MXPA00003528A - Mixed surfactant system - Google Patents

Abstract

Surfactant system mixtures of mid-chain branched primary alkyl sulfate surfactants useful in cleaning compositions, especially for lower water temperature applications, formulated with higher levels (above about 20%) of linear alkyl benzene sulfonate and low levels of cationic surfactants.

Description

MIXED SYSTEM OF SURGICAL AGENT FIELD OF THE INVENTION The present invention relates to mixed surfactant system useful in laundry and cleaning compositions, especially granular and liquid detergent compositions, which comprise medium chain branched primary alkyl sulfate surfactants, alkylbenzene sulfonate surfactants and cationic surfactants. in select relative proportions. Conventional detersive surfactants comprise molecules having a water solubilizing 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 bonded to a hydrophobic alkyl, alkenyl or alkaryl containing usually from 10 to about 20 carbon atoms. Accordingly, the manufacturer of such surfactants must have access to a source of hydrophobic groups to which the desired hydrophilic can be attached through chemical means. The first source of the hydrophobic groups comprised natural fats and oils, which were converted into soaps (ie, carboxylate hydrophilic) by saponification with the base. Coconut oil and palm oil are still used in soap making, as well as for the preparation of the class of alkyl sulfate surfactants ("AS"). Other hydrophobes are available from alkylbenzenesulfonate ("LAS") surfactants. In more recent times, it has been found that certain relatively long chain alkyl sulfate compositions containing medium chain branching are preferred for use in laundry products, especially under washing conditions with cold or ice water (eg 20 ° C). 5 ° C). These medium chain branched primary alkyl sulfate surfactants, which provide a surfactant mixture which is higher in surfactant and have better solubility in water at low temperature than the linear alkyl sulfate, can be combined in an appropriate manner with one or more of the other agents traditional surfactants (for example other primary alkyl sulphates, linear alkylbenzene sulphonates, ethoxylated alkyl sulfates, nonionic surfactants, etc.) to provide improved surfactant systems. However, it has been determined that such surfactant systems containing high levels of alkylbenzene sulfonates (greater than about 20% by weight of the alkylbenzene sulfonate mixture and the medium chain branched alkyl ester) are not optimal in cleaning performance. It has been surprisingly determined that the cleaning performance of the surfactant systems comprising these medium chain branched primary alkyl sulfate surfactants having more than 14.45 carbon atoms in combination with higher levels of linear alkylbenzenesulfonate surfactant can be improved additionally by including lower levels of cationic surfactant in those surfactant systems.

PREVIOUS TECHNIQUE U.S. Patent 3,480,556 to Witt et al, November 25, 1969, EP 439,316 published July 31, 1991, and EP 684,300 published November 29, 1995 and U.S. Patents 5,245,072, 5,284,989 , 5,026,933, 3,480,556 and 4,870,038 RG Laughlin in "The Aqueous Phase Behavior of Surfactants", Academic Press, N.Y. (1994) p. 347. 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 November 23, 1989, U.S. Patent 4,102,823 and U.S. Patent GB 1,399,966, U.S. Patent 1,299,966, Matheson et al, published July 2, 1975. EP 401,462 A, assigned to Henkel, published on December 12, 1990. See also KR Wormuth and S. Zushma, Langmuir, Vol. 7, (1991), pp 2048-2053, R. Varadaraj et al., J. Phys. Chem., Vol. 95, (1991), pp. 1671, Varadaraj et al, Collloid and Interface Sei., Vol. 140 (1990), pp31-34, and Varadaraj et al., Langmuir, Vol. 6 (1990), pp 1376-1378.

The "Linear Guerber" alcohols are available with Henkel, for example EUTANOL G-16. See also Surfactant Science Series, Marcel Dekker, N.Y. (Several volumes include those entitled "Anionic Surfactants" and "Surfactant Biodegradation", the latter from RD Swiser, Second Edition, published in 1987 as Vol. 18, see especially page 20"Primary Alkyl Sulfates" and pp 35-36"Secondary Alkyl Sulfates "); and CEH Marketing Research Report "Detergent Alcohols" by R.F. Modler et al., Chemical Economics Handbook, 1993, 609.5002; Kirk Othemer's Encyclopedia of Chemical Technology, 4th Edition, Wiley, N.Y., 1991, "Alcohols, Higher Aliphatic" in Vol. 1, pp 865-913 and references thereto.

BRIEF DESCRIPTION OF THE INVENTION The present invention relates to cleaning compositions comprising surfactant systems comprising: a) from about 80% to 99% (preferably from about 85% to about 99%, more preferably from about about 90% to about 99%, and even more preferably from about 92% to about 98%) by weight of an anionic co-active mixture of branched medium chain alkyl sulphates and linear alkylbenzene sulphonates, wherein said mixture comprises : i) about 35% up to about 80% by weight of this anionic co-active mixture, of branched medium chain alkyl sulfates having the formula: R Rl R ^ I I I CH3CH2 (CH2) wCH (CH ^ xCH (CH,) and CH (CH -,) zOS? 3M wherein the total number of carbon atoms in the primary branched alkyl portion of this formula (which includes the branch R, R1 and R2) is from 14 to 20 and wherein in addition to this mixture of surfactant the total average number of atoms carbon in the primary branched alkyl portions having the above formula is within the range of more than 14.5 to 18 (preferably greater than 14.5 to about 17.5, more preferably from about 15 to about 17); R, R1 and R2 are each independently selected from hydrogen and C1-C3 alkyl (preferably methyl), provided that R, R1 and R2 are not all hydrogen and, when z is 1, at least R or R1 is not hydrogen; M is one or more cations; 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 (preferably less than about 80% of the alkyl sulfates have a total of 18 carbon atoms in the alkyl chain); and ii) from about 20% to about 65% by weight of this anionic cotensioactive mixture of C10-C16 linear alkyl benzene sulphonate; and (b) from about 1% to about 20% (preferably from about 1% to about 15%, more preferably from about 1% to about 10%, and more preferably from about 2% to about 8% ) of one or more cationic surfactant coagents, preferably C8-C14 cationic surfactants coagents. These cleaning compositions preferably comprise from about 0.1% to about 99.9% (preferably from about 1% to about 50%) by weight of the surfactant weight system and from about 0.1 to about 99.9% (preferably from about 1%). % up to about 50%) by weight of one or more adjunct ingredients of the cleaning composition. Preferably, said cleaning compositions comprise a mixture of medium chain branched primary alkyl sulfate surfactants, wherein said mixture comprises at least about 5% by weight of two or more medium chain alkyl sulphates having the formula: CH3 CH3 (CH2) aCH (CH2) jCH2 OSOjM (I) CH3 CH3 CH3 (CH2) dCH (CH2) e CHCH2 OSO3M (II) or mixtures thereof, wherein M represents one or more cations; a, bd, 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 up 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 for this surfactant mixture the average total number of carbon atoms in the branched primary alkyl portions having the above formulas are within the scale of greater than 14.5 to about 18. Such compositions may include branched chain alkyl sulfate compounds Average of the formula: CH3 CH3 (CH2) aCH (CH ^ CH; OSO3M where: a and b are integers and where a + b is 12 or 13, a is an integer from 2 to 11, b is an integer from 1 to 10 and M is selected from sodium, potassium, ammonium and substituted ammonium. The most preferred embodiments of such compounds include an alkyl sulfate compound of said formula wherein M is selected from sodium, potassium and ammonium. Other medium chain alkyl sulfate compounds that may be included have the formula: CH3 CH3 CH3 (CH2) dCH (CH2) e CHCH2 OSO3M where d and e are integers and d + e is from 10 or 11; and where also when d + e = 10, d is an integer from 2 to 9 and e is an integer from 1 to 8; when d + e = 8, d is an integer from 2 to 10 and e is an integer from 1 to 9; and M is selected from sodium, potassium, ammonium and substituted ammonium, more preferably sodium, potassium and ammonium, more preferably sodium. The present invention also relates to a method for cleaning fabrics comprising contacting a fabric in need of cleaning with an aqueous solution of a cleaning composition as described herein. All percentages, ratios and proportions herein are given by weight, unless otherwise specified. All temperatures are in degrees Celsius (° C) unless otherwise specified. All documents cited in the relevant part are incorporated herein by reference.

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to mixtures of surfactant people comprising medium chain branched alkyl sulfate surfactants, linear alkyl benzene sulphonate surfactants and cationic surfactants, and to cleaning compositions containing such surfactant systems. For the purposes of that invention, it is recognized that other surfactants may be optionally present in the surfactant system according to the present invention, such as nonionic surfactants (alkyl ethoxylates) and other anionic surfactants (e.g. linear alkyl sulfate). Such optional surfactants are described in greater detail hereinafter. However, for the purposes of calculating the relative amounts of the essential components of the mixtures of the surfactant system herein, only the weight of those essential components in the surfactant system are considered. Therefore, the anionic cosentioactive mixture of the medium chain branched alkyl sulphates and the linear alkyl benzene sulphonates comprise from about 80% to about 99% (more preferably from about 92% to about 98%) by weight of the total weight of those essential surfactants plus the essential cationic surfactant. Any optional surfactants present are not included in this total weight). The cationic surfactant therefore comprises from about 1% to about 20% >; (more preferably from about 2% to about 8%) by weight of the total weight of the essential surfactants.

In addition, the essential anionic surfactants are combined in selected proportions related to each other. With respect to the total weight only of the essential medium chain branched alkyl sulfate and the linear alkylbenzene sulfonate, the medium chain branched alkyl sulphate is present in the compositions of this invention from about 35% to about 80%. The linear alkylbenzene sulfonate is present from about 20% to about 65% by weight of the total weight of the essential anionic surfactants.

Medium Chain Branched Alkyl Sulfate The branched surfactant compositions comprise one or more, preferably two or more, medium chain branched primary alkyl sulfate surfactants having the formula: R Rl R2 I CH3CH2 (CH2) wCH (CH2)? CH (CH2) and CH (CH2) 2pS03M The surfactant mixtures of the present invention comprise molecules having a linear primary alkyl sulfate chain structure (ie, the longest linear carbon chain that includes the sulfated carbon atom). These alkyl chain structures 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 a total number of carbon atoms for the branched primary alkyl portions within the scale greater than 14.5 to about 18. Thus, the mixtures of the present invention comprise at least one agent compound branched primary alkyl sulfate surfactant having a larger linear carbon chain of not more than 12 carbon atoms or more than 19 carbon atoms, and the total number of carbon atoms included in the branch must be at least 14 and furthermore the total average number of carbon atoms for the branched primary alkyl chain is within the range of more than 14. 5 to about 18. For example, a C16 total carbon alkyl primary sulfate surfactant having 13 atoms Carbon in the structure must have 1, 2 or 3 branching units (ie, R, R1 and / or R2) so the total number of carbon atoms in the mole molecule is at least 16. In this example, the total carbon requirement may also be met C16 having for example a propyl branching unit or three methyl branching units. R, R1 and R2 are each independently selected from hydrogen and C? -CS alkyl (preferably hydrogen or C? C alkyl ?, more preferably hydrogen or methyl and more preferably methyl), provided that R , R1 and R2 are not all hydrogen. In addition, when z is 1 at least R or R1 is not hydrogen. Although for the purposes of the present invention the surfactant compositions of the above formula do not include molecules wherein the R, R1 and R2 units are all hydrogen (ie, linear unbranched primary alkyl sulphates, it is recognized that the present invention may even comprise some amount of linear unbranched primary alkyl sulfate In addition, this primary unbranched alkyl sulfate surfactant may be present as a result of the process used to make the surfactant mixture having the requirement of one or more alkyl medium chain branched primary sulfates according to the present invention or the purposes of formulating detergent compositions with some amount of linear unbranched primary alkyl sulfate which can be mixed into the formulation of the final product.It is likewise recognized that no branched alcohol medium chain no s Ulphated can comprise some amount of the compositions of the present invention. Such materials may be present as a result of the incomplete sulphation of the alcohol used to prepare the alkyl sulfate surfactant, or those alcohols can be added separately to the present detergent compositions of the invention together with a medium chain branched alkyl sulfate surfactant according to the present invention. M is hydrogen or a salt formation cation depending on the synthesis method. Examples of salt-forming cations are lithium, sodium, potassium, calcium, magnesium, quaternary alkyl amines having the formula RJ! R6- N-R4 I. R ^ wherein R 3, R 4 R 5 and R 2 are independently hydrogen, 0 ^ 022 alkylene, branched C 4 -C 22 alkylene > C?-C6 alkanol, CÍ-C22 alkenylene, branched C 4 -C 22 alkenylene, and mixtures thereof. The preferred cations are ammonium (R3, R4, R5 and R6 equal to hydrogen), sodium, potassium, mono-, di-, and trialcanol ammonium, and mixtures thereof. The monoalkanol ammonium compounds of the present invention have R3 equal to alkanol of C ^ Ce, R4, R5 and R6 equal to hydrogen; Dialkanol ammonium compounds of the present invention having R3 and R4 equal to alkanol d-Cß. R5 and R6 equal to hydrogen, trialkanol ammonium compounds of the present invention have R3, R4 and R5 equal to alkanol of d-Ce. R6 are equal to hydrogen. The preferred alkanol ammonium salts of the present invention are quaternary mono- and di-triaminium compounds having the formulas: H3N + CH2CH2OH, H2N + (CH2CH2OH) 2, HN + (CH2CH2OH) 3 preferably M is sodium, potassium , and the C2 ammonium alkanol salts listed above, more preferred is sodium. With respect to the above 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; yw + x + y + z is an integer from 8 to 14. Certain branch points (ie, the location along the chain of the portions R, R1 and / or R2) are preferred over other branch points to along the structure of the surfactant. The following formula illustrates the average chain branching scale (ie, where the branching points are), the preferred medium chain branching scale and the most preferred medium chain branching scale for substituted mono alkyl sulphates of mono methyl the present invention. scale and ram and chain me It should be noted that the substituted monomethyl surfactants of those scales include two terminal carbon atoms of the chain and two carbon atoms immediately adjacent to the sulfate group. For surfactant mixtures comprising two or more of R, R1 or R2, the alkyl branching at the second carbon atom is within the scope of the present invention. The surfactants having longer chains than ethyl (ie, C3 alkyl substituents) on the second carbon atom, however, are less preferred. The following formula illustrates the average chain branching range, preferably the medium chain branching range and more preferably the medium chain branching range for linear dimethyl substituted alkyl sulphates of the present invention. • scala ram e e chain When the substituted dialkyl primary alkyl sulphates are combined with branched mono-substituted half-chain alkyl sulphates, the substituted dialkyl primary alkyl sulphates having one methyl substitution on the second carbon position and another methyl substitution on the preferred scale as it was indicated before, being within the present invention. Preferred surfactant blends of the present invention have at least 0.001%, more preferably at least 5%, most preferably at least 20% by weight of the RI R2 I CH3CH2 (CH2)? CH (CH2) and CH (CH7) zOS? 3M wherein the total number of carbon atoms, including the branching, is from 15 to 18, and wherein in addition to this surfactant mixture the average total number of carbon atoms in the primary branched alkyl portions having the above formula are within the scale of more than .14.5 to approximately 18; R and R2 are each independently hydrogen or d-C3 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, provided that R1 and R2 are not both hydrogen. More preferred compositions having at least 5% of the mixture comprising one or more medium chain primary alkyl sulfates wherein x + y is equal to 9 and z is equal to 2. Preferably, the surfactant mixtures comprise at least minus 5% of a branched primary chain alkyl sulfate having R1 and R2 independently hydrogen, methyl, provided that R1 and R2 are not both hydrogen; x + y is equal to 8, 9 or 10 and z is at least 2. More preferably, the mixtures of the surfactants comprise at least 20% of branched primary chain alkyl sulfate having R1 and R2 independently hydrogen , methyl, provided 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 the medium chain branched alkyl sulfate surfactants, said mixture comprising at least about 5% by weight of two or more branched chain alkyl sulphates having the formula: CH3 CH3 (CH2) aCH (CH2) bCH2 OSO, M (I) CH3 and CH3 CH3 (CH2) dCH (CH2) and CH CH2 OSOjM (II) 0 mixtures thereof, wherein M represents one or more cartons; a, bd, 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 up 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 in addition for this surfactant mixture the average total number of carbon atoms in the branched primary alkyl portions having the above formulas is within the scale greater than 14.5 to about 18. In addition the surfactant composition of the present invention may comprise a branched primary alkyl sulfate mixture having the formula R Rl R2 I I I CH3CH (CH -,) wCH (CH?) XCH (CH -,) vCH (CH -.) 2OS? 3M wherein the total number of carbon atoms per molecule, including the branches from 14 to 20, and wherein in addition to this surfactant mixture the total average number of carbon atoms in the branched primary alkyl portions having the above formula is within from the scale of more than 14.5 to about 18. R, R1 and R2 are each independently selected from hydrogen and d-C3 alkyl, provided 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 11 and w + x + y + z is from 8 to 14, provided that when R2 is an alkyl of d-C3, the ratio of agents surfactants having z equal to 1 to surfactants having z equal to 2 or more is at least about 1: 1, preferably at least 1: 5, more preferably at least about 1:10 and most preferably about 1: 100. The surfactant compositions are also preferred, when R2 is a C1-C3 alkyl, comprising less than about 20%, preferably less than 10%, more preferably less than 5%, more preferably less than 1% of primary alkyl sulphates branched having the above formula wherein z is equal to 1. The present invention further relates to novel branched primary alkyl sulfate surfactants having the formula Rl R2 I I CH3CH2 (CH2)? CH (CH7) and CH (CH,) 2OS? 3M wherein R and R2 are each independently hydrogen or C-C- alkyl, M is a water-soluble cation; x is an entry from 0 to 12; and is an integer from 0 to 12; z is an integer of at least 2 and x + y + z is from 11 to 14; on condition that. a) R1 and R2 are not both hydrogen; b) when one R1 or R2 is hydrogen and the other of R1 or R2 is methyl, then x + y + z is not 12 or 13; and c) when R1 is hydrogen and R2 is methyl, x + y is not 11 when z is 3, and x + y is not 9 when z is 5. The units R1 and R2 are independently selected from hydrogen or C- alkyl. ? -C3 (preferably hydrogen or C? -C2 alkyl?; more preferably hydrogen or methyl) provided that R and R1 are not both hydrogen. M is as defined above. For the medium chain branched alkyl sulphates of the present invention having more than one alkyl branching chain, the alkyl branching structures comprise from 12 to 18 carbon atoms. The maximum number of carbon atoms comprising the medium chain branched alkyl sulphates of the present invention including all branches is 20 carbon atoms. The preferred novel medium chain branched alkyl sulfate compounds have the formula: CH3 CH3 (CH2) aCH (CH) bCH2 OSO3M where a and b are integers and a + b is 12 or 13, a is an integer from 2 to 11, b is an integer from 1 to 10 and M is selected from sodium, potassium, ammonium and substituted ammonium. More preferred embodiments of such compounds include an alkyl sulfate compound of the formula wherein M is selected from sodium, potassium and ammonium. Also the preferred novel medium chain modified alkyl sulfate compounds have the formula CH3 CH3 CH3 (CH2) dCH (CH2) eCHCH2 OSO3M where d and e are integers and d + e is 10 or 11; and where also 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; and M is selected from sodium, potassium, ammonium and substituted ammonium, more preferably sodium, potassium and ammonium, more preferably sodium. The branched primary mono-methylalkyl sulphates are selected from the group consisting of: 3-methyl pentadecanol sulfate, 4-methyl pentadecanol sulfate, 5-methyl pentadecanol sulfate, 6-methyl pentadecanol sulfate, 7-methyl sulfate, methyl pentadecanol, 8-methyl pentadecanol sulfate, 9-methyl pentadecanol sulfate, 10-methyl pentadecanol sulfate, 11-methyl pentadecanol sulfate, 12-methyl pentadecanol sulfate, 13-methyl pentadecanol sulfate, 3-methyl sulphate methylhexadecanol, 4-methylhexadecanol sulfate, 5-methylhexadecanol sulfate, 6-methylhexadecanol sulfate, 7-methylhexadecanol sulfate, 8-methylhexadecanol sulfate, 9-methylhexadecanol sulfate, 10-methylhexadecanol sulfate, 11-methylhexadecanol sulfate, 12-methylhexadecanol sulfate, 13-methylhexadecanol sulfate, 14-methylhexadecanol sulfate, and mixtures thereof. The branched dimethyl primary alkyl sulphates are selected from the group consisting of 2,3-methyl-tetradecanol sulfate, 2,4-methyl-tetradecanol sulfate, 2,5-methyl-tetradecanol sulfate, 2-sulphate, 6-methyl-tetradecanol, 2,7-methyl-tetradecanol sulfate, 2,8-methyl-tetradecanol sulfate, 2,9-methyl-tetradecanol sulfate, 2,10-methyl-tetradecanol sulfate, 2-sulphate, 11-methyl-tetradecanol, 2, 12-methyl-tetradecanol sulfate, 2,3-pentadecanol sulfate, 2,4-methyl-pentadecanol sulfate, 2,5-methyl-pentadecanol sulfate, 2,6- sulphate methyl-pentadecanol, 2,7-methyl-pentadecanol sulfate, 2,8-methyl-pentadecanol sulfate, 2,9-methyl-pentadecanol sulfate, 2,10-methyl-pentadecanol sulfate, 2,11-methyl sulfate methyl-pentadecanol, 2,2-methyl-pentadecanol sulfate, 2,13-methyl-pentadecanol sulfate, and mixtures thereof. The following branched primary alkyl sulphates comprise 16 carbon atoms and have a branching unit and are examples of the preferred branched surfactants useful in the compositions of the present invention: 5-methylpentadecylsulfate having the formula: 6-methylpentadecyl sulfate having the formula: 7-methylpentadecylsulfate having the formula: 8-methylpentadecyl sulfate that has the formula: 9-methylpentadecyl sulfate having the formula: 1 O-methylpentadecyl sulfate 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 the preferred 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: wherein M is preferably sodium. Preparation of Branched Middle Chain Alkyl Sulphates The following reaction scheme details a general approach for the preparation of medium chain branched alkyl sulphates of the present invention. o ov M? D, v Cl ((C (- HH?; B) J __ (C-cCHH3J HH33C? ° TH "Ac20? RX? - RMgX -_ _, _. RR-_C- (CH:) 3CI 1» R_C - (CH:) 3a ¿H3 ¿H3 ; ? HOAc (CH3b a An alkyl halide is converted to a Grignard reagent and the Gringnard reagent is reacted with haloketone. After conventional acid hydrolysis, acetylation and thermal removal of acetic acid, olefin (not shown in the scheme) is produced which is hydrogenated using any hydrogenation catalyst such as Pd / C. This is favorable over others in the branching, in this illustration a 5-methyl branching is introduced in a timely manner in the reaction sequence. The formylation of the alkyl halide results from the first hydrogenation step that produces the alcohol product as shown in the scheme. This can be sulfated using any convenient sulfation agent, eg, chlorosulfonic acid, air / SO3, or oil, to produce the final branched primary alkyl sulfate surfactant. There is flexibility to extend the branching of an additional branch beyond what is achieved by an individual formulation. Such an extension can, for example, be achieved by reaction with ethylene oxide. See "Gringnard Reactions of Nonmetallic Substances", M.S. Karaxch and O. Reinmoth, Prentice-Hall, N.Y., 1954; J. Org. Chem., J. Cason and W.R. Winans, Vol. 15 (1950), pp. 139-147; J. Org. Chem. J. Cason et al., Vol. 13 (1948), pp 239-248; J. Org. Chem., J. Cason et al., Vol. 14 (1949), pp 147-154; and J. Org. Chem. J. Cason et al., Vol. 15 (1950), pp. 135-138 all of which are incorporated by reference herein. In variations of the above procedure, alternate haloketones or Gringnard reagents can be used. Halogenation PBr3 of alcohol from formylation or ethoxylation can be used to achieve interactive chain extensions. The preferred medium chain branched alkyl sulphates of the present invention can also be easily prepared as follows: (P) 3 P -Br ^ CH3CV (PhftP * (Ph) 3P < A conventional bromoalcohol is reacted with triphenylphosphine followed by sodium hydride, suitably in dimethylsulfoxide / tetrahydrofuran, to form a Wittig adduct. The Wittig adduct is reacted with an alpha methyl ketone, forming an alcoholate branched by internally unsaturated methyl. The hydrogenation followed the sulfation which produces the desired branched primary chain alkyl sulphate. Although the Wittig approach does not allow the practitioner to extend the hydrocarbon chain, according to the Grignard sequence, the Wittig typically achieves higher productions. See Agricultural and Biological Chemistry, M. Horiike et al., Vol. 42 (1978), pp 1963-1965 included herein by reference. The alternative synthetic process according to the invention can be used to prepare the branched primary alkyl sulphates. The medium chain branched alkyl sulphates can further be synthesized formulated in the presence of conventional homologs, for example to any of those that can be formed in an industrial process that produces the 2-alkyl branching as a result of hydroformylation. The medium chain branched surfactant mixtures of the present invention are routinely added to other known commercial alkyl sulfates contained in the final laundry product formulation. In certain preferred embodiments of the surfactant mixtures of the present invention, especially those derived from a fossil fuel source involving commercial processes, they comprise at least 1 medium chain branched primary alkyl sulfate, preferably at least 2, more preferably at least 5, more preferably at least 8. Particularly suitable for the preparation of certain Mixtures of surfactant of the present invention are "oxo" reactions wherein a branched chain olefin is subject to catalytic isomerization and hydroformylation prior to sulfation. Preferred processes resulting in such mixtures use fossil fuels such as the starting material. Preferred processes utilize the Oxo reaction in linear (alpha or internal) olefins with a limited amount of branching. Suitable olefins can be made by dimerization of linear or internal alpha olefins, by controlled oligomerization of linear olefins of low molecular weight by structural rearrangement of the detergent-scale olefins by dehydrogenation / rearrangement of the detergent-scale paraffin structure or by Fischer-Tropsch reaction. Those reactions will generally be controlled to: 1) give a large proportion of olefins in the desired detergent scale (while allowing the addition of one carbon atom in the subsequent Oxo reaction). 2) produces a limited number of branches, preferably of medium chain, 3) produces branches d-C3, more preferably ethyl, more preferably methyl, 4) limit or eliminate the gem branch of alkyl, that is, to avoid the formation of atoms of quaternary carbon.

Suitable olefins can withstand the Oxo reaction to give primary alcohols either directly or indirectly through corresponding aldehydes. When an internal olefin is used, an Oxo catalyst is normally used which is capable of pre-isomerization before the internal olefins mainly for alpha olefins. While an internal isomerization to alpha catalysed separately (ie it is not Oxo) could be done, this is optional. On the other hand, in the olefin formation stage, it results directly in an alpha olefin (for example, with Fischer-Tropsch high pressure olefins of the detergent range), then the use of a Oxo catalyst of somerization is not only possible but favorite. The outline below summarizes this process. I H2, CO i | The process described herein gives 5-methyl-hexadecyl sulfate in greater proportion than the less preferred 2,4-dimethylpentadecyl sulfate. This mixture is desirable under the bonds and bonds of the present invention in that each product comprises a total of 17 carbon atoms with linear alkyl chains having at least 13 carbon atoms. The following examples provide methods for synthesizing various compounds useful in the compositions of the present invention. EXAMPLE 1 Preparation of 7-methylhexadecyl sodium sulfate Synthesis of bromide (6-hydroxy-hexyl) triphenylphosphonium 6-bromo-1-hexanol (500 g, 500 g) was added to a 5L triple-necked round bottom flask equipped with nitrogen inlet, condenser, thermometer, mechanical stirrer and nitrogen outlet. 2.76 mol), triphenylphosphine (768 g, 2.9 mol) and acetonitrile (1800 ml) under nitrogen. The reaction mixture was heated to reflux for 72 hours. The reaction mixture is cooled to room temperature and transferred to a 5L laboratory beaker. The product is recrystallized from the anhydrous ethyl ether (1.5L) at 10 ° C. Vacuum filtration followed by washing with ethyl ether and drying in a vacuum oven at 50 ° C for 2 hours, produces 1140 g of the desired product as white crystals. Synthesis of 7-methylhexadecene-1-ol In a 5-L 3-neck round bottom flask equipped with mechanical stirring, nitrogen inlet, dropping funnel, thermometer and nitrogen outlet were added 70.2 g of 60% sodium hydride ( 1.76 mol) in mineral oil. The mineral oil is removed by washing with hexanes. The anhydrous dimethyl sulfoxide (500ml) is added to the flask and the mixture is heated to 70 ° C until the hydrogen evolution stops. The reaction mixture is cooled to room temperature followed by the addition of a 1L tetrahydrofuran anhydide (6-hydroxyhecyl) triphenylphosphonium bromide (443.4g, 1 mol) is formed in hot anhydrous condimethyl sulfoxide paste (50 ° C, 500ml) and It is added slowly to the reaction mixture through the dropping funnel while maintaining it at 25-30 ° C. the mixture is stirred for 30 minutes at room temperature at which time 2-undecanene (187g, 1.1 mol) is slowly added through a dropping funnel. The reaction is slightly exothermic and it needs to be cooled to maintain it at 25-30 ° C. The mixture is stirred for 18 hours and then poured into a 5L laboratory beaker containing 1L of purified water with stirring. The oil phase (upper) is allowed to separate in a separatory funnel and the water phase is removed. The water phase is washed with hexanes (500ml) and the organic phase is separated and combined with the oil phase from washing with water. The organic mixture is then extracted with 3 times water (500ml each) followed by vacuum distillation to collect the transparent oil product (132g) at 140 ° C and 1mm Hg. Hydrogenation of methylhexadene-1-ol In a 3L lined rotary autoclave was added 7-methylhexadecene-1 -ol (130g, 0.508 mol), methanol (300ml) and platinum on carbon (10% by weight, 35). the mixture is hydrogenated at 180 ° C under 1200 psig of hydrogenation for 13 hours cooled and filtered under vacuum through Celite 545 with washing of Celite 545 in an appropriate manner with methylene chloride. If required, the filtration can be repeated to remove the traces of the Pt catalyst and the magnesium sulfate can be used to dry the product. The product solution is concentrated in a rotary evaporator to obtain a clear oil (124g). Sulfation of 7-methylhexadecanol In a dry 1L 3-necked round-bottomed flask equipped with a nitrogen inlet, dropping funnel, thermometer, mechanical agitation and nitrogen outlet, chloroform (300ml) and 7-methylhexadecanol (124g, 0.484) are added. mol). Chlorosulfonic acid (60g, 0.508 mol) is added slowly to the stirred mixture while maintaining it at 25-30 ° C with an ice bath. Once the evolution of HCl is stopped (1 hr), sodium methoxide (25% in methanol) is added slowly in a tank, the temperature is maintained at 25-30 ° C until an aliquot at 5% concentration in water maintains a pH of 10.5. Hot ethanol is added to the mixture. The mixture is filtered under vacuum immediately. The filtrate is concentrated to a paste in a rotary evaporator, cooled and then poured into 2L of ethyl ether. The mixture is frozen at 51 ° C at which point crystallization occurs and is filtered under vacuum. The crystals are dried in a vacuum oven at 50 ° C for 3 hours to obtain a white solid (136g, 92% activated by SO3 cat titration).

EXAMPLE II Synthesis of 7-methylpentadecyl sodium sulfate Synthesis of (6-hydroxyhexyl) Trifenylphosphonium Bromide In a 5-L round 3-necked flask equipped with nitrogen inlet, condenser, thermometer, mechanical stirring and nitrogen outlet is added 6-bromo-1-hexanol (500g, 2.76 mol) , triphenylphosphine (768g, 2.9 mol) and acetonitrile (1800 ml) under nitrogen. The reaction mixture is heated to reflux for 72 hours. The reaction mixture was cooled to room temperature and transferred into a 5L laboratory beaker. The product is recrystallized from anhydrous ethyl ether (1.5L) at 10 ° C. Filtration of the mixture followed by washing the white crystals with ethyl ether and drying in a vacuum oven at 50 ° C for 2 hours gives 1140 g of the desired product. Synthesis of 7-methylpentadecen-1-ol In a 5-L 3-neck round bottom flask equipped with mechanical stirring, nitrogen inlet, dropping funnel, thermometer and nitrogen outlet is added 80g of 60% sodium hydride (2.0 mol) in mineral oil. The mineral oil is removed by washing with hexanes. The dimethyl sulfoxide anhydride (500 ml) is added to the flask and heated to 70 ° C until the hydrogen evolution stops. The reaction mixture in cooled to room temperature followed by the addition of 1L of anhydrous tetrahydrofuran (6-hydroxyhexyl) triphenylphosphonium bromide (443.4g, 1 mole) is formed into paste with anhydrous dimethyl sulfoxide (50 ° C, 500 ml) and Add slowly to the reaction mixture through the dropping funnel while maintaining the reaction at 25-30 ° C. The reaction is stirred for 30 minutes at room temperature at which time 2-decanene (171.9g, 1.1 mol) is slowly added through a dropping funnel. The reaction is slightly exothermic and cooling is needed to maintain at 25-30 ° C. The mixture is stirred for 18 hours and then poured into a separatory funnel containing 600 ml of purified water and 300 ml of hexanes. After stirring the oil phase (upper) the water phase is allowed to separate and removed. The extractions of the oil phase are continued using water until both phases are transparent. The organic phase is collected, vacuum distilled and purified by liquid chromatography (90:10 hexanes: ethyl acetate, silica gel stationary phase) to obtain a clear oil product (119.1g).

Hydrogenation of 7-methylpentadecen-1 -ol In a 3L glass lined rotary autoclave (Autoclave Engineers), 7-methylpentadecen-1 -ol (122g, 0.508mol), methanol (300ml) and platinum in carbon (10% by weight) are added. weight, 40g). The mixture is hydrogenated at 180 ° C under 1200 psig of hydrogen for 13 hours, cooled and filtered under vacuum through Celite 545 with washing of Celite 545 with methylene chloride. The organic mixture is still dark from the platinum catalyst so that the filtration process is repeated with concentration on a rotary evaporator; The dilution is carried out with methylene chloride (500ml) and magnesium sulfate is added to dry the product. Filtering in vacuo through Celite 545 and concentration filtrate on a rotary evaporator to obtain a clear oil (119g). Sulfation of 7-methylpentadecanol A 3-neck dry 1L tube equipped with a nitrogen inlet, dropping funnel, thermometer, mechanical agitation and nitrogen outlet is added chloroform (300ml) and 7-methylpentadecan (199g, 0.496 mol). The chlorosulfonic acid (61.3g, 0.52 mol) is added slowly to the stirred mixture by keeping it at 25-30 ° C with an ice bath. Once the evolution of HCl has stopped (1 hr), sodium methoxide (25% in methanol) is slowly added while maintaining the temperature at 25-30 ° C until an aliquot at 5% concentration in water maintains a pH of 10.5. To the mixture is added methanol (1L) and 300 ml of 1-butanol. The vacuum filtration of the inorganic salt is precipitated and the methanol is removed from the filtrate on a rotary evaporator. It cools at room temperature, 1L of diethyl ether is added and left to stand for 1 hour. The precipitate is collected by vacuum filtration. The product is dried in a vacuum oven at 50 ° C for 3 hours to obtain a white solid (82g, 90% activated by titration of cat SO3) EXAMPLE III Synthesis of sodium 7-methylheptadecyl sulfate Synthesis Bromide of (6-Hydroxyhexyl) ) Triphenylphosphonium In a 5L 3-necked round bottom flask equipped with nitrogen inlet, condenser, thermometer, mechanical stirring and nitrogen outlet is added 6-bromo-1-hexanol (500g, 2.76 mol), triphenylphosphine (768g, 2.9) mol) and acetonitrile (1800 ml) under nitrogen.The reaction mixture is heated to reflux for 72 hours.The reaction mixture is cooled to room temperature and transferred to a 5L laboratory beaker.The product is recrystallized from ether Anhydrous diethyl ether (1.5L) at 10 ° C. Vacuum filtration of the mixture followed by washing the white crystals with diethyl ether and drying in a vacuum oven at 50 ° C. for 2 hours gives 1140g of the desired product. of 7-methylheptadecen-1-ol In a dry 5L 3-neck round bottom flask equipped with mechanical stirring, nitrogen inlet, dropping funnel, thermometer and nitrogen outlet is added 80g of 60% sodium hydride ( 2.0 mol in mineral oil. The mineral oil is removed by washing with hexanes. The anhydrous dimethyl sulfoxide (500ml) is added to the flask and heated to 70 ° C until the evolution of the nitrogen is stopped. The reaction mixture is cooled to room temperature followed by the addition of 1L of anhydrous tetrahydrofuran (6-hydroxyhexyl) triphenylphosphonium bromide (443.4g, 1 mol) with hot dimethyl sulfoxide anhydride (50 ° C, 500ml) and added to the Reaction mixture through the dropping funnel while maintaining the reaction at 25-30 ° C. the reaction is stirred for 30 minutes at room temperature at which time 2-dodecanone (184.3 g, 1.1 mol) is slowly added slowly through a dropping funnel. The reaction is slightly exothermic and is cooled if necessary to maintain at 25-30 ° C. The mixture is stirred for 18 hours and then poured into a separatory funnel containing 600ml of purified water and 300ml of hexanes. After shaking the alcohol phase (upper) it is allowed to separate and the water phase is removed which is turbid. The extractions are continued using water until the water phase and the organic phase become transparent. The organic phase is collected and purified by liquid chromatography (silica gel stationary phase, mobile phase hexanes to obtain a transparent oil product (116g) HNMR of the final product (in deuterium oxide) indicates a CH2-OSO3 + multiple band 3.8 ppm resonance CH2-CH2-OSO3 multiple band 1.5 ppm resonance CH2 of the alkyl chain in the resonance of 0.9-1.3 ppm resonance and branch point CH-CH3 overlapping the terminal methyl group R-CH2 -CH3 at 0.8 ppm resonance 7-methylheptadecen-1 -ol hydrochlorination In a 3L glass lined rotary autoclave (Autoclave Engineers) 7-Methylheptadecen-1 -ol (116g, 0.433mol) methanol (300ml) is added and platinum on carbon (10% by weight, 40g) The mixture is hydrogenated at 180 ° C under 1200 psig of hydrogen for 13 hours, cooled and vacuum filtered through Celite 545 with washing of Celite 545 with methylene chloride The vacuum filter through Celite 545 and the Concentration of the filtrate in a rotary evaporator are done to obtain a clear oil (108g). Sulfation of 7-methylheptadenacol In a 1L 3-necked round bottom flask equipped with a nitrogen inlet, dropping funnel, thermometer, mechanical stirring and nitrogen outlet is added chloroform (300ml) and 7-methylheptadecanol (102g, 0.378mol ). The chlorosulfonic acid (46.7g, 0.40 mol) is added slowly to the stirred mixture while maintaining it at 25-30 ° C with an ice bath. Once the evolution of HCl has stopped (1 hour), sodium methoxide is added slowly (25% in methanol) while the temperature is maintained at 25-30 ° C until an aliquot at 5% concentration in water maintains a pH of 10.5. Hot methanol (45 ° C, 1) is added to the mixture to dissolve the branched sulphate followed immediately by vacuum filtration to remove the inorganic salt precipitate and repeated a second time. The filtrate is then cooled to 5 ° C at which point 1 L of ethyl ether is added and allowed to stand for 1 hour. The precipitate is collected by vacuum filtration. The product is dried in a vacuum oven at 50 ° C for 3 hours to obtain a white solid (89g, 88% active by cat. SO 3 titration). HNMR of the final product (uterine oxide) indicates a CH2-OSO3 multiple band of 3.8 ppm resonance, CH2-CH2-OSO3-multiple band at 1.5 ppm resonance. CH2 of the alkyl chain at 0.9-1.3 ppm resonance and the branch point CH-CH3 which overlaps the terminal methyl group R-CH2-CH3 at 0.8 ppm resonance. The mass spectrometry data shows a molecular ion peak with a mass of 349.1 which corresponds to the 7-methylheptadecyl sulfate ion. As shown, it is the methyl branching in position 7 due to the loss of 29 mass units in that position. The following two analytical methods for characterizing the branching in the present invention are useful for surfactant compositions: 1) Separation and identification of Components in Fatty Alcohols (before sulfation or after hydrolysis of alcohol sulfate for analytical purposes) . The position and length of the branching found in the precursor fatty alcohol materials is determined by GC / MS techniques [see D.J. Harvey, Biomed. Environ. Mass Spectrom (1989), 18 (9), 719-23; D. J. Harvey, J. M Tiffany, J. Chromatogr, (1984), 301 (1), 173-87; K. A. Karlsson. B. E. Samuelsson, G. O. Steen, Chem. Phys. Lipids (1973), 11 (1), 17-38]. 2) Identification of Fatty Alcohol Sulphate Components Separated by MS / MS. The position and length of the branching can also be determined by spraying techniques of lon-MS / MS or FAB-MS / MS in previously isolated fatty alcohol sulfate components. The total carbon atoms on average of the branched primary alkyl sulphates herein can be calculated from the hydroxyl value of the precursor fatty alcohol mixture or from the hydroxyl value of the alcohols recovered by extraction after hydrolysis of the sulphate mixture. of alcohol according to common procedure in such as are determined in "Bailey's Industrial Oil and Fat Products", Volume 2, Fourth Edition, edited by Danil Swern, pp 440-441. Alkyl Benzene Sulfonate Linear Linear alkyl benzene sulfonate surfactants are well known. There are anionic surfactants selected from alkali metal salts of alkyl benzenesulfonic acids in which the alkyl group contains from about 10 to 16 carbon atoms, in straight or branched chain configuration. (See U.S. Patents 2,220,099 and 2,477,383 incorporated herein by reference). Especially preferred are linear straight-chain sodium and potassium alkyl benzene sulphonates (LAS) in which the average number of carbon atoms in the alkyl group is 10 to 14. The sodium Cn-C1 LAS is especially preferred. Cationic Surfactants Non-limiting examples of cationic surfactants useful herein typically at levels from about 0.1% to about 50% by weight include the choline ester quaternary compounds and the alkoxylated quaternary ammonium surfactant compounds (AQA ) and similar. The cationic co-surfactants useful as components of the surfactant system is the cationic choline ester-type surfactant which are preferably water-dispersible, more preferably water-soluble compounds having surfactant properties and comprising at least one ester (ie -COO-) in bond and at least one canonically loaded group. Suitable cationic ester surfactants include choline ester surfactants which have been described, for example, in U.S. Patent Nos. 4,228,042, 4,239,660 and 4,260,529. The preferred cationic ester surfactants are those having the formula wherein R1 is a linear or branched alkyl, alkenyl or alkynyl chain of C5-C31 or M + N + (R6R7R8) (CH2) S; X and Y independently, are selected from the group consisting of COO, OCO, O, CO, OCOO, CONH, NHCO, OCONH and NHCOO wherein at least one of X or Y is a group COO, OCO, OCOO, OCOHN or NHCOO; R2, R3, R, Re,? and R8 are independently selected from the group consisting of alkyl, alkenyl, hydroxyalkyl, hydroxyalkenyl and alkaryl groups having from 1 to 4 carbon atoms; and R5 is independently H or an alkyl group of d-C3; where the values of m, n, syt independently are located on the scale from 0 to 8, the value of b is located on the scale from 0 to 20, and the values of a, u and v independently are 0 or 1, with the condition that at least one of uov must be 1; and where M is a counter ion. Preferably, R2, R3 V R4 are independently selected from CH3 and -CH2CH2OH. Preferably M is selected from the group consisting of halide, methyl sulfate, sulfate and nitrate, more preferably methyl sulfate, chloride, bromide or iodide. Preferred water-dispersible cationic ester preferred agents are choline esters having the formula: wherein R ^ is a linear or branched alkyl chain of d? -C? 9.

Particularly preferred choline esters of this type include the quaternary methylammonium halides of steroyl-choline ester (R1 = C17 alkyl), quaternary methylammonium halides of palmitoyl-choline ester (R1 = C15 alkyl), quaternary methylammonium halides of myristoyl-choline ester (R1 = C13 alkyl), quaternary methylammonium halides of lauroyl-choline ester (R = Cu alkyl), quaternary methylammonium halides of cocoyl-choline ester (R1 = Cn.Cp alkyl), quaternary methylammonium halides of ceboyl-choline ester (R = C5-C-17 alkyl), and mixtures thereof. Particularly preferred choline esters given above can be prepared by direct esterification of a fatty acid of the desired chain length with dimethylaminoethanol in the presence of an acid catalyst. The reaction product is then quaternized with a methyl halide, preferably in the presence of a solvent such as ethanol, propylene glycol or preferably a fatty alcohol ethoxylate such as C 10 -C 18 fatty alcohol ethoxylate having a degree of ethoxylation from 3 to 10%. to 50 ethoxy groups per mole forming the desired cationic material. They can also be prepared by direct esterification of a long chain fatty acid of the desired chain length together with 2-haloethanol in the presence of an acidic catalyst material. The reaction product is then quaternized with trimethylamine, forming the desired cationic material.

Other suitable cationic ester surfactants have the following structural formulas wherein d may be from 0 to 20.

In a preferred aspect, those cationic ester surfactants are hydrolysable under conditions of a laundry washing method. The cationic co-surfactants useful herein include also quaternary ammonium ammonium surfactant (AQA) compounds (referred to herein as "AQA compounds") having the formula: wherein R1 is a linear or branched alkyl or alkenyl portion containing from about 8 to about 18 carbon atoms, preferably 10 to about 16 carbon atoms, more preferably about 10 to about 14 carbon atoms; R2 is an alkyl group containing from one to three carbon atoms, preferably methyl; R3 and R4 can vary independently and are selected from hydrogen (preferred), methyl and ethyl; X "is an anion such as chloride, bromide, methylsulfate, sulfate or the like, sufficient to provide electrical neutrality.A and A 'can vary independently and are each selected from d-C4 alkoxy, especially ethoxy (i.e. , -CH2CH20-) mixed propoxy, butoxy and ethoxy / propoxy, p is from 0 to about 30, preferably 1 to about 4 and q is 0 to about 30, preferably 1 to about 4 and more preferably from about 4; both p and q are 1. See also EP 2,084, published May 30, 1979 by The Procter &Gamble Company, which discloses cationic surfactant coagents of this type which are useful herein The AQA compounds of the hydrocarbyl substituent R is C8-Cn especially Cio, which improve the dissolution speed of the washing granules, especially under cold water conditions compared to the super-long chain materials Accordingly, the C8-Cn AQA surfactants may be preferred by some formulators. The levels of the AQA surfactants can be used to prepare the finished laundry detergent compositions can range from about 0.1% to about 5%, typically from about 0.45% to about 2.5% by weight. Accordingly, the following are non-limiting specific examples of AQA surfactants used herein. It should be understood that the degree of alkoxylation noted herein for the AQA surfactants is reported as an average, following common practice for conventional ethoxylated nonionic surfactants. This is because the ethoxylation reactions typically produce mixtures of materials with different degrees of ethoxylation. Therefore it is not uncommon to report total EO values different from the full numbers, for example "EO2.5", "EO3.5" and the like. Designation R1 R2 ApR3 A'gR4 AQA-1 (also referred to as Coconut Methyl EO2) Cl2"d CH3 EO EO AQA-2 C12-C1 ß CH3 (EO) 2 EO AQA-3 (Coconut Methyl EO4) C12-C14 CH3 (EO) 2 (EO) 2 AQA-5 C12-C1 CH3 (EO) 2 (EO) 3 AQA-6 Cl2"C? CH3 (EO) 2 (EO) 3 AQA-7 C8-C 18 CH3 (EO) 3 (EO) 2 AQA-8 Ci2"C? CH3 (EO) 4 (EO) 4 AQA-9 C? 2-C14 C2H5 (EO) 3 (EO) 3 AQA-10 Ci2"C? S C3H (EO) 3 (EO) 4 AQA-11 C 12" C- | 8 CH; propoxy (EO) 3 AQA-12 Ci oC) s C2H5 (? so-propoxy) 2 (EO) 3 AQA-13 Ci 0-C18 CH3 (EO / PO) 2 (EO) 3 AQA-14 C8-C18 CH3 (EO) 15 * (EO) 15 AQA-15 Cío CH3 EO EO AQA-17 C9-C1 and CH3-EO 3.5 Avg-AQA-18 C12 CH3-EO 3.5 Avg-AQA-19 C8-C? 4 CH3 (EO) 10 (EO)? Or AQA-20 of C2H5 (EO) ) 2 (EO), AQA-21 Cl2"C1 C2H5 (EO) 5 (EO) 3 AQA-22 C12-C18 C3H Bu (EO) 2 * Ethoxy, optionally blocked at the end with methyl or ethyl. The preferred bis-ethoxylated cationic surfactants herein are available under the trade name ETHOQUAD from Akzo Nobel Chemicals Company. The highly preferred bis-AQA compounds for use herein are of the formula Rl .CH.CH.OH T -iV X CH3 'CHoCH, OH wherein R1 is C10-C18 hydrocarbyl and mixtures thereof, preferably C10, C12, C14 alkyl, and X is any convenient anion to provide charge equilibrium, preferably chloride. With reference to the general AQA structure noted above, since in a preferred compound R1 is derived from coconut (C12-C14 alkyl) the fatty acids of the fraction, R2 is methyl and ApR3 and A'qR4 are each monoethoxy, this preferred type of compound is preferred herein as "CocoMeEO2) or" AQA-1"in the above list Other preferred AQA compounds include compounds of the formula: wherein R is C 10 -C 18 hydrocarbyl, preferably C 1 or C 14 alkyl, independently p is 1 to about 3 and q is 1 to about 3, R 2 is d-C 3 alkyl, preferably methyl, and X is an anion, especially chloride. Other compounds of the above type include those in which the ethoxy (CH2CH2O) (EO) units are replaced by butoxy (Bu), isopropoxy [CH (CH3) CH2O] and units [CH2CH (CH3O] (l-Pr) or n-units propoxy (Pr), or mixtures of EO and / or Pr and / or i-Pr units. The additional cationic co-surfactants described, for example in "Surfactant Science Series, Volume 4, Cationic Surfactants" or in "Industrial Surfactants Handbook The classes of cationic surfactants useful in such references include quaternary amide compounds (ie, Lexquat AMG &Schercoquat CAS) glycidyl ether quaternary compounds (ie, Cyostat 609), polypropoxy quaternary compounds (Emcol CC-9). ), alkylammonium cyclic compounds (ie, pyridinium or imidazolinium quaternary compounds) and / or benzoalkonium quaternary compounds It is noted that the formulation of the compositions of the present invention may involve simple mixing of the ingredients e) surfactant agent or the pre-formation of a complex of these co-cationic surfactants with one or more of the anionic surfactants, as well as any other method of forming the surfactant systems. Next, several additional ingredients that may be used in the compositions of this invention are illustrated, but are not intended to be limited thereto. While the combination of the surfactant system with the additional compositional ingredients can be provided as finished products in the form of liquids, gels, sticks or the like using conventional techniques, the manufacture of granular laundry detergents herein requires some special processing in order to achieve optimal processing. Accordingly, the manufacture of laundry granules will now be described separately in the granule manufacturing section (below), for the convenience of the formulator.

INDUSTRIAL APPLICABILITY Surfactant systems of this type can be used in all cleaning formations. The detergent compositions of the invention can therefore contain additional detergent components. The precise nature of these additional components and the levels of incorporation thereof will depend on the physical form of the composition and the precise nature of the cleaning operation for which they are used. Branched longer chain derivatives are more soluble than expected and short chain derivatives clean better than expected. Cleaning compositions herein include, but are not limited to: granular, bar form and liquid laundry detergents, hand dishwashing compositions in liquid form; liquid, gel and bar shape personal cleaning products; shampoos; toothpastes; hard surface cleaners and the like. Such compositions may contain a variety of conventional detersive ingredients. The following list of such ingredients is for the convenience of the formulator and not in the form of limitation of the types of ingredients that may be used with the branched-chain surfactants herein. The compositions of the invention preferably contain one or more additional components selected from surfactants, formers, alkalinity systems, organic polymeric compounds, foam suppressors, slurry suspension and antiredeposition agents and corrosion inhibitors. Bleaching Compounds - Bleeding Agents and Bleeding Activators. The detergent compositions herein preferably additionally contain bleaching agents or bleaching compositions containing a bleaching agent and one or more bleach activators. Bleach activators will typically be at levels of from about 1% to about 30%, more commonly from about 5% to about 20% of the detergent composition, especially for fabric washing. If present, the amount of the bleach activators will typically be from 0.1% to about 60%, more commonly from about 0.5% to about 40% of the bleaching composition comprising the bleach activator plus the agent bleach. The bleaching agents used herein may be any of the bleaching agents useful for detergent compositions in textile cleaning, hard surface cleaning or other cleaning purposes that are known or will be known. These include oxygen bleaches as well as other bleaching agents. Perborate bleaches, for example sodium perborate (e.g. mono or tetrahydrate) can be used herein. Another category of bleaching agent that can be used without restriction includes percaboxylic acid bleaching agents and salts thereof. Suitable examples of this class of agents include magnesium monoperoxy phthalate hexahydrate, the magnesium salt of meta-chloro perbenzoic acid, 4-nonylamino-4-oxoperoxybutyric acid and diperoxydecanedioic acid. Such bleaching agents are described in U.S. Patent 4,483,781, published November 20, 1984, U.S. Patent Application 740,446, Burns et al, filed June 3, 1985, European Patent Application 0,133,354, Banks et al, published. on February 20, 1985, and U.S. Patent 4,412,934 Chung et al, published November 1, 1983. Highly preferred bleaching agents also include 6-nonylamino-6-oxoperoxycaproic acid as described in U.S. Patent 4,634,551 issued 6 January 1987, for Burns et al. Peroxygen bleaching agents can also be used. Suitable peroxygen bleach compounds include sodium carbonate peroxyhydrate and the equivalent "percabonate" bleaches, sodium carbonate peroxyhydrate, urea peroxyhydrate, and sodium peroxide. Persulfate bleach (for example OXONE, commercially manufactured by DuPont) can also be used. A preferred percarbonate bleach comprises dry particles having an average particle size in the range of about 500 to about 1000 microns no more than about 10% by weight of said particles which is less than about 200 microns and no more than about 10% by weight of the particles that is greater than 1250 microns. Optionally, the percarbonate can be coated with silicate, borate or water soluble surfactants. Percarbonate is available from various commercial sources such as FMC, Solvay and Tokai Denka. Mixtures of bleaching agents can also be used. Peroxygen bleaching agents, perborates, percarbonates, etc., are preferably combined with bleach activators, which leads to in situ production in aqueous solution, (i.e. during the washing process) of the peroxy acid corresponding to the activator bleaching. Non-limiting examples of activators are described in U.S. Patent 4,015,854 published April 10, 1990 to Mao et al, and U.S. Patent 4,412,934. The activators of nonanoloxybenzene sulfonate (NOBS) and tetraacetyl ethylenediamine (TAED) are typical and mixtures thereof can be used. See also U.S. Patent 4, 634,551 for other typical bleaches and activators useful herein. The highly preferred amido derivative bleach activators are those of the formulas: R 1 N (R 5) C (O) R 2 C (O) L or R 1 C (O) N (R 5) RC (O) L wherein R 1 is an alkyl group which it contains from about 6 to about 12 carbon atoms. R2 is an alkylene containing from 1 to about 6 carbon atoms. R5 is H or alkyl, aryl, or alkynyl containing from 1 to 10 carbon atoms and L is any suitable leaving group. A leaving group is any group that is placed from the bleach activator as a consequence of the nucleophilic attack on the bleach activator by the perhydrolysis anion. A preferred leaving group is phenylsuiphonate. Preferred examples of bleach activators of the above formulas include (6-octanamido-caproyl) oxybenzenesulfonate, (6-nonaamidocarpoyl) oxybenzenesulfonate, (6-decanomido-caproyl) oxybenzenesulfonate, and mixtures thereof as described in the patent U.S. 4,634,551, incorporated herein by reference. Another class of bleach activators comprises activators of the benzoxacin type described by Hodge et al in U.S. Patent 4,966,723, issued October 30, 1990 incorporated herein by reference. A highly preferred activator of the benzoxacin type is: Even another class of preferred bleach activators include acyl lactam activators, especially axial caprolactams and acyl valerolactams of the formulas: wherein R6 is H or an alkyl, aryl, alkoxyaryl, or alkaryl group containing from 1 to about 12 carbon atoms. The highly preferred lactam activators include benzoyl caprolactam, octanoyl caprolactam, 3,5,5-trimethylhexanoyl caprolactam, nonanoyl caprolactam, decanoyl caprolactam, undecenoyl caprolactam, benzoyl valerolactam, octanoyl valerolactam, decanoyl valerolactam, unecenoyl valerolactam, nonanoyl valerolactam, 3,5 , 5-trimethylhexanoyl valerolactam and mixtures thereof. See also U.S. Patent 4,545,784 issued to Sanderson on October 8, 1985, incorporated herein by reference which discloses acyl caprolactams, including benzoyl caprolactam, absorbed in sodium perborate. Bleaching agents other than oxygen bleaching agents are also known in the art and can be used herein. One type of oxygen-free bleaching agent of particular interest includes photoactivated bleaching agents such as sulfonated zinc and aluminum / delta-cyclocyanins. See U.S. Patent 4,033,719 issued July 5, 1977, to Holcombe et al. If used, the detergent compositions will typically contain from about 0.025% to about 1.25% by weight, of such bleaches especially phthalocyanine zinc sulfonate. If desired, the bleaching components can be catalyzed by means of a manganese component. Such compositions are well known in the art and include, for example, the manganese-based catalysts described in U.S. Patents 5,244,594; 5,194,416; 5,114,606; and European Patent Application Requests Nos. 549,271A1, 549,272A1, 544,440A2 and 544.490490A1; preferred examples of these catalysts include Mn'v2 / uO) 3 (1, 4,7-trimethyl-1, 4,7-triazacyclonone) 2 (PF6) 2m Mn "2 (uO) 1 (u-OAc) 2 ( 1, 4, 7-trimethyl-1, 4,7-triazacyclononane) 2 (CIO4) 2, Mnlv4 (uO) 6 (1,4,7-triazacyclone) 4 (CIO4) 4, MnmMnlv4 (uO) 1 (u -OAc4) 2- (1,4,7-tpmethyl-1,4,7-triazacyclonone) 2 (CI04) 3, Mn? V (1, 4, 7-trimethyl-1, 4,7-triazacilononano) - (OCH3) 3 (PF6) and mixtures thereof Other catalysts which are bleached on a metal basis include those described in U.S. Patents 4,430,243 and U.S. Patent 5,114,611.The use of manganese with several complete ligands to improve bleaching is also reported in the following U.S. Patents 4,728,455, 5,284,944, 5,246,612, 5,256,779, 5,280,117, 5,274,147, 5,153,161, and 5,227,084 As a practical matter, and not by way of limitation, the compositions and processes herein can be adjusted to provide the order of at least one part per ten million species of cataliz Active bleaching agent in the aqueous wash liquor and preferably, will provide from 0.1 ppm to about 700 ppm, more preferably from about 1 ppm to about 500 ppm, of the catalyst species in the laundry liquor. The cobalt bleach catalysts used herein are known and described, for example, in M. L. Tobe, "Hydrolysis Base of Metal Complexes", Adv. Inorg. Bioionorg. Mech., (1983), 2, pages 1-94. The most preferred cobalt catalyst herein is the salts of cobalt pentaamine acetate having the formula [Co (NH3) 5OAc] Ty, wherein "OAc" represents an acetate portion and "Ty" is an anion, and especially cobalt chloride pentaamine acetate, [Co (NH3) 5OAc] CI2; as [Co (NH3) 5OAc) 2; [Co (NH3) 5OAc] (PF6) 2; [Co (NH3) 5OAc] (S04); [Co (NH3) 5OAc] (BF4) 2; and [Co (NH3) 5OAc] (N03) 2 (donder "PAC"). These cobalt catalysts are readily prepared by known methods such as those taught for example in the Tobe article and references cited therein, in U.S. Patent 4,810,410 to Diakun et al, published March 7, 1989.; L. Chem. Ed. (1989), 66, (12), 1043-45; The Synthesis and Characterization of Inorganic Compounds, W. L. Jolly (Prentice-Hall, 1970), pp. 461-3; Inoro. Chem, 18. 1479-1502 (1979); Inorg. Chem. 21. 2881-2885 (1982); Inoro. Chem. 18 2023-2025 (1979); Inorg. Synthesis, 173-176 (1960); and Journal of Phvsical Chemistrv 56, 22-25 (1952). As a practical point and not by way of limitation, the cleaning compositions and processes herein can be adjusted to provide the order of at least one part per million of the active bleach catalyst species in the aqueous washing medium, and preferably will provide from about 0.01 ppm to about 25 ppm, more preferably from about 0.5 ppm to about 10 ppm and more preferably from about 0.1 ppm to about 5 ppm, of the bleach catalyst species in the wash liquor. In order to obtain such levels in the wash liquor of an automatic washing process, typical compositions herein will comprise from about 0.0005% to about 0.2%, more preferably from about 0.004% to about 0.08%, of the bleaching, especially manganese or cobalt catalysts by weight of the cleaning compositions. Enzymes Enzymes are preferably included in current detergent compositions for a variety of purposes, including the removal of stains based on protein, based on carbohydrate or based on triglyceride from substrates, for the prevention of stain transfer of concealment in washing of fabrics and for fabric restoration. Suitable enzymes include proteases, amylases, lipases, celluloses, peroxidases and mixtures thereof of any suitable origin, such as of animal, vegetable, bacterial, fungal and yeast origin. Preferred choices without influenced by factors such as pH activity and / or optimal stability, thermostability and stability to active detergents, formers and the like. In this regard, fungal or bacterial enzymes are preferred, such as bacterial amylases and proteases and fungal cellulases.

The detersive enzymes as used herein, represent any enzyme that has a stain removal, or otherwise a beneficial effect on a hard surface cleaner, laundry or personal care detergent composition. Preferred detersive enzymes are hydrolases such as proteases, amylases, and lipases. Preferred enzymes for laundry purposes include, but are not limited to, proteases, cellulases, lipases and peroxidases. Highly preferred for automatic dishwashing are amylases and / or proteases that include currently commercially available types and improved types which, although increasingly compatible with bleaching through successive improvements, have a residual degree of susceptibility to the deactivation of bleaching. Enzymes are usually incorporated in detergent or detergent additive compositions at levels sufficient to provide an effective amount of cleaning. The term effective cleaning amount refers to a quality capable of producing a cleaning, stain removal, dirt removal, bleaching, deodorization or freshness improving effect on substrates such as fabrics, tableware and the like. In practical terms for current commercial preparations, typical amounts are up to about 5 mg by weight, more preferably 0.01 mg to 3 mg, of active enzyme per gram of the detergent composition. Established otherwise, the compositions herein will typically comprise from 0.001% to 5%, preferably 0.01% .1% by weight of a commercial enzyme preparation. Protease enzymes are usually present in commercial preparations at levels sufficient to provide from 0.005 to 0.1 Anson units (AU) of activity per gram of composition. For certain detergents, such as automatic dishwashing, it may be desirable to increase the active enzyme content of the commercial preparation in order to minimize the total amount of materials that are not catalytically active and thus improve the formation knit / film or other final results. Higher active levels may also be desirable in highly concentrated detergent formulations. Suitable examples of proteases are subtilisins that are obtained from particular strains of B. subtilis and B. licheniformis. Another suitable protease is obtained from a strain of Bacillus that has a maximum activity through the pH range of 8-12, developed and sold by ESPERASE® Novo Industries A / S of Denmark, hereinafter "Novo". The preparation of this enzyme and analogous enzymes is described in GB 1,243,784 to Novo. Other suitable proteases include ALCALASE® and SAVINASE® from Novo and MAXATASE® from International Bio-Synthetics, Inc., The Netherlands, as well as Protease A as described in EP 130,756, January 9, 1985 and Protease B as described in EP 303,761, April 28, 1987 and EP 130,756, A, January 9, 1985. See also that a high pH protease from Bacillus sp. NCIMB 40338 described in WO 9318140 A for Novo. Enzymatic detergents comprising protease, one or more other enzymes and a reversible protease inhibitor are described in WO 92003529 A to Novo. Other preferred proteases include those of WO 9510591 A to Procter & Gamble. When desired, a protease having decreased absorption and increased hydrolysis is available as described in WO 9507791 A Procter / Gamble. A recombinant trypsin-like protease for detergents suitable herein is described in WO 9425583 to Novo. In more detail, an especially preferred protease, referred to as "Protease D" is a variant of carbonyl hydrolase having an amino acid sequence not found in nature, which is derived from a precursor carbonyl hydrolase by substitution of a different amino acid from a plurality of amino acid residues at a position in such hydrolase carbonyl equivalent to the +76 position, preferably also in combination with one or more amino acid residue positions of equivalents to those selected from the group consisting of +99, +101, +103, +104, +107, +123, +27, +105, +109, +126, +128, +133, +156, +166, +195, +197, +204, +206, +210, +216, +217, +218, +222, +260, +265 and / or +274 according to the numbering of Bacillus amyloliquefaciens subtilisin, as described in WO 95/10615, published on April 20, 1995 by Genecor International. Useful proteases are also described in PCT publications WO 95/30010 published on November 9, 1995, by The Procter & amp; amp;; 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: Amylases suitable herein, especially for, but not limited to, automatic washing purposes, include, for example, α-amylases described in GB 1,296,839 for Novo; RAPIDASE® International Bio-Synthetics, Inc., and TERMAMYL® Novo, FUNGAMYL® from Novo is especially useful. The engineering of the enzymes for improved stability, for example oxidative stability is known. See, for example, J. Biological Chem. Vol. 260, No. 11, June 1985, p. 6518-6521. Certain preferred embodiments of the present composition can utilize amylases having improved stability in detergents such as automatic fret washing types, especially improved oxidative stability as measured against a TERMAMYL® benchmark in commercial use in 1993. Those preferred amylases in the present share the characteristics of being amylases of improved stability, characterized to a minimum degree by a measurable improvement of one or more of: oxidative stability for example, to hydrogen peroxide / tetraacetylenediamine in solution regulated in its pH 9- 10; thermal stability, for example, at common wash temperatures such as about 60 ° C; or alkaline stability, for example, at a pH from about 8 to 11, measured against the amylase of the previously identified reference point. The stability can be measured using any of the technical tests described. See, for example, the references described in WO 9402597. Amylases of improved stability can be obtained from Novo or Genencor International. One class of highly preferred amylases herein has the common property of being derived using the site-directed mutagenesis of one or more of the Bacillus amylases, especially the Bacillus a-amylases, regardless of whether one, two or multiple strains of amylases are present. the intermediate precursors. The amylases of improved oxidant stability against the above-identified reference amylases are preferred for use especially in bleaching, more preferably oxygen bleaching, unlike chlorine bleaching, compositions herein. Preferred amylases include (a) an amylase according to the above incorporated WO 9402597, Novo, February 3, 1994, as further illustrated by a mutant in which the substitution is made using alanine or threonine, preferably threonine, of the residue of methionine located at position 197 of B. licheniformis alpha-amylase known as TERMAMYL® or variation of the homologous position of a similar parent amylase, such as B. amyloliquefaciens, B. subtilis or B. stearothermophilus; (b) amylases of improved stability as described by Genencor International, in a document entitled "Oxidatively Resistant alpha-Amylases presented at the 207th American Chemical Society National Meeting, March 13-17, 1994, by C. Mitehinsen, in which it was observed that bleaching in automatic dishwashing detergents inactivates alpha-amylases although improved oxidase stability amylases were made by Genencor from B. licheniformis NCIB8061, Methionine (Met), was identified as the most likely residue to be modified, Met was replaced, one at a time, in positions 8, 15, 197, 256, 304, 366 and 438 guiding the specific mutants, particularly the M197L and M197T with M197T which is the most stable expressed variant.The stability was measured in CASCADE® and SUNLIGHT®; ) particularly the amylases preferred herein include the amylase variants having further modification in the immediate parent as described in WO 9510603 A and are available from the transferee Novo, like DURAMYL®. Other particularly preferred oxidatively stable amylases include those described in WO 9418314 to Genencor International and WO 9402597 to Novo. Any other amylase of improved oxidant stability can be used, for example, as derived by site-directed mutagenesis of hybrid chimeric parent forms or single mutants of the available amylases. Other preferred enzyme modifications are accessible. See WO 9509090 A a Novo.

Other amylase enzymes include those described in WO 95/26397 and in the co-pending application of Novo Nordisk PCT / DK96 / 00056. Specific amylase enzymes for use in detergent compositions of the present invention include α-amylases characterized by having a specific activity at least 25% higher than the specific activity of Termamyl® in a temperature range of 25 ° C to 55 ° C and a pH value in the range of 8 to 10, as measured by Phadebas® a-amylase. (Such a Phadebas® α-amylase assay is described on pages 9-10, WO 95/26397). Also included herein are a-amylases that are at least 80% homologous with the amino acid sequences shown in the SEC listings. ID. These enzymes are preferably incorporated in laundry detergent compositions at a level of 0.00018% to 0.060% pure enzyme by weight of the total composition, more preferably from 0.00024% to 0.048% pure enzyme by weight of the total composition. The cellulases usable herein include the types of bacteria and fungi, preferably having an optimum pH between 5 and 9. US Patent 4,435,307 Barbesgoard, et al., March 6, 1984, describes suitable fungal celluloses from the Humicola strain insolens or Humicola DSM1800 or a fungus producer of cellulose 212 that belongs to the genus Aeromonas and the cellulose extracted from hepatopancreas of a marine mollusk. Dolabella Auricular Solander. Suitable cellulases are also described in GB-A-2,075,028; GB-A-2,095,275 and DE-OS-2,247,832. CAREZYME® and CELLUZYME® (Novo) are especially useful. See also WO 9117243 to Novo. Suitable lipase enzymes for use in detergents include those produced by microorganisms of the Pseudomonas group, such as Pseudomonas stuizeri ATCC, 19,154, as described in GB 1,372,034. See also lipases in Japanese Patent Application 53,204487, open to the public on February 24, 1978. This lipase is available from Amano Pharmaceutical Co. Ltd., Nagoya, Japan, under the trade name Lipasa P "Amano" or "Amano-P". Other suitable commercial lipases include Amano-CES, lipases ex Chromabacter viscosum, e.g., Chromobacter viscosum var. lipolyticum NRRLB 3673 from Toyo Jozo co., Tagata, Japan; Chromobacter viscosum lipases from U.S. Biochemical Corp., U.S. A. and Disoynth. Col. The Netherlands, and the lipases ex Pseudomonas gladioli. The enzyme LIPOLASE® derived from Humicola lanuginosa and commercially available from Novo, see also EPO 341,947, is a preferred lipase for use herein. Variants of lipase and amylase stabilized against peroxidase enzymes as described in WO 9414951 for Novo. See also WO 9205249 and RD 94359044. 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 found wide application as an additive for fabric washing products. It is available from Novo Nordisk under the trade name Lipolase ™ as noted above. In order to optimize the Lipolase stain removal performance, Novo Nordisk has made a number of variants. As described in WO 92/05249, the D96L variant of the native Humicola lanuginosa lipase improves the efficiency of removal of the fatty spot by a factor of 4.4 over 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 (5-500,000 LU / liter) of the variant of lipase per liter of washing liquor. The present invention provides the benefit of improved whiteness maintenance on fabrics by using low levels of the D96L variants in detergent compositions containing the medium chain branched primary alkylsulfur surfactants in the manner described herein, especially when D96L is used. at the scale levels of approximately 50 LU to approximately 8500 LU per liter of the wash solution. Cutinase enzymes suitable for use herein are described in WO 8809367 A to Genencor. Peroxidase enzymes can be used in combination with oxygen sources, for example, percarbonate, perborate, hydrogen peroxide, etc., for "solution bleaching" or to prevent the transfer of stains or pigments removed from the substrates during the wash to other substrates present in the washing solution. Known peroxidases include horseradish peroxidase, ligninase, and haloperoxidases such as chlorine or bromoperoxidase. Peroxidase-containing detergent compositions are described in WO 89099813 A October 19, 1989 to Novo and WO 8909813 A to Novo. A scale of enzyme materials and means for their incorporation into synthetic detergent compositions is also disclosed in WO 9307263 A and WO 9307260 A for Genencor International WO 9808694 A for Novo, and U.S. 3,553,139 on January 5, 1971, for McCarty et al. The enzymes are also described in U.S. 4,101,457, Place et al., July 18, 1978, and in U.S. 4,507,219, Hughes, March 26, 1985. Useful enzyme materials for liquid detergent formulations and their incorporation into such formulations are described in U.S. 4,261,868, Hora et al. on April 14, 1981. Enzymes for use in detergents can be stabilized by various techniques. Enzyme stabilization techniques are described and exemplified in U.S. 3,600,319, August 17, 1971, Gedge et al. EP 199,405, and EP 200,586, on October 29, 1986, Venegas. Enzyme stabilization systems are also described in, for example, U.S. 3,519,570. A Bacillus, sp. Useful AC13 that provides proteases, xylanases and cellulases is described in WO 9401532 a for Novo. Enzyme Stabilization System - Enzyme-containing compositions herein may optionally comprise from about 0.001% to about 10%, preferably from about 0.005% to about 8%, most preferably from about 0.01% to about 6% by weight of an enzyme stabilization system. The enzyme stabilizing system can be any stabilizing system that is compatible with the detersive enzyme. Such a system can be inherently provided by other formulation assets, or it can be added separately, for example, by the formulator or the manufacturer of the detergent enzymes. Such stabilization systems may, for example, comprise calcium ion, boric acid, propylene glycol, short chain carboxylic acids, boronic acids and mixtures thereof and are designed to address the different stabilization problems depending on the type and physical form of the detergent composition. A stabilization approach is the use of water soluble sources of calcium and / or magnesium ions in the finished compositions that provide such ions to the enzymes. Calcium ions are generally more effective than magnesium ions and are preferred herein only if one type of cation is being used. Typical detergent compositions, especially liquid, will comprise from 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 the finished detergent composition, although it is possible the variation depending on factors that include the multiplicity, type and levels of enzymes incorporated. Water-soluble calcium or magnesium salts are preferably employed including, for example, calcium chloride, calcium hydroxide, calcium formate, calcium malate, calcium maleate, calcium hydroxide and calcium acetate; More generally, calcium sulfate or magnesium salts corresponding to the exemplified calcium salts can be used. The increased levels of calcium and / or magnesium can of course be useful, for example, to promote the constant action of fat of certain types of surfactant. Another approach to stabilization is through the use of borate species. See Severson, U.S. 4,537,706. Borate stabilizers, when used, may be at levels of up to 10% or more of the composition although more typically, levels of up to about 3% by weight of boric acid or other borate compounds such as borax or the Orthoborate are suitable for the use of liquid detergent. Substituted boric acids such as phenylboronic acid, butanboronic acid, p-bromophenylboronic acid or the like may be used in place of boric acid and reduced levels of total boron in detergent compositions may be possible through the use of such substituted boron derivatives . The stabilization systems of certain cleaning compositions, for example, automatic dishwashing compositions, may further comprise from 0 to about 10%, preferably from about 0.01% to about 6% by weight of chlorine bleach deoxidants added to avoid that chlorine bleach species present in many water supplies attack and inactivate enzymes, especially under alkaline conditions. While chlorine levels in water can typically be low in the range from 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, for example, during the washing of Frets or cloth can be relatively large, consequently, the stability of the enzyme to chlorine in use is sometimes problematic. Since perborate or percarbonate, which have the ability to react with chlorine bleach may be present in some of the present compositions in amounts counted from separate parts of the stabilizer system, the use of additional stabilizers against chlorine may more generally, it is not essential, although improved results can be obtained from its use. Suitable chlorine deoxidizing anions are widely known and readily available and, if used, may be salts containing ammonium cations with sulfite, bisulfite, thiosulfite, thiosulfate, iodide, etc. Antioxidants such as carbamate, ascorbate, etc., organic amines such as ethylenediaminetetraacetic acid (EDTA) or alkali metal salt thereof, monoethanolamine (MEA), and mixtures thereof can likewise be used, inhibitor systems of special enzymes can be incorporated so that the different enzymes have maximum compatibility. Other conventional deoxidants such as bisulfate, nitrate, chloride, hydrogen peroxide sources such as sodium perborate tetrahydrate, sodium perborate monohydrate and sodium percarbonate as well as phosphate, condensed phosphate, acetate, benzoate, citrate, formate, lactate, malate, tartrate , salicylate, etc., and mixtures thereof may be used if desired. In general, since the deoxidizing function of chlorine can be carried out by ingredients listed separately under better recognized functions (for example, hydrogen peroxide sources), there is no absolute requirement to add a chlorine deoxidizer unless a set that executes that function for the desired degree is absent from an enzyme-containing environment of the invention; even after the deoxidizer is added only for optimal results. In addition, the formulator can exercise a normal chemistry ability by avoiding the use of any enzyme or stabilizer deoxidizer that is primarily incompatible as formulated, with other reactive ingredients. In relation to the use of ammonium salts, such salts can simply be mixed with the detergent composition although they are prone to absorb water and / or release ammonium during storage. Accordingly, such materials if present are desirably protected in a particle as described in US 4,652,392, Baginski et al. Enhancers - Detergent builders are selected from aluminosilicates and silicates preferably included in the compositions herein, for example, to help control the ore, especially Ca and / or Mg, the hardness in the wash water, or to assist in the removal of particle stains from the surface.

Suitable silicate builders include water-soluble types and hydride solids and include those having chain, layered or three-dimensional structures, as well as amorphous or unstructured liquid types. Preferred are the alkali metal silicates, particularly those liquids and solids having an SiO2: Na2O ratio in the range of 1.6: 1 to 3.2: 1, including particularly those for the purpose of automatic dishwashing, silicates with a ratio of 2. hydrated solids, sold by PQ Corp. under the trade name BRITESIL®, for example, BRITESIL H20; and layered silicates, for example, those described in U.S. 4,664,839; May 12, 1987, H.P. rieck, NaSKS-6, sometimes abbreviated "SKS-6" is a silicate of morphology of crystalline-laden aluminum-free Na2SiO5 sold by Hoechst and especially preferred in granular laundry compositions. See the preparation methods in German documents DE-A-3, 417,649 and DE-A-3,742,043. Other layered silicates such as those having the general formula NaMSixO2x.1 and H2O wherein M is sodium or hydrogen, x is a number from 1.9 to 4, preferably 2 and y is a number from 0 to 20, preferably 0, may also or from alternative way used in the present. The layered silicates of Hoechst also include NaSKS-5, NaSKS-7 and NaSKS-11, as the silicate forms in layer a, β and β. Other silicates may be useful such as magnesium silicate, which may serve as a frothing agent in granules, as a stabilizing agent for bleach, and as a component of foam control systems.

Also suitable for use herein are the crystallized ion exchange materials synthesized or hydrides thereof having a chain structure and a composition represented by the following general formula in an anhydride form: xM2O'ySiO2zM'O wherein M is Na and / or K, M 'is Ca and / or Mg: y / x is 0.5 to 2.0 and z / x is 0.005 to 1.0 as taught in the US 5,427,711 Sakaguchi et al., June 27, 1995. Aluminosilicate builders are especially useful in granular detergents, although they can also be incorporated in liquids, pastes or gels. Suitable for purposes of the present are those that have the empirical formula [M2 (AIO2) 2 (SiO2) and] xH2O where z and v are integers of at least 6, the molar ratio of zav is in the range of 1.0 to 0.5 and x is an integer from 15 to 264. Aluminosilicates can be crystalline or amorphous, of natural occurrence or synthetically derived. One method of aluminosilicate production is in U.S. 3,985,669, Krummel, et al. on October 12, 1976. Preferred synthetic crystalline aluminosilicate ion exchange materials are available as Zeolite A, Zeolite P (B), Zeolite X and, to any extent that this differs from Zeolite P, the so-called Zeolite MAP. Natural types, which include clinoptilolite can be used. Zeolite A has the formula Na12 [(A102) i2 (SiO2) i2] -xH2O where x is from 20 to 30, especially 27. Dehydrated zeolites (x = 0-10) can also be used. Preferably, the aluminosilicate has a particle size of 0.1-10 microns in diameter.

The detergent builders in place of, or in addition to the silicates and the aluminosilicates described heretofore heretofore can be included in the current compositions for example to help control the mineral, especially calcium and / or magnesium, the hardness in the water of washing or to assist in the removal of particle stains from surfaces. The enhancers can be operated by a variety of mechanisms including the formation of soluble or insoluble complexes with hardness ions, by ion exchange, and offering a more favorable surface for the precipitation of the hardness ions that are the surface of the items that are going to be cleaned. The level of improver can vary widely depending on the final use and the physical form of the composition. Improving detergents typically comprise at least about 1% of the improver. Liquid formulations typically comprise from about 5% to about 50%, most commonly from 5% to 35% of the improver. Granular formulations typically comprise from about 10% to about 80%, more preferably 15% to about 50% of the weight improver of the detergent composition. The lower or higher levels of breeders are not excluded. For example, certain detergent additive or formulations of high surfactant content may not be incorporated. Suitable improvers herein can be selected from the group consisting of phosphates, and polyphosphates, especially the sodium salts; carbonates, bicarbonates, sesquicarbonates and carbonate minerals other than sodium carbonate or sesquicarbonate; organic mono, di, tri and tetracarboxylates especially water-soluble non-surfactant carboxylates in the form of acid, sodium, potassium or alkanolammonium salt, as well as oligomeric or water-soluble low molecular weight polymer carboxylates including aliphatic and aromatic types; and phytic acid. These may be supplemented by borates, for example for pH regulation purposes or by sulfates, especially sodium sulfate or any other fillers or carriers that may be important for the engineering of the stable surfactant and / or the detergent compositions containing improver. . Improver mixtures, sometimes referred to as "enhancer systems" can be used and typically comprise two or more conventional improvers, optionally complemented by chelators, pH regulators or fillers, although the latter materials are generally accounted for separately when describing amounts of materials in the present. The term relative amounts of surfactant and builder in the detergents herein, preferred builder systems are typically formulated in a weight ratio of surfactant to builder from about 60: 1 to about 1:80. Certain preferred laundry detergents have a 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.

Frequently preferred P-containing detergent builders were allowed by the legislation and include, but are not limited to, alkali metal, ammonium and alkanolammonium salts of polyphosphates exemplified by tripolyphosphates, pyrophosphates, vitreous polymeric metaphosphates and phosphonates. Suitable carbonate builders include alkaline earth metal and alkaline carbonates as described in German Patent Application No. 2,321,001 published November 15, 1973, although sodium bicarbonate, sodium carbonate, sodium sesquicarbonate and other minerals of carbonate such as trona or any convenient multiple salts of sodium carbonate and calcium carbonate such as those having the composition 2Na2CO3.CaCO3 when they are anhydrous and even calcium carbonates include calcite, aragonite and vaterin, especially in forms which have ample Surface areas relative to compact calcite may be useful, for example, as sediments or for use in synthetic detergent bars. Suitable organic detergent builders include polycarboxylate compounds which include water-soluble non-surfactant dicarboxylates and tricarboxylates. More typically the improving carboxylates have a plurality of carboxylate groups, preferably at least 3 carboxylates. The carboxylate builders can be formulated in acid in partially neutral, neutral or base form. When in the salt form, the alkali metals such as sodium, potassium and lithium and the alkanolammonium salts are preferred. Polycarboxylate builders include ether polycarboxylates, such as oxydisuccinate, see Berg. U.S. 3,128,287, April 7, 1964, and Lamberti et al., U.S. 3,635,830, on January 18, 1972; "TMS / TDS" improvers of U.S.4, 663, 071, Bush et al., May 5, 1987, and other carboxylates include cyclic and alicyclic compounds such as those described in U.S. Patent 3,923,679; 3,835,163; 4,158,635; 4,120,874 and 4,102,903. Other suitable builders are ether hydroxypolycarboxylates, copolymers of maleic anhydride with ethylene or vinyl methyl ether; 1, 4,5-trihydroxybenzene-2,4,6-trisulfonic acid; carboxymethyloxysuccinic acid; the various alkali metal, ammonium and substituted ammonium salts of polyacetic acids such as ethylenediaminetetraacetic acid and nitrilotriacetic acid; as well as melific acid, succinic acid, polymaleic acid, benzene, 3,5-tricarboxylic acid, carboxymethyloxysuccinic acid and soluble salts thereof. Citrates, for example citric acid and soluble salts thereof, are important carboxylate builders for example, for heavy duty liquid detergents, due to availability from renewable and biodegradable sources. The citrates may be useful in granular compositions especially in combination with zeolite and / or layered silicates. Oxydisuccinates are also especially useful in such compositions and combinations. When allowed and especially in the formulation of bars used for hand washing operations and in granular laundry compositions, alkali metal phosphates such as sodium tripolyphosphates, sodium pyrophosphate and sodium orthophosphate can be used. Phosphonate builders such as ethan-1-hydroxy-1,1-diphosphonate and other known phosphonates such as those of U.S. 3,159,581; 3,213,030; 3,422,021; 3,400,148 and 3,422,137 can also be used and may have desirable flaking properties. Certain detersive surfactants or their short chain homologs also have an enhancer action. For unambiguous accounting purposes, when they have surfactant capability, those materials are added as detersive surfactants. Preferred types for enhancer functionality are illustrated by: 3, 3-dicarboxy-4-oxa-1,6-hexanodiates and the related compounds described in U.S. No. 4,566,984, Bush, January 28, 1986. Succinic acid improvers include succinic alkyl and C5-C20 alkenyl acids and salts thereof. Succinate builders also include: laurylsuccinate, myristylsuccinate, palmitylsuccinate, 2-dodecenylsuccinate (preferred), 2-pentadecenylsuccinate and the like, lauryl succinates are described in European Patent Application 86200690.5 / 0200263, published on November 5. from 1986. Fatty acids for example, C12-C18 monocarboxylic acids can also be incorporated into composicones as surfactant / mejador agent materials alone or in combination with the aforementioned enhancers especially citrate and / or succinate improvers, to provide additional enhancer activity. Other suitable polycarboxylates are described in U.S. 4,144,226, Crutchfield et al., March 13, 1979, and in U.S. 3,308,067, Diehl, March 7, 1967. See also Diehl, U.S. 3,723,322. Other types of inorganic improver materials that can be used have the formula (Mx), Cay (CO3) 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 of which is soluble in water and the equation S, = 1-15 (x) multiplied by the valence of Mi) + 2y = 2x is satisfied so that the formula has a neutral or "balanced" charge. Those breeders are referred to herein as "Mineral Enhancers". Hydration waters or anions other than carbonate may be added provided the overall charge is balanced or neutral. The load or valence effects of such anions must be added to the right side of the previous equation. Preferably, a water-soluble cation selected from the group consisting of hydrogen, water-soluble metals, hydrogen, boron, ammonium, silicon and mixtures thereof, more preferably sodium, potassium, hydrogen, lithium, ammonium and mixtures thereof, is present. of them, sodium and potassium, which are the most preferred. Non-limiting examples of non-carbonated anions include those selected from the group consisting of chlorine, sulfate, fluoride, oxygen, hydroxide, silicon dioxide, chromate, nitrate, borate, and mixtures thereof. Preferred improvers of this type in their simplest forms are selected from the group consisting of Na2Ca (CO3) 2, K2Ca (CO3) 2, Na2Ca2 (CO3) 3, NaKCa (CO3) 2, NaKCa2 (CO3) 3, K2Ca2 (CO3) 3, and combinations thereof. An especially preferred material for the improver described herein is Na 2 Ca (CO 3) 2 in any of its crystalline modifications. Suitable improvers of the type defined above are further illustrated by and include, the natural or synthetic forms of any one or combinations of the following minerals: Afghanite, Andersonite, AsheroftineY, Beyerite, Borcarite, Burbankite, Butschllite, Cancrinite, Carbocernaite, Carletonite, Davyne, 'DonnayiteY, Fairchildite, Ferrisurite, Franzinite, Gaudefroyite, Gaylussite, Girvasite, Gregoryite, Jouravskite, KamphaugiteY, Kettnerite, Khanneshite, LepersonniteGd, Liottite, MckelveyiteY, Microsonmite, Mroseite, Natrofairchildite, Nyerereite, RemonditeCe, Sarofanite, Schrockingerite, Shortite, Surite, Tunisite, Tuscanite, Tyrolite, Vishnevite, and Zemkorite. Preferred mineral forms include Nyererite, Fairchildite and Shorite. Detersive Surfactants The detergent compositions according to the present invention additionally preferably comprise additional surfactants, also referred to herein as co-surfactants. It is understood that the surfactant systems prepared in the manner of the present invention can be used individually in cleaning compositions or in combinations with other detersive surfactants. Typically, fully formulated cleaning compositions will contain a mixture of types of surfactants in order to obtain a broad scale cleaning performance over a variety of stains and grime and under a variety of conditions of use. An advantage of the branched chain surfactants of the present invention is the ability to be easily formulated in combination with other known types of surfactants. Non-limiting examples of the additional surfactants that can be commonly used herein at levels from about 1% to about 55% by weight, include unsaturated sulfates such as oleyl sulfate, C10-C18 alkyl alkoxysulfates ("AEXS especially EO 1-8 ethoxylates), C10-C18 alkyl alkoxycarboxylates (especially the EO 1-5 ethoxycarboxylates), the C10-18 glycerol ether sulphates, the C10-C18 alkyl polyglycosides and their corresponding sulphated polyglycosides, and the esters of C12-C18 alpha-sulfonated fatty acids Nonionic surfactants such as ethoxylated C 10 -C 8 alcohols and alkylphenols (for example, C 10 -C 18 EO (1-10) can also be used. Conventional surfactants such as C 2 -C 18 betaines and sulfobetaines ("sultaines") C 10 -C 18 amine oxides and the like can also be included in the general compositions. N-C10-C18 N-alkyl polyhydroxy can also be used. Typical examples include C12-C18 N-methylglucamides. See WO 9,206,154. Other sugar-derived surfactants include the N-alkoxy polyhydroxy acid amides, such as N- (3-methoxypropyl) of C 10 -C 18 glucamide. The N-propyl through the N-hexyl C 2-C18 glucamides can be used for low foaming. The conventional C? 0-C20 soaps can also be used. If high foaming is desired, branched chain C10-C16 soaps can be used. A wide range of these co-surfactants can be used in the detergent compositions of the present invention. A typical listing of anionic, non-ionic, ampholytic and zwitterionic classes and especially of those co-surfactants is given in US Patent 3,664,961, published for Norris on May 23, 1972. The amphoteric surfactant co-agents are also described in detail "Amphoteric Surfantants, Second Edition", EG Lomax, Editor (published in 1996, by Marcel Dekker, Inc.) Laundry detergent compositions of the present invention typically comprise in total from about 0.1% to about 35%, preferably from about 0.5% to about 15%, by weight of surfactant coagents. The additional co-surfactants selected are further identified as follows. (1) Anionic Co-Agents: Non-limiting examples of anionic co-surfactants useful herein, typically at levels from about 0.1% to about 50% by weight, include C10-C2o, branched chain primary alkyl sulfates and random ("AS"), the secondary alkyl sulphates C10-C18 (2.3) of the formula CH3 (CH2) x (CHOSO3 M +) CH3 and CH3 (CH2) and (CHOS03"M +) CH2CH3 where xy (y + 1 ) are integers of at least about 7, preferably about 9, and M is a cation of solubilization in water, especially sodium, unsaturated sulfates such as oleyl sulfate, alpha-sulfonated fatty acid esters C10-C18, polyglycosides of C10-C18 sulfated alkyl, C10-C18 alkyl alkoxy sulfates ("AEXS"; especially ethoxy sulfates EO 1-7), and C10-C18 alkyl alkoxy carboxylates, (especially the ethoxycarboxylates EO 1-5). C12-C18 betaines and sulfobetaines ("sultaines"), C10-C18 amine oxides and the like can also be included in the general compositions. Conventional C10-C16 soaps can also be used. If foaming is desired, the branched chain C10-d6 soaps can be used. Other conventional useful anionic co-surfactants are noted in standard texts. The alkyl alkoxy sulfate surfactants used herein are preferably water soluble salts or acids of the formula RO (A) mSO 3 M wherein R is an unsubstituted C 10 -C 24 alkyl or hydroxyalkyl group having a C 1 or C alkyl component C24, preferably a C12-C18 alkyl or hydroxyalkyl, more preferably C12-C15 alkyl or hydroxyalkyl, A is an ethoxy or propoxy unit, m is greater than zero, typically 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, calcium, magnesium etc.), ammonium or substituted ammonium cation Alkyl ethoxylated sulphates as well as alkyl propoxylated sulfates are contemplated in US Pat. I presented. Specific examples of substituted ammonium cations include ethanol, triethanol, methyl-dimethyl, trimethylammonium cations and quaternary ammonium cations such as tetrametal ammonium cations and dimethyl piperidinium cations and those derivatives of alkylamines such as ethylamine, diethylamine, triethylamine, mixtures thereof and similar. Exemplary surfactants are C12-C15 alkyl polyethoxylate (1.0) sulfate (C12 C 5E (1.0) M), C12-C15 alkyl polyethoxylate (2.25), sulfate (C12-C15E (2.25) M), C12-C alkyl polyethoxylate ? 5 (3.0 =) sulfate (C12-C15E (3.0) M), and C12-C15 alkyl polyethoxylate (4.0) sulfate (C12-C15 E (4.0) M), where M is conveniently selected from sodium and potassium . The alkyl sulfate surfactants useful herein are preferably water soluble salts or acids of the formula R0S03M wherein R is preferably a C10-C24 hydrocarbyl, preferably an alkyl or hydroxyalkyl having a C10-C18 alkyl component, more preferably an alkyl or C12-C15 hydroxyalkyl, and M is H or a cation, for example, an alkali metal cation (eg, sodium, potassium, lithium), or ammonium or substituted ammonium (eg, methyl, dimethyl and trimethylammonium in the form of cations and quaternary ammonium cations such as tetramethylammonium and dimethylpiperidinium cations and quaternary ammonium cations derived from alkylamines such as ethylamine, diethylamine, triethylamine and mixtures thereof and the like).

Other suitable anionic surfactants which may be used are alkyl ester sulphonate surfactants which include linear esters of C8-C2o carboxylic acid (ie fatty acids) which are sulfonated with gaseous SO3 according to "The Journal of the American Oil Chemists Society ", 52 (1975), pp. 323-329. Suitable starting materials will include natural fatty substances as derived from bait, palm oil, etc. The preferred alkyl ester sulfonate surfactant, especially for laundry applications, comprises alkyl ester sulphonate surfactants of the structural formula: R3-CH (SO3M) -C (O) -OR4 wherein R3 is a C8 hydrocarbyl C2o, preferably an alkyl, or a combination thereof, R4 is a hydrocarbyl of d-C6, preferably an alkyl, or combination thereof, and M is a cation that forms a water-soluble salt with the alkyl ester sulphonate . Suitable salt formation cations include metals such as sodium, potassium and lithium and substituted or unsubstituted ammonium cations, such as monoethanolamine, diethanolamine, and triethanolamine. Preferably, R 3 is C 1 or C 16 alkyl and R 4 is methyl, ethyl or isopropyl. Especially preferred are the methyl ester sulfonates wherein R 3 is C 0- alkyl Other anionic co-surfactants useful for detersive purposes can be included in the laundry detergent compositions of the present invention. These may include salts (including, for example, sodium, potassium, ammonium and substituted ammonium salts such as mono, di and triethanolamine in the form of salts) of soap. The C8-C22 primary and secondary alcansulfonates, C8-C24 olefinsulfonates, sulfonated polycarboxylic acids prepared by sublimation of the pyrolyzed product of the alkaline earth metal citrates, for example, as described in British Patent Specification No. 1,082,179. The C8-C24 alkyl polyglycol ether sulphates (containing up to 10 moles of ethylene oxide), aiqu ilg licerol sulfonates, fatty alkyl glycerol sulfonates, fatty oleoyl glycerol sulfonates, alkyl phenol ethylene ether sulfates, parafin sulfonates, alkyl phosphates, isethionates such as acyl isethionates, N- acyl taurates, alkyl succinamates and sulfosuccinates, monoesters of sulfosuccinates (especially saturated and unsaturated C12-d8 monoesters) and diesters of sulfosuccinates (especially saturated and unsaturated C6-d2 diesters), alkylpolysaccharide sulfates such as alkyl polyglucoside sulfates (the compounds are not nonionic sulfates described below) and the alkylpolyethoxycarboxylates such as those of the formula RO (CH 2 CH-2O) k-CH 2 COO-M + wherein R is a C 8 -C 22 alkyl, k is an integer from 0 to 10 and M it is a soluble salt forming cation. Resin acids and hydrogenated resin acids are also suitable such as rosin, hydrogenated rosin, and hydrogenated resin acids and resin acids present in, or derived from, bait oil. Additional examples are described 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 U.S. Patent 3,929,678, published December 30, 1975, to Laughlin et al., Column 23, line 58 to column 29, line 23 (incorporated herein by reference). ). Another suitable anionic co-surfactant is the disulfates. Preferred disulfate surfactants have the formula A- X'M 'R B- Y M wherein R is an alkyl, substituted alkyl, alkenyl, aryl, alkaryl, ether, ester, amine or amide group of chain length Ci to C28. preferably C3 to C2, more preferably, C8 to C2o or hydrogen; A and B are independently selected from alkyl, substituted alkyl and alkenyl groups of chain length d to C28 preferably d to C5, more preferably d or C2, or a covalent bond and A and B in total contain at least 2 atoms; A, B and R in total contain from 4 to about 31 carbon atoms; X and Y are anionic groups selected from the group consisting of sulfate and sulfonate, provided that at least one of X or Y is a sulfate group; and M is a cationic portion, preferably a substituted or unsubstituted ammonium ion or an alkali metal or alkaline earth metal ion. The most preferred disulfate surfactants have the formula as above where R is an alkyl group of chain length from C10 to C18. A and B are independently d or C2, X and Y are sulfate groups and M is a potassium, ammonium or sodium ion. See U.S. Patent Application 08 / 882,217, filed June 28, 1996, assigned to Procter & Gamble. Proxy Case No. 6162. When included herein, the laundry detergent compositions of the present invention typically comprise from about 0.1% to about 50%, preferably from about 1% to about 40% by weight of a surfactant. anionic (2) Nonionic Surfactant Co-Agents Non-limiting examples of nonionic surfactants useful herein typically at levels of from about 0.1% to about 50% by weight include alkoxylated alcohols (AE) and alkylphenols, polyhydroxy fatty acid amides (PFAA), alkyl polyglycosides (APG), glycerol esters of Cío-de Y the like. More specifically, the condensation products of the primary and secondary aliphatic alcohols from 1 to about 25 moles of ethylene oxide (AE) are suitable for use as a nonionic surfactant in the present invention. 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. The condensation products of alcohols having an alkyl group containing from about 8 to about 20 carbon atoms, more preferably from about 10 to about 18 carbon atoms, with about 1 to about 10 moles, preferably 2 to 7, are preferred. more preferably 2 to 5, of ethylene oxide per mole of alcohol. Especially preferred nonionic surfactants of this type are ethoxylates of primary alcohol Cg-C15 containing 3-12 moles of ethylene oxide per mole of alcohol, particularly the primary alcohols C12-C15 containing 5-10 moles of ethylene per mole of alcohol. Examples of commercially available nonionic surfactants of this type include: Tergitol ™ 15-S-9 (the condensation product of linear alcohol with 9 moles of ethylene oxide C? RC1s) and Tergitol ™ 24-L-6 NMW (the condensation product of the primary alcohol C12-C14 with 6 moles of ethylene oxide with a narrow molecular weight distribution), both sold by Union Carbide Corporation, Neodol ™ 45-9 (the condensation product of the linear C14-C15 alcohol with 9 moles of ethylene oxide), Neodol ™ 23-3 (the condensation product of the linear C 2 -C 13 alcohol with 3 moles of ethylene oxide), NeodolTm 45-7 (the linear C14-C15 alcohol condensation product with 7 moles of ethylene oxide) and Neodol ™ 45-5 (the condensation product of linear C14-C15 alcohol with 5 moles of ethylene oxide) sold by Shell Chemical Company, Kyro ™ EOB (the condensation product of C13 alcohol -15 with 9 moles of ethylene oxide), sold by The Procter / Gamble Company; and Genapol, LA 030 or 050 (the condensation product of C 12 -C 14 alcohol with 3 or 5 moles of ethylene oxide), sold by Hoechst. The preferred range of HLB in those nonionic surfactants AE is 8 to 17, and most preferred of 8-14. The condensers with propylene oxide and butylene oxides can also be used. Another class of preferred nonionic co-surfactants for use herein are the polyhydroxy fatty acid amide surfactants of the formula R- > C- N - Z, O R wherein R1 is H, or hydrocarbyl C, 4 2 -hydroxy ethyl, 2-hydroxypropyl or a mixture thereof, R2 is C5-31 hydrocarbyl and Z is a polyhydroxyhydrocarbyl having a linear hydrocarbyl chain with minus three hydroxyl directly connected to the chain, or an alkoxylated derivative thereof. Preferably, R1 is methyl, R2 is an alkyl d? -15 or C15-? alkyl or alkenyl chain such as coconut alkyl or mixtures thereof and Z is derived from a reducing sugar such as glucose, fructose, maltose, lactose, in a reduced amination reaction. Typical examples include the C12-C18 N-methylglucamides and C12-d4.

See U.S. 5,194,639 and 5,298,636. The polyhydroxy N-alkoxy fatty acid amides may also be used: see U.S. 5,489,393. Also useful as a non-ionic co-surfactant agent in the present invention are the alkylpolysaccharides such as those described in USPatent 4,565,647, Filling, published January 21, 1986, having a hydrophobic group containing from about 6 to about 30 atoms carbon, preferably from about 10 to about 16 carbon atoms, and a polysaccharide, for example, a polyglycoside, hydrophilic group having 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 saccharide. Any reducing saccharide containing 5 or 6 carbon atoms can be used for example, portions of glucose, galactose and galactosyl can be substituted for the glucosyl portions (optionally the hydrophobic group is attached at positions 2, 3, 4, etc, providing in this way a glucose or galactose as opposed to a glycoside or galactoside). The intersaccharide bonds may be, for example, between a position of the additional saccharide units and positions 2, 3, 4 and / or 6 in the preceding saccharide units. Preferred alkyl polyglycosides have the formula R2O (CnH2nO) r (glycosyl) x wherein R2 is selected from the group consisting of alkyl, alkylphenyl, hydroxyalkyl, hydroxyalkylphenyl and mixtures thereof in which 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 glycosyl is preferably derived from glucose. To prepare these compounds, the alcohol or alkylpolyethoxy alcohol is first formed and then reacted with glucose or a glucose source to form the glucoside (attached at position 1). The additional glycosyl units can be linked between their position 1 and the preceding glycosyl units at positions 2, 3, 4 and / or 6, preferably predominantly at position 2. Compounds of this type and their use in the detergents are described in EP-B 0 070 077, 0 075 006 and 0 094 118. The condensates of polyethylene oxide, polypropylene and polybutylene of alkylphenols are also suitable for use as the non-ionic surfactants of the surfactant systems of the present invention with the polyethylene oxide condensates that are preferred. These compounds include the condensation products of alkylphenols having an alkyl group containing from 6 to about 14 carbon atoms, preferably from about 8 to about 14 carbon atoms, either in straight or branched chain configuration, with the alkylene. In a preferred embodiment, the ethylene oxide is present in an amount equal to about 2 to about 25 moles, more preferably about 3 to about 15 moles, of ethylene oxide per mole of alkylphenol. Conventionally available nonionic surfactants of this type include Igepal ™ CO-630 sold by GAF Corporation; and Triton ™ X-45, X-114, X-100 and X-102, all sold by Rohm & Haas Company. These surfactants are commonly referred to as alkylphenol alkoxylates (eg, alkyl phenol ethoxylates). The condensation products of ethylene oxide with a hydrophobic base formed with the condensation of propylene oxide with propylene glycol are also suitable as the use for the additional nonionic surfactant in the present invention the hydroblic portion of those compounds will preferably have a molecular weight from about 1500 to about 1800 and will exhibit insolubility in water. The addition of polyoxyethylene portions for this hydrophobic portion tends to increase the water solubility of the molecules as a whole and the liquid character of the product is retained to the point where the polyoxyethylene content is about 50% of the total weight of the condensation product , which corresponds to condensation with up to about 40 moles of ethylene oxide. Examples of compounds of this type include some commercially available surfactants such as Pluronic ™ sold by BASF. Also suitable for use as the nonionic surfactant of the nonionic surfactant system of the present invention are the condensation products of ethylene oxide with the product resulting from the reaction of propylene oxide and ethylenediamine. The hydrophobic portion of these products consists of the reaction product of ethylenediamine and the excess propylene oxide and generally has a molecular weight from about 2500 to about 3000. This hydrophobic portion is condensed with ethylene oxide to the extent that the condensation product it contains from about 40% to about 80% by weight of poly-oxyethylene and has a molecular weight of from about 5,000 to about 11,000. Examples of this type of nonionic surfactant include those commercially available Tetronic ™ compounds sold by BASF. Preferred nonionics are also the amine oxide surfactants. The compositions of the present invention may comprise amine oxide according to the general formula I R1 (EO) x (PO) and (BO) zN (O) (CH2R) 2.qH2O (I) In general, it can be seen that the structure (I) provides a long chain portion (R1 (EO) x (PO) and (BO) z and two short chain portions CH2R '; R is preferably selected from hydrogen, methyl and -CH2OH. a primary or branched portion that can be saturated or unsaturated, preferably R1 is a primary alkyl moiety When x + y + z = 0, R1 is a hydrocarbyl portion having chain length from about 8 to about 18. When x + y + z is different from 0, R1 can be longer, having a chain length in the range of C12-C24 The general formula also covers amine oxides where x + y + z = 0, R, = C8-C18, R '= H and q = 0.2, preferably 2. These amine oxides are illustrated by the alkydimethylamine oxide C12-? 4, the oxide of hexa decyldimethylamine, octadecylamine oxide and its hydrates, especially dihydrates as described in U.S. Patents 5,075,501, and 5,071,594, incorporated herein by reference. The invention also encompasses amine oxides wherein x + y + z is nonzero, specifically x + y + z is from about 1 to about 10, R1 is a primary alkyl group containing from 8 to about 24 carbon atoms, preferably from about 12 to about 16 carbon atoms; in these embodiments y + z is preferably 0 and x is preferably from about 1 to about 6, more preferably from about 2 to about 4. EO represents ethyleneoxy; PO represents propyleneoxy; and BO represents butyleneoxy. Such amine oxides can be prepared by conventional synthetic methods, for example, by reaction of alkyl ethoxy sulfates with dimethylamine followed by oxidation of the ethoxylated amine with hydrogen peroxide. The highly preferred amine oxides herein are solutions at room temperature. The amine oxides suitable for use herein are made commercially by a number of suppliers including Akzo Chemie, Ethyl Corp., and Procter &; Gamble. See the McCutcheon's compilation and the Kirk-Othmer review article for manufacturers of alternative amine oxides. While in certain preferred embodiments, R 'is H, there is some parameter with respect to having R' slightly greater than H. Specifically, the invention further encompasses embodiments wherein R 'is CH2OH such as hexadecylbis (2-hydroxyethyl) amine oxide , ceboyl oxide (2-hydroxyethyl (amine, stearylbis (2-hydroxyethyl) amine oxide and oleylbis (2-hydroxyethyl) amine oxide, dodecyldimethylamine oxide dihydrate, Polymeric Stain Release Agent - The compositions according to with the present invention may optionally comprise one or more stain releasing agents.The stain releasing agents are characterized by having hydrophilic segments to hydrophilize the surface of hydrophobic fibers such as polyester and nylon and hydrophobic segments to be deposited on hydrophobic fibers and remain due until the termination of the wash cycle and therefore serve as an anchor for the hydrophilic segments. It is recommended that the stains that occur subsequent to the treatment with the stain-releasing agent be cleaned more easily in subsequent washing procedures. If used, the 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 all included herein by reference, disclose stain release polymers suitable for us in this invention. U.S. 5,691,298 Gosselink et al., Published November 25, 1997; U.S. Patent 5,599,782 Pan et al., Published February 4, 1997; U.S. Patent No. 5,415,807 Gosselink et al., Published May 16, 1995; U.S. Patent 5,182,043, Morrall et al., Published January 26, 1993; U.S. Patent 4,956,447 Gosselink et al., Published September 11, 1990; U.S. Patent 4,976,879 Maldonado et al., Published December 11, 1990; U.S. Patent 4,968,451 Scheibel et al., Published November 6, 1990; U.S. Patent No. 4,925,577 Borcher Sr. et al., Published May 15, 1990; U.S. Patent 4,861,512 Gosselink, published August 29, 1989; U.S. Patent 4,877,896 Maldonato et al., Published October 31, 1989; U.S. Patent 4,702,857 Gosselink et al., Published October 27, 1987; U.S. Patent 4,711,730 Gosselink et al., Published December 8, 1987; U.S. Patent 4,721,580 Gosselink published January 26, 1988; North American Patent 4,000,093 Nicol et al., Published December 28, 1976; U.S. Patent 3,959,230, Hayes, published May 25, 1976; US Patent 3,893,929, Basadur, published July 8, 1975; and European Patent Application 0 219 048, published on April 22, 1987 by Kud et al. Suitable additional spot release agents are described in U.S. Patent 4,201,824, Voilland et al., U.S. Patent 4,240,918 Lagasse et al .; U.S. Patent 4,525,524 Tung et al .; U.S. Patent 4,579,681 Ruppert et al; U.S. Patent 4,220,918; U.S. Patent 4,787,898; EP 279,134 A, 1988 to Rhone-Poulenc Chemic; EP 457,205 A to BASF (1991); and from 2,335,044 to Unilever N.V. 1974; all incorporated herein by reference. Clay Stain Removal / Anti Repositioning Agent - The compositions of the present invention can optionally also contain water-soluble ethoxylated amines having clay stain removal and anti-redeposition properties. Granular detergent compositions containing these compounds typically contain from about 0.01% to about 10% by weight of the water-soluble ethoxylated amines.; liquid detergent compositions typically contain about 0.01% to about 5%.

The most preferred stain release and anti-redeposition agent is ethoxylated tetraethylenepentamine. Illustrative ethoxylated amines are further described in U.S. Patent 4,597,898, VanderMeer, published July 1, 1986. Another group of preferred clay stain removal and anti-redeposition agents are the preferred cationic compounds described in the European Patent Application. 111,965, Oh and Gosselink, published June 27, 1984. Other clay stain removal / anti redeposition agents that can be used include the ethoxylated amine polymers described in European Patent Application 111,984, Gosselink, published June 27. of 1984; the zwitterionic polymers described in European Patent Application 112,592, Gosselink published on July 4, 1984, and the amine oxides described in US Pat. No. 4,548,744, Connor, published October 22, 1985. Other stain removal agents of Clay and / or anti redeposition known in the art can be used in the compositions herein. See U.S. Patent 4,891,160, VanderMeer, published January 2, 1990 and WO 95/32272, published November 30, 1995. Another type of preferred antiredeposition agent includes carboxymethylcellulose (CMC) materials. These materials are well known in the art. Polymeric Dispersing Agents - Polymeric dispersing agents can be advantageously used 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 known in the art may also be used. It is considered, although not intended to be limited by theory, that polymeric dispersing agents improve the performance of the detergent improver in general; when used in combination with other enhancers (including lower molecular weight polycarboxylates) by inhibition of crystal growth, peptization of particle stain release and anti redeposition. 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 the polymeric polycarboxylates of the present or monomeric segments that do not contain carboxylate radicals such as vinylmethylether, styrene, ethylene, etc., are suitably provided so that the segments do not constitute more than about 40% by weight. Particularly suitable polymeric polycarboxylates can be derived from acrylic acid. Such acrylic acid-based polymers which are useful herein are the water-soluble salts of the polymerized acrylic acid. The average molecular weight of such polymers in the acid form preferably ranges from about 2,000 to 10,000, more preferably from about 4,000 to 7,000, and more preferably from about 4,00 to 5,000. Water-soluble salts of such acrylic acid polymers may include, for example, the alkali metal, ammonium salts and substituted ammonium salts. Soluble polymers of this type are known materials. The use of polyacrylates of this type and detergent compositions has been described for example in Diehl, US Patent 3,308,067, published on March 7, 1967. The acrylic / maleic based copolymers can also be used as a preferred component of the dispersing agent. anti redeposition. Such materials include the water soluble salts of copolymers of acrylic acid and maleic acid. The molecular weight of such copolymers in the acid form preferably ranges from about 2, 000 to 100,000, more preferably from about 5,000 to 75,000, more preferably from about 7,000 to 65,000. The ratio of the acrylate to maleate segments in such 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 such 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 September 3, 1986, which they also describe such polymers comprising hydroxypropylacrylate. Even other useful dispersing agents include the maleic / acrylic / vinyl alcohol terpolymers. Such materials are also described in EP 193,360, including for example, the terpolymer 45/45/10 of acrylic / maleic / vinyl alcohol. Other polymeric materials that may be included is polyethylene glycol (PEG). PEG can exhibit dispersing agent performance as well as act as an anti-redeposition clay stain removal agent. The typical molecular weight varies for this purpose in the 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. Polyaspartate and polyglutamate as dispersing agents can also be used, especially in conjunction with zeolite improvers. Dispersing agents such as polyaspartate preferably have an average molecular weight of about 10,000. Brightener - Any optical brighteners or other whitening or bleaching agent known in the art, can be incorporated at levels typically from about 0.01% to about 1.2% by weight in the detergent compositions of this invention. Commercial optical brighteners that may be useful in the present invention may be classified into subgroups, which include, but are not necessarily limited to, stilbene, pyrazoline, coumarin, carboxylic acid, methyncynins, dibenzothiophene-5,5-dioxide, azole derivatives , heterocycles of 5 and 6 ring members and other miscellaneous agents. Examples of such brighteners are described in "The Production and Application of Fluorescent Brightening Agents," M. Zahrandnik, Published by John Wiley & amp;; Sons, New York (1982). Specific examples of optical brighteners that are useful in the compositions herein are those identified in U.S. Patent 4,790,856, issued to Wixon on December 13, 1988. These brighteners include the PHORWHITE series of brighteners from Verona. Other brighteners described in this reference include Tinopal UNPA, Tinopal CBS and Tinopal 5BM; available from Ciba-Geigy; Artic White CC and Artic White CWD, 2- (4-styryl-phenyl) -2H-naphtho [1, -d] triazoles; 4,4'-bis (1, 2,3-triazol-2-yl) -stilbenes; 4,4'-bis (styryl) bisphenyls; and the aminocoumarins. Specific examples of these brighteners include 4-methyl-7-diethyl-amino coumarin; 1,2-bis (benzimidazol-2-yl) ethylene; 1,3-diphenyl-pyrazolines; 2,5-bis (benzoxazol-2-yl) thiophene; 2-styrene-naphtho [1,2-d] oxazole; and 2- (stilben-4-yl) -2H-naphtho [1,2-d] triazole. See also US Patent 3,646,015, published on February 29, 1972 to Hamilton. Dye Transfer Inhibitory Agents - The compositions of the present invention can be one or more materials effective to inhibit the transfer of dyes from one fabric to another during the washing process. Generally, such dye transfer inhibiting agents include polyvinyl pyrrolidone polymers, polyamine N-oxide polymers, copolymers of N-vinylpyrrolidone and N-vinylimidazole, manganese phthalocyanine, peroxidases and mixtures thereof. If used, these agents typically comprise from about 0.01% to about 10% by weight of the composition, preferably from about 0.01% to 5% and more preferably from about 0.05% to about 2%. More specifically, the preferred polyamine N-oxide polymers for use herein contain units having the following structural formula: R-Ax-P; wherein P is a polymerizable unit to which an N-O group can be attached or the N-O group can be part of the polymerizable unit or the N-O group can be attached to both units; A is one of the following structures: -NC (O) -, -C (O) O-, -S-, -O-, -N =; x is 0 or I; and R is aliphatic, ethoxylated aliphatic, aromatic, heterocyclic or alicyclic groups or any combination thereof to which the nitrogen of the N-O group can be attached or the N-O group is part of those groups. Preferred polyamine N-oxides are those wherein R is a heterocyclic group such as pyridine, pyrrole, imidazole, pyrrolidine, piperidine and derivatives thereof. The N-O group can be represented by the following general structures: O O I (R?)? - N- (R2) y: = N- (R,)? (R3) z wherein R-i, R2, 3 are aliphatic, aromatic, heterocyclic or alicyclic groups or combinations thereof; x, y and z are 0 and 1; and the nitrogen of the N-O group can be attached or be part of any of the aforementioned groups. The amine oxide unit of the polyamine N-oxides has a pKa < 10, preferably pKa < 7, more preferably pKa < 6. Any polymer structure can be used as long as the amine oxide polymer formed is water soluble and has dye transfer inhibition properties. Examples of suitable polymeric structures are polyvinyls, polyalkylenes, polyesters, polyethers, polyamides, polmides, polyacrylates and mixtures thereof. These polymers include random or block copolymers where one type of monomer is an amine N-oxide and the other type of monomer is N-oxide. The amine N-oxide polymers typically have an amine to amine N-oxide ratio of 10: 1 to 1: 1,000,000. However, the number of amine oxide groups present in the polyamine oxide polymer can be varied by appropriate copolymerization or by an appropriate degree of N-oxidation. Polyamine oxides can be obtained in almost any degree of polymerization. Typically, the average molecular weight is within the range of 500 to 1,000,000; most preferred 1,000 to 500,000; more preferred 5,000 to 100,000. This preferred class of materials can be referred to as "PVNO". The most preferred polyamine N-oxide useful in the detergent compositions herein is the poly (4-vinylpyridine) N-oxide which as an average molecular weight of about 50,000 and a ratio of amine to amine N-oxide of approximately 1: 4. Copolymers of the polymers of N-vinylpyrrolidone and N-vinylimidazole (referred to as a class as "PVPVI") are also preferred for use herein. Preferably, the PVPVI has an average molecular weight scale from 5,000 to 1,000,000, more preferably from 5,000 to 200,000 and more preferably from 10,000 to 20,000. (The average molecular weight scale is determined by photodispersion as described in Barth, et al., Chemical Analysis, Vol. 113. "Modern Methods of Polymer Characterization," the descriptions of which are incorporated herein by reference.) PVPVI copolymers typically have a molar ratio of N-vinylimidazole to N-vinylpyrrolidone from 1: 1 to 0.2: 1, more preferably from 0.8: 1 to 0.3: 1, more preferably from 0.6: 1 to 0.4: 1. These copolymers can be linear or branched. The compositions of the present invention may also employ a polyvinylpyrrolidone ("PVP") having an average molecular weight of from about 5,000 to about 400,000, preferably from about 5,000 to about 200,000 and more preferably from about 5,000 to about 50,000. PVPs are known to people experienced in the detergent field; see for example, EP-A-262,897 and EP-A-256,696, incorporated herein by reference. Compositions containing PVP may also contain polyethylene glycol ("PEG") having an average molecular weight of from about 500 to about 100,000, preferably from about 1,000 to about 10,000. Preferably, the ratio of PEG to PVP in a bse of ppm provided in wash solutions is from about 2: 1 to about 50: 1, and more preferably from about 3: 1 to about 10: 1. The detergent compositions of the chair can optionally contain from about 0.005% to 5% by weight of certain types of hydrophilic optical brighteners that also provide a dye transfer inhibiting action. If used, the composicons herein will preferably comprise from about 0.01% to 1% by weight of such optical brighteners. The optical brighteners useful in the present invention are those having the structural formula: wherein Ri is selected from anilino, N-bis-hydroxyethyl and NH-2-hydroxyethyl, R2 is selected from N-2-bis-hydroxyethyl, N-2-hydroxyethyl-N-methylamino, morphino, chloro and amino; and M is a salt-forming cation such as sodium or potassium. When in the above formula, R ^ is anilino, R2 is N-2-bis-hydroxyethyl and M is a cation such as sodium, the brightener is 4,4'-bis [(4-anilino-6- (N- 2-bis-hydroxyethyl) -s-triazin-2-yl) amino] -2,2'-stibendisulfonic acid and disodium salt. These particular brightener species are sold commercially under the name of Tinopal-UNPA-GX by Ciba-Geigy Corporation. Tinopal-UNPA-GX is the preferred hydrophilic optical brightener useful in the detergent compositions herein. When in the above formula R ^ is anilino, R2 is N-2-hydroxyethyl-N-2-methylamino and M is a cation such as sodium, the brightener is disodium salt of 4,4'-bis [(4-anilino -6- (N-2-hydroxyethyl-N-methylamino) -s-triazin-2-yl) amino] -2,2'-stilbenedisulfonic acid. These particular brightener species are commercially distributed under the name Tinopal 5BM-GX from Ciba-Geigy Corporation. When in the above formula, R ^ is anilino, R2 is morphino and M is a cation such as sodium, the brightener is a sodium salt of 4,4'-bis [(4-anilino-6-morpholino-s- triazin-2-yl) amino] -2,2'-stilbenedisulfonic acid. These particular brightener species are sold commercially under the name Tinopal AMS-GX from Ciba-Geigy Corporation.

The specific optical brightener species selected for use in the present invention provide especially effective dye transfer inhibition performance benefits when used in combination with the selected polymeric dye transfer inhibiting agents described heretofore. The combination of such selected polymeric materials (e.g., PVNO and / or PVPVI) with such selected optical brighteners (e.g., Tinopal UNPA-GX, Tinopal 5BM-GX and / or Tinopal AMS-GX) provides better transfer inhibition. of dye in aqueous washing solutions than those of two detergent compositions when used alone. Without being bound by theory, it is considered that such brighteners work in this way because they have a high affinity for the fabrics in the wash solution and therefore they deposit relatively quickly on these fabrics. The extent to which the brighteners are deposited on the fabrics in the wash solution can be defined by a parameter called the "elimination coefficient". The elimination coefficient is in general as the ratio of a) the polishing material deposited on the cloth to b) the initial polish concentration in the wash liquor. Brighteners with relatively high elimination coefficients are most suitable for inhibiting dye transfer in the context of the present invention. Of course, it will be appreciated that other types of conventional optical brightener compounds can finally be used in the compositions herein to provide "gloss" benefits of conventional fabric instead of an actual dye transfer inhibition effect. Such use is conventional and well known for detergent formulations. Chelating Agents - The detergent compositions herein may optionally contain one or more iron and / or manganese chelating agents. Such chelating agents may be selected from the group consisting of amino carboxylates, amino phosphonates, polyfunctionally substituted aromatic chelating agents and mixtures thereof as defined herein. Without intending to link to theory, it is considered that the benefit of these materials is due in part to their exceptional ability to remove the iron and manganese ions from the washing solutions through the formation of soluble chelates. Aminocarboxylates useful as optional chelating agents include ethylenediaminetetraacetates, N-hydroxyethylethylenediaminetriates, nitri otri acetates, ethylenediamine tetrapropionates, triethylenetetraminehexacetates, diethylenetriaminpentaacetates, and salts of ethanoldiglycine, alkali metal, ammonium and ammonium substituted herein and mixtures thereof. The aminophosphonates are also suitable for use as chelating agents in the compositions of the invention when they allow low levels of total phosphorus in the detergent compositions and include ethylene diamine tetrakis (methylene phosphonates) as DEQUEST. Preferred, these amino phosphonates for not containing alkyl or alkenyl groups with more than about 6 carbon atoms. Polyfunctionally substituted aromatic chelating agents are also useful in the compositions herein. See U.S. Patent 3,812,044, published May 21, 1974, to Connor et al. Preferred compounds of this type in the acid form are dihydroxydisulfobenzenes such as 1,2-dihydroxy-3,5-disulfobenzene. A preferred biodegradable chelator for use herein is ethylene diamine disuccinate ("EDDS") especially the [S, S] isomer as described in U.S. Patent 4,704,233, November 3, 1987, to Hartman and Perkins. The compositions herein may also contain water-soluble methyl glycine diacetic acid (MGDA) salts (or acid form) as a chelator or co-builder useful with for example, insoluble builders such as zeolites, layered silicates and the like. If these chelating agents are used they will generally comprise from about 0.1% to about 15% by weight of the detergent compositions herein. More preferably, if the chelating agents are used they will comprise from about 0.1% to about 3.0% by weight of such compositions. Foam suppressants - Compounds for reducing or suppressing foaming can be incorporated into the compositions of the present invention. The suppression of foams may be of particular importance in the so-called "high concentration cleaning process" as described in U.S. 4,489,455 and 4,489,574 and in front-loading European-style washing machines. A wide variety of materials can be used as foam suppressors, and foam suppressors are well known to those skilled in the art. See for example, Kirk Othmer Encyclopedia of Chemical Technology, Third Edition, Volume 7, pages 430-447 (John Wiley &; Sons, Inc., 1979). A category of foam suppressant of particular interest covers monocarboxylic fatty acid and soluble salts thereof. See U.S. Patent 2,954,347, published September 27, 1960 for Wayne, St. John. The monocarboxylic fatty acids and salts thereof used as suds suppressors typically have hydrocarbyl chains of 10 to 24 carbon atoms, preferably 12 to 18 carbon atoms. Suitable salts include the alkali metal salts, such as sodium, potassium and lithium and ammonium and alkanolammonium salts. The detergent compositions herein may also contain non-surfactant foam suppressants. These include, for example: high molecular weight hydrocarbons such as paraffin, fatty acid esters (for example, triglycerides of fatty acid), fatty acid esters of monovalent alcohols, C18-C40 aliphatic ketones (for example, stearone), etc. Other foam inhibitors include N-alkylated amino triazines such as tri or hexa-alkylmelamines or di to tetra-alkyldiamin chlortriazines formed as cyanuric chloride products with two or three moles from a primary or secondary amine containing from 1 to 24 atoms carbon, propylene oxide and monostearyl phosphates such as monostearyl alcohol, phosphate ester and di-alkali metal of monostearyl (eg, K, Na and Li) phosphates and phosphate esters. Hydrocarbons such as paraffin and haloparaffin can be used in liquid form. The liquid hydrocarbons will be liquid at room temperature and atmospheric pressure and will have a pour point in the range of about -40 ° C to about 50 ° C and a minimum boiling point of not less than about 110 ° C (atmospheric pressure). It is also known how to use the wax hydrocarbons, preferably having a boiling point below about 100 ° C. Hydrocarbons constitute a preferred category of foam suppressant for detergent compositions. The hydrocarbon foam suppressors are described, for example, in US Pat. No. 4,265,779, published May 5, 1981 for Gandolfo et al. The hydrocarbons therefore include aliphatic, alicyclic, aromatic and saturated or unsaturated heterocyclic hydrocarbons having from about 12 to about 70 carbon atoms. The term "paraffin" as used in this discussion of foam suppressant is intended to include mixtures of true paraffins and cyclic hydrocarbons. Another preferred category of non-surfactant foam suppressors comprises silicone foam suppressors. This category includes the use of polyorganosiloxane oils, such as polydimethylsiloxane, polyorganosiloxane disions or emulsions, oils or resins, and combinations of polyorganosiloxane with silica particles, wherein the polyorganosiloxane is chemoabsorbed or fused to the silica. Silica foam suppressors are well known in the art and for example, are described in US Patent 4,256,779, published May 5, 1981, to Gandolfo et al., And European Patent Application No. 89407851, published on February 7, 1990, by Starch, MS Other foam suppressors are described in U.S. Patent 3,455,839 which relates to compositions and processes for defoaming aqueous solutions incorporated in the same small amounts of polydimethylsiloxane fluids. Silicone mixtures and silanated silicas are described, for example, in German Patent Application DOS 2,124,526. Silicone defoamers and foam control agents in granular detergent compositions are described in US Pat. Nos. 3,933,672 Bartolorta et al., And in US Patent 4,652,392, Baginski et al., Published March 24, 1987. A suppressant illustrative silicone-based foam for use herein is a foam suppressing amount of a foam control agent consisting essentially of: (i) polydimethylsiloxane fluid having a viscosity from about 20 cs to about 1,500 cs at 25 ° C C. (ii) from about 5 to about 50 per 100 parts by weight of (i) siloxane resin composed of (CH3) 3SiO1 2 of SiO2 units in relation to (CH3) 3 SiO1 2 and SiO2 units of about 0.6: 1 at about 1.2: 1; Y (iii) from about 1 to about 20 parts per 100 parts by weight of (i) of a solid silica gel. In the silicone foam suppressant used herein, the solvent for the continuous phase is made of certain polyethylene glycols or polyethylene polypropylene glycols in the form of copolymers or mixtures thereof (preferred) or polypropylene glycol. The primary silicone foam suppressor is branched / interlaced and preferably non-linear. To illustrate this point further, liquid laundry detergent compositions with suppressors with controlled foams will optionally comprise from about 0.001 to about 1, preferably from about 0.01 to about 0.7, more preferably from about 0.05 to about 0.5%, by weight of such a suppressant. silicone foams comprising (1) a non-aqueous emulsion of a primary defoaming agent which is a mixture of (a) a polyorganosiloxane, (b) a resinous siloxane or a silicon resin-producing silicone compound, (c) a material finely divided filler and (d) a catalyst to promote the removal of the components of the mixture (a), (b) and (c) to form silanolates; (2) at least one nonionic silicone surfactant; and (3) polyethylene glycol or a polyethylene-polypropylene glycol copolymer having a solubility in water at room temperature of more than about 2% by weight and without polypropylene glycol. Similar quantities can be used in granular composicons, gels, etc. See also U.S. Patents 4,978,471, Starch, published December 18, 1990, and 4,983,316, Starch, published January 8, 1991, 5,288,431, Huber et al, published February 22, 1994, and US Patents 4,639,489 and 4,749,740 , Aizawa et al in column 1, line 46 to column 4, line 35. The silicone foam suppressant preferably comprises polyethylene glycol and a polyethylene glycol / polypropylene glycol copolymer all having an average molecular weight of less than about 1,000, preferably between about 100 and 800. The polyethylene glycol and the polyethylene / polypropylene copolymers herein have a solubility in water at room temperature of more than about 2% by weight, preferably more than about 5% by weight. The preferred solvent herein is polyethylene glycol having an average molecular weight of less than about 1,000, more preferably between about 100 and 800; more preferably between 200 and 400 and a polyethylene glycol / polypropylene glycol copolymer, preferably PPG 200 / PEG 300. It is preferred that there be a weight ratio of between about 1: 1 and 1:10, more preferably between 1: 3 and 1 : 6, ethylene-polypropylene glycol polyethylene glycol copolymer.

The preferred silicone foam suppressors used herein do not contain polypropylene glycol, particularly of molecular weight 4,000. Preferably they also do not contain block copolymers of ethylene oxide and propylene oxide, such as PLURONIC L101. Other foam suppressors useful herein include secondary alcohols (e.g., 2-alkyldensands) and mixtures of such alcohols with silicone oils such as the silicones described in U.S. 4,798,679, 4,075,118 and EP 150,872. Secondary alcohols include C6-C6 alkyl alcohols having a d-C16 chain. A preferred alcohol is 2-butyl octanol, which is available from Condea under the trade name ISOFOL 12. Mixtures of the secondary alcohols are available under the tradename ISALCHEM 123 from Enichem. The mixed foam suppressors typically comprise mixtures of alcohol + silicone in a weight ratio of 1: 5 to 5: 1. For any detergent compositions that are used in automatic laundry washing machines, the foams should not be formed to the extent that they exceed the flow of the washing machine. The foam suppressors, when used, are preferably present in an amount of foam suppression. By "foam suppression amount" is meant that the composition formulator can select an amount of this foam control agent that will sufficiently control the foams to result in a low foaming laundry detergent for use in washing machines of automatic laundry. Compositions herein will generally comprise from 0% to about 10% of the foam suppressant. When used as suds suppressors, the monocarboxylic fatty acids and salts therein will typically be present in amounts of up to about 5% by weight of the detergent composition. Preferably, from about 0.5% to about 3% of the fatty monocarboxylate foam suppressant is used. Silicone foam suppressors are typically used in amounts of up to about 2.0% by weight of the detergent composition, although larger amounts can be used. This upper limit is practical in nature mainly due to the interest of keeping costs reduced to a minimum and the effectiveness of lower amounts for foaming effective control. Preferably from about 0.01% to about 1% of the silicone foam suppressant, more preferably from about 0.25% to about 0.5% is used. As used herein, these weight percent values include any silica that can be used in combination with polyorganosiloxane, as well as any adjunct materials that may be used. The monostearyl phosphate foam suppressors are generally used in amounts ranging from about 0.1% to about 2% by weight of the composition. The hydrocarbon foam suppressors are typically used in amounts ranging from 0.01% to approximately 5.0% although higher levels can be used. The alcohol foam suppressors are typically 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 the performance of additional fat removal. Such materials are described in WO 91/08281 and PCT 90/01815 on page 4 and following, incorporated herein by reference. Chemically, these materials comprise polyacrylates having one ethoxy chain side 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 with ester to the polyacrylate structure to provide a "structure" of "combined" polymer type. The molecular weight can vary, or typically ranges from about 2000 to about 50,000. Such alkoxylated polycarboxylates can comprise from about 0.05% to about 10% by weight of the compositions herein. Fabric Softeners - Various fabric softeners through washing, especially the non-detectable smectite clays of US Patent 4,062,647, Storm and Nirschl, published on December 13, 1977, as well as other softening clays known in the art can optionally be used common way at levels from about 0.5% to about 10% by weight in the current compositions to provide fabric softening benefits concurrently with washing of the same. The clay softeners can be used in combination with amine and cationic softeners as described for example in U.S. Patent 4,375,416, Crisp et al, March 1, 1983 and U.S. Patent 4,291,071, Harris et al, issued September 22. from 1981. Perfumes - Perfumes and perfumery ingredients useful in the compositions herein and processes comprising a wide variety of natural and synthetic chemical ingredients, including but not limited to aldehydes, ketones, esters and the like. Various natural extracts and essences are also included which may comprise complex mixtures of ingredients such as orange oil, lemon oil, rose extract, lavender, musk, patchuli, balsamic essence, sandalwood oil, pine oil, cedar and the like. The finished perfumes may comprise extremely complex mixtures of such ingredients. The finished perfumes typically comprise from about 0.01% to about 2% by weight of the detergent compositions herein and the individual perfumery ingredients can comprise from about 0.0001% to about 90% of a finished perfume composition. 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 nhalene; methyl ionone; ionone gamma methyl; methyl cedrylonone; methyl dihydrojasmonate; Methyl 1, 6, 10-trimethyl-2,5,9-cyclododecatrien-1-yl ketone; ketone; 7-acetyl-1,1, 3,4,4,6-hexamethyltetralin; 4-acetyl-6-tert-butyl-1,1-dimethyl indane; para-hydroxy-phenyl-butanone, benzophenone; methyl beta-naphthyl ketone; 6-acetyl-1,1,2,3,3,5-hexamethyl indan; 5-acetyl-3-isopropyl-1,1,2,6-tetramethyl indan; 1-dodecanal, 4- (4-hydroxy-4-methylphenyl) -3-cyclohexen-1-carboxaldehyde; 7-hydroxy-3,7-dimethylocaranal; 10-undecen-1 -al; iso-hexenyl ciciohexyl carboxaldehyde; tricyclohexane formyl; condensation products of hydroxy-citronellal and methyl anthranilate, condensation products of hydroxy-citronellal and indole, condensation products of phenyl-acetaldehyde and indole; 2-methyl-3- (para-tert-butylphenyl) -propionaldehyde; ethyl vanillin; heilotropin; hexyl cinnamic aldehyde; cinnamic amyl aldehyde; 2-methyl-2- (para-iso-propylphenyl) propinaldehyde; coumarin; gamma decalactone; cyclopentadecanolide, 16-hydroxy-9-hexadecenoic acid lactone; 1,3,4,6,7,8-hexahydro-4,6-6,7,8,8-hexamethylcyclopenta-gamma-2-benzopyran; beta-naphthol methyl ether; ambroxane; dodecahydro-3a, 6,6,9a-tetramethylnaphtho [2,1 bjfuran; cedrol, 5- (2,2,3-trimethyIcyclopent-3-enyl) -3-methylpentan-2-ol; 2-ethyl-4- (2,2,3-trimethyl-3-cyclopenten-1-yl) -2-buten-1 -ol; caryophyllene alcohol; tricyclodecenyl propionate; tricyclodecenyl acetate; benzyl salicylate; Cedaryl acetate; and para- (tert-butyl) cyclohexylacetate. Particularly preferred perfume materials are those that provide the great odor enhancements in the finished product compositions containing cellulases. These perfumes include but are not limited to: hexyl cinnamic aldehyde; 2-methyl-3- (para-tert-butylphenyl) propionaldehyde; 7-acetyl-1, 2,3,4,5,6,7,8-octahydro-1,1,6,7-tetramethyl naphthalene; 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, 1 bjfuran; anisaldehyde; coumarin; cedrol; vanilla; Cyclopentadecanolide; tricyclodecenyl acetate; and tricyclodecenyl propionate. Other perfume materials include essential oils, resinoids and resins from a variety of sources including, but not limited to: Peruvian balm, Olibanum resinoid, stretcha, labadanum resin, nutmeg, cassia oil, benzoin resin, corianda , and bleach. Even other perfume chemicals include phenylethyl alcohol, terpineol, linaleol, linalyl acetate, geraniol, nerol, 2- (1,1-dimethylethyl) -cyclohexanol acetate, benzyl acetate, and eugenol. Carriers such as diethyl phthalate can be used in the finished perfume compositions. Other Ingredients - A wide variety of other ingredients useful in detergent compositions can be included in the compositions herein, including other active ingredients, carriers, hydrotropes, process aids, dyes or pigments, solvents for liquid formulations, solid fillers for compositions of bar, etc. If high foaming is desired, foaming promoters, such as C10-C16 alkanolamides can be incorporated into the compositions, typically at levels of 1% -10%. The monoethanol and the C10-C14 diethanol amides illustrate a typical class of such foaming promoters. The use of such foaming promoters with adjunct high foaming surfactants such as the amine oxides, betaines and sultaines noted above is also advantageous. If desired, the water-soluble magnesium and / or calcium salts, such as MgCl 2, MgSO 4, CaCl 2, CaSO 4 and the like, can be added at levels of, typically 0.1% -2% to provide additional foaming and to improve the yield of removal of fat. Various detersive ingredients employed in the compositions herein may optionally be stabilized by absorption of such ingredients in a porous hydrophobic substrate., then coating the substrate with a hydrophobic coating or preferably the detersive ingredient is mixed with surfactant before being absorbed into the porous substrate. In use, the detersive ingredient is released from the substrate in the aqueous wash liquor, 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 solution containing 3% -5% of the nonionic ethoxylated alcohol surfactant C13-15 (EO 7). Typically, the enzyme / surfactant solution is 2.5X the weight of silica. The resulting powder is dispersed with stirring in silicone oil (various viscosities of silicone oil in the range of 500-12,500 can be used). The resulting silicone oil dispersion is emulsified or from another manure added to the final detergent matrix. Hereby, ingredients such as the aforementioned enzymes, bleaches, bleach activators, bleach catalysts, photoactivators, dyes, fluorescers, fabric conditioners and hydrolyzable surfactants can be "protected" by use in detergents, including the compositions of liquid laundry detergent. The liquid detergent compositions may contain water and other solvents as carriers. The primary or secondary low molecular weight alcohols exemplified by methanol, ethanol, propanol and isopropanol are suitable. Monohydric alcohols are preferred for solubilization of the surfactant, although polyols such as those containing from 2 to about 6 carbon atoms and from 2 to 6 hydroxy groups (for example, 1,3-propanediol, ethylene glycol, glycerin, and 1) are preferred. , 2-propanediol) can be used. The compositions may contain from 5% to 90%, typically from 10% to 50% of such carriers. The detergent actions herein will be preferably formulated so that during use in aqueous washing operations, the wash water will have a pH of between about 6.5 and about 11, preferably between about 7.5 and 10.5. The liquid fret lava product formulations preferably have a pH between about 6.8 and about 9.0. Laundry products are typically at a pH of 9-11. Techniques for controlling pH at recommended use levels include the use of pH, alkali, acid regulators, etc., and are well known to those skilled in the art. Form of the Compositions The compositions according to the invention can take a variety of physical forms including granular, tablet, bar and liquid forms. The compositions are particularly so-called concentrated granular detergent compositions adapted to be added to a washing machine by means of a dispensing device placed in the drum of the machine with the load of soiled fabric. The average particle size of the components of granular compositions according to the invention should preferably be no more than 5% of the particles that are greater than 1.7 mm in diameter and no more than 5% of the particles that are less than 0.15. mm in diameter. The term "average particle size" as defined herein is calculated by sieving a sample of the composition in a number of fractions (typically 5 fractions) in a series of Tyler sieves. The fractions by weight obtained in this way are plotted against the opening size of the sieves. The average particle size is taken to make the size of the opening through which 50% by weight of the sample could pass. The bulk density of the granular detergent compositions according to the present invention typically have a bulk density of at least 600 g / liter, more preferably from 650 g / liter to 1200 g / liter. The density in volume is measured by means of a simple funnel of a bowl device consisting of a conical funnel rigidly molded on a base and provided with a flap valve at its lower end to allow the contents of the funnel to be emptied into an axially aligned cylindrical bowl placed underneath of the funnel. The funnel is 130 mm high and has internal diameters of 130 mm and 40 mm in its respective upper and lower extremities. It is mounted so that the lower end is 140 mm above the upper surface of the base. The bowl has a general height of 90 mm, an internal height of 87 mm and an internal diameter of 84 mm. Its nominal volume is 500 mi. To carry out a measurement, the funnel is filled with dust by pouring by hand, the flap valve is opened and the powder is allowed to fill the bowl. The full bowl is removed from the structure and the excess powder removed from the bowl is by past the implement of the straight edge eg a knife through its upper edge. The filled bowl is then weighed and the value obtained by the weight of the duplicated powder to provide a volume density in grams / liter. The reproduced measurements are made if required. Agglomerate particles of surfactant system The surfactant system is preferably present in granular compositions in the form of agglomerated particles, which may take the form of flakes, minute particles, lumps, nodes, slats, although preferably they take the form of granules The most preferred way to process the particles is by agglomeration powders (eg, aluminosilicate, carbonate) with high-activity branched primary chain alkyl sulphate pastes and to control the particle size of the resulting agglomerates within the specified limits. Such a process involves mixing an effective amount of powder with a medium chain high activity branched primary alkylsulfate paste in one or more agglomerates such as a pot agglomerator, a knife mixer Z or more preferably an in-line mixer such as those manufactured by Schugi (Holland) BV, 29 Chroomstraat 8211, AS Lelystad, The Netherlands, and Gebruder Lodige Maschinebau GmbH, D-4790 Paderborn 1, Elsenerstrasse 7-9, Postfach 2050, Germany. More preferably, a high shear mixer is used such as a Lodige CB (trademark). A high activity branched primary chain alkyl sulphate paste comprising from 50 wt% to 95 wt%, preferably 70 wt% to 85 wt% of branched primary medium chain alkyl sulfate is typically used. The paste can be pumped into the agglomerator at a temperature high enough to maintain a viscosity that can be pumped, but low enough to avoid degradation of the surfactants used. A pulp operating temperature of 50 ° C to 80 ° C is typical. Laundry Washing Method The laundry machine methods herein typically comprise treating the washing of stains with an aqueous washing solution in a washing machine having dissolved or dispersed an effective amount of a machine laundry detergent composition in accordance with the invention. By an effective amount of the detergent composition is meant from 20 grams to 300 grams of dissolved or dispersed products in a volume wash solution of 5 to 65 liters, as are the typical product doses and volumes of wash solution commonly used in conventional machine washing methods. As noted, the surfactant system that is used herein in the detergent compositions, preferably in combination with other detersive surfactants, at levels that are effective to achieve at least a directional improvement in cleaning performance. In the context of such a washing composition, such "use levels" may vary depending not only on the type and severity of the stains and grime, but also on the temperature of the wash water, the volume of the wash water and the type of washing machine. As can be seen from the above, the amount of medium chain branched primary alkyl sulfate surfactant used in the washing machine washing context may vary depending on the habits and practices of the user, the type of washing machine and the like.

In a preferred use aspect, a dispensing device is employed in the washing method. The dispensing device is charged with the detergent product and is used to introduce the product directly into the drum of the washing machine before the start of the washing cycle. Its volume capacity must be such that it is capable of containing sufficient detergent product as would normally be used in the washing method. Once the washing machine has been loaded with the washing load, the spout device containing the detergent product is placed inside the drum. At the beginning of the water washing cycle of the washing machine, it is introduced into the drum and the drum rotates periodically. The design of the dispensing device must be such as to allow the containment of the dry detergent product even though it allows the release of this product during the washing cycle in response to its agitation as the drum rotates and also as a result of its contact with the washing water. To allow the release of the detergent product during washing, the device may possess a number of openings through which the product can pass. Alternatively, the device can be made of a material that is liquid permeable, but impermeable to the solid product, which allows the release of the dissolved product. Preferably, the detergent product will be released rapidly at the start of the wash cycle thereby providing high, localized transient concentrations of the product in the drum of the washing machine at this stage of the wash cycle.

The preferred dispensing devices are reusable and are designed in such a way that the integrity of the container is maintained both in the dry state and during the wash cycle. Especially preferred dispensing devices for use with the composition of the invention have been described in the following patents GB-B-2, 157,717, GB-B-2, 157,718, EP-A-0201376, EP-A-0288345 and EP -A-0288346. An article by J. Bland published in Manufacturing Chemist, November 1989, pages 41-46 also describes especially preferred dispensing devices for use with granular laundry products which are of a type commonly known as the "granule". Another preferred assortment device for use with the compositions of this invention is described in PCT Patent Application No. WO94 / 11562. Especially preferred dispensing devices are described in European Patent Application Publication Nos. 0343069 and 0343070. This application describes a device comprising a flexible sheet in the form of a bag extending from a support ring defining a hole, the orifice that is adapted to admit enough product to the bag for a washing cycle in a washing process. A portion of the washing medium flows through the orifice into the bag, dissolves the product and the solution passes out through the hole in the washing medium. The support ring is provided with a masking arrangement to prevent discharge of the undissolved dampened product, this arrangement typically comprising walls extending radially from a central mass in a spoke wheel configuration, in a similar structure in which the walls have a helical shape. Alternatively, the dispensing device may be a flexible container such as a bag or bag. The bag may be of fibrous construction coated with a waterproof protective material to retain the contents as described in European Published Patent Application No. 0018678. Alternatively, it may be formed of a water-insoluble synthetic polymeric material provided with a seal of edge or closure designed for rupture in aqueous medium as described in European Published Patent Application Nos. 0011500, 0011501, 0011502 and 0011968. A convenient form of the fragile water enclosure comprises a water soluble adhesive placed along and sealed an edge of a sack formed of a waterproof polymeric film such as polyethylene or polypropylene. Dishwashing method to machine Any suitable methods to wash machine or clean dirty dishes, particularly dirty cutlery are contemplated. A preferred machine dishwashing method comprises treating the selected soiled articles from cutlery, glasses, bowls, silver and cutlery services and mixtures thereof with an aqueous liquid having dissolved or dispersed therein an amount effective of a machine-washed dishwashing composition according to the invention. By an effective amount of the machine dishwashing composition will be understood from 8 to 60 g of products dissolved or dispersed in a volume wash solution of 3 to 10 liters as are the typical doses of product and volumes of solution of washing commonly used in conventional machine dishwashing methods. Packaging of the Compositions The commercially sold executions of the bleaching compositions can be packaged in any suitable container including those constructed of paper, cardboard, plastic materials and any suitable laminates. A preferred packaging embodiment is described in European Application No. 94921505.7. In the following examples, the abbreviations of the various ingredients used for the compositions have the following meanings. C12 linear alkyl sodium benzenesulfonate MBAS, medium chain branched primary alkyl (total carbon average = x) LMFAA sulphate C-12-14 alkyl N-methylglucamide Cp-C10 amidopyridylamine amido Fatty acid C12- fatty acid C14 (C12 / 14) Fatty acid Blocked Palm Seed Fatty Acid (TPK) Fatty Acid (RPS) Flaxseed Fatty Acid Borax Sodium Tetraborate Decahydrate PAA Polyacrylic Acid (pm = 4500) PEG Polyethylene Glycol (pm = 4600) MES SAS alkyl ester sulfonate Alkyl sulfate secondary NaPS Parafin sodium sulfonate C45AS C1-C15 linear sodium alkylsulfate CxyEzS C1x-C1y sodium and sulfur-containing alkylsulphate with z moles of ethylene oxide CyxEz C 1 x 1 branched primary alcohol and condensed with z-oxide averages ethylene QAS Ethoquad C / 12 or R2 N + (CH3) 2 (C2H4OH) with R2 = C12-C? 4 TFAA alkyl N-methyl glucamide C16-C18 STPP Sodium tripolyphosphate anhydrous Zeolite A Aluminiosilicate sodium hydrate of the formula Na12 (A102SiO2) 12.27H2O having a primary particle size in the range of 0.1 to 10 mis NaSKS-6 Silicate in crystalline layers of the formula d-Na2S¡O5 Carbonate Anhydrous sodium carbonate with a particle size between 200 μm and 900 μm.

Bicarbonate Anhydrous sodium bicarbonate with a particle size distribution between 400 μm and 1200 μm Silicato amorphous sodium silicate (SiO2: Na2.2.0 ratio) Sodium sulphate anhydrous sodium sulfate MA / AA 1: 4 maleic / acrylic acid copolymer , average molecular weight of approximately 70,000. CMC Sodium Carboxymethylcellulose Protease Protein activity enzyme 4KNPU / g sold by NOVO Industries A / S under the trade name Savinase Cellulase Activity cellulite enzyme 1000 CEVU / g sold by NOVO Industries A / S under the trademark Carezyma Amylase Activity amylolytic enzyme 60KNU / g sold by NOVO Industries A / S under the trademark Termamyl 60T. Lipase Enzyme I activity policy 100kLU / g sold by NOVO Industries A / S under the trade name Lipolase PB4 Sodium perborate tetrahydrate of nominal formula NaBO2.3H2O.H2O2. PBI Anhydrous sodium perborate whitener of nominal formula NaBO2.H2O2. Percarbonate Sodium percarbonate of the nominal formula NaDCC sodium dichloroisocyanurate NOBS Nonaxoyloxybenzene sulfonate in the sodium salt form. TAED Tet raacetyldi ethylenediamine DTPMP Diethylenetriamine penta (methylene phosphonate). sold by Montanto under the trade name Dequest 2060 Photoactivated Sulfonated Zinc Ftolicianin encapsulated in soluble polymer of dextrin bleach Brightener 1 4,4'-b¡s (2-sulphotyryl) biphenyl disodium Brightener 24,4'-b¡s (4-anilino-6-morpholino-1, 3,5-triazin-2-yl) amino) stilben -2,2'-disul fonato.

HEDP 1, 1-hydroxyethane diphosphoric acid SRP1 Esters blocked at the end with sulfobenzoyl with oxyethylene oxy and terephthaloyl structures. Silicone antifoam Polydimethylsiloxane foam controller with siloxane-oxyalkylene copolymer as a dispersing agent with a ratio of such a foam controller to such a dispersing agent of 10: 1 to 100: 1. DTPA Diethylenetriamine pentaacetic acid.

In the following examples all the levels are classified as% 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 ratios used are expressed as percentages by weight unless otherwise specified. Example 1 The following laundry detergent compositions A to D were 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 Laundry detergent compositions O to Q are prepared according to the invention: Example 5 Branched sulfated surfactants of sodium salts are made by the reaction of the appropriate branched alcohols with chlorosulfonic acid in ethyl ether. The resulting acid is neutralized with a stoichiometric amount of sodium methoxide in methanol and the solvents are evaporated by vacuum oven. Branched alcohols are made from linear olefins (alpha and / or internal olefins), which have been molecularly re-arranged by exposure to the appropriate catalysts. None of the additional carbons are added in this re-arrangement, but the initial olefin is shaken so that it now contains one or more branched alkyls along the main alkyl chain. As the olefin moiety remains intact through this molecular re-arrangement, a CH2OH group is then added by hydroformylation chemistry. The following Shell Research test alcohol samples are sulfated. 13C-NMR Resultants for Prepared Branched Alcohols i Total Number of Carbones 16 17 18 Average Number of Lots 2.0 1.7 1 I Solutions of laundry prototype formulas are prepared as shown in the following. ? \ Example 6 The following high density detergent formulations, according to the present invention, are prepared: EXAMPLE 7 The following liquid laundry detergent compositions AA to CC are prepared according to the invention: Example 8 The following liquid laundry detergent compositions DD to FF are prepared according to the invention:

Claims (9)

1. Cleaning compositions comprising surfactant systems comprising: (a) from 80% to 99% by weiof a blend of anionic surfactant coagent of branched medium chain alkyl sulphates and linear alkylbenzene sulphonates, wherein said mixture comprises: (i) from 35% to 80%, by weiof this mixture of anionic surfactant coagent of branched medium chain alkyl sulfates having the formula: R Rl R2! ? ? ? i CH3CH2 (CH2) wCH (CH2)? CH (CH2) and CH (CH2) zOS? 3M wherein the total number of carbon atoms in the branched primary alkyl portion of this formula, including the branching R, R1 and R2, is from 14 to 20, and wherein in addition to this surfactant mixture the average total number of carbon atoms in the branched primary alkyl portions having the above formula is within the range of more than 14.5 to 18, preferably from 15 to 17; R, R1 and R2 are each independently selected from hydrogen and alkyl CT-C3, preferably methyl, provided that R, R1 and R2 are not all hydrogen and, when z is 1, at least R or R1 is not hydrogen; M is one or more cations; 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 (ii) from 20% to 65% by weiof this mixture of anionic surfactant coagent, linear C 0-C 16 alkylbenzenesulfonate; and b) from 1% to 20%, by weiof one or more cationic surfactant coagents.

2. A composition according to claim 1, characterized in that at least 0.001% by weiof the mixture comprises one or more medium chain branched alkyl sulfates having the formula: Rl CH3CH2 (CH2) xCH (CH2) and CH (CH2) zOS? 3M wherein the total number of carbon atoms, including the branching, is from 15 to 18, and wherein also for this surfactant mixture the average total number of carbon atoms in the branched primary alkyl portions having the above formula is within the scale of more than 14.5 to 18; R, R1 and R2 are each independently hydrogen or C ^ -C3 alkyl, M is a soluble cation; 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 provided that R1 and R2 are not both hydrogen.

3. Cleaning compositions comprising: (1) from 0.1% to 99.9% by weiof a surfactant system, wherein said surfactant system comprises: (a) from 80% to 99% by weiof a mixture of anionic surfactant coagent of branched medium chain alkyl sulfates and linear alkylbenzene sulphonates, wherein said mixture comprises: (i) from 35% to 80% by weiof this mixture of anionic surfactant coagent, of branched medium chain alkyl sulphates having the formula : I R Rl R2 I I I CH3CH2 (CH2) wCH (CH2)? CH (CH2) and CH (CH,) zOS? 3M wherein the total number of carbon atoms per molecule, including the branch is from 14 to 20, and wherein in addition to this mixture of surfactant the average total number of carbon atoms in the primary branched alkyl portions having the above formula is within the range of more than 14.5 to 18, R, R and R2 are each independently selected from hydrogen and C1-C3 alkyl, provided 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; z is an integer of at least 1; and w + x + y + z is from 8 to 14; provided that when R2 is an alkyl of CT-CS the ratio of surfactants having z equal to 1 to surfactants having z of 2 or more is at least 1: 1, preferably at least 1 : 10, and more preferably at least 1: 100; and (ii) from 20% to 65% by weight of this mixture of anionic surfactant coagent, linear C10-C16 alkylbenzenesulfonate; and (2) from 0.1% to 99.9% by weight of one or more adjunct ingredients of the cleaning composition.

4. A cleaning composition according to claim 3, characterized in that the amount of branched surfactants, when R2 is an alkyl of d-Cs, comprises less than 20% of branched primary alkyl sulphates having the above formula wherein z is equal to 1.

5. A cleaning composition according to any of claims 1 to 3, comprising a mixture of medium chain branched primary alkyl sulfate surfactants wherein said mixture comprises at least 5% by weight of two or more branched medium chain alkyl sulfates having the formula: CH3 CH3 (CH ^ CH (CH ^ CH, OSOjM CH3 CH3 i J CH3 (CH ^ CH (CH2) e CH CH2 OSQ, M or mixtures thereof, wherein 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 from 2 to 9 and b is an integer from 1 up 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 for this surfactant mixture the average total number of carbon atoms in the primary branched alkyl portions having the above formula is within the range of more than 14.5 to 18.

6. A cleaning composition in accordance with a any of claims 1 to 5, characterized in that the branched primary chain alkyl sulfate comprises one or more branched mono-methyl alkyl sulfates selected from the group comprising: 3-methyl pentadecanolsulfate, 4-methyl pentadecanolsulfate, 5-methyl pentadecanolsulfate , 6-methyl pentadecanolsulfate, 7-methyl pentadecanolsulfate, 8-methyl pentadecanolsulfate, 9-methyl pentadecanolsulfate, 10-methyl pentadecanolsulfate, 11-methyl pentadecanolsulfate, 12-methyl pentadecanolsulfate, 13-methyl pentadecanolsulfate, 3-methyl hexadecanolsulfate, 4-methyl hexadecanolsulfate , 5-methyl hexadecanolsulfate, 6-methyl hexadecanolsulfate, 7-methyl hexadecanolsulfate, 8-methyl hexade canolsulfate, 9-methyl hexadecanolsulfate, 10-methyl hexadecanolsulfate, 11-methyl hexadecanolsulfate, 12-methyl hexadecanolsulfate, 13-methyl hexadecanolsulfate, 14-methyl hexadecanolsulfate and mixtures thereof. A cleaning composition according to any one of claims 1 to 5, characterized in that the medium chain branched primary alkyl sulfate comprises one or more di-methyl branched primary alkyl sulphates selected from the group comprising: 2,3- methyl-tetradecanolsulfate, 2,4-methyl-tetradecanolsulfate, 2,5-methyl-tetradecanolsulfate, 2,6-methyl-tetradecanolsulfate, 2,7-methyl-tetradecanolsulfate, 2,8-methyl tetradecanolsulfate, 2,9-methyltetradecanolsulfate , 2,10-methyl tetradecanolsulfate, 2,11-methyl-tetradecanolsulfate, 2,12-methyl tetradecanolsulfate, 2,3-methyl-pentadecanolsulfate, 2,4-methyl pentadecanolsulfate, 2,5-methyl-pentadecanolsulfate, 2,6- methyl pentadecanolsulfate, 2,7-methyl-pentadecanolsulfate, 2,8-methyl pentadecanolsulfate, 2,9-methyl-pentadecanolsulfate, 2,10-methyl pentadecanolsulfate, 2,11-methyl-pentadecanolsulfate, 2,12-methyl pentadecanolsulfate, 2, 13-metii-pentadecanolsulfate, and mixtures thereof. 8. A cleaning composition according to any one of claims 1 to 5, characterized in that M is selected from the group consisting of sodium, potassium, calcium, magnesium, quaternary alkylamines having the formula: wherein R3, R4, R5 and R6 are independently selected from hydrogen, Ci-Cß alkylene, C4-C6 branched alkylene, C?-C6 alkenylene alkanoy, C4-C6 alkenylene and mixtures thereof. 9. A method for cleaning fabrics, the method comprising contacting a fabric in need of cleaning with an aqueous solution of a cleaning composition according to any of claims 1-8.