MXPA01004008A - Laundry detergents comprising modified alkylbenzene sulfonates - Google Patents

Abstract

Modifiedalkylbenzene sulfonate surfactant mixtures comprise a mixture of specific branched and non-branched alkylbenzene sulfonate compounds, and are further characterised by 2/3-phenyl index of 257-10000. Detergent and cleaning products containing these mixtures are also claimed.

Description

LAUNDRY DETERGENTS COMPRISING MODIFIED ALKYLBENCENSULPHONATES FIELD OF THE INVENTION The present invention relates to particular types of alkylbenzene sulfonate surfactant mixtures which contain branching and are adapted for use in laundry products and for cleaning by controlling the composition parameters, especially a 2/3-phenyl index and an index 2 -methyl-2-phenyl, as well as detergent and cleaning products containing these mixtures of surfactants, alkylbenzene precursors for mixtures of surfactants, and methods for preparing the precursors as well as mixtures of surfactants. The compositions herein are especially useful for washing fabrics in laundry.

BACKGROUND OF THE INVENTION Historically, highly branched alkylbenzenesulfonate surfactants, such as those based on tetrapropylene, known as "ABS" or "TPBS", have been used in detergents. However, it was discovered that they are very poorly biodegradable.

A long period followed to improve the manufacturing processes of alkylbenzenesulfonates, making them as linear as is practically possible, hence the acronym "LAS". The overwhelming part of a large manufacturing technique of linear alkylbenzenesulfonate surfactants is directed towards this objective. All relevant large-scale commercial procedures of alkylbenzene sulfonates in current use are directed to linear alkylbenzene sulphonates. However, linear alkylbenzenesulfonates are not without limitations; for example, they would be more desirable if they improve their properties for cleaning in hard water and / or cleaning in cold water. They can often fail to produce good cleaning results, for example when formulated with non-phosphate builders and / or when used in hard water areas. As a result of the limitations of alkylbenzene sulfonates, consumer cleaning formulations have often needed to include a higher level of co-surfactants, builders, and other additives that would be needed given a higher alkylbenzene sulfonate. The alkylbenzene sulfonate detergent technique is full of references that teach the pros and cons of almost every aspect of those compositions. In addition, there are technical teachings and misunderstandings that are believed to be flawed about the operating mechanism of LAS under conditions in use, particularly in the area of hardness tolerance. The volume of such references degrades the technique as a whole and makes it difficult to select the useful lessons from the useless without repeated experimentation. To further understand the state of the art, it must be appreciated that there has been not only a lack of clarity as to which path to take to fix the unresolved problems of LAS linear, but also a range of misunderstood concepts, not only in the understanding of biodegradation but also in basic mechanisms of LAS operation in the presence of hardness. In addition, although the essentially linear alkylbenzene sulfonate surfactants, which are currently marketed, are relatively simple to define and analyze compositions, the compositions containing branched surfactants and linear alkylbenzenesulfonate are complex. A large number, for example hundreds, of different chemical species are possible in said mixtures. According to this there is an onerous burden of experimentation if it is desired to improve said compositions so that they can better clean fabrics in detergent compositions while at the same time remaining biodegradable. The knowledge of the formulator is key to guiding this effort. Yet another unsolved problem in the manufacture of alkylbenzene sulfonate is to make more effective use of current LAB supply materials. It would be very desirable, both from the point of view of yield and from an economic point of view, to better utilize certain desirable types of branched hydrocarbons.

Accordingly, there is an unmet need for further improvements in mixtures of alkylbenzenesulfonate surfactants, especially with respect to those which offer one or more of the advantages of superior cleaning, hardness tolerance, satisfactory biodegradability, and cost.

TECHNICAL BACKGROUND USES. 5,659,099, U.S.A. 5,393,718, U.S.A. 5,256,392, U.S.A. 5,227,558, U.S.A. 5,139,759, U.S.A. 5,164,169, U.S.A. 5,116,794, U.S.A. 4,840,929, U.S.A. 5,744,673, U.S.A.5,522,984, U.S.A. 5,811, 623, U.S.A. ,777,187, WO 9,729,064, WO 9,747573, WO 9,729,063, U.S.A. 5,026,933; USES. 4,990,718; USES. 4,301, 316; USES. 4,301, 317; USES. 4,855,527; USES. 4,870,038; USES. 2,477,382; EP 466,558, 1/15/92; EP 469,940, 2/5/92; FR 2,697,246, 4/29/94; SU 793,972, 1/7/81; USES. 2,564,072; USES. 3,196,174; USES. 3,238,249; USES. 3,355,484; USES. 3,442,964; USES. 3,492,364; USES. 4,959,491; WO 88/07030, 9/25/90; USES. 4,962,256, U.S.A. ,196,624; USES. 5,196,625; EP 364,012 B, 2/15/90; USES. 3,312,745; USES. 3,341, 614; USES. 3,442,965; USES. 3,674,885; USES. 4,447,664; USES. 4,533,651; USES. 4,587,374; USES. 4,996,386; USES. 5,210,060; USES. ,510,306; WO 95/1761, 7/6/95; WO 95/18084; USES. 5,510,306; USES. ,087,788; USES. 4,301, 316; USES. 4,301, 317; USES. 4,855,527; USES. 4,870,038; USES. 5,026,933; USES. 5,625,105 and U.S.A. 4,973,788. The manufacture of alkylbenzenesulfonate surfactants has recently been reviewed. See Vol. 56 in the series "Surfactant Science", Marcel Dekker, New York, 1996, including in particular chapter 2 entitled "Alkylarylsulfonates: History, Manufacture, Analysis and Environmental Properties", pages 39-108 which includes 297 literature references . Analytical methods related to surfactants are described in the series "Surfactant Science", vol. 73, Marcel Dekker, New York, 1998, and in the series "Surfactant Science", vol. 40, Marcel Dekker, New York, 1992. The documents referred to herein are incorporated in the entirety. Also consult the co-pending patent applications of E.U.A. No. 60 / 053,319, attorney's file No. 6766P, filed on July 21, 1997, No. 60 / 053,318, attorney's file No. 6767P, filed on July 21, 1997, No. 60 / 053,321, record of Counsel No. 6768P, filed on July 21, 1997, No. 60 / 053,209, attorney's file No. 6769P, filed on July 21, 1997, No. 60 / 053,328, attorney's file No. 6770P, filed on April 21, 1997 July 1997, No. 60 / 053,186, attorney's file No. 6771 P, filed on July 21, 1997, and the technique referred to therein.

BRIEF DESCRIPTION OF THE INVENTION It has been surprisingly discovered that certain mixtures of alkylbenzene sulfonate surfactants, hereinafter referred to as "mixtures of modified alkylbenzene sulfonate surfactants", which offer one or more, or even several, of the advantages outlined above. The discovery of these mixtures solves important problems of the type described in the background. Thus, according to a first embodiment of the present invention, a new mixture of modified alkyl benzene sulfonate surfactant is provided. This new mixture of surfactants comprises, preferably consists essentially of: (a) from 60% to 95% by weight, preferably from 65% to approximately 90%, more preferably from 70% to approximately 85%, of a mixture of branched alkylbenzene sulphonates that have the formula (I): (O In which L is an aliphatic acyclic portion consisting of carbon and hydrogen, said L has two methyl terms and said L has no substituents other than A, R1 and R2, and wherein said mixture of branched alkylbenzene sulfonates contains two or more, preferably at least three, optionally more, of said branched alkylbenzene sulphonates differing in molecular weight from the anion of said formula (I) and wherein said mixture of branched alkylbenzene sulphonates has: - A sum of carbon atoms in R1, L and R2 from 9 to 15, preferably from 10 to 14; - An average aliphatic carbon content, ie, based on R1, L and R2 and excluding A, from about 10.0 to about 14.0 carbon atoms, preferably from 11.0 to about 13.0, more preferably from about 11.5 to about 12.5; M is a cation or a mixture of cations, preferably M is selected from H, Na, K, Ca, Mg and mixtures thereof, more preferably M is selected from H, Na, K and mixtures thereof, furthermore preferably, M is selected from H, Na and mixtures thereof, M has a valence q, typically from 1 to 2, preferably 1; a and b are selected integers such that said branched alkylbenzene sulphonates are electroneutral (a is typically 1 to 2, preferably 1, b is 1); R1 is C1-C3 alkyl, preferably C1-C2 alkyl, more preferably methyl; R2 is selected from H and C1-C3 alkyl (preferably H and C1-C2 alkyl, more preferably H and methyl, more preferably H and methyl with the proviso that by at least about 0.5, more preferably 0.7, more preferably from 0.9 to 1.0 mole fraction of said branched alkylbenzenesulfonates R2 is H); A is a benzene portion (typically A is the -CßH-i- portion, with the SO3 portion of the formula (I) in the para position to the L portion, although in some proportion, usually not more than about 5%, preferably from 0 to 5% by weight, portion S03 is ortho- to L); and (b) from 5% to about 40% in weight, preferably from about 10% to about 30%, more preferably from 15% to about 30%, of a mixture of unbranched alkylbenzene sulphonates having the formula (II): (II) In which a, b, M, A and q are as defined above and Y is an unsubstituted linear aliphatic portion consisting of carbon and hydrogen having two methyl terms, and wherein said Y has a sum of carbon atoms from 9 to 15, preferably from 10 to 14, and said Y having an average aliphatic carbon content of from about 10.0 to about 14.0, preferably from 11.0 to about 13.0, more preferably from about 11.5 to 12.5 carbon atoms; and wherein said mixture of modified alkylbenzene sulfonate surfactants is further characterized by a 2/3-phenyl index of from 275 to about 10,000, preferably from 350 to about 1200, more preferably from about 500 to about 700; and also preferably wherein said mixture of modified alkylbenzene sulfonate surfactants has a 2-methyl-2-phenyl index of less than about 0.3, preferably less than about 0.2, more preferably less than about 0.1, even more preferably, from 0 to 0.05. The first embodiment of the present invention also encompasses the novel mixtures of modified alkyl benzene sulfonate surfactants as defined on the basis of their preparation. Said new mixtures of surfactants include those comprising, preferably consisting essentially of: the product of a process comprising the steps of: (I) alkylating benzene with an alkylation mixture; (II) sulfonate the product of (I); and (optionally but most preferably) (III) nalizing the product of (II); wherein said alkylation mixture comprises: (a) from 1% to about 99.9%, by weight of branched C9-C20 monoolefins (preferably C9-C15, more preferably C10-C14), said branched monoolefins have identical structures those of the branched monoolefins formed by dehydrogenation of branched paraffins of formula R1LR2 in which L is an aliphatic acyclic portion consisting of carbon and hydrogen and containing two terminal methyls; R1 is C1 to C3 alkyl; and R2 is selected from H and C1 to C3 alkyl; and (b) from 0.1% to about 85%, by weight of linear C9-C20 aliphatic olefins (preferably C9-C15, more preferably C10-C14); wherein said alkylation mixture contains said branched C9-C20 monoolefins having at least two different carbon numbers on said C9-C20 scale, and has an average carbon content of from 9.0 to about 15.0 carbon atoms (preferably from about 10.0 to about 14.0, more preferably from 11.0 to about 13.0, even more preferably from 11.5 to about 12.5); and wherein said components (a) and (b) are in a weight ratio of at least about 15:85 (preferably having the branched component (a) in excess of the linear component (b), for example 51% or more in weight of (a) and 49% or less of (b), more preferably 60% to 95% by weight of (a) and 10% to 35% of (b), still more preferably 70% to 85% in weight of (a) and 15% to 30% of (b) in which those percentages by weight exclude any other materials, for example diluting hydrocarbons, which may be present in the process). Similarly, the invention encompasses a novel mixture of alkylbenzenesulfonate surfactants comprising, preferably consisting essentially of: the product of a process comprising the steps, in sequence, of: (I) alkylating benzene with an alkylation mixture; (II) sulfonate the product of (I); and (III) nalizing the product of (II); wherein said alkylation mixture comprises: (a) from 1% to about 99.9%, by weight of a branched alkylating agent selected from: (i) C9-C20 internal monoolefins (preferably from C9-C15, more preferably from C10-C14) R1LR2 in which L is an acyclic olefinic portion consisting of carbon and hydrogen and containing two terminal methyls; (ii) C9-C20 alpha monoolefins (preferably C9-C15, more preferably C10-C14) R1AR2 wherein A is an alpha-olefinic acyclic moiety consisting of carbon and hydrogen and containing a terminal methyl and a terminal olefinic methylene; (Ii) vinylidene monoolefins of C9-C20 (preferably C9-C15, more preferably C10-C14) R1BR2 in which B is an acyclic vinylidene olefin moiety consisting of carbon and hydrogen and containing two terminal methyl and one olefinic methylene internal; (iv) C9-C20 primary alcohols (preferably C9-C15, more preferably C10-C14) R1QR2 wherein Q is an acyclic aliphatic primary terminal alcohol portion consisting of carbon, hydrogen and oxygen and containing a terminal methyl; (v) C9-C20 primary alcohols (preferably C9-C15, more preferably C10-C14) R1ZR2 wherein Z is a non-terminal aliphatic acyclic primary alcohol moiety consisting of carbon, hydrogen and oxygen and containing two terminal methyls; and (vi) mixtures thereof; wherein in any of (i) - (vi) said R1 is C1 to C3 alkyl; and R2 is selected from H and C1 to C3 alkyl; and (b) from 0.1% to about 85%, by weight of a linear C9-C20 alkylating agent (preferably C9-C15, more preferably C10-C14) selected from linear C9-C20 aliphatic olefins (preferably C9) -C15, more preferably C10-C14) linear C9-C20 aliphatic alcohols (preferably C9-C15, more preferably C10-C14) and mixtures thereof; wherein said alkylation mixture contains the branched alkylating agents having at least two different carbon numbers on said C9-C20 scale, (preferably C9-C15, more preferably C10-C14) and has an average carbon content of 9.0 to about 15.0 carbon atoms, preferably from about 10.0 to about 14.0, more preferably from 11.0 to about 13.0, even more preferably from 11.5 to about 12.5); and wherein said components (a) and (b) are in a weight ratio of at least about 15:85 (preferably having the branched component (a) in excess of the linear component (b), for example 51% or more in weight of (a) and 49% or less of (b), more preferably 60% to 95% by weight of (a) and 5% to 40% of (b), still more preferably 65% to 90% in weight of (a) and 10% to 35% of (b), still more preferably 70% to 85% by weight of (a) and 15% to 30% of (b), in which those percentages by weight exclude any other materials, for example diluent hydrocarbons, which may be present in the process). According to a second embodiment of the present invention, a variety of detergent compositions are provided, especially laundry detergent compositions, which comprise the mixture of modified alkyl benzene sulfonate surfactants of the first embodiment. Said detergent compositions generally contain an amount of the modified alkyl benzene sulfonate surfactant useful in helping to clean fabrics, and amounts of laundry-specific detergent adjuncts which distinguish the preferred compositions herein from compositions that are used in non-laundry detergent fields. A detergent composition according to the second embodiment of the present invention is a new detergent composition comprising, preferably consisting essentially of: (a) from about 1% to about 50%, preferably from 2% to about 30% by weight, of modified alkyl benzene sulfonate surfactant mixture of the first embodiment, wherein said modified alkyl benzene sulfonate surfactant mixture has a 2-methyl-2-phenyl index of less than about 0.3, preferably from 0 to 0.2, more preferably no more 0.1, more preferably still, no more than about 0.05; (b) from about 0.000001% to about 10%, preferably from about 0.01% to about 2%, of a member selected from the group consisting of optical brighteners, colorants, photobleaches, hydrophobic bleach activators and metal bleach catalysts transition, preferably at least two of said component members, more preferably at least two of said component members include an optical brightener as one of the component members; (c) from 0.1% to about 40% by weight, preferably not more than 30%, of surfactants which are selected from the group consisting of cationic surfactants, nonionic surfactants, anionic surfactants, and amine oxide surfactants (more preferably at least one cationic surfactant is present at a level of 0.2% to about 5% by weight, or at least one nonionic surfactant is present at a level of 0.5% a Í "3? Te" ssi *, aiáiiÍ? Ík .. about 25% by weight, or at least one alkyl sulfate surfactant or an alkyl (polyalkoxy) sulfonate surfactant is present at a level of 0.5% to about 25% by weight); and (d) from about 10% to about 99% conventional cleaning aids (other than any of (a) - (c)); with the proviso that when said detergent composition comprises any alkylbenzene sulfonate surfactant other than said mixture of modified alkyl benzene sulphonate surfactants (e.g. as a result of mixing in the detergent composition one or more commercially available, especially linear, alkylbenzene sulphonate surfactants, typically linear of C10-C14), said detergent composition is further characterized by a total 2/3-phenyl index of at least about 200, preferably at least about 250, more preferably at least about 350, even more preferably, at least about 500, in wherein said 2/3-phenyl index is determined by measuring the 2/3-phenyl index, as defined herein, in a combination of said mixture of modified alkylbenzenesulfonate surfactants and any other alkylbenzenesulfonate that will be added to said detergent composition , said combination For measurement purposes, it is prepared from aliquots of the mixture of modified alkyl benzene sulphonate surfactants and the other alkylbenzene sulphonate which has not yet been exposed to any other component of the detergent composition; and with the additional proviso that when said detergent composition comprises any alkylbenzene sulfonate surfactant other than the mixture of modified alkyl benzene sulphonate surfactants (eg, as a result of combining in the detergent composition one or more commercially available, especially linear, alkylbenzene sulphonate surfactants). , typically linear of C 10 -C 14), said detergent composition is further characterized by a total 2-methyl-2-phenyl index of less than about 0.3, preferably from 0 to 0.2, more preferably not more than 0.1, even more preferably, not more than 0.05, wherein said 2-methyl-2-phenyl index will be determined by measuring the 2-methyl-2-phenyl index, as defined herein, in a combination of said mixture of modified alkyl benzene sulfonate surfactants and any another alkylbenzene sulfonate that will be added to said detergent composition, said combination, for For purposes of measurement, it is prepared from aliquots of the mixture of modified alkyl benzene sulphonate surfactants and the other alkylbenzene sulfonate which has not yet been exposed to any other component of the detergent composition. These arrangements may seem somewhat unusual, however they are consistent with the spirit and scope of the present invention, which encompasses a number of economical but less preferred methods in terms of total cleaning performance, such as combining the modified alkyl benzene sulfonate surfactants. with conventional linear alkylbenzenesulfonate surfactants either during synthesis or - ^. Also, as the detergent analysis practitioners know, a number of detergent auxiliaries (paramagnetic materials such as certain transition metal bleach catalysts) for example, and sometimes even water) are able to interfere with the methods for determining the parameters of modified alkylbenzenesulfonate surfactant mixtures as described below, hence, wherever possible, the analysis on dry materials should be conducted. before mixing them in the detergent compositions The invention, on the other hand, is not designed to encompass any conventional alkylbenzene sulfonate composition or the detergent compositions derived therefrom., such as those based exclusively on linear alkylbenzenesulfonates prepared by any process, or exclusively on known branched alkylbenzene sulfonates in an unacceptable manner, such as ABS or TPBS. According to a third embodiment of the present invention, a new mixture of modified alkylbenzene is provided. This new alkylbenzene mixture is useful for making the modified alkylbenzene sulfonate surfactant mixtures of the first embodiment, and comprises, preferably consists essentially of: (a) from about 60% to about 95% (preferably from about 65% to about 90) %, more preferably from about 70% to about 85%) by weight of a mixture of branched alkylbenzenes having the formula (I): XL I A (OR In which L is an aliphatic acyclic portion consisting of carbon and hydrogen and that has two terms methyl; and wherein said mixture of branched alkylbenzenes contains two or more compounds of said formula (I) differing in molecular weight and wherein said mixture of branched alkylbenzenes is characterized by a sum of carbon atoms in R1, R2 and L of 9 to 15, preferably 10 to 14; and an average aliphatic carbon content (ie, excluding A), based on the sum of R1, L and R2, from about 10.0 to about 14.0, preferably from about 11.0 to about 13.0, more preferably from 11.5 to 12.5 atoms. carbon; and further, in which L has no substituents other than A, R1 and R2; R1 is C1-C3 alkyl, (preferably C1-C2 alkyl, more preferably methyl); R2 is selected from H and C1-C3 alkyl (preferably H and C1-C2 alkyl, more preferably H and methyl, more preferably H and methyl with the proviso that at least about 0.5, more preferably 0.7, more preferably from 0.9 to 1.0 mole fraction of said branched alkylbenzenesulfonates R2 is H); A is a benzene (non-sulfonated) portion (-CßHs- has no different substituents except L); and (b) from 5% to about 40% (preferably from about 10% to about 35%, more preferably from 15% to about %) by weight of a mixture of unbranched alkylbenzene sulphonates having the formula (II): Y I A (ll) In which A is a benzene (non-sulfonated) portion (-CßH5- has no different substituents except L) and Y is an unsubstituted linear aliphatic portion consisting of carbon and hydrogen having two methyl terms, and in which Y has from 9 to 15 carbon atoms in total (preferably from 10 to 14) and said mixture of unbranched alkylbenzenes has an average aliphatic carbon content (ie, carbon content excluding A) of from about 10.0 to about 14.0 carbon atoms, preferably from 11.0 to about 13.0 carbon atoms. carbon, more preferably from about 11.5 to 12.5 carbon atoms; and wherein said modified alkylbenzene mixture is further characterized by a 2/3-phenyl index of from 275 to about 10,000, preferably from 350 to about 1200, more preferably from about 500 to about 700; and a 2-methyl-2-phenyl index of less than about 0.3, preferably from * h ^ á ^ e m O at about 0.2, more preferably not more than about 0.1, even more preferably, 0.05 or less. According to other embodiments of the present invention, a number of alternate and less preferred embodiments are encompassed therein, such as those in which there is a combination of the novel mixture of modified alkyl benzene sulfonate surfactants of the invention with one or more than other alkylbenzenesulfonate surfactants. In practical terms, said combination is achieved before the sulfonation and detergent formulation, but the result is a mixture of surfactants or detergent composition containing a combination of the new modified alkylbenzenesulfonate surfactant with other known alkylbenzene sulphonates. Said alternate embodiments of the invention include, but are not limited to, those herein referred to as "medium 2/3-phenyl surfactant mixtures". Said mixtures of surfactant essentially contain useful amounts of the modified alkylbenzene sulfonate surfactant, together with other known alkylbenzene sulphonates subject to the specific conditions of the 2/3-phenyl index of the total composition. Such compositions include: a 2/3-phenyl average surfactant mixture consisting essentially of: from 1% (preferably at least about 5%, more preferably at least about 10%) to 60% (in a mode preferably less than 50 %, more preferably less than about 40%) by weight of a first surfactant of alkylbenzenesulfonate, wherein said first alkylbenzenesulfonate surfactant is a mixture of alkylbenzene sulfonate surfactants modified in accordance with the first embodiment; and b) from 40% (in an embodiment preferably at least about 50%, more preferably at least about 60%) to about 99% (preferably less than 95%, more preferably less than about 90%) by weight of a second surfactant of alkylbenzenesulfonate, wherein said second alkylbenzenesulfonate surfactant is a mixture of alkylbenzene sulfonate surfactants different from the mixture of alkylbenzene sulphonate surfactants modified according to the first embodiment, and wherein said second alkylbenzene sulfonate surfactant has an index 2/3-phenyl of from 75 to about 160 (typically said second alkylbenzenesulfonate surfactant is a commercial C10-C14 linear alkylbenzenesulfonate surfactant, for example, DETAL® process LAS or HF process LAS, although in general any linear commercial type (LAS) or branched (ABS, T PBS)); with the proviso that said average 2/3 phenyl surfactant mixture has a 2/3-phenyl index of from about 160 to about 275 (preferably from about 170 to about 265, more preferably from about 180 to about 255). Of course it is equally possible within the spirit and scope of the invention to prepare any combination of the modified alkylbenzene sulfonate surfactant mixture of the invention with any known commercial linear or branched alkylbenzene sulphonate surfactant. The preferred embodiments of the cleaning composition also contain specific cleaning auxiliaries which are defined below. Moreover, the invention encompasses less preferred but sometimes useful modalities for its normal purposes, such as the addition of hydrotrope precursors and / or useful hydrotropes such as C1-C8 alkylbenzenes, more typically toluenes, eumens, xylenes, naphthalenes, or sulfonated derivatives of any of said materials, minor amounts of any other materials, such as tri-branched alkylbenzene sulphonate surfactants, dialkylbenzenes and their derivatives, dialkyltetralins, wetting agents, processing aids, and the like. It will be understood that, with the exception of hydrotropes, it will not be usual practice in the present invention to include any such materials. It will also be understood that said materials, as long as they interfere with the analytical methods, will not be included in samples of compositions that are used for analytical purposes. The aforementioned embodiments and other aspects of the present invention are described and illustrated in more detail in the following detailed description. All percentages, ratios and proportions herein are by weight, unless otherwise specified. All temperatures are in degrees Celsius (° C) unless otherwise specified. All the documents cited are in part relevant, incorporated herein by reference.

DETAILED DESCRIPTION OF THE INVENTION First Mode: A.- Mixtures of modified alkylbenzenesulfonate surfactants The present invention encompasses a modified alkyl benzene sulfonate surfactant mixture comprising (preferably, consisting essentially of): (a) from 60% to 95% by weight, (preferably from 65% to about 90%, more preferably from 70% by weight) about 85%), of a mixture of branched alkylbenzene sulfonates having the formula (I): (0) In which L is an aliphatic acyclic portion consisting of carbon and hydrogen, said L has two methyl terms and said L has no substituents other than A, R1 and R2; and wherein said mixture of branched alkylbenzene sulphonates contains two or more, (preferably at least three, optionally more), said branched alkylbenzene sulphonates differing in molecular weight from the anion of said formula (I) and wherein said mixture of branched alkylbenzene sulphonates it has a sum of carbon atoms in R1, L and R2 of 9 to 15, (preferably 10 to 14); an average aliphatic carbon content, (ie, based on R1, L and R2 and excluding A), from about 10.0 to about 14.0 carbon atoms (preferably from 11.0 to about 13.0, more preferably from about 11.5 to about 12.5); M is a cation or a mixture of cations, (preferably selected from H, Na, K, Ca, Mg and mixtures thereof, more preferably selected from H, Na, K and mixtures thereof, even more preferably, it is selected from H, Na and mixtures thereof), has a valence q, (typically 1 to 2, preferably 1); a and b are selected integers such that said branched alkylbenzene sulphonates are electroneutral (a is typically 1 to 2, preferably 1, b is 1); R is C 1 -C 3 alkyl, (preferably C 1 -C 2 alkyl, more preferably methyl); R2 is selected from H and C1-C3 alkyl (preferably H and C1-C2 alkyl, more preferably H and methyl, more preferably H and methyl with the proviso that at least about 0.5, more preferably 0.7, more preferably from 0.9 to 1.0 mole fraction of said branched alkylbenzenesulfonates R2 is H); A is a benzene portion (typically A is the -C6H- portion, with the SO3 portion of the formula (I) in the para- position to the L portion, although in some proportion, usually not more than about 5%, preferably from 0 to 5% by weight, the SO3 portion is ortho- to L); and (b) from about 5% to about 40% by weight, (preferably from about 10% to about 35%, more preferably from 15% to about 30%), of a mixture of unbranched alkylbenzene sulphonates having the formula (II) ): (II) In which a, b, M, A and q are as defined above and Y is an unsubstituted linear aliphatic portion consisting of carbon and hydrogen having two methyl terms, and wherein said Y has a sum of carbon atoms from 9 to 15, preferably from 10 to 14, and said Y having an average aliphatic carbon content of from about 10.0 to about 14.0, (preferably from 11.0 to about 13.0, more preferably from 11.5 to 12.5 carbon atoms); and wherein said mixture of modified alkylbenzene sulfonate surfactants is further characterized by a 2/3-phenyl index of from 275 to about 10,000, (preferably from 350 to about 1200, more preferably from about 500 to about 700).

A mixture of preferred modified alkyl benzene sulphonate surfactants has M selected from H, Na, K and mixtures thereof, said a = 1, said b = 1, said q = 1, and said mixture of modified alkyl benzene sulphonate surfactants has a 2-methyl-2-phenyl index of less than about 0.3, preferably less than about 0.2, more preferably from 0 to about 0.1. Said mixture of alkylbenzene sulfonate surfactants modified in accordance can be manufactured as the product of a process using as catalyst a zeolite selected from mordenite, ofretite and H-ZSM-12 in at least partially acidic form, preferably an acid mordenite (in general certain forms of zeolite beta can be used as an alternative but are not preferred). The modalities described in terms of their manufacture, as well as the appropriate catalysts, are further detailed below. Another mixture of modified modified alkylbenzene sulfonate surfactants according to the first embodiment of the invention consists essentially of said mixture of branched alkylbenzene sulphonates and unbranched alkylbenzene sulphonates, wherein said 2-methyl-2-phenyl index of said mixture of surfactants of Modified alkylbenzene sulfonate is less than 0.1, and wherein in said mixture of branched and unbranched alkylbenzene sulphonates, said average aliphatic carbon content is from about 1.5 to about 12.5 carbon atoms; said R is methyl; R2 is selected from H and methyl with the proviso that at least 0.7 mole fraction of said modified alkylbenzene sulphonates R2 is H; and wherein said sum of carbon atoms in R1, L and R2 is from 10 to 14; and further wherein in said mixture of unbranched alkylbenzene sulphonates, said Y has a sum of carbon atoms of 10 to 14 carbon atoms, said average aliphatic carbon content of the unbranched alkylbenzene sulphonates is from 11.5 to about 12.5 carbon atoms , and said M is a monovalent cation or mixture of cations selected from H, Na and mixtures thereof.

Definitions: Methyl term.- The terms "methyl term" and / or "terminal methyl" mean the carbon atoms which are the terminal carbon atoms in alkyl portions, ie L, and / or Y of the formula (I) and Formula (II) respectively are always linked to three hydrogen atoms. That is, they will form a CH3- group. To explain this better, the following structure shows the two terminal methyl groups in an alkylbenzenesulfonate: methyl The term "AB" in the present when used without further qualification is an abbreviation for "alkylbenzene" of the so-called "hard" or nonbiodegradable type, which with the sulfonation forms "ABS". The term "LAB" herein is an abbreviation for "linear alkylbenzene" of the currently commercial type, more biodegradable, which at the sulfonation forms linear alkylbenzene sulfonate, or "LAS". The term "MLAS" herein is an abbreviation for the modified alkylbenzene sulfonate blends of the invention. Impurities: The surfactant mixtures herein are preferably substantially free of selected impurities of tri-branched impurities, dialkyltetralin impurities and mixtures thereof. By "substantially free" it means that the amounts of said impurities are insufficient to contribute positively or negatively to the cleaning effectiveness of the composition. Typically there is less than 5%, preferably less than about 1%, more preferably about 0.1% or less of the impurity, ie, typically none of the impurities is practically detectable.

Illustrative Structures To better illustrate the possible complexity of mixtures of modified alkylbenzenesulfonate surfactants of the invention and the resulting detergent compositions, the following structures (a) to (v) are illustrative of some of the many preferred compounds of formula (I).

These are only a few of hundreds of preferred possible structures that form the bulk of the composition, and should not be considered as limiting the invention. (a) (b) (c) () (e) C ,- 1 , .

(¡) (I) (k) (I) (m) (n) - &- (o) (P) (q) (r) (s) (t) (u) (v) Structures (w) and (x) non-limitingly illustrate less preferred compounds of formula (I) which may be present, at lower levels than the structures of preferred types illustrated above, in the mixtures of modified alkylbenzenesulfonate surfactants of the invention and the resulting detergent compositions. (w) (x) The structures (y), (z) and (aa) illustrate in a non-limiting manner compounds widely within the formula (I) that are not preferred but may be present in the mixtures of alkylbenzene sulfonate surfactants of the invention and the resulting detergent compositions. (and Z) (aa) (bb) * - •%. , # • _.

The structure (bb) is illustrative of a tri-branched structure not within the formula (I), but which may be present as an impurity.

First Mode: B.- Mixtures of modified alkylbenzenesulfonate surfactants defined on the basis of their preparation.

Preferably the modified alkyl benzene sulphonate surfactant mixtures herein are the product of sulfating a modified alkylbenzene (in reference to the well-known types of tetrapropylene or AB) in which the modified alkyl benzene is produced by alkylating benzene with a branched olefin, different to tetrapropylene, and more in particular the lightly branched types which are described in greater detail below, on an acid mordenite type catalyst or other suitable catalyst as defined elsewhere herein. In certain cases, the compositions herein may be prepared by combination. Thus, the invention includes a detergent composition utilizing a mixture of alkylbenzene sulfonate surfactants modified in accordance with the first embodiment in which said mixture of modified alkyl benzene sulphonate surfactants is prepared by a process comprising a step selected from: i) combining a mixture of linear and branched alkylbenzene sulphonate surfactants having a 2/3-phenyl index of 500 to 700 with a mixture of alkylbenzenesulfonate surfactants having a 2/3-phenyl index of 75 to 160 and (ii) ) combining a mixture of linear and branched alkylbenzenes having a 2/3-phenyl index of from 500 to 700 with a mixture of alkylbenzene having a 2/3-phenyl index of from 75 to 160 and sulfonating said combination. Broadly speaking, the mixtures of modified alkyl benzene sulphonate surfactants herein can be made by the steps of: (I) Alkylating benzene with an alkylation mixture; (II) Sulfonate the product of (I); and (optionally but most preferably) (III) Neutralizing the product of (II). Provided that the alkylation catalysts and suitable process conditions are used as taught herein, the product of step (I) is a modified alkylbenzene mixture according to the invention. Provided that the sulfonation is conducted under generally known and reproducible conditions from the manufacture of LAS, see for example the literature references cited herein, the product of step (II) is a mixture of alkylbenzenesulfonic acid modified according to the invention. With the proviso that the neutralization step (III) is conducted as generally taught in the present, the product of step (III) is a mixture of modified alkylbenzenesulfonate surfactants according to the invention. Because the neutralization may be incomplete, mixtures of the acid and neutralized forms of the modified alkylbenzene sulfonate systems present in all proportions, for example, from about 1000: 1 to 1: 1000 by weight, are also part of the present invention. In general, the largest critical points are in step (I). The preferred modified alkylbenzene sulfonate surfactant mixtures herein comprise the product of a process comprising the steps of: (I) alkylating benzene with an alkylate mixture; (II) sulfonate the product of (I); and (optionally but most preferably) (III) neutralizing the product of (II); wherein said alkylation mixture comprises: (a) from 1% to about 99.9%, by weight of branched C9-C20 monoolefins (preferably C9-C15, more preferably C10-C14), said branched monoolefins have identical structures those of the branched monoolefins formed by the dehydrogenation of branched paraffins of formula R1LR2 in which L is an aliphatic acyclic portion consisting of carbon and hydrogen and containing two terminal methyls; R1 is C1 to C3 alkyl; and R2 is selected from H and C1 to C3 alkyl; and (b) from 0.1% to about 85%, by weight of linear C9-C20 aliphatic olefins (preferably C9-C15, more preferably C10-C14); wherein said alkylation mixture contains said branched C9-C20 monoolefins having at least two different carbon numbers on said C9-C20 scale, and has an average carbon content of 9.0 to about 15.0 carbon atoms (preferably about 10.0 to about 14.0, more preferably from 11.0 to about 13.0, even more preferably from 11.5 to about 12.5); and wherein said components (a) and (b) are in a weight ratio of at least about 15:85 (preferably having the branched component (a) in excess of the linear component (b), for example 51% or more by weight of (a) and 49% or less of (b), more preferably 60% to 95% by weight of (a) and from 5% to 40% of (b), still more preferably from 65% to 90% by weight of (a) and from 10% to 35% of (b), even more preferably from 70% to 85% by weight of (a) and from 15% to 30% of (b) in which those percentages by weight exclude any other materials, for example diluting hydrocarbons, which may be present in the process). Also encompassed herein are mixtures of modified alkyl benzene sulfonate surfactants consisting essentially of the product of a process comprising the steps, in sequence, of: (I) alkylating benzene with an alkylation mixture; (II) sulfonate the product of (I); and (III) neutralizing the product of (II); in which said The alkylation mixture comprises: (a) from 1% to about 99.9%, by weight of a branched alkylating agent selected from: (i) C9-C20 internal monoolefins (preferably C9-C15, more preferably C10-C14) ) R1LR2 in which L is an olefinic moiety ^ ^ ^^^ acyclic consisting of carbon and hydrogen and containing two terminal methyls; (I) alpha C9-C20 monoolefins (preferably C9-C15, more preferably C10-C14) R1AR2 wherein A is an alpha-olefinic acyclic moiety consisting of carbon and hydrogen and containing a terminal methyl and an olefinic methylene terminal; (iii) vinylidene monoolefins of C9-C20 (preferably C9-C15, more preferably C10-C14) R1BR2 in which B is an acyclic vinylidene olefin moiety consisting of carbon and hydrogen and containing two terminal methyl and an internal olefinic methylene; (iv) C9-C20 primary alcohols (preferably C9-C15, more preferably C10-C14) R1QR2 wherein Q is an acyclic aliphatic primary terminal alcohol portion consisting of carbon, hydrogen and oxygen and containing a terminal methyl; (v) C9-C20 primary alcohols (preferably C9-C15, more preferably C10-C14) R1ZR2 wherein Z is a non-terminal aliphatic acyclic primary alcohol moiety consisting of carbon, hydrogen and oxygen and containing two terminal methyls; and (vi) mixtures thereof; wherein in any of (i) - (vi) said R1 is C1 to C3 alkyl; and R2 is selected from H and C1 to C3 alkyl; and (b) from 0.1% to about 85%, by weight of a linear C9-C20 alkylating agent (preferably C9-C15, more preferably C10-C14) selected from linear C9-C20 aliphatic olefins (preferably C9) -C15, more preferably C10-C14) linear C9-C20 aliphatic alcohols (preferably C9-C15, more preferably C10-C14) and mixtures thereof; wherein said alkylation mixture contains the branched alkylating agents having at least two different carbon numbers on said C9-C20 scale, (preferably C9-C15, more preferably C10-C14) and has an average carbon content of 9.0 to about 15.0 carbon atoms, (preferably from about 10.0 to about 14.0, more preferably from 11.0 to about 13.0, even more preferably from 11.5 to about 12.5); and wherein said components (a) and (b) are in a weight ratio of at least about 15:85 (preferably having the branched component (a) in excess of the linear component (b), for example 51% or more by weight of (a) and 49% or less of (b), more preferably from 60% to 95% by weight of (a) and from 5% to 40% of (b), even more preferably 65% by weight 90% by weight of (a) and from '0% to 35% of (b), even more preferably from 70% to 85% by weight of (a) and from 15% to 30% of (b), in the which those percentages by weight exclude any other materials, for example hydrocarbon diluents, which may be present in the process). In more highly preferred embodiments, the invention encompasses a mixture of modified alkyl benzene sulfonate surfactants prepared in accordance with the steps outlined above in which said alkylation mixture consists essentially of: (a) from 0.5% to about 47.5% , by weight of a branched alkylating agent selected from: (i) internal monoolefins of C9-C20 R1LR2 in which L is an acyclic olefinic portion consisting of carbon and hydrogen and containing two terminal methyls; (ii) C9-C20 alpha monoolefins R1AR2 wherein A is an alpha-olefinic acyclic moiety consisting of carbon and hydrogen and containing a terminal methyl and a terminal olefinic methylene; and (iii) mixtures thereof; wherein in any of (i) - (iii) said R1 is methyl, and R2 is H or methyl with the proviso that in at least 7 molar fractions of the total of said monoolefins, R2 is H; and (b) from 0.1% to about 25%, by weight of linear C9-C14 aliphatic olefins; and (c) from about 50% to about 90% by weight of carrier materials selected from paraffins and inert non-paraffin solvents; wherein said alkylation mixture contains the branched alkylating agents having at least two different carbon numbers on said C9-C14 scale, and has an average carbon content of 1.5 to about 12.5 carbon atoms; and wherein said components (a) and (b) are in a weight ratio of 51:49 to about 90:10. Other mixtures of alkylbenzene sulfonate surfactants modified herein are manufactured by the processes outlined above in which in step (I), said alkylation is carried out in the presence of an alkylation catalyst, said alkylation catalyst is a solid alkylation catalyst intermediate acidity porous, and step (II) comprises the removal of components other than monoalkylbenzene before contacting the product of step (I) with the sulfonation agent.

Also included is the mixture of alkylbenzene sulfonate surfactants modified in accordance with the process outlined above in which said alkylation catalyst is other than a member selected from the group consisting of HF, AICI3, sulfuric acid and mixtures thereof. This is the case when the alkylation catalyst is selected from the group consisting of non-fluorinated acid mordenite type catalysts, fluorinated acid mordenite type catalysts and mixtures thereof. The catalysts are described in more detail below. The methods are tolerant to variations, for example, conventional steps may be added before, in parallel with, or after the outlined steps (I), (II) and (III). This is especially the case to accommodate the use of hydrotropes or their precursors. In this way the invention encompasses a mixture of alkylbenzene sulfonate surfactants modified in accordance with the process outlined above in which a hydrotrope, precursor of hydrotropes, or mixtures thereof is added after step (I); or the hydrotrope, the hydrotrope precursor, or mixtures thereof are added during or after step (II) and before step (III); or a hydrotrope can be added during or after step (III).

Sulfonation and Manipulation or Neutralization (Steps II / III) In general, the sulfonation of modified alkylbenzenes in the current process can be achieved using any of the well-known sulphonation systems, including those described in "Detergent Manufacture Including Zeolite Builders and other New Materials, "Ed. Sittig, Noyes Data Corp., 1979, as well as Vol. 56 of the" Surfactant Science "series, Marcel Dekker, New York, 1996, including in particular chapter 2 entitled" Alkylarylsulfonates: History, Manufacture, Analysis and Environmental Properties ", pages 39-108 that includes 297 literature references. This work provides access to a large amount of literature describing various procedures and procedural steps, not only sulfonation but also dehydrogenation, alkylation, alkylbenzene distillation and the like. Common sulfonation systems useful herein include sulfuric acid, chlorosulfonic acid, oil, sulfur trioxide, and the like. Sulfur trioxide / air is especially preferred. Details of sulfonation using an appropriate mixture of sulfur trioxide / air are provided in U.S. Patent No. 3,427,342, Chemithon. The sulfonation processes are further described extensively in "Sulfonation Technology in the Detergent Industry", W.H. de Groot, Kluwer Academic Publishers, Boston, 1991. Any manipulation steps can be used in the present procedure. The common practice is to neutralize after sulfonation with any suitable alkali. In this way the neutralization step can be conducted using selected alkali of sodium, potassium, ammonium, magnesium and substituted ammonium alkali and mixtures thereof. Potassium may aid in solubility, magnesium may promote yield in soft water, and substituted ammonium may be useful for formulating specialty variations of the surfactants of the moment. The invention encompasses any of those forms derived from the modified alkyl benzene sulfonate surfactants as produced by the present process and their use in consumer product compositions. Alternatively, the acid form of the surfactants herein can be added directly to acid cleaning products, or can be mixed with cleaning ingredients and then neutralized. The hydrotropes or hydrotrope precursors useful herein can be selected in general from any suitable hydrotrope or hydrotrope precursor, including lower alkyl (C 1 -C 8) aromatics and their sulfonic acids and sulfonate salts, but are more typically based on a sulfonic acid or sodium sulfonate salt of toluene, eumen, xylene, naphthalene or mixtures thereof. The hydrotrope precursors are selected from any suitable hydrotrope precursor typically toluene, eumen, xylene, naphthalene or mixtures thereof. A hydrotrope precursor is a compound that during step (III), ie the sulfonation step, becomes a hydrotrope.

In terms of process conditions for alkylation, the invention encompasses a mixture of modified alkyl benzene sulfonate surfactants in which in step (I) said alkylation is carried out at a temperature of 125 ° C to 230 ° C (preferably of about 175). ° C at about 215 ° C) and at a pressure of 3.5 kg / cm2 to about 70.3 kg / cm2 (preferably from 7.0 kg / cm2 to about 17.5 kg / cm2). Preferably in step (I) said alkylation is carried out at a temperature of 175 ° C to 215 ° C, at a pressure of 7.0 kg / cm2 at about 17.5 kg / cm2 and a time of about 0.01 hour to about 18 hours (preferably, as fast as possible, more typically from 0.1 hour to about 5 hours). If desired, said alkylation can be conducted in one or more stages. The different stages of the process can be conducted in different manufacturing facilities. Typically in practice, LAB manufacturers will lead step (I), with the detergent manufacturers conducting step (III). Step (I) is typically driven by anyone, or can even be driven by a third group of manufacturers. In general it has been found that it is preferable in step (I) to couple together the use of relatively low temperatures (e.g. 175 ° C at about 215 ° C) with reaction times of medium duration (1 hour to about 8 hours) at the scales indicated above. It is even possible to "target" a desirably low 2-methylo-2-phenyl index in the compositions of the present invention ai¿aaaa ¡& j ^^^ j | M selected a relatively low reaction temperature, for example about 190 ° C, and monitor the progress of the reaction by any convenient means (for example sampling and NMR analysis) to ensure adequate completion while minimizing the 2-methyl-2-phenyl index. In addition, it is contemplated that the "step" of alkylation (I) herein may be "in stages" so that two or more reactors operating under different conditions at the defined scales may be useful. By operating a plurality of said reactors, it is possible to allow material with a less preferred 2-methyl-2-phenyl index to be formed initially and, from Surprisingly, converting said material into a material with a more preferred 2-methyl-2-phenyl index. In terms of the selection of the sulfonation agent, the invention encompasses a mixture of modified alkyl benzene sulphonate surfactants in which step (II) is carried out using A sulphonation agent is selected from the group consisting of sulfur trioxide, mixtures of sulfur trioxide / air, and sulfuric acid (including oil). Chlorosulfonic acid or other known sulfonating agents, although less commercially relevant, are also useful and are included for use in the invention. Although in general, the neutralization step (III) can be carried out with any suitable alkali, the invention includes a mixture of modified alkyl benzene sulphonate surfactants in which said step (III) is carried out using a basic salt, said salt basic has a cation which is selected from the group consisting of alkali metal, alkaline earth metal, ammonium, substituted ammonium, and mixtures thereof and an anion selected from hydroxide, oxide, carbonate, silicate, phosphate and mixtures thereof. The preferred basic salt is selected from the group consisting of sodium hydroxide, sodium silicate, potassium hydroxide, potassium silicate, magnesium hydroxide, ammonium hydroxide, and mixtures thereof.

Alkylation catalyst To secure the modified alkylbenzenesulfonate surfactant mixtures of the invention, the present invention uses a particularly defined alkylation catalyst. Said alkylation catalyst is a porous solid alkylation catalyst of intermediate acidity which is defined in detail below. Particularly preferred alkylation catalysts comprise at least partially acidified alkylated fluorinated mordenites, at least partially dealuminated non-fluorinated mordenites, and mixtures thereof. Numerous alkylation catalysts are unsuitable for making the modified alkylbenzene mixtures and the modified alkylbenzene sulfonate surfactant mixtures herein. Unsuitable alkylation catalysts include any of: sulfuric acid, aluminum chloride, and HF. Nonacid calcium mordenites, and many others, are also inadequate. Other catalysts, such as UOP DETAL® process catalysts are also unsuitable, at least in their current commercial executions. In fact, none of the alkylation catalysts currently used for alkylation in the commercial production of C10-C14 linear alkylbenzenesulfonates for detergents for use in laundry products are suitable. In contrast, the appropriate alkylation catalysts herein are selected from moderately acidic form-selective alkylation catalysts, preferably of the zeolite type. The zeolite catalyst which is used for the alkylation step (I) is preferably selected from the group consisting of mordenite, HZSM-12 and ofretite, any of them in at least partially acidic form. Mixtures can be used and the catalysts can be combined with binders, etc., as described hereinafter. More preferred, the zeolite is substantially in acid form and is contained in a catalyst pellet containing a conventional binder and wherein said catalyst pellet further contains at least about 1%, preferably at least 5%, more typically from 50% to about 90% of said zeolite. More generally, an appropriate alkylation catalyst is typically at least partially crystalline, more preferred substantially crystalline not including binders or other materials used to form catalyst pellets, aggregates or mixed materials. In addition, the catalyst is typically at least partially acidic. The calcite form of completely exchanged mordenite, for example, is inappropriate while the H form of the mordenite is appropriate. The pores that characterize the zeolites useful in the present alkylation process may be substantially circular, uniform pores of about 6.2 Angstroms, or preferably they may be somewhat elliptical, such as in the mordenite. It should be understood that, in any case, the zeolites used as catalysts in the alkylation step of the present process have a larger pore size intermediate between that of the large pore zeolites, such as the X and Y zeolites, and the zeolites of relatively small pore size ZSM-5 and ZSM-11, and preferably between about 6 Angstroms and about 7 Angstroms. In effect, zeolite ZSM-5 has been tested and found inoperable in the present invention. The pore size dimensions and crystalline structures of certain zeolites are specified in ATLAS OF ZEOLITE STRUCTURE TYPES by W. M. Meier and D. H. Olson, published by the Structure Commission of the International Zeolite Association (1978 and more recent editions) and distributed by Polycrystal Book Service, Pittsburgh, Pa. The zeolites useful in the alkylation step of the The present methods generally have at least 10% of the cationic sites thereof occupied by ions other than the alkali or alkaline earth metals. Typically, but not limited to, the replacement ions include ammonium, hydrogen, rare earth, zinc, copper and aluminum. From In this group, particular preference is given to ammonium, hydrogen, rare earths or combinations thereof. In a preferred embodiment, the zeolites are converted to the predominantly hydrogenated form, generally by replacing the alkali metal ion or other ion originally present with hydrogen ion precursors, for example ammonium ions, which after calcining give the hydrogenated form. This exchange is conveniently carried out by contacting the zeolite with an ammonium salt solution, for example, ammonium chloride, using well-known ion exchange techniques. In certain preferred embodiments, the degree of The replacement is such that a zeolite material is produced in which at least 50% of the cationic sites are occupied by hydrogen ions. The zeolites can be subjected to various chemical treatments, including alumina extraction (dealuminization) and combination with one or more metal components, particularly the metals of the groups IIB, III, IV, VI, VII and VIII. It is also contemplated that the zeolites may, in some cases, be desirably subjected to thermal treatment, including vaporization or calcination in air, hydrogen or an inert gas, for example nitrogen or helium. An appropriate modifier treatment imposes the vaporization of The zeolite is contacted with an atmosphere containing from about 5 to about 100% steam at a temperature of about 250 ° C to 1000 ° C. Vaporization can last for a period of between about 0.25 and about 100 It can be carried out at pressures ranging from subatmospheric pressures to several hundred atmospheres. In practicing the desired alkylation step of the present process, it may be useful to incorporate the intermediate pore size crystalline zeolites described above into another material, for example a binder or a temperature resistant matrix and other conditions used in the process. Such matrix materials include synthetic or naturally occurring substances as well as inorganic materials such as clay, silica and / or metal oxides. The matrix materials may be in the form of gels including mixtures of silica and metal oxides. The latter can be either naturally or in the form of gels or gelatinous precipitates. Clays present in nature that can be mixed with zeolites include those from the families of montmorillonite and kaolin, whose families include sub-bentonites and kaolins commonly known as clays Dixie, McNamee-Georgia and Florida or others in the which the main constituent mineral is haloisite, kaolinite, diquita, nacrite or anaoxite. Such clays can be used in the raw state as originally extracted from the mine or initially subjected to calcination, acid treatment or chemical modification. In addition to the above materials, the intermediate pore size zeolites used in the present invention can be combined with a porous matrix material, such as alumina, silica-alumina, silica-magnesium, silica-zirconium, silica-thorium, silica-beryllium and silica-titanium, as well as ternary combinations, such as silica-alumina-thorium, silica-aluminum- <; zirconium, silica-alumina-magnesium, and silica-magnesium-zirconium. The matrix may be in the form of a co-gel. The relative proportions of the finely divided zeolite and the inorganic oxide gel matrix can vary widely, the zeolite content being between about 1 to about 99% by weight and more generally on the scale of about 5 to about 80% by weight of the mixed material. A group of zeolites including some useful for the alkylation step herein has a silica: alumina ratio of at least 2: 1, preferably at least 10: 1, preferably at least 20: 1. The silica: alumina ratios referred to in this specification are structural or framework relationships, that is, the ratio for the tetrahedron S¡O to the AIO. In practice, the silica: alumina ratios as determined by various physical and chemical methods are acceptable for use herein. It should be understood that such methods may give some variation in an acceptable manner. For example, a non-detailed chemical analysis may include the determination of aluminum, which is present in the form of cations associated with the acid sites in the zeolite, thus giving a somewhat deficient experimentally determined ratio of silica: alumina. Similarly, if the ratio is determined by thermogravimetric analysis (TGA) of ammonia desorption, a low ammonia titre can be obtained if the cationic aluminum prevents the exchange of the ammonium ions on the acid sites. These disparities are well known in the art. They can be particularly problematic when certain treatments such as the subsequently described dealumination methods are employed which results in the presence of free aluminum of the zeolite structure. Therefore care must be taken to ensure that the ratio of the silica: alumina structure is correctly determined to the extent acceptable to the practitioner of the technique. When the zeolites have been prepared in the presence of organic cations they are catalytically inactive, possibly because the intracristal free space is occupied by organic cations originating from the formation solution. These can be activated by heating them in an atmosphere at 540 ° C for one hour, for example, followed by exchange in basic medium with ammonium salts and then calcination at 540 ° C in the air. The presence of organic cations in the formation solution may not be absolutely essential for the formation of the zeolite; but it seems to be that it favors the formation of this special type of zeolite. Some natural zeolites can sometimes be converted to zeolites of the desired type by various activation methods and other treatments such as exchange in basic medium, vaporization, alumina extraction and calcination. The zeolites preferably have a density of crystalline structure, in the dry hydrogenated form, not substantially below about 1.6 g / cm 3. The dry density for known structures can be calculated from the number of silicon atoms plus aluminum atoms per 1000 cubic Angstroms, as is given, for example on page 19 of the article Zeolite Structure by W.M. Meier included in "Proceedings of the Conference on Molecular Sieves, London, April 1967", published by the Society of Chemical Industry, London 1968. Reference is made to this document for a discussion of crystal structure density. An additional discussion of the crystal structure density, together with values for some typical zeolites, is given in the patent E.U.A. No. 4,016,218, to which reference is made. When synthesized in the alkali metal form, the zeolite is conveniently converted to the hydrogenated form (acid), generally by intermediate formation of the ammonium form by ammonium ion exchange and calcination of the ammonium form to give the hydrogenated form. It has been found that although the hydrogenated form of the zeolite catalyses the reaction successfully, the zeolite may also be partially in the metalalkaline form and / or the form of other metal salts. EP 466,558 discloses an alkylation catalyst of the mordenite acid type which can also be used herein which has a total atomic ratio of Si / Al of 15-85 (15-60), Na content in weight less than 1000 ppm (preferably less than 250 ppm), having a minimum or no content of extra Al species; the elemental mesh volume as defined in EP 466,558 is below 2.760 nm3. The patent E.U.A. No. 5,057,472 is equally useful for preparing alkylation catalysts herein and refers to concurrent dealumination and ion exchange of a zeolite containing Na ion. ria-IÉ-? rtÉ ^^ ugly '< ^^ feA? ^ --- A ^ '* 1 acid-stable, preferably mordenite, affected by contact of the zeolite with a solution of HNO3 0.5-3 (preferably 1-2.5) M containing enough NH3N3 to exchange completely the Na + ions by NH4 + ions and H + ions. The resulting zeolites can have a ratio of 5 SiO2: AI2O3 from 15: 1 to 26: 1, preferably 17: 1 to 23: 1, and preferably calcined until at least partially converting the NH + / H + form to the H + form. Optionally, although not necessarily desired in particular in the present invention, the catalyst may contain a Group VIII metal (and optionally also an inorganic oxide) together with the calcined zeolite. of the '472 patent. Another acid mordenite catalyst useful for the alkylation step herein is described in the U.S.A. 4,861, 935 which refers to a hydrogenated mordenite incorporated with alumina, the composition having a surface area of at least 580 m2 / g.

Other mordenite-acid-based catalysts useful for the alkylation step herein include those described in US Pat. 5,243,116 and E.U.A. 5,198,595. Even another alkylation catalyst useful herein is described in the U.S.A. 5,175,135 which is a zeolite based on acid mordenite having a silica / alumina molar ratio of At least 50: 1, a symmetry index of at least 1.0 as determined by X-ray diffraction analysis, and a porosity such that the total pore volume is on the scale of about 0.18 cc / g to about 0.45 cc / g and the ratio of the combined meso- and macropore volume to the total pore volume is from about 0.25 to about 0.75. Particularly preferred alkylation catalysts herein include the Zeocat ™ FM-8 / 25H acid mordenite based catalysts available from Zeochem; CBV 90 A available from Zeolyst International, and LZM-8 available from UOP Chemical Catalysts as well as fluorinated versions of the above commercial catalysts. Fluorinated mordenites can be prepared in a number of ways. A method for providing a particularly useful fluorinated mordenite is described in U.S. Patent No. 5,777,187. The invention encompasses preferred embodiments in which the mordenites are fluorinated, but also has other preferred embodiments in which the mordenitaes are non-fluorinated. More generally, any alkylation catalyst herein can be used with the proviso that the alkylation catalyst can: (a) accommodate branched defines as described elsewhere herein in the smallest pore diameter of said catalyst and (b) alkylate benzene selectively with said branched olefins and optionally mixtures thereof with unbranched olefins The acceptable selectivity is in accordance with a 2/3-phenyl index of about 275 to about 10,000 as defined in In other words, the catalyst selections herein are made in part with the intention of minimizing the formation of internal alkylbenzene (e.g., 4-phenyl, 5-phenyl ...). present invention have unexpectedly discovered that the control of alkylbenzenesulfonate isomers in the surfactant mixtures of the present invention and In conjunction with the introduction of limited methyl branching, it is very useful to improve its performance. The present invention connects this discovery with the discoveries of the synthetic chemicals in the present invention, which have determined how to control the internal isomer content while providing limited methyl branching in modified alkylbenzene sulfonate surfactant mixtures in accordance with the prescriptions of the formulator. The degree to which the internal isomer content needs to be controlled can vary depending on the product application to the consumer and whether the best performance or a balance between yield and cost is directly required. In absolute terms, the amount of internal isomer such as internal alkylbenzene isomer is preferably always kept below 25% by weight, although for best results, from 0 to 10%, preferably less than about 5% by weight. The "internal alkylbenzene" isomers as defined herein include alkylbenzenes having phenyl adhesion to an aliphatic chain at the 4, 5, 6 or 7 position. Without wishing to be limited by theory, there are two reasons why believes that the preferred alkylation catalysts are the zeolite type selective catalysts described above, especially mordenites. The first reason is to provide the selectivity of formation of preferred compounds such as branched and unbranched 2-phenyl and 3-phenylalkylbenzenes. This selectivity is measured by the 2/3-phenyl index. The second reason is to control the amount of quaternary alkylbenzenes and consequently the quaternary alkylbenzene sulphonates. Results with alkylation catalysts such as HF can give fairly high levels of quaternary alkylbenzenes as shown in the literature (see J. Org. Chem. Vol. 37, No. 25, 1972). This contrasts with the surprise discovery as part of the present invention that low levels of quaternary alkylbenzenes can be achieved in catalyzed reactions of benzene with branched olefins, as characterized by the 2-methyl-2-phenyl index. Even though the olefins which are used are substantially diramified, as illustrated herein, a low 2-methyl-2-phenyl index of less than 0.1 can be obtained in a surprising manner.

Second modality Detergent compositions. The present invention has numerous detergent composition embodiments, including the detergent composition comprising: (a) from about 1% to about 50%, preferably from 2% to about 30% by weight, of modified alkylbenzene sulfonate surfactant mixture of the first embodiment, wherein said modified alkyl benzene sulfonate surfactant mixture has a 2-methyl-2-phenyl index of less than about 0.3, preferably from 0 to 0.2, more preferably not more than 0.1, more preferably, not more than approximately 0.05; (b) from about 0.000001% to about 10%, preferably from about 0.01% to about 2%, of a member that is selected from the group consisting of optical brighteners, dyes, photobleaches, hydrophobic bleach activators and metal bleach catalysts transition, preferably at least two of said component members, more preferably at least two of said component members include an optical brightener as one of the component members; (c) from 0.1% to about 40% by weight, (preferably not more than about 30%), of surfactants which are selected from the group consisting of cationic surfactants, nonionic surfactants, anionic surfactants, and surfactants. amine oxide (more preferably at least one cationic surfactant is present at a level of 0.2% to about 5% by weight, or at least one nonionic surfactant is present at a level of 0.5% to about 25% by weight , or at least one alkyl sulfate surfactant or an alkyl (polyalkoxy) sulfonate surfactant is present at a level of 0.5% to about 25% by weight); and (d) from about 10% to about 99% conventional cleaning aids (other than any of (a) - (c)); with the proviso that when said detergent composition comprises any alkylbenzene sulfonate surfactant other than said mixture of modified alkyl benzene sulphonate surfactants (e.g. as a result of mixing in the detergent composition one or more commercially available, especially linear, alkylbenzene sulphonate surfactants, typically linear of C10-C14), said detergent composition is further characterized by a total 2/3-phenyl index of at least about 200, preferably at about 250, more preferably at least about 350, even more preferably, at least about 500, wherein said 2/3-phenyl index is determined by measuring the 2/3-phenyl index, as defined herein, in a combination of said mixture of modified alkylbenzenesulfonate surfactants and any other alkylbenzenesulfonate that will be added to said detergent composition , said combination n, for measurement purposes, it is prepared from aliquots amounts of the surfactant blend modified alkylbenzene and of other alkylbenzene that has not been exposed to any other component of the detergent composition; and with the additional proviso that when said detergent composition comprises any alkylbenzene sulfonate surfactant other than the mixture of modified alkyl benzene sulfonate surfactants (for example, as a result of combining in the detergent composition one or more commercial alkylbenzene sulfonate surfactants) , especially linear, typically linear C10-C14), said detergent composition is further characterized by a total 2-methyl-2-phenyl index of less than about 0.3, preferably from 0 to 0.2, more preferably not more than 0.1, even more preferably, not more than 0.05, in which said 2-methyl-2-phenyl ester index will be determined by measuring the 2-methyl-2-phenyl index, as defined herein, in a combination of said mixture of modified alkyl benzene sulfonate surfactants and any other alkylbenzene sulfonate to be added to said detergent composition, said combination, for measurement purposes, is prepared from aliquots of the mixture. of modified alkylbenzene sulfonate surfactants and the other alkylbenzenesulfonate which has not yet been exposed to any other component of the detergent composition. Preferably, said conventional cleaning aid comprises from about 0.1% to about 5% of a cationic surfactant, such as one selected from C8-C16 alkylammonium salts, linear and branched, substituted and unsubstituted. Numerous variations of the detergent compositions of the present invention are useful. Such variations include: • The detergent composition that is substantially free of alkylbenzene sulfonate surfactants other than the modified alkyl benzene sulphonate surfactant mixture. • The detergent composition comprising, in said component (c), at least about 0.1%, preferably not more than about 10%, more preferably not more than about %, more preferably, no more than about 1%, of a commercial linear C 10 -C 14 alkylbenzenesulfonate surfactant. The detergent composition comprising, in said component (c), at least about 0.1%, preferably not more than about 10%, more preferably not more than about 5%, more preferably, not more than about l%, of a highly branched commercial alkylbenzene sulfonate surfactant (for example TPBS or tetrapropylbenzenesulfonate). • The detergent composition comprising, in said component (c), a nonionic surfactant at a level of from about 0.5% to about 25% by weight of said detergent composition, and wherein said nonionic surfactant is a polyalcoxylated alcohol in blocked or unblocked form that has: - a hydrophobic group selected from linear C10-C26 alkyl, branched C10-C16 alkyl from C1-C3 in the middle part of its chain, branched C10-C16 alkyl from guerbet, and mixtures thereof, and - a hydrophilic group selected from 1-15 ethoxylates, 1-15 propoxylates, 1-15 butoxylates and mixtures to* . m of them, in blocked or unblocked form. (When they are not blocked, a primary -OH portion is also present and when they are blocked, a terminal portion of the -OR form is also present in which R is a hydrocarbyl portion of C 1 -C 6, optionally comprising a primary alcohol or , preferably when present, a secondary one: The detergent composition comprising, in said component (c), an alkyl sulfate surfactant at a level of about 0.5%, to about 25% by weight of said detergent composition, wherein said alkyl sulfate surfactant has a hydrophobic group selected from linear C10-C18 alkyl, branched C10-C18 alkyl from C1-C3 in the middle part of its chain, branched C10-C18 alkyl from guerbet, and mixtures thereof and a cation selected from Na, K, and mixtures thereof • The detergent composition comprising, in said component (c), an alkyl (polyalkoxy) sulfate surfactant at a level of about 0.5% to about 25% by weight of said detergent composition, and wherein said alkyl (polyalkoxy) sulfate surfactant has a hydrophobic group selected from linear C10-C16 alkyl, branched C10-C16 alkyl of C1-C3 in the middle part of its chain, branched C10-C16 alkyl of guerbet, and mixtures thereof, and - a hydrophilic group of (polyalkoxy) sulfate selected from 1-15 polyethoxysulfate, 1-15 polypropoxylsulfate, 1-15 polybutoxy sulfate, 1-15 mixed poly (ethoxy / propoxy / butoxy) sulfates and mixtures of the mlsfins, in blocked or unblocked form; and a cation selected from Na, K and mixtures thereof. • The detergent composition in the form of a heavy-duty liquid detergent. • The detergent composition that has the shape of a synthetic laundry detergent bar. • The detergent composition that has the shape of a heavy duty granule. • The detergent composition having the form of a heavy duty granule and wherein said conventional cleaning aid (d) comprises from about 10% to about 50% by weight of said detergent composition of a non-phosphate builder. • The detergent composition having the form of a heavy duty granule and wherein said conventional cleaning aid (d) comprises from about 10% to about 50% by weight of said detergent composition of a phosphate builder; and • The detergent composition having the form of a heavy duty granule and wherein said conventional cleaning aid (d) comprises as said phosphate builder a member selected from the group consisting of sodium tripolyphosphate. In addition, the present invention includes a detergent composition comprising (preferably consisting essentially of): (a) from about 1% to about 95%, by weight (preferably from 0.5% to about 50%, more preferably from about 1%, preferably at least 2%, more preferably at least 4%, more preferably at least 6%, even more preferably from 8% to about 35%) of modified alkyl benzene sulfonate surfactant mixture according to the invention; (b) from about 0.00001% to about 99.9%, (preferably from about 5% to about 98%, more preferably from about 50% to about 95%) of conventional cleaning aids other than surfactants; and (c) from 0% to about 50%, by weight (in some preferred embodiments, 0% and in others preferably from about 0.1% to about 30%, more typically from about 0.2% to about 10%) of a surfactant other than the mixture of modified alkyl benzene sulfonate surfactants; with the proviso that when said detergent composition comprises any other alkylbenzene sulfonate other than the alkylbenzene sulfonate of said mixture of modified alkyl benzene sulphonate surfactants, said mixture of modified alkyl benzene sulphonate surfactants and the other alkylbenzene sulfonate, as a mixture, has a 2/3-phenyl index total of at least about 275 to 10,000, (preferably from less than about 350 to about 1200, more preferably from about 500 to about 700).

The invention also encompasses a detergent composition consisting essentially of: (a) from about 1% to about 50% (preferably from 1% to about 35%), by weight of alkylbenzene sulfonate surfactant mixture modified in accordance with the first embodiment of the invention; (b) from about 0.00001% to about 99.9%, (preferably from about 5% to about 98%, more preferably from about 50% to about 95%) of conventional cleaning aids other than surfactants; and (c) from 0.1% to approximately 50% (preferably from about 0.1% to about 35%, more typically from about 1% to about 15%) by weight of surfactants other than alkylbenzene sulfonates (preferably, one or more surfactants that are selected from the group consisting of cationic surfactants , surfactants non-anionic, and anionic surfactants other than alkylbenzene sulfonates, more preferably in which a cationic surfactant is present at a level of 0.2% to about 5%); and (d) from 0.1% to about 95% water. Likewise, part of the invention is a composition or detergent consisting essentially of: (a) from about 0.1% to about 95%, by weight of mixture of alkylbenzene sulfonate surfactants modified according to the first embodiment; Hj m ^^^ j ^ na ^ (b) from about 0.00001% to about 99.9% of conventional cleaning aids other than surfactants. More generally, the detergent compositions can include mixtures of modified alkyl benzene sulfonate surfactants together with any conventional cleaning aid other than surfactants, such as those in which the auxiliary is selected from the group consisting of detergency builders, detersive enzymes , bleaching systems, brighteners, polymers at least partially soluble in water or dispersible in water, abrasives, bactericides, oxidation inhibitors, dyes, solvents, hydrotropes, perfumes, thickeners, antioxidants, processing aids, foam impellers, foam suppressors, pH regulators, antifungal agents, mold control agents, insect repellents, anti-corrosion auxiliaries, chelators and mixtures thereof. Also more generally, the detergent compositions of the invention may be in the form of a liquid, powder, agglomerate, paste, tablet, bar, gel or granule. With respect to the modalities of the detergent composition and the methods of its uses, such as a method comprising treating a fabric with the detergent composition of the invention. Said methods are part of the present invention.

Third modality Mixtures of Modified Alkyl Benzene The present invention also includes a modified alkylbenzene mixture comprising (preferably consisting essentially of): (a) from 60% to about 95% (preferably from about 65% to about 90%, more preferably from about 70%) % to about 85%) by weight of a mixture of branched alkylbenzenes having the formula (I): XLX I A (Wherein L is an aliphatic acyclic portion consisting of carbon and hydrogen and has two methyl terms and wherein said mixture of branched alkylbenzenes contains two or more compounds of formula (I) that differ in molecular weight from the anion of said formula (I) and in which said mixture of branched alkylbenzenes is characterized by a sum of carbon atoms in R1, R2 and L of 9 to 15, preferably 10 to 14, and an average aliphatic carbon content (i.e. A), based on the sum of R1, L and R2, from about 10.0 to about 14.0, preferably from 11.0 to about 13.0, more preferably from about 11.5 to about 12.5 carbon atoms, and in addition in which L has no different substituents A, R1 and R2, R1 is C1-C3 alkyl, (preferably C1-C2 alkyl, more preferably methyl), R2 is selected from H and C1-C3 alkyl (preferably H and C1-C2 alkyl, more preferably H and methyl, more preferably H and methyl with the proviso that in at least about 0.5, more Preferably 0.7, more preferably 0.9 to 1.0 mole fraction of said branched alkylbenzene sulphonates R2 is H); A is a benzene portion (typically A is the benzene (non-sulfonated) portion (CßHs- having no substituents other than L), and (b) from 5% to about 40% (preferably from about 10% to about 35%, more preferably from 15% to about 30%) by weight of a mixture of Unbranched O-alkylbenzenes having the formula (II): Y I A (ll) In which A is a benzene portion typically A is the benzene (non-sulfonated) portion (C6H5- which has no substituents other than L) and Y is an unsubstituted linear aliphatic portion consisting of carbon and hydrogen having two methyl terms , and in which Y has from 9 to 15 carbon atoms in total (preferably from 10 to 14) and said mixture of Unbranched alkylbenzenes have an average aliphatic carbon content of about 10.0 to about 14.0 carbon atoms, preferably 11.0 to about 13.0 carbon atoms, more preferably about 11.5 to 12.5 carbon atoms. carbon; and wherein said modified alkylbenzene mixture is further characterized by a 2/3-phenyl index of from 275 to about 10,000, preferably from 350 to about 1200, more preferably from about 500 to about 700; and a 2-methyl-2-phenyl index of less than about 0.3, preferably from 0 to about 0.2, more preferably not more than about 0.1, even more preferably, 0.05 or less. In another example, the invention includes a modified alkylbenzene mixture comprising: I) from about 20% to about 99%, (or more, preferably 40% or more, more preferably more than half, for example, 60% or more, even more preferably 70% or more), by weight of a first alkylbenzene mixture, in which said first mixture of modified alkylbenzene (itself a modified type of alkylbenzene mixture according to the invention) consists of Essentially from: a) from 60% to about 95% by weight of a mixture of branched alkylbenzenes having the formula (I): XL I A (I) In which L is an aliphatic acyclic portion consisting of carbon and hydrogen and has two methyl terms and in which said mixture of branched alkylbenzenes contains two or more compounds of formula (I) differing in molecular weight and in which said mixture of alkylbenzenes It is characterized by a sum of carbon atoms in R1, R2 and L from 9 to 15, preferably from 10 to 14; and an average aliphatic carbon content based on the sum of R1, L and R2, from about 10.0 to about 14.0, preferably from 11.0 to about 13.0, more preferably from about 11.5 to about 12.5 carbon atoms; and in which L has no substituents other than A, R1 and R2; R1 is C1-C3 alkyl, (preferably C1-C2 alkyl, more preferably methyl); R2 is selected from H and C1-C3 alkyl (preferably H and C1-C2 alkyl, more preferably H and methyl, more preferably H and methyl with the proviso that at least about 0.5, more preferably 0.7, more preferably from 0.9 to 1.0 mole fraction of said branched alkylbenzenesulfonates R2 is H); A is a benzene (non-sulfonated) portion (C6H5- which has no substituents other than L); and (b) from 5% to about 40% by weight (preferably not more than about 35%, more preferably not more than about 30%) of a mixture of unbranched alkylbenzenes having the formula (II): Y I A (ll) In which A is a benzene (non-sulfonated) portion (C6H5- which has no substituents other than A) and Y is an unsubstituted linear aliphatic portion consisting of carbon and hydrogen having two terms Other embodiments: Mixtures of 2/3 phenyl surfactant medium The present invention also encompasses mixtures of modified alkylbenzenesulfonate surfactant which are more particularly called "2/3 phenyl middle surfactant mixtures". Said mixtures are not the most preferred ones offered by the invention, but they can be very economical. In this way the invention includes a medium 2/3 phenyl surfactant mixture consisting essentially of: from 1% (preferably at least about 5%, more preferably at least about 10%) to 60% (in a preferably less embodiment) 50%, more preferably less than about 40%), by weight of a first alkylbenzenesulfonate surfactant, wherein said first alkylbenzenesulfonate surfactant is a mixture of alkylbenzene sulfonate surfactants modified in accordance with the first embodiment; and 40% (in one embodiment preferably at least about 50%, more preferably at least about 60%) to about 99% (preferably: less than 95%, more preferably less than about 90%), by weight of a second alkylbenzene sulfonate surfactant, wherein said second alkylbenzene sulfonyl surfactant is a mixture of alkylbenzene sulphonate surfactants other than the mixture of alkylbenzene sulphonate surfactants modified according to the first embodiment, and wherein said second surfactant of alkylbenzenesulfonate has a 2/3-phenyl index of 75 to about 160 (Typically said second acylbenzenesulfonate surfactant is a commercial linear C10-C14 alkylbenzenesulfonate surfactant, for example DETAL® process LAS or HF process LAS, although in general any linear (LAS) or branched commercial type (LAS) may be used. ABS, TPBS)); with the proviso that said average 2/3 phenyl surfactant mixture has a 2/3-phenyl index of from about 160 to about 275 (preferably from about 170 to about 265, more preferably from about 180 to about 255). Of course it is also possible within the spirit and scope of the invention to prepare any combination of the modified alkylbenzene sulfonate surfactant mixture of the invention with any known commercial linear or branched akylbenzene sulfonate surfactant. Also included is a detergent composition comprising (preferably consisting essentially of): (a) from about 1% to about 95%, by weight (preferably from 0.5% to about 50%, more preferably from about 1% to about 35% ) of 2/3-phenyl medium surfactant mixture as defined above; (b) from about 0.00001% to about 99.9%, (preferably from about 5% to anionic surfactants other than alkylbenzene sulfonates, more preferably in which a cationic surfactant is present at a level of 0.2% to about 5%); with the proviso that when said detergent composition comprises any other alkylbenzene sulfonate other than the alkylbenzenesulfonate of said 2/3-phenyl middle surfactant mixture, said mixture of 2/3-phenyl middle surfactant and the other alkylbenzene sulfonate, as a mixture , has a total 2/3-phenyl index of from about 160 to about 275. Also included herein is a detergent composition consisting essentially of: (a) from about 1% to about 50%, by weight of agent mixture 2/3-phenyl medium surfactant as defined above; (b) from about 0.1% to about 98.8%, of conventional cleaning aids other than surfactants; (c) from 0.1% to about 50% by weight of surfactants other than alkylbenzene sulphonates (preferably, one or more surfactants which are selected from the group consisting of cationic surfactants, anionic surfactants, and anionic surfactants other than alkylbenzene sulphonates, more preferably in which a cationic surfactant is present at a level of 0.2% a about 5%); and (d) from about 0.1% to about 98.8% water. In additional embodiments of the 2/3-phenyl medium type, a detergent composition is included which consists essentially of: (a) from about 0.1% to about 95%, preferably from 1% to about 50% by weight of the surfactant mixture of 2 / 3- middle phenyl as defined above; and (b) from about 0.00001% to about 99.9%, of cleaning aids different conventional to surfactants. The processes for preparing a mixture of 2/3-phenyl middle surfactant include those comprising a step which is selected from: combining the first alkylbenzene sulfonate surfactant and the second surfactant : or alkylbenzenesulfonate; and (ii) combining the non-sulfonated precursor of the first alkylbenzenesulfonate surfactant and the non-sulfonated precursor of the second alkylbenzenesulfone surfactant and sulfonating said combination.

EXAMPLES OF PREPARATION EXAMPLE 1 Mixture of 4-methyl-4-nonanol, 5-methyl-5-decanol, 6-methyl-6-undecanol and 6-methyl-6-dodecanol 20 (A starting material for branched olefins) A mixture of 4.65 g of 2-pentanone, 20.7 g of 2-hexanone, 5.10 g of 2-heptanone, 36.7 g of 2-octanone and 72.6 g of diethyl ether are sa ^ B ^^ added to an addition funnel. The ketone mixture is then added by dripping for a period of 2.25 hours to a 3-L round bottom flask stirred with nitrogen blanket, equipped with a reflux condenser and containing 600 ml of 2.0 M n-bromide. -pentylmagnesium in diethyl ether and an additional 400 ml of diethyl ether. After the addition is complete, the reaction mixture is stirred an additional 2.5 hours at 20 ° C. The reaction mixture is then added to 1 kg of crushed ice with stirring. To this mixture is added 393.3 g of 30% sulfuric acid solution. The aqueous acid layer is drained and the remaining ether layer is washed twice with 750 ml of water. The ether layer is then evaporated under vacuum to yield 176.1 g of a mixture of 4-met: '- 4-nonanol, 5-methyl-5-decanol, 6-methyl-6-undecanol and 6-methyl-6-dodecanol .

EXAMPLE 2 Mixture of substantially mono methyl branched olefin with random branching (A branched olefin mixture which is an alkylating agent for preparing alkylbenzenes according to the invention) a) A sample of 174.9 g of the branched monomethyl alcohol mixture of example 1 is added to a 500 ml three-necked round bottom flask with nitrogen blanket, equipped with a Dean Stark separator and a reflux condenser together with 35.8 g of a zeolite catalyst * - »- *" * * - ^ - * »* Selective form (Acid mordenite catalyst Zeocat® FM-8 / 25H) With mixing, the mixture is then heated to approximately 110-155 ° C and water and some olefin are collected over a period of 4-5 hours in the Dean Stark separator The conversion of the alcohol mixture of Example 1 to a substantially non-random methyl branched olefin mixture is now complete. The substantially non-random branched methyl which remains in the flask together with the substantially non-random methyl branched olefin mixture collected in the Dean Stark separator is recombined and filtered to remove the catalyst.The solid filter cake is washed twice with 100-fold portions. ml of hexane The hexane filtrate is evaporated under vacuum and the resulting product is combined with the first filtrate to give 148.2 g of a substantially non-random methyl branched olefin mixture b) The olefin mixture of example 2a is com bina with 36 g of a form-selective zeolite catalyst (acid mordenite catalyst Zeocat® FM-8 / 25H) and reacted according to example 2 a with the following changes. The reaction temperature is raised to 190-200 ° C over a period of about 1-2 hours to randomize the specific branching positions in the olefin mixture. The mixture of substantially monomethyl branched olefin with the randomized branch remaining in the flask together with the substantially monomethyl branched olefin mixture with randomized branch collected in the Dean Stark separator are combined and filtered to remove the catalyst. The solid filter cake is washed twice with 100 ml portions of hexane. The hexane filtrate is evaporated under vacuum and the resulting product is combined with the first filtrate to give 147.5 g of a substantially branched monomethyl olefin mixture with randomized branching.

EXAMPLE 3 Alkylbenzene mixture substantially mono methyl branched With a 2/3-phenyl index of about 550 and a 2-methyl-2-phenyl index of about 0.02 (a mixture of modified alkylbenzene according to the invention) 147 g of the substantially monomethyl branched olefin mixture of example 2 and 36 g of a shape-selective zeolite catalyst (acid mordenite catalyst Zeocat® FM-8 / 25H) are added to a stirred steel 7,570 L stainless steel autoclave. . The residual olefin and the catalyst in the container are washed in the autoclave with 300 ml of n-hexane and the autoclave is sealed. From outside the autoclave cell, 2000 g of benzene (contained in an insulated container and added by an isolated pump system inside the isolated autoclave cell) are added to the autoclave. The autoclave is purged twice with N2 17.5 kg / cm2 gravimetric, and then charged to N2 4.21 kg / cm2 gravimetric. The mixture is stirred and heated to about 200 ° C for about 45 minutes. The autoclave ^ ^ f * is cooled to approximately 20 ° C overnight. The valve that leads from the autoclave to the benzene condenser and to the collection tank is opened. The autoclave is heated to approximately 120 ° C with continuous benzene collection. By the time the reactor reaches 120 ° C, no more benzene is collected. The reactor is then cooled to 40 ° C and 750 g of n-hexane is pumped into the autoclave with mixing. The autoclave is then drained to remove the reaction mixture. The reaction mixture is filtered to remove the catalyst and the n-hexane is removed under vacuum. The product is distilled under vacuum (1-5 mm Hg). The mixture of substantially monomethyl branched alkylbenzene with a 2/3-phenyl number of about 550 and a 2-methyl-2-phenyl index of about 0.02 is collected from 76 ° C-130 ° C (167 g).

EXAMPLE 4 Alkylbenzenesulfonic acid mixture substantially mono methyl branched with a 2/3-phenyl index of about 550 and a 2-methyl-2-phenyl index of about 0.02 (a mixture of modified alkylbenzenesulfonic acid according to the invention) The product of Example 3 is sulphonated with one molar equivalent of chlorosulfonic acid using methylene chloride as the solvent. The methylene chloride is removed to give 210 g of a substantially monomethyl branched alkylbenzene sulfonic acid mixture with a 2/3-phenyl number of about 550 and a 2-methyl-2-phenyl index of about 0.02.

EXAMPLE 5 Mixture of substantially mono methyl branched alkylbenzenesulfonate, sodium salt with a 2/3-phenyl number of about 550 (a mixture of modified alkylbenzenesulfonate surfactant according to the invention) The product of Example 4 is neutralized with one molar equivalent of sodium methoxide in methanol and the methanol is evaporated to give 225 g of a substantially monomethyl branched alkylbenzenesulfonate mixture, sodium salt with a 2/3-phenyl index of about 550 and a 2-methyl-2-phenyl index of about 0.02.

EXAMPLE 6 Substitution of substantially linear alkylbenzene with a 2/3-phenyl index of about 550 and a 2-methyl-2-phenyl index of about 0.02 (a mixture of alkylbenzene to be used as a component of modified alkylbenzenes) A mixture of substantially linear alkylbenzene chain lengths with a 2/3-phenyl index of about 550 and a 2-methyl-2-phenyl index of about 0.02 is prepared using a zeolite-selective, form-structured catalyst (Zeocat acid mordenite catalyst). ® FM-8 / 25H). A mixture of 15.1 g of Neodene®10, 136.6 g of Neodene®1112, 89.5 g of Neodene®12, and 109.1 g of 1-tridezene is added to an agitated stainless steel 7.570 L autoclave, together with 70 g of a shape selective zeolite catalyst (acid mordenite catalyst Zeocat® FM-8 / 25H). Neodene is a trade name for olefins from Shell Chemical Company. The residual olefin and the catalyst in the container are washed in the autoclave with 200 mL of n-hexane and the autoclave is sealed. From outside the autoclave cell, 2500 g of benzene (contained in an insulated container and added by an isolated pump system inside the isolated autoclave cell) are added to the autoclave. The autoclave is purged twice with N2 17.57 kg / cm2 gravimetric, and then charged to N2 4.21 kg / cm2 gravimetric. The mixture is stirred and heated to about 200-205 ° C for about 4 hours and then cooled to 70-80 ° C. The valve that leads from the autoclave to the benzene condenser and to the collection tank is opened. The autoclave is heated to approximately 120 ° C with continuous collection of benzene in the collection tank. By the time the reactor reaches 120 ° C, no more benzene is collected. The reactor is then cooled to 40 ° C and 1 kg of n-hexane is pumped into the autoclave with mixing. The autoclave is then drained to remove the reaction mixture. The reaction mixture is filtered to remove the catalyst and the n-hexane is evaporated under low vacuum. The product is then distilled under high vacuum (1-5 mm Hg). The substantially linear alkylbenzene mixture with a 2/3-phenyl number of about 550 and a 2-methyl-2-phenyl index of about 0.02 is collected from 85 ° C-150 ° C (426.2 g).

EXAMPLE 7 Mixture of substantially linear alkylbenzenesulfonic acid with a 2/3-phenyl number of about 550 and a 2-methyl-2-phenyl index of about 0.02 (a mixture of alkylbenzenesulfonic acid to be used as a component of modified alkylbenzenesulfonic acid mixtures in accordance with the invention) 422. 45 g of the product of Example 6 are sulfonated with one molar equivalent of chlorosulfonic acid using methylene chloride as -solvent. The methylene chloride is removed to give 574 g of a substantially linear alkylbenzenesulfonic acid mixture with a 2/3-phenyl number of about 550 and a 2-methyl-2-phenyl index of about 0.02.

EXAMPLE 8 Mixture of substantially linear alkylbenzenesulfonate, sodium salt with a 2/3-phenyl number of about 550 (a mixture of alkylbenzenesulfonate surfactant to be used as a component of modified alkylbenzenesulfonate surfactant mixtures according to the invention) The substantially linear alkylbenzene sulfonic acid mixture of Example 7 is neutralized with one molar equivalent of sodium methoxide in methanol and the methanol is evaporated to give 613 g of a substantially linear alkylbenzenesulfonate mixture, sodium salt with a 2/3-phenyl number. of about 550 and a 2-methyl-2-phenyl index of about 0.02 EXAMPLE 9 6,10-dimethyl-2-undecanol (A starting material for branched olefins) To a glass autoclave lining is added 299 g of geranylacetone, 3.8 g of 5% ruthenium in carbon and 150 ml of methanol. The glass liner is sealed inside a 3L stainless steel tilting autoclave and the autoclave is purged one time with N2 17.57 kg / cm2 gravimetric once with H2 17.57 kg / cm2 gravimetric and then loaded with H2 7.03 kg / gravimetric cm2. With mixing, the reaction mixture is heated. At approximately 75 ° C, the reaction starts and begins to consume H2 and exotherms at 170-180 ° C. In 10-15 minutes, the temperature has dropped to 100-110 ° C and the pressure has dropped to 35.15 kg / cm2 gravimetric. The autoclave is increased to 70.30 kg / cm2 gravimetric with H2 and mixed at 100-110 ° C for 1 hour and an additional 40 minutes with the reaction consuming additional 11.25 kg / cm2 gravimetric H2 but at which time no H2 consumption is observed . Upon cooling the autoclave at 40 ° C, the reaction mixture is removed, filtered to remove the catalyst and concentrated by Evaporation of methanol under vacuum to yield 297.75 g of 6,10-dimethyl-2-undecanol.

EXAMPLE 10 5 -dimethyl-2-decanol (A starting material for branched olefins) To a glass autoclave lining is added 249 g of 5,7-dimethyl-3,5,9-decatrien-2-one, 2.2 g of 5% ruthenium in carbon and 200 ml of methanol. The glass liner is sealed inside a 3L stainless steel tilting autoclave and the autoclave is purged one time with N2 17.57 kg / cm2 gravimetric once with H2 17.57 kg / cm2 gravimetric and then loaded with H235.15 kg / gravimetric cm2. With mixing, the reaction mixture is heated. At approximately 75 ° C, the reaction starts and begins to consume H2 and exotherms at 170 ° C. In 10 minutes, the temperature has dropped to 115-120 ° C and the pressure has fallen to 19.98 kg / cm2 gravimetric. The autoclave is increased to 70.30 kg / cm2 gravimetric with H2 and mixed at 110-115 ° C for 7 hours and 15 additional minutes and then cooled to 30 ° C. The reaction mixture is removed from the autoclave, filtered to remove the catalyst and concentrated by evaporation of methanol under vacuum to yield 225.8 g of 5,7-dimethyl-2-decanol.

EXAMPLE 11 4,8-dimethyl-2-nonanol (A starting material for branched olefins) A mixture of 671.2 g of citral and 185.6 g of diethyl ether is added to an addition funnel. The citral mixture is then added by dripping over a period of five hours to a 5 L round bottom flask., 3-neck agitated, with nitrogen blanket, equipped with a reflux condenser containing 1.6 L of 3.0 M solution of methylmagnesium bromide and an additional 740 ml of diethyl ether. The reaction flask is placed in an ice water bath to control the exotherm and subsequent ether reflux. After the addition is complete, the ice water bath is removed and the reaction is allowed to mix for an additional 2 hours at 20-25 ° C at which point the reaction mixture is added to 3.5 kg of crushed ice with good agitation . To this mixture is added 1570 g of 30% sulfuric acid solution. The aqueous acid layer is drained and the remaining ether layer is washed twice with 2 L of water. The ether layer is concentrated by evaporating the ether under vacuum to yield 720.6 g of a mixture of 4,8-dimethyl-3,7-nonadien-2-ol. To a glass autoclave lining is added 249.8 of the 4,8-dimethyl-3,7-nonadien-2-ol, 5.8 g of 5% ruthenium in carbon and 200 ml of n-hexane. The glass liner is sealed inside a 3L stainless steel tilting autoclave and the autoclave is purged twice with N2 17.57 kg / cm2 gravimetric once with H2 17.57 kg / cm2 gravimetric and then loaded with H2 7.03 kg / gravimetric cm2. With the mixture, the reaction begins and begins to consume H2 and exotherms at 75 ° C. The autoclave is heated to 80 ° C, increased to 35.15 kg / cm2 gravimetric with H2, mixed for 3 hours and then cooled to 30 ° C. The reaction mixture is removed from the autoclave, filtered to remove the catalyst and concentrated by evaporating n-hexane under vacuum to yield 242 g of 4,8-dimethyl-2-nonanol.

EXAMPLE 12 Mixture of substantially branched dimethyl olefin with random branching (A branched olefin mixture which is an alkylating agent for preparing modified alkylbenzenes according to the invention) To a 2 L, round bottom, 3-neck flask with nitrogen blanket, equipped with thermometer, mechanical stirrer and a Dean Stark separator with reflux condenser is added 225 g of 4,8-dimethyl-2-nonanol (example 11), 450 g of 5,7-dimethyl-2-decanol (example 10), 225 g of 6,10-dimethyl-2-undecanol (example 9), and 180 g of a zeolite-selective catalyst (catalyst of acid mordenite Zeocat® FM-8 / 25H). With mixing, the mixture is heated (135-160 ° C) to the point where water and some olefin are expelled and collected in the Dean Stark separator at a moderate rate. After a few hours, the water collection becomes slower and the temperature rises to 180-195 ° C where the reaction is allowed to mix for an additional 2-4 hours. The branched dimethyl olefin mixture remaining in the flask together with the branched dimethyl olefin mixture is recombined and filtered to remove the catalyst. The catalyst filter cake is suspended with 500 ml of hexane and filtered in vacuo. The catalyst filter cake is washed twice with 100 ml of hexane and the filtrate is concentrated by evaporation of the hexane under vacuum. The resulting product is combined with the first filtrate to give 820 g of a branched dimethyl olefin mixture with random branching.

EXAMPLE 13 Mixture of substantially dimethyl branched alkylbenzene with random branching and a 2/3-phenyl index of about 600 and a 2-methyl-2-phenyl index of about 0.04 (a mixture of modified alkylbenzene according to the invention) 820 g of the branched dimethyl olefin mixture of example 12 and 160 g of a shape-selective zeolite catalyst (acid mordenite catalyst Zeocat® FM-8 / 25H) are added to a stirred stainless steel 7.570 L autoclave. and the autoclave is sealed. The autoclave is purged twice with N2 5.62 kg / cm2 gravimetric and then charged to N2 4.21 kg / cm2 gravimetric. From outside the autoclave cell, 3000 g of benzene (contained in an insulated container and added by an isolated pump system inside the isolated autoclave cell) are added to the autoclave. The mixture is stirred and heated from 205 ° C to about 210 ° C. The reaction continues for about 10 minutes at which time samples of the reaction mixture are taken. The 10 minute sample is filtered to remove the catalyst and pulled under vacuum to the mixture to remove any residual traces of benzene. The sample is distilled under vacuum (1-5 mm Hg). The mixture of branched dimethyl alkylbenzene with random branching and a 2/3-phenyl index of about 600 and a 2-methyl-2-phenyl index of about 0.26 is collected from 90 ° C-140 ° C. The reaction continues at 205 ° C to about 210 ° C for about 8 hours. The autoclave is cooled to approximately 30 ° C overnight. The valve that leads from the autoclave to the benzene condenser and to the collection tank is opened. The autoclave is heated to approximately 120 ° C with continuous benzene collection. By the time the reactor reaches 120 ° C, no more benzene is collected and the reactor is then cooled to 40 ° C. The autoclave is then drained to remove the reaction mixture. The reaction mixture is filtered to remove the catalyst and pulled under vacuum in the mixture to remove any residual traces of benzene. The product is distilled under vacuum (1-5 mm Hg). The mixture of branched dimethyl alkylbenzene with random branching and a 2/3-phenyl index of about 600 and a 2-methyl-2-phenyl index of about 0.04 is collected from 90 ° C-140 ° C.

EXAMPLE 14 Mixture of substantially dimethyl branched alkylbenzenesulfonic acid with random branching and a 2/3-phenyl index of about 600 and a 2-methyl-2-phenyl index of about 0.04 (a mixture of modified alkylbenzenesulfonic acid according to the invention) The branched dimethyl alkylbenzene product of Example 13 is sulphonated with one molar equivalent of chlorosulfonic acid using methylene chloride as a solvent with HCl evolving as a side product. The resulting sulfonic acid product is concentrated by evaporation of methylene chloride under vacuum. The substantially dimethyl branched alkylbenzene sulfonic acid mixture has a 2/3-phenyl number of about 600 and a 2-methyl-2-phenyl index of about 0.04.

EXAMPLE 15 Mixture of substantially dimethyl branched alkylbenzene sulphonic acid, sodium salt, with random branching and a 2/3-phenyl index of about 600 and a 2-methyl-2-phenyl index of about 0.04 (a mixture of modified alkyl benzene sulphonate surfactant) in accordance with the invention) The branched dimethyl alkylbenzene sulphonic acid mixture of example 14 is neutralized with one molar equivalent of sodium methoxide in methanol and the methanol is evaporated to give a mixture of solid branched dimethyl alkylbenzene sulfonate, sodium salt, with random branching and a 2/3 index phenyl of about 600 and a 2-methyl-2-phenyl index of about 0.04.

EXAMPLE 16 Mixtures of modified aliphenylbenzene sulphonate surfactant according to the invention (type 2/3-average phenyl) The mixtures are prepared from: I) Mixture of modified alkylbenzenesulfonate surfactant according to the invention having a 2/3-phenyl index of about 550 (according to example 5). II) Sodium salt of commercial linear alkylbenzenesulfonate surfactant of Cu 7 (average) (type HF) having a 2/3-phenyl index of approximately 100. In the following table the percentages are by weight: B 25% 15% 38% 75% 85% 62% Each of the above mixtures has a 2/3-phenol ratio on the scale of about 160 to about 275.

EXAMPLE 17 Mixtures of modified aliphenylbenzenesulfonate surfactant according to the invention (type 2/3-phenyl medium) The mixtures are prepared from: I) Modified alkylbenzene sulfonate surfactant mixture according to the invention having a 2/3-phenyl index of about 550 (according to example 5) II) Sodium salt of alkylbenzene sulfonate surfactant linear commercial of Cn. (average) (DETAL® type) having a 2/3-phenyl index of approximately 150. In the following table the percentages are by weight: A B 25% 15% 10% 75% 85% 90% Each of the above mixtures has a 2/3-phenyl index in the range from about 160 to about 275.

EXAMPLE 18 Mixtures of modified albuylbenzenesulphonic acid according to the invention (type 2/3-phenyl middle) The mixtures are prepared from: I) Mixture of modified alkylbenzenesulfonic acid surfactant according to the invention having a 2/3-phenyl index of about 550 (according to example 4). II) Commercial linear alkylbenzenesulfonic acid of Cn 7 • (average) (type HF) having a 2/3-phenyl index of approximately 100. In the following table the percentages are by weight: B 25% 15% 38% 75% 85% 62% Each of the above mixtures has a 2/3-phenyl index in the range from about 160 to about 275.

EXAMPLE 19 Mixtures of modified albulebenzenesulphonic acid according to the invention (type 2/3-average phenyl) The mixtures are prepared from: I) Modified alkylbenzenesulfonic acid mixture according to the invention having a 2/3-phenyl index of about 550 (according to example 4). II) Commercial linear alkylbenzenesulfonic acid of Cn 7 (average) (DETAL® type) having a 2/3-phenyl index of approximately 100. In the following table the percentages are by weight: B 25% 15% 10% 75% 85% 90% Each of the above mixtures has a 2/3-phenyl index in the range from about 160 to about 275.

EXAMPLE 20 Mixtures of modified alkylbenzene according to the invention (type 2/3-phenyl medium) The mixtures are prepared from: I) Modified alkylbenzene mixture according to the invention having a 2/3-phenyl index of about 550 (according to example 3). II) Commercial linear alkyl benzene of C11 7 (average) (type HF) which has a 2/3-phenyl index of about 100. In the following table the percentages are by weight: B 25% 15% 38% 75% 85% 62% 15 Each of the above mixtures has a 2/3-phenyl index on the scale of about 160 to about 275.

EXAMPLE 21 Mixtures of modified alkylbenzene according to the invention (type 2/3-phenyl middle) The mixtures are prepared from: I) Modified alkylbenzene mixture according to the invention having a 2/3-phenol ratio of about 550 (according to example 3). II) Commercial linear alkylbenzene of Cu 7 (average) (DETAL® type) having a 2/3-phenyl index of about 150. In the following table the percentages are by weight: B I 25% 15% 10% II 75% 85% 90% Each of the above mixtures has a 2/3-phenyl index in the range from about 160 to about 275.

EXAMPLE 22 Mixture of modified alkylbenzene according to the invention With a 2/3-phenyl index of approximately 550 and a 2-methyl-2-phenyl index of approximately 0.02 110. 25 g of the substantially monomethyl branched olefin mixture of example 2, 36.75 g of an unbranched olefin mixture (decene: undecene: dodecene: tridecene ratio of 2: 9: 20: 18) and 36 g of a selective zeolite catalyst of form (acid mordenite catalyst Zeocat® FM-8 / 25H) are added to a stirred stainless steel 7.570 L autoclave. The residual olefin and the catalyst in the container are washed in the autoclave with 300 mL of n-hexane and the autoclave is sealed. From outside the autoclave cell, 2000 g of benzene (contained in an insulated container and added by an isolated pump system inside the isolated autoclave cell) are added to the autoclave. The autoclave is purged twice with N2 17.57 kg / cm2 gravimetric, and then charged to N2 4.21 kg / cm2 gravimetric. The mixture is stirred and heated to about 200 ° C for about 4-5 hours. The autoclave is cooled to approximately 20 ° C overnight. The valve that leads from the autoclave to the benzene condenser and to the collection tank is opened. The autoclave is heated to approximately 120 ° C with continuous benzene collection. By the time the reactor reaches 120 ° C, no more benzene is collected. The reactor is then cooled to 40 ° C and 750 g of n-hexane is pumped into the autoclave with mixing. The autoclave is then drained to remove the reaction mixture. The reaction mixture is filtered to remove the catalyst and the n-hexane is removed under vacuum. The product is distilled under vacuum (1-5 mm Hg). The mixture of modified alkylbenzene with a 5 2/3-phenyl index of about 550 and a 2-methyl-2-phenyl index of about 0.02 is collected from 76 ° C-130 ° C (167 g).

EXAMPLE 23 Mixture of modified alkylbenzenesulfonic acid according to the invention (mixture of branched and unbranched a-alkylbenzenesulfonic acid) with a 2/3-phenyl index of about 550 and a 2-methyl-2-phenyl index of about 0.02.

The modified alkyl benzene mixture of Example 22 is sulfonated with one molar equivalent of chlorosulfonic acid using methylene chloride as the solvent. The methylene chloride is removed to give 210 g of a mixture of modified alkylbenzenesulfonic acid with a 2/3-phenyl index of about 550 and a 2-methyl-2-phenyl index of approximately 0.02.

Example 26 Mix of modified alkylbenzenesulfonate, sodium salt according to the invention - (mixture of branched and unbranched alkylbenzene sulfonate, sodium salt) with a 2/3-phenyl number of about 550 and an index 2-methyl-2-phenyl of about 0.02 The modified alkylbenzenesulfonic acid of Example 23 is neutralizes with a molar equivalent of sodium methoxide in methanol and the methanol is evaporated to give 225 g of a modified alkylbenzenesulfonate mixture, sodium salt, with a 2/3-phenyl index of approximately 550 and a 2-methyl-2-index. 2-phenyl of about 0.02.

Methods for determining the composition parameters (2/3-phenyl index, 2-methyl-2-phenyl index) of mixed systems of alkylbenzene / alkylbenzenesulfonate / alkylbenzenesulfonic acid.

It is well known in the art to determine the parameters of composition of conventional linear alkylbenzenes and / or highly branched alkylbenzene sulfonates (TPBS, ABS). See, for example, Surfactant Science Series, Volume 40, Chapter 7 and Surfactant Science Series, volume 73, chapter 7. Typically this is done through The GC and / or GC mass spectroscopy for alkylbenzenes and HPLC for alkylbenzenesulfonates or sulphonic acids. The 13C NMR is also commonly used. Another common practice is desulphonation. This allows GC and / or mass GC spectrography to be used, because the sulfonation converts the sulphonates or sulphonic acids to the alkylbenzenes that are detectable by such methods. In general, the present invention provides unique and relatively complex mixtures, and similarly complex surfactant mixtures of alkylbenzenesulfonates and / or alkylbenzenesulfonic acids. The composition parameters of said compositions can be determined using variations and combinations of methods known in the art. The sequence of methods that will be used depends on the composition that will be characterized as follows: trfi -TíiáMft * -ft raa & ^ aSiife, -.

S? F.

* Typically preferred when the material contains more than 10% impurities such as dialkylbenzenes, olefins, paraffins, hydrotropes, dialkylbenzenesulfonates, etc. , CG Equipment: • Hewlett Packard HP5890 Series II 20 gas chromatograph equipped with a split / non-split injector and FID. • Scientific capillary column J & W DB-1 HT, 30 meters, 0.25 mm dia, 0.1 μm film thickness, cat. No. 1221131 • Restek Septos Red 11 mm cat. No. 22306 • 4mm Restek gooseneck entry sleeve with a carb. Cap. No. 20799-209.5 '• O-ring for Hewlett Packard Cat inlet liner. No. 5180-4182. 5 • Methylene chloride J.T. Baker grade HPLC cat. No. 9315-33, or equivalent. • 2 ml GC self-ampoules with folded tips, or equivalent.

Preparation of the sample: • Weigh 4-5 mg of sample in a 2 ml GC self-ampoule. • Add 1 ml of methylene chloride J.T. Baker HPLC grade, Cat. 9315-33 to the CG ampoule, seal with caps (caps) with 11 mm Teflon coating for folded vial, Part No. HP5181-1210 using crimping tool, Part No. HP8710-0979 and mix well. • The sample is now ready for injection in the CG.

CG Parameters: Carrier Gas: Hydrogen Column head pressure: 0.630 kg / cm2 Flows: Column flow @ 1 ml / min.

^ S ^^ g ^.

Division fan @ 3 ml / min. Septum purge @ 1 ml / min. Injection: Automatic HP 7673 (Autosampler) syringe of 10 ul, injection of 1 ul. Injector temperature: 350 ° C. Detector temperature: 400 ° C. Oven temperature program: Initial 70 ° C sustained 1 minute. Speed: 1 ° C / min. Final 180 ° C sustained 10 min.

The standards required for this method are 2-phenyloctane and 2-phenylpentadecane, each freshly distilled at a purity greater than 98%. Operate both standards using the conditions that are specified above to define the retention time for each standard. This defines a retention time scale which is the retention time scale that will be used to characterize any alkylbenzenes or mixtures of alkylbenzenes in the context of this invention (e.g., test samples). Then operate the test samples for which the composition parameters will be determined. The test samples pass the CG test with the proviso that more than 90% of the total CG area percentage is within the retention time scale defined by the two standards. The test samples that pass the GC test can be used directly in the NMR1 and NMR2 test methods. Test samples that do not pass the CG test must be further purified until the test samples pass the CG test.

Desulfonation (DE) The desulfonation method is a standard method that is described in "The Analysis of Detergents and Detergent Products", by G.F. Longman on pages 197-199. Two other useful descriptions of this standard method are given on page 230-231 of volume 40 of Surfactant Science Series edited by T.M. Schmitt: "Analysis of Surfactants" and on page 272 of volume 73 of the Surfactant Science Series: "Anionic Surfactants" edited by John Cross. This is an alternative method to the HPLC method, which is described herein, for the evaluation of branched and unbranched alkylbenzene sulfonic acid and / or salt mixtures (mixtures of modified alkylbenzenesulfonic acid and / or salts). This method provides a means for converting the mixture of sulphonic acid and / or salt into the branched and unbranched alkylbenzene mixtures which can then be analyzed by means of the GC and NMR1 and NMR2 NMR methods described in FIG. I presented. £ * * - &amp! ¡É® & J & 0 & HPLC Consult L.R. Snyder and J.J. Kirkiand, "Introduction to Modern Liquid Chromatography ", 2nd ed., Wiley, NY, 1979.

Apparatus Suitable HPLC system, Millipore Division or equivalent HPLC pump with Waters model 600 or He sprayer and equivalent temperature control Waters 717 injector / injector, or equivalent Waters 48-position Tray or equivalent for automating Waters PDA 996 UV detector or equivalent Fluorescence detector Waters 740 or equivalent Waters 860 system or equivalent data / integrator Ampoules and covers of Millipore No. 78514 and auto 78515 of 4 ml capacity HPLC column, X2 Supelcosil LC18, 5 μm, 4.6 mm x 25 cm, Supelcosil No 58298. Rheodyne entry filter 0.5um x 3mm Rheodyne column No. 7335 Millipore membrane filters SJHV M47 10, CL eluent disposable filter funnel with 0.45 μm membrane. Sartorius weighs or equivalent; accuracy ± 0.0001 g. Vacuum Sample clarification equipment with pumps and filters, Waters, No. WAT085113.

Reagents Standard material LAS of C8 sodium p-2-octylbenzenesulfonate. Standard material LAS of C15 sodium p-2-pentadecylbenzenesulfonate.

Process A.- Preparation of HPLC mobile phase 1.- Mobile phase A a) Weigh 11.690 g of sodium chloride and transfer to a 2000 ml volumetric flask. Dissolve in 200 ml of HPLC grade water. b) Add 800 ml of acetonitrile and mix. Dilute to volume after the solution reaches room temperature. This prepares a solution of 100 mM NaCl / 40% ACN. c) Filter through a membrane filter of eluent of LC and degas before use. 2.- Mobile phase B.- Prepare 2000 ml of 60% acetonitrile in HPLC grade water. Filter through a CL eluent membrane filter and degas before use.

B.- Internal standard solution of C8 and C15. 1.- Weigh 0.050 g of a standard of 2-phenyloctylbenzenesulfonate and 0.050 g of another standard of 2-phenylpentadecane sulphonate and quantitatively transfer to 5 a volumetric 100-ml flask. 2.- Dissolve with 30 ml of ACN and dilute to volume with HPLC grade water. This prepares ca. 1500 ppm of mixed standard solution.

C- Sample solutions 1.- Wash solutions.- Transfer 250 μl of the standard solution to a 1 ml self-cleaning vial and add 750 μl of the washing solution. Cover and place in the auto tray. 2.- Alkylbenzenesulfonic acid or albuylbenzenesulfonate.- Weigh 0.10 g of the alkylbenzenesulfonic acid or salt and transfer quantitatively to a 100 ml volumetric flask. Dissolve with 30 ml of ACN and dilute to volume with HPLC grade water. Transfer 250 μl of the solution standard to a 1 ml self-vial and add 750 μl of the sample solution. Cover and place in the self-cleaning tray. If the solution is excessively cloudy, filter through a membrane of 0.45 um before «Ís = ß? AßSi sAíal? SÉfSi, -. i HI ^ to transfer to the auto vial. Cover and place in the self-cleaning tray. D.- HPLC System 1.- Prime the HPLC pump with mobile phase. Install column and column inlet filter and equilibrate with eluent (0.3 ml / min for at least 1 hour). 2.- Operate the samples using the following HPLC conditions: Mobile phase A 100 mM NaCl / 40% ACN Mobile phase B 40% H2O / 60% ACN Time 0 minutes 100% mobile phase A 0% mobile phase B Time 75 minutes 5% mobile phase A 95% mobile phase B Time 98 minutes 5% mobile phase A 95% mobile phase B Time 110 minutes 100% mobile phase A 0% phase mobile B Time 120 minutes 100% mobile phase A 0% mobile phase B Note: A s time delay gradient may be required depending on the dead volume of the HPLC system. Flow rate: 1.2 ml / min. Temperature: 25 ° C Hex spray speed: 50 ml / hour UV detector: 225 nm Fluorescence detector:? = 225 nm,? = 295 nm with sensitivity to 10 x. Operating time: 120 min. Injection volume: 10 μL 5 Duplicate injections 2 Data rate: 0.45 MB / hour Resolution: 4.8 nm. 3. - The column should be washed with 100% water followed by 100% acetonitrile and stored in 80/20 ACN / water. The HPC elution time of the 2-phenyloctylbenzenesulfonate defines the lower limit and the elution time of the standard 2-phenylpentadecanesulfonate defines the highest limit of the HPLC analysis relative to the alkylbenzenesulfonic acid / salt mixture of the invention. If 15 90% of the components of the alkylbenzenesulfonic acid / salt mixture have retention times within the scale of the above standards then the sample can be further defined by NMR 3 and 4 NMR methods. If the alkylbenzene sulfonic acid / salt contains 10% or 20 more components outside the retention limits defined by the standards then the sample must be further purified by the HPLC-P method or by the methods of DE, DIS. j ^ j ^^ g ^ i ^ Sj ^^ ígg ^^? ^^^^ £ ^^^ »^ jg HPLC preparation (HPLC-P) Alkylbenzenesulfonic acids and / or salts containing substantial impurities (10) % or larger) are purified by preparative HPLC. Consult L.R. Snyder and J.J. Kirkiand, "Introduction to Modern 5 Liquid Chromatography", 2nd ed., Wiley, NY, 1979. This is routine for the person skilled in the art. A sufficient amount must be purified to meet the requirements of NMR 3 and RMN 4.

Preparation CL method using Mega Bond Elut Sep 10 Pak® (HPLC-P). Alkylbenzenesulfonic acids and / or salts containing substantial impurities (10% or greater) can also be purified by a CL method (also defined herein as HPLC-P). This method is currently preferred over the purification of HPLC column preparation. As much as 500 mg of unpurified MLAS salts can be loaded in a Mega Bond Elut Sep Pak® of 10 g (60 ml) and with optimized chromatography the MLAS salt can be isolated and ready for freeze drying within 2 hours. A sample of 100 mg of modified alkyl benzene sulfonate salt 20 can be loaded into a 5 g (20 ml) Elut Sep Pak® Mega Bond and ready within the same amount of time.

M? V? ÍÍÁ *** TiititfMlttlT.MHiif ll "i liíifi f - '^^^^^^^^^^^^^^^^^ mk A.- Instrumentation: HPLC: Waters gradient pump model 600E, model 717 , Waters Millenium PDA, Millenium Data Manager (v. 215) Mega Bond Elut: joined phase of C18, Varian 5g or 10g, PN: 1225-6023, 1225-6031 with adapters HPLC Columns: Supelcosil LC-18 (X2), 250x4.6mm, 5mm, No. 58298. Analytical weighing: mettler model AE240, capable of weighing samples at ± 0.01 mg B.- Accessories Volumetric: glass, 10 ml Graduated cylinder: 1 L. Ampoules HPLC autoclave: 4 ml glass ampoules with Teflon lids and inserts and low volume glass pipette capable of accurately delivering volumes of 1, 2 and 5 ml C- Reagents and Water Chemicals (DI-H2O): distilled, deionized water from a Millipore Millipore system or equivalent Acetonitrile (CH3CN): Baker's HPLC grade sodium chloride or Baker's glass equivalent analyzed or equivalent D.- Conditional HPLC units Aqueous phase preparation: A: To 600 ml of DI-H2O contained in a graduated cylinder of 1 L, add 5,845 of sodium chloride: Mix well and add 400 ml of ACN. Mix well. B: A 400 ml of DI-H2O contained in a 1 L graduated cylinder, add 600 ml of ACN and mix well. Reserve A: 60/40 H2O / CAN with salt and Reserve B: 40/60, H2O / ACN. Operating conditions: Gradient: 100% for 75 min. 5% A / 95% B for 98 min. 5% A / 95% B for 110 min. 100% A for 125 min. Column temperature: Not thermofixed (ie, room temperature). HPLC flow rate: 1.2 mL / min. Injection volume: 10 mL Operating time: 125 minutes. UV detection: 255 nm. Conc. >4 mg / ml.

BALANCE OF SEP PAK (BOND ELUT, 5G) 1.- Pass 10 ml of the solution containing 25/75 H2O / ACN to sep pak by applying a positive pressure with a syringe of 10 ce at a rate of ~ 40 drops / min. Do not allow the sep pak to dry. | ¿.. 4 É É É É 2. 2. 2. 2. Hacer 10 10 10 10 10 10 10 10 10 10 10 10 10 10 10 10 10 10 10 10 10 10 10 10 10 No No No No No No No No No No No No No No No No No No. Maintain a level of solution (x 1mm) in the head of the sep pak. 3.- The sep pak is now ready for sample loading.

LOAD / SEPARATION AND ISOLATION OF MLAS SAMPLE 4.- Weigh < 200 mg of sample in a 1-dram vial and add 2 ml of 70/30 H2O / ACN. Sonicate and mix well. 5.- Load the sample in Bond Elut and with positive pressure from a syringe of 10 seconds to start the separation. Rinse the vial with 1 ml (x2) portions of the 70/30 solution and load into the sep pak. Keep ~ 1mm of the solution on the head of the sep pak. 6.- Pass 10 ml of 70/30 in the Bond Elu with positive pressure from a syringe of 10 ce at a speed of ~ 40 drops / min. 7.- 4.- Repeat this with 3 ml and 4 ml and collect the effluent if impurities are of interest.

ISOLATION AND COLLECTION OF MLAS 1.- Pass 10 ml of solution containing 25/75 H20 / ACN with positive pressure from a 10-ce syringe and collect the effluent. fff ^ • * «f Mr 'Repeat this with another 10 ml and again with 5 ml. The isolated MLAS is now ready for freeze drying and subsequent characterization. 2.- Rotovaporize until ACN is removed and freeze the remaining H2O. The sample is now ready for chromatography. Note: when the Mega Bond Elut Sep Pak (10g version) is incorporated, up to 500 mg of sample can be loaded in the sep pak and with solution volume adjustments, the effluent can be ready for freeze drying within 2 hours.

BALANCE OF SEP PAK (BOND ELUT, 5G) 1- Pass 20 ml of the solution containing 25/75 H2O / ACN ai sep pak using laboratory air or regulated cylinder air J at a rate that will allow ~ 40 drops / min. Positive pressure can not be used from a syringe because it is not enough to move the solution through the sep pak. Do not allow the sep pak to dry. 2.- Immediately pass 20 ml (x2) and an additional 10 ml of a solution containing 70/30 H2O / ACN in the same way as in No. 1. Do not allow the sep pak to dry. Maintain a solution level (~ 1 mm) on the head of the sep pak. 3.- The sep pak is now ready for sample loading.

LOAD / SEPARATION AND ISOLATION OF MLAS SAMPLE 1.- Weigh < 500 mg of sample in a 2-dram vial and add 5 ml of 70/30 H2O / ACN. Sonicate and mix well. 2.- Load the sample in Bond Elut and with positive pressure from an air source start the separation. Rinse the vial with 2 ml portions (x2) of the 70/30 solution and put in the sep pak. Keep ~ 1mm of solution on the head of the sep pak. 3.- Pass 20 ml of 70/30 in the Bond Elu with positive pressure from an air source at a speed of ~ 40 drops / min. Repeat this with 6 ml and 8 ml and collect the effluent if impurities are of interest.

ISOLATION AND COLLECTION OF MLAS 1.- Pass 20 ml of solution containing 25/75 H20 / ACN with positive pressure from an air source and collect the effluent. 2.- Repeat this with another 20 ml and again with 10 ml. This isolated fraction contains the pure MLAS. 3. The isolated MLAS is now ready for freeze drying and subsequent characterization. 4. Rotovaporize until ACN is removed and freeze the remaining H2O. The sample is now ready for chromatography. - + ^ * m * i £ 2 -. ^^^ Note: Adjustments in organic modifier concentration may be necessary for optimal separation and isolation.

DISTILLATION (DIS) A 5-liter, round-bottom, 3-necked flask with 24/40 joints is equipped with a magnetic stirrer bar. A few boiling flakes (Hengar Granules, Catalog No. 136-C) are added to the flask. A vigreux condenser 24.03 cm long with a 24/40 union is placed in the neck of the center of the flask. A water cooled condenser attaches to the top of the vigreux condenser that is equipped with a calibrated thermometer. A vacuum receiving flask is adhered to the end of the condenser. A glass stopper is placed in a side arm of the 5-liter flask and a calibrated thermometer in the other. The vigreux flask and condenser are wrapped with aluminum wrap. To the 5 liter flask, 2270 g of an alkylbenzene mixture containing 10% or more of impurities is added as defined by the GC method. A vacuum line leading from a vacuum pump is adhered to the receiving flask. The alkylbenzene mixture in the 5 liter flask is stirred and vacuum is applied to the system. Once the maximum vacuum is reached (at least 2.54 cm Hg pressure by gauge or less), the alkylbenzene mixture is heated by an electric heating mantle. The distillate is collected in two fractions. Fraction A is collected from about 25 ° C to about 90 ° C as measured by the calibrated thermometer at the top of the vigreux column. Fraction B is collected from about 90 ° C to about 155 ° C as measured by the calibrated thermometer at the top of the vigreux column. Fraction A and container residues (high boiling) are discarded. Fraction B (1881 g) contains the alkylbenzene mixture of interest. The method can be scaled according to the needs of the practitioner provided that a sufficient amount of the alkylbenzene mixture remains for evaluation by RMN 1 and NMR 2 NMR methods.

AIDIFICATION (AC) The salts of alk acids > The benzenesulfonic acids are acidified by common means such as reaction in a solvent with HCl or sulfuric acid or by the use of an acid resin such as Amberlyst 15. Acidification is routine for the person skilled in the art. After acidifying all solvents are removed, especially any moisture, so that the samples are anhydrous and solvent-free. Note: For all the following NMR test methods, the chemical changes of the NMR spectrum are referred either externally or internally to TMS in CDCI3, ie chloroform.

RMN 1 13C-NMR 2/3-phenyl index for mixtures of alouylbenzene. A sample of 400 mg of an alkylbenzene mixture is dissolved in 1 ml of deuterated anhydrous chloroform containing 1% v / v of TMS as reference and placed in a standard NMR tube. The 13 C-NMR is operated on the sample on a 300 MHz NMR spectrometer using a recycle time of 20 seconds, a pulse amplitude of 13C of 40 ° and heteronuclear decoupling of gate. At least 2000 scrutinies are recorded. The 13 C-NMR spectrum region between about 145.00 ppm to about 150.00 ppm is integrated. The 2/3-phenyl index of an alkylbenzene mixture is defined by the following equation: 2/3-phenyl index = (Integral from about 147.65 ppm to about 148.05 ppm) / (Integral from about 145.70 ppm to about 146.15 ppm) x 100 NMR 2 13C-NMR 2-methyl-2-phenyl index A sample of 400 mg of an anhydrous alkylbenzene mixture is dissolved in 1 ml of deuterated anhydrous chloroform containing 1% v / v of TMS as reference and placed in an NMR tube standard. The 13C-NMR USE- * ~ -... • «&.,., - is operated on the sample on a 300 MHz NMR spectrometer using a recycle time of 20 seconds, a pulse amplitude of 13C 40 ° and gate heteronuclear decoupling. At least 2000 scrutinies are recorded. The 13 C-NMR spectrum region between about 145.00 ppm to about 150.00 ppm is integrated. The 2-methyl-2-phenyl index of an alkylbenzene mixture is defined by the following equation: 2-methyl-2-phenyl index = (Integral from about 149.35 ppm to about 149.80 ppm) / (Integral from about 145.00 ppm to about 150.00 ppm).

RMN 3 13C-NMR index 2/3-phenyl for mixtures of alkylbenzenesulfonic acid. A 400 mg sample of an anhydrous alkylbenzene sulfonic acid mixture is dissolved in 1 ml of deuterated anhydrous chloroform containing 1% v / v TMS as a reference and placed in a standard NMR tube. The 13 C-NMR is operated on the sample on a 300 MHz NMR spectrometer using a recycle time of 20 seconds, a pulse amplitude of 13 C of 40 ° and heteronuclear gate decoupling. At least 2000 scrutinies are recorded. The 13 C-NMR spectrum region between approximately 152.50 ppm at ^. ^^^^^ áj ^^^^^^ approximately 156.90 ppm is integrated. The 2/3-phenyl index of an alkylbenzenesulfonic acid mixture is defined by the following equation: 2/3-phenyl index = (Integral from about 154.40 ppm to about 154.80 ppm) / (Integral from about 152.70 ppm to about 153.15 ppm) x 100 RMN 4 13C-NMR 2-methyl-2-phenyl ester for mixtures of alkylbenzenesulfonic acid. A 400 mg sample of an anhydrous alkylbenzene sulphoic acid mixture is dissolved in 1 ml of deuterated anhydrous chloroform containing 1% v / v TMS as a reference and placed in a standard NMR tube. The 13 C-NMR is operated on the sample on a 300 MHz NMR spectrometer using a recycle time of 20 seconds, a pulse amplitude of 13 C of 40 ° and heteronuclear gate decoupling. At least 2000 scrutinies are recorded. The 13 C-NMR spectrum region between about 152.50 ppm to about 156.90 ppm is integrated. The 2-methyl-2-phenyl index for a mixture of alkylbenzenesulfonic acid is defined by the following equation: 2-methyl-2-phenol index = (Integral from about 156.40 ppm to about 156.65 ppm) / (Integral from about 152.50 ppm to about 156.90 ppm).

DETERMINENT COMPOSITIONS IN DETAILED The new modified alkylbenzenesulfonate surfactant mixtures of the present invention can be incorporated into cleaning compositions, so-called "detergent compositions" herein because the preferred ones of said compositions are for laundry cleaning, especially for used in household washing machines or for hand washing. These compositions can be in any conventional form, that is, in the form of a liquid, powder, agglomerate, paste, tablet, bar, gel or granule. The detergent compositions of the present invention can be used more generally in a wide range of consumer cleaning product compositions including powders, liquids, granules, gels, pastes, tablets, bags, bars, types supplied in double-compartment containers , spray or foam detergents and other forms of homogenous or multiphasic consumer cleaning products. They can be used or applied by hand and / or can be applied in unitary or freely alterable dosing, or by automatic assortment means, or are useful in apparatuses such as washing or dishwashing machines or can be used in institutional cleaning contexts, including for example, for personal cleaning in public facilities, for washing bottles, for cleaning surgical instruments or for cleaning electronic components. They can be used in aqueous or non-aqueous cleaning systems. They may have a broad pH range, for example from about 2 to about 12 or higher, although alkaline detergent compositions having a pH of about 8 to about 11 are among the preferred embodiments, and may have a broad scale of alkalinity that may include very high alkalinity reserves such as in uses such as drain drainage where tens of grams of NaOH equivalent can be present per 100 grams of formulation, varying between 1-10 grams of NaOH equivalent and scales of moderate to low alkalinity of liquid hand cleaners, up to the acidic side as in acidic cleaners for hard surfaces. Also included are the high foaming and low foaming detergent types, as well as the types to be used in all known aqueous and non-aqueous consumer cleaning product processes. Consumer cleaning product compositions are described in "Surfactant Science Series", Marcel Dekker, New York, volumes 1-67 et seq. The liquid compositions in particular are described in detail in volume 67, "Liquid Detergents", Ed. Kuo-Yann Lai, 1997, ISBN 0-8247-9391-9, incorporated herein by reference. The most classic formulations, especially granular types, are described in "Detergent Manufacture including Zeolite Builders and Other New Materials", Ed. M. Sittig, Noyes Data Corporation, 1979, incorporated by reference. See also Encyclopedia of Chemical Technology by Kirk Othmer. The compositions of cleaning products for the consumer (detergent compositions) herein include, but are not limited to: Light duty liquid detergents (LDL): those compositions include compositions having magnesium ions that improve the surfactant (see for example WO 97/00930 A; GB 2,292,562 A; 5,376,310, US 5,269,974, USA 5,230,823, USA 4,923,635, USA 4,681, 704, USA 4,316,824, UA 4,133,779) and / or organic diamines and / or various foam stabilizers and / or foamer enhancers such as amine oxides (see for example US 4,133,779) and / or skin sensing modifiers of types of surfactant, emollient and / or enzymatic including proteases; and / or anti microbial agents; a more complete patent list is given in Surfactant Science Series, vol. 67 pages 240-248. Heavy Duty Liquid Detergents (HDL): These compositions include the "structured" or multi-phase liquid types (see for example, US 4,452,717, US 4,526,709, US 4,530,780, US 4,618,446, US 4,793,943, US 4,659,497, US 4,871, 467, US. 4,891, 147; USA 5,006,273; USA 5,021, 195; USA 5,147,576; USA 5,160,655) and "unstructured" or isotropic and in general can be aqueous or non-aqueous (see, for example, EP 738,778 A; WO 97/00937 A; WO 97/00936 A; EP 752,466 A; DE 19623623 A; WO 96/10073 A; WO 96/10072 A; USES. 4,647,393; USES. 4,648,983; USES. 4,655,954; USES. 4,661, 280; EP 225,654; USES. 4,690,771; USES. 4,744,916; USES. 4,753,750; USES. 4,950,424; USES. 5,004,556; USES. 5,102,574; WO 94/23009); and can be with bleach (see for example U.S.A. 4,470,919; USES. 5,250,212; EP 564,250; USES. 5,264,143; USES. ,275,753; USES. 5,288,746; WO 94/11483; EP 598,170; EP 598,973; EP 619,368; USES. 5,431, 848; USES. 5,445,756) and / or enzymes (see for example U.S.A. 3,944,470, U.S.A. 4,111, 855; U.S.A. 4,261, 868; U.S.A. 4,287,082; USES. 4,305,837; USES. 4,404,115; USES. 4,462,922; USES. 4,529.5225; USES. 4,537,706; USES. 4,537,707; USES. 4,670,179; USES. 4,842,758; USES. 4,900,475; USES. 4,908,150; USES. 5,082,585; USES. ,156,773; WO 92/19709; EP 583,534; EP 583,535; EP 583,536; WO 94/04542; USES. 5,269,960; EP 633,311; USES. 5,422,030; USES. 5,431, 842; USES. 5,442,100) or without bleach and / or enzymes. Other patents that refer to liquid heavy duty detergents are tabulated or listed in Surfactan Science Series, Vol. 67, pages 309-324. Heavy duty granular detergents (HDG): these compositions include so-called "compact" or agglomerated or otherwise non-spray dried, as well as granules called "spongy" or "densified" spray-dried or spray-dried types. Phosphate and non-phosphate types are included. Such detergents may include the most common anionic surfactant based types or may be so-called "high nonionic surfactant" types in which commonly the nonionic surfactant is contained in or on an absorbent such as zeolites or other porous salts inorganic The manufacture of HDGs is described in, for example, EP 753,571 A; WO 96/38531 A; USES. 5,576,285; USES. 5,573,697; WO 96/34082 A; USES. 5,569,645; EP 739,977 A; USES. 5,565,422; EP 737,739 A; WO 96/27655 A; USES. 5,554,587; WO 96/25482 A; WO 96/23048 A; WO 96/22352 A; EP 709,449 A; WO 96/09370 A; USES. 5,496,487; USES. 5,489,392 and EP 694,608 A. "Softening detergents" (STW): these compositions include the various types of granular or liquid products (see for example EP 753,569 A, US 4,140,641, US 4,639,321, USA 4,751, 008, EP 315,126, US 4,844,821; USA 4,844,824, USA 4,873,001, USA 4,911, 852, USA 5,017,296, EP 422,787) which soften by washing and in general can have organic (for example, quaternary) or inorganic (for example, clay) softeners. Hard surface cleaners (HSC): these compositions include cleaners for all purposes such as cream cleaners and liquid cleaners for all purposes; spray cleaners for all purposes including glass cleaners and tile and spray cleaners with bleach; and bathroom cleaners including types for mold removal, which contain bleach, antimicrobial, acid, neutral and basic. See, for example, EP 743,280 A; EP 743,279 A. Acid cleaners include those of WO 96/34938 A. Bar soaps (BS &HW): these compositions include bars for personal cleansing as well as so-called laundry rods (see, for example WO 96/35772 A ); including types of synthetic detergent (syndet) and soap based and types with softener (see U.S.A. 5,500,137 or WO 96/01889 A); said compositions may include those made by common soapmaking techniques such as bar extrusion and / or more unconventional techniques such as casting, absorbing surfactant on a porous support, or the like. Other bar soaps are also included (see, for example BR 9502668, WO 96/04361 A; WO 96/04360 A; E.U.A. 5,540,852). Other detergents for hand washing include those described in GB 2,292,155 A and WO 96/01306 A. Shampoos and conditioners (S &C): (consult, for example, WO 96/37594 A; WO 96/17917 A; 96/17590 A; WO 96/17591 A). Said compositions generally include simple shampoos and types called "two in one" or "with conditioner". Liquid soaps (LS): these compositions include so-called "antibacterial" and conventional types, as well as those with or without skin conditioners and include types suitable for use in tí ^? ^ tM pump dispensers, and by other means such as devices supported on the wall that are used institutionally. Fabric softeners (FS): these compositions include conventional liquid types and concentrated liquids (see, for example EP 754,749 A; WO 96/21715 A; USA 5,531,910; EP 705,900 A; USA 5,500,138) as well as the types they are added to the dryer or supported by a substrate (see, for example, US 5,562,847, US 5,559,088, EP 704,522 A). Other fabric softeners include solids (see, for example U.S.A. 5,505,866). Special Purpose Cleaners (SPC) including household dry cleaning systems (see, for example, WO 96/30583 A, WO 96/30472 A, WO 96/30471 A, U.S.A. 5,547,476, WO 96/37652 A); pre-treatment products with laundry bleach (see EP 751, 210 A); pretreatment products for fabric care (see, for example EP 752,469 A); liquid detergent types for fine fabrics, especially the high foaming variety; rinse aid for dishwashing; liquid whiteners including chlorine type and oxygenated bleach type, and disinfectants, mouth rinses, denture cleaners (see, for example, WO 96/19563 A, WO 96/19562 A), car or carpet shampoos or cleansers (see, for example EP 751, 213 A, WO 96/15308 A), hair rinses, shower gels, bath foams and personal care cleaners (see, for example, WO 96/37595 A, WO 96/37592 A, WO 96 / 37591 A; WO 96/37589 A; WO 96/37588 A; GB 2,297,975 A; GB 2,297,762 A; GB 2,297,761 A; WO 96/17916 A; WO 96/12468 A) and metal cleaners; as well as cleaning aids such as bleach additives and "stain adherents" or other types of pre-treatment including special foam type cleaners (see, for example EP 753,560 A; EP 753,559 A; EP 753,558 A; EP 753,557 A; EP 753,556 A) and anti-sunlight fading treatments (see, for example WO 96/03486 A; WO 96/03481 A; WO 96/03369 A) are also covered. Detergents with long-lasting perfume (see, for example, U.S.A. 5,500,154; WO 96/02490) are becoming increasingly popular and their use with the surfactant mixtures herein is contemplated.

Materials and Methods auxiliary for laundry or cleaning: In general, a laundry or cleaning assistant is any material that is required to transform a composition that contains only the minimum essential ingredients (here the essential mixture of modified alkylbenzene sulfonate surfactant) in a composition useful for laundry purposes or other consumer cleaning products. In preferred embodiments, the laundry or cleaning aids are easily recognizable to those skilled in the art since they are absolutely characteristic of laundry or cleaning products, especially of laundry or cleaning products designed for direct use by the consumer in a domestic environment .

The precise nature of these additional components, and the levels of incorporation thereof, will depend on the physical form of the composition and the nature of the cleaning operation for which it will be used. Preferably, the auxiliary ingredients if used with bleach should have good stability therewith. Certain preferred detergent compositions herein must be free of boron and / or free of phosphate as required by law. The levels of auxiliaries are from about 0.00001% to about 99.9% by weight of the compositions. The levels of use of the total compositions can vary widely depending on the designed application, varying for example from a few ppm in solution to the so-called "direct application" of the compositions for pure cleaning to the surface to be cleaned. Common auxiliaries include detergency builders, surfactants, enzymes, polymers, bleaches, bleach activators, catalytic materials and the like excluding any materials already defined hereinbefore as part of the essential component of the compositions of the invention. Other auxiliaries herein may include foam enhancers, foam suppressors (antifoams) and the like, various active ingredients or specialized materials such as dispersing polymers (eg from BASF Corp. or Rohm & amp;; Haas), colored dots, agents for silver care, anti oxidation and / or anti corrosion, dyes, fillers, germicides, alkalinity sources, hydrotropes, anti oxidants, enzyme stabilizing agents, pro-perfumes, perfumes, agents of solubility, carriers, processing aids, pigments, and, for liquid formulations, solvents, as described in detail below. Quite typically, the laundry or cleaning compositions herein such as laundry detergents, laundry detergent additives, hard surface cleaners, synthetic and soap based laundry bars, liquid and solid fabric softeners and for fabric treatment , and treatment articles of all types will require several auxiliaries, although certain products formulated in a simple manner, such as bleach additives, may only require, for example, an oxygen bleaching agent and a surfactant as described herein. A complete list of materials and auxiliary methods for laundry or cleaning can be found in the provisional patent application of E.U.A. No. 60 / 053,318, filed July 21, 1997, and assigned to Procter & Gamble. Detersive Surfactants.- The instant compositions desirably include a detersive surfactant which is used as a co-surfactant with the mixtures of essential surfactants. Because the present invention relates to surfactants, in the descriptions of the preferred embodiments of the detergent compositions of the invention, the surfactant materials are described and counted separately from the auxiliaries not surfactant. Detersive surfactants are illustrated extensively in U.S. Patent No. 3,929,678, December 30, 1975 to Laughiin, et al, and in U.S.A. 4,259,217, March 31, 1981, Murphy; in the series "Surfactant Science", Marcel Dekker, Inc., New York and Basel; in "Handbook of Surfactants", M.R. Porter, Chapman and Hall, 2nd ed., 1994; in "Surfactants in Consumer Products", Ed. J. Falbe, Springer-Verlag, 1987; and in numerous patents related to detergents assigned to Procter & Gamble and other manufacturers of detergents and consumer products. The detersive surfactant herein includes anionic, nonionic, zwitterionic or amphoteric types of surfactants known to be used as cleaning agents in fabric washing, but does not include completely foam-free or completely insoluble surfactants (although these may be use as optional auxiliaries). Examples of the type of surfactant that is considered optional for the present purposes are relatively uncommon compared to surfactants for cleaning but include, for example, common fabric softening materials such as dioctadecyldimethylammonium chloride. In more detail, detersive surfactants useful herein, typically at levels of about 1% to about 55%, by weight, include suitably: (1) conventional alkylbenzene sulfonates, including hard types (ABS, TPBS), or linear and prepared by known methods such as various solid HF or HF processes, for example DETAL® (UOP), or made using other Lewis acid catalysts, for example AICI3, or made using acid silica / alumina or made from chlorinated hydrocarbons; (2) olefinsulfonates, including alpha-olefin sulfonates and sulfonates derived from fatty acids and fatty esters; (3) alkyl or alkenyl sulfosuccinates, including the diester and half-ester types as well as sulfosuccinamates and other types of sulfonate / carboxylate surfactant such as sulfosuccinates derived from ethoxylated alcohols and alkanolamides; (4) paraffin or alkane sulfonate and alkyl or alkenyl carboxy sulfonate types, including the product of adding bisulfite to alpha olefins; (5) alkylnaphthalenesulfonates; (6) alkyl isethionates and alkoxypropanesulphonates, as well as fatty estersaturated esters, fatty esters of ethoxylated isethionate and other ester sulfonates such as the 3-hydroxypropanesulfonate ester or AVENEL S types; (7) benzene, eumeno, toluene, xylene, and naphthalene sulfonates, useful especially for their hydrotropic properties; (8) alkyl ether sulfonates; (9) alkylamide sulfonates; (10) salts or esters of alpha-sulfo fatty acid and internal esters of fatty sulfo acid; (11) alkylglyceryl sulfonates; (12) ligninsulfonates; (13) petroleum sulfonates, sometimes known as heavy alkylate sulfonates; (14) diphenyl oxide disulfonates; (15) linear or branched alkyl or alkenyl sulfates; (16) alkyl or alkoxylated alkylphenol sulfates and the corresponding polyalkoxylates, sometimes known as alkyl ether sulfates, as well as alkenyl alkoxy sulfates or alkenyl polyalkoxy sulfates; (17) alkylamide sulfates or alkenyl amide sulfates, including sulphated alkanolamides and their alkoxylates and polyalkoxylates; (18) sulphated oils, sulfated alkyl glycerides, sulfated alkyl polyglycosides or sulfated sugar derived surfactants; (19) alkylalkoxycarboxylates and alkylpolyalkoxycarboxylates, including salts of galacturonic acid; (20) alkyl ester carboxylates and alkenyl ester carboxylates; (21) alkyl or alkenyl carboxylates, especially conventional soaps and a,? -dicarboxylates, also including alkyl and alkenyl succinates; (22) alkyl or alkenyl amide alkoxy- and polyalkoxy carboxylates; (23) types of alkyl and alkenyl amidocarboxylate surfactants, including sarcosinates, taurides, glycinates, aminopropionates and iminopropionates; (24) amide soaps, sometimes referred to as fatty acid cyanamides; (25) alkylpolyaminocarboxylates; (26) phosphorus-based surfactants, including alkyl or alkenyl phosphate esters, alkyl ether phosphates including their alkoxylated derivatives, salts of phosphatidic acid, salts of alkyl phosphonic acid, alkyl di (polyoxyalkylene alkanol) phosphates, amphoteric phosphates such as lecithins; and phosphate / carboxylate, phosphate / sulfate and phosphate / sulfonate types; (27) nonionic surfactants of the Pluronic and Tetronic type; (28) the so-called EO / PO block polymers, including the types of diblock and triblock EPE and PEP; (29) fatty acid polyglycol esters; (30) alkyl or alkylphenol blocked and unblocked ethoxylates, propoxylates and butoxylates including polyethylene glycol ethers of fatty alcohols; (31) The present invention also relates to fatty alcohols, especially where they are useful as viscosity modifying surfactants or present as unreacted components of other surfactants (32). N-alkyl polyhydroxy fatty acid, especially alkyl N-alkylglucamides; (33) nonionic surfactants derived from mono- or polysaccharides or sorbitan, especially alkyl polyglycosides, as well as fatty acid esters of sucrose; (34) esters of ethylene glycol, propylene glycol , glycerol- and polyglyceryl and their alkoxylates, especially glycerol ethers and fatty acid / glycerol monoesters and diesters; (35) aldobionamide surfactants; (36) types of non-ionic alkylsuccinimide surfactants; - acetylenic alcohol surfactants, such as SURFYNOLS; (38) alkanolamide surfactants and their alkoxylated derivatives including fatty acid alkanolamides and polyglycol fatty acid alkanolamide ethers; (39) alkylpyrrolidones; (40) alkylamine oxides, including oxidized or polyalkoxylated amine oxides and amine oxides derived from sugars; (41) alkylphosphine oxides; (42) sulfoxide surfactants; (43) amphoteric sulfonates, especially sulfobetaines; (44) amphoteric betaine type, including aminocarboxylate derivative types; (45) amphoteric sulfates such as alkylammonium polyethoxysulfates; (46) alkylamines and fatty and petroleum derived amine salts; (47) alkylimidazolines; (48) alkylamidoamines and their alkoxylate and polyalkoxylate derivatives; (49) conventional cationic surfactants, including water-soluble alkyltrimethylammonium salts. In addition, the types of surfactants are included more unusual, such as: (50) alkylamidoamine oxides, carboxylates and quaternary salts; (51) sugar-derived surfactants modeled after any of the more conventional non-sugar types mentioned above; (52) fluoro surfactants; (53) bio surfactants; (54) organosilicon or fluorocarbon surfactants; (55) Gemini surfactants, other than the diphenyl oxide disulfonates referred to above, including those derived from glucose; (56) polymeric surfactants including amfopolicarboxiglicinates; and (57) ball-shaped surfactants, in summary any known surfactant for aqueous or non-aqueous cleaning. In any of the above detersive surfactants, the hydrophobic chain length is typically in the general scale of Cd-C20, with chain lengths in the range of C8-C18 being generally those reported, especially when laundry washing is to carry out in cold water. The selection of chain lengths and the degree of alkoxylation for conventional purposes are taught in the standard texts. When the detersive surfactant is a salt, any compatible anion, including H (ie, the acid or partially acid form of a partially acidic surfactant), Na, K, Mg, ammonium or alkanolammonium may be present, or combinations of cations. Mixtures of detersive surfactants having different charges, especially anionic / cationic mixtures, are usually preferred. £ ^ aájmeí jm H & ^ j ^^ anionic / nonionic, anionic / nonionic / cationic, anionic / nonionic / amphoteric, nonionic / cationic, and nonionic / amphoteric. In addition, any detersive surfactant can be substituted, often with desirable results for washing with cold water, by mixtures of other detersive detersive surfactants in some other similar manner having chain lengths, degree of unsaturation or branching, degree of alkoxylation ( especially ethoxylation), insertion of substituents such as ether oxygen atoms into hydrophobic ones, or any combinations thereof, different. Preferred among the detersive surfactants identified above are: C9-C20 linear alkylbenzenesulfonates, acids, sodium and ammonium, particularly linear C10-C15 secondary alkylbenzene sulphonates, although in some regions, β can use ABS (1); olefin sulfonate salts, (2), that is, material made by reacting olefins, particularly C10-C20 alpha olefins, with sulfur trioxide and then neutralizing and hydrolyzing the reaction product; C7-C12 dialkylsulfosuccinates of sodium and ammonium, (3); alkanemonosulfonates, (4), such as those derived by reacting C8-C20 alpha-olefins with sodium bisulfite and those derivatives by reacting paraffins with SO2 and Cl2 and then hydrolyzing with a base to form a random surfactant; salts or esters of fatty alpha-sulfo acid, (10); sodium alkyl glyceryl sulphonates, (11), especially those ethers of higher alcohols derived from tallow oil or wood and synthetic alcohols derived from petroleum; alkyl or alkenyl sulfates, (15), which may be primary or secondary, saturated or unsaturated, branched or unbranched. Such compounds when branched can be random or regular. When they are secondary, said compounds preferably have the formula CH3 (CH2) x (CHOSO3"M +) CH3 or CH3 (CH2) and (CHOSO3" M +) CH2CH3 wherein xe (y +1) are integers of at least 7, preferably at minus 9 and M is a cation soluble in water, preferably sodium. When unsaturated, sulfates such as oleum sulfate are preferred, although sodium and ammonium alkyl sulfates, especially those produced by sulfating C8-C18 alcohols, produced for example from tallow or coconut oil are also useful; also preferred are alkyl or alkenyl ether sulphates, (16), especially ethoxysulfates having about 0.5 moles or higher ethoxylation, preferably 0.5-8; alkyl ether carboxylates, (19), especially EO 1-5 ethoxycarboxylates; fatty acid soaps (21), preferably the most water-soluble types; amino acid type surfactants, (23), such as sarcosinates, especially oleylsarcosinate; phosphate esters, (26); alkyl or alkylphenol ethoxylates, propoxylates and butoxylates, (30), especially the ethoxylates "AE", including the so-called narrow-alkylethoxylates and C6-C12 alkylphenol-alkoxylates as well as the products of primary or secondary, branched or branched C8-C18 aliphatic alcohols or linear with ethylene oxide, generally 2-30 EO; N-alkyl polyhydroxy fatty acid amides, especially the C12-C18 N-methylglucamides, (32), see WO 9206154, and N-alkoxy polyhydroxy fatty acid amides, such as C10-C18 N- (3-methoxypropyl) glucamides although the N-propyl up to the C12-C18 N-hexyl glucamides can be used for low foaming; alkyl polyglycosides, (33); amine oxides, (40), preferably N-alkyldimethylamine oxides and their dihydrates; sulfobetaines or "sultaines", (43); betaines (44); and gemini surfactants. Suitable cationic surfactants for use in the present invention are those having a long chain hydrocarbyl group. Examples of such cationic co-surfactants include ammonium surfactant co-agents such as alkyldimethyl ammonium halides and those co-surfactants having the formula: [R2 (O3) y] [R4 (OR3) and] 2R5N +? - in which R ^ is an alkyl or alkylbenzyl group having from 8 to 18 carbon atoms in the alkyl chain, each R3 is selected from the group consisting of -CH2CH2-, -CH2CH (CH3) -, -CH2CH (CH2OH) -, - CH2CH2CH -, and mixtures thereof; each R 4 is selected from the group consisting of C 1 -C 4 alkyl, C 1 -C 4 hydroxyalkyl, of benzyl ring formed by joining the two groups R4, -CH2CHOH- CHOHCOR6CHOHCH2OH, wherein R6 is any hexose or hexose polymer having a molecular weight less than about 1000, and hydrogen when and not being 0; R ^ is the same as R4 O is an alkyl chain in which the total number of carbon atoms of R ^ plus R ^ is not greater than about 18; each y is from 0 to approximately 10 and the sum of the values y is from 0 to approximately 15; and X is any compatible anion. Examples of other suitable cationic surfactants are described in the following documents, all of which are incorporated herein by reference in their entirety: M.C. Publishing Co., Detergents & McCutcheon emulsifiers, (American Edition, 1997); Schwartz, et al, Surface Active Agents, Their Chemistry and Technology, New York; Interscience Publishers, 1949; patent of E.U.A. No. 3,155,591; patent of E.U.A. No. 3,929,678; patent of E.U.A. No. 3,959,461, patent of E.U.A. No. 4,387,090, and patent of E.U.A. No. 4,228,044. Examples of suitable cationic surfactants are those corresponding to the general formula: In which R-i, R2, R3 and R are independently selected from an aliphatic group of 1 to about 22 carbon atoms or an aromatic, alkoxy, polyoxyalkylene, alkylamido, hydroxyalkyl, aryl or alkylaryl group having up to about 22 carbon atoms; and X is a salt forming anion such as those selected from halogen radicals, (eg, chloride, bromide), acetate, citrate, lactate, glycolate, The phosphate, nitrate, sulfate, and alkylsulfate can be contained in the aliphatic groups, in addition to carbon and hydrogen atoms, ether bonds, and other groups such as amino groups. example those of about 12 carbons, or higher, can be saturated or unsaturated, it is preferred when Ri, R 2, R 3 and R 4 are independently selected from C 1 to C 22 alkyl. Cationic materials containing two long and long alkyl chains are especially preferred. two short alkyl chains or those containing a long alkyl chain and three short alkyl chains The long alkyl chains in the compounds described in the preceding paragraph have from about 12 to about 22 carbon atoms, preferably from about 16 to about 22 carbon atoms, and short alkyl chains in the compounds described in the preceding paragraph or have from 1 to about 3 carbon atoms, preferably from 1 to about 2 carbon atoms. Suitable levels of cationic detersive surfactant herein are from about 0.1% to about 20%, preferably from about 1% to about 15%, although much higher levels, for example up to 30% or more, can be useful, especially in nonionic: cationic (ie, limited or anionic free) formulations. However, the most preferred compositions combine the cationic surfactant at a low level, for example from about 0.1% to about 5%, preferably no more than about 2%, with the modified alkylbenzenesulfonate surfactant mixtures of the invention . Another type of useful surfactants are the so-called dianionics. These are surfactants having at least two anionic groups present on the surfactant molecule. Some suitable dianionic surfactants are further described in the co-pending of E.U.A. No. 60 / 020,503 (File No. 6160P), 60 / 020,772 (File No. 6161 P), 60 / 020,928 (File No. 6158P), 60 / 020,832 (File No. 6159P) and 60 / 020,773 (File No. 6162P), all filed on June 28, 1996, and 60 / 023,539 (File No. 6192P), 60 / 023,493 (File No. 6194P), 60 / 023,540 (File No. 6193P) and 60 / 023,527 (File No. 6195P) submitted on August 8, 1996, the descriptions of which are incorporated herein by reference. Additionally and preferably, the surfactant may be a branched alkyl sulfate, branched alkylalkoxylate, branched alkoxylated alkylsulfate. These surfactants are further described in No. 60/061, 971 Attorney File No. 6881 P of October 14, 1997, No. 60/061, 975 Attorney File No. 6882P of October 14, 1997, No. 60 / 062,086 Attorney File No. 6883P of October 14, 1997, No. 60/061, 916 Attorney File No. 6884P of October 14, 1997, No. 60/061, 970 Attorney's Record No. 6885P of October 14, 1997, No. 60 / 062,407 Attorney File No. 6886P of October 14, 1997. Other Agents Suitable branched chain middle surfactants can be found in U.S. Patent Applications Serial Nos. 60 / 032,035 (File No. 6401 P), 60/031, 845 (File No. 6402P), 60/031 , 916 (File No. 6403P), 60/031, 917 (File No. 6404P), 60/031, 761 (File No. 6405P), 60/031, 762 (File No. 6406P) and 60/031, 844 (File No. 6409P). Also suitable are mixtures of these branched surfactants with conventional linear surfactants for use in the present compositions. Suitable levels of anionic detersive surfactants herein are in the range of from about 1% to about 50% or higher, preferably from about 2% to about 30%, more preferably from about 5% to about 20% by weight of the detergent composition. Suitable levels of nonionic detersive surfactants herein are from about 1% to about 40%, preferably from about 2% to about 30%, more preferably from about 5% to about 20%. Desirable weight ratios of anionic: nonionic surfactants in combination include from 1.0: 9.0 to 1.0: 0.25, preferably 1.0: 1.5 to 1.0: 0.4.

Desirable weight ratios of anionic: cationic surfactants in combination include from 50: 1 to 5: 1, more preferably 35: 1 to 15: 1. Suitable levels of cationic detersive surfactants herein are from about 0.1% to about 20%, preferably from about 1% to about 15%, although much higher levels, for example up to 30% or more, may be useful, especially in nonionic formulations: cationic (ie, limited or free of anionic). The amphoteric and zwitterionic detersive surfactants when present are normally useful D levels on the scale from about 0.1% to about 20% by weight of the detergent composition. Frequently the levels will be limited to approximately 5% or less, especially when the amphoteric is expensive. Detersive Enzymes.- Enzymes are preferably included in the present detergent compositions for a variety of purposes, including the removal of protein-based stains, based on carbohydrates or triglyceride-based substrates, for the prevention of refugee dye transfer. in washing fabrics in laundry, and for fabric restoration. Recent descriptions of enzymes in detergents useful herein include combinations of bleach / amylase / protease (EP 755,999 A, EP 756,001 A, EP 756,000 A); chondriotinase (EP 747,469 A); Protease variants (WO 96/28566 A; WO ^^^^^^^^^^^^^^^^^^ jj ^ j ^^^ i ^^^ 96/28557 A; WO 96/28556 A; WO 96/25489 A); xylanase (EP 709.425 A); keratinase (EP 747,470 A); lipase (GB 2,297,979 A; WO 96/16153 A; WO 96/12004 A; EP 698,659 A; WO 96/16154); cellulase (GB 2,294,269 A; WO 96/27649 A; GB 2,303,147 A); termitase (WO 96/28558 A). More generally, suitable enzymes include proteases, amylases, lipases, cellulases, peroxidases, xylanases, keratinases, chondriotinases; termitases, cutinases and mixtures thereof of any suitable origin, such as vegetable, animal, bacterial, fungal and yeast. Preferred selections are influenced by factors such as pH activity and / or optimum stability, thermostability, and stability to active detergents, builders and the like. In this regard, bacterial or fungal enzymes are preferred, such as bacterial amylases and proteases and fungal cellulases. Suitable enzymes are also described in the patents of E.U.A. Nos. 5,672,272, 5,679,630, 5,703,027, 5,703,034, 5,705,464, 5,707,950, 5,707,951, 5,710,115, 5,710,116, 5,710,118, 5,710.1 19, and 5,721,202. "Detersive enzyme", as used herein, means any enzyme that has a beneficial effect of cleaning, stain removal or any other beneficial effect in a detergent composition for laundry, hard surface cleaning or personal care. Preferred detersive enzymes are hydrolases such as proteases, amylases and lipases. Enzymes that are preferred for laundry purposes include, but are not limited to, proteases, cellulases, lipases and peroxidases. Amylases and / or proteases are widely preferred, including commercially available types and improved types which, while becoming increasingly compatible with bleach due to successive improvements, still have a degree of susceptibility to deactivation of the bleach. Enzymes are normally incorporated in detergent or detergent additive compositions at levels sufficient to provide an "effective cleaning amount". The term "effective cleaning amount" refers to any amount capable of producing a cleaning, stain removal, soiling, whiteness, deodorizing or freshness removing effect on substrates such as fabrics, tableware and the like. In practical terms for current commercial preparations, typical amounts are up to about 5 mg by weight, more typically about 0.01 mg to about 3 mg, of active enzyme per gram of the detergent composition. Stated otherwise, the compositions herein will typically consist of from about 0.001% to about 5%, preferably 0.01% -1% by weight of a commercial enzyme preparation. Protease enzymes are normally present in such commercial preparations at levels sufficient to provide from 0.005 to 0.1 Anson units (AU) of activity per gram of composition. For certain detergents, it may be desirable to increase the active enzyme content of the commercial preparation in order to minimize the total amount of non-catalytically active materials and thereby improve spatter / film formation or other final results. Higher active levels in highly concentrated detergent formulations may also be desirable. Suitable examples of proteases are subtilisins that are obtained from particular strains of B. subtilis and B. licheniformis. A suitable protease is obtained from a strain of Bacillus, which has a maximum activity through the pH scale of 8-12, developed and sold as ESPERASE® by Novo Industries A S of Denmark, hereinafter "Novo". The preparation of this enzyme and analogous enzymes is described in GB 1, 243,784, to Novo. Other suitable proteases include ALCALASE® and SAVINASE® from Novo and MAXATASE® from International Bio-Synthetics, Inc., The Netherlands; as Protease A as described in EP 130,756 A, of January 9, 1985 and Protease B as described in EP 303,761 A, of April 28, 1987 and EP 130,756 A, of January 9, 1985. See also High pH protease from Bacillus sp. NCIMB 40338 described in WO 9318140 A to Novo. Enzymatic detergents comprising protease, one or more other enzymes and a reversible protease inhibitor are described in WO 9203529 A to Novo. Other proteases that are preferred include those of WO 9510591 A to Procter & amp;; Gamble. When desired, a protease having decreased adsorption and increased hydrolysis is available as described in WO 9507791 to Procter & Gamble. A recombinant trypsin-like protease for detergents suitable herein is described in WO 9425583 to Novo. In more detail, a protease that is especially preferred, called "Protease D" is a variant of carbonyl hydrolase having an amino acid sequence that is not found in nature, which is derived from a carbonylhydrolase precursor by substituting a different amino acid for a plurality of amino acid residues at a position in said carbonyl hydrolase equivalent to position +76, preferably also in combination with one or more amino acid residue positions equivalent to those selected from the group consisting of +99, +101, +103, +104, +107, +123, + 27, +105, +109, +126, +128, +135, +156, +166, +195, +197, +204, +206, +210, +216, +217, +218, +222, +260, +265, and / or +274 according to the numeration of Bacillus arriyloliquefaciens subtilisin as described in WO 95/10615, published April 20, 1995 by Genencor International. Useful proteases are also described in PCT publications: WO 95/30010, published November 9, 1995 by The Procter & Gamble Company; WO 95/30011, published November 9, 1995 by The Procter & Gamble Company and WO 95/29979, published November 9, 1995 by The Procter & Gamble Company. Amylases suitable herein include, for example, alpha-amylases described in GB 1, 296, 839 to Novo; RAPIDASE®, International Bio-Synthetics, Inc. and TERMAMYL®, Novo. FUNGAMYL® by Novo is especially useful. The genetic manipulation of the enzymes is known for improved stability, for example, oxidative stability. See, for example, J. Biological Chem, Vol. 260, No. 11, June 1985, p. < * .í'fc- í's'tssteAfS í "'* - '- - "• -« * - "» - - - »^ -' ^^ 6518-6521. Certain preferred embodiments of the present compositions can make use of amylases having improved stability in detergents, especially improved oxidative stability as measured against a reference point of TERMAMYL® in commercial use in 1993. These preferred amylases in the present share the characteristics of being "improved stability" amylases, characterized, at a minimum, by a measurable improvement in one or more of: oxidative stability, for example, to hydrogen peroxide / tetraacetylethylenediamine in pH-regulated solution at pH 9-10; thermal stability, for example, at common wash temperatures such as about 60 ° C; or alkaline stability, for example, at a pH of about 8 to about 11, measured against the amylase of the reference point identified above. Stability can be measured using any of the technical tests described in the art. See, for example, the references described in WO 9402597. The improved stability amylases can be obtained from Novo or Genencor International. A class of highly preferred amylases herein has the common property of being derived using the site-directed mutagenesis of one or more of the Bacillus amylases, especially the Bacillus alpha-amylases, regardless of whether one, two or multiple strains of Amylases are the immediate precursors. It is preferred to use the oxidative amylases of improved stability vs. the reference amylase identified above, especially in bleaching compositions, most preferably of oxygenated bleach, other than chlorine bleach, of the detergent compositions herein. Preferred amylases include a) an amylase according to WO 9402597, Novo, Feb. 3, 1994, previously incorporated, as further illustrated by a mutant in which it is substituted, using alanine or threonine, preferably threonine, the residue of methionine located at position 197 of the alpha-amylase of B. lichemiformis, known as TERMAMYL®, or the variation of the homologous position of a similar progenitor amylase, such as B. amyloliquefaciens, B. subtilis or B. stearothermophilus; b) improved stability amylases as described by Genencor International in a document entitled "Oxidatively Resistant alpha-Amylases", presented at the 207th American Chemical Society National Meeting, March 13-17, 1944, by C. Mitchinson. It is mentioned that the bleaches in detergents for the automatic dishwashing inactivate alpha-amylases, * but that amylases have been made of oxidant stability improved by Genencor from B. licheniformis NCIB8061. Methionine (Met) was identified as the residue most likely to be modified. The Met was substituted, one at a time, in positions 8, 15, 197, 256, 304, 366 and 438 leading to specific mutants, particularly important being the MI97L and MI97T variants, with the variant M197T being the most stable expressed variant. The stability was measured in CASCADE® and SUNLIGHT®; (c) the particularly preferred amylases herein include the amylase variants having further modification in the immediate parent such as those described in WO 9510603 A and available from the Novo transferee, such as DURAMYL®. Another oxidizing amylase of improved stability which is particularly preferred includes that described in WO 9418314 to Genencor International and WO 9402597 to Novo. Any other oxidative amylase of improved stability can be used, for example as derived by site-directed mutagenesis of known chimeric, hybrid or simple mutant progenitor forms of available amylases. Other preferred enzyme modifications are also accessible. See WO 9509909 to Novo. Other amylase enzymes include those described in WO 95/26397 and in the co-pending application by Novo Nordisk PCT / DK96 / 00056. Specific amylase enzymes for use in the detergent compositions of the present invention include the alfe-amylases characterized in that they have a specific activity at least 25% higher than the specific activity of Termamyl® at a scale of. temperatures of 25 ° C to 55 ° C and a pH value on the scale of 8 to 10, measured by the Phadebas® alpha-amylase activity test. (Said Phadebas® alpha-amylase activity test is described on pages 9-10 of WO 95/26397). Also included herein are alpha-amylases that are at least 80% homologous to the amino acid sequences shown in the SEQ ID listings in the references. These enzymes are preferably incorporated in laundry detergent compositions at a level of about 0.00018% to 0.060% pure enzyme by weight of the total composition, preferably about 0.00024% to 0.048% pure enzyme by weight of the total composition.

Cellulases that can be used herein include bacterial and fungal types, preferably having an optimum pH between 5 and 9.5. The U.S.A. 4,435,307, Barbesgoard et al, March 6, 1984, describes suitable fungal cellulases of the DSM 1800 strain of Humicola insolens or Humicola, or a cellulase-producing fungus 212 belonging to the genus Aeromonas, and the cellulase extracted from the hepatopancreas of a marine mollusk. , 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. CAREZYME® and CELLUZYME® (Novo) are especially useful. See also WO 9117243 to Novo. Lipase enzymes suitable for detergent use include those produced by microorganisms of the Pseudomonas group, such as Pseudomonas stutzeri ATCC 19,154 as described in GB 1, 372, 034. Also see lipases in Japanese Patent Application 53,20487, open to public inspection on February 24, 1978. This lipase is available from Amano Pharmaceutical Co. Ltd., Nagoya, Japan, under the tradename Lipase P "Amano," or "Amano-P." Other suitable commercial lipases include Amano-CES, lipases ex Chromobacter viscosum, e.g., Chromobacter viscosum var. lipoliticum NRRLB 3673, from Toyo Jozo Co., Tagata, Japan; Chromobacter viscosum lipases from U.S. Biochemical Corp, E.U.A. and Disoynth Co., Holland and lipases ex Pseudomonas gladioli. The LIPOLASE® enzyme derived from Humicola lanuginosa and commercially available from Novo, see also EP 341, 947, is a preferred lipase for use in the A ^^^ aAl ,. * ^ mm ^.

I presented. Variants of lipase and amylase stabilized against peroxidase enzymes are described in WO 9414951 A to Novo. See also WO 9205249 and RD 94359044. Cutinase enzymes suitable for use herein are described in WO 8809367 A to Genencor. The peroxidase enzymes can be used in combination with oxygen sources, for example, percarbonate, perborate, hydrogen peroxide, etc., for "bleaching in solution" or to avoid the transfer of dyes or pigments removed from substrates during the operations of washing to other substrates present in the washing solution. Known peroxidases include horseradish peroxidase, ligninase, and haloperoxidases such as chloro- or bromo-peroxidase. Peroxidase-containing detergent compositions are described in WO 89099813 A, October 19, 1989 to Novo and WO 8909813 A to Novo. A variety of enzyme materials and means for their incorporation into synthetic detergent compositions are also described in WO 9307263 A and WO 9307260 A to Genecor International, WO 8908694 A to Novo and U.S. Pat. 3,553,139, January 5, 1971 to McCarty et al. Additionally, enzymes are described in the U.S. patent. 4,101, 457, Place et al, July 18, 1978 and in the patent of E.U.A. 4,507,219, Hughes, March 26, 1985. Enzyme materials useful for liquid detergent formulations and their incorporation into such formulations are described in US Pat. 4,261, 868, Hora et al, April 14, 1981. Enzymes for use in detergents can be stabilized by various techniques. Enzyme stabilization techniques are described and illustrated in the U.S. patent. 3,600,319, of August 17, 1971 to Gedge et al, in EP 199,405 and EP 200,586, of October 29, 1986, 5 Venegas. Enzyme stabilization systems are also described, for example, in E.U.A. 3,519,570. A Bacillus sp. Useful AC13, which gives proteases, xylanases and cellulases, is described in WO 9401532 A to Novo. Detergency builders. - Detergency builders are preferably included in the compositions herein, for example to help control mineral hardness, especially Ca and / or Mg in the wash water, or to assist in the removal and / or suspension of particulate dirt from surfaces and sometimes to provide alkalinity and / or regulatory action of pH. In solid formulations, builders often serve as absorbers for agents surfactants. Alternatively, certain compositions can be formulated with fully water-soluble builders, either organic or inorganic, depending on the intended use. Suitable silicate detergency builders include water-soluble and water-soluble types, and include those that have a Chain, layer or three-dimensional structure, as well as amorphous-solid silicates or other types, for example, specially adapted for use in unstructured liquid detergents. Alkali metal silicates are preferred, particularly those liquids and solids that have a rfa ^ SiO2 ratio: Na2? in the range from 1.6: 1 to 3.2: 1, including 2-ratio solid aqueous silicates marketed by PQ Corp. under the trademark BRITESIL®, eg, BRITESIL H2O; and stratified silicates, for example, those described in the U.S.A. 4,664,839, of May 12, 1987, H. P. Rieck. NaSKS-6, sometimes abbreviated "SKS-6", is a crystalline and aluminum-free crystallized layered d-Na2SiO5 silicate sold by Hoechst, and is especially preferred in granular laundry compositions. See preparation methods in the German application DE-A-3,417,649 and DE-A-3,742,043. Other layered silicates, such as those having the general formula NaMSixO x + 1 and H 2 O in which 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, also or alternatively can be used herein. The stratified silicates of Hoechst also include NaSKS-5, NaSKS-7 and NaSKS-11 as the alpha, beta and gamma stratified silicate forms. Other silicates can also be useful, such as magnesium silicate, which serve as a tightening agent in granulated formulations, as a stabilizing agent for bleach, and as a component of foam control systems. Also suitable for use herein are crystalline ion exchange materials synthesized or hydrates thereof having chain structure and a composition represented by the following general formula in the form of anhydride: xM2O and Si2zM'O wherein M is Na and / or K, M 'is Ca and / or Mg; y / x is 0.5 to 2.0 and z / x is 0.005 to 1.0 as taught in E.U.A. 5,427,711, Sakaguchi et al, June 27, 1995. Aluminosilicate builders, such as zeolites, are especially useful in granular detergents, but can also be incorporated into liquids, pastes or gels. Suitable for the purposes of the present are those having the empirical formula: [Mz (AIO2) z (SiO2) v] xH2 ?, in which z and v are integers of at least 6, M is an alkali metal, preferably Na and / or K, the molar ratio of zav is on the scale of 1.0 to 0.5, and x is an integer of 15 to 264. Aluminosilicates can be crystalline or amorphous, occurring naturally or derived synthetically. An aluminosilicate production method is in E.U.A. 3,985,669, Krummel et al, October 12, 1976. Preferred synthetic crystalline aluminosilicate ion exchange materials are available as Zeolite A, Zeolite P (B), Zeolite X and, as far as is different from Zeolite P, the so-called Zeolite MAP. Natural types, including clinoptilolite, can be used. Zeolite A has the formula: Na-i2 [(Al? 2) i2 (Si? 2) i2_'xH2? wherein x is from 20 to 30, especially 27. Dehydrated zeolites can also be used (x = 0-10). Preferably, the aluminosilicate has a particle size of 0.1 -10 microns in diameter. The builders instead of or in addition to the silicates and aluminosilicates described hereinbefore can optionally be included in the compositions herein, for example to assist in controlling the mineral hardness, especially of Ca and / or Mg in the water iViftfirí-ftrr ^ firrtpii? n washing, or to assist in the removal and / or suspension of dirt particles of surfaces. The detergency builders can operate through a variety of mechanisms including formation of soluble and insoluble complexes with hardness ions, by ion exchange, and offering a more favorable surface to the precipitation of hardness ions of which are the surfaces of the articles to be cleaned. The level of builder can vary widely depending on the final use and the physical form of the composition. Detergent builder detergents typically comprise at least about 1% builder. Liquid formulations typically comprise from about 5% to about 50%, more typically from 5% to 35% builder. The granulated formulations typically comprise about 10% to about 80%, more typically 15% to 50%, detergent builder by weight of the detergent composition. Lower or higher levels of builders are not excluded. For example, certain formulations of detergent additive or high surfactant content may not be improved in detergency. The builders suitable herein can be selected from the group consisting of phosphates and polyphosphates, especially the sodium salts; carbonates, bicarbonates, sesquicarbonates and carbonate minerals other than carbonate or sodium sesquicarbonate; organic mono-, di-, tri-, and tetracarboxylates, especially the carboxylates which are not surface-active surfactants in the form of an acid, sodium, potassium or alkanolammonium salt, as well as oligomeric or water-soluble low molecular weight polymeric carboxylates, including aliphatic and aromatic types; and tific acid. These can be supplemented with borates, for example, for pH regulation purposes, or by sulfates, especially sodium sulfate and any other fillers or carriers that may be important for the design of stable detergent compositions containing surfactants and / or builders. of detergency. Mixtures of builders, sometimes called "builder systems," can be used, and typically comprise two or more conventional builders, complemented with chelating agents, pH regulators or fillers, although the latter materials are taken in account separately when describing the quantities of materials herein. In terms of relative amounts of surfactant and builder in the present detergents, the preferred builder systems are typically formulated at a weight ratio of surfactant to builder of from about 60: 1 to about 1: 80 Certain laundry detergents that are preferred have said ratio in the range of 0.90: 1.0 to 4.0: 1.0, more preferably 0.95: 1 to 3.0: 1.0. Frequently preferred phosphate-containing builders where permitted by law include, but are not limited to, the alkali metal, ammonium and alkanolammonium salts of polyphosphates, illustrated by the tripolyphosphates, pyrophosphates, vitreous polymeric meta-phosphates; and phosphonates. Suitable carbonate builders include alkali metal and alkali metal carbonates as described in German Patent Application No. 2,321,001 published November 15, 1973, although sodium bicarbonate, sodium carbonate, sodium sesquicarbonate and other carbonate minerals such as trona or any convenient multiple salts of sodium carbonate and calcium carbonate such as those having the composition 2Na2CO3 CaCO3 when they are anhydrous, and even calcium carbonates including calcite, aragonite and vaterite, especially the forms have high surface areas relative to compact calcite may be useful, for example as seeds or for use in synthetic detergent bars. Suitable "organic builders", as described herein for use in cleaning compositions, include polycarboxylate compounds, including dicarboxylates and tricarboxylates that are non-surfactant and water soluble. More typically, the builder polycarboxylates have a plurality of carboxylate groups, preferably at least 3 carboxylates. The carboxylate builders can be formulated in acid, partially neutral, neutral or overbased form. When they are in the salt form, the metalalkaline salts, such as sodium, potassium and lithium, or alkanolammonium salts, are preferred. Polycarboxylate builders include ether polycarboxylates, such as oxydisuccinate, see Berg, E.U.A. 3,128,287, of April 7, 1964, and Lamberti et al, E.U.A. 3,635,830, of January 18, 1972; detergent builders "TMS / TDS" 5 from E.U.A. 4,663,071, Bush et al, May 5, 1987; and other ether carboxylates including cyclic and alicyclic compounds, such as those described in U.S. Pat. 3,923,679; 3,835,163; 4,158,635; 4,120,874 and 4,102,903. Other suitable organic builders are the Ether-hydroxypolycarboxylates, maleic anhydride copolymers with ethylene or vinyl methyl ether, 1,3-trihydroxybenzene-2,4,6-trisulfonic acid; carboxymethyloxy-succinic acid, the various metaalkaline, ammonium and substituted ammonium salts of polyacetic acids such as ethylenediaminetetraacetic acid and nitrilotriacetic acid; as well as melific acid, succinic acid, acid Polymaleic acid, benzene-1, 3,5-tricarboxylic acid, carboxymethyloxysuccinic acid and soluble salts thereof. The citrates, for example, citric acid and soluble salts thereof, are important carboxylate builders, for example, for heavy-duty liquid detergents, due to their availability from renewable resources and their capacity for biodegradation. The citrates can also be used in granular compositions, especially in combination with zeolite and / or layered silicates. Oxydisuccinates are also especially useful in said tlÉi ffWr "" ^ - ^^ compositions and combinations. Where metalalkaline phosphates such as sodium tripolyphosphates, sodium pyrophosphate and sodium orthophosphate 5 are permitted, and especially in the formulation of bars used for hand washing operations, can be used. Phosphonate builders such as eta n-1-hydroxy-1,1-diphosphonate and other known phosphonates, for example, those of E.U.A. may also be used and may have anti-fouling properties. 3,159,581; 3,213,030; 3,422,021; 3,400,148 and 3,422,137. Certain detersive surfactants or their short chain homologs also have a builder action. For purposes of consideration of non-ambiguous formula, when they have surfactant capacity, these materials are taken into account as detersive surfactants. Preferred types of builder functionality are illustrated by: 3,3-dicarboxy-4-oxa-1,6-hexanedioates and the related compounds described in E.U.A. 4,566,984, Bush, January 28, 1986. Succinic acid builders include alkyl and alkenyl succinic acids of C5-C20 and salts thereof. Succinate builders also include: lauryl succinate, myristylsuccinate, palmityl succinate, 2-dodecenylsuccinate (preferred), 2- or pentadecenylsuccinate, and the like. Lauryl succinates are described in European patent application 86200690.5 / 0,200,263, published on November 5, 1986. Fatty acids, for example, C12-C18 monocarboxylic acids, can also be incorporated into the compositions as surfactant / enhancer materials of detergency alone or in combination with the aforementioned detergency builders, especially citrate and / or succinate builders, to provide additional detergency builder activity. Other polycarboxylates are described in E.U.A. 4,144,226, Crutchfield et al, March 13, 1979 and in E.U.A. 3,308,067, Diehl, March 7, 1967. See also Diehl, E.U.A. 3,723,322. Other types of inorganic builders materials that can be used have the formula (Mx) iCay (C03) z in the which xei are integers from 1 to 15, and is an integer from 1 to 10, z is an integer from 2 to 25, M, are cations, at least one of which is soluble in water, and the equation? I = 1-15 (x, multiplied by the valence of M,) + 2y = 2 is satisfied in such a way that the formula has a neutral or "balanced" charge. These detergency builders are called in this "breeders" Mineral detergency, examples of such detergency builders, their use and preparation can be found in U.S. Patent No. 5,707,959.Another suitable class of inorganic builders are magnesiosilicates, see, WO97 / 0179.

Oxygen Oxygen Agents The cleaning compositions of the present invention may preferably comprise, as part or all of the conventional auxiliary materials, an "oxygen bleaching agent". The agents Oxygenated bleaches useful in the present invention can be any of the known oxidizing agents for laundry purposes, hard surface cleaning, automatic dishwashing or denture cleaning. Oxygenated bleaches or mixtures thereof are preferred, although other oxidizing bleaches, such as oxygen, an hydrogen peroxide producing enzyme system, or hypohalogenites such as chlorine bleach such as hypochlorite may also be used. Oxygenated bleach "systems" generally contain two or more materials that contribute to oxygenated bleaching, commonly a source of oxygen bleach, such as perborate or even oxygen from the air, and a catalyst and / or a bleach activator. Oxygenated oxygenated peroxygen bleaches include hydrogen peroxide, inorganic peroxohydrates, organic peroxohydrates and organic peroxyacids, including hydrophilic and hydrophobic mono- or di-peroxyacids. These may be peroxycarboxylic acids, peroxy m idic acids, amidoperoxycarboxylic acids, or their salts, including calcium, magnesium or mixed cation salts. Peracids of various types can be used both in free form and as precursors known as "bleaching agents" or "bleach promoters" which, when combined with a source of hydrogen peroxide, are perhydrolyzed to release the corresponding peracid. Also useful in the present invention as oxygen bleaches are inorganic peroxides such as Na2O2, superoxides such as K02, organic hydroperoxides such as eumenohydroperoxide and t-butyl hydroperoxide, and inorganic peroxyacids and their salts such as the salts of peroxosulfuric acid, especially the potassium salts of peroxodulphuric acid and, most preferably, of peromonusulfuric acid, including the commercial form of triple salt sold as OXONE by Dupont and also any commercially available equivalent form as CUROX from Akzo or CAROAT from Degussa. Some organic peroxides, such as dibenzoyl peroxide, may be useful, especially as additives and not as a major oxygenated bleach. Mixed oxygenated bleach systems are generally useful, as are blends of any oxygenated bleaching agents with bleaching agents, organic catalysts, known enzymatic catalysts and mixtures thereof; in addition such mixtures may include additional brighteners, photobleaches and dye transfer inhibitors of the types already known in the art. As mentioned, oxygenated whiteners that are preferred include peroxohydrates, sometimes known as peroxyhydrates or peroxohydrates. They are organic or, more commonly, inorganic salts that can release hydrogen peroxide easily. Peroxohydrates are the most common examples of "hydrogen peroxide source" materials and include perborates, percarbonates, perfosphates and percilicates. Suitable peroxohydrates include sodium carbonate peroxyhydrate and commercially equivalent "percarbonate" bleaches, and any of the so-called sodium perborate hydrates, with "tetrahydrate" and "monohydrate" being preferred; although sodium pyrophosphate peroxyhydrate can be used. Some of these peroxohydrates are available in processed forms with coatings, such as silicate and / or borate and / or waxy materials and / or surfactants, or have a particle geometry, such as compact spheres, that improve storage stability. As organic peroxohydrates, urea peroxohydrate may also be useful in the present. The percarbonate bleach includes, for example, dry particles having an average particle size in the range of about 500 microns to about 1000 microns, no more than about 10% by weight or said particles being smaller than about 200 microns and no greater of about 10% by weight of said particles, being larger than approximately 1,250 microns. Percarbonates and perborates are widely available in the market, for example from FMc, Solvay and Tokai Denka. The organic percarboxylic acids useful herein as the oxygen bleach include magnesium monoperoxyphthalate hexahydrate, available from Interox, m-chloro perbenzoic acid and its salts, 4-nonylamino-4-oxoperoxybutyric acid and diperoxydecanediodic acid and its salts. Such bleaches are described in the U.S. patent. No. 4,483,781, in the patent application of E.U.A. No. 740,446, to Bums et al, filed June 3, 1985, EP-A 133,354, issued February 20, 1985, and the US patent. No. 4,412,934. The organic percarboxylic acids usable herein include those which contain one, two or more peroxy groups, and may be aliphatic or aromatic. The most preferred oxidants also include 6-nonylamino-6-oxoperoxycaproic acid (NAPAA) as described in the US patent. No. 4,634,551. An extensive and comprehensive list of useful oxygenated bleach, including inorganic peroxohydrates, organic peroxohydrates, and organic peroxyacids, including hydrophilic and hydrophobic mono- or di-peroxyacids, percarboxylic acids, peroxymetric acids, amidoperoxycarboxylic acids, or their salts including calcium salts , magnesium or mixed cations, can be found in the US patents 5,622,646 and 5,686,014. Other useful peracids and bleach activators of the present invention are in the family of imidoperacids and bleach activators. These include phthaloylimidoperoxycaproic acid and related substituted arylimido and acyloxynitrogen derivatives. For listings of such components, preparations and their incorporation into laundry compositions including both granules and liquids, see U.S. Pat. 5,487,818; E.U.A. 5,470,988; E.U.A. 5,466,825; E.U.A. 5,419,846; E.U.A. 5,415,796; E.U.A. 5,391, 324; E.U.A. 5,328,634; E.U.A. 5,310,934; E.U.A. 5,279,757; E.U.A. 5,246,620; E.U.A. 5,245,075; E.U.A. 5,294,362; E.U.A. 5,423,998; E.U.A. 5,208,340; E.U.A. 5,132,431 and E.U.A. 5,087,385. Useful diperoxy acids include, for example, 1,2-diperoxydecanedioic acid (DPDA); 1, 9-diperoxyazelaic acid; diperoxy fibers, diperoxysebacic acid and diperoxyisophthalic acid; 2-5-decyldiperoxybutane-1,4-dioic acid and 4,4'-sulfonylbisperoxybenzoic acid. More generally, the terms "hydrophilic" and "hydrophobic" which are used in the present invention in connection with any oxidants, especially peracids, and in connection with bleach activators, in the first instance, are based on whether a given oxidant plays effectively bleaching dyes in a solution, thus avoiding discoloration and the fabric becoming grayish and / or removing more hydrophilic stains such as tea, wine and grape juice, in this case it is called "hydrophilic". When the oxidant or bleach activator has a significant stain removal, improvement in whiteness or cleaning effect in percudidas, greasy, carotenoides, or other hydrophobic spots, called "hydrophobic". The terms are also applicable when referring to peracids or bleach activators that are used in combination with a source of hydrogen peroxide. The current commercial brands for the hydrophilic performance of oxidizing systems are: TAED or peracetic acid, which correspond to hydrophilic bleaching. NOBS or NAPAA are the corresponding marks for hydrophobic bleaching. The terms "hydrophilic", "hydrophobic" and "hydrotropic" with reference to the oxidants including peracids and here also some way bleach activators have been used ^^. ? A ^^ extended more closely linked to literature. See especially Kirk Othmer's Encyclopedia of Chemical Technology, Vol. 4, pages 284-285. This reference provides a chromatographic retention time and some criteria based on the important concentration of micelles, and is useful for identifying and / or characterizing the preferred subclasses of hydrophobic, hydrophilic and hydrotropic oxidants and bleach activators that can be used in the present invention.

Bleach activators Bleach activators useful herein include amide, midas, esters and anhydrides. Typically, at least a portion of substituted or unsubstituted acyl connected covalently to a leaving group as in structure R-C (0) -L. In a pre-used mode of use, the bleach activators are combined with a source of hydrogen peroxide, such as perborates or percarbonates, in a single product. Conveniently, the single product leads to in situ production in an aqueous solution (ie, during the washing process) of the percarboxylic acid corresponding to the bleach activator. The product itself can be hydrated, for example a powder, since the water is controlled in quantity and mobility, in such a way that the storage stability is acceptable. Alternatively, the product may be solid or anhydrous liquid. In another embodiment, the bleach activator or oxygen bleach is incorporated in a pretreatment product, such as a stain remover; the previously treated, stained substrates can then be exposed to other treatments, for example to a source of hydrogen peroxide. With respect to the structure of the previous bleach activator RC (0) L, the atom in the residual group which is connected to the peracid-forming acyl portion R (C) 0- is mainly O or N. The bleach activators may be have peracid forming moieties positively or negatively charged and / or residual groups charged positively or negatively. One or more peracid forming moieties or residual groups may be present. See, for example, the patents of E.U.A. Nos. 5,595,967, 5,561, 235, 5,560,862 or the bis- (peroxy-carbonic) system of the U.S. patent. No. 5,534,179. Mixtures of bleach activators can also be used. The pL3 bleach activators may be replaced with electron donating or electron releasing portions, either in the leaving group or in the peracid forming portion or portions, changing their reactivity and making them more or less adequate at a particular pH for the washing conditions. For example, groups that attract electrons such as N02 improve the effectiveness of bleach activators created for use in light pH wash conditions (for example from about 7.5 to about 9.5). An extensive and exhaustive description of suitable bleach activators and suitable residual groups, as well as how to determine suitable activators, can be found in the U.S. Pat. 5,686,014 and 5,622,646. ^^ ^ é If activators include cationic bleach types quaternary carbamato-, quaternary carbonate-, quaternary ester- and quaternary amide-providing a peroxyimidic acid cation scale, peroxycarbonic or peroxycarboxylic washing. An analogous but non-cationic group of bleach activators is available when the quaternary derivatives are not desired. In more detail, cationic activators include activators substituted with quaternary ammonium from WO 96-06915, U.S. 4,751, 015 and 4,397,757, EP-A-284292, EP-A-331, 229 and EP-A-03520. Also useful are cationic nitriles as described in EP-A-303,520 and in European patent specification 458,396 and 464,880. Other nitrile types that have electron-withdrawing substituents are described in E.U.A. 5,591, 378. Other descriptions of bleach activators are included in GB 836,988; 864,798; 907,356; 1, 003,310 and 1, 519,351; German Patent No. 3,337,921; EP-A-0185522; EP-A-0174132; EP-A-0120591; the patents of E.U.A. Nos. 1, 246,339; 3,332,882; 4,128,494; 4,412,934 and 4,675,393, and sulfonatophenol ester of the alkanoyl amino acids described in the U.S. patent. 5,523,434. Suitable bleach activators include any type of acetylated diamine, either hydrophilic or hydrophobic in character. Of the above classes of bleach precursors, preferred classes include esters, including acyl phenols sulfonates, acylalkyl phenols sulfonates or acyloxybenzenesulfonates (residual group OBS); the acylamides; and the peroxyacid precursors substituted with quaternary ammonium including the cationic nitriles. Preferred bleach activators include N, N, N'N'-tetraacetylethylenediamine (TAED) or any of its close relatives including triacetyl or other non-symmetrical derivatives. TAED and acetylated carbohydrates such as pentaacetatoglucose and tetraacetylxylose are preferred hydrophilic bleach activators. Depending on the application, acetyltrietilcitrate, a liquid, as well as phenylbenzoate can also be used. Preferred activators include hydrophobic bleaching nonanoiloxibencensulfonato sodium (NOBS or SNOBS), N- (alcanoilaminoalcanoiloxibencensulfonatoá as 4- [N- (nonanoyl) aminohexanoiloxi] -bencensulfona.oo (NACA-OBS) as described in US 5,534,642 Patent and EPA 355 384 A1 0, substituted amide types described in greater detail below, such as activators related to NAPAA, and activators related to certain imidoperacid bleaches, for example as described in US patent No. 5,061, 807, issued on 29 October 1991 and assigned to Hoechst Aktiengesellschaft of Frankfurt, Germany and the patent application to open Japanese (Kokai) No. 4-28799. Another group of peracids and bleach activators herein are those derived from acyclic imidoperoxycarboxylic acids and salts thereof, see U.S. Patent No. 5,415,796, and acids , .- j & Cyclical imidopercarboxylic and salts thereof, see E.U.A patents 5,061, 807, 5,132,431, 5,654,269, 5,246,620, 5,419,864 and 5,438,147. Other suitable bleach activators include sodium 4-benzoyloxybenzenesulfonate (SBOBS); Sodium 1-methyl-2-benzoyloxybenzene-4-sulfonate; Sodium 4-methyl-3-benzoyloxybenzoate (SPCC); Ammonium trimethyl tolyloxybenzenesulfonate; or sodium 3,5,5-trimethyl-hexanoyloxybenzenesulfonate (STHOBS). The bleach activators can be used in a quantity up to 20%, preferably 0.1-10% by weight, of the composition, although higher levels, of 40% or more, are acceptable, for example in bleaching additive product forms. highly concentrated or forms designed for automatic dosing in household appliances. The highly preferred bleach activators useful herein are substituted amide and an exhaustive and extensive description of those activators can be found in the U.S. Patents. 5,686,014 and 5,622,646. Other useful activators, described in the patent of E.U.A. No. 4,966,723, are of the benzoxazine type, such as a C6H4 ring to which a C (0) OC (R1) = N- portion is fused at positions 1, 2. A highly preferred activator of the benzoxazine type is: Depending on the activator and the exact application, it is possible to obtain good whitening results from whitening systems which during use have a pH of from about 6 to about 13, preferably from about 9.0 to about 10.5. Typically, for example, activators with electron-withdrawing portions are used for near neutral or subneutral pH scales. Alkalis or pH regulating agents can be used to ensure said pH. Acyl-lactam activators are very useful herein, especially the acylcaprolactams (see for example WO 94-28102 A) and acylvalerolactams (see E.U.A. 5,503,639). See also E.U.A. 4,545,784 which describes acylcaprolactams, including benzoylcaprolactam adsorbed on sodium perborate. Fn certain preferred embodiments of the invention, NOBS, lactam activators, imide activators or functional amide activators, especially the more hydrophobic derivatives, are conveniently combined with hydrophilic activators such as TAED, usually in weight proportions of hydrophobic activator: TAED in the scale from 1: 5 to 5: 1, preferably around 1: 1. Other suitable lactam activators are the modified alpha, see WO 96-22350 A1, July 25, 1996. Lactam activators, especially the most hydrophobic types, are conveniently used in combination with TAED, typically in weight proportions of caprolactam activators or amide derivatives: TAED in the ratio of 1: 5 to 5: 1, preferably about 1: 1. See also bleach activators having a residual cyclic amidine group described in the U.S. patent. 5,552,556. Non-limiting examples of additional activators useful herein may be found in E.U.A. 4,915,854, E.U.A. 4,412,934 and 4,634,551. The hydrophobic activator of nonanoyloxybenzenesulfonate (NOBS) and the hydrophilic activator of tetraacetylethylenediamine (TAED) are common, and mixtures thereof can also be used. Additional activators useful herein include those of U.S.A. 5,545,349, which is also incorporated herein by reference.

Transition metal bleach catalyst: If desired, the 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 US Pat. 5,246,621, patent of E.U.A. 5,244,594; patent of E.U.A. 5,194,416; patent of E.U.A. 5,114,606; European patents us. 549,271 A1, 549,272A1, 544,440A2, 544,490A1; and PCT applications PCT / IB98 / 00298 (attorney's file No. 6527X), PCT / IB98 / 00299 (attorney's file No. 6537), PCT / IB98 / 00300 (attorney's file No. 6525XL &), and PCT / IB98 / 00302 (attorney's file No. 6524L #); Preferred examples of those catalysts include Mn? 2 (u-0) 3 (1, 4,7-trimethyl-1, 4 (7-triazaclononan) 2 (PF6) 2, Mnl "2 (u-0)? (U- OAc) 2 ( 1, 4,7-trimethyl-1, 4,7-triazacyclononan) 2 (CIO4) 2, Mnlv4 (uO) 6 (1, 4,7-triazacyclononan) 4 (CI04) 4, Mn '"- Mnlv4 (u- 0) 1 (u-OAc) 2- (1, 4,7-trimethyl-1, 4,7-triazacyclononan) 2 (CI04) 3, Mn? V (1, 4,7-trimethyl-1, 4,7 -triazacyclononan) - (OCH3) 3 (PF6), and mixtures thereof Other metal-based bleach catalysts include those described in US Patents 4,430,243, 5,114,611 5,622,646 and 5,686,014 The use of manganese with several complex ligands to improve bleaching is also reported in the following US patents: 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 The cobalt bleach catalysts useful herein are known, and are described, for example, in M L. Tobe, "Base Hydrolysis of Transition-Metal Complexes", Adv. Inorg. Bioinorg. Mech., (1983), 2, pages 1-94 The most preferred cobalt catalyst useful in to present are the salts of pentaamine acetate which has the formula [Co (NH3) 5? Ac] Ty, in which "OAc" represents an acetate portion and "Ty" is an anion, and especially cobalt acetate chloride pentaamine, [Co (NH3) 5OAc] CI2; as well as [Co (NH3) 5OAc] (OAc) 2; [Co (NH3) 5OAc] (PF6) 2; [Co (NH3) 5OAc] (S04); [Co (NH3) 5OAc] (BF4) 2; and [Co (NH3) 5OAc] (N03) 2 (in the present "CAP"). These cobalt catalysts are readily prepared by known methods, as taught for example in the Tobe article and references cited therein, and in the US patent. 4,810,410, to Diakun et al, March 7, 1989. The compositions herein may also suitably include as a bleach catalyst the class of transition metal complexes of a rigid macropolycyclic ligand. The phrase "macropolicíclico rigid ligand" is sometimes abbreviated as "MRL". A useful MRL is [MnByclamCI2], where "biciclama" is (5,12-dimethyl-1, 5,8,12-tetraaza-bicyclo [6.6.2] hexadecan). See PCT applications PCT / IB98 / 00298 (attorney's file No. 6527X), PCT / IB98 / 00299 (attorney's file No. 6537), PCT / IB98 / 00300 (attorney's file No. 6525XL &), and PCT / IB98 / 00302 (attorney's file No. 6524L #). The amount used is a catalytically effective amount, suitably about 1 ppb or more, for example up to about 99.9%, more typically about 0.001 ppm or more, preferably from 0.05 ppm to 500 ppm (in which "ppb" denotes parts by weight). billion in weight and "ppm" denotes parts per million by weight). As a practical matter, and not by way of limitation, the cleaning compositions and methods herein can be adjusted to provide on the order of at least one part per 100 million species of active bleach catalyst in the aqueous washing medium. , and will preferably provide from 0.01 ppm to 25 ppm, more preferably from 0.05 ppm to 10 ppm, and more preferably from 0.1 ppm to 5 ppm, of the bleach catalyst species in the wash liquor. In order to obtain said levels in the washing liquid of an automatic washing process, the typical compositions herein will comprise from 0.0005% to 0.2%, more preferably from 0.004% to 0.08%, of bleach catalyst, especially catalyst of manganese or cobalt, by weight of the cleaning compositions.

Enzymatic sources of hydrogen peroxide In a different lane of the bleach activators illustrated hereinabove, another suitable hydrogen peroxide generating system is a combination of a C 1 -C 4 alkanol oxidase and a C 1 -C 4 alkanol, especially a combination of methanol oxidase (MOX) and ethanol. Said combinations are described in WO 94/03003.

Other enzymatic materials related to the bleach, such as peroxidases, haloperoxidases, oxidases, superoxide dismutases, catalases and their enhancers or, more commonly inhibitors, can be used as optional ingredients in the compositions of the moment. Oxygen transfer agents and precursors Also useful herein are any of the known organic bleach catalysts, oxygen transfer agents or precursors thereof. These include the compounds themselves and / or their precursors, for example any ketone suitable for the production of dioxiranes and / or any of the heteroatom-containing analogs of dioxirane or dioxirane precursors, such as sulfonimines R1R2C = NS? 2R3, see EP 446 982 A, published in 1991 and sulfonyloxaziridines, see EP No. 446,981 A published in 1991. Preferred examples of such materials include hydrophilic or hydrophobic ketones, used especially in conjunction with monoperoxysulfates to produce dioxiranes in situ, and / or the mines described in E.U.A. 5,576,282 and references described therein. The oxygen bleaches preferably used in conjunction with said oxygen transfer agents or precursors include percarboxylic acids and salts, acids and percarbon salts, acid and peroxymonosulfuric salts, and mixtures thereof. See also E.U.A. 5,360,568; E.U.A. 5,360,569; E.U.A. 5,370,826 and E.U.A. 5,442,066. Although oxygenated bleaching systems and / or their precursors may be susceptible to decomposition during storage in the presence of moisture, air (oxygen and / or carbon dioxide) and traces of metals (especially rust or simple salts or colloidal oxides of transition metals) and when subjected to light, stability can be improved by adding common sequestrants (chelators) and / or polymeric dispersants and / or a small amount of antioxidant to the bleaching system or product. See, for example, E.U. & 545,349. Antioxidants are commonly added to detergent ingredients that vary from enzymes to surfactants. Their presence is not necessarily inconsistent with the use of an oxidizing bleach; for example, introduction of a barrier system to stabilize an apparently incompatible combination of an enzyme and an antioxidant, on the one hand, and an oxygenated bleach, on the other, can be used. Although commonly known substances can be used as antioxidants, see for example the patents of E.U.A. 5,686,014, 5,622,646, 5,055,218, 4,853,143, 4,539,130 and 4,483,778. Preferred antioxidants are 3,5-di-tert-butyl-4-hydroxytoluene, 2,5-di-tert-butylhydroquinone and D, L-alpha-tocopherol.

Polymeric dirt release agent 5 The compositions according to the present invention may optionally comprise one or more soil release agents. Polymeric soil release agents are characterized to have hydrophilic segments, to hydrophilize the surface of hydrophobic fibers, such as polyester and nylon, and hydrophobic segments, to be deposited on hydrophobic fibers and remain adhered to them through the completion of the wash cycle and, therefore, thus serving as an anchor for the hydrophilic segments. This can make it possible for stains that occur after treatment with the soil release agent to be more easily cleaned in subsequent washing procedures. If used, the polymeric soil release agents will generally comprise from about 0.01% to 10.0%, preferably from about 0.1% to 5%, more preferably from about 0.2% to 3% by weight, of the composition. The following, all included herein by reference, disclose soil release polymers suitable for the present invention. USES. 5,691, 298 Gosselink et al, November 25, 1997; USES. 5,599,782, Pan et al, February 4, 1997; USES. 5,415,807, Gosselink et al, May 16, 1995; USES. 5,182,043 Morral et al, of 26 January 1993; USES. 4,956,447 Gosselink et al, from September 1, 1990; USES. 4,976,879 Maldonado et al, December 1, 1990; USES. 4,968,451 Scheibel et al, November 6, 1990; USES. 4,925,577 Borcher Sr. et al, May 15, 1990; USES. 4,861, 512 Gosselink, August 29, 1989; USES. 4,877,896, Maldonado et al, of October 31, 1989; USES. 4,702,857 Gosselink et al, October 27, 1987; USES. 4.71 1, 730 Gosselink et al, December 8, 1987; USES. 4,721, 580 Gosselink of January 26, 1988; USES. 4,000,093 Nicol et al, December 28, 1976; USES. 3,959,230 Hayes, of May 25, 1976; USES. 3,893,929 Basadur, July 8, 1975; and European patent application 0 219 048, published April 22, 1987 by Kud et al. Additional suitable soil release agents are described in U.S.A. 4,201, 824 Voillan et al; USES. 4,240,918 Lagasse et al; USES. 4,525,524 Tung et al; USES. 4,579,681 Ruppert et al; USES. 4,220,918; USES. 4,787,989; EP 279,134 A, 1988 to Rhone-Poulenc Chemie; EP 457,205 A to BASF (1991); and DE 2,335,044 to Uniliver N.V., 1974; all incorporated herein by reference.

Clay soil remover / anti-redeposition agents The compositions of the present invention may also optionally contain water-soluble ethoxylated amines having clay dirt removal and anti-redeposition properties. The granular detergent compositions containing these compounds typically they contain from about 0.01% to about 10.0% by weight of the water-soluble ethoxylated amines; Liquid detergent compositions typically contain about 0.01% to about 5%. A preferred soil remover and anti-redeposition agent is ethoxylated tetraethylenepentamine. Illustrative ethoxylated amines are more fully described in the U.S. patent. No. 4,597,898, VanderMeer, issued July 1, 1986. Another group of clay soil removers / amphibian redeposition agents are the cationic compounds described in European patent application 111, 965, Oh and Gosselink, published on June 27. of 1984. Other clay soil removers / amphibition agents that may be used include the ethoxylated amine polymers described in European patent application 111, 984, Gosselink, published Jun. 27, 1984; the zwitterionic polymers described in European Patent Application 112,592, Gosselink, published July 4, 1984; and the amine oxides described in the U.S. patent. No. 4,548,744, Connor, issued October 22, 1985. Other clay removers and / or anti-redeposition agents known in the art can be used in the compositions herein. Consult the patent of E.U.A. 4,891, 160, VanderMeer, January 2, 1990 and WO 95/32272, published November 30, 1995. Another type of preferred anti-redeposition agent includes carboxylmethylcellulose (CMC) materials. These materials are well known in the art.

Polymeric dispersion agents Polymeric dispersion agents can be advantageously used at levels of from about 0.1% to about 7%, by weight, in the compositions herein, especially in the presence of zeolite and / or layered silicate builders. Suitable polymeric dispersing agents include polymeric polycarboxylates and polyethylene glycols, although others known in the art may also be used. It is believed, although not intended to be limited by theory, that polymer dispersion agents increase the performance of the global detergency builder, when used in combination with other detergency builders (including lower molecular weight polycarboxylates) by inhibition of crystal growth, peptization of particulate soil release and anti- redeposition. Polymeric polycarboxylate materials can be prepared by polymerizing or copolymerizing suitable unsaturated monomers, preferably in their acid form. Unsaturated monomeric acids which can be polymerized to form suitable polymeric polycarboxylates include acrylic acid, maleic acid (or maleic anhydride), fumaric acid, itaconic acid, aconitic acid, mesaconic acid, citraconic acid and methylenemalonic acid. The presence of the polymeric polycarboxylates in the present or monomeric segments, which do not contain carboxylate radicals such as vinyl methyl ether, styrene, ethylene, etc., is suitable provided that said segments do not constitute more than about 40% by weight. Particularly suitable polymeric polycarboxylates can be derived from acrylic acid. The average molecular weight of such polymers in the acid form perferably varies from about 2,000 to 10,000, most preferably from about 4,000 to 7,000 and most preferably from about 4,000 to 5,000. Soluble polymers of this type are known materials. The use of polyacrylates of this type in detergent compositions has been described, for example, in Diehl, US Pat. 3,308,067, issued March 7, 1967. Copolymers based on acrylic / maleic acid may also be used as a preferred component of the. dispersing / anti-redeposition agent. Such materials include the water-soluble salts of copolymers of acrylic acid and maleic acid. The average molecular weight of said copolymers in the acid form perferrably ranges from about 2,000 to 100,000, most preferably from about 5,000 to 75,000 and most preferably from about 7,000 to 65,000. The ratio of the acrylate segments to maleate segments in said copolymers will generally be in the range of about 30: 1 to about 1: 1, more preferably about 10: 1 to 2: 1. Soluble acrylate / maleate copolymers of this type are known materials which are described in European patent application No. 66915, published on December 15, 1982, as well as in EP 193,360, published on September 3, 1986, which also describes polymers comprising hydroxypropylacrylate. Still other useful dispersing agents include the maleic / acrylic / vinyl alcohol terpolymers. Such materials are also described in EP 193,360, including, for example, terpolymer 45/45/10 maleic / acrylic / vinyl alcohol. Another polymeric material that can be included is polyethylene glycol (PEG). PEG can exhibit dispersing agent performance as well as act as a clay dirt removal / anti-redeposition agent. Typical molecular weight scales for these purposes range from about 500 to about 100,000, preferably about 1,000 to about 50,000 and most preferably about 1,500 to about 10,000. Dispersants of polyaspartate and polyglutamate, especially in conjunction with zeolite builders, can also be used. Dispersing agents such as those of polyaspartate preferably have a molecular weight (avg.) Of about 10,000. Other types of polymers that may be more desirable for purposes of biodegradability, improved bleach stability or cleaning include various hydrophobically modified terpolymers and copolymers, including those marketed by Rohm & Haas, BASF Corp., Nippon Shokubai and others for all forms of water treatment, textile treatment or detergent applications. Brightener.- Any brighteners can be incorporated J- "- - - •" * * "- - - *« »« - »- • optical or other brightening agents or whitening agents known in the art at levels typically from about 0.01% to 1.2% by weight, in the detergent compositions herein when designed for washing or treating fabrics Specific examples of optical brighteners that are useful in the present compositions are those identified in US Patent 4,790,856 issued to Wixon on December 15, 1988. These brighteners include the Verana PHORWHITE brightener series Other brighteners described in this reference include: Tinopal UNPA, Tinopal CBS and Tinopal 5BM, available from Ciba-Geigy, Arctic White CC and Arctic White CWD, 2- (4-styryl-phenyl) -2H -naphthol [1, 2-d] triazoles; 4,4'-bis- (1, 2,3-triazol-2-yl) -stilbenes; 4,4'-bis (steryl) bisphenyls; and the aminocoumarins Specific examples of these brighteners include 4-methyl-7-diethyl-aminocoumarin; 1,2-bis (-benzyl) midazol-2-yl) -ethylene; 1,3-diphenylpyrazolines; 2,5-bis (benzoxazol-2-yl) thiophene, 2-eetyryl-naphthyl- [1,2-s] oxazole; and 2- (stilbene-4-yl) -2H-naphtho- [1,2-d] triazole. See also the patent of E.U.A. 3,646,015, issued on February 29, 1972 to Hamilton. Dye transfer inhibiting agents.- The compositions according to the present invention can also include one or more effective materials to inhibit the transfer of dyes from one fabric to another during the cleaning process. In general, said dye transfer inhibiting agents include polyvinylpyrrolidone polymers, polyamine N-oxide polymers, copolymers of N-vinylpyrrolidone and N-vinylimidazole, manganese phthalocyanine, peroxidases and mixtures thereof. If used, these agents typically comprise from about 0.01% to about 10% by weight of the composition, preferably from about 0.01% to about 5%, and most preferably from about 0.05% to about 2%. See U.S. Patent No. 5,633,255 to Fredj. Guelaator Agents.- The detergent compositions herein may also optionally contain one or more chelating agents, particularly chelating agents for upstart transition metals. Those commonly found in the wash water include iron and / or manganese in colloidal or water-soluble form, and may be associated as oxides or hydroxides, or found in association with soils such as humic substances. The chelators that are preferred are those that effectively control said transition metals, especially including controlling the deposition of said transition metals or their compounds on fabrics and / or controlling undesirable oxidation reduction reactions in the washing medium and / or fabric fabrics or hard surfaces. Such chelating agents include those having low molecular weights, as well as polymeric types, typically with at least one, preferably two or more heterogeneous donor atoms such as O or N, capable of coordination to a transition metal. Common chelating agents can be selected from the group consisting of ^^^^ ^ ^ ^ B ^^^ j ^ aminocarboxylates, aminophosphates, polyfunctionally substituted aromatic chelating agents and mixtures thereof. If used, the chelating agents will generally comprise from about 0.001% to about 15% by weight of the detergent compositions herein. More preferably, if used, the chelating agents will comprise from about 0.01% to about 3.0% by weight of said compositions. Foam suppressants.- Compounds for reducing or suppressing foaming can be incorporated in the compositions of the present invention when required for designed use, especially -Wash laundry in domestic washing machines. Other compositions, such as those designed for hand laundry, may desirably be high foaming and may omit said ingredients. The suppression of foam may be of particular importance in so-called "high concentration cleaning processes" such as those described in E.U.A. 4,489,455 and 4,489,574, and in front-loading European-style washing machines. A wide variety of materials can be used as foam suppressors, and are well known in the art. See, for example, Kirk Othmer Encyclopedia of Chemical Technology, 3a. Edition, Volume 7, pages. 430-447 (John Wiley &Sons, Inc., 1979). The compositions herein will generally comprise from 0% to about 10% foam suppressant. When they are used as suds suppressors, monocarboxylic fatty acids, and salts of they will typically be present in amounts of up to about 5%, preferably 0.5% to 3% by weight of the detergent composition, although higher amounts may be used. Preferably, about 0.01% to about 1% of the silicone foam suppressant is used, most preferably about 0.25% to about 0.5%. These weight percent values include any silica that can be used in combination with polyorganosiloxane, as well as any foam suppressor auxiliaries that can be used. Monostearyl phosphate foam suppressors are used generally in amounts ranging from about 0.1% to about 2% by weight of the composition. The hydrocarbon foam suppressors are typically used in amounts ranging from about 0.01% to about 5.0%, although higher levels can be used. The alcohol foam suppressors are typically used at 0.2% - 15 3% by weight of the finished compositions. Alkoxylated polycarboxylates. The alkoxylated polycarboxylates such as those prepared from polyacrylates are useful herein to provide additional fat removal performance. Such materials are described in WO 91/08281 and PCT 90/01815, p. 4 et seq., incorporated herein by way of reference. Chemically, these materials comprise polyacrylates that have an ethoxy side chain for every 7-8 acrylate units. The side chains have the formula - (CH2CH20) m (CH2) nCH3 where m is 2-3 and n is 6-12. These chains ** "***" * »- •» -? 'llilt§É A ~ a? "- * • *" »-. * ~ ^ *. ~,?. *», t & Laterals are attached by ester to the "base structure" of the polyacrylate to provide a "comb" type polymer structure. The molecular weight may vary, but is typically in the range of about 2000 to about 50,000. Said alkoxylated polycarboxylates can comprise from about 0.05% to about 10% by weight of the compositions herein. Fabric softeners.- Various fabric softeners that soften during washing can be optionally used, especially the impalpable smectite clays of the U.S. patent. 4,062,647, Storm and Nirschi, issued December 13, 1977, as well as other softening clays known in the art, typically at levels of from about 0.5% to about 10% by weight in the compositions herein to provide softening benefits concurrently with the cleaning of fabrics Clay-based softeners can be used in combination with amine and cationic softeners as described, for example, in the US patent. 4,375,416, Crisp et al., March 1, 1983 and in the US patent. 4,291, 071, Harris et al., Issued September 22, 1981. In addition, in the laundry washing methods of the present, known fabric softeners, including biodegradable types, can be used in pre-treatment modes, main wash, back wash and dryer add-on. Perfumes.- The perfumes and perfumery ingredients useful in the present compositions and methods comprise a wide range of perfumes and perfumes.

It is a variety of natural and synthetic chemical ingredients, including, but not limited to, aldehydes, ketones, esters and the like. Also included are various natural extracts and essences which may include complex mixtures of ingredients such as orange oil, lemon oil, rose extract, lavender, musk, patchouli, balsamic essence, sandalwood oil, pine oil, cedar and the like. The finished perfumes can comprise extremely complex mixtures of said ingredients. The finished perfumes typically comprise from about 0.01% to about 2% by weight of the detergent compositions herein, and the individual perfumery ingredients can comprise from about 0.0001% to about 90% of a finished perfume composition. Other Ingredients.- A wide variety of other ingredients useful in detergent compositions can be included in the compositions herein, including other active ingredients, vehicles, hydrothopes, processing aids, dyes or pigments, solvents for liquid formulations, solid fillers for compositions in bar, etc. If high foam formation is desired, foaming agents such as C10-C16 alkanolamides, typically at levels of 1% -10%, can be incorporated into the foam-promoting compositions. C10-C14 monoethanol and diethanolamides illustrate a typical class of such foam boosters. It is also advantageous to use other suds promoters with high sudsing surfactants, such as oxides 2HMtó ¿sagg < fes »fetofa-dtea ^ M =» of amine, betaines and sultaines indicated above. If desired, soluble magnesium salts such as MgCl 2, MgSO 4, CaCl 2, CaSO 4 and the like can be added, typically, at 0.1% -2% levels, to provide additional foams and enhance the fat removal capacity, especially for liquid purposes for dishwashing. In addition, various detersive ingredients employed in the present invention can optionally be stabilized by absorbing said ingredients onto a porous hydrophobic substrate, then coating said substrate with a hydrophobic coating. Preferably, a is a detersive ingredient with a surfactant before it is absorbed into the porous substrate. In use, the detersive ingredient is released from the substrate into the aqueous wash bath, where it performs its desired detersive function. The liquid detergent compositions may contain water and other solvents as carriers. Primary alcohols are suitable or Low molecular weight secondary IJs, exemplified by methanol, ethanol, propanol and isopropanol are suitable. Monohydric alcohols are preferred as a solubilizing surfactant, but polyols such as those containing from 2 to about 6 carbon atoms and from 2 to about 6 hydroxy groups (eg, 1,3-propanediol, ethylene glycol, glycerin) can also be used. and 1,2-propanediol). The compositions may contain from 5% to 90%, typically from 10% to 50% of such vehicles. The detergent compositions herein preferably rtÉaTffiiífnif mm i jj? r --- A ^ - ^ B ^ - '^' «- * - ^ shall be formulated in such a way that, during its use in aqueous cleaning operations, the washing water has a pH of between about 6.5 and about 11, preferably between about 7.0 and 10.5, more preferably between about 7.0 to about 9.5. The liquid formulations of the dishwashing product preferably have a pH of between about 6.8 and about 9.0. Wash products typically have a pH of 9-11. Techniques for controlling pH at recommended levels of use include the use of pH, alkali, acid regulators, etc., and are well known to those skilled in the art. technique. Form of the Compositions The compositions according to the invention can take a variety of physical forms including granular form, gel, tablet, bar, and liquids. The compositions include the detergent compositions granular calls. concentrates adapted to be added to a washing machine by means of a dispensing device placed in the drum of the machine with the load of dirty cloth. The average particle size of the components of the granular compositions according to the invention should be preferably such that no more than 5% of the particles are larger than 1.7 mm in diameter and no more than 5% of the particles are less than 0.15 mm in diameter. The average particle size as defined in tOx? *, ^. . The present invention is calculated by sifting a sample of the composition in a number of fractions (typically 5 fractions) over a series of Tyler sieves. The fractions by weight obtained in this way are plotted against the opening size of the sieves. The average particle size is taken to be the size of the aperture through which 50% by weight of the sample would pass. Certain preferred granular detergent compositions according to the present invention are the high density types, now common in the market; they typically have a bulk density of at least 600 g / liter, more preferably from 650 g / liter to 1200 g / liter. High Density Detergent Composition Procedures Vain media and equipment are available for preparing high density granular detergent compositions (ie, more than about 550, preferably larger than 650 grams / liter or "g / l"), of high solubility , free-flowing.-according to the present invention. Current commercial practice in the field uses spray-drying towers to make granular laundry detergents that often have a density of less than about 500 g / l. In this process, an aqueous suspension of various heat-stable ingredients in the final detergent composition is formed into homogeneous granules by passing them through a spray-drying tower, using conventional techniques, at temperatures from about 175 ° C to about 225 °. C. However, if spray drying is used as part of the total process herein, additional or alternate process steps should be used as described below to obtain a density level (ie,> 650 g / l) required by the. modern compact detergent products, low dosage. For example, spray-dried granules from a tower can be further densified by charging a liquid such as water or a nonionic surfactant into the pores of the granules and / or subjecting them to one or more high-speed mixers / densifiers. A high speed mixer / densifier suitable for this process is a device marketed under the trade name "Lódige CB 30" or "- Lódige CB 30 Recycler" comprising a static cylindrical mixing drum having a rotating center shaft with mixing blades / cut mounted on it. When used, the ingredients for the detergent composition are introduced into the drum and the shaft / blade assembly is rotated at speeds in the 100-2500 rpm range to provide deep mixing / densification. See Jacobs, et al, patent of E.U.A. No. 5,149,455, issued September 22, 1992, and U.S. Patent No. 5,565,422, issued October 15, 1996 to Del Greco et al. Another such device includes devices marketed under the trade name "Shugi Granulator" and under the trade name "Drais K-TTP 80. Another process step that can be used to further densify spray-dried granules involves treating the dried granules. by spraying in a moderate speed mixer / densifier Equipment such as mixers / densifiers marketed under the trade name "Lódige KM" (Series 300 or 600) or "Lodige Ploughshare" are suitable for this process step. at 40-160 rpm.The residence time of the detergent ingredients in the moderate speed mixer / densifier is approximately 0.1 to 12 minutes, conveniently measured by dividing the fixed weight of the mixer / densifier by the performance (eg, kg / hour). Other useful equipment includes the device that is available under the trade name "Drais K-T 160". This process step using a moderate speed mixer / densifier (eg Lodige KM) can be used on its own or sequentially with the aforementioned high speed mixer / densifier (eg Lódige CB) to achieve the desired density. Other types of apparatus for making granules useful herein include the apparatuses described in U.S. Patent No. 2,306,898, to G.L. Heller, December 29, 1942. Although it may be more appropriate to use the high-speed mixer / densifier followed by the moderate-speed mixer / densifier, the reverse sequential mixer / densifier configuration can also be used. One or a combination of several parameters can also be used including residence times in the mixer / densifiers, operating temperatures of the equipment, temperature and / or composition of the granules, the use of ^^^.-.-, .- ^^ ^ ^ ^ ~ m Sií¿i ** ** '* &.!. M adjunct ingredients such as liquid binders and flow aids to optimize densification the spray-dried granules in the process of the invention. By way of example, consult the procedures in Appel et al, patent of E.U.A. No. 5,133,924, issued July 28, 1992; Delwel et al, patent of E.U.A. No. 4,637,891, issued January 20, 1987; Kruse et al, patent of E.U.A. No. 4,726,908, issued February 23, 1988; and Bortolotti et al, patent of E.U.A. No. 5,160,657, issued November 3, 1992. In those situations in which detergent ingredients that are particularly sensitive to heat or highly volatile are to be incorporated in the final detergent composition, processes which do not include spray towers are preferred. The formulsdor can eliminate spray-drying step by feeding, in continuous or intermittent mode, starting detergent ingredients directly into mixing equipment that is commercially available. A particularly preferred embodiment involves charging a paste of surfactant and an anhydrous material in a high speed mixer / densifier (eg Lódige CB) followed by a moderate speed mixer / densifier (eg Lódige KM) to form high detergent agglomerates. density. See Capeci et al, patent of E.U.A. No. 5,366,652, issued November 22, 1994 and Capeci et al, US patent. No. 5,486,303, issued January 23, 1996. Optionally, the liquid / solids ratio of the starting detergent ingredients in said process can be selected to obtain high density agglomerates that are more crisp and more free flowing. See Capeci et al, patent of E.U.A. No. 5,565,137, issued October 15, 1996. Optionally, the process may include one or more recycle streams of smaller particles produced by the process that can be fed back to the mixers / densifiers for further agglomeration or formation. The larger particles produced by the process can be sent to a grinding apparatus and then fed back into the mixing / densifying equipment. These additional feedback procedure steps facilitate the agglomeration formation of the starting detergent ingredients resulting in a finished composition having a uniform distribution of particle size (400-700 microns) and density (> 550 g / l). desired. See Capeci et al, patent of E.U.A. No. 5,516,1448, issued May 14, 1996 and Capeci et al, US patent. No. 5,489,392, issued February 6, 1996. Other suitable methods that do not require the use of spray-drying towers are described by Bollier et al, U.S. Pat. No. 4,828,721, issued May 9, 1989; Beerse et al, patent of E.U.A. No. 5,108,646, issued April 28, 1992; and Jolicoeurt, patent of E.U.A. No. 5,178,798, issued January 12, 1993. In another embodiment, a high density detergent composition utilizes a fluidized bed mixer. In this procedure, the various ingredients of the finished composition are combined in an aqueous slurry (typically 80% solids content) and sprayed in a fluidized bed to provide finished detergent granules. Before the fluidized bed, this process can optionally include the step of mixing the slurry using the mixer / densifier Lödige CB mentioned above or mixer / densifier "Flexomix 160", available from Shugi. Fluidized beds or movable beds of the type available under the trade name "Escher Wyss" can be used in such processes. Another suitable method that can be used herein includes feeding a liquid acid precursor of an anionic surfactant, an alkaline inorganic material (eg, sodium carbonate) and optionally other detergent ingredients in a high-speed mixer / densifier to form partially or fully neutralized anionic surfactant salt-containing particles and the other starting detergent ingredients. Optionally, the content of the high speed mixer / densifier can be sent to a moderate speed mixer / densifier (eg Lódige KM) for further mixing resulting in the finished high density detergent composition. Consult Appel et al, patent of E.U.A. No. 5,164,108, issued November 17, 1992. Optionally, the high density detergent compositions according to the present invention can be produced by combining conventional or densified spray-dried detergent granules with detergent agglomerates in various proportions (for example a ratio of 60:40 weight of granules to agglomerates) produced by one or a combination of processes discussed herein. See U.S. Patent No. 5,569,645, issued October 29, 1996 to Dinniwell et al. Additional auxiliary ingredients such as enzymes, perfumes, brighteners and the like may be sprinkled or mixed with the agglomerates, granules or mixtures thereof produced by the methods discussed herein.

Laundry Method The laundry washing methods of the present invention typically comprise treating the laundry with an aqueous washing solution in a washing machine having dissolved or supplied therein an effective amount of a washing detergent composition in the washing machine. according to the invention. For an effective amount of the detergent composition is meant from 40g to 300g of product dissolved or dispersed in a washing solution of a volume of 5 to 65 liters, which are typical doses of product and in volumes of washing solution commonly used in conventional laundry washing methods. As noted, surfactants are used herein in detergent compositions, preferably in combination with other detersive surfactants, at levels that are effective to achieve at least a directional improvement in cleaning performance. In the context of a composition for washing fabrics, said "levels of use" may vary depending not only on the type and severity of the soils and stains, but also on the temperature of the washing water, the volume of the washing water and the volume of the washing water. type of washing machine. In a preferred use aspect, a supply device is used in the washing method. The delivery device is loaded with the detergent product, and is used to introduce the product directly into the drum of the washing machine. Its volume capacity must be such that it can contain sufficient detergent product such as the one would normally be used in the washing method. Once the washing machine has been loaded with clothes, the delivery device containing the detergent product is placed inside the tub. At the beginning of the wash cycle of the washing machine, water is introduced into the tub and it rotates periodically. The design of the device The delivery should be such as to allow the dry detergent product to be contained but to then allow the release of this product during the wash cycle in response to its agitation while the tub is spinning and also as a result of its contact with the wash water. As an alternative, the delivery device can be a flexible container, such as a bag or sack. The bag may have a fibrous structure coated with a waterproof protective material to thereby retain the contents, such as that described in published European patent application No. 0018678. Alternatively, the bag may * Fc -. »-. ^^. ja ^. ^^ a ^ ...., -. ^ a ^^^ ... ar ^^ be made of a water-insoluble synthetic polymeric material provided with an edge seal or seal designed to break in the aqueous medium as described in published European patent applications Nos. 0011500, 0011501, 0011502 and 0011968. A convenient form of waterproof closure comprises a water soluble adhesive disposed along and sealing one end of a bag formed of a waterproof polymeric film such as polyethylene or polypropylene.

EXAMPLES OF DETERGENT COMPOSITION In these examples, the following abbreviations are used for a modified alkylbenzene sulfonate, sodium salt form or potassium salt form, prepared according to any of the preceding process examples: MLAS The following abbreviations are used for product auxiliary materials for cleaning: Cxy amine oxide: N-oxide of alkyldimethylamine RN (O) Me2 of given chain length Cxy where the average total carbon scale of the non-methylalkyl R portion is 10 + x to 10 + y. Amylase: Amylolytic enzyme of activity 60KNU / g marketed by Novo Industries A / S under the trade name Termamyl 60T. Alternatively, the amylase is selected from: Fungamyl®; Duramyl®; BAN®; and alpha-amylase enzymes which are described in W095 / 26397 and in the co-pending application by Novo Nordisk PCT / DK96 / 00056. APA: C8-C10 amidopropyldimethylamide. Cxy betaine: Alkyldimethylbetaine having an average total carbon scale of the alkyl portion of 10 + x to 10 + y.

Bicarbonate: Anhydrous sodium bicarbonate with a particle size distribution between 400μm and 1200μm. Borax: Na tetrahydrate tetrahydrate. BPP: Butoxy-propoxy-propanol. Brightener 1: 4,4, -b¡s (2-sulphotyryl) bifenyl disodium Brightener 2: 4,4'-bis (4-anilino-6-morpholino-1,3,5-tr! Azin-2-il) amino) disodium stilben-2: 2'-d-sulphonate CaCl2 Calcium chloride Carbonate: Na2C03 anhydrous 200μm - 900μm Cellulase: Cellulose enzyme, 1000 CEVU / g, Novo, Carezyme® Citrate: Trisodium citrate dihydrate 86.4%, 425μm - 850μm Citric acid: Citric acid, anhydrous CMC: Sodium carboxymethylcellulose CxyAS: Alkylsulfate, Na salt or other salt if specified, which has an average total carbon scale of the alkyl portion of 10 + x to 10 + y. CxyEz: commercial linear or branched ethoxylated alcohol (it does not have methyl branching in the middle part of its chain) and that has an average total carbon scale of the alkyl portion of 10 + x to 10 + and with an average of z moles of oxide of ethylene. CxyEzS: Alkylethoxylate sulfate, Na salt or other salt if specified, which has an average total carbon scale of the alkyl portion of 10 + x to 10 + and averaging z moles of ethylene oxide. Diamine: Alkyldiamine, for example, 1,3 propanediamine, Dytek EP, Dytek A, (Dupont) or selected from: dimethylaminopropylamine, 1,6-hexanediamine; 1,3-propanediamine; 2-methyl-1,5-pentanediamine; 1, 3-pentanediamine; 1-methyl-diaminopropane; 1, 3-cyclohexanediamine; 1,2 cyclohexanediamine. Dimethicone: Mixture of 40 (gum) 60 (fluid) by weight of dimethicone rubber SE-76 (G.E. Silicones Div.) / Dimethicone fluid of viscosity 350 cS. DTPA: Diethylenetriaminepentaacetic acid DTPMP: Diethylenetriaminepenta (methylenephosphonate), Monsanto, (Dequest 2060). Endolase: Endoglucanase, activity 3000 CEVU / g NOVO EtOH: Ethanol Fatty acid (C12 / 18): C12-C18 fatty acid.

Fatty acid (C12 / 14): C12-C14 fatty acid. Fatty acid (C14 / 18): Fatty acid of C14-C18. Fatty acid (RPS): Fatty acid of colaza Fatty acid (TPK) Fatty acid crowned with palm seed. Format: Format (sodium) HEDP: 1, 1-hydroxyethyl-diphosphonic acid Hydrotrope: Selected from sodium, potassium, magnesium, calcium, ammonium or water-soluble substituted ammonium salts of toluenesulfonic acid, naphthalenesulfonic acid, cumenesulfonic acid, xylene sulfonic acid. sofc! 12: Guerbet spirits of X12 (average) (Condea). Isofol 16: Guerbet alcohols of C16 (average) (Condea). LA3: Alkylbenzenesulfonate from linear (for example «to Na or K of C11.8) Lipase: Lipolytic enzyme, 100kLU / g, NOVO, Lipolase®. Alternatively, the lipase is selected from: Amano-P; M1 Lipase®; Lipomax®; D96L lipolytic enzyme variant of the original lipase derived from Humicola lanuginosa as described in E.U.A. series No. 08/341, 826; and the strain Humicola lanuginosa DSM 4106. LMFAA: N-methylalkylglucamide of C12-14. MA / AA: Copolymer 1: 4 of maleic / acrylic acid, Na salt, The average molecular weight of about 70,000. MBAxEy: Branched primary alkyl ethoxylate in the middle part of its chain (average total carbons = x, average EO = y). MBAxEyS: Primary alkyl ethoxylate sulphate branched in the middle part of its chain or modified, Na salt, (average total carbons = x, average EO = y) according to the invention (see example 9). MBAyS: Primary alkylsulphate branched in the middle part of its chain, Na salt, (average total carbons = y) - MEA: Monoethanolamine. Cxy MES: Alkylmethyl sulphonate, Na salt, which has an average total carbon scale of the alkyl portion of 10 + x to 10 + y. MgCl2: Magnesium chloride. MnCAT: Catalyst of macrocyclic manganese bleach as in EP 544,440 A or, preferably, use. { Mn (Biciclama) Cl2} in which bicyclate = 5,12-dimethyl-1, 5,8,12-tetraazabicyclo. { 6.6.2} hexadecane or a comparable macrocycle with tetra-aza bridge.

NaDCC: Sodium dichloroisocyanurate NaOH: Sodium hydroxide Cxy NaPS: Paraffinsulfonate, salt of Na, which has an average total carbon scale of the alkyl portion of 10 + x to 10 + y. NaSKS-6: Crystalline layered silicate of the formula d- Na2Si2? 5 NaTS: Sodium toluene sulphonate. NOBS: Nonanoyloxybenzenesulfonate, sodium salt LOBS: C12 oxybenzenesulfonate, sodium salt PAA: Polyacrylic acid (MW = 4500). PAE: Ethoxylated tetraethylenepentamine PAEC: ethoxylated quaternized methyldiexylenetriamine. PB1: Anhydrous sodium perborate bleach of nominal formula NaBG2? 2? 2 PEG: Polyethylene glycol (pm = 4600) Percarbonate: Sodium percarbonate of nominal formula 2Na2C03-3H202 PG: Propanediol. Photoblank: Sulfonated zinc phthalocyanine encapsulated in soluble polymer in dextrin. FOOT: Ethoxylated polyethyleneimine, water soluble.

Protease: Proteolytic enzyme, 4KNPU / g, NOVO, Savinase®. Alternatively, the protease is selected from: Maxatase®; Maxacal®; Maxapem 15®; subtilisin BPN and BPN '; Protease B; Protease A; Protease D; Primase®; Durazym®; Opticlean®; and Optimase®; and Alcalase®. QAS: R2.N + (CH3) x ((C2H40) yH) z with R2 = C8-C18 x + z = 3, x = 0 to 3, z = 0 to 3, y = 1 to 15. Cxy SAS: Alkylsulfate secondary, salt of Na having an average total carbon scale of the alkyl portion of 10 + x to 10 + y. Silicate: Sodium silicate, amorphous (ratio Si02: Na2? 2.0) Silicone antifoam: Polydimethylsiloxane foam controller with a siloxane-oxyalkylene copolymer as a dispersing agent; Foam controller ratio: dispersing agent from 10: 1 to 100: 1; or combination of fuming silica and high viscosity polydimethylsiloxane (optionally chemically modified). Solvent: Non-aqueous solvent, for example, hexylene glycol, also consult propylene glycol. SRP 1: Esters of sulfobenzoyl end blocked with «« & a ^ * e ^^^ ag ^ j ^ S base structure of oxyethylene and terephthaloyl. SRP 2: Ethoxylated sulfonated terephthalate polymer. SRP 3: Ethoxylated terephthalate polymer blocked by methyl. STPP: Sodium tripolyphosphate, anhydrous Sulfate: Sodium sulfate, anhydrous TAED: Tetraacetylethylenediamine TFAA: C16-C18 alkyl N-methylglucamide Zeolite A: Hydrated sodium aluminosilicate, Na? 2 (A102Si? 2) i2 '27H20, 0.1 - 10 microwaves Zeolite MAP: Zeolite (maximum aluminum P) detergent grade (Crosfield). Typical ingredients that are often referred to as "minor" may include perfumes, dyes, pH cuts, etc. The following example is illustrative of the present invention, but does not mean that it limits or otherwise defines its scope. All parts, percentages and relationships used herein are expressed as weight percent unless otherwise specified.

EXAMPLE 25 The following detergent compositions A to F are prepared according to the invention: fifteen te '^ * fffl- TnrTiiTi.rt.f - "" && EXAMPLE 26 The following detergent compositions G to J suitable for hand washing of soiled fabrics are prepared according to the invention: EXAMPLE 27 Compositions of cleaning products The following laundry detergent compositions K to O are prepared according to the invention. The abbreviations are as used in the preceding examples. < && amp; ? ÉMm ** ** ^. ^ * ^.

EXAMPLE 28 Non-limiting examples P-Q of a non-aqueous liquid laundry detergent composition containing bleach are prepared as follows: PQ Component% by weight Scale (% by weight) Liquid phase MLAS 15 1-35 LAS 12 0-35 C24E5 14 10-20 Solvent or 27 20-30 hexylene glycol Perfume 0.4 0-1 Solid phase Protease 0.4 0-1 Citrate 4 3 -6 PB1 3.5 2-7 NOBS 8 2-12 Carbonate 14 5-20 DTPA 1 0-1.5 Brightener 1 0.4 0-0.6 Antifoam 0.1-0-0.3 silicone minor rest Rest The resulting heavy duty anhydrous liquid laundry detergent provides excellent stain and dirt removal performance when used in normal fabric washing operations. fe ^ t AÉFEAiii ^ '^ gg & EXAMPLE 29 The following examples R-V further illustrate the present invention with respect to shampoo formulations.

. ^ S-, ^ M # e,

Claims (53)

1. NOVELTY OF THE INVENTION CLAIMS 1. A modified alkylbenzene sulfonate surfactant mixture comprising: (a) from 60% to 95% by weight of a mixture of branched alkylbenzene sulphonates having the formula (I): (I) In which L is an aliphatic acyclic portion consisting of carbon and hydrogen, said L has two methyl terms and said L has no substituents other than A, R1 and R2; and wherein said mixture of branched alkylbenzene sulphonates contains two or more of said branched alkylbenzene sulphonates which differ in molecular weight from the anion of said formula (I) and wherein said mixture of branched alkylbenzene sulphonates has: - a sum of carbon atoms in R1 , L and R2 from 9 to 15; - an average aliphatic carbon content of 10.0 to 14.0 carbon atoms; M is a cation or a mixture of cations that has a valence q; a and b are integers selected such that said branched alkylbenzene sulphonates are electroneutral; R1 is C1-C3 alkyl; R2 is selected from H and C1-C3 alkyl; A is a benzene portion; and (b) from 5% to about 40% by weight of a mixture of unbranched alkylbenzene sulphonates having the formula (II): (II) in which a, b, M, A and q are as defined above and Y is an unsubstituted linear aliphatic portion consisting of carbon and hydrogen having two methyl terms, and wherein said Y has a sum of atoms of 10 carbon from 9 to 15, preferably from 10 to 14, and said Y has an average aliphatic carbon content of 10.0 to 14.0; and wherein said mixture of modified alkyl benzene sulfonate surfactants is further characterized by a 2/3-phenyl index of 275 to 10,000. 2.- A mixture of alkylbenzenesulfonate surfactants 15 modified according to claim 1, further characterized in that M is selected from H, Na and K and mixtures thereof; a = 1; b = 1; q = 1; and said mixture of modified alkylbenzenesulfonate surfactants has a 2-methyl-2-phenyl index of less than 0.3. 3.- A mixture of surfactants of Modified alkylbenzenesulfonate according to any of claims 1 to 2 further characterized in that said 2-methyl-2-phenyl index is from 0 to 0.1. 4. A mixture of surfactants of modified alkylbenzene sulfonate according to any of claims 1 to 3 further characterized in that it is the product of a process using as catalyst a zeolite selected from mordenite, ofretite and H-ZSM-12 in at least partially acidic form. 5. A mixture of modified alkyl benzene sulfonate surfactants according to any of claims 1 to 4 further characterized in that said catalyst is an acid mordenite. 6. A detergent composition comprising: a) from 0.1% to 95% by weight of mixture of alkylbenzene sulfonate surfactants modified according to any of claims 1 to 5; b) from 0.00001% to 99.9% by weight of conventional cleaning aids other than surfactants; and c) from 0% to 50% by weight, of surfactant different from that of the mixture of modified alkylbenzene sulphonate surfactants; with the proviso that when said detergent composition comprises any other alkylbenzene sulfonate other than the alkylbenzene sulfonate of the mixture of modified alkyl benzene sulphonate surfactants, said mixture of modified alkyl benzene sulphonate surfactants and the other alkylbenzene sulfonate, as a mixture, have a 2/3-phenyl index total of 275 to 10,000. 7. A detergent composition consisting essentially of: a) from 1% to 50% by weight of mixture of alkylbenzene sulfonate surfactants modified in accordance with any of the ^ g ^ Ü claims 1 to 5; b) from 0.00001% to 99.9% by weight of conventional cleaning aids other than surfactants; and c) from 0.1% to 50% by weight, of surfactants other than alkylbenzene sulfonates; and d) from 0.1% to 95% water. 8. A detergent composition consisting essentially of: a) from 0.1% to 95% by weight of mixture of modified alkylbenzenesulfonate surfactants according to any of claims 1 to 5; and b) from 0.00001% to 99.9% by weight of conventional cleaning aids other than surfactants. 9. A medium phenyl 2/3-phenyl surfactant mixture consisting essentially of: a) from 1% to 60% by weight of a first alkylbenzenesulfonate surfactant, wherein said first alkyl benzene sulfonate surfactant is a mixture of alkylbenzenesulfonate surfactants according to any of claims 1 to 5; and b) from 40% to 99% by weight of a second alkylbenzene sulfonate surfactant, wherein said second alkylbenzene sulfonate surfactant is a mixture of alkylbenzene sulfonate surfactants other than the mixture of modified alkyl benzene sulphonate surfactants in accordance with any of claims 1 to 5; and wherein said second alkylbenzenesulfonate surfactant has a 2/3-phenyl index of 75 to 160; with the proviso that said mixture of 2/3-phenyl surfactant has a 2/3-phenyl index of 160 to 275. 10. - A detergent composition comprising: a) from 0.1% to 95% by weight of 2/3-phenyl medium surfactant mixture according to claim 9; b) from 0.00001% to 99.9% by weight of conventional cleaning aids other than surfactants; and c) from 0% to 50% by weight of a surfactant other than the mixture of 2/3-phenyl middle surfactants; with the proviso that when said detergent composition comprises any other alkylbenzenesulfonate other than the alkylbenzenesulfonate of the mixture of 2/3-phenyl middle surfactants, said mixture of 2/3-phenyl middle surfactants and the other alkylbenzene sulfonate, as a mixture, they have a total 2/3-phenyl number of 160 to 275. 11. A detergent composition consisting essentially of: a) from 1% to 50% by weight of 2/3-phenyl middle surfactant mixture in accordance with claim 9; b) from 0.1% to 98.8% by weight of conventional cleaning aids other than surfactants; c) from 0.1% to 50% by weight of surfactants other than alkylbenzene sulphonates; and d) from 0.1% to 98.8% by weight, water. 12. A detergent composition consisting essentially of: a) from 0.1% to 95% by weight of a 2/3-phenyl medium surfactant mixture according to claim 9; and b) from 0.00001% to 99. 9% by weight of conventional cleaning aids other than surfactants. 13. A process for preparing a medium phenyl 2/3-phenyl surfactant mixture according to claim 9 comprising a step selected from: i) combining said first alkylbenzenesulfonate surfactant and the second alkylbenzene sulfonate surfactant; and ii) combining the non-sulfonated precursor of the first alkylbenzenesulfonate surfactant and the non-sulfonated precursor of the second alkylbenzenesulfonate surfactant and sulfonating said combination. 14. A detergent composition comprising: a) from 1% to 50% by weight of the product according to claim 13; and b) from 0.00001% to 99.9% by weight of conventional cleaning aids other than surfactants. 15. A mixture of surfactants according to any of claims 1 to 5 further characterized in that said mixture of modified alkylbenzene sulfonate surfactants is prepared by a process comprising a step that is selected from: i) combining a mixture of agents linear and branched alkylbenzene sulphonate surfactants having a 2/3-phenyl index of from 500 to 700 with a mixture of alkylbenzenesulfonate surfactants having a 2/3-phenyl index of from 75 to 160 and ii) combining a mixture of linear alkylbenzenes and branched having a 2/3-phenyl index of from 500 to 700 with a mixture of alkylbenzenes having a 2/3-phenyl index of from 75 to 160 and sulfonating said combination. 16.- A detergent composition in accordance with any FIG. 6-8, 10-12 and 14 further characterized in that said conventional cleaning aid other than surfactants is selected from the group consisting of builder, detersive enzymes, bleaching systems, brighteners, polymers at least partially soluble or dispersible in water, abrasives, bactericides, oxidation inhibitors, dyes, solvents, hydrotropes, perfumes, thickeners, antioxidants, processing aids, foam enhancers, suds suppressors, pH regulators, anti fungal agents, control agents mold, insect repellents, anti-corrosion aids, chelators, and mixtures thereof. 17. A detergent composition according to any of claims 6-8, 10-12 and 14 and 16, further characterized in that said cleaning composition is in the form of a liquid, powder, agglomerate, paste, tablet, bar, gel or granule. 18. A method comprising treating a fabric with the detergent composition according to any of claims 6-8, 10-12, 14, 16 and 17. 19. A mixture of alkylbenzene sulfonate surfactants modified in accordance with any of claims 1 to 5 consisting essentially of said mixture of branched alkylbenzene sulphonates and unbranched alkylbenzene sulphonates, in which the 2-methyl-2-phenyl index of the mixture of modified alkyl benzene sulphonate surfactants is less than 0.1, and in the which in said mixture of branched and unbranched alkylbenzenesulfonates, the average aliphatic carbon content is from 11.5 to 12.5 carbon atoms; R1 is methyl; R2 is selected from H and methyl with the proviso that in at least 0.7 mole fraction of said branched alkylbenzene sulphonates R2 is H; and in which the sum of carbon atoms in R1, L and R2 is from 10 to 14; and further wherein, in said mixture of unbranched alkylbenzene sulphonates, said Y has a sum of carbon atoms of 10 to 14 carbon atoms, the average aliphatic carbon content of the unbranched alkylbenzene sulphonates is 11.5 to 12.5 carbon atoms, and M is a monovalent cation or mixture of cations selected from H, Na and mixtures thereof. 20. A mixture of modified alkylbenzene sulfonate surfactants comprising the product of a process comprising the steps of: (I) alkylating benzene with an alkylation mixture; (II) sulfonate the product of (I); and (III) neutralizing the product of (II); wherein said alkylation mixture comprises: (a) from 1% to 99.9%, by weight of branched C9-C20 monoolefins, said branched monoolefins have structures identical to those of the branched monoolefins formed by the dehydrogenation of branched paraffins of the formula R1LR2 in which L is an aliphatic acyclic portion consisting of carbon and hydrogen and containing two terminal methyls; R1 is C1 to C3 alkyl; and R2 is selected from H and C1 to C3 alkyl; and (b) from 0.1% to 85%, by weight of linear C9-C20 aliphatic olefins; wherein said alkylation mixture contains said branched C9-C20 monoolefins having at least two different carbon numbers on said C9-C20 scale, and has an average carbon content of 9.0 to 15.0 carbon atoms; and wherein said components (a) and (b) are in a weight ratio of at least about 15:85. 21. A mixture of modified alkylbenzenesulfonate surfactants consisting essentially of the product of a process comprising the steps, in sequence, of: (I) alkylating benzene with an alkylation mixture; (II) sulfonate the product of (I); and (III) neutralizing the product of (II); wherein said alkylation mixture comprises: (a) from 1% to 99.9%, by weight of a branched alkylating agent selected from: (i) internal monoolefins of C9-C20 R1LR2 in which L is an acyclic olefinic moiety consisting of carbon and hydrogen and containing two terminal methyls; (I) C9-C20 alpha monoolefins R1AR2 in which A is an alpha-olefinic acyclic moiety consisting of carbon and hydrogen and containing a terminal methyl and a terminal olefinic methylene; (iii) vinylidene monoolefins of C9-C20 R BR2 in which B is an acyclic vinylidene olefin moiety consisting of carbon and hydrogen and containing two terminal methyl and an internal olefinic methylene; (iv) C9-C20 primary alcohols R1QR2 wherein Q is an acyclic aliphatic primate terminal alcohol moiety consisting of carbon, hydrogen and oxygen and containing a terminal methyl; (v) primary alcohols of C9-C20 R1ZR2 in which Z is a non-terminal aliphatic acyclic primary alcohol moiety consisting of carbon, hydrogen and oxygen and containing two terminal methyls; and (vi) mixtures thereof; wherein in any of (?) - (vi) R1 is C1 to C3 alkyl; and R2 is selected from H and C1 to C3 alkyl; and (b) from 0.1% to 85%, by weight of a linear C9-C20 alkylating agent selected from linear aliphatic olefins of C9-C20 linear C9-C20 aliphatic alcohols and mixtures thereof; wherein said alkylation mixture contains the branched alkylating agents having at least two different carbon numbers on said C9-C20 scale, and has an average carbon content of 9.0 to 15.0 carbon atoms; and wherein said components (a) and (b) are in a weight ratio of at least 15:85. 22. A mixture of modified alkylbenzene sulfonate surfactants according to claim 20 further characterized in that said alkylation mixture consists essentially of: (a) from 0.5% to 47.5%, by weight of said branched alkylating agent selected from: i) internal monoolefins of C9-C20 R1LR2 in which L is an acyclic olefinic moiety consisting of carbon and hydrogen and containing two terminal methyls; (ii) C9-C20 alpha monoolefins R1AR2 in which A is an alpha-olefinic acyclic moiety consisting of carbon and hydrogen and which confers a terminal methyl and a terminal olefinic methylene; (iii) mixtures thereof; wherein in any of (i) - (iii) R1 is methyl, and R2 is H or methyl with the proviso that in at least 0.7 mole fraction of the total of said monoolefins, R2 is H; and (b) from 0.1% to 25%, by weight of linear C9-C14 aliphatic olefins; and c) from 50% to 98.9% by weight of carrier materials selected from paraffins and inert non-paraffin solvents; wherein said alkylation mixture contains the branched alkylating agents having at least two different carbon numbers on said C9-C20 scale, and has an average carbon content of 11.5 to 12.5 carbon atoms; and wherein said components (a) and (b) are in a weight ratio of 51:49 to 90:10. 23. A mixture of modified alkyl benzene sulfonate surfactants according to any of claims 20 to 22 further characterized in that in step (I), the alkylation is carried out in the presence of an alkylation catalyst, said alkylation catalyst is a solid porous alkylation catalyst of intermediate acidity, and step (II) comprises the removal of components other than monoalkylbenzene before contacting the product of step (I) with the sulfonation agent. 24. A mixture of modified alkyl benzene sulfonate surfactants according to any of claims 20 to 23 further characterized in that said alkylation catalyst is other than a member selected from the group consisting of HF, AICI3, sulfuric acid, and mixtures thereof. the same. 25. A mixture of modified alkyl benzene sulfonate surfactants according to any of claims 20 to 24 further characterized in that a hydrotrope, a hydrotrope precursor, or mixtures thereof are added after step (- 26.- A mixture of modified alkylbenzene sulfonate surfactants according to any of claims 20 to 25 further characterized in that a hydrotrope, a hydrotrope precursor, or mixtures thereof is added during or after step (II) and before step (III). A mixture of modified alkyl benzene sulfonate surfactants according to any of claims 20 to 26 further characterized in that a hydrotrope is added during or after step (III). 28.- A mixture of alkylbenzene sulfonate surfactants modified in accordance with any of claims 20 to 27 further characterized in that said alkylation catalyst The ion is selected from the group consisting of non-fluorinated acid mordenite type catalysts, fluorinated acid mordenite type catalyst and mixtures thereof. 29. A mixture of modified alkylbenzenesulfonate surfactants according to any of claims 20 to 28 further characterized in that in said step (I) the alkylation is carried out at a temperature of 125 ° C to 250 ° C and at a pressure of3. 51 kg / cm2 gravimetric at 70.30 kg / cm2 gravimetric. 30. A mixture of modified alkyl benzene sulfonate surfactants according to any of claims 20 to 29 further characterized in that in said step (I) the alkylation is carried out at a temperature of 175 ° C to 215 ° C and at a pressure of 70.30. kg / cm2 gravimetric at 17.57 kg / cm2 gravimetric and a time of 0.01 hours to 18 hours. 31. A mixture of modified alkylbenzene sulfonate surfactants according to any of claims 20 to 30, further characterized in that said step (III) is carried out using a basic salt, said salt having a cation selected from the group consisting of metalalkalono, alkaline earth metal, ammonium, substituted ammonium, and mixtures thereof and an anion selected from hydroxide, oxide, carbonate, silicate, phosphate and mixtures thereof. 32. A mixture of modified alkylbenzene sulfonate surfactants according to any of claims 20 to 31 further characterized in that said basic salt is selected from the group consisting of sodium hydroxide, sodium silicate, potassium hydroxide, potassium silicate, hydroxide of magnesium, ammonium hydroxide and mixtures thereof. 33. A mixture of modified alkylbenzene sulfonate surfactants according to any of claims 20 to 32 further characterized in that said step (II) is carried out using a sulfonating agent selected from the group consisting of sulfur trioxide, trioxide mixtures of sulfur / air, and sulfuric acid. 34. - A detergent composition comprising: a) from 0.1% to 95% by weight of mixture of modified alkylbenzene sulfonate surfactants according to any of claims 20 to 33; and b) from 0.00001% to 99.9% by weight of conventional cleaning aids. 35.- A detergent composition according to claim 34 further characterized in that said auxiliary agent for conventional cleaning is selected from the group consisting of builder, detersive enzymes, bleaching systems, surfactants other than the product of step (III), brighteners, polymers at least partially soluble or dispersible in water, polysaccharides, abrasives, bactericides, oxidation inhibitors, dyes, solvents, hydrotropes, perfumes, thickeners, antioxidants, processing aids, foam enhancers, foam suppressors, pH regulators, agents anti fungal or mold control, insect repellents, anti-corrosion aids, chelators, and mixtures thereof. 36. A detergent composition according to any of claims 34 to 35, further characterized in that said detergent composition is in the form of a liquid, powder, agglomerate, paste, tablet, bar, gel or granule. 37.- A method comprising treating a fabric with a detergent composition according to any of claims 34 to 36. 38.- A modified alkylbenzene mixture comprising: ? n the 60% to 95% by weight of a mixture of branched alkylbenzenes that have the formula (I): * R2 < ') in which L is an aliphatic acyclic portion consisting of carbon and hydrogen and has two methyl terms, and wherein said mixture of branched alkylbenzenes contains two or more compounds of said formula (I) which differ in molecular weight and in which said mixture of branched alkylbenzenes is characterized by - a sum of carbon atoms in R1, R2 and L of 9 to 15, preferably 10 to 14; and - an average aliphatic carbon content based on the sum of R1, L and R2 of 10.0 to 14.0 carbon atoms; and further, in which L has no substituents other than A, R1 and R2; R1 is C1-C3 alkyl; R2 is selected from H and C1-C3 alkyl; A is a benzene portion; and (b) from 5% to about 40% by weight of a mixture of unbranched alkylbenzenes having the formula (II): Y I A (ll) wherein A is a benzene portion and Y is an unsubstituted linear aliphatic portion consisting of carbon and hydrogen having two methyl terms, and wherein said Y has from 9 to 15 carbon atoms in total and said alkylbenzene mixture unbranched has an aliphatic carbon content of 10.0 to 14.0 carbon atoms; and wherein said mixture of modified alkylbenzenes is further characterized by a 2/3-phenyl index of 275 to 10,000, and a 2-methyl-2-phenyl index of less than 0.3. 39. A modified alkylbenzene mixture comprising: (i) from 20% to 99% by weight of a first alkylbenzene mixture, wherein said first alkylbenzene mixture consists essentially of: a) from 60% to 95% by weight weight of a mixture of branched alkylbenzenes having the formula (I): XLX I 10 A (in which L is an aliphatic acyclic portion consisting of carbon and hydrogen and having two methyl terms, and wherein said mixture of branched alkylbenzenes contains two or more compounds of said formula 15 (I) which differ in molecular weight and in which said mixture of branched alkylbenzenes is characterized by - a sum of carbon atoms in R1, R2 and L of 9 to 15; and - an average aliphatic carbon content based on the sum of R1, L and R2 of 10.0 to 14.0 carbon atoms; and further, in which L has no substituents other than A, R1 and R2; R1 is C1-C3 alkyl; R2 is 20 selects from H and C1-C3 alkyl; A is a benzene portion; and (b) from 5% to about 40% by weight of a mixture of unbranched alkylbenzenes having the formula (II): e feí ÉÉ? É &J Y 1 A (ll) wherein A is a benzene portion and Y is an unsubstituted linear aliphatic portion consisting of carbon and hydrogen having two methyl terms, and wherein said Y has from 9 to 15 carbon atoms in total and said alkylbenzene mixture unbranched has an aliphatic carbon content of 10.0 to 14.0 carbon atoms; and wherein said first alkylbenzene mixture has a 2/3-phenyl index of 275 to 10,000; and ii) the remainder, not more than 80% by weight, of a second mixture of alkylbenzenes, wherein said second alkylbenzene mixture has a 2/3-phenyl index of 75 to 160; and wherein said mixture of modified alkylbenzenes has a total 2/3-phenyl number of from 165 to 10,000. 40.- A detergent composition comprising: a) from 1% to 50% by weight of modified alkylbenzene sulfonate surfactant mixture according to any of claims 1 to 5, wherein said mixture of modified alkylbenzene sulfonate surfactants has a 2-methyl-2-phenyl index of less than 0.3; b) from 0.000001% to 10% by weight of a member selected from the group consisting of optical brighteners, dyes, photobleaches, hydrotropic bleach activators, and transition metal bleach catalysts: c) from 0.1 to 40% by weight of surfactants that are selected from the group consisting of cationic surfactants, ^^ g l ^ gi nonionic surfactants, anionic surfactants, and amine oxide surfactants; and d) from 10% to 99% by weight of conventional cleaning aids; with the proviso that when said detergent composition comprises any other alkylbenzenesulfonate surfactant agent different from the mixture of modified alkyl benzene sulphonate surfactants, said detergent composition is further characterized by a total 2/3-phenyl number of at least 200, in which said 2/3-total phenyl index is determined by measuring the 2/3-phenyl index, as defined herein, in a combination of said mixture of modified alkyl benzene sulphonate surfactants and any other alkylbenzenesulfonate that will be added to the detergent composition, said combination, for measurement purposes, is prepared from aliquots of the mixture of modified alkyl benzene sulfonate surfactants and the other alkylbenzene sulfonate which has not yet been exposed to any other component of the detergent composition; and with the additional proviso that when said detergent composition comprises any alkylbenzene sulfonate surfactant other than the mixture of modified alkyl benzene sulphonate surfactants, said detergent composition is further characterized by a total 2-methyl-2-phenyl index of less than 0.3, wherein said 2-methyl-2-phenyl total number is determined by measuring the 2-methyl-2-phenyl index, as defined herein, in a combination of said mixture of modified alkyl benzenesulfonate surfactants and any other alkylbenzene sulfonate which will be added to the detergent composition, said combination, for measurement purposes, is prepared from aliquots of the mixture of modified alkylbenzenesulfonate surfactants and the other alkylbenzenesulfonate which has not yet been exposed to any other component of the detergent composition . 41. A detergent composition according to claim 40, further characterized in that the cationic surfactant is selected from C8-C16 alkylammonium salts, linear and branched, substituted and unsubstituted. 42. A detergent composition according to claim 40, further characterized in that it is substantially free of alkylbenzene sulfonate surfactants other than the mixture of modified alkyl benzene sulphonate surfactants. 43. A detergent composition according to claim 40, further characterized in that it comprises, in said component c), at least 0.1% by weight, of a linear C10-C24 linear alkylbenzenesulfonate surfactant. 44. A detergent composition according to claim 40, further characterized in that it comprises, in said component c), at least 0.1% by weight, of a commercially highly branched alkylbenzene sulfonate surfactant. 45. A detergent composition according to claim 40, further characterized in that it comprises, in said component c), a nonionic surfactant at a level of 0.5% to 25% by weight of said detergent composition, and wherein said nonionic surfactant is a polyalkoxylated alcohol in blocked or unblocked form having: a hydrophobic group selected from C10-C16 linear alkyl, C10-C16 alkyl branched in the middle part of its C1-C3 chain, C10 alkyl C16 branched from guerbet, and mixtures thereof and a hydrophilic group selected from 1-15 ethoxylated, 1-15 propoxylated, 1-15 butoxylated and mixtures thereof, in blocked or unblocked form. 46. A detergent composition according to claim 40, further characterized in that it comprises, in said component c), an alkyl sulfate surfactant at a level of 0.5% to 25% by weight of said detergent composition, and wherein said alkylsulfate surfactant has a hydrophobic group selected from C10-C16 linear alkyl, C10-C16 alkyl branched in the middle part of its C1-C3 chain, branched C10-C16 alkyl from guerbet, and mixtures thereof and a cation selected from Na, K and mixtures thereof. 47. A detergent composition according to claim 40, further characterized in that it comprises, in said component c), an alkyl (polyalkoxy) sulfate surfactant at a level of 0.5% to 25% by weight of said detergent composition, and wherein said alkyl (polyalkoxy) sulfate surfactant has a hydrophobic group selected from linear C10-C16 alkyl, C10-C16 alkyl branched in the middle part of its C1-C3 chain, branched C10-C16 alkyl guerbet, and mixtures thereof and a hydrophilic (polyalkoxy) sulfate group selected from 1-15 polyethoxysulfate, 1-15 polypropoxysulfate, 1-15 polybutoxysulfate, 1-15 poly (ethoxy / propoxy / butoxy) sulfates mixed, and mixtures of the same, in blocked or unblocked form; and a selected cation of Na, K and mixtures thereof. 48. A detergent composition according to any of claims 40 to 47 that has the form of a heavy-duty liquid detergent. 49.- A detergent composition according to any of claims 40 to 47 that has the form of a synthetic laundry detergent bar. 50.- A detergent composition according to any of claims 40 to 47 that has the form of a heavy duty granule. 51. A detergent composition according to any of claims 40 to 47 and 50 which has the form of a heavy-duty granule and in which said conventional cleaning aid (d) comprises from 10% to 50% by weight of said detergent composition of a non-phosphate builder. 52. A detergent composition according to any of claims 40 to 47 and 50 having the form of a heavy-duty granule and wherein said conventional cleaning aid (d) comprises from 10% to 50% by weight of said detergent composition of a phosphate builder. 53. A detergent composition according to any of claims 40 to 47 and 50 having the form of a heavy-duty granule and wherein said conventional cleaning aid (d) comprises as said phosphate builder a member which is selected from the group consisting of sodium tripolyphosphate.