MXPA97003719A - Compositions whitening detergents containing effective whitening activators at low perhidrox concentrations - Google Patents

Abstract

Bleaching detergent compositions containing particular whitening activators are provided. Excellent bleaching is ensured by the selection of whitening activators that operate with good results in slightly alkaline washing conditions or in the presence of reduced levels of hydrogen peroxide

Description

COMPOSITIONS WHITENING DETERGENTS CONTAINING EFFECTIVE WHITENING ACTIVATORS AT LOW CONCENTRATIONS OF PERHYDROXYL FIELD OF THE INVENTION The present invention relates to improved bleaching detergent compositions which are bleach activators. The activators bl, > .,, > .es improve bleaching by sources of hydrogen peroxide such as perborate.

BACKGROUND OF THE INVENTION The formulation of detergent compositions that effectively eliminate a variety of stains and discolorations of fabrics under widely used conditions of use, for example in an extension of the countries of the Pacific Rim continues to be a considerable challenge for the industry. clothes detergent. The problems associated with formulating effective cleaning and bleaching systems have truly been exacerbated by legislation that limits the use of effective ingredients such as phosphate detectors in many regions of the world. Most conventional cleaning compositions may also contain mixtures of various detersive surfactants to remove a wide variety of soils and surface stains. In addition, various detersive enzymes, soil suspending agents, non-match detergents, optical brighteners, and the like can be added to drive full cleaning operation. Many cleansing compositions formulated wholly having a bleaching action, contain oxygen bleach, which may be a percarbonate perborate compound. While the perborates and perc-rbonatos are quite effective at high temperatures, they lose much of their whitening function at low to moderate temperatures, increasingly favored in the use of the product by the consumer. Accordingly, several bleach activators such as tet raacetiietilendiarni (TAED) and nonanoi Joxibencensul fonate (NOBS) have been developed to activate the bleaching action of perborate and percarbonate tr-birds of a wide temperature scale. NOBS is particularly effective on "stained" fabrics. One limitation with the activators, such as TAED widely marketed, is that the wash solution or liquid should have a pH of about 10 or more for better results. Since soils, especially foodstuffs, are often acidic, the detergent products are frequently alkaline or are regulated enough to maintain a high pH, so that the bleach-cleaning system can operate effectively through washing . However, this need opposes the provision of softer formulations that can improve their compatibility with fabrics, glassware and / or leather. In impieza operations with a lower pH of JO, many of the bleach activators lose their effectiveness or suffer from competent side reactions that produce ineffective byproducts. Therefore, the search for more effective activator materials continues, especially for use in alkaline washing liquids gently or with decreased levels of perborate or other sources of hydrogen peroxide. Improved activator materials must be safe, effective, and typically designed to interact with soils and difficult stains. Several activators have been described in the literature. Many are esoteric and expensive, and therefore difficult to commercialize, especially in certain countries, such as Hsia parishes, where local sources of raw materials are not available. It has now been determined that certain selected bleach activators are unexpectedly effective in removing age and stains from fabrics and hard surfaces such as dishes, even under alkaline, low wash conditions, or with decreased levels of peroxide. of hydrogen. These activators also advantageously have high ratios of rates of perhydrolysis to hydrolysis and of perhydrolysis for the formation of diacylperoxide. Without being 1 imitated by the theory, these unusual velocity relationships lead to a number of significant benefits for the present activators, including increased efficiency, avoidance of waste byproduct formation wasted in the wash, improved color compatibility, improved enzyme compatibility, and improved stability in the storage. Bleaching solutions, when selected and used as described herein, are provided using the activators in a variety of conditions, including high dirt conditions, give excellent results. The activators are designed or selected to work well on a wide range of washing or soaking temperatures. In summary, the compositions and methods herein provide substantial advancement over those known in the art, as will be seen from the descriptions hereinafter.

TECHNICAL BACKGROUND Bleach activators of various types are described in U.S. Pat. 4,545,784; 4,013,575; 3,075,921; 3,637,339; 3,177,148; 3,042,621; 3,812,247; 3,775,332; 4,778,618; 4,790,952; EP 257,700; UO 94/18299; UO 94/18298; UO 93/20167; UO 93/12067; and in JJP 02115154. Other references include Aikawa CA 85: 1086z; Stehlicek OR 108: 187402w; Tshida OA 88: 169981y; Ki r Oth er, Encyclopedia of Chemical Technology, Vol. 7, 4"a edition, 1993, p. 1072-1117; K k Othmer, Encyclopedia of Chemical Technology, VoJ. 4, edition, pp. 271-299; Kirk Othrner, Encyclopedia of Chemical Technology, Vol. 9, 44th edition, pp. 567-620.

BRIEF DESCRIPTION OF THE INVENTION The present invention provides a bleaching detergent composition having a low level of soiling and containing: (a) from about 0.1% to about 20%, preferably from about 0.2% to about 10%, most preferably from about 0.4% to about 4% of a bleach activator having a selectivity coefficient of perhydrolysis, KP / KD, of at least 5, rnuy prefen blernen-t e of at least 50, and an efficiency coefficient of perhydrolytic acid of pH at least about 0.15, preferably at least about 0.30, most preferably at least about 0.5; and (b) from about 0.2% to about 40%, preferably from about 0.5% to about 35%, preferably preferably from about 1% to about 25% of a source of hydrogen peroxide; the amounts of (b) being based on weight being expressed considering the total source of hydrogen peroxide as distinct from a molar or "available oxygen base" that can be used from time to time, as indicated elsewhere. the present. The terms "soil level resistivity", "perhydrolism selectivity coefficient" and "perhí drol i sis efficiency coefficient with low pH" are defined in detail hereinafter. Preferred bleach activators for component (a) include, but are not limited to, any of the following: p-nitrobenzoylcaprolactan; p-mtrobenxoyl-val ero lactam; linear or branched C2-C9 alkylsulfomlbenzoylcaprolact ina; alkylsul fonylbenzoyl valerolactarna C2-C9 linear or branched; linear or branched C 2 -C 9 alkyloxy sul fom lbenzoi lcaprolactarna; to the linear or branched C2-C9 fomlbenzoylvalerolac-tarna loxisul; alkyl (arnmo) sulfonyl benzylcaprolactane linear or branched C2-C9; alky 1-Way) -sulfonylbenzoi 1 valerolacta a of C2-C9 linear or branched; 2-f? Roilcap olactama; 2 -furoyl valerolactam; 3- fu roí 1 cap lactama; 3-furo? Lvalerolactarna; 5-n? Tro-2-furo? 1-caprol ctarna; 5-n? Tro-2-furo? Lvalerolactarna; J -na ti-caprolactam; l ~ naft 11 --valerolactam; and mixtures thereof. More preferably in these embodiments, the bleach activator is selected from the group consisting of the linear or branched C 2 -C 9 cyclohexyl caprolactam qi ilsul foni lbenzoyl; alq? i lsulfom lbenzoi 1-valerolactarna of C2-C9 linear or branched; alkyloxysul fonyl-benzoylcaprolactam of linear or branched C2 ~ C; linear or branched O 2-C 9 alkyloxy sulfonylbenzoylvalerolactam; linear or branched alkyl (arnide) sulphomyl benzoyl-caprolactam C2-C9; straight or branched alkyl (anino) sulfonylbenzoylvalerolactan of O2-C9; 2 ~ furo? Lca? Rolactarna; 2-furo Ivalere-lactam; 3-furo? 1-caprolactam; 3- uroylvalerolactan; 5-n? Tro-2 -furoil-caprolactarna; 5-n? Tro ~ 2-furo? L-valerolaci loves; and mixtures of the same. In preferred embodiments, detergent compositions are provided in which said components (b) and (a) are in a ratio of about 3: 1 to about 20: 1, expressed on a base of (b) :( a) in units of the moles of H2O2 released by said source of hydrogen peroxide to the moles of bleach activator. The compositions of the invention may also contain (c) from about 0.1% to about 50% detersive ingredients that do not contain soap to reduce the pH; Such ingredients are a particularly convenient solution to the problem of compensating for the tendencies of raising the pH of common sources of nitrogen peroxide such as sodium salts or perborate salts. Such compensation may be desirable in certain embodiments, for example, gentle compositions compatible with the skin. In certain preferred embodiments, from about 0.01% to about 5% of a soil release polymer can be added for their fabric care benefits. In a highly preferred embodiment, detersive ingredients that do not contain soap to reduce the proper pH in the present essentially consist of about 1% to about 25% of one or more members selected from the group consisting of: ( i) ionic detersive surfactants which do not contain soap, - (11) polyrnene dispersants; (m) transition metal chelators; and (iv) mixtures thereof. To illustrate in more detail, said detersive ingredient containing no soap to reduce the pH may be an ionic detersive surfactant selected from the group consisting of ammonium detersive surfactants in at least partially acidic form; surfactants will be polar; zwitterionic surfactants; and mixtures thereof. The advantage of the previous component is to combine in a single material the cleaning functionality of a surfactant with the ability to fine-tune the formulation so that it releases a specific scale of pH. To be clear, if the bleach activators selected are used in the present, such tuning would adversely affect the bleaching performance. The surfactants that are normally neutral can be added for their common cleaning function, although it is evident that such surface-active agents do not have measurable effects that lower the pH. Another preferred surfactant that can also be added to the composition but does not markedly bind the pH is a detersive surfactant agent derived from sugars such as an alkyl-N-methyl glucosamide. The ethoxylated nonionic detersive surfactants are also neutral for the purposes of the present invention. The preferred probabilities of the bleaching detergent compositions herein are solid. Preferred compositions include granules. For storage reasons, especially in hot countries such as Saudi Arabia, it is preferred that a bleach-selected activator has a melting point of about 30 ° C or more, preferably 50 ° C or more. The present bleaching detergent compositions may further contain an alkaline builder, such as a phosphate salt, preferably at a level not to exceed about 35%. In other highly preferred embodiments of the bleaching detergent composition, the alkaline source of hydrogen peroxide is a sodium perborate such as a sodium perborate nonohydrate or a sodium perborate tetrahydrate, and the pH reducing system of the detersive ingredients which Do not contain combatible soap is present at a level of approximately 1% to approximately 12%.

Desirably desirable, as noted, is the additional inclusion of a soil release polymer. When present, the soil release polymer is refrably a member selected from the group consisting of nonionic soil release polymer; dirt release polymers topped with sulfo; and mixtures thereof. Such polymers are defined and illustrated in greater detail herein below using the equivalent terms "soil release polymerization agent" or "soil release agent". In another non-limiting illustration, the invention provides a solid form detergent composition having a pH in use in the range of about 7 to about 9.5, which consists of: from about 0.4% to about 4% bleach activator having a coefficient of selectivity of perhydrol i sis of 5 or more and a coefficient of efficiency of perhi drolisi s of reduced pH of 0.3 or more; and, as formulated, from about 1% to about 12% by at least one detersive surfactant that does not contain partially acidic soap. Such a composition may further contain from about 0.1 to about 10% of a member selected from the group consisting of sodium phosphate builder salts, sodium polycarboxylate builder salts, and mixtures thereof, and about 10% more than one member selected from the group consisting of sodium chloride, sodium sulfate and mixtures thereof; optionally, the composition may further include a conventional bleach activator of alkanoyl lox benzensul fonate or a conventional activator-bleach of tetraacetyl lenedianin. The bleaching detergent compositions of this invention may include additional detergent additives that include 1 or more of the following ingredients: antiredeposition or antifouling polymers, transition metal chelators, detergency builders, fluorescent whitening agents, inhibitors of dye-transfer, perfumes, dyes and fillers. The compositions of this invention are typically formulated below the levels useful for dry cleaning of any organic solvent. Preferably the compositions are substantially free of organic solvents. Suitable detergency builders are selected from the group consisting of phosphate builders which include but are not limited to tppol, sodium phosphate, tetrasodium pyrophosphate, sodium acid pyrophosphate, cyclopene, layered silicate, zeolite n, zeolite P in its vain modifications, and mixtures of the same. In preferred embodiments, the bleaching compositions release an aqueous pH in the range of about 6.5 to about 9.5, most preferably from about 7 to about 9, preferably even from about 7.5 to about 8.5, and the level of the peroxide source of hydrogen is sufficient to provide an ionic concentration of perhydroxyl, measured at a pH of about 7.5, from about 10- * to about 1010 molar, most preferably about 10_s < about 10-8 molar. The present invention has numerous advantages, including, but not limited to, improved bleaching at reduced pH, skin-compatible hand washing formulations for laundry fabrics, which may have granule or laundry rod shapes. By "effective amount" in the present it is believed to mean-an amount that is sufficient, which is employed under any comparative test conditions, to enhance the cleanliness of a soiled surface. Likewise, the term "catalytically effective amount" refers to a quantity that is sufficient in which any comparative test conditions are employed, to enhance the cleanliness of a soiled surface. All percentages, ratios and proportions herein are by weight, unless otherwise indicated. All the documents cited, in the pertinent part, are incorporated in the preend by reference.

DETAILED DESCRIPTION OF THE INVENTION Dirt Level Resistance - It is well known to those skilled in the art that many soils found typically in detergent applications are effectively acidic in nature. As such, the type and amount of dirt found can significantly decrease the use of pH of a bleaching solution. Common body soiling, for example, may include sebaceous fatty acids, citric acid, lactic acid and the like as well as tglypephed esters < , which can hydrolyze in an aqueous alkaline environment to produce additional carboxylic acid species. The response of a bleaching solution to the introduction of acidic components can be calibrated by measuring the change in the pH of said solution at the time of the addition of a model acid, acetic acid. The "Level Resistance" ("SLOW") of a bleaching solution is determined as follows: A 1 kg sample of bleach-a is stirred for 30 minutes and -did immediately afterwards. The pH measured is'. , not pHi. After determining the pHi, 30 ml of an acetic acid (prepared by diluting 1 ml of glacial acetic acid with distilled water, deionized to a total volume of 1000 ml) are added to said bleaching solution and the resulting mixture is stirred for 5 minutes, after which a second pH (pHf) is measured. The dirt level resistance, denoted as s, is defined by the equation s = lOxí? D; where r - Hi - pHf,? - 62 / pHi, and where, when pHi > ? He, 6 = Hi - pHc, and when pHi < ? Hc, 6 = 0. Said pHc is the critical pH, given by pHc = pKa pyridic + pKc where pKc is the critical pK given by pKc - 100C (1 / pKa er acid) - (i / pHpr? F) 1 10 wherein the acid pKaper is the aqueous ka of the per-acid species present in the normal solution, and Hprßf is the preferred pH, adjusted equal to the midpoint of the most preferred wash pH scale of 7.5- 8.5. . When two or more peracid species are present, the value of pKapBr acid The lowest level is used to calculate 6. The soil level resistance of any particular detergent formulation can be designated based on its value of s as shown in the table above. -, continuation. twenty ? Performance Bleach Activator Component Enhanced - The bleaching detergent compositions of the present invention contain a particular bleach-activating component. The activator-essential is selected to have particular properties so that it is more effective in promoting bleaching under certain conditions of use in which TOED or similar conventional cleaning activators are relatively inefficient and ineffective. A preferred group of essential activators contains compounds having one or more RC (0) ~ portions that produce a peracid RC (0) -OOH in perhydrolysis (reaction with perhydroxy, -OOH). R is selected so that the difference in aqueous pKa between acetic acid and the carboxylic acid anion, RC (0) OH, of said peracid is at least 0.6, preferably at least about 1.2. When it is established that the difference in aqueous Ka between acetic acid and the carboxylic acid analog, RC (0) 0H, of a per- cid is at least 0.6, the following subtraction is made, in the order indicated: pKa (CH3C (0) 0H) -? Ka (RC (0) OH). These improved performance bleach activators also have a pH perhydrolysis efficiency coefficient (a practical measure of peracid formation defined hereinafter in the following) of chicken less about 0.15, preferably at least about 0.3, and a ratio of p / v > 5, preferably kp / ko. 30, still highly preferred kp / l-D > 50, where kp is the constant velocity for the perhydrol isis of the activator bleaches of improved performance and kn is the constant velocity for the formation of a diacylperoxide, RC (0) OOC (0) R, of the best working whitening activator do. The activators herein preferably comprise one or more portions, L, which act as leaving groups in the per-hydrolysis. In this way, the preferred improved performance blanking activators herein have the formula RC (0) ~ L. The preferred leaving groups, L, comprise at least one tri-coordinated nitrogen atom connecting covalently L to RC (0) -. In addition, the preferred improved functioning bleach activators are capable of forming a maximum of one molar equivalent of said perhydric acid in the perhydrolyse and have kμl 10 ~? s-i and a ratio kp / kH ^ 1, more preferably kp / kμ >; 2, wherein kH is the constant rate for the hydrolysis of the improved activator-bleach and said constant rate for per-hydrolysis. In general, R and L can be neutral independently or can be charged either positively or negatively. In the preferred compositions, both R and L are neutral, wherein L is typically selected from suitably substituted or unsubstituted lactams, 4,5-dihydroirnidazoles of 2-aikel, and mixtures thereof, and R is illustrated by p-nitrophenyl or, more preferably, an alkylsulfonylphenyl portion. Suitable portions R are illustrated at a later length. In preferred embodiments, R can be connected to -C (0) - through a carbon atom that is part of an aromatic ring, and L can be selected such that its conjugated acid, HL, has an aqueous Ka in the scale of about 13 to less than approximately 17. In other highly preferred embodiments, the bleaching activator enhanced as a total, or simply its leaving group, L, is free of any heterocyclic portion wherein a The hydrogen atom is attached to a carbon atom that is a1 a for both a carbomlo group or ur heteroatom ulti valen-t e. In highly preferred embodiments, these compositions also consist of a bleach catalyst - at levels described in the art. Bleaching solutions consisting of such compositions have a particularly significant bleaching performance improvement as compared to other identical solutions in which a conventional bleach activator with TAED is used in place of the improved performance bleach activator. This invention also includes bleaching detergent compositions containing novel, performance enhancing bleach activating compounds having the formula RC (0) -L, wherein L is selected from the group consisting of lactams and 4,5-ddro? rn? dazoles; R is selected 1 (1 of the group consisting of phenyl substituted with more than one chloro, bromo or nitro substituent; furan or furan substituted with one or more substituyeptes chlorine, bromine, nitro, alkyl sulfomyl or ap lalkylsulfonyl; 1-naft? Lo; 1-substituted naphthyl; or 2-naphthale substituted with one or more substituyent. chlorine, bromine or nitro; formulas pag. 9 and mixtures of the others; wherein in each structure a is independent of 0 or 1, b is 0 or 1, and A is selected from 0 and NR2 wherein R2 is H or methyl; and wherein a is 1 and A is 0, R 1 is selected from alkyl, aplaxyl, alkoxy, aploxy, alkylamino and anlamino; when a is l and A is different from 0, i is selected from alkyl and aplakyl. RCYO Portions) - In preferred bleach activators useful herein, R is non-lunitely illustrated by phenyl or electronegatively substituted selected from the group consisting of p-chlorophenyl, m-chlorophenyl, p-mofofemlo, 3,5-d? Chlorophen? lo and 3,5-dimtrofenyl and mixtures thereof. Also in other preferred embodiments, R is selected from l-sulphonylphene, rilalkylsuifonyl-emlo, alkylsulfonyl-naphthyl, aplakyl-sulphonyl-naphthyl and mixtures of the same. Note that when naphthyl is selected, unsubstituted 1-naphthol or 1- or 2-naphthyl is substituted. Other examples of preferred bleach activates include those in which R is a substituted or unsubstituted furan and wherein R is substantially free of chloro or nitro substituyontes. Starting Groups - The portions L in the improved performance whitening activators of the compounds of this invention are preferably selected from the group consisting of unsubstituted lactams, substituted lactams,? -radio-4,5-dichloro? substituted or unsubstituted dazoles and mixtures thereof. Particularly preferred examples of L are those that are selected from the group consisting of: formulas pag. 10 Enhanced Performance Bleach Activator Compounds - In the preferred improved performance bleach activator compounds useful in the bleaching solutions of this invention, L is as indicated supra and R is selected from the group consisting of: (I): formula pag. 10 wherein a is independently 0 or 1, b is 0 or 1, A is selected from 0 and NR2 wherein R2 is H or methyl; when a is 0 or when a is 1 and A is 0, PA is selected from alkyl, aplaxyl, alkoxy, aploxy, alkylaryl and aplarnino; when a is 1 and A is different from 0, R * is selected from alkyl and aplakyl; and (II) substituted furan or furan, with the formula: formulas p. 10 wherein T is selected from the group consisting of H, O2, Br, alkyl and aplayl quilo. In a highly preferred embodiment of the yield enhancement activator-bleach, L is preferably selected from the group consisting of: formulas pag. 10 and R the group consisting of: formulas pag, J 1 wherein R1 is selected from alkylalkyl, alkoxy, aploxy, alkylamine and arylamino; and T is selected from the group consisting of H, Br and O2. Compositions consisting of these novel compounds are also included within the scope of this invention. Critical character of per »- '^ analysis and velocity pK«. According to the invention, whitening compositions are provided, in which the bleaching activators need to respect the ka-functionalities and criticalities that refer to perhydrol speeds of 1 sis, hydrolysis and diacylperoxide formation. The efficiency of the peri-hydrolysis is important to select the bleach activator.All these cripcalities will be better understood and appreciated in light of the following description.PK value - The acids in which the organic chemists have been traditionally concerned include a scale, from the weakest acids to the strongest ones, of approximately 60 pK units.Since not a single solvent is suitable on a wide scale, the establishment of comprehensive scales of acidity requires the use of different solvent vanes., one might expect to build a universal acidity scale by relating the results obtained in different solvent systems to one another. Mainly because solute-solvent interactions affect the balance between acid-base in different solvents, it has not been proven that it is possible to establish such a scale. The water is taken as the normal solvent to establish an acidity scale. It is convenient, with a high dielectric constant, and is effective in solvent ions. The equilibrium acidities of a host of compounds (eg, carboxylic acids and phenols) have been determined in water. The data collections of pK can be found in Pei pn, DD "D ssociat on Constants of Organic Bases ln Aqueous Solution "; Butterworths: London, 1965 and Suppleinen-t, 1973; Serjeant, E. P .; Dempsey, B. "Ionisation Constants of Organic Acids m Aqueous Solution"; ? nd ed., Pergarnrnon Press: Oxford, 1979. Experimental methods for determining pKa values are described in the original documents. The values of Ka that fall between 2 and 10 can be used with great confidence, however, the values removed additionally are from this scale, the greater the degree of skepticism with which they should be seen.

For acids that are very hard to be investigated in water solution, more acidic media such as acetic acid or mixtures of water with percropic or sulfuric acid are commonly used; For acids that are too weak to be tested in water, solvents such as liquid ammonia, cyclohexyllamine and d-methylsulfoxide have been used. The Harnrnett H0 acidity function has allowed the aqueous acidity scale, which has a practical Ka scale of approximately 0 12 that will be extended in the region of negative pKa values by approximately the same scale. The use of acid functions H_ employing strong and cosolvent bases has extended similiarly the scale up by approximately 12 pKa units. The invention includes the use of starting groups whose conjugated acids are considered weak; they have water pK values greater than about 13. Establishing only that a certain compound has an aqueous pKa above about 13 is sincere. As mentioned earlier, values that are much higher than this are difficult to measure with confidence without resorting to the use of an acidity function. Measurement of the acidity of weak acids using the method H_, which has the advantage of a normal aqueous state is adequate to determine whether the conjugated acid, HL, of the starting group L, has an aqueous pKa greater than about 13 or less of approximately 17. However, it is also restricted because (1) it requires the extrapolation to r-birds of variable solvent media and (2) the errors made in the determination of the indicator of the values of? Ka are cumulative. For this and other reasons, Bord ell and his collaborators have developed a scale of acidity in di et ilsulfoxido (DMSO). This solvent has the advantage of a relatively high dielectric constant (e = 47); the ions are therefore diassociated so that the problems of differential ion pairings are reduced. Although the results refer to a normal state in DMSO instead of water, a link to the scale of aqueous Ka has been made. When acidities measured in water or on a water-based scale are compared with those measured in DMSO, acids whose conjugate bases have their localized charge are stronger acids in water; Acids whose conjugate bases have their delocalized charge on a wide scale are usually comparable in strength. Bordwell details his findings in a 1988 article (Acc. Chem. Res. 1988, 21, 456-463). The procedures for the measurement of? Ka in DMSO are found in documents referenced in that article. Definitions of H, kp and KD - In the expressions mentioned below, the choice about using the concentration of a nucleus or its anion in the velocity equation was made as a matter of convenience. One skilled in the art will realize that measuring the pH of the solution provides a convenient means of directly measuring the concentration of hydroxide ions present. One skilled in the art will further recognize that the use of the total concentrations of hydrogen peroxide and perac provide the convenient means for determining the rate constants I-P and kD. The terms, such as RC (0) L, used in the following definitions and in the conditions for the determination of H, kp and 1-D, are illustrative of a general bleach activator structure and are not limited to any structure of bleach-specific activator of the present. Definition of kp R0 (O) L + HO- RC (0) 0- * HL The speed of the reaction shown above is given by Velocity = kH CRC (0) l_KHO-] The constant speed for hydrolysis of the bleach activator - (kH) is the second order rate constant for the bi-olecular reaction between activator-bleach and hydroxide anion as determined under the conditions specified below. Definition of kp RC (0) L + H2O2 RC (0)? 2H • HL The speed of the reaction above is given by Speed = p CRC (?) L3CH2? 2] t where [H2O2 IT represents the total concentration of hydrogen peroxide and is equal to CH2O2I + CHO2"" 1. The rate constant for the perhydrolysis of the bleach activator (kp) is the constant second order rate for the bimolecular reaction between bleach activator and hydrogen peroxide as determined under the conditions specified below. Definition of kp RC (0) L + RC (0) 02C (0) R + HL The speed of the reaction shown above is given by Velocity-kDCRC (0) L] CRC (0) 02Hp where [RC (0)? 2H3T represents the total concentration of peracid and is equal to CRC (0)? 2H.l + rRC (0)? 2-] The rate constant for the formation of a diacylperoxide from the bleach activator ( kp), is the second order rate constant for the bimolecular reaction between bleach activator and perishing anion, is calculated from the previously defined ko '. The value-for koy is determined under the conditions specified later. Definition of the perhydrolysis selectivity coefficient - The perhydrolysis selectivity coefficient is defined as the Kp / Ko ratio in which Kp and KD are as defined above.

Conditions for the determination of speed constants Hydrolysis - A set of experiments is completed to measure the hydrolysis rate of a bleach activator RC (0) L in aqueous solution at a total ionic strength of IM adjusted by the addition of NaCl. The temperature is maintained at 35.0 ± 0.1 ° C and the pH of the solution is regulated with NaHCO3 + Na2C03. A solution of the activator ([RC (0) L] = 0.5 rnM) is reacted with varying concentrations of NaOH under conditions of stopped flow and the speed of the reaction is optically mimicked. The reactions or pseudo first-order conditions are carried out to determine the bimolecular rate constant for the hydrolysis of the bleach activator (H). Each kinetic test is repeated at least five times with approximately eight different concentrations of hydroxide anions. All kinetic tracings give satisfactory adaptations to a law of kinetic velocity of first order and a diagram of the first order velocity constant observed against the concentration of hydroxide anion is linear over the investigated region. The slope of this line is the derivative second order velocity constant μ. Perhydrolysis - A set of experiments is completed to measure the velocity of perhi drolisi s of an activator bleach RC (0) L in aqueous solution of pH = 10.0 with a 1M ionic strength adjusted by the addition of NaCl. The temperature is maintained at 35.0 ± 0.1 ° C and La 20 solution is regulated at pH with Nal-IC? 3 + N 2C03- A solution of the activator ([RC (0) L] = 0.5 rnM) is reacted with varying concentrations of sodium perborate under conditions of stopped flow and velocity of the reaction is momentreated optically. The reactions or pseudo-first-order conditions are carried out to determine the bimolecular velocity constant for the perhydrolyzate of the activator-bleach (kp). Each kinetic test is repeated at least five times with approximately eight different concentrations of sodium perborate. All the kinetic tracings give satisfactory adaptations to a law of kinetic velocity of first order and a diagram of the first order velocity constant observed against the total concentration of hydrogen peroxide is linear over the investigated region. The slope of this line ee the second order speed constant derived kp "One skilled in the art recognizes that this rate constant is different from, but related to, the second order rate constant for the reaction of a bleach activator with the anion of hydrogen peroxide (knuc). The ratio of these velocity constants is given by the following equation: knuc = kP i (Ka + CH + / K) where ka is the acid dissociation constant for hydrogen peroxide.

Formation of diacylperoxide - A set of experiments is completed to measure the rate of formation of a diacylperoxide RC (0) 02C (0) R from an activator-bleach RC (0) L in aqueous solution of pH = 10.0 with ionic strength total of 1M adjusted by the addition of NaCl. The temperature is maintained at 35.0 ± 0.1 ° C and the solution is regulated at pH with NaHC? 3 + Na2C03. A solution of the activator (CRC (O) L] - 0.5 M) is reacted with varying concentrations of peracid under conditions of stopped flow and the rate of reaction. It is monitored optically. Reactions are carried out under pseudo first order conditions to determine the bimolecular velocity constant ko'- Each kinetic test is repeated at least five times with approximately eight different concentrations of peracid anion. All kinetic traces give sat- isfactory adaptations to a law of first order kinetic velocity and a diagram of the first-order velocity constant observed against the total peracid concentration is linear over the investigated region. The decline of this line is the second order velocity constant derived o '. The bimolecular velocity constant for the formation of a diacylperoperoxide from a peracid anion (ko) is calculated according to D = kD '. { (Ka + CH +] / K.}, Where Ka is the acid dissociation constant for the RC (0)? 2H peracid A person skilled in the art will recognize that pKa values for peracids fall on a relatively large scale narrow from about 7 to about 8.5 and that a | >; H = 10..0, when Ka approximately 10-8,. { (?to + LH +] / Ka} - 1 and D = kD '. Test for low pH perhydrolysis efficiency -This method is applicable as a test to verify any RC (0)? 2l- bleaching activators (without ignoring any improved bleach activator structure specific to the present) by confirming the formation of a peracid analyte RO (0)? 2H. The minimum parameter for the efficiency of low pH perhi drolysis (LPE) is a coefficient, as defined above, > 0.15 within 10 minutes when testing ba or the conditions specified later. Test protocol - Deionized and distilled water (495 rnl, adjusted to a pH of 7.5 with NaH2 PO4 and N2HP0 «) s added to a 1000 rnl beaker and heated to 40 - * 1 ° C. Three hundred and seventy-five (375) g of 30% hydrogen peroxide concentration is added to the beaker and the mixture is stirred for two minutes before adding a solution of 5 rnl containing 100 rng of activator (pre-dissolved in 5 ml. of an organic solvent (e.g., methanol or dirnetiiforrnamide)). The initial data point is added one minute later. A second sample is removed after 10 minutes. Aliquots of sample (2 rnl.) Are examined through analytical HPLC for the quantitative determination of perac or RC (0)? 2H.

Sample aliquots are mixed individually with 2 rnL of a 5 ° C solution pre-in acetyl acetyl / acetic acid (86/14) and placed in a 5 ° C controlled temperature controlled automotive for subsequent injection over the CLAR column. The high performance liquid chromatography of the authentic peracid under a certain set of conditions establishes the characteristic retention time (tR) for the analyte. The conditions for chromatology will vary depending on the fraction of interest and should be chosen to allow baseline separation of the peracid from other analytes. A normal calibration curve (peak area versus concentration) is constructed using the acid peracid. The analyte peak area of the 10-minute sample of the above-described test is subsequently converted to a generated ppn for the determination of the LPE amount. It is considered that a bleach activator is acceptable when a value of the coefficient of efficiency of per idrolis s of low pH, LPE-L "(p? M of generated peracid) / (pprn of theoretical per-acid)]> 0.15 is obtained In ten minutes under the specified test conditions, as a matter of fact, by comparison with 4.5-saturated cyclic modalities of the present bleach activators, the closely related chemical compounds known in which the 4,5-position is unsaturated have surprisingly higher hydrolysis rates.

Specifically, acetyl uranidazole has a kH greater than 10.0 M_1 s-1: therefore, this invention does not encompass the irnidazole as a starting group. Source of hydrogen peroxide - A source of hydrogen peroxide herein is any convenient compound or mixture that under conditions of consumer use-provides an effective amount of hydrogen peroxide. The levels can vary widely and are typically from about 0.5% to about 70%, and from about 0.5% to about 25% by weight of the bleach compositions. The source of hydrogen peroxide used herein may be any convenient source, including the hydrogen peroxide itself. For example, perborate, e.g., sodium perborate (any hydrate, but preferably mono- or tetrahydrate), peroxy-sodium carbonate peroxide or equivalent percarbonate salts, perox sodium pyrophosphate hydrate, urea peroxyhydrate or peroxide of hydrogen can be used herein. Mixtures of any suitable hydrogen peroxide sources can also be used. A preferred percarbonate bleach comprises dry particles having an average particle size on the scale of about 500 micrometers to about 1000 micrometers., not more than about 10% by weight of said particles being less than about 200 microliters and not greater than about 10% by weight of said particles being less than about 1250 microns. Optionally, the percarbonate can be coated with water soluble, borate or silicate surfactants. Percarborate is available from vain commercial sources such as FMC, Solvay and Tokai Denka. Detersive Surfactants - Surfactants are useful herein for the usual cleaning power and are generally used at the usual levels useful as detergents. Some non-limiting examples of surfactants useful herein fall into two classes: those that can act as a detersive ingredient that is not soap to reduce pH, and those that can not. Within the first of these two classes are the conventional alkyl benzene sulfonates Cn-Ciß ("SAL"), and the C10-C20 ("SA") primary alkyl, branched chain and random sulphates, alkyl sulfates C? or ~ secondary Ci8 (2,3) CH3 (CH2)? (CH0S03-M +) CH3 and CH3 (CH2) and (CH0S03"M +) CH2CH3 where x and (y + l) are whole numbers of at least appropiate 7, preferably of at least 9, and M is a cation soluble in water, especially sodium, unsaturated sulfates, such as oleyl sulfate, the alkylalkoxysulfates of Cío-Ciß ("AE? S", especially ethoxysulfates EO 1- 7), Cila-Ciß cosily sulfates (especially ethoxycarboxylates EO 1-5), and alpha-sulphonated fatty acid esters of Ci2 ~ Ci8- If desired, they can be included in the compositions general, conventional amphoteric surfactants, such as C12-C18 betaines and sulfobetaines ("sultamas"), Cio-Ciß aminooxides and the like. Optional surfactants, ie those of the second of the above-identified classes, which can normally serve for the reduction of pH in the present, include the glycerol ethers Cio-Cis and s? R corresponding sulfated glycosides; the alkylethoxylates Ci2 ~ C? ß ("AE") including those called to the narrow-stranded qui leteoxylates and the C6-C12-alkyl-phenolalkyalates (especially the ethoxylates and the mixed ethoxylate / propoxylates). Other preferred optional surfactants include the N-alkyl pol 1 hydroxy fatty acid amides which can also be used. Some typical examples include the N-rnetyl glu canudas C12-C18- See UO 9,206,154. Other surfactants include the N-alkoxypolyhydroxydiol amides, such as the N- (3-methoxypyrol) glucamide C? O-C? B. The N-propyl- to N-hexylglucarbons C12-Cie can be used for reduced foaming. Optionally, conventional soaps C8-C20 can also be used. If high foaming is desired, branched-chain Cio-Ciß soaps can be used. Mixtures of ammonium and nonionic surfactants are especially useful. Other conventional useful surfactants are listed in regular texts.

Attached Ingredients - Whilst the bleaching additives effective herein may contain only whitening activators of the invention, fully formulated laundry compositions also typically contain other adjunct ingredients to improve or modify performance. Some typical, non-limiting examples of such ingredients are described in the appendix below for the convenience of the formulator. Bleaching Catalysts - If desired, bleaching compounds can be catalyzed by a manganese compound. Such compounds are well known in the art and include, for example, the manganese-based catalysts described in the U.S. Patent. 5,246,621, Patent of E.U.A. 5,244,594; U.S. Patent A. 5,194,416; Patent of E.U.A. 5,114,606; and Publication of Sol. .tud of European Patent Nos. 549,271A1, 549,272Al, 544,44 .12, and 544,490A1. Preferred examples of these catalysts include Mn? V2 (? -0) 3 (1,, 7-tprnethyl-i, 4,7-tr? Azac? Clononane) 2 (PFe) 2, Mn113: 2 (u-O)? (u-0Ac) 2 ~ (1,4, 7-tpmet? ll, 4,7-tr? azac? clononane) 2 - (CIO4) 27 MnIV4 (uO) e - (1, 4,7-tpazac? clononane )4 . { CIO4 7 Mn-m - niv4 - (u-O)? (u-0Ac) 2 - (1,4, 7-t nmeti 1-1, 4, 7- triazaei clononane) 2- (C10) 3, niy (1,4,7-tprneti ll, 4,7-tpazac Clononan) - (0CH3) 3 - (PFß), and mixtures thereof. Other metal-based bleach catalysts include those described in the U.S. Patent. 4,430,243 and Patent of E.U.A. 5.1L4.611. The use of manganese with several Complex ligands for improving bleaching are also recorded in the following U.S. Patent Nos: 4,728,455; 5,284,944; 5,246,612; 5,256,779; 5,280,117; 5,274,147; 5,153,161; and 5,227,084. Said manganese may be combined previously to form a compound with ethylendiarnma dieuccinate or added separately, for example as a sulfate salt, with ethylene diamine disuccinate. (See U.S. Application No. of Sene 08 / 210,186, filed March 17, 1994.) Other transition materials in said transition catalysts containing transition metals include iron and copper. Notably, the preferred embodiments of the present invention in which the wash pH is in the range of about 6.5 to about 9.5 and one of the enhanced performance whitening activators is selected to be selected from those indicated above in combination with one of the aforementioned bleaching catalysts guarantee a whitening effect particularly superior, in comparison with other compositions identical in other respects in which conventional whitening activators are used, such as TAED (see hereinafter) instead of the whitening activator. enhanced performance. As a practical matter, and not by way of limitation, the bleaching compositions and methods of the bleach can be adjusted to provide on the order of at least one part per ten million of the active bleach catalyst variety in aqueous wash solution, and will provide about 0.1 pprn to about 100 ppm, most preferably from about 1 ppm to about 50 ppm, of the catalyst variety in the aqueous laundry solution. Conventional bleach activators - "Conventional activators" herein are any blinding activators that do not adhere to the conditions "Jadas in connection with intensifying performance bleach activators. Numerous conventional bleach activators are known and optionally included in the bleaching compositions present. Many non-limiting examples of activators are described in the U.S. Patent. 4,915,854, issued April 10, J990 to Mao and others, and the U.S. Patent. 4,412,934. The activators of nonanoyloxybenzene fonate (NOBS) and tetraacetyletiyenndiarnm (TAED) are typical and mixtures thereof can also be used. The activators of nonanoyloxybenzenesulfonate (NOBS) and tet acetylethylenediarin (TAED) are typical and mixtures thereof can also be used. See also the previous reference of E.U.A. 4,634,551 for other typical bleach activators. Some bleach activators derived from arnide are those of the formulas: RiN (RS) C (0) R 2c (0) L or RiC (0) N (RS) R 2 C (0) L in which R 1 is an alkyl group containing approximately 6 to about 12 carbon atoms, R 2 is an alkylene which contains from 1 to about 6 carbon atoms, RS is H or alkyl, aplo or alkyl containing from about 1 to about 10 carbon atoms, and L any suitable party group. A further illustration of the conventional, optional activators of the above formulas include (6-octanarne-do-caproyl) -oxa-benzenesulfonate, (6-nonam? Docapro?) Ox-benzenesulfonate, (6-decanarido-caproyl) ox? benzenesulfonate, and mixtures thereof, as described in the US Patent. 4,634,551. Another class of conventional bleach activators comprises the benzoxacin-type activators described by Hodge et al. In the U.S. Patent. 4,966,723, issued October 30, 1990. Another claye of bleach activators includes acyl-lactase activators that do not provide the benefits and critical characters described herein. Some examples of optional lactam activators include octanoyl capro-lactarin, 3,5,5-tpmethylhexanoylcaprolactam, nonanoilca rolactama, decanoylcaprolactane,? ndecenoi lcaprolacta a, octa noi 1vale olactam, decano-11-valerolactam, undecenoyl valero-lactarine, nonanoilvalerelact ma, 3,5,5-tprnet? l hexane-l-lactate, and mixtures thereof. Bleaching agents other than the hydrogen peroxide sources are also known in the art and can be used herein as adjunct ingredients. One type of bleaching agent that does not contain oxygen of particular interest includes the photoactivated bleaching agents, such as the sulphonated aluminum and / or zinc phthalocyamines. See US Pat. No. 4,033,718, issued to Holocornbe et al. On July 5, 1977. If used, the detergent compositions will typically contain from about 0.025% to about 1.25%, by weight, of such bleaches especially zinc phthalate. sulfonated Organic Peroxides, Especially Diacyl Peroxides - are extensively illustrated in Kirk Othmer, Encylopedia of Chemical Technology, Vol. 17, John Uiley and Sons, 1982 on pages 27-90 and especially pages 63-72, all incorporated herein by reference. Also illustrated are suitable organic peroxides, especially diacyl peroxides in "Initiators for Polymer Production", Akzo Chemicals Inc., Product CataJog, Bulletm Mo. 88-57, incorporated by reference. Preferred diacyl peroxides herein either purely or formulated for granule, powder or tablet forms of the blotting compositions constitute solids at 25 ° C, e.g. the powder form CADETC *) BPO 78 of debenzoyl peroxide, from Akzo. Preferred organic peroxides, especially diactium peroxides, for such bleaching compositions have melting points above 40 ° C, preferably above 50 ° C. Additionally, organic peroxides with SADTs (as defined in the preceding Akzo publication) of 35 ° C or more, most preferably 70 ° C or more are preferred. Some non-limiting examples of diacyl peroxides useful herein include dibenzoyl peroxide, lauroyl peroxide, and dicynyl peroxide. The dibenzoyl peroxide is preferred. In some cases, diacyl peroxides are commercially available which contain substances such as dioctyl phthalate. In general, particularly for automatic dishwashing applications, it is preferred to use diactyl peroxides which are substantially free of fatty phthatates since these can form spots on dishes and glassware. Substituted Quaternary Bleach Activators -The present combinations also contain substituted Quaternary bleach activators (QSBA). The QSBAs are further illustrated in the U.S. Patent. 4,539,130, September 3, 1985, and the U.S. Patent. No. 4,283,301. British Patent 1,382,594, published on February 5, 1975, discloses a class of QSBA optionally suitable for use herein. The Patent of E.U.A. 4,818,426 issued April 4, 1989 describes another class of OSBA. See also the U.S. Patent. 5,093022 published March 3, 1992 and 4,904,406, issued on February 27, 11990. Additionally, the QSBAs are described in EP 552, 812 Al published on 28 July 1993, and EP 540,090 A2, published May 5, 1993. Detergency builders - Builders may optionally be included in the compositions herein to help control the hardness of minerals. Inorganic and organic builders can be used. Builders are typically used in fabric washing compositions to help remove particulate soils. The level of detergent reduction can vary widely depending on the final use of the composition and its desired physical form. When present, the compositions * will typically comprise at least about 1% detergency builder. Granulated formulations typically comprise about 1"!" at about 80%, typically about 15% at approximately the weight of the detergency builder. However, lower or higher detergency builder levels are not excluded. Detergents for detergents for inorganic detergents and containing P include, but are not limited to, the alkali metal, ammonium and canola salts or polyphosphate salts (exemplified by phosphorus, pyrophosphate and glassy polymetallic meta-phosphates). , phosphonates, phytic acid, silicates, carbonates (including bicarbonates and sesquicarbonates), sulphates and aluninosilicates. However, phosphate builders are required in some scenarios. Importantly, the compositions herein work surprisingly well even in the presence of so-called "weak" detergency builders (compared to phosphates) such as treatment, or in the so-called "subconstruction" situation that could occur- with rne Zeolite or silicate builders are ratified. Examples of silicate builders are alkali metal silicates, particularly those having a ratio of S 2: Na 2? in the scale from 1.6: 1 to 3.2: 1 and layered silicates, such as the layered sodium silicates described in U.S. Patent 4,664,839, issued May 12, 1987 to H. P. Riec. NaSKS-6 is the trade name for a crystalline layered silicate sold by Hoechst (commonly abbreviated as "SK -6"). Unlike zeolitj builders, the NaSKS-6 silicate builder does not contain aluminum. NaSKS-6 has the morphological form of stratified silicate delta-Na2S? 0s and can be prepared by all such as those described in German Application DE-A-3,417,649 and DE-A-3, 742, 043 SKS-6 is highly preferred ratified silicate for use herein, but other layered silicates, such as those having the general formula NaMSi 2x +? yH2? wherein M is sodium or hydrogen, x is a number from 1.9 to 4, preferably 2, and y is a number from 0 to 20, preferably 0 may be used herein. Some other stratified silicates from Hoechst include NaSKS-5, NaSK5-7 and NaSKS-11 as the alpha, beta and gamma forms. Other silicates can also be used, such as magnesium silicate, which can serve as a tightening agent in granulated formulations, as a stabilizing agent for oxygen bleaches, and as a component of foam control systems. Examples of carbonate detec- tion enhancers are alkali metal and alkali metal carbonates as described in German Patent Application No. 2,321,001 published November 15, 1973. 5e Sodium carbonate grades and types can be used. and sodium sesquicarbonate, vanes of which are particularly useful as carrier-is of other ingredients, especially detersive surfactants. The detergents of detergents are useful in the present invention. The aluminosilica detergent builders are of great importance in most heavy duty granular detergent compositions currently marketed, and can also be an important detergency ingredient in liquid detergent formulations. Alurinosilicate builders include those that have the empirical formula: Mz (zAl? 2) and 3xH2 ?, where z and y are integers of at least 6, the molar ratio of zay is on the scale of about 1.0 to about 0.5 , and x is an integer from about 15 to about 264. Useful alurninosilicate ion exchange materials are commercially available. These can be of crystalline or amorphous structure and they can be naturally occurring or synthetically derived. A method for producing alummosilicate ion exchange materials is described in US Pat. No. 3,985,669, Kru rne] and others issued on October 12, 1976. Preferred synthetic alumino-illate ion exchange materials useful herein are available under the designations Zeolite A, Zeolite P (B), Zeolite MAP and Zeolite X. In a particularly preferred embodiment, the crystalline aluminosilicate ion exchange material has the formula: ai2 HA102) i2 (S1O2) i2 HxH2? where x is around - from 20 to about 30, special I ment of 27. The material is known as Zeolite A. Dehydrated zeolites (x = 0 - 10) can also be used herein. Preferably, the alummosilicate has a particle size of about 0.1-10 microns in diameter. Organic builders suitable for the purposes of the present invention include, but are not limited to, a wide variety of polycarboxylate compounds. As used herein, "polycarboxylates" refers to compounds having a plurality of carboxylate groups, preferably at least 3 carboxylates. Polycarboxylate builders can generally be added to the composition in acid form, but can also be added in the form of a neutralized salt. When used in the salt form, alkali metals such as sodium, potassium and lithium, or alkanola onium salts are preferred.

Included among the poly carboxylate detergent builders are a variety of useful material categories. An important category of poly carboxylate detergency builders include ether polycarboxylates, including oxydisuccina, as described in Berg, US Patent 3,128,287, issued April 7, J964, and Lamberti et al., US Patent 3,635,830. , issued on January 18, 1972. See also "TMS / FDS" detergent builders of U.S. Patent 4,663,071, requested from Bush et al. on May 5, 1987. Suitable ether polyboxes also include cyclic compounds , particularly aicyclic compounds, such as those described in US Patent 3,923,679; 3,835,163; 4,158,635; 4,120,874 and 4,102,903. Other useful builders include the hydroxypolycarboxylates of ether, copolymers of rhenal anhydride with ethylene or vinyl methyl ether, 1,3,5-tphi-drox-benzene-2,4,6-tri-sulfonic acid, and carboxymethyl loxysuccinic acid. , the vain metal salts of alkali, ammonium and substituted ammonium of polyacetic acids such as ethylendia m tetraacetic acid and methylploacetic acid, as well as polycarboxylates, or methyl acid, succinic acid, oxydi succinic acid, polyalielic acid, acid 1,3,5-tpcarboxylic benzene, carboxymethyoioxyacid, and soluble salts thereof. The citrate detergency builders, eg, citric acid and soluble salts thereof (particularly sodium salt), are polycarboxylate builders of particular importance for heavy duty liquid detergent formulations because of their ready availability. of renewable resources and their biodegradability. The citrates can also be used in granular compositions, especially in combination with aeolith and / or layered silicate builders. Sodium oxides are also especially useful in such compositions and combinations. Also suitable in the detergent compositions of the present invention are the 3,3-d-carboxy-4-oxa-1, 6-hexanedioates and the related compounds described. in the US patent No. 4,566,984, Bush, issued January 28, 1986. Useful succinic acid detergency enhancers include succinic alkyl acids and C5-C20 uenyl and salts thereof. A particularly preferred compound of this type is dodecenylsuccinic acid. Specific examples of succime builders include: laupl scycium, mip stilsuccinate, palrnithylsuccinate, 2-dodecemlsuccinate (preferred), 2-pentadecenylsuccina and the like. Lauplsuccinates are the preferred detergency builders in this group, and are described in European patent application 86200690.5 / 0,200,263, published on November 5, 1986. Other suitable polycarboxylates are described in the U.S.A. 4,144,226, Crutehfiel et al., Issued March 13, 1979 and in the U.S. patent. 3,308,067, üiehl, issued March 7, 1967. See also Patent of U.S.A. Diehl, 3,723,322. Fatty acids, e.g., rnonocarbox acids lios of C12-C18, can also be incorporated into the compositions by themselves, or in combination with the aforementioned detergency builders, especially citrate and / or succinating builders, to provide additional builder activity. Such use of fatty acids will generally result in decreased foaming, which would be considered by the fornulator. In situations where phosphorus-based builders can be used, and especially in the bar formulations used for hand-washing operations, various alkali metal phosphates such as the well-known sodium tppoli osphates, pyrophosphate, can be used. of sodium and sodium orthophosphate. Phosphonate builders can also be used as ethan-1-hydroxy-1,1-d? phosphonate and other known phosphonates (see, for example, U.S. Patents 3,159,581, 3,213,030, 3,422,021, 3,400,148 and 3,422,137). Chelating Agents - The detergent compositions of the present invention may also optionally contain one or more chelating agents of iron and / or manganese and / or copper, e.g. acetic acid diethylenetria mopentaacet ico (AüfP).

More generally, chelating agents suitable for use herein may be selected from the group consisting of oxycarboxylates, polyphosphonates, poly-substituted aromatic chelating agents, and mixtures of the same. Without pretending to be limited by theory, it is believed that the benefit of these materials is due in part to their exceptional ability to separate iron and manganese ions from wash solutions through the formation of soluble chelates; Other benefits include the prevention of inorganic films or pellets. Other chelating agents for use in the present are the DEQUEST (R) commercial senes and the chelators of Monsanto, DuPont and Naleo. The arnmocarboxylates useful as chelating agents include ethylene tert-acetates, N-hydroxyethylene dianatriacetates, nitroyl acetates, lendiary-nitro-propionates, t-ethyl-erethameth-acetaacetates, ethylene-n-pentane-phenacetates and ethylene glycines, alkali metal salts, ammonium and substituted ammonium thereof and mixtures thereof. The ammophosphonates are also suitable for use as chelating agents in the compositions of the invention when at least two levels of total phosphorus are allowed in detergent compositions, and include ethylene dialysis (methylphosphonates) with DEQUEST. It is preferred that these arninophosphonates do not contain alkyl or alkenyl groups with more than six carbon atoms. Poly-functionally substituted aromatic chelating agents are also useful in the compositions herein. See patent of E.U.A. 3,812,044, issued May 21, 1974 to Connor and others. Preferred compounds of this type in the form of acid are the dihydroxy disulfobenzenes, such as 1,2-d? H? Drox? -3,5-d? Solfobenzene. A preferred biodegradable chelator for use herein is ethylene diamine discinaccine (EDDS), especially the CS isomer, Sl described in U.S. Pat. 4, ^ 04,233, on November 3 to Hartrnan and Per ns. If used, these chelating agents will generally comprise from about 0.1% to about 10% by weight of the detergent compositions herein. Most preferably the chelating agents will comprise from about 0.1% to about 3.0% by weight of said compositions. Enzymes - Enzymes can be included in the < b, formulations herein for a wide variety of laundry purposes of fabrics, including, for example, the removal of protein-based stains, based on carbohydrates or triglycerides, and to prevent the transfer of migratory dyes and restoring fabrics. Enzymes to be incorporated include proteases, amylases, lipases, cellulases and peroxidases, as well as mixtures thereof. Other types of enzymes can also be included. They can be of any suitable origin, such as vegetable, animal, bacterial, mycotic and yeast origin. However, their choice is governed by many factors such as pH activity and / or optimum stability, thermal stability, stability against active detergents, detergency enhancers, etc. In this regard, bacterial and fungal enzymes, such as bacterial amylases and proteases and fungal cellulases, are preferred. Enzymes are normally incorporated at levels sufficient to provide up to about 5 mg by weight, very typically from about 0.01 mg to about 3 mg of active enzyme per gram of composition. In other words, compositions of the present typically comprise from about 0.001% to about 5%, preferably 0.01% -1% by weight of a commercial enzyme preparation. Protease enzymes are commonly present in such commercial preparations at levels sufficient to provide 0.005 to 0.1 Anson units (AU) of activity per gram of composition. Suitable examples of proteases are eubtiii ciñas that are obtained from particular strains of B.subtil i s and B.lichem forrns. Another suitable protease is obtained from a Bacillus strain that has maximum activity throughout the pH regime of 8-12, developed by Novo Indudtnes A / S under registered JA ESPERASE. The preparation of this enzyme and analogous enzymes is described in British Patent Specification No.1,243, 784 by Novo. The commercially available proteolytic enzymes suitable for removing protein-based stains include those sold under the trademarks ALCALASE and SAVINASE of Novo Industries A / S (Denmark) and MAXATASE of International Bio-Synthetics, Tnc. (Netherlands). Other proteases include Protease A (see European Patent Application 130,756 published January 9, 1985) and Protease B (see European Patent Application No. of Sene 87303761.8, filed April 28, 1987 and the European Patent Application. 130,756, Bott et al., Published on January 9, 1985). A preferential protease, referred to as "Protease D" is a variant of carbonylhydrolase having an amino acid sequence not found in nature, which is derived from a carbonylhydrolase precursor by replacing a different amino acid with a multitude of amino acid residues at a position of said equivalent lhydrolase carbon to position +76 in combination with one or more amino acid residue positions equivalent to those selected from the group q? e consists of +99, +101, +103, +107 and +123 in the subtiiism Bacill? s arnyloliquefaciens , co or described in the patent applications of A. Baec, OK Ghosh, P.P. Greycar, R.R. Bott and L.J. Uilson, entitled "Protease-Contai ni ng Cleaning Cornpositions" which has the Sene No. of E.U.A. 08 / 136,797 (Case 5040 of P &G), and "Bleachmg Co positions Co prismg Protease Enzymes" which has the Serial No. E.U.A. 08 / 136,626. Amylases include, for example, or-arnilases described in British Patent Specification No. 1,296, 839 (Novo), RAPIDASE, International Bio-Syntheti, Inc. and TERMAMYL. The cellulases usable in the present invention include both bacterial and fungal cellulases. Preferably, they should have an optimum pH of between 5 and 9.5. Suitable cellulases are described in the U.S.A. 4,435,307, Barbesgoard et al., Issued March 6, 1984, which describes fungal cellulase produced by Hú icola msolens and chain Hurnicola DSM1800 or a cellulase fúngiea 212 producer belonging to the genus Aerornonas, and cellulase extracted from the hepatopancreas of a mollusk marine (Dolabella Auricular Solander). Suitable cellulases are also described in GB-A-2,075,028; GB-A-2,095,275 and DE-OS-2,247,832. The CAREZYME (Novo) ee especially u il. The enzymes or raisins suitable for use in detergents include those produced by microorganisms of the Pseudomonas group, such as Pse? Domona stutze i ATCC 19. 154, as described in British Patent 1,372,034. See also lipasae in Japanese Patent Application 53,20487, open for public inspection on February 24, 1987. This lipase is available from Amano Pharrnaceutical Co. Ltd., Nagoya, Japan, under the registered trademark Lipasa P "Amano ", which is hereinafter referred to as" Amano-P ". Other commercial lipases include Arnano-CES, Jipases from ex Chrornobacter viscosu, e.g. Chromobacter viscosum var. lipolycturn NRRLB 3673, available commercially from Toyo Jozo Co., Tagata, Japan; and also the Chromobacter viscosum lipases from U.S. Boichemical Corp., E.U.A. and Disoynth Co., The Netherlands, and the lipases of ex Pseudomonas gl dioli. The LIPOLASE enzyme derived from Hurnicol lanuginosa and which is commercially available from Novo (see also EPO 341,947) is a preferred lipase for use herein. Peroxidase enzymes are used in combination oxygen supplies, V.gr., percarbonate, perborate, persulfate, hydrogen peroxide, etc. They are used for "bleaching solutions", that is, to avoid transfer of dyes or pigments removed from the substrates during the washing operations to other substrates in the washing solution. Peroxidase enzymes are known in the art and include, for example, ruminal peroxidase, ligmnasa and halogenoperoxidase such as chloroperoxidase and bromoperoxidase. Detergent compositions containing peroxidase are described, for example, in International Application PCT UO 89/099813, published October 19, 1989 by 0. Kirk. assigned to Novo Industries A / S. A wide variety of enzyme materials and means for their incorporation into synthetic detergent compositions are described in the U.S. Patent. 3,553,139 issued on January 5, 1971 to McCarty et al. Additionally, enzymes are described in the U.S. Patent. 4,101,457, Place et al., Issued July 18, 1978 and < The Patent of E.U.A. 4,507,219, Hughes, both issued March 26, 1985. Enzyme materials useful for liquid detergent formulations and their incorporation into such formulations are described in the U.S. Pat. 4, 261,868, Hora et al., Issued April 14, 1981. Enzymes for detergents can be stabilized by various techniques. Enzyme stabilization techniques are described and illustrated in the U.S. Patent. 3,600,319 issued August 7, 1971 to Gedge, et al., And in European Patent Application Publication No. O 199 405, Application No.86200586.5, published October 29, 1986, Venegas. Enzyme stabilization systems are also described, for example, in the U.S. Patent. 3,519,570. Polymeric Dirt Release Agents - Any polymeric soil release agent known to those of skill in the art may optionally be employed in the compositions and methods of this invention. The polymeric dirt release agents are characterized by having both hydrophilic segments, to hydrophilize the surface of the hydrophobic fibers, such as polyester and nylon, and hydrophobic segments to deposit on the hydrophobic fibers and remain adhered thereto by the termination of the hydrophobic fibers. the washing and rinsing cycles and, in this way, serve as an anchor for these hydrophilic segments. This may allow stains that are present after a treatment with the soil release agent to be more easily cleaned in subsequent washing procedures. Polymeric soil release agents useful herein include especially those soil release agents that have: (a) one or more nonionic hydrophilic components that consist especially of (i) polyacetylene segments with a degree of polyvailability of - at least 2, or di) oxypropylene or polyoxypropyl segments or with a degree of polymerization of 2 to 10, wherein said hydrophilic segment does not encompass any oxypropylene unit unless it is attached to the adjacent positions at each end by ether linkages, or (m) a mixture of oxyalkylene units containing oxyethylene and from 1 to about 30 oxypropylene units wherein said mixture contains a sufficient quantity of full oxie units such that the hydrophilic component has hydrophilicity sufficiently large to increase the hydrophilicity of the conventional surfaces of synthetic polyether fibers on the deposit of the agent of dirt release on such a surface, said hydrophilic segments probably containing at least about 25% oxyethylene units and very preferably, especially for such components having approximately 20 to 30 oxypropylene units, at least about 50% oxyethylene units; or (b) one or more hydrophobic components containing (i) segments of C3 oxyalkylene terephthalate, wherein, if said hydrophobic components also contain oxyethylene terephthalate, the ratio of oxytene terephthalate units to those of oxyalkylene terephthalate C3 is about 2: 1 or less, (ii) the C4-C6 alkylene segments or C-C6 oxyoalkylene or mixtures thereof, (111) polyvinyl ether segments, preferably polyvinyl acetate, having a degree of polymerization of at least 2, or (iv) substituents of ether to the Ci-C4-cyclic or C4-hydroxyalkyl ether, or mixtures thereof, wherein said substituents are present in the form of alkyl Ci-C4 ether with derivatives of C4 alkyl hydroxyl ether celluloses, or mixtures thereof and such cellulose derivatives are amphiphilic, whereby it has a sufficient level of C1-C4 alkyl ether units and / or C4 hydroxyalkyl ether to be deposited therein. on the conventional surfaces of synthetic polyester fiber and retain a sufficient level of hydrophilic, once adhered to such conventional synthetic fiber surfaces to increase the hydrophilicity of fiber surface, to a combination of (a) and () . Typically, the polyacrylate segments of (a) (.?) Will have a degree of polymerization of about 200, although higher levels may be used, preferably from 3 to about 150, most preferably from 6 to approximately 100. Some hydrophobic segments of suitable oxyalkylene C-C include, but are not limited to, extreme ends of poly-material release agents such as M03S (CH2) nOCH2CH2? -, where M is sodium and n is an integer of .sup.-6, as described by the USA 4,721,580 issued January 26, 1988 to Gossel nk. Polluting soil release agents useful in the present invention also include cellulose derivatives such as hydroxy ether cellulosic polymers, copolyme copolymer blocks of ethylene terephthalate or propylene terephthalate with polyethylene oxide or polypropylene oxide terephthalate, and the like. Such agents are commercially available and include cellulose hydroxyethers such as METHOCEL (Dow). Cellulosic soil release agents for use herein also include those selected from the group consisting of C-alkyl, C 1 -C 4 alkyl and C 4 hydroxyalkyl; see the Paternal < - US 4,000,093, issued December 28, 1976 to 1N.I.O1 et al. Dirt release agents characterized by hydrophobic segments of polyvinyl ester include polyvinyl ester graft copolymers, for example, vinylic esters Ci-Cβ, preferably polyvinyl acetate grafted onto polyalkylene oxide base structures, such as polyethylene oxide base structures, see European Patent Application 0 219 048, published April 22, 1987 by Kud et al. Some commercially available dirt release agents of this kind include SOKALAN material type, for example, SOKALAN HP-22, available from BASF (West Germany) One type of preferred soil release agent is a block copolymer. of ethylene terephthalate and polyethylene oxide terephthalate (PEO) .The molecular weight of this polymeric dirt release agent is on an ap about 25,000 to about 55,000. See U.S. Pat. 3,959,230 to Hays, issued May 25, 1976 and the Patent of L.U.A. 3,893,929 to Basadur issued July 8, 1975. Another preferred polimepco soil release agent is a polyester with repeating units of ethylene terephthalate units containing 10-15% by weight of ethylene terephthalate units together with 90% by weight. -80% by weight of units of polyexylate terephthalate, derived from a polyexyethylene glycol of average molecular weight 300-5,000. Some examples of this polymer include the available corneal material ZELCON 5126 (from Dupont) and MILEASE T (from IC1). See also U.S. Patent 4,702,857, issued October 27, 1987 to Gosselmk. Another agent p >The preferred dirt release oligomer is a sulphonated product of a substantially linear ester oligomer consisting of an oligomeric ester base structure of terephthaloyl and oxyalkylenoxy repeating units and terminal portions covalently bonded to the base structure. These soil release agents are described in detail in the US patent. 4,968,451, issued November 6, 1990 to J.J. Scheibel and E.P. Gosselink. Other suitable polymeric soil release agents include the terephthalate polyesters of the U.S. Patent. 4,711,730, issued December 8, 1987 to Gosselmk et al., The oligo-epic esters of extreme finishing of the U.S. Patent. 4,721,580, issued on January 26, 1988 to Gosselink, and the oligomeric polyester-block compounds of the U.S. Patent. 4,702,857, issued October 17, 1987 to Gosselink. Preferred polyfunctional release agents also include the soil release agents of US Pat. 4,877,896, issued on October 31, 1989 to Maldonado et al., Which describes ammonium end-capped terephthalate esters, especially sulphonates. A further preferred dirt release agent is an oligo with repeating units of terephthaloyl units, sulfoi soterephthaloyl units, oxyethyleneoxy units and ox? -1, 2-propylene. The repeating units form the base structure of an oligomer and are preferably terminated with end-caps of modified isethionate. A particularly preferred soiling release agent of this type consists of approximately 1 unit of sulfoi sotaloyl, 5 units of terephthaloyl, units of oxyethenoxy and ox? -1, 2-propylenenoxy in a ratio of about 1.7 to about 1.8, and two end cap units of sodium 2- (2-hydroxylethoxy) ethanesulphonate. These sulfur end cap release agents also contain from about 0.5% to about 20%, the weight of the oligomer, of a crystalline reducing stabilizer, preferably selected from the group consisting of sulfonate, xylene, sulfonate of eumeno, toluene sulfonate, and mixtures thereof. If the soil release agents are used they will typically contain from about 0.01% to about 10.0% by weight, of the detergent compositions herein, typically from about .L% to about 5%, preferably from about 0.2% to approximately 3.0%. Other Ingredients - The usual detersive ingredients may include one or more other detersive detersive materials to help enhance the performance of the cleaner, the treatment of the substrate to be cleaned, or to modify the aesthetics of the detergent composition. The usual detersive adjunct materials of the detergent compositions include the ingredients set forth in the U.S. Patent. No.3, 936, 537, and others. The adjunct materials that can also be included in the detergent compositions employed in the present invention, at their conventional levels established in the art for use (generally from 0% to about 20% of the detergent ingredients, preferably of about 0.5% to about 10%), include other active ingredients such as dispersing polymers from BASF Corp. or Rohm to Haas; color smears, anti-rust and / or anti-corrosion agents, dyes, fillers, optical brighteners, germicides, alkalinity sources, hydrotropes, antioxidants, penis stabilizing agents, perfumes, solubilizing agents, dirt removal agents and anti-rredeposition agents clay, vehicles, processing aids, pigments, solvents for liquid formulations, fabric softeners, static control agents, solid fillers for bar compositions, etc. Dye migration inhibiting agents, including polyamide N-oxides such as polyvinyl-N-oxide, can be used. The color migration inhibiting agents above are amply illustrated by polyvinylpyridone and copolymers of N-irn dazo and N-vi-mlpyrplidone. If a high foaming is desired, foam creamers such as Cio-Ciß alkanolarnides can be incorporated into the compositions, typically at levels of 1% -10%. Cio-C1 inenoethanol and diethanolamides illustrate a typical class of such foam improvers. The use of foam boosters with high foaming surfactants such as the amines, betaines and sultams mentioned above is also advantageous. If desired, soluble magnesium salts such as MgCl 2, MgS 4 and the like can be added, typically at levels of 0.1% -2%, to provide additional foam and to improve the fat removal performance. Brightener - Any optical brighteners or brighteners or whitening agents known in the art can be incorporated at levels typically from about 0.05% to about 1.2% by weight, in the detergent compositions herein. Commercial optical brighteners that may be useful in the present invention can be classified into subgroups, including, but not necessarily limited to, stilbene derivatives, pyrazoline, curnapna, carboxylic acid, ethmocyanates, dibenzothiophon-5-dioxide, azoles, heterocyclics of 5 and 6 members, and other diverse agents. Examples of such brighteners are described in "The Production and Application of Fluorescent Bpghtenmg Agents," M. Zahrad ik, published by John Uiley & amp;; Sons, New York (1982). Specific examples of optical brighteners that are useful in the present compositions are those identified in the U.S.A. 4,790,865 issued to Uixon on December 3, 1988. These brighteners include the PHOROWHITE polishing system from Verona. Other brighteners described in this reference include Ti nopal UNPA, Tinopal CBS and Tmopal 5BM; available from Ciba-Geigy; Artic White CC and Artic Uhite CUD, available from Hi lton-üavis, based in Italy; 2- (4-est? r? l-phen? l) -2H-naphthoCl, 2-d] tr.iazol.es; 4,4'-bis (1, 2,3-triazol-2-yl) -stilbenes; 4,4'-bisteethyryl) bi .sphenyls; and the aminocurnariñas. Specific examples of these brighteners include 4 ~ metii-7-diet.i.l-arninocurnariña; 1,2-bis (benzhnidazol-2-yl) ethylene; 1,3-diphenyl-pyrazolines; 2,5-bis (benzoxazol-2-yl) thiophene; 2-estiri.L-naphtholll, 2-dloxazole; and 2- (stilben-4-yl) -2H-naphtho-Cl, 2-dUtriazoi. See also patent of E.U.A. 3,646,015, issued February 29, 1972 to Hamilton. Here anionic brighteners are preferred. Various detersive ingredients employed in the present compositions can optionally be further stabilized by absorbing said ingredients on a porous hydrophobic substrate, subsequently coating said substrate with a hydrophobic coating. Preferably, the detersive ingredient is mixed with a surfactant before being absorbed into the porous substrate. During use the detersive ingredient is released from the substrate in the aqueous washing liquid, where it performs its desired detersive function. To illustrate this technique in more detail, a porous hydrophobic silica (trade name SIPERNAT DIO, Degussa) is mixed with a proteolytic enzyme solution containing 3% -5% nonionic ethoxylated alcohol surfactant of Ci3-i5 (EO 7). ). Typically, the enzyme / surfactant solution is 2.5X ee of silica. The resulting powder is dispersed with agitation in silicone oil (various viscosities of silicone oil can be used in the range of 500-12,500). The resultant ilicon oil dispersion is e ulsified or otherwise added to the final detergent matrix. By this means, ingredients such as enzymes, bleaches, bleach activators, bleach catalysts, photoactivators, colorants, fluororecers, fabric conditioners and hydrolyzable surfactants mentioned above can be "protected" for use in detergents, including liquid laundry detergents. . Bleaching compositions in granular form typically characterize the water content, for example, to less than about 12% free water, for better storage stability. The storage stability of the bleaching detergent compositions can still be enhanced by limiting the content of the compositions of active adventitious substances in oxidation reduction reactions such as rust and other indications of transition metals in an inconvenient manner. Certain bleaching compositions may be further limited in their total content of halogen ions, or any particular halogen may be substantially absent, e.g. bromide. Bleaching stabilizers such as stanols can be added for improved stability and liquid formulations can be substantially non-aqueous if desired.

The following examples illustrate the bleach activators of the invention and the bleach detergent compositions which can be prepared using the bleach activators, but are not intended to be limiting thereof. All the material of the examples I-XXX satisfy the functional limitations in the present.

EXAMPLE I N- 1 - (METILSULFONIL) BENZ0IL.1CAPROLACTAMA All the glassware is dried perfectly and the reaction is maintained under an inert atmosphere (argon) all the time. While stirring, 5.0 g (25.0 mmol) of (4-ethylsulfonyl) benzoic acid (Aldrich) and 5.5 L (75.0 mmol) of thionyl chloride (Aldpch, d = 1631 </ nol), are added at 100 rnL of tetrahydrofuran. (THF - Aldrich, HPLC grade) in a three-necked round bottom flask equipped with reflux condenser, addition funnel and magnetic stirrer. The resulting reaction mixture is heated to reflux and stirred for 16 hours. After cooling to room temperature, the solvent and excess thionyl chloride are removed by evaporation under reduced pressure. The recrystallization of the solid residue of toluene followed by drying at high vacuum produces a pure (4-rnet? Isulfom 1) benzoyl chloride as a white crystalline solid.

In a subsequent reaction, 2.33 g (20.6 mmol) of caprolactam (Aldrich) and 2.30 g (22.7 mmol) of tr-? Et iam? Na (Aldrich, d = 0.726 g / mol) are added, at 50 nm of THF ( Aldrich, HPLC grade) in a three-necked round bottom flask equipped with a reflux condenser, addition funnel and magnetic stirrer. The addition of a solution of 4.50 g (20.6 mmol) of the (4-rnet? Is? Lfo l) -benzoyl chloride in 50 rnL of T? F precedes dropwise over a period of 30 minutes and the mixture is heated The resulting reaction is refluxed and stirred for 16 hours. After cooling to room temperature, the THF is removed by evaporation under reduced pressure, the solid residue is dissolved in chloroform and extracted several times with distilled water, the organic layer is dried over a2 SO4, filtered, concentrated The precipitate is collected by suction filtration, rinsed with hexane and dried in vacuo to give NC (4-rnet? lysulonyl) benzole] caprolact as a solvent. solid white, crystalline.

EXAMPLE II N- [(-METILSULFONIL? BENZOIL3 VALEROLACTAMA It is synthesized as N-1"(4-methylsulphyl) -benzoyl caprolact ma (Example 1) using valerolact ma (Aldrich) in place of caprolactam.

EXAMPLE III N-C (4-METHYL-5-PHONYL) BENZOIL-3-VALEROLACTAMA The synthesis of NL "(4-eti.isufononyl) benzoyl Kcapro-lactarna proceeds as for the NC (4-methylisulfonyl) benzoyl] -caprolactam (Example I) using (4-ethylsui fon.l) benzoic acid instead of (4-rnetisulphonyl) benzoic acid) (4-Ethyl-sulphonyl) benzoic acid can be synthesized from 2-chloropropionic acid and 4- (chlorosul-fonyl) benzoic acid according to the procedure, by Brown, R.

U. J. Org. Che. 1991, 56, 4974-4976.

EXAMPLE IV N-C (4-ETILSULFONIL) BENZOIL3VALEROLACTAMA It is synthesized as for N-C (4-ethyl-sulphonyl) -benzoyl-U-procactam (Example III) using valerolactar (Aldrich) instead of caprolactam.

EXAMPLE V N- [(4-PENTILSULFONIL) BENZOIL3CAPR0LACTAMA It is synthesized as for N-C (4-ethylhexyl) -benzoylcaprolactam (Example III) using 2-brornohexanoic acid (Aldrich) instead of 2-chloropropionic acid.

EXAMPLE VI N-C (4-PENTILSULFONIL) BENZOIL3VALEROLACTAMA It is synthesized as for N-C (4-? Ent? I sulfoml) -benzole lUcaprolactam (Example V) using valerolactar (Aldrich) in place of caprolactam.

EXAMPLE VII N-C -HEPTISTIFQNIL) BENZOIL3CAPROLACTAMA It is synthesized as for N-C (4-et? Lsulfoni-1) -benzole-13-caprolactam (Example III) using 2-bromooctanoic acid (Aldrich) in place of 2-chloropropion? Co acid.

EXAMPLE VIII N-C (4-HEPTILSULFONIL) BENZOIL3VALEROLACTAMA It is indicated as for the N-C (4-heptyisul fom l) -benzoyl or caprolacta a (Example VID using valerolactam (Aldri ch) instead of caprolactane.

EXAMPLE EX N- (2-FUROIL) VALEROLACTAMA All the glassware is dried perfectly and the reaction is maintained under an inert atmosphere (argon) all the time. While stirring, 20.0 g (0.18 mol) of 2-phoronic acid (Aldrich) and 40.0 rnL (0.53 nmol) of thionyl chloride (Aldpch, d = 1631 g / mol) are added, at 300 rnL of THF (Aldrich). , HPLC grade) in a single neck, round bottom flask equipped with a reflux condenser and magnetic stirrer. The resulting reaction is heated to reflux and stirred for 16 hours. After cooling to room temperature, the solvent and excess thiom chloride are removed by evaporation under reduced pressure to give 2-furole chloride. In a subsequent section, 9.2 g (92 mmol) of valerolacta are added (Aldrich and 14.1 inL (101 rnrnol) triethylanine (Aldrich, d = 0.726 g / mol), to 150 rnL of THF (Aldrich, HPLC grade) in a Three-necked round bottom flask, equipped with reflux condenser, addition funnel and magnetic stirrer.Addition of a solution of J2.0 g (H2 mrnol) of furoyl chloride in 150 rnL of TI-IF proceeds got exhausts for a period of 30 minutes and the resulting reaction mixture is heated to reflux and stirred for 16 hours, after cooling to room temperature, the THF is evaporated off under reduced pressure, the residue solid in chloride is redissolved. of ethylene and extracted several times with 5% aqueous hydrochloric acid and then deionized water, the organic layer was dried over Na 2 SO 3, filtered, concentrated by removal of the solvent and poured into hexane to precipitate the product. The precipitate is collected by suction filtration, rinsed with h exano and dried in vacuo to give N- (2-furoyl) valerolactam as a white, crystalline solid.

EXAMPLE X N- (2-FUROIL) CAPROLACTAMA It is synthesized as for N- (2-furoi.J.) Valerolactam (Example IX) using caprolactam (Aldrich) instead of valerolactam.

EXAMPLE XI N- (3-FUROIL) CAPROLACTAMA It is synthesized as for N- (2-furoyl) caprolactam (Example X) using 3-furoic acid in place of 2-furoic acid.

EXAMPLE XII N- (3-FUROIL) VALEROLACTAMA It is synthesized as for the N- (3-furoyl) calolactan (Example XI) using valerolactam (Al dri ch) in caprolactam.

EXAMPLE XIII N- (5-NITRO-2-FUROIL) CAPROLACTAMA It is synthesized as for the N- (2-furoil) cap rolactarna 7J (Example XI) using 5-n-2-furo-co acid in place of 2-urea ico acid.

EXAMPLE XIV N- (5-NITRO-2-FUROIL) VALERQLACTAMA It is synthesized as for N- (5-mt ro-2-furoi 1) caprolactam (Example XTIT) using valerolactam (Aldrich) instead of caprelactane.

EXAMPLE XV N- (5-BROMO-2-FUROIL) CAPROLACTAMA It is synthesized with caprolactane N- (2-furo? 1) (Example X) using 2-phoric acid 5-brornox instead of 2-phoric acid.

EXAMPLE XVI N- (5-BROMINE-2-FUROIL) VALEROLACTAMA It is synthesized as for N- (5-brorno ~ 2-furoyl) caprolactam (Example XV) using valerolactam (Aldrich) in place of caprolactam.

EXAMPLE XVII N- (1-NAFTOIL) CAPROLACTAMA It is synthesized as for N- (2-uroyl) caprolactam (Example X) using 1-natoic acid in place of 2-furoic acid.

EXAMPLE XVIII N- (1-NAFTOIL) VALEROLACTAMA It is synthesized as for N- (1-n to.l) -caprolactam (Example XVII) using valerolactam (Aldrich) in place of caprolactam.

EXAMPLE XIX N- (3, 5-DINITR0BENZ0IL) CAPROLACTAMA All the glassware is dried perfectly and the reaction is maintained under an inert atmosphere (argon) all the time. While stirring, 2.33 g (20.6 mmol) of caprolactam (Aldrich) and 2.30 g (22.7 mmol) of triethylamine (Aldrich, d = 0.726 g / mol) are added at 100 rnL. of toluene (Aldrich) in a three-necked round bottom flask equipped with reflux condenser, addition funnel and mechanical stirrer to give a pale yellow, clear solution. The addition of a solution of 4.75 g (20.6 mmol) of 3,5-dini trobenzoyl chloride (Aldrich) to 100 L of toluene proceeds dropwise over a period of 30 minutes. The mixture is heated to the resulting reaction under reflux and stirred for 16 hours after cooling to room temperature., the reaction is filtered to separate the hydrochloride from tetthylamine and pour into a separating funnel. After dilution with 300 rnl of chloroform, the organic solution is extracted with 5% aqueous HCl, 5% aqueous NaOH and finally water. The organic layer is dried over Na2S? , it is filtered and the solvent is removed by evaporation under reduced pressure. The recrystallization of the crude product of toluene followed by drying in vacuo gives N- (3,5-d? Mtrobenzoyl) caprolactam as a yellow, crystalline solid.

EXAMPLE XX N- (3, 5 -DINITROBENZOIL) VALEROLACTAMA It was synthesized as for M- (3,5-d? Mt robenzoi 1) -capr-olactam (Example XIX) using valere lactam (Aldrich) instead of caprolactam.

EXAMPLE XXI N- (3, 5-DICLORQBENZOIL) CAPROLACTAMA It was synthesized as the N- (4-nitrobenzoyl) -caprolactane (Example XXIII) using 3,5-dichlorobenzoyl chloride (Aldrich) in place of 4-nitrobenzoyl chloride.

EXAMPLE XXII N- (3, 5-DICLOROBENZOIL) VALEROLACTAMA It was synthesized as N- (3,5-dichlorobenzoyl) caprolactam (Example XXI) using valerolactar (Aldrich) instead of caprolactam. Examples XXIII-XXX exemplify methods for synthesizing compounds generically described in previous references.

EXAMPLE XXIII N- C-NITROBENZOIL)) CAPROLACTAMA All the glassware was dried perfectly and the reaction was maintained under an inert atmosphere (argon) all the time. While stirring, 43.0 g (0.38 mmol) of caprolactam (Aldrich) and 58.2 L (0.42 mmol of trieti.lami.na (Aldrich, d = 0.726 g / mol) were added to 150 rnL of THF (Aldrich, HPLC grade). ) in a three-necked round bottom flask equipped with a reflux condenser, addition funnel and mechanical stirrer to give a clear pale yellow solution.The addition of a solution of 70.5 g (0.38 mol) of 4- Nitrobenzoyl (Aldrich) 100 L of THF is added dropwise over a period of 1 hour.The dark yellow, nebulous reaction mixture is refluxed and stirred for 16 hours, after cooling to room temperature, the reaction is filtered to separate the elorohi drato from tpetiiamine and pour it into a separatory funnel.After dilution with chloroform, the organic solution is extracted twice with 5% aqueous HCl, twice with 5% aqueous NaOH and finally once with the water. neutral deionized The organic layer is dried over a2 O4 or MgS? and the solvent is removed by evaporation under reduced pressure. The recrystallization of the crude product of toluene, followed by drying in vacuo, gives N- (4-mt robenzoyl) caprolactane as a crystalline solid, light yellow.

EXAMPLE XXIV N- (4-NITROBENZOIL) VALEROLACTAMA It is synthesized as for the N- (4-n? T robenzoi 1) ca? o-lactase (Example XXIII) using valerolactam (Aldrich) instead of caprolact ma.

EXAMPLE XXV N- (3-NITROBENZOIL) CAPROLACTAMA It is synthesized as for the N- (4-n? T robenzo l) ca-ro-lactarna (Example XXIIT) using 3-nitrobenzoi chloride (Aldpch) instead of 4-mtrobenzoyl chloride lo.

EXAMPLE XXVI N- (3-NITROBENZOIL) VALEROLACTAMA It is synthesized as for N ~ (3-nitrobenzoyl) caprolactam (Example XXV) using valerolactam (Aldrich) instead of caprolactna.

EXAMPLE XXVII It is synthesized as for N- (4-nitrobenzoyl) caprolactam (Example XXIII) using 3-chlorobenzoyl chloride (Aldrich) in place of 4-nitrobenzoyl chloride.

EXAMPLE XXVIII N- (3-CHLOROBENZOIL) VALEROLACTAMA It is synthesized as for N- (3-chlorobenzoyl) caprolactam (Example XXVII) using valerolactam (Aldrich) in place of caprolactane.

EXAMPLE XXIX N- (4-CHLOROBENZOIL) CAPROLACTMA It is synthesized as for N- (4-nitrobenzoyl) capro-lactam (Example XXIII) using 4-chlorobenzoyl (Aldrich) in place of 4-nitrobenzoyl chloride.

EXAMPLE XXX N- (4-CHLORINE ENZOIL) VALEROLACTAMA It is synthesized as for the N-- (4-chlorobenzoyl) caprolactam (Example XXIX using valerolactam (Aldrich) in place of the capitol.

EXAMPLE XXXI Bleaching detergent compositions which are in the form of granular laundry detergents are exemplified by the following formulations: A B C D E Bleach Activator + 2.30 2.30 3.00 4.60 2.30 Sodium Percarbonate 5.30 0.00 0.00 12.00 0.00 Perborate Monohydrate 0.00 5.30 9.00 0.00 5.30 Alkylbenzene Sodium Sodium 12.00 0.00 12.00 0.00 21.00 Linear C45AE0.6S 0.00 15.00 0.00 15.00 0.00 N-Oxide of Dimethylarnine C2 0.00 2.00 0.00 2.00 0.00 Arnidopropilbetaine C12 of 1.50 0.00 1.50 0.00 0.00 Coco N-Methylglucarnide of Palm 1.70 2.00 1.70 2.00 0.00 Di ethylhydroxy- chloride 1.50 0.00 1.50 0.00 0.00 ethylammonium C12 AE23-6.5T 2.50 3.50 2.50 3.50 1.00 Activator- Conventional 0.00 0.00 0.00 0.00 0.00 (NOBS) Activador Convenitiva 0.00 0.00 0.00 0.00 0.00 (TAED) Sodium tripolisphosphate 25.00 25.00 '.00 15.00 25.00 Ceolita A 0.00 0.00 0.00 0.00 0.00 Aerolytic Acid Copolymer 0.00 0.00 0.00 0.00 1.00 and Maleic Acid polyacrylic acid, partial- 3.00 3.00 3.00 3.00 0.00 neutralized mind. Dirt Free Agent 0.00 0.00 0.50 0.40 0.00 Carboxirneti1 cellulose 0.40 0.40 0.40 0.40 0.40 Sodium Carbonate 2.00 2.00 2.00 0.00 8.00 Sodium Silicate 3.00 3.00 3.00 3.00 6.00 Sodium Bicarbonate 5.00 5.00 5.00 5.00 5.00 Savinasa (4P) 1.00 1.00 1.00 1.00 0.60 Terrnanil (60T) 0.40 0.40 0.40 0.40 0.40 Lipolase (100T) 0.12 0.12 0.12 0.1.2 0.12 Carecima (5T) 0.15 0.15 0.15 0.15 0.15 Dietilenetriaminopenta- 1.60 1.60 1.60 1.60 0.40 (rneti len phosphonic).

Brightener 0.20 0.20 0.20 0.05 0.20 Photoblank 0.50 0.00 0.25 0.00 0.00 Phthalocyamine sulphonated zinc. MgS04 2.20 2.20 2.20 2.20 0.64 N 2S04 rest rest rest rest rest Any of the above compositions is used to wash fabrics at a concentration of 3500 pprn in water, 25 ° C and a 15: 1 aguarropa ratio. The characteristic pH is approximately 9.5, but can be adjusted by altering the ratio of the acid to the sodium salt form of the alkylbenzene sulfonate. The results are excellent, particularly with respect to bleaching as compared to the otherwise identical compositions in those which are used TAED, NOBS or benzyl leaprolactane with equal weight as a complete substitute by the essential bleach activator. In particular, novel enhanced performance bleach activators, such as those in Examples III-XII, provide superior results and are highly preferred.

EXAMPLE XXXII Whitening detergent compositions having the granular laundry detergent form are exemplified by the following formulations.

A B C D E Activator Bleach + 2.30 3.00 2.30 1.75 2.00 Sodium Percarbonate 5.30 0.00 0.00 0.00 0.00 Perborate Monohydrate 0.00 9.00 1.7.60 9.60 9.00 Sodium. Alkylbenzene sulfonate 21.00 12.00 0.00 12.00 12.00 linear. C45AE0.6S 0.00 0.00 15.00 0.00 0.00 N-Oxide of Dimethylamine C2 0.00 0.00 2.00 0.00 0.00 Amidopropilbetaina C12 of 0.00 1.50 0.00 1.50 1.50 Coconut. Palma N-Methylglucamide 0.00 1.70 2.00 1.70 1.70 Dimethylhydroxy- 1.00 1.50 0.00 1.50 1.50 ethylammonium C12 AE23-6.5T 0.00 2.50 3.50 2.50 2.50 C25E3S 0.00 4.00 0.00 4.00 4.00 Conventional Activator 0.00 0.00 0.00 1.50 0.00 (NOBS) Conventional Activator 0.00 0.00 0.00 0.00 1.00 (TAED) Tripoliefosfato from 25.00 15.00 25.00 15.00 15.00 Sodium. Ceolita A 0.00 0.00 0.00 0.00 0.00 Acrylic Acid Copolymer 0.00 0.00 0.00 0.00 0.00 and Maleic Acid.

Poliacplico acid, 0.00 3.00 3.00 3.00 3.00 partially neutralized. Release Agent 0.30 0.50 0.00 0.50 0.50 Dirt. Carboximetil cel ulosa 0.00 0.40 0.40 0.40 0.40 Carbonado de Sodium 0.00 2.00 2.00 2.00 2.00 2.00 Sodium Silicate 6.00 3.00 3.00 3.00 3.00 Bi carbonate of Sodium 2.00 5.00 '..00 5.00 5.00 Savmasa (47) 0.60 1.00 1.00 1.00 i.00 Terrnamil (60T) 0.40 0.40 0.40 0.40 0.40 Lipolase (100T) 0.12 0.12 0.12 0.12 0.12 Carecina (5T) 0.15 0.15 0.15 0.15 0.15 Acid Dietiientpamino- 0.40 0.00 1.60 0.00 0.00 pentametii enfosfo co. Abplainer 0.20 0.30 0.20 0.30 0.30 Photoblank Ftalociamna 0.25 n.oo 0.00 0.00 o.on Zinc Sul onada. MgS04 0.64 0.00 2.20 0.00 0.00 Na2S04 rest rest rest rest rest Any of the above compositions is used to wash fabrics at a concentration of 3500 ppm in water, ° C and a ratio of aguarropa of 15: J. The pH character '! is about 9.5 but can be adjusted by altering the ratio of the acid to the sodium salt form of the alkylbenene sulfonate. The results are excellent, particularly with respect to bleaching as compared to other compositions in other identical respects in which TAED, NOBS or benzoylcaprolactam in equal weight is used as a complete substitute for the essential bleach activator. In particular, the novel activator Enhanced performance bleaches, such as those in Examples III-XII, provide superior results and are highly preferred.

EXAMPLE XXXIII Bleaching detergent compositions which are in the form of granular laundry detergents are exemplified by the following formulations.

A B Bleach Activator + 2.30 4.60 Sodium per-carbonate 5.30 12. UO Sodium Perborate Monohydrate 0.00 0.00 Linear Alkylbenzene Sulfonate 1.2.00 0.00 C45AE0.5S 0.00 15.00 N-Oxide of Di ethylamine 0.00 2.00 Arnidopropilbetaina of Coco C12 1.50 0.00 Palma N-Methylglucamide 1.70 2.00 Dirnetyl Hydroxyethyl Chloride - 1.50 0.00 ammonium C12 AE23-6.5T 2.50 3.50 C25E3S 4.00 0.00 Conventional Activator (NOBS) 0.00 0.00 Conventional Activator (TAED) 0.00 0.00 Sodium Tripolisphosphate 25.00 0.00 Ceolite A 0.00 20.00 Copolymer of Acrylic Acid and 0.00 0.00 Maleic Acid. Polyacrylic acid, partially 3.00 3.00 neutralized. Dirt Release Agent 0.00 0.40 Carboxymethyl cellulose 0.40 0.40 Sodium Carbonate 2.00 0.00 Sodium Silicate 3.00 3.00 Sodium Bicarbonate 5.00 5.00 Savinasa (4T) 0.00 1.00 Termamilo (60T) 0.00 0.40 Lipolase (100T) 0.00 0.12 Carecima (5T) 0.00 0.1.5 Acid Dietilerntriarni openta (rnetilen- 1.60 Phosphonic 1.60, Brightener 0.20 0.05 Photoblanker Phthalocyanine 0.50 0.00 Zinc Sulfonated MgSO4 2.20 2..20 Na2S04 Rest rest Any of the above compositions is used to wash fabrics at a concentration of 3500 ppm in water, 25 ° C and a water: clothing ratio of 15: 1 . The characteristic pH is about 9.5 but can be adjusted by altering the proportion of the acid to the sodium salt form of the alkyl alcohol benzene. The results are excellent, particularly with respect to bleaching with comparison with identical other compositions in which it is used in equal weight as a complete substitute for the activating bleached essence. In particular, novel enhanced performance bleach activators, such as those of Examples IJI-X1I, provide superior results and are highly preferred.

EXAMPLE XXXIV The bleaching compositions having the granular laundry detergent form are identical to those of any of Examples XXXI-XXXI1I. Any of the compositions for washing fabrics under "high dirt" conditions is used. The conditions of "high dirt" are achieved in any of two possible ways. In the first step, consumer packages of excessively soiled fabrics can be used, the level of dirt being high enough that when a portion of the composition is dissolved in the presence of tap water together with the soiled fabrics in a domestic washing machine In the US, the pH of the water for washing is on scales of about 6.5 to about 9.5 pH, very characteristically about 7 to about 9.5. Alternatively, it is convenient for analysis purposes, when excessively soiled tissues are not available, to use the following procedure: the pH of the washing solution is adjusted after the dissolution of the product and the addition of the test tissue using HCl aqueous so that the pH is on the scale of about 6.5 to about 9.5 pH. The test tissues are a clean or slightly dirty lump of consumer tissues; Additional samples of test tissue containing bleaching spots are characteristically added. The fabrics are washed at about 25 ° C with excellent results, particularly with respect to bleaching as compared to other compositions in other identical respects where TAED, NOBS or be zoil caproJactam in equal weight is used as a substitute compound of the bleach activator. -identified with *. In particular, the novel enhanced performance bleach activators, such as those of Examples TII-XII, provide superior results and are highly efficient.

EXAMPLE XXXV A bleaching detergent powder contains the following: Component% in Weight Whitening Activator- according to 5 to which was from the Fiery ls I-XXXII1. 10 Sodium Perborate tetrahydrate. Sulphonate of Alkylbenzene 8 Li neal C12 - Phosphate (as Tp pol 1 sfos fa or 9 of Sodium). Sodium Carbonate 20 Talcum 15 Rinse Aid, Perfume 0.3 Sodium Chloride 25 Water and Minor Ingredients * rest for 100% EXAMPLE XXXVI A suitable clothing rod is prepared for hand-washing soiled fabrics by normal extrusion procedures and contains the following: Component X in Weight Activator Whitening according to any of the Examples I-XXX. Sodium Perborate Tetrahydrate 12. Alkylbenzene sulfonate 30 Linear C12. Phosphate (co-or Sodium Tripolisphosphate) Sodium Carbonate 5 Sodium Pyrophosphate 7 Coconut Monoetanolarni 2 Zeolite A (0.1-10 microns) 5 Carboxymethylcellulose 0.2 Polyacrylate (pm 1400) 0.2 Brightener, Perfume 0.2 Protease 0.3 CaSO4 1 MgSO4 1 gua 4 Filler * rest for 100% * Suitable materials can be selected such as CaC? 3, talc, clay, silicates, and the like. Acid fillers can be used to reduce the pH. Bar tissue is washed with excellent results.

Claims (12)

NOVELTY OF THE INVENTION CLAIMS

1. A bleaching detergent composition containing: (a) from about 0.1% to about 20% of a bleach activator having a KP / KD perhydrolysis selectivity coefficient of at least about 5 and a perhydrolyse efficiency coefficient of pH reduced by at least approximately 0.15; and (b) from about 0.2% to about 40% of a source of hydrogen peroxide; having such bleaching detergent low resistivity to the level of dirt.

2. A bleaching detergent composition, according to claim 1, further comprising (e) approximately 0.1% to about 50% detersive ingredients that do not contain soap to reduce the pH.

3. A composition according to claim 1, further characterized in that said components (b) and (a) are in a ratio of about 3: J to about 20: 1, such as is expressed on a base of (b) (a) in the units of moles of H2O2 released by said source of hydrogen peroxide to the moles of the bleach activator.

4. A composition according to claim 3, further characterized in that said detersive ingredients that do not contain soap to reduce the pH substantially comprise from about 1% to about 25% of one or more members selected from the group consisting of (i) ionic detersive surfactants which do not contain soap; (n) polyrneric dispersants; (111) transition metal sieves; (IV) mixtures thereof.

5. A composition according to claim 4, further characterized in that the detersive ingredients that do not contain soap to reduce the pH contain at least one ionic detersive surfactant selected from the group consisting of ammonium detersive surfactants at least in partially acid form; semi-polar surfactants; zwitteponic surfactants; and mixtures thereof.

6. A composition according to claim 5, further comprising a detersive surfactant derived from sugar-.

7. A composition according to claim 6, further characterized in that said bleach activator has a melting point of about 30 ° C or higher.

8. A composition according to claim 5, further characterized in that said Soil Release polymer is a member selected from the group consisting of nonionic soil release polymers; Polymers of Release of dirt with ends topped in sul o; and mixtures thereof.

9. A detergent composition in a solid form that releases a pH in use on a scale of 7 to 9.5 and that consists of

0. 4% to 4% of a whitening activator having a perih drolisi s selectivity coefficient of 5 or greater and a reduced pH perhydrolysis efficiency coefficient of 0.3 or higher; and from 1% to 12% of at least one detersive surfactant which is not partially acidic soap.

10. A detergent composition in solid form according to claim 9, which further contains 0.1 to 10% of a member selected from the group consisting of sodium phosphate detergent-enhancing bases, poly carboxy lato sodium and mixtures thereof; and 10% or more of a member selected from the group consisting of sodium chloride, sodium sulfate and mixtures thereof. U.

A detergent composition in solid form according to claim 10, further comprising a bleach activator selected from bleach activators of alkanedyloxy benzene sulfonate and the bleach activator of tetracetyl letile diamine.

12. A detergent composition in solid form which contains from 0.1% to 10% of a bleach activator having a perhydrolysis selectivity coefficient of 5 or greater and a coefficient of efficiency of perhydrolysis of reduced pH of 0.3 or higher.; and from 0.01% to 5% of a soil release polymer.