MXPA01007343A - Dishwashing compositions comprising modified alkylbenzene - Google Patents

Abstract

The present invention relates to surfactant mixtures, improved detergent and cleaning products containing particular types of alkylbenzenesulfonate surfactants.

Description

COMPOSITIONS FOR WASHING THORMS THAT INCLUDE MODIFIED ALKYLBENZENS FIELD OF THE INVENTION The present invention relates to dishwashing compositions comprising particular types of improved mixtures of alkylbenzenesulfonate surfactants which are adapted for use by controlling the parameters of compositions, especially a 2/3-phenyl index and a 2-methyl index -2-phenyl.

BACKGROUND OF THE INVENTION Historically, highly branched alkylbenzene sulphonate surfactants, such as those based on tetrapropylene, known as "ABS" or "TPBS", were used in detergents. However it was discovered that they had a very deficient biodegradable capacity. A prolonged period followed by improvement procedures for the preparation of alkylbenzenesulfonates, made them as linear as possible, hence the acronym "LAS". The overwhelming of a vast technique for the preparation of linear alkylbenzenesulfonate surfactants is directed towards this objective. All large commercial scale alkylbenzene sulphonate processes in use today are directed to linear alkylbenzene sulphonates. However, linear alkylbenzene sulphonates have limitations; for example, they would be more desirable if they improved with respect to cleaning properties with hard water and / or with cold water. Often they can not produce optimal cleaning results, for example when used in areas with hard water. As a result of the limitations of alkylbenzene sulfonates, consumer cleaning formulas have often needed to include a higher level of co-surfactants, builders and other additives that would have been necessary due to a higher alkylbenzene sulfonate. The alkylbenzene sulfonate detergent technique is replete with references that teach for and against almost every aspect of these compositions. Furthermore, it is believed that there are erroneous descriptions and technical misunderstandings about the operating mechanism of LAS under conditions of use, particularly in the area of hardness tolerance. The volume of these references devalues the technique completely and makes it difficult to select the useful teachings from the useless without repeated experimentation. In order to better understand the state of the art, it must be appreciated that not only has there been a lack of clarity as to where to go to solve the unresolved problems of the linear LAS, but also a variety of misunderstandings, not only in the understanding of biodegradation, but also in basic mechanisms of LAS operation in the presence of hardness.

Also, although the essentially linear alkylbenzene sulfonate surfactants that exist on the market today are compositions that are defined and analyzed with relative simplicity, compositions containing linear and branched alkylbenzene sulphonate surfactants are complex. In general, such compositions can be varied greatly with the content of one or more different types of branching at any number of positions in the aliphatic chain. A vast number, for example hundreds, of different chemical species is possible in these mixtures. Consequently there is an onerous spill of experimentation if it is desired to improve said compositions so that they can better cleanse in detergent compositions, and at the same time remain biodegradable. The knowledge of the formulator is the key to guide this effort. Even another problem that has not been solved in the manufacture of alkylbenzene sulfonate is the use of the materials used to supply LAB. It would be very desirable, from the point of view of yield and from the economic point of view, to better utilize certain desirable types of branched hydrocarbons. Therefore, there is a substantial need still unsatisfied to further improve mixtures of aiquilbenzene sulfonate surfactants, especially with respect to those which offer one or more advantages of superior cleaning, hardness tolerance, satisfactory biodegradable capacity and price.

TECHNICAL BACKGROUND E.U.A. 5,659,099; E.U.A. 5,393,718; E.U.A. 5,256,392; E.U.A. 5,227,558; E.U.A. 5,139,759; E.U.A. 5,164,169; E.U.A. 5,116,794; E.U.A. 4,840,929; E.U.A. 5,744,673; E.U.A. 5,522,984; E.U.A. 5,811, 623; E.U.A. 5,777,187; WO 9,729,064; WO 9,747,573; WO 9,729,063; E.U.A. 5,026,933; E.U.A. 4,990,718; E.U.A. 4,301, 316; E.U.A. 4,301, 317; E.U.A. 4,855,527; E.U.A. 4,870,038; E.U.A. 2,477,382; EP 466,558, 1/15/92; EP 469,940, 02/02/92; FR 2,697,246, 04/29/94; SU 793,972, 1/7/81; E.U.A. 2,564,072 E.U.A. 3,196,174; E.U.A. 3,238,249; E.U.A. 3,355,484; E.U.A. 3,442,964 E.U.A. 3,492,364; E.U.A. 4,959,491; WO 88/07030, 09/25/90; E.U.A 4,962,256; E.U.A. 5,196,624; E.U.A. 5,196,625; EP 364,012 B, 02/15/90 E.U.A. 3,312,745; E.U.A. 3,341, 614; E.U.A. 3,442,965; E.U.A. 3,674,885 E.U.A. 4,447,664; E.U.A. 4,533,651; E.U.A. 4,587,374; E.U.A. 4,996,386 E.U.A. 5,210,060; E.U.A. 5,510,306; WO 95/17961, 06/07/95; WO 95/18084 E.U.A. 5,510,306; E.U.A. 5,087,788; E.U.A. 4,301, 316; E.U.A. 4,301, 317 E.U.A. 4,855,527; E.U.A. 4,870,038; E.U.A. 5,026,933; E.U.A. 5,625,105 and E.U.A. 4,973,788. See Vol. 56 in "Surfactant Science" series, Marcel Dekker, New York, 1996, which includes in particular Chapter 2, entitled "Alkylarylisulfonates: History, Manufacture, Analysis and Environmental Properties", pages 39-108, "Surfactant Science" series, Vol. 73, Marcel Dekker, New York, 1998 and "Surfactant Science" series, Vol. 40, Marcel Dekker, New York, 1992. See also US patent applications Copending No. 60 / 053,319, Case No. 6766P filed on July 21, 1997; No. 60 / 053,318, case No. 6767P filed on July 21, 1997; No. 60 / 053,321, case No. 6768P filed on July 21, 1997; No. 60 / 053,209, case No. 6769P filed on July 21, 1997; No. 60 / 053,328, case No. 6770P filed on July 21, 1997; No. 60 / 053,186, case No. 6771 P filed on July 21, 1997 and the technique mentioned herein. The documents referred to herein are incorporated in their entirety.

BRIEF DESCRIPTION OF THE INVENTION It has now been determined that the use of certain mixtures of alkylbenzene sulfonate, hereinafter "mixtures of modified alkylbenzene sulfonate surfactants", as described in detail below, result in improved cleaning of difficult food stains, grease / oil removal. , improved benefits in the stability of the product in solution, wipes and low temperature, compared to the use of LAS in conventional detergent compositions. Hand dishwashing compositions according to the first embodiment of the present invention comprises: (i) from about 0.01% to about 95%, preferably from about 1% to about 50%, preferably about 2% to about 30% by weight of composition of a modified alkylbenzene sulfonate surfactant mixture comprising: a) from about 15% to about 99% by weight, preferably from about 15% to about 60%, more preferably from about 20% to about 40% by weight of surfactant mixture, a mixture of branched alkylbenzene sulphonates having the formula (I).

(Wherein L is an aliphatic acyclic part consisting of carbon and hydrogen, said L has two methyl endings and L has no substituent other than A, R1 and R2, and wherein said mixture of branched alkylbenzene sulfonates contains two or more , preferably at least three, optionally more, of said branched alkylbenzene sulphonates differing in molecular weight from the anion of the formula (I), and wherein the branched alkylbenzene sulphonate mixture has: - a sum of carbon atoms in R1, L and R2 from 9 to 15, preferably from 10 to 14, - an average aliphatic carbon content, ie, based on R1, L and R2 and excluding A, from about 10.0 to about 14.0 carbon atoms, preferably from about 11.0 to about a to about 13.0, more preferably from about 11.5 to about 12.5; M is a cation or mixture of cations, preferably M is selected from H, Na, K, Ca, Mg and mixtures thereof, more preferably M is selected from H, Na, k and mixtures thereof, more preferably still, M is selected from H, Na and mixtures thereof, M has a valence q, almost always from 1 to 2, preferably 1; a and b are selected integers such that the branched alkylbenzene sulphonates are electroneutral (it is almost always 1 to 2, preferably 1, b is 1); R1 is C1.3 alkyl, preferably C2-2 alkyl, more preferably methyl, R2 is selected from H and C1.3 alkyl (preferably H and C1-2 alkyl, more preferably H and methyl, more preferably H and methyl as long as at least 0.5, more preferably 0.7, more preferably 0.9 to 1.0 molar fraction of said branched alkylbenzenesulfonates, R2 is H); A is a part of benzene (almost always A is the part -C6H4-, with the SO3 part of the formula (I) in position para- to the part of L, although in some proportion, usually not greater than about of 5%, preferably from 0 to 5% by weight, part SO3 is ortho to L); and b) from about 1% to about 85%, preferably from about 40% to about 85%, more preferably from about 60% to about 80% by weight of surfactant mixture, from a mixture of alkylbenzene sulfonates not branched having the formula (II): di) wherein a, b, M, A and q are as previously defined in the present and Y is an unsubstituted linear aliphatic part consisting of carbon and hydrogen having two methyl ends, and wherein said Y has a sum of atoms carbon from 9 to 15, preferably from 10 to 14, and said Y has an average aliphatic carbon content of from about 10.0 to about 14.0, preferably from about 11.0 to about 13.0, more preferably from 11.5 to 12.5 atoms. carbon; and wherein said mixture of modified alkyl benzene sulphonate surfactants is also characterized by a 2/3-phenyl index of from about 160 to about 275, preferably from about 170 to about 265, more preferably from about 180 to about 225.; and also preferably wherein said mixture of modified alkyl benzene sulphonate surfactants has a 2-methyl-2-phenyl index of less than about 0.3, preferably less than about 0.2, more preferably less than about 0J, still more preferably from 0 to 0.05; (ii) from about 0.00001% to about 99.9% by weight of a composition of a conventional hand dishwashing aid; wherein said composition is also characterized by a 2/3-phenyl index of from about 160 to about 275. The compositions for washing dishes by hand according to the second embodiment of the present invention comprise: (i) a mixture of surfactants of modified alkylbenzenesulfonates, preferably from about 0.01% to about 95%, more preferably from about 1% to about 50%, even more preferably from about 2% to about 30% by weight of composition, which comprises product of a process comprising the steps of: (I) renting benzene with an alkylation mixture in the presence of a zeolite beta catalyst; (II) sulfonate the product of (I); and (III) as an option but most preferably neutralize the product of (II); wherein said alkylation mixture comprises: a) from about 1% to about 99.9% by weight of the alkylation mixture of branched C9-C20 monoolefins (preferably C9-C15, more preferably Cio-Cu), said monoolefins Branched have structures identical to those of the branched monoolefins which are formed by the dehydrogenation of branched paraffins of the formula R1LR2, wherein L is an aliphatic acyclic part consisting of carbon and hydrogen and contains two terminal methyls; R1 is C1 to C3 alkyl; and R2 is selected from H and alkyl from Ci to C3; and b) from about 0.1% to about 85% by weight of alkylation mixture of linear aliphatic olefins of C9-C20 (preferably C9-C15, more preferably C10-C14); wherein the alkylation mixture contains said branched C9-C20 monoolefins (preferably C9-C15, more preferably Cio-Cu) having at least two different carbon numbers on the C8-C20 scale (preferably of C9-C15, more preferably C? 0-Cu), and has an average carbon content of about 9.0 to about 15.0 carbon atoms (preferably from about 10.0 to about 14.0, more preferably about 11.0 at about 13.0, still more preferably from about 11.5 to about 12.5); and wherein components a) and b) are in a weight ratio of at least about 15:85, preferably with a branched component a) in excess of linear component b), for example 51% or more by weight of a) and 49% or less of b), more preferably 60% to 95% by weight of a) and 5% to 40% of b), still more preferably 65% to 90% by weight of a) and 10 % to 35% of b), more preferably still 70% to 85% by weight of a) and 15% to 30% of b), where these percentages by weight exclude any other material, for example diluting hydrocarbons that may be present in the procedure; (ii) from about 0.00001% to about 99.9% by weight composition of a conventional dishwashing aid; wherein the composition is further characterized by a 2/3-phenyl index of about 275 to about 10,000. Hand dishwashing compositions according to the third embodiment of the present invention comprise: (i) a mixture of modified alkyl benzene sulphonate surfactants, preferably from about 0.01% to about 95%, more preferably about 1% at about 50%, even more preferably from about 2% to about 30% by weight of composition, consisting essentially of a process comprising the steps, in sequence, of: (I) renting benzene with an alkylation mixture in the presence of a zeolite beta catalyst; (II) sulfonate the product of (I); and (III) neutralizing the product of (II); wherein said alkylation mixture comprises: a) from about 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 C9-C20 (preferably of C9-C15, more preferably of Cio-Cu) R1LR2, wherein L is an olefinic acyclic part consisting of carbon and hydrogen and containing two terminal methyls; B) C9-C20 alpha monoolefins (preferably C9-C15, more preferably C o C) R1 AR2, wherein A is an alpha-olefinic acyclic part consisting of carbon and hydrogen and containing a terminal methyl and a methylene terminal olefinic; C) C9-C20 vinylidene monoolefins (preferably C9-C15, more preferably C? 0-C14) R1BR2, wherein B is an acyclic vinylidene-olefin part consisting of carbon and hydrogen and containing two terminal methyls and one methylene internal olefinic; D) C9-C20 primary alcohols (preferably C9-C15, more preferably Cio-Cu) R1QR2, wherein Q is an aliphatic acyclic part of the primary terminal alcohol consisting of carbon, hydrogen and oxygen and containing a terminal methyl; E) C9-C20 primary alcohols (preferably C9-C15, more preferably C10-Cu) R1ZR2, wherein Z is an aliphatic acyclic part of primary non-terminal alcohol consisting of carbon, hydrogen and oxygen and containing two terminal methyls; and F) mixtures thereof; wherein in any of A) - F), R1 is C1 to C3 alkyl and R2 is selected from H and C1 to C3 alkyl; and b) from about 0.1% to about 85% by weight of linear alkylating agent alkylation mixture of C9-C20 (preferably C9-C15, more preferably C? 0-Cu) selected from linear aliphatic olefins of C9-C20 (preferably C8-C5, more preferably C0-C), linear C9-C20 aliphatic alcohols (preferably C9-C15, more preferably C or C) and mixtures thereof; wherein the alkylation mixture contains the branched alkylating agents having at least two different carbon numbers on said scale of C9-C20 (preferably C9-C15, more preferably Cio-Cu), and has a content carbon averages from about 9.0 to about 15.0 carbon atoms, preferably from about 10.0 to about 14.0, more preferably from about 11.0 to about 13.0, still more preferably from about 11.5 to about 12.5; and wherein components a) and b) are in a weight ratio of at least about 15:85 (preferably with a branched component a) in excess of linear component b), for example 51% or more by weight of a) and 49% or less of b), more preferably 60% to 95% by weight of a) and 5% to 40% of b), still more preferably 65% to 90% by weight of a) and 10 % to 35% of b), more preferably still 70% to 85% by weight of a) and 15% to 30% of b), where these percentages by weight exclude any other material, for example diluting hydrocarbons that may be present in the procedure); (ii) from about 0.00001% to about 99.9% by weight composition of a conventional dishwashing aid; wherein the composition is further characterized by a 2/3-phenyl index of from about 160 to about 275. The modalities mentioned above and other aspects of the present invention are fully described and exemplified in the detailed description that follows. 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, in a relevant part, are incorporated herein by reference.

DETAILED DESCRIPTION OF THE INVENTION On the other hand, the invention is not intended to encompass any conventional hand dishwashing composition in general, such as those based exclusively on linear alkylbenzenesulfonates made by any process, or exclusively on unacceptably branched alkylbenzene sulphonates, such as ABS or TPBS. It is preferred that when the detergent compositions of the present invention comprise any alkylaminobenzene sulfonate surfactant other than said mixture of modified alkyl benzene sulphonate surfactants (e.g. as a result of the combination, in the detergent composition, of one or more alkylbenzene sulphonate surfactants of C? 0-Cu almost always linear, especially linear and commercial), said composition is also characterized by a general 2/3-phenyl index of at least about 200, preferably at least about 250, more preferably so less about 350, still more preferably at least about 500, wherein said general 2/3-phenyl index is determined by measuring the 2/3-phenyl index, as defined herein, in a mixture combination of modified alkylbenzenesulfonate surfactants and any other alkylbenzenesulfonate that is added to the composition, said combination, for measurement purposes, is prepared from aliquots of the modified alkylbenzene sulfonate surfactant mixture and the other alkylbenzene sulfonate not yet exposed to any other component of the composition; and further provided that the composition comprises any alkylbenzene sulfonate surfactant other than the modified alkyl benzene sulphonate surfactant mixture (e.g. as a result of the combination, in the detergent composition, of one or more C14-C13 alkylbenzenesulfonate surfactants) always linear, especially linear and commercial), said composition is also characterized by a general 2-methyl-2-phenyl index of less than about 0.3, preferably from 0 to 0.2, more preferably no greater than about OJ, more preferably still not greater than about 0.05, wherein the general 2-methyl-2-phenyl index is determined by measuring the 2-methyl-2-phenyl index, as defined herein, in a combination of said agent mixture. modified alkylbenzenesulfonate surfactants and any other alkylbenzenesulfonate that is added to the composition, said combination, for the purposes of med. It is prepared from aliquots of the modified alkyl benzene sulfonate surfactant mixture and the other alkylbenzene sulfonate not yet exposed to any other component of the composition. These arrangements may seem somewhat unusual, but are compatible with the spirit and scope of the present invention, which encompasses several economical but less preferred approaches depending on the general cleaning performance, such as the combination of modified alkylbenzene sulfonate surfactants with conventional linear alkylbenzenesulfonate surfactants, either during synthesis or during formulation in the composition. In addition, as is known to experts in the analysis of hand dishwashing, several auxiliaries to wash dishes by hand (paramagnetic materials and sometimes even water) have the ability to interfere with methods to determine the parameters of mixtures of surfactants of alkylbenzenesulfonate, as described hereinafter. Consequently, where possible, the analysis should be carried out on dry materials before mixing them in the compositions.

In a preferred embodiment, the mixture of modified alkyl benzene sulfonate surfactants in the hand dishwashing composition according to the composition according to the first embodiment is prepared by a process comprising a step selected from: combining a mixture of alkylbenzene sulfonate surfactants branched or linear having a 2/3-phenyl index of 500 to 700 with a mixture of alkylbenzenesulfonate surfactants having a 2/3-phenyl index of 75 to 160 (almost always, this alkylbenzenesulfonate surfactant is a surface active agent) of linear C10-C14 linear alkylbenzene sulphonate, for example LAS of DETAL® procedure or LAS of HF process, although in general any linear type (LAS) or branched type (ABS, TPBS) can be used commercially); and combining a mixture of linear and branched alkyi-benzenes having a 2/3-phenyl analog of from 500 to 700 with an alkylbenzene mixture having a 2/3-phenyl index of from 75 to 160 and sulfonating said combination. Also, the invention encompasses the addition of useful hydrotrope precursors and / or hydrotropes, such as C?-C8 alkylbenzenes, more often toluenes, eumens, xylenes, naphthalenes or sulfonated derivatives of any such materials, minor amounts of any material , such as trirramified alkylbenzene sulphonate surfactants, dialkylbenzenes and their derivatives, dialkyltetralins, wetting agents, processing aids and the like. It will be understood that, with the exception of the hydrotropes, it will not be a common practice in the present invention to include any such materials. Similarly, it will be understood that said materials, in case of and when they interfere with analytical methods, will not be included in samples of compositions used for analytical purposes. A mixture of modified alkyl benzene sulfonate surfactants according to the first embodiment of this invention has M selected from H, Na, K and mixtures thereof, a = 1, b = 1, q = 1, and the mixture of agents modified alkylbenzenesulfonate surfactants has a 2-methyl-2-phenyl index of less than about 0.3, preferably less than about 0.2, more preferably from 0 to about OL With regard to the composition there are methods of use, such as the method of contacting dirty dishes that need to be cleaned with a pure solution or an aqueous solution of the composition of the invention. Said methods may include as an option the step of diluting the composition in water. In addition, the composition can be applied, either purely or as an aqueous solution, directly to the dish or surface to be cleaned or directly to a cleaning utensil, such as a sponge or washcloth. Said methods are part of this invention. That mixture of alkylbenzene sulphonate surfactants modified accordingly can be made as the product of a process using as catalyst a zeolite selected from mordenite, offerite and H-ZSM-12 at least in partially acid form, preferably an acid mordenite (in general certain forms of beta zeolite can be used as an alternative, but are not preferred). The modalities described according to their preparation, as well as the suitable catalysts, are further detailed in the following. Another preferred mixture of modified alkylbenzenesulfonate surfactants according to the first embodiment of the invention consists essentially of said mixture of branched alkylbenzene sulphonates and unbranched alkylbenzene sulphonates, wherein the 2-methyl-2-phenyl index of the alkylbenzene sulfonate surfactant mixture modified is less than about OJ, and wherein in said mixture of branched and unbranched alkylbenzenesulfonates, said average aliphatic carbon content is from about 11.5 to about 12.5 carbon atoms; R1 is methyl; R is selected from H and methyl, provided that at least about 0.7 mole fraction of the branched alkylbenzenesulfonates R2 is H; and wherein the sum of carbon atoms in R1, L and R2 is from 10 to 14; and wherein also in the mixture of unbranched alkylbenzene sulphonates, Y has a sum of carbon atoms of 10 to 14, said average aliphatic carbon content of the unbranched alkylbenzene sulphonates is from about 11.5 to about 12.5 carbon atoms, and M is a monovalent cation or mixture of cations which is selected from H, Na and mixtures thereof.

Definitions Methyl endings The terms "methyl endings" and / or "terminal methyl" mean the carbon atoms which are terminal carbon atoms in alkyl portions, ie L, and / or Y of the formula (I) and the formula ( II) respectively are always linked to three hydrogen atoms; that is, they will form a CH3- group. To better explain this, the structure below shows the two terminal methyl groups in an alkylbenzene sulfonate.

The term "AB" herein, when used without another qualifier, is an abbreviation of "alkylbenzene" of the so-called "hard" or non-biodegradable type which in sulfonation forms "ABS". The term "LAB" herein is an abbreviation of "linear alkylbenzene" of the most biodegradable type on the market today, which in sulfonation forms linear alkylbenzenesulfonate or "LAS". The term "MLAS" herein is an abbreviation of the modified alkylbenzene sulfonate mixtures of the invention.

Impurities The presently preferred surfactant mixtures do not have substantial impurities selected from triturated impurities, dialkyltetralin impurities and mixtures thereof. "They do not have substantial impurities" means that the amounts of said impurities are not sufficient to contribute positively or negatively to the cleaning effectiveness of the composition. Almost always, there is less than about 5%, preferably less than about 1%, more preferably about 0.1% or less of the impurity, i.e., practically almost never any of the impurities can be detected.

Illustrative Structures To better illustrate the possible complexity of the modified alkylbenzenesulfonate surfactant mixtures of the invention and the resulting detergent compositions, the structures a) to v) below are illustrative of some of the many preferred compounds of the formula (I). These are only some of hundreds of possible preferred structures that make up the volume of the composition, and should not be considered as limits of the invention. (k) (I) (s) (t) The structures w) and x) non-limitingly illustrate less preferred compounds of the formula (I) which may be present, at lower levels than the types of preferred structures illustrated above, in the mixtures of modified alkyl benzene sulphonate surfactants. of the invention and the resulting detergent compositions.

The structures y), z) and aa) in a non-limiting manner illustrate compounds broadly in the formula (I) that are not preferred, but which may be present in the modified alkylbenzenesulfonate surfactant mixtures of the invention and the resulting detergent compositions . (z) Structure bb) is illustrative of a tri-branched structure that is not in formula (I), but may be present as an impurity. Preferably, the branched alkylbenzene sulfonate is the product of the sulfonation of a branched alkylbenzene, wherein the branched alkylbenzene is produced by the alkylation of benzene with a branched olefin on a zeolite beta catalyst which may be fluorinated or non-fluorinated, more preferably , the beta catalyst of zeolite is a beta catalyst of zeolite acid. The beta catalysts of acid zeolite are beta catalysts of calcined zeolite treated with HF. Broadly speaking, mixtures of alkylbenzene sulphonate surfactants modified herein can be made by the steps of: (I) alkylating benzene with an alkylation mixture; (II) sulfonate the product of (I); and (as an option, but very preferably) (III) neutralizing the product of (II).

Provided that suitable alkylation catalysts and process conditions are used as taught herein, the product of step (I) is a modified alkylbenzene mixture according to the invention. On condition that the sulfonation is carried out under generally known conditions and can be reapplied from the preparation of LAS, see for example the references of the written material mentioned herein, the product of step (II) is a mixture of modified alkylbenzenesulfonic acid according to the invention. Provided that step (III) of neutralization is carried out as taught in general herein, the product of step (III) is a mixture of modified alkylbenzenesulfonate surfactants according to the invention. Since the neutralization may be incomplete, mixtures of the acidic and neutralized forms of these modified alkylbenzene sulfonate systems in all proportions, for example from about 1000: 1 to 1: 1000 by weight, are also part of this invention. In general, the greatest difficulties are in step (I). In this way, it is also preferred that in step (I) the alkylation be carried out at a temperature of about 125 ° C to about 230 ° C, preferably from about 175 ° C to about 215 ° C and at a pressure of about 3.51 kg / cm2 to about 70.3 kg / cm2, preferably about 7.03 kg / cm2 to about 17.57 kg / cm2. The time for this alkylation reaction may vary, however, it is more preferred that the time for this alkylation is from about 0.01 hours to about 18 hours, more preferably, as fast as possible, more often from about OJ hours to about 5 hours, or from about OJ hours to about 3 hours. In general in step (I) it is preferable to couple 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) at the scales indicated previously. In addition, it is contemplated that the "step" (I) of alkylation in the present may be "stratified", so that two or more reactors operating under different conditions in the defined scales may be useful. With the operation of a plurality of said reactors it is possible to allow the material with the least preferred 2-methyl-2-phenyl index to be formed initially, and to suddenly convert said material into material with a 2-methyl-2-index. -phenyl preferred. Accordingly, a sudden discovery as part of the present invention is that low levels of quaternary alkylbenzenes can be obtained in catalyzed beta reactions of benzene zeolite with branched olefins, as characterized by a 2-methyl-2-phenyl index lower than OL Catalyst. Alkylation The present invention employs an alkylation catalyst defined in particular. Said catalyst comprises a zeolite of medium porosity and moderate acidity which is defined in detail hereinafter. A preferred alkylation catalyst in particular comprises a non-fluorinated beta-acidic zeolite at least partially deacylated or an at least partially acidified fluorinated beta-zeolite dealuminized. It is easily determined that numerous alkylation catalysts are not suitable. Unsuitable alkylation catalysts include the process catalysts DETAL®, aluminum chloride, HF and many others. Actually, no alkylation catalyst that is used today for alkylation in the commercial production of linear alkyl detergents sulfonates is suitable. In contrast, the suitable alkylation catalyst herein is selected from alkylation catalysts with moderate acidity and selective figure, preferably with zeolite. More paticularly, the zeolite in said catalysts for the alkylation step I is preferably selected from the group consisting of ZSM-4, ZSM-20 and beta zeolite, more particularly beta zeolite, in at least partially acidic form. More preferably, the zeolite in step I (alkylation step) is in substantially acidic form and is contained in a catalyst pellet comprising a conventional binder and further wherein said catalyst pellet comprises at least about 1%, more preferably at least 5%, more often from 50% to about 90%, of the zeolite, wherein the zeolite is preferably a beta zeolite. More generally, the suitable alkylation catalyst is almost always at least partially crystalline, more preferably substantially crystalline without including binders or other materials used to form pellets, aggregates or mixed catalyst materials. Also, the catalyst is almost always beta zeolite at least partially acidic. This catalyst is useful for the alkylation step identified as step I in the claims that appear later. The largest pore diameter that characterizes the zeolites useful in the present alkylation process may be in the range of 6 Angstroms to 8 Angstroms, as in the beta zeolite. It should be understood that in any case, the zeolites used as catalysts in the alkylation step of this process have a higher pore size intermediate between that of the large pore zeolite, such as the X and Y zeolites, and the pore size zeolites. relatively smaller, such as modemita, offerita, HZSM-12 and HZSM-5. In fact, it has been tried and discovered that ZSM-5 is inoperable in the present invention. Measurements of pore size and crystalline structures of certain zeolites are specified in ATLAS OF ZEOLITE STRUCTURE TYPES of W.M. Meier and D.H. Olson, published by the Structure Commission of the International Zeolite Association (1978 and later editions) and distributed by Polycrystal Book Service, Pittsburgh, Pa.

The zeolites useful in the alkylation step of this process generally have at least 10 percent of the cationic sites thereof occupied by ions other than alkali or alkaline earth metals. Typical but non-limiting replacement ions include ammonium, hydrogen, lanthanides, zinc, copper and aluminum. Of this group, the particular reference is ammonium, hydrogen, lanthanides or combinations thereof. In a preferred embodiment, the zeolites are converted to the hydrogen form predominantly, generally by replacement of the alkali metal or other ion present with hydrogen ion precursors, eg, ammonium ions, which are calcined to produce the hydrogen form. This exchange is effected for convenience by contacting the zeolite with an ammonium salt solution, for example ammonium chloride, using the known ion exchange techniques. In certain preferred embodiments, the degree of replacement is such as to produce a zeolite material 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 (dealumination) and combination with one or more metal components, in particular the metals of Groups IIB, III, IV, VI, VII and VIII. It is also contemplated that the zeolites, in some cases, may be subjected if desired to thermal treatment, including vaporization or calcination in air, hydrogen or an inert gas, for example nitrogen or helium.

A suitable modification treatment causes the vaporization of the zeolite by contact with an atmosphere containing from about 5 to about 100% steam at a temperature of about 250 ° C to 1000 ° C. Vaporization can last between about 0.25 and about 100 hours and can be carried out at pressures ranging from sub-atmospheric to several hundred atmospheres. With the practice of the desired alkylation step of this process, it may be useful to incorporate the crystalline zeolites of intermediate pore size which are described above in another material, for example a binder or temperature resistant matrix and other conditions employed in the process . Said matrix materials include synthetic substances or as they occur 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 that include mixtures of silica and metal oxides. The latter may be as they occur in the nature or in the form of gels or gelatinous precipitates. The clays as they occur in nature that can be made mixed with the zeolite include those from the montmorillonite and kaolin families, which include sub-bentonites and kaolins commonly known as clays Dixie, McNamee-Georgia and Florida or others in which the main mineral constituent is haloysite, kaolinite, dike, nacrite or anauxite. These clays can be used in the raw state as they are extracted or initially subjected to calcination, acid treatment or chemical modification.

In addition to the foreign materials, the intermediate pore size zeolites used herein may be composed of a porous matrix material, such as alumina, silica-alumina, silica -magnesia, silica-zirconia, silica-silica, silica. - berilia and silica - titania, as well as ternary combinations, such as silica - alumina - toria, silica - alumina - zirconia, silica - alumina - magnesia and silica - magnesia - zirconia. The matrix can be in the form of a cogel. The relative proportions of finely divided zeolite and inorganic oxide gel matrix can vary widely, where the zeolite content varies between about 1 to about 99% by weight and more often on the scale of about 5 to about 80% by weight. 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 10J, preferably at least 20: 1. The silica: alumina ratios referred to in this specification are the structural or general framework relationships, that is, the relationship for the tetrahedra SiO4 to AIO. This relationship may vary from the silica: alumina ratio determined by various physical and chemical methods. For example, a large-scale chemical analysis can include aluminum that is present in the form of cations related to the acid sites in the zeolite, thus giving a silica: alumina ratio. Similarly, if the ratio is determined by thermogravimetric analysis (TGA) of ammonia desorption, a low ammonia titration can be obtained, if the cationic aluminum prevents the exchange of the ammonium ions at the acid sites. These disparities are somewhat problematic when using certain treatments, such as the desaluminization methods described below, which result in the presence of ionic aluminum without the zeolite structure. Care must be taken to ensure that the general framework ratio of silica: alumina is determined correctly. When the zeolites are prepared in the presence of organic cations, they are almost always inactive in catalysis, perhaps because the intracrystalline free space is occupied by organic cations of the forming solution. They can be activated by heating in an inert atmosphere at 540 ° C for one hour, for example, followed by a base exchange with ammonium salts, after calcination at 540 ° C in air. The presence of organic cations in the forming solution may not be essential at all for the formation of the zeolite, but seems to favor the formation of this special type of zeolite. Some natural zeolites can sometimes be converted to zeolites of the desired type through various activation procedures and other treatments, such as base exchange, vaporization, alumina extraction and calcination. Preferably, the zeolites have a general framework density of crystals, in the form of dry hydrogen, 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 per 1000 cubic Angstroms, as given, for example on page 19 of the article Zelite Structure of 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 an explanation of the general framework density of crystals. Another explanation of the overall frame density of crystals, together with values for some typical zeolites, is found in the U.S. patent. No. 4,016,218, to which reference is made. When synthesized in the alkali metal form, the zeolite is conveniently converted to the hydrogen form, generally by the intermediate formation of the ammonium form, as a result of ammonium ion exchange and calcination of the ammonium form to produce the form of hydrogen. It has been found that although the hydrogen form of the zeolite catalyses the reaction successfully, the zeolite may also be partly in the alkali metal form. Preferred zeolite catalysts include beta zeolite, HZSM-4, HZSM20 and HZSM-38. The most preferred catalyst is beta zeolite acid. A suitable beta zeolite for use herein is described in E.U.A. 3,308,069 to which reference is made for details of this zeolite and its preparation. Beta zeolite catalysts in the acid form are also commercially available as Zeocat PB / H from Zeochem. Other beta zeolite catalysts suitable for use can be obtained from UOP Chemical Catalyst and Zeolyst International.More generally, the alkylation catalysts can be employed herein, so long as the alkylation catalyst 1) can be adjusted to a smaller pore diameter of said catalyst, said branched olefins described herein and 2) to be rented. benzene selectively with the branched olefins and / or mixing with unbranched olefins with sufficient selectivity to provide the 2/3-phenyl index values as defined herein. In a preferred mode, a hydrotrope or hydrotrope precursor is added either after step (I), during or after step (II) and before step (III) or during or after step (III). The hydrotropes are selected from any suitable hydrotrope, almost always a sulfonic acid or sodium sulfonate salt of toluene, cumene, xylene, naphthalene or mixtures thereof. The hydrotrope precursors are selected from any suitable hydrotrope precursor, usually toluene, cumene, xylene, naphthalene or mixtures thereof.

Sulfonation and treatment or neutralization (steps (ll / lll) Preferably, the sulfonation step (ll) is carried out using a sulphonation agent, preferably selected from the group consisting of sulfuric acid, sulfur trioxide with or without air, acid chlorosulfonic acid, fuming sulfuric acid and mixtures thereof, and is preferable in step (II) removing components other than monoalkylbenzenes prior to contacting the product of step (I) with the sulfonation agent.

In general, the sulfonation of the alkylbenzenes modified in the present process can be carried out using any of the known sulfonating systems, including those described in "Detergent Manufacture Including Zeolite Builders and other New Materials", Ed. Sittig., Noyes Data Corp., 1979, as well as in Vol. 56 in "Surfactant Science" series, Marcel Dekker, New York, 1996, including in particular in chapter 2 entitled "Alkylaryl sulfonates: History, Manufacture, Analysis and Environmental Properties", pages 39- 108, which includes 297 references of written material. This work gives access to a large number of written materials describing procedures and procedural steps, not only of sulfonation, but also of dehydrogenation, alkylation, alkylbenzene distillation and the like. Common sulfonating systems useful herein include sulfuric acid, chlorosulfonic acid, fuming sulfuric acid, sulfur trioxide, and the like. Sulfur trioxide / air is especially preferred. The details of sulfonation employing a suitable mixture of air / sulfur trioxide are found in E.U.A. 3,427,342, Chemithon. The sulfonation processes are described in much greater detail in "Sulfonation Technology in the Detergent Industry", W.H. de Groot, Kluwer Academic Publishers, Boston, 1991. Any convenient treatment steps can be employed in the present process. The common practice is to neutralize after sulfonation with any suitable alkali. In this way, the neutralization step can be carried out using a selected alkali of sodium, potassium, ammonium, magnesium and substituted ammonium alkalis and mixtures thereof. Potassium can aid in solubility, magnesium can promote the performance of mild water, and substituted ammonium can be useful for formulating specialty variations of these surfactants. The invention encompasses any of these forms derived from the modified alkylbenzenesulfonate surfactants as produced by the present process and their use in compositions of the product to consumers. Alternatively, the acid form of these surfactants can be added directly to acidic cleaning products, or they 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 having a cation selected from the group consisting of alkali metal, alkaline earth metal, ammonium, substituted ammonium and mixtures thereof, and a selected anion of the hydroxide, 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, ammonia hydroxide and mixtures thereof. The methods are tolerant to variation, for example conventional steps may be added before, in parallel with, or after the steps mentioned (I), (II) and (III). This is the case in particular to adjust the use of hrdrótropos or their precursors.

EXAMPLES OF PREPARATION EXAMPLE 1 Mixture of 4-methyl-4-nonanol, 5-methyl-5-decanol, 6-methyl-β-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 dropwise over a period of 2.25 hours to a stirred, nitrogen-blanketed two-liter 2 L ball flask equipped with a reflux condenser and containing 600 ml of n-bromide. Pentylmagnesium 2.0 M in diethyl ether and 400 ml more 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 broken 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. Then, the ether layer is 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-dodecanoi.

EXAMPLE 2 Mixture of branched olefin substantially mono methyl with randomized branching. an alkylating agent for preparing modified alkylbenzenes according to the invention a) A sample of 174.9 g of the branched mono methyl alcohol mixture of Example 1 is added to a stirred three-neck, nitrogen-blanketed 500 ml ball flask equipped with a Dean Stark trap and a reflux condenser. together with 35.8 g of a shape-selective zeolite catalyst (acid mordenite catalyst Zeocat ™ FM-8 / 25H). When mixing, then the mixture is heated to about 110-155 ° C and water and some olefin are collected over a period of 4-5 hours in the Dean Stark trap. The conversion of the alcohol mixture of Example 1 to a substantially non-randomized methyl branched olefin mixture is now complete and the reaction mixture is cooled to 20 ° C. The substantially non-randomized 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-randomized methyl branched olefin mixture. b) The olefin mixture of example 2a is combined with 36 g of a shape selective zeolite catalyst (acid mordenite catalyst Zeocat ™ FM-8 / 25H) and reacted according to example 2a with the following changes. The reaction temperature was raised to 190-200 ° C for a period of about 1-2 hours to randomize the positions of specific branches in the olefin mixture. The reaction mixture is cooled to 20 ° C. The substantially mono-methyl branched olefin mixture with the randomized branch 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 147.5 g of a substantially mono methyl branched olefin mixture with randomized branching.

EXAMPLE 3 Mixture of branched alkylbenzene substantially mono methyl with a 2/3-phenyl index of about 200 and a 2-methyl-2-phenyl index of about 0.005 (A mixture of modified alkylbenzene according to the invention) 147 g of the substantially mono methyl branched olefin mixture of example 2 and 36 g of a shape selective zeolite catalyst (Zeocat ™ PB / H acid zeolite beta catalyst) are added to a 7.56 liter stirred stainless steel autoclave. The olefin residue and catalyst in the vessel are washed in the autoclave with 300 ml of n-hexane and the autoclave is sealed. From the outside of the autoclave cell, 2000 g of benzene (contained in an insulated container and added by an isolated pumping system inside the isolated autoclave cell) are added to the autoclave.; The latter is purged twice with 17.57 kg / cm2 of N2, and then charged to 4.21 kg / cm2 of N2. The mixture is stirred and heated to about 200 ° C for about 4-6 hours. The autoclave is cooled to around 20 ° C during the night. The valve is opened by going from the autoclave to the benzene condenser and to the collection tank. The autoclave is heated to around 120 ° C with continuous collection of benzene. By the time the reactor reaches 120 ° C, no more benzene is collected. Then, the reactor is cooled to 40 ° C and 750 g of n-hexane are pumped into the autoclave, which is drained to remove the reaction mixture. The reaction mixture is filtered to remove the catalyst and the n-hexane is removed under vacuum. The product is distilled under vacuum (1-5 mm Hg). The mixture of branched alkylbenzene substantially mono methyl with a 2/3-phenyl index 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 branched alkylbenzenesulfonic acid substantially mono methyl 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 sulfone 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 branched alkylbenzenesulfonic acid substantially mono methyl with a 2/3-phenyl index of about 200 and a 2-methyl-2-phenyl index of about 0.005.

EXAMPLE 5 Mixture of sodium salt, branched alkyl mono-benzenesulfonate substantially mono methyl with a 2/3-phenyl index of about 200 and index 2-methyl-2-phenyl of about 0.005 (A mixture of modified alkylbenzenesulfonate surfactants 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 sodium salt, branched alkylbenzene sulfonate substantially mono methyl with a 2/3-phenyl index 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 index of about 200 and a 2-methyl-2-phenyl index of about 0.02 is prepared using a zeolite-shape catalyst (Zeocat acid-zeolite catalyst). ™ PB / H). A mixture of 15.1 g of Neodene (R) 10, 136.6 g of Neodene (R) 1112, 89.5 g of Neodene (R) 12 and 109.1 g of 1-tridecene is added to a stirred stainless steel autoclave of 7.56 liters together with 70 g of a shape selective catalyst (Zeocat ™ PB / H acid zeolite catalyst). Neodene is a brand for olefins from Shell Chemical Company. The olefin residue and catalyst in the vessel are washed in the autoclave with 200 ml of n-hexane and the autoclave is sealed. From the outside of the autoclave cell, 2500 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 latter is purged twice with 17.57 kg / cm2 of N2, and then charged to 4.21 kg / cm2 of N2. The mixture is stirred and heated to about 170-175 ° C for about 18 hours, then cooled to 70-80 ° C. The valve is opened by going from the autoclave to the benzene condenser and to the collection tank. The autoclave is heated to around 120 ° C with continuous collection of benzene in the collection tank. By the time the reactor reaches 120 ° C, no more benzene is collected. Then, the reactor is cooled to 40 ° C and 1 kg of n-hexane is pumped into the autoclave, which is drained to remove the reaction mixture. The reaction mixture is filtered to remove the catalyst and the n-hexane is evaporated under low vacuum conditions. The product is then distilled in high vacuum (1-5 mm Hg). The substantially linear alkylbenzene mixture with 2/3-phenyl index of about 200 and a 2-methyl-2-phenylene 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 v 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 index of about 200 v a 2-methyl-2-phenyl index of about 0.02 (A mixture of alkylbenzenesulfonate surfactants to be used as a component of agent mixtures modified alkylbenzenesulfonate surfactants 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 sodium salt mixture, substantially linear alkylbenzenesulfonate with a 2/3-phenyl index of about 200 and a 2-methyl-2-phenyl index of about 0.02.

EXAMPLE 9 6.1Q-Dimethyl-2-undecanol (A starting material for branched olefins) To a glass vessel for autoclaving are added 299 g of geranylacetone, 3.8 g of 5% ruthenium on carbon and 150 ml of methanol. The glass vessel is sealed inside a 3 L stainless steel oscillating autoclave, and the latter is purged once with 17.57 kg / cm2 of N2, once with 17.57 kg / cm2 of H2 and then loaded with 70.3 kg / cm2 of H2. The reaction mixture is heated by mixing. At around 75 ° C, the reaction starts and starts to consume H2 and gives off heat at 170-180 ° C. In 10-15 minutes, the temperature drops to 100-110 ° C and the pressure drops to 35.15 kg / cm2. The autoclave is supercharged at 70.3 kg / cm2 with H2 and mixed at 100-110 ° C for another hour and 40 minutes, where the reaction consumes an additional 11.24 kg / cm2 of H2, but at that time no longer observed consumption of H2. Upon cooling the autoclave at 40 ° C, the reaction mixture was removed, filtered to remove the catalyst and concentrated by evaporation of methanol under vacuum to yield 297.75 g of 6J0-dimethyl-2-undecanol.

EXAMPLE 10 5,7-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 stainless steel oscillating autoclave of 3 L, and the latter is purged once with 17.57 kg / cm2 of N2, once with 17.57 kg / cm2 of H2 and then loaded with 35.15 kg / cm2 of H2. The reaction mixture is heated by mixing. At around 75 ° C, the reaction starts and begins to consume H2 and gives off heat at 170 ° C. In 10 minutes, the temperature drops to 115-120 ° C and the pressure drops to 18.98 kg / cm2. The autoclave is supercharged at 70.3 kg / cm2 with H2, mixed at 110-115CC for 7 more hours and 15 minutes, 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 dropwise over a period of five hours to a stirred, nitrogen-blanketed 5 L three-necked ball flask equipped with a reflux condenser and containing 1.6 L of bromide solution. methylmagnesium 3.0 M and 740 ml more diethyl ether. The reaction flask is placed in an ice water bath to control exotherm and subsequent ether reflux. After the addition is complete, the ice water bath is removed and the reaction is allowed to mix for a further 2 hours at 20-25 ° C, at which time the reaction mixture is added by mixing with 3.5 kg of broken ice. 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. Then, the ether layer is concentrated by evaporation of the ether under vacuum to yield 720.6 g of 4,8-dimethyl-3,7-nonadien-2-ol. To a glass cladding 249.8 g of the 4 are added, 8-dimethyl-3,7-nonadien-2-ol, 5.8 g of 5% palladium on activated carbon and 200 ml of n-hexane. The glass liner is sealed inside a 3 L stainless steel oscillating autoclave and the latter is purged twice with 17.57 kg / cm2 of N2, once with 17.57 kg / cm2 of H2 and then charged with 7.03 kg / cm2 of H2. When mixing, the reaction starts and begins to consume H2 and gives off heat at 75 ° C. The autoclave is heated to 80 ° C, supercharged at 35.15 kg / cm2 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 evaporation of n-hexane under vacuum to yield 242 g of 4,8-dimethyl-2-nonanol.

EXAMPLE 12 Mixture of branched olefin substantially dimethyl with randomized branching (A mixture of branched olefin which is an alkylating agent for preparing modified alkylbenzenes according to the invention) To a 2-L three-necked ball flask with nitrogen blanket, equipped with a thermometer, mechanical stirrer and a Dean Stark trap 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-undecanoI (example 9) and 180 g of a shape selective zeolite catalyst (acid mordenite catalyst) Zeocat ™ FM-8 / 25H). When mixing, the mixture is heated (135-160 ° C) to the point where water and some olefin are carried and collected in the Dean Stark trap at a moderate speed. After a few hours, the speed of the water collection decreases and the temperature rises to 180-195 ° C, where the reaction is allowed to mix for another 2-4 hours. The dimethyl branched olefin mixture remaining in the flask together with the dimethyl branched olefin mixture which was distilled is combined again and filtered to remove the catalyst. The catalyst filter cake is suspended with 500 ml of hexane and filtered in vacuo. The catalyst filter cake is washed twice with 100 ml of hexane and the concentrated filtrate by evaporation of hexane under vacuum. The resulting product is combined with the first filtrate to give 820 g of a mixture of branched dimethyl olefin with randomized branching.

EXAMPLE 13 Mixture of substantially dimethyl branched alkylbenzene with randomized branching and 2/3-phenyl index of about 200 and 2-methyl-2-phenyl index of about 0.04 (A mixture of modified alkylbenzene according to the invention) 820 g of the dimethyl branched olefin mixture of example 12 and 160 g of a form selective zeolite catalyst (Zeocat ™ PB / H acid beta zeolite catalyst) are added to a 7.56 liter stirred stainless steel autoclave and the autoclave it is sealed; the latter is purged twice with 5.62 kg / cm2 of N2, and then charged to 4.21 kg / cm2 of N2. From the outside of the autoclave cell, add 3000 g of benzene (contained in an insulated container and added by an isolated pump system inside the isolated autoclave cell) to the autoclave. The mixture is stirred and heated to about 205 ° C for about 8 hours. The autoclave is cooled to around 30 ° C overnight. The valve is opened by going from the autoclave to the benzene condenser and to the collection tank. The autoclave is heated to around 120 ° C with continuous collection of benzene. By the time the reactor reaches 120 ° C, no more benzene is collected and then the reactor is cooled to 40 ° C. The autoclave is drained to remove the reaction mixture; This is filtered to remove the catalyst and pulled under vacuum in the mixture to remove any residual traces of benzene. The product is distilled under vacuum (1-5 mm Hg). The mixture of branched dimethyl alkylbenzene with randomized branching and 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 randomized 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 the example 13 is sulfonated with one molar equivalent of chlorosufonic acid using methylene chloride as solvent with evolved HCl as a secondary product. The resulting sulfonic acid product is concentrated by evaporation of methylene chloride under vacuum. The resulting sulphonic acid product has a 2/3-phenyl index of about 200 and a 2-methyl-2-phenyl index of about 0.04.

EXAMPLE 15 Mixture of sodium salt, branched substantially alkybenzene sulphonic acid dimethyl with randomized branching and 2/3-phenyl index of about 200 and a 2-methyl-2-phenyl index of about 0.04 (A mixture of alkylbenzene sulphonate surfactants modified 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 solid mixture of sodium salt, branched dimethyl alkylbenzene sulfonate with randomized 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 number of about 200 and a 2-methyl-2-phenyl index of about 0.01 (A mixture of modified alkylbenzene 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 number of about 200 and a 2-methyl-2-index. phenyl of about 0.01 EXAMPLE 17 Mix of salts and linear and branched alkylbenzene sulfonic acid with a 2/3-phenyl number of about 200 and a 2-methyl-2-phenyl index of about 0.01 (Mixtures of modified alkyiiebenzenesulfonic acid and mixtures of salts of the invention) a) Mixture of modified alauylbenzenesulfonic acid of the invention The modified alkylbenzene mixture resulting from example 16 is sulfone with one molar equivalent of chlorosulfonic acid using methylene chloride as solvent with evolved HCl as a by-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 index of about 200 and a 2-methyl-2-phenyl index of about 0.01. b) Sodium salt mixture, modified alkylbenzene sulphonate of the invention The product of Example 17a) is neutralized with one molar equivalent of sodium methoxide in methanol and the methanol is evaporated to give a solid mixture of sodium salt, modified alkylbenzene sulphonate of the invention with a 2/3-phenyl index of about 200 and a 2-methyl-2-phenyl index of about 0.01.

Methods for determining composition parameters (2/3-phenyl index, 2-methyl-2-phenyl index) of mixed alkylbenzene / alkylbenzenesulfonate / alkylbenzenesulfonic acid systems The determination of compositional parameters of conventional linear alkylbenzenes is well known in the art. / or highly branched alkylbenzene sulphonates (TPBS, ABS). See for example Surfactant Science Series, volume 40, chapter 7 and Surfactant Science Series, volume 73, chapter 7. Almost always, this is carried out by GC and / or GC mass spectroscopy for alkylbenzenes and HPLC for alkylbenzenesulfonates or acids sulphonic; 13C NMR is also commonly used. Another common practice is desulphonation. This allows GC and / or GC mass spectroscopy to be used, since the desulfonation converts sulphonates or sulfonic acids to alkylbenzenes that are treatable by these methods. In general, the present invention provides mixtures of unique and relatively complex alkylbenzenes, and mixtures of surfactants of similar complexity of alkylbenzenesulfonates and / or alkylbenzenesulfonic acids. The composition parameters of said compositions can be determined using variations and combinations of methods known in the art. The sequence of methods to be used depends on the composition that will be characterized as follows: Composition to be Sequence of methods (the methods separated by characterizing commas are carried out in sequence, others can be performed in parallel) Alkylbenzene mixtures GC, RMN1 NMR2 Alkylbenzene mixtures GC, DIS, GC, NMR1 NMR2 with impurities1 'Acid mixtures Option 1: HPLC, RMN4 alkylbenzenesulfonic NMR4 Option 2: HPLC, DE, RMN1 RMN2 Salt mixtures of Option 1: HPLC, AC, RMN3 RMN4 alkylbenzenesulfonate Option 2: HPLC, DE, RMN1 NMR2 Acid mixtures Option 1: HPLC, HPLC-P, HPLC, RMN4 alkylbenzenesulfonic RMN4 with Option 2: HPLC, DE, DIS, GC, RMN1 NMR2 impurities * Option 1 salt mixtures: HPL, HPLC-P, HPLC, AC, NMR4 RMN4 alkylbenzenesulfonate with Option 2: HPLC, DE, DIS, GC, RMN1 NMR2 impurities * * Typically preferred when the material contains more than about 10% impurities, such as dialkylbenzenes, olefins, paraffins, hydrotropes, dialkylbenzenesulfonates, etc.

GC Equipment: • Hewlett Packard HP5890 Series II gas chromatograph, equipped with an FID and an injector with divisions / without divisions • Scientific capillary column J & DB-1 HT, 30 meters, 0.25 mm id, 0J um film thickness cat # 12221131 • Restek Lite Red 11mm Cat Seal # 22306 • Restek 4mm Gooseneck Entrance Sleeve with a Carbofrit cat # 20799-209.5 • Hewlett Packard Cat Entrance Liner Packing # 5180-4182 • HPLC grade methylene chloride J.T. Baker cat # 9315-33 or equivalent • Self-contained 2 ml GC vials with top flange or equivalent Sample preparation • Weigh 4-5 mg of sample in a 2 ml GC auto vial • Add 1 ml of methylene chloride of HPLC grade J.T. Baker, cat # 9315- 33 to GC vial, seal with Teflon coated covers (lids) for vials with flange, part # HP5181-1210 using a bending instrument, part # HP8710-0979 and mix well • Sample is now ready for injection in the GC GC Parameters Carrier gas: hydrogen Column head pressure: 0.63 kg / cm2 Flows: Column flow at 1 ml / min. Ventilation divided at ~ 3 ml / min. Septum purge at 1 ml / min. Injection: Auto HP7673, syringe 10 ul, injection 1 ul Injector temperature: 350 ° C Detector temperature: 400 ° C Homogen temperature program: initial 70 ° C, wait: 1 min. Proportion 1 ° C / min. End 180 ° C, wait: 10 min. The standards required for this method are 2-phenyloctane and 2-phenylentadecane, each fresh from distillation at a purity greater than 98%. Both standards are made using the conditions specified above to define the retention time for each rule. This defines a ratio of retention time that is in the proportion of retention time that will be used to characterize any of the alkylbenzenes or alkylbenzene mixtures in the context of this invention (e.g., test samples). The test samples are then carried out for which the composition parameters are determined. The test samples pass the GC test, provided that more than 90% of the total GC area percentage is within the proportion of retention time 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 should be further purified by distillation until the test sample passes the GC test.

Desulfonation (DE) The desulphonation method is a normal method described in G.F. "The Analysis of Detergents and Detergent Products". Longman on pages 197-199. Two other useful descriptions of this normal method are found on pages 230-231 of volume 40 of Surfactant Science Series, edited by TM Schmitt: "Analysis of Surfactants" and on page 272 of volume 73 of Surfactant Science Series: "Anionic Surfactants ", edited by John Cross. This is an alternative method for the HPLC method, described herein, for the evaluation of mixtures of branched and unbranched alkylbenzenesulfonic acid and / or salt (mixtures of salt and / or modified alkylbenzenesulfonic acid). The method provides a means for converting the mixture of sulphonic acid and / or salt into branched and unbranched alkylbenzene mixtures which can be analyzed by the GC and NMR, NMR1 and NMR2 methods described herein.

HPLC See S.R. Ward, Anal. Chem., 1989, 61, 2534; DJ. Pietrzyk and S. Chen, Univ. Lowa, Dept. of Chemistry.

Apparatus Adequate Waters HPLC System Millipore Division or equivalent HPLC pump with He and Waters sprayer, model 600 or equivalent Temperature control Waters 717 injector or equivalent or 48-position Tray for Waters or automatic equivalent Waters PDA 996 UV detector or equivalent Fluorescence detector Waters 740 or equivalent data / integrator Waters 860 or equivalent Vials of auto and covers Capacity 4 ml, Millipore # 78514 and # 78515 HPLC column, X82 Supelcosil LC18, 5μm, 4.6 mm x 25 cm, Supelcosil # 58298 Rheodyne column inlet filter 0.5 μm x 3 mm Rheodyne # 7335 LC Millipore SJHV M47 10 elution membrane filters, disposable filter funnel with membrane 0.45 μm Sartorius balance or equivalent; Accuracy ± 0.0001 g Vacuum Sample clarification equipment with pumps and filters, Waters # WAT085113 Reagents Normal material of LAS C8 Sodium-p-2-octylbenzene sulfonate Normal material of LAS C15 Sodium-p-2-pentadecylbenzene sulfonate 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 an LC eluent membrane filter and degas before use. 2) Mobile phase B Prepare 2000 ml of 60% acetonitrile in HPLC grade water. Filter through an LC eluent membrane filter and degas before use.

B. Normal internal solution of C8 v C15 1) Weigh standards of 0.050 g of 2-phenoctylbenzenesulfonate and 0.050 g 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 HPLC grade water. This prepares a 1500 ppm solution of the mixed standard.

C. Sample solutions 1) Washing solutions: Transfer 250 μl of the normal solution to a 1 ml self-vial and add 750 μl of the washing solution. Cover and place in the tray for self. 2) Alkylbenzenesulfonic acid or alkylbenzenesulfonate: Weigh OZOg of 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 normal solution to a 1 ml self-vial and add 750 μl of the sample solution.

Cover and place in the tray for self. If the solution has an excess of turbidity, it is filtered through a 0.45 μm membrane before transferring to the auto vial. Cover and place in the self-cleaning tray.

D. HPLC system 1) Prepare the HPLC pump with the mobile phase. Install the column and the inlet filter of the column and equilibrate with eluent (0.3 ml / min for at least 1 hour). 2) Perform the samples using the following HPLC conditions: Mobile phase A 100 mM NaCl / 40% ANC Mobile phase B 40% H2O / 60% ACN Time 0 min. 100% mobile phase A 0% mobile phase B Time 75 min. 5% mobile phase A 95% mobile phase B Time 98 min. 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 gradient delay time of 5-10 minutes may be necessary, depending on the dead volume of the HPLC system.

Flow rate 1.2 ml / min. Temperature 25 ° C Proportion of He sprayer 50 ml / hour UV detector 225 nm Fluorescence detector? = 225 nm,? = = 295 nm with sensitivity at 10 x Execution time 120 min. Injection volume 10 μl Replica injections 2 Data proportion 0.45 MB / hour Resolution 4.8 nm 3) The column should be washed with 100% water followed by 100% acetonitrile and stored in 80/20 ACN / water. The HPLC elution time of the 2-phenyloctylbenzenesulfonate defines the lower limit and the elution time of the 2-phenylpentadecane sulphonate standard defines the upper limit of the HPLC analysis that relates 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 previous standards, then the sample can be further defined by NMR3 and NMR4 methods. If the alkylbenzene sulfonic acid / salt mixture contains 10% or more of components outside the retention limits defined by the standards, then the mixture must be further purified by the HPLC-P method or by methods DE, DIS.

Preparative HPLC (HPLC-P) Alkylbenzenesulfonic acids and / or salts containing substantial impurities (10% or greater) are purified by HPLC. See, for example Surfactant Science Series, Volume 40, Chapter 7 and Surfactant Science Series, Volume 73, Chapter 7. This is routine for those skilled in the art. A sufficient quantity must be purified to meet the requirements of NMR3 and RMN4.

Preparative LC 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 an LC method (also referred to herein as HPLC- P). In fact, this method is preferred over preparative HPLC column purification. As many as 500 mg of unpurified MLAS salts can be loaded in a 10 g (60 ml) Elut Sep Pak® Mega Bond and with optimized chromatography, the purified MLAS salt can be isolated and ready for freeze drying in 2 hours. A sample of 100 mg of modified alkylbenzene sulfonate salt can be loaded into a 5 g (20 ml) Bond Elut Sep Pak and ready at the same time.

A) HPLC instrumentation: Waters Model 600E gradient pump, Model 717 model, Waters Millennium PDA, Millenium data controller (v. 2.15) Mega Bond Elut: C18 joined phase, Varian 5g or 10 g, PN: 1225-6023, 1225-6031 with adapters HPLC Columns: Supelcosil LC-18 (X2), 250 x 4.6 mm, 5 mm; # 58298 Laboratory scale: Mettier model AE240, which can weigh samples to ± 0.01 mg.

B) Volumetric accessories: glass, 10 ml Graduated cylinder: 1 L HPLC self-priming vials: 4 ml glass vials with Teflon and pipette covers and low volume glass inserts that can accurately deliver volumes of 1, 2 and 5 ml.

O Reagents and chemical substances Water (DI-H2O): deionized and distilled water from a Millipore Millipore system or equivalent Acetonitrile (CH3CH): Baker's HPLC grade or equivalent, Baker's sodium chloride crystal analyzed or equivalent.

D) HPLC conditions Preparation of the aqueous phase: A) To 600 ml of DI-H O contained in a graduated cylinder of 1 L, 5.845 of sodium chloride is added; mix well and 400 ml of ACN are added; It mixes well. B) To 400 ml of Dl-H20 contained in a 1L graduated cylinder add 600 ml of ACN and mix well. Tank A: 60 / 40m H2O / CAN with salt and Tank B: 40/60, H2O / ACN Conditions of implementation: Gradient: 100% A for 75 minutes, 5% A / 95% B for 98 minutes, 5% A / 95% B for 110 minutes, 100% A for 125 minutes.

Column temperature Without thermostat control (ie, room temperature) HPLC flow rate 1.2 ml / minute Injection volume 10 ml Delivery time 125 minutes UV detection 225 nm Conc. > 4 mq / ml Balance of Sep Pak (Bond Elut, 5 q) 1) Pass 10 ml of a solution containing 25/75 H2O / ACN in the Sep Pak applying positive pressure with a 10 cc syringe at a rate of ~ 40 drops / minute; it should be avoided that the Sep Pak dries. 2) Immediately pass 10 ml (x3) of a solution containing 70/30 H2O / ACN in the same manner as in # 1; it should be avoided that the Sep Pak it dries; maintain a solution level (-1 mm) in the head of the Sep Pak. 3) Now the Sep Pak is ready to load the sample.

Sample charge / separation and MLAS insulation 4) Weigh < 200 mg of the sample in a vial of 1772 g and add 2 ml of 70/30 H2O / ACN. Sonicate and mix well.

) Load the sample in Bond Elut and with positive pressure from a syringe of 10 cc 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 solution in the head of the Sep Pak. 6) Pass 10 ml of 70/30 in Bond Elut with positive pressure from a 10 cc syringe at a rate of -40 drops / minute. 7) Repeat this with 3 ml and 4 ml and collect the effluent, if there is interest in the impurities.

Isolation and collection of MLAS 1) Pass 10 ml of solution containing 25/75 H2O / ACN with positive pressure from a 10 cc syringe and collect the effluent. Repeat this with another 10 ml and once again with 5 ml. The isolated MLAS is now ready for freeze drying and subsequent characterization. 2) Place in a rotary evaporator until the ACN is removed and freeze the remaining H2O. Now the sample is ready for chromatography. Note: By incorporating the Mega Bond Elut Sep Pak (version 10 g), up to 500 mg of the sample can be loaded in the Sep Pak and with volume adjustments of the solution, the effluent can be ready for freeze drying in 2 hours .

Balance of Sep Pak (Bond Elut, 10 q) 1) Pass 20 ml of a solution containing 25/75 H2O / ACN in the Sep Pak using laboratory air or regulated cylinder air at a rate that allows -40 drops / minute . Positive pressure can not be used from a syringe because it is not enough to move the solution through the Sep Pak. The Sep Pak should be prevented from drying out. 2) Immediately pass 20 ml (x2) and 10 ml more of a solution containing 70/30 H2O / ACN in the same way as in # 1. The Sep Pak should be prevented from drying out. Maintain a solution level (-1 mm) in the head of the Sep Pak. 3) Now the Sep Pak is ready to load the sample.

Sample loading / separation and isolation of MLAS 1) Weigh < 500 mg of sample in a vial of 3544 g and add 5 ml of 70/30 H2O / ACN. Sonicate and mix well. 2) Load the sample in Bond Elut and with positive pressure from an air source begin the separation. Rinse the vial with 2 ml portions (x2) of the 70/30 solution and place 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 Elut with positive pressure from an air source at a rate of -40 drops / minute. Repeat this with 6 ml and 8 ml and collect the effluent to be interested in the impurities.

Isolation and collection of MLAS 1) Pass 20 ml of solution containing 25/75 H2O / ACN with positive pressure from an air source and collect the effluent. 2) Repeat this with another 20 ml and once again with 10 ml. This isolated fraction contains pure MLAS. 3) Isolated MLAS is now ready for freeze drying and subsequent characterization. 4) Place in a rotary evaporator until the ACN is eliminated and freeze the remaining H2O. The sample is now ready for chromatography. Note: Adjustments in organic modifier concentration may be necessary to achieve optimum separation and isolation.

Distillation (DIS) A 5-liter three-necked ball flask with 24/40 splices is equipped with a magnetic stir bar. Some boiling fragments (Hengar granules, catalog # 136-C) are added to the flask. A Vigreux condenser 24.13 cm in length with a 24/40 splice is placed in the central neck of the flask. A water-cooled condenser is attached to the top of the Vigreux condenser that is equipped with a calibrated thermometer. A flask receiving vacuum is attached to the end of the condenser. A frosted glass plug is placed on a side arm of the 5-liter flask and a calibrated thermometer on the other. The flask and the Vigreux condenser are wrapped in aluminum foil. To the 5 liter flask is added 2270 g of an alkylbenzene mixture containing 10% or more impurities, as defined by the GC method. A vacuum line running from a vacuum pump is attached 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 per manometer 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 on the top of the Vigreux column. Fraction B is collected from about 90 ° C to about 155 ° C, as measured by the calibrated thermometer in the upper part of the Vigreux column. Fraction A and container residues (high boiling point) are discarded. Fraction B 81881 g) contains the alkylbenzene mixture of interest. The method can be scaled according to the needs of the expert, as long as the sufficient amount of the alkylbenzene mixture remains after distillation for evaluation by RMN1 and NMR2 NMR methods.

Acidification (AC) Alkylbenzenesulfonic acid salts are acidified by common means, such as reaction in a solvent with HCl or sulfuric acid or by the use of an acid resin, such as Amberlyst 15. Acidification is routine for those skilled in the art. technique. After acidification all solvents are removed, especially any moisture, so that the samples are anhydrous and do not have solvents.

Note: For the rest of the NMR test methods that follow, the chemical changes of the NMR spectrum are considered externally with respect to CDCI3, that is, chloroform.

RMN1 2/3-phenyl index of 13 C-NMR for alkylbenzene mixtures A sample of 400 mg of an alkylbenzene mixture is dissolved in 1 ml of anhydrous deuterated chloroform containing 1% v / v of TMS, as a reference, and placed in a normal NMR tube. The 13 C NMR is performed on the sample on a 300 MHz NMR spectrometer using a recycle time of 20 seconds, a 13 C pulse amplitude of 40 ° and interrupted heteronuclear uncoupling. At least 2000 readings are recorded. The 13 C NMR spectrum region is integrated between about 145.00 ppm to about 150.00 ppm. 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 of about 145.70 ppm to about 146.15 ppm) x 100 NMR2 2-Methyl-2-phenyl Index of 13 C NMR A sample of 400 mg of an anhydrous alkylbenzene mixture is dissolved in 1 ml of anhydrous deuterated chloroform containing 1% v / v of TMS, as a reference, and placed in a normal NMR tube. The 13 C NMR is performed on the sample on a 300 MHz NMR spectrometer using a recycle time of 20 seconds, a 13 C pulse amplitude of 40 ° and interrupted heteronuclear uncoupling. At least 2000 readings are recorded. The 13 C NMR spectrum region is integrated between about 145.00 ppm to about 150.00 ppm. The 2-methyl-2-phenyl index of an alkylbenzene mixture is defined by the following equation: 2-methyl-2-phenyl index = (integral of about 149.35 ppm to about 149.80 ppm) (integral of about 145.00 ppm to about of 150.00 ppm) NMR3 Index 2/3-phenyl of 13 C NMR for mixtures of alkylbenzenesulfonic acid A sample of 400 mg of an anhydrous alkylbenzene sulfonic acid mixture is dissolved in 1 ml of anhydrous deuterated chloroform containing 1% v / v of TMS, as a reference, and It is placed in a normal MRI tube. The 13 C NMR is performed on the sample on a 300 MHz NMR spectrometer using a recycle time of 20 seconds, a 13 C pulse amplitude of 40 ° and interrupted heteronuclear uncoupling. At least 2000 readings are recorded. The 13 C NMR spectrum region is integrated between about 152.50 ppm to about 156.90 ppm. The 2/3-phenyl index of a mixture of alkylbenzenesulfonic acid is defined by the following equation: 2/3-phenyl index = (integral of about 154.40 ppm to about 154.80 ppm) / (integral of about 152.70 ppm to about 153.15 ppm) x 100 RMN4 2-methyl-2-phenyl index of 13, C NMR for mixtures of alkylbenzenesulfonic acid A sample of 400 mg of an anhydrous alkylbenzene sulfonic acid mixture is dissolved in 1 ml of anhydrous deuterated chloroform containing 1% v / v of TMS, as a reference, and placed in a normal NMR tube. The 13 C NMR is performed on the sample on a 300 MHz NMR spectrometer using a recycle time of 20 seconds, a 13 C pulse amplitude of 40 ° and interrupted heteronuclear uncoupling. At least 2000 readings are recorded. The 13 C NMR spectrum region is integrated between about 152.50 ppm to about 156.90 ppm. The 2-methyl-2-phenyl index for a mixture of alkylbenzenesulfonic acid is defined by the following equation: index 2-methyl-2-phenyl = (integral from about 156.40 ppm to about 156.65 ppm) / (about 152.50 ppm integral) at about 156.90 ppm) In one embodiment of the present invention, the hand dishwashing compositions have substantially no alkylbenzenesulfonate surfactants other than the modified alkyl benzene sulfonate surfactant mixture.; that is, no alkylbenzene sulfonate surfactant other than the modified alkylbenzene sulfonate surfactant mixture is added to the detergent compositions. In another embodiment of the present invention, the 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%, with even more preferably not more than about 1% of a commercial 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 an additional surfactant at least about 0.1%, preferably not more than about 10%, more preferably not more than about 5%, more preferably not more than about 1% of a commercially highly branched alkylbenzene sulfonate surfactant. For example TPBS or tetrapropylbenzenesulfonate The present invention encompasses less preferred, but sometimes useful, modalities for its normal purposes, such as the addition of useful hydrotrope precursors and / or hydrotropes, such as C?-C8 alkylbenzenes, more often toluenes, eumens, xylenes, naphthalenes or the sulfonated derivatives of any of those materials, minor amounts of any other material, such as trirramified alkylbenzenesulfonate surfactants, dialkylbenzenes and their derivatives, dialkyltretralins, wetting agents, processing aids and the like. It will be understood that, with the exception of the hydrotropes, it will not be a usual practice in this invention to include any of those materials. In a similar way it will be understood that these materials, if and when they interfere with analytical methods, will not be included in samples of compositions used for analytical purposes. Numerous variations of these detergent compositions are useful. Said variations include: the hand dishwashing composition which substantially does not have alkylbenzenesulfonate surfactants other than said modified alkylbenzene surfactant mixture; - the hand washing composition comprising, in said component (ii), at least about 0.1%, preferably not more than about 10%, more preferably not more than about 5%, still more preferably no more than about 1% of a commercial linear C 1 -C C alkyl-benzenesulfonate 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%, more preferably not yet more than about 1% of a commercially highly branched alkylbenzene sulfonate surfactant (eg, TPBS or tetrapropylbenzenesulfonate); - the hand dishwashing composition comprising, in said component (iii), a nonionic surfactant at a level of from about 0.5% to about 25% by weight of the detergent composition, and wherein said surfactant does not The ionic is a polyalkoxylated alcohol in a crowned or uncrowned form having: a hydrophobic group selected from C10-C6 linear alkyl, C10-C16 alkyl branched in the middle part of the C1-C3 chain, C10-C alkyl 6 branched Guerbet and mixtures thereof, and a hydrophilic group selected from 1-15 ethoxylates, 1-15 propoxylates, 1-15 butoxylates and mixtures thereof, in crowned or uncoated form. (When they are in non-coronated form, a terminal primary -OH part is also present, and when they are in crowned form, a terminal part of the -OR form is also present, wherein R is a hydrocarbyl part of C? -C6) optionally comprising a primary alcohol or, preferably when present, a secondary alcohol); - the hand dishwashing composition comprising, in said component (iii), an alkyl sulfate surfactant at a level of from about 0.5% to about 25% by weight of the detergent composition, wherein said alkyl sulfate surfactant has a hydrophobic group selected from linear C10-C18 alkyl, C? or C? 8 alkyl branched in the middle part of the C1-C3 chain, branched C? 0-C? 8 alkyl Guerbet and mixtures thereof and a cation selected from 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 the detergent composition, wherein said agent Alkyl (polyalkoxy) sulfate surfactant has: a hydrophobic group selected from C10-C16 linear alkyl, C? 0-C? 6 alkyl branched in the middle part of the C1-C3 chain, branched C-C16 alkyl, Guerbet and mixtures thereof, and a hydrophilic group of (poiialkoxy) sulfate selected from 1-15 polyethoxysulfate, 1-15 polypropoxysulfate, 1-15 polybutoxysulfate, 1-15 mixed poly (ethoxy / propoxy / butoxy) sulfates and mixtures thereof , crowned or not crowned; and a cation selected from Na, K and mixtures thereof. It is preferred that the hand dishwashing composition comprises an alkyl (polyalkoxy) sulfate surfactant having a hydrophobic group selected from linear C 0 -C 6 alkyl, branched C 10 -C 6 alkyl in the middle part of the C1-C3 chain, Guerbet branched C? 0-C? 6 alkyl and mixtures thereof; and a hydrophilic group of (polyalkoxy) sulfate selected from 1-15 polyethoxysulfate, 1-15 polypropoxysulfate, 1-15 polybutoxysulfate, 1-15 mixed poly (ethoxy / propoxy / butoxy) sulfates and mixtures thereof, in crowned or non-crowned form crowned and a cation selected from Na, K and mixtures thereof. It is preferred that when the hand dishwashing composition comprises a nonionic surfactant, it is a polyalkoxylated alcohol in the form of a crowned or non-capped form selected from a C 1 or C 6 linear alkyl group, branched C 10 -C 16 alkyl. in the middle part of the chain C1-C3, branched C10-C16 alkyl, Guerbet and mixtures thereof, and a hydrophilic group selected from 1-15 ethoxylates, 1-15 propoxylates, 1-15 butoxylates and mixtures thereof , crowned or not crowned. When they are in non-crowned form, there is also a terminal part -OH terminal, and when they are in crowned form, a terminal part of the -OR form is also present, wherein R is a hydrocarbyl part of C? -C6, optionally comprising a primary alcohol or, preferably when present, a secondary alcohol. It is preferred that the hand dishwashing composition comprises an alkyl sulfate surfactant having a hydrophobic group selected from linear C10-C16 alkyl, C10-C18 alkyl branched in the middle part of the C1-C3 chain, C-alkyl 0-C16 branched 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 unitary or altered doses freely, or through automatic dispensing means. They can be used in aqueous or non-aqueous cleaning systems. They may have a very varied pH, for example from about 2 to about 12 or greater, although alkaline detergent compositions having a pH from about 8 to about 11 are among the preferred embodiments, and may have a wide variety of preservatives. alkalinity. The types of high foaming and low foaming are covered, as well as the types that are used in all aqueous and non-aqueous cleaning procedures of the product for the consumer. The hand dishwashing compositions may be in any conventional form, namely, in the form of a liquid, powder, agglomerate, paste, tablet, bar, gel, liquid gel microemulsion, liquid crystals or granules.

Conventional methods and aids for hand dishwashing In general, a conventional hand dishwashing aid is any material necessary to transform a composition containing only the minimum essential ingredients (hereinafter the mixture of modified alkylbenzene sulfonate surfactants) into a useful composition for washing dishes by hand. In preferred embodiments, those skilled in the art can readily recognize conventional hand dishwashing aids as absolutely characteristic of cleaning products. The precise nature of these additional components and their levels of incoforation will depend on the physical form of the composition and the nature of the cleaning operation for which they will be used. The levels of conventional hand dishwashing aids are from about 0.00001% to about 99.9% by weight of the composition. The levels of use of the general compositions can vary widely, depending on the intended application, ranging from, for example, low ppm in solution to what is termed "direct application" of the pure cleaning composition to the surface to be cleaned. Preferably, the conventional hand dishwashing aid is selected from the group consisting of detergency builders, detersive enzymes, surfactants other than the mixture of modified alkylbenzenesulfonate surfactants, almost always selected from anionic, cationic, amphoteric, zwitterionic, non-ionic and mixtures thereof, water-dispersible or at least partially water-soluble polymers, abrasives, bactericides, stain inhibitors, dyes, solvents, hydrotropes, perfumes, thickeners, antioxidants, processing aids, foam boosters, foam suppressants, pH regulators, antifungal agents, mold control agents, insect repellents, anticorrosive auxiliaries, chelators and mixtures thereof. More preferably, the conventional cleaning aid comprises one or more of: The product cleaning compositions for the consumer are described in "Surfactant Science Series", Marcel Dekker, New York, volumes 1-67 and subsequent. The liquid compositions in particular are described in detail in volume 67, "Liquid Detergents", Ed. Kuo-Yann Lai, 1997, ISBN 0-8247-9391-9, which is incorporated herein by reference. The most classic formulations, especially those of granule type, are described in "Detergent Manufacture Including Zeolite Builders and Other New Materials," Ed. M. Sitting, Noyes Data Corporation, 1979, which is incorporated by reference. See also Kirk Othmer's Encyclopedia of Chemical Technology. Detergents with long-lasting perfume (see for example E.U.A. 5,500,154, WO 96/02490) are becoming increasingly popular and their use is envisaged together with the surfactant mixtures herein. In general, a conventional hand dishwashing aid is any material necessary to transform a composition containing only the minimum essential ingredients (hereinafter, the essential mixture of modified alkylbenzene sulfonate surfactants) into a composition useful for washing dishes by hand . In preferred embodiments, those skilled in the art can readily recognize conventional hand dishwashing aids as absolutely characteristic of cleaning products.

The precise nature of these additional components and their levels of incorporation will depend on the physical form of the composition and the nature of the cleaning operation for which they will be used. Common auxiliaries include builders, surfactants, enzymes and polymers, and the like. Other auxiliaries herein may include foam boosters, foam suppressors (antifoams) and the like, various active ingredients or specialized materials, such as dispersing polymers (eg, from BASF Corp., or Rohm & amp;; Haas), color spots, silver care, anti-stain and / or anti-corrosive agents, dyes, fillers, germicides, alkalinity sources, hydrotropes, antioxidants, enzyme stabilizing agents, pro-perfumes, perfumes, solubilizing agents, vehicles, auxiliaries of processing, pigments, and for liquid formulations, solvents, as described in detail herein. Very often, the compositions herein may require several auxiliaries, although certain products formulated in a simple manner may require a single auxiliary. A comprehensive list of suitable auxiliary methods and materials for cleaning or laundry can be found in the provisional patent application of E.U.A. No. 60 / 053,318, filed July 21, 1997, and assigned to Procter & Gamble. The modified alkylbenzenesulfonate surfactants of this invention can be used in a wide variety of formulations for washing dishes by hand. This novel surfactant system can be used as a partial or total replacement of conventional LAS in existing hand dishwashing compositions. Formulations wherein the modified alkylaminobenzene sulfonate surfactants of this invention can be used as a supplement to the existing surfactant system or as a partial or total replacement for LAS in the surfactant system including, but not limited to: WO 98/122290; E.U.A. 5728668; WO 98/05745; E.U.A. 5756441; E.U.A. 5714454; E.U.A. 5712241; E.U.A. 5707955; E.U.A. 4,133,779; WO 97/47717; E.U.A. 5688754; E.U.A. 5665689; WO 9738073; E.U.A. 5696073; WO 97/38071; WO 97/00930 A; GB 2,292,562 A; E.U.A. 5,376,310; E.U.A. ,269,974; E.U.A. 5, 230,823; E.U.A. 4,923,635; E.U.A. 4,681, 704; E.U.A. 4,316,824; E.U.A.4,133,779; E.U.A.5700773; WO 9735947; WO 97/34976; E.U.A. 5629279; WO 9715650; E.U.A. 5616548; E.U.A. 5610127; E.U.A. 5565421; WO 96/31586; E.U.A. 5561106; E.U.A. 5552089; WO 96/22347; E.U.A.5503779; E.U.A.5480586; EP 573329; E.U.A.5382386; EP 487169; E.U.A. 5096622; EP 431050; E.U.A. 5102573; E.U.A. 4772425; E.U.A. 4725337; EP 228797; E.U.A. 4556509; E.U.A. 4454060; E.U.A. 4554098; E.U.A.4430237; E.U.A.4877546; E.U.A.4064076; E.U.A.410456; E.U.A. 3944663; E.U.A.4040989; E.U.A.4102826; E.U.A.5767051; E.U.A.5780417; WO 97/26315; E.U.A. 5290482; E.U.A. 3954679; E.U.A. 5700331; E.U.A. 56798877; E.U.A.5565419; WO 98/22569; E.U.A.5736496; E.U.A.5733560; E.U.A. 574169; E.U.A. 5733860; E.U.A. 5741770; E.U.A. 5719114; E.U.A. 5604195; EP 848749; EP 839177; E.U.A. 5646104; E.U.A. 5580848; EP 781324; E.U.A. 5415812; E.U.A. 5435936; E.U.A. 5082584; E.U.A. 5393468.

Detersive Surfactants The compositions in question desirably include a detersive surfactant employed as a surfactant coagent with the mixtures of essential surfactants. Since the present invention relates to surfactants, in the descriptions of the preferred embodiments of the detergent compositions, the surfactant materials are described and counted separately from auxiliaries which are not surfactants. Detersive surfactants are widely illustrated in US Pat. No. 3,929,678, December 30, 1975 to Laughlin, et al, and US patent. No. 4,259,217, March 31, 1981, to Murphy; in the series "Surfactant Science", Marcel Dekker, Inc., New York and Basel; in "Handbook of Surfactants", M.R. Porter, Chapman and Hall, 2nd edition, 1994; "Surfactants n Consumer Products", Ed. J. Falbe, Springer-Verlag, 1987, and numerous patents related to detergents, assigned to Procter & Gamble and other manufacturers of detergents and consumer products. The detersive surfactant herein includes anionic, nonionic, cationic, zwitterionic or amphoteric types of the surfactant known to be used as a cleaning agent, but does not include completely foam-free or completely insoluble surfactants (although these may be used as optional auxiliaries) . In more detail, the detersive surfactants useful herein include suitably: (1) conventional alkylbenzenesulfonates, which encompass hard (ABS, TPBS) or linear types and which are made by known procedures, such as various HF or HF solids, for example, DETAL® process (UOP), or which are made using other Lewis acid catalysts, for example AICI3, or made using acid / alumina silica or from chlorinated hydrocarbons; (2) olefin sulfonates, including α-olefin sulfonates and sulfonates derived from fatty acids and fatty esters, (3) alkyl or alkenyl sulfosuccinates, which include diester and half ester types, as well as sulfosuccinates and other types of surfactants sulfonate / carboxylate, such as sulfosuccinates derived from ethoxylated alcohols and alkanolamides; (4) paraffin or alkane sulfonate and alkyl or alkenyl carboxy sulfonate types, which include the product for adding bisulfite to alpha olefins; (5) alkylnaphthalenesulfonates; (6) alkyl isethionates and alkoxypropanesulfonates, as well as fatty esters of fatty esters, fatty esters of alkoxylated isethionate and other ester sulphonates, such as the 3-hydroxypropanesulfonate ester or AVANEL S types; (7) benzene, cumene, toluene, xylene and naphthalene sulfonates, useful in particular for their hydrotrope forming properties; (8) alkyl ether sulfonates; (9) amide alkyl sulfonates; (10) esters or salts of a-sulfo fatty acids and esters of internal sulfo fatty acids; (11) alkyl glyceryl sulfonates; (12) ligninsulfonates; (13) petroleum sulfonates, sometimes known as heavy alkylate sulfonates; (14) diphenyl oxide disulfonates; (15) linear or branched alkyl sulfates or alkenyl sulfates; (16) alkyl sulfates or alkylphenol alkoxylate and the corresponding polyalkoxylates, sometimes known as alkyl ether sulfates, as well as alkenyl alkoxy sulfates or alkenyl polyalkoxy sulfates; (17) amide alkylsulfates or amide alkenyl sulfates, including sulphated alkanolamides and their alkoxylates and polyalkoxylates; (18) sulphated oils, sulfated alkyl glycerides, sulfated alkyl polyglycosides or sulfated sugar-derived surfactants; (19) alkyl alkoxycarboxylates and alkylpolyacoxycarboxylates, including salts of galacturonic acid; (20) alkyl ester carboxylates and alkenyl ester carboxylates; (21) alkyl or alkenyl carboxylate, especially conventional soaps and a, tp-dicarboxylates, which also include the alkyl- and alkenyl succinates; (22) alkoxy- and polyalkoxy carboxylates of alkyl or alkenyl amide; (23) types of alkyl and alkenyl amidocarboxylate surfactants; (24) amide soaps, sometimes referred to as fatty acid cyanamides; (25) alkylpolyaminocarboxylates; (26) phosphorus-based surfactants, including alkyl or alkenyl phosphate esters, alkyl ether phosphates including their alkoxylated derivatives, salts of fopsatidic acid, salts of alkylphosphonic acid, di (polyoxyalkylene alkanol) alkyl phosphates, amphoteric phosphates , such as lecithins; and phosphate / carboxylate, phosphate / sulfate and phosphate / sulfonate types; (27) nonionic surfactants of the Pluronic and Tetronic type; (28) the so-called EO / PO block polymers, which include the EPE and PEP types of diblock or triblock; (29) polyglucolic esters of fatty acids; (30) alkyl or alkylphenol capped or uncoated ethoxylates, propoxylates and butoxylates including polyethylene glycol ethers of fatty alcohol; (31) fatty alcohols, especially where they are useful as viscosity modifying surfactants or which are present as unreacted components of other surfactants; (32) N-alkyl polyhydroxy fatty acid amides, especially the alkyl N-alkylglucamides; (33) nonionic surfactants derived from mono- or polysaccharides or sorbitan, especially the alkyl polyglucosides, as well as fatty acid esters of sucrose; (34) esters of ethylene glycol, propylene glycol, glycerol and polyglyceryl and their alkoxylates, especially glyceryl ethers and the monoesters and fatty acid diesters / glycerol; (35) aldobionamide surfactants; (36) types of nonionic surfactants of alkylsuccinimide; (37) acetylenic alcohol surfactants, such as SURFYNOLS; (38) alkanolamide surfactants and their alkoxylated derivatives including fatty acid alkanolamides and polyglycol fatty acid alkanolamide ethers; (39) alkylpyrrolidones; (40) alkylamine oxides, including alkoxylated or polyalkoxylated amine oxides and amine oxides derived from sugars; (41) alkylphosphine oxides; (42) sulfoxide surfactants; (43) amphoteric sulfonates, especially sulfobetaines; (44) amphoteric betaine type, including types derived from aminocarboxylate; (45) amphoteric sulfates, such as alkylammonium polyethoxysulfates; (46) salts of amine and fatty alkylamines and petroleum derivatives; (47) alkylimidazolines; (48) alkylamidoamines and their alkoxylate and polyalkoxylate derivatives; and (49) conventional cationic surfactants, including water-soluble alkyltrimethylammonium salts. Also included are the most unusual types of surfactants, such as: (50) alkylamidoamine oxides, carboxylates and quaternary salts; (51) sugar-derived surfactants modeled after any of the conventional types that are not sugars referred to above; (52) fluorosurfactants; (53) biosurfactants; (54) organosilicon or fluorocarbon surfactants; (55) twin surfactants, other than the diphenyl oxide disulfonates referred to above, including those derived from glucose; (56) polymeric surfactants, including amphipicarboxyglycinates; (57) Bolaform surfactants; in short, any known surfactant for aqueous or non-aqueous cleaning. In any of the above detersive surfactants, the hydrophobic chain length is almost always on the C8-C20 general scale, of which the chain lengths on the C8-C18 scale are preferred, especially when the washing will be carried out in cold water. The selection of chain lengths and the degree of alkoxylation for conventional purposes is described in the standard texts. When the detersive surfactant is a salt, any compatible cation may be present, including H (ie, the acid or partially acid form of a potentially acidic surfactant may be used), Na, K, Mg, ammonium or alkanolammonium, or combinations of cations. Mixtures of detersive surfactants having different fillers are usually preferred, especially anionic / cationic, anionic / nonionic, anionic / nonionic / cationic, anionic / nonionic / amphoteric, nonionic / cationic and nonionic / amphoteric mixtures. In addition, any detersive surfactant can be replaced, often with desirable results for washing in cold water, by mixtures of otherwise similar detersive surfactants having different chain lengths, degree of unsaturation or branching, degree of alkoxylation (especially, ethoxylation), insertion of substituents, such as oxygen ether atoms in the hydrophobes, or any combination thereof. Among the above-identified detersive surfactants which are preferred are: C9-C20 linear alkylbenzenesulfonates of acid, sodium and ammonium, in particular linear C10-C5 alkylbenzenesulfonates in particular of sodium, although in some ABS regions they can be used (1 ); olefin sulphonate salts, (2) that is, material made by reaction of olefins, in particular α-olefins of C? or C20,, with sulfur trioxide and then the neutralization and hydrolysis of the reaction product; sodium and ammonium C7-C? 2 dial dialkylsulfosuccinates, (3) alkane monosulfonates, (4) as derivatives by the reaction of α-olefins of Cß-C20 con with sodium bisulfite and those derived by the reaction of paraffins with SO2 and Cl2 and then hydrolysis with a base to form a random sulfonate; salts or a-sulfo esters of fatty acids (10); sodium alkyl glyceryl sulphonates (11), especially the ethers of the higher alcohols derived from tallow or coconut oil and synthetic alcohols derived from petroleum; alkyl or alkenyl sulfates (15) which may be primary or secondary, saturated or unsaturated, branched or unbranched. Such compounds, when branched, can be random or regular. When they are secondary, it preferably has the formula CH3 (CH2) x (CHOSO3"M +) CH3 or CH3 (CH2) and (CHOSO3" M +) CH2CH3, where xy (y +1) are integers of at least 7, preferably at least 9 and M is a water-soluble cation, preferably sodium. When they are not saturated, sulfates such as oleyl sulfate are preferred, while sodium and ammonium alkyl sulfates, especially those produced by sulfonation of C 8 -C 8 alcohols, produced for example from tallow or coconut oil are also useful.; also preferred are alkyl or alkenyl ether sulfates (16), especially ethoxysulfates having about 0.5 moles or more of ethoxylation, preferably 0.5-8; the alkyl ether carboxylates (19), especially EO 1-5 ethoxycarboxylates; soaps or fatty acids (21), preferably the most water-soluble types; amino acid-type surfactants (23), such as sarcosinates, especially oleic sarcosinate; phosphate esters, (26); alkyl or alkylphenol ethoxylates, propoxylates and butoxylates (30), especially the ethoxylates "AE", which include the so-called narrow alkyl alkyl ethoxylates and phenolic alkoxylates of C6-C12 alkyl, as well as the products of C8-C alcohols? 8 linear or branched, primary or secondary aliphatic with ethylene oxide, in general 2-30 EO; N-alkyl polyhydroxy fatty acid amides, in particular C12-C8 methylglucamides (32), see WO 9206154, and N-alkoxy polyhydroxy fatty acid amides, such as C10-C18 N- (3-methoxypropyl) glucamide , whereas N-propyl to N-hexyl C12-C18 glucamides can be used for low foam formation; alkyl polyglucosides (33); amine oxides (40), preferably N-alkyl dimethylamine oxides and their dihydrates; sulfobetaines or "sultaines" (43); betaines (44); and twin surfactants. Suitable cationic surfactants for use in the present invention include those having a long chain hydrocarbyl group. Examples of such cationic surfactant coagents include ammonium surfactant coagents, such as alkyldimethylammonium halides, and surfactant coagents having the formula: [R2 (OR3) and] [R4 (OR3) and] 2R5N +? - wherein R2 is an alkyl or alkylbenzyl group having 8 to 18 carbon atoms in the alkyl chain, each R3 is selected from the group consisting of -CH2CH2-, -CH2CH (CH3) -, CH2CH (CH2OH) -, -CH2CH2CH2-, and mixtures thereof; each R 4 is selected from the group consisting of C 1 -C 4 alkyl, C 1 -C 4 hydroxyalkyl, benzyl ring structures formed by the joining of the two groups R 4, -CH 2 CHOH-CHOHCOR 6 CHOHCH 2 OH, wherein R 6 is any hexose or polymer of hexose having the molecular weight less than about 1000, and hydrogen when and not being 0; R5 is the same as R4 or is an alkyl chain, wherein the total number of carbon atoms of R2 plus R5 is not greater than about 18; each y is from 0 to about 10 and the sum of the values of y is from 0 to about 15; and X is any compatible anion. Examples of other suitable cationic surfactants are described in the following documents, which are incorporated herein by reference in their entirety: M.C. Publishing Co., McCutcheon's, Detergents & Emulsifiers, (American edition, 1997); Schwartz, et al., Surface Active Agents, Their Chemistry and Technology, New York: Interscience Publishers, 1949; patent of E.U.A. No. 3,155,591; patent of E.U.A. No. 3,929,678; patent of E.U.A. No. 3,959,461, patent of E.U.A. No. 4,387,090 and patent of E.U.A. No. 4,228,044. Examples of suitable cationic surfactants are those corresponding to the general formula: wherein R, R2, R3 and R4 are independently selected from an aliphatic group of 1 to about 22 carbon atoms or an aromatic, alkoxy, polyoxyalkylene, alkylamido, hydroxyalkyl, aryl or alkylaryl group having up to about 22 carbon atoms; and X is a salt forming anion, as selected from halogen radicals, (eg, chloride, bromide), acetate, citrate, lactate, glycolate, phosphate nitrate, sulfate and alkyl sulfate. The aliphatic groups may contain, in addition to carbon and hydrogen atoms, ether linkages, and other groups, such as amino groups. Longer chain aliphatic groups, for example those of about 12 carbons, or more, can be saturated or unsaturated. It is preferred when Ri, R2, R3 and R4 are selected from C1 to C alkyl. In particular, cationic materials containing two long alkyl chains and two short alkyl chains or those containing one long alkyl chain and three short alkyl chains are preferred. The long alkyl chains in the compounds described in the preceding sentence have from about 12 to about 22 carbon atoms, preferably from about 16 to about 22 carbon atoms, and the short alkyl chains in the compounds described in The above sentence has from 1 to about 3 carbon atoms, preferably from 1 to about 2 carbon atoms. Suitable levels of cationic detersive surfactant herein are from about 0.1% to about 20%, preferably from about 1% to about 15%, although much higher levels can be employed, for example, up to about 30% or more. more, especially in non-ionic formulations: cationic (ie, limited or no anions). A possible use of cationic surfactants is a grease release agent. The cationic surfactants can be used alone or in combination with solvents and / or solubilizing agents. See patent of E.U.A. No. 5552089.

Another type of surfactants useful is what are called dianionic. These are surfactants having at least two anionic groups present in the surfactant molecule. Suitable dianionic surfactants are further described in the co-pending of E.U.A. Serial No. 60 / 020,503 (Case No. 6160P), 60 / 020,772 (Case No. 6161 P), 60 / 020,928 (Case No. 6158P), 60 / 020,832 (Case No. 6159P) and 60 / 020,773 (Case No. 6162P), all filed on June 28, 1996, and 60 / 023,539 (Case No. 6192P), 60/023493 (Case No. 6194P), 60 / 023,540 (Case No. 6193P) and 60 / 023,527 (Case No. 6195P) filed on August 8, 1996, and whose descriptions are incorporated herein by reference. In addition and preferably, the surfactant can be a branched alkyl sulfate in the middle part of the chain, branched alkylalkoxylate in the middle part of the chain, or branched alkylalkoxylate in the middle part of the chain. These surfactants are also described in No. 60/061, 971, Legal case No. 6881 P of October 14, 1997, No. 60/061, 975, Legal case No. 6882P of October 14, 1997, No. 60 / 062,086, Legal case No. 6883P of October 14, 1997, No. 60/061, 916, Legal case No. 6884P of October 14, 1997, No. 60/061, 970, Legal case No. 6885P of the October 14, 1997, No. 60 / 062,407, Legal Case No. 6886P of October 14, 1997. Other suitable branched surfactants in the middle part of the chain can be found in the US patent. Serial No. 60 / 032,035 (Case No. 6401 P), 60/031, 845 (Case No. 6402P), 60/031, 916 (Case No. 6403P), 60/031, 917 (Case No. 6404P) , 60/031, 761 (Case No. 6405P), 60/031, 762 (Case No. 6406P) and 60/031, 844 (Case No. 6409P). Mixtures of these branched surfactants with conventional linear surfactants are also suitable for use in the compositions herein. Combinations of surfactants are also envisaged. One such combination would be the modified alkyl benzene sulfonate surfactants of this invention that form a negatively charged complex with an alkyl carbonate surfactant. See the patent of E.U.A. No. 5736496. As an alternative, these alkylene carbonate surfactants can be combined with the modified alkylbenzenesulfonate surfactants of this invention and do not form a negatively charged complex; such as the compositions in the U.S.A. No. 5,733,860. In any type of alkylene carbonate surfactants suitable for the composition include those of the formula: wherein R1 is a Cn alkyl group, R2 is H or is an alkyl group Cm, where n + m is a number of 11-14; Another possible combination with the modified alkylbenzenesulfonate surfactant is with a monoalkyl succinamate, more preferably from about 0.5 to about 6% by weight of a C 1 to C 8 monoalkyl succinamate, wherein the alkyl group can be ethoxylated up to With 8 moles of ethylene oxide, the monoalkyl succinamate has the structure: wherein R is an aliphatic radical, of 10 to 18 carbon atoms, and M is a cation selected from the group consisting of sodium, potassium, ammonium and alkanolamine. See the patent of E.U.A. No. 5480586. Suitable levels of anionic detersive surfactants herein are in the range of from about 1% to about 50% or more, preferably from about 2% to about 30%, still more preferably about 5%. % to about 205 by weight of the detergent compositions. Suitable levels of nonionic detersive surfactant herein are from about 1% to about 40%, preferably from about 2% to about 30%, more preferably from about 5% to about 20%.

Desirable weight ratios of anionic: nonionic surfactants in combination range from 1.0: 9.0 to 1.0: 0.25, preferably 1.0: 1.5 to 1.0: 0.4. Desirable weight ratios of anionic: cationic surfactants in combination include from 50: 1 to 5: 1, more preferably 35: 1 to 15: 1. Suitable levels of cationic detersive surfactant herein are from about 0.1% to about 20%, preferably from about 1% to about 15%, although much higher levels, for example, up to about 30% or more can be especially useful in non-ionic formulations: cationic (ie, limited or no anions). When present, amphoteric or zwitterionic surfactants are useful at levels in the range from about 0.1% to about 20% by weight of the detergent composition. Often, levels will be limited to around 5% or less, especially when the amphoteric is expensive.

Surfactant The composition will preferably contain at least about 0.01%, more preferably at least about 0. 1%, still more preferably at least about 0.2%, even more preferably still at least about 0.5% by weight of said surfactant composition. The composition will also preferably contain no more than about 90%, more preferably no more than about 70%, more preferably not more than about 60%, even more preferably not more than about 35% by weight of said composition of surfactant. The anionic surfactants useful in the present invention are preferably selected from the group consisting of linear alkylbenzene sulfonate, alpha olefin sulphonate, paraffin sulphonates, alkyl ester sulphonates, alkyl sulfates, alkyl alkoxysulfate, alkylsulfonates, alkyl alkoxycarborxylate, alkoxylated alkylsulfates, sarcosinates, taurinates and mixtures thereof. When present, the anionic surfactant will almost always be present in an effective amount. More preferably, the composition may contain at least about 0.5%, more preferably at least about 5%, still more preferably at least about 10% by weight of said anionic surfactant composition. The composition also preferably contains no more than about 90%, more preferably no more than about 50%, more preferably not more than about 30% by weight of said anionic surfactant composition. Alkyl sulfate surfactants are another type of anionic surfactant of importance for use herein. In addition to providing an excellent general cleaning capacity in use in combination with fatty acid polyhydroxyamides (see below), including optimal grease / oil cleaning over a wide variety of temperatures, wash concentrations and wash times, the dissolution of alkyl sulfates can be obtained, as well as the improved formulation capability in liquid detergent formulations are salts or water-soluble acids of the formula ROSO3M , wherein R is preferably a C 0 -C 24 hydrocarbyl, preferably alkyl or hydroxyalkyl having a C 0 -C 24 alkyl component, more preferably C 12 -C 18 alkyl or hydroxyalkyl, and M is H or a cation, for example an alkali metal cation (Group IA) (for example sodium, potassium, lithium), substituted or unsubstituted ammonium cations, such as methyl-, dimethyl- and trimethylammonium and quaternary ammonium cations, for example tetramethylammonium and dimethyl piperidinium, and cations derived from alkanolamines, such as ethanolamine, diethanolamine, triethanolamine and mixtures thereof. Alkyl chains of C? 2-C? 6 are almost always preferred for lower wash temperatures (for example below about 50 ° C) and alkyl chains of C? 6-C? 8 are preferred for washing temperatures. higher (for example above about 50 ° C). Alkoxylated alkylsulphate surfactants are another category of useful anionic surfactant. These surfactants are water-soluble salts or acids typically of the formula RO (A) mSO 3 M, wherein R is an alkyl or hydroxyalkyl group of C 0 -C 24 having a C 10 -C 24 alkyl component, preferably an alkyl or hydroxyalkyl C12-C20, more preferably C12-C18 alkyl or hydroxyalkyl, A is an ethoxy or propoxy unit, m is greater than zero, almost always between about 0.5 and about 6, more preferably between about 0.5 and about 3, and M is H or a cation which may be, for example, a metal cation (for example sodium, potassium, lithium, etc.), ammonium cation or substituted ammonium cation. The ethoxylated alkyl sulphates, as well as the propoxylated alkyl sulphates are contemplated herein. Specific examples of substituted ammonium cations include methyl-, dimethyl-, trimethyl-ammonium and quaternary ammonium cations, such as tetramethylammonium, dimethyl piperidyl and cations derived from alkanolamines, for example monoethanolamine, diethanolamine and triethanolamine and mixtures thereof . Exemplary surfactants are alkyl sulfate (1.0) of C 2 -C 8 polyethoxylate, alkylsulfate (2.25) of C 2 -C 8 polyethoxylate, alkylsulfate (3.0) of C 2 -C 8 polyethoxylate, and C2-C18 polyethoxylate alkylsulfate (4.0), where M is selected for convenience of sodium and potassium. The surfactants that are used herein can be made from natural or synthetic alcohol supply materials. Chain lengths represent hydrocarbon distributions, including branching. The anionic surfactant component may comprise alkyl ether alkyl sulfates and sulfates, derived from conventional alcohol sources, for example, natural alcohols, synthetic alcohols, such as those sold under the trademark of NEODOL ™, ALFOL ™, LIAL ™ , LUTENSOL ™ and the like. The alkyl ether sulfates are also known as polyethoxylate alkyl sulphates. Examples of suitable anionic surfactants are found in "Surface Active Agents and Detergents" (Vol. I and II of Schwartz, Perry and Berch). A variety of such surfactants are also generally described in the US patent. No. 3,929,678, issued December 30, 1975 to Laughlin et al, in column 23, line 58 to column 29, line 23. One type of anionic surfactant that can be used encompasses the alkyl ether sulfonates. These are desirable because they can be made from renewable sources other than petroleum. The preparation of the alkyl ester sulfonate surfactant component can be carried out according to known methods which are described in the written material of the art. For example, the linear esters of C8-C20 carboxylic acids can be sulfonated with gaseous SO3 according to "The Journal of the American Oil Chemists Society", 52 (1975), pp. 323-329. Suitable starting materials would include substances of natural acids, as derived from oils of tallow, palm and coconut, etc. The preferred alkyl ester sulfonate surfactant, especially for laundry applications, comprises alkyl ester sulphonate surfactants of the structural formula: wherein R3 is a C8-C2o hydrocarbyl, preferably alkyl, or combination thereof, R4 is a C -CT hydrocarbyl, preferably alkyl, or combination thereof, and M is a soluble salt forming cation. Suitable salts include metal salts, such as sodium, potassium and lithium salts, and substituted and unsubstituted ammonium salts, such as methyl, dimethyl, trimethyl and quaternary ammonium cations, for example, tetramethyl ammonium. and dimethyl piperdinium, and cations derived from alkanolamines, for example monoethanol-amine, diethanolamine and triethanolamine. Preferably, R3 is C10-C16 alkyl, and R4 is methyl, ethyl or isopropyl. Especially preferred are methyl ester sulfonates, wherein R3 is C-Cie alkyl. Other anionic surfactants useful for detersive purposes can also be included in the compositions thereof. These may include salts (including, for example, sodium, potassium, ammonium and substituted ammonium salts, such as mono-, di- and triethanolamine salts) of soap, linear Cg-C2o alkylbenzenesulfonates, primary or secondary alkanesulfonates of Cs-Cz = C8-C24 olefinsulfonates, sulfonated polycarboxylic acids prepared by sulfonation of the pyrolyzed product of alkaline earth metal citrates, for example as described in British Patent Specification No. 1, 082,179, alkyl glycerol sulfonates, fatty acyl glycerol sulfonates, oleyl glycerol fatty sulfates, ethylene oxide ether alkylphenol sulphates, paraffin sulphonates, alkyl phosphates, isothionates, such as acyl isothionates, N-acyl taurates, fatty acid amides of methyl tauride, alkyl succinamates and sulfosuccinates, sulfosuccinate monoesters (in particular saturated and unsaturated C? 2-C? 8 monoesters) sulfosuccinate diesters (especially saturated Ce-Cu diesters and not sa tures), N-acyl sarcosinates, alkylpolysaccharide sulfates, such as the alkyl polyglycoside sulphates (the non-sulphonated nonionic compounds described below), branched primary alkyl sulphates, alkyl polyethoxy carboxylates, such as those of the formula RO (CH2CH20) kCH2COO-M +, wherein R is a C8-C22 alkyl, k is an integer from 0 to 10, and M is a soluble salt-forming cation, and fatty acids esterified with isethionic acid and neutralized with sodium hydroxide. Resin acids and hydrogenated resin acids are also suitable, such as resin, hydrogenated resin and resin acids and hydrogenated resin acids present or liquid resin derivatives. Other examples are provided in "Surface Active Agents and Detergents" (Vol. I and II by Schwartz, Perry and Berch). A variety of such surfactants are also generally described in the US patent. No. 3,929,678, issued December 30, 1975 to Laughlin et al, in column 23, line 58 to column 29, line 23. Nonionic detergent surfactants - suitable nonionic detersive surfactants are generally generally described in US Pat. the US patent No. 3,929,678, Laughlin et al, issued December 30, 1975, in column 13, line 14 to column 16, line 6, incorporated herein by reference. Exemplary non-limiting classes of useful nonionic surfactants include: alkyl ethoxylate, alkanoyl glucosamide, C12-C8 alkyl ethoxylates ("AE"), including the so-called narrow peak alkyl ethoxylates and phenolic alkyl alkoxylates of C6- C12 (especially ethoxylates and ethoxy / mixed propoxy), and mixtures thereof. When present, the surfactant will almost always be present in an effective amount. More preferably, the composition may contain at least about 0.1%, more preferably at least about 0.2%, even more preferably at least about 0.5% by weight of said nonionic surfactant composition. The composition will also preferably contain no more than about 20%, more preferably no more than about 15%, more preferably not more than about 10% by weight of said nonionic surfactant composition. The condensates of polyethylene oxide, polypropylene and polybutylene of alkyl phenols. In general, polyethylene oxide condensates are preferred. These compounds include the condensation products of alkyl phenols having an alkyl group containing from about 6 to about 12 carbon atoms in a straight chain or branched chain configuration with the alkylene oxide. In a preferred embodiment, the ethylene oxide is present in an amount equal to about 5 to about 25 moles of ethylene oxide per mole of alkyl phenol. The commercially available nonionic surfactants of this type include Igepal® CO-630, marketed by GAF Corporation; and Triton® X-45, X-114, X-100 and X-102, all marketed by Rohm & Haas Company. These compounds are commonly referred to as alkyl phenol alkoxylates, (for example alkyl phenol ethoxylates). The condensation products of aliphatic alcohols of about 1 to about 25 moles of ethylene oxide. The alkyl chain of the aliphatic alcohol may be straight or branched, primary or secondary, and generally contains from about 8 to about 22 carbon atoms. In particular, the condensation products of alcohols having an alkyl group containing from about 10 to about 20 carbon atoms from about 2 to about 18 moles of ethylene oxide per mole of alcohol are preferred. Examples of commercially available nonionic surfactants of this type include Tergitol® 15-S-9 (the condensation product of C11-C15 linear secondary alcohol with 9 moles of ethylene oxide), Tergitol® 24-L- 6 NMW (the primary alcohol condensation product of Ci2-C with 6 moles of ethylene oxide with a narrow molecular weight distribution), both marketed by Union Carbide Corporation; Neodol® 45-9 (the linear condensation product of C14-C15 with 9 moles of ethylene oxide), Neodol® 23-6.5 (the linear C12-C3 alcohol condensation product with 6.5 moles of ethylene), Neodol® 45-7 (the linear condensation product of C14-C? 5 with 7 moles of ethylene oxide), Neodol® 45-4 (the condensation product of C14-C15 linear alcohol with 4 moles of ethylene oxide), marketed by Shell Chemical Company, and kyro® EOB (the condensation product of C 3 -C 5 alcohol with 9 moles of ethylene oxide), marketed by The Procter & Gamble Company. Other nonionic surfactants available on the market include Dobanol 91-8®, marketed by Shell Chemical Co. and Genapol UD-080® marketed by Hoechst. This category of surfactant is generally referred to as "alkyl ethoxylates". The condensation products of ethylene oxide with a hydrophobic base formed by the condensation of propylene oxide with propylene glycol. The hydrophobic portion of these compounds preferably has a molecular weight of about 1500 to about 1800 and exhibits insolubility in water. The addition of polyoxyethylene portions to this hydrophobic portion tends to increase the water solubility of the molecule as a whole, and the liquid character of the product is retained to the t where the polyoxyethylene content is about 50% of the total product weight. of condensation, which corresponds to the condensation to approximately 40 moles of ethylene oxide. Examples of compounds of this type include certain commercially available Plurionic® surfactants, marketed by BASF. The condensation products of ethylene oxide with the product resulting from the reaction of propylene oxide and ethylene diamine. The hydrophobic part of these products consists of the reaction product of ethylenediamine and excess propylene oxide, and in general has a molecular weight of about 2500 to about 3000. This hydrophobic part is condensed with ethylene oxide to the extent that the product of condensation contains from about 40% to about 80% by weight of polyoxyethylene and has a molecular weight of from about 5,000 to about 11,000. Examples of this type of nonionic surfactant include certain Tetronic® compounds commercially available, marketed by BASF. Examples of ethylene oxide-propylene oxide block copolymers suitable for uses herein are described in greater detail in Pancheri / Mao; patent of E.U.A. No. 5,167,872, issued December 2, 1992. This patent is incorporated herein by reference. Preferred alkyl polyglycosides have the formula R2O (CnH2nO) t (glucosyl) x wherein R2 is selected from the group consisting of alkyl, alkyl phenyl, hydroxyalkyl, hydroxyalkyl phenyl and mixtures thereof, wherein the alkyl groups contain from about 10 to about 18, preferably from about 12 to about 14, carbon atoms; n is 2 or 3, preferably 2; t is from 0 to about 10, preferably 0; and x is from about 1.3 to about 10, preferably from about 1.3 to about 3, more preferably from about 1.3 to about 2.7. The glucosyl is preferably derived from glucose. To prepare these compounds, the alcohol or alkyl polyethoxy alcohol is first formed and then reacted with glucose, or a source of glucose, to form the glucoside (linkage at position 1). The additional glucosyl units can then be linked between their position 1 and the preceding glucosyl units of position 2-, 3-, 4- and / or 6, preferably predominantly the 2-position. The alkylpolysaccharides described in the U.S.A. No. 4,565,647, Filling, issued January 21, 1986, having a hydrophobic group containing from about 6 to about 30 carbon atoms, preferably from about 10 to about 16 carbon atoms and a polysaccharide, for example a polyglucoside, a hydrophilic group containing from about 1.3 to about 10, preferably from about 1.3 to about 3, more preferably from about 1.3 to about 2.7 units of saccharides. Any reducing saccharide containing 5 or 6 carbon atoms can be used, for example the glucose, galactose and galactosyl portions can be substituted for the glucosyl portions. (As an option, the hydrophobic group is attached to the 2-, 3-, 4-, etc. positions, to thereby give a glucose or galactose, as opposed to a glycoside or galactoside). The intersaccharide linkages can be, for example, between position one of the additional saccharide units and positions 2-, 3-, 4- and / or 6- of the preceding saccharide units. As an option, and less desirable, there may be a polyalkylene oxide chain linking the hydrophobic part and the polysaccharide part. The preferred alkylene oxide is ethylene oxide. Typical hydrophobic groups include alkyl groups, whether saturated or unsaturated, branched or unbranched containing from about 8 to about 18, preferably from about 10 to about 16, carbon atoms. Preferably, the alkyl group is a saturated straight-chain alkyl group. The alkyl group can contain up to about 3 hydroxy groups and / or the polyalkylenoxide chain can contain up to about 10, preferably less than 5, parts of alkylene oxide. The alkyl polysaccharides are octyl, nonyl, decyl, undecyldecyl, tridecyl, tetradecyl, pentadecyl, hexadecyl, heptadecyl and octadecyl, di-, tri-, tetra-, penta- and hexaglucosides, galactosides, lactosides, glucoses, fructosides, fructose and / or Galactoses Suitable mixtures include coconut alkyl, di-, tri-, tetra- and pentaglucosides and tallow alkyl tetra-, penta- and hexa-glucosides. Another type of suitable nonionic surfactant comprises a mixture (herein after referred to as an ethoxylated glycerol type compound), which is a mixture of an esterified ethoxylated polyhydric alcohol, a partially esterified ethoxylated polyhydric alcohol and a non-esterified ethoxylated polyhydric alcohol, wherein the preferred polyhydric alcohol is glycerol, and the compound is: formula (I) formula (II) wherein w equals one to four, more preferably one. B is selected from the group consisting of hydrogen or a group represented by. wherein R is selected from the group consisting of an alkyl group having 6 to 22 carbon atoms, more preferably 11 to 15 carbon atoms and alkenyl groups having 6 to 22 carbon atoms, more preferably 11 to 15 carbon atoms carbon, wherein a hydrogenated alkyl tallow chain or an alkyl coconut chain is most preferred, wherein at least one of the groups B is represented by.

C P- R ' and R 'is selected from the group consisting of hydrogen and methyl groups; x, y and z have a value between 0 and 60, more preferably 0 to 40, as long as (x + y + z) equals 2 to 100, preferably 4 to 24 and more preferably 4 to 19, where in the formula (I), the weight ratio of monoester / diester / triester is 45 to 90/5 to 40/1 to 20, more preferably 50 to 90/9 to 32/1 to 12, where the weight ratio of the formula (I) to the formula (II) is a value between 3 to 0.02, preferably 3 to 0J, more preferably 1.5 to 0.2, where it is even more preferred that there is more of the formula (II) than of the formula (I) in the mixture that forms the compound. The ethoxylated glycerol compound which can be employed in the composition herein is made by Kao Corporation and sold under the trade name Levenol, such as levenol F-200, which has an average EO of 6 and a molar ratio of fatty acid of coco to glycerol of 0.55 or Levenol V501 / 2 which has an average EO of 17 and a molar ratio of tallow fatty acid to glycerol of 1.0. It is preferred that the molar ratio of the fatty acid to glycerol be less than 1.7, more preferably less than 1.5 and more preferably less than 1.0. The ethoxylated glycerol type compound has a molecular weight of 400 to 1600, and a pH (50 grams / liter of water) of 5-7. Levenol compounds are basically non-irritating to human skin and have a primary biodegradable capacity greater than 90%, as measured by the Wickbold Bias-7d method. Two examples of the Levenol compounds are Levenol V-501/2 which has 17 ethoxylated groups and is derived from tallow fatty acid with a fatty acid to glycerol ratio of LO and a molecular weight of 1465 and Levenol F-200 has 6 ethoxylated groups and is derived from coconut fatty acid with a fatty acid to glycerol ratio of 0.55. Levenol F-200 and Levenol V-501/2 are composed of a mixture of formula (I) and formula (II). The Levenol compounds have algae growth inhibition ecoxicity values > 100 mg / liter; acute toxicity for Daphniae > 100 mg / liter and acute fish toxicity > 100 mg / liter. The Levenol compounds have a ready biodegradable capacity greater than 60% which is the minimum value required in accordance with the measurement of OECD 301 B to be acceptably biodegradable. The polyesterified nonionic compounds which are also useful in these compositions are Crovol PK-40 and Crovol PK-70, made by Croda GMBH of the Netherlands. Crovol PK-40 is a polyoxyethylene (12) palm kernel glyceride having 12 EO groups. The Crovol PK-70 which is preferred is a polyoxyethylene Palm Grain Glyceride (45) having 45 EO groups. More information on these nonionic surfactants can be found in the US patent. No. 5719114. Another type of suitable nonionic surfactant comprises polyhydroxy fatty acid amides. These materials are described in more detail in Pan / Gosselink; patent of E.U.A. No. 5,332,528; Issued on July 26, 19994, which is incorporated herein by reference. These polyhydroxy fatty acid amides have a general structure of the formula. where. R1 is H, C1-C4 hydrocarbyl, 2-hydroxyethyl, 2-hydroxy propyl or a mixture thereof, preferably C1-C4 alkyl, more preferably C1 or C2 alkyl, more preferably still alkyl C1 (ie, methyl); and R2 is a C5-C31 hydrocarbyl, preferably straight chain C7-C19 alkyl or alkenyl, more preferably straight-chain C9-C17 alkyl or alkenyl, more preferably still C11-C15 alkyl or alkenyl chain straight, or mixtures thereof; and Z is a polyhydroxyhydrocarbyl having a linear hydrocarbyl chain with at least 3 hydroxyls directly connected to the chain, or an alkoxylated derivative (preferably ethoxylated or propoxylated) thereof. Z will preferably be derived from a reducing sugar in a reductive amine reaction; more preferably Z will be a glycylil. Suitable reducing sugars include glucose, fructose, maltose, lactose, galactose, mannose and xylose. High-dextrose corn syrup, high-fructose corn syrup and high-maltose corn syrup, as well as the individual sugars mentioned above, can be used as starting materials. These corn syrups can produce a mixture of sugar components for Z. It should be understood that it is by no means intended to exclude other suitable starting materials. Z will preferably be selected from the group consisting of -CH2- (CHOH) n-CH20H, -CH (CH20H) - (CHOH) n-1-CH20H, -CH2- (CHOH) 2 (CHOR ') (CHOH) - CH20H, and alkoxylated derivatives thereof, wherein n is an integer from 3 to 5, inclusive, and R 'is H or a cyclic or aliphatic monosaccharide. Most preferred are glycityls, where n is 4, in particular -CH2- (CHOH) 4-CH20H. R 'can be, for example, N-methyl, N-ethyl, N-propyl, N-isopropyl, N-butyl, N-2-hydroxyethyl or N-2-hydroxypropyl. R2-CO-N < it can be, for example, cocamide, stearamide, oleamide, lauramide, myristamide, capricamide, palmitamide, seboamide, etc. Z can be 1-deoxyglucitol, 2-deoxyfructityl, 1-deoxymaltityl, 1-deoxylactityl, 1-deoxygalactityl, 1-deoxyanityl, 1 -deoxytrotothiathityl, etc. Methods for making fatty acid polyhydroxyamides are known in the art. In general, they can be prepared by reacting an alkylamine with a reducing sugar in a reductive amination reaction to form a corresponding N-alkyl polyhydroxyamine, and then reacting the N-alkyl polyhydroxyamine with a fatty aliphatic ester or triglyceride in a condensation step. / amidation to form the product of N-alkyl, N-polyhydroxy fatty acid amide. Methods for making compositions containing polyhydroxy fatty acid amides are described, for example in British patent specification 809,060, published February 18, 1959, by Thomas Hedley & Co., Ltd., patent of E.U.A. No. 2,965,576, issued December 20, 1960 to E.R. Wilson and patent of E.U.A. No. 2,703,798, Anthony M. Schwartz, issued March 8, 1955 and patent of E.U.A. No. 1, 985,424, issued on December 25, 1934 to Piggott, each of which are incorporated by reference. Examples of such surfactants include C10-C18 N-methyl, or N-hydroxypropyl, glucamides. N-propyl N-hexyl C12-C16 glucamides can be used to produce low foaming. Preferred amides are C8-C20 ammonia amides, monoethanolamides, diethanolamides, and sopropanolamides. Another suitable class of surfactants are the alkanolamide surfactants, which include the amides of ammonia, monoethanol and diethanolamides of fatty acids having an acyl portion containing from about 8 to about 18 carbon atoms. These materials are represented by the formula: wherein R1 is a saturated or unsaturated hydroxy aliphatic hydrocarbon group having from about 7 to 21, preferably from about 11 to 17 carbon atoms; R 2 represents a methylene or ethylene group; and m is 1, 2 or 3, preferably 1. Specific examples of said amides are coconut fatty acid amide of monoethanol amine and fatty acid amide of diethanolamine dodecyl. These acyl parts can be derived from glycerides as they occur in nature, for example, coconut oil, palm oil, soybean oil and tallow, but can be derived synthetically, for example, by the oxidation of petroleum or by hydrogenation of carbon monoxide by the Fischer-Tropsch process. The monoethanolamides and diethanolamides of C 12 -C 14 fatty acids are preferred.

Amphoteric Surfactants Amphoteric surfactants can be incorporated as an option in the detergent compositions herein. These surfactants can be described in detail as aliphatic derivatives of secondary or tertiary amines, or aliphatic derivatives of heterocyclic secondary and tertiary amines in which the aliphatic radical can be straight or branched chain. One of the aliphatic substituents contains at least about 8 carbon atoms, almost always from about 8 to about 18 carbon atoms, and at least one contains an anionic water-soluble group, for example carboxy, sulfonate, sulfate. See the patent of E.U.A. No. 3,929,678 to Laughlin et al, issued December 30, 1975 in column 19, lines 18-35 by examples of ampholytic surfactants. The preferred amphoteric includes C12-C18 betaines and sulfobetaines ("sultaines"), C10-C18 amine oxides and mixtures thereof. When present, the surfactant will almost always be present in an effective amount. More preferably, the composition may contain at least about 0.1%, more preferably at least about 0.2%, still more preferably at least about 0.5% by weight of said amphoteric surfactant composition. The composition will also preferably contain no more than about 20%, more preferably no more than about 15%, more preferably not more than about 10% by weight of said amphoteric surfactant composition. The amine oxides are amphoteric surfactants and include water-soluble amine oxides containing an alkyl part of from about 10 to about 18 carbon atoms and 2 portions selected from the group consisting of alkyl groups and hydroxyalkyl groups containing from about 1 to around 3 carbon atoms; the water-soluble phosphine oxides containing an alkyl part of about 10 to about 18 carbon atoms and 2 parts selected from the group consisting of alkyl groups and hydroxyalkyl groups containing from about 1 to about 3 carbon atoms; and water-soluble sulfoxides containing an alkyl part of from about 10 to about 18 carbon atoms, and a portion selected from the group consisting of alkyl and hydroxyalkyl portions of from about 1 to about 3 carbon atoms. Preferred amine oxide surfactants have the formula O I R3 (OR4)? N (R5), wherein R3 is an alkyl, hydroxyalkyl or alkylphenyl group or mixtures thereof containing from about 8 to about 22 carbon atoms; R 4 is an alkylene or hydroxyalkylene group containing from about 2 to about 3 carbon atoms or mixtures thereof; x is from 0 to about 3; each R 5 is an alkyl or hydroxyalkyl group containing from about 1 to about 3 carbon atoms or a polyethylene oxide group containing from about 1 to about 3 ethylene oxide groups. The R5 groups can be linked together, for example, through an oxygen or nitrogen atom, to form an annular structure. These amine oxide surfactants in particular include C 10 -C 18 alkyldimethylamine oxides and C 8 -C 12 alkoxy ethyl dihydroxy ethylamine oxides. When present, the amine oxide surfactant will almost always be present in an effective amount. More preferably, the composition may contain at least about 0.1%, more preferably at least about 0.2%, still more preferably at least about 0.5% by weight of said amine oxide surfactant composition . The composition will also preferably contain no more than about 20%, more preferably no more than about 155, more preferably not more than about 10% by weight of said amine oxide surfactant composition.

Examples of suitable amine oxide surfactants are found in "Surface Active Agents and Detergents" (Vol. I and II of Shcwartz, Perry and Berch). Suitable betaine surfactants include those of the general formula: OR RN .G + «? (OR1 ') 2 ~~ Fr * CCr wherein R is a hydrophobic group selected from alkyl groups containing from about 10 to about 22 carbon atoms, preferably from about 12 to about 18 carbon atoms, alkylaryl and arylalkyl groups containing a similar number of carbon atoms with a benzene ring that is treated as equivalent to about 2 carbon atoms, and similar structures interrupted by amino or ether bonds; each R1 is an alkyl group containing from 1 to about 3 carbon atoms; and R2 is an alkylene group containing from 1 to about 6 carbon atoms. Examples of preferred betaines are dodecyl dimethyl betaine, cetyl dimethyl betaine, dodecyl amidopropyldimethyl betaine, tetradecyldimethyl betaine, tetradecylamidopropyldimethyl betaine, and dodecyldimethylammonium hexanoate. Other suitable amidoalkyl betaines are described in the U.S. Patents. Nos. 3,950,417; 4,137,191; and 4,375,421; and British Patent GB No. 2,103,236, which are incorporated herein by reference.

Zwitterionic surfactants Zwitterionic surfactants can also be incorporated into the detergent compositions thereof. These surfactants can be further described as derivatives of secondary and tertiary amines, derivatives of heterocyclic secondary and tertiary amines or quaternary ammonium derivatives, quaternary phosphonium or tertiary sulfonium compounds. See the patent of E.U.A. No. 3,929,678 to Laughlin et al, issued December 30, 1975 in column 19, line 38 to column 22, line 48 for examples of zwitterionic surfactants. The ampholytic and zwitterionic surfactants are generally used in combination with one or more anionic and / or nonionic surfactants.

Detersive Enzymes Enzymes are preferably included in the detergent compositions herein for a variety of purposes, including the removal of protein, carbohydrate or triglyceride stains from substrates. Recent descriptions of enzymes in detergents useful herein include chondrothinase (EP 747,469 A); protease variants (WO 96/28566 A, WO 96/28557 A, WO 96/28556 A, WO 96/25489 A) xylanase (EP 709,452 A); keratinase (EP 747,470 A); lipase (GB 2,297,979 A; WO 96/16153 A; WO 96/12004 A; EP 698,659 A; WO 96/16154 A); cellulase (GB 2,294,269 A; WO 96/27649 A; GB 2,303,147 A); termitase (WO 96/28558 A). More generally, suitable enzymes include cellulases, hemicellulases, proteases, glucoamylases, amylases, lipases, cutinases, pectinases, xylanases, keratinases, reductases, oxidases, phenoloxidases, lipoxygenases, ligninases, pullulanases, tannases, condriotinasas, termitasas, fenotsanasas, malanases , ß-glucanases, arablnosidases or mixtures thereof of any suitable origin, such as vegetable, animal, bacterial, fungal and yeast. Preferred selections are influenced by factors such as pH activity and / or stability optima, thermostability and stability to activate detergents, builders and the like. In this regard bacterial or fungal enzymes are preferred, such as bacterial amylases and proteases and fungal cellulases. A preferred combination is a detergent composition having a cocktail of conventional applicable enzymes such as protease, amylase, lipase, cutinase and / or cellulase. Suitable enzymes are also described in the patents of E.U.A. Nos. 5,677,272, 5,679,630, 5,703,027, 5,703,034, 5,705,464, 5,707,950, 5,707,951, 5,710,115, 5,710,116, 5,710,118, 5,710,119 and 5,721, 202. Preferably, the composition will contain at least about 0.0001%, more preferably at least about 0.0005%, with still more preference at least about 0.001% by weight of the enzyme composition. The cleaning composition will also preferably contain no more than about 5%, more preferably no more than about 2%, more preferably not more than about 1% by weight of the enzyme composition. As used herein, "detersive enzyme" means any enzyme that has a cleaning, stain removal, or otherwise beneficial effect in cleaning compositions. Preferred detersive enzymes are hydrolases, such as proteases, amylases and lipases. Amylases and / or proteases are highly preferred, including types available on the market today and improved types. Enzymes are usually incorporated in detergent additive detergent compositions at levels sufficient to provide an "effective amount of cleaning". The term "effective cleaning amount" refers to any amount with the ability to produce an effect to improve cleaning, stain removal, grime removal, bleaching, deodorization or freshness on substrates such as fabrics, tableware and the like. In practical terms for current commercial preparations, typical amounts are up to about 5 mg by weight, more often 0.01 mg to 3 mg of active enzyme per gram of the detergent composition. Put another way, the compositions herein will almost always comprise from 0.001% to 5%, preferably 0.01% - 1% by weight of a commercial enzyme preparation. Typically, protease enzymes are present in such commercial preparations at levels sufficient to provide 0.005 to 0J Anson units (AU) of activity per gram of composition.

For certain detergents it may be desirable to increase the active enzyme content of the commercial preparation to minimize the total amount of materials that are not cytically active and thereby improve stain formation / film formation and other final results. Higher active levels may also be desirable in highly concentrated detergent formulations.

Proteolytic Enzyme The proteolytic enzyme can be of animal, vegetable or microorganism origin (preferably). Proteases for use in the detergent compositions herein include (but are not limited to) proteases of the trypsin, subtilisin, chymotrypsin and elastase type. The use of proteolytic enzymes of the subtilisin type is preferred herein. In particular, the bacterial serine proteolytic enzyme obtained from Bacillus subtilis and / or Bacillus licheniformis is preferred. Suitable proteolytic enzymes include Novo Industri A / S Alcalasa® (preferably), Esperasa®, Savinasa® (Copenhagen, Denmark), Gist-brocades' Maxa®, Maxacal® and Maxapem 15® (Maxacal® processed protein) (Delft, Holland) and subtilisin BPN and BPN '(preferably), which are available in the market. Preferred proteolytic enzymes are also bacterial modified serine proteases, such as those made by Genencor International, Inc. (San Francisco, California) which are described in European patent 251,446B, issued December 28, 1994 (in particular pages 17, 24 and 98) and which are also referred to herein as "Protease B". The patent of E.U.A. No. 5,030,378, Venegas, issued July 9, 1991, refers to a modified bacterial serine proteolytic enzyme (Genencor International) which is referred to herein as "Protease A" (the same as BPN '). In particular, see columns 2 and 3 of the US patent. No. 5,030,378 for a complete description, including amino acid sequence, of Protease A and its variants. Other proteases are sold under the trade names: Primasa, Durazym, Opticlean and Optimasa. The preferred proteolytic enzymes are selected from the group consisting of Alcalase ® (Novo industry A S), BPN ', Protease A and Protease B (Genencor) and mixtures thereof. Protease B is most preferred. "The proteases described in the patent of E.U.A. No. 5,470,733 are of particular interest for use in this invention. Also the proteases described in the co-pending application USSN 08 / 136,797 can be included in the detergent composition of the invention. Another preferred protease, termed "Protease D" is a carbonyl hydrolase variant having an amino acid sequence not found in nature, which is derived from a precursor carbonyl hydrolase by substitution of a different amino acid for a plurality of amino acid residues in a position in said carbonyl hydrolase equivalent to the +76 position, preferably also in combination with one or more residual amino acid positions equivalent to those selected from the group consisting of +99, +101, +103, +104, +107, +123, +27, +105, +109, +126, +128, +135, +156, +166, +195, +197, +204, +206, +210, +216, +217, +218 , +222, +260, +265 and / or +274, in accordance with the numeration of subtilisin Baciilus amyloliquefaciens, as described in WO 95/10615, published April 20, 1995 by Genencor International (A. Baeck et al. , entitled "Protease-Containing Cleaning Compositions" that have the serial number of USA 08 / 322,676, presented on 13 October 1994). Useful proteases are also described in the PCT publications: WO 95/30010 published November 9, 1995 by The Procter & Gamble Company; WO 95/30011 published November 9, 1995 by The Procter & Gamble Company; WO 95/29979 published November 9, 1995 by The Procter & Gamble Company. The protease enzyme can be incorporated into the compositions according to the invention at a level of 0.0001% to 2% active enzyme by weight of the composition. Preferably, the composition will contain at least about 0.0001%, more preferably at least about 0.0002%, more preferably at least about 0.0005%, with still more preference at least about 0.001% of active enzyme by weight of the protease enzyme composition. The composition will also preferably contain no more than about 2%, more preferably no more than about 0.5%, more preferably no more than about 0.1%, more preferably not more than about 0.05% of active enzyme by weight of the composition of enzyme protease.

Amylase Amylases (a and / or ß) can be included to remove carbohydrate spots. Suitable amylases are Termamyl® (Novo Nordisk), Fungamyl® and BAN® (Novo Nordisk). Enzymes can be of any origin, such as vegetable, animal, bacterial, fungal and yeast. Preferably, the composition will contain at least about 0.0001%, more preferably at least about 0.0002%, more preferably at least about 0.0005%, with still more preference at least about 0.001% of active enzyme by weight of the amylase enzyme composition. The composition will also preferably contain no more than about 2%, more preferably no more than about 0.5%, more preferably no more than about 0.1%, more preferably not more than about 0.05% of active enzyme by weight of the composition of enzyme amylase. Amylase enzymes also include those described in WO 95/26397 and co-pending application of Novo Nordisk PCT / DK96 / 00056. Other specific amylase enzymes for use in the detergent compositions of the present invention, therefore, include: (a) α-amylases, characterized by having a specific activity at least 25% greater than the specific activity of Termamyl® on a scale of temperature from 25 ° C to 55 ° C and at a pH value in the range of 8 to 10, measured by the Phadebas® α-amylase activity test. That Phadebas® α-amylase activity test is described on pages 9-10, WO 95/26397. (b) The a-amylases according to (a) which comprise the amino acid sequence appearing in the listings of SEQ ID in the reference cited above, or an α-amylase that is at least 80% homologous with the sequence of amino acids shown in the SEQ ID. (c) The α-amylases conforming to (a) obtained from an alkalophilic Bacillus species, comprising the following amino acid sequence at the N-terminus: His-His-Asn-Gly-Thr-Asn-GIy-Thr-Met- Met-GIn-Tyr-Phe-Glu-Trp-Tyr-Leu-Pro-Asn-Asp. A polypeptide is considered to be X% homologous to the mother amylase if a comparison of the respective amino acid sequences, performed through algorithms, as described by Lipman and Pearson in Science 227, 1985 p. 1435, yields an identity of X%. (d) The α-amylase confers a (a-c), wherein the α-amylase can be obtained from a Bacillus alkalophilic species; and in particular of any of the strains NCIB 12289, NCIB 12512, NCIB 12513 and DSM 935. In the context of this invention, the term "can be obtained from" is intended not only to indicate an amylase produced by a Bacillus strain. but also an amylase encoded by a DNA sequence isolated from said Bacillus strain and produced in a host organism transformed with said DNA sequence. (e) The α-amylase showing a positive immune cross-reactivity with antibodies raised against an α-amylase having an amino acid sequence corresponding respectively to those α-amylases in (α-d). (f) The variants of the following mother α-amylases which (i) have one of the amino acid sequences corresponding respectively to those α-amylases in (ae), or (ii) have at least 80% homology with a or more amino acid sequences, and / or exhibits immune cross-reactivity with an antibody produced against an α-amylase having one of said amino acid sequences, and / or is encoded by a DNA sequence that hybridizes to the same probe as a sequence of DNA encoding an α-amylase having one of said amino acid sequences, in which variants: 1. at least one amino acid residue of said mother α-amylase has been deleted; and / or 2. at least one amino acid residue of said α-amylase has been replaced by a different amino acid residue; and / or 3. at least one amino acid residue has been inserted relative to said mother α-amylase; that variant that has an α-amylase activity and has at least one of the following properties in relation to said mother α-amyiase: increase in thermostability, increase of stability towards oxidation, reduction of dependence on Ca ion, increase in stability and / or α-amylolytic activity in neutral at relatively high pH values, increase in a-amylolytic activity at relatively high temperature and increase or decrease in isoelectric point (pl), to better match the pl value for a-amylase variant to the pH of the medium. Such variants are described in patent application PCT / DK96 / 00056. Other amylases suitable herein include, for example, α-amylases described in GB 1, 296, 839 to Novo.; RAPIDASA®, International Bio-Synthetics, Inc., and TERMAMYL®, Novo. FUNGAMYL® by Novo is especially useful. Enzyme technology to achieve improved stability, for example, oxidation stability, is known. See, for example, J. Biological Chem., Vol. 260, No. 11, June 1985, p. 6518-6521. Certain preferred embodiments of the compositions herein may resort to amylases having improved stability in detergents, such as types for automatic dish washing, especially improved oxidation stability, as measured against a reference point of TERMAMYL® in commercial use in 1993. These preferred amylases share the characteristic of being "improved stability" amylases, characterized, at a minimum, by a measurable improvement, at one or more of: oxidation stability, for example to hydrogen peroxide / tetraacetylethylenediamine in buffer solution of pH 9-10; thermal stability, for example, at common wash temperatures, such as about 60 ° C; or alkaline stability, for example, at a pH of about 8 to about 11, measured against the reference point amylase identified above. The stability can be measured using any technical test described in this field. See, for example, the references described in WO 9402597. Amylases with improved stability can be obtained from Novo or Genencor International. A class of highly preferred amylases herein have the common state of being derived using site-directed mutagenesis of one or more of the Bacillus amylases, especially the Bacillus α-amylases, regardless of whether one, two or multiple amylase strains are the same. immediate precursors. The amylases of improved oxidation stability against the amylase mentioned above are preferred to be used, especially in bleaching, more preferably oxygen bleaching, as it is different from the chlorine bleach detergent compositions herein. Said preferred amylases include (a) an amylase according to WO 9402597, Novo, February 3, 1994, incorporated hereinbefore, as will be illustrated below by a mutant whose substitution is made using alanine or threonine, preferably threonine, of the methionine residue located at position 197 of B. licheniformis alfa-amylase, known as TERMAMYL®, or the homologous position variation of a similar mother amylase, such as B. amyloliquefaciens, B. subtilis or B. stearothermophilus; (b) amylases of improved stability, as described by Genencor International in a document entitled "Oxidative Resistant alpha-Amylases", presented at the 207th National Meeting of the American Chemical Society, March 13-17, 1994, by C. Mitchinson. It was pointed out that the bleaches in detergents for automatic dish washing deprive the alpha-amylases of activity, but that Genencor has made amylases of improved oxidative stability from B. licheniformis NCIB8061. Methionine (Met) was identified as the most likely residue to modify. Met was substituted, one at a time, in positions 8,15, 197, 256, 304, 366 and 438, resulting in specific mutants, which are M197L and M197T in particular important, of which the variant M197T is the variant expressed more stable. The stability was measured in CASCADE® and SUNLIGHT®; (c) preferred amylases in particular include variants of amylases having further modification in the immediate mother amylase, as described in WO 9510603 A, and are available from the Novo transferee, such as DURAMYL®. Another amylase of improved oxidative stability that is particularly preferred includes those described in WO 9418314 to Genencor International and WO 9402597 to Novo. Any other amylase of improved oxidative stability can be employed, for example as derived by direct site-site mutagenesis from stock forms of chimeric, hybrid or simple mutants of available amylases. Other modifications of preferred enzymes are accessible. See WO 9509909 A to Novo. Cellulases that can be used herein include bacterial and fungal types, preferably having an optimum pH between 5 and 9.5, the US patent. No. 4,435,307, Barbesgoard et al, March 6, 1984, describes suitable fungal cellulases of Humicola insolens or strain Humicola DSM 1800 or a cellulase 212 that produces fungi belonging to the genus Aeromonas, and cellulase extracted from the hepatopancreas of a marine mollusc, Dolabella Auricle Solander. Suitable celiacias are also described in GB-A-2,075,028; GB-A-2,095,275 and DE-OS-2,247,832. CAREZYME® and CELLUZYME® (Novo) are especially useful. See also WO 9117243 to Novo. The composition preferably will contain at least about 0.0001%, more preferably at least about 0.0002%, more preferably at least about 0.0005%, still more preferably at least about 0.001% active enzyme by weight of the composition of cellulase and / or peroxidase enzymes. The composition will also preferably contain no more than about 2%, more preferably no more than about 0.5%, more preferably no more than about 0.1%, more preferably not more than about 0.05% active enzyme by weight of the composition of cellulase enzyme and / or peroxidase. Also suitable are cutinases [EC 3. L 1.50] which can be considered as a special type of lipase, mainly lipases that do not require external activation. The addition of cutinases to detergent compositions have been described in e.g. WO-A-88/09367 (Genencor).

Lipase Suitable lipase enzymes include those produced by microorganisms of the Pseudomonas group, such as Pseudomonas stutzeri ATCC 19,154, as described in British Patent 1, 372, 034. Suitable lipases include those that exhibit a positive immune cross reaction with the lipase antibody, produced by the microorganism Pseudomonas fluorescens lAM 1057. This lipase is available from Amano Pharmaceutical Co. Ltd., Nagoya, Japan, under the trade name Lipase P "Amano", hereinafter referred to as "Amano-P". Other suitable lipases are lipases such as M1 Lipase® and Lipomax® (Gist-Brocades). Other suitable commercial lipases include Amano-CES, lipases ex Chromobacter viscosum, for example Chromobacter viscosum var. lipoluticum NRRLB 3673 from Toyo Jozo Co., Tagata, Japan; Chromobacter viscosum lipases from U.S. Biochemical Corp., U.S.A. and Disoynth Co., The Netherlands, and lipases ex Pseudomonas gladioli. The LIPOLASA® enzyme derived from Humicola lanuginosa and commercially available from Novo, see also EP 341, 947, is a preferred lipase for use herein. Lipase and amylase variants stabilized against peroxidase enzymes are described in WO 9414951 A to Novo. See also WO 9205249 and RD 94359044. The highly preferred lipases are the lipolytic enzyme variant D96L of the virgin lipase derived from Humicola lanuginosa, as described in E.U.A. Serial No. 08/341, 826. (See also patent application WO 92/05249 viz, in which the residue (D) of aspartic acid of the virgin lipase ex Humicola lanuginosa in position 96 is changed to Leucine (L) In accordance with this nomenclature, said substitution of aspartic acid to Leucine in position 96 is shown as: D96L Preferably, the strain of Humicola lanuginosa DSM 4106 is used. Despite the large number of publications on lipase enzymes, only the lipase derived from Humicola lanuginosa and produced in Aspergillus Oryzae as a host has so far discovered a broad application as an additive for washing products, it is available from Novo Nordisk under the trade name Lipolasa® and Lipolasa Ultra®, as already indicated.To optimize the stain removal performance of Lipolase, Novo Nordisk has made several variants.As described in WO 92/05249, the D96L variant of virgin lipase Humicola lanuginosa improves the effectiveness of removing tallow stains by a factor 4.4 on the wild-type lipase (enzymes compared in an amount ranging from 0.075 to 2.5 mg of protein per liter). The research description No. 35944 published on March 10, 1994, by Novo Nordisk describes that the lipase variant (D96L) can be added in an amount corresponding to 0.001-100 mg (5-5,000,000 LU / liter) variant lipase per liter of washing solution. The composition preferably will contain at least about 0.0001%, more preferably at least about 0.0002%, more preferably at least about 0.0005%, with still more preference at least about 0.001% of active enzyme in weight of the lipase enzyme composition. The composition will also preferably contain no more than about 2%, more preferably no more than about 0.5%, more preferably no more than about 0.1%, more preferably not more than about 0.05% active enzyme by weight of the enzyme composition lipase. Various carbohydrase enzymes that impart antimicrobial activity may also be included in the present invention. Said enzymes include endoglucosidase, endoglucosidase Type II and glucosidase, as described in the patents of E.U.A. Nos. 5, 041, 236, 5,395,541, 5,238,843 and 5,356,803, the disclosures of which are incorporated herein by reference. Of course, other enzymes that have antimicrobial activity can be used, as well as include peroxidases, oxidases and other enzymes. A variety of materials and enzymatic means for incorporation into synthetic detergent compositions are also described in WO 9307263 A and WO 9307260 A for Genencor International, WO 8908694 A for Novo, and E.U.A. No. 3,553,139, January 5, 1971 to McCarty et al. Enzymes are described in more detail in E.U.A. No. 4,101, 457, Place et al, July 18, 1978, and E.U.A. No. 4,507,219, Hughes, March 26, 1985. Enzymatic materials useful for liquid detergent formulations, and their incorporation into those formulations are described in E.U.A. No. 4,261, 868, Hora et al, April 14, 1981. Enzymes for use in detergents can be stabilized by various techniques. Enzyme stabilization techniques are described and exemplified in E.U.A. Do not. 3,600,319, August 17, 1971, Gedge et al, EP 199,405 and EP 200,586, October 29, 1986, Venegas. Enzyme stabilization systems are also described, for example, in E.U.A. No. 3,519,570. A Bacillus sp. useful AC13, which gives proteases, xylanases and cellulases, is described in WO 9401532 A for Novo. It is also possible to include an enzyme stabilization system in the compositions of this invention when any enzyme is present in the composition.

Enzyme Stabilization System Preferred compositions herein may further comprise from about 0.001% to about 10%, preferably from about 0.005% to about 8%, more preferably from about 0.01% to about 6% by weight of an enzyme stabilization system. This can be any stabilization system that is compatible with the protease and other enzymes used in the compositions herein. Such stabilization systems may comprise calcium ion, boric acid, propylene glycol, short chain carboxylic acid, boric acid, polyhydroxyl compounds and mixtures thereof, as described in US Pat. Nos. 4,261, 868, Hora et al, issued April 14, 1981; 4,404,115, Tai, issued September 13, 1983; 4,318,818, Letton et al; 4,243,543, Guildert et al, issued January 6, 1981; 4,462,922, Boskamp, issued July 31, 1984; 4,532,064, Boskamp, issued July 30, 1985; and 4,537,707, Severson Jr., issued August 27, 1985, which are incorporated herein by reference. The composition preferably will contain at least about 0.001%, more preferably at least about 0.005%, most preferably at least about 0.001% by weight of the composition of enzyme stabilization system. The composition will also preferably contain no more than about 10%, more preferably no more than about 8%, no more than about 6% active enzyme by weight of the enzyme stabilization system composition. A stabilizing range is the use of water-soluble sources of calcium and / or magnesium in the finished compositions that provide said ions to the enzymes. In general, calcium ions are more effective than magnesium ions and are preferred herein, if only one type of cation is being used. Typical detergent compositions, especially liquid, will comprise from about 1 to about 30, preferably from about 2 to about 20, more preferably from about 8 to about 12 millimoles of calcium ion per liter of finished detergent composition, although variation is possible depending on factors that include the multiplicity, type and levels of enzymes incorporated. Preferably, the water-soluble calcium or magnesium salts are used, including, for example, calcium chloride, calcium hydroxide, calcium formate, calcium malate, calcium maleate, calcium hydroxide and calcium acetate; More generally, calcium or magnesium sulfate salts corresponding to the exemplified calcium salts can be used. Of course, other increases in calcium and / or magnesium levels may be useful, for example to promote the short-fat action of certain types of surfactants. However, it is especially preferred that the composition does not contain any added calcium ion, and it is even more preferred that the composition has no calcium ion. Another approach to stabilization is through the use of borate species. See Severson, E.U.A. No. 4,537,706. Borate stabilizers, when used, may be in levels of up to 10% or more of the composition, although more often, levels of up to about 3% by weight of boric acid or other borate compounds, such as borax or orthoborate, are Suitable for use in liquid detergents. The substituted boric acids, such as phenylboronic acid, butanoboric acid, p-bromophenylboronic acid or the like can be used in place of boric acid and reduced levels of total boron can be possible in detergent compositions, despite the use of said substituted boron derivatives. In addition, from 0% to about 10%, preferably from about 0.01% to about 6% by weight of chlorine bleach or oxygen bleach radical scavengers can be added to the compositions of the present invention to prevent the species Chlorine bleach present in many water supplies attack and inhibit the activity of enzymes, especially under alkaline conditions. Although chlorine levels in water can be small, almost always on the scale of about 0.5 ppm to about 1.75 ppm, the available chlorine in the total volume of water that comes in contact with the enzyme during dishwashing is large. the common, consequently, the stability of the enzymes in use can be problematic. Anions of suitable radical scavengers are salts containing ammonium cations. These may be selected from the group consisting of reducing materials such as sulfite, bisulfite, thiosulphite, thiosulfate, iodide, etc., antioxidants such as carbonate, ascorbate, etc., organic amines such as ethylenediaminetetraacetic acid (EDTA) or alkali metal salt thereof and monoethanolamine (MEA), and mixtures thereof. Other conventional radical scavenging anions such as sulfate, bisulfate, carbonate, bicarbonate, percarbonate, nitrate, chloride, borate, sodium perborate tetrahydrate, sodium perborate monohydrate, percarbonate, phosphate, condensed phosphate, acetate, benzoate, citrate, formate, lactate, malate, tartrate, salicylate, etc. and mixtures thereof.

Detergency Enhancers The detergency builders are optionally included in the compositions herein. In solid formulations, builders sometimes serve as absorbers for surfactants. As an alternative, certain compositions can be formulated with water-soluble builders completely, either organic or inorganic, depending on the intended use. Suitable silicate builders include hydrated and water-soluble solid types and include those having a chain, layer or three-dimensional structure, as well as amorphous solid silicates or other types, for example especially adapted for use in unstructured liquid detergents. The preferred alkali metal silicates, in particular the liquids and solids having an SiO2: Na2O ratio in the 1.6: 1 to 3.2: 1 scale, which includes silicates of 2 solid hydrated ratios marketed by PQ Corp., under the trade name BRITESIL ®, for example BRITESIL H2O; and layered silicates, for example those described in E.U.A. No. 4,664,839, May 12, 1987, H.P. Rieck NaSKS-6, sometimes abbreviated "SKS-6", is a silicate of d-Na2SiOs morphology without crystalline layer aluminum, marketed by Hoechst and is especially preferred in granule compositions. See preparative methods in DE-A-3,417,649 German and DE-A-3, 742,043. Other layered silicates, such as those having the general formula NaMSi 2? +1 and H2 ?, where M is sodium or hydrogen, x is a number from 1.9 to 4, preferably 2, and y is a number of 0 to 20, preferably 0, may alternatively be used herein. Hoechst silicates also include NaSKS-5, NaSKS-7 and NaSKS-11, as the layered silicate forms a, β and β. Other silicates may also be useful, such as magnesium silicate, which can serve as a contrast enhancement agent in granules, and as a component of foam control systems. Also suitable for use herein are crystalline ion exchange materials synthesized or hydrates thereof having the chain structure and a composition represented by the following general formula in the form of anhydride: xM2O and SiO2.zM'O, where M is Na and / or K, M 'is Ca and / or Mg; y / x is 0.5 to 2.0 and z / x is 0.005 to LO as described in E.U.A. No. 5,427,711, Sakaguchi et al, June 27, 1995. Aluminosilicate builders, such as zeolites, are useful especially in detergents in granules, but may also be incorporated in liquids, pastes or gels. Those that are suitable for the purposes of this are those that have the empirical formula: [Mz (AIO2) z (S¡O2) v] xH2O, where z and v are integers of at least 6, M is an alkali metal, Na and / or K preference, the molar ratio of zav is on the scale of LO at 0.5, and x is an integer from 15 to 264. Aluminosilicates can be crystalline or amorphous, derivative as it occurs in nature or synthetic . An aluminosilicate production method is in E.U.A. No. 3,985,669, to Krummel, et al, October 12, 1976. Synthetic crystalline aluminosilicate ion exchange materials are available as Zeolite A, Zeoite p (b), Zeolite X, and to any degree this differs from Zeolite P, the so-called Zeolite MAP. Natural types, including clinoptilolite, can be used. Zeolite A has the formula Na? 2 [(AIO2) i2 (SiO2) i2] -xH2 ?, where x is from 20 to 30, especially 27. Dehydrated zeolites can also be used (x = 0 -10). Preferably, the aluminosilicate has a particle size of 0J-10 microns in diameter. Detergency builders in place of or in addition to the silicates and aluminosilicates described above as an option can be included in the compositions herein, for example to help control mineral hardness, especially Ca and / or Mg, in wash water or to help eliminate dirt on surface particles. Builders can operate through a variety of mechanisms including the formation of soluble or insoluble complexes with hardness values, by means of ion exchange, and offering a surface more favorable to the precipitation of hardness particles that are the surfaces of articles that are going to be cleaned. The level of builder can vary widely, depending on the final use and the physical form of the composition. Almost always detergent builder detergents comprise at least about 1% builder. Liquid formulations almost always comprise about 5% to about 50%, most often 5% to 35% builder. Granule formulations almost always comprise from about 10% to about 80%, more often 15% to 50%, by weight improver of the detergent composition. The lower or higher levels of builders are not excluded. For example, certain formulations may lack an enhancer, ie the compositions do not contain any builder, as in some hand dishwashing compositions. The detergency builders herein can be selected from the group consisting of phosphates and polyphosphates, especially the sodium salts; carbonates, bicarbonates, sesquicarbonates and mineral carbonates other than sodium carbonate or sesquicarbonate; organic mono-, di-, tri- and tetracarboxylates, in particular carboxylates which are not water-soluble surface-active agents in acid, sodium, potassium or alkanolammonium salt form, or low molecular weight, oligomeric or water-soluble polymer carboxylates, which include aliphatic and aromatic types; and phytic acid. These can be complemented by borates, for example, for pH regulation purposes, or by sulfates, especially sodium sulfate and any other filler or vehicles that may be important for the technology of detergent compositions containing detergency builders and / or agents stable surfactants. Mixtures of builders, sometimes referred to as "builders systems," can be used and almost always comprise two or more conventional builders, as an option supplemented by chelators, pH regulators or fillers, although the latter generally count for separated when describing quantities of materials in the present. In terms of relative amounts of surfactant and builder in the detergents herein, preferred builder systems are almost always formulated in a weight ratio of surfactant to builder of about 60: 1 to about 1: 80 Certain laundry detergents that are preferred have said ratio in the range of 0.90: 1.0 to 4.0: 1.0, more preferably 0.95: 1.0 to 3.0: 1.0. Often preferred P-containing builders, where allowed by legislation, include but are not limited to alkali metal, ammonium and alkanolammonium salts of polyphosphates exemplified by tripolyphosphates, pyrophosphates, vitreous polymer meta-phosphates, and phosphonates. Suitable carbonate builders include alkali metal and alkaline earth metal carbonates, as described in German Patent Application No. 2,321,001, published November 15, 1973, although sodium bicarbonate, sodium carbonate, sodium sesquicarbonate and other carbonate minerals, such as trona or any convenient multiple salt of sodium carbonate and calcium carbonate, such as those having the composition 2Na2C03.CaC03, when it is anhydrous, and even calcium carbonates, which include calcite, aragonite and vaterite, especially shapes that have large surface areas relative to compact calcite, may be useful for example as seeds. Suitable "organic builders" as described herein for use in cleaning compositions include polycarboxylate compounds, including dicarboxylates that are not water-soluble surfactants and tricarboxylates. More often, polycarboxylates with builders have a plurality of carboxylate groups, preferably at least 3 carboxylates. The carboxylate builders can be formulated in acid, partially neutral, neutral or with base form. When they are in the salt form, the alkali metals, such as sodium, potassium and lithium, or alkanolammonium salts, are preferred. Polycarboxylate builders include the polycarboxylates of ether, such as oxydisuccinate, see Berg, E.U.A. No. 3,128,287, April 7, 1964, and Lamberti et al, E.U.A. No. 3,635,830, January 18, 1972; detergency builders "" TMS / TDS "US No. 4,663,071, Bush et al, May 5, 1987, and other ether carboxylates including cyclic and alicyclic compounds, such as those described in US Patent Nos. 3,923,679; 3,835,163; 4,158,635; 4,120,874 and 4,102,903 Other suitable detergent builders for organic detergents are ether hydroxypolycarboxylates, maleic anhydride copolymers with ethylene or vinyl methyl ether; 1, 3,5-trihydroxybenzene-2,4,6-trisulfonic acid; carboxymethyloxysuccinic acid; the various alkali metal, ammonium and substituted ammonium salts of polyacetic acids, such as eilendiamintetraacetic acid and nitrilotriacetic acid; as well as a melitic acid, succinic acid, polymaleic acid, benzene, 3,5-tricarboxylic acid, carboxymethyloxysuccinic acid and soluble salts thereof. Citrates, for example salts of dihydric acid and soluble thereof are important carboxylate builders, for example for light duty liquid detergents, thanks to their availability from renewable resources and their biodegradable capacity. The citrates can also be used in granular compositions, especially in combination with zeolite and / or layered silicates. The oxydisuccinates are also useful especially in those compositions and combinations. When permitted, and especially in the formulation of bars, alkali metal phosphates, such as sodium tripolyphosphates, sodium pyrophosphate and sodium orthophosphate can be employed. Phosphonate builders, such as ethan-1-hydroxy-1, 1-disphosphonate and other known phosphonates, for example those of E.U.A. No. 3,159,581; 3,213,030; 3,422,021; 3,400,148 and 3,422,137 may also be used and may have desirable descaling properties. Certain detersive surfactants or their short chain homologs also have an action of builders. In order to have a precise formula, when they have the capacity of surfactants, these materials are added as detersive surfactants. Preferred types for builder functionality are illustrated by: 3,3-dicarboxy-4-oxa-1,6-hexanedioates and the related compounds described in E.U.A. No. 4,566,984, Bush, January 28, 1986. Succinic acid builders include the C5-C20 alkyl and alkenyl succinic acids and salts thereof. Succinate builders also include: lauryl succinate, myristiisuccinate, palmitiisuccinate, 2-dodecenylsuccinate (preferred), 2-pentadecenylsuccinate and the like. The lauryl succinates are described in European patent application 86200690.5 / 0,200,263, published on November 5, 1986. Fatty acids, for example, C 2 -CI 8 monocarboxylic acids, can also be incorporated into the compositions as agent materials surfactants / detergency builders alone or in combination with the aforementioned detergency builders, especially citrate and / or succinate builders, to provide an additional builder activity. Other suitable polycarboxylates are described in E.U.A. No. 4,144,226, Crutchfield et al, March 13, 1979 and in E.U.A. No. 3,308,067, Diehl, March 7, 1967. See also Diehl, E.U.A. No. 3,723,322. Other types of inorganic builders materials that can be used have the formula (Mx) i Cay (C03) z, where xei are integers from 1 to 15, and is an integer from 1 to 10, z is an integer from 2 to 25, M, are cations, at least one that is water-soluble, and the equation Si = 1-15 (x, multiplied by the valence of M,) + 2y = 2z is satisfied so that the formula has a neutral charge or "balanced". These builders are preferred herein as "mineral builders", examples of these builders, their use and preparation can be found in the US patent. No. 5,707,959. Another suitable class of inorganic builders is the magnesiosilicates, see WO 97/0179. Polycarboxylate builders suitable for use herein include maleic acid, citric acid, preferably in the form of a hydrosoluble salt, succinic acid derivatives of the formula R-CH (COOH) CH2 (COOH), wherein R is C10-20 alkyl or alkenyl, preferably C12-16, or R can be substituted with hydroxyl, sulfo sulfoxyl or sulfone substituents. Also provided are mixtures of these suitable polycarboxylate builders, such as a mixture of maleic acid and citric acid. Specific examples include lauryl succinate, mirisityl succinate, palmityl succinate 2-dodecenylsuccinate, 2-tetradecenyl succinate. Succinate builders are preferably used in the form of their water-soluble salts, which include sodium, potassium, ammonium and alkanolammonium salts. Other suitable polycarboxylates are oxodisuccinates and mixtures of monosuccinic acid of tartrate and disuccinic tartrate acid, such as those described in E.U.A. No. 4,663,071. Especially for the liquid embodiment herein, the fatty acid builders suitable for use herein are saturated or unsaturated C10-18 fatty acids, as well as the corresponding soaps. Preferred saturated species have from 12 to 16 carbon atoms in the alkyl chain. The preferred unsaturated fatty acid is oleic acid. Another preferred builder system for liquid compositions is based on dodecenyl succinic acid and citric acid. The composition will preferably contain at least about 0.2%, more preferably at least about 0.5%, still more preferably at least about 3%, even more preferably at least about 5% by weight composition of detergency improver. The cleaning composition will also preferably contain no more than about 50%, more preferably no more than about 40%, more preferably not more than about 30%, even more preferably not more than about 25% by weight of said detergent builder composition.

Divalent Ions The presence of magnesium (divalent) ions improves the cleaning of greasy soils for various compositions, ie, compositions containing alkyl ethoxy sulfates and / or polyhydroxy fatty acid amides. This is especially true when the compositions are used in soft water containing few divalent units. It is believed, without wanting to be limited to the theory, that the magnesium ions increase the compaction of surfactants in the oil / water interface, so that the tension of the entrecara is reduced and the fat cleaning is improved. The compositions of the invention containing magnesium ions exhibit optimum fat removal, exhibit softness to the skin and provide optimum storage stability. It has been suddenly discovered that the combination of the modified alkylbenzenesulfonate surfactants of this invention with magnesium ions provides the same cleaning benefits as an LAS / Mg cleaning system, but with the additional advantage that the forming system is Dissolves faster when adding water. The composition will preferably contain at least about 0.01%, more preferably at least about 0.015%, still more preferably at least about 0.02%, even more preferably at least about 0.025% by weight of said composition of divalent ones. The cleaning composition will also preferably contain no more than about 5%, more preferably no more than about 2.5%, more preferably not more than about 1%, even more preferably not more than about 0.05% by weight of said composition of divalent ions. Preferably, the divalent ions are added as a salt of hydroxide, chloride, acetate, formate, oxide or nitrate to the compositions of this invention. It is preferred that when the compositions of this invention include divalent units, they are magnesium ions. The formulation of such compositions which do not contain divalent units in alkaline pH matrices can be difficult, due to the incompatibility of the divalent ions, in particular magnesium, with hydroxide ions. When both divalent and alkaline pH are combined with the surfactant mixture of this invention, fat cleaning is achieved which is superior to that obtained with alkaline pH or divalent alone. Even during storage, the stability of these compositions becomes deficient, due to the formation of hydroxide precipitates. Therefore, chelating agents that appear earlier may also be necessary.

Diamines It is preferred that the diamines used in the present invention have substantially no impurities; that is, by "substantially none" it is understood that the diamines are pure above 95%, that is, preferably 97%, more preferably 99%, more preferably even 99.5%, without impurities. Examples of impurities that may be present in commercially available diamines include 2-methyl-1,3-diaminobutane and alkylhydropyrimidine. It is also believed that the diamines should not have any oxidation reagent, to avoid the degradation of diamines and ammonia formation. Also, if the amine oxide and / or other surfactants are present, the amine oxide or surfactant should not have hydrogen peroxide. The preferred level of hydrogen peroxide in the amine oxide or paste of amine oxide surfactants is 0-40 ppm, more preferably 0-15 ppm. The amine impurities in the amine oxide and the betaines, if present, should be reduced as much as possible to the levels previously referred to for hydrogen peroxide. The preparation of the compositions that do not have hydrogen peroxide is important when they contain an enzyme. The peroxide can react with the enzyme and destroy any performance benefit that the enzyme adds to the composition. Even small amounts of hydrogen peroxide can cause problems with formulations that contain enzymes. Nevertheless, the dlamin can react with any peroxide present and act as an enzyme stabilizer and prevent the hydrogen peroxide from reacting with the enzyme. The only disadvantage of this stabilization of enzymes by diamine is that it is believed that the nitrogen compounds produced cause odors. The behavior of diamine as an enzyme stabilizer also prevents it from providing the benefits to the composition for which it was originally intended, in order to carry out, mainly, fat cleaning, foaming, dissolution and stability in low temperature. It is therefore preferred to reduce as much as possible the amount of hydrogen peroxide present as an impurity in the compositions of the invention, either by using components that do not substantially have hydrogen peroxide and / or by using antioxidants other than diamine, although this may act as an enzyme stabilizer, given the possible generation of malodorous compounds and the reduction in the amount of diamine available, present to perform its basic role. It is further preferred that the compositions of this invention have no "bad smell"; that is, that the smell of the upper space does not generate a negative olfactory response from the consumer. This can be achieved in many ways, including the use of perfumes to hide any undesirable odor, the use of stabilizers, such as antioxidants, chelators, etc., and / or the use of diamines that do not have substantially impurities. It is believed, without wishing to be limited to the theory, that the impurities present in the diamines are the cause of most malodours in the compositions of this invention. These impurities can be formed during the preparation and storage of the diamines. They can also be formed during the preparation and storage of the composition of the invention. The use of stabilizers, such as antioxidants and chelators, inhibit and / or prevent the formation of these impurities in the composition from the time of preparation to final use by the user and even more. Accordingly, it is still more preferred to eliminate, suppress and / or prevent the formation of these malodours by the addition of perfumes, stabilizers and / or the use of diamines which substantially do not have impurities. One type of preferred organic diamines is one in which pK1 and pK2 are in the range of about 8.0 to about 11.5, preferably in the range of about 8.4 to about 11, more preferably from about 8.6 to about 10.75. Preferred materials for yield and delivery considerations are 1, 3-bis (methylamino) -cyclohexane, 1.3 propan diamine (pK1 = 10.5, pK2 = 8.8), 1,6 hexane diamine (pK1 = 11; pK2 = 10 ), 1,3 pentan diamine (Dytek EP) (pK1 = 10.5, pK2 = 8.9), 2-methyl 1,5-pentan diamine (Dytek A) (pK1 = 11.2, pK2 = 10.0). Other preferred materials are the primary diamines / primary diamines with alkylene spacers ranging from C4 to C8. It is generally believed that primary diamines are preferred over secondary and tertiary diamines.

Definition of pK1 and pK2 As used herein, "pKal" and "pKa2" are amounts of a type generally known to those skilled in the art as "pKa", which is used in the present in the same manner as commonly he is known among experts in the field of chemistry. The values referred to herein can be obtained from written material, such as "Critical Stability Constants: Volume 2, Amines" by Smith and Martel, Plenum Press NY and London, 1975. Additional information on pKas can be obtained from written material relevant business, such as the information provided by Dupont, a provider of diaminas. As a definition that works in the present, the pKa of the diamines is specified in a completely aqueous solution at 25 ° C and for an ionic resistance between OJ at 0.5 M. The pKa is an equilibrium constant that can change with temperature and resistance ionic; in this way, the values reported in the written material sometimes do not match, depending on the measurement method and conditions. To eliminate ambiguity, the relevant conditions and / or references used for pKas of this invention are as defined herein or in "Critical Stability Constants: Volume 2, Amines". A typical method of measurement is the potentiometric titration of acid with sodium hydroxide and the determination of pKa by suitable methods, as described and referenced in "The Chemist's Ready Reference Handbook" by Shugar and Dean, McGraw Hill, NY, 1990. It has been determined that substituents and structural modifications that decrease to pK1 and pK2 below about 8.0 are not desirable and cause yield losses. This may include substitutions that carry ethoxylated diamines, hydroxy ethyl substituted diamines, oxygen diamines in the beta (and less in gamma) position to the nitrogen in the spacer group (e.g., Jeffamine EDR 148). In addition, ethylenediamine-based materials are not suitable. Some of the diamines useful herein can be defined by the following structure: wherein R2-5 are independently selected from H, methyl, -CH3CH2 and ethylene oxides; Cx and Cv are independently selected from methylene groups or branched alkyl groups, where x + y is from about 3 to about 6; and A is present as an option and is selected from parts that donate or withdraw electrons, chosen to adjust the pKas of the diamine to the desired scale. If A is present, then x and y must be 1 or greater. Alternatively, the diamines may be the organic diamines with a molecular weight less than or equal to 400 g / mol. It is preferred that these diamines have the formula: wherein each R6 is independently selected from the group consisting of hydrogen, linear or branched C1-C4 alkyl, alkyleneoxy having the formula: - (R70) mR8 wherein R7 is linear or branched C2-C4 alkylene and mixtures thereof same; R8 is hydrogen, C1-C4 alkyl and mixtures thereof; m is from 1 to about 10; X is a unit selected from: i) linear C3-C10 alkylene, branched C3-C6 alkylene, C3-C10 cyclic alkylene, branched C3-C10 cyclic alkylene, an alkyleneneoxyalkylene having the formula: - (R70) ) mR7- wherein R7 and m are the same, as defined hereinbefore; ii) linear alkylene of C3-C10, linear branched of C3-C10, cyclic of C3-C10, arylene of C6-C? 0, wherein said unit comprises one or more parts that donate electrons or withdraw electrons, which provide said diamine with a pKa greater than 8; and iii) mixtures of (i) and (ii), as long as the diamine has a pKa of at least 8. Examples of preferred diamines include the following: dimethyl aminopropyl amine, 1,6-hexanediamine, 1,3 propan diamine, 2-methyl-1,5-pentanediamine, 1,3-pentanediamine (available under the trademark Dytek EP), 1,3-diaminobutane, 1,2-bis (2-aminoethoxy) ethane (available under the trade name) Jeffamina EDR 148), isophorone diamine, 1,3-bis (methylamine) -cyclohexane and mixtures thereof.Polymeric foam stabilizer The compositions of this invention may optionally contain a polymeric foam stabilizer. These polymeric foam stabilizers provide extended foam volume and foam life without sacrificing the short grease ability of liquid detergent compositions. These polymeric foam stabilizers are preferably selected from: i) (N, N-dialkylamino) alkyl acrylate ester homopolymers having the formula: wherein each R is independently hydrogen, C -C8 alkyl and mixtures thereof, R1 is hydrogen, CrC6 alkyl and mixtures thereof, n is from 2 to 6; and (ii) copolymers of (i) and wherein R1 is hydrogen, C1-C6 alkyl and mixtures thereof; as long as the ratio of (ii) to (i) is from about 2 to 1 to about 1 to 2. The molecular weight of the polymeric foam enhancer, determined by conventional gel permeation chromatography, is about 1,000. to around 2,000,000. preferably from about 5,000 to about 1,000,000, more preferably from about 10,000 to about 750,000, more preferably from about 20,000 to about 500,000, still more preferably from about 35,000 to about 200,000. The polymeric foam stabilizer as an option may be present in the form of a salt, either an inorganic or organic salt, for example the (N, N-dialkylamino) alkyl acrylate ester citrate, sulfate or nitrate salt. A preferred polymeric foam stabilizer is (N, N-dialkylamino) alkyl acrylate ester, namely The composition will preferably contain at least about 0.01%, more preferably at least about 0.05%, still more preferably at least about 0.1% by weight of the polymeric foam enhancer composition. The composition will also preferably contain no more than about 15%, more preferably no more than about 10%, more preferably not more than about 5% by weight of the polymeric foam enhancer composition. Other suitable polymeric foam stabilizers, including protenaceous foam stabilizers and zwitterionic foam stabilizers, can be found in PCT / US98 / 24853, filed on November 20, 1998 (Case No. 6938), PCT / US98 / 24707, filed on November 20, 1998 (Case No. 6939), PCT / US98 / 24699, filed on November 20, 1998 (Case No. 6943) and PCT / US98 / 24852, filed on November 20, 1998 (Case No. 6944) ).

Another suitable type of foam stabilizers are cationic copolymer stabilizers, which contain approximately more than 50% by weight of units derived from acrylamide, methacrylamide or a mixture thereof, 0.5 to 2% pendant quaternary nitrogen, and OJ to 10. % of hydrophobic groups of C.sub.8-24 pendants, preferably the copolymer contains, approximately by weight, 55 to 95% units derived from acrylamide, methacrylamide or a mixture thereof, 4 to 30% functional units in hydrophilic form having the molecular configuration of units derived from at least one monomer containing a quaternary ammonium group, unsaturated monoethylenically, and 1 to 15% units derived from at least one monomer containing a hydrophobic group of C.sub .8-24, not monoethylenically saturated, free of quaternary nitrogen. It is more preferred that the monomer containing a quaternary ammonium group has the formula: wherein Ri is H or CH3, R2 and R3 are independently CM alkyls, R4 is C1-4 alkyl, C2.3 hydroxyalkyl or benzyl R2, R3 and R4 contain less than 9 carbon atoms, Z is a forming anion of water-soluble salt, and M can be -CO-X-, then X is -O- or -NR5-, R5 is H or alkyl of C and x is 1-6, or M can be phenylene, then x is 1; and that the monomer containing a hydrophobic group has the formula where Ri is H or CH3, X is -O- or -NR7-, Y is -C2H40- or -C3H7O-, and is 0-60, when X is -O-, R6 is hydrocarbyl of Cs-24 , and when X is -NR7-, R6 is hydrocarbyl of C _24 and R is H or hydrocarbyl C _24, wherein at least one of Rβ and R is hydrocarbyl of C8.24. For more details on these cationic copolymer stabilizers, see U.S. Pat. No. 4454060.

Thickener The detergent compositions for washing dishes herein may also contain from about 0.2% to 5% of a thickener. More preferably, said thickener will comprise from about 0.5% to 2.5% of the compositions herein. Suitable thickeners include hydroxy ethyl cellulose, hydroxyethyl methyl cellulose, carboxy methyl cellulose, Quatrisoft LM200 and the like. A preferred thickener is hydroxypropyl methylcellulose. The composition may preferably contain at least about 0.1%, more preferably at least about 0.2%, still more preferably at least about 5% by weight of the thickener composition. The composition will also preferably contain no more than about 5%, more preferably no more than about 3%, more preferably not more than about 2.5% by weight of the thickener composition. The hydroxypropyl methylcellulose polymer has a number average molecular weight of about 50,000 to 125,000 and a viscosity of 2% by weight of aqueous solution at 25 ° C. (ADTMD2363) from approximately 50,000 to around 100,000 cps. A particularly preferred hydroxypropyl cellulose polymer is Methocel® J75MS-N, wherein an aqueous solution of 2.0% by weight at 25 ° C has a viscosity of about 75,000 cps. Especially preferred hydroxypropyl cellulose polymers are surface treated, such as the hydroxypropyl cellulose polymer will readily disperse at 25 ° C in an aqueous solution having a pH of at least about 8.5. When formulated in the dishwashing detergent compositions of the present invention, the hydroxypropyl methylcellulose polymer must impart a Brookfield viscosity of about 500 to 3500 cps at 25 ° C to the detergent composition. More preferably, the hydroxypropyl methylcellulose material will impart a viscosity of about 1000 to 3000 cps at 25 ° C. For purposes of this invention, the viscosity is measured with a Brookfield LVTDV-11 viscometer using an RV # 2 spindle at 12 r.p.m. Clay thickeners are also suitable for use as thickeners. A suitable clay thickener is Laponite. When Laponite clay is used, it is present in the present composition at a concentration of about 0.25% to about 2.0% by weight, more preferably about 0.5 to about 1.75% by weight; it is a colored clay which as an option has at least about 5.0% by weight of tetrapotasium pyrophosphate peptizer, which is Laponite RDS. The particle size of Laponite RDS produced by Laponite Inorganics of Great Britain has a particle size < 2% greater than 250 microns, a density in volume of approximately 1000 kg / m.sup.3, and a surface area of approximately 330 m.sup.3 / g. Laponite RD does not have a peptizer and has a particle size < 2% greater than 250 microns, a surface area of approximately 370 m.sup.2 / g and a density in volume of approximately 1000 Kg / m.sup.3. When the compositions contain an abrasive, the dishwashing composition may also contain an expandable colloid forming clay which functions as a thickening agent for the formula and as a suspending agent for the abrasive. These expandable clays are those classified geologically as smectites and attapulgites. The appropriate smectite clays are the montmorillonite clays that are basically hydrated aluminosilicates and the hectorites that are basically hydrated magnesium silicates. It should be understood that the proportion of hydration water in the smectite clays varies with the manner in which the clay has been processed. Nevertheless, the amount of water present is not important, because the expandable characteristics of hydrated smectite clays are dictated by the fenestrated structure of the silicate. In addition, the deficit loads in the smectite are compensated by cations such as sodium, calcium, potassium, etc., which are sorbed between the mineral matrix structure of the clay in three layers (two tetrahedral and one octahedral). Smectite clays used in the liquid compositions are commercially available under various trade names, such as Thixogel No. 1 and Gelwhite GP from Georgia Kaolin Company (both montmorillonites) and Veegum Por and Veegum F from R.T. Vanderbilt (both hectoritas). A preferred clay is Gelwhite GP, which is a colloidal montmorillonite clay of high viscosity sold by Georgia Kaolin Company. This clay contains around 6% to 10% by weight of water and is a mixture of the following oxides: 59% SIO.sub.2, 21% Al.sub.3 O.sub.3, 1% Fe.sub. 2 O.sub.3, 2.4% CaO, 3.8% MgO, 4.1% Na.sub.2 O and 0.4% K.sub.2 O. 100% by weight of the clay passes through a 200 mesh screen. It disperses easily in water, but requires maximum expansion in water before use. This expansion of the clay is important to eliminate the formation of liquid layers. During this expansion process, the clay / water mixture forms a substantial viscosity. It is also thixotropic and, consequently, presents an elastic limit for a clay / water mixture of Gelwhite GP, because at this point the other physical properties of the final composition are acceptable, for example, pouring capacity, dispersability, suspension capacity and formation of liquid layers. (The term "layering" refers to the amount - in millimeters - of clear liquid visible on the surface of the finished formula after standing at 49 degrees C for one week and for ten weeks). A clay / water mixture that has an elastic limit of 350 dynes / cm.sup.2 is acceptable, regardless of the concentration of Gelwhite GP. The elastic limit is usually measured using a container and slotted rotor HAAKE rv12, MVIP, E = 0.3, R = 100 or = 113 min, of 18 minutes of permanence. Another expandable clay material suitable for use in liquid compositions is geologically classified as attapulgite, a magnesium-rich clay. A typical attapulgite analysis produces 55.02% SiO.sub.2; 10.24% Al.sub.2 O.sub.3; 3.53% Fe.sub.2 O.sub.3; 10.49% MgO; 0.47% K.sub.2 Ó; 9.73% H.sub.2 O removed at 150 degrees C and 10.13% H.sub.2 O removed at higher temperatures. These clays have a small particle size, where 100% of the clay passes through a 200 mesh screen. Attapulgite clays are commercially available under various trade names, such as Attagel 40, Attagel 50 and Attagel 150 from Engelhard Minerals & Chemicals Corporation. Of course, mixtures of attapulgite clays are also suitable for providing combination properties that are not obtained from any previous clay class. In order to achieve the desired expansion, a slurry of clay in water is subjected to mixing with high shear for a time sufficient to substantially hydrate the clay completely before it is introduced into the organic portion of the formulation. For example, the desired expansion can be carried out by a high speed shear stress of 8% aqueous clay dispersion for 25 minutes. When the clay is substantially completely hydrated, the viscosity of the aqueous suspension increases dramatically, and then, the expansion process allows the use of lower concentrations of clay. For example, the clay concentrations in only 1% to 1.55% and up to a maximum of 3%, preferably 1.2% to 2% by weight are effective to stabilize the abrasive composition of the invention, without adversely affecting the capacity of dispersion in water. As already indicated, the clay / water mixture used in the described composition preferably has an elastic limit of about 350 dians / cm 2, but satisfactory abrasive compositions can be prepared with aqueous clay dispersions having an elastic limit of only 300 dynes / cm2 and up to 450 dynes / cm2. The water-soluble low density abrasives mentioned above are suspended in the liquid dishwashing composition and their concentration ranges from 3% to 15%, preferably from 5% to 15% by weight. If desired, small amounts, for example, 1% to 255 by weight (based on the total weight of abrasive in the composition), of crystalline abrasives having a Mohns hardness of 2 to 7, such as a calcium carbonate or silica, can be substituted for part of the low density abrasive, as long as a substantially stable liquid washing composition is produced.

Abrasive These cleaning compositions as an option may contain from about 0 to about 20% by weight, more preferably from about 0.5 to about 10% by weight of an abrasive. Preferably, the abrasive is selected from the group consisting of amorphous hydrated silica, calcite, which is a limestone calcium carbonate, and polyethylene powder particles and mixtures thereof. A suitable amorphous silica (oral grade) to improve the degreasing capacity of the composition is provided by Zeoffin. The average particle size of the Zeoffin silica is from 8 to 10 mm. Its apparent density is 0.32 to 0.37 g / ml. Another silica is Tixosil 103, manufactured by Rhone-Poulec. A Crosfield amorphous hydrated silica of different particle sizes (9, 15 and 300 mm), and the same bulk density was also used. A polyethylene powder suitable for use in this invention has a particle size of about 200 to about 500 microns and a density of about 0.91 to about 0.99 g / liter, more preferably about 0.94 to about 0.96. Another preferred abrasive is calcite, which is used in a concentration of about 0% to 20% by weight, more preferably 1% by weight to 10% by weight and is made by J.M. Huber Corporation of Illinois. Calcite is a limestone consisting basically of calcium carbonate and 1% to 5% of magnesium carbonate, which has an average particle size of 5 microns and oil absorption (erased) of about 10 and a hardness of about 3.0 Mohs .

Solvents A variety of water miscible liquids may be employed, such as lower alkanols, diols, other polyols, ethers, amines and the like. In particular, C1-C4 alkanols are preferred. Said solvents may be present in the compositions herein to the extent of about 1% to 8%. When present, preferably, the composition will contain at least about 0.01%, more preferably at least about 0.5%, still more preferably at least about 1% by weight of the solvent composition. The composition will also preferably contain no more than about 20%, more preferably no more than about 10%, more preferably not more than about 8% by weight of the solvent composition. These solvents may be used in conjunction with an aqueous liquid vehicle, such as water, or may be employed without the presence of any aqueous liquid vehicle. Solvents are broadly defined as compounds that are liquid at temperatures of 20 ° C - 25 ° C and are not considered as surfactants. One of the distinguishing characteristics is that solvents tend to exist as discrete entities, rather than vast mixtures of compounds. Examples of solvents suitable for the present invention include methanol, ethanol, propanol, isopropanol, 2-methyl prirrolidinone, benzyl alcohol and morpholine n-oxide. Among these preferred solvents are methanol and isopropanol. Suitable solvents for use in this invention include ethers and diethers having from 4 to 14 carbon atoms, preferably from 6 to 12 carbon atoms, and more preferably from 8 to 10 carbon atoms. Also other suitable solvents are alkoxylated glycols or glycols, alkoxylated aromatic alcohols, aromatic alcohols, aliphatic branched alcohols, alkoxylated aliphatic branched alcohols, linear alkoxylated C1-C5 alcohols, linear C1-C5 alcohols and C8-C14 alkyl and cycloalkyl hydrocarbons , C6-C16 glycol ethers and mixtures thereof. Suitable glycols which may be used herein are in accordance with the formula HO-CR1 R2-OH, wherein R1 and R2 independently are H or a saturated or unsaturated and / or cyclic aliphatic hydrocarbon chain. Suitable glycols to be used herein are dodecane glycol and / or propanediol. Propylene glycols are also suitable, such as those with molecular weight in the range of about 100 to 1000. A suitable polypropylene glycol has a molecular weight of about 2700. Suitable alkoxylated glycols that can be used herein are in accordance with the formula R- (A) n- R 1 -OH, wherein R is H, OH, a saturated or unsaturated linear alkyl of 1 to 20 carbon atoms, preferably 2 to 15, and more preferably 2 to 10, wherein R 1 is H or an alkyl linear saturated or unsaturated of 1 to 20 carbon atoms, preferably 2 to 15 and more preferably 2 to 10, is already an alkoxy group, preferably ethoxy, methoxy and / or propoxy and n is from 1 to 5, preferably 1 to 2. Suitable alkoxylated glycols to be used herein are methoxy octadecanol and / or ethoxyethoxyethanol.

Suitable alkoxylated aromatic alcohols which can be used herein are according to the formula R (A) n-OH, wherein R is an aryl group substituted with alkyl or unsubstituted with alkyl of 1 to 20 carbon atoms, preferably of 2 to 15, and more preferably from 2 to 10, wherein A is an alkoxy group, preferably butoxy, propoxy and / or ethoxy, and n is an integer from 1 to 5, preferably 1 to 2. Suitable alkoxylated aromatic alcohols they are benzoxyethanol and / or benzoxypropanol. Suitable aromatic alcohols which can be used in this invention are according to the formula R-OH, where R is an aryl group substituted with alkyl or unsubstituted with alkyl of 1 to 20 carbon atoms, preferably 1 to 15, and more preferably from 1 to 10. For example, a suitable aromatic alcohol to be used herein is benzyl alcohol. Suitable aliphatic branched alcohols which may be employed herein are in accordance with the formula R-OH, wherein R is a saturated or unsaturated branched alkyl group of 1 to 20 carbon atoms, preferably 2 to 15, and with greater preference of 5 to 12. Branched aliphatic alcohols are particularly suitable to be used in the present invention include 2-ethylbutanol and / or 2-methylbutanol. Suitable alkoxylated aliphatic branched alcohols which may be employed herein are in accordance with the formula R (A) n-OH, wherein R is a saturated or unsaturated branched alkyl group of 1 to 20 carbon atoms, preferably 2 carbon atoms. to 15, and more preferably from 5 to 12, wherein A is an alkoxy group, preferably butoxy, propoxy and / or ethoxy, and n is an integer from 1 to 5, preferably 1 to 2. Alkoxylated branched aliphatic alcohols Suitable include 1-methylpropoxyethanol and / or 2-methylbutoxyethanol. Suitable C 1 -C 5 alkoxylated linear alcohols which can be used herein are according to the formula R (A) n-OH, wherein R is a saturated or unsaturated linear alkyl group of 1 to 5 carbon atoms, preferably from 2 to 4, wherein A is an alkoxy group, preferably butoxy, propoxy and / or ethoxy, and n is an integer from 1 to 5, preferably 1 to 2. Suitable C-C5 alkoxylated aliphatic linear alcohols are butoxy propoxy propanol (n-BPP), butoxyethanol, butoxypropanol, ethoxyethanol or mixtures thereof. Butoxy propoxy propanol is commercially available under the trade name n-BPP® from Dow Chemical. Suitable linear C1-C5 alcohols which may be employed herein are according to the formula R-OH, wherein R is a saturated or unsaturated linear group of 1 to 5 carbon atoms, preferably 2 to 4. Suitable linear C1-C5 alcohols are methanol, ethanol, propanol and mixtures thereof. Other suitable solvents include, but are not limited to, butyl diglycol ether (BDGE), butyl triglycol ether, tert-amyl alcohol, and the like. Particular preferred solvents which may be employed herein are butoxy propoxy propanol, butyl diglycol ether, benzyl alcohol, butoxypropanol, ethanol, methanol, isopropanol and mixtures thereof.

Other solvents suitable for use herein include propylene glycol derivatives, such as n-butoxypropanol or n-butoxypropoxypropane, water-soluble CARBITOL R solvents or water-soluble CELLOSOLVE R solvents; the water-soluble CARBITOL R solvents are compounds of the 2- (2-alkoxyethoxy) ethanol class, wherein the alkoxy group is derived from ethyl, propyl or butyl; A preferred water-soluble carbitol is 2- (2-butoxyethoxy) ethanol also known as butyl carbitol. The water-soluble CELLOSOLVE R solvents are compounds of the class 2-alkoxyethoxy ethanol, where 2-butoxyethoxyethanol is preferred. Other suitable solvents include benzyl alcohol, and diols such as 2-ethyl-1,3-hexanediol and 2,2,4-trimethyl-1,3-pentanediol and mixtures thereof. Some preferred solvents for use herein are n-butoxypropoxypropanol, BUTYL CARBITOL® and mixtures thereof. These solvents can also be selected from the group of compounds comprising ether derivatives of mono-, di- and tri-ethylene glycol, propylene glycol ethers, butylene glycol and mixtures thereof. The molecular weights of these solvents are preferably less than 350, more preferably between 100 and 300, even more preferably between 115 and 250. Examples of preferred solvents include, for example, n-hexyl ether of mono-ethylene glycol, ether n-Butyl of mono-propylene glycol and tripropylene glycol methyl ether. The ethylene glycol and propylene glycol ethers are commercially available from the Dow Chemical Company, under the tradename "Dowanol" and from Arco Chemical Company, under the trade name "Arcosolv". Other preferred solvents including n-hexyl ether of mono- and di-ethylene glycol are available from Union Carbide Company.

Solubilization Agent The compositions of the present invention may optionally contain from about 0 wt% to about 12 wt%, more preferably about 1 wt% to about 10 wt%, of at least one solubilizing agent which may be a hydrotrope, such as sodium xylene sulfonate, or sodium cumen sulfonate, mono- or dihydroxy C2-3 alkanols, such as ethanol, isopropanol and propylene glycol and mixtures thereof. The solubilization agents are included in order to control the clear turbidity properties at low temperature. As an option, urea can be used in the instant composition as a supplemental solubilizing agent at a concentration of from 0 to about 10% by weight, more preferably from about 0.5% by weight to about 8% by weight. Other suitable solubilizing agents are glycerol, water-soluble polyethylene glycols having a molecular weight of 300 to 600, polypropylene glycol of the formula HO (CH3CHCH20) nH, wherein n is a number of 2 to 18, mixtures of polyethylene glycol and polypropylene glycol (Synalox) and monoalkyl ethers of C? -C6 and esters of ethylene glycol and propylene glycol having the structural formulas R (X) nOH and R? (X) nOH, wherein R is an alkyl group of C Cß, R1 is an acyl group of C2 -C4, X is (OCH2CH2) or (OCH2 (CH3) CH) and n is a number from 1 to 4. Representative elements of the polypropylene glycol include dipropylene glycol and polypropylene glycol having a molecular weight of 200 to 1000, for example polypropylene glycol 400. Other satisfactory glycol ethers are ethylene glycol monobutyl ether (butyl cellosolve), diethylene glycol monobutyl ether (butyl carbitol), triethylene glycol monobutyl ether, monobutyl ether mono, di, tri propylene glycol, monobutyl ether tetraethylene glycol, monomethyl ether of mono, di, tripropylene glycol, propylene glycol monomethyl ether, ethylene glycol monohexyl ether, diethylene glycol monohexyl ether, propylene glycol tertiary butyl ether, ethylene glycol monoethyl ether, ethylene glycol monomethyl ether, ethylene glycol monopropyl ether, monopentyl ether ethylene glycol, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol monopropyl ether, diethylene glycol monopentyl ether, triethylene glycol monomethyl ether, triethylene glycol monoethyl ether, triethylene glycol monopropyl ether, triethylene glycol monopentyl ether, triethylene glycol monohexyl ether, mono, di, tripropylene glycol, monopropyl ether of mono, di tripropylene glycol, monopentyl ether of mono, di, tripropylene glycol, monohexyl ether of mono, di, tripropylene glycol, monomethyl ether of mono, di, tributylene glycol, monoethyl ether of mono, di, tributylene glycol, monopropyl ether of mono, di, tributylene glycol, monobutyl ether of mono, di, tributylene glycol, monopentyl ether of mono, di, tributylene glycol and monohexyl ether of mono, di, tributylene glycol, ethylene glycol monoacetate and propionate of dipropylene glycol.

Polymeric dirt release agent The compositions according to the present invention can optionally comprise one or more soil release agents. The polymeric soil release agents are characterized by having both hydrophilic segments, to hydrophilize the surface of hydrophobic fibers, such as polyester and nylon, and hydrophobic segments, to deposit on hydrophobic fibers and remain adhered thereto until the conclusion of the cycle of hydrophobic fibers. washed and, thus, serve as an anchor for the hydrophilic segments. This may allow stains that occur after treatment with the soil release agent to be easier to clean in subsequent washing procedures. If used, the soil release agents will generally comprise from about 0.01% to about 10%, preferably from about 0.1% to about 5%, more preferably from about 0.2% to about 3% by weight of the composition. The following, included by reference, disclose suitable soil release polymers for use in the present invention. E.U.A. No. 5,691, 298 Gosselink et al, issued November 25, 1997; E.U.A. No. 5,599,782 Pan et al, issued February 4, 1997; E.U.A. No. 5,415,807 Gosselink et al, issued May 16, 1995; E.U.A. No. 5,182,043 Morrall et al, issued January 26, 1993; E.U.A. No. 4,956,447 Gosselink et al, issued September 11, 1990; E.U.A. Do not. 4,976,879 Maldonado et al, issued December 11, 1990; E.U.A. No. 4,968,451 Scheibel et al, issued November 6, 1990; E.U.A. No. 4,925,577 Borcher, Sr. et al, issued May 15, 1990; E.U.A. No. 4,861, 512 Gosselink, issued August 29, 1989; E.U.A. No. 4,877,896 Maldonado et al, issued October 31, 1989; E.U.A. No. 4,702,857 Gosselink et al, issued October 27, 1987; E.U.A. No. 4,711, 730 Gosselink et al, issued December 8, 1987; E.U.A. No. 4,721,580 Gosselink, issued January 26, 1988; E.U.A. No. 4,000,093 Nico et al, issued December 28, 1976; E.U.A. No. 3,959,230 Hayes, issued May 25, 1976; E.U.A. No. 3,893,929 Basadur, issued July 8, 1975; and European patent application 0 219 048, published April 22, 1987 by Kud et al. Other suitable soil release agents are described in E.U.A. No. 4,201, 824 Voilland et al; E.U.A. No. 4,240,918 Lagasse et al; E.U.A. No. 4,525,524 Tung et al; E.U.A. No. 4,579,681 Ruppert et al; E.U.A. No. 4,220,918; E.U.A. No. 4,787,989; EP 279,134 A, 1988 to Rhone-Poulenc Chemie; EP 457,205 A for BASF (1991); and DE 2,335,044 to Unilever N.V., 1974; which are incorporated herein by reference.

Polymeric Fat Release Agents The compositions of this invention may also optionally contain polymeric fat release agents. Suitable polymeric fat release agents include those of the formula: wherein x is hydrogen or an alkali metal cation and n is a number from 2 to 16, Ri is selected from the group consisting of methyl or hydrogen, R 2 is a straight or branched chain alkyl group from Ci to C12, and R3 is a straight or branched chain alkyl group from C2 to Cie and, and is of such value that it provides a molecular weight of from about 5,000 to about 15,000. See the patent of E.U.A. No. 5573702.

Soil removal / anti-redeposition clay agents The compositions of this invention may also contain as an option water-soluble ethoxylated amines having clay, dirt removal and anti-redeposition properties. Detergent compositions in granules containing these compounds almost always contain from about 0.01% to about 10.0% by weight of the water-soluble ethoxylated amines; Liquid detergent compositions almost always contain from about 0.01% to about 5%. A preferred etch and anti-redeposition agent is ethoxylated tetraethylenepentamine. Exemplary ethoxylated amines are described in greater detail in the U.S.A. No. 4,597,898, VanderMeer, issued July 1, 1986. Another group of soil removal / anti-redeposition clay agents are the cationic compounds described in European patent application 111, 965, Oh and Gosselink, published June 27. of 1984. Other soil release / anti-redeposition clay agents that may be used include the ethoxylated amine polymers described in European Patent Application 11 1,984, Gosselink, published June 27, 1984; the zwitterionic polymers described in European Patent Application 112,592, Gosselink, published July 4, 1984; and the amine oxides described in the U.S.A. No. 4,548,744, Connor, issued October 22, 1985. Other soil release and / or anti-redeposition clay agents that are known in the art can also be used in the compositions herein. See the patent of E.U.A. No. 4,891, 160, VanderMeer, issued January 2, 1990 and WO 95/32272, published November 30, 1995. Another type of preferred anti-redeposition agent includes carboxy methyl cellulose (CMC) materials. These materials are well known in the art.

Polymeric Dispersing Agents Polymeric dispersing agents can be used for convenience at levels from about 0.1% to about 7% by weight in the compositions herein, especially in the presence of zeolite and / or layered silicate builders. Suitable polymeric dispersing agents include polymeric polycarboxylates and polyethylene glycols, although others already known in the art may also be used. It is believed, though it is not intended bound by theory, the dispersants polymeric improve the overall performance of builders when used in combination with other builders (including polycarboxylates low molecular weight) for inhibition of crystal growth, release of dirt in particles, peptization and antiredeposition. The polymeric polycarboxylate materials can be prepared by polymerization or copolymerization of suitable unsaturated monomers, preferably in their acid form. The 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 in polymeric polycarboxylates or monomeric segments, which do not contain any carboxylate radical, such as vinyl methyl ether, styrene, ethylene, etc., is suitable, as long as those segments do not constitute more than about 40% by weight. Suitable polymeric polycarboxylates in particular can be derived from acrylic acid. Said acrylic acid-based polymers which are useful herein are the water-soluble salts of polymerized acrylic acid. The average molecular weight of such polymers in the acid form of preference ranges from about 2,000 to 10,000, more preferably from about 4,000 to 7,000, and even more preferably from about 4,0100 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 been described, for example, in Diehl, U.S. Pat. No. 3,308,067, issued March 7, 1967. Acrylic / maleic based copolymers can also be used as a preferred component of the dispersing / anti-redeposition agent. Such materials include water-soluble salts of copolymers of acrylic acid and maleic acid. The average molecular weight of those polymers in acid form preferably ranges from about 2,000 to 100,000, more preferably from about 5,000 to 75,000, even more preferably from about 7,000 to 65,000. The ratio of acrylate to maleate segments in those copolymers will generally vary from about 30.1 to about 1: 1, more preferably from about 10: 1 to 2: 1. The water-soluble salts of said acrylic acid / maleic acid copolymers 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. 66915, published on December 15, 1982, as well as in EP 193,360, published on September 3, 1986, which also describes the polymers comprising hydroxypropylacrylate. Even other useful dispersing agents include the maleic / acrylic / vinyl alcohol terpolymers. These materials are also described in EP 193,360, which include for example, the acrylic / maleic / vinyl alcohol terpolymer. Another polymeric material that can be included is polyethylene glycol (PEG). The PEG can exhibit performance of the dispersing agent, as well as act as a dirt removing / anti-redeposition clay agent. Typical molecular weight scales for these purposes range 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. Dispersants of polyaspartate and polyglutamate, especially in conjunction with zeolite builders, can also be used. Dispersing agents such as polyaspartate preferably have a molecular weight (average) of about 10,000. Other types of polymer that may be more desirable for biodegradable capacity, improved bleach stability, or cleaning purposes include various hydrophobically modified terpolymers and copolymers, including those marketed by Rohm & amp; amp; amp;; Haas, BASF Corp., Nippon Shokubai and others for all the ways of water treatment, textile treatment or detergent applications.

Guelating Agents The compositions herein may also optionally contain one or more chelating agents, in particular chelating agents for adventitious transition metals. Those which are commonly found in washing water include iron and / or manganese in the form of particles or colloid, water soluble, and may be associated as oxides or hydroxides, or they are in relation to soils such as humic substances. Preferred chelators are those which effectively control said transition metals, which especially include deposition of control of said transition metals or their compounds in fabrics and / or undesirable reduction-oxidation reactions of control in the washing medium and / or on hard surfaces or fabrics. Said chelating agents include those having low molecular weights, as well as polymeric types, almost always having at least one, preferably two or more donor heteroatoms, such as O or N, capable of coordination to a transition metal. Common chelating agents can be selected from the group consisting of aminocarboxylates, aminophosphonates, polyfunctionally substituted aromatic chelating agents and mixtures thereof. The aminocarboxylates useful as optional chelating agents include ethylenediaminetetracetates, N-hydroxyethyl ethylenediamine triacetates, nitrile triacetates, ethylenediamine tetraproprinates, triethylenetetramine hexacetates, diethylenetriaminpentaacetates and ethanoldi glycins, alkali metals, ammonium and their substituted ammonium salts and mixtures thereof. Also suitable are aminophosphonates for use as chelating agents in the compositions of the invention, when at least low levels of total phosphorus are allowed 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. The aromatic chelating agents substituted in polyfunctional form are also useful in the compositions herein. See the patent of E.U.A. No. 3,812,044, issued March 21, 1974 to Connor et al. Preferred compounds of this type in acid form are dihydroxydisulfobenzenes, such as 1,2-dlhydroxy-3,5-disulfobenzene. A preferred biodegradable chelator for use herein is ethylene diamine disuccinate ("EDDS"), especially the [S, S] isomer, as described in the U.S.A. No. 4,704,233, November 3, 1987, to Hartman and Perkins. The compositions herein may also contain water-soluble salts of methylglyc- indiacetic acid (MGDA) (or acid form) as a chelator or co-builder. Similarly, so-called "weak" detergency builders, such as citrate, can also be used as chelating agents.

If used, the chelating agents will generally comprise from about 0.001% to about 15% by weight of the detergent compositions herein. More preferably, if used, the chelating agents will comprise from about 0.01% to about 3.0% by weight of said compositions.

Foam suppressants Compounds for reducing or suppressing foaming can be incorporated into the compositions of this invention, when required for the intended use, especially laundry in laundry appliances. Other compositions, such as those designed for hand washing, may desirably be high in foaming and may omit those ingredients. The suppression of foam may be of particular importance in what is referred to as the "high concentration cleaning process", as described in the US patent. No. 4,489,574 and European-style washing machines that are loaded from the front. A wide variety of materials such as suds suppressors can be employed and are well known in the art. See for example, Kirk Othmer Encyclopedia of Chemical Technology, third edition, volume 7, pages 430-447 (Wiley, 1979). The compositions herein generally comprise from 0% to about 10% foam suppressant. When used as suds suppressors, the monocarboxylic fatty acids, and their salts, will almost always be present in amounts up to about 5%, preferably 0.5% - 3% by weight of the detergent composition, although higher amounts may be employed. Preferably from about 0.01% to about 1% silicone foam suppressant, more preferably from about 0.25% to about 0.5% is used. These weight percent values include any silica that can be used in combination with polyorganosiloxane, as well as any auxiliary foam suppressor material that can be used. In general, monostearylphosphate foam suppressors are used, in amounts ranging from about 0.1% to about 2% by weight of the composition. Hydrocarbon foam suppressors are almost always used in amounts ranging from about 0.01% to about 5.0%, although higher levels can be used. The alcohol foam suppressors are almost always used in 0.2% - 3% by weight of the finished compositions.

Alkoxylated polycarboxylates Alkoxylated polycarboxylates, such as those prepared from polyacrylates are useful herein to provide additional performance in the removal of fat. Such materials are described in WO 91/08281 and PCT 90/01815 in p. 4 and seq, which is incorporated herein by reference. Chemically, these materials comprise polyacrylates having an ethoxy side chain for every 7-8 acrylate units. The side chains are of the formula - (CH2CH2O) m (CH2) nCH3, where m is 2-3 and n is 6-12.

The side chains are linked in ester to the polyacrylate "backbone" to provide a "comb" polymer type structure. The molecular weight can vary, but is almost always on the scale of about 2000 to about 50,000. Said alkoxylated polycarboxylates may comprise from about 0.05% to about 10% by weight of the compositions herein.

Perfumes The perfumes and perfumery ingredients useful in these present compositions and methods comprise a wide variety of natural and synthetic chemical ingredients, including, but not limited to, aldehydes, ketones, esters and the like. Also included are various natural extracts and essences which may comprise complex mixtures of ingredients, such as orange oil, lemon oil, rose extract, lavender, musk, patchouli, balsam essence, sandalwood oil, pine oil, cedar and Similar. The finished perfumes may comprise too complex mixtures of said ingredients. Almost always, the finished perfumes comprise from about 0.01% to about 2% by weight of the detergent compositions herein, and the individual perfumery ingredients may comprise from about 0.0001% to about 90% of a finished perfume composition.

Non-limiting examples of perfume ingredients useful herein include: 7-acetyl-1, 2,3,4,5,6,7,8-octahydro-1,1,6,7-tetramethyl naphthalene; methyl ionone; gamma methyl ionone; methyl cedrilone; methyl dihydrojasmonate; methyl 1, 6,10-trimethyl-2,5,9-cyclododecatrien-1-yl ketone; 7-acetyl-1, L3,4,4,6-hexamethyl tetralin; 4-acetyl-6-tert-butyl-1 J -dimethyl indane; para-hydroxy-phenyl-butanone; benzophenone; methyl beta-naphthyl ketone; 6-acetyl-1, L2,3,3,5-hexameitl indan; 5-Acetyl-3-isopropyl-1,1, 2,6-tetramethyl indan; 1-dodecanal, 4- (4-hydroxy-4-methyl-fentyl) -3-cyclohexen-1 -carboxaldehyde; 7-hydroxy-3,7-dimethyl ochatanal; 10-undecen-1-al; iso-hexenyl ciciohexyl carboxaldehyde; tricyclohexane formyl; condensation products of hydroxy-citronellal and methyl-antanylate, condensation products of hydroxy-citronellal and indole, condensation products of phenyl-acetaldehyde and indole; 2-methyl-3- (para-tert-butylphenyl) -propionaldehyde; ethyl vanillin; heliotropin; hexyl aldehyde cinnamic; amyl aldehyde cinnamic, 2-methyl-2- (para-iso-propylphenyl) -prop -onaldehyde; coumarin; gamma decalactone; Cyclopentadecanolide; 16-hydroxy-9-hexadecenic acid lactone; 1, 3,4,6,7,8-hexahydro-4,6,6,7,8,8-hexamethylcyclopenta-gamma-2-benzopyran; methyl ether of beta-naphthol; amboxano; dodecahydro-3a, 6,6,9a-tetramethyl-naphtho [2,1 bjfuran; cedrol, 5- (2,2,3-trimethylcyclopent-3-enyl) -3-methylpentan-2-ol; 2-ethyl-4- (2,2,3-triemethyl-3-cyclopenten-1-yl) -2-buten-1-ol; caryophyllene alcohol; tricyclodecenyl propionate; tricyclodecenyl acetate; benzyl salicylate; cedril acetate; and para- (tert-butyl) cyclohexyI acetate. Preferred perfume materials in particular are those that provide the most marked improvements in odors in compositions of the finished product containing cellulases. These perfumes include, but are not limited to; hexyl aldehyde cinnamic; 2-methyl-3- (para-tert-butylphenyl) -propionaldehyde; 7-acetyl-1, 2,3,4, 5,6,7,8-octahydro-1,1,6,7-tetramethylnaphthalene; benzyl salicylate; 7-acetyl-1, 1, 3,4,4,6-hexamethyl tetralin; para-tert-butyl cyclohexyl acetate; methyl dihydro jasmonate; methyl ether of beta-naphthol; methyl beta-naphthyl ketone; 2-methyl-2- (para-iso-propylphenyl) -propionaldehyde; 1, 3,4,6,7,8-hexahydro-4,6,6,7,8,8-hexamethyl-cyclopenta-gamma-2-benzopyran; dodecahydro-3a, 6,6,9a-tetramethylnaphtho [2,1b] furan; anisaldehyde; coumarin; cedrol; vanillin; Cyclopentadecanolide; tricyclodecenyl acetate, and tricyclodecenyl propionate. Other perfume materials include essential oils, resinoids and resins from a variety of sources that include, but are not limited to: Peru balm, olibanum resinoid, stretch, ladanum resin, myristic, cassia oil, benzoin resin, coriander and lavandin. Even other perfuming chemicals include phenylethyl alcohol, terpineol, linalool; iinally acetate, geraniol, nerol, 2- (1 J-dimethylethyl) -cyclohexanol acetate, benzyl acetate and eugenol. Vehicles such as diethyl phthalate can be employed in the finished perfume compositions. Instead of the perfume, especially in microemulslons, the compositions may employ an essential oil or a water-soluble organic compound, such as a water-soluble hydrocarbon having from 6 to 18 carbons, such as a paraffin or isoparaffin, such as isoparH, sodecane, alpha-pinene, beta-pinene, decanol and terpineol. Suitable essential oils are selected from the group consisting of: Anetol 20/21 natural, foreign anise seed, global brand anise seed oil, Balsamo (Peru), basil oil (India), black pepper oil, oleoresin of black pepper 40/20, Bois de Rose (Brazil) FOB, borneol flakes (China), camphor oil, white, synthetic technical camphor powder, Cananga oil (Java), cardamom oil, cassia oil (China) ), cedar oil (China) BP, cinnamon bark oil, cinnamon leaf oil, citronella oil, clove bud oil, clove leaf, coriander (Russia), coumarin grade 69, C. (China) , aldehyde cyclamino, diphenyl oxide, ethyl vanillin, eucalyptus, eucalyptus oil, Eucalyptus citriodora, fennel oil, geranium oil, ginger oil, ginger oleoresin (India), white grapefruit oil, guaiac oil, balsam balao, heliotropin, isobornyl acetate, isolongiphenol, juniper oil ina, L-methyl acetate, lavender oil, lemon oil, distilled lime oil, Litsea cubeba oil, longifollar, menthol crystals, methyl cedril ketone, methyl chavicol, methyl salicylate, musk abelmosk, musk ketone, xylol of musk, myristic oil, orange oil, patchouli oil, peppermint oil, ethyl phenyl alcohol, pepper oil, pepper leaf oil, rosemary, sandalwood oil, Sandenol, sage oil, amaryllis sage, oil of sassafras, mint oil, lavender, Tagetes, tea tree oil, vanillin, vetiver oil (Java), wintergreen.

Composition pH The dishwashing compositions of the invention will be subjected to acidic forces created by food stains when used, i.e., diluted and applied to dirty dishes. If a composition with a pH greater than 7 will be more effective, as an option it may contain a pH regulating agent with the ability to provide a more alkaline pH in general in the composition and in diluted solutions, ie from approximately 0.1% to 0.4 % by weight of aqueous solution of the composition. The pKa value of this pH regulating agent should be from about 0.5 to LO pH units below the desired pH value of the composition (determined as described above). Preferably, the pKa of the pH regulating agent should be from about 7 to about 10. Under these conditions, the pH regulating agent controls the pH much more effectively, while using the lower amount thereof. It is preferred that the compositions of this invention have a pH (measured at 10% aqueous solution) of from about 2.0 to about 12.5, more preferably from about about, more preferably from about about. The pH regulating agent may be an active detergent by itself or it may be a low molecular weight organic or inorganic material that is used in this composition only to maintain an alkaline pH. Preferred pH regulating agents for the compositions of this invention are nitrogen-containing materials. Some examples are amino acids, such as lysine or lower alcohol amines, such as mono-, di- and triethanolamine. Other preferred nitrogen-containing pH regulating agents are tri (hydroxymethyl) amino methane (HOCH2) 3CNH3 (TRIS), 2-amino-2-ethyl-1,3-propanediol, 2-amino-2-methyl-propanol, 2-amino- 2-methyl-1, 3-propanol, disodium glutamate, N-methyl diethanolamide, 1,3-diamino-propanol N, N'-tetra-methyl-1,3-diamino-2-propanol, N, N-bis ( 2-hydroxyethyl) glycine (bicine) and N-tris (hydroxymethyl) methyl glycine (tricine). Mixtures of any of the above are also acceptable. Inorganic sources of pH / alkalinity regulators include the alkali metal carbonates and alkali metal phosphates, for example sodium carbonate, sodium polyphosphate. For other pH regulators, see McCutcheon EMULSIFIERS AND DETERGENTS, US edition, 1997, McCutcheon Division, MC Publishing Company Kirk and WO 95/07971, which are incorporated herein by reference. The composition preferably will contain at least about 0.1%, more preferably at least about 1%, most preferably at least about 2% by weight of the pH regulating agent composition. The composition will also preferably contain no more than about 15%, more preferably no more than about 10%, more preferably not more than about 8% by weight of the pH regulating agent composition. 19 Hydrotropes The aqueous liquid carrier may comprise one or more materials that are hydrotropes. Hydrotropes suitable for use in the compositions herein include C1-C3 alkylaryl sulfonates, C6-C2 alkanols, carboxylic sulfates and sulphonates of C-Cβ, urea, Ci-Cβ hydroxycarboxylates, C1-C4 carboxylates, organic diacids of C2-C4 and mixtures of these hydrotrope materials. The liquid detergent composition of this invention preferably comprises from about 0.5% to 8% by weight of the liquid detergent composition of a hydrodrope selected from alkali metal and calcium xylene and toluene sulphonates. C1-C3 alkylarylsulfonates include xylene sulfonates of sodium, potassium, calcium and ammonium; toluens sodium, potassium, calcium and ammonium sulphonates; sodium, potassium, calcium and ammonium sulphonates; and substituted or unsubstituted sodium, potassium, calcium and ammonium naphthalenes and mixtures thereof. Suitable sulfate or sulfonate carboxylic salts of Ci-Cs are any water-soluble salt or organic compound comprising from 1 to 8 carbon atoms (exclusive of substituent groups), which are substituted with sulfate or sulfonate and have at least one carboxyl group. The organic compound substituted may be cyclic, acyclic or aromatic, ie benzene derivatives. Alkyl compounds that are preferred have from 1 to 4 carbon atoms substituted with sulfate or sulfonate and have from 1 to 2 carboxylic groups. Examples of this type of hydrotrope include sulfosuccinate salts, sulfophthalic salts, sulfoacetic salts, salts of m-sulfobenzoic acid and diester sulfosuccinates, preferably sodium or potassium salts, as described in U.S. Pat. No. 3,915,903. C 1 -C 4 hydroxycarboxylates and C 1 -C 4 carboxylates suitable for use herein include acetates and propionates and citrates. The C2-C4 diacids to be used herein include succinic, glutaric and adipic acids. Other compounds that provide suitable hydrotropic effects for use herein as a hydrotrope include C6-C2 alkanols and urea. Preferred hydrotropes for use herein are sodium, potassium, calcium and ammonium sulphonate cumenes; sodium, potassium, calcium and ammonium xylene sulfonate; toluene sulfonate of sodium, potassium, calcium and ammonium and mixtures thereof. Sodium cumenesulfonate and calcium xylene sulfonate and mixtures thereof are preferred. These preferred hydrotrope materials may be present in the composition to the extent of from about 0.5% to 8% by weight. The composition preferably will contain at least about 0.1%, more preferably at least about 0.2%, more preferably at least about 0.5% by weight of the hydrotrope composition. The composition preferably also will contain no more than about 15%, more preferably no more than about 105, more preferably not more than about 8% by weight of the hydrotrope composition.

Other Ingredients The detergent compositions may further comprise one or more detersive auxiliaries selected from the following: soil release polymers, polymer dispersants, polysaccharides, abrasives, batericides, stain inhibitors, color stabilizers, colorants, electrolytes (such as NaCl , etc.), antifungal or mold control agents, insect repellents, hydrotropes of acaricidal agents, processing aids, foam enhancers, brighteners, anticorrosive aids and stabilizing antioxidants. A wide variety of other ingredients useful in detergent compositions can be included in the compositions herein, including other ingredients, carriers, antioxidants, processing aids, dyes or pigments, solvents for liquid formulations, solid fillers for stick compositions, etc. If high foam formation is desired, foam enhancers, such as C10-C16 alkanolamides, can be incorporated into the compositions, almost always at levels of 1% -10%. The monoethanol amines of C-C and diethanol amines illustrate a typical class of such foam enhancers. The use of these foam enhancers with auxiliary foaming surfactants, such as amine oxides, betaines and sultaines mentioned above, is also convenient. As an option an antioxidant may be added to the detergent compositions of this invention; can be any conventional antioxidant used in detergent compositions, such as 2,6-di-tert-butyl-4-methylphenol (BHT), carbamate, ascorbate, thiosulfate, monoethanolamine (MEA), diethanolamine, triethanolamine, etc. It is preferred that the antioxidant, when present, be present in the composition from about 0.001% to about 5% by weight. Various detersive ingredients employed in the compositions herein as an option can also be stabilized by absorption of said ingredients in a hydrophobic substrate pores, and then by coating the substrate with a hydrophobic coating. Preferably, the detersive ingredient is mixed with a surfactant before being absorbed into the porous substrate. In use, the detersive ingredient is released from the substrate in the aqueous wash solution, where it performs its intended detersive function. To illustrate this technique in greater detail, a porous hydrophobic silica (trademark SIPERNAT D10, DeGussa) is mixed with a proteolytic enzyme containing 35 - 5% of nonionic surfactant (EO 7) of ethoxylated alcohol of C? 3.15. Often, the enzyme / surfactant solution is 2.5 X the weight of the silica. The resulting powder is dispersed with stirring in silicone oil (various viscosities of silicone oil can be employed in the range of 500-12,500). The resulting silicone oil dispersion is emulsified or otherwise added to the final detergent matrix. Through this means, the ingredients, such as the aforementioned enzymes, bleach, bleach activators, bleach catalysts, photoactivators, dyes, microorganos fluorescenss, fabric conditioners and hydrolyzable surfactants can be "protected" for use in detergents, including liquid laundry detergent compositions.

Form of the Composition The compositions herein may be in any form of those conventional for hand dishwashing compositions, such as paste, liquid, granules, powder, gel, liquid gel, liquid microemulsion crystals and mixtures thereof. . Extremely preferred embodiments are in liquid or gel form. The liquid compositions can be aqueous or non-aqueous. When the composition is an aqueous liquid, it will preferably also contain a vehicle for aqueous liquid in which the other components of the essential or optional compositions are dissolved, dispersed or suspended. When the composition is an aqueous liquid, the composition preferably will contain at least about 5%, more preferably at least about 10%, still more preferably at least about 30% by weight of the vehicle composition for aqueous liquid.

The composition will also preferably contain no more than about 95%, more preferably no more than about 60%, more preferably not more than about 50% by weight of the vehicle composition for aqueous liquid. An essential component of the vehicle for aqueous liquid, of course, is water. However, the vehicle for aqueous liquid may contain other materials that are liquid, or that dissolve in the vehicle for liquid, at room temperature and that may also serve for another function in addition to that of a simple filler. Such materials may include, for example, hydrotropes and solvents. The low molecular weight primary or secondary alcohols exemplified by methanol, ethanol, propanol and isopropanol are suitable. Monohydric alcohols are preferred to solubilize surface active agents, but polyols such as those containing from 2 to about 6 carbon atoms and from 2 to about 6 hydroxy groups (for example 1,3-propanediol, ethylene glycol, glycerin) can also be used. and 1,2-propanediol). An example of the process for making granules of the detergent compositions herein is as follows: - modified alkylbenzenesulfonate, citric acid, sodium silicate, sodium sulfate perfume, diamine and water are added, heated and mixed through a support. The resulting suspension is spray-dried in the form of granules.

An example of the process for making the liquid detergent compositions herein is as follows: - Free water and citrate are added and dissolved. To this solution is added amine oxide, betaine, ethanol, hydrotrope and nonionic surfactant. If free water is not available, citrate is added to the previous mixture, then stirred until dissolved. At this point, an acid is added to neutralize the formulation. It is preferred that the acid be chosen from organic acids, such as maleic and citric acids, however, inorganic mineral acids can also be used. In preferred embodiments, these acids are added to the formulation after the addition of diamine. To the last one, AExS is added.

Non-aqueous liquid detergents The preparation of liquid detergent compositions comprising a non-aqueous vehicle medium can be carried out in accordance with the descriptions of the US patents. Nos. 4,753,570; 4,767,558; 4,772,413; 4,889,652; 4,892,673; GB-A-2, 158,838; GB-A-2,195,125; GB-A-2,195,649; E.U.A. 4,988,462; E.U.A. 5,266,233; EP-A-225,654 (6/16/87); EP-A-510,762 (10/28/92); EP-A-540,089 (5/5/93); EP-A-540,090 (5/5/93); E.U.A. 4,615,820; EP-A-565,017 (10/13/93); EP-A-030,096 (10/6/81), incorporated herein by reference. Said compositions may contain various detersive ingredients in particles suspended stably therein. Said non-aqueous compositions, accordingly, comprise a LIQUID PHASE and, as an option, but preferably, a SOLID PHASE, as described in greater detail hereinafter and in the references mentioned. The compositions of this invention can be used to form aqueous wash solutions for use in hand dishwashing. In general, an effective amount of those compositions is added to the water to form said aqueous solutions for cleaning or soaking. The aqueous solution thus formed then makes contact with the dishes, the dishes and the kitchen utensils. An effective amount of the detergent compositions herein added to water to form aqueous cleaning solutions may comprise sufficient amounts to form about 500 to 20,000 ppm of composition in aqueous solution. More preferably, from about 800 to 5,000 ppm of the detergent compositions herein will be in aqueous cleaning solution. The following examples are illustrative of this invention, but are not intended to limit or otherwise define its scope. All parts, percentages and ratios used herein are expressed as a percentage by weight, unless otherwise specified. In the following examples all levels are indicated in% by weight of the composition.

EXAMPLES OF DETERGENT COMPOSITIONS In these examples the following abbreviations are used for a modified alkylbenzene sulfonate, sodium salt form or potassium salt form, prepared according to any of the examples of the above process: MLAS The following abbreviations are used for auxiliary materials of cleaning products : Amine Oxide Cxy: N-Oxide of alkyldimethylamine RN (0) Me2 of chain length determined Cxy where the average total carbon scale of the non-methyl alkyl part R is 10 + x to 10 + y Cxy APG: Alkyl polyglycosides of the formula R20 (CnH2nO) t (glycosyl) x of Cxy of determined length, where R2 is an alkyl of C o-? 8; n is 2 or 3, t is from 0 to about 10, preferably 0; and x is from about 1.3 to about 2.7. The glycosyl is preferably derived from glucose. Amylase: The amylolytic enzyme with activity of 60 KNU / g, sold by Novo Industries A / S under the trademark Termamyl 60T. Alternatively, the amylase is selected from: Fungamyl®, Duramyl®; BAN®; and enzymes to amylase, described in WO 95/26397 and in the co-pending application by Novo Nordisk PCT / DK96 / 00056. APA: C8-C10 amidopropyldimethylamine.

Cxy betaine: Alkyldimethyl betaine having an average total carbon scale of alkyl part of 10 + x to 10 + and calcium salt: calcium chloride, calcium sulfate, calcium hydroxide and mixtures thereof. Carbonate: Na2C03 anhydrous, 200μm - 900μm Citrate: Trisodium citrate dihydrate, 86.4%, 425μm - 850μm Citric acid: Citric acid, Anhydrous CMC: Sodium carboxymethylcellulose CxyAS: Alkylsulfate, Na salt or other salt, if specified which has an average total carbon scale of alkyl part of 10 + x to 10 + and CxyEz: commercial linear or branched alcohol ethoxylate (which has no methyl branching in the middle of the chain) and which has a part average total carbon scale of alkyl of 10 + x to 10 + and moles z average of ethylene oxide. CxyExS: Ethoxylated alkylsulfate, salt of Na (or other salt, if specified) that has an average total carbon scale of alkyl part of 10 + x to 10 + y and an average of z moles of ethylene oxide DEA: Dietanolamine Diamine: Alkyldiamine , for example 1.3 propane diamine, Dytek EP, Dytek A, (Dupont) or selected from: dimethyl aminopropylamine; 1,6-hexanediamine; 1, 3 propane diamine; 2-methyl-1,5-pentane diamine; 1,3-pentanediamine; 1-methyl-diaminopropane; 1, 3 cyclohexane diamine; 1,2 cydohexane diamine; 1, 3-bis (methylamine) -cyclohexane DTPA: Diethylenetriamine pentaacetic acid DTPMP: Penta diethylenetriamine (methylene phosphonate), Monsanto (Dequest 2060) EtOH: Ethanol Hydrotrope: Selected from sodium, potassium, magnesium, calcium salts, ammonium or water-soluble substituted ammonium of toluenesulfonic acid, naphthalenesulfonic acid, cumenesulfonic acid, xylene sulfonic acid. LAS: Linear alkylbenzenesulfonate (for example C11.8, Na or K salt) Lipase: Lipolytic enzyme, 100kLU / g, NOVO, Lipolasa®. Alternatively, the lipase is selected from: Amano-P; M1 Lipase®; Lipomax®; D96L lipolytic enzyme variant of virgin lipase derived from Humicola lanuginosa, as described in E.U.A. series No. 08/341, 826; and the strain of Humicola lanuginosa DS, 4106. LMFAA: N-methylglucamide of C12-14 alkyl MA / AA: Copolymer 1: 4 maleic / acrylic acid, Na salt, average molecular weight 70,000 MBAxEy: Primary alkyl ethoxylate branched in part average of the chain (average total carbons = x; average EO = y) MBAxEys: Alkylsulfate primary ethoxylate modified or branched in the middle of the chain, salt of Na (average total carbons = x; average EO = y) in accordance with the invention (see example 9). MBAyS: Primary alkyl branched in the middle part of the chain, salt of Na (average total carbons = y) MEA: Monoethanolamine CxyMES: Methyl ester alkylsulphonate, Na salt that has an average total carbon scale of alkyl part of 10+ xa 10 + y Magnesium salt: Magnesium chloride, magnesium sulfate, magnesium hydroxide and mixtures thereof NaOH: Sodium hydroxide Cxy NaPS: Paraffin sulfonate, sodium salt having an average total carbon scale of alkyl part of 10 + x to 10 + and NaTS: Toluen sulfonate Sodium PAA: Polyacrylic acid (molecular weight = 4500) PAE: Ethoxylated tetraethylenepentamine PEG: Polyethylene glycol (molecular weight = 4600) PG = Propanediol Protease: Proteolytic enzyme, 4KNPU / g, NOVO, Savinasa®. Alternatively, the protease is selected from: Maxatasa®, Maxacal®; Maxapem 15®; subtilisin BPN and BPN '; Protease B; Protease A; Protease D; Primase®; Durazym®; Opticlean®; and Optimase®; and Alcalase®. Cxy SAS: secondary alkylsulfate, Na salt having an average total carbon scale of alkyl part of 10 + x to 10 + and Silicate: sodium silicate, amorphous (SiO2: Na20, ratio 2.0) Solvent: Hexylene glycol, ethanol or propylene glycol STPP : Sodium tripolyphosphate, anhydrous Foaming intensification polymer: (N, Nd-Emethylamino) alkyl acrylate homopolymer; (N, N-diemthylamino) ethyl methacrylate; copolymers of dimethylaminoethyl methacrylate / dimethylacrylamide; Poly homopolymer (DMAM); Poly copolymer (DMAM-co-AA) (2: 1); polypeptide comprising Lys, Ala, Glu, Tyr (5: 6: 2: 1) having a molecular weight of about 52,000 daltons Sulfate: Sodium sulfate, anhydrous TFA: C16-C18 alkyl N-methyl glucamide Typical ingredients which are often referred to as "minors" may include perfumes, dyes, pH indicator fragments, etc. The following example is illustrative of the present invention, but is not intended to limit or otherwise define its scope. All the parts, percentages and relationships used are expressed as percentage by weight unless otherwise noted.EXAMPLE 18 EXAMPLE 19 EXAMPLE 20 EXAMPLE 21 EXAMPLE 22 EXAMPLE 23 EXAMPLE 24 EXAMPLE 25 A B C D E AE0.6S 6 10 13 15 20 Amine oxide 6.5 6.5 7.5 7.5 7.5 C10E8 3 3 4.5 4.5 4.5 MLAS (according to example 20 16 13 11 6 4) Diamine 0.5 0.5 1.25 1 0 Magnesium salt 0.2 0.4 1.0 0 0.2 Intensification polymer 0 0.2 0.5 0.2 0.5 foam Hydrotrope 1.5 1.5 1 1 1 Ethanol 8 8 8 8 8 Sodium chloride 0.5 0.5 0 0.2 PH 9 9 9 8 10 F G H I AE0.6S 6 10 13 20 Amine oxide 6.50 6.50 6.50 7.20 MLAS (according to example 20 16 13 11 5) Intensification polymer 0.20 0.20 0.20 0.22 foam Hydro-troph 1.50 1.50 3.50 2.0 Polypropylene glycol (PM 2700) 1 1 1 1 C10E8 3.00 3.00 3.00 3.30 Diamine 0.50 0 0. 0.55 Magnesium salt 0.22 0 0.5 0 Sodium chloride 0.5 - 0.5 - Water and several BAL. BAL. BAL. BAL. Viscosity (cps at 70F) 150 330 650 330 pH at 10% 8.3 9.0 9.0 9.0 JK AE0.6S 14.8 20 MLAS (according to example 15) 14 8 Amine oxide 7.20 7.20 Citric acid 3.00 - Maleic acid - 2.50 Magnesium salt 0.22 0J Sodium chloride 0.5 - Intensification polymer 0.22 0.22 foam Cumene sodium sulfonate 3.30 3.30 Ethanol 6.50 6.50 C10E8 - - C11E9 3.33 3.33 Diamine 0.55 0.55 Perfume 0.31 0.31 Water BAL. BAL. Viscosity (cps at 70F) 330 330 pH at 10% 9.0 9.0 EXAMPLE 26 A B C D E MLAS 14.2 14.3 6.5 13.1 10 AE1S - - 21.3 14 AE0.8S 16.8 20.5 AS 9.6 - AE3S 11.4 APG - - 10 7 Amida MEA 4.0 3.8 3.8 MEA / DEA 2.9 2 Betaine - 1.5 C10E8 4.0 4.0 Salt of Mg 0.3 0.29 0.35 0.2 0.3 Water and ingredients cbp cbp cbp cbp cbp minors 100% 100% 100% 100% 100% F G H I J MLAS 27 8 15 13 13 AE1S 9 5 5 22 AE0.8S 11 AS AE3S APG 2 4 2 1 1 Amida MEA 1 MEA / DEA 2 1 1 2 Betaine 0.3 C10E8 Mg salt Water and ingredients cbp cbp cbp cbp cbp minors 100% 100% 100% 100% 100% K L M N O MLAS 7 20 19 22 18.4 AE1S 9 13 11 AE0.8S 21 AS AE3S 18.4 APG 6 Amida MEA 1 4.3 MEA / DEA 2 2 Betaine 2 C10E8 1 2 Mg salt Water and ingredients cbp Cbp cbp cbp cbp minor 100% 100% 100% 100% 100% EXAMPLES OF ADDITIONAL SYNTHESIS EXAMPLE 27 Mixture of linear and branched alkylbenzene with a 2/3-phenyl index of approximately 200 and a 2-methyl-2-phenyl index of approximately 0.02 (Alkylbenzene mixture according to the invention) 110. 25 g of the substantially mono methyl branched olefin mixture of example 2, 36.75 g of an unbranched olefin mixture (decene: undecene: dodecene: tridecene ratio of 2: 9: 20: 18) and 36 g of a Form selective zeolite (Zeocat ™ PB / H acid beta zeolite catalyst) is added to a stirred stainless steel autoclave of 7.56 liters. The olefin residue and catalyst in the vessel are washed in the autoclave with 300 ml of n-hexane and the autoclave is sealed. From the outside of the autoclave cell are added 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 latter is purged twice with 17.57 kg / cm2 of N2, and then charged to 4.21 kg / cm2 of N2. The mixture is stirred and heated to about 200 ° C for about 4-5 hours. The autoclave is cooled to around 20 ° C during the night. The valve is opened by going from the autoclave to the benzene condenser and to the collection tank. The autoclave is heated to around 120 ° C with continuous collection of benzene. By the time the reactor reaches 120 ° C, no more benzene is collected. Then, the reactor is cooled to 40 ° C and 750 g of n-hexane are pumped into the autoclave, which is 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 modified 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 28 Mix of alkylbenzenesulfonic acid modified 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-phenol number of about 0.02.

The modified alkyl benzene mixture of Example 27 is sulfone 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. 2 EXAMPLE 29 Mixture of sodium salt, modified alkylbenzenesulfonate according to the invention (mixture of sodium salt, branched and unbranched alkylbenzenesulfonate) with a 2/3-phenyl number of about 200 and a 2-methyl-2-phenyl index of about 0.02.

The modified alkylbenzenesulfonic acid of Example 28 is neutralized with one molar equivalent of sodium methoxide in methanol and the methanol is evaporated to give 225 g of a mixture of sodium salt, modified alkylbenzenesulfonate with a 2/3-phenyl index of about 200 and a 2-methyl-2-phenyl index of about 0.02.

EXAMPLE 30 The detergent compositions as in Examples 18-26 are repeated substituting MLAS with the product of Example 29.

Claims (1)

1. NOVELTY OF THE INVENTION CLAIMS L- A hand dishwashing detergent composition characterized in that it comprises: (i) from 0.01% to 95% by weight of composition of a modified alkylbenzene sulfonate surfactant mixture comprising: a) from 15% to 99% by weight of mixture of surfactants, a mixture of branched alkylbenzene sulphonates having the formula (I). (I) wherein L is an aliphatic acyclic part consisting of carbon and hydrogen, said L has two methyl endings and the L has no substituent other than A, R1 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 the formula (I), and wherein the branched alkylbenzene sulphonate mixture 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 mixture of cations that has a valence q; a and b are selected integers such that the branched alkylbenzene sulphonates are electroneutral; R1 is C1-3 alkyl, R2 is selected from H and C1-3 alkyl; A is a part of benzene; and b) from 1% to 85% by weight of surfactant mixture, of a mixture of unbranched alkylbenzene sulphonates having the formula (II): ("0. where a, b, M, A and q are as previously defined in the present y, Y is an unsubstituted linear aliphatic part consisting of carbon and hydrogen having two methyl ends, and wherein said Y it has a sum of carbon atoms of 9 to 15, preferably 10 to 14, and said Y has an average aliphatic carbon content of 10.0 to 14.0, and wherein said mixture of modified alkylbenzenesulfonate surfactants is also characterized by a 2/3-phenyl index from 160 to 275; (ii) from 0.00001% to 99.9% by weight composition of a conventional hand dishwashing aid, wherein said composition is also characterized by a 2/3-phenyl 160 to 275. 2.- The detergent composition for washing dishes by hand according to claim 1, further characterized in that said M is selected from H, Na, K and mixtures thereof, a = 1, b = 1, q = 1 and the mixture of modified alkylbenzenesulfonate surfactants t It has a 2-methyl-2-phenol index less than 0.3. 3. The detergent composition for hand washing according to claim 2, further characterized in that said modified alkylbenzene sulfonate mixture is the product of a process using beta zeolite as a catalyst. 4. The mixture of modified alkylbenzenesulfonate surfactants according to claim 3, further characterized in that said catalyst is in at least partially acidic form. 5. The hand dishwashing detergent composition according to claim 2, further characterized in that it consists essentially of said mixture of branched alkylbenzene sulphonates and unbranched alkylbenzene sulphonates, wherein the 2-methyl-2-phenyl index of said mixture of modified alkylbenzenesulfonate is less than 0J, and in said mixture of branched and unbranched alkylbenzenesulfonates, the average aliphatic carbon content is from 11.5 to 12.5 carbon atoms; R1 is methyl; R 2 is selected from H and methyl, so long as at least 0.7 mole fraction of branched alkyl alkylbenzenesulfonates is H; and wherein the sum of carbon atoms in R1, L and R2 is from 10 to 14; and also wherein in the 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 11.5 to 12. 5 carbon atoms, and M is a monovalent cation or mixture of cations selected from H, Na and mixtures thereof. 6. A detergent composition for washing dishes by hand characterized in that it comprises: (i) a mixture of modified alkyl benzene sulfonate surfactants comprising the product of a process comprising the steps of: (I) alkylating benzene with an alkylation mixture in 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 99.9% by weight of the alkylation mixture of branched C9-C2o monoolefins, said branched monoolefins having structures identical to those of the branched monoolefins which are formed by the dehydrogenation of branched paraffins of the formula R1LR2, wherein L is an aliphatic acyclic part consisting of carbon and hydrogen and contains two terminal methyls; R1 is C 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 alkylation mixture of C9-C20 linear aliphatic olefins; wherein the alkylation mixture contains said branched C9-C20 monoolefins having at least two different carbon numbers on the C9-C2o scale, and has an average carbon content of 9.0 to 15.0 carbon atoms; and wherein components a) and b) are in a weight ratio of at least 15:85; (ii) from 0.00001% to 99.9% by weight composition of a conventional hand dishwashing aid; wherein the composition is further characterized by a 2/3-phenyl index of 160 to 275. 7. - A hand dishwashing detergent composition characterized in that it comprises: (i) a modified alkylbenzene sulfonate surfactant mixture consisting essentially of the product of a process comprising the steps, in sequence, of: (I) alkylating benzene with a alkylation mixture in the presence of a beta zeolite 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-C2 or R1LR2, wherein L is an olefinic acyclic part consisting of carbon and hydrogen and containing two terminal methyls; B) alpha monoolefins of C9-C20 R1AR2, wherein A is an alpha-olefinic acyclic part consisting of carbon and hydrogen and containing a terminal methyl and a terminal olefinic methylene; C) vinylidene monoolefins of C9-C20 R1BR2, wherein B is an acyclic vinylidene-olefin part consisting of carbon and hydrogen and containing two terminal methyls and an internal olefinic methylene; D) C9-C20 primary alcohols R1QR2, wherein Q is an aliphatic acyclic part of the primary terminal alcohol consisting of carbon, hydrogen and oxygen and containing a terminal methyl; E) primary alcohols of C8-C2 or R1ZR2, wherein Z is an aliphatic acyclic part of primary non-terminal alcohol consisting of carbon, hydrogen and oxygen and containing two terminal methyls; and F) mixtures thereof; wherein in any of A) - F), R1 is C1 to C3 alkyl and R2 is selected from H and C1 to C3 alkyl; and b) from 0.1% to 85% by weight of C9-C20 linear alkylating agent alkylation mixture selected from linear aliphatic olefins of C9-C20, linear aliphatic alcohols of Cg-C20 and mixtures thereof; wherein the alkylation mixture contains the branched alkylating agents having at least two different carbon numbers on said C9-C20 scale, and has an average carbon content of 9.0 to 15.0 carbon atoms; and wherein components a) and b) are in a weight ratio of at least about 15:85; (ii) from 0.00001% to 99.9% by weight composition of a conventional hand dishwashing aid; wherein the composition is further characterized by a 2/3-phenyl index of 160 to 275. 8. The detergent composition for washing dishes by hand according to claim 7, further characterized in that the alkylation mixture consists essentially of: a ) from 0.5% to 47.5% by weight of alkylation mixture of said branched alkylating agent selected from: G) internal monoolefins of Cg-Cu R1LR2, wherein L is an olefinic acyclic part consisting of carbon and hydrogen and containing two terminal methyls; H) alpha monoolefins of C9-Cu R1AR2, wherein A is an alpha-olefinic acyclic part consisting of carbon and hydrogen and containing a terminal methyl and a terminal olefinic methylene; and J) mixtures thereof; wherein in any of G), H) and J), R1 is methyl and R2 is H or methyl, as long as at least 0.7 mole fraction of the total of said monoolefins, R2 is H; and b) from 0.1% to 25% by weight of linear aliphatic olefins of Cg-Cu; and c) from 50% to 98.9% by weight of alkylation mixture of carrier materials selected from paraffins and inert non-paraffin solvents; wherein said alkylation mixture contains those branched alkylating agents having at least two different carbon numbers on said Cg-Cu scale and having an average carbon content of 11.5 to 12.5 carbon atoms; and wherein said components a) and b) are in a weight ratio of 51:49 to 90:10. 9. The composition for washing dishes by hand according to any of claims 6-8, further characterized in that in step (II) comprises the removal of components other than monoalkylbenzene before contact of the product of step (I) with the sulfonation agent. 10. The composition for washing dishes by hand according to any of claims 6-8, further characterized in that a hydrotrope, hydrotrope precursor or mixtures thereof is added after step (I). 11. The composition for washing dishes by hand according to any of claims 6-8, further characterized in that a hydrotrope, hydrotrope precursor or mixtures thereof is added during or after step (II) and before passage ( III). 12. The composition for washing dishes by hand according to any of claims 6-8, further characterized in that a hydrotrope is added during or after step (III). 13. - The hand dishwashing composition according to any of claims 6-8, further characterized in that said acid beta zeolite catalyst is a calcined beta zeolite catalyst treated with HF. 14. The composition for washing dishes by hand according to any of claims 6-8, further characterized in that in step (I) said alkylation is carried out at a temperature of 125 ° C to 230 ° C and at a pressure of 3.51 kg / cm2 at 70.3 kg / cm2. 15. The composition for washing dishes by hand according to any of claims 6-8, further characterized in that in step (I) said alkylation is carried out at a temperature of 175 ° C to 215 ° C and at a pressure of 7.03. kg / cm2 to 17.57 kg / cm2, and a time of 0.01 hours to 18 hours. 16. The hand dishwashing composition according to any of claims 6-8, further characterized in that step (II) is carried out using a sulfonation agent selected from the group consisting of sulfur trioxide, sulfur trioxide / mixtures of air and sulfuric acid. 17. A composition for washing dishes by hand comprising: (i) from 0.01% to 95% by weight of composition of a mixture of modified alkylbenzenesulfonate surfactants comprising: a) from 15% to 99% by weight of the mixture of surfactants, a mixture of branched alkylbenzene sulphonates having the formula (I). (I) wherein L is an aliphatic acyclic part consisting of carbon and hydrogen, said L has two methyl endings and the L has no substituent other than A, R1 and R2; and wherein said mixture of branched alkylbenzene sulphonates contains two or more of said branched aiquilbenzene sulphonates which differ in molecular weight from the anion of the formula (I), and wherein the branched alkylbenzene sulphonate mixture 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 mixture of cations that has a valence q; a and b are selected integers such that the branched alkylbenzene sulphonates are electroneutral; R1 is C1.3 alkyl, R2 is selected from H and C1.3 alkyl; A is a part of benzene; and b) from 1% to 85% by weight of surfactant mixture, of a mixture of unbranched alkylbenzene sulphonates having the formula (II): (ll) where a, b, M, A and q are as defined e in the present and Y is an unsubstituted linear aliphatic part consisting of carbon and hydrogen having two methyl ends, and wherein said Y has a sum of carbon atoms of 9 to 15, preferably 10 to 14, and said Y has an average aliphatic carbon content of 10.0 to 14.0; and wherein said mixture of modified alkylbenzenesulfonate surfactants is also characterized by a 2/3-phenyl index of 160 to 275; and wherein said mixture of modified alkyl benzene sulfonate surfactants has a 2-methyl-2-phenyl index of less than 0.3; (I) from 0.00001% to 99.9% by weight composition of a conventional hand dishwashing aid; and (iii) from 0.00001% to 99.9% 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; as long as the composition comprises any alkylbenzene sulfonate surfactant other than said modified alkyl benzene sulphonate surfactant mixture, the composition is also characterized by a general 2/3-phenyl index of at least 160, wherein said 2 / 3- index General phenyl is determined by measuring the 2/3-phenyl index, as defined herein, in a combination of the mixture of modified alkylbenzenesulfonate surfactants and any other alkylbenzenesulfonate which is added to the detergent composition, said combination, for the purposes of measurement, is prepared from aliquots of the modified alkylbenzene sulfonate surfactant mixture and the other alkylbenzenesulfonate not yet exposed to any other component of the composition; and further provided that the composition comprises any alkylbenzene sulfonate surfactant other than the modified alkyl benzene sulphonate surfactant mixture, said composition is also characterized by a general 2-methyl-2-phenyl index of less than 0.3, wherein the General methyl-2-phenyl is determined with the measurement of the 2-methyl-2-phenyl index, as defined herein, in a combination of said modified alkyl benzene sulfonate surfactant mixture and any other alkylbenzenesulfonate is added to the composition, said combination, for measurement purposes, is prepared from aliquots of the modified alkyl benzene sulfonate surfactant mixture and the other alkylbenzene sulfonate not yet exposed to any other component of the detergent composition. 18. The hand dishwashing composition according to claim 17, further characterized in that it has substantially no alkylbenzenesulfonate surfactants other than said mixture of modified alkyl benzene sulphonate surfactants. 19.- The composition for washing dishes by hand according to claim 17, further characterized in that it comprises, in said component (iii), at least 0.1% of a linear C 1 -C 8 alkylbenzenesulfonate surfactant having an index of 2 / 3-phenyl from 75 to 160. 20.- The composition for washing dishes by hand according to claim 17, further characterized in that it comprises, in said component (ii), at least 0.1% of an alkylbenzene sulfonate surfactant. highly branched commercial. 21. The composition for washing dishes by hand according to claim 17, further characterized in that it comprises, in said component (iii), a nonionic surfactant at a level of 0.5% to 25% by weight of the detergent composition , and wherein said nonionic surfactant is a polyalkoxylated alcohol in a crowned or uncrowned form having: a hydrophobic group selected from C10-C16 linear alkyl, C? 0-C16 alkyl branched in the middle part of the C1 chain -C3, branched C10-C16 alkyl, Guerbet and mixtures thereof, and a hydrophilic group selected from 1-15 ethoxylates, 1-15 propoxylates, 1-15 butoxylates and mixtures thereof, in crowned or uncoated form. 22. The composition for washing dishes by hand according to claim 17, further characterized in that it comprises, in said component (iii), an alkyl sulfate surfactant at a level of 0.5% to 25% by weight of said detergent composition, wherein the alkyl sulfate surfactant has a hydrophobic group selected from linear C10-C18 alkyl, C10-C18 alkyl branched in the middle part of the C1-C3 chain, branched C? 0-C? 8 alkyl Guerbet and mixtures of them, and a cation selected from Na, K and mixtures thereof. 23. The hand washing dish detergent composition according to claim 17, further characterized in that it comprises, in said component (iii), an alkyl (polyalkoxy) sulfate surfactant at a level of 0.5% to 25% by weight of the detergent composition, wherein said alkyl (polyalkoxy) sulfate surfactant has a hydrophobic group selected from C10-C16 linear alkyl, C10-C6 alkyl branched in the middle part of the C1-C3 chain, C10 alkyl -C16 branched Guerbet and mixtures thereof; and a hydrophilic group of (polyalkoxy) sulfate selected from 1-15 polyethoxysulfate, 1-15 polypropoxysulfate, 1-15 polybutoxysulfate, 1-15 mixed poly (ethoxy / propoxy / butoxy) sulfates and mixtures thereof, in crowned or non-crowned form crowned and a cation selected from Na, K and mixtures thereof. 24. The detergent composition for washing dishes by hand according to any of claims 1 to 23, further characterized in that it comprises, said conventional hand dishwashing aid is selected from the group consisting of surfactants other than (i), detergency builders, detersive enzymes, water dispersible or at least partially water soluble polymers, abrasives, bactericides, stain inhibitors, dyes, solvents, hydrotropes, perfumes, thickeners, anitoxidants, processing aids, foam enhancers, foam suppressors, foam stabilizers, diamines, vehicles, enzyme stabilizers, antioxidants, polysaccharides, pH regulators, antifungal agents, mold control agents, insect repellents, anticorrosive aids, chelators and mixtures thereof. 25. The composition for washing dishes by hand according to any of claims 1 to 24, further characterized in that said composition is in the form of a liquid, powder, paste, gel, liquid gel, microemulsion or granule. 26. The detergent composition for washing dishes by hand according to any of claims 1 to 25, further characterized in that it comprises a surfactant, wherein the surfactant is selected from the group consisting of anionic, nonionic, amphoteric, zwitterionic and mixtures thereof. 27. The detergent composition for washing dishes by hand according to any of claims 1 to 26, further characterized in that it comprises an organic diamine, wherein said diamine is selected from the group consisting of: wherein R2-5 are independently selected from H, methyl, ethyl and ethylene oxides; Cx and Cv are independently selected from methylene groups or branched alkyl groups, wherein x + v is from 3 to 6; A is optionally present and is selected from parts that donate or withdraw electrons that are chosen to adjust the pKa diamine to the desired scale; where if A is present, then x and y must be 2 or greater. 28. The composition for washing dishes by hand according to any of claims 1 to 27, further characterized in that it comprises an organic diamine, wherein said diamine has the formula: wherein each R6 is independently selected from the group consisting of hydrogen, linear or branched C1-C4 alkyl, alkyleneoxy having the formula: - (R7O) mR8 wherein R7 is linear or branched C2-C4 alkylene, and mixtures thereof; R8 is hydrogen, C1-C4 alkyl, and mixtures thereof; m is from 1 to 10; X is a unit selected from: (i) C3-C10 linear alkylene, C3-C10 branched alkylene, C3-C10 cyclic alkylene, branched C3-C10 cyclic alkylene, an alkyleneneoxyalkylene having the formula: - (R70) mR7- wherein R7 and m are the same, as defined hereinbefore; (ii) C3-C10 linear alkylene, branched linear C3-C10, C3-C10 cyclic, C6-C6 arylene, wherein said unit comprises one or more electron donating or electron withdrawing parts, which provide said diamine with a pKa greater than 8; and (iii) mixtures of (i) and (ii), as long as the diamine has a pKa of at least 8. The detergent composition for washing dishes by hand according to any of claims 27-28, further characterized in that the diamine is selected from the group consisting of dimethyl aminopropyl amine, 1,6-hexanediamine, 1,3 propanediamine, 2-methyl 1,5-pentanediamine, 1,3-pentanediamine, 1,3-diaminobutane, 1,2-bis (2-aminoethoxy) ethane, isophorone diamine, 1,3-bis (methylamine) -cyclohexane and mixtures thereof. 30. The detergent composition for washing dishes by hand according to any of claims 1-29, further characterized in that it comprises an anionic surfactant, wherein said anionic surfactant is selected from the group consisting of alkyl sulfates, alkylalkoxy sulfates, linear alkylfenzene sulphonate , alpha olefin sulphonate, paraffin sulfonates, methyl ester sulfonates, alkylsulfonates, alkoxylated alkylsulfates, sarcosinates, taurinates, alkyl alkoxycarboxylate and mixtures thereof. 31. The detergent composition for washing dishes by hand according to any of claims 1-30, further characterized in that it comprises a nonionic surfactant, wherein said nonionic surfactant is selected from the group consisting of alkyl ethoxylates, polyhydroxyamides of fatty acid, alkyl polyglucosides, alkyl ethoxylates and mixtures thereof. 32. - The hand dishwashing detergent composition according to any of claims 1-31, further characterized in that it comprises an amphoteric surfactant, wherein said amphoteric surfactant is selected from the group consisting of betaines, sulfobetaines, amine oxide and mixtures thereof. 33. The detergent composition for washing dishes by hand according to any of claims 1-32, further characterized in that it comprises a polymeric foam stabilizer that is selected from the group consisting of: (i) homopolymers of esters of (N, N-dialkylamino) alkyl acrylate having the formula: wherein each R is independently hydrogen, alkyl of C -Cs and mixtures thereof, R1 is hydrogen, C-Cß alkyl and mixtures thereof, n is from 2 to 6; and (ii) copolymers of (i) and wherein R1 is hydrogen, C1-C6 alkyl and mixtures thereof; as long as the ratio of (ii) to (i) is from 2 to 1 to 1 to 2; and wherein said polymeric foam stabilizer has a molecular weight of 1, 000 to 2,000,000 daltons. 34. The detergent composition for washing dishes by hand according to any of claims 1-33, further characterized in that it comprises an enzyme, wherein said enzyme is selected from the group consisting of amylase, protease, cellulase, lipase and mixtures thereof. the same. 35.- The composition for washing dishes by hand according to any of claims 1 to 34, further characterized in that it comprises from 0.01% to 7% by weight of composition of a divalent ion selected from the group consisting of magnesium, calcium and mixtures thereof; and 36.- A method for washing dishes, said method comprises contact with dirty dishes that need cleaning with an aqueous solution of the composition as claimed in any of claims 1 -35. 37. The method according to claim 36, further characterized in that it comprises the step of diluting said composition with water. 38.- The method according to claim 36, further characterized in that it comprises the step of applying said composition directly to a sponge or cloth for washing. 39.- The composition for washing dishes by hand according to claim 1, further characterized in that said mixture of modified alkylbenzenesulfonate surfactants is prepared by a process comprising a step selected from: combining a mixture of branched alkylbenzene sulfonate surfactants and linear having a 2/3-phenyl index of from 500 to 700 with a mixture of alkylbenzenesulfonate surfactants having a 2/3-phenyl index of from 75 to 160; and combining a mixture of branched and linear alkylbenzenes having a 2/3-phenyl index of from 500 to 700 with a mixture of alkylbenzene having a 2/3-phenyl index of from 75 to 160 and sulfonating said combination.