co-inventors, issued August 12, 1986. Preferred crystalline, synthetic, preferred alurine ion exchange materials in the present, they are available under the designations Zeolite A, Zeolite P (B) (including those described in EPO 384,070) and Zeolite X. Preferably the aluminosilicate has a particle size of 0.1 to 10 microns in diameter. Organic detergents, suitable for the purposes of the present invention include, but are not limited to, a wide variety of polycarboxylate compounds, such as ether polycarboxylates, including oxydisuccina, such as those described herein. U.S. Patent No. 3,128,287, issued April 7, 1964, and in U.S. Patent 3,635,830, Lamberti et coinventores, issued January 18, 1972. See also "TMS / TDS" improvers of U.S. Patent 4,663,071, issued to Bush and co-inventors on May 5, 1987. Suitable ether polycarboxylates also include cyclic compounds, particularly alicyclic compounds, such as those described in US Patents 3,923,679, 3,835,163, 4,158,635, 4,120,874 and 4,102,903. Other useful builders include the hydroxa polycarboxylates of ether, the copolymers of magnesium anhydride with ethylene or with vinyl ether, 1,3,5-tr? H? Drox? Benzene-2,4,6-tr? S Co-and carboxymethyloxy acid; lae salts of alkali metal, ammonium and substituted ammonium salts, of polyacetic acids, such . such as ethylene glycoltetraacetic acid and nitrilotropic acid, as well as polycarboxylic acids, such as rnicitic acid, succinic acid, oxydiscic acid, polyalkyl acid, benzene-1, 3, 5-hydrocarboxylic acid, carboxy ethyloxysuccinic acid and its soluble salts. The builders of the detergency of time, for example, citric acid and its soluble salts (particularly the sodium salt) are the detergent builders of - "" - "- polycarboxylate or preferred, which can also be used in granular compositions, especially in combination with zeolite and / or with layered silicate builders. Also suitable in the detergent compositions of the present invention are 3, 3-d? Carbox? -4-oxa ~ 1,6-hexanediolates and the related compounds described in US Pat. No. 4,566,984, issued to Bush on January 28, 1986. In the situations in which phosphorus-based products can be used, and especially in For the formulation of laundry operations by hand, the various alkali metal phosphates can be used, such as the well-known sodium tripolyphosphates, sodium pyrophosphate and sodium ortho-ate. Phosphonate builders, such as etan-l-hydrox? - 1, 1-di phosphono or and other known phosphates (see, for example, US Patents 3,159,581, 3,213,030, 3,422,021, 3,400,148 and 3,422,137), they can also be used. If the detergent compositions are used in the detergent compositions herein, they are used at levels of 1% to 80% by weight, preferably 5% to 60% by weight, better still, of 10%. to 50% by weight. (8) additives «additional detergents Optionally, detergent ingredients can "" "- including one or more other detergent additives or other materials to help or promote cleaning performance, the treatment of the substrate to be cleaned, or to modify the aesthetics of the detergent composition. The usual detergent additives of the detergent compositions include the ingredients set forth in US Patent No. 3,936,587, to Baskerville and co-inventors, incorporated herein by reference. Said auxiliaries, * which may be included in the detergent compositions employed in the present invention, at their established levels - the conventional technique (generally from 0% to 30% of the detergent ingredients, preferably from 0.5% to 20% ), include color reflectors, foam reinforcers, foam suppressors, anti-rust and / or anti-corrosion agents, soil-suspending agents, soil-release agents, dyes, fillers, optical brighteners, germicidal lobes, alkalinity sources, hydrotropes, antioxidants, aids, solvents, solubilizing agents, agents that remove clay soils and prevent their redeposition, dispersing agents polirnepcos, auxiliaries processing, fabric softening components, static control agents, etc. The detergent compositions herein can be in any of the different physical forms known to those skilled in the art, for example, granules / powders, liquids, bar-ras, gels or pastes. detergents for washing clothes, including those which are suitable for use in the machine washing or hand washing method, or both; dishwashing detergents, which include detergents for automatic dishwashing machines; hard surface cleaners, or other known detergents, preferably laundry detergents.

AXIS? PLQ I In the following example, "Comparative A" and "Comparative B" are used in detergent compositions outside the scope of the present invention, while "Example 1" is used in a detergent made in accordance with this invention. The whiteness performances of comparatives A and B are deficient, compared to Example 1. Additionally, Example 1 has less color opacity than the comparative f, because it uses a lower level of TAED. Data: Washing clothes test. Compare- Compare- EXAMPLE B.- Dio.

C14- alkyl sulphate 9.00 9.00 9.00 AE3S of C12-i3 2.00 2.00 2.00 It is (Je C 12-14 4.00 4.00 4.00 N-rnet? Lglucam? Of acid "fatty of C 2-.?4 2.00 2.00 2.00 Alurnmosi licato de Na 14.00 14.00 14.00 Silica in layers (SKS-6) 12.00 12.00 12.00 Citric acid 4.00 4.00 4.00 Car-bonato 8.00 8.00 8.00 CompareComparaEjerntivo A.- tivo B.- DiO 1 Copolymer of acrylic acid / naleic acid 5.00 5.00 5.00 Aflojador- dirt polymer 0.5 0.5 0.5 Ca cel ulose -boximet.il 0.5 0.5 0.5 0.03 0.03 Zinc alociamnsulfonato MO 0.03 0.8 0.8 0.8 0.3 0.3 0.3 Poly Abpllantador dirnetil siloxane 0.4 0.4 0.4 0.5 0.5 0.5 0 Perfume Per Na carbonate (13.5 %) 22.5 22.5 22.5 5 TAED (100%) 6.3 5.0 5.0 Savmase (13 KNPU) 0.55 0.55 0.81 ípase (165 KLU) 0.15 0.15 0.15 0 Carezyrne (2000 CEVU) 0.09 0.09 0.1 Pentarnet ILEN sulfonate fos dietiientparní na (100%) 0.51 0.51 0.8 -5 BBI 57 5 72 Test method - Whiteness 0 The operation of the three compositions (comparatives A and B and example 1) was compared in tests in a six-cycle, full-scale washer-to-machine, using neol 701 washers. Each complete wash cycle comprised only one cycle of main wash. The temperature setting at 40 ° C was selected for each wash cycle and water was used at 25 ° C, with Germán hardness (Ca: Mg = 3: 1). Each wash load comprised four pieces of 15 cx 30 cc, each of: clean, white terry towel; and knitted cotton and cotton fabrics. Before the first complete wash cycle 0 began, the laundry load was placed together, "- > n a strip of stained cloth, sold by EMPA Insti-tute, Switzerland, under the trademark "Test strip for combined washing EMPA No. 103", comprising a strip of eight cotton test samples, each with a size 12 x 12 cm, which are: bleached cotton without optical brightener, cotton with normal EMPA dirt, cotton soiled with blood; cotton soiled with cocoa, cotton soiled with blood / milk / carbon black; cotton dyed with sulfur black; fal odon raw and cotton soiled with red wine, together with a dispensing device of the "granulated" type containing 75 g of the detergent product, in the tub of the washing machine. For each of the five subsequent complete wash cycles, the same amount of detergent product and stained cloth strip was used. At the end of the sixth complete wash cycle, the washing load was removed from the machine, dried in the air and then the whiteness / percidity of the three types of fabric was determined.

The whiteness The whiteness / percudido of each piece of cloth was determined by a panel of experts. The averaged, combined results of the series of comparisons are as noted below, using the comparative composition A as the common reference. Comparative A Comparative B Example 1 Reference 37:63 73: 27 * = statistically significant at the 95% safety level.

Test method - The opaqueness of the color of the fabric The "fabric color opaque" operation of the three compositions (comparative A and B and example 1) was compared in tests on a full-scale washing machine, using Miele 698 washers. The short wash setting (temperature - 40) was used. ° C) and water was used at 25 °, Germ n hardness (Ca: Mg = 3: 1). For each type of product the laundry load consisted of a single sample of purple wool fabric (sensitive to bleaching) of 43 x 43 crn, and a ballast load of 2 white sheets. Before starting the first complete washing cycle, the washing load was placed in the tub of the washing machine together with a dispensing device of the "granulette" type containing 75 g of the detergent product. The purple wool sample was placed in such a way that it was adjacent to the dispensing "mouth" of the granulette. After the first revolution of the short wash cycle, a stopwatch was started. The cycle was interrupted after 10 minutes from this time and the laundry load was removed from the tma. The purple wool sample is dried before any color opacity is determined in the wool sample being treated. -or The above procedure was repeated four times for each type of product, each time using a sample of fresh purple wool.

Determination of Color Opacity The darkening or loss of the color of the four samples of purple wool obtained from the internal procedure, for each type of product, was determined by a panel of experts, using as reference a sample of unwashed purple wool. The combined average results of the series of comparisons are given below: Comparison- Comp a- Exemplary f ive B P 1 Opaquent color (% damage) 30% 30% 50% EXAMPLE. 2 Ingredient (%) Alkylbenzenesulfonate 1 me 21 Tripoli sodium phosphate 31.5 Acrylic acidic acid 1 Sodium carbonate 18 Sodium silicate 8.6 Sodium perborate monohydrate 2.O Oxybenzenesulphonate of nonanoyl l.fa Diethylpentaacetic acid diuretic 1.6 Savinase / Ban 6.0 / 170T 0.8 Carboxymethylcellulose 0.4 Lipolase 100T 0.12 Miscellaneous r-es-t o EXAMPLE 3 Ingredient-t% fopn? L tion Substance of alkyl sulfate of Ca. -. 9.00 N-rneti ≥glucamicja of fatty acid from Cía ... 2.00 De-teratogenic emulsifier Na aluminosilicate 14.00 Layered silicate (SKS-6) 12.00 Citric acid 4.00 Regula or Carbonate 8.00 Ingredient% formulation Polymer Acrylic acid copolymer / rnaleic acid 5.00 Sludge-absorbing polymer 0.5 Ca rboxime ti icel ulosa 0.5 Enairna Savmase (13 KNPU) 1.0 L polase (165 KLU) 0.3 Cellulase (1000 Cevu) 0.3 Endogluconase A (5000 Scevu) 0.1 Termamyl (120T) C.5 Bl NAEDER TAED 5.00 Percarbonate of Na Phthalocyst nsul zinc fonate 0.03 A Chelator Penta neti diethylenetriarnine phosphonate 0.8 Minor Ingredients MgSO * 0.8 Brightener 0.3 Polydi etilsiloxano 0.4 Perfume 0.5

Claims (23)

NOVELTY OF THE INVENTION CLAIMS

1. - A detergent composition comprising bleach-, characterized in that it comprises from 5% to 95% by weight of detergent surfactant; from 0% to 80% by weight of detergency builder; from 0.5% to 40% by weight of per-oxygenated bleach; from 0.01% to 10% by weight of activator of ^ bleach; from 0.1% to 10% by weight of chelator; and from 0.05% to 5% by weight of enzymes selected from the group consisting of proteases, amylases, lipases, cellulases and their mixtures; wherein the detergent composition has a biological bleach index ("IBB") of more than 65, as defined by the formula: TAB3 CfiBlCBP] IBB = 4TC] + 26TE] -. + 320 12 where: Te] = [chelator level (% by weight) x (number of chelator groups in the chelator)] / (chelator molecular weight) x 1,000; TE] = percentage by weight of enzymes selected from the group consisting of proteases, alas, lipases, cellulases and their mixtures, in the detergent composition; assuming normal activities of the protease 13 KNPU, amil sa 300 KNU, lipase 165 i U and cellulase 2000 Cevu; ] = [(% by weight of bleach activator) x (a factor of 6 for J30BS), a factor of 6 for catimonic activators, a factor of 550 for complex manganese activators, and a factor of 4 for all bleach activators)] / (molecular weight of bleach activator) x 1,000; and CBP] = (% by weight of peroxy bleach) x (% of oxygen available from the peroxygen bleach) / 100.

2. A detergent composition according to claim 1, further characterized by having an index of biological bleach of more than 75.

3. A detergent composition according to claim 1, further characterized in that the peroxygenated bleach comprises an alkali metal percarbonate.

4. A detergent composition in accordance with the vindication 1, which was also adopted because the bleach activator is selected from the group consisting of tetraacet letilendiamma, benzol lcaprolactam, sulfonate (6- nonanarnidocaproiDoxibenzene, nonanoyloxybenzenesulphone) - sodium or sodium benzoyl loxibencene sulphonate, bleach activators substituted with quaternary ammonium and quaternary phosphine, ionic alkyl compounds, manganese (III) or (IV) di nuclear complexes, and mixtures thereof. 6. A detergent composition according to claim 1, further characterized in that the activator of bleach has the formula: C-L wherein L is a substitutable group in which the conjugate acid of the anion formed in L has a pKa of 4 to 13. • - 7.- A detergent composition of according to claim 1, further characterized in that the chelator is selected from the group consisting of diethylenetriamine pentanetiienphosphonates, ethylene diamine ethylene diamine phosphonates, diethylene magnesium pentaacetates, ethylenediarnine dieuccinates, ethylene diamine tetraacetates and mixtures thereof. 8. A detergent composition according to the cation 1, further characterized in that the enzymes are selected from the group consisting of proteases, amylases and their mixtures. 9. A detergent composition according to claim 1, further characterized in that it comprises from 1% to 30% by weight of peroxygen bleach. 10. A detergent composition according to claim 1, further characterized in that it comprises from 0.2% to 7% by weight of bleach activator. 11. A detergent composition according to claim V, further characterized in that it comprises from 0.2% to 7% by weight of chelator. 12. A detergent composition according to claim 1, further characterized in that it comprises from 0.1% to 3% by weight of enzymes. 13. A detergent composition containing bleach, characterized in that it comprises from 5% to 95% by weight of detergent surfactant; from 0% to 80% by weight of . oe detergency speaker; bleaching and chelating agent and / or nzinas; where the levels of bleaching agent, chelator and enzymes are defined by the formulas: IXJ-f - LXJ CZ ^ L l / aCX] 0 where "f" means "final" and "o" means "original"; where CX] is the sum of bleaching agents, in% ^ "3n weight, in the composition, calculated at 100% activity, wherein the bleaching agents are selected from the group consisting of: (i) peroxygen bleach and ac-t bleach ivador, (n) organic peroxyacid, and (m) nerves of them, where CY] is the sum of chelators, in percentage by weight, in the composition, - where CZ] is the sum of Enzymes, in percentage by weight, in the composition, where the weight percentage is calculated on the basis of the normal activities of the enzyme, of 13 KNPU pair-proteases, 300 KNU for apples, 165 KLU for lipases and 2,000 Cevu for cellulases, and normal activities for other types of enzyme, where "a" is less than 1, where CX] 0 is between 3% and 80%, where CY] 0 is between 0% and 10%, and where CZ] 0 is between 0.01% and 10% 14. - A detergent composition according to claim 13, further characterized why 0.5 i "a" < 1. 1

5. A detergent composition according to claim 13, further characterized in that TY] »is between 0% and 3%. 1

6. A detergent composition according to claim 13, further characterized in that CZ] "is between 0.05% and 5%. 1

7. A detergent composition according to claim 13, further characterized in that CY] C> is 0, and where? Y1? (CX] 0 -CX], -) / 3. detergent according to claim 13, further characterized in that it comprises from 1% to 30% by weight of peroxygen bleaching compound 19. A detergent composition according to claim 13, further characterized in that the bleaching agent is peroxygen bleach and an activator of bleach, and where the detergent composition compresses 1% to 7% by weight of peroxygen bleach and from 0.2% to 7% in v. 5? of bleach activator. 20. A detergent composition according to claim 13, further characterized in that it comprises from 0.2% to 7% by weight of chelator. 21. A detergent composition in accordance with claim 13, further characterized in that it comprises 0.05% to 5% by weight of enzymes, selected from the group consisting of proteases, amylases, lipases, cellulases and mixtures thereof. 22. A detergent composition according to claim 13, further characterized in that the peroxygenated bleach is selected from the group consisting of alkali metal percarbonates, alkali metal perbor-ate atohydrides, metal perborate tetrahydrates. alkaline and mixtures of them. 23.- A detergent composition in accordance with the - claim 13, further characterized in that the chelator is selected from the group consisting of arninophosphonate chelating agents, aminocarboxylate chelating agents and mixtures thereof.