MXPA01007351A - Aqueous heavy duty liquid detergent compositions comprising modified alkylbenzene sulfonates - Google Patents

Abstract

The present invention relates to aqueous based heavy-duty liquid detergent compositions containing a modified alkylbenzene sulfonate surfactant (MABS), as co-surfactant (alkyl polyhydroxy fatty acid amide and/or alkyl amidopropyl dimethyl amine) and an aqueous liquid carrier. The MABS comprises a mixture of specific branched and non-branched alkylbenzene sulfonate compounds, which are further characterised by a 2/3-phenyl index of 160-275.

Description

COMPOSITIONS DETERGENTS LIQUID AQUEOUS FOR HEAVY WORKING COMPRISING ALKYLBENCENSULPHONATES MODIFIED FIELD OF THE INVENTION The present invention relates to liquid heavy duty laundry detergent products which are aqueous in nature and which include particular types of improved alkylbenzene sulfonate surfactant mixtures adapted for use by controlling the composition parameters, especially a 2/3 index -phenyl and a 2-methyl-2-phenyl index.

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 linear alkylbenzene sulfonate surfactant manufacturing technique is directed towards this goal. All the relevant large-scale commercial procedures of alkylbenzenesulfonates 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 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 way to take to fix the unresolved problems of linear LAS, but also a range of misconceptions, 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 sulphonate surfactants, which are currently marketed, are relatively simple compositions to be defined and analyzed, the linear and branched alkylbenzene sulfonate surfactant compositions are complex. In general such compositions can be very varied, containing one or more different types of branching at any of a number of positions on the aliphatic chain. 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 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 a substantial unmet need for further improvements in mixtures of alkylbenzenesulfonate surfactants, especially with respect to those that 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. ,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. 5,196,624; USES. ,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. 5,510,306; WO 95/1761, 7/6/95; WO 95/18084; USES. 5,510,306; USES. 5,087,788; USES. 4,301, 316; USES. 4,301, 317; USES. 4,855,527; USES. 4,870,038; USES. 5,026,933; USES. ,625,105 and U.S.A. 4,973,788. Consult Vol. 56 in the series "Surfactant Science ", Marcel Dekker, New York, 1996, including in particular the chapter 2 entitled "Alkylarylsulfonates: History, Manufacture, Analysis and Environmental Properties", pages 39-108, "Surfactant Science" series, vol. 73, Marcel Dekker, New York, 1998, and in the series "Surfactant Science", vol. 40, Marcel Dekker, New York, 1992. Also consult the co-pending patent applications of E.U.A. No. 60 / 053,319, attorney's file No. 6766P, filed on the 21st July 1997, No. 60 / 053,318, attorney's file No. 6767P, filed July 21, 1997, No. 60 / 053,321, attorney's file No. 6768P, filed 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 July 21, 1997, No. 60 / 053,186, attorney's file No. 6771 P, filed on July 21, 1997, and the technique referred to in them. The documents referred to herein are incorporated in their entirety.

BRIEF DESCRIPTION OF THE INVENTION The present invention provides heavy-duty aqueous liquid detergent compositions comprising mixtures of modified alkylbenzene sulfonate surfactants. Specifically, the present invention comprises a heavy-duty aqueous liquid detergent composition. Heavy-duty water-based laundry liquid laundry detergent compositions comprise surfactants selected from nonionic detersive surfactant, anionic detersive surfactant, zwitterionic detersive surfactant, amine oxide detersive surfactant, and mixtures thereof. Specifically, the first embodiment of the present invention comprises a laundry detergent composition for work Weighing water-based composition comprising: (i) from 5% to 70% by weight of the composition, of a mixture of modified alkybenzenesulfonate surfactants comprising: (a) from 15% to 99% by weight of surfactant mixture , of a mixture of branched alkylbenzene sulphonates having the formula (I): (Wherein 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 than said branched alkylbenzene sulphonates differing in molecular weight of the anion of said formula (I) and in which said mixture of branched alkylbenzene sulphonates has: - A sum of carbon atoms in R1, L and R2 of 9 to 15; of average aliphatic carbon of about 10.0 to about 14.0 carbon atoms, M is a cation or mixture of cations having a valence q, a and b are selected integers such that said branched alkylbenzenesulfonates are electroneutral; is C alquilo-C3 alkyl; R 2 is selected from H and C C 3 alkyl; A is a benzene portion; and (b) from 1% to about 85% by weight of surfactant mixture, 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 has an average aliphatic carbon content of about 10.0 to about 14.0; and wherein said mixture of modified alkyl benzene sulfonate surfactants is further characterized by a 2/3-phenyl index of 160 to 275; (ii) From about 0.1 to about 8% of a co-surfactant composition selected from the group consisting of alkyl polyhydroxy fatty acid amide, alkylamidopropyl dimethylamine and mixtures thereof; and (iii) From about 30% to about 95% of an aqueous liquid carrier; wherein said composition is further characterized by a 2/3-phenyl index of from 160 to about 275. Specifically, the second embodiment of the present invention comprises a heavy-duty aqueous-based laundry detergent composition comprising: (i) a mixture of modified alkylbenzene sulphonate surfactants comprising the product of a process comprising the steps of: (!) alkylating benzene with an alkylation mixture in the presence of a beta zeolite catalyst: (II) sulfonate the product of (I); and (III) neutralizing the product of (II); wherein said alkylation mixture comprises: (a) from 1% to about 99.9%, by weight of the alkylation mixture of branched C9-C20 monoolefins having structures identical to those of the branched monoolefins formed by the dehydrogenation of paraffins Branches of formula RT R2 in which L is an aliphatic acyclic portion consisting of carbon and hydrogen and containing two terminal methyls; R 1 is C 1 to C 3 alkyl; and R2 is selected from H and alkyl from Ci to C3; and (b) from 0.1% to about 85%, by weight of the alkylation mixture of linear aliphatic olefins of Cg-C2o; wherein said alkylation mixture contains said branched C9-C2o monoolefins having at least two different carbon numbers on said Cg-C2o scale, and having an average carbon content of 9.0 to about 15.0 carbon atoms; and wherein said components (a) and (b) are in a weight ratio of at least about 15:85; (ii) From about 0.1 to about 8% of a co-surfactant composition selected from the group consisting of alkyl polyhydroxy fatty acid amide, alkylamidopropyl dimethylamine and mixtures thereof; and (iii) From about 30% to about 95% of an aqueous liquid carrier; wherein said composition is further characterized by a 2/3-phenyl index of from 160 to about 275. Specifically, the third embodiment of the present invention comprises a heavy duty aqueous-based laundry detergent composition comprising: (i) a mixture of modified alkylbenzene sulfonate surfactants consisting essentially of the product of a process comprising the steps, in sequence, of: (I) alkylating benzene with an alkylation mixture in the presence of a zeolite beta catalyst: (II) sulphonate the product of (I); and (III) neutralizing the product of (II); wherein said alkylation mixture comprises: (a) from 1% to about 99.9%, by weight of the alkylation mixture of a branched alkylating agent selected from the group consisting of: (A) internal monoolefins of Cg-C2o of R1LR2 wherein L is an olefinic acyclic portion consisting of carbon and hydrogen and containing two terminal methyls; (B) alpha C9-C2o monoolefins of R1AR2 in which A is an alpha-olefinic acyclic moiety consisting of carbon and hydrogen and containing a methyl terminal and an olefinic methylene terminus; (C) C9-C2o vinylidene monoolefins of R1BR2 in which B is an acyclic vinylidene olefin moiety consisting of carbon and hydrogen and containing two methyl terminals and an internal olefinic methylene; (D) C9-C2o primary alcohols of R1QR2 in which Q is an aliphatic acyclic terminal alcohol moiety consisting of carbon, hydrogen and oxygen and contains a methyl terminal; (E) primary C9-C2o alcohols of R1ZR2 in which Z is a non-terminal primary aliphatic acyclic alcohol moiety consisting of carbon, hydrogen and oxygen and contains two methyl terminals; and (F) mixtures thereof; wherein in any of (A) - (F) said R1 is Ci to C3 alkyl and R2 is selected from H and Ci to C3 alkyl; and (b) from 0.1% to about 85%, by weight of the mixture of alkylation of a C9-C20 linear alkylating agent selected from linear aliphatic olefins of C9-C20, linear aliphatic alcohols of C9-C2o 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 about 15.0 carbon atoms; and wherein said components (a) and (b) are in a weight ratio of at least about 15:85; (ii) From about 0.1 to about 8% of a co-surfactant composition selected from the group consisting of alkyl polyhydroxy fatty acid amide, alkylamidopropyl dimethylamine and mixtures thereof; and (iii) From about 30% to about 95% of an aqueous liquid carrier; wherein said composition is further characterized by an index 2/3-phenyl from 160 to about 275. Specifically, the fourth embodiment of the present invention comprises a heavy-duty aqueous-based laundry detergent composition comprising: (i) from 5% to about 70% by weight of the composition of a mixture of modified alkyl benzene sulfonate surfactants comprising: (a) from 15% to 99% by weight of surfactant mixture, a mixture of branched alkylbenzene sulphonates having the formula (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, R and R2; and wherein said mixture of branched alkylbenzene sulphonates contains two or 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; - An average aliphatic carbon content of about 10.0 to about 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 C3 alkyl; R2 is selected from H and CrC3 alkyl; A is a benzene portion; and (b) from 1% to about 85% by weight of surfactant mixture, of a mixture of unbranched alkylbenzene sulphonates which they have the formula (II): (ll) 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 has an average aliphatic carbon content of about 10.0 to about 14.0; and wherein said mixture of modified alkylbenzene sulfonate surfactants is further characterized by a 2/3-phenyl index of 160 to 275 and wherein said mixture of modified alkyl benzene sulphonate surfactants has a 2-methyl-2-phenyl acid less than about 0.3; (ii) From about 0.1 to about 8% of a co-surfactant composition selected from the group consisting of alkyl polyhydroxy fatty acid amide, alkylamidopropyl dimethylamine and mixtures thereof; (Ii) from about 0.00001% to about 99.9% of the composition of a surfactant selected from the group consisting of anionic surfactants other than those of (i), nonionic surfactants, zwitterionic surfactants, agents cationic surfactants, amphoteric surfactants and mixtures thereof; and (iv) From about 30% to about 95% of an aqueous liquid carrier; with the proviso that when said detergent composition comprises any alkylbenzene sulfonate surfactant other than said mixture of modified alkyl benzene sulfonate surfactants, said detergent composition is further characterized by a total 2/3-phenyl index of at least about 160, 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 alkyl benzene sulfonate surfactants and any other alkylbenzene sulfonate that will be added to said detergent composition, said combination, for measurement purposes, is prepared from aliquots of the mixture of modified alkybenzenesulfonate surfactants and the another alkylbenzene sulfonate that 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 about 0.3. , wherein said 2-methyio-2-phenyl total index will be determined by measuring the 2-methyl-2-phenyl index, as defined herein, in a combination of said agent mixture.

Modified alkyiibenzenesulfonate surfactants and any other alkylbenzenesulfonate that will be added to said detergent composition, said combination, for measurement purposes, 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. Detergent compositions as defined herein will also comprise from 1% to 80% by weight of the composition of additional detergent ingredients such as builders, enzymes, dyes, bleaching agents, bleach activators, color spots, builders. organic, inorganic alkalinity sources and mixtures thereof. The abovementioned embodiments and other aspects of the present invention are described and illustrated more fully 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 The aqueous liquid detergent compositions of this invention comprise a mixture of modified alkyl benzene sulfonate surfactants. The essential and optional components of the mixture of modified alkyl benzene sulfonate surfactants and other optional materials of the aqueous liquid detergent compositions herein, as well as the form, preparation and use of the composition, are described in greater detail as follows: (All concentrations and relationships are on a weight basis unless otherwise specified). The invention, on the other hand, is not designed to encompass any of the completely conventional liquid detergent compositions, such as those based exclusively on linear alkylbenzene sulphonates made by any process, or exclusively on unacceptably branched alkylbenzene sulphonates, such as ABS or TPBS. It is preferred that when the detergent compositions comprise 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 commercial, especially linear alkylbenzene sulphonate surfactants, typically C10 linear -C1), 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 less about 350, still 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 surfactant mixture. of modified alkylbenzenesulfonate and any other alkylbenzenesulfonate to be added to the composition, said combination, for measurement purposes, 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 another component of the composition; and with the additional proviso that when said composition comprises any alkylbenzene sulfonate surfactant other than the mixture of modified alkyl benzene sulphonate surfactants (for example, as a result of combining in the composition one or more commercial, especially linear, alkylbenzene sulphonate surfactants, typically Cio-Cu linear), said 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 alkylbenzene sulfonate surfactants and any other alkylbenzene sulfonate to be added to said composition, said combination, for measurement purposes, is prepared from aliquots of the surfactant mixture of alkylbenzene sulfonate modified 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, encompassing a number of economical but less preferred methods in terms of overall cleaning performance, such as combining modified alkyl benzene sulfonate surfactants. with conventional linear alkylbenzenesulfonate surfactants either during synthesis or during formulation of the composition. In addition, as hand dishwashing analysis practitioners are well aware, a number of hand dishwashing aids (paramagnetic materials and sometimes even water) are capable of interfering with the methods for determining the parameters of agent mixtures. alkylbenzenesulfonate surfactant as described below. Hence, whenever possible, the analysis on dry materials should be carried out before mixing them in the compositions. In a preferred embodiment the mixture of modified alkylbenzenesulfonate surfactants in the hand dishwashing composition according to the composition according to the first embodiment is prepared by a process comprising a step which is selected from: Combining a mixture of branched and linear 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 from 75 to about 160 (typically this alkylbenzenesulfonate surfactant is a linear C 0-Cu linear alkylbenzenesulfonate surfactant, for example, LAS of process DETAL® or LAS of procedure HF although in general any commercial type linear (LAS) or branched (ABS, TPBS)) can be used; and combining a mixture of branched and linear alkylbenzenes 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. Moreover, the invention encompasses the addition of useful hydrotrope precursors and / or hydrotropes, such as Ci-Cs alkylbenzenes, more typically toluenes, eumens, xlenes, naphthalenes, or the sulfonated derivatives of any such 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. Likewise, it will be understood that said materials, if and when they interfere with the analytical methods, will not be included in samples of compositions that are used for analytical purposes. A mixture of preferred modified alkyl benzene sulfonate surfactants has M selected from H, Na, K and mixtures thereof, said a = 1, said b = 1, said q = 1, and said mixture of agents Modified alkylbenzene sulfonate surfactants have 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. In relation to the composition there are the methods of their use, such as a method of contacting dirty table linen in need of cleaning with a solution either pure or aqueous of the composition of the invention. Such methods may optionally include the step of diluting the composition with water. Additionally, the composition can be applied, either pure or as an aqueous solution, directly to the tablecloth or surface to be cleaned or directly to a cleaning implement, such as a sponge or washing cloth. Said methods are part of the present invention. Said mixture of alkylbenzene sulfonate surfactants modified accordingly can be manufactured as the product of a process using as catalyst a zeolite selected from mordenite., offerita 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 alkyl benzene sulfonate surfactants according to the first embodiment of the invention consists essentially of said mixture of branched alkylbenzene sulphonates and unbranched alkylbenzene sulphonates, in which said 2-methyl-2-phenyl index of said mixture of modified alkylbenzenesulfonate surfactants is less than 0.1, and wherein in said mixture of branched and unbranched alkylbenzene sulphonates, said average aiiphatic carbon content is from about 11.5 to about 12.5 carbon atoms; said R1 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" means 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 attached 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 current commercial type, more biodegradable, which at the sulfonation forms linear alkylbenzenesulfonate, 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 impurities selected from 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 impurities is practically detectable.

Illustrative structures. To better illustrate the possible complexity of mixtures of modified alkylbenzenesulfonate surfactants of the invention and the resultant 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. (m) (n) (o) (P) (q) (r) (s) (t) (u) (v) Structures (w) and (x) non-limitingly illustrate less preferred compounds of formula (I) that may be present, at lower levels than the structures of preferred types illustrated above, in the modified alkylbenzene sulfonate surfactant mixtures 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 which may be present in the mixtures of modified alkylbenzenesulfonate surfactants of the invention and 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. Preferably the branched alkylbenzene sulfonate is the product of sulfonating a branched alkybenzene in which the branched alkyl benzene is produced by alkylating benzene on a zeolite beta catalyst which may be fluorinated or non-fluorinated, more preferably the zeolite beta catalyst is a zeolite beta acid catalyst. Preferred beta zeolite catalysts are catalysts of calcined zeolite beta treated with HF. Broadly speaking, the mixtures of modified alkyl benzene sulfonate surfactants herein can be made by the steps of: (I) Alkylate 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. Provided that the neutralization step (III) is conducted as generally taught herein, the product of step (III) is "a mixture of alkylbenzene sulfonate surfactants modified in accordance with the invention. The neutralization may be incomplete, the mixtures of the acid and neutralized forms of the modified alkylbenzenesulfonate systems present in all proportions, for example, from about 1000: 1 to 1: 1000 by weight, are also part of the present invention. , the largest critical points are in step (I). Therefore, it is further preferred that in step (I) the alkylation is carried out at a temperature of 125 ° C to 230 ° C, preferably about 175 ° C to 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. The time for this alkylation reaction may vary, however it is further preferred that the time for this alkylation be from 0.01 hours to about 18 hours, more preferably, as fast as possible, more typically from 0.1 hours to about 5 hours, or from about 0.1 hours to about 3 hours. In general it has been found that it is preferable in step (I) to couple together the use of relatively low temperatures (for example 175 ° C to about 215 ° C) with reaction times of medium duration (1 hour to about 8 hours) in the scales indicated above. 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 on 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, surprisingly, to convert said material into a material with a 2-methyl-2-phenyl index. more preferred. It is therefore a surprising discovery as part of the present invention that low levels of quaternary alkylbenzenes can be achieved in reactions catalyzed by benzene beta zeolite with branched olefins, as characterized by a 2-methyl-2-phenyl index of less than 0.1.

Alkylation catalyst The present invention uses a particularly defined alkylation catalyst. Said alkylation catalyst comprises a medium pore zeolite of moderate acidity which is defined in detail below. A particularly preferred alkylation catalyst comprises at least partially dealuminated, non-fluorinated zeolite beta, or at least partially dealuminated fluorinated acid. Numerous alkylation catalysts are easily determined to be unsuitable. Unsuitable alkylation catalysts include the catalysts of the DETAL® process, aluminum chloride, HF, and many others. In fact, none of the alkylation catalysts currently used for alkylation in the commercial production of linear alkyl detergents sulfonates is suitable. In contrast, the appropriate alkylation catalysts herein are selected from moderately acid selective alkylation catalysts, preferably of the zeolite type. More particularly, the zeolite in said catalysts for the step I alkylation step is preferably selected from the group consisting of ZSM-4, ZSM-20, and beta zeolite, more preferably beta zeolite, in at least partially acidic form. More preferably, the zeolite in step I (the alkylation step) 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%, preference for what at least 5%, more typically from 50% to about 90%, of said zeolite, wherein said zeolite is preferably a beta zeolite. More generally, an appropriate alkylation catalyst is typically at least partially crystalline, more preferably substantially crystalline not including binders or other materials used to form catalyst pellets, aggregates or mixed materials. Moreover, the catalyst is typically at least partially acidic beta zeolite. This catalyst is useful for the alkylation step identified as step I in the following claims. The largest pore diameter that characterizes the zeolites useful in the present alkylation process may be in the range of 6.2 Angstroms to 8 Angstroms, such as in the beta zeolite. 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 smaller pore size, such as mordenite, bid, HZSM-12 and HZSM-5. In effect, ZSM-5 has been tested and found inoperable in the present invention. The pore size and crystal structure dimensions of certain zeolites are specified in ATLAS OF ZEOLITE STRUCTURE TYPES by WM Meier and DH Olson, published by the Structure Commission of the International Zeolite Association (1978 and later editions) and distributed by Polycrystal Book Service , Pittsburgh, Pa. Zeolites useful in the alkylation step of the procedures present 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. Of 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 upon 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 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 extraction of alumina (dealuminization) and combination with one or more metal components, particularly the metals of 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 on contact with an atmosphere containing from about 5 to about 100% steam at a temperature of about 250 ° C to 1000 ° C. The vaporization can last for a period of between about 0.25 and about 100 hours and 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 could 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 substances or substances present in nature 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, nacrita or anaoxita. 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-alumina-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, with the zeolite content on the scale 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 that includes some useful for the alkylation step herein has a silica: alumina ratio of 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 relationship for tetrahedron SIO4 to AIO4. This ratio may vary from the silica: alumina ratio determined by various physical and chemical methods. For example, a non-detailed chemical analysis may include aluminum which is present in the form of cations associated with the acid sites in the zeolite, thus giving a low silica: alumina ratio. 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 ammonium ions on the sites acids. These disparities are particularly problematic when certain treatments are employed such as the subsequently described dealumination methods which result in the presence of free ionic aluminum of the zeolite structure. Therefore, care must be taken to ensure that the ratio of the silica: alumina structure is determined correctly. When the zeolites have been prepared in the presence of organic cations they are catalytically inactive, possibly because the intracrystalline free space is occupied by organic cations originating from the formation solution. These can be activated by heating them in an inert atmosphere at 540 ° C for one hour, for example, followed by base exchange with ammonium salts and then calcination at 540 ° C in 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 base exchange, 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 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 crystal structure density, together with values for some zeolites. Typical is given in U.S. Patent No. 4,016,218, to which reference is made.When it is synthesized in the alkali metal form, the zeolite is conveniently converted to the hydrogenated form, generally by intermediate formation of the ammonium form as a result of ammonium 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 alkali metal form. Preferred zeolite catalysts include zeolite beta, HZSM-4, HZSM-20 and HZSM-38. The most preferred catalyst is zeolite beta acid. A suitable beta zeolite for use herein is described in the U.S.A. No. 3,308,069, to which reference is made for details of this zeolite and its preparation. The zeolite beta catalysts in acid form are also commercially available as Zeocat PB / H from Zeochem. Other suitable zeolite beta catalysts for use can be provided by UOP Chemical Catalysts and Zeolyst International. More generally, the alkylation catalysts herein can be used with the proviso that the alkylation catalyst (1) can accommodate branched olefins as described elsewhere in the present in the smaller pore diameter of said catalyst and (b) alkylate benzene selectively with said branched olefins and / or mix with unbranched olefins with sufficient selectivity to provide the 2/3-phenyl index values defined in I presented. In a preferred embodiment, a hydrotrope or hydrotrope precursor is added either after step (I), during or after step (II) and before step (III) and during or after step (III). The hydrotropes are selected from any suitable hydrotrope, typically 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, eumeno, xylene, naphthalene or mixtures thereof.

Sulfonation and Handling or Neutralization (Steps ll / III) Preferably the sulfonation step (I i) is carried out using a sulfonation agent, preferably selected from the group consisting of sulfuric acid, sulfur trioxide with or without air, chlorosulfonic acid, oil, and mixtures thereof. Additionally, it is preferable in step (II) to remove components other than monoalkylbenzene before contacting the product of step (I) with the sulfonation agent. In general, the sulfonation of modified alkylbenzenes in the current process can be accomplished using any of the well known sulfonation systems, including those described in "Detergent Manufacture Including Zeollte Builders and other New Materials", Ed. Sittig, Noyes Data Corp., 1979, as well as in Vol. 56 of 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. 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 performance in soft water, and substituted ammonium may be useful in 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. Preferably the neutralization step (III) is carried out using a basic salt. Preferably the basic salt dyes a cation selected from the group consisting of alkali metal, alkaline earth metal, ammonium, substituted ammonium, and mixtures thereof and a selected anion of hydrogen, oxide, carbonate, silicate, phosphate and mixtures thereof. More preferably the basic salt is selected from the group consisting of sodium hydroxide, potassium hydroxide, magnesium hydroxide, calcium hydroxide, ammonium hydroxide, and mixtures thereof. The methods are tolerant to variation, 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.

EXAMPLES OF PREPARATION EXAMPLE 1 Mixture of 4-methyl-4-nonanol, 5-methyl-5-decanol, 6-methyl-6-undecanol and 6-methyl-6-dodecanol (A starting material for branched olefins) A mixture of 4.65 g of 2-pentanone, 20.7 g of 2-hexanone, 51.0 g of 2-heptanone, 36.7 g of 2-octanone and 72.6 g of diethyl ether is 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-methyl-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 (an alkylating agent for preparing modified 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-neck round bottom flask with nitrogen blanket, agitated equipped with a Dean Stark separator and a reflux condenser together with 35.8 g of a shape-selective zeolite catalyst (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 and the reaction mixture is cooled to 20 ° C. The substantially non-random methyl branched olefin mixture remaining in the flask is 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 148.2 g of a substantially non-random methyl branched olefin mixture. b) The olefin mixture of example 2a is combined with 36 g of a form-selective zeolite catalyst (acid mordenite catalyst) Zeocat® FM-8 / 25H) and reacted according to example 2a 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 reaction mixture is cooled to 20CC. The mixture of substantially monomethyl branched olefin with remaining randomized branch in the flask is 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 200 and a 2-methyl-2-phenyl index of about 0.005 (a modified alkylbenzene mixture according to the invention) 147 g of the substantially branched monomethyl branched olefin mixture with randomized branching of example 2 and 36 g of a zeolite-selective catalyst (Zeocat® PB / H zeolite beta-acid catalyst) are added to a 7.570 L stainless steel autoclave , agitated. The residual oiefina 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, add 2000 g of benzene (contained in an insulated container and added by an isolated pump system inside the isolated autoclave cell) 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 4-6 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 evaporated under vacuum. The product is then distilled under high vacuum (1-5 mm Hg). The mixture of substantially monomethyl branched alkylbenzene with a 2/3-phenyl number of about 200 and a 2-methyl-2-phenyl index of about 0.005 is collected from 76 ° C-130 ° C (167 g).

EXAMPLE 4 Mixture of substantially mono methyl branched alkylbenzenesulfonic acid with a 2/3-phenyl index of about 200 and a 2-methyl-2-phenyl index of about 0.005. (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 200 and a 2-methyl-2-phenyl index of about 0.005.

EXAMPLE 5 Mixture of substantially mono methyl branched alkylbenzenesulfonate, sodium salt with a 2/3-phenyl index of about 200 and a 2-methyl-2-phenyl index of about 0.005. (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 mixture of substantially monomethyl branched alkylbenzenesulfonate, sodium salt with a 2/3-phenyl number of about 200 and a 2-methyl-2-phenyl index of about 0.005.

EXAMPLE 6 Substitution of substantially linear alkylbenzene with a 2/3-phenyl index of about 200 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 number of about 200 and a 2-methyl-2-phenyl index of about 0.02 is prepared using a shape-selective zeolite catalyst (acid-beta zeolite catalyst). Zeocat® PB / H). A mixture of 15.1 g of Neodene® 10, 136.6 g of Neodene® 1 12, 89.5 g of Neodene® 12, and 109.1 g of 1-tridecene is added to a stirred stainless steel 7,570 L autoclave, along with 70 g of a shape-selective zeolite catalyst (Zeocat® PB / H zeolite beta acid catalyst). 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 a isolated vessel and added by means of an isolated pumping system inside the isolated autoclave cell) 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 at 170-175 ° C for about 18 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 120CC 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 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 200 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 index of about 200 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 200 and a 2-methyl-2-phenyl index of about 0.02.

EXAMPLE 8 Mixture of substantially linear alkylbenzenesulfonic acid with a 2/3-phenyl number of about 200 and a 2-methyl-2-phenyl index of about 0.02 (a mixture of alkylbenzenesulfonate surfactant which will be used as a component of agent mixtures. modified alkylbenzenesulfonate surfactant according to the invention) The substantially linear alkylbenzenesulfonic 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 the substantially linear alkylbenzenesulfonate mixture, sodium salt with a 2/3-phenyl number of about 200 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 are added 299 g of geranylacetone, 3.8 g of 5% ruthenium on carbon and 150 ml of methanol. The glass liner is sealed inside a 3L stainless steel tilting autoclave and the autoclave is purged once with N2 17.57 kg / cm2 gravimetric, once with H2 17.57 kg / cm2 gravimetric and then loaded with H2 70.03 kg / cm2 gravimetric. 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 on 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 H 35.15 kg / cm2 gravimetric. With mixing, the mixture of reaction. 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, 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 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 palladium on 5% activated 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 / cm2 gravimetric. 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 flask, 3-neck, 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 ( acid mordenite catalyst Zeocat® FM-8 / 25H). 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 speed. 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 is 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 200 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 (Zeocat® PB / H zeolite beta catalyst) 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 to about 205 ° 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 alkyl benzene with random branching and a 2/3-phenyl index of about 200 and a 2-methyl-2-phenyl index of about 0.04 is collected from 88 ° C-160 ° C.

EXAMPLE 14 Mixture of substantially dimethyl branched alkylbenzenesulfonic acid with random branching and a 2/3-phenyl index of about 200 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 resulting sulfonic acid mixture has a 2/3-phenyl number of about 200 and a 2-methyl-2-phenyl index of about 0.04.

EXAMPLE 15 Mixture of substantially dimethyl branched alkylbenzenesulfonic acid, sodium salt, with random branching and a 2/3-phenyl index of about 200 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 200 and a 2-methyl-2-phenyl index of about 0.04.

EXAMPLE 16 Mixture of linear and branched alkylbenzenes with a 2/3-phenyl index of about 200 and a 2-methyl-2-phenyl index of about 0.01 (a modified alkylbenzene mixture according to the invention) A modified alkylbenzene mixture is prepared by combining 147.5 g of the product of example 3 and 63.2 g of the product of example 6. The resulting modified alkylbenzene mixture has a 2/3-phenyl about 200 and a 2-methyl-2-phenyl index of about 0.01.

EXAMPLE 17 A mixture of linear and branched alkylbenzene sulfonic acid and salts with a 2/3 phenyl number of about 200 and a 2-methyl-2-phenyl index of about 0.01. (mixtures of modified alkylbenzenesulfonic acid and salt mixtures of the invention) a) Mixture of modified alkylbenzenesulfonic acid of the invention. The modified alkylbenzene mixture resulting from example 16 is sulfonated with one molar equivalent of chlorosulfonic acid using methylene chloride as a solvent with HCl evolving as a secondary product. The resulting sulfonic acid product is concentrated by evaporation of methylene chloride under vacuum. The resulting modified alkylbenzene sulfonic acid product has a 2/3-phenyl number of about 200 and a 2-methyl-2-phenyl index of about 0.01. b) Modified alkylbenzene sulfonate mixture, sodium salt, of the invention. The product of Example 17 a) is neutralized with one molar equivalent of sodium methoxide in methanol and the methanol is evaporated to give the mixture of the invention of solid modified alkylbenzene sulfonate, sodium salt, with a 2/3-phenyl number of about 200 and a 2-methyl-2-phenyl index of about 0.01.

Methods to determine composition parameters (index 2/3-phenyl, 2-methyl-2-phenyl index) of mixed systems of alkylbenzene / alkylbenzenesulfonate / alkylbenzenesulfonic acid It is well known in the art how to determine the compositional parameters 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 by GC and / or mass GC for the alkylbenzenes and HPLC for the 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 of alkylbenzenes, 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 the methods known in the art. The sequence of methods that will be used depends on the composition that will be characterized as follows: * 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 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 Red lite Septa 11mm 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. • 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 the sample in a 2 ml GC auto vial. • Add 1 ml of methylene chloride J.T. Baker HPLC grade, Cat. 9315-33 to the CG vial, seal with caps (lids) with 11 mm Teflon coating for folded vial, Part No. HP5181- 1210 using a folder 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: 0.63 kg / cm2 Flows: Column flow @ 1 ml / min. Division fan @ 3 ml / min. Septum purge @ 1 ml / min. Injection: Automatic HP 7673 (Autosampler) syringe of 10 μl, injection of 1 μl. 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 which 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 GC test must be further purified by distillation until the test samples pass the GC test.

Desulfonation (DE) The desulphonation method is a standard method described in 'The Analysis of Detergents and Detergent Products', by GF 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 TM 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 method of HPLC, as described herein, for evaluation of branched and unbranched alkylbenzene sulphonic acid and / or salt mixtures (Mixtures of modified alkylbenzenesulfonic acid and / or salts) The method provides a means to convert the sulfonic acid mixture and / or salt in the branched and unbranched alkylbenzene mixtures which are then can be analyzed by means of CG and NMR methods NMR1 and NMR2 which are described in the present.

HPLC S. R. Ward, Anal. Chem., 1989, 61, 2534; D. J. Pietrzyk and S. Chen, Univ. Lowa, Dept. of Chemistry. Apparatus Suitable HPLC system Waters Division of Millipore or eq. HPLC pump with He Waters model 600 sprinkler or equivalent and temperature control Waters Model 717 or equivalent or equivalent Tray of 48 Waters self or equivalent positions Waters PDA996 UV detector or equivalent Waters 740 fluorescence detector or equivalent Waters 860 data system / lntegrator or equivalent Milllpore No. 78514 and No. 78515 autoclaves and caps 4 ml capacity Column HPLC, X82 Supelcosil LC18, 5 μm, 4.6 mm x 25 cm, Supelcosil No. 58298 Rheodyne 0.5 mm x 3 mm column inlet filter Rheodyne No. 7335 LC Millipore SJHV M47 10 eluent membrane filters, disposable membrane filter funnel of 0.45 μm Weighs Sartorius or equivalent; accuracy of ± 0.0001 g. Vacuum Cleaner Sample clarification equipment with pumps and filters, Waters No. WAT0851 13 Reagents Standard material LAS of C8 sodium p-2-octylbenzenesulfonate Standard material LAS of C15 sodium p-2-pentadecylbenzenesulfonate.

Process A. HPLC mobile phase preparation 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 transfer quantitatively to a 100 ml volumetric flask. 2.- Dissolve with 30 ml of ACN and dilute to volume with water grade HPLC. This prepares ca. 1500 ppm of mixed standard solution.

C. Sample solutions 1. Solutions for washing. Transfer 250 μl of the standard solution to a 1 ml autoload vial and add 750 μl of the wash solution. Cover and place in the auto tray. 2. Alkylbenzenesulfonic acid or alkylbenzenesulfonate. 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 standard solution to a 1 ml autologous 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 0.45 μm membrane before transferring to the auto vial. Cover and place in the self-cleaning tray.

D. HPLC system 1.- Start the HPLC pump with mobile phase. Install column and column inlet filter and equilibrate with eluent (0.3 ml / min for at less 1 hour). 2.- Operate the samples using the following HPLC conditions: Mobile phase A 100 mM NaCI / 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 min. 100% Mobile phase A 0% Mobile phase B Time 120 min. 100% Mobile phase A 0% Mobile phase B Note: A delay time gradient of 5-10 minutes 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 Duplicate injections 2 Data rate: 0.45 MB / hour Resolution: 4.8 nm. 3.- The column must 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 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 NMR 4 methods. If the alkylbenzenesulfonic acid / salt mixture contains 10% or more of components outside the retention limits defined by the standards then the sample must be further purified by the HPLC-P method or by the DE methods, DIS.

Preparation HPLC (HPLC-P) Alkylbenzenesulfonic acids and / or salts containing substantial impurities (10% or greater) are purified by preparative HPLC. See, for example Surfactant Science Series, volume 40, chapter 7 and Surfactant Science Series, volume 73, chapter 7. This is routine for the person skilled in the art. A sufficient amount must be purified to meet the requirements of NMR 3 and NMR 4.

Distillation (DIS) A 5-liter, round bottom, 3-necked flask with 24/40 joints is equipped with a magnetic stir 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.

Preparation CL method using Mega Bond Elut Sep 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 alkylbenzene sulfonate salt can be loaded into a 5 g (20 ml) Elut Sep Pak® Mega Bond and listed within the same amount of time.

A. HPLC instrumentation: Waters gradient pump model 600E, model 717, Walen Millenium PDA, Millenium Data Manager (v. 215). Mega Bond Elut: united phase of C18, Varies 5g or 10g, PN: 1225-6023, 1225-6031 with adapters. HPLC Columns: Supelcosil LC-18 (X2), 250x4.6mm, 5mm; No. 58298. Analytical weighing: mettier model AE240, capable of weighing samples at ± 0.01 mg.

B. Accessories. Volumetric: glass, 10 ml. Graduated cylinder: 1 L. HPLC autologous ampoules: 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 (Dl-H20): 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. HPLC conditions Aqueous phase preparation: A: To 600 ml of Dl-H20 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: To 400 ml of Dl-H20 contained in a graduated cylinder of 1 L, 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% to 95% B for 98 min. 5% A / 95% B for 1 10 min. 100% A for 125 min. Column temperature: Not thermofixed (ie, room temperature). HPLC flow rate: 1.2 mL / min. Injection volume: 10 mL. Operation time: 125 minutes. UV detection: 255 nm. Conc. > 4 mg / ml.

Balancing sep pak (bond elut, 5q) 1.- Pass 10 ml of the solution containing 25/75 H20 / ACN to sep pak by applying a positive pressure with a 10 cc syringe at a speed of ~ 40 drops / min . Do not allow the sep pak to dry. 2. - Immediately pass 10 ml of the solution containing 70/30 H2O / ACN in the same manner 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 sample isolation of mine 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 10 cc syringe start the separation. Rinse the vial with 1 ml (x2) portions of the 70/30 solution and load into the sep pak. Keep - 1 mm 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 10 cc syringe 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 mine 1.- Pass 10 ml of solution containing 25/75 H20 / ACN with positive pressure from a 10 cc syringe and collect the effluent. Repeat this with another 10 ml and again with 5 ml. The isolated MLAS is now ready for freeze drying and subsequent characterization. 2.- Rotovaporizar until ACN is removed and dried by freezing 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.

Balancing sep pak (bond elut, 5g) 1.- Pass 20 ml of the solution containing 25/75 H20 / ACN to sep pak using laboratory air or regulated cylinder air 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.- Pass immediately 20 ml (x2) and an additional 10 ml of a solution containing 70/30 H20 / ACN in the same way as in No. 1. Do not allow the sep pak to dry. Maintain a level of solution (x 1 mm) in the head of the sep pak. 3.- The sep pak is now ready for sample loading.

Load / separation and sample isolation of mine 1.- Weigh < 500 mg of sample in a 2-dram vial and add 5 ml of 70/30 H20 / 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 portions of 2 ml (x2) of the 70/30 solution and put in the sep pak. Keep ~ 1 mm of solution in 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 mine 1.- Pass 20 ml of solution containing 25/75 H20 / ACN with positive pressure from an air source and collecting 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. Note: Adjustments in organic modifier concentration may be necessary for optimal separation and isolation.

Acidification (AC) The salts of alkylbenzenesulfonic acids are acidified by common means such as reaction in a solvent with HCl or sulfuric acid or by the use of an acidic resin such as Amberlyst 15. Acidification is routine for one skilled in the art. After acidifying, all are eliminated Solvents, especially any moisture, so that the samples are anhydrous and free of solvent. 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.

NMR 1 13 C-NMR index 2/3-phenyl for mixtures of alkylbenzene. A 400 mg sample of an alkylbenzene 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 13C-NMR spectrum region between approximately 145. 00 ppm to approximately 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 13 J / C-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 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 recitation 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 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). 3 C-NMR 13C-RMN 2/3-phenyl index 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. 13C-NMR is operated on the sample on a 300 MHz NMR spectrometer using a recycle time of 20 seconds, a gate width of 13C of 40 ° and heteronuclear decoupling of the gate. 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 2/3-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 NMR 4 13C-NMR 2-methyl-2-phenyl index 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 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-phenyl index = (Integral from about 156.40 ppm to about 156.65 ppm) / (integrally from about 152.50 ppm to about 156.90 ppm). In one embodiment of the present invention, hand dishwashing compositions are substantially free of alkylbenzene sulfonate surfactants other than the mixture of modified alkyl benzene sulfonate surfactants. That is, no alkylbenzene sulfonate surfactant other than the mixture of modified alkyl benzene sulphonate surfactants is added to the detergent compositions. In another embodiment of the present invention, hand dishwashing compositions may contain as an additional surfactant at least about 0.1%, preferably not more than about 10%, more preferably not more than about 5%, even more preferably not more than about 1%, of a commercially available linear C 1 -C C alkylbenzenesulfonate surfactant. It is further preferred that the commercial Cι-C linear alkylbenzenesulfonate surfactant have a 2/3-phenyl index of from 75 to 160. In another embodiment of the present invention, hand dishwashing compositions may contain as a surfactant additional at least about 0.1%, preferably not more than about 10%, more preferably not more than about 5%, even more preferably not more than about 1%, of a commercially highly branched alkylbenzene sulfonate surfactant. For example TPBS or tetrapropylbenzene sulfonate.

The present invention encompasses less preferred embodiments for its normal but sometimes useful purposes, such as the addition of useful hydrotrope precursors and / or hydrotropes, such as C? -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. Likewise, it will be understood that said materials, if and when they interfere with the analytical methods, will not be included in samples of compositions that are used for analytical purposes. Numerous variations of the hand dishwashing compositions are useful. Such variations include: • The hand dishwashing composition that is substantially free of alkylbenzene sulfonate surfactants other than the mixture of modified alkyl benzene sulfonate surfactants; The hand dishwashing composition comprising, in said component (iii), at least about 0.1%, preferably not more than about 10%, more preferably not more than about 5%, even more preferably not more than about 1%, of a commercial linear C 1 or C 14 alkylbenzenesulfonate surfactant; The hand dishwashing composition comprising, in said component (iii), at least about 0.1%, preferably not more than about 10%, more preferably not more than about 5%, even more preferably not more than about 1 %, of a commercially highly branched alkyl benzene sulfonate surfactant. (For example TPBS or tetrapropylbenzene sulfonate); • The hand dishwashing composition comprising, in said component (iii), a nonionic surfactant at a level of 0.5% to about 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 linear C10-C16 alkyl, branched C? 0-C? 6 alkyl of C? -C3 in the middle part of its chain, branched C10-C16 alkyl of guerbet, and mixtures thereof, and a hydrophilic group selected from 1-15 ethoxylates, 1-15 propoxylates, 1-15 butoxylates and mixtures thereof, in blocked or unblocked form. (When they are unblocked, a terminal 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 Cß, optionally comprising a primary alcohol or , preferably when present, a secondary one.); • The composition for dishwashing by hand that includes, in said component (iii), an alkyl sulfate surfactant at a level of from about 0.5% to about 25% by weight of said detergent composition, wherein said alkyl sulfate surfactant has a hydrophobic group selected from C10-C18 linear alkyl , branched C? -C? 8 alkyl of C? -C3 in the middle part of its chain, branched C10-C18 alkyl of guerbet, and mixtures thereof and a selected cation of Na, K, and mixtures thereof . The hand dishwashing composition comprising, in said component (iii), an alkyl (polyalkoxy) sulfate surfactant at a level of from 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 from C? -C3 in the middle part of its chain, branched C10-C16 alkyl from guerbet, and mixtures thereof, and a hydrophilic (polyalkoxy) sulfate group selected from 1-15 polyethoxylsulfate, 1-15 polypropoxylsulfate, 1-15 polybutoxysulfate, 1-15 poly (ethoxy / propoxy / butoxy) sulfates mixed and mixtures thereof. themselves, in blocked or unblocked form; and a cation selected from Na, K and mixtures thereof. It is preferred that when the hand dishwashing composition comprises an alkyl (polyalkoxy) sulfate surfactant having a hydrophobic group selected from linear C 0 -C 16 alkyl, branched C 10 -C 16 alkyl of C 1 -C 3, in the middle part of its chain, C10-C16 alkyl branched from guerbet, and mixtures thereof, and a hydrophilic group of (polyalkoxy) sulfate selected from 1-15 polyethoxylsulfate, 1-15 polypropoxylsulfate, 1-15 polybutoxysulfate, 1-15 poly (ethoxy / propoxy / butoxy) sulfates mixed and mixtures thereof, in blocked or unblocked form; and a cation selected from Na, K and mixtures thereof. It is preferred that when the hand dishwashing composition comprises a non-ionic surfactant, it is a polyalkoxylated alcohol in blocked or unblocked form having a hydrophobic group selected from linear alkyl of C? 0-C? 6 > C10-C16 branched alkyl of CrC3 in the middle part of its chain, branched C10-Ci6 alkyl of guerbet, and mixtures thereof, and a hydrophilic group selected from 1-15 ethoxylates, 1-15 propoxylates, 1-15 butoxylates and mixtures thereof, in blocked or unblocked form. When they are unblocked, a terminal primary -OH portion is also present and when they are blocked, a terminal portion of the -OR form in which R is a hydrocarbyl portion of C C6) optionally comprising a primary alcohol is also present, preferably when present, a secondary one. It is preferred that when the dishwashing composition by hand comprises an aikyl sulfate surfactant having a hydrophobic group selected from linear C 1 or C 8 alkyl, branched C 10 -C 15 alkyl of C C 3 in the middle part of its chain , C-or C-C branched alkyl of guerbet, and mixtures thereof and a cation selected from Na, K, and mixtures thereof.

The hand dishwashing compositions of the present invention can be used or applied by hand and / or can be applied in unit dosage or freely alterable, or by means of automatic assortment. They can be used in aqueous and non-aqueous cleaning systems. They can have a broad pH range, for example from about 2 to about 12 or higher, although detergent compositions having a pH of about 8 to about 11 are among the preferred embodiments, and can have a broad scale of alkalinity reserve . The types of high foam formation and low foam formation are covered, as well as the types to be used in all procedures of aqueous and non-aqueous cleaning products for the consumer.

Heavy-duty water-based liquid detergents Surfactants The present invention also encompasses water-based liquid detergent compositions. Aqueous liquid detergent compositions preferably comprise from about 10% to about 98%, preferably from about 30% to about 95%, by weight, of an aqueous liquid carrier which is preferably water. Additionally, the aqueous liquid detergent compositions of the present invention comprise a surfactant system containing preferably one or more co-detersive surfactants in addition to the branched surfactants described above. Additional co-surfactants may be selected from nonionic detersive surfactant, anionic detersive surfactant, zwitterionic detersive surfactant, amine oxide detersive surfactant, and mixtures thereof. The surfactant system typically comprises from about 5% to about 70%, preferably from about 15% to about 30%, by weight of the detergent composition.

Anionic Surfactant Anionic surfactants include Cu-C? 8 alkylbenzenesulfonates (LAS) and primary, branched and random chain C-020 alkyl sulfates (AS), secondary C? Or C? 8 alkyl sulfates (2) , 3) of the formula CH3 (CH2) x (CHOSO3'M +) CH3 and CH3 (CH2) and (CHOSO3-M +) CH CH3 where x and (y +1) are integers of at least 7, preferably of at least 9 and M is a water-soluble cation, especially sodium, unsaturated sulfates such as oleyl sulfate, C? 0-C? 8 alkylalkoxy sulfates ("AEXS", especially ethoxy sulfates EO 1-7), C 0- alkylalkoxycarboxylates C? 8 (especially the EO 1-5 ethoxycarboxylates), the glycerol ethers of C? 0-? S, the alkyl polyglycosides of C? OC? 8 and their corresponding sulfated polyglycosides, and the alpha-sulfonated fatty acid esters of C 2-C? 8. Generally speaking, the anionic surfactants useful herein are described in the U.S.A. No. 4,285,841, issued on 25 August 1981, and in the patent of E.U.A. No. 3,919,678, Laughlin et al, issued December 30, 1975. Useful anionic surfactants include water-soluble salts, particularly the metalalkali, ammonium and alkylammonium salts (eg, monoethanolammonium or triethanolammonium), of organic sulfuric reaction products having in their molecular structure an alkyl group containing from about to about 20 carbon atoms and an ester group of sulfonic acid or sulfuric acid. (Included in the term "alkyl" is the alkyl portion of aryl groups). Examples of this group of synthetic surfactants are the alkyl sulfates, especially those which are obtained by sulfating the higher alcohols (C 8 -C 8 carbon atoms), such as those produced by reducing the glycerides of bait or coconut oil. Other anionic surfactants useful herein are the water-soluble salts of alkylphenol ethylene oxide sulfates containing from about 1 to about 4 ethylene oxide units per molecule and from about 8 to about 12 carbon atoms in the alkyl group. Other anionic surfactants useful herein include the water-soluble salts of esters of α-sulfonated fatty acids containing from about 6 to 20 carbon atoms in the fatty acid group and from about 1 to 10 carbon atoms in the ester group; the water-soluble salts of 2-acyloxy-alkan-1-sulfonic acids containing about 2 to 9 carbon atoms in the acyl group and from about 9 to about 23 carbon atoms in the alkane portion; the water-soluble salts of olefin sulfonates containing from about 12 to 24 carbon atoms; and b-alkoxy alkanesulfonates containing from about 1 to 3 carbon atoms in the alkyl group and from about 8 to 20 carbon atoms in the alkane portion. The anionic surfactants which are particularly preferred herein are the alkyl polyethoxylated sulfates of the formula: RO (C2H4O) xSO3"M + wherein R is an alkyl chain, saturated or unsaturated, having from about 10 to about 22 carbon atoms, M is a cation which makes the compound soluble in water, especially an alkali metal, ammonium, or substituted ammonium cation, and x is on average from 1 to about 15. Preferred alkyl sulfate surfactants are the primary and secondary alkyl sulfates of non-ethoxylated C? 2_? 5. Under washing conditions in cold water, ie less than about 18.3 ° C, it is preferred that there is a mixture of said ethoxylated and non-ethoxylated alkyl sulphates. Examples of fatty acids include capricious, lauric, myristic, palmitic, stearic, arachidic, and behenic acid. Other fatty acids include palmitoleic, oleic, linoleic, linolenic, and ricinolenic acid.

Nonionic surfactant. Conventional non-ionic and amphoteric surfactants include alkyl ethoxylates of (AE) including the so-called narrow peak alkyl ethoxylates and C6-C2 alkoxylated alkyl phenols (especially ethoxylated and mixed ethoxy / propoxy). The N-alkyl polyhydroxy fatty acid amides of C? 0-C? 8 can also be used. See WO 9,206,154. Other surfactants derived from sugar include the N-alkoxy polyhydroxy fatty acid amides, such as N- (3-methoxypropyl) glucamide of C? O-C? 8. The N-propyl up to N-hexyl glucamides of C? 2-C? 8 can be used for low foaming. Conventional C10-C 6 soaps can also be used. Examples of nonionic surfactants are described in the U.S.A. No. 4,285,841, Barrat et al, issued August 25, 1981. Preferred examples of such surfactants include ethoxylated alcohols and ethoxylated alkylphenols of the formula R (OC2H4) nOH, in which R is selected from the group consisting of aliphatic hydrocarbons containing from about 8 to about 15 carbon atoms and alkylphenyl radicals in which the alkyl groups contain from about 8 to about 12 carbon atoms, and the average value of n is from 5 to about 15. Those surfactants are describe more fully in the US patent No. 4,284,532, Leikhim et al, issued August 18, 1981. Particularly preferred are ethoxylated alcohols having an average of about 10 to about 15 carbon atoms in the alcohol and an average degree of ethoxylation of about 6 to about 12 friols of ethylene oxide per mole of alcohol. Mixtures of anionic and nonionic surfactants are especially useful. Other conventional useful surfactants are listed in standard texts, including C? 2-C? 8 betaines and sulfobetaines (sultaines).

Amine Oxide Surfactants The compositions herein also contain amine oxide surfactants of the formula: R1 (EO) x (PO) and (BO) zN (O) (CH2R ') 2 * qH2O (I) In In general, it can be seen that the structure (I) provides a long chain portion R1 (EO) x (PO) and (BO) z and two short chain portions, CH2R '. R 'is preferably selected from hydrogen, methyl and -CH2OH. In general, R1 is a primary or branched hydrocarbyl portion which may be saturated or unsaturated, preferably, R1 is a primary alkyl portion. When x + y + z = 0, R1 is a hydrocarbyl portion having chain length from about 8 to about 18. When x + y + z is different from 0, R1 may be somehow longer, having a length of chain on the scale of C? 2-C24. The general formula also encompasses amine oxides in which x + y + z = 0, R1 is H and q is 0-2, preferably 2. These amine oxides are illustrated by C2-alkyldimethyl amine oxide, oxide of hexadecyldimethyl amine, octadecyl amine oxide and its hydrates, especially the hydrates as described in US Pat. 5,075,501 and 5,071, 594, incorporated herein by reference. The invention also encompasses amine oxides in which x + y + z is non-zero, specifically x + y + z is from about 1 to about 10, R1 is a primary alkyl group containing from 8 to about 24 carbons, preferably from about 12 to about 16 carbon atoms; in those embodiments y + z is preferably 0 and x is preferably from about 1 to about 6, more preferably from about 2 to about 4; EO represents ethyleneoxy; PO represents propyleneoxy; and BO represents butyleneoxy. Said amine oxides can be prepared by conventional synthetic methods, for example, by the reaction of alkyleoxy sulfates with dimethylamine followed by oxidation of the ethoxylated amine with hydrogen peroxide. The amine oxides which are highly preferred herein are solids at room temperature, more preferably have melting points in the range of 30 ° C to 90 ° C. Amine oxides suitable for use herein are commercially made by a number of suppliers, including Akzo CEIME, Ethyl Corp., and Procter &; Gamble. See McCutcheon's compilation and Kirk Othmer's review article for alternative manufacturers of amine oxides. Preferred commercially available amine oxides are solid ADMOX 16 and ADMOX 18, ADMOX 12 and especially ADMOX 14 dihydyl dihydrate from Ethyl Corp. Preferred embodiments include sodium dihydrate dodecyl dimethylamine, hexadecyldimethylamine oxide dihydrate, octadecyldimethylamine oxide dihydrate, hexadecyltris (ethyleneoxy) dimethylamine oxide, tetradecyldimethylamine oxide dihydrate, and mixtures thereof. While in some of the preferred embodiments R 'is H, there is some latitude with respect to having R' slightly larger than H. Specifically, the invention further encompasses embodiments in which R 'is CH20H, such as hexadecylbis oxide ( 2-hydroxyethyl) amine, cebobis (2-hydroxyethyl) amine oxide, stearylbis (2-hydroxyethyl) amine oxide, and oleylbis (2-hydroxyethyl) amine oxide.

Detergency builders The compositions herein also optionally but preferably contain up to about 50%, more preferably from about 1% to about 40%, even more preferably from about 5% to about 30%, by weight of a builder material . The higher or lower levels, however, does not mean that they are excluded. Detergent builders may optionally be included in the compositions herein to assist in controlling mineral hardness. Inorganic as well as organic builders can be used. Builders are typically used in fabric washing compositions to aid in the removal of particulate soils. Detergent builders are described in the US patent. No. 4,321, 165, Smith et al, issued on 23 March 1982. Preferred builders for use in liquid detergents herein are described in the U.S.A. No. 4,282,532, Leikhim et al, issued August 18, 1981. Examples of silicate builders are alkali metal silicates, particularly those having a ratio of Yes? 2: Na2? in the scale of 1.6: 1 to 3.2: 1, and layered silicates, such as the layered sodium silicates described in the U.S.A. 4,664,839, from May 12, 1987 to H. P. Rieck. NaSKS-6 is the registered trademark for a crystalline layered silicate sold by Hoechst (commonly abbreviated herein as "SKS-6"). Unlike zeolite builders, the NaSKS-6 silicate builder does not contain aluminum. The NaSKS-6 has the form of d-Na2Si? 5 silicate stratified morphology. It can be prepared by the preparation methods as described in the German application DE-A-3, 417,649 and DE-A-3,742,043. SKS-6 is a highly preferred stratified silicate for use herein, but other layered silicates, such as those having the general formula NaMSix? 2? + - |. yH2? wherein M is sodium or hydrogen, x is a number from 1.9 to 4, preferably 2, and y is a number from 0 to 20, preferably 0, can be used herein. Several other stratified silicates from Hoechst include NaSKS-5, NaSKS-7 and NaSKS-11 as the a, β and α forms. As noted above, d-Na2S05 (NaSKS-6 form) is most preferred for use herein. Other silicates can also be useful, such as, for example, magnesium silicate, which can serve as a stabilizing agent for oxygen bleaches, and as a component of foam control systems. Examples of carbonate builders are the alkali metal and alkali metal carbonates as described in German Patent Application No. 2,321,001 published November 15, 1973. Aluminosilicate builders are useful in the present invention . The aluminosilicate builders can be a very important detergency builder ingredient in liquid detergent formulations. The aluminosilicate builders include those that have the empirical formula: Mz (z (AIO2) and] -xH2O in which z, w and y are integers of at least 6, the molar ratio of z to y is in the scale from 1.0 to about 0.5, and x is an integer from 15 to about 264. Useful aluminosilicate ion exchange materials are commercially available. These aluminosilicates can be crystalline or amorphous in structure and can be aluminosilicates that occur naturally or synthetically derived. A method for the production of aluminosilicate ion exchange materials is described in the U.S.A. 3,985,669, Krummel et al, issued October 12, 1976. The preferred synthetic crystalline aluminosilicate ion exchange materials useful herein are available under the designations Zeolite A, Zeolite P (B), Zeolite MAP and Zeolite X. In an especially preferred embodiment, the material of ion exchange of crystalline aluminosilicate has the formula: Na12 [(Al? 2) i2 (Si02) i2 xH2? wherein x is from about 20 to about 30, especially about 27. This material is known as Zeolite A. Dehydrated zeolites (x = 0-10) can also be used herein.

Preferably, the aluminosilicate has a particle size of 0.1-10 microns in diameter. Organic builders suitable for the purposes of the present invention include, but are not limited to, a wide variety of polycarboxylate compounds. As used herein, "polycarboxylate" refers to compounds having a plurality of carboxylate groups, preferably at least 3 carboxylates. Polycarboxylate builders can generally be added to the composition in acid form, but can also be added in the form of a neutralized salt. When used in the salt form, the alkali metal salts, such as sodium, potassium and lithium, or alkanolammonium are preferred. Included among the polycarboxylate builders there is a wide variety of categories of useful materials. An important category of polycarboxylate builders encompasses ether polycarboxylates, including oxydisuccinate, as described in Berg, U.S. 3,128,287, issued April 7, 1964, and Lamberti et al, patent of E.U.A. 3,635,830, issued January 18, 1972. See also detergency builders "TMSCTDS" of the U.S. patent. 4,663,071, issued to Bush et al, on May 5, 1987. Suitable ether polycarboxylates also include cyclic compounds, particularly 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 useful organic builders include the ether hydroxypolycarboxylates, copolymers of maleic anhydride with ethylene or vinyl methyl ether, 1,3-trihydroxybenzene-2,4,6-trisulfonic acid and carboxymethyloxy-succinic acid, the various alkali metal salts, ammonium and substituted ammonium of polyacetic acids such as ethylenediaminetetraacetic acid and nitrilotriacetic acid, as well as polycarboxylates such as mellitic acid, succinic acid, oxydisuccinic acid, polymaleic acid, benzene-1, 3,5-tricarboxylic acid, carboxymethyloxysuccinic acid and soluble salts of the same. Citrate builders, for example, citric acid and soluble salts thereof (particularly sodium salt), are polycarboxylate builders of particular importance for heavy-duty liquid detergent formulations because of their availability from renewable sources and its biodegradability. Oxydisuccinates are also especially useful in said compositions and combinations. Also suitable in the detergent compositions of the present invention are the 3,3-dicarboxy-4-oxa-1,6-hexanedioates and the related compounds described in the US patent. 4,566,984, Bush, issued January 28, 1986. Useful succinic acid builders they include the C5-C20 alkyl and alkenyl succinic acids and salts thereof.

A particularly preferred compound of this type is dodecenylsuccinic acid. Specific examples of succinate builders include: laurylsuccinate, myristylsuccinate, palmitylsuccinate, 2-dodecenylsuccinate (preferred), 2-pentadecenylsuccinate, and the like. Lauryl succinates are the preferred builders of this group and are described in European patent application 86200690.5 / 0,200,263, published on November 5, 1986. Other suitable polycarboxylates are described in US Pat. No. 4,144,226, Crutchfield et al, issued March 13, 1979 and in the US patent. No. 3,308,067, Diehl, issued March 7, 1967. See also Diehl, patent of E.U.A. No. 3,723,322. Fatty acids, for example, monocarboxylic acids of C12- C- | 8 >; they may also be incorporated into the compositions as single materials, or in combination with the aforementioned builders, especially citrate and / or succinate builders, to provide additional builder activity. The use of fatty acids will generally result in a decrease in foaming, which should be taken into account by the formulator. In situations where phosphorus-based builders can be used, the various alkali metal phosphates such as the well-known sodium tripolyphosphates, sodium pyrophosphate and sodium orthophosphate can be used. You can also use the breeders of phosphonate detergency such as ethane-1-hydroxy-1,1-diphosphonate and other known phosphonates, (see, for example, U.S. Patent Nos. 3,159,581, 3,213,030, 3,422,021, 3,400,148 and 3,422,137).

Other optional components of the composition. In addition to the liquid and solid phase components as described herein above, water-based detergent compositions may contain, and preferably will, various other optional components. Said optional components may be in liquid or solid form. The optional components can be dissolved in the liquid phase or they can be dispersed within the liquid phase in the form of fine particles or droplets. Some of the other materials that may optionally be used in the compositions herein are described in greater detail as follows: Optional inorganic detergency builders. The detergent compositions herein may also optionally contain one or more types of inorganic detergency builders in addition to those listed here above which also function as alkalinity sources. Such optional inorganic builders may include, for example, aluminosilicates such as zeolites. The aluminosilicate zeolites, and their use as builders, are described more fully in Corkill et al, U.S.

No. 4,605,509; issued August 12, 1986, the description of which is incorporated herein by reference. Also crystalline layered silicates, such as those described in this US patent. 509, are also suitable for use in the detergent compositions herein. If used, optional inorganic builders may comprise from about 2% to 15% by weight of the compositions herein.

Optional enzymes The detergent compositions herein may also optionally contain one or more types of detergent enzymes. Said enzymes may include proteases, amylases, cellulases and lipases. Such materials are known in the art and are commercially available. Non-aqueous liquid detergents herein can be incorporated in the form of suspensions, "marumas" or "lozenges". Another suitable type of enzyme comprises those in the form of enzyme suspensions in nonionic surfactants, for example the enzymes marketed by Novo Nordisk under the trade name "SL" or the microencapsulated enzymes marketed by Novo Nordisk under the trade name "LDP" . Enzymes that are added to the compositions herein in the form of conventional enzyme lozenges are especially preferred for use herein. Said pellets will generally be in the size range of about 100 to 1,000 microns, more preferably of about 200 to 800 microns and will be suspended through the non-aqueous liquid phase of the composition. It has been found that the tablets in the compositions of the present invention, in comparison with other forms of enzymes, exhibit enzyme stability especially desirable in terms of retention of enzyme activity over time. Thus, compositions using enzyme pellets do not need to contain conventional stabilizing enzyme such as those that frequently must be used when enzymes are incorporated in aqueous liquid detergents. If used, the enzymes will normally be incorporated in the non-aqueous liquid compositions herein at levels sufficient to provide up to about 10 mg by weight, more typically from about 0.01 mg to about 5 mg, of active enzyme per gram of the composition. Established otherwise, the non-aqueous liquid detergent compositions herein will typically comprise from about 0.001% to 5%, preferably from about 0.01% to 1% by weight, of a commercial enzyme preparation. Protease enzymes, for example, are normally present in such commercial preparations at levels sufficient to provide 0.005 to 0.1 Anson units (AU) of activity per gram of composition.

Optional Chelating Agents The detergent compositions herein may also optionally comprise a chelating agent that serves to chelate ions of metal, for example, iron and / or manganese. Said chelating agents therefore serve to form complexes with metal impurities in the composition that would otherwise tend to deactivate the components of the composition such as the peroxygen bleaching agent. Useful chelating agents may include aminocarboxylates, phosphonates, aminophosphonates, polyfunctionally substituted aromatic chelating agents, and mixtures thereof. Aminocarboxylates useful as optional chelating agents include ethylenediaminetetracetates, A / -hydroxyethyl-ethylenediaminetriacetates, nitrilotriacetates, ethylene diamine tetraproprionates, triethylenetetraamine hexacetates, dthylenetriaminepentaacetates, ethylenediamineadisuccinates and ethanololdiglicines. The alkali metal salts of these materials are preferred. The aminophosphonates are also suitable for use as chelating agents in the compositions of this invention when at least low levels of total phosphorus are acceptable in detergent compositions, and include ethylene diamine tetrakis (methylene phosphonates) as DEQUEST. Preferably, these aminophosphonates do not contain alkyl or alkenyl groups with more than about 6 carbon atoms. Preferred chelating agents include hydroxyethyldiphosphonic acid (hedp), diethylenetriamine penta acetic acid (DTPA), ethylenediamineedisuccinic acid (EDDS) and dipicolinic acid (DPA) and mixtures thereof. If used, the chelating agent can comprise from around 0. 1% to about 4% by weight of the compositions herein. More preferably, the chelating agent will comprise from about 0.2% to 2% by weight of the detergent compositions herein.

Thickening, Viscosity Control and / or Dispersing Agents Optional The detergent compositions herein may also optionally contain a polymeric material which serves to improve the ability of the composition to maintain its components in solid particles in suspension. Said materials therefore act as thickeners, viscosity control agents and / or dispersants. These materials are usually polymeric polycarboxylates but may include other polymeric materials such as polyvinylpyrrolidone (PVP) or polyamide resins. The 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 methiienmalonic acid. The presence of monomeric segments in the polymeric polycarboxylates herein, which do not contain carboxylate radicals such as vinyl methyl ether, styrene, ethylene, etc., is provided suitably so that said segments do not constitute more than about 40% by weight of the polymer. Particularly suitable polymeric polycarboxylates can be derived from acrylic acid. Said acrylic acid-based polymers which are useful herein are the water-soluble salts of the polymerized acrylic acid. The average molecular weight of such polymers in acid form is preferably in the range of from about 2,000 to 100,000, more preferably from about 2,000 to 10,000, even more preferably from about 4,000 to 7,000, and more preferably from about 4,000 to 5,000. The water-soluble salts of said acrylic acid polymers may include, for example, the alkali metal salts. Soluble polymers of this type are known materials. The use of polyacrylates of this type in detergent compositions has already been described, for example, in Diehl, the patent of E.U.A. No. 3,308,067, issued March 7, 1967. Such materials can also perform a detergency builder function. If used, thickeners, viscosity control agents and / or dispersants should be present in the compositions herein to the extent of from about 0.1% to 4% by weight. More preferably, said materials may comprise from about 0.5% to 2% by weight of the detergent compositions herein.

Optional 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. If used, dirt materials can contain approximately 0. 01% to about 50% by weight of the composition herein. The preferred soil remover and anti-redeposition agent is ethoxylated tetraethylenepentamine. Illustrative ethoxylated amines are more fully described in the U.S.A. 4,597,898, VanderMeer, issued July 1, 1986. Another group of preferred clay soil removers / anti-redeposition agents are the cationic compounds described in European patent application 111, 965, Oh and Gosselink, published on 27 June 1984. Other clay soil removers / anti-redeposition agents that may be used include the ethoxylated amine polymers described in European patent application 111, 984, Gosselink, published June 27, 1984; the zwitterionic polymers described in European patent application 112,592, Gosselink, published July 4, 1984; and the amine oxides which are described in the US patent. No. 4,548,744, Connor, issued October 22, 1985. Other clay removers and / or anti-redeposition agents known in the art can also be used in the compositions herein. Another type of anti-redeposition agent preferred includes the carboxylmethylcellulose (CMC) materials. These materials are well known in the art.

Peroxygen blanching agent with optional blanching activators Peroxygen bleaching agents can be organic or inorganic in nature. Inorganic peroxygen bleaching agents are often used in combination with a bleach activator. Useful organic peroxygen bleaching agents include percarboxylic acid bleaching agents and salts thereof. Suitable examples of this class of agents include magnesium monoperoxyphthalate hexahydrate, the magnesium salt of meta-chloro perbenzoic acid, 4-nonylamino-4-oxoperoxybutyric acid and diperoxydecanedioic acid. Said bleaching agents are described in the patent of E.U.A. No. 4,483,781, hartman, issued November 20, 1984; [European patent application EP-A-133,354, Banks, et al, published February 20, 1985; and the patent of E.U.A. No. 4,412,934, Chung et al, issued November 1, 1983. The most highly preferred bleaching agents include 6-nonylamino-6-oxoperoxycaproic acid (NAPAA) as described in the U.S. patent. No. 4,634,551, issued January 6, 1987, to Burns, et al.

The inorganic peroxygen bleaching agents can also be used in the detergent compositions herein. In fact, inorganic bleaching agents are preferred. Such inorganic peroxygen compounds include alkali metal perborate and percarbonate materials, more preferably percarbonates. For example, sodium perborate (for example, mono- or tetrahydrate) can be used. Suitable inorganic bleaching agents may also include sodium or potassium carbonate peroxyhydrate and equivalent "percarbonate" bleaches, sodium pyrophosphate peroxyhydrate, urea peroxyhydrate, and sodium peroxide. Persulfate bleach can also be used (for example, OXONE, manufactured commercially by Du Pont). Inorganic peroxygen bleaches will often be coated with water-soluble silicate, borate, sulfate or surfactants. For example, coated percarbonate particles are available from various commercial sources such as FMC, Solvay Interox, Tokai Denka and Degussa. Inorganic peroxygen bleaching agents, for example perborates, percarbonates, etc., are preferably combined with bleach activators, which leads to in situ production in aqueous solution (i.e., during the use of the compositions herein for washing / bleaching fabrics) of the peroxyacid corresponding to the bleach activator. Several non-limiting examples of activators are described in the U.S. patent. No. 4,915,854, issued April 10, 1990 to Mao et al.; and in the patent of E.U.A. No. 4,412,934, issued on November 1, 1 983 to Chung et al. The activators of nonaniloxybenzene sulfonate (NOBS) and tetraacetyl ethylenediamine (TAED) are typical. Mixtures thereof can also be used. See also the patent of E.U.A. No. 4,634,551 to which reference was made above, for other typical bleaches and activators useful herein. Other useful amide-derived bleach activators are those of the formulas: R) lp MN (^ DR5a \) ^ C (nO \) DR2'-C ^ (A0) \? L or D R1OO (? O \) MN (DR5 °) \ DR2 * -CC (0) L In that R1 is an alkyl group containing from about 6 to about 12 carbon atoms, R2 is an alkylene containing from 1 to about 6 carbon atoms, R5 is H or alkyl, aryl, or aralkyl containing from about 1 to about 10 carbon atoms, and L is any suitable residual group, for example, oxybenzene sulfonate, -OOH, -OOM. A residual group is any group that is displaced from the bleach activator as a consequence of the nucleophilic attack on the bleach activator by the perhydrolysis anion. A preferred residual group is phenol sulfonate. Preferred examples of bleach activators of the above formulas include (6-octanamido-caproyl) oxybenzenesulfonate, (6-nonamido-caproxy) oxybenzenesulfonate, (6-decanamido-caproyl) oxybenzenesulfonate, and mixtures thereof as described in the US Pat. USA No. 4,634,551 which was referred to above. Said mixtures are characterized herein as (C8-C6alkyl 0-caproyl) oxybenzene sulfonate. Another class of useful bleach activators comprises the benzoxazine activators described by Hodge et al, in the U.S. patent. No. 4,966,723, issued October 30, 1990, incorporated herein by reference. A highly preferred benzoxazine type activator is: Still another class of useful bleach activators includes lactam activators, especially acyl caprolactams and acyl valerolactams of the formulas: Where R is H or an alkyl, aryl, alkoxyaryl, or alkaryl group containing 1 to about 12 carbon atoms. Highly preferred lactam activators include benzoyl caprolactam, octanoyl caprolactam, 3,5,5-trimethylhexanoyl caprolactam, nonanoyl caprolactam, decanoyl caprolactam, undecenoyl caprolactam, benzoyl valerolactam, octanoyl valerolactam, decanoyl valerolactam, undecenoyl valerolactam, 3,5,5- trimethylhexanoyl valerolactam, and mixtures thereof. See also the patent of E.U.A. No. 4,545,784, issued to Sanderson, October 8, 1985, incorporated herein by reference, which discloses acyl caprolactams, including benzoyl caprolactams, absorbed in sodium perborate. If peroxygen bleaching agents are used, they will generally comprise from about 0.1% to 30% by weight of the composition. More preferably, the peroxygen bleaching agent will be present to the extent of about 5% to 20% by weight of the composition. If used, the bleach activators may comprise from about 0.5% to 20%, more preferably from about 3% to 10% by weight of the composition. Frequently, the activators are used so that the molar ratio of bleaching agent to activator is in the range of about 1: 1 to 10: 1, more preferably of about 1.5: 1 to 5: 1. In addition, it has been found that bleach activators, when agglomerated with certain acids such as citric acid, are more chemically stable.

Optional whitening catalysts If desired, the catalyst compounds can be catalyzed by means of a manganese compound. Such compounds are well known in the art and include, for example, the manganese-based catalysts described in the U.S.A. No. 5,246,621, patent of E.U.A. Do not. ,244,594; patent of E.U.A. No. 5,194,416; patent of E.U.A. No. 5,114,606; and published European patent applications Nos. 549,271 A1, 549,272A1, 544,440A2, and 544,490A1. Preferred examples of these catalysts include MnlV2 (u-0) 3 (1) 4,7-trimethyl-1, 4,7-triazacyclononane) 2- (PF5) 2, Mn '|| 2 (u-0) - | (u- OAc) 2 (1, 4,7-trimetiM, 4,7-triazacyclononane) 2- (Cl? 4) 2, Mn'V4 (u-0) e (1, 4,7-triazacyclononane) 4- (Cl? 4) 2, (u-OAc) 2 (1, 4,7-trimethyl-1, 4,7-triazacyclononane) 2- (Cl 4) 3 Mn'v (1,4,7-trimethyl-1,4,7-triazacyclononane ) - (OCH3) 3 (PFß) j and mixtures thereof. Other metal-based bleach catalysts include those described in the U.S.A. No. 4,430,243 and the patent of E.U.A. No. 5,114,611. The use of manganese with several complex ligands to improve bleaching is also reported in the following U.S. 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. As a practical aspect, and not by way of limitation, the compositions and methods herein can be adjusted to provide on the order of at least one part per ten million of the active bleach catalyst species in the washing medium. water, and preferably will provide from about 0.1 ppm to about 700 ppm, more preferably from about 1 ppm to about 500 ppm, of the bleach catalyst species in the wash liquor. Cobalt-based 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 catalysts useful herein are cobalt pentamine acetate salts having the formula [ Co (NH3) 5OAc] Ty, in which "Oac" represents an acetate portion, and "Ty" is an anion, and especially cobalt pentaminacetate chloride, [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"). Those cobalt-based catalysts are readily prepared by known methods, such as taught for example in Tobe's article and references cited therein, in the U.S. Patent No. 4,810,410, to Diakun et al, issued March 7, 1989, J. Chem. Ed. (1989), 66 (12), 1043-45; The Synthesis and Characterization of Inorganic Compounds, WL Jolly, (Prentice-Hall; 1979), pp. 461-3; Inorg. Chem., 18, 1497-1502 (1979); Chem .. 21, 2881-2855 (1982); Inorg. Chem. 18, 2023-2025 (1979); Inorganic Synthesis, 173-176 (1960); and Journal of Phvsical Chemistrv. 56, 22-25 (1952). As a practical aspect, and not by way of limitation, the compositions and methods of the present may be adjusted to provide on the order of at least one part per one hundred million of the active bleach catalyst species in the washing medium. aqueous, and preferably will provide from about 0.01 ppm to about 25 ppm, more preferably from about 0.05 ppm to about ppm, and more preferably from about 0.1 ppm to about 5 ppm, of the bleach catalyst species in the wash solution. In order to obtain such levels in the washing solution of an automatic washing process, typical compositions herein will comprise from about 0.0005% to about 0.2%, more preferably from about 0.004% to about 0.08%, of bleach catalyst , especially manganese or cobalt catalysts, by weight of the cleaning compositions.

Polishes, suppressors of foams, dyes and / or optional perfumes The detergent compositions herein can also optionally contain polishes, foam suppressants, dyes and / or perfumes. Such brighteners, suds suppressors, silicone oils, dyes and perfumes must be compatible and non-reactive, of course, with the other components of the composition in a non-aqueous environment. If present, the brighteners, foam suppressors, colorants and / or perfumes will typically comprise from about 0.0001% to 2% by weight of the compositions present.

Polymeric dirt release agent Any polymeric soil release agent known to those skilled in the art can optionally be used in the compositions and methods of this invention. The polymeric soil release agents are characterized by having both hydrophilic segments, to hydrophilize the surface of the hydrophobic fibers, such as polyester and nylon, and hydrophobic segments to be deposited on hydrophobic fibers and to remain adhered thereto through the completion of the washing and rinsing cycles, 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. Examples of polymeric soil release agents useful herein include the U.S.A. No. 4,721, 580, of January 26, 1988 to Gosselink; the patent of E.U.A. No. 4,000,093, of December 28, 1976 to Nicol, et al; European patent application 0 219 048, published on April 22, 1987 by Kud et al; the patent of E.U.A. 4,702,857, dated October 27, 1987 to Gosselink; the patent of E.U.A. No. 4,968,451, issued November 4, 1990 to J.J. Scheibel. Commercially available soil release agents include the SOKALAN type material, for example SOKALAN HP-22, available from BASF, Germany. See also the patent of E.U.A. No. 3,959,230 to Hays of May 25, 1976 and the patent of E.U.A. No. 3,893,929 to Basadur, July 8, 1975. Examples of this polymer include commercially available material ZELCON 5126 from Dupont and MILEASE T from ICI. Other suitable polymeric soil release agents include the terephthalate polyesters of the U.S.A. No. 4,711, 730 issued December 8, 1987 to Gosselink et al., The blocked end anionic oligomeric esters of the U.S. patent. No. 4,721, 580, issued January 26, 1988 to Gosselink et al, and the oligomeric polyester block compounds of the U.S.A. No. 4,702,857, issued October 27, 1987 to Gosselink. Preferred polymeric soil release agents also include the soil release agents of the U.S.A. No. 4,877,896, issued on October 31, 1989 to Maldonado et al. If used, the soil release agents will generally comprise from about 0.01% to about 10.0%, by weight of the detergent compositions herein, typically from about 0.1% to about 5%, preferably from about 0.2% to about 3.0% .

Chelating Agents The detergent compositions herein may also optionally contain one or more iron and / or manganese chelating agents. Such chelating agents can be selected from the group consisting of aminocarboxylates, aminophosphonates, polyfunctionally substituted aromatic chelating agents, and mixtures thereof, all as they are defined here above. Without wishing to be bound by theory, it is believed that the benefit of these materials is due in part to their exceptional ability to remove iron and manganese ions from the wash solutions by formation of soluble chelates. Aminocarboxylates useful as optional chelating agents include ethylenediamine tetracetates, N-hydroxyethylethylenediamine triacetates, nitrile triacetates, ethylenediamine tetraproprionates, triethylenetetraamine hexacetates, diethylenetriamine pentaacetates, and ethanoldiglicines, alkali metal, ammonium, and substituted ammonium salts of the same and mixtures thereof. Aminophosphonates are also suitable for use as chelating agents in the compositions of the invention when at least low levels of total phosphorus are acceptable in detergent compositions., and include ethylene diamine tetrakis (methylene phosphonates) as DEQUEST. Preferably, these aminophosphonates do not contain alkyl or alkenyl groups with more than 6 carbon atoms. Polyfunctionally substituted aromatic chelating agents are also useful in the compositions herein. See the patent of E.U.A. ?or. 3,812,044, issued May 21, 1974, to Connor et al. Preferred compounds of this type in acid form are the dihydroxydisulfobenzenes such as 1,2-dihydroxy-3,5-di-sulfobenzene. A preferred biodegradable chelator for use herein is ethylene diamine disuccinate ("EDDS"), especially the isomer [S, S] as described in the patent of E.U.A. 4,704,233, from November 3, 1987, to Hartman and Perkins. If used, the chelating agents will preferably comprise from about 0.1% to about 10% by weight of the detergent compositions herein. More preferably, if used, the chelating agents will comprise from about 0.1% to about 3.0% by weight of said compositions.

Clay soil removal / 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. Liquid detergent compositions typically contain about 0.01% or about 5% of those compositions. The most preferred soil remover and anti-redeposition agent is ethoxylated tetraethylenepentamine. Illustrative ethoxylated amines are more fully described in the U.S.A. 4,597,898, VanderMeer, issued July 1, 1986. Another group of clay soil removers / anti-redeposition agents are the cationic compounds described in European patent application 1 11, 965, Oh and Gosselink, published on 27 June 1984. Other clay soil removers / anti-redeposition agents that can be used include the ethoxylated amine polymers described in European Patent Application 111, 984, Gosselink, published on June 27, 1984; the zwitterionic polymers described in European patent application 112,592, Gosselink, published July 4, 1984; and the amine oxides which are described in the US patent. No. 4,548,744, Connor, issued October 22, 1985. Other clay removers and / or anti-redeposition agents known in the art can also be used in the compositions herein. Another type of preferred anti-redeposition agent includes the carboxylmethylcellulose (CMC) materials. These materials are well known in the art.

Polymeric Dispersing Agents Polymeric dispersing agents can be used advantageously at levels from 0.1% to about 7%, by weight, in the compositions herein, especially in the presence of zeolite builders 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 it is not desired to be limited by theory, that dispersing polymeric agents improve the overall performance of the builder, when used in combination with other builders (including lower molecular weight polycarboxylates) by growth inhibition. of crystal, peptization of release of dirt into particles, and anti-redeposition.

The 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 monomeric segments in the polymeric polycarboxylates herein, which do not contain carboxylate radicals such as vinyl methyl ether, styrene, ethylene, etc., is suitably provided so that said segments do not constitute more than about 40% by weight. Particularly suitable polymeric polycarboxylates can be derived from acrylic acid. Said acrylic acid-based polymers which are useful herein are the water-soluble salts of the polymerized acrylic acid. The average molecular weight of said polymers in acid form is preferably in the scale of about 2, 000 to 10,000, more preferably from about 4,000 to 7,000, and more preferably from about 4,000 to 5,000. The water-soluble salts of said acrylic acid polymers may include, for example, the alkali metal, ammonium and substituted ammonium salts. Soluble polymers of this type are known materials. The use of polyacrylates of this type in detergent compositions has already been described, for example, in Diehl, U.S. Pat. No. 3,308,067, issued on March 7, 1967.

Acrylic / maleic based copolymers can 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 acid form is preferably in the range of from about 2,000 to 100,000, more preferably from about 5,000 to 75,000, more preferably from about 7,000 to 65,000. The ratio of acrylate to maleate segments in said copolymers will preferably be in the range of from about 30: 1 to about 1: 1, more preferably from about 10: 1 to 2: 1. The water-soluble salts of said copolymers of acrylic acid and maleic acid may include, for example, the alkali metal, ammonium and substituted ammonium salts. Soluble acrylate / maleate copolymers of this type are known materials which are described in European Patent Application No. 66,915, published on December 15, 1982, as well as in EP 193,360, published on September 3, 1986, which also describes said polymers comprising hydroxypropylacrylate. Still other useful dispersing agents include maleic / acrylic / polyvinyl alcohol terpolymers. Such materials are also described in EP 193,360, including, for example, the terpolymer 45/45/10 of maleic / acrylic / polyvinyl 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. The scale Typical molecular weight for these purposes is in the range of from about 500 to about 100,000, preferably from about 1,000 to about 50,000, more preferably from about 1,500 to about 10,000. The dispersing agents of polyaspartate and polyglutamate, especially in conjunction with zeolite builders, can also be used. Dispersing agents such as polyaspartate preferably have a molecular weight (avg.) Of about 10,000.

Dye transfer inhibition agents The compositions herein may also include one or more materials effective to inhibit the transfer of dyes from one fabric to another during the cleaning process. Generally, said dye transfer inhibiting agents include polyvinylpyrrolidone polymers, polyamine N-oxide polymers, copolymers of N-vinylpyrrolidone and N-vinylimidazole, manganese phthalocyanine, peroxidase, and mixtures thereof. If used, these agents will typically comprise from about 0.01% to about 10% by weight of the composition, preferably from about 0.01% to about 5%, and more preferably from about 0.05% to about 2%. More specifically, the preferred polyamine N-oxide polymers for use herein contain units having the following structural formula: R-Ax-P; in which P is a polymerizable unit to which an N-O group may be adhered or the N-O group may be part of the polymerizable unit or the N-O group may be attached to both units; A is one of the following structures: -NC (O) -, -C (0) 0, -S-, -O-, -N =; x is 0 or 1; and R are aliphatic, aliphatic, ethoxylated, aromatic, heterocyclic or alicyclic groups or any combination thereof to which the nitrogen of the N-O group may be attached or the N-O group is part of these groups. Preferred polyamine N-oxides are those in which R is a heterocyclic group such as pyridine, pyrrole, imidazole, pyrrolidine, piperidine and derivatives thereof. The N-O group can be represented by the following general structures: wherein Ri, R2 and R3 are aliphatic, aromatic, heterocyclic or alicyclic groups or combinations thereof, x, y, and z are 0 or 1; and the nitrogen of the N-O group may be attached or be part of any of the groups mentioned above. The amine oxide unit of the polyamine N-oxides has a pKa < 10, preferably pKa < 7, more preferred pKa < 6. Any polymer base structure can be used as long as the formed amine N-oxide polymer is water-soluble and has dye transfer inhibition properties. Examples of suitable polymeric base structures are polyvinyls, polyalkylenes, polyesters, polyethers, polyamide, polyimides, polyacrylates and mixtures thereof. These polymers include block or random copolymers wherein one type of monomer is an amine N-oxide and the other type of monomer is an N-oxide. The amine N-oxide polymers typically have an amine to amine N-oxide ratio of 10: 1 to 1: 1,000,000. However, the number of amine oxide gropresent in the polyamine oxide polymer can be varied by suitable copolymerization or by a suitable degree of N-oxidation. Polyamine oxides can be obtained in almost any degree of polymerization. Typically, the average molecular weight is within the range of 500 to 1,000,000 more preferred from 1,000 to 500,000; most preferred from 5,000 to 100,000: This preferred class of materials can be referred to as "PVNO". The most preferred polyamine N-oxide useful in the detergent compositions herein is poly (4-vinylpyridine-N-oxide) which has an average molecular weight of about 50,000 and an amine to amine N-oxide ratio of about 1: 4 Copolymers of N-vinylpyrrolidone and N-vinylimidazole polymers (referred to as a "PVPVI" class) are also preferred for use herein. Preferably the PVPVI have an average molecular weight scale of 5,000 to 50,000, more preferably 5,000 to 200,000, and more preferably 10,000 to 20,000. (The average molecular weight scale is determined by light scattering as described in Barth, et al, Chemical Analysis, vol 113. "Modern Methods of Polymer Characterization", the description of which is incorporated herein by reference). The PVPVI copolymers typically have a molar ratio of N-vinylimidazole to N-vinylpyrrolidone from 1: 1 to 0.2: 1, more preferably from 0.8: 1 to 0.3: 1, more preferably from 0.6: 1 to 0.4: 1. These copolymers can be linear or branched. The compositions of the present invention may also use polyvinylpyrrolidone ("PVP") having an average molecular weight of from about 5,000 to about 400,000, preferably from about 5,000 to about 200,000, and more preferably from about 5,000 to about 50,000. PVP's are known to experts in the field of detergents; see, for example, EP-A-262,897 and EP-A-256,696, incorporated herein by reference. The PVP-containing compositions may also contain polyethylene glycol ("PEG") having an average molecular weight of from about 500 to about 100,000, preferably from about 1,000 to about 10,000. Preferably, the ratio of PEG to PVP based on ppm delivered in wash solutions is from about 2: 1 to about 50: 1, and more preferably from about 3: 1 to about 10: 1. The detergent compositions herein may also optionally contain from about 0.005% to 5% by weight of certain types of hydrophilic optical brighteners that also provide a dye transfer inhibiting action. If they are used, the compositions of the present will preferably comprise from about 0.01% to 1% by weight of said optical brighteners. The hydrophilic optical brighteners useful in the present invention are those having the structural formula: wherein R-] is selected from anilino, N-2-bis-hydroxyethyl and NH-2-hydroxyethyl; R 2 is selected from N-2-bis-hydroxyethyl, N-2-hydroxyethyl-N-methylamino, morphino, chloro and amino; and M is a salt-forming cation such as sodium or potassium. When in the above formula, R ^ is anilino, R2 is N-2-bis-hydroxyethyl and M is a cation such as sodium, the brightener is 4,4'-bis [(4-anilino-6- ( N-2-b-Sihydroxyethyl) -s-triazin-2-yl) amino] -2,2'-stilbenedisulfonic acid and the disodium salt. This particular brightener species is marketed under the trade name Tinopal UNPA-GX by Ciba-Geigy Corporation. The Tinopal UNPA-GX is the preferred hydrophilic optical brightener useful in the detergent compositions herein. When in the above formula R-] is anilino, R2 is N-2-hydroxyethyl-N-2-methylamino and M is a cation such as sodium, the brightener is the disodium salt of 4,4'-bis [4] -anilino-6- (N-2-hydroxyethyl-N-methylamino) -s-triazin-2-yl) amino] -2,2'-stilbenedisulfonic acid. This particular kind of brightener is marketed commercially under the trade name Tlnopal 5BM-GX by Ciba-Geigy Corporation. When in the previous formula R < | is anilino, R2 is morphino and M is a cation such as sodium, the brightener is the sodium salt of 4,4'-bis [(4-anilino-6-morphino-s-triazin-2-yl)] amino] 2,2'-stilbenedisulfonic acid. This particular kind of brightener is sold commercially under the trade name Tinopal AMS-GX by Ciba-Geigy Corporation. The specific optical brightener species selected for use in the present invention provides especially effective dye transfer inhibition benefits when used in combination with the selected polymeric dye transfer inhibition agents described herein above. The combination of said selected polymeric materials (e.g., PVNO and / or PVPVI) with said selected optical brighteners (e.g., Tinopal UNPA-GX, Tinopal 5BM-GX and / or Tinopal AMS-GX) provides significant dye transfer inhibition. better in aqueous washing solutions than any of these two components of detergent composition achieves when used alone. Without being limited by theory, it is believed that such brighteners work in this manner because they have high affinity for fabrics in the wash solution and therefore they deposit relatively fast on those fabrics. The degree to which the brighteners are deposited on fabrics in the washing solution can be defined by a parameter called the "exhaustion coefficient". The depletion coefficient is in general as the ratio of a) the polishing material deposited on a cloth a b) the initial concentration of polish in the washing liquid. Brighteners with relatively high depletion coefficients are most suitable for inhibiting dye transfer in the context of the present invention. Of course, it will be appreciated that other types of conventional optical brightener compounds can optionally be used in the compositions herein to provide conventional "gloss" fabric benefits, rather than a true dye transfer inhibition effect. Said use is conventional and well known for detergent formulations.

FORM OF COMPOSITION The heavy-duty water-based liquid detergent compositions described herein may contain water and other solvents as carriers. The low molecular weight primary and secondary alcohols exemplified by methanol, ethanol, propanol and isopropanol are suitable. Monohydric alcohols are preferred to solubilize the 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 said carriers.

The detergent compositions herein will preferably be formulated so that, during use in aqueous cleaning operations, the wash water will have a pH of between about 6.5 and about 11, preferably between about 7.5 and 11. The techniques for controlling the pH Recommended levels of use include the use of pH, alkali, acid regulators, etc., and are well known to those skilled in the art.

Preparation and use of the composition. The heavy-duty water-based liquid detergent compositions of the present invention can be made by mixing and combining the desired ingredients with the desired solvent. In a typical procedure for preparing said compositions, the essential components and certain preferred optionals will be combined in a particular order and under certain conditions. The compositions of this invention, prepared as described above, can be used to form aqueous wash solutions for use in washing and bleaching fabrics. Generally, an effective amount of said compositions is added to water, preferably in a conventional automatic fabric washing machine, to form said washing / bleaching solutions. The aqueous wash / bleach solution formed in this manner is then contacted, preferably under agitation, with the fabrics which will be washed and bleached therewith.

An effective amount of the liquid detergent compositions herein that is added to water to form wash / bleach solutions may comprise sufficient amounts to form about 500 to 7,000 ppm of composition in aqueous solution. More preferably, about 800 to 3,000 ppm of the detergent compositions herein will be provided in aqueous wash / bleach solution. The following examples illustrate the preparation and performance advantages of the modified alkyl benzene sulfonate surfactant mixtures containing the aqueous liquid detergent compositions of the present invention. However, said examples do not necessarily mean that they limit or define in any other way the scope of the present invention. All parts, percentages and relationships used in the presentation are expressed as a percentage by weight unless otherwise specified. In the following examples, the abbreviations for the various ingredients that are used for the compositions have the following meanings. In the following examples, the following abbreviation is used for a modified alkylbenzene sulfonate, sodium salt form or potassium salt form, prepared according to any of the preceding process examples: MLAS.

ABBREVIATIONS LAS: Linear sodium alkylbenzene sulfonate MBASX: Primary sodium alkylsulfate branched in the middle part of its chain (average total carbon = x) MBAEXSZ: Primary sodium alkyl sulphate branched in the middle part of its chain (average total carbon = x) ethoxylated ( EO average = x), sodium salt. MBAEX Alkylated ethoxylate (average EO = x) branched primary in the middle part of its chain (average total carbons = x).

Endolase: Endoglunase enzyme activity 3000CEVU / g sold by Novo Industries PS MEA: Monoethanolamine PG: Propanediol BPP: Butoxy-propoxy-propanol EtOH: Ethanol NaOH: Sodium hydroxide solution NaTS: Sodium toluene sulfonate Citric acid: Anhydrous citric acid CxyFA: Fatty acid of C1x-C1y CxyEz: A primary alcohol of C- | xC 'an average of z moles of ethylene oxide Carbonate: Anhydrous sodium carbonate with a size of average particle of 200μm and 900μm Citrate: Trisodium citrate dihydrate of 86.4% activity with a particle size distribution of between 425μm and 850μm TFAA: N-methylglucamide of alkyl of C ^ Q- ^ Q LMFAA: alkyl N-methylglucamide of C? 2-14 APA: C8-C10 amidopropyldimethylamine Fatty acid (C12 / 14) C12-C14 fatty acid Fatty acid (TPK) Fatty acid of palm kernel blocked Fatty acid (RPS): Fatty acid of colaza seed. Borax: Decahydrate tetraborate of Na PAA: Polyacrylic acid (MW = 4500) PEG: Polyethylene glycol (MW = 4600) MES: Estersulfonate alchemyl ether SAS: Alkylsulfate secondary NaPS: Paraffinsulfonate of sodium C45AS: Alkylsulphate linear of sodium of C14-C15 CxyAS: Alkylsulphate of sodium (or other salt if specified) of C- | xC-jy CxyEzS: Sodium alkylsulfate of C-jx-C- | and condensed with z moles of ethylene oxide (or other salt if specified) AQA: R2.N + (CH3) x ((C2H4?) And H) z with R2 = CQ-C ^ Q X + Z = 3, x = 0 to 3, z = 0 to 3, y = 1 to 15.

STPP: Anhydrous sodium tripolyphosphate Zeolite A: Hydrated sodium aluminosilicate of the formula Na? 2 (A102Si? 2) i2- 27H 0, which has a primary particle size on the scale of 0.1 to 10 micras NaSKS-6: Stratified silicate crystalline of the formula d-Na2Si2? 5 Carbonate: Anhydrous sodium carbonate with an average particle size between 200μm and 900μm Bicarbonate Anhydrous sodium bicarbonate with a particle size distribution between 400μm and 1200μm Silicate: Amorphous sodium silicate (Si? 2 ratio: Na20 = 2.0) Sulphate : Anhydrous sodium sulfate PAE: Ethoxylated tetraethylene pentaamine (15-18) PIE: Ethoxylated polyethylenimine PAEC: Diethylentriamine ethoxylated methylated quaternized MA / AA: Copolymer of 1: 4 maleic / acrylic acid, average molecular weight approximately 70,000 CMC: Sodium Carboxymethylcellulose Protease: Proteolytic enzyme of activity 4KNPU / g sold under the trade name Savinase by Novo Industries A / S Cellulase: Cellulite enzyme of activity 1000CEVU / g sold by Novo Industries A / S under the trade name Carezyme Amylase: amyolitic enzyme of activity 60KNU / g sold by Novo Industries A / S under the trade name Termamyl 120T Lipase: Lipolytic enzyme of activity 100kLU / g sold by Novo Industries A S under the trade name Lipolase PB1: Anhydrous sodium perborate bleach of nominal formula NaB 2-H2 2 Percarbonate: Sodium percarbonate of nominal formula 2Na2C03.3H202 NaDCC: Sodium dichloroisocyanurate NOBS: Nonanoyloxybenzenesulfonate in the form of sodium salt TAED: Tetraacetylethylenediamine DTPMP: Diethylenetriaminpenta (methylene phosphonate) marketed by Monsanto under the trade name Dequest 2060. Photoactivated bleach: Sulfonated zinc phthalocyanine bleach encapsulated in dextrin-soluble polymer Brightener 1: 4,4'-bis (2-sulfoestyl) biphenyl disodium Brightener 2: 4,4, -b, (4-anilino-6-morpholino-1,3,5-triazin-2-yl) amino) stilben -2: 2'-disodium disulfonate HEDP: 1, 1-hydroxydanediphosphonic acid SRP 1: Esters of end blocked with sulfobenzoyl with structure of base of oxyethylenexl and terephthaloyl SRP 2. Polymer of sulfonated ethoxylated terephthalate SRP 3: Polymer of ethoxylated terephthalate methyl blocked Antifoams Silicone: Polydimethylsiloxane foam controller with a siloxane-oxyalkylene copolymer as a dispersing agent with a ratio of said foam controller to said dispersing agent from 10: 1 to 100: 1. Isofol 16: Trademark of Condea for Guerbet alcohols of C16 (average) CaCl2: Calcium chloride MgCl2: Magnesium chloride DTPA: Diethylenetriaminepentaacetic acid EXAMPLE 18 The liquid detergent compositions are made according to the following: It was discovered that the above liquid detergent compositions (A-D) are very efficient in removing a wide range of fabric stains and soils under various conditions of use.

EXAMPLE 19 The following compositions (E to J) are heavy duty aqueous laundry detergent compositions for laundry according to with the present invention.

The following examples illustrate water-based liquid detergent compositions according to the present invention.

EXAMPLE 20 Aqueous heavy-duty water-based liquid laundry detergent compositions F to J which comprise the branched surfactants in the middle part of their chain are presented hereinafter. invention.

EXAMPLE 21 The following aqueous laundry liquid laundry detergent compositions K to O are prepared according to the invention: EXAMPLE 22 The following aqueous liquid laundry detergent compositions P a T are prepared according to the invention.

EXAMPLE 23 Next, heavy-duty laundry-based liquid laundry detergent compositions comprising the branched surfactants in the middle part of their chain of the present invention are presented.

Examples of additional syntheses EXAMPLE 24 Mix of linear and branched alkylbenzene With a 2/3-phenyl index of about 200 and a 2-methyl-2-phenyl index of about 0.02 (mixture of alkylbenzene according to the invention) 110. 25 g of the substantially monomethyl branched olefin mixture of example 2, 36 g of an unbranched olefin mixture (decene: undecene: dodecene: tridecene ratio of 2: 9: 20: 18) and 36 g of a zeolite catalyst selective form (zeolite beta acid catalyst Zeocat® PB / H) 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 17.5 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 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 collection of benzene. 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 are 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). A mixture of substantially monomethyl branched alkylbenzene with a 2/3-phenyl index of about 200 and a 2-methyl-2-phenyl index of about 0.02 is collected from 76 ° C-130 ° C (167 g).

EXAMPLE 25 Mixture of modified alkylbenzenesulfonic acid according to the invention (mixture of branched and unbranched alkylbenzenesulfonic acid) with a 2/3-phenyl number of about 200 and a 2-methyl-2-phenyl index of about 0.02.

The modified alkyl benzene mixture of Example 24 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 200 and a 2-methyl-2-phenyl index of about 0.02.

EXAMPLE ^ ß Mixture 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 200 and a 2-methyl-2-index phenyl of about 0.02 The modified alkenylbenzene sulfonic acid of example 25 is neutralized with one molar equivalent of sodium methoxide in methanol and the methanol is evaporated to give 225 g of a modified alkylbenzene sulfonate mixture, sodium salt with a 2/3-phenyl index of about 200 and a 2-methyl-2-phenyl index of about 0.02.

EXAMPLE 27 The detergent compositions as in Examples 18-23 are repeated, substituting MLAS with the product of Example 25.

Claims (28)

NOVELTY OF THE INVENTION CLAIMS

1. A heavy-duty water-based liquid detergent composition comprising: (i) from 5% to 70% by weight of the composition, of a mixture of modified alkylbenzenesulfonate surfactants comprising: (a) from 15% to 99% by weight of surfactant mixture, of a mixture of branched alkylbenzene sulphonates having the formula (I): T R7L [Mq®] b SO, (I) wherein 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 about 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 C? -C3 alkyl; R2 is selected from H and C? -C3 alkyl; A is a benzene portion; and (b) from 1% to about 85% by weight of surfactant mixture, of a mixture of unbranched alkylbenzene sulphonates having the formula (II): (II) wherein 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 has an average aliphatic carbon content of about 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 160 to 275; (ii) From 0.1 to 8% of a co-surfactant composition selected from the group consisting of fatty acid alkyl polyhydroxy, alkylamidopropyl dimethylamine and mixtures thereof; and (ii) From 30% to 95% of an aqueous liquid carrier; wherein said composition is further characterized by a 2/3-phenyl index of 160 to 275.

2.- The detergent composition in accordance with the claim 1, further characterized in that said M is selected from H, Na, K and mixtures thereof, said a = 1, said b = 1, said q = 1, and said mixture of modified alkylbenzene sulfonate surfactants has an index 2 - methyl-2-phenyl of less than 0.3.

3. The detergent composition in accordance with the claim 2, further characterized in that said 2-methyl-2-phenol index is from 0 to 0.1.

4. The detergent composition in accordance with the claim 3, further characterized in that said mixture of modified alkyl benzene sulphonate surfactants is the product of a process using a beta zeolite as a catalyst.

5.- The detergent composition in accordance with the claim 4, further characterized in that said catalyst is in at least partially acidic form.

6. The detergent composition according to claim 2, further characterized in that it consists essentially of said mixture of branched alkylbenzenesulfonates and unbranched alkylbenzene sulfonates, wherein said 2-methyl-2-phenyl index of the mixture of modified alkyl benzene sulfonate surfactants is less than 0.1, and in which in said mixture of branched and unbranched alkylbenzenesulfonates, the average aliphatic carbon content is from 1.1 to 12.0 carbon atoms; said R1 is methyl; R2 is selected from H and methyl with the proviso that 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 also in the which in said mixture of unbranched alkylbenzene sulphonates, Y has a sum of carbon atoms of 10 to 14 carbon atoms, the average aliphatic carbon content of the unbranched alkylbenzene sulphonates is 11.0 to 12.0 carbon atoms, and said M is a monovalent cation or mixture of selected cations of H, Na and mixtures thereof.

7 '.- A heavy-duty water-based liquid detergent composition comprising: (i) a mixture of modified alkylbenzene sulfonate surfactants comprising the product of a process comprising the steps of: (I) alkylating benzene with a mixture of alkylation in the presence of a zeolite beta catalyst; (ll) 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 the alkylation mixture of branched Cg-C2o monoolefins having structures identical to 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 alkyl from Ci to C3; and (b) from 0.1% to 85%, by weight of the alkylation mixture of C9-C2o linear aliphatic olefins; wherein said alkylation mixture contains said branched C9-C20 monoolefins having at least two different carbon numbers on said C9-C2o 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; (ii) From 0.1 to 8% of a co-surfactant composition selected from the group consisting of alkyl polyhydroxy fatty acid amide, alkylamidopropyl dimethylamine and mixtures thereof; and (iii) 30% to 95% of an aqueous liquid carrier; wherein said composition is further characterized by a 2/3-phenyl index of from 160 to 275.

8. A heavy-duty water-based liquid detergent composition comprising: (i) a mixture of modified alkylbenzene sulfonate surfactants consisting of essentially the product of a process comprising the steps, in sequence, of: (I) alkylating benzene with an alkylation mixture in the presence of a zeolite beta catalyst; (ll) 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 the alkylation mixture of a branched alkylating agent selected from the group consisting of: (A) internal monoolefins of Cg-C2o of R1LR2 in which L is an olefinic acyclic portion consisting of carbon and hydrogen and containing two terminal methyls; (B) Cg-C20 alpha monoolefins of R1AR2 wherein A is an alpha-olefinic acyclic moiety consisting of carbon and hydrogen and containing a methyl terminal and an olefinic methylene terminus; (C) C9-C2o vinylidene monoolefins of R1BR2 in which B is an acyclic vinylidene olefin moiety consisting of carbon and hydrogen and containing two methyl terminals and an internal olefinic methylene; (D) C9-C2o primary alcohols of R1QR2 in which Q is an aliphatic acyclic terminal alcohol moiety consisting of carbon, hydrogen and oxygen and contains a methyl terminal; (E) C9-C20 primary alcohols of R1ZR2 in which Z is a portion of alcohol non-aliphatic primary acyclic terminal consisting of carbon, hydrogen and oxygen and contains two methyl terminals; and (F) mixtures thereof; wherein in any of (A) - (F) said R1 is Ci to C3 alkyl and R2 is selected from H and Ci to C3 alkyl; and (b) from 0.1% to 85%, by weight of the alkylation mixture of a C9-C20 linear alkylating agent selected from linear C9-C2 aliphatic olefins, 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 Cg-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; (ii) From 0.1 to 8% of a co-surfactant composition selected from the group consisting of fatty acid alkyl polyhydroxy, alkylamidopropyl dimethylamine and mixtures thereof; and (iii) 30% to 95% of an aqueous liquid carrier; wherein said composition is further characterized by a 2/3-phenyl index of 160 to about 275.

9. The detergent composition according to claim 8, further characterized in that said alkylation mixture consists essentially of: (a) 0.5% to 47.5%, by weight of the alkylation mixture of said branched alkylating agent selected from: (G) Cg-Cu internal monoolefins of R1LR2 in which L is an olefinic acyclic portion consisting of carbon and hydrogen and contains two terminal methyls; (H) alpha C9-Cu monoolefins of R1AR2 in which A is an acyclic portion alpha-oleifin consisting of carbon and hydrogen and containing a methyl terminal and an olefinic methylene terminal; and (J) mixtures thereof; wherein in any of (G), (H) and (J) said 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 the mixture of linear aliphatic olefins of C9-d4; and (c) from 50% to 98.9% by weight of the alkylation mixture of selected carrier materials of paraffins and inert non-paraffin solvents; wherein said alkylation mixture contains the branched alkylating agents having at least two different carbon numbers on said Cg-Cu scale, and has an average carbon content of 11.0 to 12.0 carbon atoms; and wherein said components (a) and (b) are in a weight ratio of 51:49 to 90:10.

10. The detergent composition according to claim 9, further characterized in that in step (II) comprises the removal of components other than monoalkylbenzene before contacting the product of step (I) with a sulfonation agent.

11. The detergent composition according to claim 9, further characterized in that a hydrotrope, hydrotrope precursor, or mixtures thereof are added after step (I).

12. The detergent composition according to claim 9, further characterized in that a hydrotrope, hydrotrope precursor, or mixtures thereof are added during or after step (II) and before step (III).

13. - The detergent composition according to claim 9, further characterized in that a hydrotrope is added during or after step (III).

14. The detergent composition according to claim 9, further characterized in that the zeolite beta acid catalyst is a calcined beta zeolite catalyst treated with HF.

15. The detergent composition according to claim 9, further characterized in that in step (I) the alkylation is carried out at a temperature of 125 ° C to 215 ° C, at a pressure of 3.51 kg / cm2 gravimetric at 7.03 kg / cm2 gravimetric.

16. The detergent composition according to claim 9, further characterized in that in step (I) the alkylation is carried out at a temperature of 175 ° C to 215 ° C, at a pressure of 7.03 kg / cm2 gravimetric at 17.5 kg / cm2 gravimetric and at a time of 0.01 hours to 18 hours.

17. The detergent composition according to claim 9, further characterized in that step (II) is carried out using a sulfonating agent selected from the group consisting of sulfur trioxide, mixtures of sulfur trioxide / air, and sulfuric acid.

18. A heavy-duty water-based liquid detergent composition comprising: (i) from 5% to 70% by weight of the composition of a mixture of modified alkylbenzenesulfonate surfactants comprising: (a) from 15% to 99% % by weight of surfactant mixture, from a mixture of branched alkylbenzene sulphonates having the formula (I): (I) wherein 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 C? -C3 alkyl; R2 is selected from H and C? -C3 alkyl; A is a benzene portion; and (b) from 1% to 85% by weight of surfactant mixture, of a mixture of unbranched alkylbenzene sulphonates having the formula (II): (II) wherein 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 has an average aliphatic carbon content of 10.0 to 14.0; and wherein said mixture of modified alkylbenzene sulfonate surfactants is further characterized by a 2/3-phenyl index of 160 to 275 and wherein said mixture of modified alkylbenzene sulphonate surfactants has a 2-methyl-2-phenyl less than 0.3; (ii) From 0.1 to 8% of a co-surfactant composition selected from the group consisting of fatty acid amide alkyl polyhydroxy, alkylamidopropyl dimethylamine and mixtures thereof; (iii) from 0.00001% to 99.9% of the composition of a surfactant selected from the group consisting of anionic surfactants other than those of (i), nonionic surfactants, zwitterionic surfactants, cationic surfactants, amphoteric surfactants and mixtures thereof; and (iv) From 30% to 95% of an aqueous liquid carrier; with the proviso that when said detergent composition comprises any alkylbenzenesulfonate surfactant agent different from said agent mixture. Modified alkylaminobenzene sulfonate surfactants, said detergent composition is further characterized by a total 2/3-phenyl number of at least 160, wherein said 2/3-phenyl index is determined by measuring the 2/3-phenyl index, as defined in US Pat. present, in a combination of said mixture of modified alkylbenzenesulfonate surfactants and any other alkylbenzene sulfonate to be added to said detergent composition, said combination, for measurement purposes, is prepared from aliquots of the alkylbenzene sulfonate surfactant mixture. modified 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 will be determined by measuring the 2-methyl-2-phenyl index, as defined herein, in a combination of said mixture of modified alkylbenzenesulfonate surfactants and any other alkylbenzene sulfonate which will be added to said detergent composition, said combination, for measurement purposes, is prepared from aliquots of the mixture of modified alkyl benzene sulphonate surfactants and the other alkylbenzenesulfonate which has not yet been exposed to any other component of the composition Detergent.

19.- The detergent composition in accordance with the claim 18, further characterized in that it is substantially free of alkylbenzene sulfonate surfactants other than the mixture of modified alkyl benzene sulphonate surfactants.

20. The detergent composition according to claim 18, comprising, in said component (iii), at least 0.1% of a commercial linear alkylbenzenesulfonate surfactant of C10-Cu having a 2/3-phenyl index of 75. to 160.

21. The detergent composition according to claim 18, comprising, in said component (iii), at least 0.1% of a highly branched commercial alkylbenzene sulfonate surfactant.

22. The detergent composition according to claim 18, comprising, in said component (iii), 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 linear C 0 -C 0 alkyl, branched C 10 -C 16 alkyl of C C 3 in the middle part of its chain, C10-C16 branched-chain alkyl, 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.

23. The detergent composition according to claim 18, comprising, in said component (iii), an alkyl sulfate surfactant at a level of 0.5% to 25% by weight of said detergent composition, and wherein said alkyl sulfate surfactant has a hydrophobic group selected from linear C? or C? 8 alkyl, branched C? -C3 alkyl of C? -C3 in the middle part of its chain, C-C3 alkyl ? oC? 8 of branched guerbet, and mixtures thereof and a selected coffee of Na, K and mixtures thereof.

24. The detergent composition according to claim 18, comprising, in said component (iii), a surfactant of alkyl (polyalkoxy) sulfate at a level of 0.5% to 25% by weight of said detergent composition, in the wherein said alkyl (polyalkoxy) sulfate surfactant has a hydrophobic group selected from C10-C16 linear alkyl, branched C10-C16 alkyl from C C3 in the middle part of its chain, branched-chain C10-C16 alkyl, and mixtures thereof; and a hydrophilic (polyalkoxy) sulfate group selected from 1-15 polyethoxysulfate, 1-15 polypropoxysulfate, 1-15 polybutoxysulfate, mixed poly (ethoxy / propoxy / butoxy) sulfates and mixtures thereof, in blocked or unblocked form; and - a cation selected from Na, K and mixtures thereof.

25. The detergent composition according to any of claims 1 to 24, further comprising conventional detergent additives selected from the group consisting of detergency builders, bleaching compounds, polymeric dispersing agents, anti-redeposition agents, polymeric release agents, etc. dirt, enzymes, additional co-surfactants and mixtures thereof.

26.- The detergent composition in accordance with any of claims 1 to 25, which additionally comprises 6-nonylamino-6-oxoperoxycaproic acid.

27. The detergent composition according to any of claims 1 to 26, further comprising an activator of Bleach, wherein said bleach activator is selected from the group consisting of (6-octamido-caproyl) oxybenzenesulfonate, (6-nonanamidocaproyl) oxybenzenesulfonate, (6-decanamido-caproxy) oxybenzenesulfonate, and mixtures thereof.

28. The detergent composition according to claim 18, further characterized in that said mixture of modified alkylbenzene sulfonate surfactants is prepared by a process comprising a step selected from: combining a mixture of linear and branched alkylbenzene sulphonate surfactants having a 2/3-phenyl index of 500 to 700 with a mixture of surfactants X-^ -15 of alkylbenzenesulfonate having a 2/3-phenyl index of 75 to 160; and combining a mixture of branched and linear alkylbenzenes 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 mixture.