MXPA00003518A - Detergent composition with a selected surfactant system containing a mid-chain branched surfactant - Google Patents

Abstract

A detergent composition, having a selected surfactant system for improved performance, especially under high water hardness and low temperature wash water conditions is disclosed. The detergent composition includes a mid-chain branched primary alkyl sulfate surfactant in combination with a linear alkylbenzene sulfonate surfactant, and linear alkyl sulfate surfactant at optimally selected relative proportions. Additionally, the detergent composition contains up to about 5%of an alkyl ethoxylated sulfate surfactant and up to about 5%of a nonionic surfactant while unexpectedly having improved performance with such relatively low levels of a nonionic surfactant.

Description

COMPOSITION DETERGENT WITH AN AGENT SYSTEM ELECTED SURFACTANT THAT CONTAINS A SURGICAL AGENT BRANCHED IN THE MIDDLE REGION OF THE CHAIN FIELD OF THE INVENTION The present invention generally relates to a detergent composition having a surfactant system for improved performance. In particular, the detergent composition includes a primary alkylsulphate surfactant branched in the middle region of the chain in combination with an alkylbenzene sulfonate surfactant, and a linear alkyl sulfate surfactant, resulting in a surfactant system which causes the The composition has an improved cleaning performance, especially under low temperature washing conditions.

BACKGROUND OF THE INVENTION Conventional detersive surfactants comprise molecules having a water-soluble substituent (hydrophilic group) and an oleophilic substituent (hydrophobic group). Such surfactants typically comprise hydrophilic groups such as carboxylate, sulfate, sulfonate, amine oxide, polyoxyethylene, and the like, attached to an alkyl, alkenyl or hydrophobic aryl which usually contains from about 10 to about 20 carbon atoms. In this way, manufacturers of such surfactants must have access to a source of hydrophobic groups to which the desired hydrophilic may be linked by chemical means. The first source of hydrophobic groups comprised natural fats and oils, which were converted into soaps (ie, carboxylate hydrophilic) by saponification with base. Coconut oil and palm oil are still used to make soap, as well as to make the class of alkyl sulfate surfactants ("AS"). Other hydrophobes are available from petrochemicals, including alkylated benzene which is used to make alkylbenzene sulfonate ("LAS") surfactants. In general, alkyl sulfates are well known to those skilled in the art of detersive surfactants. The alkyl sulphates were developed as a functional improvement over the traditional soap surfactants and have been found to possess improved solubility and surfactant characteristics. Of the alkyl sulfate surfactants, the linear alkyl sulphates are the most commonly used and are the most easily obtained. For example, linear long chain alkyl sulphates, such as tallow alkyl sulphate, have been used in laundry detergents. However, these have important cleaning performance limitations, especially with the tendency to lower wash temperatures.

Thus, there is a need for a detergent composition that includes a surfactant capable of providing improved cleaning at lower wash temperatures (e.g. between 20 and 5 ° C). In addition, even detergent compositions containing surfactants with the desired performance may still exhibit improved performance. In particular, certain detergent compositions containing selected surfactants, such as the medium chain branched surfactants, typically include other ingredients such as builders, enzymes and the like which can have deleterious effects on the overall cleaning performance of the composition. At this point, there is still a need for a detergent composition exhibiting improved performance, especially under washing water conditions at low temperatures and relatively high water hardness.

TECHNICAL BACKGROUND The patents of E.U.A. 3,480,556 to deWitt, et al., Issued November 25, 1969; EP 439,316, published by Lever on July 31, 1991 and EP 684,300 published by Lever on November 29, 1995, describe the beta-branched alkyl sulfates. EP 439,316, discloses certain laundry detergents containing a branched primary commercial C14 / C15 alkyl sulfate, called LIAL 145 sulfate. The latter is believed to present 61% branching at position 2; 30% of the above involves branching with a hydrocarbon chain having four or more carbon atoms. The patent of E.U.A. No. 3,480,556 discloses mixtures of 10 to 90 parts of a straight chain primary alkylsulfate and 90 to 10 parts of a beta-branched primary alcohol sulfate (branched at position 2) of the formula R2 R CHCH2OS03X wherein the total number of carbon atoms ranges from 12 to 20 and R1 is a straight chain alkyl radical containing from 9 to 17 carbon atoms and R2 is a straight chain alkyl radical containing from 1 to 9 carbon atoms (exemplified 67% of 2-methyl and 33% of branched 2-ethyl). As noted hereinabove, R.G. Laughiin in "The Aqueous Phase Behavior of Surfactants", Academic Press, N.Y. (1994) p. 347 describes the observation that when the branching away from the 2-alkyl position towards the center of the hydrophobic alkyl there is a decrease in Krafft temperatures. See also Finger et al., "Detergent alcohols - the effect of alcohol structure and molecular weight on surfactant properties", J. Amer. Oil Chemists' Society, Vol. 44, p. 525 (1967) and Technical Bulletin, Shell Chemical Co., SC: 364-80. EP 342,917 A, Unilever, published on November 23, 1989 discloses laundry detergents containing a surfactant system, wherein the main anionic surfactant is an alkyl sulfate having a "broad scale" of alkyl chain lengths (The experiment seems to involve the mixture of coconut and tallow chain length surfactants). The patent of E.U.A. 4,102,823 and GB 1, 399,966 describe other laundry compositions containing conventional alkyl sulphates. The patent GB 1 299 966, Matheson et al., Published July 2, 1975, describes a detergent composition wherein the surfactant system comprises a mixture of sodium tallow alkyl sulphate and nonionic surfactants. The methyl substituted sulfates include the known "isostearyl sulfates; these are typical mixtures of isomeric sulfates having a total of 18 carbon atoms. For example, EP 401, 462 A, assigned to Henkel, published on December 12, 1990, discloses certain isostearyl alcohols and ethoxylated isostearyl alcohols and their sulfation to produce the corresponding alkyl sulfates such as sodium isostearyl sulfate. See also K.R. Wormuth and S. Zushma, Langmuir, Vol. 7, (1991), pp 2048-2053 (technical studies on a number of branched alkylsulphates, especially the "branched Guerbet" type; R. Varadaraj et al., J. Phys. Chem., Vol. 95, (1991), pp 1671-1676 (describing the surface tensions of a variety of "Guerbet's linear" and "Guerbet's branched"), the class of surfactants including alkyl sulfates); Varadaraj et al., J. Colloid and Interface Sci., Vol. 140, (1990), pp. 31-34 (in relation to foaming data for surfactants including C12 and C13 alkyl sulphates containing 3 and 4 branches of methyl, respectively); and Varadaraj et al., Langmuir, Vol. 6 (1990), pp 1376-1378 (which describes the micropolarity of aqueous micellar solutions of surfactants including branched alkyl sulphates). "Linear Guerbet" alcohols are available from Henkel, for example EUTANOL G-16. The primary alkyl sulphates derived from alcohols made by oxo reaction on oligomers of propylene or n-butylene are described in the patent of E.U.A. No. 5,245,072 assigned to Mobil Corp. See also the patent of E.U.A. 5,284,989, assigned to Mobil Oil Corp. (a method to produce substantially linear hydrocarbons by oligomerization of a low oleofin at elevated temperatures with intermediate pore and constricted pore siliceous zeolite acid), and U.S. Patents. 5,026,933 and 4,870,038, both from Mobil Oil Corp. (a process for producing substantially linear hydrocarbons by the oligomerization of a low oleofin at elevated temperatures with ZSM-23 siliceous acid zeolite). See also: Surfactant Science Series, Marcel Dekker, N.Y. (Various volumes include those titled "Anionic Surfactants" and "Surfactant Biodegradation," the last by R.D. Swisher, second edition, published in 1987 as volume 18; see especially pages 20-24 of "Hidrophobic groups and their sources"; pp. 28-29 of "Alcohols", pp. 34-35 of "Primary Alkil Sulfates" and pp. 35-36 of "Secondary Alkil Sulfates"); and the literature on "high" alcohols or "detergents" from which alkyl sulfates are typically made, including: CEH's market research information "Detergent Alcohols" from R.F. Modler et al., Chemical Economics Handbook, 1993, 609.5000-609.5002; Kirk Othmer's Encyclopedia of Chemical Technology, 4th Ed Wiley, N.Y. 1991, "Alcohols, Higher Aliphatic" in Vol. 1, pp 865-913 and references cited therein.

BRIEF DESCRIPTION OF THE INVENTION The invention covers the needs in the art of providing a detergent composition, which has a selected surfactant system for improved performance, especially under water conditions for high hardness and low temperature washing. The detergent composition includes a branched primary alkylsulphate surfactant in the middle region of the chain ("MBAS") in combination with a linear alkylbenzene sulphonate ("LAS") surfactant, and a linear alkyl sulfate surfactant ("AS") to relative proportions optimally selected. Additionally, the detergent composition contains up to about 5% of an ethoxylated alkyl sulfate surfactant and up to about 5% of a nonionic surfactant (eg, ethoxylated alkyl sulfate surfactant ("AE")), although unexpectedly it exhibits improved performance with such relatively low levels of a nonionic surfactant.

In accordance with one aspect of the invention, a detergent composition is provided. The detergent composition comprises: A) a linear alkylbenzene sulfonate surfactant; B) a branched surfactant in the middle region of the chain, wherein the weight ratio of the linear alkylbenzenesulfonate surfactant to the branched surfactant in the middle region of the chain is from about 1: 3 to about 4: 1; C) a linear alkyl sulfate surfactant, wherein the weight ratio of the linear alkylbenzenesulfonate surfactant to the linear alkyl sulfate surfactant is about: 2: 1; D) up to about 5% by weight of an ethoxylated alkyl surfactant; and E) up to about 5% by weight of an ethoxylated alkyl sulfate surfactant; where the branched surfactant in the middle region of the chain has the formula: Ab-X-B wherein a) Ab is a branched alkyl portion in the middle region of the chain, hydrophobic from 9 to 22 total carbons in the portion, preferably from about C12 near C18, which has: 1) a more linear carbon chain long attached to the -XB portion on a scale of 8 to 21 carbon atoms; 2) one or more C1-C3 alkyl portions branching from this longest linear carbon chain; 3) at least one of the branching alkyl portions is attached directly to a carbon of the longest linear carbon chain at a position within the carbon 2 position scale, counting from the # 1 carbon that joins the -XB portion to the carbon position -2, the terminal carbon minus 2 carbons; and 4) the surfactant composition has an average total number of carbon atoms in the Ab-X portion in the above formula within the range of more than 14.5 to about 18; b) B is a hydrophilic portion chosen from sulfates, sulfonates, amine oxides, polyoxyalkylene, alkoxylated sulfates, polyhydroxy portions, glycerol phosphate sulfonate esters, polygluconates, polyphosphate esters, phosphonates, sulfosuccinates, sulfosuccinatamines, polyalkoxylated carboxylates, glucamides, taurinates, sarcosinates, glycinates, isethionate dialkanolamides, monoalkanolamides, monoalkanolamide sulphates, diglycolamides, diglycolamide sulphates, glycerol esters, glycerol ester sulfates, glycerol ethers, glycerol ether sulphates, polyglycerol ethers, polyglycerol ether sterols, sorbitan esters, polyalkoxylated sorbitan esters, ammonium alkenesulfonates, amidopropyl betaines, alkylated quaternary compounds, alkylated / polyhydroxyalkylated quaternary compounds, alkylated quaternary compounds, alkylated / polyhydroxylated oxopropyl quaternary compounds, imidazolines, 2-yl succinates, alkyl esters sulfonated and sulfonated fatty acids; and c) X is -CH2-. The invention also provides a method for washing soiled fabrics, which comprises the step of the soiled fabric contacting an effective amount of a composition as described herein in an aqueous solution. In this wayIt is an object of the present invention to provide a detergent composition containing an improved surfactant system that exhibits improved cleaning at low temperatures of the wash water and increased resistance to water hardness. It is also an object of the invention to provide a detergent composition that cleans a wide range of stains and dirt that is more stable with other detergent ingredients, such as enzymes. All percentages, ratios and proportions herein are given by weight, unless stated otherwise. All temperatures are in degrees Ceisius (° C), unless otherwise specified. All documents cited herein are in part relevant, incorporated herein by reference.

DETAILED DESCRIPTION OF THE INVENTION The invention is directed to a detergent composition, preferably granular, that contains a branched surfactant in the middle region of the chain as detailed herein below and a variety of other surfactants that have been carefully chosen to be included in the composition Detergent to present optimal performance. Specifically, the composition includes a linear aikilbenzenesulfonate surfactant which can have a variety of chain lengths, as detailed herein, the above-mentioned branched surface active agent of the above-mentioned chain, and a linear alkyl sulfate surfactant. It has been found that by including such surfactants at chosen weight ratios, the composition of the invention unexpectedly achieves a superior cleaning performance. Unexpectedly, it has also been discovered that the relative levels of nonionic surfactants, such as ethoxylated alkyl, in the composition can be reduced without adversely affecting performance. Although optional, it has unexpectedly been found that the detergent composition of the invention may substantially not contain ethoxylated alkyl and ethoxylated alkyl sulfate surfactants without detrimentally affecting the overall cleaning performance of the composition. Preferably, the weight ratio of said linear alkylbenzenesulfonate surfactant people to said branched surfactant in the middle region of the chain is from about 1: 3 to about 4: 1, most preferably from about 1: 1 to about 3. : 1, very much preferably from about 2: 1 to about 3: 1. Additionally, the weight ratio of the linear alkylbenzenesulfonate surfactant to the linear alkyl sulfate surfactant is from about 2: 1 to about 20: 1, most preferably from about 4: 1 to about 10: 1, much very preferably from around 5: 1 to around 8: 1. The detergent composition of the invention also includes up to about 5% by weight of an ethoxylated alkyl sulfate surfactant and up to about 5% of an ethoxylated alkyl surfactant, preferably from about 0.01% to about 4%, very much preferably from about 0.01% to about 3% by weight of the composition. Optionally, the detergent composition of the present invention may include auxiliary detergent ingredients chosen from the group consisting of enhancers, enzymes, fillers, brighteners, bleaching agents and mixtures thereof. The preferred auxiliary detergent ingredients are selected from the group consisting of polyethylene glycol, polyacrylate and mixtures thereof. The additional auxiliary detergent ingredients are selected from the group consisting of improvers, enzymes, fillers, brighteners, bleaching agents and mixtures thereof. The surfactant system of the present invention includes a branched surfactant in the middle region of its chain as indicated below. In such surfactants, certain branching points (eg, localization along the chain of the portions R, R1 and / or R2 in the above formula) are preferred over other branch points along the structure of base of the surfactant. The formula below illustrates the branching scale in the middle region of the chain (ie, where the branching points occur), the branching scale in the middle region of the chain that is preferred and the branching scale in the middle region of the chain that it prefers especially for branched mono-methyl alkyl A ^ portions useful in accordance with the present invention.

CH3CH2CH2CH2CH2CH2 (CH2) 1-7CH2CH2CH2CH2CH2- I eessccaallaa mmuuvy p prreeffeerriiddaa I preferred scale - branching scale in the middle region of the chain It should be noted that for substituted mono-methyl surfactants these scales exclude the two terminal carbon atoms of the chain and the carbon atom immediately adjacent to the -X-B group. The following formula illustrates the branching scale in the middle region of the chain, the branching scale in the middle region of the chain that is preferred, and the branching scale in the middle region of the chain. chain which is especially preferred for substituted di-methyl alkyl AD portions useful in accordance with the present invention.

CH3CH2CH2CH2CH2CH2 (CH2)? - 6CH2CH2CH2CH2CH2- t t t I very preferred scale t I t scale preferred branching scale in the middle region of the chain Branched surfactant compositions that are preferred and useful in detergent compositions in accordance with the present invention are described in greater detail herein below. (1) Branched primary alkyl sulfate surfactants in the middle region of the chain The branched surfactant compositions of the present invention may comprise two or more branched primary alkyl sulfate surfactants in the middle region of their chain having the formula R R R CH3CH2 (CH2) wCH (CH2)? CH (CH2) and CH (CH2) zOS03M The surfactant mixtures of the present invention comprise molecules having a linear primary alkyl sulfate chain base structure (ie, the longest linear carbon chain that includes the sulfated carbon atom). These base structures of the alkyl chain comprise from 12 to 19 carbon atoms; and further the molecules comprise a branched primary alkyl moiety having at least a total of 14, but not more than 20, carbon atoms. In addition, the surfactant mixture has an average total number of carbon atoms for the branched primary alkyl portions in the range of more than 14.5 to about 17.5. In this manner, the blends of the present invention comprise at least one primary branched alkyl sulfate surfactant compound having a longer linear carbon chain of not less than 12 carbon atoms or more than 19 carbon atoms, and The total number of carbon atoms including the branch must be at least 14, and furthermore the total average number of carbon atoms for the branched primary alkyl chains is within the range of more than 14.5 to about 17.5. For example, a primary total alkyl sulfate surfactant of 16 total carbon atoms having 13 carbon atoms, in the base structure must have 1, 2 or 3 branching units (ie, R, R1 and / or R2) thereby the total number of carbon atoms in the molecule is at least 16. In this example, the requirement of 16 total carbons can be met either by having, for example, a propyl branching unit or three methyl branching units. R, R1 and R2 are each independently selected from hydrogen and C1-C3 alkyl (preferably hydrogen or C1-C2 alkyl, most preferably hydrogen or methyl, and especially methyl is preferred), with the proviso that R, R ^ and R2 are not all hydrogen. Further, when z is 1, at least R or R "1 is not hydrogen, although for the purposes of the surfactant compositions of the present invention the above formula does not include molecules in which the units R, R1 and R2 are all hydrogen (ie, unbranched linear primary alkyl sulphates), it should be recognized that the compositions of the present invention may further comprise a certain amount of unbranched linear primary alkyl sulfate In addition, this unbranched linear primary alkyl sulfate surfactant may be present as a result of the process used to make the surfactant mixture having the requirement of having one or more branched primary alkyl sulphates in the middle region of its chain according to the present invention, or for the purposes of formulating detergent compositions, a certain amount of unbranched, linear primary alkyl sulfate can be mixed into the final product formulation. Furthermore, it should be similarly recognized that the branched alcohol in the middle region of its non-sulfated chain may comprise a certain amount of the compositions of the present invention. Such materials may be present as a result of the incomplete sulfation of the alcohol used to prepare the alkyl sulfate surfactant, or these alcohols may be added separately to the detergent compositions of the present invention together with a branched alkyl sulfate surfactant in the middle region of your chain in accordance with the present invention. M is hydrogen or a salt-forming cation depending on the synthesis method. Examples of salt-forming cations are lithium, sodium, potassium, calcium, magnesium, and quaternary alkylamines having the formula: R3 ß l + 4 R - N - R R " wherein R3, R4, R5 and R6 are independently hydrogen, C-J-C22 alkylene. C4-C22 branched alkylene, C- | -C6 alkanol, C- | -C22 alkenylene of C4-C22 branched alkenylene and mixtures thereof. The preferred cations are ammonium (R3, R4, R5 and R6 are equal to hydrogen), sodium, potassium, mono-, di- and trialkanolammonium, and mixtures thereof. The monoalkanolammonium compounds of the present invention have R equal to alkanol of C- | -Cβ, R 4, R 5 and igual equal to hydrogen; the dialkanolammonium compounds of the present invention have R3 and R4alkal to C-i-C alkanol, R ^ and R ^ equal to hydrogen; the compounds of trialkanolammonium of the present invention have R, R4 and R5 equal to C-j-Cβ alkanol, R ^ equal to hydrogen. Preferred alkanolammonium salts of the present invention are the mono-, di- and quaternary triammonium compounds having the formulas: H3N + CH2CH2OH, H2N + (CH2CH2OH) 2, HN + (CH2CH20H) 3 The preferred M is salts of sodium, potassium and alkanolammonium of C2 listed above; there is a greater preference for sodium. With respect to the previous formula, w is an integer from 0 to 13; x is an integer from 0 to 13; and is an integer from 0 to 13; z is an integer of at least 1; and w + x + y + z is an integer from 8 to 14. Preferred surfactant mixtures of the present invention have at least 0.001%, most preferably at least 5%, especially at least 20% in weight, of the mixture of one or more branched primary alkyl sulphates having the formula: R FT CH3CH2 (CH2)? CH (CH2) and CH (CH2) zOS03M wherein the total number of carbon atoms, including the branching, is from 15 to 18, and wherein in addition to this mixture of surfactant the total average number of carbon atoms in the branched primary alkyl portions having the above formula is in the range of more than 14.5 to about 17.5; R ^ and R2 are each independently hydrogen or CrC3 alkyl; M is a cation soluble in water; x is from 0 to 11; and is from 0 to 11; z is at least 2; and x + y + z is from 9 to 13; with the proviso that R1 and R2 are not both hydrogen. Greater preference is given to compositions having at least 5% of the mixture comprising one or more branched primary alkyl sulphates in the middle region of its chain where x + y equals 9 and z is at least 2. Preferably, the mixtures of surfactant comprise at least 5% of a branched primary alkyl sulfate in the middle region of its chain having R 1 and R 2 independently being hydrogen, methyl, with the proviso that R 2 and R 2 are not both hydrogen; x + y are equal to 8, 9 or 10 and z is at least 2. Most preferably, the surfactant mixtures comprise at least 20% of a branched primary alkyl sulfate in the middle region of its chain having R "1 and R2 independently being hydrogen, methyl , with the proviso that R1 and R2 are not both hydrogen, x + y is equal to 8, 9 or 10 and z is at least 2.

Preferred detergent compositions according to the present invention, for example a fabric washing tool, comprise from about 0.001% to about 99% of a mixture of branched primary alkyl sulfate surfactants in the middle region of its chain, said mixture it comprises at least about 5% by weight of two or more branched alkyl sulphates in the middle region of its chain having the formula: C 3 (I) CH 3 (CH 2) aCH (CH 2) DCH 2 OSO 3 M CH3 CH3 (II) CH3 (CH2) dCH (CH2) eCHCH2 OS03M or mixtures thereof; where M represents one or more cations, a, b, d and e are integers, a + b is from 10 to 16, d + e is from 8 to 14 and where also when a + b = 10, a is an integer of 2 to 9 and b is an integer from 1 to 8; when a + b = 11, a is an integer from 2 to 10 and b is an integer from 1 to 9; when a + b = 12, a is an integer from 2 to 11 and b is an integer from 1 to 10; when a + b = 13, a is an integer from 2 to 12 and b is an integer from 1 to 11; when a + b = 14, a is an integer from 2 to 13 and b is an integer from 1 to 12; when a + b = 15, a is an integer from 2 to 14 and b is an integer from 1 to 13; when a + b = 16, a is an integer from 2 to 15 and b is an integer from 1 to 14; when d + e = 8, d is an integer from 2 to 7 and e is an integer from 1 to 6; when d + e = 9, d is an integer from 2 to 8 and e is an integer from 1 to 7; when d + e = 10, d is an integer from 2 to 9 and e is an integer from 1 to 8; when d + e = 11, d is an integer from 2 to 10 and e is an integer from 1 to 9; when d + e = 12, d is an integer from 2 to 11 and e is an integer from 1 to 10; when d + e = 13, d is an integer from 2 to 12 and e is an integer from 1 to 11; when d + e = 14, d is an integer from 2 to 13 and e is an integer from 1 to 12; wherein also for this surfactant mixture, the total average number of carbon atoms in the primary alkyl portions Branches that have the above formulas are within the range of more than 14.5 to about 17.5.

In addition, the surfactant composition of the present invention may comprise a mixture of branched primary alkyl sulphates having the formula: R R 1 R2 I I I CH3CH2 (CH) wCH (CH2) xCH (CH2) and CH (CH2) z0S03M wherein the total number of carbon atoms per molecule, including the branching, is from 14 to 20, and wherein in addition to this mixture of surfactant, the total average number of carbon atoms in the branched primary alkyl portions having the previous formula is on the scale from more than 14.5 to about 17.5; R, R1 and R2 are each independently selected from hydrogen and C? -C3 alkyl; with the condition of that R, R "and R2 are not all hydrogen, M is a water-soluble cation, w is an integer from 0 to 13, x is an integer from 0 to 13, and is an integer from 0 to 13; an integer from 0 to 13, z is an integer of at least 1, and w + x + y + z is 8 a 14; with the proviso that in the cases that R2 is an alkyl of C-1-C3, the ratio of surfactants having z equal to 1 to surfactants having z of 2 or more is at least about 1: 1, preferably at least about 1: 5, most preferably at least about 1: 10 and especially preferably at least about 1: 100. Also preferred are surfactant compositions wherein R2 is a C1-C3 alkyl, comprising less than about 20%, preferably less than about 10%, most preferably less than 5%, and especially less than 1% is preferred. branched primary alkyl sulphates having the above formula wherein z is equal to 1. The branched mono-methyl primary alkyl sulphates are selected from the group consisting of: 3-methylpentadecanolsulfate, 4-methylpentadecanolsulfate, 5-methylpentadecanolsulfate, 6-methylpentadecanolsulfate, 7-methylpentadecanolsulfate 8-metilpentadecanolsulfato, 9-metilpentadecanolsulfato, 10-metilpentadecanolsulfato, 11 metilpentadecanolsulfato, 12-metilpentadecanolsulfato, 13-metilpentadecanolsulfato, 3-metilhexadecanolsulfato, 4-metilhexadecanolsulfato, 5-metilhexadecanolsulfato, 6-metilhexadecanolsulfato, 7-metilhexadecanolsulfato, 8-metilhexadecanolsulfato 9 - methylhexadecanolsulfate, 10-methylhexadecanolsulfate, 11-methylhexa decanolsulfate, 12-methylhexadecanolsulfate, 13-methylhexadecanolsulfate, 14-methylhexadecanolsulfate and mixtures thereof. Preferred branched di-methyl primary alkyl sulphates are selected from the group consisting of: 2,3-methyltetradecanolsulfate, 2,4-methyltetradecanolsulfate, 2,5-methyltetradecanolsulfate, 2,6-methyltetradecanolsulfate, 2,7-methyltetradecanolsulfate, 2, 8-methyltetradecanolsulfate, 2,9-methyltetradecanolsulfate, 2,10-methyltetradecanolsulfate, 2,11-methyltetradecanolsulfate, 2,12-methyltetradecanolsulfate, 2,3-methylpentadecanolsulfate, 2,4-methylpentadecanolsulfate, 2,5-methylpentadecanolsulfate, 2,6- methylpentadecanolsulfate, 2,7-methylpentadecanolsulfate, 2,8-methylpentadecanolsulfate, 2,9-methylpentadecanolsulfate, 2,10-methylpentadecanolsulfate, 2,11-methylpentadecanolsulfate, 2,12-methylpentadecanolsulfate, 2,13-methylpentadecanolsulfate, and mixtures thereof. The following branched primary alkyl sulphates comprising 16 carbon atoms and having a branching unit are examples of branched surfactants useful in the compositions of the present invention: 5-methylpentadecylsulfate having the formula: 6-methylpentadecylsulfate having the formula: -methylpentadecyl sulfate that has the formula: 8-methylpentadecylsulfate having the formula: 9-methylpentadecylsulfate having the formula: -methylpentadecylsulfate having the formula: wherein M is preferably sodium. The following branched primary alkyl sulphates comprising 17 carbon atoms and having two branching units are examples of branched surfactants according to the present invention: 2,5-dimethylpentadecylsulfate having the formula: 2,6-dimethylpentadecylsulfate having the formula: 2,7-dimethylpentadecylsulfate having the formula: 2,8-dimethylpentadecylsulfate having the formula: 2,9-dimethylpentadecylsulfate having the formula: 2,10-dimethylpentadecylsulfate having the formula: M wherein M is preferably sodium. (2) Branched primary alkylpolyoxyalkylene surfactant in the middle region of its chain The branched surfactant compositions of the present invention may comprise one or more branched primary alkylpolyoxyalkylene surfactants in the middle region of their chain having the following formula: R R1 R? CH3CH2 (CH2) wCH (CH2) xCH (CH2) and CH (CH2) z (EO / PO) mOH The surfactant mixtures of the present invention comprise molecules having a linear primary polyoxyalkylene chain base structure (ie, the longest linear carbon chain including the alkoxylated carbon atom). These base structures of the alkyl chain comprise from 12 to 19 carbon atoms; and in addition the molecules comprise a branched primary alkyl portion having at least a total of 14, but not more than 20, carbon atoms. In addition, the surfactant mixture has an average total number of carbon atoms for branched primary alkyl portions within the range of more than 14.5 to about 17.5. In this manner, the blends of the present invention comprise at least one polyoxyalkylene compound having a longer linear carbon chain having not less than 12 and not more than 19 carbon atoms, and the total number of carbon atoms, including the branching, it must be at least 14, and furthermore the total average number of carbon atoms for the branched primary alkyl chains is within the range of more than 14.5 to about 17.5. For example, a primary polyoxyalkylene surfactant of 16 total carbons (in the alkyl chain) having 15 carbon atoms in the base structure must have a methyl branching unit (whether R, R 1 or R 2 is methyl) with which the total number of carbon atoms in the molecule is at least 16. R, R1 and R2 are each independently selected from hydrogen and C1-C3 alkyl (preferably hydrogen or C1-C2 alkyl, most preferably hydrogen or methyl, and methyl is especially preferred), with the proviso that R, R1 and R2 are not all hydrogen. Also, when z is 1, at least R or R ^ is not hydrogen.

Although for the purposes of the surfactant compositions of the present invention the above formula does not include molecules in which the R, R 1 and R 2 units are all hydrogen (ie, unbranched linear primary polyoxyalkylenes), it should be recognized that the compositions of The present invention may also comprise a certain amount of unbranched linear primary polyoxyalkylene. In addition, this unbranched linear primary polyoxyalkylene surfactant may be present as a result of the process used to make the surfactant mixture having the branched primary polyoxyalkylenes in the middle region of its chain necessary in accordance with the present invention, or for the For purposes of formulating detergent compositions, a certain amount of unbranched linear primary polyoxyalkylene may be mixed in the final product formulation. Furthermore, it should be recognized in the same way that the branched alcohol in the middle region of its non-alkoxylated chain may contain a certain amount of the polyoxyalkylene-containing compositions of the present invention. Such materials may be present as a result of the incomplete alkoxylation of the alcohol used to prepare the polyoxyalkylene surfactant, or these alcohols may be added separately to the detergent compositions of the present invention together with a branched polyoxyalkylene surfactant in the middle region of its chain according to the present invention.

With respect to the previous formula, w is an integer from 0 to 13; x is an integer from 0 to 13; and is an integer from 0 to 13; z is an integer of at least 1; and w + x + y + z is an integer from 8 to 14.

EO / PO are alkoxy portions, preferably selected from mixed ethoxy, propoxy and ethoxy / propoxy groups, most preferably ethoxy, wherein m is at least about 1, preferably on the scale of about 3 to about 30, most preferably about 5 to about 20 and especially about 5 to about 15 is preferred. The portion (EO / PO) m may be, or a distribution with average degree of alkoxylation (eg, ethoxylation and / or propoxylation) corresponding to am, or can be an individual specific chain with alkoxylation (eg, ethoxylation and / or propoxylation) with the exact number of units corresponding to m. The surfactant mixtures of the present invention have at least 0.001%, most preferably at least 5%, more preferably at least 20% by weight, of the mixture of one or more branched primary alkylpolyoxyalkylenes having the formula: R R1 R2 l l l CH3CH2 (CH) xCH (CH2) and CH (CH2) z (EO / PO) mOH wherein the total number of carbon atoms, including the branching, is from 15 to 18, and wherein in addition, for this surfactant mixture, the total average number of carbon atoms in the primary branched alkyl portions having the formula previous is on the scale of more than 14.5 to about 17.5; R1 and R2 are each independently hydrogen or C? -C3 alkyl; x is from 0 to 11; and is from 0 to 11; z is at least 2; and x + y + z is from 9 to 13; with the proviso that R1 and R2 are not both hydrogen; and EO / PO are alkoxy portions selected from mixed ethoxy, propoxy and ethoxy / propoxy groups, most preferably ethoxy, wherein m is at least about 1, preferably on the scale of about 3 to about 30, most preferably about 5 to about 20 and more preferably from about 5 to about 15. There is a greater preference for compositions having at least 5% of the mixture comprising one or more branched primary polyoxyalkylenes in the middle region of their chain, wherein z is at least 2. Mixtures of surfactant comprise at least %, preferably at least about 20% of a branched primary alkyl polyoxyalkylene in the middle region of its chain having R ^ and R2 independently being hydrogen or methyl, with the proviso that R1 and R2 are not both hydrogen; x + y is equal to 8, 9 or 10 and z is at least 2. Preferred detergent compositions according to the present invention, for example a fabric washing tool, comprise from about 0.001% to about 99% of a mixture of primary branched alkylpolyoxyalkylene surfactants in the middle region of their chain, said mixture comprises at least about 5% by weight of one or more branched alkylpolyoxyalkylenes in the middle region of their chain having the formula: C, 3 (I) CH3 (CH2) aCH (CH2) bCH2 (EO / PO) mOH CH3 CH3 (II) CH3 (CH2) dCH (CH2) eCHCH2 (EO / PO) mOH or mixtures thereof; where a, b, d and e are integers, a + b is from 10 to 16, d + e is from 8 to 14 and where also when a + b = 10, a is an integer from 2 to 9 and b is an integer from 1 to 8; when a + b = 11, a is an integer from 2 to 10 and b is an integer from 1 to 9; when a + b = 12, a is an integer from 2 to 11 and b is an integer from 1 to 10; when a + b = 13, a is an integer from 2 to 12 and b is an integer from 1 to 11; when a + b = 14, a is an integer from 2 to 13 and b is an integer from 1 to 12; when a + b = 15, a is an integer from 2 to 14 and b is an integer from 1 to 13; when a + b = 16, a is an integer from 2 to 15 and b is an integer from 1 to 14; when d + e = 8, d is an integer from 2 to 7 and e is an integer from 1 to 6; when d + e = 9, d is an integer from 2 to 8 and e is an integer from 1 to 7; when d + e = 10, d is an integer from 2 to 9 and e is an integer from 1 to 8; when d + e = 11, d is an integer from 2 to 10 and e is an integer from 1 to 9; when d + e = 12, d is an integer from 2 to 11 and e is an integer from 1 to 10; when d + e = 13, d is an integer from 2 to 12 and e is an integer from 1 to 11; when d + e = 14, d is an integer from 2 to 13 and e is an integer from 1 to 12; and wherein additionally for this surfactant mixture the total average number of carbon atoms in the primary branched alkyl portions having the above formulas is within the range of more than 14.5 to about 17.5; and EO / PO are alkoxy portions selected from mixed ethoxy, propoxy and ethoxy / propoxy groups, wherein m is at least about 1, preferably on the scale from about 3 to about 30, most preferably from about 5 to about 20, and especially preferred from about 5 to about 15. In addition, the surfactant composition of the present invention may comprise a mixture of branched primary alkyl polyoxyalkylenes having the formula: R R1 R2 I I I CH3CH2 (CH2) wCH (CH2)? CH (CH2) and CH (CH2) z (EO / PO) mOH wherein the total number of carbon atoms per molecule, including branching, is from 14 to 20, and wherein in addition to this mixture of surfactant the total average number of carbon atoms in the branched primary alkyl portions having the formula previous is on the scale of more than 14.5 to about 17.5; R, R1 and R2 are each independently selected from hydrogen and CrC3 alkyl; with the proviso that R, R1 and R2 are not all hydrogen; w is an integer from 0 to 13; x is an integer from 0 to 13; and is an integer from 0 to 13; z is an integer of at least 1; and w + x + y + z is from 8 to 14; EO / PO are alkoxy portions preferably selected from mixed ethoxy, propoxy and ethoxy / propoxy groups, wherein m is at least about 1, preferably on the scale of about 3 to about 30, most preferably about 5. to about 20 and especially about 5 to about 15; with the proviso that when R2 is an alkyl of C C3 the ratio of surfactants having z equal to 2 or more to surfactants having z of 1 is at least about 1: 1, preferably at least about 1.5: 1, most preferably at least about 3: 1 and especially at least about 4: 1 is preferred. Also preferred are surfactant compositions wherein R2 is a CrC3 alkyl, comprising less than about 50%, preferably less than about 40%, most preferably less than about 25%, and especially less than about 20% is preferred. of branched primary alkyl polyoxyalkylene having the above formula, wherein z is equal to 1. The branched mono-methyl primary alkyl ethoxylates are selected from the group consisting of: 3-methylpentadecanoletoxylate, 4-methylpentadecanoletoxylate, 5-methylpentadecanoletoxylate, 6-methylpentadecanolethoxylate, 7-metilpentadecanoletoxilato, pentadecanoletoxilato methyl 8-, 9-metilpentadecanoletoxilato, 10-metilpentadecanoletoxilato 11 -metilpentadecanoletoxilato, 12-metilpentadecanoletoxilato, 13-metilpentadecanoletoxilato, 3-metilhexadecanoletoxilato, 4-metilhexadecanoletoxilato, 5-metilhexadecanoletoxilato, 6-metilhexadecanoletoxilato, 7-metilhexadecanoletoxilato, 8 -metilhexadecanolet Oxylate, 9-methylhexadecanoletoxylate, 10-methylhexadecanoletoxylate, 11-methylhexadecanoletoxylate, 12-methylhexadecanoletoxylate, 13-methylhexadecanoletoxylate, 14-methylhexadecanoletoxylate and mixtures thereof, wherein the compounds are ethoxylated with an average degree of ethoxylation of about 5 to about 15. Preferred branched di-methyl primary alkyl ethoxylates are selected from the group consisting of: 2,3-methyltetradecanolethoxylate, 2,4-methyltetradecanolethoxylate, 2,5-methyltetradecanolethoxylate, 2,6-methyltetradecanolethoxylate, 2,7-methyltetradecanolethoxylate, 2,8-methyltetradecanoletoxylate, 2,9-methyltetradecanoletoxylate, 2,10-methyltetradecanolethoxylate, 2,11-methyltetradecanolethoxylate, 2,12-methyltetradecanolethoxylate, 2,3-methylpentadecanolethoxylate, 2,4-methylpentadecanolethoxylate, 2,5-methylpentadecanolethoxylate, 2 , 6-methylpentadecanoletoxilato, 2,7-methylpentadecanoletoxilato, 2,8-methylpentadecanoletoxilato, 2,9-methylpentadecanoletoxilato, 2,10-methylpentadecanoletoxilato, 2,11-methylpentadecanol-ethoxylate, 2,12-methylpentadecanoletoxilato, 2,13- methylpentadecanoletoxilato and mixtures thereof, wherein the compounds are ethoxylated with an average degree of ethoxylation of about 5 to about 15. (3) Branched primary alkoxylated alkyl sulfate surfactants in the middle region of its chain The branched surfactant compositions of the present invention may comprise one or more (preferably a mixture of two or more) branched primary alkoxylated alkyl sulfate surfactants in the middle region of your chain that have the formula R R1 R2 I I I CH3CH2 (CH2) wCH (CH2)? CH (CH2) and CH (CH2) z (EO / PO) mO S03M The surfactant mixtures of the present invention contain molecules having a linear primary alkoxylated sulfate chain base structure (ie, the longest linear carbon chain including the alkoxysulphated carbon atom). These alkyl base structures comprise from 12 to 19 carbon atoms; and furthermore the molecules comprise a branched primary alkyl portion having at least a total of 14 and no more than 20 carbon atoms. In addition, the surfactant mixture has an average total number of carbon atoms for branched primary alkyl portions within the range of more than 14.5 to about 17.5. In this manner, the mixtures of the present invention comprise at least one alkoxylated sulfate compound having a longer linear carbon chain of not less than 12 carbon atoms or more than 19 carbon atoms, and the total number of atoms of carbon including the branching must be at least 14, and in addition the total average number of carbon atoms for the branched primary alkyl chains is within the range of more than 14.5 to about 17.5. For example, a primary alkoxylated alkylsulfate surfactant of 16 total carbons (in the alkyl chain) having 15 carbon atoms in the base structure must have a methyl branching unit (whether R, R ^ O R2 is methyl) ) whereby the total number of carbon atoms in the primary alkyl portion of the molecule is 16. R, R1 and R2 are each independently selected from hydrogen and C1-C3 alkyl (preferably hydrogen or C-1 alkyl) C2, most preferably hydrogen or methyl, and methyl is especially preferred), with the proviso that R, R1 and R2 are not all hydrogen. Also, when z is 1, at least R or R ^ is not hydrogen. Although for the purposes of the surfactant compositions of the present invention the above formula does not include molecules in which the units R, R ^ and R2 are all hydrogen (ie, linear unbranched primary alkoxylated sulfates), it should be recognized that the Compositions of the present invention may comprise even a certain amount of unbranched linear primary alkoxylated sulfate. In addition, this unbranched linear primary alkoxylated sulfate surfactant may be present as a result of the process used to make the surfactant mixture having the branched primary alkoxylated sulphates in the middle region of its chain necessary in accordance with the present invention, or for the purposes of formulating detergent compositions, a certain amount of unbranched linear primary alkoxylated sulfate can be mixed in the final product formulation. It should also be recognized that a certain amount of branched alkyl sulfate in the middle region of its chain may be present in the compositions. This is typically the result of the sulfation of a non-alkoxylated alcohol which remains after the incomplete alkoxylation of the branched alcohol in the middle region of its chain used to prepare the alkoxylated sulfate of the present. However, it should be recognized that the separate addition of said branched alkyl sulphates in the middle region of their chain is also contemplated by the compositions of the present invention. Furthermore it should be recognized in the same way that the branched alcohol in the middle region of its unsulfated chain (including the polyoxyalkylene alcohols) may comprise a certain amount of the alkoxylated sulfate-containing compositions of the present invention. Such materials may be present as a result of the incomplete sulfation of the alcohol (alkoxylated or non-alkoxylated) used to prepare the alkoxylated sulfate surfactant, or these alcohols can be added separately to the detergent compositions of the present invention together with an alkoxylated sulfate surfactant branched in the middle region of its chain according to the present invention. M is as described above in the present. With respect to the previous formula, w is an integer from 0 to 13; x is an integer from 0 to 13; and is an integer from 0 to 13; z is an integer of so Minus 1; and w + x + y + z is an integer from 8 to 14. EO / PO are alkoxy portions, preferably selected from mixed ethoxy, propoxy and ethoxy / propoxy groups, wherein m is at least about 0.01, preferably on the scale of about 0.1 to about 30, most preferably about 0.5 to about 10 and is especially preferred about from 1 to around 5. The portion (EO / PO) m can be, or a distribution with average degree of alkoxylation (eg, ethoxylation and / or propoxylation) corresponding to m or can be an individual specific chain with alkoxylation (e.g., ethoxylation and / or propoxylation) with the exact number of units corresponding to m. The surfactant mixtures of the present invention have at least 0.001%, most preferably at least 5%, especially at least 20% by weight of the mixture, of one or more branched primary alkoxylated alkyl sulphates having the formula : R1 R2 I I CH3CH2 (CH2) CH (CH2) CH (CH2) (EO / PO) mO S03M wherein the total number of carbon atoms, including the branching, is from 15 to 18, and in addition for this mixture of surfactant, the total average number of carbon atoms in the branched primary alkyl portions having the above formula is in the scale greater than 14.5 to about 17.5; R1 and R2 are each independently hydrogen or CrC3 alkyl; M is a cation soluble in water; x is from 0 to 11; and is from 0 to 11; z is at least 2; and x + y + z is from 9 to 13; with the proviso that R1 and R2 are not both hydrogen, and EO / PO are selected alkoxy portions of ethoxy, propoxy, and ethoxy / propoxy mixed groups, wherein m is at least about 0.01, preferably within the scale of about from 0.1 to about 30, more preferably from about 0.5 to about 10, and more preferably from about 1 to about 5. More preferred are compositions having at least 5% of the mixture comprising one or more sulfates branched primary alkoxylates in the middle region of its chain wherein z is at least 2. Preferably, the surfactant mixtures comprise at least 5%, preferably at least about 20%, of a branched primary alkoxylated alkylsulfate in the middle region of its chain having R1 and R2 independently being hydrogen or methyl, with the proviso that R1 and R2 are not both hydrogen; x + y are equal to 8, 9 or 10 and z is at least 2. Preferred detergent compositions according to the present invention, for example a fabric washing tool, comprise from about 0.001% to about 99% of a mixture of branched primary alkoxylated alkyl sulfate surfactants in the middle region of its chain, said mixture comprising at least about 5% by weight of one or more branched alkoxylated alkyl sulphates in the middle region of its chain having the formula: (I) CH3 (CH2) aCH (CH2) bCH2 (EO / PO) mO SO3M CH3 CH3 (II) CH3 (CH2) dCH (CH2) eCHCH2 (EO / PO) mO S03M or mixtures thereof; where M represents one or more cations, a, b, d and e are integers, a + b is from 10 to 16, d + e is from 8 to 14 and where also when a + b = 10, a is an integer of 2 to 9 and b is an integer from 1 to 8; when a + b = 11, a is an integer from 2 to 10 and b is an integer from 1 to 9; when a + b = 12, a is an integer from 2 to 11 and b is an integer from 1 to 10; when a + b = 13, a is an integer from 2 to 12 and b is an integer from 1 to 11; when a + b = 14, a is an integer from 2 to 13 and b is an integer from 1 to 12; when a + b = 15, a is an integer from 2 to 14 and b is an integer from 1 to 13; when a + b = 16, a is an integer from 2 to 15 and b is an integer from 1 to 14; when d + e = 8, d is an integer from 2 to 7 and e is an integer from 1 to 6; when d + e = 9, d is an integer from 2 to 8 and e is an integer from 1 to 7; when d + e = 10, d is an integer from 2 to 9 and e is an integer from 1 to 8; when d + e = 11, d is an integer from 2 to 10 and e is an integer from 1 to 9; when d + e = 12, d is an integer from 2 to 11 and e is an integer from 1 to 10; when d + e = 13, d is an integer from 2 to 12 and e is an integer from 1 to 11; when d + e = 14, d is an integer from 2 to 13 and e is an integer from 1 to 12; wherein also for this surfactant mixture, the total average number of carbon atoms in the branched primary alkyl portions having the above formulas is within the range of more than 14.5 to about 17.5; and EO / PO are portions alkoxy selected from ethoxy, propoxy, and mixed ethoxy / propoxy groups, wherein m is at least about 0.01, preferably within the range of from about 0.1 to about 30, more preferably from about 0.5 to about 10, and more preferably from about 1 to about 5. In addition, the surfactant composition of the present invention may comprise a mixture of branched primary alkoxylated alkyl sulfates having the formula: R R 1 R2 III CH3CH2 (CH2) wCH (CH2)? CH (CH2) and CH (CH2) z (EO / PO) mO S03M wherein the total number of carbon atoms per molecule, including branching, is from 14 to 20, and wherein in addition to this mixture of surfactant the total average number of carbon atoms in the primary branched alkyl portions having the formula previous is on the scale of more than 14.5 to around 17.5; R, R1 and R2 are each independently selected from hydrogen and CrC3 alkyl; with the proviso that R, R1 and R2 are not all hydrogen; M is a cation soluble in water; w is an integer from 0 to 13; x is an integer from 0 to 13; and is an integer from 0 to 13; z is an integer of at least 1 and w + x + y + z is from 8 to 14; and EO / PO are selected alkoxy portions of ethoxy, propoxy, and mixed ethoxy / propoxy groups, wherein m is at least about 0.01, preferably within the range of about 0.1 to about 30, more preferably about 0.5. to about 10, and more preferably from about 1 to about 5, provided that when R2 is a CrC3 alkyl the ratio of surfactants having z equal to 1 to surfactants having z of 2 or more is at least about 1: 1, preferably at least about 1: 5, most preferably at least about 1: 10 and more preferably at least about 1: 100. Also preferred are surfactant compositions wherein R2 is a CrC3 alkyl, comprising less than about 50%, preferably less than about 40%, most preferably less than about 25%, more preferably less than 20% of branched primary alkoxylated alkyl sulphates having the above formula wherein z equals 1. The preferred mono-methyl branched primary alkyl ethoxylates are selected from the group consisting of: ethoxylated 3-methylpentadecanolsulfate, ethoxylated 4-methylpentadecanolsulfate, ethoxylated 5-methylpentadecanolsulfate, 6-metilpentadecanolsulfato ethoxylate, 7-metilpentadecanolsulfato ethoxylate, 8-metilpentadecanolsulfato ethoxylate, ethoxylated metilpentadecanolsulfato 9-, 10-metilpentadecanolsulfato ethoxylate, 11-metilpentadecanolsulfato ethoxylate, 12-metilpentadecanolsulfato ethoxylate, 13-metilpentadecanolsulfato ethoxylate, 3-metilhexadecanolsulfato ethoxylate, 4-metilhexadecanolsulfato ethoxylated 5-methylhe ethoxylated xadecanolsulfate, ethoxylated 6-methylhexadecanolsulfate, ethoxylated 7-methylhexadecanolsulfate, ethoxylated 8-methylhexadecanolsulfate, ethoxylated 9-methylhexadecanolsulfate, ethoxylated 10-methylhexadecanolsulfate, ethoxylated 11-methylhexadecanolsulfate, ethoxylated 12-methylhexadecanolsulfate, ethoxylated 13-methylhexadecanolsulfate, ethoxylated 14-methylhexadecanolsulfate and mixtures of these, wherein the compounds are ethoxylated with an average degree of ethoxylation of from about 0.1 to about 10. The branched dimethyl primary ethoxylated alkyl sulfates that are preferred are selected from the group consisting of: ethoxylated 2,3-methyltetradecanolsulfate, 2, Ethoxylated 4-methyltetradecanolsulfate, ethoxylated 2,5-methyltetradecanolsulfate, ethoxylated 2,6-methyltetradecanolsulfate, ethoxylated 2,7-methyltetradecanolsulfate, ethoxylated 2,8-methyltetradecanolsulfate, ethoxylated 2,9-methyltetradecanolsulfate, ethoxylated 2,10-methyltetradecanolsulfate, 2.11 -methytetradecanolsulfate ethoxylate, 2,12-methyl ethoxylated tradecanolsulfate, ethoxylated 2,3-methylpentadecanolsulfate, ethoxylated 2,4-methylpentadecanolsulfate, ethoxylated 2,5-methylpentadecanolsulfate, Ethoxylated 2,6-methylpentadecanolsulfate, ethoxylated 2,7-methylpentadecanolsulfate, ethoxylated 2,8-methylpentadecanolsulfate, ethoxylated 2,9-methylpentadecanolsulfate, ethoxylated 2,10-methylpentadecanolsulfate, ethoxylated 2,11 -methylpentadecanolsulfate, ethoxylated 2,12-methylpentadecanolsulfate, Ethoxylated 2,13-methylpentadecanolsulfate and mixtures thereof, wherein the compounds are ethoxylated with an average degree of ethoxylation of from about 0.1 to about 10 The following examples are representative of other detergent surfactants useful in the present detergent composition. The water-soluble salts of the higher fatty acids, i.e., "soaps", are anionic surfactants useful in the compositions herein. The above includes alkali metal soaps such as the sodium, potassium, ammonium and alkylolammonium salts of higher fatty acids containing from about 8 to about 24 carbon atoms, preferably from about 12 to about 18 carbon atoms. . The soaps can be made by direct saponification of fats oils or by neutralization of free fatty acids. Particularly useful are the sodium and potassium salts of the fatty acid mixtures derived from coconut oil and bait, that is, sodium or potassium soap from bait and coconut. Additional anionic surfactants which are suitable for use herein include the water soluble salts, preferably the alkali metal, ammonium and alkylolammonium salts, of organic sulfuric reaction products having an alkyl group in their molecular structure straight chain containing from about 10 to about 20 carbon atoms and an ester group of sulfonic acid or sulfuric acid. (Included in the term "alkyl" is the alkyl portion of acyl groups). Examples of such groups of synthetic surfactants are sodium and potassium alkyl sulfates, especially those obtained by sulfation of higher alcohols (Cs-iß carbon atoms), such as those produced by the reduction of glycerides from bait or coconut oil.; and the sodium and potassium alkylbenzene sulphonates in which the alkyl group contains from about 9 to about 15 carbon atoms, in straight chain, for example, those of the type described in the U.S.A. 2,220,099 and 2,477,383. Especially valuable are linear straight-chain alkylbenzenesulfonates in which the average number of carbon atoms in the alkyl group is from about 11 to 13, abbreviated as Cu-13 LAS. Other suitable anionic surfactants for use herein are alkyl glyceryl sodium ether sulfonates, especially those ethers of higher alcohols derived from bait and coconut oil; sulfonates and monoglyceride sulphates of sodium coconut oil fatty acid sodium; sodium or potassium of ethylene oxide per molecule and wherein the alkyl groups contain from about 8 to about 12 carbon atoms; and sodium or potassium salts of alkylethylene oxide ether sulfates containing from about 1 to about 10 ethylene oxide units per molecule and wherein the alkyl group contains from about 10 to about 20 carbon atoms.

In addition, suitable anionic surfactants include the water-soluble salts of alpha-sulfonated fatty acid esters containing from about 6 to 20 carbon atoms in the fatty acid group and from about 1 to 10 carbon atoms in the ester group; the water-soluble salts of 2-acyloxyalkane-1-sulfonic acids containing from about 2 to 9 carbon atoms in the acyl group and from about 9 to about 23 carbon atoms in the alkane portion; alkyl ether sulphates containing from about 10 to 20 carbon atoms in the alkyl group and from about 1 to 30 moles of ethylene oxide; water-soluble salts of olefin and paraffin sulfonates containing from about 12 to 20 carbon atoms; and beta-alkyloxy alkane sulfonates containing from about 1 to 3 carbon atoms in the alkyl group and from about 8 to 20 carbon atoms in the alkane portion. Preferred essential anionic surfactants for the detergent composition are the linear alkylbenzene sulphonate of Cio-iß and the alkyl sulfate of C-? O-18- If desired, the low molecular weight alkylsulfate paste (less than about 25% water) It can be the sole ingredient in the surfactant paste. Most preferred are alkyl, linear or branched C10-18 alkyl sulfates of any primary, secondary or tertiary. A preferred embodiment of the present invention is wherein the surfactant paste comprises from about 20% to about 40% of a mixture of linear sodium alkylbenzenesulfonate of C? O-? 3 and C? 2-16 alkyl sulfate in a weight ratio of about 2: 1 to 1: 2.

Water-soluble nonionic surfactants are also useful in the instant invention. Such non-ionic materials include compounds produced by the condensation of alkylene oxide groups (hydrophilic in nature) with an organic hydrophobic group, which may be aliphatic or aromatic alkyl in nature. The length of the polyoxyalkylene group that condenses with any particular hydrophobic group can be easily adjusted to produce a water-soluble compound having the desired degree of balance between hydrophilic and hydrophobic elements. Suitable nonionic surfactants include the polyethylene oxide condensates of alkylphenols, ie, the condensation products of alkylphenols having an alkyl group containing from about 6 to 15 carbon atoms, either in straight chain configuration or branched chain, with about 3 to 12 moles of ethylene oxide per mole of alkylphenol. Included are the water-soluble and water-dispersible condensation products of aliphatic alcohols containing from 8 to 22 carbon atoms, either in straight or branched chain configuration, with 3 to 12 moles of ethylene oxide per mole of alcohol. An additional group of nonionic surfactants for use herein are semi-polar nonionic surfactants including water-soluble amine oxides containing an alkyl portion of about 10 to 18 carbon atoms and two selected portions of the group of alkyl and hydroxyalkyl portions of about 1 to 3 carbon atoms; water-soluble phosphine oxides containing an alkyl portion of about 10 to 18 carbon atoms and two portions selected from the group consisting of alkyl groups and hydroxyalkyl groups containing from about 1 to 3 carbon atoms; and water soluble sulfoxides containing an alkyl portion of about 10 to 18 carbon atoms and a portion selected from the group consisting of alkyl and hydroxyalkyl portions of about 1 to 3 carbon atoms. Preferred nonionic surfactants are of the formula R1 (OC2H4) nOH, wherein R1 is an alkyl group of Cio-C-iß or an alkylphenyl group of C8-C2, and n is from 3 to about 80. Particularly Preferred are the condensation products of C? 2-C? alco alcohols with from about 5 to about 20 moles of ethylene oxide per mole of alcohol, that is, C 12 -C 3 alcohol condensed with about 6.5 moles of ethylene oxide per mole of alcohol. Additional suitable nonionic surfactants include polyhydroxy fatty acid amides. Examples are cocoamide of N-methyl N-1-deoxyglucityl and N-methyl N-1-deoxyglucityl oleamide. The methods for making the polyhydroxy fatty acid amides are known and can be found in Wilson, U.S. Pat. No. 2,965,576 and Schwartz, U.S. Patent No. 2,703,798, the disclosures of which are incorporated herein by reference. Ampholytic surfactants include derivatives of aliphatic or aliphatic derivatives of heterocyclic secondary and tertiary amines in which the aliphatic portion can be straight or branched chain and wherein one of the aliphatic substituents contains from about 8 to 18 carbon atoms and less an aliphatic substituent contains a water-soluble anionic group. Zwitterionic surfactants include derivatives of aliphatic, quaternary, amino, phosphonium and sulfonium compounds in which one of the aliphatic substituents contains from about 8 to 18 carbon atoms. Cationic surfactants can also be included in the present invention. Cationic surfactants comprise a wide variety of compounds characterized by one or more organic hydrophobic groups in the cation and generally by a quaternary nitrogen associated with an acid radical. Pentavalent nitrogen ring compounds are also considered quaternary nitrogen compounds. Suitable anions are halides, methylisulfate and hydroxide. Tertiary amines may have characteristics similar to cationic surfactants in wash solution of pH values less than about 8.5. A more complete description of these and other cationic surfactants useful herein can be found in U.S. Patent 4,228,044, Cambre, issued October 14, 1980, incorporated herein by reference. Cationic surfactants are often used in detergent compositions to provide softening and / or antistatic benefits to the fabric. Antistatic agents that provide some benefit of softness and which are preferred herein are the quaternary ammonium salts described in US Pat. No. 3,939,537, Baskerville, Jr. et al., Issued February 3, 1976, the description of which is incorporated herein. in the present by reference.

Detersive Detergent Ingredients The detergent composition of the invention may include one or more adjunct detergent ingredients as described herein. The compositions of the invention can contain all forms of organic detergent compounds, soluble in water, while the builder material is compatible with all these materials. In addition to a detersive surfactant, at least one suitable adjunct detergent ingredient is preferably included in the detergent composition. The adjunct detergent ingredient is preferably selected from the group consisting of detergency builders, enzymes, bleaching agents, bleach activators, foam suppressants, soil release agents, brighteners, performes, hydrotropes, dyes, pigments, polymeric dispersing agents , pH control agents, chelators, processing aids, crystallization aids, and mixtures thereof. The following list of detergent ingredients and mixtures thereof that may be used in the compositions herein is representative of the detergent ingredients, but is not intended to be imitative.

One or more detergency builders may be used in conjunction with the builder material described herein for further performance improvement of the compositions described herein. For example, the detergency builder may be selected from the group consisting of aluminosilicate, crystalline layered silicates, MAP zeolites, citrates, amorphous silicates, polycarboxylates, sodium carbonates, and mixtures thereof. The ingredient sodium carbonate can serve as the inorganic alkaline material when a liquid acid precursor of the medium chain branched surfactant is used. Other suitable auxiliary detergency builders are described below. Preferred builders include aluminosilicate and sodium carbonate exchange materials. The aluminosilicate ion exchange materials used herein as a builder preferably have a high ion and calcium exchange capacity and a high exchange rate. Without intending to be limited by theory, it is believed that said high calcium ion exchange rate and capacity are a function of several interrelated factors that are derived from the method by which the aluminosilicate ion exchange material is produced. In this regard, the aluminosilicate ion exchange materials used herein are preferably produced in accordance with Corkill et al, U.S. No. 4,605,509 (Procter &Gamble), the disclosure of which is incorporated herein by reference.

Preferably, the aluminosilicate exchange material is in the "sodium" form since the potassium and hydrogen forms of the instant aluminosilicate do not exhibit high exchange rate and capacity as provided by the sodium form. Additionally, the aluminosilicate ion exchange material is preferably in the overdried form to facilitate the production of tightening detergent agglomerates as described herein. The alumosilicate ion exchange materials used herein preferably have particle size diameters that optimize their effectiveness as builders. The term "particle size diameter" as used herein represents the average particle size diameter of a given aluminosilicate ion exchange material as determined by conventional analytical techniques, such as microscopic determination and electron microscopy. sweep (SEM). The diameter of the preferred particle size of the aluminosilicate is from about 0.1 microns to about 10 microns, more preferably from about 0.5 microns to about 9 microns. More preferably, the diameter of particle size is from about 1 miera to about 8 micras. Preferably, the exchange material of aluminosilicate has the formula: Na2 [(AI02) z. (Si02) y] xH20 where z and "y" are integers of at least 6, the molar ratio of zay is around from 1 to about 5 and x is from about 10 to about 264. More preferably, the aluminosilicate has the formula. Na12 [(AI02) 12. (S02)? 2] xH20 where x is from about 20 to about 30, preferably around 27. Such preferred aluminosilicates are commercially available, for example, under the designations Zeolite A , Zeolite B and Zeolite X. Alternatively, naturally occurring or synthetically derived aluminosilicate ion exchange materials for use herein can be manufactured as described in Krummel et al, US Patent No. 3,985,669, the disclosure of which is incorporated herein by reference. The aluminosilicates used herein are further characterized by their ion exchange capacity which is at least about 200 mg equivalent of CaC03 hardness / gram, calculated on an anhydrous basis, and which is preferably on the scale of about 300 to 352 mg equivalents of CaC03 hardness / gram. Additionally, the instant aluminosilicate ion exchange materials are further characterized by their calcium ion exchange rate which is at least about 2 grains of Ca ++ / 3.78 liters / minute / -gram / 3.78 liters, and more preferably on a scale of about 2 grains of Ca ++ / 3.78 liters / minute / -gram / 3.78 liters, about 6 grains of Ca ++ / 3.78 liters / minute / -gram / 3.78 liters.

In order to more clearly explain the present invention, reference is made to the following examples, which are intended to be illustrative only and are not intended to be limiting in scope. In the following examples, the abbreviations for the various ingredients used for the compositions have the following meanings.

In the following examples all the levels are mentioned as percent by weight of the composition. The following examples are illustrative of the present invention, but are not intended to limit or otherwise define its scope. All parts, percentages and relationships used herein are expressed as weight percent unless otherwise specified.

EXAMPLE 1 The following laundry detergent compositions A to D are prepared according to the invention: EXAMPLE 2 The following laundry detergent compositions E to F are prepared according to the invention: EXAMPLE 3 The following laundry detergent compositions J to O are prepared according to the invention: EXAMPLE 4 The following laundry detergent compositions P a S repair according to the invention: EXAMPLE 5 The following laundry detergent compositions T a X are prepared according to the invention: EXAMPLE 6 The following detergent compositions for laundry AND DD are prepared according to the invention: Having thus described the invention in detail, it will be apparent to those skilled in the art that various changes can be made without departing from the scope of the invention and the invention is not considered to be limited to what is described in the specification.

Claims (11)

NOVELTY OF THE INVENTION CLAIMS

1. - A detergent composition comprising: (A) a linear alkylbenzenesulfonate surfactant; (B) a branched surfactant in the middle region of the chain, wherein the weight ratio of the linear alkylbenzenesulfonate surfactant to the branched surfactant in the middle region of the chain is from about 1: 3 to about 4: 1; (C) a linear alkyl sulfate surfactant, wherein the weight ratio of the linear alkylbenzenesulfonate surfactant to the linear alkyl sulfate surfactant is from about 2: 1 to about 20: 1; (D) up to about 5% by weight of an ethoxylated alkyl surfactant; and (E) up to about 5% by weight of an ethoxylated alkyl sulfate surfactant; wherein the branched surfactant in the middle region of the chain has the formula: Ab-XB wherein (a) Ab is a branched alkyl portion in the middle region of the chain, hydrophobic from C9 to C22 total carbons in the portion , preferably from about C12 to about C18, having: (1) a longer linear carbon chain attached to the -XB portion on the scale of 8 to 21 carbon atoms; (2) one or more C? -C3 alkyl portions branching from said longer linear carbon chain; (3) at least one of the branching alkyl portions is attached directly to a carbon of the longest linear carbon chain at a position within the carbon 2 position scale, counting from carbon # 1 which is joins the -XB portion to the carbon position -2, the terminal carbon minus 2 carbons; and (4) the surfactant composition has an average total number of carbon atoms in the Ab-X portion in the above formula within the range of more than 14.5 to about 18; (b) B is a selected hydrophilic portion of sulphates, sulfonates, amine oxides, polyoxyalkylene, alkoxylated sulfates, polyhydroxy portions, glycerol phosphate sulfonate esters, polygluconates, polyphosphate esters, phosphonates, sulfosuccinates, sulfosuccinatamines, polyalkoxylated carboxylates, glucamides, taurinates , sarcosinates, glycinates, isethionates dialkanolamides, monoalkanolamides, monoalkanolamide sulphates, diglycolamides, diglycolamide sulphates, glycerol esters, glycerol ester sulfates, glycerol ethers, glycerol ether sulphates, polyglycerol ethers, polyglycerol ether sulphates, sorbitan esters, polyalkoxylated sorbitan esters, ammonium alkenesulfonates, amidopropyl betaines , alkylated quaternary compounds, alkylated / polyhydroxyalkylated quaternary compounds, alkylated quaternary compounds, alkylated / polyhydroxylated oxopropyl quaternary compounds, imidazolines, 2-yl-succinates, alkyl esters sulphonated and sulfonated fatty acids; and c) X is -CH2-.

2. The composition according to claim 1, further characterized in that said weight ratio of said linear alkylbenzenesulfonate surfactant to a branched surfactant in the middle region of the chain is from about 1: 1 to about 3: 1.

3. The composition according to claim 1, further characterized in that said weight ratio of said linear alkylbenzenesulfonate surfactant to a branched surfactant in the middle region of the chain is from about 0.8: 1 to about 1.5. :1.

4. The composition according to claim 1, further characterized in that said composition is substantially free of ethoxylated alkyl sulfate surfactants and alkyl ethoxylated surfactants.

5. The composition according to claim 1, further characterized in that it comprises an adjunct detergent ingredient selected from the group consisting of polyethylene glycol, polyacrylate and mixtures thereof.

6. The composition according to claim 1, further characterized in that said alkyl ethoxylated surfactant is present in an amount of from about 0.01% to about 4% by weight of said composition.

7. The composition according to claim 1, further characterized in that said alkyl ethoxylated surfactant is present in an amount of from about 0.1% to about 3% by weight of said composition.

8. The composition according to claim 1, further characterized in that it includes adjunct detergent ingredients selected from the group consisting of detergency builders, enzymes, fillers, brighteners, bleaching agents, and mixtures thereof.

9. The composition according to claim 1, further characterized in that the Ab portion is a branched primary alkyl portion having the formula: R R 1 R2 CH 3 CH 2 (CH 2) w CH (CH 2) CH CH (CH 2) y CH (CH 2) y CH (CH2) 2- wherein the total number of carbon atoms in the primary branched alkyl portion of said formula, including the branching of R, R1, and R2, is from 13 to 19; R, R1 and R2 are independently selected from the hydrogen and the CrC3 alkyl, with the proviso that R, R1 and R2 are not all hydrogen and, when z is 0, at least R or R1 is not hydrogen; w is an integer from 0 to 13; x is an integer from 0 to 13; and is an integer from 0 to 13; z is an integer from 0 to 13; and w + x + y + z is from 7 to 13.

10. The composition according to claim 1, further characterized in that the Ab portion is a branched primary alkyl portion having the formula selected from: CH3 (I) CH3 (CH2) aCH (CH2) bCH2 (EO / PO) mO SO3M CH. CH. (II) CH3 (CH2) dCH (CH2) eCHCH2 (EO / PO) mO S03M or mixtures thereof; where M represents one or more cations, a, b, d and e are integers, a + b is from 10 to 16, d + e is from 8 to 14 and where in addition, when a + b = 10, a is an integer from 2 to 9 and b is an integer from 1 to 8; when a + b = 11, a is an integer from 2 to 10 and b is an integer from 1 to 9; when a + b = 12, a is an integer from 2 to 11 and b is an integer from 1 to 10; when a + b = 13, a is an integer from 2 to 12 and b is an integer from 1 to 11; when a + b = 14, a is an integer from 2 to 13 and b is an integer from 1 to 12; when a + b = 15, a is an integer from 2 to 14 and b is an integer from 1 to 13; when a + b = 16, a is an integer from 2 to 15 and b is an integer from 1 to 14; when d + e = 8, d is an integer from 2 to 7 and e is an integer from 1 to 6; when d + e = 9, d is an integer from 2 to 8 and e is an integer from 1 to 7; when d + e = 10, d is an integer from 2 to 9 and e is an integer from 1 to 8; when d + e = 11, d is an integer from 2 to 10 and e is an integer from 1 to 9; when d + e = 12, d is an integer from 2 to 11 and e is an integer from 1 to 10; when d + e = 13, d is an integer from 2 to 12 and e is an integer from 1 to 11; when d + e = 14, d is an integer from 2 to 13 and e is an integer from 1 to 12;

11. - A laundry method for soiled fabrics comprising the step of contacting said soiled fabrics with an effective amount of a composition according to claim 1 in an aqueous solution.