MXPA02002127A

MXPA02002127A - Formulation components resistant towards decomposition by aromatization, compositions and laundry methods employing same.

Info

Publication number: MXPA02002127A
Application number: MXPA02002127A
Authority: MX
Inventors: Gregory Scot Miracle
Original assignee: Procter & Gamble
Priority date: 1999-08-27
Filing date: 2000-08-25
Publication date: 2002-09-18
Also published as: CN1250692C; BR0014149B1; CA2381888A1; MA25605A1; ATE323147T1; AU6935400A; EP1206515B1; DE60027307D1; DE60027307T2; CA2381888C; ES2262534T3; JP2003508584A; CN1384865A; TR200200459T2; AU771521B2; WO2001016273A1; EP1206515A1; AR027845A1; CZ2002688A3; BR0014149A

Abstract

Bleach boosting compounds selected from the group consisting of bleach boosters comprising quaternary imine cations, zwitterions, polyions having a net charge of from about plus;3 to about 3 and mixtures thereof, bleaching species comprising oxaziridinium cations, zwitterions, polyions having a net charge of from about plus;3 to about 3 and mixtures thereof, and mixtures thereof are disclosed. The bleach boosting compounds increase bleaching effectiveness even in lower temperature solutions and provide improved stability toward unwanted bleach boosting compound decomposition. The bleach boosting comprounds are ideally suited for inclusion into bleaching compositions including those with detersive surfactants and enzymes. Also provided is a method for laundering a fabric employing the bleach boosting compounds, and a laundry additive product employing the bleach boosting compounds.

Description

COMPONENTS OF FORMULATION RESISTANT TO DECOMPOSITION BY AROMATIZATION. COMPOSITIONS AND METHODS OF LAUNDRY THAT USE THE SAME FIELD OF THE INVENTION This invention relates to formulation components such as bleach-increasing compounds with greater stability, and laundry compositions and methods employing bleaching-enhancing compounds with increased stability. More particularly, this invention relates to bleacher augmentations of quaternary imines and / or oxaziridinium whitening species, compositions and laundry methods employing quaternary imines to increase bleaching and / or oxaziridinium bleaching species.

BACKGROUND OF THE INVENTION Oxygen bleaching agents have become increasingly popular in recent years in products for household cleaning and personal care to facilitate the removal of stains and dirt. Bleaching agents are especially desirable for their stain removal, dirty laundry, bleaching and sanitizing properties. Oxygen bleaching agents have found particular acceptance in laundry products such as detergents, fret dishwashers and hard surface cleaners. Oxygen bleaching agents, however, are somewhat limited in their effectiveness. Some disadvantages that are frequently found include 5 damage to the fabric's color and damage to the accessories of the washing machines, specifically the rubber hoses that these devices could have. In this way, the colder the solution in which they are used, the less whitening action is less effective. Temperatures greater than 60 ° C are typically required for the effectiveness of the oxygen bleach agent 10 in solution. To solve the temperature dependence mentioned above, a class of compounds known as "activators of the • bleached "has been developed." Bleach activators, typically perhydrolyzable acyl compounds having such a leaving group 15 such as oxybenzenesulfonate, react with the active oxygen group, typically hydrogen peroxide or its anion, to form a more effective peroxyacid oxidant. It is the peroxyacid compound which then oxidizes the material of the stains and dirt. However, bleach activators are also somewhat dependent on temperature. The • 20 bleach activators are most effective at warm temperatures close to 40 ° C to 60 ° C. In water with temperatures below 40 ° C, the peroxyacid compound loses some of its bleaching effectiveness.

Attempts have been made as disclosed in U.S. Patent Nos. 5,360,568, 5,360,569 and 5,370,826 all to Madison et al., To develop a bleaching system that is effective when the temperature conditions in the water are lower. However, the bleached dihydroisoquinolinium augmentations in these references, when combined with peroxygen compounds, undergo undesirable decomposition, including the formation of inactive aromatic isoquinolinium, which causes a reduction in the efficiency of the enhancer. • For that reason, researchers have been pursuing with strength and vigor effective bleaching agents that do not undergo decomposition. Accordingly, there continues to be a need for effective bleach-enhancing compounds and compositions containing bleaching-enhancing compounds that provide bleaching. 15 still effective at lower water temperatures and provide stability to the undesirable decomposition of the bleach-enhancing compound.

BRIEF DESCRIPTION OF THE INVENTION • This need is met by the present invention wherein bleacher-enhancing compounds with longer duration are provided, specifically bleaching augmentations and / or bleaching species. The bleach activating compounds of the present invention provide superior bleaching effectiveness even at lower water temperatures and also prevent undesirable decomposition. A bleaching composition that contains a compound Bleacher enhancer together with or without a peroxygen source, wherein said bleach boosting compound is selected from the group consisting of: (a) a bleach booster chosen from the group A composed of aryliminium cations, aryliminium zwitterions, aryliminium pollones having a net charge of about +3 to -3 and mixtures of the 10 same; (b) a bleach species selected from the group consisting of oxaziridinium cations, oxaziridinium zwitterions, oxaziridinium polyesters having a net charge of +3 to -3 and mixtures thereof; and (c) mixtures of f are provided in a first embodiment. In accordance with another embodiment of the present invention, a cationic or zwitterionic compound enhances the bleaching of clothing. In accordance with yet another aspect of the present invention, there is provided a method for laundry of fabrics that need laundry comprising the contact of the fabric with a solution of • Laundry having a bleaching composition according to the present invention as described herein. In accordance with another aspect of the present invention, a laundry additive product containing an agent is provided. "-" * "** bleach booster selected from the group consisting of: (a) bleach booster chosen from the group consisting of aryliminium cations, aryliminium zwitterions, aryliminium polyols having a net charge of about +3 to -3 and mixtures thereof, (b) a bleach species selected from the group consisting of oxaziridinium cations, zwitterions oxaziridinium, oxaziridinium polyesters having a net charge of +3 to -3 and mixtures thereof, and (c) mixtures thereof. Accordingly, it is the object of the present invention to provide the same.

Provide: a bleach activating compound that demonstrates improved performance even in lower temperature solutions and also that avoids undesirable aromatization; a bleaching composition ^ including a quaternary imine bleach booster and / or oxaziridinium bleaching species; a method for washing a fabric using a quaternary imine bleach booster and / or oxaziridinium whitening species; and a laundry additive product having a quaternary imine bleach booster and / or oxaziridinium whitening species. These, and other objects, features and advantages of the present invention will be recognized by a person skilled in the art from the following description and the appended claims. All percentages, ratios and proportions here are based on weight unless otherwise indicated. All documents cited here are incorporated by reference.

DETAILED DESCRIPTION OF THE INVENTION The present invention discloses novel and very useful bleaching boosting compounds ("bleach boosters", "bleach species" and mixtures thereof), compositions and methods employing novel bleach boosting compounds. The bleaching-enhancing compounds of the present invention provide high bleaching effectiveness even in lower temperature applications while preventing decomposition by undesirable aromatization, resulting in better performance. The bleach-enhancing compounds of the present invention act together with or without, preferably, conventional peroxygen bleach sources to give the aforementioned bleaching effectiveness and prevention of aromatization.

Definitions "Peroxide source" as used herein, means the materials that generate peroxygen compounds, which may include the peroxygen compounds themselves. Examples include, but are not limited to, bleach activators, peracids, percarbonate, perborate, hydrogen peroxide, bleach-enhancing compounds, and / or bleach species (eg, oxaziridinium).

"Peroxygen compounds" as used herein include peracids and peroxides (eg, hydrogen peroxide, alkyl hydroperoxides, etc.). "Peracid" as used herein means a peroxy acid such as a peroxycarboxylic acid and / or peroxymonosulfuric acid (trade name) OXONE) and its salts. Bleaching Augmentants The bleaching augmentators of the present invention are preferably bleached enhancing agents of quaternary imines, preferably, bleaching aids of the present invention are selected from the group consisting of aryliminium cations, aryliminium zwitterions, and / or polys aryliminium having a net charge of +3 to -3 and mixtures thereof, wherein said bleach boosters have the formulas [I] and [II]: Jil É ni if? A initflii. i É, .M - ^^^ > ^ jt «> fa ». ^^ ... ^ aA.Ml?¿ite. ^ __ ^ _ tj __ ^ _____. üM_ & _tofc_tjM__.

Where t is 0 or 1; R1-R4 are substituted or unsubstituted radicals selected from the group consisting of H, alkyl, cycloalkyl, aryl, heterocyclic ring, nitro, halo, cyano, sulfonate, sulfonate, alkoxy, keto, carboxylic and carboxylic radicals; either of the two R1-R4 neighborhoods can combine to form a fused aryl, fused carboxylic or ring heterocyclic fused; R5 is a substituted or unsubstituted radical selected from group consisting of H, alkyl, cycloalkyl, alkaryl, aryl, aralkyl, ring heterocyclic, nitro, halo, cyano, sulfonate, alkoxy, keto, carboxylic, and radicals carboalkoxy; R6 can be a substituted or unsubstituted, saturated or unsaturated radical, selected from the group consisting of H, alkyl, cycloalkyl, alkaryl, aryl, aralkyl, heterocyclic ring, and a radical represented by the formula: -To- (Z Where Z "is covalently bound to T0, and Z" is chosen from the compound group by -C02 \ -S03", -OSO3", -S02"is already 1 or 2, T0 is selected from the group consisting of: (1) - (CH (R12)) - or - (C (R12) 2) - wherein R 12 is independently chosen from H or C C 8 alkyl, (2) -CH 2 (C 6 H 4) -; - CH- C V-CHj- - CH2-C v-CH2- (3) I; (4) OH; (5) - (CH2) d (E) (CH2) f- where d is from 2 to 8, F is from 1 to 3 and E is - (C (O) O-; (6) -C (0 ) NR 13 -where R 13 is H or C C 4 alkyl; Where x is equal to 0 - 3; J, when present, is independently selected from the group consisting of -CR18R19-, -CR18R19CR20R21-, and -CR18R19CR20R21CR22R23-; R 14 -R 23 are substituted or unsubstituted radicals chosen from the straight or branched group consisting of H, C C 8 alkyls, cycloalkyls, alkaryls, aryls, aralkyls, alkylenes, heterocyclic rings, alkoxys, arylcarbonyls, carboxyalkyls and amide groups; wherein R7-R10 are substituted or unsubstituted radicals independently chosen from the group consisting of H, linear or branched C? -C-? 2 alkyls, alkylenes, alkoxys, aryls, alkaryls, aralkyls, cycloalkyls, and heterocyclic rings, further provided that when t is 0, neither R7 nor R8 can be H, and that when t is 1, either R7 and R8, or R9 and R10, are not H; wherein any of R1-R10 can be joined with any of R1-R10 to form part of a common ring. Preferred bleach species include, but are not limited to: (1) oxaziridinium cations of the formula [III] wherein R25 is H or methyl, and R26 is selected from the group of substituted or unsubstituted radicals of an alkyl C linear or branched d4, C3-C- cycloalkyl, and C6-C-? 4 aryl; (2) oxaziridinium zwitterions of the formula [IV] wherein R25 is H or methyl, and R26 has the formula: -To- (Z ") a Preferred bleach boosters include, but are not limited to: (1) aryliminium cations of the formula [I] wherein R5 is H or methyl, and R6 is selected from the group of radicals substituted or unsubstituted by a linear or branched CC? 4 alkyl, C3-C cycloalkyl, and C6-C aryl 4 (2) aryliminium zwitterions of the formula [II] wherein R5 is H or methyl, and R6 has the formula: -T0- (Z-) a Where Z "is covalently bound to T0, and Z" is chooses from the group consisting of -C02", and -OSO3", is already 1 or 2; (3); aryliminium cations of the formula [I] wherein R6 is selected from the group consisting of a C? -C, alkyl? substituted or unsubstituted linear or branched, or aryliminium zwitterions of the formula [II] wherein R6 is a radical represented by the formula: -T0- (Z-) a Where Z "is -C02 \ -S03", or OS03"a is 1 and T0 is chosen from the group consisting of: Where p is an integer from 2 to 4, and R45 is independently selected from the group consisting of H and substituted or unsubstituted linear or branched C-i-Ciß alkyl; and (4) arylminium polyions having a net negative charge where R5 is H, Z "is -C02", -S03"or -OS03" is already 2. Preferred bleach boosters include, but are not limited to (1) ) aryliminium cations of the formula [I] wherein R-R5 are H, and R6 is a substituted or unsubstituted linear or branched C-alkyl; (2) aryliminium zwitterions of the formula [II] wherein R1 - R5 are H, and R6 has the formula: -To- (Z Where Z "is covalently bound to T0, and Z" is selected from the group consisting of - C02", -S03" and -OS03"is already 1. In addition, it is desirable that the aryliminium cations, aryliminium zwitterions and aryliminium polyions have a net charge of +3 to -3, all of the formula [I] and [II] ] are substituted in pairs Whitening Enhancers in substituted pairs of the present invention inhibit or prevent the decomposition of cations, zwitterions, and polions by means of aromatization The aromatization (decomposition) reaction of 6-membered ring boosters it is well known in the area, as exemplified without being limited by theory, in Hanquet et al., Tetrahedron 1993, 49, pp. 423-438 and as stated below: Bleached substitution aids in pairs increase the turnover of the active bleach booster by "blocking" the aromatization induced by the base, as fully described above. Such substitution, without being limited in theory, can also inhibit or prevent the decomposition of cations, zwitterions, and polions by means of other pathways of decomposition. Other means of decomposition include, but are not limited to, attack on the bleach enhancing compound and / or on the bleach species by nucleophiles including but not limited to attack by the hydroxide anion, perhydroxide anion, carboxylate anion, percarboxylate anion and other nucleophiles present under washing conditions. The quaternary imine bleach boosters of the present invention act in conjunction with the peroxygen source to give a more effective bleaching system. The peroxygen sources are well known in the area and the peroxygen source employed in the present invention can contain any of these well-known sources, including peroxygen compounds as well as compounds that under the conditions of consumer use provide an effective amount of peroxygen. n situ The source of peroxygen may include a source of hydrogen peroxide, the in situ formation of a peracid anion through the reaction of a source of hydrogen peroxide and a bleach activator, the preformed peracid compounds or the source mixtures. of compatible peroxygen. Of course, a person skilled in the art will recognize that other sources of peroxygen can be employed without departing from the scope of the invention. a- The source of hydrogen peroxide can be any suitable source of hydrogen peroxide and present at such levels as 10 describes fully in U.S. Patent No. 5,576,282. For example, the source of hydrogen peroxide can be chosen from the group consisting of perborate compounds, percarbonate compounds, perphosphate compounds and mixtures thereof. The bleach activator can be chosen from the group 15 composed of tetraacetylenediamine, sodium octanoyloxybenzene sulfonate, sodium nonanoyloxybenzene sulfonate, sodium decanoyloxybenzene sulfonate, sodium lauroyloxybenzene sulfonate, (6-octanamido-caproyl) oxybenzenesulfonate, (6-nonanamido-caproyl) oxybenzenesulfonate, (6- decanamido-caproyl) oxybenzenesulfonate, and mixtures thereof. The preferred activators are chosen from the group consisting of ethylene diamine tetraacetyl (TAED), benzoylcaprolactam (BzCL), 4-nitrobenzoylcaprolactam, 3-chlorobenzoylcaprolactam, benzoyloxybenzenesulfonate (BOBS), nonanoyloxybenzenesulfonate (NOBS), phenylbenzoate (PhBz), decanoyloxybenzenesulfonate. (C10-OBS), benzoylvalerolactam (BZVL), octanoyloxybenzenesulfonate (C8-OBS), perhydrolyzable esters, sodium salt of 4- [N- (nonanoyl) amino hexanoyloxy] -benzene sulfonate (NACA-OBS) an example of which is described in the Patent of 5 EUA No. 5,523,434, lauroyloxybenzenesulfonate or dodecanoyloxybenzenesulfonate (LOBS or C? 2-OBS), 10-undecenoyloxybenzenesulfonate (UDOBS or Cn-OBS with unsaturation in the ? L position 10), and decanoyloxybenzoic acid (DOBA) and mixtures thereof, preferably benzoylcaprolactam and benzoylvalerolactam. Between the Preferred Bleach Activators Particularly in the pH range of 8 to 9.5 are those chosen to have a leaving group OBS or VL. Other preferred bleach activators are those • described in US Pat. No. 5,698,504 Christie et al., Issued December 16, 1997; UAE 5,695,679 Christie et al., Issued December 9, 1997; USA 15 5,686,401 Willey et al., Issued November 11, 1997; USA 5,686,014. Hartshorn et al., Issued November 11, 1997; US 5,405,412 Willey et al., Issued April 11, 1995; US 5,405,413 Willey et al., Issued April 11, 1995; US 5,130,045 Mitchel et al., Issued July 14, 1992; and US 4,412,934 Chung et al., issued November 1, 1983, and 20 co-pending US patent applications Nos. Serial No. 08 / 709,072, 08 / 064,564, all of which are incorporated herein by reference. The substituted quaternary bleach activators can also be included. The detergent compositions present comprise a substituted quaternary bleach activator (ABCS) or a substituted quaternary peracid (PCS); preferably, the first. Preferred ABCS structures are described below in US 5,686,015 Willey et al., Issued November 11, 1997; US 5,654,421 Taylor et al., Issued August 5, 1997; USA 5,460,747 Gosselink et al., Issued October 24, 1995; US 5,584,888 Miracle et al., Issued December 17, 1996; and US 5,578,136 Taylor et al., issued November 26, 1996, all of which are incorporated herein by reference. Highly preferred bleach activators useful herein are those substituted by amides as described in US 5,698,504, and US 5,695,679, and US 5,686,014 each of which are cited above. Preferred examples of such bleach activators include: (6-octanamidocaproyl) oxybenzenesulfonate, (6-nonanamidocaproyl) oxybenzenesulfonate, (6-decanamidocaproyl) oxybenzenesulfonate and mixtures thereof. Other useful activators, disclosed in US 5,698,504, US 5,695,679, US 5,686,014 each of which is cited above and US 4,966,723 Hodge et al., Issued October 30, 1990, include activators of the benzoxazin type, such as a CßH ring. to which an entity -C (0) OC (R1) = N- joins in positions 1, 2. Depending on the activator and the precise application, good bleaching results can be obtained from bleaching systems having a pH in use of from 6 to 13, preferably from 9.0 to 10.5.

-AAn.? * Í.L ¿i i .. artiA ^ AY.a¿ Typically, for example, activators with entities that withdraw electrons use for almost neutral or sub-neutral pH ranges. The alkalis and buffering agents can be used to ensure such a pH.

Acyl lactam activators, as described in the USA 5,698,504, US 5,695,679 and US 5,686,014, each of which is cited up here, they are very useful here, especially the acyl caprolactams (see for example WO 94-28102 A) and acyl valerolactams (see EUA 5,503,639 Willey and col., issued April 2, 1996 incorporated herein by reference). The preformed peracid compound as used herein is any convenient compound that is stable and under the conditions of Consumer use provide an effective amount of peracid anion. The Bleach boosters of the present invention may of course be used in conjunction with a preformed peracid compound selected from the group consisting of percarboxylic acids and salts, and mixtures thereof, examples of which are described in U.S. Patent No. 5,576,282 to Miracle et al. A class of organic peroxycarboxylic acids have the general formula: O II Y-R-C-O-OH Wherein R is a substituted alkylene or alkylene group containing from 1 to about 22 carbon atoms or a phenylene or substituted phenylene group, and Y is hydrogen, halogen, alkyl, aryl, .C (0) OH or -C ( O) OOH.

Organic peroxy acids suitable for use in the present invention may have either one or two peroxy groups and may be either aliphatic or aromatic. When the organic peroxycarboxylic acid is aliphatic, the unsubstituted acid has the general formula: 5 O II Y- (CH2) n-C-0-OH Where Y can be, for example, H, CH 3, CH 2 Cl, C (0) OH, or C (0) OOH; And n áFk is an integer from 0 to 20. When the organic perocarboxylic acid is aromatic, the unsubstituted acid has the general formula: 10 O II Y-C6H4-C-Q-OH Where Y can be, for example, hydrogen, alkyl, alkylhalogen, halogen, C (O) OH or C (0) OOH. Typical useful monoperoxy acids include alkyl and aryl peroxyacids such as: (i) peroxybenzoic acid and peroxybenzoic acid with substitution in the ring, for example, peroxy-a-naphthoic acid, monoperoxyphthalic acid (magnesium salt hexahydrate), and o-carboxybenzamidoperoxyhexanoic acid (salt sodium); • 20 (ii) aliphatic, substituted aliphatic and arylalkylmonoperoxy acids, for example, peroxylauric acid, peroxystearic acid, N-nonanoylaminoperoxycaproic acid (NAPCA), N, N- (3-) acid .t A O.JL ?. ? ± k4., A., k? J * & ^ Í. , r - * ^ j & B ^ i, ^^ fc¡ ^? ^ ^ ^ ^ &&&?? ^ ^ ^ .. fe fe fe fe fe fe fe fe oct oct oct oct oct oct oct oct oct oct oct oct amino amino amino amino amino amino amino amino amino amino amino amino amino amino N, N-phthaloylaminoperoxycaproic (PAP); (iii) amidoperoxyacids, for example, monononylamide of either peroxysuccinic acid (NAPSA) or peroxyadipic acid (NAPAA). Typical peroxyacids useful herein include the alkyl diperoxy acids and aryldiperoxy acids, such as: (iv) 1,2-diperoxydecanedioic acid; (v) 1,9-diperoxyazelaic acid; (vi) diperoxy fibersic acid; Dyperoxysebacic acid and diperosiisophthalic acid; (vii) 2-decyliperoxybutane-1,4-dioic acid; (viii) 4,4'sulfonylbisperoxybenzoic acid.

• Such bleaching agents are disclosed in U.S. Patent 4,483,781, Hartman, issued November 20, 1984, U.S. Patent 15 4,634,551 to Burns et al., European Patent Application 0,133,354, Banks et al., Published February 20. of 1985, and US Patent 4,412,934, Chung et al., issued November 1, 1983. Sources also include 6-Nonylamino-6-oxoperoxycaproic acid as fully described in US Patent 4,634,551, issued on 6 January 1987 to Burns et al. The # 20 persulfate compounds such as for example OXONE, manufactured commercially by E.l. DuPont de Nemours of Wilmington, DE, may also be employed as a suitable source of peroxymonosulfuric acid.

A bleach activator as used herein is any compound which when used in conjunction with a source of hydrogen peroxide leads to the in situ production of the peracid corresponding to the bleach activator. Various non-limiting examples of activators are fully disclosed in U.S. Patent No. 5,576,282, U.S. Patent 4,915,854 and U.S. Patent 4,412,934. See also US 4,634,551 for other typical bleaches and activators useful herein. The quaternary mineral bleach booster of the present invention acts in conjunction with a peroxygen source to increase bleaching effectiveness. Without being bound by theory, it is believed that the bleach booster reacts with the peroxygen source to form a more active whitening species, a quaternary oxaziridinium compound. The oxaziridinium compound has a high activity at lower temperatures relative to the peroxygen compound. The oxaziridinium compound is represented by the formulas [III] and [IV]: [llO [IV] ÍAA .AÍ., 1 ata. * ^^ ¿2¡ ^ Í? &? ** jtmZ *., a¡t? l? ** L j Where t is 0 or 1; R31-R34 are substituted or unsubstituted radicals selected from the group consisting of H, alkyl, cycloalkyl, aryl, ring heterocycle, nitro, halo, year, sulfonate, alkoxy, keto, carboxylic, and carboalkoxy radicals; and either of the two vicinal R31-R34 may be combined to form a fused aryl, fused carbocyclic ring or fused heterocyclic ring; R25 is a substituted or unsubstituted radical selected from the group consisting of H, alkyl, alkaryl, aryl, aralkyl, heterocyclic ring, nitro, halo, cyano, sulfonate, alkoxy, 9-cet0 > carboxylic, and calboalkoxy radicals, and R26 may be a substituted or unsubstituted, saturated or unsaturated radical, selected from the group consisting of H, Alkyl, cycloalkyl, alkaryl, aryl, aralkyl, heterocyclic ring, and a radical represented by the formula: -To- (Z ") a • Where Z" is covalently bound to T0, and Z "is selected from the group of - C02", - SO3", -OSO3", -S02" and -OS02"is already 1 or 2; T0 is chosen from the composite group 15 by (1) - (CH (R12)) - or - (C (R12) 2) - wherein R12 is independently chosen from H or C8 alkyl; (2) -CH2 (C6H4) -; 20 (5) - (CH2) d (E) (CH2) r wherein d is from 2 to 8; f is from 1 to 3 and E is -C (0) 0-; (6) -C (0) NR13, wherein R13 is H or d-C4 alkyl; f "¥ f« ''..?.? - b? Jt * áb Where x equals 0 - 3; J, when present, is independently selected from the group consisting of -CR39R40-, -CR39R40CR41R42-, and 10 -. 10-CR39R40CR41R42 CR43R44-; R35-R44 are substituted or unsubstituted radicals chosen from the straight or branched group consisting of H, C1-C18 alkyls, cycloalkyls, alkaryls, aryls, aralkyls, alkylenes, heterocyclic rings, alkoxys, arylcarbonyls, carboxyalkyls and amido groups; wherein R27-R30 are substituted or unsubstituted radicals independently chosen from the group Composed of H, linear or branched CC? 2 alkyls, alkyls, alkoxys, aryls, alkaryls, aralkyls, cycloalkyls, and heterocyclic rings, additionally provided that when t is 0, neither R27 nor R28 can be H, and that when t is 1, either R27 and R28, or both R29 and R30, are not H; wherein any R25-R34 can be joined together with any other R25-R34 to be part of a • 20 common ring. In addition, R25-R30 and R31-R34 may be the same as R5-R10 and R1-R4, respectively, of the bleaching booster of formulas [I] and [II]. Such oxaziridinium compounds can be produced from the quaternary imine of the present invention with the reactions: [11O Y Bleach Species- The bleach species (oxaziridinium) can also be used directly in accordance with the present invention. The bleach species of the present invention are preferably selected from the group consisting of oxaziridinium cations, oxaziridinium zwitterions, oxaziridinium polyesters having a net charge of +3 to -3, and mixtures thereof, said oxaziridinium compounds having the formulas y [IV ]: [110 [IV] Where t is 0 or 1; R31-R34 are substituted or unsubstituted radicals selected from the group consisting of H, alkyl, cycloalkyl, aryl, ring heterocycle, nitro, halo, cyano, sulfonate, alkoxy, keto, carboxylic, and carboalkoxy radicals; and either of the two vicinal R31-R34 may be combined to form a fused aryl, fused carbocyclic ring or fused heterocyclic ring; R25 is a substituted or unsubstituted radical selected from the group consisting of H, alkyl, alkaryl, aryl, aralkyl, heterocyclic ring, nitro, halo, cyano, sulfonate, alkoxy, keto, carboxylic, and calboalkoxy radicals, and R26 may be a radical substituted or unsubstituted, saturated or unsaturated, selected from the group consisting of H, alkyl, cycloalkyl, alkaryl, aryl, aralkyl, heterocyclic ring, and a radical represented by the formula: -T0- (Z ") a Where Z "is covalently bound to T0, and Z" is chosen from the group of -C02", - SO3", -OSO3", -S02"and -OS02" is already 1 or 2; T0 is selected from the group consisting of (1) - (CH (R12)) - +0 - (C (R12) 2) - in where R12 is independently chosen of H or d-Cß alkyl; (2) -CH2 (C6H4) -; - CH- C V-CH- - CH- C V-CHj- (3) I; (4) OH; (5) - (CH2) d (E) (CH2) f- wherein d is from 2 to 8; f is from 1 to 3 and E is -C (0) 0-; (6) -C (0) NR13, wherein R13 is H or d-C4 alkyl; H I - C- (7); Y Where x is equal to 0 - 3; J, when it is present, it is chosen independently of the group composed of -CR39R40-, -CR39R40CR 1R42-, and -CR39R40CR41R42CR43R44-; R ^ -R44 are substituted or unsubstituted radicals chosen from the straight or branched group consisting of H, d-C8 alkyls, cycloalkyls, alkaryls, aryls, aralkyls, alkylenes, heterocyclic rings, alkoxys, arylcarbonyls, carboxyalkyls and amido groups; where R27-R30 are substituted or unsubstituted radicals independently chosen from the group consisting of H, linear or branched C1-C12 alkyls, alkylanes, alkoxys, aryls, alkaryls, aralkyls, cycloalkyls, and heterocyclic rings, further provided that when t is 0, neither R27 nor R28 can be H, and that when t is 1, either R27 and R28, or both R29 and R30, are not H; wherein any R25-R34 can be joined together with any other R25-R34 to form part of a common ring. In addition, R25-R30 and R31-R34 may be the same as R5-R10 and R1-R4. respectively, of the bleacher of formulas [I] and [II]. Preferred bleach species include, but are not limited to: (1) oxaziridinium cations of the formula [III] wherein R25 is H or methyl, and R26 is selected from the group of substituted or unsubstituted radicals by C-C alkyl linear or branched, C3-d cycloalkyl, and Ce-Cu aryl; (2) oxaziridinium zwitterions of the formula [IV] wherein R25 is H or methyl, and R26 has the formula: -T0- (Z-) a Where Z "is covalently bound to T0, and Z" is selected from the group of -CO2", -S03", -OSO3", is already 1 or 2; (3) the oxaziridinium cations of the formula [III] wherein R26 is selected from the group consisting of substituted or unsubstituted linear or substituted CC? 4 alkyl; branched, or oxaziridinium aryliminium of the formula [IV] wherein R26 is a radical represented by the formula: -T0- (Z Where Z "is -C02", -S03"or -OS03" a is 1 and T0 is chosen of the group consisting of: Where p is an integer from 2 to 4, and R45 is independently selected from the group consisting of H and substituted or unsubstituted linear or branched C? -C? 8 alkyl; and (4) aryliminium polyions having a net negative charge wherein R25 is H, Z "is -C02", -S03"or -OS03" is already 2. The bleacher-enhancing compounds of the present invention can be used with or without, preferably with a source of 10 peroxygen in a bleaching composition. In the bleaching compositions of the present invention, the peroxygen source may be present at levels of 0.1% (1 ppm) to about 60% (600 ppm) by weight of the composition, and preferably 1% (10 ppm) to about 40% (400 ppm) by weight of the composition, and the bleach-enhancing compound and / or the The species of bleach may be present from 0.00001% (0.0001 ppm) to 10% (100 ppm) by weight of the composition, and preferably from 0.0001% (0.001 ppm) to about 2% (20 ppm) by weight of the composition. composition, preferably from 0.005% (0.05 ppm) to about 0.5% (5 ppm), even more preferably from 0.01% (0.1 ppm) to 0.2% (2 ppm). Preferably of 20 0.02% (0.2 ppm) to about 0.1% (1 ppm). Preferably, the bleaching compositions of the present invention comprise an amount of bleach-enhancing compound and / or bleach species such as the resulting concentration of the bleach-increasing compound in a wash solution from 0.001 ppm to about 5 ppm. In addition, preferably the bleaching compositions of the present invention comprise an amount of peroxygen compound, when present, and an amount of the bleach-enhancing compound and / or bleach species, so that the resulting molar ratio of said peroxygen compound with respect to The bleach boosting compound and / or bleach species in a wash solution is preferably greater than 1: 1, preferably greater than 10: 1, even more preferably 50: 1. Preferred molar ratio ranges of peroxygen compound to the range of bleach-increasing compound range from 30,000: 1 to about 10: 1, even more preferably from 10,000: 1 to about 50: 1, even more preferably 5,000: 1 to about 100: 1, even more preferable from 3,500: 1 to about 150: 1. The conversion values (in ppm) are given for the purpose of example, based on the concentration of the product in use of 1000 ppm. A 1000 ppm wash solution of a product containing 0.2% bleach-increasing compound by weight results in a bleacher-increasing compound concentration of 2 ppm. Similarly, a 3500 ppm wash solution of a product containing 0.2% bleach-increasing compound by weight results in a bleach-increasing compound concentration of 6.5 ppm.

The method for releasing the bleaching-enhancing compounds of the present invention and the method for releasing bleaching compositions (products) containing such bleaching-enhancing compounds which are especially useful in the methods of the present invention with the bleaching-enhancing compounds and compositions containing therein that satisfy the preferred method for bleaching a stained substrate in an aqueous medium with a peroxygen source and with a bleach-enhancing compound whose structure is defined herein and wherein said medium contains active oxygen from the peroxygen compound of 0.05 to about 250 ppm per liter of medium, and said bleach boosting compound of 0.001 ppm to about 5 ppm, preferably from 0.01 ppm to about 3 ppm, preferably from 0.1 ppm to about 2 ppm, and more preferable from 0.2 ppm to about 1 ppm. Such a preferred method for bleaching a stained substrate in an aqueous medium with a peroxygen source and with a bleach-increasing compound is of particular value for those applications in which the color security of the stained substrate in need of cleaning is a concern. In such applications the preferred embodiment (eg, 0.01 ppm to about 3 ppm) is of particular importance to achieve acceptable security in the color of the fabrics. For other applications in which the color security of the stained substrate in need of cleaning is less important, a higher concentration in use may be preferred.

The bleaching compositions of the present invention can be advantageously employed in laundry applications including, but not limited to, bleaching of stains, inhibition of dye transfer, and whitening, hard surface cleaning, automatic dishwashing applications, as well as cosmetic applications. , dentures, teeth, hair and skin. However, due to the unique advantage of high bleaching effectiveness in lower temperature solutions, the bleaching-enhancing compounds of the present invention are ideally compatible for laundry applications such as bleaching of fabrics through the use of detergents containing bleaching or fabric bleaching additives. In addition, the bleaching-enhancing compounds of the present invention can be employed in granular and liquid compositions. Accordingly, the bleaching compositions of the present invention may include several additional ingredients that are desirable in laundry applications. Such ingredients include detergent surfactants, bleach catalysts, detergency builders, chelating agents, enzymes, polymeric soil release agents, brighteners and various ingredients. Compositions including any of these various additional ingredients preferably have a pH of from 6 to 12, preferably from 8 to 10.5 in a 1% solution of the bleaching composition.

,?? A "Yík. The bleaching compositions preferably include at least one detergent surfactant, at least one chelating agent, at least one detergent enzyme and preferably have a pH of at least one detergent enzyme. 6 to 12, preferably from 8 to 10.5 in a 1% solution of the bleaching composition. In accordance with another aspect of the present invention, cationic or zwitterionic bleach-enhancing compounds are provided. Such bleaching-enhancing compounds are preferably chosen from the group consisting of: [Q [IQ 15 [IV] [II And mixtures thereof; wherein the formula [I] and [II] t is 0 or 1; R1-R4 are substituted or unsubstituted radicals selected from the group consisting of H, alkyl, cycloalkyl, aryl, heterocyclic ring, nitro, halo, cyano, sulfonate, alkoxy, keto, carboxylic, and carboalkoxy radicals; either of the two R1-R4 neighbors can be combined to form a fused aryl, ring fused carbocyclic or heterocyclic ring; R5 is a substituted or unsubstituted radical replace selected from the group consisting of H, alkyl, cycloalkyl, alkaryl, aryl, aralkyl, heterocyclic ring, nitro, halo, cyano, sulfonate, alkoxy, keto, carboxylic, and carboalkoxy radicals; R6 can be a substituted or unsubstituted, saturated or unsaturated radical, selected from the group consisting of H, alkyl, cycloalkyl, alkaryl, aryl, aralkyl, heterocyclic ring, and a radical represented by the formula: -T0- (Z ") a Where Z "is covalently bound to T0, and Z" is selected from the group consisting of -C02", -S03", -OSO3", -S02", OS02"is already 1 or 2; T0 is selected from the group consisting of : (1) - (CH (R12)) - or - (C (R12) 2) - wherein R12 is independently chosen from H or C? -C8 alkyl; (2) -CH2 (C6H4) -; - CH2-C-CH2- - CH- C v-CH- (3) I; (4) OH; (5) - (CH2) d (E) (CH2) f- wherein d is from 2 to 8, F is from 1 to 3 and E is - (C (O) O-; (6) -C (0) NR 13 -where R 13 is H or C C 4 alkyl; H I -C- (7); Y Where x is equal to 0 - 3; J, when present, is independently selected from the group consisting of -CR18R19-, -CR18R19CR20R21-, and -CR18R19CR20R2 CR22R23-; R14-R23 are substituted or unsubstituted radicals selected from the straight or branched group consisting of H, C? -C, 8 alkyls, cycloalkyls, alkaryls, aryls, aralkyls, alkylenes, heterocyclic rings, alkoxys, arylcarbonyls, carboxyalkyls and amide groups; wherein R7-R10 are substituted or unsubstituted radicals independently chosen from the group consisting of H, linear or branched C? .C? 2 alkyls, alkyls, alkoxys, aryls, alkaryls, aralkyls, cycloalkyls, and heterocyclic rings, further provided that when t is 0, neither R7 nor R8 can be H, and that when t is 1, either R7 and R8, or R9 and R10, are not H; wherein any R1-R10 can be joined with any R1-R10 to form part of a common ring; and in where for formulas [III] and [IV] t is 0 or 1; R31-R34 are substituted or unsubstituted radicals selected from the group consisting of H, alkyl, cycloalkyl, aryl, ring heterocycle, nitro, halo, cyano, sulfonate, alkoxy, keto, carboxylic, and carboalkoxy radicals; and either of the two R31-R34 neighborhoods can combine to form a fused aryl, fused carbocyclic ring or fused heterocyclic ring; R25 is a substituted or unsubstituted radical selected from the group consisting of H, alkyl, alkaryl, aryl, aralkyl, heterocyclic ring, nitro, halo, cyano, sulfonate, alkoxy, keto, carboxylic, and calboalkoxy radicals, and R26 can be a substituted or unsubstituted radical, saturated or unsaturated, chosen from the group consisting of H, alkyl, cycloalkyl, alkaryl, aryl, aralkyl, heterocyclic ring, and a radical represented by the formula: -To- (Z Where Z "is covalently bound to T0, and Z" is chosen from the group of -CO2 \ - S03", -OSO3", -S02"and -OSO2" is already 1 or 2; T0 is chosen of the compound group by (1) - (CH (R12)) - or - (C (R12) 2) - wherein R12 is independently chosen from H or d-C8 alkyl; (2) -CH2 (C6H4) -; - CH- C-CH2- - CH2-C-CH2- (3) I; (4) OH; (5) - (CH2) d (E) (CH2) f- wherein d is from 2 to 8; f is from 1 to 3 and E is -C ()) O-; (6) -C (0) NR13, wherein R13 is H or C4 alkyl; Where x is equal to 0 - 3; J, when present, is independently selected from the group consisting of -CR39R40-, -CR39R40CR41R42-, and _CR39R40CR41R42CR43R44_. R35.R44 are radIcaIs SUStItItIoN oR SUStItItIoR chosen from the straight or branched group consisting of H, d-C8 alkyls, 5-cycloalkyls, alkaryls, aryls, aralkyls, alkylenes, heterocyclic rings, alkoxys, arylcarbonyls, carboxyalkyls and amido groups; wherein R27-R30 are substituted or unsubstituted radicals independently chosen from the group consisting of H, linear or branched C C 2 2 alkyls, alkylenes, alkoxys, aryls, alkaryls, aralkyls, cycloalkyls, and heterocyclic rings, provided 10 further that when t is 0, neither R27 nor R28 can be H, and that when t is 1, either R27 and R28, or both R29 and R30, are not H; wherein any R25-R34 can be joined together with any other R ^ -R34 to form part of a common ring. In another embodiment of the present invention, a method for laundering a fabric that needs washing is provided. The method Preferred comprises contacting the fabric with a solution of . laundry. The fabric can be almost any fabric capable of being washed under normal conditions of consumer use. The laundry solution contains a bleaching composition, as written fully herein. The water temperatures used in this laundry method range from 20 0 ° C to about 50 ° C. The ratio of water to the fabric is preferably from 1: 1 to 15: 1. The washing solution may additionally include at least one additional ingredient selected from the group consisting of surfactants detergents, chelating agents, detergent enzymes and mixtures thereof. Preferably, the laundry solution has a pH of 6 to 12, preferably 8 to 10.5 in a 1% solution of the bleaching composition. In accordance with another aspect of the present invention, an additive product for laundry is provided. The laundry additive product contains a bleach-enhancing compound, as fully described above. Such an additive laundry product would ideally be compatible for inclusion in a washing process when additional bleaching effectiveness is desired, such cases may include, but are not limited to, laundry with low temperature solutions. It is desirable that the laundry additive product also include a source of peroxygen, as fully described above. The laundry additive product may also include powder or liquid compositions containing a source of hydrogen peroxide or a peroxygen source as defined above. In addition, if the laundry additive product includes a source of hydrogen peroxide, it is desirable that the laundry additive product additionally include a bleach activator, as fully described above. Preferably, the laundry additive product is packaged in dosage form to be added to the laundry process where a peroxygen source is employed and a high bleaching effectiveness is desired.

* Jt "* l_f_fií? - - itit • - •" * .-, ~ «- ^. * - ^^« ¡t ^ t »tfty?» - «- MMuJÍrthjM. ,? »IiHi? F Such individual dosage form may comprise a tablet, tablet, gelcap or other single dosage unit to increase the volume of composition if desired. Suitable fillers or carrier materials can be chosen, but not limited to various salts of sulfates, carbonates and silicates as well as talc, clay and the like. The fillers or carriers for the liquid compositions may be water or low molecular weight primary and secondary alcohols including polyols and diols. Examples include methanol, ethanol, propanol and isopropanol. Monohydric alcohols can also be used, comparisons 10 can contain from 5% to about 90% of such materials. Acidic fillers can be used to reduce the pH. When the bleaching boosting compounds of the • present invention are different from zwitterion aryliminium or zwitterion oxaziridinium, a compatible counter ion is also present to balance the 15 load.

Bleaching compositions containing bleaching-enhancing compounds In addition to the use of bleaching-enhancing compounds The bleaching compounds discussed above, the bleach-enhancing compounds of the present invention can be employed together with or without, preferably with a peroxygen source in other bleaching compositions, regardless of their form. For example, the compounds Bleach boosters can be used in a laundry additive product. In the bleaching compositions of the present invention, the peroxygen source may be present at levels of 0.1% to 60% by weight of the composition, and preferably from 1% to 40% by weight of the composition. In one composition, the bleach booster may be present from 0.001% to 10% by weight of the composition, and preferably from 0.005% to 5% by weight of the composition. In the bleaching compositions of the present invention, the peroxygen source may be present at levels from 0.1% (1 ppm) to 60% (600 ppm), 1% (10 ppm) to 40% (400 ppm) by weight of The composition, and the bleaching-enhancing compound may be present from 0.00001% (0.0001 ppm) to about 10% (100 ppm) by weight of the composition, and preferably from 0.0001% (0.001 ppm) to about 2%. (20 ppm) by weight of the composition, preferably from 0.005% (0.05 ppm) to about 0.5% (5 ppm), even more preferably from 0.01% (0.1 ppm) to about 15 0.2% (2 ppm). Preferably from 0.02% (0.2 ppm) to about 0.1% (1 ppm). The conversion values (in ppm) are given by way of example, based on the concentration in use of 1000 ppm. A washing solution with 1000 ppm of a product containing 0.2% bleach-increasing compound by weight results in a concentration of • 20 bleach boosting compound of 2 ppm. Similarly, a 3500 ppm wash solution of a product containing 0.2% bleach-increasing compound by weight results in a bleach-increasing compound concentration of 6.5 ppm.

The preferred concentration of bleach-enhancing compound is based on a molecular weight of the bleaching-enhancing compound of about 300 grams / mole, although the increasing compounds of the bleaching may preferably have molecular weights of 150 to 1000 grams / mole, or even higher for the polymeric or oligomeric whitening enhancing compounds. For example, in the bleaching compositions of the present invention, when the bleach-increasing compound is more preferably present at 0.005% (0.05 ppm) to about 0.5% (5 ppm), the molar concentration (M) of the The bleaching boosting compound will be from 1.7 x 10"8M to 1.7 x 10'5M.) If a higher molecular weight bleaching compound is to be used in the bleaching compositions of the present invention, the • preferred molar concentration will remain unchanged, while the preferred weight concentration (in ppm) will increase accordingly. By For example, a bleaching-enhancing compound with a molecular weight of about 600 grams / mol would preferably be present from 0.01% (0.1 ppm) to about 1.0% (10 ppm). For oligomeric or polymeric bleach-enhancing compounds, the most preferred molar concentration will be based on the monomeric unit associated with the iminium active site or • 20 oxaziridinium. The bleaching compositions of the present invention can be used advantageously in laundry applications, hard surface cleaning, automatic dishwashing applications, as well as cosmetic applications such as dentures, teeth, hair and skin. However, due to the unique advantages of high color security in cold and possibly lukewarm water solutions due to possible increased stability, the bleach-enhancing compounds of the present invention are ideally compatible for laundry applications such as bleaching. fabrics through the use of detergents that contain bleach or laundry bleach additives. In addition, the bleaching-enhancing compounds of the present invention can be employed in granular and liquid compositions. The bleach-increasing compounds and the bleaching composition comprising the bleach-enhancing compounds can be used as antimicrobial agents and disinfectants. Accordingly, the bleaching compositions of the present invention may include several additional ingredients that are desirable in laundry applications. Such ingredients include detergent surfactants, bleach catalysts, detergency builders, chelating agents, enzymes, polymeric soil release agents, brighteners and various ingredients. Compositions including any of these various additional ingredients preferably have a pH of from 6 to 12, preferably from 8 to 10.5 in a 1% solution of the bleaching composition. The bleaching compositions preferably include at least one detergent surfactant, at least one chelating agent, at least one detergent enzyme and preferably have a pH of from 6 to 12, preferably from 8 to 10.5 in a 1% solution of the bleaching composition. In another embodiment of the present invention, a method for laundering a fabric that needs washing is provided. The preferred method comprises contacting the fabric with a laundry solution. The fabric can be almost any fabric capable of being washed under normal conditions of consumer use. The laundry solution contains a bleaching composition, as written fully herein. The water temperatures used in this laundry method range from 0 ° C to about 50 ° C. The ratio of water to fabric is preferably from 1: 1 to 15: 1. The washing solution may additionally include at least one additional ingredient selected from the group consisting of detergent surfactants, chelating agents, detergent enzymes and mixtures thereof. Preferably, the laundry solution has a pH of 6 to 12, preferably 8 to 10.5 in a 1% solution of the bleaching composition. In accordance with another aspect of the present invention, a laundry additive product is provided. The laundry additive product contains a bleach-enhancing compound, as fully described above. Such a laundry additive product would ideally be compatible for inclusion in a washing process when additional bleaching effectiveness is desired, such cases may include, but are not limited to, laundry with low temperature solutions. It is desirable that the laundry additive product also include a source of peroxygen, as fully described above. He The laundry additive product may also include powder or liquid compositions containing a source of hydrogen peroxide or a peroxygen source as defined above. 91 In addition, if the laundry additive product includes a source of hydrogen peroxide, it is desirable that the laundry additive product 10 further includes a bleach activator, as fully described above. Preferably, the laundry additive product is packaged in 9 ^ dosage form to be added to the laundry process where a source of peroxygen is used and a high bleaching effectiveness is desired. Such a single dosage form may comprise a tablet, tablet, gelcap or other single dosage unit to increase the volume of composition if desired. Suitable fillers or carrier materials can be chosen, but not limited to various salts of sulfates, carbonates and *? silicates as well as talc, clay and the like. The filling materials or 20 carriers for the liquid compositions can be water or low molecular weight primary and secondary alcohols including polyols and diols. Examples include methanol, ethanol, propanol and isopropanol. Monohydric alcohols can also be used, comparisons can contain from 5% to about 90% of such materials. Acidic fillers can be used to reduce the pH. A preferred bleaching composition is a bleaching composition comprising: (a) a source of peroxygen; and (b) bleach-enhancing compounds; wherein the bleaching boosting compounds are They become active in a washing solution containing said bleaching composition a period of time after said source of bleaching. 10 peroxygen becomes active. The peroxygen source, as discussed above, is preferably selected from the group consisting of: (i) preformed peracid compounds selected from the group consisting of percarboxylic acids and salts, acids and percarbon salts, acids and perimidic salts, acids and peroxymonosulfuric salts, and mixtures thereof, and (ii) sources of hydrogen peroxide selected from the group consisting of perborate compounds, percarbonate compounds, phosphate compounds and mixtures thereof, and a bleach activator. Bleaching system- In addition to bleaching augmentation • 20 of the present invention, the bleaching compositions of the present invention preferably comprise a bleaching system. Bleaching systems typically comprise a peroxygen source. The peroxygen sources are well known in the area and the peroxygen source employed in the present invention can contain any of these well-known sources, including peroxygen compounds as well as compounds that under the conditions of consumer use provide an effective amount of peroxygen. In situ. The source of peroxygen can include a source of hydrogen peroxide, in situ formation of a peracid anion through the reaction of a source of hydrogen peroxide and a bleach activator, preformed peracid compounds or mixtures of the appropriate peroxygen sources . Of course, a person skilled in the art will recognize that other sources of peroxygen can be employed without departing from the scope of the invention. Preferably, the peroxygen source is selected from the group consisting of: (i) preformed peracid compounds selected from the group consisting of acids and percarboxylic salts, acids and percarbon salts, acids and perimidic salts, acids and peroxymonosulfuric salts, and mixtures thereof, and (ii) hydrogen peroxide sources chosen from the group consisting of perborate compounds, percarbonate compounds, phosphate compounds and mixtures thereof, and a bleach activator. When present, the peroxygen sources (peracids and / or sources of hydrogen peroxide) will typically be at levels of 1%, preferably from 5% to 30%, preferably to about 20% by weight of the composition. If present, the amount of bleach activator will typically be 0.1%, preferably from 0.5% to about 60%, preferably of 40% by weight, of the bleaching composition containing the bleaching agent plus the bleach activator. to. Preformed Peracids - The preformed peracid compound as used herein is any convenient compound that is stable and that Under the conditions of consumer use provide an effective amount of the peracid anion. The bleach-enhancing compounds of the present invention can of course be used with a peracid compound preformed from the group consisting of acids and percarboxylic salts, acids and percarbon salts, acids and perimidic salts, acids and peroxymonosulfuric salts, and mixtures thereof, examples of which they are described in U.S. Patent No. 5,576,282 to Miracle et al. A class of suitable organic peroxycarboxylic acids have the general formula: O II Y-R-C-O-OH Where R is an alkylene or substituted alkylene group that contains from 1 to about 22 carbon atoms or a phenylene or substituted phenylene group, and Y is hydrogen, halogen, alkyl, aryl, -C (0) OH or -C (0) OOH. Organic peroxyacids suitable for use in the present invention can have either one or two peroxy groups and can be either aliphatic or aromatic. When the organic peroxycarboxylic acid is aliphatic, the unsubstituted acid has the general formula: Where Y may be, for example, H, CH 3, CH 2 Cl, C (O) OH, or C (O) OOH; And n is an integer from 0 to 20. When the organic perocarboxylic acid is aromatic, the unsubstituted acid has the general formula: II Y-CRH? - C-O-OH 5 6 4 Where Y can be, for example, hydrogen, alkyl, alkylhalogen, halogen, C (0) OH or C (O) OOH.

Useful typical monoperoxy acids include the alkyl and aryl peroxyacids such as: 10 (i) peroxybenzoic acid and peroxybenzoic acid with substitution in the ring, for example, peroxy-a-naphthoic acid, monoperoxyphthalic acid (salt) of magnesium hexahydrate), and o-carboxybenzamidoperoxyhexanoic acid (sodium salt); (ii) aliphatic, substituted aliphatic and arylalkyl monoperoxy acids, 15 for example, peroxylauric acid, peroxystearic acid, N-nonanoylaminoperoxycaproic acid (NAPCA), N, N- (3-octylsuccinoyl) aminoperoxycaproic acid (SAPA) and N, N-phthaloylaminoperoxycaproic acid (PAP); (iii) amidoperoxyacids, for example, monononylamide from either Peroxysuccinic acid (NAPSA) or peroxyadipic acid (NAPAA). Typical peroxyacids useful herein include diperoxy acids alkyl and aryldiperoxy acids, such as: (iv) 1,2-diperoxydecanedioic acid; •, $ & • tfcL-fc. * A.?*? . * L ± t • * • - &** **. R.1. (v) 1, 9-diperoxyazelaic acid, (vi) diperoxybrassilic acid, diperoxisebacic acid and diperosisophthalic acid, (vii) 2-decyliperoxybutane-1,4-dioic acid. (viii) 4,4'sulfonylbisperoxybenzoic acid Such bleaching agents are disclosed in U.S. Patent 4,483,781, Hartman, issued November 20, 1984, U.S. Patent 4,634,551 to Burns et al., European Patent Application 0,133,354, Banks et al., published February 20, 1985, and U.S. Patent 4,412,934, Chung et al., issued November 1, 1983. The sources also include 6-Nonylamino-6-oxoperoxycaproic acid as fully described in US Pat. U.S. Patent 4,634,551, issued January 6, 1987 to Burns et al. Persulfate compounds such as for example OXONE, commercially manufactured by DuPont de Nemours of Wilmington, DE, may also be employed as a suitable source of peroxymonosulfuric acid. Sources of peroxide hydrogen - The hydrogen peroxide source can be any source of hydrogen peroxide and present at such levels as fully described in U.S. Patent No. 5,576,282. For example, the source of hydrogen peroxide can be chosen from the group comprising perborate compounds, percarbonate compounds, perphosphate compounds and mixtures thereof. The sources of hydrogen peroxide are described in detail and are incorporated here Kirk Othmer's Encyclopedia of Chemical Technology, 4th Ed (1992, John Wiley &Sons), Vol. 4, pp. 271-300"Bleachin Agents (Survey)", include the various forms of sodium perborate and sodium percarbonate, including various coated and modified forms. The preferred source of hydrogen peroxide used herein can be any convenient source, including the hydrogen peroxide itself. For example, perborate, for example, sodium perborate (any hydrated salt but preferably mono or tetra hydrated), sodium carbonate peroxyhydrate or its equivalent percarbonate salts, sodium pyrophosphate peroxyhydrate, urea peroxyhydrate, or sodium peroxide can be used here. . Also available are available oxygen sources such as persulfate bleaches (e.g., OXONE, manufactured by DuPont). Sodium perborate monohydrate and sodium percarbonate are particularly preferred. Mixtures of any convenient hydrogen peroxide source can also be used. A preferred percarbonate bleach comprises dry particles having an average particle size in the range of 500 micrometers to 1,000 micrometers, not more than 10% by weight of said particles being less than 200 micrometers and not more than 10% by weight of said particles is larger than 1, 250 micrometers. Optionally, the percarbonate can be coated with water-soluble silicate, borate or surfactants. Percarbonate is available from various commercial sources such as FMC, Solvay and Tokai Denka.

The compositions of the present invention may also contain as a bleaching agent a chlorine-type bleaching material, such agents are well known in the art, and include for example sodium dichloroisocyanurate ("NaDCC"). However, chlorine-type bleaches are less preferred for compositions containing enzymes. b. Bleach activators - Preferably, the peroxygen source in the composition is formulated with an activator (peracid precursor). The activator is present at 0.01% levels, preferably from 0. 5%. more preferably from 1% to 15%, preferably to 10%, most preferably from 8% by weight of the composition. A bleach activator as used herein is any compound that when used in conjunction with a source of hydrogen peroxide leads to the in situ production of the peracid corresponding to the bleach activator. Various non-limiting examples of activators are fully described in U.S. Patent No. 5,576,282, U.S. Patent 4,915,854 and U.S. Patent 4,412,934. See also US 4,634,551 for other typical bleaches and activators useful herein. Preferred activators are selected from the group consisting of ethylene diamine tetraacetic acid (TAED), benzoylcaprolactam (BzCL), 4-nitrobenzoylcaprolactam, 3-chlorobenzoylcaprolactam, benzoyloxybenzenesulfonate (BOBS), nonanoyloxybenzenesulfonate (NOBS), phenylbenzoate (PhBz), decanoyloxybenzenesulfonate (C? 0-OBS), benzoylvalerolactam (BZVL), octanoyloxybenzenesulfonate (C8-OBS), perhydrolyzable esters, and mixtures of them, preferably benzoylcaprolactam and benzoylvalerolactam. Preferred activators of the bleach in the pH range of 8-9.5 are those that have a leaving group OBS or VL. Preferred hydrophobic bleach activators, include, but are not limited to, nonanoyloxybenzenesulfonate (NOB), sodium salt of 4- [N- (nonanoyl) amino hexanoyloxy] -benzene sulfonate (NACA-OBS) an example of which is described in U.S. Patent No. 5,523,434, lauroyloxybenzenesulfonate or dodecanoyloxybenzenesulfonate (LOBS or C12-OBS), 10-undecenoyloxybenzenesulfonate (UDOBS or Cn-OBS with unsaturation in the 10-position), and decanoyloxybenzoic acid (DOBA). Preferred bleach activators are those described in Pat EUA 5,698,504 Christie et al., Issued December 16, 1997; UAE 5,695,679 Christie et al., Issued December 9, 1997; USA 5,686,401 Willey et al., Issued November 11, 1997; US 5,686,014 Hartshorn et al., Issued November 11, 1997; USA 5,405,412 Willey and • col., Issued on April 11, 1995; US 5,405,413 Willey et al., Issued April 11, 1995; US 5,130,045 Mitchel et al., Issued July 14, 1992; and US 4,412,934 Chung et al., issued November 1, 1983, and co-pending US patent applications Nos. 08 / 709,072, 08 / 064,564, all of which are incorporated herein by reference. The molar ratio of peroxygen bleach compound (as AvO) to the bleach activator in the present invention ÍL Ajf fk? .kdü.i.f.t? Fc ,. it generally ranges from at least 1: 1, preferably close to 20: 1, more preferably from 10: 1 to 1: 1, preferably 3: 1. Substituted quaternary bleach activators may also be included. The bleaching compositions present preferably comprise a substituted quaternary bleach activator (ABCS) or a substituted quaternary peracid (PCS); preferably, the first. Preferred ABCS structures are described below in US 5,686,015 Willey et al., Issued November 11, 1997; US 5,654,421 Taylor et al., Issued August 5, 1997; USA 5,460,747 Gosselink et al., Issued October 24, 1995; US 5,584,888 Miracle et al., Issued December 17, 1996; and US 5,578,136 Taylor et al., issued November 26, 1996, all of which are incorporated herein by reference. The highly preferred bleach activators useful herein are those substituted by amides as described in US 5,698,504, and US 5,686,014 each of which are cited above. Preferred examples of such bleach activators include: (6-octanamidocaproi) oxybenzenesulfonate, (.beta.-nanoamidocaproyl) oxybenzenesulfonate, (6-decanamidocaproyl) oxybenzenesulfonate and mixtures thereof. Other useful activators, revealed in the US 5,698,504, USA 5,695,679, US 5,695,679, US 5,686,014 each of which is cited above and US 4,966,723 Hodge et al., Issued October 30, 1990, include activators of the benzoxazin type, such as a CßH4 ring to which it binds in the positions 1, 2 an entity -C (0) OC (R1) = N-. Depending on the activator and the precise application, good bleaching results can be obtained from bleaching systems having a pH in use of from 6 to 13, preferably from 9.0 to 10.5. Typically, for example, activators with electron withdrawing entities are used for near-neutral or sub-neutral pH ranges. The alkalis and buffering agents can be used to ensure such a pH. Acyl lactam activators, as described in US 5,698,504, US 5,695,679 and US 5,686,014, each of which is cited above, are very useful here, especially acyl caprolactams (see for example WO 94-28102 A) and acyl valerolactams (see US 5,503,639 Willey et al., issued April 2, 1996 incorporated herein by reference). d. Organic peroxides especially diacyl peroxides - In addition to the bleaching agents described above, the bleaching compositions of the present invention may optionally include organic peroxides. Organic peroxides are amply illustrated in Kirk Othmer, Encyclopedia of Chemical Technology, Vol. 17, John Wiley and Sons, 1982 on pages 27-90 and especially on pages 63-72, all incorporated herein by reference. If a diacyl peroxide is used, it will preferably be one that exerts a minimal adverse impact on the spots / films. and. Metal-containing bleach catalysts - Bleaching compositions may also optionally include metal-containing bleach catalysts, preferably manganese and cobalt-containing catalysts. One type of metal-containing bleach catalyst is a catalyst system containing a cation of a transition metal of defined bleach catalytic activity, such as copper, iron, titanium, ruthenium, tungsten, molybdenum, or manganese cations, a cation auxiliary metallic that has little or no catalytic activity of the bleached, such as zinc or aluminum cations, and a sequestrant having defined stability constants for the catalytic and auxiliary metal cations, especially ethylenediaminetetraacetic acid, ethylenediaminetetra (methylenephosphonic acid) and the water soluble salts thereof. Such catalysts are disclosed in US 4,430,243 Bragg, issued February 2, 1982. i. Manganese metal complexes - If desired, the compositions herein can be catalyzed by means of a manganese compound. Such compounds and levels of use are well known in the art and include, for example, the manganese-based catalysts disclosed in US 5,576,282 Miracle et al., Issued November 19, 1996.; US 5,246,621 Favre et al., Issued September 21, 1993; US 5,244, 594 Favre et al., Issued September 14, 1993; US 5,194,416 Jureller et al., Issued March 16, 1993; US 5,114,606 van Vliet et al., Issued t t '- | -ln # fiÍ? llA "* - t" "" ^ J1 * • - »•« ** »'» • - - • * - ^ ** »~ .-» - ». ..kku? **** -, a * &amp?? *? K t aa? * »~~.?. ? dakAá on May 19, 1992; and European Pat. Pub. App. Nos. 549,271 A1, 549,272 A1, 544,440 A2, and 544,490 A1; Preferred examples of these catalysts include MnIV2 (u-0) 3 (1, 4,7-trimethyl-1, 4,7-triazacyclononane) 2- (PF6) 2, Mn '"2 (u-0) 1 ( u-OAc) 2 (1, 4,7-trimethyl-1, 4,7-triazacyclononane) 2- (CI04) 2> Mn? v4 (u-0) 6 (1, 4,7-triazacyclononane) 4- (CI04) 4, Mn "lMnlv4 (u-0) 1 (u-OAc) 2 (1, 4,7-trimethyl-l, 4,7-triazacyclononane) 2- (CI04) 3, Mn? V ( 1, 4,7-trimethyl-1, 4,7-triazacyclononane) - (OCH 3) 3 (PF 6), and mixtures thereof. Other metal-based catalysts include those disclosed in US 4,430,243 included by reference herein above and US 5,114,611 van Kralingen, issued May 19, 1992. The use of manganese with various complex ligands to increase bleaching is also reported in the following: US 4,728,455 Rerek, issued March 1, 1988; US 5,284,944 Madison, issued February 8, 1994; US 5,246,612 van Dijk et al., Issued September 21, 1993; US 5,256,779 Kerschner et al., Issued October 26, 1993; US 5,280,117 Kerschner et al., Issued January 18, 1994; USA 5,274,147 Kerschner et al., Issued December 28, 1993; USA 5,153,161 Kerschner et al., Issued October 6, 1992; and US 5,277,084 Martens et al., issued July 13, 1993. ii. Cobalt metal complexes - The cobalt catalysts useful herein are known, and are described, for example, in US 5,597,936 Perkins et al., Issued January 28, 1997; US 5,595,967 Miracle et al., January 21, 1997; US 5,703,030 Perkins et al., Issued December 30, 1997; and M. L. Tobe, "Hydrolysis Base of Transition-Metal liÉAÍÁAAÉtl * fc¡fc - * "'ki £ l¡íJ¡rX £ i XÍte Complexes", Adv. Inorg. Bioinorg. Mech., (1983), 2, pages 1-94. The most preferred cobalt catalyst useful herein are the cobalt pentaamino acetate salts having the formula [Co (NH3) 5OAc] Ty, where "OAc" represents an acetate entity and "Ty" is an anion, and especially chloride of cobalt pentaamine acetate formula [Co (NH3) 5? Ac] CI2; as well as [Co (NH3) 5OAc] (OAc) 2; [Co (NH3) 5? Ac] (PF6) 2; [Co (NH3) 5OAc] (S04); [Co (NH3) 5OAc] (BF4) 2; and [Co (NH3) 5OAc] (N03) 2 (here "PAC"). These cobalt catalysts are readily prepared by known methods, such as those taught in the example in US 5,597,936, US 5,595,967, US 5,703,030, cited above, the Tobe article and references cited herein, and in US Patent 4,810,410, to Diakun et al., issued March 7, 1989; J. Chem. Ed. (1989), 66 (12), 1043-45; The Synthesis and Characterization of Inorganic Compounds, W. L. Jolly (Prentice-Hall, 1970), pp. 461-3; Inorg. Chem., 18. 1497.1502 (1979); Inoro. Chem. 21, 2881-2885 (1982); Inorg. Chem., 18, 2023-2025 (1979); Inorg. Synthesis, 173-176 (1960); and Journal of Phvsical Chemistrv, 56, 22-25 (1952). iii. Transition metal complexes of rigid macropolycyclic ligands - The compositions herein can also suitably include as bleach catalysts a complex of a transition metal of a rigid macropolyclic ligand. The phrase "macropolicíclico rigid ligand" is sometimes abbreviated as "LRM" in the discussion below. The amount used is a catalytically effective amount, compatible about 1 ppb or more, for example up to 99.9%, more typically about 0.001 ppm or more, preferably from 0.05 ppm to 500 ppm (where "ppb" means parts per billion by weight and "ppm" means parts by weight). million in weight). The transition metals compatible for example, Mn are illustrated hereafter. "Macropolycilic" means that an LRM is a macrocycle and is polycyclic. "Polycyclic" means at least bicyclic. The term "rigid" as used herein includes "having a superstructure" and "cross-bridges". "Rigid" has been defined as the forced opposite of flexibility: see D.H. Busch., Chemical Reviews. (1993), 93, 847-860, incorporated by reference. More particularly, "rigid" as used herein means that the LRM must be decidedly stiffer than a macrocycle ("original macrocycle") that is otherwise identical (has the same ring size and number of atoms in the main ring) but that it lacks superstructures (especially liaison entities or, preferably cross bridge entities) found in LRMs.

To determine the comparative stiffness of macrocyclics with and without superstructures, the practitioner will use the free form (not the metal-bonded form) of the macrocycles. It is well known that rigidity is useful for comparing macrocycles; Suitable tools for determining, measuring or comparing stiffness include computational methods (see, for example, Zimmer, Chemical Reviews, (1995), 95 (38), 2629-2648 or Hancock et al., Inorganic Chimica Acta. (1989 ), 164, 73-84. i - * > *** & "? . ..? .. .... .... ".... *. . ^. t 1 *** ^ * ^. ^ * - ** ^^ .. ^^^? d? ktoklM The LRMs mentioned here are a special type of ultra-rigid ligand that has crossed bridges. A "cross bridge" is illustrated without limitations in 1.11 hereafter. In 1.11, the crossed bridge is an entity -CH2CH2-. Bridge with N1 and N8 in the illustrative structure. By In comparison, a bridge "on the same side", for example if a bridge were to be introduced through N1 and N12 at 1.11, would not be enough to constitute a "cross bridge" and therefore would not be preferred. ^ Compatible metals in rigid ligand complexes include Mn (ll), Mn (lll), Mn (IV), Mn (V), Fe (ll), Fe (lll), Fe (IV), Co (l) , Co (ll), 10 Co (lll), Ni (l), Ni (ll), Ni (lll), Cu (ll), Cu (lll), Cr (ll), Cr (lll), Cr (IV), Cr (V) , Cr (VI), V (lll), V (IV), V (V), Mo (IV), Mo (V), Mo (VI), W (IV), W (V), W (VI), Pd (ll), Ru (ll), Ru (lll), and Ru (IV). Preferred transition metals in the instantaneous transition metal catalyst include manganese, iron and chromium. More generally, the LRMs (and the catalysts of 15 corresponding transition metals) mentioned herein comprise: (a) at least one macrocycle main ring containing four or more heteroatoms; and (b) a covalently connected non-metallic superstructure capable of increasing the rigidity of the macrocycle, preferably chosen from • 20 (i) a bridge superstructure, such as a linkage entity; (ii) a cross-bridge superstructure, such as a cross bridge link entity; Y (iii) combinations thereof. The term "superstructure" is used herein as defined in the literature by Busch et al., See, for example, Busch's articles in "Chemical Reviews". The preferred superstructures here not only increase the stiffness of the original macrocycle but also favor the bending of the macrocycle to coordinate with a metal in a groove. The compatible superstructures can be remarkably simple, for example a link entity such as any of those illustrated in Formula A and Formula B. Below, they can be used \ / (CH2) n Formula A Where n is an integer, for example from 2 to 8, preferably less than 6, typically 2 to 4, or Formula B Where m and n are integers from 1 to 8, preferably from 1 to 3; Z is N or CH; and T is a compatible substituent, for example, H, alkyl, trialkylammonium, halogen, nitro, sulfonate or the like. The aromatic ring in ? A jl. J ¿__¿ «_ > _________J___. * ± *? Jk ± '~ t * &? ^^^ 1.10 can be replaced by a saturated ring, in which the Z atom that connects inside the ring can have N, O, S or O The LRMs are illustrated without limitations later by the following compound: Formula C This is an LRM according to the invention which is a very preferred cyclam derivative, with crossed bridges, substituted with methyl (all tertiary nitrogen atoms). Formally, this ligand is called 5,12-dimethyl-1, 5,8,12-tetraazabicyclo [6.6.2] hexadecane using an extended von Baeyer system. See "A Guide to lUPAC Nomenclature of Organic Compounds: Recommendations 1993", R. Panic, W.H. Powell and J-C Richer (Eds.), Blackwell Scientific Publications, Boston, 1993; see especially section R-2.4.2.1. The catalysts for transition metal bleaching of the Macrocyclic Rigid Ligands that are compatible for use in the compositions of the invention can generally include known compounds wherein they meet the definition given herein, as well as, more preferably, any of a large number of novel compounds malAs- expressly designed for the laundry or cleaning uses present, and are illustrated without limitations by any of the following: Dichloro-5,12-dimethyl-1, 5,8,12-tetraazabicyclo [6.6.2] hexadecane Manganese ( II) Diacuo-5,12-dimethyl-1, 5,8,12-tetraazabicyclo [6.6.2] hexadecane Manganese (II) 5 Hexafluorophosphate Acuo-hydroxy-5,12-dimethyl-1, 5,8,12-tetraazabicyclo [6.6.2] hexadecane manganese (III) hexafluorophosphate I Diacuo-5,12-dimethyl-1, 5,8,12-tetraazabicyclo [6.6.2] hexadecane Manganese (II) tetrafluoroborate 10 Dichloro-5,12-dimethyl- 1, 5,8,12-tetraazabicyclo [6.6.2] hexadecane Manganese (lll) hexafluorophosphate Dichloro-5,12-di-n-butyl-1, 5,8,12-tetraazabicyclo [6.6.2] hexadecane Manganese (II) ) Dichloro-5, 12-dibenzyl-1, 5,8, 12-tetraazabicyclo [6.6.2] hexadecane Manganese (l I) 15 Dichloro-5-n-butyl-12-methyl-1, 5,8,12- tetraaza-bicyclo [6.6.2] hexadecane. Manganese (ll) Dichloro-5-n-octyl-12-methyl-1, 5,8,12-tetraazabicyclo [6.6.2] hexadecane Manganese (II) Dichloro-5-n-butyl-12-methyl-1, 5 , 8,12-tetraaza-bicyclo [6.6.2] hexadecane 20 Manganese (ll) f. Other Mangueadocatalysts - The compositions mentioned herein may have one or more different bleach catalysts. The preferred bleach catalysts are the zwitterionic bleach catalysts, which are described in U.S. Patent No. 5,576,282 (especially 3- (3,4-dihydroisoquinolinio) propane sulfonate Other bleach catalysts include cationic bleach catalysts are described in US Pat. 5,360,569, 5,442,066, 5,478,357, 5,370,826, 5,482,515, 5,550,256 and WO 95/13351, WO 95/13352, and WO 95/13353. As a practical matter, and not as a limitation, the cleaning compositions and processes here can be adjusted to give the order of at least one part per one hundred million of the active catalyst species of the bleached in the aqueous wash medium, and will preferably give from 0.01 ppm to 25 ppm, preferably from 0.05 ppm to 10 ppm, and preferably from 0.1 ppm to 5 ppm, of the species of bleach catalyst in the water of • washed. To obtain such levels in the wash water in an automatic washing process, typical compositions herein will contain about 15 0.0005% to 0.2%, preferably 0.004% to 0.08%, of bleaching catalyst, especially manganese or cobalt catalysts. , by weight of the cleaning compositions. Preferably, the source of hydrogen peroxide is chosen from? group composed of perborate compounds, percarbonate compounds, phosphate compounds and mixtures thereof, and a bleach activator. Preferably, the bleach activator is selected from the group consisting of hydrophobic bleach activators as disclosed herein. kst., t ^ * - H? ? i? HAA? Ft T "iftif" - "" - -'- - • * - * • - »** '• *. - .- *"' - "-» > * * * * --- -. "- ** • ** -. *. ^ * - ^ É? * JÍ? Í? M The purpose of such bleaching composition is to mitigate the undesirable decomposition of the bleach booster, and Allow the peracid to achieve bleaching performance on a fabric that needs cleaning, such as a stained cloth, in a wash solution before the bleach booster becomes available The period between the activation of the peracid in a wash solution and the activation of the bleaching-enhancing compounds that become active can be in the range of from 1 second to 24 hours.Alternatively, as the bleaching-enhancing compounds are relatively stable in the wash solution, the peracid can become active in the washing solution after the bleaching-enhancing compound becomes active or available The purpose of a delayed addition of bleaching composition (which may or may not be used in conjunction with this invention) it is to allow the peracid to reach its maximum bleaching performance in a fabric that needs cleaning, such as a soiled cloth, in a washing solution prior to the introduction of the bleaching enhancing compound. In other words, a bleaching composition containing a bleach-enhancing compound that becomes active in a wash solution after a fabric in need of cleaning has been added to the wash solution. Methods for the delayed (controlled) addition of bleaching-enhancing compounds are fully described in the co-pending co-pending US Provisional Patent Application *. ¿* I * f- * Í? T ** «~ i .. ^ ** f * e? * XG! J * J. *? Al * Jk entitled "Controlled Availability of Formulation Components, Compositions and Laundry Methods Employing Them" filed on August 27, 1999 (P &G Attorney Act Number 7749P ). Alternatively, since the bleach-enhancing compounds may have improved stability, a bleaching composition containing a bleach-enhancing compound that becomes active in a wash solution may be used before a fabric in need of cleaning has been added to the bleach. the washing solution. The bleaching compositions of the present invention, described heretofore, one or more cleaning adjunct materials, preferably compatible with the bleach booster (s) and / or any enzyme present in the bleaching composition. The term "compatible", as used herein, means that the materials of the bleaching composition do not reduce the bleaching activity of the bleach booster and / or any enzymatic activity present in the bleaching composition to such an extent that the bleach booster and / or enzyme is not effective as desired during normal use situations. The term "accompanying cleaning materials", as used herein, means any liquid, solid or gaseous material chosen from the particular type of bleaching composition desired in the form of the product (eg, liquid, granule, powder, bar, paste; spray; tablet; gel; foaming composition), whose materials are also preferably compatible with the protease enzyme (s) and bleaching agent (s) used in the composition. The granular compositions may also be in "compact" form and the liquid compositions may also be in a "concentrated" form. The specific selection of the attached cleaning materials is easily made by considering the surface, the article or fabric to be cleaned, and the desired shape of the composition for cleaning conditions during use (for example, through the use of the wash detergent). Examples of suitable adjunct cleaning materials include, but are not limited to surfactants, detergency builders, bleaches, bleach activators, bleach catalysts, other enzymes, enzyme stabilizer systems, chelators, optical brighteners, soil release polymers, agents transfer of dyes, dispersants, foam suppressors, dyes, perfumes, dyes, filler salts, hydrotropes, photoactivators, fluorescers, fabric conditioners, hydrolyzable surfactants, preservatives, anti-oxidants, anti-shrinking agents, anti-wrinkle agents, germicides, fungicides, colored specks, silver care, anti-fogging and / or anti-corrosion agents, alkalinity sources, solubilizing agents, carriers, process aids, pigments and agents to control the pH as described in the US Patents Nos. 5,705,464, 5,710,115, 5,698,504, 5,695,679 and 5,646,101. The specific materials of the bleaching composition are exemplified in detail hereafter.

If the attached cleaning materials are not compatible with the protease variant (s) in the bleaching compositions, then compatible methods can be used to keep the cleaning materials attached and the variant (s) of protease separated (without being in 5 contact each other) until the combination of the two components is adequate. Compatible methods may be any method known in the art, such as gelcaps, encapsulation, tablets, physical separation, etc. Such bleaching compositions include detergent compositions for cleaning hard surfaces, without limits in form (for example: 10 liquid, granular, paste, foam, spray, etc,); detergent compositions for cleaning fabrics, without limit in form (for example, granular, liquid, bar formulations, etc.); compositions for washing dishes (without limit in form and including automatic dish washing with granular or liquid forms); oral whitening compositions, without limit in the form (for 15 examples, dentifrices, toothpaste and mouthwash formulations); Y . denture whitening compositions, without limit in form (eg, liquid, tablet). The fabric bleaching compositions of the present invention are primarily designed to be used in the wash cycle of 20 a washing machine; however, other uses can be contemplated, such as pre-treatment product for very dirty fabrics, or soaking product; the use is not necessarily limited to the context of the washing machine of laundry, and the compositions of the present invention may be used alone or in combination with compositions compatible with hand washing. The bleaching compositions may include from 1% to 99.9% by weight of the composition of the cleaning materials attached. As used herein, "bleach compositions that are not for fabrics" include bleaching compositions for hard surfaces, fretting compositions, oral bleaching compositions, denture bleaching compositions and personal cleansing compositions. When the bleaching compositions of the present invention are formulated as compositions suitable for use in a laundry washing method and a builder compound and additionally one or more adjunct cleaning materials preferably chosen from organic polymeric compounds, bleaching agents, additional enzymes , suds suppressors, dispersants, calcium-hydroxide-soap dispersants, soil and anti-redeposition agents for dirt and corrosion inhibitors. The laundry compositions may also have softening agents, such as additional cleaning materials attached. The compositions of the present invention can also be used as detergent additive products in solid or liquid form. Such additive products are designed to complement or increase the performance of conventional detergent compositions and can be added at any stage of the cleaning inmate. When formulated as compositions for use in manual dish washing methods, the compositions of the invention preferably contain a surfactant and preferably other adjunct cleaning materials chosen from the organic polymeric compounds, foam-boosting agents, metal ions of the group II, solvents, hydrotropes and additional enzymes. If necessary, the density of laundry detergent compositions 10 ranges from 400 to 1200 g / liter, preferably 500 to 950 g / liter of composition measured at 20 ° C. The "compact" form of bleaching compositions here • is best reflected by density and in terms of composition, by the amount of inorganic filler salt; the inorganic filler salts are ingredients 15 conventional detergent compositions in powder form; in conventional detergent compositions, the filler salts are present in substantial amounts, typically 17-35% by weight of the total composition. In compact compositions, the filler salt is j? present in quantities not exceeding 15% of the total composition, of 20 preferably not exceeding 10%, preferably not exceeding 5% by weight of the composition. The inorganic filler salts, as they mean in the present compositions are chosen from salts of alkaline or alkaline earth metals of sulphates and chlorides. A preferred filler salt is sodium sulfate. The liquid bleaching compositions according to the present invention may also be in "concentrated" form, in such case, the liquid bleaching compositions according to the present invention will have a lower amount of water, compared to conventional liquid detergents. Typically the water content of the • Concentrated liquid bleaching composition is preferably less than 40%, preferably less than 30%, preferably less than 20% by weight 10 of the bleaching composition.

Attached cleaning materials 9 Although not essential for the purposes of the present invention, several conventional attachments illustrated hereinafter are 15 suitable for use in the instant bleaching compositions and can be desirably incorporated into preferred embodiments of the invention, for example to assist or increase cleaning performance, for the treatment of the substrate to be cleaned, or to modify ? k the aesthetics of bleaching composition, as is the case of perfumes, 20 dyes, dyes or the like. The precise nature of these additional components, and the levels of incorporation thereof, will depend on the physical form of the composition and the nature of the cleaning operation for which they are to be used. Unless otherwise indicated, the Bleaching compositions of the invention can, for example, be formulated as granular or powder or "high-yield" washing agents, especially laundry detergents; washing agents in the form of gel or paste for all purposes, especially so-called high-performance liquid types; liquid line fabric detergents; agents for the manual washing of frets or dish washing agents for light tasks, especially those of the type that produce a lot of foam; agents For automatic dishwashers, including various types of tablet, granular, liquid and rinsing aid for domestic maintenance and institutional use; liquid cleaning agents and disinfectants, including antimicrobial types of hand washing, laundry bars, mouth rinses, denture cleaners, shampoos for cars or carpets, cleaners for the bathroom; hair shampoos or hair rinses; gels for shower and foam baths and metal cleaners; as well as cleaning aids such as bleach additives and "stain absorbing" or pre-treatment types. Surfactants - The compositions of the present invention preferably contain a detergent surfactant. The detergent surfactant is typically selected from the group consisting of anionic, nonionic, cationic, ampholytic, zwitterionic, and mixtures thereof. By choosing a type and amount of detergent surfactant, together with other adjunct ingredients disclosed herein, the present detergent compositions can be formulated for use in the context of laundry and cleaning. Ü_tl .___ > , _l_¿__ Í, A * .j * ¿i, 1l «. *. s« - - ".- J..i, -...,, ja» "...» _. ... t ..__ jwfai, ___ »r.» J- «j? tui» to «aij ..- iiiafci? rp * &.. --NIA & ¡.uid? t?«? * .- R fabrics or in other different cleaning applications, especially including the washing of frets.The particular surfactants used can therefore vary widely depending on the particular end use planned.The suitable surfactants are described below. Ionic, anionic, cationic, amphoteric and zwitterionic are given in "Surface Active Agents and Detergents" (Vol.I and II by Schwartz, Perry and Berch.) A variety of such surfactants are also generally disclosed in US Patent 3,929,678 , issued December 30, 1975 to Laughiin, et al., Column 23, line 58 to Column 29, line 23. The surfactant is typically present at a level of 0.1%, preferably 1%, more preferable about 5% in weight of the composition whitening to about 99.9%, preferably about 80%, more preferably about 35%, more preferably 30%, by weight of the bleaching compositions. Anionic surfactants - The anionic surfactants useful in the present invention are preferably selected from the group consisting of, linear alkyl benzene sulphonate, alpha olefin sulfonate, paraffin sulphonates, alkyl ester sulphonates, alkyl sulfates, alkoxy alkyl sulfates.

Alkyl sulphonates, alkoxy alkoxy carboxylate, alkyl akoxylated sulfates, sarcosinates, taurinates, and mixtures thereof. An effective amount, typically from 0.5% to about 90%, preferably from about 5% to 60%, more preferably from 10 to 30%, by weight of the anionic detergent surfactant can be used in the present invention. i.? k? k - l ^ ** ^ * J ** ~ * .- < -.--. *? i- * k. .... ^ .-. ^ > ^. ? ^ t k ?? v? lt * »** ^» **** ^^^ The alkyl sulfate surfactants are another type of anionic surfactant of importance to be used here. In addition to providing excellent overall cleaning capacity when used in combination with the polyhydroxy fatty acid amides (see below), 5 including good grease / oil cleaning over a wide range of temperatures, wash concentrations, and wash times , the dissolution of alkyl sulfates can be obtained, as well as improved formulation capacity in liquid detergent formulations are with the water soluble salts or acids of the formula ROSO3M wherein R Preferably it is C Co-C2 hydrocarbyl, preferably an alkyl or a hydroxyalkyl having a C10-C20 alkyl component, more preferably a Ci2-C ?8 alkyl or hydroxyalkyl, and M is H or a cation, e.g., a alkali metal cation (group IA) (for example, sodium, potassium, lithium), substituted or unsubstituted ammonium cations such as methyl-, dimethyl-, and trimethyl-ammonium and 15 quaternary ammonium cations, for example, tetramethylammonium and dimethylpiperidinium, and cations from alkanolamines such as ethanolamine, diethanolamine, triethanolamine, and mixtures thereof, and the like. Typically, C12-C16 alkyl chains are preferred for lower wash temperatures (e.g., below 50 ° C) and 20 prefer C16-C18 alkyl chains for higher wash temperatures (for example, above 50 ° C). Alkoxylated alkyl sulfate surfactants are another category of useful anionic surfactants. These surfactants are salts or water soluble acids typically of the formula RO (A) mS03M wherein R is an unsubstituted C ?o-C 24 alkyl or hydroxyalkyl group having a C? or C24 alquilo alquilo alkyl component, preferably a C12-C20 alquilo alkyl or hydroxyalkyl, preferably Ci2-d8 alkyl or hydroxyalkyl, A is an ethoxy or propoxy unit, m is greater than zero, typically between 0.5 and 6 more preferably between 0.5 and about 3, and M is H or a cation which may be, for example , a metal cation (for example, sodium, potassium, lithium, etc.), ammonium cation or substituted ammonium cation. Ethoxylated alkyl sulfates as well as propoxylated alkyl sulfates are contemplated herein. Specific examples of substituted ammonium cations include methyl-, dimethyl-, trimethyl-ammonium and quaternary ammonium cations, such as tetramethylammonium, dimethyl piperidinium and cations derived from alkanolamines, eg, monoethanolamide, diethanolamide, and triethanolamide, and mixtures thereof. Exemplary surfactants are polyethoxylated Ci.sub.2 -C.sub.18 alkyl sulfate (1.0), C.sub.2 -C.sub.1-8 polyethoxylated alkyl sulphate (2.25), polyethoxylated C.sub.2 -C.sub.C.sub.8 alkyl sulfate (3.0), and sulfate of polyethoxylated d2-C18 alkyl (4.0) wherein M is conveniently selected from sodium and potassium. The surfactants to be used here can be made from natural or synthetic alcohol reserves. The lengths of the chains represent the average distributions of hydrocarbons, including branching. Additionally and preferably, the surfactant may be a branched alkyl sulphate half chain, alkoxylated alkyl branched half chain, or alkoxylated alkyl sulphate branched to the middle of the chain. These surfactants are further described in No. 60/061, 971, Num. Of the record of the lawyer 6881 P October 14, 1997, No. 60/061, 975, Num. Of the record of the lawyer 6882P October 14, 1997, No. 60 / 062,086, Num. of lawyer 6883P October 14, 1997, No. 60/061, 916, Num. record of attorney 6884P October 14, 1997, No. 60/061, 970, Num. record of attorney 6885P October 14, 1997, 60 / 062,407, No. 6886P attorney's note October 14, 1997. Other compatible surfactants branched to the middle of the chain can be found in US Patent Applications Nos. Serial No. 60 / 032,035 (Num Acta 6401 P)., 60/031, 845 (Minutes No. 6402P), 60/031, 916 (Minutes No. 6403P), 60/031, 917 (Minutes No. 6404P), 60/031, 761 (Minutes No. 6405P), 60 / 031,762 (Act No. 6406P) and 60 / 031,844 (Act No. 6409P). Mixtures of these branched surfactants with conventional linear surfactants are also suitable for use in the present composition. Other preferred anionic surfactants are so-called modified alkyl benzene sulphonate surfactants, or MLAS. Some compatible MLAS surfactants, methods for making them and exemplary compositions are further described in U.S. patent applications no. of series 60 / 053,319 (Minutes No. 6766P), 60 / 053,318 (Minutes No. 6767P). 60 / 053,321 (Minutes No. 6768P), 60 / 053,209 (Minutes No. 6769P), 60 / 053,328 (Minutes No. 6770P), 60 / 053,186 (Minutes No. 6771 P), 60 / 055,437 (Minutes No. 6796P) , 60 / 105,017 (Acta Num. 7303P), and 60 / 104,962 (Acta Num. 7304P).

BÁ * a «.l * müfc ^. ..

Examples of suitable anionic surfactants are given in "Surface Active Agents and Detergents" (Vol. I and II by Schwartz, Perry and Berch).

Non-ionic detergent surfactants - Surfactants Suitable non-ionic detergents are generally disclosed in U.S. Patent 3,929,678, Laughiin et al., Issued December 30, 1975, in column 13, line 14 to column 16, row 6, incorporated here by reference. Non-limiting exemplary classes of useful nonionic surfactants include: amine oxides, alkyl ethoxylate, amide glucose alkanoyl, alkyl 0 betaines, sulfobetaine and mixtures thereof. The amine oxides are semi-polar nonionic surfactants and include water-soluble amine oxides containing an alkyl entity of 10 to 18 carbon atoms and 2 entities selected from the group consisting of alkyl groups and hydroxyalkyl groups containing from 1 to 3 atoms of 5 carbon; water-soluble phosphine oxides containing an alkyl entity of 10 to 18 carbon atoms and 2 entities selected from the group consisting of by alkyl groups and hydroxyalkyl groups containing from 1 to 3 carbon atoms; and water soluble sulfoxides containing an alkyl entity of 10 to 18 carbon atoms and one entity chosen from the group consisting of 0 alkyl or hydroxyalkyl entities of 1 to 3 carbon atoms.

Semi-polar non-ionic detergent surfactants include the amine oxide surfactants having the formula O R3 (OR4) xN (R5) 2 IX- Where R3 is an alkyl, hydroxyalkyl or alkyl phenyl group or mixtures thereof containing from 8 to 22 carbon atoms; R4 is an alkylene or hydroxyalkylene group containing from 2 to 3 carbon atoms or mixtures thereof; x is 0 to 3; and each R 5 is an alkyl or hydroxyalkyl group of 1 to 3 carbon atoms or polyethylene oxide group of 1 to 3 of ethylene oxide groups. The R5 groups can be linked together, for example, through an oxygen or nitrogen atom, to form a ring structure. These amine oxide surfactants in particular include amine oxides C 1 or C 8 alkyl dimethyl and oxides of amine ethyl dihydroxy ethyl alkoxy C 8 -C 12. Preferably the amine oxide is present in the composition in an effective amount, more preferably from 0.1% to 20%, still more preferably from 0.1% to 15%, even more preferably from 0.5% to 10% by weight- The oxide condensates of polyethylene, polypropylene and polybutylene of alkyl phenols. In general, polyethylene oxide condensates were preferred. These compounds include the condensation products of alkyl phenols having an alkyl group having from 6 to 12 carbon atoms in the straight or branched chain configuration with the alkylene oxide. In a preferred embodiment, the ethylene oxide is present in an amount equal to 5 to 25 mol of ethylene oxide per mol of phenol alkyl. Commercially available nonionic surfactants of this type include Igepal® CO-630, marketed by GAF Corporation; and Triton® X-45, X-114, X-100, and X-102, all marketed by the Rohm & Haas. These compounds are commonly regarded as alkyl phenol alkoxylates, (eg, alkyl phenol ethoxylates). The condensation products of aliphatic alcohols with 1 to 25 mol of ethylene oxide. The alkyl chain of the aliphatic alcohol may be linear or branched, primary or secondary, and generally contains from 8 to 22 carbon atoms. Particularly preferred are the condensation products of alcohols having an alkyl group having from 10 to 20 carbon atoms with 2 to 18 mol of ethylene oxide per mole of alcohol. Examples of commercially available nonionic surfactants of this type 10 include Tergitol® 15-S-9 (the condensation product of the secondary linear C11-C15 alcohol with 9 mol of ethylene oxide), Tergitol® 24-L-6 NMW (the condensation product of the C? 2 alcohol) Primary C-4 with 6 mol of ethylene oxide with a narrow molecular weight distribution), both marketed by Union Carbide Corporation; Neodol® 45-9 (the product of 15 condensation of d-d5lineal alcohol with 9 mole of ethylene oxide), Neodol® 23-6.5 (the condensation product of linear C12-C13 alcohol with 6.5 mole of ethylene oxide), Neodol® 45-7 (the product of condensation of linear C-C-15 alcohol with 7 mol of ethylene oxide), Neodol® 45-4 (the condensation product of the linear dCi5 alcohol with 4 mol of * ^ 20 ethylene), marketed by Shell Chemical Company, and Kyro® EOB (the condensation product of C-13-C15 alcohol with 9 mol of ethylene oxide), marketed by The Procter & Gamble Company. Other commercially available nonionic surfactants include Dobanol 91-8® marketed by Shell Chemical Co. and genapol UD-080® marketed by Hoechst. This category of non-ionic surfactants is generally considered to be "alkyl ethoxylates." The preferred alkyl polyglucosides have the formula 5 R20 (CnH2nO) t (glycosyl) x Wherein R2 is selected from the group consisting of alkyl, alkyl-phenyl, hydroxyalkyl, hydroxyalkylphenyl, and mixtures thereof in which the ^ alkyl groups contain from 10 to 18, preferably from 12 to 14, carbon atoms; n is 2 or 3, preferably 2; t is 0 to 10, preferably 0; and x is 10 1.3 to 10, preferably from 1.3 to 3, more preferably from 1.3 to 2.7. The glycosyl comes preferentially from glucose. To prepare these compounds, the alcohol or alkylpolyethoxy alcohol is first formed and then reacts with • glucose, or a source of glucose, to form the glucoside (annex in position 1). The additional glycosyl units can then be bound between the 15 position 1 and the preceding glycosyl units 2-, 3-, 4-, and / or 6-position, of predominantly position 2.

The amide surfactants of fatty acids that have the Formula: O # R6CN (R7)? Where R6 is an alkyl group containing from 7 to 21 (preferably from 9 to 17) carbon atoms and each R7 is selected from the group consisting of hydrogen, CrC 4 alkyl, hydroxyalkyl CrC 4, and - (C 2 H 0) x H wherein x ranges from 1 to 3. Preferred amides are C 8 -C 2 ammonium amides. monoethanolamides, diethanolamides, and isopropanolamides. Preferably the nonionic surfactant, when present in the composition, is present in an effective amount, preferably from 0.1% to 20%, even more preferably from 0.1% to 15%, even more preferably from 0.5% to 10% in weigh. 10 Polyhydroxy fatty acid amide surfactant - The detergent compositions herein may also have an effective amount of polyhydroxy fatty acid amide surfactant. By quantity "Effective" it is understood that the formulator of the composition may choose an amount of polyhydroxy fatty acid amide to be incorporated into the 15 compositions that will improve the cleaning performance of the detergent composition. In general, for conventional levels, the incorporation of 1%, by weight, the polyhydroxy fatty acid amide will increase the cleaning performance. The detergent compositions herein typically comprise 20% by weight, polyhydroxy fatty acid amide surfactant, preferably from 3% to 30%, of the polyhydroxy fatty acid amide. The surfactant component of polyhydroxy fatty acid amide comprises compounds of the structural formula: R2CNZ Wherein: R1 is H, hydrocarbyl C, 2-hydroxyethyl, 2-hydroxypropyl, or mixtures thereof, preferably alkyl d-d, more preferably Ci or C2 alkyl, more preferably Ci-alkyl (ie, methyl); and R2 is a C5-C31 hydrocarbyl, preferably linear alkyl chain C-C2 or alkenyl, more preferred Cg-C alkyl? linear chain or alkenyl, more preferred linear chain C11-C5 alkyl or alkenyl, 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 • it will preferably come from a reducing sugar in a reductive amination reaction; more preferably Z will be a glycityl. The sugars 15 compatible reductants include glucose, fructose, maltose, lactose, galactose, mannose, and xylose. As raw materials, high fructose corn syrup, and high maltose corn syrup can be used as well as in the individual sugars listed above. These corn syrups can give a mixture of sugar components for Z. It should be understood that • 20 no medium is not intended to exclude other compatible raw materials. Z will preferably be chosen from the group consisting of -CH2- (CHOH) n-CH2OH, -CH (CH2OH) - (CHOH) n-rCH2OH, -CH2- (CHOH) 2 (CHOR ') (CHOH) -CH2OH, and alkoxylated derivatives thereof, in where n is an integer from 3 to 5, inclusive, and R 'is H or a cyclic or aliphatic monosaccharide. Most preferred are glycityls wherein n is 4, especially -CH2- (CHOH) 4-CH2OH. R 'can be, for example, N-methyl, N-ethyl, N-propyl, N-isopropyl, 5-N-butyl, N-2-hydroxyethyl, or N-2-hydroxypropyl. R2-CO-N < it can be, for example, cocamide, stearamide, oleamide, lauramide, myristamide, caoricamide, palmitamide, tallowamide, etc.

# Z can be 1-deoxyglucityl, 2-deoxifructityl, 1-deoxymaltityl, 1-deoxylactityl, 1-deoxygalactityl, 1-deoxyxanityl, 1-deoxymaltotriotityl, etc. The methods for making polyhydroxy fatty acid amides are known in the art. In general, these can be made by reacting an alkyl amine with a reducing sugar in a reductive amination reaction to form a corresponding N-alkyl polyhydroxyamine, and then reacting the N-alkyl-polyhydroxyamine with a fatty aliphatic ester or 15 triglyceride in a condensation / amidation step to form the product N-alkyl, N-polyhydroxy fatty acid amide. Processes for making compositions containing polyhydroxy fatty acid amides are disclosed, for example, in G.B. Patent Specification 809,060, published February 18, 1959 by Thomas Hedley & Co., Ltd., US Patent 2,965,576, issued on 20 December 20, 1960 to E.R. Wilson, and US Patent 2,703,798, Anthony M. Schwartz, issued March 8, 1955, and US Patent 1, 985,424 issued December 25, 1934 to Piggott, each of which is incorporated herein by reference.

Diamnes - Preferred liquid detergent compositions, such as light duty liquid, LDL compositions, useful in the methods of the present invention may additionally have one or more diamines, preferably an amount of diamine such that the proportion of anionic surfactant present in relation to with the diamine is from 40: 1 to 2: 1. Said diamines provide a high removal of fatty material and fatty foods while maintaining adequate levels of foam. Diamines suitable for use in the compositions of the present invention have the formula: Wherein each R20 is independently selected from the group consisting of hydrogen, straight or branched C4 alkyl, alkyleneoxy having the formula: - (R210) and R22- wherein R21 is straight or branched C2-C4 alkylene, and mixtures thereof; R22 is hydrogen, alkyl d-d, and mixtures thereof; and it is 1 to 10; X is a unit chosen from: i) C3-C10 linear alkylene, branched C3-C10 alkylene, cyclic C3-C10 alkylene, branched C3-C10 cyclic alkylene, an alkylene-alkylene-alkylene having the formula: - (R210) and R21- Where R21 and they are the same as defined above; ii) linear C3-C10 alkylene, branched linear C3-C10, cyclic C3-C10, branched cyclic C3-C10 alkylene, Ce-C19 arylene, wherein said unit comprises one or more donor or electron donor entities that said diamine provides a pKa greater than 8; and iii) mixtures of (i) and (ii) as long as said diamine has a pKa of at least 8. Preferred diamines of the present invention have a pKi and pK2 which are each in the range of 8 to 11.5, preferably in the range of 8.4 to 11, more preferably from 8.6 to 10.75. for the purposes of the present invention the term "pKa" equally well represents the terms "pK and" PK2"either separately or collectively, the term pKa as used herein throughout the present specification in the same manner as it is used by those experienced in the area pKa values are easily obtained from standard literature sources eg "Critical Stability Constants: Volume 2, Amines" by Smith and Martel, Plenum Press, NY and London, (1975) As a definition applied here, the pKa values of the diamines are specified by being measured in an aqueous solution at 25 ° C having an ionic strength of 0.1 to 0.5 M. As used herein, the pKa is an equilibrium constant depending on the temperature, on the ionic strength, therefore, the value reported by the references of the literature, not measured in the manner described above, may not be in agreement with the values and intervals that c they comprise the present invention. For eliminate ambiguity, relevant conditions and / or references used for the pKa's of this invention are as defined herein or in "Critical Stability Constants: Volume 2, Amines". A typical method of measurement is the potentiometric titration of acid with sodium hydroxide and the determination of pKa by suitable methods as described and referenced in "The Chemist's Ready Reference Handbook" by Shugar and Dean, McGraw 'Hill, NY, 1990 The preferred diamines for performance and delivery considerations are 1, 3-bis (methylamino) cyclohexane, 1,3-diaminopropane (pK = 10.5, pK2 = 8.8), 1,6-diaminohexane (pK -? = 11, pK2 = 10), 1, 3.diaminopentane (Dytek EP) (pK ^ IO.5, pK2 = 8.9), 2-methyl-1,5-diaminopentane (Dytek A) (pK = 11.2, pK2 = 10.0). Other preferred materials are the primary / primary diamines having alkylene spacers ranging from C4-C8. In general, primary diamines are preferred over secondary and tertiary diamines. The following are non-limiting examples of diamines suitable for the present invention. 1-N, N-dimethylamino-3-aminopropane having the formula: 1, 6-diaminohexane having the formula: 1, 3 formula: 2-methyl-1, 5-diaminopentane having the formula: 1, 3-diaminopentane, available under the trade name Dytek EP, which has the formula: 1,3-diaminobutane having the formula: Jeffamine EDR 148, a diamine having an alkyleneoxy skeleton, having the formula: , NH "H.N ^ O" 3-methyl-3-aminoethyl-5-dimethyl-1-aminocyclohexane (diamine isophorone) having the formula: . and 1,3-bis (methylamino) cyclohexane which has the formula: . * * Additional Detergent Components The following are non-limiting examples of additional detergent components (adjunct ingredients) useful in the bleaching compositions, especially laundry detergent compositions, of the present invention, said adjunct ingredients include builders, optical brighteners, soil release polymers , dye transfer agents, dispersants, enzymes, foam suppressors, dyes, perfumes, dyes, filler salts, hydrotropes, photoactivators, fluorescers, fabric conditioners, hydrolyzable surfactants, preservatives, anti-oxidants, chelators, stabilizers, anti-aging agents shrinkage, anti-wrinkle agents, germicides, fungicides, anti-corrosion agents, and mixtures thereof. Detergency builders - The bleaching compositions of the present invention preferably comprise one or more detergent builders or builders systems. When present, the compositions will typically comprise at least 1% builder, preferably about 5%, more preferably 10% to 80%, preferably 50%, more preferably 30% by weight, of detergent builder.

The level of builder can vary widely depending on the final use of the composition and its desired physical form. When present, the compositions will typically have at least 1% builder. The formulations typically comprise 5% to 50%, more typically about 5% to about 30%, by weight, of detergent builder. Granular formulations typically comprise from 10% to 80%, more typically from 15% to 50% by weight, of the detergent improver. However, it does not mean that lower or higher levels of builder will be excluded. Inorganic detergent builders or P-containing detergents include, but are not limited to, the alkali metal, ammonium and alkanolammonium salts of polyphosphates (exemplified by the tripolyphosphates, pyrophosphates, and glassy polymeric meta-phosphates), phosphonates, phytic acid , silicates, carbonates (including bicarbonates and sesquicarbonates), sulfates, and aluminosilicates. However, non-phosphate builders are required in some scenarios. In an important way, the compositions here work surprisingly well even in the presence of the so-called "weak" builders (compared to phosphates) such as citrate, or in the so-called "sub-built" situation that can occur with zeolite or builders. Layered silicates Examples of silicate builders are alkali metal silicates, especially those having a SiO2: Na20 ratio in the range of 1.6: 1 to 3.2: 1 and layered silicates, such as Layered sodium silicates described in US 4,664,839 Rieck, issued May 12, 1987. NaSKS-6 is the trademark of a layered crystalline silicate marketed by Hoechst (commonly abbreviated herein as "SKS-6"). Unlike zeolite builders, the Na SKS-6 silicate builder does not contain aluminum. NaSKS-6 has the delta-Na2Si? 5 morphology of the layered silicate form. It can be prepared by methods such as those described in German DE-A-3,417,649 and DE-A-3,742,043. SKS-6 is the highly preferred layered silicate for use herein, but other layered silicates, such as those having the general formula NaMSix? 2x + i and H20, wherein M is hydrogen, x is a number from 1.9 to 4, preferably 2, and y is a number from 0 to 20, preferably 0 can be used here. Different layered silicates from Hoechst include NaSKS-5, NaSKS-7 and NaSKS-11, such as the alpha, beta, and gamma forms. As noted above, the delta-Na2Si? 5 form (NaSKS-6 form) is most preferred to be used herein. Other silicates may also be useful such as for example magnesium silicate, which can serve as a curling agent in granular formulations, as a stabilizer for oxygen bleaches, and as a component of foam control systems. Examples of carbonate builders are alkaline earth and alkaline carbonates as disclosed in German Patent Application No. 2,321,001 published November 15, 1973. Aluminosilicate builders are useful in the present invention. Aluminosilicate builders are of great importance in most of the high performance granular detergent compositions currently marketed, and can also be a significant detergency enhancing ingredient in liquid detergent formulations. The aluminosilicate builders include those that have the empirical formula: [Mz (zAI02) and] xH20 where z and y are integers of at least 6, the molar ratio of zay is in the range of 1.0 to 0.5, and x is an integer from 15 to 264. Useful aluminosilicate ion exchange materials are commercially available. These aluminosiíicatos can have amorphous or crystalline structure and can be aluminosilicatos that are in the nature or obtained by synthesis. A method for producing aluminosilicate ion exchange materials is disclosed in US 3,985,669, Krummel et al., Issued October 12, 1976. The synthetic crystalline aluminosilicate ion exchange materials useful herein are available under the names of Zeolite A, Zeolite P (B), Zeolite MAP and Zeolite X. In an especially preferred embodiment, the crystalline aluminosilicate ion exchange material has the formula: Na12 [(AI02) i2 (Si02)? 2] xH20 where x is from 20 to 30 , especially 27. This material is known as Zeolite A. Dehydrated zeolites (x = 0-10) can also be used here. Preferably, the aluminosilicate has a particle size of 0.1-10 microns in diameter. ? * "\ ** t f ^^ .. *: *. * - ..

Organic detergent builders suitable for the purposes of the present invention include, but are not limited to, a wide variety of polycarboxylate compounds. As used herein, "polycarboxylate" refers to compounds having a plurality of carboxylate groups, preferably at least 3 carboxylates. The polycarboxylate builder generally can be added to the composition in the acid form, but it can also be added in the form of a neutralized salt. When used in its salt form, alkali metals, such as sodium, potassium and lithium, or alkanolammonium salts are preferred. Included among the polycarboxylate builders are a variety of useful material categories. An important category of carboxylate builders encompasses polycarboxylate ether, including oxydisuccinate, as disclosed in US 3,128,287 Berg, issued April 7, 1964, US 3,635,830 Lamberti et al., issued January 18, 1972, and US 3,936,448 Lamberti, issued February 3, 1976. See also detergent builders of "TMS TDS" from US 4,663,071 Bush et al., issued May 5, 1987. Suitable polycarboxylate ether also include cyclic compounds, especially alicyclic compounds, such as those described in US 3,923,679 Rapko, issued on 2 December 1975; US 4,158,635 Crutchfield et al., Issued June 19, 1979; US 4,120,874 Crutchfield et al., Issued 17 October 1978; and US 4,102,903 Crutchfield et al., issued July 25, 1978. Other detergency builders for useful detergents include hydroxypolycarboxylate ether, co-polymers of maleic anhydride with ethylene or methyl vinyl ether, 1,3-trihydroxy acid benzene-2,4,6-trisulfonic, and carboxymethyloxysuccinic acid, the various alkali metals, ammonium and substituted ammonium salts of polyacetic acids such as ethylenediamine tetraacetic acid and nitrilotriacetic acid, as well as polycarboxylates such as methyl acid, succinic, oxydisuccinic acid, polymaleic acid, benzene 1, 3,5-tricarboxylic acid, carboxymethyloxysuccinic acid, soluble salts thereof. Citrate builders, for example, citric acid and soluble salts thereof (especially the sodium salt), are polycarboxylate builders of particular importance for formulations of high-performance liquid detergents because of their availability from resources renewable and its biodegradability. The citrates can also be used in granular compositions, especially in combination with zeolite and / or layered silicate builders. Oxydisuccinates are also especially useful in such compositions and combinations. They are also suitable for the bleaching compositions of the present invention the 3,3- icarboxi-4-oxa-1,6-hexanedioates and related compounds disclosed in US 4,566,984, Bus, issued January 28, 1986. The builders of useful succinic acid they include the C5-C20 alkyl or alkenyl succinic acids and the salts thereof. A particularly preferred compound of this type is dodecenylsuccinic acid. Specific examples of succinate builders include: laurylsuccinate, myristylsuccinate, palmitylsuccinate, 2-dodecenylsuccinate (preferred), 2-pentadecenylsuccinate and the like. Lauryl succinates are the preferred builders of this group, and are described in European Patent Application 86200690.5 / 0,200,263, published November 5, 1986. Other compatible polycarboxylates are disclosed in US 4,144,226, Crutchfield et al. March 1979, and US 3,308,067 issued March 7, 1967. See also Diehl US Patent 3,723,322. Fatty acids, for example, C12-C18 monocarboxylic acids, may also be incorporated into the compositions alone, or in combination with the aforementioned builders, especially citrate and / or succinate builders, to provide activity. additional upgrader. Such use of fatty acids will generally result in a decrease in foam, which should be taken into account by the formulator. In situations where phosphorus-based detergency builders can be used, and especially in the formation of sticks for manual laundry operations, the various alkali metal phosphates such as the well-known sodium tripolyphosphates, sodium pyrophosphate and the like can be used. sodium orthophosphate. Detergency builders ? I ^ * ^ faith Aj% lM "to phosphate such as ethane-1-hydrox -1,1 -difosfonato and other known phosphonates (see, for example, US 3,159,581 Patent;? 3,213; 030; 3,422,021; 3,400,148 and 3,422,137) can also be used. guelatadores Agents - The bleaching compositions herein may also optionally comprise one or more agents chelators of iron and / or manganese. Chelators such agents can be selected from the group consisting of carboxylates, phosphonates amino, polyfunctionally-substituted aromatic chelators and agents mixtures thereof, all as defined hereinafter. Without intending to be bound by theory, it is believed that the benefit of these materials is due in part to their exceptional ability to remove iron and manganese ions from solutions by the formation of soluble chelates. Examples of suitable chelating agents and levels of use are described in U.S. Patent Nos. 5, 576,282 and 5,728,671. A preferred biodegradable chelator for use herein is ethylene diamine disuccinate ("EDDS"), especially the [S, S] isomer as described in US Patent 4,704,233, November 3, 1987, to Hartman and Perkins. The compositions herein may also have water-soluble salts of methyl glycine diacetic acid (MGDA) (or the acid form) as a useful chelator or co-builder with, for example, insoluble builders such as zeolites, layered silicates and Similar.

If used, these chelating agents generally contain 0.1% by weight of the bleach compositions herein, to about 15%, more preferably 3.0% by weight of the bleaching compositions mentioned herein. 5 Dye transfer inhibiting agents - Bleaching compositions of the present invention may also include one or more compounds, dye transfer inhibiting agents, To inhibit the transfer of dyes from one fabric to another of solubilized and suspended dyes found during the laundry of fabrics and operations 10 conditioning involving colored fabrics. Compatible polymeric dye transfer inhibiting agents include, but are not limited to, polyvinylpyrrolidone polymers, polyamine N-oxide polymers, co-polymers of N-vinylpyrrolidone and N-vinylimidazole, polyvinyloxazolidones and polyvinylimidazoles or mixtures thereof. . Examples of such dye transfer inhibiting agents are disclosed in U.S. Patent Nos. 5,707,950 and 5,707,951. Compatible dye transfer inhibiting agents include, but are not limited to, entangled polymers. The entangled polymers are polymers whose skeleton is interconnected to a certain degree; These links can be of a chemical or physical nature, possibly with active groups in the skeleton or in the branches. The crosslinked polymers have been described in Journal of Polymer Science, volume 22, pages 1035-1039.

In one embodiment, the entangled polymers are made in such a way that they form a rigid three-dimensional structure, which can trap dyes in the pores formed by the three-dimensional structure. In another embodiment, the interlaced polymers trap dyes by turgor. Compatible crosslinked polymers are described in co-pending European Patent Application 94870213.9. The addition of such polymers increases the performance of the enzymes within the bleaching compositions mentioned herein. The dye transfer inhibiting agents have the ability to complex or adsorb washed out stains of stained fabrics before the dyes have the opportunity to bind to other articles in the wash. When present in the bleaching compositions herein, the dye transfer inhibiting agents are present at levels of 0.0001%, preferably 0.01%, more preferably 0.05% by weight of the bleaching composition to about 10%, more preferably near from 2%, more preferably 1% by weight of the bleaching compositions. Dispersants - The bleaching compositions of the present invention may also have dispersants. The compatible water-soluble organic salts are homo- or co-polymeric acids or their salts, in which the polycarboxylic acids contain at least two carboxyl radicals separated from one another by not more than two carbon atoms.

Polymers of this type are disclosed in GB-A-1,596,756. Examples of such salts are polyacrylates of molecular mass 2000-5000 and their co-polymers with maleic anhydride, such co-polymers having a molecular weight of 1,000 to 100,000. Especially, the co-polymer of acrylate and methacrylate such as 480N having a molecular weight of 4000, at a level of 0.5-20% by weight of the composition can be added in the detergent compositions of the present invention. The compositions of the invention may contain a peptizing compound of calcium carbonate and soap, having a dispersing potency of calcium hydroxide and soap (LSDP), as hereinafter defined as not more than 8, preferably not more than 7. , more preferably not more than 6. The calcium carbonate soap peptizer compound is preferably present at a level of 0% to 20% by weight. A numerical measure of the effectiveness of a soap calcium carbonate peptizer is given by the dispersing power of soap calcium carbonate (LSDP) which is determined using the calcium carbonate soap dispersant test as described in an article by HC Borghetty and C.A. Bergman, J. Am. Oil. Chem. Soa, volume 27, pages 88-90, (1950). This dispersion test of calcium carbonate from soap is widely used by practitioners in this area being considered in, for example, the following review articles; W.N. Linfield, Surfactant science series, Volume 7, page 3; W.N. Linfield, Tenside surf. Det., Volume 27, pages 159-163, (1990); and M.K. Nagarajan, W.F. Masier, Cosmetics and Toiletries, volume 104, pages 71-73, (1989). The LSDP is the proportion in weight% of the dispersing agent with respect to the sodium oleate required to disperse the calcium carbonate deposits of the soap formed by 0.025 g of sodium oleate in 30 ml of water of equivalent hardness of 333 ppm (CaCO3). (Ca: Mg = 3: 2) The surfactants that have a good peptizing capacity of the calcium carbonate of the soap will include certain amine oxides, betaines, sulphobetaines, alkyl ethoxysulfates and ethoxylated alcohols The exemplary surfactants that have an LSDP of no more of 8 to be used in accordance with the present invention include Ciß-Ciß dimethyl amine oxide, C 12 -C 18 alkyl ethoxy sulfates with an average degree of ethoxylation of 1-5, particularly C 12 -C 15 surfactant alkyl ethoxysulfate with a degree of ethoxylation of quantity 3 ( LSDP = 4), and C14-C15 alcohols ethoxylated with an average degree of ethoxylation of either 12 (LSDP = 6) or 30, sold under the trademarks Lutensol A012 and Lutensol A030 res ctively, by BASF GmbH. The compatible soap calcium carbonate polymeric peptizers for use herein are described in the M.K. Nagarajan, W.F. Masier, found in Cosmetics and Toiletries, volume 104, pages 71-73, (1989). Hydrophobic bleaches such as 4- [N-octanoyl-6-aminohexanoyl] benzene sulfonate, 4- [N-nonane? L] -6-aminohexane? L] benzene -.- * sulfonate, 4- [N-decanoyl-6-aminohexanoyl] benzene sulfonate and mixtures thereof; and nonanoyloxy benzene sulfonate together with hydrophilic / hydrophobic bleach formulations can also be used as soap carbonate calcium carbonate compounds. Enzymes - The bleaching compositions may have in addition to the amylase of the present invention one or more detergent enzymes that provide cleaning performance and / or fabric care benefits. Such enzymes may include proteases, amylases, cellulases and lipases. These can be incorporated into the non-aqueous liquid bleaching compositions herein in the form of suspensions, "marumes" or "prills". Another suitable type of enzyme comprises those in the form of suspensions of enzymes in nonionic surfactants, for example, the enzymes marketed by Novo Nordisk under the trademark "SL" or the microencapsulated enzymes marketed by Novo Nordisk under the trademark "LDP " Suitable enzymes and levels of use are described in U.S. Patent No. 5,576,282. Enzymes added to the compositions herein in the form of prills of conventional enzymes are especially preferred for use herein. Such prills will generally be in a size range of 100 to 1,000 microns, preferably 200 to 800 microns and will be suspended through the nonaqueous liquid phase of the composition. The prills in the compositions of the present invention have been found, compared to other forms of enzymes, which show an enzyme stability j and ^ ^ ¡^ | . ^^. .., »-Aa especially desirable in terms of retention of enzymatic activity over time. In this way, compositions using enzyme prills need to have no conventional enzyme stabilizers such as those which are frequently used when the enzymes are incorporated into aqueous liquid detergents. Examples of compatible enzymes include, but are not limited to, hemicellulases, peroxidases, proteases, cellulases, xylanases, lipases, phospholipases, esterases, cutinases, pectinases, keratanases, reductases, oxidases, phenoloxidases, lipoxygenases, ligninases, pullulanases, tanases, pentosanases, malanases, β-glucanases, arabinosidases, hyaluronidase, chondroitinase, laccase, known amylases, mannanases, xyloglucanases and mixtures thereof. A preferred combination is one that has a cocktail of conventional enzymes applicable as a protease, lipase, sutinase and / or cellulase together with the amylase of the present invention. Examples of such compatible enzymes are disclosed in U.S. Patent Nos. 5,576,282, 5,728,671 and 5,707,950. Suitable proteases are the subtilisins that are obtained from particular strains of B. subtilis and B. licheniformis (subtilisin BPN and BPN '). A compatible protease is obtained from a strain of Bacillus, which has maximum activity throughout the pH range of 8-12, developed and sold as ESPERASE® by Novo Industries A / S of Denmark, hereinafter "Novo". The preparation of this enzyme and analogous enzymes is described in GB 1,243,784 to Novo. Other compatible proteases include ALCALASE®, M ^? F * 1 ^ - "- * ^ --- • - ~ * ^^ - ** - J - * '- -" ** - * - * - • * - g ^ fa »DURAZYM ® and SAVINASE® by Novo and MAXATASE®, MAXACAL®, PROPERASE® and MAXAPEM® (protein designed by Maxacal) by Gist-Brocades. Proteolytic enzymes also encompass bacterial serine proteases, such as those described in European Patent Application Serial No. 87 303761.8, filed on April 28, 1987 (especially pages 17.24, and 98), and which are incorporated herein by reference. called here "Protease B", and in European Patent Application 199,404, Venegas, published October 29, 1986, which refers to a modified bacterial serine proteolytic enzyme which is called "Protease A" here. More preferable is what is called here "Protease C", which is a variant of a Bacillus alkaline serine protease in which lysine replaced arginine at position 27, tyrosine replaced valine at position 104, serine replaced asparagine at position 123, and alanine replaced threonine at position 274. Protease C is described in EP 90915958: 4, corresponding to WO 91/06637, published May 16, 1991. The genetically modified variants, especially the Protease C, are also included here. See also a high pH protease from Bacillus sp. NCIMB 40338 described in WO 93/18140 to Novo. Enzymatic detergents containing protease, one or more enzymes, and a reversible protease inhibitor are described in WO 92/03529 to Novo. When desired, a protease having decreased adsorption and high hydrolysis is available as described in WO 95/07791 to Procter & Gamble. A recombinant trypsin-like protease for detergents suitable herein is described in WO 94/25583 to Novo.

In more detail, the protease referred to as "Protease D" is a carbonyl hydrolase variant having an amino acid sequence that is not found in nature, which comes from a carbonyl hydrolase precursor substituting a different amino acid for a plurality of residues of 5. amino acids at a position in said carbonyl hydrolase equivalent to the position +76, preferably also in combination with one or more positions of amino acid residues equivalent to those chosen from the • group consisting of +99, +101, +103, +104, +107, +123, +27, +105, +109, +126, +128, +135, +156, +166, +195, + 197, +204, +206, +210, +216, +217, 10 +218, +222, +260, +265, and / or +274 according to the Bacillus amyloliquefaciens subtilisin numbering, as described in WO 95/10615 published April 20, 1995 by Genencor International. Also compatible for the present invention are the proteases described in patent applications EP 251 446 and WO91 / 06637 and the BLAP® protease. 15 described in WO91 / 02792. The proteolytic enzymes are incorporated in the bleaching compositions of the present invention at a level of from 0.0001% to 2%, preferably from 0.001% to 0.2%, more preferably from 0.005% to 0.1% pure enzyme per weight of the composition. ^ Useful proteases are also described in publications PCT: WO 95/30010 published November 9, 1995 by The Procter & Gamble Company; WO 95/30011 published November 9, 1995 by The Procter & Gamble Company; WO 95/29979 published November 9, 1995 by The Procter & Gamble Company.

Other particularly useful proteases are the variants of the multiply substituted proteases comprising a substitution of an amino acid residue with another amino acid residue that appears in nature at a position of the amino acid residue corresponding to position 103 of the subtilisin of Bacillus amyloliquefaciens in combination with a substitution of an amino acid residue with another amino acid residue that appears in nature at one or more positions of amino acid residues corresponding to positions 1, 3, 4, 8, 9, 10, 12, 13, 16, 17, 18, 19, 20, 21, 22, 24, 27, 33, 37, 38, 42, 43, 48, 55, 57, 58 , 61, 62, 68, 72, 75, 76, 77, 78, 79, 86, 87, 89, 97, 98, 99, 101, 102, 104, 106, 107, 109, 111, 114, 116, 117 , 119, 121, 123, 126, 128, 130, 131, 133, 134, 137, 140, 141, 142, 146, 147, 158, 159, 160, 166, 167, 170, 173, 174, 177, 181 , 182, 183, 184, 185, 188, 192, 194, 198, 203, 204, 205, 206, 209, 210, 211, 212, 213, 214, 215, 216, 217, 218, 222, 224, 227 , 228, 230, 232, 236, 237, 238, 240, 242, 243, 244, 245, 246, 247, 248, 249, 251, 252, 253, 254, 255, 256, 257, 258, 259, 260 , 261, 262, 263, 265, 268, 269, 270, 271, 272, 274, and 275 of the subtilisin of Bacillus amyloliquefaciens; wherein when said protease variant includes a substitution of amino acid residues at positions corresponding to positions 103 and 76, there is also a substitution of an amino acid residue at one or more amino acid residue positions other than the residues positions of amino acids corresponding to positions 27, 99, 101, 104, 107, 109, 123, 128, 166, 204, 206, 210, 216, 217, 218, 222, 260, 265, or 274 of the subtilisin of Sac / 7 / s 1 amyloliquefaciens and / or multiply substituted protease variants comprising a substitution of an amino acid residue with another amino acid residue that appears in nature at one or more amino acid residue positions corresponding to positions 62, 212, 230, 232, 252 and 257 of Bacillus amyloliqueafciens subtilisin as described in PCT Pubiished Application Nos. WO 99/20727, WO 99/20726, and WO 99/20723 all owned by The Procter & Gamble Company. More preferable the protease variant includes a substitution chosen from the group consisting of: 12/76/103/104/130 222/245/261; 62/103 / t 04/159/232/236/245/248/252; 62/103/1 4/159 / 13/232/236/245/248/252; 62/101/103/104/159/212 213/232/236/245/248/252; 68/103/1 4/159/232/236/245; 68/103/104/159/230/232/236/245; 68/103/104/159/209/232/236/245; 68/103/104/159/232/236/245/257; 15 68/76/103/104/159/213/232/236/245/260; 68/103/104/159/213/232/236 245/248/252; 68/103/104/159/183/232/236/245/248/252; 68/103/104/159/185/232/236/245/248/252; 68/103/104/159/185/210/232/236/245/248/252; 68/103/104/159/210/232/236/245/248 252; 68/103/104/159/213/232/236/245; ^ p 98/103/104/159/232/236/245/248/252; 20 98/102 103 104/159/212232236/245/248/252; 101/103/104/159/232/236245/248/252; 102/103/104 159/232/236/245/248/252; 103/104/159/230236/245; 103/104/159/232/236/245/248/252; 103/104/159/217/232/236/245/248/252 103/104/130/159/232/236/245/248252 103/104/131/159/232/236/245/248/252 103 / 104/159/213/232/236/245/248/252; Y Even more preferable the protease variant includes a substitution assembly selected from the group consisting of: 12R / 76D / 103A / 104T / 130T 222S / 245R / 261 D; 62D 103A / 104? / 159D / 232V / 236H / 245R / 248D / 252K; 62D / 103 A / 1041 / 159D / 213R / 232V / 236H / 245R / 248D / 252; 68A / 103 A / 1041/1 9D / 209W 232V / 236H / 245R; 68A / 76D / 103A / 1041 / I59D 213R 232V / 236H / 245R / 260A; 68A 103A / I04I / 159D / 213E / 232V / 236H / 245R 248D / 2S2K; 68A / 103A / 104I / 159D / 183D / 232V / 236H / 245R / 248D / 252K; 68A / 103A / 1041 / 159D / 232V / 236H / 245R; 68 A / 103 A / 1041 / 159D 230V / 232V / 236H / 245R; 68A / 103A / 1041 / 159D / 232V / 236H 245R / 257V; 68A 103 A / 1041 / 159D 213G / 232V / 236H / 245R / 248D / 252K; 68A / 103A / 1O4I / 159D / 185D / 232V / 236H 245R / 248D / 252K; 68A / 103A / 104I / 159D / 185D / 210i 232V / 236H 245R / 248D / 252K; 68 A / 103 A / 1041 / 159D / 210L 232V / 236H / 245R / 248D 252K; 68A 103A / 104I / 159D / 213G / 232V / 236H / 245R; 98L / 103A 1041 / 159D / 232V / 236H / 245R / 248D / 252K; 98L / 102A / 103A / 1041 / 159D ^ 12G / 232V / 236H / 245R / 248D / 252K; 101G / 103A / 104I / 159D / 232V / 236H / 245R / 248D / 252K; 102A 103A / 104I / 159D 232V / 236H 245R / 248D / 252K; Preferably the protease variant includes the replacement set 101/103/104/159/232/236/245/248/252, preferably 101 G / 103A 1041 / 159D / 232V / 236H / 245R / 248D / 252K. Cellulases that can be used in the present invention include bacterial or fungal cellulases. Preferably, they will have an optimum pH between 5 and 9.5. Compatible cellulases disclosed in U.S. Patent 4,435,307, Barbesgoard et al, disclose a fungal cellulase produced at from Humicola insolens. Compatible cellulases are also disclosed in GB-A-2,075,028; GB-A-2,095,275 and DE-OS-2,247,832. Examples of such cellulases are cellulases produced by a strain of Humicola insolens (Humicola grísea var. Thermoidea), especially the strain Humicola DSM 1800. Other compatible cellulases are cellulases originated from Humicola insolens having a molecular weight of about 50KDa, a isoelectric point of 5.5 and having 415 amino acids; and an endoglucanase ~ 43kD from Humicola insolens, DSM 1800, exhibiting cellulase activity; a preferred endoglucanase component has the amino acid sequence disclosed in PCT Patent Application No. WO 91/17243. Compatible cellulases are also the EGIII cellulases of Trichoderma longibrachiatum described in WO 94/21801, Genencor, published September 29, 1994. Especially compatible cellulases described in the European Patent Application No. 91202879.2, filed on November 6, 1991 (Novo). ). Carezyme and Celluzyme (Novo Nordisk A / S) are especially useful. See also W091 / 17243. Peroxidase enzymes are known in the area, and include, for example, horseradish peroxidase, ligninase and haloperoxidase such as chloro- and bromo-peroxidase. Bleaching compositions containing peroxidase are disclosed, for example, in U.S. Patent Nos. 5,576,282, 5,728,671 and 5,707,950, PCT International Applications WO 89/099813, WO89 / 09813 and in European Patent Application EP No. 91202882.6, filed on November 6, 1991 and EP No. 96870013.8, filed on February 20, 1996. The laccase enzyme is also compatible. Preferred enhancers are substituted phenothiazine and phenoxyazine 10-Phenothiazinepropionic acid (PPT), 10-ethylphenothiazine-4-5-carboxylic acid (EPC), 10-phenoxazinpropionic acid (POP) and 10-methylphenoxacin (described in WO 94/12621) and syringatos substituted (alkyl substituted C3-C5 syringytes) and phenols. Sodium percarbonate or perborate are preferred sources of hydrogen peroxide. Said peroxidases are normally incorporated in the bleaching composition at levels of 0.0001% to 2% of active enzyme by weight of the bleaching composition. Other preferred enzymes that may be included in the bleaching compositions of the present invention include lipids. Suitable lipase enzymes for the use of detergent include those produced by microorganisms of the Pseudomonas group, such as Pseudomonas stutzeri ATCC 19,154, as disclosed in British Patent 1, 372,034. Suitable lipases include those which show a positive cross-immunological reaction with the lipase antibody, which is produced by the microorganism Pseudomonas fluorescent lAM 1057. 20 lipase is available from Amano Pharmaceutical Co. Ltd., Nagoya, Japan, under the trade name Lipasa P "Amano," hereinafter referred to as "Amano-P". Other compatible commercial lipases include Amano-CES, ex Chromobacter viscosum lipases, eg, Chromobacter viscosum. ^ Á jk & £ fe ^ kj? 8, var. Lipolythicum NRRLB 3673 from Tokio Jozo Cp., Tagata, Japan; Chromobacter viscosum lipases from U.S. Biochemical Corp., U.S.A. and Disoynth Co., The Netherlands, and lipases ex Pseudomonas gladioli. Especially compatible lipases are lipases such as M1 LIPASE® and LIPOMAX® (Gist-Brocades) and LIPOLASE® and LIPOLASE ULTRA® (Novo) which have been found to be very effective when used in combination with the compositions of the present invention . J ^ < And also compatible are cutinases [EC 3.1.1.50] that can be considered as a special type of lipase, called lipases that do not 10 require interphase activation. The addition of cutinases to bleaching compositions has been described in, for example, WO 88/09367 (Genencor). The lipases and / or cutinases are normally incorporated into the bleaching composition at levels of 0.0001% to 2% active enzyme by weight of the bleaching composition. 15 The known amylases (a and / or ß) can be included to remove carbohydrate spots. WO 94/02597, Novo Nordisk A / S published on February 3, 1994, describes cleaning compositions incorporating mutant amylases. See also W094 / 18314, Genencor, published August 18, 1994 and WO95 / 10603. Novo Nordisk A / S, published on April 20, 1995.

Other known amylases for use in bleaching compositions include the α and β amylases. The α-amylases are known in the area and include those disclosed in US Patent 5,003,257; EP 252,666; WO91 / 00353; FR 2,676,456; EP 285,123; EP 525,610; EP 368,341; Y British Patent Specification No. 1, 296,839 (Novo). Another compatible amylase are amylases with increased stability including PURAFACT OX AM® described in WO 94/18314, published August 18, 1994 and WO 96/05295, Genencor, published on February 22, 1996 and 5 variants of Novo amylase. Nordisk A / S, disclosed in WO 95/10603, published in April 1995. Examples of commercial products of α-amylases are TERMAMYL®, BAN®, FUNGAMYL® and DURAMYL®, all available from Novo Nordisk A / S Denmark, W095 / 26397 describes other amylases 10 compatible: α-amylases characterized by having a specific activity of at least 25% greater than the specific activity of TERMAMYL® at a temperature range of 25 ° C to 55 ° C and at a pH value in the range of 8 to 10, as measured by the Phadebas® a-amylase activity assay. Other amylolitic enzymes with improved properties with respect to the level of 15 activity and the combination of thermostability and a higher level of activity • are described in W095 / 35382. The compositions of the present invention may also have a mannanase enzyme. Preferably, the mannanase is selected from the group consisting of: three enzymes degrading mannan: EC 3.2.1.25: ß- 20 mannosidase, EC 3.2.1.78: Endo-1, 4-ß-mannosidase, considered here as "mannanase" and EC 3.2.1.100: 1, 4-ß-mannobiosidase, and mixtures thereof. (IUPAC Classification- Enzyme nomenclature, 1992 ISBN 0-12-227165-3 Academic Press).

More preferably, the treatment compositions of the present invention, when a mannanase is present, comprises a β-1,4-mannosidase (E.C. 3.2.1.78) considered as mannanase. The term "mannanase" or "galactomannanase" denotes a mannanase enzyme defined according to area and officially named mannan endo-1, 4-beta-mannosidase and has the alternative names beta-mannanase and endo-1, 4- mannan and catalyzing the reaction; random hydrolysis of 1, 4-beta-D-mannosidic bonds in mannans, galactomannans, glucomannans, and galactoglucomannans. Particularly, mannanases (EC 3.2.1.78) constitute a group of polysaccharides that degrade mannans and denote enzymes that are able to break down poly chains containing mannose units, that is, they are capable of breaking glycosidic bonds in mannans, glucomannans, galactomannans and galactogluco-manans. The mannans are polysaccharides that have a skeleton composed of trusses with ß-1, 4- bonds; glucomannans are polysaccharides that have a skeleton or more or less alternating mañosa and glucose regularly with ß-1, 4 bonds; galactomannans and galactoglucomannans are mannans and glucomannans with galactose side chains with a-1, 6 bonds. These compounds can be acetylated. The degradation of galactomannans and galactoglucomannans is facilitated by total or partial removal of galactose side chains, subsequent degradation of acetylated mannans, Glucomannan, galactomannan and galactogluco-mannan is facilitated by total or partial deacetylation. The acetyl groups can be removed by alkalis or mannitol acetylesterases. Oligomers that are released from the mannanases or by a combination of mannanases and a-galactosidase and / or 5 acetyl mamanic esterases can subsequently be degraded to release free maltose by β-mannosidase and / or β-glucosidase. Mannanases have been identified in several Bacillus organisms. For example, Talbot et al., Appl. Environ. Microbiol., Vol. 56, No. 11, pp. 3505-3510 (1990) describes a beta-mannanase from Bacillus stearothermophilus in 10 form of dimers having a molecular weight of 162 kDa and an optimum pH of 5.5-7.5. Mendoza et al., World J. Microbiol. Biotech., Vol. 10, No. 5, pp. 551-555 (1994) describes a beta-mananase from Bacillus subtilis having a molecular weight of 38 kDa, an optimal activity at pH 5.0 and 55C and a pl of 4.8. JP-03047076 reveals a beta-mananase from Bacillus 15 sp., Which has a molecular weight of 373 kDa measured by gel filtration, an optimum pH of 8-10 and a pl of 5.3-5.4. JP-63056289 discloses the production of an alkaline, thermostable beta mannanase that hydrolyzes the beta-1, 4-D-mannopyranoside bonds of, for example, mannans and produces hand-oligosaccharides. JP- 63036774 is related to the microorganisms Bacillus FERM P-8856 that 20 produces beta-mannanase and beta-mannosidase at an alkaline pH. JP-08051975 discloses alkaline beta-mannanases from Bacillus sp. alkalophilics. AM-001. A purified mannanase of Bacillus amyloliquefaciens useful in bleaching pulp and paper and a method of preparation thereof is disclosed in WO 97/11164. WO 91/18974 describes a hemicellulase such as a glucanase, xylanase or mannanase active at an extreme pH and temperature. WO 94/25576 discloses an enzyme of Aspergillus aculeatus, CBS 101.43, which exhibits mannanase activity which may be useful for the degradation or modification of the cell wall material of plants or algae. WO 93/24622 discloses an isolated mannanase from Trichoderma reseei useful for bleaching lignocellulosic pulps. A hemicellulase capable of degrading hemicellulose containing mannan is described in WO 91/18974 and a purified mannanase from Bacillus amyloliquefaciens is described in W097 / 11164. Preferably, the mannanase enzyme will be an alkaline mannanase as defined below, more preferably, a mannanase originating from a bacterial source. Above all, the laundry detergent composition of the present invention will comprise an alkaline mannanase chosen from the mannanase of the Bacillus agaradhaerens strain NICMB 40482; Mannase from Bacillus subtilis strain 168, gen yght; the mannase from Bacillus sp. I633 and / or mannase from Bacillus sp. AAI12. The most preferred mannanase for inclusion in the detergent compositions of the present invention in the mannanase enzyme originated from Bacillus sp. I633 as described in co-pending Danish patent application No. PA 1998 01340. The terms "mannanase alkaline enzyme" are designed to encompass an enzyme which has an enzyme activity of at least 10%, preferably at least 25%, more preferably at least 40% of its maximum activity at a given pH ranging from 7 to 12, preferably 7.5 to 10.5. The alkaline mannanase of Bacillus agaradhaerens NICMB 40482 is described in co-pending US patent application Serial No. 5 09/111, 256. More specifically, this mannanase is: i) a polypeptide produced by Bacillus agaradhaerens, NCIMB 40482; or ^ P ii) a polypeptide containing an amino acid sequence as shown in positions 32-343 of SEQ ID NO: 2 as shown in U.S. Patent Application Serial No. 09/111, 256; or iii) an analogue of the polypeptide defined in i) or ii) that is at least 70% homologous with said polypeptide, or is derived from said polypeptide by substitution, deletion or addition of one or more amino acids, or is immunologically reactive with an antibody polyclonal culture against said polypeptide in purified form. Also encompassed is the corresponding isolated polypeptide having mannanase activity selected from the group consisting of: (a) polynucleotide molecules that encode a polypeptide having mannanase activity and comprising a nucleotide sequence • 20 as shown in SEQ ID NO: 1, from nucleotide 97 to nucleotide 1029 as shown in U.S. Patent Application Serial No. 09/111, 256; (b) homologs of species of (a); 4, - < (c) polynucleotide molecules encoding a polypeptide having mannanase activity that is at least 70% identical to the amino acid sequence of SEQ ID NO: 2 of amino acid residue 32 to amino acid residue 343 as shown in the application U.S. Patent Series No. 09/111, 256; (d) molecules complementary to (a), (b) or (c); and (e) degenerate nucleotide sequences of (a), (b), (c) or (d). Plasmid pSJ1678 comprising the polynucleotide molecule (the DNA sequence) encoding said mannanase has been transformed into a strain of Escherichia coli which was deposited by the inventors in accordance with the Budapest Treaty on International recognition of the deposit of Microorganisms for the purposes of the Patent Procedure in Deutsche Sammiung von Mikroorganismen und Zellkulturen GmbH, Macheroder Weg 1b, D-38124 Braunschweig, Federal Republic of Germany, May 18, 1998 under the number of DSM 12180 disposition. A second most preferred enzyme is the mannanase of Bacillus subtilis strain 168, which is described in the US patent application Serial No. 09 / 095,163. More specifically, this mannanase is: i) encoded by the coding part of the DNA sequence shown in SEQ ID No. 5 shown in U.S. Patent Application Serial No. 09 / 095,163 or an analogue of said sequence; I ii) is a polypeptide comprising an amino acid sequence as shown in SEQ ID NO: 6 shown in U.S. Patent Application Serial No. 09 / 095,163; or iii) is an analogue of the polypeptide defined in ii) which is at least 70% homologous with said polypeptide, or is derived from said polypeptide by substitution, deletion or addition of one or more amino acids, ie reactivates immunologically with a polyclonal antibody cultured against said polynucleotide in purified form. The corresponding isolated polypeptide also encompasses said mannanase activity chosen from the group consisting of: (a) polynucleotide molecules that encode a polypeptide having morning activity and comprising a nucleotide sequence as shown in SEQ ID NO: 5, as shown in U.S. Patent Application Serial No. 09 / 095,163; (b) homologs of species of (a); (c) polynucleotide molecules encoding a polypeptide having mannanase activity that is at least 70% identical to the amino acid sequence of SEQ ID NO: 6 as shown in U.S. Patent Application Serial No. 09 / 095,163; (d) molecules complementary to (a), (b) or (c); and (e) degenerate nucleotide sequences of (a), (b), (c) or (d).

A third preferred mannanase is described in the Danish Patent Application No. PA 1998 01340. More specifically, this mannanase is: i) a polypeptide produced by Bacillus sp. I633; ii) a polypeptide comprising an amino acid sequence as shown in positions 33-340 of SEQ ID NO: 2 as shown in Danish patent application No. PA 1998 01340; or iii) an analogue of the polypeptide defined in i) or ii) that is at least 65% homologous with said polypeptide, or comes from said polypeptide by substitution, deletion or addition of one or several amino acids, that is to say reactive immunologically with a polyclonal antibody cultured against said polynucleotide in purified form. Also encompassed is the corresponding isolated polynucleotide molecule from the group consisting of: (a) polynucleotide molecules encoding a polypeptide having morning activity and comprising a nucleotide sequence as shown in SEQ ID NO: 1 from nucleotide 317 to nucleotide 1243 , as shown in the application of Danish Patent No. PA 1998 01340; (b) homologs of species of (a); (c) polynucleotide molecules that encode a polypeptide having mannanase activity that is at least 65% identical to the amino acid sequence of SEQ ID NO: 2 of amino acid residue 33 to the residue of i) ajtAÉ ^ i ^^ J, ¿A.Jta ^ amino acid 340 as shown in the Danish patent application No. PA 1998 01340; (d) molecules complementary to (a), (b) or (c); and (e) degenerate nucleotide sequences of (a), (b), (c) or (d). 5 The plasmid pBXM3 containing the polynucleotide molecule (the DNA sequence) encoding a mannanase has been transformed into a strain of Escherichia coli which was deposited by the inventors in accordance with the Budapest Treaty on International recognition of the deposit of Microorganisms for the purposes of the 10 Patent Procedure an Deutsche Sammiung von Mikroorganismen und Zellkulturen GmbH, Macheroder Weg 1 b, D-38124 Braunschweig, Federal Republic of Germany, on May 29, 1998 under deposit number DSM 12197. • A preferred fourth mannanase is described in the co-pending patent application. Danish slope No. PA 1998 01340. More specifically, this 15 mornings is: i) a polypeptide produced by Bacillus sp. AAI12; I) a polypeptide comprising an amino acid sequence as shown in positions 25-362 of SEQ ID NO: 2 as shown in Danish patent application No. PA 1998 01341; or iii) an analogue of the polypeptide defined in i) or ii) that is at least 65% homologous with said polypeptide, or comes from said polypeptide by substitution, deletion or addition of one or several amino acids, ie reactive immunologically with a polyclonal antibody cultured against said polynucleotide in purified form. Also encompassed is the corresponding isolated polynucleotide molecule of the group consisting of: (a) polynucleotide molecules encoding a polypeptide having mannanase activity and comprising a nucleotide sequence as shown in SEQ ID NO: 1 from nucleotide 225 to nucleotide 1236 , as shown in the Danish patent application No. PA 1998 01341; (b) homologs of species of (a); (c) polynucleotide molecules encoding a polypeptide having mannanase activity that is at least 65% identical to the amino acid sequence of SEQ ID NO: 2 from amino acid residue 25 to amino acid residue 362 as shown in the application for Danish patent No. PA 1998 01341; (d) molecules complementary to (a), (b) or (c); and (e) degenerate nucleotide sequences of (a), (b), (c) or (d). Plasmid pBXM1 containing the polynucleotide molecule (the DNA sequence) encoding a mannanase has been transformed into a strain of Escherichia coli which was deposited by the inventors in accordance with the Budapest Treaty on the International Recognition of the Deposit of Microorganisms For the Purposes of the Patent Procedure in the Deutsche Sammiung von Mikroorganismen und Zellkulturen GmbH, Macheroder Weg 1 b, D-38124 nschweig, Federal Republic of Germany, on October 7, 1998 under deposit number DSM 12433. Mannanase, when present, is incorporated into the treatment compositions of the present invention preferably at level from 0.0001% to 2%, more preferably from 0.0005% to 0.1%, more preferred from 0.001% to 0.02% pure enzyme by weight of the composition. The compositions of the present invention may also have a xyloglucanase enzyme. Xyloglucanases compatible for the purpose of the present invention are enzymes having specific activity for xyloglucan, preferably at a level of 0.001% to about 1%, more preferably 0.01% to 0.5%, by weight of the composition. As used herein, the term "endoglucanase activity" means the ability of the enzyme to hydrolyse 1, 4-β-D-glycosidic bonds present in any cellulosic material, such as cellulose, cellulose derivatives, lichenine, β-D -glucan, or xyloglucan. The endoglucanase activity can be determined according to methods known in the art, examples of which are described in WO 94/14953 and hereafter. One unit of endoglucanase activity (for example, CMCU, AVIU, XGU or BGU) is defined as the production of 1 μmol of reducing sugar / min of a glucan substrate, the substrate being glucan, for example, CMC (CMCU), Avicell turgente acid (AVIU), xyloglucano (XGU) or cereal ß-glucan (BGU). The reducing sugars are determined as described in WO 94/14953 and here on. The specific activity of an endoglucanase towards a substrate is defined as units / mg of protein. Enzymes with the highest activity are XGU endoglucanase activity (hereinafter "specific for xyloglucan"), whose enzyme: i) is encoded by a DNA sequence composed of or included in at least one of the following sequences partial (a) ATTCATTTGT GGACAGTGGA C (SEQ ID NO: 1) (b) GTTGATCGCA CATTGAACCA (SEQ ID NO: 2) (c) ACCCCAGCCG ACCGATTGTC (SEQ ID NO: 3) (d) CTTCCTTACC TCACCATCAT (SEQ ID NO: 4) ( e) TTAACATCTT TTCACCATGA (SEQ ID NO: 5) (f) AGCTTTCCCT TCTCTCCCTT (SEQ ID NO: 6) (g) GCCACCCTGG CTTCCGCTGC CAGCCTCC (SEQ ID NO: 7) (h) GACAGTAGCA ATCCAGCATT (SEQ ID NO: 8) (i) ) AGCATCAGCC GCTTTGTACA (SEQ ID NO: 9) (j) CCATGAAGTT CACCGTATTG (SEQ ID NO: 10) (k) GCACTGCTTC TCTCCCAGGT (SEQ ID NO: 11) (I) GTGGGCGGCC CCTCAGGCAA (SEQ ID NO: 12) (m) ACGCTCCTCC AATTTTCTCT (SEQ ID NO: 13) (n) GGCTGGTAGT AATGAGTCT (SEQ ID NO: 14) (o) GGCGCAGAGT TTGGCCAGGC (SEQ ID NO: 15) (p) CAACATCCCC GGTGTTCTGG G (SEQ ID NO: 16) (q) AAAGATTCAT TTGTGGACAG TGGACGTTGA TCGCACATTG AACCAACCCC AGCCGACCGA TTGTCCTTCC TTACCTCACC ATCATTTAAC ATCTTTTCAC CATGAAGCTT TCCCTTCTCT CCCTTGCCAC CCTGGCTTCC GCTGCCAGCC TCCAGCGCCG CACACTTCTG CGGTCAGTGG GATACCGCCA CCGCCGGTGA CTTCACCCTG TACAACGACC TTTGGGGCGA GACGGCCGGC ACCGGCTCCC AGTGCACTGG AGTCGACTCC TACAGCGGCG ACACCATCGC TTGTCACACC AGCAGGTCCT GGTCGGAGTA GCAGCAGCGT CAAGAGCTAT GG.G.AAG.G ÍSFO m NO- M Ó (r) CAGCATCTCC ATTGAGTAAT CACGTTGGTG TTCGGTGGCC CGCCGTGTTG CGTGGCGGAG GCTGCCGGGA GACGGGTGGG GATGGTGGTG GGAGAGAATG TAGGGCGCCG TGTTTCAGTC CCTAGGCAGG ATACCGGAAA ACCGTGTGGT AGGAGGTTTA TAGGTTTCCA GGAGACGCTG TATAGGGGAT AAATGAGATT GAATGGTGGC CACACTCAAA CCAACCAGGT CCTGTACATA CAATGCATAT ACCAATTATA CCTACCAAAA AAAAAAAAAA AAAAAAAAAA AAAA (SEQ ID NO: 18) 10 Or in a homologous sequence that also encodes a polypeptide specific for xyloglucan with endoglucanase activity, i) is immunologically reactive with an antibody cultured against a highly purified endoglucanase encoded by the DNA sequence defined in i) and from Aspergillus aculeatus, CBS 101.43, and is 15 specifies for xyloglucan. More specifically, as used herein the term "specific for xyloglucan" means that the endoglucanase enzyme exhibits its highest endoglucanase activity on a xyloglucan substrate, and preferably less 75% activity, more preferably less than 50% activity, more 20 preferably less than 25%, on other cellulose-containing substrates such as carboxymethyl cellulose, cellulose, or other glucans.

Preferably, the specificity of an endoglucanase towards xyloglucan is further defined as a certain relative activity as the release of reducing sugars under optimal conditions obtained by incubating the enzyme with xyloglucan and the other substrate to be analyzed, respectively. For example, specificity can be defined as xyloglucan activity to β-glucan (XGU / BGU), xyloglucan activity to 5 carboxy methyl cellulose (XGU / CMCU), or xyloglucan activity to Avicell turgid acid (XGU / AVIU), which is preferably greater than 50, such as 75, 90 or 100.

• The term "from" as used herein refers not only to an endoglucanase produced by strain CBS 101.43, but also a 10 endoglucanase encoded by a DNA sequence isolated from strain CBS 101.43 and produced in a host organism transformed with said DNA sequence. The term "homologue" as used herein indicates a • polypeptide encoded by DNA that hybridizes to the same probe as the DNA that encodes a specific endoglucose enzyme for low xyloglucan 15 certain conditions specified (such as pre-soaking in 5xSSC and pre-hybridized for 1 hour at -40 ° C in a 5xSSC solution, dxDenhardt solution, and 50 μg of denatured and sonicated bovine thymus DNA, followed by hybridization in the same solution supplemented with 50 μCi of _f probe labeled 32-P-dCTP for 18 hours at -40 ° C and washing three times in 20 2xSSC, 0.2% SDS at 40 ° C for 30 minutes). More specifically, the term is designed to refer to a DNA sequence that is at least 70% homologous to any of the sequences shown above that encode a specific endoglucanase for xyloglucan, including ..%, J. __. tab > , .__, _ .. (.. «... ...»., ~ T «imfci? Ft -fii'itiíah-HH. -'pipifenii- less 75%, at least 80%, at least 90% or even at least 95% with any of the sequences shown above The term is designed to include modifications of any of the DNA sequences shown above, such as nucleotide substitutions that do not result in another amino acid sequence of the polypeptide encoded by the sequence, but which correspond to the use of the host organism codon within which a DNA construct comprising any of the DNA sequences is introduced or nucleotide substitutions that give rise to a different sequence of amino acids and thus, possibly, a sequence of different amino acids and, therefore, possibly a different protein structure that can give rise to a mutant endoglucanase with different properties than the natural enzyme.Other examples of possible modifications are insertion of one or more nuclei within the sequence, the addition of one or more nucleotides either at the end of the sequence, or the deletion of one or more nucleotides either at the end or within the sequence. The endoglucanase specific for xyloglucan useful in the present invention is preferably one having a ratio XGU / BGU, XGU / CMU and / or XGU / AVIU (as defined above) or more than 50, such as 75, 90 or 100. In addition , the endoglucanase specified for xyloglucan is substantially devoid of activity towards β-glucan and / or has a maximum of 25% as such per maximum 10% or about 5% activity towards carboxymethyl cellulose and / or Avicell when the activity towards xyloglucan is 100%. In addition, the endoglucanase specific for xyloglucan of the invention is preferably substantially devoid of transferase activity, an activity that has been observed for most endoglucanases 5 specific for xyloglucan of plant origin. The endoglucanase specific for xyloglucan can be obtained from fungal species A. aculeatus, as described in WO 94/14953. Microbial endoglucanases specific for xyloglucan have also been described in WO 94/14953. The specific endoglucanases 10 for xyloglucan from plants have been described, but these enzymes have transferase activity and therefore should be considered inferior to the microbial endoglucanases specific for xyloglucan provided that • Desire extensive degradation of xyloglucan. An additional advantage of a microbial enzyme is that it can, in general, be produced in amounts 15 higher in a microbial host, than enzymes from other sources. Xyloglucanase, when present, is incorporated into the treatment compositions of the invention preferably at a level of from 0.0001% to 2%, more preferably from 0.0005% to 0.1%, more preferably from 0.001% to 0.02% pure enzyme by weight of the composition. • The enzymes mentioned above can be of any compatible origin, such as vegetable, animal, bacterial, fungal and yeast origin. The purified and unpurified forms of these enzymes can be used. Also included by definition are the enzyme mutants natural Mutants can be obtained for example, by protein engineering and / or genetics, chemical and / or physical modifications of natural enzymes. The common practice is also the expression of the enzyme by means of host organisms in which the genetic material responsible for the production of enzymes has been cloned. Said enzymes are normally incorporated in the bleaching composition at levels of 0.0001% to 2% of active enzyme by weight of the bleaching composition. The enzymes can then be added as individual ingredients separately (prills, granulates, stabilized liquids, etc. Containing an enzyme) or as mixtures of two or more enzymes (eg, co-granulates). Other suitable detergent ingredients that can be added are sensors for the oxidation of enzymes. Examples of such enzyme oxidation scavengers are ethoxylated tetraethylene polyamines. A range of enzyme materials and means for their incorporation into synthetic bleaching compositions are also disclosed in WO 93/07263 and WO 93/07260 to Genencor International WO 89/08694 to Novo, and US 3,553,139, January 5, 1971 to McCarty. and col. The enzymes are further disclosed in US 4,101,457, Place et al., July 18, 1978, and in US 4,507,219, Hughes, March 26, 1985. Useful enzyme materials for liquid detergent formulations, and their incorporation into such formulations are disclosed in US 4,261, 868, Hora et al, April 14, 1981. líi ¿___-.___? ____ s_____; > ____! ____- •? - - ¥ "" "VL * ßll * A? Rí *»? UA ... XA. ^? * Ib? JMá.í Enzyme Stabilizers - Enzymes for use in detergents can be stabilized by various techniques. of enzymes are disclosed and exemplified in US 3,600,319, August 17, 1971, Gedge et al, EP 199,405 and EP 200,586, October 29, 1986, Venegas Enzyme stabilization systems are also described, for example, in US 3,519,570 A Bacillus AC13 species that gives proteases, xylanases and cellulases is described in WO 9401532 to Novo.The enzymes employed herein can be stabilized by the presence of water soluble sources of calcium and / or magnesium ions in the finished compositions that provide Such ions to enzymes Suitable enzyme stabilizers and levels of use are described in U.S. Patent No. 5,576,282.

Other Detergent Ingredients - The bleaching compositions herein may also optionally have one or more of the following: polymeric dispersing agents, clay-grime / anti-redeposition removers, brighteners, suds suppressors, dyes, perfumes, elasticizing agents the structure, fabric softeners, carriers, hydrotropes, process aids and / or pigments. Suitable examples of such other detergent ingredients and levels of use are found in U.S. Patent No. 5,576,282.

Cleaning methods - In addition to the methods for cleaning fabrics, frets and other hard surfaces, and parts of the body by personal cleansing products, described herein, the invention described herein also encompasses a laundry pre-treatment process for fabrics that are soiled or stained which directly comprises contacting said stains and / or dirt with a very concentrated form of the established bleaching composition before washing such fabrics using conventional aqueous wash solutions. Preferably, the bleaching composition remains in contact with the grime / stain for a period of about 30 seconds to 24 hours before washing the substrate with grime / stain in a conventional manner. More preferably, the pre-treatment times will vary from 1 to 180 minutes. The following examples are intended to exemplify the compositions of the present invention, but are not necessarily designed to limit or otherwise define the scope of the invention. In the following examples some known abbreviations are used for people experienced in the area, consistent with the established disclosure.

EXAMPLES OF SYNTHESIS Example 1 Preparation of 1- (4,4-dimethyl-3,4-dihydroisoquinoline) decan-2-sulfate (7): Step 1: Preparation of dimethylbenzylcyanide (2): A 1L three-necked ball flask equipped with two addition funnels, a side arm adapter, an ammonium hydroxide trap, a reflux condenser, a mechanical stirrer, thermometer and adapter, and a gas frit diffuser is charged with dimethyl sulfoxide (200 mL) and chill in an ice bath. The methyl chloride gas diffuses into the dimethyl sulfoxide with stirring. After 15 minutes, sodium hydroxide (50% aqueous solution, 32.9 g) and benzyl cyanide (i, 11.7 g, 1 equiv) are added simultaneously as solutions separately by the two 15 addition funnels at a rate that does not allow the temperature increases to more than 35 ° C. After the addition of sodium hydroxide and benzyl cyanide is complete, the reaction is stirred at room temperature as the methyl chloride continues to diffuse into the solution. After 1 h, the flow of methyl chloride (38.8 g total, 3.8 equiv) is stopped and the reaction ^ w 20 is extracted with toluene (3 x 100 mL) and ether (100 mL). The combined organic phases are washed with saturated sodium bicarbonate solution (2 x 100 mL), saturated saline solution (100 mL), dried over sodium sulfate, and .uA '^ r É É ~ ~ ~??? "- - -» "" • • • • • • • concentra concentra concentra concentra concentra concentra concentra concentra concentra concentra concentra concentra La La La La La La La La La La La La La La La La La next reaction: Step 2: Preparation of 1-amino-2,2-dimethyl-2-phenylethane (3): A 250 ml three-necked ball flask equipped with a pressure equalizing dropping funnel, argon gas inlet and reflux condensers is Charge with anhydrous diethyl ether (100 mL) and cool in an ice bath. Lithium aluminum hydride powder (3.68 g, 2 equiv) is slowly added to the reaction mixture. Upon completion of the addition, dimethylbenzyl cyanide (2, 7.00 g, 1 equiv) is added dropwise over fifteen minutes. The reaction is allowed to warm slowly to room temperature overnight with stirring. Water (7.0 mL) is added over 15 minutes followed by sodium hydroxide (15% aqueous solution, 7.0 mL). The mixture is stirred for approximately 1 h, and additional water (21.0 mL) is added. The reaction is diluted with diethyl ether (100 mL) and filtered in vacuo. The filter cake is washed with diethyl ether (8 x 50 mL) and the combined organic phases are dried over magnesium sulfate, and concentrated in vacuo to give 3. The preparation is represented by the following reaction: Step 3: Preparation of 4.4-dimethyl-3,4-dihydroisoquinolone (4): A 50 mL beaker equipped with a magnetic stir bar and distillation apparatus loaded with 1-amino-2,2- dimethyl-2-phenylethane (4.15 g, 1 equiv) and fc acid (6.65 g, 3.5 equiv) is stirred at 100 ° C for 1 hour, after that time another portion of fc acid is added (2 mL, 0.9 equiv) ). After stirring for an additional 1 hour, the mixture is heated to 200 ° C and vacuum is applied. When the unreacted fc acid and water are removed, the remaining oil, N-fl-β-β-dimethyl-β-phenethylamine, is cooled to room temperature. A 100 ml ball flask equipped with a side arm adapter, an addition funnel and mechanical stirrer is charged with polysulfuric acid (29.7 g) and phosphorus pentoxide (4.74 g). This mixture is stirred and heated at 180 ° C for 1 hour, and cooled to 150 ° C. The N-f-β, β-d-methyl-β-phenethylamine (5.31 g, 1 equiv) is melted and added as a jet to the acid mixture. The reaction is heated to 180 ° C and left stirring overnight. The reaction mixture is cooled to 60 ° C and slowly mixed with ice water (250 mL). The diluted reaction mixture is washed with diethyl ether (2 x 100 mL). The aqueous solution is stirred and kept cool in a & £ tí * PW l?. ?? * b¿2á¿l ??, ¿títdl * k, acetone / dry ice bath as a saturated aqueous solution of potassium hydroxide is added. When the pH of the mixture reaches a value of 9, the mixture is extracted with diethyl ether (4 x 100 mL). The organic phases are washed with buffer at pH 10 (200 mL), dried over magnesium sulfate, and condensed in vacuo to give 4. The preparation is represented by the following reaction: Step 4: Preparation of cyclic 1,2-decanediol sulfate (6): A 500 ml three-necked ball flask equipped with a mechanical stirrer, equalizing pressure addition funnel, and a reflux condenser is charged with 1 , 2-decanediol (5.8.72 g, 50.0 mmol) and 50 mL of carbon tetrachloride. Upon dissolving 1, 2-decanediol, thionyl chloride (5.5 mL, 75 mmol) is added dropwise at room temperature, and the reaction is heated to 60 ° C. After 2 hours, the reaction is cooled by an ice bath. Water (50 mL) and acetonitrile (75 mL) are added. Ruthenium chloride hydrate (0.131 g, 0.50 mmol) and sodium periodate (21.4 g, 100 mmol) are added and the reaction mixture is stirred at room temperature for 1 hour. The mixture is extracted with diethyl ether (4 x 175 mL), the organic phases are washed with water (5 x 100 mL), sodium bicarbonate The saturated solution (3 x 100 mL), saturated saline solution (2 x 100 mL), filtered through celite / silica gel, and dried over sodium sulfate. magnesium. The clear liquid is concentrated to give 6, a clear oil. The preparation is represented by the following reaction: Step 5: Preparation of 1- (4,4-dimethyl-3,4-dihydroxyaguinoline) decane-2-sulfate (7): A 100 mL ball flask equipped with a magnetic stir bar is charged with 4,4-dimethyl-3,4-dihydroisoquinoline (2.45 g, 15.4 mmol) and acetonitrile (15.2 mL). To this solution is added in one portion 1,2-decanediol sulphate (4.78 g, 16.0 mmol). The reaction mixture becomes thick within 5 minutes, and more acetonitrile (60 mL) is added. The reaction is stirred overnight. The precipitate is collected, washed with acetone, and allowed to air dry to give 7. The preparation is represented by the following reaction: EXAMPLE ll Preparation of 1- (3,3-dimethyl-3,4-dihydroisoquinoline) decane-2-sulfate (H): Step 1: Preparation of N-formyl-aa-dimethyl-β-phenethylamine (9): A flask 1-L three-necked ball equipped with thermometer and adapter, mechanical stirrer, reflux condenser, ammonium hydroxide trap, and pressure equalizer addition funnel is charged with glacial acetic acid (83.0 mL), and cooled in an ice bath. Sodium cyanide (16.3 g, 1 equiv) and a solution of concentrated sulfuric acid in acetic acid (160 g / 83.0 mL) are added at a rate slow enough to maintain a temperature below 20 ° C (CAUTION: take great care to avoid contact with poisonous gas). 2-Methyl-1-phenyl-2-propanol (8, 50.0 g, 1 equiv) is slowly added to the reaction mixture, which is stirred overnight at room temperature. The solution is aerated with argon for 3 hours, and poured into ice water (300 mL). An oil layer is formed, and separated and stored. The aqueous phase is neutralized to pH 7 with sodium carbonate and extracted with diethyl ether (3 x 200 mL). The organic phases are combined with the oil separated above, dried over magnesium sulfate, and concentrated to give 9. The preparation is represented by the following reaction: Step 2: Preparation of 3,3-dimethyl-3,4-dihydroisoquinoline (10): A 1 L three neck necked flask equipped with side arm adapter, addition funnel and mechanical stirrer is charged with polysulfuric acid (378 g) and phosphorus pentoxide (60.4 g). This mixture is stirred and heated at 180 ° C for 1 hour, and cooled to about 150 ° C. The N-formyl-α, α-dimethyl-β-phenethylamine is melted and added as a jet to the acid mixture. The reaction is heated to 180 ° C and left stirring overnight. The reaction mixture is cooled to 100 ° C and slowly mixed with ice water (2 L). The diluted reaction mixture is then filtered through celite®. The filtrate is washed with diethyl ether (2 x 100 mL). The aqueous solution is stirred and kept cool in an acetone / dry ice bath as a saturated aqueous solution of potassium hydroxide is added. When the pH of the mixture reaches a value of 9, the mixture is extracted with diethyl ether (4 x 100 mL). The organic phases are washed with a buffer of pH 10 (200 mL), dried over magnesium sulfate, and condensed in vacuo to yield 4. the preparation is represented by the following reaction: Step 3: Preparation of 3,3-dimethyl-3,4-dihydroisoquinoline tetrafluoroborate (11): A ball flask equipped with a magnetic stir bar at 0 ° C is charged with trimethyloxonium tetrafluoroborate (Meerwin salt, 1.13 g, 7.7 mmol) and methylene chloride (15 mL). To the stirred solution is added a solution of 3,3-dimethyl-3,4-dihydroisoquine (1.11 g, 7.0 mmol) in methylene chloride (40 mL) over a period of 5 minutes. The heterogeneous solution is allowed to warm to a room temperature, and it is stirred all night. The solution is concentrated, and the resulting oil is added with ethanol, resulting in re-crystallization to give 11. The preparation is represented by the following reaction: 10 11 EXAMPLE III Preparation of 1,1-diphenyl-3-duryl pseudoisoindolium tetrafluoroborate (15): Step 1: Preparation of 1,1-diphenyl-3-duryl pseudoindole (12) as described in the area, as in Fuson, R.C et al. J. Org. Chem. 1951, 16, 648. Step 2: Preparation of cyclic 1,2-hexanediol sulfate (14): 5 A 500 mL three-necked ball flask equipped with mechanical stirrer, pressure equalizing addition funnel, and a reflux condenser is charged with 1,2-hexanediol (13, 5.91 g, 50.0 mmol) and • 50 mL of carbon tetrachloride. Upon dissolving 1, 2-hexanediol, thionyl chloride (5.5 mL, 75 mmol) is added dropwise at room temperature, and the The reaction is heated to 60 ° C. After 2 hours, the reaction is cooled by an ice bath. Water (50 mL) and acetonitrile (75 mL) are added. Ruthenium chloride hydrate (0.131 g, 0.50 mmol) and sodium periodate (21.4 g, 100 mmol) are added and the reaction mixture is stirred at room temperature for 1 hour. The mixture is extracted with diethyl ether (4 x 175 mL), The organic phases are washed with water (5 x 100 mL), saturated sodium bicarbonate (3 x 100 mL), saturated saline solution (2 x 100 mL), filtered through celite / silica gel, and dried over magnesium sulphate. The clear liquid is concentrated to give 7, a clear oil. The preparation is represented by the following reaction: • 13 14 Step 3: Preparation of 1, 1-diphenyl-3-duryl pseudoisoindolinio tetrafluoroborate (15): 1, 1-diphenyl-3-duryl-pseudoisoindole is added to a 200 mL beaker equipped with a magnetic stirring bar. (12, 5.55 g, 20.0 mmol) and acetonitrile (30 mL). To this solution is added in one portion the cyclic sulfate of 1,2-hexanediol (14, 2.60 g, 22.0 mmol). The reaction mixture becomes thick at 5 minutes, and additional acetonitrile (60 mL) is added. The reaction is stirred overnight. The precipitate is collected, washed with acetone, and allowed to air dry to give 15. The preparation is represented by the following reaction: EXAMPLES OF FORMULATIONS EXAMPLE IV The detergent compositions having the form of granular laundry detergents are exemplified by the following formulations. ABCDE Compound 0.05 0.01 0.13 0.04 0.07 bleach booster * Conventional activator 0.00 2.00 1.20 0.70 0.00 (NOBS) Conventional activator 3.00 0.00 2.00 0.00 0.00 (TAED) Conventional activator 3.00 0.00 0.00 0.00 2.20 (NACA-OBS) Sodium percarbonate 5.30 0.00 0.00 4.00 0.00 Sodium perborate 0.00 5.30 3.60 0.00 4.30 monohydrate Alkylbenzenesulfonate 12.00 0.00 12.00 0.00 21.00 linear C45AE0.6S 0.00 15.00 0.00 15.00 0.00 C2 N-oxide 0.00 2.00 0.00 2.00 0.00 Dimethylamine C12 Coco amidopropyl 1.50 0.00 1.50 0.00 0.00 betaine N-methyl glucamide 1.70 2.00 1.70 2.00 0.00 palm Chloride of C12 1.50 0.00 1.50 0.00 0.00 dimethylhydroxyethylammonium AE23-6.5T 2.50 3.50 2.50 3.50 1.00 C25E3S 4.00 0.00 4.00 0.00 0.00 Sodium tripolyphosphate 25.00 25.00 15.00 15.00 25.00 Zeolite A 0.00 0.00 0.00 0.00 0.00 Co-polymer of acid 0.00 0.00 0.00 0.00 1.00 Acrylic / Maleic acid Polyacrylic acid, 3.00 3.00 3.00 3.00 0.00 partially neutralized Release agent 0.00 0.00 0.50 0.40 0.00 gm Carboxymethylcellulose 0.40 0.40 0.40 0.40 0.40 0.40 Sodium carbonate 2.00 2.00 0.00 0.00 Sodium silicate 3.00 3.00 3.00 3.00 6.00 Sodium bicarbonate 5 00 5 00 500 5 00 500 Savinasa (4T) 1.00 1.00 1.00 1.00 0.60 Termamyl (60T) 0.40 0.40 0.40 0.40 0.40 Lipolase (1 OOT) 0.12 0.12 0.12 0.12 0.12 Carezyme (5T) 0.15 0.15 0.15 0.15 0.15 Dietilentraiminpenta 1.60 1.60 1.60 1.60 0.40 (methylene phosphonic acid) Brightener 0.2 0.20 0.20 0.05 0.20 Zinc phthalocyanine 0.50 0.00 0.25 0.00 0.00 sulfonated Photoblank MgS04 2.20 2.20 2.20 2.20 0.64 Na2S04 balance balance balance balance * 1- (4.4-dmetme-3.4-d? H? Droisoau? Nol? Na) dean -2-sulfate DreDarated according to EXAMPLE 1.

• Any of the above compositions is used to wash 10 fabrics at a concentration of 3500 ppm in water, 25 ° C, and a ratio of 15: 1 water: clothing. The typical pH is approximately 9.5 but can be adjusted by altering the proportion of the acid with respect to the sodium salt form of alkylbenzenesulfonate. 15 EXAMPLE V Bleaching detergent compositions having the form of granular laundry detergents are exemplified by the following formulations. 20 A B C D E Compound 0.26 0.38 0.04 0.03 0.01 bleach booster * Conventional activator 0.00 0.00 0.00 0.50 0.00 (NOBS) Conventional activator 1.80 1.00 2.50 3.00 1.00 (TAED) Conventional activator 3.00 0.00 0.00 2.50 0.00 (NACA-OBS) Sodium percarbonate 5.30 0.00 0.00 0.00 0.00 Sodium perborate 0.00 9.00 17.60 9.00 9.00 monohydrate Alkylbenzenesulfonate 21.00 12.00 0.00 12.00 12.00 linear C45AE0.6S 0.00 0.00 15.00 0.00 0.00 C2 N-oxide 0.00 0.00 2.00 0.00 0.00 Dimethylamine C12 Coco amidopropyl 0.00 1.50 0.00 1.50 1.50 betaine N-methyl glucamide 0.00 1.70 2.00 1.70 1.70 palm Chloride of C12 1.00 1.50 0.00 1.50 1.50 dimethylhydroxyethylammonium AE23-6.5T 0.00 2.50 3.50 2.50 2.50 C25E3S 4.00 • 0.00 4.00 0.00 4.00 Sodium tripolyphosphate 25.00 15.00 25.00 15.00 15.00 Zeolite A 0.00 0.00 0.00 0.00 0.00 Co-acid polymer 0.00 0.00 0.00 0.00 0.00 acrylic / Maleic acid 10 Polyacrylic acid, 0.00 3.00 3.00 3.00 3.00 partially neutralized 0.30 0.50 0.50 0.50 0.00 0.50 0.50 0.75 0.50 grick Carboxymethylcellulose 0.00 0.40 0.40 0.40 0.40 Carbonate 0.00 2.00 2.00 2.00 2.00 2.00 • Sodium silicate 6.00 3.00 3.00 3.00 3.00 Sodium bicarbonate 2.00 5.00 5.00 5.00 5.00 Savinasa (4T) 0.60 1.00 1.00 1.00 1.00 Termamyl (60T) 0.40 0.40 0.40 0.40 0.40 Lipolase (100T) 0.12 0.12 0.12 0.12 0.12 15 Carezyme (5T) 0.15 0.15 0.15 0.15 0.15 Dietilentraiminpenta 0.40 0.00 1.60 0.00 0.00 (methylene phosphonic acid) Brightener 0.20 0.30 0.20 0.30 0.30 Phthalocyanine zinc 0.25 0.00 0.00 0.00 0.00 sulphonated Any of the above compositions is used to wash 20 fabrics at a concentration of 3500 ppm in water, 25 ° C, and a proportion of 15: 1 water: clothes. The typical pH is approximately 9.5 but can be adjusted by altering the proportion of the acid with respect to the sodium salt form of alkylbenzenesulfonate.

EXAMPLE VI A bleaching detergent powder that confers the following ingredients: Component% by weight Bleacher booster compound * 0.07 TAED 2.0 Sodium perborate tetrahydrate 10 C12 linear alkylbenzene sulphonate 8 Phosphate (as sodium tripolyphosphate) 9 Sodium carbonate 20 Talcum 15 Brightener, perfume 0.3 Sodium chloride 25 Water and minors Cbp 100 % * 1- (4,4-dimethyl-3,4-dihydroisoquinoline) decane-2-sulfate prepared according to EXAMPLE 1.

EXAMPLE VII A laundry bar suitable for manually washing soiled fabrics is prepared by standard extrusion processes and comprises following: Component% by weight Bleaching boosting compound1 0.2 TAED 1.7 NOBS 0.2 Sodium perborate tetrahydrate 12 C12 linear alkyl benzene sulphonate 30 Phosphate (as sodium tripolyphosphate) 10 Sodium carbonate 5 Sodium pyrophosphate 7 Coconut monoethanolamide 2 Zeolite A (0.1 - 10 microns) 5 Carboxymethylcellulose 0.2 Polyacrylate (mm 1400) 0.2 Brightener, perfume 0.2 < & Protease 0.3 CaSO4 1 MgSO4 1 Water 4 Filler2 cbp 100% 11- (4,4-dimethyl-3,4-dihydroisoquinoline) decane-2-sulfate prepared according to EXAMPLE 1. 2Can be chosen from suitable materials such as CaCO3 , talc, clay, silicates, and the like.

Acidic fillers can be used to reduce the pH.

EXAMPLE HIV A laundry detergent composition for use in Washing machines are prepared by standard methods and comprise the following composition: Component% by weight Bleaching booster compound * 0.82 TAED 7.20 Sodium perborate tetrahydrate 9.2 Sodium carbonate 23.74 Anionic surfactant 14.80 Aluminum silicate 21.30 Silicate 1.85 Diethylenetriaminepentaacetic acid 0.43 Polyacrylic acid 2.72 Brightener 0.23 Polyethylene glycol 1.05 Sulphate 8.21 Pefrume 0.25 Water 7.72 Help for the process 0.10 Miscellaneous 0.43 * 1- (4,4-dimethyl-3,4-dihydroisoquinoline) decane-2-sulfate prepared according to EXAMPLE 1.

The composition is used to wash fabrics at a solution concentration of 1000 ppm at a temperature of 20-40 ° C and a water to cloth ratio of about 20: 1.

EXAMPLE IX Component% by weight Bleach boosting compound * 1.0 TAED 10.0 Sodium perborate tetrahydrate 8.0 Sodium carbonate 21.0 Anionic surfactant 12.0 Aluminum silicate 18.0 Diethylenetriaminepentaacetic acid 0.3 Nonionic surfactant 0.5 Polyacrylic acid 2.0 Brightener 0.3 Sulphate 17.0 Perfume 0.25 Water 6.7 Miscellaneous 2.95 * 1 - (4) 4-dimethyl-3,4-dihydroisoquinoline) decane-2-sulfate prepared according to EXAMPLE 1.

The composition is used as a laundry aid to wash fabrics at a solution concentration of approximately 850 ppm at a temperature of 20-40 ° C and a water to cloth ratio of approximately 20: 1. Although particular modalities of the theme of the invention, it will be obvious that those experienced in the area who can make various changes and modifications of the subject of the invention without depart from the spirit and scope of the invention. It is designed to cover, in the appended claims, all such modifications that are within the scope of this invention. The compositions of the present invention can be suitably prepared by any process chosen by the formulator, non-limiting examples of which are described in U.S. Patent Nos. 5,691, 297; 5,574,005; 5,569,645; 5,565,422; 5,16,448; 5,489,392; and 5,486,303. In addition to the foregoing examples, the bleaching systems of the present invention can be formulated into any suitable laundry detergent composition, non-limiting examples of which are described in U.S. Patent Nos. 5,679,630; 5,565,145; 5,478,489; 5,470,507; 5,466,802; 5,460,752; 5,458,810; 5,458,809; and 5,288,431. Having described the invention in detail with reference to preferred embodiments and examples, it is clear to those experienced in the area that various changes can be made without departing from the scope of the invention and the invention is not considered to be limited to those described. in the specification.

LIST OF SEQUENCES < 110 > The Procter & Gamble Company Miracle, Gregory Dykstra, Robert < 120 > COMPONENTS OF THE FORMULATION RESISTANT TO THE DECOMPOSITION BY AROMATIZATION, COMPOSITIONS AND LAUNDRY METHODS THAT EMPLOY THEMSELVES < 130 > 7754 < 150 > 60 / 151,175 < 151 > 1999-08-27 < 160 > 18 < 170 > Patentln version 3.0 < 210 > 1 < 211 > 21 < 212 > DNA < 213 > Aspergillus aculeatus < 400 > 1 attcatttgt ggacagtgga c 21 < 210 > 2 < 211 > 20 < 212 > DNA < 213 > Aspergillus aculeatus < 400 > 2 gttgatcgca cattgaacca 20 < 210 > 3 < 211 > 20 < 212 > DNA < 213 > Aspergillus aculeatus < 400 > 3 accccagccg accgattgtc 20 < 210 > 4 < 211 > 20 < 212 > DNA < 213 > Aspergillus aculeatus < 400 > 4 cttccttacc tcaccatcat 20 < 210 > 5 < 211 > 20 < 212 > DNA < 213 > Aspergillus aculeatus < 400 > 5 ttaacatctt ttcaccatga 20 < 210 > 6 < 211 > 20 < 212 > DNA < 213 > Aspergillus aculeatus < 400 > 6 agctttccct tctctccctt 20 < 210 > 7 < 211 > 28 < 212 > DNA < 213 > Aspergillus aculeatus < 400 > 7 • gccaccctgg cttccgctgc cagcctcc 28 < 210 > 8 < 211 > 20 < 212 > DNA 10 < 213 > Aspergillus aculeatus < 400 > 8 gacagtagca atccagcatt 20 < 210 > 9 91 < 211 > 20 < 212 > DNA < 213 > Aspergxllus aculeatus < 400 > 9 agcatcagcc gctttgtaca 20 15 < 210 > 10 < 211 > 20 < 212 > DNA < 213 > Aspergillus aculeatus < 400 > 10 ccatgaagtt caccgtattg 20 < 210 > 11 • < 211 > 20 < 212 > DNA 20 < 213 > Aspergillus aculeatus < 400 > 11 gcactgcttc tctcccaggt 20 < 210 > 12 < 211 > 20 < 212 > DNA < 213 > Aspergillus aculeatus < 400 > 12 gtgggcggcc cctcaggcaa 20 < 210 > 13 < 211 > 20 < 212 > DNA < 213 > Aspergillus aculeatus < 400 > 13 acgctcctcc aattttctct 20 < 210 > 14 < 211 > 19 < 212 > DNA < 213 > Aspergillus aculeatus < 400 > 14 ggctggtagt aatgagtct 19 < 210 > 15 < 211 > 20 < 212 > DNA 10 < 213 > Aspergillus aculeatus < 400 > 15 ggcgcagagt ttggccaggc 20 < 210 > 16 < 211 > 21 # < 212 > DNA < 213 > Aspergillus aculeatus < 400 > 16 caacatcccc ggtgttctgg g 21 15 < 210 > 17 < 211 > 347 < 212 > DNA < 213 > Aspergillus aculeatus < 400 > 17 aaagattcat ttgtggacag tggacgttga tcgcacattg aaccaacccc agccgaccga 60 ttgtccttcc ttacctcacc atcatttaac atcttttcac catgaagctt tcccttctct 120 cccttgccac cctggcttcc gctgccagcc tccagcgccg cacacttctg cggtcagtgg 180 20 gataccgcca ccgccggtga cttcaccctg tacaacgacc tttggggcga gacggccggc 240 accggctccc agtgcactgg agtcgactcc tacagcggcg acaccatcgc ttgtcacacc 300 agcaggtcct ggtcggagta gcagcagcgt caagagctat gccaacg 347 - < 210 > 18 < 211 > 294 < 212 > DNA < 213 > Aspergillus aculeatus < 400 > 18 cagcatctcc attgagtaat cacgttggtg ttcggtggcc cgccgtgttg cgtggcggag 60 gctgccggga gacgggtggg gatggtggtg ggagagaatg tagggcgccg tgtttcagtc 120 cctaggcagg ataccggaaa accgtgtggt aggaggttta taggtttcca ggagacgctg 180 tataggggat aaatgagatt gaatggtggc cacactcaaa ccaaccaggt cctgtacata 240 aaaaaaaaaa aaaa accaattata caatgcatat cctaccaaaa aaaaaaaaaa 294 »I >

Claims

NOVELTY OF THE INVENTION CLAIMS 1. A bleaching composition containing a bleach-enhancing compound in conjunction with or without a peroxygen source, wherein said bleach-enhancing compound is selected from the group consisting of: (a) a bleaching enhancer of the group consisting of aryliminium cations, zwitterions aryliminium, aryliminium polions having a net charge of about +3 to -3 and mixtures thereof; said bleach booster has the formulas [I] and [II]: [Q [IQ where t is 0 or 1; R1-R4 are substituted or unsubstituted radicals selected from the group consisting of H, alkyl, cycloalkyl, aryl, heterocyclic ring, nitro, halo, cyano, sulfonate, sulfonate, alkoxy, keto, carboxylic and carboxylic radicals; either of the two vicinal R1-R4 can be combined to form a fused, fused carbocyclic aryl or fused heterocyclic ring; R5 is a substituted or unsubstituted radical selected from the group consisting of H, alkyl, cycloalkyl, alkaryl, aryl, aralkyl, heterocyclic ring, nitro, halo, cyano, sulfonate, alkoxy, keto, carboxylic, and carboalkoxy radicals; R6 can be substituted or unsubstituted, saturated or unsaturated radical selected from the group consisting of H, alkyl, cycloalkyl, alkaryl, aryl, aralkyl, heterocyclic ring, and a radical represented by the formula: -T0- (Z wherein Z "is covalently bonded to T0, and Z" is selected from the group consisting of -CO2". -SO3", -OSO3", -SO2" is either 1 or 2; T0 is selected from the group consisting of: (1) - ( CH (R12)) - or - (C (R12) 2) - wherein R12 is independently chosen from H or C? -C8 alkyl; (2) -CH2 (C6H4) -; - CH2- VC-CH2- - CHj-C-CHj- (3) I; (4) OH (5) - (CH2) d (E) (CH2) r where d is from 2 to 8, F is from 1 to 3 and E is - (C (O) O-; (6) -C (0) NR13-wherein R13 is H or C1-C4 alkyl; H I -C- (7); Y where x is equal to 0 - 3; J, when present, is independently selected from the group consisting of -CR18R19-, -CR ^ R ^ CR8R21-, and _CR18R19CR20R21CR22R23_. R14_R23 8n RADIQUE | is SUStItItIoN oUr SUStItItIon chosen from the straight or branched group consisting of H, Ci-Ciß alkyls, cycloalkyls, alkaryls, aryls, aralkyls, alkylenes, heterocyclic rings, alkoxys, arylcarbonyls, carboxyalkyls and amide groups; wherein R7-R10 are substituted or unsubstituted radicals independently chosen from the group consisting of H, linear or branched C1-C12 alkyls, alkyls, alkoxys, aryls, alkaryls, aralkyls, cycloalkyls, and heterocyclic rings, further provided that when t is 0 , neither R7 nor R8 can be H, and that when t is 1, either R7 and R8, or R9 and R10, are not H; wherein any of R1-R10 can be joined with any of R1-R10 to form part of a common ring; (b) a bleach species selected from the group consisting of oxaziridinium cations, oxaziridinium zwitterions, oxaziridinium polyesters having a net charge of +3 to -3 and mixtures thereof; and mixtures of same, said oxaziridinium compound is represented by the formulas [III] and [IV]: [IV] where t is 0 or 1; R ^ -R34 are substituted or unsubstituted radicals selected from the group consisting of H, alkyl, cycloalkyl, aryl, ring heterocycle, nitro, halo, cyano, sulfonate, alkoxy, keto, carboxylic, and carboalkoxy radicals; and either of the two vicinal R ^ -R34 may be combined to form a fused aryl, fused carbocyclic ring or fused heterocyclic ring; R25 is a substituted or unsubstituted radical selected from the group consisting of H, alkyl, alkaryl, aryl, aralkyl, heterocyclic ring, nitro, halo, cyano, sulfonate, alkoxy, keto, carboxylic, and calboalkoxy radicals, and R26 may be a radical substituted or unsubstituted, saturated or unsaturated, chosen from the group consisting of H, alkyl, cycloalkyl, alcaplo, aryl, aralkyl, heterocyclic ring, and a radical represented by the formula: -T0- (Z ") a wherein Z" is covalently bound to T0, and Z "is selected from the group -C02" , - SO3", -OSO3", -SO2"and -OSO2" is already 1 or 2; T0 is selected from the group consisting of (1) - (CH (R12)) - or - (C (R12) 2) - wherein R12 is independently chosen from H or C? -C8 alkyl; (2) -CH2 (C6H4) -; - CH2-C V-CH2- - CHj-C-CHg- (3) I; (4) OH; (5) - (CH2) d (E) (CH2) r wherein d is from 2 to 8; f is from 1 to 3 and E is -C (0) 0-; (6) -C (0) NR13, wherein R13 is H or C1-C4 alkyl; H I - C- (7); Y where x is equal to 0 - 3; J, when present, is independently selected from the group consisting of -CR ^ R40-, -CR ^ R ^ CR ^ R42-, and -CR ^ R ^ CR ^ R42 CR ^ R44-; R ^ -R44 are substituted or unsubstituted radicals t mÁ, í 'éíi > k &?. go? * ,, ... k? s k, *. ...... ..., ___ ^ __ j_ ^ -. ^. | «J? t». ^ _ b_? t ________ * _ ^^ chosen from the linear or branched group consisting of H, C1-C18 alkyls, cycloalkyls , alkaryls, aryls, aralkyls, alkylenes, heterocyclic rings, alkoxys, arylcarbonyls, carboxyalkyls and amido groups; wherein R ^ -R30 are substituted or unsubstituted radicals independently chosen from the group consisting of H, linear or branched C1-C12 alkyls, alkylenes, alkoxys, aryls, alkaryls, aralkyls, cycloalkyls, and heterocyclic rings, further provided that when t is 0, neither R27 nor R28 can be H, and that when t is 1, either R27 and R28, or both R29 and R30, are not H; wherein any R ^ -R34 can be joined together with any other R ^ -R34 to form part of a common ring; and (c) mixtures thereof. The bleaching composition according to claim 1 further characterized in that said bleach-increasing compound comprises from 0.001% to about 10% by weight of said composition, and said source of peroxygen, when present, comprises from 0.01% to about 60% by weight of said composition. 3. The bleaching composition according to claim 1 further characterized in that said source of peroxygen, when present, is selected from the group consisting of: (a) Performed preformed compounds selected from the group consisting of percarboxylic acids and salts, acids and percarbon salts , acids and perimidic salts, acids and peroxy monosulf salts, and mixtures thereof, and (b) hydrogen peroxide sources chosen from the group consisting of compounds perborate, percarbonate compounds, phosphate compounds and mixtures thereof, and a bleach activator. 4. The bleaching composition according to claim 1 further characterized in that R6 is represented by the formula: -T0- (Z ") a Where Z" is covalently bound to T0, and Z "is selected from the group consisting of -C02", -SO3", and -OSO3", is already 1 or 2; and To is: where x is equal to 0 - 3; J, when present, is independently selected from the group consisting of -CR18R19-, -CR ^ R ^ CR ^ R21-, and -CR18R19CR20R21CR22R23-; R ^ -R23 are substituted or unsubstituted radicals chosen from the straight or branched group consisting of H, C1-C18 alkyls, cycloalkyls, alkaryls, aryls, aralkyls, alkylenes. 5. The bleaching composition according to claim 4 further characterized in that said bleach booster is a zwitterion aryliminium wherein R5 is H or methyl, is already 1. The bleaching composition according to claim 4 further characterized in that said booster of the bleached is an arylliminium polion that has a negative net charge where R5 is H or methyl and a is 2. The bleaching composition according to claim 1 further characterized in that said Bleached is an aryliminium cation wherein R 5 is H or methyl, and R 8 is H or substituted or unsubstituted or substituted C 1 -C 14 linear or branched alkyl and cycloalkyl. 8. The bleaching composition in accordance with • claim 1 further characterized in that said bleach booster is an aryliminium cation wherein R6 is selected from the compound group 10 by a substituted or unsubstituted linear or branched C1-C14 alkyl and cycloalkyl, or said bleach enhancer is a zwitterion aryliminium wherein R6 is a radical represented by the formula: where Z "is -CO2 ', -SO3", or 0S03"a is 1 and T0 is chosen from the group 15 composed of: wherein p is an integer from 2 to 4, and R45 is independently selected from the group consisting of H and substituted or unsubstituted linear or branched C1-C18 alkyl and cycloalkyl. 9. The bleaching composition according to claim 1 further characterized in that said bleach species is an oxaziridinium cation wherein R26 is selected from the group of substituted or unsubstituted radicals of a C1-C14 linear or branched, substituted or unsubstituted or cycloalkyl alkyl or said bleach species is a zwitterion oxaziridinium wherein R26 is a radical depicted by the formula: -T0- (Z-) a wherein Z "is -CO2", -SO3"or -OSO3"; a is 1; and T0 is chosen from the group consisting of: wherein p is an integer from 2 to 4, and R45 is independently selected from the group consisting of H and substituted or unsubstituted or linear or branched C1-C18 alkyl or cycloalkyl. 10. The bleaching composition according to claim 1 further characterized in that said bleaching species is an oxaziridinium polion having a negative net charge wherein R25 is H or methyl, Z "is -C02", -S03"or -OS03" and 2. The bleaching composition according to claim 1 further characterized in that said bleaching species is an oxaziridinium polion having a negative net charge wherein R25 is H or methyl, and R26 is selected from the group consisting of a radical represented by the formula: -T0- (Z ") a where Z" is -C02", -SO3" or -OSO3"is already 1; and T0 is chosen from the group consisting of: wherein p is an integer from 2 to 4, and R45 is independently selected from the group consisting of H and substituted or unsubstituted or substituted C1-C18 linear or branched alkyl and cycloalkyl. 12. The bleaching composition according to claim 1 further characterized in that said bleaching composition further contains a surfactant. 13. The bleaching composition according to claim 12 further characterized in that said surfactant is an anionic surfactant. 14. The bleaching composition according to claim 1 further characterized in that said bleaching composition further comprises an enzyme. 15. The bleaching composition according to claim 1 further characterized in that said bleaching composition further comprises a chelating agent. 16. A cationic or zwitterionic compound enhancer of bleaching in the laundry chosen from the group consisting of: [Q PO [IV] [11O and mixtures thereof; wherein the formula [I] and [II] t is 0 or 1; R1-R4 are substituted or unsubstituted radicals selected from the group consisting of H, alkyl, cycloalkyl, aryl, heterocyclic ring, nitro, halo, cyano, sulfonate, alkoxy, keto, carboxylic, and carboalkoxy radicals; either of the two vicinal R1-R4 can be combined to form a fused aryl, fused carbocyclic ring or heterocyclic ring; R5 is a substituted or unsubstituted radical selected from the group consisting of H, alkyl, cycloalkyl, alkaryl, aryl, aralkyl, heterocyclic ring, nitro, halo, cyano, sulfonate, alkoxy, keto, carboxylic, and carboalkoxy radicals; R6 can be a substituted or unsubstituted, saturated or unsaturated radical, selected from the group consisting of H, alkyl, cycloalkyl, alkaryl, aryl, aralkyl, heterocyclic ring, and a radical represented by the formula: -T0- (Z ") a Where Z "is covalently bound to T0, and Z" is selected from the group consisting of -C02", -SO3", -OSO3", -S02", OS02"is already 1 or 2; T0 is selected from the group consisting of: (1) - (CH (R12)) - or - (C (R12) 2) - wherein R12 is independently selected from H or Ci-Cβ alkyl; (2) -CH2 (C6H) -; (5) - (CH2) d (E) (CH2) r where d is from 2 to 8, F is from 1 to 3 and E is - (C (O) O-; (6) -C (0) NR 3-wherein R 13 is H or C 1 -C 4 alkyl; H I - C- (7); Y where x is equal to 0 - 3; J, when present, is independently selected from the group consisting of -CR18R19-, -CR ^ R ^ CR ^ R21-, and _CR18R19CR20R21CR22R23_. R14_R23 SQn radjca | en SUStitItItS Or Without SUStItItIon chosen from the linear or branched group consisting of H, C1-C18 alkyls, cycloalkyls, alkaryls, aryls, aralkyls, alkylenes, heterocyclic rings, alkoxys, arylcarbonyls, carboxyalkyls and amide groups; wherein R7-R10 are substituted or unsubstituted radicals independently chosen from the group consisting of H, linear or branched C1.C12 alkyls, alkylenes, alkoxys, aryls, alcaplos, aralkyls, cycloalkyls, and heterocyclic rings, further provided that when t is 0 , neither R7 nor R8 can be H, and that when t is 1, either R7 and R8, or R9 and R10, are not H; wherein any R1-R10 can be joined with any R1-R10 to form part of a common ring; and wherein for formulas [III] and [IV] t is 0 or 1; R ^ -R34 are substituted or unsubstituted radicals selected from the group consisting of H, alkyl, cycloalkyl, aryl, ring heterocycle, nitro, halo, cyano, sulfonate, alkoxy, keto, carboxylic, and carboalkoxy radicals; and any of the two vicinal R ^ -R34 may be combined to form a fused aryl, fused carbocyclic ring or fused heterocyclic ring; R25 is a substituted or unsubstituted radical selected from the group consisting of H, alkyl, alkaryl, aryl, aralkyl, heterocyclic ring, nitro, halo, cyano, sulfonate, alkoxy, keto, carboxylic, and calboalkoxy radicals, and R26 may be a radical substituted or unsubstituted, saturated or unsaturated, selected from the group consisting of H, alkyl, cycloalkyl, alkaryl, aryl, aralkyl, heterocyclic ring, and a radical represented by the formula: -To- (Z ") a Where Z" is covalently bonds to T0, and Z "is selected from the group of -CO2", - S03", -OSO3", -SO2"and -OSO2" is already 1 or 2; T0 is chosen from the composite group - CH2-C V-CH2- - CH2-C-CH2- (3) I; (4) OH; by (1) - (CH (R12)) - or - (C (R12)) - wherein R12 is independently chosen from H or C? -C8 alkyl; (2) -CH2 (C6H4) -; (5) - (CH2) d (E) (CH2) r wherein d is from 2 to 8; f is from 1 to 3 and E is -C ()) 0-; (6) -C (0) NR13, wherein R13 is H or C? -C alkyl; where x is equal to 0 - 3; J, when present, is independently selected from the group consisting of -CR ^ R40-, -CR ^ R ^ CR ^ R42-, and _CR39R40CR41R42CR43R44_. R35.R44 ^ radjca | is SUBSTITUTE? chosen from the straight or branched group consisting of H, C? -C8 alkyls, cycloalkyls, alkaryls, aryls, aralkyls, alkylenes, heterocyclic rings, alkoxys, arylcarbonyls, carboxyalkyls and amido groups; wherein R ^ -R30 are substituted or unsubstituted radicals independently chosen from the group consisting of H, linear or branched C1-C12 alkyls, alkylenes, alkoxys, aryls, alkaryls, aralkyls, cycloalkyls, and heterocyclic rings, further provided that when t is 0, neither R27 nor R28 can be H, and that when t is 1, either RZf and R, or both R > 29, and, D R30, do not be H; where any R 25 - R34 can be joined together with any other R ^ -R34 to form part of a common ring. 17. A method for washing a fabric that needs to be washed, characterized in that it comprises contacting said fabric with a solution of 5 laundry having a bleaching composition as claimed in claim 1. 18. An additive product for laundry characterized in that F comprises a bleach-enhancing compound selected from the group consisting of: (a) a bleach booster chosen from the compound group 10 by aryliminium cations, aryliminium zwitterions, and / or aryliminium polions having a net charge of +3 to -3 and mixtures thereof, wherein said bleach boosters have the formulas [I] and [II]: where t is 0 or 1; R1-R4 are substituted or unsubstituted radicals selected from F group consisting of H, alkyl, cycloalkyl, aryl, heterocyclic ring, nitro, halo, cyano, sulfonate, sulfonate, alkoxy, keto, carboxylic and carbocyclic radicals; either of the two vicinal R1-R4 can be combined to form a fused, fused carbocyclic aryl or fused heterocyclic ring; R5 is a substituted or unsubstituted radical selected from the group composed of H, alkyl, cycloalkyl, alkaryl, aryl, aralkyl, heterocyclic ring, nitro, halo, cyano, sulfonate, alkoxy, keto, carboxylic, and carboalkoxy radicals; R6 can be a substituted or unsubstituted, saturated or unsaturated radical, selected from the group consisting of H, alkyl, cycloalkyl, alkaryl, aryl, aralkyl, heterocyclic ring, and a radical represented by the formula: -To- (Z ") a where Z "is covalently bound to T0, and Z" is chosen from the compound group F by -C02", -SO3", -OSO3", -SO2" and a is 1 or 2; T0 is selected from the group consisting of: (1) - (CH (R12)) - or - (C (R12) 2) - where R12 is independently chosen 10 H or C? -C8 alkyl; (2) -CH2 (C6H4) -; 15 (5) - (CH2) d (E) (CH2) f- where d is from 2 to 8, F is from 1 to 3 and E is - (C (O) O-; (6) -C ( 0) NR13-wherein R13 is H or C1-C4 alkyl; H I -c- (7); and • 20 (8) where x is equal to 0 - 3; J, when present, is independently selected from the group consisting of -CR18R19-, -CR ^ R ^ CR ^ R21-, and _CR18R19CR20R21CR22R23_. R14_R23 SQn radiCA | is SUStItItIoN oR SUStItItIoN chosen from the straight or branched group consisting of H, C1-C18, aikiles, cycloalkyls, alkaryls, aryls, aralkyls, alkylenes, heterocyclic rings, alkoxys, arylcarbonyls, carboxyalkyls and amide groups; wherein R7-R10 are substituted or unsubstituted radicals independently chosen from the group ^ composed of H, linear or branched C1-C12 alkyls, alkylenes, alkoxys, aplos, alkaryls, aralkyls, cycloalkyls, and heterocyclic rings, provided 10 further that when t is 0, neither R7 nor R8 can be H, and that when t is 1, either R7 and R8, or R9 and R10, are not H; wherein any of R1-R10 can be joined with any of R1-R10 to form part of a common ring; (b) a whitening species selected from the group consisting of oxaziridinium cations, zwitterions oxaziridinium, oxaziridinium polyesters, 15 have a net charge of +3 to -3 and mixtures thereof, said oxaziridinium compound is represented by formulas [III] and [IV]: pi [IV] where t is 0 or 1; R ^ -R34 are substituted or unsubstituted radicals selected from the group consisting of H, alkyl, cycloalkyl, aryl, ring heterocycle, nitro, halo, cyano, sulfonate, alkoxy, keto, carboxylic, and carboalkoxy radicals; and any of the two vicinal R ^ -R34 may be combined to form a fused aryl, fused carbocyclic ring or fused heterocyclic ring; R25 is a substituted or unsubstituted radical selected from the group consisting of H, alkyl, alkaryl, aryl, aralkyl, heterocyclic ring, nitro, halo, cyano, sulfonate, alkoxy, • keto, carboxylic, and calboalkoxy radicals, and R26 can be a substituted or unsubstituted, saturated or unsaturated radical, selected from the group consisting of H, alkyl, cycloalkyl, alkaryl, aryl, aralkyl, heterocyclic ring, and a radical represented by the formula: Z "is selected from the group of -CO2", - SO3", -OSO3", -SO2"and -OSO2" and a is 1 or 2; T0 is chosen from the composite group by (1) - (CH (R12)) - or - (C (R12) 2) - wherein R12 is independently chosen from H or C? -C8 alkyl; (2) -CH2 (C6H4) -; 20 (5MCH2) d (E) (CH2) r wherein d is from 2 to 8; f is from 1 to 3 and E is -C (0) 0-; (6) -C (0) NR13, wherein R13 is H or C1-C4 alkyl; .fa AJ * • where x equals 0 - 3; J, when present, is independently selected from the group consisting of -CR ^ R40-, -CR ^ R ^ CR ^ R42-, and 10 -. 10 -CR R ^ CR ^ R42 CR ^ R44-; R ^ -R44 are substituted or unsubstituted radicals chosen from the straight or branched group consisting of H, C1-C18 alkyls, cycloalkyls, alkaryls, aryls, aralkyls, alkylenes, heterocyclic rings, $ alkoxys, arylcarbonyls, carboxyalkyls and amido groups; wherein R ^ -R30 are substituted or unsubstituted radicals independently chosen from the group 15 composed of H, linear or branched C1-C12 alkyls, alkyls, alkoxys, aryls, alkaryls, aralkyls, cycloalkyls, and heterocyclic rings, additionally provided that when t is 0, neither R27 nor R28 can be H, and that when t is 1, either R27 and R28, or both R29 and R30, are not H; where any • R25_R34 can join together with any other R ^ -R34 to be part of a 20 common ring; and (c) mixtures thereof. 19. The laundry additive product according to claim 18 further characterized in that R6 is selected from the group composed of C1-C14 alkyl or cycloalkyl, linear or branched, substituted or unsubstituted, or R6 is a radical represented by the formula: -T0- (Z ") a wherein Z" is -C02", -S03", or OS03"a is 1 and T0 is chosen from the group 5 composed of: wherein p is an integer from 2 to 4, and R45 is independently selected from the group consisting of H and substituted or unsubstituted linear or branched C1-C18 alkyl and cycloalkyl. 20. The additive product of the laundry in accordance with the # claim 19 further characterized in that R1-R4 are independently chosen from the group consisting of H, alkyl, and alkoxy, R5 is selected from H or methyl, and R6 is selected from the group consisting of a linear or branched C1-C14 alkyl or substituted unsubstituted and cycloalkyl, or R6 is a radical represented by the formula: -T0- (Z ") af wherein Z" is -SO3", or OSO3" a is 1. 20 21. The additive product for laundry according to with claim 18, further characterized in that said laundry product is in a dosage form chosen from the group consisting of a pill, tablet, caplet, gelcap or other individual dosage form. 22. The laundry additive product according to claim 18 further characterized in that said laundry additive further includes a suitable carrier 23. The bleaching composition according to claim 3 further characterized in that said bleach activator is selected from the group consisting of: ethylene tetraacetyl diamine (TAED), benzoylcaprolactam (BzCL), 4-nitrobenzoylcaprolactam, 3-chlorobenzoylcaprolactam, benzoyloxybenzenesulfonate (BOBS), nonanoyloxybenzenesulfonate (NOBS), phenylbenzoate (PhBz), Decanoyloxybenzenesulfonate (Cio-OBS), benzoylvalerolactam (BZVL), octanoyloxybenzenesulfonate (Cß-OBS), perhydrolyzable esters, sodium salt of 4- [N- (nonanoyl) amino hexanoyloxy] -benzene sulfonate (NACA-OBS); lauroyloxybenzenesulfonate or dodecanoyloxybenzenesulfonate (LOBS or C12-OBS), 10-undecenoyloxybenzenesulfonate (UDOBS), and decanoyloxybenzoic acid 15 (DOBA) and mixtures thereof. •